| United States Patent Application |
20170341942
|
| Kind Code
|
A1
|
|
HARPER, JR.; Charles L.
|
November 30, 2017
|
METHODS AND SYSTEMS FOR LARGE SCALE CARBON DIOXIDE UTILIZATION FROM LAKE
KIVU VIA A CO2 INDUSTRIAL UTILIZATION HUB INTEGRATED WITH ELECTRIC POWER
PRODUCTION AND OPTIONAL CRYO-ENERGY STORAGE
Abstract
Lake Kivu contains .about.50 million tonnes (MT) dissolved biomethane.
Efficient use is problematic from massive associated CO.sub.2: .about.600
MT. Conventional extraction scrubs CO.sub.2 with .about.50% overall
CH.sub.4 loss, and returns .about.80% CO.sub.2 into the deep lake,
preserving a catastrophe hazard threatening >2 M people. Methods and
systems are disclosed coupling: (1) efficient CH.sub.4+CO.sub.2
degassing; (2) optional oxyfuel power generation and CO.sub.2 power cycle
technologies; and (3) CO.sub.2 capture, processing, storage and use in a
utilization hub. The invention optimally allows power production with
>2.times. improved efficiency plus cryo-energy storage and large-scale
greentech industrialization. CO.sub.2-utilizing products can include:
Mg-cements/building materials, algal products/biofuels, urea, bioplastics
and recycled materials, plus CO.sub.2 for greenhouse agriculture,
CO.sub.2-EOR/CCS, off-grid cooling, fumigants, solvents, carbonation,
packaging, ores-, biomass-, and agro-processing, cold pasteurization,
frack and geothermal fluids, and inputs to produce methanol, DME, CO,
syngas, formic acid, bicarbonate and other greentech chemicals, fuels,
fertilizers and carbon products.
| Inventors: |
HARPER, JR.; Charles L.; (Villanova, PA)
|
| Applicant: | | Name | City | State | Country | Type | Harper Biotech LLC d/b/a Simbuka Energy, LLC | Villanova | PA | US | | |
| Family ID:
|
60421375
|
| Appl. No.:
|
15/603670
|
| Filed:
|
May 24, 2017 |
Related U.S. Patent Documents
| | | | |
|
| Application Number | Filing Date | Patent Number | |
|---|
| | 62340818 | May 24, 2016 | | |
|
|
| Current U.S. Class: |
1/1 |
| Current CPC Class: |
C02F 2303/10 20130101; F25J 2260/30 20130101; C02F 2301/046 20130101; C12M 43/06 20130101; F25J 3/04533 20130101; Y02W 10/33 20150501; F25J 3/0209 20130101; F25J 2260/44 20130101; Y02P 20/151 20151101; Y02W 10/30 20150501; C01B 32/50 20170801; C02F 2103/007 20130101; C12M 43/08 20130101; F25J 2215/04 20130101; Y02E 50/343 20130101; F25J 3/0233 20130101; C02F 9/00 20130101; Y02P 20/152 20151101; C02F 1/20 20130101; C02F 2101/10 20130101; F01K 7/16 20130101; C02F 1/66 20130101; C02F 3/322 20130101; C02F 2101/32 20130101; F25J 2205/20 20130101; F25J 2210/66 20130101; Y02W 10/37 20150501; F01K 25/103 20130101; F25J 2260/80 20130101; Y02C 20/40 20200801; C02F 1/008 20130101; Y02E 50/30 20130101; F25J 3/04563 20130101; C05D 7/00 20130101; F25J 3/0266 20130101; C12M 21/04 20130101; Y02C 10/12 20130101 |
| International Class: |
C01B 32/50 20060101 C01B032/50; C02F 9/00 20060101 C02F009/00; C05D 7/00 20060101 C05D007/00; C12M 1/00 20060101 C12M001/00; F01D 15/10 20060101 F01D015/10; F01K 7/16 20060101 F01K007/16; F01K 25/10 20060101 F01K025/10; F25J 1/00 20060101 F25J001/00; H05K 7/20 20060101 H05K007/20 |
Claims
1. A method for obtaining and utilizing carbon dioxide gas from a body of
water containing dissolved carbon dioxide gas and methane gas, said
method comprising the steps of: (a) extracting water from at least one
extraction depth of the body of water to obtain extracted water; (b)
degassing the extracted water in at least one stage of degassing so as to
provide degassed water and extracted gases comprising carbon dioxide gas
and methane gas in at least one flow; (c) optionally combusting the
extracted gases with oxygen to provide an exhaust gas comprising carbon
dioxide and water; and (d) feeding to a utilization hub the carbon
dioxide gas from at least one of step (b) and step (c), wherein the
utilization hub is configured to collect the carbon dioxide gas for
storage, distribution, processing and/or utilization.
2. The method of claim 1, further comprising utilizing the carbon dioxide
collected by the utilization hub to perform at least one process selected
from the group consisting of fertilizing growth of plants, fertilizing a
biozone of Lake Kivu, lowering a pH of water returned into Lake Kivu,
adjusting a pH of water exiting from a vacuum degassing system, adjusting
a pH of water fed to an algal growth sector, cultivating algae, supplying
a cryogenic energy storage reservoir, heating or cooling a supercritical
CO.sub.2 power cycle heat engine power generator, delivering pressurized
carbon dioxide by pipeline, delivering pressurized carbon dioxide by
tanks including by pressurized tank trucks, producing dry ice, storing,
producing and distributing refrigerated liquefied and/or solidified
carbon dioxide, producing a magnesium-based cement or concrete, producing
urea, producing formic acid, producing oxalic acid, producing acetic
acid, producing a solvent, producing carbon monoxide, producing a
pyrethrum pesticide, producing an asphyxiant, producing a food packaging
gas, pasteurizing milk, beer or an agricultural juice, processing an
agricultural, food, forest, textile, waste or biofuel product, cleaning a
textile, treating leather, extracting geothermal energy, producing a
fuel, producing a syngas, producing a chemical via a formate and/or by an
oxalic acid platform, producing a chemical by gas fermentation based on a
microbial Wood Ljundahl pathway, producing a chemical by a synthetic
pathway including carbon dioxide as a reactant, producing a plastic
including carbon dioxide as an ingredient, producing carbonic acid,
producing a carbonated and/or CO.sub.2 pressurized beverage, producing
sodium bicarbonate, producing a fracking fluid, producing silicic acid,
producing microsilica, producing iron, producing nickel, processing an
ore to produce a plant and/or aquatic fertilizer, processing an ore by
solution extraction of one or more metals using supercritical carbon
dioxide optionally injected into an ore zone, producing an elemental
carbon product, producing oxygen gas, and injecting carbon dioxide via
drillholes into subterranean strata for geostorage.
3. The method of claim 1, wherein step (c) is conducted and the carbon
dioxide collected in step (d) is solely from the exhaust gas provided in
step (c).
4. The method of claim 1, further comprising generation of electrical
power.
5. The method of claim 1, wherein deep gas trapping layers of the body of
water possess in their volume average a CO.sub.2/CH.sub.4 ratio greater
than 4, and more than 98 wt. % of the CH.sub.4 dissolved in the water is
extracted by the extracting step.
6. The method of claim 5, wherein the body of water is Lake Kivu and the
method reduces a risk of a limnic eruption.
7. The method of claim 1, further comprising extracting from the
extracted water at least one product selected from the group consisting
of ammonium, ammonia, phosphorous, magnesium and calcium.
8. The method of claim 4, further comprising: supplying the electrical
power to a compression and refrigeration system; cooling with the
compression and refrigeration system at least one gas to form at least
one liquefied gas, wherein the at least one gas is at least one of
oxygen, nitrogen, carbon dioxide that has been extracted from the
extracted water, carbon dioxide that has been formed in a combustion of
associated methane and methane that has been degassed from the extracted
water; storing the at least one liquefied gas in at least one insulated
storage tank; releasing from the at least one insulated storage tank a
liquid flow of the at least one liquefied gas; optionally increasing a
pressure of the liquid flow of the at least one liquefied gas; heating
the liquid flow to form a subcritical gas flow or a supercritical fluid
flow, wherein at least a portion of the heating is optionally conducted
by heat exchange with a closed system heat engine; driving a turbine with
a subcritical gas flow or with a supercritical fluid flow to generate
electricity; and optionally driving a turbine within a closed system heat
engine to generate electricity.
9. The method of claim 1, wherein the degassed water provided in step (b)
is transported for water treatment, and the method further comprises the
steps of: (i) photosynthetic treatment of the degassed water by growth of
an algal biomass to convert bicarbonate anions to carbon fixed by
photosynthesis into biomass and hydroxyl anions in the degassed water,
such that the pH of the degassed water is increased and bicarbonate
anions are converted into carbonate anions and magnesium and calcium
precipitate out of the degassed water onto algal cells to provide
de-densified water and flocculated biomass precipitate; (ii) separating
the de-densified water from the flocculated biomass precipitate; (iii)
optionally additionally treating the degassed water by electrochemical
methods such that the pH of the degassed water is further increased and
additional magnesium and calcium precipitate out of the degassed water to
provide further de-densified water and magnesium and calcium precipitate;
(iv) optionally separating the further de-densified water from magnesium
and calcium precipitate; (v) optionally adjusting the pH of the
de-densified water or further de-densified water by adding thereto a
volume of the carbon dioxide gas collected by the utilization hub from at
least one of step (b) and step (c); and (iv) reinjecting into Lake Kivu a
return flow of the de-densified water or further de-densified water
separated from the biomass and precipitate, wherein the return flow is
reinjected into Lake Kivu at a reinjection depth which is shallower than
the extraction depth and which is density matched with the de-densified
water or further de-densified water.
10. The method of claim 1, wherein the utilization hub supplies a stream
of carbon dioxide into the biozone of Lake Kivu as a carbon fertilizing
source supporting photoautotrophic bioproductivity.
11. The method of claim 1, wherein the utilization hub supplies a stream
of carbon dioxide which is injected into: (i) post-degassing return flow
water containing nutrients that are being diffused into a biozone of Lake
Kivu; (ii) de-densified high-pH post-degassing return flow water that is
being injected into Lake Kivu underneath the biozone; and/or (iii)
post-degassing return flow water for pH control.
12. The method of claim 1, wherein the utilization hub supplies a stream
of carbon dioxide to a horticultural greenhouse.
13. The method of claim 1, wherein the utilization hub supplies a stream
of carbon dioxide which is injected into algal growth biocultures.
14. The method of claim 1, wherein the utilization hub supplies a stream
of carbon dioxide to a compressor to provide compressed carbon dioxide,
the compressed carbon dioxide is optionally stored in a storage tank, and
the compressed carbon dioxide is distributed through pipelines.
15. The method of claim 1, wherein the utilization hub supplies a stream
of carbon dioxide gas to a compression and refrigeration system to
provide compressed refrigerated liquid carbon dioxide and/or solid carbon
dioxide, and wherein the method optionally comprises at least one of the
additional steps of: (i) storing the compressed refrigerated liquid
and/or solid carbon dioxide; (ii) further cooling the compressed
refrigerated liquid carbon dioxide to provide dry ice; (iii) storing the
dry ice; (iv) using the stored dry ice as cryogenic energy with recovery
to generate power; and (v) distributing the dry ice.
16. A system configured to perform the method of claim 1.
17. The system of claim 16, which comprises: a water degassing system;
and a carbon dioxide utilization hub in fluid communication with the
water degassing system.
18. The system of claim 17, wherein the water degassing system comprises:
an intake pipe system; at least one bubble capture unit positioned
upwards along a system of degassing pipes; at least one degassing
catalyst unit positioned further upwards along the system of degassing
pipes; a bubbly flow turbine configured to capture and recycle power from
jetting foam flow at a top of the system of degassing pipes, wherein the
bubbly flow turbine is also configured to function as a foam separator;
at least one vacuum degassing unit positioned at the top of the system of
degassing pipes; and a water flow turbine capturing and recycling power
in a downward outflow of degassed water from the vacuum degassing unit.
19. The system of claim 16, which comprises: a water degassing system; an
oxyfuel power generation system in fluid communication with the water
degassing system; and a carbon dioxide utilization hub in fluid
communication with the oxyfuel power generation system.
20. The system of claim 19, wherein the oxyfuel power generation system
comprises a power generator and an air separation unit configured to
provide oxygen for combustion.
21. The system of claim 20, wherein the water degassing system comprises:
an intake pipe system; at least one bubble capture unit positioned
upwards along a system of degassing pipes; at least one degassing
catalyst unit positioned further upwards along the system of degassing
pipes; a bubbly flow turbine configured to capture and recycle power from
jetting foam flow at a top of the system of degassing pipes, wherein the
bubbly flow turbine is also configured to function as a foam separator;
at least one vacuum degassing unit positioned at the top of the system of
degassing pipes; and a water flow turbine capturing and recycling power
in a downward outflow of degassed water from the vacuum degassing unit.
22. The system of claim 21, further comprising a return flow system which
comprises: an outflow pipe from the water degassing system; pipe systems
connecting flow to at least one water treatment system; a return flow
pipe system and horizontal diffuser to reinject degassed water into the
body of water at a specified depth; and flow control valve systems with
emergency shut-off capabilities.
23. The system of claim 22, which further comprises: flow connection by
pipes and channels to and from at least one surface water treatment
system that decreases water density in the degassed water flow; and an
inlet system configured to allow admixture of relatively low density
near-surface water from the body of water into the return flow for
reinjection at a specified depth.
24. The system of claim 23, which further comprises a system configured
for combustion preparation processing and transfer of degassed gas into
the oxyfuel power generation system.
25. The system of claim 24, which further comprises a control system
configured for physical monitoring, system-wide functional integration
and emergency response safety assurance.
26. The system of claim 25, which is configured to extract more than 98
wt. % of CH.sub.4 dissolved in a body of water having a CO.sub.2/CH.sub.4
ratio greater than 4.
27. A carbon dioxide utilization hub comprising: (a) pipes and control
valves configured for transferring exhaust gases; (b) pumps configured
for compressing and transferring the exhaust gases into at least one of a
storage tank, a gas processing tank and a heat exchange system; (c) at
least two of a storage tank for pressurized gas, a gas dehydration system
and a heat exchange system; (d) at least one compressor for compressing
dehydrated carbon dioxide; (e) at least one storage tank for storing
compressed dehydrated carbon dioxide; (f) at least one dispensing valve
for dispensing compressed dehydrated carbon dioxide from at least one
storage tank storing compressed dehydrated carbon dioxide; (g) at least
one refrigeration system for compressing and refrigerating dehydrated
carbon dioxide gas into liquefied refrigerated carbon dioxide; (h) at
least one of: (i) at least one insulated tank for storing dehydrated
liquefied refrigerated carbon dioxide, (ii) at least one insulated tank
for storing liquefied refrigerated nitrogen, (iii) at least one insulated
tank for storing liquefied refrigerated oxygen, and (iv) at least one
dispensing valve for dispensing at least one cryogenic refrigerated
liquids selected from the group consisting of carbon dioxide, nitrogen
and oxygen; (i) power generation cryoenergy recovery systems utilizing at
least one of the following cryoenergy storing inputs: (i) liquefied
refrigerated carbon dioxide, (ii) liquified refrigerated nitrogen and
(iii) liquefied refrigerated oxygen; (j) gas dispensing valves and pipes
for transferring and dispensing at least one warmed gas emerging from
cryoenergy recovery systems; and (k) at least one pressurizable reaction
chamber configured to provide a mixture of carbon dioxide and water vapor
under controlled and time-varying conditions of pressure, mixing ratio,
temperature and time and admitting product producing forms containing at
least one of the following carbon dioxide and water vapor absorbing
substances: magnesium hydroxide, calcium carbonate, hydrated magnesium
carbonates, concrete-forming aggregate, pozzolans, steel rebar,
microsilica and plant materials.
28. The method of claim 1, wherein the utilization hub supplies at least
one of liquefied natural gas, compressed natural gas and adsorbed natural
gas.
29. The method of claim 4, further comprising supplying the electrical
power to a compression and refrigeration system; cooling with the
compression and refrigeration system at least one gas to form at least
one liquefied gas, wherein the at least one gas is at least one of
oxygen, nitrogen, carbon dioxide that has been extracted from the
extracted water, carbon dioxide that has been formed in a combustion of
associated methane and methane that has been degassed from the extracted
water; and cooling a server with the at least one liquefied gas.
30. A process for generating data, said process comprising: providing a
server; cooling the server with at least one liquefied gas; and
generating the data from the server, wherein the at least one liquefied
gas comprises at least one of oxygen, nitrogen, carbon dioxide and
methane from Lake Kivu water.
Description
BACKGROUND OF THE INVENTION
1. Field of Invention
[0001] The invention relates to methods, systems and apparatus for safe,
efficient, environmentally responsible extraction and utilization of Lake
Kivu deepwater resources, particularly deployed for power generation from
biogas directly combined with "green" industrial utilization of massive
associated CO.sub.2 to secure local safety, generate employment,
accelerate regional economic growth, build a global R&D network hub for
Rwanda, and create a globally significant demonstration of the business
viability of very large scale CO.sub.2 "Carbon Capture and Utilization"
(CCU).
2. Description of Related Art
[0002] A major challenge of the contemporary age is to halt the continuing
increase in the CO.sub.2 concentration of the Earth's atmosphere.
Important related agendas are to develop new large-scale ways to utilize
CO.sub.2 commercially with economic viability. For example, it is
desirable to recycle CO.sub.2 rather than to continue to utilize drilled
flows of subterranean CO.sub.2 for use in Enhanced Oil Recovery (EOR)
operations. These flows amount to roughly 60 millions of tonnes CO.sub.2
per year in the US (Wallace and Kuuskraa, 2014). Mostly they are obtained
from drilling wells that tap high-purity CO.sub.2 reserves present in
large trapped geo-pressurized accumulations analogous to those of natural
gas (methane, NG, CH.sub.4).
[0003] The huge amount of dissolved CO.sub.2 (.about.600 million tonnes)
trapped at depth in Lake Kivu stands in a different category. It presents
a mortal threat in the region as well as to the ecosystem of Lake Kivu.
It is only temporarily trapped in the deep lake. It will be released to
the atmosphere by a catastrophic natural process of runaway convective
release within a century or two unless preventative action is taken to
degas a substantial fraction of the reserve.
[0004] Two options have been considered and debated between scientific
experts, engineers and governmental leaders engaged in planning for
large-scale utilization of Lake Kivu's deepwater biomethane resource.
Like the CO.sub.2, this resource is present as dissolved gas. It amounts
to .about.50 million tonnes of CH.sub.4. The two options are: (i) an
environmentally unattractive option to degas Lake Kivu's CO.sub.2 and, in
parallel with utilization of its biomethane, to vent the degassed
CO.sub.2 to the atmosphere, or (ii) return extracted CO.sub.2 to the
depths of the lake employing a simple process broadly within the design
space of the type of extraction system first developed by Belgian
engineers in the 1950s (for the first methane fueled powerplant developed
on Lake Kivu in .about.1960). The second option extends the risk faced by
the local population of a possible mass catastrophe. In its maximal
extent, such a catastrophe has the potential to asphyxiate more than two
million people. Therefore, neither choice is attractive.
[0005] Related art is described in three categories. The first is directly
related art. This comprises two pending patent applications by the
inventor focused on solving specific problems of Lake Kivu deepwater
resources utilization. US 2015/0354451 A1 relates to a method for safe,
efficient, economically productive, environmentally responsible,
extraction and utilization of dissolved gases in deep waters of a lake
susceptible to limnic eruptions in which methane is accompanied by
abundant carbon dioxide. This method applies a technology known as
oxyfuel combustion in combination with an innovative modality of
degassing of Lake Kivu deepwater gas. Oxyfuel combustion has been
developed as a way to develop drilled acid- and sour-gas reserves,
yielding power and a stream of exhaust comprised of water vapor plus
nominally pure CO.sub.2. The inventor's disclosure in US 2015/0354451 A1
shows how Lake Kivu deepwater gas can be developed by an innovative
modified method that obtains gas dissolved in deepwater by extraction
within an upward flow of water, degasses it, and then produces three
outputs. These are: (i) power; (ii) an exhaust of water vapor plus
nominally pure CO.sub.2; and (iii) a stream of degassed nutrient-rich
deepwater utilizable in various valuable ways. U.S. Patent Application
Publication No. 20160257577 A1 relates to a method for treating
nutrient-rich dense deepwater from Lake Kivu. Also of broadly-related
interest is the patent of Evgeny Yantovsky, 2002. U.S. Pat. No.
6,477,841, "Closed Cycle Power Plant" which concerns the connection of a
lake to a zero emissions power plant (Yantovsky and McGovern, 2006;
Yantovsky, 2008, 2009; Yantovsky et al., 2009, chapter 8).
[0006] The second category of related art is industrial CO.sub.2
production from drilled sources. Lake Kivu is not a drilled source. The
extraction of CO.sub.2 from Lake Kivu deepwater is based on pipe
extraction within an open body of water. CO.sub.2 flows upwards in pipes
or risers in a dissolved state in water. A brief description is provided
in following describing the development of industrial CO.sub.2 capture
from drilled artesian well sources in the late 19.sup.th century. These
sources combine drilling-based access to the resource with CO.sub.2
flowing upwards in water in a dissolved state. Brief mention also is made
of the development of very large CO.sub.2 drilled gas well reservoirs
exploited mostly in the Western USA. These are gas wells. Carbon dioxide
rises upwards in the wells without being dissolved in water. Such
discussions provide pertinent background covering the extraction of
CO.sub.2 by methods and systems using drilling to access the resource.
[0007] The third category is contextually related art. This type of
related art covers a wide range of aspects of CO.sub.2 utilization for
industrial purposes such as variously are, or may be, contained within
embodiments of the invention, involving carbon dioxide utilization.
Related art involving CO.sub.2 utilization is presented at extended
length herein. Doing so is appropriate for describing related art in
order to promote clear understanding of three aspects of pertinent
knowledge. These are: (i) the nested set of quite different problems the
invention has been created to solve; (ii) the nature of a core aspect of
the invention which is open to, and seeks, incorporation of many highly
diverse technologies for CO.sub.2 utilization, and related "greentech"
industrial production activities; and (iii) a wide and diverse background
to the inventive art involved, knowledge of which provides a teaching to
facilitate practice of the invention.
[0008] Carbon dioxide has never been sourced for industrial utilization
from a dissolved source present in a lake. Lake sources of concentrated
dissolved CO.sub.2 that potentially are utilizable as CO.sub.2 sources in
large flows (greater than 100,000 tonnes per year) over extended periods
of time are unknown in the world, with one exception only: that being the
focus of the present disclosure. Also, whereas methane has been obtained
and utilized from a dissolved source in a lake (Lake Kivu), carbon
dioxide has never been sourced from a lake in a manner wherein associated
dissolved methane also is co-extracted and utilized within an efficiently
coordinated process such that neither CO.sub.2 nor methane is wasted. In
general, CO.sub.2-dominated hyper-"acid" natural gas occurrences of the
type present in Lake Kivu's deepwater are widely considered to be
unattractive to develop. For example, Indonesia's CO.sub.2-rich
(.about.71% mole fraction CO.sub.2) offshore "East Natuna" giant field
has been known since 1970, but has been left undeveloped (Wikipedia: East
Natuna Gas Field; Batubara et al., 2014. Estimated recoverable methane:
.about.46 Trillion Cubic Feet, TCF).
[0009] Neither Government overseeing the development of Lake Kivu's
deepwater resources has expressed potential utility for the CO.sub.2
present in the lake (e.g., Expert Working Group on Lake Kivu Extraction,
2009, 2010; Ndimubanzi, 2014). Carbon dioxide is not considered to be a
resource in the common document called "Management Prescriptions for the
Development of Lake Kivu Resources," (Expert Working Group on Lake Kivu
Extraction, 2009, 2010). Lake Kivu's CO.sub.2 has been considered to be a
threat, an environmental nuisance, and an obstacle to be overcome for
obtaining power efficiently from the dissolved methane that is present.
[0010] In East Africa, CO.sub.2 is supplied for industrial use, especially
beverage carbonation (including beer), by the Kenyan company Carbacid
(CO.sub.2) Limited (http://www.carbacid.co.ke). Carbacid obtains its
CO.sub.2 from a Kereita Forest spring source. This source has been
developed by drilling to create an artesian well that exsolves CO.sub.2
upon depressurization as the flow approaches the surface. Uncapped, it
provides a fountaining jet of water and CO.sub.2. (See photo of the
initial fountain jet in: http://www.carbacid.co.ke/about/). Carbon
dioxide is upwelling in the crust in the region as a consequence of rift
tectonics and associated active volcanism (cf, Lee et al., 2016).
Carbacid's source of CO.sub.2 is identical in design with that of the
world's first large-scale industrial CO.sub.2 capture plant developed in
Herste Germany in the late 19.sup.th century in an area of mineral
springs near Paderborn, (Muller, undated). The Herste source was drilled
and developed for CO.sub.2 capture in 1894-5 by Carl Gustav Rommenholler,
founder of Kohlensaurewerke C. G. Rommenholler GmbH (Schwedt, 2015: Quinn
and Jones, 1936). Rommenholler patented his artesian well CO.sub.2
extraction and capture method with E. Leehrmann in 1887 (Almqvist, 2003;
Wender, 1901)
[0011] Both Carbacid's and Rommenholler's sources of CO.sub.2 are
equivalent in design to those drilled by the founders of the German
sparkling mineral water company Gerolsteiner, operating since 1888
(www.gerolsteinder.de) in the German town of Gerolstein. Gerolsteiner
extracts the mineral water, and the CO.sub.2 it uses to re-carbonate it,
from a drilled artesian well fountaining water and CO.sub.2. Initially,
Gerolsteiner's first source in 1888 fountained a jet of water and
CO.sub.2 to a height of over 50 meters. (See photos in:
https://www.gerolsteiner.de/de/gerolsteiner-brunnen/historie/;
http://www.eat-drink-etc.com/showcase/Gerolsteiner; Gerolsteiner, 2013,
2015). Gerolsteiner's present day sources are similar to the nearby
CO.sub.2-exsolving "cold geysers" drilled in the region in the village of
Wallenborn bei Gerolstein (Menhert, 2016), and also in Andernach in the
Geopark Vulkanland Eifel nearby (Wikipedia: Andernach Geser). Several
such drilled cold geysers exist in the USA (Kaushik, 2015). (Glennon et
al., 2004 provides a worldwide inventory of both natural and man-made
cold geysers). Carbon dioxide in the volcanic Eifel region of Germany
bubbles up in large amounts from the bottom of a volcanic crater lake,
the Laacher See, but is not captured for use (Goepel et al., 2014).
Artificially created cold geysers historically associated with carbonated
mineral water bottling and German-style CO.sub.2 capture operations
include those in Saratoga Springs N.Y. (Quinn and Jones, 1936; Millet,
2015; Sarasota Springs Heritage Area Visitor Center, 2009; Stoddard,
1895). Carbon dioxide is captured for the carbonation of many well-known
mineral waters by methods identical to that practiced by Carbacid and
Gerolsteiner. It is separated from the depressurization flows of artesian
wells and redissolved under pressure into mineral waters during the
bottling process. Prominent examples of bottled sparkling mineral waters
obtained by this method include: Appolinaris and Selters (Germany),
Perrier and Badoit (France), San Pelligrino and Ferrarelle (Italy),
Walsdquelle (Austria), and Borsec (Romania), (LaMoreaux and Tanner,
2002).
[0012] Well sources used for bottling mineral waters with CO.sub.2 capture
from upflow degassing are non-polluting. They typically do not contain
dissolved substances that cause eutrophication when released into surface
water river flows. The design of extraction systems therefore does not
involve engineering to avoid surface water pollution. Such sources also
are selected for a high purity of CO.sub.2 emission thereby avoiding the
need to refine the gas to remove contaminating gases such as methane,
nitrogen and hydrogen sulfide. Separating minor (<30% molar) amounts
of methane from major amounts of CO.sub.2 is a capital- and
energy-intensive process (e.g., ExxonMobil's Controlled Freeze Zone.TM.
CFZ.TM., process. Thomas and Denton, 1988; Northrop and Valencia, 2009;
Kelley et al., 2011; Herbertson et al., 2011; Parker et al., 2011;
Boschee, 2012; Condon and Kelman, 2012; Finn and O'Brian, 2014; Denton et
al., 2015; Lang et al., 2015).
[0013] On Lake Kivu, the standard separation process in use (described
herein) is wasteful of methane (in total >.about.40% is wasted). As
practiced, it also uses up a substantial fraction of produced power
(.about.>12%) for gas-cleaning operations (CO.sub.2 removal).
[0014] Other natural sources of CO.sub.2 include drilled wells in
historical areas of CO.sub.2 emission in Kizildere Turkey (Wikipedia:
Kizildere Geothermal Power Plant), in Machachi Ecuador ("Agua y Gas de
Sillunchi," Thorhallsson, 1997), in and near Repcelak, Hungary, and in
the Becej area of Serbia. The CO.sub.2-specialized industrial gases
company Linde has built CO.sub.2 capture plants in all three areas.
Locations of shallow-drilled artesian jet-type CO.sub.2 wells used for
dry ice production include Ashland Oregon USA (Klicktat Mineral Springs;
Schafer, 1955; Wagner, 1959: Buckhorn Springs, 2015), the Salton Volcanic
Domes of Imperial Valley, Calif. (Calvin and Pace, 2016), and Ankavan,
Armenia (Hennenberger et al., 2000).
[0015] Commercial plants for obtaining CO.sub.2 from geothermal sources of
hot water/steam linked with geothermal power production include:
Kizildere, Turkey (noted above), Miravalles, Costa Rica, and Haedarendi,
Iceland (Chaves, 1996). The production of CO.sub.2 in these plants
requires separation of hydrogen sulfide.
[0016] The world's largest natural sources for CO.sub.2 utilized
industrially are deep-drilled gas wells in the USA in the states of New
Mexico, Utah, Colorado, Wyoming and Missouri (Broadhead et al., 2009;
Johnson, 2011; DiPietro et al., 2012; Allis et al., undated; DOE/NETL,
2015b). Mostly these sources yield high grade CO.sub.2. There is no
separation of CO.sub.2 gas from water in production from these deep gas
wells.
[0017] Apart from drilled wells, major sources of industrially utilized
CO.sub.2 include: natural gas cleaning/purification plants, ethanol
plants, breweries, distilleries, hydrogen plants (using natural gas
inputs), ammonia plants (also using natural gas inputs), ethylene glycol
plants, biogas cleaning operations, cement plants, refineries and fossil
fuel-burning powerplants. (For overview perspectives, see: Garvey and
Turley, 2011; Cockerill, 2016).
[0018] Rwanda is a dynamic East African nation with strong economic growth
and an agenda to double the national per capita GDP growth rate,
averaging .about.4% per annum in constant dollar terms. The nation has
made impressive strides forward building a lawful order with expanding
peace and prosperity in the interval since it experienced a catastrophic
genocidal disaster in 1994. Rwanda's Parliament and executive leadership
have created a set of well-defined national goals in "Rwanda 2020" and
associated "EDPRS2" documents (see: "Government of Rwanda" in
references). Reaching these goals requires a new phase of rapid
industrialization. Rapid industrialization is necessary to create new
modalities of economic livelihood with increased productivity for the
large fraction of Rwanda's citizens living mostly by traditional
agriculture. At present, more than 80% of Rwanda's total population of
.about.11 million people live in rural situations. Their main economic
activity is traditional forms of agriculture and husbandry
(plantain/banana, corn/maize, cassava, soy and green beans, millet, rice,
potatoes, sweet potatoes, sorghum, carrots, tomatoes, sugar cane, coffee,
tea, goats, sheep, chickens, pigs, dairy and beef cattle, etc.). Most
live predominantly without access to electricity or to self-owned
motorized equipment. Industrialization in Rwanda appropriately will
involve several million people diversifying their activity into new types
of jobs utilizing modern technologies.
[0019] According to the Executive Secretary of the UN Economic Commission
for Africa, Carlos Lopes, optimally advantageous industrialization in
Rwanda and other countries in Sub-Saharan Africa (SSA) should include
three characteristics. They are: (i) substantial value addition to
natural resources prior to export; (ii) industrialization leapfrogging to
utilize new clean "greentech" technologies; and (iii) expansion of trade
between the nations within Sub-Saharan Africa's rapidly growing markets
(Lopes, 2015b).
[0020] Rural electrification with a low cost of power is a clear and
obvious agenda. Low cost power is necessary to accelerate economic
growth. Low-cost engine fuels also are necessary for rapid
industrialization. Low cost electricity and low-cost engine fuels
together provide a critical foundation for industrialization to build
upon. However, Rwanda is in a situation of high cost electricity
(>US$0.20/kWh) and high cost engine fuels (>US$1.2/liter). This
situation is preventing realization of the country's economic goals.
[0021] Rwanda possesses an unusual and abundant energy resource: 50% of a
large reserve of natural biogas (methane: CH.sub.4), .about.50 million
tonnes (MT). This biogas is dissolved in the depths of a large lake, Lake
Kivu. Lake Kivu is shared geographically .about.50:50 between Rwanda and
the Democratic Republic of Congo (DRC). The gas exists together in Lake
Kivu's deepwater with an extremely high amount of associated carbon
dioxide, .about.600 MT. Also present are abundant dissolved Mg--Na--K--Ca
bicarbonates plus dissolved NP (nitrogen and phosphorus) and other trace
element fertilizers.
[0022] Lake Kivu deepwater methane has been used for electric power
production since the 1950s, but many problems exist and many substantial
opportunities for additional resource utilization have not been realized.
[0023] Lake Kivu's reserve of dissolved CO.sub.2 is deep-sourced in the
mantle and crust. It is geothermally injected into the deep lake. A large
upward flux of CO.sub.2 is associated with the active volcanic province
adjacent to the lake's northern boundary and situated within the
structure of the Albertine rift. Lake Kivu's deepwater acts as a trap for
this ascending CO.sub.2. Gases build-up over time. They are released
catastrophically in irregularly periodic convective runaway events called
"limnic eruptions." Artificial extraction of deepwater CO.sub.2 changes
the dynamics from all-at-once events to a steady rate of removal over
time. However, artificial CO.sub.2 extraction does not increase the
overall CO.sub.2 emission rate averaged over a timescale of hundreds of
years. The overall CO.sub.2 flux from the crust into the atmosphere in
the region is set by underlying natural processes of tectono-magmatic
transport. These transport processes make the northern Lake Kivu sector
one of the largest natural emission sources of CO.sub.2 in the world.
(For the same reason, geothermal energy producing nations avoid
accounting for CO.sub.2 emissions associated with geothermal energy. See:
Arnannsson, 2003, 2005.) Time-averaged emission from the Nyiragongo
volcano alone is estimated to be the highest flux in the world for any
volcano: .about.19 million tonnes of CO.sub.2 per annum (MTA), (Burton et
al., 2013).
[0024] The presence of so much geothermally-derived CO.sub.2 associated
with biogas creates a major technical challenge to efficient extraction
and use of Lake Kivu's biomethane. In US 2015/0354451 A1, the inventor
disclosed a method and system for creating both efficient power and
long-term lake safety by "total degassing" (CH.sub.4 and CO.sub.2
together) of Lake Kivu deepwater. The invention utilizes feeding of both
gases, unseparated, into an oxyfuel combustor supplied with oxygen gas
via an Air Separation Unit (ASU). It also organizes return flow of the
deepwater into the lake in a fully degassed state. One aspect of the
output of this power production method is that it generates a
post-combustion exhaust comprised of a mixture of condensable steam plus
nearly pure CO.sub.2.
[0025] In U.S. Patent Application Publication No. 20160257577 A1, the
inventor further disclosed a method and system for total degassing with
treatment of the return flow of degassed water in such a way to decrease
its density by creating abundant photosynthetic bioproducts and
precipitated magnesium hydroxide [brucite: Mg(OH).sub.2]. This allows
replacement of degassed and de-densified water just below the base of the
lake's biozone, thereby optimizing long-term lake safety, capturing a
very large component of valuable methane otherwise lost, and creating
useful products in the de-densification process. Production of
precipitated brucite then allows large scale production of eco-concrete
and related building materials by utilizing CO.sub.2 and steam to
carbonate and hydrate Mg-cement and Mg-cement-pozzolan compositions. The
bioprocessing of return flow water additionally produces very large
quantities of algal biomass and associated products. Overall, the method
offers .about..times.2.5 factor increase in electricity production per
unit of methane present in Lake Kivu, relative to standard technologies.
The method also adds a large factor multiplier to overall industrial
productivity by production of bioproducts and eco-concretes and related
building materials with value greatly exceeding that of electricity. In
this method, however, deepwater bicarbonate ion provides the main carbon
source for photosynthetic bioproduction, rather than CO.sub.2.
[0026] None of these disclosures have addressed how optimally to utilize
the full scale of the massive quantities of deepwater CO.sub.2 released
by a "total degassing" process. Environmental stewardship as well as
industrialization opportunity makes CO.sub.2 utilization a vital unsolved
problem and inventive challenge. The scale of the potential flux, ranging
up to .about.20 million tonnes per year CO.sub.2 in total for a 30 year
extraction time, makes Lake Kivu the world's most dynamic opportunity for
developing advanced industrialized CO.sub.2 utilization on a large scale.
Many technologies exist matched with attractive market opportunities in
the region and beyond. Meeting such a challenge in the situation of Lake
Kivu in the center of Africa is non-trivial. It requires inventive new
technology in several different types combined together.
[0027] Industrializing systems of innovative machines are necessary to a
long-term better economic future for hundreds of millions of people in
Sub-Saharan Africa (SSA). Long-term economic development is a consequence
of "market creating" industrialization: the creation of systems of
innovative machines managed with the capability to allow people to
transform basic resources into valuable and exportable products
efficiently, on a large scale, with market competitiveness, thereby
creating new high-value trade, high-value employment and widespread
prosperity (Economic Commission for Africa, 2014, 2015; Lopes, 2015a,b;
Arkhangelskaya and Taylor, 2014; Taylor, 2014a,b; African Transformation
Report, 2014; Christensen, 2014; Mezue et al., 2015). Industrialization
based on industrial technology transfer creating a basis for production
and export trade has long been the core driver of spectacular economic
growth in rapidly developing countries over the past 50 years. The
dynamic of successful 20.sup.th century industrialization has operated
through various modes of change including entrepreneurship, new
scientific and engineering insights, capital investment, government
policies and wartime emergencies (Maddison, 2001, 2005, 2007, 2008).
Underneath all of these aspects of understanding, it can be useful to
recognize that growth in employment and prosperity fundamentally is built
upon mechanical productivity: that is machines. Innovative systems of
machines drive enhancements in human productivity. (Typically these are
factories. However, systems of machines also include IT-based coordinated
productivity.) Machines provide the basic nexus for the multiplication of
output per person of goods and services. Machines are the sine qua non,
the without-which-nothing, whereby human activity is multiplied
drastically in economic productivity, thereby advancing prosperity
(Lewis, 2004).
[0028] The creation of systems of industrial machines to produce low-cost
power is a doubly foundational aspect of industrialization. Electricity
is one of the basic forms of industrial power. Yet roughly 600 million
citizens in SSA are disconnected from access to electricity needed to
power machines necessary to leverage economic productivity.
[0029] The Manufacturing Value Added (MVA) percentage of GDP is an index
for accessing national performance in industrial productivity (UNIDO,
undated). MVA has fallen drastically in SSA over the past 40 years: from
.about.18% to .about.10%, while simultaneously MVA has expanded massively
in East Asia (Rowden, 2013). Per capita manufacturing value addition in
Rwanda, a country with massive gains in governance and growth but still
mainly exporting commodity dried coffee beans, tea leaves and raw
minerals, was .about.$30 per person per year in 2014 (with MVA at 6% of
GDP). This may be compared to .about.$1,900 for China, .about.$6,000 for
the USA and .about.$10,000 for Singapore (UNIDO, 2015; GlobalEconomy.com,
undated). Such statistics indicate a massive industrialization gap
consistent with Rwanda scoring as one of the world's least industrialized
societies in UNIDO reports (UNIDO, 2013, 2015). An estimated 83% of
Rwandans inhabit rural regions where they live mostly by farming activity
(NISR, 2014; de la Victoire, 2014), working with their hands using
baskets and hoes as their major form of technology leverage. Rwanda has
outstanding potential from its many reforms, thriving capital city and
rapidly rising per capita GDP. Its low industrialization represents one
of the greatest opportunities in the world for rapid human betterment.
Rwandan leaders are aware of this challenge and opportunity. They have
established a policy to encourage very rapid growth in the industrial
economy (Economic Commission for Africa, 2015b; Ministry of Trade and
Industry, 2011). Turning policies into realities, however, will require
installing systems of industrial machines on a large scale through
private enterprise and governmental joint ventures with the private
sector. Future growth depends especially on "moving up the value chain"
(Kaberuka, 2015) by both processing traditional products such as coffee,
tea and minerals to add value, and by creating completely new modes of
production for export. Overall, sustained development of Rwanda and other
countries in Sub-Saharan Africa depends on success in accelerating
industrialization in energy, manufacturing and technologically modernized
agriculture (Economic Commission for Africa, 2015a; African
Transformation Report, 2014).
[0030] Systems of industrial machines require both policy support and
intrinsic profitability to grow rapidly through initial capital
investment with follow-on investment pursuing demonstrated success. Areas
of particular promise will demonstrate industrial clustering potential
from the presence of abundant low-cost resources and associated
opportunities to transform these resources into locally useful and/or
exportable products possessing substantial value-addition. Successful
cluster development, however, additionally requires attracting many
highly innovative technically trained people (Porter, 1998; Wadhwa, 201).
That sometimes is not easy in Africa, though Rwanda benefits from a very
impressive returning diaspora. While resource extraction productivity can
operate in isolation, as in the case of offshore oil platforms, and
whereas broadband Internet communications now can create global virtual
video-community networks easily, the development of clustering sufficient
for industrial-economic take-off, and the rapid growth of knowledge
capital more generally (Hanushek and Woessmann, 2015, 2016), still
requires the ability to attract many high-talent people to a region.
[0031] Lake Kivu is one of the most elegantly beautiful and
climatologically attractive regions in the world. Though relatively
little known, its future holds tremendous potential (Kivu Belt, 2013).
[0032] Systems of industrial machines are a key to greentech
transformation to achieve "green economy" environmental goals (UNEP,
2014, 2015). The increase of carbon dioxide (CO.sub.2) in the atmosphere
from industrial activity is widely considered to have generated a
substantial global risk from the possibility of major climatic system
instabilities (IPCC, 2015). Accordingly, one of the challenges of the age
is to find solutions to address this risk. Talented people all over the
world are focused on this task. Attractive solutions especially will
avoid constraining economic growth, in particular growth that benefits
emerging market economies where the need for development is great, as in
Sub-Saharan Africa. One agenda being widely pursued is to develop ways to
create power, fuels and industrial products in ways that absorb, utilize
and recycle, rather than emit, CO.sub.2, and that do so with superior
performance in the competitive economic marketplace. Despite intense
research and many impressive scientific-technological breakthroughs, only
limited substantially scaled examples exist in industry. The largest
quantities of utilized CO.sub.2 are injected into oil wells via
CO.sub.2-based Enhanced Oil Recovery (CO.sub.2-EOR, Meyer, 2007: Al-Mjeni
et al., 2010/2011; Muggeridge et al., 2015). Most of this CO.sub.2,
however, is not recycled. It is obtained from natural wells.
[0033] The agenda to create new industries based on industrial CO.sub.2
recovery and utilization recycling (Benson, 2015) is described by the
terms "carbon capture utilization" (CCU) and "carbon dioxide utilization"
(CDU, Styring et al., 2011). In recent years, huge international effort
has been invested to develop new scientific insights and technologies
pertinent to CO.sub.2 utilization. A large quantity of literature exists
on CCU/CDU (hereafter: CCU). It includes an industry overview (Prize
Capital, L L C, 2011) plus many books (Goosmann, 1906; Aresta and Forti,
1987/2011; DOE, 1993; Halman, 1993; Sullivan et al., 1993; Inui et al.,
1998; National Academy of Sciences, 2001; Creutz and Fujita, 2001; Song
et al., 2002; Aresta 2003, 2010; DeSimone and Tumas, 2003; Liu and
Mallinson, 2003; Olah and Goeppert, 2006; Hu, 2011; Yang et al., 2012;
Suib, 2013; De Falco et al., 2013; Anastas et al., 2014; Aresta and van
Eldik, 2014; Bhanage and Arai, 2014; Centi and Parathoner, 2014; Styring
and Quadrelli, 2014; Aresta and Dibenedetto, 2015; Aresta et al., 2015;
Jin et al., 2015; Morreale and Shi, 2015; Surampalli et al., 2015). The
field includes a dedicated research journal publishing articles since
2013, the Journal of CO.sub.2 Utilization (JCOU). It includes several
annual conference series, including the International Conference on
CO.sub.2 Utilization (ICCDU), (Aresta, 2015), the Carbon Capture,
Utilization and Storage Conference series organized by the United States
Energy Association, USEA (USEA, undated), the Conference on Carbon
Dioxide as Feedstock for Fuels, Chemicals and Polymers series
(http://co2-chemistry.eu/past), the Carbon Dioxide Utilization Summit
series organized by Active Communications International (ACI), the
European Carbon Capture and Storage conferences, and the Guangdong
International Carbon Capture Utilization and Storage Conference series
(http://www.gdccus.org). The literature of CCU includes an abundance of
technical review papers, for example: Behr, 1987, 1988; Mortensen, 1987;
Braunstein et al., 1988; Darensbourg and Holtcamp, 1996; Leitner, 1996;
Shaikh and Sivaram, 1996; Kendal et al., 1999; Taylor et al., 2000;
Arekawa et al., 2001; Creutz and Fujita, 2001; Song, 2002; Beckman, 2003,
2004; Mazzotti et al., 2005; Aresta, 2006; Omae, 2006, 2012; Sugimoto and
Inoue, 2006; Aresta and Dibenedetto, 2007; Darensbourg, 2007; Jitaru,
2007; Haring, 2008; Sakakura et al., 2007; Benson et al., 2009; He et
al., 2009, 2010; Munshi and Bhaduri, 2009; Ramsey et al., 2009; Glueck et
al., 2010; Riduan and Zhang, 2010; Jiang et al., 2010; Dai et al., 2010;
Darensbourg, 2010, 2014; Mikkelsen et al., 2010; Darensbourg et al.,
2010; CCUS-China, 2011; Cokoja et al., 2011, 2015; Global CCS
Institute/Parsons Brinckerhoff, 2011; Yang et al., 2011; Centi et al.,
2011, 2013; Quadrelli et al., 2011; Mohamed and Eastoe, 2011; Peters et
al., 2011; Savile and Lalonde, 2011; Viswanathan, 2011/2014; Wang et al.,
2011; Darensbourg and Wilson, 2012; Fukuoka, 2012; Lu and Darensbourg,
2012; Holscher et al., 2012; Jessop et al., 2012; Jin et al., 2012; Kumar
et al., 2012; Laumb et al., 2012; Pearson et al., 2012; Sumida, 2012;
Tsuji and Fujihara, 2012; Ackiewicz et al., 2013; Appel et al., 2013;
Aresta et al., 2013, 2014; 2015; Bocin-Dimitru et al., 2013; Costentin et
al., 2013; Gao et al., 2013; Yang et al., 2012; Hawkins, 2013; Harriman,
2013; Hendriks et al., 2013; Oman et al., 2013; Kondratenko et al., 2013;
Geerlings and Zevenhoven, 2013; Power et al., 2013; Zakkour, 2013; ADEME,
2014; Araujo et al., 2014; Centi and Perathoner, 2014; Huang and Tan,
2014; Matthessen et al., 2014; Patel et al., 2014; Sanna et al., 2014;
Silva and Meireles, 2014; Ravanchi and Sahebdelfar, 2014; Shi et al.,
2015; Taherimehr and Pescarmona, 2014; Urakawa and Sa, 2014;
Alissandratos and Easton, 2015; Behrens, 2015; Demirel et al., 2015; Wang
et al., 2015; Cuellar-Franca and Azapagic, 2015; Durre and Eikmanns,
2015; Lee et al., 2015; Liu, Q., et al., 2015; Luca and Fenwick, 2015;
Ampelli et al., 2015; Alvarez-Guerra et al., 2015; Kenis, 2015; Kortlever
et al., 2015; Lim, 2015; Shi et al., 2015; Romanov et al., 2015; Su et
al., 2015; Theulen, 2015; Wang et al., 2015; White et al., 2015;
Wuppertal Institute, 2015; Xin et al., 2015; and Porosoff et al., 2016.
The field of CCU includes long-established industrial examples such as:
sodium bicarbonate production (Wikipedia: Solvay process), salycilic acid
production (Rocke, 1993), and carbon monoxide production (from coal
reacting with CO.sub.2, Hunt at al., 2013), used in mineral ores smelting
and cyclic organocarbonates production (North, 2012). Long established
examples also include: urea production from ammonia; neutralization of
industrial alkaline residues including high-pH alkaline wastewaters
(Linde, undated; Garmo and Escudero, 2014; Gomes et al., 2016);
production of precipitated fine calcium carbonate white pigment used in
paper making and many other industries (Lopez-Periago et al., 2010);
chemicals production based on Grignard reagent carboxylations (Silverman
and Rakita, 2005; Wu et al., 2014); and carbonation-precipitation of
CaCO.sub.3 as a purification step in sugar refining (Moodley et al.,
2002; Varelius, 2014). The field of CCU also includes various direct
CO.sub.2 uses such as, for example: dry ice, insecticidal fumigants, fire
extinguishing gas (Makowa/NAFED, undated), refrigerant gas (Bodinus,
1999), supercritical CO.sub.2 solvent and reaction medium applications,
food preservation/storage gas, and horticultural plant feeding employing
the CO.sub.2 fertilization effect applied in commercial greenhouses
(Mortensen, 1987; Allen et al., 1996; Blom, 2015). The field of CCU also
includes developments with recent rapid industrial growth on a large
scale: CO.sub.2-based Enhanced Oil Recovery (EOR) as well as the use of
CO.sub.2 as a fracking fluid or as a component in fracking fluids. It
includes power storage technologies for stabilizing intermittent
renewable electric power input via "power-to-gas" methanization of
CO.sub.2 using hydrogen generated by water electrolysis, operating
commercially in Germany (Schiermeier, 2013; Wikipedia: Power to gas;
Hydrogenics, undated; ETOGAS, 2015; Schlumberger, 2014; Prokofyeva,
2014). It includes industrial "green chemistry" with many possibilities,
amongst which a prominent commercial example is polyurethane foam
manufacture by the German manufacturing giant Bayer using CO.sub.2 input
to create "CO.sub.2-polyols" (Langanke et al., 2014; Prokofyeva and
Gurtler, 2015a,b; see also: www.novomer.com, and additionally Chapman et
al., 2015 describing similar activity by the UK company Econic). Another
related example is a promising effort to industrialize large-scale
production of industrially useful glycerol carbonate from CO.sub.2
reacting with industrially abundant glycerol (North et al., 2010;
CyclicCO.sub.2R, undated; North, 2012; Sonatti et al., 2013; Castro-Osma
et al., 2014). Recent breakthroughs in CCU include a new mode of cement
and concrete manufacture based on Mg(OH).sub.2 rather than CaCO.sub.3.
This technology incorporates CO.sub.2 rather than releases it
(www.tececo.com; Harrison, 2013; Al Tabbaa, 2013). CCU also includes an
embryonic technology revolution developing many new technologies for
artificial photosynthesis to produce "electrofuels," "solar fuels," and
other industrial "solar chemicals" from inputs of CO.sub.2, water and
light (Goodson, 2015).
[0034] Also, wherever algae species are grown commercially and under
photoautotrophic conditions, CO.sub.2 typically is utilized as an input
carbon source. Examples include the US-based algae companies Earthrise
(www.earthrise.com), Cyanotech, (www.cyanotech.com; www.nutrex.com),
Algenol (www.algenol.com), Sapphire Energy (www.sapphireenergy.com),
Heliae (www.heliae.com), Aurora Algae (www.aurorainc.com), Cellana
(www.cellana.com), Algae-2-Omega (www.Algae20mega.com), Qualitas-Health
(www.qualitas-health.com), Bioprocess Algae (www.bioprocessalgae.com),
Algae Systems (www.algaesystems.com), the Israeli companies NBT
(https://www.d-factoryalgae.eu/42-eng-nbt.html) and Algatech
(www.algatech.com), FEBICO in Taiwan,
(http://www.febico.com/en/page/Facility/facility.html), Yaeyama Chlorella
in Japan (www.yaeyamachlorella.com), Parry Nutraceuticals in India
(www.parrynutraceuticals.com), and Roquette Klotze in Germany
(www.algomed.de), (ABO, 2015; Burlew, 1953; Benemann et al., 1987;
Benemann and Oswald, 1996; Benemann, 1997, 2003; Anderson, 2005; Gershwin
and Belay, 2008; Linde, 2010; Liu and Hu, 2013; Richmond and Hu, 2013;
Borowitzka and Borowitzka, 1988; Borowitzka and Moheimani, 2013; Carr,
2015; Sapphire, 2015; Woods, 2015; Anton, 2015; Legere, 2015; Global CCS
Institute, 2011-Appendix E; Lundquist et al., 2010; Craggs et al., 2012:
Ben-Amotz, 2011; Boussiba, 2015).
[0035] For applicability of CCU in Sub-Saharan Africa, a key to future
success will be the development and demonstration of large-scale
profitable examples. Early examples will require special circumstances.
Ideally, these will include: (i) freely available and nearly pure
CO.sub.2; (ii) high-value product options; (iii) strong market demand
such products at a high price point; (iv) strong long-term rapid growth
potential (v), a favorable business environment for investment, and (vi)
industrial cluster-forming potential. A strategic factor of special
interest for cluster-forming potential is the world-historic significance
of CCU. The prospect of developing major components of a carbon-recycling
economy creates a powerful attractor for entrepreneurs, investors and
high-talent engineers and scientists as well as to institutions involved
in research and development towards a green economy. This factor adds
another aspect of attraction to already attractive arena of being
involved in transforming the lives of hundreds of millions of people
Sub-Saharan Africa towards prosperity.
[0036] Human industrial and agricultural activities release .about.35
gigatonnes of CO.sub.2 into the Earth's atmosphere each year, about half
of which accumulates. At present anthropogenic release of CO.sub.2 is
causing an annual increase in the CO.sub.2 concentration of the Earth's
atmosphere of .about.0.5% per year. Pre-industrial CO.sub.2 prior to
.about.1750 was about 280 ppm. Today it is .about.400 ppm. Growth is
.about.2 ppm per annum, with an accelerating growth trend as developing
countries rapidly industrialize. Carbon dioxide is a radiation-trapping
"greenhouse" gas. Increase in its atmospheric abundance generates a
climatological warming tendency. It also generates ocean acidification
from increased CO.sub.2 uptake into seawater. A worldwide coalition of
governments is concerned about risks from climate change and ocean
acidification. This coalition is seeking to decrease the flux of CO.sub.2
released by human activities into the atmosphere. However, the rapid
industrial development of developing countries, a vital matter for the
alleviation of mass poverty, drives accelerating growth in world CO.sub.2
output. Hence a conundrum exists. Strategies that encourage the
persistence of mass poverty are unlikely to succeed. Therefore a key
challenge is to transform new industrialization, especially in developing
countries, from standard high-CO.sub.2 modes to "greentech" modes. A key
focus for this agenda relates to the combustion of the .about.4 billion
tonnes of coal mined each year (BP, 2015), almost all of the carbon (12
grams per mole) of which is converted to CO.sub.2 (44 grams per mole).
[0037] One aspect of this agenda is industrialization of CO.sub.2
utilization technologies: to invert the situation of CO.sub.2 being a
waste into CO.sub.2 being a carbon source input into industrial
production. To be useful for environmental purposes, industrial CO.sub.2
utilization requires the development of profitable uses for CO.sub.2 in
large quantities, especially involving, wherever possible, carbon
recycling as well as inputs of renewable sources of power (Olah et al.,
2011). Scale matters. To make a substantial impact on atmospheric carbon
accumulation, overall CO.sub.2 utilization targets worldwide should sum
to at least, say, 10% of the human CO.sub.2 emissions rate of .about.35
billion tonnes (35.times.10.sup.9 T) per year (=.about.10 billion tonnes
elemental carbon per year). The agenda and challenge is to inaugurate a
new mode of dynamic industrialization wherein new modes of CO.sub.2
utilization contribute substantially to economic growth. This requires
new forms of industrial production at a total CO.sub.2 utilization scale
of several billion tonnes per year. This challenge therefore unavoidably
must be focused predominantly on products in areas of very large-scale
production in terms of mass. Such arenas include agriculture and wood
production, mining and metallurgy, fuels extraction and production,
plastics manufacture, and the production of cement-based building
materials and aggregate such as provide the inputs into the production of
concrete. Concrete (cement+aggregate+water), for example, is produced on
a global scale of roughly 30 billion tonnes per annum (Smil, 2013;
Armstrong, 2013). For comparison, world liquid transport fuels production
is about 5 BTA, (USEIA, 2015; BP, 2015), world iron ore production is
about 3 BTA (USGS, 2015), world roundwood production is about 1.5 BTA
(FAO, 2014), world plastics production is about 0.3 BTA (Gourmelon, 2015)
and world aluminum ore bauxite production and processing is about 0.25
MTA (USGS, 2015). Examples of industrial CO.sub.2 utilization linking
with these large scale forms of production include: (i) structural
capture into cements and concretes; (ii) sequestering CO.sub.2
underground via processes of enhanced oil recovery, EOR (NETL/DOE, 2010),
(iii) utilizing CO.sub.2 as a carbon source for energy storage in
transportation fuels by CO.sub.2 reduction with hydrogen obtained from
renewable sources by water electrolysis; (iv) creating CO.sub.2-sourced
replacement for petrochemicals in plastics manufacture such as for
example polyethylene and polyurethane; (v) increasing agricultural
productivity both by CO.sub.2 plant feeding and high-yield sustainable
forest management; and (vi) developing low-cost mining and ore processing
technologies extracting major industrial metals such as iron and/or
nickel and/or aluminum using processes that mineralize carbon.
[0038] A major challenge moving forward is to create economically viable
examples of conglomerated CO.sub.2 utilization industrial networks. In
such networks, waste CO.sub.2 would create a basis for industrialization
across a range of specific modes of CO.sub.2 utilization. This task has
not been achieved. No examples exist. The world's largest mode of
industrial CO.sub.2 utilization, CO.sub.2-EOR, is dominated by CO.sub.2
pipeline networks in the United States (NETL/DOE, 2010; Department of
Energy, 2015). And the CO.sub.2 used in EOR in the United States is
predominantly derived from CO.sub.2 wells and not from recycling of
industrial waste CO.sub.2 sources.
[0039] The X-Prize Foundation (www.xprize.org) launched the US$20 million
"NRG Cosia Carbon X-Prize" in 2015 to incentivise major breakthroughs in
large scale CO.sub.2 utilization (http://carbon.xprize.org; Lim, 2015).
[0040] Lake Kivu possesses a density-stratified convectively stable
("meromictic") structure. A relatively shallow oxygenated convecting
"bio-zone" exists from the surface down to 30 to 70 meters, varying
according to seasonality and storm intensity. Below .about.100 meters,
trapped gases are present in a stack of anoxic layers known collectively
as the "monimolimnion." In these, the water density increases in a
stepwise manner down to a maximum depth of 485 meters. Lake Kivu's main
methane reserve is below 250 meters. It contains a total amount of
dissolved methane (CH.sub.4) of about 32 million tons (approximately 1.5
trillion cubic feet, TCF). Dissolved CO.sub.2 also is present: about 423
million tons (Capart and Kuffrath, 1956; Schmitz and Kuffrath, 1955;
Tietze, 1978, 1980a,b; 2000, 2007 Wuest et al., 2009, 2012; Tassi et al.
2009). The dissolved deepwater gas below Lake Kivu's density
discontinuity at 250 meters has a molar ratio:
CO.sub.2/CH.sub.4.about.4.8. Lake Kivu's deepwater also is nutrient-rich
(Tassi et al. 2009). Descy et al., (2012) provides comprehensive overview
perspectives on Lake Kivu.
[0041] Pipes originating in the depths of Lake Kivu below 250 meters
connecting to the surface can auto-siphon, transporting expanding bubbly
flows upwards without a necessity for pumping (Halbwachs, website; Tassi
et al., 2009).
[0042] The deepest and most methane-rich resource zone in Lake Kivu is
called the "Main Resource Zone" (MRZ). The trapped gas resource in the
MRZ, .about.32 million tonnes of methane, has the capability, in
principle, to provide approximately 1,000 megawatts continuous power over
a period of 30 years if extracted and combusted with high efficiency.
[0043] The presence of an estimated approximately 500 million tonnes of
associated CO.sub.2 trapped at depth in Lake Kivu in the MRZ and PRZ
presents a major efficiency challenge. Methane typically cannot be
combusted efficiently for power production in the presence of large
amounts of CO.sub.2. Pre-combustion separation of CO.sub.2 by various
differential extraction and gas-cleaning technologies requires
substantial power production efficiency loss as well as large capital
investment in equipment.
[0044] A staged system based on the differential gas solubility of
CH.sub.4 and CO.sub.2 in water at different pressures has been used in
Lake Kivu by all power projects. The design was developed and patented by
the company L'Union Chimique Belge in 1953-1962 (Patent: 1954, published
1957: Kingdom of Belgium patent 531780, l'UNION CHIMIQUE BELGE S. A.,
"PROCEDE D'EXPLOITATION DE GAZ DISSOUS DANS DES EAUX PROFONDES. Related
references: Capart, 1954, 1960; Borgniez, 1960; Capart et al, 1957/8;
Capart and Kufferath, 1956, 1962; Tietze and Maier-Reimer, 1977; Williams
Brothers Engineering Company/USAID, 1979; Descy et al., 2012; Halbwachs,
2011: European patent application: EP 2 357 318 A1). The design was
developed using the limnological data of Damas (1937a,b), Capart and
Kufferath, (1956), Verbeke (1957), and others. The design and principles
are detailed on the website of Dr. Michel Halbwachs (Halbwachs, website)
and elsewhere (Tietze and Maier-Reimer, 1977; Williams Brothers
Engineering Company/USAID, 1979; Maj/YLEC Consultants, 2009; Antares
Offshore LLC website, undated; Tietze 1980b, 2000, 2007; Wuest et al.,
2009, 2012; Osterdijk and Heencamp, 2012).
[0045] The main engineering challenge of separating the extreme amount of
CO.sub.2 associated with methane can be overcome with oxyfuel combustion
technology linked with a total degassing process. This technology has the
capability to combust Lake Kivu's CO.sub.2-rich gas directly, yielding
power with high thermal efficiency and without loss of methane and energy
from CO.sub.2 separation processing. This solution is described the
inventor's U.S. Patent Application Publications Nos. 20150354451 A1 and
20160257577 A1.
[0046] The presence of so much CO.sub.2 trapped at depth in Lake Kivu
presents a serious threat of mass asphyxiation of the .about.2M people
living in close proximity to the lake within its basin (Baxter et al.,
1989; Costa and Chiodini, 2015). The danger is from the possibility of
very large scale convective runaway gas release "limnic eruption"
(Sigurdsson et al., 1987; Kling et al., (1987); Tietze, (1992); Zhang,
(1996); Halbwachs et al., (2004); Schmid et al., (2004, 2005); Zhang and
Kling, (2006); Halbwachs, (2014); and Vaselli et al. (2015). Mass
asphyxiations from much smaller scale limnic eruptions that occurred in
small volcanic lakes in Cameroon in the 1980s have been described by
Baxter et al., (1989); Tietze (1992); Eby et al., (2006); Costa and
Chiodini, (2015); and Kling, (undated). A future event in Lake Kivu
likely would be triggered by lake bottom volcanism in the northern sector
of the lake. Bathymetric surveys have revealed the presence of several
volcanogenic cones on the deep lake bottom. The natural quasi-periodicity
of convective runaway events is approximately every 1,000 years. The last
event occurred .about.900 years ago. This is known from studies of
sediment cores from Lake Kivu which reveal evidence of past convective
runaway events in the lake. All appear to have been triggered by volcanic
activity according to the evidence found in these cores (Haberyan and
Hecky, 1987; Ross, 2013a,b; Hecky and Reinthal, 2010; Ross et al., 2013,
2014, 2015. However, see also: Zhang et al., 2014). Wauthier et al.,
(2012, 2015) presented evidence connecting Lake Kivu's continental rift
environment to the extensive volcanism adjacent to it in the north and by
rift-related fracturing and deep magmatic dike intrusion to the various
volcanic cones present at depths below 300 meters in the northern sector.
Volcanic plumbing in this system was activated in the 2002 eruption near
to the shore of the lake, but fortunately not underneath it. The recent
work of Ross and Wauthier and their colleagues has illuminated important
aspects of Lake Kivu's danger. These insights suggest degassing removal
of CO.sub.2 from the deep lake will be urgently prudent to protect both
human populations and Lake Kivu's ecosystem.
[0047] Commercially viable industrial utilization of CO.sub.2 in
large-scale flows (that is, exceeding .about.100,000 tonnes per year)
must connect sources to sinks in an economically efficient manner, either
by adjacent proximity or pipeline systems. Long distance transport of
CO.sub.2 can be expensive, adding a cost in the range of US$15 to $35 per
tonne for compression and transport on the scale of about 500 km (Kuang
et al., 2015. For detailed analysis, see: Doctor et al., 2005). Long
distance CO.sub.2 pipeline systems exist only in certain areas of the US
and Canada (Noothout et al., 2014; Denbury, 2011; IPCC, 2005 chapter 4;
Ortiz et al., 2013; Department of Energy, 2015). The world's most
extensive CO.sub.2 pipeline system includes almost 3,000 miles of
pipeline. It connects through Denver City, NW Texas. Denver City is the
world's largest CO.sub.2 distribution hub (Clark, 2014). Its pipeline
network connects into another pipeline network to the south coordinated
via the McCamey hub in McCamey, Tex. These interconnected networks
distribute CO.sub.2 for enhanced oil recovery throughout the Permian
Basin (EOR, Muggeridge et al., 2015; Al-Mjeni et al., 2010/2011). The
Denver City hub distributes about 30 million tonnes (MTA) of CO.sub.2 per
annum for EOR injection into old low-productivity oilfields to rejuvenate
oil extraction (Powerplantccs, undated; Kuuskraa and Wallace, 2014;
Wallace and Kuuskraa, 2014). This CO.sub.2 mostly is obtained from
natural wells: Sheep Mountain, McElmo Dome and Doe Canyon in Colorado,
and Bravo Dome in New Mexico. In 2010 and 2012, a major new source of
industrial CO.sub.2 came on line via Occidental petroleum's Century Gas
Processing Plant located in Fort Stockton Tex. located about 160 miles
south of Denver City. The Century plant added a CO.sub.2 extraction
capacity exceeding 8 MTA into the hub system (Century Plant Fact Sheet,
2014; ZeroCO.sub.2, undated). This added to other industrially-sourced
CO.sub.2 input into West Texas regional pipeline systems from a network
of five CO.sub.2 sources from ammonia production and natural gas
"sweetening" (CO.sub.2- and H.sub.2S-removal) plants developed in
.about.1972. These include the Pikes Peak, Grey Ranch, Puckett, Mitchell,
and Terell gas sweetening plants, plus the Val Verde ammonia plant. This
network provided the first basis for using CO.sub.2 on a large
commercial-scale for EOR in the USA (Meyer, 2007; Gao et al., 2013). Ever
since, this system has piped purified CO.sub.2, between 1 and 2 million
tonnes per year, 132 km to a Val Verde Texas distribution hub for
distribution for EOR use (Benson, 2015; MIT, 2015). Detailed maps of
these Permian Basin collection and distribution systems are provided by
Moore (2005), Melzer (2007), Husted (2009) and Department of Energy
(2015). Beginning in 1976, supercritical CO.sub.2 was pumped .about.100
km from an ammonia plant to the Lick Creek oilfield in southern Arkansas
for immiscible CO.sub.2-EOR flooding in a depleted heavy oil field (Reid
et al., 1981). An additional system utilizing anthropogenic CO.sub.2
exists in Texas near Houston. About 1 MTA waste CO.sub.2 is captured from
an industrial steam reformer hydrogen plant within the Valero refinery in
Port Arthur. This CO.sub.2 is piped 159 km for EOR injection into the
Hastings oil field near Houston (Haszeldine, 2015).
[0048] CO.sub.2 utilization for greenhouse fertilization is widespread.
Greenfield Specialty Alcohols (www.gfsa.com) of Chatham, Ontario (Canada)
operates in a local industrial symbiosis with the greenhouse tomato
grower Truly Green Farms (http://www.trulygreenfarms.ca). Ethanol
production provides waste heat and CO.sub.2 to the greenhouses (Jessen,
2013; GreenEnergyFutures, 2014). A similar situation exists in Sweden
linking a distillery with a tomato grower (Advantage Environment, 2013).
In 2015, the company Linde Gas Turkey commissioned a CO.sub.2
purification and liquefaction plant to capture geothermal CO.sub.2 from
the Zorlu Energy geothermal power plant near Denizli in order to supply
an initiative to create an "Organized Greenhousing Zone" in the region
(Cockerill, 2015).
[0049] Close proximity allows CO.sub.2 to be routed efficiently between
sources and utilizers without the need to purchase land use rights,
construct transport pipeline systems and pay energy costs for compressing
CO.sub.2 for extended transfer. Proximity-based industrial collaborations
linking CO.sub.2 producers and users are reviewed briefly in following.
Most involve urea production. The industrial production of ammonia
(NH.sub.3) creates CO.sub.2 waste via the process of methane reforming.
Most of it can be cycled into the production of urea (for example:
Agrium, 2015; Wikipedia: Urea; Perez-Fortes et al., 2014). Urea is
produced by combining ammonia and CO.sub.2 to form ammonium carbamate via
an exothermic reaction, 2NH.sub.3+CO.sub.2.fwdarw.H.sub.2NCOONH.sub.4,
followed by an endothermic "urea conversion" dehydration reaction:
H.sub.2NCOONH.sub.4.fwdarw.(NH.sub.2).sub.2CO+H.sub.2O. Natural gas is
the dominant hydrogen source input into the Haber-Bosch (Smil, 2000) and
Bosch-Meiser processes for ammonia and urea production, respectively. The
carbon present in the input natural gas is mostly transformed into
CO.sub.2 in the process of industrial hydrogen production. Ammonia
(NH.sub.3) is produced using the resulting hydrogen (H.sub.2). This is
done by fixing nitrogen (N.sub.2) obtained from air via Haber-Bosch
synthesis: 3H.sub.2+N.sub.2.fwdarw.2NH.sub.3.
[0050] The Saudi Arabia Basic Industries Corporation (SABIC) is creating
the world's largest CO.sub.2 purification and liquefaction plant in
Jubail Industrial City, Saudi Arabia (Linde, 2013a; World of Chemicals,
2013). This plant will pipe CO.sub.2 waste from two ethylene glycol
plants to be utilized in nearby urea and methanol plants. It is planned
that most of the CO.sub.2 eventually will be used for CO.sub.2-EOR.
Additional examples of plans for proximity CCU in heavy industry under
development include: (i) Masdar City in the UAE (Masdar/Al Reyadah,
undated), and (ii) possibly the Jurong Island Eco-Industrial Park in
Singapore (Pan et al., 2015; For an overview analysis see: Singapore
report, 2014).
[0051] A team of Louisiana State University engineers focused on CCU
examined the US lower Mississippi River Corridor (MRC) complex of
large-scale heavy industries in chemicals and energy. Their aim was to
understand and promote opportunities for large-scale CCU implementation
(Hertwig et al., 2002; Xu et al., 2003, 2005; and Indala, 2004). This
group concluded there was substantial potential for profitability from
CCU implementation coordinating CO.sub.2 flows between producers and
users. They especially noted possibilities for future development based
on new CCU-favorable modes of industrial chemicals production. This
hoped-for development has not yet taken place. Nonetheless, development
of networked CCU in the wider region has grown hugely by connection with
CO.sub.2-EOR. In 2011, Denbury (www.denbury.com; Schnacke, 2015)
completed its .about.700 km US$1B CO.sub.2 "Green pipeline" network
crossing the MRC. The "Green" pipeline links a natural CO.sub.2 source,
Jackson Dome in central Mississippi State to EOR locations in and near
Houston, Tex. (Denbury 2009a,b; Denbury, 2011). At present, CO.sub.2 from
the Geismar Louisiana ammonia plant owned by Potash Corporation/PCS
Nitrogen adds to CO.sub.2 flow into this pipeline. Additional
anthropogenic industrial CO.sub.2 inputs are planned and in development
(Kuuskraa and Wallace, 2014; Wallace and Kuuskraa, 2014; Kuuskraa, 2014).
These include an expected .about.3 million tonnes per year (MTA) of
CO.sub.2 to be captured from the integrated gasification combined cycle
(IGCC) clean coal "Kemper Project" .about.500 MW power plant in
Mississippi expected. This plant is expected to start-up in 2016
(www.kemperproject.org; Wikipedia: Kemper Project; Sarkus, 2015; Wilson,
2015).
[0052] Denbury's "Green" CO.sub.2 pipeline from mid-state in Mississippi
to Houston Tex. follows a CO.sub.2-EOR-focused business model. Hasan et
al., (2014) evaluated the technology and economics of CCU industrial
ecology. These authors estimated a cost basis for CO.sub.2 of
.about.US$40 per tonne "captured and managed" in the US with predominant
CO.sub.2-EOR utilization. Subground CO.sub.2 storage management in the US
and Canada is beginning to link with CO.sub.2-EOR, as there is potential
for favorable economics extracting large quantities of oil left behind
after conventional extraction flows have dried up (Carter, 2012; Godec et
al., 2013; Kuuskraa et al., 2013: OECD/IEA, 2015; IEA, 2015, 2016). A
prominent well-studied example that combines CO.sub.2-EOR and
CO.sub.2-sequestration is the "IEA GHG Weyburn-Midale CO.sub.2 Monitoring
and Storage Project." CO.sub.2 from the Great Plains Synfuel Plant in
Beulah, N. Dak. (USA) is piped 323 km for injection into the Weyburn and
Midale oilfields in Saskatchewan, Canada (Wikipedia entry: Weyburn-Midale
Carbon Dioxide Project; Whittaker et al., 2011; NETL/DOE, 2015; PTRC,
undated; Cenovus Energy, undated; Apache, undated). More than 25 million
tonnes of injected anthropogenic CO.sub.2 already have been stored in
these oilfields via CO.sub.2-EOR stimulation of oil production. The
average rate of injection has been .about.3 million tonnes (MT) CO.sub.2
per year. About 40 to 60 MT CO.sub.2 is expected to be sequestered in the
course of extracting approximately 215 million barrels of excess oil
production overall (Whittaker et al., 2011). CO.sub.2-EOR with associated
CO.sub.2 sequestration is a relatively well-developed technology in the
USA. The an overall injection rate for US CO.sub.2-EOR is about 60
million tonnes CO.sub.2 per year (MTA), circa 2015 (Hill et al., 2013).
This generates in excess of 100 million barrels per year of incremental
crude oil production (NETL/DOE, 2010; Hill et al., 2013. See Jaramillo et
al., 2009, Azzolina et al., 2015 and Cooney et al., 2015, for CO.sub.2
Life Cycle Analysis, LCA, of CO.sub.2 EOR). At present, however, for
viable industrial production processes other than CO.sub.2-EOR and
natural gas-based urea production, special circumstances and innovation
appear to be required to bring together captured CO.sub.2 output
availability at low cost with value-creating CCU on a large scale.
[0053] Plentiful rift-based oils are present in the Albertine graben in
Western Uganda bordering the Eastern DRC (Lirong et al., 2004a,b; Gao,
2012; Abeinomugisha and Kasande, 2012; Karp et al., 2012). Substantial
reserves have been proven on the eastern shore of Lake Albert. A total of
.about.6.5 billion barrels is estimated for Uganda in this area (Nakhle,
2015; OIES, 2015). Recoverable reserves are estimated at roughly 1.5 to 2
billion barrels (OIES, 2015; Nakhle, 2015; Jarrett, 2014; Powell, 2014).
Exploration blocks to the south near Rwanda bordering Lake Edward also
have been drilled with substantial oils reserves discovered (URN, 2010).
Discussions of pipeline technologies for the possibility of the transport
of the Albertine rift's crude to the distant East African coast indicate
most oils are heavy (API .about.19 to 33), viscous (cP .about.40), and
wax-rich (.about.19%). Heating and/or solvent addition is required both
for extraction and pipeline transport of this type of crude. Reports
suggest the oils pour only above 40.degree. C., and will flow efficiently
in pipes only above 60.degree. C. (Jarvie et al., 2007: Deep Earth, 2015;
Ochan and Amusugut, 2012; Open Oil, 2012). Operational problems in
producing and transporting such oils include precipitative clogging by
wax and asphaltene precipitation both of the reservoir during extraction,
as well as pipeline clogging above ground. Oils of this type are
expensive to extract and trade at a discount. Efficient production
requires specialized technologies (Oil in Uganda, 2014).
[0054] Oil reservoir rocks in the Albertine Graben in the region of Lake
Albert typically are sandstones, often with calcium carbonate pore
cementing (Ochan and Amusugut, 2012; Karp et al., 2012).
[0055] Hard-to-produce heavy oils are abundant worldwide. They exist in
amounts exceeding the scale of all conventional reserves prior to
extraction. Heavy oils represent a major focus of effort for development
of economically viable extractive technologies (Chopra et al., 2010;
Alboudwarej et al., 2006). CO.sub.2-EOR typically is considered to be a
technique restricted to non-heavy oils (NETL/DOE, 2010; Shell, 2012).
However, injected CO.sub.2 has long been used successfully to pressurize
depleted heavy oil fields via immiscible CO.sub.2 flooding (Gao et al.,
2013; Emadi et al., 2011). Prominent examples reviewed by Gao et al.,
(2013) include the Lick Creek Field in Southern Arkansas (USA, Reid and
Robinson, 1981), the Wilmington Field near Los Angeles, the Bati Raman
field in SE Turkey (See also: Kok and Ors, 2012; Ansarizadeh et al.,
2015), the Liaohe Field in NE China, and the Forest and Oropouche fields
in Trinidad. In most CO.sub.2-EOR operations, a substantial fraction of
CO.sub.2 remains sequestered in the formation. And CO.sub.2 co-produced
with oil can be separated and recycled into continuing CO.sub.2-EOR
injection. Consequently, efforts are being made to develop efficient
heavy oil extraction technologies to expand use of CO.sub.2 in heavy oil
production combining extractive efficiency goals with environmental
CO.sub.2 sequestration goals (Whittaker, 2015; Emadi et al., 2011; Gao et
al., 2013).
[0056] One such strategy is known as VAPEX (vapor extraction). VAPEX has
been extensively piloted in the field. It is based on phase
transformation for vapor extraction without a necessity for heat addition
(Butler and Mokrys, 1991; Upreti et al., 2007). As VAPEX technologies
have developed, CO.sub.2 addition has become prominent. VAPEX operates by
the solvent action of horizontally injected solvent-gas "vapor chambers."
These mobilize heavy oils on their expanding peripheries. This creates
flow conditions for solvent-mobilized oil migration into adjacent
horizontal extraction well systems. Efficient VAPEX injection schemes
include CO.sub.2 admixed with depressurization-recoverable light
hydrocarbon gas co-solvents such as propane. Recent results have refined
understanding of this method for field applications. In particular,
recent research has found CO.sub.2 to be an optimal co-solvent with
propane (Tchambak et al., 2012; Torabi et al., 2012; Jahaveri, 2013;
Bayat et al., 2015a,b,c; Mohammadpoor and Torabi, 2014, 2015a,b). A
general advantage of CO.sub.2 injection under both miscible and
immiscible conditions is CO.sub.2 absorption into heavy oil causing
viscosity decrease and volumetric swelling. This creates reservoir
pressurization and oil mobilization, increasing extraction performance
(Klins, 1982; Sahin et al., 2007, 2012; Gao et al., 2013). Future
developments are likely to utilize CO.sub.2 across a range of
cost-minimized injection technologies that simultaneously sequester
CO.sub.2 while producing heavy oils efficiently. CO.sub.2 already can be
utilized across a range of circumstances and technologies in heavy, waxy
and asphaltene-rich oil production. A key economic factor apart from the
market price of oil is the availability large quantities of
pipeline-accessible low-cost CO.sub.2 (Wei et al., 2015; Advanced
Research International, 2006).
[0057] Examples of further innovations utilizing CO.sub.2 in EOR include:
(i) Carbonated Water Injection (Shu, 1982: U.S. Pat. No. 4,441,555,
"Carbonated waterflooding for viscous oil recovery"; Perez et al., 1992;
Sohrabi et al., 2011; Gao et al., 2013; Zuo and Benson, 2013; Mosavat,
2014; Seyyedi and Sohrabi, 2015); (ii) surfactant-generated CO.sub.2
foams (Enik and Olsen, 2011; Sohrabi, 2012, 2013; Daraei et al., 2015;
Sagir et al., 2015); and (iii) alkali (including sodium carbonate)
stabilization of CO.sub.2 foams (Farzaneh and Sohrabi, 2015). Carbonated
Water Injection (CWI) has long been known to be a means of increasing
reservoir porosity in carbonate host rock oil reservoirs (Holm, 1959).
Success in oil recovery enhancement from CO.sub.2 dissolving of carbonate
host rock to increase porosity is well demonstrated in the Bati Raman
field of SE Turkey (Sahin et al., 2007). CWI can be a useful method for
liberating oil in low porosity reservoir sandstones cemented by calcium
carbonate (Qiao et al., 2015).
[0058] CO.sub.2 increasingly is being used as a fracking fluid to promote
"tight" oil production from low-porosity sources. CO.sub.2 and
CO.sub.2-admixed fluids used in such advanced fracking efforts exhibit
certain advantages in some rock types for both gas and oil extraction
(Schlumberger, undated; Praxair, undated; Song, 2013; Jacobs, 2014;
Sorensen et al., 2014; Geiver, 2015; Fergus, 2015; Gong and Yu, 2015;
Jung et al., 2015; Middleton et al., 2015; Yu et al., 2015).
[0059] CO.sub.2 is utilized for enhanced recovery of natural gas. Enhanced
Gas Recovery (EGR) proceeds by injection of CO.sub.2 into gas fields for
the purpose of re-pressurizing natural gas flow into extraction wells.
The field has been researched for over 15 years (Oldenburg and Benson,
2001; Oldenberg, et al., 2001; Oldenberg, 2003a,b). It couples increased
resource extraction with CO.sub.2 sequestration. The basic process seeks
to avoid mixing of natural gas with injected CO.sub.2. The role of
CO.sub.2 is to pressurize methane along a moving front of expanding
CO.sub.2 from injection sites towards extraction wells (TNO, 2008; van
der Meer et al., 2009; Hughes et al., 2012; Hussen et al., 2012; Honari
et al., 2013, 2015; Kuhn et al., 2012, 2013; Khan et al., 2013a,b; Gou et
al., 2014; Leeuwenburgh et al., 2014; Klimkowski et al., 2015; Kuhn,
2015). EGR research suggests it will be extended for use in the arena of
"tight gas" (fracking-based extraction), (Li and Ellsworth, 2014; Kulga
et al., 2014).
[0060] CO.sub.2 similarly can be utilized by injection into deep coalbed
deposits as a means of enhancing the extraction fraction of coalbed
methane (CBM) while simultaneously sequestering CO.sub.2 in a
"CO.sub.2-ECBM" process (Busch and Gensterblum, 2011; Godec et al., 2014;
Li and Fang, 2014; Litynski et al., 2014). The technology has been shown
to be effective, especially with special reservoir development involving
co-injected nitrogen and involving other technologies to avoid porosity
closure due to coal swelling from CO.sub.2 absorption. Commercial takeoff
of this form of CO.sub.2 utilization, however, appears to require a
carbon tax environment with sequestration credit payments (Sloss, 2015).
[0061] The European CO.sub.2 Test Centre Mongstad (CO.sub.2-TCM) is
located near Bergen Norway on the site of Norway's largest oil refinery.
A natural gas power plant is present within the industrial complex. The
CO.sub.2-TCM is one of the world's largest industrial joint ventures for
development of large-scale CO.sub.2 capture technologies (MIT, 2015b).
CCU, however, was not a component of the venture until development of the
"CO.sub.2 to Bio Project" in 2011-2012 (CO.sub.2BIO, 2012). CO.sub.2BIO
is focused on utilizing CO.sub.2 as carbon source food input into
photosynthetic algal biocultures to produce aquaculture feeds rich in the
long-chain omega-3 lipids DHA and EPA. CO.sub.2BIO project produced a
report (Kleivdal et al., 2012) and a start-up company, CO.sub.2BIO AS
(www.co2bio.no). The initial agenda of the company is to create a
piloting project at Mongstad. Norway is the world's leading nation in
production and innovation in salmon aquaculture. Scientists and fisheries
and government leaders recognize an important long-term strategic
necessity for the development of very large-scale business-viable
production of algae-derived omega-3-rich aquaculture feeds, especially
for salmon. This is necessary to replace unsustainable and escalating use
of forage fish for feeds. Escalating use of wild-caught forage fish for
aquaculture/mariculture feeds is grossly harmful to the sustainability of
world forage fish populations and their associated fisheries (Sorensen et
al., 2011; Kleivdal et al., 2013; BlueBio, 2013; Reitan, 2013. See also:
SARF, 2014). The Norwegian Parliament has granted US$1M to CO.sub.2BIO in
a research consortium to create a 350 square meter greenhouse pilot
testing facility adjacent to the Mongstad CO.sub.2-TCM. Construction was
scheduled to begin in 2015 (Holm, 2015; Kleivdal, 2015). However,
CO.sub.2BIO perhaps is unlikely to create large-scale algal production
operations adjacent to Mongstad. Mongstad therefore is not an example of
a CCU-focused industrial eco-park.
[0062] Eco-Industrial Parks (EIPs, see Wikipedia entry and, Making Lewes,
undated) are a widespread mode of industrial aggregation focused on
systematic recycling of waste outputs into production inputs, often
described by the term "industrial ecology" (Garner and Keoleian, 1995).
To date, no EIP has been developed with a core focus on carbon capture
utilization (CCU). A few examples exist of "industrial symbiosis" between
paired companies. The Ulsan Eco-Industrial Park in Korea includes a
linkage between a zinc plant producing waste CO.sub.2 and steam, and a
paper plant using CO.sub.2 and steam. These plants are connected by a 3.8
km pipeline (Park, 2013). The Herdersbrug eco-industrial park in Belgium
has qualified itself as "carbon neutral." However, it does not
incorporate any CCU industrial activities (Block et al., 2011). The
"Industrial Estate Moerdijk," in the Netherlands, includes an
"Experimental Garden." This eco-park section connects CO.sub.2-produced
in a sewage incinerator with CO.sub.2 use by the Swiss company, Omya.
Omya produces precipitated fine calcium carbonate sold into the paper
industry as a whitener pigment (GreenPort, 2009). Shell Chemicals also
supplies waste CO.sub.2 to Omya at this location (Royston, 2012).
"Bioport Terneuzen" is an eco-park located in the Dutch port of Zeeland,
between Antwerp and Rotterdam. It includes a coordinated CO.sub.2
industrial symbiosis between several CO.sub.2 and heat producers,
including a Yara fertilizer plant, and a network of adjacent commercial
greenhouses, "Glastuinbouw Terneuzen" (WarmCO.sub.2, undated; Rijckaert,
2009; Nuhoff-Isakhanyan et al., 2015). Iceland's Svartsengi Geothermal
Resource Park combines geothermal power and district heating operations
connected with Carbon Recycling International's "George Olah CO.sub.2 to
Renewable Methanol Plant" (Prakash, 2013, 2014). CRI's methanol plant
utilizes electrolytic hydrogen (using geothermal power) and
geothermally-derived CO.sub.2 flux from the powerplant (Hettinga, 2013;
Sigurbjornsson, 2013). Industrial ecology parks based on CO.sub.2
production linked with diversified utilization have been strategized
(Meylan, 2015), and modeled (Norstebo et al., 2012). However, none thus
far have been specifically designed.
[0063] CO.sub.2 hubs may be defined as industrial methods, designs and
realizations having three main components interlinked to each other. The
first is one or more CO.sub.2 sources. Sources may be natural, such as
extraction from a drilled CO.sub.2 well. Or they may be from natural
source via an industrial separation process such as removal from natural
gas in natural gas upgrading. Or CO.sub.2 sources may capture CO.sub.2
from industrial waste gas streams, for example by capture-separation of
CO.sub.2 from post-combustion exhaust of a powerplant. Sources inputting
CO.sub.2 into a hub system may involve combinations of any or all of
these source types. The second component is that which connects the first
component to the third component focused on utilization of CO.sub.2. This
second is the core of the hub. It is that which distributes and, if
necessary beforehand separates and purifies CO.sub.2, and if necessary
stores and variously, as needed, compresses and/or refrigerates, the
CO.sub.2 obtained from sources. This is a system of tanks, pumps,
compressors, gas treatment facilities, valve systems and pipelines. The
third component is the sink for CO.sub.2 utilization and/or
sequestration. This involves methods, designs and realizations which
sequester and/or utilize CO.sub.2. Utilization involves industrial and/or
agricultural and/or aquacultural use for purposes gaining economic
utility from consuming a supply of CO.sub.2. Thus far, all CO.sub.2 hubs,
strategized, planned or realized, principally are focused on CO.sub.2
sequestration, CO.sub.2-EOR, or greenhouse horticulture, or urea or
methanol production. With the exception of the Green Pipeline system
(which is geographically dispersed over a very long distance and is not
per se a hub), no CO.sub.2 hubs yet exist where the principle focus for
CO.sub.2 distribution involves a gathering together of industrial
activities assembled for the purpose of waste CO.sub.2 utilization
different from providing supply for CO.sub.2-EOR alone, or for greenhouse
horticulture alone, or for CO.sub.2-EOR and greenhouse horticulture in
combination (as planned for the Port of Rotterdam), or for urea
production alone, or for methanol production alone, or for calcium
carbonate production alone. (For a partial global summary, see: Der,
2014, slide #9 and Haszeltine, 2015, slide 38.)
[0064] Rotterdam provides a city-centered model of a CO.sub.2 hub linking
captured CO.sub.2 outputs from refinery and bioethanol production waste
to agricultural use of CO.sub.2 in greenhouse culture of flowers and
vegetables (Rotterdam Climate Initiative, 2011; OCAP, 2012; van
Engelenburg, 2012; Linde, 2013b, 2014; Ros et al., 2014; Port of
Rotterdam, undated). The Port of Rotterdam's distribution network handles
.about.0.5 MTA CO.sub.2. It supplies almost 600 greenhouses via a
.about.300 km network of pipelines. Greenhouse demand for the CO.sub.2,
however, is seasonal whereas CO.sub.2 source output is roughly constant
over time. Plans remain uncertain for a possible major scale-up called
the ROAD project. ROAD aims to integrate the existing CO.sub.2 hub with a
new pipeline network for offshore subsea CO.sub.2 storage linked with
offshore CO.sub.2-EOR (Carbon Capture Journal, 2014; Read et al., 2014;
Read 2015a,b; Tillema, 2015). The City of Rotterdam's agenda is to
develop the largest-scale CO.sub.2 hub in Europe. The plan involves a
network of companies called "CINTRA," an acronym for "Carbon In
Transport," (CINTRA Factsheet, 2011). CINTRA is part of the ROAD
initiative. ROAD is an acronym in Dutch for: "Rotterdam capture and
storage demonstration." It is a sub-unit of the Rotterdam Climate
Initiative (Tillema, 2015; Read, 2015a,b; van Tongeren, 2011; Radgen,
2015; Read et al., 2014; Neele et al., 2014; Singh and Haines, 2014;
www.rotterdamclimateinitiative.nl; IEAGHG, 2015). The agenda for the
CINTRA consortium is: (i) to create the Port of Rotterdam CO.sub.2 hub
linking incoming CO.sub.2 from a network of onshore pipelines into a
network of subsea offshore CO.sub.2 pipelines, and (ii) also to create a
capacity for loading of liquified CO.sub.2 onto transport ships docking
in the Port of Rotterdam (Loeve et al., 2013), and into the tanks of
tanker trucks for road deliveries.
[0065] Creation of the type of capacity the Port of Rotterdam plans for
diversified CO.sub.2 delivery requires a compression pumping station with
temporary storage for pressurized CO.sub.2, as well as a
refrigeration-liquefaction plant and adjacent storage tanks for liquid
CO.sub.2 sufficient in volume to allow rapid loading onto transport ships
(Groensmit, 2010; van der Ben, 2011; de Wolff et al., 2013). An
engineering overview for a CO.sub.2 hub operating in a port is provided
by Suzuki et al., (2013).
[0066] The Belgian Port of Antwerp is developing plans to reproduce
Rotterdams's example. Antwerp hosts the largest integrated refinery
complex in Europe (Callebaut, 2015). Most other European initiatives for
large-scale CCU, are focused on CCS, variously linking North Sea CO.sub.2
sequestration-storage together with CO.sub.2-EOR opportunities. These
efforts are reviewed by Kjarstad et al., (2014), Brownsort et al.,
(2015), and Scottish Enterprise--SCCS, (undated).
[0067] Links between CO.sub.2 emitters and CO.sub.2 utilization for
greenhouse fertilization are widespread. Greenfield Specialty Alcohols
(www.gfsa.com) of Chatham, Ontario (Canada) operates in a local
industrial symbiosis with the greenhouse tomato grower Truly Green Farms
(http://www.trulygreenfarms.ca). Ethanol production provides waste heat
and CO.sub.2 to the greenhouses (Jessen, 2013; GreenEnergyFutures, 2014).
A similar situation exists in Sweden linking a distillery with a tomato
grower (Advantage Environment, 2013). In 2015, the company Linde Gas
Turkey commissioned a CO.sub.2 purification and liquefaction plant to
capture geothermal CO.sub.2 from the Zorlu Energy geothermal power plant
near Denizli to supply an initiative to create an "Organized Greenhousing
Zone" in the region (Cockerill, 2015).
[0068] Temporary CO.sub.2 storage associated with utilization is required
for "dry fracking" of oil and gas extraction wells with CO.sub.2.
Injections of CO.sub.2 to dry frack a single well may require up to 6,000
tonnes of CO.sub.2 (Sears and Feve, 2014). Stored CO.sub.2, if in
refrigerated liquid form, typically is reheated before subterranean
injection (Liebscher et al., 2013).
[0069] Capabilities for cryogenic capture and storage of gases can be an
important mode in advanced powerplant operations. Cryogenic capturing of
CO.sub.2 can be useful for purification of input natural gas containing
associated CO.sub.2 in addition to being an effective means of capturing
CO.sub.2 in post-combustion exhaust. Cryocapture and storage of various
gases, including O.sub.2, N.sub.2, CO.sub.2, CH.sub.4 and air, can be
used as a means of high-efficiency power storage via Cryogenic Energy
Storage, CES (see: Wikipedia entry: Cryogenic Energy Storage;
www.highview-power.com; Highview Power Storage, 2014, 2017;
www.dearman.co.uk; Center for Low Carbon Futures, 2013; Strahan, 2013;
Brett and Barnett, 2014; Abdo et al., 2015; Morgan et al., 2015; Starns
et al., 2015; Liquid Air Energy Network, undated; Tweed, 2015;
www.keukaenergy.com; Zhang et al., 2015a,b; Chen et al., 2009;
www.sesinnovation.com; Baxter, 2015, 2015 video, 2016a,b; Baxter et al.,
2016; Safdarnejad et al., 2015; U.S. Pat. No. 9,410,736, Baxter, 2011,
"System and Methods For Integrated Energy Storage And Cryogenic Carbon
Capture"; Jensen, 2015; Ebahimzadeh, 2016; Fazlollahi, 2016; Fazlollahi
and Baxter, 2015). Cryogenic production of such liquified gases by an Air
Separation Unit (ASU) equipped with adjunct CES power generators can
allow a powerplant to store and release energy as needed in order to vary
its sales electricity output over time while producing power from its
main power source at a continuous rate of output, if desired. If a
powerplant operates with air cryo-processing, as for example an oxyfuel
powerplant does to provide O.sub.2 gas into combustion, then such a
powerplant can use CES to modulate its disposition of electric power over
time. The plant uses its power output "internally" to build-up stored
cryoenergy reserves. It then converts these cryo-energy reserves in times
of high demand (and high prices) in order to maximize sales of electric
power. CES systems store cryogenically liquified gases in one or more
thermally insulated reservoirs. Additionally, a powerplant with cryogenic
energy storage capacities can provide valuable grid-balancing services
both for power intake and output. These can be useful especially for
incorporation of renewable power inputs into an electric power grid. Wind
and solar inputs, as well as small- and micro-hydropower inputs, often
are highly irregular and unpredictable in time and scale.
[0070] Both liquefied oxygen and nitrogen are produced by an ASU if it is
of the cryogenic type. Both gases can be sold as pressurized bottled
and/or cryogenic gas products. Both can be utilized for cryogenic energy
storage for electric power output modulation. Uses for pressurized or
liquefied oxygen are many. Uses for pressurized and/or cold liquefied
N.sub.2 also are many. They include: (i) cooling-refrigeration, such as
of a data center, or for transportation cooling food storage in trucks;
(ii) fumigation of stored crops or of horticultural greenhouses overnight
(by blowing-in an N.sub.2 or N.sub.2--CO.sub.2 atmosphere to asphyxiate
oxygen-respiring pests) with or without cooling; (ii) N.sub.2-EOR,
"waterless" N.sub.2-fracking, and "waterless" N.sub.2 cryogenic fracking
(Higgins, 2015; Cai et al., 2015; Cha et al., 2015; Crawford, 2015);
(iii) solvent switching in switchable ionic liquids using CO.sub.2 as a
switching gas and N.sub.2 for return; (iv) canopy gas for algal biomass
production in situations where avoidance of atmospheric O.sub.2 is
desired; (v) sparging gas for removal of O.sub.2 and/or CO.sub.2 from
solution (Al-Mashhadani et al., 2012); (vi) numerous medical and
laboratory uses; (vii) rapid deep freezing of foods; (viii) a carrier gas
for chemically reducing uses of carbon monoxide, for example tin
smelting; (ix) input into the production of chemicals, for example
ammonia and urea; (x) for humane animal slaughter, (xi) pressurizing gas
input for beer preparation, and (xii) cryogenic energy storage (CES).
[0071] Both gaseous and liquefied nitrogen gas (LN.sub.2) is a byproduct
of air separation by cryogenic air separation units used to obtain
separated oxygen for purposes such as oxyfuel combustion. In the process
of air separation, liquefied nitrogen is used to cool incoming air via
heat exchange processes. This recycles cryo-energy and creates waste
flows of pure N.sub.2 gas that can be utilized. Excess liquid nitrogen
also is created as a waste in so far as it does not need to be saved for
use in oxycombustion. It can be vented to the atmosphere. This can be
done as a means of generating electricity, utilizing cryo-energy. A
power-generating turbine based on LN.sub.2 runs by the expansion of
liquid nitrogen into gas consequent of heat exchange with the ambient
atmosphere. It uses the same logic and design as liquid air engines and
power generators (https://en.wikipedia.org/wiki/Cryogenic_energy_storage;
www.dearman.co.uk; https://en.wikipedia.org/wiki/Liquid_nitrogenvehicle).
Additional efficiency-boosting aspects of integration of ASU nitrogen
with an oxyfuel powerplant are described in Aneke and Wang, (2015).
[0072] Professor Larry L. Baxter of Brigham Young University, and several
university collaborators and co-workers in a start-up company, SES
Innovation (www.sesinnovation.com), have developed commercialized
technologies for efficient cryogenic capture of CO.sub.2 from coal-based
power plant flue gases. Baxter's technologies connect CO.sub.2 capture
and storage with powerplant cryogenic energy storage. They allow the
powerplant to operate with an efficient stable power output over 24 hour
cycles while maximizing the sale of electricity at times of high demand
(and higher sales price), minimizing electricity sales at times of lower
demand (and lower sales prices). Such output variability can be supported
by using electricity internally to build-up cryogenic coolant reserves at
times of lower demand within the 24 hour cycle. Stored cryogenic reserves
of cryo-energy then are utilized to produce power at times of high
demand. Systems designed by SES Innovation also allow dry ice production,
refrigeration of natural gas into LNG, and utilization of liquid nitrogen
for power production in the case of power plants linked with Air
Separation Units (ASUs) such as oxyfuel power plants (Baxter, 2015,
2016a,b; Safdarnejad et al., 2015; Fazlollahi et al., 2015; Ebrahimzadeh,
2016; Ebrahimzadeh, et al., 2016; a,b; Fazlollahi, 2016; Jensen et al.,
2015; http://www.sesinnovation.com/technology/carbon_capture/ES/; Baxter,
U.S. Pat. No. 8,715,401 B2, "Methods and systems for condensable vapors
from gases"; Baxter, US 2013/0139543 A1, "Systems and methods for
integrated energy storage and cryogenic carbon capture"; Baxter and
Bence, U.S. Pat. No. 8,764,885 B2, "Systems and methods for separating
condensable vapors from gases by direct-contact heat exchange"; Baxter,
US 2011/0226010 A1, "Carbon dioxide capture from flue gas"; Baxter, U.S.
Pat. No. 8,963,347 B2, "Methods and systems for generating power from a
turbine using pressurized nitrogen"; Baxter: WO2013062922A1, "System and
Methods For Integrated Energy And Cryogenic Carbon Capture"; Fazlollahi
and Baxter, 2017; Fazlollahi et al., 2016a,b) The energy cost for
CO.sub.2 capture in Baxter and colleagues' latest model for application
of their (bolt-on) technology to a coal-fired power plant is:
0.74MJe/kgCO.sub.2 (Jensen et al., 2015). Cryogenic separation of
associated CO.sub.2 from natural gas also is a function that can be
coupled with the cryogenic capacities noted above developed by Baxter and
colleagues. Round trip efficiency for cryo-energy storage by LNG is
expected to be able to exceed 95% (Park et al., 2017).
[0073] Cryogenic separation is the standard technology for obtaining large
quantities of oxygen gas for industrial purposes such as oxyfuel
combustion. However, another technology exists approaching large-scale
commercial applicability. This is Ion Transport Membrane technology
(ITM). The US company Air Products (www.airproducts.com) has developed
and piloted a modular ITM technology. Progress to date suggests it may be
capable of being scaled to a minimum .about.2000 TPD output size module
needed for clean coal oxyfuel powerplants (Repasky et al., 2012, 2013a,b,
2014; Anderson et al., 2011, 2015).
[0074] CCU is well developed in the greenhouse horticulture industry. It
provides the carbon feed source for accelerated photosynthesis at
enhanced CO.sub.2 concentrations, typically 2.times. to 3.times. the
present atmospheric concentration of 400 ppm (dry air molecular mole
fraction). In the interval 1998 and 2003, the Dutch company Ecofys
developed a "closed" greenhouse model incorporating a powerplant within
the greenhouse system producing electric power, heat and CO.sub.2 (Opdam
et al., 2005; et al., 2005; Gelder et al., 2005). This created a CCU
business model based on combining CO.sub.2 production for horticulture
with natural gas electric power generation using small powerplants
installed individually within greenhouse complexes. The new mode of
high-efficiency greenhouse horticulture spread rapidly (van der Veen,
2012). General Electric (GE), Cummins Engine, and Rolls Royce all offer
natural gas-powered combined heat and power (CHP) generator systems for
greenhouse use. These systems generate electrical power for greenhouse
and heating and lighting and other operations. They also provide CO.sub.2
from the engine's exhaust plus waste heat. Engine exhaust is cleaned of
CO and nitrogen oxides (GE, undated; Commercial Greenhouse Grower, 2012).
In the Netherlands, greenhouse businesses using CHP systems sell excess
power locally or into the grid (Tasin, 2005; Campernolle et al., 2011;
Clarke Energy, undated; Yates, 2012; De Wit, 2014; Power Engineering,
2014; GE, undated). CHP exemplifies profitable CCU. At cold times of the
year when greenhouses need heat and often use artificial lighting,
systems can have close to 100% utilization of the total chemical energy
of the natural gas utilized by the CHP engine power generator. One
example of a CHP user is the Dutch tomato growers cooperative "Prominent
Growers" (District Energy, 2015). Another is the very large Thanet Earth
greenhouse complex in SE England. Thanet Earth combines three different
greenhouse companies, together utilizing GE CHP systems for combined
power, heat and CO.sub.2 (WSGA, undated). Another example is greenhouse
tomato grower Springhill Nursery near Evesham in England. Springhill
powers its CHP powerplant with biogas from on-site anaerobic digestion
(HDC, 2014). Wright Salads, Ltd., of the Isle of Wight is another
UK-based greenhouse grower using CHP systems (36 MW), (Bower, 2013). A
prominent example in the USA and Canada is Houweling's Tomatoes.
Howelings operates GE CHP-based greenhouses in Southern California
(Yates, 2012) and BC Canada (Houwelings, undated). In 2014, Houwelings
built a third high-tech greenhouse in Mona, Utah. This greenhouse is
linked with power, waste CO.sub.2 and heat from an adjacent power plant
burning natural gas (Houweling's, 2014, undated; Abcarian, 2015). None of
these systems, however, offer multi-product CCU platforming beyond
horticultural products.
[0075] "Agriport A7" (http://www.agriporta7.nl;
http://www.bezoekagriport.nl/en/home-2) is a Dutch coordinated private
association cluster of greenhouse growers and related packaging and
logistics companies operating on a very large scale: >1000 hectares.
Agriport utilizes several GE CHP systems (Nuhoff-Isakhanyan et al., 2015;
Smits, 2014; Buurma and Ruijs, 2011; Neville, 2009; Vale, 2008). It has
expanded to include associated livestock, dairy and fish production.
Agriport A7 additionally includes a 38-hectare Microsoft data center
utilizing local electricity produced from natural gas. It provides waste
heat into the greenhouse complex. Moreover, Agriport A7 has accreted a
business park (Metropolitan Food Clusters, 2013). However, CCU has not
been developed at Agriport A7 beyond the core industrial symbiosis
connecting CHP systems with greenhouses.
[0076] The urban vertical greenhouse design company Plantagon offers an
urban vision for greenhouse-linked CHP (Plantagon, undated, 2015).
[0077] CO.sub.2 began to be used as a refrigerant system thermodynamic
fluid in the 1850s. It became the dominant refrigerant for 100 years (Kim
at al., 2004; Pearson, 2005; Austin and Sumathy, 2011; Harris, 2014). For
over 75 years it has been known that heat engine CO.sub.2 power cycles
(that is, heat engines using CO.sub.2 as a thermodynamic "working fluid")
are potentially hyper-efficient and have great potential (Hochstein,
1940; Angelino, 1968; Feher, 1968; Yantovskii et al., 1993, 2009; Wall et
al., 1995; Ausubel, 1999, 2004; Dostal et al., 2004; Bahamonde Noriega,
2012; Kim et al., 2012; DOE/NETL, 2012; Wright, 2012). Possibilities
include fossil-fueled open system turbine power. Closed-cycle heat engine
applications of CO.sub.2 power cycle technology include solar-thermal
power converters, nuclear power systems, geothermal power systems,
hyper-efficient jet engines, and solar-electric propulsion (Brown, 2000;
Ahn et al., 2015; Ausubel, 2004; Daniels, 2015; Colonna, 2016; Schuwer,
2015; Neises and Turchi, 2014; Rochau, 2011, 2014; Cleanenergyauthority,
2012; Lee et al., 2012; Wright, 2012; Wright et al., 2012;
http://energy.sandia.gov/energy/renewable-energy/supercritical-co2/;
McClung et al., 2014; Tahil, 2014; Yeom, 2015; USDOE, undated). The
expected advantages of commercial development of CO.sub.2 power cycle
heat engines using supercritical CO.sub.2 are astonishing. They include
powerplant thermal efficiency boosting to .about.70% with radical
reduction in the volumetric size and complexity, hence cost, of turbo
machinery. The volume of space taken up by machinery can be decreased by
roughly a factor of .about.100. This is consequent of a much higher
density of the jetting supercritical fluid that transfers its flow
momentum into the extracted rotational power of spinning turbine blade
systems. Cost reduction scaling eventually should be by a factor of
.about..times.0.1 or better (Rochau, 2014; Wright, 2012). Environmental
advantages also are impressive via the possibility of compact Zero
Emissions Power Plants (ZEPPs). These provide streams of nearly pure
CO.sub.2 waste for utilization and sequestration without any necessity
for complicated, costly and energy-absorbing "CO.sub.2 capture" from
powerplant exhaust (Yantovskii et al., 1993; Ausubel, 1999; 2004; Foy and
Yantovski, 2006; Yantovsky et al., 2009). In an oxyfueled ZEPP, whether
using a supercritical CO.sub.2 power cycle or not, the exhaust is a
mixture of CO.sub.2 and condensable water such that "CO.sub.2 capture" is
unnecessary. Only CO.sub.2 sequestration or utilization is needed.
[0078] Commercialization of a closed CO.sub.2 cycle system has been
accomplished by the US company Echogen (www.echogen.com) for power
production utilizing waste heat. Echogen supercritical CO.sub.2 cycle
systems add a second heat engine onto power systems to capture waste
heat. This boosts efficiency via bolt-on Combined Cycle Power (CCP). The
resulting output boosting is about one third on a constant fuel input
basis (Persichilli et al., 2012; Held, 2014; Echogen, 2012, 2014. See
also: www.tharenergyllc.com and Chordia, 2015).
[0079] Three start-up companies appear to be creating additional
commercial supercritical CO.sub.2 closed cycle heat engines. Peregrine
Turbine Technologies, LLC, (www.Peregrineturbine.com), based in the State
of Maine, USA, appears to be creating a compact power-generating
multi-fuel turbine heat engine based on a closed supercritical CO.sub.2
power cycle (Fishell, 2015; Valigra, 2015; Young, 2015). Supercritical
Technologies, Inc., (www.supercritical.tech) based near Seattle, in the
state of Washington, USA, appears to be creating a waste heat recovery
unit with a diurnal load-balancing energy storage capability using the
freezing and melting of water ice (Wright et al., 2014). Infinity Turbine
(www.infinityturbine.com) appears to be developing a waste heat capturing
heat engine.
[0080] The technology giant GE (General Electric) is developing a
supercritical CO.sub.2 power cycle turbine system. Initially, this
development activity is focused in the area of converting solar-thermal
energy into electricity (Allhart, 2016; Kalra et al., 2014; Hofer, 2016;
Apr. 13, 2016 online video, "May carbon dioxide turbine address clean
power generation?": https://www.youtube.com/watch?v=MsyUX4Qr5Vw).
[0081] Oxyfuel combustion technology has been developed for open cycle
turbine power production fueled by natural gas (Foy and Yantovski, 2006;
Jerica and Fesharski, 1995; Clean Energy Systems, 2006; Hammer et al.,
2009; Revzani et al., 2009; Woolat and Franco, 2009; Yantovsky et al.,
2009; Thimsen, 2014; Daniels, 2015; Hu and Yan, 2015; Stanger et al.,
2015). Modern commercialized oxyfuel turbines burning natural gas can
have high overall energy conversion (fuel to electricity) efficiencies
approaching 60%, including the energy used to obtain oxygen, typically
via an air separation unit, ASU. This high efficiency is retained with
intake of fuel gas containing extremely high associated CO.sub.2. Carbon
dioxide then acts as the primary carrier gas or "working fluid" in the
absence of the N.sub.2 intake that accompanies air as the source of
oxygen feeding into combustion. An oxyfuel turbine system burning natural
gas with very high associated CO.sub.2 and highly compressed intake
represents an open supercritical CO.sub.2 power cycle system. (NB: a
non-combusting working fluid is needed to keep turbine temperatures low
enough to be within an operational range. For combustion of pure methane
with pure oxygen, the "flame" is too hot for containment and momentum
transfer by flow through turbine fan blades.) The CO.sub.2 concentration
in methane fuel input gas in high thermal efficiency operations may
exceed 93% by mass in a two-component fueling mixture. Water vapor also
operates as an effective working liquid. Oxyfuel turbines utilizing an
infeed of 02 plus a CH.sub.4+(CO.sub.2+H.sub.2O) fuel mix exhaust a hot
mixture of CO.sub.2+steam. This may be used for various purposes directly
or with various degrees of condensation of the water vapor.
[0082] Oxyfuel turbine systems operating commercially in the oil and gas
arena have been developed by the US company Clean Energy Systems
(www.CleanEnergySystems.com) in partnership with the German technology
giant Siemens, and in concert with sales and field implementation by the
Danish oil and gas production company Maersk Oil (Anderson, 2001;
Anderson and Bischoff, 2003; Anderson et al., 2004, 2008, 2009, 2010,
2014; Siemens and Clean Energy Systems, 2006, 2012; Husted, 2009;
Devanna, 2007, 2011, 2012, 2013; MacAdam and Anderson, 2007; MacAdam et
al., 2007; Kapteijn et al., 2011, 2012; Clean Energy Systems, 2012;
Hollis et al., 2012; Peters, 2012; Hende and Bek-Pedersen, 2012; Pronske,
2013; Alford, 2014; Maersk Oil, 2012, 2013; Maslin, 2014; Henni, 2014;
Maersk Oil and CES, undated; www.cleanenergysystems.com; Several
presentations and videos may be viewed at
http://trigen.propeoplelabs.com). Maersk's initial "Trigen" system is a
modified 43 MW Siemens turbine. Its power rating has been increased to
.about.150 MW running in oxyfuel mode with high-CO.sub.2 fuel gas. The
modified turbine is known as an "OFT900" (Clean Energy Systems, 2012
video).
[0083] A turbine system for power generation combining oxyfuel combustion
with a supercritical CO.sub.2 power cycle (hence with a highly compressed
CO.sub.2-rich fuel infeed) is being developed for application for various
fuels, including natural gas, by a consortium including NET Power
(https://netpower.com), 8 Rivers Capital, CB&I, Exelon, and the
turbine-specialized Japanese technology giant Toshiba (Lu, 2014; Isles,
2014; Dodge, 2014; NET Power, 2013, 2015; Toshiba, 2013, 2014; Sasaki,
2014; Davison, 2015; 8 Rivers, 2015; Lignite Energy Council, 2015; Iwai
and Itoh, 2015; Iwai et al., 2015). The technology is known as the "Allam
cycle." It was developed by the British inventor Rodney John Allam, OBE,
winner of the 2012 Global Energy Prize (Allam, 2013; Allam et al., 2013,
2014; Allam et al., 2013: U.S. Pat. No. 8,596,075, System and method for
high efficiency power generation using a carbon dioxide circulating
working fluid; Global Energy Prize, 2012, 2013; BBC, 2013). Allam cycle
heat engines represent a massive breakthrough innovation for power
generation efficiency, system cost, and environmental advantages. The
Allam cycle uses CO.sub.2 inflow as a powerful efficiency advantage. It
therefore inverts the usual problem that high CO.sub.2 inflow with
methane fuel causes a decrease of power generation efficiency. Allam
cycle power generating systems include two design types: (i) a single
turbine version (Allam et al., 2013) and (ii) a double turbine version
(Allam et al., 2014). Several additional patents by Allam and colleagues
have been granted under 8 Rivers Capital, LLC as assignee. The design
recycles exhaust CO.sub.2 into the oxyfueled infeed gas flow. Thermal
efficiency for natural gas fueling (including oxygen generation) with
this exhaust recycling is expected to be .about.59% (Tata, 2015). While
Allam cycle technology is novel and advanced, capital costs for
powerplants are expected to decrease because of the simplification and
miniaturization effects of the supercritical CO.sub.2 power cycle on
turbine components.
[0084] Supercritical CO.sub.2 power cycle heat engines are a promising new
technology with wide application and a high technological readiness
level. Echogen's line of closed-cycle engines entered the commercial
power sector in .about.2014. Field testing of Toshiba's 50 MW natural gas
Allam cycle turbine engine is scheduled for .about.2016. Toshiba's
system, if successful, will offer CO.sub.2 outputs suitable for Carbon
Capture Sequestration (CCS) and Carbon Capture Utilization (CCU), --a
winning combination. Supercritical CO.sub.2 cycle heat engines offers
participants entry into a new greentech power economy via a fundamentally
superior technology relative to the classic use of steam in heat engines
that has energized the industrialization revolution for over 300 years
(Irfan, 2015). Linked with CCS and CCU, supercritical CO.sub.2 power
cycle technologies offer the possibility of widescale success of
strategies developed in the EU over the past decade to develop ZEPPs:
zero emissions electric power plants burning fossil fuels (cf.,
http://www.zeroemissionsplatform.eu/about-zep.html; ZEP, 2006, 2007;
Hage, 2007). These technologies also represent a key step towards
practical CCS in the US power generation sector. They have been
recognized accordingly in overviews of the US Department of Energy's most
recent Technology Readiness Assessment (DOE/NETL, 2015), and in its
latest Quadrennial Technology Review (DOE, 2015a,b; Daniels, 2015; Orr,
2015; http://www.netl.doe.gov/research/coal/energy-systems/turbines/super-
critical-co2-power-cycles; http://energy.gov/supercritical-co2-tech-team).
The USDOE has supported the commercial realization of innovative oxyfuel
turbine technologies since 2000 (Siemens, 2006; MacAdam and Anderson,
2007; Dennis, 2014). A global overview of research activities on
supercritical CO.sub.2 power cycles is provided in the PhD thesis of
Monge (2014).
[0085] Additional modes of CO.sub.2 utilization are many and varied.
[0086] CO.sub.2 can be utilized to increase the value of coffee exports
using a CO.sub.2 packaging atmosphere. In comparison with green coffee
stored in the traditional way in jute bags, bagging in sealed
CO.sub.2-filled bags has been demonstrated to increase quality evaluation
scores for green coffee. Evaluation was made for specialty grade status
after 12 months storage in hermetically sealed bags injected with
CO.sub.2 (Borem et al., 2013; Ribero et al., 2011).
[0087] CO.sub.2 has long been used as an asphyxiating and poisoning agent
for insect pests. It is especially useful as a non-pesticide "organic"
agent for fumigation of silos and other harvest storage containers (Jay,
1971; Jay & Pearman, 1973; Ryan, 2008a; Timlick, 2014). CO.sub.2 is
applied either directly as an asphyxiant, or together with low O.sub.2
(Neven 2003), or in combination with other specific poisoning agents such
as phosphine (ECO.sub.2FUME: Wilson, 2001; Cytec, undated; Valizadegan et
al., 2014), ethyl formate (Vapormate.TM.: Ryan and Bishop, 2003; Linde,
undated), ethanol vapor (Arevalo-Galarza et al., 2010) and various
insecticides (ENVIROSOL, Ryan, 2008b). CO.sub.2 is widely used in
Thailand as a storage insecticide applied to plastic-sealed bag stacks of
rice (FFTC, 2004). This method also has been tested with excellent
results in Spain (Rudevets et al., 2009; Pons et al., 2010) and Portugal
(Carvalho et al., 2012). Grain storage utilizing CO.sub.2 pest-control is
practiced in China on large scale (Daolin et al., 2007), especially in
combination with phosphine (Boaxing, 2008). Plastic silo bags are the
world's newest grain storage technology. The world's largest storage
facility using this technology is in Sudan. Silo bags are advertised to
be pest-resistant. This is because grain respiration inside them uses up
oxygen which is transformed into CO.sub.2. This automatically creates a
gas environment that kills insects (GrainSaver, undated). However, this
process does not stop early infestations before CO.sub.2 build-up. Direct
injection of a CO.sub.2 atmosphere into grain-filled silo bags before
sealing has been demonstrated to be a successful insecticidal method by
Milanesio, (2010, cited in Cardoso et al., 2012).
[0088] Vapormate.TM. is a combination of CO.sub.2 with ethyl formate,
noted above. It is widely used for insecticidal treatment of fresh fruit,
vegetables and other commodities prepared for export (Linde, 2014).
ECO.sub.2FUME is fumigant gas comprised of CO.sub.2 with 2% phosphine gas
(Cytec, undated).
[0089] CO.sub.2 also has been developed as a solvent-propellent for
outdoor industrial spraying of pyrethrum as a natural biological
insecticide (Trade names: Pestigas, Turbocide, SupaPy. Ryan et al., 2015;
www.supagas.com.au). This use was pioneered by the Tasmanian company
Botanical Resources Australia, BRA. BRA is the world's largest pyrethrum
grower (Ryan et al., 2015; http://www.botanicalra.com.au). CO.sub.2
utilization relates to pyrethrum-based organic insecticide production in
three ways. First, growth of Pryrethrum chrysanthemum plants (Tanacetum
cinerariifolium) is enhanced substantially by CO.sub.2 addition, with
increased pyrethrin yield per plant and shortened the period of growth to
harvest (Suraweera et al., 2015). Second, high-pressure CO.sub.2 is used
for extraction and refining of the insecticidal components in the dried
flowers (details provided below). Third, pyrethrum insecticides may be
purveyed in bottles of pressurized CO.sub.2 acting as both a solvent and
propellant, as noted above.
[0090] CO.sub.2 has been proposed and tested as an overnight insecticidal
fumigant for greenhouse horticulture in concentrations up to .about.10%
without harm to tomatoes. This method has demonstrated a .about.50% kill
rate on aphids (Goerke et al., 2005). It can be used in combination with
N.sub.2 for atmospheric replacement to exclude oxygen. This method has
been used for fumigation to kill snails in orchid greenhouse culture
(Pontaweesap et al., 2011). It is likely to be highly potent more
generally for insecticidal fumigation.
[0091] CO.sub.2 can be used for cold sterilization of milk, beer and
juices by "cold pasteurization" (Garcia-Gonzalez et al., 2007;
Spilimbergo et al., 2011; King, 2014). This method functions by means of
"dense phase" CO.sub.2 chemical interaction under high-pressure and
without heat addition. High pressure dense phase CO.sub.2 destroys the
cell membranes of bacteria and/or yeast. The method was developed and
tested for cold pasteurization of beer by the research group of Murat
Balaban at the University of Florida (Folkes, 2004; Dagan and Balaban,
2006; Balaban: U.S. Pat. No. 6,994,878B2; Balaban and Ferrentino, 2012).
Balaban's work was done in association with commercialization by Praxair
of a nearly identical method for cold-pasteurizing orange juice under
process trademark "Better Than Fresh.TM." (Connery et al., 2005; Kincal
et al., 2005; Fabroni et al. 2010). Taste testing showed no
distinguishable taste differences from unpasteurized beer.
[0092] Many studies have validated the use of dense phase CO.sub.2 for
sterilization-pasteurization of milk without application of heat
(Hotchkiss et al 2006: U.S. Pat. No. 7,041,327 B2; Werner and Hotchkiss,
2006; Hotchkiss et al., 2006; Damar and Balaban, 2006; Di Giacomo et al.,
2009; Singh et al., 2011; Hongmai et al., 2014; Zhou et al., 2015;
Bonnaillie and Tomasula, 2015; Ceni et al., 2016). This technology is
fully ready for industrial application in situations where large
quantities of food grade CO.sub.2 are available at low cost (Hagemeyer et
al., 2013: U.S. Pat. No. 8,563,067 B2). Low pressure CO.sub.2 also is
used as a milk preservative both for refrigerated raw milk (de los
Reyes-Gavilan et al., 2005). It also is used in modified atmosphere
packaging (MAP) to extend the shelf-life of pasteurized milk (Hotchkiss
et al., 1999; Singh et al., 2011). CO.sub.2 is a superior input for
optimization-modification of the pH of milk for cheesemaking (Air
Liquide, undated),
[0093] Apple juice (Ferrintio et al., 2009; Yuk et al., 2010), carrot
juice (Park et al., 2002) coconut water (Damar et al., 2009) and tomato
paste (Parton et al., 2007) similarly can be sterilized by cold
processing under pressure with dense phase CO.sub.2.
[0094] Low-pressure CO.sub.2 is utilized as a packing preservative in
modified atmosphere packaging (MAP) of many types of food (Linde,
undated; WITT, undated; Wikipedia: Modified atmosphere). Modified
Atmosphere Packaging (MAP) utilizes CO.sub.2 to extend the freshness
timescale of various fruits and vegetables, often in combination with low
O.sub.2 (Mattos et al., 2012). Two examples where packaging in a
CO.sub.2-enriched (and low-O.sub.2) atmosphere is known to add
substantially to shelf-life and flavor development are mangos (Galvis et
al., 2005; Ullah et al., 2009) and avocados (Kassim et al., 2013).
Enhanced CO.sub.2 is believed to suppress Krebs cycle enzyme reactions in
these and other fruits (Kader, 1986).
[0095] CO.sub.2 is a well-developed plant fertilizer input in greenhouse
horticulture (Enoch and Kimball, 1986; Atwell et al., 1999; BOC, undated;
Jablonski et al., 2002; De Gelder et al., 2012, 2014; Bishop et al.,
2014; Rodriguez et al., 2015). The scale of the effect of CO.sub.2
enhancement depends broadly on whether the plant utilizes a C3 or a C4
photosynthetic system (Taub, 2010; Sage and Zhu, 2011). Gains in C3
plants tend to be large. Sometimes they exceed a .times.2 yield doubling.
Gains from CO.sub.2 use in typical greenhouse-grown C3 crop yields range
from about a third for cucumbers and tomatoes (Atwell et al., 1999;
Dannehl at al., 2013) to 60% for roses (BOC, undated; Beeson and Graham,
1991). Greenhouse technology gains, especially the development of
low-ventilation quasi-closed systems, have driven a yield increase trend
over decades. The trend is due to gains from growth under enhanced
CO.sub.2. Yields for tomatoes in Dutch greenhouses, for example, have
more than doubled in two decades between 1983 and 2013: from .about.280
tonnes of fresh tomatoes per hectare per year to .about.625 tonnes (de
Gelder et al., 2012, 2014; Selina, 2015). C3 tubers are expected to have
an especially strong root crop yield response to enhanced CO.sub.2
(Miglietta et al., 2000). For example, cassava root dry mass more than
doubles with exposure to CO.sub.2.about.1.5.times. atmospheric (Rosenthal
et al., 2012). Other C3 tubers, such as Irish potatoes also respond to
CO.sub.2 fertilization with strongly enhanced growth (Haverkort et al.,
2013; Miglietta et al., 2000), sometimes as high as .times.2 (NIPCC,
2014). Sweet potato enhancements can be doubled (Czeck, 2014). Carrots,
radishes and turnips exhibit tuber mass yield increases up to doubling
(Idso and Kimball, 1989; Azam et al., 2013). Cotton (Gossypium hirsutum
L.), a C3 plant, yields increase by more than 40% (Mauney et al., 1994).
Ginger root (rhizome) mass more than doubles (Gaasemzadeh and Jaafar,
2011). The yield of the herb thyme (Thymus vulgaris) is more than doubled
when grown under enhanced CO.sub.2 (Tisserat, 2002). Thyme's active
herbal substance thymol, when grown in air with ultra-highly enriched
CO.sub.2, exhibited 317.times. the concentration of thymol compared to
thyme shoots grown in identical conditions except under normal
atmospheric CO.sub.2 (Tisserat and Vaughn, 2001). Yields from orange
trees (C3) double (Kimball, 2013). Dutch growers claim eggplant (C3)
yields are doubled (Rijckaert, 2009). Common beans (C3) exhibit yield
gains of 77% under enhanced CO.sub.2 (Bunce, 2014). Onion crops exhibit
increases from 32% to 44% (Daymondi et al., 1997). Grape (C3) yields
increase 36% (Kurooka et al., 1990). Orchid horticulture utilizes
CO.sub.2 in various special ways relating to the specialized ways orchids
use CO.sub.2 biologically via Crassulacean Acid Metabolism, CAM, with
nocturnal carbon uptake (Gouk et al., 1997, 1999; Yong et al., 1999;
Drennan and Nobel, 2000; Hew and Yong, 2004; Texiera da Silva, 2013).
Some growth increase effects in orchids from extreme CO.sub.2 enrichment
have been observed to exceed a factor of twenty (Norikane et al., 2013).
Vanilla (Vanila planifolia) is an orchid crop with obligate CAM
metabolism. It is grown extensively in Uganda and Madagascar. Rice, a C3
plant, exhibits enhancements of .about.20 to 35% with strong variability
by both cultivar and temperature condition (Wang et al., 2015; Hasegawa
et al., 2013; Baker et al., 1990). Some US strains have shown crop yield
increases as high as 71% with elevated CO.sub.2 (Baker, 2004). C4
corn/maize yield enhancements are substantial only in relation to
increased drought resistance and fertilizer levels (Bunce, 2014).
Enhanced sugar production from sugar cane (C4) with enhanced CO.sub.2 is
in in the range of .about.20 to 30% (Madan et al., 2014). Banana and
plantain (C3) biomass gains increase very strongly with CO.sub.2
enrichment (Schaeffer at al., 1996, 1999). However, no detailed studies
of fruit yields are published. The C3 bamboo species Aulonemia aristulata
exhibits a very strong CO.sub.2 effect with approximate doubling of
biomass growth (Grambone-Guarantini et al., 2013). Seedlings of the C3
tree species Eucalyptus grandis and Eucalyptus cladocalyx F. Muell., also
exhibit approximate doubling of biomass accretion with enhanced CO.sub.2
(Conroy et al., 1992; Gleadow et al., 1998). Similarly, oil palm
seedlings show very strong biomass growth response to excess CO.sub.2.
Photosynthesis rates are observed to triple with 3.times. atmospheric
CO.sub.2 (Ibrahim et al., 2010; Jaafar and Ibrahim, 2012; Ibrahim and
Jaafar, 2012). Banana, for which waste can be used for paper production
(Hussain and Tarar, 2014), is now grown commercially in greenhouses on a
scale from 100 to 5,000 hectares per country in: the Canary Islands,
Morocco, South Africa, Spain, Turkey, Israel and Cyprus (Gubbuk and
Pekmezci, 2004).
[0096] Spain's large complex of greenhouses on the Mediterranean coast
linked with a desalination plant near Almeria exemplifies the development
of economic clustering dynamics in greenhouse horticulture (Perez-Mesa et
al., 2015; Pardossi et al., 2004; FAO, 2013). About 30,000 hectares are
under greenhouse cultivation adjacent to Almeria (Jackson, 2015; Pardossi
et al., 2004). Annual revenues average about US$90,000 per hectare
(Hortidaily, 2014). Greenhouse horticulture has a long record of success
in boosting economic development in the Almeria region (Aznar-Sanchez et
al., 2011). Greenhouse horticulture also has been a source of
agro-industrialization in developing countries. Columbia is well known
for a landmark early success in developing flower exports (McQuaid,
2011). Columbia's example has been followed by Mexico, Morocco, Kenya,
and Ethiopia. Kenya now has three agri-export clusters: fish, coffee and
greenhouse-grown flowers. Mexico has developed three fruit clusters in
avocados, lemons and pineapples in addition to extensive greenhouse
cultivation of tomatoes (Galvez-Nogales, 2010; Selina, 2015). China has
been the most rapid large-scale developer of greenhouse production for
food production. Almost 4 million hectares are estimated to be under some
form of greenhouse protection in China (Yang, 2015). Ghana is considering
developing high intensity greenhouse vegetables production with advisory
assistance from Dutch expertise of Wageningen University (Saavedra et
al., 2014). South Africa and Australia are also building-up their
agriculture sectors in greenhouse production by collaboration with Dutch
experts (de Visser and Dijkxhoorn, 2011; Bundock, 2010). Burney et al.,
(2010) have advocated agricultural intensification as an excellent
strategy for CO.sub.2 utilization for mitigation of atmospheric CO.sub.2
build-up. Greenhouse horticulture, especially using CO.sub.2
fertilization into new closed system air handling technologies, is
potentially an attractive way to utilize CO.sub.2 while simultaneously
boosting food security and exports in developing countries. Greenhouse
horticulture also can offer an attractive mode of labor market
industrialization for farmers who have an innate appreciation for, and
understanding of, plant cultivation. However, low-cost CO.sub.2 typically
is unavailable in developing countries.
[0097] The amount of CO.sub.2 input for use in greenhouse horticulture
relates to several variables. These include especially the desired degree
of enhancement over atmospheric concentration and the rate of ventilation
of air into and out of the greenhouse (Nederhoff, 2004). Some rough
numbers are: (i) from the OCAP distribution network in Rotterdam (OCAP,
2012): .about.400,000 tonnes CO.sub.2 in a year supplied .about.2,000
heactares of greenhouses for an average utilization of .about.200 tonnes
per hectare per year; and (ii) from Nederhoff (2004) in New Zealand:
.about.7.5 grams CO.sub.2 per square meter per hour averaged over a
24-hour basis with a high-productivity focus: .about.660 tonnes per
hectare per year. Therefore, for 10,000 hectares, (a square: 10
km.times.10 km), an intermediate usage of .about.400 tonnes CO.sub.2 per
hectare per year sums to .about.4 million tonnes CO.sub.2 utilization per
year. Edwards (2008) provides a detailed treatment of CO.sub.2
utilization in greenhouses based on the bio-intake basis of plant
photosynthesis.
[0098] The use of CO.sub.2 in the cultivation of medicinal ginseng root
demonstrates a different type of biotechnological horticulture focused on
very high value products. North American ginseng root takes several years
to grow in the wild or under cultivation. It sells wholesale to Asian
processors for a price exceeding US$2,000 per kilogram (Maher, 2014). Ali
et al., (2005) demonstrated rapid growth of ginseng root tips in
CO.sub.2-enriched bioreactors, with strong increase in production of the
specific phenolic substances desired for medicinal use. Ginseng also has
been grown industrially in cell culture suspensions since the 1990s
(Yesil-Celiktas et al., 2010; Thanh et al., 2014). CO.sub.2 used in this
manner acts as a stressor rather than as a photosynthetic carbon source
in ginseng root growth in bioreactors (Kim et al., 2002).
[0099] Coffee plantlets have been grown in mass culture in enhanced
CO.sub.2 photoautotrophic conditions (Afreen et al. 2002), for example in
temporary root immersion bioreactors by the company Nestle (Ducos wt al.,
2007).
[0100] The anti-malarial drug artemisinin is produced by the plant,
Artemisia annua L. Mass propagations of high-producing clones of this
plant use an acclimatization step involving photoautotrophic growth with
CO.sub.2-enriched air (Supaibulwattana et al., 2011). The use of CO.sub.2
in photoautotrophic micropropagation of plants is a well-known
horticultural biotechnology (e.g., Hayadhi et al., 1993; Xiao et al.,
2011). This technology uses CO.sub.2-enriched air for transitioning and
"hardening" young plants to survive post the changeover from heterotrophy
to photoautotrophy. This can be done in so-called mist bioreactors. These
bioreactors create rooted plantlets on a mass scale from liquid mass
cultures of cell-derived plant embryo clones (Fei and Weathers, 2014). An
example of a company producing agricultural products via this method is
Rootec (www.rootec.com).
[0101] Potentially a very large scale use for CO.sub.2 is as a carbon
source in the production of microalgae (both prokaryotic cyanobacterial
algae and eukaryotic algae, both microalgae and macroalgae). Algae is
produced for various uses ranging from biofertilizer and beneficial crop
innoculant (Benemann, 1979; Connelly, 2014; Wang et al., 2015; Prasanna
et al., 2015; Rana et al., 2015; Renuka et al., 2015), to bioplastics
input (Zeller et al., 2013), to bio-asphalt (Audo et al., 2015), to
high-protein "superfood" (Hug and Von Der Weid, 2011; www.cyanotech.com;
www.earthrise.com), to biofuel (Brennan and Owende, 2010; Lundquist et
al., 2010; Benemann, 2013; E4Tech, 2014), to high-value nutraceuticals
and pharmaceuticals (Fichtali and Senanayake, 2010; Cuellar-Bermudez et
al., 2014; Stefan and Boussiba, 2014). CO.sub.2 typically is diffused by
bubbling in photobioreactors or into downflow bubble-diffuser trenches in
circulating open pond systems of the Oswald type (Oswald, 1962, 1988;
Richmond and Hu, 2013; Weissman and Goebel, 1987). Alternately, for pH
above .about.10, CO.sub.2 input can be coupled with a cyclic pH-swing
process. This process absorbs CO.sub.2 by converting dissolved sodium
carbonate into dissolved sodium bicarbonate. This is operated in a
diurnal cycle that balances the pH decrease of CO.sub.2 addition at night
with the opposite process of pH increase driven by algal photosynthesis
during the day (Chi et al., 2011, 2013).
[0102] Algal biomass processing can utilize CO.sub.2 in various ways. Lee
et al., (2015) have demonstrated a method for pressurized CO.sub.2 to be
used as a coagulation agent for algal harvesting. Supercritical and other
forms of CO.sub.2 can be used for product extractions from algal biomass
(for example: Aresta et al., 2005; Soh and Zimmerman, 2011, 2012; Soh et
al., 2014; Du et al., 2015; Goto et al., 2015). Of particular interest,
low-energy-cost CO.sub.2 switchable solvent systems have been proposed by
Boyd et al., (2012) and Du et al., (2013, 2015) for lipids extraction
from wet algal biomass.
[0103] CO.sub.2 can be utilized industrially as a thermal energy transport
fluid for efficient geothermal energy extraction. Low viscosity and a
strong thermosiphon convective plume effect are the key physical
advantages. CO.sub.2 is injected in supercritical (deep pressurized)
conditions as the working fluid for geothermal heat extraction, sometimes
creating mixtures with circulating geothermal waters (Brown, 2000; Preuss
2006, 2008; Atrens et al., 2009a,b,c, 2010a,b, 2011a,b, 2014; Atrens and
Gurgenci, 2013; Randolph, 2011; Randolph and Saar, 2010, 2011a,b,c, 2013;
Global CCS Institute, 2011; Eastman and Muir, 2012, 2013; US 2011/0100002
A1; U.S. Pat. No. 8,991,510 B2; Randolph et al., 2013; Garapati et al.,
2014; Eastman, 2014; Adams et al., 2014, 2015a,b; Ismail, 2013; Carroll
and Stillman, 2014; Mohan et al., 2015; Xu et al., 2015; Plaksina and
White, 2016). Attractively, this technology can be linked with geological
sequestration of CO.sub.2. Two US start-up companies are developing this
technology: (i) Green Fire Energy (www.greenfireenergy.com) and (ii) Heat
Mining Company LLC, apparently renamed TerraCOH Inc.
(www.terracoh-age.com). Plans are afoot for possible future application
in Australia (Xu et al., 2015). A first field trial has been made via a
USDOE-funded partnership between the Lawrence Berkeley National
Laboratory and the sc-CO.sub.2 power cycle heat engine company Echogen.
This trial tested geothermal energy extraction by CO.sub.2-injection in
the SECARB Cranfield CCS site in Mississippi (Krotz, 2011; Freifield et
al., 2013, undated).
[0104] East Africa is a prime location for geothermal power in the context
of continental rifting and volcanism. Kenya has .about.600 MW of
installed and operating geothermal power
(https://en.wikipedia.org/wiki/Geothermal_power in Kenya). Kenya also has
been utilizing geothermally associated CO.sub.2 in its greenhouse
horticulture industry, with waste heat utilized in pyrethrum drying
(Mangi, 2013; Omeda and Simiyu, 2015). Rwanda aims to develop its
geothermal energy resources.
[0105] CO.sub.2 is used very widely in industry as a supercritical solvent
(Srinivas and King, 2010; Peach and Eastoe, 2014; Hellivan, 2012; King,
2014). CO.sub.2 has vast potential for future "tuned solvent" development
used in combination with ionic liquids (Keskin et al., 2007).
Supercritical CO.sub.2 is an environmentally benign reaction medium for
many forms of chemical synthesis (Tanchoux and Leitner, 2002). For
example, botanical extractions using supercritical CO.sub.2 (sc-CO.sub.2)
include: tea and coffee decaffeination (U.S. Pat. No. 4,260,639; Zosel,
1978; Lack and Seidlitz, 2012), extraction and refining of vanilla
oleoresin and vanillin from vanilla beans (Nguyen et al., 1991;
Castillo-Ruz et al., 2011; Runco, 2015), extracting insecticidal
pyrethrum components (pyrethrin I & II) and oleoresin from dried
pyrethrum flowers (Pan et al., 1995; Ryan et al., undated; Botanical
Resources Australia Pty. Ltd., undated; Kiriamiti et al., 2003a,b, 2006),
extracting hops flavor extraction from hops for use in the beer brewing
industry (Schmidt et al., undated), extracting rose oil from roses
(https://en.wikipedia.org/wiki/Rose_oil), extracting thymol from the herb
thyme (Prado et al., 2009), extracting onion flavor oil from onion,
extracting ginger flavor oleoresin from ginger root, extracting the
anti-malarial drug artemisinin from the plant Artemisia annua
(Padayatchi, 2004), extracting mango butter from waste mango kernels
(Yimsiri et al., 2011; Jahurul et al., 2014), extracting and/or refining
the high-value nutraceutical astaxanthin as an oleoresin from algal
biomass (Cyanotech, 2015; King, 2013), as well as from krill and
crustacean and copepod waste (Sanchez-Camargo et al., 2011, 2012, 2014;
Ali-Nehari et al., 2012), extracting and purifying high-value omega-3
nutraceutical oils and anti-oxidant carotenoids from algal biomass
(Natex, undated; Shen et al., 2011; King, 2013), extracting medicinal and
nutraceutical triterpanoid-rich extracts from bamboo (Jiao et al., 2007;
Lu et al., 2010; Nirmala and Bisht, 2015; Zhang et al., U.S. Pat. No.
7,811,997 B2, "Composition containing total triterpanoid sapogenins
extracted from bamboo, and the preparation method and use thereof."), and
extracting and purifying the blood-pressure-reducing flavonoid
nutraceutical epicatechin from tea leaves (Bermejo et al., 2015), and
cacao beans (Murga et al., 2000; Sarmento et al., 2008; Gadkari and
Balaramanm 2015 King and Srivivas, 2014). Supercritical CO.sub.2 can be
used as a basis for simplified palm oil and palm kernel oil refining
(Manan et al., 2009; Akanda et al., 2012; Mursillo and Bolanos, 2013;
Setapar et al., 2014; Zaidul et al., 2007). Sc--CO.sub.2 also allows
extraction of valuable substances from palm oil such as beta-carotene,
alpha-tocopherol (Setapar et al., 2014; Murcillo and Bolanos, 2013), and
squalene (Stavroulias and Panayioyou, 2005; Popa et al., 2014, 2015).
[0106] Squalene (C.sub.30H.sub.60) is a bioactive nutraceutical (a
triterpenic hydrocarbon) present in olive oil and palm oil and in the
waste materials from processing of both (Ramirez-Torrez wt al., 2010). It
is particularly enriched in amaranth seed oil: .about.3 to 10% (He and
Corke, 2003; Caselato-Sousa and Amaya-Farfan, 2012; Rodas and Bressani,
2009). Squalene has been shown to be extractable efficiently from palm
oil, palm oil waste and from amaranth seeds using supercritical CO.sub.2
(He et al., 2002; He and Corke, 2003; He et al., 2003; Westerman et al.,
2006; May et al., 2009; Czaplicki et al., 2012; Norhidayah et al., 2012;
Akgun et al., 2013; Wejnerowska et al., 2013; Yunus, 2015; Brunner et al.
2011: U.S. Pat. No. 8,048,462 B2, "Process for production of highly
enriched fractions of natural compounds from palm oil with supercritical
and near critical fluids"). Squalene appears to be a substantially
beneficial dietary supplement (Spanova and Daum, 2011; Popa et al. 2014,
2015). It has a long history in traditional and neo-traditional medicine
in Japan where it is obtained as shark liver oil. Squalene has been
widely discussed as a likely causative agent involved in
epidemiologically detected benefits of the "Mediterranean diet" via its
presence in olive oil (Strandberg et al., 1990). In direct examination,
it exhibits moderately well demonstrated cardiac and cancer prevention
effects in humans (Spanova and Daum, 2011). For example, dietary
supplementation has been demonstrated by clinical trial to have a similar
scale of beneficial effect to conventional medical statin therapy,
(substantially reducing bulk cholesterol and LDL, while increasing HDL).
Dietary supplementation of squalene was found to act well in combination
with statin therapy, generating a substantially synergistic effect on
blood chemistry (Chen et al., 1996. See also: Hamadate et al., 2015).
[0107] "Amaranth" describes a plant genus with many species and varieties
worldwide. As in the case of quinoa, agricultural use of amaranth seed
began in pre-Columbian South America as a traditional food staple.
Amaranth leaves are also cooked as a kind of spinach. Amaranth recently
has become a part of a major trend in demand for gluten-free alternatives
to wheat (Maisto, 2011; Caselato-Sousa and Amaya-Farfan, 2012; Coles,
2014; Wikipedia: "Amaranth grain"). The plant is abundant in Africa
(Cernansky, 2015), especially in Rwanda. Due to its rapid growth and
abundantly leafy form (often as a weed), it is known there as "the plant
from the gods" and goes by the name "dodo" (Todd, 2013). The food company
Innovesca (www.innovesca.com) has initiated efforts to industrialize
Rwandan amaranth. Squalene extraction from amaranth seed is an example of
ways supercritical CO.sub.2 can be utilized strategically in new market
creation. Extracting high-value nutraceutical oil from amaranth seed
leaves behind a defatted protein-rich secondary product.
[0108] Supercritical CO.sub.2 can be used as a solvent for tire recycling
by devulcanization of tire-derived "crumb" rubber particles containing
the carbon black component added to manufacture tires (Zhang, 2002; Zhang
and Tzoganakis, 2004; Tzoganakis, undated; Meysami and Tzoganakis, 2009;
Meysoumi, 2012; McCoy, 2015; U.S. Pat. No. 7,189,762 B2, Tzoganakis,
"Method of modifying crosslinked rubber"). This process has been
industrialized by the Canadian company Tyromer (www.tyromer.com) in a
partnership with the rubber supplier Airboss Rubber Compounding (CNW
Group, 2015). Industrial routinization of this technology may offer the
possibility to manufacture new tires using components of recycled
material.
[0109] Supercritical CO.sub.2 can be used to recycle polystyrene waste
such as styrofoam packaging material. Polystyrene recycling can use waste
polystyrene to create new molded styrofoam packaging materials. The
production of many packaged exports requires the availability of
use-specific molded styrofoam packaging. The new technology is described
in the PhD thesis of Cristina Munoz Gutierrez of the University of
Castilla-La Mancha, Cuidad Real, Spain (Gutierrez, 2014), and in several
associated papers (Gutierrez et al., 2010, 2012, 2013a,b,c, 2014a,b,c,
2015). The technology has four main process stages. Polystyrene waste is
first dissolved in limonene to separate it from associated non-dissolving
waste. Second, supercritical CO.sub.2 is used as an anti-solvent to
remove most of the limonene from polystyrene, (which precipitates with
some admixed limonene). Third, CO.sub.2 is used as a foam-forming blowing
agent to form new molded polystyrene foam parts by pressure absorption
and depressurization. Fourth, CO.sub.2 is used as a wash to clean remnant
limonene from the polystyrene foam.
[0110] Supercritical CO.sub.2 extraction is a high-yield, low-waste,
energy-efficient method to obtain limonene from citrus peel wastes (Read,
2009; McKenzie et al., 2004; Atti-Santos et al., 2005; Ferhat et al.,
2007; Suetsuga et al., 2013). Limonene is a widely produced natural
product. It has well-known uses in cosmetics, perfumes, as a natural
biocide, and as an input into a wide variety of chemical synthesis
reactions in the new bioeconomy (Ciriminna et al., 2014).
[0111] Limonene oxide is produced by reaction of limonene with O.sub.2 in
supercritical CO.sub.2 as reaction medium (Corazza et al., 2003; Lima et
al., 2005). Limonine oxide and CO.sub.2, in turn, are copolymerizable
into the high-quality CCU bioplastic, limonene polycarbonate (Byrne et
al., 2004; Yang et al., 2005; Scott, 2006; Bahr et al., 2012; Hauenstein
et al., 2015).
[0112] A new mode of biorefinery uses high-pressure CO.sub.2 as a
biosolvent and bioprocessing liquid in various combinations, also in
mixtures with water and ethanol (King and Srinivas, 2014; King, 2014;
Schievano et al., 2015). Prominent supercritical CO.sub.2 specialized
companies pioneering such uses include: (i) Evonik (Evonik, undated
website materials), the company that pioneered tea decaffeination, (ii)
NATECO.sub.2 (www.nateco2.de), which pioneered extraction of hops
extracts for the beer industry, and (iii) Fayecon (www.fayecon.com),
which has pioneered a wide range of industrial uses of supercritical
CO.sub.2. Supercritical CO.sub.2 offers a way to separate foodstuff
substances "toxin-free" in the absence of residual organosolvent toxins
(commonly hexane). This allows both the extracted and residual components
to be marketable on this basis, as noted above for amaranth seed. Further
examples include: (i) decaffeination of tea and coffee to provide
decaffeinated products as well as marketable natural caffeine used in the
caffeination of beverages, and (ii) defatting of whole macadamia nuts to
provide macadamia oil and diet macadamia nuts (Silva et al., 2008).
Separated caffeine has market value. It is a natural biopesticide. It is
especially effective against slugs, snails and frogs (Hollingsworth et
al., 2002, 2003; Kim et al., 2010; Raloff, undated). Supercritical
CO.sub.2 also can be used to separate whey protein isolate from whey
waste from cheese-making (Bonnaillie and Tomasula, 2012; Yver at al.,
2012). Whey protein isolates are popular protein additives to
high-nutrition health drinks. Rice can be processed with milling and
sc-CO.sub.2 treatments into a main component of ultra-purified white rice
(RiceMate, undated). Supercritical CO.sub.2 processing can produce
several bran-based biproducts including rice bran oil, fiber- and
protein-rich defatted bran, and the nutraceuticals .gamma.-oryzanol and
tocopherol (King, 2014; Natex, undated; Tomita et al., 2014).
[0113] CO.sub.2 is utilized as a non-CFC-based heat transfer refrigerant
fluid in cooling systems (Belman-Flores et al., 2014; Sarkar, 2012;
Cavallini, 2004; Evans, 2010). This technology is being extensively
commercialized in the supermarket refrigeration sector.
[0114] CO.sub.2 is utilized commercially as a cryogenic refrigerant. Dry
ice allows CO.sub.2 to be utilized as a cargo transport coolant. Dry ice
can provide off-grid refrigeration linked with the delivery of kegs of
beer and other beverages. Dry ice chilling therefore can allow draft
dispensing from kegs, thereby avoiding the expense of bottles and
bottling on off-grid locations. Cold liquified CO.sub.2 also is used as a
refrigeration coolant in the trucking sector (Tassou et al., undated).
This method has ecological and cost advantages over diesel engine-based
refrigeration systems if liquid CO.sub.2 is captured from industrial
exhaust, and if it is purified/compressed/cooled efficiently (Thermo
King, undated; Sustania 100, 2013).
[0115] Solidified CO.sub.2 or "dry ice" has been commercialized since 1925
and has many uses. It can be useful as a way to provide refrigeration to
off-grid locations connected with periodic delivery of food and beverage
supplies requiring cool storage (FPA, 2006;
http://www.dryicesouthafrica.co.za). Typically, dry ice is manufactured
from pressurized liquid CO.sub.2 by Joule-Thompson depressurization
cooling (Rusli et al., 2014). This is wasteful of both energy and
CO.sub.2 unless recycled. An alternate efficient method is to manufacture
dry ice blocks by cooling liquid CO.sub.2 in block molds (Eastman, U.S.
Pat. No. 2,138,758, "Manufacture of carbon dioxide ice"). This method can
be practiced in locations where large-scale cryogenic facilities are
available.
[0116] Compressed CO.sub.2 is utilized as for industrial blasting in
situations of flammability danger such as coal mines and silo blockages.
The company "Cardox" manufactures systems for these purposes (Cardox.
Undated).
[0117] Liquid/supercritical CO.sub.2 is used for water-free, waste-free
dry cleaning of clothing using a variety of surfactant additives and
mechanical washing modes (www.solvaircleaning.com;
www.tersussolutions.com; Taylor et al., 2000; DeSimone, 2002; Stewart,
2003; van Roosmalen, 2003; van Roosmalen et al., 2003a,b; Sutanto, 2014;
Sutanto et al., 2014a,b; CompanyWeek, 2015). This technology was patented
and industrialized in the 1990s (Taylor et al., 2000; DeSimone et al.,
U.S. Pat. No. 5,783,082, "Cleaning process using carbon dioxide as a
solvent and employing molecularly engineered surfactants." Iliff et al.,
U.S. Pat. No. 5,412,958, "Liquid/supercritical carbon dioxide/dry
cleaning system.").
[0118] Supercritical CO.sub.2 is used industrially for water-free and
waste-free dying of textiles (www.dyecoo.com; Knittel et al., 1993; Saus
et al., 1993; Montero et al., 2000; Bach et al., 2002; van der Kraan,
2005; DyeCoo, 2010; Liao and Chang, 2012; Yeh Group, undated; Huntsman,
2013).
[0119] Supercritical CO.sub.2 is used for dehydration-drying (Brown, 2010;
Brown et al., 2008, 2010; Khalloufi et al., 2010; Benali and Boumghar,
2014; Hofland, 2014; Wikipedia entry: Supercritical drying). This is a
new technology in specific application to foods drying. It is being
industrialized by the Dutch company CO2DRY (www.co2dry.com), created by
Feyecon (www.feyecon.com; Feyecon, undated; Agterof et al. U.S. Pat. No.
8,187,655 B2, "Dehydration method."). Supercritical CO.sub.2 can
dehydrate foods at temperatures not higher than 35 degrees centigrade.
Water absorbed into supercritical CO.sub.2 can be removed by membrane
separation methods (Koziara, undated; Lohaus et al., 2015).
[0120] Supercritical CO.sub.2 is used as a replacement diluent-solvent for
paint and adhesives spraying with .about.80% reduction of environmentally
harmful volatile organic compounds (VOCs). This process was
industrialized by Union Carbide in .about.1990 using the process
trademark, "UNICARB" (Busby et al., 1990; Nielsen et al., 1993; Copeland,
1994; Lewis et al., 1997; Donahue, undated; Lee et al., U.S. Pat. No.
5,027,742, "Supercritical fluids as diluents in liquid spray applications
of coatings." Hoy et al., U.S. Pat. No. 5,203,843, "Liquid spray
applications of coatings with supercritical fluids as diluents and
spraying from an orifice.")
[0121] High pressure CO.sub.2 is used for a variety of broadly related
methods for spraying applications to generate fine powders, aggregates
and micro-encapsulations. The simplest method is
depressurization-precipitation from pressurized CO.sub.2 solvent
solutions. It is known as the Rapid Expansion from Saturated Solutions,
(RESS) process. Examples include the formation of fine particulate sprays
of chocolate-rich and cocoa butter-rich particles onto fine confectionary
foods (Letourneau et al., 2005, 2007). Other related methods identified
by acronyms and utilizing high-pressure CO.sub.2 include: the
Supercritical Anti-solvent (SAS) process, the Particles from Gas
Saturated Solutions (PGSS) process, the Concentrated Powder Form (CPF)
process, the Continuous Powder Coating Spraying (CPCSP) process, the
Carbon dioxide Assisted Nebulization with a Bubble Dryer (CAN-BD)
process, the Supercritical Enhanced Atomization (SEA) process, the
Supercritical Fluid Assisted Atomization (SAA) process, the
Depressurization of an Expanded Liquid Organic Solution (DELOS) process,
the Gaseous Anti-Solvent (GAS) process, the Aerosol Solvent Extraction
(ASES) process, and the Solution Enhanced Dispersion by Supercritical
Fluids (SEDS) process (Lack et al., 2005; Nunes and Duarte, 2011). These
CO.sub.2-utilizing technologies have many applications across a range of
business areas such as foods, nutraceuticals, cosmetics and
pharmacological/medical products manufacture. These methods noted above
have been widely reviewed (Lack et al., 2005; Martin and Cocero, 2008;
Cocero et al., 2009; Maryin et al., 2010; Augustin and Hemar, 2011;
Kalani and Yunus, 2011; Khosravi-Darani and Mozafari, 2011; Montes et
al., 2011; Munin and Edwards-Levy, 2011; Nunes and Duarte, 2011;
Onwulata, 2012; Priamo et al., 2013; Santo et al., 2013; Fahim et al.,
2014; Natu and Every, 2014; Silva and Meireles, 2014; Mishra, 2015).
[0122] Tea (Camellia sinensis) is a significant global crop with relevance
for CO.sub.2-based value-add processing into nutraceuticals and
pharmacological treatments using supercritical CO.sub.2. This is for
differential caffeine and polyphenols extractions as well as via the
particle trapping and encapsulation methods noted above (PGSS method) for
powdered products. These methods are important for efficient capture of
polyphenols in tea into nutraceutical products (Sajilata et al., 2008),
particularly its abundant oxygen-sensitive medically beneficial catechins
(Liu et al., 2015). For efficient processing, tea polyphenols need to be
protected against oxidative destruction in both production and storage
(Meterc et al., 2007, 2008; Sosa et al., 2011; Gadkari and Balaraman,
2014). Dietary intake of tea polyphenol flavanoids is known from numerous
human studies, including numerous double-blind placebo-controlled
clinical trials, to increase in human health by a variety of effects
including blood pressure reduction, favorable blood lipids modulation,
and glucose/insulin control (Liu et al., 2013; Onakpoya et al., 2014;
Peng et al., 2014; Sonoda et al., 2015). An example of a former tea
estate transformed into a nutraceutical production site is the Senteeko
Estate of Mpumalanga, South Africa (SAASTA, 2014).
[0123] Mango peel waste and mango leaves have been recognized as another
source of catechins-rich polyphenols suitable for nutraceuticals
production (Maslbo and He, 2008; Jahurul et al., 2015). Supercritical
CO.sub.2 extraction has been demonstrated to be an effective extraction
method (Pereira and Meireles, 2007; Garcia-Mendoza et al., 2015).
[0124] Eucalyptol (1,8-cineole) is the main compound present in eucalyptus
oil. Along with various phytonutrients, it can be extracted efficiently
using supercritical CO.sub.2. Extracts are obtained from leaves of
several different Eucalyptus tree species (Milner et al., 1997; Francisco
et al., 2001; Zhao and Zhang, 2014). Eucalyptus leaves are an ancient
traditional medicinal remedy of the Aboriginal peoples of Australia. The
first medicinal eucalyptus oil was produced for sale in Australia in
1852: "Bosisto's Parrot Brand Eucalyptus Oil." This product may have been
Australia's first novel indigenous export product. It is still produced
and sold today (Abbott, undated; Kruszeinicki, 2015). Use of eucalyptus
oil as an inhalant for relief of nasal and throat congestion spread
rapidly in Europe and the United States (Fox, 1927). Eucalyptus oil
continues in this use to the present, along with menthol and camphor.
More recently, nutraceutical substances have been obtained from
eucalyptus leaves by supercritical CO.sub.2 extraction and Supercritical
Anti-Solvent (SAS) particle formation methods (Chinnarasu et al., 2015).
[0125] The sweet potato tuber is the most productive food crop grown in
the tropics when considered in terms of edible energy yield per hectare
(Woolfe, 1992). Sweet potato is in the seventh largest food crop
worldwide. It is grown predominantly in developing countries and very
extensively in Sub-Saharan Africa. The leaves of the sweet potato plants
are protein-rich (25 to 30%, An et al., 2013), widely eaten cooked in
Asia, and contain high-levels of medicinally beneficial phytonutrients,
typically exceeding those of kale and spinach (Islam et al., 2002; Islam,
2006; Menelaou et al., 2006; Truong et al., 2006; Lako et al., 2007;
Johnson and Pace 2010; Karna et al., 2011; Nagai et al., 2011;
Ghasemzadeh et al., 2012; Hue et al., 2012; Gundala et al., 2013; Luo et
al., 2013; Mohanraj and Sivasnakar, 2014; Sani et al., 2014; Sun et al.,
2014; Praderio, 2015; Dorman, 2015; Xi et al., 2015). Hence sweet potato
can be cultivated on a "two-for-one" basis, harvesting both leaves and
tubers. Leaves may be harvested by pruning during the period of tuber
growth and also by co-harvesting leaves and stems at the time of tuber
harvest. Sweet potato leaf phytonutients are efficiently extractable by
supercritical CO.sub.2 (Chen et al., 2011). The residue of CO.sub.2
extraction processing of sweet potato leaves is a low-fat, high-fiber,
protein-rich, marketable powder. Separated sweet potato phytonutrients
were commercialized in 2007 under the brand name "Toyo-KanSho" by the
company Toyo Bio-Pharma (Nutraceuticals World, 2007; Yoshimoto et al.,
2005; Shimada et al., 2010).
[0126] High-pressure CO.sub.2 can be used for efficient "green" processing
of harvested stevia (Stevia rebaudiani) leaves to obtain non-caloric
stevia glycoside food sweeteners. These sweeteners are much-favored by
diabetics and dieters worldwide. They are sold directly and in many food
preparations as sugar-substitutes under a variety of trade names. The
sought after molecules principally are two: (i) stevioside (typically
.about.6% by weight in the dried leaf), and (ii) a more valuable but less
abundant (.about.1.5%) molecule: rebaudioside A. Rebaudioside A is the
most sought-after substance. It has a taste most similar to sucrose with
the least aftertaste. CO.sub.2-based extraction methods for stevia
initially were developed in Japan. German and US patents followed, for
example: U.S. Pat. No. 5,112,610, U. Kienle, 1990, "Method of making a
natural sweetener based on stevia rebaudiana, and use thereof." In a
first stage of processing with carbon dioxide, according to Kienle's
method, supercritical CO.sub.2 can be used as an initial washing step in
order to remove several Sc--CO.sub.2 extractable bitter phytonutrient
substances from stevia dry leaves or dry leaf powder, leaving the
(CO.sub.2-insoluble) stevia glycosides behind with the leaf material. In
a second stage of processing, supercritical CO.sub.2 together with polar
co-solvent water and/or ethanol or methanol admixed can be used to
extract stevia glycosides from the pre-cleaned powder. Extraction by
supercritical CO.sub.2 in the presence of polar co-solvents can yield
equivalent or superior yields relative to conventional water extraction
(Nishiyama et al., 1992; Pasquel et al., 2000; Yoda et al., 2003; Erkucuk
et al., 2009; Abou-Arab et al., 2010; Lemus-Mondaca et al., 2012;
Abadalbasit et al., 2014; Jentzer et al., 2015). Third, decrease of the
pressure and temperature conditions of the supercritical mixed solvent
from step 2 can obtain a sub-critical liquid-liquid phase separation.
Stevia glycosides then are present in the non-CO.sub.2 phase dissolved in
water and/or ethanol or methanol. Stevia processing with CO.sub.2 thereby
also can allow separation and collection of valuable components of stevia
leaf phytonutrients and related substances from the first and/or third
stages of processing noted above (Pasquel et al., 2000; Yoda et al.,
2003; Yildaz-Ozturk at al., 2015).
[0127] High-pressure CO.sub.2 has been demonstrated to provide an
environmentally benign replacement for water in several steps in the
industrial processing of animal skins into tanned leather (Perre et al.,
2003; Hu and Deng, 2015). Water-based tanning is a high pollution
intensity process. High-pressure CO.sub.2 functions as a green solvent in
the processes of deliming (Yang et al., 2009), enzymatic unhairing (Li et
al., 2007), degreasing (Marsal et al., 2000), and tanning (Renner et al.,
2009, 2012; Onem et al., 2015).
[0128] Small pressurized CO.sub.2 reservoirs are used for propellant
release firing in paintball guns. These guns are used for military
training and recreational sport (Kingman Group, undated).
[0129] Gaseous CO.sub.2 has a range of medical uses. Inhaled, it can
modulate respiration and consciousness. Breathing CO.sub.2 has potent
anesthetic effects under certain conditions relative to oxygen levels.
CO.sub.2 is said to have been the first gaseous anesthetic used
surgically almost 200 years ago (Duncum, 1947). It was used in human
anesthesia in combination with other anesthetic agents into the
mid-20.sup.th century. Today CO.sub.2 is used as an anesthetic in the
humane slaughter of animals. This is by anesthetic "stunning" followed by
"controlled atmosphere killing." This combination of methods is commended
by the organization PETA (People for the Ethical Treatment of Animals,
PETA, undated). CO.sub.2-based anesthetic slaughtering is widely used,
especially with pigs (Holst, 2001; MPS, undated; Butina, undated; SFK
Leblanc, undated). Chicken processors increasingly are using CO.sub.2
stunning systems (Praxair, undated; Neuman, 2010; Meyn, undated), winning
PETA commendation. Reviews are provided by Lombolt (undated), Grandin
(2013), and Grandin and Smith (undated). A home-built system for small
farm use is described by Rice et al., (2014).
[0130] Large scale industrialization of methods utilizing CO.sub.2 to
produce sodium carbonate (Na.sub.2CO.sub.3) and bicarbonate (NaHCO.sub.3)
has been in existence since the 1860s. The ammonia-soda process was
industrialized by the Belgian chemist Ernest Solvay
(https://en.wikipedia.org/wiki/Solvay_process;
https://en.wikipedia.org/wiki/Ernest_Solvay), founder of the Belgian
chemicals giant Solvay S.A (www.solvay.com). Similar methods were
developed by the chemist Ludwig Mond
(https://en.wikipedia.org/wiki/Ludwig Mond), co-founder of the British
chemicals giant Imperial Chemicals Industries (ICI), now owned by Tata.
The Chinese chemical engineer Hou Debang
(https://en.wikipedia.org/wiki/Hou_Debang) later developed a more
efficient variant known as the modified Solvay process. Debang's process
avoids limestone input and gains ammonium chloride (a fertilizer) output
with ammonia input. Recently, a new greentech variation on the
ammonia-soda process was described by the Swiss chemist Martin Forster:
the "MgCl.sub.2/MgO modified ammonia soda process" (Forster, 2012, 2014).
Forster's method utilizes solar thermal energy or low-grade heat
(.about.525 C). It has the overall process formula:
2NaCl+H.sub.2O+CO.sub.2.fwdarw.Na.sub.2CO.sub.3+2HCl. It therefore
co-produces hydrochloric acid and does not require limestone input.
Provided low-cost NaCl salt input is available, processes of this type
can utilize CO.sub.2 industrially to produce sodium bicarbonate and/or
sodium carbonate along with hydrochloric acid.
[0131] Sodium bicarbonate (NaHCO.sub.3) has been manufactured industrially
by CO.sub.2 carbonation of sodium carbonate since the mid-19th century.
The method utilizes natural deposits of sodium carbonate
(Na.sub.2CO.sub.3, "soda ash"), natron (Na.sub.2CO.sub.3.10H.sub.2O),
trona (Na.sub.2CO.sub.3.2H.sub.2O.NaHCO.sub.3), and also natural alkali
brines (Wikipedia: "Sodium Bicarbonate"; Church & Dwight, website; Howe,
1928; Mineral Information Service, 1959; Garrett, 1995; Kostick, 1992,
1998; Cho et al., 2008). Deposits of soda ash, natron, trona, and
associated alkali brines, are found on a very large scale in the state of
Wyoming in the USA, and also in Turkey, China, Egypt, Sudan, Ethiopia,
Botswana, Kenya, and Tanzania. Carbonation with CO.sub.2 and water to
produce sodium bicarbonate follows the exothermic low-temperature
chemical reaction:
Na.sub.2CO.sub.3+H.sub.2O+CO.sub.2.fwdarw.2NaHCO.sub.3, (with precipitate
composition control dependent upon temperature and CO.sub.2
concentration. Eugster, 1966; Lowenstain and Demicco, 2006).
Industrializations of this process utilizing the minerals noted above,
and alkali brines, are extensive. Industrial processes have been widely
patented beginning at least by 1911 (Wrinkle and Paddock, 1911: U.S. Pat.
No. 1,000,138, "Method of obtaining bicarbonate of soda"). Substantial
recent focus has been on the use of the Na-carbonate system in the
capture of CO.sub.2 in flue gases. Technology developments for CO.sub.2
capture include sodium bicarbonate production (Huttenhuis et al., 2015)
as well as cyclical processes of CO.sub.2 capture and purification from
powerplant flue gases via carbonation-hydration of sodium carbonate to
produce sodium bicarbonate as a CO.sub.2 capture process. This is
followed by a regeneration step of decarbonation-dehydration back to
sodium carbonate, yielding purified CO.sub.2 (Liang, 2003; Liang et al.,
2004; Nelson et al., 2009; Ficicilar and Dogu, 2006; Knuutila et al.,
2009, 2010a,b; Spigarelli and Kawatra, 2013; Zhao et al., 2013; Stolaroff
and Bourcier, 2014).
[0132] High pH alkaline brines (rich in sodium carbonate) are strong
CO.sub.2 absorbers from the atmosphere. They exhibit very high
productivity for algal biomass growth of the "soda lake" type. CO.sub.2
absorption lowers the pH of the brine, whereas photosynthesis raises it.
This is the consequence of a pH-dependent transformation of the ion
balance. There are two Na.sup.+ cations per CO.sub.3.sup.2- anion at
higher pH, whereas Na.sup.+ cations are balanced by one HCO.sub.3.sup.-
anion each at lower pH. Photosynthetic growth of algal biomass transforms
carbon from bicarbonate anions into organic matter, causing an increase
in pH. This is because algal cells capturing HCO.sub.3.sup.- anions as a
CO.sub.2 source regulate pH by importing H.sup.+. They do so in response
to the H .about.consuming (and thereby OH.sup.--producing) equilibrium
governing photosynthetic utilization of the bicarbonate ion as a carbon
source: H.sup.++HCO.sub.3.sup.-.revreaction.CO.sub.2+H.sub.2O. As
photosynthesis consumes CO.sub.2 and boosts the pH in the medium cells
inhabit, lake surface CO.sub.2 absorption increases transporting more
CO.sub.2 into solution. Alkaline brines therefore function as CO.sub.2
pumps in two different modes. These are: (i) first, as noted above, by
inorganic "mineralization" pumping CO.sub.2 into sodium bicarbonate
precipitates (requiring continued input of both CO.sub.2 and sodium
carbonate), and (ii) second by photosynthetic pumping of the carbon in
CO.sub.2 into biomass.
[0133] Shulin Chen's research group at Washington State University (Chi et
al., 2011, 2013, 2014) has shown how CO.sub.2 utilization can employ
these aspects of carbonate chemistry. The process is a "pH swing" cycle.
CO.sub.2 is absorbed into high pH sodium carbonate-rich solutions at
night. This decreases pH to create bicarbonate ion dominance. Algal
photosynthesis during the day absorbs this CO.sub.2 (via bicarbonate),
increasing pH. Photosynthetic production of biomass thereby transforms
the remaining Na.sup.+-balanced bicarbonate anions (HCO.sub.3.sup.-) in
solution into a population of carbonate anions (CO.sub.3.sup.2-), each of
which is charge-balanced by two sodium cations. Hence, combining
carbonate chemistry for CO.sub.2 absorption at night with aqueous
photobiology for its uptake during the day, allows carbonate-rich
bioculture solutions, inorganically to absorb, and photobiologically to
fix CO.sub.2 in a diurnal day-night cycle. Additional utility from
CO.sub.2 capture into a carbonate system follows from the ability of a
high-pH sodium carbonate solution to be used to absorb and transport
algal-bioavailable CO.sub.2 in the form of bicarbonate anion in solution.
This capacity can avoid gas compression by transportation of bicarbonate
in situations where sources and sinks are separated only by a few
kilometers (Chi et al., 2011). (See also: Guangmin et al., 2014).
[0134] Carbon dioxide is a thermodynamic end state for energy release in
processes of hydrocarbon combustion. Lower energy states exist, however,
when considered relative to mineralized states of carbon as carbonates.
This is why most of the carbon in the Earth's
crust-hydrosphere-atmosphere system is present in the crust in the form
of carbonate rocks and minerals rather than as CO.sub.2 elsewhere.
Therefore, carbon dioxide can be utilized as a heat-releasing fuel via
mineral weathering. CO.sub.2, however, is not a fuel that allows
trivially practical access to the energy it carries. Yet, very
substantial energy is released in endothermic chemical transformations of
CO.sub.2 reacting with minerals such as olivine to produce hydrated and
non-hydrated carbonate minerals (Schuiling, 2013). Olivine weathering
also can produce hydrogen gas and reduce CO.sub.2 into methane ethane and
propane by a process of serpentinization (Akinfiev et al., 2005; Neubeck
et al., 2011; Schrenk et al., 2013). CO.sub.2 energy release technologies
based on the weathering of olivine and related minerals and rocks have
not yet been commercialized. The Dutch company Innovation Concepts, BV
(www.innovationconcepts.eu) is focused on this task. Energy release from
olivine carbonation may be important in the future in contexts relating
to the industrial utilization of olivine combined with agendas for very
large scale carbon sequestration.
[0135] Carbon dioxide can be utilized in large quantities via new forms of
ore processing. Supercritical CO.sub.2 can be used for low-energy
extraction of lithium (Li) from lithium-bearing pegmatite minerals such
as spudomene, petalite, zinnwaldite, amblygonite, lepidolite and
triphylite. Lithium is in high and rapidly growing demand globally due to
its use in Li-ion batteries. Typically lithium is sold from the mining
sector in the chemical form of lithium carbonate: Li.sub.2CO.sub.3. A new
method for lithium ore processing by CO.sub.2 to extract lithium is
described in a patent granted to Pedro Mauel Brito da Silva Correia
(2015, U.S. Pat. No. 9,028,789 B2: "Process to produce lithium carbonate
directly from aluminosilicate mineral"). This method requires inputs of
CO.sub.2, water and sodium bicarbonate. It uses high pressure and modest
heating in the range 200 to 600 C. It operates without requiring acids.
It therefore does not generate acidic processing waste. Related methods
utilizing CO.sub.2 are described in a patent application by the Finnish
company Outec: US 2015/0044124 A1: Marika Tilhonen and Liisa Haavanlammi,
"Method for recovering lithium carbonate," and in presentations by
Nogueira (2011) and Margarido et al., (2014), described as "carbonate
pressure leaching."
[0136] A second ore processing method utilizing CO.sub.2 is focused on
dissolving the mineral olivine [(Mg,Fe, +minor Ni).sub.2SiO.sub.4]. It
uses a chemical process of "carbon mineralization" (Power et al., 2013).
This mimics natural weathering. [Forsterite weathering:
MgSiO.sub.4+4CO.sub.2+4H.sub.2O.fwdarw.2Mg.sup.2++4HCO.sub.3.sup.-+H.sub.-
4SiO.sub.4.sup.0]. The method hugely accelerates the reaction rate without
use of acids or high-temperature processing. The main element of the
process is high-pressure processing of finely ground olivine in
supercritical CO.sub.2 and water with NaHCO.sub.3 additive. It has been
shown to dissolve finely ground olivine by more than 70% within two hours
(Eikland et al., 2015; Gadikota et al., 2014; Gerdemann et al., 2007;
Chen et al., 2006; O'Connor et al., 2005; for an overview see: Sanna et
al., 2014, and Kelemen et al., 2011). Additional insights on optimizing
olivine dissolution utilizing CO.sub.2 and various additives have been
published by the ETH-Swiss group of Marco Mazzotti and colleagues
(Prigiobbe et al. 2009a,b, 2013a,b; Mazzotti, 2011; Prigiobbe and
Mazotti, 2011). Olivine CO.sub.2-dissolution processes yield mostly
magnesium carbonates along with extractable forms of nickel, silicic acid
(H.sub.4SiO.sub.4) and/or nano-silica (SiO.sub.2), and oxidized forms of
iron. Methods have been developed for the purpose of fixation of waste
CO.sub.2 by mineral carbonation. However, such methods likely can allow
extractive industrialization of byproducts, for example metals production
for iron, nickel, and possibly also magnesium. An example is the
byproducts monetization agenda being developed by the mining company
Orica in Australia. This is for very large scale carbonation of
serpentinite for CO.sub.2 sequestration (Brent et al., 2011; Brent, 2013,
2014; see also Ramao et al., 2015). Nickel production is a possibility.
Large-scale production of nickel via olivine carbonation with CO.sub.2
has been proposed by Santos et al., (2015). It also was considered by
Thorliefson (2011) for the Duluth Complex in the state of Minnesota in
the USA. Huge untapped dunite reserves exist in many world locations.
Development of an olivine carbonation method of nickel (and iron and
nano-silicon) production offers huge potential for very large scale
CO.sub.2 utilization. World nickel demand is .about.2 million tonnes per
annum (MTA). It is growing at about 10% per year (Pinizzotto, 2015).
Nickel contents in olivine obtained from the olivine-dominated rock type
dunite often are .about.0.3% Ni by weight. For comparison, a good quality
of viable lateritic nickel ore is .about.2% Ni. Some world class nickel
ore deposits are well below 1% Ni (see: page 11 diagram in Emery et al.,
undated). For example, Australia's largest nickel-producing mine, Mount
Keith, has an ore grade of 0.5% nickel (Wilson et al., 2014). If half of
the present scale of world nickel demand (at .about.2 MTA Ni) were to be
satisfied via olivine carbonation processing, with Ni at .about.0.3
weight percent and a CO.sub.2/olivine mass ratio corresponding to
4CO.sub.2/MgSiO.sub.4, then the scale of associated CO.sub.2
utilization-sequestration into Mg carbonates would be .about.500 MTA of
CO.sub.2 capture-mineralization. (CO.sub.2 utilization-sequestration in
this process is .about.500.times.Ni production, by weight, for a 0.3% Ni
ore grade.) This is roughly 1.5% of total present day world anthropogenic
CO.sub.2 emissions. For nickel at US$10,000/tonne, a CO.sub.2 utilization
subsidy of US$20/tonne CO.sub.2 for carbon sequestration would add
$10,000/tonne to Ni sales (or neutralize a $20/tonne cost for obtaining
usable CO.sub.2). Iron often exceeds 10% by weight in olivine. Therefore,
associated iron production could exceed 30.times. nickel at 30 MTA.
Carbonation of ground olivine obtained from dunite bodies has been widely
discussed as a potentially realistic means of very large scale carbon
sequestration (Voormeij and Simandi, 2004; Schuiling and Krijgsman, 2006;
Teir et al., 2010; Kohler et al., 2010, 2013; Schuiling et al., 2011;
Schuiling and de Boer, 2011, 2013; Hartmann et al., 2013; Schuiling,
2014; Smartstones, 2014). The Mount Keith nickel mine in SW Australia is
one of the world's largest reserves of Ni ore. It has a minerology of
predominantly methamorphosed dunite (olivine). It has been strategized as
having the capability to become the world's largest CO.sub.2
sequestration operation at 4 MTA CO.sub.2 by carbonation of mine tailings
(Wilson et al., 2014: Power et al., 2014). Developing nickel mining via
carboration processing of olivine would integrate Ni-production directly
with CO.sub.2 fixation, with co-production of iron, silicon and
Mg-carbonates products. Realism for large-scale operations likely would
require a profit-based situation where the value of a primary target
product, such as nickel, exceeds production cost (Priestnall, 2014;
Santos, 2014). The use of CO.sub.2 in nickel ore processing is known. A
CO.sub.2 processing step is presented in the 1973 patent disclosure of Y.
Sato et al., of the Nippon Yakin Kogyo Company: U.S. Pat. No. 3,765,873,
"Method of producing ferro-nickel or metallic nickel." And a new process
for laterite nickel ore processing with inclusion of CO.sub.2-carbonation
for magnesium separation has been described by Zhai et al., (2010). A
positive factor for olivine carbonation on a large-scale, as noted above,
is that the reaction is exothermic (Schuiling, 2013). Breakdown products
of olivine carbonation can be useful as plant fertilizer (Berge et al.,
2012; www.greensand.nl), especially in conditions of silicon, iron and
magnesium demand, with nickel removed. Silicic acid fertilization can be
of particular importance for the productivity of rice and banana (Guntzer
et al., 2012; Fortunato et al., 2012; Kablan et al., 2012; Meena et al.,
2014). CO.sub.2-dissolution of olivine also can be an effective way to
create nutrient Si- and Fe-rich nutrient water for the production of
algal products from biocultures of algal diatoms (Schuiling, 2012, 2014).
[0137] Olivine carbonation utilizing CO.sub.2 can be arranged to produce
nano-silica. Nano-silica is useful as a pozzolanic cement strengthening
additive in Portland cement (Lazaro et al., 2012, 2013; Gupta, 2013,
2014; Maheswaran et al., 2013; Singh et al., 2013; Yu et al., 2014;
Quercia Bianci and Brouwers, 2015). Adding nano-silica additive into
cement in modest amounts can add 40% to compressive strength to concrete
made with it. It also accelerates hydration-setting, decreases porosity
and Ca-leaching, and increases durability (Sing et al., 2013).
Nano-silica transforms ordinary concrete into a high-performance
concrete, allowing a higher aggregate-to-cement volume ratio and
associated cost savings.
[0138] An additional use for CO.sub.2 is via processes for alumina
production from aluminosilicate ores as alternatives to the traditional
alumina sources of bauxite. Aluminosilicate ores include nepheline
(Na.sub.3KAl.sub.4Si.sub.4O.sub.16)-rich nephelinite, typically in the
form of igneous nephelene syenite rock, and also separated aluminum
feldspars (KAlSi.sub.3O.sub.8--NaAlSi.sub.3O.sub.8--CaAl.sub.2Si.sub.2O.s-
ub.8) such as the very common granitic mineral orthoclase
(KAlSi.sub.3O.sub.8). Orthoclase can be processed to produce a potassium
fertilizer co-product. Anorthite (CaAl.sub.2Si.sub.2O.sub.8) can be
processed to produce calcium carbonate as a co-product to alumina.
Anorthite often is present in high purity in massive igneous cumulate
complexes known as "anorthosite" massifs. Archibald filed a patent in
1942 for the Canadian company Nephiline Products Limited. His method
utilizes the mineral nephiline to produce alumina. It involves limestone
addition and carbonization steps with CO.sub.2: U.S. Pat. No. 2,420,852,
"Recovery of alumina from ores." A similar method has long been used in
alumina production from nephelinite ores in the Soviet Union/Russia
(Smirnov, 1996; Volsky, 21012). A recent publication describing a similar
technique is Qui et al., (2015). A more recent process focused on
anorthosite ore has been developed by the Norwegian company Nordic Mining
(Nordic Mining, undated, 2011; Fossum, 2014; Aranda and Mastin: Norwegian
patent granted in 2015: number 20140317, "En ny fremgangsmate for
fremstilling av alumina og karbonat fra aluminiumrike materialer med
integerert CO.sub.2 utnyttelse"; also: WO 2015137823 A1, "Alumina and
carbonate production method from al-rich materials with integrated
CO.sub.2 utilization."). The method obtains separated alumina,
precipitated calcium carbonate and precipitated silica from HCl-leached
aluminum-rich silicate minerals, particularly from anorthite from
anorthosite ore. Carbon dioxide is used to separate calcium from aluminum
chloride by precipitation of CaCO.sub.3 from HCl acid solution of the
mineral concentrate. A method for liberating potassium from potassium
feldspar (orthoclase) with CO.sub.2 carbonation has been described by Xie
et al., (2013, 2015). The method dissolves orthoclase hydrothermally in
the presence of CO.sub.2 with added calcium chloride and triethanolamine.
Variant methods have been described by Ye et al., (2014) and Wang et al.,
(2014). Future developments in this arena perhaps may be able to obtain
separated alumina, silica, calcium carbonate, and potassium salts. The
most interesting strategic possibility will be in the potential use of
supercritical solutions of CO.sub.2 plus water and reaction-accelerating
substances to dissolve anorthite and/or K-feldspar efficiently at modest
temperatures.
[0139] The "weathering" reaction of CO.sub.2 with silicate minerals mostly
is exothermic. Therefore mineral carbonation is a thermodynamically
favored modality for CO.sub.2 utilization and sequestration. However
reaction kinetics often are very slow. Therefore accelerating mineral
dissolution with low-energy, low-cost and low-waste methods is an
important technology development challenge. Kakizawa et al., (2001), Tier
at al., (2007), Ghoorah (2014), Ghoorah et al., (2014a,b), and
Dlugogorski et al., in a patent application (US 2014/0065039, "Extraction
of alkali metals and/or alkaline earth metals for use in carbon
sequestration") have shown that weak solutions of acetic or formic acid
can very strongly accelerate silicate mineral weathering under various
conditions.
[0140] Titanium separation is an additional potential use for CO.sub.2 in
ore processing. The mineral ilmentite (FeTiO.sub.3) is often used as a
titanium ore. Carbochlorination treatment with chlorine gas and carbon
monoxide produces separable Ti in the form of titanium tetrachloride
(TiCl.sub.4). Titanium is separated from iron by a wide variety of
additional thermochemical methods in ilmenite processing. All are
multi-stage and energy intensive (Zhang et al., 2011) with the exception
of recent developments of low-temperature chlorination methods using
carbon tetrachloride, CCl.sub.4, sometimes in combination with Cl.sub.2
(Fu et al., 2009; Norazharuddin et al., 2015), thereby combining
chlorination with reduction. Tolley and Tester (1989), Tolley et al.,
(1992), and Tolly and Whitehead in U.S. Pat. No. 4,853,205,
"Supercritical fluid halide separation process," all have shown that
TiCl.sub.4 is soluble at low temperature in supercritical CO.sub.2. This
insight combined with the new CCl.sub.4-based chlorination process likely
can allow an efficient separation of titanium from ilmenite in a "green
chemistry" treatment process utilizing CO.sub.2.
[0141] Tantalum- and niobium-rich "coltan" ores can be processed using
carbon tetrachloride or silicon tetrachloride liquids reacting with ores
to chlorinate niobium and tantalum at relatively low temperatures
(Shainyan et al., 2008). Green chemistry advocate James Clark of the
University of York has called for the development of a broadly similar
green process for tantalum separation from coltan ores (York, 2014). An
industrial niobium (Nb) and tantalum (Ta) separation processing method
for coltan ores possibly could be developed utilizing tetrachlorides
followed either by evaporation or by supercritical CO.sub.2 liquid-liquid
extraction to obtain separated Nb- and Ta-pentaclorides. A patent
application for the use of carbon tetrachloride is: Terakhov et al.,
WO2015039219 A1, "Process for recovering tantalum and niobium with carbon
tetrachloride."
[0142] Rare Earth Elements (REE) are an important strategic resource with
rapidly increasing demand globally (McLellan et al., 2013). A fascinating
proposal put forward by Arab et al., (2104, 2015) is to mine REEs by an
extraction method of percolative leaching. Percolative leaching uses
CO.sub.2 injected into a REE-carrying ore zone at depth sufficient for
CO.sub.2 to be in a supercritical state. If realized, this mode of mining
would involve either multiple drill holes, some for injection and some
for collection, or alternately a single-hole flow reversing system with
injection followed by collection. Use of horizontal drilling and
fracture-generating injection technologies ("fracking") can be imagined.
If developed, this proposed technology could provide a revolutionary mode
for REE mining. Other elements potentially leachable by this
CO.sub.2-based method include gold (Glennon et al., 1999, 2003; Glennon,
2003; van Zyl, 2007) and uranium (Wang et al., 2013). Carbonatites and
solidified magma bodies and plutons associated with highly alkaline
volcanic provinces are an obvious target geology for testing this
technology as a consequence of their typical REE enrichment (Verplanck
and Van Gosen, 2011).
[0143] Magnesite (MgCO.sub.3) ores can be purified by leaching and
re-precipitation using pressurized CO.sub.2, as demonstrated by Amer,
(2010). Magnesite obtained from olivine dissolution-carbonation can be
used as an additive in concrete production. It also can be decarbonated
(with CO.sub.2 recycling, if desired) to create magnesium oxide for use
in cement production and also for producing "MgO board." MgO board (e.g.,
http://magobp.com) is a superior form of interior wall-building
"wallboard" material. Its use is directly analogous to the (gypsum-based)
"drywall" wallboard used very widely in construction. MgO board, however,
possesses superior surface hardness, fire-resistance, mold-resistance,
and installation workability relative to conventional drywall (Thomas,
2007; http://magobp.com/benefits/;
https://en.wikipedia.org/wiki/Magnesium_oxide_wallboard). It is widely
manufactured and used in China. The main cementitious process in its
manufacture is based on the hydration of reactive MgO to micro-brucite,
Mg(OH).sub.2. CO.sub.2 utilization via carbonation-hydration in producing
MgO board in a CO.sub.2-rich atmosphere is possible, but not yet
commercialized. Also, wallboard can be made with direct incorporation of
magnesium carbonates, as disclosed in a 1933 patent: U.S. Pat. No.
1,896,689, Spenser, "Building Material and Method of Making the Same."
[0144] CO.sub.2 utilization on a very large scale is possible by mass
production of new types of cement and concrete, which structurally
incorporate CO.sub.2. This innovation has substantial environmental
significance because Portland cement manufacture is responsible for
.about.9% of world total anthropogenic CO.sub.2 emissions. The new mode
of cement production is a consequence of the possibility to use magnesium
(Mg) as a full or partial replacement for calcium (Ca), (Harrison, 2003,
2004, 2006, 2013, 2014, 2015a,b; Al-Tabbaa, 2013; Imbabi et al., 2012;
Glasser et al., 2016; Evans, 2008, 2009, 2010; Evans and Vlasopoulos,
2010). The technology for the production of CO.sub.2-utilizing Mg-based
"eco-cements" and "eco-concretes" has been described and demonstrated by
several institutions worldwide. These include, most notably: TecEco
(www.tececo.com), a business created by the Australian
inventor-entrepreneur John W. Harrison (Harrison, 2003, 2004, 2006, 2013,
2014, 2015a,b and U.S. Pat. No. 7,347,896 B2: "Reactive Magnesium Oxide
Cements"), and the Cambridge University research group of Professor Abir
Al-Tabbaa, in connection with the Cambridge-based David Ball Group plc
(http://www.davidballgroup.co.uk; WO2013178967 A1: Martin et al.,
"Cementitious binders, activators and methods for making concrete.") via
a former PhD student Martin Liska (Vandeperre and Al-Tabbaa, 2007; Liska
et al., 2008, 2012a,b; Liska and Al-Tabbaa, 2008, 2009, 2012; Unluer and
Al-Tabbaa, 2013, 2014, 2015a,b; Unluer, 2015). CO.sub.2-incorporating
Mg-based cements can be produced by at least three different modes to
generate a cementitious matrix. One is to produce the dry cement mix
containing reactive MgO (periclase) and/or magnesium hydroxide,
Mg(OH).sub.2 (brucite), then hydrate and carbonate the cement during
setting to form a range of cementitious magnesium carbonate hydrates. At
the present level of technology, this requires setting within a
thermally-controlled pressure chamber providing CO.sub.2 and steam
(Unluer, 2015). Cementitious hydrated Mg-carbonates include: nesquahonite
[MgCO.sub.3.3H.sub.2O], landsfordite [MgCO.sub.3.5H.sub.2O],
hydromagnesite [4MgCO.sub.3.Mg(OH).sub.2.4H.sub.2O], and dypingite
[4MgCO.sub.3.Mg(OH).sub.2.5H.sub.2O]. Another mode is to produce the dry
cement mix with Mg present in the already carbonated form of the
anhydrous Mg-carbonate magnesite (MgCO.sub.3), then to
hydrate-transform-recrystallize it into hydrated carbonate phases during
setting (Glasser et al., 2015). This method requires setting with thermal
control, therefore within temperature-controlled premises. For
optimality, it may require pressurized gas environment control also. This
mode sequesters CO.sub.2 if the input magnesite been produced by
carbonation of brucite. The third type of CO.sub.2-utilizing Mg-based
cement and concrete can be produced beginning directly with hydrated
Mg-carbonates in the dry cement formulation prior to use. In such cases,
cementitious transformations are obtainable by cycling changes in
temperature with or without hydration, and/or CO.sub.2, and/or steam
injection, in order to control transformation and recrystallization
conditions, for example from nesquahonite to recrystallized nesquahonite
via a thermal cycle exceeding nesquahonite's stability range. This mode
may be possible for conventional pouring without need for a pressure
chamber, requiring only the ability to heat-up the mixed concrete prior
to pouring (Glasser et al., 2016). Such a mode sequesters CO.sub.2 if the
input phases have been produced by carbonation-hydration of brucite.
Overall, a great many types of situations are possible via variable input
chemistries, mixtures with conventional Portland cement, pozzolanic
matrix additions, pozzolanic aggregate additions, CO.sub.2 and/or steam
input carbonation, and preparation, pouring and curing techniques.
Production methods may range from casting and setting blocks and
reinforced section within confined vessels under pressurized CO.sub.2
with or without steam, to pouring and setting in the field like ordinary
concretes made with Portland cement. The field of creating and
industrializing Mg-based CO.sub.2-utilizing cement and concrete
technologies has a big future. However, it has only begun to be
demonstrated in research labs and in a few pioneering industrial
applications. Some of the demonstrated building materials exhibit
superior properties of strength in comparison to conventional Portland
cement. However, CO.sub.2-utilizing Mg-based cements involving hydrated
Mg-carbonates require careful formulation and preparation as well as use
limitations to low temperatures (<.about.50 degrees C., Morgan et al.,
2015). The latter is especially important due to thermal instabilities in
the hydrated Mg-carbonates comprising the cementitious matrix,
particularly nesquahonite. Nesquahonite has an excellent property in that
it in cements it forms in strongly cementitious crystal whisker networks.
However, it has a poor thermal stability range limiting for practical
purposes to less than .about.50 degrees centigrade (Walling and Provis,
2015; Unluer and Al-Tabbaa, 2015b; Highfield et al., 2013).
[0145] Carbonated Mg-based cements are different from Mg-based phosphatic
cements such as Sorel cement (Shand, 2016). They also differ from
non-carbonated MgO-based cements produced from magnesite or Mg-rich
dolomite or dolomitic limestone inputs which are kiln-fired to drive-off
CO.sub.2 to produce reactive MgO. (That is: prepared from MgCO.sub.3 in
direct analogy to Portland cement using CaO obtained by decarbonation of
CaCO.sub.3 limestone, then cured by various hydration reactions.) Such
reactive MgO-based cements are well-known for high performance. In New
York State, the high performance of historic "Rosendale" cements and
concretes is due to high magnesium in the limestone used to make it
(TecEco, undated). Kiln-firing "calcination" of high Mg limestone
generates MgO and Mg-carbonates in addition to the usual CaO content
which is the main input into the formula of Portland cement. MgO-based
concretes have been used extensively in China in dam construction. Their
volume stability during curing is especially prized. See: Zheng et al.,
1991; Du, 2005; Premier, undated; Mo et al., 2014).
[0146] By contrast, CO.sub.2-utilizing Mg-based cements do not begin with
a CO.sub.2 releasing decarbonation step to prepare reactive MgO. The
basic difference with respect to the calcium system is two-fold. First,
both MgO and Mg(OH).sub.2 can be obtained without using natural
MgCO.sub.3 (magnesite) as a natural starting material, whereas CaO (burnt
lime) and Ca(OH).sub.2 (calcium hydroxide Portlandite) are very rare in
the Earth's crust. They typically are obtained by high-temperature
kiln-firing of limestone: CaCO.sub.3.fwdarw.CaO+CO.sub.2. By contrast,
magnesium hydroxide (brucite) can be obtained from natural deposits or by
precipitation from either seawater or alkaline freshwaters and brines
obtained from lakes or wells. Brucite then can be heated above 500 C to
dehydrate it into reactive MgO (Shand, 2006; Alvarado et al., 2000).
Second, CO.sub.2-utilizing cements are based on a cementitious
carbonate-hydrate mineralogy, whereas the setting of Portland cement
predominantly is based on hydration mineralogy.
[0147] In U.S. Patent Application Publication No. 20160257577 A1, the
present inventor disclosed a method and system that included a process of
obtaining precipitate comprised predominantly of magnesium hydroxide in
large quantities from Lake Kivu. The obtaining of this flux of
precipitate was from a process of water treatment of return flow water
following extractive degassing of an upflow of deepwater.
[0148] CO.sub.2 also is utilized for carbonation of ordinary Portland
cement in the solidification of pre-cast building materials. Two
companies, Solidia Technologies (Riman, 2012; Sadu and Cristofaro, 2013;
DeCristofaro and Sahu, 2014, 2015a,b; DeCristofaro et al., 2014;
DeCristofaro, 2015; Jain et al., 2013, 2014, 2015), in partnership with
LaFarge (Lafarge, 2015), and CarbonCure Technologies (www.carboncure.com;
Monkman and Shao, 2010; Monkman, 2012; Monkman and Niven, 2010; Divon,
2015), have industrialized such processes for manufacturing pressed
masonry blocks (known in the USA as "cinder blocks"). These companies
variously carbonate and hydrate mold-injected masonry blocks in the
processes of injection and curing.
[0149] Pressure carbonation with supercritical CO.sub.2 has been
well-demonstrated to enhance the strength and durability of a variety of
composite objects molded with Portland cements and concretes (Rubin et
al., 2003; Garcia-Gonzalez et al., 2007, 2008; Knopf et al., 1999;
Fernandez Bertos et al., 2004; Farahi et al., 2007, 2013; Farahi, 2009).
This technique was developed at Los Alamos National Lab in the 1990s
(Rubin et al., 1997; Taylor et al., 1997). It led to a patent and a
company producing products such as roofing tiles under the trade name
"supramics" (Jones, 2001; Jones, 1996: U.S. Pat. No. 5,518,540: "Cement
treated with high-pressure CO.sub.2."). High-strength carbonated
cement-bonded particleboard incorporating woody biomass is, for example,
produced by rapid exposure to supercritical CO.sub.2 (Suh et al., 2000;
Hermawan et al., 2000, 2001; Maail et al., 2011). This method includes
cement-bonded particleboard made with oil palm frond waste material
(Hermawan et al., 2002). The method, however, has never taken off
industrially. The obvious reason is that facilities for high-pressure
carbonation treatment of molded building materials with supercritical
CO.sub.2 are rare and expensive, and also because CO.sub.2 typically
obtained for such uses is costly. However, such reasons are not
fundamental impediments that apply to all circumstances.
[0150] High-value medical products for human implantation can be made with
technologies developed for making molded composite materials
incorporating carbonates formed by interactions with supercritical
CO.sub.2 (e.g., Garcia-Gonzalez et al., 2015).
[0151] Pressurized CO.sub.2 is used in the production of the remarkable,
newly discovered, magnesium carbonate material "Upsalite.RTM."
(Wikipedia: Upsalite; Forsgren et al., 2013; Frykstrand et al., 2014; TCE
News, 2013; Yousefi, undated). Upsalite is an anhydrous micro- and
macroporous form of magnesium carbonate, MgCO.sub.3. It possesses an
astonishingly large surface area of .about.800 square meters per gram.
Upsalite is a powerfully hygroscopic desiccant, functioning effectively
at low humidity. It also has been shown to be effective as a biologically
harmless, space-efficient, absorbant binding material for time-extended
diffusional drug release in pharmaceutical tablets. (Zhang et al., 2016;
Frykstrand et al., 2015). The Swedish company Disruptive Materials
(www.disruptivematerials.com) has been created to pursue market
development for Upsalite.RTM..
[0152] The input and degassing of CO.sub.2 into and out of aqueous
solutions can be utilized for pH control and precipitation control.
Decrease in pH is achieved by acidifying addition of CO.sub.2 into
solution, such as by sparging. The pH of an aqueous solution containing
CO.sub.2 and/or bicarbonate and/or carbonate anions can increased by
removal of CO.sub.2 from solution by equilibration with gas and by
bubbling aeration, stirring, sparging with CO.sub.2-free gases (e.g.,
N.sub.2) and by vacuum degassing. For an example of CO.sub.2
acidification, Ferreira et al, (2012) used CO.sub.2 input to decrease and
thereby stabilize the pH of an aqueous bioculture of spirulina algae
housed in a recirculating photobioreactor. The increase of pH driven by
photosynthetic activity of the algae was thereby balanced by CO.sub.2
input acidification which also feeds the algae as a carbon source via
bicarbonate ion. For an example of the opposite process, degassing
CO.sub.2 to increase pH, Cohen and Kirchmann, (2004) reported degassing
of wastewater samples wherein use of atmospheric air as the stripping gas
increased pH from a start at pH 8.3 to an equilibrium pH of 8.5, whereas
using pure N.sub.2 instead of air increased the endpoint pH to 10.3. This
method was developed to allow precipitation of wastewater phosphorus as
struvite to realize P-recycling (Cohen, 2001; see also: Fatteh et al.,
2008a,b, 2010; Radev et al., 2015). Oliver et al., (2014) reported
similar findings of pH increase to precipitate nesquahonite by CO.sub.2
removal from a solution of magnesium carbonate by gas stripping with
N.sub.2. These authors reported additional results for CO.sub.2 removal
by algal biological CO.sub.2 uptake, and by accelerated conversion of
bicarbonate to aqueous CO.sub.2 by addition of carbonic anhydrase.
Nitrogen sparging to remove fermentation-CO.sub.2 from (acidic) pickle
brining operations is reviewed by Fleming (1979). Lisitsin at al., (2008)
have shown that CO.sub.2 stripping can precipitate calcium and magnesium
from desalination feed waters as a method of water softening pretreatment
replacing the use of chemical alkali addition. Israeli Technion
scientists have further demonstrated methods based on CO.sub.2 stripping
to precipitate calcium from brackish waters prior to reverse osmosis
membrane desalination (Hasson et al., 2011; Segev et al., 2011, 2013).
Geroni et al., (2012) have demonstrated an analogous CO.sub.2-stripping
method for removing dissolved iron and associated metals from mine water.
CO.sub.2 degassing to increase the pH of river water samples containing
calcium and magnesium in solution is used as a method to determine
potential precipitative scaling of these elements in industrial
water-cooling applications (Gauthier et al., 2012; Chao et al., 2014;
Hamdi and Tlili, 2016). Circulating geothermal fluids rich in Mg, Ca and
CO.sub.2 will precipitate Mg and Ca out of solution under surface
conditions with CO.sub.2 degassing and consequent pH increase, as in the
case of natural travertine deposition (Pentacost, 2005; Rodrigo-Naharro
et al., 2013) and scale deposit clogging of pipes in geothermal energy
operations (Wasch, 2014). Also, Spilling et al., (2010) demonstrated
micro-precipitation of calcium carbonate and magnesium hydroxide onto
diatoms in a photosynthetic algal bioculture by the simple process of
discontinuing the CO.sub.2 supply such that pH was increased by
photosynthetic CO.sub.2 removal from solution. This process is known as
algal autoflocculation (Sukenik and Shelef, 1984). The Controlled
Hydrodynamic Cavitation (CHC) method of Ecowater Systems provides an
additional example (Ecowater Systems, undated). The German company
Budenheim (www.budenheim.com) developed an industrial method for
phosphorus recovery from waste streams that uses CO.sub.2 for pH control
in both directions via a "pH swing" method: the Budenheim Carbonic Acid
Process (Stossel, 2013; Ewart et al., 2014; Wollman and Moller, 2015).
This method removes phosphorus from sewage sludge first by injection of
CO.sub.2 at high pressure to solubilize organic P into dissolved
inorganic phosphorus (DIP) in an acidic liquid phase for a liquid/solid
separation step. A CO.sub.2 vacuum degassing step follows. This
precipitates P from the separated solution under high-pH conditions. To
decrease pH, CO.sub.2 pressure can be applied by sparging into and/or by
providing CO.sub.2 gas pressure over a solution. This can be done to keep
magnesium and/or calcium in solution in conditions where pH is low enough
to prevent precipitative saturation conditions from being reached. Such
procedures are common in "recarbonation" steps following the lime-soda
ash process for water softening (Butler, 1982; Wang et al., 2004; Messer,
2013). Thus CO.sub.2-based pH modification can provide control over
mineral precipitation, particularly magnesium hydroxide, and various
magnesium and calcium carbonates. The systematics of aqueous carbonate
chemistry are presented in Butler (1982, 1989), Emerson, (1975), Stumm
and Morgan, (3 editions: 1970, 1981, 1996), Langmuir, (1997), Zeebe and
Wolf-Gladrow, (2001), Bustos-Serrano, (2010), Talling, (2010), Millero,
(2013), Munhoven (2013a,b), and Orr et al., (2015). Various computational
models exist. These include PHREEQC
(http://wwwbrr.cr.usgs.gov/projects/GWC_coupled/phreeqc/;
www.hydrochemistry.eu; de Moel et al., 2015) and The Geochemists
Workbench (www.gwb.com; Bethke, 2008). A detailed understanding of
CO.sub.2 degassing and consequent pH increase and precipitation has been
obtained from the study of cave waters and speleothems (e.g., Holland et
al., 1964; Dreybrodt, 1980, 2013; Hansen et al., 2013). A 1-page summary
overview is provided by Railsback, (2006). Detailed systematics for
CO.sub.2 degassing from large scale water flows and in relation to
carbonate water chemistry have been developed for application in
aquaculture operations, particularly recirculating aquaculture systems
(RAS), (Grace and Piedrahita, 1993, 1994; Summerfelt et al., 2000, 2003,
2015; Moran 2010a,b; Timmons et al., 2001, 2002; Timmons and Ebeling,
2007, 2010, 2013). The degassibility of CO.sub.2 from alkaline solutions
differs greatly as a function of pH (Hardy et al., 2007; Willauer et al.,
2008, 2009a,b, 2010a,b, 2011, 2012a,b, 2014; DiMascio et al., 2010;
Eisaman et al., 2012). High pH carbonate waters do not contain
appreciable dissolved CO.sub.2 in solution. They absorb CO.sub.2 from air
(e.g., Clark et al., 1992). Once dissolved into water, this CO.sub.2 is
rapidly transformed into bicarbonate and carbonate anions. Under
conditions of exposure to CO.sub.2-free air, or N.sub.2, or vacuum,
high-pH alkaline solutions degas CO.sub.2 only very slowly. This is a
consequence of the (pH-increasing) slow kinetics of the process of the
combined dehydroxylation (HCO.sub.3.sup.-.fwdarw.CO.sub.2+OH.sup.-) and
dehydration (H.sup.++HCO.sub.3.sup.-.fwdarw.CO.sub.2+H.sub.2O) of
bicarbonate anion in aqueous solution into dissolved CO.sub.2 (Grace and
Piedrahita, 1993, 1994; Stumm and Morgan, 1996; Schulz et al., 2006; Guo
et al., 2009; Cohen and Kirschmann, 2004; Moran, 2010).
[0153] Chemically, Lake Kivu deepwater is a CO.sub.2-rich Mg(Na)-carbonate
water type of geothermal derivation (Tassi et al., 2009). Its condition
at depth is a natural example of CO.sub.2-based pH control over Mg and Ca
precipitation. Deepwater from 375 meters depth has 15.6 millimolar (mM)
magnesium at pH=6.15 (Tassi et al., 2016). This is approximately
100.times. saturation for a solution fully degassed under surface
conditions at 1 atmosphere without atmospheric CO.sub.2 equilibration.
This follows from the solubility product for magnesium hydroxide
Ksp=[Mg.sup.2+][OH.sup.-].sup.2=1.5.times.10.sup.11. This relation
determines a molar solubility of 0.16 mM/l solubility for Mg(OH).sub.2
and a pH=10.5 for a saturated equilibrium solution at 25.degree. C. with
no CO.sub.2 gas equilibrium present. This condition is modulated to
sub-saturation in Mg(OH).sub.2 and in Mg- and Ca-carbonates by CO.sub.2
in situ in Lake Kivu at 375 meters, as a consequence of the acidifying
effect of dissolved CO.sub.2 generating a pH of 6.15. There is extremely
high dissolved CO.sub.2 at 375 m depth in Lake Kivu: 62 mM/l, (2.7 g/l),
(Tassi et al., 2009). Magnesium hydroxide precipitates from aqueous
solution at this Mg concentration at pH.about.10 once CO.sub.2 in gas in
equilibrium with the solution reaches a partial pressure
.about.10.sup.-6, well below its present atmospheric partial pressure:
.about.4.times.10.sup.-4 atm (Stumm and Morgan, 1996 edition 2, FIG. 5.2;
Hanchen et al., 2008; Zolotov, 2014). Such circumstances are observed in
hyperalkaline springs in Oman, but are rare in terrestrial surface waters
(Neal and Stanger, 1984; Cipolli et al., 2004; Paukert et al., 2012;
Chavagnac et al., 2013a,b; Monnin et al., 2014; Olsson et al., 2014).
[0154] Recent years have observed massive effort to develop industrialize
CCU via organic synthesis. A review is provided by Liu et al., (2015).
Major advances have been obtained in scientific insight such as
overcoming endothermic constraints in the catalytic copolymerization of
CO.sub.2 as a C1 feedstock combining with olefins (e.g., Nakano et al.,
2014) and polycarbonates. CO.sub.2-copolymerized polypropylene carbonate
(PPC) is 44% CO.sub.2 by weight (Darensbourg and Wilson, 2012). This can
provide a major savings with respect to petrochemicals-sourced carbon
mass. Hence, some methods have been industrialized. A prominent example
was developed by Asahi Kasei Chemicals Corporation of Japan. Asahi's
process produces polycarbonate plastics using inputs of CO.sub.2 and
ethylene oxide (Fukuoka, 2012; Fukuoka et al., 2003, 2007, 2010).
Polycarbonates have been manufactured industrially in China since 2004
utilizing CO.sub.2 and propylene oxide (Wang et al., 2011).
[0155] Carbon dioxide can be utilized as a low-cost feedstock for
producing CO.sub.2 polyols in polyurethane production. CO.sub.2 comprises
roughly 50% of the mass of the CO.sub.2 polyols produced with CO.sub.2
incorporation as polycarbonate via alternating copolymerization of carbon
dioxide and epoxides. Industrialization of this process verifies the
practicality of CO.sub.2 utilization in plastics manufacturing
(Taherimehr and Pescarmona, 2014). A substantial economic logic supports
the production of plastics using CO.sub.2 polyols because, as noted
above, carbon from low-cost CO.sub.2 replaces carbon from high-cost
petroleum-based products. For example, the cost of carbon from CO.sub.2
at .about.US$50/tonne can be compared to the cost of carbon from
petroleum-derived propylene oxide at .about.US$2,000/tonne. Polyurethane
is used, for example, to produce mattress foam (Langanke et al., 2013;
von der Assen and Bardow, 2014; PU Magazine, 2013).
[0156] The German chemical giant Bayer has pioneered a
CO.sub.2-utilization "Dream" technology (Prokofyeva and Gurtler, 2015)
with German Government support (FMER, 2014). Bayer will commence
production of .about.5,000 metric tons per year of CO.sub.2 polyols in
Dormagen, Germany beginning in early 2016 under the name of its spin-off
company "Covestro" (www.covestro.com; Smock, 2015). The US company
Novomer (www.novomer.com) developed and commercialized a similar
CO.sub.2-polyols production technology in 2014 (Anderson et al., 2012,
2013; Sawant, 2013; Novomer, 2013, 2014, 2015, and undated; Bioplastics,
2014). Novomer's technology originated in research at Cornell University
(Allen et al., 2006). The British start-up company Econic Technologies
(www.econic-technologies.com) is developing a similar industrialization
of CO.sub.2 polyols production (Kember, 2013; Sorlien, 2014; Broadwith,
2015). Econic's technology is based on research at Imperial College,
London (Kember and Williams, 2012; Buchard et al., 2012; Chapman et al.,
2015; Romain and Williams, 2015; Williams et al., 2015).
[0157] In the conventional process, polyurethane is produced by reacting
polyols with isocyanate, typically with both polyols and isocyanate being
petrochemical derivatives. It now is possible for almost all of the
component inputs for polyeurethane foam to be obtained from
CO.sub.2-polyols plus plant-sourced materials (Bonnaillie, 2007;
Bonnaillie and Wool, 2007; Wool: U.S. Pat. No. 8,633,257 B2). A wide
range of non-petrochemicals-based "green" production chemistries for
polyurethane manufacture using bio-oils (and sometimes CO.sub.2 in
additional modalities) have been developed and industrialized by
companies such as Dow, BASF, Bayer, Cargill, Bio-Based, and Urethane Soy
Systems (Llgadas et al., 2010; Bahr and Mulhaupt, 2012; He et al., 2013;
Blattman et al., 2014; Ji et al., 2015; Lee and Deng, 2015; Wikipedia:
Natural oil polyols; Dow, undated). Algal oil as well as palm oils have
been demonstrated as feedstocks (Petrovic et al., 2013; Jennewein, 2015;
Arniza et al., 2015). The Malaysian company "Polygreen" has fully
industrialized manufacture of polyols from palm oil (Polygreen, website).
CO.sub.2 also is utilized as a foaming agent in polyurethane production
(Kim and Youn, 2000; Bonnaillie, 2007; Bonnaillie and Wool, 2007; Wool:
U.S. Pat. No. 8,633,257 B2; Jacobs et al., 2008; Hicks et al., undated).
[0158] The Nottinghman University research group of Professor Steve Howdle
coordinating with the European Union's REFINE project (www.fp7-refine.eu;
REnewable FunctIoNal MatErial) is seeking to develop methods for
low-temperature, low-cost, industrial polymerization-plasticization
reactions of bio-derived monomers dissolved within supercritical CO.sub.2
as a reaction medium (Howdle, 2001; Curia et al., 2015; Leitner, 2002;
Kemmere and Meyer, 2005).
[0159] A possibility for CO.sub.2 utilization is hydrogen peroxide
(H.sub.2O.sub.2) production. Hydrogen peroxide is a basic input into many
low-waste "green chemistry" processes, for example in the globally very
high volume production of polypropylene plastics via propylene oxide
(C.sub.3H.sub.6O) produced from propylene (C.sub.3H.sub.6). Propylene
(propene) typically is produced in industry petrochemically or via
coal-based syngas processes, or via dehydrogenation of propane. Hydrogen
peroxide utilization allows a low waste synthesis of propylene oxide from
propylene via the reaction:
C.sub.3H.sub.6+H.sub.2O.sub.2.fwdarw.C.sub.3H.sub.6O+H.sub.2O.
Considerable effort has been invested attempting to develop an industrial
method using supercritical CO.sub.2 as the reaction medium for hydrogen
peroxide production via cleantech "direct methods" (that is, by:
H.sub.2+O.sub.2.fwdarw.H.sub.2O.sub.2), (Hancu et al., 2002a,b; Chen and
Beckman, 2007; Chen, 2007; Garcia-Serna et al., 2014; Pashkova and
Dittmeyer, 2015; Edwards et al., 2015). Direct production of
H.sub.2O.sub.2 was industrialized by EVONIK and industrial partners using
a nano-Pd--Pt "NXCAT" catalyst process developed by Bing Zhou at
Headwaters Technology Innovation, Inc. This process used methanol as the
reaction medium rather than scCO.sub.2. It typically couples into
propylene oxide production in its industrial applications, hence named
the "HPPO" technology (Zhou, 2007, 2008; ThyssenKrupp, undated). The
combined process now operates globally on a huge scale. The hydrogen
peroxide synthesis component of the process, however, can operate in
scCO.sub.2 as well as in methanol. This was demonstrated initially by
Chen and Beckman, (2007).
[0160] Propylene production also can utilize CO.sub.2. As noted above,
propylene (propene) is a basic input into industrial plastics manufacture
on a huge scale globally. Propylene has been demonstrated by Dow to be
bio-manufacturable by fermentation utilizing commodity sugar input,
though not in an economically competitive manner (Rodriguez et al., 2014;
Nextant, 2009). Sugars derived from future lignocellulosic biorefining
may change the economics. At present, forms of "bio-polypropylene" can be
produced industrially from commodity polypropylene that is dilution-mixed
together with up to more than 50% treated algal biomass input, grown on
CO.sub.2 (Zeller et al., 2013; Cereplast, 2013; Algix, 2014). Moreover,
O.sub.2 inputs into hydrogen peroxide can be obtained as a byproduct of
electrolytic CO.sub.2 reduction processes, whereas H.sub.2 can be
obtained from biorefinery processing of algal and other types of biomass
grown on CO.sub.2. Therefore CO.sub.2 utilization inputs can be
substantial in propylene-based bioplastics production. Propylene and
ethelyne are manufactured industrially (together with gasoline and
propane outputs) on a large scale worldwide from natural gas inputs via
methanol in Lurgi's Gas-to-Chemicals (GTC) and Methanol-to-Propylene
(MTP) technologies (Koempel et al., 2005; Jasper and El-Halwagi, 2015) as
well as in broadly similar UOP-Honeywell Methanol-to-Olefins (MTO)
catalytic gas-phase synthesis processes (UOP, 2007, 2013, 2014). Methanol
synthesis from natural gas via syngas processing can use substantial
CO.sub.2 input for process optimization (Luu et al., 2015; Milani et al.,
2015).
[0161] Research developments indicate that economically industrializable
catalysts may allow electrocatalytic production of ethylene
(C.sub.2H.sub.4, also known as "ethene") by reduction of CO.sub.2
according to the overall reaction:
2CO.sub.2+2H.sub.2O.fwdarw.C.sub.2H.sub.4+3O.sub.2 (Kuhl et al., 2012;
Ogura, 2013; Chen et al., 2015; Roberts et al., 2015). Worldwide
production of ethylene exceeds that of any other organic molecule
produced by reaction. Ethylene typically is produced by steam cracking of
petroleum. Its major use is in plastics manufacture by polymerization
into polyethylene. Polyethylene is the largest volume of any type of
plastic produced worldwide. Catalytic carbonylation of ethylene with
carbon monoxide allows a range of chemical synthesis reactions alternate
to Fischer-Tropsch synthesis (Makaryan et al., 2015). Ethylene is
oligomerizable into diesel and other liquid transport fuels (Heveling et
al., 1998; OCMOL, undated). The EU "OCMOL" (Oxidative Coupling of Methane
followed by Oligimerization to Liquids) consortium initiative
(www.ocmol.eu) brought together a large group of chemicals and energy
companies to develop this capacity. Thus far, "ethylene-to-liquids"
processes have been industrialized on a pilot scale by the company
Siluria Technologies. Siluria's processes allow attractive small-scale
synthesis alternatives to large-scale indiustrial Fischer-Tropsch
synthesis of fuels, plastics and other industrial chemicals
(www.siluria.com). They were developed for stranded natural gas
utilization by a methane-to-ethylene process of oxidative coupling of
methane, followed by ethylene-to-liquids processing. Ethylene may become
a basic output in the development of so-called "solar fuels" using
electricity from solar and/or other renewable sources to power water
hydrolysis and CO.sub.2 reduction to ethylene followed by transformation
into liquid transport fuels. A reasonable basis in both science and
economics has been demonstrated by Singh et al., (2015).
[0162] Methanol is produced utilizing CO.sub.2 via direct catalytic
conversion/reduction/hydrogenation via the reaction: CO.sub.2+3H.sub.2
CH.sub.3OH+H.sub.2O. This can be an environmentally attractive form of
CO.sub.2 utilization. Methanol production from CO.sub.2 and H.sub.2
inputs depends for economic viability and environmental value upon the
availability of either bio-hydrogen (as by enymatic processing of
lignocellulosic sugars, for example) or low-cost electricity to obtain
hydrogen by water electrolysis (Olah et al., 2009, 2011). A piloting
scale industrial example (4,000 tonnes per year production) has been
created in Iceland by the company Carbon Recycling International (CRI:
www.carbonrecycling.is). CRU uses geothermally-generated CO.sub.2 and
electricity for electrolysis. The project demonstrates the base level of
the CO.sub.2-cycling "methanol economy" advocated by George Olah. In
Olah's vision, methanol can be used directly, or as a hydrogen-carrier,
or as an input in various ways for industrial production. One large-scale
example of the latter, the "methanol pathway" in industrial production,
is plastics manufacturing. The methanol pathway already operates on a
huge scale globally. It is growing rapidly due to the economic incentives
of switchover to natural gas feedstocks from petroleum feedstocks.
Methanol is a conveniently transportable product of natural gas reforming
via well-known long-industrialized synthesis gas ("syngas") processeing
(Methanex, 2015). China is especially active making this switch,
replacing petroleum with methanol in the manufacture of plastics and
industrial chemicals. China imports methanol from the USA where it is
manufactured from very low cost natural gas. World methanol production
circa 2015 exceeds 60 million tonnes per year. Therefore
industrialization conditions are excellent for connecting
CO.sub.2-utilizing direct synthesis of methanol (from CO.sub.2 and
H.sub.2), wherever feasable economically, with industrial chemicals,
fuels and plastics production. (Further details are provided below.)
[0163] CO.sub.2 provides a basis for "green chemistry" chemical processing
with wide flexibility for many different kinds of food, chemicals, fuels
and biorefining processes, used in various combinations and states of
pressure, temperature and gas-expansion with water, methanol, ethanol,
ionic liquids and various other solvents (Aitkin and Poliakoff, 2009;
Srinivas and King, 2010; King, 2014; Soh, 2014; Keskin et al., 2007;
Medina-Gonzalez et al., 2014; Jutz et al., 2011; Hintermair et al., 2010:
Francio et al., 2015; Wei et al., 2002; Fadhel et al., 2010; Jutz, 2009;
Jessop and Subramanian, 2009; Jessop, undated; Jessop et al., 2005, 2011,
2012). For example, CO.sub.2 utilization in the form new "smart solvents"
processing allows a technologies suite for developing greentech
production across a wide range of tasks in industrial chemicals
manufacture and biorefining. Algal biomass biorefining is another example
where extraction processes utilizing supercritical and dense CO.sub.2
alone as well as in mixtures with water, methanol and other solvents have
been demonstrated (Soh and Zimmerman, 2011, 2012; Bjornsson et al., 2012;
Soh et al., 2014; Goto et al., 2015; Du et al., 2013, 2015; Boyd et al.,
2012; Reyes et al., 2014; Paudel et al., 2015). The capability to extract
lipids from wet algal biomass is a particularly significant breakthrough
involving CO.sub.2 utilization, as well as DME (Goto et al., 2015) which
can be produced utilizing CO.sub.2 input (as noted elsewhere herein).
[0164] In 2005, Professor Philip Jessop of Queens University in Canada
developed a powerful "green chemistry" method of "switchable solvents."
Switchable solvents utilize CO.sub.2 and N.sub.2 to switch the polarities
and/or miscibility properties of ionic liquid solvents (Jessop, undated;
Jessop and Subramanian, 2009; Jessop et al., 2005, 2011, 2012;
http://www.switchablesolutions.com; Phan, 2008; Phan et al., 2008, 2009;
Kerton, 2009; Mercer, 2012; Durelle, 2014; Vanderveen et al., 2014;
Durelle et al., 2015; Boniface et al., 2016). The nature of the process
can include "switchable hydrophilicity" triggered by CO.sub.2 absorption
into, and exsolution out of, a switchable solvent. This capacity can
switch a miscible water-solvent mixture into an immiscible situation of
water separated from a (switched) hydrophobic solvent. Phan et al., 2009
demonstrated use of this method for the extractive separation of soybean
oil from flaked dried soybeans. Extraction of soybean oil into a
switchable solvent was followed by addition of water, causing an
immiscibility separation between the desired extracted oil product and a
water phase into which the solvent was separeated and dissolved. By
addition of bubbled CO.sub.2 to this solvent-in-water phase, a
"switching" of solvent polarity resulted. This created a 2-phase
miscibility situation of water separated from a solvent-+-CO.sub.2 phase.
The latter phase allowed recovery of the solvent upon removal of
dissolved CO.sub.2 by removing the CO.sub.2 atmosphere with nitrogen
bubbling. Boyd et al., (2012) and Du et al., (2013, 2015) have applied
this type of method to lipid extraction from wet algal biomass. Solvent
swithing with CO.sub.2 allows solvent processing of wet algal biomass
without an energy intensive biomass drying step. It also allows lipid
extraction with solvent recycling. Such methods avoid the energy
intensive step of distillation-separation for solvent recovery. CO.sub.2
provides the "switch" that allows water separation and solvent recycling
via miscibility rather than distillation.
[0165] Additional methods pioneered by the Jessop group have created
CO.sub.2-switchable dehydration agents for the removal of water from
organic liquids without distillation. A significant example of the
capability of this method is removal of water from ethanol (Boniface et
al., 2016).
[0166] Carbon dioxide can be utilized for carbon monoxide (CO) production.
One example is via the endothermic reverse Boudouard reaction:
CO.sub.2+C.revreaction.2CO (Lahijani et al., 2014a; Wikipedia: Boudouard
reaction). This reaction has been shown to be modifiable usefully to
lower temperatures with microwave stimulation (Hunt, 2013; Lahijani et
al., 2014b). Carbon monoxide is useful as a primary reducing agent in
mineral smelting for value addition to mineral concentrates. The classic
reaction is coal gasification to CO in an atmosophere of CO.sub.2.
However, the Boudouard reaction also is useful without coal input in
syngas production from biomass and/or municipal waste using inputs of
CO.sub.2 such as pure CO.sub.2, or CO.sub.2--O2, or CO.sub.2-steam.
[0167] CO.sub.2 addition into biomass gasification is useful in two modes.
The first is that it acts as a "gasifying agent." CO.sub.2 addition into
biomass gasification tends to increase both gasification extent and
thermal efficiency, as described in a subsequent section. The second mode
is via CO.sub.2 utilization in conversion of (undesirable) char output
within biomass gasification: increasing CO production from reduced carbon
via the Boudouard reaction, thereby increasing the overall CO yield in
syngas production (Kwon et al., 2009; Rafidah et al., 2011; Lahijani et
al., 2014; Prabowo et al., 2014, 2015a,b; Yi et al., 2015). In some
situations where CO directed into chemicals manufacture, CO.sub.2 overall
is net absorbed. CO.sub.2-enhanced biomass gasification can be utilized
as a form of advanced greentech for combined power and hydrocarbon
chemicals manufacture. Many options are helpfully categorized and
reviewed by Yi at al., (2015).
[0168] Another mode of production of carbon monoxide from CO.sub.2 is by
electrolysis, also known as "CO.sub.2 splitting." Intense research has
yielded a variety of potential modes of electrolytic CO.sub.2 splitting
to produce CO and O.sub.2 in catalyzed aqueous reaction systems (Whipple
and Kentis, 2010; Rosen et al., 2011, 2012; Chen et al., 2012; Tornow et
al., 2012; Lu et al., 2013, 2015; DiMeglio and Rosenthal, 2013; Jhong et
al., 2013; Kumar et al., 2012; Kumar et al., 2013; Saheli-Khojin et al.,
2013; Asadi et al., 2014; Medina-Ramos et al., 2014, 2015; Costentin et
al., 2014; Jones et al., 2014; Ma et al., 2014; Masel et al., 2014; Rosen
et al., 2015; Mao and Hatton, 2015; Shen et al., 2015). A breakthrough in
efficiency is the use of Au.sub.25 nanoclusters as an electrocatalyst,
allowing a production efficiency of .about.3.8 MWh per tonne of CO.sub.2
split into separated CO and O.sub.2 streams (Kauffman et al., 2015).
"Dioxide Materials" is a start-up company created as a result of research
cited above created at the University of Illinois. Dioxide Materials
seeks to develop commercially scaled systems using a combination of
electrolytic CO.sub.2 and H.sub.2O-splitting, producing CO, H.sub.2 and
O.sub.2. The purpose is to utilize CO.sub.2 and renewable electricity as
an alternate mode of production of fuels and industrial chemicals,
replacing petroleum-based fuels and chemicals (www.dioxidematerials.com;
ARPA-E, 2013; Masel et al., 2014; Dioxide Materials, 2014). In addition
to carbon monoxide, direct production of formic acid by combined water
and CO.sub.2 electrolysis is included within the company's agenda
(Whipple and Kenis, 2010; Whipple et al., 2010; Jhong et al., 2013; Masel
et al., 2014).
[0169] A non-aqueous modality of CO production from CO.sub.2 of particular
interest is electrolysis in molten lithium carbonate, Li.sub.2CO.sub.3,
developed by Valery Kaplan and colleagues in Igor Lubomirsky's research
group at the Weizmann Institute in Israel (Valery et al., 2010; U.S. Pat.
No. 8,906,219 B2). The net electrochemical reaction is:
CO.sub.2.fwdarw.CO+1/2O.sub.2. It proceeds via Li.sub.2CO.sub.3
(molten).fwdarw.Li.sub.2O.sub.(dissolved)+CO.sub.(gas)+1/2O.sub.2(gas),
balanced by continuous CO.sub.2 influx:
Li.sub.2O.sub.(dissolved)+CO.sub.2 (gas).fwdarw.Li.sub.2CO.sub.3
(molten). The process operates at .about.900 degrees centigrade. It
exhibits close-to-100% Faradaic and thermodynamic efficiency. It provides
separated gas flows of CO and O.sub.2 at the cathode and anode
respectively.
[0170] A promising closely related mode of CO.sub.2 utilization is the
method of electrolytic CO.sub.2 splitting in molten lithium carbonate
developed by the research group of Stuart Licht at George Washington
University (Ren et al., 2015; Li et al., 2015; Armitage, 2015; Licht et
al., 2016). This method splits CO.sub.2 into carbon nanofibers
(C.sub.CNF) and O.sub.2 gas. It operates with near 100% Coulombic
efficiency. (One mole of reduced carbon product is produced by .about.4
moles of applied electric charge.) Between 8 MWh and 16 MWh of energy
input are expected to be required for practical production of 1 tonne of
carbon nanofiber/nanotubes product, according to Ren et al., 2015, and
Licht et al., 2016. The lower end of this energy input range reaches and
exceeds carbon neutrality for utilization of CO.sub.2 when compared to
the amount of CO.sub.2 waste generated by generating process input power
efficiently combusting natural gas. Using solar power input of course can
make this process strongly CO.sub.2 absorbing. The method offers a
possibility for mass production of C.sub.CNF at a low cost with minimized
expenditure of energy and with essentially zero associated waste. A key
question for the future is whether this method can be refined to produce
carbon nanofibers efficiently in the high value forms of either Multiple
Walled Carbon Nanotubes (MWCNs), which have substantial value at
.about.US$100,000/kg, or Single Walled Carbon Nanotubes (SWCNs), which
have extreme value in the range of .about.US$1,000,000/kg (Wilkinson,
2015). SWCNs are distinctive for being low density (.about.1.4 g/cubic
cm), while exhibiting the highest tensile strength (up to .about.100 GPa)
of any known material along their tube direction, also with the highest
stiffness (elastic modulus) of any known material along their tube
direction. Industrial use of MWCNs and SWCNs has been developing since
the key publication heralding their discovery in 1991 (Ijima, 1991). A
high cost of production has been a substantial impediment against rapid
uptake involving a very wide variety of high tech uses involving strength
as well as electronic properties. In principal, wires manufactures from
carbon nanotubes could replace copper windings in electric motors. Carbon
nanotubes could create the world's strongest, lightest-weight ropes and
bullet-proof armor. They also can add substantial strength into aluminum
Al-alloy and other metals as nano-composites. These materials also may
have many future electronic uses: in batteries, capacitors, computational
integrated circuits, photovoltaics and light-emitting materials.
Substantial early-stage industrialization using large quantities has been
relatively simple thus far. It has followed the technology of fiberglass,
using carbon nanotubes as a strengthening agent in materials created with
epoxy matrix similar to other "carbon fiber" composites, only stronger
and lighter. An example of a manufacturer is the company Zyvex
Technologies (http://www.zyvextech.com). Zyvex has manufactured a range
of epoxy resin based products using advanced carbon tube fibers in
composites. These have been used in aerospace materials, superlight
military drone-boat hull fabrication, and various uses for lightweight
strong materials in high-end sports equipment ranging from bicycle wheels
to baseball bats to lacrosse sticks to sailboat masts. The world market
for carbon nanofibers, however, is small at present: perhaps less than
10,000 tonnes per year (Sherman, 2007; Johnson, 2014; Davenport, 2015;
McKenna, 2015). Energy efficient production of these very high strength
nanomaterials can be environmentally favorable in the context of life
cycle analysis (Khanna et al., 2008). If produced at low cost using an
efficient industriaization of the Licht method or developed analogs,
CO.sub.2 utilization to produce carbon nanofibers has substantial
potential for both export and local manufacturing industrialization. The
range of applications is immense for a low-cost production process (De
Volder et al., 2013; Wikipedia: Potential applications of carbon
nanotubes; NNI, 2014; Agarwal et al., 2010). The Licht method
electrolyzes CO.sub.2 absorbed into solution in a molten salt of lithium
carbonate, Li.sub.2CO.sub.3, in the range .about.725 to 800 degrees
centigrade. Production of C-nanofibers proceeds according to the net
reaction: CO.sub.2.fwdarw.C.sub.CNF+O.sub.2. This is via:
Li.sub.2CO.sub.3
(molten).fwdarw.Li.sub.2O.sub.(dissolved)+C.sub.CNF(solid)+O.sub.2(gas)
with fiber nucleation initiated and catalyzed by trace zinc and nickel. A
continuous process cycle is created by continuous absorbtion-infusion of
CO.sub.2: Li.sub.2O.sub.(dissolved)+CO.sub.2
(gas).fwdarw.Li.sub.2CO.sub.3 (molten) with removal of the products
C.sub.CNF and pure O.sub.2, with the latter being an additionally useful
co-product. Other similar electrochemical CO.sub.2 splitting technologies
producing O.sub.2 and carbon filamentrary material in molten alkali salt
and chlor-alkali salt systems have been demonstrated by Yin at al.,
(2013) and Ge et al., (2015). The latter reports production of a form of
amorphous carbon useful as negative electrode material for Li-ion
batteries. The general opportunity of molten carbonates for CO.sub.2
utilization is reviewed by Chery et al., (2015).
[0171] Other methods have been developed for CO.sub.2 utilization by
reduction to produce high-value pure carbon products. These include: C60
(Chen and Lou), Y-junction carbon nanotubes (Lou et al., 2006), diamond
(Lou et al., 2003a,b, 2004) and dense nanoporous graphene useful as the
energy storage material in high-power supercapacitors (Xing et al., 2015;
Science News, 2014). Graphene and other C-based supercapacitor
technologies have created many start-up companies.
[0172] CO.sub.2 can be utilized as an input to produce formic acid
(HCO.sub.2H) via a number of catalyzed hydrogenation methods following
the overall formulae: CO.sub.2+H.sub.2.fwdarw.HCO.sub.2H and
CO.sub.2+H.sub.2O.fwdarw.HCO.sub.2H+1/2O.sub.2. The Norwegian Company Det
Noeske Veritas, DNV-GL (https://www.dnvgl.com/) developed an innovation
agenda in the area of renewable energy management addressing
environmental risk. DNV decided to develop a CCU expertise to produce
formic acid (DNV, 2011; Sridhar et al., 2012; Agarwal et al., 2011).
DNV's techno-economic analysis (DNV, 2011) indicates formic acid offers a
potentially economically attractive mode for industrializinging a
power-to-liquids (PTL) technology: the transformation of electric power,
CO.sub.2 and water into industrial hydrocarbon liquids, including but not
limited to fuels. The attractiveness of electrochemical formic acid
production according to DNV's analysis follows four factors: (i) the
possibility to store electrical energy with carbon recycling; (ii)
technological potential based on efficiency performance for the
hydrogenation and de-hydrogenation of formate; (iii) formic acid
industrial utility apart from its specific use for energy storage; and
(iv) a market price situation for formic acid favoring the electricity
inputs required for electrolytic hydrogenation. In respect of the fourth
factor, DNV estimated that the electric power input cost for
CO.sub.2-recycling electrolytic production was less than half of the
commodity price of formic acid. (This price is based on the dominant
production method of methyl formate hydrolysis employed by the formic
acid producers BASF and Kemira-Taminco. Methyl formate is produced from
methanol and carbon monoxide inputs. Robledo-Diez, 2012.) An electricity
input cost estimate is based on .about.4 MW-h per tonne of formic acid
produced (DNV, private communication). This corresponds to an electricity
input price of .about.$400/tonne of 100% formic acid at a power cost of
.about.US$0.10/kW-h. There has been special interest in Europe in both
PTL and Power-To-Gas (CH.sub.4) CO.sub.2-recycling power-storage
technologies. This interest is for stabilizing the intrinsically
irregular streams of electric power generated by wind and solar energy.
Stabilizing strategies that direct excess electric power flows into
synfuels and industrial chemicals production are attractive if there are
prospects for combining economic profitability with environmental
sustainability. Formic acid (H.sub.2CO.sub.2) possibly can operate with
superior performance in this function as a CO.sub.2-based hydrogen
carrier, allowing a carbon neutral process if renewable power sources are
utilized. Formic acid therefore provides a basis for a "hydrogen
battery."
[0173] The US start-up company "Liquid Light" (www.llchemical.com)
developed out of electrocatalyst innovations at Princeton University in
the PhD thesis of Emily Cole, advised by Professor Andrew Bocarsly (Cole,
2009; Cole and Bocarsly, 2010; Cole et al., 2010). The company has
developed, patented and demonstrated several electrochemical methods of
reduction of CO.sub.2 into formate and formic acid (U.S. Pat. No.
8,562,811 B2). These methods require inputs of CO.sub.2 and electricity.
External hydrogen gas inputs are not required because hydrogen is
provided by the electrochemical process which includes water-splitting.
Liquid Light also has developed methods for CO.sub.2 electrochemical
reduction to produce other industrial biochemicals. The company is
focused especially on monoethelyne glycol (MEG) used in many industrial
processes including production of plastic beverage bottles made from
polyethelene terephthalate, PET (Law, 2015a,b). Estimates provided in
Parajuli et al., (2014) indicated electric power input costs in excess of
the market price of formic acid. However, these authors noted this was
based substantially on a low process selectivity, CO.sub.2-to-formate of
only 40%, with expectations of future enhancement. (A process improvement
increase to 60% was documented in White et al., 2014.) Success in this
agenda could offer useful opportunities for electrochemical production of
formic acid utilizing CO.sub.2 input. More broadly, Liquid Light
represents an exciting agenda for industrializing CO.sub.2 recycling into
industrial chemicals via electrochemical technologies. As indicated by
the company's name, a distinctive aspect of its vision is eventually to
use photoelectric power and/or direct photocatalytic reduction of
CO.sub.2 (White et al., 2014; Bocarsly, 2014). At present, Liquid Light's
main focus is on developing its CO.sub.2-utilization core platform for
formate electrosynthesis linking to oxalic acid then MEG production for
use in PET beverage bottles manufacture (Zhu et al., 2013; Law, 2015a,b;
SRI Equity Research, 2015).
[0174] An imidazolium-modified gold catalyst developed by Toshiba has been
demonstrated to allow production of ethylene glycol by electrochemical
reduction of carbon dioxide with high Faradaic efficiency (Tamura et al.,
2015).
[0175] Hydrothermal conversion of CO.sub.2 and water into formic acid is a
biomimetic mode of CO.sub.2 utilization developed by Fangmin Jin and
collaborators. This method couples CO.sub.2 reduction with
water-splitting catalyzed by the oxidation of zero-valent metals (Al, Mn,
Fe, Zn, Mn), especially zinc in the presence of copper, in a
metal/metal-oxide redox cycle (Wu et al., 2009; Jin et al., 2011, 2012,
2014; Zhang et al., 2011; Lyu et al., 2014; Chen et al., 2015; Demirel et
al., 2015; Yao et al., 2015; Zeng, 2014; Wang et al., 2015a,b; Zhong et
al., 2015). Similar CO.sub.2-utilizing methods have been demonstrated for
hydrothermal conversion of CO.sub.2 into methanol (Guan et al., 2003; Huo
et al., 2012; Lyu et al., 2015; Ren et al., 2015.)
[0176] Formic acid is an industrial chemical with growing use globally. It
has traditional utility as a pickling agent in the tanning of hides, as a
preservative in silage animal feeds, and as a coagulant in the production
of rubber. Ecologically beneficial uses replacing polluting industrial
processes are of particular interest in the area of papermaking. Formic
acid has been known as an economically attractive wood pulping agent
since 1983 (Bucholtz and Jordan, 1983). It has been a pulping component
in the environmentally beneficial "Organosolv" suite of technologies
widely used in the pulp and paper industry, with special application to
in the delignification of eucalyptus wood (Baeza et al., 1991). Rousu et
al., (2002) first demonstrated the utility of formic acid as the basis
for an ecologically attractive closed-cycle greentech pulping process for
fibrous agricultural waste integrated with biorefining: the "Chempolis"
process. The Rousu family industrialized this process in Finland via
their company Chempolis (www.chempolis.com). Formic acid can be used in
the hydrolysis of bamboo cellulose to liberate sugars with high
efficiency (Sun et al., 2008; Zhuang and Li, 2012; Kupainem, 2012;
Hagesawa et al., 2013; Li et al., 2014). Similarly, formic acid can be
used to depolymerize bamboo lignin, and other sources of lignin, into
valuable aromatic products such as, for example, vanillin (Rahimi et al.,
2014). Additionally, formic acid can be used as an effective delignifying
pulping agent for banana stem waste in papermaking (Mire et al., 2005;
Jahan et al., 2007; Sridach, 2010; Sannigrahi and Ragauskas, 2013).
Formic acid biomass treatment technology utilizing bamboo and banana tree
waste and other non-food forms of biomass has many potential future
bio-production applications additional to the direct one of papermaking.
These range from sugars separation and production (from bamboo:
principally glucose .about.41% and xylose .about.22% by weight: Li et
al., 2012) to high-efficiency catalysis-based and also enzymatic
bio-hydrogen production from sugars (Li et al., 2015; del Campo et al.,
2013; Rollin et al., 2015), to fine bio-chemicals production in many and
various modalities (Philbrook et al., 2013), to ethanol production by
fermentation (Littlewood et al., 2013). Xylose can be processed into the
valuable "tooth-friendly" food sweetener sugar-alcohol "birch sugar"
xylitol (Dupont-Danisco trade name: "Xivia") which inhibits dental decay
and is medically indicated for sucrose substitution for diabetics. Dupont
is a major manufacturer of xylitol in the alternative sweeteners industry
(Dupont, 2012).
[0177] Chempolis (www.chempolis.com) has successfully industrialized
formic acid pulping via its formic acid-based biorefining process and
plant design. Chempolis' plants are able to intake both tree wood and
other non-wood biomass such as bamboo, banana stem waste, papyrus reeds,
and corn/maize, and sorghum stover. The company's industrialized
technologies include: (i) environmentally benign pulping ("formicofib")
with co-production of potassium fertilizer and biochemicals including
acetic acid, furfural, glucose and pentose sugars; and (ii) non-food
cellulosic ethanol production ("formicobio"), (www.chempolis.com,
various). Chempolis is developing biorefineries utilizing formic acid
technologies in China, India and Indonesia. The chemistry of organic acid
solvent effects in woody biomass breakdown and conversion reactions,
including that of formic acid, is reviewed by Shuai and Luterbacher
(2016).
[0178] CO.sub.2 can provide related industrial value in the area of
biomass preparation as a lignin solvent, as a sugars-releasing cellulose
hydrolyzing agent, and as a mechanically explosive microshredding biomass
agent for pulp production for paper and for pretreatment of both woody
and non-woody for biorefining into chemicals and biofuels. The uses of
CO.sub.2 in this area include: (i) carbonic acid pretreatment (Walsum and
Shi, 2004; Walsum et al. 2007; Jian et al., 2009), (ii) supercritical
CO.sub.2 pretreatment sometimes including micro-disaggregating
pressure-release "CO.sub.2 explosion" (Puri and Mamers, 1983; Zheng,
1995, 1998; Srinivasan and Ju, 2010; Narayanaswamy et al., 2011; Santos
et al., 2011; Gu, 2013; Gu et al., 2013; Gurgel et al., 2014; Maurya et
al., 2015; Relvas et al., 2015), and (iii) pressurized bi-phasic
CO.sub.2--H.sub.2O thermal pretreatment (Li and Kiran, 1988; Luterbacher
et al., 2010, 2012a,b). These techniques allow CO.sub.2 to be used as an
effective agent for biomass pretreatment in a number of specific
contexts, such as, for example, xylose separation for xylitol production
from bamboo and/or banana stem waste as an extractive value-capturing
process integrated into pulping processes for papermaking. The
CO.sub.2-specialized company, the Linde Group (www.linde-worldwide.com)
has developed several additional uses for CO.sub.2 in papermaking (Linde,
2012). These include soap acidulation, pulp washing, and process pH
control and stabilization (Haring, 2008).
[0179] Supercritical CO.sub.2 can be used for intake biomass treatment for
the production of viscose textiles made from wood, bamboo and banana stem
waste based on regenerated cellulose, (Zhang et al., 2013; Saxena, 2013;
Lenzing, 2012; Medina-Gonzalez et al., 2012).
[0180] CO.sub.2 provides an effective recovery mechanism for the
lignocellulosic biomass solvent .gamma.-valeractone (GVA). CO.sub.2
generates a biphasic immiscibility separation. A GVA plus CO.sub.2 phase
autoseparates from a sugars-rich aqueous phase. This phenomenon creates
the possibility of recovery-recycling of GVL in GVL-based biorefining
scenarios utilizing CO.sub.2 (Lueterbacher et al., 2014, 2015a,b;
Luterbacher and Luterbacher, 2015; Fang and Sixta, 2015; Han et al.,
2015; Shuai et al., 2016; Shuai and Luterbacher, 2016).
[0181] Formic acid is used as a fuel in Direct Formic Acid Fuel Cells
(DFAFCs). This technology is well demonstrated as a form of
high-efficiency, high energy density battery, recharagable by reloading
formic acid. The technology was developed in the University of Illinois
(Yeom et al., 2003; Ha et al., 2004). It was thereafter (abortively)
industrialized by a group of large companies linked with the company
Tekion (Wikipedia entry: "Formic Acid Fuel Cell"). Applied research
continues, as reviewed by Wang et al., 2014). The University of
Eindhoven's "Team FAST" is building a formic acid-powered car
(www.teamfast.nl). There also is active start-up industrialization. The
Mantra Venture Group (www.mantraenergy.com) has demonstrated a multi-fuel
fuel cell called a Mixed-Reactant Fuel Cell (MRFC) which can function as
a DFAFC (Mantra Energy Alternatives, undated). Formic acid also may be
used in formic acid reformers providing hydrogen into fuel cells. This
technology has been industrialized by Neah Power (www.neahpower.com). It
is used in drones made by Silent Falcon UAS Technologies
(www.silentfalconuas.com). Larger-scale industrialization of formic
acid-based energy and hydrogen storage technologies is possible. A
thermodynamic and economic analysis by Singh et al. (2015) shows that
formic acid is in general a highly attractive business target for
electrochemical CO.sub.2 reduction to produce a commodity chemical with
energy-carrying capacity. Research efforts developing improved
efficiencies in catalysis and production modes for CO.sub.2 hydrogenation
to formic acid and formate have been proceeding with rapidity and many
successes (Leitner, 1999; Li and Oloman, 2005, 2006, 2007; Oloman and Li,
2008; Whipple and Kenis, 2010; Whipple et al., 2010; Enthaler et al.,
2010; Agarwal et al., 2011; Boddien et al., 2011; Hull et al., 2012;
Martindale and Compton, 2012; Wesselbaum et al., 2012; Fujita et al.,
2013; Jhong et al., 2013; Junge and Beller, 2013; Czaun et al., 2013;
Beller and Bornscheuer, 2014; Zhang et al., 2014a,b; Jin et al., 2014;
Filonenko et al., 2014; Schmidt, 2014; Moret et al., 2014; Takeda et al.,
2014; Lu et al., 2014; Watkins and Bocarsly, 2014; Blas Molinos, 2015;
Cheng et al., 2015; Wang et al., 2015; Zhang et al., 2015; Su et al.,
2015a,b; Lee et al., 2015; Kortlever at al., 2015; Kothandaraman et al.,
2015; Min and Kanan, 2015; Zhang et al., 2015; Del Castillo et al., 2015;
Yoo et al., 2015; Gao et al., 2016).
[0182] CO.sub.2 can be hydrogeneted to formate in non-photosynthetic
bioengineered systems (Jajesniak et al., 2014; Alissandratos and Easton,
2015). Future CO.sub.2 utilization may produce formic acid
biocatalytically by enzymatic biotechnologies, either whole cell or
cell-free, following initial work by Thauer, (1972), Ruschig et al.,
(1976), Klibanov et al., (1982), Obert and Dave, (1999), Miyatani and
Amao, (2002), Lu et al., (2006) and Reda et al., (2008). Reviews have
been provided by Lanjekar et al., (2011), Beller and Bornscheuer, (2014),
Jajesniak et al., (2014), and Shi et al., (2015). A major breakthrough
was made by Schuchmann and Muller (2013; see also Pereira, 2013). These
researchers demonstrated that a single enzyme, "hydrogen-dependent carbon
dioxide reductase" (HDCR), was able to hydrogenate CO.sub.2 into formate
efficiently and with a very high turnover rate without additional
cofactors. They further demonstrated a whole-cell formate production
technique that intakes CO.sub.2 plus H.sub.2, or CO plus H.sub.2
(syngas), and outputs formate.
[0183] CO.sub.2 utilization to produce formic acid can be combined with
biotechnologies for biofuels production by microbial electrosynthesis. A
formic-acid based "electromicrobial" system for electrolytic CO.sub.2
utilization coupled with biosynthesis of biofuels such as butanol was
developed by the UCLA group of James C. Liao (Liao, 2013; Li et al.,
2012). This work provided a basis for the start-up company Easel
Biotechnologies, LLC (www.easelbio.com). Easel Biotechnologies is focused
on bioproduction of electrofuels.
[0184] The start-up biotechnology company Gingko Bioworks
(www.gingkobioworks.com) bioengineered chemoautotrophic microbes capable
of transforming formate input into a variety of biochemicals and biofuels
(Lane, 2015).
[0185] Carbon dioxide can be utilized by the co-electrolysis (or
"co-splitting") of CO.sub.2 and H.sub.2O together in high-temperature
solid oxide electrolyzer cells (SOECs). With intake of CO.sub.2, H.sub.2O
and electric power, SOECs yield an anode output of pure O.sub.2 gas and a
cathode output of syngas (H.sub.2 and CO), according to the net reaction:
H.sub.2O+CO.sub.2.fwdarw.O.sub.2+(H.sub.2+CO), (Ebbesen et al., 2009;
Ebesen and Mogensen, 2009; Graves, 2010; Graves et al., 2011; Mogensen,
2013; Chen et al., 2013; Stempien et al., 2013; Badwal et al., 2014).
This technlogy allows storage of electrical energy (typically
intermittant renewable energy when in excess) into methanol, DME and
other synthetic liquid fuel outputs of syngas production (GTL). SOEC
co-electrolyzer systems also can provide oxygen output. The technology is
integrable with various modes of biomass gasification and upgrading
(CO.sub.2 methanification) and power generation, and with syngas
production as noted above. Overall, CO.sub.2 utilization-recycling via
co-electrolysis with water in SOECs is a substantially promising and
flexible "green" technology likely to be implemented in Europe future
low-CO.sub.2 energy and fuels economy. SOEC co-electrolysis and related
technologies have been developed in a serious manner in Denmark with
initial industrialization by the company Haldor Topsoe collaborating with
a large research group at the Technical University of Denmark (Minh and
Mogensen, 2013; Ridjan et al., 2013; Ryde, 2014; Hansen, 2015; Jensen,
2015). The German company "Sunfire GmbH" (www.sunfire.de) has
commercialized a SOEC-based Power-to-Liquids system. Sunfire's method
uses H.sub.2 produced in a SOEC from steam (with O.sub.2 byproduct). This
H.sub.2 is reacted with CO.sub.2 input into syngas flowing into
Fischer-Tropsch reactors. The combined process produces diesel and other
synfuels with 70% capture of energy input into caloric value output in
the synfuels (Sunfire, 2014). Development activity for SOEC
co-electrolysis in the US is reviewed by Stoots (2011). Research
describing a technologically different modality to co-electrolyze
CO.sub.2 and H.sub.2O with variability control in the H.sub.2/CO ratio of
syngas output has been described by Kang et al., (2014). Also, Walsh et
al., (2014) demonstrated a potentially low-cost modality of
co-electrolysis of CO.sub.2 and H.sub.2O catalyzed in an aqueous flow
using a molybdenum catalyst with multi-walled cabon nanotubes. The
process yields an H.sub.2/CO molar ratio of 2, ideal for methanol
production.
[0186] Professor Jacob Karni of the Weizmann Institute developed a thermal
process for the co-dissociation "splitting" of CO.sub.2 plus water vapor
(Karni, 2011) into syngas and oxygen. Research of his group led to the
formation of the start-up company NCF/NewC O.sub.2-Fuels
(http://www.newco2fuels.co.il/about/). This company is now a subsidiary
of Australia-based GreenEarth Energy, Ltd
(http://www.greenearthenergy.com.au).
[0187] Carbon dioxide can be utilized combined with methane for syngas
production by catalyzed gas phase reactions for Gas-to-Liquids (GTL)
production of methanol and higher molecular weight hydrocarbon fuels. For
example, carbon dioxide can be utilized via the endothermic "dry
reforming" reaction CO.sub.2+CH.sub.4.revreaction.2CO+2H.sub.2 to produce
syngas with H.sub.2/CO=1, though the net ratio is lower due to heat
production required by the reaction. (See: Noureldin et al., 2015). One
well-established example of commercialized industrial CO production by
dry reforming natural gas or LPG with CO.sub.2 is the "Calcor" process.
This process was created by the German company Caloric Anlagenbau GmbH
(Tuener et al., 2001).
[0188] Several modes exist for CO.sub.2 input into syngas production in
combination with natural gas for the purpose of producing methanol and/or
other synthetic fuels and chemicals (Luu et al., 2015). "Methane
oxyforming" (sometime called "Oxy-CO.sub.2 reforming") utilizes inputs of
methane, CO.sub.2, water and O.sub.2. It involves combinations of steam
reforming of methane (CH.sub.4+H.sub.2O.fwdarw.CO+3H.sub.2), dry
reforming of methane (CH.sub.4+CO.sub.2.fwdarw.2CO+2H.sub.2), and partial
oxidation reforming of methane (CH.sub.4+1/2O.sub.2.fwdarw.CO+2H.sub.2).
With inclusion of dry reforming, this combination utilizes CO.sub.2,
yielding the net reactions:
3CH.sub.4+O.sub.2+CO.sub.2.fwdarw.4CO+6H.sub.2, and
5CH.sub.4+2O.sub.2+CO.sub.2.fwdarw.6CO+10H.sub.2 (York et al., 2007;
Jiang et al., 2010). A variation known as "tri-reforming" adds-in the
catalytic combustion of methane, releasing heat:
CH.sub.4+2O.sub.2.fwdarw.CO.sub.2+2H.sub.2O. Tri-reforming has been
developed as a possible widespead industrial modality of utilizing impure
CO.sub.2 from flue gases to create synthetic fuels ("synfuels") and
chemicals by Fisher-Tropsch and related processes (Song, 2001, 2006; Song
and Pan, 2004; Jiang et al., 2010). Fisher-Tropsch GTL historically has
been limited to very large scale industrial complexes (Lewis, 2013).
However, the situation has changed drastically with the development of a
new market for small-scale GTL plants. The plants are being created for
the utilization of "stranded gas" all over the world (Jacobs, 2013). Most
of the existing companies involved are reviewed in a 2014 Word Bank
report and slide deck by Fleisch, (2012, 2014). Companies include: Oberon
Fuels (www.oberonfuels.com, Oberon Fuels, undated), Velosys
(www.Velocys.com, Velosys, undated), CompactGTL (www.compactGTL.com,
CompactGTL, undated), GasTechno (www.GasTechno.com, GasTechno, undated;
Breidenstein, 2015), Greyrock Energy (www.greyrock.com, Grey Rock Energy,
undated) and Maverick Synfuels/(www.mavericksynfuels.com;
www.mavericknorthstar.com). Small-scale GTL plants allow the conversion
of "stranded" natural gas obtained from pipeline-isolated wells, into
valuable products in combination with inputs of CO.sub.2, water and
sometimes separated oxygen, combined in various mixtures. Maverick has a
line of small "Oasis" GTL plants focused on methanol production (Maverick
Synfuels, 2014, undated).
[0189] Another process utilizing CO.sub.2 is the production of acetic acid
(CH.sub.3COOH, or CH.sub.4CO.sub.2). Acetic acid is the active substance
in vinegar obtained by fermentation of ethanol. It is a basic input into
many industrial synthesis processes. World demand is .about.12 million
tonnes per year circa 2015 (Tweddle, 2014). Acetic acid produced for
industrial use typically has been made by a non-biological syngas
production process via methanol. To produce acetic acid, methanol is
carbonylated with input of carbon monoxide, initially via the "Monsanto
process" and later in the "Cativa process." In 2014, BP announced it had
developed an improved large-scale industrial synthesis via the "SaaBre
process," based on coal-to-syngas and/or natural gas reforming
(Pavlechenko, 2014). BP announced it would apply the new synthesis method
in a large facility planned for Oman (2b1st Consulting, 2014). The Gas
Technology Institute is developing a direct catalytic gas synthesis GTL
production process for acetic acid based on CO.sub.2 and methane inputs
(CCEMC, 2014). Acetate also can be produced using CO.sub.2 directly by
electrochemical reduction of CO.sub.2. For example, impressive lab
results were described by Yanming Liu et al. (2015) for an aqueous system
using a non-metallic catalyst: nitrogen-doped nanodiamond deposited on
the surface of an array of silicon micropillars.
[0190] Industrial bioproduction of acetic acid has been practiced for many
centuries via the fermentive oxidation of ethanol by aerobic acetic acid
bacteria (Ebner and Sellmer-Wilsberg, 2002; Raspor and Goranovic, 2008;
Mamlouk and Gullo, 2013). An historic step towards CO.sub.2 utilization
in acetic acid bioproduction relates to the discovery of an
acetone-butanol fermentation process used in the production of explosive
munitions (smokeless powder cordite). A major breakthrough was developed
by Chaim Weizmann, later first President of Israel, who patented a
high-productivity process based upon the fermenting capacities of the
aneorobic acetogenic (Hartmanis and Gatenbeck, 1984; Millat et al., 2011,
2013; Jeon et al., 2012) acetone-producing bacterium Clostridium
acetobutylicum. This was in the UK in 1915 in the urgent wartime
emergency of WWI (Jones and Woods, 1986; Krabben, 2014; Weizmann
Magazine, 2015). Weizmann's method fed biocultures with various feed
sources such as corn and potato mash starch and molasses glucose.
However, more recently, broadly related industrial acetate bioproduction
methods have been developed using gas inputs of CO.sub.2 and/or CO, with
and without H.sub.2 addition, as carbon sources (Barker et al., 1945;
Levy et al., 1981a,b; Worden et al., 1991: Daniell et al., 2012). Such
processes follow what is believed possibly to be the oldest carbon-fixing
process on Earth, utilizing CO.sub.2 and CO.sub.2+H.sub.2 inputs
(Poehlein et al., 2012) in a process known as gas fermentation. Acetic
acid is produced by microbial gas fermentation with input of both syngas
and CO.sub.2+H.sub.2 mixtures (Daniell et al., 2012; Liew et al., 2013;
Khan et al., 2014; Latif et al., 2014; Kantzow et al., 2015; Devarapalli
and Atiyeh, 2015; Durre and Eikmanns, 2015; Nybo et al., 2015). Acetate
production from CO.sub.2+H.sub.2 gas fermentation is by cell excretion
into the surrounding water medium. Therefore producing cells do not have
to be harvested. Productivity can be extremely high in specialized
bioreactors. Yields up to 148 g.sup.-1 d.sup.-1 acetate have been
observed via a continuous dilution process of extraction from cell
cultures of gas fermenting Acetobacterium woodii (Kantzow et al., 2015).
[0191] LanzaTech (www.lanzatech.com) is a dynamic global company focused
on carbon recycling via gas fermentation biotechnology (Kopke et al.,
2010, 2011; Daniell et al., 2012; Liew et al., 2013; Harmon, 2015,
Holmgren, 2015). LanzaTech and two other companies, INEOS Bio and
Coskata, have industrialized gas fermentation for commodity ethanol
production from syngas (Kopke et al., 2011; Durre and Eikmanns, 2015).
LanzaTech and its several industrial partner companies utilize process
gas (for example from steel mill operations) and/or syngas (for example
from biomass gasification) to feed microbes in large bubbled tanks
yielding ethanol and other output commodity chemicals. LanzaTech also can
utilize CO.sub.2-rich input gas compositions. For example, the company's
website describes a partnership with the Indonesian oil and gas and
petrochemicals company Petronas to industrialize a process to utilize
CO.sub.2 by gas fermentation with CO.sub.2+H.sub.2 inputs using
LanzaTech's genetically engineered platform organism (De Guzman, 2012).
The process described uses gas fermentation to produce acetic acid. This
then feeds a second fermentation process producing lipids. These lipids
can be separated into two components: high-value nutraceuticals and a
residue used for biofuels production (Daniell et al., 2012; LanzaTech,
website; Goyal, 2014; Holmgren, 2014). LanzaTech's biological synthesis
utilizing CO.sub.2 employs what is thought to be the one of the Earth's
oldest metabolic pathways. This is the Wood-Ljungdahl pathway of
microbial CO.sub.2 reduction/fixation utilizing hydrogen to produce
acetic acid. The Wood-Ljungdahl pathway proceeds according to the overall
stochiometry:
4H.sub.2+2CO.sub.2.fwdarw.CH.sub.3COO.sup.-+H.sup.++2H.sub.2O, (Wood,
1991; Wood and Ljungdahl, 1991; Drake, 1994; Ragsdale and Pierce, 2008;
Fuchs, 2011; Schuchmann and Muller, 2014). It is one of the modes whereby
methane is produced in Lake Kivu via an acetogeneisis pathway in its
sediments (Tietze at al., 1980; Leigh et al., 1981; Schoell et al., 1988;
Lliros Dupre, 2009; Bhattarai et al., 2012; Pasche et al., 2011; Wuest et
al., 2012).
[0192] An example of the Wood-Ljungdahl pathway operating is another
industrial CCU mode: adding CO.sub.2 to increase methane production in
the anerobic digestion of sewage (Bajon Fernandez, 2014; Bajon Fernandez
et al., 2014, 2015; Yasiin et al., 2015; Koch et al., 2016).
[0193] A modified mode of CO.sub.2 utilization to produce acetate via the
Wood-Ljungdahl pathway without hydrogen addition is "microbial
electrosynthesis." Microbial electrosynthesis requires inputs of CO.sub.2
and electricity. The biology involved is a recent discovery. It is
fascinatingly interesting as well as open to innovations from synthetic
biology to create new product output modes (Cheng et al., 2009; Lovely,
2010, 2011, 2012, 2015; Nevin et al., 2010, 2011; Rabaey and Rozendal,
2010; Rabaey et al., 2011; Lovley and Nevin, 2011, 2013; Jeon et al.,
2012; Li et al., 2012; Logan and Rabaey, 2012; Hawkins et al., 2013;
Lovely et al., 2013; Wang and Ren, 2013; Zaybak et al., 2013; Lovely and
Malvankar, 2015; Bengelsdorf et al., 2013; Ueki et al., 2014; Xu et al.,
2014; Bertsch and Muller, 2015; Durre and Eikmnns, 2015; Jourdin et al.,
2015; Patil et al., 2015; Tremblay and Zhang, 2015; Gildemyn et al.,
2015; Choi and Sang, 2016; www.electrofuels.org; www.geobacter.org).
LanzaTech has developed a pilot-scale commercial biology platform to
produce acetate and other commodity chemicals with this type of
biotechnology (Mihalcea, 2015; Holmgren, 2015; Lai, 2015; Griffin, 2015)
via both methods: (i) CO+H.sub.2 and/or CO.sub.2+H.sub.2 gas
fermentation, and (ii) "electrotrophic" microbial electrosynthesis
utilizing CO.sub.2+electrons as inputs. The company also has developed a
platform using heterotrophic algae to transform acetate into the
high-value omega-3 nutraceutical fatty acid DHA (Asian Scientist, 2014;
Holmgren, 2014). OakBio is an additional start-up biotech company active
in similar areas: utilizing CO.sub.2-rich flue gases from cement
production as inputs into gas fermentation to produce bioplastics
(OakBio, 2014; Theulen, 2015a,b).
[0194] CCU to convert CO.sub.2 to methane can be by means of a biological
phenomenon called "electromethanogenesis" (Cheng et al., 2009)
Electromethanogenesis can convert CO.sub.2 into CH.sub.4 using the input
of electrons directly consumed by electrotrophic microbes (Van
Eerten-Jansen et al., 2012, 2013 2015; Van Eerten-Jansen, 2014; Hara et
al., 2013; Lohner et al., 2014). H.sup.+ in water serves as the hydrogen
source (Batlle-Vilanova et al., 2015; Fu et al., 2015; Beese-Vasbender et
al., 2015; Tremblay and Zhang, 2015). Or electromethanogenesis can use
other biological utilizations of electron inputs. Some very interesting
laboratory results have been obtained using methanogenic microbes
indigenous to depleted oil fields with interest to discover methods to
produce methane underground via CO.sub.2 flooding with electrical input
(Kobayashi et al., 2012; Kuramochi et al., 2013; Sato et al., 2013; Fu et
al., 2015; Maeda et al., 2015; Mu et al., 2014; Mu and Moreau, 2015;
Vilcaez, 2015; Koide and Yamazaki, 2001; Beecy et al., 2001). This effort
offers a new horizon in the field of Microbial Enhanced Oil Recovery,
MEOR (Youssef et al., 2009). Very high conversion CUU efficiencies to
produce methane and various biochemicals have been observed for
hyperthermotrophic systems involving both H.sub.2 pathways and direct
electrotrophs (Keller et al., 2013, 2015; Sato et al., 2013; Hawkins et
al., 2011, 2013; Hawkins, 2014; Maeda et al., 2015; Zeldes et al., 2015).
These findings follow basic quantitative insights into biological
thermodynamic as well as engineering process efficiencies. They suggest
that CCU optimalities for "biosolar fuels" and "biosolar chemicals" are
likely to be found in this direction (Hawkins et al., 2011, 2013;
Bar-Even et al., 2012a,b; Ducat and Silver, 2012; Frock and Kelly, 2012;
Fast and Papoutsakis, 2012;). It is too early to know if such biological
power-to-gas methods utilizing CO.sub.2 will have sufficient efficiency
to have commercial potential. The observations and insights are quite new
and important, especially as the barriers to economic viability for
biofuels other than ethanol are very substantial (Papoutsakis, 2015;
Dimitrou et al., 2015; Han et al., 2015; Roken and Greenblatt, 2015) and
require large efficiency improvements. No technoeconomic models have been
published. The US company Cambrian Innovation
(www.cambrianinnovation.com), however, already is using
electromethanogenesis commercially in industrial water cleaning
applications (Cambrian Innovation, 2013, 2015)
[0195] C-4 succinic acid (C.sub.4H.sub.6O.sub.4) has many uses as a
precursor chemical to polymers, resins, and solvents and as a food
additive. It is a widely produced worldwide by biological fermentation
(Cok et al., 2013). Lanzatech has developed a way to produce succinic
acid via its gas fermentation platform utilizing CO.sub.2+H.sub.2 input.
Gunnarsson et al., (2014) have demonstrated a labaratory method for
fermenting succinic acid with input of glucose and biogas (60% CH.sub.4,
40% CO.sub.2, molar ratio). This provides a combined method for CCU and
biogas upgrading to remove CO.sub.2.
[0196] Overall, the new microbial gas fermentation industry has a highly
promising future. It rapidly is developing wide-ranging flexibility
through combinations of the diversity of natural capacities combined with
the massive capabilities of synthetic biology to which recently has been
added a new horizon of "electrotrophic" biotechnology connecting with
renewable sources of electric power. The field offers many exciting
possibilities for future CO.sub.2 utilization (Durre and Eikmanns, 2015).
[0197] C-5 isoprene (C.sub.5H.sub.8, also known as 2-methyl-1,3-butadiene)
is a core component in the production of synthetic rubber used in the
manufacture of tires. The development of "bioisoprene" is an example of
substituting a bio-based synthesis process for a petrochemicals-based
process. Three company partnerships have developed bioisoprene production
for ecological bio-tire manufacture: (i) Genencore/Dupont and Goodyear;
(ii) Amyris and Michelin, and (iii) Ajinomoto and Bridgestone (Scandola,
2015). All of the bioproduction methods involved utilize non-gas carbon
sources. Isoprene has been targeted for production via gas fermentation
by LanzaTech as well as the US chemical giant DuPont. DuPont is seeking
patent protection for a syngas-based gas fermentation method: Beck et
al., 2014 US 2014/0234926 A1, "Recombinant anaerobic acetogenic bacteria
for production of isoprene and/or industrial bio-products using synthesis
gas." The new method compliments methods created by the start-up company
Genencor (now merged with Dupont), collaborating with Goodyear, to create
"bioisoprene" with glucose feeding of biocultures (Genencor, 2010; Whited
et al., 2010; Straathof, 2013; Benko, 2012; ETC Group, 2014). Isoprene
separates from biocultures as a gas, thereby conveniently avoiding
distillation separation methods. It may become possible to bioproduce
isoprene efficiently by gas fermentation. This could be a strategic
modality for CCU, perhaps also including sourcing hydrogen via new
"bio-GTL" natural gas fermentation technologies being developed (Harmon,
2015).
[0198] Dimethyl ether (DME: CH.sub.3OCH.sub.3) production is a "mini-GTL"
modality for CO.sub.2 and methane co-utilization. DME is an alternative
fuel that can replace both propane and diesel (Semelsberger et al., 2006;
Fleisch et al., 2012; GGFR-Fleisch, 2014). DME is useful as a propane/LPG
replacement by blending or total substitution. It can be used within the
propane/LPG infrastructure. It has substantially lower heating value
compared to LPG. However, it fills more mass into standard LPG bottles.
In competition between these two factors, the energy per bottle fill is
82% relative to LPG (IDA, 2010). Therefore DME can provide bottled home
and business cooking gas based on a methane source, alternate to propane.
DME replaces diesel fuel with minor engine modifications plus fuel
storage in LPG-type tanks. It has the highest well-to-tank efficiency
ratio of any transport fuel made from natural gas (Semelsberger et al.,
2006). DME also is environmentally attractive because it is
clean-burning. It has attractive performance relative to diesel. Oberon
Fuels (www.oberonfuels.com) is specialized in a two-stage syngas-process
production of methanol followed by DME utilizing inputs of methane and
CO.sub.2 (see: Lautzenberg, undated). Oberon's optimal target input
mixture is 72% CH.sub.4 and 28% CO.sub.2, volume percent (corporate
website and Corradini et al., 2014: U.S. Pat. No. 8,809,603 B2). A
different tri-reforming technology exists for single-step synthesis of
DME. It is via a syngas process using inputs of methane, steam and
CO.sub.2. The process was industrialized by the Korea Gas Coporation,
KOGAS in the mid-2000s (Cho et al., 2009, 2011; Chung et al., 2012; Zhang
et al., 2015). DME can be a useful non-toxic chemical for processing
biomaterials.
[0199] DME is an attractive substance for highly efficient low temperature
extraction of lipids from wet algal biomass. This is via a method
allowing efficient recycling of DME in the vapor phase (Kanda, 2011;
Kanda et al., 2012, 2015; Boonnoun et al., 2014; Goto et al., 2015).
[0200] Methanol (CH.sub.3OH) production is one industrial mode of using
CO.sub.2 on a potentially very large scale, offering an attractive liquid
fuel modality for hydrogen storage (Behrens, 2015; Wang et al., 2015;
Perez-Fortes et al., 2016; Al-Kalbani et al., 2016). Methanol and its
derivative DME have been advocated with a biomass source as the basis of
a green fuels economy by the Nobel prize winning chemist George Olah and
colleagues at USC (Olah et al., 2009; Goeppert et al., 2014). Methanol is
a well-demonstrated and well-established substitution-blending additive
in gasoline/petrol. Methanol's long industrialized dehydration
derivative, DME, is produced traditionally via the catalyzed dehydration
reaction: 2 CH.sub.3OH.fwdarw.(CH.sub.3).sub.2O+H.sub.2O. Or, as noted
above, it may be produced by single-step syngas tri-reforming of natural
gas with additional CO.sub.2 and steam inputs. Methanol is produced
industrially in China from coal and in the US from natural gas. Methanol
is used in China mainly as an alternative basis for petrochemicals
production. It was widely promoted as a transport fuel in China in the
interval 1998 to 2008. It remains widely blended into transport fuel
there (CleanTechnica, 2013; Yang and Jackson, 2012; Prakash and Olah,
2014). Methanol is well demonstrated as an efficient clean-burning fuel
in retrofitted diesel engines. The diesel engine manufacturer Wartsilla
is involved in extensive conversion, converting ships active in the North
Sea from bunker diesel fuel to methanol (Haraldson, 2015). Methanol also
can be used as a battery-like hydrogen storage fluid. It has .about.31%
electricity-to-electricity efficiency (Behrens, undated). Matthias Beller
and his research group in Rostock, Germany, have developed several
efficient calaytic modes for methanol dehydrogenation (Boddien et al.,
2011; Nielsen et al., 2013; Alberico et al., 2013; Sponholz et al. 2014;
Monney et al., 2014; Alberica and Nielsen, 2015), contributing further
towards the potential realization of a possible "methanol economy." This
agenda would generate electricity via H.sub.2 inputs from methanol
dehydrogenation. The resulting H.sub.2 flows would power fuel cell
electricity generators.
[0201] In principle, the thermodynamically most efficient modality of
methanol production from methane avoids a syngas step utilizing CO.sub.2.
Optimal production from natural gas, in principle, proceeds with input of
pure O.sub.2 by a single-step reaction of partial oxidation via
CH.sub.4+1/2O.sub.2.fwdarw.CH.sub.3OH (Jiang et al., 2010). However,
catalysis for efficient production via this reaction has not yet been
developed (Zhang et al., 2003: Khirsariya an Mewada, 2013). The company
GasTechno appears to have developed a commercially workable modality by
reaction flow recycling (Breidenstein, 2015; Fleisch, undated). Many
methanol plants operate by inputs of natural gas plus CO.sub.2 in order
to produce syngas with a target composition optimal for methanol
production: H.sub.2/CO.about.2.0. This ratio supports the efficient,
long-industrialized, one-step, gas-phase catalyzed reaction:
2H.sub.2+CO.revreaction.CH.sub.3OH (Lewis, 2013; Behrens, 2015). This
highly selective syngas reaction was first industrialized by ICI in 1966
(Chen, undated).
[0202] The Danish technology company Haldor Topsoe is a leading specialist
in catalytic syngas and fuel-cell processes, operating worldwide (Hansen
and Clausen, 2015). The company's capabilities portfolio includes
Gas-to-Liquids (GTL) methanol production from natural gas, with over
forty plants constructed worldwide (Aasberg-Petersen et al., 2011; Haldor
Topsoe, undated; Hansen, 2012a,b, 2014a,b,c, 2015a,b,c,d,e,f,g). Haldor
Topsoe's capabilities portfolio also includes advanced greentech designs
and plant constructions for syngas production from biomass inputs, for
Power-to-Gas (PTG) producing Synthetic Natural Gas (SNG), and for
CO.sub.2-utilizing Power-to-Fuels (PTF) technologies. In EU strategies,
Haldor Topsoe's technologies are expected to expand to be used for
grid-balancing as required for expanding renewable electricity inputs.
The agenda is to produce transportation fuels, including methanol, as
well as using methanol for electricity-to-electricity energy storage.
[0203] Haldor Topsoe has developed processes for converting inputs of
CO.sub.2, steam and electric power into outputs of methanol and oxygen
gas (Hansen, 2014ab, 2015a,c,f,g; Hansen et al., 2011). This technology
innovatively combines the operation of a Solid Oxide Electrolysis Cell
with a methanol reactor transforming syngas into methanol over a solid
catalyst.
[0204] A recent method for efficient methanol production from syngas with
the target composition by partial oxidation of methane has been developed
by Olah and his research group. It is called "oxidative bi-reforming"
(Olah et al., 2013a,b, 2015; Santos et al., 2015; Kumar et al., 2015;
Olah and Prakash patents: U.S. Pat. Nos. 7,906,559 B2; 8,697,759 B1 and
patent application: 2012/0115965 A1). Oxidative bi-reforming operates via
a first stage of oxy-fueled methane combustion to produce a hot
pressurized mixture of CO.sub.2 and steam:
CH.sub.4+2O.sub.2.fwdarw.CO.sub.2+2 H.sub.2O. Additional methane in
3.times. the combusted amount is then added for the second step. This
produces a syngas-steam mixture with the right composition for methanol
production ("metgas"): 3CH.sub.4+CO.sub.2+2H.sub.2O.fwdarw.4CO+8H.sub.2.
The full net reaction then is 4CH.sub.4+2O.sub.2.fwdarw.4CH.sub.3OH. It
is exothermic. This reaction utilizes the CO.sub.2 created internally by
the combustion component of the synthesis. If, however, a mixture of hot
steam and CO.sub.2 already is available in the right molar ratio as an
industrial by-product, then bi-reforming can simplify to its second stage
process with a CO.sub.2-utilizing net reaction:
3CH.sub.4+CO.sub.2+2H.sub.2O.fwdarw.4CH.sub.3OH. It becomes a CO.sub.2
utilization process for methanol production by addition of methane
utilizing inputs of CO.sub.2 and steam. Additional insights into the
utilization of CO.sub.2 in syngas production routes to methanol are
provided by Baltrusaitis and Luyben (2015).
[0205] A goal of recent research is to develop improved methods of
low-cost industrial catalytic hydrogenation of CO.sub.2 to methanol using
H.sub.2 inputs. Hydrogen inputs may be obtained indirectly, such as
H.sub.2 obtained from water splitting using renewable electricity (Olah,
2013; Goeppert et al., 2014; Behrens, 2014, 2015; Demirel et al., 2015;
Wang et al., 2015; Studt et al., 2014, 2015), or from the chlor-alkali
process for chlorine (Cl.sub.2) manufacture by electrolysis of NaCl (Kiss
et al., 2016). Or hydrogen may be obtained via integrated chemical
processes that include water-splitting, for example hydrothermal methods
with coupled metal/metal-oxide redox cycling (Jin et al., 2012; Huo et
al., 2012; Demirel et al., 2015; Lyu et al., 2015; Ren et al., 2015).
Hydrothermal processing also can reduce formic acid into methanol with
coupled metal/metal-oxide redox cycling (Zeng et al., 2011, 2014; Liu et
al., 2012; Yao et al., 2012). Industrialization of CO.sub.2 hydrogenation
to methanol using hydrogen from water-splitting with renewable power has
been achieved in Grindavik Iceland at the George Olah Plant
(www.carbonrecycling.is; Wikipedia entry: Carbon Recycling International;
Tran, 2010, 2011; Harp et al., 2015).
[0206] Professor Atsushi Urakawa at the ICIQ in Tarragona, Spain, created
a one-pass catalyst method for converting high-pressure H.sub.2 and
CO.sub.2 inputs into methanol or DME with high selectivity (Bansode and
Urakawa, 2014; Bansode, 2014; Urakawa and Bansode, U.S. Pat. No.
9,133,084, "Process for the preparation of methanol and methanol-derived
products from carbon oxides.") This method also allows production of
alkane or alkene products with a coupled second reactor.
[0207] CO.sub.2 can be utilized in combination with methanol to produce
dimethyl carbonate (DMC) according to the CO.sub.2-utilizing reaction:
2CH.sub.3OH+CO.sub.2.fwdarw.(CH.sub.3O).sub.2CO+H.sub.2O. DMC has
potential for large-scale industrial use. It is an eco-friendly solvent
used in the manufacture of paints. It also has very large scale
potential, well-demonstrated, as a pollution-decreasing oxygenating
additive to gasoline and diesel fuels (Honda et al., 2013). It moreover
is used as an electrolyte in Li-ion batteries, as well as as a base
material for polycarbonates production. Four synthesis routes, three
reacting supercritical CO.sub.2 with methanol, and the standard
industrial process combining O.sub.2 and CO with methanol are reviewed by
Saavalianen et al., (2015), Wen et al., (2015), Santos et al., (2014) and
Rivetti et al., (1996). Several electrolytic methods also are known. And
at least two industrialization agendas are ongoing for a
CO.sub.2-utilizing direct reaction method (Austrian Institute of
Tecnology, 2015; CCEMC-E3Tec Services, L L C, 2014).
[0208] CO.sub.2 also can be utilized in combination with ethanol to
produce diethyl carbonate (DEC) according to the reaction:
CH.sub.3CH.sub.2OH+CO.sub.2.fwdarw.(CH.sub.3CH.sub.2O).sub.2CO+H.sub.2O
(Gasc et al., 2009; Leino, 2015; Prymack et al., 2015). DEC is a widely
used feedstock in various synthesis routes in petrochemical productions.
And, like DMS, it has potential for large-scale future utilization as an
oxygenating cleanfuel additive for both gasoline and diesel. It also is
used as an electrolyte in Li-ion batteries.
[0209] Syngas for methanol production is obtainable by other means such as
from biomass gasification. A full demonstration exists on an industrial
scale in Sweden (Gillberg, 2012, 2013; Ridjan et al., 2013; Kolmogoren,
2014; Danish Methanol Association, 2011; Pedersen and Schultz, 2012;
BioMCN, 2013; Landalv, 2014). Syngas with the desired composition,
H.sub.2/CO .about.2.0, can be produced from biomass by two modes
involving input of CO.sub.2 as a biomass gasifying agent/reactant. These
are: (i) by input of CO.sub.2 reacting with dried biomass with or without
steam, or (ii) by input of CO.sub.2 with wet slurry biomass promoting
gasification reactions in highly pressurized supercritical water. The
latter situation is especially advantageous for use of harvested algal
biomass that has not been dried or centrifuged to remove intra-cell water
(thus saving a large component of energy expenditure). Biomass
gasification with input of CO.sub.2 reacting with dried biomass with or
without steam has been researched extensively. Results indicate that
CO.sub.2 input can be modulated to obtain a target output of syngas with
the ratio H.sub.2/CO .about.2.0. Reaction chemistries are observed with
high gasification yields and thermal efficiency in conditions with or
without steam (Butterman and Castaldi, 2007, 2008, 2009a,b, 2010, 2011;
Prabowo et al., 2014, 2015a,b,c; Kwon et al., 2015; Yi et al., 2015).
[0210] Biomass gasification in supercritical water with CO.sub.2 input has
been modeled by Frietas and Guirardello (2012, 2013, 2015). Model results
suggest CO.sub.2 input modulation to obtain H.sub.2/CO .about.2.0
(optimal for methanol production) is possible. However, the high pressure
and temperature process conditions are non-trivial for industrialization.
Also the output syngas contains CO.sub.2. Overall, CO.sub.2-enhanced
biomass gasification does not absorb CO.sub.2 in the net of the
reactions. However, it has the effect of suppressing the formation of
excess CO.sub.2 over input CO.sub.2 in the output in comparison with
syngas production without CO.sub.2 input. CO.sub.2 input increases
gasification efficiency. Importantly, it also reduces the problematic
formation of tars and chars. Biomass gasification of algal biomass in
supercritical water also has the special advantage of allowing nutrient
recycling by salts separation immiscibility between an aqueous phase and
other oil-rich and/or gas phases (Yakaboylu et al., 2015).
[0211] A potentially large-scale future mode of CCU may follow from a
cell-free electrosynthesis method of"artificial photosynthesis." The
method utilizes enzymes in an electrical water splitting system to
transform CO.sub.2 and water into O.sub.2 and carbohydrates such as
sugars or starch. Energy stored in sugars is expected to become an
efficient power storage method via enzymatic hydrogen release and also
eventually, via carbohydrate fuel cells. This vision is being pursued by
Percival Zhang and his research group at Virginia Tech (Zhang, 2010,
2011, 2013; Zhang and Huang, 2012; Zhang et al., 2012). Zhang's group has
developed a cell-free method of enzymatic production of hydrogen from
biomass (e.g., Rollin et al., 2015). Shi et al., (2015) provide a review
of the field of enzymatic conversion of CO.sub.2. Future developments in
"artificial photosynthesis" technology development may benefit from from
the fact that carbon dioxide reduction to methane and C2 hydrocarbons can
be catalyzed by a single biomimetic enzyme, a remodeled nitrogenase (Yang
et al., 2012; Rebelein et al., 2014, 2015).
[0212] More generally, solar power linked with electrolytic
water-splitting and CO.sub.2-utilizing "artificial photosynthesis"
(Ciamician, 1912; Inoue et al., 1979; RSC, 2012; Purchase and de Groot,
2015) produces "solar fuels" (Harriman, 2013; https://rtsfi.rti.org/RTSFI
what.html) and "solar chemicals" (Gates, 2015). This is an active and
rapidly expanding field of research, device invention and entrepreneurial
company formation (Olah, 2005; Olah et al., 2006; Barton et al., 2008;
Walter et al., 2010; Lewis, 2011; Meyer et al., 2011; Lewis and Nocera,
2012; RSC, 2012; Barber and Tran, 2013; Handoko et al., 2013; Lewis,
2013, 2016; Berardi et al., 2014; Cox et al., 2014; Grahn et al., 2014;
Ronge et al., 2014; Schlumberger, 2014; Wang et al., 2014; Ashford et
al., 2015; Bonke et al., 2015; Alissandratos and Easton, 2015; Fenwick et
al., 2015; Izumi, 2015; Kim et al., 2015; Su et al., 2015; Highfield,
2015; May et al., 2015; Modestino and Haussener, 2015; Peter, 2015;
Schreier et al., 2015; Shin et al., 2015; Torella et al., 2015; Wang et
al., 2015; White et al., 2015; Wikipedia: "Artificial photosynthesis";
Martin, 2016; Purchase and de Groot, 2016). The field includes many
different technology modalities. It is being funded by the support of
several governments in strategic programs (Faunce, 2012; Marshall, 2014).
It is experiencing a high rate of innovation towards the possibility of
industrial take-off (Herron et al., 2015). Three basic agendas are
involved: (i) direct photochemical CO.sub.2 reduction; (ii) CO.sub.2
electrochemical reduction via electrochemistry or electro-biochemistry
powered by solar-sourced electricity; and (iii) electrolysis of water to
produce H.sub.2 followed by use of this H.sub.2 for independent CO.sub.2
hydrogenation or electrochemical reduction or thermochemical reaction
with CO.sub.2 into product chemicals (such as formic acid, methane,
methanol, etc.). Efforts to commercially industrialize artificial
photosynthesis include large companies such as Panasonic, Toshiba and
Lockheed-Martin (Nagata, 2015), as well as start-ups such as Liquid Light
(www.llchemical.com), HyperSolar (www.hypersolar.com), Dioxide Materials
(www.dioxidematerials.com), Sun Catalytix (purchased by www.lockheed
martin.com), Sunfire (www.sunfire.de), and NewCO.sub.2Fuels
(www.newco2fuels.co.il).
[0213] This vision for artificial photosynthesis connects with business
initiatives creating large-scale photovoltaic (PV) and concentrated solar
power (CSP) electricity production units in high radiation intensity
desert areas, for example Nur Energie in the desert of North Africa
(www.nurenergie.com). Large solar power facilities in deserts eventually
will produce fuels and industrial chemicals once doing so becomes
economically competitive with long distance electricity sales and/or with
the market cost of liquid fossil fuels used for transportation. The
commercial future for the "solar economy" of artificial photosynthesis
and CSP chemicals production (e.g., www.newco2fuels.co.il;
www.solar-jet.aero; Romero and Steinfeld, 2012; Marxer et al., 2015)
using CO.sub.2 as a carbon source is presently (circa 2015) overshadowed
by low-cost fossil fuels. However, both PV and CSP technologies are
following well-demonstrated innovation trends of increasing efficiencies
with decreasing costs in their industrial applications. Also, the science
of catalyst design for industry is progressing rapidly. Moreover, most
technologies for CO.sub.2 electrochemical reduction can utilize power
from a variety of additional renewable sources including hydropower, wind
power and biomass- and biogas-based power. Therefore, industrialization
of CO.sub.2 reduction electrochemistries is generally to be expected for
the future. The agenda for artificial photosynthesis with CO.sub.2
recycling (the "solar chemical" agenda) is gaining traction in an
environment of widespread and growing international commitment to develop
efficient CO.sub.2 recycling as a key part of a green technology
transformation of the world energy economy on a very large scale (e.g.,
Gates, 2015; www.breakthroughenergycoalition.com; King et al., 2015;
King, 2016; Carrington, 2015; www.globalapolloprogramme.org;
www.nurenergie.com; Moller, 2012; Wikipedia entry: Desretec;
www.desertec.org; www.desertenergy.org; Trieb, 2013; Schlumberger, 2014).
Favorable situations include locations where large quantities of purified
CO.sub.2 are available for free or at very low cost, where "green"
venture-subsidies and low-cost investment capital are available, where
low-cost electricity is available (for example from hydropower and/or
future advanced low-cost solar mega-arrays), where co-produced O.sub.2
can be utilized efficiently for oxyfuel combustion, and where prices are
high for products due to suituations such as, for example, remoteness
from ports. A "solar fuels roadmap" for South Africa is reviewed by van
Ravenswaay et al., (2015).
[0214] The East African region contains very high solar radiation
intensity regions, especially in typically cloudless regions of
northwestern Uganda, NW Tanzania, and in northern and western Kenya.
These areas are observable in GeoModel Solar's time-averaged horizontal
irradiation map of Africa (Solargis, 2011). Some areas are favorable for
the development of large solar arrays. An example is the 40 MW solar PV
array being developed for installation in northern Kenya by the company
Greenmillenia Energy, Ltd (www.greenmillenia.com; Breakbulk, 2015. A plan
to create a much larger 320 MW PV solar park in central Kenya has been
announced (Kumar, 2015). Also, a 50 MV PV solar park being developed by
the Chinese firm CJIC in east-central Kenya (Nduire, 2015). Power from
such arrays can be transported efficiently over long distances by high
voltage direct current (HVDC). Technologies for grid development using
HVDC technology are developing rapidly. Effective use of large inputs of
solar power feeding directly into industrialized artificial
photosynthesis will be favored by the development of efficient energy
storage methods for load balancing to provide a continuous and level
power output.
[0215] Despite these many, scientific and engineering insights, designs,
teachings, products, methods, systems, business activities, safety
threats, development-industrialization needs, and ecologically
significant opportunities having to do with Lake Kivu, its deepwater
resources, and CO.sub.2 utilization, no efforts have been made to design
inventive methods and/or systems to co-extract and co-utilize the lake's
abundant CO.sub.2 resource in the context of extracting and utilizing its
methane resource. Accordingly, there is a need, a problem, and a
spectacular opportunity to solve the problem by invention of a new method
and system.
[0216] All references cited herein are incorporated herein by reference in
their entireties.
BRIEF SUMMARY OF THE INVENTION
[0217] Accordingly, the invention comprises a method for obtaining and
utilizing carbon dioxide gas from a body of water containing dissolved
carbon dioxide gas and methane gas, said method comprising the steps of:
(a) extracting water from at least one extraction depth of the body of
water to obtain extracted water; (b) degassing the extracted water in at
least one stage of degassing so as to provide degassed water and
extracted gases comprising carbon dioxide gas and methane gas in at least
one flow; (c) optionally combusting the extracted gases with oxygen to
provide an exhaust gas comprising carbon dioxide and water; and (d)
feeding to a utilization hub the carbon dioxide gas from at least one of
step (b) and step (c), wherein the utilization hub is configured to
collect the carbon dioxide gas for storage, distribution, processing
and/or utilization.
[0218] In certain embodiments, the method further comprises utilizing the
carbon dioxide collected by the utilization hub to perform at least one
process selected from the group consisting of fertilizing growth of
plants, fertilizing a biozone of Lake Kivu, lowering a pH of water
returned into Lake Kivu, adjusting a pH of water exiting from a vacuum
degassing system, adjusting a pH of water fed to an algal growth sector,
cultivating algae, supplying a cryogenic energy storage reservoir,
heating or cooling a supercritical CO.sub.2 power cycle heat engine power
generator, delivering pressurized carbon dioxide by pipeline, delivering
pressurized carbon dioxide by tanks including by pressurized tank trucks,
producing dry ice, storing, producing and distributing refrigerated
liquefied and/or solidified carbon dioxide, producing a magnesium-based
cement or concrete, producing urea, producing formic acid, producing
oxalic acid, producing acetic acid, producing a solvent, producing carbon
monoxide, producing a pyrethrum pesticide, producing an asphyxiant,
producing a food packaging gas, pasteurizing milk, beer or an
agricultural juice, processing an agricultural, food, forest, textile,
waste or biofuel product, cleaning a textile, treating leather,
extracting geothermal energy, producing a fuel, producing a syngas,
producing a chemical via a formate and/or by an oxalic acid platform,
producing a chemical by gas fermentation based on a microbial Wood
Ljundahl pathway, producing a chemical by a synthetic pathway including
carbon dioxide as a reactant, producing a plastic including carbon
dioxide as an ingredient, producing carbonic acid, producing a carbonated
and/or CO.sub.2 pressurized beverage, producing sodium bicarbonate,
producing a fracking fluid, producing silicic acid, producing
microsilica, producing iron, producing nickel, processing an ore to
produce a plant and/or aquatic fertilizer, processing an ore by solution
extraction of one or more metals using supercritical carbon dioxide
optionally injected into an ore zone, producing an elemental carbon
product, producing oxygen gas, and injecting carbon dioxide via
drillholes into subterranean strata for geostorage.
[0219] In certain embodiments of the method, step (c) is conducted and the
carbon dioxide collected in step (d) is solely from the exhaust gas
provided in step (c).
[0220] In certain embodiments, the method further comprises generation of
electrical power.
[0221] In certain embodiments of the method, deep gas trapping layers of
the body of water possess in their volume average a CO.sub.2/CH.sub.4
ratio greater than 4, and more than 98 wt. % of the CH.sub.4 dissolved in
the water is extracted by the extracting step.
[0222] In certain embodiments of the method, the body of water is Lake
Kivu and the method reduces a risk of a limnic eruption.
[0223] In certain embodiments, the method further comprises extracting
from the extracted water at least one product selected from the group
consisting of ammonium, ammonia, phosphorous, magnesium and calcium.
[0224] In certain embodiments, the method further comprises: supplying the
electrical power to a compression and refrigeration system; cooling with
the compression and refrigeration system at least one gas to form at
least one liquefied gas, wherein the at least one gas is at least one of
oxygen, nitrogen, carbon dioxide that has been extracted from the
extracted water, carbon dioxide that has been formed in a combustion of
associated methane and methane that has been degassed from the extracted
water; storing the at least one liquefied gas in at least one insulated
storage tank; releasing from the at least one insulated storage tank a
liquid flow of the at least one liquefied gas; optionally increasing a
pressure of the liquid flow of the at least one liquefied gas; heating
the liquid flow to form a subcritical gas flow or a supercritical fluid
flow, wherein at least a portion of the heating is optionally conducted
by heat exchange with a closed system heat engine; driving a turbine with
a subcritical gas flow or with a supercritical fluid flow to generate
electricity; and optionally driving a turbine within a closed system heat
engine to generate electricity.
[0225] In certain embodiments of the method, the degassed water provided
in step (b) is transported for water treatment, and the method further
comprises the steps of: (i) photosynthetic treatment of the degassed
water by growth of an algal biomass to convert bicarbonate anions to
carbon fixed by photosynthesis into biomass and hydroxyl anions in the
degassed water, such that the pH of the degassed water is increased and
bicarbonate anions are converted into carbonate anions and magnesium and
calcium precipitate out of the degassed water onto algal cells to provide
de-densified water and flocculated biomass precipitate; (ii) separating
the de-densified water from the flocculated biomass precipitate; (iii)
optionally additionally treating the degassed water by electrochemical
methods such that the pH of the degassed water is further increased and
additional magnesium and calcium precipitate out of the degassed water to
provide further de-densified water and magnesium and calcium precipitate;
(iv) optionally separating the further de-densified water from magnesium
and calcium precipitate; (v) optionally adjusting the pH of the
de-densified water or further de-densified water by adding thereto a
volume of the carbon dioxide gas collected by the utilization hub from at
least one of step (b) and step (c); and (iv) reinjecting into Lake Kivu a
return flow of the de-densified water or further de-densified water
separated from the biomass and precipitate, wherein the return flow is
reinjected into Lake Kivu at a reinjection depth which is shallower than
the extraction depth and which is density matched with the de-densified
water or further de-densified water.
[0226] In certain embodiments of the method, the utilization hub supplies
a stream of carbon dioxide into the biozone of Lake Kivu as a carbon
fertilizing source supporting photoautotrophic bioproductivity.
[0227] In certain embodiments of the method, the utilization hub supplies
a stream of carbon dioxide which is injected into: (i) post-degassing
return flow water containing nutrients that are being diffused into a
biozone of Lake Kivu; (ii) de-densified high-pH post-degassing return
flow water that is being injected into Lake Kivu underneath the biozone;
and/or (iii) post-degassing return flow water for pH control.
[0228] In certain embodiments of the method, the utilization hub supplies
a stream of carbon dioxide to a horticultural greenhouse.
[0229] In certain embodiments of the method, the utilization hub supplies
a stream of carbon dioxide which is injected into algal growth
biocultures.
[0230] In certain embodiments of the method, the utilization hub supplies
a stream of carbon dioxide to a compressor to provide compressed carbon
dioxide, the compressed carbon dioxide is optionally stored in a storage
tank, and the compressed carbon dioxide is distributed through pipelines.
[0231] In certain embodiments of the method, the utilization hub supplies
a stream of carbon dioxide gas to a compression and refrigeration system
to provide compressed refrigerated liquid carbon dioxide and/or solid
carbon dioxide, and the method optionally comprises at least one of the
additional steps of: (i) storing the compressed refrigerated liquid
and/or solid carbon dioxide; (ii) further cooling the compressed
refrigerated liquid carbon dioxide to provide dry ice; (iii) storing the
dry ice; (iv) using the stored dry ice as cryogenic energy with recovery
to generate power; and (v) distributing the dry ice.
[0232] The invention further comprises a system configured to perform the
method of the invention.
[0233] In certain embodiments, the system comprises: a water degassing
system; and a carbon dioxide utilization hub in fluid communication with
the water degassing system.
[0234] In certain embodiments of the system, the water degassing system
comprises: an intake pipe system; at least one bubble capture unit
positioned upwards along a system of degassing pipes; at least one
degassing catalyst unit positioned further upwards along the system of
degassing pipes; a bubbly flow turbine configured to capture and recycle
power from jetting foam flow at a top of the system of degassing pipes,
wherein the bubbly flow turbine is also configured to function as a foam
separator; at least one vacuum degassing unit positioned at the top of
the system of degassing pipes; and a water flow turbine capturing and
recycling power in a downward outflow of degassed water from the vacuum
degassing unit.
[0235] In certain embodiments, the system comprises: a water degassing
system; an oxyfuel power generation system in fluid communication with
the water degassing system; and a carbon dioxide utilization hub in fluid
communication with the oxyfuel power generation system.
[0236] In certain embodiments of the system, the oxyfuel power generation
system comprises a power generator and an air separation unit configured
to provide oxygen for combustion.
[0237] In certain embodiments of the system, the water degassing system
comprises: an intake pipe system; at least one bubble capture unit
positioned upwards along a system of degassing pipes; at least one
degassing catalyst unit positioned further upwards along the system of
degassing pipes; a bubbly flow turbine configured to capture and recycle
power from jetting foam flow at a top of the system of degassing pipes,
wherein the bubbly flow turbine is also configured to function as a foam
separator; at least one vacuum degassing unit positioned at the top of
the system of degassing pipes; and a water flow turbine capturing and
recycling power in a downward outflow of degassed water from the vacuum
degassing unit.
[0238] In certain embodiments, the system further comprises a return flow
system which comprises: an outflow pipe from the water degassing system;
pipe systems connecting flow to at least one water treatment system; a
return flow pipe system and horizontal diffuser to reinject degassed
water into the body of water at a specified depth; and flow control valve
systems with emergency shut-off capabilities.
[0239] In certain embodiments, the system further comprises: flow
connection by pipes and channels to and from at least one surface water
treatment system that decreases water density in the degassed water flow;
and an inlet system configured to allow admixture of relatively low
density near-surface water from the body of water into the return flow
for reinjection at a specified depth.
[0240] In certain embodiments, the system further comprises a system
configured for combustion preparation processing and transfer of degassed
gas into the oxyfuel power generation system.
[0241] In certain embodiments, the system further comprises a control
system configured for physical monitoring, system-wide functional
integration and emergency response safety assurance.
[0242] In certain embodiments, the system is configured to extract more
than 98 wt. % of CH.sub.4 dissolved in a body of water having a
CO.sub.2/CH.sub.4 ratio greater than 4.
[0243] The invention further provides a carbon dioxide utilization hub
comprising: (a) pipes and control valves configured for transferring
exhaust gases; (b) pumps configured for compressing and transferring the
exhaust gases into at least one of a storage tank, a gas processing tank
and a heat exchange system; (c) at least two of a storage tank for
pressurized gas, a gas dehydration system and a heat exchange system; (d)
at least one compressor for compressing dehydrated carbon dioxide; (e) at
least one storage tank for storing compressed dehydrated carbon dioxide;
(f) at least one dispensing valve for dispensing compressed dehydrated
carbon dioxide from at least one storage tank storing compressed
dehydrated carbon dioxide; (g) at least one refrigeration system for
compressing and refrigerating dehydrated carbon dioxide gas into
liquefied refrigerated carbon dioxide; (h) at least one of: (i) at least
one insulated tank for storing dehydrated liquefied refrigerated carbon
dioxide, (ii) at least one insulated tank for storing liquefied
refrigerated nitrogen, (iii) at least one insulated tank for storing
liquefied refrigerated oxygen, and (iv) at least one dispensing valve for
dispensing at least one cryogenic refrigerated liquids selected from the
group consisting of carbon dioxide, nitrogen and oxygen; (i) power
generation cryoenergy recovery systems utilizing at least one of the
following cryoenergy storing inputs: (i) liquefied refrigerated carbon
dioxide, (ii) liquefied refrigerated nitrogen and (iii) liquefied
refrigerated oxygen; (j) gas dispensing valves and pipes for transferring
and dispensing at least one warmed gas emerging from cryoenergy recovery
systems; and (k) at least one pressurizable reaction chamber configured
to provide a mixture of carbon dioxide and water vapor under controlled
and time-varying conditions of pressure, mixing ratio, temperature and
time and admitting product producing forms containing at least one of the
following carbon dioxide and water vapor absorbing substances: magnesium
hydroxide, calcium carbonate, hydrated magnesium carbonates,
concrete-forming aggregate, pozzolans, steel rebar, microsilica and plant
materials.
[0244] In certain embodiments of the method, the utilization hub supplies
at least one of liquefied natural gas, compressed natural gas and
adsorbed natural gas.
[0245] In certain embodiments, the method further comprises supplying the
electrical power to a compression and refrigeration system; cooling with
the compression and refrigeration system at least one gas to form at
least one liquefied gas, wherein the at least one gas is at least one of
oxygen, nitrogen, carbon dioxide that has been extracted from the
extracted water, carbon dioxide that has been formed in a combustion of
associated methane and methane that has been degassed from the extracted
water; and cooling a server with the at least one liquefied gas.
[0246] The invention further comprises a process for generating data, said
process comprising: providing a server; cooling the server with at least
one liquefied gas; and generating the data from the server, wherein the
at least one liquefied gas comprises at least one of oxygen, nitrogen,
carbon dioxide and methane from Lake Kivu water.
BRIEF DESCRIPTION OF SEVERAL VIEWS OF THE DRAWINGS
[0247] The invention will be described in conjunction with the following
drawings in which reference numbers and their corresponding component
names are identified in a listing herein (this listing also indicating
like items according to like names across the set of figures), and
referenced in descriptive discussions in the text according to a
convention "X.Y", where "X" is the figure number, and "Y" represents
numerical component item labels appearing within figure X, and wherein:
[0248] FIG. 1 is a simplified schematic and conceptual representation of
the method and system of the invention shown as a process flow divided
into five boxes representing different functional groupings of different
components of the whole such as may be present in various embodiments. A
representation of the Modified Staged Degassing System (MSDS) submethod
and subsystem is shown by items 13 and 14. (See FIG. 8 for an overview of
the MSDS.)
[0249] FIG. 2 is a schematic representation of an embodiment of the
invention shown with additional detail relative to FIG. 1. Only the
modality utilizing a Total Degassing System (TDS) is shown. The variant
modality utilizing a Modified Staged Degassing System (MSDS) is not
shown. FIG. 2 represents the invention in the context of some aspects
present in other related disclosures by the inventor involving the
utilization of Lake Kivu deepwater resources and relating especially to
the return flow of degassed water into the lake (34, 35, 36a,b,c). The
figure is shown partly in vertical plane perspective: for Lake Kivu
represented with three water layers, 23a,b,c. Otherwise, the figure is
shown in non-spatially oriented representation of process flows. Box 1 is
an inset showing the invention overall in its combinative aspect as a
combination of submethods and subsystems (for the TDS modality only),
where numerical labels correspond to identical labels elsewhere in FIG.
2. Box 2 illustrates aspects of the operations of the CO.sub.2
Utilization Hub (CO.sub.2-UH) and its twenty "main modes" of CO.sub.2
utilization. Box 3 is another inset. It illustrates adjunct utilization
of excess liquid nitrogen and/or oxygen (via flow vectors 39 and/or 40
and/or 42) to cool one or more large refrigeration utilization
facilities, such as, for example, a digital data center (43).
[0250] FIG. 3 is a schematic representation of an embodiment of the
receiving (1, 2), processing, storage, and purveying aspects of the
CO.sub.2 Utilization Hub (CO.sub.2-UH), with additional inclusion of the
storage and utilization of liquefied nitrogen and oxygen in certain
preferred embodiments. Most production flows ("process trains") proceed
from left to right. Five types of production flows are illustrated as
horizontal sequences, left-to-right, stacked vertically (22, 23, 24, 25,
26). An additional dashed box (36) represents optional cryo-energy
storage capacities utilizing liquefied gases.
[0251] FIG. 4 is a symbolic representation of an embodiment of the
invention disclosed herein construed as a method and system of
jobs-creation via greentech industrialization (7) in the Lake Kivu region
measured by performance metrics reporting upon these factors symbolized
by icons within item 8.
[0252] FIG. 5 is a comparative representation shown mostly in vertical
plane schematic representation. The figure compares basic aspects of an
embodiment of the invention (shown in Box 2) in with existing practiced
technology, (as shown in Box 1), for extracting methane and generating
power from Lake Kivu deepwater (circa 2015: SDS). Only the modality of
the invention utilizing a TDS (rather than a MSDS) is shown in Box 2.
[0253] FIG. 6 is a schematic representation of cryogenic aspects of the
invention including energy storage.
[0254] FIG. 7 is a purely symbolic "hub-&-spokes" representation of
embodiments of the CO.sub.2-UH (and, more broadly, of the invention
overall) located at Lake Kivu functioning as a hub (1) center for a
global network (2: large circle plus associated box containing icons).
The network can connect together many and various worldwide
collaborations (3, 4, 5, 6, 7, 8, 9, 10, 11, 12 . . . ) with companies,
research institutions and philanthropic agendas attracting talent into
the overall venture. Entities work together in concert with respect to
addressing the challenge to create business-scalable innovations in
CO.sub.2 utilization recycling. Icons inside the dashed box represent
multiple types of aspects of such a hub-and-spokes global network.
[0255] FIG. 8 is a schematic representation in vertical plane of: (i) in
Box 1: a 2-stage representation of the Staged Degassing System (SDS)
method invented by Belgian engineers in the 1950's and later practiced on
Lake Kivu; and (ii) in Box 2: a modification of this staged method (MSDS,
shown for 2-stages). The MSDS provides a means for separated degassing of
CO.sub.2, thereby allowing CO.sub.2 utilization by adaptation of
conventional operations. Box 3 illustrates a schematic representation of
several pH control options utilizing CO.sub.2 inputs (21a,b, 22, 25, 27)
and removals: 21a,b, 23, 24) in two different modalities of return flow:
(15) and (16-through-20). These modalities of return flow (15, 20) into
shallow layers of Lake Kivu are different from (deep) return flow
according to the standard modality of the SDS method (9a, 9b, 13). Both
represent modes of CO.sub.2 utilization by injection into Lake Kivu (for
a range of various reasons).
[0256] FIG. 9 republishes FIG. 1 except with addition of detail within Box
4. This extra detail shows several ways by which embodiments of the
invention utilize CO.sub.2 via a range of (optional) modes of
injection-dissolution into return flow, as well as by (optional) direct
diffusion into the lake. (Such injection of dissolution-absorbed CO.sub.2
into higher-level layers does not enhance threat risks of limnic
eruption).
LISTING AND BRIEF DISCUSSION OF REFERENCE NUMBERS APPEARING IN THE FIGURES
[0257] A listing of reference numbers and their corresponding component
names follows. These are provided according to the convention "X.Y" noted
above. X represents the figure number. Y represents the component or item
number label within figure X. References to numbered boxes in the figures
sometimes differ from numbered items, but always in a simple and clear
manner. In FIGS. 2 and 8 only, box numbers are differentiated from item
label numbers. For example, FIG. 2 contains three boxes labeled "Box 1,"
"Box 2," and "Box 3," but also contains separate items numbered 1, 2 and
3. These clearly are illustrated as distinct entities. In such cases
(also in FIG. 8), "X.BoxY" in the text is used to reference "Box Y" in
the figure, these being different from items in the same figure labeled
"Y" (referenced "X.Y" in the text). Boxes sometimes are labeled simply by
numerals as ordinary items, (though as boxes indicating associated
operationally integrated collections of items). Boxes also sometimes are
identified with numerical labels surrounded by a small solid line box
possessing rounded corners. Use of such small boxes with rounded corners
surrounding number labels is a form of highlighting for purposes of
clarity. Such highlighted labels always identify larger boxes. This
highlighting can be seen in an obvious way in FIG. 1 for boxes labeled
one through five. A listing follows upon this basis. The listing lists
all labeling reference numbers in the figures. These are ordered via the
"X.Y" convention. Label numbers are provided by item-component names
and/or brief descriptions:
[0258] 1. Aspects of FIG. 1 that are not shown within Box 4 are
illustrated in FIG. 9. These are left out of FIG. 1 to avoid excessive
complication. FIG. 1 mainly illustrates the process flow of degassing
into oxy-fuel combustion into utilization of CO.sub.2 representing an
invention that, overall, creates an integrated method and/or system for
Lake Kivu Carbon Capture Utilization (CCU) in combination with the
"traditional" agenda of electric power production, while also increasing
lake safety over time.
[0259] 1.Box1. Box 1 represents a Total Degassing System (TDS, as
labeled), generating efficient degassing of both methane and carbon
dioxide together.
[0260] 1.Box2. Box 2 represents an Oxy-Fueled Combustion Power System,
(OXFCPS, as labeled). The Box contains icons representing methane
combustion driving turbine blades.
[0261] 1.Box3. Box 3 represents a CO.sub.2 Utilization Hub, (CO.sub.2-UH),
as labeled. This generates product flows indicated by the black
rightwards arrows jointly within Box 3 and Box 8.
[0262] 1.Box4. Box 4 contains and thereby groups together a variety of
useful outflows of pipe-delivered CO.sub.2 (shown by arrows) from the
CO.sub.2-UH. These outflows are into injection-dissolution Lake Kivu in a
range of modes, including integration of injection into a Return Flow
System (7), and serving a variety of purposes. Details are provided in
FIG. 9.
[0263] 1.Box5. The dashed box labeled (5) connects together boxes 2 and 3.
This connection represents a capacity for systems-integrative cryogenic
energy storage utilizing refrigerated-liquified gases. Details are
provided in FIG. 6.
[0264] 1.6. Deepwater extraction method and/or system.
[0265] 1.7. Return Flow System (sometimes labeled with the acronym RFS) as
a main vector (7), also showing different plumbing options (7a, 7b) as
well as integration into methods and/or systems for density reduction by
removal of dissolved substances and also by removal of CO.sub.2 by
degassing.
[0266] 1.Box8. Box 8 represents the set of product flows out of the
CO.sub.2-UH. Icons indicate different product transport modes applicable
at Lake Kivu (which lacks a railway link at present). Air transport is
not shown, but is available.
[0267] 1.9. Labels 9a,b,c represent Lake Kivu according to three different
layers. (The actual density structure of the lake is more complicated
than shown by three layers.) 9a represents the biozone. 9c represent the
resources-rich deepwater zone. 9b represents (a combination of)
intermediate layers.
[0268] 1.10. Arrow 10 most directly represents an oxygen input for
oxy-fueled combustion of methane in the OXFCPS (Box 2). Arrow 10 also may
be construed to include an Air Separation Unit (ASU, not shown. See FIG.
2) for the production of O.sub.2 as well as co-production of N.sub.2 both
in liquid (LN.sub.2) and gaseous (N.sub.2) forms.
[0269] 1.11. Arrow 11 indicates a method and/or system of mass transfer of
degassed gas (containing both methane and carbon dioxide) from the TDS
(Box 1) into the OXFCPS (Box 2).
[0270] 1.12. Arrow 12 indicates a method and/or system of mass transfer of
postcombustion gas (containing both carbon dioxide and water vapor) from
the OXFCPS (Box 2) into the CO.sub.2-UH (Box 3).
[0271] 1.13. A small dashed box 13 (within Box 1 and labeled MSDS)
represents an optional embodiment of the invention described as the
Modified Staged Degassing System (and/or method). It is further
illustrated in detail in FIG. 8. The MSDS method and/or system lacks an
OXFCPS. Hence the CO.sub.2 flux obtained from it is shown being provided
directly (14) into the CO.sub.2-UH (Box 3).
[0272] 1.14. Item 14 is a CO.sub.2 transfer line specific to the MSDS, as
noted above.
[0273] 1.15. Item 15 represents one or more CO.sub.2 transfer lines
(typically pipes) exporting CO.sub.2 from the CO.sub.2-UH (Box 3), as
product flows (8), into Lake Kivu via a range of possible and optional
sub-methods and/or sub-systems. (See FIG. 9 for detail for items not
shown in FIG. 1: 15a, 15b, 15c, 15d, 15e, 16, 17, 18, and 19.)
[0274] 1.20. Label 20 indicates a set of icons on top of Box 3 as well as
to its right. These indicate various exemplary aspects of greentech
industrialization in the CO.sub.2-UH (top), including product export
(side).
[0275] 2.Box1. Box 1 is a symbolic inset indicating the invention as a
combination of submethods and subsystems (specifically for the
TDS-to-OXFCPS modality embodiment) with numbers corresponding to labeled
items elsewhere in the diagram.
[0276] 2.Box2. Box 2 contains a core aspect of the invention, Carbon
Capture Utilization (CCU) via greentech industrial processing and
manufacturing using CO.sub.2 and consequent productive outputs/outflows.
Specifically, Box 2 encloses an illustration of the CO.sub.2-UH (21)
incorporating twenty different modes of CO.sub.2 distribution and
Carbon-Capturing product production and export. Productive flows exiting
the CO.sub.2-UH are shown as black arrows.
[0277] 2.Box3. Box 3 is a symbolic inset illustrating optional adjunct
utilization of liquefied nitrogen and oxygen (LN.sub.2, LO.sub.2) for
provision of cooling in a Digital Data Center (43: DDC), where items 39,
40 and 42 reference storage-directed flow vectors illustrated in the main
part of the figure. (Note: A cryogenic ASU {item 27} produces LN.sub.2,
LO.sub.2.) Such provision of cryogenic LN.sub.2 and LO.sub.2 is a
capacity of some embodiments of the invention via adjunct capacities of
the CO.sub.2-UH.
[0278] NB: Items 2.1 through 2.20 are all CO.sub.2 utilization modes
described in Table 2.
[0279] 2.1. One (1) represents (CO.sub.2 provided to) local greenhouse
horticulture.
[0280] 2.2. Two (2) represents (CO.sub.2 provided to) Lake Kivu Biozone
fertilization (with two different injection-dissolution options noted as
2a and 2b).
[0281] 2.3. Three (3) represents (CO.sub.2 provided to) Return Flow System
(RFS) for purposes of pH lowering.
[0282] 2.4. Four (4) represents (CO.sub.2 provided to) return flow water
treatment of a variety of types involving CO.sub.2 injection for pH
control.
[0283] 2.5. Five (5) represents (CO.sub.2 provided to) algal production
(including bicarbonate).
[0284] 2.6. Six (6) represents (CO.sub.2 provided by) high-pressure
pipeline delivery.
[0285] 2.7. Seven (7) represents (CO.sub.2 provided by) refrigerated
delivery (as liquid and/or solid).
[0286] 2.8. Eight (8) represents CO.sub.2 incorporated into production of
eco-cements and concretes and related materials.
[0287] 2.9. Nine (9) represents (CO.sub.2 utilized in) urea production
from ammonia.
[0288] 2.10. Ten (10) represents (CO.sub.2 input into) production of
formic acid.
[0289] 2.11. Eleven (11) represents (CO.sub.2 input into) production of
carbon monoxide.
[0290] 2.12. Twelve (12) represents (CO.sub.2 input into) production of
pyrethrum biopesticide. (Compressed CO.sub.2 is a diluent carrier fluid
in canisters for spraying.)
[0291] 2.13. Thirteen (13) represents (CO.sub.2 use in various processes
of) forest products processing and production.
[0292] 2.14. Fourteen (14) represents CO.sub.2 use in geothermal energy
extraction (typically by pipeline delivery).
[0293] 2.15. Fifteen (15) represents various CO.sub.2 uses in fuels and
chemicals production.
[0294] 2.16. Sixteen (16) represents CO.sub.2 uses as an input into syngas
production.
[0295] 2.17. Seventeen (17) represents CO.sub.2 use as an input into
syngas manufacturing of fuels and chemicals.
[0296] 2.18. Eighteen (18) represents CO.sub.2 use in gas fermentation
production of various products (typically with hydrogen gas inputs).
[0297] 2.19. Nineteen (19) represents plastics production incorporating
CO.sub.2 in various modalities.
[0298] 2.20. Twenty (20) represents production of a variety of high-value
carbon products by reduction of CO.sub.2. (For example C-nanotubes.)
[0299] 2.21. Label 21 identifies a stippled box containing a combination
of elements that together an example of a (large-scale multi-product
example embodiment of a CO.sub.2-Utilization Hub: CO.sub.2-UH). Note that
a CO.sub.2-UH in some embodiments includes large areas of
algal/phytoplanktonic production which additionally may include
zooplanktonic as well as fish production in various embodiments, and
where injection can function as a CO.sub.2-fertilizing carbon source for
photosynthesis.
[0300] 2.22. Item 22 is a method and/or system of upward extractive flux
of gas-rich deepwater into a Total Degassing System (24: TDS) 2.23.
Labels 23a, 23b, and 23c together identify Lake Kivu in upper, middle,
and lower layers, respectively, as shown.
[0301] 2.24. Item 24 is a Total Degassing System (TDS) receiving deepwater
flux (22) and splitting its output into fluxes of degassed gas (25) and
degassed water (34).
[0302] 2.25. Item 25 is a method and/or system and/or apparatus of gas
transfer (with hydrogen sulfide scrubbing if/as needed and gas
compression and/or gas dehydration if/as needed). The transfer couples
the flow of gas exiting from degassing and coordinates it to be fed into
the Oxy-Fueled Combustion Power System (OXFCPS) and/or method.
[0303] 2.26. Item 26 is an Oxy-Fueled Combustion Power System (OXFCPS)
and/or method. The OXFCPS receives transferred gas from item 25. It
exhausts a mixture of nominally pure carbon dioxide and water vapor into
a gas transfer exhaust system and/or method (28) transferring gas into an
exhaust receiving and gas processing unit (30) within the CO.sub.2-UH
(21).
[0304] 2.27. Item 27 is a method and/or system of oxygen transfer into the
Oxy-Fueled Combustion Power System (26: OXFCPS) and/or method. In FIG. 2,
as shown, the source is an Air Separation Unit (27: ASU); however other
types of sources may provide input oxygen into combustion.
[0305] 2.28. Item 28 is a method and/or system and/or apparatus of gas
(CO.sub.2+H.sub.2O) transfer for directing post-combustion hot exhaust
gases from the Oxy-Fueled Combustion Power System (26: OXFCPS) into a
gas-receiving processing, storage and purveying unit (30) within the
OXFCPS (21).
[0306] 2.29. Item 29 is the transfer of power provided by the OXFCPS (26).
This may be mechanical power or electrical power. An associated icon
indicates production of electric power into a distribution grid.
[0307] 2.30. Item 30 is a gas-receiving processing, storage and
purveying/distribution unit (30) within the OXFCPS (21).
[0308] 2.31. Item 31 indicates an optional transfer flux of oxygen from
the CO.sub.2-UH into the oxygen supply for combustion in the OXFCPS. Such
a flow, for example, might be sourced as waste from electrolytic hydrogen
production from water operating within the CO.sub.2-UH, and/or from
CO.sub.2 splitting or other processes of CO.sub.2 deoxygenation.
[0309] 2.32. Item 32 identified a generic flux of inputs (including power)
into the CO.sub.2-UH (21) other than the gas inputs specified by specific
labels (28, 39, 42).
[0310] 2.33. Item 33 is an arrow representing the accumulation of all of
the flux of product outputs out of the CO.sub.2-UH.
[0311] 2.34. Item 34 is a connecting method and/or system for transferring
degassed deepwater from a Total Degassing System (24: TDS) into a Return
Flow System (RFS: 35, 36a,b,c). Typically this involves pipes, pumps and
valves.
[0312] 2.35. Item 35 represents the reception, storage, coordinating
delivery and water-treatment parts of the overall Return Flow System
(RFS: 35, 36a,b,c). In some embodiments, item 35 will include extensive
operations for water treatment. As shown (2, 3, 4), these may involve
connections with CO.sub.2 export from the CO.sub.2-UH (21).
[0313] 2.36. As shown, item 36 has three distinct modalities: 36a, 36b,
and 36c. The differences are for different return flow water densities
corresponding to different depth of reinjection into Lake Kivu.
Differences correspond mostly to whether or not de-densification water
treatment occurs, and if so, to what degree. Reinjection flux vector 36c
represents diffusive fertilizing injection of post-degassing deepwater,
(which may be without de-densification water treatment).
[0314] 2.37. Item 37 represents flows of CO.sub.2 proceeding from
treatment and storage (in unit 30) into forms of production that
transform CO.sub.2 into carbon-containing products. Types of processed
CO.sub.2 are obtained from treatment of OXFCPS exhaust (in unit 30) with
storage and disposition of it (in unit 30) into utilizing production
activities within the wider parts of the overall CO.sub.2-UH (21).
[0315] 2.38. Item 38 is labeled within the Box 1 inset. It is the large
circle that also is labeled as "Lake Kivu." It represents both the domain
of operations specific to Lake Kivu as well as the combinative domain of
the invention as an integration of component sub-methods and/or
sub-systems.
[0316] 2.39. Item 39 is a flux vector representing transfer of nitrogen
gas, typically in liquefied form, into storage within unit 30. Typically,
embodiments will include cryogenic methods and/or systems for transfer of
liquefied nitrogen.
[0317] 2.40. Item 40 is a flux vector representing general production and
use of liquefied nitrogen (LN.sub.2), for example, for use in Digital
Data Center (43) cooling, or more generally for sale.
[0318] 2.41. Item 41 represents input of air or air-like gas into the Air
Separation Unit (ASU: 27). "Air-like gas" here refers to gas obtained
from canopies over areas of photosynthetic activity such as, for example,
covered algal growth operations producing oxygen.
[0319] 2.42. Item 42 is a flux vector representing transfer of oxygen gas,
typically in liquefied form, into storage within unit 30. Typically,
embodiments will include cryogenic methods and/or systems for transfer of
liquefied oxygen.
[0320] 2.43. Item 43 is a small box labeled within the inset Box 3. It
represents a Digital Data Center (DDC) receiving cooling flows labeled
39, 40 and 42, these numbers referring to items shown elsewhere in the
figure (all three associated with the ASU, 27).
[0321] 2.44. Item 44 is a flux vector representing the potential of
utilization of flows of gaseous nitrogen after use in cooling a Digital
Data Center (DDC: 43), for various purposes, for example in algal
production operations and/or in horticultural uses.
[0322] 2.45. Item 45 is a flux vector representing the potential of
utilization of flows of gaseous oxygen after use in cooling a Digital
Data Center (DDC: 43), for example for oxyfuel combustion operations.
[0323] 3.1. Item 1 is identical to item 12 in FIG. 1 and item 28 in FIG.
2. It is a transfer flux of exhaust from the OXFCPS into the CO.sub.2-UH
(which is detailed in FIG. 3). The flux is comprised of a hot and
nominally pure mixture of carbon dioxide and water vapor.
[0324] 3.2. Item 2 is an optional component present in some high
efficiency embodiments: a Heat Exchanger Power Production Unit (HEPPU)
obtaining post-combustion power from heat present in the OXFCPS exhaust.
Such units also can function as water separators by condensation of water
vapor upon cooling (3, illustrated by an icon).
[0325] 3.3. Item 3 represents a water separation capacity by condensation.
This water separation capacity also is shown as first stages within a
process trains labeled 22 and 24. It also is shown as a stage within
process train 23.
[0326] 3.4. Item 4 is a 3-way valve allowing input of CO.sub.2 into a
treatment chamber (5) possessing pressurization (10) capacity for
pressurized "carbonization" (CO.sub.2 absorption) into the production of
eco-cements and concretes and other building materials.
[0327] 3.5. Item 5 is a treatment chamber described immediately above.
[0328] 3.6. Item 6 represents post-production product storage for
carbonated building materials, as indicated by icons.
[0329] 3.7. Item 7 represents building materials product export/delivery
by truck.
[0330] 3.8. Item 8 represents building materials product export/delivery
by ship.
[0331] 3.9. Item 9 represents a storage capacity within process train 23.
It is for storage, along with cooling and dehydration (3), of moderately
compressed (10) carbon dioxide prior to further compression (10) prior to
pipeline export (11a, 11b).
[0332] 3.10. The label 10 and an associated icon represents a CO.sub.2
compressor. This label and icon appears in several locations in the
figure.
[0333] 3.11a,b. Pipe-&-valve icons labeled 11a and 11b indicate a range of
pipeline delivery systems at various pressures and pipeline diameters for
local distribution/delivery of relatively low-pressure
(non-supercritical) CO.sub.2.
[0334] 3.12. Tank icons labeled 12 represent a tank farm storage depot for
pre-delivery storage of relatively high-pressure (typically
supercritical) non-refrigerated CO.sub.2.
[0335] 3.13. Pipe-&-valve icon labeled 13 represents pipeline(s) delivery
of relatively high-pressure (typically supercritical) non-refrigerated
CO.sub.2.
[0336] 3.14. Pipe-&-valve icon labeled 14 represents by-truck delivery of
relatively high-pressure (typically supercritical) non-refrigerated
CO.sub.2.
[0337] 3.15 a,b. Items 15a and 15b represent pipeline connections within
the CO.sub.2-UH that supply high pressure CO.sub.2 into refrigeration
stages for liquification (15a) and dry ice production (15b).
[0338] 3.16. The icon set labeled 16 indicates a cryogenic capacity for
liquification of CO.sub.2 with associated insulated tank storage (17).
This capacity may be identical with or supplementary to an Air Separation
Unit (ASU, illustrated in other figures). In relation to the dashed box
labeled 36, this cryogenic capacity may include refrigeration of other
gases: oxygen and nitrogen, along with insulated tank storage (30, 31).
[0339] 3.17. Insulated tank storage for refrigerated liquid CO.sub.2.
[0340] 3.18. Insulated by-truck transport of refrigerated liquid CO.sub.2.
[0341] 3.19. The icon set labeled 19 indicates a cryogenic capacity for
solidification of CO.sub.2 into dry ice, with associated cool storage
(20).
[0342] 3.20. Icon 20 represents dry ice storage.
[0343] 3.21. Icon 21 represents by-truck transport/delivery of dry ice.
Transport/delivery additionally may be by any other means as well,
including boat and motorcycle.
[0344] 3.22. Label 22 (inside a highlighting circle) indicates a process
train for CO.sub.2 utilization for the production of eco-cement and
concrete products produced with absorption of CO.sub.2 (and also water
vapor for hydration).
[0345] 3.23. Label 23 (inside a highlighting circle) indicates a process
train for CO.sub.2 utilization as relatively unprocessed gas delivered at
relatively low pressures.
[0346] 3.24. Label 24 (inside a highlighting circle) indicates a process
train for CO.sub.2 production/delivery as relatively high pressure gas.
[0347] 3.25. Label 25 (inside a highlighting circle) indicates a process
train for CO.sub.2 production/delivery as refrigerated liquified gas.
[0348] 3.26. Label 26 (inside a highlighting circle) indicates a process
train for CO.sub.2 production/delivery as dry ice.
[0349] 3.27. Label 27 represents crossover transfer if/as needed from
high-pressure CO.sub.2 storage to low-pressure delivery.
[0350] 3.28. Label 28 represents control over the temperature and water
vapor content of CO.sub.2 input into carbonation and hydration facilities
for eco-cement and concrete and related products production (=process
train 22).
[0351] 3.29. Label 29 identifies a cryogenic energy storage method,
system, capability or unit utilizing liquefied liquefied nitrogen and/or
liquefied oxygen (and/or CO.sub.2 linkage, not shown except as two-sided
vector 34).
[0352] 3.30. Label 30 indicates an icon representing tank (or tank farm)
storage of refrigerated liquefied oxygen.
[0353] 3.31. Label 31 indicates an icon representing tank (or tank farm)
storage of refrigerated liquefied nitrogen.
[0354] 3.32. Label 32 indicates connectivity of the cryogenic energy
storage capacity (29) with tank(s) for insulated storage of liquid
oxygen.
[0355] 3.33. Label 33 indicates connectivity of the cryogenic energy
storage capacity (29) with tank(s) for insulated storage of liquid
nitrogen.
[0356] 3.34. Label 34 indicates that in some embodiments, there can be
connectivity of cryogenic energy storage methods and/or systems (29) with
production and storage of solid CO.sub.2.
[0357] 3.35. Label 35 of a two-sided arrow represents a gas transfer
linkage between cryogenic energy storage capacities (29) connecting (32)
to liquid oxygen storage (30). The transfer linkage connects (outside of
the figure) into the intake oxygen supply into oxyfuel combustion
(OXFCPS) and to the Air Separation Unit (ASU, not shown) oxygen supply
that produces liquid oxygen in cases where oxygen separation from air is
via cryogenic methods.
[0358] 3.36. Label 36 represents the overall capacity of the linkage with
the cryogenic capabilities of the ASU to provide refrigeration into
process trains 25 and 26. In some embodiments this capacity includes and
integrates cryogenic energy storage (29).
[0359] 3.37. Icon 37 indicates a general capacity for provision/sales of
refrigerated liquid oxygen.
[0360] 3.38. Icon 38 indicates a general capacity for provision/sales of
refrigerated liquid nitrogen.
[0361] 3.39. Label 39 indicates a transfer capacity for connecting stored
refrigerated liquefied CO.sub.2 into specialized cryogenic energy storage
for CO.sub.2 (40).
[0362] 3.40. Item 40 indicates options for inclusion in some embodiments
of specialized cryogenic energy storage utilizing liquid CO.sub.2.
[0363] 3.41. Item 41 indicates embodiments that include integration of
cryogenic CO.sub.2 energy storage into cryogenic energy storage methods
and/or systems utilizing LN.sub.2 and/or LO.sub.2 (29). (NB: As indicated
by item 40, cryogenic energy storage methods and/or systems utilizing
CO.sub.2 may be separate from cryogenic energy storage utilizing LN.sub.2
and/or LO.sub.2 (29).)
[0364] 4.1. Item 4.1 is a schematic flux vector representing methods
and/or system of extraction and separation of Lake Kivu deepwater (12).
Deepwater is directed into several components (2) for utilization
operations, shown involving, for CO.sub.2, a CO.sub.2-Utilization Hub
(CO.sub.2-UH) utilizing combined CO.sub.2 (10, 11) from deepwater
degassing (3) as well as combustion (9) of co-extracted deepwater methane
(6).
[0365] 4.2. Dashed box 2 represents the cumulate of utilizable resource
components of Lake Kivu deepwater (12).
[0366] 4.3. Box 3 represents one component: degassed deepwater CO.sub.2.
[0367] 4.4. Box 4 represents another component: deepwater bicarbonate ion.
[0368] 4.5. Box 5 represents additional chemically dissolved resource
components such as dissolved Mg and Ca cations as well as NPK fertilizers
and additional important fertilizing trace elements.
[0369] 4.6. Box 6 represents degassed deepwater biomethane.
[0370] 4.7. Box 7 represents a CO.sub.2-Utilization Hub (CO.sub.2-UH),
with icons indicating its aspect as a basis for jobs-creating greentech
industrialization.
[0371] 4.8. Box 8 represents the outcomes of greentech industrialization
exemplified by jobs, economic growth and increased per capita GDP.
[0372] 4.9. Box 9 represents power production via combustion with
efficient carbon capture.
[0373] 4.10. Arrow 10 represents efficient carbon (CO.sub.2) capture with
transfer into a CO.sub.2-Utilization Hub (CO.sub.2-UH).
[0374] 4.11. Arrow 11 represents capture and transfer of deepwater
CO.sub.2 into a CO.sub.2-Utilization Hub (CO.sub.2-UH). NB: This capture
and transfer can be routed through combustion (9) in the case of a Total
Degassing System (TDS) combined with oxyfueled combustion.
[0375] 4.12. Label 12 indicates resource-rich Lake Kivu deepwater.
[0376] 5.1. Box 1 encloses a representation of the standard, practiced
"Staged Degassing System" (SDS) of methane extraction and power
production on Lake Kivu showing both the return of CO.sub.2 into the
deepwater layer, and loss of postcombustion CO.sub.2 to the atmosphere.
[0377] 5.2. Box 2 encloses a representation of one mode of Lake Kivu
deepwater resource extraction and utilization disclosed herein: the
method and/or system of total degassing (TDS) combined with CO.sub.2
utilization.
[0378] 5.3. Label three (3) marks the a-depth inlet of Lake Kivu deepwater
for methane extraction in the Staged Degassing System (SDS) method and/or
system.
[0379] 5.4. A stippled box labeled four (4) indicates a two-staged
degassing system.
[0380] 5.5. The numerical label five (5) represents the reinjection of
dissolved CO.sub.2 (from Stage-1) into Lake Kivu's deepwater reservoir
after degassing by the SDS method.
[0381] 5.6. The numerical label six (6) represents the reinjection of
dissolved CO.sub.2 (from Stage-2, dissolved in "washing water") into Lake
Kivu's biozone after degassing by the SDS method.
[0382] 5.7. Label seven (7) marks a gas (methane-rich gas) transfer line
from an offshore floating platform (12a) to an onshore power-generating
facility (8).
[0383] 5.8. Label eight (8) marks an icon representing an onshore
power-generating facility. (Placed onshore due to the very large sizes
and weights of piston engine power generators utilized in the SDS
method.)
[0384] 5.9. Label nine (9) indicates that CO.sub.2 formed from combustion
in the SDS method is not captured. This CO.sub.2 is released into the
atmosphere.
[0385] 5.10. Label ten (10) marks a depth inlet of Lake Kivu deepwater for
methane extraction in the Total Degassing System (TDS) method and/or
system.
[0386] 5.11. Label eleven (11) indicates a floating platform (also icon
12b) in the TDS-OXFCPS method and/or system (Box 2). As shown, the figure
in Box 2 shows the possibility that the platform could include power
plant operations (13). OXFCPS turbines utilizing a CO.sub.2 power cycle
are much smaller than power generation operations utilizing large and
heavy piston-type gas burning engines (8).
[0387] 5.12. Labels 12a and 12b both indicate icons representing floating
offshore platforms.
[0388] 5.13. Label 13 indicates an icon representing power generation, in
this case situated on a floating platform (11, 12b).
[0389] 5.14. Label 14 indicates that degassed CO.sub.2 is captured and
enters a CO.sub.2-UH in the TDS-OXFCPS method (Box 2).
[0390] 5.15. Label 15 indicates that combustion-formed CO.sub.2 is
captured and enters a CO.sub.2-UH in the TDS-OXFCPS method (Box 2).
[0391] 5.16. Label sixteen (16) indicates a CO.sub.2-UH, shown with icons
representing greentech industrialization.
[0392] 5.17. Label seventeen (17) indicates a transition depth in Lake
Kivu separating a resource-rich deepwater reservoir below an upper
reservoir without concentrated resources. (This is a simplified
representation. The actual situation is multi-layered.) For comparison,
Box 2 indicates that this transition depth can move downwards (from 17 to
18) over time in some embodiments of the TDS method and other advanced
methods of utilizing Lake Kivu deepwater resources (when return flow
water can be de-densified so that it can be returned in higher-level
layers and "push down" the depth of the transition later over time, as
shown by arrows: 17 to 18).
[0393] 5.18. Label eighteen (18) indicates the time trend of deepening of
a transition layer boundary in some embodiments of the TDS method and
other advanced methods of utilizing Lake Kivu deepwater resources.
[0394] 5.19. Label nineteen (19, located in Box 1) indicates one aspect of
methane loss or "slip" occurring in the SDS method. This loss is due to
non-total degassing at the stage-1 transition wherein gas is degassed at
a depth typically of .about.20 meters.
[0395] 5.20. Label twenty (20, located in Box 1) indicates another aspect
of methane loss or "slip" in the SDS method. This loss is due to
re-dissolution of methane degassed in Stage-1 into "washing water"
degassed gas is bubbled through in Stage-2 operations for the purpose of
CO.sub.2 separation.
[0396] 5.21. Label twenty-one (21) indicates a set of icons representing
products output and transport from the CO.sub.2-UH (16).
[0397] 5.22. Label twenty-two (22) is a dashed circle within Box 1. It
circles Stage-1 degassing operations whereby an upflow of deepwater (3)
is separated into two fractions. These are: (i) a gas fraction which
proceeds upward (23), and (ii) a water fraction containing most of the
CO.sub.2 in solution (5) and some of the methane remaining in solution
(19).
[0398] 5.23. Label twenty-three (23) indicates the upflow of degassed gas
proceeding upwards into Stage-2 separation by means of bubbling up
through an intensely showered downflow of near surface "washing water"
(24).
[0399] 5.24. Label twenty-four (24) represents a "washing water" flow of
near-surface water (which absorbs CO.sub.2 into solution) through Stage-2
"water washing" within Stage-2 (25). This water flows out of Stage 2 (25)
and is reinjected into Lake Kivu's upper (above 17) Biozone (vector 6
carrying a load of re-dissolved CO.sub.2).
[0400] 5.25. Label twenty-five (25) indicated a sector secured to a
floating platform (4, 12a) within which Stage-2 "water washing" occurs.
Typically this is in an above-water tower supported on top of a floating
platform.
[0401] 5.26. Label twenty-six (26) labels an upflow vector indicating an
upward flow of Lake Kivu deepwater containing water (unfilled outer
arrow), dissolved CO.sub.2 (black inner vector) and methane (thin
stippled core vector).
[0402] 5.27. Label twenty-seven (27) indicates a total degassing separator
wherein water is shown being separated into a return flow (28, 29, 30),
while degassed gas flows upwards into oxyfueled combustion (13) for power
generation (as indicated by icons).
[0403] 5.28. Label twenty-eight (28) indicates an early pre-treatment part
of a Return Flow System (RFS).
[0404] 5.29. Label twenty-nine (29) indicates a water treatment phase in
flow through a Return Flow System (RFS)
[0405] 5.30. Label thirty (30) indicates relatively shallow injection of
return flow into the water column (causing "push down" 17 to 18) of the
transition layer.
[0406] 5.31. Label 31 indicates reinjection of CO.sub.2-carrying (5)
return flow water into the deepwater reservoir from which the
methane-bearing deepwater (3) was obtained. Methane loss or "slip" (5)
also is shown.
[0407] 6.1. Box 1 identifies/contains the OXFCPS and its intersections
with various cryogenic energy storage components (Boxes 2, 3, 4, 22, and
23).
[0408] 6.2. Box 2 identifies/contains an Air Separation Unit (ASU)
integrated with part of a CRyogenic Processing Unit (Box 22: CRPU) and
liquefied gases storage units (Box 4, Box 28).
[0409] 6.3. CRyo-Energy Recovery Unit (Box 3: CRERU) showing its various
interconnections with other components.
[0410] 6.4. CO.sub.2-UH (Box 4) with LN.sub.2, LO.sub.2, LCO.sub.2 and LNG
storage capacities (Box 28).
[0411] 6.5. Item 5 represents a Digital Data Center (DDC) with capacities
for being cooled by inputs of either or both cold gaseous N.sub.2 (12)
and LN.sub.2 (11).
[0412] 6.6. Item 6 represents a flow transfer of liquified oxygen
(LO.sub.2) from a cryogenic condenser source (29) in an Air Separation
Unit-Cryo-Production Unit (Box 2: ASU-CRPU) into one or more storage
tanks (23) within a cryo-storage domain for liquefied gases (28) obtained
from air (or air-like) inputs (14).
[0413] 6.7. Item 7 represents a flow transfer of liquified nitrogen
(LN.sub.2) from a cryogenic condenser source (29) in an Air Separation
Unit-Cryo-Production Unit (Box 2: ASU-CRPU) into one or more storage
tanks (24) within a cryo-storage domain for liquefied gases (28) obtained
from air (or air-like) inputs (14).
[0414] 6.8. Item 8 represents a flow transfer of gaseous CO.sub.2 and/or
liquified carbon dioxide (LCO.sub.2) from a cryogenic condenser source
(30) intersecting (via Box 22: CESSI) with CO.sub.2-carrying
post-combustion exhaust created in the OXFCPS (Box 1) and stored into one
or more storage tanks (25) within a cryo-storage domain for liquefied
gases (28) possessing general cryogenic capacities or integration into
other cryogenic capacities within the overall system (27b, as indicated
by the icon), and existing as a part of the CO.sub.2-UH (Box 4 and
detailed in FIG. 3).
[0415] 6.9. Item 9 represents a flow transfer of liquified carbon dioxide
(LCO.sub.2) from storage (25) into a CO.sub.2-specific heat exchanger
turbine system (within Box 22: CESSI, as indicated by icons) that
converts the cryogenic energy stored in liquefied CO.sub.2 into
mechanical, then electric power (18a).
[0416] 6.10. Item 10 represents a flow transfer of liquified oxygen
(LO.sub.2) from storage (23) into an O.sub.2-specific heat exchanger
turbine system (within Box 22: CESSI, as indicated by icons) that
converts the cryogenic energy stored in liquefied O.sub.2 into
mechanical, then electric power (18b).
[0417] 6.11. Item 11 represents a flow transfer of liquified nitrogen
(LN.sub.2) from storage (24) into an N.sub.2-specific heat exchanger
turbine system (within Box 22: CESSI, as indicated by icons) that
converts the cryogenic energy stored in liquefied N.sub.2 into
mechanical, then electric power (18c).
[0418] 6.12. Item 12 is a captured flow of cold gaseous nitrogen from the
outflow of the part of the Cryo-Energy Recovery Unit (Box 3: CRERU) that
recovers cryo-energy stored in LN.sub.2. This cold gas is directed as a
coolant flow into a Digital Data Center (5: DDC).
[0419] 6.13. Item 13 represents a flow transfer of (utilizable) warmed-up
nitrogen gas out of the Digital Data Center (5) after absorbing heat.
[0420] 6.14. Input of air (or air-like gas) into the Air Separation
Unit--Cryogenic Processing Unit (Box 2: ASU-CRPU).
[0421] 6.15. Black arrow 15 indicates inflow of electric power from the
grid (33) into an electricity handling nexus (Box 41) integrated into the
OXFCPS (Box 1).
[0422] 6.16. The black arrow labeled 16 indicates outflow of electric
power into the grid (33) from an electricity handling nexus (Box 41) that
is integrated into the OXFCPS (Box 1).
[0423] 6.17. Black arrow 17 indicates deployment of electric power from
the electricity handling nexus (Box 41) into the ASU-CRPU (Box 2) to
power cryogenic condensation of gases.
[0424] 6.18. Black arrows 18, 18a, 18b, and 18c indicate power inputs into
the electricity handling nexus (Box 41) from in the Cryo-Energy Recovery
Unit (Box 3: CRERU).
[0425] 6.19. Black arrow 19 indicates power provision from the electricity
handling nexus (41) in the OXFCPS (Box 1) into the CO.sub.2-UH (Box 4)
with its cryogenic capacities (27b) integrated with those (27a) in the
Air Separation Unit--Cryogenic Processing Unit (Box 2: ASU-CRPU).
[0426] 6.20. Item 20 represents electrical power input from solar and/or
wind power arrays. Typically these will be situated at remote locations
with respect to Lake Kivu.
[0427] 6.21. Item 21 represents the connection of electric power inputs
from solar and/or wind power arrays into the electricity handling nexus
(Box 41) integrated with the OXFCPS (Box 1). The invention's optional
inclusion of cryo-energy storage capacities allows energy storage of
irregular inputs of renewable energy and consequently an important
potential function in grid-balancing.
[0428] 6.22. Box 22 ("CESSI") represents systems/methods of integration
described as, "Cryogenic Energy Storage Systems Integration" (CESSI)
coupling together an Oxy-Fuel Combustion Power System (Box 1: OXFCPS), an
integrated Air Separation Unit --Cryo-Production Unit (Box 2: ASU-CRPU),
a Cryo-Energy Recovery Unit (Box 3: CRERU), as well as a cryo-storage
domain for liquefied gases (Box 28) functioning as a cryo-energy
power-storage battery (26, as indicated by the battery icons).
[0429] 6.23. Liquefied oxygen (LO.sub.2) storage in a tank or tank farm.
[0430] 6.24. Liquefied nitrogen (LN.sub.2) storage in a tank or tank farm.
[0431] 6.25. Liquefied carbon dioxide (LCO.sub.2) storage in a tank or
tank farm.
[0432] 6.26. Iconic representation of liquefied gases storage as a power
battery.
[0433] 6.27. Items/icons 27a and 27b represent integrated cryogenic
systems serving the ASU-CRPU (Box 2) and the cryo-storage domain (Box 28)
within the CO.sub.2-UH (Box 4)
[0434] 6.28. Box 28 (dashed box) contains the cryo-storage domain within
the CO.sub.2-UH (Box 4)
[0435] 6.29. Item 29 is a refrigerating heat exchanging air condensing
unit within the ASU-CRPU (Box 2).
[0436] 6.30. Item 30 represents refrigerating heat exchanging condensing
unit for refrigeration of CO.sub.2 to liquid within the CESSI (Box 22),
exporting liquefied CO.sub.2 (8) into tank storage (25). This capacity
may be considered to be identical to capacities labeled 27a and 27b for
the specific case of the refrigeration-liquification of CO.sub.2.
[0437] 6.31. Item 31 is a captured flow of cold gaseous oxygen from the
outflow of the part of the Cryo-Energy Recovery Unit (Box 3: CRERU) that
recovers cryo-energy stored in LO.sub.2. This cold gas is directed as a
coolant flow into input into oxy-fueled combustion in the OXFCPS (Box 1).
[0438] 6.32. Flux arrow 32 is a flow of post-combustion exhaust from the
OXFCPS (Box 1) into the CO.sub.2-UH (Box 4). A note below the label
clarifies an important matter that is not otherwise shown in the figure:
that the exhaust flow is connected to heat exchange capacities within the
CRERU-CESSI.
[0439] 6.33. An icon labeled thirty-three (33) represents connectivity
with the grid. [Arrows fifteen (15) and sixteen (16) represent power
flows into and out of the electricity handling nexus (Box 41) from and to
the grid (33), respectively, indicating (cryogenic) power storage
capacities as well as the conventional powerplant power production
capacities.]
[0440] 6.34. The tank icon is labeled representing both LNG storage as
well as a capacity for use of LNG in cryo-processing CH.sub.4--CO.sub.2
mixtures to obtain additional LNG and extracted dry ice (e.g., Baxter:
WO2013062922A1, "System and Methods For Integrated Energy And Cryogenic
Carbon Capture.") Interconnection details are not shown in FIG. 6 (or in
other figures).
[0441] 6.35. Cryogenic production capacity for LNG as well as for
separation of CO.sub.2 as noted immediately above
[0442] 6.36. Box thirty-six (36) represents specialized cryogenic
operations for LNG production as well as for separation of CO.sub.2 as
noted for item 6.34.
[0443] 6.37. Flux vector representing inflow of biomethane with CO.sub.2
into LNG-specialized operations noted above.
[0444] 6.38. Source of biomethane with CO.sub.2 (=Lake Kivu deepwater via
degassing operations).
[0445] 6.39. Flux vector representing the flow of separated biomethane
with CO.sub.2 from LNG-specialized operations.
[0446] 6.40. Flux vector representing a general capacity for Natural Gas
(NG) production (LNG, CNG, and ANG). This production follows cryogenic
CO.sub.2 separation within LNG (item 35, by means of the elegant methods
pioneered by Larry Baxter and colleagues). Output flux vector 40 also can
indicate an output into energy storage via both LNG cryoenergy and LNG
fuel energy (though icon/item 34 itself indicates this capacity).
[0447] 6.41. Label forty-one, (Box) 41, represents an electricity handling
nexus whereby grid (33) power inputs (15) and outputs (16), as well as
special inputs (21) of renewable power sources (20), are integrated into
the OXFCPS (Box 1) NB: Label thirty-three (33) indicates the grid in
connection to the electric power producing powerplant component of the
OXFCPS.
[0448] 7. FIG. 7 is purely conceptual representing the invention in terms
of its potential for global network creation by offering an attractive
opportunity for the coordinated realization of many CO.sub.2-utilizing
technologies.
[0449] 7.1. Item one (1) is the CO.sub.2-Utilization Hub (1: CO.sub.2-UH)
represented as the hub of a wheel-like hub-&-spokes network in which each
spoke (3, 4, 5, 6, 7. 8, 9, 10, 11, 12 . . . ) is a specific
collaboration for a type of CO.sub.2 utilization.
[0450] 7.2. Item two (2) is the larger circle representing the outer wheel
hosting spokes at a (global) distance from the hub but connecting into
it. A box connecting to this large circle on the lower left represents by
icons various aspects or types of collaborations. Also represented is its
worldwide global aspect, attracting talent into the project as well as
possessing an openness to host new inventive modes of CO.sub.2
utilization.
[0451] 7.3 through 7.12 are described in section 7.1 above.
[0452] 8. FIG. 8 provides a systems comparison. The comparison is focused
on the modification of a conventional Staged Degassing System (SDS, Box
1). An SDS is shown with two stages as practiced on Lake Kivu. It is
compared with a Modified Staged Degassing System (Box 2) allowing carbon
(CO.sub.2) capture as well as utilization of non-degassed resources in
the degassed return flow water. FIG. 8 contains Box 1 enclosing a Staged
Degassing System (SDS), Box 2 enclosing a Modified Staged Degassing
System (MSDS), and Box 3, (which is within Box 2), enclosing two modes of
Return Flow Systems. These two RFS modes are different from deep
reinjection modes indicated (depth not to scale) in items 9a, 9b, and 13.
Note that in FIG. 8, the three box numbers noted above are distinct from
item numbers 1, 2 and 3.
[0453] 8.Box1. Box 1 encloses a representation of a Staged Degassing
System (SDS).
[0454] 8.1. Item 1 (shown in both boxes 1 and 2) represents a deepwater
extraction pipe or riser.
[0455] 8.Box2. Box 2 encloses a representation of a Modified Staged
Degassing System (MSDS).
[0456] 8.2. Item 2 (shown in both boxes 1 and 2) represents a stage-1
degassing and separation chamber, with a degassing surface positioned at
depth D (10), showing how water flows up into the chamber, over a
barrier, and then down reinjection pipes or risers (9a and 9b)
[0457] 8.Box3. Box 3, (which is within Box 2), encloses two modes of
Return Flow Systems. One (15) is for diffusive admixing of degassed
deepwater into the biozone as a mode of (carefully monitored and
controlled) lake fertilization with controlled CO.sub.2 injection (27,
28). The other (proceeding along the surface, 16) is a water treatment
water de-densification bioproduction and Mg, Ca-precipitation system,
also with controllable CO.sub.2 input (e.g., 22, 25) and removal (e.g.,
25) capacities.
[0458] 8.3. Item three (3), (shown in both boxes 1 and 2) represents a gas
transfer line transferring degassed gas upwards from Stage-1 degassing
into Stage-2 gas cleaning operations (4, 5, 6, 7, 8).
[0459] 8.4. Item four (4) represents an enclosed chamber, typically a
tower, wherein gas flow from Stage-1 rises upwards through either via a
bubbling upflow or upwards through a showered and/or packing-mediated
trickling (6) downflow of water obtained from a near-surface location
(5). The "washing water" is then expelled (7) into the biozone carrying
absorbed CO.sub.2 that has been "cleaned" during the upwards gas flow.
Cleaned methane gas consequently containing a reduced amount of CO.sub.2
is extracted at the top of the tower (8) for use in combustion. Bubble
flow is indicated in the diagram. However, as noted herein, such a
gas-cleaning tower may not use bubbling gas flow. It may contain packing
materials promoting large area trickle flow interaction between the
percolating down-flowing water and the up-flowing gas that is in close
contact with the down-flowing water within the tower.
[0460] 8.5. Item five (5) represents near-surface extraction of water to
supply gas "washing water" with pumped flow (6) to the top of the
gas-washing tower (4).
[0461] 8.6. Item six (6) represents a pumped near-surface extraction of
water to supply "washing water" with pumped flow (6) to the top of the
gas-washing tower (4).
[0462] 8.7. Item seven (7) represents return flow (typically via one or
more pipes) of the flow of gas-washing water into the biozone.
[0463] 8.8. Item eight (8) represents the gas extractor area (including
gas extraction line) at the top of the gas-cleaning tower. In a bubbled
flow, this is a gas zone above the surface of the mixed flow. In a tower
operating by trickling flow, it is simply the area where the
upward-flowing gas is extracted (in combination with the extraction line,
and typically but not necessarily involving pumped control of gas flow).
[0464] 8.9a,b. Items nine (9a and 9b) represent return flow reinjection
pipes. Depths are not shown to scale. Reinjection in the modes
illustrated by necessity must be in the deepwater layer due to the
density of the water (changed only to a modest degree by degassing).
[0465] 8.10. Double-sided arrow ten (10, shown within Box 1) represents a
depth, D, for a degassing surface within the Stage-1 degassing chambers
shown in Boxes 1 and 2.
[0466] 8.11. Item eleven (11) shown within Box 2 represents a key
modification of the SDS method and/or system. This modification ports
water after Stage-1 degassing upwards into a second stage of degassing,
thereby allowing degassing and capture of CO.sub.2 as well as utilization
of additional resources present in return flow water, by modification
(such as of existing systems or designs).
[0467] 8.12. Item twelve (12) represents a second degassing chamber for
separation of CO.sub.2 from the return flow. As illustrated, valves
(indicated by bow tie icons) allow directing of return flow into
different types of systems.
[0468] 8.13. Item thirteen (13) represents one such return flow system:
conventional reinjection at depth similar to 9a and 9b.
[0469] 8.14. Item fourteen (14) represents extraction of CO.sub.2 out of
the top of the second degassing chamber for separation of CO.sub.2 from
the return flow (12).
[0470] 8.15. Item fifteen (15) represents (an array of) pipe diffusers for
diffusive admixing of degassed return flow deepwater into Lake Kivu's
biozone (as a mode of controlled lake fertilization).
[0471] 8.16. Item sixteen (16) represents a mode of water treatment of
return flow.
[0472] 8.17a,b. Item seventeen (17a,b) represents a capacity for CO.sub.2
content control corresponding to vectors 21a,b. Capacity 17a represents
control for CO.sub.2 input into the return flow. Capacity 17b represents
control for CO.sub.2 removal such as by sparging and/or vacuum extraction
of dissolved gas the return flow. Such capacities also are pH control
capacities.
[0473] 8.18. Item eighteen (18) indicates a water biotreatment zone
(typically involving algal growth in some embodiments). In some
embodiments, as shown, CO.sub.2 inputs (22) are staged along the flow.
[0474] 8.19. Item nineteen (19) represents a capacity for two functions.
The first is for CO.sub.2 extraction (as indicated by vector 24), such as
by sparging and/or by vacuum extraction of dissolved gas the return flow.
The second is for precipitation of Mg and Ca from solution according to a
variety of possible methods and/or systems.
[0475] 8.20. Item twenty (20) represents return flow reinjection at a
lesser depth than in the cases of return flow without de-densifying water
treatment (that is: 9a, 9b, 13).
[0476] 8.21a,b. Item twenty-one (21a,b) is a double-sided arrow
representing a capacity for either CO.sub.2 input (21a), or CO.sub.2
extraction (21b), with directionality specified as needed.
[0477] 8.22. Item twenty-two (22) indicates a capacity for input of
CO.sub.2 into water treatment operations (18), typically involving algal
growth.
[0478] 8.23. Item twenty-three (23) represents modes of CO.sub.2 removal
from solution prior to entry into unit/process/method/system 19.
[0479] 8.24. Item twenty-four (24) indicates a capacity for CO.sub.2
removal from unit 19.
[0480] 8.25. Item twenty-five (25) indicates a capacity for CO.sub.2
injection into unit 26.
[0481] 8.26. Item twenty-six (26) represents a capacity for CO.sub.2
dissolution into the return flow (20).
[0482] 8.27. Item twenty-seven (27) indicates a capacity for pumping
CO.sub.2 into the return flow modality shown as item 15, via a CO.sub.2
injection-dissolution unit labeled 28.
[0483] 8.28. Item twenty-eight (28) represents a CO.sub.2
injection-dissolution unit for return flow being diffused in a carefully
controlled manner into the biozone via (typically an array of) pipe
diffusers (15).
[0484] 9. FIG. 9 adds detail to FIG. 1. It does so within Box 4 (that is
left empty in FIG. 1). Boxes 1 through three, and items 1 through 14,
excepting items 7a and 7b, are identical to those displayed in FIG. 1.
Therefore, below, names of items and brief associated contextual
descriptions are provided only for the following labeled items: 7a and
7b, and items 15a,b,c,d,e, 16, 17, 18 and 19. (The set of icons labeled
as item 20 is identical in FIG. 9 as in FIG. 1.)
[0485] 9.7 a,b. Items labeled seven (7a and 7b) indicate different
modalities of return flow. Flow vector 7a corresponds to a method and/or
system similar to item 15 in the previous figure (8.15). Flow vector 7b
corresponds to return flow input entering into a water treatment method
and/or system (as is shown, for example, in FIG. 8, items 17a.b, 18, 19,
and 26).
[0486] 9.15 a,b,c,d,e. Items fifteen (15 a through e) indicate CO.sub.2
input flows from a CO.sub.2 Utilization Hub (1: CO.sub.2-UH) into a range
of components of return flow operations (15a,b,d, e) as well as by direct
diffusion-dissolution (15c) into the lake's biozone via an array of gas
diffusers. Item 15a indicates pH-controlling CO.sub.2
injection-dissolution into return flow after "total degassing" via a TDS
method and/or system (Box 1: TDS). Item 15b indicates CO.sub.2
injection-dissolution into return flow water treatment operations similar
to those shown in FIG. 8, box 3 in a flow series beginning with item 16
(8.16). Item 15c indicates CO.sub.2 injection-dissolution directly into
Lake Kivu's biozone by gas diffuser pipes as noted above. Item 15d
indicates CO.sub.2 injection-dissolution into return flow directed into a
water diffusion system diffusing return flow water into Lake Kivu's
biozone. Item 15e indicates injection of CO.sub.2 into reinjection pipe
systems (18) carrying water out from water treatment (16). This form of
CO.sub.2 injection-dissolution is a mode of pH control (de-alkalization).
[0487] 9.16. Item sixteen (16) represents a water treatment sector
utilizing biological processes such as algal photosynthesis. Such
operations are known as Biological Production Units (BPUs).
[0488] 9.17. Item seventeen (17) represents a water treatment unit for
precipitation of Mg and Ca. In some embodiments, this involves algal
flocculation and harvesting.
[0489] 9.18. Item eighteen (18) represents return flow reinjection pipe
systems carrying water out from water treatment (16) and in some
embodiments utilizing CO.sub.2 injection-dissolution (15e) as a mode of
pH control (de-alkalization).
[0490] 9.19. Item/vector nineteen (19) represents materials extractions
supporting products production (8) modes based upon de-densifying water
treatment of the return flow of degassed deepwater. Flow vector 19 should
be considered as delivering materials into the CO.sub.2 Utilization Hub
(CO.sub.2-UH: Box 1), for example Mg and Ca precipitates and algal
biomass.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS OF THE INVENTION
[0491] The disclosure of the invention presented herein is a teaching. It
reveals to the Republic of Rwanda, and more broadly to the Kivu region of
the DRC, an unprecedented possibility and opportunity for global
leadership in advanced greentech industrialization, specifically in
productive utilization of CO.sub.2 in amounts equal to the world's
largest industrial flows of CO.sub.2. The location of Lake Kivu close to
the geographical center of the African continent offers an economically
favored opportunity for CO.sub.2-utilizing industrial production of
products that are expensive to import from the coast. CO.sub.2
utilization also offers ways to produce a large number of high-value
export products. The scale of the opportunity is very large within its
context. A doubling of Rwanda's rate of per capita economic growth is
possible.
[0492] Carbon dioxide has never been extracted from a lake for industrial
use. No prior art exists in this specific category of activity. Carbon
dioxide has been vented from lakes in Cameroon and in Spain (Halbwachs et
al., 2004; Kling et al., 2005; Sanchez-Espana et al., 2014) for safety
purposes using auto-siphoning pipe-jet fountains. There has been no
capture and utilization of the gas.
[0493] Lake Kivu's dissolved gases trapped at depth are a mixture of
methane and CO.sub.2. This situation presents a difficulty: too much
CO.sub.2 is present for efficient combustion such that gas-cleaning
stages are required, causing substantial efficiency losses. This problem
has been solved by the inventor in a previous disclosure documented
herein presenting a method and system of "total gas" extraction into an
oxyfuel combustion heat engine that exhausts nominally pure CO.sub.2
(excepting water vapor which can be removed easily if desired). The
situation also presents a difficulty for the use of the CO.sub.2 present,
as noted, in a vast store in Lake Kivu of approximately 600 million
tonnes. The invention disclosed herein discloses a method and system that
allows hyper-efficient utilization and effective separation of both
methane and CO.sub.2. This is via two variant processes: one involving
modification of existing methane degassing methods, systems, designs and
apparatus, and the other in conjunction with the oxyfuel method of power
generation which utilizes unseparated "total gas" degassed by deepwater
extraction degassing without a separation method separating CO.sub.2 from
methane. It is surprising that it can be possible to unlock Lake Kivu's
resources in such efficient ways without wasting either CO.sub.2 or
methane. In the present disclosure, the primary focus is on unlocking
Lake Kivu's CO.sub.2 resource in coordination with efficient capture and
use of Lake Kivu's biomethane reserve. Degassing CO.sub.2 additionally
can secure lake safety against a limnic eruption mega-catastrophe. This
is a vital associated goal.
[0494] As noted herein, industrial sources of CO.sub.2, when obtained from
natural occurrences, typically are nominally pure. A particularly
pertinent example is the Kereita Forest spring source (actually a drilled
fountaining jet of water and CO.sub.2) used by the Kenyan company
Carbacid (CO.sub.2) Limited (www.carbacid.co.ke). Carbacid (CO.sub.2)
Limited provides and sells CO.sub.2 from this source for use in beverage
carbonation all over East Africa. It is ironic that businesses operating
on the shores of Lake Kivu buy Carbacid CO.sub.2 obtained from the
distant Kereita Forest while 600 million tonnes is trapped nearby, and
when nearby volcanoes and mazuku vents bordering the lake naturally emit
perhaps as much as 30 million tonnes CO.sub.2 per year into the local
atmosphere. Another ironic aspect is the way the standard technology
practiced on Lake Kivu returns CO.sub.2 into the depths of the lake (and
thereby extends the mortal danger from a possible limnic eruption). As
the MSDS method and system disclosed herein shows, CO.sub.2 can de
degassed by a relatively simple design modification. However, when the
standard design was created, it was not obvious how such large amounts of
degassed CO.sub.2 could be used, whereas it generally is well understood
that venting CO.sub.2 to the atmosphere is environmentally problematic.
The present disclosure provides the surprising insight that many useful
uses exist. These sum together to a very large scale of potential
CO.sub.2 utilization. Unlocking Lake Kivu's trapped mega-source of
CO.sub.2 offers a transformation by the creation of a massive flux of
purified, naturally-sourced CO.sub.2 herein estimated roughly as .about.9
million tonnes per year. That is a surprise.
[0495] Separating CO.sub.2 by means of modifying the traditional staged
degassing system design (SDS to MSDS as shown in FIG. 8) yields CO.sub.2
with residual methane present. It does not yield a purified CO.sub.2.
(Avoiding methane wastage is one of the efficiency gains of the variant
process based on total degassing followed by oxyfuel combustion.) This
type of methane-laced CO.sub.2 has a special utility as an aquatic carbon
source. When carbon dioxide in injected into the biozone, any
accompanying methane can be utilized by oxidizing bacteria present in the
biozone. Such bacteria can utilize methane as an energy source and also
as a carbon source. Their growth can increase overall bioproductivity.
[0496] A particular challenge the invention addresses is CO.sub.2
utilization on a scale sufficient to match the scale of CO.sub.2 degassed
in power plant operations obtaining Lake Kivu's methane and degassing its
deepwater CO.sub.2. For the Rwandan side of the lake this scale is
roughly 10 million tonnes of CO.sub.2 per year. That approximately equals
the largest single source CO.sub.2 extraction flux in the world (from a
CO.sub.2 well used to supply CO.sub.2 for EOR in west Texas, USA). Herein
it is shown that at least 1/3.sup.rd of powerplant (OXFCPS) CO.sub.2 flux
can be utilized valuably in direct connection with treatment of
powerplant return flow reinjection into the lake. It is shown that this
fraction increases to over 1/2 with inclusion of related CO.sub.2
utilization processes set by levels of different resources present in the
deepwater. Several other CO.sub.2 utilization processes can boost the
overall level of CO.sub.2 utilization to match the total level of flux.
The invention demonstrates that it is possible to utilize the full scale
of CO.sub.2 flux in an industrially productive manner. This is shown in
Table 2.
[0497] The Lake Kivu region is magnificently attractive. The area has
strong eco-tourism potential. It could be spectacular for real estate
development. Accelerated development of the area will require concrete
and other building materials for roads, culverts, bridges, runways, dams,
buildings, tunnels, piers, docks and walkways. Magnesium-mineralized
CO.sub.2 can provide a source of mineral carbonate mass for advanced
construction materials sourced from CO.sub.2 combining with precipitated
magnesium hydroxide, and also via carbonation of additional pozzolanic
materials from abundant local volcanic ash sources. The region possesses
densely populated hyper-fertile lands with a strong farming tradition. It
is a situation likely to be enthusiastic for the development of
CO.sub.2-boosted very-high-yield greenhouse horticulture. Farmers can
utilize urea made with deepwater CO.sub.2 and bio-ammonium to intensify
crop yields in the region, and to expand agro-production for exporting
flowers, high-value specialty foods, plant extracts and other exports.
These can include a wide variety of potential nutraceutical and
pharmaceutical products linked with CCU. Pyrethrum production offers a
substantial opportunity for organic biopesticide production linked with
CO.sub.2 because it is a longstanding crop in the region. The wider
region also has huge potential for minerals/metals extraction with
value-add ore processing. A low-cost CO.sub.2 supply can assist several
modes of metals extraction and value-add processing, as noted herein.
These range from use of carbon monoxide in smelting tin to new
technologies of coltan value-add refining, to dunite-olivine carbonation
for production of silicon-, magnesium-, and iron-rich plant fertilizers,
as well as eco-nickel from Mg-carbonate mineralization of CO.sub.2. The
wider Lake Kivu region has huge potential for dry ice distribution. Dry
ice can provide efficient off-grid refrigeration linked with beverage and
food distribution. To the west, the great Congo forests have substantial
potential for sustainable forestry products development. Production
possibilities exist in many areas of CO.sub.2-utilizing industrial
technology, ranging from bioplastics to biochemicals to biosynthetic
textiles, to paper, xylitol, wallboard production and biofuels. All of
these types of forest biomass-related products utilize CO.sub.2, and some
use formic acid that can be produced from CO.sub.2. To the east are huge
reserves of alkaline brines and soda ash already being used for sodium
bicarbonate production. Sodium bicarbonate can be used in high-value
algal products production. It also is useful in biomass and mineral ores
processing. To the north, multi-billion barrel opportunities exist for
extraction of oils supported by CO.sub.2-EOR technologies. Oil fields
exist in the range 150 to 400 km distant from Lake Kivu. To the east,
radiation-optimal locations for solar power arrays in NW Tanzania, NW
Kenya and NE Uganda. These areas are attractive for solar power
generation for the purpose of powering production of CO.sub.2-utilizing
"solar fuels"/"electrofuels" production. High voltage wires can transport
solar power from these regions to the CO.sub.2 supply at Lake Kivu. Lake
Kivu biomethane can be used with CO.sub.2 input to produce Gas-to-Liquids
(GTL) biomethanol for transport fuel admixing. Large-scale algae
production utilizing CO.sub.2 as a carbon source offers opportunities for
high-value nutraceuticals and pharmaceuticals production as well as
biofuels, bio-asphalt, bio-nitrogen and bio-char fertilizers,
CO.sub.2-utilizing bioplastics, and other green chemicals. In the future,
many attractive commercialized technologies will emerge for large-scale
CO.sub.2 utilization, for example, high-value carbon nanofiber and
nanotubes production from CO.sub.2.
[0498] Numbers describing resource abundances in Lake Kivu deepwater and
deepwater inflows are provided in Table 1 scaled to 100 MW for electric
power output. Estimates of potential practical scales for the examples
provided of 20 "main mode" possibilities for CO.sub.2 utilization shown
in Table 2. These are scaled to roughly a 400 MW power output. The
comparison shows that CO.sub.2 output at this scale (.about.9 MTA
CO.sub.2) can be utilized practically.
TABLE-US-00001
TABLE 1
LAKE KIVU DEEPWATER RESOURCES & ANNUAL FLUXES
Kivu Total MRZ conc. 100 MW scale*
Resource (Resource zone, tonnes) (per 1000 litres) (T: tonnes/yr)
Methane ~47 Million T*** ~250 grams ~132,000 T/yr
CO.sub.2 (from CH4 ~363,000 T/yr
combustion):
CO.sub.2 (gas) ~400 Million T** ~3.5 kg ~1.9 Million T/yr
CO.sub.2 (total degassed + ~2.3 Million T/yr
combustion):
HCO.sub.3.sub.- ~500 Million T** ~4.2 kg ~2.2 Million T/yr
Ammonium ~12 MT (UE)** ~60 g (NH.sub.4.sup.+) ~53,000 T (UE)/yr
Phosphorus ~0.6 MT (P)** ~5 g (P) ~2,600 T (P)/yr
Magnesium ~35 MT (Mg)** ~300 g (Mg) ~156,000 T (Mg)/yr
MRZ = Main Resource Zone. MRZ volume: ~118 km3 deepwater.
*Deepwater extraction/use scaled to 100 MW power output for the method and
system disclosed herein: 0.53 cubic km deepwater/yr
**Main Resource Zone (MRZ) only.
***Methane total estimate for Lake Kivu for all zones reported by Wuest et
al., (2012). Other concentrations from Tassi et al., (2009).
UE = Urea Equivalent mass.
TABLE-US-00002
TABLE 2
CO.sub.2 UTILIZATION MODES & ESTIMATES
Scale Potential (MTA)
(Million Tonnes
Mode of CO.sub.2 Utilization CO2 per Annum) Notes
1. Local greenhouse horticulture ~2 area: ~5,000 hectares
2. Lake Kivu biozone CO.sub.2-fertilization ~2 scaled to ~400 MW
3. Lake Kivu return flow pH-lowering ~1 scaled to ~400 MW
4. pH control, return flow water treatment n.e. Precip. control & algal
C-source
5. Algal production (incl. bicarbonate): ~0.5 to 5 >35 tonnes
dryweight/ha/yr
6. High-pressure CO.sub.2 pipeline delivery ~1 to 4 mostly for
CO.sub.2-EOR
7. Refrigerated CO.sub.2 delivery: ~0.1 liquid CO.sub.2 & dry ice
8. Eco-concrete & related materials: ~0.7 scaled to Mg-hydroxide flux
9. Urea production from NH.sub.3: ~0.3 scaled to NH.sub.4.sup.+ flux
10. CO.sub.2 to formic acid: ~0.01 many & various uses
11. CO.sub.2 to carbon monoxide (CO): ~0.01 for example tin smelting
12. CO.sub.2-pyrethrum biopesticide: ~0.02 e.g., BRA: Botan. Res. Austr.
13. Forest products CO.sub.2 processing: n.e. e.g., Chempolis (formic
acid)
14. CO.sub.2-geothermal energy extraction: n.e. emerging technology
15. Fuels & chemicals production: n.e. many companies
16. CO.sub.2 + H.sub.2O to syngas: MeOH, DME: n.e. e.g., Haldor Topsoe
17. CO.sub.2 to oxalic acid platform: n.e. e.g., LiquidLight
18. CO.sub.2 + H.sub.2 into gas fermentation: n.e. e.g., LanzaTech
19. CO.sub.2 into plastics: n.e. e.g., Covestro, Novomer
20. CO.sub.2 into high-value C-products n.e. e.g., C-nanotubes
TOTAL, ESTIMATED SOURCES: ~>9 MTA
CO.sub.2 output, 400 MW power plant: ~9 MTA
n.e. = not estimated
[0499] A reasonable scale for application of the invention disclosed
herein is .about.400 MW of total electrical power generation. This scale
is based on combustion efficiency optimization suggested by a business
partnership that manufactures advanced oxyfuel turbine systems. A
reference scale target for CO.sub.2 utilization therefore is set by the
sum of degassed CO.sub.2 and combustion-created CO.sub.2 for 400 MW on
power output. This result is: 9 MT CO.sub.2/yr. Input data for this
calculation are provided in Table 1. A rough maximum scale for CO.sub.2
utilization corresponds to degassing of the entire budget of CO.sub.2 in
Lake Kivu (.about.600 million tonnes) in .about.30 years plus 50 MT
biomethane converted to CO.sub.2 mass (=138 MT CO.sub.2). This amounts to
a production of roughly 700 to 750 MT CO.sub.2 in 30 years, hence up to:
.about.25 MTA CO.sub.2. This maximum CO.sub.2 utilization opportunity
scale is close to the world's largest scale of CO.sub.2 utilization in
the context of a CO.sub.2 pipelines hub: .about.30 MTA CO.sub.2 through
the West Texas Denver City hub for CO.sub.2-EOR. Note that removal of
Lake Kivu's deepwater CO.sub.2 is essential for long-term human safety in
the Lake Kivu basin involving millions of human lives as well as the
ecological survival of Lake Kivu's fauna (which periodically has been
destroyed by past limnic eruptions).
[0500] The system of the invention comprises subsystems including a carbon
dioxide utilization hub (CO.sub.2-UH). In certain embodiments, the system
comprises two or three coupled subsystems shown in FIG. 1: (i) TDS or
MSDS variant; (ii) OXFCPS (not present in the MSDS variant); and (iii)
CO.sub.2-UH. Other embodiments additionally comprise other subsystems
such as at least one CO.sub.2 utilization subsystem expressed as a
specific modality or associated set of modalities of production and
output operating via the CO.sub.2-UH. Certain embodiments of the
invention differ from one another only in the nature and quantity of
these CO.sub.2 utilization subsystems supplied with CO.sub.2 by the
CO.sub.2-UH.
[0501] CO.sub.2 utilization subsystems suitable for use in the invention
are not particularly limited in scope or quantity. The hundreds of
possibilities for CO.sub.2 utilization described herein are exemplary
rather than exclusive. The twenty different subsystems or main modes of
CO.sub.2 utilization described below and in Table 2 above exemplify a
wide spectrum of embodiments of the invention. Potential CO.sub.2
utilization scales are cited where it has seemed reasonable to do so, but
such scales are not intended to have a limiting effect on the scope of
the invention. Certain preferred embodiments presented under the
categories of the twenty main modes of CO.sub.2 utilization included in
the following sections are not exclusive of one another. They may be
performed independently or in any of a large number of combinations. The
listing and illustration of twenty main modes is not meant to be
delimiting. The general concept of a CO.sub.2 Utilization Hub is that it
is open to the incorporation of new modality types (as is illustrated in
FIG. 7). This aspect of openness is a preferred embodiment of the
invention.
[0502] The invention disclosed herein solves a major unsolved
technological problem of practical CO.sub.2 utilization on a large scale
in the context of a developing economy remote from railway connections
and oceanic ports. Specifically, the major challenge is CO.sub.2
utilization: to degas and then productively utilize Lake Kivu's huge
(.about.600 million tonnes) supply of deepwater dissolved CO.sub.2.
Simultaneously, certain embodiments of the invention solve five
additional big problems and challenges: (i) efficient power production
utilizing Lake Kivu's deepwater methane with avoidance of wastage of a
limited resource; (ii) insuring lake safety (as well as resource loss)
against the possibility of mega-catastrophe from CO.sub.2 asphyxiation
via a runaway "limnic eruption" degassing event; (iii) building-up
regional development on a large scale via industrialization; (iv) power
load balancing in various contexts including load balancing for the local
and national power grid and for intake and industrial utilization of
solar power; and (v) creating a globally strategic demonstration of large
scale CO.sub.2 industrial utilization as a major contribution towards
solving problems of rapid and accelerating CO.sub.2 accumulation in the
atmosphere.
[0503] FIG. 1, shows a novel method and system based upon linking specific
opportunities of Lake Kivu power production to a large and diverse body
of technological insight and innovation on CO.sub.2 utilization such as
is documented very extensively herein as a teaching. This teaching
clarifies the background and nature of the invention, especially in the
context of generic conventional beliefs that CO.sub.2 is useless in the
context of Lake Kivu and, if degassed, would be vented and hence an
environmental nuisance.
[0504] The inventive embodiment shown in FIG. 1 integrates insight on
CO.sub.2 utilization into an overall method and system for Lake Kivu
deepwater gas extraction and use via a core combination of three
submethods and subsystems. These are shown within boxes 1, 2 and 3 as
represented in the figure: (i) degassing in a total degassing system
(TDS: 1) that includes extracting (6) gas-rich deepwater (9c) from Lake
Kivu (9a,b,c); (ii) power production and CO.sub.2-dominated exhaust
creation by means of an oxyfuel combustion power system (OXFPCS: 2) which
intakes (and includes production of) pure oxygen for oxy-combustion (10);
and (iii) receiving, processing and utilizing CO.sub.2 in a CO.sub.2
utilization hub (CO.sub.2-UH: 3), with the overall activity generating
electrical power as well as various types of product streams from various
modalities of CO.sub.2 utilization (8). Flow vectors, (11, 12) are shown
connecting these boxes with flow compositions as identified. In addition
to the three core submethods and subsystems (1, 2, 3), two additional
boxes are shown in dashed outline (4, 5). These represent non-core
aspects of the process flow of the invention. Box 4 includes a set of
five modalities of CO.sub.2 utilization, but these are shown in detail
only in FIG. 9 (FIG. 9: 15a,b,c,d,e). These are abbreviated as a single
flow-designating arrow (15) in FIG. 1. Box 5 represents cryo-energy
storage capacities linking the OXFCPS (2) to the CO.sub.2-UH (3) where
cryogenically liquefied gases are stored. Embodiments with this capacity
are included and preferred. They allow the powerplant to provide electric
power load-balancing services for its own output as well as for solar
power inputs into the operations of the CO.sub.2-UH. Further expansion of
cryo-energy storage capacities, included as a preferred embodiment, also
may allow load-balancing services to be provided to the grid. This is
done via the powerplant's (included) Air Separation Unit (ASU), which is
shown in FIG. 1 only as item 10 providing oxygen gas for oxyfueled
combustion. Thus, in the full modality of incorporation of the capacity
indicated by box 5 within the invention, the ASU operates in an expanded
modality embodiment as a Cryo-Production Unit (ASU-CRPU. FIG. 6 and
associated text provide further detail). Note, however, that the ASU
providing oxygen into oxyfueled combustion is not limited to a cryogenic
method. Non-cryogenic modalities of provision of oxygen herein are
included as embodiments such as, for example, ion transport membranes
(ITMs) and other oxygen-selective membrane separation methods.
[0505] The modalities of CO.sub.2 utilization shown in FIG. 1, box 4 are
aspects of the extended function (8) of the CO.sub.2-UH (box 3). They are
shown as a separate box because they all recycle CO.sub.2 from one part
of Lake Kivu (9c) to a variety of uses within, and floating on, the
lake's biozone (9a). These uses provide a means to utilize CO.sub.2 in a
substantial fraction of the total flow
[0506] FIG. 1 represents the core aspect of the invention as a combinative
integration of three submethods and subsystems represented by the three
boxes labeled 1, 2 and 3, with their interconnections 11 and 12. A
variant of this core is represented wherein a modification of the
standard degassing method (SDS: Staged Degassing System: see FIG. 8) is
shown identified by the acronym MSDS (10, 14). This variant represents a
modification of the Belgian method (of methane purification by staged
separation/removal of CO.sub.2 using gas-water partitionings
differentiating between methane and CO.sub.2) that has been designed and
deployed on Lake Kivu ever since it was created in the 1950s. The MSDS
method is illustrated in FIG. 8 and described in associated text.
[0507] In FIG. 1, the MSDS is indicated by item 13 (representing a
CO.sub.2 degasser within a MSDS) connecting (14) into the
CO.sub.2-Utilization Hub (3). Item 13 transfers CO.sub.2 flux into a
CO.sub.2-UH from a MSDS-type degassing system and method that degasses
deepwater CH.sub.4 and CO.sub.2 separately. (For details see FIG. 8.)
[0508] The invention does not subsist in its constituent submethods and
subsystems. FIG. 1 describes the invention in its aspect of being an
integrative combination of submethods and subsystems. Shown for the TDS
variation is an integration of three submethods and subsystems. These are
labeled 1, 2 and 3 described by the acronyms, TDS (for: Total Degassing
System), OXFCPS (for: Oxy-Fuel Combustion Power System) and CO.sub.2-UH
(CO.sub.2 Utilization Hub), respectively. Vertical plane perspective is
employed only for Lake Kivu (9) with gas-rich water extraction (6) from
deep in the lake (9c), and degassed water flow return (7) connecting via
the TDS (1) located partly above the surface of the lake.
[0509] Embodiments of the TDS and the OXFCPS suitable for use in the
present invention are disclosed by the inventor in U.S. Patent
Application No. 62/007,912, filed Jun. 4, 2014. The present invention is
not limited to such embodiments, however.
[0510] The OXFCPS is a submethod and/or subsystem which combusts methane
present within the degassed gas transferred from the TDS. It transforms
released energy into mechanical power extracted via a heat engine.
Typically, but not always, this power is transformed into electricity.
The central aspect of oxyfuel combustion is that the method and system
inputs nominally pure oxygen into combustion rather than air (with its
associated large component of nitrogen gas accompanying oxygen gas). The
OXFCPS here defined incorporates sourcing of separated oxygen in some
form of Air Separation Unit (ASU), but is open with respect to the
specific technologies employed for oxygen separation. Methods and systems
used may be traditional cryogenic air separation or newer ion transport
membrane (ITM) processes, or any effective method. All are herein
included in embodiments: any separation process or processes such as may
provide nominally pure oxygen into oxyfuel combustion. It is not
necessary for atmospheric air to be input. Other input gas sources are
possible.
[0511] The OXFCPS defined herein may or may not include one or more
supercritical CO.sub.2 power cycles. The OXFCPS facilitates efficient use
of a total gas input from the TDS, containing methane efficiently
extracted, modified only as needed for H.sub.2S removal and/or removal of
water vapor, and efficiently combusted under oxyfuel conditions forming
an exhaust stream of easily separable CO.sub.2+H.sub.2O. A strong
efficiency advantage may optionally be supplied by intake compression of
the "total gas" inflow into a supercritical CO.sub.2 power cycle.
[0512] The CO.sub.2-UH is a submethod and/or subsystem of the invention
described and defined in its basic attributes as follows. Detailed
physical specifications for components may be many and varied such as
correspond to matters of design at a level of detail unrelated to the
inventive art disclosed herein. Such matters are known to those skilled
in the art. The CO.sub.2-UH: (i) receives exhaust either from the OXFCPS
comprised of a nominally two-component mixture of CO.sub.2 and steam, or
in the variant MSDS-based method and system as CO.sub.2 and water vapor;
(iii) processes this gas flow initially, if and as needed, for example in
some embodiments via heat exchange energy capture, and in some other
embodiments by gas dehydration, or with combination of both; (iv)
partitions and directs the resulting gas flow into one or more process
trains; (v) prepares and produces such flows through one or more of these
process trains for utilization in one or more ways, for example as a mode
of raw gas (in some process trains), or in various grades and forms of
CO.sub.2 (in other process trains), and/or uses the resulting gas flows
from one or more of these process trains to produce products requiring
CO.sub.2 inputs (in other process trains) and/or requiring the use of
CO.sub.2 in their production (in other process trains). In certain
preferred embodiments, one or more process trains may share cryogenic
functions with the ASU component of the OXFCPS. In certain preferred
embodiments, process trains purposed for CO.sub.2 refrigeration are
co-utilized for cryogenic gas processing, storage and dispersing of
liquid nitrogen and liquid oxygen and/or liquefied natural gas (LNG). In
summary, the CO.sub.2-UH in its operation transforms the flow of
CO.sub.2-containing exhaust from the OXFCPS into flows of various
CO.sub.2 products, and/or CO.sub.2-containing products, and/or products
manufactured with the use of CO.sub.2. In some preferred embodiments,
these features are supplemented by add-on capabilities for receiving,
storing and dispensing pressurized and/or liquefied nitrogen and
pressurized and/or liquefied oxygen and pressurized and/or liquefied
natural gas. Sometimes these supplemented capacities support the storage
and recovery of cryo-energy such as can be useful for varying power
output to the grid and/or for grid balancing, sometimes involving
cryogenically storing inputs of time-varying power inputs from the grid
such as renewable power sources (see FIG. 6). Production of purified NG
and LNG also opens up possibilities, herein included as preferred
embodiments, for conventional energy storage as well as providing the
capacity for sales of LNG, Compressed Natural Gas (CNG), and Absorbed
Natural Gas (ANG) if/as desired. Production of LNG also offers a mode of
dry ice production as a byproduct of CO.sub.2 separation from biogas
(Fazlollahi and Baxter, 2017). Such dry ice also can be used for
cryo-energy storage via the methods developed by Larry Baxter and
colleagues (explanations and publications posted on
https://sesinnovation.com)
[0513] FIG. 2 provides further detail to illuminate the representation
made in FIG. 1 but does not include illustration of the MSDS-based
variant shown in FIGS. 1 and 8. FIG. 2 shows in schematic representation
the invention as an industrial process arising out of Lake Kivu's layered
structure represented by arrows, circles and boxes. Deepwater resources
of dissolved gases are extracted (22), and then utilized (26, 21, 1, 2,
3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20). These
deepwater resources are present principally, (but not exclusively), in
Lake Kivu's so-called Main Resource Zone (23c). FIG. 2, box 2 encloses
schematically the method and system of a CO.sub.2-UH (21) organizing the
transformation of inputs (28; 32; 39), especially CO.sub.2 plus water
vapor (28), into outputs (item 33), comprising twenty or more main modes
(represented in FIG. 2 by vectors 1 through 20). The industrial process
creates products that include electric power (29) produced by an oxyfuel
combustion power production method and/or system (26; 27; 28; 29)
including an air separation unit (27). In the TDS-based variant of the
invention, the power production method and system is the OXFCPS. It is
shown as a circle (26) linking together a nexus of inflows (25; 27) of
fuel gases (25; 27) and outflows of power (29) and post-combustion
exhaust (28). The main carbon source input into the CO.sub.2-UH is the
post-combustion exhaust (28) expelled by the OXFCPS. The CO.sub.2-UH
receives, stores, dispenses and utilizes this exhaust, which is comprised
mostly of carbon dioxide and water, either in the form of vapor or
condensed liquid water. It uses electric power, either internally
produced by the powerplant (as represented by output vector 29), or from
any other source. Inputs of any type needed for production are
represented by vector 32. These inputs enter into the CO.sub.2-UH. The
industrial process (and method and/or system) also produces a suite of
carbon-containing (and hence carbon-capturing) industrial products [1
through 20 as outputs (33) of CO.sub.2-UH (21)]. Outputs are created by
means of submethods and/or subsystems organized within an integrated
CO.sub.2-UH submethod and/or subsystem (21) shown with outputs (1 to 20)
within box 2. The CO.sub.2-UH is defined herein to include within its
domain any modality and combination of modalities of CO.sub.2 utilization
and associated product outflow based upon CO.sub.2 inflows obtained from
Lake Kivu in the course of deepwater methane-based power production,
including both deepwater CO.sub.2 and CO.sub.2 formed from combustion of
deepwater methane (or, in the case of the MSDS method and/or system,
deepwater CO.sub.2 only).
[0514] FIG. 2 shows Lake Kivu on the bottom left in vertical slice
perspective in three layers (23 a, b, c). These are: the bottom "Main
Resource Zone" (23c: MRZ: .about.250 to .about.485 meters depth), the
near-surface "BioZone" (23a: BZ, 0 to .about.80 meters depth) and a
middle zone (23b: .about.250 to .about.80 meters depth). The middle zone
as shown is a combination of two zones: the "Potential Resource Zone"
(PRZ) and the "Intermediate Zone" (IZ), represented in scientific and
engineering reports describing the gas resources and limnological
structure of the lake (Descy et al., 2012; Wuest et al., 2012a,b). The
industrial process begins with the extraction of deepwater in a system of
flow organized by one or more riser pipe submethods and subsystems (22).
See, e.g., US 2015/0354451 A1. These submethods and/or subsystems
transport deepwater rich in dissolved methane and CO.sub.2 into a
degassing submethod and/or subsystem (24). This should be considered to
include the riser or risers (22) themselves. The degassing submethod
and/or subsystem (22, 24) separates the inflow of gas-rich water (22)
into outflows of separated degassed water (34) and separated gases (25).
Separated degassed water is transferred by a submethod and/or subsystem
of return flow pipes, pumps and containing reservoirs (34, 35) that
variously control the reinjection of return flow waters into Lake Kivu
via various options (36a, 36b, 36c). These reinjection options are not
exclusive of one another. Preferred embodiments thereof are described, as
noted herein, in other disclosures focused on Lake Kivu made by the
inventor. The variant MSDS-based form of the invention is shown in FIG.
1.
[0515] As shown in FIG. 2, separated gas from the TDS (22, 24, 25, as
shown in box 1) comprised mostly of CO.sub.2 plus methane plus water
vapor is transported and processed, if and as needed, for input into an
oxyfuel combustion system (26, 27) into which oxygen is added via an air
separation unit (27) which is a component of the powerplant (26, 27).
Combustion of methane with pure oxygen transforms the input gases (25,
27, 31) into mechanical power used to generate electric power (29) and an
output exhaust stream (28) comprised of mostly CO.sub.2 plus condensable
water vapor. FIG. 2 shows a post-combustion exhaust stream (28). It
provides oxyfuel powerplant combustion exhaust of carbon dioxide and
steam as input into a CO.sub.2 utilization hub (CO.sub.2-UH, item: 21).
In the variant MSDS-based form of the invention, the connection between
the degassing system and the CO.sub.2-UH is simpler, as represented by
item 14 in FIG. 1.
[0516] CO.sub.2 is provided in post-combustion exhaust expelled by the
OXFPCS (which may or may not be a combined cycle). It also is provided by
degassed CO.sub.2 from a MSDS. These sources of CO.sub.2 initially enter
a processing, storage and purveying/distribution unit (30), shown in FIG.
3. This unit (30) processes, handles and stores input exhaust (28) and
disperses the flow into different streams. (It is the subject of FIG. 3,
which in part displays its components, methods, systems and activities.)
These streams are comprised of CO.sub.2 products in different forms
symbolized by eight specific arrows corresponding to modalities of use
(1, 2, 3, 4, 5, 6, 7, 8). A flux vector labeled as item 37 represents the
use of any of these CO.sub.2 product streams internally within the
CO.sub.2 utilization hub for additional modes of product manufacture
utilizing CO.sub.2 (8 through 20). (Note that arrow number 8 is
intermediate. It is both a mode of CO.sub.2 product and a mode of
creating products utilizing CO.sub.2.) Overall, in the sum of any to all
of its preferred embodiments, the CO.sub.2-UH can produce an overall
output of products shown as vector 33. This output is comprised of one or
more of a suite of carbon-containing and purified and non-purified
CO.sub.2 products, plus products produced using CO.sub.2 in some way but
not incorporating its carbon. One non-purified CO.sub.2 product is a
stream of "raw" (unprocessed or relatively unprocessed) CO.sub.2 and
steam or condensed water (vectors 1, 2, 3 and 4). It may be disseminated
and diffused into the biozone (23a: BZ) of Lake Kivu in order to provide
a carbon source for photoautotrophic bioproductivity, as shown for
vectors 2a and 2b. Or this form of CO.sub.2 may be provided to local
greenhouses, as shown by vector 1.
[0517] As shown in FIG. 2 by flux vector 31, oxygen gas output may be
obtained as a byproduct of chemical production and/or bio- or
artificial-photosynthetic processes and/or water electrolysis in the
CO.sub.2-UH (21). Such oxygen may be used for increased power production
efficiency by supplying a component of oxygen otherwise provided by the
Air Separation Unit (27, utilizing atmospheric air input shown as vector
41).
[0518] As shown in FIG. 2, the ASU (27) also produces liquefied nitrogen
gas, (LN.sub.2) separated from oxygen gas (39, 40). Some of this LN.sub.2
is used internally within the ASU for cryogenic energy recovery by means
of cooling incoming air via a heat exchange process. In certain preferred
embodiments, excess LN.sub.2 from the ASU is provided (42) into the gas
processing, storage and handling unit (30) of the CO.sub.2-UH, as shown
by vector 39. Or it may be provided otherwise for other purposes, as
shown by vector 40.
[0519] FIG. 2, Box 3, illustrates adjunct utilization of excess liquid
nitrogen and/or oxygen (via flow vectors 39 and/or 40 and/or 42) to cool
one or more large refrigeration utilization facilities (43), such as, for
example, a digital data center. Flow vectors 39 and 42 flow into the
liquefied gas storage units within the gas-processing (30) sector of the
CO.sub.2-UH (21), (see process train 25, units 30 and 31 in FIG. 3). In
FIG. 2, box 3, the vectors labeled 39 and 42 indicate either direct flow
from the ASU (27) or flow from LN.sub.2 and LO.sub.2 storage facilities
as shown in FIG. 3. (In FIG. 3, LO.sub.2 and LN.sub.2 storage units 30
and 31 connect via insulated pipe transfer systems labeled 37 and 38,
respectively.) Post-cooling flows of gasified N.sub.2 (44) are available
for various uses such as, for example, can be engaged to pH control and
related algae culturing operations as illustrated partially in FIG. 8,
Box 3, return flow water treatment (flow direction 16). Post-cooling
flows of gasified LO.sub.2 (45) are provided into oxyfuel combustion
(item 27). Aspects of such gas plumbing associated with utilization of
cryo-energy for cooling as well as for cryo-storage of energy are
represented in FIG. 6 and explained in accompanying text describing the
utilization of LO.sub.2 and/or LN.sub.2 and/or refrigerated liquefied
O.sub.2 (LCO.sub.2 or LCO.sub.2) for this purpose. For reasons of already
considerable complexity, FIG. 2 avoids representing these aspects of the
invention. They are reserved for FIG. 6 and its explanations.
[0520] In certain preferred embodiments, LN.sub.2 is utilized for
cryoenergy storage for load balancing purposes, facilitating the
operation of the OXFCPS (shown in FIGS. 1 and 2). This stored energy is
released by heat exchange with atmospheric air and/or powerplant exhaust,
whereby the phase-changed expanding gas drives a power-producing turbine
heat engine. See FIG. 6.
[0521] In certain preferred embodiments, storage of liquefied oxygen
(LO.sub.2) similarly provides stored cryo-energy. Similarly, this
cryo-energy is released by heat exchange with the atmosphere, and/or
powerplant exhaust, whereby the phase-changed expanding gas drives a
power-producing turbine heat engine wherewith and whereby the warmed-up
O.sub.2 emerging is fed into oxy-combustion in the OXFCPS. See FIG. 6.
[0522] In certain preferred embodiments, refrigerated liquid CO.sub.2 is
utilized for cryoenergy storage for load balancing purposes, thereby
facilitating the operation of the OXFCPS powerplant (shown in FIGS. 1 and
2). Stored cryo-energy present in the CO.sub.2-UH as stored refrigerated
liquid CO.sub.2 is releasable by conversion into electricity by heat
exchange with atmospheric air and/or by heat exchange with the exhaust of
the powerplant. The phase-changing expanding gas drives a power-producing
turbine. In this way, refrigeration-liquefaction of CO.sub.2 is used as a
CO.sub.2 storage mechanism for energy storage. (Of course
refrigerated-liquefied CO.sub.2 also is sold into the market as a product
of the CO.sub.2-UH.) The refrigeration-liquefaction process requires
input of power from the powerplant, typically at night when power demand
from the grid is low. In a day-night cycle, a substantial fraction of
this cryogenically stored energy is recovered, typically during the day,
when power demand from the grid is high. Phase-changing expanding
CO.sub.2 gas is warmed by heat exchange. For best system efficiency, this
heat exchange is via cooling the intake of air fed into the ASU and/or by
utilizing exhaust heat from the powerplant as a higher temperature heat
source. After the phase-changing expansion of CO.sub.2 drives a
power-producing turbine engine, the warmed-up gas then is fed into
various modes of utilization via the CO.sub.2-UH. Further representation
and discussion of this capacity for CO.sub.2 utilization is provided in
FIG. 6 and its accompanying discussion.
[0523] In certain preferred embodiments, the CO.sub.2-UH, and/or the ASU
cryosystem, and/or both working in concert, receives inputs of solar
power transmitted by one or more long-distance transmission wires,
transmitted to support various modes of production utilizing CO.sub.2
inputs, or transmitted in the context of a need for load balancing.
Cryogenic energy storage using practically liquefiable gases, N.sub.2,
and/or O.sub.2, and/or CO.sub.2 allows balancing of the irregularity of
flows of solar power into the grid such that a continuous regularized
flow of power input may be sustained into CO.sub.2-utilizing modes of
production. Additionally, the cryogenic energy manipulation and storage
capabilities of the overall method and system of the invention provides
capacities suitable to serve load-balancing needs that are generic for
solar power provision into the grid. Turn-around power storage
efficiencies by such methods are expected to be >60% (power out/power
in), and possibly as high as 95%, as described in references cited herein
(cf, Park et al., 2017). Certain preferred embodiments include this
capability to receive solar power and provide energy storage for load
balancing to regularize the input of solar power to the grid.
[0524] In certain preferred embodiments, the CO.sub.2-UH, and/or the ASU
cryosystem, and/or both working in concert, provide(s) cryogenic energy
storage load-balancing services for the management of one or more
electrical power grids connecting into the invention as implemented (in
the same manner as described for the input of solar power in the section
immediately above).
[0525] FIG. 2, box 1 is a schematic representation showing the
delimitation of the invention in relation to Lake Kivu and in respect to
various elements diagrammed within the figure and the names of the
submethods and subsystems indicated by their acronyms. (An equivalent
diagram is not shown for the simpler case of the MSDS-based variation of
the invention. FIG. 1, box 13 and CO.sub.2 flow line 14 are sufficient
for this purpose in combination with detail provided in FIG. 8.) The
invention has specific applicability to problems and challenges of Lake
Kivu (represented by the circle labeled number 38 which also represents
the combinative domain of the invention), specifically to safe,
efficient, optimally productive deepwater resources utilization. The
invention solves problems and challenges of Lake Kivu such as efficient
power production, securing long-term lake safety, environmental
responsibility, and economic innovativeness and productivity by utilizing
CO.sub.2. It does so by combining submethods and/or subsystems within
three subdomains operating in inter-coordination. These are shown as
circles within the larger circle marked "Lake Kivu" (38) in Box 1: (i)
deepwater extraction (22), degassing (22, 24), and gas transfer and
processing for dehydration and/or H.sub.2S removal (25), if and as
needed, preparatory to oxyfuel combustion; (ii) oxyfuel combustion (26,
27) with inputs of separated deepwater gases (25) and oxygen (27, 31),
and outputs of electric power (29) and exhaust comprising nearly pure
CO.sub.2 with condensable H.sub.2O (28); and (iii) a CO.sub.2-UH
submethod and/or subsystem (21) which produces, in the limited set of
examples provided for purposes of description, a suite of twenty main
modes of carbon-containing product production (1 through 20, and in sum:
33) including CO.sub.2 for biozone input (vectors 2a, 2b and 3),
utilizing the input of exhaust (28) expelled from the oxyfuel power plant
(26, 27). Note that 20 modes are provided only for reasons of limiting
the discussion to a reasonable package of examples, whereas the invention
is generically open to any modes of CO.sub.2 utilization such as might
support realistic business activities or at least developmental research
and development in order to create business activities via developmental
investment.
[0526] FIG. 2, box 2 shows aspects of the operation of the CO.sub.2
utilization hub (21: CO.sub.2-UH). The CO.sub.2-UH (21) transforms the
exhaust (28) from the OXFCPS (26, 27) plus additional inputs (32), into
horticultural, aquacultural, and industrial output main modes (1, 2, 3,
4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 33). Table
2 lists them and provides additional information.
[0527] FIG. 3 provides detail on five types of gas processing trains
present within the CO.sub.2-UH (as shown in FIG. 2 as item 30 without any
detail). Note that the process shown in process train 22 is different
from processing trains that produce CO.sub.2 products. Train 22, however,
demonstrates production utilizing relatively "raw" CO.sub.2 with respect
to the exhaust output of the OXFCPS. These trains and their various
combinations are all preferred embodiments. In FIG. 3, the five
processing trains are labeled 22, 23, 24, 25 and 26. Horizontal dashed
lines separate these five processing trains. FIG. 3 exhibits four cases
of the production of CO.sub.2 products (rows marked by circles numbered
23, 24, 25, 26), and one case of manufacturing a product incorporating
CO.sub.2 (22). The five different submethods and subsystems of receiving,
processing, storing and purveying CO.sub.2 (rows 23, 24, 25, 26), and
CO.sub.2-incorporating products (row 22) are referred to herein as
"process trains." A dashed box (dashed box 36) encloses a representation
of subsystems and submethods present in certain preferred embodiments.
These connect and integrate cryogenic capacities of the OXFCPS involving
liquefied nitrogen (31) and oxygen (30), with cryogenic capacities of
process trains 25 and 26.
[0528] FIG. 3 shows the initial reception of raw exhaust (1) from the
OXFCPS or MSDS (as shown in FIGS. 1 and 2). Initial processing of OXFCPS
raw exhaust gas, in certain preferred embodiments, includes capture of
heat energy by a heat exchanger connected to a power production unit.
Such a submethod and/or subsystem, a Heat Exchanger Power Production Unit
(2: HEPPU) is represented by (and/or identical to) a fence-like symbol
within box 2. A drain, shown as an icon labeled 3 (present in four
locations within the figure), drains condensed water from the HEPPU (2).
In some embodiments, this heat exchanger power unit is a part of the
OXFCPS. In other embodiments, the HEPPU (2) is included within the
CO.sub.2-UH. FIG. 3 shows it as the latter. The distinction is simply a
definitional choice. FIG. 3 shows five different modalities of CO.sub.2
handling, processing and disposition for use (22, 23, 24, 25, 26). In one
case (22), CO.sub.2 is directly utilized. This utilization is in a sense
referring to the transformation of CO.sub.2 into a product that is not
itself CO.sub.2, or otherwise more broadly refers to any industrial
process that utilizes CO.sub.2 but that is not overlapping with CO.sub.2
processing into other forms of CO.sub.2. In the others cases (23, 24, 25,
26), CO.sub.2 in various forms is modified and made available for
delivery as a CO.sub.2 product. Thus four of the five modalities are for
CO.sub.2 products as shown for process trains 23, 24, 25, and 26.
[0529] In FIG. 3, the process train modality, labeled 23, is production of
relatively unprocessed gas into short-term process storage (9). This
storage (9) is shown as a pressurizable chamber allowing condensation and
removal of water (icon: 3) prior to pumping (10) of stored CO.sub.2 for
use. The next flow stage in this process train is low-pressure pipeline
delivery (11a, b). The double representation (11a and 11b) indicates a
multiplicity of uses, but does not indicate either a necessity of
multiple uses or an absence of multiplicity for outputs of the other
process trains shown. CO.sub.2 in this relatively low-pressure form
delivered by pipelines is for local and/or semi-local horticultural
and/or aquacultural and/or return-flow-modifying uses, as shown in FIG.
2.
[0530] In FIG. 3, the process train modality labeled 24 is production of
dehydrated pressurized gas. Dehydration steps (icon 3: shown in four
locations) may in some embodiments precede compression (10), as shown.
(High pressure is indicated by two compressor symbols.) CO.sub.2
processed in this modality typically is stored in one or more tanks, or
in a farm or farms of such tanks (12) prior to export by one or more
high-pressure pipelines (13) or by pressurized tank truck (14).
Distribution of high pressure CO.sub.2 internally within the CO.sub.2-UH
is shown by item 15 showing two uses: 15a and 15b. Flow vector 15a
represent transfer from pressure storage of CO.sub.2 into refrigeration
processing into refrigerated liquefied CO.sub.2, whereas the extension
(15b) represents a transfer directly into refrigeration for dry ice
production, if desired. Flow vector 27 indicates that compressed CO.sub.2
may be supplied into outputs of process train 23.
[0531] In FIG. 3, the process train labeled 25 is refrigerated liquefied
CO.sub.2 production, storage and disposition (18, 22, 39). Storage is in
one or more thermally insulated liquid CO.sub.2 tanks (17), or in a farm
or farms of such tanks (17), prior to export by refrigerated tank trucks
(18), or transfer by insulated pipeline (22) into dry ice production
(process train 26), storage (20) and delivery (21).
[0532] In FIG. 3, flow vector 39 represents transfer of stored
refrigerated liquid CO.sub.2 by insulated pipeline for recovery of
cryo-energy. One of the functions of the CO.sub.2-UH facility is storage
of refrigerated liquid CO.sub.2 (17: "LCO.sub.2") by means of
refrigeration energy input. This energy can be recovered such that
storage of LCO.sub.2 acts as a battery. For recovery of energy stored in
this way, the cold liquid is transferred through an insulated pipeline
(39) to a heat exchanger and turbine energy extraction system
(represented by item 40). Heat exchange with the atmosphere (preferably
via the air intake of the ASU), or with powerplant exhaust, causes a
phase-changing expansion of CO.sub.2. This flow of expanding gas drives a
turbine generating electrical power for export into the grid, typically
for load balancing purposes. (An overview of this cryo-system for energy
storage is provided in FIG. 6.) In some embodiments, this capacity for
cryogenic energy storage in the CO.sub.2-UH facility includes additional
storage of liquefied N.sub.2 (31, "LN2") or liquefied O.sub.2 (30,
"LO2"), or both, as shown. These additional capacities for LN.sub.2,
LO.sub.2 and LCO.sub.2 handling for cryo-energy storage are described in
subsequent sections. They have the capacity to provide load-balancing
services for three uses. These uses are: (i) for energy storage
internally to allow variable power output into the grid for the
powerplant (OXFCPS); (ii) to provide energy storage capacity for the
grid, if desired; and (iii) to provide energy storage capacity to handle
irregular renewable power inputs for CO.sub.2-UH production modes (such
as "solar fuels" and/or "wind fuels" and/or "hydro fuels" production
using CO.sub.2 as a carbon source), if desired.
[0533] The process train modality labeled 26 in FIG. 3 is dry ice
production by refrigeration (19) of CO.sub.2 supplied by other process
trains (15b, 22). Dry ice is stored in an insulated storage warehouse
(20) prior to delivery by truck (21), typically with thermal insulation
storage and/or packaging. In some embodiments, dry ice is used for
cryogenic energy storage. (Note that specific system linkages are not
illustrated for this use).
[0534] In FIG. 3, the process train labeled 22 shows CO.sub.2 utilized for
transformation of CO.sub.2 into CO.sub.2-containing products and/or more
broadly for production utilizing CO.sub.2 in conditions that may require
time-varying steps of CO.sub.2 input in different conditions of
temperature, pressure and steam and/or water vapor content according to
production recipes. This may occur within the CO.sub.2-UH defined within
a local or semi-local geographical domain. Process train 22 provides an
example of a type of CO.sub.2 utilization via a pressure chamber for
carbonation. Gas proceeds by a choice (28, typically determined and
directed by means of a valve) for processing with or without, a
dehydration step (3). The gas flow proceeds though a valve disposition
subsystem (4). This valve disposes flow to proceed without or with
degrees of compression (10) into a processing chamber unit (5). The unit
shown (5) is meant to be representative of many different modalities of
CO.sub.2 utilization involving many different types of industrial
CO.sub.2 use. Simply for example, in FIG. 3 it (5) is shown by icons
representing a carbonation-reaction chamber appropriate for the
carbonation of cementitious building materials. After a suitable period
of carbonation, materials created in a processing unit (5) are stored
and/or possibly cured under gas composition, temperature and humidity
controls in a warehouse (6), before being purveyed by means of any
appropriate mode of transportation, as represented in the figure
symbolically by truck (7) and ship (8) icons. Again, many other
modalities of industrial processing for utilizing CO.sub.2 could be
represented for this modality of CO.sub.2 utilization involving a process
recipe of scheduled inputs with variability of composition and state. The
carbonation pressure chamber mode, as shown (5), is one example only. It
includes the main processing steps of gas preparation by purification
and/or compression followed by one or more processes of product
manufacture utilizing CO.sub.2, a large number of which are referenced
herein.
[0535] In FIG. 3, box 36 represents an integrative linkage of cryogenic
capacities between the OXFCPS (not shown) and the two cryogenic process
trains labeled 25 and 26. This linkage exists in certain preferred
embodiments. A double-sided arrow (35) represents a capacity for flow in
both directions between the ASU-OXFCPS complex (as shown in FIG. 2) and
process train 25 for liquefied nitrogen and/or oxygen and/or carbon
dioxide. This linkage adds handling, storage and disposition of liquid
oxygen (30, 32) and liquid nitrogen (31, 33) to process train 25, which
otherwise is a process train with cryogenic capacities specialized only
in the freezing, handling, storage and dispersal of liquefied CO.sub.2
(17, 18). As shown by icons within box 29, the linkage also included the
capacity to generate electric power by releasing cryo-energy by venting
LN.sub.2 to the atmosphere or to various uses via a heat engine (33) and
similarly via a heat engine by gasifying LO.sub.2 into the OXFCPS (32 via
35). An icon representing refrigeration within box 29 represents the
capacity of the linkage (represented by box 36) to provide refrigeration
into process trains 25 and 26, drawing from the cryogenic capabilities of
the ASU (if the ASU is of the cryogenic modality). In certain preferred
embodiments, the linkage (36, 29, 32) also gasifies stored liquefied
oxygen (30) via a heat engine power generator (represented by icons
within 29) connecting to the O.sub.2 intake supply for oxyfuel combustion
(via 35). The linkage labeled as number 34 offers the possibility to
contribute cryogenic cooling into the cryogenic capacity of the process
train dedicated to produce dry ice (26). Overall, in certain preferred
embodiments, this integration (symbolized by box 29 and box 36) connects
(35) the CO.sub.2-UH to the Air Separation Unit (ASU) within the OXFCPS.
The linkage makes cryogenic cooling available to be used in the cryogenic
process trains 25 and 26, specifically to the cooling units labeled 16
and 19. Further detail is provided in FIG. 6.
[0536] The linkage represented within box 36 plus items 39 and 40
establish a cryo-energy storage capability for the invention overall,
connecting with the ASU-OXFCPS complex. A capacity to store cryogenic
energy is a method of storage for electric power. Cryogenic energy
storage allows the capacity to vary the level of electricity export into
the receiving grid while from the oxyfuel powerplant operates at a
constant optimal rate of internal power production. It can also provide
additional energy storage grid services as noted above. For natural gas
oxyfuel turbines, a connected oxygen-supplying (14) ASU typically draws
.about.10% of the powerplant's internal power production when operated
continuously at a constant level of production of oxygen. The use of
cryogenic energy storage is valuable to powerplant operations. It allows
diurnal modulation of power export output to be by up to a scale of a
roughly 20% spread between high and low output to the grid with constant
continuous internal power production by the central turbine(s) system
burning degassed Lake Kivu methane. That is to say, a 20% spread would be
the difference in power export to the grid for a daily cycle with 12
hours of ASU oxygen production on, followed by 12 hours with ASU oxygen
production off. The operation of such a modality of energy storage is
dependent upon the operational capacity of the ASU. Operating by
cryogenic energy storage in this 12-hours-on, 12-hours-off mode requires
capacity to operate the ASU at a level of production .about.2.times. the
rating for round-the-clock continuous oxygen production. As noted above,
additional cryo-energy storage may be obtained by operating separate
power-generating heat engine turbines utilizing cryo-energy stored in
insulated reservoirs of liquefied nitrogen and oxygen (as shown in FIG.
3, items 30 and 31). LCO.sub.2 also may be used in cryogenic energy
storage (17, 39, 40). The method and system of these cryo-energy-tapping
heat engine turbines and their heat exchangers are represented by two
icons placed in the upper sector of Box 29 shown in FIG. 3. (The system
of item 40 recovering cryo-energy stored in LCO.sub.2 is not shown
extensively in FIG. 3. It is shown in FIG. 6.) This box represents a part
of the interconnections between the ASU (as shown in FIG. 2: item 27) and
the component of the CO.sub.2-UH identified by item 30 in FIG. 2. (In
FIG. 2, these connections are labeled 33 for LN.sub.2, 32 for LO.sub.2
and 41 and 40 for LCO.sub.2). Generalized sales/delivery of LO.sub.2 and
LN.sub.2 is shown by pipeline icons (37 and 38). Flow vector 34 shows
interconnection of cryogenic systems storing LCO.sub.2 with dry ice
storage and manufacture (the process train labeled 26).
[0537] FIG. 4 represents the invention disclosed herein as a method and
system for industrializing economic development. According to the
invention, Lake Kivu deepwater processing creates a multiplicity of
outputs that can be described by economic metrics. Such economic metrics
are causally linked to the product flows shown in FIGS. 1, 2 and 3 as
measures of economic output. Shown on the left side of the diagram are
extracted (1) Lake Kivu deepwater (12) resource flows (labeled: 3, 4, 5,
6, and altogether: 2). These, variously in the middle of the diagram (9,
10, 11), are shown inputting CO.sub.2 (that would otherwise be waste)
into a productive, jobs-creating, CO.sub.2 utilization Hub (7,
illustrated with exemplary, non-limiting icons), while simultaneously
efficiently combusting methane (6) to produce power (9) in an optimal
manner with efficient carbon capture (10). Lake Kivu deepwater (12)
contains (Box 2) several types of useful resources (sub-boxes: 3, 4, 5,
6). Lake Kivu's deepwater is extracted (1) with its dissolved resources
flowing into separation operations (Box 2, which encloses Boxes 3, 4, 5
and 6). Each sub-box represents different types of utilizable substances,
as noted. All can be directed into useful industrial production. The
invention disclosed herein pertains primarily to the utilization of
methane (Box 6) and CO.sub.2 (Box 3), both degassed from Lake Kivu
deepwater via transformation into a stream of CO.sub.2 and steam exhaust
entering a CO.sub.2-UH (item 7), whereby the submethods and subsystems of
oxyfuel combustion, or MSDS in the variant form of the invention (both as
described herein but not shown in FIG. 4) provides means for
transformation. The flux of CO.sub.2 from degassing (11) joins together
with a flow of CO.sub.2 produced (10) by methane combustion (9) in the
TDS modality. This provides (as represented by transfer vector 10) a
material basis for CO.sub.2 utilization in a CO.sub.2 utilization hub
(CO.sub.2-UH, item 7). As indicated by representative icons, the
CO.sub.2-UH (7) creates jobs, industrial production, and consequent
economic growth (item 8). Note that dissolved magnesium (Mg) may be
co-utilized with CO.sub.2 in the production of materials containing
Mg-carbonates. Also, ammonium ion (NH.sub.4+) may be co-utilized with
CO.sub.2 both in the production of urea as well as in the nutrient
fertilization of algal biocultures which may co-fertilized with CO.sub.2.
These resources are identified together in Box 5 labeled "other
substances." Utilizations of dissolved magnesium and/or NH.sub.4+ are,
however, optional features of the invention disclosed herein. The
utilization of dissolved magnesium is described in an independent
disclosure by the inventor in U.S. Patent Application Publication No.
20160257577 A1.
[0538] FIG. 5 illustrates and summarizes several benefits of the invention
disclosed herein, shown in Box 2, in comparison with existing (circa
2016) technology shown in box 1. The figure highlights aspects whereby
the invention offers substantial contributions to power production
efficiency, lake safety, environmental stewardship and economic
development. The invention is indicated in Box 2 only its TDS-based
modality. TDS refers to the method of a Total Degassing System. The MSDS
(Modified Staged Degassing System) variant is not shown in FIG. 5. (FIG.
8 provides details.) Black vectors illustrate CO.sub.2 flux through
systems. (Except for vector 24 which represents flow of near-surface
water.) These, in comparison, highlight the CO.sub.2-utilizing aspect of
the invention via a CO.sub.2 Utilization Hub (16). The existing
technology practiced on Lake Kivu utilizes the method of staged
degassing" (SDS) for gas extraction and cleaning prior to combustion. As
illustrated (Box 1), the SDS method proceeds in (minimally) two stages. A
first stage of separation is enclosed by a dashed oval (22). Item 22 is a
gas-water separator. It is located at a specified depth corresponding to
a useful pressure for fractionation to optimize the CH.sub.4/CO.sub.2
ratio and minimize CH.sub.4 retention losses in solution through the
degassing process. Typically the preferred depth is .about.20 meters. A
substantial fraction (.about.>20%) of methane remains in solution and
is returned to the deep lake (19) in the return flow of water (31) which
also contains .about.80% of the initial concentration of CO.sub.2 (5). A
second stage (25) utilizes scrubbing with water to absorb CO.sub.2. The
process uses near-surface water that is not saturated in CO.sub.2. The
scrubbing process acts by gas-water equilibrium between gas bubbles
and/or gas flow of stage-1 interacting/equilibrating with
CO.sub.2-undersaturated near-surface water. Gas bubbles and/or flows
upwards through a platform-supported (4, icon 12a) scrubbing device (25).
This process preferentially resorbs CO.sub.2 (with respect to CH.sub.4)
back into solution. Some methane is absorbed into solution in stage-2 and
plumbed back into the lake (20). Hence methane is lost in both stages so
that the flux of methane piped (7) into conventional piston engines (8)
is substantially reduced. This "slip" wastage is shown for both stages:
19 and 20. One aspect of the comparison shows that utilization of
CO.sub.2 in a CO.sub.2-UH (16) creates a basis for large-scale industrial
development (16, 21), represented by icons. Another aspect is securing
lake safety against limnic eruption such as may be triggered by sub
lacustrine volcanism or other types of triggering phenomena. Lake Kivu's
main density discontinuity is presently located at .about.260 meters
depth. It is represented by a dashed horizontal line (17). CO.sub.2 flux
is represented with black vectors in both boxes in the figure (3, 5, 6,
9, 10, 14, 15, 25). CH.sub.4 flux is represented with stippled vectors in
both boxes in the figure (3, 7, 10, 19, 20, 23). Water flux is shown as
flow vector 3-to-31 in box 1. In Box 2, water flux is shown as flow via a
deepwater inlet (10) to intake (26) into a gas-water separator (27).
Water flow proceeds out of the separator via directed flow (28) into
de-densifying water treatment (29). Flow then continues back into the
lake (30) where it is released well above the main density discontinuity
(17). The de-densifying water treatment method and system (29) have been
disclosed by the inventor in U.S. Patent Application Publication No.
20160257577 A1.
[0539] In Box 2 (which represents the invention) of FIG. 5, utilization of
CO.sub.2 is facilitated by an initial process of total degassing. This is
via a total degassing system, TDS (27), hosted in a floating structure
(11), linked with an icon representing a water-borne platform (12b).
Return flow in the TDS-based method, as noted above, does not return
CO.sub.2 and CH.sub.4 into the lake. By contrast, in the SDC-method (Box
1), most of the CO.sub.2 flowing upwards into the intake (3) is returned
into Lake Kivu (5, 6). Most is being returned (5) into to the gas-rich
deepwater reservoir existing below the main density discontinuity (17).
Such a situation preserves and extends a dangerous condition due to
limnic eruption catastrophe hazard. In Box 2 (representing the
invention), return flow can be de-densified (in item 29) such that it can
be reinjected into the lake above the main density discontinuity (30).
This increases lake safety. It does so by drawing down the volume of the
gas-rich deep layer. This drawing down "deflation" is illustrated in Box
2 as a time transition. It is shown by small downward arrows illustrating
movement of line 17 to a later situation identified by line 18.
[0540] FIG. 5 illustrates a key factor of inefficiency in the standard
(SDS-based) method. This is the loss or "slip" of methane shown as
vectors 19 and 20. Methane returned via stage-2 into Lake Kivu's bio-zone
upper layer (20) is irrevocably lost by biological capture and
metabolism, typically by bacteria. Methane "slip" lost into the lake's
deeper resource zone (19) remains extractable in principle. However, in
practice, this methane is not extractable. This is for two reasons.
First, return of this "slip" methane into the deep layer is associated
with dilution of the methane concentration in the deepwater reservoir
over time. Dilution increases extraction inefficiency. Late in the
extraction, inefficiency increases drastically. Effectively this means
that the returned methane is lost. Second, some actual operations are not
returning the flow (indicated as 31, 5, 19) into the deep lake below the
main density discontinuity (17). Water is being mixed with near surface
water and reinjected at a higher level in a depth range where it is not
extractable by the SDS method. Mixing-in near-surface water also
oxygenates the flow such that methane is lost by bacterial uptake. Direct
methane losses in the SDS-based method are roughly one third. Indirect
methane losses via the effect of dilution of the deep layer add
additional degrees of inefficiency.
[0541] Overall, the invention disclosed herein and in the related
disclosures of U.S. Patent Application Publications Nos. 20150354451 A1
and 20160257577 A1 creates an efficiency gain of approximately .times.2.4
in terms of total power produced by an OXFCPS (13) from the lake in
comparison to the SDS-based method. The use of supercritical CO.sub.2
power cycle technology can increase this factor to .about..times.3.0.
[0542] FIG. 6 illustrates special cryogenic aspects of the invention.
These aspects are diverse and powerfully versatile. They include
cryo-energy storage (23, 24, 25, 28) and recovery (3, 18, 29, 30), as
well as provision of coolant flows of liquid (11) and/or cold (12)
nitrogen to a Digital Data Center (5, DDC). Cryogenic aspects also
include capacities for powerplant (1, 33) temporal load-balancing (18),
provision of grid balancing services (15, 16), utilization of remote
solar and/or wind power (20) inputs (21), and production and utilization
of LNG (36, see below) and other forms of NG (40), such as CNG and ANG.
Irregular solar and wind power inputs may be stored and used in
power-absorbing modes of production within the CO.sub.2-UH (Box 4), for
example production of H.sub.2, O.sub.2 and "solar chemicals," including
carbon-recycling, hydrogen-binding "solar fuels" such as methanol and/or
DME. FIG. 6 illustrates detail that is not provided in Box 5 shown in
FIG. 1. Cryogenic aspects of the invention are illustrated in all
modalities based upon the three different available gases: N.sub.2,
O.sub.2 and CO.sub.2. These are all present in preferred embodiments of
the invention, as is any subset using only one or only two of these
gases. A particular utilization of nitrogen gas also is shown. It is for
cooling of a Digital Data Center (DDC, 5). Cryogenic equipment for air
separation and other gas cooling tasks exists within an Air Separation
Unit (2). This unit is shown functioning with expanded capacities as a
CRyogenic Processing Unit (2, ASU-CRPU). This expanded capacity may be
shared with the CO.sub.2-UH (box 4), as shown (via same number labeling
of the cryo-production icons: 27a and 27b, however not represented
spatially in connection in the figure). Or separate cryogenic facilities
may exist within the CO.sub.2-UH (Box 4) supplied with power (17, 19)
from the powerplant (icon in Box 1) and/or from the grid (15, 33), if
desired. Open arrows with single ends (such as, for example, 6 through
13) represent matter flows. Solid black arrows represent flows of
electric power. (Power may be mechanically transmitted and/or more
typically transmitted by wires as electric power. Of course power is
supplied into (16) the grid (33).) Two double-ended arrows appear within
Box 22 (CESSI). These connect to heat exchanger icons labeled 29 and 30.
They represent options of connectivity shared by a CRyo-Energy Recovery
Unit (Box 3: CRERU), which is adjunct to both the Air Separation Unit
(ASU, Box 2) and the OXyFuel Combustion Power System (Box 1, OXFCPS).
These options of connectivity of the CRERU (Box 3) connect cryogenic heat
engine power generator systems (shown within Box 22) with the heat
sources of the air intake (14) of the Air Separation Unit's
CRyo-Production Unit (Box 2: ASU-CRPU), and/or with the CO.sub.2 and
water vapor exhaust (32) of the OXyFuel Combustion Power System (Box 1:
OXFCPS). Again, these connections are symbolized by heat exchanger icons
29 and 30, respectively, linked to the center of Box 22 (CESSI) by the
double-ended arrows. The power generator systems are symbolized by icons
shown in the inner part of Box 22 (CESSI) within the CRERU (Box 3). These
icons are shown as three pairs. They illustrate power sources connecting
to power transmission wires (18a, 18b and 18c). These power sources
tapping stored cryo-energy provide recovered stored power (18) into a
nexus of electrical power regulation and disposition (dashed Box 41)
connecting the powerplant (Box 1) to the grid (33, 15, 16). These systems
(18a, 18b, 18c) extract stored cryo-energy, respectively, from flows of
stored (25) refrigerated liquid CO.sub.2 (9, LCO.sub.2), stored (23)
liquid oxygen (6, 10, LO.sub.2), and stored (24) liquid N.sub.2 (7, 11,
LN.sub.2). Liquified Natural Gas (LNG) also optionally is stored (34)
within the CO.sub.2-UH (Box 4). LNG provides very high efficiency
cryo-energy storage with efficiencies above 90% for round trip energy
storage. LNG also of course provides efficient storage of chemical energy
that can be transported as well as sold in various forms, LNG, CNG and
ANG (40). Inclusion of cryogenic capacities for LNG production
additionally provides the basis for a method and/or system for LNG
production via cryo-separation of methane from carbon dioxide, (with
CO.sub.2 separating in the form of dry ice according to elegant methods
patented and demonstrated by Larry Baxter and colleagues). Dashed Box 36
indicates a specialized domain for such LNG-based operations, possessing
LNG-specialized cryo-capacities (35) with CO.sub.2 separation capacity.
This domain (35) intakes a mixed gas inflow (37), degassed from a Lake
Kivu deepwater source (38). It produces outflows of separated solidified
and/or liquified CO.sub.2 (39) and LNG (40). LNG cryo-energy production
and storage therefore also serves as a mode of CO.sub.2 processing
appropriate as a valuable capacity of a CO.sub.2-UH for the production of
dry ice and/or LCO.sub.2 as well as for cryo-energy storage. Storage of
cryogenic liquids is provided within a cryo-storage domain (28) within
the CO.sub.2-UH (Box 4). This domain (within dashed Box 28) functions
both for liquefied gases storage generally as well as in the capacity of
a power-storage battery as indicated by an icon (26). Cryogenic energy
storage systems can possess attractively high round trip efficiency and
flexibility, as has been well demonstrated. As shown by the icons, heat
engine power generator systems (within Box 22, CESSI) are comprised of
heat exchange equipment combined with gas flow turbine generators. The
Air Separation Unit (2, ASU-CRPU) produces liquid oxygen (6: LO.sub.2)
and liquid nitrogen (7: LN.sub.2) for energy storage as well as O.sub.2
gas for direct intake into combustion in the OXFCPS (1). After passing
through heat exchangers linked to power generating turbines, gas flows
are distributed as follows. Cold nitrogen gas (12) is distributed as a
cooling flow (to 5: a Digital Data Center, DDC, or other facility
requiring large cooling flows), and may be otherwise directed (13) for
additional uses after serving its function. Warmed-up nitrogen (13)
exiting the DDC (5) may be utilized for various purposes. Oxygen gas (31)
is fed into oxyfuel combustion (1). Carbon dioxide gas (8) is returned to
the CO.sub.2-UH for disposition for utilization (4).
[0543] Such cryo-processing and cryo-energy storage capabilities are
expanded and used, if desired, for load balancing of solar power (20)
and/or wind power and/or hydropower inputs (21) flowing into the
electricity handling nexus (Box 41) of the powerplant (Box 1), or some
adjunct electrical facility if/as needed. Cryogenic energy storage
capabilities present in some preferred embodiments thereby allow power
storage as well as utilization of inputs (21) of solar and/or other
sources of renewable power (20) plus CO.sub.2 within the CO.sub.2-UH (4)
for production of "solar chemicals," including "solar fuels." Efficiency
factors are reported within research reports incorporated into this
disclosure. The development of such capabilities for solar power
utilization in support of CO.sub.2 utilization is very highly desirable.
This is from the perspective of the global need for economically useful
innovations in the development of solar and/or other renewable sources of
power, for example, demonstrating economically viable large-scale cases
of "artificial photosynthesis" based upon solar power inputs. The
invention offers this possibility utilizing carbon dioxide both as a
cryo-energy storage liquid and as a carbon source.
[0544] FIG. 7 introduces a perspective of the invention as a collaboration
and talent attractor. This perspective is based upon the international
strategic significance of large scale CO.sub.2 utilization combined with
national economic development in a region that has suffered massive
catastrophes and that also is extraordinarily beautiful as well as
subject to a pleasantly attractive climate year round. FIG. 7 shows a
preferred embodiment of the invention in its aspect being an open hub
attracting the development of a global network. The focus of the
invention is the internationally strategic goal to create commercially
viable new examples of very large scale CO.sub.2 utilization. The NRG
Cosia carbon X-Prize competition (http://carbon.xprize.org) exemplifies
this situation. The invention creates an opportunity to attract talent,
capital, interest, publicity, and innovative new ideas and technologies.
The CO.sub.2-UH (Box 1), representing the invention overall, provides a
global focus hub for the growth of an international network represented
by the large peripheral circle (2) and its connected box ("Box")
containing a group of icons representing several different modalities of
collaboration. This network structures collaborations with companies,
research institutions, financing institutions, non-profit funders and
philanthropic agendas. Each collaboration is represented by a spoke
(double-ended arrow) connecting to a numbered ball situated on the
network circle. There is no closed number of collaborations. (Each
collaboration is represented by a ball and spoke combination: 3, 4 5, 6,
7, 8, 9, 10, 11, 12.) This openness is shown by the " . . . " following
the number identifying the twelfth ball-and-spoke. Components of the hub
work in concert on the challenge of creating business-scalable
innovations in carbon utilization recycling. The icons inside the dashed
box represent the multiple aspects of the network: research, training,
e-platformed networking and knowledge dissemination, for-profit business
and non-profit charitable involvements, new ventures formation,
technology pilot projects, networked brainstorming, etc. The
hub-structured open aspect of the CO.sub.2-UH (1) creates an intrinsic
attractiveness with an open modularity for adding and developing specific
modalities of CO.sub.2 utilization within a common framework.
[0545] FIG. 8 shows a system, method and apparatus concept that modifies
the standard "staged" gas extraction technology presently utilized on
Lake Kivu (Box 1: SDS), as shown by items 13 and 14 in FIG. 1. The
modification is into a system, method and apparatus concept (Box 2)
possessing the capability to degas CO.sub.2 in a flow sequence following
after stages 1 and 2. This method and system of modification makes it
possible to create a CO.sub.2-UH connected to an existing conventional
staged gas extracting and powerplant operation/apparatus. This type of
modification, and/or method, and/or system is an embodiment of the
invention. This method and system of modification also makes it possible
to design and develop a staged extraction powerplant system that degasses
CO.sub.2 and therefore that can be constructed with addition of a
CO.sub.2-UH. The present disclosure is a method and system that links a
CO.sub.2-UH to a Lake Kivu deepwater degassing system. The latter may be
either of both known types: (i) a modification (MSDS) of the conventional
"staged" degassing technology; or (ii) a "total degassing technology"
(TDS). Both types of degassing system (MSDS & TDS) are variant
sub-components of the invention. Both can connect to a CO.sub.2-UH, as
shown in FIG. 1. Both can connect to return flow systems as shown in Box
3 of FIG. 8.
[0546] FIG. 8, Box 1 illustrates the conventional staged method (SDS) as
follows. Deepwater enters a riser system (1) via auto-siphoning flow,
and/or with pumping assistance. Flowing upwards, it enters a degassing
system (1, 2). Degassed gas is collected at a depth (10) below the
surface of Lake Kivu indicated as "D." This depth typically is selected
to optimize both CH.sub.4 yield and the CH.sub.4/CO.sub.2 ratio in a
situation of a divergence of two factors: (i) maximizing the degree of
methane extraction by degassing (which increases with decreasing D); and
(ii) minimizing the degree of CO.sub.2 extraction by degassing (which
also increases with decreasing D). Gas obtained by stage-1 degassing is
separated from the deepwater flow (2, 9a) and directed to flow upward (3)
in a contained gas transfer riser system. In some designs, this gas
enters into a 2.sup.nd stage gas-cleaning process positioned near to the
lake's surface. (Some designs clean gas in a 2.sup.nd stage below the
surface. Others clean gas above the surface in bubble or trickle towers.)
As shown, the gas-cleaning process utilizes near surface water (5, 6, 7).
This water is pumped (5) upwards (6) and released downwards to flow
downwards inside a bubble or trickle tower (4), then out of it (7) and
back into the lake. This method and system absorbs and removes CO.sub.2
preferentially from the gas flow (3). Cleaned gas is collected and
extracted at the top of the chamber by exit flow (8, which may be pumped
in some embodiments) at the completion of the gas-cleaning process. It is
then provided by pipeline into combustion (not shown). The 2.sup.nd-stage
"water washing" method is designed to minimize methane "slip" loss and
maximize the CH.sub.4/CO.sub.2 ratio of the gas exiting the overall
multi-stage system (8). However, methane slip from both stages may be as
high or higher than 30%, whereas power output utilization for the water
pumping process (5) may be as high higher than 12% of total power output.
For this and other reasons, the standard staged method and system shown
in FIG. 8, Box 1 is only 1/2 to 1/3rd as efficient in power production
efficiency relative to the "total degassing oxyfuel combustion" method
and system disclosed in US 2015/0354451. Despite these limitations, it
may be modified as shown in Box 2 to degas CO.sub.2 for utilization and
in order to degas the deep lake to increase lake safety. Bow tie symbols
represent flow valves. If flow is directed away from conventional return
flow (9b) and into a diversion line (11), then the redirected flow auto
siphons into a degassing chamber (12). This process degasses a
substantial fraction of degassable CO.sub.2 into the gas phase as an
extraction flow (14). (The remainder remains in solution.) Thus, a
conventional Staged Degassing System (SDS, Box 1) is modifiable, as
shown, into a modified system that degasses a substantial faction of
CO.sub.2 (MSDS, Box 2, with or without the additional modifications shown
in Box 3). The CO.sub.2 degasser separates a flow of CO.sub.2 gas (14)
out of solution in the return flow (11). The resulting doubly degassed
return flow may be injected into the deep lake in the conventional manner
(13). Otherwise it may be diverted into additional modifications as shown
in Box 3.
[0547] Box 3 within Box 2 shows how a MSDS can connect by additional
modification into submethods and subsystems for organizing deepwater
return flow as have been disclosed by the inventor in U.S. Patent
Application Publication No. 20160257577 A1. The method and system and
apparatus design concept illustrated within Box 2 is applicable to both
types of deepwater degassing method and system: staged degassing as shown
in FIG. 8, and the total degassing," as disclosed by the inventor in U.S.
Patent Application Publication No. 20150354451 A1. As specified in FIG. 1
and in FIG. 2, Box 1, the invention does not include a return flow system
in its most basic form of definition. However, certain preferred
embodiments connect "main modes" of CO.sub.2 utilization in the
CO.sub.2-UH connect into types of return flow system. Therefore these
modalities and the return flow systems they connect into are described in
the following sections.
[0548] Three non-exclusive options are shown within Boxes 2 and 3 of FIG.
8 for the fully degassed return flow of deepwater. These are: (i)
conventional deep reinjection (13), identical to that shown as 9a and 9b;
(ii) admixing into the biozone of Lake Kivu (15) as a means of
fertilization to boost ecosystem output; and (iii) return flow with
inclusion of de-densifying water treatment by algal growth (18) and
mineral precipitation (19), thereby allowing reinjection of the
de-densified return flow into the Intermediate Zone (IZ) of Lake Kivu,
(as disclosed by the inventor in U.S. Patent Application Publication No.
20160257577 A1).
[0549] FIG. 8, Box 3 shows various different modalities for CO.sub.2
utilization in the context of the return flow options shown. Two of these
involve CO.sub.2 injection diffusers into the return flow. These
diffusers are indicated as 28 and 26. Item 28 represents a diffuser for
CO.sub.2 input (27 into 28) into a component of return flow directed into
Lake Kivu's biozone (0 to .about.80 meters depth) for biozone
fertilization (as shown in item 15, a diffuser). This flux of CO.sub.2
corresponds to CO.sub.2 injection vector 2b in FIG. 2. (Vector 2a in FIG.
2 represents a CO.sub.2 diffusion system separate from that for
nutrient-rich return flow water.) CO.sub.2 diffusion into Lake Kivu's
biozone via flux (27) released into diffuser(s) (28) corresponds to mode
2 in Table 1. Item 26 represents a pH-balancing diffuser. It diffuses
CO.sub.2 input (25) into the flows of de-densified return flow reinjected
into Lake Kivu. This is for (optional) "recarbonation" to conversion of
carbonate anions to bicarbonate anions associated with sodium and
potassium. This flux of CO.sub.2 (25 via 26) corresponds to CO.sub.2
injection vector 3 in FIG. 2. It also corresponds to mode 3 in Table 1.
[0550] FIG. 8, Box 3 includes a 3rd additional modality for CO.sub.2
utilization by diffusion into return flow. This is in a surface flow (16)
method and system for return flow water treatment (18, 19) prior to
reinjection into Lake Kivu (26, 20). This method and system of
de-densifying water treatment is disclosed by the inventor in U.S. Patent
Application Publication No. 20160257577 A1. CO.sub.2 utilizing inputs are
shown in FIG. 8 for pH control (21a, 22). Related CO.sub.2 inputs also
provide carbon feeding for algal biomass growth in a biological water
treatment system method (21a into 17a, and 22 into 18). Items 17a and 17b
represent different possible modalities. These correspond, respectively,
to CO.sub.2 flux into (17a) and CO.sub.2 flux out of (17b) the flow, as
shown by the double arrow (21a,b). These different modalities are: (i)
first, CO.sub.2 injection into the flow (21a, 17a) representing a
pH-controlling submethod and subsystem for avoiding mineral
precipitation; and (ii) second, CO.sub.2 removal out of the flow (17b,
21b). The latter modality is not described herein. It only is illustrated
as an option included in some embodiments.
[0551] In FIG. 8, item 18 in Box 3 represents a photosynthetic method
and/or system for growing algae within the return flow over an extended
period of time. Arrows 21b, 23 and 24 represent CO.sub.2 removal as a
means of pH-raising associated with processes for precipitation of Mg and
Ca. Arrows 21a and 22 represent CO.sub.2 input into a photosynthetic
method and system for growing algae in the return flow over an extended
period of time. CO.sub.2 input provides carbon for photosynthesis. Its
photosynthetic utilization raises pH. Arrows (21 a and 22) represent a
method and system of pH control by provision of CO.sub.2 for algal carbon
source supply and in order to suppress high-pH conditions such as would
precipitate magnesium and calcium. Flux of CO.sub.2 into the bioculture
method and system (21a and 22 into 17b and 18) corresponds to CO.sub.2
injection vector 4 in FIG. 2. It also corresponds to mode 4 in Table 1.
[0552] FIG. 9 is quasi-identical to FIG. 1. The labeling in FIG. 9 is
identical to that in FIG. 1 excepting that additional detail has been
provided within dashed Box 4. Therefore the labeling is not repeated in
this section, except for items within box 4. For other items, refer to
the items list and to sections discussing FIG. 1. The focus of FIG. 9 Box
4 is upon illuminating distinct modes in the utilization of CO.sub.2
"going back" to be used within Lake Kivu (9 a,b,c) for several different
purposes. Some modes of CO.sub.2 utilization into Lake Kivu (15c, 15d,
place CO.sub.2 into the biozone (9a) for use in C-fertilizing aquatic
photosynthesis. Mode 15d does this by injection of CO.sub.2 into return
flow diffused into the biozone (7a) as a C-fertilizing flux (as shown in
FIG. 8, item 15). Mode 15c does this by direct diffusion into the biozone
without connection with admixture of return flow water. Mode 15e places
CO.sub.2 into the Intermediate Zone (9b) in a context of pH-balancing of
de-densified return flow (18) that has become high in pH via
bioproduction (16) followed by harvesting and mineral precipitation
processes (17). Injecting CO.sub.2 into this return flow (18) after
completion of de-densifying processes (16, 17) transforms its alkaline
chemistry rich in (Na- and K-complexed) carbonate anions at high-pH into
bicarbonate anions at a lesser pH. The flux of CO.sub.2 labeled 15a
injected into return flow (7) flowing out of the Total Degassing System
(Box 1) is for purposes of acidification, if and as needed, to avoid
and/or control precipitation of Mg and Ca in this flow. The flux of
CO.sub.2 labeled 15b is provided as a carbon source into photosynthesis
in (typically floating) algal growth operations (16) positioned on the
surface of Lake Kivu but not communicating with it. The open arrow
labeled 19 represents extractive flows from algal harvesting and from the
capture of Ma and Ca precipitates.
[0553] Twenty "main mode" selected examples of CO.sub.2 utilization are
described in following. These correspond to CO.sub.2 flux vectors labeled
1 through 20 shown in FIG. 2. These represent product flows (FIG. 2, Box
8) exiting the CO.sub.2-UH (FIG. 2, Box 21). Use of CO.sub.2 for
cryo-energy storage is not included in this list of "main modes" because
it mainly is not a mode whereby CO.sub.2 flows out of the CO.sub.2-UH
(21) as a product stream. The first seven of the twenty "main modes" all
are CO.sub.2 flows. The eighth mode is a transitional type. It represents
a modality of CO.sub.2 flow connecting into a building materials
production flow based upon absorption of CO.sub.2 flow and hydration into
cementitious carbonating mineralization. The eighth mode (FIG. 2, arrow
or vector 8) represents a time-varying and properties-varying flow of
CO.sub.2 input corresponding to a production recipe. CO.sub.2 products of
the CO.sub.2-UH are represented in FIG. 2 by arrows or vectors 1 through
7, and transitionally by arrow or vector 8. All provide flows of
CO.sub.2, with or without associated steam, with or without a high degree
of compression, and with or without cryo-preparation to states of liquid
CO.sub.2 and dry ice. Such product flows of CO.sub.2 can be categorized
into five types. (NB: "Types" of CO.sub.2 flows are different from "main
modes" of CO.sub.2 utilization.) Each type corresponds to a different
process train shown in FIG. 3 (22, 23, 24, 25, 26). They are as follows.
The first type of flow corresponds to process train 23 in FIG. 3. It is
relatively "raw" CO.sub.2 exhaust gas. The flow is not dehydrated or
compressed to high pressure for long-distance pipeline transport. It is
compressed only, if and as needed, to pressures sufficient for local
pipeline transport. In FIG. 2, vectors 1, 2a, 2b, 3, 4 and 5, (the last
having to do with local algal biomass feeding), are CO.sub.2 flows of
this type. The second type of CO.sub.2 flow is CO.sub.2 exhaust gas that
has been dehydrated and compressed to pressures that are sufficient for
long-distance pipeline transport. This flow is directed into pipeline
transport as needed. It corresponds to process train 24 in FIG. 3. In
FIG. 2, arrow or vector 6, and sometimes arrow or vector 5 (having to do
with algal biomass carbon source feeding, when the CO.sub.2 transport
distance is large), are CO.sub.2 flows of this second type. The third
type of CO.sub.2 flow is refrigerated CO.sub.2 in the form of liquefied
CO.sub.2. This type corresponds to process train 25 in FIG. 3. In FIG. 2,
vector 7 includes liquefied CO.sub.2. The fourth type of CO.sub.2 flow is
of frozen CO.sub.2 "dry ice." This type of flow corresponds to process
train 26 in FIG. 3. In FIG. 2, arrow or vector 7 includes solidified
CO.sub.2. The fifth type of CO.sub.2 flow is a flow with properties that
vary in time according to a product production recipe. It corresponds to
process train labeled 22 in FIG. 3. Process train 22 is drawn to display
the specific case of cement-based eco-concretes and building materials
involving cementitious carbonation and hydration. This is as an example
appropriate to display in time-varying production flow with changing
properties. In FIG. 2, arrow or vector 8 corresponds to this specific
option. In the case of eco-concrete and related building materials, it
represents a transitional situation from a CO.sub.2 product (delivery of
a CO.sub.2 and steam flow according to a time-varying recipe) to a
product created by utilizing CO.sub.2. However, this type of CO.sub.2
flow is not limited only to production of eco-concretes and related
building materials. Other products may require time-varying recipes for
the input of CO.sub.2 with or without associated steam, and at various
pressures and temperatures, for example involving
pressure-temperature-gas-composition variation schedules. The remaining
arrows or vectors, 9 through 20, represent additional "main modes" of
CO.sub.2 utilization. In these, CO.sub.2 is used as an input ingredient
or otherwise as a processing substance utilized for production of
products within the domain of the CO.sub.2-UH (FIG. 2, 21), shown in FIG.
2.
[0554] The first "main mode" of CO.sub.2 utilization (FIG. 2, arrow 1) is
CO.sub.2 fertilization in greenhouse horticulture for plant growth
acceleration and yield boosting. This mode of CO.sub.2 utilization is a
preferred embodiment. In FIG. 2, arrow 1 is shown for this use locally.
Unprocessed gas may be used for this purpose. Modest compression only is
needed for distribution via a local network of pipes. If an areal extent
of 5,000 hectares (a square area, 5 km.times.10 km) is chosen, then the
approximate CO.sub.2 utilization will be .about.2 MTA CO.sub.2 (based on
calculations given herein). The amount of CO.sub.2 utilization scales
roughly as the area of greenhouse horticulture using CO.sub.2. The
provision of large amounts of CO.sub.2 for use in distant greenhouse
horticulture on a large scale requires dehydration and pressurization of
CO.sub.2 for long-distance pipeline transportation.
[0555] The second "main mode" of CO.sub.2 utilization is Lake Kivu biozone
fertilization. This mode of CO.sub.2 utilization is a preferred
embodiment. It is represented as flow arrow 2 in FIG. 2. This vector
split into two sub-vectors, 2a and 2b. This mode of CO.sub.2 utilization
requires only unprocessed gas (as shown in the process train labeled 23
in FIG. 3). It is approximately pure CO.sub.2, except with no need for it
to be dehydrated or highly pressurized. The CO.sub.2 is injected into
Lake Kivu in two ways. First, it can be disseminated by a system of
diffusers directly into the biozone of the Lake. This is shown in FIG. 2
as vector 2a. Second, it can be disseminated into a return flow of
degassed deepwater diffused into the biozone of Lake Kivu as a nutrient
source. This is shown in FIG. 2 as vector 2b, (with CO.sub.2 dissolving
into the return flow water disseminated into the biozone shown as vector
2b connecting into the return water flow vector labeled number 36c).
Doing so under ecosystem feedback monitoring and control boosts the
lake's biological productivity and fish yield. Inventive details will be
disclosed elsewhere. An estimate for an appropriate scale of CO.sub.2
utilization for diffusion into Lake Kivu's biozone is as follows. The
natural scale of deepwater upflux from Lake Kivu's Main Resource Zone
(MRZ) has been roughly estimated to be .about.0.15 km.sup.3/yr across an
areal extent of .about.1000 km.sup.2 by Schmid and Wuest, (2012). This
flux corresponds to an influx volume from deep springs emitting
CO.sub.2-rich high-density water into the MRZ. It provides a minimum
determination of natural CO.sub.2 flux into the base of the biozone.
Using the CO.sub.2 concentration reported in Table 1 (from Wuest et al.,
2012), this determines a CO.sub.2 upflux of .about.0.5 MTA (million
tonnes per year). A more precise estimate has been obtained from
NH.sub.4.sup.+ data in the analysis of Pasche et al., (2011, 2012).
Pasche's analysis determines an upflux of .about.0.7 MTA CO.sub.2. This
natural upward flux of CO.sub.2 nutrient from below into Lake Kivu's
biozone is shut-off or diluted by some return flow injection schemes. In
such circumstances, the upward flux of CO.sub.2 into the biozone can be
replaced by artificial diffusion into the return flow flux being
reinjected into the lake. In general, increasing the CO.sub.2 flux from
below boosts the ecological productivity of the lake. It acts as a carbon
source for algal photosynthesis. Pending input-response testing in test
areas in the lake, a scientifically informed rough estimate for a
reasonable boost is at least a factor-of-three increase. This indicates a
target delivery at least .about.2 MTA of CO.sub.2 into the biozone.
[0556] The third "main mode" of CO.sub.2 utilization (FIG. 2, arrow 3) is
diffusion-dissolution of CO.sub.2 into high-pH (pH >10) return flow
water following water treatment processing by pH-raising methods. This
mode of utilization of CO.sub.2 relates the return flow water treatment
process disclosed in U.S. Patent Application Publication No. 20160257577
A1. This disclosure presents a method for treating nutrient-rich dense
deepwater from Lake Kivu in such a way that the outflow of the process
yields a de-densified water at a high pH. Addition of CO.sub.2 by
injective dissolution may be used to treat this water for purposes of pH
reduction prior to reinjection into Lake Kivu at a depth level below the
biozone, most desirably within the so-called Intermediate Zone (IZ). This
mode of CO.sub.2 utilization for pH reduction of high-pH return flow
treated water is a preferred embodiment. It is shown in FIG. 2 as
CO.sub.2 flow vector 3 connecting into return water flow vector 36b.
Sourcing for this CO.sub.2 in the CO.sub.2-UH is shown in FIG. 3 as
process train 23. This offers an opportunity to sequester CO.sub.2 in
Lake Kivu in a non-dangerous situation more than 100 meters above the
.about.260 meter deep main density discontinuity. Utilizing CO.sub.2 for
pH-balancing may be ecologically prudent even though the injection level
is under the biozone rather than within it. Lowering of pH involves
dissolving CO.sub.2 into alkaline solution causing transformation of
doubly charged carbonate anions, each associated with two sodium cations,
into singly charged bicarbonate anions, each associated with one sodium
cation. The scale of CO.sub.2 utilization via this modality depends on
the sodium concentration and the total flow of return flow water
processed according to the bio-treatment and Mg+Ca-precipitation method.
A simple rough estimate is to assume that CO.sub.2 absorption into the
high pH solution will convert all sodium-associated ions
(2Na.sup.+::1CO.sub.3.sup.2-) into sodium-associated bicarbonate ions
(2Na.sup.+::2HCO.sub.3.sup.-). This will be by addition into solution of
CO.sub.2 in the molar ratio: CO.sub.2/Na=0.5, with respect to the sodium
concentration of the water. For clarity, this assumption is coupled with
the additional simplifying assumptions that all initial sodium associated
anions at pH.about.10.5 are carbonate (CO.sub.3.sup.2-), and all final
sodium-associated anions are bicarbonate (HCO.sub.3.sup.-) at lower pH,
and that sodium (Na) is the predominant cation active in the
carbonate-bicarbonate equilibrium. (The last assumption follows from the
prior precipitative removal of both calcium and magnesium by pH
.about.10.5.) Using input data for sodium at 300 meters depth in Lake
Kivu's main basin from Tassi et al., (2009), Na .about.0.0175 moles/l, a
rough estimate for CO.sub.2 absorption into the high-pH solution is:
.about.0.0088 moles/l (=.about.0.39 grams per liter). This may be
compared to the initial CO.sub.2 concentration in the deepwater at 300
meters depth prior to degassing: CO.sub.2.about.0.055 moles/l,
.about.2.42 g/l. Therefore if all of the return flow is bio-processed and
de-densified, then .about.16%, roughly one sixth of the CO.sub.2
degassing flux, is absorbable for pH-balancing prior to reinjection into
Lake Kivu (at an appropriate density-matched depth in the interval
.about.90 meters to .about.150 meters). Adjustments for the addition of
combustion-derived CO.sub.2 and other corrections suggests that a
reasonable expectation for CO.sub.2 utilization in pH-balancing is
.about.12% of the total flux out of the OXFCPS. For an output of
.about.400 MW, this is roughly 1 MTA (Million Tonnes per Annum) of
CO.sub.2. Together therefore, biozone fertilization and return flow
pH-balancing represent the second and third "major modes" of CO.sub.2
utilization, shown in FIG. 2 as vectors 2a, 2b and 3, respectively. The
simple estimates provided herein indicate it is possible to utilize quite
a large fractional component of CO.sub.2 exhaust locally by shallow
injection in Lake Kivu for biozone fertilization and return flow
pH-balancing: altogether roughly one third of the total degassing flux of
CO.sub.2. (Note there is no increased limnic eruption risk by these
methods because the chemical state of the absorbed CO.sub.2 would be in
the form of bicarbonate anion in a chemical state close to that of water
in the biozone.)
[0557] The fourth "main mode" of CO.sub.2 utilization (FIG. 2, arrow 4) is
a pH-controlling modality preparatory to return flow into an algal growth
sector. This mode of CO.sub.2 utilization is a preferred embodiment.
CO.sub.2 input in this modality is shown in FIG. 8 as flow vector 12a
providing CO.sub.2 in item 17a. Item 17a is a diffuser. It adds CO.sub.2
into solution prior to flow into an algal growth sector identified as
item 18. No estimate for this modality is provided in table 2. The scale
of CO.sub.2 input is dependent on a range of factors having to do with
the specific conditions of degassing and specifications for control over
Mg and Ca precipitation.
[0558] The fifth "main mode" of CO.sub.2 utilization (FIG. 2, arrow 5) is
local algal production. This mode of CO.sub.2 utilization is a preferred
embodiment. CO.sub.2 is disseminated into algal biocultures both by
direct CO.sub.2 dissolution into biocultures and indirectly by addition
of sodium bicarbonate (which may be formed by water absorbing carbonation
of alkaline brine or sodium carbonate molecules, Na.sub.2CO.sub.3, into
two bicarbonate molecules NaHCO.sub.3). Degassed Lake Kivu deepwater
carries dissolved inorganic carbon accessible for algal carbon fixation
in the form of bicarbonate anion. It also carries NPK bionutrients. A
substantial crop of algae therefore can be grown to certain concentration
levels without adding any additional carbon source. However, with
addition of extra nutrients (as may be accessed by various methods of
nutrient recycling in algal production and processing), further algal
biomass can be grown if a new source of carbon is provided. CO.sub.2 can
be used as a carbon source for this purpose. It may be utilized via a
pH-lowering input chemistry, as noted herein, converting doubly-charged
carbonate anions to singly-charged bicarbonate anions. Algal production
can follow a two-step focus: (i) first, initial separation of very high
value nutraceutical compounds, followed by (ii) high-pressure
hydrothermal processing of residues with nutrient recycling for
production of biofuels, bio-asphalt and bio-fertilizers. The production
of high-value nutraceutical products depends on the species mix of algae
grown. It therefore depends on the biotechnological set-up, controls and
inputs. Many options are possible. For example, CO.sub.2 may be used to
grow diazotrophic cyanobacteria algae via P-only nutrient feeding into
biocultures. Such biocultures also may be grown under various low-oxygen
N.sub.2:CO.sub.2 canopy conditions to optimize cyanobacterial growth and
dominance conditions (Smith and Evans, 1971; Fay, 1992; Thomas et al.,
2005; Berman-Frank et al., 2005; Molot et al., 2014). This produces
cyanobacteria biomass harvestable as NP-rich biofertilizers where
nitrogen has been fixed by the diazotrophic activity of the
cyanobacteria, and where carbon has been fixed by photosynthesis from the
CO.sub.2. CO.sub.2 additionally may be utilized as a
coagulation-flocculation agent in harvesting, as noted herein. CO.sub.2
may be used for post-harvest processing to separate algal oil, including
high-value nutraceutical/pharmaceutical components. Algal biomass
production can utilize CO.sub.2 in many and different ways.
[0559] Two estimates for CO.sub.2 utilization follow relating to algal
production. If 0.5 MTA CO.sub.2 is utilized for carbonation of (1.2 MTA
of) sodium carbonate, (Na.sub.2CO.sub.3), to sodium bicarbonate,
(NaHCO.sub.3), then the amount of sodium bicarbonate produced at 100%
efficiency is: .about.1.9 MTA. Some fraction of this sodium bicarbonate
production may be used for large-scale algal production, for example
growing spirulina as a high-value protein and nutrients source for mother
and child nutritional supplement feeding addressing widespread regional
dietary protein deficiency. Second, if 1.0 MTA CO.sub.2 is directly
diffused into algal bioculture, then if .about.1/2 of that carbon is
harvestable in algal biomass, and if .about.1/2 of that carbon is
convertible into (for example) transportation biofuel carbon (therefore a
carbon mass of: 1MTA.times.12/44.times.0.25.about.80,000 tonnes/yr), then
the amount of refined biofuel (assuming an average molecular formula:
C.sub.12H.sub.23) produced is .about.93,000 tonnes per year, or
.about.110 million liters at a density of .about.0.83 tonnes per 1,000
liters. For comparison, Rwanda's total annual consumption of
transportation fuel is roughly 400 million liters. Overall, ambitious
target scales for algal bioproduction utilization for Lake Kivu CO.sub.2
ranges roughly from 0.5 to 5 MTA. The scale of direction of CO.sub.2
utilization is dependent on the techno-economics of developing
appropriate engineering biosystems for algal growth and harvesting
integrated with biomaterials processing (such as for high-value
nutraceutical/pharmaceutical oil production followed by high-pressure
hydrothermal residue processing into fertilizers, biofuels, syngas and
other products).
[0560] The sixth "main mode" of CO.sub.2 utilization is pressurized
CO.sub.2 delivery by pipeline. This mode of CO.sub.2 utilization is a
preferred embodiment. Typically, pressurized CO.sub.2 delivery by
pipeline is in high volumes over substantial distances. As this "main
mode" specifies a gas specification and associated delivery technology,
several specific "main modes" of CO.sub.2 utilization are referenced
together under this mode. All are included as preferred embodiments. Five
specific types of CO.sub.2 utilization by means of this method of
CO.sub.2 delivery are included. The first example of a potential
large-scale use of high-pressure CO.sub.2 delivered by a long pipeline is
CO.sub.2 delivered for Enhanced Oil Recovery (EOR) to the Albertine Rift
of the Uganda-DRC border region, or to any future area in the region
found to be oil-rich, including locations within the Lake Kivu basin
itself. This mode of CO.sub.2 utilization is a preferred embodiment.
Oil-bearing formations are known to exist roughly from south of Lake
Edward north along the border rift through to the northern boundary of
Lake Albert. At present, the entire extractable oil resource is estimated
to be .about.2 billion barrels. Initial oil extraction operations have
been developed on Lake Albert. This location is roughly 400 km northeast
of the northern boundary of Lake Kivu.
[0561] The second example of a potentially large-scale use of
high-pressure dehydrated CO.sub.2 delivered at a distance by CO.sub.2
pipeline is large-scale olivine carbonation. This use of CO.sub.2 for
this purpose typically would be associated with mining activity,
typically involving dunite-containing nickel-rich ore bodies. Such bodies
exist in the NE of Rwanda as well as in Tanzania and Burundi close to
their borders with Rwanda. Olivine carbonation can be a greentech method
of nickel mining when dunite deposits are available with high nickel
contents and/or that contain nickel-concentrating sulfides. Olivine
carbonation also can be used as a way to produce silicic acid together
with iron and magnesium carbonates. This mix is useful for plant feeding
as a mineral fertilizer. Uses include algal biomass fertilization focused
on diatom species (many of which require silicon feeding). Utilization of
CO.sub.2 for the production of mineral fertilizers for diatom algal
production within a Lake Kivu CO.sub.2-UH is an attractive prospect in
view of associated high-value nutraceuticals and pharmaceuticals export
potential. This mode of CO.sub.2 utilization is a preferred embodiment.
[0562] The third example is delivery of CO.sub.2 for distant greenhouse
horticultural utilization, (for example in Kenya). This mode of CO.sub.2
utilization is a preferred embodiment.
[0563] The fourth example is delivery of CO.sub.2 for use in "solar fuels"
and/or "solar chemicals" (or, more generally, "renewables-based" fuels
and chemicals) manufacture in connection with renewable electric power
provided by solar arrays and/or by wind farms, and/or from hydropower.
Pipeline export of CO.sub.2 may be combined with CO.sub.2-EOR, for
example, in eastern components of the East African rift in both Kenya and
Tanzania where there are rift oil sectors as well as zones of very high
average solar radiation intensity suitable for large solar power
generation arrays (see: Solargis, 2011). This mode of CO.sub.2
utilization is a preferred embodiment.
[0564] The fifth example is delivery of high-pressure pipeline CO.sub.2 to
areas in Kenya and Tanzania where sodium carbonate and sodium
carbonate-rich brines are mined and processed, and where CO.sub.2
carbonation can produce a sodium bicarbonate product, and where solar
radiation conditions are excellent for high-value algal biomass
production in alkaline biocultures, for example spirulina farming. This
mode of CO.sub.2 utilization is a preferred embodiment.
[0565] The seventh "main mode" of CO.sub.2 utilization involves cryogenic
treatment to create CO.sub.2 products by refrigeration, both liquid and
solid CO.sub.2. This mode of CO.sub.2 utilization is a preferred
embodiment. It is a mode of CO.sub.2 preparation and delivery rather than
a specified mode of CO.sub.2 utilization. Therefore several specified
sub-modes are included within this section as preferred embodiments.
Again, refrigerated CO.sub.2 may be in the form of liquefied CO.sub.2
and/or as dry ice. Both of these modes are shown in FIG. 3 as process
trains labeled 25 and 26, respectively. Liquefied CO.sub.2 is transported
across long distances in large amounts typically in thermally insulated
tanker trucks and large ships similar to those used for LNG
transportation. In central Africa, liquid CO.sub.2 may be transported by
insulated tanker truck. It may be delivered for many uses. These uses do
not depend on the CO.sub.2 being in a liquid form in so far as
liquefaction simply can be an efficient mode for transporting CO.sub.2
utilized in other forms. Uses include, for example, beverage carbonation,
insect protection and fumigation (for example in grain storage),
horticultural use (including algal production), wastewater pH-lowering,
tank re-filling for example for local dry ice manufacturing, food product
packaging, use in supercritical extraction processing, supercritical
CO.sub.2 dry cleaning, medical gas mixing, waterless textiles dyeing,
charging of fire extinguishing systems and refrigeration systems using
CO.sub.2 as a thermal transfer fluid, cold pasteurization of milk, beer
and juices, humane animal slaughtering, CO.sub.2 fracking or frack fluid
mixing, and lithium processing. Liquid CO.sub.2 also may be transported
by means of short-distance insulated pipelines, for example within a
geographically disseminated CO.sub.2-UH. An estimate for potential
CO.sub.2 utilization of liquid CO.sub.2 in the region is .about.50,000
tonnes per year.
[0566] Dry ice typically is transported in insulated and/or refrigerated
delivery trucks. It also can be sub-delivered in insulated packages via
motorbikes to remote off-grid locations. It is generally used as a
coolant. In the area of Lake Kivu, dry ice can be utilized to supply
needs for off-grid refrigeration. An example is delivery as a refrigerant
with beverages served chilled and/or with spoilable meats, including
fish. If beverages are supplied in kegs or other tanks, then off-grid dry
ice refrigeration makes it possible to avoid the high cost of bottles and
bottling. Dry ice also can be used as a non-wetting refrigerant to be
used within coolers and other insulated packaging for truck transport of
perishables (such as fish, milk, flowers and fruits) in trucks otherwise
not equipped for cargo refrigeration. An estimate for potential CO.sub.2
utilization as dry ice in the region may be as high as 50,000 tonnes per
year for such uses. Altogether, therefore, a rough estimate under this
sixth "main mode" of CO.sub.2 utilization is .about.100,000 tonnes per
year in total. Dry ice production is a preferred embodiment of the
invention.
[0567] The eighth "main mode" of CO.sub.2 utilization is provision of
unprocessed or mildly processed hot and wet (steam-rich) exhaust from
oxyfuel combustion into cementing mineral carbonation in the production
of concrete products and other building materials that include mineral
cements. This mode of CO.sub.2 utilization is a preferred embodiment. It
is shown in FIG. 2 as vector 8. It also is shown in FIG. 3 as the example
displayed for the representation of the process train labeled as 22. This
process can use magnesium hydroxide (brucite) as the main reactant with
CO.sub.2 for mineralization into various Mg-carbonates. Or it can
remineralize pre-carbonated nesquahonite to generate various output
carbonated and hydrated mineralogies. Or it can involve CO.sub.2
carbonation of conventional Portland cements in various ways. The use of
magnesium is of special interest for Lake Kivu. This is because it can be
obtained as a precipitated product of de-densifying return flow water
treatment according to the method disclosed by the inventor in U.S.
Patent Application Publication No. 20160257577 A1. The scale of CO.sub.2
use by this method can be estimated at a minimum scale via the flux of
precipitated magnesium associated with treatment or degassed return flow
deepwater according to the above-noted method. Magnesium hydroxide
stoichiometry is used as the example. Scaled to a 400 MW power output,
the dissolved Mg flux through the degassing system is close to 0.6 MTA of
magnesium. Given assumptions of (for example) .about.90% Mg capture and
.about.70% partitioning of return flow into an Mg-precipitating water
treatment mode, the captured Mg flux estimate is: .about.0.4 MTA Mg.
Using a nesquahonite composition, (MgCO.sub.3.3H.sub.2O), for a
carbonation target composition, the mass flow of the associated Mg-based
component of carbonated and hydrated cement is .about.2.3 MTA for the
hydrated Mg-based cement component. (For comparison, Rwanda's dominant
cement producer, CIMERWA, produces .about.0.6 MTA of dryweight Portland
cement. Bateta, 2015). The rate of CO.sub.2 consumption for cementitious
mineralization in this process is .about.0.7 MTA CO.sub.2. For concrete
with a mass ratio of >5 for aggregate-to-cement, this corresponds to
in excess of 12 million tonnes of concrete production per year. Moreover,
in concretes cementing with Mg-hydroxide ("brucite") carbonation
reactions, CO.sub.2 additionally can be mineralized by carbonation
reactions within pozzolanic aggregates. And, as an alternative, CO.sub.2
can be mineralized into ordinary cementing reactions with Portland-type
cement chemistries using pressure chambers for setting and curing.
Overall, there are many opportunities across a range of cementitious
chemistries and pozzolan addition situations. A rough estimate of
utilizable CO.sub.2 from cementitious mineralization-incorporation is:
.about.1 MTA CO.sub.2. This scale of CO.sub.2 utilization represents a
gigantic capacity for CO.sub.2-mineralizing eco-concrete production. It
represents more than a doubling of Rwanda's circa 2015 cement production
capacity. CO.sub.2-mineralizing eco-concrete and related building
materials may be factory-made as pre-cast molded stock. Advanced
CO.sub.2-mineralizing eco-concretes may be developed that can be poured
and set (and process remineralized) in the field. CO.sub.2-mineralizing
eco-concrete production are included as embodiments of the invention,
capturing degassed (and post methane combustion) Lake Kivu CO.sub.2 into
building materials.
[0568] The ninth "main mode" of CO.sub.2 utilization is urea manufacture.
This mode of CO.sub.2 utilization is a preferred embodiment. The
potential for urea production in the context of the invention disclosed
herein follows from the availability of CO.sub.2 and also from the fact
that a large flux of ammonium ion is present in Lake Kivu deepwater
passing through the TDS. Additionally, the Air Separation Unit (ASU)
component of the OXFCPS generates a large flux of purified nitrogen gas.
This can be used for ammonia (NH.sub.3) production, combining with
H.sub.2. Algal biomass processing also can use methods that allow
nutrient recycling that allows capture of ammonia. At a power production
level of 400 MW, the mass of urea equivalent for 100% capture and
conversion of NH.sub.4+ flux present in the extracted deepwater stream is
212,000 tonnes per year. This is equivalent to .about.200,000 tonnes per
year of ammonia (NH.sub.3). This number provides a useful reference
point. For urea synthesis, CO.sub.2 is used on a molar ratio basis of
CO.sub.2/NH.sub.3=1.0. Therefore a flux of .about.200,000 tonnes of
ammonia determines an intake of .about.518,000 tonnes of CO.sub.2.
Assuming, for example, a situation of capture and conversion of
.about.60% of the ammonium flux through deepwater processing, then
CO.sub.2 utilization is .about.300,000 tonnes per year and urea
production is .about.400,000 tonnes per year. No disclosure of a method
or system for removal of this ammonium from Lake Kivu deepwater is
included herein.
[0569] The tenth "main mode" of CO.sub.2 utilization is formic acid
production. This mode of CO.sub.2 utilization is a preferred embodiment.
As referenced herein, there are many possibilities for modes of
production utilizing CO.sub.2 to produce formic acid. These include
production with electrolytic hydrogen as a "solar chemical" or "solar
fuel," and hydrothermal production using water as the hydrogen source
linked with zero-valent metals redox cycling. Both CO.sub.2 and formic
acid also can be used for animal hide processing and as tanning agents in
developing a leather products industry. A reasonable target for CO.sub.2
utilization to produce formic acid is 10,000 tonnes per year. A much
larger scale of production would be possible if formic acid fuel cell
technologies were to become widespread.
[0570] The eleventh "main mode" of CO.sub.2 utilization is production of
carbon monoxide (CO). This mode of CO.sub.2 utilization is a preferred
embodiment. Carbon monoxide has use in metals smelting, especially tin
(Sn), zinc (Zn) and iron (Fe). Several modes for CO production from
CO.sub.2 have been described herein, such as, for example, that of Igor
Lubomirsky and his Weitzmann Institute colleagues. Lubomirsky's method
creates both CO and a separated stream of O.sub.2 gas useful for input
into oxyfuel combustion as shown in FIG. 2, flow vector 31. Rwanda has
long been a tin-producing country utilizing cassiterite-rich ores.
Rwandan cassiterite (SnO.sub.2) production circa 2015 is approximately
5,000 tonnes per year. Potential production capacity is much higher. A
rough estimate of the amount of CO.sub.2 needed to smelt cassiterite from
CO is a molar ratio of .about.2CO.sub.2/SnO.sub.2, corresponding to a
mass ratio of .about.0.58. Consequently, a rough estimate of CO.sub.2
potential for CO production for cassiterite smelting is .about.3,000
tonnes per year scaled to Rwandan production. Much larger amounts of
carbon monoxide could be utilized for scaled-up tin production as well as
for smelting of other metal oxide ores and for metals processing.
[0571] The twelfth "main mode" of CO.sub.2 utilization is input of
CO.sub.2 into the manufacture of pyrethrum biopesticide. This mode of
CO.sub.2 utilization is a preferred embodiment. Pyrethrum biopesticide is
sold in returnable pressurized tank bottles of CO.sub.2. CO.sub.2
functions in a dual mode as a greentech solvent and non-toxic propellant.
Pyrethrum-in-CO.sub.2 "organic" biopesticide can be used in greenhouses
as a form of insecticide that additionally provides CO.sub.2 plant
fertilization. Organic biopesticides have a potentially very large
market. In the region of Lake Kivu, this market can scale with the growth
of high-intensity greenhouse cultivation with CO.sub.2 yield boosting. A
rough estimate for CO.sub.2 utilization in this eleventh category is
included as 20,000 tonnes per year.
[0572] The thirteenth "main mode" of CO.sub.2 utilization is for CO.sub.2
use in forest products production. This mode of CO.sub.2 utilization is a
preferred embodiment. This is a wide category. Many types of inputs are
possible. An example is using supercritical CO.sub.2, formic acid and
sodium carbonate chemicals for pulping of bamboo to produce bamboo-based
chemicals (such a xylitol), paper, viscose-type bamboo textiles and
lignocellulosic biofuels. No estimate for a scale of utilization is
presented. Bioprocessing of forest products using CO.sub.2 and derivative
chemicals represents a huge opportunity in the Lake Kivu region. This is
in view of the great forests of the DRC existing to the west of the Lake.
[0573] The fourteenth "main mode" of CO.sub.2 utilization is CO.sub.2
Plume Geothermal (CPG) (and/or mixed CO.sub.2--H.sub.2O plume) extraction
of geothermal energy, possibly connected with CO.sub.2 geosequestration.
This mode of CO.sub.2 utilization is a preferred embodiment. Lake Kivu is
situated in a region with huge geothermal resources. No estimate for a
scale of utilization is presented.
[0574] The fifteenth "main mode" of CO.sub.2 utilization is fuels
production by reaction of CO.sub.2 with hydrogen, and/or water, and/or
methane in various production processes, with or without electric power
inputs, yielding methanol, dimethyl ether (DME) and other fuels and
chemicals, including those produced by mini-GTL processes. This mode of
CO.sub.2 utilization is a preferred embodiment. Many such methods are
referenced and briefly reviewed herein. Many additional methods will be
developed in the future as relatively small scale GTL technologies
develop and grow, and as new economically viable turnkey plant options
are developed to use stranded and/or otherwise flared natural gas, and
also as CO.sub.2-utilizing transport fuels production options become
commercially viable based on the need for energy storage from
intermittent supplies of renewable electric power (that is: "solar-" or
"electro-" fuels and chemicals). Methanol and DME are of particular
interest in the location of Lake Kivu. They both can be utilized as a
transport fuel fuels and fuel additives. DME also could be used as a
cost-lowering substitute for imported bottled propane gas used in home
cooking and by businesses. DME additionally can be useful for algal
products processing utilizing wet algal biomass, as noted herein. Both
methanol and DME also are of special global environmental interest. They
represent the CO.sub.2-recycling "methanol economy" vision of George Olah
and colleagues. No estimate for a scale of utilization is presented.
[0575] The sixteenth "main mode" of CO.sub.2 utilization is a special case
of the previous main mode. It is input of hot CO.sub.2 plus steam exhaust
from the OXFCPS into syngas production of methanol and DME. This mode of
CO.sub.2 utilization is a preferred embodiment. It aims to capture heat
energy from combustion for CO.sub.2 utilization purposes using the
outflow of the OXFCPS exhaust directly. It includes, for example,
application of methods and systems of technologies of the type being
developed by the Danish company Haldor Topsoe for the transformation of
inputs of CO.sub.2, steam and mechanical and/or electric power into
outputs of methanol and oxygen gas (Hansen, 2014ab, 2015a,c,f). These
methods involve designs that incorporate Solid Oxide Electrolysis Cell
(SOEC) technologies into production of syngas from CO.sub.2 and steam
mixtures. The OXFCPS submethod and subsystem described as a part of the
invention disclosed herein generates exhaust outputs of CO.sub.2, steam
and electric power. OXFCPS exhaust and power production therefore matches
inputs to the new technology being developed by Haldor Topsoe, though not
necessarily with the correct range of H.sub.2O/CO.sub.2 input ratios.
However, heat capture within the system can modulate steam addition to
reach targets for the input ratio of H.sub.2O to CO.sub.2 into the
reactor system. Extra power for CO.sub.2 plus steam electrolysis via SOEC
can be obtained additionally from renewable energy inputs transmitted by
high-voltage wires. An extra bonus is that in an integrated system,
co-produced O.sub.2 can be fed into the input into oxyfuel combustion. No
estimate for a scale of utilization is presented.
[0576] The seventeenth "main mode" of CO.sub.2 utilization is another
special case of a previous main mode. It is inputs of CO.sub.2 and water
into electrosynthesis of various chemicals via formate and oxalic acid
(H.sub.2C.sub.2O.sub.4) platforms such are being developed by the company
Liquid Light, for example for the production on mono-ethylene glycol
(MEG) for use in production of PET plastic bottles. This mode of CO.sub.2
utilization is a preferred embodiment. Use of these methods with solar
power inputs generates "solar chemicals" (including "solar fuels"). This
displaces the use of petroleum by utilizing waste CO.sub.2 as an
alternate carbon source. No estimate for a scale of utilization is
presented.
[0577] The eighteenth "main mode" of CO.sub.2 utilization is deployment of
gas fermentation biotechnologies based on the microbial Wood-Ljundahl
pathway to produce acetate and other chemicals. This mode of CO.sub.2
utilization is a preferred embodiment. It is done via inputs of either
mixtures of CO.sub.2 and H.sub.2 mixtures, or CO.sub.2 alone with
electrons provided to the microbes ("electrobiosynthesis"). As noted
herein, the company LanzaTech is developing these methods commercially.
No estimate for a scale of utilization is presented.
[0578] The nineteenth "main mode" of CO.sub.2 utilization is plastics
manufacture with chemical incorporation of CO.sub.2. This mode of
CO.sub.2 utilization is a preferred embodiment. Examples of technologies
include the processes of CO.sub.2 incorporation into CO.sub.2-polyols
developed by companies such as Novomer, Bayer/Covestro and Econic
Technologies. CO.sub.2-utilizing plastics can be produced in synergy with
the production of CO.sub.2-utilizing bioplastics, for example using algal
biomass and/or separated algal oils. No estimate for a scale of
utilization is presented.
[0579] The twentieth "main mode" of CO.sub.2 utilization is high-value
carbon products production. What is referred to by "carbon products" is
products composed mostly (though not strictly only) of forms of elemental
carbon. This mode of CO.sub.2 utilization is a preferred embodiment.
Examples of attractive possibilities are dense nanoporous graphene used
in supercapacitors, carbon nanotubes used in new battery technologies,
and carbon nanofibers used in high-strength composites. Byproduct oxygen
gas can feed O.sub.2 into the ASU oxygen supply for oxyfuel (as shown by
flow vector 31 in FIG. 2). Using an oxygen stream that otherwise might be
vented as a waste can provide an efficiency boost in cases where large
quantities of CO.sub.2 are utilized to produce carbon products by
splitting CO.sub.2 into C and O.sub.2.
[0580] An additional preferred embodiment of the invention disclosed
herein pertains to a co-product adjunct to CO.sub.2. This is purified
nitrogen in both gaseous (N.sub.2) and liquefied forms (LN.sub.2).
Purified nitrogen is co-produced with pure oxygen gas in the submethod
and subsystem of an Air Separation Unit (ASU). As shown in FIG. 2, box 1,
the OXFCPS overall is defined to be an integrative combination of items
26, 27, 28 and 29, with item 27 being an ASU. An ASU is herein defined to
be any technology that can obtain a supply of separated O.sub.2 for
infeed into oxyfuel combustion. A cryogenic air separation unit is the
conventional (but by no means the only) technology component of the
overall OXFCPS. If implemented in a specific design as an option within
the overall scope of the invention disclosed herein, a cryogenic ASU
produces an adjunct supply of liquefied nitrogen gas (N.sub.2). This is
shown in FIG. 2 as a part of item 27, yielding flows of liquid (or
gaseous) nitrogen. These flows are shown as flow vectors 39 and 40. Flow
vector 39 enters the CO.sub.2-UH (via item 30 where cryo-capacities are
present).
[0581] Production of cryo-liquefied nitrogen (LN.sub.2 or LN2) by the ASU
also is shown in FIG. 6. FIG. 6 shows a preferred embodiment utilizing
this LN.sub.2 both for cryo-energy storage and for cooling of a Digital
Data Center (DDC). Cryogenic energy provided by the ASU in the form of
LN.sub.2 (or LO.sub.2) can be used in the production of liquefied and/or
solidified CO.sub.2 within the CO.sub.2-UH (FIG. 2, item 21). Also it can
be utilized independently of the CO.sub.2-UH, as shown by flow vector 40
in FIG. 2. The capacity of the overall system to produce and store
liquefied N.sub.2 in excess of that used within the ASU (for energy
recycling efficiency) can be considered as an adjunct capacity assisting
powerplant efficiency as well as CO.sub.2 utilization. Utilization of
cold nitrogen gas also can supply Digital Data Center (DDC) cooling. This
is illustrated herein in FIG. 6 and its accompanying text. Both cold
N.sub.2 and LN.sub.2 also may be used for DDC cooling. Use of cold
nitrogen produced by OXFCPS operations as a utilization of otherwise
wasted material and associated cryo-energy can assist realization of DDC
industrialization by lessening the (often very substantial) electric
power draw of such a facility. Nitrogen gas also has numerous other
productive uses, for example in algal production where it provides a
N.sub.2 source for diazotrophic (nitrogen-fixing) cyanobacteria. It also
is useful for algal culture sparging and related uses for removal of
growth-inhibiting O.sub.2. Nitrogen gas also may provide basic chemical
inputs for various purposes into a large number of types of chemical
synthesis reactions. FIG. 6 shows a preferred embodiment (as item 13)
providing a source of "warm" nitrogen gas as an outflow of cold nitrogen
into DDC cooling. This cooling is fed either directly from stored
LN.sub.2 (FIG. 6, item 11) or from cold nitrogen gas after being used in
recovery of stored cryo-energy (cf, FIG. 6, item 18c feeding an outflow
as item 12). More generally, the overall method and system provides
nitrogen gas as outflow (FIG. 6, item 12) that is available for
utilization for any purposes.
[0582] An additional adjunct capacity of the invention is production of
Liquefied Natural Gas (LNG) and associated forms of Natural Gas (NG) that
can be produced and sold as a consequence of the capability to separate
natural gas (see FIG. 6, item 40) from an inflow of mixed NG and CO.sub.2
from Lake Kivu (FIG. 6, item 38). (NB: NG deriving from Lake Kivu is
biogas.) These associated forms of NG are highly useful for various
purposes. These can be produced and sold as adjunct capacities of the
invention in preferred embodiments. They are: (i) Compressed Natural Gas
(CNG, see Wikipedia entry:
https://en.wikipedia.org/wiki/Compressed_natural_gas), and Adsorbed
Natural Gas (ANG, see Wikipedia entry:
https://en.wikipedia.org/wiki/Adsorbed_natural_gas). The capacity to
produce NG in any of these forms (LNG, CNG, ANG) derives from a CO.sub.2
separation processing function within the CO.sub.2-UH (FIG. 6, Box 4).
This CO.sub.2 separation processing function produces dry ice and/or
LCO.sub.2. It is indicated in FIG. 6 circumscribed within Box 36 (and
including items 35, 37, 39 and 40). This adjunct capacity for NG
production is a part of the cryogenic capacities, including the cryogenic
fluids and cryo-energy storage capacities, of the invention (FIG. 6, Box
28), and is a preferred embodiment. Such an adjunct capacity has potent
potential in the locus of Lake Kivu for purposes such as: (i) providing
bottled NG (CNG and/or ANG) for home and business cooking and other
similar uses of heat energy from NG combustion; (ii) providing bottled NG
(CNG and/or ANG) as a source of fuel for internal combustion engines such
as, for example, those in motorcycles, cars and trucks modified to run on
NG. Of course, the capacity to produce LNG for CO.sub.2 separation
processing and cryo-energy storage also allows LNG to be sold as well as
used as a stored energy "backup" reservoir of both cryo-energy and
chemical energy for powerplant operations backup purposes such as may be
necessary, for example, in situations of maintenance and improvements of
extractive degassing equipment.
[0583] While the invention has been described in detail and with reference
to specific examples thereof, it will be apparent to one skilled in the
art that various changes and modifications can be made therein without
departing from the spirit and scope thereof.
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