US20090232861A1 - Extraction and sequestration of carbon dioxide - Google Patents

Extraction and sequestration of carbon dioxide Download PDF

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Publication number
US20090232861A1
US20090232861A1 US12/389,213 US38921309A US2009232861A1 US 20090232861 A1 US20090232861 A1 US 20090232861A1 US 38921309 A US38921309 A US 38921309A US 2009232861 A1 US2009232861 A1 US 2009232861A1
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carbon dioxide
sorbent
gas
water
chamber
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US12/389,213
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Allen B. Wright
Klaus S. Lackner
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KILIMANJARO ENERGY Inc
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Global Research Technologies LLC
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Priority to US12/389,213 priority Critical patent/US20090232861A1/en
Assigned to GLOBAL RESEARCH TECHNOLOGIES, LLC reassignment GLOBAL RESEARCH TECHNOLOGIES, LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LACKNER, KLAUS S., WRIGHT, ALLEN B.
Publication of US20090232861A1 publication Critical patent/US20090232861A1/en
Assigned to KILIMANJARO ENERGY, INC. reassignment KILIMANJARO ENERGY, INC. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: GLOBAL RESEARCH TECHNOLOGIES, LLC
Priority to US13/737,818 priority patent/US20130343981A1/en
Priority to US14/257,698 priority patent/US20150104554A1/en
Priority to US14/561,831 priority patent/US9527747B2/en
Abandoned legal-status Critical Current

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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01MCATCHING, TRAPPING OR SCARING OF ANIMALS; APPARATUS FOR THE DESTRUCTION OF NOXIOUS ANIMALS OR NOXIOUS PLANTS
    • A01M1/00Stationary means for catching or killing insects
    • A01M1/02Stationary means for catching or killing insects with devices or substances, e.g. food, pheronones attracting the insects
    • A01M1/023Attracting insects by the simulation of a living being, i.e. emission of carbon dioxide, heat, sound waves or vibrations
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01KANIMAL HUSBANDRY; CARE OF BIRDS, FISHES, INSECTS; FISHING; REARING OR BREEDING ANIMALS, NOT OTHERWISE PROVIDED FOR; NEW BREEDS OF ANIMALS
    • A01K67/00Rearing or breeding animals, not otherwise provided for; New breeds of animals
    • A01K67/033Rearing or breeding invertebrates; New breeds of invertebrates
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/04Carbon disulfide; Carbon monoxide; Carbon dioxide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
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    • B01D53/02Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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    • B01D53/14Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456Removing acid components
    • B01D53/1475Removing carbon dioxide
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    • B01D53/22Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D61/00Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44Ion-selective electrodialysis
    • B01D61/445Ion-selective electrodialysis with bipolar membranes; Water splitting
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D88/00Large containers
    • B65D88/74Large containers having means for heating, cooling, aerating or other conditioning of contents
    • B65D88/745Large containers having means for heating, cooling, aerating or other conditioning of contents blowing or injecting heating, cooling or other conditioning fluid inside the container
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/50Carbon dioxide
    • GPHYSICS
    • G06COMPUTING; CALCULATING OR COUNTING
    • G06QINFORMATION AND COMMUNICATION TECHNOLOGY [ICT] SPECIALLY ADAPTED FOR ADMINISTRATIVE, COMMERCIAL, FINANCIAL, MANAGERIAL OR SUPERVISORY PURPOSES; SYSTEMS OR METHODS SPECIALLY ADAPTED FOR ADMINISTRATIVE, COMMERCIAL, FINANCIAL, MANAGERIAL OR SUPERVISORY PURPOSES, NOT OTHERWISE PROVIDED FOR
    • G06Q30/00Commerce
    • G06Q30/018Certifying business or products
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2252/20Organic absorbents
    • B01D2252/204Amines
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2253/00Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10Inorganic adsorbents
    • B01D2253/102Carbon
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2253/00Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20Organic adsorbents
    • B01D2253/206Ion exchange resins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/30Sulfur compounds
    • B01D2257/302Sulfur oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
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    • B01D2257/40Nitrogen compounds
    • B01D2257/402Dinitrogen oxide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2257/00Components to be removed
    • B01D2257/50Carbon oxides
    • B01D2257/504Carbon dioxide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2259/00Type of treatment
    • B01D2259/40Further details for adsorption processes and devices
    • B01D2259/40083Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
    • B01D2259/40086Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by using a purge gas
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2259/00Type of treatment
    • B01D2259/40Further details for adsorption processes and devices
    • B01D2259/40083Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
    • B01D2259/40088Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating
    • B01D2259/4009Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating using hot gas
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2259/00Type of treatment
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    • B01D2259/414Further details for adsorption processes and devices using different types of adsorbents
    • B01D2259/4141Further details for adsorption processes and devices using different types of adsorbents within a single bed
    • B01D2259/4145Further details for adsorption processes and devices using different types of adsorbents within a single bed arranged in series
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
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    • B01D53/02Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/0462Temperature swing adsorption
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02CCAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00Capture or disposal of greenhouse gases
    • Y02C20/10Capture or disposal of greenhouse gases of nitrous oxide (N2O)
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02CCAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00Capture or disposal of greenhouse gases
    • Y02C20/40Capture or disposal of greenhouse gases of CO2
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/151Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • the present invention relates to a method and apparatus for the removal of selected gases from an environment and the disposal of the selected gases in another environment.
  • the present invention in one aspect relates to removal of selected gases from the atmosphere.
  • the invention has particular utility in connection with the extraction of carbon dioxide (CO 2 ) from the atmosphere and subsequent sequestration of the extracted CO 2 or conversion of the extracted CO 2 to useful or benign products and will be described in connection with such utilities, although other utilities are contemplated, including the extraction, sequestration or conversion of other gases from the atmosphere including NO x and SO 2 .
  • CO 2 carbon dioxide
  • CO 2 occurs in a variety of industrial applications such as the generation of electricity from coal at power plants and in the use of hydrocarbons that are typically the main components of fuels that are combusted in combustion devices, such as engines. Exhaust gas discharged from such combustion devices contains CO 2 gas, which at present is simply released to the atmosphere. However, as greenhouse gas concerns mount, CO 2 emissions from all sources will have to be curtailed. For mobile sources such as motor vehicles and airplanes the best option is likely to be the collection of CO 2 directly from the air rather than from the mobile device in the motor vehicle or airplane. The advantage of removing CO 2 from air is that it eliminates the need for storing CO 2 on the mobile device.
  • Extracting carbon dioxide (CO 2 ) from ambient air would make it possible to use carbon-based fuels and deal with the associated greenhouse gas emissions after the fact. Since CO 2 is neither poisonous nor harmful in parts per million quantities, but creates environmental problems simply by accumulating in the atmosphere, it is possible to remove CO 2 from air in order to compensate for equally sized emissions elsewhere and at different times.
  • the present disclosure provides a system, i.e. a method and apparatus for extracting a contaminant from a flow stream, such as ambient air or an exhaust stack, and for delivering the extracted contaminant for use in a secondary process.
  • a flow stream such as ambient air or an exhaust stack
  • the present disclosure is described primarily in regards to the removal and sequestration of CO 2 , though the apparatus and method of the present disclosure may be used with various other contaminants.
  • CO 2 is extracted from air and the extracted CO 2 is delivered to a secondary process where the CO 2 is transformed into an useful or benign product.
  • the CO 2 is delivered in whatever form is required for the secondary process, which may be gaseous, solid, or liquid CO 2 .
  • the secondary process may be any manufacturing, food processing, or other industrial process that uses CO 2 , such as, machining coolant and lubricant, grit blasting, e.g.
  • coffee and tea, supramics pharmaceutical manufacturing, chemical production such as for urea, methanol, inorganic carbonates, organic carbonates, polyurethanes, paint pigments, foaming agents, carbon based fuels, i.e. synthetic fuels, fumigation, e.g. of grain elevators, neutralization of alkaline water, gas shield, e.g. for welding, which are given as exemplary.
  • chemical production such as for urea, methanol, inorganic carbonates, organic carbonates, polyurethanes, paint pigments, foaming agents, carbon based fuels, i.e. synthetic fuels, fumigation, e.g. of grain elevators, neutralization of alkaline water, gas shield, e.g. for welding, which are given as exemplary.
  • a further aspect of the present disclosure provides a method and apparatus for luring CO 2 sensitive insects toward a specific location where a moisture sensitive CO 2 sorbent that is partially or fully loaded with CO 2 is exposed to moisture usually in excess of that present in the ambient air at the location.
  • the sorbent may be held in place by an open basket that is protected with a roof and a floor against accidental wetting by rain.
  • Another aspect of the present disclosure is directed to the control of the concentration of specific gases in a closed environment. While the method and apparatus of this aspect of the present disclosure will be described with specific reference to the control of carbon dioxide in the storage, for example, of bananas, but other fruits and vegetables are also contemplated by this disclosure.
  • the present invention provides a atmosphere-controlled environment for storing produce, wherein other parameters as well as carbon dioxide such as humidity may also be controlled, and a plurality of filters attached to the temperature controlled environment.
  • Yet another aspect of the present disclosure provides a system, i.e. a method and apparatus for extracting carbon dioxide (CO 2 ) from ambient air or an exhaust stack and for delivery, sequestration or conversion of the extracted CO 2 into useful or benign products.
  • CO 2 carbon dioxide
  • FIG. 1 is a schematic showing a system for capturing CO 2 in accordance with the present invention wherein CO 2 is delivered to a secondary process;
  • FIG. 2A is a schematic showing an ion exchange process for capturing CO 2 in accordance with one aspect of the present disclosure wherein multiple chambers are used in succession;
  • FIG. 2B is a schematic showing an ion exchange process for capturing CO 2 where valves are used to control flow between chambers in accordance with the present disclosure
  • FIG. 3 is a schematic showing an ion exchange process for capturing CO 2 employing activated carbon in accordance with one aspect of the present disclosure
  • FIG. 4 is a schematic of an apparatus of the present invention having an electrodialysis cell according to one embodiment of the present disclosure
  • FIG. 5 is a schematic showing a system for capturing CO 2 in accordance with the present disclosure wherein the CO 2 capture device works in tandem with an industrial process to create an essentially carbon neutral system;
  • FIG. 6 is a schematic of a method and apparatus for luring CO 2 -sensitive insects to a desired location according to one aspect of the present disclosure
  • FIG. 7 is a schematic of a method and apparatus for luring CO 2 -sensitive insects to a desired location according to one aspect of the present disclosure.
  • CO 2 capture sorbents include strongly alkaline hydroxide solutions such as, for example, sodium or potassium hydroxide, or a carbonate solution such as, for example, sodium or potassium carbonate brine. See for example published PCT Application PCT/US05/29979 and PCT/US06/029238. See also published PCT Application PCT/US07/802,229 which describes the use of solid sorbents such as ion exchange resins for removing CO 2 from the air.
  • the present invention in one aspect extracts carbon dioxide from ambient air using a conventional CO 2 extraction method or one of the improved CO 2 extraction methods disclosed in our aforesaid PCT Applications, or disclosed herein, and releases at least a portion of the extracted CO 2 to a secondary process employing CO 2 .
  • the CO 2 also may be extracted from an exhaust at the exhaust stack.
  • the present invention provides a system for removing CO 2 from a fluid stream in a capture apparatus, comprising passing the fluid stream in contact with a primary sorbent to absorb CO 2 from the fluid stream.
  • the fluid stream may be ambient air, a flue stream, or any other fluid stream from which the sorbent is capable of withdrawing CO 2 .
  • the CO 2 is then released by the primary sorbent and delivered to a secondary process.
  • the secondary process preferably is connected directly to the CO 2 capture apparatus to minimize transportation costs and potential losses associated therewith.
  • the CO 2 may be transformed into a solid or liquid state.
  • the CO 2 may further be conditioned to a specified pressure and/or temperature.
  • the secondary process may be any manufacturing, food processing, or other industrial process that uses CO 2 , such as for example, machining coolant and lubricant, grit blasting, e.g. for smoothing and paint removal, cryogenic cleaning, quick freeze processes, R744 refrigerant, dry cleaning solvent, perishable shipping container pre-cooling, perishable shipping inert environment maintenance, beverage carbonation, fire suppression, plant fertilization, horticulture, agriculture, silvaculture, aquatic algae production, enhanced oil recovery, water softening, Solvay process, propellant, pressurizing gas, e.g. for aerosol cans, inflation gas, e.g.
  • CO 2 such as for example, machining coolant and lubricant, grit blasting, e.g. for smoothing and paint removal, cryogenic cleaning, quick freeze processes, R744 refrigerant, dry cleaning solvent, perishable shipping container pre-cooling, perishable shipping inert environment maintenance, beverage carbonation, fire suppression, plant fertilization, horticulture
  • the sorbent is a strong base ion exchange resin that has a strong humidity function, that is to say, an ion exchange resin having the ability to take up CO 2 as humidity is decreased, and give up CO 2 as humidity is increased.
  • Such resins may be regenerated by contact with water, humid air, or pulses of steam.
  • the CO 2 is returned to a gaseous phase in a more concentrated form, and no liquid media are brought in contact with the collector material.
  • Other primary sorbents may be regenerated by a secondary sorbent such as weak liquid amine.
  • This amine must be capable of pulling the CO 2 content of gas mixture down so that the CO 2 partial pressure drops to about e.g., 20 to 30 mbar. Thus it can be far weaker sorbent than the primary sorbent and this allows the use of very weak amines.
  • Still other sorbent materials may be regenerated by the application of heat (utilizing a thermal swing), or vacuum pressure.
  • CO 2 is captured and removed from air on a solid phase ion-exchange resin which is placed in a plurality of chambers connected in series. See FIG. 2A .
  • the resins in the different chambers have been exposed for different length of time to the outgassing process.
  • Resins may move from chamber to chamber, or more likely as shown in FIG. 2B , the valving is changed to take a chamber from the purged end of the chain, remove its charge and fill it with a resin which is now put on the unpurged end of the chain.
  • the gas in each chamber is composed of water vapor, CO 2 and possibly an inert sweep gas. The sum of the three partial pressures monotonically declines from the upstream end of the system to the downstream end of the system.
  • the sweep gas pressure can be reduced by increasing the flow speed, but the water vapor pressure is more or less in equilibrium with the liquid water at this point.
  • the CO 2 pressure should increase in the direction of the sweep. If the water vapor is a large part of the total pressure, the water vapor pressure gradient controls the flow and it would be established by a temperature drop from one chamber to the next, while the CO 2 pressure will rise from one chamber to the next, as each chamber is adding some CO 2 to the flow. The contributions of each chamber will be limited by the rate at which the material can release CO 2 and the equilibrium pressure that particular resin can reach.
  • a simple implementation is a set of chamber organized (at least logically into a circle). All but one chamber are filled with water.
  • the water in chamber n ⁇ 1 flows into chamber n, thereby pushing the air inside this chamber out. It is either released to the outside or channeled into chamber n+1 whose water content is moving into chamber n+1.
  • the water pouring into chamber n will inundate the resin that has been replaced into this chamber.
  • the water in chamber n+1 flows into chamber n+2, but rather than obtaining water from chamber n, it pulls in air, which may be the air that resided in chamber n, or fresh air taken from the outside.
  • This procedure could be used with pure water, in which the process is a simple degassing, but it could also be performed with a carbonate solution which is turned into a bicarbonate and where the CO 2 is removed by other means.
  • CO 2 removal could be based on an evacuation (which could be achieved by operating an inverted siphon), or based on electrodialysis, or involve a secondary sorbent that is far more compact and thus allows for an easier regeneration option. It also could involve precipitation of bicarbonate from the solution in a thermal swing or a thermal swing for CO 2 release from the mixture.
  • the basic layout is independent of these ideas.
  • a variation of this idea has all chambers evacuated with the exception of chamber n ⁇ 1 which is filled with water, n which is open to the air, and n+1 which is again filled with water.
  • the nominally evacuated chambers are filled with a mixture of water vapor and CO 2 .
  • we pump water from chamber n ⁇ 1 into n displacing the air to the outside and immersing the resin in water.
  • the pump does not need to do much work, because at the same time the water in chamber n+1 is sucked into chamber n+2, while chamber n+1 fills itself with air.
  • chamber n+1 is filled with air and open to the outside.
  • Chamber n is filled with water and at vacuum pressure.
  • Chamber n+2 is filled with water and at vacuum pressure, and all other chambers are still under vacuum conditions. No net work was done, but all chambers moved by one. We can now renumber all chambers, and repeat the cycle.
  • some of the water vapor may be recovered from the system during the compression stage. This will provide sufficient heat that the system can operate at slightly elevated temperatures. Indeed it is possible to use the last step of pumping out of the gas to severely cool the resin and remove all excess water.
  • CO 2 is captured and removed from air by employing hydrophobic activated carbon materials with strong base ion exchange resins. See FIG. 3 .
  • This latter process is based on observation that activated carbon has been observed to absorb CO 2 when wet, and release the absorbed CO 2 as it dries. This is the opposite behavior from ion exchange resins. Accordingly, this makes it possible to couple solid phase ion exchange resin extractors and activated carbon extractors in sequence.
  • air is passed through the system. As the air dries the resin, it transports the water vapor to the carbon. The resin picks up CO 2 as it dries, and the activated carbon picks up CO 2 as it accepts moisture.
  • the same ion exchange resins may be used to remove excess CO 2 build-up from closed containers such as storage containers for fresh fruit or vegetables, e.g., bananas, in order to maintain a maximum level of CO 2 in the container and avoid excessive ripening or spoilage, as will be described in greater detail below.
  • CO 2 is captured using ion exchange materials and concentrated using an electrodialysis (ED) cell.
  • ED electrodialysis
  • the overall process is as follows: The ion exchange resin is washed using a basic solution, such as sodium carbonate (Na 2 CO 3 ), preferably having a pH of 11-12.
  • the resulting effluent which in the example of a sodium carbonate wash will be primarily sodium bicarbonate (NaHCO 3 ), will preferably have a pH of 9-10.
  • the effluent is then supplied to the acid side of an ED cell, where the reaction is controlled through bipolar and cationic membranes.
  • the acidic side of the cell stabilizes at a near neutral pH, at which point CO 2 evolves and is captured.
  • Osmotic pressure drives water towards the base side of the cell.
  • the basic solution is maintained near a pH of 12 and may also be used to replenish the wash fluid.
  • the present invention provides a system that is substantially carbon neutral, wherein an air capture device, such as those described herein, collects CO 2 that is released by an industrial process employing CO 2 as described above.
  • an air capture device such as those described herein, collects CO 2 that is released by an industrial process employing CO 2 as described above.
  • processes include the use of CO 2 as a refrigerant, as a dry cleaning agent or other solvent, as a fire suppression material, as an oxidation preventing shield-gas in welding or electronics manufacture, as an alternative to sand-blasting, e.g., for smoothing, or paint or rust removal, as a freezing agent in food processing, or any other process where CO 2 is utilized and is later released to the atmosphere.
  • the system effectively creates a loop that is substantially carbon neutral.
  • the air capture device may, for example, be connected the HVAC system of a building where CO 2 is released by processes therein. With the present invention, CO 2 is captured, concentrated and recycled for reuse on site.
  • the invention also may be used to generate carbon credits.
  • a manufacturer may extract CO 2 , and obtain a carbon credit which may be traded or sold, and then use the extracted CO 2 in a secondary process, eliminating the cost of purchasing or generating CO 2 for the secondary process.
  • Another aspect of the present disclosure provides an apparatus and method for using captured CO 2 to attract CO 2 sensitive insects, such as mosquitoes.
  • CO 2 sensitive insects such as mosquitoes.
  • certain insect pests like mosquitoes are attracted to sources of CO 2 , which for them is a way to find a potential victim.
  • lures have been developed for mosquitoes that release CO 2 in the environment in order to attract mosquitoes and potentially other insects.
  • a drawback of most of these devices is that they require gas cartridges of CO 2 or natural gas, propane or butane to produce CO 2 .
  • certain ion exchange materials can be used to absorb CO 2 when they are in a dry state and release it again when they get wet.
  • an application of such a material is described wherein the controlled CO 2 release is used to attract mosquitoes to a device at certain times while at other times the device recharges its CO 2 stores.
  • his aspect of the present disclosure describes a method of luring CO 2 attracted insects by using a CO 2 capture resin that when dry will collect CO 2 from the air and release it again when exposed to moisture.
  • a CO 2 capture resin that when dry will collect CO 2 from the air and release it again when exposed to moisture.
  • This disclosure describes how these resin materials can be used to lure mosquitoes to the device at certain times.
  • the device exposes resin to the air, and containing the resin in a way that is protected from water and rain. During times the device is inactive, it is dry and the resin will collect CO 2 .
  • the device includes a means of applying moisture to the resin material. Moisture application could be achieved by spraying water onto the resin surface, by wicking water into a woven wick that contains the resin material, or by any other means known in the art.
  • the device acts as a lure to attract mosquitoes away from people.
  • the device can be completely open, because no part needs to be kept away from people.
  • the device includes means of killing the pest once it enters the device. This includes but is not limited to electric discharges, or by contact insecticides embedded into the resin matrix.
  • CO 2 lure It is possible to combine the CO 2 lure with other means of attracting insects, including insects that do not respond to the presence of CO 2 .
  • These means include, but are not limited to light and heat sources, sounds, odors or pheromones. Devices of this nature can be designed for indoor and outdoor use. Indoor use in malaria regions may help suppress the incidence of mosquitoes and hence malaria.
  • Another aspect of the present disclosure relates to the capture and release of gases generated by the ripening and preservation of fruits and vegetables.
  • Many produce items i.e., fruits and vegetables
  • Methods for the packaging and shipping of such fruits and vegetables have been developed to maximize the amount of time that the produce may be stored.
  • Many methods for storing and ventilating produce are known that provide various types of bags and containers, including gas permeable membranes, that allow some control of the exposure of the produce to gases such as oxygen, ethylene, and carbon dioxide.
  • these methods do not provide optimal storage conditions and long-term storage options are still desired.
  • U.S. Patent Publication No. 2008/0008793 discloses a method for storing bananas in a controlled environment where oxygen and carbon dioxide levels are optimized in addition to the temperature. Longer periods of storage may be achieved in this environment and improved flavor characteristics may be achieved. The reference fails, however, to discuss how such levels would be reached and maintained.
  • This aspect of the present disclosure provides a method for to stabilizing the CO 2 in a room at any level between 5 ppm and 100,000 ppm.
  • the invention also serves to achieve a low absolute humidity (usually below 25 ppt of water vapor, preferably below 15 ppt, with improved performance as the absolute humidity drops even lower).
  • the method comprises circulating air through a filter box that follows one of the methods for CO 2 absorption describes in one of our aforesaid previous applications.
  • the filter may employ an ion exchange resin that is subject to a humidity swing to absorb CO 2 at the partial pressure representing the desired CO 2 level.
  • the apparatus may include a plurality of such filters operating, wherein each filter will run until the CO 2 uptake rate has slowed down to a predetermined level at which we consider the resin to be essentially fully loaded. This will probably by less than the maximum loading for the resin that can be physically be achieved, but the predetermined level may be optimized for performance at some lower level to improve the collective uptake rate.
  • the uptake rate of the resin will depend primarily on absolute humidity and to some extent on temperature, and can approach one CO 2 per positive elementary fixed charge in the resin.
  • a humidity swing regeneration step follows. Regeneration is accomplished by a change in temperature and absolute humidity, or by wetting the resin, e.g., as described, for example, in U.S. Pat. No. 4,711,645; U.S. Pat. No. 5,318,758; U.S. Pat. No. 5,914,455; U.S. Pat. No. 5,980,611; U.S. Pat. No. 6,117,404; and co-pending U.S. application Ser. No. 11/683,824, and PCT Application Serial No. PCT/US08/82505.
  • Wetting can be accomplished by either dipping the resin into DI or condensation water; by spraying or flowing such water over the resin, (such condensation water may be available from the refrigeration unit operating the storage facility, and may be augmented by condensation water recovered from our unit); by generating steam in a blast of warm air that results in water condensation on the resin material; or by exposing the resin to warm moist air (such warm air may be available from the hot side of the refrigeration unit, it may already be moist or need additional moisture.) If the moisture is added as humidity or by generating steam, it is not necessary to use DI or condensation water.
  • the moist air loaded with CO 2 is then purged from the unit.
  • Heat and water may be recovered in a heat exchange unit that reduces heating demand and water consumption.
  • the present disclosure as discussed above may be used to cover a range of applications from extremely low levels of CO 2 to extremely high levels of CO 2 . It is in principle possible to remove CO 2 from a gas stream that contains CO 2 far in excess of the levels discussed above. Levels around 1 to 10 volume percent could easily be accommodated, and operating above about 10 volume percent CO 2 is also possible. It is advantageous for this design to operate at temperatures below about 15° C., because the loading and unloading characteristics of the resin improve under these conditions.
  • Alternative options at elevated levels of CO 2 include the use of activated carbon, the use of zeolites, the use of weak based amine, or other physical sorbents such as actuated alumina for CO 2 capture instead of ion exchange resin.
  • the present invention provides a method and apparatus for the extraction of a contaminant from a gas stream.
  • the present invention will be described in reference to a method and apparatus for capturing CO 2 from ambient air; however, the invention is also applicable to handling exhaust air or other gas streams and may be used to capture hydrogen sulfide, ammonia, or other common contaminants from such gas streams.
  • the present invention In regenerating the sorbent it is necessary to dry the resin material. This opens an opportunity to combine such system with a vacuum distillation system, and use the heat of evaporation that is released when the material is drying to remove heat from the condenser inside the vacuum distillation system. Whereas the recovery of the CO 2 in most applications requires entering the resin material into a vacuum chamber, the present invention also may be used to drive a complimentary distillation process.
  • the CO 2 sorbent is often an anionic exchange resin, but here we intend to consider all humidity-sensitive CO 2 sorbents that can absorb carbon dioxide from the air when they are dry and release carbon dioxide when they have been exposed to humidity in the form of liquid water and/or partial pressures of water vapor which exceed those at ambient conditions. We will generally refer to such materials as water-sensitive CO 2 sorbents.
  • Vacuum distillation is a standard method of creating fresh water from a brine, such as seawater, brackish water or other salt rich brines pumped from underground.
  • brine is also used to refer to contaminated water that is otherwise unsuitable as fresh water, such as for example, waters contaminated with biological waste materials.
  • the term “brine” encompasses all waters contaminated with materials from which water can be separated by vacuum distillation.
  • Vacuum distillation begins with a chamber that has been at least partially evacuated. Brine is introduced into the chamber and is separated into two components: concentrated brine and fresh water product.
  • concentrated brine and fresh water product.
  • the apparatus comprises a vacuum chamber that is divided into at least two parts; an evaporator unit and a condenser unit.
  • a vacuum chamber that is divided into at least two parts; an evaporator unit and a condenser unit.
  • brine As brine is introduced into the evaporator unit, it is allowed to evaporate. In this manner the water vapor becomes separated from the contaminants in the brine.
  • the water vapor is then passed to a condenser unit, where it is allowed to condense. It is necessary to remove heat of condensation to keep from impeding further condensation in the condenser unit. This heat may be passed to the evaporator unit, enabling the evaporation to occur, by counterflow or some other method.
  • the evaporator unit which is initially evacuated, fills with water vapor.
  • the equilibrium partial pressure over the brine in the evaporator unit is a function of the temperature and of the salt content of the brine.
  • the equilibrium partial pressure over the condensate in the condenser unit is a function of the temperature. At equal temperature, the equilibrium partial pressure over the condensate is slightly higher than over the brine.
  • One way to condense the water vapor in the condenser unit is to raise the pressure, wherein the water vapor will condense at ambient temperatures. This may be accomplished using a compressor to drive up the pressure. The heat of condensation will cause the temperature to rise in the condenser unit, wherein the heat deposited by the condensation can then be transferred to the evaporator unit.
  • the compression acts in effect as a heat pump which transfers heat from the brine to the condensate, and a return heat flow balances out the total heat fluxes inside the system.
  • the heat produced by that process can be transferred to the sorbent to raise its temperature as required.
  • the heat required to drive the sorbent to the requisite temperature can also be derived from the condensation of water that has been allowed to evaporate at ambient conditions.
  • Another approach is to maintain by some other system a temperature gradient between the evaporator unit and the condenser unit, which is enough to cause a gradient in the equilibrium partial pressure that causes vapor to flow from the evaporator unit to the condenser unit.
  • a temperature differential it is necessary to provide the heat of evaporation on the evaporator unit, and remove the heat of condensation on the condenser unit of the chamber.
  • the required temperature differences are small; a few degrees between the evaporator and the condensate are sufficient. Operational temperatures can be low and could be well within the range of ambient temperatures, particularly in warmer climates.
  • One way of establishing the temperature gradient is to generate heat and transfer it to the evaporator.
  • Another way of establishing the temperature gradient is to actively remove heat on the condenser unit. This requires a heat exchange system that removes heat from the condensate. In such an operation of the device, the temperature of the brine is higher than that of the condenser unit the heat is passed through and cannot be recovered within the system. In principle it is possible to couple one or more additional heat pumps to the system, which pumps the heat removed at the condenser unit and returns it to the evaporation side.
  • the water vapor is evaporated from the brine and is partly absorbed onto the resin. This will release a substantial portion of the CO 2 or other targeted contaminant from the sorbent.
  • this step is performed in a vacuum chamber, the atmosphere of the chamber will be filled primarily with water vapor and CO 2 .
  • the vacuum chamber will also aid in the evaporation of the water vapor in the brine.
  • the concentrated brine is then removed and the water is then condensed out of the CO 2 .
  • the present invention produces a distilled water stream as well as concentrated CO 2 .
  • Providing heat to the drying resin is advantageous and one can therefore integrate a heat exchange system operating between the drying resin collector and the condenser inside the vacuum system.
  • the evaporation of the water from the resin would not produce quite enough water to make up the water losses from the system; therefore it would have to be augmented by additional brine evaporation.
  • Another aspect of the present disclosure provides a different process whereby ambient environmental temperatures are used to maintain a constant temperature at the condenser unit, i.e. by flowing ambient air, or ambient water through the heat exchanger on the brine evaporation side, and we use additional brine, e.g. seawater, to operate an evaporative cooler that creates the temperature drop necessary to force the condensation of clean water inside the vacuum chamber.
  • additional brine e.g. seawater
  • the system disclosed herein comprises a vacuum chamber with means of introducing and removing a brine, with means for removal of clean water condensate, with internal surfaces on which the brine is allowed to evaporate, and surfaces of a lower temperature where the water vapor is allowed to condense.
  • the surfaces on which the brine is evaporating are in close contact with a heat exchanger that provides the necessary heat to maintain evaporation. It is advantageous to use free heat, i.e., heat from the ambient environment, which may have been augmented by heat, e.g. from sunshine, or, e.g. waste heat.
  • the surfaces on which water vapor is allowed to condense are in close contact with a heat exchanger that uses additional brine to provide evaporative cooling required to force the condensation.
  • brine is consumed both inside and outside the chamber.
  • the maximum acceptable concentration of the discharge brine will limit the amount of evaporation that is acceptable.
  • the rate of consumption in both cases is similar.
  • the two waste streams can be combined and mixed for return to the ocean or brine reservoir.
  • the returned concentrated brine is slightly cooler than ambient temperatures.
  • CO 2 membrane that separates CO 2 from nitrogen and oxygen.
  • One option would be to use a carbonic anhydrase based membrane separation technology.
  • membranes with similar properties to the ion exchange resin discussed more fully in our other applications, (see Appendix A).
  • the thin resin membrane would transfer CO 2 according to a pressure gradient in CO 2 and against a pressure gradient in water vapor. The two combined create a net flow of CO 2 across the membrane and thus by keeping the outside of the membrane wet or in high humidity one would create two chemical potentials that will drive CO 2 across the membrane.
  • the CO 2 management is preferably integrated with de-humidification, or humidification of the air as the case may be, and it may also be integrated with the temperature control and AC handling of the air.
  • the CO 2 stabilization unit shares the air handling and blowing equipment with the other tasks, and it may be built into the same set of ducts. It can take advantage of heat and condensation water produced in the refrigeration unit.
  • the present disclosure in another aspect provides an additional use for extracted CO 2 .
  • the extracted CO 2 is employed to neutralize carbonic acid.
  • the present invention takes advantage of the fact that in sequestration, if one can drive the partial pressure of CO 2 up by about a factor of about 100, the concentrated CO 2 may then be injected into alkaline brines, to neutralize the brine.
  • hydrophobic membranes may be used to create a gas phase interface between two liquids, or between a liquid and a gas. If the brine covers one side of the membrane it is possible to pull CO 2 gas through the membrane without bringing contaminant ions in contact with the sorbent resin.
  • an alkaline brine which is preferably in a temperature range between 40 and 60° C., and use the water vapor to recover CO 2 from our resins.
  • the heated alkaline brine will provide a high level of moisture which induces the resin to give off CO 2 while it at the same time prevents the CO 2 level from rising substantially. If operated in a vacuum the process should not be transport limited. In the presence of atmospheric pressures, however, the process could be transport limited.
  • the resin which has been saturated with CO 2 in ambient air, is brought into a chamber connected to a second chamber containing wetted surfaces over which the brine flows.
  • the brine will establish a high level of humidity and the resulting high humidity air is blown over the sorbent material. In one aspect of this invention this exchange will occur with humid air entering the chamber.
  • residual air in the chamber is at least partially removed by evacuation prior to running water vapor through the chamber. As the water vapor is circulated between the wetted surfaces and the sorbent material, it carries CO 2 that is released to the alkaline brine where it is absorbed into the brine. In this implementation the resinfunctions to speed up the transfer of CO 2 from ambient air into the alkaline brine.
  • Further acceleration of the transfer of CO 2 may be achieved with other materials, such as, for example, with carbonic anhydrase that thereby would open the use of brines with relatively low levels of alkalinity e.g with a pH of 8-11. In this range one could even use seawater, even though the accelerated acidification of seawater would in many cases be counter-productive. However, this would not be the case, for example, where the source of an alkaline brine is an underground aquifer, from which brine is removed and to which it is returned once the CO 2 is absorbed.
  • the brine could also be water that has been exposed to alkaline mineral rocks such as basalt or peridotite or serpentinite rock. For example, one could percolate the water through a pile of serpentine tailings or other tailings that can release alkalinity.
  • serpentine tailings to increase alkalinity is known in the art.
  • the serpentine could be mined for this purposes It also is possible in some formations to inject water into alkaline underground systems for the purpose of enriching it with base cations. The presence of CO 2 in the water may speed up this process.
  • Another source of alkalinity could be Mg(OH) 2 that has resulted from the processing of serpentine and olivine.
  • the dissolution of limestone with air captured CO 2 is analogous to a process in which the CO 2 comes from a power plant.
  • the present invention provides a substantial advantage over a power plant in that we do not have to bring enormous amounts of lime stone to a power plant, or distribute the CO 2 from a power plant to many different processing sites, but that we can instead develop a facility where seawater, lime and CO 2 from the air come together more easily.
  • One specific implementation would be to create a small basin that is periodically flushed with seawater.
  • the CO 2 is provided by air capture devices located adjacent to or even above the water surface. Of particular interest are sites where limestone or other forms of calcium carbonate (such as empty mussel shells) are readily available as well. If we have calcium carbonate, seawater and air capture devices in one place, we can provide a way of disposing of CO 2 in ocean water without raising the pH of the water.

Abstract

The present disclosure provides a method and apparatus for extracting carbon dioxide (CO2) from a fluid stream and for delivering that extracted CO2 to controlled environments for utilization by a secondary process. Various extraction and delivery methods are disclosed specific to certain secondary uses, included the attraction of CO2-sensitive insects, the ripening and preservation of produce, and the neutralization of brine.

Description

    CROSS-REFERENCE TO RELATED APPLICATIONS
  • This application claims priority from U.S. provisional application Ser. No. 61/029,831, filed Feb. 19, 2008, Ser. No. 61/074,972 filed Jun. 23, 2008 and Ser. No. 61/079,776 filed Jul. 10, 2008.
  • FIELD OF THE INVENTION
  • The present invention relates to a method and apparatus for the removal of selected gases from an environment and the disposal of the selected gases in another environment.
  • BACKGROUND OF THE INVENTION
  • The present invention in one aspect relates to removal of selected gases from the atmosphere. The invention has particular utility in connection with the extraction of carbon dioxide (CO2) from the atmosphere and subsequent sequestration of the extracted CO2 or conversion of the extracted CO2 to useful or benign products and will be described in connection with such utilities, although other utilities are contemplated, including the extraction, sequestration or conversion of other gases from the atmosphere including NOx and SO2.
  • There is compelling evidence of a strong correlation between the sharply increasing levels of atmospheric CO2 with a commensurate increase in global surface temperatures. This effect is commonly known as Global Warming. Of the various sources of the CO2 emissions, there are a vast number of small, widely distributed emitters that are impractical to mitigate at the source. Additionally, large-scale emitters such as hydrocarbon-fueled power plants are not fully protected from exhausting CO2 into the atmosphere. Combined, these major sources, as well as others, have lead to the creation of a sharply increasing rate of atmospheric CO2 concentration. Until all emitters are corrected at their source, other technologies are required to capture the increasing, albeit relatively low, background levels of atmospheric CO2. Efforts are underway to augment existing emissions reducing technologies as well as the development of new and novel techniques for the direct capture of ambient CO2. These efforts require methodologies to manage the resulting concentrated waste streams of CO2 in such a manner as to prevent its reintroduction to the atmosphere.
  • The production of CO2 occurs in a variety of industrial applications such as the generation of electricity from coal at power plants and in the use of hydrocarbons that are typically the main components of fuels that are combusted in combustion devices, such as engines. Exhaust gas discharged from such combustion devices contains CO2 gas, which at present is simply released to the atmosphere. However, as greenhouse gas concerns mount, CO2 emissions from all sources will have to be curtailed. For mobile sources such as motor vehicles and airplanes the best option is likely to be the collection of CO2 directly from the air rather than from the mobile device in the motor vehicle or airplane. The advantage of removing CO2 from air is that it eliminates the need for storing CO2 on the mobile device.
  • Extracting carbon dioxide (CO2) from ambient air would make it possible to use carbon-based fuels and deal with the associated greenhouse gas emissions after the fact. Since CO2 is neither poisonous nor harmful in parts per million quantities, but creates environmental problems simply by accumulating in the atmosphere, it is possible to remove CO2 from air in order to compensate for equally sized emissions elsewhere and at different times.
  • BRIEF SUMMARY OF THE INVENTION
  • The present disclosure provides a system, i.e. a method and apparatus for extracting a contaminant from a flow stream, such as ambient air or an exhaust stack, and for delivering the extracted contaminant for use in a secondary process. The present disclosure is described primarily in regards to the removal and sequestration of CO2, though the apparatus and method of the present disclosure may be used with various other contaminants.
  • In accordance with one aspect of the present disclosure, CO2 is extracted from air and the extracted CO2 is delivered to a secondary process where the CO2 is transformed into an useful or benign product. The CO2 is delivered in whatever form is required for the secondary process, which may be gaseous, solid, or liquid CO2. The secondary process may be any manufacturing, food processing, or other industrial process that uses CO2, such as, machining coolant and lubricant, grit blasting, e.g. for smoothing and paint removal, cryogenic cleaning, quick freeze processes, production and use of R744 refrigerant, CO2 based dry cleaning solvents, perishable shipping container pre-cooling, perishable shipping inert environment maintenance, beverage carbonation, fire suppression, plant fertilization, horticulture, agriculture, silvaculture, aquatic algae production, enhanced oil recovery, water softening, Solvay process, propellant, pressurizing gas, e.g. for aerosol cans, inflation gas, e.g. for life rafts, supercritical CO2 extraction, semi conductor manufacturing, organic solvent, perfume aromatics, decaffeinating beverages, e.g. coffee and tea, supramics, pharmaceutical manufacturing, chemical production such as for urea, methanol, inorganic carbonates, organic carbonates, polyurethanes, paint pigments, foaming agents, carbon based fuels, i.e. synthetic fuels, fumigation, e.g. of grain elevators, neutralization of alkaline water, gas shield, e.g. for welding, which are given as exemplary.
  • A further aspect of the present disclosure provides a method and apparatus for luring CO2 sensitive insects toward a specific location where a moisture sensitive CO2 sorbent that is partially or fully loaded with CO2 is exposed to moisture usually in excess of that present in the ambient air at the location. The sorbent may be held in place by an open basket that is protected with a roof and a floor against accidental wetting by rain.
  • Another aspect of the present disclosure is directed to the control of the concentration of specific gases in a closed environment. While the method and apparatus of this aspect of the present disclosure will be described with specific reference to the control of carbon dioxide in the storage, for example, of bananas, but other fruits and vegetables are also contemplated by this disclosure. The present invention provides a atmosphere-controlled environment for storing produce, wherein other parameters as well as carbon dioxide such as humidity may also be controlled, and a plurality of filters attached to the temperature controlled environment.
  • Yet another aspect of the present disclosure provides a system, i.e. a method and apparatus for extracting carbon dioxide (CO2) from ambient air or an exhaust stack and for delivery, sequestration or conversion of the extracted CO2 into useful or benign products.
  • The extraction of the contaminant from a gas stream in any of the aspects of the present disclosure discussed above may be accomplished by using one of a number of methods such as disclosed in the several patent applications listed in Appendix A, the contents of which are incorporated herein by reference, as well as other extraction processes described in the literature and patent art, including processes which capture CO2 at the stack.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • Further features and advantages of the present invention will be seen from the following detailed description, taken in conjunction with the accompanying drawings, wherein
  • FIG. 1 is a schematic showing a system for capturing CO2 in accordance with the present invention wherein CO2 is delivered to a secondary process;
  • FIG. 2A is a schematic showing an ion exchange process for capturing CO2 in accordance with one aspect of the present disclosure wherein multiple chambers are used in succession;
  • FIG. 2B is a schematic showing an ion exchange process for capturing CO2 where valves are used to control flow between chambers in accordance with the present disclosure;
  • FIG. 3 is a schematic showing an ion exchange process for capturing CO2 employing activated carbon in accordance with one aspect of the present disclosure;
  • FIG. 4 is a schematic of an apparatus of the present invention having an electrodialysis cell according to one embodiment of the present disclosure;
  • FIG. 5 is a schematic showing a system for capturing CO2 in accordance with the present disclosure wherein the CO2 capture device works in tandem with an industrial process to create an essentially carbon neutral system;
  • FIG. 6 is a schematic of a method and apparatus for luring CO2-sensitive insects to a desired location according to one aspect of the present disclosure;
  • FIG. 7 is a schematic of a method and apparatus for luring CO2-sensitive insects to a desired location according to one aspect of the present disclosure.
  • DETAILED DESCRIPTION
  • Various methods and apparatus have been developed for removing CO2 from air. For example, we have recently disclosed methods for efficiently extracting carbon dioxide (CO2) from ambient air using sorbents that either physically or chemically bind and remove CO2 from the air. A class of practical CO2 capture sorbents include strongly alkaline hydroxide solutions such as, for example, sodium or potassium hydroxide, or a carbonate solution such as, for example, sodium or potassium carbonate brine. See for example published PCT Application PCT/US05/29979 and PCT/US06/029238. See also published PCT Application PCT/US07/802,229 which describes the use of solid sorbents such as ion exchange resins for removing CO2 from the air.
  • In broad concept, the present invention in one aspect extracts carbon dioxide from ambient air using a conventional CO2 extraction method or one of the improved CO2 extraction methods disclosed in our aforesaid PCT Applications, or disclosed herein, and releases at least a portion of the extracted CO2 to a secondary process employing CO2. The CO2 also may be extracted from an exhaust at the exhaust stack.
  • In our co-pending U.S. application Ser. No. 11/866,326, assigned to a common assignee and incorporated by reference herein, there are provided methods and apparati for extracting carbon dioxide (CO2) from ambient air and for delivering that extracted CO2 to controlled environments. Specifically, the aforementioned applications disclose the delivery of CO2 collected from ambient air or from exhaust gases for use in greenhouses or in algae cultures. The CO2 is extracted from the gas stream by an ion exchange material that when exposed to dry air absorbs CO2 that it will release at a higher partial pressure when exposed to moisture. In this process we can achieve concentration enhancements by factors of from 1 to 100.
  • In a first exemplary embodiment shown in FIG. 1, the present invention provides a system for removing CO2 from a fluid stream in a capture apparatus, comprising passing the fluid stream in contact with a primary sorbent to absorb CO2 from the fluid stream. The fluid stream may be ambient air, a flue stream, or any other fluid stream from which the sorbent is capable of withdrawing CO2. The CO2 is then released by the primary sorbent and delivered to a secondary process.
  • The secondary process preferably is connected directly to the CO2 capture apparatus to minimize transportation costs and potential losses associated therewith. Depending on the intended secondary process, the CO2 may be transformed into a solid or liquid state. The CO2 may further be conditioned to a specified pressure and/or temperature.
  • The secondary process may be any manufacturing, food processing, or other industrial process that uses CO2, such as for example, machining coolant and lubricant, grit blasting, e.g. for smoothing and paint removal, cryogenic cleaning, quick freeze processes, R744 refrigerant, dry cleaning solvent, perishable shipping container pre-cooling, perishable shipping inert environment maintenance, beverage carbonation, fire suppression, plant fertilization, horticulture, agriculture, silvaculture, aquatic algae production, enhanced oil recovery, water softening, Solvay process, propellant, pressurizing gas, e.g. for aerosol cans, inflation gas, e.g. for life rafts, supercritical CO2 extraction, semi conductor manufacturing, organic solvent, perfume aromatics, decaffeinating beverages, e.g. coffee and tea, supramics, pharmaceutical manufacturing, chemical production such as for urea, methanol, inorganic carbonates, organic carbonates, polyurethanes, paint pigments, foaming agents, carbon based fuels, i.e. synthetic fuels, fumigation, e.g. of grain elevators, neutralization of alkaline water, gas shield, e.g. for welding, Many other processes utilizing CO2 are also possible and are deemed to be within the scope of this disclosure.
  • Our aforementioned commonly owned applications disclose several potential primary sorbents that may be used to capture and remove CO2 from the air. In one approach to CO2 capture, the sorbent is a strong base ion exchange resin that has a strong humidity function, that is to say, an ion exchange resin having the ability to take up CO2 as humidity is decreased, and give up CO2 as humidity is increased. Such resins may be regenerated by contact with water, humid air, or pulses of steam. In this approach the CO2 is returned to a gaseous phase in a more concentrated form, and no liquid media are brought in contact with the collector material.
  • Other primary sorbents may be regenerated by a secondary sorbent such as weak liquid amine. This amine must be capable of pulling the CO2 content of gas mixture down so that the CO2 partial pressure drops to about e.g., 20 to 30 mbar. Thus it can be far weaker sorbent than the primary sorbent and this allows the use of very weak amines.
  • Still other sorbent materials may be regenerated by the application of heat (utilizing a thermal swing), or vacuum pressure.
  • In another example, CO2 is captured and removed from air on a solid phase ion-exchange resin which is placed in a plurality of chambers connected in series. See FIG. 2A. The resins in the different chambers have been exposed for different length of time to the outgassing process. Resins may move from chamber to chamber, or more likely as shown in FIG. 2B, the valving is changed to take a chamber from the purged end of the chain, remove its charge and fill it with a resin which is now put on the unpurged end of the chain. The gas in each chamber is composed of water vapor, CO2 and possibly an inert sweep gas. The sum of the three partial pressures monotonically declines from the upstream end of the system to the downstream end of the system. The sweep gas pressure can be reduced by increasing the flow speed, but the water vapor pressure is more or less in equilibrium with the liquid water at this point. The CO2 pressure should increase in the direction of the sweep. If the water vapor is a large part of the total pressure, the water vapor pressure gradient controls the flow and it would be established by a temperature drop from one chamber to the next, while the CO2 pressure will rise from one chamber to the next, as each chamber is adding some CO2 to the flow. The contributions of each chamber will be limited by the rate at which the material can release CO2 and the equilibrium pressure that particular resin can reach.
  • The following conceptually describes a CO2 washing system that is based on immersing the resin into liquid water and moving the water over the resin into a separate chamber where the CO2 is allowed to be released from the water.
  • A simple implementation is a set of chamber organized (at least logically into a circle). All but one chamber are filled with water. One chamber (n) is empty and filled with air. Initially chamber n is filled with air, and chamber n+1 is filled with water. Now water is pumped against a minimal pressure drop from chamber k to k+1. This will work for all values of k, except that k=n−1, n, n+1 are special cases which need further consideration. The water in chamber n−1 flows into chamber n, thereby pushing the air inside this chamber out. It is either released to the outside or channeled into chamber n+1 whose water content is moving into chamber n+1. The water pouring into chamber n will inundate the resin that has been replaced into this chamber. The water in chamber n+1 flows into chamber n+2, but rather than obtaining water from chamber n, it pulls in air, which may be the air that resided in chamber n, or fresh air taken from the outside.
  • At this point we renumber all chambers by replacing n with n−1. Thus it is again chamber n that is filled with air. We now open chamber n, and remove the regenerated resin and replace it with fully loaded resin. Before we load up chamber n, we pump the water from station n−1 to a degassing station and from there to station n+1. This water flow bypasses the currently open chamber n.
  • This procedure could be used with pure water, in which the process is a simple degassing, but it could also be performed with a carbonate solution which is turned into a bicarbonate and where the CO2 is removed by other means. CO2 removal could be based on an evacuation (which could be achieved by operating an inverted siphon), or based on electrodialysis, or involve a secondary sorbent that is far more compact and thus allows for an easier regeneration option. It also could involve precipitation of bicarbonate from the solution in a thermal swing or a thermal swing for CO2 release from the mixture. The basic layout is independent of these ideas.
  • A variation of this idea has all chambers evacuated with the exception of chamber n−1 which is filled with water, n which is open to the air, and n+1 which is again filled with water. The nominally evacuated chambers are filled with a mixture of water vapor and CO2. In this case, we pump water from chamber n−1 into n, displacing the air to the outside and immersing the resin in water. The pump does not need to do much work, because at the same time the water in chamber n+1 is sucked into chamber n+2, while chamber n+1 fills itself with air. At the end of this process chamber n+1 is filled with air and open to the outside. Chamber n is filled with water and at vacuum pressure. Chamber n+2 is filled with water and at vacuum pressure, and all other chambers are still under vacuum conditions. No net work was done, but all chambers moved by one. We can now renumber all chambers, and repeat the cycle.
  • In this case we use the water to stimulate the gas release and the freshly wetted resin in the last chamber is now topping off the CO2 which is pumped out of this chamber, letting gas flow from all other chambers into this one. The CO2 content of the water is likely to be high, however, it remains more or less constant over time as we do not extract this CO2, so after some initial transients, this CO2 reservoir will remain constant and not remove CO2 from the resin (we ignore here some small losses to the outside air which are not completely avoidable) check valves can be installed to prevent backward flow. As a result we have a water driven implementation of the CO2 release which his significantly simpler than a water vapor driven system.
  • Optionally, some of the water vapor may be recovered from the system during the compression stage. This will provide sufficient heat that the system can operate at slightly elevated temperatures. Indeed it is possible to use the last step of pumping out of the gas to severely cool the resin and remove all excess water.
  • Yet other possibilities exist. For example, it is possible to create a buffer storage for the water which makes it possible to slowly withdraw water from chamber n−1 and in a second step fill chamber n very rapidly so as to minimize the amount of time the water is in contact with air and thus can exchange gas with the outside air. The buffer itself must be able to change volume. It takes on an additional volume as it takes on the fluid from chamber n−1. It then contracts again as it pushes the same volume into chamber n.
  • Again mechanical work is related to friction losses, inertial losses, and losses to slight pressure mismatches between the various chambers. This can be adjusted for with careful thermal management.
  • In yet another example CO2 is captured and removed from air by employing hydrophobic activated carbon materials with strong base ion exchange resins. See FIG. 3. This latter process is based on observation that activated carbon has been observed to absorb CO2 when wet, and release the absorbed CO2 as it dries. This is the opposite behavior from ion exchange resins. Accordingly, this makes it possible to couple solid phase ion exchange resin extractors and activated carbon extractors in sequence. Starting with dry activated carbon and moistened resin materials air is passed through the system. As the air dries the resin, it transports the water vapor to the carbon. The resin picks up CO2 as it dries, and the activated carbon picks up CO2 as it accepts moisture. Once the resin is dry, the system is reversed, and fresh air is flowed through the activated carbon, and releases moisture back to the ion exchange resins. As the carbon dries it gives off CO2, raising the CO2 partial pressure where it can be concentrated and removed. A feature and advantage of coupling ion exchange material and activated carbon in this manner is that water is preserved, and is a simple matter of valving to reverse air flow. Alternatively, zeolite materials may be used in place of activated carbon. By stringing several air capture devices together, the ambient CO2 removed may be concentrated before passing to a secondary process.
  • The same ion exchange resins may be used to remove excess CO2 build-up from closed containers such as storage containers for fresh fruit or vegetables, e.g., bananas, in order to maintain a maximum level of CO2 in the container and avoid excessive ripening or spoilage, as will be described in greater detail below.
  • In another aspect of the present invention shown in FIG. 4, CO2 is captured using ion exchange materials and concentrated using an electrodialysis (ED) cell. The overall process is as follows: The ion exchange resin is washed using a basic solution, such as sodium carbonate (Na2CO3), preferably having a pH of 11-12. The resulting effluent, which in the example of a sodium carbonate wash will be primarily sodium bicarbonate (NaHCO3), will preferably have a pH of 9-10. The effluent is then supplied to the acid side of an ED cell, where the reaction is controlled through bipolar and cationic membranes. After an initial run, the acidic side of the cell stabilizes at a near neutral pH, at which point CO2 evolves and is captured. Osmotic pressure drives water towards the base side of the cell. The basic solution is maintained near a pH of 12 and may also be used to replenish the wash fluid.
  • In another exemplary embodiment shown in FIG. 5, the present invention provides a system that is substantially carbon neutral, wherein an air capture device, such as those described herein, collects CO2 that is released by an industrial process employing CO2 as described above. For example, such processes include the use of CO2 as a refrigerant, as a dry cleaning agent or other solvent, as a fire suppression material, as an oxidation preventing shield-gas in welding or electronics manufacture, as an alternative to sand-blasting, e.g., for smoothing, or paint or rust removal, as a freezing agent in food processing, or any other process where CO2 is utilized and is later released to the atmosphere. The system effectively creates a loop that is substantially carbon neutral. The air capture device may, for example, be connected the HVAC system of a building where CO2 is released by processes therein. With the present invention, CO2 is captured, concentrated and recycled for reuse on site.
  • The invention also may be used to generate carbon credits. Thus, a manufacturer may extract CO2, and obtain a carbon credit which may be traded or sold, and then use the extracted CO2 in a secondary process, eliminating the cost of purchasing or generating CO2 for the secondary process.
  • Another aspect of the present disclosure provides an apparatus and method for using captured CO2 to attract CO2 sensitive insects, such as mosquitoes. It is known that certain insect pests like mosquitoes are attracted to sources of CO2, which for them is a way to find a potential victim. In recent years lures have been developed for mosquitoes that release CO2 in the environment in order to attract mosquitoes and potentially other insects. A drawback of most of these devices is that they require gas cartridges of CO2 or natural gas, propane or butane to produce CO2. In related applications it has been shown how certain ion exchange materials can be used to absorb CO2 when they are in a dry state and release it again when they get wet. Here an application of such a material is described wherein the controlled CO2 release is used to attract mosquitoes to a device at certain times while at other times the device recharges its CO2 stores.
  • Referring to FIG. 6, his aspect of the present disclosure describes a method of luring CO2 attracted insects by using a CO2 capture resin that when dry will collect CO2 from the air and release it again when exposed to moisture. A number of such materials have been described in previous disclosures. This disclosure describes how these resin materials can be used to lure mosquitoes to the device at certain times.
  • It is possible to expose an amount of resin to air so as to load it with CO2. When the device is activated, e.g. in the evening the resin is exposed to humid air, or is directly wetted for example by a small water spray. As a result the resin will begin releasing CO2 therefore creating an environment that will attract mosquitoes. One implementation, for example, would be a small container filled with polymer strands of the ion exchange resins and similar materials that can be used to absorb CO2. The purpose of the CO2 release is to attract certain insects, like mosquitoes that are attracted by CO2.
  • The device exposes resin to the air, and containing the resin in a way that is protected from water and rain. During times the device is inactive, it is dry and the resin will collect CO2. The device includes a means of applying moisture to the resin material. Moisture application could be achieved by spraying water onto the resin surface, by wicking water into a woven wick that contains the resin material, or by any other means known in the art.
  • The device acts as a lure to attract mosquitoes away from people. In this case the device can be completely open, because no part needs to be kept away from people. In another implementation the device includes means of killing the pest once it enters the device. This includes but is not limited to electric discharges, or by contact insecticides embedded into the resin matrix.
  • It is possible to combine the CO2 lure with other means of attracting insects, including insects that do not respond to the presence of CO2. These means include, but are not limited to light and heat sources, sounds, odors or pheromones. Devices of this nature can be designed for indoor and outdoor use. Indoor use in malaria regions may help suppress the incidence of mosquitoes and hence malaria.
  • Another aspect of the present disclosure relates to the capture and release of gases generated by the ripening and preservation of fruits and vegetables. Many produce items, i.e., fruits and vegetables, are often stored in a temperature-controlled environment in order to control the ripening process. Methods for the packaging and shipping of such fruits and vegetables have been developed to maximize the amount of time that the produce may be stored. Many methods for storing and ventilating produce are known that provide various types of bags and containers, including gas permeable membranes, that allow some control of the exposure of the produce to gases such as oxygen, ethylene, and carbon dioxide. However, these methods do not provide optimal storage conditions and long-term storage options are still desired.
  • U.S. Patent Publication No. 2008/0008793, incorporated by reference herein, discloses a method for storing bananas in a controlled environment where oxygen and carbon dioxide levels are optimized in addition to the temperature. Longer periods of storage may be achieved in this environment and improved flavor characteristics may be achieved. The reference fails, however, to discuss how such levels would be reached and maintained.
  • This aspect of the present disclosure provides a method for to stabilizing the CO2 in a room at any level between 5 ppm and 100,000 ppm. The invention also serves to achieve a low absolute humidity (usually below 25 ppt of water vapor, preferably below 15 ppt, with improved performance as the absolute humidity drops even lower).
  • Referring to FIG. 7, the method comprises circulating air through a filter box that follows one of the methods for CO2 absorption describes in one of our aforesaid previous applications. For example, the filter may employ an ion exchange resin that is subject to a humidity swing to absorb CO2 at the partial pressure representing the desired CO2 level. The apparatus may include a plurality of such filters operating, wherein each filter will run until the CO2 uptake rate has slowed down to a predetermined level at which we consider the resin to be essentially fully loaded. This will probably by less than the maximum loading for the resin that can be physically be achieved, but the predetermined level may be optimized for performance at some lower level to improve the collective uptake rate. The uptake rate of the resin will depend primarily on absolute humidity and to some extent on temperature, and can approach one CO2 per positive elementary fixed charge in the resin.
  • Once the resin is loaded the air intake is closed or the resin filter may be moved into a separate chamber. A humidity swing regeneration step follows. Regeneration is accomplished by a change in temperature and absolute humidity, or by wetting the resin, e.g., as described, for example, in U.S. Pat. No. 4,711,645; U.S. Pat. No. 5,318,758; U.S. Pat. No. 5,914,455; U.S. Pat. No. 5,980,611; U.S. Pat. No. 6,117,404; and co-pending U.S. application Ser. No. 11/683,824, and PCT Application Serial No. PCT/US08/82505. Wetting can be accomplished by either dipping the resin into DI or condensation water; by spraying or flowing such water over the resin, (such condensation water may be available from the refrigeration unit operating the storage facility, and may be augmented by condensation water recovered from our unit); by generating steam in a blast of warm air that results in water condensation on the resin material; or by exposing the resin to warm moist air (such warm air may be available from the hot side of the refrigeration unit, it may already be moist or need additional moisture.) If the moisture is added as humidity or by generating steam, it is not necessary to use DI or condensation water.
  • The moist air loaded with CO2 is then purged from the unit. Heat and water may be recovered in a heat exchange unit that reduces heating demand and water consumption.
  • The present disclosure as discussed above may be used to cover a range of applications from extremely low levels of CO2 to extremely high levels of CO2. It is in principle possible to remove CO2 from a gas stream that contains CO2 far in excess of the levels discussed above. Levels around 1 to 10 volume percent could easily be accommodated, and operating above about 10 volume percent CO2 is also possible. It is advantageous for this design to operate at temperatures below about 15° C., because the loading and unloading characteristics of the resin improve under these conditions.
  • Alternative options at elevated levels of CO2 include the use of activated carbon, the use of zeolites, the use of weak based amine, or other physical sorbents such as actuated alumina for CO2 capture instead of ion exchange resin.
  • In broad aspect the present invention provides a method and apparatus for the extraction of a contaminant from a gas stream. The present invention will be described in reference to a method and apparatus for capturing CO2 from ambient air; however, the invention is also applicable to handling exhaust air or other gas streams and may be used to capture hydrogen sulfide, ammonia, or other common contaminants from such gas streams.
  • In co-pending PCT International Patent Application Serial No. PCT/US07/84880; U.S. Provisional Patent Application Ser. No. 60/985,586, assigned to a common assignee and incorporated by reference herein, we discuss a CO2 capture process that utilizes a humidity swing to regenerate a sorbent, releasing a mixture of CO2 and water vapor. The water vapor may be removed from the mixture by compression or cooling, either of which will cause the water vapor to condense and precipitate out of the mixture.
  • To perform the humidity swing, it often is useful to expose the sorbent to low pressure water vapor. In order to achieve the required minimum water vapor pressure, it is may be necessary to operate above ambient temperatures as the maximum water vapor pressure is significantly dependent on temperature. To that end, the aforementioned co-pending applications discuss how to transfer heat to loaded sorbents that need to be inserted into an environment that is at a higher temperature.
  • In regenerating the sorbent it is necessary to dry the resin material. This opens an opportunity to combine such system with a vacuum distillation system, and use the heat of evaporation that is released when the material is drying to remove heat from the condenser inside the vacuum distillation system. Whereas the recovery of the CO2 in most applications requires entering the resin material into a vacuum chamber, the present invention also may be used to drive a complimentary distillation process.
  • As explained in the aforementioned co-pending applications, the CO2 sorbent is often an anionic exchange resin, but here we intend to consider all humidity-sensitive CO2 sorbents that can absorb carbon dioxide from the air when they are dry and release carbon dioxide when they have been exposed to humidity in the form of liquid water and/or partial pressures of water vapor which exceed those at ambient conditions. We will generally refer to such materials as water-sensitive CO2 sorbents.
  • Vacuum distillation is a standard method of creating fresh water from a brine, such as seawater, brackish water or other salt rich brines pumped from underground. For purposes of this disclosure, brine is also used to refer to contaminated water that is otherwise unsuitable as fresh water, such as for example, waters contaminated with biological waste materials. Thus, the term “brine” encompasses all waters contaminated with materials from which water can be separated by vacuum distillation.
  • Vacuum distillation begins with a chamber that has been at least partially evacuated. Brine is introduced into the chamber and is separated into two components: concentrated brine and fresh water product. There are many ways to supply a fluid into a vacuum chamber that are known to practitioners of the state of the art. By adding and subtracting from the vacuum chamber equal volumes of incompressible fluid it is possible to design a continuous flow system that requires only minimum amount of mechanical work.
  • The apparatus comprises a vacuum chamber that is divided into at least two parts; an evaporator unit and a condenser unit. As brine is introduced into the evaporator unit, it is allowed to evaporate. In this manner the water vapor becomes separated from the contaminants in the brine. The water vapor is then passed to a condenser unit, where it is allowed to condense. It is necessary to remove heat of condensation to keep from impeding further condensation in the condenser unit. This heat may be passed to the evaporator unit, enabling the evaporation to occur, by counterflow or some other method.
  • The evaporator unit, which is initially evacuated, fills with water vapor. The equilibrium partial pressure over the brine in the evaporator unit is a function of the temperature and of the salt content of the brine. The equilibrium partial pressure over the condensate in the condenser unit is a function of the temperature. At equal temperature, the equilibrium partial pressure over the condensate is slightly higher than over the brine. Thus, in a system with constant temperature the brine would gradually dilute itself with water extracted from the condensate. The system left to itself would operate in reverse, just as saltwater will become more dilute when it is separated from fresh water with a semi-permeable osmotic membrane.
  • One way to condense the water vapor in the condenser unit is to raise the pressure, wherein the water vapor will condense at ambient temperatures. This may be accomplished using a compressor to drive up the pressure. The heat of condensation will cause the temperature to rise in the condenser unit, wherein the heat deposited by the condensation can then be transferred to the evaporator unit. The compression acts in effect as a heat pump which transfers heat from the brine to the condensate, and a return heat flow balances out the total heat fluxes inside the system.
  • Where compression is used to condense the water out of the resulting gas mixture, the heat produced by that process can be transferred to the sorbent to raise its temperature as required. Alternatively, the heat required to drive the sorbent to the requisite temperature can also be derived from the condensation of water that has been allowed to evaporate at ambient conditions.
  • Another approach is to maintain by some other system a temperature gradient between the evaporator unit and the condenser unit, which is enough to cause a gradient in the equilibrium partial pressure that causes vapor to flow from the evaporator unit to the condenser unit. In order to maintain such a temperature differential, it is necessary to provide the heat of evaporation on the evaporator unit, and remove the heat of condensation on the condenser unit of the chamber. The required temperature differences are small; a few degrees between the evaporator and the condensate are sufficient. Operational temperatures can be low and could be well within the range of ambient temperatures, particularly in warmer climates.
  • One way of establishing the temperature gradient is to generate heat and transfer it to the evaporator. Another way of establishing the temperature gradient is to actively remove heat on the condenser unit. This requires a heat exchange system that removes heat from the condensate. In such an operation of the device, the temperature of the brine is higher than that of the condenser unit the heat is passed through and cannot be recovered within the system. In principle it is possible to couple one or more additional heat pumps to the system, which pumps the heat removed at the condenser unit and returns it to the evaporation side.
  • In combination with the CO2 capture system described above, the water vapor is evaporated from the brine and is partly absorbed onto the resin. This will release a substantial portion of the CO2 or other targeted contaminant from the sorbent. When this step is performed in a vacuum chamber, the atmosphere of the chamber will be filled primarily with water vapor and CO2. The vacuum chamber will also aid in the evaporation of the water vapor in the brine. The concentrated brine is then removed and the water is then condensed out of the CO2. Thus, the present invention produces a distilled water stream as well as concentrated CO2.
  • Providing heat to the drying resin is advantageous and one can therefore integrate a heat exchange system operating between the drying resin collector and the condenser inside the vacuum system. In a typical implementation the evaporation of the water from the resin would not produce quite enough water to make up the water losses from the system; therefore it would have to be augmented by additional brine evaporation.
  • Another aspect of the present disclosure provides a different process whereby ambient environmental temperatures are used to maintain a constant temperature at the condenser unit, i.e. by flowing ambient air, or ambient water through the heat exchanger on the brine evaporation side, and we use additional brine, e.g. seawater, to operate an evaporative cooler that creates the temperature drop necessary to force the condensation of clean water inside the vacuum chamber. The amount of seawater that needs to be evaporated on the outside of the chamber to maintain a low temperature is approximately equal to the amount of brine that is converted in the vacuum distiller.
  • The system disclosed herein comprises a vacuum chamber with means of introducing and removing a brine, with means for removal of clean water condensate, with internal surfaces on which the brine is allowed to evaporate, and surfaces of a lower temperature where the water vapor is allowed to condense. The surfaces on which the brine is evaporating are in close contact with a heat exchanger that provides the necessary heat to maintain evaporation. It is advantageous to use free heat, i.e., heat from the ambient environment, which may have been augmented by heat, e.g. from sunshine, or, e.g. waste heat. The surfaces on which water vapor is allowed to condense are in close contact with a heat exchanger that uses additional brine to provide evaporative cooling required to force the condensation.
  • In the above embodiment, brine is consumed both inside and outside the chamber. The maximum acceptable concentration of the discharge brine will limit the amount of evaporation that is acceptable. The rate of consumption in both cases is similar. The two waste streams can be combined and mixed for return to the ocean or brine reservoir. The returned concentrated brine is slightly cooler than ambient temperatures.
  • Where ocean water or any water from a large body of water is used, it is not unusual for the input water is already cooler than ambient temperatures. In this case, it is possible to take advantage of the additional cooling power derived from the cool water that is in the system.
  • In addition, one might use a CO2 membrane that separates CO2 from nitrogen and oxygen. One option would be to use a carbonic anhydrase based membrane separation technology. Of particular utility are membranes with similar properties to the ion exchange resin discussed more fully in our other applications, (see Appendix A). The thin resin membrane would transfer CO2 according to a pressure gradient in CO2 and against a pressure gradient in water vapor. The two combined create a net flow of CO2 across the membrane and thus by keeping the outside of the membrane wet or in high humidity one would create two chemical potentials that will drive CO2 across the membrane.
  • Finally, there is a great synergy with the climate control of the current chamber. The CO2 management is preferably integrated with de-humidification, or humidification of the air as the case may be, and it may also be integrated with the temperature control and AC handling of the air. The CO2 stabilization unit, shares the air handling and blowing equipment with the other tasks, and it may be built into the same set of ducts. It can take advantage of heat and condensation water produced in the refrigeration unit.
  • The present disclosure in another aspect provides an additional use for extracted CO2. According to the present invention, the extracted CO2 is employed to neutralize carbonic acid. The present invention takes advantage of the fact that in sequestration, if one can drive the partial pressure of CO2 up by about a factor of about 100, the concentrated CO2 may then be injected into alkaline brines, to neutralize the brine.
  • The resins disclosed in our previous U.S. Provisional Patent Appln. 60/985,586 and PCT International Patent Appln. Serial No. PCT/US08/60672, assigned to a common assignee, make it possible to capture CO2 from the air and drive it off the sorbent with no more than excess water vapor. It also is possible to wet the resin directly with liquid water and form a carbonate, and transfer the carbonate in a second step through a membrane between the two fluids. However, in most cases, it is preferable to create a concentrated CO2 gas that then can be transferred directly into a more alkaline brine. Here again we can make direct contact between the gas and the brine, or keep them separated by a hydrophobic, porous membrane.
  • There are many applications where one has access to alkaline underground brines that can be used to drive a humidity swing with ionic exchange sorbents, even if their ion content make them unsuitable for direct contact with the resin. The present invention takes advantage of the humidity swing and transfers the CO2 through the gas phase. Alternatively, hydrophobic membranes may be used to create a gas phase interface between two liquids, or between a liquid and a gas. If the brine covers one side of the membrane it is possible to pull CO2 gas through the membrane without bringing contaminant ions in contact with the sorbent resin.
  • A particular application of this technology can be realized where some other industrial process has created a highly alkaline waste stream that needs to be neutralized before disposal. In that case, we can introduce carbonic acid, which will either cause the precipitation of insoluble carbonates, or produce soluble but neutral carbonate salts. Similar processes are disclosed in (PCT) Publication Number WO/2005/047183. As an example, consider waste streams from bauxite processing, e.g. in the Bayer process, which produces “red mud” at pH 13. According to the PCT Application cited above, between 1990 and 2003 six to seven million tons of red mud have been produced. Another example mentioned in the reference is the reprocessing or disposal of potassium hydroxide solutions from alkaline batteries. The process of the present invention would create potassium carbonate or bicarbonate producing materials that are indeed quite harmless.
  • In one aspect of the neutralization process according to the present disclosure, we propose to use an alkaline brine which is preferably in a temperature range between 40 and 60° C., and use the water vapor to recover CO2 from our resins. We then wash the CO2 out of the gas mixture with the help of the alkaline brine. The heated alkaline brine will provide a high level of moisture which induces the resin to give off CO2 while it at the same time prevents the CO2 level from rising substantially. If operated in a vacuum the process should not be transport limited. In the presence of atmospheric pressures, however, the process could be transport limited.
  • One possible approach is to have the liquor be soaked up in open cell foams such as AQUAFOAM® floral retention foam as described in our PCT Published Application No. WO2006/084008. Another is to have it trickle through a packed bed that is installed parallel to the resin recovery unit and cycles gas from the recovery unit through it. Another option is to contain the resins in a tube whose outside is covered with a material that soaks up the brine. In such a design heat transfer between inside and outside the tube is optimized.
  • The resin, which has been saturated with CO2 in ambient air, is brought into a chamber connected to a second chamber containing wetted surfaces over which the brine flows. The brine will establish a high level of humidity and the resulting high humidity air is blown over the sorbent material. In one aspect of this invention this exchange will occur with humid air entering the chamber. In another aspect, residual air in the chamber is at least partially removed by evacuation prior to running water vapor through the chamber. As the water vapor is circulated between the wetted surfaces and the sorbent material, it carries CO2 that is released to the alkaline brine where it is absorbed into the brine. In this implementation the resinfunctions to speed up the transfer of CO2 from ambient air into the alkaline brine. Further acceleration of the transfer of CO2 may be achieved with other materials, such as, for example, with carbonic anhydrase that thereby would open the use of brines with relatively low levels of alkalinity e.g with a pH of 8-11. In this range one could even use seawater, even though the accelerated acidification of seawater would in many cases be counter-productive. However, this would not be the case, for example, where the source of an alkaline brine is an underground aquifer, from which brine is removed and to which it is returned once the CO2 is absorbed. The brine could also be water that has been exposed to alkaline mineral rocks such as basalt or peridotite or serpentinite rock. For example, one could percolate the water through a pile of serpentine tailings or other tailings that can release alkalinity.
  • The use of serpentine tailings to increase alkalinity is known in the art. Alternatively, the serpentine could be mined for this purposes It also is possible in some formations to inject water into alkaline underground systems for the purpose of enriching it with base cations. The presence of CO2 in the water may speed up this process.
  • In the case of serpentine and olivine as well as basalt, this particular use of mineral sequestration would likely result in the precipitation of magnesium and/or calcium carbonate. The advantage of this method over previous attempts to directly sequester CO2 from the atmosphere is that the CO2 concentrations can be enriched by about a factor of 100, which will greatly help with the reaction kinetics.
  • Another source of alkalinity could be Mg(OH)2 that has resulted from the processing of serpentine and olivine.
  • It is also possible to use the CO2 to dissolve calcium carbonate rock that then can be put into the ocean as calcium bicarbonate. In this example it is possible to directly use seawater to drive the dissolution, and the presence of carbonic anhydrase may speed up this process dramatically. See, e.g. PCT International Patent Appln. Serial No. PCY/US08/60672, assigned to a common assignee, for a discussion of the use of carbonic anhydrase to accelerate the CO2 capture process.
  • The dissolution of limestone with air captured CO2 is analogous to a process in which the CO2 comes from a power plant. The present invention provides a substantial advantage over a power plant in that we do not have to bring enormous amounts of lime stone to a power plant, or distribute the CO2 from a power plant to many different processing sites, but that we can instead develop a facility where seawater, lime and CO2 from the air come together more easily. One specific implementation would be to create a small basin that is periodically flushed with seawater. The CO2 is provided by air capture devices located adjacent to or even above the water surface. Of particular interest are sites where limestone or other forms of calcium carbonate (such as empty mussel shells) are readily available as well. If we have calcium carbonate, seawater and air capture devices in one place, we can provide a way of disposing of CO2 in ocean water without raising the pH of the water.
  • Indeed, it is possible to install such units adjacent a coral reef area by bringing additional limestone to the site or by extracting limestone debris near the reef. If the units operate in a slight ocean current upstream of the reef, they can generate conditions that are more suitable to the growth of the coral reef. Growth conditions can be improved by raising the ion concentration product of Ca++ and CO3 −−. This product governs the rate of coral reef growth.
  • It should be emphasized that the above-described embodiments of the present device and process, particularly, and “preferred” embodiments, are merely possible examples of implementations and merely set forth for a clear understanding of the principles of the invention. Many different embodiments of the invention described herein may be designed and/or fabricated without departing from the spirit and scope of the invention. All these and other such modifications and variations are intended to be included herein within the scope of this disclosure and protected by the following claims. Therefore the scope of the invention is not intended to be limited except as indicated in the appended claims.
  • APPENDIX A
    WRIGHT 04.01PCT PCT/US05/29979
    GLOBAL 05.01 11/346,522
    GLOBAL 05.01 PCT PCT/US06/03646
    GLOBAL 05.01-P 60/649,341
    GLOBAL 05.02 PCT PCT/US06/29238
    GLOBAL 05.02-P 60/703,098
    GLOBAL 05.03-P 60/703,099
    GLOBAL 05.04-P 60/703,100
    GLOBAL 05.05-P 60/703,097
    GLOBAL 05.06-P 60/704,791
    GLOBAL 05.07-P 60/728,120
    GLOBAL 06.01-P 60/780,466
    GLOBAL 06.01/06.03 11/683,824
    GLOBAL 06.01/06.03 PCT/US07/63607
    GLOBAL 06.03-P 60/780,467
    GLOBAL 06.04-P 60/827,849
    GLOBAL 06.04/06.05 11/866,326
    GLOBAL 06.04/06.05 PCT/US07/80229
    GLOBAL 06.05-P 60/829,376
    GLOBAL 06.06 PCT PCT/US07/084880
    GLOBAL 06.06-P 60/866,020
    GLOBAL 07.01 PCT PCT/US08/60672
    GLOBAL 07.01-P 60/912,649
    GLOBAL 07.02-P 60/912,379
    GLOBAL 07.03-P 60/946,954
    GLOBAL 07.04 CIP-P 60/985,596
    GLOBAL 07.04-P 60/980,412
    GLOBAL 07.05-P 60/985,586
    GLOBAL 07.06-P 60/989,405
    GLOBAL 08.01-P 61/058,876
    GLOBAL 08.02-P 61/058,881
    GLOBAL 08.03-P 61/058,879

Claims (55)

1. A system for removing carbon dioxide from a fluid, comprising passing a stream of the fluid in contact with a sorbent to absorb and concentrate carbon dioxide from the fluid stream; releasing the carbon dioxide from the sorbent; and delivering the carbon dioxide for use in a secondary process.
2. The system of claim 1, wherein the carbon dioxide is delivered to the secondary process in a gaseous state, solid state, or liquid state, as described.
3. The system of claim 1, wherein the secondary process is selected from a group consisting of: machining coolant and lubricant, grit blasting, for smoothing or paint or rust removal, cryogenic cleaning, quick freeze processes, R744 refrigerant, dry cleaning solvent, perishable shipping container pre-cooling, perishable shipping inert environment maintenance, beverage carbonation, fire suppression, plant fertilization, horticulture, agriculture, silvaculture, aquatic algae production, enhanced oil recovery, water softening, Solvay process, propellant, pressurizing gas, e.g. for aerosol cans, inflation gas, e.g. for life rafts, supercritical CO2 extraction, semi conductor manufacturing, organic solvent, perfume aromatics, decaffeinating coffee or tea, supramics, pharmaceutical manufacturing, chemical production of urea, methanol, inorganic carbonates, organic carbonates, polyurethanes, paint pigments, foaming agents, carbon based fuels, synthetic fuels, fumigation of farm products, neutralization of alkaline waters or slurries or solid materials, and gas shields for welding or electronics manufacturing.
4. The system of claim 1, wherein the sorbent is an ion exchange membrane material.
5. The system of claim 1, wherein the carbon dioxide is released from the sorbent by exposing the sorbent to increased humidity, by using water, humid air, or pulses of steam.
6. The system of claim 1, wherein the carbon dioxide is released from the sorbent using a weak liquid amine as a secondary sorbent.
7. The method of claim 1, wherein the sorbent is a resin, and wherein the carbon dioxide is released from the sorbent utilizing a humidity swing, and wherein the resin is contained in a chamber that also contains activated carbon, further comprising the step of drying out the activated carbon to capture the carbon dioxide in a concentrated form prior to delivering the carbon dioxide for use in a secondary process.
8. The method of claim 1, wherein the carbon dioxide is released from the sorbent by washing the sorbent with a wash fluid to create an effluent, placing the effluent on the acid side of an electrodialysis cell, driving the pH of the acid side of the electrodialysis cell to a neutral pH to release carbon dioxide, prior to delivering the carbon dioxide for use in a secondary process.
9. A method for removing carbon dioxide from a gas, comprising:
bringing said gas in contact with a resin contained in a plurality of chambers, wherein a plurality of chambers are connected in series;
wetting said resin with water, wherein the water enters a first chamber and exits through a last chamber;
collecting water vapor and carbon dioxide from said resin;
separating said carbon dioxide from said water vapor; and
delivering the carbon dioxide for use in a secondary process.
10. The method of claim 9, wherein the secondary process is selected from a group consisting of: machining coolant and lubricant, grit blasting for smoothing and rust or paint removal, cryogenic cleaning, quick freeze processes, R744 refrigerant, dry cleaning solvent, perishable shipping container pre-cooling, perishable shipping inert environment maintenance, beverage carbonation, fire suppression, plant fertilization, horticulture, agriculture, silvaculture, aquatic algae production, enhanced oil recovery, water softening, Solvay process, propellant, pressurizing gas, e.g. for aerosol cans, inflation gas, e.g. for life rafts, supercritical CO2 extraction, semi conductor manufacturing, organic solvent, perfume aromatics, decaffeinating coffee or tea, supramics, pharmaceutical manufacturing, chemical production of urea, methanol, inorganic carbonates, organic carbonates, polyurethanes, paint pigments, foaming agents, carbon based fuels, i.e. synthetic fuels, fumigation of farm products, neutralization of alkaline waters or slurries or solid materials, or gas shield for welding, or electronics manufacturing.
11. The method of claim 9, wherein said plurality of chambers are connected via a plurality of valves that allow any of said plurality of chambers to serve as said first chamber or said last chamber.
12. The method as of claim 9, wherein said first chamber contains resin that was most recently saturated or partially saturated with carbon dioxide from said gas, and each successive chamber contains resin which has been wetted and carbon dioxide collected from for a greater period of time than the previous chamber, and so on, to said last chamber.
13. A system for utilization of carbon dioxide that is substantially carbon neutral, comprising a carbon dioxide capture device that collects carbon dioxide from a fluid stream produced by a process that utilizes carbon dioxide, wherein the carbon dioxide capture device delivers the captured carbon dioxide for utilization by the process.
14. The system of claim 13, wherein the process is selected from a group of processes utilizing carbon dioxide consisting of: CO2 as a refrigerant, as a dry cleaning agent or other solvent, as a fire suppression material, as an oxidation preventing shield-gas, as an alternative to sand-blasting, synthetic fuel production, plant fertilization, or as a freezing agent in food processing.
15. A method of creating tradable carbon credits which comprises extracting CO2 from ambient air at a location adjacent or remote from where the CO2 is generated, using sorbent, selling, trading or transferring the resulting CO2 credits to a third party, and using the extracted CO2 in a secondary process.
16. A method for luring CO2 sensitive insects toward a specific location where a moisture sensitive CO2 sorbent that is partially or fully loaded with CO2 is exposed to moisture usually in excess of that present in the ambient air at the location.
17. The method of claim 16, wherein the sorbent is held in place by an open basket that is protected with a roof and a floor against accidental wetting by rain.
18. The method of claim 16, wherein the sorbent is a strong base ion exchange resin.
19. The method of claim 16, wherein moisture is delivered from a spray nozzle or as a puff of steam.
20. The method of claim 16, wherein the resin is woven into a textile material that acts as a wick, can bring up water from a separate reservoir that is filled either automatically or by hand at a desired time.
21. The method of claim 16, wherein the sorbent is a resin that is embedded into polymer matrix and wherein the polymer can contain a contact active insecticide.
22. An apparatus for extracting a gaseous contaminant from a gas stream using a sorbent employing a humidity swing and for distilling a brine, comprising:
a sorbent for capturing the contaminant;
a capture unit, wherein the sorbent is exposed to the gas stream and becomes substantially saturated with the contaminant;
an evaporation unit, wherein a brine is evaporated forming a concentrated brine and water vapor, and wherein the sorbent is brought in contact with the water vapor causing the sorbent to become substantially depleted of the contaminant according to a humidity swing; and
a condensation unit, wherein the water vapor is separated from the contaminant.
23. The apparatus of claim 22, further comprising a heat exchanger for conserving the heat retained by the sorbent from the condensation unit and returning that heat to the evaporation unit.
24. The apparatus of claim 22, wherein the contaminant is carbon dioxide, and the gas stream is ambient air or an exhaust system.
25. An apparatus for stabilizing the level of carbon dioxide in an enclosed environment, comprising:
a filter unit attached to said enclosed environment, containing a sorbent material for carbon dioxide capture; and
a regenerating system for regenerating the sorbent material at least in part.
26. The apparatus of claim 25, wherein the captured carbon dioxide is delivered to the enclosed environment, to the surrounding atmosphere, or to another desired location by the operation of a plurality of louvers.
27. The apparatus of claim 25, wherein the sorbent material is an ion exchange resin subject to a humidity swing.
28. The apparatus of claim 27, wherein the regenerating system comprises one or more from a group consisting of: DI water, humid air, condensate, and jetted steam.
29. A method for stabilizing the level of carbon dioxide in an enclosed environment using the apparatus of claim 25, wherein the level of carbon dioxide is maintained within predetermined parameters.
30. The method of claim 29, further controlling the humidity in the enclosed environment.
31. The method of claim 29, wherein the level of carbon dioxide is optimized for the storage of produce.
32. The method of claim 29, wherein the level of carbon dioxide is optimized for the storage of bananas.
33. A method for extracting carbon dioxide from a gas comprising bringing a stream of the gas in contact with a sorbent, releasing the carbon dioxide from the sorbent to create a carbon dioxide-enriched gas mixture, and bringing the enriched gas mixture in contact with an aqueous solution, wherein the aqueous solution absorbs carbon dioxide from the gas mixture.
34. The method of claim 33, wherein the gas is brought in contact with the aqueous solution by bubbling the enriched gas mixture through the aqueous solution, or by flowing the gas over the aqueous solution.
35. The method of claim 33, wherein the aqueous solution is an alkaline brine, and wherein at least part of the carbon dioxide is sequestered in the alkaline brine by forming carbonate ions, thereby neutralizing the aqueous solution, and further comprising the step of returning the aqueous solution to its origin.
36. The method of claim 33, wherein the enriched gas mixture is brought in contact with the aqueous solution using a semi-permeable membrane that allows the transfer of carbon dioxide from the gas mixture to the aqueous solution; wherein the membrane is hydrophobic and contains gas-filled pores; and wherein the membrane allows the transmission of water vapor from aqueous solution to the enriched gas mixture.
37. The method of claim 33, wherein water vapor is produced from the aqueous solution to drive or partially drive the carbon dioxide from the sorbent via a humidity swing, and wherein aqueous solution and the sorbent are placed in close proximity so that heat consumed in producing the water vapor is at least in part provided by condensation of the water vapor in contact with the sorbent.
38. An apparatus, constructed to perform the method of claim 37, wherein the sorbent is contained inside a tube whose walls have a minimal heat resistance and that is open on both ends, and where the outside of the tube is wetted by the aqueous solution so as to maximize heat transfer between the inside and outside of the tube.
39. The method of claim 33, wherein the aqueous solution is contained in a sponge or foam.
40. The method of claim 33, including the step of utilizing the extracted carbon dioxide to neutralizing waste alkaline brines.
41. The method of claim 40, including the step of utilizing the extracted carbon dioxide for neutralizing alkaline brines that are produced in the production of alkaline batteries, or that are produced by injecting water into basaltic or other ultramafic or other basic rock formations, or that are formed as mining waste materials.
42. The method of claim 40, including the step of utilizing the extracted carbon dioxide for neutralizing asbestos tailings.
43. A method for adding calcium bicarbonate to seawater without changing the alkalinity of the water, comprising using a sorbent that employs a humidity swing to extract carbon dioxide from the air resulting in a gas mixture, precipitating carbonic acid from the gas mixture to dissolve an amount of limestone, forming calcium bicarbonate, and depositing the calcium bicarbonate in the seawater with any remaining carbonic acid.
44. The method of claim 43, wherein the several steps are performed upstream of a coral reef in order to increase the calcium and carbonate ion product to enhance a growth rate of the coral reef.
45. A method of stabilizing sorbent CO2 levels in storage containers of fresh produce, comprising recovering excess CO2 from the storage containers using a sorbent for CO2.
46. A method for removing a gaseous contaminant from a gas stream, comprising
placing said gas stream in contact with a sorbent, wherein the contaminant from said gas stream becomes loaded on said sorbent;
releasing the gas from said substrate by use of a humidity swing; wherein the humidity swing is performed by evaporating a brine to form concentrated brine and water vapor, and bringing the water vapor in contact with the loaded sorbent;
and condensing the water vapor to separate the water vapor from the contaminant.
47. The method of claim 46, wherein the contaminant is carbon dioxide, and the gas stream is an exhaust stream or is ambient air.
48. The method of claim 46, wherein the sorbent is a solid ion exchange material.
49. The method of claim 46, wherein a heat exchanger is used to conserve the heat of condensation and returns the heat to be used in the evaporation of the brine.
50. The method of claim 46, wherein the evaporation of the brine occurs in an evacuated space.
51. The method of claim 46, wherein at least part of the condensed water is captured and recycled.
52. The apparatus of claim 22, wherein the sorbent is a solid ion exchange material.
53. The apparatus of claim 22, wherein the condensation unit is cooled with water or seawater.
54. The apparatus of claim 22, wherein the evaporation unit is a vacuum chamber.
55. The apparatus of claim 22, wherein the evaporation unit and the condensation unit are part of the same chamber.
US12/389,213 2008-02-19 2009-02-19 Extraction and sequestration of carbon dioxide Abandoned US20090232861A1 (en)

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US14/257,698 US20150104554A1 (en) 2008-02-19 2014-04-21 Extraction and sequestration of carbon dioxide
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