WO2008151060A1 - Utilisation de la dissociation photoélectrochimique de l'eau pour produire des matériaux destinés à la séquestration du dioxyde de carbone - Google Patents

Utilisation de la dissociation photoélectrochimique de l'eau pour produire des matériaux destinés à la séquestration du dioxyde de carbone Download PDF

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WO2008151060A1
WO2008151060A1 PCT/US2008/065387 US2008065387W WO2008151060A1 WO 2008151060 A1 WO2008151060 A1 WO 2008151060A1 US 2008065387 W US2008065387 W US 2008065387W WO 2008151060 A1 WO2008151060 A1 WO 2008151060A1
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Prior art keywords
carbon dioxide
anode
cathode
base
hydrogen
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PCT/US2008/065387
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English (en)
Inventor
C. Deane Little
Joseph V. Kosmoski
Timothy C. Heffernan
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New Sky Energy, Inc.
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Publication of WO2008151060A1 publication Critical patent/WO2008151060A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/50—Processes
    • C25B1/55—Photoelectrolysis
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Definitions

  • the present invention relates to the field of hydrogen production and carbon dioxide sequestration. More specifically, the present invention relates to an integrated system that uses solar energy in combination with photoelectrochemical water electrolysis to generate hydrogen and sequester carbon dioxide.
  • the electrochemical cleavage of water has traditionally been viewed as a method of producing hydrogen and oxygen gas.
  • traditional alkaline water electrolysis two molecules of hydroxide base are produced and consumed for every molecule of hydrogen generated.
  • a variant of water electrolysis is photoelectrochemical water splitting in which sunlight directly strikes photosensitive materials immersed in water, resulting in electrical excitation and splitting of the water molecule to form hydrogen gas and hydroxide base at the cathode and oxygen gas and acid at the anode.
  • the present invention encompasses an integrated system for sequestering carbon dioxide from a gas stream and producing renewable hydrogen, oxygen, acid and base.
  • the integrated system includes a photoelectrochemical electrolysis unit, a hydrogen sequestration tank, an oxygen sequestration tank, an acid sequestration tank, a base sequestration tank and a gas contact area.
  • the photoelectrochemical electrolysis unit is adapted to split water into hydrogen and oxygen using sunlight and includes at least one cathode in a cathode region adapted to produce hydrogen and concentrated base in the form of hydroxide ions, at least one anode in an anode region adapted to produce oxygen and concentrated acid in the form of protons, and an aqueous electrolyte solution in contact with the cathode and the anode.
  • the hydrogen and base sequestration tanks collect and process hydrogen and base, respectively, produced at the cathode region.
  • the oxygen and acid sequestration tanks collect and process oxygen and acid, respectively, produced at the anode region.
  • the gas contact area is adapted to react gaseous carbon dioxide with the base generated at the cathode or a carbon dioxide sequestering solution prepared using acid generated at the anode.
  • the integrated system set out above may include additional components.
  • the carbon dioxide reacts with the hydroxide base to form carbonate salt or bicarbonate salt.
  • the hydrogen, oxygen, acid, base, carbon dioxide, carbonate salts or bicarbonate salts are processed into value-added products.
  • the integrated system produces substantially no carbon dioxide, resulting in a net removal of carbon dioxide from the gas stream.
  • the present invention encompasses a photoelectrochemical apparatus for generating renewable hydrogen and sequestering atmospheric carbon dioxide or carbon dioxide from a gas stream.
  • the apparatus includes a photoelectrochemical electrolysis unit adapted to split water into hydrogen and oxygen using sunlight, a gas contact assembly, gas supply equipment and a separation chamber.
  • the photoelectrochemical electrolysis unit is adapted to split water using sunlight and includes at least one cathode adapted to produce hydrogen and concentrated base in the form of hydroxide ions, at least one anode adapted to produce oxygen and concentrated acid in the form of protons, and an aqueous electrolyte solution.
  • the gas contact assembly is adapted to receive carbon dioxide from an air or gas stream and hydroxide ions produced in the photoelectrochemical electrolysis unit so that the carbon dioxide contacts and reacts with the hydroxide ions to form bicarbonate or carbonate ions in solution.
  • the separation chamber is connected to the gas contact assembly and is adapted to separate the bicarbonate or carbonate ions from the solution.
  • the apparatus described above may include additional components.
  • the apparatus includes gas supply equipment adapted to route carbon dioxide to the gas contact assembly.
  • the apparatus includes equipment for isolating and processing the hydrogen, oxygen, acid, base, carbonate or bicarbonate.
  • the present invention is a method of generating renewable hydrogen and sequestering carbon dioxide from a gas stream.
  • the method first includes supplying sunlight to a photoelectrochemical electrolysis unit having an anode located in an anode region and a cathode located in a cathode region. Both the anode region and cathode region are in contact with an aqueous electrolyte.
  • the method further includes producing oxygen gas and acid in the form of protons at the anode, producing hydrogen gas and base in the form of hydroxide ions, collecting the hydrogen gas, collecting the oxygen gas, removing acid from the anode region, removing base from the cathode region and contacting the hydroxide ions with a source of gaseous carbon dioxide to sequester carbon dioxide in solution as bicarbonate, carbonate or a mixture thereof.
  • the method includes reacting the bicarbonate or carbonate with the acid produced in the photoelectrochemical electrolysis unit to generate concentrated carbon dioxide gas or super critical carbon dioxide.
  • the method includes isolating and processing at least one of the hydrogen, oxygen, acid, base, carbonate or bicarbonate.
  • the method includes utilizing at least one of the hydrogen, oxygen, acid, base, carbonate or bicarbonate as a reagent to produce a value-added product containing the sequestered carbonate, bicarbonate or stable form of carbon dioxide.
  • the method includes supplying direct current electricity from an energy source to the photoelectrochemical electrolysis unit.
  • the energy source may be a renewable energy source, resulting in substantially no CO2 emissions.
  • the photoelectrochemical electrolysis unit may include additional features.
  • the photoelectrochemical electrolysis unit is one of a photovoltaic unit, a semiconductor- liquid junction unit or a photovoltaic/semiconductor-liquid junction unit.
  • the cathode is a photo-cathode.
  • the anode is a photo-anode.
  • at least one of the anode and cathode is a photo-electrode.
  • the photo-electrode is a p- or n- type semiconductor.
  • FIG. 1 is a schematic diagram of a photoelectrochemical water splitting and carbon dioxide sequestration system, according to various embodiments of the present invention.
  • FIG. 2 is a schematic diagram of a photoelectrochemical electrolysis unit of the photoelectrochemical water splitting and carbon dioxide sequestration system of FIG. 1, according to various embodiments of the present invention.
  • FIG. 3 is a schematic diagram of a photoelectrochemical electrolysis unit of the photoelectrochemical water splitting and carbon dioxide sequestration system of FIG. 1 connected to a solar source, according to various embodiments of the present invention.
  • FIG. 4 is a schematic diagram of value-added products that may be processed from the photoelectrochemical water splitting and carbon dioxide sequestration system of FIG. 1, according to various embodiments of the present invention.
  • FIG. 4 is a schematic diagram of value-added products that may be processed from the photoelectrochemical water splitting and carbon dioxide sequestration system of FIG. 1, according to various embodiments of the present invention.
  • FIG. 1 shows a schematic diagram of an integrated phototelectrochemical (PEC) water splitting and carbon dioxide sequestration system 10 for generating renewable hydrogen and capturing carbon dioxide (CO 2 ), according to one embodiment
  • PEC phototelectrochemical
  • CO 2 carbon dioxide
  • Photoelectrochemical water splitting is known in the art and is described, for example, in an article by Antonio Currao entitled “Photoelectrochemical Water Splitting", published in Vol. 61, No. 12 o ⁇ Chimia in 2007, pages 815-819, which is incorporated herein by reference.
  • renewable hydrogen is generated as a carbon negative rather than carbon neutral fuel and can be used as a large-scale application for reducing global carbon dioxide pollution.
  • the integrated PEC water splitting and carbon dioxide sequestration system 10 creates carbon negative energy strategies for producing clean hydrogen fuel and reducing atmospheric carbon dioxide.
  • carbon dioxide negative refers to the net overall reduction of carbon dioxide in the atmosphere or an air or gas stream.
  • the integrated PEC water splitting and carbon dioxide sequestration system 10 is carbon dioxide negative, it is meant that the integrated PEC water splitting and carbon dioxide sequestration system 10 removes substantially more carbon dioxide than it produces. In addition, unlike traditional methods of manufacturing hydroxide base, no substantial carbon dioxide or chlorine gas is produced.
  • the integrated PEC water splitting and carbon dioxide sequestration system 10 includes a solar energy source 12, an electrolysis unit 14 including a cathode 16, an anode 18 and an aqueous electrolyte source 20, a hydrogen sequestration tank 22, an oxygen sequestration tank 24, a base sequestration tank 26, an acid sequestration tank 28, a captured carbon dioxide apparatus 30 connected to the base sequestration tank 26, a carbon dioxide capture apparatus 32 connected to the acid sequestration tank 28, a carbon dioxide product system 34 and a fuel cell 36.
  • Suitable electrolysis units are known in the art and several electrolysis units are compatible with the present PEC water splitting and carbon dioxide sequestration system 10.
  • the electrolysis unit 14 includes a standard electrolysis apparatus driven by a photovoltaic cell, such as a solar panel, for converting sunlight to direct current.
  • the solar energy source 12 can accept direct sunlight, in which case the cathode 16 is replaced with a photo-cathode and the anode 18 is replaced with a photo-anode.
  • the photo-cathode 16 and photo-anode 18 are made from p-type semiconductors and n-type semiconductors, respectively.
  • photo-electrodes When photo-electrodes are used, the redox reaction occurs directly at the semiconductor-liquid interface.
  • the solar energy source 12 accepts solar energy from a combination of direct sunlight and a photovoltaic cell 38.
  • the cathode 16 is a photo-cathode or the anode 18 is a photo-anode. All combinations of photovoltaic driven electrodes and semiconductor -liquid junction photo-electrodes are within the scope of this invention.
  • the cathode 16 and anode 18 should be stable in aqueous solutions with a wide pH rangeand should also have band gaps and band edges suitable for trapping sunlight and splitting water.
  • the band gap of the cathode 16 or anode 18 should substantially overlap with the solar spectrum and the electron transfer energies should overlap with the dissociation energy of the water molecule.
  • a multi-step photon trapping device may be used to more comprehensively utilize the solar light spectrum.
  • direct current voltage generated by another source such as windpower, hydroelectric, geothermal or a fuel cell, can also be used to supplement the energy provided from the sun.
  • the supplemental energy provided by the direct current voltage reduces the energy required from the sun to a range that better aligns with the solar spectrum.
  • the supplemental electrical energy is generated in the fuel cell 36 using some of the hydrogen produced in the electrolysis unit 14. By using electrical energy generated by the fuel cell 36, more acid and base may also be generated. Examples of other sources of electrical energy include waste organic matter in a fuel cell or inexpensive fuels, such as methanol.
  • the electrolysis unit 14 includes the cathode 16 located in a cathode region 40, the anode 18 located in an anode region 42 and the aqueous electrolyte solution 20.
  • the cathode and anode regions 40, 42 may be separated by any suitable means, such as an ion selective membrane, an electric potential applied to at least one metal screen, or a porous glass frit.
  • ion selective membrane such as an ion selective membrane, an electric potential applied to at least one metal screen, or a porous glass frit.
  • gravity feed, active pumping, or gas pressure displacement may be used to divert basic and acidic electrolytes produced in the cathode and anode regions 40, 42 into the base and acid sequestration tanks 26, 28, respectively.
  • simple acid and base trapping resins may also be placed in contact with the aqueous electrolyte solution 20a to trap protons and hydroxide ions produced in the electrolytic unit 14 for later use.
  • the integrated PEC water splitting and carbon dioxide sequestration system 10 also includes a gas contact assembly 44, gas supply equipment 46 and a separation chamber 48.
  • the gas contact assembly 44 is connected to a gas stream containing carbon dioxide and is adapted to receive hydroxide ions so that the carbon dioxide contacts and reacts with the hydroxide ions to form bicarbonate or carbonate ions in solution.
  • the gas contact assembly 44 receives hydroxide ions from the base sequestration tank 26.
  • the gas supply equipment 46 is adapted to route a gas stream containing carbon dioxide to the gas contact assembly 44.
  • the gas supply equipment 46 is connected to the captured carbon dioxide apparatus 30 and supplies the carbon dioxide to the gas contact assembly 44.
  • the gas contact assembly 44 receives carbon dioxide directly from the captured carbon dioxide apparatus 30.
  • the captured carbon dioxide apparatus 30 and the gas contact assembly 44 are integrated into one device such that the gas contact assembly 44 receives carbon dioxide directly.
  • the PEC water splitting and carbon dioxide sequestration system 10 can function without gas supply equipment.
  • the separation chamber 48 concentrates, processes or isolates the bicarbonate and carbonate formed from the reaction of hydroxide ions with carbon dioxide in the gas contact assembly 44.
  • the aqueous electrolyte solution 20a contacts the cathode 16 and the anode 18 and is responsible for transferring charges and moving ions within the electrolysis unit 14.
  • the aqueous electrolyte source 20 may include water or any highly concentrated electrolyte solution, such as sodium, potassium, calcium, or magnesium sulfate, nitrate, phosphate, or carbonate.
  • the aqueous electrolyte includes an alkali salt that is a salt of the l(IA) or 2(1IA) groups of the periodic table.
  • Exemplary electrolytes suitable for use with the present invention include, but are not limited to: sodium sulfate, potassium sulfate, calcium sulfate, magnesium sulfate, sodium nitrate, sodium phosphate, potassium nitrate, sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium phosphate or potassium carbonate.
  • Other suitable electrolyte solutions include sea water and aqueous sea salt solutions.
  • the aqueous electrolyte source 20 contains substantially no chloride such that the integrated PEC water splitting and carbon dioxide sequestration system 10 produces essentially no chlorine gas.
  • the integrated PEC water splitting and carbon dioxide sequestration system 10 produces less than about 100 parts per million (ppm) of chlorine, particularly less than about 10 ppm of chlorine, and more particularly less than about 1 ppm of chlorine.
  • the aqueous electrolyte solution 20a is a saturated solution of sodium sulfate prepared by adding an excess of sodium sulfate to about 1000 liters of clean distilled water placed in a 1200 liter electrolyte processing and storage reservoir. The solution is maintained at about 30 degrees Celsius ( 0 C) while being mechanically mixed overnight. The resultant solution is pumped into the electrolysis unit 14 using a pump or gravity feed. Upon photoelectrochemical water splitting, the aqueous electrolyte solution 20a yields hydrogen and sodium hydroxide in the cathode region 40 while producing oxygen and sulfuric acid in the anode region 42.
  • the concentration of the aqueous electrolyte solution 20a can vary depending on the demands of the electrolysis unit 14 and the overall integrated PEC water splitting and carbon dioxide sequestration system 10.
  • the aqueous electrolyte concentration may also vary with changes in the temperature, ⁇ H ⁇ and/or the selected electrolytic salt.
  • the concentration of the aqueous electrolyte solution 20a is approximately IM.
  • a saturated aqueous electrolyte solution 20a is maintained within the electrolysis unit 14.
  • the solar energy supplied to the electrolytic unit 14 from the solar energy source 12 causes photoelectrochemical cleavage of the water in the electrolytic unit 14 to produce hydrogen and base at the cathode 16 and cathode region 40 and oxygen and acid at the anode 18 and anode region 42.
  • the rising gases within the aqueous electrolyte solution 20a cause dynamic fluid convection, which is optimized by the electrolysis design.
  • the convection flow of the aqueous electrolyte solution 20a within the cathode 16 and anode 18 minimizes the recombination of the newly generated base and acid typically experienced by traditional electrolysis units.
  • the base and acid may be further purified using ion selective membranes, semi-permeable membranes or hydrogel barriers.
  • the membranes or barriers 50 shown in FIGS.
  • the continuous production of base and acid during photoelectrochemical water splitting results in a pH difference between the cathode region 40 and the anode region 42 of the electrolysis unit 14. According to one embodiment, the difference in pH between the cathode region 40 and the anode region 42 is at least about 4 pH units.
  • the difference in pH between the cathode region 40 and the anode region 42 is at least about 6 pH units. In yet another embodiment, the difference in pH between the cathode region 40 and the anode region 42 can reach about 10 pH units or more. The difference in pH between the cathode region 40 and the anode region 42 can be maintained by preventing the catholyte formed in the cathode region 40 and the anolyte formed in the anode region 42 from combining. Alternately, the pH difference between cathode region 40 and the anode region 42 can be minimized by adding fresh electrolyte to the system via a central feed line or reservoir, or by using suitable pH buffers that allow accumulation of acid and base ions without apparent pH changes. Such a strategy may minimize the energy input required to split water.
  • the gases are routed from the cathode 16 or anode 18 to storage or flow systems designed to collect such gases.
  • the low density of the gases relative to the aqueous electrolyte solution 20a causes the gases to rise.
  • the reaction regions are designed to direct this flow up and out of the cathode 16 and the anode 18 and into adjacent integrated areas.
  • the hydrogen, base, oxygen and acid are physically diverted for collection in the hydrogen sequestration tank 22, the base sequestration tank 26, the oxygen sequestration tank 24 and the acid sequestration tank 28, respectively.
  • the hydrogen and oxygen are collected in the hydrogen sequestration tank 22 and the oxygen sequestration tank 24, respectively, and may be used to generate electricity to power a fuel cell (such as fuel cell 36).
  • the hydrogen and/or oxygen may also be used internally to react with other products of the integrated PEC water splitting and carbon dioxide sequestration system 10 to create value-added products.
  • hydrogen and/or oxygen may be removed from the integrated PEC water splitting and carbon dioxide sequestration system 10 as products to be sold or used as fuels or chemical feedstocks.
  • the base generated by the electrolysis unit 14 is sent to the base sequestration tank 26 and is sold, used as a carbon neutral commodity or chemically reacted with carbon dioxide gas to form carbonate or bicarbonate.
  • the carbon dioxide is chemically transformed to carbonate or bicarbonate salts.
  • the carbon dioxide may be captured by reacting, sequestering, removing, transforming or chemically modifying gaseous carbon dioxide in the atmosphere or gas stream.
  • the gas stream may be flue gas, fermenter gas effluent, air, biogas, landfill methane, or any carbon dioxide-contaminated natural gas source.
  • the carbonate salts may subsequently be processed to generate a variety of carbon-based products. For example, the carbonate salts may be concentrated, purified, enriched, chemically reacted, diverted, transformed, converted, distilled, evaporated, crystallized, precipitated, compressed, stored or isolated.
  • the reaction of the base with the carbon dioxide can be passive, without any air-water mixing.
  • An example of a passive reaction includes an open-air reservoir filled with hydroxide base, or a solution containing the base. This reaction is spontaneous and can be driven by increased concentrations of base.
  • the reaction can also proceed by active mechanisms involving the base or carbon dioxide.
  • An example of an active reaction includes actively spraying, nebulizing, stirring, or dripping a basic solution in the presence of the carbon dioxide.
  • carbon dioxide is actively reacted with the base by bubbling or forcing the gas stream through a column or reservoir of base generated by the electrolysis unit 14. Combinations of active and passive carbon dioxide trapping systems are also envisioned.
  • bicarbonate and carbonate salts are formed by the integrated PEC water splitting and carbon dioxide sequestration system 10. These reactions may take place within the integrated PEC water splitting and carbon dioxide sequestration system 10 or the hydroxide base may be removed from the system and transported to another site for capturing carbon dioxide from the atmosphere or a gas stream using the passive or active techniques previously described.
  • the acid produced by the electrolysis unit 14 is routed to the acid sequestration tank 28 and can be processed and removed from the integrated PEC water splitting and carbon dioxide sequestration system 10 for sale as a carbon neutral commodity. Used internally, the acid may be used to prepare certain carbon dioxide sequestering compounds, which are then used to capture carbon dioxide from the atmosphere or gas stream.
  • the acid can be reacted with a material that when exposed to a strong acid is converted to a carbon dioxide sequestering material.
  • exemplary materials that can be converted to a carbon dioxide sequestering material by reaction with a strong acid include, but are not limited to, the following: the mineral clay sepiolite, serpentine, talc, asbestos, and various mining byproducts such as asbestos mining waste.
  • the common mineral serpentine can be dissolved in sulfuric acid producing a solution of magnesium sulfate while precipitating silicon dioxide as sand. Addition of sodium hydroxide creates a mixture of magnesium sulfate and magnesium hydroxide. The process also converts toxic asbestos and asbestos waste into non-toxic carbon dioxide binding materials.
  • the carbon dioxide sequestering material may be further reacted with strong acid to release carbon dioxide gas under controlled conditions.
  • the carbon dioxide released from the carbon dioxide sequestering materials may be captured and stored for further processing.
  • the acid may also be used by the integrated PEC water splitting and carbon dioxide sequestration system 10 as a chemical reagent to create other value-added products.
  • the carbonate and bicarbonate salts are isolated after reacting the base with carbon dioxide.
  • the acid can then be combined with carbonate and bicarbonate salts, for example from the separation chamber 48, to release the carbon dioxide from the carbonate or bicarbonate salts in a controlled manner to further process the released carbon dioxide into value-added products.
  • These products may include, but are not limited to: carbon monoxide, super-critical carbon dioxide, pressurized carbon dioxide, liquid carbon dioxide or solid carbon dioxide.
  • the acid may also be used as a chemical commodity for any process requiring acid.
  • base and/or acid may be removed from the PEC water splitting and carbon dioxide sequestration system 10 and transported to another site to capture carbon dioxide from the atmosphere or a gas stream using the passive or active techniques previously described.
  • the system When powered by solar energy, the system produces the base and/or acid that may be used to capture carbon dioxide from the atmosphere or a gas stream.
  • the overall integrated PEC water splitting and carbon dioxide sequestration system 10 sequesters substantially more carbon dioxide than it creates, resulting in a net negative carbon dioxide footprint. Any significant carbon dioxide trapping makes all of the products produced by the system carbon dioxide negative, particularly those carbon products synthesized or produced from atmospheric carbon dioxide.
  • FIG.4 illustrates value-added products that may be processed from the carbon dioxide captured using the base and/or acid produced by the integrated PEC water splitting and carbon dioxide sequestration system 10. Many carbon-based products can be manufactured from carbon dioxide trapped by the integrated PEC water splitting and carbon dioxide sequestration system 10. Commercial products manufactured from carbon dioxide trapped by the integrated PEC water splitting and carbon dioxide sequestration system 10 are carbon dioxide negative, resulting in an overall net decrease in atmospheric carbon dioxide as gaseous carbon dioxide is converted to value-added carbon products.
  • Exemplary value-added products manufactured using the hydrogen, oxygen, acid and base produced by the integrated PEC water splitting and carbon dioxide sequestration system 10 include those disclosed in U.S. Patent Application Serial No. 12/062,269 entitled “Electrochemical Methods to Generate Hydrogen and Sequester Carbon Dioxide”; U.S. Patent Application Serial No. 12/062,322 entitled “Electrochemical Apparatus to Generate Hydrogen and Sequester Carbon Dioxide”; U.S. Patent Application Serial No.
  • the integrated PEC water splitting and carbon dioxide sequestration system 10 processes the value-added products from the center of the diagram outward.
  • base generated is reacted with carbon dioxide to produce carbonate and bicarbonate salts.
  • the carbon dioxide, carbonate/bicarbonate salts can in turn be converted to carbon monoxide by chemical reduction or reaction with hydrogen.
  • the combination of carbon monoxide and hydrogen is Syngas, a critical cornerstone of synthetic organic chemistry.
  • chemical building blocks such as methane, urea, ethylene glycol, acetaldehyde, formaldehyde, limestone, acetic acid, methanol, formic acid, acetone and fo ⁇ namide can be formed.
  • the value-added chemical building blocks can be removed from the integrated PEC water splitting and carbon dioxide sequestration system 10 for sale as products or remain in the integrated system for further processing to a second class of value-added products. These value-added end products are then removed from the integrated PEC water splitting and carbon dioxide sequestration system 10 and sold, resulting in profitable conversion of carbon dioxide into carbon negative products. Simultaneous production of renewable hydrogen is subsidized by sale of these carbon products, creating a carbon negative energy strategy with potentially dramatic impacts on global warming.
  • the center circle of FIG.4 depicts exemplary products that can be produced from the reaction of hydroxide base with carbon dioxide, or (in the case of carbon monoxide) by reaction of captured carbon dioxide with hydrogen.
  • These chemical compounds include carbon dioxide, carbon monoxide, carbonate and bicarbonate, all of which can be easily inter-converted. They can be further processed to create standard chemical building blocks. In many cases, the hydrogen, oxygen, acid and base generated by the electrolysis unit 14 can be used for this secondary processing.
  • the building blocks can also be further processed within the integrated PEC water splitting and carbon dioxide sequestration system 10 to make many valuable carbon based products, exemplary embodiments of which are shown in FIG. 4.
  • the commercial products manufactured from carbon dioxide trapped by the integrated PEC water splitting and carbon dioxide sequestration system 10 represent carbon negative commodities, with the integrated PEC water splitting and carbon dioxide sequestration system 10 producing an overall net decrease in gaseous carbon dioxide while creating value-added carbon products. Sale of these products may dramatically subsidize renewable hydrogen production, making clean hydrogen an inexpensive by-product of an industrial process focused on converting atmospheric carbon dioxide into valuable carbon-based products.
  • Embodiment 1 is an integrated system for sequestering carbon dioxide from a gas stream and producing renewable hydrogen, oxygen, acid and base, the integrated system comprising: a) a photoelectrochemical electrolysis unit adapted to split water into hydrogen and oxygen using sunlight; i) at least one cathode in a cathode region adapted to produce hydrogen and concentrated base in the form of hydroxide ions; and ii) at least one anode in an anode region adapted to produce oxygen and concentrated acid in the form of protons; and iii) an aqueous electrolyte solution in contact with the cathode and the anode; b) a hydrogen sequestration tank for collecting and processing the hydrogen produced at the cathode; c) an oxygen sequestration tank for collecting and processing the oxygen produced at the anode; d) an acid sequestration tank for collecting and processing the acid produced at the anode; e) a base sequestration tank for collecting and processing the base produced at the cath
  • Embodiment 2 is a photoelectrochemical apparatus for generating renewable hydrogen and sequestering atmospheric carbon dioxide or carbon dioxide from a gas stream, the apparatus comprising: a) a photoelectrochemical electrolysis unit adapted to split water into hydrogen and oxygen using sunlight, wherein the electrolysis unit comprises: i) at least one cathode adapted to produce hydrogen and concentrated base in the form of hydroxide ions; ii) at least one anode adapted to produce oxygen and concentrated acid in the form of protons; and iii) an aqueous electrolyte solution; b) a gas contact assembly adapted to receive carbon dioxide and hydroxide ions produced in the photoelectrochemical electrolysis unit so that the carbon dioxide contacts and reacts with the hydroxide ions to form bicarbonate or carbonate ions in solution; and c) a separation chamber connected to the gas contact assembly and adapted to separate the bicarbonate or carbonate ions from the solution.
  • a photoelectrochemical electrolysis unit adapted
  • the photoelectrochemical electrolysis unit is one of a photovoltaic unit, a semiconductor-liquid junction unit or a photovoltaic/semiconductor-liquid junction unit.
  • the apparatus of embodiment 2 further comprising gas supply equipment adapted to route carbon dioxide to the gas contact assembly.
  • the apparatus of embodiment 2 further comprising equipment for isolating and processing the hydrogen, oxygen, acid, base, carbonate ions or bicarbonate ions.
  • the anode is a photo-anode.
  • Embodiment 3 is a method of generating renewable hydrogen and sequestering carbon dioxide from an air or gas stream comprising: a) supplying sunlight to a photoelectrochemical electrolysis unit including an anode located in an anode region and a cathode located in a cathode region, wherein the anode and the cathode are in contact with an aqueous electrolyte; b) producing oxygen gas and acid at the anode, wherein the acid is in the form of protons; c) producing hydrogen gas and base at the cathode, wherein the base is in the form of hydroxide ions; d) collecting the hydrogen gas; e) collecting the oxygen gas; f) removing acid from the anode region; g) removing base from the cathode region; and h) contacting the hydroxide ions in the base with a source of gaseous carbon dioxide to sequester carbon dioxide in solution as bicarbonate, carbonate or a mixture thereof.
  • the photoelectrochemical electrolysis unit is one of a photovoltaic unit, a semiconductor-liquid junction unit or a photovoltaic/semiconductor-liquid junction unit.
  • the method of embodiment 3, further comprising reacting the bicarbonate or carbonate with the acid produced in the photoelectrochemical electrolysis unit to generate concentrated carbon dioxide gas or super critical carbon dioxide.
  • the method of embodiment 3, further comprising isolating and processing at least one of the hydrogen, oxygen, acid, base, carbonate or bicarbonate.

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Abstract

La présente invention a trait à un système permettant la séquestration du CO2 et la production d'hydrogène, d'oxygène, d'acide et de base renouvelables, ledit système comprenant une unité d'électrolyse photoélectrochimique, une cuve de séquestration de l'hydrogène, une cuve de séquestration de l'oxygène, une cuve de séquestration d'un acide, une cuve de séquestration d'une base et une zone de contact gazeux. L'unité d'électrolyse photoélectrochimique est apte à séparer l'eau en oxygène et en hydrogène en utilisant la lumière solaire et comprend une cathode apte à produire de l'hydrogène et une base, une anode apte à produire de l'oxygène et un acide, et une solution aqueuse d'électrolyte. Les cuves de séquestration de l'hydrogène, de la base, de l'oxygène et de l'acide servent à récupérer et à traiter l'hydrogène, la base, l'oxygène et l'acide, respectivement. La zone de contact gazeux est apte à faire réagir le CO2 soit avec la base, soit avec une solution de séquestration du CO2 préparée à partir de l'acide. Le système intégré fournit un procédé qui permet d'incorporer le CO2 dans des produits de valeur à base de carbone. La vente de ces produits négatifs en carbone permettra de subventionner la production d'hydrogène renouvelable à partir de l'eau tout en réduisant les émissions de CO2 à l'échelle mondiale.
PCT/US2008/065387 2007-05-30 2008-05-30 Utilisation de la dissociation photoélectrochimique de l'eau pour produire des matériaux destinés à la séquestration du dioxyde de carbone WO2008151060A1 (fr)

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US60/932,542 2007-05-30

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US8137444B2 (en) 2009-03-10 2012-03-20 Calera Corporation Systems and methods for processing CO2
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US8357270B2 (en) 2008-07-16 2013-01-22 Calera Corporation CO2 utilization in electrochemical systems
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US20210404072A1 (en) * 2020-06-24 2021-12-30 Jonathan Jan Hydrogen separation system and method therefor
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US7753618B2 (en) 2007-06-28 2010-07-13 Calera Corporation Rocks and aggregate, and methods of making and using the same
US7931809B2 (en) 2007-06-28 2011-04-26 Calera Corporation Desalination methods and systems that include carbonate compound precipitation
US7744761B2 (en) 2007-06-28 2010-06-29 Calera Corporation Desalination methods and systems that include carbonate compound precipitation
US7749476B2 (en) 2007-12-28 2010-07-06 Calera Corporation Production of carbonate-containing compositions from material comprising metal silicates
US7887694B2 (en) 2007-12-28 2011-02-15 Calera Corporation Methods of sequestering CO2
US7754169B2 (en) 2007-12-28 2010-07-13 Calera Corporation Methods and systems for utilizing waste sources of metal oxides
US8333944B2 (en) 2007-12-28 2012-12-18 Calera Corporation Methods of sequestering CO2
US9260314B2 (en) 2007-12-28 2016-02-16 Calera Corporation Methods and systems for utilizing waste sources of metal oxides
US8357270B2 (en) 2008-07-16 2013-01-22 Calera Corporation CO2 utilization in electrochemical systems
US7875163B2 (en) 2008-07-16 2011-01-25 Calera Corporation Low energy 4-cell electrochemical system with carbon dioxide gas
US8894830B2 (en) 2008-07-16 2014-11-25 Celera Corporation CO2 utilization in electrochemical systems
US7993500B2 (en) 2008-07-16 2011-08-09 Calera Corporation Gas diffusion anode and CO2 cathode electrolyte system
US7966250B2 (en) 2008-09-11 2011-06-21 Calera Corporation CO2 commodity trading system and method
US7815880B2 (en) 2008-09-30 2010-10-19 Calera Corporation Reduced-carbon footprint concrete compositions
US8006446B2 (en) 2008-09-30 2011-08-30 Calera Corporation CO2-sequestering formed building materials
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US8431100B2 (en) 2008-09-30 2013-04-30 Calera Corporation CO2-sequestering formed building materials
US8470275B2 (en) 2008-09-30 2013-06-25 Calera Corporation Reduced-carbon footprint concrete compositions
US8603424B2 (en) 2008-09-30 2013-12-10 Calera Corporation CO2-sequestering formed building materials
US7771684B2 (en) 2008-09-30 2010-08-10 Calera Corporation CO2-sequestering formed building materials
US8869477B2 (en) 2008-09-30 2014-10-28 Calera Corporation Formed building materials
US9133581B2 (en) 2008-10-31 2015-09-15 Calera Corporation Non-cementitious compositions comprising vaterite and methods thereof
US7829053B2 (en) 2008-10-31 2010-11-09 Calera Corporation Non-cementitious compositions comprising CO2 sequestering additives
US7790012B2 (en) 2008-12-23 2010-09-07 Calera Corporation Low energy electrochemical hydroxide system and method
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US8491858B2 (en) 2009-03-02 2013-07-23 Calera Corporation Gas stream multi-pollutants control systems and methods
US8137444B2 (en) 2009-03-10 2012-03-20 Calera Corporation Systems and methods for processing CO2
US7993511B2 (en) 2009-07-15 2011-08-09 Calera Corporation Electrochemical production of an alkaline solution using CO2
CN102770194A (zh) * 2010-01-14 2012-11-07 费伦茨·梅萨罗斯 还原烟气和大气气体中co2成分的方法及实施该方法的设备
US9493881B2 (en) 2011-03-24 2016-11-15 New Sky Energy, Inc. Sulfate-based electrolysis processing with flexible feed control, and use to capture carbon dioxide
US8945368B2 (en) 2012-01-23 2015-02-03 Battelle Memorial Institute Separation and/or sequestration apparatus and methods
US20210376413A1 (en) * 2020-05-30 2021-12-02 Solomon Alema Asfha Apparatuses and methods for carbon dioxide capturing and electrical energy producing system
US20210404072A1 (en) * 2020-06-24 2021-12-30 Jonathan Jan Hydrogen separation system and method therefor
US11850566B2 (en) 2020-11-24 2023-12-26 Aircela Inc. Synthetic fuel production system and related techniques

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