WO2011066293A1 - Production d'une solution alcaline à l'aide d'une anode à diffusion gazeuse avec une pression hydrostatique - Google Patents

Production d'une solution alcaline à l'aide d'une anode à diffusion gazeuse avec une pression hydrostatique Download PDF

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Publication number
WO2011066293A1
WO2011066293A1 PCT/US2010/057821 US2010057821W WO2011066293A1 WO 2011066293 A1 WO2011066293 A1 WO 2011066293A1 US 2010057821 W US2010057821 W US 2010057821W WO 2011066293 A1 WO2011066293 A1 WO 2011066293A1
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Prior art keywords
anode
electrolyte
cathode
exchange membrane
electrochemical
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PCT/US2010/057821
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English (en)
Inventor
Ryan J. Gilliam
Nigel Antony Knott
Bryan Boggs
Alexander Sasha Gorer
Valentin Decker
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Calera Corporation
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Publication of WO2011066293A1 publication Critical patent/WO2011066293A1/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
    • C25B1/01—Products
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/60—Preparation of carbonates or bicarbonates in general
    • 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
    • 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
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • 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
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • C25B1/01—Products
    • C25B1/14—Alkali metal compounds
    • 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
    • C25B1/01—Products
    • C25B1/14—Alkali metal compounds
    • C25B1/16—Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46152—Electrodes characterised by the shape or form
    • C02F2001/46157—Perforated or foraminous electrodes
    • C02F2001/46161—Porous electrodes
    • C02F2001/46166—Gas diffusion electrodes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/46115—Electrolytic cell with membranes or diaphragms
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/4619—Supplying gas to the electrolyte
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • an alkaline solution e.g., an aqueous NaOH solution
  • an electrochemical system by reducing water to hydroxyl ions (OH " ) and hydrogen gas (H 2 ) at the cathode, and migrating the OH " into the cathode electrolyte where they combine with cations e.g., Na + from an aqueous salt solution e.g., an NaCI solution to form the alkaline solution.
  • H 2 is oxidized to protons (H + ) and electrons (e " ), and the H + are migrated into the anode electrolyte where they combine with anions e.g., CI " from the salt solution to form an acid, e.g., hydrochloric acid.
  • the cathode electrolyte comprising the alkaline solution is mixed with carbon dioxide and a divalent cation solution e.g., CaC and/or MgSO 4 to sequester the gas as a carbonate and/or bicarbonate, e.g., CaCO3, and/or MgCO3 and/or Na2CO3 and or NaHCO3.
  • a divalent cation solution e.g., CaC and/or MgSO 4 to sequester the gas as a carbonate and/or bicarbonate, e.g., CaCO3, and/or MgCO3 and/or Na2CO3 and or NaHCO3.
  • the anode electrolyte comprising the acid is used to dissolve a mineral e.g., olivine to produce the divalent cation solution.
  • This invention pertains to an energy efficient system and method of producing an alkaline solution in the cathode electrolyte of an electrochemical system using a gas diffusion anode with an external hydrostatic pressure applied onto the gas diffusion anode.
  • the pressure applied on the anode squeezes the components of the anode for good physical and electrical contact and thereby eliminates ohmic voltage spikes at the anode that would otherwise occur due to inadequate contacts. Since a voltage spike at the anode will cause a voltage spike across the anode and cathode, the elimination of voltage spikes at the anode will reduce the energy used in the system.
  • the cell voltage is the voltage across the anode and cathode required to produce the alkaline solution, and includes the half-cell voltages for the electrochemical reactions at the anode and cathode, and the voltage required to overcome ohmic resistance in the system e.g., at the electrodes, across the electrolytes, and across ion exchange membranes in the system.
  • the external hydrostatic pressure is applied to the anode via a pressure applied to the anode electrolyte.
  • a cation exchange membrane is in contact the anode and separates the anode from the anode electrolyte, hence in some embodiments, the hydrostatic pressure on the anode is transmitted to the anode from the anode electrolyte through the cation exchange membrane.
  • the alkaline solution is produced in the cathode electrolyte by oxidizing water to OH " and H 2 at the cathode, and migrating the OH " into the cathode electrolyte to combine with cations e.g., Na+ from a salt solution to produce the alkaline solution, e.g., a NaOH solution in the cathode electrolyte.
  • cations e.g., Na+ from a salt solution to produce the alkaline solution, e.g., a NaOH solution in the cathode electrolyte.
  • H 2 is oxidized to H + and e " , and the H + are migrated into the anode electrolyte where they combine with anions e.g., CI " from the salt solution to produce an acid e.g., hydrochloric acid in the anode electrolyte.
  • anions e.g., CI " from the salt solution to produce an acid e.g., hydrochloric acid in the anode electrolyte.
  • the cathode electrolyte is the electrolyte that is configured to remove anions formed at the cathode and is usually in direct contact with the cathode; in some embodiments the cathode electrolyte my be separated from cathode by an anion exchange membrane that is configured to transmit the anions from the cathode to the cathode electrolyte. In some embodiments the cathode electrolyte may be referred to herein as the catholyte.
  • the anode electrolyte is the electrolyte that is configured to remove cations formed at the cathode and is usually in direct contact with the anode; in some embodiments the anode electrolyte my be separated from anode by an cation exchange membrane that is configured to transmit the cations from the anode to the anode electrolyte. In some embodiments the anode electrolyte may be referred to herein as the anolyte.
  • the system comprises a first cation exchange membrane in contact with the gas diffusion anode and configured to separate the gas diffusion anode from the anode electrolyte; a cathode in contact with a cathode electrolyte; and a second cation ion exchange membrane configured to separate the cathode electrolyte from the anode electrolyte.
  • an external pressure system is configured to apply a pressure on the anode electrolyte.
  • an external pressure system of at least 4 psi is transmitted to the anode via the first cation exchange membrane in contact with the anode.
  • the system is configured with a gap of 5 mm or less between the first cation exchange membrane and the second cation exchange membrane.
  • the cathode electrolyte comprises added carbon dioxide and in some embodiments, the anode electrolyte comprises a salt solution comprising sodium chloride or potassium sulfate.
  • the gas diffusion anode comprises a substrate comprising a catalyst configured to catalyze oxidization of hydrogen gas to protons.
  • the substrate comprises a first side in contact with hydrogen and an opposed second side in contact with the first cation exchange membrane.
  • the substrate first side in contact with hydrogen is hydrophobic, and the substrate second side in contact with anode electrolyte is hydrophilic.
  • the substrate is porous and is configured to diffuse hydrogen from the first side in contact with hydrogen to the second side in contact with the first cation exchange membrane.
  • the catalyst comprises platinum, ruthenium, iridium, rhodium, manganese, silver or alloys thereof.
  • the first cation exchange membrane comprises a hydrocarbon-based cation exchange membrane; in some embodiments, the first cation exchange membrane comprises a monolayer hydrocarbon-based cation exchange membrane; in some embodiments, the first cation exchange membrane comprises plolytetraflouroethylene; and in some embodiments, the first cation exchange membrane comprises sulfonated plolytetraflouroethylene.
  • the first cation exchange membrane is configured to migrate protons from the substrate into the anode electrolyte on application of a voltage across the anode and the cathode.
  • the anode electrolyte comprises hydrochloric acid; in some embodiments, the anode electrolyte comprises sulfuric acid.
  • the system is configured to produce hydrogen and hydroxyl ions at the cathode on applying the voltage across the anode and cathode. In some embodiments, the system is configured to migrate hydroxide ions from the cathode into the cathode electrolyte.
  • the system is configured to migrate cations from the anode electrolyte into the cathode electrolyte through the second cation exchange membrane.
  • the cations comprise sodium or potassium ions.
  • the system comprises a hydrogen delivery system configured to direct hydrogen to the anode.
  • the hydrogen delivery system is configured to direct hydrogen from the cathode to the anode.
  • the system is configured to maintain a temperature of 70 °C to 75 °C in the anode electrolyte. In some embodiments, the system is configured to maintain a current density of 150- 200 mA cm 2 at the cathode.
  • the system is configured to maintain a pH of 0 or less in the anode electrolyte, and 14 or more in the cathode electrolyte.
  • the system comprises a current collector in contact with the gas diffusion layer of the gas diffusion anode; in some embodiments, the current collector comprises titanium or platinum.
  • the system is comprised of a cell wall comprising a non- corrosive material.
  • the cell wall comprises a polymer e.g., polyvinyl chloride.
  • the system is operatively connected to a waste gas system and configured to dissolve carbon dioxide from the waste gas into the cathode electrolyte.
  • the system is configured to produce a carbonate and/or bicarbonate product by mixing the cathode electrolyte with a divalent cation solution.
  • the divalent cation solution comprises calcium and/or magnesium ions
  • the carbonate/bicarbonate product comprises calcium carbonate and/or magnesium carbonate and/or sodium bicarbonate and/or sodium carbonate.
  • the system is configured to dissolve a mineral with the anode electrolyte to produce the divalent cation solution.
  • the method comprises separating a gas diffusion anode from an anode electrolyte using a first cation exchange membrane in contact with the gas diffusion anode; separating the anode electrolyte from a cathode electrolyte contacting a cathode using a second cation exchange membrane; applying an external hydrostatic pressure on the anode electrolyte; producing an alkaline solution in the cathode electrolyte without producing a gas at the anode by applying a voltage across the gas diffusion anode and cathode.
  • the method comprises applying at least 4 psi of hydrostatic pressure to the anode electrolyte and transmitting this pressure to the anode via the first cation exchange membrane.
  • the method comprises oxidizing hydrogen to protons at the gas diffusion anode and migrating protons from the gas diffusion anode through the first cation exchange membrane and into the anode electrolyte.
  • the anode electrolyte comprises sodium chloride or potassium sulfate.
  • the method comprises migrating sodium or potassium ions from the anode electrolyte into the cathode electrolyte through the second cation exchange membrane. In some embodiments, the method comprises producing
  • hydrochloric acid or sulfuric acid in the anode electrolyte hydrochloric acid or sulfuric acid in the anode electrolyte.
  • the method comprises producing hydroxyl ions and hydrogen at the cathode. In some embodiments, the method comprises migrating hydroxyl ions from the cathode into the cathode electrolyte. In some embodiments, the method comprises directing hydrogen generated at the cathode to the gas diffusion anode and oxidizing the hydrogen to protons and electrons at the anode.
  • the gas diffusion anode comprises a substrate comprising a catalyst configured to catalyze oxidation of hydrogen to protons and electrons.
  • the method comprising contacting the substrate at a first side with hydrogen and contacting the substrate at an opposed second side with the first cation exchange membrane.
  • the substrate first side is hydrophobic and the substrate second side is hydrophilic; in some embodiments, the substrate is porous and is configured to diffuse hydrogen from the first side in contact with hydrogen to the second side in contact with the first cation exchange membrane.
  • the catalyst comprises platinum
  • the first cation exchange membrane comprises a hydrocarbon-based cation exchange membrane. In some embodiments, the first cation exchange membrane comprises a monolayer hydrocarbon-based cation exchange membrane. In some embodiments, the first cation exchange membrane comprises plolytetraflouroethylene; in some embodiments, the first cation exchange membrane comprises sulfonated plolytetraflouroethylene.
  • cations are migrated from the anode electrolyte into the cathode electrolyte through the second cation exchange membrane.
  • hydrogen gas is diffused through the substrate to the catalyst.
  • the method comprises adding carbon dioxide to the cathode electrolyte and producing carbonates ions and/or bicarbonate ions in the cathode electrolyte.
  • the carbon dioxide is obtained from a waste gas; in some embodiments, the waste gas is obtained from an industrial plant.
  • the industrial plant is a fossil fuelled electrical power generating plant, a cement production plant or an ore processing facility that generates carbon dioxide.
  • carbon dioxide in ambient air is excluded from the cathode electrolyte and thus the cathode electrolyte is devoid of ambient carbon dioxide.
  • the ion exchange membranes are configured such that a gap of 5mm or less is maintained between the first and second cation exchange membrane.
  • the method comprises contacting the cathode electrolyte with a divalent cation solution to produce a carbonate or bicarbonate product comprising calcium and/or magnesium.
  • the divalent cation comprises magnesium ions or calcium ions.
  • the method comprises dissolving a mineral with the anode electrolyte to produce the divalent cation solution.
  • the method comprises maintaining a pH of 7 or greater in the cathode electrolyte; in some embodiments, the method comprises maintaining a pH of between 7 and 9 in the cathode electrolyte. In some embodiments, the method comprises maintaining a pH of between 8 and 1 1 in the cathode electrolyte. In some embodiments, the method comprises maintaining a pH of less than 7 in the anode electrolyte. In some embodiments, the method comprises maintaining a pH of less than 4 in the anode electrolyte. [0045] In some embodiments, the method comprises oxidizing hydrogen gas to hydrogen ions at the anode and migrating the hydrogen ions through the first cation exchange membrane into the anode electrolyte. In some embodiments, the method comprises producing hydroxide ions and hydrogen gas at the cathode. In some embodiments,
  • the method comprises directing hydrogen gas from the cathode to the anode and oxidizing the hydrogen at the anode.
  • the method comprises migrating cations ions through the second cation exchange membrane into the cathode electrolyte.
  • the cations comprise sodium ions.
  • the method comprises producing an acid in the anode electrolyte.
  • the method comprises establishing a temperature of 70 °C to 75 °C in the anode electrolyte. In some embodiments, the method comprises establishing a current density of 150- 200 mA cm 2 at the cathode.
  • the method comprises maintaining a pH of 0 or less in the anode electrolyte, and 14 or more in the cathode electrolyte.
  • the anode and cathode are disposed in an
  • the first cation exchange membrane is configured to separate the anode from the anode electrolyte, and as this membrane will migrate H + from the anode into the anode electrolyte while blocking migration of anions e.g., CI " from the anode electrolyte into the anode, therefore by this configuration of the system and method the anode does not come in contact with an acid.
  • the catalyst at the anode is protected from contact with an acid that may otherwise form at the anode by a combination of H+ from the anode and anions from the anode electrolyte . Consequently, in the system, the efficiency of the catalyst is sustained, which will lower the voltage required across the anode and cathode, and hence lower the energy used in producing the alkaline solution.
  • the alkaline solution produced in the cathode electrolyte is mixed with carbon dioxide and a divalent cation solution to sequester the carbon dioxide as cementitous carbonate and/or bicarbonate as disclosed in commonly assigned US Patent no. 7,735,274 herein incorporated by reference in its entirety.
  • the acid produce in the anode electrolyte is used to dissolve a mineral to produce a divalent cation solution used in producing the cementitous carbonate and/or bicarbonate.
  • Fig. 1 is an illustration of an embodiment of the present gas diffusion anode.
  • FIG. 2 is an illustration of an embodiment of the present electrochemical system comprising a gas diffusion anode.
  • FIG. 3 is an illustration of an embodiment of the present electrochemical system comprising a gas diffusion anode.
  • Fig. 4 is an illustration an embodiment of the present electrochemical system integrated with a carbon dioxide sequestration system.
  • Fig. 5 is an illustration voltage potential across the anode and cathode vs. the pH of the cathode electrolyte.
  • the energy used to produce an alkaline solution is correlated to the cell voltage.
  • the cell voltage is the voltage across the anode and cathode required to produce the alkaline solution and is the cumulative voltage drops in the system, including: i) the half-cell voltages for the electrochemical reactions at the anode and cathode; ii) ohmic voltage drops due to electrical resistance e.g., at the electrodes, across the ion exchange membranes, across the electrolytes and elsewhere, and iii) the current density at the cathode required to produce a desired rate of OH " in the cathode electrolyte.
  • the cell voltage can be reduced by oxidizing H 2 gas to H + and e " at the anode while suppressing production of a gas e.g., oxygen or chlorine at the anode, and while reducing water at the cathode to OH " and H 2 gas.
  • a gas e.g., oxygen or chlorine
  • This reduction in cell voltage is achieved since in such systems H 2 gas is oxidized to H + and e " at the anode, and therefore in such systems the half-cell voltage at the anode is 0 V and therefore in the system the half-cell voltage at the anode does not contribute to the cell voltage.
  • an anode that can be used to oxidize H 2 gas to H + and e " to achieve a 0 V half-cell voltage at the anode is a gas diffusion anode as illustrated
  • the gas diffusion anode 100 comprises a conductive substrate 102 comprising a first side 106 that interfaces with the hydrogen 108 and an opposed second side 1 10 that interfaces with the anode electrolyte 1 12.
  • the side of the substrate 106 that interfaces with the hydrogen is
  • the side of the substrate 106 that interfaces with the anode electrolyte is hydrophilic and porous and will allow the anode electrolyte to diffuse therein.
  • the gas diffusion anode includes a current collector 1 14 through which electrons generated at the anode are removed from the anode via the power supply 1 16 and are conducted to the cathode to facilitate the reduction reaction at the cathode.
  • the substrate is infused with a catalyst 104 to catalyze the oxidation of hydrogen to protons and electrons.
  • the catalyst may comprise platinum, ruthenium, iridium, rhodium, manganese, silver or alloys thereof that promote oxidation of hydrogen to protons and electrons.
  • Gas diffusion anodes are commercially available e.g., from E-TEK (USA), or can be assembled from components as described in the publication titled: "Electrochemical Study of Hydrogen Diffusion Anode-membrane assembly for Membrane Electrolysis",
  • the problem can be attributed to inadequate physical and electrical contact at the anode possibly caused e.g., by poor assembly of the anode layers and/or by expansion of the anode layers due to temperature changes in the anode from ohmic heating at the anode and/or heat released by the electrochemical reaction at the anode.
  • membrane 212 configured to separate the cathode electrolyte from the anode electrolyte.
  • the first cation exchange membrane 1 14, 202 comprises a hydrocarbon-based cation exchange membrane.
  • cation exchange membranes used in the system are commercially available as discussed above, however it will be appreciated that in some embodiments, depending on the need to restrict or allow migration of a specific cation or an anion species between the electrolytes, a cation exchange membrane that is more restrictive and thus allows migration of one species of cations while restricting the migration of another species of cations may be used as, e.g., a cation exchange membrane that allows migration of sodium ions into the cathode electrolyte from the anode electrolyte while restricting migration of hydrogen ions from the anode electrolyte into the cathode electrolyte, may be used.
  • restrictive cation exchange membranes are commercially available and can be selected by one ordinarily skilled in the art.
  • the cathode electrolyte 210 comprises carbonate ions and/or bicarbonate ions.
  • the system 200 is configured to migrate cations from the anode electrolyte 206 into the cathode electrolyte 210 through the second cation exchange membrane 212.
  • the cations comprise sodium where a sodium salt e.g., sodium chloride is used, or potassium ions where a potassium salt e.g., potassium sulfate is used.
  • the system 200 is configured to maintain a pH of 0 or less in the anode electrolyte 206, and a pH of 14 or more in the cathode electrolyte 210.
  • the waste gas is obtained from an industrial plant, e.g., a power generating plant, a cement plant, or an ore smelting plant.
  • the carbon dioxide in the waste gas is greater than the concentration of carbon dioxide in the ambient atmosphere.
  • This source of carbon dioxide may also contain other gaseous and non-gaseous components of a combustion process, e.g., nitrogen gas, SO x , NO x. as is described in co-pending and commonly assigned US Provisional Patent application no. 61/223,657, titled “Gas, Liquids, Solids Contacting Methods and Apparatus", filed July 7, 2009 herein fully incorporated by reference.
  • the pH of the anode electrolyte is adjusted to a value between 0 and 7, including 0, 0.5, 1 .0, 1 .5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5 and 7, depending on the desired operating voltage across the anode and cathode.
  • carbon dioxide can be added to the electrolyte as disclosed herein to achieve a desired pH difference between the anode electrolyte and cathode electrolyte.
  • these equivalent systems are within the scope of the present invention.
  • the anode electrolyte 206 comprises a salt solution that includes sodium ions and chloride ions and the system 200 is configured to produce the alkaline solution in the cathode electrolyte 210 while also producing hydrogen ions at the anode 202, with less than 1 V across the anode 202 and cathode 208, without producing a gas at the anode; in some embodiments, the system 200 is configured to migrate the hydrogen ions from the anode 204 into the anode electrolyte 206; in some embodiments, the anode electrolyte comprises an acid; in some
  • the system 200 is configured to produce bicarbonate ions and/or carbonate ions in the cathode electrolyte 210; in some embodiments, the system is configured to migrate hydroxide ions from the cathode 208 into the cathode electrolyte 210; migrate cations, e.g., sodium ions, from the anode electrolyte 206 into the cathode electrolyte through the second cation exchange membrane 212; in some embodiments, hydrogen gas from the cathode is collected and provided to the anode through and a hydrogen gas delivery system 224.
  • the system is configured to produce bicarbonate ions and/or carbonate ions in the cathode electrolyte 210; in some embodiments, the system is configured to migrate hydroxide ions from the cathode 208 into the cathode electrolyte 210; migrate cations, e.g., sodium ions, from the anode electrolyte 206 into the cathode electrolyt
  • the system 200, 300 comprises a partition 326 that partitions the cathode electrolyte into a first cathode electrolyte portion 108A and a second cathode electrolyte portion 108B, wherein the second cathode electrolyte portion 108B, comprising added carbon dioxide, contacts the cathode 208; and wherein the first cathode electrolyte portion 108A comprising added carbon dioxide is in contact with the second cathode electrolyte portion 108B under the partition 326.
  • the system includes a hydrogen gas supply system 108, 224 configured to provide hydrogen gas to the anode 102, 204.
  • the hydrogen may be obtained from the cathode 208 or may be obtained from external source, e.g., from a commercial hydrogen gas supplier, e.g., at start-up of the system when the hydrogen supply from the cathode is insufficient.
  • the hydrogen gas is oxidized to protons and electrons; in some embodiments, un-reacted hydrogen gas is recovered and circulated at the anode.
  • the system in some embodiments includes a cathode electrolyte circulating system 344 adapted for withdrawing and circulating cathode electrolyte in the system.
  • the cathode electrolyte circulating system 344 comprises a carbon dioxide gas/liquid contactor 216 that is adapted for dissolving carbon dioxide in the circulating cathode electrolyte, and for circulating the electrolyte in the system.
  • the electrochemical system 200 may be operatively connected to a carbon dioxide sequestration system 400 for sequestering carbon dioxide to produce e.g., a carbonate and/or bicarbonate.
  • the sequestration system 400 may comprise carbonate precipitator 402 configured to precipitate carbonates and/or bicarbonates from a solution, wherein in some embodiments the carbonates and/or bicarbonates comprise calcium and/or magnesium carbonate and/or bicarbonate. Also as illustrated in Fig.
  • the anode electrolyte of the electrochemical system 200 comprising an acid e.g., hydrochloric acid and a depleted salt solution comprising low amount sodium ions is used in a mineral dissolution system 404 that is configured to dissolve minerals and produce a mineral solution comprising calcium ions and/or magnesium ions, e.g., mafic minerals such as olivine and serpentine.
  • the acid may be used for other purposes in addition to or instead of mineral dissolution e.g., use as a reactant in production of cellulosic biofules, use the production of polyvinyl chloride (PVC), and the like.
  • System appropriate to such uses may be operatively connected to the electrochemical system 200, 300, or the acid may be transported to the appropriate site for use.
  • the method comprises a step of oxidizing hydrogen gas 108, 220 to hydrogen ions at the anode 100, 204 and migrating the hydrogen ions through the first cation exchange membrane 202 into the anode electrolyte 206.
  • the method comprises producing hydroxide ions and hydrogen gas at the cathode.
  • the method comprises directing hydrogen gas from the cathode 208 to the anode 204 and oxidizing the hydrogen at the anode.
  • the method comprises migrating cations ions through the second cation exchange membrane 212 into the cathode electrolyte 210.
  • the cations are obtained from a salt solution comprising sodium ions.
  • the method comprises producing an acid, hydrochloric acid or sulfuric acid in the anode electrolyte.
  • the method comprises establishing a temperature of 70 °C to 75 °C in the anode electrolyte. In some embodiments, the method comprises establishing a current density of 150- 200 mA cm 2 at the cathode.
  • the method comprises maintaining a pH of 0 or less in the anode electrolyte, and 14 or more in the cathode electrolyte.
  • the anode and cathode are disposed in an
  • the electrochemical cell comprising cell walls comprising a non-corrosive material.
  • the cell walls comprise a polymer; in some embodiments the cell walls comprise polyvinyl chloride.
  • the method comprises maintaining a gap of 5mm or less between the first and second cation exchange membrane.
  • the system includes a gas treatment system that removes constituents in the carbon dioxide gas stream before the gas is utilized in the cathode electrolyte.
  • a portion of, or the entire amount of, cathode electrolyte comprising bicarbonate ions and/or carbonate ions/ and or hydroxide ions is withdrawn from the system and is contacted with carbon dioxide gas in an exogenous carbon dioxide gas/liquid contactor to increase the absorbed carbon dioxide content in the solution.
  • the solution enriched with carbon dioxide is returned to the cathode compartment; in other embodiments, the solution enriched with carbon dioxide is reacted with a solution comprising divalent cations to produce divalent cation hydroxides, carbonates and/or bicarbonates.
  • the pH of the cathode electrolyte is adjusted upwards by hydroxide ions that migrate from the cathode, and/or downwards by dissolving carbon dioxide gas in the cathode electrolyte to produce carbonic acid and carbonic ions that react with and remove hydroxide ions.
  • the pH of the cathode electrolyte is determined, at least in part, by the balance of these two processes.
  • the cathode electrolyte may comprise dissolved and undissolved carbon dioxide gas, and/or carbonic acid, and/ or bicarbonate ions and/or carbonate ions.
  • hydroxide ions, carbonate ions and/or bicarbonate ions produced in the cathode electrolyte, and hydrochloric acid produced in the anode electrolyte are removed from the system, while sodium chloride in the salt solution electrolyte is replenished to maintain continuous operation of the system.
  • the system can be configured to operate in various production modes including batch mode, semi-batch mode, continuous flow mode, with or without the option to withdraw portions of the hydroxide solution produced in the cathode electrolyte, or withdraw all or a portions of the acid produced in the anode electrolyte, or direct the hydrogen gas produced at the cathode to the anode where it may be oxidized.
  • the voltage across the anode and cathode can be adjusted such that gas will form at the anode, e.g., oxygen or chlorine, while hydroxide ions, carbonate ions and bicarbonate ions are produced in the cathode electrolyte and hydrogen gas is generated at the cathode.
  • gas e.g., oxygen or chlorine
  • hydroxide ions, carbonate ions and bicarbonate ions are produced in the cathode electrolyte and hydrogen gas is generated at the cathode.
  • hydrogen gas is not supplied to the anode.
  • the voltage across the anode and cathode will be generally higher compared to the embodiment when a gas does not form at the anode.
  • the cathode and anode are also operatively connected to an off-peak electrical power-supply system 1 14 that supplies off-peak voltage to the electrodes. Since the cost of off-peak power is lower than the cost of power supplied during peak power-supply times, the system can utilize off-peak power to produce an alkaline solution in the cathode electrolyte at a relatively lower cost.
  • alternative reactants can be utilized depending on the ionic species desired in cathode electroyte and/or the anode electolyte.
  • a potassium salt such as potassium hydroxide or potassium carbonate
  • a potassium salt such as potassium chloride
  • sulfuric acid is desired in the anode electrolyte
  • a sulfate such as sodium sulfate
  • the present system and method are integrated with a carbonate and/or bicarbonate solution disposal system wherein, rather than producing precipitates by contacting a solution of divalent cations with the cathode electrolyte solution to form precipitates as illustrated in Fig. 4, the system produces a solution or a slurry or a suspension comprising carbonates and/or bicarbonates.
  • the solution, slurry or suspension is disposed of in a location where it is held stable for an extended periods of time, e.g., the solution/slurry/suspension is disposed in an ocean at a depth where the temperature and pressure are sufficient to keep the slurry stable indefinitely, or in a subterranean site as described in U.S. Patent Application no.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

La présente invention se rapporte à un système électrochimique comprenant une première membrane d'échange de cations en contact avec une anode à diffusion gazeuse et configurée pour séparer l'anode à diffusion gazeuse d'un électrolyte d'anode; une cathode en contact avec un électrolyte de cathode; et une seconde membrane d'échange d'ions cationiques configurée pour séparer l'électrolyte de cathode de l'électrolyte d'anode. Dans le système, un système de pression externe est configuré pour appliquer une pression contre la première membrane d'échange de cations à travers l'électrolyte d'anode et une solution alcaline est produite dans l'électrolyte de cathode par application d'une tension à travers l'anode et la cathode; dans certains modes de réalisation, le dioxyde de carbone est nécessaire par réaction avec l'électrolyte de cathode.
PCT/US2010/057821 2009-11-30 2010-11-23 Production d'une solution alcaline à l'aide d'une anode à diffusion gazeuse avec une pression hydrostatique WO2011066293A1 (fr)

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