US20110042230A1 - Low-energy electrochemical bicarbonate ion solution - Google Patents

Low-energy electrochemical bicarbonate ion solution Download PDF

Info

Publication number
US20110042230A1
US20110042230A1 US12/989,781 US98978109A US2011042230A1 US 20110042230 A1 US20110042230 A1 US 20110042230A1 US 98978109 A US98978109 A US 98978109A US 2011042230 A1 US2011042230 A1 US 2011042230A1
Authority
US
United States
Prior art keywords
electrolyte
canceled
anode
cathode
exchange membrane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US12/989,781
Other languages
English (en)
Inventor
Ryan J. Gilliam
Bryan Boggs
Valentin Decker
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fortera Corp
Original Assignee
Calera Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Calera Corp filed Critical Calera Corp
Assigned to CALERA CORPORATION reassignment CALERA CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BOGGS, BRYAN, DECKER, VALENTIN, GILLIAM, RYAN
Assigned to CALERA CORPORATION reassignment CALERA CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BOGGS, BRYAN, DECKER, VALENTIN, GILLIAM, RYAN
Publication of US20110042230A1 publication Critical patent/US20110042230A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • 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
    • C25B1/22—Inorganic acids

Definitions

  • Bicarbonate ion solutions are used to regulate or achieve a chemical reaction or buffer the pH of a solution.
  • bicarbonate ion solutions are obtained by dissolving bicarbonate salts, e.g., sodium bicarbonate, in water.
  • bicarbonate salts e.g., sodium bicarbonate
  • producing bicarbonate salts conventionally is energy intensive and, consequently, bicarbonate ion solutions are expensive.
  • This invention pertains to a low energy system and method of producing bicarbonate ions utilizing an electrolyte and carbon dioxide in an electrochemical cell.
  • the system comprises an anode, a cathode and an electrolyte contained between ion exchange membranes in an electrochemical cell.
  • the system On applying a voltage across the anode and cathode while contacting the electrolyte with carbon dioxide, the system is capable of forming bicarbonate ions in the electrolyte without forming a gas at the electrodes, e.g., without forming hydrogen at the cathode or chlorine at the anode.
  • the system is also capable of forming an acid, e.g., hydrochloric acid in another electrolyte in contact with an ion exchange membrane; and, in various embodiments, ions of the anode can be recovered at the cathode by reusing the anode electrolyte at the cathode.
  • an acid e.g., hydrochloric acid
  • ions of the anode can be recovered at the cathode by reusing the anode electrolyte at the cathode.
  • the system comprising an anode, a cathode and an electrolyte contained between ion exchange membranes, is capable of forming bicarbonate ions in the electrolyte on applying a voltage of, e.g., less than 0.05 V across the anode and cathode while contacting the electrolyte with carbon dioxide.
  • the system is also capable of forming an acid, e.g., hydrochloric acid in another electrolyte in contact with an ion exchange membrane; and, in various embodiments, ions of the anode can be recovered at the cathode by reusing the anode electrolyte at the cathode.
  • the method comprises applying a voltage across an anode and a cathode in an electrochemical cell containing an electrolyte comprising carbon dioxide and contained between ion exchange membranes, to form bicarbonate ions in the electrolyte without forming a gas at the electrodes, e.g., without forming chlorine at the anode or hydrogen at the cathode.
  • the method is also capable of forming an acid, e.g., hydrochloric acid in another electrolyte in contact with an ion exchange membrane; and, in various embodiments, ions of the anode can be recovered at the cathode by reusing the anode electrolyte at the cathode.
  • the method comprises forming bicarbonate ions in an electrolyte contained between ion exchange membranes in an electrochemical cell by applying a voltage of less than 2.0 V, less than 1.5 V, less than 1.0 V, less than 0.5 V, less than 0.1 V or less than 0.05 V across the anode and cathode while contacting the electrolyte with carbon dioxide.
  • the system is also capable of forming an acid, e.g., hydrochloric acid in another electrolyte in contact with an ion exchange membrane; and, in various embodiments, ions of the anode can be recovered at the cathode by reusing the anode electrolyte at the cathode.
  • carbon dioxide from any convenient source can be used to contact the electrolyte between the ion exchange membranes.
  • sources include carbon dioxide dissolved in a liquid, carbon dioxide in solid form, e.g., dry ice, or gaseous carbon dioxide.
  • carbon dioxide in combustion gases of an industrial plant e.g., the stack gases of fossil fuel power-generating plants or cement plants can be used.
  • the present system and method are adaptable for batch, semi-batch or continuous flows of electrolytes, bicarbonate ions, carbon dioxide and acid in the electrochemical cell.
  • the solution comprising bicarbonates ions can be used to sequester carbon dioxide by contacting the bicarbonate ion solution with an alkaline earth metal ion solution in the presence of carbon dioxide to precipitate carbonates, e.g., to precipitate calcium and magnesium carbonates from saltwater as described in U.S. patent application Ser. No. 12/126,776, filed on May 23, 2008, herein incorporated by reference.
  • the precipitated carbonates in various embodiments, can be used as building products, e.g., cements and other building products as described in the United States Patent Applications incorporated herein by reference.
  • system and method can be used to precipitate carbonates from saltwater to produce desalinated water as described in U.S. patent application Ser. No. 12/163,205, filed on Jun. 27, 2008, herein incorporated by reference.
  • acids produced by the present method can be used to dissolve alkaline earth metal minerals to obtain alkaline earth metal cations for use in sequestering carbon dioxide as described in the United States patent applications incorporated herein by reference.
  • FIG. 1 illustrates an embodiment of the present system.
  • FIG. 2 illustrates an embodiment of the present system.
  • FIG. 3 illustrates an embodiment of the present system.
  • FIG. 4 illustrates an embodiment of the present system.
  • FIG. 5 is a flow chart of an embodiment of the present method.
  • FIG. 6 is a flow chart of an embodiment of the present method.
  • each intervening value in the range is encompassed by the invention.
  • values between the upper and lower limit of the range and any other stated and intervening value in the range are included unless the context clearly dictates otherwise.
  • upper and lower limits of smaller ranges are included in smaller ranges and are encompassed within the scope of the invention, subject to any specifically excluded limit in the stated range.
  • numerical values may be preceded by the term “about.”
  • the term “about” is used to provide literal support for the exact number that it precedes, and/or as a number that is near to or approximately the number that it precedes.
  • the near and/or approximating unrecited number may be a number that, in the context in which it is presented, provides the substantial equivalent of a specifically recited number.
  • the invention in various embodiments is described for convenience in terms of producing sodium bicarbonate ions, and optionally, hydrochloric acid.
  • the present system and method may produce other bicarbonate ions such as, e.g., potassium and calcium bicarbonate ions and other acids such as sulfuric acid, depending on the electrolytes used.
  • the present invention is directed to a low voltage system and method of forming bicarbonate ions by contacting carbon dioxide with an electrolyte salt solution positioned between ion exchange membranes in an electrochemical cell.
  • bicarbonate ions form in the solution without forming a gas at the electrodes, e.g., without forming chlorine at the anode or hydrogen at the cathode.
  • bicarbonate ions are formed in the solution on applying a voltage across the anode and cathode of less than 2.8, 2.7, 2.6, 2.5, 2.4, 2.3, 2.2, 2.1, 2.0, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1, 1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 V, and other low voltages as disclosed herein.
  • an acid solution is also formed in another electrolyte in contact with an ion exchange membrane, e.g., hydrochloric acid, in the electrochemical cell.
  • the electrolyte in contact with the anode is reused as the electrolyte at the cathode to recover anode material at the cathode.
  • system 100 comprises first electrolyte 102 and carbon dioxide 104 contained between anion exchange membrane 106 A and cation exchange membrane 108 A in an electrochemical cell 110 .
  • Electrochemical cell 100 includes anode 112 and cathode 114 ; second electrolyte 116 contacting anion exchange membrane 106 A and anode 112 ; and third electrolyte 118 contacting cation exchange 108 A membrane and cathode 114 .
  • the system is capable of forming bicarbonate ions 122 in first electrolyte 102 without forming a gas, e.g., hydrogen at cathode 114 or chlorine at anode 112 .
  • the system is capable of forming bicarbonate ions in first electrolyte 102 when a voltage of 0.2 V or less, 0.3 V or less, 0.4 V or less, 0.5 V or less, 0.6 V or less, 0.7 V or less, or 0.8 V or less is applied across the anode and cathode.
  • the system also capable of forming an acid 124 in third electrolyte solution 118 contacting cation exchange membrane 108 A as a result of transfer of protons across cation exchange membrane 108 A from first electrolyte 102 .
  • protons transferred from first electrolyte 102 to third electrolyte 118 will result in formation of an acid solution 124 in third electrolyte 118 ; thus, where third electrolyte contains chloride ions, hydrochloric acid 124 will form in third electrolyte 118 .
  • the system in various embodiments is capable of oxidizing the anode to from cations in the electrolyte in contact with the anode e.g., tin ions, in second electrolyte 116 .
  • a sacrificial anode e.g., tin, copper, iron, zinc
  • the system in various embodiments is capable of oxidizing the anode to from cations in the electrolyte in contact with the anode e.g., tin ions, in second electrolyte 116 .
  • the system is capable of forming a chloride solution in second electrolyte 116 contacting the anode, e.g., where a tin anode is used and tin ions are present in the second electrolyte 116 , stannous chloride will form in second electrolyte 116 as a result of transfer of chloride ions across anion exchange membrane 106 A from first electrolyte 102 .
  • a tin anode is used and tin ions are present in the second electrolyte 116
  • stannous chloride will form in second electrolyte 116 as a result of transfer of chloride ions across anion exchange membrane 106 A from first electrolyte 102 .
  • stannous chloride solution will form in electrolyte 116 a result of ions migrating to or from second electrolyte 116 across the ion exchange membrane in contact with second electrolyte 116 as discussed below.
  • the electrolyte solution 116 in contact with anode 112 comprising anode ions can be reused as electrolyte 118 in contact with cathode 114 to recover anode material at the cathode.
  • tin and other sacrificial metal can thus be recovered at the cathode, depending on the material used as the sacrificial anode.
  • system 100 , system 200 , system 300 and system 400 comprise inlet ports 126 A-E (where needed) for introducing substances in to the cell, e.g., for introducing fluids, gases, salts and the like into cells 110 , 202 , 302 , 402 ; and outlet ports 130 A-E (where needed) for removing fluids from the cells.
  • system 100 comprises inlet port 1268 for introducing carbon dioxide 104 into first electrolyte 102 , and inlet port 126 C for introducing sodium chloride solution 128 into first electrolyte 102 .
  • the inlet and outlet ports are adaptable for various flow protocols including batch flow, semi-batch flow, or continuous flow.
  • the system includes voltage regulator 120 for regulating voltages across the electrodes and currents through the electrolytes.
  • electrochemical cell 110 comprises first compartment 132 , second compartment 134 and third compartment 136 formed by positioning anion exchange membrane 106 A and cation exchange membrane 108 A in cell 110 such that first electrolyte 102 is separated from second electrolyte 116 and third electrolyte 118 .
  • the ion exchange membranes are positioned to contact the electrolytes on opposite surfaces such that ions from one electrolyte will migrate to another electrolyte through the ion exchange membrane without mixing of the electrolytes.
  • first electrolyte 102 is initially charged (where appropriate) with first electrolyte 102 , second electrolyte 116 , third electrolyte 118 , fourth electrolyte 206 and fifth electrolyte 404 comprising an aqueous salt solution such as a saltwater, e.g., seawater, brine, brackish water, sodium chloride, conductive fresh water and the like.
  • a saltwater e.g., seawater, brine, brackish water, sodium chloride, conductive fresh water and the like.
  • the system was initially charged with first electrolyte 102 and fifth electrolyte 404 comprising 2 M sodium chloride solution; in another embodiment the system was initially charged with first electrolyte 102 and fifth electrolyte 404 comprising 0.5 M sodium chloride solution.
  • the system can be charged initially with a salt solution, e.g., sodium chloride, at a concentration from 0.1 to 4 M, e.g., 0.1 to 2.5 M, or 0.2 to 2.0 M, or 0.1 to 1.0 M, or 0.2 to 1.0 M, or 0.2 to 0.8 M, or 0.3 to 0.7 M, or 0.4 to 0.6 M, or 0.5 to 2.5 M, or 1.0 to 2.5 M, or 1.5 to 2.5 M, or 1.7 to 2.3 M.
  • a salt solution e.g., sodium chloride
  • anion exchange membranes 106 A, 106 B and cation exchange membranes 108 A, 108 B comprise ionic membranes selectively permeable to one ion or one class of ions, e.g., cation membranes selectively permeable to sodium ions only or hydrogen ions only, or to cations generally; or anion membranes selectively permeable to chloride ions only or to anions generally, can be used.
  • anion exchange membranes 106 A, 106 B and cation exchange membranes 108 A, 108 B may comprise membranes that will function in an acid and/or basic electrolytic at pH from 1 to 14; also, the membranes may be selected to function with electrolytes wherein the temperatures ranges from about 0° C. to 100° C. or higher.
  • ion exchange membranes are commercially available, e.g., PCA GmbH of Germany supplies a suitable anion exchange membrane permeable to chloride ions and identified as PCSA-250-250; and a cation exchange membrane permeable to sodium ions and identified as PCSK 250 - 250 .
  • anode 112 comprises a sacrificial anode, e.g., tin, copper, iron, zinc.
  • a sacrificial anode such as tin
  • cations such as Sn 2+ will form in second electrolyte 116 in contact with anode 112 .
  • cations in electrolyte 116 in contact with anode 112 can be recovered by plating out the cations at the cathode 114 , e.g., using electrolyte 116 from the anode as the electrolyte at the cathode.
  • the anode material can be recovered at the cathode by switching electrolyte 116 in contact anode 112 with the electrolyte in contact with the cathode 114 when a sufficient concentration of Sn 2+ has accumulated in the electrolyte 116 , and allowing the cations to plate out at the cathode. It will also be appreciated that when sacrificial anode 112 is diminished and cathode 114 is augmented sufficiently, these electrodes may be switched so that anode 112 is transferred to replace cathode 114 and vice versa.
  • the voltage across anode 112 and cathode 114 can be regulated to form bicarbonate ions 122 in first electrolyte 102 without forming a gas, e.g., chlorine at anode 112 or hydrogen at cathode 114 .
  • a gas e.g., chlorine at anode 112 or hydrogen at cathode 114 .
  • bicarbonate ions 122 are formed when the voltage applied across anode 112 and cathode 114 is less than 2.8, 2.7, 2.6, 2.5, 2.4, 2.3, 2.2, 2.1, 2.0, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1, 1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 V. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.8 V without forming a gas at the electrodes.
  • bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.7 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.6 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.5 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.4 V without forming a gas at the electrodes.
  • bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.3 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.2 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.1 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.05 V without forming a gas at the electrodes.
  • a protonated solution e.g., hydrochloric acid 124 is formed in third electrolyte 118 .
  • the pH of the third electrolyte 118 will adjust, e.g., become more acid if protons accumulate in the electrolyte.
  • the acid formed will depend on the electrolytes used, e.g., as illustrated in FIG. 1 , where third electrolyte 118 comprises chloride ions, hydrochloric acid will form in third electrolyte 118 .
  • third electrolyte 118 With the accumulation of protons in third electrolyte 118 , the pH of this electrolyte will decrease; it will be appreciated, however, that the pH of third electrolyte may increase, decrease or remain constant depending on the rate of removal of third electrolyte from the system.
  • first electrolyte 102 initially comprises sodium chloride solution 128
  • sodium bicarbonate 122 will form in first electrolyte 102 as a consequence of the migration of protons and chloride ions from first electrolyte 102 .
  • sodium bicarbonate is an amphoteric salt that forms a mildly alkaline solution in water
  • the pH of the first electrolyte will increase (assuming that first electrolyte 102 is not removed from the system) due to formation of hydroxyl ions (OH ⁇ ) in accordance with the following reaction:
  • carbon dioxide 104 from any convenient source can be used.
  • sources include carbon dioxide dissolved in a liquid, solid carbon dioxide, e.g., dry ice, or gaseous carbon dioxide.
  • carbon dioxide in post-combustion effluent stacks of industrial plants such as power plants, cement plants and coal processing plants can be used.
  • carbon dioxide 104 may comprise substantially pure carbon dioxide or a multi-component gaseous stream comprising carbon dioxide and one or more additional gases. Additional gases and other components may include CO, SO x (e.g., SO 2 ), NO x , mercury and other heavy metals and dust particles e.g., from calcining and combustion processes.
  • one or more of these additional components can be precipitated by contacting first electrolyte 102 with a solution of alkaline earth metal ions, e.g., where SO 2 is contained in the gas stream, sulfates and sulfides of calcium and magnesium can be precipitated.
  • alkaline earth metal ions e.g., where SO 2 is contained in the gas stream
  • Multi-component gaseous streams include reducing condition streams, e.g., syngas, shifted syngas, natural gas, and hydrogen and the like, and oxidizing condition streams, e.g., flue gases from combustion.
  • gaseous streams include oxygen-containing flue gas, e.g., from a coal fired power plant, a cement plant, or a natural gas power plant; turbo charged boiler product gas; coal gasification product gas; shifted coal gasification product gas; anaerobic digester product gas; wellhead natural gas; reformed natural gas or methane hydrates; and the like.
  • gases that are not absorbed in first electrolyte 102 e.g., nitrogen, in one embodiment are vented from the system; in other embodiments, the gases are collected for other uses.
  • bicarbonate ions form in first electrolyte 102 as a result of carbon dioxide contacting water in the first electrolyte 102 , as follows:
  • first electrolyte 102 comprise Na + and Cl ⁇ ions from added sodium chloride 128
  • first electrolyte 102 by placing first electrolyte 102 between cation exchange membrane 108 A selective to transferring H + ions, and an anion exchange membrane 106 A selective to transferring of Cl ⁇ ions, and applying a voltage across the electrodes, H + will migrate through the cation exchange membrane 108 A to adjacent third electrolyte 118 .
  • Cl ⁇ will migrate from first electrolyte 102 through the anion exchange membrane 106 A to adjacent second electrolyte 116 . Consequently, in first electrolyte 102 , a solution comprising sodium bicarbonate will form.
  • the concentration of bicarbonate ions in first electrolyte 102 will adjust, e.g., increase, decrease or will not change.
  • a solution of bicarbonate ions 122 e.g., sodium bicarbonate
  • first electrolyte 102 an acid solution 124 , e.g., hydrochloric acid
  • second electrolyte 116 a chloride solution is obtained in second electrolyte 116 .
  • first electrolyte 102 and carbon dioxide 104 are contained between first anion exchange membrane 106 A and first cation exchange membrane 108 A in an electrochemical cell 202 comprising anode 112 and cathode 114 .
  • second electrolyte 116 contacts first anion exchange membrane 106 A and anode 112 ; third electrolyte 118 is contained between first cation exchange membrane 108 A and second anion exchange membrane 106 B; and fourth electrolyte 206 contacts second anion exchange membrane 1068 and cathode 114 , wherein on applying a voltage 130 across cathode 114 and anode 112 , the system forms bicarbonate ions 122 in first electrolyte 102 without forming a gas at the cathode or anode.
  • the system forms bicarbonate ions in first electrolyte 102 when a voltage of 0.4 V or less, or 0.6 V or less, or 0.8 V or less is applied across the anode and cathode.
  • bicarbonate ions 122 are formed when the voltage applied across anode 112 and cathode 114 is less than 2.8, 2.7, 2.6, 2.5, 2.4, 2.3, 2.2, 2.1, 2.0, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1, 1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 V.
  • bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.8 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.7 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.6 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.5 V without forming a gas at the electrodes.
  • bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.4 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.3 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.2 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.1 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.05 V without forming a gas at the electrodes.
  • System 200 in various embodiments will form an acid, e.g., hydrochloric acid 124 , depending on the electrolytes used.
  • the system will form a protonated solution (acid solution) in third electrolyte 118 , e.g., hydrochloric acid as a result of transfer of protons across cation exchange membrane 108 A from first electrolyte 102 ; and an ionic solution, e.g., stannous chloride will form in second electrolyte 116 as a result of chloride ions transferring across anion exchange membrane 106 from first electrolyte 102 , assuming tin ions are present in the second electrolyte 116 from oxidation of anode 112 comprising tin.
  • a protonated solution e.g., hydrochloric acid
  • an ionic solution e.g., stannous chloride
  • electrolyte 116 in contact with anode 112 is reused as electrolyte 118 in contact with cathode 114 to recover anodic metal that may have oxidized into second electrolyte 116 at anode 112 .
  • electrolyte 206 in contact with cathode 114 may be reused as electrolyte 116 in contact with anode 112 . It will be appreciated that when sacrificial anode 112 is diminished and cathode 114 is augmented sufficiently, these electrodes may be switched so that anode 112 is transferred to replace cathode 114 and vice versa.
  • system 200 includes inlet ports 126 A-E adapted for introducing materials into cell 202 , e.g., for introducing carbon dioxide 104 , sodium chloride solution 126 and other electrolytes into cell 202 ; and outlet ports 130 A-D for removing materials from the cell, e.g., removing bicarbonate solution 122 and acid 124 from the cell.
  • the inlet and outlet ports are adaptable for various flow protocols including batch flow, semi-batch flow, or continuous flow.
  • the system includes voltage/current regulator 120 for regulating currents and voltages across the anode, cathode and the electrolytes.
  • electrochemical cell 202 comprises first compartment 132 , second compartment 134 , third compartment 136 and fourth compartment 138 formed by positioning first anion exchange membrane 106 A and first cation exchange membrane 108 A to separate first electrolyte 102 from second electrolyte 116 and third electrolyte 118 , and by positioning second anion exchange membrane 1068 to separate third electrolyte 118 from fourth electrolyte 206 .
  • the ion exchange membranes in various embodiments are positioned to contact the electrolytes at opposite surfaces to allow movement of ions from one electrolyte to another electrolyte through the ion exchange membranes without mixing of the electrolytes.
  • first 102 , second 116 third 118 and fourth 206 electrolytes initially may comprise an aqueous salt solution such as a saltwater, e.g., seawater, brine, brackish water, conductive fresh water and the like.
  • a saltwater e.g., seawater, brine, brackish water, conductive fresh water and the like.
  • first electrolyte 102 initially comprised 2 M sodium chloride solution; in another embodiment first electrolyte 102 comprised 0.5 M sodium chloride solution.
  • the system may be charged initially with a salt solution, e.g., sodium chloride, at a concentration from 0.1 to 4 M, e.g., 0.1 to 2.5 M, or 0.2 to 2.0 M, or 0.1 to 1.0 M, or 0.2 to 1.0 M, or 0.2 to 0.8 M, or 0.3 to 0.7 M, or 0.4 to 0.6 M, or 0.5 to 2.5 M, or 1.0 to 2.5 M, or 1.5 to 2.5 M, or 1.7 to 2.3 M.
  • a salt solution e.g., sodium chloride
  • the voltage across anode 112 and cathode 114 can be regulated to form bicarbonate ions 122 in first electrolyte 102 without forming a gas, e.g., chlorine at anode 112 or hydrogen at cathode 114 .
  • a protonated (acid) solution 124 is formed in third electrolyte 118 in contact with cation exchange membrane 108 A by protons transferred from first electrolyte 102 .
  • the acid solution formed will depend on the electrolytes used, e.g., as illustrated in FIG.
  • the acid solution formed will comprise hydrochloric acid.
  • An acid solution is formed, in various embodiments, when the voltage applied across anode 112 and cathode 114 is less than 2.8, 2.7, 2.6, 2.5, 2.4, 2.3, 2.2, 2.1, 2.0, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1, 1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 V. In certain embodiments, an acid solution is formed when the voltage applied across the anode and cathode is less than 0.8 V without forming a gas at the electrodes.
  • an acid solution is formed when the voltage applied across the anode and cathode is less than 0.7 V without forming a gas at the electrodes. In certain embodiments, an acid solution is formed when the voltage applied across the anode and cathode is less than 0.6 V without forming a gas at the electrodes. In certain embodiments, an acid solution is formed when the voltage applied across the anode and cathode is less than 0.5 V without forming a gas at the electrodes. In certain embodiments, an acid solution is formed when the voltage applied across the anode and cathode is less than 0.4 V without forming a gas at the electrodes.
  • an acid solution is formed when the voltage applied across the anode and cathode is less than 0.3 V without forming a gas at the electrodes. In certain embodiments, an acid solution is formed when the voltage applied across the anode and cathode is less than 0.2 V without forming a gas at the electrodes. In certain embodiments, an acid solution is formed when the voltage applied across the anode and cathode is less than 0.1 V without forming a gas at the electrodes. In certain embodiments, an acid solution is formed when the voltage applied across the anode and cathode is less than 0.05 V without forming a gas at the electrodes.
  • bicarbonate ions are formed in first electrolyte 102 by carbon dioxide contacting water in the first electrolyte, as follows:
  • first electrolyte 102 comprise Na + and Cl ⁇ ions from added sodium chloride 128
  • first electrolyte 102 by placing first electrolyte 102 between cation exchange membrane 108 A selective to transferring H + ions, and anion exchange membrane 106 A selective to transferring of Cl ⁇ ions, and applying a voltage across the electrodes, H + will migrate through cation exchange membrane 108 A to adjacent third electrolyte 118 .
  • Cl ⁇ will migrate from the first electrolyte through the anion exchange membrane 106 A to adjacent second electrolyte 116 . Consequently, in first electrolyte 102 , a solution comprising sodium bicarbonate 122 will form.
  • the concentration of sodium bicarbonate 122 in first electrolyte 102 will be adjusted, e.g., increase, decrease or does not change.
  • a solution of bicarbonate ions 122 e.g., sodium bicarbonate is obtained in first electrolyte 102 ; an acid solution 124 , e.g., hydrochloric acid is obtained in third electrolyte 118 ; a chloride solution, e.g., tin chloride is obtained in second electrolyte 116 where a tin anode is used; and the fourth electrolyte 206 is depleted of chloride ions and cations, e.g., the electrolyte is depleted of Sn 2+ where the fourth electrolyte was initially charged with a tin salt, e.g., stannous chloride.
  • a tin salt e.g., stannous chloride.
  • system 300 comprises first electrolyte 102 contained between first cation exchange membrane 108 A and second cation exchange membrane 1088 and to which carbon dioxide 104 is added in an electrochemical cell 302 comprising anode 112 and cathode 114 ; second electrolyte 116 contacting second cation exchange membrane 1088 and anode 112 ; third electrolyte 118 contained between first cation exchange membrane 108 A and anion exchange membrane 106 B in electrochemical cell 302 ; and fourth electrolyte 206 contacting anion exchange membrane 106 B and cathode 114 , wherein on applying a voltage 120 across the cathode and anode the system is capable of forming bicarbonate ions 122 in first electrolyte 102 without forming a gas at cathode 114 or anode 112 .
  • electrochemical cell 302 comprises first compartment 132 , second compartment 134 , third compartment 136 and fourth compartment 138 formed by positioning first cation exchange membrane 108 A and second cation exchange membrane 1088 to separate first electrolyte 102 from second electrolyte 116 and from third electrolyte 118 ; and by positioning second anion exchange membrane 1068 to separate third electrolyte 118 from fourth electrolyte 206 .
  • the ion exchange membranes in various embodiments are positioned to contact the electrolytes at opposite surfaces to allow for movement of ions from one electrolyte to another electrolyte through the ion exchange membranes without mixing of the electrolytes.
  • first 102 , second 116 third 118 and fourth 206 electrolytes may initially comprise an aqueous salt solution, e.g., seawater, brine, brackish water, conductive fresh water and the like.
  • aqueous salt solution e.g., seawater, brine, brackish water, conductive fresh water and the like.
  • electrolytes in the system may be charged initially with a salt solution, e.g., sodium chloride, at a concentration from 0.1 to 4 M, e.g., 0.1 to 2.5 M, or 0.2 to 2.0 M, or 0.1 to 1.0 M, or 0.2 to 1.0 M, or 0.2 to 0.8 M, or 0.3 to 0.7 M, or 0.4 to 0.6 M, or 0.5 to 2.5 M, or 1.0 to 2.5 M, or 1.5 to 2.5 M, or 1.7 to 2.3 M.
  • a salt solution e.g., sodium chloride
  • the voltage across the anode 112 and cathode 114 can be regulated to form bicarbonate ions 122 in the first electrolyte 102 without forming a gas, e.g., chlorine at anode 112 or hydrogen at cathode 114 .
  • a gas e.g., chlorine at anode 112 or hydrogen at cathode 114 .
  • bicarbonate ions 122 are formed in first electrolyte 102 when the voltage applied across anode 112 and cathode 114 is less than 2.8, 2.7, 2.6, 2.5, 2.4, 2.3, 2.2, 2.1, 2.0, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1, 1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 V.
  • anode acid solution 124 is formed in third electrolyte 118 in contact with cation exchange membrane 108 A as a result of protons transferring from first electrolyte 102 .
  • the acid formed depends on the electrolytes used, e.g., as illustrated in FIG. 3 , where the first electrolyte 102 comprises sodium chloride, the acid formed comprises hydrochloric acid 124 .
  • bicarbonate ions and the acid solution are formed when the voltage applied across the anode and cathode is less than 0.8 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions and the acid solution are formed when the voltage applied across the anode and cathode is less than 0.7 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions and the acid solution are formed when the voltage applied across the anode and cathode is less than 0.6 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions and the acid solution are formed when the voltage applied across the anode and cathode is less than 0.5 V without forming a gas at the electrodes.
  • bicarbonate ions and the acid solution are formed when the voltage applied across the anode and cathode is less than 0.4 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions and the acid solution are formed when the voltage applied across the anode and cathode is less than 0.3 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions and the acid solution are formed when the voltage applied across the anode and cathode is less than 0.2 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions and the acid solution are formed when the voltage applied across the anode and cathode is less than 0.1 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions and the acid solution are formed when the voltage applied across the anode and cathode is less than 0.05 V without forming a gas at the electrodes.
  • system 300 includes inlet ports 126 A-D adapted for introducing materials into cell 302 , e.g., for introducing carbon dioxide 104 , sodium chloride solution 126 and other electrolytes into cell 302 ; and outlet ports 130 A-D for removing materials from the cell, e.g., removing bicarbonate solution 122 and acid 124 from the cell.
  • the inlet and outlet ports are adaptable for various flow protocols including batch flow, semi-batch flow, or continuous flow.
  • the system includes voltage/current regulator 120 for regulating voltages across the anode and cathode and currents through the electrolytes.
  • bicarbonate ions HCO 3 ⁇
  • second electrolyte 116 comprise Na + and Cl ⁇ ions from added sodium chloride 128
  • first electrolyte 102 between cation exchange membrane 108 A selective to transferring H + ions
  • second cation exchange membrane 108 B selective to transferring of cations, e.g., Na + ions
  • H + will migrate through first cation exchange membrane 108 A to adjacent third electrolyte 118
  • Na + will migrate from second electrolyte 116 through second cation exchange membrane 1088 to adjacent first electrolyte 102 .
  • first electrolyte 102 a solution comprising sodium bicarbonate 122 will form.
  • concentration of sodium bicarbonate in first electrolyte 102 will adjust, e.g., increase, decrease or will not change.
  • a solution of bicarbonate ions 122 e.g., sodium bicarbonate is obtained in first electrolyte 102 ; an acid solution 124 , e.g., hydrochloric acid is obtained in third electrolyte 118 ; a chloride solution, e.g., tin chloride is obtained in second electrolyte 116 where a tin anode is used; fourth electrolyte 206 is depleted of chloride ions due to chloride transfer across anion exchange membrane 1068 ; and fourth electrolyte 204 is also depleted of cations by a reduction reaction at the cathode, e.g., fourth electrolyte 206 is depleted of Sn 2+ where the fourth electrolyte was initially charged with, e.g., stannous chloride.
  • cations in electrolyte 116 in contact with anode 112 can be recovered by plating out the cations at the cathode 114 , e.g., using electrolyte 116 from the anode as the electrolyte at the cathode.
  • the anode material can be recovered at the cathode by switching electrolyte 116 in contact anode 112 with the electrolyte in contact with the cathode 114 when a sufficient concentration of Sn 2+ has accumulated in the electrolyte 116 , and allowing the cations to plate out at the cathode.
  • electrolyte 116 in contact anode 112 with the electrolyte in contact with the cathode 114 when a sufficient concentration of Sn 2+ has accumulated in the electrolyte 116 , and allowing the cations to plate out at the cathode.
  • system 400 comprises first electrolyte 102 contained between first cation exchange membrane 108 A and second cation exchange membrane 1088 ; second electrolyte 116 contacting anode 112 and separated from fifth electrolyte 404 by first anion exchange membrane 106 A; third electrolyte 118 contained between first cation exchange membrane 108 A and second anion exchange membrane 1068 ; fourth electrolyte 206 contacting second anion exchange membrane 106 B and cathode 114 ; and fifth electrolyte 404 comprising an electrolyte containing, e.g., sodium chloride solution 128 , and contained between first anion exchange membrane 106 A and second cation exchange membrane 108 B, wherein on applying a voltage across the cathode 114 and anode 112 and adding carbon dioxide 104 to first electrolyte 102 , the system is capable of forming bicarbonate ions 122 in first electrolyte 102 without forming a gas at cathode
  • electrochemical cell 402 comprises first compartment 132 , second compartment 134 , third compartment 136 , fourth compartment 138 , and fifth compartment 140 formed by positioning first cation exchange membrane 108 A and second cation exchange membrane 108 B to separate first electrolyte 102 from fifth electrolyte 404 and from third electrolyte 118 .
  • second anion exchange membrane 106 B is positioned to separate third electrolyte 118 from fourth electrolyte 206 ; and first anion exchange membrane 106 A is positioned to separate second electrolyte 116 in contact with anode 112 from fifth electrolyte 404 comprising sodium chloride solution 128 .
  • system 400 is capable of forming bicarbonate ions in first electrolyte 102 when a voltage of 0.4 V or less, or 0.6 V or less, or 0.8 V or less is applied across the anode 112 and cathode 114 .
  • first electrolyte 102 , second electrolyte 116 third electrolyte 118 , and fourth electrolyte 206 initially may comprise an aqueous salt solution such as a saltwater, e.g., sodium chloride, stannous chloride, seawater, brine, brackish water, conductive fresh water and the like.
  • a saltwater e.g., sodium chloride, stannous chloride, seawater, brine, brackish water, conductive fresh water and the like.
  • a 2 M solution of sodium chloride sodium chloride solution 128 was added to fourth compartment 140 to form fifth electrolyte 404 ; in another embodiment, initially fifth electrolyte 404 comprised 0.5 M solution of sodium chloride.
  • the fifth electrolyte 404 may be charged initially with a salt solution, e.g., sodium chloride, at a concentration from 0.1 to 4 M, e.g., 0.1 to 2.5 M, or 0.2 to 2.0 M, or 0.1 to 1.0 M, or 0.2 to 1.0 M, or 0.2 to 0.8 M, or 0.3 to 0.7 M, or 0.4 to 0.6 M, or 0.5 to 2.5 M, or 1.0 to 2.5 M, or 1.5 to 2.5 M, or 1.7 to 2.3 M.
  • a salt solution e.g., sodium chloride
  • the voltage across anode 112 and cathode 114 can be regulated to form bicarbonate ions 122 in first electrolyte 102 without forming a gas, e.g., chlorine at anode 112 or hydrogen at cathode 114 .
  • a gas e.g., chlorine at anode 112 or hydrogen at cathode 114 .
  • bicarbonate ions 122 are formed in first electrolyte 102 where the voltage applied across anode 112 and cathode 114 is less than 2.8, 2.7, 2.6, 2.5, 2.4, 2.3, 2.2, 2.1, 2.0, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, 1.2, 1.1, 1.0, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, or 0.1 V.
  • first electrolyte 102 comprises sodium chloride
  • the acid formed in third electrolyte 118 comprises hydrochloric acid.
  • bicarbonate ions and the acid solution are formed when the voltage applied across the anode and cathode is less than 0.8 V without forming a gas at the electrodes.
  • bicarbonate ions and the acid solution are formed when the voltage applied across the anode and cathode is less than 0.7 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions and the acid solution are formed when the voltage applied across the anode and cathode is less than 0.6 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions and the acid solution are formed when the voltage applied across the anode and cathode is less than 0.5 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions and the acid solution are formed when the voltage applied across the anode and cathode is less than 0.4 V without forming a gas at the electrodes.
  • bicarbonate ions and the acid solution are formed when the voltage applied across the anode and cathode is less than 0.3 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions and the acid solution are formed when the voltage applied across the anode and cathode is less than 0.2 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions and the acid solution are formed when the voltage applied across the anode and cathode is less than 0.1 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions and the acid solution are formed when the voltage applied across the anode and cathode is less than 0.05 V without forming a gas at the electrodes.
  • system 400 includes inlet ports 126 A-E adapted for introducing substances into cell 402 , e.g., for introducing carbon dioxide 104 , sodium chloride solution 128 and other electrolytes into cell 402 ; and outlet ports 130 A-E for removing substances from the cell, e.g., removing bicarbonate solution 122 and acid 124 from the cell.
  • the inlet and outlet ports are adaptable for various flow protocols including batch flow, semi-batch flow, or continuous flow.
  • the system includes voltage regulator 120 for regulating voltages across the anode and cathode and current through the electrolytes.
  • fifth electrolyte 404 comprise Na + and Cl ⁇ ions from added sodium chloride 128
  • first electrolyte 102 between cation exchange membrane 108 A selective to transferring H + ions, and second cation exchange membrane 108 B selective to transferring of cations, e.g., Na + ions, and on applying a voltage across the electrodes
  • H + will migrate through first cation exchange membrane 108 A to adjacent third electrolyte 118 .
  • Na + will migrate from fifth electrolyte 404 through second cation exchange membrane 108 B to first electrolyte 102 .
  • first electrolyte 102 a solution comprising sodium bicarbonate 122 will form.
  • concentration of sodium bicarbonate 122 in first electrolyte 102 will adjust, e.g., increase, decrease or will not change.
  • fifth electrolyte 404 will be depleted of chloride ions; consequently, fifth electrolyte will be depleted of sodium chloride, and correspondingly, the chloride ion content of the second electrolyte 116 will adjust, e.g., increase, decrease or remain constant depending on the flow of second electrolyte 116 from the system.
  • a solution of bicarbonate ions 122 e.g., sodium bicarbonate is obtained in first electrolyte 102 ; an acid solution 124 , e.g., hydrochloric acid is obtained in third electrolyte 118 ; a chloride solution, e.g., stannous chloride, is obtained in second electrolyte 116 ; fourth electrolyte 206 will be depleted of chloride ions; and fifth electrolyte 404 initially comprising sodium chloride solution 128 will be depleted of sodium and chloride ions.
  • bicarbonate ions 122 e.g., sodium bicarbonate
  • an acid solution 124 e.g., hydrochloric acid
  • a chloride solution e.g., stannous chloride
  • cations in electrolyte 116 in contact with anode 112 can be recovered by plating out the cations at the cathode 114 , e.g., using electrolyte 116 from the anode as the electrolyte at the cathode.
  • the anode material can be recovered at the cathode by switching electrolyte 116 in contact anode 112 with the electrolyte in contact with the cathode 114 when a sufficient concentration of Sn 2+ has accumulated in the electrolyte 116 , and allowing the cations to plate out at the cathode.
  • electrolyte 116 in contact anode 112 with the electrolyte in contact with the cathode 114 when a sufficient concentration of Sn 2+ has accumulated in the electrolyte 116 , and allowing the cations to plate out at the cathode.
  • present method 500 comprises step 502 of applying a voltage 120 across an anode 112 and a cathode 114 through a first electrolyte 102 comprising carbon dioxide 104 to form bicarbonate ions 122 in the first electrolyte without forming a gas at the cathode or the anode.
  • first electrolyte 102 is contained between first anion exchange membrane 106 A and first cation exchange membrane 108 A in electrochemical cell 100 ; the anion exchange membrane contacts the anode 112 through second electrolyte 116 ; and the cation exchange membrane contacts cathode 112 through third electrolyte 118 .
  • the method forms bicarbonate ions 122 in first electrolyte 102 when a voltage, e.g., 0.4 V or less, or 0.6 V or less, or 0.8 V or less is applied across the anode and cathode.
  • bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.8 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.7 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.6 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.5 V without forming a gas at the electrodes.
  • bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.4 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.3 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.2 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.1 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.05 V without forming a gas at the electrodes.
  • method 500 forms a protonated solution in third electrolyte 118 , e.g., hydrochloric acid 124 as a result of transfer of protons across first cation exchange membrane 108 A from first electrolyte 102 ; and an ionic solution, e.g., stannous chloride in second electrolyte 116 , as a result of chloride ions transferring across first anion exchange membrane 106 A from first electrolyte 102 , and tin ions forming in second electrolyte 116 by oxidation of anode 112 comprising tin.
  • third electrolyte 118 e.g., hydrochloric acid 124
  • an ionic solution e.g., stannous chloride in second electrolyte 116
  • anode 112 comprises a sacrificial anode, e.g., tin, copper, iron, zinc
  • cations such as Sn 2+ will form in second electrolyte 116 in contact with anode 112 .
  • cations in electrolyte 116 in contact with anode 112 can be recovered by plating out the cations at the cathode 114 , e.g., using electrolyte 116 from the anode as the electrolyte at the cathode.
  • anode material can be recovered at the cathode 114 by switching electrolyte 116 in contact anode 112 with the electrolyte in contact with the cathode 114 when a sufficient concentration of Sn 2+ has accumulated in the electrolyte 116 , and allowing the cations to plate out at the cathode.
  • method 600 comprises step 602 of applying a voltage 120 of less than 2.0 V, less than 1.5 V, less than 1.0 V, less than 0.5 V, less than 0.1 V or less than 0.05 V across an anode 112 and a cathode 114 through first electrolyte 102 comprising carbon dioxide 104 to form bicarbonate ions 122 in the first electrolyte.
  • the method forms bicarbonate ions in first electrolyte when a voltage, e.g., 0.4 V or less, or 0.6 V or less, or 0.8 V or less is applied across the anode and cathode.
  • bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.8 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.7 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.6 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.5 V without forming a gas at the electrodes.
  • bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.4 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.3 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.2 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.1 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.05 V without forming a gas at the electrodes.
  • first electrolyte 102 is contained between first anion exchange membrane 106 A and first cation exchange membrane 108 A in electrochemical cell 302 ; first anion exchange membrane 106 A contacts anode 112 through second electrolyte 116 ; and first cation exchange membrane 108 A contacts the cathode through third electrolyte 118 .
  • first anion exchange membrane 106 A contacts anode 112 through second electrolyte 116 ; and first cation exchange membrane 108 A contacts the cathode through third electrolyte 118 .
  • first electrolyte 102 is contained between first cation exchange membrane 108 A and second cation exchange membrane 108 B in electrochemical cell 303 ; second cation exchange membrane 1088 contacts anode 112 through second electrolyte 116 ; first cation exchange membrane 108 A separates first electrolyte 102 from third electrolyte 118 ; second anion exchange membrane 1068 separates third electrolyte 118 from fourth electrolyte 206 ; and fourth electrolyte 206 is in contact with cathode 114 .
  • method 600 forms bicarbonate ions 122 in first electrolyte when a voltage, e.g., 0.4 V or less, or 0.6 V or less, or 0.8 V or less is applied across the anode and cathode.
  • a voltage e.g., 0.4 V or less, or 0.6 V or less, or 0.8 V or less is applied across the anode and cathode.
  • method 600 forms an acid, e.g., hydrochloric acid 124 , depending on the electrolytes used.
  • the method forms a protonated solution in third electrolyte 118 , e.g., hydrochloric acid as a result of transfer of protons across first cation exchange membrane 108 A from first electrolyte 102 ; and an ionic solution, e.g., stannous chloride in second electrolyte 116 , as a result of chlorine ions transferring across first anion exchange membrane 106 A from first electrolyte 102 , and tin ions forming by oxidation of the anode 112 .
  • a protonated solution in third electrolyte 118 e.g., hydrochloric acid as a result of transfer of protons across first cation exchange membrane 108 A from first electrolyte 102
  • an ionic solution e.g., stannous chloride in second electrolyte 116
  • anode 112 comprises a sacrificial anode, e.g., tin, copper, iron, zinc
  • cations such as Sn 2+ will form in second electrolyte 116 in contact with anode 112 .
  • cations in electrolyte 116 in contact with anode 112 can be recovered by plating out the cations at the cathode 114 , e.g., using electrolyte 116 from the anode as the electrolyte at the cathode.
  • anode material can be recovered at the cathode 114 by switching electrolyte 116 in contact anode 112 with the electrolyte in contact with the cathode 114 when a sufficient concentration of Sn 2+ has accumulated in the electrolyte 116 , and allowing the cations to plate out at the cathode.
  • electrolyte 116 in contact anode 112 with the electrolyte in contact with the cathode 114 when a sufficient concentration of Sn 2+ has accumulated in the electrolyte 116 , and allowing the cations to plate out at the cathode.
  • first electrolyte 102 contained in compartment 132 , was charged with a 2 M sodium chloride solution 128 to which carbon dioxide gas 104 was added.
  • Third electrolyte 118 comprising saltwater, e.g., stannous chloride was contained in compartment 136 .
  • First anion exchange membrane 106 A separated first electrolyte 102 from second electrolyte 116 ; first cation exchange membrane 108 A separated first electrolyte 102 from third electrolyte 118 ; anode 112 formed of tin foil were placed in contact with second electrolyte 116 , and cathode 114 formed of tin foil was placed in contact with third electrolyte 118 . Voltages of 0.4 V, 0.6 V and 0.8 V were applied across anode 112 and cathode 114 in a batch mode operation for one hour.
  • first electrolyte 102 in compartment 132 increased (correlating to an increase of hydroxide ion concentration in first electrolyte 102 as described above), while the pH of third electrolyte 118 in compartment 136 decreased (correlating to an increase in protons in third electrolyte 118 as described above), without the formation of a gas, e.g., chlorine at anode 112 or hydrogen at cathode 114 .
  • a gas e.g., chlorine at anode 112 or hydrogen at cathode 114 .
  • first electrolyte 102 bicarbonate ions formed as a result of carbon dioxide contacting water in first electrolyte 102 , as follows:
  • first electrolyte 102 Na + and Cl ⁇ ions are present from the sodium chloride 128 .
  • first electrolyte 102 by placing first electrolyte 102 between first cation exchange membrane 108 A selective to transferring H + ions, and first anion exchange membrane 106 A selective to transferring of Cl ⁇ ions, and on applying a voltage across the electrodes, H + migrated through cation exchange membrane 108 A to adjacent third electrolyte 118 .
  • Cl ⁇ migrated from first electrolyte 102 through anion 106 A exchange membrane to adjacent second electrolyte 116 . Consequently, a solution comprising sodium bicarbonate 122 formed in first electrolyte 102 .
  • the pH of the first electrolyte increased in accordance with the following reaction:
  • the voltages may be adjusted up or down from these exemplary voltages; a minimum theoretical voltages 0 V or very close to 0 V, but to achieve a useful rate of production of bicarbonate ions, a practical lower limit may be in some embodiments 0.001 V or 0.01 V, or 0.1 V, depending on the desired time for bicarbonate ion production and/or pH adjustment, volume of first electrolyte solution 102 , and other factors apparent to those of ordinary skill; e.g., in some embodiments system 100 , system 200 , system 300 and system 400 and method 500 and method 600 are capable of producing bicarbonate ions at voltages as low as 0.001 V, or 0.01 V, or 0.1V, and can also produce bicarbonate ions at higher voltages if more rapid production is desired, e.g., at 0.2-2.0 V; in various embodiments the bicarbonate ions are produced with no gas formation at the anode or cathode, e.g., no formation
  • a pH difference of more than 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, or 12.0 pH units may be produced in a first electrolyte solution 102 and in third electrolyte solution 118 when a voltage of 1.0 V or less, or 0.9 V or less, or 0.8 V or less, or 0.7 V or less, or 0.6V or less, or 0.5 V or less, or 0.4 V or less, or 0.3 V or less, or 0.2 V or less, or 0.1 V or less, or 0.05 V or less is applied across the anode and cathode.
  • bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.8 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.7 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.6 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.5 V without forming a gas at the electrodes.
  • bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.4 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.3 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.2 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.1 V without forming a gas at the electrodes. In certain embodiments, bicarbonate ions are formed when the voltage applied across the anode and cathode is less than 0.05 V without forming a gas at the electrodes.
  • the present invention provides a system and method capable of producing a pH difference of more than 0.5 pH units in first electrolyte 102 and third electrolyte 118 when a voltage of 0.05 V or less is applied across the anode and cathode.
  • the invention provides a system and method capable of producing a pH difference of more than 1.0 pH units between first electrolyte 102 and third electrolyte 118 when a voltage of 0.1V or less is applied across the anode and cathode.
  • the invention provides a system and method capable of producing a pH difference of more than 2.0 pH units between a first electrolyte and third electrolyte when a voltage of 0.2 V or less is applied across the anode and cathode.
  • the invention provides a system and method capable of producing bicarbonate ions in first electrolyte 102 when a voltage of 0.4V or less is applied across the anode and cathode. In some embodiments, the invention provides a system and method capable of producing bicarbonates ions 122 when a voltage of 0.6V or less is applied across the anode and cathode. In some embodiments, the invention provides a system and method capable of producing bicarbonate ions 122 when a voltage of 0.8V or less is applied across the anode and cathode. In particular embodiments, the invention provides a system capable of producing bicarbonate ions 122 when a voltage of 1.0 V or less is applied across the anode and cathode. In some embodiments the invention provides a system capable of producing bicarbonate ions 122 in first electrolyte 102 when a voltage of 1.2 V or less is applied across the anode and cathode.
  • the voltage need not be kept constant and that the voltage applied across the anode and the cathode may be very low, e.g., 0.05V or less and that the voltage may be increased as needed as the concentration of bicarbonate ions in the solution 102 increases. In this manner, a desired bicarbonate ion concentration may be achieved with the minimum average voltage, without generating a gas at the electrodes.
  • the average voltage may be less than 80%, 70%, 60%, or less than 50% of the voltages noted in the previous paragraph for particular embodiments.
  • one or more of the initial electrolytes charged into the system may be depleted of divalent cations, e.g., the electrolytes are depleted of magnesium or calcium ion as for example where the electrolytes are taken form an ion exchange process.
  • the total concentration of divalent cations in the electrolyte solutions in contact with the ion exchange membrane or membranes is less than 0.06 mol/kg solution, or less than 0.05 mol/kg solution, or less than 0.04 mol/kg solution, or less than 0.02 mol/kg solution, or less than 0.01 mol/kg solution, or less than 0.005 mol/kg solution, or less than 0.001 mol/kg solution, or less than 0.0005 mol/kg solution, or less than 0.0001 mol/kg solution, or less than 0.00005 mol/kg solution.
  • the carbon dioxide that contacts first electrolyte 102 may initially form bicarbonate ions 122 in the first electrolyte. As bicarbonate ions are removed from first electrolyte 102 more carbon dioxide may dissolve in the electrolyte to form bicarbonate and/or carbonate ions. Depending on the pH of the first electrolyte, the balance is shifted toward bicarbonate or toward carbonate formation, as is well understood in the art. In these embodiments the pH of the first electrolyte may decrease, remain the same, or increase, depending on the rate of removal of bicarbonate and/or carbonate ions compared to rate of introduction of carbon dioxide. It will be appreciated that no bicarbonate ions need form in these embodiments, or that bicarbonate ions may not form during one period but form during another period.
  • the present system is used to produce bicarbonate ions 122 , which, when included in a solution comprising alkaline earth cations and hydroxide ions causes precipitation of carbonate and/or bicarbonate compounds such as calcium carbonate or magnesium carbonate and/or their bicarbonates.
  • carbonate and/or bicarbonate compounds such as calcium carbonate or magnesium carbonate and/or their bicarbonates.
  • divalent cations such as magnesium and/or calcium are present in the solutions used in the process, and/or are added.
  • the precipitated carbonate compound can be used as cements and other building and construction material such as aggregates and the like as described in U.S.
  • the acidified electrolyte solution 118 illustrated in FIGS. 1-4 is utilized to dissolve a calcium and/or magnesium rich mineral, such as mafic mineral including serpentine or olivine, to form a solution for precipitating carbonates and bicarbonates as described in the United States patent applications incorporated herein by reference.
  • acidified stream 118 can be used to dissolve calcium and/or magnesium rich minerals such as serpentine and olivine to from an electrolyte solution that can be charged with bicarbonate ions 122 and then made sufficiently basic to precipitate carbonate compounds.
  • Such precipitation reactions and the use of the precipitates, e.g., as in cements are described in the U.S. patent application Ser. No. 12/126,776, filed on May 23, 2008 and incorporated herein by reference.
  • the bicarbonate ion solutions of the present invention can be utilized to desalinate saltwater by removing divalent cations as insoluble carbonates, e.g., removing calcium and magnesium ions from a saltwater e.g., seawater based on the following reactions and as described in U.S. patent application Ser. No. 12/163,205, filed on Jun. 27, 2008, herein incorporated by reference:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Health & Medical Sciences (AREA)
  • Urology & Nephrology (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
US12/989,781 2009-01-28 2009-01-28 Low-energy electrochemical bicarbonate ion solution Abandoned US20110042230A1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2009/032301 WO2010087823A1 (fr) 2009-01-28 2009-01-28 Solution d'ions bicarbonates électrochimique à basse énergie

Publications (1)

Publication Number Publication Date
US20110042230A1 true US20110042230A1 (en) 2011-02-24

Family

ID=42395872

Family Applications (1)

Application Number Title Priority Date Filing Date
US12/989,781 Abandoned US20110042230A1 (en) 2009-01-28 2009-01-28 Low-energy electrochemical bicarbonate ion solution

Country Status (5)

Country Link
US (1) US20110042230A1 (fr)
EP (1) EP2240629A4 (fr)
CN (1) CN101878328A (fr)
CA (1) CA2696075A1 (fr)
WO (1) WO2010087823A1 (fr)

Cited By (49)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100002587A1 (en) * 2008-07-01 2010-01-07 Gayle Loretta Ray Noble Diagnostics for Serial Communication Busses
US20100084280A1 (en) * 2009-07-15 2010-04-08 Gilliam Ryan J Electrochemical production of an alkaline solution using co2
US20100135865A1 (en) * 2007-12-28 2010-06-03 Constantz Brent R Electrochemical methods of sequestering co2
US20100144521A1 (en) * 2008-05-29 2010-06-10 Brent Constantz Rocks and Aggregate, and Methods of Making and Using the Same
US20100140103A1 (en) * 2008-07-16 2010-06-10 Gilliam Ryan J Gas Diffusion Anode and CO2 Cathode Electrolyte System
US20100150802A1 (en) * 2008-12-11 2010-06-17 Gilliam Ryan J Processing co2 utilizing a recirculating solution
US20100219373A1 (en) * 2009-03-02 2010-09-02 William Randall Seeker Gas stream multi-pollutants control systems and methods
US20100230293A1 (en) * 2008-07-16 2010-09-16 Gilliam Ryan J Co2 utilization in electrochemical systems
US20100229725A1 (en) * 2009-03-10 2010-09-16 Kasra Farsad Systems and Methods for Processing CO2
US20100239467A1 (en) * 2008-06-17 2010-09-23 Brent Constantz Methods and systems for utilizing waste sources of metal oxides
US20100258035A1 (en) * 2008-12-24 2010-10-14 Brent Constantz Compositions and methods using substances containing carbon
US20100313793A1 (en) * 2008-09-30 2010-12-16 Constantz Brent R Reduced-carbon footprint concrete compositions
US20100313794A1 (en) * 2007-12-28 2010-12-16 Constantz Brent R Production of carbonate-containing compositions from material comprising metal silicates
US20110033239A1 (en) * 2009-08-07 2011-02-10 Brent Constantz Utilizing salts for carbon capture and storage
US20110054084A1 (en) * 2007-05-24 2011-03-03 Constantz Brent R Hydraulic cements comprising carbonate compound compositions
US20110071309A1 (en) * 2009-09-24 2011-03-24 Constantz Brent R Methods and Systems for Utilization of HCI
US20110067603A1 (en) * 2009-12-31 2011-03-24 Constantz Brent R Methods and compositions using calcium carbonate
US20110079515A1 (en) * 2009-07-15 2011-04-07 Gilliam Ryan J Alkaline production using a gas diffusion anode with a hydrostatic pressure
US20110083968A1 (en) * 2009-02-10 2011-04-14 Gilliam Ryan J Low-voltage alkaline production using hydrogen and electrocatalytic electrodes
US20110147227A1 (en) * 2009-07-15 2011-06-23 Gilliam Ryan J Acid separation by acid retardation on an ion exchange resin in an electrochemical system
US8006446B2 (en) 2008-09-30 2011-08-30 Calera Corporation CO2-sequestering formed building materials
US8691175B2 (en) 2011-04-28 2014-04-08 Calera Corporation Calcium sulfate and CO2 sequestration
US8869477B2 (en) 2008-09-30 2014-10-28 Calera Corporation Formed building materials
US8906156B2 (en) 2009-12-31 2014-12-09 Calera Corporation Cement and concrete with reinforced material
US8936773B2 (en) 2011-04-28 2015-01-20 Calera Corporation Methods and compositions using calcium carbonate and stabilizer
US8999057B2 (en) 2011-09-28 2015-04-07 Calera Corporation Cement and concrete with calcium aluminates
US9061940B2 (en) 2008-09-30 2015-06-23 Calera Corporation Concrete compositions and methods
EP2891514A1 (fr) * 2014-01-03 2015-07-08 Marcus Invest Procédé et dispositif pour le traitement de saumures
US9133581B2 (en) 2008-10-31 2015-09-15 Calera Corporation Non-cementitious compositions comprising vaterite and methods thereof
US9187834B2 (en) 2011-05-19 2015-11-17 Calera Corporation Electrochemical hydroxide systems and methods using metal oxidation
US9200375B2 (en) 2011-05-19 2015-12-01 Calera Corporation Systems and methods for preparation and separation of products
CN106745095A (zh) * 2017-01-25 2017-05-31 四川大学 利用芒硝和白云石制取纯碱联产石膏和碱式碳酸镁的方法
US9828313B2 (en) 2013-07-31 2017-11-28 Calera Corporation Systems and methods for separation and purification of products
US9880124B2 (en) 2014-11-10 2018-01-30 Calera Corporation Measurement of ion concentration in presence of organics
US9902652B2 (en) 2014-04-23 2018-02-27 Calera Corporation Methods and systems for utilizing carbide lime or slag
US9957621B2 (en) 2014-09-15 2018-05-01 Calera Corporation Electrochemical systems and methods using metal halide to form products
US10161050B2 (en) 2015-03-16 2018-12-25 Calera Corporation Ion exchange membranes, electrochemical systems, and methods
US10236526B2 (en) 2016-02-25 2019-03-19 Calera Corporation On-line monitoring of process/system
US10266954B2 (en) 2015-10-28 2019-04-23 Calera Corporation Electrochemical, halogenation, and oxyhalogenation systems and methods
US10556848B2 (en) 2017-09-19 2020-02-11 Calera Corporation Systems and methods using lanthanide halide
US10590054B2 (en) 2018-05-30 2020-03-17 Calera Corporation Methods and systems to form propylene chlorohydrin from dichloropropane using Lewis acid
US10619254B2 (en) 2016-10-28 2020-04-14 Calera Corporation Electrochemical, chlorination, and oxychlorination systems and methods to form propylene oxide or ethylene oxide
US10662447B2 (en) 2012-12-21 2020-05-26 Ee-Terrabon Biofuels, Llc System and process for obtaining products from biomass
US10718055B2 (en) 2015-06-15 2020-07-21 The Regents Of The University Of Colorado, A Body Corporate Carbon dioxide capture and storage electrolytic methods
US10847844B2 (en) 2016-04-26 2020-11-24 Calera Corporation Intermediate frame, electrochemical systems, and methods
US11118492B1 (en) 2020-04-27 2021-09-14 Stec Technology, Inc. Reactive cyclic induction system and method for reducing pollutants in marine diesel exhaust
US11377363B2 (en) 2020-06-30 2022-07-05 Arelac, Inc. Methods and systems for forming vaterite from calcined limestone using electric kiln
US11577965B2 (en) 2020-02-25 2023-02-14 Arelac, Inc. Methods and systems for treatment of lime to form vaterite
WO2024020027A1 (fr) * 2022-07-18 2024-01-25 The Regents Of The University Of Calfornia Cellule électrochimique à chambres multiples pour l'élimination de dioxyde de carbone

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2440178C2 (ru) 2006-03-10 2012-01-20 Дуглас К. КОМРИ Материалы и способы секвестрации диоксида углерода
US7993616B2 (en) 2007-09-19 2011-08-09 C-Quest Technologies LLC Methods and devices for reducing hazardous air pollutants
CN104722466A (zh) 2008-07-16 2015-06-24 卡勒拉公司 使用二氧化碳气体的低能量4-电池电化学系统
JP5761874B2 (ja) * 2010-04-22 2015-08-12 スプレイング システムズ カンパニー 電解システム
GB201021701D0 (en) * 2010-12-22 2011-02-02 Future Environmental Technologies Ltd Carbon capture of greenhouse gases
US20140370094A1 (en) 2011-11-08 2014-12-18 Tufts University Silk-based scaffold platform for engineering tissue constructs
PL3126038T3 (pl) * 2014-04-02 2021-10-11 Mangrove Water Technologies Ltd. Konwersja gazu i obróbka roztworu
CN104131311B (zh) * 2014-07-07 2016-10-19 四川大学 矿化co2制取碳酸氢钠或碳酸钠对外输出电能的方法
CN114515494B (zh) * 2022-01-21 2022-11-25 浙江大学 具有精准离子控制的直接空气捕集二氧化碳节能系统和方法

Citations (98)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1169766A (en) * 1915-10-02 1916-02-01 Hermann A Brassert Gas-washer.
US1172930A (en) * 1915-12-08 1916-02-22 Hermann A Brassert Method of and apparatus for gas-washing.
US1176747A (en) * 1915-03-04 1916-03-28 Benjamin M Ferguson Gas-scrubbing apparatus.
US1655171A (en) * 1925-06-17 1928-01-03 Bartlett Hayward Co Liquid and gas contact apparatus
US1897725A (en) * 1926-05-28 1933-02-14 Ig Farbenindustrie Ag Process for extracting carbon dioxid from gaseous mixtures and forming alkaline carbonates
US1986736A (en) * 1934-04-09 1935-01-01 James L Mauthe Gas washer
US2227465A (en) * 1938-06-11 1941-01-07 Binks Mfg Co Means for eliminating divided material in industrial processes
US2273795A (en) * 1936-12-31 1942-02-17 Nat Carbon Co Inc Electrolytic process
US2458039A (en) * 1945-10-05 1949-01-04 Bertrand H Wait Aggregate for improving portland cement concretes
US2967807A (en) * 1952-01-23 1961-01-10 Hooker Chemical Corp Electrolytic decomposition of sodium chloride
US3120426A (en) * 1959-06-24 1964-02-04 Kaiser Aluminium Chem Corp Process for the production of aragonite crystals
US3165460A (en) * 1962-04-11 1965-01-12 American Mach & Foundry Electrolytic acid generator
US3374164A (en) * 1963-06-28 1968-03-19 Ceskoslovenska Akademie Ved Electrolyzer for simultaneous preparation of chlorine and alkali carbonates
US3420775A (en) * 1967-07-05 1969-01-07 Edgar A Cadwallader Prevention of scale in saline water evaporators using carbon dioxide under special conditions
US3558769A (en) * 1965-09-24 1971-01-26 Guardian Chemical Corp Compositions for dental prophylaxis
US3721621A (en) * 1969-12-02 1973-03-20 W Hough Forward-osmosis solvent extraction
US3861928A (en) * 1970-10-30 1975-01-21 Flintkote Co Hydraulic cement and method of producing same
US3864236A (en) * 1972-09-29 1975-02-04 Hooker Chemicals Plastics Corp Apparatus for the electrolytic production of alkali
US4000991A (en) * 1975-03-27 1977-01-04 Krebs Engineers Method of removing fly ash particulates from flue gases in a closed-loop wet scrubbing system
US4002721A (en) * 1974-09-26 1977-01-11 Chevron Research Company Process improvement in the absorption of acid gas from a feed gas
US4069063A (en) * 1976-11-24 1978-01-17 Westvaco Corporation Cement composition
US4080270A (en) * 1975-01-22 1978-03-21 Diamond Shamrock Corporation Production of alkali metal carbonates in a membrane cell
US4140510A (en) * 1976-06-16 1979-02-20 Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. Process for disintegrating material containing alkali-alkali earth silicate for yielding alkali silicate or alkali carbonate solutions and materials having a large specific surface
US4188291A (en) * 1978-04-06 1980-02-12 Anderson Donald R Treatment of industrial waste water
US4246075A (en) * 1979-03-19 1981-01-20 Marine Resources Company Mineral accretion of large surface structures, building components and elements
US4253922A (en) * 1979-02-23 1981-03-03 Ppg Industries, Inc. Cathode electrocatalysts for solid polymer electrolyte chlor-alkali cells
US4312646A (en) * 1977-11-17 1982-01-26 Ciba-Geigy Corporation Gas scrubbing tower
US4315872A (en) * 1977-07-29 1982-02-16 Fuji Kasui Engineering Co., Ltd. Plate column
US4370307A (en) * 1980-02-29 1983-01-25 Martin Marietta Corporation Preparation of pure magnesian values
US4376101A (en) * 1981-11-13 1983-03-08 Exxon Research And Engineering Co. Process for removing acid gases using a basic salt activated with a non-sterically hindered diamine
US4377554A (en) * 1981-08-26 1983-03-22 Becton, Dickinson And Company Generation of microaerophilic atmosphere
US4440611A (en) * 1981-12-09 1984-04-03 The Texas A & M University System Cathodic electrochemical process for preventing or retarding microbial and calcareous fouling
US4634533A (en) * 1985-04-26 1987-01-06 Somerville Robert L Method of converting brines to useful products
US4804449A (en) * 1986-02-25 1989-02-14 Sweeney Charles T Electrolytic cell
US4899544A (en) * 1987-08-13 1990-02-13 Boyd Randall T Cogeneration/CO2 production process and plant
US5100633A (en) * 1985-11-07 1992-03-31 Passamaquoddy Technology Limited Partnership Method for scrubbing pollutants from an exhaust gas stream
US5275651A (en) * 1990-05-28 1994-01-04 Maruo Calcium Company Limited Monodisperse vaterite type calcium carbonate, its manufacturing method and method of controlling growth of particles and shape thereof
US5275794A (en) * 1991-11-20 1994-01-04 Luna Raymundo R Process for producing sodium bicarbonate from natural soda salts
US5282935A (en) * 1992-04-13 1994-02-01 Olin Corporation Electrodialytic process for producing an alkali solution
US5378279A (en) * 1990-08-10 1995-01-03 Conroy; Michel Enhanced cement mixed with selected aggregates
US5388456A (en) * 1990-07-05 1995-02-14 Kettel; Dirk Procedure in order to detect the gas potential in sedimentary basins and the oil potential obtained from this
US5595641A (en) * 1991-06-27 1997-01-21 Denora Permelec S.P.A. Apparatus and process for electrochemically decomposing salt solutions to form the relevant base and acid
US5614078A (en) * 1995-06-01 1997-03-25 Upscale Technologies, Inc. Method and apparatus for removing nitrates from water
US5855666A (en) * 1996-12-24 1999-01-05 Cement-Lock Group, L.L.C. Process for preparing environmentally stable products by the remediation of contaminated sediments and soils
US5855759A (en) * 1993-11-22 1999-01-05 E. I. Du Pont De Nemours And Company Electrochemical cell and process for splitting a sulfate solution and producing a hyroxide solution sulfuric acid and a halogen gas
US5879948A (en) * 1997-05-12 1999-03-09 Tennessee Valley Authority Determination of total mercury in exhaust gases
US5885478A (en) * 1997-10-29 1999-03-23 Fritz Industries, Inc Concrete mix water
US6024848A (en) * 1998-04-15 2000-02-15 International Fuel Cells, Corporation Electrochemical cell with a porous support plate
US6174507B1 (en) * 1998-06-05 2001-01-16 Texaco Inc. Acid gas solvent filtration system
US6180012B1 (en) * 1997-03-19 2001-01-30 Paul I. Rongved Sea water desalination using CO2 gas from combustion exhaust
US6180074B1 (en) * 1995-10-31 2001-01-30 Novacarb Method for processing flue gases containing sulphur oxides
US6186426B1 (en) * 1998-03-26 2001-02-13 Sep Gesellschaft Fur Technische Studien Comminution and distribution device for comminutable, pumpable materials
US6190428B1 (en) * 1996-03-25 2001-02-20 The United States Of America As Represented By The Secretary Of The Navy Electrochemical process for removing low-valent sulfur from carbon
US6200543B1 (en) * 1998-02-25 2001-03-13 Mississippi Lime Company Apparatus and methods for reducing carbon dioxide content of an air stream
US6200381B1 (en) * 1995-12-05 2001-03-13 Periclase Pty. Ltd. Settable composition and uses therefor
US20020009410A1 (en) * 1999-07-21 2002-01-24 G. R. International, Inc. Precisely sized precipitated calcium carbonate (PCC) crystals of preselected crystal habit, manufactured using pressure carbonation
US6352576B1 (en) * 2000-03-30 2002-03-05 The Regents Of The University Of California Methods of selectively separating CO2 from a multicomponent gaseous stream using CO2 hydrate promoters
US20030017088A1 (en) * 2001-07-20 2003-01-23 William Downs Method for simultaneous removal and sequestration of CO2 in a highly energy efficient manner
US20030027023A1 (en) * 2001-07-12 2003-02-06 Co2 Solution Inc. Process for generating electricity with a hydrogen fuel cell
US6517631B2 (en) * 1998-07-20 2003-02-11 The University Of Wyoming Research Corporation Method of producing a coal combustion ash composition
US6518217B2 (en) * 2001-05-25 2003-02-11 Changchun Institute Of Applied Chemistry, Chinese Academy Of Sciences Method of preparing of nanometer electrocatalyst for proton exchange membrane fuel cell
US6537456B2 (en) * 1996-08-12 2003-03-25 Debasish Mukhopadhyay Method and apparatus for high efficiency reverse osmosis operation
US20040014845A1 (en) * 2000-12-18 2004-01-22 Koichi Takamura Asphalt-based formulations and method of making and using the same for paving and coating applications
US20040028963A1 (en) * 2001-02-02 2004-02-12 Claudius Kormann Method and device for deionising cooling media for fuel cells
US20040040715A1 (en) * 2001-10-24 2004-03-04 Wellington Scott Lee In situ production of a blending agent from a hydrocarbon containing formation
US20040040671A1 (en) * 2002-09-04 2004-03-04 Duesel Bernard F. Treatment of spent caustic refinery effluents
US20040052865A1 (en) * 2002-09-13 2004-03-18 Gower Laurie B. Materials and methods for drug delivery and uptake
US6712946B2 (en) * 2001-06-18 2004-03-30 The Electrosynthesis Company, Inc. Electrodialysis of multivalent metal salts
US20050002847A1 (en) * 2003-05-02 2005-01-06 The Penn State Research Foundation Process for sequestering carbon dioxide and sulfur dioxide
US6841512B1 (en) * 1999-04-12 2005-01-11 Ovonic Battery Company, Inc. Finely divided metal catalyst and method for making same
US20050011770A1 (en) * 2003-07-18 2005-01-20 Tatenuma Katsuyoshi Reduction method of atmospheric carbon dioxide, recovery and removal method of carbonate contained in seawater, and disposal method of the recovered carbonate
US20050031522A1 (en) * 2001-10-23 2005-02-10 Ac Capital Management, Inc. Integrated oxygen generation and carbon dioxide absorption method apparatus and systems
US20050031515A1 (en) * 2003-08-04 2005-02-10 Graymont(Qc) Inc. Hydrated lim kiln dust recirculation method for gas scrubbing
US20050036932A1 (en) * 1998-10-29 2005-02-17 Nkk Corporation Method for reducing exhaust carbon dioxide
US20060039853A1 (en) * 2003-02-06 2006-02-23 The Ohio State University Research Foundation Separation of carbon dioxide (CO2) from gas mixtures by calcium based reaction separation (CaRS-CO2) process
US20060051274A1 (en) * 2004-08-23 2006-03-09 Wright Allen B Removal of carbon dioxide from air
US20060048517A1 (en) * 2002-09-27 2006-03-09 Sylvie Fradette Process and a plant for recycling carbon dioxide emissions from power plants into useful carbonated species
US20060057036A1 (en) * 2002-10-25 2006-03-16 Angel Ayala Hermosillo System for elimnating polluting gases produced from combustion processes
US20060060532A1 (en) * 2004-09-13 2006-03-23 The University Of South Carolina Water desalination process and apparatus
US7182851B2 (en) * 2000-11-30 2007-02-27 Rodolfo Antonio M Gomez Electrolytic commercial production of hydrogen from hydrocarbon compounds
US20070045125A1 (en) * 2005-08-25 2007-03-01 Hartvigsen Joseph J Electrochemical Cell for Production of Synthesis Gas Using Atmospheric Air and Water
US20070056487A1 (en) * 2003-04-29 2007-03-15 Anthony Edward J In-situ capture of carbon dioxide and sulphur dioxide in a fluidized bed combustor
US7314847B1 (en) * 2004-10-21 2008-01-01 The United States Of America As Represented By The United States Department Of Energy Regenerable sorbents for CO2 capture from moderate and high temperature gas streams
US20080031801A1 (en) * 2004-05-04 2008-02-07 Lackner Klaus S Carbon Dioxide Capture and Mitigation of Carbon Dioxide Emissions
US20080035036A1 (en) * 2006-06-05 2008-02-14 Bassani Dominic T Environmentally compatible integrated food and energy production system
US20080059206A1 (en) * 2006-03-14 2008-03-06 Federico Jenkins Method of distributing the cost of preserving the environment
US20080245672A1 (en) * 2007-04-03 2008-10-09 New Sky Energy, Inc. Electrochemical methods to generate hydrogen and sequester carbon dioxide
US20090001020A1 (en) * 2007-06-28 2009-01-01 Constantz Brent R Desalination methods and systems that include carbonate compound precipitation
US20090010827A1 (en) * 2005-12-20 2009-01-08 Jacobus Johannes Cornelis Geerlings Process for Sequestration of Carbon Dioxide
US20090020044A1 (en) * 2007-05-24 2009-01-22 Constantz Brent R Hydraulic cements comprising carbonate compound compositions
US20090043687A1 (en) * 2000-11-01 2009-02-12 Van Soestbergen Mark Method and System for Banking and Exchanging Emission Reduction Credits
US20100024686A1 (en) * 2007-06-28 2010-02-04 Brent Constantz Rocks and aggregate, and methods of making and using the same
US20100037653A1 (en) * 2006-04-05 2010-02-18 Enis Ben M Desalination Method and System Using Compressed Air Energy Systems
US7875163B2 (en) * 2008-07-16 2011-01-25 Calera Corporation Low energy 4-cell electrochemical system with carbon dioxide gas
US20110030586A1 (en) * 2009-08-07 2011-02-10 Brent Constantz Carbonate products for carbon capture and storage
US7887694B2 (en) * 2007-12-28 2011-02-15 Calera Corporation Methods of sequestering CO2
US20110036728A1 (en) * 2008-12-23 2011-02-17 Calera Corporation Low-energy electrochemical proton transfer system and method
US8114214B2 (en) * 2009-12-31 2012-02-14 Calera Corporation Methods and compositions using calcium carbonate

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4197421A (en) * 1978-08-17 1980-04-08 The United States Of America As Represented By The United States Department Of Energy Synthetic carbonaceous fuels and feedstocks
NL8801511A (nl) * 1988-06-14 1990-01-02 Hoogovens Groep Bv Werkwijze voor het elektrolytisch bekleden van een metalen substraat met een metalen bekledingslaag.
JP3962434B2 (ja) * 1997-06-30 2007-08-22 エレクトロシンセシス・カンパニー・インコーポレーテッド アスコルビン酸の電気化学的回収方法
US20080223727A1 (en) * 2005-10-13 2008-09-18 Colin Oloman Continuous Co-Current Electrochemical Reduction of Carbon Dioxide

Patent Citations (101)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1176747A (en) * 1915-03-04 1916-03-28 Benjamin M Ferguson Gas-scrubbing apparatus.
US1169766A (en) * 1915-10-02 1916-02-01 Hermann A Brassert Gas-washer.
US1172930A (en) * 1915-12-08 1916-02-22 Hermann A Brassert Method of and apparatus for gas-washing.
US1655171A (en) * 1925-06-17 1928-01-03 Bartlett Hayward Co Liquid and gas contact apparatus
US1897725A (en) * 1926-05-28 1933-02-14 Ig Farbenindustrie Ag Process for extracting carbon dioxid from gaseous mixtures and forming alkaline carbonates
US1986736A (en) * 1934-04-09 1935-01-01 James L Mauthe Gas washer
US2273795A (en) * 1936-12-31 1942-02-17 Nat Carbon Co Inc Electrolytic process
US2227465A (en) * 1938-06-11 1941-01-07 Binks Mfg Co Means for eliminating divided material in industrial processes
US2458039A (en) * 1945-10-05 1949-01-04 Bertrand H Wait Aggregate for improving portland cement concretes
US2967807A (en) * 1952-01-23 1961-01-10 Hooker Chemical Corp Electrolytic decomposition of sodium chloride
US3120426A (en) * 1959-06-24 1964-02-04 Kaiser Aluminium Chem Corp Process for the production of aragonite crystals
US3165460A (en) * 1962-04-11 1965-01-12 American Mach & Foundry Electrolytic acid generator
US3374164A (en) * 1963-06-28 1968-03-19 Ceskoslovenska Akademie Ved Electrolyzer for simultaneous preparation of chlorine and alkali carbonates
US3558769A (en) * 1965-09-24 1971-01-26 Guardian Chemical Corp Compositions for dental prophylaxis
US3420775A (en) * 1967-07-05 1969-01-07 Edgar A Cadwallader Prevention of scale in saline water evaporators using carbon dioxide under special conditions
US3721621A (en) * 1969-12-02 1973-03-20 W Hough Forward-osmosis solvent extraction
US3861928A (en) * 1970-10-30 1975-01-21 Flintkote Co Hydraulic cement and method of producing same
US3864236A (en) * 1972-09-29 1975-02-04 Hooker Chemicals Plastics Corp Apparatus for the electrolytic production of alkali
US4002721A (en) * 1974-09-26 1977-01-11 Chevron Research Company Process improvement in the absorption of acid gas from a feed gas
US4080270A (en) * 1975-01-22 1978-03-21 Diamond Shamrock Corporation Production of alkali metal carbonates in a membrane cell
US4000991A (en) * 1975-03-27 1977-01-04 Krebs Engineers Method of removing fly ash particulates from flue gases in a closed-loop wet scrubbing system
US4140510A (en) * 1976-06-16 1979-02-20 Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. Process for disintegrating material containing alkali-alkali earth silicate for yielding alkali silicate or alkali carbonate solutions and materials having a large specific surface
US4069063A (en) * 1976-11-24 1978-01-17 Westvaco Corporation Cement composition
US4315872A (en) * 1977-07-29 1982-02-16 Fuji Kasui Engineering Co., Ltd. Plate column
US4312646A (en) * 1977-11-17 1982-01-26 Ciba-Geigy Corporation Gas scrubbing tower
US4188291A (en) * 1978-04-06 1980-02-12 Anderson Donald R Treatment of industrial waste water
US4253922A (en) * 1979-02-23 1981-03-03 Ppg Industries, Inc. Cathode electrocatalysts for solid polymer electrolyte chlor-alkali cells
US4246075A (en) * 1979-03-19 1981-01-20 Marine Resources Company Mineral accretion of large surface structures, building components and elements
US4370307A (en) * 1980-02-29 1983-01-25 Martin Marietta Corporation Preparation of pure magnesian values
US4377554A (en) * 1981-08-26 1983-03-22 Becton, Dickinson And Company Generation of microaerophilic atmosphere
US4376101A (en) * 1981-11-13 1983-03-08 Exxon Research And Engineering Co. Process for removing acid gases using a basic salt activated with a non-sterically hindered diamine
US4440611A (en) * 1981-12-09 1984-04-03 The Texas A & M University System Cathodic electrochemical process for preventing or retarding microbial and calcareous fouling
US4634533A (en) * 1985-04-26 1987-01-06 Somerville Robert L Method of converting brines to useful products
US5100633A (en) * 1985-11-07 1992-03-31 Passamaquoddy Technology Limited Partnership Method for scrubbing pollutants from an exhaust gas stream
US4804449A (en) * 1986-02-25 1989-02-14 Sweeney Charles T Electrolytic cell
US4899544A (en) * 1987-08-13 1990-02-13 Boyd Randall T Cogeneration/CO2 production process and plant
US5275651A (en) * 1990-05-28 1994-01-04 Maruo Calcium Company Limited Monodisperse vaterite type calcium carbonate, its manufacturing method and method of controlling growth of particles and shape thereof
US5388456A (en) * 1990-07-05 1995-02-14 Kettel; Dirk Procedure in order to detect the gas potential in sedimentary basins and the oil potential obtained from this
US5378279A (en) * 1990-08-10 1995-01-03 Conroy; Michel Enhanced cement mixed with selected aggregates
US5595641A (en) * 1991-06-27 1997-01-21 Denora Permelec S.P.A. Apparatus and process for electrochemically decomposing salt solutions to form the relevant base and acid
US5275794A (en) * 1991-11-20 1994-01-04 Luna Raymundo R Process for producing sodium bicarbonate from natural soda salts
US5282935A (en) * 1992-04-13 1994-02-01 Olin Corporation Electrodialytic process for producing an alkali solution
US5855759A (en) * 1993-11-22 1999-01-05 E. I. Du Pont De Nemours And Company Electrochemical cell and process for splitting a sulfate solution and producing a hyroxide solution sulfuric acid and a halogen gas
US5614078A (en) * 1995-06-01 1997-03-25 Upscale Technologies, Inc. Method and apparatus for removing nitrates from water
US6180074B1 (en) * 1995-10-31 2001-01-30 Novacarb Method for processing flue gases containing sulphur oxides
US6200381B1 (en) * 1995-12-05 2001-03-13 Periclase Pty. Ltd. Settable composition and uses therefor
US6190428B1 (en) * 1996-03-25 2001-02-20 The United States Of America As Represented By The Secretary Of The Navy Electrochemical process for removing low-valent sulfur from carbon
US6537456B2 (en) * 1996-08-12 2003-03-25 Debasish Mukhopadhyay Method and apparatus for high efficiency reverse osmosis operation
US5855666A (en) * 1996-12-24 1999-01-05 Cement-Lock Group, L.L.C. Process for preparing environmentally stable products by the remediation of contaminated sediments and soils
US6180012B1 (en) * 1997-03-19 2001-01-30 Paul I. Rongved Sea water desalination using CO2 gas from combustion exhaust
US5879948A (en) * 1997-05-12 1999-03-09 Tennessee Valley Authority Determination of total mercury in exhaust gases
US5885478A (en) * 1997-10-29 1999-03-23 Fritz Industries, Inc Concrete mix water
US6200543B1 (en) * 1998-02-25 2001-03-13 Mississippi Lime Company Apparatus and methods for reducing carbon dioxide content of an air stream
US6186426B1 (en) * 1998-03-26 2001-02-13 Sep Gesellschaft Fur Technische Studien Comminution and distribution device for comminutable, pumpable materials
US6024848A (en) * 1998-04-15 2000-02-15 International Fuel Cells, Corporation Electrochemical cell with a porous support plate
US6174507B1 (en) * 1998-06-05 2001-01-16 Texaco Inc. Acid gas solvent filtration system
US6517631B2 (en) * 1998-07-20 2003-02-11 The University Of Wyoming Research Corporation Method of producing a coal combustion ash composition
US20050036932A1 (en) * 1998-10-29 2005-02-17 Nkk Corporation Method for reducing exhaust carbon dioxide
US6841512B1 (en) * 1999-04-12 2005-01-11 Ovonic Battery Company, Inc. Finely divided metal catalyst and method for making same
US20020009410A1 (en) * 1999-07-21 2002-01-24 G. R. International, Inc. Precisely sized precipitated calcium carbonate (PCC) crystals of preselected crystal habit, manufactured using pressure carbonation
US6352576B1 (en) * 2000-03-30 2002-03-05 The Regents Of The University Of California Methods of selectively separating CO2 from a multicomponent gaseous stream using CO2 hydrate promoters
US20090043687A1 (en) * 2000-11-01 2009-02-12 Van Soestbergen Mark Method and System for Banking and Exchanging Emission Reduction Credits
US7182851B2 (en) * 2000-11-30 2007-02-27 Rodolfo Antonio M Gomez Electrolytic commercial production of hydrogen from hydrocarbon compounds
US20040014845A1 (en) * 2000-12-18 2004-01-22 Koichi Takamura Asphalt-based formulations and method of making and using the same for paving and coating applications
US20040028963A1 (en) * 2001-02-02 2004-02-12 Claudius Kormann Method and device for deionising cooling media for fuel cells
US6518217B2 (en) * 2001-05-25 2003-02-11 Changchun Institute Of Applied Chemistry, Chinese Academy Of Sciences Method of preparing of nanometer electrocatalyst for proton exchange membrane fuel cell
US6712946B2 (en) * 2001-06-18 2004-03-30 The Electrosynthesis Company, Inc. Electrodialysis of multivalent metal salts
US20030027023A1 (en) * 2001-07-12 2003-02-06 Co2 Solution Inc. Process for generating electricity with a hydrogen fuel cell
US20030017088A1 (en) * 2001-07-20 2003-01-23 William Downs Method for simultaneous removal and sequestration of CO2 in a highly energy efficient manner
US20050031522A1 (en) * 2001-10-23 2005-02-10 Ac Capital Management, Inc. Integrated oxygen generation and carbon dioxide absorption method apparatus and systems
US20040040715A1 (en) * 2001-10-24 2004-03-04 Wellington Scott Lee In situ production of a blending agent from a hydrocarbon containing formation
US20040040671A1 (en) * 2002-09-04 2004-03-04 Duesel Bernard F. Treatment of spent caustic refinery effluents
US20040052865A1 (en) * 2002-09-13 2004-03-18 Gower Laurie B. Materials and methods for drug delivery and uptake
US20060048517A1 (en) * 2002-09-27 2006-03-09 Sylvie Fradette Process and a plant for recycling carbon dioxide emissions from power plants into useful carbonated species
US20060057036A1 (en) * 2002-10-25 2006-03-16 Angel Ayala Hermosillo System for elimnating polluting gases produced from combustion processes
US20060039853A1 (en) * 2003-02-06 2006-02-23 The Ohio State University Research Foundation Separation of carbon dioxide (CO2) from gas mixtures by calcium based reaction separation (CaRS-CO2) process
US20070056487A1 (en) * 2003-04-29 2007-03-15 Anthony Edward J In-situ capture of carbon dioxide and sulphur dioxide in a fluidized bed combustor
US20050002847A1 (en) * 2003-05-02 2005-01-06 The Penn State Research Foundation Process for sequestering carbon dioxide and sulfur dioxide
US20050011770A1 (en) * 2003-07-18 2005-01-20 Tatenuma Katsuyoshi Reduction method of atmospheric carbon dioxide, recovery and removal method of carbonate contained in seawater, and disposal method of the recovered carbonate
US20050031515A1 (en) * 2003-08-04 2005-02-10 Graymont(Qc) Inc. Hydrated lim kiln dust recirculation method for gas scrubbing
US20080031801A1 (en) * 2004-05-04 2008-02-07 Lackner Klaus S Carbon Dioxide Capture and Mitigation of Carbon Dioxide Emissions
US20060051274A1 (en) * 2004-08-23 2006-03-09 Wright Allen B Removal of carbon dioxide from air
US20060060532A1 (en) * 2004-09-13 2006-03-23 The University Of South Carolina Water desalination process and apparatus
US7314847B1 (en) * 2004-10-21 2008-01-01 The United States Of America As Represented By The United States Department Of Energy Regenerable sorbents for CO2 capture from moderate and high temperature gas streams
US20070045125A1 (en) * 2005-08-25 2007-03-01 Hartvigsen Joseph J Electrochemical Cell for Production of Synthesis Gas Using Atmospheric Air and Water
US20090010827A1 (en) * 2005-12-20 2009-01-08 Jacobus Johannes Cornelis Geerlings Process for Sequestration of Carbon Dioxide
US20080059206A1 (en) * 2006-03-14 2008-03-06 Federico Jenkins Method of distributing the cost of preserving the environment
US20100037653A1 (en) * 2006-04-05 2010-02-18 Enis Ben M Desalination Method and System Using Compressed Air Energy Systems
US20080035036A1 (en) * 2006-06-05 2008-02-14 Bassani Dominic T Environmentally compatible integrated food and energy production system
US20080245672A1 (en) * 2007-04-03 2008-10-09 New Sky Energy, Inc. Electrochemical methods to generate hydrogen and sequester carbon dioxide
US20090020044A1 (en) * 2007-05-24 2009-01-22 Constantz Brent R Hydraulic cements comprising carbonate compound compositions
US20100024686A1 (en) * 2007-06-28 2010-02-04 Brent Constantz Rocks and aggregate, and methods of making and using the same
US20090001020A1 (en) * 2007-06-28 2009-01-01 Constantz Brent R Desalination methods and systems that include carbonate compound precipitation
US7887694B2 (en) * 2007-12-28 2011-02-15 Calera Corporation Methods of sequestering CO2
US7875163B2 (en) * 2008-07-16 2011-01-25 Calera Corporation Low energy 4-cell electrochemical system with carbon dioxide gas
US20110036728A1 (en) * 2008-12-23 2011-02-17 Calera Corporation Low-energy electrochemical proton transfer system and method
US20110030586A1 (en) * 2009-08-07 2011-02-10 Brent Constantz Carbonate products for carbon capture and storage
US20110033239A1 (en) * 2009-08-07 2011-02-10 Brent Constantz Utilizing salts for carbon capture and storage
US20110035154A1 (en) * 2009-08-07 2011-02-10 Treavor Kendall Utilizing salts for carbon capture and storage
US20110030957A1 (en) * 2009-08-07 2011-02-10 Brent Constantz Carbon capture and storage
US8114214B2 (en) * 2009-12-31 2012-02-14 Calera Corporation Methods and compositions using calcium carbonate

Cited By (87)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110054084A1 (en) * 2007-05-24 2011-03-03 Constantz Brent R Hydraulic cements comprising carbonate compound compositions
US8857118B2 (en) 2007-05-24 2014-10-14 Calera Corporation Hydraulic cements comprising carbonate compound compositions
US20110132234A1 (en) * 2007-05-24 2011-06-09 Constantz Brent R Hydraulic cements comprising carbonate compound compositions
US9260314B2 (en) 2007-12-28 2016-02-16 Calera Corporation Methods and systems for utilizing waste sources of metal oxides
US20100135865A1 (en) * 2007-12-28 2010-06-03 Constantz Brent R Electrochemical methods of sequestering co2
US20110059000A1 (en) * 2007-12-28 2011-03-10 Constantz Brent R Methods of sequestering co2
US20100135882A1 (en) * 2007-12-28 2010-06-03 Constantz Brent R Methods of sequestering co2
US20100132556A1 (en) * 2007-12-28 2010-06-03 Constantz Brent R Methods of sequestering co2
US8333944B2 (en) 2007-12-28 2012-12-18 Calera Corporation Methods of sequestering CO2
US20100313794A1 (en) * 2007-12-28 2010-12-16 Constantz Brent R Production of carbonate-containing compositions from material comprising metal silicates
US20100144521A1 (en) * 2008-05-29 2010-06-10 Brent Constantz Rocks and Aggregate, and Methods of Making and Using the Same
US20100239467A1 (en) * 2008-06-17 2010-09-23 Brent Constantz Methods and systems for utilizing waste sources of metal oxides
US20100002587A1 (en) * 2008-07-01 2010-01-07 Gayle Loretta Ray Noble Diagnostics for Serial Communication Busses
US8894830B2 (en) 2008-07-16 2014-11-25 Celera Corporation CO2 utilization in electrochemical systems
US8357270B2 (en) 2008-07-16 2013-01-22 Calera Corporation CO2 utilization in electrochemical systems
US7993500B2 (en) 2008-07-16 2011-08-09 Calera Corporation Gas diffusion anode and CO2 cathode electrolyte system
US20100230293A1 (en) * 2008-07-16 2010-09-16 Gilliam Ryan J Co2 utilization in electrochemical systems
US20100140103A1 (en) * 2008-07-16 2010-06-10 Gilliam Ryan J Gas Diffusion Anode and CO2 Cathode Electrolyte System
US8603424B2 (en) 2008-09-30 2013-12-10 Calera Corporation CO2-sequestering formed building materials
US8006446B2 (en) 2008-09-30 2011-08-30 Calera Corporation CO2-sequestering formed building materials
US20100313793A1 (en) * 2008-09-30 2010-12-16 Constantz Brent R Reduced-carbon footprint concrete compositions
US8470275B2 (en) 2008-09-30 2013-06-25 Calera Corporation Reduced-carbon footprint concrete compositions
US8869477B2 (en) 2008-09-30 2014-10-28 Calera Corporation Formed building materials
US8431100B2 (en) 2008-09-30 2013-04-30 Calera Corporation CO2-sequestering formed building materials
US9061940B2 (en) 2008-09-30 2015-06-23 Calera Corporation Concrete compositions and methods
US9133581B2 (en) 2008-10-31 2015-09-15 Calera Corporation Non-cementitious compositions comprising vaterite and methods thereof
US20100150802A1 (en) * 2008-12-11 2010-06-17 Gilliam Ryan J Processing co2 utilizing a recirculating solution
US20100258035A1 (en) * 2008-12-24 2010-10-14 Brent Constantz Compositions and methods using substances containing carbon
US20110083968A1 (en) * 2009-02-10 2011-04-14 Gilliam Ryan J Low-voltage alkaline production using hydrogen and electrocatalytic electrodes
US8834688B2 (en) 2009-02-10 2014-09-16 Calera Corporation Low-voltage alkaline production using hydrogen and electrocatalytic electrodes
US9267211B2 (en) 2009-02-10 2016-02-23 Calera Corporation Low-voltage alkaline production using hydrogen and electrocatalytic electrodes
US20110226989A9 (en) * 2009-03-02 2011-09-22 William Randall Seeker Gas stream multi-pollutants control systems and methods
US20100219373A1 (en) * 2009-03-02 2010-09-02 William Randall Seeker Gas stream multi-pollutants control systems and methods
US8883104B2 (en) 2009-03-02 2014-11-11 Calera Corporation Gas stream multi-pollutants control systems and methods
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
US20100230830A1 (en) * 2009-03-10 2010-09-16 Kasra Farsad Systems and Methods for Processing CO2
US20100229725A1 (en) * 2009-03-10 2010-09-16 Kasra Farsad Systems and Methods for Processing CO2
US7993511B2 (en) 2009-07-15 2011-08-09 Calera Corporation Electrochemical production of an alkaline solution using CO2
US20110147227A1 (en) * 2009-07-15 2011-06-23 Gilliam Ryan J Acid separation by acid retardation on an ion exchange resin in an electrochemical system
US20110079515A1 (en) * 2009-07-15 2011-04-07 Gilliam Ryan J Alkaline production using a gas diffusion anode with a hydrostatic pressure
US20100084280A1 (en) * 2009-07-15 2010-04-08 Gilliam Ryan J Electrochemical production of an alkaline solution using co2
US20110030957A1 (en) * 2009-08-07 2011-02-10 Brent Constantz Carbon capture and storage
US20110033239A1 (en) * 2009-08-07 2011-02-10 Brent Constantz Utilizing salts for carbon capture and storage
US20110071309A1 (en) * 2009-09-24 2011-03-24 Constantz Brent R Methods and Systems for Utilization of HCI
US8062418B2 (en) 2009-12-31 2011-11-22 Calera Corporation Methods and compositions using calcium carbonate
US20110067603A1 (en) * 2009-12-31 2011-03-24 Constantz Brent R Methods and compositions using calcium carbonate
US8114214B2 (en) 2009-12-31 2012-02-14 Calera Corporation Methods and compositions using calcium carbonate
US8177909B2 (en) 2009-12-31 2012-05-15 Calera Corporation Methods and compositions using calcium carbonate
US8932400B2 (en) 2009-12-31 2015-01-13 Calera Corporation Methods and compositions using calcium carbonate
US8906156B2 (en) 2009-12-31 2014-12-09 Calera Corporation Cement and concrete with reinforced material
US9056790B2 (en) 2009-12-31 2015-06-16 Calera Corporation Methods and compositions using calcium carbonate
US8137455B1 (en) 2009-12-31 2012-03-20 Calera Corporation Methods and compositions using calcium carbonate
US8936773B2 (en) 2011-04-28 2015-01-20 Calera Corporation Methods and compositions using calcium carbonate and stabilizer
US8691175B2 (en) 2011-04-28 2014-04-08 Calera Corporation Calcium sulfate and CO2 sequestration
US9139472B2 (en) 2011-04-28 2015-09-22 Calera Corporation Methods and compositions using calcium carbonate and stabilizer
US9187835B2 (en) 2011-05-19 2015-11-17 Calera Corporation Electrochemical systems and methods using metal and ligand
US9200375B2 (en) 2011-05-19 2015-12-01 Calera Corporation Systems and methods for preparation and separation of products
US9187834B2 (en) 2011-05-19 2015-11-17 Calera Corporation Electrochemical hydroxide systems and methods using metal oxidation
US9957623B2 (en) 2011-05-19 2018-05-01 Calera Corporation Systems and methods for preparation and separation of products
US8999057B2 (en) 2011-09-28 2015-04-07 Calera Corporation Cement and concrete with calcium aluminates
US10662447B2 (en) 2012-12-21 2020-05-26 Ee-Terrabon Biofuels, Llc System and process for obtaining products from biomass
US9828313B2 (en) 2013-07-31 2017-11-28 Calera Corporation Systems and methods for separation and purification of products
US10287223B2 (en) 2013-07-31 2019-05-14 Calera Corporation Systems and methods for separation and purification of products
EP2891514A1 (fr) * 2014-01-03 2015-07-08 Marcus Invest Procédé et dispositif pour le traitement de saumures
FR3016164A1 (fr) * 2014-01-03 2015-07-10 Vb2M Procede et dispositif pour le traitement de saumures
US9902652B2 (en) 2014-04-23 2018-02-27 Calera Corporation Methods and systems for utilizing carbide lime or slag
US9957621B2 (en) 2014-09-15 2018-05-01 Calera Corporation Electrochemical systems and methods using metal halide to form products
US9880124B2 (en) 2014-11-10 2018-01-30 Calera Corporation Measurement of ion concentration in presence of organics
US10480085B2 (en) 2015-03-16 2019-11-19 Calera Corporation Ion exchange membranes, electrochemical systems, and methods
US10161050B2 (en) 2015-03-16 2018-12-25 Calera Corporation Ion exchange membranes, electrochemical systems, and methods
US10801117B2 (en) 2015-03-16 2020-10-13 Calera Corporation Ion exchange membranes, electrochemical systems, and methods
US10718055B2 (en) 2015-06-15 2020-07-21 The Regents Of The University Of Colorado, A Body Corporate Carbon dioxide capture and storage electrolytic methods
US10266954B2 (en) 2015-10-28 2019-04-23 Calera Corporation Electrochemical, halogenation, and oxyhalogenation systems and methods
US10844496B2 (en) 2015-10-28 2020-11-24 Calera Corporation Electrochemical, halogenation, and oxyhalogenation systems and methods
US10236526B2 (en) 2016-02-25 2019-03-19 Calera Corporation On-line monitoring of process/system
US10847844B2 (en) 2016-04-26 2020-11-24 Calera Corporation Intermediate frame, electrochemical systems, and methods
US11239503B2 (en) 2016-04-26 2022-02-01 Calera Corporation Intermediate frame, electrochemical systems, and methods
US10619254B2 (en) 2016-10-28 2020-04-14 Calera Corporation Electrochemical, chlorination, and oxychlorination systems and methods to form propylene oxide or ethylene oxide
CN106745095A (zh) * 2017-01-25 2017-05-31 四川大学 利用芒硝和白云石制取纯碱联产石膏和碱式碳酸镁的方法
US10556848B2 (en) 2017-09-19 2020-02-11 Calera Corporation Systems and methods using lanthanide halide
US10807927B2 (en) 2018-05-30 2020-10-20 Calera Corporation Methods and systems to form propylene chlorohydrin from dichloropropane using lewis acid
US10590054B2 (en) 2018-05-30 2020-03-17 Calera Corporation Methods and systems to form propylene chlorohydrin from dichloropropane using Lewis acid
US11577965B2 (en) 2020-02-25 2023-02-14 Arelac, Inc. Methods and systems for treatment of lime to form vaterite
US11118492B1 (en) 2020-04-27 2021-09-14 Stec Technology, Inc. Reactive cyclic induction system and method for reducing pollutants in marine diesel exhaust
US11377363B2 (en) 2020-06-30 2022-07-05 Arelac, Inc. Methods and systems for forming vaterite from calcined limestone using electric kiln
WO2024020027A1 (fr) * 2022-07-18 2024-01-25 The Regents Of The University Of Calfornia Cellule électrochimique à chambres multiples pour l'élimination de dioxyde de carbone

Also Published As

Publication number Publication date
CN101878328A (zh) 2010-11-03
EP2240629A4 (fr) 2013-04-24
EP2240629A1 (fr) 2010-10-20
WO2010087823A1 (fr) 2010-08-05
CA2696075A1 (fr) 2010-07-28

Similar Documents

Publication Publication Date Title
US20110042230A1 (en) Low-energy electrochemical bicarbonate ion solution
CA2700721C (fr) Systeme electrochimique a 4 cellules basse energie comportant du dioxyde de carbone gazeux
US7993511B2 (en) Electrochemical production of an alkaline solution using CO2
AU2010201006B2 (en) Low-voltage alkaline production from brines
WO2011097468A2 (fr) Séparation d'acide par rétention d'acide sur une résine échangeuse d'ions dans un système électrochimique
US20110147227A1 (en) Acid separation by acid retardation on an ion exchange resin in an electrochemical system
US20100224503A1 (en) Low-energy electrochemical hydroxide system and method
US20110083968A1 (en) Low-voltage alkaline production using hydrogen and electrocatalytic electrodes
WO2011008223A1 (fr) Production électrochimique d’une solution alcaline à l’aide de co2
EP3126038B1 (fr) Conversion de gaz et traitement d'une solution
KR20170138364A (ko) 이산화탄소의 분리 방법 및 이산화탄소 분리 시스템
WO2017158493A1 (fr) Cellules électrolytiques et leurs utilisations dans le traitement du drainage minier acide et dans la séquestration de co2
AU2009290158A1 (en) Low-energy electrochemical bicarbonate ion solution
CA2696086C (fr) Production electrochimique d'une solution alcaline au moyen de co2
US20240141510A1 (en) Carbon Capture Using Electrochemically-Produced Acid and Base
AU2009290161B2 (en) Electrochemical production of an alkaline solution using CO2
CA2694978C (fr) Production alcaline a basse tension a partir de saumures
KR20180133688A (ko) 이산화탄소의 분리 방법 및 이산화탄소 분리 시스템
CA2696096A1 (fr) Production alcaline a basse tension au moyen d'hydrogene et d'electrodes electrocatalytiques
AU2009225358A1 (en) Low energy electromechanical hydroxide system and method

Legal Events

Date Code Title Description
AS Assignment

Owner name: CALERA CORPORATION, CALIFORNIA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:GILLIAM, RYAN;BOGGS, BRYAN;DECKER, VALENTIN;REEL/FRAME:022412/0950

Effective date: 20090304

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION