US20140221684A1 - Electrochemical Co-Production of Chemicals Utilizing a Halide Salt - Google Patents
Electrochemical Co-Production of Chemicals Utilizing a Halide Salt Download PDFInfo
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- US20140221684A1 US20140221684A1 US14/246,631 US201414246631A US2014221684A1 US 20140221684 A1 US20140221684 A1 US 20140221684A1 US 201414246631 A US201414246631 A US 201414246631A US 2014221684 A1 US2014221684 A1 US 2014221684A1
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- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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- C07C29/58—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of halogen, e.g. by hydrogenolysis, splitting-off
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C25B1/24—Halogens or compounds thereof
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- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
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- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
- C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
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- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/29—Coupling reactions
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Definitions
- the present disclosure generally relates to the field of electrochemical reactions, and more particularly to methods and/or systems for electrochemical co-production of a carboxylic acid employing a recycled reactant.
- a mechanism for mitigating emissions is to convert carbon dioxide into economically valuable materials such as fuels and industrial chemicals. If the carbon dioxide is converted using energy from renewable sources, both mitigation of carbon dioxide emissions and conversion of renewable energy into a chemical form that can be stored for later use will be possible.
- the present disclosure includes a system and method for co-producing a first product and a second product.
- the system may include a first electrochemical cell, at least one second reactor, and an acidification chamber.
- the method and system for co-producing a first product and a second product may include co-producing a carboxylic acid and at least one of an alkene, alkyne, aldehyde, ketone, or an alcohol while employing a recycled halide salt.
- FIG. 1A is a block diagram of a system in accordance with an embodiment of the present disclosure
- FIG. 1B is a block diagram of a system in accordance with an embodiment of the present disclosure.
- FIG. 2A is a block diagram of a system in accordance with another embodiment of the present disclosure.
- FIG. 2B is a block diagram of a system in accordance with an embodiment of the present disclosure.
- FIG. 3A is a block diagram of a system in accordance with an additional embodiment of the present disclosure.
- FIG. 3B is a block diagram of a system in accordance with an embodiment of the present disclosure.
- FIG. 4 is a block diagram of a system in accordance with another additional embodiment of the present disclosure.
- the systems and methods of the present disclosure may include an electrochemical cell that includes an input of a recycled reactant to co-produce valuable products at both the cathode and anode sides of the electrochemical cell.
- carbon dioxide may be reduced in a catholyte region of the electrochemical cell to a carboxylate, and a halide salt is oxidized in an anode region of the electrochemical cell to a halogen.
- the carboxylate may be fed into an acidification chamber along with a hydrogen halide to form a carboxylic acid and the halide salt.
- the halide salt is then recycled to the anode region of the electrochemical cell.
- the halogen produced in the anode compartment is subsequently fed to a second reactor along with an alkane, alkene, aromatic, or other organic compound to produce a halogenated compound and a hydrogen halide.
- the halogenated compound may be further treated in a third reactor to produce an alkene, alkyne, aldehyde, ketone, or an alcohol.
- the third reactor also produces additional hydrogen halide, which may be fed to the acidification chamber.
- the method and system of the present disclosure may use a source of carbon dioxide, an alkane, alkene, aromatic or other organic compound in order to efficiently produce an alkene, alkyne, aldehyde, ketone, or an alcohol and a carboxylic acid with the recycling of halide salt.
- the organic chemical partially oxidized in the process may serve as the source of hydrogen for the reduction of carbon dioxide and acidification of the resulting carboxylic acid.
- the organic may thereby be indirectly oxidized by carbon dioxide while the carbon dioxide is reduced by the organic such that two or more products are made simultaneously.
- the halogen employed to partially oxidize an organic and provide hydrogen to the reduction of carbon dioxide or acidification of M-Carboxylate may be recycled.
- System (or apparatus) 100 generally includes an electrochemical cell 102 .
- Electrochemical cell 102 may also be referred as a container, electrolyzer, or cell.
- Electrochemical cell 102 may be implemented as a divided cell.
- the divided cell may be a divided electrochemical cell and/or a divided photo-electrochemical cell.
- Electrochemical cell 102 may include a first region 116 and a second region 118 .
- First region 116 and second region 118 may refer to a compartment, section, or generally enclosed space and the like without departing from the scope and intent of the present disclosure.
- First region 116 may include a cathode 122 .
- Second region 118 may include an anode 124 .
- First region 116 may include a catholyte whereby carbon dioxide from carbon dioxide source 106 is included in the catholyte.
- Second region 118 may include an anolyte which may include an MX 128 where M is at least one cation and X is selected from a group consisting of F, Cl, Br, I and mixtures thereof.
- An energy source 114 may generate an electrical potential between the anode 124 and the cathode 122 . The electrical potential may be a DC voltage.
- Energy source 114 may be configured to supply a variable voltage or constant current to electrochemical cell 102 .
- Separator 120 may selectively control a flow of ions between the first region 116 and the second region 118 .
- Separator 120 may include an ion conducting membrane or diaphragm material.
- Electrochemical cell 102 is generally operational to reduce carbon dioxide in the first region 116 to an M-carboxylate 130 recoverable from the first region 116 , while producing a halogen 132 recoverable from the second region 118 .
- Carbon dioxide source 106 may provide carbon dioxide to the first region 116 of electrochemical cell 102 .
- the carbon dioxide is introduced directly into the region 116 containing the cathode 122 .
- carbon dioxide source 106 may include a source of multiple gases in which carbon dioxide has been filtered from the multiple gases.
- the electrochemical cell 102 may include a first product extractor (not shown) and second product extractor (not shown).
- Product extractors may implement an organic product and/or inorganic product extractor.
- the first product extractor (not shown) is generally operational to extract (separate) a product from the first region 116 .
- the second product extractor (not shown) may extract the second product from the second region 118 .
- the first product extractor and/or second product extractor may be implemented with electrochemical cell 102 , or may be remotely located from the electrochemical cell 102 .
- first product extractor and/or second product extractor may be implemented in a variety of mechanisms and to provide desired separation methods, such as fractional distillation, without departing from the scope and intent of the present disclosure. It is further contemplated that extracted product may be presented through a port of the system 100 for subsequent storage and/or consumption by other devices and/or processes.
- An anode side of the reaction occurring in the second region 118 of the electrochemical cell 102 may include an input of a recycled reactant of MX 128 .
- the MX 128 may include a halide salt which may be a byproduct of a reaction of acidification chamber 134 .
- the MX 128 may include a halide salt where M is a cation including at least one of Li, Na, K, Cs, Mg, Ca, hydrogen ions, tetraalkyl ammonium ions such as tetrabutylammonium, tetraethylammonium, choline, and tetraalkylphosphonium ions such as tetrabutylphosphonium, tetraethylphosphonium, and in general, R 1 R 2 R 3 R 4 N or R 1 R 2 R 3 R 4 P where R 1 to R 4 are independently alkyl, cycloalkyl, branched alkyl, and aryl, and X is selected from a group consisting of F, Cl, Br, I and mixtures thereof.
- the anode side of the reaction may produce a halogen 132 which may be presented to second reactor 108 .
- System 100 may include second reactor 108 which may receive halogen 132 produced by the second region 118 of the electrochemical cell 102 after separation from the second region via a second product extractor.
- Second reactor 108 may react halogen 132 with an alkane, alkene, aromatic, or other compound 140 to produce a halogenated product or halogenated intermediate compound 144 and HX 148 .
- the HX 148 produced in the reaction may be another recycled reactant which may be recycled to the acidification chamber 134 as an input feed to the acidification chamber 134 .
- halogenated products include monohalogenated, polyhalogenated, and perhalogenated compounds to include chloroform, hydrofluorocarbons, bromoalkanes, vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene fluoride, tetrafluorethane, bromobenzene, dibromobenzene, bromoethane, dichloroethane, allyl chloride, chlorophenol, fluorosurfactants, tetrafluoroethylene, hexafluoropropylene, difluoromethane, or pentafluoroethane.
- the acidification chamber 134 of system 100 reacts the HX 148 with the M-carboxylate 130 to produce carboxylic acid 150 and MX 128 , which is recycled as an input to the second region 118 .
- the carboxylic acid 150 may be further reacted in an additional reactor with H 2 to produce at least one of a more reduced compound.
- the carboxylic acid 150 may also be reacted with an alcohol to make an ester or diester or be used in other chemical processes.
- the M-carboxylate 130 may include M-oxalate, M-formate, M-glyoxylate, M-glycolate, or M-acetate in one embodiment.
- the system 100 includes an additional reactor, shown as third reactor 152 .
- Halogenated compound 144 may be fed to third reactor 152 .
- the third reactor 152 is a dehydrohalogenation reactor.
- Third reactor 152 may perform a dehydrohalogenation reaction of the halogenated compound 144 under specific conditions to produce a second product 156 of an alkene or alkyne. Examples of products derived from the partial oxidation via halogenation and dehalogenation in the second and third reactors are in Table 1 below.
- FIG. 2A An example implementation of the system 100 shown in FIGS. 1A and 1B is shown in FIG. 2A .
- a system 200 for generating ethylene 204 and oxalic acid 206 from a recycled reactant of tetrabutylammonium bromide (TBA-bromide) 208 and carbon dioxide 106 is provided.
- Recycled reactant comprised of tetrabutylammonium bromide (TBA-bromide) 208 is fed into the second region 118 of electrochemical cell 102 , forming bromine 210 .
- the bromine 210 is extracted from the second region 118 and fed into second reactor 108 where it reacts with ethane 212 to form bromoethane 214 and hydrogen bromide 216 .
- Any byproducts of the halogenation such as 1,1 dibromoethane or 1,2 dibromoethane, may be separated and sold as a separate product, hydrogenated back to ethane for recycle, or catalytically converted to bromoethane.
- the hydrogen bromide 216 is recycled to acidification chamber 134 .
- the bromoethane 214 is fed into the third reactor 152 , which may be a dehydrohalogenation reactor.
- the bromoethane 214 is dehydrohalogenated to form ethylene 204 .
- the cathode 122 side of the reaction of the embodiment shown in FIG. 2A includes the reduction of carbon dioxide in the presence of tetrabutylammonium cations from the reaction in the second region 118 , to form tetrabutylammonium oxalate 218 .
- the tetrabutylammonium oxalate 218 is fed into the acidification chamber 134 where it reacts with the recycled hydrogen bromide 216 to produce oxalic acid 206 and tetrabutylammonium bromide 208 .
- the tetrabutylammonium bromide 208 is recycled to the second region 118 .
- the oxalic acid 206 may be further reacted in a thermal hydrogenation chamber with H 2 to form a more reduced carbon product, such as glyoxylic acid, glycolic acid, glyoxal, glycolaldeyde, ethlylene glycol, ethanol, acetic acid, actaldehyde, ethane, or ethylene.
- a thermal hydrogenation chamber such as glyoxylic acid, glycolic acid, glyoxal, glycolaldeyde, ethlylene glycol, ethanol, acetic acid, actaldehyde, ethane, or ethylene.
- water 220 may be fed into the third reactor 152 along with the bromoethane 214 to produce ethanol 222 and hydrogen bromide 216 .
- FIGS. 3A and 3B A further embodiment of a system in accordance with the present disclosure is provided in FIGS. 3A and 3B which includes electrochemical cell 102 , second reactor 108 , third reactor 152 , and an electrochemical acidification cell 302 .
- the system 300 may be used to form an alkane, alkene, alkyne, aldehyde, ketone, or an alcohol while simultaneously producing a carboxylic acid.
- electrochemical cell 102 is generally operational to reduce carbon dioxide in the first region 116 to M-carboxylate 130 while oxidizing MX 128 in the second region 118 to produce a halogen 132 recoverable from the second region 118 .
- an anode side of the reaction occurring in the second region 118 of the electrochemical cell 102 may include receiving an input of recycled reactant, MX 128 .
- the anode side of the reaction may produce a halogen 132 which may be presented to second reactor 108 .
- Second reactor 108 may react halogen 132 with an alkane, alkene, aromatic, or other organic compound 140 to produce a halogenated compound 144 and HX 148 .
- HX 148 may be another recycled reactant which may be recycled to the electrochemical acidification cell 302 as an input feed to the electrochemical acidification cell 302 .
- the halogenated compound 144 may be fed to third reactor 152 .
- Third reactor 152 may receive a caustic compound 304 generated from the electrochemical acidification cell 302 .
- the caustic compound 304 may react with the halogenated compound 144 in either an aqueous or non-aqueous based solvent, such as alcohol, 220 to produce a second product 156 as well as MX 128 .
- the second product 156 may be an alcohol. If the reaction occurs in the presence of a non-aqueous alcohol based solvent, the second product 156 may be an alkene or alkyne.
- the MX 128 produced in the third reactor 152 may be recycled to the second region 118 of the electrochemical cell 102 .
- the caustic compound 304 may include MOH in one embodiment, where M represents the cation used in the reaction.
- MOH may include NaOH or KOH in one embodiment.
- the caustic compound 304 may include a caustic metallic base in one embodiment.
- carbon dioxide source 106 may provide carbon dioxide to the first region 116 of electrochemical cell 102 .
- the carbon dioxide is introduced directly into the region 116 containing the cathode 122 .
- Carbon dioxide is reduced in the first region 116 and reacts with the ions from the anode reaction to produce M-carboxylate 130 .
- the M-carboxylate 130 may be extracted from the first region 116 and fed into an electrochemical acidification cell 302 .
- Electrochemical acidification cell 302 may include a first region 316 and a second region 318 .
- First region 316 and second region 318 may refer to a compartment, section, or generally enclosed space, and the like without departing from the scope and intent of the present disclosure.
- First region 316 may include a cathode 322 .
- Second region 318 may include an anode 324 .
- First region 316 may include a catholyte comprising water.
- Second region 318 may include an anolyte which may include HX 148 , which is provided from the second reactor 108 and/or the third reactor 152 and recycled to the anolyte.
- An energy source 314 may generate an electrical potential between the anode 324 and the cathode 322 .
- Electrochemical acidification cell may also include an acidification region 330 .
- a first separator 332 and a second separator 333 may selectively control a flow of ions between the first region 316 , acidification region 330 , and the second region 318 .
- the first separator 332 and the second separator 333 may include an ion conducting membrane or diaphragm material.
- the electrochemical acidification cell 302 may receive three different inputs. First, M-carboxylate 130 produced by the first region 116 of the electrochemical cell 102 may be fed into the acidification region 330 of the electrochemical acidification cell 302 where it is acidified to form the first product, carboxylic acid 150 , liberating M cations which are transported to the first region 316 . Second, HX 148 may be recycled from the the second reactor 108 to the second region 318 of electrochemical acidification cell 302 to form more of the halogen, liberating W cations, or protons, for transport into the acidification region 330 .
- a third input to the electrochemical acidification cell 302 may include a water source 338 which is fed to the first region 316 .
- the water 338 is reduced to H 2 and OH ⁇ at cathode 322 , and the OH— reacts with the M cations passing from the acidification region through membrane 332 to form the caustic compound 304 .
- the caustic compound 304 is then removed from the first region 316 and may be recycled as an input to the third reactor 152 .
- H 2 336 may also be produced in the first region.
- the system 300 may include an additional reactor including a thermal hydrogenation chamber 334 .
- the thermal hydrogenation chamber 334 may react the H 2 336 produced in the first region of the electrochemical acidification cell 302 as well as the first product, carboxylic acid 150 produced in the acidification region 330 of the electrochemical acidification cell 302 to produce a third product 337 .
- the third product may include glyoxylic acid, glycolic acid, glyoxal, glycolaldehyde, acetic acid, acetaldehyde, ethanol, ethane, ethylene, or ethylene glycol.
- FIG. 4 A further embodiment of a system in accordance with the present disclosure is provided in FIG. 4 which includes a first electrochemical cell 102 , second reactor 108 , third reactor 152 , a second electrochemical cell 402 , and a thermal hydrogenation chamber 334 .
- the system 400 may be used to form an alkene, alkyne, aldehyde, ketone, or an alcohol (second product 406 ) while simultaneously producing at least one of glyoxylic acid, glycolic acid, glyoxal, glycolaldehyde, acetic acid, acetaldehyde, ethanol, ethane, ethylene, or ethylene glycol (third product 404 ).
- first electrochemical cell 102 is generally operational to reduce carbon dioxide in the first region 116 to M-carboxylate 130 recoverable from the first region 116 , while oxidizing MX 128 in the second region 118 to produce a halogen 132 recoverable from the second region 118 .
- the halogen 132 may be extracted from the second region 118 and input to a second reactor.
- the second reactor 108 may react the halogen 132 with an alkane, alkene, aromatic, or other aromatic compound 140 to produce a halogenated compound 144 and HX 148 .
- HX 148 may then be recycled to an acidification chamber 134 as an input feed to the acidification chamber 134 .
- the halogenated compound 144 may be fed to third reactor 152 .
- Third reactor 152 may receive a caustic compound 304 recycled from the second two compartment electrochemical cell 402 .
- the caustic compound 304 reacts with the halogenated compound 144 in the third reactor to produce a second product 406 as well as MX 128 .
- the MX 128 may be recycled as an input feed to a second region 418 of the second electrochemical cell 402 .
- the second product 406 may be an alcohol. If the reaction occurs in the presence of a non-aqueous solvent, such as an alcohol, the second product 406 may be an alkene or alkyne. In one embodiment, the second product 406 is ethanol. In another embodiment, the second product 406 is ethylene. In another embodiment, the second product is phenol derived from benzene. In yet another embodiment, the second product is isopropanol derived from propane or propylene.
- the MX 128 produced in the third reactor 152 may be recycled as an input feed to a second region 418 of the second electrochemical cell 402 .
- the second electrochemical cell 402 may include a first region 416 and a second region 418 .
- First region 416 may include a cathode 422 .
- Second region 418 may include an anode 424 .
- First region 416 may include a catholyte comprising water.
- Second region 318 may include an anolyte which may include MX 128 , which is provided from the third reactor 152 and recycled to the anolyte.
- An energy source 414 may generate an electrical potential between the anode 424 and the cathode 422 .
- a separator 420 may control the flow of ions between the first region 416 and the second region 418 .
- the second electrochemical cell 402 may receive an input of the MX 128 produced in the third reactor 152 as an input feed to the second region 418 of the second electrochemical cell 402 where it is oxidized to produce halogen 132 , liberating M cations to be transported through separator 420 to the first region 416 .
- Halogen 132 is then removed from the second region 418 and recycled as an input to the second reactor 108 .
- An additional input to the second electrochemical cell 402 may include water 405 which is fed to the first region 416 .
- the water 405 is reduced to H 2 and OH— at cathode 422 .
- the OH ⁇ hydroxide ions react with M cations provided by the reaction at the second region 418 to form the caustic compound 304 .
- the caustic compound 304 is then removed from the first region 416 and may be recycled as an input to the third reactor 152 .
- H 2 336 may also be produced in the first region, which may be recycled as an input feed to thermal hydrogenation chamber 334 .
- Hydrogen for the thermal hydrogenation chamber 334 may be supplied from other sources as well.
- the cathode side of the reaction in the first electrochemical cell 102 consists of the reduction of carbon dioxide provided by carbon dioxide source 106 along with ions from the reaction on the anode side to form M-carboxylate 130 .
- the M-carboxylate 130 may be removed from the first region 116 and input into acidification chamber 134 .
- the acidification chamber 134 reacts the HX 148 provided by the second reactor 108 with the M-carboxylate 130 to produce the carboxylic acid 150 (first product) and MX 128 .
- the MX 128 is recycled as an input to the second region.
- the carboxylic acid 150 is then fed to thermal hydrogenation chamber 334 .
- the first product, carboxylic acid 150 from the acidification chamber 134 is then fed to thermal hydrogenation chamber 334 where it reacts with H 2 336 provided by the first region 416 of the second electrochemical cell 402 to produce the third product 404 .
- Additional H 2 may be provided from another source.
- a receiving feed may include various mechanisms for receiving a supply of a product, whether in a continuous, near continuous or batch portions.
- the structure and operation of the electrochemical cells 102 and 402 as well as the electrochemical acidification cell 302 may be adjusted to provide desired results.
- the electrochemical cells may operate at higher pressures, such as pressure above atmospheric pressure which may increase current efficiency and allow operation of the electrochemical cell at higher current densities.
- the cathode 122 and anode 124 may include a high surface area electrode structures with a void volume which may range from 30% to 98%.
- the electrode void volume percentage may refer to the percentage of empty space that the electrode is not occupying in the total volume space of the electrode.
- the advantage in using a high void volume electrode is that the structure has a lower pressure drop for liquid flow through the structure.
- the specific surface area of the electrode base structure may be from 2 cm 2 /cm 3 to 500 cm 2 /cm 3 or higher.
- the electrode specific surface area is a ratio of the base electrode structure surface area divided by the total physical volume of the entire electrode.
- surface areas also may be defined as a total area of the electrode base substrate in comparison to the projected geometric area of the current distributor/conductor back plate, with a preferred range of 2 ⁇ to 1000 ⁇ or more.
- the actual total active surface area of the electrode structure is a function of the properties of the electrode catalyst deposited on the physical electrode structure which may be 2 to 1000 times higher in surface area than the physical electrode base structure.
- Cathode 122 may be selected from a number of high surface area materials to include copper, stainless steels, transition metals and their alloys and oxides, carbon, and silicon, which may be further coated with a layer of material which may be a conductive metal or semiconductor.
- the base structure of cathode 122 may be in the form of fibrous, reticulated, or sintered powder materials made from metals, carbon, or other conductive materials including polymers.
- the materials may be a very thin plastic screen incorporated against the cathode side of the membrane to prevent the membrane 120 from directly touching the high surface area cathode structure.
- the high surface area cathode structure may be mechanically pressed against a cathode current distributor backplate, which may be composed of material that has the same surface composition as the high surface area cathode.
- cathode 122 may be a suitable conductive electrode, such as Al, Au, Ag, Bi, C, Cd, Co, Cr, Cu, Cu alloys (e.g., brass and bronze), Ga, Hg, In, Mo, Nb, Ni, NiCo 2 O 4 , Ni alloys (e.g., Ni 625, NiHX), Ni—Fe alloys, Pb, Pd alloys (e.g., PdAg), Pt, Pt alloys (e.g., PtRh), Rh, Sn, Sn alloys (e.g., SnAg, SnPb, SnSb), Ti, V, W, Zn, stainless steel (SS) (e.g., SS 2205, SS 304, SS 316, SS 321), austenitic steel, ferritic steel, duplex steel, martensitic steel, Nichrome (e.g., NiCr 60:16 (with Fe)), elgiloy (e.
- cathode 122 may be a p-type semiconductor electrode, such as p-GaAs, p-GaP, p-InN, p-InP, p-CdTe, p-GaInP 2 and p-Si, or an n-type semiconductor, such as n-GaAs, n-GaP, n-InN, n-InP, n-CdTe, n-GaInP 2 and n-Si.
- p-type semiconductor electrode such as p-GaAs, p-GaP, p-InN, p-InP, p-CdTe, n-GaInP 2 and n-Si.
- Other semiconductor electrodes may be implemented to meet the criteria of a particular application including, but not limited to, CoS, MoS 2 , TiB, WS 2 , SnS, Ag 2 S, CoP 2 , Fe 3 P, Mn 3 P 2 , MoP, Ni 2 Si, MoSi 2 , WSi2, CoSi 2 , Ti 4 O 7 , SnO 2 , GaAs, GaSb, Ge, and CdSe.
- Catholyte may include a pH range from 1 to 12 when aqueous solvents are employed, preferably from pH 4 to pH 10.
- the selected operating pH may be a function of any catalysts utilized in operation of the electrochemical cell 102 .
- catholyte and catalysts may be selected to prevent corrosion at the electrochemical cell 102 .
- Catholyte may include homogeneous catalysts. Homogeneous catalysts are defined as aromatic heterocyclic amines and may include, but are not limited to, unsubstituted and substituted pyridines and imidazoles. Substituted pyridines and imidazoles may include, but are not limited to mono and disubstituted pyridines and imidazoles.
- suitable catalysts may include straight chain or branched chain lower alkyl (e.g., C 1 -C 10 ) mono and disubstituted compounds such as 2-methylpyridine, 4-tertbutyl pyridine, 2,6 dimethylpyridine (2,6-lutidine); bipyridines, such as 4,4′-bipyridine; amino-substituted pyridines, such as 4-dimethylamino pyridine; and hydroxyl-substituted pyridines (e.g., 4-hydroxy-pyridine) and substituted or unsubstituted quinoline or isoquinolines.
- straight chain or branched chain lower alkyl e.g., C 1 -C 10
- mono and disubstituted compounds such as 2-methylpyridine, 4-tertbutyl pyridine, 2,6 dimethylpyridine (2,6-lutidine
- bipyridines such as 4,4′-bipyridine
- amino-substituted pyridines such as 4-
- the catalysts may also suitably include substituted or unsubstituted dinitrogen heterocyclic amines, such as pyrazine, pyridazine and pyrimidine.
- Other catalysts generally include azoles, imidazoles, indoles, oxazoles, thiazoles, substituted species and complex multi-ring amines such as adenine, pterin, pteridine, benzimidazole, phenonthroline and the like.
- the catholyte may include an electrolyte.
- Catholyte electrolytes may include alkali metal bicarbonates, carbonates, sulfates, phosphates, borates, and hydroxides.
- the electrolyte may comprise one or more of Na 2 SO 4 , KCl, NaNO 3 , NaCl, NaF, NaClO 4 , KClO 4 , K 2 SiO 3 , CaCl 2 , a guanidinium cation, an H cation, an alkali metal cation, an ammonium cation, an alkylammonium cation, a tetraalkyl ammonium cation, a halide anion, an alkyl amine, a borate, a carbonate, a guanidinium derivative, a nitrite, a nitrate, a phosphate, a polyphosphate, a perchlorate, a silicate, a
- the catholyte may further include an aqueous or non-aqueous solvent.
- An aqueous solvent may include greater than 5% water.
- a non-aqueous solvent may include as much as 5% water.
- a solvent may contain one or more of water, a protic solvent, or an aprotic polar solvent.
- Representative solvents include methanol, ethanol, acetonitrile, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, dimethylsulfoxide, dimethylformamide, acetonitrile, acetone, tetrahydrofuran, N,N-dimethylacetamide, dimethoxyethane, diethylene glycol dimethyl ester, butyrolnitrile, 1,2-difluorobenzene, y-butyrolactone, N-methyl-2-pyrrolidone, sulfolane, 1,4-dioxane, nitrobenzene, nitromethane, acetic anhydride, ionic liquids, and mixtures thereof.
- a catholyte/anolyte flow rate may include a catholyte/anolyte cross sectional area flow rate range such as 2-3,000 gpm/ft 2 or more (0.0076-11.36 m 3 /m 2 ).
- a flow velocity range may be 0.002 to 20 ft/sec (0.0006 to 6.1 m/sec). Operation of the electrochemical cell catholyte at a higher operating pressure allows more dissolved carbon dioxide to dissolve in the aqueous solution.
- electrochemical cells can operate at pressures up to about 20 to 30 psig in multi-cell stack designs, although with modifications, the electrochemical cells may operate at up to 100 psig.
- the electrochemical cell may operate anolyte at the same pressure range to minimize the pressure differential on a separator 120 or membrane separating the two regions.
- Special electrochemical designs may be employed to operate electrochemical units at higher operating pressures up to about 60 to 100 atmospheres or greater, which is in the liquid CO 2 and supercritical CO 2 operating range.
- a portion of a catholyte recycle stream may be separately pressurized using a flow restriction with back pressure or using a pump, with CO 2 injection, such that the pressurized stream is then injected into the catholyte region of the electrochemical cell which may increase the amount of dissolved CO 2 in the aqueous solution to improve the conversion yield.
- micro-bubble generation of carbon dioxide can be conducted by various means in the catholyte recycle stream to maximize carbon dioxide solubility in the solution.
- Catholyte may be operated at a temperature range of ⁇ 10 to 95° C., more preferably 5-60° C.
- the lower temperature will be limited by the catholytes used and their freezing points. In general, the lower the temperature, the higher the solubility of CO 2 in an aqueous solution phase of the catholyte, which would help in obtaining higher conversion and current efficiencies.
- the drawback is that the operating electrochemical cell voltages may be higher, so there is an optimization that would be done to produce the chemicals at the lowest operating cost.
- the catholyte may require cooling, so an external heat exchanger may be employed, flowing a portion, or all, of the catholyte through the heat exchanger and using cooling water to remove the heat and control the catholyte temperature.
- Anolyte operating temperatures may be in the same ranges as the ranges for the catholyte, and may be in a range of 0° C. to 95° C.
- the anolyte may require cooling, so an external heat exchanger may be employed, flowing a portion, or all, of the anolyte through the heat exchanger and using cooling water to remove the heat and control the anolyte temperature.
- Electrochemical cells may include various types of designs. These designs may include zero gap designs with a finite or zero gap between the electrodes and membrane, flow-by and flow-through designs with a recirculating catholyte electrolyte utilizing various high surface area cathode materials.
- the electrochemical cell may include flooded co-current and counter-current packed and trickle bed designs with the various high surface area cathode materials.
- bipolar stack cell designs and high pressure cell designs may also be employed for the electrochemical cells.
- Anode electrodes may be the same as cathode electrodes or different.
- Anodes 124 , 324 , and 424 may include electrocatalytic coatings applied to the surfaces of the base anode structure.
- Anolytes may be the same as catholytes or different.
- Anolyte electrolytes may be the same as catholyte electrolytes or different.
- Anolyte may comprise solvent.
- Anolyte solvent may be the same as catholyte solvent or different.
- the preferred electrocatalytic coatings may include precious metal oxides such as ruthenium and iridium oxides, as well as platinum and gold and their combinations as metals and oxides on valve metal substrates such as titanium, tantalum, zirconium, or niobium.
- precious metal oxides such as ruthenium and iridium oxides, as well as platinum and gold and their combinations as metals and oxides on valve metal substrates such as titanium, tantalum, zirconium, or niobium.
- platinum and gold and their combinations as metals and oxides on valve metal substrates such as titanium, tantalum, zirconium, or niobium.
- carbon and graphite are particularly suitable for use as anodes.
- Polymeric bonded carbon material may also be used.
- anodes may include carbon, cobalt oxides, stainless steels, transition metals, and their alloys and combinations.
- High surface area anode structures that may be used which would help promote the reactions at the anode surfaces.
- the high surface area anode base material may be in a reticulated form composed of fibers, sintered powder, sintered screens, and the like, and may be sintered, welded, or mechanically connected to a current distributor back plate that is commonly used in bipolar electrochemical cell assemblies.
- the high surface area reticulated anode structure may also contain areas where additional applied catalysts on and near the electrocatalytic active surfaces of the anode surface structure to enhance and promote reactions that may occur in the bulk solution away from the anode surface such as the reaction between bromine and the carbon based reactant being introduced into the anolyte.
- the anode structure may be gradated, so that the density of the may vary in the vertical or horizontal direction to allow the easier escape of gases from the anode structure.
- this gradation there may be a distribution of particles of materials mixed in the anode structure that may contain catalysts, such as metal halide or metal oxide catalysts such as iron halides, zinc halides, aluminum halides, cobalt halides, for the reactions between the bromine and the carbon-based reactant.
- catalysts such as metal halide or metal oxide catalysts such as iron halides, zinc halides, aluminum halides, cobalt halides, for the reactions between the bromine and the carbon-based reactant.
- anodes may include carbon, cobalt oxides, stainless steels, and their alloys and combinations.
- Separator also referred to as a membrane, between a first region and second region, may include cation ion exchange type membranes.
- Cation ion exchange membranes which have high rejection efficiency to anions may be preferred.
- Examples of such cation ion exchange membranes may include perfluorinated sulfonic acid based ion exchange membranes such as DuPont Nafion® brand unreinforced types N117 and N120 series, more preferred PTFE fiber reinforced N324 and N424 types, and similar related membranes manufactured by Japanese companies under the supplier trade names such as AGC Engineering (Asahi Glass) under their trade name Flemion®.
- multi-layer perfluorinated ion exchange membranes used in the chlor alkali industry may have a bilayer construction of a sulfonic acid based membrane layer bonded to a carboxylic acid based membrane layer, which efficiently operates with an anolyte and catholyte above a pH of about 2 or higher. These membranes may have higher anion rejection efficiency. These are sold by DuPont under their Nafion® trademark as the N900 series, such as the N90209, N966, N982, and the 2000 series, such as the N2010, N2020, and N2030 and all of their types and subtypes.
- Hydrocarbon based membranes which are made from of various cation ion exchange materials can also be used if the anion rejection is not as desirable, such as those sold by Sybron under their trade name lonac®, AGC Engineering (Asahi Glass) under their Selemion® trade name, and Tokuyama Soda, among others on the market.
- Ceramic based membranes may also be employed, including those that are called under the general name of NASICON (for sodium super-ionic conductors) which are chemically stable over a wide pH range for various chemicals and selectively transports sodium ions, the composition is Na 1 +xZr 2 Si x P 3 -xO 12 , and well as other ceramic based conductive membranes based on titanium oxides, zirconium oxides and yttrium oxides, and beta aluminum oxides.
- Alternative membranes that may be used are those with different structural backbones such as polyphosphazene and sulfonated polyphosphazene membranes in addition to crown ether based membranes.
- the membrane or separator is chemically resistant to the anolyte and catholyte and operates at temperatures of less than 600 degrees C., and more preferably less than 500 degrees C.
- a rate of the generation of reactant formed in the anolyte compartment from the anode reaction is contemplated to be proportional to the applied current to the electrochemical cell.
- the anolyte product output in this range can be such that the output stream contains little or no free bromine in the product output, or it may contain unreacted bromine.
- the operation of the extractor and its selected separation method, for example fractional distillation, the actual products produced, and the selectivity may be adjusted to obtain desired characteristics. Any of the unreacted components would be recycled to the second region.
- a rate of the generation of the formed electrochemical carbon dioxide reduction product is contemplated to be proportional to the applied current to the electrochemical cell.
- the rate of the input or feed of the carbon dioxide source 106 should be fed in a proportion to the applied current.
- the cathode reaction efficiency would determine the maximum theoretical formation in moles of the carbon dioxide reduction product. It is contemplated that the ratio of carbon dioxide feed to the theoretical moles of potentially formed carbon dioxide reduction product would be in a range of 100:1 to 2:1, and preferably in the range of 50:1 to 5:1, where the carbon dioxide is in excess of the theoretical required for the cathode reaction. The carbon dioxide excess would then be separated and recycled back to the first region 116 .
- the methods disclosed may be implemented as sets of instructions or software readable by a device. Further, it is understood that the specific order or hierarchy of steps in the methods disclosed are examples of exemplary approaches. Based upon design preferences, it is understood that the specific order or hierarchy of steps in the method can be rearranged while remaining within the disclosed subject matter.
- the accompanying method claims present elements of the various steps in a sample order, and are not necessarily meant to be limited to the specific order or hierarchy presented.
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Abstract
The present disclosure includes a system and method for co-producing a first product and a second product. The system may include a first electrochemical cell, at least one second reactor, and an acidification chamber. The method and system for co-producing a first product and a second product may include co-producing a carboxylic acid and at least one of an alkene, alkyne, aldehyde, ketone, or an alcohol while employing a recycled halide salt.
Description
- The present application claims the benefit under 35 U.S.C. §120 of U.S. patent application Ser. No. 13/724,807 filed Dec. 21, 2012. The U.S. patent application Ser. No. 13/724,807 filed Dec. 21, 2012 is incorporated by reference in its entirety.
- The U.S. patent application Ser. No. 13/724,807 filed Dec. 21, 2012 claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Application Ser. No. 61/720,670 filed Oct. 31, 2012, U.S. Provisional Application Ser. No. 61/703,231 filed Sep. 19, 2012 and U.S. Provisional Application Ser. No. 61/675,938 filed Jul. 26, 2012. Said U.S. Provisional Application Ser. No. 61/720,670 filed Oct. 31, 2012, U.S. Provisional Application Ser. No. 61/703,231 filed Sep. 19, 2012 and U.S. Provisional Application Ser. No. 61/675,938 filed Jul. 26, 2012 are incorporated by reference in their entireties.
- The U.S. patent application Ser. No. 13/724,807 filed Dec. 21, 2012 also claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Application Ser. No. 61/703,229 filed Sep. 19, 2012, U.S. Provisional Application Ser. No. 61/703,158 filed Sep. 19, 2012, U.S. Provisional Application Ser. No. 61/703,175 filed Sep. 19, 2012, U.S. Provisional Application Ser. No. 61/703,232 filed Sep. 19, 2012, U.S. Provisional Application Ser. No. 61/703,234 filed Sep. 19, 2012, U.S. Provisional Application Ser. No. 61/703,238 filed Sep. 19, 2012, U.S. Provisional Application Ser. No. 61/703,187 filed Sep. 19, 2012. The U.S. Provisional Application Ser. No. 61/703,229 filed Sep. 19, 2012, U.S. Provisional Application Ser. No. 61/703,158 filed Sep. 19, 2012, U.S. Provisional Application Ser. No. 61/703,175 filed Sep. 19, 2012, U.S. Provisional Application Ser. No. 61/703,232 filed Sep. 19, 2012, U.S. Provisional Application Ser. No. 61/703,234 filed Sep. 19, 2012, U.S. Provisional Application Ser. No. 61/703,238 filed Sep. 19, 2012 and U.S. Provisional Application Ser. No. 61/703,187 filed Sep. 19, 2012 are hereby incorporated by reference in their entireties.
- The present application incorporates by reference co-pending U.S. Patent application Ser. No. 13/724,339 filed Dec. 21, 2012, U.S. Patent application Ser. No. 13/724,878 filed Dec. 21, 2012, U.S. Patent application Ser. No. 13/724,647 filed Dec. 21, 2012, U.S. Patent application Ser. No. 13/724,231 filed Dec. 21, 2012, U.S. Patent application Ser. No. 13/724,996 filed Dec. 21, 2012, U.S. Patent application Ser. No. 13/724,719 filed Dec. 21, 2012, U.S. Patent application Ser. No. 13/724,082 filed Dec. 21, 2012 and U.S. Patent application Ser. No. 13/724,768 filed Dec. 21, 2012 now U.S. Pat. No. 8,444,844 in their entireties.
- The present disclosure generally relates to the field of electrochemical reactions, and more particularly to methods and/or systems for electrochemical co-production of a carboxylic acid employing a recycled reactant.
- Noon The combustion of fossil fuels in activities such as electricity generation, transportation, and manufacturing produces billions of tons of carbon dioxide annually. Research since the 1970s indicates increasing concentrations of carbon dioxide in the atmosphere may be responsible for altering the Earth's climate, changing the pH of the ocean and other potentially damaging effects. Countries around the world, including the United States, are seeking ways to mitigate emissions of carbon dioxide.
- A mechanism for mitigating emissions is to convert carbon dioxide into economically valuable materials such as fuels and industrial chemicals. If the carbon dioxide is converted using energy from renewable sources, both mitigation of carbon dioxide emissions and conversion of renewable energy into a chemical form that can be stored for later use will be possible.
- The present disclosure includes a system and method for co-producing a first product and a second product. The system may include a first electrochemical cell, at least one second reactor, and an acidification chamber. The method and system for co-producing a first product and a second product may include co-producing a carboxylic acid and at least one of an alkene, alkyne, aldehyde, ketone, or an alcohol while employing a recycled halide salt.
- It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not necessarily restrictive of the present disclosure. The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate subject matter of the disclosure. Together, the descriptions and the drawings serve to explain the principles of the disclosure.
- The numerous advantages of the disclosure may be better understood by those skilled in the art by reference to the accompanying figures in which:
-
FIG. 1A is a block diagram of a system in accordance with an embodiment of the present disclosure; -
FIG. 1B is a block diagram of a system in accordance with an embodiment of the present disclosure; -
FIG. 2A is a block diagram of a system in accordance with another embodiment of the present disclosure; -
FIG. 2B is a block diagram of a system in accordance with an embodiment of the present disclosure; -
FIG. 3A is a block diagram of a system in accordance with an additional embodiment of the present disclosure; -
FIG. 3B is a block diagram of a system in accordance with an embodiment of the present disclosure; and -
FIG. 4 is a block diagram of a system in accordance with another additional embodiment of the present disclosure. - Reference will now be made in detail to the subject matter disclosed, which is illustrated in the accompanying drawings.
- The systems and methods of the present disclosure may include an electrochemical cell that includes an input of a recycled reactant to co-produce valuable products at both the cathode and anode sides of the electrochemical cell. In one embodiment, carbon dioxide may be reduced in a catholyte region of the electrochemical cell to a carboxylate, and a halide salt is oxidized in an anode region of the electrochemical cell to a halogen. The carboxylate may be fed into an acidification chamber along with a hydrogen halide to form a carboxylic acid and the halide salt. The halide salt is then recycled to the anode region of the electrochemical cell. The halogen produced in the anode compartment is subsequently fed to a second reactor along with an alkane, alkene, aromatic, or other organic compound to produce a halogenated compound and a hydrogen halide. The halogenated compound may be further treated in a third reactor to produce an alkene, alkyne, aldehyde, ketone, or an alcohol. The third reactor also produces additional hydrogen halide, which may be fed to the acidification chamber. In one embodiment, the method and system of the present disclosure may use a source of carbon dioxide, an alkane, alkene, aromatic or other organic compound in order to efficiently produce an alkene, alkyne, aldehyde, ketone, or an alcohol and a carboxylic acid with the recycling of halide salt. The organic chemical partially oxidized in the process may serve as the source of hydrogen for the reduction of carbon dioxide and acidification of the resulting carboxylic acid. The organic may thereby be indirectly oxidized by carbon dioxide while the carbon dioxide is reduced by the organic such that two or more products are made simultaneously. Advantageously, the halogen employed to partially oxidize an organic and provide hydrogen to the reduction of carbon dioxide or acidification of M-Carboxylate may be recycled.
- Referring to
FIG. 1A , a block diagram of asystem 100 in accordance with an embodiment of the present disclosure is shown. System (or apparatus) 100 generally includes anelectrochemical cell 102.Electrochemical cell 102 may also be referred as a container, electrolyzer, or cell.Electrochemical cell 102 may be implemented as a divided cell. The divided cell may be a divided electrochemical cell and/or a divided photo-electrochemical cell.Electrochemical cell 102 may include afirst region 116 and asecond region 118.First region 116 andsecond region 118 may refer to a compartment, section, or generally enclosed space and the like without departing from the scope and intent of the present disclosure.First region 116 may include acathode 122.Second region 118 may include ananode 124.First region 116 may include a catholyte whereby carbon dioxide fromcarbon dioxide source 106 is included in the catholyte.Second region 118 may include an anolyte which may include anMX 128 where M is at least one cation and X is selected from a group consisting of F, Cl, Br, I and mixtures thereof. Anenergy source 114 may generate an electrical potential between theanode 124 and thecathode 122. The electrical potential may be a DC voltage.Energy source 114 may be configured to supply a variable voltage or constant current toelectrochemical cell 102.Separator 120 may selectively control a flow of ions between thefirst region 116 and thesecond region 118.Separator 120 may include an ion conducting membrane or diaphragm material. -
Electrochemical cell 102 is generally operational to reduce carbon dioxide in thefirst region 116 to an M-carboxylate 130 recoverable from thefirst region 116, while producing ahalogen 132 recoverable from thesecond region 118. -
Carbon dioxide source 106 may provide carbon dioxide to thefirst region 116 ofelectrochemical cell 102. In some embodiments, the carbon dioxide is introduced directly into theregion 116 containing thecathode 122. It is contemplated thatcarbon dioxide source 106 may include a source of multiple gases in which carbon dioxide has been filtered from the multiple gases. - It is contemplated that the
electrochemical cell 102 may include a first product extractor (not shown) and second product extractor (not shown). Product extractors may implement an organic product and/or inorganic product extractor. The first product extractor (not shown) is generally operational to extract (separate) a product from thefirst region 116. The second product extractor (not shown) may extract the second product from thesecond region 118. It is contemplated that the first product extractor and/or second product extractor may be implemented withelectrochemical cell 102, or may be remotely located from theelectrochemical cell 102. Additionally, it is contemplated that first product extractor and/or second product extractor may be implemented in a variety of mechanisms and to provide desired separation methods, such as fractional distillation, without departing from the scope and intent of the present disclosure. It is further contemplated that extracted product may be presented through a port of thesystem 100 for subsequent storage and/or consumption by other devices and/or processes. - An anode side of the reaction occurring in the
second region 118 of theelectrochemical cell 102 may include an input of a recycled reactant ofMX 128. TheMX 128 may include a halide salt which may be a byproduct of a reaction ofacidification chamber 134. For example, theMX 128 may include a halide salt where M is a cation including at least one of Li, Na, K, Cs, Mg, Ca, hydrogen ions, tetraalkyl ammonium ions such as tetrabutylammonium, tetraethylammonium, choline, and tetraalkylphosphonium ions such as tetrabutylphosphonium, tetraethylphosphonium, and in general, R1R2R3R4N or R1R2R3R4P where R1 to R4 are independently alkyl, cycloalkyl, branched alkyl, and aryl, and X is selected from a group consisting of F, Cl, Br, I and mixtures thereof. The anode side of the reaction may produce ahalogen 132 which may be presented tosecond reactor 108. -
System 100 may includesecond reactor 108 which may receivehalogen 132 produced by thesecond region 118 of theelectrochemical cell 102 after separation from the second region via a second product extractor.Second reactor 108 may reacthalogen 132 with an alkane, alkene, aromatic, orother compound 140 to produce a halogenated product or halogenatedintermediate compound 144 andHX 148. TheHX 148 produced in the reaction may be another recycled reactant which may be recycled to theacidification chamber 134 as an input feed to theacidification chamber 134. Examples of halogenated products include monohalogenated, polyhalogenated, and perhalogenated compounds to include chloroform, hydrofluorocarbons, bromoalkanes, vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene fluoride, tetrafluorethane, bromobenzene, dibromobenzene, bromoethane, dichloroethane, allyl chloride, chlorophenol, fluorosurfactants, tetrafluoroethylene, hexafluoropropylene, difluoromethane, or pentafluoroethane. - The
acidification chamber 134 ofsystem 100 reacts theHX 148 with the M-carboxylate 130 to producecarboxylic acid 150 andMX 128, which is recycled as an input to thesecond region 118. Thecarboxylic acid 150 may be further reacted in an additional reactor with H2 to produce at least one of a more reduced compound. Thecarboxylic acid 150 may also be reacted with an alcohol to make an ester or diester or be used in other chemical processes. The M-carboxylate 130 may include M-oxalate, M-formate, M-glyoxylate, M-glycolate, or M-acetate in one embodiment. - In one embodiment shown in
FIG. 1B , thesystem 100 includes an additional reactor, shown asthird reactor 152.Halogenated compound 144 may be fed tothird reactor 152. In one embodiment, thethird reactor 152 is a dehydrohalogenation reactor.Third reactor 152 may perform a dehydrohalogenation reaction of thehalogenated compound 144 under specific conditions to produce asecond product 156 of an alkene or alkyne. Examples of products derived from the partial oxidation via halogenation and dehalogenation in the second and third reactors are in Table 1 below. -
TABLE 1 Organic Feed Oxidation Product(s) Methane Methanol, formaldehyde, formic acid, ethylene, longer chain compounds such as ethane Ethane Ethanol, acetaldehyde, acetic acid, ethylene glycol, ethylene, acetylene, longer chain compounds such as butane Ethene (Ethylene) Acetylene Propane Propanol, isopropanol, propanone, acetone, propanoic acid, lactic acid, propylene glycol, propylene Butane Butanol, butane, butadiene Isobutane Isobutanol, isobutylene Benzene Phenol Toluene Benzyl alcohol, benzyl aldehyde, benzoic acid Xylene Terephthalic acid, isophthalic acid, phthalic acid Ethyl benzene Styrene - An example implementation of the
system 100 shown inFIGS. 1A and 1B is shown inFIG. 2A . Asystem 200 for generatingethylene 204 andoxalic acid 206 from a recycled reactant of tetrabutylammonium bromide (TBA-bromide) 208 andcarbon dioxide 106 is provided. Recycled reactant comprised of tetrabutylammonium bromide (TBA-bromide) 208 is fed into thesecond region 118 ofelectrochemical cell 102, formingbromine 210. Thebromine 210 is extracted from thesecond region 118 and fed intosecond reactor 108 where it reacts withethane 212 to formbromoethane 214 andhydrogen bromide 216. Any byproducts of the halogenation, such as 1,1 dibromoethane or 1,2 dibromoethane, may be separated and sold as a separate product, hydrogenated back to ethane for recycle, or catalytically converted to bromoethane. Thehydrogen bromide 216 is recycled toacidification chamber 134. Thebromoethane 214 is fed into thethird reactor 152, which may be a dehydrohalogenation reactor. Thebromoethane 214 is dehydrohalogenated to formethylene 204. - The
cathode 122 side of the reaction of the embodiment shown inFIG. 2A includes the reduction of carbon dioxide in the presence of tetrabutylammonium cations from the reaction in thesecond region 118, to formtetrabutylammonium oxalate 218. Thetetrabutylammonium oxalate 218 is fed into theacidification chamber 134 where it reacts with therecycled hydrogen bromide 216 to produceoxalic acid 206 andtetrabutylammonium bromide 208. Thetetrabutylammonium bromide 208 is recycled to thesecond region 118. Theoxalic acid 206 may be further reacted in a thermal hydrogenation chamber with H2 to form a more reduced carbon product, such as glyoxylic acid, glycolic acid, glyoxal, glycolaldeyde, ethlylene glycol, ethanol, acetic acid, actaldehyde, ethane, or ethylene. - In another embodiment shown in
FIG. 2B ,water 220 may be fed into thethird reactor 152 along with thebromoethane 214 to produceethanol 222 andhydrogen bromide 216. - A further embodiment of a system in accordance with the present disclosure is provided in
FIGS. 3A and 3B which includeselectrochemical cell 102,second reactor 108,third reactor 152, and anelectrochemical acidification cell 302. Thesystem 300 may be used to form an alkane, alkene, alkyne, aldehyde, ketone, or an alcohol while simultaneously producing a carboxylic acid. - As shown in
FIGS. 3A and 3B ,electrochemical cell 102 is generally operational to reduce carbon dioxide in thefirst region 116 to M-carboxylate 130 while oxidizingMX 128 in thesecond region 118 to produce ahalogen 132 recoverable from thesecond region 118. Specifically, an anode side of the reaction occurring in thesecond region 118 of theelectrochemical cell 102 may include receiving an input of recycled reactant,MX 128. The anode side of the reaction may produce ahalogen 132 which may be presented tosecond reactor 108. -
Second reactor 108 may reacthalogen 132 with an alkane, alkene, aromatic, or otherorganic compound 140 to produce ahalogenated compound 144 andHX 148.HX 148 may be another recycled reactant which may be recycled to theelectrochemical acidification cell 302 as an input feed to theelectrochemical acidification cell 302. Thehalogenated compound 144 may be fed tothird reactor 152.Third reactor 152 may receive acaustic compound 304 generated from theelectrochemical acidification cell 302. Thecaustic compound 304 may react with thehalogenated compound 144 in either an aqueous or non-aqueous based solvent, such as alcohol, 220 to produce asecond product 156 as well asMX 128. If the reaction occurs in the presence of an aqueous solvent, thesecond product 156 may be an alcohol. If the reaction occurs in the presence of a non-aqueous alcohol based solvent, thesecond product 156 may be an alkene or alkyne. TheMX 128 produced in thethird reactor 152 may be recycled to thesecond region 118 of theelectrochemical cell 102. - The
caustic compound 304 may include MOH in one embodiment, where M represents the cation used in the reaction. An example of MOH may include NaOH or KOH in one embodiment. Thecaustic compound 304 may include a caustic metallic base in one embodiment. - Meanwhile,
carbon dioxide source 106 may provide carbon dioxide to thefirst region 116 ofelectrochemical cell 102. In some embodiments, the carbon dioxide is introduced directly into theregion 116 containing thecathode 122. Carbon dioxide is reduced in thefirst region 116 and reacts with the ions from the anode reaction to produce M-carboxylate 130. The M-carboxylate 130 may be extracted from thefirst region 116 and fed into anelectrochemical acidification cell 302. -
Electrochemical acidification cell 302 may include afirst region 316 and asecond region 318.First region 316 andsecond region 318 may refer to a compartment, section, or generally enclosed space, and the like without departing from the scope and intent of the present disclosure.First region 316 may include acathode 322.Second region 318 may include ananode 324.First region 316 may include a catholyte comprising water.Second region 318 may include an anolyte which may includeHX 148, which is provided from thesecond reactor 108 and/or thethird reactor 152 and recycled to the anolyte. Anenergy source 314 may generate an electrical potential between theanode 324 and thecathode 322. Electrochemical acidification cell may also include anacidification region 330. Afirst separator 332 and asecond separator 333 may selectively control a flow of ions between thefirst region 316,acidification region 330, and thesecond region 318. Thefirst separator 332 and thesecond separator 333 may include an ion conducting membrane or diaphragm material. - The
electrochemical acidification cell 302 may receive three different inputs. First, M-carboxylate 130 produced by thefirst region 116 of theelectrochemical cell 102 may be fed into theacidification region 330 of theelectrochemical acidification cell 302 where it is acidified to form the first product,carboxylic acid 150, liberating M cations which are transported to thefirst region 316. Second,HX 148 may be recycled from the thesecond reactor 108 to thesecond region 318 ofelectrochemical acidification cell 302 to form more of the halogen, liberating W cations, or protons, for transport into theacidification region 330. The protons displace or replace the M cations of the M-carboxalate in theacidification region 330, which then pass throughmembrane 332 intoregion 316 of the catholyte. Thehalogen 316 produced in thesecond region 318 of theelectrochemical acidification cell 302 is then removed from thesecond region 318 and recycled as an input to thesecond reactor 108. A third input to theelectrochemical acidification cell 302 may include awater source 338 which is fed to thefirst region 316. Thewater 338 is reduced to H2 and OH− atcathode 322, and the OH— reacts with the M cations passing from the acidification region throughmembrane 332 to form thecaustic compound 304. Thecaustic compound 304 is then removed from thefirst region 316 and may be recycled as an input to thethird reactor 152.H 2 336 may also be produced in the first region. - In one embodiment shown in
FIG. 3B , thesystem 300 may include an additional reactor including athermal hydrogenation chamber 334. Thethermal hydrogenation chamber 334 may react theH 2 336 produced in the first region of theelectrochemical acidification cell 302 as well as the first product,carboxylic acid 150 produced in theacidification region 330 of theelectrochemical acidification cell 302 to produce athird product 337. The third product may include glyoxylic acid, glycolic acid, glyoxal, glycolaldehyde, acetic acid, acetaldehyde, ethanol, ethane, ethylene, or ethylene glycol. - A further embodiment of a system in accordance with the present disclosure is provided in
FIG. 4 which includes a firstelectrochemical cell 102,second reactor 108,third reactor 152, a secondelectrochemical cell 402, and athermal hydrogenation chamber 334. Thesystem 400 may be used to form an alkene, alkyne, aldehyde, ketone, or an alcohol (second product 406) while simultaneously producing at least one of glyoxylic acid, glycolic acid, glyoxal, glycolaldehyde, acetic acid, acetaldehyde, ethanol, ethane, ethylene, or ethylene glycol (third product 404). - As shown in
FIG. 4 , firstelectrochemical cell 102 is generally operational to reduce carbon dioxide in thefirst region 116 to M-carboxylate 130 recoverable from thefirst region 116, while oxidizingMX 128 in thesecond region 118 to produce ahalogen 132 recoverable from thesecond region 118. Thehalogen 132 may be extracted from thesecond region 118 and input to a second reactor. - The
second reactor 108 may react thehalogen 132 with an alkane, alkene, aromatic, or otheraromatic compound 140 to produce ahalogenated compound 144 andHX 148.HX 148 may then be recycled to anacidification chamber 134 as an input feed to theacidification chamber 134. Thehalogenated compound 144 may be fed tothird reactor 152.Third reactor 152 may receive acaustic compound 304 recycled from the second two compartmentelectrochemical cell 402. Thecaustic compound 304 reacts with thehalogenated compound 144 in the third reactor to produce asecond product 406 as well asMX 128. TheMX 128 may be recycled as an input feed to asecond region 418 of the secondelectrochemical cell 402. - If the reaction of the
halogenated compound 144 and thecaustic compound 304 in thethird reactor 152 occurs in the presence of water, thesecond product 406 may be an alcohol. If the reaction occurs in the presence of a non-aqueous solvent, such as an alcohol, thesecond product 406 may be an alkene or alkyne. In one embodiment, thesecond product 406 is ethanol. In another embodiment, thesecond product 406 is ethylene. In another embodiment, the second product is phenol derived from benzene. In yet another embodiment, the second product is isopropanol derived from propane or propylene. - The
MX 128 produced in thethird reactor 152 may be recycled as an input feed to asecond region 418 of the secondelectrochemical cell 402. The secondelectrochemical cell 402 may include afirst region 416 and asecond region 418.First region 416 may include acathode 422.Second region 418 may include an anode 424.First region 416 may include a catholyte comprising water.Second region 318 may include an anolyte which may includeMX 128, which is provided from thethird reactor 152 and recycled to the anolyte. Anenergy source 414 may generate an electrical potential between the anode 424 and thecathode 422. Aseparator 420 may control the flow of ions between thefirst region 416 and thesecond region 418. - The second
electrochemical cell 402 may receive an input of theMX 128 produced in thethird reactor 152 as an input feed to thesecond region 418 of the secondelectrochemical cell 402 where it is oxidized to producehalogen 132, liberating M cations to be transported throughseparator 420 to thefirst region 416.Halogen 132 is then removed from thesecond region 418 and recycled as an input to thesecond reactor 108. An additional input to the secondelectrochemical cell 402 may includewater 405 which is fed to thefirst region 416. Thewater 405 is reduced to H2 and OH— atcathode 422. The OH− hydroxide ions react with M cations provided by the reaction at thesecond region 418 to form thecaustic compound 304. Thecaustic compound 304 is then removed from thefirst region 416 and may be recycled as an input to thethird reactor 152.H 2 336 may also be produced in the first region, which may be recycled as an input feed tothermal hydrogenation chamber 334. Hydrogen for thethermal hydrogenation chamber 334 may be supplied from other sources as well. - The cathode side of the reaction in the first
electrochemical cell 102 consists of the reduction of carbon dioxide provided bycarbon dioxide source 106 along with ions from the reaction on the anode side to form M-carboxylate 130. The M-carboxylate 130 may be removed from thefirst region 116 and input intoacidification chamber 134. Theacidification chamber 134 reacts theHX 148 provided by thesecond reactor 108 with the M-carboxylate 130 to produce the carboxylic acid 150 (first product) andMX 128. TheMX 128 is recycled as an input to the second region. Thecarboxylic acid 150 is then fed tothermal hydrogenation chamber 334. - The first product,
carboxylic acid 150 from theacidification chamber 134 is then fed tothermal hydrogenation chamber 334 where it reacts withH 2 336 provided by thefirst region 416 of the secondelectrochemical cell 402 to produce thethird product 404. Additional H2 may be provided from another source. - It is contemplated that a receiving feed may include various mechanisms for receiving a supply of a product, whether in a continuous, near continuous or batch portions.
- It is further contemplated that the structure and operation of the
electrochemical cells electrochemical acidification cell 302 and may be adjusted to provide desired results. For example, the electrochemical cells may operate at higher pressures, such as pressure above atmospheric pressure which may increase current efficiency and allow operation of the electrochemical cell at higher current densities. - Additionally, the
cathode 122 andanode 124 may include a high surface area electrode structures with a void volume which may range from 30% to 98%. The electrode void volume percentage may refer to the percentage of empty space that the electrode is not occupying in the total volume space of the electrode. The advantage in using a high void volume electrode is that the structure has a lower pressure drop for liquid flow through the structure. The specific surface area of the electrode base structure may be from 2 cm2/cm3 to 500 cm2/cm3 or higher. The electrode specific surface area is a ratio of the base electrode structure surface area divided by the total physical volume of the entire electrode. It is contemplated that surface areas also may be defined as a total area of the electrode base substrate in comparison to the projected geometric area of the current distributor/conductor back plate, with a preferred range of 2× to 1000× or more. The actual total active surface area of the electrode structure is a function of the properties of the electrode catalyst deposited on the physical electrode structure which may be 2 to 1000 times higher in surface area than the physical electrode base structure. -
Cathode 122 may be selected from a number of high surface area materials to include copper, stainless steels, transition metals and their alloys and oxides, carbon, and silicon, which may be further coated with a layer of material which may be a conductive metal or semiconductor. The base structure ofcathode 122 may be in the form of fibrous, reticulated, or sintered powder materials made from metals, carbon, or other conductive materials including polymers. The materials may be a very thin plastic screen incorporated against the cathode side of the membrane to prevent themembrane 120 from directly touching the high surface area cathode structure. The high surface area cathode structure may be mechanically pressed against a cathode current distributor backplate, which may be composed of material that has the same surface composition as the high surface area cathode. - In addition,
cathode 122 may be a suitable conductive electrode, such as Al, Au, Ag, Bi, C, Cd, Co, Cr, Cu, Cu alloys (e.g., brass and bronze), Ga, Hg, In, Mo, Nb, Ni, NiCo2O4, Ni alloys (e.g., Ni 625, NiHX), Ni—Fe alloys, Pb, Pd alloys (e.g., PdAg), Pt, Pt alloys (e.g., PtRh), Rh, Sn, Sn alloys (e.g., SnAg, SnPb, SnSb), Ti, V, W, Zn, stainless steel (SS) (e.g., SS 2205,SS 304,SS 316, SS 321), austenitic steel, ferritic steel, duplex steel, martensitic steel, Nichrome (e.g., NiCr 60:16 (with Fe)), elgiloy (e.g., Co—Ni—Cr), degenerately doped p-Si, degenerately doped p-Si:As, degenerately doped p-Si:B, degenerately doped n-Si, degenerately doped n-Si:As, and degenerately doped n-Si:B. These metals and their alloys may also be used as catalytic coatings on the various metal substrates. Other conductive electrodes may be implemented to meet the criteria of a particular application. For photo-electrochemical reductions,cathode 122 may be a p-type semiconductor electrode, such as p-GaAs, p-GaP, p-InN, p-InP, p-CdTe, p-GaInP2 and p-Si, or an n-type semiconductor, such as n-GaAs, n-GaP, n-InN, n-InP, n-CdTe, n-GaInP2 and n-Si. Other semiconductor electrodes may be implemented to meet the criteria of a particular application including, but not limited to, CoS, MoS2, TiB, WS2, SnS, Ag2S, CoP2, Fe3P, Mn3P2, MoP, Ni2Si, MoSi2, WSi2, CoSi2, Ti4O7, SnO2, GaAs, GaSb, Ge, and CdSe. - Catholyte may include a pH range from 1 to 12 when aqueous solvents are employed, preferably from pH 4 to pH 10. The selected operating pH may be a function of any catalysts utilized in operation of the
electrochemical cell 102. Preferably, catholyte and catalysts may be selected to prevent corrosion at theelectrochemical cell 102. Catholyte may include homogeneous catalysts. Homogeneous catalysts are defined as aromatic heterocyclic amines and may include, but are not limited to, unsubstituted and substituted pyridines and imidazoles. Substituted pyridines and imidazoles may include, but are not limited to mono and disubstituted pyridines and imidazoles. For example, suitable catalysts may include straight chain or branched chain lower alkyl (e.g., C1-C10) mono and disubstituted compounds such as 2-methylpyridine, 4-tertbutyl pyridine, 2,6 dimethylpyridine (2,6-lutidine); bipyridines, such as 4,4′-bipyridine; amino-substituted pyridines, such as 4-dimethylamino pyridine; and hydroxyl-substituted pyridines (e.g., 4-hydroxy-pyridine) and substituted or unsubstituted quinoline or isoquinolines. The catalysts may also suitably include substituted or unsubstituted dinitrogen heterocyclic amines, such as pyrazine, pyridazine and pyrimidine. Other catalysts generally include azoles, imidazoles, indoles, oxazoles, thiazoles, substituted species and complex multi-ring amines such as adenine, pterin, pteridine, benzimidazole, phenonthroline and the like. - The catholyte may include an electrolyte. Catholyte electrolytes may include alkali metal bicarbonates, carbonates, sulfates, phosphates, borates, and hydroxides. The electrolyte may comprise one or more of Na2SO4, KCl, NaNO3, NaCl, NaF, NaClO4, KClO4, K2SiO3, CaCl2, a guanidinium cation, an H cation, an alkali metal cation, an ammonium cation, an alkylammonium cation, a tetraalkyl ammonium cation, a halide anion, an alkyl amine, a borate, a carbonate, a guanidinium derivative, a nitrite, a nitrate, a phosphate, a polyphosphate, a perchlorate, a silicate, a sulfate, and a hydroxide. In one embodiment, bromide salts such as NaBr or KBr may be preferred.
- The catholyte may further include an aqueous or non-aqueous solvent. An aqueous solvent may include greater than 5% water. A non-aqueous solvent may include as much as 5% water. A solvent may contain one or more of water, a protic solvent, or an aprotic polar solvent. Representative solvents include methanol, ethanol, acetonitrile, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, dimethylsulfoxide, dimethylformamide, acetonitrile, acetone, tetrahydrofuran, N,N-dimethylacetamide, dimethoxyethane, diethylene glycol dimethyl ester, butyrolnitrile, 1,2-difluorobenzene, y-butyrolactone, N-methyl-2-pyrrolidone, sulfolane, 1,4-dioxane, nitrobenzene, nitromethane, acetic anhydride, ionic liquids, and mixtures thereof.
- In one embodiment, a catholyte/anolyte flow rate may include a catholyte/anolyte cross sectional area flow rate range such as 2-3,000 gpm/ft2 or more (0.0076-11.36 m3/m2). A flow velocity range may be 0.002 to 20 ft/sec (0.0006 to 6.1 m/sec). Operation of the electrochemical cell catholyte at a higher operating pressure allows more dissolved carbon dioxide to dissolve in the aqueous solution. Typically, electrochemical cells can operate at pressures up to about 20 to 30 psig in multi-cell stack designs, although with modifications, the electrochemical cells may operate at up to 100 psig. The electrochemical cell may operate anolyte at the same pressure range to minimize the pressure differential on a
separator 120 or membrane separating the two regions. Special electrochemical designs may be employed to operate electrochemical units at higher operating pressures up to about 60 to 100 atmospheres or greater, which is in the liquid CO2 and supercritical CO2 operating range. - In another embodiment, a portion of a catholyte recycle stream may be separately pressurized using a flow restriction with back pressure or using a pump, with CO2 injection, such that the pressurized stream is then injected into the catholyte region of the electrochemical cell which may increase the amount of dissolved CO2 in the aqueous solution to improve the conversion yield. In addition, micro-bubble generation of carbon dioxide can be conducted by various means in the catholyte recycle stream to maximize carbon dioxide solubility in the solution.
- Catholyte may be operated at a temperature range of −10 to 95° C., more preferably 5-60° C. The lower temperature will be limited by the catholytes used and their freezing points. In general, the lower the temperature, the higher the solubility of CO2 in an aqueous solution phase of the catholyte, which would help in obtaining higher conversion and current efficiencies. The drawback is that the operating electrochemical cell voltages may be higher, so there is an optimization that would be done to produce the chemicals at the lowest operating cost. In addition, the catholyte may require cooling, so an external heat exchanger may be employed, flowing a portion, or all, of the catholyte through the heat exchanger and using cooling water to remove the heat and control the catholyte temperature.
- Anolyte operating temperatures may be in the same ranges as the ranges for the catholyte, and may be in a range of 0° C. to 95° C. In addition, the anolyte may require cooling, so an external heat exchanger may be employed, flowing a portion, or all, of the anolyte through the heat exchanger and using cooling water to remove the heat and control the anolyte temperature.
- Electrochemical cells may include various types of designs. These designs may include zero gap designs with a finite or zero gap between the electrodes and membrane, flow-by and flow-through designs with a recirculating catholyte electrolyte utilizing various high surface area cathode materials. The electrochemical cell may include flooded co-current and counter-current packed and trickle bed designs with the various high surface area cathode materials. Also, bipolar stack cell designs and high pressure cell designs may also be employed for the electrochemical cells.
- Anode electrodes may be the same as cathode electrodes or different.
Anodes - Separator also referred to as a membrane, between a first region and second region, may include cation ion exchange type membranes. Cation ion exchange membranes which have high rejection efficiency to anions may be preferred. Examples of such cation ion exchange membranes may include perfluorinated sulfonic acid based ion exchange membranes such as DuPont Nafion® brand unreinforced types N117 and N120 series, more preferred PTFE fiber reinforced N324 and N424 types, and similar related membranes manufactured by Japanese companies under the supplier trade names such as AGC Engineering (Asahi Glass) under their trade name Flemion®. Other multi-layer perfluorinated ion exchange membranes used in the chlor alkali industry may have a bilayer construction of a sulfonic acid based membrane layer bonded to a carboxylic acid based membrane layer, which efficiently operates with an anolyte and catholyte above a pH of about 2 or higher. These membranes may have higher anion rejection efficiency. These are sold by DuPont under their Nafion® trademark as the N900 series, such as the N90209, N966, N982, and the 2000 series, such as the N2010, N2020, and N2030 and all of their types and subtypes. Hydrocarbon based membranes, which are made from of various cation ion exchange materials can also be used if the anion rejection is not as desirable, such as those sold by Sybron under their trade name lonac®, AGC Engineering (Asahi Glass) under their Selemion® trade name, and Tokuyama Soda, among others on the market. Ceramic based membranes may also be employed, including those that are called under the general name of NASICON (for sodium super-ionic conductors) which are chemically stable over a wide pH range for various chemicals and selectively transports sodium ions, the composition is Na1+xZr2SixP3-xO12, and well as other ceramic based conductive membranes based on titanium oxides, zirconium oxides and yttrium oxides, and beta aluminum oxides. Alternative membranes that may be used are those with different structural backbones such as polyphosphazene and sulfonated polyphosphazene membranes in addition to crown ether based membranes. Preferably, the membrane or separator is chemically resistant to the anolyte and catholyte and operates at temperatures of less than 600 degrees C., and more preferably less than 500 degrees C.
- A rate of the generation of reactant formed in the anolyte compartment from the anode reaction is contemplated to be proportional to the applied current to the electrochemical cell. The anolyte product output in this range can be such that the output stream contains little or no free bromine in the product output, or it may contain unreacted bromine. The operation of the extractor and its selected separation method, for example fractional distillation, the actual products produced, and the selectivity may be adjusted to obtain desired characteristics. Any of the unreacted components would be recycled to the second region.
- Similarly, a rate of the generation of the formed electrochemical carbon dioxide reduction product, such as CO, is contemplated to be proportional to the applied current to the electrochemical cell. The rate of the input or feed of the
carbon dioxide source 106 should be fed in a proportion to the applied current. The cathode reaction efficiency would determine the maximum theoretical formation in moles of the carbon dioxide reduction product. It is contemplated that the ratio of carbon dioxide feed to the theoretical moles of potentially formed carbon dioxide reduction product would be in a range of 100:1 to 2:1, and preferably in the range of 50:1 to 5:1, where the carbon dioxide is in excess of the theoretical required for the cathode reaction. The carbon dioxide excess would then be separated and recycled back to thefirst region 116. - In the present disclosure, the methods disclosed may be implemented as sets of instructions or software readable by a device. Further, it is understood that the specific order or hierarchy of steps in the methods disclosed are examples of exemplary approaches. Based upon design preferences, it is understood that the specific order or hierarchy of steps in the method can be rearranged while remaining within the disclosed subject matter. The accompanying method claims present elements of the various steps in a sample order, and are not necessarily meant to be limited to the specific order or hierarchy presented.
- It is believed that the present disclosure and many of its attendant advantages will be understood by the foregoing description, and it will be apparent that various changes may be made in the form, construction and arrangement of the components without departing from the disclosed subject matter or without sacrificing all of its material advantages. The form described is merely explanatory, and it is the intention of the following claims to encompass and include such changes.
Claims (21)
1. A method for co-producing M-carboxylate and a halogen, the method comprising the steps of:
contacting a first region of an electrochemical cell having a cathode with a catholyte comprising carbon dioxide;
contacting a second region of the electrochemical cell having an anode with an anolyte comprising an MX where M is at least one cation and X is selected from the group consisting of F, Cl, Br, I and mixtures thereof;
applying an electrical potential between the anode and the cathode of the electrochemical cell sufficient to produce the M-carboxylate recoverable from the first region of the electrochemical cell and the halogen recoverable from the second region of the electrochemical cell;
reacting the halogen from the second region of the electrochemical cell with one of an alkane, an alkene, or an aromatic to produce a halogenated compound and HX.
2. The method according to claim 1 , further comprising:
recycling the HX back to an acidification chamber.
3. The method according to claim 2 , further comprising:
reacting the M-carboxylate with the HX via the acidification chamber to produce a carboxylic acid and MX, the MX being recycled to an input of the second region of the electrochemical cell.
4. The method according to claim 3 , further comprising:
reacting the halogenated compound via a third reactor to produce a second product and HX, the HX being recycled to the acidification chamber.
5. The method according to claim 1 , wherein the halogen includes at least one of F2, Cl2, Br2 or I2.
6. The method according to claim 1 , wherein the halogenated compound includes at least one of a brominated compound, benzyl bromide, (1-bromethyl)benzene, perhalocarbon, bromoethane, vinyl chloride, dichloroethane, allyl chloride, chlorophenol, bromobenzene, vinyl bromide, vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, difluoromethane, or pentafluoroethane.
7. The method according to claim 4 , wherein the second product is at least one of an alkane, an alkene, an alkyne, an alcohol, an aldehyde, or a ketone.
8. The method according to claim 4 , wherein the third reactor includes water.
9. The method according to claim 8 , wherein the second product is an alcohol.
10. The method according to claim 4 , wherein the carboxylic acid is oxalic acid.
11. The method according to claim 4 , further comprising:
feeding the carboxylic acid to a thermal hydrogenation chamber, the thermal hydrogenation chamber comprising H2; and
forming a third product in the thermal hydrogenation chamber.
12. The method according to claim 11 , wherein the third product includes at least one of glyoxylic acid, glycolic acid, glyoxal, glycolaldeyde, ethylene glycol, ethanol, acetic acid, acetaldehyde, ethane, or ethylene.
13. The method according to claim 1 , wherein the cathode and the anode of the first electrochemical cell and the second electrochemical cell are separated by an ion permeable barrier that operates at a temperature less than 600 degrees C.
14. The method according to claim 13 , wherein the ion permeable barrier includes one of a polymeric or inorganic ceramic-based ion permeable barrier.
15. The method according to claim 1 , wherein the catholyte is a liquid and the anolyte is a gas.
16. A method for co-producing M-carboxylate and bromine, the method comprising the steps of:
contacting a first region of an electrochemical cell having a cathode with a catholyte comprising carbon dioxide;
contacting a second region of the electrochemical cell having an anode with an anolyte comprising an MBr where M is at least one cation;
applying an electrical potential between the anode and the cathode of the electrochemical cell sufficient to produce the M-carboxylate recoverable from the first region of the electrochemical cell and the bromine recoverable from the second region of the electrochemical cell;
reacting the bromine from the second region of the electrochemical cell with an alkane to produce a halogenated compound and HBr.
17. The method according to claim 16 , further comprising:
recycling the HBr back to an acidification chamber.
18. The method according to claim 17 , further comprising:
reacting the M-carboxylate with the HBr via the acidification chamber to produce a carboxylic acid and MBr, the MBr being recycled to an input of the second region of the electrochemical cell.
19. The method according to claim 18 , wherein the alkane is ethane.
20. The method according to claim 19 , wherein the halogenated compound is bromoethane.
21. The method according to claim 20 , wherein M is tetrabutylammonium.
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Families Citing this family (99)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102317244A (en) | 2009-01-29 | 2012-01-11 | 普林斯顿大学 | Carbonic acid gas is converted into organic product |
US8500987B2 (en) | 2010-03-19 | 2013-08-06 | Liquid Light, Inc. | Purification of carbon dioxide from a mixture of gases |
US8845877B2 (en) | 2010-03-19 | 2014-09-30 | Liquid Light, Inc. | Heterocycle catalyzed electrochemical process |
US8721866B2 (en) | 2010-03-19 | 2014-05-13 | Liquid Light, Inc. | Electrochemical production of synthesis gas from carbon dioxide |
US10047446B2 (en) * | 2010-07-04 | 2018-08-14 | Dioxide Materials, Inc. | Method and system for electrochemical production of formic acid from carbon dioxide |
US8845878B2 (en) | 2010-07-29 | 2014-09-30 | Liquid Light, Inc. | Reducing carbon dioxide to products |
US8568581B2 (en) | 2010-11-30 | 2013-10-29 | Liquid Light, Inc. | Heterocycle catalyzed carbonylation and hydroformylation with carbon dioxide |
US8961774B2 (en) | 2010-11-30 | 2015-02-24 | Liquid Light, Inc. | Electrochemical production of butanol from carbon dioxide and water |
US9090976B2 (en) | 2010-12-30 | 2015-07-28 | The Trustees Of Princeton University | Advanced aromatic amine heterocyclic catalysts for carbon dioxide reduction |
WO2013006711A1 (en) | 2011-07-06 | 2013-01-10 | Liquid Light, Inc. | Reduction of carbon dioxide to carboxylic acids, glycols, and carboxylates |
KR20140050037A (en) | 2011-07-06 | 2014-04-28 | 리퀴드 라이트 인코포레이티드 | Carbon dioxide capture and conversion to organic products |
US20130105304A1 (en) | 2012-07-26 | 2013-05-02 | Liquid Light, Inc. | System and High Surface Area Electrodes for the Electrochemical Reduction of Carbon Dioxide |
US8647493B2 (en) | 2012-07-26 | 2014-02-11 | Liquid Light, Inc. | Electrochemical co-production of chemicals employing the recycling of a hydrogen halide |
US20140206896A1 (en) * | 2012-07-26 | 2014-07-24 | Liquid Light, Inc. | Method and System for Production of Oxalic Acid and Oxalic Acid Reduction Products |
US8641885B2 (en) | 2012-07-26 | 2014-02-04 | Liquid Light, Inc. | Multiphase electrochemical reduction of CO2 |
US10329676B2 (en) | 2012-07-26 | 2019-06-25 | Avantium Knowledge Centre B.V. | Method and system for electrochemical reduction of carbon dioxide employing a gas diffusion electrode |
US9175407B2 (en) | 2012-07-26 | 2015-11-03 | Liquid Light, Inc. | Integrated process for producing carboxylic acids from carbon dioxide |
WO2014043651A2 (en) | 2012-09-14 | 2014-03-20 | Liquid Light, Inc. | High pressure electrochemical cell and process for the electrochemical reduction of carbon dioxide |
KR20150056635A (en) * | 2012-09-19 | 2015-05-26 | 리퀴드 라이트 인코포레이티드 | Electrochemical co-production of chemicals utilizing a halide salt |
JP6067344B2 (en) * | 2012-11-20 | 2017-01-25 | 株式会社東芝 | Photochemical reaction system |
US9285112B2 (en) * | 2013-01-29 | 2016-03-15 | University Of Kentucky Research Foundation | Method for energy storage to utilize intermittent renewable energy and low-value electricity for CO2 capture and utilization |
US9689078B2 (en) * | 2013-03-06 | 2017-06-27 | Ceramatec, Inc. | Production of valuable chemicals by electroreduction of carbon dioxide in a NaSICON cell |
JP6142010B2 (en) * | 2013-03-15 | 2017-06-07 | ヘレラ アルトゥーロ ソリス | Electrochemical method and system for producing glucose |
EP2985365B1 (en) * | 2013-03-29 | 2019-03-13 | JX Nippon Oil & Energy Corporation | Electrochemical reduction device and production method for hydrogenated product of aromatic compound |
FR3007425B1 (en) * | 2013-06-20 | 2016-07-01 | Ifp Energies Now | NOVEL PROCESS FOR THE PRODUCTION OF FORMIC ACID |
FR3007424B1 (en) * | 2013-06-20 | 2016-07-01 | Ifp Energies Now | PROCESS FOR THE PRODUCTION OF FORMIC ACID BY ELECTROCATALYTIC REDUCTION IN THE GAS PHASE OF CO2 |
WO2014208019A1 (en) * | 2013-06-28 | 2014-12-31 | パナソニックIpマネジメント株式会社 | Methanol production apparatus, methanol production method, and electrode for use in methanol production |
CN105764838B (en) * | 2013-11-20 | 2019-03-01 | 佛罗里达大学研究基金会有限公司 | Carbon dioxide reduction on carbonaceous material |
JP6224226B2 (en) * | 2014-03-24 | 2017-11-01 | 株式会社東芝 | Photoelectrochemical reaction system |
EP3157897B1 (en) * | 2014-06-19 | 2020-09-02 | Avantium Knowledge Centre B.V. | Integrated process for co-production of carboxylic acids and halogen products from carbon dioxide |
US10774431B2 (en) | 2014-10-21 | 2020-09-15 | Dioxide Materials, Inc. | Ion-conducting membranes |
CN104478033B (en) * | 2014-12-02 | 2016-10-05 | 浙江工商大学 | A kind of based on solar energy with the photoelectrocatalysidevice device of powered by wave energy |
US20160222528A1 (en) * | 2015-02-03 | 2016-08-04 | Alstom Technology Ltd | Method for electrochemical reduction of co2 in an electrochemical cell |
US10975480B2 (en) | 2015-02-03 | 2021-04-13 | Dioxide Materials, Inc. | Electrocatalytic process for carbon dioxide conversion |
JP6615175B2 (en) | 2015-02-27 | 2019-12-04 | 国立研究開発法人科学技術振興機構 | Electrochemical reduction of carbon dioxide |
WO2016178948A1 (en) * | 2015-05-05 | 2016-11-10 | Ohio University | Electrochemical cells electrochemical methods |
WO2016186505A1 (en) * | 2015-05-21 | 2016-11-24 | Avantium Knowledge Centre B.V. | Process for the purification of a carboxylic acid-containing composition |
DE102015212503A1 (en) * | 2015-07-03 | 2017-01-05 | Siemens Aktiengesellschaft | Reduction process and electrolysis system for electrochemical carbon dioxide recovery |
PT3320576T (en) * | 2015-07-08 | 2022-02-08 | Agora Energy Tech Ltd | Redox flow battery with carbon dioxide based redox couple |
WO2017034522A1 (en) * | 2015-08-21 | 2017-03-02 | C2F, Inc. | Photochemically converting carbon dioxide into useful reaction products such as ethanol |
US10465303B2 (en) | 2015-09-15 | 2019-11-05 | Kabushiki Kaisha Toshiba | Producing system of reduction product |
DE102016200858A1 (en) * | 2016-01-21 | 2017-07-27 | Siemens Aktiengesellschaft | Electrolysis system and process for electrochemical ethylene oxide production |
US20170241026A1 (en) * | 2016-02-23 | 2017-08-24 | Kabushiki Kaisha Toshiba | Electrochemical reaction device |
DE102016202840A1 (en) * | 2016-02-24 | 2017-08-24 | Siemens Aktiengesellschaft | Process and apparatus for the electrochemical use of carbon dioxide |
CN109643813B (en) | 2016-05-03 | 2022-06-07 | 欧普斯12公司 | For CO2Reactors with advanced architecture for electrochemical reactions of CO and other chemical compounds |
DE102016209451A1 (en) | 2016-05-31 | 2017-11-30 | Siemens Aktiengesellschaft | Apparatus and method for the electrochemical use of carbon dioxide |
US11352705B2 (en) * | 2016-08-12 | 2022-06-07 | California Institute Of Technology | Hydrocarbon oxidation by water oxidation electrocatalysts in non-aqueous solvents |
US11452969B2 (en) | 2016-09-02 | 2022-09-27 | The Board Of Trustees Of The University Of Alabama | Reducing acid gases from streams |
JP6636885B2 (en) | 2016-09-12 | 2020-01-29 | 株式会社東芝 | Reduction catalyst and reduction reactor |
JP6870956B2 (en) | 2016-10-27 | 2021-05-12 | 株式会社東芝 | Electrochemical reactor |
KR101793711B1 (en) * | 2016-11-04 | 2017-11-07 | 한국에너지기술연구원 | Device and Method for preparing carbonate and/or formate from carbon dioxide |
WO2018112653A1 (en) | 2016-12-21 | 2018-06-28 | Isca Management Ltd. | Removal of greenhouse gases and heavy metals from an emission stream |
JP2018153735A (en) * | 2017-03-16 | 2018-10-04 | 株式会社東芝 | Chemical reaction system |
WO2018170252A1 (en) * | 2017-03-16 | 2018-09-20 | Battelle Energy Alliance, Llc | Methods, systems, and electrochemical cells for producing hydrocarbons and protonation products through electrochemical activation of ethane |
CN107142492B (en) * | 2017-06-01 | 2019-08-27 | 中国科学技术大学 | A kind of trans-utilization method of CO |
KR20200026916A (en) * | 2017-07-03 | 2020-03-11 | 코베스트로 도이칠란트 아게 | Electrochemical Method for Synthesis of Diaryl Carbonate |
EP3679177A4 (en) * | 2017-09-07 | 2021-08-11 | The Trustees of Princeton University | Binary alloys and oxides thereof for electrocatalytic reduction of carbon dioxide |
EP3691771B1 (en) * | 2017-10-02 | 2023-08-16 | Battelle Energy Alliance, LLC | Methods and systems for the electrochemical reduction of carbon dioxide using switchable polarity materials |
US11668012B2 (en) | 2017-12-11 | 2023-06-06 | Battelle Energy Alliance, Llc | Methods for producing hydrocarbon products and hydrogen gas through electrochemical activation of methane |
KR20210018783A (en) | 2018-01-22 | 2021-02-18 | 오푸스-12 인코포레이티드 | System and method for carbon dioxide reactor control |
DE102018202335A1 (en) | 2018-02-15 | 2019-08-22 | Linde Aktiengesellschaft | Plant for the electrochemical production of a CO-containing gas product |
US11105006B2 (en) * | 2018-03-22 | 2021-08-31 | Sekisui Chemical Co., Ltd. | Carbon dioxide reduction apparatus and method of producing organic compound |
US11731920B2 (en) * | 2018-08-06 | 2023-08-22 | Battelle Energy Alliance, Llc | Methods for co-producing hydrocarbon products and ammonia |
US11193212B2 (en) * | 2018-09-25 | 2021-12-07 | Sekisui Chemical Co., Ltd. | Synthetic method and synthetic system |
US12049683B2 (en) | 2018-10-23 | 2024-07-30 | University Of Kansas | Methods for recovering metals from metal-containing materials |
CN111188053B (en) * | 2018-11-14 | 2021-05-14 | 万华化学集团股份有限公司 | Method for preparing carbonate by utilizing Kolbe reaction by-product |
DE102018009198A1 (en) * | 2018-11-22 | 2020-05-28 | Linde Aktiengesellschaft | Process for changing the operating mode of an electrolysis plant and electrolysis plant |
KR20210108387A (en) | 2018-11-28 | 2021-09-02 | 오푸스-12 인코포레이티드 | Electrolyzer and how to use it |
US11417901B2 (en) | 2018-12-18 | 2022-08-16 | Twelve Benefit Corporation | Electrolyzer and method of use |
US11920248B2 (en) * | 2018-12-18 | 2024-03-05 | Prometheus Fuels, Inc | Methods and systems for fuel production |
US20220064805A1 (en) * | 2018-12-29 | 2022-03-03 | Cemvita Factory, Inc. | Electrochemical methods and systems for producing monosaccharides |
CN111484407B (en) * | 2019-01-25 | 2023-04-07 | 新发药业有限公司 | Preparation method of 1-halogenated-2-methyl-4-substituted carbonyloxy-2-butene |
CN110438521B (en) * | 2019-07-15 | 2021-09-21 | 华南理工大学 | Method for selectively demethylating N-methyl-N- (2-cyanoethyl) aniline under electrochemical condition |
CN110713437B (en) * | 2019-10-29 | 2021-06-08 | 福州大学 | Device and method for preparing oxalic acid by hydrolyzing oxalate |
EP3819259A1 (en) * | 2019-11-06 | 2021-05-12 | Covestro Deutschland AG | Method for the production of isocyanates and polyurethanes with improved sustainability |
EP4065753A1 (en) | 2019-11-25 | 2022-10-05 | Twelve Benefit Corporation | Membrane electrode assembly for co x reduction |
US11001549B1 (en) | 2019-12-06 | 2021-05-11 | Saudi Arabian Oil Company | Electrochemical reduction of carbon dioxide to upgrade hydrocarbon feedstocks |
US11814738B2 (en) * | 2020-01-30 | 2023-11-14 | Avantium Knowledge Centre B.V. | Electrochemical production of formate |
CN111304672B (en) * | 2020-03-18 | 2022-03-29 | 大连理工大学 | H-shaped fixed bed carbon dioxide reduction electrolytic cell and application |
CN111548269B (en) * | 2020-04-29 | 2023-10-27 | 兰州大学 | Preparation method of diaryl methane structural compound |
CN111575726B (en) * | 2020-05-27 | 2021-10-01 | 上海科技大学 | Electrochemical reactor for electrochemical reduction of carbon dioxide |
CN111676484A (en) * | 2020-06-17 | 2020-09-18 | 深圳大学 | Method and system for reducing energy consumption, electrolyzing water, producing hydrogen and symbiotically producing value-added chemicals |
US20230279563A1 (en) * | 2020-07-28 | 2023-09-07 | Électro Carbone Inc. | Electrochemical cell for carbon dioxide reduction towards liquid chemicals |
JP2023546172A (en) | 2020-10-20 | 2023-11-01 | トゥエルブ ベネフィット コーポレーション | Semi-interpenetrating and cross-linked polymers and membranes thereof |
CN112195481B (en) * | 2020-11-02 | 2021-12-10 | 上海漫关越水处理有限公司 | Method for synthesizing tetramethoxyethane by membrane electrolysis |
US20220205113A1 (en) * | 2020-12-31 | 2022-06-30 | Uop Llc | Electrocatalytic hydrogen recovery from hydrogen sulfide and application of the circular hydrogen economy for hydrotreatment |
WO2022192153A1 (en) * | 2021-03-08 | 2022-09-15 | The Regents Of The University Of California | Sugar formation from co2 electroreduction |
US12054805B2 (en) | 2021-04-28 | 2024-08-06 | University Of Kansas | Methods for recovering metals using oxalate compounds |
US20240252980A1 (en) * | 2021-05-20 | 2024-08-01 | Battelle Energy Alliance, Llc | Direct air capture reactor systems and related methods of transporting carbon dioxide |
US20230010993A1 (en) * | 2021-07-12 | 2023-01-12 | Dioxycle | Carbon dioxide extraction electrolysis reactor |
CN113429254A (en) * | 2021-07-22 | 2021-09-24 | 浙江解氏新材料股份有限公司 | Efficient synthesis method of 2, 4-dichlorofluorobenzene based on ceramic packed tower |
WO2023036857A1 (en) * | 2021-09-09 | 2023-03-16 | Totalenergies Onetech | Process for the production of hydrogen through electrification of water gas shift reaction |
US12018392B2 (en) | 2022-01-03 | 2024-06-25 | Saudi Arabian Oil Company | Methods for producing syngas from H2S and CO2 in an electrochemical cell |
CN114411169B (en) * | 2022-01-25 | 2023-12-26 | 山西大学 | Photoelectrocatalysis hydrogen production and nitroarene in-situ hydrogenation integrated device and application |
EP4227442A1 (en) | 2022-02-14 | 2023-08-16 | Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO | Paired electrochemical synthesis of oxymethylene dimethyl ethers |
WO2023187781A1 (en) * | 2022-03-31 | 2023-10-05 | Hys Energy Ltd | Hydrogen production by electrochemical decomposition of saline water using sulfur dioxide or bisulfite as an anode depolarizer |
US11939284B2 (en) | 2022-08-12 | 2024-03-26 | Twelve Benefit Corporation | Acetic acid production |
US11846034B1 (en) * | 2022-11-23 | 2023-12-19 | Dioxycle | Carbon monoxide electrolyzers used with reverse water gas shift reactors for the conversion of carbon dioxide into added-value products |
CN116716484B (en) * | 2023-08-11 | 2023-10-03 | 云南贵金属实验室有限公司 | Method for recovering palladium and dimethylglyoxime from palladium-refining palladium-removing slag |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2060880A (en) * | 1933-09-23 | 1936-11-17 | Du Pont | Process of producing ethylene glycol |
US3720591A (en) * | 1971-12-28 | 1973-03-13 | Texaco Inc | Preparation of oxalic acid |
US20040006246A1 (en) * | 2001-06-20 | 2004-01-08 | Sherman Jeffrey H. | Method and apparatus for synthesizing olefins, alcohols, ethers, and aldehydes |
Family Cites Families (222)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1280622A (en) | 1915-05-08 | 1918-10-08 | Launcelot W Andrews | Process for manufacturing oxalates. |
US1962140A (en) | 1928-04-18 | 1934-06-12 | Dreyfus Henry | Manufacture of hydroxy carboxylic acids |
FR853643A (en) | 1938-05-04 | 1940-03-23 | Ig Farbenindustrie Ag | Process for producing halogenated hydrocarbons |
US2967806A (en) | 1953-04-02 | 1961-01-10 | Hooker Chemical Corp | Electrolytic decomposition with permselective diaphragms |
US3236879A (en) | 1957-10-10 | 1966-02-22 | Montedison Spa | Preparation of alpha-beta, deltaepsilon unsaturated carboxylic acids and esters |
US3019256A (en) | 1959-03-23 | 1962-01-30 | Union Carbide Corp | Process for producing acrylic acid esters |
US3088990A (en) | 1960-04-25 | 1963-05-07 | Standard Oil Co | Energy conversion system |
US3220941A (en) | 1960-08-03 | 1965-11-30 | Hooker Chemical Corp | Method for electrolysis |
NL293359A (en) | 1962-06-02 | |||
US3293292A (en) | 1962-12-07 | 1966-12-20 | Union Oil Co | Butane oxidation |
NL129705C (en) | 1963-11-04 | |||
GB1096847A (en) | 1964-03-27 | 1967-12-29 | Ethyl Corp | A process for the production of primary aliphatic hydrocarbon halides |
US3326998A (en) | 1964-04-20 | 1967-06-20 | Phillips Petroleum Co | Catalytic dehydrohalogenation of alkyl halides in presence of nitrogen-containing compounds |
US3352935A (en) | 1964-04-20 | 1967-11-14 | Phillips Petroleum Co | Dehydrohalogenation process |
US3401100A (en) | 1964-05-26 | 1968-09-10 | Trw Inc | Electrolytic process for concentrating carbon dioxide |
US3347758A (en) | 1964-09-25 | 1967-10-17 | Mobil Oil Corp | Electrochemical preparation of aromatic esters |
US3344046A (en) | 1964-10-23 | 1967-09-26 | Sun Oil Co | Electrolytic preparation of organic carbonates |
US3341616A (en) | 1966-01-10 | 1967-09-12 | Phillips Petroleum Co | Dehydrohalogenation process and catalyst |
DE1618405A1 (en) | 1967-04-20 | 1971-03-25 | Bayer Ag | Process for the electrochemical production of olefin oxides |
US3479261A (en) | 1967-05-15 | 1969-11-18 | North American Rockwell | Electrochemical method for recovery of sulfur oxides |
US3560354A (en) | 1967-10-16 | 1971-02-02 | Union Oil Co | Electrolytic chemical process |
GB1203434A (en) | 1967-10-23 | 1970-08-26 | Ici Ltd | Oxidation of organic materials |
DE1668102A1 (en) | 1968-02-28 | 1971-06-03 | Hoechst Ag | Process for the production of acetylene |
US3649482A (en) | 1968-11-04 | 1972-03-14 | Continental Oil Co | Cathodic process for the preparation of tetraalkyl lead compounds |
US3636159A (en) | 1968-12-19 | 1972-01-18 | Phillips Petroleum Co | Hydroformylation process and catalyst |
US3919114A (en) * | 1969-11-21 | 1975-11-11 | Texaco Development Corp | Synthesis gas process |
JPS4829721Y1 (en) | 1969-12-28 | 1973-09-10 | ||
JPS4829721B1 (en) | 1970-12-26 | 1973-09-13 | ||
BE787771A (en) | 1971-08-20 | 1973-02-19 | Rhone Poulenc Sa | PREPARATION OF GLYOXYLIC ACID |
US3764492A (en) | 1972-01-10 | 1973-10-09 | Monsanto Co | Electrolytic preparation of esters from organo halides |
GB1425022A (en) | 1972-05-03 | 1976-02-18 | Petrocarbon Dev Lts | Process for the oxidation of olefins |
US3824163A (en) | 1972-07-19 | 1974-07-16 | Electronic Associates | Electrochemical sulfur dioxide abatement process |
US4147599A (en) | 1977-07-19 | 1979-04-03 | Diamond Shamrock Corporation | Production of alkali metal carbonates in a cell having a carboxyl membrane |
DE2301032A1 (en) | 1973-01-10 | 1974-07-25 | Dechema | Oxalic acid prodn. - by electro-chemical reductive dimerisation of carbon dioxide |
NL175835B (en) * | 1973-04-17 | 1984-08-01 | Shell Int Research | Process for preparing a hydrogen-rich gas from a carbon monoxide-containing gas using a nickel and / or cobalt and molybdenum-containing catalyst. |
DE2343054C2 (en) | 1973-08-25 | 1975-10-09 | Basf Ag, 6700 Ludwigshafen | Process for the electrochemical production of pinacols |
JPS5052010U (en) | 1973-09-10 | 1975-05-20 | ||
US4011275A (en) * | 1974-08-23 | 1977-03-08 | Mobil Oil Corporation | Conversion of modified synthesis gas to oxygenated organic chemicals |
US3959094A (en) | 1975-03-13 | 1976-05-25 | The United States Of America As Represented By The United States Energy Research And Development Administration | Electrolytic synthesis of methanol from CO2 |
US4088682A (en) | 1975-07-03 | 1978-05-09 | Jordan Robert Kenneth | Oxalate hydrogenation process |
US4087470A (en) | 1976-06-23 | 1978-05-02 | Chevron Research Company | Process for the production of ethylene glycol |
US4072583A (en) | 1976-10-07 | 1978-02-07 | Monsanto Company | Electrolytic carboxylation of carbon acids via electrogenerated bases |
JPS53101311U (en) | 1977-01-20 | 1978-08-16 | ||
JPS53101311A (en) | 1977-02-10 | 1978-09-04 | Mitsubishi Chem Ind Ltd | Preparation of 1,2,3,4-butaneteracarboxylic acid |
DE2814807A1 (en) | 1977-04-19 | 1978-10-26 | Standard Oil Co | PROCESS FOR OXIDATING BUTANE TO ACETIC ACID |
JPS53132504A (en) | 1977-04-26 | 1978-11-18 | Central Glass Co Ltd | Dehalogenation of halogenated hydrocarbons |
IL54408A (en) | 1978-03-31 | 1981-09-13 | Yeda Res & Dev | Photosynthetic process for converting carbon dioxide to organic compounds |
US4299981A (en) | 1978-06-05 | 1981-11-10 | Leonard Jackson D | Preparation of formic acid by hydrolysis of methyl formate |
JPS5576084A (en) | 1978-12-01 | 1980-06-07 | Takeda Chem Ind Ltd | Method and apparatus for production of vitamin b1 and intermediate thereof |
US4245114A (en) | 1978-12-19 | 1981-01-13 | Halcon Research And Development Corporation | Glycol ester preparation |
DE2953388C2 (en) | 1979-01-23 | 1986-07-24 | Institut elektrochimii Akademii Nauk SSSR, Moskau/Moskva | Process for the preparation of 1,2-dichloroethane |
IT1122699B (en) * | 1979-08-03 | 1986-04-23 | Oronzio De Nora Impianti | RESILIENT ELECTRIC COLLECTOR AND SOLID ELECTROLYTE ELECTROCHEMISTRY INCLUDING THE SAME |
GB2058839B (en) | 1979-09-08 | 1983-02-16 | Engelhard Min & Chem | Photo electrochemical processes |
US4267070A (en) | 1979-10-30 | 1981-05-12 | Nefedov Boris K | Catalyst for the synthesis of aromatic monoisocyanates |
DE3066199D1 (en) | 1979-11-01 | 1984-02-23 | Shell Int Research | A process for the electroreductive preparation of organic compounds |
DK3981A (en) | 1980-01-07 | 1981-07-08 | Albright & Wilson | PROCEDURE FOR PREPARING HYDROXY COMPOUNDS BY ELECTROCHEMICAL REDUCTION |
US4253921A (en) | 1980-03-10 | 1981-03-03 | Battelle Development Corporation | Electrochemical synthesis of butane-1,4-diol |
US4510214A (en) | 1980-10-03 | 1985-04-09 | Tracer Technologies, Inc. | Electrode with electron transfer catalyst |
CH645393A5 (en) | 1981-02-19 | 1984-09-28 | Ciba Geigy Ag | HARDENABLE MIXTURES OF POLYEPOXIDE COMPOUNDS AND N-CYANLACTAMES AS HARDENERS. |
IL67047A0 (en) | 1981-10-28 | 1983-02-23 | Eltech Systems Corp | Narrow gap electrolytic cells |
US4450055A (en) | 1983-03-30 | 1984-05-22 | Celanese Corporation | Electrogenerative partial oxidation of organic compounds |
US4476003A (en) | 1983-04-07 | 1984-10-09 | The United States Of America As Represented By The United States Department Of Energy | Chemical anchoring of organic conducting polymers to semiconducting surfaces |
US4560451A (en) | 1983-05-02 | 1985-12-24 | Union Carbide Corporation | Electrolytic process for the production of alkene oxides |
DE3320219A1 (en) * | 1983-06-03 | 1984-12-06 | Henkel KGaA, 4000 Düsseldorf | CONTINUOUS, CATALYTIC EPOXIDATION OF DOUBLE OLEFINIC BINDINGS WITH HYDROGEN PEROXIDE AND FORMIC ACID |
DE3334863A1 (en) | 1983-09-27 | 1985-04-11 | Basf Ag, 6700 Ludwigshafen | Process for obtaining aqueous glyoxylic acid solutions |
US4523981A (en) | 1984-03-27 | 1985-06-18 | Texaco Inc. | Means and method for reducing carbon dioxide to provide a product |
US4547271A (en) | 1984-09-12 | 1985-10-15 | Canada Packers Inc. | Process for the electrochemical reduction of 7-ketolithocholic acid to ursodeoxycholic acid |
US4589963A (en) | 1984-12-07 | 1986-05-20 | The Dow Chemical Company | Process for the conversion of salts of carboxylic acid to their corresponding free acids |
US4595465A (en) | 1984-12-24 | 1986-06-17 | Texaco Inc. | Means and method for reducing carbn dioxide to provide an oxalate product |
US4563254A (en) | 1985-02-07 | 1986-01-07 | Texaco Inc. | Means and method for the electrochemical carbonylation of nitrobenzene or 2-5 dinitrotoluene with carbon dioxide to provide a product |
US4661422A (en) | 1985-03-04 | 1987-04-28 | Institute Of Gas Technology | Electrochemical production of partially oxidized organic compounds |
US4608132A (en) | 1985-06-06 | 1986-08-26 | Texaco Inc. | Means and method for the electrochemical reduction of carbon dioxide to provide a product |
US4673473A (en) | 1985-06-06 | 1987-06-16 | Peter G. Pa Ang | Means and method for reducing carbon dioxide to a product |
US4608133A (en) | 1985-06-10 | 1986-08-26 | Texaco Inc. | Means and method for the electrochemical reduction of carbon dioxide to provide a product |
US4619743A (en) | 1985-07-16 | 1986-10-28 | Texaco Inc. | Electrolytic method for reducing oxalic acid to a product |
US4810596A (en) | 1985-10-18 | 1989-03-07 | Hughes Aircraft Company | Sulfuric acid thermoelectrochemical system and method |
US5443804A (en) | 1985-12-04 | 1995-08-22 | Solar Reactor Technologies, Inc. | System for the manufacture of methanol and simultaneous abatement of emission of greenhouse gases |
US4732655A (en) | 1986-06-11 | 1988-03-22 | Texaco Inc. | Means and method for providing two chemical products from electrolytes |
US4702973A (en) | 1986-08-25 | 1987-10-27 | Institute Of Gas Technology | Dual compartment anode structure |
US4756807A (en) | 1986-10-09 | 1988-07-12 | Gas Research Institute | Chemically modified electrodes for the catalytic reduction of CO2 |
ATE56711T1 (en) | 1987-03-25 | 1990-10-15 | Degussa | PROCESS FOR THE CATALYTIC EPOXYDATION OF OLEFINS WITH HYDROGEN PEROXIDE. |
JPS6415388U (en) | 1987-05-23 | 1989-01-26 | ||
JPS6415388A (en) | 1987-07-07 | 1989-01-19 | Terumo Corp | Electrode for reducing gaseous carbon dioxide |
JPH0775784B2 (en) | 1987-12-03 | 1995-08-16 | 株式会社中央製作所 | Resistance welding machine capable of multiple types of welding |
US5155256A (en) | 1988-04-11 | 1992-10-13 | Mallinckrodt Medical, Inc. | Process for preparing 2-bromoethyl acetate |
US4968393A (en) | 1988-04-18 | 1990-11-06 | A. L. Sandpiper Corporation | Membrane divided aqueous-nonaqueous system for electrochemical cells |
DE69027304T2 (en) | 1989-01-17 | 1997-01-23 | Davy Process Technology Ltd., London | Continuous process for the production of carboxylic acid esters |
US4950368A (en) | 1989-04-10 | 1990-08-21 | The Electrosynthesis Co., Inc. | Method for paired electrochemical synthesis with simultaneous production of ethylene glycol |
DE68903760T2 (en) | 1989-08-07 | 1993-04-08 | Euratom | METHOD FOR REMOVING NITROGEN COMPOUNDS FROM LIQUIDS. |
US5106465A (en) | 1989-12-20 | 1992-04-21 | Olin Corporation | Electrochemical process for producing chlorine dioxide solutions from chlorites |
US5294319A (en) | 1989-12-26 | 1994-03-15 | Olin Corporation | High surface area electrode structures for electrochemical processes |
US5084148A (en) | 1990-02-06 | 1992-01-28 | Olin Corporation | Electrochemical process for producing chloric acid - alkali metal chlorate mixtures |
JP3038393B2 (en) | 1990-05-30 | 2000-05-08 | 石川島播磨重工業株式会社 | Molten carbonate fuel cell power generator with CO 2 separation device using LNG cold energy |
US5074974A (en) | 1990-06-08 | 1991-12-24 | Reilly Industries, Inc. | Electrochemical synthesis and simultaneous purification process |
US5096054A (en) * | 1990-06-11 | 1992-03-17 | Case Western Reserve University | Electrochemical method for the removal of nitrogen oxides and sulfur oxides from flue gas and other sources |
US5290404A (en) | 1990-10-31 | 1994-03-01 | Reilly Industries, Inc. | Electro-synthesis of alcohols and carboxylic acids from corresponding metal salts |
US5198086A (en) | 1990-12-21 | 1993-03-30 | Allied-Signal | Electrodialysis of salts of weak acids and/or weak bases |
US5107040A (en) | 1991-05-15 | 1992-04-21 | The Dow Chemical Company | Dehydrohalogenation using magnesium hydroxide |
JPH07118886B2 (en) | 1991-07-10 | 1995-12-18 | アドバンス・コージェネレーションシステム技術研究組合 | How to join rotor core and rotor bar |
US5246551A (en) | 1992-02-11 | 1993-09-21 | Chemetics International Company Ltd. | Electrochemical methods for production of alkali metal hydroxides without the co-production of chlorine |
ATE138425T1 (en) | 1992-02-22 | 1996-06-15 | Hoechst Ag | ELECTROCHEMICAL PROCESS FOR PRODUCING GLYOXYLIC ACID |
US5223102A (en) * | 1992-03-03 | 1993-06-29 | E. I. Du Pont De Nemours And Company | Process for the electrooxidation of methanol to formaldehyde and methylal |
US5300369A (en) | 1992-07-22 | 1994-04-05 | Space Systems/Loral | Electric energy cell with internal failure compensation |
EP0614875A1 (en) | 1993-03-12 | 1994-09-14 | Ube Industries, Ltd. | Method of producing a glycolic acid ester |
DE4318069C1 (en) | 1993-06-01 | 1994-03-31 | Cassella Ag | Prodn. of methyl 5-bromo-6-methoxy-1-naphthoate - used as tolrestat intermediate, comprises reaction of methyl 6-methoxy-1-naphthoate with bromine in presence of oxidising agent |
JP3458341B2 (en) | 1993-07-12 | 2003-10-20 | 有限会社コヒーレントテクノロジー | Method for producing washing water containing hydrogen ions or hydroxyl ions in excess of counter ions and obtained washing water |
JP3343601B2 (en) | 1993-10-26 | 2002-11-11 | 関西電力株式会社 | Method for producing hydrocarbons from carbon dioxide |
US6010612A (en) * | 1993-11-22 | 2000-01-04 | E.I. Du Pont De Nemours And Company | Production of isocyanate using chlorine recycle |
NO300038B1 (en) | 1995-05-12 | 1997-03-24 | Norsk Hydro As | Process for the preparation of products containing double salts of formic acid |
US5514492A (en) | 1995-06-02 | 1996-05-07 | Pacesetter, Inc. | Cathode material for use in an electrochemical cell and method for preparation thereof |
DE19531408A1 (en) | 1995-08-26 | 1997-02-27 | Hoechst Ag | Process for the preparation of (4-bromophenyl) alkyl ethers |
DE19543678A1 (en) | 1995-11-23 | 1997-05-28 | Bayer Ag | Process for direct electrochemical gas phase phosgene synthesis |
IN190134B (en) | 1995-12-28 | 2003-06-21 | Du Pont | |
US6024935A (en) | 1996-01-26 | 2000-02-15 | Blacklight Power, Inc. | Lower-energy hydrogen methods and structures |
FR2747694B1 (en) | 1996-04-18 | 1998-06-05 | France Etat | CATHODE FOR THE REDUCTION OF CARBON DIOXIDE AND METHOD OF MANUFACTURING SUCH A CATHODE |
AU3376697A (en) | 1996-06-05 | 1998-01-05 | Southwest Research Institute | Cylindrical proton exchange membrane fuel cells and methods of making same |
AR010696A1 (en) | 1996-12-12 | 2000-06-28 | Sasol Tech Pty Ltd | A METHOD FOR THE ELIMINATION OF CARBON DIOXIDE FROM A PROCESS GAS |
US5928806A (en) | 1997-05-07 | 1999-07-27 | Olah; George A. | Recycling of carbon dioxide into methyl alcohol and related oxygenates for hydrocarbons |
US6271400B2 (en) | 1997-10-23 | 2001-08-07 | The Scripps Research Institute | Epoxidation of olefins |
US6171551B1 (en) | 1998-02-06 | 2001-01-09 | Steris Corporation | Electrolytic synthesis of peracetic acid and other oxidants |
US20020122980A1 (en) | 1998-05-19 | 2002-09-05 | Fleischer Niles A. | Electrochemical cell with a non-liquid electrolyte |
US6267864B1 (en) | 1998-09-14 | 2001-07-31 | Nanomaterials Research Corporation | Field assisted transformation of chemical and material compositions |
JP2000104190A (en) | 1998-09-30 | 2000-04-11 | Mitsui Chemicals Inc | Production of metahydroxybenzaldehyde |
US6251256B1 (en) | 1999-02-04 | 2001-06-26 | Celanese International Corporation | Process for electrochemical oxidation of an aldehyde to an ester |
US6274009B1 (en) | 1999-09-03 | 2001-08-14 | International Dioxide Inc. | Generator for generating chlorine dioxide under vacuum eduction in a single pass |
CN101104147A (en) | 1999-11-22 | 2008-01-16 | 陶氏环球技术公司 | Composition with catalyzing function |
EP1112997B1 (en) | 1999-12-28 | 2009-05-13 | Mitsubishi Chemical Corporation | Process for producing diaryl carbonate |
US6447943B1 (en) | 2000-01-18 | 2002-09-10 | Ramot University Authority For Applied Research & Industrial Development Ltd. | Fuel cell with proton conducting membrane with a pore size less than 30 nm |
KR100391845B1 (en) | 2000-02-11 | 2003-07-16 | 한국과학기술연구원 | Synthesis of Alkylene Carbonates using a Metal Halides Complex containing Pyridine Ligands |
US6828054B2 (en) | 2000-02-11 | 2004-12-07 | The Texas A&M University System | Electronically conducting fuel cell component with directly bonded layers and method for making the same |
FR2806073B1 (en) * | 2000-03-07 | 2002-06-07 | Air Liquide | PROCESS FOR PRODUCING CARBON MONOXIDE BY REVERSE RETROCONVERSION WITH AN ADAPTED CATALYST |
JP3505708B2 (en) | 2000-06-12 | 2004-03-15 | 本田技研工業株式会社 | Single cell for polymer electrolyte fuel cell, method for manufacturing the same, polymer electrolyte fuel cell, and method for regenerating the same |
US6380446B1 (en) | 2000-08-17 | 2002-04-30 | Dupont Dow Elastomers, L.L.C. | Process for dehydrohalogenation of halogenated compounds |
US6656873B2 (en) | 2001-06-14 | 2003-12-02 | Sanjay Chaturvedi | Mixed metal oxide catalyst |
US6465699B1 (en) | 2001-06-20 | 2002-10-15 | Gri, Inc. | Integrated process for synthesizing alcohols, ethers, and olefins from alkanes |
GB0116505D0 (en) | 2001-07-06 | 2001-08-29 | Univ Belfast | Electrosynthesis of organic compounds |
AU2003214890A1 (en) | 2002-01-24 | 2003-09-09 | The C And M Group, Llc | Mediated electrochemical oxidation of halogenated hydrocarbon waste materials |
US6949178B2 (en) | 2002-07-09 | 2005-09-27 | Lynntech, Inc. | Electrochemical method for preparing peroxy acids |
AU2003303104A1 (en) | 2002-08-21 | 2004-10-18 | Battelle Memorial Institute | Photolytic oxygenator with carbon dioxide and/or hydrogen separation and fixation |
AU2003270437A1 (en) | 2002-09-10 | 2004-04-30 | The C And M Group, Llc | Mediated electrochemical oxidation of inorganic materials |
US20040115489A1 (en) | 2002-12-12 | 2004-06-17 | Manish Goel | Water and energy management system for a fuel cell |
EP1443091A1 (en) | 2003-01-31 | 2004-08-04 | Ntera Limited | Electrochromic compounds |
CA2526438A1 (en) | 2003-05-19 | 2004-12-02 | Michael Trachtenberg | Methods, apparatuses, and reactors for gas separation |
US7378011B2 (en) | 2003-07-28 | 2008-05-27 | Phelps Dodge Corporation | Method and apparatus for electrowinning copper using the ferrous/ferric anode reaction |
FR2863911B1 (en) | 2003-12-23 | 2006-04-07 | Inst Francais Du Petrole | CARBON SEQUESTRATION PROCESS IN THE FORM OF A MINERAL IN WHICH THE CARBON IS AT THE DEGREE OF OXIDATION +3 |
US10629947B2 (en) | 2008-08-05 | 2020-04-21 | Sion Power Corporation | Electrochemical cell |
US7462752B2 (en) | 2004-04-21 | 2008-12-09 | Shell Oil Company | Process to convert linear alkanes into alpha olefins |
EP1748509B1 (en) | 2004-04-22 | 2017-03-01 | Nippon Steel & Sumitomo Metal Corporation | Fuel cell and gas diffusion electrode for fuel cell |
JP5114823B2 (en) | 2004-05-31 | 2013-01-09 | 日産自動車株式会社 | Photoelectrochemical cell |
JP2008535778A (en) | 2005-01-07 | 2008-09-04 | コンビマトリックス・コーポレイション | Method for electrochemically performing isolated Pd (0) catalytic reaction with an electrode array device |
US9057136B2 (en) * | 2005-04-12 | 2015-06-16 | University Of South Carolina | Production of low temperature electrolytic hydrogen |
US7767358B2 (en) | 2005-05-31 | 2010-08-03 | Nextech Materials, Ltd. | Supported ceramic membranes and electrochemical cells and cell stacks including the same |
DE102005032663A1 (en) | 2005-07-13 | 2007-01-18 | Bayer Materialscience Ag | Process for the preparation of isocyanates |
EP1942087A1 (en) | 2005-10-05 | 2008-07-09 | Daiichi Sankyo Company, Limited | Method for dehydrohalogenation of organic halogen compound |
JP2009511740A (en) * | 2005-10-13 | 2009-03-19 | マントラ エナジー オールターナティヴス リミテッド | Continuous cocurrent electrochemical reduction of carbon dioxide |
US20090062110A1 (en) | 2006-02-08 | 2009-03-05 | Sumitomo Chemical Company Limited | Metal complex and use thereof |
US20100051859A1 (en) | 2006-04-27 | 2010-03-04 | President And Fellows Of Harvard College | Carbon Dioxide Capture and Related Processes |
SE530266C2 (en) | 2006-06-16 | 2008-04-15 | Morphic Technologies Ab Publ | Process and reactor for the production of methanol |
EP1933330A1 (en) | 2006-12-11 | 2008-06-18 | Trasis S.A. | Electrochemical 18F extraction, concentration and reformulation method for radiolabeling |
FI121271B (en) | 2007-01-19 | 2010-09-15 | Outotec Oyj | Process for the preparation of hydrogen and sulfuric acid |
CN103227339B (en) | 2007-04-03 | 2016-03-09 | 新空能量公司 | Produce renewable hydrogen and retain electro-chemical systems, the apparatus and method of carbon dioxide |
US8277631B2 (en) | 2007-05-04 | 2012-10-02 | Principle Energy Solutions, Inc. | Methods and devices for the production of hydrocarbons from carbon and hydrogen sources |
AU2008254937C1 (en) | 2007-05-14 | 2013-05-30 | Grt, Inc. | Process for converting hydrocarbon feedstocks with electrolytic recovery of halogen |
TW200911693A (en) | 2007-06-12 | 2009-03-16 | Solvay | Aqueous composition containing a salt, manufacturing process and use |
US7906559B2 (en) | 2007-06-21 | 2011-03-15 | University Of Southern California | Conversion of carbon dioxide to methanol and/or dimethyl ether using bi-reforming of methane or natural gas |
EP2167706B1 (en) | 2007-07-13 | 2017-11-15 | University of Southern California | Electrolysis of carbon dioxide in aqueous media to carbon monoxide and hydrogen for production of methanol |
TW200920721A (en) | 2007-07-13 | 2009-05-16 | Solvay Fluor Gmbh | Preparation of halogen and hydrogen containing alkenes over metal fluoride catalysts |
US8152988B2 (en) | 2007-08-31 | 2012-04-10 | Energy & Enviromental Research Center Foundation | Electrochemical process for the preparation of nitrogen fertilizers |
TWI423946B (en) | 2007-11-14 | 2014-01-21 | Shell Int Research | Process for the preparation of alkylene glycol |
JP5439757B2 (en) | 2007-12-07 | 2014-03-12 | ソニー株式会社 | Fuel cells and electronics |
EP2078697A1 (en) | 2008-01-08 | 2009-07-15 | SOLVAY (Société Anonyme) | Process for producing sodium carbonate and/or sodium bicarbonate from an ore mineral comprising sodium bicarbonate |
WO2009108327A1 (en) | 2008-02-26 | 2009-09-03 | Grimes, Maureen A. | Production of hydrocarbons from carbon dioxide and water |
US8282810B2 (en) | 2008-06-13 | 2012-10-09 | Marathon Gtf Technology, Ltd. | Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery |
WO2010008836A2 (en) | 2008-06-23 | 2010-01-21 | Arizona Board Of Regents For And On Behalf Of Arizona State University | Bicarbonate and carbonate as hydroxide carriers in a biological fuel cell |
US7993500B2 (en) * | 2008-07-16 | 2011-08-09 | Calera Corporation | Gas diffusion anode and CO2 cathode electrolyte system |
JP5493572B2 (en) | 2008-08-11 | 2014-05-14 | 株式会社豊田中央研究所 | Photocatalyst and reduction catalyst using the same |
JP5428328B2 (en) * | 2008-12-24 | 2014-02-26 | 栗田工業株式会社 | Microbial power generation method and microbial power generation apparatus |
CN102317244A (en) | 2009-01-29 | 2012-01-11 | 普林斯顿大学 | Carbonic acid gas is converted into organic product |
US8163429B2 (en) | 2009-02-05 | 2012-04-24 | Ini Power Systems, Inc. | High efficiency fuel cell system |
WO2010093716A1 (en) | 2009-02-10 | 2010-08-19 | Calera Corporation | Low-voltage alkaline production using hydrogen and electrocatlytic electrodes |
FR2944031B1 (en) | 2009-04-06 | 2013-06-14 | Commissariat Energie Atomique | ELECTROCHEMICAL CELL WITH ELECTROLYTE FLOW COMPRISING THROUGH ELECTRODES AND METHOD OF MANUFACTURE |
US20100270167A1 (en) | 2009-04-22 | 2010-10-28 | Mcfarland Eric | Process for converting hydrocarbon feedstocks with electrolytic and photoelectrocatalytic recovery of halogens |
US9099720B2 (en) | 2009-05-29 | 2015-08-04 | Medtronic, Inc. | Elongate battery for implantable medical device |
US7993511B2 (en) | 2009-07-15 | 2011-08-09 | Calera Corporation | Electrochemical production of an alkaline solution using CO2 |
WO2011011521A2 (en) | 2009-07-23 | 2011-01-27 | Ceramatec, Inc. | Decarboxylation cell for production of coupled radical products |
CA2782690A1 (en) | 2009-12-02 | 2011-06-09 | Board Of Trustees Of Michigan State University | Carboxylic acid recovery and methods related thereto |
WO2011067873A1 (en) | 2009-12-04 | 2011-06-09 | パナソニック株式会社 | Method for reducing carbon dioxide, and carbon dioxide reduction catalyst and carbon dioxide reduction apparatus used therein |
US20110114502A1 (en) | 2009-12-21 | 2011-05-19 | Emily Barton Cole | Reducing carbon dioxide to products |
CA2787640C (en) | 2010-01-25 | 2015-01-06 | Ramot At Tel-Aviv University Ltd | Electrochemical systems and methods of operating same |
US20110186441A1 (en) | 2010-01-29 | 2011-08-04 | Conocophillips Company | Electrolytic recovery of retained carbon dioxide |
US8703089B2 (en) | 2010-03-03 | 2014-04-22 | Ino Therapeutics Llc | Method and apparatus for the manufacture of high purity carbon monoxide |
AU2011227129A1 (en) | 2010-03-18 | 2012-10-11 | Blacklight Power, Inc. | Electrochemical hydrogen-catalyst power system |
US8500987B2 (en) | 2010-03-19 | 2013-08-06 | Liquid Light, Inc. | Purification of carbon dioxide from a mixture of gases |
US8721866B2 (en) | 2010-03-19 | 2014-05-13 | Liquid Light, Inc. | Electrochemical production of synthesis gas from carbon dioxide |
US8845877B2 (en) | 2010-03-19 | 2014-09-30 | Liquid Light, Inc. | Heterocycle catalyzed electrochemical process |
US20110237830A1 (en) | 2010-03-26 | 2011-09-29 | Dioxide Materials Inc | Novel catalyst mixtures |
US8591718B2 (en) * | 2010-04-19 | 2013-11-26 | Praxair Technology, Inc. | Electrochemical carbon monoxide production |
CN101879448B (en) | 2010-06-24 | 2012-05-23 | 天津大学 | Ordered structure catalyst for hydrogenation of oxalic ester for preparing ethylene glycol and preparation method thereof |
US9045407B2 (en) | 2010-06-30 | 2015-06-02 | Uop Llc | Mixtures used in oxidizing alkyl aromatic compounds |
US8933265B2 (en) | 2010-06-30 | 2015-01-13 | Uop Llc | Process for oxidizing alkyl aromatic compounds |
US8884054B2 (en) | 2010-06-30 | 2014-11-11 | Uop Llc | Process for oxidizing alkyl aromatic compounds |
US20130180865A1 (en) | 2010-07-29 | 2013-07-18 | Liquid Light, Inc. | Reducing Carbon Dioxide to Products |
US8845878B2 (en) | 2010-07-29 | 2014-09-30 | Liquid Light, Inc. | Reducing carbon dioxide to products |
US8524066B2 (en) | 2010-07-29 | 2013-09-03 | Liquid Light, Inc. | Electrochemical production of urea from NOx and carbon dioxide |
US9062388B2 (en) | 2010-08-19 | 2015-06-23 | International Business Machines Corporation | Method and apparatus for controlling and monitoring the potential |
US8389178B2 (en) | 2010-09-10 | 2013-03-05 | U.S. Department Of Energy | Electrochemical energy storage device based on carbon dioxide as electroactive species |
JP2013544957A (en) | 2010-09-24 | 2013-12-19 | デット ノルスケ ベリタス エーエス | Method and apparatus for electrochemical reduction of carbon dioxide |
WO2012046362A1 (en) | 2010-10-06 | 2012-04-12 | パナソニック株式会社 | Method for reducing carbon dioxide |
US8568581B2 (en) | 2010-11-30 | 2013-10-29 | Liquid Light, Inc. | Heterocycle catalyzed carbonylation and hydroformylation with carbon dioxide |
US8961774B2 (en) | 2010-11-30 | 2015-02-24 | Liquid Light, Inc. | Electrochemical production of butanol from carbon dioxide and water |
US9090976B2 (en) | 2010-12-30 | 2015-07-28 | The Trustees Of Princeton University | Advanced aromatic amine heterocyclic catalysts for carbon dioxide reduction |
WO2012096987A1 (en) | 2011-01-11 | 2012-07-19 | Calera Corporation | Systems and methods for soda ash production |
JP6021074B2 (en) | 2011-02-28 | 2016-11-02 | 国立大学法人長岡技術科学大学 | Carbon dioxide reduction and fixation system, carbon dioxide reduction and fixation method, and method for producing useful carbon resources |
US8562811B2 (en) | 2011-03-09 | 2013-10-22 | Liquid Light, Inc. | Process for making formic acid |
CN102190573B (en) * | 2011-03-30 | 2013-11-27 | 昆明理工大学 | Method for preparing formic acid through electrochemical catalytic reduction of carbon dioxide |
SA112330516B1 (en) | 2011-05-19 | 2016-02-22 | كاليرا كوربوريشن | Electrochemical hydroxide systems and methods using metal oxidation |
US9551076B2 (en) | 2011-05-31 | 2017-01-24 | Clean Chemistry, Inc. | Electrochemical reactor and process |
WO2013006711A1 (en) | 2011-07-06 | 2013-01-10 | Liquid Light, Inc. | Reduction of carbon dioxide to carboxylic acids, glycols, and carboxylates |
CN103348039A (en) | 2011-08-31 | 2013-10-09 | 松下电器产业株式会社 | Method for reducing carbon dioxide |
US8641885B2 (en) | 2012-07-26 | 2014-02-04 | Liquid Light, Inc. | Multiphase electrochemical reduction of CO2 |
US8647493B2 (en) | 2012-07-26 | 2014-02-11 | Liquid Light, Inc. | Electrochemical co-production of chemicals employing the recycling of a hydrogen halide |
US20130105304A1 (en) | 2012-07-26 | 2013-05-02 | Liquid Light, Inc. | System and High Surface Area Electrodes for the Electrochemical Reduction of Carbon Dioxide |
-
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- 2012-12-21 US US13/724,878 patent/US8647493B2/en active Active
- 2012-12-21 US US13/724,719 patent/US9303324B2/en active Active
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- 2013-04-16 US US13/863,988 patent/US9080240B2/en active Active
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-
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- 2016-04-01 US US15/089,126 patent/US20160355931A1/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2060880A (en) * | 1933-09-23 | 1936-11-17 | Du Pont | Process of producing ethylene glycol |
US3720591A (en) * | 1971-12-28 | 1973-03-13 | Texaco Inc | Preparation of oxalic acid |
US20040006246A1 (en) * | 2001-06-20 | 2004-01-08 | Sherman Jeffrey H. | Method and apparatus for synthesizing olefins, alcohols, ethers, and aldehydes |
Non-Patent Citations (2)
Title |
---|
Liansheng et al,Journal of South Central University Technology, Electrode Selection of Electrolysis with Membrane for Sodium Tungstate Solution, 1999, 6(2), pp. 107-110. * |
Zaragoza Dorwald, Side Reactions in Organic Synthesis, 2005, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, Preface. Pg. IX. * |
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US9080240B2 (en) | 2015-07-14 |
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