US20140124379A1 - Electrochemical Co-Production of Chemicals Employing the Recycling of a Hydrogen Halide - Google Patents
Electrochemical Co-Production of Chemicals Employing the Recycling of a Hydrogen Halide Download PDFInfo
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- US20140124379A1 US20140124379A1 US14/152,417 US201414152417A US2014124379A1 US 20140124379 A1 US20140124379 A1 US 20140124379A1 US 201414152417 A US201414152417 A US 201414152417A US 2014124379 A1 US2014124379 A1 US 2014124379A1
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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
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- 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
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- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts 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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- C25B3/00—Electrolytic production of organic compounds
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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
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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
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- 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 chemicals employing the recycling of a hydrogen halide.
- 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 may be stored for later use will be possible.
- the present disclosure includes a system and methods for producing a first product from a first region of an electrochemical cell having a cathode and a second product from a second region of the electrochemical cell having an anode.
- the method may include a step of contacting the first region with a catholyte comprising carbon dioxide.
- the method may include another step of contacting the second region with an anolyte comprising a recycled reactant.
- the method may include a step of applying an electrical potential between the anode and the cathode sufficient to produce a first product recoverable from the first region and a second product recoverable from the second region.
- the second product may be removed from the second region and introduced to a secondary reactor.
- the method may include forming the recycled reactant in the secondary reactor.
- FIG. 1 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 additional embodiment of the present disclosure.
- FIG. 3 is a block diagram of a system in accordance with an additional embodiment of the present disclosure.
- FIG. 4 is a block diagram of a system in accordance with an additional embodiment of the present disclosure.
- FIG. 5 is a flow diagram of a method of electrochemical co-production of products in accordance with an embodiment of the present disclosure
- FIG. 6 is a flow diagram of a method of electrochemical co-production of products in accordance with another embodiment of the present disclosure.
- FIG. 7 is a block diagram of a system in accordance with an additional embodiment of the present disclosure.
- FIG. 8 is a block diagram of a system in accordance with an additional embodiment of the present disclosure.
- the electrochemical co-production of products may include production of a first product, such as reduction of carbon dioxide to carbon-based products including one, two, three, and four carbon chemicals, at a cathode side of an electrochemical cell with co-production of a second product, such as a halide (e.g., X 2 , where X is F, Cl, Br, I, or mixtures thereof), at the anode of the electrochemical cell where the anolyte comprises a recycled reactant, where the recycled reactant is preferably HX.
- a first product such as reduction of carbon dioxide to carbon-based products including one, two, three, and four carbon chemicals
- a second product such as a halide (e.g., X 2 , where X is F, Cl, Br, I, or mixtures thereof)
- a halide e.g., X 2 , where X is F, Cl, Br, I, or mixtures thereof
- System (or apparatus) 100 generally includes an electrochemical cell (also referred as a container, electrolyzer, or cell) 102 , a carbon dioxide source 104 , a secondary reactor 106 , a carbon-based reactant source 108 , a first product extractor 110 (configured to extract a first product 112 ), a second product extractor 114 (configured to extract a second product 116 ), and an energy source 118 .
- electrochemical cell also referred as a container, electrolyzer, or cell
- carbon dioxide source 104 also referred as a container, electrolyzer, or cell
- secondary reactor 106 a carbon-based reactant source 108
- first product extractor 110 configured to extract a first product 112
- second product extractor 114 configured to extract a second product 116
- an energy source 118 energy source
- 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 120 and a second region 122 .
- First region 120 and second region 122 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 120 may include a cathode 124 .
- Second region 122 may include an anode 126 .
- First region 120 may include a catholyte whereby carbon dioxide is dissolved in the catholyte.
- Second region 122 may include an anolyte which may include a recycled reactant (e.g., HX, where X is F, Cl, Br, I and mixtures thereof).
- a source of HX may be operably connected to second region 122 .
- Energy source 118 may generate an electrical potential between the anode 126 and the cathode 124 . The electrical potential may be a DC voltage.
- Energy source 118 may be configured to supply a variable voltage or constant current to electrochemical cell 102 .
- a separator 128 may selectively control a flow of ions between the first region 120 and the second region 122 .
- Separator 128 may include an ion conducting membrane or diaphragm material.
- Electrochemical cell 102 is generally operational to reduce carbon dioxide in the first region 120 to a first product 112 recoverable from the first region 120 while producing a second product 116 recoverable from the second region 122 .
- Cathode 124 may reduce the carbon dioxide into the first product 112 that may include one or more compounds.
- Examples of the first product 112 recoverable from the first region 120 by the first product extractor 110 may include carbon monoxide, formic acid, formaldehyde, methanol, methane, oxalate, oxalic acid, glyoxylic acid, glyoxylate, glycolic acid, glycolate, glyoxal, glycolaldehyde, ethylene glycol, acetic acid, acetate, acetaldehyde, ethanol, ethane, ethylene, lactic acid, lactate, propanoic acid, propionate, acetone, isopropanol, 1-propanol, 1,2-propylene glycol, propane, propylene, 1-butanol, 2-butanone, 2-butanol, butane, butene, a carboxylic acid, a carboxylate, a ketone, an aldehyde, and an alcohol.
- Carbon dioxide source 104 may provide carbon dioxide to the first region 120 of electrochemical cell 102 .
- the carbon dioxide is introduced directly into the region 120 containing the cathode 124 .
- carbon dioxide source 104 may include a source of a mixture of gases in which carbon dioxide has been separated and filtered from the gas mixture.
- First product extractor 110 may include an organic product and/or inorganic product extractor.
- First product extractor 110 is generally operational to extract (separate) the first product 112 from the first region 120 .
- the extracted first product 112 may be presented through a port of the system 100 for subsequent storage and/or consumption by other devices and/or processes.
- the anode side of the reaction occurring in the second region 122 may include a recycled reactant 130 , may be a gas phase, liquid phase, or solution phase reactant, supplied to the second region 122 .
- the second product 116 recoverable from the second region 122 may be derived from the oxidation of HX.
- Second product extractor 114 may extract the second product 116 from the second region 122 . Examples of the second product 116 recoverable from the second region 122 by the second product extractor 114 may include F 2 , Cl 2 , Br 2 , and I 2 , and mixtures thereof.
- the extracted second product 116 may be presented through a port of the system 100 for subsequent storage and/or consumption by other devices and/or processes. It is contemplated that first product extractor 110 and/or second product extractor 114 may be implemented with electrochemical cell 102 , or may be remotely located from the electrochemical cell 102 . Additionally, it is contemplated that first product extractor 110 and/or second product extractor 114 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.
- second product 116 may be presented to another reactor, such as a secondary reactor 106 , where the recycled reactant 130 is a product of a reaction of the second product 116 recovered from the second region 118 of the electrochemical cell 102 with a carbon-based reactant from the carbon-based reactant source 108 .
- the secondary reactor 106 may include the carbon-based reactant therein to react with the second product 116 .
- the carbon-based reactant may include, for example, an alkane, an alkene, an aromatic, or another organic compound.
- a third product 132 produced by secondary reactor 106 as an additional product of a reaction at secondary reactor 106 may include a halogenated organic compound or halogenated intermediate that may be further converted to another product.
- Recycled reactant 130 may be recycled back to the second region 122 as an input feed to the second region 122 of electrochemical cell 102 . It is contemplated that an additional source of recycled reactant may be further supplied as an input feed to the second region 122 of the electrochemical cell 102 without departing from the scope and intent of the present disclosure.
- electrochemical cell 102 may be capable of simultaneously producing two or more products with high selectivity.
- the organic chemical partially oxidized in the reaction may serve as the source of hydrogen for the reduction of carbon dioxide.
- 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 may be employed to partially oxidize an organic and provide hydrogen halide which may be recycled to the electrochemical cell 102 and used for the reduction of CO 2 .
- a preferred embodiment of the present disclosure may include production of organic chemicals, such as carbon dioxide reduction products, at the cathode while simultaneously using a hydrogen halide feed to the anode for production of X 2 , which is subsequently used to generate additional products.
- organic chemicals such as carbon dioxide reduction products
- FIG. 2A a system 200 for co-production of a carbon dioxide reduction product 202 and a fourth product 138 , preferably one or more of an alkene, an alcohol, and an olefin, is shown. Examples of some possible fourth products and the organic compound from which they are derived are in Table 1 below.
- the oxidation of the recycled reactant 130 preferably HX, where X is F, Cl, Br, I, and mixtures thereof, in the second region 122 produces protons and electrons that are utilized to reduce carbon dioxide in the first region 120 .
- the oxidation of the recycled reactant 130 may produce the second product 116 , which is preferably X 2 , which may be reacted in the secondary reactor 106 to selectively produce the third product 132 , preferably a halogenated compound.
- the third product 132 may be isolated or it may be supplied to a third reactor 134 for additional reactions to generate a fourth product 138 and the recycled reactant 130 .
- Third reactor 134 may include a feed of water, or hydroxide ion, 136 to produce an alkene or alcohol and the recycled reactant 130 .
- the third reactor 134 does not receive water, or hydroxide ion, as a reactant and instead produces the recycled reactant and one or more of an alkyne and an alkene.
- the recycled reactant 130 formed in the third reactor 134 may be recycled back to the second region 122 as an input feed to the second region 122 of electrochemical cell 102 either as a pure anhydrous gas or in a liquid phase.
- FIG. 2B a block diagram of a system 200 in accordance with an additional embodiment of the present disclosure is shown. Similar to the embodiment shown in FIG. 2A , FIG. 2B is a block diagram of a system in accordance with an additional embodiment of the present disclosure wherein the recycled reactant 130 is hydrogen bromide (HBr) 202 , the second product 116 is Br 2 204 , the third product 132 is bromoethane 206 , and the fourth product 138 is ethanol 208 .
- Bromine (Br 2 ) may be supplied to secondary reactor 106 and reacted with ethane 210 to produce HBr 202 , which is recycled as an input feed to the second region 122 , and bromoethane 206 .
- Bromoethane 206 may be supplied to third reactor 134 and reacted with water from water source 136 to produce HBr 202 , which is recycled as an input feed to the second region 122 , and ethanol 208 .
- water is not reacted in third reactor 134 , and the bromoethane 206 is reacted to produce HBr 202 and one or more of an alkyne or an alkene such as ethylene.
- the carbon dioxide reduction product of FIG. 2B preferably includes one or more of acetate and acetic acid 212 .
- the carbon dioxide reduction product is acetic acid and when ethanol 208 is produced in third reactor 134 , then the molar ratios of the product may be 1 acetic acid:4 ethanol because acetic acid production from CO 2 is an 8 electron process and ethanol from ethane is a two electron process.
- the mass ratios may be 1:3.
- Systems 300 , 400 provide additional embodiments to systems 100 , 200 of FIGS. 1-2 to co-produce a first product and second product.
- first region 120 of electrochemical cell 102 may produce a first product of H 2 310 which is combined with carbon dioxide 332 in a reactor 330 which may perform a reverse water gas shift reaction.
- This reverse water gas shift reaction performed by reactor 330 may produce water 334 and carbon monoxide 336 .
- Carbon monoxide 336 along with H 2 310 may be combined at second reactor 338 .
- Reactor 338 may cause a reaction by utilizing H 2 310 from the first region 120 of the electrochemical cell 102 , such as a Fischer-Tropsch-type reaction, to reduce carbon monoxide to a product 340 .
- Product 340 may include methane, methanol, hydrocarbons, glycols, and olefins.
- Second reactor 338 may also include transition metals such as iron, cobalt, and ruthenium as well as other transition metal oxides as catalysts, on inorganic support structures that may promote the reaction of CO with hydrogen at lower temperatures and pressures.
- Second region 122 may co-produce X 2 342 , where X is F, Cl, Br, I, and mixtures thereof.
- the X 2 is Br 2 .
- the X 2 342 may be introduced to the third reactor 106 , which may have a feed input of an alkane, an alkene, an alkyne, and an aromatic compound 344 , for production of a halogenated compound 312 .
- the alkane 344 is ethane and the halogenated compound 312 is bromoethane.
- Halogenated compound 312 may be isolated, or may be supplied to a fourth reactor 314 to generate products such as an alkene 318 and a hydrogen halide recycled reactant 320 , which is recycled back as an input feed to the second region 122 .
- the alkene 318 is ethylene and the hydrogen halide recycled reactant 320 is hydrogen bromide (HBr).
- alkane 344 may be other types of carbon-based reactants, including various types of alkanes, alkenes, or aromatic compounds while halogenated compound 312 may also refer to any type of halogenated compound that may be supplied to a fourth reactor 314 to produce various types of alkenes, alcohols, aldehydes, ketones, glycols, or olefins without departing from the scope or intent of the present disclosure.
- first region 120 of electrochemical cell 102 may produce a first product of carbon monoxide 410 which is combined with water 432 in a reactor 430 which may perform a water gas shift reaction.
- This water gas shift reaction performed by reactor 430 may produce carbon dioxide 434 and H 2 436 .
- Carbon monoxide 410 and H 2 436 may be combined at second reactor 438 .
- Second reactor 438 may cause a reaction, such as a Fischer-Tropsch-type reaction, to reduce carbon monoxide to a product 440 .
- Product 440 may include methane, methanol, hydrocarbons, glycols, or olefins by utilizing H 2 436 from the water gas shift reaction.
- Carbon dioxide 434 may be a byproduct of water gas shift reaction of reactor 430 and may be recycled as an input feed to the first region 120
- Water 406 which may include a hydrogen halide, may be an additional product produced by the first region 120 and may be recycled as another input feed to the first region 120 .
- Second reactor 438 may also include transition metals and their oxides, such as iron and copper oxides as catalysts, on inorganic support structures that may promote the reaction of CO with hydrogen at lower temperatures and pressures.
- Second region 122 may co-produce X 2 442 , where X is F, Cl, Br, I and mixtures thereof.
- the X 2 is Br 2 .
- the X 2 442 may be introduced to the third reactor 106 , which may have a feed input of an alkane, an alkene, an alkyne, and an aromatic compound 444 , for production of a halogenated compound 412 .
- an alkane 444 is ethane and the halogenated compound 412 is bromoethane.
- Halogenated compound 412 may be isolated, or may be supplied to a fourth reactor 414 to generate byproducts such as an alkene 418 and a hydrogen halide recycled reactant 420 , which is recycled back as an input feed to the second region 122 .
- the alkene 418 is ethylene and the hydrogen halide recycled reactant 420 is hydrogen bromide (HBr).
- alkane 444 may be other types of carbon-based reactants, including various types of alkanes, alkenes, or aromatic compounds while halogenated compound 412 may also refer to any type of halogenated compound that may be supplied to a fourth reactor 414 to produce various types of alkenes, alkynes, alcohols, aldehydes, ketones, glycols, or olefins without departing from the scope or intent of the present disclosure.
- reactions occurring at the first region 120 may occur in a catholyte which may include water, methanol, acetonitrile, propylene carbonate, ionic liquids, or other catholytes. They may also occur in the gas phase, though liquid phase may be preferred.
- the reactions occurring at the second region 122 may be in a gas phase or may occur in liquid phase, for example, in an aqueous or non-aqueous solution.
- the structure and operation of the electrochemical cell 102 may be adjusted to provide desired results.
- the electrochemical cell 102 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 124 and anode 126 may include a high surface area electrode structure 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 124 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 124 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 128 from directly touching the high surface area cathode structure.
- the high surface area cathode structure may be mechanically pressed or physically bonded against a cathode current distributor back plate, which may be composed of material that has the same surface composition as the high surface area cathode.
- cathode 124 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-GalnP 2 and p-Si, or an n-type semiconductor, such as n-GaAs, n-GaP, n-InN, n-InP, n-CdTe, n-GalnP 2 and n-Si.
- p-type semiconductor electrode such as p-GaAs, p-GaP, p-InN, p-InP, p-CdTe, n-GalnP 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 if an aqueous solvent or electrolyte is 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., 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.
- 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-dimethyla
- 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 or a non-aqueous 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, ⁇ -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 may 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 128 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 backpressure 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 may 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.
- Anode 126 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, bonded, 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 128 also referred to as a membrane, between first region 120 and second region 122 , may include cation ion exchange type membranes.
- Cation ion exchange membranes which have a 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 a 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 may also be used if the anion rejection is not as desirable, such as those sold by Sybron under their trade name Ionac®, 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.
- Method 500 may be performed by system 100 and system 200 as shown in FIGS. 1-2 .
- Method 500 may include producing a first product from a first region of an electrochemical cell having a cathode and a second product from a second region of the electrochemical cell having an anode.
- Method 500 of electrochemical co-production of products may include a step of contacting the first region with a catholyte comprising carbon dioxide 510 .
- method 500 may include contacting the second region with an anolyte comprising a recycled reactant 520 .
- Method 500 may further include applying an electrical potential between the anode and the cathode sufficient to produce a first product recoverable from the first region and a second product recoverable from the second region 530 .
- Method 500 may additionally include removing the second product from the second region 540 .
- Method 500 may additionally include introducing the second product to a secondary reactor 550 .
- method 500 may include forming the recycled reactant in the secondary reactor 560 .
- a first product produced at the first region may be recoverable from the first region and the recycled reactant produced in the secondary reactor may be recycled to the second region.
- Method 600 may be performed by system 100 and system 200 as shown in FIGS. 1-2 .
- Method 600 may include producing a first product from a first region of an electrochemical cell having a cathode and a second product from a second region of the electrochemical cell having an anode.
- Method 600 of electrochemical co-production of products may include a step of contacting the first region with a catholyte comprising carbon dioxide 610 .
- method 600 may include receiving a feed of a recycled reactant at the second region of the electrochemical cell, the recycled reactant is HX where X is selected from the group consisting of F, Cl, Br, I and mixtures thereof 620 .
- Method 600 may further include contacting the second region with an anolyte comprising the recycled reactant 630 .
- Method 600 may additionally include applying an electrical potential between the anode and the cathode sufficient to produce a first product recoverable from the first region and a diatomic halide product, X 2 , recoverable from the second region 640 .
- Method 600 may additionally include removing the diatomic halide product from the second region 650 . Further, method 600 may include introducing the diatomic halide product to a secondary reactor 660 . Method 600 may also include forming the recycled reactant in the secondary reactor 670 .
- a first product produced at the first region may be recoverable from the first region and the recycled reactant produced in the secondary reactor may be recycled to the second region.
- HBr is introduced to the second region 122 of a two compartment cell 102 having first region 120 and second region 122 that is separated by cation exchange membrane 128 .
- HBr may be circulated with a pump in an anolyte circulation loop where HBr may be converted to Br 2 as a gas or liquid in the second region, where H + ions crossing the membrane 128 into the first region 120 .
- Br 2 may be collected as a liquid stream containing HBr 3 , (i.e., bromine combined with HBr), which may serve as an oxidizer for the formation of bromoethane from the reaction of bromine with ethane in reactor 701 , which may then be converted to ethanol using a reaction with water or alkali hydroxide in reactor 702 .
- HBr 3 i.e., bromine combined with HBr
- carbon dioxide is reacted on a high surface area cathode to produce, in this example, sodium acetate.
- a circulation pump may be used to provide sufficient mass transfer to obtain a high Faradaic efficiency conversion to acetate.
- the product acetate overflows the catholyte loop, and may be converted to the acid form in the acidification unit using either an electrochemical acidification unit or by direct mixing with HBr and may be then purified and concentrated in a separate unit (not shown).
- the electrochemical cell may be operated at a current density of greater than 3 kA/m 2 (300 mA/cm 2 ), or in suitable range of 0.5 to 5 kA/m 2 or higher if needed.
- the current density of the formation of bromine from HBr may easily be operated at even higher current densities.
- the cell may be operated in a liquid phase in both the anode and cathode compartments, or in a preferred embodiment, may be liquid phase in the cathode compartment with a gas phase anode compartment wherein gas phase HBr is fed directly to the anode.
- the operating voltage of the system at a current density of 1 kA/m 2 may be between 1.0-2.5 volts, where the half cell voltage of anolyte reaction may be between 0.6V and 1.2V.
- the comparable cell voltage using a 1 M sulfuric acid anolyte with the formation of oxygen operating at 1 kA/m 2 may likely be between 2.0V and 4V.
- the HBr anolyte concentration may be in the range of 5 wt % to 50 wt %, more preferably in the range of 10 wt % to 40 wt %, and more preferably in the 15 wt % to 30 wt % range, with a corresponding 2 to 30 wt % bromine content as HBr 3 in the solution phase.
- the HBr content in the anolyte solution may control the anolyte solution conductivity, and thus the anolyte compartment IR voltage drop. If the anode is run with gas phase HBr, then HBr concentrations will approach 100% by wt % in anhydrous conditions.
- the anode may preferably include a polymeric bound carbon current distributor anode and incorporate a high surface area carbon felt with a specific surface area of 50 cm 2 /cm 3 or more that fills the gap between the cathode back plate and the membrane, thus having a zero gap anode.
- Metal and/or metal oxide catalysts may be added to the anode in order to decrease anode potential and/or increase anode current density.
- An example is the use of a RuO 2 catalyst.
- the cathode may also be a number of high surface area materials, which may include copper, stainless steels, carbon, and silicon, which may be further coated with a layer of material which may be a conductive metal or semiconductor.
- high surface area cathode structure is mechanically pressed against the cathode current distributor backplate, which may be composed of material that has the same surface composition as the high surface area cathode.
- the operating Faradaic current efficiency of the anode may preferably between 90 to 100%, and the acetate Faradaic current efficiency may preferably be between 25 and 100%.
- the flow circulation of the anolyte and catholyte may be such that it provides sufficient flow for the reactions.
- Br 2 produced at the anode in second region 122 may be reacted with ethane to make bromoethane and HBr.
- the bromoethane may then be reacted with water to form ethanol and HBr.
- the reaction product may contain up to 15% byproduct of dibromoethane (1,1 dibromoethane and/or 1,2 dibromoethane).
- These byproducts may be sold or chemically converted into a non-Br containing compound such as acetylene or acetaldehyde in order to reclaim the Br.
- These byproducts may also be catalytically converted into 1-bromoethane or hydrogenated back to ethane.
- the reaction of bromoethane to ethanol may be catalyzed by a base such as NaOH, by magnesium or similar metals that have a high affinity for Br, or by a zeolite containing metal reaction sites.
- a base such as NaOH
- magnesium or similar metals that have a high affinity for Br
- a zeolite containing metal reaction sites may be catalyzed by a base such as NaOH, by magnesium or similar metals that have a high affinity for Br, or by a zeolite containing metal reaction sites.
- the HBr byproduct from the reactors making bromoethane and ethanol may be recycled back to the anode portion of the cell. Br is thus conserved and H is made available for CO 2 reduction.
Abstract
Description
- The present application claims the benefit under 35 U.S.C. §120 of U.S. patent application Ser. No. 13/724,878 filed Dec. 21, 2012. The U.S. patent application Ser. No. 13/724,878 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. 61/703,229 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. 61/703,229 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. 13/724,878 filed Dec. 21, 2012 also claims the benefit under 35 U.S.C. §119(e) of 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. 61/703,231 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. 61/703,158 filed Sep. 19, 2012, U.S. Provisional Application Ser. No. 61/703,175 filed Sep. 19, 2012, U.S. Provisional Application Ser. No. 61/703,231 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 U.S. patent application Ser. No. 13/724,878 filed Dec. 21, 2012 incorporates by reference co-pending U.S. patent application Ser. No. 13/724,339, U.S. patent application Ser. No. 13/724,647, U.S. patent application Ser. No. 13/724,231, U.S. patent application Ser. No. 13/724,807, U.S. patent application Ser. No. 13/724,996, U.S. patent application Ser. No. 13/724,719, U.S. patent application Ser. No. 13/724,082, and U.S. patent application Ser. No. 13/724,768 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 chemicals employing the recycling of a hydrogen halide.
- 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 may be stored for later use will be possible.
- The present disclosure includes a system and methods for producing a first product from a first region of an electrochemical cell having a cathode and a second product from a second region of the electrochemical cell having an anode. The method may include a step of contacting the first region with a catholyte comprising carbon dioxide. The method may include another step of contacting the second region with an anolyte comprising a recycled reactant. The method may include a step of applying an electrical potential between the anode and the cathode sufficient to produce a first product recoverable from the first region and a second product recoverable from the second region. The second product may be removed from the second region and introduced to a secondary reactor. The method may include forming the recycled reactant in the secondary reactor.
- 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. 1 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 additional embodiment of the present disclosure; -
FIG. 3 is a block diagram of a system in accordance with an additional embodiment of the present disclosure; -
FIG. 4 is a block diagram of a system in accordance with an additional embodiment of the present disclosure; -
FIG. 5 is a flow diagram of a method of electrochemical co-production of products in accordance with an embodiment of the present disclosure; -
FIG. 6 is a flow diagram of a method of electrochemical co-production of products in accordance with another embodiment of the present disclosure; -
FIG. 7 is a block diagram of a system in accordance with an additional embodiment of the present disclosure; and -
FIG. 8 is a block diagram of a system in accordance with an 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.
- Referring generally to
FIGS. 1-8 , systems and methods of electrochemical co-production of products with a recycled halogen halide fed to an anode are disclosed. It is contemplated that the electrochemical co-production of products may include production of a first product, such as reduction of carbon dioxide to carbon-based products including one, two, three, and four carbon chemicals, at a cathode side of an electrochemical cell with co-production of a second product, such as a halide (e.g., X2, where X is F, Cl, Br, I, or mixtures thereof), at the anode of the electrochemical cell where the anolyte comprises a recycled reactant, where the recycled reactant is preferably HX. - Before any embodiments of the disclosure are explained in detail, it is to be understood that the embodiments may not be limited in application per the details of the structure or the function as set forth in the following descriptions or illustrated in the figures. Different embodiments may be capable of being practiced or carried out in various ways. Also, it is to be understood that the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. The use of terms such as “including,” “comprising,” or “having” and variations thereof herein are generally meant to encompass the item listed thereafter and equivalents thereof as well as additional items. Further, unless otherwise noted, technical terms may be used according to conventional usage. It is further contemplated that like reference numbers may describe similar components and the equivalents thereof.
- Referring to
FIG. 1 , a block diagram of asystem 100 in accordance with an embodiment of the present disclosure is shown. System (or apparatus) 100 generally includes an electrochemical cell (also referred as a container, electrolyzer, or cell) 102, acarbon dioxide source 104, asecondary reactor 106, a carbon-basedreactant source 108, a first product extractor 110 (configured to extract a first product 112), a second product extractor 114 (configured to extract a second product 116), and anenergy source 118. -
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 120 and asecond region 122.First region 120 andsecond region 122 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 120 may include acathode 124.Second region 122 may include ananode 126.First region 120 may include a catholyte whereby carbon dioxide is dissolved in the catholyte.Second region 122 may include an anolyte which may include a recycled reactant (e.g., HX, where X is F, Cl, Br, I and mixtures thereof). A source of HX may be operably connected tosecond region 122.Energy source 118 may generate an electrical potential between theanode 126 and thecathode 124. The electrical potential may be a DC voltage.Energy source 118 may be configured to supply a variable voltage or constant current toelectrochemical cell 102. Aseparator 128 may selectively control a flow of ions between thefirst region 120 and thesecond region 122.Separator 128 may include an ion conducting membrane or diaphragm material. -
Electrochemical cell 102 is generally operational to reduce carbon dioxide in thefirst region 120 to afirst product 112 recoverable from thefirst region 120 while producing asecond product 116 recoverable from thesecond region 122.Cathode 124 may reduce the carbon dioxide into thefirst product 112 that may include one or more compounds. Examples of thefirst product 112 recoverable from thefirst region 120 by thefirst product extractor 110 may include carbon monoxide, formic acid, formaldehyde, methanol, methane, oxalate, oxalic acid, glyoxylic acid, glyoxylate, glycolic acid, glycolate, glyoxal, glycolaldehyde, ethylene glycol, acetic acid, acetate, acetaldehyde, ethanol, ethane, ethylene, lactic acid, lactate, propanoic acid, propionate, acetone, isopropanol, 1-propanol, 1,2-propylene glycol, propane, propylene, 1-butanol, 2-butanone, 2-butanol, butane, butene, a carboxylic acid, a carboxylate, a ketone, an aldehyde, and an alcohol. -
Carbon dioxide source 104 may provide carbon dioxide to thefirst region 120 ofelectrochemical cell 102. In some embodiments, the carbon dioxide is introduced directly into theregion 120 containing thecathode 124. It is contemplated thatcarbon dioxide source 104 may include a source of a mixture of gases in which carbon dioxide has been separated and filtered from the gas mixture. -
First product extractor 110 may include an organic product and/or inorganic product extractor.First product extractor 110 is generally operational to extract (separate) thefirst product 112 from thefirst region 120. The extractedfirst product 112 may be presented through a port of thesystem 100 for subsequent storage and/or consumption by other devices and/or processes. - The anode side of the reaction occurring in the
second region 122 may include arecycled reactant 130, may be a gas phase, liquid phase, or solution phase reactant, supplied to thesecond region 122. Thesecond product 116 recoverable from thesecond region 122 may be derived from the oxidation of HX.Second product extractor 114 may extract thesecond product 116 from thesecond region 122. Examples of thesecond product 116 recoverable from thesecond region 122 by thesecond product extractor 114 may include F2, Cl2, Br2, and I2, and mixtures thereof. - The extracted
second product 116 may be presented through a port of thesystem 100 for subsequent storage and/or consumption by other devices and/or processes. It is contemplated thatfirst product extractor 110 and/orsecond product extractor 114 may be implemented withelectrochemical cell 102, or may be remotely located from theelectrochemical cell 102. Additionally, it is contemplated thatfirst product extractor 110 and/orsecond product extractor 114 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. - Furthermore,
second product 116 may be presented to another reactor, such as asecondary reactor 106, where therecycled reactant 130 is a product of a reaction of thesecond product 116 recovered from thesecond region 118 of theelectrochemical cell 102 with a carbon-based reactant from the carbon-basedreactant source 108. For instance, thesecondary reactor 106 may include the carbon-based reactant therein to react with thesecond product 116. The carbon-based reactant may include, for example, an alkane, an alkene, an aromatic, or another organic compound. Athird product 132 produced bysecondary reactor 106 as an additional product of a reaction atsecondary reactor 106 may include a halogenated organic compound or halogenated intermediate that may be further converted to another product.Recycled reactant 130 may be recycled back to thesecond region 122 as an input feed to thesecond region 122 ofelectrochemical cell 102. It is contemplated that an additional source of recycled reactant may be further supplied as an input feed to thesecond region 122 of theelectrochemical cell 102 without departing from the scope and intent of the present disclosure. - Through the co-production of the
first product 112 and thesecond product 116, the overall energy requirement for making each of thefirst product 112 andsecond product 116 may be reduced by 50% or more. In addition,electrochemical cell 102 may be capable of simultaneously producing two or more products with high selectivity. The organic chemical partially oxidized in the reaction may serve as the source of hydrogen for the reduction of carbon dioxide. 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 may be employed to partially oxidize an organic and provide hydrogen halide which may be recycled to theelectrochemical cell 102 and used for the reduction of CO2. - A preferred embodiment of the present disclosure may include production of organic chemicals, such as carbon dioxide reduction products, at the cathode while simultaneously using a hydrogen halide feed to the anode for production of X2, which is subsequently used to generate additional products. Referring to
FIG. 2A , asystem 200 for co-production of a carbondioxide reduction product 202 and afourth product 138, preferably one or more of an alkene, an alcohol, and an olefin, is shown. Examples of some possible fourth products and the organic compound from which they are derived are in Table 1 below. The oxidation of therecycled reactant 130, preferably HX, where X is F, Cl, Br, I, and mixtures thereof, in thesecond region 122 produces protons and electrons that are utilized to reduce carbon dioxide in thefirst region 120. The oxidation of therecycled reactant 130 may produce thesecond product 116, which is preferably X2, which may be reacted in thesecondary reactor 106 to selectively produce thethird product 132, preferably a halogenated compound. Thethird product 132 may be isolated or it may be supplied to athird reactor 134 for additional reactions to generate afourth product 138 and therecycled reactant 130.Third reactor 134 may include a feed of water, or hydroxide ion, 136 to produce an alkene or alcohol and therecycled reactant 130. - Alternatively, the
third reactor 134 does not receive water, or hydroxide ion, as a reactant and instead produces the recycled reactant and one or more of an alkyne and an alkene. Therecycled reactant 130 formed in thethird reactor 134 may be recycled back to thesecond region 122 as an input feed to thesecond region 122 ofelectrochemical cell 102 either as a pure anhydrous gas or in a liquid phase. -
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 - Referring to
FIG. 2B , a block diagram of asystem 200 in accordance with an additional embodiment of the present disclosure is shown. Similar to the embodiment shown inFIG. 2A ,FIG. 2B is a block diagram of a system in accordance with an additional embodiment of the present disclosure wherein therecycled reactant 130 is hydrogen bromide (HBr) 202, thesecond product 116 isBr 2 204, thethird product 132 isbromoethane 206, and thefourth product 138 isethanol 208. Bromine (Br2) may be supplied tosecondary reactor 106 and reacted withethane 210 to produceHBr 202, which is recycled as an input feed to thesecond region 122, andbromoethane 206.Bromoethane 206 may be supplied tothird reactor 134 and reacted with water fromwater source 136 to produceHBr 202, which is recycled as an input feed to thesecond region 122, andethanol 208. In another embodiment of the disclosure, water is not reacted inthird reactor 134, and thebromoethane 206 is reacted to produceHBr 202 and one or more of an alkyne or an alkene such as ethylene. The carbon dioxide reduction product ofFIG. 2B preferably includes one or more of acetate andacetic acid 212. When the carbon dioxide reduction product is acetic acid and whenethanol 208 is produced inthird reactor 134, then the molar ratios of the product may be 1 acetic acid:4 ethanol because acetic acid production from CO2 is an 8 electron process and ethanol from ethane is a two electron process. The mass ratios may be 1:3. - Referring to
FIGS. 3 and 4 with block diagrams ofsystems Systems systems FIGS. 1-2 to co-produce a first product and second product. - Referring specifically to
FIG. 3 ,first region 120 ofelectrochemical cell 102 may produce a first product ofH 2 310 which is combined withcarbon dioxide 332 in areactor 330 which may perform a reverse water gas shift reaction. This reverse water gas shift reaction performed byreactor 330 may producewater 334 and carbon monoxide 336. Carbon monoxide 336 along withH 2 310 may be combined atsecond reactor 338.Reactor 338 may cause a reaction by utilizingH 2 310 from thefirst region 120 of theelectrochemical cell 102, such as a Fischer-Tropsch-type reaction, to reduce carbon monoxide to aproduct 340.Product 340 may include methane, methanol, hydrocarbons, glycols, and olefins.Water 306, which may include a hydrogen halide, may be an additional product produced by thefirst region 120 and may be recycled as an input feed to thefirst region 120.Second reactor 338 may also include transition metals such as iron, cobalt, and ruthenium as well as other transition metal oxides as catalysts, on inorganic support structures that may promote the reaction of CO with hydrogen at lower temperatures and pressures. -
Second region 122 may co-produceX 2 342, where X is F, Cl, Br, I, and mixtures thereof. In an embodiment, the X2 is Br2. TheX 2 342 may be introduced to thethird reactor 106, which may have a feed input of an alkane, an alkene, an alkyne, and anaromatic compound 344, for production of ahalogenated compound 312. In an embodiment, thealkane 344 is ethane and thehalogenated compound 312 is bromoethane.Halogenated compound 312 may be isolated, or may be supplied to afourth reactor 314 to generate products such as analkene 318 and a hydrogen haliderecycled reactant 320, which is recycled back as an input feed to thesecond region 122. In an embodiment, thealkene 318 is ethylene and the hydrogen haliderecycled reactant 320 is hydrogen bromide (HBr). It is contemplated thatalkane 344 may be other types of carbon-based reactants, including various types of alkanes, alkenes, or aromatic compounds whilehalogenated compound 312 may also refer to any type of halogenated compound that may be supplied to afourth reactor 314 to produce various types of alkenes, alcohols, aldehydes, ketones, glycols, or olefins without departing from the scope or intent of the present disclosure. - Referring to
FIG. 4 ,first region 120 ofelectrochemical cell 102 may produce a first product ofcarbon monoxide 410 which is combined withwater 432 in areactor 430 which may perform a water gas shift reaction. This water gas shift reaction performed byreactor 430 may producecarbon dioxide 434 andH 2 436.Carbon monoxide 410 andH 2 436 may be combined atsecond reactor 438.Second reactor 438 may cause a reaction, such as a Fischer-Tropsch-type reaction, to reduce carbon monoxide to aproduct 440.Product 440 may include methane, methanol, hydrocarbons, glycols, or olefins by utilizingH 2 436 from the water gas shift reaction.Carbon dioxide 434 may be a byproduct of water gas shift reaction ofreactor 430 and may be recycled as an input feed to thefirst region 120Water 406, which may include a hydrogen halide, may be an additional product produced by thefirst region 120 and may be recycled as another input feed to thefirst region 120.Second reactor 438 may also include transition metals and their oxides, such as iron and copper oxides as catalysts, on inorganic support structures that may promote the reaction of CO with hydrogen at lower temperatures and pressures. -
Second region 122 may co-produceX 2 442, where X is F, Cl, Br, I and mixtures thereof. In an embodiment, the X2 is Br2. TheX 2 442 may be introduced to thethird reactor 106, which may have a feed input of an alkane, an alkene, an alkyne, and anaromatic compound 444, for production of ahalogenated compound 412. In an embodiment, analkane 444 is ethane and thehalogenated compound 412 is bromoethane.Halogenated compound 412 may be isolated, or may be supplied to afourth reactor 414 to generate byproducts such as analkene 418 and a hydrogen haliderecycled reactant 420, which is recycled back as an input feed to thesecond region 122. In an embodiment, thealkene 418 is ethylene and the hydrogen haliderecycled reactant 420 is hydrogen bromide (HBr). It is contemplated thatalkane 444 may be other types of carbon-based reactants, including various types of alkanes, alkenes, or aromatic compounds whilehalogenated compound 412 may also refer to any type of halogenated compound that may be supplied to afourth reactor 414 to produce various types of alkenes, alkynes, alcohols, aldehydes, ketones, glycols, or olefins without departing from the scope or intent of the present disclosure. - It is contemplated that reactions occurring at the
first region 120 may occur in a catholyte which may include water, methanol, acetonitrile, propylene carbonate, ionic liquids, or other catholytes. They may also occur in the gas phase, though liquid phase may be preferred. The reactions occurring at thesecond region 122 may be in a gas phase or may occur in liquid phase, for example, in an aqueous or non-aqueous solution. - It is further contemplated that the structure and operation of the
electrochemical cell 102 may be adjusted to provide desired results. For example, theelectrochemical cell 102 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 124 andanode 126 may include a high surface area electrode structure 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 124 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 124 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 128 from directly touching the high surface area cathode structure. The high surface area cathode structure may be mechanically pressed or physically bonded against a cathode current distributor back plate, which may be composed of material that has the same surface composition as the high surface area cathode. - In addition,
cathode 124 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-GalnP2 and p-Si, or an n-type semiconductor, such as n-GaAs, n-GaP, n-InN, n-InP, n-CdTe, n-GalnP2 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 if an aqueous solvent or electrolyte is 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 and acids such as NaBr, KBr, or HBr 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 or a non-aqueous 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, γ-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 may 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 128 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 backpressure 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 may 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.
Anode 126 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. For example, for HBr, acid anolytes, and oxidizing water generating oxygen, 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. For bromine and iodine anode chemistry, carbon and graphite are particularly suitable for use as anodes. Polymeric bonded carbon material may also be used. For other anolytes, comprising alkaline or hydroxide electrolytes, 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, bonded, or mechanically connected to a current distributor back plate that is commonly used in bipolar electrochemical cell assemblies. In addition, 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. In 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. For other anolytes comprising alkaline, or hydroxide electrolytes, anodes may include carbon, cobalt oxides, stainless steels, and their alloys and combinations. -
Separator 128, also referred to as a membrane, betweenfirst region 120 andsecond region 122, may include cation ion exchange type membranes. Cation ion exchange membranes, which have a 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 a 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 may also be used if the anion rejection is not as desirable, such as those sold by Sybron under their trade name Ionac®, 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. - Referring to
FIG. 5 a flow diagram of amethod 500 of electrochemical co-production of products in accordance with an embodiment of the present disclosure is shown. It is contemplated thatmethod 500 may be performed bysystem 100 andsystem 200 as shown inFIGS. 1-2 .Method 500 may include producing a first product from a first region of an electrochemical cell having a cathode and a second product from a second region of the electrochemical cell having an anode. -
Method 500 of electrochemical co-production of products may include a step of contacting the first region with a catholyte comprisingcarbon dioxide 510. Next,method 500 may include contacting the second region with an anolyte comprising arecycled reactant 520.Method 500 may further include applying an electrical potential between the anode and the cathode sufficient to produce a first product recoverable from the first region and a second product recoverable from thesecond region 530.Method 500 may additionally include removing the second product from thesecond region 540.Method 500 may additionally include introducing the second product to asecondary reactor 550. Further,method 500 may include forming the recycled reactant in thesecondary reactor 560. Advantageously, a first product produced at the first region may be recoverable from the first region and the recycled reactant produced in the secondary reactor may be recycled to the second region. - Referring to
FIG. 6 a flow diagram of amethod 600 of electrochemical co-production of products in accordance with an embodiment of the present disclosure is shown. It is contemplated thatmethod 600 may be performed bysystem 100 andsystem 200 as shown inFIGS. 1-2 .Method 600 may include producing a first product from a first region of an electrochemical cell having a cathode and a second product from a second region of the electrochemical cell having an anode. -
Method 600 of electrochemical co-production of products may include a step of contacting the first region with a catholyte comprisingcarbon dioxide 610. Next,method 600 may include receiving a feed of a recycled reactant at the second region of the electrochemical cell, the recycled reactant is HX where X is selected from the group consisting of F, Cl, Br, I andmixtures thereof 620.Method 600 may further include contacting the second region with an anolyte comprising therecycled reactant 630.Method 600 may additionally include applying an electrical potential between the anode and the cathode sufficient to produce a first product recoverable from the first region and a diatomic halide product, X2, recoverable from thesecond region 640.Method 600 may additionally include removing the diatomic halide product from thesecond region 650. Further,method 600 may include introducing the diatomic halide product to asecondary reactor 660.Method 600 may also include forming the recycled reactant in thesecondary reactor 670. Advantageously, a first product produced at the first region may be recoverable from the first region and the recycled reactant produced in the secondary reactor may be recycled to the second region. - Referring now to
FIG. 7 , an embodiment of anelectrochemical system 700 for the co-production of acetic acid and ethanol is shown. The overall equation for the desired reaction may be 2CO2+4C2H6+2H2O→CH3COOH+4C2H5OH. HBr is introduced to thesecond region 122 of a twocompartment cell 102 havingfirst region 120 andsecond region 122 that is separated bycation exchange membrane 128. HBr may be circulated with a pump in an anolyte circulation loop where HBr may be converted to Br2 as a gas or liquid in the second region, where H+ ions crossing themembrane 128 into thefirst region 120. Alternatively, Br2 may be collected as a liquid stream containing HBr3, (i.e., bromine combined with HBr), which may serve as an oxidizer for the formation of bromoethane from the reaction of bromine with ethane inreactor 701, which may then be converted to ethanol using a reaction with water or alkali hydroxide inreactor 702. - On the cathode side in
first region 120, carbon dioxide is reacted on a high surface area cathode to produce, in this example, sodium acetate. A circulation pump may be used to provide sufficient mass transfer to obtain a high Faradaic efficiency conversion to acetate. The product acetate overflows the catholyte loop, and may be converted to the acid form in the acidification unit using either an electrochemical acidification unit or by direct mixing with HBr and may be then purified and concentrated in a separate unit (not shown). - The electrochemical cell may be operated at a current density of greater than 3 kA/m2 (300 mA/cm2), or in suitable range of 0.5 to 5 kA/m2 or higher if needed. The current density of the formation of bromine from HBr may easily be operated at even higher current densities. The cell may be operated in a liquid phase in both the anode and cathode compartments, or in a preferred embodiment, may be liquid phase in the cathode compartment with a gas phase anode compartment wherein gas phase HBr is fed directly to the anode.
- The operating voltage of the system at a current density of 1 kA/m2 may be between 1.0-2.5 volts, where the half cell voltage of anolyte reaction may be between 0.6V and 1.2V. In comparison, the comparable cell voltage using a 1 M sulfuric acid anolyte with the formation of oxygen operating at 1 kA/m2 may likely be between 2.0V and 4V.
- In the case of a liquid anolyte, the HBr anolyte concentration may be in the range of 5 wt % to 50 wt %, more preferably in the range of 10 wt % to 40 wt %, and more preferably in the 15 wt % to 30 wt % range, with a corresponding 2 to 30 wt % bromine content as HBr3 in the solution phase. The HBr content in the anolyte solution may control the anolyte solution conductivity, and thus the anolyte compartment IR voltage drop. If the anode is run with gas phase HBr, then HBr concentrations will approach 100% by wt % in anhydrous conditions.
- The anode may preferably include a polymeric bound carbon current distributor anode and incorporate a high surface area carbon felt with a specific surface area of 50 cm2/cm3 or more that fills the gap between the cathode back plate and the membrane, thus having a zero gap anode. Metal and/or metal oxide catalysts may be added to the anode in order to decrease anode potential and/or increase anode current density. An example is the use of a RuO2 catalyst.
- The cathode may also be a number of high surface area materials, which may include copper, stainless steels, carbon, and silicon, which may be further coated with a layer of material which may be a conductive metal or semiconductor. There is a very thin plastic screen against the cathode side of the membrane to prevent the membrane from touching the high surface area cathode structure. The high surface area cathode structure is mechanically pressed against the cathode current distributor backplate, which may be composed of material that has the same surface composition as the high surface area cathode.
- The operating Faradaic current efficiency of the anode may preferably between 90 to 100%, and the acetate Faradaic current efficiency may preferably be between 25 and 100%. The flow circulation of the anolyte and catholyte may be such that it provides sufficient flow for the reactions.
- Br2 produced at the anode in
second region 122 may be reacted with ethane to make bromoethane and HBr. The bromoethane may then be reacted with water to form ethanol and HBr. Though high selectivity for bromoethane may be generally observed, the reaction product may contain up to 15% byproduct of dibromoethane (1,1 dibromoethane and/or 1,2 dibromoethane). These byproducts may be sold or chemically converted into a non-Br containing compound such as acetylene or acetaldehyde in order to reclaim the Br. These byproducts may also be catalytically converted into 1-bromoethane or hydrogenated back to ethane. The reaction of bromoethane to ethanol may be catalyzed by a base such as NaOH, by magnesium or similar metals that have a high affinity for Br, or by a zeolite containing metal reaction sites. The HBr byproduct from the reactors making bromoethane and ethanol may be recycled back to the anode portion of the cell. Br is thus conserved and H is made available for CO2 reduction.
Claims (9)
Priority Applications (1)
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US14/152,417 US20140124379A1 (en) | 2012-07-26 | 2014-01-10 | Electrochemical Co-Production of Chemicals Employing the Recycling of a Hydrogen Halide |
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US201261675938P | 2012-07-26 | 2012-07-26 | |
US201261703158P | 2012-09-19 | 2012-09-19 | |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10987624B2 (en) | 2016-12-21 | 2021-04-27 | Isca Management Ltd. | Removal of greenhouse gases and heavy metals from an emission stream |
Families Citing this family (94)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010088524A2 (en) | 2009-01-29 | 2010-08-05 | Princeton University | Conversion of carbon dioxide to organic products |
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 |
US8500987B2 (en) | 2010-03-19 | 2013-08-06 | Liquid Light, Inc. | Purification of carbon dioxide from a mixture of gases |
US10047446B2 (en) * | 2010-07-04 | 2018-08-14 | Dioxide Materials, Inc. | Method and system for electrochemical production of formic acid from carbon dioxide |
US8592633B2 (en) | 2010-07-29 | 2013-11-26 | Liquid Light, Inc. | Reduction of carbon dioxide to carboxylic acids, glycols, and carboxylates |
US8845878B2 (en) | 2010-07-29 | 2014-09-30 | Liquid Light, Inc. | Reducing carbon dioxide to products |
US8961774B2 (en) | 2010-11-30 | 2015-02-24 | Liquid Light, Inc. | Electrochemical production of butanol from carbon dioxide and water |
US8568581B2 (en) | 2010-11-30 | 2013-10-29 | Liquid Light, Inc. | Heterocycle catalyzed carbonylation and hydroformylation with carbon dioxide |
US9090976B2 (en) | 2010-12-30 | 2015-07-28 | The Trustees Of Princeton University | Advanced aromatic amine heterocyclic catalysts for carbon dioxide reduction |
AU2012278948A1 (en) | 2011-07-06 | 2014-01-16 | Liquid Light, Inc. | Carbon dioxide capture and conversion to organic products |
US9267212B2 (en) | 2012-07-26 | 2016-02-23 | Liquid Light, Inc. | Method and system for production of oxalic acid and oxalic acid reduction products |
US9175407B2 (en) | 2012-07-26 | 2015-11-03 | Liquid Light, Inc. | Integrated process for producing carboxylic acids from carbon dioxide |
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 |
WO2015195149A1 (en) * | 2014-06-19 | 2015-12-23 | Liquid Light, Inc | Integrated process for co-production of carboxylic acids and halogen products from carbon dioxide |
US8641885B2 (en) | 2012-07-26 | 2014-02-04 | Liquid Light, Inc. | Multiphase electrochemical reduction of CO2 |
US8821709B2 (en) | 2012-07-26 | 2014-09-02 | Liquid Light, Inc. | System and method for oxidizing organic compounds while reducing carbon dioxide |
US20130105304A1 (en) | 2012-07-26 | 2013-05-02 | Liquid Light, Inc. | System and High Surface Area Electrodes for the Electrochemical Reduction of 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 |
CN104640816A (en) * | 2012-09-19 | 2015-05-20 | 液体光有限公司 | 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 |
WO2014138272A1 (en) * | 2013-03-06 | 2014-09-12 | Ceramatec, Inc. | Production of valuable chemicals by electroreduction of carbon dioxide in a nasicon cell |
CA2907015C (en) * | 2013-03-15 | 2018-02-20 | Arturo Solis Herrera | Electrochemical process 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 |
US10815576B2 (en) * | 2013-11-20 | 2020-10-27 | University Of Florida Research Foundation, Incorporated | Carbon dioxide reduction over carbon-containing materials |
WO2015146014A1 (en) * | 2014-03-24 | 2015-10-01 | 株式会社 東芝 | Photoelectrochemical reaction system |
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 |
WO2016136433A1 (en) * | 2015-02-27 | 2016-09-01 | 国立研究開発法人科学技術振興機構 | Electrochemical reduction of carbon dioxide |
US11788193B2 (en) * | 2015-05-05 | 2023-10-17 | Ohio University | Electrochemical cells and 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 |
CN108140862B (en) * | 2015-07-08 | 2021-07-20 | 阿戈拉能量技术有限公司 | 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 |
US10648091B2 (en) | 2016-05-03 | 2020-05-12 | Opus 12 Inc. | Reactor with advanced architecture for the electrochemical reaction of CO2, 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 |
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 |
EP3649278A1 (en) * | 2017-07-03 | 2020-05-13 | Covestro Deutschland AG | Electrochemical process for synthesizing diaryl carbonates |
WO2019051268A1 (en) * | 2017-09-07 | 2019-03-14 | The Trustees Of Princeton University | Binary alloys and oxides thereof for electrocatalytic reduction of carbon dioxide |
WO2019070526A1 (en) * | 2017-10-02 | 2019-04-11 | 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 |
US20210395857A1 (en) * | 2018-10-23 | 2021-12-23 | 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 |
US11578415B2 (en) | 2018-11-28 | 2023-02-14 | 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 |
EP3899092A1 (en) | 2018-12-18 | 2021-10-27 | Opus 12 Incorporated | Electrolyzer and method of use |
WO2020139538A1 (en) * | 2018-12-29 | 2020-07-02 | 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 |
JP2023505051A (en) | 2019-11-25 | 2023-02-08 | トゥエルブ ベネフィット コーポレーション | Membrane electrode assembly for COx reduction |
US11001549B1 (en) * | 2019-12-06 | 2021-05-11 | Saudi Arabian Oil Company | Electrochemical reduction of carbon dioxide to upgrade hydrocarbon feedstocks |
EP4097276A1 (en) * | 2020-01-30 | 2022-12-07 | 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 |
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 |
WO2022246415A1 (en) * | 2021-05-20 | 2022-11-24 | Battelle Energy Alliance, Llc | Direct air capture reactor systems and related methods of capturing 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 |
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 |
WO2024035474A1 (en) | 2022-08-12 | 2024-02-15 | 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 (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3919114A (en) * | 1969-11-21 | 1975-11-11 | Texaco Development Corp | Synthesis gas process |
US3957962A (en) * | 1973-04-17 | 1976-05-18 | Shell Oil Company | Process for the preparation of hydrogen-rich gas |
US4011275A (en) * | 1974-08-23 | 1977-03-08 | Mobil Oil Corporation | Conversion of modified synthesis gas to oxygenated organic chemicals |
US4584390A (en) * | 1983-06-03 | 1986-04-22 | Henkel Kommanditgesellschaft Auf Aktien | Continuous process for the catalytic epoxidation of olefinic double bonds with hydrogen peroxide and formic acid |
US20120277465A1 (en) * | 2010-07-29 | 2012-11-01 | Liquid Light, Inc. | Reduction of carbon dioxide to carboxylic acids, glycols, and carboxylates |
Family Cites Families (220)
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 |
US2060880A (en) | 1933-09-23 | 1936-11-17 | Du Pont | Process of producing ethylene glycol |
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 |
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 |
BE791653A (en) | 1971-12-28 | 1973-05-21 | Texaco Development Corp | ELECTROLYTIC PROCESS FOR THE PREPARATION OF 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 |
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 | ||
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 |
EP0028430B1 (en) | 1979-11-01 | 1984-01-18 | Shell Internationale Researchmaatschappij B.V. | A process for the electroreductive preparation of organic compounds |
NO154094C (en) | 1980-01-07 | 1986-07-16 | Bush Boake Allen Ltd | PROCEDURE FOR THE PREPARATION OF HYDROXY COMPOUNDS WITH THE FORM OF ROH 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 |
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 |
ATE138904T1 (en) | 1989-01-17 | 1996-06-15 | Davy Process Techn Ltd | CONTINUOUS PROCESS FOR PRODUCING 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 |
EP0412175B1 (en) | 1989-08-07 | 1992-12-02 | European Atomic Energy Community (Euratom) | Method for removing nitrogen compounds from a liquid |
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 |
US5474658A (en) | 1992-02-22 | 1995-12-12 | Hoechst Ag | Electrochemical process for preparing 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 |
WO1997047052A1 (en) | 1996-06-05 | 1997-12-11 | 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 |
IL149742A0 (en) | 1999-11-22 | 2002-11-10 | Dow Chemical Co | A process for the conversion of ethylene to vinyl chloride, and novel catalyst compositions useful for such process |
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 |
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 |
KR100391845B1 (en) | 2000-02-11 | 2003-07-16 | 한국과학기술연구원 | Synthesis of Alkylene Carbonates using a Metal Halides Complex containing Pyridine Ligands |
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 |
TW574071B (en) | 2001-06-14 | 2004-02-01 | Rohm & Haas | Mixed metal oxide catalyst |
US7161050B2 (en) | 2001-06-20 | 2007-01-09 | Grt, Inc. | Method and apparatus for synthesizing olefins, alcohols, ethers, and aldehydes |
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 |
CA2496554A1 (en) | 2002-08-21 | 2004-10-07 | 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 |
US20070004023A1 (en) | 2003-05-19 | 2007-01-04 | 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 |
WO2005104275A1 (en) | 2004-04-22 | 2005-11-03 | Nippon Steel 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 |
WO2006074335A2 (en) | 2005-01-07 | 2006-07-13 | Combimatrix Corporation | Process for performing an isolated pd(0) catalyzed reaction electrochemically on an electrode array device |
WO2006110780A2 (en) * | 2005-04-12 | 2006-10-19 | 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 |
WO2007040259A1 (en) | 2005-10-05 | 2007-04-12 | Daiichi Sankyo Company, Limited | Method for dehydrohalogenation of organic halogen compound |
CA2625656C (en) | 2005-10-13 | 2014-12-09 | Mantra Energy Alternatives Ltd. | Continuous electro-chemical reduction of carbon dioxide |
US20090062110A1 (en) | 2006-02-08 | 2009-03-05 | Sumitomo Chemical Company Limited | Metal complex and use thereof |
ATE545456T1 (en) | 2006-04-27 | 2012-03-15 | Harvard College | CARBON DIOXIDE COLLECTION AND RELATED METHODS |
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 |
US20080245660A1 (en) | 2007-04-03 | 2008-10-09 | New Sky Energy, Inc. | Renewable energy system for hydrogen production and carbon dioxide capture |
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 |
JP2010527358A (en) | 2007-05-14 | 2010-08-12 | ジーアールティー インコーポレイテッド | Process for converting hydrocarbon feedstock 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 |
TW200920721A (en) | 2007-07-13 | 2009-05-16 | Solvay Fluor Gmbh | Preparation of halogen and hydrogen containing alkenes over metal fluoride catalysts |
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 |
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 |
US9142852B2 (en) | 2008-06-23 | 2015-09-22 | 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 |
WO2010088524A2 (en) | 2009-01-29 | 2010-08-05 | Princeton University | Conversion of carbon dioxide to organic products |
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 |
WO2010124041A1 (en) | 2009-04-22 | 2010-10-28 | Grt, Inc. | 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 |
BR112012013158A2 (en) | 2009-12-02 | 2016-03-01 | Univ Michigan State | method of producing an alkyl ester of a carboxylic acid and method for isolating diethyl succinate |
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 |
EP2529441B1 (en) | 2010-01-25 | 2016-05-04 | Ramot at Tel Aviv University, Ltd. | Method of manufacturing proton-conducting membranes |
WO2011094153A1 (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 |
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 |
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 |
US8884054B2 (en) | 2010-06-30 | 2014-11-11 | Uop Llc | Process for oxidizing alkyl aromatic compounds |
US8933265B2 (en) | 2010-06-30 | 2015-01-13 | Uop Llc | Process for oxidizing alkyl aromatic compounds |
US8845878B2 (en) | 2010-07-29 | 2014-09-30 | Liquid Light, Inc. | Reducing carbon dioxide to products |
US20130180865A1 (en) | 2010-07-29 | 2013-07-18 | 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 |
US9145615B2 (en) | 2010-09-24 | 2015-09-29 | Yumei Zhai | Method and apparatus for the 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 |
US8961774B2 (en) | 2010-11-30 | 2015-02-24 | Liquid Light, Inc. | Electrochemical production of butanol from carbon dioxide and water |
US8568581B2 (en) | 2010-11-30 | 2013-10-29 | Liquid Light, Inc. | Heterocycle catalyzed carbonylation and hydroformylation with carbon dioxide |
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 |
WO2012118065A1 (en) | 2011-02-28 | 2012-09-07 | 国立大学法人長岡技術科学大学 | System for reducing and immobilizing carbon dioxide, method for reducing and immobilizing carbon dioxide, 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 |
WO2012166997A2 (en) | 2011-05-31 | 2012-12-06 | Clean Chemistry, Llc | Electrochemical reactor and process |
JP5236125B1 (en) | 2011-08-31 | 2013-07-17 | パナソニック株式会社 | How to reduce carbon dioxide |
US8821709B2 (en) | 2012-07-26 | 2014-09-02 | Liquid Light, Inc. | System and method for oxidizing organic compounds while reducing carbon dioxide |
US8641885B2 (en) | 2012-07-26 | 2014-02-04 | Liquid Light, Inc. | Multiphase electrochemical reduction of CO2 |
US20130105304A1 (en) | 2012-07-26 | 2013-05-02 | Liquid Light, Inc. | System and High Surface Area Electrodes for the Electrochemical Reduction of Carbon Dioxide |
-
2012
- 2012-12-21 US US13/724,082 patent/US8821709B2/en active Active
- 2012-12-21 US US13/724,996 patent/US8691069B2/en active Active
- 2012-12-21 US US13/724,768 patent/US8444844B1/en active Active
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- 2013-04-16 US US13/863,988 patent/US9080240B2/en active Active
- 2013-09-25 US US14/036,571 patent/US20140034506A1/en not_active Abandoned
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- 2014-01-10 US US14/152,417 patent/US20140124379A1/en not_active Abandoned
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- 2014-08-27 US US14/470,700 patent/US20140367274A1/en not_active Abandoned
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2016
- 2016-04-01 US US15/089,126 patent/US20160355931A1/en not_active Abandoned
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3919114A (en) * | 1969-11-21 | 1975-11-11 | Texaco Development Corp | Synthesis gas process |
US3957962A (en) * | 1973-04-17 | 1976-05-18 | Shell Oil Company | Process for the preparation of hydrogen-rich gas |
US4011275A (en) * | 1974-08-23 | 1977-03-08 | Mobil Oil Corporation | Conversion of modified synthesis gas to oxygenated organic chemicals |
US4584390A (en) * | 1983-06-03 | 1986-04-22 | Henkel Kommanditgesellschaft Auf Aktien | Continuous process for the catalytic epoxidation of olefinic double bonds with hydrogen peroxide and formic acid |
US20120277465A1 (en) * | 2010-07-29 | 2012-11-01 | Liquid Light, Inc. | Reduction of carbon dioxide to carboxylic acids, glycols, and carboxylates |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10987624B2 (en) | 2016-12-21 | 2021-04-27 | Isca Management Ltd. | Removal of greenhouse gases and heavy metals from an emission stream |
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US20130134049A1 (en) | 2013-05-30 |
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US8647493B2 (en) | 2014-02-11 |
US20160355931A1 (en) | 2016-12-08 |
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US20130118910A1 (en) | 2013-05-16 |
US8444844B1 (en) | 2013-05-21 |
US20140194641A1 (en) | 2014-07-10 |
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