CA2579133A1 - Method for producing fuel from captured carbon dioxide - Google Patents
Method for producing fuel from captured carbon dioxide Download PDFInfo
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- CA2579133A1 CA2579133A1 CA002579133A CA2579133A CA2579133A1 CA 2579133 A1 CA2579133 A1 CA 2579133A1 CA 002579133 A CA002579133 A CA 002579133A CA 2579133 A CA2579133 A CA 2579133A CA 2579133 A1 CA2579133 A1 CA 2579133A1
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- fuel
- reaction
- khco3
- hydrogen
- fuel cell
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000000446 fuel Substances 0.000 title claims abstract description 52
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 50
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000011736 potassium bicarbonate Substances 0.000 claims abstract description 13
- 235000015497 potassium bicarbonate Nutrition 0.000 claims abstract description 13
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims abstract description 13
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims abstract description 13
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000008246 gaseous mixture Substances 0.000 claims abstract description 8
- 235000015320 potassium carbonate Nutrition 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 38
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 31
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000003487 electrochemical reaction Methods 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 230000005587 bubbling Effects 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 6
- -1 from the atmosphere Chemical compound 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000005431 greenhouse gas Substances 0.000 description 4
- 238000002407 reforming Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 235000011116 calcium hydroxide Nutrition 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001991 steam methane reforming Methods 0.000 description 2
- 229910010092 LiAlO2 Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/12—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—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 oxides of carbon exclusively
- C07C29/151—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 oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1516—Multisteps
- C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Inert Electrodes (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a method for producing combustible fuels from a gaseous mixture containing carbon dioxide, which comprises: (i) capturing CO2 from said gaseous mixture by means of K2CO3, thus forming KHCO3; (ii) releasing the CO2 from said KHCO3; and (iii) subsequently producing fuel from the released CO2 by reaction with hydrogen.
Description
METHOD FOR PRODUCING FUEL FROM CAPTURED CARBON
DIOXIDE
FIELD OF THE INVENTION
The present invention relates to a method for capturing carbon dioxide from a gaseous mixture containing carbon dioxide, e.g., from the atmosphere, and subsequently using this carbon dioxide for the production of fuel.
BACKGROUND OF THE INVENTION
Greenhouse gases include carbon dioxide, methane, nitrous oxide and water vapor. While greenhouse gases occur naturally in the atmosphere, human activities also produce greenhouse gas emissions and are responsible for creating new ones.
Carbon dioxide (C02) is the most common greenhouse gas released by human activities, resulting from the extensive use of fossil fuel (coal, petroleum, natural gas). One of the main challenges modem civilization is facing is the increase of carbon dioxide in the atmosphere, affecting the greenhouse effect and global warming. Another problem arises from the extensive use of fossil fuel thus diminishing the global fuel reserves.
Renewable energy sources, that capture their energy from existing flows of energy, from on-going natural processes, such as sunshine, wind, flowing water, biological processes and geothermal heat flows, can be used for generating electricity, and there is a growing demand for methods of producing fuel using electricity.
Numerous attempts for extracting CO2 directly from car exhausts or power plants have been made, most of them involving reactions of exhausted gases with organic amine compounds or strong bases like calcium hydroxide or sodium hydroxide. In processes using organic amines, a solution of amine and water is contacted with the gas, whereby the amine and the CO2 undergo a chemical reaction forming a rich amine that is soluble in the water. The rich amine solution is pumped to a desorber where it is heated, reversing the reaction and releasing pure CO2 gas.
The disadvantage of this method is the fact that organic amine bases are expensive and unstable.
Carbon dioxide and mixtures containing it have been proposed for production of combustible fuels. For example, US Patent No. 4,140,602 discloses a chemical method for combustible fuel production by converting carbon dioxide in the atmosphere to a carbonate such as an alkali carbonate, following which the recovered carbonate is combined with hydrogen gas to produce combustible fuels e.g. methane and methanol. The method includes the additional step of reacting the alkali carbonate with calcium hydroxide to form calcium carbonate. The disadvantages of this method resides in the use of the strong base compound Ca(OH)2, forming CaCO3, that requires considerable amount of energy for the thermal release of COZ.
SUMMARY OF THE INVENTION
The present invention relates to a method for producing combustible fuels from a gaseous mixture containing carbon dioxide, which comprises:
(i) capturing CO2 from said gaseous mixture by means of K2C03, thus forming KHCO3;
(ii) releasing the COZ from said KHCO3 ; and (iii) subsequently producing fuel from the released CO2 by reaction with hydrogen.
DETAILED DESCRIPTION OF THE INVENTION
The method of the present invention enables the production of combustible fuels, using as preferred starting material the highly available atmospheric carbon dioxide, and retuniulg the CO2 produced by fuel combustion to the atmosphere, thus maintaining the equilibrium of the CO2 in the atmosphere. The method is based on well known in the art reactions such as thermal catalytic and electrochemical reactions, utilizing the reversibility of these reactions and carrying out the reverse reaction by modifying the operating pressure and/or the electrical voltage supplied to the process.
DIOXIDE
FIELD OF THE INVENTION
The present invention relates to a method for capturing carbon dioxide from a gaseous mixture containing carbon dioxide, e.g., from the atmosphere, and subsequently using this carbon dioxide for the production of fuel.
BACKGROUND OF THE INVENTION
Greenhouse gases include carbon dioxide, methane, nitrous oxide and water vapor. While greenhouse gases occur naturally in the atmosphere, human activities also produce greenhouse gas emissions and are responsible for creating new ones.
Carbon dioxide (C02) is the most common greenhouse gas released by human activities, resulting from the extensive use of fossil fuel (coal, petroleum, natural gas). One of the main challenges modem civilization is facing is the increase of carbon dioxide in the atmosphere, affecting the greenhouse effect and global warming. Another problem arises from the extensive use of fossil fuel thus diminishing the global fuel reserves.
Renewable energy sources, that capture their energy from existing flows of energy, from on-going natural processes, such as sunshine, wind, flowing water, biological processes and geothermal heat flows, can be used for generating electricity, and there is a growing demand for methods of producing fuel using electricity.
Numerous attempts for extracting CO2 directly from car exhausts or power plants have been made, most of them involving reactions of exhausted gases with organic amine compounds or strong bases like calcium hydroxide or sodium hydroxide. In processes using organic amines, a solution of amine and water is contacted with the gas, whereby the amine and the CO2 undergo a chemical reaction forming a rich amine that is soluble in the water. The rich amine solution is pumped to a desorber where it is heated, reversing the reaction and releasing pure CO2 gas.
The disadvantage of this method is the fact that organic amine bases are expensive and unstable.
Carbon dioxide and mixtures containing it have been proposed for production of combustible fuels. For example, US Patent No. 4,140,602 discloses a chemical method for combustible fuel production by converting carbon dioxide in the atmosphere to a carbonate such as an alkali carbonate, following which the recovered carbonate is combined with hydrogen gas to produce combustible fuels e.g. methane and methanol. The method includes the additional step of reacting the alkali carbonate with calcium hydroxide to form calcium carbonate. The disadvantages of this method resides in the use of the strong base compound Ca(OH)2, forming CaCO3, that requires considerable amount of energy for the thermal release of COZ.
SUMMARY OF THE INVENTION
The present invention relates to a method for producing combustible fuels from a gaseous mixture containing carbon dioxide, which comprises:
(i) capturing CO2 from said gaseous mixture by means of K2C03, thus forming KHCO3;
(ii) releasing the COZ from said KHCO3 ; and (iii) subsequently producing fuel from the released CO2 by reaction with hydrogen.
DETAILED DESCRIPTION OF THE INVENTION
The method of the present invention enables the production of combustible fuels, using as preferred starting material the highly available atmospheric carbon dioxide, and retuniulg the CO2 produced by fuel combustion to the atmosphere, thus maintaining the equilibrium of the CO2 in the atmosphere. The method is based on well known in the art reactions such as thermal catalytic and electrochemical reactions, utilizing the reversibility of these reactions and carrying out the reverse reaction by modifying the operating pressure and/or the electrical voltage supplied to the process.
The reaction between the CO2 and K2C03 in step (i) may be performed by bubbling air in water through an aqueous solution of K2C03 or by spraying droplets of K2C03 in aqueous solution into a stream of air. In both methods, the atmospheric COa reacts with the K2C03 to form KHCO3 according to the following reaction:
K2C03 + H20 + CO2 4 2KHCO3 In the next step, CO2 is released from the KHCO3.
In one embodiment of the invention, the CO2 is released by heating the KHCO3 to a temperature sufficient to liberate the CO2, according to the following reaction, thus recycling the K2CO3:
2KHCO3 + Heat 4 K2C03 + H20 + CO2 In another embodiment, the CO2 is released from the KHCO3 obtained by an electrochemical process, according to the following reaction:
HC03- - e 4 -OH + CO2 4(-OH) 4 2H20 + 02 The CO2 obtained in step (ii) is then reacted with hydrogen to produce combustible fuels, such as methane and methanol.
In one embodiment, in which heat source producing very high temperatures is available, the reaction of COZ and hydrogen is conducted as a thermal catalytic reaction. One possible thermal catalytic reaction is a reverse operation of methane reforming. In steam methane reforming, methane is brought into contact with (excess) steam at high temperature and pressure, typically 800-1000 C and 30-bar, over a catalyst, to produce a mixture of H2, CO and CO2. In the industry, the process is usually carried out in fixed bed or fluidized bed membrane reactors, using a Ni as the preferred catalyst, because of its low cost, or a noble metal catalyst such as Ru, Rli, Pd, Ir or Pt. The reverse methane reforming according to the invention is carried in the same type of reactors and using the same catalysts as in steam methane reforming, but using pressures varying according to the characteristics of the specific process, said pressure being always higher than the pressure used for the methane reforming.
In another embodiment, the reaction of CO2 and hydrogen according to the invention is an electrochemical process, such as a reverse operation of a fuel cell.
A fuel cell is an electrochemical energy conversion device that converts the chemical energy of a fuel, e.g. hydrogen, and an oxidant, e.g. oxygen, to electrical energy and heat, without combustion. The device is similar to a battery but, unlike a battery, the fuel cell is designed for continuous replenishment of the reactants consumed, i.e., the fuel and the oxidant are typically stored outside of the fuel cell and transferred into the fuel cell as the reactants are consumed. In a typical fuel cell, the fuel is consumed at the anode and the oxidizer is consumed at the cathode.
There are several types of fuel cells, each using a different chemistry. Fuel cells are usually classified by the type of electrolyte they use, and include phosphoric acid-based, proton exchange membrane, solid polymer, molten carbonate, solid oxide, alkaline, direct methanol, regenerative, zinc-air and protonic ceramic fuel cells.
In a fuel cell, if a hydrocarbon, such as methane, is the fuel, said hydrocarbon is reacted with oxygen obtained by electrolysis of water within the cell, thus forming CO2 and hydrogen and generating electricity.
According to the present invention, a reverse operation of a fuel cell is carried out whereby electricity is supplied to a fuel cell containing C02, that reacts with hydrogen formed in situ by electrolysis of water, thus producing the desired hydrocarbon, e.g. methane fuel. The electrical voltage supplied to the process is determined based on the characteristics of the specific process performed but it is always higher than the electrical voltage generated in the opposite process, namely, the regular operation of the fuel cell.
In one preferred embodiment, the electrochemical process corresponds to an inverted direct methanol fuel cell (DMFC) and the fuel obtained is methanol.
DMFCs are low-temperature fuel cells operating at temperatures of 30-130 C
and using liquid methanol as the electrolyte, according to the reaction:
CH3OH + 3/202 4 CO2 + 2H2O
The central component of DMFCs is the membrane electrode assembly, composed of membrane, catalyst and diffusion layers. The membrane may be a polymer with acid groups that are capable of splitting off protons and has them migrate through the membrane. The diffusion layer passes the fuels to the catalyst layer and removes the combustion products. In the catalyst layers, the electrochemical reaction takes place, in which chemical energy is converted into electric energy. The catalyst is provided with additives to apply it as a paste on a substrate, and it is usually based on a noble metal, such as platinum and platinum/ruthenium.
].0 According to the present invention, the catalysts used for the reverse operation of the DMFC are the same used in the regular operation mode of the methanol fuel cell, and other parameters such as temperature and electrical voltage supplied to the process are determined based on the characteristics of the specific process performed.
In another preferred embodiment, the electrochemical process corresponds to an inverted molten carbonate fuel cell (MCFC) and the fuel obtained is a hydrocarbon, such as methane.
MCFCs are high-temperature fuel cell operating at temperatures of 600-650 C, and thus can achieve higher fuel-to-electricity and overall energy use efficiencies than low temperature fuel cells. The electrolyte used in MCFCs is an alkali carbonate such as Na2CO3, K2C03, Li2CO3 or combinations thereof, that may be retained in a ceramic matrix, e.g. of LiAlO2. In the fuel cell, the alkali carbonates melt into a highly conductive molten salt with carbonate ions providing ionic conduction through the electrolyte matrix. Nickel and nickel oxide are adequate to promote reaction on the anode and cathode, respectively, and expensive catalysts (noble metals) are not required.
The fuel consumed in MCFCs is usually a natural gas, mainly methane, and in this case methane and steam are converted into a hydrogen-rich gas inside the fuel cell stack (a process called "internal reforming"). The overall reaction performed within the cell is:
K2C03 + H20 + CO2 4 2KHCO3 In the next step, CO2 is released from the KHCO3.
In one embodiment of the invention, the CO2 is released by heating the KHCO3 to a temperature sufficient to liberate the CO2, according to the following reaction, thus recycling the K2CO3:
2KHCO3 + Heat 4 K2C03 + H20 + CO2 In another embodiment, the CO2 is released from the KHCO3 obtained by an electrochemical process, according to the following reaction:
HC03- - e 4 -OH + CO2 4(-OH) 4 2H20 + 02 The CO2 obtained in step (ii) is then reacted with hydrogen to produce combustible fuels, such as methane and methanol.
In one embodiment, in which heat source producing very high temperatures is available, the reaction of COZ and hydrogen is conducted as a thermal catalytic reaction. One possible thermal catalytic reaction is a reverse operation of methane reforming. In steam methane reforming, methane is brought into contact with (excess) steam at high temperature and pressure, typically 800-1000 C and 30-bar, over a catalyst, to produce a mixture of H2, CO and CO2. In the industry, the process is usually carried out in fixed bed or fluidized bed membrane reactors, using a Ni as the preferred catalyst, because of its low cost, or a noble metal catalyst such as Ru, Rli, Pd, Ir or Pt. The reverse methane reforming according to the invention is carried in the same type of reactors and using the same catalysts as in steam methane reforming, but using pressures varying according to the characteristics of the specific process, said pressure being always higher than the pressure used for the methane reforming.
In another embodiment, the reaction of CO2 and hydrogen according to the invention is an electrochemical process, such as a reverse operation of a fuel cell.
A fuel cell is an electrochemical energy conversion device that converts the chemical energy of a fuel, e.g. hydrogen, and an oxidant, e.g. oxygen, to electrical energy and heat, without combustion. The device is similar to a battery but, unlike a battery, the fuel cell is designed for continuous replenishment of the reactants consumed, i.e., the fuel and the oxidant are typically stored outside of the fuel cell and transferred into the fuel cell as the reactants are consumed. In a typical fuel cell, the fuel is consumed at the anode and the oxidizer is consumed at the cathode.
There are several types of fuel cells, each using a different chemistry. Fuel cells are usually classified by the type of electrolyte they use, and include phosphoric acid-based, proton exchange membrane, solid polymer, molten carbonate, solid oxide, alkaline, direct methanol, regenerative, zinc-air and protonic ceramic fuel cells.
In a fuel cell, if a hydrocarbon, such as methane, is the fuel, said hydrocarbon is reacted with oxygen obtained by electrolysis of water within the cell, thus forming CO2 and hydrogen and generating electricity.
According to the present invention, a reverse operation of a fuel cell is carried out whereby electricity is supplied to a fuel cell containing C02, that reacts with hydrogen formed in situ by electrolysis of water, thus producing the desired hydrocarbon, e.g. methane fuel. The electrical voltage supplied to the process is determined based on the characteristics of the specific process performed but it is always higher than the electrical voltage generated in the opposite process, namely, the regular operation of the fuel cell.
In one preferred embodiment, the electrochemical process corresponds to an inverted direct methanol fuel cell (DMFC) and the fuel obtained is methanol.
DMFCs are low-temperature fuel cells operating at temperatures of 30-130 C
and using liquid methanol as the electrolyte, according to the reaction:
CH3OH + 3/202 4 CO2 + 2H2O
The central component of DMFCs is the membrane electrode assembly, composed of membrane, catalyst and diffusion layers. The membrane may be a polymer with acid groups that are capable of splitting off protons and has them migrate through the membrane. The diffusion layer passes the fuels to the catalyst layer and removes the combustion products. In the catalyst layers, the electrochemical reaction takes place, in which chemical energy is converted into electric energy. The catalyst is provided with additives to apply it as a paste on a substrate, and it is usually based on a noble metal, such as platinum and platinum/ruthenium.
].0 According to the present invention, the catalysts used for the reverse operation of the DMFC are the same used in the regular operation mode of the methanol fuel cell, and other parameters such as temperature and electrical voltage supplied to the process are determined based on the characteristics of the specific process performed.
In another preferred embodiment, the electrochemical process corresponds to an inverted molten carbonate fuel cell (MCFC) and the fuel obtained is a hydrocarbon, such as methane.
MCFCs are high-temperature fuel cell operating at temperatures of 600-650 C, and thus can achieve higher fuel-to-electricity and overall energy use efficiencies than low temperature fuel cells. The electrolyte used in MCFCs is an alkali carbonate such as Na2CO3, K2C03, Li2CO3 or combinations thereof, that may be retained in a ceramic matrix, e.g. of LiAlO2. In the fuel cell, the alkali carbonates melt into a highly conductive molten salt with carbonate ions providing ionic conduction through the electrolyte matrix. Nickel and nickel oxide are adequate to promote reaction on the anode and cathode, respectively, and expensive catalysts (noble metals) are not required.
The fuel consumed in MCFCs is usually a natural gas, mainly methane, and in this case methane and steam are converted into a hydrogen-rich gas inside the fuel cell stack (a process called "internal reforming"). The overall reaction performed within the cell is:
CH4+02 4 C02 +2H2 According to the present invention, the operating conditions for the reverse operation of the MCFC (temperature and pressure) are similar to these in the regular operation mode of this cell. The exact conditions, as well as the voltage supplied to the process, are determined based on the characteristics of the specific process performed.
The methane or methanol obtained by the method of the invention may later be converted into longer hydrocarbons, using known chemical reactions.
The methane or methanol obtained by the method of the invention may later be converted into longer hydrocarbons, using known chemical reactions.
Claims (11)
1. A method for producing combustible fuels from a gaseous mixture containing carbon dioxide, which comprises:
(i) capturing CO2 from said gaseous mixture by means of K2CO3, thus forming KHCO3;
(ii) releasing the CO2 from said KHCO3 ; and (iii) subsequently producing fuel from the released CO2 by reaction with hydrogen.
(i) capturing CO2 from said gaseous mixture by means of K2CO3, thus forming KHCO3;
(ii) releasing the CO2 from said KHCO3 ; and (iii) subsequently producing fuel from the released CO2 by reaction with hydrogen.
2. The method of claim 1, wherein said gaseous mixture is air.
3. The method of claim 2, wherein the capture of CO2 is performed by bubbling air in water through an aqueous solution of K2CO3.
4. The method of claim 2, wherein the capture of CO2 is performed by spraying droplets of K2CO3 aqueous solution into a stream of air.
5. The method of any one of claims 1 to 4, wherein the CO2 in step (ii) is released from the KHCO3 by heating the KHCO3 to a temperature sufficient to liberate the CO2, thus recycling the K2CO3.
6. The method. of any one of claims 1 to 4, wherein the CO2 in step (ii) is released from the KHCO3 by an electrochemical process.
7. The method of any one of claims 1 to 6, wherein the reaction of CO2 with hydrogen in step (iii) is a catalytic thermal reaction.
8. The method of any one of claims 1 to 6, wherein the reaction of CO2 with hydrogen in step (iii) is an electrochemical reaction.
9. The method of claim 8, wherein said electrochemical reaction corresponds to a reverse operation of a fuel cell and the hydrogen is produced in situ.
10. The method of claim 9, wherein said electrochemical reaction corresponds to a reverse operation of a direct methanol fuel cell (DMFC) and the fuel produced is methanol.
11. The method of claim 6, wherein said electrochemical reaction corresponds to a reverse operation of a molten carbonate fuel cell (MCFC) and the fuel produced is a hydrocarbon such as methane.
Applications Claiming Priority (3)
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US58686904P | 2004-07-12 | 2004-07-12 | |
US60/586,869 | 2004-07-12 | ||
PCT/IL2005/000739 WO2006006164A2 (en) | 2004-07-12 | 2005-07-12 | Method for producing fuel from captured carbon dioxide |
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CA2579133A1 true CA2579133A1 (en) | 2006-01-19 |
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CA002579133A Abandoned CA2579133A1 (en) | 2004-07-12 | 2005-07-12 | Method for producing fuel from captured carbon dioxide |
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US (1) | US20080072496A1 (en) |
EP (1) | EP1778583A2 (en) |
KR (1) | KR20070067676A (en) |
AU (1) | AU2005261273A1 (en) |
CA (1) | CA2579133A1 (en) |
RU (1) | RU2007105092A (en) |
WO (1) | WO2006006164A2 (en) |
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FR2912421B1 (en) * | 2007-02-14 | 2010-08-20 | Charzat Claude Maurice | PROCESS FOR THE PRODUCTION OF SUBSTITUTE TO CARBOHYDROGENIC PRODUCTS OF FOSSIL ORIGIN, PROVIDING THE TOTAL RECYCLING OF THE CARBON DIOXIDE FROM THEIR USE |
GB2457929A (en) * | 2008-02-28 | 2009-09-02 | David James Benton | Process to extract carbon dioxide from air |
WO2010019378A2 (en) | 2008-08-13 | 2010-02-18 | Schlumberger Technology Corporation | Plug removal and setting system and method |
EP2382174A4 (en) | 2009-01-29 | 2013-10-30 | Trustees Of The University Of Princeton | Conversion of carbon dioxide to organic products |
AU2010320483A1 (en) | 2009-11-20 | 2012-07-12 | Cri Ehf | Storage of intermittent renewable energy as fuel using carbon containing feedstock |
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US8784661B2 (en) * | 2010-02-13 | 2014-07-22 | Mcallister Technologies, Llc | Liquid fuel for isolating waste material and storing energy |
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PL3401410T3 (en) | 2010-06-26 | 2021-11-29 | Virdia, Llc | Methods for production of sugar mixtures |
IL206678A0 (en) | 2010-06-28 | 2010-12-30 | Hcl Cleantech Ltd | A method for the production of fermentable sugars |
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US9090976B2 (en) | 2010-12-30 | 2015-07-28 | The Trustees Of Princeton University | Advanced aromatic amine heterocyclic catalysts for carbon dioxide reduction |
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EP2694594A4 (en) | 2011-04-07 | 2015-11-11 | Virdia Ltd | Lignocellulose conversion processes and products |
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EP2729600A2 (en) | 2011-07-06 | 2014-05-14 | Liquid Light, Inc. | Carbon dioxide capture and conversion to organic products |
US9056275B2 (en) | 2011-08-18 | 2015-06-16 | Arizona Board Of Regents, A Body Corporate Of The State Of Arizona Acting For An On Behalf Of Arizona State University | Capture and release of carbon dioxide |
US9617608B2 (en) | 2011-10-10 | 2017-04-11 | Virdia, Inc. | Sugar compositions |
WO2013112619A1 (en) | 2012-01-23 | 2013-08-01 | Battelle Memorial Institute | Separation and/or sequestration apparatus and methods |
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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 |
US4609440A (en) * | 1985-12-18 | 1986-09-02 | Gas Research Institute | Electrochemical synthesis of methane |
US4609441A (en) * | 1985-12-18 | 1986-09-02 | Gas Research Institute | Electrochemical reduction of aqueous carbon dioxide to methanol |
US4919910A (en) * | 1988-08-17 | 1990-04-24 | Church & Dwight Co., Inc. | Process for the production of potassium bicarbonate |
EP1125337A2 (en) * | 1998-10-27 | 2001-08-22 | Quadrise Limited | Electrical energy storage compound |
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2005
- 2005-07-12 US US11/631,967 patent/US20080072496A1/en not_active Abandoned
- 2005-07-12 KR KR1020077003333A patent/KR20070067676A/en not_active Application Discontinuation
- 2005-07-12 RU RU2007105092/04A patent/RU2007105092A/en not_active Application Discontinuation
- 2005-07-12 WO PCT/IL2005/000739 patent/WO2006006164A2/en active Application Filing
- 2005-07-12 AU AU2005261273A patent/AU2005261273A1/en not_active Abandoned
- 2005-07-12 CA CA002579133A patent/CA2579133A1/en not_active Abandoned
- 2005-07-12 EP EP05758924A patent/EP1778583A2/en not_active Withdrawn
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WO2006006164A3 (en) | 2009-05-07 |
RU2007105092A (en) | 2008-08-20 |
AU2005261273A1 (en) | 2006-01-19 |
KR20070067676A (en) | 2007-06-28 |
WO2006006164A2 (en) | 2006-01-19 |
US20080072496A1 (en) | 2008-03-27 |
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