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WO2011070124A2 - Procédé catalytique amélioré pour la réaction de dioxyde de carbone avec de l'hydrogène - Google Patents

Procédé catalytique amélioré pour la réaction de dioxyde de carbone avec de l'hydrogène Download PDF

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Publication number
WO2011070124A2
WO2011070124A2 PCT/EP2010/069305 EP2010069305W WO2011070124A2 WO 2011070124 A2 WO2011070124 A2 WO 2011070124A2 EP 2010069305 W EP2010069305 W EP 2010069305W WO 2011070124 A2 WO2011070124 A2 WO 2011070124A2
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Prior art keywords
carbon dioxide
hydrogen
catalyst
reaction product
water
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PCT/EP2010/069305
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English (en)
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WO2011070124A3 (fr
Inventor
Paul O'connor
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FRUITFUL INNOVATIONS BV
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FRUITFUL INNOVATIONS BV
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Priority to EP10790760A priority Critical patent/EP2509913A2/fr
Priority to CA2783681A priority patent/CA2783681A1/fr
Priority to BR112012013909A priority patent/BR112012013909A2/pt
Priority to AU2010329860A priority patent/AU2010329860A1/en
Priority to CN2010800610854A priority patent/CN102712467A/zh
Publication of WO2011070124A2 publication Critical patent/WO2011070124A2/fr
Publication of WO2011070124A3 publication Critical patent/WO2011070124A3/fr
Priority to US13/490,486 priority patent/US8754269B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • 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
    • C07C29/153—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 characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/50—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon dioxide with hydrogen
    • 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
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1022—Fischer-Tropsch products
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
    • 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
    • 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
    • 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
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • 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
    • Y02P20/584—Recycling of catalysts

Definitions

  • the invention relates generally to the conversion of carbon dioxide to hydrocarbons and more particularly to a catalytic process for the conversion of carbon dioxide to hydrocarbons.
  • the prior art processes generally comprise a number of reaction steps.
  • DE 101 56 975 Al discloses a four-step process.
  • carbon dioxide is isolated from the earth's atmosphere.
  • water is dissociated by electrolysis into hydrogen and oxygen.
  • the carbon dioxide is reacted with the hydrogen to form carbon monoxide and water.
  • a mixture of the carbon monoxide and additional hydrogen is converted to hydrocarbons and water.
  • DE 203 20 020 Ul discloses an integrated plant for the production of cement and hydrocarbons. Electric energy from a nuclear plant is used to dissociate water to form hydrogen. Carbon dioxide is reacted with hydrogen in a reverse water gas shift reactor to form carbon monoxide, which in turn is reacted in a Fischer-Tropsch reactor to form hydrocarbons.
  • GB 2 418 430 A discloses a process in which carbon dioxide is enriched from the atmosphere, or a carbon dioxide rich flue gas is used. Carbon dioxide is reacted with hydrogen to hydrocarbons in a Fischer-Tropsch reaction. The document does not disclose how the carbon dioxide/hydrogen mixture is converted to the syngas feedstock required for the Fischer-Tropsch reaction.
  • GB 2 459 430 A discloses a process wherein carbon dioxide is extracted from the atmosphere by chemical and physical extraction. The carbon dioxide is subjected to catalytic hydrogenation in the presence of hydrogen obtained from electrolysis of water. In one embodiment carbon dioxide is reacted with hydrogen to methanol; in turn, methanol is converted to hydrocarbons in a Fischer-Tropsch process. In a second embodiment carbon dioxide is reacted to octane using two catalysts, a salt in addition to a nickel hydrogenation catalyst.
  • US Patent No. 4,339,547 discloses a process in which carbon dioxide is extracted from the atmosphere, for example using NaOH to form Na 2 C0 3 .
  • Hydrogen is produced by electrolysis. Carbon dioxide is reacted with hydrogen over a copper catalyst to form methanol. Methanol is converted to hydrocarbons over a zeolite catalyst.
  • WO 00/25380 discloses a process for storing solar energy.
  • solar energy is converted to electric energy using photovoltaic cells.
  • the electric energy is used in electrolysis to form hydrogen.
  • the hydrogen is reacted with carbon dioxide to form methanol, which is used as a fuel in a methanol fuel cell to generate electric energy.
  • WO 99/20713 discloses an intricate process in which carbon dioxide generated in the combustion of a fossil fuel, such as methane, is reacted with hydrogen in a Sabatier reactor over a nickel catalyst.
  • WO 2007/108014 discloses a process in which carbon dioxide from an industrial combustion process is reacted with hydrogen from water electrolysis to form methanol. The methanol is converted to hydrocarbons in the Mobil methanol-to- gasoline (MTG) process.
  • MTG Mobil methanol-to- gasoline
  • the present invention addresses these problems by providing a process for reacting carbon dioxide with hydrogen, said process comprising the steps of:
  • step (ii) contacting the catalytic material of step (i) with hydrogen at a temperature in the range of from 25 °C to 1000 °C, preferably from 200 °C to 500 °C, whereby a reaction product is formed.
  • Another aspect of the invention comprises a method for regenerating the catalyst by contacting the catalyst after use in step (ii) with carbon dioxide.
  • Various prior art processes are based on a reaction of carbon dioxide with hydrogen as a step towards the production of hydrocarbons.
  • the processes vary in the source of the carbon dioxide reactant.
  • carbon dioxide is captured from the atmosphere, for example by chemical or physical extraction.
  • Other processes are integrated with an industrial process that inherently produces carbon dioxide, for example the combustion of fossil fuels in a power plant, or the decomposition of lime stone in the manufacture of cement.
  • a third class of process comprises the
  • Processes that use a flue gas of a combustion process as the carbon dioxide source suffer from geographic and capacity constraints associated with integrated processes. That is, the hydrocarbon production plant must be located in close proximity of the carbon dioxide generating plant, and the capacity of the hydrocarbon production plant must closely match the carbon dioxide production rate of the plant with which it is integrated. [0017] Processes that rely on carbon dioxide capture are more flexible in terms of the geographic location and the capacity of the hydrocarbon production plant. However, these processes introduce a new inefficiency in that the material used for capturing the carbon dioxide must be decomposed to free the captured carbon dioxide.
  • the present invention addresses the carbon dioxide sourcing issue by providing a process for reacting carbon dioxide with hydrogen, said process comprising the steps of:
  • step (ii) contacting the catalytic material of step (i) with hydrogen at a temperature in the
  • the catalyst used in step (ii) is a material that is suitable for capturing carbon dioxide. This eliminates the need for decomposing the carbon dioxide sequestering material in order to free up the carbon dioxide for reaction with hydrogen. Instead, the process of the invention provides carbon dioxide at the location where it is most needed, i.e., the surface of the catalyst. Hydrogen molecules, because of their small size, quickly and easily diffuse into the pores of the catalyst.
  • reaction product of step (ii) can comprise carbon monoxide, as in a reverse water gas shift reaction.
  • reaction product comprises methanol.
  • reaction product comprises a mixture of hydrocarbons.
  • the hydrocarbons preferably comprise a mixture of alkanes.
  • the hydrocarbon mixture may further comprise a mixture of olefins.
  • composition of the reaction product will be largely determined by factors such as the reaction temperature, the hydrogen pressure, the presence or not of additional carbon dioxide, and the nature of the catalyst.
  • nature of the catalyst plays an important role in determining the composition of the reaction product. For example, a reverse water gas shift catalyst favors the formation of carbon monoxide; a hydrogenation catalyst favors the formation of methanol; and a Sabatier catalyst or a Fischer-Tropsch catalyst favors the formation of hydrocarbons.
  • the catalyst composition may contain a second component for providing, for example, hydrogenation functionality or Fischer- Tropsch functionality.
  • An example of a tri-component catalyst composition is one comprising a first component providing carbon dioxide adsorption functionality; a second component providing reverse water gas shift functionality; and a third component providing Fischer-Tropsch functionality.
  • the catalyst composition can comprise a metal oxide, for example an oxide of a
  • the divalent metal can comprise an alkaline earth metal, in particular calcium and/or magnesium.
  • the trivalent metal can, for example, be aluminum.
  • catalyst compositions comprising hydrotalcite or a
  • hydrotalcite-like material refers to materials having the general crystal structure of hydrotalcite and wherein part or all of the magnesium ions are replaced with ions of another divalent metal, and/or part or all of the aluminum ions are replaced with ions of another trivalent metal.
  • the catalyst composition can further comprise a transition metal.
  • transition metals are those selected from the group consisting of Fe, Ni, Co, Ru, Re, Zn, Au, and mixtures thereof.
  • the carbon dioxide conversion comprises in situ hydrolysis of water. Accordingly, a preferred embodiment of the invention is a process comprising the steps of:
  • An important aspect of this embodiment of the process of the present invention is that the input of solar energy, which results in water in an activated form, takes place in the presence of the carbon source. This feature permits the carbon dioxide to react with water in the activated form.
  • This embodiment of the invention is not limited by specific forms of activated water.
  • the water molecule has one or both of the O-H bonds in an excited state, making it possible for a hydrogen radical to be split off and react with the carbon source.
  • the excited state can be achieved by irradiating water with solar photons, in particular in the UV range of the spectrum.
  • the formation of activated water can be amplified by the use of a suitable semiconductor with a band gap corresponding to the energy of photons in the visible or near ultra-violet part of the spectrum. Titanium dioxide (band gap 3 eV) is an example of a suitable
  • solar energy is used to form hydrogen radicals and/or
  • hydrogen molecules For example, solar energy can be used to generate electric energy in a photovoltaic process.
  • the electric energy can be used for electrolysis of water molecules, whereby hydrogen in atomic form (hydrogen in statu nascendi) is formed.
  • This form of hydrogen is far more reactive than molecular hydrogen.
  • Atomic hydrogen reacts readily with the carbon source.
  • a form of solar energy is used to dissociate water into hydrogen molecules.
  • molecular hydrogen can react with the carbon source, in particular in the presence of a suitable catalyst.
  • the water source does not need to meet stringent requirements in terms of purity.
  • the requirements imposed on the water quality by the process of the present invention are very low.
  • the process can be carried out with water comprising at least one contaminant.
  • the water source can comprise waste water.
  • the waste water can be
  • the water source comprises sea water.
  • Solar energy can be used in the form in which it reaches earth, that is, in the form of electromagnetic radiation in the infrared, visible, and ultraviolet parts of the spectrum, i.e., photonic energy. It can be desirable to convert this photonic energy to some other form of energy, for example to permit the energy to be temporarily stored. Temporary storage makes it possible to run the process also when the sun is not shining, for example during night time. Relatively advanced technology exists for converting solar energy to photovoltaic energy, which can be stored in rechargeable batteries, for example Li-ion batteries.
  • the process of the invention itself can be used for storing solar energy in the form of an organic compound, such as an alcohol (for example ethanol or methanol), a hydrocarbon, or a carbohydrate.
  • an organic compound such as an alcohol (for example ethanol or methanol), a hydrocarbon, or a carbohydrate.
  • the organic compound is a liquid at room temperature, for cost effective storage and transportation.
  • the organic compound can be used as a fuel in a fuel cell for generating electricity.
  • solar electricity can be made available on a 24/7 basis (24 hours per day, 7 days per week).
  • solar energy can be readily converted to yet other forms of energy, such as microwave energy. It can be desirable to convert the photovoltaic energy back to photonic energy, in the form of a laser beam, for example. Laser permits energy to be submitted to the process in a highly concentrated form.
  • solar energy is used to generate steam, for example in a
  • Concentrated Solar Thermal (CST) process uses lenses, mirrors and a tracking system to focus a large area of sunlight into a small area.
  • the concentrated heat can be used for generating steam, which can be used to generate electricity in a conventional steam generator.
  • the concentrated heat is used to raise the
  • step (iii) of the present process can be used in step (iii) of the present process, either in situ, or in a separate reactor after removing oxygen from the hydrogen stream.
  • solar energy is converted in a Photon Enhanced
  • PETE Thermionic Emission
  • semiconductor material is irradiated with solar radiation. Different from the photovoltaic (PV) process, which only uses the visible part of the spectrum, the semiconductor of the PETE process is able to convert both the visible light and the IR parts of the solar spectrum to electric energy, making the PETE process much more efficient.
  • the semiconductor material used in the PETE process must be able to withstand high temperatures. Suitable examples include gallium nitride and gallium arsenide.
  • step (ii) comprises a Fischer-Tropsch reaction.
  • the Fischer- Tropsch reaction is essentially a reaction of carbon monoxide and hydrogen, to form hydrocarbons, in particular alkanes.
  • the reaction mixture comprises carbon monoxide, which is
  • C0 2 is first reacted with hydrogen to form CO in the inverse water shift reaction, thereby providing the carbon source for the Fischer-Tropsch reaction.
  • Step (ii) is preferably carried out while solar energy is supplied to the reaction mixture, for example in the form of photonic energy.
  • step (ii) comprises a Sabatier reaction, which uses carbon dioxide as the carbon source.
  • carbon dioxide is present in a concentrated form in the process of the invention.
  • the Sabatier reaction is preferably carried out in the presence of a Sabatier catalyst.
  • catalysts comprising Ru.
  • the Sabatier catalyst comprises a
  • a Ru/Ti0 2 catalyst is reduced in an Ar/H 2 (1 :1 ratio) stream, at a temperature in the range of 200 °C to 250 °C. Full reduction of Ru0 2 requires a reduction temperature of 500 °C.
  • the Ru/Ti0 2 catalyst permits the Sabatier reaction to be carried out under
  • the catalyst is particularly effective when the reaction mixture is illuminated with solar photonic energy.
  • the catalyst is an inorganic oxide or hydroxide. Catalysts of this type can be used with a wide variety of carbon sources, including coal and synthetic polymers.
  • hydrotalcite Preferred within this class of catalysts are hydrotalcite; hydrotalcite-like materials; clays; alumina; layered hydroxy salts; mixed metal oxides; and the calcination products of any of these materials.
  • hydrotalcite-like materials refers to mixed metal oxides having the general crystal structure of hydrotalcite, and wherein all or part of the Al 3+ is replaced with another trivalent cation, and/or all or part of the Mg 2+ is replaced with another divalent cation.
  • the type of organic compounds produced in step (iii) depends on the nature of the carbon source, and the type of reaction conducted. For example, if the carbon source is carbon dioxide, and the reaction is a Sabatier reaction, the primary (or sole) reaction product is methane. If the carbon source is carbon dioxide or carbon monoxide, and the reaction is a Fischer-Tropsch reaction, the reaction product is a mixture of hydrocarbons, primarily alkanes.
  • Methane produced in a Sabatier reaction can be readily converted to methanol, using well-known prior art processes. Methanol can be used as a fuel for a fuel cell.
  • reaction product of step (ii) can be used as a feed in a subsequent conversion reaction.
  • a reaction product comprising methanol can be converted to a mixture of hydrocarbons in a methanol-to-gasoline (MTG) process.
  • a reaction product comprising carbon monoxide can be converted to a mixture of hydrocarbons in a Fischer-Tropsch (FT) process.
  • step (ii) of the process is carried out in continuous mode.
  • step (ii) the catalyst becomes depleted with carbon dioxide.
  • the catalyst can be regenerated by contacting the catalyst with carbon dioxide.
  • the catalyst is contacted with air, and is allowed to adsorb carbon dioxide from the air.
  • the catalyst is contacted with a carbon dioxide-rich gas, for example flue gas.
  • the flue gas may be generated by a power plant, for example a power plant fired with a fossil fuel.
  • the process of the present invention is particularly suitable for capturing and re-using carbon dioxide from a coal- fired power plant, as the flue gases of these power plants are particularly rich in carbon dioxide.
  • the hydrogen used in step (ii) can be from any source.
  • Preferred is "carbon-free" hydrogen, for example hydrogen produced by water electrolysis using electric power from a renewable resource.
  • renewable energy sources include solar power, wind power, and tidal power.
  • An important advantage of the process of the invention is that it can be carried out at a location where electricity from a renewable resource is abundantly available.
  • One aspect of the process of the invention is its use for storing solar energy in the form of the reaction product of step (ii) or the reaction product of a subsequent reaction step. In a preferred embodiment the process of the invention stores solar energy in the form of hydrocarbons.
  • water for the process can be of poor quality in terms of purity, so that water suitable for irrigation or for animal or human consumption does not need to be used in the process.
  • water suitable for irrigation or for animal or human consumption does not need to be used in the process.
  • sea water or brackish water can be used.
  • step (ii) of the process produces water.
  • carbon monoxide carbon monoxide
  • step (ii) Water produced in step (ii) can be recycled to the water electrolysis step.
  • the reaction product of step (ii) is a mixture of alkanes (equation 3)
  • the water produced in the reaction is easily separated from the hydrocarbon reaction products.
  • the water produced in the reaction can be readily purified to make it suitable for irrigation or even animal or human consumption.
  • this embodiment of the invention provides indirect water purification or desalination as a side benefit.
  • Reactor 10 comprises a water source 11.
  • Photovoltaic panel 20 receives solar
  • photonic energy 21 which it converts to photovoltaic energy.
  • the photovoltaic energy feeds anode 22 and cathode 23, both of which are immersed in water source 11.
  • Anode 22 and cathode 23 are optionally separated by membrane 24.
  • Tube 30 receives a catalyst 31 having carbon dioxide adsorbed thereto from an
  • Catalyst 31 is pumped to tube end 32, which is immersed in water source 11. Carbon source 31 leaves tube end 32 through holes 33.
  • Anode gas 25 is formed at anode 22.
  • Anode gas 25 can be oxygen (from the
  • Anode gas 25 is collected in a gas container (not shown).
  • Hydrogen gas 26 is formed at cathode 23. Both carbon source 31 and hydrogen gas 26 rise upward in water source 11 , and become mixed with one another. The gas mixture passes through catalyst bed 40, where carbon dioxide present on catalyst 31 is reacted with hydrogen gas 26. Reaction product 41 is a liquid hydrocarbon, which floats to the surface of water source 11.
  • reaction product comprises gaseous hydrocarbons, which are collected above the surface of water source 11.
  • the catalyst is slurried in water source 11 , which is

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  • Chemical Kinetics & Catalysis (AREA)
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  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

La présente invention concerne un procédé de réaction de dioxyde de carbone avec de l'hydrogène. Dans le procédé, un catalyseur sur lequel est adsorbé du dioxyde de carbone est mis en contact avec de l'hydrogène à une température élevée. Le catalyseur peut être régénéré par mise en contact du catalyseur appauvri avec une source de dioxyde de carbone, par exemple un gaz de combustion d'un moteur. Dans un mode de réalisation préféré, le dioxyde de carbone réagit par hydrolyse de l'eau in situ.
PCT/EP2010/069305 2009-12-10 2010-12-09 Procédé catalytique amélioré pour la réaction de dioxyde de carbone avec de l'hydrogène Ceased WO2011070124A2 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP10790760A EP2509913A2 (fr) 2009-12-10 2010-12-09 Procédé catalytique amélioré pour la réaction de dioxyde de carbone avec de l'hydrogène
CA2783681A CA2783681A1 (fr) 2009-12-10 2010-12-09 Procede catalytique ameliore pour la reaction de dioxyde de carbone avec de l'hydrogene
BR112012013909A BR112012013909A2 (pt) 2009-12-10 2010-12-09 processo para reagir dióxido de carbono com hidrogênio
AU2010329860A AU2010329860A1 (en) 2009-12-10 2010-12-09 Improved catalytic process for reacting carbon dioxide with hydrogen
CN2010800610854A CN102712467A (zh) 2009-12-10 2010-12-09 改进的用于二氧化碳与氢气反应的催化方法
US13/490,486 US8754269B2 (en) 2009-12-10 2012-06-07 Catalytic process for reacting carbon dioxide with hydrogen

Applications Claiming Priority (2)

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US28522709P 2009-12-10 2009-12-10
US61/285,227 2009-12-10

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US13/490,486 Continuation US8754269B2 (en) 2009-12-10 2012-06-07 Catalytic process for reacting carbon dioxide with hydrogen

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WO2011070124A2 true WO2011070124A2 (fr) 2011-06-16
WO2011070124A3 WO2011070124A3 (fr) 2011-10-13

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US (1) US8754269B2 (fr)
EP (1) EP2509913A2 (fr)
CN (1) CN102712467A (fr)
AU (1) AU2010329860A1 (fr)
BR (1) BR112012013909A2 (fr)
CA (1) CA2783681A1 (fr)
WO (1) WO2011070124A2 (fr)

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WO2013190065A1 (fr) * 2012-06-20 2013-12-27 Antecy B.V. Dispositif pour stockage et conversion d'énergie
WO2014040844A1 (fr) * 2012-09-11 2014-03-20 Siemens Aktiengesellschaft Installation combinée écologique pour la production de produits chimiques et pétrochimiques

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BR112012013909A2 (pt) * 2009-12-10 2016-04-26 Antecy Bv processo para reagir dióxido de carbono com hidrogênio
US9238598B2 (en) 2013-01-04 2016-01-19 Saudi Arabian Oil Company Carbon dioxide conversion to hydrocarbon fuel via syngas production cell harnessed from solar radiation
CN103721719B (zh) * 2014-01-03 2015-11-11 中国科学院山西煤炭化学研究所 一种二氧化碳加氢合成甲醇催化剂及制法和应用
EP3094652B1 (fr) 2014-01-13 2021-09-29 Baylor Research Institute Nouveaux vaccins contre le vph et maladies liées au vph
AU2017381715B2 (en) 2016-12-21 2023-11-09 Isca Management Ltd. Removal of greenhouse gases and heavy metals from an emission stream
US10583389B2 (en) 2016-12-21 2020-03-10 Genesis Systems Llc Atmospheric water generation systems and methods
CA3215266A1 (fr) 2020-05-04 2021-11-11 Infinium Technology, Llc Procede de capture de dioxyde de carbone dans l'air et conversion directe de dioxyde de carbone en carburants et produits chimiques
CN112430472A (zh) * 2020-11-06 2021-03-02 武汉大学 一种co2加氢直接制备低碳醇联产汽油的方法
IL303720A (en) 2020-12-17 2023-08-01 Genesis Systems Llc Systems and methods for atmospheric water production
IL309371A (en) 2021-07-07 2024-02-01 Genesis Systems Llc Systems and methods for producing atmospheric water by ultrasonic or microwave absorption for solvent regeneration

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Publication number Priority date Publication date Assignee Title
WO2013190065A1 (fr) * 2012-06-20 2013-12-27 Antecy B.V. Dispositif pour stockage et conversion d'énergie
WO2014040844A1 (fr) * 2012-09-11 2014-03-20 Siemens Aktiengesellschaft Installation combinée écologique pour la production de produits chimiques et pétrochimiques

Also Published As

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US20130005839A1 (en) 2013-01-03
EP2509913A2 (fr) 2012-10-17
AU2010329860A1 (en) 2012-07-26
WO2011070124A3 (fr) 2011-10-13
CN102712467A (zh) 2012-10-03
US8754269B2 (en) 2014-06-17
CA2783681A1 (fr) 2011-06-16
BR112012013909A2 (pt) 2016-04-26

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