WO2014027116A1 - Procédé pour la conversion d'une charge de départ gazeuse en composés organiques liquides - Google Patents

Procédé pour la conversion d'une charge de départ gazeuse en composés organiques liquides Download PDF

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Publication number
WO2014027116A1
WO2014027116A1 PCT/EP2013/067258 EP2013067258W WO2014027116A1 WO 2014027116 A1 WO2014027116 A1 WO 2014027116A1 EP 2013067258 W EP2013067258 W EP 2013067258W WO 2014027116 A1 WO2014027116 A1 WO 2014027116A1
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WO
WIPO (PCT)
Prior art keywords
ionic liquid
reaction
liquid
reaction mixture
carbon dioxide
Prior art date
Application number
PCT/EP2013/067258
Other languages
English (en)
Inventor
Paul O'connor
Timo ROESTENBERG
Sjoerd Daamen
Jacobus Johannes Leonardus Heinerman
Guido Mul
Recep KAS
Original Assignee
Antecy B.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Antecy B.V. filed Critical Antecy B.V.
Publication of WO2014027116A1 publication Critical patent/WO2014027116A1/fr

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Classifications

    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • 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
    • 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
    • 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
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • H01M8/0668—Removal of carbon monoxide or carbon dioxide
    • 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

Definitions

  • the invention relates generally to the conversion of a gaseous feedstock to liquid organic compounds, and more specifically to the conversion of carbon dioxide, gaseous hydrocarbons, and mixtures thereof to organic compounds, such as alkanes and alkanols, that are liquids under ambient conditions.
  • Carbon dioxide has been identified as a major contributor to climate change.
  • LPG Liquified Petroleum Gas
  • the present invention addresses these problems by providing a process for converting a gaseous feedstock selected from the group consisting of carbon dioxide, a gaseous hydrocarbon, and mixtures thereof to a reaction product that is liquid at ambient temperature and pressure, said process comprising forming a reaction mixture by contacting the gaseous feedstock with an Ionic Liquid, and supplying energy to the reaction mixture.
  • Figure 1 shows operation of an electrochemical reactor in the conversion of carbon dioxide to methanol.
  • Figure 2 shows the reactor of Figure 1 when operated as a storage battery.
  • Figure 3 shows the battery of figure 2 in discharge mode.
  • Figure 4 shows an alternate embodiment of the electrochemical reactor.
  • gaseous feedstock means a reactant that can be converted to a liquid organic compound in the process of the present invention, the reactant being a gas at ambient temperature and pressure.
  • the term encompasses carbon dioxide, gaseous hydrocarbons, and mixtures thereof
  • liquid organic compound as used herein means an organic compound that can be transported as a liquid at ambient temperature and pressure.
  • the term includes waxy compounds, such as alkanes having from 16 to 20 carbon atoms, which require slight heating to reduce their viscosity to make them pumpable.
  • the term generally includes liquid alkanols, liquid alkanes, liquid organic acids, and the like.
  • Ionic Liquids The standard definition for Ionic Liquids is "ionic compounds which are liquid at temperatures below 100 °C.” In the process of the present invention Ionic Liquids are used as a reaction medium for reactions that are carried out at temperatures below 300 °C.
  • an ionic compound is considered an Ionic Liquid within the meaning of the present invention if it is liquid at a temperature below 300 °C.
  • liquids that are highly polar, although not necessarily ionic, in particular supercritical water and supercritical carbon dioxide.
  • the present invention relates to a process for converting a gaseous feedstock selected from the group consisting of carbon dioxide, a gaseous hydrocarbon, and mixtures thereof to a reaction product that is liquid at ambient temperature and pressure, said process comprising forming a reaction mixture by contacting the gaseous feedstock with an Ionic Liquid, and supplying energy to the reaction mixture.
  • the Ionic Liquid is believed to act as a catalyst by activating C-0 bonds (in the case of carbon dioxide) or C-H bonds (in the case of gaseous hydrocarbons), thereby lowering the activation energy of the conversion reaction. Accordingly, the conversion reaction can be carried out at a temperature of 300 °C or less, preferably 200 °C or less. These low reaction temperatures offer significant advantages in terms of energy requirements.
  • the reaction mixture comprises hydrogen, in addition to the gaseous feedstock.
  • Hydrogen may be supplied to the reaction mixture from an external source, or it may be formed in situ, for example by electrolysis of water.
  • the formation of molecular hydrogen by electrolysis involves the formation of hydrogen radicals.
  • the Ionic Liquid medium acts to stabilize hydrogen radicals, and in addition is conducive to the formation of hydrogen ions, such as HH " .
  • Hydrogen radicals and hydrogen ions are more reactive than is molecular hydrogen. For this reason the in situ formation of hydrogen is preferred over hydrogen supply from an external source.
  • reaction mixture optionally comprises carbon monoxide.
  • the gaseous feedstock comprises or consists of carbon dioxide.
  • Carbon dioxide may be obtained from the flue gas of a plant that burns carbon-containing fuels, such as a coal, diesel or gas-burning power plant.
  • carbon dioxide is harvested from ambient air, for example by using a reversible adsorption process.
  • a preferred process is described in our co-pending patent applications "Materials and Process for Reversible Adsorption of Carbon Dioxide", filed as Provisional US Patent Application Serial No 61/672,331 on July 17, 2012; and "Device for Temperature Swing Process, filed as Provisional US Patent Application Serial No 61/672,333 on July 17, 2012, the disclosures of both patent applications being incorporated herein by reference.
  • the gaseous feedstock comprises or consists of gaseous hydrocarbons, in particular methane.
  • the reaction product is a liquid fuel.
  • the liquid fuel may comprise liquid organic compounds selected from the group consisting of an alkanol having from 1 to 12 carbon atoms; an alkane having from 5 to 12 carbon atoms; a carboxylic acid having from 1 to 18 carbon atoms and esters thereof; and mixtures thereof. Specific examples include methanol, octane, cetane, methyl laurate, and formic acid.
  • the liquid fuel may be used as a gasoline, a diesel fuel, a jet fuel, a kerosene, and the like.
  • the liquid fuel may be used either as is, or as a blend stock for any of these specialized uses. It may be necessary to subject the reaction mixture to a further chemical conversion to make them suitable as a liquid fuel for specialized applications, such as internal combustion engines or jet engines.
  • Such further chemical conversion may be carried out in the Ionic Liquid reaction medium, or the reaction product may be separated from the Ionic Liquid medium prior to such further chemical conversion.
  • the solubility of the reaction products in the Ionic Liquid is inversely related to the oxygen content of the reaction product.
  • methanol and ethanol may require a separation step, for example extraction, selective adsorption, distillation, or the like.
  • reaction products may be used as functional or building block chemicals.
  • functional or building block chemicals see the paper from the US National Renewable Energy Laboratory (ENREL) entitled “Top Value Added Chemicals from Biomass.”
  • the process involves endothermic reactions, and requires that energy be supplied to the reaction mixture.
  • Energy may be supplied in the form of heat, by any means known in the art. It is also possible to supply energy in the form of electric energy or as electromagnetic radiation, in particular RF and photons.
  • the Ionic Liquid is believed to act as a catalyst. It may be advantageous to use a second catalyst, in addition to the Ionic Liquid, in the reaction mixture.
  • the second catalyst can be an electro-catalyst.
  • the second catalyst can be a photo-catalyst.
  • the Ionic Liquid generally belongs to one of three classes of Ionic Liquids.
  • the first such class is organic Ionic Liquids.
  • the cation of an organic Ionic Liquid is in general organic, for example a derivative of imidazolium; pyridinium; pyrrolidinium; phosphonium; ammonium; or sulfonium.
  • the anion may be organic or inorganic.
  • organic anions include alkylsulfate; tosylate; methanesulfonate; and bis(trifluoromethyl- sulfonyl)imide.
  • examples of inorganic anions include hexafluorophosphate; tetrafluoroborate; and halide.
  • the second class is inorganic Ionic Liquids.
  • inorganic molten salts and inorganic molten salt hydrates.
  • inorganic Ionic Liquids both the cation and the anion are inorganic.
  • Molten salts are salts that are liquid in water-free condition at a temperature below 300 °C.
  • Molten salt hydrates are hydrated salts having, in the hydrated form, a melting point below 300 °C.
  • the third class consists of polar inorganic compounds in supercritical form, such as supercritical carbon dioxide and supercritical water.
  • Supercritical carbon dioxide is of particular interest, because in a reaction mixture using supercritical carbon dioxide as the Ionic Liquid, carbon dioxide fulfills the double function of reaction medium and reactant. It will be understood that in the general literature polar inorganic compounds in supercritical form are not considered Ionic Liquids. These solvents are, however, suitable for carrying out the process of the present invention and are, within the confines of this document, considered to be encompassed by the term Ionic Liquids.
  • Ionic Liquids comprising an imidazolium cation become de-protonated in the presence of a superbase. It is possible to increase the solubility of carbon dioxide in the Ionic Liquid to 1 mole carbon dioxide per mol Ionic Liquid. Moreover, the catalytic properties of the Ionic Liquid are believed to be enhanced as a result of the de-pro tonation.
  • the superbase is present in a 1: 1 molar ratio to the Ionic Liquid.
  • Organic Ionic Liquids suffer from a number of disadvantages, one of which is price. Another common disadvantage is that many organic Ionic Liquids lose their solvent properties when water is present, even in small amounts. This makes these solvents unsuitable for reactions in which water is used for in situ generation of hydrogen. In addition, many organic Ionic Liquids are reactive under the reaction conditions used in the process. For example, organic Ionic Liquids containing double carbon-carbon bonds may react with hydrogen under the reaction conditions used in the process of the invention.
  • inorganic Ionic Liquids are generally inexpensive; highly inert; and robust in the presence of water. For these reasons inorganic Ionic Liquids are preferred in many cases for use in the process of the invention.
  • Ionic Liquids having, as the cation, an alkali metal; an alkaline earth metal; or a metal from Group 12 of the IUPAC Periodic Table of the Elements: zinc, cadmium, mercury, copernicium.
  • Ionic Liquids having, as the anion, a halide.
  • the preferred halide is chloride.
  • the preferred Ionic Liquid is a molten zinc chloride hydrate, in particular zinc chloride hexahydrate.
  • FIG. 1 shows an electrochemical reactor 1 comprising a vessel 30 filled with the zinc chloride solvent 31. Immersed in solvent 31 are a first electrode 10 and a second electrode 20. An electric potential 32 is applied to electrodes 10 and 20 so that electrode 10 acts as a cathode and electrode 20 as an anode.
  • Anode 20 is surrounded by an electrically insulating, proton-permeable membrane 21 of the kind routinely employed in fuel cells. Nafion® from Dupont is an example of a suitable membrane material.
  • Anode 20 preferably comprises manganese ( ⁇ ) oxide (Mn 2 0 3 ). Alternately anode 20 may comprise an Ag 2 0/Ag redox system.
  • Electrode 10 has the form of a hollow, porous tube, made of an electrically conducting material, for example a porous metal; a hollow porous graphite rod; a hollow graphite honeycomb rod, or the like.
  • Carbon dioxide gas is supplied to cathode 10 under an overpressure that is high enough to force carbon dioxide gas through the cathode material into the solvent, yet not so high as to cause excessive formation of carbon dioxide bubbles on the surface of cathode 10.
  • water is supplied to anode 20.
  • reaction at the anode is the half reaction of the well-known water electrolysis reaction:
  • reaction (2) is the most desirable, as it results in the formation of a liquid fuel.
  • Reaction (2) can be promoted by incorporating a methanol formation catalyst in cathode 10, such as nickel.
  • the presence of nickel may also promote conversion of carbon monoxide (from reaction (3)) and hydrogen (from reaction (4) to methanol.
  • Reaction (5) is favored if the medium is proton depleted. Reaction (5) can be suppressed by increasing the proton concentration of the reaction mixture, for example by the addition of a mineral acid.
  • Hydrochloric acid is the preferred mineral acid.
  • Figure 2 shows the operation of the reactor as a storage battery for electric energy.
  • An electric voltage 32 is supplied to the electrodes, as in Figure 1. No reactants are supplied to the electrodes, however.
  • the reaction at anode 20 is oxidation of ⁇ ( ⁇ ) to Mn(IV):
  • Figure 3 shows the reactor of Figure 1 operated as a charged battery in the process of being discharged. All reactions are identical to those of Figure 2, except that the reactions proceed in opposite direction.
  • the overall reaction in an acidic environment is:
  • Figure 4 shows a second embodiment of the electrochemical reactor.
  • the electrically insulating membrane is placed intermediate the cathode and the anode.
  • the electrolyte surrounding the anode is different from the electrolyte surrounding the cathode, the former comprising, for example, MnS0 4 and/or H 2 S0 4 .
  • the reactions taking place are as described above in reaction equations (1) through (6).
  • reaction equation (5) In energy storage mode the cathode reaction is given by reaction equation (5).
  • the reaction at the anode involves oxidation of dissolved ⁇ ( ⁇ ) to solid Mn(IV), as follows:
  • stored electrical energy can be used in the conversion of carbon dioxide, with oxidation of metallic Zn to Zn 2+ and reduction of Mn(IV) to solid ⁇ ( ⁇ ) or dissolved Mn(II), for example:

Abstract

L'invention porte sur un procédé pour la conversion d'une charge de départ gazeuse en un composé organique liquide. La charge de départ gazeuse est choisie dans le groupe constitué par le dioxyde de carbone, les hydrocarbures gazeux et les mélanges de ceux-ci. La réaction de conversion est effectuée dans un liquide ionique. Le procédé est effectué dans un réacteur électrochimique. Le réacteur peut également être utilisé en tant qu'accumulateur électrique. L'énergie électrique accumulée dans le réacteur électrochimique peut être utilisée pour entraîner la réaction de conversion.
PCT/EP2013/067258 2012-08-17 2013-08-19 Procédé pour la conversion d'une charge de départ gazeuse en composés organiques liquides WO2014027116A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201261684147P 2012-08-17 2012-08-17
US61/684,147 2012-08-17

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WO2014027116A1 true WO2014027116A1 (fr) 2014-02-20

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3614059A1 (fr) * 2018-08-23 2020-02-26 Antecy B.V. Procédé et dispositif pour améliorer la qualité de l'air dans des environnements fermés

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4140602A (en) * 1975-09-02 1979-02-20 Texas Gas Transmission Corporation Method for obtaining carbon dioxide from the atmosphere and for production of fuels
US4427508A (en) * 1982-05-03 1984-01-24 Atlantic Richfield Company Light driven photocatalytic process
WO2006006164A2 (fr) * 2004-07-12 2006-01-19 Aytec Avnim Ltd. Procede de production de combustibles a partir de dioxyde de carbone capture
WO2008115933A1 (fr) * 2007-03-19 2008-09-25 Doty Scientific, Inc. Hydrocarbures et carburants à base d'alcool provenant d'une énergie renouvelable variable à très haut rendement
US20080245660A1 (en) * 2007-04-03 2008-10-09 New Sky Energy, Inc. Renewable energy system for hydrogen production and carbon dioxide capture
US20100187123A1 (en) * 2009-01-29 2010-07-29 Bocarsly Andrew B Conversion of carbon dioxide to organic products
WO2011020825A1 (fr) * 2009-08-20 2011-02-24 Fruitful Innovations B.V. Photosynthèse artificielle

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4140602A (en) * 1975-09-02 1979-02-20 Texas Gas Transmission Corporation Method for obtaining carbon dioxide from the atmosphere and for production of fuels
US4427508A (en) * 1982-05-03 1984-01-24 Atlantic Richfield Company Light driven photocatalytic process
WO2006006164A2 (fr) * 2004-07-12 2006-01-19 Aytec Avnim Ltd. Procede de production de combustibles a partir de dioxyde de carbone capture
WO2008115933A1 (fr) * 2007-03-19 2008-09-25 Doty Scientific, Inc. Hydrocarbures et carburants à base d'alcool provenant d'une énergie renouvelable variable à très haut rendement
US20080245660A1 (en) * 2007-04-03 2008-10-09 New Sky Energy, Inc. Renewable energy system for hydrogen production and carbon dioxide capture
US20100187123A1 (en) * 2009-01-29 2010-07-29 Bocarsly Andrew B Conversion of carbon dioxide to organic products
WO2011020825A1 (fr) * 2009-08-20 2011-02-24 Fruitful Innovations B.V. Photosynthèse artificielle

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3614059A1 (fr) * 2018-08-23 2020-02-26 Antecy B.V. Procédé et dispositif pour améliorer la qualité de l'air dans des environnements fermés

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