Classifications

• • 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
• • 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
• • 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
  • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
  • H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
• • 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
  • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
  • H01M8/184—Regeneration by electrochemical means
• • 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
• • 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
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• the invention relates generally to a device for storage and conversion of energy, and more particularly to a device capable of absorbing electric, electromagnet ic or caloric energy, storing the absorbed energy, and releasing the absorbed energy, for example as electric or as chemical energy.
• Batteries tend to be large and heavy; their efficiencies tend to be poor; and they tend to lose charge over time even when no electric energy is being taken out. Batteries also suffer from the limitation that they can only store energy that is delivered in the form of electric energy, and they can release the stored energy only in the form of electric energy.
• the conversion of excess energy to a liquid fuel is particularly attractive if the energy is to be used at a different location than where it is generated, or for propelling a vehicle, for example. This is because of the high energy density of l iquid fuels. As explained in the above cited patent appl ication the liquid fuel can be stored at the location where it is generated, for conversion back to electric energy at a later time. This is an attractive option for longer term energy storage, for example for storing solar energy generated during the summer for heating during the winter. It has however been found that the conversion of excess energy to a liquid fuel followed by conversion back to electric energy inev itably results in significant losses. For this reason it may be more cost effective to store the electric energy in some type of battery if the electric energy is intended for to be used in the near future, for example excess solar energy stored during the daytime for use after sunset.
• the present invention addresses these problems by providing a device for energy storage and conversion, containing a chemical energy cache that is capable of absorbing energy and either elcctrochemically storing the absorbed energy or el ect ro-cat a 1 y t i cal 1 y transferring the absorbed energy to a reactant.
• FIG. 1 illustrates the basic concept of the device of the present invention is so-called battery mode
• FIG. 2 illustrates the basic concept of the device of the present invention is so-called reactor mode
• FIG. 3 illustrates the basic concept of the device of the present invention with a two- step reactor for synthesizing methanol
• FIG. 4 illustrates the basic concept of the device of the present invention with a one- step reactor for synthesizing methanol ;
• FIG 5 illustrates a specific embodiment of the device of the present invention.
• FIG 6 shows operation of an electrochemical reactor in the conversion of carbon dioxide to methanol.
• FIG 7 shows the reactor of Figure 6 when operated as a storage battery.
• FIG 8 shows the battery of figure 7 in discharge mode.
• FIG 9 shows an alternate embodiment of the electrochemical reactor.
• FIG 10 illustrates an alternate embodiment wherein the system comprises multiple electrode.
• chemical energy cache means a chemical compound or a combination of interacting chemical compounds capable of absorbing and storing energy.
• single compound chemical energy caches include fluorescent and
• phosphorescent materials which absorb light energy and release it in the form of light.
• Certain solids absorb heat energy by converting to a different crystal structure, and release the absorbed heat energy while reverting back to the original crystal structure.
• Examples of combinations of interacting chemical compounds include redox couples, which comprise a reductant and an oxidant. Redox couples absorb energy when the reductant is oxidized and the oxidant is reduced, and v.v.
• Examples of chemical energy caches that are part icularly suitable for use in the present invention include organic Ionic Liquids and inorganic molten salts and inorganic molten salt hydrates.
• organic Ionic Liquids refers to compounds comprising a cation and an anion, of which at least the cation is an organic molecule.
• Organic Ionic Liquids are liquid at relatively low temperatures, having melting points, for example, at temperatures below 100°C. Examples include l-ethyi-3-methylimidazoiium tetrafluoroborate; l-butyl-3-methylimidazoiium bis(trifluoromethyisulfonyl)imide. Further examples are described in WO 03/029329 A2, the disclosures of which are incorporated herein by reference.
• inorganic molten salt refers to inorganic compounds comprising a metal cation and an inorganic anion, such as hal ide, carbonate, sulfate, and the like. Combinations of a molten metal and a molten salt containing a cation of the same metal are particularly useful as chemical energy caches for use in the present invention.
• halides of sodium, potassium and l ithium particularly the eutectic mixture of lithium chloride and potassium chloride
• chromates of alkal ine earth metals in particular calcium chromate and barium chromate
• double salts such as sodium aluminum chloride ( aA!CLi), which has a conveniently low melting point (157 °C); a mixture of MgCi 2 KG and NaCl, etc.
• inorganic molten salt hydrate refers to hydrated inorganic salts that, as a result of the hydration, have a much lower melting point than the
• Inorganic molten salt hydrates have properties that are very similar to those of organic Ionic Liquids. Inorganic molten salt hydrates offer important advantages over organic Ionic Liquids in that they are far less expensive, and in general chemically and thermally more stable. In addition, organic Ionic Liquids generally require substantially water-free conditions, whereas inorganic molten salt hydrates are tolerant of moisture, even in excess of the amount of water of hydration. On the other hand, organic Ionic Liquids can be made to meet very specific requirements.
• Examples include hydrates of the halides of alkal i and alkaline earth metals, such as Ltd. MgCK and ZnC12. Molten salt hydrates differ from normal aqueous solutions in that all the water is tightly bound within the inner hydration sphere of the cation. ZnCi 2 .4H 2 0 is particularly preferred.
• the term "ground state” as used herein refers to the chemical energy cache in a state in which it contains l ittle or no stored energy. Any energy it may have absorbed at an earlier time has been released or dissipated, and the chemical energy cache is available to absorb its full capacity of energy.
• excited state and “charged state” refer to the chemical energy cache in a state in which it stores a significant amount of releasablc energy. These terms are used interchangeably, with the proviso that if the stored energy is electric energy one w ill be inclined to refer to that state as “charged”, whereas if the stored energy is electromagnetic energy one will be incl ined to refer to that state as “excited”, in line w ith the customary usage of these terms.
• the present invention relates to a device for energy storage and conversion, containing a chemical energy cache that is capable of absorbing energy and cither electrochemically storing the absorbed energy or electro-catal ytical ly transferring the absorbed energy to a reactant.
• a chemical energy cache that is capable of absorbing energy and cither electrochemically storing the absorbed energy or electro-catal ytical ly transferring the absorbed energy to a reactant.
• the chemical energy cache can be selected to absorb one or more of a variety of energy forms, for example heat energy, electric energy, electromagnetic radiation, nuclear radiation, or a combination thereof.
• electromagnetic radiation include infrared radiation, visible light, u.v., microwave, and X-ray.
• the absorbed energy is electric energy, for example from a renewable resource such as solar energy or wind energy.
• the chemical energy cache can be a solid or a liquid.
• suitable examples of liquid chemical energy caches include organic Ionic Liquids; inorganic molten salts; and inorganic molten salt hydrates.
• the device is capable of releasing stored energy in the form of electric energy.
• the chemical energy cache in the dev ice is capable of el ect ro-catal yt ical I y transferring stored energy to a reactant, thereby catalyzing conversion of the reactant to a reaction product.
• the reaction product can be a liquid fuel .
• a reactant is water, and the reaction product is hydrogen.
• the reactant is carbon dioxide, and the reaction product is carbon monoxide.
• one or two devices electrocatal yt ical I y transfer energy to water and carbon dioxide, simultaneously forming hydrogen and carbon monoxide
• syngas The syngas mixture can be converted to, e.g., methane, methanol, Fischer- Tropsch liquid alkanes, and the like, using existing technologies.
• Carbon dioxide for use as a reactant can be generated by the combustion of a carbon-containing fuel, such as biomass or a fossil fuel. Carbon dioxide can also be produced by selectively adsorbing carbon dioxide from atmospheric air, and subsequently desorbing the adsorbed carbon dioxide.
• Water for use as a reactant can similarly be “harvested” from atmospheric air by selective adsorption followed by desorption.
• Figure 2 shows the device in its reactor mode. The absorption and storage of energy are as described for Figure 1 . While in the excited or charged state the device receiv es reactants, such as water, carbon dioxide, etc. These reactants are converted to reaction products, such as hydrogen and carbon monoxide. Reaction products are removed from the device, either as primary reaction products (hydrogen, carbon monox ide), or as secondary reaction products (methanol ). The device converts back to its ground state upon transfer of the stored energy to the reactants.
• reactants such as water, carbon dioxide, etc.
• reaction products such as hydrogen and carbon monoxide.
• reaction products are removed from the device, either as primary reaction products (hydrogen, carbon monox ide), or as secondary reaction products (methanol ).
• the device converts back to its ground state upon transfer of the stored energy to the reactants.
• Figure 3 shows a dev ice with a two-step reactor mode.
• water is converted to hydrogen (as wel l as oxygen ); in the second step carbon diox ide is reacted with hydrogen to form methanol .
• Figure 4 shows a one-step reactor mode. Water and carbon dioxide are
• FIG. 5 show s a specific embodiment of the invention.
• the dev ice contains organic Ionic Liquid and/or inorganic molten salt as the chemical energy cache.
• the device also contains a catalyst, such as a Ni catalyst.
• the catalyst is present in the form of two electrodes, a cathode and an anode (the cathode is shown schematically as one catalyst particle).
• Water and carbon dioxide are supplied as reactants.
• Energy is supplied in the form of electric energy from an array of photovoltaic cells.
• the half reaction taking place at the cathode (reduction of water to hydrogen ) is depicted schematically.
• the other half reaction is the reduction of carbon dioxide to carbon monox ide.
• oxygen is formed (not shown ). Hydrogen and carbon monoxide react catalytical ly to form methanol.
• FIG. 6 show s an electrochemical reactor 1 comprising a vessel 30 filled w ith 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 cel ls. National® from Dupont is an example of a suitable membrane material. Anode 20 preferably comprises manganese (III) oxide (Mn ⁇ Ch )- Alternately anode 20 may comprise an Ag 2 0/Ag redox system.
• Anode 20 preferably comprises manganese (III) oxide (Mn ⁇ Ch )- Alternately anode 20 may comprise an Ag 2 0/Ag redox system.
• Electrode 10 has the form of a hol low, porous tube, made of an electrical ly conducting material, for example a porous metal ; a hollow porous graphite rod; a hollow- graphite honeycomb rod, or the l ike.
• Carbon dioxide gas is supplied to cathode 10 under an overpressure that is high enough to force carbon diox ide 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 1 0.
• water is supplied to anode 20.
• the reaction at the anode is the half reaction of the well-known water electrolysis reaction : 6H 2 0 ⁇ 4H 3 0 + + 4c + 0 2 (1)
• 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.
• Figure 7 shows the operation of the reactor as a storage battery for electric energy.
• An electric voltage 32 is suppl ied to the electrodes, as in Figure 6. No reactants are suppl ied to the electrodes, however.
• reaction at cathode 1 0 is reaction (5 ):
• the reaction at anode 20 is oxidation of Mn(III) to Mn(IV): Mn 2 0 3 + 2 0ff ⁇ 2 Mn0 2 + H 2 0 + 2c " and the overall reaction equation:
• Figure 8 shows the reactor of Figure 1 operated as a charged battery in the process of being discharged. Al l reactions are identical to those of Figure 7, except that the reactions proceed in opposite direction.
• the overall reaction in an acidic environment is:
• Figure 9 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 Mn(II) to solid Mn( IV), as follows:
• the location where the electrical energy is stored and where the energy is used to perform chemical conversions are separated.
• This embodiment is illustrated at the hand of figure 10.
• the system can consist of multiple electrodes.
• the combination of the first two electrodes 40 and 4 1 by closing sw itch 43, allows energy to be stored by making an oxygen evolution reaction occur in electrolyte 45 at electrode 40, while at the same time making zinc deposition occur from electrolyte 46 on electrode 41 , according to reactions (1) and (5 ).
• switch 44 can be closed to connect electrodes 41 and 42. The previously deposited zinc will go back onto solution, according to the reverse of reaction (5).
• the energy released by this dissolution reaction can be used at electrode 42 to drive any of the reactions (2), (3), (4), (6) or combinations thereof.
• electrolytes 45, 46 and 47 can be of the nature as described previously in this patent, and that they can be, depending on their nature and composition, separated by membranes 48 and/or 49.
• Electrodes/electrolyte units for example for the recovery of the stored energy in the form of electricity, similarly to a zinc-air battery.

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Citations (8)

• 2013
  • 2013-06-20 WO PCT/EP2013/062937 patent/WO2013190065A1/fr not_active Ceased

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