WO2002062700A2 - Procede et dispositif pour la production d'hydrogene par oxydation partielle de carburants hydrocarbones - Google Patents
Procede et dispositif pour la production d'hydrogene par oxydation partielle de carburants hydrocarbones Download PDFInfo
- Publication number
- WO2002062700A2 WO2002062700A2 PCT/FR2002/000452 FR0200452W WO02062700A2 WO 2002062700 A2 WO2002062700 A2 WO 2002062700A2 FR 0200452 W FR0200452 W FR 0200452W WO 02062700 A2 WO02062700 A2 WO 02062700A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- reactor
- hydrogen
- reaction
- partial oxidation
- membrane
- Prior art date
Links
Classifications
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
- B01J19/088—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy giving rise to electric discharges
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
- B01J8/009—Membranes, e.g. feeding or removing reactants or products to or from the catalyst bed through a membrane
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0242—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical
- B01J8/025—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical in a cylindrical shaped bed
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/342—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents with the aid of electrical means, electromagnetic or mechanical vibrations, or particle radiations
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/386—Catalytic partial combustion
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
-
- 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
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
-
- 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
-
- 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
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/0053—Controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0871—Heating or cooling of the reactor
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0873—Materials to be treated
- B01J2219/0881—Two or more materials
- B01J2219/0883—Gas-gas
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0894—Processes carried out in the presence of a plasma
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
- C01B2203/0288—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step containing two CO-shift steps
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0405—Purification by membrane separation
- C01B2203/041—In-situ membrane purification during hydrogen production
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/047—Composition of the impurity the impurity being carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/066—Integration with other chemical processes with fuel cells
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0861—Methods of heating the process for making hydrogen or synthesis gas by plasma
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1076—Copper or zinc-based catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1082—Composition of support materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1217—Alcohols
- C01B2203/1223—Methanol
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1247—Higher hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/16—Controlling the process
- C01B2203/1604—Starting up the process
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
- C01B2203/84—Energy production
-
- 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 present invention relates to a process for the production of hydrogen by partial oxidation of hydrocarbon fuels activated by a plasma with or without a catalyst.
- Electric power is generated during a chemical reaction between a reducing agent, hydrogen, and an oxidant, oxygen. It is proportional to the flow rates of these two gases.
- the operation of PEMs is optimal when they are supplied with pure hydrogen.
- a hydrogen-rich gas stream containing for example N 2 , CH 4 , CO 2, etc., can be used to feed the PEM.
- these gases are inert with respect to the platinum-based catalyst which participates in the dissociation of the hydrogen molecules within the cell.
- this catalyst is quickly poisoned by a gas containing more than 10 ppm of CO.
- hydrogen has a low energy density per unit volume. The same amount of energy will therefore occupy a larger volume in the case of hydrogen than in the case of a conventional hydrocarbon.
- the storage of hydrogen gas poses problems with regard to safety aspects. It is therefore preferable to feed the PEM not from a hydrogen storage, but from a hydrocarbon or an alcohol, the hydrogen of which will be released as and when required.
- the gas obtained is therefore a mixture of H 2 , H 2 O, CO, CO 2 , C n H 2n + 2 , C n H 2n ...
- This can be done either physically by a membrane allowing the extraction of hydrogen, or chemically by a "shift” type reaction: CO + H 2 O ⁇ C0 2 + H 2 "Shift" reaction, exothermic
- the mixing and ionization of the reactants (mixture of hydrocarbons - CH, C 2 H 6 , C 3 H 8 or C 4 H 10 , and oxygen, whatever its source: H 2 O, H 2 0 + O 2 , O 2 ) are produced in a plasma reactor where the temperature reached is less than 1200 ° C. and the pressure less than 6 bar.
- a second compartment, separated from the first by a perforated ceramic or metal plate contains tubes (often nickel) with which the species come into contact, which has the consequence of increasing the conversion rate.
- a mixture containing 97.3% CH, 1.4% C 2 H 6 , 0.3% C 3 H 8 and 0.1% C 4 H 10 and pure oxygen (such that 0 2 pure / hydrocarbons: 0.48) is introduced without preheating, at a flow rate of 1.3 Nm 3 / h and a pressure of 1.5 bar in the reactor.
- the ratio of synthesis gas formed / incoming hydrocarbon is 0.97; the H 2 / CO ratio obtained is 1.4 and the electrical expenditure is 0.4 Wh / m of gas formed.
- the Johnson Matthey process (application WO 9 948 805) operates at temperatures of the order of 600 ° C. but it still requires a significant supply of heat which is carried out either using an oven or by mixing air and hydrogen.
- the reactions take place in the presence of a rhodium-based catalyst supported by refractory oxides containing cerium and zirconium cations.
- the gas formed is then purified using a catalytic "shift" stage.
- the invention of Clawson et al. (US Pat. No. 6,083,425) describes a reformer comprising several successive compartments which make it possible to chemically convert a fuel into a gas stream containing mainly hydrogen and carbon dioxide.
- the concentration of carbon monoxide in the product gas is reduced to less than 0.5% by volume.
- the fuel can be a light hydrocarbon (methane, propane), an alcohol (methanol, ethanol) or a complex fuel such as gasoline, JP-8 or kerosene.
- the first step is most often a partial thermal oxidation of the fuel at a temperature above 1000 ° C. This reaction is then spontaneous. But ignition of the mixture can be caused by a hot surface or a candle, if necessary.
- catalytic steam reforming is carried out either of another fraction of the fuel, or of fuel not converted in the first compartment, or of certain constituents of the gas stream produced in the first compartment (for example methane ).
- the catalyst proposed for carrying out this reaction at a temperature between 700 and 900 ° C. is based on nickel.
- application WO 9 934 898 describes a palladium membrane used in conjunction with a nickel-based catalyst allowing the complete conversion of the reactants during the reactions of "shift” and steam reforming of methane by continuous under-drawing. hydrogen formed.
- the invention provides a process making it possible to obtain, using relatively simple and inexpensive means, a very pure hydrogen which can be used in particular for supplying batteries at low temperatures, and this, with an increase in the conversion yields of the reactions involved.
- this process consists in carrying out, in a first compartment, a partial oxidation, at room temperature, of a hydrocarbon fuel, so as to obtain a gas stream rich in hydrogen, to rid the primary gas mixture produced in this first compartment, most of the carbon monoxide it contains, using a catalytically activated "shift" reaction in a second compartment, and to separate the hydrogen present in the secondary mixture contained in the second compartment other constituents of this mixture, thanks to a membrane.
- the above-mentioned oxidation phase inside the first enclosure can be carried out by mixing the fuel with a source of oxygen, the pressure inside the first enclosure being between 2 and 15 bar, while the temperature initially corresponding to room temperature rises due to the exothermicity of the reaction to a relatively low level, for example of the order of 600 ° C. Due to this low temperature level, unlike all other existing partial oxidation processes, the process according to the invention allows the use of standard materials in the design of the reactor body.
- Enriched air as a source of oxygen has many advantages over air, in particular because it makes it possible to significantly reduce the nitrogen content of the incoming gas but also of the gas leaving the partial oxidation reactor:
- the enriched air improves the fuel conversion efficiency because the nitrogen present, which does not react, has a diluting effect and unnecessarily takes away a non-negligible part of the thermal energy released. during the reaction.
- the increase in temperature due to the exothermicity of the partial oxidation reaction is significantly greater than with air, which favors fuel conversion and eliminates any preheating system during the priming phase.
- the enriched air allows the membrane to function better since, at equal total pressure, the partial pressure of hydrogen is higher. However, the flow of hydrogen through the membrane is a function of the difference in partial pressures of hydrogen between the upstream and downstream of the membrane.
- Figure 1 is a theoretical diagram of a hydrogen production device according to the invention.
- FIG. 2 is a diagram showing the percentage of hydrogen and oxygen as a function of time, during a partial oxidation of methane activated by plasma;
- FIG. 3 is a diagram similar to that illustrated in FIG. 2 showing the effects of plasma on the percentages of H 2 and O 2 during a partial oxidation of plasma-activated propane.
- the hydrogen production device involves two reactors 1, 2 connected to each other via a conduit 3 equipped with a heat exchanger 4.
- the first reactor 1 is designed so as to cause the partial oxidation of a hydrocarbon fuel coming from a source 5 in contact with an air stream possibly enriched in oxygen, coming from an enrichment circuit 6.
- the oxidation reaction will be initiated and maintained by means of electric arc discharges.
- These arc discharges can be produced by a spark plug 7, the electrodes of which are connected to a high-voltage pulse generator 8 capable of providing a discharge, for example every 300 ⁇ s.
- the energy of each of the landfills could be 3.2 mJ, which corresponds to an expenditure of 640 J / min, or 11 W.
- the generator 8 may therefore advantageously comprise means making it possible to vary the frequency and / or the times of emission of the electrical pulses to regulate the production of hydrogen.
- the oxygen source consists of air enriched with oxygen. In this case, self-maintenance of the oxidation reaction which occurs in the first chamber is obtained. In this case, the electric arc only serves to initiate the reaction and can then be eliminated. The consumption of this electrical energy solution is therefore considerably reduced or even canceled (in the case where a piezoelectric igniter is used).
- the enrichment circuit 6 comprises a compressor C] delivering pressurized air (for example 13 bar) in a separation unit S allowing the extraction of part of the nitrogen N 2 present in the air and a compressor C 2 making it possible to inject the enriched air coming from the separation unit into the reactor under a pressure of approximately 10 bar.
- the pressure of the gas mixture present in reactor 1 is maintained at a value of, for example, between 2 and 15 bar.
- the oxidation reaction inside this reactor is initiated and possibly maintained by the plasma generated by an electrical discharge produced by the spark plug 7.
- the average temperature within the reactor, maintained by the oxidation reaction (exothermic) is around 500 ° C to 600 ° C.
- the second reactor 2 is designed so as to obtain a “shift” reaction between the carbon monoxide present in the gas mixture originating from the first reactor 1 and water vapor, this reaction leading to the formation of carbon dioxide and of 'hydrogen.
- the water vapor comes from a steam generation circuit successively comprising a steam generator GV supplied by a water source via a pump P and the exchanger 4 which overheats the steam thanks to the heat input of the gas mixture flow from reactor 1.
- the generator GV can be eliminated, the vapor then being produced in the exchanger 4.
- the excess heat produced in the first reactor 1 can also be used to bring the second reactor to a temperature of around 500 ° C.
- the temperature prevailing in the two adjacent reactors 1, 2 is of the same order of magnitude, which avoids having to use a cooling system.
- the second reactor 2 contains a high temperature "shift" catalyst operating for example in the temperature range between 300 ° C. and 600 ° C.
- This catalyst can for example be composed of iron oxide and chromium oxide.
- the pressure inside the reactor may be of the order of 6 to 10 bar with a partial pressure of hydrogen of the order of 2 bar.
- a third reactor in which a low temperature "shift" is carried out is placed next to the second reactor 2.
- This third reactor may contain a catalyst preferably composed of copper and zinc oxide supported by l alumina which operates in the temperature range between 150 and 300 ° C.
- This reactor 2, or these two reactors, are designed to convert 70 to 99% of the carbon monoxide.
- Reactor 2 contains a hydrogen-selective membrane 9 because the operation of "PEM" type cells is optimal when they are powered by pure hydrogen.
- the membrane 9 is preferably of the metallic type. It is composed of a ceramic or porous metal support on which a layer of palladium / silver alloy is deposited. Indeed, palladium and its alloys are well known for being selectively permeable to hydrogen. This layer used to separate the hydrogen from the other gases must be fine (of the order of a micrometer) so as not to limit the flow of hydrogen too much. It must therefore be supported by a porous layer several millimeters thick which gives its rigidity and resistance to the entire membrane. Several geometries are possible: discs, plates, tubes and thermowells.
- the membrane placed in reactor 2 where a high temperature "shift" reaction takes place, thus separates it into two separate compartments.
- the first Ei converts the carbon monoxide present in the primary gas stream and the second E 2 is a collection chamber for pure hydrogen. This increases the conversion rate of carbon monoxide by continuously withdrawing the nascent hydrogen and the hydrogen contained in the primary gas stream.
- the hydrogen produced in compartment E 2 for example at a pressure of 1 bar, is substantially pure and is capable of directly supplying a fuel cell operating at low temperature.
- Figures 2 and 3 show the results obtained during the partial oxidation in the presence of air of methane at an initial temperature of 250 ° C and 300 ° C ( Figure 2) and propane at an initial temperature of 250 ° C (figure 3).
- the analysis of gases from reactor 1 is carried out using a gas chromatograph coupled to two detectors: a catharometer and a flame ionization detector.
- a catharometer and a flame ionization detector.
- the percentage of hydrogen in the gas formed reaches 6 to 8% while the oxygen concentration drops from 20 to 8-10%.
- the delay in the appearance of hydrogen can be partly attributed to the response time of the analyzer.
- the gas analyzed at the reactor outlet no longer contains hydrogen and the oxygen is again at its initial concentration.
- a mixture of gaseous products is then formed, some of which contain hydrogen: C n H 2n + 2 , C n H 2n , H 2 ...
- the hydrogen yield is the quantity of H 2 formed compared to all of the hydrogenated molecules produced during the reaction.
- Fuel conversion efficiency is defined as the amount of fuel converted relative to the fuel introduced into the reactor.
- This first stage makes it possible to form, from a hydrocarbon and an oxygen source, a mixture rich in hydrogen capable of containing CO, C0 2 , H 2 0 and the fraction of unconverted fuel. If air is used as a source of oxygen, the high proportion of nitrogen that it contains limits the progress of the reactions by a dilution effect of the reactants. It is therefore advisable to reduce the amount of nitrogen in the oxidizing gas. Studies with mixtures containing N 2 / O 2 in varying proportions have shown that the fuel conversion efficiency is optimized for an N 2/0 2 equal to 60 / 40.
- the reactor feed mixture can be by carried out either by of a bottle, either from an air enrichment module.
- the invention then comprises a complementary stage composed of an air compressor, a separating membrane and a booster.
- the membrane is composed of multiple hollow fibers of polycarbonates.
- the successive action of the plasma and of a catalyst makes it possible, in the particular case where the fuel is propane, to obtain a total conversion of the fuel.
- the hydrogen contained in the fuel is divided into 80% of dihydrogen (product of partial oxidation) and 20% of water (product of complete combustion).
- the reactor also contains a catalyst preferably composed of iron oxide and chromium oxide.
- the composition of the gas formed is as follows: 38% nitrogen, 30% hydrogen, 20% carbon monoxide, 6% water vapor, 4% carbon dioxide and 2 % of methane.
- the gas thus produced can be used directly by a fuel cell operating at high temperature of the SOFC ("Solid Oxide Fuel Cell”) or MCFC ("Molten Carbonate Fuel Cell”) type but does not make it possible to supply a fuel cell operating at low temperature such as PEM, much more demanding in terms of carbon monoxide content.
- SOFC Solid Oxide Fuel Cell
- MCFC Molten Carbonate Fuel Cell
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Toxicology (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fluid Mechanics (AREA)
- Electromagnetism (AREA)
- Mechanical Engineering (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02703659A EP1358125A2 (fr) | 2001-02-07 | 2002-02-04 | Procede et dispositif pour la production d'hydrogene par oxydation partielle de carburants hydrocarbones |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0101673A FR2820416B1 (fr) | 2001-02-07 | 2001-02-07 | Procede et dispositif pour la production d'hydrogene par oxydation partielle de carburants hydrocarbones |
FR01/01673 | 2001-02-07 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2002062700A2 true WO2002062700A2 (fr) | 2002-08-15 |
WO2002062700A3 WO2002062700A3 (fr) | 2002-11-28 |
Family
ID=8859743
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2002/000452 WO2002062700A2 (fr) | 2001-02-07 | 2002-02-04 | Procede et dispositif pour la production d'hydrogene par oxydation partielle de carburants hydrocarbones |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP1358125A2 (fr) |
FR (1) | FR2820416B1 (fr) |
WO (1) | WO2002062700A2 (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11701632B2 (en) | 2018-12-10 | 2023-07-18 | Ekona Power Inc. | Method and reactor for producing one or more products |
US12012333B1 (en) | 2022-12-19 | 2024-06-18 | Ekona Power Inc. | Methods and systems for adjusting inputs to a pyrolysis reactor to improve performance |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2872149B1 (fr) * | 2004-06-28 | 2007-10-19 | Physiques Sarl Et Chimiques | Conversion plasma-catalytique de matieres carbonees |
WO2006109294A1 (fr) * | 2005-04-12 | 2006-10-19 | C. En. Limited | Systemes et procedes pour la production d’hydrogene |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3251652A (en) * | 1962-05-17 | 1966-05-17 | Engelhard Ind Inc | Process for producing hydrogen |
GB2311790A (en) * | 1996-04-04 | 1997-10-08 | British Gas Plc | Production of synthesis gas from hydrocarbonaceous feedstock |
WO1999025649A1 (fr) * | 1997-11-17 | 1999-05-27 | Johnson Matthey Public Limited Company | Generateur d'hydrogene |
WO1999034898A1 (fr) * | 1998-01-06 | 1999-07-15 | The Regents Of The University Of California | Appareil et procede pour la recuperation simultanee d'hydrogene a partir d'eau et a partir d'hydrocarbures |
US6090312A (en) * | 1996-01-31 | 2000-07-18 | Ziaka; Zoe D. | Reactor-membrane permeator process for hydrocarbon reforming and water gas-shift reactions |
US6171574B1 (en) * | 1996-09-24 | 2001-01-09 | Walter Juda Associates, Inc. | Method of linking membrane purification of hydrogen to its generation by steam reforming of a methanol-like fuel |
-
2001
- 2001-02-07 FR FR0101673A patent/FR2820416B1/fr not_active Expired - Fee Related
-
2002
- 2002-02-04 EP EP02703659A patent/EP1358125A2/fr not_active Withdrawn
- 2002-02-04 WO PCT/FR2002/000452 patent/WO2002062700A2/fr not_active Application Discontinuation
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3251652A (en) * | 1962-05-17 | 1966-05-17 | Engelhard Ind Inc | Process for producing hydrogen |
US6090312A (en) * | 1996-01-31 | 2000-07-18 | Ziaka; Zoe D. | Reactor-membrane permeator process for hydrocarbon reforming and water gas-shift reactions |
GB2311790A (en) * | 1996-04-04 | 1997-10-08 | British Gas Plc | Production of synthesis gas from hydrocarbonaceous feedstock |
US6171574B1 (en) * | 1996-09-24 | 2001-01-09 | Walter Juda Associates, Inc. | Method of linking membrane purification of hydrogen to its generation by steam reforming of a methanol-like fuel |
WO1999025649A1 (fr) * | 1997-11-17 | 1999-05-27 | Johnson Matthey Public Limited Company | Generateur d'hydrogene |
WO1999034898A1 (fr) * | 1998-01-06 | 1999-07-15 | The Regents Of The University Of California | Appareil et procede pour la recuperation simultanee d'hydrogene a partir d'eau et a partir d'hydrocarbures |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11701632B2 (en) | 2018-12-10 | 2023-07-18 | Ekona Power Inc. | Method and reactor for producing one or more products |
US12012333B1 (en) | 2022-12-19 | 2024-06-18 | Ekona Power Inc. | Methods and systems for adjusting inputs to a pyrolysis reactor to improve performance |
Also Published As
Publication number | Publication date |
---|---|
FR2820416A1 (fr) | 2002-08-09 |
WO2002062700A3 (fr) | 2002-11-28 |
EP1358125A2 (fr) | 2003-11-05 |
FR2820416B1 (fr) | 2003-12-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
FR2757499A1 (fr) | Generateur d'hydrogene | |
CA2980664C (fr) | Systeme de production d'electricite par pile a combustible sofc avec circulation des especes carbonees en boucle fermee | |
EP2262725B1 (fr) | Procédé de démarrage d'une unité de production d'hydrogène hautement intégrée thermiquement par reformage d'une charge hydrocarbonée | |
EP2984209A1 (fr) | Procedes d'obtention de gaz combustible a partir d'electrolyse de l'eau (eht) ou de co-electrolyse avec h2o/co2 au sein d'une meme enceinte, reacteur catalytique et systeme associes | |
WO2004041425A1 (fr) | Reacteur a chauffage electrique pour le reformage en phase gazeuse | |
EP1608858A2 (fr) | Procede et dispositif de cogeneration par turbine a gaz avec chambre de postcombustion | |
EP1423331A1 (fr) | Procede et dispositif de production d'un gaz riche en hydrogene par pyrolyse thermique d'hydrocarbures | |
EP2766514A2 (fr) | Procédé et système de traitement de gaz carbonés par hydrogénation électrochimique pour l'obtention d'un composé de type cxhyoz | |
WO2001000320A1 (fr) | Catalyseur et procede de reformage de l'ethanol ainsi que systeme de pile a combustible les utilisant | |
EP1565398A1 (fr) | Procede de production de gaz de synthese | |
CA2659547C (fr) | Procede de production d'hydrogene hautement integre thermiquement par reformage d'une charge hydrocarbonee | |
FR2933391A3 (fr) | Conversion du glycerol en carburant liquide propre et renouvelable | |
EP2129622A2 (fr) | Production d'hydrogene par dissociation de l'eau en presence de sno en utilisant le couple sno2/sno dans une suite de reactions thermochimiques | |
EP1358125A2 (fr) | Procede et dispositif pour la production d'hydrogene par oxydation partielle de carburants hydrocarbones | |
FR2873306A1 (fr) | Generateur electrique et son application a l'oxydation totale ou partielle de carburants | |
WO2011148066A2 (fr) | Procédé de production anaérobie d'hydrogène | |
WO2004046029A2 (fr) | Production d'hydrogene a partir d'hydrocarbures | |
EP0318342B1 (fr) | Procédé de reformage de méthanol impur et dispositif de mise en oeuvre | |
FR2888835A1 (fr) | Procede de production d'hydrogene a partir d'hydrocarbures ou de composes hydrocarbones | |
FR2874911A1 (fr) | Systeme de reformage et procede d'alimentation en gaz riche en hydrogene pour une pile a combustible | |
FR2879026A1 (fr) | Systeme de generation d'energie electrique embarque sur un vehicule automobile equipe d'une pile a combustible et procede associe | |
FR2919118A1 (fr) | Procede de generation d'electricite et d'hydrogene comportant un reformeur hybride | |
FR2899020A1 (fr) | Systeme de pile a combustible a haut rendement |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A2 Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LR LS LT LU LV MA MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A2 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
AK | Designated states |
Kind code of ref document: A3 Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LR LS LT LU LV MA MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A3 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2002703659 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 2002703659 Country of ref document: EP |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
NENP | Non-entry into the national phase |
Ref country code: JP |
|
WWW | Wipo information: withdrawn in national office |
Country of ref document: JP |