Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
  • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
  • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
  • C10K3/04—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
• • 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
  • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
  • B01J8/1809—Controlling processes
• • 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
  • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
  • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
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  • 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
  • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
  • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
  • C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
  • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
  • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
  • C07C1/0405—Apparatus
  • C07C1/041—Reactors
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
  • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
  • C10L3/08—Production of synthetic natural gas
• • 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
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  • 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
  • C01B2203/0415—Purification by absorption in liquids
• • 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
  • C01B2203/042—Purification by adsorption on solids
  • C01B2203/043—Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
• • 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
  • C01B2203/046—Purification by cryogenic separation
• • 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
  • C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch 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
  • C01B2203/16—Controlling the process
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
  • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
  • C07C2521/04—Alumina
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
  • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
  • C07C2523/74—Iron group metals
  • C07C2523/755—Nickel
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
  • C10L2290/06—Heat exchange, direct or indirect
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
  • C10L2290/10—Recycling of a stream within the process or apparatus to reuse elsewhere therein
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
  • C10L2290/46—Compressors or pumps
• • 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
  • Y02E50/00—Technologies for the production of fuel of non-fossil origin
  • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
• • 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

Definitions

• the present invention relates to a device for the hybrid production of synthetic dihydrogen and/or synthetic natural gas, here also called synthetic methane, and a process for the hybrid production of synthetic dihydrogen and/or synthetic methane. It applies, in particular, to the field of waste and biomass recovery.
• This invention can also be applied to a synthesis gas resulting from the conversion of coal or any other hydrocarbon-based materials or any gas containing at least carbon monoxide (CO).
• Biomethane and bio-hydrogen are expected to play a major role in the global energy mix, with biomethane replacing natural gas, and bio-hydrogen replacing the hydrogen produced mainly today by reforming natural gas and to a lesser extent by electrolysis of water.
• biohydrogen replacing natural gas
• bio-hydrogen replacing the hydrogen produced mainly today by reforming natural gas and to a lesser extent by electrolysis of water.
• the expected emergence of means of mobility using these two energy vectors could lead to a significant increase in demand.
• the market for biomethane is clearly established.
• the demand for bio-hydrogen in the years to come is uncertain, as it depends on many elements, including the creation of distribution networks and the mass development of hydrogen mobility, for example.
• Methanation is the conversion of carbon monoxide or carbon dioxide in the presence of hydrogen and a catalyst or biological strain to produce methane. It is governed by the following competitive hydrogenation reactions:
• the methanation reaction is a strongly exothermic reaction with a decrease in the number of moles; According to Le Chatelier's principle, the reaction is favored by pressure and unfavorable by temperature.
• the production of methane by hydrogenation of carbon monoxide is maximum for a gas with a composition close to the stoichiometric composition, that is to say whose H2/CO ratio is close to 3.
• the syngas produced by gasification with steam, in particular of biomass is characterized by a lower H2/CO ratio, of the order of 1 to 2 when the proportion of steam to biomass at the gasification inlet is less than 1, which is the most common case in the state of the art.
• this ratio must be adjusted, either by adding hydrogen, for example from a fatal source or produced by electrolysis of water, or most often by producing hydrogen by reaction between carbon monoxide and water by the Water Gas Shift (R1) reaction, known as “WGS” and translated as “water gas reaction”:
• the WGS reaction can be carried out in a specific reactor placed upstream of the methanation.
• the two reactions of methanation and of WGS can be carried out within the same reactor; the steam needed for the WGS reaction is mixed with the synthesis gas or directly injected into the reactor.
• nickel Constituent of the catalyst or present in the material constituting the walls of the reactor
• carbon monoxide carbon monoxide
• Ni(CO) 4 nickel tetracarbonyl
• the heat released during the conversion of CO is approximately 2.7 kWh during the production of 1 Nm 3 of methane.
• the control of the reactor temperature, and therefore the elimination of the heat produced by the reaction is one of the key points for minimizing the deactivation of the catalyst (sintering, etc.) and maximizing the conversions into methane. If the reactor temperature increases, the methane production decreases sharply. If the temperature drops below 250°C, the methanation reaction is inhibited, because the kinetics become very slow.
• composition of crude SNG at the reactor outlet is closely linked to the operating conditions of the reactor (pressure, temperature, adiabatic or isothermal nature, stoichiometry, catalyst, etc.) which govern the balances and the chemical kinetics of the reactions R1, R2 and R3 . These reactions together form water and its separation is therefore required.
• Concerning the other species (CO, CO2 and H2), their respective contents depend on the operating mode of the reactor (adiabatic or isothermal) and on the other hand on the temperature and/or the pressure. From a thermodynamic point of view, a high pressure and a low temperature will considerably reduce the CO and H2 contents. Below 250°C, the methanation reaction can be strongly inhibited.
• the operating mode constitutes a lock for the simplification of the process chain.
• the reaction is limited by the thermodynamic equilibrium.
• the temperature induced can however exceed the maximum admissible temperature of the catalyst and lead to its deactivation by sintering of the active metals.
• Diluting the reaction mixture with a gas such as water vapour, CO2, or a thermal ballast makes it possible to limit the temperature.
• a gas such as water vapour, CO2, or a thermal ballast makes it possible to limit the temperature.
• One method consists for example of recycling humid gas, cooled to around 250° C., from the first reactor, towards its inlet. Practically, the industrial processes implementing equilibrium reactors consist of an arrangement of several reactors with recycling of part of the gas for some of them.
• This type of methanation system often requires a prior adjustment of the H2/CO ratio to 3 by WGS upstream to avoid coke deposition, for example.
• WGS upstream to avoid coke deposition, for example.
• the reactor In the event of strong exothermicity, the required exchange surfaces are sometimes very large.
• the reactor In the case of a cooled fixed bed reactor, in order to maximize the exchange surface area/volume ratio, the reactor generally takes the form of a multitubular reactor, the catalyst being placed inside the tubes, called “TWR” (for “Throughwall Cooled Reactor”, translated by reactor cooled through the walls).
• the cooling fluid can be water, an organic liquid or a mixture of organic liquids or even a gas (N2, CO2, etc.). Control of the outlet temperature is easy and can for example be ensured by boiling the coolant (US 2662911, US 2740803).
• the catalyst is directly impregnated with the walls of the cooled tubes to maximize the heat exchanges.
• reactor cooled by the walls consists not in placing the catalyst in the tubes, but on the contrary in integrating a dense bundle of cooled tubes within a catalytic bed (US4636365, US6958153, US4339413).
• the BWR concept resulting from the production of methanol, recently adapted for the methanation of CO2 is probably applicable to the methanation of a gasification syngas by means of a pre-WGS. It is based on a double-pass tubular reactor cooled by the walls. In this reactor, several tubes containing the catalyst are dedicated to a first pass allowing the syngas to be converted into methane. As a direct output from this pass, part of the SNG is recompressed before being mixed with the feed syngas stream. The other part of the first pass SNG is cooled to condense the water formed by the reactions. Then, the methanation is completed in a second pass through other tubes arranged in the same reactor.
• the main advantage of providing a second pass is to keep an SNG of relatively constant quality even if the first pass catalyst is gradually degraded by displacement of the reaction front.
• the implementation of a fluidized bed reactor is a simple and effective solution to limit the reaction temperature.
• the fluidization of the catalyst by the reaction mixture allows a homogenization of the temperatures and therefore the isothermality of the catalytic layer.
• the elimination of The heat produced by the reaction takes place via heat exchangers immersed within the fluidized layer with high heat transfer coefficients of the order of 400 to 600 W/Km 2 .
• the PSI methanation fluidized bed is also known (EP1568674A1, WO2009/007061 A1).
• This invention implements a cooling system constituted, similarly to the COMFLUX device, by a bundle of tubes arranged in the bed.
• the PSI patents claim a process for the production of SNG from the gasification of biomass. This process claims a methanation solution in a fluidized bed without prior treatment of the syngas on adsorption beds made of activated carbon.
• ENGIE methanation fluidized bed reactors are also known. These technologies essentially offer technical solutions for controlling the isothermality of the reactor (by superheated steam or by injection of liquid water into the reactor, for example).
• the WGS reaction (formula 2 above) is reversible and weakly exothermic, and consists in converting CO and H2O into H2 and CO2:
• thermodynamic equilibrium is favored by low temperatures, the kinetics of this reaction is nevertheless limited under these conditions if the catalyst is not appropriate.
• WGS catalysts are based on iron, chromium, copper or zinc and are implemented between 200°C and 450°C, and under a pressure of 1 bar to 35 bar. The chromium limits the sintering of the catalyst, although a replacement every 2-5 years is necessary. Cerium-based catalysts also show interesting performances for WGS conversion at high temperature. Low temperature WGS catalysts are mainly composed of copper/zinc deposited on an aluminum oxide.
• Linde proposes a method for producing hydrogen from biomass gasification.
• the biomass is gasified in air, at atmospheric pressure and up to 600°C, the syngas is cooled then introduced into a WGS reactor, the products of this reaction are cooled then introduced into an electrochemical separation and compression apparatus (7 -14 bar) allowing to separate the outgoing hydrogen at 150-350 bar.
• Haldor Topsoe makes it possible to enrich in hydrogen a syngas composed of at least 25%, 40% or 70% on a dry basis of CO and H2.
• Membrane reactors are particularly efficient for the WGS reaction.
• the membranes integrated into the reactor make it possible to continuously extract the hydrogen produced by the reaction, thus shifting the balance towards the conversion of CO into hydrogen. Thus, very high conversion rates can be achieved.
• this reactor can hardly make it possible to produce synthetic methane, because the H2 of the syngas or that produced by WGS would be continuously separated from its formation.
• An example of this type of process applied to the gasification of biomass is given in patent US201783721 from the National University of Singapore.
• Various technological solutions generally dedicated either to the production of methane or to that of hydrogen are numerous. However, none of the solutions mentioned above addresses the following technical problems:
• the present invention aims to remedy all or part of these drawbacks.
• the present invention relates to a device for the hybrid production of synthetic dihydrogen and/or synthetic methane, which comprises:
• syngas synthesis gas
• CO for “carbon monoxide”
• control system comprising means for selecting an operating configuration of the reactor and means for issuing a command representative of the selected configuration, the reactor being configured to operate according to a given configuration according to the command emitted by the means of emission.
• the conversion reactor comprises a catalytic bed comprising two separate catalysts, a first catalyst being configured to promote a Sabatier reaction at medium temperature, preferably between 250° C. and 350° C., and a second catalyst being configured to promote a reaction of the gas with water at high temperature, preferably above 350°C.
• the conversion reactor comprises a catalytic bed comprising two separate catalysts, a first catalyst being configured to promote a Sabatier reaction at medium temperature, preferably between 250° C. and 350° C., and a second catalyst being configured to promote a reaction of the gas with water at low temperature, preferably between 200°C and 250°C.
• the conversion reactor comprises a catalytic bed comprising a bifunctional catalyst, configured to promote a Sabatier reaction at medium temperature, preferably between 250° C. and 350° C., in the first configuration of the reactor and to promote a water gas reaction at high temperature in the second configuration of the reactor, preferably above 350°C.
• the conversion reactor comprises a catalytic bed comprising a bifunctional catalyst, configured to promote a Sabatier reaction at medium temperature, preferably between 250° C. and 350° C., in the first configuration of the reactor and to promote a water gas reaction at low temperature in the second configuration of the reactor, preferably between 200°C and 250°C.
• the device that is the subject of the present invention comprises, downstream of the conversion reactor, a water separator configured to supply the separated water to a water evacuation or recovery (e.g. steam production) or to an injector to feed the conversion reactor.
• a water separator configured to supply the separated water to a water evacuation or recovery (e.g. steam production) or to an injector to feed the conversion reactor.
• the device that is the subject of the present invention comprises means for compressing the syngas at a determined pressure, the outlet pressure of the compression means being determined according to the command issued by the control system. In some embodiments, the device that is the subject of the present invention comprises means for expanding the syngas at a determined pressure, the outlet pressure of the expanding means being determined according to the command issued by the control system.
• the device that is the subject of the present invention comprises a heat exchanger immersed in the conversion reactor, said heat exchanger being configured to cool or heat the reactor to a temperature determined according to the command issued by the system control.
• the device that is the subject of the present invention comprises a recirculator of at least part of the outlet gas towards the inlet for syngas, a quantity of recirculated gas being determined according to the command issued by the ordered.
• the device that is the subject of the present invention comprises, downstream of the conversion reactor:
• a methane outlet selector connected to a methane recirculator towards the syngas inlet and to a methane outlet
• the output selector for dihydrogen is configured to direct the dihydrogen to the dihydrogen output
• the methane output selector is configured to direct the methane to the methane recirculator
• the output selector for dihydrogen is configured to direct the dihydrogen to the dihydrogen recirculator and the output selector for methane is configured to direct methane to the methane outlet.
• the catalytic conversion reactor is an isothermal reactor.
• the catalytic conversion reactor is a fluidized bed reactor.
• the catalytic conversion reactor is unique.
• the present invention relates to a process for the hybrid production of synthetic dihydrogen and/or synthetic methane, which comprises:
• syngas a flow of synthesis gas comprising at least CO and preferably hh
• FIG. 1 shows, schematically, a particular embodiment of the device that is the subject of the present invention
• FIG. 2 represents, schematically and in the form of a flowchart, a first succession of particular steps of the method which is the subject of the present invention
• FIG. 3 shows, schematically and in the form of a flowchart, a second succession of particular steps of the method that is the subject of the present invention
• FIG. 4 represents, schematically and in the form of a flowchart, a third succession of particular steps of the method which is the subject of the present invention.
• synthetic methane refer, more generally, to synthetic natural gas which may include other chemical species in addition to the methane produced.
• the "average" temperatures are the temperatures between 250°C and 350°C and
• - "low” pressures are pressures strictly below a predetermined limit pressure, for example, atmospheric pressure, 2 bar or 3 bar and - “high” pressures are pressures above the predetermined limit pressure in bar.
• FIG. 1 A diagrammatic view of an embodiment of the device 100 object of the present invention is observed in FIG. 1, which is not to scale.
• This device 100 for the hybrid production of synthetic dihydrogen and/or synthetic methane comprises:
• syngas a flow of synthesis gas comprising at least CO and preferably at least hh
• control system 120 comprising means 121 for selecting an operating configuration of the reactor and means 122 for issuing a command representative of the selected configuration, the reactor being configured to operate according to a given configuration depending of the command transmitted by the transmission means.
• the inlet 105 for a gas flow generally designates any conduit allowing the routing of the syngas towards an inlet for syngas (not referenced) of the reactor 110 of conversion.
• the exact nature of the inlet 105 depends on the operating conditions determined in terms of flow rate, in particular, and the nature of the syngas to be transported.
• the inlet 105 is supplied with syngas by a gasifier 505 of waste, biomass and/or carbonaceous residues. It is noted that the terms “gasifier” and “gasification reactor” are equivalent here.
• Gasification corresponds to a thermal degradation of biomass or waste or carbonaceous residues which successively undergo drying and then devolatilization, or pyrolysis, of the organic matter to produce a carbonaceous residue (the "char"), a gas synthesis (called “syngas”), and condensable compounds (tars).
• the carbonaceous residue can then be oxidized by the gasification agent (water vapour, air, oxygen, carbon dioxide) to produce a gas mainly composed of hb and CO.
• the gasification agent water vapour, air, oxygen, carbon dioxide
• this gasifying agent may also react with tars or majority gases.
• a WGS Water Gas Shift reaction also occurs in the 505 gasification reactor.
• the pressure of gasification reactor 505 has little effect on this reaction.
• the equilibrium is strongly linked to the temperature of the reactor and to the “initial” composition of the reactants.
• the syngas obtained consists of a mixture of incondensable majority gases (H2, CO, CO2, CHU, C x ), condensable compounds (tars), particles (char, coke, elutriated bed material), and inorganic gases (alkaline , heavy metals, H2S, HCl, NH3, etc.).
• the majority gases can be transformed into numerous energy vectors, including biomethane and biohydrogen.
• the H2/CO ratio in the syngas is a determining factor. Out of the gasification reactor 505, this ratio generally does not exceed 2, but sometimes ratios greater than 6 under certain conversion conditions can be obtained.
• the device 100 comprises a means 510 for cooling the products of the gasifier 505.
• the device 100 comprises a means 515 for eliminating impurities from the products of the gasifier 505.
• This means 515 for eliminating can be positioned upstream or downstream of the means 510 cooling if the device 100 includes such a means 510 of cooling.
• removal means 515 depends on the nature of the impurities to be removed. Such removal means 515 are well known to those skilled in the art. For example, such a means 515 of elimination is a “scrubber” (translated as “absorber-neutralizer”). Such a scrubber can implement wet neutralization, dry neutralization or adsorption depending on the determined use.
• the device 100 comprises a plurality of cascade elimination means 515 integrating a multitude of unit operations or processes arranged in series or in parallel (absorption, physical and/or chemical adsorption on activated carbon, for example, zeolite, ash, or metals, etc.).
• the device 100 comprises means (not shown) for cooling the syngas and/or a compressor (not shown) for the syngas.
• the device 100 includes a means (not shown) for removing dust from the syngas.
• dust removal means is, for example, of the venturi, multicyclone or filter type.
• the device 100 comprises means 145 for compressing the syngas at a determined pressure, the outlet pressure of the compression means 145 being determined according to the command issued by the control system 120.
• This compression means 145 is, for example, a centrifugal, axial, vane, screw, lobe, piston or “scroll” type compressor. This compression means 145 is configured, for example, to bring the syngas to a pressure of between 1 and 80 bar and preferably between 1 and 15 bar.
• the device 100 comprises means 146 for expanding the syngas at a determined pressure, the outlet pressure of the expansion means being determined according to the command issued by the system 120 of ordered.
• the device 100 comprises, upstream of the entry of the syngas into the conversion reactor 110, a heat exchanger 535.
• This heat exchanger which can be a heat exchanger plates or tubes and calenders or a succession of exchangers (not shown), for example, is configured to heat or cool the syngas to a temperature compatible with the particular configuration of the conversion reactor 110.
• this exchanger 535 can make it possible to ensure a minimum reactor inlet temperature between 170° C. and 230° C. and preferably above 170° C. to avoid the formation of nickel tetracarbonyls (if catalyst or reactor with nickel base) which is a poison in the produced gas.
• the catalytic conversion reactor 110 is preferably an isothermal reactor.
• this conversion reactor 110 is an isothermal exchanger reactor cooled by the walls or a cascade of isothermal reactors. More preferably, this conversion reactor 110 is an isothermal fluidized bed reactor.
• this reactor 110 is a single isothermal fluidized bed reactor.
• this conversion reactor 110 is an isothermal reactor with a dense or bubbling fluidized bed.
• the term "dense fluidized bed isothermal reactor” means a reactor configured to operate at a temperature of between 200° C. and 600° C. and at a pressure of between 1 and 80 bar.
• This reactor 110 is configured to operate according to two configurations, or regimes, of thermodynamic equilibrium:
• the invention is not reduced to the use of a single reactor and that it can implement a plurality of reactors, of identical or distinct types, in parallel or in series to obtain the product of target reaction.
• the reactor 110 implements a catalytic bed 111.
• a catalytic bed 111 can be formed:
• bifunctional catalyst 114 configured to, depending on other reaction parameters (temperature or pressure for example), favor one or the other of the configurations.
• the catalyst promoting the Sabatier reaction can be based on Ni/Ab03, Ni/Pr/Ab03, Ruthenium, for example, and
• the catalyst promoting the WGS reaction can be for example based on Cu0/Zn0/Ab03, ZnO, Cr203, KOH/Pt/AbOs, Pt-CeOx/AbC, CUO/Al2O3, ... for conversions at low temperature , for example around 200°C or Fe203/Cr203, Au-Fe203, Au-Ce02, Au-Ti02, Ru-Zr02, Rh-Ce02, Pt-Ce02 or Pd-Ce0 2 , ... for conversions at high temperature, for example around 450°C.
• the objective of the reactor 110 is to maximize the production of synthetic methane (CH4).
• Syngas can be converted to biomethane through the catalytic methanation reaction CO, also known as the Sabatier reaction. This reaction, the kinetics of which is rapid at the temperatures used, is characterized by a very high exothermicity.
• hh and CO should be in a stoichiometric ratio of 3:1. This ratio can be obtained by carrying out a complementary WGS reaction positioned upstream of 110.
• the device 100 comprises a dedicated WGS reactor comprising specific catalysts.
• a specific catalyst is, for example, based on Cu-Zn-Al2O3, Fe 2 03/Cr 2 03.
• the complementary WGS reaction is carried out directly in conversion reactor 110.
• the device 100 comprises an injector 125 of steam into the flow of syngas and/or an injector 130 of liquid water or steam into the catalytic reactor, a quantity of water and / or steam injected by at least one injector being carried out according to the command issued by the control system 120 .
• the injector 125 can be positioned upstream or downstream of a possible recirculation, 155 or 160, described below.
• the steam injector 125 is, for example, a tapping in the inlet pipe 105 associated with a means (not shown) of production to bring water to a temperature corresponding to the state of steam at the operating conditions of entry 105 for syngas.
• the water injector 130 in the conversion reactor 110 is, for example, a liquid or steam water supply tapping in the conversion reactor 110. This tapping can be supplied with external water or else with water recycled within the device 100.
• the device 100 comprises, downstream of the conversion reactor 110, a water separator 135 configured to supply the separated water to an evacuation 140 of water or to an injector, 125 and/or 130, after its transformation into the vapor phase, for example through a heat exchanger (not shown).
• the separator 135 can be of the condenser type, for example.
• the water separator 135 is configured to dehydrate the stream produced at the outlet of the conversion reactor 110, by cooling, for example, to a temperature corresponding to a temperature lower than or equal to the dew point temperature of the water under the operating conditions. of the device 100.
• the device 100 comprises, upstream of the water separator 135, at least one heat exchanger 540.
• At least one heat exchanger 540, of the plate or tube and shell type exchanger, for example, is configured to cool the products of the conversion reactor 110 to a temperature corresponding to a temperature greater than or equal to the dew point temperature of the water. under the operating conditions of the device 100.
• the CO2 also present in the syngas can also produce CHU by CO2 methanation reaction if the hydrogen is in CO methanation over-stoichiometry.
• the objective of the reactor 110, or of the plurality of reactors 110 is to maximize the production of synthetic hydrogen.
• the WGS reaction can be implemented specifically in the same conversion reactor 110 or in a plurality of reactors 110 conversion.
• water is injected in a quantity greater than that mentioned in the case of methanation, in order to maximize the production of hydrogen.
• the products of the conversion reactor 110 comprise water in excess or in products, carbon dioxide, hydrogen and methane in proportions which vary according to the configuration implemented.
• Outlet 115 for a flow of synthetic dihydrogen and/or synthetic methane designates any pipe allowing the products of the conversion reactor 110 to be transported from the conversion reactor 110.
• the products passing through the outlet 115 are preferably brought to the specifications for use downstream of the conversion reactor 110 as described below.
• the device 100 comprises a carbon dioxide separator 520 from the stream leaving the reactor 110 for conversion.
• This separator 520 is, for example, a device configured to carry out the adsorption (physical or chemical) or the pressure swing adsorption, the membrane permeation or the cryogenics of the carbon dioxide of the flow and direct it towards an evacuation or a recovery. 530 carbon dioxide.
• the device 100 comprises at least one recirculator, 155 and/or 160, of at least part of the output gas towards the inlet 105 for syngas, a quantity of recirculated gas being determined according to the command issued by the control system 120.
• recirculator refers to a pipe for transporting a flow of gas towards the inlet 105 for syngas.
• This gas flow can be a flow of hydrogen 160 or synthetic methane 155, depending on the command issued by the control system 120.
• the control system 120 has configured the device 100 to produce hydrogen
• the residual methane is recirculated by the "recirculator” 155
• the control system 120 has configured the device 100 to produce methane
• it is the dihydrogen which is recirculated by the “recirculator” 160.
• the product whose production is maximized by the configuration of the device 100 can also be recirculated so as to keep the flow rate passing through the conversion reactor 110 constant.
• the device 100 comprises, downstream of the conversion reactor 110:
• an output selector 175 for dihydrogen connected to a recirculator 160 of dihydrogen towards the inlet 105 for syngas and to an outlet 180 of dihydrogen, device in which: - when the command issued corresponds to a configuration of the reactor to favor a reaction of gas with water, the output selector for dihydrogen is configured to direct the dihydrogen mainly towards the dihydrogen output, the methane output selector is configured to direct the methane mainly to the methane recirculator and
• the output selector for dihydrogen is configured to direct the dihydrogen mainly towards the dihydrogen recirculator and the output selector for methane is configured to direct mainly methane to the methane outlet.
• the dihydrogen content and/or the recirculated methane content are adjusted to produce a mixture of dihydrogen and methane in the given proportions.
• the residual methane and hydrogen recirculations, 155 and 160 can inject the residual gas downstream of the compression means 145, for example during the use of a membrane separation in 525.
• the hb is then obtained in the permeate , so at low pressure.
• hb is taken up by a valuation 180 downstream.
• the low pressure hb permeate is fed upstream from 145 at a lower pressure than the operating pressure of 110.
• the device 100 comprises, upstream of the output selector 175 for dihydrogen, a separator 525 for dihydrogen.
• Such a dihydrogen separator 525 is, for example, a device for performing membrane permeation, pressure swing adsorption and/or an electrocompressor and/or electrochemical compression.
• the small quantity of hydrogen present in the gas leaving the syngas conversion reactor is mainly separated from the biomethane, the latter thus being able to be recovered in the transport or distribution networks, or in a mobility station; the small quantity of hydrogen separated can be recirculated in whole or in part to the stream 105 supplying the reactor 110 for catalytic conversion of the syngas and
• the large quantity of hydrogen present in the gas leaving the syngas conversion reactor is separated from the rest of the gas, thus producing biohydrogen of sufficient purity to be recovered in an industrial network or in a mobility station; the rest of the gas can be all or part recirculated to the stream 105 feeding the reactor 110 for catalytic syngas conversion.
• the device 100 comprises means 545 for compressing the products of the reactor 110 for conversion to a determined pressure, this pressure corresponding to a nominal pressure of use of said products or to an operating pressure of the conversion reactor 110 with a view to recirculating part of the reaction products.
• This compression means 545 is, for example, a centrifugal, axial, vane, screw, lobe or “scroll” type compressor.
• the reaction products preferably have a pressure of between 4 and 80 bar.
• Means 135, 520 and 525, 545 can be interchanged.
• the device 100 comprises a heat exchanger 150 immersed in the conversion reactor, said heat exchanger being configured to cool or heat the reactor 110 to a temperature determined by depending on the command issued by the control system 120.
• Such a heat exchanger 150 is, for example, made up of horizontal, vertical or inclined tubes or a plate exchanger or cooling by the walls of the reactor 110 or the multiplicity of reactors 110.
• the control system 120 is, for example, an electronic calculation circuit configured to:
• the selection means 121 is, for example, a mechanical, electrical or electronic interface allowing the selection of a configuration from among the two available configurations.
• the transmission means 122 is, for example, an electronic control circuit, configured to adapt operating variables of the device 100 to correspond to the available configurations.
• the pressure of the conversion reactor 110 adjusted by the means 145 or 146 and/or by a pressure regulating valve (not shown) positioned downstream of 110: the pressure is a variable which greatly favors the methanation reaction.
• the reactor pressure is high, preferably greater than atmospheric pressure, and even more preferably greater than 3 bar, while it is reduced (preferably less than 3 bar, and even more preferably less at 2 bar, and even more preferably close to atmospheric pressure) for the production of biohydrogen by Water-Gas Shift,
• the temperature of the conversion reactor 110 adjusted by the systems 150 and/or 535 or the injection of water 130 the two reactions (methanation and Water-Gas Shift) are exothermic, therefore favored by low temperatures.
• the Water-Gas Shift catalyst present in the reactor 110 is active at low or high temperature.
• the temperature of the reactor is preferably between 250°C and 350°C for the production of biomethane, and preferably between 200°C and 250°C or greater than or equal to 350°C for the production of biohydrogen according to the WGS catalytic function contained in the catalytic bed 111,
• the steam flow impacts the thermodynamic equilibrium, and therefore the production of biomethane or biohydrogen.
• the vapor volume fraction in the syngas conversion reactor 110 is preferably between 0 and 30% vol and preferentially between 10 and 30% vol, against 20 to 80% vol and preferentially between 30 and 50 %vol for the production of biohydrogen. It is noted that the vapor volume fraction includes the vapor at the inlet of the syngas conversion reactor 110 and, when the reactor 110 is cooled by injection of cooling water 130, the injected water which vaporizes on contact with the hot catalytic bed 111.
• the device 100 generates a residual gas.
• the hydrogen separated from the biomethane can be recycled to the inlet 105 of the syngas conversion reactor 110 in order to be transformed into biomethane by methanation or valorized as a small production of biohydrogen.
• the residual gas (mainly composed of CHU and CO) can be recycled to the inlet 105 of the syngas conversion reactor 110 in order to increase the biohydrogen yield.
• the fractions of gas recirculated 155 and/or 160 to the inlet 105 of the syngas conversion reactor 110 can vary from 0 to 100% depending on the operating modes.
• a rise in temperature equal to or greater than 350° C. promotes the production of biohydrogen if the catalytic bed 111 contains a WGS catalyst having a WGS catalytic function at high temperature
• a drop in temperature equal to or below 250°C does not allow the methanation reaction to take place and promotes the production of biohydrogen if the catalytic bed 111 contains a WGS catalyst having a WGS catalytic function at low temperature,
• the "nominal" conditions of the process for production of biohydrogen by high temperature Water-Gas Shift can be for example the following:
• the recirculation rate 165 corresponds to the ratio between the flow in the recirculator 155 and the sum of the flows in the recirculator 155 and at the outlet 170. It is noted that the recirculation rate 175 corresponds to the ratio between the flow in the recirculator 160 and the sum of the flows in the recirculator 160 and at the outlet 180.
• the "nominal" conditions of the process for the production of biohydrogen by low-temperature Water-Gas Shift can be , for example, the following:
• composition of the various key streams of the process is as follows:
• an average temperature between 250°C and 350°C promotes the production of biomethane - preferably a reaction temperature below 350°C and preferentially below 320°C and even more preferentially below 300°C and preferentially greater than or equal to 250°C is implemented in methanation mode in order to limit the production of biohydrogen, below 250°C, the methanation reaction is limited by the kinetics, because the reactions cannot start or are not fast enough .
• composition of the various key streams of the process is as follows:
• the present invention aims to convert the syngas, for example from biomass / waste / residues, into biomethane or biohydrogen in a flexible way by simply modifying certain operating conditions while maintaining the same equipment, the same process chain and the same catalytic bed 111 .
• a hybrid reactor for the catalytic conversion of syngas in a fluidized bed using a mixture of catalysts, a single low-efficiency catalyst or a bifunctional catalyst makes it possible to carry out these conversions by operating:
• low temperature preferably between 200°C and 250°C: o low pressure, preferably between 1 and 2 bar and high water content, preferably between 30%vol and 80%vol, for the production of biohydrogen if the catalytic bed 111 contains a so-called “low temperature” WGS catalyst.
• a plurality of reactors can be implemented, in series or in parallel. While an excess of steam is conventionally used to limit the methanation reaction during the conversion of syngas into biohydrogen by the Water-Gas shift reaction, the present invention makes it possible to limit the methanation reaction by controlling the pressure, the temperature, the water vapor content, but also the methane content in the syngas conversion reactor. Indeed, by more or less recirculating the flow of residual gas rich in CHU towards the syngas conversion reactor in WGS mode, the thermodynamic equilibrium and the reaction kinetics leading to the production of biomethane are disadvantaged, which further limits the reaction. of methanation.
• FIG. 2 schematically shows an embodiment of the method 200 which is the subject of the present invention.
• This process 200 for the hybrid production of synthetic dihydrogen and/or synthetic methane comprises:
• the configuration step 215 is carried out by all of the operational adjustments described with regard to FIG. 1 with regard to the configuration for the production of biomethane or synthetic dihydrogen.
• the method 300 comprises:
• step 315 of converting a stream of syngas by implementing a conversion reactor 110 which may include a step (not referenced) of supplying water directly into the reactor 110 or into the stream (not referenced ) input,
• method 400 includes:
• step 315 of converting a stream of syngas by implementing a conversion reactor 110 which may include a step (not referenced) of supplying water directly into the reactor 110 and/or into the stream ( not referenced) input, - a first 320, second 325 and third 330 separation steps, each of these separation steps, 320, 325 and 330, being of a distinct type among:

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