Classifications

• • 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
  • C01B3/06—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
• • 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
  • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
  • C01B3/042—Decomposition of water
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B32/00—Carbon; Compounds thereof
  • C01B32/40—Carbon monoxide
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
  • C10J3/02—Fixed-bed gasification of lump fuel
  • C10J3/20—Apparatus; Plants
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
  • C10J3/02—Fixed-bed gasification of lump fuel
  • C10J3/20—Apparatus; Plants
  • C10J3/34—Grates; Mechanical ash-removing devices
  • C10J3/36—Fixed grates
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
  • C10J3/72—Other features
  • C10J3/721—Multistage gasification, e.g. plural parallel or serial gasification stages
• • 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
  • B01J2219/00002—Chemical plants
  • B01J2219/00004—Scale aspects
  • B01J2219/00006—Large-scale industrial plants
• • 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
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2200/00—Details of gasification apparatus
  • C10J2200/09—Mechanical details of gasifiers not otherwise provided for, e.g. sealing means
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
  • C10J2300/0913—Carbonaceous raw material
  • C10J2300/0916—Biomass
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
  • C10J2300/0953—Gasifying agents
  • C10J2300/0959—Oxygen
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
  • C10J2300/0953—Gasifying agents
  • C10J2300/0969—Carbon dioxide
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
  • C10J2300/0953—Gasifying agents
  • C10J2300/0973—Water
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
  • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
  • C10J2300/1656—Conversion of synthesis gas to chemicals
  • C10J2300/1659—Conversion of synthesis gas to chemicals to liquid hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
  • C10J2300/1693—Integration of gasification processes with another plant or parts within the plant with storage facilities for intermediate, feed and/or product
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
  • C10J2300/1846—Partial oxidation, i.e. injection of air or oxygen only
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
  • C10J2300/1853—Steam reforming, i.e. injection of steam only
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
  • C10J2300/1861—Heat exchange between at least two process streams
  • C10J2300/1884—Heat exchange between at least two process streams with one stream being synthesis gas
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
  • C10J2300/00—Details of gasification processes
  • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
  • C10J2300/1861—Heat exchange between at least two process streams
  • C10J2300/1892—Heat exchange between at least two process streams with one stream being water/steam
• • 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 method for treating gaseous effluents. It also relates to a system implementing the method according to the invention.
• the field of the invention is the field of the treatment of gaseous effluents. More particularly, the invention relates to the production of carbon monoxide (CO) and hydrogen (H 2 ) molecules in constant, independent, concomitant and controlled fluxes, from a fuel containing carbon elements, in particular plant biomass, and gaseous effluents.
• CO carbon monoxide
• H 2 hydrogen
• the invention can be applied in a large majority of industrial field.
• An object of the invention is to provide a method and a system for producing H 2 and CO to overcome the disadvantages of the systems of the state of the art.
• Another object of the invention is to provide a method and a system for producing H 2 and CO separately.
• Another object of the invention is to provide a method and system for producing H 2 and CO to control the amount of H 2 produced independently of the amount of CO produced.
• the invention thus proposes a method of treating a first gaseous effluent essentially comprising carbon dioxide (CO 2 ) and a second gaseous effluent comprising essentially water vapor (H 2 O), said process comprising the following steps: - generation of a first gaseous stream comprising carbon monoxide (CO) by passing said first gaseous effluent through a first layer of oxidation-reducing reactive material comprising carbon elements at high temperature, - generating a second gaseous stream essentially comprising dihydrogen (H 2 ) by passing said second gaseous effluent through a second reactive material redox layer comprising elements of carbon at high temperature, and - upgrading at least one of the first and second gas stream.
• CO carbon monoxide
• H 2 dihydrogen
• the process according to the invention makes it possible to separately produce hydrogen and carbon monoxide. Thanks to the process according to the invention, the proportions of hydrogen produced and carbon monoxide produced can be controlled separately. In addition, carbon monoxide and hydrogen are not mixed and make up two separate gas streams that are separately recoverable. In the continuation of the request we will use the chemical formulas to facilitate the reading.
• the process according to the invention comprises, during the passage of the first gaseous effluent containing essentially CO 2 , through the first layer containing carbon elements at high temperature: a reduction of the CO 2 molecules in the presence of the carbon elements at high temperature. This reduction produces carbon monoxide (CO) molecules; and
• the first gas stream obtained from the first gaseous effluent essentially comprises CO molecules.
• this first gas flow should contain only molecules of CO.
• the process according to the invention may comprise a heat exchange of at least one of the first and second gaseous flows with a heat transfer stream, this gaseous flow yielding at least a portion of its thermal energy to the heat transfer stream.
• the first and second gaseous streams can yield at least a portion of their heat energy to the heat transfer stream.
• the heat transfer stream may comprise water.
• the heat transfer stream may be water in the gaseous or liquid state. The thermal exchange of water with the first and the second gas stream then produces a third gas stream comprising high temperature water vapor.
• At least a portion of the water vapor contained in the second gaseous effluent may come from the third gaseous stream containing essentially water vapor.
• part of the second gaseous effluent can come from a facility producing a gaseous effluent containing water vapor.
• Part of the third gas stream may be mixed with the gaseous effluent from this plant to obtain the second gaseous effluent.
• the process may be started with a second gaseous effluent containing produced water by another device, system or installation requiring or not an energy supply.
• the third gas stream may be the second gaseous effluent so that the second gaseous effluent is completely produced by the process according to the invention, and the process according to the invention is then self-sufficient in thermal energy to produce the second gaseous effluent.
• second gaseous effluent second gaseous effluent.
• the method according to the invention further comprises, during the passage of the second gaseous effluent, essentially containing water vapor (H 2 O), through the second layer containing carbon elements at high temperature:
• the method according to the invention may further comprise a step of separating the CO 2 contained in the second gas stream, to provide a fourth gas stream essentially comprising CO 2 and a fifth gas stream containing essentially hydrogen H 2 .
• the fourth gas stream containing essentially CO 2 may be mixed with the first gaseous effluent.
• a portion of the first gaseous effluent can come from a facility producing a gaseous effluent containing CO 2 .
• Part of the fourth gas stream may be mixed with the gaseous effluent from this plant to obtain the first gaseous effluent.
• the process can be started with a first gaseous effluent containing CO 2 produced by another device, system or installation requiring or not an energy supply.
• the fourth gas stream may be the first gaseous effluent so that the first gaseous effluent is completely produced by the process according to the invention, and the process according to the invention is self-sufficient to generate the first gaseous effluent. .
• the first oxidoreductive layer is produced by combustion, in the presence of an oxidant, of a fuel composed of carbon elements under sub-stoichiometric conditions.
• This solid fuel may comprise plant biomass.
• plant biomass advantageously meets the criterion of solid fuel composed of carbon.
• plant biomass participates in the natural carbon cycle as follows.
• the carbon involved in the atomic composition of plant biomass comes from the essentially photosynthetic conversion of atmospheric carbon dioxide. It is therefore considered that the CO 2 resulting from the combustion of plant biomass has a neutral effect on the problem of greenhouse gases, unlike that resulting from the combustion of fossil fuels.
• plant biomass is a source of renewable energy.
• the CO 2 and hydrocarbon molecules are part of the eco-life cycle, the industry generates these molecules to excess thereby creating a deep imbalance that pollutes the ecosystem. These elements can be recycled directly by the process permanently, so they will no longer participate in greenhouse gases (GHG).
• a high-performance densification concentrates the carbon of the plant material up to 85% of the mass (instead of 50% of the source material) and the product of the technique can advantageously be of cylindrical shape, to favor the gravitational flows in the system. .
• roasting and / or densification improve the overall exploitation of the system, in particular by maintaining the quality of the solid fuel during storage.
• Plant biomass is available practically everywhere and in a profusion, its densification can be carried out on the site itself. its exploitation, as on the site of the manufacturer who installs the system implementing the method according to the invention.
• the combustion of the solid fuel can be carried out under oxidant O 2 .
• This oxidant can be injected in a targeted way in the heart of the first layer.
• At least a portion of the second oxidoreductive layer is produced by transfer or recovery of at least a portion of the high temperature carbon elements of the first layer.
• the first layer may be at a higher location than the first layer.
• the first layer may be inclined towards the second layer so that at least a portion of the high temperature carbon elements of the first layer gravitational flow from the first layer to the second layer.
• the temperature of the first layer is greater than or equal to 1000 ° C. and the temperature of the second layer is between 800 and 1000 ° C.
• the temperatures of the first and second layers can be regulated by injection an oxidant, for example I 1 O 2 .
• the method according to the invention may comprise a separation of the CO 2 and H 2 molecules present in the second gas stream, this separation providing a fifth gas stream essentially comprising H 2 .
• CO 2 is recyclable in CO by the first layer, it can be temporarily stored, liquid and / or gaseous to participate in the regulation and safety of the installation. It can also be marketed in liquid form to industrial operators. The deoxidation of this CO 2 in 2 CO also allows a withdrawal of CO, which can be compensated by a supplement of CO 2 of industrial origin, itself then removed greenhouse gases the time of a new life cycle or definitely in case of substitution of a fossil energy.
• the process according to the invention may comprise a synthesis of hydrocarbon compounds from H 2 and CO in means such as catalysts.
• the process according to the invention makes it possible to separately obtain three gaseous streams containing CO, H 2 and CO 2 which can be put in buffer tanks, to be used, in any desired dosage, in any existing hydrocarbon formulations and forthcoming, in the eco-industrial space of chemistry and petrochemistry, as well as the environment and depollution.
• the invention relates to the production of fuels and liquid and gaseous fuels for synthesis, for a substitution of petroleum products and natural gas by these fuels of vegetable and renewable origin.
• fuels and liquid and gaseous fuels for synthesis for a substitution of petroleum products and natural gas by these fuels of vegetable and renewable origin.
• the purified gases can advantageously be heated by the reaction gases before they are cooled to the purification temperature.
• the thermal cycle thus defined is complete, with no losses other than those inherent to the losses of all thermal equipment and systems.
• the energy capacity of the hydrocarbon compounds, before the catalytic synthesis is the maximum of the energy potential of the fuel used in the system according to the invention that can be obtained.
• the new source of synthesized energy is recovered:
• the synthetic biogas is conditioned to be stored and / or used as it is,
• hydrocarbon compounds for the production of substitute energy or of synthetic molecules, are conditioned to be stored in the state and / or used.
• the process according to the invention carries out a purification of at least one of the first and second gaseous effluents by combustion of combustible particles present in the first gaseous effluent and / or in the second gaseous effluent during the passage of these gaseous effluents. through the first layer and / or the second layer.
• the system according to the invention comprises an enclosure comprising: a first reactor comprising a first gate supporting a first reactive material redox layer comprising high temperature carbon elements, the first layer being crossed by the first layer; gaseous effluent providing a first gas stream comprising CO, and
• a second reactor comprising a second gate supporting a second reactive material redox layer comprising high temperature carbon elements, the second layer being traversed by the second gaseous effluent providing a second gas stream comprising H 2 .
• the system according to the invention further comprises means of upgrading at least one of the first and second gas streams.
• the system according to the invention may comprise a communication opening by which the first and second reactors communicate with each other so that at least a portion of the high temperature carbon elements of the first layer pass from the first reactor to the second reactor. reactor through the communication aperture to form at least a portion of the second layer.
• first grid supporting the first layer is located at a location higher than the second grid supporting the second layer.
• the first gate is substantially inclined toward the second gate, the lower end of the first gate being at the communication aperture so that at least a portion of the high temperature carbon elements of the first layer flows from the first reactor to the second reactor to form the second layer.
• the first zone is located above the grid and comprises an opening for introducing the gaseous effluent into the reactor and the second zone is located below said grid and comprises an opening for extracting the gas flow. Furthermore these grids can be cooled with a heat transfer fluid, which may be water, flowing or projected in these grids.
• the first reactor may comprise an opening for introducing, on the first gate, a fuel comprising carbon elements, the first layer being produced by combustion, in the presence of an oxidant, of the fuel under sub-conditions. stoichiometric. This fuel is preferably plant biomass.
• Each of the first and second reactors may further comprise means for injecting an oxidant into the reactor and more particularly to the core for the first layer of oxidation-reducing reactive material.
• This oxidant is firstly used to carry out the combustion, under substoichiometric conditions, of the fuel introduced into the first reactor and consequently of that which gravitates through the introduction opening into the second reactor and, on the other hand, on the other hand, to regulate the temperature of the two layers of oxidation-reducing reactive materials.
• the system according to the invention may further comprise means for recovering residues from each of the first and second reactors. These residues can be evacuated from each of the reactors through a discharge opening located in the bottom of the reactor and opening to at least one ashtray provided to accommodate the residues.
• the system according to the invention may further comprise at least one heat exchanger performing a heat exchange of at least one of said first and second streams with a heat transfer fluid.
• This coolant can be water.
• the heat exchanger then provides a third gas stream essentially comprising high temperature water vapor.
• the system according to the invention may further comprise a feed circuit for at least a portion of the third gas stream in the second reactor or in the second gaseous effluent.
• the system according to the invention may comprise means for separating the different gaseous compounds from the second gas stream, comprising H 2 and CO 2 obtained by oxidation-reduction of the water vapor in the presence of carbon elements. high temperature. These separation means can provide a fourth gas stream essentially comprising CO 2 and a fifth gas stream essentially comprising H 2 .
• At least a portion of the fourth gas stream can be fed into the first reactor or mixed in the first gaseous effluent by a feed circuit.
• system according to the invention may comprise means for synthesizing hydrocarbon compounds from H 2 , CO but also CO 2 obtained during the process according to the invention.
• FIG. 1 is a schematic representation of the system according to the invention
• FIG. 2 is a schematic representation of an enclosure according to the invention comprising the first and the second reactor.
• FIG 1 is a schematic representation of the system according to the invention.
• the system according to the invention comprises a chamber E comprising a first reactor 10 comprising a first reactive material redox layer comprising high temperature carbon elements and a second reactor 20 comprising a second reactive material oxidation reduction layer comprising carbon elements with high temperature.
• This reaction chamber E comprising the two reactors 10 and 20, is shown in Figure 2 and detailed below.
• the reactor 10 in the enclosure E receives biomass B to feed the reactions occurring in the reactors 10 and 20 and more particularly for producing the oxidoreductive layers in the reactors 10 and 20.
• the biomass B is preferably plant biomass whose calorific value has been optimized.
• the biomass B introduced into the first reactor 10 undergoes oxyfuel combustion under sub-stoichiometric conditions in the presence of an oxidant which is 10 2 .
• the oxygen is injected directly into the reactor 10 and possibly into the reactor 20, firstly to carry out the combustion of the biomass B and, secondly, to regulate the temperatures of the reactive material layers in the reactors 10 and 20.
• Oxygen can be industrial oxygen
• the reactor 10 receives a first gaseous effluent 11 essentially comprising carbon dioxide CO 2 .
• This gaseous effluent 11 can come, at least in part, from an external installation.
• the gaseous effluent 11 is produced by recycling the different gaseous flows produced by the system according to the invention at different stages of the process according to the invention.
• the layer of reactive material in the reactor 10 composed of carbonaceous solid fuel in substoichiometric oxycombustion, the CO 2 present in the first gaseous effluent 11 and that resulting from the combustion of the biomass are reduced to carbon monoxide.
• CO according to the reaction defined by Boudouard:
• the conversion is integral when the reaction temperature is equal to or greater than 1000 ° C.
• the CO is an industrial gas, it is the active form of the carbon entering into the synthesis catalysts.
• the CO obtained can participate in the synthesis of exploitable carbons in hydrocarbon molecules and generators of industrial products.
• the CO 2 life cycle present in the first gaseous effluent 11 and coming from the combustion of biomass B under oxidant O 2 , is thus prolonged and replaces its fossil carbon equivalent, which would have contributed to greenhouse gases. .
• the reactor 10 outputs a first gas stream 12 essentially comprising CO.
• the reactor 20 receives a second gaseous effluent 21 essentially comprising water vapor at high temperature H 2 O.
• This second gaseous effluent 21 may come, at least in part, from an external installation.
• the second gaseous effluent 21 is produced by energy recovery of the different gaseous flows produced by the system according to the invention at different stages of the process according to the invention.
• the water vapor H 2 O found in the second gaseous effluent 21 is at a very high temperature, acquired by cooling the outgoing gases of the two reactors.
• the temperature of the water vapor, which passes through the dedicated reactor of the reactor vessel 1, must be between 700 and 1000 0 C to be the conditions required for the deoxidation reaction.
• the H 2 O molecule By passing through the layer of reactive material, in the reactor 20, comprising carbon elements at high temperature, greater than or equal to 1000 ° C., the H 2 O molecule will lose its oxygen atom in favor of a carbon atom. and / or a molecule of CO (carbon monoxide) according to the formula: C + H 2 O -> CO + H 2 , then
• the reactor 20 outputs a second gas stream 22 essentially comprising H 2 dihydrogen and carbon dioxide CO 2 .
• the first gas stream 12 produced by the reactor 10 passes through a water / gas exchanger E1.
• the first gas stream 12 comprising carbon monoxide CO will transfer its excess heat to a heat transfer fluid which, in the example represented in Figure 1 is liquid water H 2 O L.
• This heat transfer fluid is at the temperature and pressure of the distribution network or a dedicated reserve.
• the first gas stream 12 will evaporate the water and provide a third gas stream 13 comprising essentially high temperature water vapor.
• the cooling of the first gas stream 12 is defined by the carbon monoxide storage set CO, located in the first gas stream 12, in a tank 14 and / or the instructions for use of this CO. This temperature may be close to the temperature of the liquid water H 2 O L entering the exchanger E1.
• the superheated steam constituting the third gas stream 13 leaving the exchanger E1 is channeled to the reactor 20 for be deoxidized as described above.
• the heat capacity of the first gas stream 12 is thus completely recycled and contributes to the overall efficiency of the process according to the invention.
• the third gas stream partly comprises the second gaseous effluent 21.
• the second gas stream 22 produced by the reactor 20 goes into an exchanger E2 similar to the exchanger E1, that is to say a water / gas heat exchanger, in which the second gas stream 22, essentially comprising H 2 and CO 2 according to the approximate and respective proportions of 2 / 3-1 / 3, will transfer its excess heat to a coolant which, in the example shown in Figure 1, is also liquid water H 2 O L .
• This heat transfer fluid is at the temperature and pressure of the distribution network or a dedicated reserve.
• the second gas stream 22 will evaporate the liquid water H 2 O L -
• a gas stream 23 essentially comprising superheated steam which is mixed with the third gas stream 13 to be returned to the reactor 20 to be deoxidized.
• the cooling of the second gaseous flow 22 is defined by the instruction for use and / or storage of the second flow gaseous 22, and / or the appropriate temperature for the best performance of a gas separator 24 realizing the separation of hydrogen H 2 and carbon dioxide CO 2 , which temperature may be close to the temperature of the liquid water entering the water. exchanger E2.
• the recovery and recycling of the thermal capacities of the first and second gas streams 12 and 22 contribute to the overall efficiency of the system according to the invention and in particular to the transfer of the energy of solid biomass to molecules of "gas energy" H 2 and CO.
• the separator 24 carries out the separation of H 2 and CO 2 .
• a fourth gas flow 25 essentially comprising carbon dioxide CO 2 and a fifth gas stream 26 essentially comprising hydrogen H 2
• the fifth gas stream 26 essentially comprising H 2 can be used as it is at the implantation site of the system according to the invention, for a hydrocarbon synthesis for example, and / or molecular hydrogenation, and or the production of electricity, in a fuel cell for example, and / or any industrial process using this gas. It can also be conditioned and / or liquefied on site to be stored in a tank 27 before further operation.
• At least a portion of the fourth gas stream substantially comprising CO 2 is intended to be reintroduced into the reactor to be recycled and reduced to CO, as described above. At least a portion of the fourth gas stream 25 thus composes the first gaseous effluent 11. In doing so, the reaction cycle is closed.
• the ratio of the energy available, by the synthesis gases, that is to say the first and the second gas stream, the energy potential of the solid fuel is maximum.
• Part of the fourth gaseous flow essentially comprising CO 2 can be liquefied so as to be stored, waiting to be used, in a tank 28 and / or to be stored as a buffer in the gaseous state, in order to regulate its operation.
• the molecules H 2 and CO can thus be produced separately, in the quantities required by use, at equal or different temperatures.
• the first and second gas streams may be operated without molecular separation after cooling in the heat exchangers E1 and E2.
• the transfer of the heating value of the solid fuel to the calorific value of the synthesis gas, H 2 and CO, is maximal. Only thermal losses, depending on the insulation used in enclosure E and peripherals, are deduced from the rate. It will then be the characteristics and qualities of the equipment, which exploits these gaseous flows 12 and 22, which will define the overall efficiency of the energy conversion.
• the solid residues R of each of the reactors 10 and 20 are recovered and discharged from the reactors 10 and 20.
• H 2 is operated as is at the site of implantation of the system, for a hydrocarbon synthesis for example, or molecular hydrogenation, or any industrial process using this gas, it will be necessary to implement a chemical separator or membrane 25 which will allow the separate management of H 2 and CO 2 .
• a chemical separator or membrane 25 which will allow the separate management of H 2 and CO 2 .
• H 2 is intended to be stored in the tank 27, in part or in whole, the current methods are cryogenics systems. Given the temperature / liquefaction pressure of H 2 , the CO 2 will be naturally liquefied during the procedure, the separation is effective.
• the system according to the invention also comprises at least one catalytic module defined according to the choice of HC hydrocarbon molecules to be produced from the H 2 and CO obtained.
• This catalyst module may comprise catalysts, synthesizers, reformers, or any other known system or device commonly used by the chemical and petrochemical industry.
• the invention makes it possible to produce H 2 and CO separately and in the desired quantity.
• the supply of the catalysis and reforming system is thus made as a function of the molecule to be obtained, the synthesis of all liquid and gaseous HC hydrocarbons is possible, it is the choice of the synthesis module 30 which is decisive.
• all types of gaseous and liquid synthesis systems can be associated with the production of both H 2 and CO molecules. These systems can coexist to be powered simultaneously.
• the synthesis can be plural and produce at the same time, gas and liquid fuel, as well as automotive fuel, with a maximum conversion efficiency, based on the energy initially held by the biomass and / or the reactive solid fuel.
• the invention presents here two independent, concomitant and simultaneous reactions in a common enclosure E comprising two reactors 10 and 20 communicating with differentiated actions.
• a common enclosure E comprising two reactors 10 and 20 communicating with differentiated actions.
• the enclosure E comprises the first CO 2 reduction reactor 10 present in the first gaseous effluent 11 and the H 2 O reduction reactor 20 present in the second gaseous effluent 21.
• the first reactor 10 comprises a first layer of reactive material 101 supported by a first gate 102.
• the gate 102 is permeable to the reaction gases and can be cooled or not.
• the layer of reactive material can also be called "first thermal base”. It consists of solid fuel oxycombustion, preferably plant biomass B, introduced on the grid by an introduction opening 103 in the form of chute.
• Biomass B can be the size of wood chips or chips / shreds of the wood industry, it can be shreds and / or sawdust and / or all vegetable matter agglomerated into pellets, briquettes, sticks, etc. It can also be silvicultural and / or agricultural biomass in the anhydrous or roasted or densified state with high carbon concentration and calibrated in cylindrical form.
• this solid fuel may be coal, peat, lignite, etc.
• the biomass B present on the gate 102 is in oxyfuel combustion.
• This oxycombustion is made possible by injection of an oxidant, preferably I 1 O 2 injected into the heart of the thermal base 101 by at least one injector 104. It is the injection of I 1 O 2 which allows the organization of specific layers in the thickness of the first thermal base 101.
• the injection of O 2 is defined to oxidize the portion (stratum) central of the first thermal base in order to generate the thermal energy necessary for all the reactions occurring at the level of the first thermal base.
• the upper part of the thermal base is defined by the continuous supply of fuel B, this zone is endothermic.
• the lower part, in direct contact with the grid 102, is defined by the Boudouard reaction, it is controlled in temperature and in molecular compositions (CO 2 / CO ratio). Its regulation is done by controlling the O 2 injected flow rate, the control of absence of CO 2 (most of the gaseous flow is composed of CO) and the supply of fuel.
• the reactor 20 comprises a layer of reactive material 201 comprising carbon elements at high temperature.
• This layer 201 can also be called second thermal base. It is supported by a second gate 202 which can be cooled or not.
• the regulation of the temperature of the thermal base 201 can be provided by injecting oxidant O 2 by at least one injector 204 disposed just above the thermal base 201.
• the two reactors 10 and 20 are separated by a wall 203 having a communication opening C through which the reactors 10 and 20 are in communication.
• the first gate 102 supporting the first thermal base 101 is substantially inclined towards the second gate 202 supporting the second thermal base 201.
• the end of the gate 102 closest to the gate 202 is disposed at the communication opening C.
• the inclination of the grid 102 and the controlled oxycombustion render the central stratum of the first thermal base 101 unstable, the ignition materials gravitate downwards.
• the high temperature solid carbon particles, from the thermal base 101, flow by gravity on the gate 202 through the opening C to form the second thermal base 201.
• the gate 202 of the reactor 20 receives the flame of solid fuel from the thermal base 101 of the reactor 10 which have flowed by gravity through the opening C.
• the reactor 10 further comprises an inlet opening 105 of the first gaseous effluent 11, comprising the CO 2 to be reduced in its upper part.
• the first gaseous effluent comes at least in part from the recycling of the fourth gas stream.
• the CO 2 present in the first gaseous effluent 11 is added to the CO 2 of the oxycombustion of the solid fuel stratum.
• At least a portion of the CO 2 present in the first effluent can also come from an industrial plant external to the system according to the invention. Thus, the life cycle of the carbon it contains may be prolonged, and its contribution to the greenhouse effect removed.
• the CO resulting from the reduction of CO 2 at the passage of the first thermal base can be reduced in a specific catalyst where it will react according to the reaction demonstrated by the physicist Boudouard: 2CO, in the presence of Nickel, exchange an atom of O in favor of a CO.
• This reaction is exothermic 172 kJ / mol and is at equilibrium around 400 0 C, this exotherm can be recycled in the process, ie 2CO - »C + CO 2 + 172 kJ / mol.
• industrial CO 2 which would otherwise contribute to the greenhouse effect, it is possible to lengthen the life cycle of carbon by regenerating the elements of native carbons, in virgin materials, whether structured or not, which enter the industrial cycle. substituting for fossil carbons.
• the CO 2 present in the first gas stream decomposes on passing the first thermal base comprising carbon elements at high temperature.
• the first gas stream 12 essentially comprising CO.
• the first gas stream 12 is discharged from the reactor 10 through an evacuation opening 106 located under the first gate 102.
• a pipe connected to this discharge opening 106 is kept in depression by an extraction system which ensures a constant depression. in the zone of the reactor 10.
• the solid residues R of the first thermal base 101, such as ash, are evacuated by gravitation through a discharge opening 107 arranged in the bottom of the first reactor 10.
• the second thermal base 201 is supplied with solid reagent by the communication opening C between the two reactors 10 and 20, which allows the flow of carbon at high temperature, carbon to red, from the first thermal base 101.
• the saturation of the second thermal base 201 is determined by the upper lip of the communication opening C.
• the material component of this second thermal base 201 is eminently reducing, its purpose is to deoxidize the vapor water to produce hydrogen and CO 2 .
• the upper layer of the second thermal base 201 fed continuously by the first thermal base 101, is at the temperature of the thermal base 101.
• This upper layer / layer is traversed by the water vapor H 2 O, contained in the second superheated gaseous effluent 21 admitted into the reactor 20 through an inlet opening 205, located in the upper part of the reactor upstream of the second thermal base 201.
• a part of this water vapor H 2 O, superheated at its deoxidation temperature, will deoxidize through the upper layer of the second thermal base 201.
• H 2 O + C -> H 2 + CO is endothermic.
• the 131 kJ / mol are provided by the thermal capacity of the upper layer of the second thermal base 201.
• the reaction temperature at this layer must be above 800 ° C., if the first deoxidation reaction of H 2 O may lower the temperature of this layer below this threshold, a injection of O 2 204 makes it possible to maintain the optimum reaction temperature.
• the lower layer of the second thermal base 201 in direct contact with the second gate 202 of the second reactor 20, provides the second "CO Shift" reaction defined by the formula
• This reaction is exothermic, 41 kJ / mol.
• the thermal energy released can be contained by the arrangement of a double partition, at this lower layer, in which a heat transfer fluid absorbs this thermal energy.
• the coolant may be water used in the exchangers E1 and E2 described above.
• the reaction "CO Shift" continues downstream of the gate 202 into the exchanger E2 where the exotherm of the reaction is dissipated to the heat transfer fluid thereof. Downstream of the second grid, the second gas stream is obtained
• the reactor 20 further comprises an evacuation opening 206 making it possible to evacuate the second stream 22 from the reactor 20.
• This evacuation opening 206 is connected to a pipework maintained in depression by an extraction system which controls and maintains a constant depression in the reactor 20.
• the solid residues R of the second thermal base 201 such as ash, are removed by gravitation through a discharge opening 207 provided in the bottom of the second reactor 20.
• the walls of the enclosure E are configured to be Controlled in temperature and regulated by conventional thermal means, the outer insulation of the enclosure is made in such a way as to limit thermal losses.
• the walls of the enclosure E may have an interior space in which a coolant can be projected to cool the walls and recover heat energy.
• the second gas stream 21 can accumulate, in this space, additional heat capacity.
• the combustion in the two reactors 10 and 20 is preferably reversed, the gaseous effluents and the gas flows having a downward direction of movement in opposition to a gravitational heat flow whose natural direction is ascending.
• the gaseous system is thus forced by mechanical extraction, not shown, which keeps the two reactors 10 and 20 in depression.
• the flow organization can nevertheless be conventional, ascending in the two reactors 10 and 20, or differentiated upward flow in one of the reactors and downward flow in the other.
• the system is thus suitable for at least two independent, concomitant and simultaneous reactions.
• the reaction in the reactor 10 thus has a triple effect: production of the thermal energy required by the system, by complete oxyfuel combustion of at least a portion of the solid fuel, - production of reagent (carbon at red at very high temperature) to enable the reaction below and supply reagent reactor 2, production of carbon monoxide CO, by the oxidation reaction: C + O 2 ⁇ CO 2 followed by the so-called Boudouard reaction: CO 2 + C -> 2 CO
• the second thermal base 201 of the reactor 2 is thus composed of carbon red, which has the property of being "redox". Any element and oxidized molecule that will pass through will be deoxidized by generating at least one carbon oxide CO.
• the system is then ready for the reduction of polluting molecules such as: SOx, NOx, Furans and Dioxins, etc. and more particularly the greenhouse gas CO 2 by prolonging its life cycle by its transformation into CO, which is a commonly used industrial gas.
• the targeted reaction is more particularly the deoxidation, in this reactor 20, of water vapor H 2 O dihydrogen H 2 which is one of the two components of hydrocarbon molecules.
• the first stage of this reaction is endothermic: 131 kJ / mol
• the second stage is exothermic: 41 kJ / mol
• the overall reaction is therefore endothermic and requires a thermal booster of 90 kJ / mol which is supplied to it by oxycombustion.
• An oxygen booster system is advantageously provided at the reactor 20 to overcome any energy deficiency.
• the gases are thus cooled at the temperatures of use for their filtration / purification (transported aerosols, carbons, residual H 2 O, etc.) and their separation, before being put into contact in a catalysis system dedicated to the defined formulation. of hydrocarbon compounds.
• the CO 2 produced by the combustion and the reactions of the source solid fuel is preferably, according to the invention, of vegetable origin (it is neutral with regard to the issue of greenhouse gases since the plant to renew absorbs its CO 2 equivalent to regrowth). Its liquefaction (for industrial use), its sequestration, its transformation into CO (as a substitute for fossil fuels) makes it possible to reduce the proportion of industrial CO 2 from fossil sources released to the atmosphere. Its recycling by the system according to the invention maximizes the conversion efficiency, the "source” energy of the initial solid fuel, energy made available by synthetic hydrocarbon compounds.
• the enclosure E is made to meet the temperature standards of the reactors 10 and 20.
• each of the reactors 10 and 20 divide each of the reactors into two zones: an area upstream of the grid and an area downstream of the grid.
• Each of the reactors receives the inlet duct of the gaseous effluent to be treated in the upstream and outlet zone of the gaseous stream obtained in the downstream zone.
• the upstream zones also comprise the O 2 injectors.
• the upstream zone of the reactor 10 further comprises the inlet opening 103 of the biomass B.
• the zones of the reactors 10 and 20 downstream comprise the extraction openings, respectively 106 and 206, first and second gaseous streams 12 and 22 obtained and the discharge openings, respectively 107 and 207, of the residues R.
• the enclosure according to the invention may be called the "Vegetable Carbon Reactor (RCV)".

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