EP3371275A1 - Procédé et installation pour la conversion chimique d'une matière carbonée avec trempe au gaz de tête - Google Patents
Procédé et installation pour la conversion chimique d'une matière carbonée avec trempe au gaz de têteInfo
- Publication number
- EP3371275A1 EP3371275A1 EP16791592.5A EP16791592A EP3371275A1 EP 3371275 A1 EP3371275 A1 EP 3371275A1 EP 16791592 A EP16791592 A EP 16791592A EP 3371275 A1 EP3371275 A1 EP 3371275A1
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- European Patent Office
- Prior art keywords
- unit
- synthesis
- quenching
- gas
- carbonaceous material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
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- 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
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- 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
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/463—Gasification of granular or pulverulent flues in suspension in stationary fluidised beds
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- 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
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/466—Entrained flow processes
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- 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
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/48—Apparatus; Plants
- C10J3/482—Gasifiers with stationary fluidised bed
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- 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
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/48—Apparatus; Plants
- C10J3/485—Entrained flow gasifiers
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- 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
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
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- 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
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- 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
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- 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
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- 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
- C01B2203/048—Composition of the impurity the impurity being an organic compound
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- 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
- C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
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- 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
- C01B2203/0495—Composition of the impurity the impurity being water
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- 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
- C01B2203/061—Methanol production
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- 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
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- 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
- C01B2203/14—Details of the flowsheet
- C01B2203/146—At least two purification steps in series
- C01B2203/147—Three or more purification steps in series
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- 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
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- 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
- C10J2300/1662—Conversion of synthesis gas to chemicals to methane (SNG)
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- 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
- C10J2300/1665—Conversion of synthesis gas to chemicals to alcohols, e.g. methanol or ethanol
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- 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
Definitions
- the present invention relates to the general field of recovery of the carbonaceous material and in particular the thermochemical treatment of the carbonaceous material to produce liquid hydrocarbons, (biofuels), petrochemical bases and / or synthetic chemicals.
- the present invention relates to a process for the chemical transformation of a carbonaceous material via a gasification and a catalytic synthesis reaction using as reagents carbon monoxide or dihydrogen, said process having a step of quenching the synthesis gas from the gasification of the carbonaceous material using the overhead gas obtained following said catalytic synthesis reaction.
- the present invention also relates to an installation for implementing such a method.
- the current processes under study or pilot scale, for converting biomass into biofuel by an FT synthesis go through a step of gasification of the biomass with steam. water to obtain a synthesis gas consisting essentially of CO and H 2 .
- the initial gasification is carried out either in a fluidized bed reactor or in a driven flow reactor.
- Fluidized bed reactors are less efficient because of the reaction temperature generally between 800 ° C and 1000 ° C, which leads to a lower conversion of biomass to CO + H2 with, for example, the generation of methane (CH 4 ). They do not require specific preparation of the biomass other than drying and medium grinding, which induce only a small loss of efficiency of the overall process. They can be adapted to the production of synthetic natural gas (or SNG for "Synthetic Natural Gas").
- the heat of the process is generally provided by the combustion of a part of the biomass (raw biomass, gas, solid residues, tars, etc.); in this case, the process is called autothermal. Part of the biomass carbon is therefore not converted to biofuel.
- the heat input of the process may be external and, preferably, of nuclear electrical origin without CO2 emission; in this case, the process is said to be allothermal, and the mass yield is higher than that obtained with an autothermal process.
- quench In processes involving driven flow reactors, a quench ("quench”, according to the English terminology) is required at the reactor outlet. It aims to cool down the synthesis gas quickly to stop the ongoing reactions and to cut down some pollutants and particles.
- quenching is typically carried out by adding from a cold flow to the stream of hot synthesis gas at the outlet of the reactor.
- quenching families which use (1) a liquid stream, the most common being water quenching, (2) a solid stream and (3) a gas stream.
- Various patents, patent applications and publications cover all of these quenching techniques.
- the method that is the subject of the latter comprises in particular a gasification step, in a driven flow reactor, of a suspension obtained by mixing carbonaceous material to be treated with water or oil and a total quenching step of synthesis gas produced by water injection.
- the carbonaceous material to be treated is advantageously bituminous coal, cokes such as oil or bituminous coal or lignite coal.
- US Patent Application 2007/051044 [3] is another example of a gasification process involving quenching with water.
- Liquid streams other than water are also conceivable.
- US Pat. No. 5,433,760 [4] describes a first step of quenching the synthesis gas using a liquid carbon quenching medium associated with a small amount of carrier gas, typically nitrogen, cooled and recycled synthesis gas, water and carbon dioxide.
- Liquid carbon quenching media include liquid hydrocarbons, asphalt, diesel, residual fuel oils, coal tar, organic waste and amines.
- Quenching with a solid flow is in particular envisaged in international application WO 94/26850 [5].
- the latter proposes to use pulverulent coal associated with a small amount of nitrogen or carbon dioxide, as carrier gas, in a first step of quenching the synthesis gas.
- the CarboV process from Choren relies on quenching with a solid flow while associating it with a recycling process flow.
- the coal resulting from a first stage of biomass transformation pyrolysis
- This process has been presented several times in international conferences and in particular in 2005 [6].
- FIGS 1A to 1E repeat this sequence of steps including the features related to different types of quenching previously mentioned.
- FIGS. 1A to 1E show a conversion reaction from carbon monoxide to steam, also called a "Water Gas Shift" reaction, which results in a loss of carbon and therefore a decrease in material yield. It should be noted, however, that this reaction may not be present for quenching other than liquid flow quenching and especially water quenching.
- the inventors have therefore set themselves the goal of proposing a process for converting biomass and more particularly any carbonaceous material, in which the material and energy yield can be increased when compared to the processes of the prior art.
- the invention proposes a method and an installation making it possible to overcome all or part of the disadvantages and difficulties encountered in the processes and installations of the prior art.
- the present invention provides a method and an installation for producing liquid hydrocarbons, (biofuels), petrochemical bases and / or synthetic chemicals from a carbon resource, by implementing a step gasification process in a flow-through reactor and a Fischer-Tropsch type synthesis step with increased material and energy yields compared to the methods of the prior art.
- the work of the inventors has shown that this object could be achieved by using, during quenching of the synthesis gas resulting from the gasification step, a by-product corresponding to the gaseous effluent resulting from the Fischer-Tropsch synthesis. also known as "overhead gas".
- overhead gas also known as "overhead gas”.
- the present invention applies not only to the chemical conversion processes of the carbonaceous feed involving a gasification step and a chemical synthesis step of Fischer-Tropsch type but, more generally, to any chemical conversion process. involving a gasification step and a chemical synthesis step in which the catalytic chemical reaction implemented uses as reagents carbon monoxide (CO) and dihydrogen (hh) and produces a recoverable liquid effluent and a recyclable gaseous effluent.
- CO carbon monoxide
- hh dihydrogen
- the present invention applies not only to chemical conversion processes of the carbonaceous feedstock implementing not only a driven flow reactor but also a fluidized bed reactor.
- the present invention proposes a method for combining, in a single step, the quenching of the synthesis gas obtained via the gasification step and the recycling of the gaseous effluent resulting from the subsequent chemical synthesis.
- this quenching and recycling corresponded to two independent steps in the processes for converting the carbonaceous material.
- the present invention relates to a method of chemical transformation of a carbonaceous material comprising at least the steps of:
- step (b) subjecting the synthesis gas produced in step (a) to quenching by adding to said synthesis gas a quenching fluid;
- step (b) subjecting the quenched effluent obtained in step (b) to a purification treatment
- step (c) subjecting the purified effluent obtained after step (c) to a catalytic synthesis reaction using as reagents carbon monoxide (CO) and dihydrogen (H 2 ) whereby a gaseous effluent and a liquid effluent are obtained ;
- CO carbon monoxide
- H 2 dihydrogen
- chemical transformation of a carbonaceous material is meant a process for producing from a carbonaceous material at least one compound selected from the group consisting of liquid hydrocarbons, (biofuels), petrochemical bases, synthetic chemicals or precursors thereof.
- liquid hydrocarbons such as liquid hydrocarbons, (biofuels), petrochemical bases, synthetic chemicals or precursors thereof.
- alkanes alkenes
- alcohols such as methanol or ethanol
- ethers such as dimethyl ether
- synthetic paraffins gasoline, kerosene, diesel, petrochemical naphtha
- lubricating oils any of their precursors.
- the process according to the present invention is similar to a BtL (for "Biomass to Liquid") process, a CtL (for “Coal to Liquid”) process or a GtL process (for "Gas to Liquid”).
- carbonaceous material is meant a material of which at least one of the constituents is an organic, synthetic or natural compound. Any carbonaceous material, solid, liquid or gas, known to those skilled in the art can be used in the context of the present invention.
- the carbonaceous material is in solid form and is optionally associated with a carbonaceous material, of identical or different nature, in solid, liquid and / or gaseous form.
- the carbonaceous material used in the context of the present invention is chosen from the group consisting of natural gas, shale gas, crude oil, light naphtha, heavy fuel oil, coal, bituminous coal, cokes such as oil or bituminous coal, lignite coal, tar sands, oil shale, organic matter of animal or vegetable origin (also known as “biomass”), an organic matter human activities and any of their mixtures.
- the carbonaceous material is an organic material of animal or vegetable origin or an organic material resulting from human activities. More particularly, the carbonaceous material used in the context of the present invention is chosen from the group consisting of agricultural productions such as dedicated productions called “energetic” such as miscanthus, switchgrass (Panicum virgatum or switchgrass) and coppice with very short rotation such as poplar or willow; crop residues such as cereal straw, corn stover and sugar cane stalks; forest production; forest production residues such as residues from wood processing; agricultural residues from livestock farming such as animal meal, manure and slurry; and organic waste.
- agricultural productions such as dedicated productions called "energetic” such as miscanthus, switchgrass (Panicum virgatum or switchgrass) and coppice with very short rotation such as poplar or willow
- crop residues such as cereal straw, corn stover and sugar cane stalks
- forest production forest production residues such as residues from wood processing
- agricultural residues from livestock farming such as animal meal
- Organic waste includes household organic waste, industrial organic waste, hospital waste, sludge from wastewater treatment, sludge from the treatment of industrial liquid effluents, sludge from silo bottoms and their mixtures.
- the industrial organic waste comprises waste from the agri-food or catering industries; packaging such as pallets, crates and plastic containers; production waste such as sawdust, falling and cutting; used products such as paper, out of service equipment and tires; and materials such as cardboard, textiles and plastics.
- dried mud is meant a sludge in the form of a solid sludge or sludge and whose dry weight% relative to the total sludge mass is greater than 50%.
- the carbonaceous material used in the present invention is solid, liquid or gaseous, the latter advantageously has a moisture content of less than 50%, ie the% by weight of water relative to the total mass of carbonaceous material is less than at 50%.
- the carbonaceous material used in the present invention may have any ash content.
- the ash content of this carbonaceous material is between 0.5 and 30% by weight.
- the ash content of a sample expressed in mass% corresponds to the ratio of the mass of the residue obtained after calcination at a defined temperature and for a given time, to the initial mass of the sample. The ash levels are measured by calcination at 550 ° C according to DIN EN 14775.
- Step (a) of the process of the invention is a conventional gasification step carried out in a driven-flow reactor or in a fluidized-bed reactor.
- step (a) consists in bringing the carbonaceous material optionally pretreated, in the presence of a gasifying agent and optionally an oxidizer, to a temperature greater than or equal to 800 ° C. and in particular between 800 ° C. and 1200 ° C. and this, under an absolute pressure of between 1 bar and 30 bars and in particular between 1 bar and 10 bars, and in particular between 1 bar and 5 bars.
- step (a) consists in bringing the optionally pretreated carbonaceous material, in the presence of a gasifying agent and optionally an oxidizer, to a temperature greater than or equal to 1000 ° C. , especially between 1200 ° C and 1800 ° C and, in particular, between 1300 ° C and 1600 ° C and this, under an absolute pressure of between 1 bar and 80 bars and in particular between 5 bars and 40 bars, and in particular between 25 bars and 35 bars.
- the high temperatures used during this gasification step make it possible to obtain a carbon conversion rate of the carbonaceous material to a high CO gas and thus to reduce the amount of unconverted carbon present in the by-products of the gasification and in particular in the ashes produced during the latter.
- These high temperatures are obtained by using one or more burner (s) present (s) in the reactor and in particular in the driven flow reactor.
- the gasifying agent or gaseous agent required for the gasification is in particular water vapor, carbon dioxide and / or oxygen.
- a gasifying agent is present in an amount sufficient to allow gasification of the carbonaceous material. Such an amount can be readily determined by those skilled in the art by routine work.
- step (a) of the process and / or when the carbonaceous material has insufficient moisture to generate a quantity of water vapor effective to allow the gasification of this carbonaceous material it may be necessary to inject in the entrained flow reactor or in the fluidized bed reactor, water vapor.
- step (a) of the process it may be necessary to inject, in the driven-flow reactor or in the fluidized-bed reactor, a suitable oxidizer in order to supply the energy for the rise in temperature and for gasification.
- a suitable oxidizer is advantageously a reactive gas comprising oxygen such as air, air enriched with oxygen or pure oxygen.
- the gasification of the carbonaceous material during step (a) of the process according to the invention produces a synthesis gas, also known under the name "syngas".
- a synthesis gas also known under the name "syngas”.
- the nature and composition of the synthesis gas obtained following step (a) of the process depend in particular on the nature of the carbonaceous material used during the gasification and the oxidizing or reducing conditions used during this step.
- the synthesis gas produced by the process according to the present invention mainly comprises hydrogen (H 2 ) and carbon monoxide (CO).
- “predominantly” is meant that H 2 and CO are present in a volume percentage relative to the total volume of synthesis gas greater than 50%, especially greater than 60% and, in particular, greater than 70%.
- the synthesis gas also contains, in a minor but significant amount, water (H 2 O) and carbon dioxide (CO 2 ) resulting from at least partial combustion of the biomass. These two compounds are not recovered in the rest of the process and can be separated before synthesis.
- minority is meant that H 2 0 and C0 2 are present in a volume percentage relative to the total volume of synthesis gas less than 50%, especially less than 40% and, in particular, less than 30%.
- the synthesis gas produced by the process according to the present invention comprises hydrogen (H 2 ), carbon monoxide (CO), carbon dioxide (CO 2 ), water (H 2 O). ) and possibly one or more other gaseous element (s), this or these last (s) being advantageously present in the form of traces.
- the respective proportion of the various elements present in the synthesis gas ie H 2 and CO depends on the nature of the carbonaceous material treated and the thermal conditions in the entrained flow reactor.
- Race element means a gaseous element present in a volume percentage relative to the total volume of the synthesis gas of less than 6%, in particular less than 4%, in particular less than 2%, and more particularly less than 1%.
- gaseous elements present in the synthesis gas produced following step (a) of the process according to the invention and especially present in trace amounts in the synthesis gas produced following step (a) of the process according to the invention, mention may be made of methane (CH 4 ), acetylene (C 2 H 2 ), ethylene (C 2 H 4 ), ethane (C 2 He), inorganic or organic aerosols, inorganic pollutants such as hydrogen sulfide (H 2 S), ammonia (N H 3), hydrochloric acid (HCI), hydrogen cyanide (HCN) and carbon oxysulfide (COS), organic compounds such as benzene (CeHe), toluene (C7H8) and polycyclic aromatic hydrocarbon
- the synthesis gas obtained following step (a) of the process according to the present invention is at a temperature greater than or equal to 1000 ° C., in particular between 1200 ° C. and 1800 ° C and, in particular, between 1300 ° C and 1600 ° C.
- Step (b) of the process according to the present invention consists in lowering the temperature of the synthesis gas to a temperature of less than or equal to 900 ° C., in particular less than or equal to 800 ° C. and, in particular, less than or equal to 700 ° C. ° C and this, by contact with a quenching effluent.
- the synthesis gas obtained following step (a) of the process according to the present invention is at a temperature greater than or equal to 800 ° C. and in particular between 800 ° C. and 1200 ° C.
- Step (b) of the process according to the present invention consists in lowering the temperature of the synthesis gas to a temperature of less than or equal to 700 ° C. and in particular of less than or equal to 600 ° C., and this, by placing it in contact with an effluent. quenching.
- One of the remarkable characteristics of the process according to the invention consists in using as quench effluent a by-product of this process, namely the gas stream obtained following the chemical synthesis step using as starting material H 2 and CO.
- step (a) and step (b) of the process according to the present invention can be carried out using a driven flow reactor designed for TGP type water quenching (for "Texaco Gasification Process"), MGP (for “Manufactured Gas Plant”), GSP (for “Gas Turbine Simulation Program”) or PDQ. (for "Prenflo with Direct Quench”).
- TGP type water quenching for "Texaco Gasification Process”
- MGP for "Manufactured Gas Plant”
- GSP for "Gas Turbine Simulation Program”
- PDQ for "Prenflo with Direct Quench”
- Step (c) of the process according to the present invention consists of a purification treatment of the quenched effluent, obtained following step (b).
- purification treatment is meant a treatment for removing compounds such as sulfur compounds, nitrogen compounds, carbon dioxide, tars, halides or alkali metals, present in the quenched effluent, obtained following step (b) and may adversely affect the catalysts used in the subsequent chemical syntheses of step (d) of the process according to the invention.
- This purification step may possibly make it possible to achieve the ratio H2 / CO adapted to the subsequent chemical synthesis step of step (d) of the process.
- Any method for removing at least one of the aforementioned elements and usually used for the purification of a synthesis gas obtained by gasification can be used in the context of the process according to the present invention.
- the purification step (c) of the process according to the present invention implements at least one step selected from the group consisting of an acid gas removal step, a halogenated compounds elimination step, a step of removal of sulfur compounds, a step of catalytic hydrolysis of carbon oxysulfide (COS) and hydrogen cyanide (HCN), a step of conversion of carbon monoxide to steam (reaction of "Water Gas Shift” ) and a final purification step on guard bed.
- the purification step (c) of the process according to the present invention does not implement a step of converting carbon monoxide to steam ("Water Gas Shift" reaction).
- the purification step (c) of the process according to the present invention implements an acid gas removal step combined with at least one other step selected from the group consisting of a halogenated compounds elimination step, a step of removing sulfur compounds, a step of catalytic hydrolysis of carbon oxysulfide (COS) and hydrogen cyanide (HCN) and a final purification step on guard bed.
- a halogenated compounds elimination step a step of removing sulfur compounds
- COS carbon oxysulfide
- HCN hydrogen cyanide
- this conversion uses high temperature catalysts, that is to say implemented at temperatures of 350 ° C, which are typically based on iron and chromium; low temperature catalysts, that is to say used at temperatures of about 200 ° C, which are typically based on copper and zinc or precious metal catalysts, whose operating temperatures are intermediate ;
- the chemical synthesis in step (d) of the process according to the invention may be any chemical synthesis in which the catalytic chemical reaction used uses CO and H 2 as reagents.
- this chemical synthesis is selected from the group consisting of catalytic synthesis of Fischer-Tropsch type, catalytic synthesis of methanol, catalytic synthesis of ethanol and catalytic synthesis of dimethyl ether.
- the Fischer-Tropsch synthesis reaction corresponds respectively to the following reaction (III) or (IV):
- the H 2 / CO ratio is advantageously between 1.5 and 3 and especially between 2 and 2.5.
- Catalytic synthesis of methanol using CO and H 2 as reagents is a reaction known to those skilled in the art.
- the latter can be carried out with a catalyst based on copper oxide at a pressure of 50 to 100 bar and at a temperature of between 180 and 270 ° C., depending on the overall reaction (V ) next :
- H 2 / CO is advantageously between 1 and 3 and in particular between 1.5 and 2.5.
- the ratio H2 / CO is advantageously between 1 and 3 and in particular between 1.5 and 2.5.
- any catalytic synthesis reaction of dimethyl ether (DME) using CO and H 2 as reagents known to those skilled in the art can be used in the context of the present invention.
- the latter may be carried out with a multifunctional catalyst of the copper oxide, zinc oxide or aluminum oxide type, according to the following main reaction (VII):
- the H 2 / CO ratio is advantageously between 0.2 and 2 and in particular between 0.5 and 1.5.
- the nature of the gaseous effluent and that of the liquid effluent obtained following step (d) of the process according to the present invention will depend on the type of synthesis implemented at this stage.
- the gaseous effluent at least a portion of which is used as a quench effluent during step (b) comprises at least one element selected from the group consisting of carbon monoxide, carbon dioxide, carbon dioxide and hydrogen and a carbon compound comprising 1 to 20 carbon atoms, said element (s) possibly being combined with water vapor.
- a carbon compound comprising from 1 to 20 carbon atoms
- a gaseous effluent used as quenching gas which would be exclusively composed of water vapor.
- the gaseous effluent used as quenching effluent during step (b) is used directly following step (d): it is not subjected to any treatment such as a purification.
- the carbonaceous material prior to the gasification step (a), the carbonaceous material may be pretreated. Any pretreatment of the organic material to destructure the latter prior to a gasification step is used in the context of the present invention.
- the pretreatment implemented in the context of the present invention comprises at least one step selected from the group consisting of a drying step, a roasting step, a granulation step and a grinding step. These steps are more particularly adapted to a carbonaceous material in solid form or comprising a solid fraction.
- the drying step optionally used in the context of the process according to the invention aims to reduce the moisture content of the organic material to be gasified, in particular to obtain a moisture content of less than 50%.
- Any technique and any drying device known to those skilled in the art can be used in the context of the invention.
- this drying is carried out at a temperature between 40 and 180 ° C, especially between 60 and 160 ° C and, in particular, between 80 and 140 ° C and for a period of between 15 min and 4 h, in particular between 30 minutes and 3 hours, and in particular between 1 and 2 hours.
- the energy required for this drying can be provided either independently to the process according to the invention, or by combustion of one of the gases produced during the latter. In this case, the energy can be supplied by the combustion of a part of the synthesis gas produced in step (a) and / or by the combustion of a part of the gaseous effluent produced in step ( d).
- roasting step is meant a step of subjecting the optionally dried carbonaceous material to a thermochemical treatment at a temperature typically between 200 and 320 ° C, to remove water and modify a portion of the carbonaceous material to make it more friable especially by breaking the fibers (case of the biomass-type carbonaceous material).
- Roasting the carbonaceous material also produces gases such as water vapor, formic acid, acetic acid, methanol, CO and carbon dioxide. This roasting step is carried out in any roasting oven known to man of career. The energy required for this roasting can be provided either independently to the process according to the invention, or by combustion of a gas produced during the latter.
- the energy can be supplied by the combustion of a part of the synthesis gas produced in step (a), by the combustion of a part of the gaseous effluent produced in step (d). and / or by burning a portion of the gases produced during this roasting. Note that these can also be used to provide the energy needed for drying.
- the method according to the present invention may also include granulation pretreatment, also known as pelletizing.
- This pretreatment consists in pressing the carbonaceous material against a sieve to obtain granules of uniform size and shape, said granules having a bulk density increased relative to the density of the carbonaceous material before granulation. Any technique and any granulation device known to those skilled in the art can be used in the context of the invention.
- the carbonaceous material used in the context of the present invention may have to undergo a grinding step to obtain residues having characteristic dimensions, less than 1 mm, especially lower than equal to 500 ⁇ and, in particular, less than or equal to 300 ⁇ . Any technique and any grinding device known to those skilled in the art can be used in the context of the invention.
- the method according to the present invention may comprise a step of adding H 2 to at least one of the effluents obtained following step (b) or following step (c) of the process.
- this addition is carried out on the purified effluent obtained following step (c) and this, prior to the synthesis step (d) of the process according to the invention.
- the H2 added during this optional additional step can be obtained independently from the process according to the invention or, conversely, be produced during this process.
- the H 2 can come from a reforming step from one or more hydrocarbon (s) produced during the process according to the invention or from one or more hydrocarbon (s) of fossil origin (CH 4 for example), an alkaline electrolysis step and / or a SOEC type high temperature electrolysis step and this, from H 2 0 or an H 2 mixture 0 / CO produced during the process according to the invention.
- the method according to the present invention may also comprise a step consisting in recovering heat energy during the process, in particular in order to increase the energy efficiency of the latter.
- the heat energy thus recovered can be used in the process according to the present invention or in any other process requiring a supply of heat energy.
- This heat energy can be recovered at any point in the process according to the present invention i.e. following the gasification step and prior to the catalytic synthesis step.
- the heat energy is recovered following the quenching step (b) and prior to the purification step (c).
- the heat energy thus recovered can, for example, be used to generate steam such as water vapor.
- steam such as water vapor.
- PSG type for "Process with Steam Generation” which has a heat recovery steam generator (HRSG).
- the present invention also relates to an installation that can be implemented in a method as defined above.
- the installation according to the invention comprises: a unit for gasification of the carbonaceous material with synthesis gas, said unit comprising at least one driven-flow or fluidized-bed reactor, in particular such as previously defined;
- quenching unit disposed at the outlet of said gasification unit; a purification unit for the quenched effluent obtained at the outlet of said quenching unit;
- a catalytic synthesis reaction unit for preparing a gaseous effluent and a liquid effluent from the purified effluent obtained at the outlet of the purification unit;
- the purification unit of the plant according to the invention comprises at least one unit selected from the group consisting of an acid gas removal unit, a halogenated compounds elimination unit, a sulfur compounds elimination unit. , a catalytic hydrolytic unit of carbon oxysulfide (COS) and hydrogen cyanide (HCN), a unit of conversion of carbon monoxide to steam (WGS unit) and a final purification unit on a bed of keep.
- the purification unit of the plant according to the invention comprises at least one acid gas elimination unit combined with at least one other stage chosen from the group consisting of a unit for eliminating halogenated compounds, a unit removal of sulfur compounds, a catalytic hydrolytic unit of carbon oxysulfide (COS) and hydrogen cyanide (HCN) and a final purification unit on guard bed. All that has previously been explained as to the purification steps applies mutatis mutandis to the purification units.
- the purification unit of the installation does not include a unit for converting carbon monoxide to steam (WGS unit).
- the catalytic synthesis reaction unit of the plant according to the invention comprises at least one unit selected from the group consisting of a Fischer-Tropsch type catalytic synthesis reactor, a catalytic synthesis reactor of methanol, a catalytic synthesis reactor ethanol and a synthesis reactor catalytic dimethyl ether. All that has previously been explained as to catalytic syntheses applies mutatis mutandis to catalytic synthesis reactors.
- the plant according to the invention may further comprise at least one pre-treatment unit for the carbonaceous material.
- This unit is arranged upstream of the gasification unit.
- this pretreatment unit comprises at least one unit selected from the group consisting of a drying unit, a roasting unit, a granulation unit and a grinding unit. All that has previously been explained as to the pretreatment steps applies mutatis mutandis to preprocessing units.
- the plant according to the present invention may further comprise means for injecting H 2 to at least one of the effluents obtained at the outlet of the quenching unit or at the outlet of the purification unit. More particularly, these means make it possible to inject H 2 into the purified effluent obtained at the outlet of the purification unit.
- the installation according to the present invention may also comprise means for recovering the heat energy of at least one of the effluents circulating in said installation.
- the heat energy is recovered at the quenched effluent obtained at the outlet of the quenching unit.
- FIGS. 1A to 1E show general diagrams of prior art biomass chemical conversion processes using water quenching without recycling (FIG. 1A), water quenching with recycling using steam reforming (FIG. 1B), quenching with a high temperature exchanger (FIG. 1C), quenching with solid recycling (FIG. 1D) and quenching with synthesis gas recirculation (FIG. 1E).
- Figure 2 shows a block diagram of a particular sequence of a method according to the invention.
- the sequence of steps of a process according to the present invention as shown in FIG. 2 is carried out with a driven flow reactor and on a preferably vegetable biomass carbon material of formula C6Hg0 4 .
- This biomass is subjected to a first preparation step consisting of a pretreatment as previously defined (Brick I).
- This pretreatment advantageously comprises one or more steps selected from a drying step, a roasting step, a granulation step and a grinding step.
- the biomass thus treated is fed into a driven flow reactor designed especially for a gas quench type PSG (for "Process with Steam Generation”).
- a gas quench type PSG for "Process with Steam Generation”
- the biomass undergoes a gasification at a temperature of 1500 ° C., under a pressure of 30 bars, in the presence of H 2 0, CO 2 and / or O 2 as a gasifier and of O 2 as oxidant ( Brick 1).
- the synthesis gas produced following this gasification step mainly comprises CO and H 2 in an H 2 / CO ratio of 0.6. It is then subjected to a quenching step so as to lower its temperature to a value of 800 ° C. (Brick 2).
- This quenching step consists of contacting the synthesis gas resulting from the gasification with at least a portion of the gaseous effluent or overhead gas, resulting from Fischer-Tropsch catalytic synthesis (Brick 5).
- the quenched effluent obtained at the outlet of the quenching unit is subjected to another treatment aimed at recovering the heat energy of this quenched effluent.
- This treatment uses a heat exchanger and a heat recovery steam generator (HRSG) (Brick 3).
- HRSG heat recovery steam generator
- the recovered effluent has a temperature of 450 ° C. and an H 2 / CO ratio of between 1.5 and 2.
- this sequence and, in general, a process according to the present invention do not have any reactor for converting carbon monoxide to steam (WGS).
- the effluent obtained following the heat exchange step (Brick 3) is cleaned so as to remove the impurities it contains up to levels acceptable for the catalytic synthesis of Fischer-Tropsch type subsequently implemented.
- Brick 4 of Figure 2 thus corresponds to a purification step of the effluent implementing a purification unit.
- This purification step is more particularly a step of removing acid gases such as hydrogen sulphide (H 2 S) or carbon dioxide (CO 2 ) contained in the quenched effluent obtained at the outlet of Brick 3 by use of chemical solvents such as monoethanolamine, diethanolamine, methyldiethanolamine or a mixture thereof and / or physical solvents such as polyethylene glycol diethyl ether, polyethylene glycol dibutyl ether or methanol.
- Processes using chemical solvents operate at temperatures in the range of 20-30 ° C and atmospheric pressure up to possibly 30 bar.
- Processes using physical solvents operate at higher pressure and lower temperature.
- the temperatures are from -30 ° C. to -60 ° C. and the pressures from 30 bars to 60 bars.
- Such purification step may be combined with one or more other purification step (s) selected from the group consisting of a halogenated compound removal step, a sulfur compound removal step, a step of catalytic hydrolysis of carbon oxysulfide (COS) and hydrogen cyanide (HCN) and a final purification step implemented on guard bed.
- a halogenated compound removal step e.g., a sulfur compound removal step
- a step of catalytic hydrolysis of carbon oxysulfide (COS) and hydrogen cyanide (HCN) e.g., a halogenated compound removal step
- COS carbon oxysulfide
- HCN hydrogen cyanide
- the purified effluent obtained at the outlet of the cleaning / purification step is subjected to a catalytic synthesis step of Fischer-Tropsch type (Brick 5) using a cobalt or iron-based catalyst and according to the following reaction (III) :
- the purified effluent obtained at the outlet of the cleaning / purification step is supplemented with H 2 so as to obtain a H 2 / CO ratio of 2.
- the H 2 used is advantageously obtained via a step of reforming, an alkaline electrolysis step and / or a high temperature electrolysis step typically at 800 ° C and this from water from the process or injected from the outside.
- the gaseous effluent obtained after the catalytic Fischer-Tropsch synthesis type predominantly comprises CH 4, C 2 H 4, C 2 H6, C3H6, C3H8, C 4 Hs, C 4 Hio and small amounts of hydrocarbons with more than 5 carbons, whereas the liquid effluent consists of a mixture of liquid hydrocarbons comprising more than 5 carbons.
- the gasification is carried out in a flux-driven reactor with a biomass mixture, H 2 0 and 0 2 so as to reach a thermal equilibrium at 1400 ° C.
- the molar ratio H 2 / CO is 0.54, against about 2 necessary for the synthesis.
- the recycle rate of the overhead gas is free from 0 to 100%, since the rest is provided by quenching with water. 0% corresponds to case 1 presented above. 100% is not conceivable due to the excessive accumulation of inerts in the gas, in particular N2 used for some inertages and partially for the injection of the solid into the RFE. A purge rate, in our case estimated at around 10% is therefore desirable. A recycling rate ranging from 10% to 90% is possible. For the calculations, the inventors worked with the recycling rate range varying between 50% and 90%.
- One of the objectives of this quenching being to convert the light hydrocarbons and in particular, the methane, the part of the reactor intended to perform the quenching and the reaction will have to be dimensioned so that a sufficient residence time is left to the gas for the transformation to operate.
- the gas passing from 1400 ° C to 800 ° C the conversion kinetics can be affected by the temperature conditions encountered by the gas.
- the conversion rate of the overhead gas can not be known precisely to date. The inventors have therefore made several calculations with 3 fixed gas conversion rates: 50%, 70% and 90%.
- each step was modeled respecting the temperature and pressure levels required in the process.
- Each reaction step was modeled by an equilibrium equation describing the chemical transformation performed (gasification, water gas shift, steam reforming, synthesis, hydrocracking). This makes sure that material balances are respected.
- the thermodynamic models included in the software make it possible to calculate the energy balances of each reaction stage, as well as those of the exchangers and compressors.
- the high temperature heat exchanger (HSRG) was not simulated in detail because there is no optimization objective on the energy balance for these calculations (no high energy integration). The cooling of the synthesis gas is still considered in the balance sheet.
- the indicators that most favorably influence the process with gas quenching are:
- the H 2 / CO molar ratio at quenching output increases by 50%, which indicates a decrease in the gas flow rate sent to the Water Gas Shift stage; the flow rate of gas sent to the Water Gas Shift stage decreases by 25%, which makes it possible to envisage a reduction in the size of the unit and therefore the associated investment and operating costs; and
- the flow rate of CH 4 decreases in synthesis input, which is favorable for the dimensions of the unit and for the reaction because the CH 4 is considered as an inert and therefore a diluent of the gas.
- the 4 indicators which are evolving unfavorably, are all in the direction of increasing the capacity of the synthesis unit by 50 to 80%. This is the flow of syngas at the entry of the synthesis, the flow rate of N 2 at the entry of the synthesis, the flow of overhead gas (C1-C4) produced and recycled to the quench (associated with a compression unit). Since these indicators are only linked to the FT synthesis unit, their unfavorable impact is counterbalanced by the fact that the investment and operating costs of this unit will be adapted to its production, which increases in the same proportions.
- This coupling is more flexible than recycling with steam reforming because the recycling rate can be set from 0 to 100% depending on the objectives sought, whereas, in the case of steam reforming, the recycling rate is imposed by the quantity of FT gas to be burned. to reform the gas (estimated at about 60%).
- the recirculation coupling of the synthesis gases FT and quench at the outlet of the gasification reactor makes it possible to significantly reduce the quantity of water consumed by the process, to reduce the size of the installations, with the exception of the unit of FT synthesis, even suppress them (steam reforming) and increase the material and energy yields.
- this coupling therefore has a favorable impact on the economics of the process.
- this coupling necessarily imposes a larger investment (management of recycling, compressor and size of FT synthesis), but it allows to significantly increase the fuel production efficiency which is very favorable in term production cost.
- this coupling is much more advantageous economically because it reduces the investment costs (vapor reforming unit removed in particular) and operating, while increasing the production of fuel.
- the increase in investment is offset by the increase in yields and the decline in utility costs, which leads to a decrease in the cost of producing fuel.
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FR1560616A FR3043340B1 (fr) | 2015-11-05 | 2015-11-05 | Procede et installation pour la conversion chimique d'une matiere carbonee avec trempe au gaz de tete |
PCT/EP2016/076752 WO2017077090A1 (fr) | 2015-11-05 | 2016-11-04 | Procédé et installation pour la conversion chimique d'une matière carbonée avec trempe au gaz de tête |
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US5431703A (en) | 1993-05-13 | 1995-07-11 | Shell Oil Company | Method of quenching synthesis gas |
US5433760A (en) | 1993-05-13 | 1995-07-18 | Shell Oil Company | Method of quenching synthesis gas |
FR2861402B1 (fr) | 2003-10-24 | 2008-09-12 | Inst Francais Du Petrole | Production de carburants liquides par un enchainement de procedes de traitement d'une charge hydrocarbonee |
DE102005041931B4 (de) | 2005-09-03 | 2018-07-05 | Siemens Aktiengesellschaft | Vorrichtung zur Erzeugung von Synthesegasen durch Partialoxidation von aschehaltigen Brennstoffen unter erhöhtem Druck mit Teilquenchung des Rohgases und Abhitzegewinnung |
DE202005021661U1 (de) | 2005-09-09 | 2009-03-12 | Siemens Aktiengesellschaft | Vorrichtung zur Erzeugung von Synthesegasen durch Partialoxidation von aus aschehaltigen Brennstoffen hergestellten Slurries und Vollquenchung des Rohgases |
US20080098654A1 (en) * | 2006-10-25 | 2008-05-01 | Battelle Energy Alliance, Llc | Synthetic fuel production methods and apparatuses |
FR2910489B1 (fr) * | 2006-12-22 | 2009-02-06 | Inst Francais Du Petrole | Procede de production d'un gaz de synthese purifie a partir de biomasse incluant une etape de purification en amont de l'oxydation partielle |
WO2011097648A2 (fr) * | 2010-02-08 | 2011-08-11 | Fulcrum Bioenergy, Inc. | Procedes pour convertir de maniere economique des dechets municipaux solides en ethanol |
FR2982857B1 (fr) * | 2011-11-21 | 2014-02-14 | Gdf Suez | Procede de production de biomethane |
FR2994980B1 (fr) * | 2012-09-05 | 2014-11-14 | Commissariat Energie Atomique | Procede de gazeification de charge de matiere carbonee, a rendement ameliore. |
FR3009308B1 (fr) * | 2013-08-01 | 2015-09-11 | Commissariat Energie Atomique | Procede de conversion thermochimique d'une charge carbonee en gaz de synthese contenant majoritairement h2 et co. |
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