EP2663619A1 - Procédé d'utilisation de l'énergie thermique des gaz en produit dans une usine appartenant à la filière btl - Google Patents

Procédé d'utilisation de l'énergie thermique des gaz en produit dans une usine appartenant à la filière btl

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Publication number
EP2663619A1
EP2663619A1 EP11855609.1A EP11855609A EP2663619A1 EP 2663619 A1 EP2663619 A1 EP 2663619A1 EP 11855609 A EP11855609 A EP 11855609A EP 2663619 A1 EP2663619 A1 EP 2663619A1
Authority
EP
European Patent Office
Prior art keywords
steam
plant
btl
gases
btl plant
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.)
Withdrawn
Application number
EP11855609.1A
Other languages
German (de)
English (en)
Other versions
EP2663619A4 (fr
Inventor
Jorma Kautto
Olli-Pekka VILJAKAINEN
Mika Timonen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Vapo Oy
Original Assignee
Vapo Oy
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Vapo Oy filed Critical Vapo Oy
Publication of EP2663619A1 publication Critical patent/EP2663619A1/fr
Publication of EP2663619A4 publication Critical patent/EP2663619A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72Other features
    • C10J3/86Other features combined with waste-heat boilers
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72Other features
    • C10J3/726Start-up
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F22STEAM GENERATION
    • F22BMETHODS OF STEAM GENERATION; STEAM BOILERS
    • F22B1/00Methods of steam generation characterised by form of heating method
    • F22B1/02Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers
    • F22B1/18Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers the heat carrier being a hot gas, e.g. waste gas such as exhaust gas of internal-combustion engines
    • F22B1/1838Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers the heat carrier being a hot gas, e.g. waste gas such as exhaust gas of internal-combustion engines the hot gas being under a high pressure, e.g. in chemical installations
    • F22B1/1846Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers the heat carrier being a hot gas, e.g. waste gas such as exhaust gas of internal-combustion engines the hot gas being under a high pressure, e.g. in chemical installations the hot gas being loaded with particles, e.g. waste heat boilers after a coal gasification plant
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72Other features
    • C10J3/82Gas withdrawal means
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00Purifying combustible gases containing carbon monoxide
    • C10K1/02Dust removal
    • C10K1/024Dust removal by filtration
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/04Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00Solid fuels
    • C10L5/40Solid fuels essentially based on materials of non-mineral origin
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01KSTEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
    • F01K13/00General layout or general methods of operation of complete plants
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01KSTEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
    • F01K17/00Using steam or condensate extracted or exhausted from steam engine plant
    • F01K17/06Returning energy of steam, in exchanged form, to process, e.g. use of exhaust steam for drying solid fuel or plant
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F22STEAM GENERATION
    • F22DPREHEATING, OR ACCUMULATING PREHEATED, FEED-WATER FOR STEAM GENERATION; FEED-WATER SUPPLY FOR STEAM GENERATION; CONTROLLING WATER LEVEL FOR STEAM GENERATION; AUXILIARY DEVICES FOR PROMOTING WATER CIRCULATION WITHIN STEAM BOILERS
    • F22D1/00Feed-water heaters, i.e. economisers or like preheaters
    • F22D1/32Feed-water heaters, i.e. economisers or like preheaters arranged to be heated by steam, e.g. bled from turbines
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0205Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0283Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/042Purification by adsorption on solids
    • C01B2203/043Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465Composition of the impurity
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06Integration with other chemical processes
    • C01B2203/062Hydrocarbon production, e.g. Fischer-Tropsch process
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08Methods of heating or cooling
    • C01B2203/0805Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0903Feed preparation
    • C10J2300/0909Drying
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913Carbonaceous raw material
    • C10J2300/0916Biomass
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953Gasifying agents
    • C10J2300/0959Oxygen
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/16Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1603Integration of gasification processes with another plant or parts within the plant with gas treatment
    • C10J2300/1621Compression of synthesis gas
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/16Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656Conversion of synthesis gas to chemicals
    • C10J2300/1659Conversion of synthesis gas to chemicals to liquid hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/16Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1687Integration of gasification processes with another plant or parts within the plant with steam generation
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/18Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1846Partial oxidation, i.e. injection of air or oxygen only
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00Combustion technologies with mitigation potential
    • Y02E20/14Combined heat and power generation [CHP]
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/10Biofuels, e.g. bio-diesel
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/30Fuel from waste, e.g. synthetic alcohol or diesel
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency
    • Y02P20/129Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

  • the invention relates to a method in accordance with the preamble of claim 1 for utilizing thermal energy of gases generated in a BtL plant.
  • the invention also relates to a use in accordance with claim 9.
  • solid biomass is gasified in a high-temperature or a low-temperature gasifier.
  • the function of a BtL factory is to convert biomass into liquid fuels (Biomass to Liquid) from syngas generally through Fischer-Tropsch synthesis.
  • the gasifier operates at a temperature higher than the ash melt temperature, more specifically at about 1200-1400 °C.
  • gasification takes place at a pressure of 1-40 bar.
  • Recently a technology has been developed particularly suited for high-temperature gasification of biomass at a gasifier pressure of about 5 bar.
  • syngas The gas generated in gasification and further subjected to purification is generally called syngas, since it is subsequently used in preparation of other products such as ammonia or long-chain aromatic hydrocarbons.
  • the raw syngas generated in gasification must be cooled and purified free from dust, whereupon other components except hydrogen and carbon monoxide need be separated from the gas stream.
  • the resulting pure syngas, i.e., hydrogen and carbon monoxide is passed to a Fischer-Tropsch reactor (FT reactor), wherein paraffinic hydrocarbons are generated in the presence of a catalyst.
  • FT reactor Fischer-Tropsch reactor
  • the FT process is typically carried out at a pressure of 20-40 bar and at a temperature of about 200 °C.
  • the wax-like product thus obtained is known as biowax.
  • the biowax taken out from the FT process requires further refining to produce therefrom fuels suited for engine use by way of, e.g., hydrogenation, cracking and distillation. Also these processes are carried out under elevated pressure (30-80 bar). Hydrogenation refers to processing in a hydrogen atmosphere, wherein double bonds between carbons are saturated. Cracking in turn refers to breaking excessively long hydrocarbon chains in a reactor. Distillation finally separates the fuel fractions from each other thus resulting in diesel fuel, naphtha, kerosene, liquefied petroleum gas, etc.
  • gasification is carried out at a pressure lower than that of the FT and refining processes, the syngas pressure must be elevated. Conventionally this step takes place after the syngas is cooled and filtered free from solid impurities. Pressure elevation is accomplished by gas compressors that are available in plural different types. Typically they can be categorized as axial, radial, piston and screw compressors. Most generally, syngas compression has been performed using axial and radial compressors.
  • compressor type is selected based on the required pressure elevation, gas composition and volume.
  • compressors are rotary equipment.
  • the mechanical energy required for compression is typically derived from an electric motor or, alternatively, from a steam or gas turbine.
  • syngas compression in a BtL plant having a gasification fuel power of 300-500 MW at a pressure of about 5 to 35 bar requires an input power of about 10-17 MW.
  • Oxygen can be prepared from air by first cooling it into liquid form and then distilling the air gases apart from each other.
  • the compressor power of an air gas plant is 10 - 15 MW for a syngas plant of 300-500 MW gasification fuel power.
  • compressors are needed in the cooling process and oxygen pressure elevation to the gasification process pressure.
  • gas streams are desired to be fed backward in the process, the pressure levels of such streams must be elevated by compression.
  • These compressors are relatively low-powered with regard to the compression power required to move the main gas stream, typically in the order of 200-700 kW per compressor.
  • the process includes liquefaction of carbon dioxide for its capture, the pressure of gaseous carbon dioxide must be elevated prior to its cooling to about 20 bar followed by cooling to -50 °C with the help of heat exchangers and an expansion valve.
  • the input power requirements of carbon dioxide compression and compressors of the cooling equipment in a BtL plant of 300-500 MW gasification fuel power is in the order of 10-15 MW, whereby the liquefied amount of carbon dioxide is about 50-75 t/h.
  • the invention is primarily directed to syngas compression, but more generally the invention may be applied to other use, for example to the process steps mentioned above that require compression.
  • a BtL process generates saturated steams at different pressure levels, especially at a high pressure, from the cooling of raw syngas and the gasifier itself. More particularly, controlled cooling of the FT synthesis releases a large volume of saturated steam at a middle-high pressure. Besides the relatively small own-use requirements of the BtL process itself, the dominatingly largest consumer of backpressure steam in the plant is biomass drying. Nevertheless, the BtL plant has plentiful inherent supply of low-pressure steam.
  • the goal is to integrate a BtL plant with another industrial plant capable of using its excess steam.
  • Advantageously steam is used, e.g., in drying paper, pulp and cardboard as well as in district heating and electricity generation. Steam available from a BtL plant reduces the fuel consumption of the factory to be integrated therewith.
  • This object of the invention relates to a situation, wherein there is a deficit of electricity and plentiful excess of saturated steam simultaneously in the BtL process. Electricity is required to energize various compressors driven by electric motors. Simultaneously, steam is delivered to a process or power plant of the integrated factory wherein the steam drives turbines producing electricity. A portion of this electricity can be returned for use in the BtL process.
  • the essential aim is to utilize the excess steam on-site and thereby reduce the quantity of purchased electricity.
  • Steam reformer is a unit generally used oil refining industry for producing hydrogen from methane and heavier hydrocarbon fractions for use in oil refinement. Reforming is accomplished by feeding steam into the gas being reformed with the help of a suitable catalyst and under high temperature. The process is also known by English terms Steam Methane Reformer (SMR) or Steam Reformer Unit (SRU). Next is described a method, wherein superheating of steam is accomplished using the SMR technique.
  • SMR Steam Methane Reformer
  • SRU Steam Reformer Unit
  • the FT process of a BtL plant and different stages of oil refinement generate various tail gases, wherefrom hydrogen can be recovered using the SMR technique.
  • the yield of the BtL process is improved and the thus produced hydrogen is more ecological, i.e., derived from a biomass as compared to a situation, wherein the hydrogen source is a fossil resource such as methane.
  • Tail gases whose free translation into Finnish is "rear-end gases" and which are generated in the Fischer-Tropsch process and subsequent postprocessing stages, stem from the biomass-based raw material of the plant and contain different kinds of light hydrocarbons.
  • hydrogen is produced from the methane of natural gas using the SMR technique: CH 4 + H 2 O -> CO + 3H 2 Now this technique is applied to the tail gases generated in the FT process.
  • gas molecules with a longer chain such as propane are reformed as follows:
  • the BtL process can be complemented with WGS and/or SMR processes for improved yield and adjustment of its hydrogen-to-carbon monoxide ratio.
  • methane for instance, the overall reaction is:
  • the steam For utilizing in the high-pressure turbine the high-pressure saturated steam resulting from cooling the raw syngas of the gasifier, the steam must be superheated, since no water condensed during the expansion of steam may be passed to the turbine.
  • Superheating can be accomplished in a separate superheater boiler or by the hot flue gases of the steam reformer which is more appropriately adaptable to the BtL process.
  • the reformer takes place the reforming the tail gas of the FT process that contains a mixture of different hydrocarbons.
  • the temperature of the gas being reformed is typically elevated to about 900-1100 °C by burning a portion of the gas or some other fuel in the boiler.
  • the process temperature is so high that the exhausted flue gases may still be used for superheating steam, which means that superheating the steam can be accomplished with a minimal extra investment to the SMR technique without the need for installing a boiler.
  • the flue gases are clean as they originate from ash-free tail gases, that is, from exhaust and surplus gases.
  • the SMR unit may also be heated using externally fed fuels such as natural gas or other combustible gases resulting from the BtL process.
  • the excess backpressure steam may be converted into electricity in a steam condensation turbine.
  • the condensing turbine may be a separate piece of equipment or integral with the syngas turbocompressor. Also the backpressure turbine can be separate from the compressor thus facilitating entirely independent operation of the compressors and turbines.
  • Figs. 1 - 3 show process flow schematics of arrangements for implementing the method according to the invention.
  • Fig. 1 shows a flow schematic for producing biofuels from solid biomass.
  • the biomass 12 being fed into the process is dried and its particle size is homogenized in raw material preprocessing step 1 suitable for feeding to the gasifier.
  • the preprocessed biomass is fed to oxygen gasification 3 having such a high temperature that makes the tar components of gas to
  • the process oxygen is prepared in oxygen plant 2.
  • Raw syngas 28 is cooled in step 4 and is filtered free from dust in process 5. Subsequently, gas pressure can be elevated by compressor 24 to the level required by FT reactor 8. Prior to the feed to the FT reactor, the carbon monoxide-hydrogen ratio of the gas is adjusted in WGS reactor 6 and from the syngas are separated other gaseous components and catalyst poisons 7 that are derouted to stream 22. The biowax resulting from the FT process is postprocessed in a refinery plant 9 into fractions 15 suitable for different uses such as biodiesel. Cooling of raw syngas 28 is carried out with the help of a heat exchanger in process 4, whereto high-pressure infeed water 20 is passed. In the heat exchanger the water is evaporated into steam and removed in saturated state.
  • gasification 3 is functional but not the downstream stages 6-9 of the process. This means that the saturated steam must be passed via a pressure reduction valve 25 to backpressure network 38 as shown in alternative 26a of Fig. 1. This operational state must be continued so long until pure syngas is received at compressor 24. Hereinafter, the compressor can be started to output compressed syngas 27.
  • compressor and turbines are permanently connected to each other by a common shaft, that is, are forced to rotate with each other either at the same speed or, via a gearbox, at different speeds, a small amount of cooling steam must be passed to the turbines when the machineries are driven by an electric motor.
  • turbine 23 is designed to be driven by saturated steam
  • the steam can be routed to the turbine via the path shown in block 26b of Fig. 1.
  • the steam is passed to the backpressure network via path 26a so long until steam reformer 10 becomes operational up to which moment the compressor has been driven by an electric motor. Subsequently, the saturated steam stream is directed to the path shown in block 26c of Fig. 1.
  • Fig. 2 is shown the layout of a steam flow network of a process related to the present invention.
  • the saturated steam stream 26c of Fig. 1 is passed via superheater 33, whereby a superheated steam stream 39 is generated suitable for feeding to turbine 23.
  • While a saturated-steam condensation turbine 24b is connected on the same shaft with a high-pressure turbine 24a and compressor 23, it can also operate as a separate machinery. Operating the machineries separate from each other allows better runnability of the plant in special situations and startup occasions. The efficacy and investment cost of a system of a fixed configuration will be more advantageous in a process running extended periods of stable operation.
  • a BtL process is substantially self-sufficient as regards to backpressure steam 38.
  • the excess steam may be utilized, e.g., in condensation-steam generation of electricity or use in heat-intensive processes such as those of a paper mill or chemical plant.
  • the synchronous motor 34 mounted on the same shaft can also perform as a generator when the combined power of turbines 24a and 24b exceeds the power demand of compressor 23.
  • the excess amount of backpressure steam 38 varies from winter to summer inasmuch as biomass drying 37 consumes in the winter even three times more steam than in the summer due to the higher moisture content of the biomass in the winter and lower temperature of drying air taken from outdoors.
  • the output of saturated high-pressure steam 26 from the gasifier and other steam generation from the BtL process 35 remain unchanged irrespective of the season.
  • to the backpressure steam network of the BtL plant can be fed also other excess steam streams, e.g., from the backpressure steam network 36 of a pulp mill, for instance.
  • a condenser 30 subsequently condensed in a condenser 30. If the cooling capacity provided by the steam condensation turbine is insufficient, the excess steam can be cooled, e.g., in an auxiliary cooler 31 connected to a waterway. The condensates 29 are returned to the process as infeed water 20.
  • FIG. 2 is also shown an intermediate cooling unit 32 for cooling the syngas 28 being compressed.
  • the number of intermediate cooling stages can be plural , e.g., 4-6.
  • the warm exit water of the intermediate cooler can be utilized, e.g., for drying the biomass raw material of the BtL plant provided that the water temperature is sufficiently high, advantageously about +50 °C or higher.
  • Fig. 3 is shown a flow schematic for an SMR process according to the invention. Together with steam 40b, combustible gases 16a not utilized in the process are fed to the SMR reactor 10, which is heated by burning a portion of the reject gases 16b and purge gases 44b of the PSA unit with the help of combustion air 13. The process generates reformed gas 17, wherefrom hydrogen is separated after cooling in PSA unit 42.
  • the PSA exit or purge gases 44 also contain combustible gases that are routed to serve as fueling the SMR unit.
  • the PSA that is, the Pressure Swing Absorption reactor is a unit capable of separating gases of different molecular weight from each other, e.g., generally hydrogen 43 from a gas mixture of carbon dioxide and hydrogen.
  • the process may also be implemented without a PSA unit by way of feeding the reformed gas stream with the help of a recirculation compressor 11 to the compressed syngas stream 27 as shown in Fig. 1.
  • the exiting flue gas 8 and reformed gas 17 are hot and thus contain enough energy at a high temperature sufficient for superheating in superheaters 33a and 33b the saturated steam 26c exiting the gasifier.
  • saturated steam at a pressure of 90 bar has a temperature of about 305 °C.
  • the temperature must be further elevated to about 500 °C.
  • the temperature of superheated steam may be adjusted by spraying 41 feed water 20 into the steam stream.
  • the temperature of flue gases 18 is still quite high allowing the flue gas to be utilized for producing steam 40 at a lower pressure on a boiler 46a and a superheater 46b, heating waters for drying biomass or, alternatively, preheating 47 the combustion air of the SMR unit in a heat exchanger 45.
  • the cooled flue gases can be discharged to chimney 19.
  • the present invention is directed to a novel method and use capable of utilizing the thermal energy of gases formed in a BtL plant for in-plant use.
  • the method offers significant benefits, more specifically by utilizing the thermal energy of gas streams generated in a BtL plant for superheating steam for driving the turbine machineries of the BtL plant and postprocessing the tail gases in order to maximize the yield of the plant's end product.
  • This goal is achieved by driving the compressors and/or electric generators of the BtL plant process stages by steam turbines using the steam streams generated in the BtL plant processes that are principally superheated by the flue gases of a steam reformer, that is, an SMR reactor 10, integrated with the BtL plant equipment. Additionally, the plant yield is maximized by recovering hydrogen 43 at a PSA unit 42.
  • a BtL plant has integrated thereto a method for utilizing the thermal energy of the flue gases 18 and/or reformed gas 17 of a steam reformer 10 for superheating 39 the steam that is used in the BtL plant for driving the syngas turbocom pressor 23, 24 and/or producing electricity as well as improving hydrogen yield 43, whereby a WGS process is included having a steam reformer 10 connected to a PSA unit 42.
  • a BtL plant generates in its FT process 8 different FT tail gases, that is, process reject gases 6, that are passed to a steam reformer 10, wherein the FT tail gases are reformed 7 in such a way that the hydrocarbons of gases 17 are reformed into hydrogen 43 and substantially into carbon monoxide and therefrom further to carbon dioxide 44, from which gas stream after cooling 33, 46 in a PSA unit 42 is recovered hydrogen 43, whereupon the remaining gases 44 are recirculated to a steam reformer 10 for heating the steam reformer 10 to a correct temperature of about 800- 100 °C.
  • Gases 17 reformed in steam reformer 10 and flue gases 18 exiting the steam reformer 10 are passed for cooling to a heat exchanger 33, whereby the thermal energy of the gas streams is used for superheating the saturated high- pressure steam 26c exiting the gasifier. In this fashion the thermal energy of gases generated in a BtL plant is utilized for superheating gases used for driving the turbine machineries of the BtL plant.
  • a process generates a large volume of saturated steam streams, e.g., those exiting from the cooling of the gasifier vessel envelope or the syngas stream.
  • superheating these gases can be accomplished with the help of the hot gases generated in the process such as the flue gas of the steam reformer.
  • Superheating is absolutely necessary to make steam usable in turbines and further for driving compressors. Resultingly, the present invention makes it possible avoid the need for acquisition of a separate superheater boiler.
  • the plant can be erected without having an another plant located nearby such as a paper mill, for instance, that is capable of using saturated steam.
  • the method according to the invention permits integration of a power plant with the process.
  • the saturated steam can be used in other processes such as drying paper and pulp or in the production of district heating energy.

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EP11855609.1A 2011-01-14 2011-12-23 Procédé d'utilisation de l'énergie thermique des gaz en produit dans une usine appartenant à la filière btl Withdrawn EP2663619A4 (fr)

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FI20115038A FI20115038L (fi) 2011-01-14 2011-01-14 Menetelmä btl-tehtaassa muodostuvien kaasujen sisältämän lämpöenergian hyödyntämiseksi
PCT/FI2011/051154 WO2012095556A1 (fr) 2011-01-14 2011-12-23 Procédé d'utilisation de l'énergie thermique des gaz en produit dans une usine appartenant à la filière btl

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FI20115038L (fi) 2012-07-15
US20130291808A1 (en) 2013-11-07
BR112013017056A2 (pt) 2019-09-24
RU2013137861A (ru) 2015-02-20
FI20115038A0 (fi) 2011-01-14
AU2011355175A1 (en) 2013-07-18
WO2012095556A1 (fr) 2012-07-19
CA2823444A1 (fr) 2012-07-19
CN103380198A (zh) 2013-10-30
EP2663619A4 (fr) 2014-06-25

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