EP2265696A2 - Procédé et dispositif de transformation de matières brutes carbonées - Google Patents

Procédé et dispositif de transformation de matières brutes carbonées

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Publication number
EP2265696A2
EP2265696A2 EP09713765A EP09713765A EP2265696A2 EP 2265696 A2 EP2265696 A2 EP 2265696A2 EP 09713765 A EP09713765 A EP 09713765A EP 09713765 A EP09713765 A EP 09713765A EP 2265696 A2 EP2265696 A2 EP 2265696A2
Authority
EP
European Patent Office
Prior art keywords
gasification
synthesis gas
gasifier
temperature
water vapor
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Withdrawn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
EP09713765A
Other languages
German (de)
English (en)
Inventor
Helmut Kammerloher
Sven Johannssen
Dragan Stevanovic
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.)
Krones AG
Original Assignee
Krones AG
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
Priority claimed from DE102008014297A external-priority patent/DE102008014297A1/de
Application filed by Krones AG filed Critical Krones AG
Publication of EP2265696A2 publication Critical patent/EP2265696A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/02—Fixed-bed gasification of lump fuel
    • C10J3/06—Continuous processes
    • C10J3/14—Continuous processes using gaseous heat-carriers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/02—Fixed-bed gasification of lump fuel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/02—Fixed-bed gasification of lump fuel
    • C10J3/06—Continuous processes
    • C10J3/16—Continuous processes simultaneously reacting oxygen and water with the carbonaceous material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C10J3/721—Multistage gasification, e.g. plural parallel or serial gasification stages
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C10J3/80—Other features with arrangements for preheating the blast or the water vapour
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C10J3/82—Gas withdrawal means
    • C10J3/84—Gas withdrawal means with means for removing dust or tar from the gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C10J3/86—Other features combined with waste-heat boilers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/02—Dust removal
    • C10K1/026—Dust removal by centrifugal forces
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/001—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by thermal treatment
    • C10K3/003—Reducing the tar content
    • C10K3/008—Reducing the tar content by cracking
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/80—Additives
    • C10G2300/805—Water
    • C10G2300/807—Steam
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0916—Biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0956—Air or oxygen enriched air
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0973—Water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/12—Heating the gasifier
    • C10J2300/1215—Heating the gasifier using synthesis gas as fuel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656—Conversion of synthesis gas to chemicals
    • C10J2300/1659—Conversion of synthesis gas to chemicals to liquid hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1671—Integration of gasification processes with another plant or parts within the plant with the production of electricity
    • C10J2300/1675—Integration of gasification processes with another plant or parts within the plant with the production of electricity making use of a steam turbine
    • 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
    • C10J2300/1687—Integration of gasification processes with another plant or parts within the plant with steam generation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1853—Steam reforming, i.e. injection of steam only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1861—Heat exchange between at least two process streams
    • C10J2300/1884—Heat exchange between at least two process streams with one stream being synthesis gas
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/145—Feedstock the feedstock being materials of biological origin
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the invention relates to a method and an apparatus for converting carbonaceous raw materials into preferably liquid fuels.
  • the invention will be described with reference to biomass, but it should be understood that the method and apparatus of the present invention may be used with other carbonaceous products.
  • the invention is particularly concerned with the production of BtL fuels (biomass to liquid). This term refers to fuels that are synthesized from biomass.
  • BtL fuel biomass to liquid
  • This term refers to fuels that are synthesized from biomass.
  • biodiesel BtL fuel is generally obtained from solid biomass, such as firewood, straw, biowaste, animal meal or reeds, ie made of cellulose or hemicellulose and not only from vegetable oil or oilseeds.
  • this synthetic biofuel has its high biomass and area yields, which are up to 4000 1 per hectare, without any competition with food.
  • this fuel has a high CO 2 ⁇ reduction potential of over 90% and its high quality is subject to no use restrictions in today's and foreseeable engine generations.
  • fuels are meant those substances which can be used as fuels for internal combustion engines, in particular but not exclusively methanol, methane, gasoline, diesel, paraffin, hydrogen and the like.
  • liquid fuels are generated under ambient conditions.
  • Synthesis gas production available Furthermore, when using air as a gasification agent, the synthesis gas produced on a high proportion of nitrogen, which in turn is the calorific value is lowered.
  • fluidized-bed gasifiers according to the "casting principle" are known from the prior art.
  • the necessary gasification energy is applied by supplying hot sand (at a temperature of 950 ° C.).
  • the preheating of this sand is in turn generated by the combustion of raw material used (in this case, biomass).
  • raw material used in this case, biomass
  • DE 102 27 074 A1 describes a process for the gasification of biomass and a plant for this purpose.
  • the substances are burned in a gas-tightly separated from a gasification reactor combustion chamber and introduced the heat energy from the combustion chamber in the gasification reactor.
  • DE 198 36 428 C2 describes methods and devices for gasification of biomass, in particular of wood pulp.
  • a Festbettentgasung in a first gasification stage is effected at temperatures up to 600 0 C and in a subsequent second gasification stage a fluidized bed gasification at temperatures between 800 ° C and 1000 0 C.
  • WO 2006/043112 a method and a plant for the treatment of biomass are known.
  • temperatures of water vapor between 800 0 C and 95O 0 C are used for gasification.
  • gasification the principle of fluidized bed gasification is used.
  • this method is not useful for the gasification of low ash melting raw materials, such as many varieties of biomass, straw and the like.
  • steam temperatures described therein in the range of 800 0 C to 950 0 C are not sufficient to ensure a completely allothermal gasification. Therefore, it is necessary to always mix in a certain amount of air, which in turn results in problems with carbon dioxide and nitrogen contents in the synthesis gas.
  • recuperative heat exchanger For heating the water vapor, a recuperative heat exchanger is used in the case of WO 2006/043112 A1. These heat exchangers have the disadvantage that they are very expensive and their maintenance is very complicated and expensive. Furthermore, this process does not use the significant waste heat from the Fischer-Tropsch reactor, which arises during the synthesis process.
  • the present invention is therefore based on the object to provide a method and an apparatus for the gasification of carbonaceous raw materials available, which allows high efficiency and high efficiency. Furthermore, a method is to be created, which in turn supplies resulting energies to the process. More specifically, a gasification process is to be specified, which allows efficient conversion of the raw material and at the same time a particularly suitable ratio between hydrogen and carbon monoxide in the synthesis gas.
  • the device according to the invention should also be suitable overall for smaller capacities and a possible decentralized operation with different starting materials in order to achieve a good economy. This is achieved by a method according to claim 1 and an apparatus according to claim 12. Advantageous embodiments and further developments are the subject of the dependent claims.
  • the carbonaceous raw materials are gasified in a gasifier in a first step, wherein heated steam is introduced into the gasifier.
  • the synthesis gas produced during the gasification is purified and, in a further step, preferably its temperature is changed.
  • the synthesis gas is cooled.
  • the synthesis gas is converted to a liquid fuel by means of a catalyzed chemical reaction, preferably using a Fischer-Tropsch reactor for this conversion.
  • the gasification is a completely allothermal gasification and the heated water vapor serves both as a gasification agent and as a heat carrier for the gasification and has a temperature which is above 1000 0 C. Under an allothermal gasification is understood that the heat input comes from the outside.
  • the method according to the invention is divided into at least 3 process steps, wherein first an allothermic gasification of the raw material (such as biomass and straw in particular) with water vapor, which serves as a gasification agent and energy carrier is made.
  • a cleaning of the gas, in particular of dust and tar, and preferably a subsequent recycling of these substances in the gasification process is performed.
  • As part of the preferred Fischer-Tropsch synethesis synthesis gas is converted into liquid fuels.
  • temperatures of at least 1000 0 C are used, but preferably temperatures of more than 1200 0 C and more preferably of more than 1400 0 C.
  • the ratio between hydrogen and carbon monoxide (H 2 / CO) is at least equal to or greater than 2, which is particularly advantageous for the downstream Fischer Tropsch synthesis is.
  • the high concentration of water vapor in the product gas also allows destruction of residual tars in a preferably downstream thermal cracker. More specifically, this destruction is easier to perform in an atmosphere with higher vapor content.
  • recuperative heat exchangers used in the prior art, it has hitherto not been possible to achieve such steam temperatures.
  • bulk generators can be used, as described, for example, in EP 0 620 909 B1 or DE
  • a synthesis gas having a particularly high H 2 / CO ratio, more specifically a ratio greater than 2, is formed.
  • another gaseous medium is fed to the gasifier together with the steam.
  • these are oxygen or air, which are heated together with the steam to the temperature of the steam and fed to the gasifier.
  • the highest temperature within the carburetor is always above the Ash melting point. In this way it can be achieved that ash is discharged in the liquid state.
  • the gasifier is preferably a fixed bed countercurrent gasifier.
  • different types of carburetors according to the prior art can be used.
  • the particular advantage of a countercurrent fixed bed gasifier is that within this reactor individual zones are formed in which different temperatures and thus different processes occur. The different temperatures are based on the fact that the respective processes are strongly endothermic and the heat only comes from below. In this way, the very high steam temperatures are utilized in a particularly advantageous manner. Since the highest steam temperatures prevail in the entry zone of the gasification agent, it is possible to always produce the conditions for a liquid ash discharge.
  • the purification of the synthesis gas preferably takes place by means of a cyclone and preferably by means of a multicyclone.
  • tars and dust can be separated and preferably recycled back into the carburetor.
  • the tar content in the product gas is relatively high. This tar should not get into the reactor for the Fischer-Tropsch synthesis, since the tar is harmful for the catalysts used there. Furthermore, the energy content of the tar is high and consequently has a negative impact on process efficiency. Therefore, the tar, together with the accumulated dust, is preferably pushed off immediately after the gasifier in a cyclone and particularly preferably in a multicyclone and further injected with a suitable pump into the high-temperature zone of the gasifier.
  • a cyclone is a centrifugal separator in which the substance to be deposited is fed tangentially in a vertical cylinder which tapers conically downwards and is thus set into a rotational movement. By acting on the dust particles centrifugal force they are thrown to the outer wall, thereby braked and sink into the underlying Staubabscheideraum.
  • a thermal cracker is particularly preferably used, which by very high temperatures, more preferably between 800 0 C and 1400 0 C and preferably by the supply of a small amount of oxygen or air, the remaining tek in breaks short-chain molecular structures.
  • the synthesis gas is thus brought to a very high temperature, whereby the long-chain molecular structures are broken. At the same time, this process removes the remaining amount of dust.
  • the cleaning in the cyclone represents a first cleaning step and the cleaning in the cracker a second cleaning step.
  • a part of the superheated gasification agent that is to say the water vapor, is additionally preferably fed through a line to the described cracker.
  • the gasification agent is used in addition to the thermal cracking.
  • the synthesis gas is cooled in a gas cooler and preferably subsequently in a condenser, wherein excess water vapor is condensed out, which can be used for heat recovery.
  • a condenser which reduces the amount of syngas and at the same time increases the proportions of the two most important components, namely CO and H 2 .
  • the condenser the residual amounts of pollutants such as dust and tars are washed out. If necessary, it is possible to finally remove residual amounts of pollutants (which are in the ppm range), for example by using a scrubber with ZnO as catalyst.
  • the synthesis gas is freed from dust by means of a cyclone, so that the tars remain in the synthesis gas. This is by electrical Heat tracing ensures that the pipes and the cyclone stretch to temperatures above the
  • Condensation temperature of the tars are kept.
  • the tars are removed in a condenser together with the water from the synthesis gas.
  • This "tar water” forms a pumpable suspension which is vaporized, superheated and returned to the gasification process.
  • the synthesis gas is preferably prepared in a CO 2 scrubber and in a heat exchanger for optimum composition and temperature for the subsequent Fischer-Tropsch synthesis.
  • the CÜ 2 amount in the synthesis gas is reduced in the mentioned CO 2 scrubber or in a PSA (Pressure Swing Absorption) / VSA (Vacuum Swing Absorption) system with molecular sieving technology to provide optimum conditions for Fischer-Tropsch synthesis and efficient energy utilization to ensure the overall system.
  • the synthesis gas is preheated to an ideal temperature for the Fischer-Tropsch synthesis.
  • the waste heat from at least one gasification-following process is preferably used for saturated steam generation. It is possible, for example, to use the waste heat from the gas cooler described for the preheating of the water for saturated steam generation. Furthermore, the heat generated in the Fischer-Tropsch reactor itself waste heat can be used for the production of saturated steam.
  • the exothermic synthesis reaction in the Fischer-Tropsch reactor requires constant and uniform cooling. Preference is given to cooling with boiling water and subsequent
  • a predetermined part of synthesis gas formed is fed to an offgas generated in the synthesis.
  • a bypass line is used, which is connected to the Fischer-Tropsch reactor.
  • Bulk regenerators emerges to use by means of a heat exchanger for an external or internal heat consumer.
  • a pressure generating device is provided which increases the pressure of the synthesis gas supplied to the conversion.
  • a gas compressor may be provided, which increases the synthesis gas after the condenser to the necessary pressure for the Fischer-Tropsch reactor.
  • the entire device can be under a pressure which is advantageous for the synthesis process in the Fischer-Tropsch reactor. In this way, the efficiency of the entire process can be increased.
  • saturated steam is superheated by means of a suitable internal or external heat source and expanded in a steam turbine before it is fed to the bulk material regenerators.
  • the entire system with the exception of the Fischer-Tropsch reactor and the steam-carrying lines, can be designed without pressure and the energy required for synthesis gas compression can be obtained from the steam turbine. In this way, the investment costs can be reduced while maintaining efficiency.
  • condensate obtained in the conversion is used as additional liquid to the condensate from the condenser for the production of saturated steam. In this way, a closed water cycle is made available.
  • the heated water vapor is used both as a gasification agent and as a heat carrier for the gasification, and has a temperature which is above 1000 0 C.
  • the Carburetor separated from the heated water vapor fed to another gaseous medium.
  • the further gaseous medium to a temperature which is below 600 0 C, preferably below 400 0 C and more preferably below 300 0 C. It would also be possible to provide room temperature.
  • the gasification is an allothermic gasification. Due to the separate supply of air and water vapor can be achieved that the air, which preferably does not contribute to the actual gasification process, does not need to be heated with, so that the overall energy efficiency of the process can be increased.
  • the present invention is further directed to an apparatus for converting carbonaceous raw materials and in particular biomass into liquid fuels, which apparatus comprises a gasifier in which carbonaceous raw materials are gasified by means of heated steam, at least one cleaning unit used to purify gasification synthesis gas is used, at least one temperature change unit for changing the temperature of the resulting synthesis gas and a conversion unit for converting the synthesis gas into liquid fuel.
  • the device has at least one heating device which heats the steam to a temperature which is above 1000 ° C.
  • the temperature change unit is preferably a cooling unit.
  • the purification unit is a cyclone and more preferably a multicyclone.
  • the device has a further cleaning unit which treats residual tars.
  • these are not exclusively the cracker described above.
  • two cooling devices are provided in the form of a gas cooler and a condenser downstream of this gas cooler.
  • the device has a conveying device, which is arranged between the cleaning unit and the carburetor and promotes a product resulting from the cleaning process, and in particular tar, into the carburetor.
  • At least two heating devices are provided, wherein at least two of these heating devices are operated in antiphase. In this way, a continuous heating process for the gasification agent can be achieved.
  • the present invention is further directed to a method of the type described above, wherein an apparatus of the type described above is used to carry out the method.
  • Fig. 1 is a schematic representation of a device according to the invention
  • FIG. 2 is a detailed view of the device of FIG. 1 for illustrating the heating of the water vapor;
  • FIG. 2 is a detailed view of the device of FIG. 1 for illustrating the heating of the water vapor;
  • FIG. 3 shows a further detailed illustration of the device from FIG. 1 for illustrating the purification of the synthesis gas
  • FIG. 4 shows a further detailed illustration of the device from FIG. 1 in a further embodiment
  • FIG. 5 shows a further detailed illustration of the device from FIG. 1 in a further embodiment
  • Fig. 6 is an alternative flow sheet diagram with a
  • Fig. 7 shows an alternative flow diagram with an air / oxygen addition after overheating of the water vapor.
  • the reference numeral 1 shows a schematic representation of a device 35 according to the invention for the conversion of carbonaceous raw materials into synthesis gas and for the subsequent liquid fuel synthesis.
  • the reference numeral 1 refers to a fixed bed countercurrent reactor.
  • the raw material 2 is introduced from above into the reactor 1 and the gasification agent 3 along a feed line 42 from below. In this way it is achieved that the gasification agent 3 and the synthesis gas produced flow through the reaction space in the opposite direction to the Brennstoffström.
  • the resulting ash in the carburetor 1 is discharged downwards, that is, along the arrow P2.
  • the synthesis gas passes via a line 44 into a cyclone or preferably a multicyclone.
  • a cyclone 4 a large part of the tar and the resulting dust is eliminated and injected with a pump 5 back into the high temperature zone of the carburetor 1.
  • the synthesis gas in which Restteer is present together with residual quantities of dust passes via a further conduit 46 into a thermal cracker 6.
  • Restteer with the amount of dust at maximum temperatures between 800 0 is C and 1400 0 C destroyed.
  • a predetermined amount of oxygen and / or air can be injected directly into the high-temperature zone and in this way a partial oxidation of the tars can be achieved (see arrow P1).
  • the synthesis gas passes via a line 48 into a gas cooler 7.
  • the synthesis gas is cooled so far that 8 excess water vapor is condensed out in the downstream condenser.
  • the amount of CO 2 in the synthesis gas can be reduced by means of a CO 2 scrubber 9 or a PSA / VSA plant with molecular sieve technology.
  • the reference numeral 10 refers to a gas preheater in which the synthesis gas is preheated to a suitable temperature for the subsequent Fischer-Tropsch synthesis taking place.
  • the reference numeral 11 refers to a Fischer-Tropsch reactor in which from the synthesis gas under suitable thermodynamic conditions, that is, under appropriate pressure and temperature of the synthetic liquid fuel 12, z. B. BtL is generated in the case of biomass gasification.
  • By-products of this synthesis are saturated steam 14 by cooling the reactor 13 and an off-gas 15 consisting of unreacted synthesis gas and gaseous synthesis products.
  • the saturated steam 14 then passes through a connecting line 50, which is split into two sub-lines 50a and 50b, in two bulk regenerators 17 and 18.
  • the water vapor is superheated to the required temperature.
  • the bulk material regenerator 18 is in a heating phase, that is, it is here in particular by the combustion of off-gas 15, which is supplied to it via a connecting line 54 from the Fischer-Tropsch reactor 11 charged with heat energy.
  • a plurality of valves 62 to 69 is used.
  • the valves 62, 63, 66 and 68 are assigned to the bulk material regenerator 17 and the valves 64, 65, 67 and 69 to the bulk material regenerator 18.
  • saturated steam 14 is also generated, which in turn is overheated in the bulk regenerators 17 and 18, in which case the chemical energy from the off-gas 15 can be used.
  • the superheated steam 3 becomes the total waste energy generated in the process supplied and so the water vapor can be heated particularly advantageous.
  • Bulk regenerators are used to achieve a particularly smooth operation.
  • FIG. 2 shows a detailed illustration of a further embodiment of the device shown in FIG. 1.
  • oxygen and / or air is introduced here along the arrow P3.
  • the oxygen can also be referred to as pebble hoppers
  • Bulk material regenerators 17 and 18 are overheated together with the steam to a very high temperature. It is possible, even with a relatively small amount of less than 10 vol.% Oxygen or air in the highly superheated gasification agent to significantly increase the temperature in the ash melting zone, to get in this way a low-viscosity ash. In addition, this measure, that is, the supply of air or oxygen, further increase the utilization of carbon and positively influence the tar formation by increasing the raw gas temperature.
  • Fig. 3 shows a further preferred embodiment of a device according to the invention.
  • a line 30 is additionally provided, via which gasification agent can be injected into the cracker 6. This measure is particularly effective if the necessary temperature in the cracker 6 is well below the gasification agent temperature and if the gasification agent has a certain proportion of oxygen or air (see Fig. 2).
  • the Tar gas control valve 21 With a Hot gas control valve 21, the carefullydüsende amount can be regulated.
  • FIG. 4 shows a further detailed representation of a preferred embodiment.
  • a further line 22 and a further control valve 23 is provided. If the amount of off-gas 15 for the heating of the gasification agent 3 in the bulk regenerators 17 and 18 is insufficient, an additional amount of synthesis gas, for example after the condenser 8, can be supplied through the bypass line 22 via this line.
  • Fig. 5 shows a further detailed representation of a preferred embodiment. If the saturated steam quantity 14 from the cooling of the Fischer-Tropsch reactor 11 is greater than the necessary amount of steam for the gasification reactor 1, the excess amount of saturated steam can be passed to an external or internal heat consumer 24 (for example a drying plant). In this way, the process efficiency can be further increased.
  • the excess saturated steam quantity is also set here by a control valve 25.
  • Fig. 6 illustrates an alternative to tar purification and removal from the product gas.
  • the product gas is freed of dust.
  • a condenser 8 the water and the tars are condensed out at a temperature of 50 0 C.
  • the pipes between the carburetor and the condenser are heated above 200 ° C., particularly advantageously above 300 ° C. It forms a tar / water mixture.
  • the tar water is optionally mixed with water and conveyed by means of the pump 20 and to a working pressure of> 1 bar, advantageously to 10 bar and particularly advantageous Brought 30 bar.
  • Fig. 7 illustrates an alternative to the gasification process in which water vapor, additionally little heated air or pure oxygen is added to the actual gasification agent in the reactor. This is done to adjust the gas composition of the product gas. In this case, this air is supplied via a further supply line 71 to the carburetor.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Processing Of Solid Wastes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne un procédé et un dispositif (35) de transformation de matières brutes carbonées, notamment de biomasse, en carburant. Selon le procédé, une gazéification allothermique des matières brutes est d'abord réalisée dans un gazéificateur (1) au moyen de vapeur d'eau chauffée (3). Après épuration et refroidissement du gaz de synthèse produit lors de la gazéification, le gaz de synthèse est transformé en carburant liquide par une réaction chimique catalysée. Selon l'invention, la vapeur d'eau chauffée est employée en tant qu'agent de gazéification et en tant que caloporteur pour la gazéification, et présente une température supérieure à 1000 °C.
EP09713765A 2008-02-28 2009-02-28 Procédé et dispositif de transformation de matières brutes carbonées Withdrawn EP2265696A2 (fr)

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DE102008014297A DE102008014297A1 (de) 2007-11-16 2008-02-28 Verfahren und Vorrichtung zur Umwandlung kohlenstoffhaltiger Rohstoffe
PCT/EP2009/001441 WO2009106357A2 (fr) 2008-02-28 2009-02-28 Procédé et dispositif de transformation de matières brutes carbonées

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EA020334B1 (ru) 2014-10-30
CN101970617B (zh) 2014-10-29
NZ587568A (en) 2012-11-30
CN101970617A (zh) 2011-02-09
WO2009106357A2 (fr) 2009-09-03
EA201070910A1 (ru) 2011-04-29
BRPI0907997A2 (pt) 2019-02-19
JP5777887B2 (ja) 2015-09-09
US20110035990A1 (en) 2011-02-17
AU2009218694A1 (en) 2009-09-03
JP2011514923A (ja) 2011-05-12
CA2716387A1 (fr) 2009-09-03
AU2009218694B2 (en) 2014-02-13
WO2009106357A3 (fr) 2010-03-25

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