+

WO2006031011A1 - Appareil de gazeification catalytique pour un combustible a biomasse raffine a faible temperature, et son procede d'utilisation - Google Patents

Appareil de gazeification catalytique pour un combustible a biomasse raffine a faible temperature, et son procede d'utilisation Download PDF

Info

Publication number
WO2006031011A1
WO2006031011A1 PCT/KR2005/001808 KR2005001808W WO2006031011A1 WO 2006031011 A1 WO2006031011 A1 WO 2006031011A1 KR 2005001808 W KR2005001808 W KR 2005001808W WO 2006031011 A1 WO2006031011 A1 WO 2006031011A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
gasification
tar
fuel
catalytic
Prior art date
Application number
PCT/KR2005/001808
Other languages
English (en)
Inventor
Sung-Kyu Kang
Hyun-Dong Shin
Original Assignee
Korea Institute Of Energy Research
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 Korea Institute Of Energy Research filed Critical Korea Institute Of Energy Research
Priority to US10/560,992 priority Critical patent/US20070094929A1/en
Priority to EP05750463A priority patent/EP1773968A4/fr
Priority to JP2006535283A priority patent/JP4243295B2/ja
Publication of WO2006031011A1 publication Critical patent/WO2006031011A1/fr

Links

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
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
    • C10J3/56—Apparatus; Plants
    • 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • 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
    • 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
    • C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
    • 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
    • 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
    • C10K1/024—Dust removal by filtration
    • 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
    • C10K1/04—Purifying combustible gases containing carbon monoxide by cooling to condense non-gaseous materials
    • C10K1/046—Reducing the tar content
    • 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
    • C10K1/16—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with non-aqueous liquids
    • C10K1/18—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with non-aqueous liquids hydrocarbon oils
    • 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
    • C10K1/20—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/023—Reducing the tar content
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • 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
    • C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
    • C01B2203/0272—Processes for making hydrogen or synthesis gas containing a decomposition step containing a non-catalytic decomposition step
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2200/00—Details of gasification apparatus
    • C10J2200/15—Details of feeding means
    • C10J2200/158—Screws
    • 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
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/093—Coal
    • 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
    • C10J2300/0946—Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
    • 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
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0983—Additives
    • 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
    • C10J2300/0983—Additives
    • C10J2300/0989—Hydrocarbons as additives to gasifying agents to improve caloric properties
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1693—Integration of gasification processes with another plant or parts within the plant with storage facilities for intermediate, feed and/or product
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1846—Partial oxidation, i.e. injection of air or oxygen only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1861—Heat exchange between at least two process streams
    • C10J2300/1869—Heat exchange between at least two process streams with one stream being air, oxygen or ozone
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1861—Heat exchange between at least two process streams
    • C10J2300/1884—Heat exchange between at least two process streams with one stream being synthesis gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1861—Heat exchange between at least two process streams
    • C10J2300/1892—Heat exchange between at least two process streams with one stream being water/steam
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates, in general, to gasification techniques for using biomass having a low inorganic ash content and a high nitrogen content as clean fuel in a local heating system of a big city.
  • the present invention relates to an apparatus and method for manufacturing a gas fuel via clean gasification of a selectively refined mixture (SOCA: Sludge-Oil-Coal Agglomerates) comprising biomass organic waste, heavy oil, and coal.
  • SOCA selectively refined mixture
  • the gas fuel obtained after clean gasification is a clean gas fuel usable in gas combustors, such as gas engines, gas turbines, vapor turbine generators, fuel cells, boilers, etc., or in heating devices.
  • the biomass is organic solid materials, which include industrial waste such as sewage sludge, pulp sludge, etc., living waste such as home waste, excretions, etc., agricultural waste, livestock excretions, or wood chips.
  • gasification techniques have begun to be used to easily prepare gas fuel or synthetic gas from coal in the absence of a catalyst.
  • the above techniques have been developed toward entrained gasification and catalytic gasification for fine coal.
  • Solid fuel is gasified along with reactive materials, such as air, oxygen, or steam, and thus, is converted into a flammable gas, condensed liquid/tar, and solid residue.
  • reactive materials such as air, oxygen, or steam
  • gasification is used to maximally convert solid fuel into gas fuel, it may be limitedly applied in a partial gasification process.
  • pyrolysis which is different from gasification, means thermal decomposition of solids in an inert atmosphere.
  • the initial state of gasification is assumed to be devolatilization of pyrolysis.
  • the fuel is decomposed into char and volatile components.
  • a final component distribution of product gas is determined through the secondary reaction between char and volatile gas. In practice, the distribution of the product varies greatly with the gasification methods and the process conditions.
  • a gas resulting from gasification typically has a low caloric value.
  • a gas having a low caloric value of 1,100-1,450 kcal/Nm 3 is obtained when gasifying coal having a caloric value of 6,850 kcal/kg.
  • the low-temperature non-catalytic gasification of coal is, in practice, performed at a temperature of not less than a melting point of ash, due to a low conversion rate.
  • the gasification of biomass having lower ash content adopts catalytic gasification, fuel having high quality may be obtained while decreasing the conversion of fuel-N into NO at a low temperature at which ash slagging does not occur.
  • waste having a high caloric value or heavy oil or to a fuel mixture containing coal.
  • waste containing chlorine ion is designed to have a retention time of 2 sec or more at 1200 0 C or higher to remove it or directly burn it after gasification.
  • a specific gasification process which produces a fuel having high quality, such as hydrogen, may be proposed.
  • a specific gasification apparatus requires a means for removing and refining large amounts of impurities, such as ash included in a raw material, and generally, also requires a quenching system to produce ash, which is melted by increasing the temperature to achieve high gasification conversion in the absence of a catalyst, into fine slag. Further, a pure oxygen or air separating device for the production of a gas having high caloric value is used, thereby increasing the driving cost or mounting cost.
  • a system is installed for indirect heating particularly by an external heat source and pyrolysis through supplying only steam to the system, and is thus used for specific purposes when economy is unimportant.
  • the partial oxidation in the absence of a catalyst is disadvantageous because high-temperature air or enriched oxygen must be used to achieve high-temperature gasification. Also, additional fuel is consumed to obtain a product gas (CO and H 2 ) having high quality. Further, expensive heat resistant material suitable for high-temperature reactions should be used, and also, the reactor has a short service life. Furthermore, about 2-5% of the free carbon that is produced by high-temperature partial combustion using a fixed- bed reactor is deposited, and the reaction efficiency is gradually decreased, thus requiring additional cost for removing the deposited material.
  • circulating low- temperature catalytic gasification in which organic hydrocarbon and water vapor are converted into a product gas in the presence of an oxide catalyst (MO), may be conducted. Therein, the catalyst is reduced and converted into a pure metal (M). A metal (M) having decreased catalytic activity is reproduced into metal oxide (MO) in a combustor.
  • the catalytic reaction is conducted at a low temperature of 400-600 0 C, and a liquid product may be produced in a very small amount.
  • the above gasification is limited to use for waste containing a higher ash content or catalytic poison.
  • the circulating reforming catalyst generally includes Ni and Co, and preferably, V, Cr, Fe, Cu, Mo, Ag, Cd, La, Ce, or perovskite catalysts, and more preferably, a precious metal having high catalytic efficiency, such as Rh or Ru.
  • a catalyst may be affixed to a support formed of oxides of at least two metals selected from among Mg, Ca, Sr, Ba, Al, Ce, Si, Ti, and Zr.
  • these catalysts since these catalysts have low activities due to catalytic poison at a low temperature, they may need to undergo high-temperature reaction or reproduction to be stably used. Consequently, free carbon is deposited on the catalyst, or reacts with the support to form another product.
  • an Ni catalyst reacts at high temperature with alumina, to produce NiAl 2 O 4 , resulting in decreased catalytic activity.
  • hexaaluminate (MeO-OAl 2 O 3 ), which has high temperature resistance, may be used as a supporter.
  • liquid waste containing large amounts of solid impurities, such as heavy metals may be gasified in a supercritical state using a reactor into which a catalyst is loaded.
  • the catalyst such as Ru, Pd, R, Pt, Au, Ir, Os, Fe, Ni, Ce, or Mn
  • the catalyst used is expensive precious metal, and is thus recovered using a gas- liquid separator to be reused.
  • the gasification may be rapidly conducted at a relatively low temperature of 700 ⁇ 850°C in the presence of an optimal catalytic composition, such as K 2 SO 4 + FeSO 4 , K 2 SO 4 + Ni(NO 3 ) 2 , or K 2 SO 4 +
  • an optimal catalytic composition such as K 2 SO 4 + FeSO 4 , K 2 SO 4 + Ni(NO 3 ) 2 , or K 2 SO 4 +
  • the solid materials for example, CaS, CaO and limestone, may be separated from each other by use of the difference in density in the reactor.
  • the ash and limestone may be separated from each other in the lower portion of the reactor. To this end, however, accurate driving is required due to a complicated reactor and process.
  • FIG. 1 is a view showing a conventional apparatus for two-stage gasification of biomass at a high temperature in the absence of a catalyst.
  • a biomass fuel is supplied to a circulating fluidized-bed heating furnace 102 from a fuel hopper 101, and then sequentially passed through a cyclone 103, a char separator 104 and a gas reforming furnace 105, to achieve two-stage pyrolysis.
  • the fuel gas is passed through a pre-heater 106 and then a gas quencher 107, whereby fly ash is collected in a collector 108 and a gas is refined in a refiner 109.
  • the above apparatus is disadvantageous because first-stage pyrolysis is conducted at 450 ⁇ 850°C, which is not high, in the absence of a catalyst, in consideration of high-temperature volatilization of heavy metal, thus obtaining a low gasification yield and generating excess tar. Hence, a process of reforming tar should be necessary to increase the gasification yield, which is conducted at 1000-1200°C in the absence of a catalyst.
  • exhaust flue gas desulfurization is considered for biomass containing a low sulfur content, pollution attributed to high content of phosphorous or fuel-N is not considered, causing secondary environmental pollution.
  • the above apparatus has the gas quencher 107 for inhibiting the dioxin conversion by chlorine ions present in the raw material.
  • FIG. 2 is a view showing a conventional apparatus for two-stage catalytic gasification of waste having high quality. Since the waste having low impurities with a high caloric value has a small amount of poisonous material, as shown in FIG. 2, a raw material undergoes first stage partial oxidation and pyrolysis using a fluidized-bed in the absence of a catalyst at about 700 ⁇ 800°C in a fluidized-bed gasifier 110, after which the temperature of the produced flammable gas is decreased to about 300°C. Then, slaked lime is added to fix Cl and S, which are then collected in a cyclone 103 to remove them.
  • the temperature of the flammable gas is increased again after passing through a gas mixer 111 and a combustor 112, and thereafter, second stage tar catalytic reforming is conducted in a gas reformer 113.
  • an NiO/MoO catalyst is active at 400 ⁇ 500°C
  • a catalyst obtained by supporting Ni, Cr and Fe to alumina is active at 800 ⁇ 1000°C.
  • the reference numeral 114 designates a boiler
  • the reference numeral 115 designates a gas-holder. Also, parts common to the apparatus shown in FIG. 1 have the same reference numerals.
  • an object of the present invention is to provide a catalytic gasification technique of poison-resistance in a first stage gasification process using a further refined fuel to increase the gasification yield at a low temperature, and then in the gasification of tar and conversion of tar-N and HCN present in a flammable gas into NH 3 in a second stage catalytic reforming process.
  • Another object of the present invention is to provide a gasification technique, using a compact apparatus without the need for a molten ash quenching system, in which the unit calories of the produced gas are increased and ash is formed not in a molten state but as fly ash, by minimizing the content of CO 2 in the gas while decreasing the energy consumption of a reaction system by decreasing the temperature of a total process.
  • the present invention provides an apparatus for low-temperature catalytic gasification of a refined biomass fuel, comprising a fuel hopper to momentarily receive refined fuel, and including a screw feeder to quantitatively feed the fuel, provided at the lower portion thereof; a catalytic circulating fluidized-bed gasifier provided in the rear of the fuel hopper, and including a shutter connected to the screw feeder, provided at a middle portion of the gasifier, and a hot air pipe and a steam pipe, provided at a lower portion thereof; a dust collector connected to the catalytic circulating fluidized-bed gasifier via a pipe extending from the upper portion of the catalytic circulating fluidized-bed gasifier to the side wall of the upper portion of the dust collector, to collect fly ash; a catalyst reformer connected to the dust collector via a pipe extending from the upper portion of the dust collector to the lower portion of the catalyst reformer, and including a lower layer of fixed filter adsorbent bed and an upper layer of fluidized catalyst bed; a heat exchanger
  • the present invention provides a method of low-temperature catalytic gasification of a refined biomass fuel, comprising a fuel supplying step of supplying a refined mixture including biomass organic waste, coal and heavy oil to the middle portion of a gasifier through screw feeder; a catalytic circulating fluidized-bed gasification step of drying, volatilizing, low-temperature catalytic gasifying, and partially burning the fuel using hot air and steam in the presence of a catalyst; a collecting step of collecting fly ash contained in the gas in the previous step; a catalyst reforming step of reforming the gas through a lower layer of filter and reforming tar-nitrogen, aromatic-nitrogen, phosphorous and sulfur through an upper layer; a heat exchanging step of cooling the gas to 200°C or less and transferring condensed liquid to a tar-storing bath; a tar scrubbing step of condensing non-converted tar or non-condensed liquid to be recovered, and gas stripping the condensed liquid; and a gas-holding step of
  • the gasification of a fuel which is initiated at a temperature lower than that of a single fuel material may be conducted at a temperature which is further decreased by using a catalyst.
  • oxygen consumption required to maintain the operation temperature is decreased, thus a desired fuel may be inexpensively produced.
  • the operation temperature of a gasifier is low, little heat is released and a slagging treatment system is not needed, thereby realizing a compact apparatus.
  • a gas product obtained by using a smaller amount of air in the present invention has the same caloric value as a gas product resulting from conventional gasification using oxygen, therefore generating economic benefits.
  • the present invention pertains to clean energy producing techniques for converting a highly refined mixture comprising sludge and coal into an inexpensive gas fuel having a high caloric value.
  • the gasification of the refined mixture comprising sludge/coal/oil is initiated, along with a material having a high initiation temperature of gasification, at a temperature lower than that of a single component.
  • gasification may be performed for a short time, hence achieving rapid gasification.
  • a low ash content and easy control of fly ash at a low temperature make it easier to decrease the size of an apparatus, leading to saved energy and efficient operation.
  • a heavy metal and a salt are present in a very small amount, a combustion post-treatment system is not needed.
  • the gasification adopts a fluidized-bed type which may be driven at a relatively low temperature.
  • the gasification is conducted at 850°C using inexpensive coarse limestone powders or particles which enable gasification at a low temperature, it may exhibit the same effects as conventional gasification at 1100°C or more in the absence of a catalyst.
  • the reformation temperature of a tar reformer is in the range of 1200°C or more, which is higher than a gasification temperature.
  • the reformation temperature is decreased to 650°C or less, and thus, the reformer of the present invention does not need an additional heat source.
  • hydrogen sulfide and phosphorous pentoxide gas acting as a catalyst poison component are fixed to be removed by the use of caustic lime, thus increasing the reformation of tar and the conversion of fuel-N into NH 3 in the presence of a catalyst.
  • tar regarded as an unnecessary material
  • unreacted tar, tar generated from the catalytic reformation, and a liquid product formed upon cooling the gas are recovered and then used for other purposes.
  • additional devices or usage methods are required to re-introduce an undesired liquid component such as tar caused by a conventional coal gasification process into the gasification process or to use it as a liquid fuel.
  • a component may be used as an agglomerating agent to form an agglomerate, it is not problematic.
  • FIG. 1 is a schematic view showing a conventional apparatus for two- stage gasification of biomass at a high temperature in the absence of a catalyst;
  • FIG. 2 is a schematic view showing a conventional apparatus for two- stage catalytic gasification of waste having high quality
  • FIG. 3 is a view showing an apparatus for two-stage catalytic gasification of a refined biomass fuel, according to the present invention
  • FIG. 4 is a view showing the gasification properties of refined sewage sludge fuel in the absence of a catalyst and in the presence of a catalyst;
  • FIG. 5 is a view showing the two-stage catalytic gasification characteristics of refined sewage sludge fuel.
  • FIG. 3 is a view showing a catalytic gasification apparatus for use in recovering an energy source in the form of gas from a refined biomass fuel, according to the present invention.
  • the refined biomass fuel which is a flammable material obtained by selectively separating and recovering an organic solid component from biomass and coal, along with oil, using an oil agglomeration or floating process, has a non ⁇ flammable inorganic material (hereinafter, referred to as 'ash') present in an amount less than 6% based on dried material, and is a solid fuel having high quality with a caloric value of 7,000 kcal/kg or more.
  • the apparatus of the present invention comprises a fuel hopper 10 for receiving fuel, a screw feeder 11 to supply the received fuel to a subsequent device, and a catalytic circulating fluidized-bed gasif ⁇ er 20 provided in the rear of the fuel hopper 10.
  • the catalytic circulating fluidized-bed gasif ⁇ er 20 includes a shutter provided at a middle portion thereof and through which the fuel is supplied from the screw feeder 11.
  • the catalytic circulating fluidized-bed gasif ⁇ er 20 has a hot air pipe 21 and a steam pipe 22 disposed in a conical lower portion thereof.
  • the hot air pipe 21 is positioned at the same level as that of the conical lower portion, and the steam pipe 22 is positioned such that its end is protruded to a height of 15 ⁇ 30 cm apart from the lower portion.
  • a small cyclone 23 may be further provided.
  • a dust collector 30 is provided in the rear of the catalytic circulating fluidized-bed gasif ⁇ er 20, and a pipe extending from the upper portion of the catalytic circulating fluidized-bed gasif ⁇ er 20 is connected to the side wall of the upper portion of the dust collector 30.
  • the dust collector 30 functions to collect fly ash in the gas in the lower portion thereof.
  • a catalyst reformer 40 is provided in the rear of the dust collector 30, and a pipe 31 extending from the upper portion of the dust collector 30 is connected to the lower portion of the catalyst reformer 40.
  • the catalyst reformer 40 has a fixed filter adsorbent bed 41 disposed in the lower portion thereof, and a fluidized catalyst bed 42 formed on the fixed filter adsorbent bed 41.
  • the fixed filter adsorbent bed 41 which is a cartridge type, may include a mixture comprising an asbestos filter, particles of alkali earth metal oxide and powdery particles of alkali metal salt.
  • the pipe 31 extending from the upper portion of the dust collector 30 is provided with a valve 32 at an intermediate position thereof that communicates with a steam pipe 33, and the pipe 31 communicates with a steam sprayer 43 disposed at the lower portion of the fixed filter adsorbent bed 41 of the catalyst reformer 40.
  • a heat exchanger 50 is provided in the rear of the catalyst reformer 40.
  • a tar scrubber 60 is provided after the heat exchanger 50, and includes a tar scrubbing chamber 61, a tar-storing bath 62 disposed at the lower portion thereof, and a circulation pump 63 for circulating tar.
  • the tar-storing bath 62 communicates with a lower pipe of each of the catalyst reformer 40 and the heat exchanger 50 via individual tar valves 64 to collect the generated tar from the catalyst 40 and the heat exchanger 50.
  • a gas-holder 70 is provided in the rear of the tar scrubber 60, and a fuel gas-storing pump 71 is disposed between the tar scrubber 60 and the gas ⁇ holder 70.
  • a refined fuel mixture which is supplied through a screw feeder 11 from a fuel hopper 10, undergoes drying, volatilization, low-temperature catalytic gasification, pyrolysis gasification and partial burning, by air or oxygen and water vapor fed via a hot air pipe 21 and a steam pipe 22 in a catalytic circulating fluidized-bed gasif ⁇ er 20. Unreacted fuel comes into contact with air or oxygen at the conical lower end of the gasifier, and thus, is completely burned.
  • the ratio of air or oxygen supplied into the catalytic circulating fluidized- bed gasifier 20 is about 0.3-0.7 based on the amount of air required for theoretical complete combustion of the refined fuel mixture, and water vapor is fed at a volume ratio of 0.5-10 times that of air.
  • the fluidized catalyst for gasification in the catalytic circulating fluidized-bed gasifier 20 includes natural limestone, lime magnesite, or caustic lime, an alkali earth metal such as calcium, magnesium or barium and oxides thereof, an alkali metal such as potassium and oxides thereof, alumina, or mixtures thereof, each of which is provided in the form of particles or coarse powders suitable for fluidization.
  • the gasification is conducted at a maximal temperature of 900°C or less by high-speed operation, for example, for a gas retention time of 2 ⁇ 4 sec.
  • partial oxidation and low-temperature catalytic pyrolysis are simultaneously conducted at 85O 0 C or less.
  • most gasification uses oxygen at a high temperature.
  • the gas may be produced to have the same caloric value as that of a conventional process using oxygen.
  • a small cyclone 23 is provided to the upper portion of the catalytic circulating fluidized-bed gasifier 20 to efficiently collect scattered catalyst or fuel agglomerate such as unreacted material and heavy tar, which is then re-circulated to the catalytic circulating fluidized-bed gasifier 20, thus completing the gasification.
  • the catalyst reformer 40 has a two-layered structure, including a lower layer of cartridge type fixed filter adsorbent bed 41 and an upper layer of fluidized catalyst bed 42.
  • adsorbent bed 41 fine fly ash is removed via an asbestos filter, and sulfur and phosphorous poisoning are chemically adsorbed and removed using potassium oxide and sodium carbonate as an adsorbent.
  • a detoxification filter may be recycled or replaced after being used for a predetermined period. For example, hydrogen sulfide (H 2 S) generated upon gasification reacts with CaO and is converted into CaS, which is then adsorbed.
  • H 2 S hydrogen sulfide
  • a vapor compound such as PH 4 -halogen reacts with Na 2 CO 3 to produce
  • the usable reformation catalyst includes a single metal, such as Ni, Fe, Co, Mo, Mn, Zr, Ti, Ce, Ru, Rh or Pt, and oxides thereof, or mixtures thereof. Such a catalyst is preferably used at 650 0 C or less.
  • the heat of reformed gas is exchanged by using the heat exchanger 50 to cool the gas to 200°C or less, and the condensed liquid is transferred in the tar- storing bath 62.
  • air or oxygen and water used in the gasification may serve as a cooling medium for heat exchange, and then be converted into hot air and steam.
  • the heat exchanger 50 may increase the energy efficiency if a metal heat exchanger made of a high-temperature material is used.
  • the non-converted tar or non-condensed liquid in the catalyst reformer 40 is condensed in the tar scrubber 60, and then recovered in the tar-storing bath 62.
  • 150°C or less is re-transferred to the upper portion of the tar scrubber 60 through the tar circulating pump 63, thus conducting gas stripping.
  • the resultant clean gas fuel is compressed and then stored temporarily in the gas-holder 70.
  • the MnO 2 catalyst was inferior in tar reformation to the NiO catalyst, by which fuel-N was converted not into ammonia but into HCN.
  • the NiO catalyst exhibited superior fuel-N reformation performance as a second catalyst.

Landscapes

  • 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)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Industrial Gases (AREA)
  • Processing Of Solid Wastes (AREA)
  • Treatment Of Sludge (AREA)
  • Catalysts (AREA)
  • Filtering Materials (AREA)

Abstract

L'invention concerne une technique de gazéification permettant de convertir une biomasse qui est difficile à traiter en un gaz combustible propre pouvant être brûlé dans un système de cogénération. Cette technique de gazéification comprend une première étape de gazéification catalytique à lit fluidisé, une seconde étape de gazéification de goudron et de reformation catalytique afin de convertir de l'azote en goudron, et du HCN dans un gaz inflammable en NH3, contrairement aux techniques de gazéification classiques. En outre, puisque la température d'un procédé de gazéification total est inférieure au point de fusion de cendres, des cendres en poudre sont générées et ainsi facilement traitées. En outre, peu de fumée est produite en raison de la basse température du procédé, et par conséquent un réacteur compact peut être conçu pour produire du gaz présentant une valeur calorique élevée. En outre, le goudron généré est récupéré et réutilisé dans d'autres procédés, et le gaz combustible contient une petite quantité d'ammoniaque.
PCT/KR2005/001808 2004-08-05 2005-06-14 Appareil de gazeification catalytique pour un combustible a biomasse raffine a faible temperature, et son procede d'utilisation WO2006031011A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US10/560,992 US20070094929A1 (en) 2004-08-05 2005-06-14 Apparatus of catalytic gasification for refined biomass fuel at low temperature and the method thereof
EP05750463A EP1773968A4 (fr) 2004-08-05 2005-06-14 Appareil de gazeification catalytique pour un combustible a biomasse raffine a faible temperature, et son procede d'utilisation
JP2006535283A JP4243295B2 (ja) 2004-08-05 2005-06-14 バイオマス精製燃料の低温触媒ガス化装置および方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2004-0061657 2004-08-05
KR1020040061657A KR100569120B1 (ko) 2004-08-05 2004-08-05 바이오메스 정제연료의 저온 촉매가스화 장치 및가스제조방법

Publications (1)

Publication Number Publication Date
WO2006031011A1 true WO2006031011A1 (fr) 2006-03-23

Family

ID=36060239

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2005/001808 WO2006031011A1 (fr) 2004-08-05 2005-06-14 Appareil de gazeification catalytique pour un combustible a biomasse raffine a faible temperature, et son procede d'utilisation

Country Status (5)

Country Link
US (1) US20070094929A1 (fr)
EP (1) EP1773968A4 (fr)
JP (1) JP4243295B2 (fr)
KR (1) KR100569120B1 (fr)
WO (1) WO2006031011A1 (fr)

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007283209A (ja) * 2006-04-17 2007-11-01 Takuma Co Ltd ガス化触媒とその製造方法およびガス化処理システム
JP2008132458A (ja) * 2006-11-29 2008-06-12 Nippon Steel Corp 炭素質原料の熱分解タールを改質してガス化するタールガス化用触媒、タールガス化方法、タールガス化ガスの利用方法、及びタールガス化用触媒の再生方法
EP2034003A1 (fr) * 2007-09-07 2009-03-11 ReSeTec Patents Geneva S.A. i.o. Procédé et appareil de production de gaz de synthèse à partir des déchets
JP2011255375A (ja) * 2011-07-21 2011-12-22 Takuma Co Ltd ガス化触媒の製造方法およびガス化処理システム
US8100995B2 (en) 2006-04-10 2012-01-24 Teknologian Tutkimuskeskus Vtt Multiple stage method of reforming a gas containing tarry impurities employing a zirconium-based catalyst
WO2012143549A1 (fr) * 2011-04-21 2012-10-26 Shell Internationale Research Maatschappij B.V. Améliorations apportées à la séparation de débits diluats
WO2012162971A1 (fr) * 2011-05-27 2012-12-06 北京神雾环境能源科技集团股份有限公司 Procédé de gazéification de charbon pulvérisé sur un lit cyclonique et son système
US8999020B2 (en) 2008-04-01 2015-04-07 Greatpoint Energy, Inc. Processes for the separation of methane from a gas stream
US9012524B2 (en) 2011-10-06 2015-04-21 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
US9034058B2 (en) 2012-10-01 2015-05-19 Greatpoint Energy, Inc. Agglomerated particulate low-rank coal feedstock and uses thereof
US9034061B2 (en) 2012-10-01 2015-05-19 Greatpoint Energy, Inc. Agglomerated particulate low-rank coal feedstock and uses thereof
US9127221B2 (en) 2011-06-03 2015-09-08 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
US9169444B2 (en) 2011-04-21 2015-10-27 Shell Oil Company Liquid fuel composition
US9217111B2 (en) 2011-04-21 2015-12-22 Shell Oil Company Process for converting a solid biomass material
US9234149B2 (en) 2007-12-28 2016-01-12 Greatpoint Energy, Inc. Steam generating slurry gasifier for the catalytic gasification of a carbonaceous feedstock
US9238779B2 (en) 2011-04-21 2016-01-19 Shell Oil Company Process for converting a solid biomass material
US9273260B2 (en) 2012-10-01 2016-03-01 Greatpoint Energy, Inc. Agglomerated particulate low-rank coal feedstock and uses thereof
US9314760B2 (en) 2012-01-20 2016-04-19 Nippon Steel & Sumitomo Metal Corporation Continuous fixed-bed catalytic reactor and catalytic reaction method using same
US9328920B2 (en) 2012-10-01 2016-05-03 Greatpoint Energy, Inc. Use of contaminated low-rank coal for combustion
US9353322B2 (en) 2010-11-01 2016-05-31 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
US9920929B2 (en) 2011-06-13 2018-03-20 Ecolab Usa Inc. Method for reducing slag in biomass combustion
US10344231B1 (en) 2018-10-26 2019-07-09 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock with improved carbon utilization
US10435637B1 (en) 2018-12-18 2019-10-08 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock with improved carbon utilization and power generation
US10464872B1 (en) 2018-07-31 2019-11-05 Greatpoint Energy, Inc. Catalytic gasification to produce methanol
US10618818B1 (en) 2019-03-22 2020-04-14 Sure Champion Investment Limited Catalytic gasification to produce ammonia and urea
US11091711B2 (en) 2016-09-21 2021-08-17 Haldor Topsøe A/S Separator system and tar reformer system
US20230132767A1 (en) * 2021-10-29 2023-05-04 Simonpietri Enterprises LLC Processing and gasification of construction and demolition materials

Families Citing this family (65)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL1030864C2 (nl) * 2006-01-06 2007-07-09 Stichting Energie Werkwijze en inrichting voor het behandelen van biomassa.
DE102006017353A1 (de) * 2006-04-11 2007-10-18 Spot Spirit Of Technology Ag Verfahren und Vorrichtung zur prozessintegrierten heißen Gasreinigung von Staub- und gasförmigen Inhaltsstoffen eines Synthesegases
FR2904405B1 (fr) * 2006-07-31 2008-10-31 Inst Francais Du Petrole Procede de preparation d'une charge contenant de la biomasse en vue d'une gazeification ulterieure
KR100784851B1 (ko) * 2007-01-12 2007-12-14 한국에너지기술연구원 저타르 배출형 바이오매스 가스화 장치
CN101611123B (zh) * 2007-02-22 2013-11-20 株式会社Ihi 燃料气化设备
JP4787966B2 (ja) * 2007-03-30 2011-10-05 国立大学法人群馬大学 含窒素廃棄物の乾式処理方法とそのための装置
CN101688135A (zh) * 2007-05-02 2010-03-31 帕尔公司 用于由可气化原料材料产生合成气的气化装置和方法
US7942943B2 (en) * 2007-06-15 2011-05-17 Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College Biomass gasifier system with low energy and maintenance requirements
US20090031698A1 (en) * 2007-07-31 2009-02-05 O'brien & Gere Engineers Inc. Liquid and Solid Biofueled Combined Heat and Renewable Power Plants
CA2704713A1 (fr) 2007-10-09 2009-04-16 Silvagas Corporation Systemes et procedes pour l'oxydation de goudrons de gaz de synthese
KR100986241B1 (ko) * 2007-10-23 2010-10-07 서울시립대학교 산학협력단 타르의 수증기 개질용 촉매 및 이를 이용한 타르의 수증기 개질방법
KR100912249B1 (ko) 2008-03-25 2009-08-14 한국에너지기술연구원 타르개질과 수트제거용 촉매반응장치
JP4966239B2 (ja) * 2008-03-28 2012-07-04 メタウォーター株式会社 有機性廃棄物処理方法、ガス化炉、改質炉、有機性廃棄物処理装置
DE102008021081A1 (de) * 2008-04-28 2009-10-29 Süd-Chemie AG Verfahren zur katalytischen Verringerung des Teergehalts in Gasen aus Vergasungsprozessen unter Verwendung eines Katalysators auf Edelmetallbasis
DE102008021084A1 (de) * 2008-04-28 2009-10-29 Süd-Chemie AG Verwendung eines Katalysators auf Edelmetallbasis zur Verringerung des Teergehalts in Gasen aus Vergasungsprozessen
FI126542B (fi) * 2008-06-13 2017-02-15 Valmet Technologies Oy Menetelmä ja laitos meesan käsittelemiseksi sekä petimateriaali
US8460410B2 (en) * 2008-08-15 2013-06-11 Phillips 66 Company Two stage entrained gasification system and process
US8499471B2 (en) * 2008-08-20 2013-08-06 The Board Of Regents Of The Nevada System Of Higher Education, On Behalf Of The University Of Nevada, Reno System and method for energy production from sludge
JP5521187B2 (ja) * 2008-09-25 2014-06-11 株式会社神鋼環境ソリューション 廃棄物をガス化する可燃ガス生成装置および可燃ガス製造方法
US8669404B2 (en) 2008-10-15 2014-03-11 Renewable Fuel Technologies, Inc. Method for conversion of biomass to biofuel
JP5572855B2 (ja) * 2009-03-24 2014-08-20 昭和シェル石油株式会社 バイオマスガス化改質触媒及びこれを用いた合成ガスの製造方法
US8668753B2 (en) * 2009-04-24 2014-03-11 G.D.O. Inc Two stage process for converting biomass to syngas
US8404910B2 (en) * 2010-02-17 2013-03-26 Uop Llc Low oxygen biomass-derived pyrolysis oils and methods for producing the same
CA2791393A1 (fr) * 2010-03-08 2011-09-15 Arthur M. Shulenberger Dispositif et procede pour la conversion de la biomasse en biocarburant
DE102011107621B4 (de) 2010-07-05 2022-11-03 Uwe Athmann Feinreinigung von Produktgasen
WO2012031041A2 (fr) 2010-09-01 2012-03-08 Starlight Energy Holdings LLC Système et procédé pour gazéifier des produits de biomasse
US20120137700A1 (en) * 2010-12-07 2012-06-07 Dennis John Werner System for Producing Power Using Low Pressure Gasification of a Stock Fuel
JP5857340B2 (ja) * 2011-03-15 2016-02-10 九州電力株式会社 石炭をチャー・原料ガス製造と発電に利用する複合システム
US9062597B2 (en) 2011-05-10 2015-06-23 Innerpoint Energy Corporation Centrifugal particle separator and method of operating the same
KR101065184B1 (ko) 2011-06-09 2011-09-19 한국에너지기술연구원 저급탄 석탄가스 생산시스템
WO2012169711A1 (fr) * 2011-06-09 2012-12-13 한국에너지기술연구원 Système de production de gaz de houille de houille maigre
US9127219B2 (en) 2011-07-19 2015-09-08 General Electric Company Additive systems for biomass gasification
JP5762318B2 (ja) * 2012-01-20 2015-08-12 新日鐵住金株式会社 連続式固定床触媒反応装置及びこれを用いた触媒反応方法
TWI447598B (zh) * 2012-06-13 2014-08-01 China Steel Corp 生質物之乾燥方法與其電腦程式產品
JP5974363B2 (ja) * 2012-06-15 2016-08-23 株式会社Ihi ガス化ガス生成装置、および、タール改質装置
KR101890950B1 (ko) * 2012-12-07 2018-08-22 에스케이이노베이션 주식회사 정유공정으로부터 배출된 폐촉매를 이용한 가스화 방법
KR20170092717A (ko) * 2013-02-14 2017-08-11 베올리아 워터 솔루션즈 앤드 테크놀러지스 써포트 바이오매스로부터의 폴리히드록시알카노에이트의 추출 방법
JP2014205806A (ja) * 2013-04-15 2014-10-30 株式会社Ihi ガス化ガス生成システム
WO2014182295A1 (fr) * 2013-05-08 2014-11-13 Innerpoint Energy Corporation Séparateur de particules centrifuge et son procédé de fonctionnement
CN103343021B (zh) * 2013-07-17 2015-06-24 王建伟 一种生物质气化燃气的余热回收与净化装置及其净化方法
KR101623476B1 (ko) * 2013-10-16 2016-06-07 한국기계연구원 반도체 제조공정용 질소산화물 제거장치
KR101537058B1 (ko) * 2014-04-04 2015-07-16 주식회사 온이엔지 고형 원료 가스화 장치 및 이를 이용한 고형 원료의 가스화 방법
US9545590B2 (en) 2015-01-16 2017-01-17 Innerpoint Energy Corporation Rotating centrifugal particle separator and gasifier having the same
KR101863359B1 (ko) * 2015-07-01 2018-06-01 한국에너지기술연구원 바이오오일의 연속 촉매 반응 장치
CN106915861B (zh) * 2015-12-24 2021-03-30 中国科学院过程工程研究所 一种基于污泥臭氧催化氧化的煤化工废水生物处理系统及其处理方法
MX2018013717A (es) * 2016-05-12 2019-06-20 Golden Renewable Energy Llc Sistema ciclonico de enfriamiento y condensacion.
AU2017282172B2 (en) 2016-06-21 2022-01-20 Golden Renewable Energy, LLC Char separator and method
US10961062B2 (en) 2016-06-21 2021-03-30 Golden Renewable Energy, LLC Bag press feeder assembly
US11066613B2 (en) * 2016-06-23 2021-07-20 Glock Ökoenergie Gmbh Method and apparatus for gasifying carbon-containing material
CN109477010B (zh) 2016-07-05 2021-07-23 戈登可再生能源有限公司 用于将废弃塑料转化成燃料的系统和工艺
JP2019137717A (ja) * 2018-02-06 2019-08-22 国立研究開発法人産業技術総合研究所 タール成分の処理方法および装置
CN108409077A (zh) * 2018-03-30 2018-08-17 中石化石油工程技术服务有限公司 含油污泥物化耦合处理方法
SI25771A (sl) * 2019-01-07 2020-07-31 Teos Perne Naprava za uplinjanje trdnih materialov z vsebnostjo ogljika, s poudarjeno koncentracijo katranov in njihovo katalitsko pretvorbo v ogljikov monoksid in vodik
CN109628158B (zh) * 2019-01-21 2024-01-16 中国科学院广州地球化学研究所 一种轻工有机固废分级热转化制备低氮高值燃气的方法
CN110129100B (zh) * 2019-05-28 2023-12-22 彭万旺 高效燃烧系统及方法
CN110484306B (zh) * 2019-08-27 2020-11-17 湖南工程学院 一种复合式生物质分级气化炉
EP3805340B1 (fr) * 2019-10-09 2023-06-07 Reissner, Markus Procédé et utilisation d'un système de production d'un mélange gazeux contenant de l'hydrogène et d'hydrogène à partir de matière synthétique
KR102437950B1 (ko) * 2020-02-28 2022-08-30 연세대학교 원주산학협력단 분사층 반응기를 이용한 증기 개질장치를 포함하는 바이오오일 가스화 시스템
JP6991647B1 (ja) * 2020-08-07 2022-02-03 株式会社エコクルジャパン 熱化学的変換方法及び熱化学的変換装置
KR102439355B1 (ko) * 2020-09-07 2022-09-01 비에이치아이 주식회사 바이오매스 가스화시스템
KR102465674B1 (ko) * 2020-11-11 2022-11-11 한국생산기술연구원 탄소 기반 첨가제 연속 재생식 가스화 장치 및 이를 이용한 합성 가스 제조 방법
CN113477186B (zh) * 2021-06-22 2022-07-01 沈阳化工大学 一种重质焦油选择性催化提质装置及其方法
US11905476B1 (en) * 2021-11-29 2024-02-20 The United States Of America, As Represented By The Secretary Of The Navy Apparatus and method for capturing renewable and non-renewable energy from biodegradable and non-biodegradable municipal waste
KR102653928B1 (ko) * 2022-01-05 2024-04-02 한국에너지기술연구원 타르 개질기 일체형 가스화기
CN115806839B (zh) * 2022-11-29 2024-05-14 华中科技大学 一种基于污泥和生物质协同气化的固废处理系统

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1989004354A1 (fr) * 1987-11-06 1989-05-18 Dansk Termo Industri A/S Procede et appareil de production d'un gaz a partir de dechets biologiques finement broyes
WO1996030464A1 (fr) * 1995-03-31 1996-10-03 University Of Hawaii Gazeification supercritique catalytique de biomasses mouillees
JP2003246990A (ja) * 2001-12-18 2003-09-05 Univ Tohoku バイオマスのガス化方法、およびそれに用いられる触媒
JP2003342588A (ja) * 2002-05-27 2003-12-03 Setec:Kk バイオマスガス化装置
JP2004149556A (ja) * 2002-10-28 2004-05-27 Nishinippon Environmental Energy Co Inc バイオマスのガス化方法及びそのガス化装置

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3115394A (en) * 1961-05-29 1963-12-24 Consolidation Coal Co Process for the production of hydrogen
US3929431A (en) * 1972-09-08 1975-12-30 Exxon Research Engineering Co Catalytic reforming process
US5213587A (en) * 1987-10-02 1993-05-25 Studsvik Ab Refining of raw gas
US4865625A (en) * 1988-05-02 1989-09-12 Battelle Memorial Institute Method of producing pyrolysis gases from carbon-containing materials
CA2368496C (fr) * 2000-02-29 2012-02-14 Mitsubishi Heavy Industries, Ltd. Four de gazeification de biomasse et systeme de synthese de methanol a l'aide du gaz produit par la gazeification de la biomasse
EP1142981A3 (fr) * 2000-03-23 2003-04-02 Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E.V. Appareillage de génération d'électricité par gazéification de biomasse suivi par l'élimination catalytique des composés du goudron
US6797253B2 (en) * 2001-11-26 2004-09-28 General Electric Co. Conversion of static sour natural gas to fuels and chemicals

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1989004354A1 (fr) * 1987-11-06 1989-05-18 Dansk Termo Industri A/S Procede et appareil de production d'un gaz a partir de dechets biologiques finement broyes
WO1996030464A1 (fr) * 1995-03-31 1996-10-03 University Of Hawaii Gazeification supercritique catalytique de biomasses mouillees
JP2003246990A (ja) * 2001-12-18 2003-09-05 Univ Tohoku バイオマスのガス化方法、およびそれに用いられる触媒
JP2003342588A (ja) * 2002-05-27 2003-12-03 Setec:Kk バイオマスガス化装置
JP2004149556A (ja) * 2002-10-28 2004-05-27 Nishinippon Environmental Energy Co Inc バイオマスのガス化方法及びそのガス化装置

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1773968A4 *

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8100995B2 (en) 2006-04-10 2012-01-24 Teknologian Tutkimuskeskus Vtt Multiple stage method of reforming a gas containing tarry impurities employing a zirconium-based catalyst
JP2007283209A (ja) * 2006-04-17 2007-11-01 Takuma Co Ltd ガス化触媒とその製造方法およびガス化処理システム
JP2008132458A (ja) * 2006-11-29 2008-06-12 Nippon Steel Corp 炭素質原料の熱分解タールを改質してガス化するタールガス化用触媒、タールガス化方法、タールガス化ガスの利用方法、及びタールガス化用触媒の再生方法
EP2034003A1 (fr) * 2007-09-07 2009-03-11 ReSeTec Patents Geneva S.A. i.o. Procédé et appareil de production de gaz de synthèse à partir des déchets
US9234149B2 (en) 2007-12-28 2016-01-12 Greatpoint Energy, Inc. Steam generating slurry gasifier for the catalytic gasification of a carbonaceous feedstock
US8999020B2 (en) 2008-04-01 2015-04-07 Greatpoint Energy, Inc. Processes for the separation of methane from a gas stream
US9353322B2 (en) 2010-11-01 2016-05-31 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
CN103597057B (zh) * 2011-04-21 2015-11-25 国际壳牌研究有限公司 有关产品物流分离的改进
US9249362B2 (en) 2011-04-21 2016-02-02 Shell Oil Company Separation of product streams
CN103597057A (zh) * 2011-04-21 2014-02-19 国际壳牌研究有限公司 有关产品物流分离的改进
US9238779B2 (en) 2011-04-21 2016-01-19 Shell Oil Company Process for converting a solid biomass material
WO2012143549A1 (fr) * 2011-04-21 2012-10-26 Shell Internationale Research Maatschappij B.V. Améliorations apportées à la séparation de débits diluats
US9217111B2 (en) 2011-04-21 2015-12-22 Shell Oil Company Process for converting a solid biomass material
US9169444B2 (en) 2011-04-21 2015-10-27 Shell Oil Company Liquid fuel composition
WO2012162971A1 (fr) * 2011-05-27 2012-12-06 北京神雾环境能源科技集团股份有限公司 Procédé de gazéification de charbon pulvérisé sur un lit cyclonique et son système
US9127221B2 (en) 2011-06-03 2015-09-08 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
US9920929B2 (en) 2011-06-13 2018-03-20 Ecolab Usa Inc. Method for reducing slag in biomass combustion
JP2011255375A (ja) * 2011-07-21 2011-12-22 Takuma Co Ltd ガス化触媒の製造方法およびガス化処理システム
US9012524B2 (en) 2011-10-06 2015-04-21 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
US9314760B2 (en) 2012-01-20 2016-04-19 Nippon Steel & Sumitomo Metal Corporation Continuous fixed-bed catalytic reactor and catalytic reaction method using same
US9273260B2 (en) 2012-10-01 2016-03-01 Greatpoint Energy, Inc. Agglomerated particulate low-rank coal feedstock and uses thereof
US9328920B2 (en) 2012-10-01 2016-05-03 Greatpoint Energy, Inc. Use of contaminated low-rank coal for combustion
US9034058B2 (en) 2012-10-01 2015-05-19 Greatpoint Energy, Inc. Agglomerated particulate low-rank coal feedstock and uses thereof
US9034061B2 (en) 2012-10-01 2015-05-19 Greatpoint Energy, Inc. Agglomerated particulate low-rank coal feedstock and uses thereof
US11091711B2 (en) 2016-09-21 2021-08-17 Haldor Topsøe A/S Separator system and tar reformer system
US10464872B1 (en) 2018-07-31 2019-11-05 Greatpoint Energy, Inc. Catalytic gasification to produce methanol
US10344231B1 (en) 2018-10-26 2019-07-09 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock with improved carbon utilization
US10435637B1 (en) 2018-12-18 2019-10-08 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock with improved carbon utilization and power generation
US10618818B1 (en) 2019-03-22 2020-04-14 Sure Champion Investment Limited Catalytic gasification to produce ammonia and urea
US20230132767A1 (en) * 2021-10-29 2023-05-04 Simonpietri Enterprises LLC Processing and gasification of construction and demolition materials
US12157863B2 (en) * 2021-10-29 2024-12-03 Simonpietri Enterprises LLC Processing and gasification of construction and demolition materials

Also Published As

Publication number Publication date
KR100569120B1 (ko) 2006-04-10
KR20060012934A (ko) 2006-02-09
EP1773968A1 (fr) 2007-04-18
EP1773968A4 (fr) 2012-03-28
US20070094929A1 (en) 2007-05-03
JP4243295B2 (ja) 2009-03-25
JP2007506856A (ja) 2007-03-22

Similar Documents

Publication Publication Date Title
US20070094929A1 (en) Apparatus of catalytic gasification for refined biomass fuel at low temperature and the method thereof
EP2598616B1 (fr) Procédé de gazéification de matière carbonée et système de gazéification
US9528057B2 (en) System and method for dual fluidized bed gasification
US20070000177A1 (en) Mild catalytic steam gasification process
US5213587A (en) Refining of raw gas
CN101932677A (zh) 用于生产富氢含量的合成气的生物质气化方法和装置
WO2004024620A2 (fr) Processus et appareil de reformage a la vapeur
JP2004149556A (ja) バイオマスのガス化方法及びそのガス化装置
JP2573681B2 (ja) 原料ガスの精製
JP2007137959A (ja) 高含水バイオマス・廃棄物のガス化方法及びそのシステム

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 2005750463

Country of ref document: EP

Ref document number: 2007094929

Country of ref document: US

Ref document number: 10560992

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 2006535283

Country of ref document: JP

AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KM KP KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

WWP Wipo information: published in national office

Ref document number: 2005750463

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 10560992

Country of ref document: US

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载