EP1649217A1 - Vergasungssystem - Google Patents
VergasungssystemInfo
- Publication number
- EP1649217A1 EP1649217A1 EP04748078A EP04748078A EP1649217A1 EP 1649217 A1 EP1649217 A1 EP 1649217A1 EP 04748078 A EP04748078 A EP 04748078A EP 04748078 A EP04748078 A EP 04748078A EP 1649217 A1 EP1649217 A1 EP 1649217A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- gasification
- combustion
- gas
- furnace
- chamber
- 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- Withdrawn
Links
- 238000002309 gasification Methods 0.000 title claims abstract description 367
- 239000007789 gas Substances 0.000 claims abstract description 275
- 238000002485 combustion reaction Methods 0.000 claims abstract description 263
- 239000000567 combustion gas Substances 0.000 claims abstract description 167
- 239000003054 catalyst Substances 0.000 claims description 70
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 55
- 239000001301 oxygen Substances 0.000 claims description 55
- 229910052760 oxygen Inorganic materials 0.000 claims description 55
- 239000002245 particle Substances 0.000 claims description 45
- 239000000463 material Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 18
- 239000011261 inert gas Substances 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- 239000004576 sand Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 7
- 239000002699 waste material Substances 0.000 abstract description 56
- 239000000428 dust Substances 0.000 description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- 238000010586 diagram Methods 0.000 description 19
- 238000000197 pyrolysis Methods 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 18
- 239000002994 raw material Substances 0.000 description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 description 16
- 238000011084 recovery Methods 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 14
- 239000002893 slag Substances 0.000 description 13
- 239000002737 fuel gas Substances 0.000 description 12
- 239000002028 Biomass Substances 0.000 description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 229940043430 calcium compound Drugs 0.000 description 8
- 150000001674 calcium compounds Chemical class 0.000 description 8
- 150000001805 chlorine compounds Chemical class 0.000 description 8
- 150000003464 sulfur compounds Chemical class 0.000 description 8
- 231100000331 toxic Toxicity 0.000 description 8
- 230000002588 toxic effect Effects 0.000 description 8
- 231100000614 poison Toxicity 0.000 description 7
- 230000008929 regeneration Effects 0.000 description 7
- 238000011069 regeneration method Methods 0.000 description 7
- 239000003440 toxic substance Substances 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- 239000003245 coal Substances 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- 238000002407 reforming Methods 0.000 description 6
- 239000003473 refuse derived fuel Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000010248 power generation Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005243 fluidization Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000002440 industrial waste Substances 0.000 description 3
- 239000010813 municipal solid waste Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000005923 long-lasting effect Effects 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
- F23G5/02—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment
- F23G5/027—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment pyrolising or gasifying stage
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN A CARRIER GAS OR AIR
- F23C13/00—Apparatus in which combustion takes place in the presence of catalytic material
- F23C13/08—Apparatus in which combustion takes place in the presence of catalytic material characterised by the catalytic material
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
- F23G5/006—General arrangement of incineration plant, e.g. flow sheets
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
- F23G5/02—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment
- F23G5/027—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment pyrolising or gasifying stage
- F23G5/0276—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment pyrolising or gasifying stage using direct heating
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
- F23G5/08—Incineration of waste; Incinerator constructions; Details, accessories or control therefor having supplementary heating
- F23G5/14—Incineration of waste; Incinerator constructions; Details, accessories or control therefor having supplementary heating including secondary combustion
- F23G5/16—Incineration of waste; Incinerator constructions; Details, accessories or control therefor having supplementary heating including secondary combustion in a separate combustion chamber
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
- F23G5/30—Incineration of waste; Incinerator constructions; Details, accessories or control therefor having a fluidised bed
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
- F23G5/44—Details; Accessories
- F23G5/46—Recuperation of heat
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J15/00—Arrangements of devices for treating smoke or fumes
- F23J15/006—Layout of treatment plant
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J15/00—Arrangements of devices for treating smoke or fumes
- F23J15/06—Arrangements of devices for treating smoke or fumes of coolers
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2201/00—Pretreatment
- F23G2201/30—Pyrolysing
- F23G2201/303—Burning pyrogases
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2201/00—Pretreatment
- F23G2201/30—Pyrolysing
- F23G2201/304—Burning pyrosolids
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2202/00—Combustion
- F23G2202/10—Combustion in two or more stages
- F23G2202/101—Combustion in two or more stages with controlled oxidant supply
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2202/00—Combustion
- F23G2202/10—Combustion in two or more stages
- F23G2202/104—Combustion in two or more stages with ash melting stage
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2203/00—Furnace arrangements
- F23G2203/50—Fluidised bed furnace
- F23G2203/502—Fluidised bed furnace with recirculation of bed material inside combustion chamber
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/26—Biowaste
- F23G2209/262—Agricultural waste
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J2217/00—Intercepting solids
- F23J2217/50—Intercepting solids by cleaning fluids (washers or scrubbers)
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23L—SUPPLYING AIR OR NON-COMBUSTIBLE LIQUIDS OR GASES TO COMBUSTION APPARATUS IN GENERAL ; VALVES OR DAMPERS SPECIALLY ADAPTED FOR CONTROLLING AIR SUPPLY OR DRAUGHT IN COMBUSTION APPARATUS; INDUCING DRAUGHT IN COMBUSTION APPARATUS; TOPS FOR CHIMNEYS OR VENTILATING SHAFTS; TERMINALS FOR FLUES
- F23L2900/00—Special arrangements for supplying or treating air or oxidant for combustion; Injecting inert gas, water or steam into the combustion chamber
- F23L2900/07002—Injecting inert gas, other than steam or evaporated water, into the combustion chambers
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23L—SUPPLYING AIR OR NON-COMBUSTIBLE LIQUIDS OR GASES TO COMBUSTION APPARATUS IN GENERAL ; VALVES OR DAMPERS SPECIALLY ADAPTED FOR CONTROLLING AIR SUPPLY OR DRAUGHT IN COMBUSTION APPARATUS; INDUCING DRAUGHT IN COMBUSTION APPARATUS; TOPS FOR CHIMNEYS OR VENTILATING SHAFTS; TERMINALS FOR FLUES
- F23L2900/00—Special arrangements for supplying or treating air or oxidant for combustion; Injecting inert gas, water or steam into the combustion chamber
- F23L2900/07005—Injecting pure oxygen or oxygen enriched air
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/30—Technologies for a more efficient combustion or heat usage
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/34—Indirect CO2mitigation, i.e. by acting on non CO2directly related matters of the process, e.g. pre-heating or heat recovery
Definitions
- the present invention relates to a gasification system for gasifying various wastes such as municipal solid wastes, industrial wastes, and waste plastics, biomass, and combustible materials such as coal and refuse-derived fuel (RDF) in a gasification furnace or chamber and recovering a valuable combustible gas produced by gasification.
- wastes such as municipal solid wastes, industrial wastes, and waste plastics, biomass, and combustible materials
- RDF refuse-derived fuel
- a gasification and slagging combustion furnace has been developed as incineration technology for wastes.
- the gasification and slagging combustion furnace has a gasification apparatus for gasifying wastes into a combustible gas and combusting the combustible gas at a high temperature immediately after gasification. Combustion at a high temperature has the following advantages.
- the volume of ash can be reduced by melting ash from the wastes.
- the ash can be made harmless by melting ash.
- the combustion efficiency can be improved, i.e., the amount of unburned combustibles can be reduced in incinerated ash, and the amount of exhaust gas is reduced by operation at a low air ratio.
- the conventional gasification and slagging combustion furnace converts the whole energy into heat as with a conventional incineration furnace.
- the conventional gasification and slagging combustion furnace has a limited efficiency of energy use.
- the conventional gasification and slagging combustion furnace cannot produce storable energy.
- a produced gas in a gasification apparatus and does not combust the produced gas but utilizes the produced gas as a product gas.
- the product gas is utilized as fuel in an electric power generator such as a gas turbine, a gas engine, or a fuel cell, or as a raw material for synthesis of liquid fuel.
- an electric power generator such as a gas turbine, a gas engine, or a fuel cell, or as a raw material for synthesis of liquid fuel.
- a cogeneration system combining electric power generation utilizing a product gas and electric power generation utilizing heat recovery.
- Such a cogeneration system has an improved efficiency of energy use. Accordingly, this type of cogeneration system has been developed not only in a field of waste treatment, but also in a field of thermal power generation.
- a cogeneration system has been utilized in a high-efficiency thermal power generating system using coal.
- the technology that utilizes a product gas as a raw material for synthesis of liquid fuel can produce storable energy from energy resources that have heretofore been discarded and is thus advantageous in future energy security including stable supply of energy and total crisis management.
- a raw material having a large amount of fixed carbon such as coal or ligneous biomass
- char containing a large amount of fixed carbon is produced in the gasification apparatus. Because such char has an extremely low combustion rate as compared to that of a volatile gas, char is accumulated in the gasification apparatus. Thus, produced char is problematic in operation of the gasification apparatus in many cases.
- the gasification apparatus comprises a fluidized-bed furnace
- char is accumulated on a surface of a fluidized bed because char has a specific gravity smaller than a bed material in the fluidized bed. Therefore, even if incombustibles are to be withdrawn together with a bed material from a furnace bottom, char cannot be withdrawn from the fluidized-bed furnace, but only a bed material is withdrawn from the fluidized-bed furnace. Thus, a char bed is formed in the fluidized-bed furnace. Specifically, a fluidized bed having a large amount of char accumulated is formed in the fluidized-bed furnace.
- a char bed inhibits fluidization of the fluidized-bed furnace and thus may cause a shutdown of the system. Since a combustion rate of char is not more than a combustion rate of a combustible gas, oxygen is usually consumed by combustion of a combustible gas prior to combustion of char. Therefore, even if oxygen is supplied into the fluidized-bed furnace in order to increase the amount of combustion of char so as to reduce the amount of char accumulated in the fluidized-bed furnace, oxygen is consumed to combust a combustible gas. Specifically, energy of the combustible gas is excessively converted into heat.
- Char can be combusted under proper conditions (e.g. combustion temperature and residence time) that are independent of conditions in the gasification apparatus.
- Oxygen supplied to combust char does not combust a product gas.
- the combustible gas is not diluted by a char combustion gas. Thus, a gas having a high heating value can be obtained.
- a conventional gasification system having a gasification apparatus for gasifying various wastes or biomass to recover a valuable combustible gas and a combustion apparatus for combusting char and tar, which are produced as residues in the gasification apparatus, releases a combustion gas from the combustion apparatus to an atmosphere.
- the present invention has been made in view of the above drawbacks. It is, therefore, an object of the present invention to provide a gasification system having a gasification furnace or chamber for gasifying various wastes such as municipal solid wastes, industrial wastes, and waste plastics, biomass, and combustible materials such as coal and refuse-derived fuel (RDF) to recover a valuable combustible gas, and a combustion furnace or chamber for combusting char and tar produced as a residue in the gasification furnace or chamber.
- the gasification system returns a combustion gas discharged from a combustion furnace or chamber to the combustion furnace or chamber and to a gasification furnace or chamber so as not to release an exhaust gas to an atmosphere and can eliminate any chimneys.
- a gasification system having a gasification furnace for gasifying a combustible to produce a combustible gas, and a combustion furnace for combusting char and/or tar produced by gasification in the gasification furnace.
- the gasification system also has a return line for returning a combustion gas discharged from the combustion furnace to the gasification furnace and the combustion furnace.
- a gasification system having an integrated gasification furnace.
- the integrated gasification furnace has a gasification chamber for gasifying a combustible to produce a combustible gas, and a combustion chamber for combusting char and/or tar produced by gasification in the gasification chamber.
- the gasification system also has a return line for returning a combustion gas discharged from the combustion chamber to the gasification chamber and the combustion chamber. According to the present invention, no exhaust gas is released to an atmosphere from the gasification system. Accordingly, the gasification system does not contaminate the atmosphere. Further, it is possible to simplify an exhaust gas treatment facility. Furthermore, the gasification system does not need any chimneys and can achieve a clean system. Oxygen may be added to the combustion gas to be returned to the combustion furnace or chamber. Steam or inert gas such as nitrogen or carbon dioxide is supplied to the gasification furnace or chamber. The combustion gas may be supplied to a portion downstream of the gasification furnace or chamber. The combustion gas to be returned to the gasification furnace or chamber may have an oxygen concentration of 5 % or less.
- the gasification furnace or chamber may have a temperature of 350 to 950°C.
- the combustion furnace or chamber may have a temperature of 600 to 1000°C.
- the gasification system may also include a slagging combustion furnace for melting ash by using a portion of the combustible gas produced by gasification in the gasification furnace or chamber. In this case, a combustion gas discharged from the slagging combustion chamber may be returned to the combustion furnace or chamber.
- the gasification system may also include a water spray gas cooler for spraying water on the combustion gas discharged from the combustion furnace or chamber.
- the gasification system may also include a scrubber disposed in a line of the combustible gas discharged from the gasification furnace or chamber, and a water spray gas cooler for spraying water discharged from the scrubber on the combustion gas discharged from the combustion furnace or chamber.
- the gasification system may also include a fluidizing gas heater for exchanging heat between the combustion gas discharged from the combustion furnace or chamber and the combustion gas to be returned to the gasification furnace or chamber and the combustion furnace or chamber-
- the gasification system may also include a high-temperature furnace for pyrolyzing tar in the combustible gas discharged from the gasification furnace or chamber.
- the gasification furnace or chamber may comprise a fluidized-bed furnace having a bed material including at least one of silica sand and catalyst particles.
- the combustion furnace or chamber may comprise a fluidized-bed furnace having a bed material including at least one of silica sand and catalyst particles.
- the gasification system may also include a gas cooling apparatus for cooling the combustible gas discharged from the gasification furnace or chamber to remove moisture from the combustible gas.
- the gasification system may also include a gas cooling apparatus for cooling the combustion gas discharged from the combustion furnace or chamber to remove moisture from the combustion gas.
- FIG. 2 is a schematic diagram explanatory of principles of a variation of a gasification system according to the present invention
- FIG. 3 is a schematic diagram showing a gasification system according to a first embodiment of the present invention
- FIG. 4 is a schematic diagram showing a gasification system according to a second embodiment of the present invention
- FIG. 5 is a schematic diagram showing a gasification system according to a third embodiment of the present invention
- FIG. 6 is a schematic diagram showing a gasification system according to a fourth embodiment of the present invention
- FIG. 7 is a schematic diagram showing a gasification furnace in a gasification system according to a fifth embodiment of the present invention
- FIG. 8 is a schematic diagram showing a gasification system according to a sixth embodiment of the present invention
- FIG. 9 is a schematic diagram showing a gasification system according to a seventh embodiment of the present invention
- FIG. 10 is a schematic diagram showing a gasification system according to an eighth embodiment of the present invention.
- FIG. 1 is a schematic diagram explanatory of principles of a gasification system according to the present invention.
- the gasification system shown in FIG. 1 has a gasification furnace 1 with a fluidized bed and a combustion furnace 2.
- various wastes and combustibles such as biomass are supplied into the gasification furnace 1, where the wastes and biomass are gasified (or pyrolyzed) to produce a combustible gas and char.
- the valuable combustible gas produced by gasification (or pyrolysis) in the gasification furnace 1 is utilized for power recovery or energy recovery, or used as a raw material for chemosynthesis- Char and tar as residues produced by gasification (or pyrolysis) in the gasification furnace 1 are introduced into the combustion furnace 2, where the char and tar are combusted by oxygen supplied into the combustion furnace 2.
- Sensible heat produced by combustion in the combustion furnace 2 is utilized as a heat source for gasification in the gasification furnace 1. Because the char and tar introduced into the combustion furnace 2 mainly contain carbon, combustion in the combustion furnace 2 produces a combustion gas containing CO 2 as a principal component. A portion of the combustion gas produced in the combustion furnace 2 is returned as a fluidizing gas to the combustion furnace 2.
- the rest of the combustion gas is returned as a fluidizing gas to the gasification furnace 1.
- a booster 3 is provided to return the combustion gas produced in the combustion furnace 2 to the combustion furnace 2 and the gasification furnace 1. Since the booster 3 is thus employed in the gasification system, a heat exchanger 4 for cooling the combustion gas and a dust collector 5 for removing dust from the combustion gas are provided downstream of the combustion furnace 2.
- the combustion gas returned to the combustion furnace 2 serves to fluidize a bed material in the combustion furnace 2 and to dilute oxygen so as to prevent local combustion in the combustion furnace 2.
- the amount of combustion gas to be returned to the combustion furnace 2 is adjusted so that the combustion furnace 2 maintains a fluidized state proper to combust char and tar in a fluidized bed of the combustion furnace 2.
- the amount of oxygen supplied to the combustion furnace 2 is slightly larger than a theoretical amount of oxygen required for stable combustion of char and tar. If oxygen is excessively supplied to the combustion furnace 2, the concentration of oxygen in the combustion gas is increased so that the combustion gas partly returned to the gasification furnace 1 combusts the combustible gas in the gasification furnace 1. Thus, the quality (or calorie) of the combustible gas is adversely lowered. It is desirable that the concentration of oxygen in the combustion gas should be 5 % or less, preferably 1 % or less. As described above, a portion of the combustion gas discharged from the combustion furnace 2 is returned to the combustion furnace 2.
- the amount of combustion gas to be returned to the combustion furnace 2 is adjusted so as to be proper for fluidization in the combustion furnace 2 and dilution of oxygen in the combustion furnace 2.
- the rest of the combustion gas is supplied to the gasification furnace 1. Specifically, no combustion gas is released to an atmosphere from the combustion furnace 2. Since no combustion gas is released to an atmosphere through a chimney, it does not matter whether the combustion gas contains CO. For example, CO may be produced by local incomplete combustion due to low combustion temperatures.
- the combustion gas supplied to the gasification furnace 1 serves to fluidize a bed material in the gasification furnace 1.
- the bed material may include at least one of silica sand and catalyst particles.
- an excessive combustion gas may be supplied downstream of the fluidized bed in the gasification furnace 1.
- an excessive combustion gas may be returned to a freeboard of the gasification furnace 1.
- the combustion gas lowers the temperature of the freeboard to lower a pyrolysis rate of tar. Therefore, the concentration of tar in the valuable combustible gas may be increased so as to cause troubles such as attachment of tar.
- the combustion gas bypasses the gasification furnace 1 so as to be supplied to a stage downstream of the gasification furnace 1, at which the produced gas has been cooled.
- the amount of combustion gas to be supplied to the gasification furnace 1 is larger than an amount proper to be supplied as a fluidizing gas to the gasification furnace 1, i.e., when wastes have low heating values and the amount of combustion is large, an excessive combustion gas may be adsorbed and fixed so that CO 2 is fixed.
- the combustion gas in the gasification system according to the present invention has a higher concentration of CO 2 as compared to an exhaust gas discharged from conventional combustion furnaces, incineration furnaces, boilers, or gasification and slagging combustion furnaces.
- the combustion gas in the gasification system according to the present invention contains no nitrogen and has a low moisture concentration. Therefore, the combustion gas in the gasification system according to the present invention is effective in fixing CO 2 . If the amount of excessive combustion gas is so large that the produced gas is excessively diluted by the excessive combustion gas, then a catalyst packed tower having a catalyst such as CaO, MgO, or K 2 O for absorbing carbon dioxide or a wet gas absorber for absorbing carbon dioxide may be provided in a produced gas line to absorb carbon dioxide so as to increase the concentration of the combustible gas in the produced gas.
- a catalyst packed tower having a catalyst such as CaO, MgO, or K 2 O for absorbing carbon dioxide or a wet gas absorber for absorbing carbon dioxide may be provided in a produced gas line to absorb carbon dioxide so as to increase the concentration of the combustible gas in the produced gas.
- the combustion gas may be cooled to condense moisture in the combustion gas and thus reduce the volume of the gas so as to increase the concentration of the combustible gas in the produced gas.
- the amount of combustion gas produced becomes large.
- a gas cooling apparatus 7 may be provided upstream of the booster 3 to cool the combustion gas.
- the gas cooling apparatus 7 moisture in the combustion gas is condensed and removed to an exterior of the system. Accordingly, the volume of the gas is reduced so as to increase the concentration of the combustible gas in the produced gas.
- a scrubber (gas cooling apparatus) 8 may be provided to cool the combustible gas. With the scrubber 8, moisture in the combustible gas is condensed and removed to an exterior of the system.
- the gasification system according to the present invention can be applied to wastes having low heating values.
- the amount of combustion gas to be supplied to the gasification furnace 1 is smaller than an amount proper to be supplied as a fluidizing gas to the gasification furnace 1, i.e., when wastes have high heating values and the amount of combustion is small, a fluidizing gas tends to be insufficient in the gasification furnace 1.
- steam (water vapor) or inert gas such as nitrogen or CO 2 may be supplied to the gasification furnace 1 to compensate an insufficient fluidizing gas.
- water discharged from a scrubber may be sprayed on a gas discharged from the combustion furnace 2 to produce steam for a fluidizing gas.
- contaminants in the water become dry ash, which is trapped by the dust collector 5 such as a bag filter.
- Waste water discharged from various processes e.g., waste water from a waste supply device with squeezing wastes to remove water content from the wastes or waste water from a waste pit, may be sprayed on a gas discharged from the combustion furnace 2 for cooling the gas.
- the fluidizing gas of the gasification furnace 1 is heated, the amount of combustion in the combustion furnace 2 can be reduced. Thus, it is possible to obtain the same advantages as in a case where a raw material has a high heating value.
- Catalyst particles may be mixed into the fluidized beds in the gasification furnace 1 and the combustion furnace 2.
- the catalyst particles serve to decompose tar and remove toxic substances under a reducing atmosphere having a low temperature in the gasification furnace 1.
- the catalyst particle may include MgO, iron oxide, Al 2 O 3 , zeolite, CaO, or a catalyst having a noble metal, such as Ni or Co.
- the catalyst particles are regenerated under an oxidizing atmosphere having a high temperature in the combustion furnace 2 so as to recover deteriorated functions of the catalyst particles.
- FIG. 3 is a schematic diagram showing a gasification system according to a first embodiment of the present invention. As shown in FIG.
- the gasification system has an integrated gasification furnace 11 including a gasification chamber 12 and a combustion chamber 13- Wastes (combustibles) are supplied into the gasification chamber 12, where the wastes are gasified (or pyrolyzed) to produce a combustible gas and char- Char and tar as residues produced by gasification (or pyrolysis) are introduced into the combustion chamber 13, where the char and tar are combusted by oxygen supplied into the combustion chamber 13.
- the gasification chamber 12 includes a fluidized bed having a temperature of 350 to 950°C. A combustion gas produced in the combustion chamber 13 is supplied as a fluidizing gas into the gasification chamber 12.
- the amount of combustion gas to be supplied to the gasification chamber 12 is adjusted so that the gasification chamber 12 maintains a proper fluidized state.
- the proper fluidized state is defined as a state in which the following conditions are met:
- the raw material is mixed with the bed material in the fluidized bed and dispersed uniformly.
- the temperature of the fluidized bed is uniform.
- a sufficient amount of bed material is circulated.
- steam or inert gas such as nitrogen or CO 2 may be supplied as a fluidizing gas to the gasification chamber 12 in addition to the combustion gas.
- the amount of steam or inert gas to be supplied to the gasification chamber 12 is adjusted so that the gasification chamber 12 maintains a proper fluidized state.
- the combustion gas from the combustion chamber 13 may be supplied to a freeboard of the gasification chamber 12-
- a produced gas is discharged from the gasification chamber 12 into a dust collector 14 such as a cyclone, where dust is removed from the produced gas.
- the produced gas is discharged from the dust collector 14 into a scrubber 15.
- the scrubber 15 the produced gas is cooled, and toxic substances such as acid gas and tar are removed from the produced gas.
- the produced gas discharged from the scrubber 15 is utilized as a fuel gas or the like. Waste water from the scrubber 15 is treated in a waste water treatment facility 16.
- Char and tar as residues produced by gasification (or pyrolysis) in the gasification chamber 12 are introduced into the combustion chamber 13, which includes a fluidized bed having a temperature of 600 to 1000°C.
- the combustion gas is discharged from the combustion chamber 13 into a boiler 17.
- the combustion gas is cooled, and a portion of dust in the combustion gas is removed.
- Steam is produced in the boiler 17 by heat recovery and supplied to a steam turbine power generator 18 to generate electric power.
- the combustion gas is discharged from the boiler 17 into a bag filter 19, where dust in the combustion gas is collected.
- the combustion gas discharged from the bag filter 19 is returned through a booster 20 to the gasification chamber 12 and the combustion chamber 13.
- the combustion chamber 13 is supplied with oxygen-containing gas such as oxygen, oxygen-enriched air, air, or mixed gas of oxygen and steam.
- the combustion chamber 13 is also supplied with the combustion gas as a fluidizing gas from the booster 20.
- the amounts of oxygen and combustion gas to be supplied to the combustion chamber 13 are adjusted so that the combustion chamber 13 maintains a proper fluidized state, and that the combustion gas has an oxygen concentration of 5 % or less, preferably 1 % or less.
- Catalyst particles may be mixed into the fluidized beds in the gasification chamber 12 and the combustion chamber 13. The catalyst particles serve to decompose tar and remove toxic substances under a reducing atmosphere having a low temperature in the gasification chamber 12.
- the catalyst particle may include MgO, iron oxide, Al 2 O 3 , zeolite, CaO, or a catalyst having a noble metal, such as Ni or Co.
- the catalyst particles are regenerated under an oxidizing atmosphere having a high temperature in the combustion chamber 13 so as to recover deteriorated functions of the catalyst particles- Ash is collected by the dust collector 14 such as a cyclone in a produced gas line and by the boiler 17 and the bag filter 19 in a combustion gas line and then stored in an ash reservoir tank 21.
- a slagging combustion furnace 22 may additionally be provided as optional equipment.
- the slagging combustion furnace 22 is supplied with ash stored in the ash reservoir tank 21, a portion of the fuel gas in the produced gas line, and a portion of the combustion gas which has been discharged from the booster 20 in the combustion gas line (if the produced gas is required to be diluted) and also with oxygen.
- the fuel gas is combusted and heated above an ash melting temperature to melt ash into slag.
- the slagging combustion furnace 22 may have a temperature of 1000 to 1400°C, preferably at least 1200°C.
- the ash melted into slag is discharged to the exterior of the system.
- the combustion gas discharged from the slagging combustion furnace 22 is returned to the combustion chamber 13.
- the combustion gas discharged from the slagging combustion furnace 22 may be treated in a conventional gas treatment facility (not shown) which is separately provided.
- a conventional gas treatment facility has a heat recovery device such as a boiler to lower the temperature of a combustion gas, an adsorbent spraying device for spraying an adsorbent such as hydrated lime or activated carbon on the combustion gas to remove hydrogen chloride and dioxin from the combustion gas, a bag filter for collecting particles in the gas, a denitrogenation catalyst tower for removing nitrogenous compounds from the combustion gas, and a chimney.
- the amount of gas introduced into the slagging combustion furnace 22 is smaller than the amount of gas introduced into a conventional gasification and slagging combustion furnace.
- FIG. 4 is a schematic diagram showing a gasification system according to a second embodiment of the present invention. As shown in FIG.
- the gasification system has an integrated gasification furnace 11 including a gasification chamber 12 and a combustion chamber 13. Wastes (combustibles) are supplied into the gasification chamber 12, where the wastes are gasified (or pyrolyzed) to produce a combustible gas and char. Char and tar as residues produced by gasification (or pyrolysis) are introduced into the combustion chamber 13, where the char and tar are combusted by oxygen supplied into the combustion chamber 13.
- the gasification chamber 12 includes a fluidized bed having a temperature of 350 to 950°C. A combustion gas produced in the combustion chamber 13 is supplied as a fluidizing gas into the gasification chamber 12.
- the amount of combustion gas to be supplied to the gasification chamber 12 is adjusted so that the gasification chamber 12 maintains a proper fluidized state.
- steam or inert gas such as nitrogen or CO 2 may be supplied as a fluidizing gas to the gasification chamber 12 in addition to the combustion gas.
- the amount of steam or inert gas to be supplied to the gasification chamber 12 is adjusted so that the gasification chamber 12 maintains a proper fluidized state.
- the combustion gas from the combustion chamber 13 may be supplied to a freeboard of the gasification chamber 12.
- a produced gas is discharged from the gasification chamber 12 into a dust collector 14 such as a cyclone, where dust is removed from the produced gas.
- the produced gas is discharged from the dust collector 14 into a scrubber 15.
- the scrubber 15 the produced gas is cooled, and toxic substances such as acid gas and tar are removed from the produced gas.
- the produced gas discharged from the scrubber 15 is utilized as a fuel gas or the like.
- Char and tar as residues produced by gasification (or pyrolysis) in the gasification chamber 12 are introduced into the combustion chamber 13, which includes a fluidized bed having a temperature of 600 to 1000°C.
- the combustion gas is discharged from the combustion chamber 13 into a gas cooler 23.
- the gas cooler 23 the combustion gas is cooled, and a portion of dust in the combustion gas is removed.
- water discharged from the scrubber 15 is sprayed on the combustion gas to cool the combustion gas and produce steam.
- Waste water discharged from various processes may be sprayed on a gas discharged from the combustion chamber 13 for cooling the gas.
- a required amount of make-up water is supplied to the scrubber 15.
- the combustion gas and the steam are discharged from the gas cooler 23 into a bag filter 19, where dust in the combustion gas is collected.
- the combustion gas discharged from the bag filter 19 is returned through a booster 20 to the gasification chamber 12 and the combustion chamber 13.
- the combustion chamber 13 is supplied with oxygen-containing gas such as oxygen, oxygen-enriched air, air, or mixed gas of oxygen and steam.
- the combustion chamber 13 is also supplied with the combustion gas as a fluidizing gas from the booster 20.
- the amounts of oxygen and combustion gas to be supplied to the combustion chamber 13 are adjusted so that the combustion chamber 13 maintains a proper fluidized state, and that the combustion gas has an oxygen concentration of 5 % or less, preferably 1 % or less.
- Catalyst particles may be mixed into the fluidized beds in the gasification chamber 12 and the combustion chamber 13.
- the catalyst particles serve to decompose tar and remove toxic substances under a reducing atmosphere having a low temperature in the gasification chamber 12.
- the catalyst particle may include MgO, iron oxide, Al 2 O 3 , zeolite, CaO, or a catalyst having a noble metal, such as Ni or Co.
- the catalyst particles are regenerated under an oxidizing atmosphere having a high temperature in the combustion chamber 13 so as to recover deteriorated functions of the catalyst particles.
- Ash is collected by the dust collector 14 such as a cyclone in a produced gas line and by the gas cooler 23 and the bag filter 19 in a combustion gas line and then stored in an ash reservoir tank 21.
- a slagging combustion furnace 22 may additionally be provided as optional equipment.
- the slagging combustion furnace 22 is supplied with ash stored in the ash reservoir tank 21, a portion of the fuel gas in the produced gas line, and a portion of the combustion gas which has been discharged from the booster 20 in the combustion gas line (if the produced gas is required to be diluted) and also with oxygen- In the slagging combustion furnace 22, the fuel gas is combusted and heated above an ash melting temperature to melt ash into slag-
- the slagging combustion furnace 22 may have a temperature of 1000 to 1400°C, preferably at least 1200°C.
- the ash melted into slag is discharged to the exterior of the system.
- the combustion gas discharged from the slagging combustion furnace 22 is returned to the combustion chamber 13.
- the combustion gas discharged from the slagging combustion furnace 22 may be treated in a conventional gas treatment facility (not shown) which is separately provided.
- steam can be supplied to the fluidizing gas by the gas cooler 23 provided on the combustion gas line. Therefore, it becomes unnecessary to provide a boiler as shown in FIG. 3.
- the gas cooler 23 does not require tap water, and thus water discharged from the scrubber 15 can be used in the gas cooler 23.
- chlorine compounds and sulfur compounds contained in a gas produced in the gasification chamber 12 are absorbed and removed, and absorption catalysts such as calcium compounds are used as at least a portion of medium particles to purify the produced gas.
- absorption catalysts such as calcium compounds are used as at least a portion of medium particles to purify the produced gas.
- the gasification system has an integrated gasification furnace 11 including a gasification chamber 12 and a combustion chamber 13. Wastes (combustibles) are supplied into the gasification chamber 12, where the wastes are gasified (or pyrolyzed) to produce a combustible gas and char. Char and tar as residues produced by gasification (or pyrolysis) are introduced into the combustion chamber 13, where the char and tar are combusted by oxygen supplied into the combustion chamber 13.
- the gasification chamber 12 includes a fluidized bed having a temperature of 350 to 950°C. A combustion gas produced in the combustion chamber 13 is supplied as a fluidizing gas into the gasification chamber 12.
- the amount of combustion gas to be supplied to the gasification chamber 12 is adjusted so that the gasification chamber 12 maintains a proper fluidized state.
- steam or inert gas such as nitrogen or CO 2 may be supplied as a fluidizing gas to the gasification chamber 12 in addition to the combustion gas.
- the amount of steam or inert gas to be supplied to the gasification chamber 12 is adjusted so that the gasification chamber 12 maintains a proper fluidized state.
- the combustion gas from the combustion chamber 13 may be supplied to a freeboard of the gasification chamber 12.
- a produced gas is discharged from the gasification chamber 12 into a dust collector 14 such as a cyclone, where dust is removed from the produced gas.
- the produced gas is discharged from the dust collector 14 into a scrubber 15.
- the scrubber 15 the produced gas is cooled, and toxic substances such as acid gas and tar are removed from the produced gas.
- the produced gas discharged from the scrubber 15 is utilized as a fuel gas or the like.
- Char and tar as residues produced by gasification (or pyrolysis) in the gasification chamber 12 are introduced into the combustion chamber 13, which includes a fluidized bed having a temperature of 600 to 1000°C-
- the combustion gas is discharged from the combustion chamber 13 through a fluidizing gas heater 24 into a gas cooler 23. In the fluidizing gas heater 24 and the gas cooler 23, the combustion gas is cooled. In the gas cooler 23, water discharged from the scrubber 15 is sprayed on the combustion gas to cool the combustion gas and produce steam.
- the combustion gas and the steam are discharged from the gas cooler 23 into a bag filter 19, where dust in the combustion gas is collected.
- the combustion gas and the steam discharged from the bag filter 19 are supplied through a booster 20 to the fluidizing gas heater 24, where the combustion gas and the steam are heated by heat exchange with the combustion gas discharged from the combustion chamber 13. Then, the combustion gas and the steam are returned to the gasification chamber 12 and the combustion chamber 13.
- the combustion chamber 13 is supplied with oxygen-containing gas such as oxygen, oxygen-enriched air, air, or mixed gas of oxygen and steam.
- the combustion chamber 13 is also supplied with the combustion gas as a fluidizing gas from the booster 20.
- the amounts of oxygen and combustion gas to be supplied to the combustion chamber 13 are adjusted so that the combustion chamber 13 maintains a proper fluidized state, and that the combustion gas has an oxygen concentration of 5 % or less, preferably 1 % or less.
- Catalyst particles may be mixed into the fluidized beds in the gasification chamber 12 and the combustion chamber 13.
- the catalyst particles serve to decompose tar and remove toxic substances under a reducing atmosphere having a low temperature in the gasification chamber 12.
- the catalyst particle may include MgO, iron oxide, Al 2 O 3 , zeolite, CaO, or a catalyst having a noble metal, such as Ni or Co.
- the catalyst particles are regenerated under an oxidizing atmosphere having a high temperature in the combustion chamber 13 so as to recover deteriorated functions of the catalyst particles- Ash is collected by the dust collector 14 such as a cyclone in a produced gas line and by the gas cooler 23 and the bag filter 19 in a combustion gas line and then stored in an ash reservoir tank 21.
- a slagging combustion furnace 22 may additionally be provided as optional equipment.
- the slagging combustion furnace 22 is supplied with ash stored in the ash reservoir tank 21, a portion of the fuel gas in the produced gas line, and a portion of the combustion gas which has been discharged from the booster 20 in the combustion gas line (if the produced gas is required to be diluted) and also with oxygen.
- the fuel gas is combusted and heated above an ash melting temperature to melt ash into slag.
- the slagging combustion furnace 22 may have a temperature of 1000 to 1400°C, preferably at least 1200°C.
- the ash melted into slag is discharged to the exterior of the system.
- the combustion gas discharged from the slagging combustion furnace 22 is returned to the combustion chamber 13.
- the combustion gas discharged from the slagging combustion furnace 22 may be treated in a conventional gas treatment facility (not shown) which is separately provided.
- a conventional gas treatment facility not shown
- the fluidizing gas can be heated in the fluidizing gas heater 24, it is possible to reduce the amount of combustion of a raw material (wastes), which are combusted in the gasification furnace 11, and also reduce the amount of oxygen to be supplied.
- This embodiment is particularly effective in a case where a raw material has a low heating value. Similar effects can be obtained when the concentration of oxygen in the fluidizing gas to be supplied to the combustion chamber 13 is increased.
- FIG. 6 is a schematic diagram showing a gasification system according to a fourth embodiment of the present invention-
- the gasification system shown in FIG. 6 has a high-temperature furnace 25 disposed between the dust collector 14 and the scrubber 15 in the gasification system shown in FIG. 5.
- a produced gas is discharged from the dust collector 14 and introduced into the high-temperature furnace 25.
- the high-temperature furnace 25 is supplied with oxygen- containing gas such as oxygen, oxygen-enriched air, air, or mixed gas of oxygen and steam, and the produced gas supplied into the high-temperature furnace 25 is partly combusted.
- oxygen- containing gas such as oxygen, oxygen-enriched air, air, or mixed gas of oxygen and steam
- the produced gas supplied into the high-temperature furnace 25 is partly combusted.
- the temperature of the interior of the high-temperature furnace 25 is increased to 900 to 1400°C, preferably about 1200°C. Accordingly, tar in the produced gas is pyrolyzed into hydrogen, carbon monoxide, and low molecular hydrocarbon.
- carbon monoxide or hydrocarbon such as methane in the produced gas reacts with steam (for example, shift reaction) so as to change the composition of the produced gas. Accordingly, the produced gas can contain a large amount of hydrogen.
- the high-temperature furnace 25 has a function to adjust the composition of the produced gas. Accordingly, a fuel gas having desired composition can be obtained by adjusting conditions of the high-temperature furnace 25. A portion of ash in the produced gas is removed in the high-temperature furnace 25. Particularly, when the high-temperature furnace 25 has a temperature higher than about 1200°C, ash contained in the produced gas is melted into slag in the high-temperature furnace 25. The molten slag falls down into a tank located at a lower portion of the high-temperature furnace 25 to form granulated slag.
- the granulated slag is discharged from the high-temperature furnace 25 by a conveyer.
- the high-temperature furnace 25 has a temperature lower than about 1200°C, ash is not melted in the high-temperature furnace 25.
- the ash is recovered by an inertial dust collector in the high-temperature furnace 25 and discharged from the bottom of the high-temperature furnace 25.
- the discharged ash is delivered to the ash reservoir tank 21 and stored therein. Then, the produced gas is discharged from the high-temperature furnace 25 into the scrubber 15.
- water may be sprayed in a gas passage at an inlet of the scrubber 15, or a gas cooler such as a water spray cooler or a boiler may be provided between the high-temperature furnace 25 and the scrubber 15.
- the high-temperature furnace 25 has a water-cooled pipe disposed in a wall thereof. Water in the water-cooled pipe is heated so as to produce steam. The produced steam may be utilized as a fluidizing gas in the gasification chamber 12. Other arrangements are the same as the gasification system in the third embodiment shown in FIG. 5.
- the high-temperature furnace 25 in the fourth embodiment shown in FIG. 6 may be applied to the first, second, and third embodiments, respectively.
- tar can be removed by pyrolysis at a high temperature even if a catalyst is not used in the gasification furnace 11. Since reaction is promoted between carbon monoxide or hydrocarbon such as methane in the produced gas and steam, it is possible to change the composition of the produced gas so as to obtain a produced gas containing a large amount of hydrogen. Further, ash can be collected or recovered as slag. Furthermore, the high-temperature furnace 25 can reliably pyrolyze tar produced in the gasification chamber 12 even if catalyst particles used in the gasification chamber 12 do not have a long-lasting function of decomposing tar.
- FIG. 7 is a schematic diagram showing a gasification furnace in a gasification system according to a fifth embodiment of the present invention.
- the gasification furnace shown in FIG. 7 comprises a twin tower circulation type gasification furnace. As shown in FIG.
- the twin tower circulation type gasification furnace has two furnaces (towers) including a gasification furnace 31 and a char combustion furnace 32.
- a bed material and char are circulated between the gasification furnace 31 and the char combustion furnace 32 so as to supply sensible heat of the bed material, which is heated by combustion heat of char in the char combustion furnace 32, to the gasification furnace 31 to provide an amount of heat required for gasification.
- FIG. 7 shows only gas paths between the gasification furnace 31 and the char combustion furnace 32. However, the gasification system practically has other paths as shown in FIGS. 3 through 6.
- wastes are supplied into the gasification furnace 31, where the wastes are gasified (or pyrolyzed) to produce a combustible gas and char.
- the gasification furnace 31 includes a fluidized bed having a temperature of 350 to 950°C.
- a gas produced in the gasification furnace 31 is accompanied with char and a bed material, which are introduced into a cyclone 33.
- gas-solid separation is performed, and the char and the bed material are returned to the char combustion furnace 32.
- the produced gas from which a portion of dust has been removed in the cyclone 33, is utilized as a fuel gas.
- char and tar as residues produced by gasification (or pyrolysis) in the gasification furnace 31 are introduced into the combustion furnace 32, where the char and tar are combusted by oxygen supplied into the combustion furnace 32.
- the combustion furnace 32 includes a fluidized bed having a temperature of 600 to 1000°C.
- a combustion gas discharged from the char combustion furnace 32 is accompanied with a bed material, which is introduced into a cyclone 34.
- gas-solid separation is performed, and the bed material is returned to the gasification furnace 31.
- the combustion gas discharged from the cyclone 34 is supplied through a drier 35 to the gasification furnace 31.
- wastes such as biomass are dried to provide a raw material.
- Oxygen is introduced into the char combustion furnace 32.
- a portion of the combustion gas discharged from the char combustion furnace 32 is also introduced into the char combustion furnace 32.
- a portion of the combustion gas discharged from the char combustion furnace 32 is supplied into the gasification furnace 31.
- steam or inert gas such as nitrogen or CO 2 is supplied into the gasification furnace 31 when the fluidizing gas is insufficient.
- FIG. 8 is a schematic diagram showing a gasification system according to a sixth embodiment of the present invention.
- the gasification system shown in FIG. 8 employs a catalyst (e.g. Al 2 O 3 ) to reform a gas (or decompose tar).
- the gasification system employs char combustion heat as heat for regenerating a deteriorated catalyst.
- the gasification system has a gasification furnace 71 and a combustion furnace 72 for combusting char (unburned carbon combustibles) produced by gasification of a raw material.
- Heat of a combustion exhaust gas produced by combustion of the char in the combustion furnace 72 is supplied to a catalyst regeneration device 73 as heat for regenerating a deteriorated catalyst.
- a raw material is supplied into the gasification furnace 71 having a temperature of 350 to 950°C, where the raw material is gasified (or pyrolyzed) to produce a combustible gas and char.
- the combustible gas produced by gasification of the raw material in the gasification furnace 71 is introduced into a gas reforming device 74, where the gas is reformed (or tar is decomposed).
- the gas reforming device 74 includes a catalyst bed having a temperature of 600 to 950°C.
- Tar and char as residues produced by gasification (or pyrolysis) in the gasification furnace 71 are introduced into the combustion furnace 72 having a temperature of 650 to 1000°C, where the tar and char are combusted by oxygen supplied into the combustion furnace 72.
- FIG. 8 shows only gas paths between the gasification furnace 71 and the combustion furnace 72. However, the gasification system practically has other paths as shown in FIGS. 3 through 6.
- gas reformation or tar decomposition
- a catalyst function of the catalyst in the gas reforming device 74 is somewhat deteriorated due to deposition of carbon or the like.
- the catalyst in the gas reforming device 74 is supplied to the gasification furnace 71.
- the catalyst supplied into the gasification furnace 71 performs gas reformation (or tar decomposition) on a gas produced by gasification (or pyrolysis) in the gasification furnace 71, a catalyst function of the catalyst is considerably deteriorated due to deposition of carbon or the like.
- the catalyst in the gasification furnace 71 is supplied to the catalyst regeneration device 73-
- the catalyst regeneration device 73 heats the deteriorated catalyst with the combustion exhaust gas from the combustion furnace 72 to 700 to 1000°C so as to regenerate the catalyst and introduces the regenerated catalyst into the gas reforming device 74.
- Oxygen is supplied to the combustion furnace 72 to combust char.
- a combustion gas (containing oxygen) produced by combustion of the char in the combustion furnace 72 is introduced into the catalyst regeneration device 73, where the catalyst is regenerated by heat of the combustion gas-
- An exhaust gas discharged from the catalyst regeneration device 73 is supplied to the gas reforming device 74, the gasification furnace 71, and the combustion furnace 72.
- FIG. 9 is a schematic diagram showing a gasification system according to a seventh embodiment of the present invention.
- FIG. 9 shows another arrangement of an integrated gasification furnace.
- the integrated gasification furnace has a gasification chamber 81, a collector 82, and a combustion chamber 83. For purposes of illustration, FIG.
- the gasification chamber 81 comprises a fluidized-bed furnace having a temperature of 350 to 950°C.
- the combustion chamber 83 comprises a fluidized-bed furnace having a temperature of 600 to 1000°C. Wastes (combustibles) are supplied into a bed in the gasification chamber 81, where gasification (or pyrolysis) of the wastes and decomposition and reformation of the produced gas are performed. Char and tar produced in the gasification chamber 81 flow into the combustion chamber 83 together with a bed material.
- the combustion chamber 83 has a dense fluidized bed or a fast fluidized bed formed at a lower portion thereof.
- the combustion chamber 83 When the combustion chamber 83 has a dense fluidized bed at a lower portion thereof, a fluidizing gas is supplied from an upper portion of the dense fluidized bed to form a fast fluidized bed at an upper portion of the combustion chamber 83.
- the combustion chamber 83 is supplied with a gas containing oxygen required for combustion-
- a combustion gas produced in the combustion chamber 83 flows into the collector 82 together with a bed material.
- scattering particles are collected, and a combustion gas is separated from the scattering particles.
- the collector 82 shown in FIG. 9 comprises a cyclone dust collector utilizing centrifugal forces. A portion of the combustion gas separated in the collector 82 is returned to the combustion chamber 83.
- the amount of combustion gas to be returned to the combustion chamber 83 is adjusted so as to be proper for fluidization in the combustion chamber 83 and dilution of oxygen in combustion chamber 83.
- the rest of the combustion gas is supplied to the gasification chamber 81 as a fluidizing gas. If the combustion gas is excessively supplied to the gasification chamber 81 as a fluidizing gas, then an excessive amount of combustion gas is supplied to a freeboard of the gasification chamber 81. If the combustion gas is insufficiently supplied to the gasification chamber 81 as a fluidizing gas, then steam or inert gas such as nitrogen or CO 2 is supplied to the gasification chamber 81. Specifically, no combustion gas is released to an atmosphere from the integrated gasification furnace shown in FIG. 9.
- the scattered particles which have been collected flow through a loop seal into the gasification chamber 81.
- Material sealing effects of the scattered particles in the loop seal prevent the produced gas and the combustion gas from mixing with each other.
- the scattered particles in the loop seal may be fluidized. In this case, it is desirable to use steam or inert gas such as nitrogen or CO 2 as a fluidizing gas in the loop seal.
- the gasification chamber 81 uses catalyst particles as at least a portion of bed materials, a gas produced by pyrolysis gasification of a raw material in the fast fluidized bed of the gasification chamber 81 is decomposed and reformed. During this process, carbon or the like is deposited on surfaces of catalyst particles, and combusted and removed in the combustion chamber 83.
- FIG. 10 is a schematic diagram showing a gasification system according to an eighth embodiment of the present invention.
- the gasification system shown in FIG. 10 has a gasification furnace 91, a combustion furnace 92, and a heat recovery furnace 93.
- FIG. 10 shows only gas paths between the gasification furnace 91, the combustion furnace 92, and the heat recovery furnace 93.
- the gasification furnace 91 comprises a fluidized-bed furnace having a temperature of 350 to 950°C.
- the combustion furnace 92 comprises a fluidized-bed furnace having a temperature of 600 to 1000°C.
- the heat recovery furnace 93 comprises a fluidized-bed furnace. Wastes are supplied to the gasification furnace 91, where the wastes are gasified (or pyrolyzed) to produce a combustible gas and char as a pyrolysis residue.
- the combustible gas is utilized as a fuel gas.
- Char is supplied into the combustion furnace 92 together with a bed material.
- the combustion furnace 92 is supplied with oxygen.
- Char supplied from the gasification furnace 91 is combusted in the combustion furnace 92.
- the combustion gas discharged from the combustion furnace 92 is returned to the combustion furnace 92, the gasification furnace 91, and the heat recovery furnace 93, respectively-
- the same amount of bed material as a bed material supplied from the gasification furnace 91 into the combustion furnace 92 is supplied to the heat recovery furnace 93.
- the heat recovery furnace 93 has a heat transfer pipe disposed in a fluidized bed of the heat recovery furnace 93. Water in the heat transfer pipe is heated so as to produce steam.
- the combustion gas supplied from the combustion furnace 92 into the heat recovery furnace 93 as a fluidizing gas is discharged from the heat recovery furnace 93 and returned to the combustion furnace 92-
- the same amount of bed material as a bed material supplied from the combustion furnace 92 into the heat recovery furnace 93 is supplied from the heat recovery furnace 93 to the gasification furnace 91.
- the combustion gas discharged from the combustion furnace 92 is returned to the gasification furnace 91 as a fluidizing gas. If the combustion gas is insufficiently discharged from the combustion furnace 92 as a fluidizing gas to the gasification furnace 91, then water vapor (steam) or inert gas such as nitrogen or CO 2 is supplied to the gasification furnace 91.
- the gasification system since no combustion gas is released to an atmosphere from the gasification system, the gasification system does not need any chimneys. According to the eighth embodiment, since no exhaust gas is released to an atmosphere from the gasification system, the gasification system does not contaminate the atmosphere. Further, it is possible to simplify an exhaust gas treatment facility. Furthermore, the gasification system does not need any chimneys and can achieve a clean system. Further, chlorine compounds and sulfur compounds contained in a gas produced in the gasification furnace 91 are absorbed and removed, and absorption catalysts such as calcium compounds are used as at least a portion of medium particles to purify the produced gas. Thus, it is possible to reduce the concentration of toxic components in the produced gas to be discharged.
- the present invention is suitable for use in a gasification system for gasifying various wastes such as municipal solid wastes, industrial wastes, and waste plastics, biomass, and combustible materials such as coal and refuse-derived fuel (RDF) in a gasification furnace or chamber and recovering a valuable combustible gas produced by gasification.
- wastes such as municipal solid wastes, industrial wastes, and waste plastics, biomass, and combustible materials
- RDF refuse-derived fuel
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Gasification And Melting Of Waste (AREA)
- Processing Of Solid Wastes (AREA)
- Chimneys And Flues (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003280471 | 2003-07-25 | ||
| PCT/JP2004/010870 WO2005010436A1 (en) | 2003-07-25 | 2004-07-23 | Gasification system |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP1649217A1 true EP1649217A1 (de) | 2006-04-26 |
Family
ID=34100869
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP04748078A Withdrawn EP1649217A1 (de) | 2003-07-25 | 2004-07-23 | Vergasungssystem |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20060137579A1 (de) |
| EP (1) | EP1649217A1 (de) |
| JP (1) | JP2007528974A (de) |
| CA (1) | CA2532022A1 (de) |
| WO (1) | WO2005010436A1 (de) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1696177A1 (de) * | 2005-02-28 | 2006-08-30 | Drechsler, Daniel | Integriertes Mehrbrennstoff- Vergasungsverfahren |
| US20070266914A1 (en) * | 2006-05-18 | 2007-11-22 | Graham Robert G | Method for gasifying solid organic materials and apparatus therefor |
| JP4875536B2 (ja) * | 2007-05-07 | 2012-02-15 | 株式会社タクマ | クロムを含有する燃料の焼却飛灰からの6価クロム溶出抑制方法及びこれに用いる燃焼装置 |
| CN101896581B (zh) * | 2007-12-12 | 2014-08-27 | 奥图泰有限公司 | 生产焦炭和燃料气的方法和装置 |
| JP5309620B2 (ja) * | 2008-03-10 | 2013-10-09 | 株式会社Ihi | ガス化設備のタール改質方法及び装置 |
| JP5476777B2 (ja) * | 2009-04-16 | 2014-04-23 | 株式会社Ihi | ガス化設備の二酸化炭素回収方法及び装置 |
| JP5762714B2 (ja) * | 2010-10-04 | 2015-08-12 | 株式会社キンセイ産業 | 乾溜ガス化焼却処理装置 |
| SI23732A (sl) * | 2011-05-09 | 2012-11-30 | KIV@KOVINSKA@INDUSTRIJA@VRANSKO@d@d | Naprava in postopek za uplinjanje |
| KR101209191B1 (ko) | 2012-05-22 | 2012-12-06 | 주식회사 동방환경기연 | 수분이 함량된 고체연료의 건류 연소장치 |
| ES2411101B2 (es) * | 2013-05-21 | 2013-10-22 | Urbaser S. A. | Procedimiento para convertir la fracción CDR en un gas de síntesis |
| CN103486578B (zh) * | 2013-09-16 | 2015-12-09 | 云南天安化工有限公司 | 一种液氮洗尾气催化燃烧的装置及方法 |
| JP6327698B2 (ja) * | 2014-02-20 | 2018-05-23 | 国立研究開発法人産業技術総合研究所 | 循環流動層ガス化システム |
| KR101428452B1 (ko) * | 2014-04-18 | 2014-08-08 | 한솔이엠이(주) | 순환유동층연소로를 이용한 폐자원 연소방법 |
| WO2016156261A1 (en) * | 2015-03-30 | 2016-10-06 | Sabic Global Technologies B.V. | Wet scrubbing high rubber graft abs particulate vent vapors |
| FI127753B (en) | 2017-06-09 | 2019-01-31 | Bioshare Ab | Recycling of chemicals from fuel streams |
| US10538706B2 (en) * | 2017-08-30 | 2020-01-21 | Circular Resources (Ip) Pte Limited | Waste processing system |
| BE1025691B1 (nl) * | 2017-11-08 | 2019-06-11 | Europem Technologies Nv | Een verbrandingsproces en een ovensysteem voor het verbranden van organische stoffen |
| JP7424861B2 (ja) * | 2020-02-28 | 2024-01-30 | 荏原環境プラント株式会社 | 原料の処理装置 |
| JP7627562B2 (ja) | 2020-10-21 | 2025-02-06 | 三機工業株式会社 | ガス化システムおよびガス化炉の運転方法 |
| JP2025158660A (ja) * | 2024-04-05 | 2025-10-17 | 荏原環境プラント株式会社 | 熱分解ガス化方法 |
| JP2025158653A (ja) * | 2024-04-05 | 2025-10-17 | 荏原環境プラント株式会社 | 熱分解ガス化システム |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4231303A (en) * | 1978-10-31 | 1980-11-04 | Showa Denki K.K. | Method for incineration of organic chlorine compound and incinerator used therefor |
| US4411204A (en) * | 1981-12-07 | 1983-10-25 | Combustion Engineering, Inc. | Method of firing a pulverized fuel-fired steam generator |
| US5411714A (en) * | 1992-04-06 | 1995-05-02 | Wu; Arthur C. | Thermal conversion pyrolysis reactor system |
| DE4235412A1 (de) * | 1992-10-21 | 1994-04-28 | Metallgesellschaft Ag | Verfahren zum Vergasen von brennbare Bestandteile enthaltenden Abfallstoffen |
| WO1998010225A1 (en) * | 1996-09-04 | 1998-03-12 | Ebara Corporation | Rotary fusing furnace and method for gasifying wastes using the rotating fusing furnace |
| JP3936115B2 (ja) * | 1999-03-12 | 2007-06-27 | 宇部興産株式会社 | 廃棄物ガス化処理におけるガスと排水と微粒スラグのリサイクル方法 |
| JP3990897B2 (ja) * | 2001-11-19 | 2007-10-17 | 株式会社荏原製作所 | ガス供給装置及びガス供給方法 |
-
2004
- 2004-07-23 EP EP04748078A patent/EP1649217A1/de not_active Withdrawn
- 2004-07-23 US US10/563,434 patent/US20060137579A1/en not_active Abandoned
- 2004-07-23 CA CA002532022A patent/CA2532022A1/en not_active Abandoned
- 2004-07-23 WO PCT/JP2004/010870 patent/WO2005010436A1/en not_active Ceased
- 2004-07-23 JP JP2006519243A patent/JP2007528974A/ja active Pending
Non-Patent Citations (1)
| Title |
|---|
| See references of WO2005010436A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2532022A1 (en) | 2005-02-03 |
| US20060137579A1 (en) | 2006-06-29 |
| WO2005010436A1 (en) | 2005-02-03 |
| JP2007528974A (ja) | 2007-10-18 |
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