US20090126271A1 - Method for gasifying solid fuel with unified gas purification and gasifier using said method - Google Patents

Method for gasifying solid fuel with unified gas purification and gasifier using said method Download PDF

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US20090126271A1
US20090126271A1 US11/916,365 US91636506A US2009126271A1 US 20090126271 A1 US20090126271 A1 US 20090126271A1 US 91636506 A US91636506 A US 91636506A US 2009126271 A1 US2009126271 A1 US 2009126271A1
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phase
reactor
gasification
gas purification
gasified
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US11/916,365
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Koubun Kyo
Takahiro Murakami
Toshiyuki Suda
Shigeru Kusama
Toshiro Fujimori
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IHI Corp
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IHI Corp
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Assigned to IHI CORPORATION reassignment IHI CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KUSAMA, SHIGERU, FUJIMORI, TOSHIRO, MURAKAMI, TAKAHIRO, SUDA, TOSHIYUKI, KYO, KOUBUN
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00Purifying combustible gases containing carbon monoxide
    • C10K1/20Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46Gasification of granular or pulverulent flues in suspension
    • C10J3/463Gasification of granular or pulverulent flues in suspension in stationary fluidised beds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46Gasification of granular or pulverulent flues in suspension
    • C10J3/54Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/58Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
    • C10J3/60Processes
    • C10J3/64Processes with decomposition of the distillation products
    • C10J3/66Processes with decomposition of the distillation products by introducing them into the gasification zone
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00Purifying combustible gases containing carbon monoxide
    • C10K1/02Dust removal
    • C10K1/026Dust removal by centrifugal forces
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00Purifying combustible gases containing carbon monoxide
    • C10K1/20Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
    • C10K1/26Regeneration of the purifying material contains also apparatus for the regeneration of the purifying material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/023Reducing the tar content
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10KPURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/04Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/18Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1807Recycle loops, e.g. gas, solids, heating medium, water
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/18Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1807Recycle loops, e.g. gas, solids, heating medium, water
    • C10J2300/1823Recycle loops, e.g. gas, solids, heating medium, water for synthesis gas

Definitions

  • the present invention relates to technique for gasifying solid fuel, and more specifically relates to technique for gasifying solid fuel highly efficiently and more cleanly.
  • the gas gasified in the high-temperatured environment is rich in CO and CO 2 and poor in H 2 ; in order to produce H 2 -enriched product gas required, for example, for a synthesizing process of GTL (Gas to Liquid), the high-temperatured gasified gas must be cooled to independently carry out CO shift reaction and removal of CO 2 .
  • a conventionally known method for concurrently removing CO during gasification of solid fuel is to absorb CO 2 in gasified gas in a gasification furnace, using a chemical such as CaO-based oxide; however, in a high-temperatured environment of 1123° K or more, there is a restriction in terms of chemical equilibrium that absorption of CO 2 requires the gasification furnace to be in a high pressure environment of 20 atm or more (see, for example, Patent References 1 and 2).
  • the gasification technique at such high pressure can be utilized practically only in large-scaled energy/fuel producing systems of several hundreds MW from a viewpoint of cost or other restrictions; in other various low-capacity systems such as a dispersed hydrogen fuel cell power and synthesis system, it has been desired that production of H 2 -enriched product gas be carried out through gasification at low or preferably normal pressure.
  • twin-circulating-fluidized-bed-type gasification technique With respect to a method for gasifying fuel through combustion of solid fuel itself (usual partial oxidation method, other method of not using a gasifying agent or auto-thermal gasification method, or other method of using a gasifying agent such as steam or CO 2 ), known is twin-circulating-fluidized-bed-type gasification technique (see, for example, Patent References 3 and 4) wherein inert gas such as CO 2 generated by combustion and N 2 fed through supply of air for combustion are prevented from being admixed in the gasified gas in such a manner that the solid fuel is gasified in the gasification furnace, the gasified char being burned in a combustion furnace separate from the gasification furnace, heat fluid medium being circulated between these gasification and combustion furnaces to transfer heat from the combustion furnace to the gasification furnace.
  • inert gas such as CO 2 generated by combustion and N 2 fed through supply of air for combustion
  • biomass is gasified in a gasification furnace adjacent to a downcomer in an environment of 873-973° K and at normal pressure, CO 2 being absorbed by CaO chemical to obtain gasified gas with high H 2 content and to accelerate the gasifying reaction, CaCO 3 thus generated being regenerated into CaO in a riser combustion furnace and being circulated to the gasification furnace together with the fluid heat medium.
  • the gasification reaction is either at high temperature of 1123° K or more (Patent References 3 and 4) or at low or medium temperature of 973° K or so (AER).
  • a catalytic function of reforming tar in gasified gas through chemical such as CaO is not compatible with a function of absorbing CO 2 in gas to accelerate gasifying reaction.
  • the invention was made in order to solve the above problems and has an object to make it possible that a function of absorbing CO 2 in gas by chemical to accelerate gasifying reaction is compatible with a catalytic function of reforming tar in gasified gas generated by the gasifying reaction and to provide a gasification method of solid fuel with unified gas purification with enabled high gasification efficiency and production of clean produced gas as well as a gasifier using said method.
  • the invention is directed to a method for gasifying solid fuel with unified gas purification, characterized in that it comprises a first process of feeding solid fuel and a gasifying agent to a reactor of pyrolysis gasification phase where said solid fuel is pyrolyzed in contact with heat medium to generate char gasified by said gasifying agent, CO 2 in gasified gas generated by said pyrolysis and gasification being absorbed by active chemical at a reaction temperature of said pyrolysis gasification phase; a second process of feeding residual char not gasified in said reactor of pyrolysis gasification phase, the heat medium low-temperatured through contribution to the pyrolysis and gasification of said solid fuel, the low-active chemical less-activated through reaction with said CO 2 and newly added inactive chemical to a reactor of char combustion phase where said char is burned by an oxidizing agent to bring about combustion heat with which said low-temperatured heat medium is heated, said low-active and inactive
  • the heat medium is heated and the low-active and newly added inactive chemicals are calcined to generate the active chemical (second process), these high-temperatured heat medium and active chemical being fed to the reactor of gasified gas purification phase where, at the high reaction temperature of the gasified gas purification phase, tar in the gasified gas is satisfactorily reformed with the active chemical functioning as catalyst, and H 2 S and HCl in the gasified gas are satisfactorily absorbed by the active chemical (third process).
  • the chemical having reformed the heat medium and tar and having absorbed H 2 S and HCl is circulated to the reactor of pyrolysis gasification phase while it possesses absorption activity of CO 2 ; in the reactor of pyrolysis gasification phase, CO 2 in gasified gas generated by the pyrolysis and gasification of the solid fuel is satisfactorily absorbed by the chemical at the low or medium reaction temperature of the pyrolysis gasification phase (first process).
  • the reaction temperature in the reactor of pyrolysis gasification phase for said pyrolysis gasification phase is controlled to 773-1073° K in harmony at least with the absorption reaction of CO 2 in the gasified gas by the active chemical.
  • reaction temperature of the pyrolysis and gasification phase in said reactor of pyrolysis gasification phase is in harmony for example with the absorption reaction of CO 2 in the gasified gas by the active chemical so that it is maintained to the low or medium temperature of 773-1073° K at which CO 2 in the gasified gas can be satisfactorily absorbed by the active chemical, so that even if the reactor of pyrolysis gasification phase is substantially at normal pressure, CO 2 in the gasified gasified gas generated by gasification is reliably absorbed by the active chemical.
  • reaction temperature in said reactor of char combustion phase can be controlled to 1073° K or more in harmony at least with re-activation and activation reactions of the low-active and inactive chemicals, respectively.
  • reaction temperature in the reactor of char combustion phase is in harmony with the re-activation and activation reactions of the low-active and inactive chemicals, respectively, and is maintained to high temperature of 1073° K or more so that the heat medium and active chemical are made sufficiently high-temperatured and the active chemical is sufficiently activated.
  • the reaction temperature in said reactor of gasified gas purification phase for said gasified gas purification phase can be controlled to the temperature of 1073° K or more in harmony at least with sufficient exhibition of the catalytic function of the active chemical to the tar reforming reaction, which is lower than the reaction temperature in the reactor of char combustion phase and higher than the reaction temperature in the reactor of pyrolysis gasification phase for the pyrolysis gasification phase.
  • reaction temperature in the reactor of gasified gas purification phase for the gasified gas purification phase is in harmony for example with exhibition of the catalytic function of the active chemical to the tar reforming reaction so that it is maintained to high temperature of 1073° K or more at which tar in the gasified gas can be satisfactorily reformed by the active chemical; the tar in the gasified gas is reliably reformed by the active chemical and at the same time H 2 S, HCl and the like are satisfactorily removed.
  • the high reaction temperature in said phase is somewhat lowered than the reaction temperature in the char combustion phase, i.e., the temperature of the particles and active chemical heated in the char combustion phase, but is reliably higher than the low or medium reaction temperature in the reactor of phase for the pyrolysis gasification phase.
  • the inactive chemical may be mineral which has, as its base, metal carbonate or hydroxide.
  • the activated active chemical such as CaO can satisfactorily absorb CO 2 in the gasified gas in the reactor of pyrolysis gasification phase and at the low or mediate reaction temperature of said phase; and in the reactor of gasified gas purification phase, it can suitably function as catalyst to satisfactorily reform the tar in the gasified gas at high reaction temperature of the phase.
  • the invention is directed to a gasifier for solid fuel with unified gas purification, characterized in that it comprises a reactor of pyrolysis gasification phase fed with the solid fuel and a gasifying agent, said solid fuel being pyrolyzed in contact with heat medium to generate char gasified by said gasifying agent, CO 2 in gasified gas generated by said pyrolysis and gasification being absorbed by active chemical at a reaction temperature of the pyrolysis and gasification; a reactor of char combustion phase fed with residual char not gasified in said reactor of pyrolysis gasification phase, the heat medium low-temperatured through contribution to the pyrolysis and gasification of said solid fuel, the low-active chemical less-activated through reaction with said CO 2 and newly added inactive chemical, said char being burned by an oxidizing agent to bring about combustion heat with which said low-temperatured heat medium is heated and said low-active and inactive chemicals are calcined to be re-activated and activated, respectively; and a reactor of pyrolysis gasification phase fed
  • the heat medium is heated and the low-active and newly added inactive chemicals are calcined to generate active chemical, so that these high-temperatured heat medium and active chemical are fed to the reactor of gasified gas purification phase where tar in the gasified gas is satisfactorily reformed with the active chemical functioning as catalyst at high reaction temperature required for tar reformation and H 2 S and HCl in the gasified gas are satisfactorily absorbed by the active chemical.
  • the chemical having reformed the tar and absorbed H 2 S and HCl is circulated together with the heat medium to the reactor of pyrolysis gasification phase while possessing the absorption activity of CO 2 , and in the reactor of pyrolysis gasification phase, CO 2 in the gasified gas generated by the pyrolysis and gasification of the solid fuel is satisfactorily absorbed by the chemical at the low or medium reaction temperature of the pyrolysis gasification required for absorption of CO 2 .
  • the reaction temperature of the pyrolysis gasification in the reactor of pyrolysis gasification phase can be controlled to 773-1073° K in harmony at least with the absorption reaction of CO 2 in the gasified gas by the active chemical.
  • the reaction temperature of the pyrolysis gasification in the reactor of pyrolysis gasification phase is in harmony for example with the absorption reaction of CO 2 in the gasified gas by the active chemical, so that it is maintained to the low or medium temperature of 773-1073° K at which CO 2 in the gasified gas can be satisfactorily absorbed by the active chemical.
  • the reactor of pyrolysis gasification phase is substantially at the normal pressure, CO 2 in the gasified gas generated by the gasification is reliably absorbed by the active chemical.
  • the reaction temperature in the reactor of char combustion phase can be controlled to 1073° K or more in harmony at least with the re-activation and activation reactions of the low-active and inactive chemicals, respectively.
  • reaction temperature in the reactor of char combustion phase is in harmony for example with the re-activation and activation reactions of the low-active and inactive chemicals, respectively, so that it is maintained to 1073° K or more.
  • the heat medium and active chemical are sufficiently high-temperatured and the active chemical is sufficiently activated.
  • the reaction temperature for tar reformation in the reactor of gasified gas purification phase can be controlled to the temperature of 1073° K or more in harmony at least with sufficient exhibition of the catalytic function of the active chemical to the tar reforming reaction, which is lower than the reaction temperature in the reactor of char combustion phase and higher than the reaction temperature in the reactor of pyrolysis gasification phase for the pyrolysis gasification.
  • reaction temperature for tar reformation in the reactor of gasified gas purification phase is in harmony for example with exhibition of the catalytic function of the active chemical to the tar reforming reaction, so that it is maintained to the high temperature of 1073° K or more at which tar in the gasified gas can be satisfactorily reformed by the active chemical.
  • the tar in the gasified gas is reliably reformed and at the same time H 2 S, HCl and the like is satisfactorily removed by the active chemical.
  • the high reaction temperature in the phase is somewhat lower than the reaction temperature in the char combustion phase, i.e., the temperature of the particles and active chemical heated in the char combustion phase, but is reliably higher than the low or medium reaction temperature for the pyrolysis gasification phase in the reactor of pyrolysis gasification phase.
  • the inactive chemical may be mineral which has, as its base, metal carbonate or hydroxide.
  • the activated active chemical such as CaO can satisfactorily absorb CO 2 in the gasified gas in the reactor of pyrolysis gasification phase at the low or medium reaction temperature for the pyrolysis and gasification and can suitably function as catalyst to sufficiently reform the tar in the gasified gas at the high temperature for tar reformation in the reactor of gasified gas purification phase.
  • the reactor of gasified gas purification phase may be larger in horizontal cross sectional area than the reactor of pyrolysis gasification phase.
  • the reactor of gasified gas purification phase may be arranged integral with the reactor of pyrolysis gasification phase, and the particle passage for circulation of the heat medium and active chemical from the reactor of gasified gas purification phase to the reactor of pyrolysis gasification phase may be arranged inside or outside of the integrated reactor of gasified gas purification phase and reactor of pyrolysis gasification phase.
  • the integrated arrangement of the reactor of gasified gas purification phase with the reactor of pyrolysis gasification phase makes the whole of the apparatus compact in size, and the inside or outside arrangement of the particle passage from the reactor of gasified gas purification phase to the reactor of pyrolysis gasification phase stabilizes the circulation of the heat medium and active chemical.
  • the whole process of gasifying the solid fuel is divided into three phases of pyrolysis gasification, char combustion and gasified gas purification.
  • Tar in the gasified gas generated by the pyrolysis gasification of the solid fuel is reformed in the gasified gas purification phase at the high reaction temperature in said phase by the active chemical.
  • the active chemical having contributed as catalyst to reforming the tar is circulated together with the heat medium to the pyrolysis gasification phase where, at the low or medium temperature in said phase, CO 2 in the gasified gas is absorbed by the same active chemical.
  • the heat medium is heated and the low-active and newly added inactive chemicals are calcined to be activated.
  • CO 2 in the gasified gas can be sufficiently absorbed at a proper reaction temperature in the pyrolysis gasification phase and tar in the gasified gas can be sufficiently reformed at a proper reaction temperature in the gasified gas purification phase; and, in the char combustion phase, the low-active and inactive chemicals can be sufficiently activated before contribution to tar reformation.
  • reaction temperatures can be independently controlled for realization of maximum reaction performances, so that the action of accelerating the gasifying reaction through absorption of CO 2 in the gas by the chemical can be made compatible with the catalytic action of reforming the tar in the gasified gas generated by the gasifying reaction.
  • the gasification of the solid fuel can be realized at high efficiency and cleanly to obtain the gasified gas with high quality.
  • the reaction temperature in said phase can be maintained to the low or medium temperature of 773-1073° K at which CO 2 in the gasified gas can be satisfactorily absorbed by the active chemical, so that even if the reactor of pyrolysis gasification phase is not at high pressure but substantially at normal pressure, CO 2 in the gasified gas generated by the gasification can be reliably absorbed by the active chemical.
  • the reaction temperature can be maintained to high temperature of 1073° K or more, so that the heat medium and active chemical can be sufficiently high-temperatured and the active chemical can be sufficiently activated.
  • reaction temperature in said phase can be maintained to high temperature of 1073° K or more at which tar in the gasified gas can be satisfactorily reformed by the active chemical, so that the tar in the gasified gas can be reliably reformed by the active chemical and at the same time H 2 S, HCl and the like can be satisfactorily removed.
  • the high reaction temperature in said phase is somewhat lower than the reaction temperature in the char combustion phase, i.e., the temperature of the particles and active chemical heated in the char combustion phase, but can be reliably higher than the low or medium reaction temperature in the reactor of pyrolysis gasification phase for said phase.
  • the inactive chemical may be mineral such as Ca(OH) 2 which has, as its base, metal carbonate such as CaCO 3 or hydroxide, so that, in the reactor of pyrolysis gasification phase, CO 2 in the gasified gas can be sufficiently absorbed by the activated active chemical such as CaO in the low or medium reaction temperature in said phase, and in the reactor of gasified gas purification phase, the tar in the gasified gas can be sufficiently reformed in the high reaction temperature in said phase.
  • the activated active chemical such as CaO in the low or medium reaction temperature in said phase
  • the tar in the gasified gas can be sufficiently reformed in the high reaction temperature in said phase.
  • the whole process of gasifying the solid fuel is divided into three phases of pyrolysis gasification, char combustion and gasified gas purification.
  • the active chemical which is circulated CO 2 in the gasified gas can be sufficiently absorbed at a proper reaction temperature in the pyrolysis gasification phase and tar in the gasified gas can be sufficiently reformed at a proper reaction temperature in the gasified gas purification phase; and, in the char combustion phase, the low-active and inactive chemicals can be sufficiently activated before contribution to tar reformation.
  • reaction temperatures can be independently controlled for realization of maximum reaction performances, so that the action of accelerating the gasifying reaction through absorption of CO 2 in the gas by the chemical can be made compatible with the catalytic action of reforming the tar in the gasified gas generated by the gasifying reaction.
  • the gasification of the solid fuel can be realized at high efficiency and cleanly to obtain the gasified gas with high quality.
  • the reaction temperature in the pyrolysis gasification can be maintained to the low or medium temperature of 773-1073° K at which CO 2 in the gasified gas can be satisfactorily absorbed by the active chemical, so that even if the reactor of pyrolysis gasification phase is not high pressure but substantially at normal pressure, CO 2 in the gasified gas generated by the gasification can be reliably absorbed by the active chemical.
  • the reaction temperature can be maintained to high temperature of 1073° K or more, so that the heat medium and the active chemical can be sufficiently high-temperatured and the active chemical can be sufficiently activated.
  • the tar reforming reaction temperature can be maintained to high temperature of 1073° K or more at which tar in the gasified gas can be satisfactorily reformed by the active chemical, so that the tar in the gasified gas can be reliably reformed by the active chemical and at the same time H 2 S, HCl and the like can be satisfactorily reformed.
  • the high reaction temperature in said phase is somewhat lower than the reaction temperature in the char combustion phase, i.e., the temperature of the particles and active chemical heated in the char combustion phase, but can be reliably higher than the low or medium reaction temperature in the reactor of pyrolysis gasification phase for said phase.
  • the inactive chemical may be mineral such as Ca(OH) 2 which has, as its base, metal carbonate such as CaCO 3 or hydroxide, so that, in the reactor of pyrolysis gasification phase, CO 2 in the gasified gas can be sufficiently absorbed by the activated active chemical such as CaO in the low or medium reaction temperature in said phase, and in the reactor of gasified gas purification phase, the tar in the gasified gas can be sufficiently reformed in the high reaction temperature for tar reformation.
  • the activated active chemical such as CaO in the low or medium reaction temperature in said phase
  • the reactor of gasified gas purification phase may be larger in horizontal cross sectional area than the reactor of pyrolysis gasification phase, so that the dwell time of the gasified gas in the reactor of gasified gas purification phase can be prolonged to sufficiently purify the gasified gas.
  • the reactor of gasified gas purification phase may be arranged integral with the reactor of pyrolysis gasification phase, so that the whole of the apparatus can be made compact in size. Moreover, the inside or outside arrangement of the particle passage from the reactor of gasified gas purification phase to the reactor of pyrolysis gasification phase can stabilize the circulation of the heat medium and active chemical.
  • FIG. 1 A view showing schematic construction of a gasifier for solid fuel with unified gas purification according to a first embodiment of the invention.
  • FIG. 2 A diagram schematically showing an operational principle of the method for gasifying solid fuel with unified gas purification according to the invention.
  • FIG. 3 A graph showing thermo gravimetric (TG) weight variation of CaCO 3 when temperature is varied with a lower CO 2 concentration.
  • FIG. 4 A graph showing chemical equilibrium on the basis of pressure and temperature in the chemical reaction of CaO with CO 2 .
  • FIG. 5 A graph showing TG weight variation of CaO when atmosphere temperature is increased to about 1000° K at normal pressure and in the presence of lower CO 2 concentration.
  • FIG. 6 A graph showing TG weight variation of CaO when atmosphere temperature is increased to about 1130° K at normal pressure and in the presence of higher CO 2 concentration.
  • FIG. 7 A view showing schematic construction of a gasifier for solid fuel with unified gas purification according to a second embodiment of the invention.
  • FIG. 8 A view showing schematic construction of a gasifier for solid fuel with unified gas purification according to a third embodiment of the invention.
  • FIG. 9 A view showing schematic construction of a gasifier for solid fuel with unified gas purification according to a fourth embodiment of the invention.
  • FIG. 1 shows schematic construction of a gasifier for solid fuel with unified gas purification according to the first embodiment of the invention. The description will be made in conjunction with FIG. 1 .
  • the gasifier using the method for gasifying solid fuel with unified gas purification according to the invention is constructed as a system with an external circulation type fluidized bed, which separately comprises, as shown in FIG. 1 , a gasification furnace (reactor of pyrolysis gasification phase) 10 , a combustion furnace (reactor of char combustion phase) 20 and a gas purification furnace (reactor of gasified gas purification phase) 30 , solid components being circulated through the furnaces 10 , 20 and 30 together with fluid heat medium (bed material such as sand).
  • a gasification furnace reactor of pyrolysis gasification phase
  • combustion furnace reactor of char combustion phase
  • gas purification furnace reactor of gasified gas purification phase
  • the gasification furnace 10 is a device with a fluidized bed 12 fed with solid fuel such as coal, biomass or various wastes and with a gasifying agent such as steamer or CO 2 for gasification (including pyrolysis) of the solid fuel through heat of the fluid heat medium heated and high-temperatured as mentioned hereinafter.
  • the gasification furnace 10 is communicated at its top with the gas purification furnace 30 , so that product gas (produced or gasified gas) gasified in the furnace 10 is fed to the gas purification furnace 30 .
  • the gasification furnace 10 is communicated at its side center through a particle classifier 40 with a lower portion of the combustion furnace 20 .
  • the particle classifier 40 serves to separate ash of the solid fuel and part of low-active chemical mentioned hereinafter, char generated through the gasification and the low-temperatured fluid heat medium and has a function of discharging and discarding the ash of the solid fuel (the ash generated by char combustion in the combustion furnace 20 ) and part of low-active chemical mentioned hereinafter and a function of feeding the char, the part of the low-active chemical and the fluid heat medium to a lower portion of the combustion furnace 20 .
  • the combustion furnace 20 is a device with a fluidized bed 22 fed with an oxidizing agent (air or O 2 ) from below for burning the char fed from the gasification furnace 10 and heating the fluid heat medium into high temperature, the furnace 20 being communicated at its top with a cyclone 50 .
  • the cyclone 50 is a device for separating the solid components from the gaseous components and has a function of discharging exhaust gas generated in the combustion furnace 20 into atmosphere and a function of feeding the high-temperatured fluid heat medium and solid components entrained in the exhaust gas to the gas purification furnace 30 .
  • the combustion furnace 20 is provided with a chemical supply pipe (inactive chemical supply means) 20 a which feeds chemical with its inactive state (inactive chemical or chemical agent) such as limestone (CaCO 3 ) to the fluidized bed 22 .
  • active chemical or chemical agent active chemical or chemical agent
  • the gas purification furnace 30 is a device for purifying the product gas fed from the gasification furnace 10 and is constructed to be capable of reforming tar in the product gas and absorbing and removing H 2 S, HCl and the like in the product gas.
  • the gas purification furnace 30 is communicated at its top with a cyclone 55 .
  • the cyclone 55 is a device for separating the solid components from the gaseous components just like the cyclone 50 and has a function of feeding the product gas purified in the gas purification furnace 30 , for example, as fuel to a gas turbine or the like and a function of returning the solid components entrained in the product gas to the gasification furnace 10 .
  • a particle pipage 15 extends from a side center of the gas purification furnace 30 into the gasification furnace 10 , whereby particles mainly constituted by the fluid heat medium are fed through the pipage 15 to the furnace 10 .
  • FIG. 2 schematically shows an operational principle of the method for gasifying solid fuel with unified gas purification according to the invention.
  • the description hereinafter is referred also to the figure.
  • solid arrows conceptually show material circulation of gas, fluid heat medium, chemical and the like and dotted arrows, heat circulation.
  • the combustion furnace 20 is fed with the char from the gasification furnace 10 and with the oxidizing agent, and the char is burned.
  • the fluidized bed 22 in the furnace 20 is fed with chemical such as limestone (CaCO 3 ), CaCO 3 or the like being heated together with the fluid heat medium by combustion heat of the char.
  • the combustion of the char lacks endothermic reaction unlike the gasification of the solid fuel in the gasification furnace 10 , so that the temperature in the combustion furnace 20 is satisfactorily increased to high temperature T 1 (for example, 1073° K or more) in harmony with CaCO 3 degradation chemical reaction with formula (16) shown in table 1 below.
  • T 1 for example, 1073° K or more
  • CaCO 3 degradation chemical reaction with formula (16) shown in table 1 below.
  • Table 1 plus (+) and minus ( ⁇ ) indicate endothermic and exothermic amounts, respectively, for ⁇ H 0 .
  • the combustion of the char is carried out differently from the gasification of the solid fuel, so that a CO 2 content in the gasified gas is lower than that in a usual gasification furnace where combustion and gasification coexist; thus, CO 2 concentration in the combustion furnace 20 is suppressed to a value as low as, for example, 10-15 mol % or so whereas that in the usual gasification furnace is 20 mol % or more.
  • FIG. 3 shows weight variation (thermo gravimetric (TG) weight variation) in TG calcination of CaCO 3 when the temperature is varied with a low CO 2 concentration. It is seen from the figure that, if CO 2 concentration is low (for example, 15 mol %), CaCO 3 starts to be calcined at temperature of 1050° K or so, whereby CaO is satisfactorily calcined as shown by chemical formula (16). The reaction conditions of the CO 2 concentration being 15 mol % and temperature being 1050° K or more are just satisfied by atmosphere in the combustion furnace 20 .
  • TG thermo gravimetric
  • the thus calcined active chemical such as CaO is fed together with the high-temperatured fluid heat medium via the cyclone 50 to the gas purification furnace 30 which is also fed with product gas gasified in the gasification furnace 10 .
  • the product gas gasified in the gasification furnace 10 is purified by the catalytic action of the above-mentioned active chemical such as CaO.
  • gas purification chemical reactions such as formulae (12)-(14) shown in Table 1 proceed by heat of the fluid heat medium and active chemical such as CaO.
  • the reaction temperature (reaction temperature in the phase, reaction temperature of reformation of tar) T 2 in the fluidized bed 32 is as high as 1073° K or more and is substantially equal to the temperature of the particles from the cyclone 50 , the catalytic function of the active chemical such as CaO to the tar reforming reaction formula (12) being sufficiently exhibited.
  • the more or less endotherm in the tar reforming reaction formula (12) somewhat lowers the temperature of the particles passing through the gas purification furnace 30 , so that actually the reaction temperature T 2 is somewhat lower than the above-mentioned T 1 in the combustion furnace 20 .
  • the fluidized bed 32 in the gas purification furnace 30 is maintained to high temperature (>1073° K) necessary to sufficiently exhibit and in harmony with the catalytic function of the active chemical to the tar reforming reaction formula (12), so that CaO or the like sufficiently exhibits the catalytic function to tar and dust (reformation of tar) or exhibit attaching function (attachment of tar and dust) and can clarify them.
  • CaO or the like exhibits oxidation function as oxidizing agent to H 2 S, HCl and the like and can absorb them.
  • tar, dust, H 2 S, HCl and the like in the product gas are sufficiently removed by CaO or the like, so that the product gas is sufficiently purified (third process).
  • CaO or the like after the purification reaction and used in the purification of the product gas is circulated together with the fluid heat medium via the particle pipage 15 to the gasification furnace 10 .
  • CaO or the like jumped together with the product gas out of the gas purification furnace 30 also undergoes the solid-gas separation by the cyclone 55 and is fed to the gasification furnace 10 .
  • reaction pressure of as low as 1-5 atm and in harmony with CO 2 absorption reaction (5) for example control of fuel treated amount is carried out to control the reaction temperature in the fluidized bed to the reaction temperature T 3 (for example 773-1073° K, more preferably 873-1023° K), i.e., to the low or medium temperature necessary for absorptive chemical reaction of CO 2 .
  • T 3 for example 773-1073° K, more preferably 873-1023° K
  • the solid fuel is gasified and CaO or the like is reacted with CO 2 for sufficient absorption of CO 2 .
  • FIG. 5 shows weight variation (thermo gravimetric or TG weight variation) of CaO when atmosphere temperature is increased to about 1000° K at normal pressure and in the presence of 10 mol % of CO 2
  • FIG. 6 shows, as comparative example, weight variation (TG weight variation) of CaO when atmosphere temperature is increased to about 1130° K at normal pressure and in the presence of 25 mol % of CO 2 .
  • the active chemical such as CaO is satisfactorily reacted with CO 2 in the product gas to absorb CO 2 , and is converted back into inactive chemical such as CaCO 3 , i.e., returned into the original chemical.
  • CaS or the like which is generated when CaO or the like is used for oxidation of H 2 S or the like, or part of the low-active chemical having been reacted in the gasification furnace 10 is separated in the particle classifier 40 and discharged together with ash for disposal.
  • CaCO 3 or the like corresponding to such lack is replenished (as newly added inactive chemical) in the form of mineral such as limestone from the chemical supply pipe 20 a to the fluidized bed 22 of the combustion furnace 20 ; thus, CaO or the like is continued to be satisfactorily generated.
  • the whole gasification process is divided into three processes or phases: the gasification furnace 10 for fuel pyrolysis and gasification (pyrolysis gasification phase, first process), the combustion furnace 20 for burning the gasified char and for calcining chemical such as CaCO 3 to obtain active chemical such as CaO (char combustion phase, second process) and the gas purification furnace 30 for purification of the product gas (gasified gas purification phase, third process).
  • the gasification furnace 10 for fuel pyrolysis and gasification pyrolysis gasification phase, first process
  • the combustion furnace 20 for burning the gasified char and for calcining chemical such as CaCO 3 to obtain active chemical such as CaO (char combustion phase, second process)
  • the gas purification furnace 30 for purification of the product gas gasified gas purification phase, third process
  • the temperatures of the respective furnaces may be readily controlled independently from each other.
  • the fluidized bed 32 may be controlled to the reaction temperature T 2 (for example, 1073° K or more), i.e., high temperature required for active CaO or the like to sufficiently exhibit the catalytic function to the tar reforming reaction;
  • the reaction temperature T 2 for example, 1073° K or more
  • the fluidized bed 12 in the presence of heat possessed by the fluid heat medium and CaO or the like circulated from the gas purification furnace 30 , for example adjustment of the fuel amount fed to the gasification furnace 10 can be carried out to control the fluidized bed 12 , in harmony with CO 2 absorption chemical reaction by CaO, to the reaction temperature T 3 (for example, 873-1023° K), i.e., the lower or medium temperature required for absorption chemical reaction of CO 2
  • the fluid heat medium is heated and CaCO 3 or the like chemical is calcined to generate active chemical such as CaO, these fluid heat medium and CaO or the like are fed to the gas purification furnace 30 ; in the fluidized bed 32 in the furnace 30 , at the predetermined reaction temperature T 2 , the product gas can be satisfactorily purified with CaO or the like being used as catalyst, so that tar, dust, H 2 S, HCl and the like in the product gas can be satisfactorily removed.
  • CO 2 in the product gas generated through gasification can be satisfactorily absorbed by active chemical such as CaO, so that combustion heat amount possessed by the product gas can be enhanced and H 2 concentration in the product gas can be enhanced (H 2 -enrichment) while gasifying reaction speed can be accelerated and further, heat supply for gasification (including fuel pyrolysis) can be stabilized.
  • active chemical such as CaO
  • the action of absorbing CO 2 in the gas by the chemical to accelerate the gasifying reaction can be compatible with the catalytic action of reforming tar in the product gas generated through the gasifying reaction.
  • part of the purified product gas may be returned to and charged together with the gasifying agent to the gasification furnace 10 ; then, heat of the product gas may be used for temperature control in the gasification furnace 10 to further stabilize heat supply for gasification (including fuel pyrolysis).
  • T 3 low or medium temperature or predetermined reaction temperature T 3 (for example, 873-1023° K)
  • various industrial waste heat for example, exhaust gas from a gas turbine
  • gasification including fuel pyrolysis
  • FIG. 7 shows schematic construction of a gasifier for solid fuel with unified gas purification according to the second embodiment of the invention. The description will be made in conjunction with FIG. 7 . In this connection, explanation is omitted with respect to portions in common with the above-mentioned first embodiment.
  • the apparatus comprises a gasification furnace 10 and a gas purification furnace 30 which are vertically connected into an integral unit, calcined active chemical such as CaO and fluid heat medium being passed into the gasification furnace 10 through a particle pipage (particle passage) 15 ′ arranged in the furnaces 30 and 10 .
  • Such integral construction of the gasification furnace 10 with the gas purification furnace 30 can make the whole of the apparatus compact in size and stabilize transfer of the fluid heat medium and active chemical such as CaO to the gasification furnace 10 , thereby further stabilizing heat supply for gasification.
  • part of the product gas purified may be returned to and charged together with the gasifying agent to the gasification furnace 10 .
  • FIG. 8 shows schematic construction of a gasifier for solid fuel with unified gas purification according to the third embodiment of the invention. The description will be made in conjunction with FIG. 8 . In this connection, explanation is made only on portions different from those in the above-mentioned second embodiment.
  • the apparatus comprises a gasification furnace 10 and a gas purification furnace 30 which are integrally constructed, a horizontal cross sectional area of the furnace 30 being larger than that of the furnace 10 .
  • Such increased horizontal cross sectional area of the gas purification furnace 30 than that of the gasification furnace 10 prolongs dwell time of the product gas, which is generated in the gasification furnace 10 , in the fluidized bed 32 of the gas purification furnace 30 , so that the product gas is further satisfactorily purified during its passage through the furnace 30 .
  • tar, dust, H 2 S, HCl and the like in the product gas can be further reliably removed in comparison with the above-mentioned second embodiment, thereby further enhancing the purification effect of the product gas.
  • part of the product gas purified may be returned to and charged together with the gasifying agent to the gasification furnace 10 .
  • FIG. 9 shows schematic construction of a gasifier for solid fuel with unified gas purification according to the fourth embodiment of the invention. The description will be made in conjunction with FIG. 9 . Also in this connection, explanation is made only on portions different from those in the above-mentioned second embodiment.
  • the apparatus comprises a gasification furnace 10 and a gas purification furnace 30 which are integrally constructed, a particle pipage (particle passage) 15 ′′ being provided as outer passage between the furnaces 30 and 10 .
  • Such communication between the gas purification furnace 30 and the gasification furnace 10 through the particle pipage 15 ′′ or outer passage brings about supply of the active chemical such as CaO and the fluid heat medium from the gas purification furnace 30 via the particle pipage 15 ′′ to the gasification furnace 10 .
  • the active chemical such as CaO
  • the fluid heat medium and active chemical part of the product gas purified is fed to the particle pipage 15 ′′, whereby enhanced is the supply of particles such as the fluid heat medium and active chemical from the gas purification furnace 30 to the gasification furnace 10 .
  • transfer of the fluid heat medium and active chemical such as CaO to the gasification furnace 10 can be further stabilized and heat supply for gasification can be further stabilized.
  • part of the product gas purified may be returned to and charged together with the gasifying agent to the gasification furnace 10 .
  • the chemical may be limestone (CaCO 3 ) and the active chemical being CaO; however, the chemical may be mineral such as Ca(OH) 2 which has, as its basis, metal carbonate such as dolomite (CaCO 3 .MgCO 3 ) or hydroxide; the active chemical may be MgO, CaO.MgO or the like.
  • the invention can be effectively utilized when tar and H 2 S in gasified gas of solid fuel are to be easily and inexpensively removed, using natural mineral and to sufficiently purify the gasified gas.

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Abstract

A function of absorbing CO2 in gas by chemical to accelerate gasifying reaction is made compatible with a catalytic function of reforming tar in gasified gas generated by the gasifying reaction to thereby make it possible to produce clean product gas with high gasification efficiency.
Gasification process is divided into three processes: a gasification furnace 10 for carrying out gasification process by pyrolysis and gasification (pyrolysis gasification phase, first process), a combustion furnace 20 for burning char to obtain calcined active chemical (char combustion phase, second process) and a gas purification furnace 30 for purifying gasified gas (gasified gas purification phase, third process). Through heat transmission by fluid heat medium and chemical and through harmony of chemical reactions in respective phases by the chemical, the gasification furnace 10 is independently controlled to a low or medium temperature (773-1073° K) which is required for gasification and which enables absorption of CO2; and the gas purification furnace 30 is controlled to a high temperature (1073° K or more) required for gas purification.

Description

    TECHNICAL FIELD
  • The present invention relates to technique for gasifying solid fuel, and more specifically relates to technique for gasifying solid fuel highly efficiently and more cleanly.
  • BACKGROUND ART
  • Gasification of solid fuel such as coal, biomass or various wastes in a gasification furnace is generally carried out in a high-temperatured environment of about 1123° K or more so as to obtain sufficient reaction speed and heat supply to the reaction. In order to attain such high-temperatured environment of about 1123° K or more in the gasification furnace, part of the solid fuel itself must be burned.
  • However, such combustion of the solid fuel itself disadvantageously deteriorates gasification efficiency of the fuel. To carry out the combustion and gasification of the fuel in one and the same reaction space or gasification furnace inevitably causes a large amount of inert gases such as CO2 and N2 to be admixed in the gasified gas, resulting in lowering in purity and heat quantity of the product gas.
  • Moreover, the gas gasified in the high-temperatured environment is rich in CO and CO2 and poor in H2; in order to produce H2-enriched product gas required, for example, for a synthesizing process of GTL (Gas to Liquid), the high-temperatured gasified gas must be cooled to independently carry out CO shift reaction and removal of CO2.
  • A conventionally known method for concurrently removing CO during gasification of solid fuel is to absorb CO2 in gasified gas in a gasification furnace, using a chemical such as CaO-based oxide; however, in a high-temperatured environment of 1123° K or more, there is a restriction in terms of chemical equilibrium that absorption of CO2 requires the gasification furnace to be in a high pressure environment of 20 atm or more (see, for example, Patent References 1 and 2).
  • The gasification technique at such high pressure can be utilized practically only in large-scaled energy/fuel producing systems of several hundreds MW from a viewpoint of cost or other restrictions; in other various low-capacity systems such as a dispersed hydrogen fuel cell power and synthesis system, it has been desired that production of H2-enriched product gas be carried out through gasification at low or preferably normal pressure.
  • Thus, it is conceivable that a gasification process with enabled high efficiency at low or medium temperature and at low pressure is indispensable for application to various energy-scale energy/fuel production systems including the above-mentioned GTL or in order to construct next-generation, highly effective electric generating systems.
  • More specifically, if gasification at low or medium temperature were put into practice, there would be no need of burning the solid fuel itself; instead, for example, various industrial waste heats such as heat of exhaust gas from a gas turbine may be utilized as heat source for gasification with expectation for high efficiency of the gasification. There would be no need of a high pressure environment; instead, for example even at a normal pressure, CO2 in the gasified gas may be satisfactorily absorbed by oxide chemical such as CaO, providing that it is at low or medium temperature.
  • With respect to a method for gasifying fuel through combustion of solid fuel itself (usual partial oxidation method, other method of not using a gasifying agent or auto-thermal gasification method, or other method of using a gasifying agent such as steam or CO2), known is twin-circulating-fluidized-bed-type gasification technique (see, for example, Patent References 3 and 4) wherein inert gas such as CO2 generated by combustion and N2 fed through supply of air for combustion are prevented from being admixed in the gasified gas in such a manner that the solid fuel is gasified in the gasification furnace, the gasified char being burned in a combustion furnace separate from the gasification furnace, heat fluid medium being circulated between these gasification and combustion furnaces to transfer heat from the combustion furnace to the gasification furnace.
  • In such gasification method with fuel gasification separate from char combustion and in order to absorb CO2 in gasified gas to produce H2-enriched product gas, there has been developed, in Europe, a gasification method called AER (Absorption Enhanced Reforming) wherein heat medium circulated between the combustion and gasification furnaces is added with CaO chemical (see Non-patent Reference 1). In the AER method, circulating fluidized bed is used; biomass is gasified in a gasification furnace adjacent to a downcomer in an environment of 873-973° K and at normal pressure, CO2 being absorbed by CaO chemical to obtain gasified gas with high H2 content and to accelerate the gasifying reaction, CaCO3 thus generated being regenerated into CaO in a riser combustion furnace and being circulated to the gasification furnace together with the fluid heat medium.
  • [Patent Reference 1] U.S. Pat. No. 4,231,760
  • [Patent Reference 2] JP2004-59816A
  • [Patent Reference 3] U.S. Pat. No. 4,568,362
  • [Patent Reference 4] AT405937B
  • [Non-Patent Reference 1] http://www.aer-gas.de
  • SUMMARY OF THE INVENTION Problems to be Solved by the Invention
  • In the existing gasification methods with separate combustion (char) and gasification (fuel), the gasification reaction is either at high temperature of 1123° K or more (Patent References 3 and 4) or at low or medium temperature of 973° K or so (AER).
  • The gasification at the low or medium temperature inevitably generates tar in large quantity. Although CaO is used as catalyst for reformation of tar in the above-mentioned AER, temperature as high as 1123° K or more is required for CaO to exhibit sufficient catalytic function to tar, as is generally known in the art.
  • Disadvantageously, in low-temperature environment of 873-973° K as in AER, tar is not sufficiently reformed, i.e., the gasified gas is not sufficiently purified. Thus, it is predicted that the gasified gas obtained in the above-mentioned AER actually contains tar in large quantity.
  • On the other hand, in the case of the gasification reaction temperature of 1123° K or more, CaO-based chemical indeed exhibits sufficient catalytic function for reformation of tar in the gasified gas; however, at such high temperature, CO2 cannot be sufficiently absorbed by CaO. As mentioned above, in order to bring about absorption of CO2, the operation pressure of the gasification furnace must be set to as high as 20 atm or more, which causes problems that gasification in high-pressure environment is costly and that application of gasification technique is restricted.
  • Thus, in fact, a catalytic function of reforming tar in gasified gas through chemical such as CaO is not compatible with a function of absorbing CO2 in gas to accelerate gasifying reaction.
  • The invention was made in order to solve the above problems and has an object to make it possible that a function of absorbing CO2 in gas by chemical to accelerate gasifying reaction is compatible with a catalytic function of reforming tar in gasified gas generated by the gasifying reaction and to provide a gasification method of solid fuel with unified gas purification with enabled high gasification efficiency and production of clean produced gas as well as a gasifier using said method.
  • Means or Measures for Solving the Problems
  • In order to attain the above-mentioned objects, according to a first aspect of the invention, the invention is directed to a method for gasifying solid fuel with unified gas purification, characterized in that it comprises a first process of feeding solid fuel and a gasifying agent to a reactor of pyrolysis gasification phase where said solid fuel is pyrolyzed in contact with heat medium to generate char gasified by said gasifying agent, CO2 in gasified gas generated by said pyrolysis and gasification being absorbed by active chemical at a reaction temperature of said pyrolysis gasification phase; a second process of feeding residual char not gasified in said reactor of pyrolysis gasification phase, the heat medium low-temperatured through contribution to the pyrolysis and gasification of said solid fuel, the low-active chemical less-activated through reaction with said CO2 and newly added inactive chemical to a reactor of char combustion phase where said char is burned by an oxidizing agent to bring about combustion heat with which said low-temperatured heat medium is heated, said low-active and inactive chemicals are calcined to be re-activated and activated, respectively; and a third process of feeding the heat medium heated in said reactor of char combustion phase and the active chemical activated as well as said gasified gas from said reactor of pyrolysis gasification phase to a reactor of gasified gas purification phase where said active chemical functions as catalyst to reform tar in said gasified gas at a reaction temperature of said gasified gas purification phase and absorbs H2S and HCl in said gasified gas to purify said gasified gas, the active chemical having contributed mainly as catalyst to purifying said gasified gas being circulated together with the heat medium to said reactor of pyrolysis gasification phase.
  • Thus, in the reactor of char combustion phase, the heat medium is heated and the low-active and newly added inactive chemicals are calcined to generate the active chemical (second process), these high-temperatured heat medium and active chemical being fed to the reactor of gasified gas purification phase where, at the high reaction temperature of the gasified gas purification phase, tar in the gasified gas is satisfactorily reformed with the active chemical functioning as catalyst, and H2S and HCl in the gasified gas are satisfactorily absorbed by the active chemical (third process). Then, the chemical having reformed the heat medium and tar and having absorbed H2S and HCl is circulated to the reactor of pyrolysis gasification phase while it possesses absorption activity of CO2; in the reactor of pyrolysis gasification phase, CO2 in gasified gas generated by the pyrolysis and gasification of the solid fuel is satisfactorily absorbed by the chemical at the low or medium reaction temperature of the pyrolysis gasification phase (first process).
  • In the first process, the reaction temperature in the reactor of pyrolysis gasification phase for said pyrolysis gasification phase is controlled to 773-1073° K in harmony at least with the absorption reaction of CO2 in the gasified gas by the active chemical.
  • Thus, the reaction temperature of the pyrolysis and gasification phase in said reactor of pyrolysis gasification phase is in harmony for example with the absorption reaction of CO2 in the gasified gas by the active chemical so that it is maintained to the low or medium temperature of 773-1073° K at which CO2 in the gasified gas can be satisfactorily absorbed by the active chemical, so that even if the reactor of pyrolysis gasification phase is substantially at normal pressure, CO2 in the gasified gas generated by gasification is reliably absorbed by the active chemical.
  • In the second process, the reaction temperature in said reactor of char combustion phase can be controlled to 1073° K or more in harmony at least with re-activation and activation reactions of the low-active and inactive chemicals, respectively.
  • Thus, the reaction temperature in the reactor of char combustion phase is in harmony with the re-activation and activation reactions of the low-active and inactive chemicals, respectively, and is maintained to high temperature of 1073° K or more so that the heat medium and active chemical are made sufficiently high-temperatured and the active chemical is sufficiently activated.
  • In the third process, the reaction temperature in said reactor of gasified gas purification phase for said gasified gas purification phase can be controlled to the temperature of 1073° K or more in harmony at least with sufficient exhibition of the catalytic function of the active chemical to the tar reforming reaction, which is lower than the reaction temperature in the reactor of char combustion phase and higher than the reaction temperature in the reactor of pyrolysis gasification phase for the pyrolysis gasification phase.
  • Thus, the reaction temperature in the reactor of gasified gas purification phase for the gasified gas purification phase is in harmony for example with exhibition of the catalytic function of the active chemical to the tar reforming reaction so that it is maintained to high temperature of 1073° K or more at which tar in the gasified gas can be satisfactorily reformed by the active chemical; the tar in the gasified gas is reliably reformed by the active chemical and at the same time H2S, HCl and the like are satisfactorily removed. In this case, owing to the more or less endotherm in the tar reforming reaction in the gasified gas purification phase, the high reaction temperature in said phase is somewhat lowered than the reaction temperature in the char combustion phase, i.e., the temperature of the particles and active chemical heated in the char combustion phase, but is reliably higher than the low or medium reaction temperature in the reactor of phase for the pyrolysis gasification phase.
  • The inactive chemical may be mineral which has, as its base, metal carbonate or hydroxide.
  • When the inactive chemical is mineral such as Ca(OH)2 which has, as its base, metal carbonate such as CaCO3 or hydroxide, then the activated active chemical such as CaO can satisfactorily absorb CO2 in the gasified gas in the reactor of pyrolysis gasification phase and at the low or mediate reaction temperature of said phase; and in the reactor of gasified gas purification phase, it can suitably function as catalyst to satisfactorily reform the tar in the gasified gas at high reaction temperature of the phase.
  • According to a second aspect of the invention, the invention is directed to a gasifier for solid fuel with unified gas purification, characterized in that it comprises a reactor of pyrolysis gasification phase fed with the solid fuel and a gasifying agent, said solid fuel being pyrolyzed in contact with heat medium to generate char gasified by said gasifying agent, CO2 in gasified gas generated by said pyrolysis and gasification being absorbed by active chemical at a reaction temperature of the pyrolysis and gasification; a reactor of char combustion phase fed with residual char not gasified in said reactor of pyrolysis gasification phase, the heat medium low-temperatured through contribution to the pyrolysis and gasification of said solid fuel, the low-active chemical less-activated through reaction with said CO2 and newly added inactive chemical, said char being burned by an oxidizing agent to bring about combustion heat with which said low-temperatured heat medium is heated and said low-active and inactive chemicals are calcined to be re-activated and activated, respectively; and a reactor of gasified gas purification phase fed with the heat medium heated in said reactor of char combustion phase, the activated active chemical and said gasified gas from said reactor of pyrolysis gasification phase, said active chemical functioning as catalyst to reform tar in said gasified gas at a tar reforming reaction temperature and absorbing H2S and HCl in said gasified gas to purify said gasified gas, the active chemical having contributed mainly as catalyst to purifying said gasified gas being circulated together with the heat medium to said reactor of pyrolysis gasification phase.
  • Thus, in the reactor of char combustion phase, the heat medium is heated and the low-active and newly added inactive chemicals are calcined to generate active chemical, so that these high-temperatured heat medium and active chemical are fed to the reactor of gasified gas purification phase where tar in the gasified gas is satisfactorily reformed with the active chemical functioning as catalyst at high reaction temperature required for tar reformation and H2S and HCl in the gasified gas are satisfactorily absorbed by the active chemical. Then, the chemical having reformed the tar and absorbed H2S and HCl is circulated together with the heat medium to the reactor of pyrolysis gasification phase while possessing the absorption activity of CO2, and in the reactor of pyrolysis gasification phase, CO2 in the gasified gas generated by the pyrolysis and gasification of the solid fuel is satisfactorily absorbed by the chemical at the low or medium reaction temperature of the pyrolysis gasification required for absorption of CO2.
  • The reaction temperature of the pyrolysis gasification in the reactor of pyrolysis gasification phase can be controlled to 773-1073° K in harmony at least with the absorption reaction of CO2 in the gasified gas by the active chemical.
  • Thus, the reaction temperature of the pyrolysis gasification in the reactor of pyrolysis gasification phase is in harmony for example with the absorption reaction of CO2 in the gasified gas by the active chemical, so that it is maintained to the low or medium temperature of 773-1073° K at which CO2 in the gasified gas can be satisfactorily absorbed by the active chemical. As a result, even if the reactor of pyrolysis gasification phase is substantially at the normal pressure, CO2 in the gasified gas generated by the gasification is reliably absorbed by the active chemical.
  • The reaction temperature in the reactor of char combustion phase can be controlled to 1073° K or more in harmony at least with the re-activation and activation reactions of the low-active and inactive chemicals, respectively.
  • Thus, the reaction temperature in the reactor of char combustion phase is in harmony for example with the re-activation and activation reactions of the low-active and inactive chemicals, respectively, so that it is maintained to 1073° K or more. As a result, the heat medium and active chemical are sufficiently high-temperatured and the active chemical is sufficiently activated.
  • The reaction temperature for tar reformation in the reactor of gasified gas purification phase can be controlled to the temperature of 1073° K or more in harmony at least with sufficient exhibition of the catalytic function of the active chemical to the tar reforming reaction, which is lower than the reaction temperature in the reactor of char combustion phase and higher than the reaction temperature in the reactor of pyrolysis gasification phase for the pyrolysis gasification.
  • Thus, reaction temperature for tar reformation in the reactor of gasified gas purification phase is in harmony for example with exhibition of the catalytic function of the active chemical to the tar reforming reaction, so that it is maintained to the high temperature of 1073° K or more at which tar in the gasified gas can be satisfactorily reformed by the active chemical. As a result, the tar in the gasified gas is reliably reformed and at the same time H2S, HCl and the like is satisfactorily removed by the active chemical. In this case, due to the more or less endotherm by the tar reforming reaction in the gasified gas purification phase, the high reaction temperature in the phase is somewhat lower than the reaction temperature in the char combustion phase, i.e., the temperature of the particles and active chemical heated in the char combustion phase, but is reliably higher than the low or medium reaction temperature for the pyrolysis gasification phase in the reactor of pyrolysis gasification phase.
  • The inactive chemical may be mineral which has, as its base, metal carbonate or hydroxide.
  • Thus, as the inactive chemical is mineral such as Ca(OH)2 which has, as its base, metal carbonate such as CaCO3 or hydroxide, the activated active chemical such as CaO can satisfactorily absorb CO2 in the gasified gas in the reactor of pyrolysis gasification phase at the low or medium reaction temperature for the pyrolysis and gasification and can suitably function as catalyst to sufficiently reform the tar in the gasified gas at the high temperature for tar reformation in the reactor of gasified gas purification phase.
  • The reactor of gasified gas purification phase may be larger in horizontal cross sectional area than the reactor of pyrolysis gasification phase.
  • This prolongs the dwell time of the gasified gas in the reactor of gasified gas purification phase, so that the gasified gas is sufficiently purified.
  • The reactor of gasified gas purification phase may be arranged integral with the reactor of pyrolysis gasification phase, and the particle passage for circulation of the heat medium and active chemical from the reactor of gasified gas purification phase to the reactor of pyrolysis gasification phase may be arranged inside or outside of the integrated reactor of gasified gas purification phase and reactor of pyrolysis gasification phase.
  • As a result, the integrated arrangement of the reactor of gasified gas purification phase with the reactor of pyrolysis gasification phase makes the whole of the apparatus compact in size, and the inside or outside arrangement of the particle passage from the reactor of gasified gas purification phase to the reactor of pyrolysis gasification phase stabilizes the circulation of the heat medium and active chemical.
  • EFFECTS OF THE INVENTION
  • According to the method for gasifying solid fuel with unified gas purification in the first aspect of the invention, the whole process of gasifying the solid fuel is divided into three phases of pyrolysis gasification, char combustion and gasified gas purification. Tar in the gasified gas generated by the pyrolysis gasification of the solid fuel is reformed in the gasified gas purification phase at the high reaction temperature in said phase by the active chemical. The active chemical having contributed as catalyst to reforming the tar is circulated together with the heat medium to the pyrolysis gasification phase where, at the low or medium temperature in said phase, CO2 in the gasified gas is absorbed by the same active chemical. Further, in the char combustion phase, the heat medium is heated and the low-active and newly added inactive chemicals are calcined to be activated. As a result, by the active chemical which is circulated, CO2 in the gasified gas can be sufficiently absorbed at a proper reaction temperature in the pyrolysis gasification phase and tar in the gasified gas can be sufficiently reformed at a proper reaction temperature in the gasified gas purification phase; and, in the char combustion phase, the low-active and inactive chemicals can be sufficiently activated before contribution to tar reformation.
  • In short, in the respective phases of pyrolysis gasification, char combustion and gasified gas purification, the reaction temperatures can be independently controlled for realization of maximum reaction performances, so that the action of accelerating the gasifying reaction through absorption of CO2 in the gas by the chemical can be made compatible with the catalytic action of reforming the tar in the gasified gas generated by the gasifying reaction.
  • Thus, the gasification of the solid fuel can be realized at high efficiency and cleanly to obtain the gasified gas with high quality.
  • In the reactor of pyrolysis gasification phase, in harmony for example with the absorption reaction of O2 in the gasified gas by the active chemical, the reaction temperature in said phase can be maintained to the low or medium temperature of 773-1073° K at which CO2 in the gasified gas can be satisfactorily absorbed by the active chemical, so that even if the reactor of pyrolysis gasification phase is not at high pressure but substantially at normal pressure, CO2 in the gasified gas generated by the gasification can be reliably absorbed by the active chemical.
  • In the reactor of char combustion phase, in harmony for example with the re-activation and activation reactions of the low-active and inactive chemicals, respectively, the reaction temperature can be maintained to high temperature of 1073° K or more, so that the heat medium and active chemical can be sufficiently high-temperatured and the active chemical can be sufficiently activated.
  • In the reactor of gasified gas purification phase, in harmony for example with exhibition of the catalytic function of the active chemical to the tar reforming reaction, the reaction temperature in said phase can be maintained to high temperature of 1073° K or more at which tar in the gasified gas can be satisfactorily reformed by the active chemical, so that the tar in the gasified gas can be reliably reformed by the active chemical and at the same time H2S, HCl and the like can be satisfactorily removed. In this case, owing to the more or less endotherm of the tar reforming reaction in said phase, the high reaction temperature in said phase is somewhat lower than the reaction temperature in the char combustion phase, i.e., the temperature of the particles and active chemical heated in the char combustion phase, but can be reliably higher than the low or medium reaction temperature in the reactor of pyrolysis gasification phase for said phase.
  • The inactive chemical may be mineral such as Ca(OH)2 which has, as its base, metal carbonate such as CaCO3 or hydroxide, so that, in the reactor of pyrolysis gasification phase, CO2 in the gasified gas can be sufficiently absorbed by the activated active chemical such as CaO in the low or medium reaction temperature in said phase, and in the reactor of gasified gas purification phase, the tar in the gasified gas can be sufficiently reformed in the high reaction temperature in said phase.
  • According to the gasifier for solid fuel with unified gas purification in the second aspect of the invention, just like the above-mentioned first aspect, the whole process of gasifying the solid fuel is divided into three phases of pyrolysis gasification, char combustion and gasified gas purification. By the active chemical which is circulated, CO2 in the gasified gas can be sufficiently absorbed at a proper reaction temperature in the pyrolysis gasification phase and tar in the gasified gas can be sufficiently reformed at a proper reaction temperature in the gasified gas purification phase; and, in the char combustion phase, the low-active and inactive chemicals can be sufficiently activated before contribution to tar reformation.
  • In short, in the respective phases of pyrolysis gasification, char combustion and gasified gas purification, the reaction temperatures can be independently controlled for realization of maximum reaction performances, so that the action of accelerating the gasifying reaction through absorption of CO2 in the gas by the chemical can be made compatible with the catalytic action of reforming the tar in the gasified gas generated by the gasifying reaction.
  • Thus, the gasification of the solid fuel can be realized at high efficiency and cleanly to obtain the gasified gas with high quality.
  • In the reactor of pyrolysis gasification phase, in harmony for example with the absorption reaction of CO2 in the gasified gas by the active chemical, the reaction temperature in the pyrolysis gasification can be maintained to the low or medium temperature of 773-1073° K at which CO2 in the gasified gas can be satisfactorily absorbed by the active chemical, so that even if the reactor of pyrolysis gasification phase is not high pressure but substantially at normal pressure, CO2 in the gasified gas generated by the gasification can be reliably absorbed by the active chemical.
  • In the reactor of char combustion phase, in harmony for example with the re-activation and activation reactions of the low-active and inactive chemicals, respectively, the reaction temperature can be maintained to high temperature of 1073° K or more, so that the heat medium and the active chemical can be sufficiently high-temperatured and the active chemical can be sufficiently activated.
  • In the reactor of gasified gas purification phase, in harmony for example with exhibition of the catalytic function of the active chemical to the tar reforming reaction, the tar reforming reaction temperature can be maintained to high temperature of 1073° K or more at which tar in the gasified gas can be satisfactorily reformed by the active chemical, so that the tar in the gasified gas can be reliably reformed by the active chemical and at the same time H2S, HCl and the like can be satisfactorily reformed. In this case, owing to the more or less endotherm of the tar reforming reaction in said phase, the high reaction temperature in said phase is somewhat lower than the reaction temperature in the char combustion phase, i.e., the temperature of the particles and active chemical heated in the char combustion phase, but can be reliably higher than the low or medium reaction temperature in the reactor of pyrolysis gasification phase for said phase.
  • The inactive chemical may be mineral such as Ca(OH)2 which has, as its base, metal carbonate such as CaCO3 or hydroxide, so that, in the reactor of pyrolysis gasification phase, CO2 in the gasified gas can be sufficiently absorbed by the activated active chemical such as CaO in the low or medium reaction temperature in said phase, and in the reactor of gasified gas purification phase, the tar in the gasified gas can be sufficiently reformed in the high reaction temperature for tar reformation.
  • The reactor of gasified gas purification phase may be larger in horizontal cross sectional area than the reactor of pyrolysis gasification phase, so that the dwell time of the gasified gas in the reactor of gasified gas purification phase can be prolonged to sufficiently purify the gasified gas.
  • The reactor of gasified gas purification phase may be arranged integral with the reactor of pyrolysis gasification phase, so that the whole of the apparatus can be made compact in size. Moreover, the inside or outside arrangement of the particle passage from the reactor of gasified gas purification phase to the reactor of pyrolysis gasification phase can stabilize the circulation of the heat medium and active chemical.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • [FIG. 1] A view showing schematic construction of a gasifier for solid fuel with unified gas purification according to a first embodiment of the invention.
  • [FIG. 2] A diagram schematically showing an operational principle of the method for gasifying solid fuel with unified gas purification according to the invention.
  • [FIG. 3] A graph showing thermo gravimetric (TG) weight variation of CaCO3 when temperature is varied with a lower CO2 concentration.
  • [FIG. 4] A graph showing chemical equilibrium on the basis of pressure and temperature in the chemical reaction of CaO with CO2.
  • [FIG. 5] A graph showing TG weight variation of CaO when atmosphere temperature is increased to about 1000° K at normal pressure and in the presence of lower CO2 concentration.
  • [FIG. 6] A graph showing TG weight variation of CaO when atmosphere temperature is increased to about 1130° K at normal pressure and in the presence of higher CO2 concentration.
  • [FIG. 7] A view showing schematic construction of a gasifier for solid fuel with unified gas purification according to a second embodiment of the invention.
  • [FIG. 8] A view showing schematic construction of a gasifier for solid fuel with unified gas purification according to a third embodiment of the invention.
  • [FIG. 9] A view showing schematic construction of a gasifier for solid fuel with unified gas purification according to a fourth embodiment of the invention.
  • EXPLANATION OF THE REFERENCE NUMERALS
    • 10 gasification furnace (reactor of pyrolysis gasification phase)
    • 12 fluidized bed
    • 14 upper fluidized bed
    • 15, 15′ and 15″ particle pipage (particle passage)
    • 20 combustion furnace (reactor of char combustion phase)
    • 20 a chemical supply pipe (inactive chemical supply means)
    • 22 fluidized bed
    • 30 gas purification furnace (reactor of gasified gas purification phase)
    • 32 fluidized bed
    • 40 particle classifier (discharge means)
    BEST MODE FOR CARRYING OUT THE INVENTION
  • Next, embodiments of the invention will be described in conjunction with accompanying drawings.
  • Embodiment 1
  • First of all, a first embodiment will be described.
  • FIG. 1 shows schematic construction of a gasifier for solid fuel with unified gas purification according to the first embodiment of the invention. The description will be made in conjunction with FIG. 1.
  • The gasifier using the method for gasifying solid fuel with unified gas purification according to the invention is constructed as a system with an external circulation type fluidized bed, which separately comprises, as shown in FIG. 1, a gasification furnace (reactor of pyrolysis gasification phase) 10, a combustion furnace (reactor of char combustion phase) 20 and a gas purification furnace (reactor of gasified gas purification phase) 30, solid components being circulated through the furnaces 10, 20 and 30 together with fluid heat medium (bed material such as sand).
  • The gasification furnace 10 is a device with a fluidized bed 12 fed with solid fuel such as coal, biomass or various wastes and with a gasifying agent such as steamer or CO2 for gasification (including pyrolysis) of the solid fuel through heat of the fluid heat medium heated and high-temperatured as mentioned hereinafter. The gasification furnace 10 is communicated at its top with the gas purification furnace 30, so that product gas (produced or gasified gas) gasified in the furnace 10 is fed to the gas purification furnace 30.
  • The gasification furnace 10 is communicated at its side center through a particle classifier 40 with a lower portion of the combustion furnace 20. The particle classifier 40 serves to separate ash of the solid fuel and part of low-active chemical mentioned hereinafter, char generated through the gasification and the low-temperatured fluid heat medium and has a function of discharging and discarding the ash of the solid fuel (the ash generated by char combustion in the combustion furnace 20) and part of low-active chemical mentioned hereinafter and a function of feeding the char, the part of the low-active chemical and the fluid heat medium to a lower portion of the combustion furnace 20.
  • The combustion furnace 20 is a device with a fluidized bed 22 fed with an oxidizing agent (air or O2) from below for burning the char fed from the gasification furnace 10 and heating the fluid heat medium into high temperature, the furnace 20 being communicated at its top with a cyclone 50. The cyclone 50 is a device for separating the solid components from the gaseous components and has a function of discharging exhaust gas generated in the combustion furnace 20 into atmosphere and a function of feeding the high-temperatured fluid heat medium and solid components entrained in the exhaust gas to the gas purification furnace 30.
  • The combustion furnace 20 is provided with a chemical supply pipe (inactive chemical supply means) 20 a which feeds chemical with its inactive state (inactive chemical or chemical agent) such as limestone (CaCO3) to the fluidized bed 22.
  • The gas purification furnace 30 is a device for purifying the product gas fed from the gasification furnace 10 and is constructed to be capable of reforming tar in the product gas and absorbing and removing H2S, HCl and the like in the product gas.
  • The gas purification furnace 30 is communicated at its top with a cyclone 55. The cyclone 55 is a device for separating the solid components from the gaseous components just like the cyclone 50 and has a function of feeding the product gas purified in the gas purification furnace 30, for example, as fuel to a gas turbine or the like and a function of returning the solid components entrained in the product gas to the gasification furnace 10.
  • A particle pipage 15 (particle passage) extends from a side center of the gas purification furnace 30 into the gasification furnace 10, whereby particles mainly constituted by the fluid heat medium are fed through the pipage 15 to the furnace 10.
  • The description will be made on mode of operation of the thus constructed gasifier using the gasification method with unified gas purification and the method for purifying gasified gas of solid fuel according to the invention.
  • FIG. 2 schematically shows an operational principle of the method for gasifying solid fuel with unified gas purification according to the invention. The description hereinafter is referred also to the figure. In FIG. 2, solid arrows conceptually show material circulation of gas, fluid heat medium, chemical and the like and dotted arrows, heat circulation.
  • As mentioned in the above, the combustion furnace 20 is fed with the char from the gasification furnace 10 and with the oxidizing agent, and the char is burned. In this connection, the fluidized bed 22 in the furnace 20 is fed with chemical such as limestone (CaCO3), CaCO3 or the like being heated together with the fluid heat medium by combustion heat of the char. More specifically, the combustion of the char lacks endothermic reaction unlike the gasification of the solid fuel in the gasification furnace 10, so that the temperature in the combustion furnace 20 is satisfactorily increased to high temperature T1 (for example, 1073° K or more) in harmony with CaCO3 degradation chemical reaction with formula (16) shown in table 1 below. In table 1, plus (+) and minus (−) indicate endothermic and exothermic amounts, respectively, for ΔH0.
  • TABLE 1
    phase main reactions ΔH0 (KJ) roles
    pyrolysis/  (1) CmHnOx→C+CO+H2+CO2+ . . . ΔH0 > 0 fuel pyrolysis
    gasification  (2) C+H2O→CO+H2O +131.3 gasification of steam
    (gasification  (3) C+CO2→2CO +172.5 gasification of CO2
    furnace)  (4) CO+H2O→CO2+H2 −41.2 CO shift
    (973 ± 50° K)  (5) CO2+CaO→CaCO3 −170.4 Absorption of CO2
     (6) C+2H2→CH4 −74.9 methanation of C
     (7) CO+3H2→CH4+H2O −206.2 methanation of CO
     (8) CO2+4H2→CH4+2H2O −165.0 methanation of CO2
     (9) CaO+H2O→Ca (OH)2 −109.0 hydration of chemical
    (10) H2S+CaO→CaS+H2O ΔH0 < 0 absorption of H2S
    (11) 2HCl+CaO→CaCl2+CO ΔH0 > 0 absorption of HCl
    gas purification (12) tar+H2O→CO+H2+CO2+ . . . ΔH0 > 0 reformation of tar
    (gas purification (13) H2S+CaO→CaS+H2O ΔH0 < 0 absorption of H2S
    furnace) (14) 2HCl+CaO→CaCl2+H2O ΔH0 > 0 absorption of HCl
    (about 1123° K)
    combustion of (15) C+O2→CO2 −393.5 combustion of char
    char (16) CaCO3→CaO+CO2 +170.4 calcining of CaCO3
    (≧1123° K) (17) 2CaS+O2→2CaO+SO2 ΔH0 > 0 regeneration of CaS
  • The combustion of the char is carried out differently from the gasification of the solid fuel, so that a CO2 content in the gasified gas is lower than that in a usual gasification furnace where combustion and gasification coexist; thus, CO2 concentration in the combustion furnace 20 is suppressed to a value as low as, for example, 10-15 mol % or so whereas that in the usual gasification furnace is 20 mol % or more.
  • Thus, in the combustion furnace 20, CaCO3 or the like is satisfactorily pyrolyzed at high temperature and with less CO2 as shown by chemical formula (16) in table 1, resulting in satisfactory calcination of the active chemical such as CaO (second process).
  • FIG. 3 shows weight variation (thermo gravimetric (TG) weight variation) in TG calcination of CaCO3 when the temperature is varied with a low CO2 concentration. It is seen from the figure that, if CO2 concentration is low (for example, 15 mol %), CaCO3 starts to be calcined at temperature of 1050° K or so, whereby CaO is satisfactorily calcined as shown by chemical formula (16). The reaction conditions of the CO2 concentration being 15 mol % and temperature being 1050° K or more are just satisfied by atmosphere in the combustion furnace 20.
  • The thus calcined active chemical such as CaO is fed together with the high-temperatured fluid heat medium via the cyclone 50 to the gas purification furnace 30 which is also fed with product gas gasified in the gasification furnace 10.
  • In the gas purification furnace 30, the product gas gasified in the gasification furnace 10 is purified by the catalytic action of the above-mentioned active chemical such as CaO.
  • More specifically, in the gas purification furnace 30, gas purification chemical reactions such as formulae (12)-(14) shown in Table 1 proceed by heat of the fluid heat medium and active chemical such as CaO. Here, because of less reaction heat, the reaction temperature (reaction temperature in the phase, reaction temperature of reformation of tar) T2 in the fluidized bed 32 is as high as 1073° K or more and is substantially equal to the temperature of the particles from the cyclone 50, the catalytic function of the active chemical such as CaO to the tar reforming reaction formula (12) being sufficiently exhibited. The more or less endotherm in the tar reforming reaction formula (12) somewhat lowers the temperature of the particles passing through the gas purification furnace 30, so that actually the reaction temperature T2 is somewhat lower than the above-mentioned T1 in the combustion furnace 20.
  • Thus, with the product gas containing tar, dust, H2S, HCl and the like, the fluidized bed 32 in the gas purification furnace 30 is maintained to high temperature (>1073° K) necessary to sufficiently exhibit and in harmony with the catalytic function of the active chemical to the tar reforming reaction formula (12), so that CaO or the like sufficiently exhibits the catalytic function to tar and dust (reformation of tar) or exhibit attaching function (attachment of tar and dust) and can clarify them. Moreover, CaO or the like exhibits oxidation function as oxidizing agent to H2S, HCl and the like and can absorb them. As a result, in the gas purification furnace 30, tar, dust, H2S, HCl and the like in the product gas are sufficiently removed by CaO or the like, so that the product gas is sufficiently purified (third process).
  • Then, CaO or the like after the purification reaction and used in the purification of the product gas is circulated together with the fluid heat medium via the particle pipage 15 to the gasification furnace 10. CaO or the like jumped together with the product gas out of the gas purification furnace 30 also undergoes the solid-gas separation by the cyclone 55 and is fed to the gasification furnace 10.
  • In the gasification furnace 10, in the presence of heat from the fluid heat medium and CaO or the like, the chemical reactions of formulae (1)-(11) shown in table 1 above proceed through intervention of the CO2 absorption activity of the chemical such as CaO; fuel pyrolysis and char gasification of formulae (1)-(3), which are highly endothermic reactions, further lowers the temperature of the above-mentioned solid matters (particles) from the gas purification furnace 30 than the above-mentioned reaction temperature T2. Then, at reaction pressure of as low as 1-5 atm and in harmony with CO2 absorption reaction (5), for example control of fuel treated amount is carried out to control the reaction temperature in the fluidized bed to the reaction temperature T3 (for example 773-1073° K, more preferably 873-1023° K), i.e., to the low or medium temperature necessary for absorptive chemical reaction of CO2.
  • Thus, in the gasification furnace 10, in the environment of low pressure and the required low or medium temperature T3, the solid fuel is gasified and CaO or the like is reacted with CO2 for sufficient absorption of CO2.
  • More specifically, in the chemical reaction of CaO with CO2, chemical equilibrium as shown in FIG. 4 exists on the basis of pressure and temperature; if interior of the gasification furnace 10 is at low pressure (for example, 1-5 atm) or even at a normal pressure (1 atm), to maintain the gasification furnace 10 at the low or medium temperature T3 (for example, 873-1023° K) enables CaO to satisfactorily absorb CO2, and the reaction in the reaction formula (5) in table 1 can be satisfactorily brought about.
  • FIG. 5 shows weight variation (thermo gravimetric or TG weight variation) of CaO when atmosphere temperature is increased to about 1000° K at normal pressure and in the presence of 10 mol % of CO2; and FIG. 6 shows, as comparative example, weight variation (TG weight variation) of CaO when atmosphere temperature is increased to about 1130° K at normal pressure and in the presence of 25 mol % of CO2. It is apparent from these figures that the weight of CaO, which does not vary at high temperature of about 1130° K even with high CO2 partial pressure, is drastically increased at the low or medium temperature of about 1000° K in the case of lower CO2 partial pressure and that CaO is satisfactorily converted into CaCO3 in the latter temperature condition.
  • Thus, in the gasification furnace 10, the active chemical such as CaO is satisfactorily reacted with CO2 in the product gas to absorb CO2, and is converted back into inactive chemical such as CaCO3, i.e., returned into the original chemical.
  • As CO2 is removed from the product gas in this manner, combustion heat amount possessed by the product gas is enhanced and H2 concentration in the product gas is enhanced (H2-enrichment). Moreover, absorption of CO2 by CaO or the like is thermolysis reaction so that gasifying reaction speed is accelerated. Moreover, such temperature control of the fluidized bed 12 in the gasification furnace 10 contributes to stabilizing heat supply for gasification (including fuel pyrolysis) (first process).
  • When the active chemical such as CaO is reacted with CO2 into low-active chemical such as CaCO3, then part of regenerable CaCO3 or the like is fed again, together with the char and the fluid heat medium low-temperatured by the fuel gasifying reaction, to the combustion furnace 20 and thus is activated again and regenerated, as mentioned above, into CaO or the like.
  • CaS or the like, which is generated when CaO or the like is used for oxidation of H2S or the like, or part of the low-active chemical having been reacted in the gasification furnace 10 is separated in the particle classifier 40 and discharged together with ash for disposal.
  • Since such disposal of CaS or the like and partial low-active chemical results in lack of CaO or the like, CaCO3 or the like corresponding to such lack is replenished (as newly added inactive chemical) in the form of mineral such as limestone from the chemical supply pipe 20 a to the fluidized bed 22 of the combustion furnace 20; thus, CaO or the like is continued to be satisfactorily generated.
  • As mentioned in the above, in the gasifier using the method for gasifying solid fuel with unified gas purification according to the invention, the whole gasification process is divided into three processes or phases: the gasification furnace 10 for fuel pyrolysis and gasification (pyrolysis gasification phase, first process), the combustion furnace 20 for burning the gasified char and for calcining chemical such as CaCO3 to obtain active chemical such as CaO (char combustion phase, second process) and the gas purification furnace 30 for purification of the product gas (gasified gas purification phase, third process).
  • Thus, the temperatures of the respective furnaces may be readily controlled independently from each other. Especially in the gas purification furnace 30, owing to heat of the high-temperatured fluid heat medium and of the active chemical such as CaO circulated from the combustion furnace 20 and in harmony for example with exhibition of the catalytic function by the active chemical to the tar reforming reaction, the fluidized bed 32 may be controlled to the reaction temperature T2 (for example, 1073° K or more), i.e., high temperature required for active CaO or the like to sufficiently exhibit the catalytic function to the tar reforming reaction; in the gasification furnace 10, in the presence of heat possessed by the fluid heat medium and CaO or the like circulated from the gas purification furnace 30, for example adjustment of the fuel amount fed to the gasification furnace 10 can be carried out to control the fluidized bed 12, in harmony with CO2 absorption chemical reaction by CaO, to the reaction temperature T3 (for example, 873-1023° K), i.e., the lower or medium temperature required for absorption chemical reaction of CO2.
  • Thus, in the fluidized bed 22 in the combustion furnace 20, the fluid heat medium is heated and CaCO3 or the like chemical is calcined to generate active chemical such as CaO, these fluid heat medium and CaO or the like are fed to the gas purification furnace 30; in the fluidized bed 32 in the furnace 30, at the predetermined reaction temperature T2, the product gas can be satisfactorily purified with CaO or the like being used as catalyst, so that tar, dust, H2S, HCl and the like in the product gas can be satisfactorily removed. Moreover, in the fluidized bed 12 in the gasification furnace 10, at the predetermined reaction temperature T3 and at the predetermined low pressure (1-5 atm), CO2 in the product gas generated through gasification can be satisfactorily absorbed by active chemical such as CaO, so that combustion heat amount possessed by the product gas can be enhanced and H2 concentration in the product gas can be enhanced (H2-enrichment) while gasifying reaction speed can be accelerated and further, heat supply for gasification (including fuel pyrolysis) can be stabilized.
  • That is, the action of absorbing CO2 in the gas by the chemical to accelerate the gasifying reaction (including fuel pyrolysis) can be compatible with the catalytic action of reforming tar in the product gas generated through the gasifying reaction.
  • Thus, while enhancing the gasification efficiency as a whole, the product gas clean, with high quality and useable for various uses can be obtained.
  • As shown in FIG. 1 as option, part of the purified product gas may be returned to and charged together with the gasifying agent to the gasification furnace 10; then, heat of the product gas may be used for temperature control in the gasification furnace 10 to further stabilize heat supply for gasification (including fuel pyrolysis).
  • To maintain the temperature in the gasification furnace 10 to the low or medium temperature or predetermined reaction temperature T3 (for example, 873-1023° K) makes it possible to utilize various industrial waste heat (for example, exhaust gas from a gas turbine) as stable heat source for gasification (including fuel pyrolysis), contributing to constructing a highly effective system.
  • Embodiment 2
  • Next, a second embodiment will be described.
  • FIG. 7 shows schematic construction of a gasifier for solid fuel with unified gas purification according to the second embodiment of the invention. The description will be made in conjunction with FIG. 7. In this connection, explanation is omitted with respect to portions in common with the above-mentioned first embodiment.
  • In the second embodiment, the apparatus comprises a gasification furnace 10 and a gas purification furnace 30 which are vertically connected into an integral unit, calcined active chemical such as CaO and fluid heat medium being passed into the gasification furnace 10 through a particle pipage (particle passage) 15′ arranged in the furnaces 30 and 10.
  • Such integral construction of the gasification furnace 10 with the gas purification furnace 30 can make the whole of the apparatus compact in size and stabilize transfer of the fluid heat medium and active chemical such as CaO to the gasification furnace 10, thereby further stabilizing heat supply for gasification.
  • As shown in FIG. 7 as option and as in the above, part of the product gas purified may be returned to and charged together with the gasifying agent to the gasification furnace 10.
  • Embodiment 3
  • Next, a third embodiment will be described.
  • FIG. 8 shows schematic construction of a gasifier for solid fuel with unified gas purification according to the third embodiment of the invention. The description will be made in conjunction with FIG. 8. In this connection, explanation is made only on portions different from those in the above-mentioned second embodiment.
  • In the third embodiment, the apparatus comprises a gasification furnace 10 and a gas purification furnace 30 which are integrally constructed, a horizontal cross sectional area of the furnace 30 being larger than that of the furnace 10.
  • Such increased horizontal cross sectional area of the gas purification furnace 30 than that of the gasification furnace 10 prolongs dwell time of the product gas, which is generated in the gasification furnace 10, in the fluidized bed 32 of the gas purification furnace 30, so that the product gas is further satisfactorily purified during its passage through the furnace 30.
  • Thus, tar, dust, H2S, HCl and the like in the product gas can be further reliably removed in comparison with the above-mentioned second embodiment, thereby further enhancing the purification effect of the product gas.
  • As shown in FIG. 8 as option and as in the above, part of the product gas purified may be returned to and charged together with the gasifying agent to the gasification furnace 10.
  • Embodiment 4
  • Next, a fourth embodiment will be described.
  • FIG. 9 shows schematic construction of a gasifier for solid fuel with unified gas purification according to the fourth embodiment of the invention. The description will be made in conjunction with FIG. 9. Also in this connection, explanation is made only on portions different from those in the above-mentioned second embodiment.
  • In the fourth embodiment, the apparatus comprises a gasification furnace 10 and a gas purification furnace 30 which are integrally constructed, a particle pipage (particle passage) 15″ being provided as outer passage between the furnaces 30 and 10.
  • Such communication between the gas purification furnace 30 and the gasification furnace 10 through the particle pipage 15″ or outer passage brings about supply of the active chemical such as CaO and the fluid heat medium from the gas purification furnace 30 via the particle pipage 15″ to the gasification furnace 10. At this time, together with these fluid heat medium and active chemical, part of the product gas purified is fed to the particle pipage 15″, whereby enhanced is the supply of particles such as the fluid heat medium and active chemical from the gas purification furnace 30 to the gasification furnace 10.
  • As a result, in comparison with the above-mentioned second embodiment, transfer of the fluid heat medium and active chemical such as CaO to the gasification furnace 10 can be further stabilized and heat supply for gasification can be further stabilized.
  • As shown in FIG. 9 as option and as in the above, part of the product gas purified may be returned to and charged together with the gasifying agent to the gasification furnace 10.
  • The description has been made with respect to the embodiments of the invention. It is to be understood that the invention is not limited to the above embodiments and that various changes and modifications may be made without leaving the scope and spirit of the invention.
  • For example, in the above embodiments, the description has been made with the chemical being limestone (CaCO3) and the active chemical being CaO; however, the chemical may be mineral such as Ca(OH)2 which has, as its basis, metal carbonate such as dolomite (CaCO3.MgCO3) or hydroxide; the active chemical may be MgO, CaO.MgO or the like.
  • With the above embodiments, the description has been made with respect to the system having outer circulation type fluidized bed; however, the invention is applicable also to a system with moving bed.
  • INDUSTRIAL APPLICABILITY
  • The invention can be effectively utilized when tar and H2S in gasified gas of solid fuel are to be easily and inexpensively removed, using natural mineral and to sufficiently purify the gasified gas.

Claims (12)

1. A method for gasifying solid fuel with unified gas purification, characterized in that it comprises
a first process of feeding solid fuel and a gasifying agent to a reactor of pyrolysis gasification phase where said solid fuel is pyrolyzed in contact with heat medium to generate char which is gasified by said gasifying agent, CO2 in gasified gas generated by said pyrolysis and gasification being absorbed by active chemical at a reaction temperature of said pyrolysis gasification phase,
a second process of feeding residual char not gasified in said reactor of pyrolysis gasification phase, the heat medium low-temperatured through contribution to the pyrolysis and gasification of said solid fuel, the low-active chemical less-activated through reaction with said CO2 and newly added inactive chemical to a reactor of char combustion phase where said char is burned by an oxidizing agent to bring about combustion heat with which said low-temperatured heat medium is heated, said low-active and inactive chemicals are calcined to be re-activated and activated, respectively, and
a third process of feeding the heat medium heated in said reactor of char combustion phase, the active chemical activated and said gasified gas from said reactor of pyrolysis gasification phase to a reactor of gasified gas purification phase where said active chemical functions as catalyst to reform tar in said gasified gas at a reaction temperature of said gasified gas purification phase and absorbs H2S and HCl in said gasified gas to purify said gasified gas, the active chemical having contributed mainly as catalyst to purifying said gasified gas being circulated together with the heat medium to said reactor of pyrolysis gasification phase.
2. A method for gasifying solid fuel with unified gas purification as claimed in claim 1, characterized in that, in said first process, the reaction temperature in said reactor of pyrolysis gasification phase for said pyrolysis gasification phase is controlled to 773-1073° K in harmony at least with the absorption reaction of CO2 in said gasified gas by said active chemical.
3. A method for gasifying solid fuel with unified gas purification as claim in claim 1, characterized in that, in said second process, the reaction temperature in said reactor of char combustion phase is controlled to 1073° K or more in harmony at least with the re-activation and activation reactions of said low-active and inactive chemicals, respectively.
4. A method for gasifying solid fuel with unified gas purification as claimed in claim 1, characterized in that, in said third process, the reaction temperature in said reactor of gasified gas purification phase for said gasified gas purification phase is controlled to temperature of 1073° K or more in harmony at least with sufficient exhibition of the catalytic function by said active chemical to said tar reforming reaction, which is lower than the reaction temperature in said reactor of char combustion phase and is higher than the reaction temperature in said reactor of pyrolysis gasification phase for said pyrolysis gasification phase.
5. A method for gasifying solid fuel with unified gas purification as claimed in any one of claims 1-4, characterized in that the inactive chemical is mineral which has, as its base, metal carbonate or hydroxide.
6. A gasifier for solid fuel with unified gas purification, characterized in that it comprises
a reactor of pyrolysis gasification phase fed with the solid fuel and a gasifying agent, said solid fuel being pyrolyzed in contact with heat medium to generate char gasified by said gasifying agent, CO2 in gasified gas generated by the pyrolysis and gasification being absorbed by active chemical at a reaction temperature of the pyrolysis and gasification,
a reactor of char combustion phase fed with residual char not gasified in said reactor of pyrolysis gasification phase, the heat medium low-temperatured through contribution to the pyrolysis and gasification of said solid fuel, the low-active chemical less-activated through reaction with said CO2 and newly added inactive chemical, said char being burned by an oxidizing agent to bring about combustion heat with which said low-temperatured heat medium is heated and said low-active and inactive chemicals are calcined to be re-activated and activated, respectively, and
a reactor of gasified gas purification phase fed with the heat medium heated in said reactor of char combustion phase, the activated active chemical and said gasified gas from said reactor of pyrolysis gasification phase, said active chemical functioning as catalyst to reform tar in said gasified gas at a tar reforming reaction temperature and absorbing H2S and HCl in said gasified gas to purify said gasified gas, the active chemical having contributed mainly as catalyst to purifying said gasified gas being circulated together with the heat medium to said reactor of pyrolysis gasification phase.
7. A gasifier for solid fuel with unified gas purification as claimed in claim 6, characterized in that the reaction temperature of said pyrolysis and gasification in said reactor of pyrolysis gasification phase is controlled to 773-1073° K in harmony with at least the absorption reaction of CO2 in said gasified gas.
8. A gasifier for solid fuel with unified gas purification as claimed in claim 6, characterized in that the reaction temperature in said reactor of char combustion phase is controlled to 1073° K or more in harmony with at least the re-activation and activation reactions of said low-active and inactive chemicals, respectively.
9. A gasifier for solid fuel with unified gas purification as claimed in claim 6, characterized in that the reaction temperature for said tar reformation in said reactor of gasified gas purification phase is controlled to temperature of 1073° K or more in harmony at least with sufficient exhibition of the catalytic function by said active chemical to said tar reforming reaction, which is lower than the reaction temperature in said reactor of char combustion phase and is higher than the reaction temperature of said pyrolysis and gasification in said reactor of pyrolysis gasification phase.
10. A gasifier for solid fuel with unified gas purification as claimed in any one of claims 6-9, characterized in that the inactive chemical is mineral which has, at its base, metal carbonate or hydroxide.
11. A gasifier for solid fuel with unified gas purification as claimed in any one of claims 6-9, characterized in that said reactor of gasified gas purification phase is larger in horizontal sectional area than said reactor of pyrolysis gasification phase.
12. A gasifier for solid fuel with unified gas purification as claimed in any one of claims 6-9, characterized in that said reactor of gasified gas purification phase and said reactor of pyrolysis gasification phase are integrally arranged,
a particle passage being arranged inside or outside of said integrated reactor of gasified gas purification phase and reactor of pyrolysis gasification phase so as to circulate said heat medium and active chemical from said reactor of gasified gas purification phase to said reactor of pyrolysis gasification phase.
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CN101213273B (en) 2011-08-10

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