WO2014094308A1 - Procédé de gazéification par pyrolyse et dispositif pour préparer du gaz riche en hydrogène sans goudron - Google Patents

Procédé de gazéification par pyrolyse et dispositif pour préparer du gaz riche en hydrogène sans goudron Download PDF

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Publication number
WO2014094308A1
WO2014094308A1 PCT/CN2012/087190 CN2012087190W WO2014094308A1 WO 2014094308 A1 WO2014094308 A1 WO 2014094308A1 CN 2012087190 W CN2012087190 W CN 2012087190W WO 2014094308 A1 WO2014094308 A1 WO 2014094308A1
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Prior art keywords
pyrolysis
gas
reactor
tar
coke
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PCT/CN2012/087190
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English (en)
Chinese (zh)
Inventor
许光文
韩江则
曾玺
高士秋
董鹏伟
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中国科学院过程工程研究所
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Priority to PCT/CN2012/087190 priority Critical patent/WO2014094308A1/fr
Publication of WO2014094308A1 publication Critical patent/WO2014094308A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
    • C10J3/60—Processes
    • C10J3/64—Processes with decomposition of the distillation products
    • C10J3/66—Processes with decomposition of the distillation products by introducing them into the gasification zone
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/04—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of powdered coal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C10J3/82—Gas withdrawal means
    • C10J3/84—Gas withdrawal means with means for removing dust or tar from the gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/02—Dust removal
    • C10K1/026—Dust removal by centrifugal forces
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/001—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by thermal treatment
    • C10K3/003—Reducing the tar content
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/001—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by thermal treatment
    • C10K3/003—Reducing the tar content
    • C10K3/005—Reducing the tar content by partial oxidation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B47/00—Destructive distillation of solid carbonaceous materials with indirect heating, e.g. by external combustion
    • C10B47/28—Other processes
    • C10B47/30—Other processes in rotary ovens or retorts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B49/00—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated
    • C10B49/02—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge
    • C10B49/04—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge while moving the solid material to be treated
    • C10B49/08—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge while moving the solid material to be treated in dispersed form
    • C10B49/10—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with hot gases or vapours, e.g. hot gases obtained by partial combustion of the charge while moving the solid material to be treated in dispersed form according to the "fluidised bed" technique
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/094—Char
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • the present invention relates to the field of solid fuel energy chemical technology, and in particular, to a pyrolysis gasification method and a pyrolysis gasification apparatus for preparing a tar-free hydrogen-rich gas. Background technique
  • Gasification of carbonaceous solid fuels is an important means of utilization.
  • the gasification process of industrial operation generally adopts an autothermal process, that is, the heat required in the gasification reaction process is provided by burning a part of the gasification raw material. Since the reaction temperature during the entire gasification process is high, it is necessary to burn more than 40% of the carbonaceous raw material to maintain the temperature required for the reaction (above lolcrc). In the process, not only a part of the gasification raw material is burned, but also a useful gas component such as H 2 , CH 4 or the like is also burned, resulting in 11 ⁇ 2 / of the obtained gas. The ratio of 0 is greatly reduced.
  • the patent: CN101045525 proposes that in a spouted bed or a fluidized bed reactor under high pressure conditions, water vapor is used as a gasification gas, and carbon dioxide is completely absorbed by adding a carbon dioxide absorbent. The purpose of increasing hydrogen yield.
  • the process is carried out under high pressure conditions, in which the carbon dioxide absorber KOH or Ca(OH) 2 agglomerates seriously, affecting the normal operation of the process.
  • the tar production situation and the treatment method in the whole process are not mentioned.
  • An object of the present invention is to provide a pyrolysis gasification method for preparing a tar-free hydrogen-rich gas in order to solve the above problems.
  • Another object of the present invention is to provide a pyrolysis gasification apparatus based on the above-described pyrolysis gasification method for preparing a tar-free hydrogen-rich gas.
  • the pyrolysis gasification method for preparing a tar-free hydrogen-rich gas of the present invention comprises the following steps:
  • the pyrolysis gas phase product and the solid product produced in the step 1) are passed into a downstream tar cracking reactor, and the tar is removed by high temperature thermal cracking, partial oxidation and pyrolysis semi-coke catalytic cracking reaction, and partial gas is generated by pyrolysis of the semi-coke.
  • the reaction is carried out to obtain pyrolysis gas and pyrolysis semi-coke.
  • the carbonaceous solid raw material is coal, biomass or other carbonaceous solid waste or the like.
  • the reaction temperature in the upstream pyrolysis reactor is 700-1000 ° C, and the heat can be obtained by using an external heat type, that is, by burning fuel or passing outside the upstream pyrolysis reactor.
  • the hot flue gas is used to provide the heat required for the reaction, and can be obtained by self-heating, that is, by using a portion of oxygen/air or the like to be reacted with the reaction raw material to release the heat released by the reaction; the downstream tar cracking reactor
  • the internal reaction temperature is 900-130 CTC, which is maintained by the heat from the upstream overflow material itself and the heat released by the oxygen-containing atmosphere and the semi-coke reaction.
  • the above specific reaction temperatures can be adjusted according to different reaction materials.
  • the pyrolysis gas obtained in the step 2) is subjected to gas-solid separation; after the pyrolysis semi-coke obtained in the step 2) is quenched, waste heat recovery is performed.
  • waste heat recovery is performed.
  • it can be connected to the quenching device 8 during the semi-coke discharge process at the same time, and high-temperature and high-pressure steam is generated by heat exchange, and the heat carried by the semi-coke is recovered while the temperature of the semi-coke is lowered.
  • an appropriate amount of calcium-based minerals or other minerals or catalysts having tar cracking ability can be added to the pyrolysis feedstock.
  • the pyrolysis gasification method for producing a tar-free hydrogen-rich gas of the present invention can be carried out under normal pressure and under pressure.
  • the pyrolysis gasification apparatus of the present invention based on the pyrolysis gasification method for preparing a tar-free hydrogen-rich gas, comprising a feeding device 1, an overflow pipe 3, and an upstream pyrolysis reactor 2 and a downstream tar cracking reactor 4 The two are connected by an overflow pipe 3, and the feeding device 1 is in communication with the upstream pyrolysis reactor 2.
  • the upstream pyrolysis reactor is preferably a rotary kiln, a fluidized bed or a dilute phase transport bed;
  • the downstream tar cracking reactor is preferably a rotary kiln, a dilute phase transport bed, a settling furnace Or a fixed bed.
  • the pyrolysis gasification apparatus may further include a cyclone separator 5, a material leg 6, a discharge tube 7 and a quenching device 8, respectively, and the downstream tar cracking reactor 4 and the quenching device 8 phases are connected, the upper material inlet of the cyclone separator 5 is connected to the quenching device 8 through a pipe, and the solid product outlet at the bottom of the cyclone separator 5 is connected to the solid product collecting device through the material leg 6.
  • the upstream pyrolysis reactor may be a first rotary kiln reactor 13, and the downstream tar cracking reactor is a second rotary kiln reactor 14.
  • the upstream pyrolysis reactor may be a fluidized bed 10 and the downstream tar cracking reactor is a second rotary kiln reactor 14. Further, the fluidized bed 10 can also be connected to a plurality of second rotary kiln reactors 14 to form a device group.
  • the upstream pyrolysis reactor may be a dilute phase transport bed 11, and the downstream tar cracking reactor is a second rotary kiln reactor 14.
  • the cyclone separator 5 In addition to the above-mentioned cyclone separator 5, the material leg 6, the defocusing tube 7 and the quenching device 8, the cyclone separator 5, the material leg 6, and the quenching device 8 may be further included, the cyclone separator 5
  • the upper material inlet is in communication with the downstream tar cracking reactor 4 via a conduit, and the solid product outlet at the bottom of the cyclone separator 5 is in communication with the quenching device 8 via the feed leg 6.
  • the upstream pyrolysis reactor is a fluidized bed 10, and the downstream tar cracking reactor may be a dilute phase transport bed 11.
  • the upstream pyrolysis reactor is a fluidized bed 10
  • the downstream tar cracking reactor may be a settling furnace
  • the gas outlet at the lower side of the side wall of the settling furnace 12 is in communication with the inlet of the cyclone separator 5, and the bottom of the settling furnace 12 is directly in communication with the quenching device 8.
  • the supply device 1 is preferably a screw feed device.
  • the main idea of the invention is to first extract the volatile matter in the carbonaceous solid fuel by pyrolysis, and then further remove the tar in the pyrolysis gas, partially vaporize the semi-coke, and adjust the conversion of the composition of the pyrolysis atmosphere.
  • the reactions are coupled together to increase the content of high quality components (H 2 , CH 4 , etc.) in the pyrolysis gas, reducing the load on subsequent conversion processes.
  • the heat required for the entire reaction can be provided by by-product pyrolysis semi-coke combustion.
  • the invention avoids the problem that the combustion of the fuel in the conventional process provides heat and simultaneously burns the volatile matter, so that the content of H 2 and CH 4 in the pyrolysis gas is low, and the amount of reforming reaction of the subsequent gas composition is large.
  • Figure 1 is a schematic view of a pyrolysis gasification apparatus of the present invention
  • FIG. 2 is a schematic view of a pyrolysis gasification device combined with a two-stage rotary kiln according to the present invention
  • FIG. 3 is a schematic view of a pyrolysis gasification device using a hot flue gas as a heat source in combination with a two-stage rotary kiln according to the present invention
  • FIG. 4 is a schematic view of a pyrolysis gasification device combining a fluidized bed and a rotary kiln according to the present invention
  • Figure 5 is a schematic view of a pyrolysis gasification device combining a fluidized bed and a plurality of rotary kiln according to the present invention
  • Figure 6 is a schematic view of a pyrolysis gasification device combining a lean phase conveying bed and a rotary kiln according to the present invention
  • FIG. 7 is a schematic view of a pyrolysis gasification device combining a fluidized bed and a dilute phase transport bed according to the present invention
  • Figure 8 is a schematic view of a pyrolysis gasification device combining a fluidized bed and a settling furnace according to the present invention
  • Feeding device 1. Upstream pyrolysis reactor 3. Irrigation pipe 4. Downstream tar cracking reactor 5. Cyclone separator 6. Material leg
  • the pyrolysis gasification method for preparing a tar-free hydrogen-rich gas of the present invention comprises the following steps:
  • the pyrolysis gas phase product and the solid product produced in the step 1) are passed into a downstream tar cracking reactor, and the tar is removed by high temperature thermal cracking, partial oxidation and pyrolysis semi-coke catalytic cracking reaction to obtain pyrolysis gas and pyrolysis half. focal.
  • the upstream pyrolysis reactor can be a rotary kiln, a fluidized bed or a dilute phase transport bed.
  • the downstream tar cracking reactor described above may be a rotary kiln, a dilute phase transport bed, a settling furnace or a fixed bed.
  • the carbonaceous solid raw material is coal, biomass or other carbonaceous solid waste.
  • the reaction temperature in the upstream pyrolysis reactor is 700-100 CTC, and the reaction temperature in the downstream tar cracking reactor is 900-1300 °C.
  • the pyrolysis gas obtained in the step 2) is subjected to gas-solid separation; the pyrolysis semi-coke obtained in the step 2) is subjected to dry quenching, and waste heat recovery is performed.
  • the pyrolysis gasification apparatus of the present invention based on the above-described pyrolysis gasification method for preparing a tar-free hydrogen-rich gas, as shown in FIG. 1, includes a feeding device 1, an overflow pipe 3, and an upstream pyrolysis reactor 2 and The downstream tar cracking reactor 4, which is in communication via an overflow pipe 3, is in communication with the upstream pyrolysis reactor 2.
  • the upstream pyrolysis reactor is preferably a rotary kiln, a fluidized bed or a dilute phase transport bed;
  • the downstream tar cracking reactor is preferably a rotary kiln, a dilute phase transport bed, a settling furnace or a fixed bed.
  • the carbonaceous solid fuel is fed into the upstream pyrolysis reactor 2 via the feed device 1 for pyrolysis.
  • the resulting pyrolysis semi-coke along with the pyrolysis gas phase product passes through the overflow pipe 3 and enters the downstream tar cracking reactor 4.
  • the pyrolysis tar is pyrolyzed at a high temperature, partially oxidized and pyrolyzed.
  • the semi-coke catalytic cracking is combined to remove a large amount of high-quality pyrolysis gas.
  • the pyrolysis gasification device may further include a cyclone separator 5, a material leg 6, a discharge tube 7 and a quenching device 8, respectively, and the downstream tar cracking reactor 4 and the quenching device 8
  • the upper material inlet of the cyclone separator 5 is in communication with the quenching device 8 via a conduit
  • the solid product outlet at the bottom of the cyclone separator 5 is in communication with the solid product collection device via the material leg 6.
  • the carbonaceous solid fuel is fed into the upstream pyrolysis reactor 2 via the feed device 1 for pyrolysis.
  • the resulting pyrolysis semi-coke along with the pyrolysis gas phase product passes through the overflow pipe 3 and enters the downstream tar cracking reactor 4.
  • the pyrolysis tar is pyrolyzed at a high temperature, partially oxidized and pyrolyzed.
  • the semi-coke catalytic cracking is combined to remove a large amount of high-quality pyrolysis gas.
  • the generated gas is subjected to gas-solid separation by the cyclone separator 5, and the resulting semi-focus is discharged to the quenching device 8 through the defocused tube 7 to perform quenching treatment.
  • the material leg 6, the defocusing tube 7 and the quenching device 8 may be further included.
  • the upper material inlet of the cyclone separator 5 is in communication with the downstream tar cracking reactor 4 via a conduit, and the solid product outlet at the bottom of the cyclone separator 5 is in communication with the quenching device 8 via the feed leg 6.
  • the carbonaceous solid fuel is fed into the upstream pyrolysis reactor 2 via the feed device 1 for pyrolysis.
  • the pyrolysis semi-coke passes through the overflow pipe 3 along with the pyrolysis gas phase product, and enters the downstream tar cracking reactor 4 for reaction.
  • the resulting gas-solid mixture enters the cyclone separator 5 for gas-solid separation, and the resulting pyrolysis half-coke enters the quenching device 8 for quenching treatment.
  • the schematic diagram of the pyrolysis gasification device combined with the two-stage rotary kiln reactor of the present embodiment is as shown in FIG. 2, and includes a feeding device 1, a first rotary kiln reactor 13, a second rotary kiln reactor 14, and a quenching device. 8. Cyclone separator 5 and material leg 6 etc.
  • a carbonaceous solid fuel for example, coal
  • a feeding device 1 such as a screw feeder
  • the reactor 13 is subjected to pyrolysis at 700-90 CTC, and the resulting mixed gas and solid product are passed through the overflow pipe 3 to the downstream second rotary kiln reactor 14.
  • a certain amount of oxygen, water vapor or the like is introduced into the second rotary kiln reactor 14 and maintained at 110 CTC.
  • thermal cracking of the pyrolysis tar, partial oxidation, and catalytic cracking of the semi-coke on the pyrolysis tar are mainly caused to remove the tar; at the same time, partial gasification of the pyrolysis coke occurs, thereby obtaining a large amount High quality pyrolysis gases.
  • the reacted product gas and pyrolysis half coke enter the quenching device 8 through the discharge tube 7, and the resulting semi-coke is subjected to quenching treatment and can be used for industrial production.
  • the gasification gas obtained by gas-solid separation of the product gas through the cyclone separator 5 is used for industrial production and civil use.
  • the solid product separated by cyclone 5 enters the solid product collection unit through feed leg 6.
  • the Xilinhot coal with a particle size of less than 5 mm was used as a raw material, and the experimental treatment capacity was 50 kg/h.
  • Gas calorific value reaches 2300kcal / Nm
  • FIG. 3 A schematic diagram of the pyrolysis gasification apparatus of the present embodiment is shown in FIG. 3.
  • a burner 9 is additionally provided outside the first rotary kiln reactor 13 in the first embodiment, with hot flue gas as the first
  • the heat source of the rotary kiln reactor 13 is the same as in the first embodiment.
  • FIG. 4 A schematic diagram of a pyrolysis gasification apparatus combining the fluidized bed of the present embodiment and a rotary kiln reactor is shown in FIG. 4, and includes a feeding device 1, a fluidized bed 10, a second rotary kiln reactor 14, and a quenching device 8. , cyclone separator 5 and material leg 6 and the like.
  • the carbonaceous solid fuel having a particle size of ⁇ 20 mm is sent to the fluidized bed reactor 10 through the feeding device 1 for pyrolysis at 700-100 CTC, and is produced.
  • the mixed gas and the solid product enter the downstream second rotary kiln reactor 14 via the overflow pipe 3.
  • a certain amount of oxygen, water vapor or the like is introduced into the second rotary kiln reactor 14 and maintained at 1300 °C.
  • thermal cracking of the pyrolysis tar, partial oxidation, and catalytic cracking of the semi-coke on the pyrolysis tar are mainly caused to remove the tar; at the same time, partial gasification of the pyrolysis coke occurs, thereby obtaining a large amount High quality pyrolysis gases.
  • the reacted product gas and pyrolysis half coke enter the quenching device 8 through the discharge tube 7, and the resulting semi-coke is subjected to quenching treatment and can be used for industrial production.
  • the gasification gas obtained by gas-solid separation of the product gas through the cyclone separator 5 is used for industrial production and civil use.
  • the solid product separated by cyclone 5 enters the solid product collection unit through feed leg 6.
  • FIG. 5 The schematic diagram of the pyrolysis gasification device of the fluidized bed of the present embodiment combined with a plurality of rotary kiln reactors is shown in FIG. 5, including the feeding device 1, the fluidized bed 10, the second rotary kiln reactor 14, and the extinguishing device.
  • the process of specifically treating the reaction material is similar to that of the embodiment 3 except that a plurality of second rotary kiln reactors 14 are connected to the fluidized bed 10 to form a device group, which increases the throughput and improves the treatment efficiency.
  • FIG. 6 A schematic diagram of a pyrolysis gasification device combining the dilute phase transport bed and the rotary kiln reactor of the present embodiment is shown in FIG. 6, and includes a feeding device 1, a dilute phase transport bed 11, a second rotary kiln reactor 14, and a quenching unit.
  • the tar-free hydrogen-rich gas is prepared by using the pyrolysis gasification device
  • several feeding devices 1 of the carbonaceous solid fuel having a particle size of ⁇ 5 mm are sent to the dilute phase conveying bed 11 for pyrolysis at 700-90 CTC, resulting in pyrolysis.
  • the mixed gas and the solid product enter the downstream second rotary kiln reactor 14 via the overflow pipe 3.
  • a certain amount of oxygen, water vapor or the like is introduced into the second rotary kiln reactor 14 and maintained at 1100 °C.
  • thermal cracking of the pyrolysis tar, partial oxidation, and catalytic cracking of the semi-coke on the pyrolysis tar are mainly caused to remove the tar; at the same time, partial gasification of the pyrolysis coke occurs, thereby obtaining a large amount High quality pyrolysis gases.
  • the reacted product gas and pyrolysis half coke enter the quenching device 8 through the discharge tube 7, and the resulting semi-coke is subjected to quenching treatment and can be used for industrial production.
  • the gasification gas obtained by gas-solid separation of the product gas through the cyclone separator 5 is used for industrial production and civil use.
  • the solid product separated by cyclone 5 enters the solid product collection unit through feed leg 6.
  • FIG. 7 A schematic diagram of a pyrolysis gasification device combining the fluidized bed and the dilute phase transport bed of the present embodiment is shown in FIG. 7, and includes a feeding device 1, a fluidized bed 10, a dilute phase transport bed 11, a quenching device 8, and a cyclone. Separator 5 and material leg 6 and the like.
  • the carbonaceous solid fuel having a particle size of ⁇ 20 mm is fed into the fluidized bed 10 through the feeding device 1 and pyrolyzed at 700-90 CTC.
  • the mixed gas and the solid product enter the dilute phase transport bed 11 through the overflow pipe 3.
  • a certain amount of oxygen, water vapor or the like is introduced into the dilute phase transport bed 11 and maintained at 1100 °C.
  • thermal cracking of the pyrolysis tar, partial oxidation, and catalytic cracking of the semi-coke on the pyrolysis tar are mainly caused to remove the tar; at the same time, partial gasification of the pyrolysis coke occurs, thereby obtaining a large amount of high quality.
  • the gasification gas and pyrolysis semi-coke obtained after gas-solid separation of the product gas and pyrolysis semi-coke through the cyclone separator 5 can be used for Industrial production and civil use.
  • the solid product separated by the cyclone separator 5 enters the quenching device 8 through the material leg 6, and is subjected to quenching treatment to be used for industrial production.
  • the Xilinhot coal with a particle size of 0.5-1.5 mm was used as a raw material, and the experimental treatment capacity was 50 kg/h.
  • Gas calorific value reaches 1500kcal/Nm
  • FIG. 8 The schematic diagram of the pyrolysis gasification device combined with the fluidized bed and the settling furnace reactor of the present embodiment is shown in Fig. 8, including the feeding device 1, the fluidized bed 10, the settling furnace 12, the quenching device 8, and the cyclone separation. 5 and the leg 6 and the like.
  • the carbonaceous solid fuel having a particle size of ⁇ 20 mm is sent to the fluidized bed 10 through the screw feeder 1 to be pyrolyzed at 700-90 CTC, and the resulting mixture is mixed.
  • the gas as well as the solid product enters the settling furnace 12 via the overflow pipe 3.
  • a certain amount of oxygen, water vapor or the like is introduced into the settling furnace 12 and maintained at 1100 °C.
  • thermal cracking of the pyrolysis tar, partial oxidation, and catalytic cracking of the semi-coke on the pyrolysis tar are mainly caused to remove the tar; at the same time, partial gasification of the pyrolysis coke occurs, thereby obtaining a large amount of high-quality pyrolysis. gas.
  • the pyrolysis semi-coke after the reaction is directly introduced into the quenching device 8 by the settling furnace 12, and the resulting semi-coke is subjected to quenching treatment and can be used for industrial production.
  • the gas of the product gas obtained by gas-solid separation by cyclone separator 5 is used for industrial production and civil use.
  • the solid product separated by the cyclone separator 5 enters the quenching device 8 through the material leg 6, and is quenched and processed for industrial production.
  • reaction raw material may be added with a certain amount of calcium-based minerals or other minerals or catalysts having tar cracking ability, all of which do not contradict the main idea of the present invention.

Abstract

La présente invention concerne un procédé et un dispositif de gazéification par pyrolyse pour préparer un gaz riche en hydrogène sans goudron, le procédé de gazéification par pyrolyse comprenant les étapes suivantes : 1) transfert par l'intermédiaire d'un dispositif d'alimentation d'une matière première solide carbonique dans un réacteur de pyrolyse en amont pour la pyrolyse aérobie pour générer un produit en phase gazeuse et un produit solide pyrolysés ; 2) transfert du produit en phase gazeuse et du produit solide pyrolysés générés dans l'étape 1) dans un réacteur de pyrolyse de goudron en aval ; élimination du goudron par pyrolyse à haute température, oxydation partielle et réaction lytique catalytique par pyrolyse de carbocharbon ; et, simultanément, pyrolyse et gazéification d'une partie du carbocharbon pour obtenir un gaz pyrolysé et du carbocharbon pyrolysé. La présente invention évite les problèmes de faible teneur en H2 et CH4 dans le gaz pyrolysé et de charge de traitement élevée dans une réaction de reformage de composition de gaz consécutive en raison du fait que dans l'art antérieur, un composant volatil est également brûlé lorsque le combustible brûle pour produire de l'énergie thermique.
PCT/CN2012/087190 2012-12-21 2012-12-21 Procédé de gazéification par pyrolyse et dispositif pour préparer du gaz riche en hydrogène sans goudron WO2014094308A1 (fr)

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