CN107760386B - Differential circulating fluidized bed pyrolysis gasification device and method thereof - Google Patents

Differential circulating fluidized bed pyrolysis gasification device and method thereof Download PDF

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CN107760386B
CN107760386B CN201610707700.3A CN201610707700A CN107760386B CN 107760386 B CN107760386 B CN 107760386B CN 201610707700 A CN201610707700 A CN 201610707700A CN 107760386 B CN107760386 B CN 107760386B
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fluidized bed
gas
slow
fast
straight pipe
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CN107760386A (en
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金渭龙
顾松园
钟思青
金永明
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
    • C10J3/56—Apparatus; Plants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C10J3/82—Gas withdrawal means
    • C10J3/84—Gas withdrawal means with means for removing dust or tar from the gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1603—Integration of gasification processes with another plant or parts within the plant with gas treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention relates to a catalytic pyrolysis gasification device of a differential circulating fluidized bed, which solves the problems of low carbon conversion rate and methane yield and poor operation stability and reliability of a gasification furnace in the prior art. The method mainly comprises the following steps: the technical scheme that the catalyst-loaded carbon-containing raw material is subjected to catalytic pyrolysis, tar decomposition and methanation reaction in the gasification section of the fast fluidized bed to generate synthesis gas rich in methanation, and semicoke particles after pyrolysis are collected and circularly introduced into the slow fluidized bed to perform combustion gasification reaction better solves the problems and can be applied to the field of coal-to-natural gas.

Description

Differential circulating fluidized bed pyrolysis gasification device and method thereof
Technical Field
The invention relates to a device and a method for catalytic pyrolysis and gasification reaction of coal, in particular to a device and a method for catalytic pyrolysis and gasification of a differential circulating fluidized bed, belonging to the field of coal gasification.
Background
Coal is used as a basic energy source and an important industrial raw material in China, and plays a vital role in the development of economic construction in China. In the coming decades, the energy structure mainly based on coal is difficult to change, but the environment problem is seriously influenced by the low-efficiency and rough utilization mode of the coal, and the sustainable development of national economy and the health of people in China are influenced. Coal gasification technology is an important way for clean and efficient utilization of coal, and is widely applied to industrial industries such as metallurgy, chemical industry, building materials, machinery and the like and industrial fuel gas.
Coal gasification technologies can be classified into a methane-rich gas type and a syngas type containing little methane, depending on the coal gas products. At present, the gas type gasification technology mainly adopts fixed bed gasification, in the case of a lurgi fixed bed gasification furnace, the concentration of methane at an outlet can reach about 10%, which is the preferred technology of a coal gas unit in the coal-to-natural gas process technology, but the problems that the content of carbon residue in coal ash is high (10-30%), the requirements on raw materials are strict, non-caking coal is generally adopted, the gasification efficiency is low, a large amount of phenol water which is difficult to treat is easily generated, and the like exist. And the outlet gas of the entrained flow gasification technology almost does not contain methane, so that the entrained flow gasification technology is very suitable for the synthesis gas type gasification technology, but the load of a subsequent methanation unit is undoubtedly increased for the fuel gas type gasification technology, and the production cost of methane is increased. The fluidized bed gasification technology has the methane content between the two, can directly use crushed coal, is suitable for coal types with low caking property and high volatile content, and has higher gasification efficiency. When raw coal and a gasifying agent are introduced, a catalyst is further added, so that a high gasification reaction rate can be ensured under a low reaction temperature condition, and meanwhile, a catalytic methanation reaction is carried out, and the synthesis gas rich in methane is obtained.
US4318712 from Exxon corporation, USA, discloses a process for directly preparing methane by coal one-step method, which comprises mixing coal and catalyst, introducing into a fluidized bed gasifier, introducing 850 deg.C high-temperature superheated steam, maintaining the reaction temperature in the gasifier at about 700 deg.C and reaction pressure at 3.5MPa, performing gasification, shift and methanation reaction under the action of the catalyst, separating methane from the syngas at the outlet of the gasifier by cryogenic separation, and separating CO + H2And mixing the recycled synthesis gas with high-temperature steam, and introducing into the fluidized bed gasification furnace again to strengthen the methanation reaction process. The process adds a complex cryogenic separation unit and the introduction of recycle syngas reduces the rate of gasification and carbon conversion.
US20070000177a1, US GPE corporation, provides a more advanced process for producing methane in one step from coal based on Exxon technology, which uses highly efficient catalysts of alkali metal carbonates or alkali metal hydroxides, and adds calcium oxide for absorbing carbon dioxide generated during the reaction process, thereby directly obtaining methane-rich gas. However, the GPE process is the same as the Exxon process, and requires superheated steam to be heated to about 850 ℃, so that energy consumption is high, retention time of coal particles is long, carbon conversion rate is low, reaction temperature is difficult to maintain under the condition of no external heat supply, and the technology is still in a research and development stage.
Patent CN201010279560.7 of xinao group proposes a process for preparing methane-rich gas by multilayer fluidized bed catalytic gasification, which divides a gasification furnace into a synthesis gas generation section, a coal methanation section and a synthesis gas methanation section, so that combustion, gasification, methanation and pyrolysis reactions are carried out in sections, and self-heating reaction is realized. However, a plurality of layers of air distribution plates and overflow channels are required to be arranged in the gasification furnace, the structure in the gasification furnace is complex, the gasification efficiency and the methane yield are low, and ash residues are easy to melt and agglomerate at a combustion section at the bottom of the fluidized bed to form massive slag which blocks an outlet and a gas distributor of the gasification furnace, so that the operation stability of the device is influenced.
The problems of low technical indexes of process operation, poor economy and stability and the like in the coal catalytic gasification technology are important bottlenecks influencing the application of the catalytic gasification technology. Based on the fact that the gasification reaction and the methanation reaction are carried out in the same reactor, the reaction kinetics is guaranteed, the thermodynamic equilibrium of the reaction is considered, the gasification reaction and the methanation reaction can be carried out in a grading mode, and methane gas in volatile components of the carbon-containing materials is fully utilized, so that the methane-rich synthetic gas is obtained. Therefore, the invention provides a technology of catalytic pyrolysis gasification of a differential circulating fluidized bed by combining a fast fluidized bed and a slow fluidized bed, and the problems are specifically solved.
Disclosure of Invention
The invention mainly solves the technical problems of low carbon conversion rate and gasification strength, low methane yield and poor operation stability of the device in the prior art, and provides a catalytic pyrolysis gasification device of a differential circulating fluidized bed.
The second technical problem to be solved by the invention is to provide a catalytic pyrolysis gasification reaction method corresponding to the first technical problem.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: a catalytic pyrolysis gasification reaction device of a differential circulating fluidized bed comprises a raw material inlet 1, a fast fluidized bed 2, a slow fluidized bed 3, a necking 4, a gas distributor 5, a slag discharging port 6, a slag hopper 7, a fast fluidized bed outlet 8, a primary cyclone separator 9, a primary ash hopper 10, a primary return straight pipe 11, a secondary cyclone separator 12, a secondary ash hopper 13, a secondary return straight pipe 14, a return device 15, a return inlet 16 and a separation device 17. The fluidized bed is characterized in that a raw material inlet 1 is connected with a fast fluidized bed 2, a slow fluidized bed 3 is connected with the fast fluidized bed 2 through a necking 4, a gas distributor 5 is positioned at the bottom of the slow fluidized bed 3, an ash bucket 7 is connected with the slow fluidized bed 3 through a slag discharge opening 6, an outlet 8 of the fast fluidized bed is connected with a primary cyclone separator 9, an outlet of the primary cyclone separator 9 is connected with a secondary cyclone separator 12, a secondary return straight pipe 14 is connected with a primary return straight pipe 11, the primary return straight pipe 11 is connected with a return device 15, and a return inlet 16 is connected with the slow fluidized bed 3.
Raw materials import 1 be located 2 bottoms of fast fluidized bed, for 2 high 0~1/3 of fast fluidized bed, raw materials import 1's angle and horizontal axis are 0~75 contained angle.
The fast fluidized bed 2 is positioned at the upper part of the slow fluidized bed 3, and the inner diameter of the slow fluidized bed 3 is larger than that of the fast fluidized bed 2 and is 1.5-5.0 times of that of the fast fluidized bed 2.
The necking 4 is used for connecting the fast fluidized bed 2 and the slow fluidized bed 3, and the necking 4 and the horizontal axis form an included angle of 30-60 degrees.
The gas distributor 5 is positioned at the bottom of the slow fluidized bed 3 and forms an included angle of less than or equal to 60 degrees with the horizontal axis, the conical surface of the gas distributor 5 is provided with gas holes, the gas holes are uniformly distributed along the circumference and are provided with 5-20 circles of gas holes, and the aperture ratio is 0.1-5%.
The junction of the second-stage feed back straight pipe 14 and the first-stage feed back straight pipe 11 is located at the lower part of the first-stage feed back straight pipe 11, the junction is lower than 1/2 of the height of the first-stage feed back straight pipe 11, and the lower end of the second-stage feed back straight pipe 14 and the horizontal axis form an included angle of 30-70 degrees.
The position of the feed back inlet 16 is located in the middle of the slow fluidized bed 3 and is 1/3-2/3 of the height of the slow fluidized bed 3, and the angle of the feed back inlet 16 and the horizontal axis form an included angle of 15-75 degrees.
The bottom of the slow fluidized bed 3 is provided with a slag discharging opening 6, and the inner diameter of the slag discharging opening 6 is 1/6-4/6 of the inner diameter of the slow fluidized bed 3.
In order to solve the second problem, the invention adopts the following technical scheme: a method for catalytic pyrolysis gasification of a differential circulating fluidized bed is characterized by comprising the following steps: the carbon-containing raw material loaded with catalyst enters a fast fluidized bed 2 through a raw material inlet 1, is in mixed contact with high-temperature synthesis gas from a necking 4 below, is rapidly fluidized under the condition of high linear velocity, generates catalytic pyrolysis, tar decomposition and methanation reaction, semicoke particles and gas products after pyrolysis enter a primary cyclone separator 9 and a secondary cyclone separator 12, the separated semicoke particles are collected in a material returning device 15, are sent to the middle part of a slow fluidized bed 3 under the action of return air and are in mixed contact with a gasifying agent from a gas distributor 5, are turbulently fluidized under the low linear velocity, generate combustion gasification reaction, the generated high-temperature synthesis gas and semicoke particles with small particle size enter the fast fluidized bed through the necking 4, the fused and agglomerated coarse slag particles fall into a slag hopper 7 below through a slag outlet 6, and a small amount of tar is separated from the gas-phase products after purification and dust removal through the secondary cyclone separator 12 through a separating device 17 Thereby obtaining a synthesis gas rich in methane.
The carbonaceous raw material in the raw material inlet is selected from lignite, bituminous coal, anthracite, petroleum coke, biomass or a mixture thereof, and the particle size of the carbonaceous raw material is less than 10 mm.
The catalyst is selected from alkali metal, alkaline earth metal, transition metal or mixture thereof; the catalyst is loaded on raw coal in a mode of an impregnation method, a dry mixing method or an ion exchange method; the loading amount of the catalyst accounts for 0.1-50% of the mass of the raw coal.
The catalyst comprises: K. at least one of Ca, Mg, Li and Ni metal elements;
the catalyst contains K2A mixture of CO and CaO;
the catalyst contains K2CO, CaO and LiO2A mixture of (a);
the catalyst contains K2A mixture of CO, MgO, and NiO;
the catalyst is added with CO2A trapping substance selected from CaO, Ca (OH)2Dolomite, limestone or other regeneratively bound CO2Solid carbonate and bicarbonate forming material for furnace CO fixation2。
The catalyst is added with a substance for promoting tar decomposition, which is selected from CaO, MgO and K2O、Li2O, NiO, olivine or dolomite, etc., can rapidly realize the decomposition of tar.
The catalyst is added with mineral bonding substances selected from CaO and Ca (OH)2Calcium salts such as limestone, or other alkali and alkaline earth metals that react with and bind to the mineral constituents of silica, alumina and other carbonaceous materials, thereby inhibiting the participation of these minerals in the reaction and resulting in catalyst deactivation.
The operating temperature in the fast fluidized bed 2 is 400-600 ℃, the operating pressure is 3-6.5 MPa, the linear speed is 1-10 m/s, the particles are fast fluidized in the bed, and the gas phase retention time is 5-15 s.
The operating temperature in the slow fluidized bed 3 is 800-1200 ℃, the operating pressure is 3-6.5 MPa, the oxygen-carbon ratio is 0.5-1.2 mol/mol, the water-carbon ratio is 0.7-1.5 mol/mol, the linear velocity is 0.1-1 m/s, the particles are turbulently fluidized in the bed, and the gas phase residence time is 10-30 s.
The returned material at the bottom of the material returning device 15 is selected from nitrogen, argon, water vapor or a mixture thereof by winnowing.
The gasification agent introduced into the gas distributor 5 is selected from air, oxygen or a mixture of oxygen-enriched air and water vapor.
Brief description of the Process used for Using the apparatus of the present invention
The method comprises the steps of enabling a catalyst-loaded carbon-containing raw material to enter a fast fluidized bed 2 through a raw material inlet 1, enabling the catalyst-loaded carbon-containing raw material to be in mixed contact with high-temperature synthesis gas from a necking 4, carrying out catalytic pyrolysis, tar decomposition and methanation reaction, enabling the operation temperature to be 400-600 ℃, enabling the pressure to be 3.0-6.5 MPa, and generating CH4、CO2And a water vapor-based gas, wherein CO2The gas will be CO in the catalyst2The trapped species become immobilized within the catalyst, thereby increasing the methane content of the outlet gas. Introducing semicoke particles and gas products subjected to pyrolysis in the fast fluidized bed 2 into a primary cyclone separator 9 and a secondary cyclone separator 12, separating and collecting the semicoke particles in a material returning device 15, feeding the semicoke particles into the middle part of the slow fluidized bed 3 under the action of return air, mixing and contacting the semicoke particles with a gasifying agent from a gas distributor 5, carrying out turbulent fluidization at a low linear speed to generate combustion gasification reaction, wherein the operating temperature is 800-1200 ℃, the pressure is 3-6.5 MPa, and CO and H are generated2、CO2、H2High-temperature gas such as O and the like enters the fast fluidized bed 2 together with the semicoke particles with smaller particle size through the necking 4, heat and reactants are provided for the reaction in the fast fluidized bed 2, the semicoke particles completely react in the slow fluidized bed, and the coarse slag particles which are agglomerated by melting under the promoting action of mineral bonding substances fall into a slag hopper 7 below through a slag discharging port 6. And the gas phase product purified and dedusted by the secondary cyclone separator 12 is separated from a small amount of tar by a separation device 17 to obtain the synthesis gas rich in methane.
The advantages of the invention are briefly described as follows:
1) by adopting a mode of combining the fast fluidized bed and the slow fluidized bed, semicoke particles generated by pyrolysis in the fast fluidized bed are introduced into the slow fluidized bed to perform combustion gasification reaction to generate high-temperature synthesis gas, necessary heat and reactants are provided for pyrolysis reaction in the fast fluidized bed, and full utilization of carbon-containing raw materials and coupling of material flow and heat flow are realized.
2) The temperature in the slow fluidized bed is high, the bed layer density is high, the combustion gasification reaction is favorably carried out, wherein the semicoke particles with larger particle size can stay in the slow fluidized bed to be turbulently fluidized, the stay time of large particles in the slow fluidized bed is prolonged, the carbon conversion rate is improved, and the semicoke particles with smaller particle size can enter the fast fluidized bed along with the air flow to circularly flow.
3) CO addition to the supported catalyst2Trapping substances, which can bind CO in the gas phase2Form solid carbonate and bicarbonate to realize CO fixation in furnace2Is favorable for promoting the shift reaction (CO + H)2O＝CO2+H2) To the right, thereby effectively regulating the H in the furnace2The ratio of/CO is controlled within a range suitable for methanation reaction, the content of methane in the outlet gas is improved, and the load of subsequent gas separation and purification is reduced.
4) The supported catalyst is added with tar decomposition promoting substances such as CaO, MgO and K2O、Li2O, NiO, olivine or dolomite, and mineral caking substances such as CaO and Ca (OH) are added to the catalyst2And limestone, which react with and bind to the mineral constituents of silica, alumina and other carbonaceous materials, thereby inhibiting these minerals from reacting with other active components of the catalyst, resulting in catalyst deactivation.
5) The carbon-containing raw material is pyrolyzed in the fast fluidized bed, has high heating rate and good heat and mass transfer effect and is in H state2、CO、CH4And in the reducing atmosphere mainly comprising water vapor, the increase of the yield of pyrolysis gas can be promoted, and the carbon conversion rate of the carbon-containing material in the pyrolysis stage is improved.
By adopting the technical scheme of the invention, through the coupling of the fast fluidized bed and the slow fluidized bed, the catalytic pyrolysis, tar decomposition and methanation reaction are carried out in the fast fluidized bed, and the catalytic combustion gasification reaction is carried out in the slow fluidized bed, so that the carbon conversion rate at the outlet of the gasification device can reach 95%, and the methane content in the outlet synthesis gas is 75%.
Drawings
FIG. 1 is a schematic flow diagram of a differential circulating fluidized bed catalytic pyrolysis gasification device:
in FIG. 1, 1 is a raw material inlet; 2 is a fast fluidized bed; 3 is a slow fluidized bed; 4, necking; 5 is a gas distributor; 6 is a slag discharge port; 7 is a slag hopper; 8 is a fast fluidized bed outlet; 9 is a first-stage cyclone separator; 10 is a first-level ash bucket; 11 is a primary feed back straight pipe; 12 is a secondary cyclone separator; 13 is a secondary ash bucket; 14 is a secondary feed back straight pipe; 15 is a feed back device; 16 is a feed back inlet; and 17 is a separation device. A is a carbon-containing raw material of a supported catalyst; b is a gasifying agent; c is return gas; d is tar; e is synthesis gas rich in methanation; f is coarse slag.
The carbon-containing raw material A loaded with catalyst enters a fast fluidized bed 2 from a raw material inlet 1, is back-mixed and contacted with high-temperature synthesis gas from a lower necking 4, and is fast fluidized under the condition of higher linear velocity, and the catalyst contains CO2Trapping, tar decomposition and mineral substance bonding substances, performing catalytic pyrolysis, tar decomposition and methanation reactions, allowing pyrolyzed semicoke particles and gas products to enter a primary cyclone separator 9 and a secondary cyclone separator 12, collecting the separated semicoke particles in a return device 15 through a primary ash bucket 10, a primary return straight pipe 11, a secondary ash bucket 13 and a secondary return straight pipe 14, feeding the separated semicoke particles into the middle part of a slow fluidized bed 3 through a return inlet 16 under the action of return gas C, mixing and contacting with a gasifying agent B from a gas distributor 5, performing turbulent fluidization at a low linear velocity to perform combustion gasification reaction, allowing the generated high-temperature synthesis gas and semicoke particles with small particle size to enter a fast fluidized bed 2 through a reducing port 4 to provide heat and reactants for the fast fluidized bed, and allowing the fused and agglomerated coarse slag F particles to fall into a slag bucket 5 below through a lower slag port 6, and a small amount of tar D is separated from the gas-phase product purified and dedusted by the secondary cyclone 12 through a separation device to obtain the synthesis gas E rich in methane.
The present invention will be further illustrated by the following examples, but is not limited to these examples.
Detailed Description
[ example 1 ]
The utility model provides a differential circulating fluidized bed catalytic pyrolysis gasification reaction unit, fast fluidized bed internal diameter 0.2m, linear velocity 2m/s, gaseous phase dwell time 10s, slow fluidized bed internal diameter 0.5m, linear velocity 0.2m/s, gaseous phase dwell time 15s, the raw materials import is located 1/8 of fast fluidized bed height, throat and horizontal axis contained angle 45, the inclined plane of gas distributor is 30 with the contained angle of horizontal axis, be equipped with 10 rings of gas pockets on the gas distributor conical surface, the percent opening is 1.5%, lower slag notch internal diameter 0.2 m.
Inner Mongolian lignite and 10% K are selected for experiments2CO3Mixing the catalyst with 10% of CaO, adding the mixture into a fast fluidized bed from a raw material inlet, mixing and contacting the mixture with high-temperature synthetic gas from a necking to perform pyrolysis, tar decomposition and methanation reactions, wherein the operating temperature is 500 ℃, the operating pressure is 3.5MPa, generating the synthetic gas rich in methane, and discharging CH in the synthetic gas4Concentration 75%, methane yield 0.82Nm3The tar yield was 0.5% per kg. Semicoke particles in the synthesis gas at the outlet are separated by the primary cyclone separator and the secondary cyclone separator and are circularly sent into the slow fluidized bed through the feed back device to perform combustion gasification reaction with oxygen and water vapor from the gas distributor, the oxygen-carbon ratio is controlled to be 1.0mol/mol, the water vapor-coal ratio is controlled to be 1.2mol/mol, the operating temperature of the slow fluidized bed is 1000 ℃, the operating pressure is 3.5MPa, the generated high-temperature synthesis gas and semicoke particles with smaller particle size enter the fast fluidized bed through a necking to provide reactants and heat for the reaction in the furnace, the molten and agglomerated coarse slag particles are discharged into a slag hopper through a slag discharging port, and the carbon conversion rate at the outlet of the gasification device reaches 96%.
[ example 2 ]
The utility model provides a differential circulating fluidized bed catalytic pyrolysis gasification reaction unit, fast fluidized bed internal diameter 0.2m, linear velocity 2m/s, gaseous phase dwell time 15s, slow fluidized bed internal diameter 0.5m, linear velocity 0.2m/s, gaseous phase dwell time 15s, the raw materials import is located 1/8 of fast fluidized bed height, throat and horizontal axis contained angle 45, the inclined plane of gas distributor is 30 with the contained angle of horizontal axis, be equipped with 10 rings of gas pockets on the gas distributor conical surface, the percent opening is 1.5%, lower slag notch internal diameter 0.2 m.
Inner Mongolian lignite and 10% K are selected for experiments2CO3Mixing the catalyst with 10% of CaO, adding the mixture into a fast fluidized bed from a raw material inlet, mixing and contacting the mixture with high-temperature synthetic gas from a necking to perform pyrolysis, tar decomposition and methanation reactions, wherein the operating temperature is 500 ℃, the operating pressure is 3.5MPa, generating the synthetic gas rich in methane, and discharging CH in the synthetic gas4Concentration 77%, methane yield 0.86Nm3The tar yield was 0.3% per kg. Semicoke particles in the synthesis gas at the outlet are separated by the primary cyclone separator and the secondary cyclone separator and are circularly sent into the slow fluidized bed through the feed back device to perform combustion gasification reaction with oxygen and water vapor from the gas distributor, the oxygen-carbon ratio is controlled to be 1.0mol/mol, the water vapor-coal ratio is controlled to be 1.2mol/mol, the operating temperature of the slow fluidized bed is 1000 ℃, the operating pressure is 3.5MPa, the generated high-temperature synthesis gas and semicoke particles with smaller particle size enter the fast fluidized bed through a necking to provide reactants and heat for the reaction in the furnace, the molten and agglomerated coarse slag particles are discharged into a slag hopper through a slag discharging port, and the carbon conversion rate at the outlet of the gasification device reaches 97%.
[ example 3 ]
The utility model provides a differential circulating fluidized bed catalytic pyrolysis gasification reaction unit, fast fluidized bed internal diameter 0.2m, linear velocity 2m/s, gaseous phase dwell time 10s, slow fluidized bed internal diameter 0.5m, linear velocity 0.2m/s, gaseous phase dwell time 20s, the raw materials import is located 1/8 of fast fluidized bed height, throat and horizontal axis contained angle 45, the inclined plane of gas distributor is 30 with the contained angle of horizontal axis, be equipped with 10 rings of gas pockets on the gas distributor conical surface, the percent opening is 1.5%, lower slag notch internal diameter 0.2 m.
Inner Mongolian lignite and 10% K are selected for experiments2CO3Mixing the catalyst with 10% of CaO, adding the mixture into a fast fluidized bed from a raw material inlet, mixing and contacting the mixture with high-temperature synthetic gas from a necking to perform pyrolysis, tar decomposition and methanation reactions, wherein the operating temperature is 500 ℃, the operating pressure is 3.5MPa, generating the synthetic gas rich in methane, and discharging CH in the synthetic gas4Concentration 75%, methane yield 0.84Nm3The tar yield was 0.5% per kg. Semicoke in export syngasThe particles are separated by the primary cyclone separator and the secondary cyclone separator and are circularly sent into the slow fluidized bed through the feed back device to perform combustion gasification reaction with oxygen and water vapor from the gas distributor, the oxygen-carbon ratio is controlled to be 1.0mol/mol, the water vapor-coal ratio is controlled to be 1.2mol/mol, the operating temperature of the slow fluidized bed is 1000 ℃, the operating pressure is 3.5MPa, the generated high-temperature synthesis gas and semicoke particles with smaller particle size enter the fast fluidized bed through a necking to provide reactants and heat for the reaction in the furnace, the fused and agglomerated coarse slag particles are discharged into a slag hopper through a slag discharging port, and the carbon conversion rate at the outlet of the gasification device reaches 98%.
[ example 4 ]
The utility model provides a differential circulating fluidized bed catalytic pyrolysis gasification reaction unit, fast fluidized bed internal diameter 0.2m, linear velocity 2m/s, gaseous phase dwell time 10s, slow fluidized bed internal diameter 0.5m, linear velocity 0.2m/s, gaseous phase dwell time 15s, the raw materials import is located 1/8 of fast fluidized bed height, throat and horizontal axis contained angle 45, the inclined plane of gas distributor is 30 with the contained angle of horizontal axis, be equipped with 10 rings of gas pockets on the gas distributor conical surface, the percent opening is 1.5%, lower slag notch internal diameter 0.2 m.
Inner Mongolian lignite and 10% K are selected for experiments2CO3+8％CaO+2％Li2Mixing O catalyst, adding into the fast fluidized bed from the raw material inlet, mixing with high temperature synthetic gas from the throat, performing pyrolysis, tar decomposition and methanation reaction at 500 deg.C under 3.5MPa to obtain synthetic gas rich in methane, and discharging CH in the synthetic gas4Concentration 78% and methane yield 0.90Nm3The tar yield was 0.1% per kg. Semicoke particles in the outlet synthesis gas are separated by a primary cyclone separator and a secondary cyclone separator and are circularly sent into a slow fluidized bed through a feed back device to perform combustion gasification reaction with oxygen and water vapor from a gas distributor, the oxygen-carbon ratio is controlled to be 1.0mol/mol, the water vapor-coal ratio is controlled to be 1.2mol/mol, the operating temperature of the slow fluidized bed is 1000 ℃, the operating pressure is 3.5MPa, the generated high-temperature synthesis gas and semicoke particles with smaller particle size enter the fast fluidized bed through a necking to provide reactants and heat for the reaction in the furnace, and the melted and agglomerated coarse slag particles are communicated with a first-stage cyclone separator and a second-stage cyclone separatorThe carbon is discharged into a slag hopper through a slag discharging port, and the carbon conversion rate of the outlet of the gasification device reaches 99%.
[ example 5 ]
The utility model provides a differential circulating fluidized bed catalytic pyrolysis gasification reaction unit, fast fluidized bed internal diameter 0.2m, linear velocity 2m/s, gaseous phase dwell time 10s, slow fluidized bed internal diameter 0.5m, linear velocity 0.2m/s, gaseous phase dwell time 15s, the raw materials import is located 1/8 of fast fluidized bed height, throat and horizontal axis contained angle 45, the inclined plane of gas distributor is 30 with the contained angle of horizontal axis, be equipped with 10 rings of gas pockets on the gas distributor conical surface, the percent opening is 1.5%, lower slag notch internal diameter 0.2 m.
Inner Mongolian lignite and 10% K are selected for experiments2CO3Mixing the catalyst of + 8% of MgO and 2% of NiO, adding the mixture into the fast fluidized bed from a raw material inlet, mixing and contacting the mixture with high-temperature synthetic gas from a throat, carrying out pyrolysis, tar decomposition and methanation reaction at the operating temperature of 500 ℃ and the operating pressure of 3.5MPa to generate synthetic gas rich in methane, and discharging CH in the synthetic gas4Concentration 79%, methane yield 0.91Nm3The tar yield was 0.01% per kg. Semicoke particles in the synthesis gas at the outlet are separated by the primary cyclone separator and the secondary cyclone separator and are circularly sent into the slow fluidized bed through the feed back device to perform combustion gasification reaction with oxygen and water vapor from the gas distributor, the oxygen-carbon ratio is controlled to be 1.0mol/mol, the water vapor-coal ratio is controlled to be 1.2mol/mol, the operating temperature of the slow fluidized bed is 1000 ℃, the operating pressure is 3.5MPa, the generated high-temperature synthesis gas and semicoke particles with smaller particle size enter the fast fluidized bed through a necking to provide reactants and heat for the reaction in the furnace, the molten and agglomerated coarse slag particles are discharged into a slag hopper through a slag discharging port, and the carbon conversion rate at the outlet of the gasification device reaches 99%.
[ example 6 ]
The utility model provides a differential circulating fluidized bed catalytic pyrolysis gasification reaction unit, fast fluidized bed internal diameter 0.2m, linear velocity 2m/s, gaseous phase dwell time 10s, slow fluidized bed internal diameter 0.5m, linear velocity 0.2m/s, gaseous phase dwell time 15s, the raw materials import is located 1/8 of fast fluidized bed height, throat and horizontal axis contained angle 45, the inclined plane of gas distributor is 30 with the contained angle of horizontal axis, be equipped with 10 rings of gas pockets on the gas distributor conical surface, the percent opening is 1.5%, lower slag notch internal diameter 0.2 m.
Inner Mongolian lignite and 10% K are selected for experiments2CO3Mixing the catalyst with 10% of CaO, adding the mixture into a fast fluidized bed from a raw material inlet, mixing and contacting the mixture with high-temperature synthetic gas from a necking to perform pyrolysis, tar decomposition and methanation reactions, wherein the operating temperature is 500 ℃, the operating pressure is 3.5MPa, generating the synthetic gas rich in methane, and discharging CH in the synthetic gas4Concentration 75%, methane yield 0.87Nm3The tar yield was 0.3% per kg. Semicoke particles in the synthesis gas at the outlet are separated by the primary cyclone separator and the secondary cyclone separator and are circularly sent into the slow fluidized bed through the feed back device to perform combustion gasification reaction with oxygen and water vapor from the gas distributor, the oxygen-carbon ratio is controlled to be 1.2mol/mol, the water vapor-coal ratio is controlled to be 1.2mol/mol, the operating temperature of the slow fluidized bed is 1100 ℃, the operating pressure is 3.5MPa, the generated high-temperature synthesis gas and semicoke particles with smaller particle size enter the fast fluidized bed through a necking to provide reactants and heat for the reaction in the furnace, the molten and agglomerated coarse slag particles are discharged into a slag hopper through a slag discharging port, and the carbon conversion rate at the outlet of the gasification device reaches 99%.
[ COMPARATIVE EXAMPLE 1 ]
A coal gasification reaction device in the traditional two-step coal-to-methane process is adopted, a Lurgi fixed bed gasification furnace is taken as an example, coal is selected as inner Mongolia coal in an experiment, the operating pressure is 3.5MPa, and the average operating temperature is 800 ℃. CO + H in the obtained outlet gas component255.4% in content, only 12% in methane and a methane yield of 0.2Nm3Kg, carbon conversion 90%.
[ COMPARATIVE EXAMPLE 2 ]
A catalytic gasification reaction device in a one-step process for preparing methane from coal, which is proposed by Exxon company, is adopted, and a 10% potassium carbonate catalyst is selected, wherein the operating pressure is 3.5MPa, the superheated steam is 850 ℃, and the operating temperature is 700 ℃. The experiment shows that the content of methane in the outlet gas component is 19 percent, and the yield of the methane is 0.39Nm3Per kg, carbon conversion 85%.
[ COMPARATIVE EXAMPLE 3 ]
Multilayer fluidized bed proposed by Xinao groupIn a gasification reaction device in the process of preparing the methane-rich gas by catalytic gasification, inner Mongolian lignite is taken as a raw material in an experiment, 10% of potassium carbonate catalyst is loaded, the operating pressure is 3.5MPa, and the operating temperature is 700 ℃. The methane content in the obtained outlet gas component was 8.4%, and the methane yield was 0.15Nm3Kg, carbon conversion 50%.
Figure BDA0001087609300000101
Figure BDA0001087609300000102
Figure BDA0001087609300000111

Claims (7)

1. A differential circulating fluidized bed catalytic pyrolysis gasification device comprises a raw material inlet (1), a fast fluidized bed (2), a slow fluidized bed (3), a reducing port (4), a gas distributor (5), a slag discharging port (6), a slag hopper (7), a fast fluidized bed outlet (8), a primary cyclone separator (9), a primary ash hopper (10), a primary return straight pipe (11), a secondary cyclone separator (12), a secondary ash hopper (13), a secondary return straight pipe (14), a return device (15), a return inlet (16) and a separation device (17); the fluidized bed is characterized in that a raw material inlet (1) is connected with a fast fluidized bed (2), a slow fluidized bed (3) is connected with the fast fluidized bed (2) through a reducing port (4), a gas distributor (5) is positioned at the bottom of the slow fluidized bed (3), an ash hopper (7) is connected with the slow fluidized bed (3) through a slag discharge port (6), a fast fluidized bed outlet (8) is connected with a primary cyclone separator (9), a primary cyclone separator (9) outlet is connected with a secondary cyclone separator (12), a secondary return straight pipe (14) is connected to a primary return straight pipe (11), the primary return straight pipe (11) is connected with a return device (15), and a return inlet (16) is connected with the slow fluidized bed (3); raw materials import (1) be located the bottom of fast fluidized bed (2), for 0~1/3 of fast fluidized bed (2) height, the angle and the horizontal axis of raw materials import (1) are 0~75 contained angle, the position of feed back import (16) be located slow fluidized bed (3) middle part, for 1/3~2/3 of slow fluidized bed (3) height, the angle and the horizontal axis of feed back import (16) are 15~75 contained angles.
2. The differential speed circulating fluidized bed catalytic pyrolysis gasification device according to claim 1, characterized in that the fast fluidized bed (2) is located at the upper part of the slow fluidized bed (3), and the inner diameter of the slow fluidized bed (3) is larger than that of the fast fluidized bed (2) and is 1.5-5.0 times of that of the fast fluidized bed (2).
3. The differential circulating fluidized bed catalytic pyrolysis gasification device according to claim 1, wherein the gas distributor (5) is located at the bottom of the slow fluidized bed (3) and forms an included angle of less than or equal to 60 degrees with the horizontal axis, the conical surface of the gas distributor (5) is provided with gas holes, the gas holes are uniformly arranged along the circumference, 5-20 circles of gas holes are arranged, and the aperture ratio is 0.1-5%.
4. The differential speed circulating fluidized bed catalytic pyrolysis gasification device according to claim 1, characterized in that the connection position of the secondary return straight pipe (14) and the primary return straight pipe (11) is located at the lower part of the primary return straight pipe (11), the connection position is lower than 1/2 of the height of the primary return straight pipe (11), and the lower end of the secondary return straight pipe (14) forms an included angle of 30-70 degrees with the horizontal axis.
5. A differential circulating fluidized bed catalytic pyrolysis gasification reaction-method adopts the differential circulating fluidized bed catalytic pyrolysis gasification device of any one of claims 1 to 4, and is characterized by mainly comprising the following steps: the carbon-containing raw material loaded with catalyst enters the fast fluidized bed (2) through the raw material inlet (1) to be mixed and contacted with high-temperature synthesis gas from the lower necking (4), fast fluidization is carried out under the condition of higher linear velocity, and catalytic heat is generatedDecomposing, decomposing tar and performing methanation reaction, feeding the pyrolyzed semicoke particles and gas products into a primary cyclone separator (9) and a secondary cyclone separator (12), collecting the separated semicoke particles in a feed back device (15), is fed into the middle part of the slow fluidized bed (3) under the action of the return air and is mixed and contacted with a gasifying agent B from a gas distributor (5), turbulent fluidization is carried out at a lower linear velocity to generate combustion gasification reaction, the generated high-temperature synthesis gas and semi-coke particles with smaller particle size enter a fast fluidized bed through a necking (4), the melted and agglomerated coarse slag particles fall into a slag hopper (7) below through a slag discharging opening (6), and a small amount of tar is separated from the gas-phase product purified and dedusted by the secondary cyclone separator (12) through a separation device (17) to obtain the synthesis gas rich in methane, wherein the catalyst is selected from the following components: K. at least one of Ca, Mg, Li and Ni metal elements; the catalyst contains K2CO3CaO and Li2Mixtures of O, or K2CO3A mixture of MgO and NiO.
6. The differential speed circulating fluidized bed catalytic pyrolysis gasification reaction-method according to claim 5, characterized in that the catalyst is loaded on raw coal by means of impregnation, dry mixing or ion exchange; the loading amount of the catalyst accounts for 0.1-50% of the mass of the raw coal.
7. The differential speed circulating fluidized bed catalytic pyrolysis gasification reaction-method according to claim 5, characterized in that the operating temperature in the fast fluidized bed (2) is 400-600 ℃, the operating pressure is 3-6.5 MPa, the linear velocity is 1-10 m/s, the particles are fast fluidized in the bed, and the gas phase residence time is 5-15 s; the operating temperature in the slow fluidized bed (3) is 800-1200 ℃, the operating pressure is 3-6.5 MPa, the oxygen-carbon ratio is 0.5-1.2 mol/mol, the water-carbon ratio is 0.7-1.5 mol/mol, the linear velocity is 0.1-1 m/s, particles are turbulently fluidized in the bed, and the gas phase residence time is 10-30 s.
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