CN107760384B - Efficient device and method for preparing methane-rich synthesis gas through catalytic coal gasification - Google Patents

Efficient device and method for preparing methane-rich synthesis gas through catalytic coal gasification Download PDF

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CN107760384B
CN107760384B CN201610707698.XA CN201610707698A CN107760384B CN 107760384 B CN107760384 B CN 107760384B CN 201610707698 A CN201610707698 A CN 201610707698A CN 107760384 B CN107760384 B CN 107760384B
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fluidized bed
furnace
gasification
methanation
pyrolysis
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CN107760384A (en
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金渭龙
顾松园
钟思青
高攀
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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
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—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
    • C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
    • 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
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/093—Coal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0983—Additives
    • C10J2300/0986—Catalysts
    • 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
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656—Conversion of synthesis gas to chemicals
    • C10J2300/1662—Conversion of synthesis gas to chemicals to methane (SNG)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1807—Recycle loops, e.g. gas, solids, heating medium, water
    • 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 an efficient device and method for preparing methane-rich synthetic gas by catalytic coal gasification, and solves the problems of low carbon conversion rate and gasification intensity, low methane yield, high energy consumption and poor operation stability of a gasification furnace in the prior art. The invention consists of a fluidized bed gasification furnace and a fluidized bed pyrolysis methanation furnace, and is characterized in that a raw material inlet is positioned at the upper part of the fluidized bed pyrolysis methanation furnace, the bottom of the fluidized bed pyrolysis methanation furnace is connected with the bottom of the fluidized bed gasification furnace, and a synthesis gas guide pipe connected with an outlet at the upper part of the fluidized bed gasification furnace extends into the bottom of the pyrolysis methanation furnace. The method mainly comprises the following steps: the technical scheme is that the coal sample loaded with the catalyst and the high-temperature synthesis gas are subjected to catalytic pyrolysis and methanation reactions in the fluidized bed pyrolysis methanation furnace, and the pyrolyzed semicoke particles and coal ash particles enter the fluidized bed gasification furnace to be subjected to combustion gasification reactions.

Description

Efficient device and method for preparing methane-rich synthesis gas through catalytic coal gasification
Technical Field
The invention relates to a high-efficiency coal catalytic gasification device and method, in particular to a catalytic gasification reaction device and method combining a fluidized bed pyrolysis methanation furnace and a fluidized bed gasification furnace for a staged reaction, and belongs to the field of coal catalytic gasification.
Background
Rich coal, poor oil and little gas are energy structural characteristics of China, and the demand for natural gas is increasing along with the rapid development of economy of China and the acceleration of urbanization pace. The natural gas yield of China is the amount which cannot meet the demand of natural gas, the contradiction between supply and demand is increasingly prominent, the supply gap can only be made up by relying on import, and the energy safety of China is greatly influenced. Because China is a big coal country and the yield of coal is rich, the conversion of coal into natural gas is an important way for clean and efficient utilization of coal, and because the energy conversion rate is high, the method is suitable for the national situation of China, effectively relieves the contradiction between supply and demand of natural gas, and becomes an important direction in the research field of the current coal chemical industry.
The common technology for producing natural gas from coal at present is to convert coal into synthetic gas (CO + H)2) The method for obtaining SNG by methanation needs to go through the following steps: gasification, shift cooling, purification, methane synthesis and the like, namely a two-step process for preparing natural gas from coal. The method has the disadvantages of high reaction energy consumption, more heat loss and more reaction devices, so the process is more complicated. However, the one-step coal-based natural gas technology takes coal as a raw material, methane is directly synthesized under the action of a catalyst, and the synthesis gas rich in methane is obtained by performing catalytic gasification, catalytic conversion and catalytic methanation reactions in the same reaction.
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. The combustion, gasification, methanation reaction and pyrolysis reaction are carried out in sections, and the 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.
In the above technology, because the endothermic gasification reaction and the exothermic methanation reaction are carried out in the same reactor, both the reaction kinetics and the thermodynamic equilibrium of the reaction need to be ensured, which limits the operating temperature of the reaction, resulting in a lower gasification reaction rate as a limiting reaction and a lower equilibrium concentration of methane as a methanation equilibrium reaction. Therefore, the gasification and methanation reactions can be carried out in a grading manner, the gasification reactor carries out rapid catalytic gasification reaction to generate synthesis gas, and the pyrolysis methanation reactor carries out catalytic pyrolysis and methanation reactions to generate low-temperature methane-enriched synthesis gas. Therefore, the gasification and methanation reactions can be considered to be carried out in a grading way, and a technology for preparing the methane-rich synthetic gas through catalytic coal gasification, which has the advantages of high gasification intensity, high gasification reaction rate, high methanation degree, simple process, stable operation and high efficiency, can be researched.
Disclosure of Invention
The invention mainly solves the technical problems of low carbon conversion rate and gasification strength, low methane yield, high energy consumption and poor operation stability in the prior art, and provides an efficient device for preparing methane-rich synthetic gas by catalytic gasification of coalReacting to generate high-temperature synthesis gas, introducing the high-temperature synthesis gas into a pyrolysis methanation furnace through a guide pipe, and loading the high-temperature synthesis gas containing CO2And carrying out low-temperature pyrolysis and methanation reaction under the action of the catalyst of the captured and mineral bonded substances to generate the synthesis gas rich in methane. Realizes material balance, improves gasification intensity, carbon conversion rate and methane yield, and reduces system energy consumption.
The second technical problem to be solved by the invention is to provide a catalytic 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: the utility model provides a device of rich methane synthetic gas of efficient coal catalytic gasification, includes raw materials import 1, fluidized bed gasifier 2, gasifying agent gas distributor 3, gasifier export 4, synthetic gas pipe 5, fluidized bed pyrolysis methanation furnace 6, fluidization wind gas distributor 7, semicoke import 8, pyrolysis methanation furnace export 9, cyclone 10, ash bucket 11, feed back straight tube 12, feed back device 13, feed back import 14, separator 15, lower sediment mouth 16, sediment fill 17 are constituteed. The fluidized bed pyrolysis methanation furnace is characterized in that a raw material inlet 1 is connected with a fluidized bed pyrolysis methanation furnace 6, the bottom of the fluidized bed pyrolysis methanation furnace 6 is connected with the bottom of a fluidized bed gasification furnace 2, a fluidized bed gasification furnace outlet 4 is connected with the fluidized bed pyrolysis methanation furnace 6 through a synthesis gas guide pipe 5, a fluidized bed gasification furnace outlet 9 is connected with a cyclone separator 10, the bottom of the cyclone separator 10 is connected with an ash hopper 11 and a return straight pipe 12, a return device 13 is connected with the fluidized bed gasification furnace 2 through a return inlet 14, an outlet above the cyclone separator 10 is connected with a separating device 15, and the bottom of the fluidized bed gasification furnace 2 is connected with a slag hopper 17 through a slag discharge.
The position of the raw material inlet 1 is 1/2-1/1 of the fluidized bed pyrolysis methanation furnace at 6 heights, and the angle of the raw material inlet 1 and the horizontal axis form an included angle of 0-75 degrees.
Fluidized wind gas distributor 7 be located fluidized bed pyrolysis methanation furnace 6 bottom, be the level setting, be equipped with the gas pocket on the fluidized wind gas distributor 7, the gas pocket is evenly arranged along the circumference, is equipped with 10 ~ 30 circles of gas pockets, the percent opening is 0.1 ~ 5%.
The inner diameter of the fluidized bed pyrolysis methanation furnace 6 is larger than that of the fluidized bed gasification furnace 2 and is 1.1-3.0 times of the inner diameter of the fluidized bed gasification furnace 2.
The semi-coke inlet 8 is positioned at the bottom of the fluidized bed gasification furnace 2 and is 1/8-1/3 of the height of the fluidized bed gasification furnace 2.
The gasification agent gas distributor 3 is positioned at the bottom of the fluidized bed gasification furnace 2, forms an included angle of less than or equal to 60 degrees with the horizontal axis, is provided with a slag outlet 16 at the center, is provided with gas holes on the conical surface of the gasification agent gas distributor 3, is uniformly arranged along the circumference, is provided with 5-20 circles of gas holes, and has the aperture ratio of 0.1-5%.
The height of the synthesis gas guide pipe 5 is more than 3/4 of the height of the fluidized bed pyrolysis methanation furnace 6, the synthesis gas guide pipe extends into the bottom of the fluidized bed pyrolysis methanation furnace 6, and the inner diameter of the synthesis gas guide pipe 5 is 1/8-1/3 of the inner diameter of the fluidized bed pyrolysis methanation furnace 6.
The inner diameter of the cyclone separator 11 is 1.5-2 times of the inner diameter of the ash bucket 12.
The bottom of the material returning device 13 is communicated with material returning air which is used for loosening and fluidizing the fly ash separated by the cyclone separator 10.
The position of the feed back inlet 14 is located at the bottom of the fluidized bed gasification furnace 2 and is 1/8-1/3 of the height of the fluidized bed gasification furnace 2, and the angle of the feed back inlet 14 and the horizontal axis form an included angle of 15-75 degrees.
In order to solve the second problem, the invention adopts the following technical scheme: a high-efficiency method for preparing methane-rich synthesis gas by catalytic coal gasification is characterized by comprising the following steps: the coal sample A loaded with catalyst enters the fluidized bed pyrolysis methanation furnace 6 through the raw material inlet 1, is mixed and contacted with high-temperature synthesis gas from a synthesis gas guide pipe 5 and fluidized air C of a fluidized air gas distributor 7 to carry out pyrolysis and methanation reactions, the pyrolyzed semicoke particles enter the fluidized bed gasification furnace 2 through a semicoke inlet 8, the methane-rich synthesis gas and coal ash particles at an upper pyrolysis methanation furnace outlet 9 enter a cyclone separator 10, the separated coal ash particles are returned to the bottom of the fluidized bed gasification furnace 2 under the action of a material returning device 13 and return air D, a combustion gasification reaction is carried out in the fluidized bed gasification furnace 2, the generated high-temperature synthesis gas enters the fluidized bed pyrolysis methanation furnace 6 through the guide pipe 5, the melt agglomerated coarse slag particles G fall into a slag hopper 17 at the lower part through a slag outlet 16, gas phase products purified and dedusted by the cyclone separator 10 separate tar E through a separating device 15, obtaining the synthesis gas F rich in methane.
Coal samples in the raw material inlet 1: lignite, bituminous coal, anthracite, petroleum coke, biomass or a mixture thereof, and the particle size is less than or equal to 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 is added with CO2Trapping substances (e.g. CaO, Ca (OH)2Etc.) and mineral bonding substances, can realize CO fixation in the furnace2And the catalyst deactivation is suppressed.
The fluidized air introduced into the fluidized air distributor 7 is inert gas selected from nitrogen, argon, helium and the like.
The gasification agent introduced into the gasification agent gas distributor 3 is air, oxygen or a mixture of oxygen-enriched air and water vapor.
The operation temperature in the fluidized bed pyrolysis methanation furnace 6 is 400-600 ℃, the operation pressure is 3-6.5 MPa, and the linear speed is 0.1-5 m/s.
The oxygen-carbon ratio in the fluidized bed gasification furnace 2 is 0.5-1.2 mol/mol, the water-carbon ratio is 0.7-1.5 mol/mol, the operating temperature is 800-1200 ℃, the operating pressure is 3-6.5 MPa, and the linear velocity is 0.1-10 m/s.
The synthesis gas guide pipe 5 is used for guiding high-temperature synthesis gas generated by gasification in the fluidized bed gasification furnace to enter the bottom of the fluidized bed pyrolysis methanation furnace 6.
The returned material at the bottom of the material returning device 10 is selected from nitrogen, argon, water vapor or a mixture thereof by winnowing.
The technological process adopted by the equipment of the invention is briefly described as follows:
the coal sample loaded with catalyst enters the fluidized bed through a raw material inletIn the pyrolysis methanation furnace, mixing the pyrolysis methanation furnace with high-temperature synthesis gas from a synthesis gas guide pipe and fluidized air of a fluidized air gas distributor to perform catalytic pyrolysis and methanation reactions, wherein the operation temperature is 400-600 ℃, the pressure is 3.0-6.5 MPa, and CH is generated4、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. The semicoke pyrolyzed in the fluidized bed pyrolysis methanation furnace enters the fluidized bed gasification furnace through a semicoke inlet, coal ash particles in methane-rich synthesis gas at the outlet of the pyrolysis methanation furnace are introduced into the fluidized bed gasification furnace through a cyclone separator and a material returning device, and are subjected to combustion gasification reaction with a gasification agent from a gasification agent gas distributor at the operating temperature of 800-1200 ℃ and the pressure of 3-6.5 MPa to generate CO and H2、CO2And the high-temperature gas enters the fluidized bed pyrolysis methanation furnace through the synthesis gas guide pipe, so that heat and reactants are provided for pyrolysis and methanation reactions in the pyrolysis methanation furnace. Coarse slag particles generated in the fluidized bed gasification furnace fall into a slag hopper through a slag discharging opening at the bottom. And (3) after tar is separated from the methane-rich synthetic gas at the outlet of the cyclone separator through a separation device, sending the methane-rich synthetic gas to a subsequent washing and cooling chamber, and performing desulfurization and denitrification to obtain the purified methane-rich synthetic gas.
The advantages of the invention are briefly described as follows:
1) the catalytic gasification device combining the fluidized bed gasification furnace and the fluidized bed pyrolysis methanation furnace is adopted to carry out low-temperature pyrolysis and methanation reaction in the fluidized bed pyrolysis methanation furnace, semicoke and coal ash particles which are completely pyrolyzed enter the fluidized bed gasification furnace to carry out high-temperature catalytic gasification reaction, so that the gasification reaction rate and the carbon conversion rate are improved, the fluidized bed pyrolysis methanation furnace can reach higher methane equilibrium concentration, and methane generated by pyrolysis is fully utilized, and the aims of high gasification efficiency and methane yield are fulfilled.
2) The high-temperature synthesis gas at the outlet of the fluidized bed gasification furnace is introduced into the bottom of the fluidized bed pyrolysis methanation furnace through the synthesis gas guide pipe, flows upwards in the furnace after flowing out of the guide pipe, and is subjected to catalytic methanation reaction, so that the retention time of the high-temperature gas in the methanation furnace is prolonged, the heat transfer can be effectively promoted, and the methanation reaction is balanced at a low temperature.
3) CO addition to the supported catalyst2Trapping substances, e.g. CaO and Ca (OH)2Or the like, or mineral bonding substances are added, CO can be realized in the 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 concentration of methane in the outlet gas can be increased, and the load of subsequent gas separation and purification is reduced.
According to the technical scheme, the fluidized bed pyrolysis methanation furnace and the gasification furnace are combined, catalytic pyrolysis and catalytic methanation reactions are carried out in the fluidized bed pyrolysis methanation furnace, semicoke and coal ash particles which are completely pyrolyzed are introduced into the fluidized bed gasification furnace to be subjected to catalytic combustion gasification reactions, and generated high-temperature synthesis gas is introduced into the bottom of the fluidized bed pyrolysis methanation furnace through the guide pipe, so that circulation of heat flow and material flow is realized, and the purpose of full utilization is achieved. The conversion rate of carbon at the outlet of the gasification device can reach 95%, the methane content in the outlet synthesis gas reaches 75%, and the gasification device has the characteristics of high gasification strength, high energy utilization rate and simple and compact structure, greatly reduces equipment investment and production cost, and has good application prospect.
Drawings
Fig. 1 is a schematic flow diagram of an efficient device for preparing methane-rich synthesis gas by catalytic coal gasification:
in fig. 1, 1 is a raw material inlet, 2 is a fluidized bed gasification furnace, 3 is a gasifying agent gas distributor, 4 is a gasification furnace outlet, 5 is a synthesis gas guide pipe, 6 is a fluidized bed pyrolysis methanation furnace, 7 is a fluidized air gas distributor, 8 is a semicoke inlet, 9 is a pyrolysis methanation furnace outlet, 10 is a cyclone separator, 11 is an ash bucket, 12 is a return straight pipe, 13 is a return device, 14 is a return inlet, 15 is a separation device, 16 is a slag discharge port, and 17 is a slag bucket. A is a coal sample of a supported catalyst; b is a gasifying agent; c is fluidized wind; d is return air; e is tar; f is methane-rich synthesis gas; g is coarse slag.
The coal sample A loaded with catalyst enters the fluidized bed pyrolysis methanation furnace 6 through the raw material inlet 1, is mixed and contacted with high-temperature synthesis gas from the synthesis gas guide pipe 5 and fluidized air C of the fluidized air gas distributor 7 to carry out pyrolysis and methanation reactions, the pyrolyzed semicoke particles enter the fluidized bed gasification furnace 2 through the semicoke inlet 8, the methane-rich synthesis gas and coal ash particles at the outlet 9 of the upper pyrolysis methanation furnace enter the cyclone separator 10, the coal ash particles separated from the cyclone separator 10 are returned to the bottom of the fluidized bed gasification furnace 2 under the action of the material returning device 13 and the material returning air D to carry out combustion gasification reactions in the fluidized bed gasification furnace 2, the generated high-temperature synthesis gas enters the fluidized bed pyrolysis methanation furnace 6 through the guide pipe 5 to participate in the methanation reactions, and the fused and agglomerated coarse slag particles G fall into the slag hopper 17 below through the slag outlet 16, the gas phase product purified and dedusted by the cyclone separator 10 is separated from the tar E by the separation device 15 to obtain the primarily purified synthesis gas F 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 device of rich methane synthetic gas of efficient coal catalytic gasification system, fluidized bed pyrolysis methanation furnace internal diameter 1.0m, height 12m, the raw materials import height is located the 2/3 of fluidized bed pyrolysis methanation furnace height, fluidized bed gasification furnace internal diameter 0.8m, height 15m, the semicoke import is located the 1/8 of fluidized bed gasification furnace height, the feed back import is located the 1/4 of fluidized bed gasification furnace height, the length that the synthetic gas pipe stretched into in the fluidized bed pyrolysis methanation furnace is 9m, account for the 3/4 of methanation furnace height.
Inner Mongolian lignite and 10% K are selected for experiments2CO3Mixing the catalyst with 5 percent of CaO, adding the mixture into a fluidized bed pyrolysis methanation furnace from a raw material inlet, introducing nitrogen into a fluidized air distributor to enable the raw material to be turbulently fluidized in the furnace, mixing and contacting the raw material with high-temperature synthetic gas from a guide pipe, carrying out pyrolysis and methanation reactions, wherein the operating temperature is 500 ℃, the operating pressure is 3.5MPa, generating the synthetic gas rich in methane, and outputting CH in the synthetic gas4The concentration is 75 percentMethane yield 0.82Nm3In terms of/kg. Coal ash particles in the methane-rich synthetic gas are collected through a cyclone separator and a material returning device and are circularly sent into a fluidized bed gasification furnace, semicoke particles generated in the fluidized bed pyrolysis methanation furnace enter the fluidized bed gasification furnace through a semicoke inlet, the coal ash particles and the semicoke particles are subjected to combustion gasification reaction with oxygen and water vapor from a gasifying agent 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 fluidized bed gasification furnace is 1000 ℃, the operating pressure is 3.5MPa, the generated high-temperature synthetic gas enters the fluidized bed pyrolysis methanation furnace through a synthetic gas guide pipe, reactants and sensible heat are provided for methanation reaction and pyrolysis reaction in the furnace, and the carbon conversion rate at the outlet of the gasification device reaches 96%.
[ example 2 ]
The utility model provides a device of rich methane synthetic gas of efficient coal catalytic gasification system, fluidized bed pyrolysis methanation furnace internal diameter 1.0m, height 12m, the raw materials import height is located the 2/3 of fluidized bed pyrolysis methanation furnace height, fluidized bed gasification furnace internal diameter 0.8m, height 15m, the semicoke import is located the 1/8 of fluidized bed gasification furnace height, the feed back import is located the 1/4 of fluidized bed gasification furnace height, the length that the synthetic gas pipe stretched into in the fluidized bed pyrolysis methanation furnace is 10m, account for the 5/6 of methanation furnace height.
Inner Mongolian lignite and 10% K are selected for experiments2CO3Mixing the catalyst with 5 percent of CaO, adding the mixture into a fluidized bed pyrolysis methanation furnace from a raw material inlet, introducing nitrogen into a fluidized air distributor to enable the raw material to be turbulently fluidized in the furnace, mixing and contacting the raw material with high-temperature synthetic gas from a guide pipe, carrying out pyrolysis and methanation reactions, wherein the operating temperature is 500 ℃, the operating pressure is 3.5MPa, generating the synthetic gas rich in methane, and outputting CH in the synthetic gas4Concentration 80%, methane yield 0.89Nm3In terms of/kg. Coal ash particles in the methane-rich synthetic gas are collected through a cyclone separator and a material returning device and are circularly sent into the fluidized bed gasification furnace, semicoke particles generated in the fluidized bed pyrolysis methanation furnace enter the fluidized bed gasification furnace through a semicoke inlet, the coal ash particles and the semicoke particles are subjected to combustion gasification reaction with oxygen and water vapor from a gasifying agent gas distributor, and the oxygen-carbon ratio is controlled to be 1.0 mol/HAnd mol, controlling the steam-coal ratio to be 1.2mol/mol, controlling the operating temperature of the fluidized bed gasification furnace to be 1000 ℃ and the operating pressure to be 3.5MPa, enabling the generated high-temperature synthesis gas to enter the fluidized bed pyrolysis methanation furnace through the synthesis gas guide pipe, providing reactants and sensible heat for methanation reaction and pyrolysis reaction in the furnace, and enabling the carbon conversion rate at the outlet of the gasification device to reach 96%.
[ example 3 ]
The utility model provides a device of rich methane synthetic gas of efficient coal catalytic gasification system, fluidized bed pyrolysis methanation furnace internal diameter 1.0m, height 12m, the raw materials import height is located the 2/3 of fluidized bed pyrolysis methanation furnace height, fluidized bed gasification furnace internal diameter 0.8m, height 15m, the semicoke import is located the 1/8 of fluidized bed gasification furnace height, the feed back import is located the 1/4 of fluidized bed gasification furnace height, the length that the synthetic gas pipe stretched into in the fluidized bed pyrolysis methanation furnace is 9m, account for the 3/4 of methanation furnace height.
Inner Mongolian lignite and 10% K are selected for experiments2CO3Mixing the catalyst with 10 percent of CaO, adding the mixture into a fluidized bed pyrolysis methanation furnace from a raw material inlet, introducing nitrogen into a fluidized air distributor to enable the raw material to be turbulently fluidized in the furnace, mixing and contacting the raw material with high-temperature synthetic gas from a guide pipe, carrying out pyrolysis and methanation reactions, wherein the operating temperature is 500 ℃, the operating pressure is 3.5MPa, generating the synthetic gas rich in methane, and outputting CH in the synthetic gas4Concentration 85%, methane yield 0.93Nm3In terms of/kg. Coal ash particles in the methane-rich synthetic gas are collected through a cyclone separator and a material returning device and are circularly sent into a fluidized bed gasification furnace, semicoke particles generated in the fluidized bed pyrolysis methanation furnace enter the fluidized bed gasification furnace through a semicoke inlet, the coal ash particles and the semicoke particles are subjected to combustion gasification reaction with oxygen and water vapor from a gasifying agent 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 fluidized bed gasification furnace is 1000 ℃, the operating pressure is 3.5MPa, the generated high-temperature synthetic gas enters the fluidized bed pyrolysis methanation furnace through a synthetic gas guide pipe, reactants and sensible heat are provided for methanation reaction and pyrolysis reaction in the furnace, and the carbon conversion rate at the outlet of the gasification device reaches 98%.
[ example 4 ]
The utility model provides a device of rich methane synthetic gas of efficient coal catalytic gasification system, fluidized bed pyrolysis methanation furnace internal diameter 1.0m, height 12m, the raw materials import height is located the 2/3 of fluidized bed pyrolysis methanation furnace height, fluidized bed gasification furnace internal diameter 0.8m, height 15m, the semicoke import is located the 1/8 of fluidized bed gasification furnace height, the feed back import is located the 1/4 of fluidized bed gasification furnace height, the length that the synthetic gas pipe stretched into in the fluidized bed pyrolysis methanation furnace is 9m, account for the 3/4 of methanation furnace height.
Inner Mongolian lignite and 10% K are selected for experiments2CO3Mixing the catalyst with 5 percent of CaO, adding the mixture into a fluidized bed pyrolysis methanation furnace from a raw material inlet, introducing nitrogen into a fluidized air distributor to enable the raw material to be turbulently fluidized in the furnace, mixing and contacting the raw material with high-temperature synthetic gas from a guide pipe, carrying out pyrolysis and methanation reactions, wherein the operating temperature is 500 ℃, the operating pressure is 3.5MPa, generating the synthetic gas rich in methane, and outputting CH in the synthetic gas4Concentration 76% and methane yield 0.86Nm3In terms of/kg. Coal ash particles in the methane-rich synthetic gas are collected through a cyclone separator and a material returning device and are circularly sent into a fluidized bed gasification furnace, semicoke particles generated in the fluidized bed pyrolysis methanation furnace enter the fluidized bed gasification furnace through a semicoke inlet, the coal ash particles and the semicoke particles are subjected to combustion gasification reaction with oxygen and water vapor from a gasification agent 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 fluidized bed gasification furnace is 1100 ℃, the operating pressure is 3.5MPa, the generated high-temperature synthetic gas enters the fluidized bed pyrolysis methanation furnace through a synthetic gas guide pipe, reactants and sensible heat are provided for methanation reaction and pyrolysis reaction in the furnace, 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 ]
The gasification reaction device in the process of preparing the methane-rich gas by catalytic gasification of the multilayer fluidized bed proposed by Xinao group is adopted, and the experiment selects the inner Mongolia lignite as the raw material, the load of the inner Mongolia lignite is 10 percent of potassium carbonate catalyst, 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 BDA0001087608180000081
Figure BDA0001087608180000091

Claims (8)

1. An efficient device for preparing methane-rich synthesis gas by catalytic coal gasification comprises a raw material inlet (1), a fluidized bed gasification furnace (2), a gasification agent gas distributor (3), a gasification furnace outlet (4), a synthesis gas guide pipe (5), a fluidized bed pyrolysis methanation furnace (6), a fluidized air gas distributor (7), a semicoke inlet (8), a pyrolysis methanation furnace outlet (9), a cyclone separator (10), an ash hopper (11), a return straight pipe (12), a return device (13), a return inlet (14), a separation device (15), a slag discharging port (16) and a slag hopper (17); it is characterized in that the raw material inlet (1) is connected with the fluidized bed pyrolysis methanation furnace (6), the bottom of the fluidized bed pyrolysis methanation furnace (6) is connected with the bottom of the fluidized bed gasification furnace (2), the outlet (4) of the fluidized bed gasification furnace is connected with the fluidized bed pyrolysis methanation furnace (6) through the synthesis gas conduit (5), the outlet (9) of the pyrolysis methanation furnace is connected with the cyclone separator (10), the bottom of the cyclone separator (10) is connected with the ash hopper (11) and the return straight pipe (12), the feed back device (13) is connected with the fluidized bed gasification furnace (2) through the feed back inlet (14), an outlet above the cyclone separator (10) is connected with the separating device (15), the bottom of the fluidized bed gasification furnace (2) is connected with the slag hopper (17) through the slag discharge port (16); wherein, the position of raw materials import (1) does the fluidized bed pyrolysis methanation furnace (6) height 1/2 ~ 1, the angle and the horizontal axis of raw materials import (1) are 0 ~ 75 contained angle, the height of synthesis gas pipe (5) does more than the 3/4 of fluidized bed pyrolysis methanation furnace (6) height, stretch into to the bottom of fluidized bed pyrolysis methanation furnace (6), the internal diameter of synthesis gas pipe (5) does 1/8 ~ 1/3 of fluidized bed pyrolysis methanation furnace (6) internal diameter.
2. The efficient device for preparing the methane-rich synthetic gas through catalytic coal gasification according to claim 1, wherein the fluidized air distributor (7) is located at the bottom of the fluidized bed pyrolysis methanation furnace (6) and is horizontally arranged, the fluidized air distributor (7) is provided with air holes, the air holes are uniformly arranged along the circumference, 10-30 circles of air holes are formed, and the aperture ratio is 0.1-5%.
3. The efficient device for preparing the methane-rich synthesis gas through catalytic coal gasification according to claim 1, wherein the gasifying agent gas distributor (3) is located at the bottom of the fluidized bed gasification furnace (2) and forms an included angle of less than or equal to 60 degrees with a horizontal axis, a slag discharge port (16) is formed in the center, air holes are formed in the conical surface of the gasifying agent gas distributor (3), the air holes are uniformly arranged along the circumference, 5-20 circles of air holes are formed, and the aperture ratio is 0.1-5%.
4. The efficient device for preparing the methane-rich synthetic gas through catalytic coal gasification according to claim 1, wherein the position of the feed back inlet (14) is located at the bottom of the fluidized bed gasification furnace (2) and is 1/8-1/3 of the height of the fluidized bed gasification furnace (2), and the angle of the feed back inlet (14) forms an included angle of 15-75 degrees with a horizontal axis.
5. A kind ofThe method for preparing the methane-rich synthetic gas by the high-efficiency coal catalytic gasification adopts any one of the high-efficiency coal catalytic gasification devices of claims 1-4, and is characterized by mainly comprising the following steps: a coal sample (A) loaded with a catalyst enters the fluidized bed pyrolysis methanation furnace (6) through the raw material inlet (1), is mixed and contacted with high-temperature synthesis gas from the synthesis gas guide pipe (5) and fluidized air (C) of the fluidized air gas distributor (7) to carry out pyrolysis and methanation reactions, pyrolyzed semicoke particles enter the fluidized bed gasification furnace (2) through the semicoke inlet (8), methane-rich synthesis gas and coal ash particles at the upper part of the pyrolysis methanation furnace outlet (9) enter the cyclone separator (10), the separated coal ash particles are returned to the bottom of the fluidized bed gasification furnace (2) under the action of the material returning device (13) and the material returning air (D), the combustion gasification reaction is carried out in the fluidized bed gasification furnace (2), and the generated high-temperature synthesis gas enters the fluidized bed pyrolysis methanation furnace (6) through the synthesis gas guide pipe (5), the fused and agglomerated coarse slag particles (G) fall into the slag hopper (17) below through the slag discharge opening (16), and gas-phase products dedusted by the cyclone separator (10) are separated from tar (E) through the separation device (15) to obtain synthesis gas (F) rich in methane; wherein the catalyst contains CO2Trapping material and mineral binding material.
6. The method for preparing the methane-rich synthetic gas through the high-efficiency catalytic coal gasification of claim 5, wherein the catalyst is selected from alkali metals, alkaline earth metals, transition metals or a mixture thereof; the catalyst is loaded on raw coal in a manner of impregnation method, dry mixing method or ion exchange method; the loading capacity of the catalyst accounts for 0.1-50% of the mass of the raw coal.
7. The efficient method for preparing the methane-rich synthesis gas through catalytic coal gasification according to claim 5, wherein the operating temperature in the fluidized bed pyrolysis methanation furnace (6) is 400-600 ℃, the operating pressure is 3-6.5 MPa, and the linear velocity is 0.1-5 m/s; the oxygen-carbon ratio in the fluidized bed gasification furnace (2) is 0.5-1.2 mol/mol, the water-carbon ratio is 0.7-1.5 mol/mol, the operating temperature is 800-1200 ℃, the operating pressure is 3-6.5 MPa, and the linear speed is 0.1-10 m/s.
8. The method for preparing the methane-rich synthetic gas through the high-efficiency coal catalytic gasification is characterized in that the synthetic gas conduit (5) is used for guiding the high-temperature synthetic gas generated through the gasification in the fluidized bed gasification furnace (2) to the bottom of the fluidized bed pyrolysis methanation furnace (6).
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102021037A (en) * 2009-09-14 2011-04-20 新奥科技发展有限公司 Method and apparatus for preparing methane by catalytic gasification of coal
CN104031703A (en) * 2013-03-06 2014-09-10 中国石油天然气股份有限公司 Method and device for preparation of natural gas synthesis gas from coal

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102021037A (en) * 2009-09-14 2011-04-20 新奥科技发展有限公司 Method and apparatus for preparing methane by catalytic gasification of coal
CN104031703A (en) * 2013-03-06 2014-09-10 中国石油天然气股份有限公司 Method and device for preparation of natural gas synthesis gas from coal

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