CN107916140B - Circulating fluidized bed-entrained flow combined gasification method and device - Google Patents

Circulating fluidized bed-entrained flow combined gasification method and device Download PDF

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CN107916140B
CN107916140B CN201610882443.7A CN201610882443A CN107916140B CN 107916140 B CN107916140 B CN 107916140B CN 201610882443 A CN201610882443 A CN 201610882443A CN 107916140 B CN107916140 B CN 107916140B
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fluidized bed
circulating fluidized
nozzle
raw material
bed reactor
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CN107916140A (en
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霍威
钟思青
金渭龙
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
    • C10J3/48—Apparatus; Plants
    • C10J3/485—Entrained flow gasifiers
    • 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
    • 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
    • C10J2300/0983—Additives
    • C10J2300/0986—Catalysts
    • 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 circulating fluidized bed-entrained flow combined gasification method and a device, which solve the problems of poor coal adaptability, low carbon conversion rate and the like in the prior art. The invention adopts the combination of a circulating fluidized bed reactor and a fluidized bed reactor, and comprises the following steps: the low-rank coal containing the catalyst reacts with the gasifying agent in the circulating fluidized bed reactor to generate the methane-rich synthetic gas, ash slag of the low-rank coal containing the catalyst is used as a raw material of the fluidized bed reactor and the catalyst is sent into the fluidized bed reactor through a nozzle to collide with the high-rank coal or the petroleum coke, and the low-rank coal containing the catalyst reacts under the action of the gasifying agent to generate the synthetic gas, so that carbon residue in the ash slag of the circulating fluidized bed reactor is effectively utilized, the carbon conversion rate is improved, and the adaptability of the low-rank coal to the high-rank coal and.

Description

Circulating fluidized bed-entrained flow combined gasification method and device
Technical Field
The invention belongs to the field of coal gasification, and particularly relates to a gasification method and a gasification device for a circulating fluidized bed and a fluidized bed gasification section.
Background
China is a country which takes coal as a main energy structure and cannot change for a long time in the future, and according to statistics, coal reaches 66% in the primary energy consumption structure of China. With the increasing shortage of petroleum resources, the effective utilization of coal resources has become a strategy for sustainable development of energy in China. The reserve of low-rank coal in China accounts for more than 55% of the total amount of coal resources, but the low-rank coal has high water content, low coalification degree and low direct combustion efficiency, thereby not only wasting resources, but also polluting the environment and causing the emission of acid rain, PM2.5, SOx, NOx and other greenhouse gases. Therefore, coal conversion techniques aimed at reducing pollution have received great attention. Among the coal utilization technologies, coal gasification is a basic technology for coal energy conversion and is also the most important process in the development of coal chemical industry. The realization of the efficient and clean utilization of coal is the key for realizing the sustainable development of energy in China and is an effective way for solving the global energy and environment problems.
Typical coal gasification technologies can be divided into three categories: fixed bed gasification, entrained flow gasification and fluidized bed gasification. The fixed bed gasification is characterized by being suitable for gasification and gas production of lump coal or crushed coal, and has the advantages of low equipment investment cost, mature technology and the like; but the coal type limitation is strict, and the method is only suitable for high-quality lump coal or crushed coal, and causes the defects of high production cost and the like. Although entrained-flow bed gasification solves the problem of high production cost, has the characteristics of less pollution, capability of continuously producing gas and the like, the coal type has poor adaptability, and low-order inferior coal with low heat value, high ash content and high moisture content cannot be treated. The fluidized bed gasification can not only meet the characteristic of continuous gas production of coal gasification, but also has moderate production capacity, small environmental pollution and can directly use various cheap powder raw materials. Therefore, the efficient utilization of fluidized bed gasification is an effective way for solving low-rank coal and other various cheap powder raw materials, and is also one of gas production ways with low cost and high efficiency. However, the conventional fluidized bed gasification has a particle residence time lower than that of the fixed bed and a gasification reaction temperature lower than the ash melting point of the raw material, so that the carbon conversion rate is relatively low. Most of the fluidized bed gasification technologies today have a carbon conversion rate of only 65-85%, so that a considerable amount of carbon residue in the coal ash and cinder is not effectively utilized.
In order to solve the disadvantages of the conventional process, the chinese patent CN201010279560.7 discloses a multi-layer fluidized bed catalytic gasification process, which comprises a gasification furnace divided into a syngas generation section, a coal methanation section and a syngas methanation section. The combustion, gasification, methanation and pyrolysis reactions are carried out in sections, and the reaction degree and the temperature distribution of each section are controlled. Although the carbon conversion rate is improved along with the addition of the catalyst and the coal subsection treatment, and the control degree of the product components is high. However, in the pyrolysis section above the gasification furnace, fine pulverized coal escapes from the gasification furnace without reaction, so that the carbon content of the fly ash is high, and the unreacted coal coke is back-mixed to the slag hole at the bottom of the gasification furnace and directly discharged from the gasification furnace, so that the carbon conversion rate in the reaction process is low. The carbon conversion is still substantially below 90%.
The chinese invention patent CN201410499747.6 proposes a dry slagging fluidized bed gasification reaction device, and simultaneously adopts a two-stage gasification method to divide the furnace chamber into an upper section and a lower section, and unreacted particles continue gasification reaction in a second stage reaction chamber, thereby effectively improving the carbon conversion rate (up to 90-95%).
Although the existing fluidized bed technology or patent improves the condition of low carbon conversion rate of the traditional fluidized bed gasification to a certain extent, the carbon conversion rate of the traditional fluidized bed gasification still can not reach the level of 99 percent of the carbon conversion rate of a fixed bed and a fluidized bed, and a lot of carbon residues still exist in ash residues. Therefore, it is necessary to solve the problem of excessive carbon residue in fluidized bed gasification ash.
Disclosure of Invention
One of the technical problems to be solved by the invention is to overcome the defects of the prior art and provide a circulating fluidized bed-entrained flow combined gasification device, which effectively improves the overall carbon conversion rate of gasification, solves the problem that low-rank coal is difficult to utilize and realizes the characteristic of diversified gasification products.
The second technical problem to be solved by the present invention is a circulating fluidized bed-entrained flow combined gasification method corresponding to the first technical problem.
In order to solve the technical problem, the invention provides a circulating fluidized bed-entrained flow combined gasification device, which is characterized in that: the device comprises a circulating fluidized bed riser 1, a first cyclone separator 2, a gas separation device 3, a circulating fluidized bed downcomer 4, a return pipe 5, a gas distributor 6, a first slag hopper 7, a first nozzle 8, a fluidized bed reactor 9, a second nozzle 10, a second slag hopper 11, a second cyclone separator 12 and a washing tower 13; the middle upper part of the circulating fluidized bed riser 1 is provided with an inlet of a first raw material A, and the side surface of the upper part of the circulating fluidized bed riser 1 is connected with a first cyclone separator 2, and is connected with a gas separation device 3 after the first cyclone separator 2; the lower part of the first cyclone separator 2 is connected with a circulating fluidized bed downcomer 4; a loosening wind C inlet is arranged at the position 1/10-1/8 away from the bottom of the circulating fluidized bed downcomer 4, and the side surface of the lower part of the circulating fluidized bed downcomer 4 is connected with a return pipe 5; the lower part of the material returning pipe 5 is connected with the middle lower part of the circulating fluidized bed lifting pipe 1; the lower part of the circulating fluidized bed riser 1 is provided with a gas distributor 6 for the first gasification agent B to enter; the lower part of the gas distributor 6 is connected with a first slag hopper 7; the lower part of the first slag hopper 7 is connected with a first nozzle 8; one side of the first nozzle 8 is provided with an inlet of a second gasifying agent F, and the other side is connected with a fluidized bed reactor 9; the upper middle part of the fluidized bed reactor 9 is connected with a second nozzle 10 at one side opposite to the first nozzle 8, the bottom of the fluidized bed reactor 9 is connected with a second slag hopper 11, and the side surface of the lower middle part of the fluidized bed reactor 9 is connected with a second cyclone separator 12 and a water washing tower 13 after being connected with the second cyclone separator 12.
In the technical scheme, the first nozzle (8) and the second nozzle (10) both adopt a double-flow-channel structure, wherein one side of the flow channel is used for the second gasifying agent (F) to pass through, and the other side of the flow channel is used for the raw material powder particles and the conveying carrier gas to pass through.
In the technical scheme, the first nozzle (8) and the second nozzle (10) are oppositely arranged; the angle between the inlet direction of the nozzle vertical airflow bed reactor (9) and the horizontal plane is-5 degrees.
In order to solve the second technical problem, the invention provides a circulating fluidized bed-entrained flow combined gasification method which is characterized by comprising the following steps:
a. reaction in circulating fluidized bed riser 1: the first raw material A is added from the middle upper part of a circulating fluidized bed lifting pipe 1, is mixed with circulating semicoke from a return pipe 5, and is contacted with a first gasifying agent B sent from a gas distributor 6 to realize catalytic gasification reaction, so as to generate synthesis gas rich in methane and high-temperature semicoke particles, the high-temperature semicoke particles are carried by the synthesis gas to enter a first cyclone separator 2, the synthesis gas is sent to a gas separation device 3 for purification and separation treatment after separation, and a first product gas D and CO are obtained2The high-temperature semicoke particles are separated by the first cyclone separator 2 and then are sent into a descending pipe 4 of the circulating fluidized bed for continuous reaction; the first raw material A is a low-rank coal raw material containing a catalyst;
b. reaction in circulating fluidized bed downcomer 4: the high-temperature semicoke particles enter the descending pipe 4 of the circulating fluidized bed, are contacted with the loosening air C from the middle lower part of the descending pipe 4 of the circulating fluidized bed, generate weak gasification reaction, and are continuously sent to the riser 1 of the circulating fluidized bed through the return pipe 5 to perform circulating gasification reaction under the action of the loosening air C;
c. ash treatment of circulating fluidized bed reactor: continuously carrying out the processes of the step a and the step b by the high-temperature semicoke particles, finally forming first ash E along with the consumption of combustible materials in the particles, and falling into a first slag hopper 7 from the circulating fluidized bed lifting pipe 1 through a gas distributor 6 by the self gravity; CO of the first ash E separated by the gas separation apparatus 32The mixture is conveyed to a first nozzle 8 of the fluidized bed reactor and is used as a raw material and a catalyst of the fluidized bed reactor to continue to react;
d. reaction in the entrained-flow reactor 9: the first ash E and the second gasifying agent F are premixed at the head part of the first nozzle 8, injected into the airflow bed reactor 9 and collided with the premixed second raw material G and the second gasifying agent F from the second nozzle 10, mineral substances contained in the first ash E and a catalyst in the unreacted first raw material A have catalytic action on the surface of the second raw material G, and have violent catalytic gasification reaction to generate crude synthesis gas, fly ash and second ash;
e. treatment of the reaction products in the entrained-flow reactor 9: the second ash slag falls to a second slag hopper 11 through self gravity to be collected, the fly ash is carried by the crude synthesis gas and sent to a second cyclone separator 12 for gas-solid separation, the separated crude synthesis gas is further sent to a water scrubber 13 for purification processing treatment, and finally a second product gas H is obtained.
The first raw material A is a low-rank coal raw material containing a catalyst, and the second raw material G is high-rank coal or petroleum coke. Wherein the low-rank coal raw material is lignite, the high-rank coal raw material is anthracite, and the catalyst is one of cheap papermaking black liquor, industrial waste alkali or plant ash.
The particle diameters of the lignite and the catalyst in the first raw material A are both less than 300 mu m, and the average particle diameter of the second raw material G is less than about 250 mu m.
The first gasifying agent B consists of water vapor and oxygen, and the volume ratio of the water vapor to the oxygen is controlled to be 100: 20-25. The loosening wind C consists of water vapor and oxygen, and the volume ratio of the water vapor to the oxygen is controlled to be 100: 5-10. The second gasifying agent F is air.
The operating pressures of the circulating fluidized bed reactor and the air flow bed reactor are both more than or equal to 4.0MPa, the operating temperature of the circulating fluidized bed reactor is 850 ℃ and the operating temperature of the air flow bed reactor is 1650 ℃ and 1400 ℃.
The methane-rich synthesis gas generated by the gasification reaction in the circulating fluidized bed reactor is CO obtained after being separated by the first cyclone separator 2 and the gas separation equipment 3 in sequence2The raw materials of the first nozzle 8 and the second nozzle 10 in the fluidized bed reactor 9 are conveyed with gas and enter the fluidized bed reactor 9 together to participate in gasification reaction.
Brief description of the invention
The method combines a circulating fluidized bed reactor and a fluidized bed reactor for use, and mainly carries out catalytic gasification reaction of low-rank coal in the circulating fluidized bed reactor to generate synthesis gas rich in methane; high-order coal, even petroleum coke and gasification ash of the circulating fluidized bed reactor are introduced into the air-flow bed reactor, and the catalytic gasification of the high-order coal or the petroleum coke and the secondary utilization of the ash in the circulating fluidized bed reactor are realized by using mineral substances and unreacted catalysts contained in the ash. CO produced by reaction in a circulating fluidized bed reactor2After separation, the gasified ash residue of the circulating fluidized bed reactor is taken as conveying gas to be sent into the entrained flow reactor and taken as a gasifying agent to react the raw materials in the entrained flow reactor, thereby reducing the additional N2And Ar, etc. cost of conventional transport gases.
The technical scheme of the invention adopts a method that the nozzles in the entrained-flow bed reactor are oppositely distributed, and the oppositely arranged nozzles adopt different raw materials, one side of the nozzles is carbon-containing substances with poor reactivity, such as high-order coal or petroleum coke, and the other side of the nozzles is ash residue containing a catalyst obtained after gasification of the circulating fluidized bed reactor, so that the ash residue generated by gasification of the circulating fluidized bed reactor and the unreacted catalyst can be secondarily utilized, the problem of utilization of residual carbon in the ash residue generated by gasification of the circulating fluidized bed is solved, the rate of gasification reaction of the high-order coal or petroleum coke is improved by utilizing the catalytic action of the ash residue, the carbon conversion rate is improved, and the carbon conversion rate of the. In addition, the circulating fluidized bed reactor and the entrained flow reactor are coupled into a whole, so that the coal adaptability is improved, the coal can process raw materials with wide span from low-order inferior coal to high-order coal and even petroleum coke, the catalytic gasification is realized to produce a methane-rich gas product, the gasification is realized in the entrained flow reactor to produce the synthesis gas, the purpose of product diversification is achieved, and the method has the characteristics of high gasification strength and the like and has good application prospect.
Drawings
FIG. 1 is a schematic diagram of a circulating fluidized bed-entrained flow combined gasification unit provided by the present invention.
In the figure, 1-circulating fluidized bed riser; 2-a first cyclone separator; 3-a gas separation device; 4-a downcomer of the circulating fluidized bed; 5-a material returning pipe; 6-a gas distributor; 7-a first slag hopper; 8-a first nozzle; 9-an entrained flow gasifier; 10-a second nozzle; 11-a second slag hopper; 12-a second cyclone separator; 13-a water washing tower; a-a first feedstock; b-a first gasifying agent; c-loosening wind; d-a first product gas; e-first ash; f-a second gasifying agent; g-a second starting material; h-second product gas.
Detailed Description
The features of the invention will be described in more detail below with reference to the accompanying drawings and examples.
[ example 1 ]
Lignite raw material containing papermaking black liquor is conveyed into a hearth of a circulating fluidized bed riser tube 1 from a raw material inlet, reacts with a gasifying agent with the ratio of oxygen to water vapor being 20:100 from a gas distributor 6 at the operation temperature of 700 ℃ to generate methane-rich synthetic gas and high-temperature semicoke particles, and is separated by a first cyclone separator 2 to obtain methane-rich first product gas D and CO which can be used as industrial fuel2Wherein the first product gas D contains the effective component H2CO and CH4The contents are 41.3%, 19.6% and 6.5% respectively. And the high-temperature semicoke particles continue to carry out gasification reaction in the circulating fluidized bed reactor. As the combustible in the high-temperature semicoke particles is continuously consumed, first ash E is finally formed and falls to the second place from the circulating fluidized bed riser pipe 1 through the gas distributor 6A slag hopper 7. CO of the first ash E separated by the gas separation apparatus 32And (3) conveying the mixture to a first nozzle 8 of the fluidized bed reactor to be used as a raw material and a catalyst of the fluidized bed reactor for continuous reaction. The first ash E and the second gasifying agent F are premixed at the head of the first nozzle 8, injected into the entrained-flow reactor 9 and collided with the anthracite raw material G premixed from the second nozzle 10 and air, the angle between the vertical direction of the first nozzle 8 and the second nozzle 10 to the inlet direction of the entrained-flow reactor (9) and the horizontal plane is 0 degree, and the violent catalytic gasification reaction is carried out at the operation temperature of 1400 ℃ to generate synthetic gas, wherein the effective component H in the synthetic gas2The CO contents were 24.5% and 63.4%, respectively. During this period, the feedstock carbon conversion for the entire system was 99%.
[ example 2 ]
Lignite raw material containing papermaking black liquor is conveyed into a hearth of a circulating fluidized bed riser tube 1 from a raw material inlet, reacts with a gasifying agent with the ratio of oxygen to water vapor of 25:100 from a gas distributor 6 at the operation temperature of 850 ℃ to generate methane-rich synthetic gas and high-temperature semicoke particles, and is separated by a first cyclone separator 2 to obtain methane-rich first product gas D and CO which can be used as industrial fuel2Wherein the first product gas D contains the effective component H2CO and CH4The contents are 39.9%, 20.1% and 7.1% respectively. And the high-temperature semicoke particles continue to carry out gasification reaction in the circulating fluidized bed reactor. As the combustibles in the high temperature char particles are continuously consumed, first ash E is finally formed and falls from the circulating fluidized bed riser 1 via the gas distributor 6 into the first hopper 7. CO of the first ash E separated by the gas separation apparatus 32And (3) conveying the mixture to a first nozzle 8 of the fluidized bed reactor to be used as a raw material and a catalyst of the fluidized bed reactor for continuous reaction. The first ash E and the second gasifying agent F are premixed at the head part of the first nozzle 8, injected into the entrained-flow reactor 9 and collided with the anthracite raw material G premixed from the second nozzle 10 and air, the angle between the vertical direction of the first nozzle 8 and the second nozzle 10 to the inlet direction of the entrained-flow reactor (9) and the horizontal plane is 0 DEG, and the violent catalytic gasification reaction is generated at the operation temperature of 1650 ℃ to generate syntheticGas, the effective component H in the synthesis gas2The CO contents were 24.1% and 64.4%, respectively. During this period, the feedstock carbon conversion for the entire system was 99%.
[ example 3 ]
Lignite raw material containing papermaking black liquor is conveyed into a hearth of a circulating fluidized bed riser tube 1 from a raw material inlet, reacts with a gasifying agent with the ratio of oxygen to water vapor of 25:100 from a gas distributor 6 at the operation temperature of 850 ℃ to generate methane-rich synthetic gas and high-temperature semicoke particles, and is separated by a first cyclone separator 2 to obtain methane-rich first product gas D and CO which can be used as industrial fuel2Wherein the first product gas D contains the effective component H2CO and CH4The contents are 39.9%, 20.1% and 7.1% respectively. And the high-temperature semicoke particles continue to carry out gasification reaction in the circulating fluidized bed reactor. As the combustibles in the high temperature char particles are continuously consumed, first ash E is finally formed and falls from the circulating fluidized bed riser 1 via the gas distributor 6 into the first hopper 7. CO of the first ash E separated by the gas separation apparatus 32And (3) conveying the mixture to a first nozzle 8 of the fluidized bed reactor to be used as a raw material and a catalyst of the fluidized bed reactor for continuous reaction. The first ash E and the second gasifying agent F are premixed at the head of the first nozzle 8, injected into the airflow bed reactor 9 and collided with petroleum coke raw material G premixed from the second nozzle 10 and air, the angle between the vertical airflow bed reactor (9) inlet direction of the first nozzle 8 and the second nozzle 10 and the horizontal plane is 0 degree, and the violent catalytic gasification reaction is carried out at the operation temperature of 1650 ℃ to generate synthetic gas, wherein the effective component H in the synthetic gas2The CO contents were 28.2% and 61.0%, respectively. During this period, the feedstock carbon conversion for the entire system was 99%.
[ example 4 ]
Lignite raw material containing papermaking black liquor is conveyed into a hearth of a circulating fluidized bed lifting pipe 1 from a raw material inlet, reacts with a gasifying agent with the ratio of oxygen to water vapor of 25:100 from a gas distributor 6 at the operation temperature of 850 ℃ to generate synthesis gas rich in methane and high-temperature semicoke particles, and is separated by a first cyclone separator 2 to obtain the lignite raw material capable of being used as paper making black liquorFirst product gas D rich in methane and CO as industrial fuel2Wherein the first product gas D contains the effective component H2CO and CH4The contents are 39.9%, 20.1% and 7.1% respectively. And the high-temperature semicoke particles continue to carry out gasification reaction in the circulating fluidized bed reactor. As the combustibles in the high temperature char particles are continuously consumed, first ash E is finally formed and falls from the circulating fluidized bed riser 1 via the gas distributor 6 into the first hopper 7. CO of the first ash E separated by the gas separation apparatus 32And (3) conveying the mixture to a first nozzle 8 of the fluidized bed reactor to be used as a raw material and a catalyst of the fluidized bed reactor for continuous reaction. The first ash E and the second gasifying agent F are premixed at the head of the first nozzle 8, injected into the entrained-flow reactor 9 and collided with the anthracite raw material G premixed from the second nozzle 10 and air, the angle between the vertical direction of the first nozzle 8 and the second nozzle 10 to the air-flow reactor (9) and the horizontal plane is 15 degrees, the violent catalytic gasification reaction is carried out at the operation temperature of 1650 ℃ to generate synthetic gas, and the effective component H in the synthetic gas2The CO contents were 21.0% and 61.4%, respectively. During this period, the feedstock carbon conversion for the entire system was 86%.
[ example 5 ]
Lignite raw material containing papermaking black liquor is conveyed into a hearth of a circulating fluidized bed riser tube 1 from a raw material inlet, reacts with a gasifying agent with the ratio of oxygen to water vapor of 25:100 from a gas distributor 6 at the operation temperature of 850 ℃ to generate methane-rich synthetic gas and high-temperature semicoke particles, and is separated by a first cyclone separator 2 to obtain methane-rich first product gas D and CO which can be used as industrial fuel2Wherein the first product gas D contains the effective component H2CO and CH4The contents are 39.9%, 20.1% and 7.1% respectively. And the high-temperature semicoke particles continue to carry out gasification reaction in the circulating fluidized bed reactor. As the combustibles in the high temperature char particles are continuously consumed, first ash E is finally formed and falls from the circulating fluidized bed riser 1 via the gas distributor 6 into the first hopper 7. First ash E is formed by adding N2Delivering to the first nozzle 8 of the fluidized bed reactor as the raw material of the fluidized bed reactorAnd the catalyst continues to react. The first ash E and the second gasifying agent F are premixed at the head of the first nozzle 8, injected into the entrained-flow reactor 9 and collided with the anthracite raw material G premixed from the second nozzle 10 and air, the angle between the vertical direction of the first nozzle 8 and the second nozzle 10 to the air-flow reactor (9) and the horizontal plane is 0 degree, and the violent catalytic gasification reaction is carried out at the operation temperature of 1650 ℃ to generate synthetic gas, wherein the effective component H in the synthetic gas2The CO contents were 23.8% and 62.1%, respectively. During this period, the feed carbon conversion for the entire system was 97%.
[ COMPARATIVE EXAMPLE 1 ]
Adopting traditional non-catalytic gasification technology of a winkler fluidized bed, adopting brown coal as a raw material, wherein the gasification pressure is 0.1MPa, the gasification temperature is 850 ℃, and the effective component H at an outlet is2CO and CH4The sum of the contents reaches 78.5%, but the carbon conversion rate is only 81%.
[ COMPARATIVE EXAMPLE 2 ]
The ash fusion fluidized bed gasification device proposed by Shanxi coal gasification adopts brown coal, the gasification pressure is 1.0Mpa, the gasification temperature is 1100 ℃, and the effective component H at the outlet is2CO and CH4The content sum is 85%, but the carbon conversion rate is only 70-90%.
[ COMPARATIVE EXAMPLE 3 ]
Adopts a two-stage dry slagging fluidized bed gasification device provided by Shanghai boiler plant, Inc., the raw material of lignite is gasified under the pressure of 0.5Mpa at the gasification temperature of 1000 ℃, and the effective component H at the outlet2CO and CH4The total content is up to 91%, and the carbon conversion rate is 90-95%.
Figure BDA0001127390990000081
From the technical comparison of the tables, it can be obtained that the technology of the invention has very wide raw material adaptability, is superior to the traditional technology and similar technologies at home and abroad, and realizes combined gasification, the carbon conversion rate is up to 99 percent, which is more than 5 percent higher than that of the similar technologies.

Claims (10)

1. A combined gasification device of a circulating fluidized bed and an entrained flow bed is characterized in that: the device comprises a circulating fluidized bed lifting pipe (1), a first cyclone separator (2), gas separation equipment (3), a circulating fluidized bed descending pipe (4), a material return pipe (5), a gas distributor (6), a first slag hopper (7), a first nozzle (8), a fluidized bed reactor (9), a second nozzle (10), a second slag hopper (11), a second cyclone separator (12) and a washing tower (13); the middle upper part of the circulating fluidized bed lifting pipe (1) is provided with an inlet of a first raw material (A), the side surface of the upper part of the circulating fluidized bed lifting pipe (1) is connected with a first cyclone separator (2), and a gas separation device (3) is connected behind the first cyclone separator (2); the lower part of the first cyclone separator (2) is connected with a circulating fluidized bed downcomer (4); a loosening air (C) inlet is arranged at the position 1/10-1/8 away from the bottom of the circulating fluidized bed downcomer (4), and the side surface of the lower part of the circulating fluidized bed downcomer (4) is connected with a return pipe (5); the lower part of the material returning pipe (5) is connected with the middle lower part of the circulating fluidized bed lifting pipe (1); the lower part of the circulating fluidized bed lifting pipe (1) is provided with a gas distributor (6) for the first gasifying agent (B) to enter; the lower part of the gas distributor (6) is connected with a first slag hopper (7); the lower part of the first slag hopper (7) is connected with a first nozzle (8); one side of the first nozzle (8) is provided with an inlet of a second gasifying agent (F), and the other side of the first nozzle is connected with a fluidized bed reactor (9); the upper middle part of the fluidized bed reactor (9) is connected with the second nozzle (10) at the opposite side of the first nozzle (8), the bottom of the fluidized bed reactor (9) is connected with a second slag hopper (11), the side surface of the lower middle part of the fluidized bed reactor (9) is connected with a second cyclone separator (12) and a washing tower (13) after being connected with the second cyclone separator (12), wherein the first nozzle (8) and the second nozzle (10) are oppositely arranged.
2. The combined circulating fluidized bed-entrained flow gasification apparatus of claim 1, wherein: the first nozzle (8) and the second nozzle (10) both adopt a double-flow-channel structure, wherein one side of the flow channel is used for the second gasifying agent (F) to pass through, and the other side of the flow channel is used for the raw material powder particles and the conveying carrier gas to pass through.
3. The combined circulating fluidized bed-entrained flow gasification apparatus of claim 1, wherein: the angle between the inlet direction of the nozzle vertical airflow bed reactor (9) and the horizontal plane is-5 degrees.
4. A circulating fluidized bed-entrained flow combined gasification method using the circulating fluidized bed-entrained flow combined gasification apparatus according to claim 1, comprising the steps of:
a. reaction in circulating fluidized bed riser (1): a first raw material (A) is added from the middle upper part of a circulating fluidized bed lifting pipe (1), is mixed with circulating semicoke from a return pipe (5), and is contacted with a first gasifying agent (B) sent from a gas distributor (6) to realize catalytic gasification reaction to generate synthesis gas rich in methane and high-temperature semicoke particles, the high-temperature semicoke particles are carried by the synthesis gas to enter a first cyclone separator (2), the synthesis gas is sent to a gas separation device (3) for purification and separation treatment after separation, and first product gas (D) rich in methane and CO are obtained2The high-temperature semicoke particles are separated by the first cyclone separator (2) and then are sent into a descending pipe (4) of the circulating fluidized bed for continuous reaction; the first raw material (A) is a low-rank coal raw material containing a catalyst;
b. reaction in a circulating fluidized bed downcomer (4): the high-temperature semicoke particles enter a descending pipe (4) of the circulating fluidized bed, are contacted with loosening air (C) from the middle lower part of the descending pipe (4) of the circulating fluidized bed, generate weak gasification reaction, and are continuously sent to a lifting pipe (1) of the circulating fluidized bed through a material returning pipe (5) under the action of the loosening air (C) to perform circulating gasification reaction;
c. ash treatment of circulating fluidized bed reactor: continuously carrying out the processes of the step a and the step b by the high-temperature semicoke particles, finally forming first ash (E) along with the consumption of combustible substances in the particles, and falling into a first slag hopper (7) from the circulating fluidized bed lifting pipe (1) through a gas distributor (6) by the self gravity; CO separated from the first ash (E) by the gas separation device (3)2The mixture is conveyed to a first nozzle (8) of the fluidized bed reactor and is used as a raw material and a catalyst of the fluidized bed reactor to continue reaction;
d. reaction in a entrained flow reactor (9): the first ash (E) and a second gasifying agent (F) are premixed at the head of a first nozzle (8), injected into an airflow bed reactor (9) and collided with a second raw material (G) and the second gasifying agent (F) premixed from a second nozzle (10), minerals contained in the first ash (E) and a catalyst in an unreacted first raw material (A) have a catalytic action on the surface of the second raw material (G) to generate a violent catalytic gasification reaction, and a crude synthesis gas, fly ash and the second ash are generated;
e. treatment of the reaction products in the entrained-flow reactor (9): the second ash slag falls to a second slag hopper (11) through self gravity to be collected, the fly ash is carried by the crude synthesis gas and sent to a second cyclone separator (12) for gas-solid separation, the separated crude synthesis gas is further sent to a water washing tower (13) for purification processing treatment, and finally a second product gas (H) is obtained.
5. The circulating fluidized bed-entrained flow combined gasification process of claim 4, wherein: the first raw material (A) is a low-rank coal raw material containing a catalyst, and the second raw material (G) is high-rank coal or petroleum coke.
6. The circulating fluidized bed-entrained flow combined gasification process of claim 4, wherein: the low-rank coal raw material is lignite, the high-rank coal raw material is anthracite, and the catalyst is at least one of cheap papermaking black liquor, industrial waste alkali or plant ash.
7. The circulating fluidized bed-entrained flow combined gasification process of claim 4, wherein: the particle sizes of the lignite and the catalyst in the first raw material (A) are both less than 300 mu m, and the particle size of the second raw material (G) is less than 250 mu m.
8. The circulating fluidized bed-entrained flow combined gasification process of claim 4, wherein: the first gasifying agent (B) consists of water vapor and oxygen, and the volume ratio of the water vapor to the oxygen is controlled to be 100: 20-25; the loosening wind (C) consists of water vapor and oxygen, and the volume ratio of the water vapor to the oxygen is controlled to be 100: 5-10; the second gasifying agent (F) is air.
9. The circulating fluidized bed-entrained flow combined gasification process of claim 4, wherein: the operation pressure of the circulating fluidized bed reactor and the operation pressure of the fluidized bed reactor are both more than or equal to 4.0MPa, the operation temperature of the circulating fluidized bed reactor is 850 ℃ and the operation temperature of the fluidized bed reactor is 1650 ℃ respectively.
10. The circulating fluidized bed-entrained flow combined gasification process of claim 4, wherein: the methane-rich synthesis gas generated by the gasification reaction in the circulating fluidized bed reactor is separated by a first cyclone separator (2) and a gas separation device (3) in sequence to obtain CO2The raw materials of a first nozzle (8) and a second nozzle (10) in the fluidized bed reactor (9) are conveyed with gas and enter the fluidized bed reactor (9) together to participate in gasification reaction.
CN201610882443.7A 2016-10-10 2016-10-10 Circulating fluidized bed-entrained flow combined gasification method and device Active CN107916140B (en)

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CN112725038B (en) * 2019-10-29 2021-12-17 中国石油化工股份有限公司 Coal and petroleum coke co-gasification system and method
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CN2608507Y (en) * 2003-02-12 2004-03-31 田原宇 Two stage pulverized coal circulating fluidized bed gasification device
CN101440310A (en) * 2007-11-23 2009-05-27 山东科技大学 Process for fluidized bed classification gasification of dust coal
CN103450946A (en) * 2013-09-02 2013-12-18 张荣光 Fluidized-bed gasification reaction device with independent combustion chamber and fluidized-bed gasification reaction method
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