CN107760382A - Catalytic coal gasifaction method - Google Patents
Catalytic coal gasifaction method Download PDFInfo
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- CN107760382A CN107760382A CN201610710753.0A CN201610710753A CN107760382A CN 107760382 A CN107760382 A CN 107760382A CN 201610710753 A CN201610710753 A CN 201610710753A CN 107760382 A CN107760382 A CN 107760382A
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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
- C10J3/466—Entrained flow processes
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- 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
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- 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
- C10J3/721—Multistage gasification, e.g. plural parallel or serial gasification stages
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- 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
- C10J3/723—Controlling or regulating the gasification process
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- 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
- C10J2300/0916—Biomass
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- 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
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- 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
- C10J2300/0943—Coke
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- 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
- C10J2300/0953—Gasifying agents
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- 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
- C10J2300/0953—Gasifying agents
- C10J2300/0973—Water
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- 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
- C10J2300/0953—Gasifying agents
- C10J2300/0973—Water
- C10J2300/0976—Water as steam
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- 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
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- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/1625—Integration of gasification processes with another plant or parts within the plant with solids treatment
- C10J2300/1628—Ash post-treatment
- C10J2300/1631—Ash recycling
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- 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)
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- 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
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Abstract
The present invention relates to a kind of catalytic coal gasifaction method, mainly solve in catalytic gasification course of reaction that carbon loss vector is high in reactor outlet flying dust and bottom ashe, and the problem of capacity usage ratio is low.The present invention comprises the following steps by using the combined catalysis gasification method of two reactors：The carbon raw material of supported catalyst is passed through in first reactor simultaneously with gasifying agent and oxidant, carries out part burning and gasification reaction, produces synthesis gas and one-level slag, and the synthesis gas with carbon containing flying dust, which enters in gas-solid separator, separates flying dust, then passes through CO2Absorption plant obtains syngas product, partially synthetic gas, which then circulates, to be passed through in first reactor, the flying dust separated is passed through second reactor with one-level slag and carries out completely burned reaction, generate carbon residue content relatively low two level slag and high-temperature gas product, high-temperature gas product is passed through the technical scheme of first reactor again, preferably solve above mentioned problem, can be applied to producing synthesis gas from coal field.
Description
Technical field
The present invention relates to a kind of method of catalytic coal gasifaction, more particularly it relates to using two reactor phase groups
The catalytic coal gasifaction method of conjunction.
Background technology
China is a coal big country, possesses abundant coal resources, with the fast development of China's economy, the life of coal
Yield and consumption figure climb up and up, and the coal production in China in 2014 reaches 38.7 hundred million tons, close to the half of world wide production,
China has become the coal production state and consumption of coal state of global maximum.The direct burning of coal discharges substantial amounts of dirty in utilizing
Thing is contaminated, causes many regional hazes in China to take place frequently, drastically influence environmental problem.Coal Gasification Technology be realize coal it is clean, efficiently,
The key technology of comprehensive utilization, is the important channel of coal conversion, and synthesis of chemicals, combined cycle generation and coal generation
One of key technology with natural gas.At present, various kinds of coal gas technology successfully realizes industrial applications, using on-catalytic gas
Change technology, efficiency of carbon con version is improved by cost of HTHP, this just brings, and coal gas intensity of cooling is big, gas purification is difficult, energy
The problems such as consumption is high, to equipment requirement harshness.However, the catalytic gasification process of coal not only increases gasification reaction speed, while
Gasification reaction temperature is significantly reduced, is achieved the gentle gasification of coal.Many building-up processes can also be carried out simultaneously,
In the presence of catalyst, can while coal gasification the industrial chemicals such as synthesizing methane, methanol, ammonia, shorten technological process.Its
In the synthesis gas rich in methane directly produced by the method for catalytic coal gasifaction, be an important research side of catalytic coal gasifaction
To.
Patent US4318712 discloses a kind of technique of coal one-step method methane, is passed through after catalyst is premixed with coal dust
In reactor, gasifying agent uses superheated steam, while also serves as the reaction temperature in thermal source maintenance reaction device.The temperature of superheated steam
Spend for 850 DEG C, gasification reaction temperature control is at 700 DEG C or so.Coal carries out gasified reverse in the presence of catalyst with superheated steam
Should, while it is passed through CO and H2Based on circulation synthesis gas, strengthen stove in methanation reaction, directly obtain methane rich synthesis gas.
GPE companies of the U.S. are based on proposing a kind of advanced preparing methane from coal technique (patent on the basis of above-mentioned technology
20070000177A1), alkali carbonate or alkali metal hydroxide are used as catalyst, stove is controlled yet by superheated steam
Interior reaction temperature is reacted at 700 DEG C or so, and with coal dust in the presence of catalyst, directly obtains methane-rich gas.Its
Main technical characterstic is in addition to using efficient methanation catalyst, during being also added into calcium oxide to absorbing reaction
Caused carbon dioxide, further improve the content of methane.
Superheated steam need to be heated to 850 DEG C or so by both the above technique, and energy consumption is higher, under conditions of no outer heat supply
It is difficult to maintenance reaction temperature.And because high temperature is unfavorable for the generation of methane, reaction temperature general control is at 700 DEG C, carbon and water
Gasification reaction speed between steam is slow, and the wear rate and conversion ratio of carbon are relatively low.
Patent CN201010279560.7 discloses a kind of multicompartment fluidized bed catalytic gasification methane technology, by gasification furnace point
Section, coal methanation section and synthesis gas methanation section are produced for synthesis gas.Make burning, gasification, methanation reaction and pyrolytic reaction point
Duan Jinhang, the extent of reaction and Temperature Distribution of each section of control, so as to improve methane production.But the pyrolysis section above gasification furnace
In, tiny fine coal is unreacted just to be run out of from gasification furnace so that the carbon content of flying dust is higher, and the complete coal tar of unreacted
Back-mixing is directly discharged from gasification furnace to the furnace bottom cinder notch that gasifies, causes the efficiency of carbon con version in course of reaction relatively low.Coal particle is in gas
When change residing time in furnace is 2~3h, efficiency of carbon con version is maintained essentially in the range of 60~90%.
In summary, catalytic coal gasifaction technology uses single-reactor substantially, due to that need to consider methanation reaction, limits
Its reaction temperature, reaction rate and efficiency of carbon con version is caused to reduce.The race leakage of carbon containing flying dust and the gasification thick slag of furnace bottom in synthesis gas
Direct discharge, largely also contribute to the lifting of efficiency of carbon con version.For the utilization rate of energy, carbon residue is still containing big
The calorific value not being fully utilized is measured, and does not refer to the utilization of this part carbon residue in the catalytic coal gasifaction method proposed.Cause
And it is necessary to develop a kind of catalytic coal gasifaction method that can improve efficiency of carbon con version and energy utilization efficiency.
The content of the invention
The present invention solves the technical problem of in existing catalytic coal gasifaction method, flying dust and furnace bottom that furnace roof is taken out of
The problem of the problem of carbon loss content is high in the lime-ash of discharge and capacity usage ratio are low, there is provided a kind of new to be used to improve carbon
The catalytic coal gasifaction method of conversion ratio and capacity usage ratio.
To solve the above problems, the technical solution adopted by the present invention is as follows：A kind of method of catalytic coal gasifaction, including it is following
Step：The carbon raw material of supported catalyst is passed through in first reactor simultaneously with gasifying agent and oxidant, carry out part burning and
Gasification reaction, synthesis gas and one-level slag are produced, the synthesis gas with carbon containing flying dust, which enters in gas-solid separator, isolates flying dust
Come, then pass through CO2Absorption plant, obtain high concentration CO and H2Syngas product, using partially synthetic gas as circulation synthesis gas lead to
Enter in first reactor, for adjusting the gas componant in reactor, target product CH is improved so as to reach4The purpose of yield.
The carbon containing flying dust that gas-solid separator is separated is passed through in second reactor with the complete one-level slag of unreacted, in the work of oxidant
Completely burned reaction, generation phosphorus content relatively low two level slag and high-temperature gas product are carried out under.Two caused by second reactor
Level slag is expelled directly out reactor, and high-temperature gas product is then passed through in first reactor the supplement as thermal source and gasifying agent.
In above-mentioned technical scheme, described first reactor is selected from：Fixed-bed gasification furnace, fluidized-bed gasification furnace and air-flow
Bed gasification furnace.Described second reactor is selected from：Fixed-bed gasification furnace, fluidized-bed gasification furnace, airflow bed gasification furnace and melting bed
Gasification furnace.
The carbon raw material of supported catalyst, gasifying agent, oxidant and anti-from second are passed through in described first reactor
Answer the high-temperature gas product of device.Optionally, circulation synthesis gas in part can also be passed through in first reactor.
Carbon containing lime-ash and carbon containing flying dust and oxidant from first reactor are passed through in described second reactor.
Reaction condition in described first reactor is：Reaction pressure 0-6.5MPa, 600-1200 DEG C of reaction temperature, gas
Phase linear velocity 0.1-10.0m/s.Reaction condition in second reactor is：Reaction pressure 0-6.5MPa, reaction temperature 800-
1600 DEG C, gas phase linear velocity 0.1-10.0m/s.
Carbon ratio in described first reactor is relatively low, controls in the range of 0.2-0.7mol/mol.Second reaction
Carbon ratio in device is higher, controls in the range of 0.8-1.2mol/mol.
Described carbon raw material is selected from least one of coal, petroleum coke, biomass and its mixture.
Described catalyst is selected from least one of alkali metal, alkaline-earth metal, transition metal and its mixture.Such as carbon
At least one of sour potassium, sodium carbonate, potassium hydroxide, sodium hydroxide, calcium hydroxide, ferric nitrate or nitric acid molybdenum；
Preferable technical scheme is the composite catalyst that catalyst is potassium carbonate and ferric nitrate in above-mentioned technical proposal.
Preferable technical scheme is that catalyst is potassium carbonate and ferric nitrate in above-mentioned technical scheme, and their weight ratio is
(7~9):(3~1).
Described catalyst is supported on carbon raw material in a manner of infusion process, dry pigmentation or ion-exchange etc..
The load capacity of described catalyst accounts for the 0.1~30% of raw coal quality.
Described gasifying agent is selected from aqueous water, vapor, carbon dioxide and its mixture.
Described oxidant is selected from air, oxygen-enriched air, oxygen and its mixture.
Described first reactor is connected with second reactor, and first reactor is connected with gas-solid separator, gas-solid
Separator passes through CO2Absorption plant is connected with first reactor.
Described first reactor and second reactor can be combined in one, can also be respectively arranged at two reactors
In.
Described gas-solid separator is selected from cyclone separator, settler, filter etc. and combinations thereof device.
Described CO2Absorption plant is selected from the things such as low-temp methanol method, polyglycol dimethyl ether process, Ammonia Process and Girbotal process
Reason and chemical absorption process.
Described circulation synthesis gas is through CO2Absorption plant, remove CO2Again the part of first reactor is passed through after gas
Synthesis gas.The gas flow of described circulation synthesis gas accounts for the 0~70% of synthesis gas total flow.
Advantages of the present invention brief introduction
(1) first reactor lays particular emphasis on catalytic gasification reaction, and second reactor lays particular emphasis on combustion reaction, and both have effective group
Close, compensate for reaction temperature in first reactor it is low caused by efficiency of carbon con version it is relatively low the problem of, improve efficiency of carbon con version, solve
The problem of efficiency of carbon con version is low in catalytic gasification course of reaction.
(2) first reactor is made by adjusting circulation synthesis gas and the proportioning of oxidant and gasifying agent in first reactor
In a certain specific region H2/ CO the progress of forced mathaneization reaction, reaches than increase and improves target product CH4The mesh of yield
's.
(3) operation temperature in second reactor is higher, and gas-solid reaction speed is fast, and caused high-temperature gas product is directly logical
Enter in first reactor, thermal source and gasifying agent are provided for the gasification reaction in first reactor, realize heat and logistics
Coupling, improve the utilization ratio of energy.
Brief description of the drawings
Fig. 1 is the schematic diagram of catalytic coal gasifaction provided by the invention.
Fig. 2 is the combined embodiment schematic diagram of two fluid beds.
Carbon raw material, gasifying agent and the oxidant of supported catalyst are passed through in first reactor simultaneously, in the work of catalyst
Gasification reaction is carried out under, produces synthesis gas and one-level slag.Synthesis gas with carbon containing flying dust, which will enter in gas-solid separator, to fly
Ash is separated, then passes through CO2Absorption plant, obtain high concentration CO and H2Syngas product, using partially synthetic gas as circulation
Synthesis gas is passed through in first reactor, and for adjusting the gas componant in reactor, target product CH is improved so as to reach4Yield
Purpose.Caused one-level slag is passed through in second reactor in the flying dust and first reactor separated through gas-solid separator
Combustion reaction, generation carbon content relatively low two level slag and high-temperature gas product are carried out in the presence of oxidant.Two level slag directly from
Discharged in reactor, the gaseous product of high temperature be passed through in first reactor be used as in first reactor catalytic gasification heat source for reaction and
The supplement of gasifying agent.
The carbon raw material added in the present invention in first reactor is mixed with catalyst, and the catalyst is catalyzed during the course of the reaction
Combustion reaction, gasification reaction, transformationreation and methanation reaction.Carbon ratio is relatively low in first reactor, controls in 0.2-
In the range of 0.7mol/mol, part burning and gasification reaction are substantially carried out.Heat caused by combustion reaction disclosure satisfy that gasification
The consumption of heat and heat waste in reaction zone, and provide necessary heat and gasifying agent for gasification reaction.And first reactor
Interior most of region is in reducing atmosphere, CO, H2、CO2、H2O and CH4Exist simultaneously, in the presence of catalyst, transformationreation
Balance can be rapidly reached with methanation reaction.And after being passed through circulation synthesis gas, improve CO and H in reactor2Content, it is dilute
CO is released2Content, the balance for promoting transformationreation moves right, and improves H2/ CO ratio, while also promote methane
Change the movement of reaction balance, improve outlet CH4Yield.But due in first reactor operation temperature it is relatively low, typically exist
In the range of 600-1200 DEG C, the speed of gasification reaction is still relatively low, and the carbon content in the one-level slag and flying dust of outlet is higher.
Combustion reaction is substantially carried out in second reactor, its reaction raw materials derives from the carbon containing flying dust of first reactor outlet
With the one-level slag of reactor bottom.Carbon containing flying dust is separated by gas-solid separating device, is collected and fed into second reactor,
And one-level slag is passed directly into second reactor.Because the carbon ratio in second reactor is higher (0.8-1.2mol/mol), instead
Answer speed fast, burning is more complete, the carbon residue in flying dust and one-level slag is changed into CO rapidly2And H2O, in caused two level slag
Carbon residue is practically free of, reactor can be expelled directly out.Operation temperature is higher in second reactor, typically in 900-1600 DEG C of scope
It is interior, and combustion rate is very fast in the presence of catalyst in one-level slag and ash content, improve efficiency of carbon con version and carbon residue
Utilization rate.High-temperature gas product caused by burning, which is then passed through in first reactor, in second reactor is used as heat in first reactor
Source and the supplement of gasifying agent, the coupling of hot-fluid and logistics between reactor is realized, reduces the oxygen demand in first reactor,
Improve the utilization ratio of energy.
Contain CO, H in the synthesis gas separated in gas-solid separator2、CO2、H2O and CH4Deng gas, pass through CO2Absorb
Device removes the CO in synthesis gas2Gas, improve CO and H2Concentration.Lead to 0-70% synthesis gas as circulation synthesis gas
Enter in first reactor, for adjusting some region of gas composition in reactor, strengthen reacting condition and methanation reaction mistake
Journey, so as to improve target product CH4Yield.
The integrated mode of above-mentioned first reactor and second reactor is selected from：Fixed bed-fluidized bed, fixed bed-air flow bed,
Fluid bed-fluid bed, fluid bed-air flow bed, fluid bed-melting bed, air flow bed-air flow bed, air flow bed-melting bed etc..First
Reactor and second reactor can be arranged up and down by aditus laryngis, are combined in one, can also be connected by pipeline, set respectively
It is placed in two reactors.
Below by embodiment, the invention will be further elaborated, but is not limited only to the present embodiment.
Embodiment
【Embodiment 1】
It is two combined embodiment schematic diagrams of fluid bed referring to Fig. 2.10%K will be impregnated2CO3The coal dust of catalyst adds
In one-level fluidized-bed reactor (first reactor), and oxygen and vapor are transported to fluidized-bed reactor at air distribution plate
In.Make coal dust and oxidant, gasifying agent generating unit divided combustion and gasification reaction in the presence of catalyst.Caused conjunction after reaction
Carbon containing flying dust is separated by cyclone separator into gas, the synthesis gas after flying dust is removed and passes through CO2Absorption plant, absorb and close
Into the CO in gas2Gas.And by 30% through CO2Synthesis gas after absorption, circulation, which is passed through in one-level fluidized-bed reactor, adjusts gasification
H in stove in upper zone2/ CO ratio, strengthen transformationreation and the progress of methanation reaction.The reaction temperature of gasification furnace
At 700 DEG C, Stress control is generated with CH in 3.5MPa for control4、CO、H2Deng active principle and CO2, a small amount of H2S and NH3Deng
Gaseous product, wherein CH4Concentration be 25%.It is left in 0.5mol/mol because in one-level fluidized-bed reactor, carbon ratio is relatively low
The right side, gasification reaction speed is slower, thus efficiency of carbon con version is less than 80%.The flying dust that cyclone separator is separated and collected is together with one-level stream
In lime-ash input two level fluidized-bed reactor caused by fluidized bed reactor bottom (second reactor).Oxygen is anti-from two level fluid bed
Answer and be passed through at the air distribution plate of device, combustion reaction is carried out with one-level slag and flying dust.Because the carbon ratio in two level fluid bed is higher, reach
To 1.0mol/mol, be substantially carried out quick combustion reaction, the control of its reaction temperature at 1000 DEG C, Stress control in 3.5MPa,
1000 DEG C of generation is with CO2And H2High-temperature gas product based on O, and one-level fluidized-bed gasification furnace bottom is passed through, it is one-level fluid bed
The gasification reaction of interior heat absorption supplements thermal source and gasifying agent.In lime-ash caused by two level fluidized-bed reactor outlet at bottom hardly
Carbon containing carbon residue, efficiency of carbon con version have reached 99.0%.
【Embodiment 2】
It is two combined embodiment schematic diagrams of fluid bed referring to Fig. 2.10%K will be impregnated2CO3The coal dust of catalyst adds
In one-level fluidized-bed reactor (first reactor), and oxygen and vapor are transported to fluidized-bed reactor at air distribution plate
In.Make coal dust and oxidant, gasifying agent generating unit divided combustion and gasification reaction in the presence of catalyst.Caused conjunction after reaction
Carbon containing flying dust is separated by cyclone separator into gas, the synthesis gas after flying dust is removed and passes through CO2Absorption plant, absorb and close
Into the CO in gas2Gas.And by 30% through CO2Synthesis gas after absorption, circulation, which is passed through in one-level fluidized-bed reactor, adjusts gasification
H in stove in upper zone2/ CO ratio, strengthen transformationreation and the progress of methanation reaction.The reaction temperature of gasification furnace
At 700 DEG C, Stress control is generated with CH in 3.5MPa for control4、CO、H2Deng active principle and CO2, a small amount of H2S and NH3Deng
Gaseous product, wherein CH4Concentration be 25%.It is left in 0.5mol/mol because in one-level fluidized-bed reactor, carbon ratio is relatively low
The right side, gasification reaction speed is slower, thus efficiency of carbon con version is less than 80%.The flying dust that cyclone separator is separated and collected is together with one-level stream
In lime-ash input two level fluidized-bed reactor caused by fluidized bed reactor bottom (second reactor).Oxygen is anti-from two level fluid bed
Answer and be passed through at the air distribution plate of device, combustion reaction is carried out with one-level slag and flying dust.Because the carbon ratio in two level fluid bed is higher, reach
To 1.1mol/mol, be substantially carried out quick combustion reaction, the control of its reaction temperature at 1000 DEG C, Stress control in 3.5MPa,
1000 DEG C of generation is with CO2And H2High-temperature gas product based on O, and one-level fluidized-bed gasification furnace bottom is passed through, it is one-level fluid bed
The gasification reaction of interior heat absorption supplements thermal source and gasifying agent.In lime-ash caused by two level fluidized-bed reactor outlet at bottom hardly
Carbon containing carbon residue, efficiency of carbon con version have reached 99.5%.
【Embodiment 3】
It is two combined embodiment schematic diagrams of fluid bed referring to Fig. 2.7%K will be impregnated2CO3With 3% nitric acid iron catalyst
Coal dust add in one-level fluidized-bed reactor (first reactor), and oxygen and vapor are transported to fluidisation at air distribution plate
In bed reactor.Make coal dust and oxidant, gasifying agent generating unit divided combustion and gasification reaction in the presence of catalyst.After reaction
Caused synthesis gas is separated carbon containing flying dust by cyclone separator, is removed the synthesis gas after flying dust and is passed through CO2Absorb dress
Put, absorb the CO in synthesis gas2Gas.And by 30% through CO2Synthesis gas after absorption, circulation are passed through one-level fluidized-bed reactor
H in middle regulation gasification furnace in upper zone2/ CO ratio, strengthen transformationreation and the progress of methanation reaction.Gasification furnace
Reaction temperature control at 700 DEG C, Stress control is generated with CH in 3.5MPa4、CO、H2Deng active principle and CO2, it is a small amount of
H2S and NH3Deng gaseous product, wherein CH4Concentration be 27%.Because in one-level fluidized-bed reactor, carbon ratio is relatively low,
0.5mol/mol or so, gasification reaction speed is slower, thus efficiency of carbon con version is less than 80%.What cyclone separator was separated and collected flies
Ash is together with (second reactor) in lime-ash input two level fluidized-bed reactor caused by one-level fluidized-bed reactor bottom.Oxygen from
It is passed through at the air distribution plate of two level fluidized-bed reactor, combustion reaction is carried out with one-level slag and flying dust.Due in two level fluid bed
Carbon ratio is higher, reaches 1.0mol/mol, is substantially carried out quick combustion reaction, and the control of its reaction temperature is at 1000 DEG C, pressure
Control in 3.5MPa, 1000 DEG C of generation is with CO2And H2High-temperature gas product based on O, and be passed through under one-level fluidized-bed gasification furnace
Portion, the gasification reaction for heat absorption in one-level fluid bed supplement thermal source and gasifying agent.Two level fluidized-bed reactor outlet at bottom produces
Carbon residue carbon is practically free of in raw lime-ash, efficiency of carbon con version has reached 99.9%.
【Embodiment 4】
It is two combined embodiment schematic diagrams of fluid bed referring to Fig. 2.10%K will be impregnated2CO3The coal dust of catalyst adds
In one-level fluidized-bed reactor (first reactor), and oxygen and vapor are transported to fluidized-bed reactor at air distribution plate
In.Make coal dust and oxidant, gasifying agent generating unit divided combustion and gasification reaction in the presence of catalyst.Caused conjunction after reaction
Carbon containing flying dust is separated by cyclone separator into gas, the synthesis gas after flying dust is removed and passes through CO2Absorption plant, absorb and close
Into the CO in gas2Gas.And by 50% through CO2Synthesis gas after absorption, circulation, which is passed through in one-level fluidized-bed reactor, adjusts gasification
H in stove in upper zone2/ CO ratio, strengthen transformationreation and the progress of methanation reaction.The reaction temperature of gasification furnace
At 700 DEG C, Stress control is generated with CH in 3.5MPa for control4、CO、H2Deng active principle and CO2, a small amount of H2S and NH3Deng
Gaseous product, wherein CH4Concentration be 32%.It is left in 0.5mol/mol because in one-level fluidized-bed reactor, carbon ratio is relatively low
The right side, gasification reaction speed is slower, thus efficiency of carbon con version is less than 80%.The flying dust that cyclone separator is separated and collected is together with one-level stream
In lime-ash input two level fluidized-bed reactor caused by fluidized bed reactor bottom (second reactor).Oxygen is anti-from two level fluid bed
Answer and be passed through at the air distribution plate of device, combustion reaction is carried out with one-level slag and flying dust.Because the carbon ratio in two level fluid bed is higher, reach
To 1.0mol/mol, be substantially carried out quick combustion reaction, the control of its reaction temperature at 1000 DEG C, Stress control in 3.5MPa,
1000 DEG C of generation is with CO2And H2High-temperature gas product based on O, and one-level fluidized-bed gasification furnace bottom is passed through, it is one-level fluid bed
The gasification reaction of interior heat absorption supplements thermal source and gasifying agent.In lime-ash caused by two level fluidized-bed reactor outlet at bottom hardly
Carbon containing carbon residue, efficiency of carbon con version have reached 99.0%.
【Comparative example 1】
Catalytic gasification reaction unit in the one-step method preparing methane from coal technique proposed using Exxon companies, from 10% carbon
Sour potassium catalyst, operating pressure 3.5MPa, 850 DEG C of superheated steam, 700 DEG C of operation temperature.Experiment is obtained in exit gas component
Methane content 19%, methane production 0.39Nm3/ kg, efficiency of carbon con version 85%.
【Comparative example 2】
Gasification reaction in the technique of the multicompartment fluidized bed catalytic gasification methane-rich gas proposed using Xin Ao groups is filled
Put, from the potassium carbonate that catalyst is 10%, operating pressure 3.5MPa, 700 DEG C of operation temperature.Test obtained exit gas group
CO+H in point2Content 64.2%, methane content 8.4%, methane production 0.15Nm3/ kg, efficiency of carbon con version 50%.
Claims (10)
- A kind of 1. method of catalytic coal gasifaction, it is characterised in that comprise the following steps：The carbon raw material of supported catalyst and gasification Agent and oxidant are passed through in first reactor simultaneously, carry out part burning and gasification reaction, produce synthesis gas and one-level slag；Carry The synthesis gas of carbon containing flying dust, which enters in gas-solid separator, separates flying dust, then passes through CO2Absorption plant obtains synthesis gas production Thing, partially synthetic gas are passed through in first reactor as circulation synthesis gas；Isolated flying dust is together with one-level in gas-solid separator In slag input second reactor, completely burned reaction is carried out in the presence of oxidant, generates two level slag and high-temperature gas product； High-temperature gas product is passed directly into first reactor.
- 2. catalytic coal gasifaction method according to claim 1, it is characterised in that described carbon raw material is selected from coal, oil Burnt, biomass and its mixture, described gasifying agent are selected from aqueous water, vapor, carbon dioxide and its mixture, described oxygen Agent is selected from air, oxygen-enriched air, oxygen and its mixture.
- 3. catalytic coal gasifaction method according to claim 1, it is characterised in that described catalyst is selected from alkali metal, alkaline earth At least one of metal, transition metal；Described catalyst is supported in a manner of infusion process, dry pigmentation or ion-exchange On carbon raw material；The load capacity of described catalyst accounts for the 0.1~30% of raw coal quality.
- 4. catalytic coal gasifaction method according to claim 1, it is characterised in that load is passed through in described first reactor The carbon raw material of catalyst, gasifying agent, oxidant, high-temperature gas product and circulation synthesis gas, one-level is passed through in second reactor Slag, flying dust and oxidant.
- 5. catalytic coal gasifaction method according to claim 1, it is characterised in that the reaction condition of described first reactor For：Reaction pressure 0-6.5MPa, 600-1200 DEG C of reaction temperature, gas phase linear velocity 0.1-10.0m/s, the reaction of second reactor Condition is：Reaction pressure 0-6.5MPa, 800-1600 DEG C of reaction temperature, gas phase linear velocity 0.1-10.0m/s.
- 6. catalytic coal gasifaction method according to claim 1, it is characterised in that described first reactor is selected from fixed bed Gasification furnace, fluidized-bed gasification furnace and airflow bed gasification furnace, second reactor are selected from fixed-bed gasification furnace, fluidized-bed gasification furnace, gas Fluidized gas producer and molten bath gasifica tion stove.
- 7. catalytic coal gasifaction method according to claim 1, it is characterised in that the scope of the carbon ratio in first reactor For 0.2-0.7mol/mol, the scope of the carbon ratio in second reactor is 0.8-1.2mol/mol.
- 8. catalytic coal gasifaction method according to claim 1, it is characterised in that described first reactor and the second reaction Device is combined in one or is respectively arranged in two reactors.
- 9. catalytic coal gasifaction method according to claim 1, it is characterised in that described first reactor cinder notch and second Reactor feed mouth is connected, and second reactor gas vent is connected with first reactor, the gas vent of first reactor It is connected with gas-solid separator, gas-solid separator bottom is connected with second reactor charging aperture, gas-solid separator top gas Outlet and CO2Absorption plant is connected, and portion gas is connected as circulation synthesis gas with first reactor, and remainder is direct Into upstream device.
- 10. catalytic coal gasifaction method according to claim 9, it is characterised in that the flow of described circulation synthesis gas accounts for conjunction Into the 0~70% of gas total flow.
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| CN111826207A (en) * | 2020-07-03 | 2020-10-27 | 新奥科技发展有限公司 | Gasification ash treatment device and method and coal catalytic gasification system |
| CN111826206A (en) * | 2019-04-15 | 2020-10-27 | 乔治洛德方法研究和开发液化空气有限公司 | Method for controlling slagging gasification process on line and equipment for gasification process |
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| CN108753359A (en) * | 2018-05-10 | 2018-11-06 | 新奥科技发展有限公司 | A kind of carrying method and catalytic coal gasifaction method of catalyst |
| CN111826206A (en) * | 2019-04-15 | 2020-10-27 | 乔治洛德方法研究和开发液化空气有限公司 | Method for controlling slagging gasification process on line and equipment for gasification process |
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| CN110172362B (en) * | 2019-05-16 | 2021-05-11 | 新奥科技发展有限公司 | Catalytic coal gasification method |
| CN111826207A (en) * | 2020-07-03 | 2020-10-27 | 新奥科技发展有限公司 | Gasification ash treatment device and method and coal catalytic gasification system |
| CN113753856A (en) * | 2021-09-27 | 2021-12-07 | 太原理工大学 | Organic solid waste gasification integrated efficient hydrogen and methane production process |
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