CN106635176A - Coal catalytic gasification method - Google Patents

Coal catalytic gasification method Download PDF

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Publication number
CN106635176A
CN106635176A CN201611196781.1A CN201611196781A CN106635176A CN 106635176 A CN106635176 A CN 106635176A CN 201611196781 A CN201611196781 A CN 201611196781A CN 106635176 A CN106635176 A CN 106635176A
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coal
silicate
aluminate
catalyst
alkali metal
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CN106635176B (en
Inventor
王志青
梅艳钢
黄戒介
房倚天
余中亮
聂伟
宋双双
李俊国
张永奇
赵建涛
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Shanxi Institute of Coal Chemistry of CAS
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Shanxi Institute of Coal Chemistry of CAS
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B01J23/04—Alkali metals
    • 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
    • C10J3/02—Fixed-bed gasification of lump fuel
    • C10J3/06—Continuous processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/48—Apparatus; Plants
    • C10J3/482—Gasifiers with stationary fluidised bed
    • 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
    • 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
    • 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
    • Y02P20/584—Recycling of catalysts

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a coal catalytic gasification method. The coal catalytic gasification method comprises the following steps: mixing aluminate of alkali metal and/or a silicate catalyst with coal to obtain coal loaded with the catalyst, adding the coal loaded with the catalyst into a gasification furnace to be gasified, putting gasification slag in water, stirring for reacting for 1-2 hours at the temperature of 20-90 DEG C, then filtering and washing a filter cake, so that a solution containing aluminate and/or silicate is obtained. The coal catalytic gasification method provided by the invention has the advantages that the catalyst can be easily recycled and corrosion is low.

Description

A kind of method of catalytic coal gasifaction
Technical field
The invention belongs to coal gasification field, and in particular to a kind of method of catalytic coal gasifaction.
Background technology
Coal gasification is Coal Chemical Industry common techniques, the leading technology of core technology sum.Traditional gasification furnace is to reach high carbon to turn Rate, big treating capacity, generally in high temperature, high pressing operation, harsh operating condition make gasification furnace manufacture and running cost it is high, Fluctuation of service.And as the catalytic gasification of new type coal gasification mode gasification can be made real under conditions of more gently It is existing.Meanwhile, catalytic gasification energy modulation coal gas composition, with preferable prospects for commercial application.
At present, the most frequently used catalyst of catalytic gasification is Na2CO3With K2CO3Deng base metal catalysts.Alkali-metal addition Gasification reaction speed can be significantly improved, reaction temperature is reduced.But Na2CO3With K2CO3It is relatively low Deng base metal catalysts fusing point, Gasification has part and evaporate into gas phase, and also to equipment for gasification heavy corrosion is produced while causing catalyst loss.Additionally, During catalytic gasification reacts, alkali metal can generate the nepheline without catalytic action and silicon with the siulica-alumina mineral qualitative response in coal Aluminate, and the nepheline for generating is difficult to realize alkali-metal recovery by water-soluble process that this causes catalyst to lose with aluminosilicate Living and catalyst reclaims difficult.Therefore, the recovery of base metal catalysts and alkali-metal volatilization, etching problem is that restriction coal is urged The major obstacle of activating QI chemical industry.
The content of the invention
It is an object of the present invention to provide a kind of method that catalyst is easily reclaimed, corrodes little catalytic coal gasifaction.
Technical proposal that the invention solves the above-mentioned problems is：
The present invention be with alkali metal aluminate and/or silicate as catalyst, the catalyst have difficult inactivation, fusing point it is high, The characteristics of volatility is low.Aluminate and/or silicate obtain the coal of supported catalyst after mixing with certain proportion with coal.With Na2CO3、K2CO3Compare Deng base metal catalysts, aluminate, silicate catalyst fusing point are high, volatility is low and stable, therefore not Readily volatilized and inactivation.In addition, after the coal gasification of supported catalyst, its lime-ash is obtained containing catalyst after washing filtering Solution, so as to realize the recovery of catalyst.
The present invention is a kind of method of catalytic coal gasifaction, is comprised the following steps：
(1) when using low-order coal, alkali metal quality is the 1-4.5wt% of ature of coal amount, when using high-order coal, alkali Metallic element quality is the 1-6.5wt% of ature of coal amount, and alkali-metal aluminate and/or silicate catalyst and coal mixing are mixed The coal of supported catalyst is obtained after conjunction；
(2) coal of supported catalyst is added and is gasified in gasification furnace, the operation temperature of gasification is 600-1200 DEG C, pressure Power 0-8MP, gasifying agent is air, oxygen, water vapour, CO2One or more；
(3) gasification slag is put in water, in temperature 20-90 DEG C, stirring reaction 1-2h, then after filtering and wash filter cake, The solution containing aluminate and silicate is obtained, the addition of wherein water is 1-100 times of gasification slag amount.
Described alkali metal aluminate is sodium aluminate, sodium metaaluminate, potassium aluminate, and silicate is sodium silicate, potassium silicate.
Described low-order coal is peat, brown coal, jet coal, bottle coal.
Described high-order coal is lean coal, meager coal, anthracite.
Described gasification furnace is fixed-bed gasification furnace, fluidized-bed gasification furnace or airflow bed gasification furnace.
The addition total amount of the gasifying agent is 1.3-8 times of ature of coal amount.
The spraying is comprised the following steps：
(1) alkali metal aluminate and/or silicate are weighed according to load capacity, on the basis of coal add 0.5-10 times go from Sub- water is simultaneously heated to 40-90 DEG C；
(2) alkali metal aluminate and/or silicate are loaded on coal in the form of spraying, and at 80-110 DEG C 2-12h is dried, Obtain the coal of supported catalyst.
The mechanical mixing is comprised the following steps：
By alkali-metal aluminate and/or silicate catalyst and coal mixing, 3- is ground on oscillating mill after mixing After 10min, the coal that mechanical mixing prepares supported catalyst is obtained.
Impregnation method as above comprises the steps：
(1) alkali-metal aluminate and/or silicate are added in water and are sufficiently stirred for, obtain containing aluminate and/ Or the solution of silicate, water addition be aluminate, 20-100 times of silicate quality；
(2) when using low order brown coal, by the 1-4.5wt% that alkali metal quality is ature of coal amount, when using high-order coal When, it is the 1-6.5wt% of ature of coal amount by alkali metal quality, during coal to be poured into the solution of preparation, keep stirring at 40-90 DEG C Mix, until forming pulpous state thick liquid.
(3) the slurry shape material for obtaining is dried 2-12h at 80-150 DEG C, obtains the coal of supported catalyst.
Advantages of the present invention is as follows with technique effect：
1st, alkali metal aluminate, silicate have higher fusing point, and alkali-metal volatile quantity very little, urges in gasification The loss of agent is few, and the corrosion to the furnace apparatus that gasify is less；
2nd, gasify lime-ash melt temperature it is higher (>1200 DEG C), it is to avoid the phenomenon of melting slagging scorification is produced in gasification；
3 and traditional Alkali-Metal Na2CO3、K2CO3Compare, catalyst recovery yield height (85-98%), alkali metal corrosivity are little.
Specific embodiment
The present invention is described in further details below by embodiment, but invention protection domain does not limit to interior with described Hold.
Embodiment 1：The present embodiment with low-order coal North SinKiang peat as sample, with sodium aluminate as catalyst, using fixed bed gas Change stove, sodium aluminate is loaded on peat by solution dipping method, catalyst support step is as follows：
1) mass ratio of water and sodium aluminate is 20, and mixture is stirred to being completely dissolved at 60 DEG C；
2) alkali metal Na mass for ature of coal amount 1wt%, will peat add solution in, stirring and keeping temperature until Form slurry like material；
3) the coal slurry like material for obtaining is dried 12h at 110 DEG C, obtains the peat of supported catalyst.
The North SinKiang peat of load sodium aluminate is taken, fixed-bed gasification furnace is added, alkali metal Na mass is ature of coal amount 1wt%, gasification temperature is 600 DEG C, pressure 0.1MP, using air and CO2Gasification, air/coal mass ratio is 1.8, CO2/ ature of coal Amount is than being 3.Residue after gasifying is 20 by liquid-solid ratio, and gasification slag is put in water, under temperature 50 C, after stirring leaching 1h, is passed through After filter and filter cake is washed, obtain the solution containing sodium aluminate and sodium silicate.Charcoal percent conversion is shown in catalyst recovery yield after reaction Table one.
Embodiment 2：The present embodiment with the little Longtan Brown Coal of low order as sample, with sodium aluminate as catalyst, using fluid bed gas Change furnace gas, catalyst is loaded on coal by mechanical mixing, catalyst support step is as follows：
Alkali metal Na mass is the 4wt% of ature of coal amount, and coal is obtained after grinding 5min on vibration coal pulverizer with sodium aluminate To the brown coal of mechanical mixing load.
The brown coal of load sodium aluminate are taken, fluidized-bed gasification furnace is added, alkali metal Na mass is ature of coal amount 4wt%, is pressed Power is 1MP, and gasification temperature is 900 DEG C, and gasifying agent is air and water vapour, and air/coal mass ratio is 2.4, water vapour/ature of coal amount Than for 2.Residue after gasifying is 40 by liquid-solid ratio, and gasification slag is put in water, and under temperature 50 C, after stirring leaching 1h, Jing is filtered Afterwards and filter cake is washed, obtain the solution containing sodium aluminate and sodium silicate.Charcoal percent conversion is shown in Table with catalyst recovery yield after reaction One.
Embodiment 3：The present embodiment, with sodium aluminate and sodium silicate as catalyst, is adopted with high-order Jincheng Anthracite as sample Airflow bed gasification furnace gasifies, and sodium aluminate and sodium silicate is loaded on anthracite by spraying, and catalyst support step is as follows：
1) sodium aluminate and sodium silicate mass ratio are 1, and water is 10 with the mass ratio of sodium aluminate, and water is with sodium silicate mass ratio 10, mixture is stirred to being completely dissolved at 60 DEG C；
2) alkali metal Na mass is the 6.5wt% of ature of coal amount, and catalyst solution is loaded in the form of spraying coal On, 12h is dried at 110 DEG C, obtain the coal of supported catalyst.
Take the coal of supported catalyst, add airflow bed gasification furnace, alkali metal Na mass is ature of coal amount 6.5wt%, aluminum Sour sodium is 1 with sodium silicate mass ratio, and pressure is 3MP, and gasification temperature is 1200 DEG C, and gasifying agent is oxygen and water vapour, oxygen/coal Mass ratio is 0.8, and water vapour/coal mass ratio is 3.Residue after gasifying is 60 by liquid-solid ratio, gasification slag is put in water, in temperature 70 At DEG C, after stirring leaching 1h, after filtering and filter cake is washed, obtain the solution containing sodium aluminate and sodium silicate.Carbon after reaction Conversion ratio is shown in Table one with catalyst recovery yield.
Embodiment 4：The present embodiment with the little Longtan Brown Coal of low-order coal as sample, with potassium silicate as catalyst, using fixed bed Gasification furnace, is loaded to potassium silicate on brown coal by solution dipping method.Catalyst support step is as follows：
1) mass ratio of water and potassium silicate is 40, and mixture is stirred to being completely dissolved at 60 DEG C；
2) alkali metal element K quality for ature of coal amount 2wt%, will brown coal add solution in, stirring and keeping temperature until Form slurry like material；
3) the coal slurry like material for obtaining is dried 12h at 110 DEG C, obtains the brown coal of supported catalyst.
The coal of load potassium silicate is taken, fixed-bed gasification furnace is added, alkali metal element K quality is ature of coal amount 2wt%, and pressure is 5MP, gasification temperature is 1100 DEG C, and gasifying agent is oxygen, and oxygen/coal mass ratio is 1.5.Residue after gasifying is 80 by liquid-solid ratio, will Gasification slag is put in water, at 80 DEG C of temperature, after stirring leaching 1h, after filtering and washs filter cake, obtain containing potassium aluminate with The solution of potassium silicate.Charcoal percent conversion is shown in Table one with catalyst recovery yield after reaction.
Embodiment 5：The present embodiment with Jincheng Anthracite as sample, with potassium aluminate as catalyst, using fluidized-bed gasification furnace Gasification, catalyst is loaded to potassium aluminate on anthracite using solution dipping method.Catalyst support step is as follows：
1) mass ratio of water and potassium aluminate is 40, and mixture is stirred to being completely dissolved at 60 DEG C；
2) alkali metal element K quality is the 4wt% of ature of coal amount, and anthracite is added in solution, and simultaneously keeping temperature is straight for stirring To formation slurry like material；
3) the coal slurry like material for obtaining is dried 12h at 110 DEG C, obtains the Jincheng Anthracite of supported catalyst.
The coal of load potassium aluminate is taken, fluidized-bed gasification furnace is added, alkali metal element K quality is ature of coal amount 4wt%, and pressure is 2MP, gasification temperature is 1000 DEG C, and gasifying agent is air, and air/coal mass ratio is 7.Residue after gasifying is 90 by liquid-solid ratio, by gas Slugging is put in water, at 90 DEG C of temperature, after stirring leaching 1h, after filtering and washs filter cake, is obtained containing potassium aluminate and silicon The solution of sour potassium.Charcoal percent conversion is shown in Table one with catalyst recovery yield after reaction.
Embodiment 6：The present embodiment with low-order coal North SinKiang peat as sample, with sodium metaaluminate as catalyst, using air flow bed Gasification furnace gasifies, and sodium metaaluminate is loaded on the peat of North SinKiang by solution dipping method.Catalyst support step is as follows：
1) mass ratio of water and sodium metaaluminate is 80, and mixture is stirred to being completely dissolved at 60 DEG C；
2) alkali metal Na mass for ature of coal amount 2wt%, will peat add solution in, stirring and keeping temperature until Form slurry like material；
3) the coal slurry like material for obtaining is dried 12h at 110 DEG C, obtains the peat of supported catalyst.
The peat of load sodium metaaluminate is taken, airflow bed gasification furnace is added, alkali metal Na mass is ature of coal amount 2wt%, Pressure is 3MP, and gasification temperature is 1100 DEG C, and gasifying agent is air and CO2, air/coal mass ratio is 2, CO2/ coal mass ratio is 2. Residue after gasifying is 20 by liquid-solid ratio, and gasification slag is put in water, under temperature 70 C, after stirring leaching 1h, after filtering and is washed Filter cake is washed, the solution containing sodium aluminate and sodium silicate is obtained.Charcoal percent conversion is shown in Table one with catalyst recovery yield after reaction.
Embodiment 7：The present embodiment with Jincheng Anthracite as sample, with potassium silicate, sodium silicate as catalyst, using fixed bed Gasification furnace, is loaded to potassium silicate, sodium silicate on anthracite by solution dipping method.Catalyst support step is as follows：
1) sodium silicate and potassium silicate mass ratio are 1.3, and water is 40 with catalyst total mass ratio, and mixture is stirred at 60 DEG C To being completely dissolved；
2) alkali metal Na mass is the 3wt% of ature of coal amount, and alkali metal element K quality is the 3wt% of ature of coal amount, by nothing Bituminous coal is added in solution, stirs and keeping temperature is until form slurry like material；
3) the coal slurry like material for obtaining is dried 12h at 110 DEG C, obtains the Jincheng Anthracite of supported catalyst.
The coal of carrying alkali metal is taken, fixed-bed gasification furnace is added, the load capacity of base metal catalysts is 6wt%, Na：K=1 (mass ratio), pressure is 2MP, and gasification temperature is 900 DEG C, and gasifying agent is oxygen and water vapour, and oxygen/coal mass ratio is 0.5, water Steam/coal mass ratio is 3.Residue after gasifying is 20 by liquid-solid ratio, and gasification slag is put in water, at 80 DEG C of temperature, stirring leaching After 1h, after filtering and filter cake is washed, obtained containing sodium silicate and potassium silicate, the solution of sodium aluminate and potassium aluminate.Carbon after reaction Conversion ratio and catalyst recovery yield be shown in Table one.
Embodiment 8：The present embodiment with North SinKiang peat as sample, with sodium silicate as catalyst, using fluidized gasification furnace gas Change, sodium silicate is loaded on the peat of North SinKiang by solution dipping method.Catalyst support step is as follows：
1) mass ratio of water and sodium silicate is 60, and mixture is stirred to being completely dissolved at 60 DEG C；
2) alkali metal Na mass for ature of coal amount 3wt%, will peat add solution in, stirring and keeping temperature until Form slurry like material；
3) the coal slurry like material for obtaining is dried 12h at 110 DEG C, obtains the North SinKiang peat of supported catalyst.
The North SinKiang peat of load sodium silicate is taken, fluidized-bed gasification furnace is added, alkali metal Na mass is ature of coal amount 3wt%, pressure is 2MP, and gasification temperature is 1100 DEG C, and gasifying agent is oxygen and CO2, oxygen/coal mass ratio is 0.7, CO2/ ature of coal Amount is than being 3.Residue after gasifying is 20 by liquid-solid ratio, and gasification slag is put in water, at 80 DEG C of temperature, after stirring leaching 1h, is passed through After filter and filter cake is washed, obtain the solution containing sodium silicate.Charcoal percent conversion is shown in Table one with catalyst recovery yield after reaction.
Embodiment 9：The present embodiment with little Longtan Brown Coal as sample, with sodium aluminate and potassium aluminate as catalyst, using air-flow Bed gasification furnace gasifies, and sodium aluminate and potassium aluminate is loaded on little Longtan Brown Coal by solution dipping method, catalyst support step It is as follows：
1) sodium aluminate and potassium aluminate mass ratio are 1.4, and water is 50 with sodium aluminate and potassium aluminate total mass ratio, and mixture is 60 Stir at DEG C to being completely dissolved；
2) alkali metal Na mass is the 1wt% of ature of coal amount, and alkali metal element K quality is the 1wt% of ature of coal amount, will be brown Coal is added in solution, stirs and keeping temperature is until form slurry like material；
3) the coal slurry like material for obtaining is dried 12h at 110 DEG C, obtains the little Longtan Brown Coal of supported catalyst.
The little Longtan Brown Coal of supported catalyst, addition airflow bed gasification furnace are taken, the load capacity of base metal catalysts is 2wt%, Na：K=1 (mass ratio), pressure is 1MP, and gasification temperature is 1000 DEG C, and gasifying agent is air and water vapour, air/coal Mass ratio is 3, and water vapour/coal mass ratio is 3.Residue after gasifying is 20 by liquid-solid ratio, gasification slag is put in water, in 80 DEG C of temperature Under, after stirring leaching 1h, after filtering and filter cake is washed, obtain the solution containing sodium aluminate Yu potassium aluminate.Carbon turns after reaction Rate is shown in Table one with catalyst recovery yield.
Comparative example 1：With North SinKiang peat as sample, using fixed-bed gasification furnace, gasifying agent is air and CO to the present embodiment2, The mass ratio of air/coal is 1.8, CO2The mass ratio of/coal is 4, and gasification temperature is 600 DEG C, and pressure is 0.1MP.Determine after reaction Charcoal percent conversion.
Comparative example 2：With little Longtan Brown Coal as sample, using fluidized-bed gasification furnace, gasifying agent is air and water to the present embodiment Steam, the mass ratio of air/coal is 2.4, and the mass ratio of water vapour/coal is 2, and gasification temperature is 900 DEG C, and pressure is 1MP.Reaction After determine charcoal percent conversion.
Comparative example 3：With Jincheng Anthracite as sample, using airflow bed gasification furnace, gasifying agent is oxygen and water to the present embodiment Steam, the mass ratio of oxygen/coal is 0.8, and the mass ratio of water vapour/coal is 5, and gasification temperature is 1200 DEG C, and pressure is 3MP.Instead Should after determine charcoal percent conversion.
Comparative example 4：The present embodiment with Jincheng Anthracite as sample, with Na2CO3For catalyst, using fixed-bed gasification furnace, By mechanical mixing by Na2CO3Load on anthracite.Catalyst support step is as follows：
Alkali metal Na mass is the 6wt% of ature of coal amount, by coal and Na2CO3It is put on vibration coal pulverizer and grinds after 5min Obtain the anthracite of mechanical mixing supported catalyst.
Take Na2CO3Coal, add fixed-bed gasification furnace, alkali metal Na mass be ature of coal amount 6wt%, pressure is 2MP, Gasification temperature is 900 DEG C, and gasifying agent is oxygen and water vapour, and oxygen/coal mass ratio is 0.5, and water vapour/coal mass ratio is 3.Gas It is 20 to change residue by liquid-solid ratio, and gasification slag is put in water, at 80 DEG C of temperature, after stirring leaching 1h, after filtering and is washed Filter cake, obtains containing Na2CO3Solution.Charcoal percent conversion is shown in Table one with catalyst recovery yield after reaction.
Table one. charcoal percent conversion and catalyst recovery yield in the embodiment under different condition

Claims (9)

1. a kind of method of catalytic coal gasifaction, it is characterised in that comprise the following steps：
（1）When using low-order coal, alkali metal quality is the 1-4.5 wt% of ature of coal amount, when using high-order coal, alkali metal Element quality is the 1-6.5 wt% of ature of coal amount, alkali-metal aluminate and/or silicate catalyst and coal is mixed, after mixing Obtain the coal of supported catalyst；
（2）The coal of supported catalyst is added and is gasified in gasification furnace, the operation temperature of gasification is 600-1200 DEG C, pressure 0- 8 MP, gasifying agent is air, oxygen, water vapour, CO2One or more；
（3）Gasification slag is put in water, in temperature 20-90 DEG C, stirring reaction 1-2 h, then after filtering and filter cake is washed, obtain Solution containing aluminate and/or silicate, the addition of wherein water is 1-100 times of gasification slag amount.
2. a kind of method of catalytic coal gasifaction as claimed in claim 1, it is characterised in that described alkali metal aluminate is aluminum Sour sodium, sodium metaaluminate or potassium aluminate, silicate is sodium silicate or potassium silicate.
3. a kind of method of catalytic coal gasifaction as claimed in claim 1, it is characterised in that described low-order coal is peat, brown Coal, jet coal or bottle coal.
4. a kind of method of catalytic coal gasifaction as claimed in claim 1, it is characterised in that described high-order coal is lean coal, meager coal Or anthracite.
5. a kind of method of catalytic coal gasifaction as claimed in claim 1, it is characterised in that described gasification furnace is fixed bed gas Change stove, fluidized-bed gasification furnace or airflow bed gasification furnace.
6. a kind of method of catalytic coal gasifaction as claimed in claim 1, it is characterised in that the addition total amount of the gasifying agent is 1.3-8 times of ature of coal amount.
7. a kind of method of catalytic coal gasifaction as claimed in claim 1, it is characterised in that the spraying is comprised the following steps：
（1）Alkali metal aluminate and/or silicate are weighed according to load capacity, 0.5-10 times of deionized water is added on the basis of coal And it is heated to 40-90 DEG C；
（2）Alkali metal aluminate and/or silicate are loaded on coal in the form of spraying, and 2-12 h are dried at 80-110 DEG C, are obtained To the coal of supported catalyst.
8. a kind of method of catalytic coal gasifaction as claimed in claim 1, it is characterised in that the mechanical mixing includes following Step：
By alkali-metal aluminate and/or silicate catalyst and coal mixing, 3-10 is ground on oscillating mill after mixing After min, the coal that mechanical mixing prepares supported catalyst is obtained.
9. a kind of method of catalytic coal gasifaction as claimed in claim 1, it is characterised in that described impregnation method includes as follows Step：
（1）Alkali-metal aluminate and/or silicate are added in water and are sufficiently stirred for, obtained containing aluminate and/or silicon The solution of hydrochlorate, water addition be aluminate, 20-100 times of silicate quality；
（2）It is the 1-4.5 wt% of ature of coal amount by alkali metal quality when using low order brown coal, when using high-order coal, presses Alkali metal quality is the 1-6.5 wt% of ature of coal amount, during coal to be poured into the solution of preparation, is kept stirring at 40-90 DEG C, directly To formation pulpous state thick liquid；
（3）The slurry shape material for obtaining is dried 2-12 h at 80-150 DEG C, obtains the coal of supported catalyst.
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CN109110771A (en) * 2018-09-12 2019-01-01 中国科学院山西煤炭化学研究所 A method of waterglass is prepared using catalytic gasification lime-ash
CN109107595A (en) * 2018-09-12 2019-01-01 中国科学院山西煤炭化学研究所 A kind of method of carbon dioxide-water-alcohol system recycling base metal catalysts

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CN102476008A (en) * 2010-11-30 2012-05-30 新奥科技发展有限公司 Method for recovering and recycling alkali metal catalyst
CN104449865A (en) * 2014-10-16 2015-03-25 中国科学院山西煤炭化学研究所 Method for improving catalytic coal gasification activity and catalyst recovery rate

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CN102476008A (en) * 2010-11-30 2012-05-30 新奥科技发展有限公司 Method for recovering and recycling alkali metal catalyst
CN104449865A (en) * 2014-10-16 2015-03-25 中国科学院山西煤炭化学研究所 Method for improving catalytic coal gasification activity and catalyst recovery rate

Cited By (2)

* Cited by examiner, † Cited by third party
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CN109110771A (en) * 2018-09-12 2019-01-01 中国科学院山西煤炭化学研究所 A method of waterglass is prepared using catalytic gasification lime-ash
CN109107595A (en) * 2018-09-12 2019-01-01 中国科学院山西煤炭化学研究所 A kind of method of carbon dioxide-water-alcohol system recycling base metal catalysts

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