CN106635176B - Catalytic coal gasification method - Google Patents

Catalytic coal gasification method Download PDF

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CN106635176B
CN106635176B CN201611196781.1A CN201611196781A CN106635176B CN 106635176 B CN106635176 B CN 106635176B CN 201611196781 A CN201611196781 A CN 201611196781A CN 106635176 B CN106635176 B CN 106635176B
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coal
catalyst
gasification
mass
alkali metal
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CN106635176A (en
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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

A catalytic coal gasification method comprises the steps of mixing an alkali metal aluminate and/or silicate catalyst with coal to obtain catalyst-loaded coal, adding the catalyst-loaded coal into a gasification furnace for gasification, putting gasification slag into water, stirring and reacting at the temperature of 20-90 ℃ for 1-2h, filtering, and washing a filter cake to obtain a solution containing aluminate and/or silicate. The invention has the advantages of easy recovery of the catalyst and little corrosion.

Description

Catalytic coal gasification method
Technical Field
The invention belongs to the field of coal gasification, and particularly relates to a catalytic coal gasification method.
Background
Coal gasification is a common technology, a core technology and a leading technology in coal chemical industry. In order to achieve high carbon conversion rate and large treatment capacity, the traditional gasification furnace is usually operated at high temperature and high pressure, and the harsh operating conditions cause high manufacturing and operating costs and unstable operation of the gasification furnace. The catalytic gasification as a novel coal gasification mode can realize the gasification process under a mild condition. Meanwhile, the catalytic gasification can modulate the composition of coal gas, and has better industrial application prospect.
At present, the most commonly used catalyst for catalytic gasification is Na2CO3And K2CO3And the like. The addition of alkali metal can significantly increase the gasification reaction rate and reduce the reaction temperature. But Na2CO3And K2CO3When the melting point of the alkali metal catalyst is lower, part of the alkali metal catalyst is volatilized to a gas phase in the gasification process to produceThe loss of the catalyst and the serious corrosion to gasification equipment are generated. In addition, during the catalytic gasification reaction, alkali metal reacts with silicon-aluminum mineral in coal to generate nepheline and aluminosilicate which have no catalytic effect, and the generated nepheline and aluminosilicate are difficult to realize alkali metal recovery through a water-soluble process, so that the catalyst is deactivated and difficult to recover the catalyst. Therefore, the problems of recovery of the alkali metal catalyst and volatilization and corrosion of the alkali metal are major obstacles restricting the industrialization of the catalytic gasification of coal.
Disclosure of Invention
The invention aims to provide a coal catalytic gasification method with easily-recovered catalyst and small corrosion.
The technical scheme for solving the problems is as follows:
the invention uses alkali metal aluminate and/or silicate as catalyst, which has the characters of hard deactivation, high melting point and low volatility. Mixing aluminate and/or silicate with coal in a certain proportion to obtain the coal loaded with the catalyst. With Na2CO3、K2CO3The aluminate and silicate catalysts have a higher melting point, lower volatility and are more stable than the alkali metal catalysts, and therefore are less likely to volatilize and deactivate. After the coal gasification of the catalyst-supporting coal, the ash is washed with water and filtered to obtain a catalyst-containing solution, thereby recovering the catalyst.
The invention relates to a method for catalytic gasification of coal, which comprises the following steps:
(1) when low-rank coal is used, the mass of the alkali metal element is 1-4.5 wt% of the mass of the coal, when high-rank coal is used, the mass of the alkali metal element is 1-6.5 wt% of the mass of the coal, and the aluminate and/or silicate catalyst of the alkali metal and the coal are mixed to obtain the coal loaded with the catalyst;
(2) the coal loaded with the catalyst is added into a gasification furnace for gasification, the operation temperature of the gasification is 600-1200 ℃, the pressure is 0-8MP, and the gasification agent is air, oxygen, water vapor and CO2One or more of (a);
(3) putting the gasified slag into water, stirring and reacting for 1-2h at the temperature of 20-90 ℃, filtering and washing a filter cake to obtain a solution containing aluminate and silicate, wherein the addition amount of the water is 1-100 times of the mass of the gasified slag.
The alkali metal aluminate is sodium aluminate, sodium metaaluminate and potassium aluminate, and the silicate is sodium silicate and potassium silicate.
The low-rank coal is peat, lignite, long flame coal and gas coal.
The high-rank coal is lean coal, lean coal and anthracite.
The gasification furnace is a fixed bed gasification furnace, a fluidized bed gasification furnace or an entrained flow gasification furnace.
The total amount of the gasification agent is 1.3-8 times of the mass of the coal.
The spraying method comprises the following steps:
(1) weighing alkali metal aluminate and/or silicate according to the loading amount, adding 0.5-10 times of deionized water based on coal, and heating to 40-90 ℃;
(2) and (3) loading the alkali metal aluminate and/or silicate on coal in a spray form, and drying at 80-110 ℃ for 2-12h to obtain the coal loaded with the catalyst.
The mechanical mixing method comprises the following steps:
mixing the aluminate and/or silicate catalyst of alkali metal with coal, grinding for 3-10min on a vibration grinder after mixing to obtain the coal loaded with the catalyst by a mechanical mixing method.
The impregnation method comprises the following steps:
(1) adding aluminate and/or silicate of alkali metal into the removed water, and fully stirring to obtain a solution containing aluminate and/or silicate, wherein the adding amount of water is 20-100 times of the mass of aluminate and silicate;
(2) when low-rank brown coal is used, the coal is poured into the prepared solution in an amount of 1 to 4.5 wt% based on the mass of the alkali metal element of 1 to 6.5 wt% based on the mass of the coal when high-rank coal is used, and the stirring is maintained at 40 to 90 ℃ until a slurry-like viscous liquid is formed.
(3) Drying the obtained slurry-state substance at 80-150 ℃ for 2-12h to obtain the coal loaded with the catalyst.
The invention has the following advantages and technical effects:
1. the alkali metal aluminate and silicate have higher melting points, the volatilization amount of alkali metal is very small in the gasification process, the loss of the catalyst is less, and the corrosion to gasification furnace equipment is less;
2. the melting temperature of gasified ash is high (1200 ℃), and the phenomenon of melting and slagging in the gasification process is avoided;
3. with the conventional alkali metal Na2CO3、K2CO3Compared with the prior art, the catalyst has high recovery rate (85-98%) and low alkali metal corrosion.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1: in the embodiment, the low-rank coal northern Xinjiang peat is used as a sample, sodium aluminate is used as a catalyst, a fixed bed gasification furnace is adopted, and the sodium aluminate is loaded on the peat by a solution impregnation method, wherein the catalyst loading step is as follows:
1) the mass ratio of water to sodium aluminate is 20, and the mixture is stirred at 60 ℃ until the mixture is completely dissolved;
2) adding peat into the solution, stirring and keeping the temperature until slurry substances are formed, wherein the mass of the alkali metal element Na is 1 wt% of that of the coal;
3) the obtained coal slurry-like substance is dried for 12h at 110 ℃ to obtain peat loaded with catalyst.
Adding northern peat loaded with sodium aluminate into a fixed bed gasification furnace, wherein the mass of an alkali metal element Na is 1 wt% of the mass of coal, the gasification temperature is 600 ℃, the pressure is 0.1MP, and air and CO are adopted2Gasification with air/coal mass ratio of 1.8, CO2The mass ratio of coal/coal was 3. And (3) putting the gasification residues into water according to the liquid-solid ratio of 20, stirring and leaching for 1h at the temperature of 50 ℃, filtering, and washing a filter cake to obtain a solution containing sodium aluminate and sodium silicate. The carbon conversion and catalyst recovery after the reaction are shown in table one.
Example 2: in the embodiment, low-order little quan lignite is used as a sample, sodium aluminate is used as a catalyst, a fluidized bed gasification furnace is adopted for gasification, the catalyst is loaded on the coal by a mechanical mixing method, and the catalyst loading steps are as follows:
the mass of the alkali metal element Na is 4 wt% of the mass of the coal, and the lignite loaded by the mechanical mixing method is obtained after the coal and the sodium aluminate are ground for 5min on a vibration coal mill.
The method comprises the steps of adding lignite loaded with sodium aluminate into a fluidized bed gasification furnace, wherein the mass of an alkali metal element Na is 4 wt% of the mass of coal, the pressure is 1MP, the gasification temperature is 900 ℃, the gasification agent is air and water vapor, the mass ratio of air to coal is 2.4, and the mass ratio of water vapor to coal is 2. And putting the gasification residues into water according to the liquid-solid ratio of 40, stirring and leaching for 1h at the temperature of 50 ℃, filtering, and washing a filter cake to obtain a solution containing sodium aluminate and sodium silicate. The carbon conversion and catalyst recovery after the reaction are shown in table one.
Example 3: the embodiment uses high-order jin city anthracite as a sample, uses sodium aluminate and sodium silicate as catalysts, adopts entrained flow gasification furnace gasification, loads the sodium aluminate and the sodium silicate on the anthracite through a spraying method, and the catalyst loading steps are as follows:
1) the mass ratio of sodium aluminate to sodium silicate is 1, the mass ratio of water to sodium aluminate is 10, the mass ratio of water to sodium silicate is 10, and the mixture is stirred at 60 ℃ until the mixture is completely dissolved;
2) the mass of the alkali metal element Na is 6.5 wt% of the mass of the coal, the catalyst solution is loaded on the coal in a spray mode, and the coal is dried for 12 hours at the temperature of 110 ℃ to obtain the coal loaded with the catalyst.
The coal loaded with the catalyst is added into an entrained-flow bed gasification furnace, the mass of an alkali metal element Na is 6.5 wt% of the mass of the coal, the mass ratio of sodium aluminate to sodium silicate is 1, the pressure is 3MP, the gasification temperature is 1200 ℃, the gasification agent is oxygen and water vapor, the mass ratio of oxygen to coal is 0.8, and the mass ratio of water vapor to coal is 3. And putting the gasification residues into water according to the liquid-solid ratio of 60, stirring and leaching for 1h at the temperature of 70 ℃, filtering, and washing a filter cake to obtain a solution containing sodium aluminate and sodium silicate. The carbon conversion and catalyst recovery after the reaction are shown in table one.
Example 4: in the embodiment, the low-rank coal, small Longtan lignite is used as a sample, potassium silicate is used as a catalyst, a fixed bed gasification furnace is adopted, and potassium silicate is loaded on the lignite through a solution impregnation method. The catalyst loading steps are as follows:
1) the mass ratio of water to potassium silicate is 40, and the mixture is stirred at 60 ℃ until the mixture is completely dissolved;
2) adding lignite into the solution, stirring and keeping the temperature until a pasty substance is formed, wherein the mass of the alkali metal element K is 2 wt% of that of coal;
3) the obtained coal slurry-like substance was dried at 110 ℃ for 12 hours to obtain catalyst-loaded lignite.
The coal loaded with potassium silicate is added into a fixed bed gasification furnace, the mass of the alkali metal element K is 2 wt% of the mass of the coal, the pressure is 5MP, the gasification temperature is 1100 ℃, the gasification agent is oxygen, and the mass ratio of the oxygen to the coal is 1.5. And putting the gasified residues into water according to the liquid-solid ratio of 80, stirring and leaching for 1h at the temperature of 80 ℃, filtering, and washing a filter cake to obtain a solution containing potassium aluminate and potassium silicate. The carbon conversion and catalyst recovery after the reaction are shown in table one.
Example 5: in this embodiment, the anthracite from jin city is used as a sample, potassium aluminate is used as a catalyst, a fluidized bed gasification furnace is used for gasification, and the catalyst adopts a solution impregnation method to load the potassium aluminate on the anthracite. The catalyst loading steps are as follows:
1) the mass ratio of water to potassium aluminate is 40, and the mixture is stirred at 60 ℃ until the mixture is completely dissolved;
2) adding anthracite into the solution, stirring and keeping the temperature until a pasty substance is formed, wherein the mass of the alkali metal element K is 4 wt% of that of the coal;
3) the obtained coal slurry-like substance is dried for 12 hours at the temperature of 110 ℃ to obtain the catalyst-loaded Jincheng anthracite.
Adding potassium aluminate-loaded coal into a fluidized bed gasification furnace, wherein the mass of an alkali metal element K is 4 wt% of the mass of the coal, the pressure is 2MP, the gasification temperature is 1000 ℃, the gasification agent is air, and the mass ratio of air to coal is 7. And putting the gasified residues into water according to the liquid-solid ratio of 90, stirring and leaching for 1h at the temperature of 90 ℃, filtering, and washing a filter cake to obtain a solution containing potassium aluminate and potassium silicate. The carbon conversion and catalyst recovery after the reaction are shown in table one.
Example 6: in the embodiment, northern peat of low-rank coal is taken as a sample, sodium metaaluminate is taken as a catalyst, an entrained flow gasifier is adopted for gasification, and the sodium metaaluminate is loaded on the northern peat by a solution impregnation method. The catalyst loading steps are as follows:
1) the mass ratio of the water to the sodium metaaluminate is 80, and the mixture is stirred at the temperature of 60 ℃ until the mixture is completely dissolved;
2) adding peat into the solution, stirring and keeping the temperature until slurry substances are formed, wherein the mass of the alkali metal element Na accounts for 2 wt% of that of the coal;
3) the obtained coal slurry-like substance is dried for 12h at 110 ℃ to obtain the peat loaded with the catalyst.
Adding peat loaded with sodium metaaluminate into an entrained-flow bed gasification furnace, wherein the mass of an alkali metal element Na is 2 wt% of the mass of coal, the pressure is 3MP, the gasification temperature is 1100 ℃, and the gasification agent is air and CO2Air/coal mass ratio of 2, CO2The mass ratio of coal/coal was 2. And (3) putting the gasification residues into water according to the liquid-solid ratio of 20, stirring and leaching for 1h at the temperature of 70 ℃, filtering, and washing a filter cake to obtain a solution containing sodium aluminate and sodium silicate. The carbon conversion and catalyst recovery after the reaction are shown in table one.
Example 7: in this embodiment, the anthracite coal from jin city is used as a sample, potassium silicate and sodium silicate are used as catalysts, and the potassium silicate and the sodium silicate are loaded on the anthracite coal by a solution impregnation method through a fixed bed gasification furnace. The catalyst loading steps are as follows:
1) the mass ratio of the sodium silicate to the potassium silicate is 1.3, the total mass ratio of the water to the catalyst is 40, and the mixture is stirred at 60 ℃ until the mixture is completely dissolved;
2) adding anthracite into the solution, stirring and keeping the temperature until a pasty substance is formed, wherein the mass of the alkali metal element Na is 3 wt% of that of the coal, and the mass of the alkali metal element K is 3 wt% of that of the coal;
3) the obtained coal slurry-like substance is dried for 12 hours at the temperature of 110 ℃ to obtain the catalyst-loaded Jincheng anthracite.
Adding coal loaded with alkali metal into a fixed bed gasification furnace, wherein the load of an alkali metal catalyst is 6 wt%, and Na: k is 1 (mass ratio), the pressure is 2MP, the gasification temperature is 900 ℃, the gasification agent is oxygen and water vapor, the mass ratio of oxygen to coal is 0.5, and the mass ratio of water vapor to coal is 3. And putting the gasification residues into water according to the liquid-solid ratio of 20, stirring and leaching the gasification residues for 1h at the temperature of 80 ℃, filtering, and washing a filter cake to obtain a solution containing sodium silicate, potassium silicate, sodium aluminate and potassium aluminate. The carbon conversion and catalyst recovery after the reaction are shown in table one.
Example 8: in this example, northern peat is used as a sample, sodium silicate is used as a catalyst, a fluidized bed gasification furnace is used for gasification, and sodium silicate is loaded on northern peat by a solution impregnation method. The catalyst loading steps are as follows:
1) the mass ratio of water to sodium silicate is 60, and the mixture is stirred at 60 ℃ until the mixture is completely dissolved;
2) adding peat into the solution, stirring and keeping the temperature until slurry substances are formed, wherein the mass of the alkali metal element Na accounts for 3 wt% of that of the coal;
3) the obtained coal slurry-like substance is dried for 12 hours at the temperature of 110 ℃ to obtain the catalyst-loaded northern Xinjiang peat.
Adding northern peat loaded with sodium silicate into a fluidized bed gasification furnace, wherein the mass of an alkali metal element Na is 3 wt% of the mass of coal, the pressure is 2MP, the gasification temperature is 1100 ℃, and the gasification agents are oxygen and CO2Oxygen/coal mass ratio of 0.7, CO2The mass ratio of coal/coal was 3. And (3) putting the gasified residues into water according to the liquid-solid ratio of 20, stirring and leaching for 1h at the temperature of 80 ℃, filtering, and washing a filter cake to obtain a solution containing sodium silicate. The carbon conversion and catalyst recovery after the reaction are shown in table one.
Example 9: in the embodiment, the small quan lignite is taken as a sample, sodium aluminate and potassium aluminate are taken as catalysts, an entrained flow gasifier is adopted for gasification, the sodium aluminate and the potassium aluminate are loaded on the small quan lignite through a solution impregnation method, and the loading steps of the catalysts are as follows:
1) the mass ratio of sodium aluminate to potassium aluminate is 1.4, the total mass ratio of water to sodium aluminate and potassium aluminate is 50, and the mixture is stirred at 60 ℃ until the mixture is completely dissolved;
2) adding lignite into a solution, stirring and keeping the temperature until a pasty substance is formed, wherein the mass of the alkali metal element Na is 1 wt% of that of coal, and the mass of the alkali metal element K is 1 wt% of that of the coal;
3) and drying the obtained coal slurry substance at 110 ℃ for 12h to obtain the catalyst-loaded Xiaolongtan lignite.
Adding catalyst-loaded little Longtan lignite into an entrained flow gasifier, wherein the loading capacity of an alkali metal catalyst is 2 wt%, and the Na: k is 1 (mass ratio), the pressure is 1MP, the gasification temperature is 1000 ℃, the gasification agent is air and water vapor, the mass ratio of air to coal is 3, and the mass ratio of water vapor to coal is 3. And (3) putting the gasified residues into water according to the liquid-solid ratio of 20, stirring and leaching for 1h at the temperature of 80 ℃, filtering, and washing a filter cake to obtain a solution containing sodium aluminate and potassium aluminate. The carbon conversion and catalyst recovery after the reaction are shown in table one.
Comparative example 1: in this example, northern peat is used as a sample, a fixed bed gasifier is used, and air and CO are used as gasifying agents2Air/coal mass ratio of 1.8, CO2The mass ratio of coal/coal is 4, the gasification temperature is 600 ℃, and the pressure is 0.1 MP. After the reaction, the carbon conversion was determined.
Comparative example 2: in the embodiment, the little Longtan lignite is taken as a sample, a fluidized bed gasification furnace is adopted, a gasification agent is air and water vapor, the mass ratio of air to coal is 2.4, the mass ratio of water vapor to coal is 2, the gasification temperature is 900 ℃, and the pressure is 1 MP. After the reaction, the carbon conversion was determined.
Comparative example 3: in the embodiment, the Jincheng anthracite is taken as a sample, an entrained flow gasifier is adopted, a gasifying agent is oxygen and water vapor, the mass ratio of oxygen to coal is 0.8, the mass ratio of water vapor to coal is 5, the gasification temperature is 1200 ℃, and the pressure is 3 MP. After the reaction, the carbon conversion was determined.
Comparative example 4: in this example, the sample is anthracite from Jincheng, and Na is used2CO3As catalyst, a fixed bed gasification furnace is adopted, and Na is mixed mechanically2CO3Loaded on anthracite. The catalyst loading steps are as follows:
the mass of the alkali metal element Na is that of coal6 wt% of coal and Na2CO3Grinding the coal powder on a vibration coal mill for 5min to obtain the anthracite loaded with the catalyst by a mechanical mixing method.
Taking Na2CO3The coal is added into a fixed bed gasification furnace, the mass of the alkali metal element Na is 6 wt% of the mass of the coal, the pressure is 2MP, the gasification temperature is 900 ℃, the gasification agent is oxygen and water vapor, the mass ratio of the oxygen to the coal is 0.5, and the mass ratio of the water vapor to the coal is 3. Adding gasification residue into water at a liquid-solid ratio of 20, stirring and leaching at 80 deg.C for 1 hr, filtering, and washing filter cake to obtain product containing Na2CO3The solution of (1). The carbon conversion and catalyst recovery after the reaction are shown in table one.
TABLE-carbon conversion and catalyst recovery in the examples under different conditions
Figure BDA0001188199150000081

Claims (3)

1. A method of catalytic coal gasification, comprising the steps of:
(1) when low-rank coal is used, the mass of the alkali metal element is 1-4.5 wt% of the mass of the coal, when high-rank coal is used, the mass of the alkali metal element is 1-6.5 wt% of the mass of the coal, an aluminate catalyst of alkali metal is mixed with the coal, and the coal loaded with the catalyst is obtained after mixing, and deliming is not needed;
the aluminate catalyst of alkali metal is sodium aluminate, sodium metaaluminate or potassium aluminate;
(2) adding the coal loaded with the catalyst into a gasification furnace for gasification to obtain gasification residue containing a mixture of the catalyst and coal ash;
(3) and putting gasification residues containing a mixture of the catalyst and the coal ash into water, stirring, filtering, and washing a filter cake to obtain a solution containing aluminate, thereby realizing the recovery of the catalyst.
2. The method of claim 1, wherein the low-rank coal is peat, lignite, long flame coal or gas coal.
3. The process of claim 1, wherein the high rank coal is lean, lean or anthracite.
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