CN108728174B - Catalyst recovery method for coal catalytic gasification reaction - Google Patents

Catalyst recovery method for coal catalytic gasification reaction Download PDF

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Publication number
CN108728174B
CN108728174B CN201710266391.5A CN201710266391A CN108728174B CN 108728174 B CN108728174 B CN 108728174B CN 201710266391 A CN201710266391 A CN 201710266391A CN 108728174 B CN108728174 B CN 108728174B
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alkali
catalytic gasification
solution
catalyst
grinding
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CN108728174A (en
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朱艳芳
王金利
魏士新
吴�琳
蔡进
张�杰
黄先亮
吴学其
徐本刚
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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China Petroleum and Chemical Corp
Research Institute of Nanjing Chemical Industry Group Co Ltd
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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
    • C10J3/72—Other features
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • 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
    • 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)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)
  • Catalysts (AREA)

Abstract

A catalyst recovery method for coal catalytic gasification reaction. The method comprises three steps of pretreatment of catalytic gasification residues, alkali dissolution and alkali washing absorption. (1) After quenching the catalytic gasification residues, collecting and grinding the catalytic gasification residues under the condition of air isolation; (2) adding an alkali solution into the material prepared in the step (1) for alkali dissolution; (3) and (3) adding an alkali solution into the material prepared in the step (2) to perform alkali washing absorption digestion reaction. Washing and centrifuging the product of (3) for multiple times, and extracting a separation solution. The patent develops a technology for recovering the catalyst by ventilating and alkali washing, and test results show that when the water-slag ratio is 2, the total potassium recovery rate reaches 98.8 percent. The method for recovering the catalyst has the advantages of simple process, environmental protection, low energy consumption and high recovery rate.

Description

Catalyst recovery method for coal catalytic gasification reaction
Technical Field
The invention relates to a method for recovering a catalyst for catalytic coal gasification reaction, and belongs to the technical field of catalytic coal conversion.
Background
Coal accounts for 79% of world energy reserves and is the most abundant fossil energy. Among the coal utilization technologies, the coal gasification technology is the basis and key for clean and efficient utilization and conversion of coal. The coal catalytic gasification technology is a representative technology of a novel coal gasification technology, coal and a catalyst are uniformly mixed according to a certain proportion, and the catalyst dispersed on the surface of the coal better contacts with a gasification agent through erosion slotting action, so that the gas-solid reaction rate is accelerated.
The U.S. Exxon company established a catalytic gasification unit of 1t/d scale in the 70 s of the 20 th century and conducted a great deal of process research. In recent years, GPE company in the United states successfully copies 1t/d test on the basis of Exxon technology, perfects partial technology and develops 'blue gas' (blue gas) for producing SNG by catalytic gasificationTM) Technology ", a commercial demonstration project (" May-Flowery "project) was built in Boston, USA. The technology has the advantages of low water consumption ratio, high heat efficiency and good environmental protection benefit. The technology is popularized and contacted with the domestic Tang group and the universal group. GPE in patent US2009/0165382a1 proposes a set of catalyst recovery schemes: after quenching and water washing, the catalyst semi-coke is in contact reaction with alkali metal hydroxide, and the product is further reacted with CO2Contact reaction to remove residual CO2And after the generated gas is separated from the generated gas, carrying out slag-liquid separation to obtain a catalyst solution. Washing the slag with water to obtain a dilute solution containing a small amount of catalyst; alkali metal hydroxide contact reaction and CO2The purpose of the contact reaction is to convert the insoluble salt into the soluble salt and dissolve and recover the soluble salt.
Much research has been carried out in the aspects of coal catalytic gasification and catalyst recovery in China. The Xinao energy company develops a pilot test research of a coal catalytic gasification technology of 300t/d, adopts a scheme of multi-section fluidized bed (pyrolysis section, catalytic gasification section and combustion gasification section) for fractional gasification and ash fusion slag removal, and is suitable for different coal types. By washing with water (soluble K)+Easy to dissolve in water) + hydrothermal digestion (converting insoluble potassium salt to soluble K+With the aid of basic substances Ca (OH)2Can make the KAlSiO difficult to be compatible4Formation of more insoluble Ca3Al2SiO4(OH)8Simultaneously, KOH is released; ) And recovering the catalyst, wherein the recovery rate of the catalyst is 92-93%. The complete process technology of a large-scale coal catalytic gasification device is developed by combining a tripod project at present. In addition, some colleges and research institutions such as east China university, Zhejiang university, Shanxi coal chemical institute have literature and patent reports, but most of them stay in the laboratory.
Common coal gasification catalysts are alkali metals, alkaline earth metals, transition metals and the like, wherein hydroxides and carbonates of alkali metals are accepted as the monomer catalysts with the highest efficiency. Compared with direct coal gasification, the catalytic coal gasification technology has obvious advantages, but the catalytic coal gasification has not been industrialized so far, mainly because a large amount of alkaline substances are remained in the slag after catalytic gasification, and the direct discharge of alkaline ash slag causes serious pollution to the environment, and more importantly, the high catalyst cost causes the catalytic gasification technology to lose economic benefits.
In conclusion, the alkali metal catalyst has large load, easy inactivation, high catalyst cost, immature recovery process, pollution of alkali-containing ash, no economic benefit of the alkali metal coal catalytic gasification technology and other factors, and restricts the large-scale popularization of coal catalytic gasification.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides a catalyst recovery method for catalytic coal gasification reaction, and can provide a catalyst recovery method with simple process, environmental protection, low energy consumption and high recovery rate
The technical scheme is as follows: the invention provides a catalyst recovery method for coal catalytic gasification reaction, which comprises the steps of pretreatment of catalytic gasification residues, alkali dissolution and alkali washing absorption, and is characterized by comprising the following steps:
step 1): after quenching the catalytic gasification residues, collecting and grinding the catalytic gasification residues under the condition of air isolation;
step 2): adding an alkali solution into the material prepared in the step 1) for alkali dissolution;
step 3): adding an alkali solution into the material prepared in the step 2) for alkali washing absorption to generate a digestion reaction.
Step 4): washing and centrifuging the product obtained in the step 3) for multiple times, and extracting the separated liquid.
Typically, the collecting and grinding atmosphere is N2The particle size of the residue after grinding is 0.250 to 0.425 mm.
The alkali liquor in the step 2) is KHCO3The pH is controlled at7~9。
The atmosphere for dissolving the alkali in the step 2) is CO2The temperature is 80-150 ℃, the pressure is 1.2-2.5 MPa, the stirring speed is 200-800 r/min, and the time is 20-60 min.
The alkali liquor in the step 3) is organic calcium salt or inorganic calcium salt, preferably one or more than two of calcium hydroxide, calcium oxide, calcium gluconate, calcium acetate and calcium oleate.
The alkali dissolving atmosphere in the step 3) is N2Or air, the temperature is 150-220 ℃, the pressure is 1.5-2.5 MPa, the stirring speed is 200-800 r/min, and the time is 1-4 h.
The invention has the following effects:
1. green and environment-friendly, and simple process. The catalyst is collected and ground under the condition of air isolation, potassium sulfide in residues is reduced from being oxidized into various inert substances without catalytic activity, such as sulfide, thiosulfate, sulfate and the like after being exposed to air, the collection of sulfur is reduced, and meanwhile, water consumption is reduced in the process of absorbing alkali solution and alkali washing.
2. The recovery rate is improved, the pH value is controlled during alkaline dissolution, the concentration of silicon in the residue is reduced, the generation of silicide without catalytic activity is inhibited, and CO is introduced2Removing the potassium aluminosilicate without catalytic activity so that the potassium exists in the form of soluble potassium salt; alkali washing absorption takes alkali as a dissolving agent, and KAlSiO which is a slightly soluble salt4The bond between Al-O and Si-O is broken, and the difficult-to-dissolve potassium salt is converted into soluble potassium salt, so that the recovery rate of the active component is improved. Test results show that when the mass ratio of the grain slag is 2, the total potassium recovery rate reaches 98.8 percent.
3. The alkali dissolving process supplements the unrecoverable active ingredients, and prepares for the subsequent cyclic utilization of the catalyst, and the process is simple.
Detailed Description
The process of the present invention is described in detail below with reference to examples, but the examples are only illustrative and are not intended to limit the scope of the present invention.
Example 1
In N2Weighing 1g of catalyst residue under the atmosphere, grinding to 60-100 meshes, and adding KHCO3Catalyst residues treated by solution additionIn the slag, PH is 9, introducing CO into the reaction kettle2The temperature is 150 ℃, the pressure is 1.2MPa, the stirring speed is 300r/min, and the time is 20 min. Then adding the calcium hydroxide solution into a reaction kettle, wherein the mass ratio of the alkaline residue is 8:1, and the atmosphere is N2The temperature is 220 ℃, the pressure is 2.5MPa, the stirring speed is 300r/min, and the time is 4 h. The product was then washed with water 3 times and centrifuged, and the separated liquid was extracted. The mass ratio of the grain slag is 14:1, and the total potassium recovery rate is 96.8 percent
Example 2
In N2Weighing 1g of catalyst residue under the atmosphere, grinding to 60-100 meshes, and adding KHCO3Adding the solution into the treated catalyst residue, adjusting the pH to 8, introducing CO into a reaction kettle2The temperature is 150 ℃, the pressure is 1.2MPa, the stirring speed is 300r/min, and the time is 30 min. Then adding the calcium hydroxide solution into a reaction kettle, wherein the mass ratio of the alkaline residue is 4:1, and the atmosphere is N2The temperature is 220 ℃, the pressure is 2MPa, the stirring speed is 400 r/min, and the time is 2 h. The product was then washed with water 3 times and centrifuged, and the separated liquid was extracted. The mass ratio of the grain slag is 6:1, and the total potassium recovery rate is 97.2 percent
Example 3
In N2Weighing 1g of catalyst residue under the atmosphere, grinding to 60-100 meshes, and adding KHCO3Adding the solution into the treated catalyst residue, adjusting the pH to 8, introducing CO into a reaction kettle2The temperature is 150 ℃, the pressure is 1.2MPa, the stirring speed is 300r/min, and the time is 30 min. Then adding the calcium oleate solution into a reaction kettle, wherein the mass ratio of the alkaline residue is 2:1, the atmosphere is air, the temperature is 160 ℃, the pressure is 2MPa, the stirring speed is 400 r/min, and the time is 2 h. The product was then washed with water 3 times and centrifuged, and the separated liquid was extracted. The mass ratio of the grain slag is 2:1, and the total potassium recovery rate is 98.8 percent
Example 4
In N2Weighing 1g of catalyst residue under the atmosphere, grinding to 60-100 meshes, and adding KHCO3Adding the solution into the treated catalyst residue, adjusting the pH to 8, introducing CO into a reaction kettle2The temperature is 150 ℃, the pressure is 1.2MPa, the stirring speed is 300r/min, and the time is 30 min. Then adding calcium oleate solution into a reaction kettle, wherein the mass ratio of the alkaline residue is 2:1, and the atmosphere is N2Temperature of 160 ℃, pressure of 2MPa and stirring speed of 400r/min, time 2 h. The product was then washed with water 3 times and centrifuged, and the separated liquid was extracted. The mass ratio of the grain slag is 4:1, and the total potassium recovery rate is 97.4 percent
Example 5
In N2Weighing 1g of catalyst residue under the atmosphere, grinding to 60-100 meshes, and adding KHCO3Adding the solution into the treated catalyst residue, adjusting the pH to 8, introducing CO into a reaction kettle2The temperature is 150 ℃, the pressure is 1.2MPa, the stirring speed is 400 r/min, and the time is 20 min. Then adding the calcium acetate solution into a reaction kettle, wherein the ratio of caustic sludge to caustic sludge is 2:1, the atmosphere is air, the temperature is 160 ℃, the pressure is 2.5MPa, the stirring speed is 800 r/min, and the time is 2 hours. The product was then washed with water 3 times and centrifuged, and the separated liquid was extracted. The mass ratio of the grain slag is 5:1, and the total potassium recovery rate is 96.8 percent
Example 6
In N2Weighing 1g of catalyst residue under the atmosphere, grinding to 60-100 meshes, and adding KHCO3Adding the solution into the treated catalyst residue, adjusting the pH to 9, introducing CO into the reaction kettle2The temperature is 150 ℃, the pressure is 1.2MPa, the stirring speed is 300r/min, and the time is 30 min. Then adding the calcium gluconate solution into the reaction kettle, wherein the ratio of alkali to residue is 8:1, the atmosphere is air, the temperature is 160 ℃, the pressure is 2.5MPa, the stirring speed is 400 r/min, and the time is 2 hours. The product was then washed with water 3 times and centrifuged, and the separated liquid was extracted. The mass ratio of the grain slag is 1:1, and the total potassium recovery rate is 96.3 percent
The results of the above examples show that under the process conditions of the present invention, the recovery rate of total potassium reaches more than 96%, wherein under the process conditions of example 3, the mass ratio of water to slag is 2:1, and the recovery rate of total potassium is 98.8%.

Claims (1)

1. A catalyst recovery method for coal catalytic gasification reaction comprises pretreatment of catalytic gasification residues, alkali dissolution and alkali washing absorption, and is characterized by comprising the following steps:
step 1): after quenching the catalytic gasification residues, collecting and grinding the catalytic gasification residues under the condition of air isolation to obtain residues;
step 2): adding the residue obtained in the step 1) into an alkali solution for alkali dissolution;
step 3): adding an alkali solution into the material prepared in the step 2) for alkali washing absorption to generate a digestion reaction;
step 4): washing and centrifugally separating the product obtained in the step 3), and extracting a separation solution;
said collecting and grinding in step 1) is at N2The grinding is carried out under an atmosphere, and the particle size of the residue after grinding is 0.250-0.425 mm.
The alkali solution in the step 2) is KHCO3The pH of the aqueous solution is controlled to be 7-9, and the alkaline solution is CO2The reaction is carried out under the atmosphere, the temperature is 80-150 ℃, the pressure is 1.2-2.5 MPa, the stirring speed is 200-800 r/min, and the time is 20-60 min.
The alkali solution in the step 3) is one or more of calcium hydroxide, calcium oxide, calcium gluconate, calcium acetate and calcium oleate; the alkaline wash absorption is in N2Or the reaction is carried out in an air atmosphere at the temperature of 150-220 ℃, the pressure of 1.5-2.5 MPa, the stirring speed of 200-800 r/min and the time of 1-4 h.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101484554A (en) * 2006-06-01 2009-07-15 格雷特波因特能源公司 Catalytic steam gasification process with recovery and recycle of alkali metal compounds
CN101910370A (en) * 2007-12-28 2010-12-08 格雷特波因特能源公司 Catalytic gasification process with recovery of alkali metal from char
CN104815673A (en) * 2015-03-11 2015-08-05 新奥科技发展有限公司 Recovery method for potassium catalyst in coal catalytic gasification ash

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101484554A (en) * 2006-06-01 2009-07-15 格雷特波因特能源公司 Catalytic steam gasification process with recovery and recycle of alkali metal compounds
CN101910370A (en) * 2007-12-28 2010-12-08 格雷特波因特能源公司 Catalytic gasification process with recovery of alkali metal from char
CN104815673A (en) * 2015-03-11 2015-08-05 新奥科技发展有限公司 Recovery method for potassium catalyst in coal catalytic gasification ash

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
中温煤-水蒸气气化过程催化剂的回收利用研究;陈杰;《中国优秀硕士学位论文库》;20120105;正文第29-42页 *

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Address after: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699

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Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd.

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