CN114405240B - Method for preparing denitration material by using gas slag - Google Patents

Method for preparing denitration material by using gas slag Download PDF

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Publication number
CN114405240B
CN114405240B CN202111683838.1A CN202111683838A CN114405240B CN 114405240 B CN114405240 B CN 114405240B CN 202111683838 A CN202111683838 A CN 202111683838A CN 114405240 B CN114405240 B CN 114405240B
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denitration
gas slag
gas
coal gas
slag
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CN114405240A (en
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王亚丽
晁思聪
柳小楼
邓浩然
韩晓宁
崔素萍
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Beijing University of Technology
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Beijing University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/304—Alkali metal compounds of sodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/306—Alkali metal compounds of potassium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/602—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • 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
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding

Abstract

A method for preparing a denitration material by using coal gas slag belongs to the technical field of chemical waste treatment. The coal gas slag particles are placed in a grinding device and ground to the fineness of 200 meshes to obtain coal gas slag powder; mixing the gas slag powder with potassium hydroxide solution with the concentration of 3-4 mol/L according to the proportion of 3: mixing the materials according to the mass ratio of 5-6, standing and soaking for 3 hours after the materials are fully mixed, and drying the mixed liquid after stirring. When the oxygen content of the denitration material prepared by the coal gas slag is 1%, the denitration rate can be maintained to be more than 75% in a high temperature area, and the denitration rate can be up to more than 90%.

Description

Method for preparing denitration material by using gas slag
Technical Field
The invention belongs to the technical field of chemical waste treatment and the field of environmental protection, and particularly relates to treatment and reutilization of gas slag, which is used for flue gas treatment of a cement kiln.
Background
The energy structure in China uses coal as main energy at present, and after the coal gasification technology is applied, a large amount of gas slag can be generated although combustible gas can be prepared. The recycling treatment and utilization of the gas slag are the important problems which are always puzzled in the chemical industry, and the landfill or stacking is used as the main treatment mode at present, so that the land is occupied, a series of ecological environment problems such as soil pollution, water source pollution and the like can be caused, and the resource waste is caused. The proper gas slag treatment method is researched, the resource recycling of the waste slag is realized, the waste is changed into valuable, the gas slag treatment method is fully and effectively applied to the industry, and the gas slag treatment method has important significance for environmental protection and sustainable development of the coal industry.
Many scholars research the influence of oxides on NOx emission, and waste residues or metal oxides are used as additives to be mixed with coal dust, so that the generation of NOx is reduced from the source. The coal gas slag is generated by incomplete combustion of coal and oxygen or oxygen-enriched air to generate CO and H 2 In the process of (1), inorganic mineral substances in the coal undergo different physical-chemical transformation and are accompanied with residual carbon particles in the coalSolid residue formed. The chemical composition mainly comprises SiO 2 、Al 2 O 3 、CaO、Fe 2 O 3 Etc. At present, the removal of nitrogen oxides by utilizing gas slag is studied, but the effect is poor. By modifying the surface of the glass body in different ways, the surface-densified glass body can be destroyed, so that an internal channel is opened, and the denitration activity is excited.
The alkali modification is to react alkaline corrosive substances with inorganic silicon aluminum materials at a certain temperature to form a pore channel structure on the surface in situ so as to improve the adsorptivity of the materials.
The invention aims to develop an inorganic denitration material for a cement preheater by taking coal gas slag as a raw material and grinding, alkali dissolution, constant-temperature impregnation and the like as modification means. The raw materials comprise: gas slag, potassium hydroxide powder and deionized water; the device comprises: grinder, centrifuge, dryer, etc. The invention has the following advantages: the granularity of the coal gasification slag is reduced by grinding, the specific surface area of the coal gasification slag is increased, and the full contact between the coal gasification slag and nitrogen oxides is facilitated; further alkali dissolution is carried out to react substances such as Al, si and the like contained on the surface to form a new structure, so that the catalytic activity is increased, a large number of pore channels are exposed, the specific surface area is increased, and the full contact of the gas slag and nitrogen oxides is facilitated; in addition, active group sites can be exposed, and the load of alkali metal ions is increased, so that the purposes of improving the carrier and the activation property of the gas slag are achieved in many aspects. The method can fully utilize the gas slag, and truly realize waste recycling.
Disclosure of Invention
A method for preparing a denitration material for a cement preheater by taking gas slag as a raw material, which is characterized by comprising the following steps:
1. grinding the gas slag particles, putting the gas slag particles into a grinding device, grinding for 3-6 times to obtain the fineness of 200-mesh sieve, and obtaining gas slag powder
2. The gas slag powder is prepared by the following steps of 3: 5-3: 6 (mass ratio) is added into potassium hydroxide solution with the concentration of 3-4 mol/L, after the mixture is fully mixed, the mixture is stood for soaking for 3 hours, and the stirred mixture is dried.
3. The prepared denitration material is placed in a denitration testing device to test denitration efficiency, the catalyst dosage is 0.5g, the smoke composition is omega (NO) =1000 ppm, omega (O) 2 )＝1％，N 2 In order to balance the gas, the gas flow rate is 450mL/min, the temperature is raised to 800 ℃ and 900 ℃ at the room temperature of 25 ℃, the components and the content of the outlet flue gas at different temperature points are tested, and the change of the denitration rate along with the temperature is calculated, so that the denitration performance of the denitration material is characterized. When the oxygen content of the denitration material prepared by the coal gas slag is 1%, the denitration rate can be maintained to be more than 75% in a high temperature area, and the denitration rate can be up to more than 90%.
Detailed Description
KOH modified gasifiable slag composition (%)
SiO 2 Al 2 O 3 CaO Fe 2 O 3 K 2 O Na 2 O MgO
KOH 50.41 14.3084 9.9644 9.4243 9.8428 1.7472 1.919
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
And (3) placing the gas slag particles into a grinding device, and grinding to the fineness of 200 meshes to obtain gas slag powder. The gas slag powder is prepared by the following steps of 3:5.8 (the ratio of slag to alkali solution) is added into potassium hydroxide solution with the concentration of 3mol/L, after the mixture is fully mixed, the mixture is stood for soaking for 3 hours, and the mixed solution after stirring is dried, so that the denitration material is prepared. The prepared denitration material is placed in a denitration test device to test the denitration efficiency, the catalyst dosage is 0.5g, the smoke component is 1000ppm NO, omega (O) 2 )＝1％，N 2 In order to balance the gas, the denitration efficiency basically increases gradually along with the temperature rise when the gas flow rate is 450mL/min, and the denitration rate can reach 77.8% when the temperature reaches 800 ℃.
Example 2
And (3) placing the gas slag particles into a grinding device, and grinding to the fineness of 200 meshes to obtain gas slag powder. The gas slag powder is prepared by the following steps of 3:6.1 (the ratio of slag to alkali solution) is added into potassium hydroxide solution with the concentration of 4mol/L, after the mixture is fully mixed, the mixture is stood for soaking for 3 hours, and the mixed solution after stirring is dried, so that the denitration material is prepared. The prepared denitration material is placed in a denitration test device to test the denitration efficiency, the catalyst dosage is 0.5g, the smoke component is 1000ppm NO, omega (O) 2 )＝1％，N 2 In order to balance the gas, the denitration efficiency basically increases gradually along with the temperature rise when the gas flow rate is 450mL/min, and the denitration rate can reach 75.0% when the temperature reaches 800 ℃.
Example 3
Grinding the gas slag particlesGrinding to fineness of 200 mesh sieve to obtain gas slag powder. The gas slag powder is prepared by the following steps of 3:5.8 (the ratio of slag to alkali solution) is added into potassium hydroxide solution with the concentration of 3mol/L, after the mixture is fully mixed, the mixture is stood for soaking for 3 hours, and the mixed solution after stirring is dried, so that the denitration material is prepared. The prepared denitration material is placed in a denitration test device to test the denitration efficiency, the catalyst dosage is 0.5g, the smoke component is 1000ppm NO, omega (O) 2 )＝1％，N 2 In order to balance the gas, the denitration efficiency basically increases gradually along with the temperature rise when the gas flow rate is 450mL/min, and the denitration rate can reach 74.0% when the temperature reaches 900 ℃.
Example 4
And (3) placing the gas slag particles into a grinding device, and grinding to the fineness of 200 meshes to obtain gas slag powder. The gas slag powder is prepared by the following steps of 3:6.1 (the ratio of slag to alkali solution) is added into potassium hydroxide solution with the concentration of 4mol/L, after the mixture is fully mixed, the mixture is stood for soaking for 3 hours, and the mixed solution after stirring is dried, so that the denitration material is prepared. The prepared denitration material is placed in a denitration test device to test the denitration efficiency, the catalyst dosage is 0.5g, the smoke component is 1000ppm NO, omega (O) 2 )＝1％，N 2 In order to balance the gas, the denitration efficiency basically increases gradually with the temperature rise when the gas flow rate is 450mL/min, and the denitration rate is 96.0% when the temperature reaches 900 ℃.

Claims (1)

1. The application of preparing the denitration material for the cement preheater based on taking the gas slag as the raw material is characterized in that the preparation method of preparing the denitration material for the cement preheater by taking the gas slag as the raw material comprises the following steps:
1) Grinding treatment of the coal gas slag particles: placing the coal gas slag particles into a grinding device, and grinding to the fineness of 200 meshes to obtain coal gas slag powder;
2) Mixing the gas slag powder with 3-4 mol/L potassium hydroxide solution according to the ratio of 3: mixing the materials according to the mass ratio of 5-6, standing and soaking for 3 hours after the materials are fully mixed, and drying the mixed liquid after stirring;
the application is specifically as follows: is placed on the take-off deviceThe denitration efficiency is tested in the denitration test device, the catalyst dosage is 0.5g, the smoke composition is omega (NO) =1000 ppm, omega (O) 2 )=1%，N 2 In order to balance the gas, the gas flow rate is 450mL/min, the temperature is raised to 800-900 ℃ at the room temperature of 25 ℃, and the components and the content of the outlet smoke at different temperature points are tested.
CN202111683838.1A 2021-12-22 2021-12-22 Method for preparing denitration material by using gas slag Active CN114405240B (en)

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Family Cites Families (5)

* Cited by examiner, † Cited by third party
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CN103936134B (en) * 2014-05-06 2015-12-09 南京大学 A kind of method utilizing synthetic ammonia gasification Slag treatment phenolic wastewater
JP6400379B2 (en) * 2014-08-08 2018-10-03 三菱日立パワーシステムズ株式会社 Denitration method for combustion exhaust gas
CN109529896A (en) * 2018-12-29 2019-03-29 西安科技大学 A kind of coal-burning power plant's denitration demercuration catalyst and preparation method thereof
CN112452144B (en) * 2020-11-05 2023-06-09 北京工业大学 Method for preparing denitration material for cement preheater from gasified slag
CN113499778B (en) * 2021-06-30 2023-06-30 北京工业大学 High-temperature flue gas denitration catalyst for coal gas slag cement kiln and preparation method of high-temperature flue gas denitration catalyst

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