Coke oven flue gas denitration agent catalyst and preparation method thereof
阅读说明：本技术 一种焦炉烟气脱硝剂催化剂及其制备方法 (Coke oven flue gas denitration agent catalyst and preparation method thereof ) 是由 路璐 刘海东 修旭明 祁振营 孟兆杰 于 2021-09-16 设计创作，主要内容包括：本申请公开了一种焦炉烟气脱硝剂催化剂及其制备方法,属于焦炉烟气废气处理技术领域,该脱硝剂催化剂,其由第一组分、第二组分和制孔剂制备而成；按照重量份数计,第一组分由以下原料制备而成：凹凸棒土40-60份、活性炭纤维20-40份、浸渍液50-70份和纳米氧化物30-50份；第二组分为阴离子交换树脂,按照重量份数计,其由以下原料制备而成：聚丙烯酸酯60-80份、改性剂40-60份、酸10-20份、催化剂10-20份和卤代烷20-40份；制孔剂为甲苯。该脱硝剂催化剂中改性后的第一组分能够均匀分散在树脂孔隙中,使烟气中的三氧化硫与氨水反应生成的铵盐不会包裹在脱硝剂催化剂的表面,增强了脱硝效果,吸附后的树脂经过去离子水和乙醇冲洗即可再生使用,其制备方法简单,可工业化推广。(The application discloses a coke oven flue gas denitration agent catalyst and a preparation method thereof, which belong to the technical field of coke oven flue gas waste gas treatment, wherein the denitration agent catalyst is prepared from a first component, a second component and a pore-forming agent; the first component is prepared from the following raw materials in parts by weight: 40-60 parts of attapulgite, 20-40 parts of activated carbon fiber, 50-70 parts of impregnation liquid and 30-50 parts of nano oxide; the second component is anion exchange resin which is prepared from the following raw materials in parts by weight: 60-80 parts of polyacrylate, 40-60 parts of modifier, 10-20 parts of acid, 10-20 parts of catalyst and 20-40 parts of alkyl halide; the pore-forming agent is toluene. The modified first component in the denitration agent catalyst can be uniformly dispersed in pores of the resin, so that ammonium salt generated by reaction of sulfur trioxide in flue gas and ammonia water cannot wrap the surface of the denitration agent catalyst, the denitration effect is enhanced, the adsorbed resin can be regenerated and reused after being washed by deionized water and ethanol, and the preparation method is simple and can be industrially popularized.)
1. The coke oven flue gas denitration agent catalyst is characterized by being prepared from a first component, a second component and a pore-forming agent;
the first component is prepared from the following raw materials in parts by weight: 40-60 parts of attapulgite, 20-40 parts of activated carbon fiber, 50-70 parts of impregnation liquid and 30-50 parts of nano oxide;
the second component is anion exchange resin which is prepared from the following raw materials in parts by weight: 60-80 parts of polyacrylate, 40-60 parts of modifier, 10-20 parts of acid, 10-20 parts of catalyst and 20-40 parts of alkyl halide; the pore-making agent is toluene.
2. The coke oven gas denitration agent catalyst of claim 1, wherein the activated carbon fiber is polyacrylonitrile-based carbon fiber or polyvinyl alcohol-based activated carbon fiber.
3. The coke oven flue gas denitration agent catalyst of claim 1, wherein the impregnation liquid is a potassium phosphate solution and/or a sodium carbonate solution.
4. The coke oven gas denitration agent catalyst of claim 3, wherein the impregnation solution is a potassium phosphate solution and a sodium carbonate solution, and the volume ratio of the potassium phosphate solution to the sodium carbonate solution is (1-2): 1.
5. The coke oven flue gas denitration agent catalyst as claimed in claim 1, wherein the nano oxide is nano calcium oxide and nano alumina, and the mass ratio of the nano calcium oxide to the nano alumina is (1-3): 1.
6. The coke oven gas denitration agent catalyst as claimed in claim 1, wherein the structural general formula of the polyacrylate is as shown in formula 1
Wherein n is 1000-2000.
7. The coke oven gas denitration agent catalyst as claimed in claim 1, wherein the modifier is 3-aminobenzoic acid, and the structural formula of the modifier is as shown in formula 2
8. The coke oven flue gas denitration agent catalyst of claim 1, wherein the acid is concentrated sulfuric acid or p-toluenesulfonic acid, the alkyl halide is any one of ethyl bromide and propyl bromide, and the catalyst is potassium permanganate.
9. The coke oven gas denitration agent catalyst as claimed in claim 8, wherein the structural formula of the anion exchange resin is as shown in formula 3
Wherein R is1 and R2 are the same and are C2H4Or C3H6R3 is CH3And n is 1000-2000.
10. The preparation method of the coke oven flue gas denitration agent catalyst as set forth in any one of claims 1 to 9, characterized by comprising the steps of:
(1) grinding attapulgite and activated carbon fiber to 40-60 meshes, adding an impregnation solution, impregnating at 50-70 ℃ for 1-3h, adding nano oxide, uniformly stirring, keeping the temperature at 60-80 ℃ for 2-3h, and cooling to room temperature to obtain a first component;
(2) adding polyacrylate and a modifier into a reactor, adding acid, stirring uniformly, heating to 120-150 ℃, reacting for 1-3h, cooling to room temperature, and adding water for washing;
(3) adding alkyl halide and catalyst, heating to 30-35 deg.C, stirring and reacting for 6-10h to obtain a second component;
(4) mixing the first component and the second component, heating to 60-80 deg.C, adding pore-forming agent, stirring, cooling, drying, and pulverizing.
Technical Field
The application relates to a coke oven flue gas denitration catalyst and a preparation method thereof, belonging to the technical field of coke oven flue gas waste gas treatment.
Background
The coking industry is the second largest domestic coal-fired household second to thermal power generation, however, a large amount of sulfur dioxide and nitrogen oxide exist in coke oven flue gas generated by coal burning, nitrogen monoxide and nitrogen dioxide in the atmosphere seriously damage the ecological environment and harm human health, and therefore, the coke oven flue gas can be discharged after being subjected to desulfurization and denitrification treatment.
In the prior art, spraying ammonia water is usually used for denitration, but because the residual sulfur trioxide in the coke oven flue gas and the ammonia water are used for producing ammonium salt which is attached to and wraps the surface of the denitration catalyst, the denitration agent can lose effectiveness after thermal desorption for several times, cannot be regenerated, has high cost and has general denitration effect.
Disclosure of Invention
In order to solve the problems, the denitration catalyst for the coke oven flue gas and the preparation method thereof are provided, the denitration catalyst adopts anion exchange resin to be fully mixed with the modified first component, and pore-making agent is used to change the resin into macroporous adsorption resin, so that the modified first component can be uniformly dispersed in pores of the resin, ammonium salt generated by reaction of sulfur trioxide in the flue gas and ammonia water is attached to the edges of the pores and cannot be coated on the surface of the denitration catalyst, the adsorption area is increased, the denitration effect is enhanced, the adsorbed resin can be regenerated and reused after being washed by deionized water and ethanol, and the production cost is reduced.
According to one aspect of the application, a coke oven flue gas denitration agent catalyst is provided, which is prepared from a first component, a second component and a pore-forming agent;
the first component is prepared from the following raw materials in parts by weight: 40-60 parts of attapulgite, 20-40 parts of activated carbon fiber, 50-70 parts of impregnation liquid and 30-50 parts of nano oxide;
the second component is anion exchange resin which is prepared from the following raw materials in parts by weight: 60-80 parts of polyacrylate, 40-60 parts of modifier, 10-20 parts of acid, 10-20 parts of catalyst and 20-40 parts of alkyl halide; the pore-making agent is toluene.
Preferably, the pore-forming agent is added in an amount of 5 to 10% by mass of the total mass of the first component and the second component.
Optionally, the activated carbon fiber is polyacrylonitrile-based carbon fiber or polyvinyl alcohol-based activated carbon fiber.
Optionally, the impregnation fluid is a potassium phosphate solution and/or a sodium carbonate solution.
Preferably, the impregnation liquid is a potassium phosphate solution and a sodium carbonate solution, and the volume ratio of the potassium phosphate solution to the sodium carbonate solution is (1-2): 1.
Optionally, the nano-oxide is nano-calcium oxide and nano-aluminum oxide, and the mass ratio of the nano-calcium oxide to the nano-aluminum oxide is (1-3): 1.
Optionally, the structural general formula of the polyacrylate is shown as formula 1
Wherein n is 1000-2000.
Optionally, the modifier is 3-aminobenzoic acid, and the structural formula of the modifier is shown as formula 2
Optionally, the acid is concentrated sulfuric acid or p-toluenesulfonic acid, the alkyl halide is any one of ethyl bromide and propyl bromide, the catalyst is potassium permanganate, and the pore-making agent is toluene.
Optionally, the anion exchange resin has a structural formula shown in formula 3
Wherein R1 and R2 are the same and are C2H4Or C3H6R3 is CH3And n is 1000-2000.
According to another aspect of the application, a preparation method of any one of the coke oven flue gas denitration agent catalysts is provided, and the preparation method comprises the following steps:
(1) grinding attapulgite and activated carbon fiber to 40-60 meshes, adding an impregnation solution, impregnating at 50-70 ℃ for 1-3h, adding nano oxide, uniformly stirring, keeping the temperature at 60-80 ℃ for 2-3h, and cooling to room temperature to obtain a first component;
(2) adding polyacrylate and a modifier into a reactor, adding acid, stirring uniformly, heating to 120-150 ℃, reacting for 1-3h, cooling to room temperature, and adding water for washing;
(3) adding alkyl halide and catalyst, heating to 30-35 deg.C, stirring and reacting for 6-10h to obtain a second component;
(4) mixing the first component and the second component, heating to 60-80 deg.C, adding pore-forming agent, stirring, cooling, drying, and pulverizing.
Preferably, the particle size of the crushed denitration catalyst is 50 to 100 mesh.
In the present application, "room temperature" means 25 ℃.
Benefits of the present application include, but are not limited to:
1. according to the coke oven flue gas denitration agent catalyst, firstly, the active carbon fiber is subjected to oxidation modification by using impregnation liquid and nano oxides, the number and the surface polarity of the microporous structure of the active carbon fiber are increased, and the contact area between the attapulgite and the active carbon fiber is increased, so that sulfides such as sulfur dioxide are fully absorbed.
2. According to the coke oven flue gas denitration agent catalyst, the hydroxyl in the polyacrylate is reacted with the carboxyl in the 3-aminobenzoic acid by using the modifier, the resin is attached with methylamino, and the methylamino is alkylated by using the alkyl halide, so that the modified anion exchange resin can adsorb nitrogen oxide and nitrogen oxide ions, the adsorption capacity is large, and the resin can be desorbed by flushing, and the regeneration and the utilization of the resin are realized.
3. According to the coke oven flue gas denitration agent catalyst, the first component and the second component are mixed and added with the pore-making agent, so that the anion exchange resin is changed into the macroporous adsorption resin, and the adsorption component in the first component can be uniformly dispersed in gaps inside and on the surface of the resin, so that the contact area of flue gas and the whole denitration agent catalyst is increased, the effective specific surface area of adsorption is also increased, the ammonium salt formed by sulfur trioxide and ammonia water is dispersed and adsorbed on the edge of the pore, and the whole denitration agent catalyst cannot be wrapped and fail; and the whole denitration catalyst can be regenerated and reused by washing with deionized water and ethanol, so that the production cost is reduced.
4. According to the preparation method of the coke oven flue gas denitration agent catalyst, the first component is uniformly wrapped and dispersed by the resin, and meanwhile, the contact area with the flue gas and the adsorption capacity of the resin are increased.
5. The preparation method of the coke oven flue gas denitration agent catalyst has the advantages of simple process, low cost and easy industrial production.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and catalysts in the examples of the present application were commercially available, wherein the attapulgite was a type FZ-40 of the new material feizhou company.
The mesh number of the crushed denitration catalyst prepared in the examples and the comparative examples is 60 meshes.
Example 1 preparation of denitrifier catalyst No. 1
In the denitrifier catalyst 1#, the first component is prepared from the following raw materials in parts by weight: 50 parts of attapulgite, 30 parts of polyacrylonitrile-based carbon fiber and 60 parts of impregnation liquid, wherein the impregnation liquid is a mixed solution of a potassium phosphate solution and a sodium carbonate solution, the volume ratio of the potassium phosphate solution to the sodium carbonate solution is 1:1, 40 parts of nano oxide is adopted, the nano oxide is nano calcium oxide and nano aluminum oxide, and the mass ratio of the nano calcium oxide to the nano aluminum oxide is 2: 1;
the second component is an anion exchange resin,the composite material is prepared from the following raw materials in parts by weight: 70 portions of polyacrylate with the structural formula shown as formula 1 (wherein R1 and R2 are C)2H4N is 1500), 50 parts of 3-aminobenzoic acid, 15 parts of concentrated sulfuric acid, 15 parts of potassium permanganate and 30 parts of bromoethane;
the pore-forming agent is toluene, and the addition amount of the pore-forming agent is 8 percent of the total mass of the first component and the second component.
The preparation method of the denitration agent catalyst 1# comprises the following steps:
(1) grinding attapulgite and activated carbon fiber to 50 meshes, adding an impregnation solution, impregnating at 60 ℃ for 2h, adding nano oxide, stirring uniformly, keeping the temperature at 70 ℃ for 2h, and cooling to room temperature to obtain a first component;
(2) adding polyacrylate and a modifier into a reactor, adding acid, stirring uniformly, heating to 130 ℃, reacting for 2 hours, cooling to room temperature, and adding water to clean;
(3) adding alkyl halide and a catalyst, heating to 33 ℃, and stirring for reacting for 8 hours to obtain a second component;
(4) mixing the first component and the second component, heating to 70 ℃, adding toluene, stirring uniformly, cooling, drying, crushing and granulating to obtain the denitration agent catalyst No. 1.
Example 2 preparation of denitrifier catalyst No. 2
In the denitrifying agent catalyst 2#, a first component is prepared from the following raw materials in parts by weight: 40 parts of attapulgite, 20 parts of polyacrylonitrile-based carbon fiber and 50 parts of impregnation liquid, wherein the impregnation liquid is a mixed solution of a potassium phosphate solution and a sodium carbonate solution, the volume ratio of the potassium phosphate solution to the sodium carbonate solution is 2:1, 30 parts of nano oxide is adopted, the nano oxide is nano calcium oxide and nano aluminum oxide, and the mass ratio of the nano calcium oxide to the nano aluminum oxide is 1: 1;
the second component is anion exchange resin which is prepared from the following raw materials in parts by weight: 60 portions of polyacrylate with the structural formula shown as formula 1 (wherein R1 and R2 are C)2H4N is 1000), 40 parts of 3-aminobenzoic acid, 10 parts of concentrated sulfuric acid, 10 parts of potassium permanganate and 20 parts of bromoethane;
the pore-forming agent is toluene, and the addition amount of the pore-forming agent is 5% of the total mass of the first component and the second component.
The preparation method of the denitration agent catalyst 2# comprises the following steps:
(1) grinding attapulgite and activated carbon fiber to 40 meshes, adding an impregnation solution, impregnating at 50 ℃ for 1h, adding nano oxide, stirring uniformly, keeping the temperature at 60 ℃ for 2h, and cooling to room temperature to obtain a first component;
(2) adding polyacrylate and a modifier into a reactor, adding acid, stirring uniformly, heating to 120 ℃, reacting for 1h, cooling to room temperature, and adding water to clean;
(3) adding alkyl halide and a catalyst, heating to 30 ℃, and stirring for reacting for 6 hours to obtain a second component;
(4) mixing the first component and the second component, heating to 60 ℃, adding toluene, stirring uniformly, cooling, drying, crushing and granulating to obtain the denitration agent catalyst No. 2.
Example 3 Denitrifier catalyst 3#
In the denitrifying agent catalyst 3#, a first component is prepared from the following raw materials in parts by weight: 60 parts of attapulgite, 40 parts of polyvinyl alcohol-based active carbon fiber and 70 parts of impregnation liquid, wherein the impregnation liquid is a mixed solution of a potassium phosphate solution and a sodium carbonate solution, the volume ratio of the potassium phosphate solution to the sodium carbonate solution is 2:1, 50 parts of nano oxide is adopted, the nano oxide is nano calcium oxide and nano aluminum oxide, and the mass ratio of the nano calcium oxide to the nano aluminum oxide is 3: 1;
the second component is anion exchange resin which is prepared from the following raw materials in parts by weight: 80 parts of polyacrylate with a structural formula shown as formula 1 (wherein R1 and R2 are C)3H6N is 2000), 60 parts of 3-aminobenzoic acid, 20 parts of p-toluenesulfonic acid, 20 parts of potassium permanganate and 40 parts of bromopropane;
the pore-forming agent is toluene, and the addition amount of the pore-forming agent is 10% of the total mass of the first component and the second component.
The preparation method of the denitration agent catalyst 3# comprises the following steps:
(1) grinding attapulgite and activated carbon fiber to 60 meshes, adding the impregnation liquid, impregnating for 3h at 70 ℃, adding nano oxide, stirring uniformly, keeping the temperature for 3h at 80 ℃, and cooling to room temperature to obtain a first component;
(2) adding polyacrylate and a modifier into a reactor, adding acid, stirring uniformly, heating to 150 ℃, reacting for 3 hours, cooling to room temperature, and adding water to clean;
(3) adding alkyl halide and a catalyst, heating to 35 ℃, and stirring for reaction for 10 hours to obtain a second component;
(4) mixing the first component and the second component, heating to 80 ℃, adding toluene, stirring uniformly, cooling, drying, crushing and granulating to obtain the denitration agent catalyst No. 3.
Comparative example 1 preparation of comparative denitration agent catalyst 1#
Comparative example 1 is different from example 1 in that comparative example 1 uses the first component alone to prepare a comparative denitration agent catalyst # 1, does not use the second component and the pore-forming agent, and the parts of raw materials and the preparation method are the same as those of the first component in example 1.
Comparative example 2 preparation of comparative denitration agent catalyst 2#
Comparative example 2 is different from example 1 in that comparative example 2 uses the second component and the pore-forming agent to prepare a comparative denitration agent catalyst # 2, does not use the first component, and the parts of raw materials and the preparation method are the same as those of the first component in example 1.
Comparative example 3 preparation of comparative denitration agent catalyst # 3
Comparative example 3 is different from example 1 in that comparative example 3 uses commercially available 40-mesh activated carbon instead of activated carbon fiber, and the other portions are the same as example 1.
Comparative example 4 preparation of comparative denitration agent catalyst No. 4
Comparative example 4 is different from example 1 in that comparative example 4 does not use a nano-oxide, and the other portions are the same as example 1.
Comparative example 5 preparation of comparative denitration agent catalyst # 5
Comparative example 5 is different from example 1 in that the mass ratio of nano calcium oxide to nano aluminum oxide in the nano oxide used in comparative example 5 is 5:1, and the rest is the same as example 1.
Comparative example 6 preparation of comparative denitration agent catalyst 6#
Comparative example 6 is different from example 1 in that comparative example 6 does not modify polyacrylate, and does not add modifier, acid, catalyst and alkyl halide, and the rest is the same as example 1.
Example 4 denitration Effect test
And (3) testing conditions are as follows: respectively introducing the same components and the same volume of mixed gas into a denitration device, wherein the flow rates of the gases in all groups are the same and are 200ml/min, respectively testing the denitration effects of the denitration agent catalyst No. 1-3 and the comparative denitration agent catalyst No. 1-6, wherein the volume fractions of the gases in the mixed gas are NO 40%, and NO 62 25％，SO2 15％，SO310％，O28 percent and the balance of hydrogen.
The denitration effect test results are shown in table 1.
The results show that the denitration catalyst obtained by using the raw material components and parts and the preparation method defined by the application has high denitration efficiency, the denitration efficiency of the denitration catalyst 1# reaches 98%, and the denitration efficiencies of the denitration catalyst 2# and the denitration catalyst 3# are both more than 95%.
Contrast denitration agent catalyst 1# and contrast denitration agent catalyst 2# all make exclusive use of first component or second component, final denitration efficiency is all lower, less than 60%, show that what adopt in this application makes effective adsorbed component homodisperse with first component, the mixed preparation of second component and system hole agent, effective adsorption area is big, and sulfur trioxide and the ammonium salt that the aqueous ammonia formed can the dispersion absorption at the hole edge, can not live whole denitration agent catalyst parcel and lose efficacy or reduce denitration efficiency.
Different raw materials are adopted for comparing the 3# to 6# of the denitration agent catalyst respectively or are not modified, and then the raw material proportion is changed, so that the final denitration efficiency is obviously lower than that of the 1# to 3# of the denitration agent catalyst, which shows that the types, proportions and modified preparation methods of the raw materials defined in the application can influence the final denitration efficiency.
The above are merely examples of the present application, and the scope of the present application is not limited by these specific examples, but is defined by the claims of the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical idea and principle of the present application should be included in the protection scope of the present application.