CN112121816A - Low-temperature catalyst special for waste incineration - Google Patents

Low-temperature catalyst special for waste incineration Download PDF

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Publication number
CN112121816A
CN112121816A CN202011148341.5A CN202011148341A CN112121816A CN 112121816 A CN112121816 A CN 112121816A CN 202011148341 A CN202011148341 A CN 202011148341A CN 112121816 A CN112121816 A CN 112121816A
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parts
catalyst
vanadium
waste incineration
temperature
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林勇
李军营
吴道君
王辉
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Hubei Qunyouchangwu Environmental Protection Technology Co ltd
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Hubei Qunyouchangwu Environmental Protection Technology Co ltd
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    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • 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
    • 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
    • B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
    • B01J35/61—

Abstract

A special low-temperature catalyst for waste incineration is characterized in that the catalyst comprises the following components in parts by weight: nano titanium dioxide powder, silicon dioxide powder, a main catalyst, a rare earth element cocatalyst, a manganese-containing cocatalyst, lactic acid, stearic acid, glass fiber, hydroxypropyl methyl cellulose, polyoxyethylene and ammonia water. The invention can simultaneously remove NOx and organic matters (dioxin and the like), the removal efficiency reaches 90% at 130 ℃, the denitration efficiency reaches 100% at 200 ℃, and the removal rate of the dioxin is more than 80%. The catalyst is suitable for the environmental protection fields of tail gas denitration and the like of waste incineration power generation and other waste incineration.

Description

Low-temperature catalyst special for waste incineration
Technical Field
The invention relates to a special low-temperature catalyst for waste incineration, which has good heat exchange performance, denitration activity and a wider temperature window.
Background
With the acceleration of the urbanization process and the continuous improvement of the living standard, the production amount of the domestic garbage is increased day by day, and the phenomenon of 'garbage enclosing city' appears in multiple cities. The waste incineration power generation is utilized, so that the problem of waste treatment is solved, waste is turned into wealth, electric energy is generated, and the environmental value and the economic value are high. The number of new garbage incineration power plants in China is increased year by year, the proportion of incineration methods in the household garbage treatment mode is increased year by year, and the incineration treatment capacity of urban garbage in national cities accounts for more than 50% of the total treatment capacity by the end of 2020. But the inevitable domestic garbage can generate flue gas containing harmful substances such as particulate matters, HCL, SO2, NOx, dioxin and the like in the incineration process.
The requirement of strict national standards on the pollution control of waste incineration has been provided for many years in 2019, and ultralow emission has been put forward in part of provinces and markets, however, flue gas pollutant removal processes such as 'SNCR denitration + dry deacidification + activated carbon injection + bag dedusting + wet deacidification' and the like widely used in the industry cannot meet the requirement of deep purification, especially, the purification of NOx and organic matters (containing dioxin) still has a large promotion space, and the research and development of a flue gas pollutant deep purification technology which can be integrated into the existing process, is low in investment cost and high in purification efficiency are urgently needed.
Among the numerous flue gas denitration methods, the Selective Catalytic Reduction (SCR) technology is the most widely used flue gas denitration method in the developed countries at present. However, the existing SCR catalyst is mostly based on vanadium, and when the temperature of the vanadium-based catalyst is below 180 ℃, the denitration efficiency of the catalyst is rapidly reduced, and when the temperature is below 160 ℃, the denitration efficiency of the catalyst is very low, so that the SCR catalyst is difficult to be industrially applied. And simultaneously, the removal of dioxin in the waste incineration flue gas is also a difficult problem. Therefore, the development of a special catalyst for purifying waste incineration flue gas is the most economical and suitable choice for simultaneously removing NOx and organic matters (dioxin and the like) under the low-temperature condition, on one hand, the requirement of environmental protection can be met, and on the other hand, the successful application of the technology contains huge economic benefits and environmental benefits. The invention of the catalyst aims to simultaneously remove NOx and dioxin in waste incineration flue gas.
Disclosure of Invention
The invention provides a special low-temperature catalyst for waste incineration, which aims to solve the technical problem.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a low-temperature catalyst special for waste incineration comprises the following components in parts by weight: 52-81 parts of nano titanium dioxide powder, 2.7-4.5 parts of silicon dioxide powder, 6-22 parts of main catalyst, 1-15 parts of rare earth element cocatalyst, 0-20 parts of manganese-containing cocatalyst, 2 parts of lactic acid, 0.3 part of stearic acid, 5 parts of glass fiber, 0.5-3 parts of hydroxypropyl methyl cellulose, 0.6 part of polyoxyethylene and 7 parts of ammonia water.
Preferably, the main catalyst is a ferrovanadium compound, wherein vanadium accounts for 1-10% of the total amount of the ferrovanadium compound.
Preferably, the ferrovanadium compound comprises a vanadium-containing main catalyst raw material and an iron-containing main catalyst raw material, the vanadium-containing main catalyst raw material is ammonium metavanadate, vanadium pentoxide and elemental vanadium, and the iron-containing main catalyst raw material is one or more of ferrous iron nitrate, ferrous oxalate, ferric oxide and elemental iron.
Preferably, the rare earth element promoter is at least one of cerium nitrate, lanthanum nitrate, cerium oxide and lanthanum oxide.
Preferably, the manganese-containing promoter is at least one of manganese oxalate, manganese dioxide, manganese nitrate and manganese acetate.
A preparation method of a special low-temperature catalyst for waste incineration comprises the following steps:
1) weighing vanadium-containing main catalyst raw materials and iron-containing main catalyst raw materials, mixing, calcining at 650 ℃ for 4h, taking out, and performing ball milling for 8h to obtain vanadium-iron compound powder for detection and standby application;
2) mixing pug, weighing nano titanium dioxide powder and silicon dioxide powder mixed powder, the vanadium iron compound powder prepared in the step 1), a manganese-containing cocatalyst, a rare earth element cocatalyst and stearic acid, and putting into a mixing roll for dry mixing for 20 min;
3) measuring 50% lactic acid, diluting with water, adding into the uniformly mixed solid powder, stirring for 10min, and adding 20% ammonia water;
4) adding glass fiber and pulp cotton, stirring for 15min, slowly adding monoethanolamine, continuously stirring for 20min, and adding distilled water step by step according to the principle of small amount of multiple times;
5) adding a binder, slowly adding hydroxypropyl methyl cellulose, stirring for l0min, and adding polyoxyethylene to prepare a catalyst mud material with excellent plasticity;
6) and (3) carrying out vacuum forming extrusion on the tempered catalyst mud, drying at the final temperature of 60 ℃, and calcining at the final temperature of 400 ℃ to finally obtain the finished catalyst.
Preferably, in the step 1), the vanadium-containing main catalyst raw material and the iron-containing main catalyst raw material are mixed according to a ratio of 1: 10-20, calcined at a temperature of 500-1200 ℃ for 4 hours, and then ground into fine particles with a particle size of 1-5 μm by a ball mill.
The invention adopts the nano-scale titanium dioxide, increases the specific surface area of the catalyst as much as possible, and is beneficial to the denitration efficiency of the catalyst under the low-temperature condition.
The forming method of the catalyst is characterized by firstly preparing a vanadium-iron compound, wherein vanadium accounts for 1-10% of the total amount of the vanadium-iron compound, the calcining temperature is 800-1200 ℃, and vanadium-iron forms a eutectic body. The mixture is crushed into particles with the particle size of 1-5 mu m by a crusher. The subsequent catalyst is integrally formed, so that the uniformity of the active component is ensured.
The invention can simultaneously remove NOx and organic matters (dioxin and the like), the removal efficiency reaches 90% at 130 ℃, the denitration efficiency reaches 100% at 200 ℃, and the removal rate of the dioxin is more than 80%. The catalyst is suitable for the environmental protection fields of tail gas denitration and the like of waste incineration power generation and other waste incineration.
Detailed Description
In order to facilitate an understanding of the invention, the following examples are given to more fully describe the invention. The present invention may, however, be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Example 1
1) Weighing 5 parts of ammonium metavanadate and 70 parts of ferrous oxalate, mixing, calcining at 650 ℃ for 4 hours, taking out, and performing ball milling for 8 hours to obtain ferrovanadium compound powder for detection and later use;
2) mixing pugs, weighing 52 parts of nano titanium dioxide powder, 2.7 parts of silicon dioxide powder mixed powder, 20 parts of vanadium-iron compound powder prepared in the step 1), 10 parts of manganese oxalate, 10 parts of cerium nitrate and 0.3 part of stearic acid, and putting into a mixing roll to dry mix for 20 min;
3) weighing 2 parts of lactic acid with the concentration of 50%, diluting the lactic acid with water to 25 parts, adding the diluted lactic acid into the uniformly mixed solid powder, stirring the mixture for 10 minutes, and adding 7 parts of ammonia water with the concentration of 20%;
4) adding 5 parts of glass fiber and 3.6 parts of pulp cotton, stirring for 15min, slowly adding 6.5 parts of monoethanolamine, continuously stirring for 20min, and adding 120 parts of distilled water step by step according to the principle of small amount and multiple times;
5) adding a binder, slowly adding 0.5 part of hydroxypropyl methyl cellulose, stirring for l0min, and then adding 0.6 part of polyoxyethylene to prepare a catalyst mud material with excellent plasticity;
6) and (3) carrying out vacuum forming extrusion on the tempered catalyst mud, drying at the final temperature of 60 ℃, and calcining at the final temperature of 400 ℃ to finally obtain the finished catalyst.
Example 2
1) Weighing 5 parts of ammonium metavanadate and 70 parts of ferrous oxalate, mixing, calcining at 650 ℃ for 4 hours, taking out, and performing ball milling for 8 hours to obtain ferrovanadium compound powder for detection and later use;
2) mixing pugs, weighing 60 parts of nano titanium dioxide powder, 3.1 parts of silicon dioxide powder mixed powder, 22 parts of ferrovanadium compound powder prepared in the step 1), 20 parts of manganese oxalate, 15 parts of lanthanum nitrate and 0.3 part of stearic acid, and putting into a mixing roll to dry mix for 20 min;
3) weighing 2 parts of lactic acid with the concentration of 50%, diluting the lactic acid with water to 25 parts, adding the diluted lactic acid into the uniformly mixed solid powder, stirring the mixture for 10 minutes, and adding 7 parts of ammonia water with the concentration of 20%;
4) adding 5 parts of glass fiber and 3.6 parts of pulp cotton, stirring for 15min, slowly adding 6.5 parts of monoethanolamine, continuously stirring for 20min, and adding 120 parts of distilled water step by step according to the principle of small amount and multiple times;
5) adding a binder, slowly adding 3 parts of hydroxypropyl methyl cellulose, stirring for l0min, and then adding 0.6 part of polyoxyethylene to prepare a catalyst mud material with excellent plasticity;
6) and (3) carrying out vacuum forming extrusion on the tempered catalyst mud, drying at the final temperature of 60 ℃, and calcining at the final temperature of 400 ℃ to finally obtain the finished catalyst.
Example 3
1) Weighing 10 parts of ammonium metavanadate and 90 parts of ferrous oxalate, mixing, calcining at 650 ℃ for 4 hours, taking out, and performing ball milling for 8 hours to obtain ferrovanadium compound powder for detection and later use;
2) mixing pugs, weighing 70 parts of nano titanium dioxide powder, 3.5 parts of silicon dioxide powder mixed powder, 15 parts of ferrovanadium compound powder prepared in the step 1), 20 parts of manganese oxalate, 10 parts of cerium nitrate and 0.3 part of stearic acid, and putting into a mixing roll to dry mix for 20 min;
3) weighing 2 parts of lactic acid with the concentration of 50%, diluting the lactic acid with water to 25 parts, adding the diluted lactic acid into the uniformly mixed solid powder, stirring the mixture for 10 minutes, and adding 7 parts of ammonia water with the concentration of 20%;
4) adding 5 parts of glass fiber and 3.6 parts of pulp cotton, stirring for 15min, slowly adding 6.5 parts of monoethanolamine, continuously stirring for 20min, and adding 120 parts of distilled water step by step according to the principle of small amount and multiple times;
5) adding a binder, slowly adding 2 parts of hydroxypropyl methyl cellulose, stirring for l0min, and then adding 0.6 part of polyoxyethylene to prepare a catalyst mud material with excellent plasticity;
6) and (3) carrying out vacuum forming extrusion on the tempered catalyst mud, drying at the final temperature of 60 ℃, and calcining at the final temperature of 400 ℃ to finally obtain the finished catalyst.
Example 4
1) Weighing 10 parts of ammonium metavanadate and 90 parts of ferrous oxalate, mixing, calcining at 650 ℃ for 4 hours, taking out, and performing ball milling for 8 hours to obtain ferrovanadium compound powder for detection and later use;
2) mixing pug, weighing 290 parts of nano titanium dioxide powder and silicon dioxide powder mixed powder, 10 parts of ferrovanadium compound powder prepared in the step 1), 5 parts of manganese oxalate, 5 parts of cerium nitrate and 0.3 part of stearic acid, and putting into a mixing roll for dry mixing for 20 min;
3) weighing 2 parts of lactic acid with the concentration of 50%, diluting the lactic acid with water to 25 parts, adding the diluted lactic acid into the uniformly mixed solid powder, stirring the mixture for 10 minutes, and adding 7 parts of ammonia water with the concentration of 20%;
4) adding 5 parts of glass fiber and 3.6 parts of pulp cotton, stirring for 15min, slowly adding 6.5 parts of monoethanolamine, continuously stirring for 20min, and adding 120 parts of distilled water step by step according to the principle of small amount and multiple times;
5) adding a binder, slowly adding 1.5 parts of hydroxypropyl methyl cellulose, stirring for l0min, and then adding 0.6 part of polyoxyethylene to prepare a catalyst mud material with excellent plasticity;
6) and (3) carrying out vacuum forming extrusion on the tempered catalyst mud, drying at the final temperature of 60 ℃, and calcining at the final temperature of 400 ℃ to finally obtain the finished catalyst.
Example 5
1) Weighing 10 parts of ammonium metavanadate and 40 parts of ferrous oxalate, mixing, calcining at 650 ℃ for 4 hours, taking out, and performing ball milling for 8 hours to obtain ferrovanadium compound powder for detection and later use;
2) mixing pugs, weighing 81 parts of nano titanium dioxide powder, 4.5 parts of silicon dioxide powder mixed powder, 6 parts of ferrovanadium compound powder prepared in the step 1), 22 parts of manganese oxalate, 15 parts of cerium nitrate and 0.3 part of stearic acid, and putting into a mixing roll for dry mixing for 20 min;
3) weighing 2 parts of lactic acid with the concentration of 50%, diluting the lactic acid with water to 25 parts, adding the diluted lactic acid into the uniformly mixed solid powder, stirring the mixture for 10 minutes, and adding 7 parts of ammonia water with the concentration of 20%;
4) adding 5 parts of glass fiber and 3.6 parts of pulp cotton, stirring for 15min, slowly adding 6.5 parts of monoethanolamine, continuously stirring for 20min, and adding 120 parts of distilled water step by step according to the principle of small amount and multiple times;
5) adding a binder, slowly adding 2.5 parts of hydroxypropyl methyl cellulose, stirring for l0min, and then adding 0.6 part of polyoxyethylene to prepare a catalyst mud material with excellent plasticity;
6) and (3) carrying out vacuum forming extrusion on the tempered catalyst mud, drying at the final temperature of 60 ℃, and calcining at the final temperature of 400 ℃ to finally obtain the finished catalyst.
Comparative example
Firstly, a certain amount of TiO is added2And (nanometer) stirring in a kneader, adding glass fiber (0.1-0.3 mm), argil, a binder and the like, mixing in the kneader, and stirring for 1 hour. Then a certain proportion of (CH)3COO）2Mn·4H2O and Ce (NO)3）3·6H2Respectively dissolving O, uniformly spraying into a kneader, controlling the water content, stirring for 2h, coating the kneaded paste on a steel mesh, and roasting at 400-500 ℃ for 2h to obtain Mn-Ce/TiO2A low temperature catalyst.
The catalysts prepared by the methods of examples 1 to 5 and the comparative example were cut to 40mm × 40mm × 50mm, and placed in an SCR catalyst evaluation apparatus at a space velocity of 6250h-1The initial concentration of NO in the flue gas is 600ppm, NO215ppm, 10% of steam water and 1:1 of ammonia nitrogen, and the measured data are shown in Table 1.
TABLE 1 data table of activity evaluation results of examples 1 to 5 and comparative examples
Reaction temperature C NOx conversion% Conversion of toluene% Conversion of acetone%
Example 1 160 90 30 50
Example 2 160 90 60 75
Example 3 160 95 70 95
Example 4 160 95 80 90
Example 5 200 100 90 95
Comparative example 160 55 22 35
As can be seen from Table 1, the denitration efficiency of the catalyst provided by the invention is over 90%, and the catalyst has better denitration performance compared with a comparative example.
The catalyst is prepared into a ferrovanadium compound, and the ferrovanadium compound is crushed into particles of 1-5 microns by a crusher. The subsequent catalyst is integrally formed, so that the uniformity of the active component is ensured. The catalyst is suitable for the industries of waste incineration, synergetic removal of dioxin and nitrogen oxides in the delayed period and denitration at the low temperature of 130-200 ℃ in other industries.
The embodiments of the present invention are described only for the preferred embodiments of the present invention, and not for the limitation of the concept and scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the concept of the present invention shall fall within the protection scope of the present invention, and the claimed technology of the present invention shall be fully described in the claims.

Claims (7)

1. A special low-temperature catalyst for waste incineration is characterized in that the catalyst comprises the following components in parts by weight: 52-81 parts of nano titanium dioxide powder, 2.7-4.5 parts of silicon dioxide powder, 6-22 parts of main catalyst, 1-15 parts of rare earth element cocatalyst, 0-20 parts of manganese-containing cocatalyst, 2 parts of lactic acid, 0.3 part of stearic acid, 5 parts of glass fiber, 0.5-3 parts of hydroxypropyl methyl cellulose, 0.6 part of polyoxyethylene and 7 parts of ammonia water.
2. The special low-temperature catalyst for waste incineration as claimed in claim 1, wherein the main catalyst is a vanadium-iron compound, wherein vanadium accounts for 1-10% of the total amount of the vanadium-iron compound.
3. The special low-temperature catalyst for waste incineration as claimed in claim 1, wherein the vanadium-iron compound comprises a vanadium-containing main catalyst material and an iron-containing main catalyst material, the vanadium-containing main catalyst material is ammonium metavanadate, vanadium pentoxide or elemental vanadium, and the iron-containing main catalyst material is one or more of ferrous iron nitrate, ferrous oxalate, ferric oxide and elemental iron.
4. The special low-temperature catalyst for waste incineration as claimed in claim 1, wherein the rare earth element promoter is at least one of cerium nitrate, lanthanum nitrate, cerium oxide and lanthanum oxide.
5. The special low-temperature catalyst for waste incineration as claimed in claim 1, wherein the manganese-containing promoter is at least one of manganese oxalate, manganese dioxide, manganese nitrate and manganese acetate.
6. The preparation method of the special low-temperature catalyst for waste incineration according to claim 1, characterized by comprising the following steps:
1) weighing vanadium-containing main catalyst raw materials and iron-containing main catalyst raw materials, mixing, calcining at 650 ℃ for 4h, taking out, and performing ball milling for 8h to obtain vanadium-iron compound powder for detection and standby application;
2) mixing pug, weighing nano titanium dioxide powder and silicon dioxide powder mixed powder, the vanadium iron compound powder prepared in the step 1), a manganese-containing cocatalyst, a rare earth element cocatalyst and stearic acid, and putting into a mixing roll for dry mixing for 20 min;
3) measuring 50% lactic acid, diluting with water, adding into the uniformly mixed solid powder, stirring for 10min, and adding 20% ammonia water;
4) adding glass fiber and pulp cotton, stirring for 15min, slowly adding monoethanolamine, continuously stirring for 20min, and adding distilled water step by step according to the principle of small amount of multiple times;
5) adding a binder, slowly adding hydroxypropyl methyl cellulose, stirring for l0min, and adding polyoxyethylene to prepare a catalyst mud material with excellent plasticity;
6) and (3) carrying out vacuum forming extrusion on the tempered catalyst mud, drying at the final temperature of 60 ℃, and calcining at the final temperature of 400 ℃ to finally obtain the finished catalyst.
7. The preparation method of the special low-temperature catalyst for waste incineration according to claim 6, wherein the vanadium-containing main catalyst raw material and the iron-containing main catalyst raw material in the step 1) are mixed according to a ratio of 1: 10-20, calcined for 4 hours at a temperature of 500-1200 ℃, and then ground into fine particles of 1-5 μm by a ball mill.
CN202011148341.5A 2020-10-23 2020-10-23 Low-temperature catalyst special for waste incineration Pending CN112121816A (en)

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CN113509941A (en) * 2021-06-19 2021-10-19 南通润启环保服务有限公司 Hazardous waste incineration denitration catalyst and preparation method thereof
CN115779911A (en) * 2022-12-12 2023-03-14 湖北群有长物环保科技有限公司 Preparation method of denitration catalyst with CO as reducing agent under low-temperature condition

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CN108341665A (en) * 2017-12-09 2018-07-31 湖北神雾热能技术有限公司 A kind of low-temperature catalyzed denitration of rare-earth-based, accumulation of heat one composite ceramic material

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CN102861595A (en) * 2012-09-20 2013-01-09 浙江天蓝环保技术股份有限公司 Honeycombed SCR (selective catalytic reduction) denitrification catalyst for low-temperature flue gas denitrification and preparation method thereof
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Publication number Priority date Publication date Assignee Title
CN113509941A (en) * 2021-06-19 2021-10-19 南通润启环保服务有限公司 Hazardous waste incineration denitration catalyst and preparation method thereof
CN115779911A (en) * 2022-12-12 2023-03-14 湖北群有长物环保科技有限公司 Preparation method of denitration catalyst with CO as reducing agent under low-temperature condition

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