CN108856234B - Method for recycling defective products and cut materials in production process of honeycomb type denitration catalyst - Google Patents
Method for recycling defective products and cut materials in production process of honeycomb type denitration catalyst Download PDFInfo
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- CN108856234B CN108856234B CN201710336110.9A CN201710336110A CN108856234B CN 108856234 B CN108856234 B CN 108856234B CN 201710336110 A CN201710336110 A CN 201710336110A CN 108856234 B CN108856234 B CN 108856234B
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- 230000002950 deficient Effects 0.000 title claims abstract description 48
- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 239000000463 material Substances 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000004064 recycling Methods 0.000 title claims abstract description 12
- 238000005520 cutting process Methods 0.000 claims abstract description 22
- 239000002002 slurry Substances 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 238000004806 packaging method and process Methods 0.000 claims abstract description 4
- 238000009270 solid waste treatment Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 11
- MYHPJINPUDBKHX-UHFFFAOYSA-N [Si].[W].[Ti] Chemical compound [Si].[W].[Ti] MYHPJINPUDBKHX-UHFFFAOYSA-N 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000011863 silicon-based powder Substances 0.000 claims description 9
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000013543 active substance Substances 0.000 claims description 4
- 238000004537 pulping Methods 0.000 claims description 3
- 238000002372 labelling Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 11
- 239000003546 flue gas Substances 0.000 abstract description 11
- 239000002699 waste material Substances 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000001125 extrusion Methods 0.000 abstract description 4
- 125000004122 cyclic group Chemical group 0.000 abstract description 3
- 239000002910 solid waste Substances 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
The invention discloses a method for recycling defective goods and cut-off materials in the production process of a honeycomb type denitration catalyst, which adjusts the production process flow of the catalyst into mixing, pre-extrusion, vacuum extrusion, primary drying, sorting defective goods and collecting, secondary drying, sorting defective goods and collecting, cutting, collecting cut-off materials, calcining, sorting defective goods and packaging; then, carrying out slurrying on defective products and cut materials generated before the calcining process, and analyzing the slurry concentration to prepare for mixing and adding; sending the calcined defective products to a solid waste treatment department; the invention has the advantages that: the catalyst defective products and the cut materials can be recovered to the raw material state effectively to the maximum extent and are not changed, the harmless treatment and the resource utilization of the waste catalyst are realized, and the catalyst is used for preparing a new flue gas denitration catalyst, so that the rapid cyclic utilization of resources is realized, zero-risk waste production is realized, the process is simple, and the operability is strong.
Description
Technical Field
The invention relates to a method for recycling hazardous waste (HW49 and other waste), in particular to a method for recycling defective products and cut-off materials in the production process of a honeycomb type denitration catalyst in the production process of an SCR flue gas denitration catalyst, and belongs to the field of recycling of hazardous waste (HW49 and other waste).
Background
The Selective Catalytic Reduction (SCR) flue gas denitration technology has the advantages of high denitration rate, low price, almost no secondary pollution, small limitation of flue gas components and the like, and thus, the technology becomes a mainstream technology for removing nitrogen oxides (NOx) in coal-fired flue gas, flue gas and other waste gases. "our country thermal power plant denitration is reformed transform and is concentrated on 2012-2014, 2016 after, except old unit denitration transformation demand and newly-built unit denitrification facility installation, because the catalyst needs to be changed about 3 years-5 years later, the unit that has installed flue gas denitrification facility since 2012 will gradually get into the change period of denitration catalyst, and this will continuously increase denitration catalyst's market demand. At present, the total usage amount of SCR denitration catalysts in China reaches 80 ten thousand cubic meters (ten thousand cubic meters), 2016 is achieved, denitration catalysts installed before 2012 enter a replacement period, the total amount is about 10 ten thousand cubic meters, and by 2018, the amount of waste SCR denitration catalysts replaced every year reaches 25 ten thousand cubic meters. If calculated according to 2% of defective products and cut materials, 5000m of defective products and cut materials are produced every year; most factories collect the solid waste to be treated or sold to solid waste departments, which causes resource waste to production enterprises and increases production cost. Seriously affects the normal operation of enterprises and forms great environmental pressure on the soil and water in China.
The traditional process is shown in figure 1, the treatment design of solid wastes (defective products and cutting materials) is simple, the production cost of the SCR flue gas denitration catalyst applied to the industry at present is greatly increased, the selling unit price is sharply reduced, and the enterprise profit is sharply reduced at the same time. If a new process is not designed, enterprises can increase profits in order to reduce production cost, and solid wastes generated in the production process can not be sent to relevant departments to be processed at the expense; and the toxic vanadium in the catalyst enters natural environment (particularly water) under various actions, which brings serious harm to the environment. Therefore, the defective products and the cutting materials in the production process of the flue gas denitration catalyst must be reasonably treated according to certain specifications and regulations, so that the production cost of enterprises is reduced, and the environment is protected. However, it should be noted that the currently available waste catalyst recycling process is mostly dedicated to extracting vanadium, tungsten and titanium and has few examples, and no research and patent on direct recycling of waste SCR flue gas denitration catalysts in manufacturing enterprises is reported.
Disclosure of Invention
In order to solve the problems, the invention designs a method for recycling defective products and cut materials in the production process of the honeycomb type denitration catalyst, which can effectively recover the defective products and the cut materials of the catalyst to the maximum extent that the raw material state is not changed, realize the harmless treatment and resource utilization of the waste catalyst, and prepare a new flue gas denitration catalyst, thereby realizing the rapid cyclic utilization of resources, realizing the zero-risk waste production, and having simple process and strong operability.
The technical scheme of the invention is as follows:
a method for recycling defective products and cut materials in the production process of a honeycomb type denitration catalyst comprises the following steps:
(1) the production process flow of the catalyst is to adjust cutting to be before calcination, and the adjusted cutting is as follows: mixing, pre-extruding, vacuum extruding, primary drying, sorting and collecting defective products, secondary drying, sorting and collecting defective products, cutting, collecting and cutting off materials, calcining, sorting defective products and packaging;
sorting the products after the primary drying and the secondary drying are finished, sorting and collecting the defective products without entering the next working section, and marking the project names and the active substance content; and cutting the secondary dried qualified product according to the project requirements, collecting the cut material, and labeling the project name and the active substance content.
(2) Carrying out slurrying on defective products and cut materials generated before the calcining process, and analyzing the slurry concentration to prepare for mixing and adding;
(3) the calcined defective products were sent to a solid waste disposal department.
The pulping method in the step (2) comprises the following steps: according to defective products and cutting materials: water =1:4 by weight ratio, and the mixture was put into a slurrying tank and continuously stirred for 4 hours to decompose all the defective products uniformly in water.
Wherein, the ammonium metavanadate solution is prepared in the step (2) according to the slurry concentration, and the formula is as follows:
y=z-200*x%*n
wherein: y is the addition amount of ammonium metavanadate;
z is the amount of ammonium metavanadate to be added when no slurry is added;
x% is the slurry concentration;
and n is the mass percentage of the ammonium metavanadate in the catalyst before slurrying.
Further, 200kg of slurry, titanium-tungsten powder, titanium-tungsten-silicon powder and deionized water are added during mixing in the step (1) (the first step);
the titanium tungsten powder is added in an amount of =300kg-200kg x%. 0.8, wherein: 300kg is the addition amount of the original formula, x% is the slurry concentration, and 0.8 is the mass percentage of the titanium tungsten powder in the formula;
the addition of the titanium-tungsten-silicon powder is =100kg-200kg x% 0.1, wherein 100kg is the original addition of the titanium-tungsten-silicon powder, x% is the slurry concentration, and 0.1 is the mass percentage of the titanium-tungsten-silicon powder in the formula;
the deionized water is added in an amount of =250kg-200kg (1-x%), wherein 250kg is the original addition amount, 200kg is the amount of the added slurry, and x% is the slurry concentration.
The invention has the advantages that:
(1) the process is suitable for large-scale production, the existing production equipment can be utilized, the defective products and the cutting catalyst generated in the production process can be safely, efficiently and economically treated by the process, and the original process cannot be recycled;
(2) the sizing process does not produce any internal structural change to the molecular morphology of the raw material, and compared with the original titanium tungsten powder micro-morphology characterization map, the micro-morphology characterization map after sizing has no obvious difference, the micro-particles are dispersed uniformly, and the agglomeration or agglomeration phenomenon does not occur;
(3) the solid waste treatment process is simple, the investment can be saved, and the cost can be reduced;
(4) and defective products and cutting materials generated in the production process are used, so that the rapid cyclic utilization of resources is realized.
The invention is further illustrated by the following figures and examples.
Drawings
FIG. 1 is a flow chart of a conventional processing method;
FIG. 2 is a flow chart of a method according to an embodiment of the present invention.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.
The percent in the present invention means mass percent unless otherwise specified; but the percentage of the solution, unless otherwise specified, means that 100ml of the solution contains several grams of solute; the percentage between the liquids refers to the ratio of the volumes at 20 ℃.
Example 1
As shown in fig. 2, a method for recycling defective products and cut materials in the production process of a honeycomb type denitration catalyst comprises the following steps:
1) and the production process flow of the catalyst is adjusted as follows: mixing, pre-extruding, vacuum extruding, primary drying, sorting and collecting defective products, secondary drying, sorting and collecting defective products, cutting, collecting and cutting off materials, calcining, sorting defective products and packaging;
2) preparing ammonium metavanadate (the final active component of the catalyst is 0.5 percent by mass), adding 40L of deionized water into an ammonium metavanadate dissolving tank, adding 4.54kg of monoethanolamine, heating to 90 ℃, adding 4.54kg of ammonium metavanadate, continuously heating to 98 ℃, and keeping for 30 min;
3) mixing, namely adding 275kg of titanium-tungsten powder, 96kg of titanium-tungsten silicon powder, 1.5kg of stearic acid, 50L of ammonia water, 200kg of slurry, 85L of deionized water and 7.5kg of lactic acid with the mass fraction of 50%, mixing, and mixing;
4) the pre-extrusion and vacuum extrusion methods are unchanged;
5) weighing 200kg of defective products generated by primary drying and secondary drying and cutting-off materials (the content of active ingredients is 0.6%) generated by cutting, adding into a slurry tank, adding 800kg of deionized water, and continuously stirring for 4 hours, wherein the analyzed slurry concentration is 16.27%; the first-stage drying and sorting defective products do not enter second-stage drying, the second-stage drying and sorting defective products and cutting materials do not enter calcining, the first-stage drying defective products, the second-stage drying defective products and the cutting materials are collected, active ingredients are labeled, and the pulp melting process is carried out;
the specific surface areas of the slurried defective products, the cut-off materials and the titanium-tungsten powder are changed within the range shown in the following table:
6) and collecting the calcined defective products and sending the calcined defective products to a solid waste unit for treatment.
The raw materials used in the invention are common raw materials in the production in the field, can be obtained from the market, and do not influence the production result; the various devices adopted in the invention are conventional devices used in the production process in the field, and the operation, parameters and the like of each device are carried out according to the conventional operations without special points.
Claims (1)
1. A method for recycling defective products and cut materials in the production process of a honeycomb type denitration catalyst is characterized by comprising the following steps:
(1) the production process flow of the catalyst is to adjust cutting to be before calcination, and the adjusted cutting is as follows: mixing, pre-extruding, vacuum extruding, primary drying, sorting and collecting defective products, secondary drying, sorting and collecting defective products, cutting, collecting and cutting off materials, calcining, sorting defective products and packaging;
(2) carrying out slurrying on defective products and cut materials generated before the calcining process, and analyzing the slurry concentration to prepare for mixing and adding;
(3) sending the calcined defective products to a solid waste treatment department;
sorting the products after the primary drying and the secondary drying are finished, sorting and collecting the defective products without entering the next working section, and marking the project names and the active substance content; cutting the secondary dried qualified product according to the project requirements, collecting the cut material, and labeling the project name and the active substance content;
200kg of slurry, titanium tungsten powder and titanium tungsten silicon powder are added during mixing in the step (1), and deionized water is added;
the method for pulping in the step (2) comprises the following steps: according to defective products and cutting materials: putting water into a pulping pool in a weight ratio of 1:4, and continuously stirring for 4 hours to decompose all defective products into water uniformly;
and (3) preparing an ammonium metavanadate solution according to the concentration of the slurry, wherein the formula is as follows:
y＝z-200kg*x％*n
wherein: y is the addition amount of ammonium metavanadate;
z is the amount of ammonium metavanadate added when the slurry is not added;
x% is the slurry concentration;
n is the mass percentage of ammonium metavanadate in the catalyst before slurrying;
the addition amount of the titanium tungsten powder is 300kg-200kg x% 0.8, wherein: 300kg is the addition amount of the original formula, x% is the slurry concentration, and 0.8 is the mass percentage of the titanium tungsten powder in the formula;
the adding amount of the titanium tungsten silicon powder is 100kg-200kg x% 0.1, wherein 100kg is the original adding amount of the titanium tungsten silicon powder, x% is the slurry concentration, and 0.1 is the mass percentage of the titanium tungsten silicon powder in the formula;
the addition amount of the deionized water is 250kg to 200kg (1-x%), wherein 250kg is the original addition amount, 200kg is the amount of the added slurry, and x% is the concentration of the slurry.
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| JP4516275B2 (en) * | 2003-01-24 | 2010-08-04 | 株式会社デンソー | Cordierite ceramic body manufacturing method |
| CN101979135B (en) * | 2010-10-21 | 2012-07-04 | 张丽莉 | Catalyst for removing NOx and preparation method thereof |
| CN102049317A (en) * | 2010-12-15 | 2011-05-11 | 重庆远达催化剂制造有限公司 | Recycling method of denitration catalyst waste and denitration catalyst prepared from denitration catalyst waste |
| KR101425375B1 (en) * | 2013-01-08 | 2014-07-31 | 한국과학기술연구원 | post-treatment method of carbon materials using dehydrocyclization and post-treated carbon materials using the same and polymer composite materials comprising thereof |
| CN103752347B (en) * | 2014-01-26 | 2015-11-18 | 南京宇行环保科技有限公司 | A kind of preparation method of Faveolate denitration catalyst |
| CN103736482B (en) * | 2014-01-26 | 2015-06-17 | 南京宇行环保科技有限公司 | Preparation method of continuous extrusion SCR (Selective Catalytic Reduction) denitration honeycomb catalyst |
| CN104741113B (en) * | 2015-04-02 | 2017-07-14 | 易能环境技术有限公司 | A kind of inexpensive denitrating catalyst and preparation method thereof |
| CN105126818B (en) * | 2015-08-28 | 2017-08-22 | 湖北省轻工业科学研究设计院 | A kind of wear-resisting anti-poisoning honeycomb fashion SCR denitration and preparation method thereof |
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