CN110743628A - Activating and regenerating agent for recovering activity of vanadium titanium-based SCR denitration catalyst of thermal power plant - Google Patents
Activating and regenerating agent for recovering activity of vanadium titanium-based SCR denitration catalyst of thermal power plant Download PDFInfo
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- CN110743628A CN110743628A CN201911000257.6A CN201911000257A CN110743628A CN 110743628 A CN110743628 A CN 110743628A CN 201911000257 A CN201911000257 A CN 201911000257A CN 110743628 A CN110743628 A CN 110743628A
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
- B01J38/52—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids oxygen-containing
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
- B01J38/54—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids halogen-containing
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
- B01J38/62—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids organic
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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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
- B01J38/66—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts using ammonia or derivatives thereof
Abstract
The invention discloses an activation regenerant for recovering the activity of a vanadium titanium-based SCR denitration catalyst of a thermal power plant, which comprises an activation regenerant A and an activation regenerant B, wherein the activation regenerant A and the activation regenerant B respectively comprise the following components in parts by weight: the activating and regenerating agent A comprises tetrabutylammonium fluoride, citric acid, sulfamic acid, alkylphenol ethoxylates and the balance of deionized water solvent; the activating and regenerating agent B comprises ammonium orthovanadate, ammonium paratungstate and the balance of deionized water solvent; the chemical agents are superior grade pure, and the deionized water is secondary deionized water or more grade pure water. The invention is applied to a thermal power plant, is used for activating and regenerating the catalyst of the SCR denitration system, can greatly improve the activity of the SCR denitration catalyst, not only reduces the denitration cost, but also reduces the secondary environmental pollution caused by landfill of the waste catalyst, and has important economic benefit.
Description
Technical Field
The invention relates to the technical field of SCR denitration in a thermal power plant, in particular to a regenerant for activating an SCR denitration catalyst.
Background
The nitrogen oxide in the flue gas discharged from a thermal power plant is one of the main atmospheric pollutants, and is also the main substance causing photochemical smog, acid rain and destroying the ozone layer. The Selective Catalytic Reduction (R) flue gas denitration technology is the most mature and effective method for controlling the standard emission of NOx at present. With the continuous increase of the service life of the SCR denitration catalyst, the activity of the catalyst is gradually reduced, so that the requirement of SCR denitration cannot be met, and the denitration catalyst needs to be replaced once being inactivated.
In the SCR denitration technology, the price of a catalyst serving as a core is high, the cost accounts for 40-60% of that of the SCR catalysis technology, and anatase-supported V is adopted2O5-WO3/TiO2The service life of the catalyst is 3-5 years, the catalyst exceeding the service life basically loses activity, and because the price of a new catalyst in the market is higher, a large amount of funds are consumed by directly replacing the catalyst; and the waste catalyst is used as solid waste, and if the waste catalyst is not properly disposed of, the waste catalyst will pollute the environment, and the capital and land for disposing the waste catalyst will further increase the cost of the denitration technology, so that most users can consider the regeneration treatment of the catalyst.
The catalyst inactivated by poisoning can be recycled by a regeneration method, and the regeneration cost of the catalyst is only 40-50% of the cost of the updated catalyst, so that the development of regeneration research on the SCR denitration catalyst can reduce the denitration cost and reduce the secondary environmental pollution generated by landfill of the waste catalyst, and has important practical significance.
The main reasons for the deactivation of the vanadium-titanium-based SCR denitration catalyst are pore blockage on the surface of the catalyst, fly ash deposition, alkali metal and alkaline earth metal poisoning, thermal sintering and the like. Firstly, the fly ash deposited on the surface of the catalyst can also become a physical barrier even if the fly ash does not react with the catalyst, so that reaction gas can not reach the pores of the catalyst for catalytic reaction; secondly, the extremely small particle size of the salt is also a major cause of the plugging of the catalyst pores.
In addition, the deposition of compounds of alkali metals and alkaline earth metals on the catalyst surface can cause severe deactivation of the catalyst. Previous studies have shown that catalyst poisoning by sodium compounds is a major cause of catalyst deactivation; larsson et al observed KCl and K with ICP-AES2The depth of SO4 immersion in the surface layer of the catalyst indicates that different types of potassium salts accumulate in different locations and concentrations in the surface layer of the catalyst and cause different levels of deactivation. According to the research on the catalyst system by CHEN and the like, the deactivation of the catalyst is directly related to the alkalinity of metal by researching the precursor of the poisoning substance loaded on the vanadium-titanium catalyst, and the toxicity of the catalyst is sequentially K & gt Na & gt Ca & gt Mg according to the alkalinity. In view of the above, the above-mentioned researchers' research results on the deactivation of catalyst poisoning will be used to develop a total catalyst activating and regenerating agent.
Disclosure of Invention
The invention aims to provide an activating and regenerating agent for a vanadium titanium-based inactivated SCR denitration catalyst in a thermal power plant, which is used for improving the activity of the vanadium titanium-based SCR denitration catalyst and reducing the denitration cost.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows.
An activation regenerant for recovering the activity of a vanadium titanium-based SCR denitration catalyst in a thermal power plant comprises an activation regenerant A and an activation regenerant B, wherein the activation regenerant A and the activation regenerant B respectively comprise the following components in parts by weight: the activating and regenerating agent A comprises 0.1-0.3% of tetrabutylammonium fluoride (TBAF), 10.0-15.0% of citric acid, 3.0-5.0% of sulfamic acid, 1.0-2.0% of alkylphenol polyoxyethylene, and the balance of deionized water solvent, wherein the total amount of raw materials is 100.0%; the activating and regenerating agent B comprises 3.0-5.0% of ammonium orthovanadate, 15-25.0% of ammonium paratungstate and the balance of deionized water solvent, and the total amount of the raw materials is 100.0%; the chemical agents are superior grade pure, and the deionized water is secondary deionized water or more grade pure water.
The activating and regenerating agent A and the activating and regenerating agent B for recovering the activity of the vanadium titanium-based SCR denitration catalyst in the thermal power plant respectively comprise the following components in parts by weight: the activating and regenerating agent A comprises 0.2-0.3% of tetrabutylammonium fluoride (TBAF), 12.0-13.0% of citric acid, 4.0-5.0% of sulfamic acid, 1.5-1.8% of alkylphenol polyoxyethylene, and the balance of deionized water solvent, wherein the total amount of raw materials is 100.0%; the activating and regenerating agent B comprises 3.0-4.0% of ammonium orthovanadate, 20-22.0% of ammonium paratungstate and the balance of deionized water solvent, and the total amount of the raw materials is 100.0%.
Due to the adoption of the technical scheme, the technical progress of the invention is as follows.
In the invention, citric acid and sulfamic acid in the activating regenerant A can dissolve metal substances which cause performance poisoning, such as alkali metals blocked in the denitration catalyst; tetrabutylammonium fluoride (TBAF) can dissolve SiO insoluble in other acids (such as sulfuric acid and the like)2Substances, further improving the cleaning efficiency of the catalyst; alkylphenol ethoxylates is a high-efficiency active agent and has the effect of improving the reaction efficiency; a proper amount of tetrabutylammonium fluoride (TBAF) is added into the regenerant, so that large-particle deactivated substances can be quickly disintegrated, the surfactant can more easily play a role, and the regeneration cleaning efficiency is improved. The ammonium orthovanadate and the ammonium paratungstate in the activating regenerant B have the functions of recovering and improving the activity of important elements of vanadium and tungsten in the catalyst.
The invention is applied to a thermal power plant, is used for activating and regenerating a catalyst of a vanadium-titanium-based SCR denitration system, is mainly used for removing the surface and deep hole blockage and deposited fly ash of the catalyst, and the deactivation faults of alkali metal and alkaline earth metal poisoning, thermal sintering and the like, thereby greatly improving the activity of the SCR denitration catalyst, not only reducing the denitration cost, but also reducing the secondary environmental pollution caused by the landfill of the waste catalyst, and has important economic and social significance.
Drawings
FIG. 1 is a graph comparing denitration efficiency after the same catalyst is regenerated under different activation modes.
Detailed Description
An activation regenerant for recovering the activity of a vanadium titanium-based SCR denitration catalyst in a thermal power plant comprises an activation regenerant A and an activation regenerant B, wherein the activation regenerant A and the activation regenerant B respectively comprise the following components in parts by weight.
The activating and regenerating agent A comprises 0.1-0.3% of tetrabutylammonium fluoride (TBAF), 10.0-15.0% of citric acid, 3.0-5.0% of sulfamic acid, 1.0-2.0% of alkylphenol polyoxyethylene, and the balance of deionized water solvent, wherein the total amount of raw materials is 100.0%. The activating and regenerating agent B comprises 3.0-5.0% of ammonium orthovanadate, 15-25.0% of ammonium paratungstate and the balance of deionized water solvent, and the total amount of the raw materials is 100.0%. The chemical agents are superior grade pure, and the deionized water is secondary deionized water or more grade pure water.
The present invention will be described in further detail below with reference to specific embodiments thereof.
Example 1
Preparing an activation regenerant A and an activation regenerant B: in two different and special SCR denitration catalyst cleaning devices, deionized water is used as a solvent to respectively prepare an activation regenerant A and an activation regenerant B. Wherein, the activating regenerant A comprises 0.2 percent of tetrabutylammonium fluoride (TBAF), 15.0 percent of citric acid, 3.0 percent of sulfamic acid, 1.0 percent of high-efficiency active agent alkylphenol polyoxyethylene, and the balance of deionized water solvent, and the total amount of the raw materials is 100.0 percent; 4.0 percent of ammonium orthovanadate, 18.0 percent of ammonium paratungstate and the balance of deionized water solvent in the activating and regenerating agent B, wherein the total amount of the raw materials is 100.0 percent. Respectively mechanically stirring the activation regenerant A and the activation regenerant B until the activation regenerant A and the activation regenerant B are uniformly mixed.
The activating and regenerating agent prepared in example 1 is used for activating the SCR denitration catalyst: firstly, cleaning the surface deposited ash of a failed SCR denitration catalyst by using a soft brush, and removing dirt and blocking impurities on the surface by combining a hard brush; secondly, putting the SCR denitration catalyst with the surface dirt removed completely into a cleaning device containing an activating and regenerating agent A for soaking and cleaning for 30 min; then placing the mixture in a cleaning device containing an activation regenerant B, soaking for 20min, and taking out; and finally, drying the taken-out SCR denitration catalyst for 3 hours by using dry air, and finishing the regeneration of the catalyst.
Example 2
Preparing an activation regenerant A and an activation regenerant B: in two different and special SCR denitration catalyst cleaning devices, deionized water is used as a solvent to respectively prepare an activation regenerant A and an activation regenerant B. Wherein, the activating regenerant A comprises 0.3 percent of tetrabutylammonium fluoride (TBAF), 12.0 percent of citric acid, 5.0 percent of sulfamic acid, 2.0 percent of high-efficiency active agent alkylphenol polyoxyethylene, and the balance of deionized water solvent, and the total amount of the raw materials is 100.0 percent; the activating and regenerating agent B comprises 5.0% of ammonium orthovanadate, 22.0% of ammonium paratungstate and the balance of deionized water solvent, and the total amount of the raw materials is 100.0%. Respectively mechanically stirring the activation regenerant A and the activation regenerant B until the activation regenerant A and the activation regenerant B are uniformly mixed.
The activating and regenerating agent prepared in example 2 is used for activating the SCR denitration catalyst: firstly, cleaning the surface deposited ash of a failed SCR denitration catalyst by using a soft brush, and removing dirt and blocking impurities on the surface by combining a hard brush; secondly, putting the SCR denitration catalyst with the surface dirt removed completely into a cleaning device containing an activating and regenerating agent A for soaking and cleaning for 25 min; then placing the mixture in a cleaning device containing an activation regenerant B, soaking for 25min, and taking out; and finally, drying the taken-out SCR denitration catalyst for 3 hours by using dry air, and finishing the regeneration of the catalyst.
Example 3 to example 5
Examples 3 to 5 are different from example 1 in the weight ratio of each component in the activated regenerant a and the activated regenerant B, as shown in the following table.
Comparative examples 1 to 3
Comparative example 1 is to activate the deactivated vanadium-titanium-based SCR denitration catalyst by using ultrasonic waves of the prior art, comparative example 2 is to activate the deactivated vanadium-titanium-based SCR denitration catalyst by using a bubbling regeneration technique of the prior art, comparative example 3 is to activate the deactivated vanadium-titanium-based SCR denitration catalyst by using a leaching regeneration technique of the prior art, and the vanadium-titanium-based SCR denitration catalyst activated by the three comparative examples and example 1 is used for denitration treatment under the same conditions, and the denitration efficiency is shown in fig. 1.
As can be seen from FIG. 1, the activity of the SCR denitration catalyst can be greatly improved by activating the deactivated SCR denitration catalyst, and the recovery rate is nearly 100%.
In addition, in terms of cost, compared with the method of directly replacing the fresh catalyst, the method for activating the inactivated vanadium-titanium-based SCR denitration catalyst can save the cost by more than 50%, for example, a 500MW coal-fired power station, the activated and regenerated SCR denitration catalyst can be recycled, 500-1000 ten thousand yuan can be saved every year, and the method is economic and obvious.
Claims (2)
1. An activation regenerant for recovering activity of vanadium titanium-based SCR denitration catalyst in a thermal power plant is characterized in that: the composite material comprises an activation regenerant A and an activation regenerant B, wherein the activation regenerant A and the activation regenerant B respectively comprise the following components in parts by weight:
activating and regenerating agent A: 0.1-0.3% of tetrabutylammonium fluoride, 10.0-15.0% of citric acid, 3.0-5.0% of sulfamic acid, 1.0-2.0% of alkylphenol polyoxyethylene, and the balance of deionized water solvent, wherein the total amount of the raw materials is 100.0%;
activating the regenerant B: 3.0-5.0% of ammonium orthovanadate, 15-25.0% of ammonium paratungstate and the balance of deionized water solvent, wherein the total amount of raw materials is 100.0%;
the chemical agents are superior grade pure, and the deionized water is secondary deionized water or more grade pure water.
2. The activating and regenerating agent for recovering the activity of the vanadium titanium based SCR denitration catalyst in the thermal power plant as claimed in claim 1, wherein: the activating regenerant A and the activating regenerant B respectively comprise the following components in parts by weight:
activating and regenerating agent A: 0.2-0.3% of tetrabutylammonium fluoride, 12.0-13.0% of citric acid, 4.0-5.0% of sulfamic acid, 1.5-1.8% of alkylphenol polyoxyethylene, and the balance of deionized water solvent, wherein the total amount of the raw materials is 100.0%;
activating the regenerant B: 3.0-4.0% of ammonium orthovanadate, 20-22.0% of ammonium paratungstate and the balance of deionized water solvent, wherein the total amount of the raw materials is 100.0%.
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Citations (6)
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| CN103143402A (en) * | 2011-12-07 | 2013-06-12 | 徐树元 | Flue gas denitrification catalyst on-line regeneration cleaning liquid and preparation method thereof |
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| CN104562054A (en) * | 2014-12-10 | 2015-04-29 | 中核四川环保工程有限责任公司 | Chemical efficient detergent as well as preparation method and using method thereof |
| CN105080622A (en) * | 2015-09-14 | 2015-11-25 | 中建中环工程有限公司 | Regeneration method for inactivated selective catalytic reduction (SCR) denitration catalyst |
| CN107921420A (en) * | 2015-07-10 | 2018-04-17 | 三菱日立电力系统株式会社 | The renovation process of denitrating catalyst and the cleaning agent of the regenerative system of denitrating catalyst and denitrating catalyst |
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- 2019-10-21 CN CN201911000257.6A patent/CN110743628A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102764675A (en) * | 2011-05-05 | 2012-11-07 | 中国科学院城市环境研究所 | Formula for coal-fired flue gas denitrification catalyst activity regeneration |
| CN103143402A (en) * | 2011-12-07 | 2013-06-12 | 徐树元 | Flue gas denitrification catalyst on-line regeneration cleaning liquid and preparation method thereof |
| CN103143401A (en) * | 2011-12-07 | 2013-06-12 | 徐树元 | Flue gas denitrification catalyst on-line regeneration activator liquid and preparation method thereof |
| CN104562054A (en) * | 2014-12-10 | 2015-04-29 | 中核四川环保工程有限责任公司 | Chemical efficient detergent as well as preparation method and using method thereof |
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Application publication date: 20200204 |