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CN-120695817-B - Integrated ceramic catalytic filter tube and preparation method and application thereof

CN120695817BCN 120695817 BCN120695817 BCN 120695817BCN-120695817-B

Abstract

The invention discloses an integrated ceramic catalytic filter tube and a preparation method and application thereof, belonging to the field of industrial flue gas treatment. The integrated ceramic catalytic filter tube comprises a ceramic filter tube substrate and a catalytic coating, wherein the raw materials of the catalytic coating comprise noble metal catalytic slurry and vanadium-based catalytic slurry, the noble metal catalytic slurry comprises a noble metal catalyst, the noble metal catalyst takes Nb-CeO 2 /WO 3 as a carrier and platinum and/or palladium as active ingredients, and the mass ratio of the active ingredients to the carrier is (0.1-0.15): 1. The catalytic coating obtained by compounding two different active catalytic slurries can mutually compensate the problem of insufficient activity of the other side in different temperature ranges, so that the overall multi-pollutant removal efficiency of the catalytic coating is improved, and the ceramic filter tube with a porous structure is used as a matrix material, so that the distribution of the catalytic slurries is facilitated, the interception of particle pollutants is facilitated, and the denitration and dust removal integration and the efficient treatment of the smoke multi-pollutants are realized.

Inventors

  • WANG HONGMING
  • CHEN JIANJUN
  • CUI DENG
  • MI JINXING
  • CHEN KAI
  • WU ZHAOXING

Assignees

  • 安徽紫朔环境工程技术有限公司
  • 清华大学

Dates

Publication Date
20260505
Application Date
20250623

Claims (6)

  1. 1. The integrated ceramic catalytic filter tube is characterized by comprising a ceramic filter tube substrate and a catalytic coating, wherein the raw materials of the catalytic coating comprise noble metal catalytic slurry and vanadium-based catalytic slurry; The noble metal catalyst slurry comprises a noble metal catalyst, wherein the noble metal catalyst takes Nb-CeO 2 /WO 3 as a carrier and takes metal platinum and/or palladium as active components, and the mass ratio of the active components to the carrier is (0.1-0.15): 1; the noble metal catalytic slurry comprises the following raw materials, by mass, 4-8wt% of a noble metal catalyst, 10-14wt% of a surfactant and the balance of water; The Nb-CeO 2 /WO 3 carrier comprises (0.4-0.6) cerium salt, tungsten salt and niobium salt in a mass ratio of (0.05-0.1); the noble metal catalyst is prepared by the following steps: Respectively dissolving cerium salt and tungsten salt in an alcohol solvent, then dropwise adding the cerium salt solution into the tungsten salt solution, stirring and mixing for 3-4 hours, standing for 20-25 hours, drying and calcining to obtain a CeO 2 /WO 3 carrier, dispersing niobium salt in water, adjusting the pH value to be neutral, adding the CeO 2 /WO 3 carrier, uniformly stirring, aging for 2-3 hours at 70-75 ℃, and finally carrying out suction filtration, washing, drying and calcining to obtain the Nb-CeO 2 /WO 3 carrier; Dissolving noble metal salt in water, adding a Nb-CeO 2 /WO 3 carrier, raising the temperature to 80-90 ℃, reacting for 2-3 hours, washing, drying and roasting to obtain a noble metal catalyst; The vanadium-based catalyst slurry comprises, by mass, 8-15% of a vanadium-based catalyst, 10-12% of a dispersing agent and the balance of water, wherein the vanadium-based catalyst comprises (90-92) titanium dioxide and (8-10) vanadium-based active ingredients.
  2. 2. The integrated ceramic catalytic filter tube of claim 1, wherein the vanadium-based active component comprises 93-94 wt% of ammonium metavanadate and 6-7 wt% of a catalytic promoter, and the catalytic promoter comprises ammonium metatungstate and/or ammonium heptamolybdate.
  3. 3. The integrated ceramic catalytic filter tube of claim 1, wherein the precious metal catalytic slurry has a loading of 0.05-0.15 wt% on the ceramic filter tube substrate, and the vanadium-based catalytic slurry has a loading of 10-20 wt% on the ceramic filter tube substrate.
  4. 4. The integrated ceramic catalytic filter tube of claim 1, wherein the catalytic coating is formed by coating a precious metal catalytic slurry on the surface of the ceramic filter tube substrate and then coating a vanadium-based catalytic slurry; Or the catalytic coating is formed by coating vanadium-based catalytic slurry on the surface of the ceramic filter tube matrix and then coating noble metal catalytic slurry; or the catalytic coating is formed by mixing noble metal catalytic slurry with vanadium-based catalytic slurry and then jointly coating the mixed catalytic slurry on the surface of the ceramic filter tube matrix.
  5. 5. A method for preparing an integrated ceramic catalytic filter tube according to any one of claims 1-4, comprising the following process steps: s1, dispersing a noble metal catalyst in water, adding a surfactant, and uniformly mixing to obtain noble metal catalytic slurry; s2, dispersing titanium dioxide in water, stirring and dispersing, then raising the temperature to 50-100 ℃, adding vanadium-based active ingredients, stirring and dissolving to form a vanadium-based catalyst, then adding a dispersing agent, and uniformly mixing to obtain vanadium-based catalytic slurry; S3, coating the noble metal catalytic slurry and the vanadium-based catalytic slurry on the surface of the ceramic filter tube substrate subjected to the drying treatment, forming a catalytic coating after drying, and finally roasting for 2-3 hours at 300-400 ℃ to obtain the integrated ceramic catalytic filter tube.
  6. 6. Use of an integrated ceramic catalytic filter tube according to any one of claims 1-4, characterized in that the integrated ceramic catalytic filter tube is used for the co-removal of industrial flue gas dust and multi-pollutants.

Description

Integrated ceramic catalytic filter tube and preparation method and application thereof Technical Field The invention relates to the field of industrial flue gas treatment, in particular to an integrated ceramic catalytic filter tube and a preparation method and application thereof. Background The coke is mainly used as a fuel and a recovery agent for iron making, and has wide application in a plurality of industries such as metallurgy, casting, chemical industry and energy. The coke yield in China is the first in the world, and biomass boilers, refractory material furnaces and the like in coke production and other industries have remarkable influence on energy structures, so that the rapid development of the industry in China can be greatly promoted. But coke production is also accompanied by serious atmospheric pollution problems. The flue gas generated by the coke oven and the medium and small industrial kiln has a large amount of conventional and non-conventional pollutants such as sulfur dioxide, dust, nitrogen oxides, non-methane total hydrocarbon and the like, and the long-term accumulation of the pollutants in the atmosphere can seriously damage the environment and damage the life health safety of human beings, so that with the gradual importance of environmental protection, the method has important significance on how to treat the pollutants effectively. The prior control measures for various pollution in the coke oven flue gas mainly comprise source control and terminal treatment, wherein the source control comprises blast furnace gas heating, flame path temperature reduction, air excess coefficient reduction, waste gas circulation and sectional heating technology, coke oven reinforcement, coke oven serial leakage reduction and the like, and the source control helps to reduce the generation of pollutants from the source. The tail end treatment comprises desulfurization, denitration, dust removal and other processes, wherein the common flue gas tail end treatment process is to carry out desulfurization, denitration and dust removal on flue gas respectively through different equipment, and is a series treatment process, but the process treatment unit used by the process method is more, the occupied area is large, the flow is complex, the process control is complex, and related equipment capable of treating non-methane total hydrocarbon is not available. In order to solve the problem, a dust-nitre catalytic filter tube is provided for the denitration and dedusting steps in industrial flue gas, and the cooperative treatment of various pollutants in the flue gas can be realized, but the current treatment means has poor removal efficiency, low removal rate at low temperature, no effective removal of non-methane total hydrocarbons in the flue gas and no efficient non-methane total hydrocarbon treatment method. Disclosure of Invention The invention provides an integrated ceramic catalytic filter tube and a preparation method and application thereof, which can solve the problems that various pollutants in industrial flue gas are difficult to efficiently remove in a synergic way and a method for efficiently treating non-methane total hydrocarbons is lacked in the prior art. In a first aspect, the invention provides an integrated ceramic catalytic filter tube, which comprises a ceramic filter tube matrix and a catalytic coating, wherein the raw materials of the catalytic coating comprise noble metal catalytic slurry and vanadium-based catalytic slurry; The noble metal catalyst slurry comprises a noble metal catalyst, wherein the noble metal catalyst takes Nb-CeO 2/WO3 as a carrier and takes metal platinum and/or palladium as an active ingredient, and the mass ratio of the active ingredient to the carrier is (0.1-0.15): 1. Preferably, the content of SiO 2 in the ceramic filter tube matrix is 40-60%, the content of Al 2O3 is 10-30%, and the specific surface area of the ceramic filter tube matrix is 10-15 m 2/g. By adopting the technical scheme, the noble metal catalytic liquid and the vanadium-based catalytic liquid are compounded on the ceramic filter tube, the denitration efficiency of the catalytic coating can be greatly improved by compounding the noble metal catalytic liquid and the vanadium-based catalytic liquid, the noble metal active ingredients can show good catalytic activity in a low-temperature zone, nitrides can be converted into nontoxic nitrogen and water, the vanadium-based active ingredients can realize pollutant conversion in a medium-high-temperature zone, and the problem of insufficient activity can be mutually compensated by different catalysts in different temperature zones, so that the overall high denitration rate is maintained. And the addition of the noble metal catalytic slurry can catalyze and remove non-methane total hydrocarbon in industrial flue gas, wherein the non-methane total hydrocarbon refers to all volatile hydrocarbon except methane, including alkane, alkene, aromatic hy