CN112675833A - SCR catalyst module and preparation method thereof - Google Patents

SCR catalyst module and preparation method thereof Download PDF

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CN112675833A
CN112675833A CN202011572634.6A CN202011572634A CN112675833A CN 112675833 A CN112675833 A CN 112675833A CN 202011572634 A CN202011572634 A CN 202011572634A CN 112675833 A CN112675833 A CN 112675833A
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scr catalyst
donor
sio
hydrogel
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汪澜
盛斌
卢蓓
盛树堂
李冰冰
孙花英
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Zhejiang Shengwang Environmental Engineering Co ltd
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Zhejiang Shengwang Environmental Engineering Co ltd
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Abstract

The invention discloses an SCR catalyst module and a preparation method thereof, wherein the SCR catalyst module comprises an active component and a hardening component, and the active component is as followsIs less composed of V2O5Or WO3One of (1); the hardening component is Al2O3‑SiO2(ii) a The hardening component forms a nano silicon-aluminum gel film network on the surface of the active component. The nano silicon-aluminum gel film network can effectively reduce the abrasion loss of the SCR denitration catalyst and prolong the service life of the SCR denitration catalyst.

Description

SCR catalyst module and preparation method thereof
Technical Field
The invention relates to the technical field of emission reduction of atmospheric pollutants, in particular to an SCR catalyst module and a preparation method thereof.
Background
NOx is one of the main atmospheric pollutants because of its strong environmental problems such as acid rain, photochemical smog, haze, ozone layer destruction, etc., and threatens human health. In the field of removal of fixed source NOx of industrial kilns, the most mature technology in the world is selective catalytic reduction denitration (SCR). The SCR catalyst is a core component of the technology, and the chemical composition and the physical structure of the SCR catalyst have a crucial influence on the denitration efficiency.
Research on SCR catalysts began in the middle and late 19 th century and has been commercialized for years. At present, the commercial SCR denitration catalyst is basically V2O5-WO3(MoO3)/TiO2A catalyst. However, industrial flue gas in China, such as coal-fired power plants, cement industry, glass industry and the like, contains high-content dust, trace heavy metals and SO2And the like. When flue gas passes through the gas flow channels of the catalyst, the catalyst can be abraded, blocked and poisoned under high space velocity conditions. The catalyst can recover activity through regeneration after being blocked and poisoned; however, catalyst attrition is not regenerable, which is an important factor in reducing the denitration efficiency and life of SCR catalysts.
Therefore, it is an urgent technical problem to be solved by those skilled in the art to provide an SCR catalyst module capable of reducing the abrasion of the end of the catalyst module.
Disclosure of Invention
In order to solve the technical problem, the invention provides an SCR catalyst module and a preparation method thereof.
According to one aspect of the present application, there is providedAn SCR catalyst module is provided, comprising an active component and a hardening component, the active component comprising at least V2O5Or WO3One of (1); the hardening component is Al2O3-SiO2(ii) a The hardening component forms a nano silicon-aluminum gel film network on the surface of the active component.
Optionally, a hardening constituent Al2O3-SiO2From gamma-Al2O3And SiO2And (3) reacting.
Optionally, the active ingredient comprises V2O5Or WO3；
V in the active ingredient2O5Is prepared by vanadium donor reaction; in the active ingredient WO3Is prepared by the reaction of a tungsten donor;
the vanadium donor is metavanadate;
the tungsten donor is tungstate, metatungstate or paratungstate.
Optionally, the active ingredient comprises V2O5Or WO3；
V in the active ingredient2O5Is prepared by vanadium donor reaction; in the active ingredient WO3Is prepared by the reaction of a tungsten donor;
the vanadium donor is selected from one or more of sodium metavanadate, ammonium metavanadate or potassium metavanadate;
the tungsten donor is selected from one or more of ammonium metatungstate, ammonium paratungstate, ammonium tungstate or tungsten nitrate.
According to another aspect of the present application, there is provided a method of preparing an SCR catalyst module, comprising the steps of:
s1, dissolving vanadium donor and/or tungsten donor and template agent in deionized water or absolute ethyl alcohol, stirring for reaction to obtain gel containing active components, and calcining to obtain primary catalyst;
s2, adding the biomass ash treated by the acidic solution into the alkaline solution, mixing and stirring to obtain a biomass ash mixed solution, filtering the biomass ash mixed solution to obtain a filter residue, and dissolving the filter residue by ammonia water to obtain the product mainly containing SiO2The first solution of (a); mixing gamma-Al2O3Dissolving the powder in absolute ethyl alcohol to prepare the gamma-Al2O3Solution to gamma-Al2O3Adding a predetermined amount of the first solution into the solution, reacting to obtain a second solution, and placing the second solution into absolute ethyl alcohol for solvent replacement to obtain Al2O3-SiO2A hydrogel;
s3 impregnating the primary catalyst with Al2O3-SiO2In the hydrogel, Al is added to the primary catalyst2O3-SiO2After the hydrogel is adsorbed, Al is adsorbed2O3-SiO2And (3) placing the primary catalyst of the hydrogel in a preset drying atmosphere for drying, and calcining to obtain the SCR catalyst module.
Optionally, an SCR catalyst may also be added to the template gel in step S1, which is specifically performed by:
dissolving vanadium donor and/or tungsten donor and template agent in deionized water or absolute ethyl alcohol, stirring and reacting to obtain gel containing active components, soaking the SCR catalyst in the gel containing active components, adsorbing the gel containing active components by the SCR catalyst, and calcining to obtain the primary catalyst.
Optionally, step S1 specifically includes:
dissolving a vanadium donor, a tungsten donor and a template in deionized water or absolute ethyl alcohol to prepare a mixed solution, placing the mixed solution at the temperature of 30-50 ℃, carrying out oil bath reaction at a constant temperature for 2-48 hours, then carrying out magnetic stirring and heating on the mixed solution to obtain a gel containing active components, and obtain a template hydrogel, wherein the concentration of the vanadium donor in the mixed solution is 0.5-5 mol/L, the concentration of the tungsten donor in the mixed solution is 2-5 mol/L, and the concentration of the template is 0.02-0.3 g/ml;
dipping an SCR catalyst into template hydrogel, after the SCR catalyst adsorbs the template hydrogel, after the SCR catalyst adsorbing the template hydrogel is dried, placing the dried SCR catalyst in a nitrogen atmosphere for calcination, and calcining at the temperature of 350-600 ℃ for 1-10 hours to obtain the primary catalyst.
Optionally, step S2 specifically includes:
pyrolyzing the biomass particles to obtain biomass ash, and treating the biomass ash with an acidic solution;
adding biomass ash treated by an acidic solution into an alkaline solution to prepare a biomass ash mixed solution with the biomass ash concentration of 0.05-5 g/mL, filtering the biomass ash mixed solution to obtain filter residue, and adding ammonia water into the filter residue to adjust the filter residue to be neutral or weakly alkaline to obtain a first solution;
adding 6-10% of gamma-Al into absolute ethyl alcohol according to volume percentage2O3Uniformly stirring to obtain gamma-Al2O3The molar ratio of aluminum to silicon is 0.5-8: 1, and adding gamma-Al into the solution2O3Adding the first solution into the solution, and performing ultrasonic dispersion to obtain a second solution;
placing the second solution in 3-20 times volume of absolute ethyl alcohol for solvent replacement for 12-24 hours, and repeating for 3-6 times to obtain Al2O3-SiO2A hydrogel.
Alternatively, the specific operation of pyrolyzing the biomass particles to obtain the biomass ash in step S21 is as follows:
adding 0.02 wt% -0.05 wt% of auxiliary agent into biomass particles with the particle size of 40-80 meshes to form a biomass particle mixture, wherein the auxiliary agent is selected from one or more of potassium chloride, potassium dihydrogen phosphate, calcium hydroxide and sodium carbonate;
placing the biomass particle mixture in an oxygen-free atmosphere, and carrying out pyrolysis treatment at the pyrolysis temperature of 500-1000 ℃ for 15-60 minutes to obtain biomass ash;
and treating the biomass ash by using a mixed acid of hydrochloric acid and nitric acid, wherein the volume ratio of the hydrochloric acid to the nitric acid in the mixed acid is 1: 0.3-3.
Optionally, step S3 specifically includes:
impregnating the primary catalyst with Al2O3-SiO2In the hydrogel, Al is added to the primary catalyst2O3-SiO2After the hydrogel is adsorbed, Al is adsorbed2O3-SiO2The primary catalyst of the hydrogel is placed in CO2In the atmosphere, at a temperature of 30-120 DEG CDrying for 3-12 hours, then carrying out heat treatment at the temperature of 900-.
The SCR catalyst module comprises an active component, a template agent and a hardening component, wherein the hardening component forms a nano silicon-aluminum gel film network on the surface of the active component. The nano silicon-aluminum gel film network can effectively reduce the abrasion loss of the SCR denitration catalyst and prolong the service life of the SCR denitration catalyst.
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The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a flow chart of a method of making an SCR catalyst module in an embodiment.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. It should be noted that, in the embodiments and examples of the present application, the feature vectors may be arbitrarily combined with each other without conflict.
NOx is one of the main atmospheric pollutants because of its strong environmental problems such as acid rain, photochemical smog, haze, ozone layer destruction, etc., and threatens human health. In the field of removal of fixed source NOx of industrial kilns, the most mature technology in the world is selective catalytic reduction denitration (SCR). The SCR catalyst is a core component of the technology, and the chemical composition and the physical structure of the SCR catalyst have a crucial influence on the denitration efficiency.
Research on SCR catalysts began in the middle and late 19 th century and has been commercialized for years. Commercial SCR denitration catalyst at presentIs substantially V2O5-WO3(MoO3)/TiO2A catalyst. However, industrial flue gas in China, such as coal-fired power plants, cement industry, glass industry and the like, contains high-content dust, trace heavy metals and SO2And the like. When flue gas passes through the gas flow channels of the catalyst, the catalyst can be abraded, blocked and poisoned under high space velocity conditions. The catalyst can recover activity through regeneration after being blocked and poisoned; however, catalyst attrition is not regenerable, which is an important factor in reducing the denitration efficiency and life of SCR catalysts.
The application provides an SCR catalyst module comprising an active component and a hardening component, the active component comprising at least V2O5Or WO3One kind of (1). The hardening component is Al2O3-SiO2And the hardening component forms a nano silicon-aluminum gel film network on the surface of the active component. The nano silicon-aluminum gel film network can effectively reduce the abrasion loss of the SCR denitration catalyst and prolong the service life of the SCR denitration catalyst.
The SCR catalyst module of the present application comprises an active component and a hardening component, the active component comprising at least V2O5Or WO3One kind of (1).
The hardening component is Al2O3-SiO2And the hardening component forms a nano silicon-aluminum gel film network on the surface of the active component.
The hardening component forms a nano silicon-aluminum gel film network on the surface of the catalyst, and the nano silicon-aluminum gel film network is a micro-nano multiphase rough structure, so that the surface energy can be greatly reduced, and the super-hydrophobic property is achieved, thereby realizing the antistatic property and preventing smoke dust friction; al (Al)2O3-SiO2The formed nano silicon-aluminum gel film network has the advantages of increased film flux, high mechanical strength, pollution resistance, uniform film aperture and thin film wall, and can remarkably relieve the pollution of dust and trace heavy metals to the catalyst module by covering the surface of the catalyst module, so that the catalyst module has a self-cleaning function. The nano silicon-aluminum gel film network can effectively ventilate, insulate water and prevent dust, and effectively slow down the smoke of the catalyst module at high airspeedThe wear in the channels improves the wear resistance of the catalyst module, thereby improving the service life of the catalyst module. And Al2O3-SiO2The cost is low, and the method is simple and easy to obtain.
Wherein the hardening component Al2O3-SiO2From gamma-Al2O3And SiO2And (3) reacting to obtain the compound.
γ-Al2O3In the structure of (1), oxygen ions are approximately cubic face-centered close packing, Al3+Is irregularly distributed in the channel O2-The octahedron and the tetrahedron gaps are formed by the enclosing. gamma-Al2O3The porous material has an internal surface area of hundreds of square meters per gram, has strong adsorption capacity and catalytic activity, and can be regenerated and reused after being heated below 175 ℃ for 6-8 h.
γ-Al2O3Has better high-temperature performance, but has gel state gamma-Al2O3After 1000 ℃, phase change can occur, the structure collapses, and gamma-Al2O3And SiO2Formed Al2O3-SiO2Better high temperature stability, Al2O3-SiO2The nano silicon-aluminum gel film network formed on the catalyst module has good high-temperature stability, and can reduce the high-temperature abrasion of the catalyst module in high-temperature flue gas.
Wherein the active component comprises V2O5Or WO3. V in the active ingredient2O5Is prepared by vanadium donor reaction; in the active ingredient WO3Is prepared by reacting tungsten donor.
The vanadium donor is metavanadate. The tungsten donor is tungstate, metatungstate or paratungstate.
As one embodiment of the present application, the active component includes V2O5Or WO3。
V in the active ingredient2O5Is prepared by vanadium donor reaction; in the active ingredient WO3Is prepared by reacting tungsten donor.
The vanadium donor is selected from one or more of sodium metavanadate, ammonium metavanadate or potassium metavanadate.
The tungsten donor is selected from one or more of ammonium metatungstate, ammonium paratungstate, ammonium tungstate or tungsten nitrate.
As one embodiment of the present application, an SCR catalyst module includes an SCR catalyst, an active component including at least V, and a hardening component2O5Or WO3One of (1), the hardening component is Al2O3-SiO2And the hardening component forms a nano silicon-aluminum gel film network on the surface of the active component.
In this embodiment, the added SCR catalyst can be a molded dried SCR catalyst monomer or a regenerated SCR catalyst. The denitration performance of the SCR catalyst is reduced after the SCR catalyst is used for a period of time, the service life of the SCR denitration catalyst is only 2-3 years, the cost of the SCR catalyst is very high, and the inactivated SCR catalyst has extremely strong toxic action on human bodies and the environment if not properly treated. If the deactivated catalyst is subjected to regeneration treatment, the service life of the SCR catalyst can be effectively prolonged. And the denitration effect and the anti-attrition effect of the regenerated SCR catalyst may be deteriorated.
In the embodiment, the introduction of the active component can reduce defects (such as pores, microcracks and the like) generated in the preparation and processing of the SCR catalyst, when the added SCR catalyst is a regenerated SCR catalyst, the active component can repair or slow down the microcracks generated in the actual gas denitration application process of the SCR catalyst to a certain extent, so that the surface of the SCR catalyst is hardened, the wear resistance of the SCR catalyst is further improved, the method is suitable for recycling the regenerated SCR catalyst, and the treated regenerated catalyst has good denitration capability and wear resistance.
As a preferred example of this embodiment, the active ingredient comprises V2O5And WO3(ii) a V in the active component by mass fraction2O50.3-3 wt% of SCR catalyst, and WO in active component3Accounting for 0.5-5 wt% of the SCR catalyst.
The preparation method of the SCR catalyst module comprises the following steps:
s1, dissolving vanadium donor and/or tungsten donor and template agent in deionized water or absolute ethyl alcohol, stirring for reaction to obtain gel containing active components, and calcining at low temperature to obtain primary catalyst;
s2, adding the biomass ash treated by the acidic solution into the alkaline solution, mixing and stirring to obtain a biomass ash mixed solution, filtering the biomass ash mixed solution to obtain a filter residue, and dissolving the filter residue by ammonia water to obtain the product mainly containing SiO2The first solution of (a); mixing gamma-Al2O3Dissolving the powder in absolute ethyl alcohol to prepare the gamma-Al2O3Solution to gamma-Al2O3Adding a predetermined amount of the first solution into the solution, reacting to obtain a second solution, and placing the second solution into absolute ethyl alcohol for solvent replacement to obtain Al2O3-SiO2A hydrogel.
S3 impregnating the primary catalyst with Al2O3-SiO2In the hydrogel, Al is added to the primary catalyst2O3-SiO2After the hydrogel is adsorbed, Al is adsorbed2O3-SiO2And (3) placing the primary catalyst of the hydrogel in a preset drying atmosphere for drying, and calcining to obtain the SCR catalyst module.
In step S2, biomass ash is used as a wear-resistant reprocessed silicon donor, and waste materials are used to reduce production costs. The method comprises the steps of enabling biomass ash to pass through an acid solution, dissolving the biomass ash treated by the acid solution with the alkali solution, separating silicon dioxide in the biomass ash by an alkali cooking precipitation method, filtering to obtain filter residue, and dissolving the filter residue with ammonia water to obtain the biomass ash mainly containing SiO2First solution of (2), SiO in the first solution2The concentration of (A) is 80-95 wt%.
After the first solution and the second solution are mixed, SiO in the first solution2And gamma-Al in the second solution2O3Reacting to obtain Al2O3-SiO2Hydrogel, Al2O3-SiO2The hydrogel has the advantages of uniform accumulation and dispersion of active components, and high desulfurization and denitrification activity.
Step S3In the method, nano Al is formed on the surface of the primary catalyst by an immersion method2O3-SiO2Gel film, nano Al after heat treatment2O3-SiO2Sintering of gel, nano Al2O3-SiO2The gel particles are mutually bonded and strengthened to form a nano silicon-aluminum gel film network on the surface of the catalyst. The nano silicon-aluminum gel film network has a multiphase rough structure, can greatly reduce the surface energy, is similar to the surface of a catalyst with a self-cleaning structure, can effectively ventilate, insulate water and prevent dust, and finally greatly improves the wear resistance of the catalyst.
As an embodiment of the present application, an SCR catalyst may be further added to the template gel in step S1, which is specifically performed by:
dissolving a vanadium donor and/or a tungsten donor and a template agent in deionized water or absolute ethyl alcohol, stirring for reaction to obtain gel containing an active component, soaking the SCR catalyst in the gel containing the active component, and calcining after the SCR catalyst is adsorbed by the gel containing the active component to obtain the primary catalyst.
In this embodiment, the added SCR catalyst can be a molded dried SCR catalyst monomer or a regenerated SCR catalyst.
In this example, the SCR catalyst was impregnated in an active component-containing gel, and after the SCR catalyst was adsorbed by the active component-containing gel, it was calcined to obtain a primary catalyst. The gel coated SCR catalyst containing the active component is used for supplementing the active component, and the denitration capability of the SCR catalyst is improved.
As an embodiment of the present application, step S1 specifically operates as follows:
dissolving a vanadium donor, a tungsten donor and a template agent in deionized water or absolute ethyl alcohol to prepare the template agent hydrogel, carrying out oil bath reaction for 2-48 hours at a constant temperature at the temperature of 30-50 ℃, and then magnetically stirring and heating the composite solution to obtain the gel containing the active component, thereby obtaining the template agent hydrogel.
Dipping an SCR catalyst into template hydrogel, after the SCR catalyst adsorbs the template hydrogel, after the SCR catalyst adsorbing the template hydrogel is dried, placing the dried SCR catalyst in a nitrogen atmosphere for calcination, and calcining at the temperature of 350-600 ℃ for 1-10 hours to obtain the primary catalyst.
As an embodiment of the present application, the specific operation of dissolving the vanadium donor, the tungsten donor and the template in deionized water or absolute ethanol to prepare a mixed solution in step S1 is as follows:
dissolving a vanadium donor, a tungsten donor and a template agent in deionized water or absolute ethyl alcohol to prepare a mixed solution, wherein the concentration of the vanadium donor in the mixed solution is 0.5-5 mol/L, the concentration of the tungsten donor in the mixed solution is 2-5 mol/L, and the concentration of the template agent in the mixed solution is 0.02-0.3 g/ml.
The vanadium donor is selected from one or more of sodium metavanadate, ammonium metavanadate or potassium metavanadate.
The tungsten donor is selected from one or more of ammonium metatungstate, ammonium paratungstate, ammonium tungstate or tungsten nitrate.
The template agent is selected from a biopolymer or an anionic surfactant, and can form a molecular membrane on the surface of the SCR denitration catalyst module to prevent the loss of active components.
As an embodiment of the present application, the template is selected from rice flour, starch, maltodextrin, chitosan, gelatin, glucose, Sodium Dodecyl Sulfate (SDS), and the like, has biodegradability, surface activity and good compatibility, and can form a polymer film on the surface of the SCR denitration catalyst to prevent the loss of the active components of the catalyst.
As an embodiment of the present application, step S2 specifically operates as follows:
pyrolyzing the biomass particles to obtain biomass ash, and treating the biomass ash with an acidic solution;
adding the biomass ash treated by the acidic solution into an alkaline solution to prepare a biomass ash mixed solution with the biomass ash concentration of 0.05-5 g/mL, filtering the biomass ash mixed solution to obtain filter residue, and adding ammonia water into the filter residue to adjust the filter residue to be neutral or weakly alkaline to obtain a first solution.
Adding 6-10% of gamma-Al into absolute ethyl alcohol according to volume percentage2O3Uniformly stirring to obtain gamma-Al2O3The molar ratio of aluminum to silicon is 0.5-8: 1, and adding gamma-Al into the solution2O3And adding the first solution into the solution, and performing ultrasonic dispersion to obtain a second solution.
Placing the second solution in 3-20 times volume of absolute ethyl alcohol for solvent replacement for 12-24 hours, and repeating for 3-6 times to obtain Al2O3-SiO2A hydrogel.
As an embodiment of the present application, the operation of pyrolyzing biomass particles to obtain biomass ash in step S21 is specifically as follows:
adding 0.02 wt% -0.05 wt% of auxiliary agent into biomass particles with the particle size of 40-80 meshes to form a biomass particle mixture, wherein the auxiliary agent is selected from one or more of potassium chloride, potassium dihydrogen phosphate, calcium hydroxide and sodium carbonate.
And (3) putting the biomass particle mixture in an oxygen-free atmosphere, and carrying out pyrolysis treatment at the pyrolysis temperature of 500-1000 ℃ for 15-60 minutes to obtain biomass ash.
And treating the biomass ash by using a mixed acid of hydrochloric acid and nitric acid, wherein the volume ratio of the hydrochloric acid to the nitric acid in the mixed acid is 1: 0.3-3.
As an embodiment of the present application, the operation of pyrolyzing biomass particles to obtain biomass ash in step S21 is specifically as follows:
preparing biomass raw materials for later use, wherein the biomass raw materials comprise one or more of sorghum straws, peanut stalks, coconut shells, soybean stalks, walnut shells, corncobs, corn stalks, green bamboos, rice hulls, woods, oil algae, kelp, peach trees, pine trees and the like.
The biomass raw material is subjected to particle size grading control through a crusher and a vibrating screen machine, and biomass particles within the particle size range of 40-80 meshes are screened for later use.
Adding 0.02 wt% -0.05 wt% of auxiliary agent into biomass particles with the particle size of 40-80 meshes to form a biomass particle mixture, wherein the auxiliary agent is selected from one or more of potassium chloride, potassium dihydrogen phosphate, calcium hydroxide and sodium carbonate.
Placing the biomass particle mixture in a rotary calcining kiln, wherein the rotary calcining kiln is pure N2Gas atmosphere, pure CO2Gas atmosphere or N2And CO2And (3) in the mixed atmosphere, rotating the biomass particle mixture in a rotary calcining kiln at the rotating speed of 0.3-3.2 r/min, and pyrolyzing at the pyrolysis temperature of 500-1000 ℃ for 15-60 min to obtain biomass ash.
As a preferred embodiment of the present application, the biomass material is sorghum straw, under the condition, biomass ash obtained by pyrolyzing sorghum straw reacts to obtain a first solution, SiO2The concentration of (A) is 90% or more.
As an embodiment of the present application, step S3 specifically operates as follows:
impregnating the primary catalyst with Al2O3-SiO2In the hydrogel, Al is added to the primary catalyst2O3-SiO2After the hydrogel is adsorbed, Al is adsorbed2O3-SiO2The primary catalyst of the hydrogel is placed in CO2Drying at 30-120 ℃ for 3-12 hours in the atmosphere, then carrying out heat treatment at 900-1000 ℃ for 0.5-1 hour, and calcining to obtain the SCR catalyst module.
In step S3, the primary catalyst is re-impregnated with Al2O3-SiO2In the hydrogel, a nano silicon-aluminum gel film network is formed on the surface of the catalyst by an immersion method; after the heat treatment process, the nano particles are sintered, so that the bonding and the strengthening of the nano particles are realized. The nano silicon-aluminum gel film network covers the surface of the SCR catalyst module, so that the air permeability, water resistance and dust resistance can be effectively realized, and the wear resistance of the SCR catalyst module is greatly improved.
As an embodiment of the present application, a method of preparing an SCR catalyst module includes the steps of:
preparation of a primary catalyst: dissolving ammonium metavanadate, ammonium metatungstate and starch in absolute ethanol, adding ammonium metavanadate, ammonium metatungstate and starch into the absolute ethanol, controlling the concentration of the starch to be 0.02g/ml, stirring and reacting for 24 hours at constant temperature in an oil bath at 30 ℃, heating under magnetic stirring to obtain gel containing active components, dipping the SCR catalyst in the gel containing the active components, dipping for 12 hours under the condition of water bath vacuum pumping at 20 ℃, drying for 12 hours at 50 ℃ after the SCR catalyst is adsorbed by the gel containing the active components, calcining for 6 hours in a nitrogen atmosphere furnace at 350 ℃ and calcining to obtain the primary catalyst.
Preparation of Al2O3-SiO2The hydrogel specifically comprises the following steps:
the grain size of the sorghum straws is graded and controlled by a crusher and a vibrating screen machine, and biomass particles with the grain size range of 40-80 meshes are screened out. Adding 0.02 wt% of calcium hydroxide into the biomass particles to form a biomass particle mixture, and placing the biomass particle mixture in a rotary calcining kiln, wherein the rotary calcining kiln is pure N2And (3) in a gas atmosphere, rotating the biomass particle mixture in a rotary calcining kiln at the rotating speed of 1.5r/min, and pyrolyzing at the pyrolysis temperature of 500 ℃ for 60min to obtain biomass ash.
With HCl-HNO3Treating biomass ash with 5 wt% of mixed acid containing HCl and HNO3In a ratio of 1: 0.3; adding the biomass ash subjected to mixed acid treatment into an alkaline solution to prepare a biomass ash mixed solution with the biomass ash concentration of 0.1g/mL, wherein the alkaline solution is mainly NaOH and is supplemented with a small amount of alkaline solution of NaCl and HDTMA; mixing and stirring the biomass ash mixed solution at the temperature of 60 ℃ for 3h, after the reaction is finished, cooling, carrying out centrifugal suction filtration, passing through a cation filter to obtain filter residue, adding 1mol/L ammonia water into the filter residue to adjust the pH of the filter residue to 7.5, and carrying out ultrasonic treatment in an ultrasonic cleaner for several seconds to uniformly mix the solution to obtain a first solution;
adding 6 percent of gamma-Al into absolute ethyl alcohol by volume percentage2O3Uniformly stirring to obtain gamma-Al2O3Solution of gamma-Al in molar ratio of Al to Si of 5:12O3Adding the first solution into the solution, mixing and stirring for 0.5h, performing ultrasonic dispersion for 0.5h, adding 0.5g of ammonia water after the solution is in a uniform state, continuously performing ultrasonic dispersion for 0.5h, and standing at 20 ℃ for 48h to obtain a second solution.
Placing the second solution in 5 times volume of absolute ethyl alcohol for solvent replacement for 12 hours, repeating for 3 times to obtain Al2O3-SiO2A hydrogel.
Impregnating the primary catalyst inAl2O3-SiO2In the hydrogel, Al is added to the primary catalyst2O3-SiO2After the hydrogel is adsorbed, Al is adsorbed2O3-SiO2The primary catalyst of the hydrogel is placed in CO2In the atmosphere, the temperature is 30-120 ℃ for 3-12 hours, then the SCR catalyst module is obtained by processing at 900-1000 ℃ for 0.5-1 hour and calcining.
Preparing an SCR catalyst module: impregnating the primary catalyst with Al2O3-SiO23h in the hydrogel, adding Al to the primary catalyst2O3-SiO2After the hydrogel is adsorbed, Al is adsorbed2O3-SiO2The primary catalyst of the hydrogel is placed in CO2Drying at 30 ℃ for 3h in the atmosphere, treating at 900 ℃ for 0.5h, and calcining to obtain the SCR catalyst module
Specific embodiments of the SCR catalyst module are listed below:
examples
Table 1 shows some examples of specific amounts of components in an SCR catalyst module according to the invention. It is noted that the specific amounts of the components of the SCR catalyst module of the present invention are not limited to the data in table 1.
TABLE 1 SCR catalyst Module content examples
Figure BDA0002855551260000121
Wherein, the SCR catalyst of the embodiment 1-1 to the embodiment 1-4 is SCR catalyst material of Sibo Ying environmental protection science and technology corporation, the cargo number is SBY-14-776;
the SCR catalyst of examples 2-1 to 2-4 is an SCR catalyst material of Gem eco-Tech Co., Ltd, having a product number of TC 875043-2E.
Comparative test example
The performance of the SCR catalyst modules of examples 1-1 to 1-4, 2-1 to 2-4 and the SCR catalyst materials of comparative examples 1 and 2 was tested.
Wherein the SCR catalyst material of comparative example 1 is produced by Sibering environmental protection science and technology Co., Ltd, and has a product number of SBY-14-776;
the SCR catalyst material of comparative example 2 was prepared from environmental protection technologies of Gem, Inc., having a product number of TC 875043-2E.
And (3) wear performance testing: and (3) placing the catalyst to be tested in a constant-temperature oven at 120 +/-5 ℃ for continuous drying, then taking out and weighing, respectively recording as Mi, naturally cooling to room temperature, and then placing in a catalyst abrasion test platform for testing. I (arranged in turn as W) are placed in the test sample chamber1、W2……Wi) Adjusting the air speed and the feeding amount of a sample (quartz powder and the like), wearing for 2 hours, taking out, blowing dust on the surface of the sample by using compressed air, drying the sample in a constant-temperature oven at 120 +/-5 ℃, taking out and measuring the weight of the experimental sample, and respectively recording the weight as M1、M2……MiAnd W is used for calculating the abrasion rate and the abrasion loss of the sample.
And (3) life test: and the data screening module screens data points in a corresponding interval of the flue gas temperature and the flue gas flow rate with the longest operation time by calling the operation data of the SCR denitration device within nearly 1 year of the SCR denitration activity evaluation device and removes data points with abnormal parameters. And the life evaluation module calculates the critical activity of the catalyst when the catalyst reaches the service life through the operating parameters such as NOx inlet concentration and flue gas flow of the denitration device and pollutant emission standards, and further obtains the residual service life of the catalyst according to the activity attenuation rule of the catalyst.
And (3) testing the strength performance: and placing the molded catalyst on a platform of a testing machine, continuously pressurizing, and reading a maximum pressure value when the pressure suddenly drops. The apparatus can test the axial and radial mechanical strength of the catalyst.
And (3) testing the denitration activity: the catalyst to be tested is placed in a reactor of a catalyst evaluation device, and the simulated flue gas has the composition (volume ratio) of 800ppm NOx and NH3The flow rate was 1ml/min, 100ppm SO2，6％O2，12％CO2HCl flow 40ml/min, N2As carrier gas, the space velocity is 60000h-1And (6) carrying out testing. Specifically, as shown in table 2.
TABLE 2 SCR catalyst Module Performance test and comparison results
Figure BDA0002855551260000131
Figure BDA0002855551260000141
According to table 2, the abrasion weight loss rate of the SCR catalyst module is reduced by 18.8-25% compared with that of the existing SCR catalyst; the service life of the catalyst is improved by 15-25% compared with that of the existing SCR catalyst; the catalyst activity is improved by 4-13.3% compared with that of the existing SCR catalyst; the strength performance is also superior to the existing SCR catalyst.
It is to be noted that, in this document, the terms "comprises", "comprising" or any other variation thereof are intended to cover a non-exclusive inclusion, so that an article or apparatus including a series of elements includes not only those elements but also other elements not explicitly listed or inherent to such article or apparatus. Without further limitation, an element defined by the phrase "comprising … …" does not exclude the presence of additional like elements in the article or device comprising the element.
The above embodiments are merely to illustrate the technical solutions of the present invention and not to limit the present invention, and the present invention has been described in detail with reference to the preferred embodiments. It will be understood by those skilled in the art that various modifications and equivalent arrangements may be made without departing from the spirit and scope of the present invention and it should be understood that the present invention is to be covered by the appended claims.

Claims (10)

1. An SCR catalyst module comprising an active component and a hardening component, the active componentThe component at least comprises V2O5Or WO3One of (1);
the hardening component is Al2O3-SiO2；
The hardening component forms a nano silicon-aluminum gel film network on the surface of the active component.
2. The SCR catalyst module of claim 1, wherein the hardening component Al2O3-SiO2From gamma-Al2O3And SiO2And (3) reacting.
3. The SCR catalyst module of claim 1, wherein the active component comprises V2O5Or WO3；
V in the active ingredient2O5Is prepared by vanadium donor reaction; among the active ingredients WO3Is prepared by the reaction of a tungsten donor;
the vanadium donor is metavanadate;
the tungsten donor is tungstate, metatungstate or paratungstate.
4. The SCR catalyst module of claim 1, wherein the active component comprises V2O5Or WO3；
V in the active ingredient2O5Is prepared by vanadium donor reaction; among the active ingredients WO3Is prepared by the reaction of a tungsten donor;
the vanadium donor is selected from one or more of sodium metavanadate, ammonium metavanadate or potassium metavanadate;
the tungsten donor is selected from one or more of ammonium metatungstate, ammonium paratungstate, ammonium tungstate or tungsten nitrate.
5. A method of making an SCR catalyst module, comprising the steps of:
s1, dissolving vanadium donor and/or tungsten donor and template agent in deionized water or absolute ethyl alcohol, stirring for reaction to obtain gel containing active components, and calcining to obtain primary catalyst;
s2, adding the biomass ash treated by the acidic solution into the alkaline solution, mixing and stirring to obtain a biomass ash mixed solution, filtering the biomass ash mixed solution to obtain a filter residue, and dissolving the filter residue by ammonia water to obtain the product mainly containing SiO2The first solution of (a); mixing gamma-Al2O3Dissolving the powder in absolute ethyl alcohol to prepare the gamma-Al2O3Solution to gamma-Al2O3Adding a predetermined amount of first solution into the solution, reacting to obtain a second solution, and placing the second solution into absolute ethyl alcohol for solvent replacement to obtain Al2O3-SiO2A hydrogel;
s3 impregnating the primary catalyst with the Al2O3-SiO2In the hydrogel, the Al is added to the primary catalyst2O3-SiO2After the hydrogel is adsorbed, Al is adsorbed2O3-SiO2And placing the primary catalyst of the hydrogel in a preset drying atmosphere for drying, and calcining to obtain the SCR catalyst module.
6. The method according to claim 5, wherein the SCR catalyst is further added to the template gel in step S1, and the method comprises the following specific steps:
dissolving a vanadium donor and/or a tungsten donor and a template agent in deionized water or absolute ethyl alcohol, stirring and reacting to obtain gel containing an active component, soaking an SCR catalyst in the gel containing the active component, and calcining after the gel containing the active component is adsorbed by the SCR catalyst to obtain the primary catalyst.
7. The preparation method according to claim 5, wherein the step S1 specifically comprises the following steps:
dissolving a vanadium donor, a tungsten donor and a template in deionized water or absolute ethyl alcohol to prepare a mixed solution, placing the mixed solution at the temperature of 30-50 ℃, carrying out oil bath reaction at a constant temperature for 2-48 hours, then carrying out magnetic stirring and heating on the mixed solution to obtain a gel containing active components, and obtain a template hydrogel, wherein the concentration of the vanadium donor in the mixed solution is 0.5-5 mol/L, the concentration of the tungsten donor is 2-5 mol/L, and the concentration of the template is 0.02-0.3 g/ml;
dipping an SCR catalyst into the template hydrogel, after the SCR catalyst adsorbs the template hydrogel, after the SCR catalyst adsorbing the template hydrogel is dried, putting the dried SCR catalyst into a nitrogen atmosphere for calcination, and calcining at the temperature of 350-600 ℃ for 1-10 hours to obtain the primary catalyst.
8. The preparation method according to claim 5, wherein the step S2 specifically comprises the following steps:
pyrolyzing biomass particles to obtain biomass ash, and treating the biomass ash with an acidic solution;
adding biomass ash treated by an acidic solution into an alkaline solution to prepare a biomass ash mixed solution with the biomass ash concentration of 0.05-5 g/mL, filtering the biomass ash mixed solution to obtain filter residue, and adding ammonia water into the filter residue to adjust the filter residue to be neutral or weakly alkaline to obtain a first solution;
adding 6-10% of gamma-Al into absolute ethyl alcohol according to volume percentage2O3Uniformly stirring to obtain gamma-Al2O3The molar ratio of aluminum to silicon is 0.5-8: 1, and adding gamma-Al into the solution2O3Adding the first solution into the solution, and performing ultrasonic dispersion to obtain a second solution;
placing the second solution in absolute ethyl alcohol with the volume being 3-20 times of that of the second solution for solvent replacement for 12-24 hours, and repeating for 3-6 times to obtain Al2O3-SiO2A hydrogel.
9. The method of claim 8, wherein the step S21 of pyrolyzing biomass particles to obtain biomass ash is specifically performed by:
adding 0.02 wt% -0.05 wt% of auxiliary agent into biomass particles with the particle size of 40-80 meshes to form a biomass particle mixture, wherein the auxiliary agent is selected from one or more of potassium chloride, potassium dihydrogen phosphate, calcium hydroxide and sodium carbonate;
placing the biomass particle mixture in an oxygen-free atmosphere, and carrying out pyrolysis treatment at the pyrolysis temperature of 500-1000 ℃ for 15-60 minutes to obtain biomass ash;
and treating the biomass ash by using a mixed acid of hydrochloric acid and nitric acid, wherein the volume ratio of the hydrochloric acid to the nitric acid in the mixed acid is 1: 0.3-3.
10. The preparation method according to claim 5, wherein the step S3 specifically comprises the following steps:
impregnating the primary catalyst with the Al2O3-SiO2In the hydrogel, the Al is added to the primary catalyst2O3-SiO2After the hydrogel is adsorbed, Al is adsorbed2O3-SiO2The primary catalyst of the hydrogel is placed in CO2Drying at 30-120 ℃ for 3-12 hours in the atmosphere, then carrying out heat treatment at 900-1000 ℃ for 0.5-1 hour, and calcining to obtain the SCR catalyst module.
CN202011572634.6A 2020-12-23 2020-12-23 SCR catalyst module and preparation method thereof Pending CN112675833A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107597198A (en) * 2017-09-11 2018-01-19 北京方信立华科技有限公司 A kind of SCR denitration hardening hydrosol and preparation method thereof and method for curing
CN111715302A (en) * 2020-04-08 2020-09-29 上海大学 Anti-poisoning metal oxide denitration catalyst and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107597198A (en) * 2017-09-11 2018-01-19 北京方信立华科技有限公司 A kind of SCR denitration hardening hydrosol and preparation method thereof and method for curing
CN111715302A (en) * 2020-04-08 2020-09-29 上海大学 Anti-poisoning metal oxide denitration catalyst and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
叶恒棣: "《冶金工业出版社》", 31 May 2019 *
沈岳松等: "Ti-Al-Si-Ox 脱硝催化剂载体的组分优化及性能研究", 《无机材料学报》 *

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