CN117019143A - Denitration, decarbonization and deamination three-effect composite catalyst and preparation method thereof - Google Patents

Denitration, decarbonization and deamination three-effect composite catalyst and preparation method thereof Download PDF

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CN117019143A
CN117019143A CN202310898990.4A CN202310898990A CN117019143A CN 117019143 A CN117019143 A CN 117019143A CN 202310898990 A CN202310898990 A CN 202310898990A CN 117019143 A CN117019143 A CN 117019143A
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drying
cerium
solution
zirconium
precursor
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马帅
朱礼强
杭小玲
董立娜
常晨阳
刘金亮
韩雪茹
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Cecep Liuhe Tianrong Shandong Catalyst Co ltd
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Cecep Liuhe Tianrong Shandong Catalyst Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6527—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

The application provides a preparation method of a denitration, decarbonization and deamination three-way composite catalyst, which comprises the following steps: preparation of zirconium-cerium-tungsten composite oxide-TiO 2 Composite powder; preparing a vanadium compound solution; preparing a mixed pug; further processing the mixed pug to obtain a precursor; loading metal palladium or metal platinum or metal palladium and platinum on the precursor; and drying and calcining the loaded precursor to obtain the three-effect composite catalyst. The catalyst provided by the application adopts zirconium-cerium-tungsten composite oxide-TiO 2 Is a carrier, V 2 O 5 Pd or V 2 O 5 -Pt or V 2 O 5 Pd-Pt as active component, wherein V 2 O 5 The component can remove NO in the flue gas x Pd component, pt component, pd and Pt component can be removedCO、NH 3 And also on hydrocarbons (C) x H y ) The dioxin also has oxidation effect, so that the pollution of the discharged flue gas to the atmosphere can be effectively reduced.

Description

Denitration, decarbonization and deamination three-effect composite catalyst and preparation method thereof
Technical Field
The application relates to the technical field of denitration catalysts, in particular to a denitration, decarbonization and deamination three-way composite catalyst and a preparation method thereof.
Technical Field
At present, with the development of industry, the discharge amount of smoke is greatly increased, and the discharge of the smoke generates serious pollution to the environment, so that the smoke has attracted wide attention in all countries of the world. The pollutants in industrial flue gases mainly include nitrogen oxides (NO x )、SO 2 Dust, HCl, dioxin, CO, etc. Nitrogen Oxides (NO) x ) Mainly comprises NO and NO 2 、N 2 O、N 2 O 5 Wherein the NO accounts for more than 90 percent and is one of the main pollutants for global atmosphere pollution. Nitrogen Oxides (NO) x ) The emission of the water-based paint can generate environmental problems such as photochemical smog, acid rain, ozone layer damage and the like, and seriously affects the living environment and living quality of people. Carbon monoxide (CO) is colorless, odorless, inflammable and explosive gas, has strong toxicity, is one of the common toxic gases at present, and is called as a non-known poison in the 21 st century. In recent years, the requirements of China on ecological environment construction are continuously improved, and NO is treated x CO becomes a necessary requirement for the development of an environment-friendly society.
The denitration catalyst in the prior art has single function and can only remove single NO independently x The components, but the flue gas discharged in industry usually contains various pollutants, and the multi-component pollutants in the flue gas cannot be comprehensively removed when the existing denitration catalyst is used for treating the flue gas. The general preparation method of the conventional SCR denitration catalyst in the prior art comprises the following steps: (1) Tungsten oxide-TiO 2 Preparing composite powder; (2) preparation of a vanadium compound solution; (3) mixing treatment; (4) Catalytic actionPreparing a chemical agent pug; (5) further treating the catalyst pug.
The catalyst prepared by this method is described as V 2 O 5 As active component, tiO 2 As a carrier, only NO can be removed x Other components in the flue gas cannot be removed.
In the specification of the Chinese patent publication No. CN106000435B, a denitration catalyst is provided, which is improved based on a honeycomb SCR catalyst in the prior art, and the denitration activity of the catalyst is improved by increasing oxygen species and oxygen vacancies on the surface of the catalyst. Although the catalyst promotes the progress of the SCR reaction, the catalyst still can only independently remove single NO x The components, which are not removed from other harmful components in the flue gas.
Disclosure of Invention
The application provides a denitration, decarbonization and deamination three-way composite catalyst and a preparation method thereof. The catalyst provided by the application can not only remove NO in the flue gas x Reduction to N 2 And also to CO, NH 3 Hydrocarbon (C) x H y ) Dioxin also has an oxidation effect, so that the pollution of the components in the smoke to the atmosphere is reduced.
In order to achieve the above effects, in a first aspect, the present application provides a method for preparing a denitration, decarbonization, deamination three-way composite catalyst, comprising the steps of:
Preparing a carrier; firstly, uniformly mixing a cerium compound, a zirconium compound and a tungsten compound, and then dissolving the mixture in water to form a zirconium-cerium-tungsten composite oxide aqueous solution; secondly, adding TiO into the zirconium-cerium-tungsten composite oxide aqueous solution 2 Uniformly mixing to obtain a mixture, drying, calcining and grinding the mixture to obtain the zirconium-cerium-tungsten composite oxide-TiO 2 Composite powder as the carrier; wherein the molar ratio of the carrier to the cerium compound, the zirconium compound and the tungsten compound is 1: (0.035 to 0.350), 1: (0.049-0.247), 1: (0.131-0.262);
preparing a vanadium compound solution; wherein, according to the mass percent of the carrier and the ammonium metavanadate of 1 (0.5% -2.5%), the ammonium metavanadate for preparing the vanadium compound solution is weighed;
preparing a precursor; wherein the zirconium-cerium-tungsten composite oxide-TiO 2 Mixing and stirring the composite powder, the vanadium compound solution, the forming additive and pure water to obtain mixed pug; molding and processing the mixed pug into a honeycomb blank; drying and calcining the honeycomb blank to obtain the precursor;
preparing a three-way composite catalyst; firstly, dipping the precursor in a mixed solution of 0.05% -1.0% of platinum solution and 0.05% -1.0% of palladium solution, wherein the dipping time is 30-60min, or dipping the precursor in 0.05% -1.0% of platinum solution, the dipping time is 30-60min, or dipping the precursor in 0.05% -1.0% of palladium solution, the dipping time is 30-60min, and the loaded precursor is obtained; secondly, drying and calcining the loaded precursor to obtain a denitration, decarbonization and deamination three-effect composite catalyst;
Wherein the cerium compound comprises: one or more of cerium nitrate, cerium acetate, cerium sulfate, and cerium chloride; the zirconium compound comprises: one or more of zirconium nitrate, zirconium sulfate and zirconium chloride; the tungsten compound comprises: one or more of ammonium tungstate, ammonium meta-tungstate and ammonium paratungstate.
In one possible embodiment, the zirconium cerium tungsten composite oxide-TiO 2 The particle size of the composite powder is as follows: d50 is less than or equal to 5 mu m; d90 is less than or equal to 10 mu m.
In one possible embodiment, the preparing a vanadium compound solution includes: dissolving the weighed ammonium metavanadate into a monoethanolamine solution, and uniformly stirring to obtain a vanadium compound solution; wherein the mass fraction of the monoethanolamine solution is 5% -12%, and the temperature is 80 ℃ -100 ℃.
In one possible embodiment, the forming aid comprises one or more of lactic acid, carboxymethyl cellulose, polyethylene oxide, starch; the addition amount of the forming auxiliary agent is 0.3-5% of the mass of the carrier.
In one possible embodiment, the shaping the kneaded pug into a honeycomb green body includes:
pretreating the mixed pug to obtain a pug blank, and forming the pug blank to obtain a honeycomb blank;
Wherein, the pretreatment is as follows: and ageing the mixed pug for 10-14 hours, and filtering and pre-extruding to form a pug blank body with uniform humidity.
In one possible embodiment, the drying and calcining the honeycomb blank to obtain a precursor includes:
drying the honeycomb embryo, controlling the drying temperature within 55-65 ℃ and the drying period within 11 days, and ending the drying when the weight reduction rate of the honeycomb embryo reaches more than 25%;
and (3) calcining the honeycomb blank after the drying is finished, wherein the calcining temperature is controlled to be 450-550 ℃ and the calcining time is more than 35 hours.
In one possible embodiment, the calcination temperature of the mixture in the formulated carrier is from 400 ℃ to 500 ℃.
In one possible embodiment, the drying and calcining the supported precursor to obtain the denitration, decarbonization and deamination three-way composite catalyst comprises:
drying the loaded precursor at the drying temperature of 50-60 ℃ for more than or equal to 70 hours;
and calcining the loaded precursor after the drying is finished.
In one possible embodiment, the calcination temperature of the loaded precursor is 380-420 ℃ and the calcination time is 20-30 h.
In one possible embodiment, the palladium compound solution comprises one or more of palladium nitrate, palladium chloride, palladium sulfate.
In one possible embodiment, the platinum compound solution comprises one or more of chloroplatinic acid, platinum chloride, platinum nitrate.
In a second aspect, the application provides a denitration, decarbonization and deamination three-way composite catalyst, which is prepared by adopting the preparation method of the denitration, decarbonization and deamination three-way composite catalyst.
The three-way composite catalyst provided by the application has the following specific reactions with the action of smoke:
(1) Denitrification reaction:
NO+NH 3 +O 2 →N 2 +H 2 O；
NO 2 +NH 3 +O 2 →N 2 +H 2 O；
NO x is NO, NO 2 、N 2 O、N 2 O 5 Wherein NO accounts for more than 90%, is one of main pollutants of global atmospheric pollution, and the NO in the flue gas can be removed after the flue gas passes through the catalyst x Reduction to N 2 And the pollution to the atmosphere is reduced.
(2)NH 3 Oxidizing:
①NH 3 +O 2 →NO+H 2 O NO+NH 3 +O 2 →N 2 +H 2 O
②NH 3 +O 2 →N 2 +H 2 O
in the denitration process of the catalyst, ammonia and NO are required to be sprayed x The oxidation-reduction reaction is carried out, the excessive ammonia injection can also cause the pollution of the atmosphere, and the catalyst provided by the application can make NH 3 Oxidation to N 2 The emission can reduce the pollution of the atmosphere.
NH 3 Oxidation can be divided into two cases, the first being NH 3 Oxidation to NO, reduction of NO to N 2 Discharging; the second is to directly carry out NH 3 Oxidation to N 2 And (5) discharging.
(3) CO oxidation: CO+O 2 →CO 2 +H 2 O
CO is colorless, odorless, inflammable and explosive gas, has strong toxicity, is one of the common toxicants at present, and the developed catalyst contains Pd and Pt which can oxidize the Pd and Pt into CO 2 And the emission is reduced, and the pollution to the atmosphere is reduced.
(4) The application providesCatalyst vs. hydrocarbon (C) x H y ) Dioxins also have an oxidizing effect and can be oxidized to CO 2 And the emission is reduced, and the pollution to the atmosphere is reduced.
Pd and Pt can oxidize hydrocarbons to CO 2 Discharging, wherein the reaction is as follows: c (C) x H y +O 2 →CO 2 +H 2 O。
Pd and Pt can oxidize dioxin into CO 2 Discharging and reacting: c (C) x H y Cl z O 2 +O 2 →CO 2 +H 2 O+HCl。
The beneficial technical effects of the application are as follows:
the catalyst provided by the application adopts zirconium-cerium-tungsten composite oxide-TiO 2 Is a carrier, V 2 O 5 Pd or V 2 O 5 -Pt or V 2 O 5 Pd-Pt as active component, wherein V 2 O 5 The component can remove NO in the flue gas x Pd and Pt components can remove CO and NH 3 And also on hydrocarbons (C) x H y ) The dioxin also has oxidation effect, so that the pollution of the discharged flue gas to the atmosphere can be effectively reduced.
The catalyst carrier provided by the application contains tungsten oxide and zirconium oxide, so that the thermal stability of the catalyst can be improved, and the oxygen storage property of the catalyst can be improved by containing cerium oxide.
Drawings
FIG. 1 is a schematic diagram of steps of a preparation method of a denitration, decarbonization and deamination three-way composite catalyst.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present application more apparent, the technical solutions of the present application will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Example 1
The embodiment provides a preparation method of a denitration, decarbonization and deamination three-way composite catalyst, which comprises the following steps:
s101: by zirconium-cerium-tungsten composite oxide-TiO 2 The composite powder is used as a carrier, and the molar ratio of the carrier to the cerium compound, the zirconium compound and the tungsten compound is 1: (0.035 to 0.350), 1: (0.049-0.247), 1: (0.131-0.262), the cerium compound, the zirconium compound and the tungsten compound are respectively weighed and completely dissolved in water to form an aqueous solution of the zirconium-cerium-tungsten composite oxide.
S102: adding TiO into the zirconium-cerium-tungsten composite oxide aqueous solution 2 Uniformly mixing to obtain a mixture, standing the mixture for 18-30h, then carrying out spray drying, evaporating water, calcining at 400-500 ℃, and grinding the calcined mixture to obtain the zirconium-cerium-tungsten composite oxide-TiO 2 Composite powder;
the cerium compound comprises one or more of cerium nitrate, cerium acetate, cerium sulfate and cerium chloride; the zirconium compound comprises one or more of zirconium nitrate, zirconium sulfate and zirconium chloride; the tungsten compound comprises one or more of ammonium tungstate, ammonium meta-tungstate and ammonium paratungstate.
S103: weighing ammonium metavanadate according to the mass percentage of the carrier to the ammonium metavanadate of 1 (0.5% -2.5%), dissolving the ammonium metavanadate in a monoethanolamine solution at 80-100 ℃, and uniformly stirring to obtain a vanadium compound solution;
the mass fraction of the monoethanolamine solution is 5% -12%.
S104: the zirconium-cerium-tungsten composite oxide-TiO 2 Mixing and stirring the composite powder, the vanadium compound solution, the forming additive and pure water to fully mix the raw materials to obtain mixed pug;
s105: pretreating the mixed pug to obtain a pug blank with uniform humidity, and forming the pug blank to obtain a honeycomb blank;
S106: drying and calcining the honeycomb blank to obtain a precursor;
s107: dipping the precursor in a mixed solution obtained by mixing 0.05% -1.0% of platinum solution and 0.05% -1.0% of palladium solution for 30-60min, or dipping the precursor in the 0.05% -1.0% of platinum solution for 30-60min, or dipping the precursor in the 0.05% -1.0% of palladium solution for 30-60min, so that metal palladium and metal platinum are uniformly loaded on the precursor, and a loaded precursor is obtained;
the palladium compound solution comprises one or more of palladium nitrate, palladium chloride and palladium sulfate; the platinum compound solution comprises one or more of chloroplatinic acid, platinum chloride and platinum nitrate.
S108: and drying and calcining the loaded precursor to obtain the denitration, decarbonization and deamination three-effect composite catalyst.
In one possible implementation, the zirconium cerium tungsten composite oxide-TiO obtained in S102 2 The particle size of the composite powder is as follows: d50 is less than or equal to 5 mu m; d90 is less than or equal to 10 mu m.
In a possible embodiment, the forming aid in S104 includes one or more of lactic acid, carboxymethyl cellulose, polyethylene oxide, starch; the addition amount of the forming auxiliary agent is 0.3-5% of the mass of the carrier.
In one possible embodiment, the pH of the pug in S104 is 7.0 to 8.0, and the water content is 28% to 30%.
In one possible embodiment, the pre-treatment in S105 includes mud aging and filtering; and ageing the mixed pug for 10-14h, and filtering and pre-extruding to form pug blank with uniform humidity.
In a possible embodiment, the drying and calcining the honeycomb blank in S106 to obtain a precursor includes:
the drying temperature is controlled within 55-65 ℃, the drying period is about 11 days, and the drying is finished when the weight reduction rate of the honeycomb embryo reaches more than 25%;
and (3) calcining the honeycomb blank after the drying is finished, wherein the calcining temperature is controlled to be 450-550 ℃ and the calcining time is more than 35 hours.
In one possible embodiment, the drying temperature in the step S108 is 50-60 ℃ for more than or equal to 70 hours; the calcination temperature is 380-420 ℃ and the time is 20-30 h.
In the catalyst obtained by the preparation method of the denitration, decarbonization and deamination three-effect composite catalyst provided by the embodiment of the application, zirconium-cerium-tungsten composite oxide-TiO 2 Is a carrier, V 2 O 5 Pd or V 2 O 5 -Pt or V 2 O 5 Pd-Pt as active component, wherein V 2 O 5 The component can remove NO in the flue gas x Pd and Pt components can remove CO and NH 3 And also on hydrocarbons (C) x H y ) The dioxin also has oxidation effect, so that the pollution of the discharged smoke to the atmosphere can be effectively reduced; the carrier contains tungsten oxide and zirconium oxide, so that the thermal stability of the catalyst can be improved, and the oxygen storage property of the catalyst can be improved by containing cerium oxide.
Example 2
The embodiment provides a preparation method of a denitration, decarbonization and deamination three-way composite catalyst, which comprises the following steps:
(1) Cerium-tungsten composite oxide-TiO 2 Preparation of composite powder:
respectively weighing 10kg of cerium nitrate, 10kg of zirconium nitrate and 50kg of ammonium metatungstate, respectively dissolving the cerium nitrate and the zirconium nitrate in water, mixing the solutions after the dissolution is completed, and adding 930kg of TiO 2 Mixing the zirconium-cerium-tungsten compound solution and TiO 2 Uniformly mixing, standing the mixture for 18h, performing spray drying, rapidly evaporating water, calcining, setting the calcining temperature to 400 ℃, grinding the solid into powder after calcining, and controlling the particle size of the powder to be as follows: d50 is less than or equal to 5 mu m; d90 is less than or equal to 10 mu m.
(2) Preparation of vanadium compound solution:
5kg of ammonium metavanadate is weighed and dissolved in a monoethanolamine solution with the temperature of 80-100 ℃, the mass of the monoethanolamine solution is 5.6kg, and the solution is stirred uniformly and the volume is fixed to 50L.
(3) And (3) preparing a mixed pug:
weighing zirconium ceriumTungsten composite oxide-TiO 2 632kg of composite powder, 50L of vanadium compound solution, 6.5kg of lactic acid, 3.25kg of starch, 3kg of carboxymethyl cellulose, 7kg of polyethylene oxide, 120kg of pure water and 120kg of ammonia water, and mixing the raw materials fully together, stirring for 5-6h, and obtaining the pug after uniform mixing.
(4) Shaping a pug blank:
aging the mixed pug for 10 hours, filtering and pre-extruding to form a pug blank with uniform humidity, putting the pug blank into a forming machine, and extruding the honeycomb blank by a die.
(5) Further treatment of the honeycomb embryo:
and (3) putting the formed honeycomb blank into a drying room for drying, controlling the drying temperature to be 60 ℃, controlling the drying period to be about 11 days, and ending the drying when the weight reduction rate of the honeycomb blank reaches more than 25%.
And after the drying is finished, placing the honeycomb blank into a kiln for calcination, wherein the calcination temperature is set at 450 ℃, and the calcination period is more than 35 hours. And (5) after the calcination is finished, obtaining a precursor.
(6) Palladium compound, platinum compound loading:
the high-concentration palladium nitrate solution is diluted to 0.05%, the high-concentration platinum nitrate solution is diluted to 0.05%, the two diluted solutions are mixed, and the precursor is immersed in the mixed solution of the two diluted solutions for 30min.
(7) Precursor loading and further processing:
and (3) putting the loaded precursor into a drying room for drying, wherein the drying temperature is set to 55 ℃, and the drying period is 72 hours.
And after the drying is finished, the loaded precursor is put into a kiln for calcination, the calcination temperature is set at 400 ℃, and the calcination period is 28 hours. And (5) after the calcination is finished, obtaining the product.
Catalyst performance test prepared based on the preparation method of example 2:
the equipment used for the test is as follows: catalyst performance evaluation reaction device; the flue gas conditions are designed, and are specifically shown in table 1;
table 1 design flue gas conditions
At the same temperature of 380 ℃, different inlets NO were tested separately x Denitration efficiency at the concentration, and the obtained results are shown in table 2;
TABLE 2 same temperature, different inlet NO x Denitration efficiency at concentration
The denitration efficiency at different inlet CO concentrations was tested at the same temperature of 380 ℃ to obtain the results shown in Table 3;
TABLE 3 decarburization efficiency at the same temperature and different inlet CO concentrations
At the same temperature of 380 ℃, different inlets NH are respectively tested 3 Denitration efficiency at the concentration, and the obtained results are shown in table 4;
TABLE 4 same temperature, different inlets NH 3 Deamination efficiency at content
Inlet NO x The concentration was 250mg/Nm 3 The inlet CO concentration was 1500mg/Nm 3 The denitration and decarbonization efficiencies measured at different temperatures were compared as shown in table 5;
table 5 comparison of denitration and decarbonization efficiencies at different temperatures
At inlet NH 3 Deamination efficiency at the same content and different temperatures is shown in table 6;
TABLE 6 Inlet NH 3 Deamination efficiency at the same content and different temperatures
The embodiment provides a preparation method of a denitration, decarbonization and deamination three-way composite catalyst, wherein the molar ratio of the obtained carrier to cerium compound, zirconium compound and tungsten compound is 1:0.035, 1:0.049, 1: the catalyst of 0.131 is immersed in a mixed solution of 0.05 percent of palladium solution and 0.05 percent of platinum solution, the denitration efficiency reaches 83 to 88 percent, the decarbonization efficiency reaches 78 to 83 percent, and the deamination efficiency reaches 91 to 96 percent.
Example 3
The embodiment of the application also provides a preparation method of the denitration, decarbonization and deamination three-way composite catalyst, which comprises the following steps:
(1) Zirconium cerium tungsten composite oxide-TiO 2 Preparation of composite powder:
respectively weighing 100kg of cerium nitrate, 50kg of zirconium nitrate and 100kg of ammonium metatungstate, respectively dissolving the cerium nitrate and the zirconium nitrate in water, mixing the solutions after the dissolution is completed, and adding 750kg of TiO 2 Mixing the zirconium-cerium-tungsten compound solution and TiO 2 Uniformly mixing, standing the mixture for 30 hours, performing spray drying, rapidly evaporating water, calcining, setting the calcining temperature to 450 ℃, grinding the solid into powder after calcining, and controlling the particle size of the powder to be as follows: d50 is less than or equal to 5 mu m; d90 is less than or equal to 10 mu m.
(2) Preparation of vanadium compound solution:
23kg of ammonium metavanadate is weighed and dissolved in a monoethanolamine solution with the temperature of 80-100 ℃, the mass of the monoethanolamine solution is 26.4kg, and the solution is stirred uniformly and the volume is fixed to 100L.
(3) And (3) preparing a mixed pug:
weighing zirconium-cerium-tungsten composite oxide-TiO 2 650kg of composite powder, 50L of vanadium compound solution, 6.5kg of lactic acid, 3.25kg of starch and 3kg of carboxymethyl cellulose,7kg of polyethylene oxide, 120kg of pure water and 120kg of ammonia water, and mixing the raw materials together fully, stirring for 5-6h, and obtaining the pug after uniform mixing.
(4) Shaping a pug blank:
aging the mixed pug for 14 hours, filtering and pre-extruding to form a pug blank with uniform humidity, putting the pug blank into a forming machine, and extruding the formed honeycomb catalyst blank through a die.
(5) Further treatment of the honeycomb embryo:
and (3) putting the formed honeycomb blank into a drying room for drying, controlling the drying temperature to be 60 ℃, controlling the drying period to be about 11 days, and ending the drying when the weight reduction rate of the honeycomb blank reaches more than 25%.
And after the drying is finished, placing the honeycomb blank into a kiln for calcination, wherein the calcination temperature is set at 530 ℃, and the calcination period is more than 35 hours. And (5) after the calcination is finished, obtaining a precursor.
(6) Palladium compound, platinum compound loading:
the high-concentration palladium nitrate solution is diluted to a concentration of 1.0%, the high-concentration platinum nitrate solution is diluted to a concentration of 1.0%, the two diluted solutions are mixed, and the precursor is immersed in the mixed solution of the two diluted solutions for 50min.
(7) Precursor loading and further processing:
and (3) putting the loaded precursor into a drying room for drying, wherein the drying temperature is set to 55 ℃, and the drying period is 72 hours.
And after the drying is finished, the loaded precursor is put into a kiln for calcination, the calcination temperature is set at 400 ℃, and the calcination period is 28 hours. And (5) after the calcination is finished, obtaining the product.
Catalyst performance test prepared based on the preparation method of example 3:
the flue gas conditions are designed, and are specifically shown in table 7;
table 7 design flue gas conditions
At the same temperature of 380 ℃, different inlets NO were tested separately x Denitration efficiency at the concentration, and the obtained results are shown in table 8;
TABLE 8 same temperature, different inlet NO x Denitration efficiency at concentration
The denitration efficiency at different inlet CO concentrations was tested at the same temperature of 380 ℃ to obtain the results shown in Table 9;
TABLE 9 decarburization efficiency at the same temperature and different inlet CO concentrations
At the same temperature of 380 ℃, different inlets NH are respectively tested 3 Denitration efficiency at the concentration, and the obtained results are shown in table 10;
TABLE 10 same temperature, different inlet NH 3 Deamination efficiency at content
Inlet NO x The concentration was 250mg/Nm 3 The inlet CO concentration was 1500mg/Nm 3 The denitration and decarbonization efficiencies measured at different temperatures were compared as shown in table 11;
table 11 comparison of denitration and decarbonization efficiencies at different temperatures
At inlet NH 3 Deamination efficiency at the same content and different temperatures is shown in table 12;
TABLE 12 Inlet NH 3 Deamination efficiency at the same, different temperatures
The embodiment provides a method for preparing a denitration, decarbonization and deamination three-effect composite catalyst, wherein the molar ratio of a carrier to a cerium compound, a zirconium compound and a tungsten compound is 1:0.353, 1:0.247, 1: in the catalyst of 0.262, the catalyst is immersed in a mixed solution of a 1.0% palladium solution and a 1.0% platinum solution, the denitration efficiency reaches 89% -94%, the decarbonization efficiency reaches 87% -95%, and the deamination efficiency reaches 93% -98%.
Example 4
The embodiment also provides a preparation method of the denitration, decarbonization and deamination three-way composite catalyst, which comprises the following steps:
(1) Zirconium cerium tungsten composite oxide-TiO 2 Preparation of composite powder:
respectively weighing 55kg of cerium nitrate, 30kg of zirconium nitrate and 75kg of ammonium metatungstate, respectively dissolving the cerium nitrate and the zirconium nitrate in water, mixing the solutions after the dissolution is completed, and adding 840kg of TiO 2 Mixing the zirconium-cerium-tungsten compound solution and TiO 2 Uniformly mixing, standing the mixture for 30 hours, performing spray drying, rapidly evaporating water, calcining, setting the calcining temperature to 500 ℃, grinding the solid into powder after calcining, and controlling the particle size of the powder to be as follows: d50 is less than or equal to 5 mu m; d90 is less than or equal to 10 mu m.
(2) Preparation of vanadium compound solution:
weighing 10kg of ammonium metavanadate, dissolving the ammonium metavanadate in a monoethanolamine solution with the temperature of 80-100 ℃, stirring the solution uniformly and fixing the volume to 60L, wherein the mass of the monoethanolamine solution is 11.2 kg.
(3) Preparing a catalyst pug:
weighing zirconium-cerium-tungsten composite oxide-TiO 2 650kg of composite powder, 50L of vanadium compound solution, 6.5kg of lactic acid, 3.25kg of starch, 3kg of carboxymethyl cellulose, 7kg of polyethylene oxide, 120kg of pure water and 120kg of ammonia water, and mixing the raw materials fully together, stirring for 5-6h, and obtaining the pug after uniform mixing.
(4) Shaping a pug blank:
and ageing the mixed pug for 12 hours, filtering and pre-extruding to form a pug blank with uniform humidity, putting the pug blank into a forming machine, and extruding the formed honeycomb catalyst blank through a die.
(5) Further treatment of the honeycomb embryo:
and (3) putting the formed honeycomb blank into a drying room for drying, controlling the drying temperature to be 60 ℃, controlling the drying period to be about 11 days, and ending the drying when the weight reduction rate of the honeycomb blank reaches more than 25%.
And after the drying is finished, placing the honeycomb blank into a kiln for calcination, wherein the calcination temperature is set at 530 ℃, and the calcination period is more than 35 hours. And (5) after the calcination is finished, obtaining a precursor.
(6) Palladium compound, platinum compound loading:
the high-concentration palladium nitrate solution is diluted to 0.5%, the high-concentration platinum nitrate solution is diluted to 0.5%, the two diluted solutions are mixed, and the precursor is immersed in the mixed solution of the two diluted solutions for 50min.
(7) Precursor loading and further processing:
and (3) putting the loaded precursor into a drying room for drying, wherein the drying temperature is set to 55 ℃, and the drying period is 72 hours.
And after the drying is finished, the loaded precursor is put into a kiln for calcination, the calcination temperature is set at 500 ℃, and the calcination period is 28 hours. And (5) after the calcination is finished, obtaining the product.
Catalyst performance test prepared based on the preparation method of example 4: the flue gas conditions are designed, and are specifically shown in table 13;
Table 13 design flue gas conditions
At 380 DEG CRespectively testing different inlets NO at the same temperature x Denitration efficiency at the concentration, and the obtained results are shown in table 8;
TABLE 14 same temperature, different inlet NO x Denitration efficiency at concentration
The denitration efficiency at different inlet CO concentrations was tested at the same temperature of 380 ℃ to obtain the results shown in Table 9;
TABLE 15 decarburization efficiency at the same temperature and different inlet CO concentrations
At the same temperature of 380 ℃, different inlets NH are respectively tested 3 Denitration efficiency at the concentration, and the obtained results are shown in table 10;
TABLE 16 same temperature, different inlet NH 3 Deamination efficiency at content
Inlet NO x The concentration was 250mg/Nm 3 The inlet CO concentration was 1500mg/Nm 3 The denitration and decarbonization efficiencies measured at different temperatures were compared as shown in table 17;
table 17 comparison of denitration and decarbonization efficiencies at different temperatures
At inlet NH 3 Deamination efficiency at the same content and different temperatures is shown in table 18;
TABLE 18 Inlet NH 3 Deamination efficiency at the same, different temperatures
The embodiment provides a method for preparing a denitration, decarbonization and deamination three-effect composite catalyst, wherein the molar ratio of a carrier to a cerium compound, a zirconium compound and a tungsten compound is 1:0.194, 1:0.148, 1: in the catalyst of 0.196, the catalyst is immersed in a mixed solution of 0.5 percent palladium solution and 0.5 percent platinum solution, the denitration efficiency reaches 86 to 91 percent, the decarburization efficiency reaches 83 to 89 percent, and the deamination efficiency reaches 92 to 97 percent.
Example 5
The embodiment also provides a preparation method of the denitration, decarbonization and deamination three-way composite catalyst, which comprises the following steps:
(1) Cerium-tungsten composite oxide-TiO 2 Preparation of composite powder:
respectively weighing 10kg of cerium nitrate, 10kg of zirconium nitrate and 50kg of ammonium metatungstate, respectively dissolving the cerium nitrate and the zirconium nitrate in water, mixing the solutions after the dissolution is completed, and adding 930kg of TiO 2 Mixing the zirconium-cerium-tungsten compound solution and TiO 2 Uniformly mixing, standing the mixture for 18h, performing spray drying, rapidly evaporating water, calcining, setting the calcining temperature to 400 ℃, grinding the solid into powder after calcining, and controlling the particle size of the powder to be as follows: d50 is less than or equal to 5 mu m; d90 is less than or equal to 10 mu m.
(2) Preparation of vanadium compound solution:
5kg of ammonium metavanadate is weighed and dissolved in a monoethanolamine solution with the temperature of 80-100 ℃, the mass of the monoethanolamine solution is 5.6kg, and the solution is stirred uniformly and the volume is fixed to 50L.
(3) And (3) preparing a mixed pug:
weighing zirconium-cerium-tungsten composite oxide-TiO 2 650kg of composite powder, 50L of vanadium compound solution, 6.5kg of lactic acid, 3.25kg of starch, 3kg of carboxymethyl cellulose, 7kg of polyethylene oxide, 120kg of pure water and 120kg of ammonia water, and mixing the raw materials fully together, stirring for 5-6h, and obtaining the pug after uniform mixing.
(4) Forming a honeycomb blank:
aging the mixed pug for 10 hours, filtering and pre-extruding to form a pug blank with uniform humidity, putting the pug blank into a forming machine, and extruding the honeycomb blank by a die.
(5) Further treatment of the honeycomb embryo:
and (3) putting the formed honeycomb blank into a drying room for drying, wherein the drying temperature is set to be 60 ℃, the drying period is 12 days, and when the weight reduction rate of the honeycomb blank reaches more than 25%, the drying is finished.
And (3) calcining the honeycomb blank after the drying is finished, wherein the calcining temperature is set at 450 ℃, and the calcining period is more than 35 hours. And (5) after the calcination is finished, obtaining a precursor.
(6) Loading of palladium compound:
and diluting the high-concentration palladium nitrate solution to a concentration of 0.05%, and immersing the precursor in the palladium nitrate diluted solution for 30min.
(7) Precursor loading and further processing:
and (3) placing the loaded precursor into a drying room for drying, wherein the drying temperature is set to 55 ℃, and the drying period is more than 96 hours.
And (3) calcining the loaded precursor after the drying is finished, wherein the calcining temperature is set at 400 ℃, and the calcining period is 28h. And (5) after the calcination is finished, obtaining the product.
Catalyst performance test prepared based on the preparation method of example 5:
The equipment used for the test is as follows: catalyst performance evaluation reaction device; the flue gas conditions were designed as shown in table 19;
table 19 design flue gas conditions
At the same temperature of 380 ℃, different inlets NO were tested separately x Denitration efficiency at the concentration, and the obtained results are shown in table 20;
TABLE 20 same temperature, different inlet NO x Denitration efficiency at concentration
The denitration efficiency at different inlet CO concentrations was tested at the same temperature of 380 ℃ to obtain the results shown in Table 21;
TABLE 21 decarburization efficiency at the same temperature and different inlet CO concentrations
At the same temperature of 380 ℃, different inlets NH are respectively tested 3 Denitration efficiency at the concentration, and the obtained results are shown in table 22;
TABLE 22 same temperature, different inlet NH 3 Deamination efficiency at content
Inlet NO x The concentration was 250mg/Nm 3 The inlet CO concentration was 1500mg/Nm 3 The denitration and decarbonization efficiencies measured at different temperatures were compared as shown in table 23;
table 23 comparison of denitration and decarbonization efficiencies at different temperatures
At inlet NH 3 Deamination efficiency at the same content and different temperatures is shown in table 24;
TABLE 24 Inlet NH 3 Deamination efficiency at the same content and different temperatures
The embodiment provides a method for preparing a denitration, decarbonization and deamination three-effect composite catalyst, wherein the molar ratio of a carrier to a cerium compound, a zirconium compound and a tungsten compound is 1:0.035, 1:0.049, 1: in the catalyst of 0.131, the catalyst is immersed in a palladium solution of 0.05 percent, the denitration efficiency reaches 83 to 88 percent, the decarbonization efficiency reaches 65 to 80 percent, and the deamination efficiency reaches 86 to 91 percent.
Example 6
(1) Cerium-tungsten composite oxide-TiO 2 Preparation of composite powder:
respectively weighing 100kg of cerium nitrate, 50kg of zirconium nitrate and 100kg of ammonium metatungstate, respectively dissolving the cerium nitrate and the zirconium nitrate in water, mixing the solutions after the dissolution is completed, and adding 750kg of TiO 2 Mixing the zirconium-cerium-tungsten compound solution and TiO 2 Uniformly mixing, standing the mixture for 18h, performing spray drying, rapidly evaporating water, calcining, setting the calcining temperature to 400 ℃, grinding the solid into powder after calcining, and controlling the particle size of the powder to be as follows: d50 is less than or equal to 5 mu m; d90 is less than or equal to 10 mu m.
(2) Preparation of vanadium compound solution:
23kg of ammonium metavanadate is weighed and dissolved in a monoethanolamine solution with the temperature of 80-100 ℃, the mass of the monoethanolamine solution is 26.4kg, and the solution is stirred uniformly and the volume is fixed to 100L.
(3) And (3) preparing a mixed pug:
weighing zirconium-cerium-tungsten composite oxide-TiO 2 650kg of composite powder, 50L of vanadium compound solution, 6.5kg of lactic acid, 3.25kg of starch, 3kg of carboxymethyl cellulose, 7kg of polyethylene oxide, 120kg of pure water and 120kg of ammonia water, and mixing the raw materials fully together, stirring for 5-6h, and obtaining the pug after uniform mixing.
(4) Forming a honeycomb blank:
aging the mixed pug for 10 hours, filtering and pre-extruding to form a pug blank with uniform humidity, putting the pug blank into a forming machine, and extruding the honeycomb blank by a die.
(5) Further treatment of the honeycomb embryo:
and (3) putting the formed honeycomb blank into a drying room for drying, wherein the drying temperature is set to be 60 ℃, the drying period is 12 days, and when the weight reduction rate of the honeycomb blank reaches more than 25%, the drying is finished.
And (3) calcining the honeycomb blank after the drying is finished, wherein the calcining temperature is set at 450 ℃, and the calcining period is more than 35 hours. And (5) after the calcination is finished, obtaining a precursor.
(6) Loading of palladium compound:
and diluting the high-concentration palladium nitrate solution to a concentration of 0.1%, and immersing the precursor in the palladium nitrate diluted solution for 30min.
(7) Precursor loading and further processing:
and (3) placing the loaded precursor into a drying room for drying, wherein the drying temperature is set to 55 ℃, and the drying period is more than 96 hours.
And (3) calcining the loaded precursor after the drying is finished, wherein the calcining temperature is set at 400 ℃, and the calcining period is 28h. And (5) after the calcination is finished, obtaining the product.
Catalyst performance test prepared based on the preparation method of example 6:
the equipment used for the test is as follows: catalyst performance evaluation reaction device; the flue gas conditions were designed as shown in table 25;
table 25 design flue gas conditions
At the same temperature of 380 ℃, different inlets NO were tested separately x Denitration efficiency at the concentration, and the obtained results are shown in table 26;
table 26 same temperature, different inlet NO x Denitration efficiency at concentration
The denitration efficiency at different inlet CO concentrations was tested at the same temperature of 380 ℃ to obtain the results shown in Table 27;
TABLE 27 decarburization efficiency at the same temperature and different inlet CO concentrations
At the same temperature of 380 ℃, different inlets NH are respectively tested 3 Denitration efficiency at the concentration, and the obtained results are shown in table 28;
TABLE 28 same temperature, different inlet NH 3 Deamination efficiency at content
Inlet NO x The concentration was 250mg/Nm 3 The inlet CO concentration was 1500mg/Nm 3 The denitration and decarbonization efficiencies measured at different temperatures were compared as shown in table 29;
table 29 comparison of denitration and decarbonization efficiencies at different temperatures
At inlet NH 3 Deamination efficiency at the same content and different temperatures is shown in table 30;
TABLE 30 Inlet NH 3 Deamination efficiency at the same content and different temperatures
The embodiment provides a method for preparing a denitration, decarbonization and deamination three-effect composite catalyst, wherein the molar ratio of a carrier to a cerium compound, a zirconium compound and a tungsten compound is 1:0.353, 1:0.247, 1:0.262 of catalyst, is immersed in 1.0 percent of palladium solution, the denitration efficiency reaches 89 to 94 percent, the decarbonization efficiency reaches 84 to 89 percent, and the deamination efficiency reaches 89 to 94 percent.
Example 7
The preparation method of the denitration, decarbonization and deamination three-way composite catalyst comprises the following steps:
(1) Zirconium cerium tungsten composite oxide-TiO 2 Preparation of composite powder:
respectively weighing 55kg of cerium nitrate, 30kg of zirconium nitrate and 75kg of ammonium metatungstate, respectively dissolving the cerium nitrate and the zirconium nitrate in water, mixing the solutions after the dissolution is completed, and adding 840kg of TiO 2 Mixing the zirconium-cerium-tungsten compound solution and TiO 2 Uniformly mixing, standing the mixture for 30 hours, performing spray drying, rapidly evaporating water, calcining, setting the calcining temperature to 500 ℃, grinding the solid into powder after calcining, and controlling the particle size of the powder to be as follows: d50 is less than or equal to 5 mu m; d90 is less than or equal to 10 mu m.
(2) Preparation of vanadium compound solution:
weighing 10kg of ammonium metavanadate, dissolving the ammonium metavanadate in a monoethanolamine solution with the temperature of 80-100 ℃, stirring the solution uniformly and fixing the volume to 60L, wherein the mass of the monoethanolamine solution is 11.2 kg.
(3) And (3) preparing a mixed pug:
weighing zirconium-cerium-tungsten composite oxide-TiO 2 650kg of composite powder, 50L of vanadium compound solution, 6.5kg of lactic acid, 3.25kg of starch, 3kg of carboxymethyl cellulose, 7kg of polyethylene oxide, 120kg of pure water and 120kg of ammonia water, and mixing the raw materials fully together, stirring for 5-6h, and obtaining the pug after uniform mixing.
(4) Forming a honeycomb blank:
aging the mixed pug for 10 hours, filtering and pre-extruding to form a pug blank with uniform humidity, putting the pug blank into a forming machine, and extruding the honeycomb blank by a die.
(5) Further treatment of the honeycomb embryo:
and (3) putting the formed honeycomb blank into a drying room for drying, wherein the drying temperature is set to be 60 ℃, the drying period is 12 days, and when the weight reduction rate of the honeycomb blank reaches more than 25%, the drying is finished.
And (3) calcining the honeycomb blank after the drying is finished, wherein the calcining temperature is set at 450 ℃, and the calcining period is more than 35 hours. And (5) after the calcination is finished, obtaining a precursor.
(6) Loading of palladium compound:
and diluting the high-concentration palladium nitrate solution to a concentration of 0.5%, and immersing the precursor in the palladium nitrate diluted solution for 30min.
(7) Precursor loading and further processing:
and (3) placing the loaded precursor into a drying room for drying, wherein the drying temperature is set to 55 ℃, and the drying period is more than 96 hours.
And (3) calcining the loaded precursor after the drying is finished, wherein the calcining temperature is set at 400 ℃, and the calcining period is 28h. And (5) after the calcination is finished, obtaining the product.
Catalyst performance test prepared based on the preparation method of example 7: the flue gas conditions are designed, and are shown in table 31;
Table 31 design flue gas conditions
At the same temperature of 380 ℃, different inlets NO were tested separately x Denitration efficiency at the concentration, and the obtained results are shown in table 32;
TABLE 32 same temperature, different inlet NO x Denitration efficiency at concentration
The denitration efficiency at different inlet CO concentrations was tested at the same temperature of 380 ℃ to obtain the results shown in Table 33;
TABLE 33 decarburization efficiency at the same temperature and different inlet CO concentrations
At the same temperature of 380 ℃, different inlets NH are respectively tested 3 Denitration efficiency at the concentration, and the obtained results are shown in table 34;
table 34 same temperature, different inlet NH 3 Deamination efficiency at content
Inlet NO x The concentration was 250mg/Nm 3 The inlet CO concentration was 1500mg/Nm 3 The denitration and decarbonization efficiencies measured at different temperatures were compared as shown in table 35;
table 35 comparison of denitration and decarbonization efficiencies at different temperatures
At inlet NH 3 Deamination efficiency at the same content and different temperatures is shown in table 36;
TABLE 36 Inlet NH 3 Deamination efficiency at the same, different temperatures
The embodiment provides a preparation method of a denitration, decarbonization and deamination three-way composite catalyst, wherein the mass ratio of a carrier to cerium, zirconium and tungsten is 1:0.194, 1:0.148 and 1:0.196 respectively, the carrier is immersed in 0.5% palladium solution, the denitration efficiency reaches 86% -91%, the decarbonization efficiency reaches 77% -81% and the deamination efficiency reaches 87% -93%.
Example 8
The embodiment provides a preparation method of a denitration, decarbonization and deamination three-way composite catalyst, which comprises the following steps:
(1) Cerium-tungsten composite oxide-TiO 2 Preparation of composite powder:
respectively weighing 10kg of cerium nitrate, 10kg of zirconium nitrate and 50kg of ammonium metatungstate, respectively dissolving the cerium nitrate and the zirconium nitrate in water, mixing the solutions after the dissolution is completed, and adding 930kg of TiO 2 Mixing the zirconium-cerium-tungsten compound solution and TiO 2 Uniformly mixing, standing the mixture for 18h, performing spray drying, rapidly evaporating water, calcining, setting the calcining temperature to 400 ℃,after calcination, the solid is ground into powder, and the particle size of the powder is controlled to be: d50 is less than or equal to 5 mu m; d90 is less than or equal to 10 mu m.
(2) Preparation of vanadium compound solution:
5kg of ammonium metavanadate is weighed and dissolved in a monoethanolamine solution with the temperature of 80-100 ℃, the mass of the monoethanolamine solution is 5.6kg, and the solution is stirred uniformly and the volume is fixed to 50L.
(3) And (3) preparing a mixed pug:
weighing zirconium-cerium-tungsten composite oxide-TiO 2 650kg of composite powder, 50L of vanadium compound solution, 6.5kg of lactic acid, 3.25kg of starch, 3kg of carboxymethyl cellulose, 7kg of polyethylene oxide, 120kg of pure water and 120kg of ammonia water, and mixing the raw materials fully together, stirring for 5-6h, and obtaining the pug after uniform mixing.
(4) Forming a honeycomb blank:
aging the mixed pug for 10 hours, filtering and pre-extruding to form a pug blank with uniform humidity, putting the pug blank into a forming machine, and extruding the honeycomb blank by a die.
(5) Further treatment of the honeycomb embryo:
and (3) putting the formed honeycomb blank into a drying room for drying, wherein the drying temperature is set to be 60 ℃, the drying period is 12 days, and when the weight reduction rate of the honeycomb blank reaches more than 25%, the drying is finished.
And (3) calcining the honeycomb blank after the drying is finished, wherein the calcining temperature is set at 450 ℃, and the calcining period is more than 35 hours. And (5) after the calcination is finished, obtaining a precursor.
(6) Loading of platinum compound:
the high-concentration platinum nitrate solution is diluted to a concentration of 0.05%, and the precursor is immersed in the platinum nitrate diluted solution for 30min.
(7) Precursor loading and further processing:
and (3) placing the loaded precursor into a drying room for drying, wherein the drying temperature is set to 55 ℃, and the drying period is more than 96 hours.
And (3) calcining the loaded precursor after the drying is finished, wherein the calcining temperature is set at 400 ℃, and the calcining period is 28h. And (5) after the calcination is finished, obtaining the product.
Catalyst performance test prepared based on the preparation method of example 8:
The equipment used for the test is as follows: catalyst performance evaluation reaction device; the flue gas conditions are designed, and are shown in table 37;
table 37 designs flue gas conditions
At the same temperature of 380 ℃, different inlets NO were tested separately x Denitration efficiency at the concentration, and the obtained results are shown in table 38;
table 38 same temperature, different inlet NO x Denitration efficiency at concentration
The denitration efficiency at different inlet CO concentrations was tested at the same temperature of 380 ℃ to obtain the results shown in Table 39;
table 39 decarburization efficiency at the same temperature and different inlet CO concentrations
At the same temperature of 380 ℃, different inlets NH are respectively tested 3 Denitration efficiency at the concentration, and the obtained results are shown in table 40;
table 40 same temperature, different inlets NH 3 Deamination efficiency at content
Inlet NO x The concentration was 250mg/Nm 3 The inlet CO concentration was 1500mg/Nm 3 The denitration and decarbonization efficiencies measured at different temperatures were compared as shown in table 41;
table 41 comparison of denitration and decarbonization efficiencies at different temperatures
At inlet NH 3 Deamination efficiency at the same content and different temperatures is shown in table 42;
table 42 entry NH 3 Deamination efficiency at the same content and different temperatures
The embodiment provides a method for preparing a denitration, decarbonization and deamination three-effect composite catalyst, wherein the molar ratio of a carrier to a cerium compound, a zirconium compound and a tungsten compound is 1:0.035, 1:0.049, 1: in the catalyst of 0.131, the catalyst is immersed in 0.05 percent platinum solution, the denitration efficiency reaches 83 to 88 percent, the decarbonization efficiency reaches 69.6 to 75.5 percent, and the deamination efficiency reaches 84.4 to 90.2 percent.
Example 9
(1) Cerium-tungsten composite oxide-TiO 2 Preparation of composite powder:
respectively weighing 100kg of cerium nitrate, 50kg of zirconium nitrate and 100kg of ammonium metatungstate, respectively dissolving the cerium nitrate and the zirconium nitrate in water, mixing the solutions after the dissolution is completed, and adding 750kg of TiO 2 Mixing the zirconium-cerium-tungsten compound solution and TiO 2 Uniformly mixing, standing the mixture for 18h, performing spray drying, rapidly evaporating water, calcining, setting the calcining temperature to 400 ℃, grinding the solid into powder after calcining, and controlling the particle size of the powder to be as follows: d50 is less than or equal to 5 mu m; d90 is less than or equal to 10 mu m.
(2) Preparation of vanadium compound solution:
23kg of ammonium metavanadate is weighed and dissolved in a monoethanolamine solution with the temperature of 80-100 ℃, the mass of the monoethanolamine solution is 26.4kg, and the solution is stirred uniformly and the volume is fixed to 100L.
(3) And (3) preparing a mixed pug:
weighing zirconium cerium tungstenComposite oxide-TiO 2 650kg of composite powder, 50L of vanadium compound solution, 6.5kg of lactic acid, 3.25kg of starch, 3kg of carboxymethyl cellulose, 7kg of polyethylene oxide, 120kg of pure water and 120kg of ammonia water, and mixing the raw materials fully together, stirring for 5-6h, and obtaining the pug after uniform mixing.
(4) Forming a honeycomb blank:
aging the mixed pug for 10 hours, filtering and pre-extruding to form a pug blank with uniform humidity, putting the pug blank into a forming machine, and extruding the honeycomb blank by a die.
(5) Further treatment of the honeycomb embryo:
and (3) putting the formed honeycomb blank into a drying room for drying, wherein the drying temperature is set to be 60 ℃, the drying period is 12 days, and the drying is finished when the weight reduction rate of the catalyst blank is detected to be more than 25%.
And (3) calcining the honeycomb blank after the drying is finished, wherein the calcining temperature is set at 450 ℃, and the calcining period is more than 35 hours. And (5) after the calcination is finished, obtaining the honeycomb precursor.
(6) Loading of platinum compound:
the high-concentration platinum nitrate solution is diluted to a concentration of 1.0%, and the precursor is immersed in the platinum nitrate diluted solution for 30min.
(7) Precursor loading and further processing:
and (3) placing the loaded precursor into a drying room for drying, wherein the drying temperature is set to 55 ℃, and the drying period is more than 96 hours.
And (3) calcining the loaded precursor after the drying is finished, wherein the calcining temperature is set at 400 ℃, and the calcining period is 28h. And (5) after the calcination is finished, obtaining the product.
Catalyst performance test prepared based on the preparation method of example 9:
the equipment used for the test is as follows: catalyst performance evaluation reaction device; the flue gas conditions were designed as shown in table 43;
table 43 design flue gas conditions
At the same temperature of 380 ℃, different inlets NO were tested separately x Denitration efficiency at the concentration, and the obtained results are shown in table 44;
table 44 same temperature, different inlet NO x Denitration efficiency at concentration
The denitration efficiency at different inlet CO concentrations was tested at the same temperature of 380 ℃ to obtain the results shown in Table 45;
table 45 decarburization efficiency at the same temperature and different inlet CO concentrations
At the same temperature of 380 ℃, different inlets NH are respectively tested 3 Denitration efficiency at the concentration, and the obtained results are shown in table 46;
table 46 same temperature, different inlet NH 3 Deamination efficiency at content
Inlet NO x The concentration was 250mg/Nm 3 The inlet CO concentration was 1500mg/Nm 3 The denitration and decarbonization efficiencies measured at different temperatures were compared as shown in table 47;
table 47 comparison of denitration and decarburization efficiencies at different temperatures
At inlet NH 3 Deamination efficiency at the same content and different temperatures is shown in table 48;
table 48 Inlet NH 3 Deamination efficiency at the same content and different temperatures
The embodiment provides a method for preparing a denitration, decarbonization and deamination three-effect composite catalyst, wherein the molar ratio of a carrier to a cerium compound, a zirconium compound and a tungsten compound is 1:0.353, 1:0.247, 1: in the catalyst of 0.262, the catalyst is immersed in a platinum solution of 1.0%, the denitration efficiency reaches 89% -94%, the decarbonization efficiency reaches 82% -87%, and the deamination efficiency reaches 88% -93%.
Example 10
The embodiment provides a preparation method of a denitration, decarbonization and deamination three-way composite catalyst, which comprises the following steps:
(1) Zirconium cerium tungsten composite oxide-TiO 2 Preparation of composite powder:
respectively weighing 55kg of cerium nitrate, 30kg of zirconium nitrate and 75kg of ammonium metatungstate, respectively dissolving the cerium nitrate and the zirconium nitrate in water, mixing the solutions after the dissolution is completed, and adding 840kg of TiO 2 Mixing the zirconium-cerium-tungsten compound solution and TiO 2 Uniformly mixing, standing the mixture for 30 hours, performing spray drying, rapidly evaporating water, calcining, setting the calcining temperature to 500 ℃, grinding the solid into powder after calcining, and controlling the particle size of the powder to be as follows: d50 is less than or equal to 5 mu m; d90 is less than or equal to 10 mu m.
(2) Preparation of vanadium compound solution:
weighing 10kg of ammonium metavanadate, dissolving the ammonium metavanadate in a monoethanolamine solution with the temperature of 80-100 ℃, stirring the solution uniformly and fixing the volume to 60L, wherein the mass of the monoethanolamine solution is 11.2 kg.
(3) And (3) preparing a mixed pug:
weighing zirconium-cerium-tungsten composite oxide-TiO 2 650kg of composite powder, 50L of vanadium compound solution, 6.5kg of lactic acid, 3.25kg of starch, 3kg of carboxymethyl cellulose, 7kg of polyethylene oxide, 120kg of pure water and 120kg of ammonia water, and mixing the raw materials fully together, stirring for 5-6h, and obtaining the pug after uniform mixing.
(4) Forming a honeycomb blank:
aging the mixed pug for 10 hours, filtering and pre-extruding to form a pug blank with uniform humidity, putting the pug blank into a forming machine, and extruding the honeycomb blank by a die.
(5) Further treatment of the honeycomb embryo:
and (3) putting the formed honeycomb blank into a drying room for drying, wherein the drying temperature is set to be 60 ℃, the drying period is 12 days, and when the weight reduction rate of the honeycomb blank reaches more than 25%, the drying is finished.
And (3) calcining the honeycomb blank after the drying is finished, wherein the calcining temperature is set at 450 ℃, and the calcining period is more than 35 hours. And (5) after the calcination is finished, obtaining a precursor.
(6) Loading of platinum compound:
and diluting the high-concentration platinum nitrate solution to a concentration of 0.5%, and immersing the precursor in the platinum nitrate diluted solution for 30min.
(7) Precursor loading and further processing:
and (3) placing the loaded precursor into a drying room for drying, wherein the drying temperature is set to 55 ℃, and the drying period is more than 96 hours.
And (3) calcining the loaded precursor after the drying is finished, wherein the calcining temperature is set at 400 ℃, and the calcining period is 28h. And (5) after the calcination is finished, obtaining the product.
Catalyst performance test prepared based on the preparation method of example 10: the flue gas conditions were designed as shown in table 49;
Table 49 design flue gas conditions
At the same temperature of 380 ℃, different inlets NO were tested separately x Denitration efficiency at the concentration, and the obtained results are shown in table 50;
table 50 same temperature, different inlet NO x Denitration efficiency at concentration
The denitration efficiency at different inlet CO concentrations was tested at the same temperature of 380 ℃ to obtain the results shown in Table 51;
table 51 decarburization efficiency at the same temperature and at different inlet CO concentrations
At the same temperature of 380 ℃, different inlets NH are respectively tested 3 Denitration efficiency at the concentration, and the obtained results are shown in table 52;
table 52 same temperature, different inlet NH 3 Deamination efficiency at content
Inlet NO x The concentration was 250mg/Nm 3 The inlet CO concentration was 1500mg/Nm 3 The denitration and decarbonization efficiencies measured at different temperatures were compared as shown in table 53;
table 53 comparison of denitration and decarburization efficiencies at different temperatures
At inlet NH 3 Deamination efficiency at the same content and different temperatures is shown in table 54;
table 54 entry NH 3 Deamination efficiency at the same, different temperatures
The embodiment provides a preparation method of a denitration, decarbonization and deamination three-way composite catalyst, wherein the mass ratio of a carrier to cerium, zirconium and tungsten is 1:0.194, 1:0.148 and 1:0.196 respectively, the carrier is immersed in 0.5% platinum solution, the denitration efficiency reaches 86% -91%, the decarbonization efficiency reaches 76% -80% and the deamination efficiency reaches 86% -89%.
The foregoing is merely illustrative of the present application, and the present application is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present application. The scope of the application is therefore defined by the appended claims.

Claims (10)

1. The preparation method of the denitration, decarbonization and deamination three-way composite catalyst is characterized by comprising the following steps:
preparing a carrier; firstly, uniformly mixing a cerium compound, a zirconium compound and a tungsten compound, and then dissolving the mixture in water to form a zirconium-cerium-tungsten composite oxide aqueous solution; secondly, adding TiO into the zirconium-cerium-tungsten composite oxide aqueous solution 2 Uniformly mixing to obtain a mixture, drying, calcining and grinding the mixture to obtain the zirconium-cerium-tungsten composite oxide-TiO 2 Composite powder as the carrier; wherein the molar ratio of the carrier to the cerium compound, the zirconium compound and the tungsten compound is 1: (0.035 to 0.350), 1: (0.049-0.247), 1: (0.131-0.262);
preparing a vanadium compound solution; wherein, according to the mass percent of the carrier and the ammonium metavanadate of 1 (0.5% -2.5%), the ammonium metavanadate for preparing the vanadium compound solution is weighed;
Preparing a precursor; wherein the zirconium-cerium-tungsten composite oxide-TiO 2 Mixing and stirring the composite powder, the vanadium compound solution, the forming additive and pure water to obtain mixed pug; molding and processing the mixed pug into a honeycomb blank; drying and calcining the honeycomb blank to obtain the precursor;
preparing a three-way composite catalyst; firstly, dipping the precursor in a mixed solution of 0.05% -1.0% of platinum solution and 0.05% -1.0% of palladium solution, wherein the dipping time is 30-60min, or dipping the precursor in 0.05% -1.0% of platinum solution, the dipping time is 30-60min, or dipping the precursor in 0.05% -1.0% of palladium solution, the dipping time is 30-60min, and the loaded precursor is obtained; secondly, drying and calcining the loaded precursor to obtain a denitration, decarbonization and deamination three-effect composite catalyst;
wherein the cerium compound comprises: one or more of cerium nitrate, cerium acetate, cerium sulfate, and cerium chloride; the zirconium compound comprises: one or more of zirconium nitrate, zirconium sulfate and zirconium chloride; the tungsten compound comprises: one or more of ammonium tungstate, ammonium meta-tungstate and ammonium paratungstate.
2. The method according to claim 1, wherein the zirconium-cerium-tungsten composite oxide-TiO 2 The particle size of the composite powder is as follows: d50 is less than or equal to 5 mu m; d90 is less than or equal to 10 mu m.
3. The method of preparing according to claim 1, wherein the preparing the vanadium compound solution comprises:
dissolving the weighed ammonium metavanadate into a monoethanolamine solution, and uniformly stirring to obtain a vanadium compound solution; wherein the mass fraction of the monoethanolamine solution is 5% -12%, and the temperature is 80 ℃ -100 ℃.
4. The method of claim 1, wherein the forming aid comprises one or more of lactic acid, carboxymethyl cellulose, polyethylene oxide, starch; the addition amount of the forming auxiliary agent is 0.3-5% of the mass of the carrier.
5. The method of claim 1, wherein the shaping the kneaded pug into a honeycomb green body comprises:
pretreating the mixed pug to obtain a pug blank, and forming the pug blank to obtain a honeycomb blank;
wherein, the pretreatment is as follows: and ageing the mixed pug for 10-14 hours, and filtering and pre-extruding to form a pug blank body with uniform humidity.
6. The method of claim 1, wherein drying and calcining the honeycomb green body to obtain a precursor comprises:
drying the honeycomb embryo, controlling the drying temperature within 55-65 ℃ and the drying period within 11 days, and ending the drying when the weight reduction rate of the honeycomb embryo reaches more than 25%;
and (3) calcining the honeycomb blank after the drying is finished, wherein the calcining temperature is controlled to be 450-550 ℃ and the calcining time is more than 35 hours.
7. The method of claim 1, wherein the calcination temperature of the mixture in the formulated carrier is from 400 ℃ to 500 ℃.
8. The preparation method of claim 1, wherein the drying and calcining the supported precursor to obtain the denitration, decarbonization and deamination three-way composite catalyst comprises the following steps:
drying the loaded precursor at the drying temperature of 50-60 ℃ for more than or equal to 70 hours;
and calcining the loaded precursor after the drying is finished.
9. The method according to claim 8, wherein the calcination temperature for calcining the supported precursor is 380 to 420 ℃ and the calcination time is 20 to 30 hours.
10. A denitration, decarbonization and deamination three-way composite catalyst, which is characterized by being prepared by adopting the preparation method of the denitration, decarbonization and deamination three-way composite catalyst as claimed in any one of claims 1-9.
CN202310898990.4A 2023-07-21 2023-07-21 Denitration, decarbonization and deamination three-effect composite catalyst and preparation method thereof Pending CN117019143A (en)

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