CN108355680B - Catalyst for cooperatively controlling multiple pollutants in fixed source flue gas and preparation method thereof - Google Patents

Catalyst for cooperatively controlling multiple pollutants in fixed source flue gas and preparation method thereof Download PDF

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CN108355680B
CN108355680B CN201810263144.4A CN201810263144A CN108355680B CN 108355680 B CN108355680 B CN 108355680B CN 201810263144 A CN201810263144 A CN 201810263144A CN 108355680 B CN108355680 B CN 108355680B
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cerium
sulfated
composite oxide
catalyst
vanadium
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CN108355680A (en
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陈雄波
岑超平
刘莹
方平
唐志雄
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South China Institute of Environmental Science of Ministry of Ecology and Environment
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/864—Removing carbon monoxide or hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8643—Removing mixtures of carbon monoxide or hydrocarbons and nitrogen oxides
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8678—Removing components of undefined structure
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
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    • B01D2251/206—Ammonium compounds
    • B01D2251/2062—Ammonia
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    • B01D2255/2065—Cerium
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2257/00—Components to be removed
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2258/0283—Flue gases
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    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

The invention discloses a catalyst for cooperatively controlling various pollutants in fixed source flue gas and a preparation method thereof. The active component of the catalyst is sulfated vanadium-cerium composite oxide, the carrier is sulfated titanium-aluminum composite oxide, the sulfated vanadium-cerium composite oxide is a complex of vanadium pentoxide, cerium dioxide, vanadyl sulfate and sulfuric acid, and the sulfated titanium-aluminum composite oxide is a complex of titanium dioxide, aluminum oxide, titanyl sulfate and aluminum sulfate. Under the action of the catalyst, NOx is substituted by NH3Selectively reduced to nitrogen and water, CO and VOCs being O2Oxidation to CO2And water. The catalyst is especially suitable for treating the smoke of fixed sources such as coal-fired, gas-fired, biomass-fired boilers, garbage incinerators and the like.

Description

Catalyst for cooperatively controlling multiple pollutants in fixed source flue gas and preparation method thereof
Technical Field
The invention belongs to the technical field of air pollution control, and particularly relates to a catalyst for cooperatively controlling various pollutants in fixed source flue gas and a preparation method thereof.
Background
The atmospheric emission source is divided into a mobile source and a fixed source, the common mobile source comprises an automobile, a ship and the like, and the common fixed source comprises a boiler (a power plant boiler and an industrial boiler), a kiln (a glass kiln, a ceramic kiln and a cement kiln), a garbage incinerator and the like. The fixed atmosphere pollution source can discharge particulate matters and sulfur dioxide (SO)2) Carbon monoxide (CO), nitrogen oxides (NOx), Volatile Organic Compounds (VOCs). The commonly used particulate purification technology comprises electrostatic dust collection, cloth bag dust collection, cyclone dust collection and the like, and the commonly used SO2The purification technology comprises a wet method, a semi-dry method, a dry method and the like, the commonly used NOx purification technology comprises Selective Catalytic Reduction (SCR), selective non-catalytic reduction (SNCR), oxidation absorption and the like, the commonly used VOCs control technology comprises a combustion method (catalytic combustion or thermal combustion), an adsorption method and the like, and CO is usually purified by the combustion method. In a fixed source flue gas treatment project, various single pollutant control technologies are generally required to be combined and connected in series, so that the defects of high cost, large occupied area, high operation and maintenance difficulty and the like are caused, and the development of a multi-pollutant cooperative control technology has important significance.
The catalytic method is one of the methods capable of realizing the cooperative control of various pollutants, and is generally applied to the purification of automobile exhaust. The concentration of Hydrocarbons (HC) and CO in the tail gas of the gasoline vehicle is high, the three-way catalyst (noble metal is the main active substance) can efficiently and simultaneously purify NOx, HC and CO at 500-850 ℃, and the gas substances participating in the reaction are NOx, HC, CO and O2. In the tail gas purification of diesel vehicles, because the HC concentration is relatively low, catalysts such as ammonia gas, vanadium-tungsten-titanium, molecular sieves, silver-aluminum and the like are required to be added to purify NOx and CO efficiently and simultaneously at the temperature of 200-450 ℃, and mainly NOx, CO and NH participating in the reaction3And O2. However, the application of the catalytic method in the fixed-source multi-pollutant cooperative control is very rare at present, and the main reason is the lack of a high-efficiency catalyst. Taking a biomass boiler as an example, the concentrations of NOx, CO and VOCs in the flue gas are high, but the temperature of the flue gas is usually only 150-450 ℃,the application temperature range of the automobile exhaust three-way catalyst is not met, and the VOCs and CO are difficult to purify due to the influence of low ammonia and smoke temperature although various diesel vehicle catalysts can realize the high-efficiency purification of NOx. Busca et al even found that conventional commercial vanadium-based denitration catalysts have limited purification effects on certain HC and oxygen-containing VOCs without introduction of ammonia gas [ Evaluation of V2O5–WO3–TiO2and alternative SCR catalysts in the present invention of VOCs, Catalysis Today 53(1999) 525-533. In addition, the flue gas of a fixed source usually contains SO2Substances such as K, Na, Ca and the like can cause the poisoning and inactivation of the catalyst, and the patent 201410040277.7 finds that the poisoning and inactivation of the catalyst in the smoke of the biomass boiler are particularly serious.
Therefore, the development of a suitable catalyst is the key of a catalytic method for the synergistic control of the fixed-source smoke multiple pollutants. The catalyst for the synergistic purification of a plurality of pollutants in the flue gas of a fixed source has the characteristics of low operation temperature (150-450 ℃), high simultaneous purification efficiency of the pollutants (particularly, the inhibition of ammonia gas on the oxidation of VOCs and CO is avoided), strong sulfur resistance and alkali metal/alkaline earth metal poisoning resistance, and the like.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention mainly aims to provide a catalyst for cooperatively controlling various pollutants in fixed source flue gas.
The invention also aims to provide a preparation method of the catalyst for synergistically controlling multiple pollutants in the smoke of a fixed source.
In order to achieve the purpose, the invention adopts the following technical scheme:
the catalyst for synergistic control of several pollutants in fixed source fume has the active component of sulfated composite vanadium-cerium oxide and the carrier of sulfated composite titanium-aluminum oxide.
The sulfated vanadium-cerium composite oxide is a composite of vanadium pentoxide, cerium dioxide, vanadyl sulfate and cerium sulfate.
The sulfated titanium-aluminum composite oxide is a composite of titanium dioxide, aluminum oxide, titanyl sulfate and aluminum sulfate.
Preferably, the mass fraction of the carrier is 80-99.5%, and the mass fraction of the active component is 0.5-20%.
The preparation method of the catalyst for cooperatively controlling various pollutants in the flue gas of the fixed source comprises the following steps:
(1) weighing a cerium precursor and a vanadium precursor, dissolving the cerium precursor and the vanadium precursor in an excessive oxalic acid solution, heating and stirring the mixture in a water bath at 60-80 ℃ to form an emulsion, then adding an excessive sulfuric acid solution, heating and stirring the mixture in a water bath at 60-80 ℃ to form an emulsion, and drying the emulsion at 60-100 ℃ to obtain a sulfated vanadium-cerium composite oxide;
(2) weighing titanium dioxide and aluminum oxide, soaking in an excessive sulfuric acid solution, stirring for 4 hours, carrying out suction filtration, drying at 60-100 ℃, and finally roasting at 500-700 ℃ for 1-4 hours to obtain a sulfated titanium-aluminum composite oxide;
(3) mixing the sulfated vanadium-cerium composite oxide and the sulfated titanium-aluminum composite oxide, grinding the mixture into powder, adding excessive water, stirring the mixture for 4 hours, drying the mixture at the temperature of between 60 and 100 ℃, and finally roasting the mixture for 2 to 6 hours at the temperature of between 350 and 550 ℃.
Preferably, when the sulfated vanadium-cerium composite oxide is prepared in the step (1), the molar ratio of V/Ce is controlled to be 0.2-5.
Preferably, the cerium precursor in step (1) is one or more of cerium nitrate, cerium carbonate, cerium oxalate and cerium dioxide.
Preferably, the vanadium precursor in step (1) is one or both of ammonium metavanadate and vanadium pentoxide.
Preferably, the concentration of the sulfuric acid solution in the steps (1) and (2) is 0.05-2.5 mol/L.
Preferably, in the step (2), the molar ratio of Ti/Al is controlled to 1 to 50 when preparing the sulfated titanium-aluminum composite oxide.
Preferably, the titanium dioxide and the alumina in the step (2) can be selected from various crystal forms of commercial products, and the specific surface area of the titanium dioxide is not less than 40m2(g) specific surface area of alumina of not less than 100m2/g。
The catalyst for the synergistic purification of a plurality of pollutants in the flue gas of a fixed source must still have excellent oxidation-reduction characteristics at a low temperature of the flue gas, and needs to be in NH state3In the presence of the catalyst, the reduction of NOx and the oxidation of CO and VOCs can be simultaneously realized. Vanadium pentoxide, cerium dioxide, vanadyl sulfate and cerium sulfate form multiple active centers on the surface of the catalyst, so that competition of different reactions on a single active center is avoided. The active points of vanadium pentoxide, cerium dioxide and cerium sulfate can efficiently catalyze NOx and NH3The oxidation reaction of CO and VOCs can be efficiently catalyzed by the active points of vanadium pentoxide and vanadyl sulfate through SCR reaction, and a large amount of chemical adsorption oxygen can be provided for the oxidation reaction of CO and VOCs by cerium oxide.
The catalyst for the synergistic purification of various pollutants in the fixed source flue gas also has strong capability of resisting sulfur and alkali metal/alkaline earth metal poisoning. SO (SO)2The resulting catalyst poisoning is mainly caused by the deactivation of the active components after the formation of sulfates, and SO2And NH3The ammonium sulfate generated by the reaction is deposited on the surface of the catalyst to hinder the catalytic reaction. The sulfate of vanadium and cerium still has good catalytic activity, and cerium oxide can accelerate the decomposition of sulfur ammonium salt, so that the catalyst has excellent sulfur resistance. The alkali/alkaline earth metal-induced catalyst poisoning results primarily from the destruction of the acid sites and the modification of the morphology of the active metal component. Because the carrier of the catalyst is subjected to sulfation treatment, the surface acidity of the carrier is greatly enhanced, the damage of alkali metal/alkaline earth metal to the acid sites of the catalyst is relieved, and the introduced sulfate can be combined with the alkali metal/alkaline earth metal to prevent the alkali metal/alkaline earth metal from contacting with active metal components, so that the catalyst has excellent alkali metal/alkaline earth metal poisoning resistance.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) under the action of the catalyst of the invention, NOx is substituted by NH3Selectively reduced to nitrogen and water, CO and VOCs being O2Oxidation to CO2And water; the catalyst has the purification efficiency of 95-100% for NOx and the purification efficiency of higher than 90% yetto 450 ℃ for CO at the temperature of 280-450 DEG C100 percent, the purification efficiency of VOCs is higher than 85 to 100 percent; the catalyst has the purification efficiency of 30-95% for NOx, higher than 20-90% for CO and higher than 20-85% for VOCs at the temperature of 150-280 ℃.
(2) The catalyst disclosed by the invention can simultaneously purify various pollutants, reduce treatment facility units, reduce investment cost and operation cost and reduce occupied land.
(3) The catalyst disclosed by the invention has excellent sulfur resistance and alkali metal/alkaline earth metal poisoning resistance, and has very long service life.
(4) The catalyst disclosed by the invention is particularly suitable for treating flue gas of fixed sources such as coal-fired, gas-fired, biomass-fired boilers, garbage incinerators and the like.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
The catalyst for cooperatively controlling various pollutants in fixed source flue gas has the active components of sulfated vanadium-cerium composite oxide and sulfated titanium-aluminum composite oxide as the carrier, and the preparation method comprises the following steps:
(1) weighing 2.52g of cerium nitrate and 0.51g of ammonium metavanadate, dissolving in excessive oxalic acid solution, heating and stirring in a water bath at 60 ℃ to form emulsion, then adding excessive 0.25mol/L sulfuric acid solution, heating and stirring in a water bath at 60 ℃ to form emulsion, and drying at 80 ℃ to obtain the sulfated vanadium-cerium composite oxide.
(2) 8.516g of titanium dioxide and 0.5427g of alumina are weighed, dipped in excessive 0.25mol/L sulfuric acid solution, stirred for 4 hours, filtered, dried at 80 ℃, and finally roasted for 4 hours at 600 ℃ to obtain sulfated titanium-aluminum composite oxide.
(3) Mixing the sulfated vanadium-cerium composite oxide and the sulfated titanium-aluminum composite oxide, grinding into powder, adding excessive water, stirring for 4 hours, drying at 80 ℃, and finally roasting at 450 ℃ for 2 hours. The mass fraction of the active component of the prepared catalyst is about 12.5 percent.
Coal fired boilers were simulated in the laboratory to produce flue gas containing a variety of pollutants. Taking 0.5g of the prepared catalyst with the mesh size of 40-60, putting the catalyst into a fixed bed reactor, and introducing smoke and ammonia gas; after catalytic reaction, the purification efficiency of NOx, CO and VOCs reaches 100% at 320 ℃, and the purification efficiency is not reduced within 48 hours.
Example 2
The catalyst for cooperatively controlling various pollutants in fixed source flue gas has the active components of sulfated vanadium-cerium composite oxide and sulfated titanium-aluminum composite oxide as the carrier, and the preparation method comprises the following steps:
(1) weighing 2.52g of cerium oxide and 0.2667g of vanadium pentoxide, dissolving in excessive oxalic acid solution, heating and stirring in water bath at 80 ℃ to form emulsion, then adding excessive 0.05mol/L sulfuric acid solution, heating and stirring in water bath at 80 ℃ to form emulsion, and drying at 100 ℃ to obtain the sulfated vanadium-cerium composite oxide.
(2) 8.516g of titanium dioxide and 10.853g of alumina are weighed, dipped in excessive 0.05mol/L sulfuric acid solution, stirred for 4 hours, filtered, dried at 100 ℃, and finally roasted for 1 hour at 700 ℃, so as to obtain the sulfated titanium-aluminum composite oxide.
(3) Mixing the sulfated vanadium-cerium composite oxide and the sulfated titanium-aluminum composite oxide, grinding into powder, adding excessive water, stirring for 4 hours, drying at 100 ℃, and finally roasting at 550 ℃ for 6 hours. The mass fraction of the active component of the prepared catalyst is about 9.5 percent.
Biomass boilers were simulated in the laboratory to produce flue gas containing a variety of pollutants. Taking 0.5g of the prepared catalyst with the mesh size of 40-60, putting the catalyst into a fixed bed reactor, and introducing smoke and ammonia gas; after catalytic reaction, the NOx purification efficiency reaches 85 percent at 250 ℃, the CO purification efficiency reaches 80 percent, the purification efficiency of VOCs reaches 65 percent, and the purification efficiency is not reduced within 48 hours.
Example 3
The catalyst for cooperatively controlling various pollutants in fixed source flue gas has the active components of sulfated vanadium-cerium composite oxide and sulfated titanium-aluminum composite oxide as the carrier, and the preparation method comprises the following steps:
(1) weighing 2.6g of cerium oxalate and 2.79g of ammonium metavanadate, dissolving in excessive oxalic acid solution, heating and stirring in a water bath at 70 ℃ to form emulsion, then adding excessive 1mol/L sulfuric acid solution, heating and stirring in a water bath at 70 ℃ to form emulsion, and drying at 60 ℃ to obtain the sulfated vanadium-cerium composite oxide.
(2) Weighing 8.5g of titanium dioxide and 1g of alumina, soaking in excessive 1mol/L sulfuric acid solution, stirring for 4 hours, filtering, drying at 60 ℃, and finally roasting at 500 ℃ for 2 hours to obtain the sulfated titanium-aluminum composite oxide.
(3) Mixing the sulfated vanadium-cerium composite oxide and the sulfated titanium-aluminum composite oxide, grinding into powder, adding excessive water, stirring for 4 hours, drying at 60 ℃, and finally roasting at 350 ℃ for 4 hours. The mass fraction of the active component of the prepared catalyst is about 20 percent.
Refuse incineration was simulated in the laboratory, producing flue gases containing a variety of pollutants. Taking 0.5g of the prepared catalyst with the mesh size of 40-60, putting the catalyst into a fixed bed reactor, and introducing smoke and ammonia gas; after catalytic reaction, the NOx purification efficiency reaches 70 percent at 200 ℃, the CO purification efficiency reaches 50 percent, the purification efficiency of VOCs reaches 45 percent, and the purification efficiency is not reduced within 48 hours.
Example 4
The catalyst for cooperatively controlling various pollutants in fixed source flue gas has the active components of sulfated vanadium-cerium composite oxide and sulfated titanium-aluminum composite oxide as the carrier, and the preparation method comprises the following steps:
(1) weighing 2.52g of cerium carbonate and 0.51g of ammonium metavanadate, dissolving in excessive oxalic acid solution, heating and stirring in a water bath at 70 ℃ to form emulsion, then adding excessive 0.25mol/L sulfuric acid solution, heating and stirring in a water bath at 70 ℃ to form emulsion, and drying at 90 ℃ to obtain the sulfated vanadium-cerium composite oxide.
(2) Weighing 7g of titanium dioxide and 0.38g of alumina, soaking in an excessive 2.5mol/L sulfuric acid solution, stirring for 4 hours, filtering, drying at 90 ℃, and finally roasting at 600 ℃ for 4 hours to obtain the sulfated titanium-aluminum composite oxide.
(3) Mixing the sulfated vanadium-cerium composite oxide and the sulfated titanium-aluminum composite oxide, grinding into powder, adding excessive water, stirring for 4 hours, drying at 70 ℃, and finally roasting at 400 ℃ for 2 hours. The mass fraction of the active component of the prepared catalyst is about 14.5 percent.
Biomass combustion was simulated in the laboratory to produce flue gas containing a variety of pollutants. Taking 0.5g of the prepared catalyst with the mesh size of 40-60, putting the catalyst into a fixed bed reactor, and introducing smoke and ammonia gas; after catalytic reaction, the purification efficiency of NOx, CO and VOCs reaches 100% at 320 ℃, and the purification efficiency is not reduced within 48 hours.
Example 5
The catalyst for cooperatively controlling various pollutants in fixed source flue gas has the active components of sulfated vanadium-cerium composite oxide and sulfated titanium-aluminum composite oxide as the carrier, and the preparation method comprises the following steps:
(1) weighing 0.252g of cerium nitrate and 0.12g of ammonium metavanadate, dissolving in excessive oxalic acid solution, heating and stirring in a water bath at 60 ℃ to form emulsion, then adding excessive 0.25mol/L sulfuric acid solution, heating and stirring in a water bath at 60 ℃ to form emulsion, and drying at 80 ℃ to obtain the sulfated vanadium-cerium composite oxide.
(2) Weighing 35.1g of titanium dioxide and 0.96g of alumina, soaking in excessive 0.5mol/L sulfuric acid solution, stirring for 4 hours, filtering, drying at 80 ℃, and finally roasting at 600 ℃ for 4 hours to obtain the sulfated titanium-aluminum composite oxide.
(3) Mixing the sulfated vanadium-cerium composite oxide and the sulfated titanium-aluminum composite oxide, grinding into powder, adding excessive water, stirring for 4 hours, drying at 80 ℃, and finally roasting at 450 ℃ for 5 hours. The mass fraction of the active component of the prepared catalyst is about 0.5 percent.
Biomass combustion was simulated in the laboratory to produce flue gas containing a variety of pollutants. Taking 0.5g of the prepared catalyst with the mesh size of 40-60, putting the catalyst into a fixed bed reactor, and introducing smoke and ammonia gas; after catalytic reaction, the purification efficiency of NOx, CO and VOCs reaches 100% at 320 ℃, and the purification efficiency is not reduced within 48 hours.
Example 6
The catalyst for cooperatively controlling various pollutants in fixed source flue gas has the active components of sulfated vanadium-cerium composite oxide and sulfated titanium-aluminum composite oxide as the carrier, and the preparation method comprises the following steps:
(1) weighing 3g of cerium nitrate and 1g of ammonium metavanadate, dissolving in excessive oxalic acid solution, heating and stirring in a water bath at 60 ℃ to form emulsion, then adding excessive 0.5mol/L sulfuric acid solution, heating and stirring in a water bath at 60 ℃ to form emulsion, and drying at 80 ℃ to obtain the sulfated vanadium-cerium composite oxide.
(2) Weighing 10g of titanium dioxide and 2g of alumina, soaking in excessive 0.5mol/L sulfuric acid solution, stirring for 4 hours, filtering, drying at 80 ℃, and finally roasting at 600 ℃ for 4 hours to obtain sulfated titanium-aluminum composite oxide.
(3) Mixing the sulfated vanadium-cerium composite oxide and the sulfated titanium-aluminum composite oxide, grinding into powder, adding excessive water, stirring for 4 hours, drying at 80 ℃, and finally roasting at 450 ℃ for 2 hours. The mass fraction of the active component of the prepared catalyst is about 12.5 percent.
Biomass combustion was simulated in the laboratory to produce flue gas containing a variety of pollutants. Taking 0.5g of the prepared catalyst with the mesh size of 40-60, putting the catalyst into a fixed bed reactor, and introducing smoke and ammonia gas; after catalytic reaction, the purification efficiency of NOx, CO and VOCs reaches 100% at 320 ℃, and the purification efficiency is not reduced within 48 hours.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (8)

1. A catalyst for synergistically controlling multiple pollutants in fixed source flue gas is characterized in that an active component of the catalyst is sulfated vanadium-cerium composite oxide, a carrier is sulfated titanium-aluminum composite oxide, the sulfated vanadium-cerium composite oxide is a composite of vanadium pentoxide, cerium dioxide, vanadyl sulfate and cerium sulfate, and the sulfated titanium-aluminum composite oxide is a composite of titanium dioxide, aluminum oxide, titanyl sulfate and aluminum sulfate;
the mass fraction of the carrier is 80-99.5%, and the mass fraction of the active component is 0.5-20%;
the preparation method of the catalyst for cooperatively controlling various pollutants in the fixed source flue gas comprises the following steps:
(1) weighing a cerium precursor and a vanadium precursor, dissolving the cerium precursor and the vanadium precursor in an excessive oxalic acid solution, heating and stirring the mixture in a water bath at 60-80 ℃ to form an emulsion, then adding an excessive sulfuric acid solution, heating and stirring the mixture in a water bath at 60-80 ℃ to form an emulsion, and drying the emulsion at 60-100 ℃ to obtain a sulfated vanadium-cerium composite oxide;
(2) weighing titanium dioxide and aluminum oxide, soaking in an excessive sulfuric acid solution, stirring for 4 hours, carrying out suction filtration, drying at 60-100 ℃, and finally roasting at 500-700 ℃ for 1-4 hours to obtain a sulfated titanium-aluminum composite oxide;
(3) mixing the sulfated vanadium-cerium composite oxide and the sulfated titanium-aluminum composite oxide, grinding the mixture into powder, adding excessive water, stirring the mixture for 4 hours, drying the mixture at the temperature of between 60 and 100 ℃, and finally roasting the mixture for 2 to 6 hours at the temperature of between 350 and 550 ℃.
2. The method for preparing the catalyst for the cooperative control of multiple pollutants in the flue gas of the fixed source according to claim 1, is characterized by comprising the following steps:
(1) weighing a cerium precursor and a vanadium precursor, dissolving the cerium precursor and the vanadium precursor in an excessive oxalic acid solution, heating and stirring the mixture in a water bath at 60-80 ℃ to form an emulsion, then adding an excessive sulfuric acid solution, heating and stirring the mixture in a water bath at 60-80 ℃ to form an emulsion, and drying the emulsion at 60-100 ℃ to obtain a sulfated vanadium-cerium composite oxide;
(2) weighing titanium dioxide and aluminum oxide, soaking in an excessive sulfuric acid solution, stirring for 4 hours, carrying out suction filtration, drying at 60-100 ℃, and finally roasting at 500-700 ℃ for 1-4 hours to obtain a sulfated titanium-aluminum composite oxide;
(3) mixing the sulfated vanadium-cerium composite oxide and the sulfated titanium-aluminum composite oxide, grinding the mixture into powder, adding excessive water, stirring the mixture for 4 hours, drying the mixture at the temperature of between 60 and 100 ℃, and finally roasting the mixture for 2 to 6 hours at the temperature of between 350 and 550 ℃.
3. The preparation method of the catalyst for synergistically controlling multiple pollutants in the flue gas with the fixed source according to claim 2, wherein when the sulfated vanadium-cerium composite oxide is prepared in the step (1), the molar ratio of V to Ce is controlled to be 0.2-5.
4. The method according to claim 2, wherein the cerium precursor in step (1) is one or more of cerium nitrate, cerium carbonate and cerium oxalate.
5. The method according to claim 2, wherein the vanadium precursor in step (1) is ammonium metavanadate.
6. The method for preparing the catalyst for synergistically controlling multiple pollutants in the flue gas with the fixed source according to claim 2, wherein the concentration of the sulfuric acid solution in the steps (1) and (2) is 0.05-2.5 mol/L.
7. The method for preparing the catalyst for synergistically controlling multiple pollutants in the flue gas with fixed source according to claim 2, wherein when the sulfated titanium-aluminum composite oxide is prepared in the step (2), the molar ratio of Ti/Al is controlled to be 1-50.
8. The method for preparing the catalyst for synergistically controlling multiple pollutants in fixed-source flue gas according to claim 2, wherein the specific surface area of the titanium dioxide in the step (2) is 40m2More than g, the specific surface area of the alumina is 100m2More than g.
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