CN105170140A - High-efficient SCR (Selective Catalytic Reduction) catalyst applicable to denitration reaction and preparation method of catalyst - Google Patents
High-efficient SCR (Selective Catalytic Reduction) catalyst applicable to denitration reaction and preparation method of catalyst Download PDFInfo
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- CN105170140A CN105170140A CN201510670430.9A CN201510670430A CN105170140A CN 105170140 A CN105170140 A CN 105170140A CN 201510670430 A CN201510670430 A CN 201510670430A CN 105170140 A CN105170140 A CN 105170140A
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Abstract
The invention provides a high-efficient SCR (Selective Catalytic Reduction) catalyst applicable to a denitration reaction and a preparation method of the catalyst, and belongs to the technical field of catalytic purification of exhaust emissions of motor vehicles. The catalyst is prepared by taking ordered mesopore titanium dioxide as a carrier, and taking one of vanadium and manganese as an active ingredient and using a rotary evaporation method. The catalyst provided by the invention has the advantages that by virtue of a long-range order pore channel of the ordered mesopore titanium dioxide and high specific surface area, the dispersion of a loaded substance is promoted, so that the contact area between the active ingredients namely the vanadium and the manganese and a reactant is increased, and the reaction activity of the catalyst is improved.
Description
Technical field
The invention belongs to catalysis method purifying motor exhaust emissions technical field, especially relate to a kind of efficient SCR catalyst being applied to denitration reaction and preparation method thereof.
Background technology
Along with the development of society, the pollution of current environment becomes a large problem.Nitrogen oxide (NO
x) be one of topmost pollutant in air, it has stronger bio-toxicity, and the respiratory system of energy intense stimulus human body, has a strong impact on the health of people.And NO
xor the main cause that acid rain and photochemical fog etc. produce.Along with the development of Chinese Automobile Industry ' grows, NO
xdischarge constantly aggravate.Therefore, effectively NO is processed
xpollutant is very meaningful and necessary.SCR (SCR, i.e. selectivecatalyticreduction) technology has been proved to be the most effective diesel vehicle NO
xone of removal technology.SCR technology general principle is under the effect of catalyst, utilizes NH
3deng reducing agent, optionally by the NO in diesel exhaust gas
xbe reduced into harmless nontoxic N
2and H
2o, realizes NO
xeffective removal.The key of this technology is the use of high performance catalyst.
Since from nineteen eighty-three, large-scale commercial applications SCR system is applied to coal-fired power plant first time by Japan, SCR catalyst just starts the pollution being widely used for processing nitrogen oxide, and the transformation efficiency developing into current NO can break through 80%-90%.And the present situation of just current China, study one more effective, cheap, activity performance remarkably, has the denitrating catalyst of stability and high strength, becomes the task of top priority.In order to reduce the waste gas that internal combustion engine of motor vehicle produces, NH
3-SCR and urea-SCR also uses vehicle maintenance service aspect more and more, such as be arranged on the Diesel engine of heavy vehicle and passenger train, in practical application, Problems existing is generally, when cold-starting automobile or short distance travel, create a large amount of nitrogen oxide, so how to carry out improvement to reduce reaction temperature interval, it is the direction that SCR catalyst one of being applied in motor vehicle exhaust gases process needs research.
Summary of the invention
Given this, the present invention is intended to propose a kind of efficient SCR catalyst being applied to denitration reaction and preparation method thereof, effectively to solve the problem of existing SCR catalyst low temperature active difference.
For achieving the above object, technical scheme of the present invention is achieved in that a kind of efficient SCR catalyst being applied to denitration reaction, in described catalyst, active component vanadium or manganese load are on mesoporous TiO 2, and wherein the mass fraction of active component vanadium or manganese is 1% ~ 5%.
A kind of preparation method being applied to the efficient SCR catalyst of denitration reaction, titania support is comprised the steps: to be scattered in deionized water, do not stop at normal temperatures to stir, then adding the precursor solution of vanadium or manganese, after mixing, is 50 ~ 100 DEG C in temperature, the rotating speed of Rotary Evaporators is under the condition of 60-90r/m, rotary evaporation, until evaporating water, then puts into Muffle furnace, roasting 2-4 hour under 350 DEG C of conditions.
Further, in described catalyst, the mass fraction of active component vanadium or manganese is 2%.
Further, described catalyst carrier titanium dioxide utilizes solvent evaporation method to prepare, and the specific area of its titanium dioxide is 217.14m
2g
-1, the average pore size of its titanium dioxide is 5.5nm.
Further, described catalyst before carrying out SCR reaction need under oxygen atmosphere 350 DEG C within roasting 2-4 hour, carry out pretreatment.
Further, described catalyst 2%V/TiO
2when carrying out SCR reaction, NO conversion ratio can reach 100% between 280 DEG C to 350 DEG C, described catalyst 2%Mn/TiO
2when carrying out SCR reaction, NO conversion ratio can reach 100% at the middle-temperature section of 150 DEG C to 250 DEG C.
Further, described vanadium presoma is sodium metavanadate, and described sodium metavanadate is dissolved in oxalic acid and forms vanadium precursor solution.
Further, described manganese presoma is four water manganese nitrates, and described four water manganese nitrates are dissolved in deionized water and form manganese precursor solution.
Relative to prior art, a kind of efficient SCR catalyst being applied to denitration reaction of the present invention and preparation method thereof has following advantage: catalyst of the present invention uses ordered mesoporous silica dioxide as carrier, catalyst activity performance can be promoted, mainly due to the high-specific surface area of silica, highly regular hole shape and larger aperture, active component can be distributed more equably, regular duct improves the density of avtive spot, and also promote the diffusion of reactant and product, the pore volume that high-ratio surface sum is larger enhances its load capacity and adsorption capacity, mesoporous titanic oxide material is better than non-mesoporous type, be due to mesoporous type material not only can with active component generation surface reaction, more can material bodies mutually in react.
Accompanying drawing explanation
The accompanying drawing forming a part of the present invention is used to provide a further understanding of the present invention, and embodiments of the invention and explanation thereof, for explaining the present invention, do not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 is 2%V/TiO
2and 2%Mn/TiO
2the XRD figure of catalyst.Do not demonstrate the peak of vanadium and violent oxide in wide-angle XRD collection of illustrative plates in figure, illustrate that vanadium and violent active specy high uniformity have been dispersed on carrier titanium dioxide, and exist with amorphous phase.
Fig. 2 is 2%V/TiO
2and 2%Mn/TiO
2the adsorption-desorption isothermal of catalyst.Can find out that the adsorption-desorption isothermal of these two kinds of catalyst belongs to IV type curve, and have typical H1 type and return stagnant ring, therefore illustrate that these two kinds of catalyst have more regular size and mesoporous existence, the shape in hole is cylindric.
Fig. 3 is 2%V/TiO
2and 2%Mn/TiO
2the graph of pore diameter distribution of catalyst.Can find out that the pore-size distribution of these two kinds of catalyst samples is narrower, 2%V/TiO
2and 2%Mn/TiO
2most probable pore size be respectively 6.1nm and 5.3nm.
Detailed description of the invention
It should be noted that, when not conflicting, the embodiment in the present invention and the feature in embodiment can combine mutually.
Embodiment 1: Kaolinite Preparation of Catalyst 2%V/TiO
2and 2%Mn/TiO
2
Take the anion surfactant triblock copolymer ((EO) of 3.2g
100(PO)
65(EO)
100, F127, molecular weight 12600) be scattered in 60mL absolute ethyl alcohol, then 4.6mL acetic acid and 1.48mL hydrochloric acid is added successively, stir at normal temperatures, after surfactant disperses completely, slowly add 7.0mL butyl titanate (relative density 0.966) again, vigorous stirring is after 1 hour, solution is transferred in evaporating dish, in relative humidity 40% time (relative humidity is controlled by unsaturated carbonate potassium solution), solvent volatilization is carried out in 40 DEG C of baking ovens, 65 DEG C of baking ovens are put into after 48 hours, take out after 24 hours, put into Muffle furnace, temperature programming to 350 DEG C calcining 4 hours, heating rate is 2 DEG C/min.
Taking the 1.0g titania support prepared with said method is scattered in deionized water, do not stop at normal temperatures to stir, then take 0.05g sodium metavanadate to be dissolved in 5mL oxalic acid and to form solution, this solution is joined and is dispersed with in the deionized water of titanium dioxide, after mixing, at temperature 60 C, the rotating speed of Rotary Evaporators is under the condition of 80r/m, and rotary evaporation, until evaporating water, then puts into Muffle furnace, under 350 DEG C of conditions, roasting 2 hours, obtains 2%V/TiO after roasting
2catalyst.
Taking the 1.0g titania support prepared with said method is scattered in deionized water, do not stop at normal temperatures to stir, then take 0.07g tetra-water manganese nitrate to be dissolved in 5mL deionized water and to form solution, being joined by this solution is dispersed with in the deionized water of titanium dioxide, after mixing, at temperature 60 C, the rotating speed of Rotary Evaporators is under the condition of 80r/m, rotary evaporation is until evaporating water, then Muffle furnace is put into, under 350 DEG C of conditions, roasting 2 hours, obtains 2%Mn/TiO after roasting
2catalyst.
Embodiment 2: catalyst 2%V/TiO
2and 2%Mn/TiO
2react for SCR
Take the pretreated 2%V/TiO of 0.4g
2or 2%Mn/TiO
2catalyst loads in fixed bed reactors, and wherein the mist of reaction gas consists of [NO]=[NH
3]=1000ppm, [O
2]=6.7%, He is Balance Air, gas speed is 10000mL/ (gh), temperature controller is utilized to be carried out in the scope of 100 DEG C to 500 DEG C by reaction controlling, often heat up 50 DEG C and carry out one-shot measurement, no matter for reactant concentration or production concentration, all at a given temperature, within every 30 minutes, survey 4 data, average.Use 2%V/TiO
2during catalyst, NO conversion ratio can reach 100% between 280 DEG C to 350 DEG C, uses 2%Mn/TiO
2time, NO conversion ratio can reach 100% at the middle-temperature section of 150 DEG C to 250 DEG C.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. be applied to an efficient SCR catalyst for denitration reaction, it is characterized in that, in described catalyst, active component vanadium or manganese load are on mesoporous TiO 2, and wherein the mass fraction of active component vanadium or manganese is 1% ~ 5%.
2. a kind of efficient SCR catalyst being applied to denitration reaction according to claim 1, is characterized in that: in described catalyst, the mass fraction of active component vanadium or manganese is 2%.
3. a kind of efficient SCR catalyst being applied to denitration reaction according to claim 1, it is characterized in that: described catalyst carrier titanium dioxide utilizes solvent evaporation method to prepare, the specific area of its titanium dioxide is 217.14m
2g
-1, the average pore size of its titanium dioxide is 5.5nm.
4. a kind of efficient SCR catalyst being applied to denitration reaction according to claim 1, is characterized in that: described catalyst before carrying out SCR reaction need under oxygen atmosphere 350 DEG C within roasting 2-4 hour, carry out pretreatment.
5. a kind of efficient SCR catalyst being applied to denitration reaction according to claim 1, is characterized in that: described catalyst 2%V/TiO
2when carrying out SCR reaction, NO conversion ratio can reach 100% between 280 DEG C to 350 DEG C, described catalyst 2%Mn/TiO
2when carrying out SCR reaction, NO conversion ratio can reach 100% at the middle-temperature section of 150 DEG C to 250 DEG C.
6. one kind is applied to the preparation method of the efficient SCR catalyst of denitration reaction, it is characterized in that: comprise the steps: titania support to be scattered in deionized water, do not stop at normal temperatures to stir, then adding the precursor solution of vanadium or manganese, after mixing, is 50 ~ 100 DEG C in temperature, the rotating speed of Rotary Evaporators is under the condition of 60-90r/m, rotary evaporation, until evaporating water, then puts into Muffle furnace, roasting 2-4 hour under 350 DEG C of conditions.
7. a kind of preparation method being applied to the efficient SCR catalyst of denitration reaction according to claim 6, it is characterized in that: described vanadium presoma is sodium metavanadate, described sodium metavanadate is dissolved in oxalic acid and forms vanadium precursor solution.
8. a kind of preparation method being applied to the efficient SCR catalyst of denitration reaction according to claim 6, it is characterized in that: described manganese presoma is four water manganese nitrates, described four water manganese nitrates are dissolved in deionized water and form manganese precursor solution.
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Cited By (5)
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| CN106984301A (en) * | 2017-04-24 | 2017-07-28 | 中盐金坛盐化有限责任公司 | A kind of ordered mesopore structure manganese cerium titanium catalyst and preparation method and purposes |
| CN109201043A (en) * | 2018-11-14 | 2019-01-15 | 清华大学盐城环境工程技术研发中心 | A method of preparing mesoporous manganese titanium low-temperature denitration catalyst |
| CN110508275A (en) * | 2019-08-21 | 2019-11-29 | 上海应用技术大学 | A kind of mesoporous material load manganese dioxide-catalyst and preparation method thereof |
| CN116328783A (en) * | 2023-02-01 | 2023-06-27 | 襄阳泽东化工集团股份有限公司 | Preparation method of high-stability SCR denitration catalyst |
| CN117045823A (en) * | 2023-10-11 | 2023-11-14 | 四川美文鑫彩新材料科技有限公司 | Mesoporous hollow copper single-atom carbon sphere, preparation method and application |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110508275A (en) * | 2019-08-21 | 2019-11-29 | 上海应用技术大学 | A kind of mesoporous material load manganese dioxide-catalyst and preparation method thereof |
| CN110508275B (en) * | 2019-08-21 | 2022-08-26 | 上海应用技术大学 | Mesoporous material loaded manganese dioxide catalyst and preparation method thereof |
| CN116328783A (en) * | 2023-02-01 | 2023-06-27 | 襄阳泽东化工集团股份有限公司 | Preparation method of high-stability SCR denitration catalyst |
| CN117045823A (en) * | 2023-10-11 | 2023-11-14 | 四川美文鑫彩新材料科技有限公司 | Mesoporous hollow copper single-atom carbon sphere, preparation method and application |
| CN117045823B (en) * | 2023-10-11 | 2023-12-19 | 四川美文鑫彩新材料科技有限公司 | Mesoporous hollow copper single-atom carbon sphere, preparation method and application |
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Application publication date: 20151223 |