CN104324728A - Mesoporous composite oxide catalyst for purifying tail gases and preparation method thereof - Google Patents

Mesoporous composite oxide catalyst for purifying tail gases and preparation method thereof Download PDF

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CN104324728A
CN104324728A CN201410616590.0A CN201410616590A CN104324728A CN 104324728 A CN104324728 A CN 104324728A CN 201410616590 A CN201410616590 A CN 201410616590A CN 104324728 A CN104324728 A CN 104324728A
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composite oxides
mesoporous composite
catalyst
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CN104324728B (en
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陈英
陈航榕
施剑林
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Shanghai Institute of Ceramics of CAS
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Shanghai Institute of Ceramics of CAS
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Abstract

The invention relates to a mesoporous composite oxide catalyst for purifying tail gases and a preparation method thereof. The composition chemical formula of the mesoporous composite oxide catalyst is V2O5- WO3-CuOx-Al2O3/ZrO2-TiO2, wherein the ratio of the mass of V to the mass sum of ZrO2 and TiO2 is not larger than 10%, the ratio of the mass of W to the mass sum of ZrO2 and TiO2 is not larger than 20%, the ratio of the mass of Cu to the mass sum of ZrO2 and TiO2 is not larger than 10%, the ratio of the mass of Al to the mass sum of ZrO2 and TiO2 is not larger than 5%, and the value range of x is that x is not smaller than 0 and is not larger than 1.

Description

The mesoporous composite oxides Catalysts and its preparation method of tail gas clean-up
Technical field
The present invention relates to a kind of NH 3-SCR catalyst and preparation method thereof, particularly relates to and a kind ofly has composite oxide catalysts of crystallization meso-hole structure and preparation method thereof, belong to environmental catalysis field of purification.
Background technology
Diesel vehicle obtains apply more and more widely with its low oil consumption, high-power feature, but be form one of nitric acid type acid rain and photochemical fog, the Air Pollutants that damages the ozone layer from the nitrogen oxide (NOx) in exhaust gas from diesel vehicle, there is very strong toxicity, bring serious harm to natural environment and human being's production life.Therefore, eliminate nitrogen oxide and become a urgent problem in current field of Environment Protection.
At present, ammine selectivity catalytic reduction method (NH 3-SCR) be considered to NO under excess oxygen xremove one of most effective method, its general principle is NH 3as reducing agent, under the effect of catalyst, by NO xetc. being reduced into harmless N 2and H 2o, the key of this technology is to use high performance catalyst.Wherein V 2o 5-WO 3/ TiO 2catalyst system and catalyzing is due to its higher catalytic performance, and application of having succeeded in stationary source (coal-fired plant flue gas) and moving source (exhaust gas from diesel vehicle) denitration, but also there is a lot of problem, the heat endurance as catalyst is poor, low temperature NH 3-SCR activity is not enough.Therefore need to carry out performance optimization to meet the requirement of exhaust gas from diesel vehicle discharge to such catalyst system and catalyzing.
Summary of the invention
The present invention is intended to overcome the step of existing exhaust gas catalytic conversion at aspect of performance, the invention provides a kind of mesoporous composite oxides Catalysts and its preparation method of tail gas clean-up.
The invention provides a kind of mesoporous composite oxides catalyst of tail gas clean-up, the constitutional chemistry of described mesoporous composite oxides catalyst is V 2o 5-WO 3-CuO x-Al 2o 3/ ZrO 2-TiO 2, wherein, the quality of V and ZrO 2, TiO 2the quality of quality and Zhi Bi≤10%, W and ZrO 2, TiO 2the quality of quality and Zhi Bi≤20%, Cu and ZrO 2, TiO 2the quality of quality and Zhi Bi≤10%, Al and ZrO 2, TiO 2the span of quality and Zhi Bi≤5%, x is 0≤x≤1, preferably 0 < x≤1.
Preferably, described mesoporous composite oxides catalyst has meso-hole structure, and mesoporous aperture is 5-30nm, and described mesoporous composite oxides catalyst crystallization degree is high, and specific area is 60-200m 2/ g.
Preferably, described mesoporous composite oxides catalyst can use at 200-500 DEG C.
Again, present invention also offers a kind of preparation method of above-mentioned mesoporous composite oxides catalyst, described method comprises:
1) pore creating material, soluble vanadium vanadic salts, soluble vanadium tungsten salt, soluble vanadium mantoquita, soluble vanadium aluminium salt, oxalic acid Homogeneous phase mixing in water are obtained the first mixed liquor;
2) zirconium source and titanium source are dispersed in alcoholic solution obtain the second mixed liquor (as far as possible the effect of alcoholic solution makes the hydrolysis rate in zirconium source and titanium source reach unanimity, and makes them mix better, obtains uniform zirconium titanium carrier);
3) by step 1) the first mixed liquor and step 2 of preparing) the second mixed liquor of preparing obtains the 3rd mixed liquor, and wherein in the 3rd mixed liquor, the ratio of metallic element meets the ratio of metallic element in described mesoporous composite oxides SCR catalyst;
4) by step 3) the 3rd mixed liquor prepared 100-150 DEG C of hydro-thermal, then filter, to wash and dry, be precipitated thing;
5) by step 4) sediment that obtains 400-600 DEG C of roasting, obtain described mesoporous composite oxides catalyst;
Or directly vanadic salts, tungsten salt, mantoquita, aluminium salt, oxalic acid, zirconium-n-propylate and tetrabutyl titanate are mixed with the 3rd mixed liquor, carry out steps 4 successively) and step 5), prepare described mesoporous composite oxides catalyst.
Preferably, step 1) in, mixed uniformly mode is at 20-50 DEG C of heating water bath and stirs 2-6h, and pore creating material is Brij-35 and/or P123.
Preferably, step 2) in, zirconium source comprises zirconium-n-propylate, zirconium-n-butylate, zirconium tert-butoxide and/or ethanol zirconium etc., and titanium source comprises butyl titanate and/or isopropyl titanate etc.
Preferably, step 2) in, the alcohol in alcoholic solution is ethanol and/or isopropyl alcohol etc., and in alcoholic solution, the mass fraction of alcohol is 80-100%.
Preferably, step 2) in, homodisperse mode is at stirring at room temperature 1-5 hour.
Preferably, step 4) in, the 3rd mixed liquor is first stirred 6-12 hour at 20-50 DEG C of heating water bath, then within hydro-thermal 20-30 hour, (in this operation, heating water bath the function stirred is accelerate dissolution, makes reactant mix better at 100-150 DEG C; The material scatter that hydro-thermal reaction synthesizes is good and purity is high).
Preferably, step 5) in, roasting 3-6 hour.
Beneficial effect of the present invention:
1, compared to commercial catalyst, obtained mesoporous composite oxides crystallization material has more excellent low-temperature catalytic activity and wider Process window, can up to 71% 150 DEG C of conversion efficiencies to NO, the 200-500 DEG C of conversion that can realize higher than 92%NO, (test condition is: NO concentration 500ppm, NH 3concentration 500ppm, O 2concentration 5%, He makes Balance Air, and total gas flow rate is 200mL/min, and air speed is 40,000 ~ 60,000h -1.)；
2, using two kinds of surfactant B rij-35 and P123 as mesoporous pore creating material, by hydrothermal crystallization method, preparation synthesizes various active component as equally loaded mesoporous ZrO_2-TiO2 (ZT) base composite oxidate catalyst such as V2O5, WO3, CuOx, Al2O3.
Accompanying drawing explanation
Fig. 1 shows mesoporous composite oxides catalysis material obtained in an embodiment of the invention and the N of other catalysis material 2adsorption-desorption figure;
Fig. 2 shows the V obtained by the embodiment of the present invention one 2o 5-WO 3-CuO x-Al 2o 3/ ZrO 2-TiO 2, made carrier material ZrO in embodiment five 2-TiO 2and the XRD collection of illustrative plates of anatase titanium dioxide;
Fig. 3 shows the V obtained by the embodiment of the present invention one 2o 5-WO 3-CuO x-Al 2o 3/ ZrO 2-TiO 2tEM electromicroscopic photograph and EDS collection of illustrative plates and embodiment five in made carrier material ZrO 2-TiO 2tEM electromicroscopic photograph;
Fig. 4 shows the V obtained by the embodiment of the present invention one 2o 5-WO 3-CuO x-Al 2o 3/ ZrO 2-TiO 2sEM electromicroscopic photograph;
Fig. 5 shows the V obtained by the embodiment of the present invention one 2o 5-WO 3-CuO x-Al 2o 3/ ZrO 2-TiO 2with the H of the made commercial catalyst V-W/Ti of comparative example one (commercial catalyst) 2-TPR spectrogram;
Fig. 6 shows the V prepared in an embodiment of the invention 2o 5-WO 3-CuO x-Al 2o 3/ ZrO 2-TiO 2with the made commercial catalyst V-W/Ti of comparative example one (commercial catalyst) to conversion rate of NOx spectrogram.
Detailed description of the invention
Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that accompanying drawing and following embodiment are only for illustration of the present invention, and unrestricted the present invention.
The invention belongs to environmental protection technical field; for the deficiency of conventional commercial catalyst (V-W/Ti) catalytic performance; design a kind of New Type of Mesoporous composite oxidant SCR (Selective Catalytic Reduction) denitrating catalyst for diesel car tail gas refining and preparation method thereof, make it that there is higher heat endurance and good low-temperature catalytic activity.Catalyst is expressed from the next: V 2o 5-WO 3-CuO x-Al 2o 3/ ZrO 2-TiO 2; Wherein, ZrO 2-TiO 2be meso-hole structure zirconium titanium composite oxides carrier (representing with ZT), the weight percent content of preferred catalytic active component V, W, Cu, Al is respectively 0 ~ 10%, 0 ~ 20%, 0 ~ 10%, 0 ~ 5% of ZT vehicle weight.
Described V 2o 5with the load in addition of the form of vanadic salts, can be ammonium salt inorganic salts.
Described WO 3with the load in addition of the form of tungsten salt, can be ammonium salt inorganic salts.
Described CuO xwith the load in addition of the form of mantoquita, can be the inorganic salts such as sulfate, nitrate of solubility.
Described Al 2o 3with the load in addition of the form of aluminium salt, can be nitrate or the organic alkoxide of solubility.
Described zirconium titanium composite oxides carrier is single Detitanium-ore-type, and its specific area is 100-150m 2/ g.
Again, present invention also offers a kind of diesel car tail gas refining method for preparing catalyst, comprise the following steps:
1. getting 4.5gBrij-35,3.7gP123 and 1g oxalic acid is dissolved in 100mL water, the vanadic salts calculated by the weight percent content of V, W, Cu, Al, tungsten salt, mantoquita, aluminium salt add in the oxalic acid solution of configuration, stirs 2-6h at 20-50 DEG C of heating water bath;
2. 1.2ml zirconium-n-propylate is got and 8.8ml butyl titanate is added drop-wise in the ethanolic solution of 40ml, stirring at room temperature 1-5h;
3. the solution that 2. step prepares is added dropwise in the solution that 1. step prepare, stirs 6-12h at 20-50 DEG C of heating water bath;
4. mixed liquor is proceeded to in water heating kettle, at 100-150 DEG C of hydro-thermal 24h, then washing and filtering 80-120 DEG C of drying;
5. the catalyst fines that step is 4. dried is positioned in Muffle furnace, at 400-600 DEG C of roasting 3-6h, obtains V 2o 5-WO 3-CuO x-Al 2o 3/ ZrO 2-TiO 2catalyst fines.
The present invention adopts two kinds of surfactants to be composite shuttering, and by hydrothermal crystallization method, prepare active component uniform load, have the ZT base composite oxidate catalyst of meso-hole structure, preparation process is simple and convenient.Composite mesoporous catalyst of the present invention 200-500 DEG C, air speed is 40000-60000h -1condition under, repeatedly carry out catalysis test to sample, its conversion rate of NOx all reaches more than 92%.
The composite oxides crystallization material with meso-hole structure that the present invention is prepared with hydrothermal crystallization method, for NH 3-SCR reacts, and its advantage is:
1, compared to commercial catalyst, obtained mesoporous composite oxides crystallization material has more excellent low-temperature catalytic activity and wider Process window, can up to 71% 150 DEG C of conversion efficiencies to NO, the 200-500 DEG C of conversion that can realize higher than 92%NO, (test condition is: NO concentration 500ppm, NH 3concentration 500ppm, O 2concentration 5%, He makes Balance Air, and total gas flow rate is 200mL/min, and air speed is 40,000 ~ 60,000h- 1);
2, using two kinds of surfactant B rij-35 and P123 as mesoporous pore creating material, by hydrothermal crystallization method, preparation synthesizes various active component as V 2o 5, WO 3, CuO x, Al 2o 3deng the mesoporous ZrO of equally loaded 2-TiO 2(ZT) base composite oxidate catalyst.
Fig. 1 is the N of mesoporous composite oxides catalysis material obtained in the invention process 2adsorption-desorption figure;
The V of Fig. 2 obtained by the embodiment of the present invention one 2o 5-WO 3-CuO x-Al 2o 3/ ZrO 2-TiO 2with carrier material ZrO made in embodiment five 2-TiO 2xRD collection of illustrative plates.Can find out, above-mentioned bi-material is all in single anatase structured (PDF:21-1272);
The V of Fig. 3 obtained by the embodiment of the present invention one 2o 5-WO 3-CuO x-Al 2o 3/ ZrO 2-TiO 2with carrier material ZrO made in embodiment five 2-TiO 2tEM electromicroscopic photograph.As can be seen from 3a, carrier ZT is polycrystalline state, and has obvious pore passage structure.Catalyst V after load active component 2o 5-WO 3-CuO x-Al 2o 3/ ZrO 2-TiO 2(as Fig. 3 b) still maintains polycrystalline structure and the pore passage structure of carrier ZT, and without any reunion or precipitation, illustrates that active component has been highly dispersed in carrier ZT all.The EDS collection of illustrative plates of Fig. 3 c correspond to the region of Fig. 3 b, and sample V prepared by hydrothermal crystallization method is described 2o 5-WO 3-CuO x-Al 2o 3/ ZrO 2-TiO 2the existence of middle V, W, Cu, Al, Zr, Ti, O element, confirms that active component has successfully been loaded on carrier;
The V of Fig. 4 obtained by the embodiment of the present invention one 2o 5-WO 3-CuO x-Al 2o 3/ ZrO 2-TiO 2sEM electromicroscopic photograph can find material V from the SEM photo of Fig. 4 a 2o 5-WO 3-CuO x-Al 2o 3/ ZrO 2-TiO 2there is obvious mesopore orbit structure.The dispersion that corresponding distribution diagram of element (Fig. 4 c) demonstrates the high uniformity of active component in whole carrier is further schemed with the STEM in Fig. 4 b;
The V of Fig. 5 obtained by the embodiment of the present invention one 2o 5-WO 3-CuO x-Al 2o 3/ ZrO 2-TiO 2with the H of the made commercial catalyst V-W/Ti of comparative example one (commercial catalyst) 2-TPR spectrogram.Compared with commercial catalyst, V 2o 5-WO 3-CuO x-Al 2o 3/ ZrO 2-TiO 2catalyst material has larger peak area and more redox peak, and V is described 2o 5-WO 3-CuO x-Al 2o 3/ ZrO 2-TiO 2there is higher redox ability.In addition, V 2o 5-WO 3-CuO x-Al 2o 3/ ZrO 2-TiO 2material oxidation reduction peak temperature, well below commercial catalyst, illustrates that it has more excellent low-temperature catalytic activity;
Fig. 6 shows the V prepared in an embodiment of the invention 2o 5-WO 3-CuO x-Al 2o 3/ ZrO 2-TiO 2with the made commercial catalyst V-W/Ti of comparative example one (commercial catalyst) to conversion rate of NOx spectrogram (relative to commercial catalyst V-W/Ti, synthesized catalyst V 2o 5-WO 3-CuO x-Al 2o 3/ ZrO 2-TiO 2up to 71%, can realize the conversion higher than 92%NOx at 200-500 DEG C 150 DEG C of conversion efficiencies to NO, have more excellent low-temperature catalytic activity and wider Process window, catalytic activity is obviously better than commercial catalyst).
Below some exemplary embodiments are listed further better the present invention to be described.Should understand; the above-mentioned embodiment that the present invention describes in detail; and following examples are only not used in for illustration of the present invention and limit the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.In addition, concrete proportioning, time, temperature etc. in following technological parameter are also only exemplary, and those skilled in the art can select suitable value in the scope of above-mentioned restriction.
Embodiment one
1. getting 4.5gBrij-35,3.7gP123 and 1g oxalic acid is dissolved in 100mL water, the ammonium metavanadate calculated by weight percent content by V, W, Cu, Al, ammonium metatungstate, cupric sulfate pentahydrate, aluminium isopropoxide add in the oxalic acid solution of configuration, stirs 3h at 30 DEG C of heating water baths;
2. get 1.2ml zirconium-n-propylate and 8.8ml butyl titanate is added drop-wise in the ethanolic solution of 40ml, stirring at room temperature is to forming a clear solution;
3. the solution that 2. step prepares is added dropwise in the solution that 1. step prepare, at 30 DEG C of heating water baths and to stir 12h to mixed liquor be uniform emulsion;
4. mixed liquor is proceeded to in water heating kettle, at 120 DEG C of hydro-thermal 24h, then use ethanol washing and filtering and 100 DEG C of dryings;
5. the catalyst fines that step is 4. dried is positioned in Muffle furnace, at 500 DEG C of roasting 4h, obtains V 2o 5-WO 3-CuO x-Al 2o 3/ ZrO 2-TiO 2catalyst fines, its specific area is in table 1;
V in Fig. 3 2o 5-WO 3-CuO x-Al 2o 3/ ZrO 2-TiO 2for the XRD collection of illustrative plates of the made catalysis material of the present embodiment, can find out except the diffraction maximum of anatase from spectrogram, there is no the characteristic peak of other other new metal oxides obvious, illustrate that doped chemical substantially enters the skeleton of carrier or is highly dispersed in the middle of carrier (Fig. 3).
Embodiment two
1. getting 4.5gBrij-35,3.7gP123 and 1g oxalic acid is dissolved in 100mL water, the ammonium metavanadate calculated by the weight percent content by V, W, Cu, ammonium metatungstate, copper nitrate add in the oxalic acid solution of configuration, stirs 3h at 30 DEG C of heating water baths;
2. get 1.2ml zirconium-n-propylate and 8.8ml butyl titanate is added drop-wise in the ethanolic solution of 40ml, stirring at room temperature is to forming a clear solution;
3. the solution that 2. step prepares is added dropwise in the solution that 1. step prepare, at 30 DEG C of heating water baths and to stir 12h to mixed liquor be uniform emulsion;
4. mixed liquor is proceeded to in water heating kettle, at 120 DEG C of hydro-thermal 24h, then use ethanol washing and filtering and 100 DEG C of dryings;
5. the catalyst fines that step is 4. dried is positioned in Muffle furnace, at 500 DEG C of roasting 4h, obtains V 2o 5-WO 3-CuO x/ ZrO 2-TiO 2catalyst fines, its specific area is in table 1.
Embodiment three
1. getting 4.5gBrij-35,3.7gP123 and 1g oxalic acid is dissolved in 100mL water, the ammonium metavanadate calculated by the weight percent content by V, W, Al, ammonium metatungstate, nine water aluminum nitrates add in the oxalic acid solution of configuration, stirs 3h at 30 DEG C of heating water baths;
2. get 1.2ml zirconium-n-propylate and 8.8ml butyl titanate is added drop-wise in the ethanolic solution of 40ml, stirring at room temperature is to forming a clear solution;
3. the solution that 2. step prepares is added dropwise in the solution that 1. step prepare, at 30 DEG C of heating water baths and to stir 12h to mixed liquor be uniform emulsion;
4. mixed liquor is proceeded to in water heating kettle, at 120 DEG C of hydro-thermal 24h, then use ethanol washing and filtering and 100 DEG C of dryings;
5. the catalyst fines that step is 4. dried is positioned in Muffle furnace, at 500 DEG C of roasting 4h, obtains V 2o 5-WO 3-Al 2o 3/ ZrO 2-TiO 2catalyst fines, its specific area is in table 1.
Embodiment four
1. getting 4.5gBrij-35,3.7gP123 and 1g oxalic acid is dissolved in 100mL water, the ammonium metavanadate calculated by the weight percent content by V, W, ammonium metatungstate add in the oxalic acid solution of configuration, stirs 3h at 30 DEG C of heating water baths;
2. get 1.2ml zirconium-n-propylate and 8.8ml butyl titanate is added drop-wise in the ethanolic solution of 40ml, stirring at room temperature is to forming a clear solution;
3. the solution that 2. step prepares is added dropwise in the solution that 1. step prepare, at 30 DEG C of heating water baths and to stir 12h to mixed liquor be uniform emulsion;
4. mixed liquor is proceeded to in water heating kettle, at 120 DEG C of hydro-thermal 24h, then use ethanol washing and filtering and 100 DEG C of dryings;
5. the catalyst fines that step is 4. dried is positioned in Muffle furnace, at 500 DEG C of roasting 4h, obtains V 2o 5-WO 3/ ZrO 2-TiO 2catalyst fines, its specific area is in table 1.
Embodiment five
1. to get 4.5gBrij-35 and 3.7gP123 be dissolved in 100mL water, stirs 3h at 30 DEG C of heating water baths;
2. get 1.2ml zirconium-n-propylate and 8.8ml butyl titanate is added drop-wise in the ethanolic solution of 40ml, stirring at room temperature is to forming a clear solution;
3. the solution that 2. step prepares is added dropwise in the solution that 1. step prepare, at 30 DEG C of heating water baths and to stir 12h to mixed liquor be uniform emulsion;
4. mixed liquor is proceeded to in water heating kettle, at 120 DEG C of hydro-thermal 24h, then use ethanol washing and filtering and 100 DEG C of dryings;
5. the catalyst fines that step is 4. dried is positioned in Muffle furnace, at 500 DEG C of roasting 4h, obtains ZrO 2-TiO 2catalyst fines;
ZrO in Fig. 3 2-TiO 2for the XRD collection of illustrative plates of the present embodiment institute prepared material, can find out that from spectrogram obtained zirconium titanium composite oxides carrier is single Detitanium-ore-type.
Comparative example one
After commercial cellular shape catalyst is pulverized through compressing tablet, sieve, obtain and test Kaolinite Preparation of Catalyst same particle size scope, being designated as V-W/Ti (commercial catalyst).
Mesoporous composite oxides catalysis material prepared by table 1 and the specific area parameter of commercial catalyst
Sample Specific area (m 2/g)
V 2O 5-WO 3-CuO x-Al 2O 3/ZrO 2-TiO 2 102
V 2O 5-WO 3-CuO x/ZrO 2-TiO 2 98
V 2O 5-WO 3-Al 2O 3/ZrO 2-TiO 2 111
V 2O 5-WO 3/ZrO 2-TiO 2 104
V-W/Ti(commercial catalyst) 54

Claims (10)

1. a mesoporous composite oxides catalyst for tail gas clean-up, is characterized in that, the constitutional chemistry of described mesoporous composite oxides catalyst is V 2o 5-WO 3-CuO x-Al 2o 3/ ZrO 2-TiO 2, wherein, the quality of V and ZrO 2, TiO 2the quality of quality and Zhi Bi≤10%, W and ZrO 2, TiO 2the quality of quality and Zhi Bi≤20%, Cu and ZrO 2, TiO 2the quality of quality and Zhi Bi≤10%, Al and ZrO 2, TiO 2the span of quality and Zhi Bi≤5%, x is 0≤x≤1.
2. mesoporous composite oxides catalyst according to claim 1, it is characterized in that, described mesoporous composite oxides catalyst has meso-hole structure, and mesoporous aperture is 5-30nm, described mesoporous composite oxides catalyst crystallization degree is high, and specific area is 60-200m 2/ g.
3. mesoporous composite oxides catalyst according to claim 1 and 2, is characterized in that, described mesoporous composite oxides catalyst can use at 200-500 DEG C.
4. the preparation method of arbitrary described mesoporous composite oxides catalyst in claim 1-3, it is characterized in that, described method comprises:
1) pore creating material, solubility vanadic salts, soluble tungsten salt, soluble copper salt, aluminum soluble salt, oxalic acid Homogeneous phase mixing in water are obtained the first mixed liquor;
2) zirconium source and titanium source are dispersed in alcoholic solution obtain the second mixed liquor;
3) the first mixed liquor, the step 2 prepared by step 1)) the second mixed liquor of preparing is mixed to get the 3rd mixed liquor, and wherein in the 3rd mixed liquor, the ratio of metallic element meets the ratio of metallic element in described mesoporous composite oxides SCR catalyst;
4) the 3rd mixed liquor step 3) prepared, 100-150 DEG C of hydro-thermal, then filters, washs and drying, be precipitated thing;
5) sediment step 4) obtained, 400-600 DEG C of roasting, obtains described mesoporous composite oxides catalyst;
Or directly vanadic salts, tungsten salt, mantoquita, aluminium salt, oxalic acid, zirconium-n-propylate and tetrabutyl titanate are mixed with the 3rd mixed liquor, carry out step 4) and step 5) successively, prepare described mesoporous composite oxides catalyst.
5. preparation method according to claim 4, is characterized in that, in step 1), mixed uniformly mode is at 20-50 DEG C of heating water bath and stirs 2-6h, and pore creating material comprises Brij-35 and/or P123.
6. the preparation method according to claim 4 or 5, is characterized in that, step 2) in, zirconium source comprises zirconium-n-propylate, zirconium-n-butylate, zirconium tert-butoxide and/or ethanol zirconium, and titanium source comprises butyl titanate and/or isopropyl titanate.
7., according to described preparation method arbitrary in claim 4-6, it is characterized in that, step 2) in, the alcohol in alcoholic solution comprises ethanol and/or isopropyl alcohol, and in alcoholic solution, the mass fraction of alcohol is 80-100%.
8., according to described preparation method arbitrary in claim 4-7, it is characterized in that, step 2) in, homodisperse mode is at stirring at room temperature 1-5 hour.
9. according to described preparation method arbitrary in claim 4-8, to it is characterized in that, in step 4), the 3rd mixed liquor is first stirred 6-12 hour at 20-50 DEG C of heating water bath, then at 100-150 DEG C of hydro-thermal 20-30 hour.
10., according to described preparation method arbitrary in claim 4-9, it is characterized in that, in step 5), roasting 3-6 hour.
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