CN101961653B - Composite oxide catalytic combustion catalyst as well as preparation method and application thereof - Google Patents

Abstract

The invention discloses a composite oxide catalytic combustion catalyst. The catalyst uses cordierite honeycomb ceramics as a carrier, and a composite oxide is loaded as an active component. The composite oxide is composed of Cu, Mn, Ce, An oxide composed of Zr and Ti, the loading of the composite oxide is 2-20wt%, and the ratio of Cu, Mn, Ce, Zr, Ti in the composite oxide is 1.0:0.5-8.0: 0.5-8.0: 0.2-2.0: 0.2-4.0. The invention also discloses a preparation method of the composite oxide catalytic combustion catalyst and its application in catalytic combustion to eliminate industrial volatile organic waste gas pollution. The active component and fuel of the catalyst of the present invention are loaded onto the surface of the honeycomb ceramic carrier in one step in the form of sol, and burned on the surface of the cordierite at 400-700°C to form a composite oxide active layer with high dispersion, high specific surface area and high activity.

Description

A kind of composite oxide catalytic combustion catalyst and its preparation method and application

(1) Technical field

The invention relates to the technical field of air pollution control, in particular to a composite oxide catalytic combustion catalyst, a preparation method thereof, and an application in catalytic combustion of volatile organic waste gases (VOCs).

(2) Background technology

Volatile organic waste gases (VOCs) are produced in petrochemical, coating, pharmaceutical, rubber and other production processes, as well as printing, baking varnish, degreasing of electronic components, film and fabric coating and other processes. Its large amount of discharge not only has a negative impact on the local ecological environment and the earth's environment, but also brings serious harm to human health. According to the different types of VOCs and the places where they are generated, different treatment methods can be adopted. For some VOCs with high concentration and single components, it is suitable to adopt methods such as condensation, liquid absorption and activated carbon adsorption to effectively recycle organic compounds. However, for the VOCs actually emitted by most industries, the concentration is often low, the composition is relatively complex, and the recycling value is not great, so the use of destruction technology is a more feasible method. Compared with biodegradation, photocatalysis and thermal incineration technology, catalytic combustion technology is more efficient, energy-saving and environmentally friendly. It uses catalysts to make organic waste gas burn flamelessly at a lower ignition temperature and decompose into carbon dioxide and Water vapor, and release a large amount of heat to realize the self-heating of the reaction.

At present, the preparation of monolithic composite oxide catalysts with cordierite ceramics as a carrier usually adopts suspension dip coating technology [Barbero, B.P., L. Costa-Almeida, et al. Chemical Engineering Journal, 2008, 139 (2): 430-435; Lu Hanfeng, Huang Haifeng, Chen Yinfei, Journal of Chemical Engineering of Universities, 2009,] and direct wet impregnation technology [CN200510062205.3; CN92100437.0], suspension dipping requires the synthesis of highly active nano-composite oxide particle catalysts, and then adding Prepare a slurry with water and a binder, and coat a layer of catalyst oxide particles on the surface of cordierite by dip coating technology. This preparation process is complicated, and the coating of composite oxide particles is not firm, the loss of slurry is large, and the preparation cost is high. Direct wet impregnation technology (Vergunst T, Applied Catalysis A: General, 2001, 213: 179-187.Lou, J.C, Environmental Engineering Science, 2009, 26 (7): 1267-1273) directly impregnates metal nitric acid on the surface of the carrier Salt solution has the advantages of simple process and low price, but the prepared catalyst active components often have low specific surface area, poor dispersion, and are easy to interact with the surface of the carrier, so it is difficult to form an oxide active phase.

(3) Contents of the invention

The purpose of the present invention is to provide an in-situ combustion preparation method for the disadvantages of complex process, high cost, low specific surface area, poor dispersion and difficult formation of active phase of the composite oxide in the existing suspension dip coating and direct impregnation preparation technology, Without coating and binder, the surface oxide can be highly dispersed on the surface of cordierite, and the formed composite oxide active phase has high specific surface area and high activity, which is suitable for catalytic combustion to degrade various VOCs.

The technical scheme that the present invention adopts is as follows:

A composite oxide catalytic combustion catalyst, the catalyst uses cordierite honeycomb ceramics as a carrier, loaded with a composite oxide as an active component, and the composite oxide is composed of Cu, Mn, Ce, Zr, Ti oxide, the loading of the composite oxide is 2 to 20wt%, and the ratio of the amount of Cu, Mn, Ce, Zr, Ti in the composite oxide is 1.0: 0.5 to 8.0: 0.5 to 8.0: 0.2～2.0: 0.2～4.0. Cu, Mn, Ce, Zr, and Ti in the composite oxide referred to in the present invention refer to respective metal ions of Cu, Mn, Ce, Zr, and Ti in the composite oxide. Called Cu, Mn, Ce, Zr, Ti.

The oxide composed of Cu, Mn, Ce, Zr and Ti is obtained by calcining a mixture of water-soluble Cu salt, Mn salt, Ce salt, Zr salt and Ti salt at a temperature of 400-700°C. The oxygen content in the resulting composite oxide was determined.

The ratio of Cu, Mn, Ce, Zr and Ti in the composite oxide is preferably 1.0:1-5:1-5:0.2-0.5:0.4-0.8.

The loading amount of the composite oxide is measured by the mass of the carrier cordierite honeycomb ceramics.

The composite oxide catalytic combustion catalyst of the present invention can be prepared according to the following methods: (1) preparation of active component sol impregnation solution: get copper nitrate, manganese nitrate, cerium nitrate, zirconium nitrate and titanyl sulfate with deionized water, prepare Forming a metal salt solution with a total concentration of metal ions of 0.5 to 2.0 mol/L, the ratio of the amount of Cu, Mn, Ce, Zr, Ti in the metal salt solution is 1.0: 0.5 to 8.0: 0.5 to 8.0: 0.2 ～2.0: 0.2～4.0, preferably 1.0: 1～5: 1～5: 0.2～0.5: 0.4～0.8, then add cross-linking agent in metal salt solution, described cross-linking agent is polyethylene glycol (average molecular weight 200～2000) or citric acid, preferably citric acid, the ratio of the amount of the crosslinking agent substance to the total substance amount of the metal ion in the metal salt solution is 0.05～2.0: 1.0, and the sol solution is obtained after stirring and dissolving; then Adding fuel to the sol solution, stirring until the solution is transparent and clear, and standing still to obtain the active component sol impregnation solution, the fuel is urea, glycine or alanine, and the amount of the fuel is the same as that of the metal ion in the sol solution. The ratio of the total substance amount is 0.2～4.0:1.0;

(2) Take the honeycomb ceramics made of cordierite and completely immerse them in the active component sol impregnating liquid prepared in step (1), take them out after fully impregnating them, blow off the residual liquid with high-pressure airflow, and ventilate and dry at room temperature for 1 to 8 hours. Obtain the catalyst precursor of the loaded active component gel; the catalyst precursor of the loaded active component gel is dried at 50-100°C for 20-40 hours, then roasted at 400-700°C for 3-8 hours, taken out and cooled Then re-immerse in the above-mentioned active component sol impregnating solution, repeat the above operation until the loading amount of the active component on the surface of the honeycomb ceramic is 2-20 wt%, and the composite oxide catalytic combustion catalyst is obtained.

In the step (1), the fuel is preferably urea.

The ratio of the substance amount of the fuel to the total substance amount of metal ions in the sol solution is preferably 0.5˜2.0:1.0.

In the step (1), the standing time is usually 1 to 4 hours.

In the step (2), the time for the full immersion is 1 to 2 hours.

The present invention also provides the preparation method of described composite oxide catalytic combustion catalyst, and described method comprises the following steps:

(1) Preparation of active component sol impregnation solution: take copper nitrate, manganese nitrate, cerium nitrate, zirconium nitrate and titanyl sulfate with deionized water, and prepare a metal salt solution with a total concentration of metal ions of 0.5 to 2.0 mol/L. The ratio of the amount of Cu, Mn, Ce, Zr, Ti in the metal salt solution is 1.0: 0.5～8.0: 0.5～8.0: 0.2～2.0: 0.2～4.0, and then add the crosslinking agent in the metal salt solution , the crosslinking agent is citric acid or polyethylene glycol with an average molecular weight of 200 to 2000, and the ratio of the amount of the substance of the crosslinking agent to the total amount of the metal ion in the metal salt solution is 0.05 to 2.0 : 1, after stirring and dissolving, the sol solution is obtained; then, fuel is added to the sol solution, stirred until the solution is transparent and clear, and left standing to obtain the active component sol impregnating liquid, the fuel is urea, glycine or alanine, and the fuel The ratio of the amount of substance to the total amount of substance of metal ions in the sol solution is 0.2～4.0:1;

(2) Take the honeycomb ceramics made of cordierite and completely immerse them in the active component sol impregnating liquid prepared in step (1), take them out after fully impregnating them, blow off the residual liquid with high-pressure airflow, and ventilate and dry at room temperature for 1 to 8 hours. Obtain the catalyst precursor of the loaded active component gel; the catalyst precursor of the loaded active component gel is dried at 50-100°C for 20-40 hours, then roasted at 400-700°C for 3-8 hours, taken out and cooled Then re-immerse in the above-mentioned active component sol impregnating solution, repeat the above operation until the loading amount of the active component on the surface of the honeycomb ceramic is 2-20 wt%, and the composite oxide catalytic combustion catalyst is obtained.

The composite oxide catalytic combustion catalyst of the present invention can be applied to catalytic combustion to eliminate industrial volatile organic waste gas pollution, and the waste gas is benzene, toluene, xylene, chlorobenzene, methylene chloride, n-hexane, cyclohexane , isopropanol, ethyl acetate, acetone, acetaldehyde, ethanol, methyl methacrylate or dimethylformamide, etc.

More specifically, the catalytic combustion is carried out on a gas-solid reaction device: take the catalyst, usually cut into a cylindrical shape, and place it in the isothermal zone of the reaction tube. The raw material gas and air enter in two ways, and the raw material gas passes through 0 ° C ice The water bath then merges with another channel of air into the reaction tube, where the catalytic combustion reaction is carried out through the action of a catalyst. The catalytic combustion reaction temperature is 150-450°C, and the space velocity is GHSV=5000h ^-1 .

The beneficial effects of the present invention are mainly reflected in: (1) the active component elements are all transition metals and rare earth metal oxides, do not contain precious metals, and have low cost; (3) The active component gel burns on the surface of cordierite at 400-700°C to form a composite oxide active layer with high dispersion, high specific surface area and high activity.

(4) Description of drawings

Fig.1 Surface SEM images of cordierite honeycomb ceramics.

The surface SEM picture of the composite oxide catalytic combustion catalyst that Fig. 2 embodiment 1 makes.

(5) Specific implementation methods

The present invention is further described below in conjunction with specific embodiment, but protection scope of the present invention is not limited thereto:

Example 1

Weigh 3.02 grams of Cu(NO ₃ ) ₂ ·3H ₂ O, 4.48 grams of 50 wt% Mn(NO ₃ ) ₂ aqueous solution, 27.13 grams of Ce(NO ₃ ) ₃ ·6H ₂ O, 2.54 grams of Zr(NO ₃ ) ₄ , 0.8 g of TiOSO ₄ was added to a certain amount of deionized water to prepare a 100 ml transparent solution with a total metal ion concentration of 1.0 mol/L. Then add 19.21 grams of citric acid as cross-linking agent in this solution, stir and dissolve to form transparent sol solution; Then add 3 grams of urea in sol. Stir until the solution turns into a clear and transparent solution, and let it stand for 2 hours to obtain the active component sol impregnation solution.

Take 2.5g of cordierite honeycomb ceramic carrier, immerse it in the active component sol impregnation solution, let it stand for 1 hour, take out the honeycomb ceramic, blow off the surface and the remaining flowing liquid in the pores with a high-pressure air gun, and maintain the permeability of the honeycomb ceramic. Ventilate and dry for 5 hours, then dry at 60°C for 24 hours, then bake at 500°C for 4 hours, and obtain a primary impregnated catalyst after cooling.

Re-impregnate the catalyst impregnated once in the above-mentioned active component sol impregnation solution for the second time, and repeat subsequent operations (including drying and roasting) to obtain a monolithic composite oxide catalyst with a composite oxide loading of 7.2wt%. . The SEM image of the catalyst surface is shown in Figure 2.

Example 2

Weigh 3.02 grams of Cu(NO ₃ ) ₂ ·3H ₂ O, 8.95 grams of 50 wt% Mn(NO ₃ ) ₂ aqueous solution, 21.7 grams of Ce(NO ₃ ) ₃ ·6H ₂ O, 2.12 grams of Zr(NO ₃ ) ₄ , 1.0 g of TiOSO ₄ was added to a certain amount of deionized water to prepare a 100 ml transparent solution with a total metal ion concentration of 1.0 mol/L. Then add 19.21 grams of citric acid as cross-linking agent in this solution, stir and dissolve to form transparent sol solution; Then add 3 grams of urea in sol. Stir until the solution turns into a clear and transparent solution, and let it stand for 2 hours to obtain the active component sol impregnation solution.

Take 2.5g of cordierite honeycomb ceramic carrier, immerse it in the active component sol impregnation solution, let it stand for 1 hour, take out the honeycomb ceramic, blow off the surface and the remaining flowing liquid in the pores with a high-pressure air gun, and maintain the permeability of the honeycomb ceramic. Ventilate and dry for 5 hours. The catalyst precursor was dried at 50°C for 24 hours and calcined at 500°C for 4 hours to obtain a primary impregnated catalyst.

Re-impregnate the catalyst impregnated once in the above-mentioned active component sol impregnation solution for the second time, repeat the subsequent operations (including drying and roasting), and then a monolithic composite oxide catalyst with a composite oxide loading of 6.98wt% can be obtained .

Example 3

Weigh 3.02 grams of Cu(NO ₃ ) ₂ ·3H ₂ O, 13.43 grams of 50 wt% Mn(NO ₃ ) ₂ aqueous solution, 16.28 grams of Ce(NO ₃ ) ₃ ·6H ₂ O, 1.70 grams of Zr(NO ₃ ) ₄ , 1. 20 grams of TiOSO ₄ were added to a certain amount of deionized water to prepare a 100 ml transparent solution with a total metal ion concentration of 1.0 mol/L. Then, 19.21 grams of citric acid was added to the solution as a cross-linking agent, stirred and dissolved to form a transparent sol solution; then 1.2 grams of urea was added to the sol. Stir until the solution turns into a clear and transparent solution, and let it stand for 1 hour to obtain the active component sol impregnation solution.

Take 2.5g of cordierite honeycomb ceramic carrier, immerse it in the active component sol, place it for 2 hours, take out the honeycomb ceramic, blow off the residual flowing liquid on the surface and in the pores with a high-pressure air gun, maintain the permeability of the honeycomb ceramic, and ventilate at room temperature Dry for 1h. The catalyst precursor was dried at 60°C for 40 hours and calcined at 400°C for 8 hours to obtain a primary impregnated catalyst.

Re-impregnate the impregnated catalyst for the second time in the above-mentioned active component sol impregnation solution, and repeat the subsequent operations (including drying and roasting) to obtain a monolithic composite oxide catalyst with a composite oxide loading of 7.28wt%. .

Example 4

Weigh 3.02 grams of Cu(NO ₃ ) ₂ ·3H ₂ O, 17.91 grams of 50 wt% Mn(NO ₃ ) ₂ aqueous solution, 10.85 grams of Ce(NO ₃ ) ₃ ·6H ₂ O, 1.28 grams of Zr(NO ₃ ) ₄ , 1.40 g of TiOSO ₄ was added to a certain amount of deionized water to prepare a 100 ml transparent solution with a total metal ion concentration of 1.0 mol/L. Then add 19.21 grams of citric acid as cross-linking agent in this solution, stir and dissolve to form transparent sol solution; Then add 6 grams of urea in sol. Stir until the solution turns into a clear and transparent solution, and let it stand for 4 hours to obtain the active component sol impregnation solution.

Take 2.5g of cordierite honeycomb ceramic carrier, immerse it in the active component sol, place it for 2 hours, take out the honeycomb ceramic, blow off the residual flowing liquid on the surface and in the pores with a high-pressure air gun, maintain the permeability of the honeycomb ceramic, and ventilate at room temperature Dry 8h. The catalyst precursor was dried at 80°C for 24 hours and calcined at 700°C for 3 hours to obtain a primary impregnated catalyst.

Re-impregnate the catalyst impregnated once in the above-mentioned active component sol impregnation solution for the second time, and repeat subsequent operations (including drying and roasting) to obtain a monolithic composite oxide catalyst with a composite oxide loading of 7.56 wt%. .

Example 5

Weigh 1.05 g of Cu(NO ₃ ) ₂ ·3H ₂ O, 12.45 g of 50 wt% Mn(NO ₃ ) ₂ aqueous solution, 15.10 g of Ce(NO ₃ ) ₃ ·6H ₂ O, 2.95 g of Zr(NO ₃ ) ₄ , Add a certain amount of deionized water to 2.78 grams of TiOSO ₄ to prepare 100 ml of a transparent solution with a total metal ion concentration of 1.0 mol/L. Then add 19.21 grams of citric acid as cross-linking agent in this solution, stir and dissolve to form transparent sol solution; Then add 3 grams of urea in sol. Stir until the solution turns into a clear and transparent solution, and let it stand for 2 hours to obtain the active component sol impregnation solution.

Take 2.5g of cordierite honeycomb ceramic carrier, immerse it in the active component sol impregnation solution, let it stand for 1 hour, take out the honeycomb ceramic, blow off the surface and the remaining flowing liquid in the pores with a high-pressure air gun, and maintain the permeability of the honeycomb ceramic. Ventilate and dry for 5 hours. The catalyst precursor was dried at 60°C for 24 hours and calcined at 500°C for 4 hours to obtain a primary impregnated catalyst.

Re-impregnate the catalyst impregnated once in the above-mentioned active component sol impregnating solution for the second time, and repeat the subsequent operations (including drying and roasting) to obtain a monolithic composite oxide catalyst with a composite oxide loading of 7.51wt%. .

Example 6

Weigh 2.42 grams of Cu(NO ₃ ) ₂ ·3H ₂ O, 1.79 grams of 50 wt% Mn(NO ₃ ) ₂ aqueous solution, 34.72 grams of Ce(NO ₃ ) ₃ ·6H ₂ O, 1.02 grams of Zr(NO ₃ ) ₄ , 0.32 g of TiOSO ₄ was added to a certain amount of deionized water to prepare a 100 ml transparent solution with a total metal ion concentration of 1.0 mol/L. Then add 19.21 grams of citric acid as cross-linking agent in this solution, stir and dissolve to form transparent sol solution; Then add 3 grams of urea in sol. Stir until the solution turns into a clear and transparent solution, and let it stand for 2 hours to obtain the active component sol impregnation solution.

Take 2.5g of cordierite honeycomb ceramic carrier, immerse it in the active component sol impregnation solution, let it stand for 1 hour, take out the honeycomb ceramic, blow off the surface and the remaining flowing liquid in the pores with a high-pressure air gun, and maintain the permeability of the honeycomb ceramic. Ventilate and dry for 5 hours. The catalyst precursor was dried at 50°C for 24 hours and calcined at 500°C for 4 hours to obtain a primary impregnated catalyst.

Re-impregnate the impregnated catalyst for the second time in the above-mentioned active component sol impregnation solution, and repeat the subsequent operations (including drying and roasting) to obtain a monolithic composite oxide catalyst with a composite oxide loading of 9.73wt%. .

Example 7

Weigh 1.72 g of Cu(NO ₃ ) ₂ ·3H ₂ O, 20.46 g of 50 wt% Mn(NO ₃ ) ₂ aqueous solution, 2.48 g of Ce(NO ₃ ) ₃ ·6H ₂ O, 0.48 g of Zr(NO ₃ ) ₄ , 4.57 grams of TiOSO ₄ were added to a certain amount of deionized water to prepare 100 ml of a transparent solution with a total metal ion concentration of 1.0 mol/L. Then add 19.21 grams of citric acid as cross-linking agent in this solution, stir and dissolve to form transparent sol solution; Then add 3 grams of urea in sol. Stir until the solution turns into a clear and transparent solution, and let it stand for 2 hours to obtain the active component sol impregnation solution.

Take 2.5g of cordierite honeycomb ceramic carrier, immerse it in the active component sol impregnation solution, let it stand for 1 hour, take out the honeycomb ceramic, blow off the surface and the remaining flowing liquid in the pores with a high-pressure air gun, and maintain the permeability of the honeycomb ceramic. Ventilate and dry for 5 hours. The catalyst precursor was dried at 50°C for 24 hours and calcined at 500°C for 4 hours to obtain a primary impregnated catalyst.

Re-impregnate the impregnated catalyst for the second time in the above-mentioned active component sol impregnation solution, and repeat the subsequent operations (including drying and roasting) to obtain a monolithic composite oxide catalyst with a composite oxide loading of 9.73wt%. .

Example 8

Weigh 3.02 grams of Cu(NO ₃ ) ₂ ·3H ₂ O, 22.38 grams of 50 wt% Mn(NO ₃ ) ₂ aqueous solution, 5.43 grams of Ce(NO ₃ ) ₃ ·6H ₂ O, 0.85 grams of Zr(NO ₃ ) ₄ , Add a certain amount of deionized water to 1.6 grams of TiOSO ₄ , and prepare 100 ml of a transparent solution with a total metal ion concentration of 1.0 mol/L. Then, 38.42g of citric acid was added into the solution as a cross-linking agent, stirred and dissolved to form a transparent sol solution; then 24.0g of urea was added into the sol. Stir until the solution turns into a clear and transparent solution, and let it stand for 2 hours to obtain the active component sol impregnation solution.

Take 2.5g of cordierite honeycomb ceramic carrier, immerse it in the active component sol, place it for 1 hour, take out the honeycomb ceramic, blow off the residual flowing liquid on the surface and in the pores with a high-pressure air gun, maintain the permeability of the honeycomb ceramic, and ventilate at room temperature Dry for 5h. The catalyst precursor was dried at 100°C for 20 hours and calcined at 600°C for 4 hours to obtain a primary impregnated catalyst.

Re-impregnate the catalyst impregnated once in the above-mentioned active component sol impregnation solution for the second time, and repeat subsequent operations (including drying and roasting) to obtain a monolithic composite oxide catalyst with a composite oxide loading of 7.42wt%. .

Example 9

The monolithic composite oxide catalyst was prepared according to the method of Example 2, other conditions were the same, the difference was that the addition of citric acid was 9.6 g, and glycine was used as fuel, and the addition was 3.75 grams.

Example 10

Prepare integral composite oxide catalyst according to the method for embodiment 2, other conditions are identical, difference is to adopt the polyethylene glycol of average molecular weight 500 as crosslinking agent, the consumption of polyethylene glycol is 10.0g, adopts alanine as Fuel, the addition amount is 4.45 grams.

Example 11

The catalytic combustion activity test of the monolithic composite oxide catalyst prepared according to Example 2 was carried out on a gas-solid reaction device: the cylindrical ceramic honeycomb catalyst was placed in the isothermal zone of the reaction tube. The raw material gas and air enter in two ways, and the air intake air velocity is controlled by a mass flow meter (D07-11A/ZM). The inlet concentration of organic compounds is 5000mg/m ³ , the catalytic combustion reaction temperature is 150-400°C, the space velocity is 5000h ^-1 , and the reaction tail gas is analyzed online by Agilent 6890N chromatograph, and the reactions at different conversion rates of different organic gases are recorded Temperature, the results are shown in Table 1. It can be seen from Table 1 that the catalyst prepared by the present invention has relatively high catalytic activity, especially for the exhaust gas of oxygen-containing organic compounds.

Table 1 Catalytic combustion activity of various VOCs

Example 12

The catalyst prepared by the method of the above-mentioned Examples 1-10 was evaluated by the catalytic combustion of ethyl acetate under the device described in Example 11, and the results are shown in Table 2.

Table 2 embodiment prepares the catalytic combustion ethyl acetate activity of catalyst

Claims (5)

1. composite oxide catalytic combustion catalyst; It is characterized in that described catalyst is a carrier with the ceramic honey comb of cordierite; It is active component that load has composite oxides; The oxide that said composite oxides are made up of Cu, Mn, Ce, Zr, Ti, the load capacity of said composite oxides are 2～20wt%, and the ratio of the amount of substance of Cu, Mn, Ce, Zr, Ti is 1.0: 0.5～8.0: 0.5～8.0: 0.2～2.0: 0.2～4.0 in the said composite oxides; Described composite oxide catalytic combustion catalyst prepares by following method:

(1) preparation active component sol impregnation liquid: get copper nitrate, manganese nitrate, cerous nitrate, zirconium nitrate and titanyl sulfate and use deionized water; Be mixed with the metal salt solution that the metal ion total concentration is 0.5～2.0mol/L; The ratio of the amount of substance of Cu, Mn, Ce, Zr, Ti is 1.0: 0.5～8.0: 0.5～8.0: 0.2～2.0: 0.2～4.0 in the said metal salt solution; In metal salt solution, add crosslinking agent then; Said crosslinking agent is that citric acid or mean molecule quantity are 200～2000 polyethylene glycol; The ratio of total amount of substance of metal ion is 0.05～2.0: 1 in the amount of substance of said crosslinking agent and the metal salt solution, obtains sol solution after the stirring and dissolving; In sol solution, add fuel then; Leave standstill after being stirred to the transparent clarification of solution; Obtain active component sol impregnation liquid, said fuel is urea, glycine or alanine, and the ratio of total amount of substance of metal ion is 0.2～4.0: 1 in the amount of substance of said fuel and the sol solution;

(2) ceramic honey comb of getting cordierite is immersed in the active component sol impregnation liquid that step (1) makes fully; Fully take out the dipping back; High pressure draught is blown away remaining liquid, and aeration-drying is 1～8 hour under the room temperature, obtains the catalyst precarsor of load active component gel; The catalyst precarsor of load active component gel is following dry 20～40 hours at 50～100 ℃; Again 400～700 ℃ of roasting temperatures 3～8 hours; Again be immersed in the above-mentioned active component sol impregnation liquid after taking out cooling; The load capacity that repeats the active component on aforesaid operations to ceramic honey comb surface is 2～20wt%, makes said composite oxide catalytic combustion catalyst.

2. composite oxide catalytic combustion catalyst as claimed in claim 1 is characterized in that in the said step (1), said fuel is urea.

3. composite oxide catalytic combustion catalyst as claimed in claim 1 is characterized in that in the said step (1), and the ratio of total amount of substance of metal ion is 0.5～2.0: 1.0 in the amount of substance of said fuel and the sol solution.

4. the preparation method of composite oxide catalytic combustion catalyst as claimed in claim 1 is characterized in that described method may further comprise the steps:

(1) preparation active component sol impregnation liquid: get copper nitrate, manganese nitrate, cerous nitrate, zirconium nitrate and titanyl sulfate and use deionized water; Be mixed with the metal salt solution that the metal ion total concentration is 0.5～2.0mol/L; The ratio of the amount of substance of Cu, Mn, Ce, Zr, Ti is 1.0: 0.5～8.0: 0.5～8.0: 0.2～2.0: 0.2～4.0 in the said metal salt solution; In metal salt solution, add crosslinking agent then; Said crosslinking agent is that citric acid or mean molecule quantity are 200～2000 polyethylene glycol; The ratio of total amount of substance of metal ion is 0.05～2.0: 1 in the amount of substance of said crosslinking agent and the metal salt solution, obtains sol solution after the stirring and dissolving; In sol solution, add fuel then; Leave standstill after being stirred to the transparent clarification of solution; Obtain active component sol impregnation liquid, said fuel is urea, glycine or alanine, and the ratio of total amount of substance of metal ion is 0.2～4.0: 1 in the amount of substance of said fuel and the sol solution;

(2) ceramic honey comb of getting cordierite is immersed in the active component sol impregnation liquid that step (1) makes fully; Fully take out the dipping back; High pressure draught is blown away remaining liquid, and aeration-drying is 1～8 hour under the room temperature, obtains the catalyst precarsor of load active component gel; The catalyst precarsor of load active component gel is following dry 20～40 hours at 50～100 ℃; Again 400～700 ℃ of roasting temperatures 3～8 hours; Again be immersed in the above-mentioned active component sol impregnation liquid after taking out cooling; The load capacity that repeats the active component on aforesaid operations to ceramic honey comb surface is 2～20wt%, makes said composite oxide catalytic combustion catalyst.

5. composite oxide catalytic combustion catalyst as claimed in claim 1 is eliminated the application in the industrial volatile Organic Waste Gas Pollution at catalytic combustion, and described waste gas is benzene,toluene,xylene, chlorobenzene, carrene, n-hexane, cyclohexane, isopropyl alcohol, ethyl acetate, acetone, acetaldehyde, ethanol, methyl methacrylate or dimethyl formamide.

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