CN101961653A - Composite oxide catalytic combustion catalyst as well as preparation method and application thereof - Google Patents
Composite oxide catalytic combustion catalyst as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a composite oxide catalytic combustion catalyst. In the catalyst, honeycomb ceramics made of cordierite is used as a carrier and loads a composite oxide used as an active constituent, wherein the composite oxide is composed of Cu, Mn, Ce, Zr and Ti and has the loading of 2-20wt%, and in the composite oxide, the molar ratio of Cu to Mn to Ce to Zr to Ti is 1.0:0.5-8.0:0.5-8.0:0.2-2.0:0.2-4.0. The invention further discloses a preparation method of the composite oxide catalytic combustion catalyst and the application of the composite oxide catalytic combustion catalyst in catalytic combustion for removing industrial volatile organic waste gas pollution. A composite oxide active layer with high dispersity, high-specific area and high activity can be formed by the steps of loading the active constituent of the catalyst and fuel onto the surface of the honeycomb ceramics in one step in a sol form, and combusting on the surface of the cordierite at 400-700 DEG C.
Description
(1) technical field
The present invention relates to the air pollution control technique field, particularly a kind of composite oxide catalytic combustion catalyst and preparation method thereof, and the application in catalytic combustion volatility organic exhaust gas (VOCs).
(2) background technology
Volatile organic exhaust gas (VOCs) results from production processes such as petrochemical industry, coating, pharmacy, rubber, and technical process such as degreasing of printing, baking vanish, electronic devices and components, film fabric coating.Its a large amount of dischargings not only produce negative influence to local region environment, earth environment, also bring serious harm to human health simultaneously.According to variety classes and the generation place of VOCs, can adopt different processing methods.The VOCs that some concentration are higher and component is single, the suitable methods such as condensation, liquid absorption and charcoal absorption that adopt, the organifying compound is effectively recycled.Yet for the VOCs of most of industrial actual discharge, its concentration is often lower, and composition is also comparatively complicated, recycles to be worth not quite, and therefore adopting destroy technology is comparatively feasible method.Be compared to biological degradation method, photocatalysis and thermal incineration technology, more efficient, the energy-conservation and environmental friendliness of catalytic combustion technology, it is to make organic compounds carry out flameless combustion under lower initiation temperature by catalyst, resolve into carbon dioxide and steam, and emit a large amount of heat realization responses from heat supply.
Suspension dip-coating technology [Barbero is adopted in the monolithic devices composite oxide catalysts preparation that with the cordierite ceramic is carrier at present usually, B.P., L.Costa-Almeida, et al.Chemical Engineering Journal, 2008,139 (2): 430-435; Lu Hanfeng, Huanghai Sea wind, Chen Yinfei, colleges and universities' Chemical Engineering journal, 2009 ,] and directly wet dipping technique [CN200510062205.3; CN92100437.0], the suspension dip-coating requires the synthetic earlier highly active nano composite oxide beaded catalyst that has, add entry and binder making slurries then, by the dip-coating technology at cordierite surface-coated one deck catalyst oxidation composition granule, this complicated process of preparation, and the composite oxide particle coating is insecure, the slurries loss amount is big, the preparation cost height.Directly wet dipping technique (Vergunst T, Applied Catalysis A:General, 2001,213:179-187.Lou, J.C, Environmental Engineering Science, 2009,26 (7): 1267-1273) then directly at carrier surface impregnating metal nitrate solution, have simple, the cheap advantage of technology, but often specific area is low for prepared catalyst activity component, bad dispersibility, and easy and carrier surface interacts, and is difficult for forming the active phase of oxide.
(3) summary of the invention
The present invention seeks at complex process, cost height and composite oxides specific area in existing suspension dip-coating and the direct impregnation technology of preparing low, bad dispersibility, be difficult for forming the shortcoming of active phase, a kind of situ combustion preparation method is provided, need not coating and binding agent, oxide on surface can high degree of dispersion on the cordierite surface, formed composite oxides activity has high-specific surface area and high activity mutually, the suitable catalytic combustion all kinds of VOCs that degrade.
The technical solution used in the present invention is as follows:
A kind of composite oxide catalytic combustion catalyst, described catalyst is a carrier with the ceramic honey comb of cordierite, it is active component that load has composite oxides, described composite oxides are the oxide of being made up of Cu, Mn, Ce, Zr, Ti, the load capacity of described composite oxides is 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 described composite oxides.Cu in the composite oxides of indication of the present invention, Mn, Ce, Zr, Ti are meant Cu in the composite oxides, Mn, Ce, Zr, Ti metal ion separately, for the simplification of explaining, all are called Cu, Mn, Ce, Zr, Ti in the present invention.
The described oxide of being made up of Cu, Mn, Ce, Zr, Ti is that the mixture by water-soluble Cu salt, Mn salt, Ce salt, Zr salt, Ti salt obtains at 400～700 ℃ of roasting temperatures, and the content of oxygen is determined in the composite oxides that obtain after the roasting.
In the described composite oxides ratio of the amount of substance of Cu, Mn, Ce, Zr, Ti be preferably 1.0: 1～5: 1～5: 0.2～0.5: 0.4～0.8.
The load capacity of described composite oxides is to measure with the quality of the ceramic honey comb of carrier cordierite.
Composite oxide catalytic combustion catalyst of the present invention can prepare by the following method: (1) preparation active component sol impregnation liquid: get copper nitrate, manganese nitrate, cerous nitrate, zirconium nitrate and titanyl sulfate deionized water, be mixed with the metal salt solution that the metal ion total concentration is 0.5～2.0mol/L, Cu in the described metal salt solution, Mn, Ce, Zr, the ratio of the amount of substance of Ti is 1.0: 0.5～8.0: 0.5～8.0: 0.2～2.0: 0.2～4.0, preferred 1.0: 1～5: 1～5: 0.2～0.5: 0.4～0.8, in metal salt solution, add crosslinking agent then, described crosslinking agent is polyethylene glycol (mean molecule quantity 200～2000) or citric acid, optimization citric acid, the ratio of total amount of substance of metal ion is 0.05～2.0: 1.0 in described crosslinking agent amount of substance 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, described fuel is urea, glycine or alanine, and the ratio of total amount of substance of metal ion is 0.2～4.0: 1.0 in the amount of substance of described 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, repetition aforesaid operations to the load capacity of the active component on ceramic honey comb surface is 2～20wt%, makes described composite oxide catalytic combustion catalyst.
In the described step (1), described fuel is preferably urea.
The ratio of total amount of substance of metal ion is preferably 0.5～2.0: 1.0 in the amount of substance of described fuel and the sol solution.
In the described step (1), described time of repose is generally 1～4 hour.
In the described step (2), the time of described abundant dipping is 1～2 hour.
The present invention also provides the preparation method of described composite oxide catalytic combustion catalyst, and 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 deionized water, be mixed with the metal salt solution that the metal ion total concentration is 0.5～2.0mol/L, Cu in the described metal salt solution, Mn, Ce, Zr, the ratio of the amount of substance of Ti is 1.0: 0.5～8.0: 0.5～8.0: 0.2～2.0: 0.2～4.0, in metal salt solution, add crosslinking agent then, described 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 described 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, described 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 described 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, repetition aforesaid operations to the load capacity of the active component on ceramic honey comb surface is 2～20wt%, makes described composite oxide catalytic combustion catalyst.
Composite oxide catalytic combustion catalyst of the present invention can be applicable to catalytic combustion and eliminates industrial volatile Organic Waste Gas Pollution, 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 etc.
More specifically, described catalytic combustion carries out on the gas-solid reaction device: get described catalyst, usually machinable becomes cylindrical, place the reaction tube isothermal region, unstripped gas and air divide two-way to enter, and unstripped gas converges with another road air then by 0 ℃ of ice-water bath and enters reaction tube, carries out catalyst combustion reaction through catalyst action in reaction tube, described catalyst combustion reaction temperature is 150～450 ℃, and air speed is GHSV=5000h
-1
Beneficial effect of the present invention is mainly reflected in: (1) active component element is transition metal and rare-earth oxide, does not contain noble metal, and cost is low; (2) active component loads to the honeycomb ceramic carrier surface with one step of solation, need not coating and binding agent, and technology is easy; (3) the active component gel in the cordierite surface combustion, can form high dispersive, high-specific surface area and highly active composite oxides active layer under 400-700 ℃.
(4) description of drawings
The surperficial SEM figure of the ceramic honey comb of figure .1 cordierite.
The surperficial SEM figure of the composite oxide catalytic combustion catalyst that figure .2 embodiment 1 makes.
(5) specific embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1
Take by weighing 3.02 gram Cu (NO
3)
23H
2Mn (the NO of O, 4.48 gram 50wt%
3)
2The aqueous solution, 27.13 gram Ce (NO
3)
36H
2O, 2.54 gram Zr (NO
3)
4, 0.8 the gram TiOSO
4, add a certain amount of deionized water, being mixed with the metal ion total concentration is the 100ml clear solution of 1.0mol/L.Add 19.21 gram citric acids then as crosslinking agent in this solution, stirring and dissolving forms transparent sol solution; In colloidal sol, add 3 gram urea then.Stirring becomes clear solution until dissolving, leaves standstill 2 hours, obtains active component sol impregnation liquid.
Get cordierite honeycomb ceramic carrier 2.5g, it is immersed in the active component sol impregnation liquid, placed 1 hour, take out ceramic honey comb, high pressure air rifle is blown away working fluid remaining in surface and the duct, keeps the permeability of ceramic honey comb, aeration-drying 5h under the room temperature, descended dry 24 hours at 60 ℃ then,, obtain impregnated catalyst after the cooling 1 time again 500 ℃ of roastings 4 hours.
The catalyst of 1 dipping is flooded in above-mentioned active component sol impregnation liquid again for the second time, repeat subsequent operation (comprising drying, roasting), can make the monolithic devices composite oxide catalysts of composite oxide supported amount 7.2wt%.Catalyst surface SEM figure sees accompanying drawing 2.
Embodiment 2
Take by weighing 3.02 gram Cu (NO
3)
23H
2Mn (the NO of O, 8.95 gram 50wt%
3)
2The aqueous solution, 21.7 gram Ce (NO
3)
36H
2O, 2.12 gram Zr (NO
3)
4, 1.0 the gram TiOSO
4, add a certain amount of deionized water, being mixed with the metal ion total concentration is the 100ml clear solution of 1.0mol/L.Add 19.21 gram citric acids then as crosslinking agent in this solution, stirring and dissolving forms transparent sol solution; In colloidal sol, add 3 gram urea then.Stirring becomes clear solution until dissolving, leaves standstill 2 hours, obtains active component sol impregnation liquid.
Get cordierite honeycomb ceramic carrier 2.5g, it is immersed in the active component sol impregnation liquid, placed 1 hour, take out ceramic honey comb, high pressure air rifle is blown away working fluid remaining in surface and the duct, keeps the permeability of ceramic honey comb, aeration-drying 5h under the room temperature.Catalyst precarsor descended dry 24 hours at 50 ℃, again 500 ℃ of roastings 4 hours, obtained impregnated catalyst 1 time.
The catalyst of 1 dipping is flooded in above-mentioned active component sol impregnation liquid again for the second time, repeat subsequent operation (comprising drying, roasting), can make the monolithic devices composite oxide catalysts of composite oxide supported amount 6.98wt%.
Embodiment 3
Take by weighing 3.02 gram Cu (NO
3)
23H
2Mn (the NO of O, 13.43 gram 50wt%
3)
2The aqueous solution, 16.28 gram Ce (NO
3)
36H
2O, 1.70 gram Zr (NO
3)
4, 1.20 the gram TiOSO
4, add a certain amount of deionized water, being mixed with the metal ion total concentration is the 100ml clear solution of 1.0mol/L.Add 19.21 gram citric acids then as crosslinking agent in this solution, stirring and dissolving forms transparent sol solution; In colloidal sol, add 1.2 gram urea then.Stirring becomes clear solution until dissolving, leaves standstill 1 hour, obtains active component sol impregnation solution.
Get cordierite honeycomb ceramic carrier 2.5g, it is immersed in the active component colloidal sol, placed 2 hours, take out ceramic honey comb, high pressure air rifle is blown away working fluid remaining in surface and the duct, keeps the permeability of ceramic honey comb, aeration-drying 1h under the room temperature.Catalyst precarsor descended dry 40 hours at 60 ℃, again 400 ℃ of roastings 8 hours, obtained impregnated catalyst 1 time.
The catalyst of 1 dipping is flooded in above-mentioned active component sol impregnation liquid again for the second time, repeat subsequent operation (comprising drying, roasting), can make the monolithic devices composite oxide catalysts of composite oxide supported amount 7.28wt%.
Embodiment 4
Take by weighing 3.02 gram Cu (NO
3)
23H
2Mn (the NO of O, 17.91 gram 50wt%
3)
2The aqueous solution, 10.85 gram Ce (NO
3)
36H
2O, 1.28 gram Zr (NO
3)
4, 1.40 the gram TiOSO
4, add a certain amount of deionized water, being mixed with the metal ion total concentration is the 100ml clear solution of 1.0mol/L.Add 19.21 gram citric acids then as crosslinking agent in this solution, stirring and dissolving forms transparent sol solution; In colloidal sol, add 6 gram urea then.Stirring becomes clear solution until dissolving, leaves standstill 4 hours, obtains active component sol impregnation solution.
Get cordierite honeycomb ceramic carrier 2.5g, it is immersed in the active component colloidal sol, placed 2 hours, take out ceramic honey comb, high pressure air rifle is blown away working fluid remaining in surface and the duct, keeps the permeability of ceramic honey comb, aeration-drying 8h under the room temperature.Catalyst precarsor descended dry 24 hours at 80 ℃, again 700 ℃ of roastings 3 hours, obtained impregnated catalyst 1 time.
The catalyst of 1 dipping is flooded in above-mentioned active component sol impregnation liquid again for the second time, repeat subsequent operation (comprising drying, roasting), can make the monolithic devices composite oxide catalysts of composite oxide supported amount 7.56wt%.
Embodiment 5
Take by weighing 1.05 gram Cu (NO
3)
23H
2Mn (the NO of O, 12.45 gram 50wt%
3)
2The aqueous solution, 15.10 gram Ce (NO
3)
36H
2O, 2.95 gram Zr (NO
3)
4, 2.78 the gram TiOSO
4, add a certain amount of deionized water, being mixed with the metal ion total concentration is the 100ml clear solution of 1.0mol/L.Add 19.21 gram citric acids then as crosslinking agent in this solution, stirring and dissolving forms transparent sol solution; In colloidal sol, add 3 gram urea then.Stirring becomes clear solution until dissolving, leaves standstill 2 hours, obtains active component sol impregnation liquid.
Get cordierite honeycomb ceramic carrier 2.5g, it is immersed in the active component sol impregnation liquid, placed 1 hour, take out ceramic honey comb, high pressure air rifle is blown away working fluid remaining in surface and the duct, keeps the permeability of ceramic honey comb, aeration-drying 5h under the room temperature.Catalyst precarsor descended dry 24 hours at 60 ℃, again 500 ℃ of roastings 4 hours, obtained impregnated catalyst 1 time.
The catalyst of 1 dipping is flooded in above-mentioned active component sol impregnation liquid again for the second time, repeat subsequent operation (comprising drying, roasting), can make the monolithic devices composite oxide catalysts of composite oxide supported amount 7.51wt%.
Embodiment 6
Take by weighing 2.42 gram Cu (NO
3)
23H
2Mn (the NO of O, 1.79 gram 50wt%
3)
2The aqueous solution, 34.72 gram Ce (NO
3)
36H
2O, 1.02 gram Zr (NO
3)
4, 0.32 the gram TiOSO
4, add a certain amount of deionized water, being mixed with the metal ion total concentration is the 100ml clear solution of 1.0mol/L.Add 19.21 gram citric acids then as crosslinking agent in this solution, stirring and dissolving forms transparent sol solution; In colloidal sol, add 3 gram urea then.Stirring becomes clear solution until dissolving, leaves standstill 2 hours, obtains active component sol impregnation liquid.
Get cordierite honeycomb ceramic carrier 2.5g, it is immersed in the active component sol impregnation liquid, placed 1 hour, take out ceramic honey comb, high pressure air rifle is blown away working fluid remaining in surface and the duct, keeps the permeability of ceramic honey comb, aeration-drying 5h under the room temperature.Catalyst precarsor descended dry 24 hours at 50 ℃, again 500 ℃ of roastings 4 hours, obtained impregnated catalyst 1 time.
The catalyst of 1 dipping is flooded in above-mentioned active component sol impregnation liquid again for the second time, repeat subsequent operation (comprising drying, roasting), can make the monolithic devices composite oxide catalysts of composite oxide supported amount 9.73wt%.
Embodiment 7
Take by weighing 1.72 gram Cu (NO
3)
23H
2Mn (the NO of O, 20.46 gram 50wt%
3)
2The aqueous solution, 2.48 gram Ce (NO
3)
36H
2O, 0.48 gram Zr (NO
3)
4, 4.57 the gram TiOSO
4, add a certain amount of deionized water, being mixed with the metal ion total concentration is the 100ml clear solution of 1.0mol/L.Add 19.21 gram citric acids then as crosslinking agent in this solution, stirring and dissolving forms transparent sol solution; In colloidal sol, add 3 gram urea then.Stirring becomes clear solution until dissolving, leaves standstill 2 hours, obtains active component sol impregnation liquid.
Get cordierite honeycomb ceramic carrier 2.5g, it is immersed in the active component sol impregnation liquid, placed 1 hour, take out ceramic honey comb, high pressure air rifle is blown away working fluid remaining in surface and the duct, keeps the permeability of ceramic honey comb, aeration-drying 5h under the room temperature.Catalyst precarsor descended dry 24 hours at 50 ℃, again 500 ℃ of roastings 4 hours, obtained impregnated catalyst 1 time.
The catalyst of 1 dipping is flooded in above-mentioned active component sol impregnation liquid again for the second time, repeat subsequent operation (comprising drying, roasting), can make the monolithic devices composite oxide catalysts of composite oxide supported amount 9.73wt%.
Embodiment 8
Take by weighing 3.02 gram Cu (NO
3)
23H
2Mn (the NO of O, 22.38 gram 50wt%
3)
2The aqueous solution, 5.43 gram Ce (NO
3)
36H
2O, 0.85 gram Zr (NO
3)
4, 1.6 the gram TiOSO
4, add a certain amount of deionized water, being mixed with the metal ion total concentration is the 100ml clear solution of 1.0mol/L.Add the 38.42g citric acid then as crosslinking agent in this solution, stirring and dissolving forms transparent sol solution; In colloidal sol, add 24.0g urea then.Stirring becomes clear solution until dissolving, leaves standstill 2 hours, obtains active component sol impregnation solution.
Get cordierite honeycomb ceramic carrier 2.5g, it is immersed in the active component colloidal sol, placed 1 hour, take out ceramic honey comb, high pressure air rifle is blown away working fluid remaining in surface and the duct, keeps the permeability of ceramic honey comb, aeration-drying 5h under the room temperature.Catalyst precarsor descended dry 20 hours at 100 ℃, again 600 ℃ of roastings 4 hours, obtained impregnated catalyst 1 time.
The catalyst of 1 dipping is flooded in above-mentioned active component sol impregnation liquid again for the second time, repeat subsequent operation (comprising drying, roasting), can make the monolithic devices composite oxide catalysts of composite oxide supported amount 7.42wt%.
Embodiment 9
Method according to embodiment 2 prepares whole composite oxide catalysts, and other conditions are identical, and the addition of different is citric acid is 9.6g, and the employing glycine is a fuel, and addition is 3.75 grams.
Embodiment 10
Method according to embodiment 2 prepares whole composite oxide catalysts, and other conditions are identical, and different is to adopt the polyethylene glycol of mean molecule quantity 500 as crosslinking agent, and the consumption of polyethylene glycol is 10.0g, and the employing alanine is a fuel, and addition is 4.45 grams.
Embodiment 11
The catalytic combustion activity test of the monolithic devices composite oxide catalysts for preparing by embodiment 2 is carried out on the gas-solid reaction device: the cylinder ceramic honeycomb catalyst is placed the reaction tube isothermal region.Unstripped gas and air divide two-way to enter, with mass flowmenter (D07-11A/ZM) control air inlet air speed, unstripped gas is pressed with the control organic steam by 0 ℃ of ice-water bath, converges with another road air then to enter reaction tube, and control organic compound inlet gas concentration is 5000mg/m
3, described catalyst combustion reaction temperature is 150～400 ℃, air speed adopts 5000h
-1, reaction end gas adopts the on-line analysis of Agilent 6890N chromatogram, and the reaction temperature when writing down different organic gas differentiated yields the results are shown in Table 1.As shown in Table 1, the catalyst of the present invention's preparation has advantages of high catalytic activity, especially at oxygen-containing organic compound waste gas.
The activity of all kinds of VOCs of table 1 catalytic combustion
Embodiment 12
With the catalyst of the foregoing description 1-10 method preparation, by carrying out the evaluation of ethyl acetate catalytic combustion, result such as table 2 under the embodiment 11 described devices.
Table 2 embodiment prepares the catalytic combustion ethyl acetate activity of catalyst
Claims (8)
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 described composite oxides are made up of Cu, Mn, Ce, Zr, Ti, the load capacity of described composite oxides is 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 described composite oxides.
2. composite oxide catalytic combustion catalyst as claimed in claim 1 is characterized in that the described oxide of being made up of Cu, Mn, Ce, Zr, Ti is that mixture by water-soluble Cu salt, Mn salt, Ce salt, Zr salt, Ti salt obtains at 400～700 ℃ of roasting temperatures.
3. composite oxide catalytic combustion catalyst as claimed in claim 2 is characterized in that described composite oxide catalytic combustion catalyst prepares by the following method:
(1) preparation active component sol impregnation liquid: get copper nitrate, manganese nitrate, cerous nitrate, zirconium nitrate and titanyl sulfate deionized water, be mixed with the metal salt solution that the metal ion total concentration is 0.5～2.0mol/L, Cu in the described metal salt solution, Mn, Ce, Zr, the ratio of the amount of substance of Ti is 1.0: 0.5～8.0: 0.5～8.0: 0.2～2.0: 0.2～4.0, in metal salt solution, add crosslinking agent then, described 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 described 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, described 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 described 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, repetition aforesaid operations to the load capacity of the active component on ceramic honey comb surface is 2～20wt%, makes described composite oxide catalytic combustion catalyst.
4. composite oxide catalytic combustion catalyst as claimed in claim 3 is characterized in that in the described step (1), described fuel is urea.
5. composite oxide catalytic combustion catalyst as claimed in claim 3 is characterized in that in the described 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 described fuel and the sol solution.
6. the preparation method of composite oxide catalytic combustion catalyst as claimed in claim 2 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 deionized water, be mixed with the metal salt solution that the metal ion total concentration is 0.5～2.0mol/L, Cu in the described metal salt solution, Mn, Ce, Zr, the ratio of the amount of substance of Ti is 1.0: 0.5～8.0: 0.5～8.0: 0.2～2.0: 0.2～4.0, in metal salt solution, add crosslinking agent then, described 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 described 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, described 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 described 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, repetition aforesaid operations to the load capacity of the active component on ceramic honey comb surface is 2～20wt%, makes described composite oxide catalytic combustion catalyst.
7. composite oxide catalytic combustion catalyst as claimed in claim 1 is eliminated 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.
8. application as claimed in claim 7, it is characterized in that described catalytic combustion carries out on the gas-solid reaction device: get described catalyst, place the reaction tube isothermal region, unstripped gas and air divide two-way to enter, unstripped gas converges with another road air then by 0 ℃ of ice-water bath and enters reaction tube, carry out catalyst combustion reaction through catalyst action in reaction tube, described catalyst combustion reaction temperature is 150～450 ℃, and air speed is GHSV=5000h
-1
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| CN103252242A (en) * | 2012-02-16 | 2013-08-21 | 中国石油化工股份有限公司 | Non-noble metal catalyst used for catalytic combustion of PTA exhaust gas and preparation method thereof |
| CN103758613A (en) * | 2014-01-27 | 2014-04-30 | 黄育新 | Automobile exhaust soot particle trapping burner |
| CN104107700A (en) * | 2013-04-16 | 2014-10-22 | 中国科学院兰州化学物理研究所 | Industrial organic exhaust gas combustion catalyst and preparation method thereof |
| CN104998655A (en) * | 2015-07-22 | 2015-10-28 | 中国科学院过程工程研究所 | Integral cordierite catalyst and preparation method and application thereof |
| CN106552642A (en) * | 2016-11-03 | 2017-04-05 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of titanium dichloride load cobalt manganese composite oxide and preparation and application |
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| CN103252242B (en) * | 2012-02-16 | 2015-04-01 | 中国石油化工股份有限公司 | Non-noble metal catalyst used for catalytic combustion of PTA exhaust gas and preparation method thereof |
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| CN106552642A (en) * | 2016-11-03 | 2017-04-05 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of titanium dichloride load cobalt manganese composite oxide and preparation and application |
| CN108067230A (en) * | 2016-11-11 | 2018-05-25 | 中国石油化工股份有限公司抚顺石油化工研究院 | A kind of preparation method of non-precious metal catalyst |
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| CN106881081A (en) * | 2017-03-15 | 2017-06-23 | 武汉工程大学 | A kind of three-dimensional ordered mesoporous manganese-cerium composite oxide catalyst and its preparation method and application |
| CN106881081B (en) * | 2017-03-15 | 2019-12-06 | 武汉工程大学 | Three-dimensional ordered mesoporous manganese-cerium composite oxide catalyst and preparation method and application thereof |
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| CN107754809A (en) * | 2017-10-23 | 2018-03-06 | 浙江工商大学 | The Cu Mn Zr composite catalysts and preparation method of degraded VOCs waste gas |
| CN107754809B (en) * | 2017-10-23 | 2020-04-21 | 浙江工商大学 | Cu-Mn-Zr composite catalyst for degrading VOCs waste gas and preparation method thereof |
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| CN108607544B (en) * | 2018-05-03 | 2021-01-15 | 青岛大学 | Low-temperature catalytic oxidation catalyst for volatile organic compounds and preparation and application thereof |
| CN108619887A (en) * | 2018-05-17 | 2018-10-09 | 绍兴市鼎泰节能环保科技有限公司 | A kind of exhaust treatment system |
| CN112169787A (en) * | 2019-07-04 | 2021-01-05 | 重庆鲍斯净化设备科技有限公司 | Catalyst for removing hydrocarbon substances by low-temperature combustion and preparation method thereof |
| CN110729493A (en) * | 2019-10-08 | 2020-01-24 | 成都新柯力化工科技有限公司 | Continuous production method for improving dispersibility of fuel cell catalyst slurry |
| CN110833833A (en) * | 2019-11-14 | 2020-02-25 | 西安凯立新材料股份有限公司 | Non-noble metal composite oxide honeycomb catalyst for catalytic combustion of low-carbon hydrocarbons |
| CN112958088A (en) * | 2021-03-23 | 2021-06-15 | 河南神马尼龙化工有限责任公司 | Preparation method of biochar catalyst for synergistically purifying volatile organic pollutants |
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