CN101269335B - Sulfureous resistant four-effect catalyst for purifying tail gas of vehicle - Google Patents

Abstract

The invention relates to a performance-optimized anti-sulfur four-way catalyst for purifying automobile tail gas. The first is to prepare a glass coating solution, and then repeatedly immerse the alloy metal carrier in the glass coating solution for coating, after drying and calcining, the glass coating is obtained on the carrier, and then repeatedly immersing in the mixed solution of zirconium and titanium salt, precious metal The catalyst solution is also dried and calcined to obtain an anti-sulfur four-way catalyst for vehicles used for purifying automobile exhaust with alloy metal as a carrier. The four-way catalyst of the present invention has the following advantages: 1) PM and NOx are catalyzed on the same catalytic bed; 2) _SO2 has no effect on the catalytic efficiency when the concentration of SO is 500-800 ppm; 3) compared with other catalysts The catalyst has high anti-sulfur performance and is supported by metal. The engine that meets Euro III emission can meet the use requirements of Euro IV and above emission standards in the laboratory, bench test and practical application.

Description

Anti-sulfur four-way catalyst for purifying automobile exhaust

technical field

The invention belongs to the field of exhaust gas purification of automobiles (including diesel vehicles and gasoline vehicles), and in particular relates to an anti-sulfur four-way catalyst for purifying automobile exhaust with optimized performance.

technical background

The development of the automobile industry has brought convenience to human transportation, but it has also brought serious air pollution. The tail gas emitted by automobiles mainly contains PM, NOx, CO, and HC, which can cause acid rain and urban photochemical smog, affect the ecological environment, and endanger human health. In order to solve this problem, the installation of exhaust catalytic converters is an external purification method commonly used in various countries. Catalyst is the core part of the catalytic converter, it must meet the requirements of high conversion rate, good heat resistance, long service life and good anti-toxicity. The development and research level of four-way catalysts directly means the comprehensive level of modern automobiles, because the development technology of automobile exhaust purification catalysts is one of the modern automobile technologies. SO ₂ in automobile exhaust has a great influence on the activity of the catalyst, and is an important factor restricting the catalytic performance and service life of the catalyst. In particular, the content of SO ₂ in the tail gas of diesel vehicles is relatively high, and the content of oxygen in the tail gas is as high as 5-19%. It is easier to further oxidize the SO ₂ in the tail gas into SO ₃ , thereby forming sulfate and sulfite. The active site is covered, and the catalyst cannot be regenerated in this state, which has a greater poisoning effect on the catalyst. Traditional automotive catalysts are generally divided into three categories: (1) noble metals are used as active components. Although they have high activity, they are expensive and prone to sintering deactivation at high temperatures. The development of non-precious metal autocatalysts has been carried out. (2) Non-noble metal catalysts with composite oxides or mixtures of transition elements as active components, among which perovskite composite oxides are the most studied. Non-precious metal catalysts have good catalytic activity, which is similar to that of noble metals, but their adsorption capacity is strong and their desorption is difficult, especially for _SO2 adsorption, so sulfur poisoning is extremely prone to occur. (3) Catalysts containing rare earth elements. At present, precious metal deposits are extremely scarce in my country, but rare earth deposits are very abundant, and the output ranks first in the world. The price of rare earth elements is cheap, so the development of rare earth catalysts is compatible with my country's national conditions.

Replacing precious metal catalysts with rare earth metal oxides, transition metal oxides and alkaline earth metal oxide catalysts should be an inevitable trend of the development of the times, and this is a correct choice in line with my country's national conditions. The addition of rare earth elements can improve the binding strength and thermal stability of the catalyst carrier and the anti-poisoning ability of the catalyst, especially the anti-sulfur poisoning ability of the catalyst.

Contents of the invention

The object of the present invention is to provide a sulfur-resistant four-way catalyst for purifying automobile exhaust gas on an alloy metal carrier of an automobile exhaust processor, which is resistant to sulfur and high temperature oxidation, and has a strong combination ability with the metal carrier. The sulfur-resistant four-way catalyst for purifying automobile exhaust of the present invention is prepared by the following method:

1. Metal carrier pretreatment:

The alloy metal carrier is a commercially available nickel-chromium-iron alloy material with high temperature resistance. The integrated honeycomb structure with a pore density of 100-500 meshes is made by using the manufacturing method of the engine exhaust processor with a convoluted structure developed by us. Chinese patent: 200610016967.4, engine exhaust processor with convoluted structure with metal as carrier). Surface treatment of the carrier, specifically:

1) Completely immerse the honeycomb structure alloy metal carrier in a mixed solution of ammonia water, KOH or NaOH and hydrogen peroxide with a concentration of 3% to 40%, the volume ratio of the two is 4:1 to 6:1, and the alkali washes to remove Oil stains on the metal surface, ultrasonic cleaning for 0.5 to 3 hours, and then drying;

2) Completely immerse the above-mentioned alloy metal carrier in a mixture of hydrochloric acid and hydrogen peroxide with a concentration of 3% to 40%, the volume ratio of the two is 4:1 to 6:1, neutralize the lye and remove it by pickling at the same time The oxide on the surface of the metal carrier is pickled for 1 to 40 minutes, and then dried;

3) The above-mentioned alloy metal carrier is completely immersed in deionized water, and ultrasonically cleaned for 0.5 to 3 hours to remove surface acid radical ions, etc., and then dried;

4) The above-mentioned alloy metal carrier is completely immersed in absolute ethanol for cleaning, and ultrasonically cleaned for 0.5 to 3.5 hours, thereby enhancing the dispersion ability of the metal carrier, making the catalyst more uniformly dispersed, and then drying;

5) The SEM of the surface of the carrier after the above-mentioned alloy metal carrier is roasted at 600-1000°C under air conditions is shown in Figure 2. It is obvious from the SEM image that the carrier after pretreatment by this method has an obvious ratio of The treated (SEM of the untreated support is shown in Figure 1) has a larger specific surface area.

2. Preparation of glass coating sol-gel solution:

1) Using distilled water as a solvent, prepare copper nitrate trihydrate (Cu(NO ₃ ) ₂ 3H ₂ O) solution with a mass concentration of 5-40%, nickel nitrate hexahydrate (Ni(NO ₃ ) ₂ 6H 5-50% ₂ O) solution, 5-50% manganese nitrate hexahydrate (Mn(NO ₃ ) ₂ 6H ₂ O) solution and 5-50% cobalt nitrate hexahydrate Co(NO ₃ ) ₂ 6H ₂ O solution, and then the 2 ～4 kinds of above-mentioned nitrate solutions are mixed in equal volumes; repreparing mass concentration is 5～38% aluminum nitrate nonahydrate (Al(NO ₃ ) ₃ 9H ₂ O) solution, 5%～20% boric acid solution, and then 10 ～30g of the above nitrate mixed solution, 10～15g of aluminum nitrate solution and 10～20g of boric acid solution are mixed, and stirred at a temperature of 20～60°C for 1～3 hours until all the salts are completely dissolved;

2) take by weighing 2～12ml mass concentration be the ethanol of 60%～95%, the distilled water of 0.5～1.5ml, 0.1～2ml mass concentration be the concentrated nitric acid of 65%～80%, after three kinds of solutions are mixed and stirred evenly, Then weigh 9-27ml of tetraethyl orthosilicate, slowly, intermittently, and pour it into the above three mixed solutions with strong stirring at the same time, finally forming a transparent mixed solution;

3) Adjust the pH value of the solution prepared in step 2) to 1-5; then take 10-35 grams of the mixed solution prepared in step 2), and slowly inject the obtained solution into 30-65 grams of the mixed solution in step 1). In the liquid, while vigorously stirring, the final mixed liquid is a sol-gel solution of the glass coating;

3. Preparation of catalyst solution:

1) The nitrates of zirconium and titanium plus distilled water are respectively prepared into solutions with a certain mass concentration. The mass concentration of zirconium nitrate in the final system is 1-25%, and the mass concentration of titanium nitrate is 3-40%. Stir at low temperature for 0.1 to 2.5 hours until all salts are completely dissolved;

2) Dilute the nitrate or chlorate of platinum, rhodium or palladium with distilled water, and prepare noble metal salt solutions with a mass concentration of 0.5 to 5%, 0.5 to 3%, and 0.5 to 4% respectively, and then mix the above 1 to 3 kinds The noble metal salt solution is mixed to obtain a noble metal catalyst solution;

4. Coating process of coating and catalyst:

1) Repeatedly immerse the honeycomb alloy metal carrier in the glass coating solution for coating, drain the alloy metal carrier after each coating, blow dry with a hair dryer after draining, and then perform the next dipping coating, Coating 2-10 times, do not dry after the last coating, directly use absorbent cotton to dry the metal carrier in the air at room temperature for 5-15 hours, then dry in the air at 60-180°C to constant weight , take out after cooling with the furnace;

2) Baking the dried honeycomb alloy metal carrier with glass coating in the air at a temperature of 500-1000°C in a muffle furnace for 1-30 minutes, thereby preparing glass on the surface of the honeycomb alloy metal carrier Coating, the final glass coating accounts for 4 to 10% of the weight of the alloy metal carrier, and the SEM of the glass coating is shown in Figure 3, showing a larger specific surface area;

3) Immerse the glass-coated honeycomb alloy metal carrier into the mixture of zirconium and titanium salt prepared in method 3, and repeatedly immerse the honeycomb alloy metal carrier into the mixture of zirconium and titanium salt. After each coating, drain the alloy metal carrier, dry it with a hair dryer, and then perform the next dip coating, coating 2 to 10 times, and do not apply after the last coating Blow dry, directly use absorbent cotton to dry the metal carrier in the air at room temperature for 5-15 hours, then dry in the air at a temperature of 60-180°C to constant weight, and take it out after cooling in the furnace;

4) Roast the dried honeycomb alloy metal carrier with zirconium and titanium salt catalysts in the air at a temperature of 500-1000°C in a muffle furnace for 1-4 hours, thereby preparing on the surface of the honeycomb alloy metal carrier Obtain the catalyzer containing zirconia, titania, catalyst SEM is shown in Fig. 4, shows larger specific surface area;

5) Repeatedly immerse the alloy metal carrier with zirconia, titanium oxide and glass coating in the prepared precious metal catalyst solution for coating, drain the alloy metal carrier after each coating, and use Dry it with a hair dryer, and then carry out the next dipping coating until the weight of the metal carrier increases by 2-10%. After the last coating, dry it at a temperature below 180°C, and then bake it at a constant temperature of 600-1000°C for 0.5-5 hours. Activation and setting treatment, and then obtain the anti-sulfur four-way catalyst for vehicles with alloy metal as the carrier.

The technical effects of the present invention are: the four-way catalyst of the present invention has the following advantages: 1) PM and NOx are catalyzed on the same catalytic bed; 2) _SO Concentration is 500～800ppm, without any influence on catalytic efficiency; 3) Compared with other catalysts, the catalyst has high sulfur resistance and is supported by metals.

The new metal carrier we choose has the following advantages: 1) The geometric surface area is large, so that the volume of the purifier is reduced. Under the condition of obtaining the same purification performance, the active components (especially precious metal components) used as catalysts can be saved; 2) good preheating performance and smaller back pressure; 3) large specific surface area and the combination performance of transition layer and catalyst Good; 4) High mechanical strength, etc. Therefore, the metal carrier and the anti-sulfur four-way catalyst of the present invention have great popularization and application value.

Apply the anti-sulfur four-way catalyst prepared by the present invention, and its catalytic effect is:

1) When the concentration of _SO2 is 500-800ppm, the light-off temperature of the catalyst in the exhaust gas is below 200°C, and the conversion rate of SOF (aromatic hydrocarbons in the exhaust gas) is higher than 90%, based on the Euro III diesel engine , after passing through the catalyst and the particulate filter, the PM emission in the exhaust gas meets the standards above Euro IV or even Euro V;

2) When the concentration of _SO2 is 500-800ppm, based on the Euro III diesel engine, the conversion rate of CO and HC meets the Euro V standard after passing through the catalyst and the particulate filter;

3) When the concentration of SO ₂ is 500-800ppm, based on the Euro III diesel engine, after passing through the catalyst, the NOx emission in the tail gas meets the Euro IV standard.

In a word, the anti-sulfur four-way catalyst can make the engine meeting Euro III emission meet Euro IV or above emission standard in the laboratory, bench test and practical application, and can meet the low emission requirements of gasoline vehicles and diesel vehicles.

Description of drawings:

Figure 1: SEM surface topography photo of the metal carrier without any treatment;

Figure 2: SEM surface topography photo of the metal carrier after surface pretreatment;

Figure 3: SEM surface topography photo of the glass coating on the metal carrier;

Figure 4: SEM surface topography photo of the catalyst loaded on the glass-coated metal carrier;

specific implementation plan

This patent is to illustrate the present invention with specific embodiments, but not to limit the present invention. Any method that can be used in automobile engine exhaust gas purification processors to prepare four-way catalysts on metal supports involves metal oxides As the main component or related non-metal oxides, and any form of metal salt (such as nitrate, chlorate, etc.) Catalysts are all within the protection scope of our rights.

Example 1:

Get 5 grams of aluminum nitrate nonahydrate (Al(NO ₃ ) ₃ 9H ₂ O), 5 grams of nickel nitrate hexahydrate (Ni(NO ₃ ) ₂ 6H ₂ O); 5 grams of cobalt nitrate hexahydrate (Co(NO ₃ ) ₂ 6H ₂ (0) 5 grams of distilled water 10ml are added respectively, then the aqueous solutions of each nitrate are mixed, after taking 1 gram of boric acid and 10 grams of distilled water to make a solution, mix with the nitrate mixed solution, and stir for 0.5 hour at a temperature of 25° C. until all The salt is completely dissolved, and 40 grams of the mixed solution of nitrate and boric acid is taken out.

Weigh 2ml of ethanol with a concentration of 80%, 1ml of water, and 0.1ml of concentrated nitric acid with a concentration of 65%, mix the three solutions and stir evenly, then weigh 15ml of tetraethyl orthosilicate, slowly, intermittently, and simultaneously Stir vigorously and pour into the above-mentioned three mixed solutions, finally form a transparent mixed solution, adjust the pH value of the solution to 4 with hydrochloric acid, then take 15 grams of the mixed solution adjusted by the pH value, and slow down the obtained solution Slowly pour into the mixed solution of 40 grams of nitrate and boric acid, while vigorously stirring, the final mixed solution is a sol-gel solution for glass coating.

The alloy metal treated by the metal carrier pretreatment method in step 1 is made into a strip-shaped carrier, put into the above-mentioned glass coating solution, and the honeycomb alloy metal carrier is repeatedly immersed in the glass coating solution for coating. Drain the alloy metal carrier after coating, dry it with a hair dryer, and then carry out the next dip coating, coating 4 times, do not blow dry after the last coating, directly use absorbent cotton to make the metal carrier in the air Dry in the shade at room temperature for 8 hours, then dry in the air at 60°C to constant weight, take it out after cooling in the furnace, and place the dried glass-coated alloy metal carrier in the air at a temperature of 500°C Baking in a muffle furnace for 2 minutes, thereby preparing a glass coating on the surface of the alloy metal carrier, and finally the glass coating accounts for 5% of the weight of the alloy metal carrier.

Take 2.5 grams and 5 grams of nitrates of zirconium and titanium respectively, and then add 10ml of distilled water to prepare a solution with a certain mass concentration, then mix the two solutions and stir at a temperature of 50°C for 10 minutes until all the salts are completely dissolved . Take 0.1 g of nitrate compounds of platinum and palladium respectively, add 10 ml of distilled water to dilute and mix respectively to prepare a precious metal catalyst solution.

The alloy metal carrier coated with the glass coating is immersed in the prepared mixed solution of zirconium and titanium salt by means of dip coating, and the alloy metal carrier is repeatedly immersed in the mixed solution of zirconium and titanium salt for coating. Drain the alloy metal carrier after one coating, and blow it dry with a blower, and then carry out the next dipping coating, coating 4 times, do not dry it after the last coating, directly use absorbent cotton to make the metal carrier in the Dry in the air at room temperature for 5 hours, then dry in air at 60°C until constant weight, and take it out after cooling in the furnace. The dried alloy metal carrier with zirconium and titanium salt catalysts was calcined in a muffle furnace for 4 hours at a temperature of 500° C. in air, so that a catalyst containing zirconia and titanium oxide was prepared on the surface of the alloy metal carrier.

The precious metal catalyst layer is prepared on the glass coating with zirconia and titania by dip coating, and the alloy metal carrier with zirconia, titania and glass coating is repeatedly immersed in the prepared platinum and palladium. Coating in the mixed liquid solution, drain the alloy metal carrier after each coating, dry it with a hair dryer, and then carry out the next dip coating until the weight of the metal carrier increases by 5%, and the last coating After coating, it is dried at 60°C, and then roasted at a constant temperature of 500°C for 4 hours for activation and setting treatment, thereby obtaining a sulfur-resistant four-way catalyst for vehicles with alloy metal as a carrier.

Like this by scanning electron microscope as shown in Fig. 3, 4 just can see on the alloy support that coated one deck glass coating of the present invention and catalyst (thickness is 2 microns), measure by XPS again at last coated on the alloy support The coated coating and catalyst components (mass content) are aluminum dioxide (Al ₂ O ₃ ) 8%, nickel oxide (NiO) 10%, cobalt oxide (CoO) 15%, boron trioxide (B ₂ O ₃ ) 5%, silicon dioxide (SiO ₂ ) 49%, zirconia (ZrO ₂ ) 4%, titanium oxide (TiO) 8%, platinum (Pt) 0.5%, palladium (Pd) 0.5%.

Example 2:

Get 5 grams of aluminum nitrate nonahydrate (Al(NO ₃ ) ₃ 9H ₂ O), 5 grams of manganese nitrate (Mn(NO ₃ ), 5 grams of copper nitrate trihydrate (Cu(NO ₃ ) ₂ 3H ₂ O), add 10ml of distilled water, then mix the aqueous solutions of nitrates, take 1 gram of boric acid and 10ml of distilled water to make a solution, mix it with the mixed solution of nitrates, stir at 30°C for 0.5 hours, until all the salts are completely dissolved, and take out the nitrates 35 grams of mixed solution with boric acid.

Weigh 3ml of ethanol with a concentration of 80%, 2ml of water, and 0.1ml of concentrated nitric acid with a concentration of 65%, mix the three solutions and stir evenly, then weigh 20ml of tetraethyl orthosilicate, slowly, intermittently, and simultaneously Stir vigorously and pour into the above three mixed solutions to finally form a transparent mixed solution, adjust the pH value of the solution to 4, then take 20 grams of the mixed solution with adjusted pH value, and slowly inject the solution Into the mixed solution of 35 grams of nitrate and boric acid, vigorously stir simultaneously, the mixed solution that finally forms is the sol-gel solution of glass coating.

The alloy metal treated by the metal carrier pretreatment method in step 1 is made into a strip-shaped carrier, put into the above-mentioned glass coating solution, and the honeycomb alloy metal carrier is repeatedly immersed in the glass coating solution for coating. Drain the alloy metal carrier after coating, dry it with a hair dryer, and then carry out the next dip coating, coating 5 times, do not dry it after the last coating, directly use absorbent cotton to make the metal carrier in the air Dry in the shade at room temperature for 8 hours, then dry in the air at 60°C to constant weight, take it out after cooling in the furnace, and place the dried glass-coated alloy metal carrier in the air at a temperature of 600°C Baking in a muffle furnace for 2 minutes, thereby preparing a glass coating on the surface of the alloy metal carrier, and finally the glass coating accounts for 5% of the weight of the alloy metal carrier.

Take zirconium and titanium nitrates or other forms of zirconium and titanium salts as 1.5 grams and 7.5 grams respectively, and then add 10ml of distilled water to prepare a solution with a certain mass concentration, then mix the two solutions and stir at a temperature of 50°C 10 minutes until all the salt is completely dissolved. Take 0.1 g of platinum and palladium noble metal salt compounds, respectively add 10 ml of distilled water to dilute and mix to prepare a noble metal catalyst solution.

The alloy metal carrier coated with the glass coating is immersed in the prepared mixed solution of zirconium and titanium salt by means of dip coating, and the alloy metal carrier is repeatedly immersed in the mixed solution of zirconium and titanium salt for coating. Drain the alloy metal carrier after one coating, blow it dry with a blower, and then carry out the next dipping coating, coating 5 times, do not dry it after the last coating, directly use absorbent cotton to make the metal carrier in the Dry in the air at room temperature for 5 hours, then dry in air at 60°C until constant weight, and take it out after cooling in the furnace. The dried alloy metal carrier with zirconium and titanium salt catalysts was calcined in a muffle furnace for 4 hours at a temperature of 600° C. in air, so that a catalyst containing zirconium oxide and titanium oxide was prepared on the surface of the alloy metal carrier.

The precious metal catalyst layer is prepared on the glass coating with zirconia and titania by dip coating, and the alloy metal carrier with zirconia, titania and glass coating is repeatedly immersed in the prepared platinum and palladium. Coating in the mixed liquid solution, drain the alloy metal carrier after each coating, dry it with a hair dryer, and then perform the next dip coating until the weight of the metal carrier increases by 6%, and the last coating After coating, it is dried at 60°C, and then roasted at a constant temperature of 600°C for 4 hours for activation and setting treatment, thereby obtaining a sulfur-resistant four-way catalyst for vehicles with alloy metal as a carrier.

Like this by scanning electron microscope as shown in Fig. 3, 4 just can see on the alloy support that coated one deck glass coating of the present invention and catalyst (thickness is 1 micron), measure by XPS again at last coated on the alloy support The coated coating and catalyst components (mass content) are aluminum dioxide (Al ₂ O ₃ ) 8%, manganese oxide (MnO) 12%, copper oxide (CuO) 16%, boron trioxide (B ₂ O ₃ ) 6%, silicon dioxide (SiO ₂ ) 51%, zirconia (ZrO ₂ ) 2%, titanium oxide (TiO) 4%, platinum (Pt) 0.5%, palladium (Pd) 0.5%.

Claims (3)

1. sulfureous resistant four-effect catalyst for purifying tail gas of vehicle, it is prepared by following method:

The preparation of A, glass coating sol-gel solution:

1) with distilled water is solvent, the preparation mass concentration is 5～40% nitrate trihydrate copper solution, 5～50% six water nickel nitrate solutions, 5～50% six water manganese nitrate solutions and 5～50% cobalt nitrate hexahydrate solution, then 2～4 kinds of above-mentioned nitrate solution equal-volumes is mixed; Preparing mass concentration again is 5～38% nine water aluminum nitrate solutions, 5%～20% BAS, then the above-mentioned nitrate mixed solution of 10～30g, 10～15g aluminum nitrate solution, 10～20g BAS are mixed, under 20～60 ℃ temperature, stirred 1～3 hour, and dissolved fully up to all salt;

2) taking by weighing 2～12ml mass concentration is that 60%～95% ethanol, the distilled water of 0.5～1.5ml, 0.1～2ml mass concentration are 65%～80% red fuming nitric acid (RFNA), after three kinds of solution mixing and stirring, take by weighing the positive tetraethyl orthosilicate of 9～27ml again, slowly, intermittently, powerful pouring in above-mentioned three kinds of mixed liquors of stirring simultaneously, finally form transparent mixed solution;

3) regulating step 2) the pH value of solution of preparation is 1～5; Get step 2 then) liquid mixture prepared 10～35 grams, and with in the getting solution mixed liquor that is injected into 30～65 gram step 1) slowly, powerful simultaneously the stirring, the final mixed liquor that forms is the sol-gel solution of glass coating;

The preparation of B, catalyst solution:

1) the nitrate adding distil water of zirconium and titanium is mixed with the solution of certain mass concentration respectively, final system zirconium nitrate mass concentration is 1～25%, the mass concentration of Titanium Nitrate is 3～40%, stirs 0.1～2.5 hour under 10 ℃～60 ℃ temperature, dissolves fully up to all salt;

2) with the nitrate of platinum, rhodium or palladium or the dilution of chlorate adding distil water, prepare mass concentration respectively and be 0.5～5%, 0.5～3%, 0.5～4% precious metal salt solution, then will above-mentioned 1～3 kind of precious metal salt solution mixing, obtain the precious metal catalyst agent solution;

The coating of C, coating and catalyst:

1) cellular alloying metal carrier is immersed in the glass coating solution repeatedly applies, after applying each time, the alloying metal carrier is drained, draining the back dries up with hair-dryer, and then carry out next time immersion coating, apply 2～10 times, do not dry up after last the coating, directly utilize absorbent cotton that metallic carrier was dried in the shade under room temperature 5～15 hours in air, then in air, under 60～180 ℃ of temperature, dry, take out with stove cooling back to constant weight;

2) the cellular alloying metal carrier that has glass coating that will dry is roasting 1～30 minute in Muffle furnace under 500～1000 ℃ temperature in air, thereby prepares glass coating at cellular alloying metal carrier surface;

3) will be the mode of cellular alloying metal carrier by immersion coating of coated glass coating immerse the zirconium that prepared and the mixed liquor of titanium salt, cellular alloying metal carrier is immersed repeatedly in the mixed liquor of zirconium and titanium salt and apply, after applying each time, the alloying metal carrier is drained, draining the back dries up with hair-dryer, and then carry out next time immersion coating, apply 2～10 times, do not dry up after last the coating, directly utilize absorbent cotton that metallic carrier was dried in the shade under room temperature 5～15 hours in air, then in air, under 60～180 ℃ of temperature, dry, take out with stove cooling back to constant weight;

4) the cellular alloying metal carrier that has zirconium, titanium salt catalyst that will dry is roasting 1～4 hour in Muffle furnace under 500～1000 ℃ temperature in air, thereby obtains containing the catalyst of zirconia, titanium oxide in cellular alloying metal carrier glass coating surface preparation;

5) the alloying metal carrier that will have zirconia, titanium oxide, glass coating again immerses repeatedly in the precious metal catalyst agent solution that has prepared and applies, after the coating alloying metal carrier is being drained each time, draining the back dries up with hair-dryer, and then carry out next time immersion coating, to metallic carrier weightening finish 2～10%, dry below the temperature in 180 ℃ last coating back, activated typing in 0.5～5 hour in 600～1000 ℃ of constant temperature calcinings again and handle, and then to obtain with the alloying metal be the automobile-used sulfureous resistant four-effect catalyst of purifying automobile tail gas of carrier.

2. sulfureous resistant four-effect catalyst for purifying tail gas of vehicle as claimed in claim 1 is characterized in that: the alloying metal carrier uses after surface preparation.

3. sulfureous resistant four-effect catalyst for purifying tail gas of vehicle as claimed in claim 2 is characterized in that: the surface treatment of alloying metal carrier comprises the steps,

1) the alloying metal carrier is immersed fully in the mixed solution that concentration is 3%～40% ammoniacal liquor, KOH or NaOH and hydrogen peroxide, both volume ratios are 4: 1～6: 1, and the greasy dirt of metal surface is removed in alkali cleaning, and ultrasonic wave cleaned 0.5～3 hour, then oven dry;

2) above-mentioned alloying metal carrier is immersed fully again in the mixed liquor that concentration is 3%～40% hydrochloric acid and hydrogen peroxide, both volume ratios are 4～6: 1, in and alkali lye pickling simultaneously remove the oxide of metal carrier surface, the pickling time is 1～40 minute, thereafter oven dry;

3) above-mentioned alloying metal carrier is immersed in the deionized water fully, ultrasonic wave cleaned 0.5～3 hour, flush away surface acid radical ion etc., oven dry thereafter;

4) above-mentioned alloying metal carrier is immersed in the absolute ethyl alcohol fully clean, ultrasonic wave cleaned 0.5～3.5 hour, thereby strengthened the dispersibility of metallic carrier, and it is more even that catalyst is disperseed, thereafter oven dry;

5) above-mentioned alloying metal carrier is handled at 600～1000 ℃ of roasting temperatures under air conditions.

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