CN101269335A - Sulfureous resistant four-effect catalyst for purifying tail gas of vehicle - Google Patents
Sulfureous resistant four-effect catalyst for purifying tail gas of vehicle Download PDFInfo
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- CN101269335A CN101269335A CNA200810050693XA CN200810050693A CN101269335A CN 101269335 A CN101269335 A CN 101269335A CN A200810050693X A CNA200810050693X A CN A200810050693XA CN 200810050693 A CN200810050693 A CN 200810050693A CN 101269335 A CN101269335 A CN 101269335A
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Abstract
The invention relates to an anti-sulfur four-way catalyst which is provided with optimal performance and used for purifying automobile exhaust. First, a glass coating solution is prepared, then a metal alloy carrier is repeatedly immerged into the glass coating solution for coating, drying, calcinating so as to get the glass coating on the carrier, then the glass coating is repeatedly immerged into a mixed solution composed of titanium and zirconium salts and into a precious metal catalyst solution; after being baked and calcinatied, the anti-sulfur four-way catalyst which is provided with optimal performance and used for purifying automobile exhaust and takes the alloy metal as a carrier is obtained. The four-way catalyst of the invention has the following advantages that: (1) PM and NOx are catalyzed on the same catalytic bed; (2) the catalytic efficiency is not affected if the concentration of SO2ranges from 500 to 800ppm; (3) compared with other catalysts, the catalyst has high anti-sulfur performance and takes metal as the carrier. Besides, the catalyst can ensure an engine meeting the emission of European III in a laboratory, a bench experimental testing and application to meet the requirements for emission standards above European IV.
Description
Technical field
The invention belongs to automobile (comprising diesel vehicle and gasoline car) tail gas clean-up field, be specifically related to a kind of sulfureous resistant four-effect catalyst for purifying tail gas of vehicle of performance optimization.
Technical background
Developing of automobile industry is that human traffic offers convenience, but also brings serious atmosphere pollution simultaneously.Mainly contain PM, NOx in the tail gas of motor vehicle emission, CO, HC can cause acid rain and city photochemical fog, influence ecological environment is detrimental to health.For addressing this problem, it is the external purification method that various countries generally adopt that vent gas catalytic cleaner is installed.Catalyst is the core of catalytic cleaner, and it is good that it must satisfy conversion ratio height, good heat resistance, long service life, mithridatism.The developmental research level of quadruple effect catalyst is directly meaned the level of aggregation of Hyundai Motor, because the development technique of cleaning catalyst for tail gases of automobiles is exactly one of Hyundai Motor technology.SO in the automobile exhaust
2Activity of such catalysts is had very big influence, is the catalytic performance of restriction catalyst and a key factor in service life.Especially exhaust gas from diesel vehicle SO
2Content higher, and in the tail gas content of oxygen up to 5～19%, easier of the SO in the tail gas
2Further be oxidized to SO
3Thereby, form sulfate, sulphite, the activity of such catalysts position is covered, and catalyst is non-renewable under this state, thereby catalyst is produced bigger toxic action.Traditional automotive catalyst is divided three classes substantially: (1) is active component with the noble metal, though have higher activity, but cost is very high, and at high temperature the sintering inactivation takes place easily, has therefore carried out the development of base metal automobile catalyst in recent years both at home and abroad unexpectedly mutually.(2) be the non-precious metal catalyst that active component divides with the composite oxides of transition elements or mixture, wherein studying more is calcium titanium type composite oxides.Non-precious metal catalyst has catalytic activity preferably, has the catalytic activity close with noble metal, but its high adsorption capacity and desorption are difficult, especially to SO
2Absorption, therefore sulfur poisoning very easily takes place.(3) contain the catalyst of rare earth element, China's noble metal mineral reserve are in great shortage at present, rank first in the world but the rare earth mineral reserve very enrich output, and so the rare earth low price is the compound China's national situation of exploitation rare earth catalyst.
Substituting noble metal catalyst with rare-earth oxide and transition metal oxide and alkaline earth oxide type catalyst should be the inexorable trend of era development, and this is a correct selection that tallies with the national condition.The adding of rare earth element can improve the poison resistance of bond strength, heat endurance and the catalyst of catalyst carrier, especially improves the ability of the sulfur poisoning-resistant of catalyst.
Summary of the invention
The objective of the invention is on the alloying metal carrier of vehicle exhaust processor, to provide a kind of have anti-sulphur, resistance to high temperature oxidation, with metallic carrier the sulfureous resistant four-effect catalyst for purifying tail gas of vehicle of strong binding ability is arranged.Sulfureous resistant four-effect catalyst for purifying tail gas of vehicle of the present invention is prepared by following method:
1, metallic carrier preliminary treatment:
The alloying metal carrier is resistant to elevated temperatures commercially available nichrome material, what adopt that we develop is that the winding-structured engine tail gas processing device manufacture method of carrier is made integral type alveolate texture with 100～500 order hole density (see Chinese patent for details: 200610016967.4, be the winding-structured engine tail gas processing device of carrier with the metal) with the metal.Carrier is carried out surface treatment, is specially:
1) alveolate texture 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, 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: 1～6: 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) obviously find out from the SEM figure through the pretreated carrier of the method with above-mentioned alloying metal carrier as shown in Figure 2, obviously than being that treated (SEM of untreated carrier such as Fig. 1) specific area is big in the SEM of the carrier surface after 600～1000 ℃ of roasting temperatures are handled under the air conditions.
2, the preparation of glass coating sol-gel solution:
1) with distilled water be solvent, the preparation mass concentration is 5～40% nitrate trihydrate copper (Cu (NO
3)
23H
2O) solution, 5～50% six water nickel nitrate (Ni (NO
3)
26H
2O) solution, 5～50% six water manganese nitrate (Mn (NO
3)
26H
2O) solution and 5～50% cobalt nitrate hexahydrate Co (NO
3)
26H
2O solution mixes 2～4 kinds of above-mentioned nitrate solution equal-volumes then; Prepare mass concentration again and be 5～38% nine water aluminum nitrate (Al (NO
3)
39H
2O) solution, 5%～20% BAS mix the above-mentioned nitrate mixed solution of 10～30g, 10～15g aluminum nitrate solution, 10～20g BAS then, stir under 20～60 ℃ temperature 1～3 hour, dissolve 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;
3, the preparation of 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;
4, the coated technique of 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 prepare glass coating at cellular alloying metal carrier surface, final glass coating accounts for 4～10% of alloying metal vehicle weight, the SEM of glass coating demonstrates bigger specific area as shown in Figure 3;
3) will be the mode of cellular alloying metal carrier by immersion coating of coated glass coating immerse the zirconium that method 3 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 prepare the catalyst that contains zirconia, titanium oxide at cellular alloying metal carrier surface, catalyst S EM goes into shown in Figure 4, demonstrates bigger specific area;
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 carrier.
Technique effect of the present invention is: quadruple effect catalyst of the present invention has following advantage: 1) make PM and NOx catalysis on same catalytic bed; 2) SO
2Concentration be under the condition of 500～800ppm, catalytic efficiency is had no effect; 3) very high and be carrier with respect to other the sulfur resistance of this catalyst of catalyst with the metal.
And our selected novel metal carrier has the following advantages: 1) geometrical surface is big, thereby makes the clarifier volume reduce.Under the condition that obtains identical purifying property, can save the active component of using as catalyst (particularly noble metal component); 2) the pre-good He littler back pressure of hot property; 3) greatly to combine performance good with transition zone and catalyst for specific area; 4) mechanical strength is high.Therefore, metallic carrier and sulfureous resistant four-effect catalyst of the present invention have very big application value.
Use the sulfureous resistant four-effect catalyst of the present invention's preparation, its catalytic effect is:
1) works as SO
2Concentration when being 500～800ppm, the initiation temperature of catalyst is below 200 ℃ in the tail gas, conversion ratio to SOF (arene in the tail gas) is higher than 90%, based on Europe III Diesel engine, after this catalyst and particle trapper, Europe IV even the above standard of Europe V are satisfied in the PM discharging in the tail gas;
2) work as SO
2Concentration when being 500～800ppm, based on Europe III Diesel engine, after this catalyst and particle trapper, the conversion ratio of CO and HC satisfies Europe V standard;
3) work as SO
2Concentration when being 500～800ppm, based on Europe III Diesel engine, through after this catalyst, Europe IV standard is satisfied in the NOx discharging in the tail gas.
In a word, this sulfureous resistant four-effect catalyst can make the engine that satisfies Europe III discharging satisfy the above discharge standard of Europe IV in laboratory, platform experiment test and real world applications, can satisfy the instructions for use of gasoline car and diesel vehicle low emission.
Description of drawings:
Fig. 1: the metallic carrier SEM surface topography photo that does not carry out any processing;
Fig. 2: the SEM surface topography photo of the metallic carrier after the surface preparation;
Fig. 3: the SEM surface topography photo of coated glass coating on the metallic carrier;
Fig. 4: the SEM surface topography photo on the metallic carrier of coated glass coating after catalyst-loaded;
Specific embodiments
This patent is to set forth the present invention with specific embodiments; rather than limitation of the present invention; every a kind of can being used on the automobile engine tail gas purifying processor; the method that on metallic carrier, prepares the quadruple effect catalyst; every relating to the metal oxide is main component or associated nonmetal oxide; and add any type of slaine in the glass coating (as nitrate; chlorate etc.) be auxiliary agent; and the sulfureous resistant four-effect catalyst of Tu Fuing is our rights protection scope in this way.
Embodiment 1:
Get nine water aluminum nitrate (Al (NO
3)
39H
2O) 5 grams, six water nickel nitrate (Ni (NO
3)
26H
2O) 5 grams; Cobalt nitrate hexahydrate (Co (NO
3)
26H
2O) 5 grams adding distil water 10ml respectively, then with the aqueous solution of each nitrate, get boric acid 1 gram adding distil water 10 gram wiring solution-formings after, mix with nitrate mixed solution, under 25 ℃ temperature, stirred 0.5 hour, dissolve fully, take out mixed liquor 40 grams of nitrate and boric acid up to all salt.
Take by weighing 2ml concentration and be 80% ethanol, 1ml water, 0.1ml concentration is 65% red fuming nitric acid (RFNA), after three kinds of solution mixing and stirring, take by weighing the positive tetraethyl orthosilicate of 15ml again, slowly, intermittently, powerful simultaneously pouring in above-mentioned three kinds of mixed liquors of stirring, the transparent mixed solution of final formation, the pH value of regulating this solution with hydrochloric acid is 4, get then that the pH value regulates mixed liquor 15 grams, and with in the getting solution mixed liquor that is injected into 40 gram nitrate and boric acid slowly, powerful simultaneously the stirring, the final mixed liquor that forms is the sol-gel solution of glass coating.
The alloying metal that 1 metallic carrier preprocess method is set by step handled is done carrier into strips, put into above-mentioned glass coating solution, cellular alloying metal carrier immersed in the glass coating solution repeatedly 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 4 times, do not dry up after last the coating, directly utilize absorbent cotton that metallic carrier was dried in the shade under room temperature 8 hours in air, then in air, under 60 ℃ of temperature, dry to constant weight, take out with stove cooling back, with the roasting 2 minutes in Muffle furnace under 500 ℃ the temperature in air of the alloying metal carrier that has glass coating of oven dry, thereby prepare glass coating at the alloying metal carrier surface, final glass coating accounts for 5% of alloying metal vehicle weight.
The nitrate of getting zirconium and titanium is respectively 2.5 grams and 5 grams, and the distilled water that adds 10ml more respectively is mixed with the solution of certain mass concentration, then two solution is mixed, and stirs 10 minutes under 50 ℃ temperature, dissolves fully up to all salt.The nitrate compound of getting platinum, palladium is respectively 0.1 gram, mixes preparation precious metal catalyst agent solution after adding the 10ml distilled water diluting respectively.
The alloying metal carrier of the coated glass coating mode by immersion coating is immersed the zirconium that prepared and the mixed liquor of titanium salt, the 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 4 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 hours in air, then in air, under 60 ℃ of temperature, dry, take out with stove cooling back to constant weight.With the roasting 4 hours in Muffle furnace under 500 ℃ the temperature in air of the alloying metal carrier that has zirconium, titanium salt catalyst of oven dry, thereby prepare the catalyst that contains zirconia, titanium oxide at the alloying metal carrier surface.
Method by immersion coating is having zirconia, preparation noble metal catalyst layer on the glass coating of titanium oxide, to have zirconia, titanium oxide, the alloying metal carrier of glass coating immerses the platinum that has prepared repeatedly, apply in the mixed liquor solution of palladium, 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, to metallic carrier weightening finish 5%, last coating back is in 60 ℃ of temperature oven dry, activated typing in 4 hours in 500 ℃ 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 carrier.
Just can see on the alloy carrier by ESEM such as Fig. 3,4 like this having applied one deck glass coating of the present invention and catalyst (thickness is 2 microns) that recording the coating and the catalyst composition (mass content) that apply by XPS on the alloy carrier more at last is titanium dioxide three aluminium (Al
2O
3) 8%, nickel oxide (NiO) 10%, cobalt oxide (CoO) 15%, diboron trioxide (B
2O
3) 5%, silica (SiO
2) 49%, zirconia (ZrO
2) 4%, titanium oxide (TiO) 8%, platinum (Pt) 0.5%, palladium (Pd) 0.5%.
Embodiment 2:
Get nine water aluminum nitrate (Al (NO
3)
39H
2O) 5 grams, manganese nitrate (Mn (NO
3) 5 grams, nitrate trihydrate copper (Cu (NO
3)
23H
2O) 5 grams, adding distil water 10ml respectively is then with the aqueous solution of each nitrate, after getting boric acid 1 gram adding distil water 10ml wiring solution-forming, mix, under 30 ℃ temperature, stirred 0.5 hour with nitrate mixed solution, dissolve fully up to all salt, take out mixed liquor 35 grams of nitrate and boric acid.
Take by weighing 3ml concentration and be 80% ethanol, 2ml water, 0.1ml concentration and be 65% red fuming nitric acid (RFNA), after three kinds of solution mixing and stirring, take by weighing the positive tetraethyl orthosilicate of 20ml again, slowly, intermittently, powerful simultaneously pouring in above-mentioned three kinds of mixed liquors of stirring, the transparent mixed solution of final formation, the pH value of regulating this solution is 4, get then that pH value regulates mixed liquor 20 grams, and with in the getting solution mixed liquor that is injected into 35 gram nitrate and boric acid slowly, powerful simultaneously the stirring, the final mixed liquor that forms is the sol-gel solution of glass coating.
The alloying metal that 1 metallic carrier preprocess method is set by step handled is done carrier into strips, put into above-mentioned glass coating solution, cellular alloying metal carrier immersed in the glass coating solution repeatedly 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 5 times, do not dry up after last the coating, directly utilize absorbent cotton that metallic carrier was dried in the shade under room temperature 8 hours in air, then in air, under 60 ℃ of temperature, dry to constant weight, take out with stove cooling back, with the roasting 2 minutes in Muffle furnace under 600 ℃ the temperature in air of the alloying metal carrier that has glass coating of oven dry, thereby prepare glass coating at the alloying metal carrier surface, final glass coating accounts for 5% of alloying metal vehicle weight.
Get the nitrate of zirconium and titanium or other forms of zirconium, titanium salt is respectively 1.5 grams and 7.5 grams, the distilled water that adds 10ml more respectively is mixed with the solution of certain mass concentration, then two solution are mixed, under 50 ℃ temperature, stirred 10 minutes, dissolve fully up to all salt.Get platinum, palladium precious metal salt compound and be respectively 0.1 gram, mix preparation precious metal catalyst agent solution after adding the 10ml distilled water diluting respectively.
The alloying metal carrier of the coated glass coating mode by immersion coating is immersed the zirconium that prepared and the mixed liquor of titanium salt, the 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 5 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 hours in air, then in air, under 60 ℃ of temperature, dry, take out with stove cooling back to constant weight.With the roasting 4 hours in Muffle furnace under 600 ℃ the temperature in air of the alloying metal carrier that has zirconium, titanium salt catalyst of oven dry, thereby prepare the catalyst that contains zirconia, titanium oxide at the alloying metal carrier surface.
Method by immersion coating is having zirconia, preparation noble metal catalyst layer on the glass coating of titanium oxide, to have zirconia, titanium oxide, the alloying metal carrier of glass coating immerses the platinum that has prepared repeatedly, apply in the mixed liquor solution of palladium, 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, to metallic carrier weightening finish 6%, last coating back is in 60 ℃ of temperature oven dry, activated typing in 4 hours in 600 ℃ 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 carrier.
Just can see on the alloy carrier by ESEM such as Fig. 3,4 like this having applied one deck glass coating of the present invention and catalyst (thickness is 1 micron) that recording the coating and the catalyst composition (mass content) that apply by XPS on the alloy carrier more at last is titanium dioxide three aluminium (Al
2O
3) 8%, manganese oxide (MnO) 12%, cupric oxide (CuO) 16%, diboron trioxide (B
2O
3) 6%, silica (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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| CN103977842A (en) * | 2014-06-04 | 2014-08-13 | 中国科学院重庆绿色智能技术研究院 | Method for coating motor vehicle exhaust cleaning catalyst |
| CN109201082A (en) * | 2018-09-15 | 2019-01-15 | 四川绵阳华元航升环保科技有限公司 | A kind of preparation process for the gasoline car catalyst converter meeting six standard of Europe |
| CN112642428A (en) * | 2019-10-12 | 2021-04-13 | 中国石油化工股份有限公司 | Catalyst, preparation method and application thereof, and exhaust gas treatment method |
-
2008
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Cited By (9)
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| CN102513131A (en) * | 2011-12-09 | 2012-06-27 | 十堰市登喜路实业有限公司 | Catalyst for purification of tail gas produced by military diesel offroad vehicle and coating method thereof |
| CN102513131B (en) * | 2011-12-09 | 2013-09-11 | 十堰市登喜路实业有限公司 | Catalyst for purification of tail gas produced by military diesel offroad vehicle and coating method thereof |
| CN102658184A (en) * | 2012-05-05 | 2012-09-12 | 吉林大学 | Selective urea decomposition catalyst taking honeycomb metal alloy as carrier and preparation method for catalyst |
| CN103977842A (en) * | 2014-06-04 | 2014-08-13 | 中国科学院重庆绿色智能技术研究院 | Method for coating motor vehicle exhaust cleaning catalyst |
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| CN109201082A (en) * | 2018-09-15 | 2019-01-15 | 四川绵阳华元航升环保科技有限公司 | A kind of preparation process for the gasoline car catalyst converter meeting six standard of Europe |
| CN109201082B (en) * | 2018-09-15 | 2021-04-13 | 四川绵阳华元航升环保科技有限公司 | Preparation process of gasoline car catalyst meeting Europe-six standard |
| CN112642428A (en) * | 2019-10-12 | 2021-04-13 | 中国石油化工股份有限公司 | Catalyst, preparation method and application thereof, and exhaust gas treatment method |
| CN112642428B (en) * | 2019-10-12 | 2023-05-02 | 中国石油化工股份有限公司 | Catalyst, preparation method and application thereof, and exhaust gas treatment method |
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| CN101269335B (en) | 2011-08-17 |
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