WO2010028531A1 - A prepositive oxidation catalyst for diesel vehicles and its preparation method - Google Patents

A prepositive oxidation catalyst for diesel vehicles and its preparation method Download PDF

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WO2010028531A1
WO2010028531A1 PCT/CN2008/073915 CN2008073915W WO2010028531A1 WO 2010028531 A1 WO2010028531 A1 WO 2010028531A1 CN 2008073915 W CN2008073915 W CN 2008073915W WO 2010028531 A1 WO2010028531 A1 WO 2010028531A1
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content
carrier
zirconium
catalyst
mixed
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PCT/CN2008/073915
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Chinese (zh)
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翁端
司知蠢
吴晓东
冉锐
周舟
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清华大学
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Priority to AU2008361642A priority Critical patent/AU2008361642B2/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0225—Coating of metal substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0242—Coating followed by impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1021—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20707—Titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20715—Zirconium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/01—Engine exhaust gases
    • B01D2258/012—Diesel engines and lean burn gasoline engines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/464—Rhodium

Definitions

  • the present invention relates to the field of diesel vehicle exhaust gas purification technology, and more particularly to a diesel vehicle front-end that can oxidize CO and HC in diesel vehicle exhaust gas to C0 2 and 0. Oxidation catalyst and preparation method thereof.
  • Diesel vehicle exhaust pollutants mainly include carbon monoxide (C0), hydrocarbons (HC), nitrogen oxides (NCU and particulate matter (also known as PM, composed of dry soot, liquid hydrocarbons and a small amount of sulfate), etc.
  • C0 carbon monoxide
  • HC hydrocarbons
  • NCU nitrogen oxides
  • PM particulate matter
  • the exhaust gas generated by the diesel vehicle diesel burner 3 is discharged by the exhaust gas exhaust pipe 4, and the exhaust gas treatment is divided into two types: the pre-oxidation catalyst 1 and the oxidation catalyst for DPF regeneration in the particulate matter collector 2.
  • the oxidation catalyst is combined.
  • the pre-oxidation catalyst mainly uses the temperature of the diesel exhaust gas to convert the gaseous pollutants CO and HC in the exhaust gas into C0 2 and H 2 0; the oxidation catalyst for DPF regeneration is mainly combined with the DPF in the fuel injection combustion. Oxidation of trapped particulate matter at a temperature to regenerate the DPF.
  • the tail gas temperature of the diesel vehicle is low (200 to 400 ° C), and the content of 0 2 is high (> 6%), and It contains a certain amount of S0 2 , so it is required that the oxidation catalyst for diesel vehicles has high low temperature activity and certain sulfur poisoning resistance.
  • the oxidation catalyst for diesel vehicles generally consists of the active component, the coating and the carrier (cordierite honeycomb ceramic or metal carrier).
  • Oxidation catalysts with noble metals such as platinum (Pt), rhodium (Rh) and palladium (Pd) as active components have high low temperature activity and are very suitable for the catalytic conversion of CO and HC in low temperature tail gas of light diesel vehicles.
  • Pt platinum
  • Rh rhodium
  • Pd palladium
  • Properly increasing the loading of precious metals in the oxidation catalyst can increase the conversion activity of the catalyst to CO and HC, but the increase in the precious metal content also accelerates the formation of sulfate and poisons the catalyst.
  • the catalyst is designed to reduce the loading of precious metals, add auxiliaries, modified supports and coatings to improve the sulfur toxicity of the catalyst.
  • the supported noble metal catalyst is generally prepared by a dipping method by immersing the coated carrier in a solution containing noble metal ions, purging, drying and calcining, thereby realizing the loading of the precious metal.
  • the porous structure of the carrier such as cordierite honeycomb ceramics which is widely used at present is relatively smooth, and the adhesion between the coating and the carrier surface is poor, and the coating and the catalyst are easily detached from the carrier, resulting in failure of the catalyst converter.
  • the technical solution adopted by the present invention is: a pre-oxidation catalyst for a diesel vehicle, using a honeycomb ceramic and a metal as a carrier, and preparing a zirconium salt solution, a mixed Ti0 2 powder and 0 or a mixed Ti0 2 powder and 0. Slurry, on the surface of the carrier A coating material is prepared; an oxidation catalyst for a diesel vehicle prepared by drying and calcining one or more of precious metals Pt, Rh and Pd by an equal volume method.
  • a mixed solution of zirconium salt and 0, so that the mixed solution of zirconium in terms of Zr0 2 to 0. 5 ⁇ 30wt%, Ti0 2 and then adding a mixed powder or mixed powder and Ti0 2 0 mixture, stirred l ⁇ Prepared into a slurry at 10 h.
  • the slurry solids content 5 ⁇ 50 wt%, wherein the zirconium content of 0 ⁇ 30 wt% Zr0 2 basis weight of the total solids, Ti0 2 solids total weight 50 ⁇ 100 wt% of.
  • step 2 Soak the 200 ⁇ 500 mesh honeycomb ceramic carrier in the slurry obtained in step 1 for 2 ⁇ 30 s, and use the high pressure gas to blow out the excess slurry in the channel to ensure uniformity of the surface of the honeycomb surface and the passage of the pores.
  • the carrier is dried at 100 to 200 ° C for 1 to 10 h, and the previous steps are repeated to adjust the coating weight to 30 to 150 g/L, and then calcined at 300 to 600 ° C for 1 to 5 hours to obtain a coated carrier.
  • the water absorption rate of the carrier obtained in the measurement step 2 is 2 to 30% to calculate the concentration of the impregnation solution, and the soluble salt solution of the noble metal Pt, Pd or Rh is used as a raw material, and one or several precious metals are supported by an equal amount of impregnation method.
  • the noble metal content is 0.1 to 3% of the mass of the coating material, and the carrier after impregnating the precious metal salt solution is dried at 100 to 200 ° C for 1 to 10 h, and calcined at 300 to 600 ° C for 1 to 5 hours to obtain oxidation. catalyst.
  • the honeycomb ceramic carrier is made of cordierite, mullite, silicon carbide or FeCrAl-based high temperature metal.
  • the mixed Ti0 2 powder is a mixture of Ti0 2 , W0 3 , Si0 2 and A1 2 0 3 , wherein the Ti0 2 content is 40 to 100 wt%,
  • the W0 3 content is 0 to 15 wt%
  • the Si0 2 content is 0 to 15 wt%
  • the A1 2 0 3 content is 0 to 15 wt%.
  • the solution of zirconium salt is zirconium acetate, zirconium, citric acid or a mixed solution of zirconium nitrate and water, wherein the zirconium content -5 to 0.5 in terms of Zr0 2
  • the soluble salt of the noble metal is chloroplatinic acid PtCl 6 , dinitrotetraammine platinum (NH 3 ) 4 Pt (N0 3 ) 2 , palladium chloride PdCl 2 , palladium nitrate Pd (N0 3 ) 2 , lanthanum nitrate Rh ( N0 3 ) or rhodium chloride RhCl 3 .
  • the invention has the beneficial effects of providing a high-performance formula and preparation method of a pre-oxidation catalyst for tail gas treatment of diesel vehicles; the catalyst can oxidize gaseous pollutants CO and HC in the exhaust gas to C0 at the exhaust gas temperature of the diesel vehicle.
  • FIG. 1 is a schematic diagram of a diesel vehicle exhaust gas discharge structure.
  • the exhaust gas generated by the diesel vehicle diesel burner 3 is discharged by the exhaust gas exhaust pipe 4, and the exhaust gas treatment is divided into two oxidations of the pre-oxidation catalyst 1 and the oxidation catalyst for DPF regeneration in the particulate matter trap 2.
  • the catalyst is combined.
  • the pre-oxidation catalyst prepared by the invention is an active catalyst for removing carbon monoxide hydrocarbons prepared by in-situ preparation of a zirconium salt and a mixed Ti0 2 powder on a honeycomb ceramic carrier; mainly utilizing the temperature of the diesel exhaust gas itself, the exhaust gas
  • the gaseous pollutants CO and HC are converted to C0 2 and 0; the invention is further illustrated by the following examples.
  • the water absorption of the obtained carrier was measured to be 108 g/L, and the Pt (N0 3 ) 2 solution was used as a raw material, and Pt was loaded by an equal amount of impregnation method, and the Pt content was 1% of the mass of the coating material, and the Pt (N0 3 ) 2 solution was impregnated.
  • the carrier was dried at 150 ° C for 1 h, and calcined at 450 ° C for 1 h to obtain an oxidation catalyst, and the oxidation catalyst was labeled as TiZr0-f.
  • Zirconium acetate solution zirconium content is 20 wt% in terms of Zr0 2
  • the carrier is dried at 150 ° C for 1 h and calcined at 450 ° C for 1 h to obtain a coating weight of 100 g / L.
  • Catalyst carrier The water absorption of the obtained carrier was measured to be 114 g/L.
  • the Pt (N0 3 ) 2 solution was used as the raw material, and Pt was loaded by the equivalent impregnation method. The Pt content was 1% of the mass of the coating material, and the Pt (N0 3 ) 2 solution was impregnated.
  • the carrier was dried at 150 ° C for 1 h, and calcined at 450 ° C for 1 h to obtain an oxidation catalyst, and the oxidation catalyst was labeled as TiZr5-f.
  • the preparation conditions and the preparation procedure were the same as in Example 2, and the zirconium content was adjusted to be 15 wt% of the total solid content of the slurry in terms of Zr0 2 ; an oxidation catalyst was prepared, and the oxidation catalyst was labeled as TiZrl5-f.
  • Zirconium acetate solution zirconium content is 20 wt% in terms of Zr0 2
  • the carrier is dried at 150 ° C for 1 h and calcined at 450 ° C for 1 h to obtain a coating weight of 100 g / L.
  • Catalyst carrier The water absorption of the obtained carrier was measured to be 114 g/L, and the Pd (N0 3 ) 3 solution and the Pt (N0 3 ) 3 solution were used as raw materials, and Pd and Pt were supported by an equal amount of impregnation (the molar ratio of Pd to Pt was 1: 1), the total content of Pd and Pt mixed metal is 1% of the mass of the coating material, and the carrier impregnated with Pd(N0 3 ) 2 solution and Pt (N0 3 ) 3 solution is dried at 150 ° C for 1 h at 450 ° C. An oxidation catalyst was obtained after calcination for 1 h.
  • the resulting water absorption of the support was measured as 97g / L, chloroplatinic acid? 16 ⁇ solution as raw materials, the same amount dipping load Pt, Pt content of 1% by weight of the coating material, impregnating chloroplatinic acid? 16 solution
  • the carrier was dried at 150 ° C for 1 h, and calcined at 450 ° C for 1 h to obtain an oxidation catalyst.
  • the zirconium nitrate, 0 and the mixed Ti0 2 powder (the Ti0 2 content in the mixed Ti0 2 powder is 90 wt%, the Si0 2 content is 10 wt%).
  • Proportion (zirconium nitrate: 0: Ti0 2 3.5 wt%: 60 wt% : 38wt%) mixing, stirring for 10 h to obtain a slurry for coating (solid content: 40% by weight); soaking a 200 mesh cordierite honeycomb ceramic carrier in the slurry for 10 s, and blowing excess slurry in the channel with high pressure gas In order to ensure uniformity of the surface of the honeycomb surface and the passage of the pores; then the carrier was dried at 150 ° C for 1 h, and calcined at 450 ° C for 1 h to obtain a catalyst support having a coating weight of 97 g / L.
  • the water absorption of the obtained carrier was measured to be 105 g/L, and the Pt (N0 3 ) 2 solution was used as the raw material.
  • the Pt was loaded by the equivalent amount of impregnation method, and the Pt content was 1% of the mass of the coating material, and the Pt (N0 3 ) 2 solution was impregnated.
  • the carrier was dried at 150 ° C for 1 h, and calcined at 450 ° C for 1 h to obtain an oxidation catalyst.
  • the zirconium nitrate, 0 and the mixed Ti0 2 powder (the Ti0 2 content in the mixed Ti0 2 powder is 90 wt%, the Si0 2 content is 10 wt%).
  • Proportion (zirconium nitrate: 0: Ti0 2 3.5 wt%: 60 wt% : 38wt%) mixing, stirring for 10 h to obtain a slurry for coating (solid content: 40% by weight); soaking a 200 mesh cordierite honeycomb ceramic carrier in the slurry for 10 s, and blowing excess slurry in the channel with high pressure gas To ensure uniformity of the surface of the honeycomb surface and the passage of the pores; then the carrier is dried at 150 ° C for 1 h at 450 ° C Calcination for 1 h gave a catalyst support having a coating weight of 97 g/L.
  • the water absorption of the obtained carrier was measured to be 116 g/L, Rh (N0 3 ) 3 solution was used as the raw material, Rh was loaded by the equivalent impregnation method, Rh content was 1% of the mass of the coating material, and the Rh (N0 3 ) 3 solution was impregnated.
  • the carrier was dried at 150 ° C for 1 h, and calcined at 450 ° C for 1 h to obtain an oxidation catalyst.
  • Zirconium nitrate, 0 and mixed Ti0 2 powder (ti 0 2 content in mixed Ti0 2 powder is 89 wt%, Si0 2 content is 10 wt%, A1 2 0 3 content is lwt%).
  • Proportion (zirconium nitrate: 3 ⁇ 40: Ti0) 2 3. 5wt%: 60wt%: 38wt%)
  • Mixing, stirring for 10h to obtain a slurry for coating (solid content is 40wt%); soaking 200 mesh cordierite honeycomb ceramic carrier in slurry for 10 s, The excess slurry in the tunnel is blown out with high pressure gas to ensure uniformity of the surface of the honeycomb and the passage of the pores.
  • the carrier is then dried at 150 ° C for 1 h and calcined at 450 ° C for 1 h to obtain a catalyst with a coating weight of 97 g / L.
  • Carrier The water absorption of the obtained carrier was measured to be 107 g/L, and the Pd (N0 3 ) 3 solution was used as a raw material. The Pd was loaded by an equal amount of impregnation method, and the Pd content was 1% of the mass of the coating material, and the Pd (N0 3 ) 2 solution was impregnated.
  • the carrier was dried at 150 ° C for 1 h, and calcined at 450 ° C for 1 h to obtain an oxidation catalyst.
  • Zirconium nitrate, 0 and mixed Ti0 2 powder (ti 0 2 content in mixed Ti0 2 powder is 89 wt%, Si0 2 content is 10 wt%, A1 2 0 3 content is lwt%).
  • Proportion (zirconium nitrate: 3 ⁇ 40: Ti0) 2 3. 5wt%: 60wt%: 38wt%)
  • Mixing, stirring for 10h to obtain a slurry for coating (solid content is 40wt%); soaking 200 mesh cordierite honeycomb ceramic carrier in slurry for 10 s, The excess slurry in the tunnel is blown out with high pressure gas to ensure uniformity of the surface of the honeycomb and the passage of the pores.
  • the carrier is then dried at 150 ° C for 1 h and calcined at 450 ° C for 1 h to obtain a catalyst with a coating weight of 97 g / L.
  • Carrier The water absorption of the obtained carrier was measured to be 107 g/L, and the Pd (N0 3 ) 3 solution and the Pt (N0 3 ) 3 solution were used as raw materials, and Pd and Pt were supported by an equal amount of impregnation (the molar ratio of Pd to Pt was l: l), the total content of Pd and Pt mixed metal is 1% of the mass of the coating material, and the carrier impregnated with Pd (N0 3 ) 2 solution and Pt (N0 3 ) 3 solution is dried at 150 ° C for 1 h at 450 ° C. An oxidation catalyst was obtained after calcination for 1 h.
  • the TiZrO-f catalyst obtained in Example 1, the TiZr5-f catalyst obtained in Example 2, the TiZrlO-f catalyst obtained in Example 3, and the TiZrl5-f catalyst obtained in Example 4 were cut into a size of 9 mm X.
  • a sample of 9mm X 48mm (length 48mm along the tunnel direction) is placed in a tube furnace, and 10% of the water containing steam is kept at 600 °C for 100 h. After the furnace is cooled, the hydrothermal aging sample of the catalyst is obtained. They are labeled TiZrO-a, TiZr5-a, TiZrlO-a and TiZrl5_a, respectively.
  • Example 12
  • the TiZrO-f catalyst obtained in Example 1, the TiZr5-f catalyst obtained in Example 2, the TiZrlO-f catalyst obtained in Example 3, and the TiZrl5-f catalyst obtained in Example 4 were cut into a size of 9 mm X.
  • a sample of 9mm X 48mm (length 48 in the direction of the tunnel) was placed in a tube furnace, and it was incubated at 450 ° C for 100 h with air containing S0 2 30 ppm. After the furnace was cooled, the sulfur aging sample of the catalyst was obtained. They are labeled TiZr0-s, TiZr5-s, TiZrl0_s, and TiZrl5_s, respectively.
  • Test example 1 Test example 1.
  • TiZrO-f catalyst (Example 1), TiZr5-f catalyst (Example 2), TiZrlO-f catalyst (Example 3), TiZrl5-f catalyst (Example 4), TiZrO_a catalyst (Example 11), TiZr5_a catalyst (Example 11), TiZrlO-a catalyst (Example 11), TiZrl5_a catalyst (Example 11), TiZrO_s catalyst (Example 12), TiZr5-s catalyst (Example 12), TiZrlO_s catalyst (Example 12)
  • the catalyst light-off characteristics test was carried out in an atmosphere simulating diesel exhaust gas.
  • the specific test procedure is as follows: The catalyst is cut into a test sample of size 9mmX 9mmX 48mm (length 48 in the direction of the tunnel), and the test sample is wrapped with quartz wool in the direction of the parallel hole, and placed in a stainless steel reaction tube. Simulated gas distribution into diesel exhaust, the simulated gas composition contains CO (100 ppm), C0 2 (13%), C 3 H 8 (500 ppm), NO (700 ppm), 0 2 (7%), N 2 Equilibrium, airspeed 60000h— ⁇ The reactor temperature was raised from room temperature to 450 °C at a rate of 10 °C/min. The AVL five-component analyzer was used to detect the simulated gas distribution through the catalyst after C0 and C 3 H 8 concentration.
  • the catalyst performance evaluation test results show that the developed catalyst has excellent low temperature removal effect on C0 and HC, and the catalyst has high hydrothermal stability and sulfur poisoning resistance. See Table 1 for specific examples.
  • Example 1 The catalytic oxidation effects of the catalysts on C0 and C 3 H 8 in Example 1, Example 2, Example 3, Example 4, Example 6, Example 11 and Example 12 are shown in Table 1.
  • Table 1 Catalytic oxidation effect of catalyst on C0 and C 3 H 8

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Abstract

A Prepositive oxidation catalyst for diesel vehicles and its preparation method. A slurry obtained by mixing zirconium salt solution, the powder containing titanium dioxide with water, or mixing the powder containing titanium dioxide with water, is coated on the surface of honeycomb carriers, and then dried and calcined. The carriers obtained are impregnated in the salt solution containing one or more of active components selected from Pt, Rh and Pd, then dried and calcined in order to obtain the catalyst. In the catalyst, to the coating weight, the titanium dioxide content is 50~100wt%, the zirconia content is 0~30wt%, the active components content is 0.1~3wt%.

Description

一种柴油车用前置氧化催化剂及其制备方法 技术领域 本发明属于柴油车尾气净化技术领域，特别涉及一种可将柴油车尾气中的 CO和 HC氧化为 C02和 0的柴油车前置氧化催化剂及其制备方法。 背景技术 柴油车尾气排放污染物主要包括说一氧化碳 （C0)、 碳氢化合物 （HC)、 氮氧化物 （NCU 和 颗粒物 （又称 PM， 由干碳烟、 液态烃类和少量硫酸盐组成） 等。 在图 1 中， 柴油车柴油燃烧 器 3产生的尾气由尾气排气管 4排出， 尾气处理用分为前置氧化催化剂 1和与颗粒物捕收器 2 中的 DPF再生用氧化催化剂的两种氧化催化剂相结合进行。前置氧化催化剂主要利用柴油车尾 气本身温度将尾气中的气态污染物 CO和 HC转化成 C02和书 H20; DPF再生用氧化催化剂主要与 DPF 结合在喷油燃烧温度下氧化捕集到的颗粒物， 从而使 DPF实现再生。 由于柴油机的稀燃特性， 柴油车排放的尾气温度较低 （200〜400°C )， 02含量较高 （>6%)， 并且含有一定量的 S02， 因 此要求柴油车用氧化催化剂具有高的低温活性和一定的抗硫中毒性能。 BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the field of diesel vehicle exhaust gas purification technology, and more particularly to a diesel vehicle front-end that can oxidize CO and HC in diesel vehicle exhaust gas to C0 2 and 0. Oxidation catalyst and preparation method thereof. BACKGROUND OF THE INVENTION Diesel vehicle exhaust pollutants mainly include carbon monoxide (C0), hydrocarbons (HC), nitrogen oxides (NCU and particulate matter (also known as PM, composed of dry soot, liquid hydrocarbons and a small amount of sulfate), etc. In Fig. 1, the exhaust gas generated by the diesel vehicle diesel burner 3 is discharged by the exhaust gas exhaust pipe 4, and the exhaust gas treatment is divided into two types: the pre-oxidation catalyst 1 and the oxidation catalyst for DPF regeneration in the particulate matter collector 2. The oxidation catalyst is combined. The pre-oxidation catalyst mainly uses the temperature of the diesel exhaust gas to convert the gaseous pollutants CO and HC in the exhaust gas into C0 2 and H 2 0; the oxidation catalyst for DPF regeneration is mainly combined with the DPF in the fuel injection combustion. Oxidation of trapped particulate matter at a temperature to regenerate the DPF. Due to the lean-burning characteristics of the diesel engine, the tail gas temperature of the diesel vehicle is low (200 to 400 ° C), and the content of 0 2 is high (> 6%), and It contains a certain amount of S0 2 , so it is required that the oxidation catalyst for diesel vehicles has high low temperature activity and certain sulfur poisoning resistance.
柴油车用氧化催化剂一般由活性组分、 涂层和载体 （堇青石蜂窝陶瓷或金属载体） 组成。 以铂 （Pt)、 铑 （Rh ) 和钯 （Pd) 等贵金属作为活性组分的氧化催化剂， 具有低温活性高的特 点， 非常适用于轻型柴油车低温尾气中 CO和 HC的氧化催化转化。适当提高氧化催化剂中贵金 属的负载量， 可以提高催化剂对 CO和 HC的转化活性， 但贵金属含量的提高也会加速硫酸盐的 生成而使催化剂中毒。为降低催化剂表面硫酸盐的生成量， 目前在催化剂设计中多采用降低贵 金属的负载量、 加入助剂、 改性载体和涂层的办法提高催化剂的抗硫中毒性能。  The oxidation catalyst for diesel vehicles generally consists of the active component, the coating and the carrier (cordierite honeycomb ceramic or metal carrier). Oxidation catalysts with noble metals such as platinum (Pt), rhodium (Rh) and palladium (Pd) as active components have high low temperature activity and are very suitable for the catalytic conversion of CO and HC in low temperature tail gas of light diesel vehicles. Properly increasing the loading of precious metals in the oxidation catalyst can increase the conversion activity of the catalyst to CO and HC, but the increase in the precious metal content also accelerates the formation of sulfate and poisons the catalyst. In order to reduce the amount of sulfate on the surface of the catalyst, the catalyst is designed to reduce the loading of precious metals, add auxiliaries, modified supports and coatings to improve the sulfur toxicity of the catalyst.
负载型贵金属催化剂一般采用浸渍法制备，其步骤是将带有涂层的载体浸渍在含有贵金属 离子的溶液中， 吹扫后进行烘干和焙烧， 从而实现贵金属的担载。 目前广泛采用的堇青石蜂窝 陶瓷等载体的孔结构表面比较光滑， 涂层与载体表面结合力较差， 涂层和催化剂易从载体上脱 落， 导致催化剂转化器失效。 发明内容 本发明目的在于提供一种低温活性高， 抗硫中毒性能好，催化涂层与载体的结合牢固的柴 油车前置氧化催化剂及其制备方法。  The supported noble metal catalyst is generally prepared by a dipping method by immersing the coated carrier in a solution containing noble metal ions, purging, drying and calcining, thereby realizing the loading of the precious metal. The porous structure of the carrier such as cordierite honeycomb ceramics which is widely used at present is relatively smooth, and the adhesion between the coating and the carrier surface is poor, and the coating and the catalyst are easily detached from the carrier, resulting in failure of the catalyst converter. SUMMARY OF THE INVENTION The object of the present invention is to provide a diesel fuel vehicle pre-oxidation catalyst having high low-temperature activity, good sulfur-tolerant poisoning performance, and strong binding of a catalytic coating and a carrier, and a preparation method thereof.
为了实现上述目的本发明采取的技术方案是： 一种柴油车前置氧化催化剂， 以蜂窝陶瓷和 金属为载体， 以锆盐溶液、 混合 Ti02粉料与 0或混合 Ti02粉料与 0配制料浆， 在载体表面 制备涂层材料； 采用等体积法负载贵金属 Pt、 Rh和 Pd中的一种或几种， 经过烘干和焙烧制备 的柴油车用氧化催化剂。 In order to achieve the above object, the technical solution adopted by the present invention is: a pre-oxidation catalyst for a diesel vehicle, using a honeycomb ceramic and a metal as a carrier, and preparing a zirconium salt solution, a mixed Ti0 2 powder and 0 or a mixed Ti0 2 powder and 0. Slurry, on the surface of the carrier A coating material is prepared; an oxidation catalyst for a diesel vehicle prepared by drying and calcining one or more of precious metals Pt, Rh and Pd by an equal volume method.
本发明的另一个技术方案是提供了一种柴油车前置氧化催化剂的制备方法：  Another technical solution of the present invention provides a method for preparing a diesel vehicle pre-oxidation catalyst:
具体制备步骤如下：  The specific preparation steps are as follows:
( 1 ) 将锆盐溶液和 0混合， 使混合溶液中锆含量以 Zr02计为 0. 5〜30wt%， 然后加入混 合 Ti02粉体， 或混合 Ti02粉体与 0混合， 搅拌 l〜10 h制备成料浆。 通过调节加水量， 使料 浆固含量为 5〜50 wt%, 其中锆含量以 Zr02计占总固体重量的 0〜30 wt%, Ti02占总固体重量 的 50〜 100 wt%。 (1) A mixed solution of zirconium salt and 0, so that the mixed solution of zirconium in terms of Zr0 2 to 0. 5~30wt%, Ti0 2 and then adding a mixed powder or mixed powder and Ti0 2 0 mixture, stirred l~ Prepared into a slurry at 10 h. By adjusting the amount of water, the slurry solids content of 5~50 wt%, wherein the zirconium content of 0~30 wt% Zr0 2 basis weight of the total solids, Ti0 2 solids total weight 50~ 100 wt% of.
( 2) 将 200〜500目蜂窝陶瓷载体浸泡在步骤 1所得的料浆中 2〜30 s， 用高压气体吹出 孔道中多余料浆， 以保证蜂窝表面凝胶上载均匀和孔道贯通， 之后将所得载体在 100〜200°C 烘干 1〜10 h， 重复前面步骤调节涂层重量为 30〜150 g/L， 然后于 300〜600°C焙烧 1〜5 h 得到载有涂层的载体。  (2) Soak the 200~500 mesh honeycomb ceramic carrier in the slurry obtained in step 1 for 2~30 s, and use the high pressure gas to blow out the excess slurry in the channel to ensure uniformity of the surface of the honeycomb surface and the passage of the pores. The carrier is dried at 100 to 200 ° C for 1 to 10 h, and the previous steps are repeated to adjust the coating weight to 30 to 150 g/L, and then calcined at 300 to 600 ° C for 1 to 5 hours to obtain a coated carrier.
( 3) 测量步骤 2所得载体的吸水率为 2〜30^%以计算浸渍溶液浓度， 以贵金属 Pt、 Pd 或 Rh的可溶性盐溶液为原料， 以等量浸渍法负载一种或几种贵金属， 使贵金属含量为涂层材 料质量的 0. 1〜3%， 浸渍贵金属盐溶液后的载体经过 100〜200°C烘干 1〜10 h， 300〜600°C焙 烧 1〜5 h后即得到氧化催化剂。  (3) The water absorption rate of the carrier obtained in the measurement step 2 is 2 to 30% to calculate the concentration of the impregnation solution, and the soluble salt solution of the noble metal Pt, Pd or Rh is used as a raw material, and one or several precious metals are supported by an equal amount of impregnation method. The noble metal content is 0.1 to 3% of the mass of the coating material, and the carrier after impregnating the precious metal salt solution is dried at 100 to 200 ° C for 1 to 10 h, and calcined at 300 to 600 ° C for 1 to 5 hours to obtain oxidation. catalyst.
所述蜂窝陶瓷载体的材质为堇青石、 莫来石、 碳化硅或 FeCrAl基高温金属。  The honeycomb ceramic carrier is made of cordierite, mullite, silicon carbide or FeCrAl-based high temperature metal.
所述混合 Ti02粉体为 Ti02、 W03、 Si02和 A1203的混合物， 其中 Ti02含量为 40〜100 wt%,The mixed Ti0 2 powder is a mixture of Ti0 2 , W0 3 , Si0 2 and A1 2 0 3 , wherein the Ti0 2 content is 40 to 100 wt%,
W03含量为 0〜15 wt%, Si02含量为 0〜15 wt%, A1203含量为 0〜15 wt%。 The W0 3 content is 0 to 15 wt%, the Si0 2 content is 0 to 15 wt%, and the A1 2 0 3 content is 0 to 15 wt%.
所述锆盐溶液为乙酸锆、柠檬酸锆或硝酸锆与水的混合溶液，其中锆含量以 Zr02计为 0. 5〜The solution of zirconium salt is zirconium acetate, zirconium, citric acid or a mixed solution of zirconium nitrate and water, wherein the zirconium content -5 to 0.5 in terms of Zr0 2
30 wt%。 30 wt%.
所述贵金属的可溶性盐为氯铂酸 PtCl6、 二硝基四氨铂 (NH3) 4Pt (N03) 2、 氯化钯 PdCl2、 硝 酸钯 Pd (N03) 2、 硝酸铑 Rh (N03) 或氯化铑 RhCl3。 The soluble salt of the noble metal is chloroplatinic acid PtCl 6 , dinitrotetraammine platinum (NH 3 ) 4 Pt (N0 3 ) 2 , palladium chloride PdCl 2 , palladium nitrate Pd (N0 3 ) 2 , lanthanum nitrate Rh ( N0 3 ) or rhodium chloride RhCl 3 .
本发明的有益效果是：提供了一种高性能的柴油车尾气处理用前置氧化催化剂的配方和制 备方法；催化剂在柴油车尾气温度下可以将尾气中的气态污染物 CO和 HC氧化为 C02和 0;催 化剂制备方法简单， 生产成本低， 便于工业化； 采用本发明的制备方法， 以锆盐和混合 Ti02 粉体在载体表面制备涂层可以提高涂层的表面酸度， 减少 S02在催化剂表面的吸附， 涂层与载 体结合机械性能好， 热稳定性高， 抗硫中毒性能好， 上载的贵金属经过高温老化后仍能保持较 高的分散度， 使催化剂具有优良的低温活性和抗老化性能。 附图说明 图 1为柴油车尾气排放结构示意图。 具体实施方式 本发明目的在于提供一种在蜂窝陶瓷载体上制备用于去除柴油车尾气中一氧化碳（CO)和 碳氢化合物 （HC) 的氧化催化剂活性涂层的方法。 在图 1中， 柴油车柴油燃烧器 3产生的尾气由尾气排气管 4排出， 尾气处理用分为前置氧 化催化剂 1和与颗粒物捕收器 2中的 DPF再生用氧化催化剂的两种氧化催化剂相结合进行。本 发明所制备的前置氧化催化剂为以锆盐和混合 Ti02粉体在蜂窝陶瓷载体上原位制备的去除一 氧化碳碳氢化合物的氧化催化剂活性涂层； 主要利用柴油车尾气本身温度， 将尾气中的气态污 染物 CO和 HC转化成 C02和 0; 下面列举实施例进一步说明本发明。 The invention has the beneficial effects of providing a high-performance formula and preparation method of a pre-oxidation catalyst for tail gas treatment of diesel vehicles; the catalyst can oxidize gaseous pollutants CO and HC in the exhaust gas to C0 at the exhaust gas temperature of the diesel vehicle. 2 and 0; the catalyst preparation method is simple, the production cost is low, and the industrialization is convenient; using the preparation method of the invention, preparing the coating on the surface of the carrier with the zirconium salt and the mixed Ti0 2 powder can improve the surface acidity of the coating and reduce the S0 2 The adsorption of the catalyst surface, the coating and the carrier have good mechanical properties, high thermal stability, good sulfur poisoning resistance, and the retained precious metal can maintain high dispersion after high temperature aging, so that the catalyst has excellent low temperature activity and resistance. Aging performance. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram of a diesel vehicle exhaust gas discharge structure. DETAILED DESCRIPTION OF THE INVENTION It is an object of the present invention to provide a method for preparing an oxidation catalyst active coating for removing carbon monoxide (CO) and hydrocarbons (HC) from diesel vehicle exhaust gas on a honeycomb ceramic support. In Fig. 1, the exhaust gas generated by the diesel vehicle diesel burner 3 is discharged by the exhaust gas exhaust pipe 4, and the exhaust gas treatment is divided into two oxidations of the pre-oxidation catalyst 1 and the oxidation catalyst for DPF regeneration in the particulate matter trap 2. The catalyst is combined. The pre-oxidation catalyst prepared by the invention is an active catalyst for removing carbon monoxide hydrocarbons prepared by in-situ preparation of a zirconium salt and a mixed Ti0 2 powder on a honeycomb ceramic carrier; mainly utilizing the temperature of the diesel exhaust gas itself, the exhaust gas The gaseous pollutants CO and HC are converted to C0 2 and 0; the invention is further illustrated by the following examples.
实施例 1 : Example 1
将 ¾0和混合 Ti02粉料按固含量 40%比例混合 （混合 Ti02粉料中 W03含量为 8wt%， Ti02含 量为 92wt%)，搅拌 10 h得到用以涂覆的料浆；将 200目堇青石蜂窝陶瓷载体浸泡在料浆中 10s， 用高压气体吹出孔道中多余料浆， 以保证蜂窝表面凝胶上载均匀和孔道贯通； 之后将载体在 150°C干燥 1 h， 在 450°C焙烧 lh得到涂层重量为 100g/L的催化剂载体。 测量所得载体的吸水 率为 108g/L， 以 Pt (N03) 2溶液为原料，采用等量浸渍法负载 Pt， Pt含量为涂层材料质量的 1%， 浸渍 Pt (N03) 2溶液的载体经过 150°C烘干 l h， 在 450°C焙烧 l h后即得到氧化催化剂， 将此氧 化催化剂标记为 TiZr0-f。 Mixing 3⁄40 and mixed Ti0 2 powder in a solid content of 40% (mixing Ti0 2 powder with W0 3 content of 8 wt%, Ti0 2 content of 92 wt%), stirring for 10 h to obtain a slurry for coating; The 200 mesh cordierite honeycomb ceramic carrier was immersed in the slurry for 10 s, and the excess slurry in the tunnel was blown with high pressure gas to ensure uniformity of the surface of the honeycomb and the passage of the pores. The carrier was then dried at 150 ° C for 1 h at 450 °. C calcination for 1 h gave a catalyst support having a coating weight of 100 g/L. The water absorption of the obtained carrier was measured to be 108 g/L, and the Pt (N0 3 ) 2 solution was used as a raw material, and Pt was loaded by an equal amount of impregnation method, and the Pt content was 1% of the mass of the coating material, and the Pt (N0 3 ) 2 solution was impregnated. The carrier was dried at 150 ° C for 1 h, and calcined at 450 ° C for 1 h to obtain an oxidation catalyst, and the oxidation catalyst was labeled as TiZr0-f.
实施例 2: Example 2:
将乙酸锆溶液 （锆含量以 Zr02计为 20wt%)、 0和混合 Ti02粉料 （混合 Ti02粉料中 W03含 量为 8wt%， Ti02含量为 92wt%)按比例 (Zr02: ¾0： Ti02=2wt%: 60wt%: 38wt%)混合， 搅拌 10 h 得到用以涂覆的料浆 （固含量为 40wt%); 将 200 目堇青石蜂窝陶瓷载体浸泡在料浆中 10 s, 用高压气体吹出孔道中多余料浆， 以保证蜂窝表面凝胶上载均匀和孔道贯通； 之后将载体在 150°C干燥 1 h， 在 450°C焙烧 1 h得到涂层重量为 100g/L的催化剂载体。 测量所得载体的吸 水率为 114 g/L， 以 Pt (N03) 2溶液为原料， 采用等量浸渍法负载 Pt， Pt含量为涂层材料质量的 1%， 浸渍 Pt (N03) 2溶液的载体经过 150°C烘干 l h， 在 450°C焙烧 l h后即得到氧化催化剂， 将 此氧化催化剂标记为 TiZr5-f。 Zirconium acetate solution (zirconium content is 20 wt% in terms of Zr0 2 ), 0 and mixed Ti0 2 powder (W0 3 content in the mixed Ti0 2 powder is 8 wt%, Ti0 2 content is 92 wt%) in proportion (Zr0 2 : 3⁄40: Ti0 2 = 2wt%: 60wt%: 38wt%) mixed, stirred for 10 h to obtain a slurry for coating (solid content: 40% by weight); soaking 200 mesh cordierite honeycomb ceramic carrier in slurry for 10 s The excess slurry in the tunnel is blown with high pressure gas to ensure uniformity of the surface of the honeycomb and the passage of the pores. After that, the carrier is dried at 150 ° C for 1 h and calcined at 450 ° C for 1 h to obtain a coating weight of 100 g / L. Catalyst carrier. The water absorption of the obtained carrier was measured to be 114 g/L. The Pt (N0 3 ) 2 solution was used as the raw material, and Pt was loaded by the equivalent impregnation method. The Pt content was 1% of the mass of the coating material, and the Pt (N0 3 ) 2 solution was impregnated. The carrier was dried at 150 ° C for 1 h, and calcined at 450 ° C for 1 h to obtain an oxidation catalyst, and the oxidation catalyst was labeled as TiZr5-f.
实施例 3: Example 3:
制备条件和制备程序同例 2， 调节锆含量以 Zr02计占料浆总固含量的 10wt%; 制得氧化催 化剂， 将此氧化催化剂标记为 TiZrlO-f。 Preparation conditions and preparation procedure As in Example 2, the zirconium content was adjusted to 10% by weight of the total solid content of the slurry in terms of Zr0 2 ; an oxidation catalyst was prepared, and the oxidation catalyst was labeled as TiZrlO-f.
实施例 4: Example 4:
制备条件和制备程序同例 2， 调节锆含量以 Zr02计占料浆总固含量的 15wt%; 制得氧化催 化剂， 将此氧化催化剂标记为 TiZrl5-f。 将乙酸锆溶液 （锆含量以 Zr02计为 20wt%)、 0和混合 Ti02粉料 （混合 Ti02粉料中 W03含 量为 8wt%， Ti02含量为 92wt%)按比例 (Zr02: ¾0： Ti02=2wt%: 60wt%: 38wt%)混合， 搅拌 10 h 得到用以涂覆的料浆 （固含量为 40wt%); 将 200 目堇青石蜂窝陶瓷载体浸泡在料浆中 10 s, 用高压气体吹出孔道中多余料浆， 以保证蜂窝表面凝胶上载均匀和孔道贯通； 之后将载体在 150°C干燥 1 h， 在 450°C焙烧 1 h得到涂层重量为 100g/L的催化剂载体。 测量所得载体的吸 水率为 114 g/L， 以 Pd (N03) 3溶液和 Pt (N03) 3溶液为原料， 采用等量浸渍法负载 Pd和 Pt (Pd 和 Pt的摩尔比为 1 : 1 )， Pd和 Pt混和金属总含量为涂层材料质量的 1%， 浸渍 Pd (N03) 2溶液和 Pt (N03) 3溶液的载体经过 150°C烘干 1 h， 在 450°C焙烧 1 h后即得到氧化催化剂。 The preparation conditions and the preparation procedure were the same as in Example 2, and the zirconium content was adjusted to be 15 wt% of the total solid content of the slurry in terms of Zr0 2 ; an oxidation catalyst was prepared, and the oxidation catalyst was labeled as TiZrl5-f. Zirconium acetate solution (zirconium content is 20 wt% in terms of Zr0 2 ), 0 and mixed Ti0 2 powder (W0 3 content in the mixed Ti0 2 powder is 8 wt%, Ti0 2 content is 92 wt%) in proportion (Zr0 2 : 3⁄40: Ti0 2 = 2wt%: 60wt%: 38wt%) mixed, stirred for 10 h to obtain a slurry for coating (solid content: 40% by weight); soaking 200 mesh cordierite honeycomb ceramic carrier in slurry for 10 s The excess slurry in the tunnel is blown with high pressure gas to ensure uniformity of the surface of the honeycomb and the passage of the pores. After that, the carrier is dried at 150 ° C for 1 h and calcined at 450 ° C for 1 h to obtain a coating weight of 100 g / L. Catalyst carrier. The water absorption of the obtained carrier was measured to be 114 g/L, and the Pd (N0 3 ) 3 solution and the Pt (N0 3 ) 3 solution were used as raw materials, and Pd and Pt were supported by an equal amount of impregnation (the molar ratio of Pd to Pt was 1: 1), the total content of Pd and Pt mixed metal is 1% of the mass of the coating material, and the carrier impregnated with Pd(N0 3 ) 2 solution and Pt (N0 3 ) 3 solution is dried at 150 ° C for 1 h at 450 ° C. An oxidation catalyst was obtained after calcination for 1 h.
实施例 6: Example 6:
将柠檬酸锆、 ¾0和混合 Ti02粉料（混合 Ti02粉料中 Ti02含量为 89wt%， Si02含量为 10wt%， A1203含量为 lwt%) 混合 (柠檬酸锆: ¾0： Ti02=2. 9wt%: 60wt%: 38wt%) 调节加入 0量使料浆 中固含量达到 35% (锆含量以 ZrO^†占总固含量的 10wt%)， 搅拌 10 h得到用以涂覆的料浆； 将 200目堇青石蜂窝陶瓷载体浸泡在料浆中 10s， 用高压气体吹出孔道中多余料浆， 以保证蜂 窝表面凝胶上载均匀和孔道贯通； 之后将载体在 150°C干燥 lh， 在 450°C焙烧 lh得到涂层重 量为 82g/L的催化剂载体。测量所得载体的吸水率为 97g/L， 以氯铂酸 ?^16溶液为原料， 采 用等量浸渍法负载 Pt，Pt含量为涂层材料质量的 1%，浸渍氯铂酸 ? 16溶液的载体经过 150°C 烘干 1 h， 在 450°C焙烧 1 h后即得到氧化催化剂。 The zirconium citrate, 3⁄40 and mixed Ti0 2 powder (the mixed Ti0 2 powder has a Ti0 2 content of 89 wt%, the Si0 2 content is 10 wt%, and the A1 2 0 3 content is 1 wt%) is mixed (zirconium citrate: 3⁄40: Ti0 2 = 2. 9wt%: 60wt%: 38wt%) Adjusting the amount of 0 to make the solid content in the slurry reach 35% (zirconium content is 10% by weight of ZrO^†), and stirring for 10 h to obtain Covered slurry; soak the 200 mesh cordierite honeycomb ceramic carrier in the slurry for 10 s, and use the high pressure gas to blow out the excess slurry in the tunnel to ensure uniformity of the surface of the honeycomb and the passage of the pores; then the carrier is dried at 150 ° C. Lh, calcined at 450 ° C for 1 h to obtain a catalyst support having a coating weight of 82 g / L. The resulting water absorption of the support was measured as 97g / L, chloroplatinic acid? 16 ^ solution as raw materials, the same amount dipping load Pt, Pt content of 1% by weight of the coating material, impregnating chloroplatinic acid? 16 solution The carrier was dried at 150 ° C for 1 h, and calcined at 450 ° C for 1 h to obtain an oxidation catalyst.
实施例 7: Example 7
将硝酸锆、 0和混合 Ti02粉料 （混合 Ti02粉料中 Ti02含量为 90wt%， Si02含量为 10wt%) 按比例 （硝酸锆： 0: Ti02=3. 5wt%: 60wt%: 38wt%) 混合， 搅拌 10 h得到用以涂覆的料浆 （固 含量为 40wt%); 将 200 目堇青石蜂窝陶瓷载体浸泡在料浆中 10 s, 用高压气体吹出孔道中多 余料浆， 以保证蜂窝表面凝胶上载均匀和孔道贯通； 之后将载体在 150°C干燥 1 h， 在 450°C 焙烧 l h得到涂层重量为 97g/L的催化剂载体。测量所得载体的吸水率为 105 g/L， 以 Pt (N03) 2 溶液为原料， 采用等量浸渍法负载 Pt， Pt含量为涂层材料质量的 1%， 浸渍 Pt (N03) 2溶液的载 体经过 150°C烘干 1 h， 在 450°C焙烧 1 h后即得到氧化催化剂。 The zirconium nitrate, 0 and the mixed Ti0 2 powder (the Ti0 2 content in the mixed Ti0 2 powder is 90 wt%, the Si0 2 content is 10 wt%). Proportion (zirconium nitrate: 0: Ti0 2 = 3.5 wt%: 60 wt% : 38wt%) mixing, stirring for 10 h to obtain a slurry for coating (solid content: 40% by weight); soaking a 200 mesh cordierite honeycomb ceramic carrier in the slurry for 10 s, and blowing excess slurry in the channel with high pressure gas In order to ensure uniformity of the surface of the honeycomb surface and the passage of the pores; then the carrier was dried at 150 ° C for 1 h, and calcined at 450 ° C for 1 h to obtain a catalyst support having a coating weight of 97 g / L. The water absorption of the obtained carrier was measured to be 105 g/L, and the Pt (N0 3 ) 2 solution was used as the raw material. The Pt was loaded by the equivalent amount of impregnation method, and the Pt content was 1% of the mass of the coating material, and the Pt (N0 3 ) 2 solution was impregnated. The carrier was dried at 150 ° C for 1 h, and calcined at 450 ° C for 1 h to obtain an oxidation catalyst.
实施例 8: Example 8
将硝酸锆、 0和混合 Ti02粉料 （混合 Ti02粉料中 Ti02含量为 90wt%， Si02含量为 10wt%) 按比例 （硝酸锆： 0: Ti02=3. 5wt%: 60wt%: 38wt%) 混合， 搅拌 10 h得到用以涂覆的料浆 （固 含量为 40wt%); 将 200 目堇青石蜂窝陶瓷载体浸泡在料浆中 10 s, 用高压气体吹出孔道中多 余料浆， 以保证蜂窝表面凝胶上载均匀和孔道贯通； 之后将载体在 150°C干燥 1 h， 在 450°C 焙烧 1 h得到涂层重量为 97g/L的催化剂载体。 测量所得载体的吸水率为 116 g/L， Rh (N03) 3 溶液为原料， 采用等量浸渍法负载 Rh， Rh含量为涂层材料质量的 1%， 浸渍 Rh (N03) 3溶液的载 体经过 150°C烘干 1 h， 在 450°C焙烧 1 h后即得到氧化催化剂。 The zirconium nitrate, 0 and the mixed Ti0 2 powder (the Ti0 2 content in the mixed Ti0 2 powder is 90 wt%, the Si0 2 content is 10 wt%). Proportion (zirconium nitrate: 0: Ti0 2 = 3.5 wt%: 60 wt% : 38wt%) mixing, stirring for 10 h to obtain a slurry for coating (solid content: 40% by weight); soaking a 200 mesh cordierite honeycomb ceramic carrier in the slurry for 10 s, and blowing excess slurry in the channel with high pressure gas To ensure uniformity of the surface of the honeycomb surface and the passage of the pores; then the carrier is dried at 150 ° C for 1 h at 450 ° C Calcination for 1 h gave a catalyst support having a coating weight of 97 g/L. The water absorption of the obtained carrier was measured to be 116 g/L, Rh (N0 3 ) 3 solution was used as the raw material, Rh was loaded by the equivalent impregnation method, Rh content was 1% of the mass of the coating material, and the Rh (N0 3 ) 3 solution was impregnated. The carrier was dried at 150 ° C for 1 h, and calcined at 450 ° C for 1 h to obtain an oxidation catalyst.
实施例 9: Example 9
将硝酸锆、 0和混合 Ti02粉料 （混合 Ti02粉料中 Ti02含量为 89wt%， Si02含量为 10wt%， A1203含量为 lwt%) 按比例 (硝酸锆: ¾0： Ti02=3. 5wt%: 60wt%: 38wt%) 混合， 搅拌 10 h得到 用以涂覆的料浆 （固含量为 40wt%); 将 200 目堇青石蜂窝陶瓷载体浸泡在料浆中 10 s, 用高 压气体吹出孔道中多余料浆， 以保证蜂窝表面凝胶上载均匀和孔道贯通； 之后将载体在 150°C 干燥 1 h， 在 450°C焙烧 1 h得到涂层重量为 97g/L的催化剂载体。 测量所得载体的吸水率为 107 g/L， Pd (N03) 3溶液为原料， 采用等量浸渍法负载 Pd， Pd含量为涂层材料质量的 1%， 浸 渍 Pd (N03) 2溶液的载体经过 150°C烘干 1 h， 在 450°C焙烧 1 h后即得到氧化催化剂。 Zirconium nitrate, 0 and mixed Ti0 2 powder (ti 0 2 content in mixed Ti0 2 powder is 89 wt%, Si0 2 content is 10 wt%, A1 2 0 3 content is lwt%). Proportion (zirconium nitrate: 3⁄40: Ti0) 2 = 3. 5wt%: 60wt%: 38wt%) Mixing, stirring for 10h to obtain a slurry for coating (solid content is 40wt%); soaking 200 mesh cordierite honeycomb ceramic carrier in slurry for 10 s, The excess slurry in the tunnel is blown out with high pressure gas to ensure uniformity of the surface of the honeycomb and the passage of the pores. The carrier is then dried at 150 ° C for 1 h and calcined at 450 ° C for 1 h to obtain a catalyst with a coating weight of 97 g / L. Carrier. The water absorption of the obtained carrier was measured to be 107 g/L, and the Pd (N0 3 ) 3 solution was used as a raw material. The Pd was loaded by an equal amount of impregnation method, and the Pd content was 1% of the mass of the coating material, and the Pd (N0 3 ) 2 solution was impregnated. The carrier was dried at 150 ° C for 1 h, and calcined at 450 ° C for 1 h to obtain an oxidation catalyst.
实施例 10: Example 10
将硝酸锆、 0和混合 Ti02粉料 （混合 Ti02粉料中 Ti02含量为 89wt%， Si02含量为 10wt%， A1203含量为 lwt%) 按比例 (硝酸锆: ¾0： Ti02=3. 5wt%: 60wt%: 38wt%) 混合， 搅拌 10 h得到 用以涂覆的料浆 （固含量为 40wt%); 将 200 目堇青石蜂窝陶瓷载体浸泡在料浆中 10 s, 用高 压气体吹出孔道中多余料浆， 以保证蜂窝表面凝胶上载均匀和孔道贯通； 之后将载体在 150°C 干燥 1 h， 在 450°C焙烧 1 h得到涂层重量为 97g/L的催化剂载体。 测量所得载体的吸水率为 107 g/L， 以 Pd (N03) 3溶液和 Pt (N03) 3溶液为原料， 采用等量浸渍法负载 Pd和 Pt (Pd和 Pt 的摩尔比为 l : l )，Pd和 Pt混和金属总含量为涂层材料质量的 1%，浸渍 Pd (N03) 2溶液和 Pt (N03) 3 溶液的载体经过 150°C烘干 1 h， 在 450°C焙烧 1 h后即得到氧化催化剂。 Zirconium nitrate, 0 and mixed Ti0 2 powder (ti 0 2 content in mixed Ti0 2 powder is 89 wt%, Si0 2 content is 10 wt%, A1 2 0 3 content is lwt%). Proportion (zirconium nitrate: 3⁄40: Ti0) 2 = 3. 5wt%: 60wt%: 38wt%) Mixing, stirring for 10h to obtain a slurry for coating (solid content is 40wt%); soaking 200 mesh cordierite honeycomb ceramic carrier in slurry for 10 s, The excess slurry in the tunnel is blown out with high pressure gas to ensure uniformity of the surface of the honeycomb and the passage of the pores. The carrier is then dried at 150 ° C for 1 h and calcined at 450 ° C for 1 h to obtain a catalyst with a coating weight of 97 g / L. Carrier. The water absorption of the obtained carrier was measured to be 107 g/L, and the Pd (N0 3 ) 3 solution and the Pt (N0 3 ) 3 solution were used as raw materials, and Pd and Pt were supported by an equal amount of impregnation (the molar ratio of Pd to Pt was l: l), the total content of Pd and Pt mixed metal is 1% of the mass of the coating material, and the carrier impregnated with Pd (N0 3 ) 2 solution and Pt (N0 3 ) 3 solution is dried at 150 ° C for 1 h at 450 ° C. An oxidation catalyst was obtained after calcination for 1 h.
实施例 11 : Example 11:
将实施例 1中所得的 TiZrO-f催化剂、实施例 2中所得的 TiZr5-f催化剂、实施例 3中所 得的 TiZrlO-f催化剂和实施例 4中所得的 TiZrl5-f催化剂切割成尺寸为 9mm X 9mm X 48mm (沿 孔道方向长度为 48mm) 的小样， 将其置于管式炉中， 通入含水蒸汽 10%的空气在 600 °C保温 100 h，炉冷后得到催化剂的水热老化样，分别标记为 TiZrO-a、TiZr5-a、TiZrlO-a和 TiZrl5_a。 实施例 12:  The TiZrO-f catalyst obtained in Example 1, the TiZr5-f catalyst obtained in Example 2, the TiZrlO-f catalyst obtained in Example 3, and the TiZrl5-f catalyst obtained in Example 4 were cut into a size of 9 mm X. A sample of 9mm X 48mm (length 48mm along the tunnel direction) is placed in a tube furnace, and 10% of the water containing steam is kept at 600 °C for 100 h. After the furnace is cooled, the hydrothermal aging sample of the catalyst is obtained. They are labeled TiZrO-a, TiZr5-a, TiZrlO-a and TiZrl5_a, respectively. Example 12:
将实施例 1中所得的 TiZrO-f催化剂、实施例 2中所得的 TiZr5-f催化剂、实施例 3中所 得的 TiZrlO-f催化剂和实施例 4中所得的 TiZrl5-f催化剂切割成尺寸为 9mm X 9mm X 48mm (沿 孔道方向长度为 48讓）的小样，将其置于管式炉中，通入含 S02 30ppm的空气在 450°C保温 100 h， 炉冷后得到催化剂的硫老化样， 分别标记为 TiZr0-s、 TiZr5-s、 TiZrl0_s和 TiZrl5_s。 测试例 1. 分别以 TiZrO-f催化剂 （实施例 1 )、 TiZr5-f催化剂 （实施例 2)、 TiZrlO-f催化剂 （实 施例 3)、 TiZrl5-f催化剂（实施例 4)、 TiZrO_a催化剂 （实施例 11 )、 TiZr5_a催化剂 （实施 例 11 )、 TiZrlO-a催化剂（实施例 11 )、、 TiZrl5_a催化剂 （实施例 11 )、 TiZrO_s催化剂 （实 施例 12)、 TiZr5-s催化剂 （实施例 12)、 TiZrlO_s催化剂 （实施例 12) 和 TiZrl5_s催化剂 (实施例 12) 为例， 在模拟柴油车尾气的气氛中进行催化剂起燃特性测试。 具体测试程序为： 分别将催化剂切割成尺寸为 9mmX 9mmX 48mm (沿孔道方向长度为 48讓） 的测试样， 沿平行孔 道方向以石英棉包裹测试样， 并将其置于不锈钢反应管中， 通入柴油车尾气的模拟配气， 该模 拟配气成分中含有 CO ( lOOOppm), C02 ( 13%)、 C3H8 ( 500ppm)、 NO ( 700ppm), 02 ( 7%), N2平 衡， 空速 60000h— ^ 以 10 °C/min的速度将反应器温度从室温升至 450 °C， 以 AVL五组分分析 仪在线检测模拟配气经过催化剂后 C0和 C3H8的浓度。 The TiZrO-f catalyst obtained in Example 1, the TiZr5-f catalyst obtained in Example 2, the TiZrlO-f catalyst obtained in Example 3, and the TiZrl5-f catalyst obtained in Example 4 were cut into a size of 9 mm X. A sample of 9mm X 48mm (length 48 in the direction of the tunnel) was placed in a tube furnace, and it was incubated at 450 ° C for 100 h with air containing S0 2 30 ppm. After the furnace was cooled, the sulfur aging sample of the catalyst was obtained. They are labeled TiZr0-s, TiZr5-s, TiZrl0_s, and TiZrl5_s, respectively. Test example 1. TiZrO-f catalyst (Example 1), TiZr5-f catalyst (Example 2), TiZrlO-f catalyst (Example 3), TiZrl5-f catalyst (Example 4), TiZrO_a catalyst (Example 11), TiZr5_a catalyst (Example 11), TiZrlO-a catalyst (Example 11), TiZrl5_a catalyst (Example 11), TiZrO_s catalyst (Example 12), TiZr5-s catalyst (Example 12), TiZrlO_s catalyst (Example 12) As an example of the TiZrl5_s catalyst (Example 12), the catalyst light-off characteristics test was carried out in an atmosphere simulating diesel exhaust gas. The specific test procedure is as follows: The catalyst is cut into a test sample of size 9mmX 9mmX 48mm (length 48 in the direction of the tunnel), and the test sample is wrapped with quartz wool in the direction of the parallel hole, and placed in a stainless steel reaction tube. Simulated gas distribution into diesel exhaust, the simulated gas composition contains CO (100 ppm), C0 2 (13%), C 3 H 8 (500 ppm), NO (700 ppm), 0 2 (7%), N 2 Equilibrium, airspeed 60000h— ^ The reactor temperature was raised from room temperature to 450 °C at a rate of 10 °C/min. The AVL five-component analyzer was used to detect the simulated gas distribution through the catalyst after C0 and C 3 H 8 concentration.
催化剂性能评价试验结果表明： 所研制的催化剂对 C0和 HC有优良的低温去除效果， 催化 剂具有高的水热稳定性和抗硫中毒性能， 具体实例参见表 1。  The catalyst performance evaluation test results show that the developed catalyst has excellent low temperature removal effect on C0 and HC, and the catalyst has high hydrothermal stability and sulfur poisoning resistance. See Table 1 for specific examples.
实施例 1、 实施例 2、 实施例 3、 实施例 4、 实施例 6、 实施例 11和实施例 12中催化剂对 C0和 C3H8的催化氧化效果如表 1所示。 表 1 催化剂对 C0和 C3H8的催化氧化效果 The catalytic oxidation effects of the catalysts on C0 and C 3 H 8 in Example 1, Example 2, Example 3, Example 4, Example 6, Example 11 and Example 12 are shown in Table 1. Table 1 Catalytic oxidation effect of catalyst on C0 and C 3 H 8
转化温度 （°C )  Conversion temperature (°C)
催化剂 C0 HC  Catalyst C0 HC
TiZrO 115 120 145 170TiZrO 115 120 145 170
TiZr5 140 150 160 175TiZr5 140 150 160 175
TiZrlO 145 165 175 195TiZrlO 145 165 175 195
TiZrl5 145 170 180 215TiZrl5 145 170 180 215
TiZrO-a 195 250 275 320TiZrO-a 195 250 275 320
TiZr5~a 170 225 230 265TiZr5~a 170 225 230 265
TiZrlO-a 160 210 220 235TiZrlO-a 160 210 220 235
TiZrl5~a 175 215 225 255TiZrl5~a 175 215 225 255
TiZrO-s 175 255 260 315TiZrO-s 175 255 260 315
TiZr5~s 160 215 200 230TiZr5~s 160 215 200 230
TiZrlO-s 155 175 175 200 TiZrlO-s 155 175 175 200
TiZrl5-s 185 220 210 235  TiZrl5-s 185 220 210 235

Claims

权 利 要 求 书 Claim
1.一种柴油车前置氧化催化剂， 其特征在于， 以蜂窝陶瓷和金属为载体， 以锆盐溶液、 混 合 Ti02粉料与 0或混合 Ti02粉料与 0配制料浆， 在载体表面制备涂层材料； 采用等体积法 负载贵金属 Pt、 Rh和 Pd中的一种或几种， 经过烘干和焙烧制备的柴油车用氧化催化剂。 A diesel vehicle pre-oxidation catalyst characterized in that a honeycomb ceramic and a metal are used as a carrier, a zirconium salt solution, a mixed Ti0 2 powder and a 0 or a mixed Ti0 2 powder and a 0 slurry are prepared on the surface of the carrier. A coating material is prepared; an oxidation catalyst for a diesel vehicle prepared by drying and calcining one or more of precious metals Pt, Rh and Pd by an equal volume method.
2. 根据权利要求 1所述催化剂的制备方法， 其特征在于， 实现步骤如下：  2. The method for preparing a catalyst according to claim 1, wherein the steps are as follows:
( 1 ) 将锆盐溶液和 0混合， 使混合溶液中锆含量以 Zr02计为 0. 5〜30wt%， 然后加入混 合 Ti02粉体， 或混合 Ti02粉体与 0混合， 搅拌 l〜10 h制备成料浆。 通过调节加水量， 使料 浆固含量为 5〜50 wt%, 其中锆含量以 Zr02计占总固体重量的 0〜30 wt%, Ti02占总固体重量 的 50〜100 wt%; (1) A mixed solution of zirconium salt and 0, so that the mixed solution of zirconium in terms of Zr0 2 to 0. 5~30wt%, Ti0 2 and then adding a mixed powder or mixed powder and Ti0 2 0 mixture, stirred l~ Prepared into a slurry at 10 h. By adjusting the amount of water, the slurry solids content of 5~50 wt%, wherein the zirconium content of Zr0 2 by weight of the total solids basis 0~30 wt%, Ti0 2 by weight of the total solids of 50~100 wt%;
( 2) 将 200〜500 目蜂窝陶瓷载体浸泡在步骤 1所得的料浆中 2-30 s， 用高压气体吹出 孔道中多余料浆， 以保证蜂窝表面凝胶上载均匀和孔道贯通， 之后将所得载体在 100〜200 V 烘干 1〜10 h， 重复前面步骤调节涂层重量为 30〜150 g/L， 然后于 300〜600 °C焙烧 1〜5 h 得到载有涂层的载体；  (2) Soak the 200~500 mesh honeycomb ceramic carrier in the slurry obtained in step 1 for 2-30 s, and blow out the excess slurry in the channel with high pressure gas to ensure uniformity of the surface of the honeycomb surface and the passage of the pores. The carrier is dried at 100~200 V for 1~10 h, and the previous steps are repeated to adjust the coating weight to 30~150 g/L, and then calcined at 300~600 °C for 1~5 h to obtain a coated carrier;
( 3) 测量步骤 2所得载体的吸水率为 2-30wt%， 以贵金属 Pt、 Pd或 Rh的可溶性盐溶液 为原料， 以等量浸渍法负载一种或几种贵金属， 使贵金属含量为涂层材料质量的 0. 1〜3 wt%， 浸渍贵金属盐溶液后的载体经过 100〜200 °C烘干 1〜10 h， 300〜600 °C焙烧 1〜5 h后即得 到催化剂。  (3) The water absorption of the carrier obtained in the measurement step 2 is 2-30% by weight, and the soluble salt solution of the noble metal Pt, Pd or Rh is used as a raw material, and one or several precious metals are supported by an equal amount of impregnation method, so that the precious metal content is coated. The material quality is 0.1 to 3 wt%, and the carrier after impregnating the precious metal salt solution is dried at 100 to 200 ° C for 1 to 10 h, and calcined at 300 to 600 ° C for 1 to 5 hours to obtain a catalyst.
3. 根据权利要求 1所述的柴油车前置氧化催化剂， 其特征在于， 所述蜂窝陶瓷载体的材 质为堇青石、 莫来石、 碳化硅或 FeCrAl基高温金属。  The diesel vehicle front oxidation catalyst according to claim 1, wherein the honeycomb ceramic carrier is made of cordierite, mullite, silicon carbide or FeCrAl-based high temperature metal.
4. 根据权利要求 1所述的柴油车前置氧化催化剂，其特征在于，所述混合 Ti02粉体为 Ti02、 W03、 Si02和 A1203的混合物， 其中 Ti02含量为 40〜100 wt%, W03含量为 0〜15 wt%, Si02含量 为 0〜15 wt%, A1203含量为 0〜15 wt%。 The pre-diesel oxidation catalyst according to claim 1, wherein the Ti0 2 powder is mixed Ti0 2, W0 3, a mixture of Si0 2 and A1 2 0 3, wherein the Ti0 2 content of 40 ~100 wt%, W0 3 content is 0 to 15 wt%, Si0 2 content is 0 to 15 wt%, and A1 2 0 3 content is 0 to 15 wt%.
5. 根据权利要求 1所述的柴油车前置氧化催化剂， 其特征在于， 所述锆盐溶液为乙酸锆、 柠檬酸锆或硝酸锆与水的混合溶液， 其中锆含量以 Zr02计为 0. 5〜30 wt%0 The diesel vehicle pre-oxidation catalyst according to claim 1, wherein the zirconium salt solution is a mixed solution of zirconium acetate, zirconium citrate or zirconium nitrate with water, wherein the zirconium content is 0 in terms of Zr0 2 . 5~30 wt% 0
6. 根据权利要求 2柴油车前置氧化催化剂制备方法， 其特征在于， 所述贵金属的可溶性 盐为氯铂酸 PtCl6、 二硝基四氨铂（N¾) 4Pt (N03) 2、 硝酸铂 Pt (N03) 2、 氯化钯 PdCl2、 硝酸钯 Pd (N03) 2、 硝酸铑 Rh (N03) 或氯化铑 RhCl3。 The method for preparing a diesel vehicle pre-oxidation catalyst according to claim 2, wherein the soluble salt of the noble metal is chloroplatinic acid PtCl 6 , dinitrotetraammine platinum (N 3⁄4) 4 Pt (N0 3 ) 2 , nitric acid Platinum Pt (N0 3 ) 2 , palladium chloride PdCl 2 , palladium nitrate Pd (N0 3 ) 2 , rhodium nitrate Rh (N0 3 ) or rhodium chloride RhCl 3 .
7. 根据权利要求 2所述的制备方法， 其特征在于， 所述蜂窝陶瓷载体的材质为堇青石、 莫来石、 碳化硅或 FeCrAl基高温金属。  The preparation method according to claim 2, wherein the honeycomb ceramic carrier is made of cordierite, mullite, silicon carbide or FeCrAl-based high-temperature metal.
8. 根据权利要求 2的制备方法，其特征在于，所述混合 Ti02粉体为 Ti02、 W03、 SiO^P A1203 的混合物， 其中 Ti02含量为 40〜100 wt%， W03含量为 0〜15 wt%， Si02含量为 0〜15 wt%， A1203 含量为 0〜15 wt%。 8. The production method according to claim 2, wherein said mixed powder is 2 Ti0 and Ti0 2, W0 3, SiO ^ P A1 2 0 3 The mixture has a Ti0 2 content of 40 to 100 wt%, a W0 3 content of 0 to 15 wt%, a Si0 2 content of 0 to 15 wt%, and an A1 2 0 3 content of 0 to 15 wt%.
9. 根据权利要求 2所述的制备方法， 其特征在于， 所述锆盐溶液为乙酸锆、 柠檬酸锆或 硝酸锆与水的混合溶液， 其中锆含量以 Zr02计为 0. 5〜30 wt%0 5〜30。 The zirconium content of Zr0 2 is 0. 5~30 Wt% 0
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Publication number Priority date Publication date Assignee Title
CN101352682B (en) * 2008-09-09 2012-02-08 清华大学 Method for preparing front-located oxidation catalyst for diesel car
CN103861664B (en) * 2012-12-14 2017-11-10 上海郎特汽车净化器有限公司 A kind of diesel engine vent gas oxidation catalyst
KR101550614B1 (en) * 2014-02-11 2015-09-08 현대자동차 주식회사 Catalyst carrier for purification of exhausted gas, method for preparing the same, and catalyst for purification of exhausted gas
CN109372612A (en) * 2018-11-06 2019-02-22 广州航海学院 A kind of diesel engine exhaust gas treatment device and method
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CN110721706B (en) * 2019-10-30 2023-03-28 中国石油化工股份有限公司 Oxidation catalyst for purifying CO and preparation method and application thereof
CN113713838B (en) * 2021-11-04 2022-01-04 中汽研（天津）汽车工程研究院有限公司 Preparation method of integral oxidation type catalyst for diesel vehicle
CN114768795A (en) * 2022-03-30 2022-07-22 安徽方信立华环保科技有限公司 Preparation method of honeycomb catalyst for treating CO in sintering flue gas

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5082820A (en) * 1988-11-25 1992-01-21 Nippon Shokubai Kagaku Kogyo Co., Ltd. Carrier for gas-treating catalyst, method for production thereof and gas-treating catalyst incorporating said carrier therein
CN1548225A (en) * 2003-05-21 2004-11-24 中国科学院生态环境研究中心 Prepn of oxidizing catalyst for controlling exhaust of diesel truck
CN1995713A (en) * 2006-12-13 2007-07-11 北京英泰世纪环境科技有限公司 Metal carrier triple-effect catalytic unit and method for making same
CN100998941A (en) * 2007-01-04 2007-07-18 华东理工大学 Precatalyst and its preparation method
CN101352682A (en) * 2008-09-09 2009-01-28 清华大学 Method for preparing front-located oxidation catalyst for diesel car

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5082820A (en) * 1988-11-25 1992-01-21 Nippon Shokubai Kagaku Kogyo Co., Ltd. Carrier for gas-treating catalyst, method for production thereof and gas-treating catalyst incorporating said carrier therein
CN1548225A (en) * 2003-05-21 2004-11-24 中国科学院生态环境研究中心 Prepn of oxidizing catalyst for controlling exhaust of diesel truck
CN1995713A (en) * 2006-12-13 2007-07-11 北京英泰世纪环境科技有限公司 Metal carrier triple-effect catalytic unit and method for making same
CN100998941A (en) * 2007-01-04 2007-07-18 华东理工大学 Precatalyst and its preparation method
CN101352682A (en) * 2008-09-09 2009-01-28 清华大学 Method for preparing front-located oxidation catalyst for diesel car

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YU YAO ET AL.: "Preparation of Titanium-Zirconium Mixed Oxide and its Catalytic Performance of Pt Three-way Catalysts.", JOURNAL OF INORGANIC MATERIALS., vol. 23, no. 1, January 2008 (2008-01-01), pages 71 - 76 *

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