A non-noble metal methanol fuel vehicle exhaust catalyst and its preparation method

Abstract

The present invention provides a non-noble metal methanol fuel vehicle exhaust catalyst, which comprises a catalyst coating and a catalyst carrier, and the catalyst coating is coated on the catalyst carrier; the catalyst coating comprises a catalyst active component and an active component carrier, the catalyst active component is an oxide of a non-noble metal element, and the active component carrier is Ce-Zr-Al2O3; the present invention also provides a preparation method of the non-noble metal methanol fuel vehicle exhaust catalyst, wherein the catalyst active component is prepared by a co-precipitation method or a sol-gel method, and the active component is dispersed on the Ce-Zr-Al2O3 carrier by an impregnation method to form a slurry, and then the slurry is coated on a vehicle carrier to obtain the methanol fuel vehicle exhaust catalyst. The catalyst prepared by the present invention does not contain noble metals, has a low cost, has good catalytic activity for methanol intermediate products, and has high durability.

Description

Technical Field

[0001] The present invention relates to the technical field of tail gas purification, and particularly to a non-noble metal methanol fuel vehicle tail gas catalyst and a preparation method thereof. Background Art

[0002] The development of diversified vehicle fuels can maximize the compensation for the oil supply-demand gap and achieve the sustainable development of energy and the environment. Among them, vehicle alternative fuels include natural gas, methanol, ethanol, liquefied petroleum gas, coal liquefaction, and biodiesel, etc. Methanol is rich in resources and can be regenerated, belonging to biomass energy. Therefore, the appropriate development of methanol fuel vehicles is a way to alleviate the energy problem. However, in the tail gas of methanol fuel vehicles, there are mainly pollutants such as CO, HC (hydrocarbons), HCHO, CH3OH, NOx, etc. In order to meet the emission target requirements, current methanol fuel vehicles generally use a three-way catalyst (TWC) to purify these pollutants. Noble metals such as Pt, Pd, Rh, etc., due to their good catalytic performance, can effectively catalyze the conversion of pollutants generated by methanol combustion into relatively harmless substances, helping the tail gas to meet the emission target requirements. However, noble metals have the problems of low reserves and high prices, which have an adverse impact on the control of the vehicle's overall cost, resulting in a high price for the post-treatment catalyst of methanol fuel vehicles. To reduce costs, non-noble metal catalysts have good prospects. However, compared with noble metal catalysts, the existing non-noble metal catalysts have poor effects and durability in the post-treatment of methanol vehicles and have been difficult to be actually applied. Summary of the Invention

[0003] In view of the above-mentioned disadvantages of the prior art, the purpose of the present invention is to provide a non-noble metal methanol fuel vehicle tail gas catalyst and a preparation method thereof, which are used to solve the technical problems of poor effects and durability of non-noble metal catalysts in the post-treatment of methanol vehicles in the prior art.

[0004] To achieve the above purpose and other related purposes, the present invention provides a non-noble metal methanol fuel vehicle tail gas catalyst, including a catalyst coating and a catalyst carrier, the catalyst coating is coated on the catalyst carrier; the catalyst coating includes a catalyst active component and an active component carrier, the catalyst active component is an oxide of a non-noble metal element, and the active component carrier is Ce-Zr-Al2O3.

[0005] As a preferred solution of the present invention, the oxide of the non-noble metal is selected from one or more of the oxides of Fe, Co, Mo, Cu, Mn, Ni, Mg.

[0006] As a preferred solution of the present invention, the catalyst carrier is cordierite.

[0007] The present invention also provides a method for preparing the non-noble metal methanol fuel vehicle exhaust catalyst as described above, comprising the following steps:

[0008] 1) Prepare the catalyst active component by coprecipitation or sol-gel method from the precursor of the non-noble metal element oxide;

[0009] 2) Load the catalyst active component onto the Ce-Zr-Al2O3 support by incipient wetness impregnation method, add additives, binder, and dispersant, and mix to form a slurry;

[0010] 3) Coat the slurry on the catalyst support, dry, and sinter at high temperature to obtain the non-noble metal catalyst.

[0011] As a preferred embodiment of the present invention, in step 1), the precursor of the non-noble metal element oxide is a soluble salt of the non-noble metal element.

[0012] As a preferred embodiment of the present invention, in step 1), the coprecipitation method comprises the steps of: dissolving and mixing the soluble salt of the non-noble metal element, adding an alkaline solution to precipitate it, washing and drying the precipitate, and sintering at 450-550 °C for 2-4 h to obtain the catalyst active component.

[0013] As a preferred embodiment of the present invention, in step 1), the sol-gel method comprises the steps of: dissolving and mixing the soluble salt of the non-noble metal element, adding an acidic solution to adjust the pH to 3-5, stirring at 60-100 °C to form a sol-gel, drying, and sintering at 450-550 °C for 2-4 h to obtain the catalyst active component.

[0014] As a preferred embodiment of the present invention, in step 1), the non-noble metal is selected from one or more of Fe, Co, Mo, Cu, Mn, Ni, and Mg.

[0015] As a preferred embodiment of the present invention, in step 1), the soluble salt of the non-noble metal is selected from one or more of chlorides, nitrates, and sulfates.

[0016] As a preferred embodiment of the present invention, in step 2), the content of CeO2 in the Ce-Zr-Al2O3 is 15-45 wt%, the content of ZrO2 is 0-30 wt%, and the balance is Al2O3.

[0017] As a preferred embodiment of the present invention, in step 2), the additive is Ba(OH)2.

[0018] As a preferred embodiment of the present invention, in step 2), the binder is selected from one or more of aluminosols, celluloses, and silica sols.

[0019] As a preferred embodiment of the present invention, in step 2), the dispersant is polyether polyol.

[0020] As a preferred embodiment of the present invention, in step 2), the weight percentage of each component in the slurry is as follows: the catalyst active component is 5-25 wt%, Ba(OH)2 is 0.5-2.5 wt%, the binder is 1.5-2.5 wt%, the dispersant is 0.1-0.5 wt%, and the balance is Ce-Zr-Al2O3.

[0021] As a preferred embodiment of the present invention, in step 3), the drying temperature is 70-105 °C.

[0022] As a preferred embodiment of the present invention, in step 3), the high-temperature sintering temperature is 500-600 °C.

[0023] As a preferred embodiment of the present invention, in step 3), the high-temperature sintering time is 2-4 h.

[0024] As described above, the non-noble metal methanol fuel vehicle exhaust catalyst and its preparation method of the present invention have the following beneficial effects:

[0025] The preparation method of the non-noble metal methanol fuel vehicle exhaust catalyst of the present invention prepares the catalyst active component by using the co-precipitation or sol-gel method, and disperses it on the Ce-Zr-Al2O3 carrier by the impregnation method to form a slurry, and then coats the slurry on the vehicle carrier to obtain the methanol fuel vehicle exhaust catalyst. The catalyst of the present invention does not contain noble metals, has low cost, has good catalytic activity for methanol intermediate products, and has high durability. Specific Embodiments

[0026] The following specific examples illustrate the embodiments of the present invention. Those skilled in the art can easily understand the other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention.

[0027] The first aspect of the present invention provides a non-noble metal methanol fuel vehicle exhaust catalyst, including a catalyst coating and a catalyst carrier; the catalyst coating uses the oxides of non-noble metal elements as the catalyst active component and Ce-Zr-Al2O3 as the active component carrier; the catalyst coating is coated on the catalyst carrier.

[0028] In the non-noble metal methanol fuel vehicle exhaust catalyst of the present invention, the oxides of the non-noble metals are selected from one or more of the oxides of Fe, Co, Mo, Cu, Mn, Ni, and Mg.

[0029] In a preferred embodiment of the present invention, the non-noble metal oxide is a combination of oxides of Fe, Co, Mo, and Cu. Further, the non-noble metal oxide is a combination of Fe2O3, Co3O4, MoO3, and CuO. The mass ratio of each component in the combination of Fe2O3, Co3O4, MoO3, and CuO is 0.1 to 0.3: 0.1 to 0.3: 0.1 to 0.3: 0.4 to 0.6. For example, it is 0.1 to 0.15: 0.1 to 0.3: 0.1 to 0.3: 0.4 to 0.6, 0.15 to 0.2: 0.1 to 0.3: 0.1 to 0.3: 0.4 to 0.6, 0.2 to 0.25: 0.1 to 0.3: 0.1 to 0.3: 0.4 to 0.6, 0.25 to 0.3: 0.1 to 0.3: 0.1 to 0.3: 0.4 to 0.6, 0.1 to 0.3: 0.1 to 0.15: 0.1 to 0.3: 0.4 to 0.6, 0.1 to 0.3: 0.15 to 0.2: 0.1 to 0.3: 0.4 to 0.6, 0.1 to 0.3: 0.2 to 0.25: 0.1 to 0.3: 0.4 to 0.6, 0.1 to 0.3: 0.25 to 0.3: 0.1 to 0.3: 0.4 to 0.6, 0.1 to 0.3: 0.1 to 0.3: 0.1 to 0.15: 0.4 to 0.6, 0.1 to 0.3: 0.1 to 0.3: 0.15 to 0.2: 0.4 to 0.6, 0.1 to 0.3: 0.1 to 0.3: 0.2 to 0.25: 0.4 to 0.6, 0.1 to 0.3: 0.1 to 0.3: 0.25 to 0.3: 0.4 to 0.6, 0.1 to 0.3: 0.1 to 0.3: 0.1 to 0.3: 0.4 to 0.45, 0.1 to 0.3: 0.1 to 0.3: 0.1 to 0.3: 0.45 to 0.5, 0.1 to 0.3: 0.1 to 0.3: 0.1 to 0.3: 0.5 to 0.55, or 0.1 to 0.3: 0.1 to 0.3: 0.1 to 0.3: 0.55 to 0.6.

[0030] In a preferred embodiment of the present invention, the non-noble metal oxide is a combination of oxides of Cu, Mn, Ni, and Mg. Further, the non-noble metal oxide is a combination of CuO, MnO2, NiO, and MgO. The mass ratio of each component in the combination of CuO, MnO2, NiO, and MgO is 1:0.4 to 0.6:0.1 to 0.3:0.1 to 0.3. For example, it is 1:0.4 to 0.45:0.1 to 0.3:0.1 to 0.3, 1:0.45 to 0.5:0.1 to 0.3:0.1 to 0.3, 1:0.5 to 0.55:0.1 to 0.3:0.1 to 0.3, 1:0.55 to 0.6:0.1 to 0.3:0.1 to 0.3, 1:0.4 to 0.6:0.1 to 0.15:0.1 to 0.3, 1:0.4 to 0.6:0.15 to 0.2:0.1 to 0.3, 1:0.4 to 0.6:0.2 to 0.25:0.1 to 0.3, 1:0.4 to 0.6:0.25 to 0.3:0.1 to 0.3, 1:0.4 to 0.6:0.1 to 0.3:0.1 to 0.15, 1:0.4 to 0.6:0.1 to 0.3:0.15 to 0.2, 1:0.4 to 0.6:0.1 to 0.3:0.2 to 0.25, or 1:0.4 to 0.6:0.1 to 0.3:0.25 to 0.3.

[0031] In a preferred embodiment of the present invention, the non-noble metal oxide is a combination of oxides of Co, Mo, Cu, Mn, and Ni. Further, the non-noble metal oxide is a combination of CoO, MoO2, CuO, MnO2, and NiO. The mass ratio of each component in the combination of CoO, MoO2, CuO, MnO2, and NiO is 1:0.4 - 0.6:0.1 - 0.3:0.1 - 0.3:0.1 - 0.2. For example, it is 1:0.4 - 0.45:0.1 - 0.3:0.1 - 0.3:0.1 - 0.2, 1:0.45 - 0.5:0.1 - 0.3:0.1 - 0.3:0.1 - 0.2, 1:0.5 - 0.55:0.1 - 0.3:0.1 - 0.3:0.1 - 0.2, 1:0.55 - 0.6:0.1 - 0.3:0.1 - 0.3:0.1 - 0.2, 1:0.4 - 0.6:0.1 - 0.15:0.1 - 0.3:0.1 - 0.2, 1:0.4 - 0.6:0.15 - 0.2:0.1 - 0.3:0.1 - 0.2, 1:0.4 - 0.6:0.2 - 0.25:0.1 - 0.3:0.1 - 0.2, 1:0.4 - 0.6:0.25 - 0.3:0.1 - 0.3:0.1 - 0.2, 1:0.4 - 0.6:0.1 - 0.3:0.1 - 0.15:0.1 - 0.2, 1:0.4 - 0.6:0.1 - 0.3:0.15 - 0.2:0.1 - 0.2, 1:0.4 - 0.6:0.1 - 0.3:0.2 - 0.25:0.1 - 0.2, 1:0.4 - 0.6:0.1 - 0.3:0.25 - 0.3:0.1 - 0.2, 1:0.4 - 0.45:0.1 - 0.3:0.1 - 0.3:0.1 - 0.15 or 1:0.4 - 0.45:0.1 - 0.3:0.1 - 0.3:0.15 - 0.2.

[0032] In the non-noble metal methanol fuel vehicle exhaust catalyst of the present invention, the catalyst carrier is cordierite.

[0033] The second aspect of the present invention provides a preparation method of a non-noble metal methanol fuel vehicle exhaust catalyst, comprising the following steps:

[0034] 1) Prepare the catalyst active component by coprecipitation or sol-gel method from the precursors of the non-noble metal element oxides;

[0035] 2) Load the catalyst active component onto the Ce-Zr-Al2O3 carrier by the incipient wetness impregnation method, and add additives, binders, and dispersants to form a slurry;

[0036] 3) Coat the slurry on the catalyst carrier, dry, and sinter at high temperature to obtain the non-noble metal catalyst.

[0037] The non-noble metal catalyst is a non-noble metal methanol fuel vehicle exhaust catalyst.

[0038] In the preparation method of the non-noble metal methanol fuel vehicle exhaust catalyst of the present invention, in step 1), the precursor of the non-noble metal element oxide is a soluble salt of the non-noble metal element.

[0039] In the present invention, the soluble salt of the non-noble metal element is prepared into the non-noble metal element oxide by the co-precipitation method or the sol-gel method as the catalyst active component, and then the active component is impregnated on the Ce-Zr-Al2O3 carrier and coated on the vehicle carrier to obtain the methanol fuel vehicle exhaust catalyst.

[0040] In the preparation method of the non-noble metal methanol fuel vehicle exhaust catalyst of the present invention, in step 1), the co-precipitation method includes the steps of: dissolving and mixing the soluble salt of the non-noble metal element, adding an alkaline solution to precipitate it, washing and drying the precipitate, and sintering at 450-550 °C for 2-4 h, for example, sintering is carried out at 450-460 °C, 460-470 °C, 470-480 °C, 480-490 °C, 490-500 °C, 500-510 °C, 510-520 °C, 520-530 °C, 530-540 °C or 540-550 °C, and the sintering time can be 2-3 h or 3-4 h to obtain the catalyst active component.

[0041] Among them, the alkaline solution is ammonia water.

[0042] In the preparation method of the non-noble metal methanol fuel vehicle exhaust catalyst of the present invention, in step 1), the sol-gel method includes the steps of: dissolving and mixing the soluble salt of the non-noble metal element, adding an acidic solution to adjust the pH to 3-5, such as 3-4 or 4-5, and stirring at 60-100 °C, for example, 60-65 °C, 65-70 °C, 70-75 °C, 75-80 °C, 80-85 °C, 85-90 °C, 90-95 °C or 95-100 °C to make it sol-gel, drying, and sintering at 450-550 °C for 2-4 h, for example, sintering is carried out at 450-460 °C, 460-470 °C, 470-480 °C, 480-490 °C, 490-500 °C, 500-510 °C, 510-520 °C, 520-530 °C, 530-540 °C or 540-550 °C, and the sintering time can be 2-3 h or 3-4 h to obtain the catalyst active component.

[0043] Among them, the acidic solution is selected from one or more of citric acid, nitric acid, and acetic acid. In a preferred embodiment of the present invention, the acidic solution is a citric acid solution.

[0044] In the preparation method of the non-noble metal methanol fuel vehicle exhaust catalyst of the present invention, the non-noble metal is selected from one or more of Fe, Co, Mo, Cu, Mn, Ni, and Mg.

[0045] The soluble salt of the non-noble metal is selected from one or more of chlorides, nitrates, and sulfates.

[0046] For example, the soluble salts of iron include one or more of ferric chloride, ferric sulfate, and ferric nitrate.

[0047] The soluble salts of cobalt include one or more of cobalt chloride, cobalt sulfate, and cobalt nitrate.

[0048] The soluble salts of molybdenum include one or more of molybdenum chloride, molybdenum sulfate, and molybdenum nitrate.

[0049] The soluble salts of copper include one or more of copper chloride, copper sulfate, and copper nitrate.

[0050] The soluble salts of manganese include one or more of manganese chloride, manganese sulfate, and magnesium nitrate manganese.

[0051] The soluble salts of nickel include one or more of nickel chloride, nickel sulfate, and nickel nitrate.

[0052] The soluble salts of magnesium include one or more of magnesium chloride and magnesium nitrate.

[0053] In a preferred embodiment of the present invention, the soluble salt of the non-noble metal is a nitrate.

[0054] In the preparation method of the non-noble metal methanol fuel vehicle exhaust catalyst of the present invention, in step 2), the content of CeO2 in the Ce-Zr-Al2O3 is 15-45 wt%, for example, 15-20 wt%, 20-25 wt%, 25-30 wt%, 30-35 wt%, 35-40 wt%, or 40-45 wt%, the content of ZrO2 is 0-30 wt%, for example, 0-5 wt%, 5-10 wt%, 10-15 wt%, 15-20 wt%, 20-25 wt%, or 25-30 wt%, and the balance is Al2O3.

[0055] In the preparation method of the non-noble metal methanol fuel vehicle exhaust catalyst of the present invention, in step 2), the promoter is Ba(OH)2.

[0056] In the preparation method of the non-noble metal methanol fuel vehicle exhaust catalyst of the present invention, in step 2), the binder is selected from one or more of aluminum sol, cellulose, and silica sol.

[0057] In the preparation method of the non-noble metal methanol fuel vehicle exhaust catalyst of the present invention, in step 2), the dispersant is polyether polyol. In a preferred embodiment of the present invention, the dispersant is a multi-chain polypropylene ether polyol 1105S or polyether polyol 4110 or polyether polyol GR405.

[0058] In the preparation method of the non-noble metal methanol fuel vehicle exhaust catalyst of the present invention, in step 2), the weight ratio of each component in the slurry: the catalyst active component is 5-25 wt%, for example, 5-10 wt%, 10-15 wt%, 15-20 wt% or 20-25 wt%, Ba(OH)2 is 0.5-2.5 wt%, for example, 0.5-1.0 wt%, 1.0-1.5 wt%, 1.5-2.0 wt% or 2.0-2.5 wt%, the binder is 1.5-2.5 wt%, for example, 1.5-2.0 wt% or 2.0-2.5 wt%, the dispersant is 0.1-0.5 wt%, for example, 0.1-0.2 wt%, 0.2-0.3 wt%, 0.3-0.4 wt% or 0.4-0.5 wt%, and the balance is Ce-Zr-Al2O3.

[0059] In the preparation method of the non-noble metal methanol fuel vehicle exhaust catalyst of the present invention, in step 3), the drying temperature is 70-105 °C, for example, 70-75 °C, 75-80 °C, 80-85 °C, 85-90 °C, 90-95 °C, 95-100 °C or 100-105 °C. The drying is carried out in air.

[0060] In step 3), the high-temperature sintering temperature is 500-600 °C, for example, 500-510 °C, 510-520 °C, 520-530 °C, 530-540 °C, 540-550 °C, 550-560 °C, 560-570 °C, 570-580 °C, 580-590 °C or 590-600 °C.

[0061] In step 3), the high-temperature sintering time is 2-4 h, for example, 2-3 h or 3-4 h.

[0062] Example 1

[0063] Dissolve and mix nitrates of non-noble metal elements such as Fe, Co, Mo, and Cu in a weight ratio of oxides: Fe2O3:Co3O4:MoO3:CuO = 0.2:0.15:0.15:0.5. Add ammonia water to the mixed solution for coprecipitation. Wash, filter, and dry the precipitate, and then calcine at 500 °C for 2 h to obtain the catalyst active component.

[0064] Impregnate 10% by weight of the active component in equal volume onto a Ce-Zr-Al2O3 (40% Ce, 25% Zr, the rest is Al) support, add 1.5% by weight of Ba(OH)2, 2% by weight of aluminum sol, and 0.4% by weight of polyether polyol 4110 dispersant to form a slurry. Coat the slurry on a cordierite support, dry it in air at 90 °C, and sinter it at 550 °C for 2 h to obtain the finished non-noble metal catalyst.

[0065] Example 2

[0066] Dissolve and mix nitrates of non-noble metal elements such as Fe, Co, Mo, and Cu in a weight ratio of oxides: Fe2O3:Co3O4:MoO3:CuO = 0.2:0.15:0.15:0.5. Add citric acid and ethanol to the mixed solution, stir it at 60 °C to make it sol-gel, dry the gel, and then calcine it at 500 °C for 2 h to obtain the catalyst active component.

[0067] Impregnate 10% by weight of the active component in equal volume onto a Ce-Zr-Al2O3 (40% Ce, 25% Zr, the rest is Al) support, add 1.5% by weight of Ba(OH)2, 2% by weight of aluminum sol, and 0.4% by weight of polyether polyol 4110 dispersant to form a slurry. Coat the slurry on a cordierite support, dry it in air at 90 °C, and sinter it at 550 °C for 2 h to obtain the finished non-noble metal catalyst.

[0068] Example 3

[0069] Dissolve and mix nitrates of non-noble metal elements such as Cu, Mn, Ni, and Mg in a weight ratio of oxides: CuO:MnO2:NiO:MgO = 1:0.5:0.2:0.2. Add ammonia water to the mixed solution for coprecipitation, wash, filter, and dry the precipitate, and then calcine it at 500 °C for 2 h to obtain the catalyst active component.

[0070] Impregnate 20% by weight of the active component in equal volume onto a Ce-Zr-Al2O3 (50% Ce, 15% Zr, the rest is Al) support, add 1% by weight of Ba(OH)2 and 2.5% by weight of silica sol, and 0.3% by weight of multi-chain polypropylene ether polyol 1105S, form a slurry, coat the slurry on a cordierite support, dry it in air at 90 °C, and sinter it at 550 °C for 2 h to obtain the finished non-noble metal catalyst.

[0071] Example 4

[0072] Dissolve and mix nitrates of non-noble metal elements such as Cu, Mn, Ni, and Mg in a weight ratio of oxides: CuO:MnO2:NiO:MgO = 1:0.5:0.2:0.2. Add citric acid and ethanol to the mixed solution, stir at 70 °C to form a sol-gel, dry the gel, and then calcine at 500 °C for 2 h to obtain the catalyst active component.

[0073] Impregnate 10% by weight of the active component onto a Ce-Zr-Al2O3 (40% Ce, 25% Zr, the rest is Al) support in an equal volume manner. Add 1.5% by weight of Ba(OH)2, 2% by weight of aluminum sol, and 0.4% by weight of polyether polyol GR405 dispersant to form a slurry. Coat the slurry on a cordierite support, dry in air at 90 °C, and sinter at 550 °C for 2 h to obtain the finished non-noble metal catalyst.

[0074] Example 5

[0075] Dissolve and mix nitrates of non-noble metal elements such as Co, Mo, Cu, Mn, and Ni in a weight ratio of oxides: CoO:MoO2:CuO:MnO2:NiO = 1:0.5:0.2:0.2:0.1. Add citric acid and ethanol to the mixed solution, stir at 80 °C to form a sol-gel, dry the gel, and then calcine at 500 °C for 2 h to obtain the catalyst active component.

[0076] Impregnate 20% by weight of the active component onto a Ce-Zr-Al2O3 (50% Ce, 15% Zr, the rest is Al) support in an equal volume manner. Add 1% by weight of Ba(OH)2, 2.5% by weight of aluminum sol, and 0.3% by weight of polyether polyol GR405 dispersant to form a slurry. Coat the slurry on a cordierite support, dry in air at 105 °C, and sinter at 550 °C for 2 h to obtain the finished non-noble metal catalyst.

[0077] Comparative Example 1

[0078] Use a commercial methanol catalyst (our company's product), in which the noble metal content is 50 g / ft 3 , Pt:Pd:Rh = 5:10:1.

[0079] Comparative Example 2:

[0080] Dissolve and mix nitrates of non-noble metal elements such as Cu, Mn, Ni, and Mg in a weight ratio of oxides: CuO:MnO2:NiO:MgO = 1:0.5:0.2:0.2. Add the mixed solution to ammonia water for coprecipitation, wash, filter, and dry the precipitate, and then calcine at 500 °C for 2 h to obtain the catalyst active component.

[0081] The active component with a weight ratio of 20% was impregnated onto the γ-Al2O3 support in an equal volume manner, and 1% by weight of Ba(OH)2, 2.5% by weight of silica sol, and 0.3% by weight of multi-chain polypropylene ether polyol 1105S were added to form a slurry. The slurry was coated on a cordierite support, dried in air at 90 °C, and sintered at 550 °C for 2 h to obtain the finished non-noble metal catalyst.

[0082] Comparative Example 3

[0083] The nitrates of non-noble metal elements such as Cu, Mn, Ni, and Mg were dissolved and mixed in a weight ratio of oxides: CuO:MnO2:NiO:MgO = 1:1:0.3:0.1. The mixed solution was added with ammonia water to carry out co-precipitation. The precipitate was washed, filtered, and dried, and then calcined at 500 °C for 2 h to obtain the catalyst active component.

[0084] The active component with a weight ratio of 20% was impregnated onto the Ce-Zr-Al2O3 (50% Ce, 15% Zr, and the rest is Al) support in an equal volume manner, and 1% by weight of Ba(OH)2, 2.5% by weight of silica sol, and 0.3% by weight of multi-chain polypropylene ether polyol 1105S were added to form a slurry. The slurry was coated on a cordierite support, dried in air at 90 °C, and sintered at 550 °C for 2 h to obtain the finished non-noble metal catalyst.

[0085] Comparative Example 4

[0086] The nitrates of non-noble metal elements such as Cu, Mn, Ni, and Mg were dissolved and mixed in a weight ratio of oxides: CuO:MnO2:NiO:MgO = 1:0.5:0.2:0.2. The mixed solution was added with ammonia water to carry out co-precipitation. The precipitate was washed, filtered, and dried, and then calcined at 500 °C for 2 h to obtain the catalyst active component.

[0087] The active component with a weight ratio of 20% was impregnated onto the Ce-Zr-Al2O3 (30% Ce, 25% Zr, and the rest is Al) support in an equal volume manner, and 1% by weight of Ba(OH)2, 2.5% by weight of silica sol, and 0.3% by weight of multi-chain polypropylene ether polyol 1105S were added to form a slurry. The slurry was coated on a cordierite support, dried in air at 90 °C, and sintered at 550 °C for 2 h to obtain the finished non-noble metal catalyst.

[0088] The catalysts prepared above were made into 1*3-inch catalyst samples, and the coating loading of all samples was 180 g / L. After the samples were subjected to hydrothermal aging at 850 °C for 50 hours in a tube furnace, the activity test was carried out.

[0089] The activity test was carried out on an equivalent ratio combustion methanol fuel vehicle exhaust gas simulation device. The reaction conditions were as follows: the space velocity was 60000 h -1 , the atmosphere was 1000 ppm of methanol, 100 ppm of formaldehyde, 2000 ppm of CO, 1000 ppm of NOx, 2000 ppm of O2, 28% of CO2, 15% of H2O, and balanced with N2. In the experiment, temperature programming was adopted, and the temperature was raised from room temperature to 500 °C at a rate of 10 °C per minute. At the same time, the concentrations of CO, methanol, and formaldehyde in the exhaust gas were detected. The temperature at which the conversion efficiency reached 50% was called the light-off temperature, denoted as T50; the temperature at which the conversion efficiency reached 90% was called the complete conversion temperature, denoted as T90. The test results are shown in Table 1.

[0090] Table 1 Test Results

[0091]

[0092] As can be seen from Table 1 above: Compared with the commercially available methanol fuel vehicle catalyst in Comparative Example 1, the sample in Example 3 showed comparable performance in the conversion of CO, methanol, and formaldehyde after undergoing hydrothermal aging at 850 °C for 50 hours. However, the catalyst in Example 3 of the present invention does not use precious metals, so it has a great advantage in terms of catalyst cost.

[0093] Compared with Example 3, the T50 and T90 of the catalyst prepared with γ-Al2O3 support in Comparative Example 2 were both higher than those of the catalyst in Example 3; for the catalyst prepared with a ratio of non-precious metal elements such as Cu, Mn, Ni, and Mg of 1:1:0.3:0.1 in the active component of the catalyst in Comparative Example 3, and the catalyst prepared with the support Ce-Zr-Al2O3 (30% Ce, 25% Zr, and the rest is Al) in Comparative Example 4, their T50 and T90 were both increased compared with Example 3.

[0094] In summary, the catalyst obtained by the preparation method of the non-precious metal methanol fuel vehicle exhaust gas catalyst of the present invention has the advantages of low cost, good catalytic activity for methanol intermediate combustion products, and high durability, and has great market application prospects. Therefore, the present invention effectively overcomes various disadvantages in the prior art and has high industrial utilization value.

[0095] The above embodiments are only illustrative of the principles and effects of the present invention, and are not used to limit the present invention. Any person familiar with this technology can modify or change the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or changes completed by those with ordinary knowledge in the technical field without departing from the spirit and technical ideas disclosed by the present invention should still be covered by the claims of the present invention.

Claims

1. A non-noble metal methanol fuel vehicle exhaust catalyst, characterized in that, It includes a catalyst coating and a catalyst support, and the catalyst coating is coated on the catalyst support; the catalyst coating includes a catalyst active component and an active component support, the catalyst active component is an oxide of a non-noble metal element, and the active component support is Ce-Zr-Al2O3; the oxide of the non-noble metal is a combination of CuO, MnO2, NiO, and MgO, and the mass ratio of each component in the combination of CuO, MnO2, NiO, and MgO is 1:0.4 - 0.6:0.1 - 0.3:0.1 - 0.3; the catalyst support is cordierite; the catalyst coating further includes an auxiliary agent, a binder, and a dispersant, the auxiliary agent is Ba(OH)2, the binder is selected from one or more of aluminosols, cellulose, and silica sols, and the dispersant is polyether polyol.

2. The preparation method of the non-noble metal methanol fuel vehicle exhaust catalyst according to claim 1, characterized in that, It includes the following steps: 1) Prepare the catalyst active component by coprecipitation or sol-gel method from the precursors of the oxides of non-noble metal elements; 2) Load the catalyst active component onto the Ce-Zr-Al2O3 support by incipient wetness impregnation method, add an auxiliary agent, a binder, and a dispersant, and mix to form a slurry; 3) Coat the slurry on the catalyst support, dry, and sinter at high temperature to obtain a non-noble metal catalyst.

3. The preparation method of the non-noble metal methanol fuel vehicle exhaust catalyst according to claim 2, wherein, In step 1), the precursors of the oxides of non-noble metal elements are soluble salts of non-noble metal elements.

4. The preparation method of the non-noble metal methanol fuel vehicle exhaust catalyst according to claim 3, characterized in that, It includes any one of the following features: a) In step 1), the coprecipitation method includes the steps of dissolving and mixing the soluble salts of non-noble metal elements, adding an alkaline solution to cause precipitation, washing and drying the precipitate, and sintering at 450 - 550 °C for 2 - 4 h to obtain the catalyst active component; b) In step 1), the sol-gel method includes the steps of dissolving and mixing the soluble salts of non-noble metal elements, adding an acidic solution to adjust the pH to 3 - 5, stirring at 60 - 100 °C to form a sol-gel, drying, and sintering at 450 - 550 °C for 2 - 4 h to obtain the catalyst active component.

5. The preparation method of the non-noble metal methanol fuel vehicle exhaust catalyst according to claim 4, characterized in that, It includes any one of the following features: a1) The alkaline solution is ammonia water; b1) The acidic solution is selected from one or more of citric acid, nitric acid, and acetic acid.

6. The preparation method of the non-noble metal methanol fuel vehicle exhaust catalyst according to claim 3, characterized in that, In step 1), the non-noble metal is selected from one or more of Fe, Co, Mo, Cu, Mn, Ni, and Mg; and / or, in step 1), the soluble salts of non-noble metals are selected from one or more of chlorides, nitrates, and sulfates.

7. The preparation method of the non-noble metal methanol fuel vehicle exhaust catalyst according to claim 3, characterized in that, In step 2), the content of CeO2 in the Ce-Zr-Al2O3 is 15 - 45 wt%, the content of ZrO2 is 0 - 30 wt%, and the rest is Al2O3; and / or, in step 2), the auxiliary agent is Ba(OH)2; and / or, in step 2), the binder is selected from one or more of aluminosols, cellulose, and silica sols; and / or, in step 2), the dispersant is polyether polyol.

8. The preparation method of the non-noble metal methanol fuel vehicle exhaust catalyst according to claim 7, characterized in that, In step 2), the weight percentages of the components in the slurry are as follows: the catalyst active component is 5-25 wt%, Ba(OH)₂ is 0.5-2.5 wt%, the binder is 1.5-2.5 wt%, the dispersant is 0.1-0.5%, and the balance is Ce-Zr-Al₂O₃.

9. The preparation method of the non-noble metal methanol fuel vehicle exhaust catalyst according to claim 2, characterized in that, In step 3), the catalyst carrier is cordierite; and / or, in step 3), the drying temperature is 70-105 °C; and / or, in step 3), the high-temperature sintering temperature is 500-600 °C; and / or, in step 3), the high-temperature sintering time is 2-4 h.

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