WO2010069157A1 - 乙醇燃料汽油机尾气净化催化剂及其制备方法 - Google Patents

乙醇燃料汽油机尾气净化催化剂及其制备方法 Download PDF

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WO2010069157A1
WO2010069157A1 PCT/CN2009/070086 CN2009070086W WO2010069157A1 WO 2010069157 A1 WO2010069157 A1 WO 2010069157A1 CN 2009070086 W CN2009070086 W CN 2009070086W WO 2010069157 A1 WO2010069157 A1 WO 2010069157A1
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transition metal
ethanol
zirconium
hours
mixed solution
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沈美庆
翁端
王建强
王军
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Tianjin University
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    • 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
    • B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
    • B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • B01J37/03—Precipitation; Co-precipitation
    • 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
    • B01D2255/2073—Manganese
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2255/20738—Iron
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    • B01D2255/20746—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20753—Nickel
    • 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
    • B01D2255/20761—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/40—Mixed oxides
    • B01D2255/407—Zr-Ce mixed oxides
    • 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
    • B01D2258/016—Methanol 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
    • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
    • B01J2235/15—X-ray diffraction
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the invention relates to an exhaust gas purifying technology for an ethanol fuel gasoline engine, in particular to an exhaust fuel purifying catalyst for an ethanol fuel gasoline engine and a preparation method thereof, in particular to a cerium-based oxide composite transition metal catalyst for purifying exhaust gas of an ethanol fuel gasoline engine and a preparation method thereof.
  • a transition metal is formed to form a solid solution, which improves the thermal stability and low-temperature activity of the ruthenium-based material, and promotes the improvement of catalytic performance.
  • ethanol gasoline of the two vehicles can effectively eliminate the formation of carbon deposits in the spark plug, combustion chamber, valve, and exhaust muffler parts, optimize the behavior of the working condition, avoid the failure caused by the formation of carbon deposit, and prolong the service life of the components. .
  • ethanol is a solvent with excellent performance and has a good cleaning effect, which can effectively eliminate the precipitation and condensation of fuel impurities in the gasoline tank and the fuel supply system, and has the function of clearing the oil passage.
  • ethanol gasoline increases the emissions of unburned ethanol, acetaldehyde, ether, acid and other volatile organic compounds compared to conventional gasoline vehicle exhaust emissions.
  • the catalyst used for purifying ethanol in the tail gas is mostly composed of noble metals Pt, Pd, Ag and some non-precious metals (Cu, Mn); the transition metal catalyst is cheap and easy to obtain relative to the noble metal; and in ethanol, acetaldehyde During the oxidation of organic matter, the transition metal shows better activity; however, the transition metal catalyst also has a problem of high temperature deactivation. Therefore, how to maintain the activity and thermal stability of the transition metal at high temperatures will It is the key to its application in the purification of ethanol fuel gasoline engine exhaust.
  • the object of the present invention is to provide an ethanol fuel gasoline engine exhaust gas purifying catalyst and a preparation method thereof, and use the high thermal stability of the cerium-zirconium oxygen storage material and the high-low temperature activity of the transition metal to form a solid solution by adding a transition metal to the cerium-based material. Improve the thermal stability and low temperature activity of the ruthenium-based materials and promote the improvement of catalytic performance.
  • the catalyst has the advantages of simple preparation process, low cost and high activity.
  • the ethanol fuel gasoline engine exhaust gas purifying catalyst provided by the invention is a solid solution prepared by adding a transition metal to the zirconia oxygen storage material as a raw material, and the mass composition is:
  • Transition metal 1% - 20%
  • the transition metals are Mn, Fe, Co, Ni and Cu.
  • the ethanol fuel gasoline engine exhaust gas purification catalyst provided by the present invention comprises the following steps:
  • an aqueous solution of a soluble cerium salt, a zirconium salt and a transition metal salt is reacted with citric acid and ethylene glycol to form a wet gel, dried, and calcined; specifically:
  • the transition metal (Mn, Fe, Co, Ni or Cu) doped cerium-zirconium solid solution is used as a catalyst for the purification of ethanol gasoline motor vehicles.
  • the ignition ignition temperature (T 5 ) of ethanol is 300 ⁇ 400 ° C, and the complete conversion temperature is (T 9 .) 400 ⁇ 500 °C.
  • the ethanol fuel gasoline engine exhaust gas purifying catalyst provided by the invention and the preparation method thereof are the high thermal stability of the cerium-zirconium oxygen storage material and the high-low temperature activity of the transition metal, and the transition metal (Mn, Fe) is obtained by the sol-gel method or the co-precipitation method.
  • the transition metal (Mn, Fe) is obtained by the sol-gel method or the co-precipitation method.
  • Co, Ni or Cu) doped cerium-zirconium solid solution catalyst which greatly improves the thermal stability and low-temperature activity of the cerium-based material, promotes the improvement of catalytic performance, and is used for the purification of tail gas of ethanol fuel gasoline engine, and has high removal efficiency.
  • the catalyst has the advantages of simple preparation process, low cost and high activity.
  • Figure 1 is an XRD pattern of a catalyst sample of the present invention.
  • Figure 2 is a graph showing the catalytic activity of a catalyst sample of the present invention on ethanol. detailed description
  • the cerium salt is one of cerium nitrate (111) and cerium (III) acetate.
  • the zirconium salt is one of zirconyl nitrate and zirconium acetate.
  • Manganese ions are obtained from manganese nitrate and manganese acetate; iron ions are obtained from ferric nitrate and ferric acetate; cobalt ions are obtained from cobalt nitrate and cobalt acetate; nickel ions are obtained from nickel nitrate and nickel acetate; copper ions are obtained from copper nitrate, Obtained in copper acetate.
  • the precipitating agent used in the coprecipitation method is one of ammonia water, ammonium hydrogencarbonate or ammonium nitrate.
  • Figure 1 is an XRD pattern of a catalyst sample of the present invention
  • Figure 2 is a graph showing the catalytic activity of a catalyst sample of the present invention on ethanol.
  • a is Ce0 2 - Zr0 2 - ⁇
  • b is Ce0 2 - Zr0 2 - Fe0x
  • c is Ce0 2 - Zr0 2 - Co0x
  • d is Ce0 2 - Zr0 2
  • the catalyst is used for simulating the catalytic activity test of ethanol gasoline vehicle exhaust gas: a fixed bed reactor is used, and the catalyst is taken as a 25.25 g quartz tube reactor with a diameter of 12 mm, and the reactant is a mixture of ethanol and air, and passed through 500 ml/min.
  • the air brought ethanol into the reaction system at a space velocity of 30,000 h -1 , and was programmed to raise the concentration of C0 2 in the product by infrared temperature (10 ° C / min).
  • the results of the catalytic evaluation are shown in Figure 2.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Environmental & Geological Engineering (AREA)
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  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Description

乙醇燃料汽油机尾气净化催化剂及其制备方法 技术领域
本发明涉及乙醇燃料汽油机尾气净化技术， 特别是一种乙醇燃料汽油机尾气净化催化剂 及其制备方法， 具体是一种用于乙醇燃料汽油机尾气净化的铈基氧化物复合过渡金属催化剂 及制备方法。在铈基材料中添加过渡说金属形成固熔体， 提高铈基材料的热稳定性和低温活性， 促进催化性能的提高。 背景技术
石油作为主要的汽车燃料在促进经济发展方面起书了巨大作用。 然而， 随着经济发展对能 源需求量的增加和石油不断减少及其不可再生性之间的矛盾日益突出。 同时， 石油的过度使 用造成的环境污染问题也受到人们的广泛关注。 醇类燃料以其高热值、 低污染和可再生的巨 大优势， 成为汽车燃料的替代品引起人们的高度重视。 燃料乙醇即是理想的车用替代燃料之 研究表明， 使用乙醇汽油具有以下优点： 一可以提高燃油品质。 乙醇汽油作为 "绿色" 增氧剂， 可完全替代汽油中含氧添加剂 MTBE的使用。 乙醇是很好的辛烷值改进剂， 将燃料乙 醇按 10%的比例混配入汽油， 可使辛烷值提高 2-3个单位， 提高油品的抗爆性能。 二车用乙 醇汽油由于燃烧充分， 能有效消除火花塞、 燃烧室、 气门、 排气管消声器部位积炭的形成， 优化工况行为， 避免了因积炭的形成而引起的故障， 延长部件使用寿命。 而且乙醇是一种性 能优良的溶剂， 具有很好的清洁作用， 能有效消除汽油车箱及燃油供给系统中燃油杂质的沉 淀和凝结， 具有油路疏通作用。 对乙醇燃料汽油机的排放特性研究表明， 采用乙醇汽油可以 明显改善降低碳氢化合物和一氧化碳的排放。 但是， 与普通汽油车尾气排放相比， 乙醇汽油 增加了未燃烧的乙醇， 乙醛， 乙醚， 酸等挥发性有机物的排放量。
针对乙醇燃料汽油机尾气中的乙醇等有机污染物， 国内外学者进行了探索研究。 催化净 化法目前是降低机动车尾气排放最有效的措施。 净化尾气中乙醇使用的催化剂， 大多以贵金 属 Pt、 Pd、 Ag和某些非贵金属（Cu、 Mn)作活性组分； 相对于贵金属而言， 过渡金属催化剂廉 价易得； 而且在乙醇， 乙醛等有机物的氧化过程中， 过渡金属显示了较好的活性； 但是过渡 金属催化剂也存在高温失活问题。 因此， 如何保持过渡金属在高温下的活性和热稳定性， 将 是其在乙醇燃料汽油机尾气净化应用中的关键。
发明内容
本发明的目的是提供一种乙醇燃料汽油机尾气净化催化剂及其制备方法， 利用铈锆储氧 材料的高热稳定性和过渡金属的高低温活性， 通过在铈基材料中添加过渡金属形成固熔体， 提高铈基材料的热稳定性和低温活性， 促进催化性能的提高。 该催化剂制备过程简单， 成本 低， 活性高等优点。
本发明提供的一种乙醇燃料汽油机尾气净化催化剂是以铈锆储氧材料为原料， 添加过渡 金属制成的固溶体， 质量组成为：
Ce02 50 %〜70 %
Zr02 20 %〜30 %
过渡金属： 1 %— 20 %
过渡金属为 Mn、 Fe、 Co、 Ni和 Cu。
本发明提供的乙醇燃料汽油机尾气净化催化剂包括的步骤是：
在加热和搅拌条件下， 可溶性铈盐、 锆盐和过渡金属盐的水溶液与柠檬酸及乙二醇反应 形成湿凝胶， 干燥， 焙烧； 具体为：
1 ) 按计量将铈、 锆和过渡金属的硝酸盐或铈、 锆和过渡金属的醋酸盐混合， 将制成的 水溶液与柠檬酸溶液混合，搅拌 30〜60min，得到混合溶液，其中，金属离子：柠檬酸 =0. 5〜 4， 摩尔比； 或铈、 锆和过渡金属的硝酸盐或铈、 锆和过渡金属的醋酸盐混合溶液中加入沉淀 齐 U， pH值控制在 8〜11， 搅拌反应 10〜60min， 得到混合溶液； 沉淀剂为 NH3 · H20、 N HC03 或譚 03。
2 ) 混合溶液再加入乙二醇搅拌反应 2— 4h; 乙二醇： 混合溶液 = 1 : 10〜30 (体积）。
3 ) 在 70— 80°C温度下加热反应 10— 20小时至形成湿凝胶；
4) 在 80— 120"C干燥 6— 10小时， 碾磨， 400— 600"C焙烧 3— 7小时。
采用过渡金属 （Mn、 Fe、 Co、 Ni或 Cu) 掺杂铈锆固熔体作为乙醇汽油机动车尾气净化 催化剂， 乙醇氧化起燃温度 （T5。） 为 300〜400°C， 完全转化温度为 （T9。） 400〜500°C。
本发明提供的乙醇燃料汽油机尾气净化催化剂及其制备方法是利用铈锆储氧材料的高热 稳定性和过渡金属的高低温活性， 采用溶胶一凝胶法或共沉淀法制得过渡金属 （Mn、 Fe、 Co、 Ni或 Cu)掺杂铈锆固熔体催化剂， 大大提高铈基材料的热稳定性和低温活性， 促进催化性能 的提高， 用于乙醇燃料汽油机尾气净化， 具有较高的去除效率。 该催化剂制备过程简单， 成 本低， 活性高等优点。 附图说明
图 1为本发明催化剂样品的 XRD图。
图 2为本发明催化剂样品对乙醇催化活性图。 具体实施方式
本发明结合实施例和附图进一步详细说明， 但并不是对本发明作任何限制。
实施例中的原料来源： 铈盐是硝酸铈 （111)、 醋酸铈 （III) 中的一种。 锆盐是硝酸氧锆、 醋酸锆中的一种。 锰离子从硝酸锰、 醋酸锰中获得； 铁离子从硝酸铁、 醋酸铁中获得； 钴离 子从硝酸钴、 醋酸钴中获得； 镍离子从硝酸镍、 醋酸镍中获得； 铜离子从硝酸铜、 醋酸铜中 获得。 共沉淀法采用的沉淀剂是氨水、 碳酸氢铵或硝酸氨中的一种。
图 1为本发明催化剂样品的 XRD图， 图 2为本发明催化剂样品对乙醇催化活性图。
其中， Ce02、 Zr02与过渡金属氧化物 （MOx) 的质量比为： 6: 3： 1； x=l/2、 1或 3/2， M= Mn、 Fe、 Co、 Ni或 Cu。
a为 Ce02— Zr02— Μηθχ, b为 Ce02— Zr02— Fe0x， c为 Ce02— Zr02— Co0x， d为 Ce02— Zr02
-NiOx, e为 Ce02-Zr02-Cu0xo
实施例 1
称取 Ce (N03) 3 6H20 27. 342 g， Zr0 ( N03) 2 6H20 8. 667g, Mn (N03) 2 3. 579g 配成 200ml 溶 液，称取柠檬酸 50. 4336g配成 1548ml溶液，混合均匀后，加入乙二醇 30ml，室温搅拌 30min， 80°C水浴加热 12h， 湿凝胶 10CTC干燥 8小时， 碾磨， 500°C焙烧 5小时， 制得 Ce02— Zr02— Μηθχ催化剂。
该催化剂用于模拟乙醇汽油车尾气催化活性测试： 采用固定床反应器， 取催化剂 0. 25g 装于直径为 12mm的石英管反应器中， 反应物为乙醇和空气的混合气， 通过 500ml/min的空气 将乙醇带入反应体系， 空速为 30000 h—1, 采用程序升温 （10°C/min)， 用红外检测产物中 C02 的浓度。 催化评价结果如图 2所示。
实施例 2
称取 Ce (Ac) 3 5¾0 11. 6312 g， Zr (Ac) 4 4. 4748g， Fe (Ac) 3 4. 04g 配成 200ml 溶液， 称 取柠檬酸 65. 016g配成 1548ml溶液， 混合均匀后， 加入乙二醇 30ml， 室温搅拌 30min， 80 °C 水浴加热 12h， 湿凝胶 100°C干燥 8小时， 碾磨， 500°C焙烧 5小时， 制得 Ce02— Zr02— FeOx 催化剂。 催化评价结果如图 2所示。 实施例 3
称取 Ce(N03)3 6H20 27.342 g， Zr0( N03)2 6H208.667g, Co (N03) 2 2.91g 配成 200ml 溶 液； 加入浓度为 2M NH3 · ¾0， 最终 pH值控制在 10， 持续搅拌 30min。 在持续搅拌下， 加入 乙二醇， 乙二醇： 混合溶液 =1: 20， 搅拌 3h; 然后在 70— 80°C恒温水浴加热 12h， 抽滤， 在 100°C干燥 8小时， 碾磨， 500°C焙烧 5小时， 制得 Ce02— Zr02— CoOx催化剂。 催化评价结 果如图 2所示。
实施例 4
称取 Ce(Ac)35 011.6312 g， Zr (Ac)44.4748g, Ni (CH3C00) 2.4H202.908g 配成 200ml 溶 液， 加入浓度为 2M NH4HC03， 最终 pH值控制在 10， 持续搅拌 30min。 在持续搅拌下， 加入乙 二醇， 乙二醇： 混合溶液 =1: 20， 搅拌 3h; 然后在 70— 80°C恒温水浴加热 12h， 抽滤， 在 100°C干燥 8小时， 碾磨， 500°C焙烧 5小时， 制得 Ce02_Zr02— NiOx催化剂。 催化评价结果 如图 2所示。
实施例 5
称取 Ce(N03)3 6¾027.342 g， Zr0( N03)2 6H208· 667g， Cu (N03) 23H202.416g 配成 200ml 溶 液， 加入浓度为 2M NH4N03， 最终 pH值控制在 10， 持续搅拌 30min。 在持续搅拌下， 加入乙 二醇， 乙二醇： 混合溶液 =1: 20， 搅拌 3h; 然后在 70— 80°C恒温水浴加热 12h， 抽滤， 在 100°C干燥 8小时， 碾磨， 500°C焙烧 5小时， 制得 Ce¾— Zr¾— CuOx催化剂。 催化评价结果 如图 2所示。

Claims

权 利 要 求 书
1、 一种乙醇燃料汽油机尾气净化催化剂， 它是以铈锆储氧材料为原料， 添加过渡金属 制成的固溶体， 其特征在于质量组成为：
Ce02: 50%〜70%
Zr02: 20%〜30%
过渡金属： 1%— 20%
所述的过渡金属为： Mn、 Fe、 Co、 Ni和 Cu。
2、权利要求 1所述的乙醇燃料汽油机尾气净化催化剂的制备方法， 其特征在于它包括的 步骤：
1) 按计量将铈、 锆和过渡金属的硝酸盐或铈、 锆和过渡金属的醋酸盐混合， 将制成的 水溶液与柠檬酸溶液混合， 搅拌 30〜60min， 得到混合溶液； 或
铈、锆和过渡金属的硝酸盐或铈、锆和过渡金属的醋酸盐混合溶液中加入沉淀剂， pH值 控制在 8〜11， 搅拌反应 10〜60min， 得到混合溶液；
2) 上述的混合溶液中加入乙二醇搅拌反应 2— 4h;
3) 在 70— 80°C温度下加热反应 10— 20小时至形成湿凝胶；
4) 在 80— 120"C干燥 6— 10小时， 碾磨， 400— 600"C焙烧 3— 7小时。
3、 根据权利要求 2 所述的制备方法， 其特征在于步骤 1)所述的混合溶液中金属离子： 柠檬酸 =0.5〜4， 摩尔比。
4、 根据权利要求 2 所述的制备方法， 其特征在于所述的沉淀剂为 ΝΗ3 · 0、 NH4HC03或
NH具。
5、根据权利要求 2 所述的制备方法， 其特征在于步骤 2)所述的乙二醇： 混合溶液 =1: 10〜30 (体积）。
PCT/CN2009/070086 2008-12-17 2009-01-08 乙醇燃料汽油机尾气净化催化剂及其制备方法 Ceased WO2010069157A1 (zh)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104525181A (zh) * 2015-01-09 2015-04-22 中国科学院上海高等研究院 用于碳烟颗粒催化燃烧的催化剂及其制备方法和应用
CN116212864A (zh) * 2021-12-03 2023-06-06 中国科学院大连化学物理研究所 共沉淀法制备的PdCeO基催化剂在甲烷燃烧中的应用
CN116550319A (zh) * 2023-06-20 2023-08-08 南昌大学 一种用于碳烟颗粒燃烧消除的催化剂及制备方法和应用
CN119143352A (zh) * 2024-11-12 2024-12-17 天津市立清源环境有限公司 一种光热裂解污水中生物质制备再生能源的处理方法

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104030349B (zh) * 2014-06-16 2016-02-10 洛阳理工学院 溶胶凝胶法合成铈掺杂稳定四方相氧化锆纳米粉的方法
CN106975491A (zh) * 2016-01-19 2017-07-25 天津科技大学 一种多孔Ce-Zr基复合氧化物催化剂的制备方法
CN106861718A (zh) * 2017-03-16 2017-06-20 山东大学 一种汽车尾气净化催化剂及其制备方法
CN108435190B (zh) * 2018-03-27 2020-12-25 上海倍绿环保科技有限公司 用于静电场协同催化氧化低浓度甲烷气体的钴铈锆复合金属氧化物催化剂及其制备方法
CN113135552B (zh) * 2020-01-19 2023-02-07 中南大学 一种氯化氢催化氧化制氯气的方法
CN117101651A (zh) * 2023-08-25 2023-11-24 昆明理工大学 一种多元铈基复合氧化物、催化剂及其制备方法与应用
CN117718063B (zh) * 2023-11-29 2025-12-12 四川光宝禾谷能源有限公司 内燃机尾气处理剂

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
JINGJING HAO ET AL.: "Complete oxidation of ethanol over Cu0.1Ce0.9Ox and Cu0.1Ce0.6Zr0.3Ox catalysts and structural characterization.", PROCEEDING OF THE 14TH NATIONAL RARE EARTH AND CATALYSIS CONGRESS, pages 48 - 55 *
LIWEI JIA ET AL.: "Dynamic oxygen storage and release over Cu0.1Ce0.9Ox and Cu0.1Ce0.6Zr0.3Ox complex compounds and structural characterization.", JOURNAL OF ALLOYS AND COMPOUNDS, vol. 473, 3 July 2008 (2008-07-03), pages 293 - 297 *
TING RAO ET AL.: "Oxidation of ethanol over Mn-Ce-0 and Mn-Ce-Zr-O complex compounds synthesized by sol-gel method.", CATALYSIS COMMUNICATIONS, vol. 8, 4 February 2007 (2007-02-04), pages 1743 - 1747 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104525181A (zh) * 2015-01-09 2015-04-22 中国科学院上海高等研究院 用于碳烟颗粒催化燃烧的催化剂及其制备方法和应用
CN116212864A (zh) * 2021-12-03 2023-06-06 中国科学院大连化学物理研究所 共沉淀法制备的PdCeO基催化剂在甲烷燃烧中的应用
CN116550319A (zh) * 2023-06-20 2023-08-08 南昌大学 一种用于碳烟颗粒燃烧消除的催化剂及制备方法和应用
CN119143352A (zh) * 2024-11-12 2024-12-17 天津市立清源环境有限公司 一种光热裂解污水中生物质制备再生能源的处理方法

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