CN101474559A - 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 PDFInfo
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- 239000000446 fuel Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 29
- 150000003624 transition metals Chemical class 0.000 claims abstract description 27
- 239000006104 solid solution Substances 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 38
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 18
- 229910052684 Cerium Inorganic materials 0.000 claims description 14
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- 206010013786 Dry skin Diseases 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 239000011240 wet gel Substances 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 238000004140 cleaning Methods 0.000 abstract description 3
- 238000000975 co-precipitation Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 238000003980 solgel method Methods 0.000 abstract description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 239000010949 copper Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- -1 acetaldehyde, transition metal Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000000703 Cerium Chemical class 0.000 description 2
- 229910002451 CoOx Inorganic materials 0.000 description 2
- 229910016553 CuOx Inorganic materials 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910015189 FeOx Inorganic materials 0.000 description 2
- 229910016978 MnOx Inorganic materials 0.000 description 2
- 229910005855 NiOx Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- BNUDRLITYNMTPD-UHFFFAOYSA-N acetic acid;zirconium Chemical compound [Zr].CC(O)=O BNUDRLITYNMTPD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- PRORZGWHZXZQMV-UHFFFAOYSA-N azane;nitric acid Chemical compound N.O[N+]([O-])=O PRORZGWHZXZQMV-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000010761 intermediate fuel oil Substances 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000003584 silencer Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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Abstract
本发明涉及一种乙醇燃料汽油机尾气净化催化剂及其制备方法，该催化剂组成：CeO2：50％～70％、ZrO2：20％～30％、过渡金属：1％－20％。采用溶胶－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。本发明通过在铈基材料中添加过渡金属形成固熔体，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。并且制备过程简单，成本低，活性高等优点。
Description
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一。
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，促进了催化性能的提高。该催化剂具有制备过程简单，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：
CeO2 50％～70％
ZrO2 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剂，pH值控制在8～11，搅拌反应10～60min，得到混合溶液；沉淀剂为NH3·H2O、NH4HCO3或NH4NO3。
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℃温度下加热反应10—20小时至形成湿凝胶；
4)在80—120℃干燥6—10小时，碾磨，400—600℃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(T50)为300～400℃，完全转化温度为(T90)400～500℃。
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—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，大大提高了铈基材料的热稳定性和低温活性，促进了催化性能的提高，用于乙醇燃料汽油机尾气净化，具有较高的去除效率。该催化剂具有制备过程简单，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(III)、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，CeO2、ZrO2与过渡金属氧化物(MOx)的质量比为：6：3：1；x＝1/2、1或3/2，M＝Mn、Fe、Co、Ni或Cu。
a为CeO2—ZrO2—MnOx，b为CeO2—ZrO2—FeOx，c为CeO2—ZrO2—CoOx，d为CeO2—ZrO2—NiOx，e为CeO2—ZrO2—CuOx。
实施例1
称取Ce(NO3)36H2O 27.342g，ZrO(NO3)26H2O 8.667g，Mn(NO3)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℃水浴加热12h，湿凝胶100℃干燥8小时，碾磨，500℃焙烧5小时，制得CeO2—ZrO2—MnOx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30000h-1，采用程序升温(10℃/min)，用红外检测产物中CO2的浓度。催化评价结果如图2所示。
实施例2
称取Ce(Ac)35H2O 11.6312g，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℃水浴加热12h，湿凝胶100℃干燥8小时，碾磨，500℃焙烧5小时，制得CeO2—ZrO2—FeOx催化剂。催化评价结果如图2所示。
实施例3
称取Ce(NO3)36H2O 27.342g，ZrO(NO3)2 6H2O 8.667g，Co(NO3)2 2.91g配成200ml溶液；加入浓度为2M NH3·H2O，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℃恒温水浴加热12h，抽滤，在100℃干燥8小时，碾磨，500℃焙烧5小时，制得CeO2—ZrO2—CoOx催化剂。催化评价结果如图2所示。
实施例4
称取Ce(Ac)35H2O 11.6312g，Zr(Ac)4 4.4748g，Ni(CH3COO)2·4H2O 2.908g配成200ml溶液，加入浓度为2M NH4HCO3，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℃恒温水浴加热12h，抽滤，在100℃干燥8小时，碾磨，500℃焙烧5小时，制得CeO2—ZrO2—NiOx催化剂。催化评价结果如图2所示。
实施例5
称取Ce(NO3)36H2O 27.342g，ZrO(NO3)26H2O 8.667g，Cu(NO3)23H2O 2.416g配成200ml溶液，加入浓度为2M NH4NO3，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℃恒温水浴加热12h，抽滤，在100℃干燥8小时，碾磨，500℃焙烧5小时，制得CeO2—ZrO2—CuOx催化剂。催化评价结果如图2所示。
Claims (5)
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：
CeO2：50％～70％
ZrO2：20％～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℃温度下加热反应10—20小时至形成湿凝胶；
4)在80—120℃干燥6—10小时，碾磨，400—600℃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NH3·H2O、NH4HCO3或NH4NO3。
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)。
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| CN104030349A (zh) * | 2014-06-16 | 2014-09-10 | 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 |
| 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 |
| 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 |
| CN108435190A (zh) * | 2018-03-27 | 2018-08-24 | 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 |
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| CN104030349A (zh) * | 2014-06-16 | 2014-09-10 | 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 |
| 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 |
| CN108435190A (zh) * | 2018-03-27 | 2018-08-24 | 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 |
| 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 |
| CN113135552A (zh) * | 2020-01-19 | 2021-07-20 | 中南大学 | 一种氯化氢催化氧化制氯气的方法 |
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