纳米晶铈锆复合氧化物催化剂的SAS法制备与表征
摘要
不断增加的汽车排放污染物已经成为危害生态环境和人体健康的越来越严重的问题。用于汽车尾气净化的铈锆复合氧化物的研究近年来成为新的研究热点。
超临界抗溶剂法(Supercritical Anti-solvents, SAS)是一种新兴的微粒化技术,在热敏炸药、聚合物、催化剂等领域具有十分广阔的应用前景。与传统的制备催化剂的方法相比较,SAS法表现出很多的优势,例如制备得到的粒子形状规则、尺寸小等。本文采用SAS法制备了铈锆复合氧化物。
采用SAS法制备了平均粒径为50~70 nm的CeO2前驱体,并采用正交试验法对制备工艺条件进行研究。结果表明,温度、浓度对CeO2前驱体的粒径影响较大;经焙烧,得到了纳米CeO2催化剂。采用SAS法制备了铈锆复合氧化物前驱体,考察了温度、压力和溶液浓度等工艺条件对铈锆共抗溶剂效应的影响。结果表明,温度对铈和锆在抗溶剂过程中有不同的影响,较高的温度下,乙酰丙酮锆比乙酰丙酮铈表现出更强的抗溶剂效应;随着压力、溶液流量增加,相对于乙酰丙酮铈,乙酰丙酮锆的抗溶剂效应逐渐降低。上述实验结果为实现不同铈锆比制备过程的可控性提供了有价值的依据。采用SAS法制备了一系列不同铈锆比的纳米铈锆复合氧化物催化剂并对其进行了表征。结果表明,和共沉淀法制备的催化剂相比,采用SAS法制备的纳米铈锆固溶体催化剂具有粒子尺寸小、形状规则、储氧量高、耗氢量大等优点;热稳定性实验结果表明,SAS法制备的催化剂具有较高的热稳定性和高温抗烧结能力。
It has become the serious problem that the increasing automotive exhaust pollution jeopardizes the ecological environment and people’s health. Cerium zirconium composite oxides have been widely used as three-way catalyst to control the automotive exhaust pollution. The study on the cerium zirconium composite oxides has become the hot topic in this field in recent years.
The supercritical antisolvent method (SAS) is a novel technique for micronization used in the fields such as preparations of explosives, polymer and catalysts precursor, showing good application potential. Compared with the common preparation methods, SAS shows excellent advantages, for example, small and narrow size distribution and regular shape. In this paper, the supercritical antisolvent is applied to prepare cerium zirconium composite oxides.
The amorphous precursor of CeO2 was prepared by the supercritical antisolvent techonology, with the average size 50~70 nm. The effects of experimental parameters were investigated by orthogonal test. The result showed that temperature and pressure influenced particle size. nano-CeO2 was obtained after calcianed at 550℃for 2 hour. Precursors of cerium zirconium composite oxides were prepared by the supercritical antisolvent, and the effects of experimental parameters on the co-antisolvent effect of Ce(acac)3 and Zr(acac)4 were investigated. It was showed that the temperature behaved distinct influences on the antisolvent of Ce(acac)3 and Zr(acac)4. Zr(acac)4 showed stronger antisolvent effect than Ce(acac)3 at higher temperature; With increasing of pressure and solution flow rate, the antisolvent effect of Zr(acac)4 became weaker, comapraed with Ce(acac)3. These conclusions provided the valuable guide for the controlled preparation of the precursor of cerium zirconium composite oxides. A series of cerium zirconium composite oxides catalyst with different Ce/Zr ratio were prepared by SAS method and then characterized. The result indicated that compared to coprecipation method, the catalyst prepared by SAS method showed considerable advantages such as smaller particle size, more regular shape and stronger OSC property and higher hydrogen consumption. The results of thermal stability tests indicated that the catalyst prepared by SAS method showed higher heat stability and the resistance to sintering, compared with the catalyst from coprecipitation method.
超临界抗溶剂法(Supercritical Anti-solvents, SAS)是一种新兴的微粒化技术,在热敏炸药、聚合物、催化剂等领域具有十分广阔的应用前景。与传统的制备催化剂的方法相比较,SAS法表现出很多的优势,例如制备得到的粒子形状规则、尺寸小等。本文采用SAS法制备了铈锆复合氧化物。
采用SAS法制备了平均粒径为50~70 nm的CeO2前驱体,并采用正交试验法对制备工艺条件进行研究。结果表明,温度、浓度对CeO2前驱体的粒径影响较大;经焙烧,得到了纳米CeO2催化剂。采用SAS法制备了铈锆复合氧化物前驱体,考察了温度、压力和溶液浓度等工艺条件对铈锆共抗溶剂效应的影响。结果表明,温度对铈和锆在抗溶剂过程中有不同的影响,较高的温度下,乙酰丙酮锆比乙酰丙酮铈表现出更强的抗溶剂效应;随着压力、溶液流量增加,相对于乙酰丙酮铈,乙酰丙酮锆的抗溶剂效应逐渐降低。上述实验结果为实现不同铈锆比制备过程的可控性提供了有价值的依据。采用SAS法制备了一系列不同铈锆比的纳米铈锆复合氧化物催化剂并对其进行了表征。结果表明,和共沉淀法制备的催化剂相比,采用SAS法制备的纳米铈锆固溶体催化剂具有粒子尺寸小、形状规则、储氧量高、耗氢量大等优点;热稳定性实验结果表明,SAS法制备的催化剂具有较高的热稳定性和高温抗烧结能力。
It has become the serious problem that the increasing automotive exhaust pollution jeopardizes the ecological environment and people’s health. Cerium zirconium composite oxides have been widely used as three-way catalyst to control the automotive exhaust pollution. The study on the cerium zirconium composite oxides has become the hot topic in this field in recent years.
The supercritical antisolvent method (SAS) is a novel technique for micronization used in the fields such as preparations of explosives, polymer and catalysts precursor, showing good application potential. Compared with the common preparation methods, SAS shows excellent advantages, for example, small and narrow size distribution and regular shape. In this paper, the supercritical antisolvent is applied to prepare cerium zirconium composite oxides.
The amorphous precursor of CeO2 was prepared by the supercritical antisolvent techonology, with the average size 50~70 nm. The effects of experimental parameters were investigated by orthogonal test. The result showed that temperature and pressure influenced particle size. nano-CeO2 was obtained after calcianed at 550℃for 2 hour. Precursors of cerium zirconium composite oxides were prepared by the supercritical antisolvent, and the effects of experimental parameters on the co-antisolvent effect of Ce(acac)3 and Zr(acac)4 were investigated. It was showed that the temperature behaved distinct influences on the antisolvent of Ce(acac)3 and Zr(acac)4. Zr(acac)4 showed stronger antisolvent effect than Ce(acac)3 at higher temperature; With increasing of pressure and solution flow rate, the antisolvent effect of Zr(acac)4 became weaker, comapraed with Ce(acac)3. These conclusions provided the valuable guide for the controlled preparation of the precursor of cerium zirconium composite oxides. A series of cerium zirconium composite oxides catalyst with different Ce/Zr ratio were prepared by SAS method and then characterized. The result indicated that compared to coprecipation method, the catalyst prepared by SAS method showed considerable advantages such as smaller particle size, more regular shape and stronger OSC property and higher hydrogen consumption. The results of thermal stability tests indicated that the catalyst prepared by SAS method showed higher heat stability and the resistance to sintering, compared with the catalyst from coprecipitation method.
引文
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[2] DIXON D J, JOHNSTON K P.Formation of microporous polymer fiber and oriented fibrils by precipitation with a compressed fluid antisolvent.J Appl PolymSCi,1993,50(11): 1929~1942
[3] THIES J, MULLER B W.Size controlled production of biodegradable microparticles with supercritical gases. European Journal of Pharm-aceutics and Bio Pharmaceutics, 1998, 45(1): 67~74
[4] GHADERI R, ARTURSSON P, CARLFORS J. A new method for preparing biodegradable microparticles and entrapment of hydrocortisone in DL-PLGA microparticles using supercritical fluids. European Journal Pha-rmaceutical Sciences, 2000, 47(10): 1~9
[5]贺文智,姜兆华,索全伶,超临界流体沉淀技术制备超细粒子研究,化学进展,2003,5(5):361~366
[6] HannaM, York P. WO 95/01 221, 1994
[7] Chattopadhyay P, Gup ta R B. Production of Antibiotic Nanoparticles Using Supercritical CO2 as Antisolvent with Enhanced Mass Transfer. Ind. Eng. Chem. Res., 2001,40: 3530~3539
[8] Chattopadhyay P, Gup ta R B. Production of griseofulvin nanoparticles using supercritical CO2 antisolvent with enhanced mass transfer. International J. of Pharmaceutics, 2001, 228:19~31
[9] Reverchon E. Supercritical antisolvent precipitation of micro-and nano- particles. J Supercrit Fluids, 1999, 15:1
[10] Debenedetti P G,et a1. Formation of protein microparticles by antisolvent precipitation.EU Pat,0542314A1, 1992
[11] Yeo S D, Lim G B, Debenedetti P G.et a1. Formation of microparticulate protein powder using a supercritical fluid antisolvent. Biotechn Bioeng, 1993, 41:341
[12] Randolph T W, Randolph A D, Mebes M. Enzymecatalyzed oxidation of cholesterol in supercritical carbon dioxide. Biotechn Prog, 1993, 9(4): 429
[13] Yeo S D, Lim G B, Debenedetti P G. Formation of microparticulate protein powder using supercritical fluid antisolvent. Biotechn Bioeng, 1993, 41(3): 341
[14] Gao Y, Mulenda T K, Shi Y F et a1. Fine particles preparation of redlake C pigment by spupercriticd fluid.J supercritical Fluids, 1998, 13(31): 369
[15] Betemo SR,洪镭,刘昆等,超临界连续GAS过程制备对苯二酚超细颗粒,华东理工大学学报,2001,27(4): 338
[16] Taki S,Badens E,Charbit G.Controlled release system formed by super-critical antisolvent coprecipitation of a herbicide and a biodegradable polymer.J Supercritical Fluids, 2001, 21: 61
[17] Randolph T W.Randolph A D.Mebes M.Enzymecatalyzed oxidation of cholesterol in supercritical carbon dioxide.Biotechn Prog, 1993, 9(4): 429
[18] Rantakyla M,Aaltonen O,Hturme M.The effect of initial drop size on particle size in the supercritical antisolvent precipitation(SAS)Technique.J Supercritical Fluids, 2002, 24(3): 251
[19]杨基础,制备超细微粒的超临界流体技术及其最新进展,第五届全国超临界流体技术及应用研讨会论文集,清华大学化学工程系
[20] Matson D W, Smith R D.supercritical fluid technologies for ceramic-processing applications. J Am, ceram soc, 1989, 72(6): 871~881
[21]俞守耕,贵金属催化净化汽车尾气中稀土氧化物的助催化和稳定化,贵金属,2002,23(2):66~70
[22] Perrichon V, Laachir A, Bergeret G et al. Reduction of Ceria with different Textures by Hydrogen and their Reoxidation by Oxygen. J Chem Soc, Faraday Trans, 1994,90(5): 773~781.
[23] Shyu J Z, Weber W H, Gandhi H S. Surface Characterization of Alumina-Supported Ceria. J Phys Chem, 1988, 92(17): 4964~4970.
[24] Murota T, Hasegawa T, Aozasa S et al, Specific heat magnetic susceptibility and electrical resistivity measurements on LaNiO3. Journal of Alloys andCompounds, 1993, 193(2): 287~289
[25]冯长根,胡玉才,王丽琼,铈锆氧化物固溶体对全钯三效催化剂性能的影响,应用化学,2003,20(2):59~162
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