从废FCC催化剂和废汽车尾气净化催化剂中回收稀土的研究进展
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摘要
以稀土元素(简称稀土)用量较大的废FCC催化剂和废汽车尾气净化催化剂为研究对象,分析总结了两类废催化剂中稀土的成分和回收方法。从废催化剂中回收稀土普遍采用先浸出、后分离提纯的方法。浸出普遍采用无机酸(多为盐酸),分离方法包括溶剂萃取法、化学沉淀法等,最后经焙烧得到稀土氧化物。为从废催化剂中高效回收稀土,可着重考察新浸出机制的引入、分离方式的选择、分离试剂的应用,以及浸出和分离条件的优化,从而为实现工业化回收提供技术支持。
The spent FCC catalyst and automobile exhaust purifying catalyst with larg dosage of rare earth elements were chosen as the study objects,and the composition and recovery methods of rare earth in the two catalysts are summarized. The general method for rare earth recovery is leaching first,then separation and purification. Inorganic acids(mostly hydrochloric acid) are often used for leaching,and solvent extraction and chemical precipitation are the methods for separation. Rare earth oxides are finally obtained by calcination. In order to efficiently recover rare earth from different spent catalysts,the introduction of new leaching mechanism,the selection of separation method,the application of separation reagent,and the optimization of leaching and separation condition should be focused,which are technical supports for commercial recycling.
The spent FCC catalyst and automobile exhaust purifying catalyst with larg dosage of rare earth elements were chosen as the study objects,and the composition and recovery methods of rare earth in the two catalysts are summarized. The general method for rare earth recovery is leaching first,then separation and purification. Inorganic acids(mostly hydrochloric acid) are often used for leaching,and solvent extraction and chemical precipitation are the methods for separation. Rare earth oxides are finally obtained by calcination. In order to efficiently recover rare earth from different spent catalysts,the introduction of new leaching mechanism,the selection of separation method,the application of separation reagent,and the optimization of leaching and separation condition should be focused,which are technical supports for commercial recycling.
引文
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[29]黄小卫,李建宁,张永奇,等.P204-P507在酸性硫酸盐溶液中对Nd3+和Sm3+的协同萃取[J].中国有色金属学报,2008,18(2):366-371.
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[37]中国石油化工股份有限公司.从含有稀土元素的废催化裂化催化剂中回收稀土元素的方法:中国,102453805 A[P].2012-05-16.
[38]任传婷,胡洁,李青,等.ICP-AES测定汽车催化剂中的助剂元素[J].光谱实验室,2013,30(3):1063-1067.
[39]Palacios M A,Gómez M M,Moldovan M,et al.Platinum-Group Elements:Quantification in Collected Exhaust Fumes and Studies of Catalyst Surfaces[J].Sci Total Environ,2000,257(1):1-15.
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[41]de Aberasturi D J,Pinedo R,de Larramendi I R,et al.Recovery by Hydrometallurgical Extraction of the Platinum-Group Metals from Car Catalytic Converters[J].Miner Eng,2011,24(6):505-513.
[42]有研稀土新材料股份有限公司.一种含稀土的铝硅物料中回收稀土方法:中国,101705380 B[P].2013-10-23.
[43]吴少娟.稀土催化材料在汽车尾气净化中的应用[J].广东化工,2010,37(8):56-58.
[44]童伟锋,董海刚,吴晓峰,等.从失效汽车尾气催化剂中提取铈和镧的研究[J].有色金属:冶炼部分,2014(5):42-44,48.
[45]Yoo S J.Metal Recovery and Rejuvenation of MetalLoaded Spent Catalysts[J].Catal Today,1998,44(1/2/3/4):27-46.
[46]深圳市格林美高新技术股份有限公司.汽车尾气净化催化剂中稀土和贵金属的回收工艺:中国,103031438 B[P].2014-08-20.
[2]陈健,吴楠.世界稀土资源现状分析与我国稀土资源可持续发展对策[J].农业现代化研究,2012,33(1):74-77.
[3]Christmann P.A Forward Look into Rare Earth Supply and Demand:A Role for Sedimentary Phosphate Deposits?[J].Proc Eng,2014,83:19-26.
[4]刘贵清,曲志平,张磊.从废催化剂中回收稀土的现状与展望[J].中国资源综合利用,2014,32(6):27-29.
[5]宗保宁,慕旭宏,孟祥堃,等.非晶态合金催化剂和磁稳定床反应工艺的创新与集成[J].石油学报:石油加工,2006,22(2):1-6.
[6]于善青,田辉平,龙军.国外低稀土含量流化催化裂化催化剂的研究进展[J].石油炼制与化工,2013,44(8):1-7.
[7]Schüler D,Buchert M,Liu R,et al.Study on Rare Earths and Their Recycling[R].Darmstadt:The Greens/EFA Group in the European Parliament,2011.
[8]刘利平,马晓建,张鹏,等.废催化剂中金属组分回收利用概述[J].工业安全与环保,2012,38(1):91-93,96.
[9]刘腾,邱兆富,杨骥,等.我国废炼油催化剂的产生量、危害及处理方法[J].化工环保,2015,35(2):159-164.
[10]王卫,宋晓军.稀土在工业催化剂中的应用进展[J].现代化工,2000,20(10):26-28.
[11]何捍卫,孟佳.采用P507(HEH/EHP)从废FCC催化剂中回收稀土[J].中南大学学报:自然科学版,2011,42(9):2651-2657.
[12]龚卫星,李艳荣.我国稀土废料回收利用技术与现状[J].中国资源综合利用,2013,31(9):36-38.
[13]李向前,马娟娟,刘峥延,等.我国稀土产品废弃物的稀土回收价值探讨[J].生态经济,2013(12):89-92.
[14]王斌,吴晓东,冉锐,等.稀土在机动车尾气催化净化中的应用与研究进展[J].中国科学:化学,2012,42(9):1315-1327.
[15]沈传松,张巍,杨骥,等.废汽车尾气三元催化剂的回收利用研究进展[J].环境污染与防治,2015,37(4):78-83.
[16]吴晓峰,董海刚,童伟锋,等.从失效汽车催化剂中回收稀土元素新工艺研究[J].稀土,2015,36(1):101-104.
[17]罗冬梅,余淑娴,郑湘娟,等.稀土及其化合物在催化中的应用[J].江西科学,2006,24(3):304-308.
[18]陈祖庇.废催化剂的处理和利用[J].炼油技术与工程,2005,35(3):1-6.
[19]郑文芳.FCC催化剂中镧和铈的浸取与分离技术[D].兰州:西北师范大学化学化工学院,2014.
[20]Innocenzi V,Ferella F,Michelis I D,et al.Treatment of Fluid Catalytic Cracking Spent Catalysts to Recover Lanthanum and Cerium:Comparison Between Selective Precipitation and Solvent Extraction[J].J Ind Eng Chem,2015,24:92-97.
[21]秦玉芳,许涛,马莹,等.废催化剂中稀土资源的回收与综合利用[J].稀土,2014,35(1):76-81.
[22]苑志伟,孟佳,赵世伟.从废FCC催化剂中回收稀土的研究[J].石油炼制与化工,2010,41(10):33-39.
[23]林伟.催化裂化催化剂生产过程中固体废弃物的综合治理[D].天津:天津大学化工学院,2007.
[24]Chi R,Zhang X,Zhu G,et al.Recovery of Rare Earth from Bastnasite by Ammonium Chloride Roasting with Fluorine Deactivation[J].Miner Eng,2004,17(9/10):1037-1043.
[25]黄桂文.我国稀土萃取分离技术的现状及发展趋势[J].江西冶金,2003,23(6):62-68.
[26]张秀英,薄其兵.稀土元素的环烷酸萃取研究进展[J].稀土,1999,20(5):49-53.
[27]罗兴华,黄小卫,朱兆武,等.2-乙基己基膦酸单2-乙基己基酯和二(2-乙基己基)磷酸从硫酸介质中协同萃取Ce(Ⅳ)的研究[J].中国稀土学报,2008,26(5):566-569.
[28]李建宁,黄小卫,朱兆武,等.P204-P507-H2SO4体系萃取稀土元素的研究[J].中国稀土学报,2007,25(1):55-58.
[29]黄小卫,李建宁,张永奇,等.P204-P507在酸性硫酸盐溶液中对Nd3+和Sm3+的协同萃取[J].中国有色金属学报,2008,18(2):366-371.
[30]张倩.新的分离方法在稀土元素分离富集中的应用研究[D].上海:上海大学,2008.
[31]邱小英.废液再生及全捞富集稀土试验研究[J].江西有色金属,2002,16(4):29-31,43.
[32]李晚霞.从废FCC催化剂中回收稀土镧和铈的研究[D].兰州:西北师范大学化学化工学院,2014.
[33]仇振琢,魏旭华.从催化剂厂废渣回收稀土的综合利用[J].石油化工,1992,21(7):474-478.
[34]韩旗英.稀土萃取分离技术现状分析[J].湖南有色金属,2010,26(1):24-27,66.
[35]付子忠,郑剑平,赵瑞卿,等.用草酸溶液从负载钕的P507中直接反萃取沉淀钕[J].湿法冶金,2004,23(1):6-15.
[36]秦玉芳.失效稀土催化剂和硅铁合金冶炼渣中稀土的回收工艺研究[D].呼和浩特:内蒙古大学化学化工学院,2013.
[37]中国石油化工股份有限公司.从含有稀土元素的废催化裂化催化剂中回收稀土元素的方法:中国,102453805 A[P].2012-05-16.
[38]任传婷,胡洁,李青,等.ICP-AES测定汽车催化剂中的助剂元素[J].光谱实验室,2013,30(3):1063-1067.
[39]Palacios M A,Gómez M M,Moldovan M,et al.Platinum-Group Elements:Quantification in Collected Exhaust Fumes and Studies of Catalyst Surfaces[J].Sci Total Environ,2000,257(1):1-15.
[40]Steinlechner S,Antrekowitsch J.Potential of a Hydrometallurgical Recycling Process for Catalysts to Cover the Demand for Critical Metals,Like PGMs and Cerium[J].JOM,2015,67(2):406-411.
[41]de Aberasturi D J,Pinedo R,de Larramendi I R,et al.Recovery by Hydrometallurgical Extraction of the Platinum-Group Metals from Car Catalytic Converters[J].Miner Eng,2011,24(6):505-513.
[42]有研稀土新材料股份有限公司.一种含稀土的铝硅物料中回收稀土方法:中国,101705380 B[P].2013-10-23.
[43]吴少娟.稀土催化材料在汽车尾气净化中的应用[J].广东化工,2010,37(8):56-58.
[44]童伟锋,董海刚,吴晓峰,等.从失效汽车尾气催化剂中提取铈和镧的研究[J].有色金属:冶炼部分,2014(5):42-44,48.
[45]Yoo S J.Metal Recovery and Rejuvenation of MetalLoaded Spent Catalysts[J].Catal Today,1998,44(1/2/3/4):27-46.
[46]深圳市格林美高新技术股份有限公司.汽车尾气净化催化剂中稀土和贵金属的回收工艺:中国,103031438 B[P].2014-08-20.