固定床雷尼金属催化剂研究进展

doi:10.16085/j.issn.1000-6613.2017-2626

摘要/Abstract

摘要： 雷尼金属催化剂具有价格低廉、工艺可控性强、技术成熟等优势，广泛用于各种有机合成加氢反应。但是雷尼型粉末催化剂存在容易粉化流失而活性降低、反应完毕后需要过滤分离催化剂等固有的缺点，仅能应用于小批量生产。固定床雷尼金属催化剂在工业装置上的应用进展较快，但现有文献散见于专利技术和新闻报道。本文介绍了固定床雷尼金属催化剂国内外的应用进展，总结了固定床雷尼金属催化剂的制备方法，主要有块状雷尼金属破碎、雷尼合金粉成型和热喷射镀层方法。分析了各种固定床雷尼金属催化剂制备方法的特点和创新点，指出国内外固定床雷尼金属催化剂已经取得一定进展，正在逐渐取代基于传统釜式工艺的粉末雷尼镍催化剂。

关键词: 固定床, 加氢, 催化剂

Abstract: Raney metal catalysts are widely used in hydrogenation reactions of organic synthesis due to the advantages of low price, controllable process, and mature technology. However, the Raney type catalyst is only used in small scale production due to the catalyst pulverization, loss of activity and the need of filtration and separation after reaction. Recently, the fixed-bed Raney metal catalyst gets more and more applications in industrial unit. However, the existing reports on the subject are rather scattered in patents and news. This paper introduces the technology development of fixed-bed Raney metal catalyst briefly, and summarizes the catalyst preparation methods including bulk Raney metal breaking and sieving, powdered Raney metal shaping, and monolith thermal spray-coating together with the analysis of their features and innovative points. It points out that certain technology progress of the fixed-bed Raney metal catalyst has been made, and it is gradually replacing the powdered Raney metal catalyst based on the autoclave-type process.

Key words: fixed-bed, hydrogenation, catalyst

中图分类号:

TQ203.4

王建强, 陈明明, 刘巍, 包莉鸿, 许中强. 固定床雷尼金属催化剂研究进展[J]. 化工进展, 2018, 37(11): 4280-4285.

WANG Jianqiang, CHEN Mingming, LIU Wei, BAO Lihong, XU Zhongqiang. Advance in fixed-bed Raney metal catalysts[J]. Chemical Industry and Engineering Progress, 2018, 37(11): 4280-4285.

参考文献

[1] 李海涛. 丁炔二醇加氢制1,4-丁二醇催化剂的失活机理与改性研究[D]. 太原:山西大学,2011. LI H T. Study of deactivation and promotion of catalyst employed in hydrogenation of butynediol to 1, 4-buttanediol[D]. Taiyuan:Shanxi University, 2011.
[2] 江志东, 陈瑞芳, 王金渠. 雷尼镍催化剂[J]. 化学工业与工程, 1997, 14(2):23-32. JIANG Z D, CHEN R F, WANG J Q. Raney-Ni catalyst[J]. Chemical Industry and Engineering, 1997, 14(2):23-32.
[3] RANEY M. Process of producing nickel catalysts:US2977327A[P]. 1958-09-26.
[4] RANEY M. Method of reclaiming catalytic material from spent catalytic material:US2139602[P]. 1935-06-17.
[5] RANEY M. Method of preparing catalytic material:US1915473[P]. 1930-12-31.
[6] RANEY M. Method of producing finely-divided nickel:US1628190[P]. 1926-05-14.
[7] TANIELYAN S, MORE S, AUGUSTINE R, et al. Continuous liquid-phase hydrogenation of 1, 4-butynediol to high-purity 1,4-butanediol over particulate Raney nickel catalyst in a fixed bed reactor[J]. Organic Process Research & Development, 2017, 21(3):327-335.
[8] 王立敏, 孙兵, 戴连欣, 等. BYD加氢制备BDO的加氢催化剂及BYD加氢制备BDO的方法:CN106140196A[P]. 2016-11-23. WANG L M, SUN B, DAI L X, et al. Hydrogenation catalyst using BYD hydrogenation to prepare BDO and method using BYD hydrogenation to prepare BDO:CN106140196A[P]. 2016-11-23.
[9] SCHMIDT S. Process for the selective production of propanols by hydrogenation of glycerol:US9586879[P]. 2014-03-14.
[10] LUO G, WANG Y, SUN D, et al. Effect of preparation process on compressive strength and hydrogenation performance of Raney-Ni/Al₂O₃ catalyst[J]. China Petroleum Processing and Petrochemical Technology, 2017, 19(2):14-20.
[11] DAI W, LU S, JIANG H, et al. Composite catalyst and preparation method therefor:US20160367972A1[P]. 2016-09-06.
[12] WOLF A, TUREK T, MLECZKO L. Structured Raney nickel catalysts for liquid-phase hydrogenation[J]. Chemical Engineering & Technololgy, 2016, 39(10):1933-1938.
[13] JIANG H, LU S, ZHANG X, et al. Effect of polyamide on selectivity of its supported Raney Ni catalyst[J]. Science China Chemistry, 2016, 59(6):776-780.
[14] JIANG H, LU S, ZHANG X, et al. Polymer-supported Raney nickel catalysts for sustainable reduction reactions[J]. Molecules, 2016, 21(7):833.
[15] A broader, better portfolio of hydrogenation catalysts. https://grace.com/chemical-processing/en-us/chemical-catalysts.
[16] 郑武正, 隆德沙加C, 斯波特尼兹罗伯特. 成型的催化剂和制备方法:CN1037283A[P]. 1989-11-22. ZHENG W Z, LUNDSAGER C, SPOTNITZ R M. Shaped catalysts and process:CN1037283A[P]. 1989-11-22.
[17] FREUND A, BERWEILER M, BENDER B, et al. Shaped, activated metal, fixed-bed catalyst:US6262307B1[P]. 1998-05-19.
[18] OSTGARD D, MOEBUS K, BERWEILER M, et al. Fixed bed catalysts:US6284703[P]. 1999-08-05.
[19] 舒茨P, 博麦斯特R, 德斯培鲁斯B, 等. 活化的阮内金属固定床催化剂及其制备方法:ZL94117063.2[P]. 2002-05-01. SCHUETZ P, BURMEISTER R, DESPEYROUX B, et al. Activated Raney metal fixed-bed catalyst and process for its preparation:ZL94117063.2[P]. 2002-05-01.
[20] OSTGARD D, MOEBUS K, BERWEILER M, et al. Fixed bed catalysts:US6489521B2[P]. 2001-06-17.
[21] OSTGARD D, BERWEILER M, RÖDER S, et al. The flexibility of the chemical and physical properties of metalystTM for the optimal performance of fixed bed reactions on activated base metal surfaces[J]. Catalysis of Organic Reactions, 2001, 82:75-89.
[22] RITTSTEIGER A, RÜFER A, SCHNEIDER S, et al. Process for producing trimethylhexamethylenediamine:US20170226044A1[P]. 2017-01-26.
[23] RÜFER A, RITTSTEIGER A, NITZ J, et al. 2-(3-(Aminomethyl)- 3,5,5-trimethylcyclohexyl)propane-1,3-diamine, a process for its production and use:US20170355662A1[P]. 2017-05-25.
[24] 赵会吉. 新型固定床Raney镍催化剂的制备、表征与活性评价[D]. 东营:中国石油大学, 2005. ZHAO H J. Preparation, characterization and activity evaluation of fixed-bed raney nickel catalyst[D]. Dongying:China University of Petroleum, 2005.
[25] OSTGARD D, BERWEILER M, RÖDER S. Process for the preparation of saturated organic compounds:US20020193618A1[P]. 2002-01-03.
[26] OSTGARD D, BERWEILER M, RÖDER S, et al. Activated base metal hllow spheres:the low density alternative for the fixed bed hydrogenation of organic compounds[J]. Catalysis of Organic Reactions, 2002, 89:273-323.
[27] BREITSCHEIDEL B, WALTER M, KRATZ D, et al. Method for the hydrogenation of carbonyl compounds:US6207865B1[P]. 1998-07- 15.
[28] TANIELYAN S, MARIN N, ALVEZ G, et al. An efficient, selective process for the conversion of glycerol to propylene glycol using fixed bed raney copper catalysts[J]. Organic Process Research & Development, 2013, 18(11):1419-1426.
[29] BECKER R, BRÖCKER F, KAIBEL G, et al. Process for preparing 1,4-butanediol by catalytic hydrogenation of 1, 4-butinediol:US6262317B1[P]. 1997-09-23.
[30] BREITSCHEIDEL B, DIEHLMANN U, RUHL T, et al. Fixed-bed Raney metal catalyst, its preparation and the hydrogenation of polymers using this catalyst:US6121188[P]. 1997-10-15.
[31] LOW F. Hydrogenation of aqueous butynediol on nickel aluminum catalyst:BE745225A1[P]. 1970-07-30.
[32] 岛津幸四郎, 立野芳明, 真柄光男, 等. 阮内催化剂,其制备方法和使用该催化剂生产糖醇的方法:CN96121302.7[P]. 1997-08-20. DAOJIN X, LIYE F, ZHENBING G, et al. Raney catalyst, process for producing it and process for producing sugar-alcohol using the same:CN96121302.7[P]. 1997-08-20.
[33] SCHMIDT S. Process for making 1,2-propane diol from hydrogenation of glycerol:US8735635B2[P]. 2010-02-23.
[34] 夏贾贾, 罗国华, 徐新, 等. 骨架镍催化剂制备及其催化烯基芳烃加氢性能的研究[J]. 工业催化, 2013, 21(7):59-63. XIA J J, LUO G H, XU X, et al. Preparation of Raney Ni catalyst and research on its catalytic hydrogenation performance for alkenyl aromatics[J]. Industrial Catalysis, 2013, 21(7):59-63.
[35] LUO G, WANG Y, SUN D, et al. Effect of preparation process on compressive strength and hydrogenation performance of Raney-Ni/Al₂O₃ catalyst[J]. China Petroleum Processing and Petrochemical Technology, 2017, 19(2):14-20.
[36] OSTGARD D, FREUND A, REHREN C, et al. Fixed-bed Raney-type catalysts:US20030120116[P]. 2002-12-04.
[37] RÜFER A, RITTSTEIGER A, NITZ J, et al. 2-(3,3,5- trimethylcyclohexyl)propane-1,3-diamine, a process for its production and use:US9862673B2[P]. 2017-05-25.
[38] JIANG H, LU S, ZHANG X, et al. Polymer-supported catalysts for clean preparation of n-butanol[J]. Catalysis Science & Technololy, 2014, 4(8):2499-2503.
[39] DAI W, JIANG H, LU S, et al. Supported catalyst, its activated form, and their preparation and use:US20150231612A1[P]. 2013-08-06.
[40] HAAKE M, DÖRSAM G, BOOS H. Thin layer catalysts based on Raney alloys, and method for the production thereof:US6998366B2[P]. 2000-12-21.
[41] CHENG W, LUNDSAGER C, SPOTNITZ R. Shaped catalysts and processes:US4895994[P]. 1988-10-18.
[42] CHENG W, CZARNECKI L, PEREIRA C. Preparation, characterization, and performance of a novel fixed-bed Raney catalyst[J]. Industrial Engineering Chemical Research, 1989, 28(12):1764-1767.
[43] TUREK T, WOLF A, MUNNICH C, et al. Shaped catalyst body, particularly for use as catalysts in hydrogenation:US20060224027A1[P]. 2006-03-06.
[44] 王玉晓, 肖钢. 一种固定床雷尼镍催化剂的制备方法:CN200810301493.7[P]. 2012-06-27. WANG Y X, XIAO G. Preparation method for fixed bed Raney nickel catalyst:CN200810301493.7[P]. 2012-06-27.
[45] 李贺, 王玉晓, 肖钢. 一种固定床雷尼镍催化剂的制备方法:CN200810300670.X[P]. 2012-09-05. LI H, WANG Y X, XIAO G. Preparation method for fixed bed Raney nickel catalyst:CN200810300670.X[P]. 2012-09-05.