乙炔气相法合成乙酸乙烯催化剂的研究进展

doi:10.16085/j.issn.1000-6613.2016-2345

摘要/Abstract

摘要： 乙炔气相法制备乙酸乙烯工艺通常采用乙酸锌/活性炭催化剂。本文综述了活性组分、载体特性、助催化剂、制备方法及催化剂失活原因的研究，指出了乙酸锌为活性组分最佳选择，对比了3种催化反应机理，讨论了活性组分最佳负载量及负载方法；简述了活性炭作为催化剂载体所具有的特性，结合有效孔径分析了载体改性对催化剂活性的提高效果，展示了竹质活性炭作为催化剂载体良好的应用前景，并总结了催化剂失活的主要原因。指出需通过改性解决催化剂载体有效孔比例低的问题，并开展抑制催化剂失活的研究。

关键词: 活性炭, 催化剂, 脱附, 失活, 磨损

Abstract: The carbon-supported zinc acetate was used as the catalyst for the gas phase synthesis of vinyl acetate from acetylene and acetic acid. Researches on active components,features of catalyst support,promoters,catalyst preparation method and deactivation mechanism were reviewed. It was pointed out that zinc acetate was the optimal active component,and the mechanisms of three kinds of catalytic reaction were compared,then the optimal loading amount of active components and the loading method were discussed. The advantages of using activated carbon as catalyst support were described,and the influence of support modification on the activity of the catalyst was analyzed in associated with the effective pore diameter. In addition,the good application prospects of bamboo activated carbon as support were affirmed. The reasons of catalyst deactivation were also summarized in this paper. Further improving the ratio of effective pores by modifications and refraining the deactivation of the catalyst are in demand.

Key words: activated carbon, catalyst, desorption, deactivation, attrition

中图分类号:

TQ426

郭秀玲, 陈光辉, 王伟文, 李建隆. 乙炔气相法合成乙酸乙烯催化剂的研究进展[J]. 化工进展, 2017, 36(09): 3293-3299.

GUO Xiuling, CHEN Guanghui, WANG Weiwen, LI Jianlong. Research progress of catalysts for synthesis of vinyl acetate from acetylene and acetic acid[J]. Chemical Industry and Engineering Progress, 2017, 36(09): 3293-3299.

参考文献

[1] NIE Ying,XIAO Ming. Production technology progress and market analysis of vinyl acetate[J]. Fine Chemical Industrial Raw Materials & Intermediates,2011,3:14-18.
[2] SAMANOS B,BOUTRY P,MONTAMAL R. The mechanism of vinyl acetate formation by gas-phase catalytic ethylene acetoxidation[J]. Journal of Catalysis,1971,23(1):19-30.
[3] SEISIRO Nakamura,TERUO Yasui. The mechanism of the palladium-catalyzed synthesis of vinyl acetate from ethylene in a heterogeneous gas reaction[J]. Journal of Catalysis,1970,17(3):366-374.
[4] 王文兴. 工业催化[M]. 北京:化学工业出版社,1978:408. WANG Wenxing. Industrial catalysis[M]. Beijing:Chemical Industry Press,1978:408.
[5] 李倩,陶敏莉,张敏华. 乙炔气相法制醋酸乙烯钯金催化剂的研究进展[J]. 分子催化,2012,26(5):478-485. LI Qian,TAO Minli,ZHANG Minhua. Research progress of acetoxylation of ethylene to form vinyl acetate over Pd-Au catalyst[J]. Journal of Molecular Catalysis,2012,26(5):478-485.
[6] 黄子政,杨林松. 乙炔法合成乙酸乙烯中乙酸锌/活性炭催化剂生产中的问题分析[J]. 石油化工,1999,28(2):124-127. HUANG Zizheng,YANG Linsong. Review on zinc acetate/C catalyst used in the synthesis of vinyl acetate[J]. Petrochemical Technology,1999,28(2):124-127.
[7] 李苹,冯良荣,李子健,等. 乙炔法气相合成醋酸乙烯催化剂的研究综述[J]. 海南大学学报(自然科学版),2006,24(4):355-360. LI Ping,FENG Liangrong,LI Zijian,et al. A research summary of vinyl acetate synthesis from acetic acid and acetylene catalyzed by active carbon-zinc acetate[J]. Journal of Hainan University(Natural Science),2006,24(4):355-360.
[8] 陈晨,林性贻,陈晓晖,等. 乙炔法合成醋酸乙烯催化剂的研究进展[J]. 工业催化,2003,11(11):7-12. CHEN Chen,LIN Xingyi,CHEN Xiaohui,et al. Advances in the catalysts for synthesis of vinyl acetate from acetylene and acetic acid[J]. Industrial Catalysis,2003,11(11):7-12.
[9] 古川淳二,満谷昭夫. 酢酸ビニル合成反応触媒の作用機構[J]. 触媒,1962,4(3):258-267.
[10] 李东霞,李桂明. 乙炔法合成醋酸乙烯催化剂研究进展[J]. 煤炭与化工,2015,38(10):39-44. LI Dongxia,LI Guiming. Research progress of acetylene method to synthesize vinyl acetate catalysts[J]. Coal and Chemical Industry,2015,38(10):39-44.
[11] 张仁文. 醋酸乙烯高效催化剂的研制[J]. 维纶通讯,1999,19(2):27-29. ZHANG Renwen. The development of efficient vinyl acetate catalyst[J]. Whalen Communication,1999,19(2):27-29.
[12] 周邦荣. 醋酸乙烯制造方法的过去、现在及将来[J]. 维纶通讯,1990(2):47-58. ZHOU Bangrong. Manufacturing method of vinyl acetate in the past,present and future[J]. VIP Information,1990(2):47-58.
[13] 周桂林,蒋毅,吕绍洁,等. 高比表面积活性炭载体结构对乙炔法合成醋酸乙烯催化剂活性的影响[J]. 石油化工,2004,33(7):608-611. ZHOU Guilin,JIANG Yi,LV Shaojie,et al. Effect of support structure on catalyst activity of high specific surface area activated cabron catalysts for vinyl acetate synthesis[J]. Petrochemical Technology,2004,33(7):608-611.
[14] 邱发礼,吕绍洁,汪怡季,等. 乙炔法合成醋酸乙烯高活性催化剂的研究[J]. 石油化工,1989,18(7):447-449. QIU Fali,LV Shaojie,WANG Yiji,et al. Study on high activity catalyst for synthesis of vinyl acetate from acetylene and acetic acid[J]. Petrochemical Technology,1989,18(7):447-449.
[15] 陈维苗,丁云杰,薛飞,等. 合成气制C₂含氧化合物Rh基催化剂中的载体效应[J]. 化工进展,2014,33(7):1753-1762. CHEN Weimiao,DING Yunjie,XUE Fei,et al. Support effect of Rh-based catalyst for CO hydrogenation to C₂-oxygenates[J]. Chemical Industry and Engineering Progress,2014,33(7):1753-1762.
[16] 贾莉. 乙炔气相法合成醋酸乙烯新型催化剂的研究[D]. 杭州:浙江大学,2003. JIA Li. Study of a new type of catalyst for the synthesis of vinyl acetate via acetylene method[D]. Hangzhou:Zhejiang University,2003.
[17] 李明,尚会建,胡国胜,等. 国内乙炔气相法制备醋酸乙烯催化剂的研究进展[J]. 河北工业科技,2009,26(5):395-399. LI Ming,SHANG Huijian,HU Guosheng,et al. Development of vinyl acetate synthesis from acetylene in gas phase in China[J]. Hebei Journal of Industrial Science and Technology,2009,26(5):395-399.
[18] 朱成文. 影响天然气乙炔法合成醋酸乙烯产量因素的研究[J]. 石油与天然气化工,2006(2):90-92. ZHU Chengwen. Study on the catalytic removal of trace olefins in aromatic hydrocarbons[J]. Chemical Engineering of Oil & Gas,2006(2):90-92.
[19] 陈凯歌,肖锋,蒋晓萍,等. 载体结构对锡铁负载型催化剂脱硝性能的影响[J]. 化工进展,2016,35(12):3919-3927. CHEN Kaige,XIAO Feng,JIANG Xiaoping,et al. Effect of pore structure on the performance of Sn-Fe supported catalyst in denitration[J]. Chemical Industry and Engineering Progress,2016,35(12):3919-3927.
[20] 孟冠华,李爱民,张全兴,等. 活性炭的表面含氧官能团及其对吸附影响的研究进展[J]. 离子交换与吸附,2006,23(1):88-94. MENG Guanhua,LI Aimin,ZHANG Quanxing,et al. Studies on the oxygen-containing groups of activated carbon and their effects on the adsorption character[J]. Ion Exchange and Adsorption,2006,23(1):88-94.
[21] 侯春燕,冯良荣,李子健,等. 乙炔法合成醋酸乙烯催化剂载体表面羧基与羰基作用机理的研究[J]. 化学学报,2009,67(13):1528-1532. HOU Chunyan,FENG Liangrong,LI Zijian,et al. Mechanism of carboxyl and carbonyl groups in carrier surface of catalyst for vinyl acetate synthesis[J]. Acta Chimica Sinica,2009,67(13):1528-1532.
[22] 陈曙,李国英,王玉庆,等. 醋酸锌/活性炭催化剂的结构与活性的关系[J]. 催化学报,1986,7(2):155-161. CHEN Shu,LI Guoying,WANG Yuqing,et al. Relation between the activity and structure of zinc acetate/activated carbon catalyst[J]. Chinese Journal of Catalysis,1986,7(2):155-161.
[23] 马秀莲,王琪. VAC催化剂载体的孔结构特性和评价[J]. 燃料化学学报,1986,14(4):88-93. MA Xiulian,WANG Qi. Characterization and evaluation of pore structure of active carbons used as support for VAC catalysis[J]. Journal of Fuel Chemistry and Technology,1986,14(4):88-93.
[24] TEMKIN O N,ABANTO-CHAVEA H I,HOANG K B. Kinetic models of vinyl acetate synthesis on new-generation zinc acetate catalysts[J]. Reaction Kinetics and Catalysis Letters,2000,41:638-654.
[25] 王春明,赵璧英,谢有畅. 盐类和化合物在载体上自发单层分散研究新进展[J]. 催化学报,2003,24(6):475-482. WANG Chunming,ZHAO Biying,XIE Youchang. Advances in the studies of spontaneous monolayer dispersion of oxides and salts on supports[J]. Chinese Journal of Catalysis,2003,24(6):475-482.
[26] XIE Youchang,TANG Youqi. Spontaneous monolayer dispersion of oxides and salts onto surfaces of dupports[J]. Advances in Catalysis,1990,37(17):1-43.
[27] 张以敏,姜浩锡. 超临界流体沉积技术制备负载型金属催化剂的研究进展[J]. 化工进展,2013,32(8):1825-1831. ZHANG Yimin,JIANG Haoxi. Preparation of supported metal catalyst via supercritical fluid deposition[J]. Chemical Industry and Engineering Progress,2013,32(8):1825-1831.
[28] 丁春生,彭芳,卢敬科,等. 改性活性炭的制备表征及吸附Zn²⁺的影响因素[J]. 中国矿业大学学报,2011,40(6):983-989. DING Chunsheng,PENG Fang,LU Jingke,et al. Preparation and characterization of modified activated carbon and their factors on adsorption for Zn²⁺[J]. Journal of China University of Mining & Technology,2011,40(6):983-989.
[29] 方士鑫,段继海,张自生,等. 活性炭的高温处理对醋酸乙烯合成催化剂性能的影响[J]. 当代化工,2015,44(11):2513-2516. FANG Shixin,DUAN Jihai,ZHANG Zisheng,et al. Effect of heat treatment of activated carbon on performance of the catalyst for vinyl acetate synthesis[J]. Contemporary Chemical Industry,2015,44(11):2513-2516.
[30] 饶兰,杨琴,蒋文伟. 竹炭基固体磺酸催化剂的制备及其催化合成癸二酸二丁酯性能研究[J]. 石油炼制与化工,2014,45(5):66-71. RAO Lan,YANG Qin,JIANG Wenwei. Preparation and performance of sulfonated charcoal-based solid acid catalyst for synthesis of dibutyl sabacate[J]. Petroleum Processing and Petrochemicals,2014,45(5):66-71.
[31] 吴学华,包桂蓉,苏有勇,等. 竹炭基固体酸催化剂的制备及其催化性能研究[J]. 化工新型材料,2012,40(4):146-148. WU Xuehua,BAO Guirong,SU Youyong,et al. Preparation and catalyst performance of carbon-based solid acid catalys from bamboo powder[J]. New Chemical Materials,2012,40(4):146-148.
[32] 林风玲,叶李艺,沙勇,等. 两步法制备竹质活性炭[J]. 过程工程学报,2006,6(2):169-172. LIN Fengling,YE Liyi,SHA Yong,et al. Preparation of activated carbon from bamboo sawdust by two-step activation[J]. The Chinese Journal of Process Engineering,2006,6(2):169-172.
[33] 周佳甜,令狐文生. 竹炭的特性及其应用研究进展[J]. 广州化工,2012,40(21):26-62. ZHOU Jiatian,LINGHU Wensheng. The characteristics of bamboo charcoal and its application[J]. Guangzhou Chemical Industry,2012,40(21):26-62.
[34] 郭敏,潘大海,贺敏,等. 负载型铬基催化材料的制备与应用[J]. 化工进展,2013,32(9):2143-2149. GUO Min,PAN Dahai,HE Min,et al. Synthesis and applications of supported Cr-based catalysts[J]. Chemical and Engineering Industry Progress,2013,32(9):2143-2149.
[35] 韩通,赵琳,岳义智,等. 镍基催化剂用于低碳醇合成反应研究进展[J]. 化工进展,2016,35(4):1087-1093. HAN Tong,ZHAO Lin,YUE Yizhi,et al. Progress on the rhodium-based catalysts for the synthesis of higher alcohol[J]. Chemical and Engineering Industry Progress,2016,35(4):1087-1093.
[36] 于政锡. 乙炔气相法合成醋酸乙烯催化剂的研究[D]. 福州:福州大学,2006. YU Zhengxi. Study of zinc acetate/activated carbon catalyst for vinyl acetate synthesis from acetylene[D]. Fuzhou:Fuzhou University,2006.
[37] 李国英,陈曙,王玉庆,等. 醋酸锌/活性炭催化剂孔结构与活性的关系[J]. 石油化工,1984,13(10):649-654. LI Guoying,CHEN Shu,WANG Yuqing,et al. Relation between the activity and pore structure of zinc acetate/activated carbon catalyst[J]. Petrochemical Technology,1984,13(10):649-654.
[38] TOSHIO Kawaguchi,JYUNJI Nakagawa,TOSHIHISA Wakasugi. Method of preparation of an activated carbon supported zinc acetate catalyst[J]. Applied Catalysis,1987,32(1/2):23-36.
[39] 马昌菊. 工业报废Zn/C催化剂失活机理的研究[J]. 金山油化纤,1993(4):1-6. MA Changju. The research on industrial scrap zinc/C catalyst deactivation mechanism[J]. Petrochemical Technology in Jinshan,1993(4):1-6.
[40] MORROW B A. The initialm echanism of vinyl acetate synthesis from acetic acid and acetylene catalyzed by active carbon-zinc acetate[J]. Journal of Catalysis,1984,86:328-332.
[41] 马雅松,刘梦溪. 高温环境下催化裂化催化剂磨损状况的研究[J]. 化学反应工程与工艺,2016,32(1):33-38. MA Yasong,LIU Mengxi. Study on attrition behavior of fluid catalytic cracking catalysts under high temperature[J]. Chemical Reaction Engineering and Technology,2016,32(1):33-38.