Chemical Industry and Engineering Progress ›› 2016, Vol. 35 ›› Issue (11): 3524-3528.DOI: 10.16085/j.issn.1000-6613.2016.11.021

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Catalytic hydrogenation of diethyl malonate into 1,3-propanediol on Cu/HMS catalyst

WU Wenbin, DING Tongmei, TIAN Hengshui   

  1. Department of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
  • Received:2016-02-29 Revised:2016-04-08 Online:2016-11-05 Published:2016-11-05

Cu/HMS催化剂上丙二酸二乙酯催化加氢制备1,3-丙二醇

吴文滨, 丁同梅, 田恒水   

  1. 华东理工大学化工学院, 上海 200237
  • 通讯作者: 田恒水,教授,博士生导师,研究方向为绿色化工、清洁工艺生产。E-mail:hstian@ecust.edu.cn。
  • 作者简介:吴文滨(1990-),男,硕士研究生。E-mail:w551wb@163.com。

Abstract: 1,3-propanediol was synthesized without generating aldehyde by-products by catalytic hydrogenation of diethyl malonate over Cu/HMS catalyst in a continuous high pressure fixed-bed reactor.Effects of raw material concentration, ratio of H2/DEM, liquid hourly space velocity, reaction temperature and reaction pressure on the hydrogenation reaction were investigated. And the main causes of the catalyst deactivation were analyzed by XRD and TEM characterizations.Under the condition of raw material concentration as 7.5wt%, ratio of H2/DEM as 400, liquid hourly space velocity as 1.8h-1, reaction temperature as 200℃ and reaction pressure as 1.8MPa, the catalyst showed good catalytic hydrogenation performance, and diethyl malonate conversion and 1,3-propanediol yield reached 93.4% and 52.8%, respectively.The catalyst was deactivated completely after 120h.From both XRD and TEM results, the main causes for the catalyst deactivation were considered as the agglomeration of particles, loss of active components or the partial oxidation to Cu+

Key words: Cu/HMS, diethyl malonate, 1,3-propanediol, catalyst, hydrogenation

摘要: 目前工业上生产1,3-丙二醇的方法存在一定局限性,为了开发出避免醛类副产物生成的1,3-丙二醇合成工艺,在高压连续固定床反应器上,以丙二酸二乙酯为原料,使用Cu/HMS催化剂催化加氢制备1,3-丙二醇。考察了原料液浓度、氢酯摩尔比、液时空速、反应温度、反应压力对反应的影响,之后进一步考察了催化剂的稳定性,并通过XRD及TEM表征分析了催化剂失活的主要原因。结果表明:在原料液质量分数7.5%、氢酯摩尔比400、液时空速1.8h-1、反应温度200℃、反应压力1.8MPa的工艺条件下,催化剂表现出了较佳的催化加氢性能,丙二酸二乙酯转化率为93.4%,1,3-丙二醇收率可达到52.8%。反应120h后催化剂完全失活,结合XRD及TEM表征,认为粒径增大、活性组分流失或被部分氧化为Cu+是催化剂失活的主要原因。

关键词: Cu/HMS, 丙二酸二乙酯, 1,3-丙二醇, 催化剂, 加氢

CLC Number: 

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