物理化学学报 >> 2016, Vol. 32 >> Issue (2): 510-518.doi: 10.3866/PKU.WHXB201511134

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气相法合成偏二氯乙烯的高稳定CsNO3/SiO2催化剂

靳燕霞1,汤岑1,孟秀清1,王小霞1,谢冠群1,2,*(),罗孟飞1,*(),李小年2   

  1. 1 浙江师范大学物理化学研究所, 先进催化材料教育部重点实验室, 浙江金华 321004
    2 浙江工业大学工业催化研究所, 绿色化学合成技术国家重点实验室培育基地, 杭州 310032
  • 收稿日期:2015-09-14 发布日期:2016-01-30
  • 通讯作者: 谢冠群,罗孟飞 E-mail:gqxie@zjnu.edu.cn;mengfeiluo@zjnu.cn
  • 基金资助:
    国家自然科学基金(21476207);浙江师范大学浙江省省属高校化学重中之重学科和先进催化材料教育部重点实验室开放课题基金(ZJHX201413)

Highly Stable CsNO3/SiO2 Catalysts for the Synthesis of Vinylidene Chloride Using a Gaseous Phase Method

Yan-Xia JIN1,Cen TANG1,Xiu-Qing MENG1,Xiao-Xia WANG1,Guan-Qun XIE1,2,*(),Meng-Fei LUO1,*(),Xiao-Nian LI2   

  1. 1 Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua 321004, Zhejiang Province, P. R. China
    2 State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology, Industrial Catalysis Institute, Zhejiang University of Technology, Hangzhou 310032, P. R. China
  • Received:2015-09-14 Published:2016-01-30
  • Contact: Guan-Qun XIE,Meng-Fei LUO E-mail:gqxie@zjnu.edu.cn;mengfeiluo@zjnu.cn
  • Supported by:
    the National Natural Science Foundation of China(21476207);Open Research Fund of Top Key Discipline ofChemistry in Zhejiang Provincial Colleges, China, and Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, China(ZJHX201413)

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摘要：

用浸渍法制备CsNO3/SiO2催化剂,用于气相催化裂解1, 1, 2-三氯乙烷(TCE)制偏二氯乙烯(VDC)反应,考察了反应温度对CsNO3/SiO2催化剂失活的影响。研究发现,在较低反应温度( < 350 ℃)时, CsNO3/SiO2催化剂容易失活,在较高反应温度(> 400 ℃)时催化剂的活性较高且不易失活。反应后CsNO3/SiO2催化剂中CsNO3物种转变为CsCl,催化剂表面存在积炭。导致催化剂失活的主要原因不是Cs物种转变和积炭,而是含氯反应产物在低温反应时难以从催化剂表面脱附。这些含氯反应产物能够高温脱附,从而使低温反应失活的催化剂再生。CsNO3/SiO2催化剂在400 ℃下100 h寿命实验中, TCE转化率和VDC选择性分别稳定为98%和78%,具有较好的工业应用前景。

关键词: 偏二氯乙烯, 1, 1, 2-三氯乙烷, CsNO3, 脱氯化氢反应, 多相反应

Abstract:

CsNO3/SiO2 catalysts were prepared using an impregnation method, and were applied in the vapor phase catalytic synthesis of vinylidene chloride (VDC) from 1, 1, 2-trichloroethane (TCE). The influence of reaction temperature on the deactivation of CsNO3/SiO2 catalysts was investigated in detail. It was found that low reaction temperatures ( < 350 ℃) lead to a rapid deactivation, while high reaction temperatures (> 400 ℃) result in a high and stable catalytic activity. During the dehydrochlorination process, CsNO3 species were transformed into CsCl, and coke was formed and deposited on the catalyst surface. However, the chemical change of the Cs species and deposited coke were not the main reason for the deactivation of CsNO3/SiO2 catalyst. Some chlorine-containing species (organic products or HCl) were formed during the reaction and were difficult to desorb from the catalyst surface, which accounts for the deactivation of CsNO3/SiO2 catalysts at low reaction temperatures. High temperature treatment (550 ℃) in a non-oxidizing atmosphere could remove the contaminants and regenerate the catalysts completely. The life test of CsNO3/SiO2 catalyst was carried out at 400 ℃ for 100 h. The TCE conversion and the selectivity to VDC remained stable at 98% and 78%, respectively, showing good prospect for industrial applications.

Key words: Vinylidenechloride, 1, 1, 2-Trichloroethane, CsNO3, Dehydrochlorination, Heterogeneous reaction