气相法合成偏二氯乙烯的高稳定CsNO<sub>3</sub>/SiO<sub>2</sub>催化剂

引用本文: 靳燕霞, 汤岑, 孟秀清, 王小霞, 谢冠群, 罗孟飞, 李小年. 气相法合成偏二氯乙烯的高稳定CsNO₃/SiO₂催化剂[J]. 物理化学学报, 2016, 32(2): 510-518. doi: 10.3866/PKU.WHXB201511134 shu

Citation: JIN Yan-Xia, TANG Cen, MENG Xiu-Qing, WANG Xiao-Xia, XIE Guan-Qun, LUO Meng-Fei, LI Xiao-Nian. Highly Stable CsNO₃/SiO₂ Catalysts for the Synthesis of Vinylidene Chloride Using a Gaseous Phase Method[J]. Acta Physico-Chimica Sinica, 2016, 32(2): 510-518. doi: 10.3866/PKU.WHXB201511134 shu

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.
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

通讯作者: 谢冠群, 罗孟飞; 谢冠群, 罗孟飞

基金项目:
国家自然科学基金(21476207) (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)资助项目 (ZJHX201413)

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:

English

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

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.
2 State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology, Industrial Catalysis Institute, Zhejiang University of Technology, Hangzhou 310032, P. R. China

Corresponding author: 谢冠群, 罗孟飞; 谢冠群, 罗孟飞

Received Date: 14 September 2015
Fund Project:
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)资助项目

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:

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沈阳化工大学材料科学与工程学院沈阳 110142

气相法合成偏二氯乙烯的高稳定CsNO₃/SiO₂催化剂

通讯作者: 谢冠群, 罗孟飞; 谢冠群, 罗孟飞

English

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

Corresponding author: 谢冠群, 罗孟飞; 谢冠群, 罗孟飞

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CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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中国化学会秘书处

气相法合成偏二氯乙烯的高稳定CsNO3/SiO2催化剂

通讯作者: 谢冠群, 罗孟飞; 谢冠群, 罗孟飞

English

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

Corresponding author: 谢冠群, 罗孟飞; 谢冠群, 罗孟飞

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

气相法合成偏二氯乙烯的高稳定CsNO₃/SiO₂催化剂

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

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