Ce助剂对V/SiO<sub>2</sub>催化CO<sub>2</sub>氧化乙苯脱氢性能的影响

引用本文: 张海新, 陈树伟, 崔杏雨, 潘大海, 秦张峰, 王建国. Ce助剂对V/SiO₂催化CO₂氧化乙苯脱氢性能的影响[J]. 物理化学学报, 2014, 30(2): 351-358. doi: 10.3866/PKU.WHXB201312021 shu

Citation: ZHANG Hai-Xin, CHEN Shu-Wei, CUI Xing-Yu, PAN Da-Hai, QIN Zhang-Feng, WANG Jian-Guo. Effect of Ce Promoter on Catalytic Performance of V/SiO₂ in Oxidative Dehydrogenation of Ethylbenzene with Carbon Dioxide[J]. Acta Physico-Chimica Sinica, 2014, 30(2): 351-358. doi: 10.3866/PKU.WHXB201312021 shu

Ce助剂对V/SiO₂催化CO₂氧化乙苯脱氢性能的影响

基金项目:
国家自然科学基金(51172154)，山西省科技攻关项目(20130313001-3)，煤转化国家重点实验室开放课题基金(J12-13-603) (51172154)，山西省科技攻关项目(20130313001-3)，煤转化国家重点实验室开放课题基金(J12-13-603)

山西省自然科学(青年)基金(2012021006-2)资助 (青年)基金(2012021006-2)

摘要:

通过N₂吸附、X射线衍射(XRD)、X射线光电子能谱(XPS)、H₂程序升温还原(H₂-TPR)、CO₂程序升温脱附(CO₂-TPD)和热重分析(TGA)等多种表征手段和催化反应性能评价，研究了铈助剂的添加对V/SiO₂催化CO₂氧化乙苯脱氢性能的影响. 结果表明，Ce助剂不仅提高了催化剂活性组分分散性和氧化还原性能，抑制了钒物种的深度还原，而且增强了催化剂碱性和CO₂吸附能力，减缓了积炭生成，从而显著提高了V-Ce/SiO₂对CO₂氧化乙苯脱氢反应的催化活性和稳定性. 在本实验中，V(0.8)-Ce(0.25)/SiO₂催化剂表现出最佳的催化性能，苯乙烯(ST)收率可达55.6%，选择性为98.5%，反应12 h 后，催化剂活性基本不变，与惰性N₂气氛比较，CO₂明显促进了乙苯脱氢反应，归因于CO₂能保持催化剂表面钒物种的高价态.

关键词:

English

Effect of Ce Promoter on Catalytic Performance of V/SiO₂ in Oxidative Dehydrogenation of Ethylbenzene with Carbon Dioxide

1.
1 College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, P. R. China;
2 State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, P. R. China;
3 Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan 030024, P. R. China
Received Date: 06 August 2013
Available Online: 23 January 2014
Fund Project:
国家自然科学基金(51172154)，山西省科技攻关项目(20130313001-3)，煤转化国家重点实验室开放课题基金(J12-13-603)

山西省自然科学(青年)基金(2012021006-2)资助

Abstract:

The effect of a Ce promoter on the catalytic properties of V/SiO₂ was investigated for the oxidative dehydrogenation of ethylbenzene (EB) to styrene (ST) with CO₂ (CO₂-ODEB). The catalysts were characterized by nitrogen adsorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), H₂ temperature-programmed reduction (H₂-TPR), CO₂ temperature-programmed desorption (CO₂-TPD), and thermogravimetric analyses (TGA). It was found that incorporation of Ce into V/SiO₂ increased the dispersion of active V species, enhanced the redox properties of the system, and inhibited deep V reduction of V⁵⁺ to V³⁺ . The Ce promoter also improves the basicity of V/SiO₂ and CO₂ adsorption on the catalyst, and suppresses coke formation. The addition of a Ce promoter greatly improves the catalytic activity and stability of V/SiO₂ towards CO₂-ODEB. The ST yield and selectivity reach 55.6% and 98.5%, respectively, for CO₂-ODEB over the most efficient catalyst, V(0.8)Ce(0.25)/SiO₂, at 550℃, and a CO₂/EB molar ratio of 20. Moreover, after reaction for 12 h, the V(0.8)Ce(0.25)/SiO₂ still shows stable catalytic activity. The ST yield in CO₂ is higher than that in an inert N₂ atmosphere, showing the significant promoting effect of CO₂ on EB dehydrogenation; this is because CO₂ is a soft oxidant and can effectively keep/regain the high valence of V for high activity with CO₂-ODEB.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

Ce助剂对V/SiO₂催化CO₂氧化乙苯脱氢性能的影响

English

Effect of Ce Promoter on Catalytic Performance of V/SiO₂ in Oxidative Dehydrogenation of Ethylbenzene with Carbon Dioxide

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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Ce助剂对V/SiO2催化CO2氧化乙苯脱氢性能的影响

English

Effect of Ce Promoter on Catalytic Performance of V/SiO2 in Oxidative Dehydrogenation of Ethylbenzene with Carbon Dioxide

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

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

Ce助剂对V/SiO₂催化CO₂氧化乙苯脱氢性能的影响

Effect of Ce Promoter on Catalytic Performance of V/SiO₂ in Oxidative Dehydrogenation of Ethylbenzene with Carbon Dioxide

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs