V2O5/MO-Al2O3 (M = Mg, Ca, Sr, Ba)催化剂用于正丁烷催化氧化脱氢反应

doi:10.1016/S1872-2067(15)60839-7

催化学报 ›› 2015, Vol. 36 ›› Issue (7): 1060-1067.DOI: 10.1016/S1872-2067(15)60839-7

V₂O₅/MO-Al₂O₃ (M = Mg, Ca, Sr, Ba)催化剂用于正丁烷催化氧化脱氢反应

徐兵^a,b, 朱雪峰^b, 曹中卫^a,b, 杨丽娜^a, 杨维慎^b

a 辽宁石油化工大学石油化工学院, 辽宁抚顺113001;
b 中国科学院大连化学物理研究所催化基础国家重点实验室, 辽宁大连116023

收稿日期:2015-02-14 修回日期:2015-03-23 出版日期:2015-06-12 发布日期:2015-07-30
通讯作者: 朱雪峰电话: (0411)84379301; 传真: (0411)84694447; 电子信箱: zhuxf@dicp.ac.cn; 杨丽娜电话: (024)56865618; 传真: (024) 56861709; 电子信箱: lnqdsd@aliyun.com
基金资助:
延长石油.

Catalytic oxidative dehydrogenation of n-butane over V₂O₅/MO-Al₂O₃ (M = Mg, Ca, Sr, Ba) catalysts

Bing Xu^a,b, Xuefeng Zhu^b, Zhongwei Cao^a,b, Lina Yang^a, Weishen Yang^b

a School of Petrochemical Engineering, Liaoning Shihua University, Fushun 113001, Liaoning, China;
b State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China

Received:2015-02-14 Revised:2015-03-23 Online:2015-06-12 Published:2015-07-30

摘要/Abstract

摘要：

采用浸渍法制备了不同V₂O₅担载量的V₂O₅/MO-Al₂O₃ (M = Mg, Ca, Sr, Ba)催化剂, 钒物种的前驱体为偏钒酸铵. 对制备的催化剂进行了一系列表征, 并对催化剂上正丁烷选择性氧化脱氢制取丁烯进行了反应研究. 表征结果(包括比表面积、X射线衍射、傅里叶红外光谱、氢气程序升温还原和拉曼光谱)显示, 不同碱土金属元素掺杂的催化剂显示不同的钒价态信息和催化性能. 其中掺杂Ca, Sr, Ba的催化剂, 正钒酸盐相很难被还原, 因此催化剂的氧化还原循环难以建立, 导致以上三种催化剂在正丁烷氧化脱氢反应中活性较低. 然而, Mg掺杂的催化剂却显示出较高的催化活性和选择性. 实验结果表明: 在Mg掺杂的载体上担载5% V₂O₅的催化剂上600 ℃时可获得高达30.3%的正丁烷转化率和64.3%的烯烃总选择性. 这与V₂O₅担载量为5%时, 在获得高度分散的钒氧化合物物种时可使MgO晶相稳定存在密切相关.

关键词: 氧化脱氢, 正丁烷, 丁烯, 氧化镁, 氧化铝, 钒基催化剂

Abstract:

V₂O₅/MO-Al₂O₃ (M = Mg, Ca, Sr, Ba) catalysts with different V₂O₅ loading were prepared by impregnation with ammonium metavanadate as the V precursor and characterized and tested for the selectively oxidative dehydrogenation of n-butane to butenes. Characterization by BET, XRD, FTIR, H₂-TPR and Raman spectra showed that the catalysts doped with different alkaline earth metals had different structure and catalytic activity. The catalysts doped with Ca, Sr or Ba had the orthovanadate phase that was difficult to reduce, so their redox cycles could not be established and they exhibited low activity. The catalysts doped with Mg showed high catalytic activity and selectivity. The catalyst with 5% V₂O₅ loading exhibited the highest n-butane conversion (30.3%) and total butene selectivity (64.3%) at 600 ℃. This was due to the well dispersed VO_x species and the existence of the MgO crystalline phase, which were both present at a V₂O₅ loading of 5%.

Key words: Oxidative dehydrogenation, n-Butane, Butene, Magnesia, Alumina, Vanadium catalyst

徐兵, 朱雪峰, 曹中卫, 杨丽娜, 杨维慎. V₂O₅/MO-Al₂O₃ (M = Mg, Ca, Sr, Ba)催化剂用于正丁烷催化氧化脱氢反应[J]. 催化学报, 2015, 36(7): 1060-1067.

Bing Xu, Xuefeng Zhu, Zhongwei Cao, Lina Yang, Weishen Yang . Catalytic oxidative dehydrogenation of n-butane over V₂O₅/MO-Al₂O₃ (M = Mg, Ca, Sr, Ba) catalysts[J]. Chinese Journal of Catalysis, 2015, 36(7): 1060-1067.

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V₂O₅/MO-Al₂O₃ (M = Mg, Ca, Sr, Ba)催化剂用于正丁烷催化氧化脱氢反应

Catalytic oxidative dehydrogenation of n-butane over V₂O₅/MO-Al₂O₃ (M = Mg, Ca, Sr, Ba) catalysts

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