nV-MCM-41催化剂的制备及其催化CO2氧化丙烷脱氢反应性能

doi:10.1016/S1872-2067(18)63048-7

催化学报 ›› 2018, Vol. 39 ›› Issue (6): 1099-1109.DOI: 10.1016/S1872-2067(18)63048-7

nV-MCM-41催化剂的制备及其催化CO₂氧化丙烷脱氢反应性能

韩再芳, 薛旭良, 吴建民, 郎万中, 郭亚军

上海师范大学化学化工系, 教育部资源化学重点实验室, 上海市稀土功能材料重点实验室, 上海 200234

收稿日期:2017-12-31 修回日期:2018-02-09 出版日期:2018-06-18 发布日期:2018-05-16
通讯作者: 郎万中
基金资助:
教育部创新团队（PCSIRT_IRT_16R49）；教育部资源化学国际联合实验室.

Preparation and catalytic properties of mesoporous nV-MCM-41 for propane oxidative dehydrogenation in the presence of CO₂

Zai-Fang Han, Xu-Liang Xue, Jian-Min Wu, Wan-Zhong Lang, Ya-Jun Guo

The Education Ministry Key Laboratory of Resource Chemistry and Shanghai Key Laboratory of Rare Earth Functional Materials, Department of Chemistry and Chemical Engineering, Shanghai Normal University, Shanghai 200234, China

Received:2017-12-31 Revised:2018-02-09 Online:2018-06-18 Published:2018-05-16
Contact: 10.1016/S1872-2067(18)63048-7
Supported by:
This work was supported by the Ministry of Education of China (PCSIRT_IRT_16R49) and the International Joint Laboratory on Resource Chemistry (IJLRC).

摘要/Abstract

摘要：

丙烯是一种重要的化工原料，其下游产品丰富，用途广泛，主要用于生产聚丙烯、丙烯腈、丙烯酸和丁醇等化工产品.丙烯的需求正在不断增长，而传统的丙烯生产方法如蒸汽裂解和石油催化裂化，存在反应温度高、积碳严重且丙烯收率较低等问题.因此研制丙烷脱氢制取丙烯的高效催化剂尤为重要.研究发现，以CO₂作为温和氧化剂进行逆水气变换反应可有效促进丙烷脱氢.催化剂主要由活性组分与载体构成，本文选择可用于活化丙烷的钒作为主要活性组分.钒氧化物在载体上的高度分散是提高丙烷脱氢反应活性的关键.MCM-41拥有较大的比表面积和高度有序的介孔结构，可更有效地分散活性位点.本文采用一步法合成了不同钒含量的nV-MCM-41催化剂（1.9-10.6wt%），并研究了其在以下条件下催化丙烷氧化脱氢制丙烯反应性能：600℃，催化剂质量0.2g，进料气体组成C₃H₈/CO₂/Ar （摩尔比）=1/4/4，进料气体总流量15mL/min.其中6.8V-MCM-41催化剂具有最高的活性，其初始丙烷转化率达58%，丙烯选择性达92%，远高于相似反应条件下早期研究的nV-SBA-15催化剂.并在四次反应-再生循环中始终保持其原来的高反应活性.本文借助于N₂吸附-脱附、拉曼光谱（Raman）、X射线光电子能谱（XPS）和热重（TG）等手段探究了不同钒含量的nV-MCM-41催化剂在丙烷脱氢反应中催化性能差异的原因.
氮气吸附-脱附结果表明，所有催化剂都存在典型的高度有序的介孔结构，并没有因为钒组分的掺杂而破坏.nV-MCM-41催化剂拥有较大比表面积，并随钒掺杂量的增加而减小.其中，10.8V-MCM-41催化剂的比表面积急剧下降，可能是由于产生了结晶的V₂O₅阻塞了孔道.Raman结果表明，当钒负载量超过6.8wt%时，出现了V₂O₅的结晶峰.另外根据单分散的四面体钒氧化物的特征峰面积发现，6.8V-MCM-41催化剂中钒物种分散度最高，与其具有最高催化活性结果一致.XPS结果也进一步证明6.8V-MCM-41钒物种的分散度最高.在连续反应过程中6.8V-MCM-41催化剂失活较快，可归结于活性钒位点的还原与催化剂表面的积碳.通过氧化再生，可恢复催化剂活性，并且在4次再生循环中始终保持其良好稳定的活性.

关键词: 丙烷脱氢, 钒氧化物, MCM-41, 介孔载体, 多相催化

Abstract:

The nV-MCM-41 catalysts were prepared by one-step hydrothermal synthesis and applied to the oxidative dehydrogenation of propane (ODHP) in the presence of CO₂. Several state-of-the-art characterization methods were performed to explore the correlation between catalytic performance and the physicochemical characterizations of the catalysts. Because moderate amounts of V species were introduced into the framework of MCM-41, the catalyst maintained a large specific surface area, a highly ordered mesoporous structure, and highly dispersed V active sites (monomeric and dimeric V oxide species), while the high-vanadium-doping catalysts caused an enhancement in the number of acidic sites and V₂O₅ crystallites. The ODHP reaction showed that the 6.8V-MCM-41 (V content 6.8 wt%) catalyst exhibits high activity and stability, and the C₃H₈/CO₂ molar ratio (1:4) was suitable. The promoting effect of CO₂on the oxidative dehydrogenation of ODHP was demonstrated as the reaction coupling mechanism and "lattice oxygen" mechanism.

Key words: Propane dehydrogenation, Vanadium oxide, MCM-41, Mesoporous support, Heterogeneous catalysis

韩再芳, 薛旭良, 吴建民, 郎万中, 郭亚军. nV-MCM-41催化剂的制备及其催化CO₂氧化丙烷脱氢反应性能[J]. 催化学报, 2018, 39(6): 1099-1109.

Zai-Fang Han, Xu-Liang Xue, Jian-Min Wu, Wan-Zhong Lang, Ya-Jun Guo. Preparation and catalytic properties of mesoporous nV-MCM-41 for propane oxidative dehydrogenation in the presence of CO₂[J]. Chinese Journal of Catalysis, 2018, 39(6): 1099-1109.

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nV-MCM-41催化剂的制备及其催化CO₂氧化丙烷脱氢反应性能

Preparation and catalytic properties of mesoporous nV-MCM-41 for propane oxidative dehydrogenation in the presence of CO₂

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