氧扩散与表面反应在VOx-Ce1‒xZrxO2催化丙烷脱氢反应中的影响

doi:10.1016/S1872-2067(23)64494-8

催化学报 ›› 2023, Vol. 52: 217-227.DOI: 10.1016/S1872-2067(23)64494-8

氧扩散与表面反应在VO_x-Ce_1‒_xZr_xO₂催化丙烷脱氢反应中的影响

孙嘉辰^a^,^b, 陈赛^a^,^b^,^c, 付东龙^a^,^b, 王伟^a^,^b^,^c, 王显辉^a^,^b, 孙国栋^a^,^b, 裴春雷^a^,^b^,^*(), 赵志坚^a^,^b^,^*(), 巩金龙^a^,^b^,^c^,^d^,^e

^a天津大学化工学院, 绿色合成与转化教育部重点实验室, 天津300072
^b天津化工协同创新中心, 天津300072
^c天津大学滨海新城国际校区, 新加坡国立大学与天津大学联合学院, 福建福州350207
^d物质绿色创造与制造海河实验室, 天津300192
^e天津大学国家储能技术产教融合创新平台, 天津300350

收稿日期:2023-05-30 接受日期:2023-07-19 出版日期:2023-09-18 发布日期:2023-09-25
通讯作者: *电子信箱: chunlei.pei@tju.edu.cn (裴春雷),zjzhao@tju.edu.cn (赵志坚).
基金资助:
国家重点研发计划(2021YFA1501302);国家自然科学基金(22121004);国家自然科学基金(22122808);物质绿色创造与制造海河实验室(CYZC202107);高校学科人才引进计划(BP0618007);科学探索奖

Role of oxygen transfer and surface reaction in catalytic performance of VO_x-Ce_1‒_xZr_xO₂ for propane dehydrogenation

Jiachen Sun^a^,^b, Sai Chen^a^,^b^,^c, Donglong Fu^a^,^b, Wei Wang^a^,^b^,^c, Xianhui Wang^a^,^b, Guodong Sun^a^,^b, Chunlei Pei^a^,^b^,^*(), Zhi-Jian Zhao^a^,^b^,^*(), Jinlong Gong^a^,^b^,^c^,^d^,^e

^aKey Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering & Technology, Tianjin University, Tianjin 300072, China
^bCollaborative Innovation Center for Chemical Science & Engineering (Tianjin), Tianjin 300072, China
^cJoint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, Fuzhou 350207, Fujian, China
^dHaihe Laboratory of Sustainable Chemical Transformations, Tianjin 300192, China
^eNational Industry-Education Platform of Energy Storage, Tianjin University, Tianjin 300350, China

Received:2023-05-30 Accepted:2023-07-19 Online:2023-09-18 Published:2023-09-25
Contact: *E-mail: chunlei.pei@tju.edu.cn (C. Pei),zjzhao@tju.edu.cn (Z. Zhao).
Supported by:
National Key R&D Program of China(2021YFA1501302);National Natural Science Foundation of China(22121004);National Natural Science Foundation of China(22122808);Haihe Laboratory of Sustainable Chemical Transformations(CYZC202107);Introducing Talents of Discipline to Universities(BP0618007);XPLORER PRIZE

摘要/Abstract

摘要：

丙烯是一种重要的化工原料, 近年来市场需求逐年上升. 丙烷直接脱氢(PDH)生产丙烯技术虽然已实现工业化应用, 但其存在反应热力学不利、催化剂成本高及使用有毒铬系催化剂等问题. 丙烷氧化脱氢(ODH)由于过度氧化严重和存在操作风险等问题阻碍了其实际应用. 化学链丙烷脱氢(CL-ODH)技术采用低成本且环境友好的可还原金属氧化物作为氧载体(氧化还原催化剂), 并利用更高效的晶格氧作为氧化剂替代传统ODH过程中的氧气, 在改善丙烷脱氢反应热力学限制的同时抑制了烷烃分子的过度氧化. 氧化还原催化剂在该过程中发挥着重要的作用, 其设计得到了研究者们的广泛关注. 目前, 铈锆储氧材料担载的钒催化剂由于在烷烃选择性氧化以及储氧能力方面的优势, 在CL-ODH领域展示出良好的应用前景. 然而, 由于体相氧传输和表面反应共同决定氧化还原催化剂的性能, 因此深入探究两者在反应过程中的作用机制对于高性能催化剂的开发至关重要.

本文构建了结构明确的VO_x-Ce_1‒_xZr_xO₂氧化还原催化剂并应用于CL-ODH反应, 通过引入Zr调控催化剂的表面和体相性质, 进而对其表面反应活性和体相供氧能力进行调节. 其中, VO_x-Ce_0.3Zr_0.7O₂样品表现出相对较高的丙烯生成速率(5.07 mmol·g_cat^‒1 h^‒1). H₂程序升温还原和C₃H₈程序升温还原结果表明, Zr的引入增强了氧化还原催化剂的低温体相供氧能力以及表面本征活性, 因此增加了活性氧物种的数量并促进了表面丙烷分子的活化. 动力学实验结果表明, VO_x-Ce_1‒_xZr_xO₂氧化还原催化剂上的脱氢反应遵循一级反应动力学规律, 说明表面反应为催化剂还原过程的速控步骤, 同时, 在快速的体相氧扩散作用下, 催化剂内部的氧物种呈现均匀分布的特点. 进一步分析表面反应过程和体相氧传输对于氧化还原催化剂表面氧物种覆盖度的影响, 建立了描述VO_x-Ce_1‒_xZr_xO₂在脱氢阶段反应模型的动力学方程. 其中, 吸附态丙烷分子的C‒H键断裂是表面反应的速控步骤, Zr的引入可以有效降低该步骤的活化能, 进而提高了氧化还原催化剂在给定表面氧物种覆盖度时对应的表面反应速率. 同时, 随着反应的进行, 为了消除VO_x_-Ce_1‒_xZr_xO₂内部产生的氧浓度梯度, 氧扩散起到了将表面反应产生的氧空位快速转移到体相的作用, 从而有效地保持了反应过程中表面活性氧的覆盖度. 并且随着Zr的引入, Ce_1‒_xZr_xO₂的储氧能力得以增强, 可容纳更多来自表面的氧空位, 从而使表面氧化活性保持更长时间. 此外, 通过拉曼光谱、X射线光电子能谱和原位漫反射红外傅立叶变换光谱等多种原位表征技术对上述反应模型进行了验证.

综上, 本文为V基氧化还原催化剂应用于CL-ODH反应过程中氧扩散和表面反应的作用提供了更深入的认识, 并为高性能氧化还原催化剂的设计提供了理论参考.

关键词: 丙烷脱氢, V基催化剂, 氧化还原化学, 表面反应, 晶格氧扩散

Abstract:

The bulk oxygen transfer and surface reaction as important parts of the chemical looping-related process are crucial for the rational design of new redox catalysts. This paper describes an experimental study on the effect of bulk oxygen transfer and surface reaction in Ce_1‒_xZr_xO₂ supported VO_x redox catalysts for the chemical looping oxidative propane dehydrogenation reaction. It was found that the introduction of Zr dictates the reaction performance of the redox catalyst by modulating the bulk oxygen transfer and surface reaction. The kinetic study reveals that the instantaneous reduction rate of the redox catalysts is determined by the H-abstraction step in the surface reaction. The introduction of Zr can reduce the activation energy of the H-abstraction step, which leads to the enhancement of the instantaneous reduction rate. Meanwhile, the oxygen supply capacity of the cerium oxide is increased by Zr, allowing the surface reaction to proceed over longer durations. Furthermore, the reaction model derived from the kinetics study is validated using a number of (quasi) in situ techniques. This study provides fundamental insights into the role of bulk oxygen transfer and surface reaction in chemical looping or related process.

Key words: Propane dehydrogenation, Vanadia catalyst, Redox chemistry, Surface reaction, Bulk diffusion

孙嘉辰, 陈赛, 付东龙, 王伟, 王显辉, 孙国栋, 裴春雷, 赵志坚, 巩金龙. 氧扩散与表面反应在VO_x-Ce_1‒_xZr_xO₂催化丙烷脱氢反应中的影响[J]. 催化学报, 2023, 52: 217-227.

Jiachen Sun, Sai Chen, Donglong Fu, Wei Wang, Xianhui Wang, Guodong Sun, Chunlei Pei, Zhi-Jian Zhao, Jinlong Gong. Role of oxygen transfer and surface reaction in catalytic performance of VO_x-Ce_1‒_xZr_xO₂ for propane dehydrogenation[J]. Chinese Journal of Catalysis, 2023, 52: 217-227.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64494-8

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图/表 5

Fig. 1. Structure characterizations of V-Ce1-xZrxO2 redox catalysts with different Zr contents. (a) XRD patterns. (b) 532 nm excited Raman specrta of the dehydrated V-Ce1-xZrxO2. (c) Vanadyl stretching region of 532 nm Raman spectra. (d) Illustration of structural for V-Ce1-xZrxO2. (e) The XPS spectra of V 2p3/2. (f) HRTEM and EDS-STEM images of V-Ce0.3Zr0.7O2.

Fig. 2. Comparisons of propane dehydrogenation over V-Ce1-xZrxO2 redox catalysts with different Zr contents. (a) Propane conversion and propylene selectivity as a function of reaction time. (b) Contribution of ODH in propylene formation. Test conditions: 600 °C, 1.4 atmospheric pressure, WHSV = 1 h-1, 0.5 g sample, C3H8/N2 = 4:21.

Fig. 3. Temperature programmed reduction and reaction of V-Ce1-xZrxO2 redox catalysts with different Zr contents. (a) H2-TPR profiles of V-Ce1-xZrxO2 (solid lines) and pure Ce1-xZrxO2 (dash lines). (b) The H2O signal of V-Ce1-xZrxO2 during C3H8-TPR.

Fig. 4. Effects of bulk oxygen transfer and surface reaction on surface oxygen coverage of V-Ce1-xZrxO2. (a) Experimental data and kinetics ftting (dashed lines) for the reduction of V-Ce1-xZrxO2 by C3H8. (b) Oxygen coverage as a function of the reaction time. (c) Dependencies of the rate constant for the first cleavage of the C-H step (k2) on the temperature. (d) Proposed reaction model over V-Ce1-xZrxO2 during dehydrogenation stage.

Fig. 5. Structural evolution of VOx over V-Ce1-xZrxO2 redox catalysts during propane dehydrogenation reaction. In situ DRIFTS spectrum of V-CeO2 (a), V-Ce0.5Zr0.5O2 (b), V-Ce0.3Zr0.7O2 (c) and V-ZrO2 (d). (e) The time profile of the normalized intensity of V=O. (f) The calculated intensity ratios of Ce3+/V=O.

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氧扩散与表面反应在VO_x-Ce_1‒_xZr_xO₂催化丙烷脱氢反应中的影响

Role of oxygen transfer and surface reaction in catalytic performance of VO_x-Ce_1‒_xZr_xO₂ for propane dehydrogenation

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