碱金属助剂对CoCu/TiO2催化剂上二氧化碳加氢合成长链烃的影响

doi:10.1016/S1872-2067(18)63086-4

催化学报 ›› 2018, Vol. 39 ›› Issue (8): 1294-1302.DOI: 10.1016/S1872-2067(18)63086-4

• 第十五届国际二氧化碳利用会议专栏 • 上一篇下一篇

碱金属助剂对CoCu/TiO₂催化剂上二氧化碳加氢合成长链烃的影响

石志彪^a,b, 杨海艳^b, 高鹏^b, 陈新庆^b, 刘洪江^a, 钟良枢^b,c, 王慧^b, 魏伟^b,c, 孙予罕^b,c

a 上海大学理学院化学系, 上海 200444;
b 中国科学院上海高等研究院, 中科院低碳转化科学与工程重点实验室, 上海 201210;
c 上海科技大学物质学院, 上海 201210

收稿日期:2018-03-18 修回日期:2018-04-23 出版日期:2018-08-18 发布日期:2018-07-04
通讯作者: 高鹏, 王慧
基金资助:
荷兰皇家壳牌集团前瞻科学基金（PT65197）；国家自然科学基金（21773286，21503260，21776296）；中国科学院青年创新促进会（20178330）；中国科学院洁净能源先导科技专项资助（XDA21090204）；上海市科学技术委员会（16DZ1206900）.

Effect of alkali metals on the performance of CoCu/TiO₂ catalysts for CO₂ hydrogenation to long-chain hydrocarbons

Zhibiao Shi^a,b, Haiyan Yang^b, Peng Gao^b, Xinqing Chen^b, Hongjiang Liu^a, Liangshu Zhong^b,c, Hui Wang^b, Wei Wei^b,c, Yuhan Sun^b,c

a Department of chemistry, College of Sciences, Shanghai University, Shanghai 200444, China;
b CAS Key Laboratory of Low-Carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, China;
c School of physical Science and Technology, ShanghaiTech University, Shanghai 201210, China

Received:2018-03-18 Revised:2018-04-23 Online:2018-08-18 Published:2018-07-04
Contact: 10.1016/S1872-2067(18)63086-4
Supported by:
This work was supported by the "Frontier Science" Program of Shell Global Solutions International B. V. (PT65197), the National Natural Science Foundation of China (21773286, 21503260, 21776296), Youth Innovation Promotion Association CAS (20178330), the "Transformational Technologies for Clean Energy and Demonstration", Strategic Priority Research Program of the Chinese Academy of Sciences (XDA21090204), and Shanghai Municipal Science and Technology Commission, China (16DZ1206900).

摘要/Abstract

摘要：

大气中CO₂浓度增加导致的温室效应以及化石燃料的匮乏正日益受到世界范围的关注.由于CO₂较强的惰性以及较高C-C偶联能垒，迄今为止大部分研究都集中在CO₂催化加氢制备各种C1化学品（如CH₄，CH₃OH，CO等），鲜有研究关注合成液态燃料（C₅₊碳氢化合物）.目前，CO₂加氢直接合成烃类主要通过CO₂基费托合成反应（CO₂-FTS）实现，即先通过逆水煤气变换反应（RWGS）将CO₂还原成CO，随后CO通过传统费托反应（FTS）加氢生成烃类化合物.在两种工业化FTS催化剂（Fe和Co基催化剂）中，钴基催化剂具有更高的反应活性和链增长能力，以及较高的机械强度和稳定性.然而，由于CO₂的惰性，造成催化剂表面物种的加氢程度更高，使得甲烷更容易生成.因而，高反应活性、高选择性催化剂的开发是实现该过程的关键.
本文采用沉积沉淀法制备了一系列双金属CoCu/TiO₂催化剂，再通过初湿浸渍法对其进行碱金属助剂（Li，Na，K，Rb和Cs）改性，并用多种表征手段系统研究了碱金属助剂对催化剂物化性质及其催化CO₂加氢制备长链烃反应的影响.结果表明，碱金属的加入对催化剂织构性质影响不大，它们在催化剂表面发生富集，且富集程度随碱金属原子序数的增加而降低.另外，碱金属的加入增强了CO₂的吸附，其中，Na改性的CoCu/TiO₂催化剂的碱性最强；同时还降低了H₂的脱附量，尤以K，Rb和Cs改性的催化剂为甚.
在250℃，5MPa，空速3000mL·g_cat^-1·h^-1和H₂/CO₂=3的反应条件下，对不同碱金属助剂改性的催化剂进行评价.结果表明，不加助剂的CoCu/TiO₂催化剂上CO₂转化率高达23.1%，但产物主要是CH₄，此时CO₂在Co活性中心上直接发生甲烷化反应；碱金属助剂的引入显著抑制了CH₄的生成，提高了长链烃的选择性，但同时也降低了CO₂转化率，并且随着碱金属原子序数增大呈现先下降后上升的趋势，表明合适的碱性强度可以更好地改性催化剂性能.其中，Na助剂改性的CoCu/TiO₂催化剂的碱性最强，且H₂的脱附量降低幅度较小，因此，该催化剂具有最高的C₅₊烃类收率，达到5.4%；同时CO₂转化率为18.4%，烃类产物中C₅₊烃类选择性为42.1%.Na助剂改性的CoCu/TiO₂催化剂还展现了良好的催化稳定性，反应200h后，CO₂转化率和C₅₊选择性分别保持18%和40%.基于碱金属助剂对催化剂物化性质与反应性能的调变规律，可进一步指导CO₂加氢直接合成长链碳催化剂的设计与合成.

关键词: 二氧化碳加氢, 长链烃, 二氧化碳费托合成, 碱金属助剂, 钴-铜基催化剂

Abstract:

CoCu/TiO₂ catalysts promoted using alkali metals (Li, Na, K, Rb, and Cs) were prepared by the homogeneous deposition-precipitation method followed by the incipient wetness impregnation method. The influences of the alkali metals on the physicochemical properties of the CoCu/TiO₂ catalysts and the catalytic performance for CO₂ hydrogenation to long-chain hydrocarbons (C₅₊) were investigated in this work. According to the characterization of the catalysts based on X-ray photoelectron spectroscopy, X-ray diffraction, CO₂ temperature-programmed desorption (TPD), and H₂-TPD, the introduction of alkali metals could increase the CO₂ adsorption and decrease the H₂ chemisorption, which could suppress the formation of CH₄, enhance the production of C₅₊, and decrease the hydrogenation activity. Among all the promoters, the Na-modified CoCu/TiO₂ catalyst provided the maximum C₅₊ yield of 5.4%, with a CO₂ conversion of 18.4% and C₅₊ selectivity of 42.1%, because it showed the strongest basicity and a slight decrease in the amount of H₂ desorption; it also exhibited excellent catalytic stability of more than 200 h.

Key words: Carbon dioxide hydrogenation, Long-chain hydrocarbons, Carbon dioxide Fischer-Tropsch synthesis, Alkali metal promoters, Cobalt-copper based catalysts

石志彪, 杨海艳, 高鹏, 陈新庆, 刘洪江, 钟良枢, 王慧, 魏伟, 孙予罕. 碱金属助剂对CoCu/TiO₂催化剂上二氧化碳加氢合成长链烃的影响[J]. 催化学报, 2018, 39(8): 1294-1302.

Zhibiao Shi, Haiyan Yang, Peng Gao, Xinqing Chen, Hongjiang Liu, Liangshu Zhong, Hui Wang, Wei Wei, Yuhan Sun. Effect of alkali metals on the performance of CoCu/TiO₂ catalysts for CO₂ hydrogenation to long-chain hydrocarbons[J]. Chinese Journal of Catalysis, 2018, 39(8): 1294-1302.

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碱金属助剂对CoCu/TiO₂催化剂上二氧化碳加氢合成长链烃的影响

Effect of alkali metals on the performance of CoCu/TiO₂ catalysts for CO₂ hydrogenation to long-chain hydrocarbons

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