不同硅铝比ZSM-5负载铁基催化剂二氧化碳加氢性能

doi:10.11949/j.issn.0438-1157.20160905

化工学报 ›› 2017, Vol. 68 ›› Issue (2): 670-678.DOI: 10.11949/j.issn.0438-1157.20160905

• 催化、动力学与反应器 • 上一篇下一篇

不同硅铝比ZSM-5负载铁基催化剂二氧化碳加氢性能

邵光印, 张玉龙, 张征湃, 张俊, 苏俊杰, 刘达, 赫崇衡, 徐晶, 韩一帆

化学工程联合国家重点实验室, 华东理工大学, 上海 200237

收稿日期:2016-07-01 修回日期:2016-08-13 出版日期:2017-02-05 发布日期:2017-02-05
通讯作者: 徐晶
基金资助:
国家自然科学基金项目（21576084，91534127）；科技部国际合作项目（2015DFG42570）。

CO₂ hydrogenation over Fe catalysts supported on ZSM-5 zeolite with different ratios of Si/Al

SHAO Guangyin, ZHANG Yulong, ZHANG Zhengpai, ZHANG Jun, SU Junjie, LIU Da, HE Chongheng, XU Jing, HAN Yifan

State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China

Received:2016-07-01 Revised:2016-08-13 Online:2017-02-05 Published:2017-02-05
Supported by:
supported by the National Natural Science Foundation of China (21576084, 91534127) and the International Cooperation Project of Ministry of Science and Technology (2015DFG42570).

摘要/Abstract

摘要：

CO₂加氢在铁基催化剂上直接制取高附加值化学品是实现其资源化利用的重要途径。通过等体积浸渍法制备了不同硅铝比（25，70，150）的ZSM-5负载的铁基催化剂，考察硅铝比对铁基催化剂上CO₂加氢性能的影响。结果表明，随着硅铝比的升高，催化剂活性先升高后降低，最优化硅铝比为70。CO₂-DRIFTS和CO₂-TPD结果显示，硅铝比为70的ZSM-5载体制备的催化剂具有较多且较强的表面碱性位，促进CO₂分子的活化解离。通过H₂-TPR、XRD、Raman等表征揭示了催化剂结构的演变过程。还原后催化剂的活性金属以单质Fe形式存在，反应过程中单质Fe向Fe₃O₄和FeC_x物种转化。不同硅铝比配位环境影响Fe与C的相互作用，影响FeC_x的生成，从而影响CO₂加氢的活性和选择性。

关键词: CO₂加氢, Fe基催化剂, ZSM-5, 硅铝比, 催化, 催化剂载体, 相变

Abstract:

CO₂ hydrogenation directly producing value added chemicals over Fe based catalysts is an important approach to achieve its resource-oriented utilization. In this work, ZSM-5 supported iron catalysts with different ratios of Si/Al (25, 70, 150) were prepared by conventional impregnation method and the effects of supports with different Si/Al ratios on the catalytic performance were investigated. The catalyst activity increased first, then decreased with the increase of Si/Al ratio, and the optimal ratio of Si/Al was 70. With the combination of CO₂-DRIFTS and CO₂-TPD, it was found that ZSM-5 (Si/Al=70) zeolite supported Fe catalyst possessed more and stronger basic sites, which promoted the dissociative activation of CO₂. The evolution of catalysts structure was explored using multiple techniques such as H₂-TPR, XRD and Raman spectroscopy. After reduction, Fe2O3 on the catalyst surface was converted into metallic iron, which was then transferred to Fe₃O₄ and FeC_x during the reaction. It was also found that the discrepancy in the interaction between Fe and C under different coordination environments (Si/Al) affects the formation of FeC_x, thereby affecting the activity and products selectivity of CO₂ hydrogenation.

Key words: CO₂ hydrogenation, Fe based catalysts, ZSM-5, Si/Al ratio, catalysis, catalyst support, phase change

中图分类号:

TQ018

邵光印, 张玉龙, 张征湃, 张俊, 苏俊杰, 刘达, 赫崇衡, 徐晶, 韩一帆. 不同硅铝比ZSM-5负载铁基催化剂二氧化碳加氢性能[J]. 化工学报, 2017, 68(2): 670-678.

SHAO Guangyin, ZHANG Yulong, ZHANG Zhengpai, ZHANG Jun, SU Junjie, LIU Da, HE Chongheng, XU Jing, HAN Yifan. CO₂ hydrogenation over Fe catalysts supported on ZSM-5 zeolite with different ratios of Si/Al[J]. CIESC Journal, 2017, 68(2): 670-678.

参考文献 32

[1]	XU S C, HE Z X, LONG R Y. Factors that influence carbon emissions due to energy consumption in China:decomposition analysis using LMDI[J]. Applied Energy, 2014, 127:182-193.
[2]	ZHONG W Y, JOANNA D H. The greenhouse effect and carbon dioxide[J]. Weather, 2014, 69(68):100-105.
[3]	GAO P, LI F, ZHAN H, et al. Influence of Zr on the performance of Cu/Zn/Al/Zr catalysts via hydrotalcite-like precursors for CO2 hydrogenation to methanol[J]. Journal of Catalysis, 2013, 298:51-60.
[4]	GNANAMANI M K, JACOBS G, HUSSEIN H, et al. Hydrogenation of carbon dioxide over Co-Fe bimetallic catalysts[J]. ACS Catal., 2016, 6(2):913-927.
[5]	PRASAD P S S, BAE J W, JUN K W, et al. Fischer-Tropsch synthesis by carbon dioxide hydrogenation on Fe-based catalysts[J]. Catal. Surv. Asia, 2008, 12:170-183.
[6]	PIEDEL T, SCHULZ H, SCHAUB G, et al. Fischer-Tropsch on iron with H2/CO and H2/CO2 as synthesis gases:the episodes of formation of the Fischer-Tropsch regime and construction of the catalysts[J]. Topics in Catalysis, 2003, 26(1/2/3/4):41-54.
[7]	DUBOIS J L, ARAKAWA H, SAYAMA K. CO2 hydrogenation over carbide catalysts[J]. Chemistry Letters, 1992, 125(1):5-8.
[8]	OZBEK M O, NIEMANTSVERDRIET J W H. Methane, formaldehyde and methanol formation pathways from carbon monoxide and hydrogen on the (001) surface of the iron carbide γ-Fe5C2[J]. Journal of Catalysis, 2015, 325:9-18.
[9]	GALLEGOS N G, ALVAREZ A M, CAGNOLI M V, et al. Selectivity to olefins of Fe/SiO2-MgO catalysts in the Fischer-Tropsch reaction[J]. Journal of Catalysis, 1996, 161(1):132-142.
[10]	PANDEY D, DEO G. Promotional effects in alumina and silica supported bimetallic Ni-Fe catalysts during CO2 hydrogenation[J]. Journal of Molecular Catalysis A:Chemical, 2014, 382:23-30.
[11]	RIEDEL T, CLAEYS M, SCHULZ H, et al. Comparative study of Fischer-Tropsch synthesis with H2/CO and H2/CO2 syngas using Feand Co-based catalysts[J]. Applied Catalysis A:General, 1999, 186(1/2):201-213.
[12]	MARTINEZ A, LOPEZ C. The influence of ZSM-5 zeolite composition and crystal size on the in situ conversion of Fischer-Tropsch products over hybrid catalysts[J]. Applied Catalysis A:General, 2005, 294(2):251-259.
[13]	KANG S H, BAE J W, et al. Fischer-tropsch synthesis using zeolite-supported iron catalysts for the production of light hydrocarbons[J]. Catalysis Letter, 2008, 125:264-270.
[14]	张俊, 张征湃, 苏俊杰, 等. 载体碱性对铁基催化剂费托合成反应的影响[J]. 化工学报, 2016, 67(2):549-556. ZHANG J, ZHANG Z P, SU J J, et al. Effect of support basicity on iron based catalysts for Fischer-Tropsch synthesis[J]. CIESC Journal, 2016, 67(2):549-556.
[15]	TORRES GALVIS H M, BITTER J H, DAVIDIAN T, et al. Iron particle size effects for direct production of lower olefins from synthesis gas[J]. Journal of the American Chemical Society, 2012, 134(39):16207-16215.
[16]	POUR A N, ZARE M, ZAMANI Y, et al. Catalytic behaviors of bifunctional Fe-HZSM-5 catalyst in Fischer-Tropsch synthesis[J]. Journal of Natural Gas Science and Engineering, 2009, 1(6):183-189.
[17]	UNRAU C J, AXELBAUM R L, CYNTHIA S L. High-yield growth of carbon nanotubes on composite Fe/Si/O nanoparticle catalysts:a Car-Parrinello molecular dynamics and experimental study[J]. J. Phys. Chem. C, 2010, 114(23):10430-10435
[18]	JIN Y, DATYE A K. Phase transformations in iron Fischer-Tropsch catalysts during temperature-programmed reduction[J]. Journal of Catalysis, 2000, 196(1):8-17.
[19]	PARKA J Y, LEA Y J, JUN K W, et al. Alumina-supported iron oxide nanoparticles as Fischer-Tropsch catalysts:effect of particle size of iron oxide[J]. Journal of Molecular Catalysis A:Chemical, 2010, 323(1/2):84-90.
[20]	FORSTER H, SCHUMANN M. Infrared spectroscopic studies on carbon dioxide adsorption in alkali-metal and alkaline-earth-metal ion-exchanged A-type zeolites[J]. J. Chem. Soc., Faraday Trans. Ⅰ, 1989, 85(5):1149-1158.
[21]	LAVALLEY J C. Infrared spectrometric studies of the surface basicity of metal oxides and zeolites using adsorbed probe molecules[J]. Catalysis Today, 1996, 27(3/4):377-401.
[22]	WEIGEL J, KOEPPEL R A, BAIKER A, et al. Surface species in CO and CO2 hydrogenation over copper/zirconia:on the methanol synthesis mechanism[J]. Langmuir, 1996, 12(22):5319-5329.
[23]	SZANYI J, KWAK J H. Dissecting the steps of CO2 reduction(1):The interaction of CO and CO2 with γ-Al2O3:an in situ FTIR study[J]. Phys. Chem. Chem. Phys., 2014, 16:15123-15125.
[24]	ZHANG X H, LIN L, ZHANG T, et al. Catalytic dehydration of lactic acid to acrylic acid over modified ZSM-5 catalysts[J]. Chemical Engineering Journal, 2016, 284:934-941.
[25]	XU L Y, WANG Q X, LIANG D B, et al. The promotions of MnO and K2O to Fe/silicalite-2 catalyst for the production of light alkenes from CO2 hydrogenation[J]. Applied Catalysis A:General, 1998, 173(1):19-25.
[26]	李静, 邓廷云, 杨林, 等. CO2吸附活化及催化加氢制低碳烯烃的研究进展[J]. 化工进展, 2013, 32(2):341-342. LI J, DENG T Y, YANG L, et al. Research progress of adsorption activation and catalytic hydrogenation of CO2[J]. Chemical Industry and Engineering Progress, 2013, 32(2):341-342.
[27]	JACOBS P A, BELLMOOS R V. Framework hydroxyl groups of H-ZSM-5 zeolites[J]. J. Phys. Chem., 1982, 86(15):3050-3052.
[28]	LU J, YANG L, XU B, et al. Promotion effects of nitrogen doping into carbon nanotubes on supported iron Fischer-Tropsch catalysts for lower olefins[J]. ACS Catalysis, 2014, 4(2):613-621.
[29]	NAM M O S S, KISHAN G, LEE M W, et al. Selective synthesis of C2-C4 olefins and C5+ hydrocarbons over unpromoted and cerium-promoted iron catalysts supported on ion exchanged Y zeolite[J]. J. Chem. Research (S), 1999:344-345.
[30]	RAVAGNAN L, SIVIERO F, LENARDI C, et al. Cluster-beam deposition and in situ characterization of carbyne-rich carbon films[J]. Physical Review Letters, 2002, 89(28):287-291.
[31]	FU D L, DAI W W, ZHANG Z P, et al. Probing the structure evolution of iron-based Fischer-Tropsch to produce olefins by Operando Raman spectroscopy[J]. ChemCatChem, 2015, 7:752-756.
[32]	BEHNER H, SPIESS W, WEDLER G, et al. Interaction of carbon dioxide with Fe(110), stepped Fe(100) and Fe(111)[J]. Surface Science, 1986, 175(2):276-286.

不同硅铝比ZSM-5负载铁基催化剂二氧化碳加氢性能

CO₂ hydrogenation over Fe catalysts supported on ZSM-5 zeolite with different ratios of Si/Al

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

参考文献 32

相关文章 15

编辑推荐

Metrics

本文评价

[1]	张双星, 刘舫辰, 张义飞, 杜文静. R-134a脉动热管相变蓄放热实验研究[J]. 化工学报, 2023, 74(S1): 165-171.
[2]	江河, 袁俊飞, 王林, 邢谷雨. 均流腔结构对微细通道内相变流动特性影响的实验研究[J]. 化工学报, 2023, 74(S1): 235-244.
[3]	吴延鹏, 刘乾隆, 田东民, 陈凤君. 相变材料与热管耦合的电子器件热管理研究进展[J]. 化工学报, 2023, 74(S1): 25-31.
[4]	范孝雄, 郝丽芳, 范垂钢, 李松庚. LaMnO₃/生物炭催化剂低温NH₃-SCR催化脱硝性能研究[J]. 化工学报, 2023, 74(9): 3821-3830.
[5]	吴雷, 刘姣, 李长聪, 周军, 叶干, 刘田田, 朱瑞玉, 张秋利, 宋永辉. 低阶粉煤催化微波热解制备含碳纳米管的高附加值改性兰炭末[J]. 化工学报, 2023, 74(9): 3956-3967.
[6]	程业品, 胡达清, 徐奕莎, 刘华彦, 卢晗锋, 崔国凯. 离子液体基低共熔溶剂在转化CO₂中的应用[J]. 化工学报, 2023, 74(9): 3640-3653.
[7]	陈杰, 林永胜, 肖恺, 杨臣, 邱挺. 胆碱基碱性离子液体催化合成仲丁醇性能研究[J]. 化工学报, 2023, 74(9): 3716-3730.
[8]	杨学金, 杨金涛, 宁平, 王访, 宋晓双, 贾丽娟, 冯嘉予. 剧毒气体PH₃的干法净化技术研究进展[J]. 化工学报, 2023, 74(9): 3742-3755.
[9]	李艺彤, 郭航, 陈浩, 叶芳. 催化剂非均匀分布的质子交换膜燃料电池操作条件研究[J]. 化工学报, 2023, 74(9): 3831-3840.
[10]	杨欣, 彭啸, 薛凯茹, 苏梦威, 吴燕. 分子印迹-TiO₂光电催化降解增溶PHE废水性能研究[J]. 化工学报, 2023, 74(8): 3564-3571.
[11]	杨菲菲, 赵世熙, 周维, 倪中海. Sn掺杂的In₂O₃催化CO₂选择性加氢制甲醇[J]. 化工学报, 2023, 74(8): 3366-3374.
[12]	李凯旋, 谭伟, 张曼玉, 徐志豪, 王旭裕, 纪红兵. 富含零价钴活性位点的钴氮碳/活性炭设计及甲醛催化氧化应用研究[J]. 化工学报, 2023, 74(8): 3342-3352.
[13]	张贲, 王松柏, 魏子亚, 郝婷婷, 马学虎, 温荣福. 超亲水多孔金属结构驱动的毛细液膜冷凝及传热强化[J]. 化工学报, 2023, 74(7): 2824-2835.
[14]	李盼, 马俊洋, 陈志豪, 王丽, 郭耘. Ru/α-MnO₂催化剂形貌对NH₃-SCO反应性能的影响[J]. 化工学报, 2023, 74(7): 2908-2918.
[15]	史昊鹏, 钟达文, 廉学新, 张君峰. 朝下多尺度沟槽翅片结构表面沸腾换热实验研究[J]. 化工学报, 2023, 74(7): 2880-2888.

不同硅铝比ZSM-5负载铁基催化剂二氧化碳加氢性能

CO2 hydrogenation over Fe catalysts supported on ZSM-5 zeolite with different ratios of Si/Al

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

参考文献 32

相关文章 15

编辑推荐

Metrics

本文评价

CO₂ hydrogenation over Fe catalysts supported on ZSM-5 zeolite with different ratios of Si/Al