铝改性介孔二氧化硅泡沫载体材料合成及其DBT加氢脱硫性能

催化学报 ›› 2017, Vol. 38 ›› Issue (8): 1347-1359.

铝改性介孔二氧化硅泡沫载体材料合成及其DBT加氢脱硫性能

宋绍彤^b, 杨旭^c, 王博^a, 周晓峰^a, 段爱军^a, 迟克彬^b, 赵震^a, 徐春明^a, 陈振涛^a, 李建梅^a

a 中国石油大学国家重油加工重点实验室, 北京 102249;
b 中国石油天然气股份有限公司石油化工研究院, 北京 100195;
c 中国石油化工股份有限公司抚顺石油化工研究院, 辽宁抚顺 113001

收稿日期:2017-04-19 修回日期:2017-06-02 出版日期:2017-08-18 发布日期:2017-08-04
通讯作者: 段爱军, 赵震
基金资助:
国家自然科学基金（21276277，U1463207）；中海油项目；中石油重大专项；广西石化资源加工及过程强化技术重点实验室开放课题（2015K003）.

Al-modified mesocellular silica foam as a superior catalyst support for dibenzothiophene hydrodesulfurization

Shaotong Song^b, Xu Yang^c, Bo Wang^a, Xiaofeng Zhou^a, Aijun Duan^a, Kebin Chi^b, Zhen Zhao^a, Chunming Xu^a, Zhentao Chen^a, Jianmei Li^a

a State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China;
b Petrochemical Research Institute, Petro China Company Limited, Beijing 100195, China;
c Fushun Research Institute of Petroleum and Petrochemicals, SINOPEC, Fushun 113001, Liaoning, China

Received:2017-04-19 Revised:2017-06-02 Online:2017-08-18 Published:2017-08-04
Supported by:
This work was supported by National Natural Science Foundation of China (21276277, U1463207), CNOOC Project, CNPC major project, and the Opening Project of Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology (2015K003).

摘要/Abstract

摘要：

介孔二氧化硅泡沫（MCFs）材料具有超大的三维球形孔结构、超大孔容（1.0-2.4 cm³/g）、高比表面（1000 m²/g）、孔径可调范围较广（24-50 nm）且球形孔道之间通过窗口（9-22 nm）联结，因此具有优良的传质性能，能够促进加氢脱硫反应.但是，与传统的微孔分子筛相比，该纯硅类介孔材料酸性较弱，不利于一些酸催化反应；因此，对纯硅材料进行金属改性以增加其酸性，从而促进催化剂的催化活性.而一般对纯硅类介孔材料采用Al，Ti，Zr等金属，铝改性主要是为纯硅载体提供酸性，而钛锆改性则是为了调变活性金属以及促进金属的分散，从而提高催化剂的加氢脱硫活性.
因此，我们主要采用后改性方法，以P123为微乳液体系中的表面活性剂，TEOS为硅源，TMB为扩孔剂，异丙醇铝为铝源，成功合成了一系列Si/Al比不同的介孔二氧化硅泡沫材料.通过改变异丙醇铝的加入量，成功合成了系列Si/Al比（x）的NiMo/Al-MCFs（x）（x=10，20，30，40和50）催化剂.对所合成的载体及相应的催化剂通过SAXS，N₂吸附脱附，SEM，Py-FTIR，UV-Vis，H₂-TPR，NH₃-TPD，HRTEM，Raman及²⁷Al MAS NMR等表征手段进行分析，并在高压加氢微反装置上对相应的NiMo负载型催化剂进行DBT HDS活性评价，系统分析了不同硅铝比对催化剂DBT HDS反应活性的影响.SAXS和SEM表征结果表明，Al后改性并没有破坏载体材料的结构；²⁷Al MAS NMR表征结果表明，后改性法能成功把Al掺杂进纯硅材料的骨架中.催化剂UV-Vis和Raman表征结果表明，当Si/Al比为20时，NiMo/Al-MCFs（20）催化剂Mo物种的带隙能量最大，且氧化钼的平均粒径较小，Mo物种在该催化剂中的分散度较好；H₂-TPR分析结果表明，NiMo/Al-MCFs（20）催化剂还原温度较低，最易还原.Py-FTIR结果表明，随着Al加入量的增大，其酸性逐渐增大，当Si/Al比为20时酸性达到最大，继续增加Al的加入量，其酸性不再增加；此外，NiMo/Al-MCFs（20）的硫化度最高，且其MoS₂的堆垛层数较低.负载活性金属后制备了NiMo/Al-MCFs（x）催化剂，将其应用于DBT加氢脱硫反应，并与传统NiMo/γ-Al₂O₃催化剂加氢脱硫反应活性作对比.研究发现，所制备的NiMo/Al-MCFs（x）系列催化剂由于具有较大孔径、比表面积及孔容和较强的酸性，因而其DBT HDS活性明显高于传统的工业NiMo/γ-Al₂O₃催化剂，且催化剂活性在硅铝比达到20时最大，最高可达96%，因此它作为加氢脱硫催化剂载体具有很大的应用前景.

关键词: 铝改性介孔二氧化硅泡沫, 硅铝比, 后合成, 加氢脱硫催化剂, 二苯并噻吩

Abstract:

A series of Al-containing mesostructured cellular silica foams (Al-MCFs) with different Si/Al molar ratios (x; x=10, 20, 30, 40, or 50) were prepared by a post synthetic method using aluminum isopropoxide as an alumina source. The corresponding NiMo catalysts supported on Al-MCFs were prepared and evaluated using dibenzothiophene (DBT) as the probe reactant. All the synthesized samples were characterized by small-angle X-ray scattering, scanning electron microscopy, nitrogen adsorption-desorption, UV-Vis diffuse reflectance spectroscopy, H₂ temperature-programmed reduction, ²⁷Al MAS NMR, temperature-programmed desorption of ammonia, pyridine-FTIR, Raman spectroscopy, HRTEM, and X-ray photoelectron spectroscopy to analyze their physicochemical properties and to gain a deeper insight of the interrelationship between the structures and the catalytic performance. The synthesis mechanism was proposed to involve the formation of Brönsted acid and Lewis acid sites through the replacement of Si⁴⁺ with Al³⁺. Aluminum introduced into MCFs by the post synthetic method has a negligible influence on the mesostructure of the parent MCFs but can form silicoaluminate materials with moderate Brönsted acidity. For Al-MCFs(x) materials, the detection of tetrahedrally coordinated Al³⁺ cations demonstrated that the Al species had been successfully incorporated into the silicon frameworks. Furthermore, the DBT hydrodesulfurization (HDS) catalytic activity of the NiMo/Al-MCFs(x) catalysts increased with increasing Si/Al molar ratio, and reached a maximum at a Si/Al molar ratio of 20. The interaction of Ni and Mo species with the support became stronger when Al was incorporated into the MCFs supports. The high activities of the NiMo/Al-MCFs catalysts for the DBT HDS were attributed to the suitable acidity properties and good dispersions of the Ni and Mo active phases.

Key words: Al-MCFs, Si/Al ratio, Post-synthesis, Hydrodesulfurization catalyst, Dibenzothiophene

宋绍彤, 杨旭, 王博, 周晓峰, 段爱军, 迟克彬, 赵震, 徐春明, 陈振涛, 李建梅. 铝改性介孔二氧化硅泡沫载体材料合成及其DBT加氢脱硫性能[J]. 催化学报, 2017, 38(8): 1347-1359.

Shaotong Song, Xu Yang, Bo Wang, Xiaofeng Zhou, Aijun Duan, Kebin Chi, Zhen Zhao, Chunming Xu, Zhentao Chen, Jianmei Li. Al-modified mesocellular silica foam as a superior catalyst support for dibenzothiophene hydrodesulfurization[J]. Chinese Journal of Catalysis, 2017, 38(8): 1347-1359.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/

https://www.cjcatal.com/CN/Y2017/V38/I8/1347

参考文献

[1] C. S. Song, X. L. Ma, Appl. Catal. B, 2003, 41, 207-238.
[2] S. A. Al-Bogami, H. I. de Lasa, Fuel, 2003, 108, 490-501.
[3] D. W. Gao, A. J. Duan, X. Zhang, Z. Zhao, H. E, J. M. Li, H. Wang, Appl. Catal. B, 2015, 165, 269-284.
[4] F. Trejo, M. S. Rana, J. Ancheyta, Catal. Today, 2008, 130, 327-336.
[5] C. T. Kresge, M. E. Leonowicz, W. J. Roth, J. C. Vartuli, J. S. Beck, Nature, 1992, 359, 710-712.
[6] R. Nava, J. Morales, G. Alonso, C. Ornelas, B. Pawelec, J. L. G. Fierro, Appl. Catal. A, 2007, 321, 58-70.
[7] G. M. Dhar, G. M. Kumaran, M. Kumar, K. S. Rawat, L. D. Sharma, B. D. Raju, K. S. R. Rao, Catal. Today, 2005, 99, 309-314.
[8] Y. Wan, D. Y. Zhao, Chem. Rev.,2007, 107, 2821-2860.
[9] D. J. N. Subagyono, M. Marshall, G. P. Knowles, A. L. Chaffee, Microporous Mesoporous Mater., 2014, 186, 84-93.
[10] P. Schmidt Winkel, W. W. Lukens Jr., D. Y. Zhao, P. D. Yang, B. F. Chmelka, G. D. Stucky, J. Am. Chem. Soc., 1999, 121, 254-255.
[11] C. Mille, R. W. Corkery, J. Mater. Chem. A, 2013, 1, 1849-1859.
[12] S. E. Baker, A. M. Sawvel, J. Fan, Q. H. Shi, N. Strandwitz, G. D. Stucky, Langmuir, 2008, 24, 14254-14260.
[13] Z. Y. Yuan, B. L. Su, J. Mater. Chem. A, 2006, 16, 663-677.
[14] Y. Li, D. H. Pan, C. Z. Yu, Y. Fan, X. J. Bao, J. Catal., 2012, 286, 124-136.
[15] R. Schmidt, D. Akporiaye, M. Stocker, O. H. Ellestad, J. Chem. Soc. Chem. Commun., 1994, 12, 1493-1494.
[16] Z. H. Luan, C. F. Cheng, W. Z. Zhou, J. Klinowski, J. Phys. Chem., 1995, 99, 1018-1024.
[17] K. R. Kloetstra, H. W. Zandbergen, H. van. Bekkum, Catal. Lett., 1995, 33, 157-163.
[18] R. B. Borade, A. Clearfield, Catal. Lett., 1995, 31, 267-272.
[19] J. M. Kim, J. H. Kwak, S. Jun, R. Ryoo, J. Phys. Chem., 1995, 99, 16742-16747.
[20] J. L. Blin, C. Otjacques, G. Herrier, B. L. Su, Langmuir, 2000, 16, 4229-4236.
[21] M. J. Cheng, Z. B. Wang, K. Sakurai, F. Kumata, T. Saito, T. Komatsu, T. Yashima, Chem. Lett., 1999, 131-132.
[22] Z. H. Luan, M. Hartmann, D. Y. Zhao, W. Z. Zhou, L. Kevan, Chem. Mater., 1999, 11, 1621-1627.
[23] Y. H. Yue, A. Gédéon, J. L. Bonardet, J. B. D' Espinose, J. Fraissard, N. Melosh, Chem. Commun., 1999, 1967-1968.
[24] D. Tr. on, A. Ungureanu, S. Kaliaguine, Phys. Chem. Chem. Phys., 2003, 5, 3534-3538.
[25] A. Ungureanu, T. V. Hoang, D. T. On, E. Dumitriu, S. Kaliaguine, Appl. Catal. A, 2005, 294, 92-105.
[26] P. Küstrowski, L. Chmielarz, R. Dziembaj, P. Cool, E. F. Vansant, J. Phys. Chem. B, 2005, 109, 11552-11558.
[27] Y. C. Liang, R. Anwander, Microporous Mesoporous Mater., 2004, 72, 153-165.
[28] E. Vilarrasa García, E. M. Ortigosa Moya, J. A. Cecilia, C. L. Cavalcante Jr., J. Jimenez Jimenez, D. C. S. Azevedo, E. Rodríguez Castellon, Microporous Mesoporous Mater., 2015, 209, 172-183.
[29] G. Berhault, M. P. De la Rosa, A. Mehta, M. J. Yácaman, R. R. Chianelli, Appl. Catal. A, 2008, 345, 80-88.
[30] J. S. Lettow, Y. J. Han, P. Schmidt Winkel, P. D. Yang, D. Y. Zhao, G. D. Stucky, J. Y. Ying, Langmuir, 2000, 16, 8291-8295.
[31] P. Schmidt Winkel, W. W. Lukens, D. Y. Zhao, P. D. Yang, B. F. Chmelka, G. D. Stucky, J. Am. Chem. Soc.,1999, 121, 254-255.
[32] S. Y. Xing, P. M. Lv, J. Y. Fu, J. Y. Wang, P. Fan, L. M. Yang, Z. H. Yuan, Microporous Mesoporous Mater., 2017, 239, 316-327.
[33] G. S. He, L. B. Sun, X. L. Song, X. Q. Liu, Y. Yin, Y. C. Wang, Energy Fuels, 2011, 25, 3506-3513.
[34] M. Gomez Cazalilla, J. M. Merida Robles, A. Gurbani, E. Rodriguez Castellon, A. Jimenez Lopez, J. Solid State Chem., 2007, 180, 1130-1140.
[35] T. Klimova, L. Peña, L. Lizama, C. Salcedo, O. Y. Gutiérrez, Ind. Eng. Chem. Res., 2009, 48, 1126-1133.
[36] L. Lizama, T. Klimova, Appl. Catal. B, 2008, 82, 139-150.
[37] I. E. Wachs, C. A. Roberts, Chem. Soc. Rev., 2010, 39, 5002-5017.
[38] M. J. Cheng, F. Kumata, T. Saito, T. Komatsu, T. Yashima, Appl. Catal. A, 1999, 183, 199-208.
[39] M. Fournier, C. Louis, M. Che, P. Chaquin, D. Masure, J. Catal., 1989, 119, 400-414.
[40] Z. K. Cao, A. J. Duan, Z. Zhao, J. M. Li, Y. C. Wei, G. Y. Jiang, J. Liu, J. Mater. Chem. A, 2014, 2, 19738-19749.
[41] P. Biswas, P. Narayanasarma, C. M. Kotikalapudi, A. K. Dalai, J. Adjaye, Ind. Eng. Chem. Res., 2011, 50, 7882-7895.
[42] D. W. Gao, A. J. Duan, X. Zhang, K. B. Chi, Z. Zhao, J. M. Li, Y. C. Qin, X. L. Wang, C. M. Xu, J. Mater. Chem. A, 2015, 3, 16501-16512.
[43] H. C. Hu, I. E. Wachs, S. R. Bare, J. Phys. Chem., 1995, 99, 10897-10910.
[44] Y. G. Wang, G. Xiong, X. Liu, X. C. Yu, L. P. Liu, J. Y. Wang, Z. C. Feng, C. Li, J. Phys. Chem. C, 2008, 112, 17265-17271.
[45] J. A. Mendoza Nieto, O. Vera Vallejo, L. Escobar Alar?on, D. Solís Casados, T. Klimova, Fuel, 2013, 110, 268-277.
[46] S. Badoga, K. C. Mouli, K. K. Soni, A. K. Dalai, J. Adjaye, Appl. Catal. B, 2012, 125, 67-84.
[47] A. J. Duan, T. S. Li, Z. Zhao, B. J. Liu, X. F. Zhou, G. Y. Jiang, J. Liu, Y. C. Wei, H. F. Pan, Appl. Catal. B, 2015, 165, 763-773.
[48] X. L. Wang, Z. Zhao, P. Zheng, Z. T. Chen, A. J. Duan, C. M. Xu, J. Q. Jiao, H. L. Zhang, Z. K. Cao, B. H. Ge, J. Catal., 2016, 344, 680-691.
[49] R. Huirache Acuña, B. Pawelec, E. Rivera Muñoz, R. Nava, J. Espino, J. L. G. Fierro, Appl. Catal. B, 2009, 92, 168-184.
[50] J. A. Z. Pieterse, S. Veefkind-Reyes, K. Seshan, L. Domokos, J. A. Lercher, J. Catal., 1999, 187, 518-520.
[51] T. Kataoka, J. A. Dumesic, J. Catal., 1988, 112, 66-79.
[52] S. Zhou, Y. Liu, J. M. Li, Y. J. Wang, G. Y. Jiang, Z. Zhao, D. X. Wang, A. J. Duan, J. Liu, Y. C. Wei, Appl. Catal. B, 2014, 158-159, 20-29.
[53] R. Huirache Acuña, T. A. Zepeda, E. M. Rivera Muñoz, R. Nava, C. V. Loricera, B. Pawelec, Fuel, 2015, 149, 149-161.
[54] C. Boissiére, A. Larbot, A. van der Lee, P. J. Kooyman, E. Prouzet, Chem. Mater., 2000, 12, 2902-2913.
[55] S. Ruthstein, V. Frydman, D. Goldfarb, J. Phys. Chem. B, 2004, 108, 9016-9022.
[56] X. F. Zhou, A. J. Duan, Z. Zhao, Y. J. Gong, H. D. Wu, J. M. Li, Y. C. Wei, G. Y. Jiang, J. Liu, Y. Zhang, J. Mater. Chem. A, 2014, 2, 6823-6833.
[57] J. C. Muijsers, T. Weber, R. M. Vanhardeveld, H. W. Zandbergen, J. W. Niemantsverdriet, J. Catal., 1995, 157, 698-705.
[58] T. Fujikawa, M. Kato, H. Kimura, K. Kiriyama, M. Hashimoto, N. Nakajima, J. Jap. Pet. Inst., 2005, 48, 106-113.
[59] H. D. Wu, A. J. Duan, Z. Zhao, D. H. Qi, J. M. Li, B. Liu, G. Y. Jiang, J. Liu,