Preparation and Characterization of Pt-Sn/SBA-15 Catalysts and Their Catalytic Performances for Long Chain Alkane Dehydrogenation

Abstract

Abstract: A series of the Pt-Sn/SBA-15 catalysts were prepared and their properties characterized by using X-ray powder diffraction(XRD),N₂ adsorption-desorption,high resolution transmission electron microscope,X-ray photoelectron spectroscopy(XPS)and H₂-temperature programmed reduction.Their performances in long chain alkane dehydrogenation were evaluated in a fixed-bed microreactor with dodecane as a model alkane.The results indicated that SBA-15 maintained the well-order mesoporous structure during the reaction.The performance of the catalyst was found not dominated by its textural properties,but by the molar ratio of Sn to Pt which governed the degree of Sn reduction.Owing to the highest degree of Sn reduction,1%(by mass)Pt-1.8%(by mass)Sn/SBA-15 showed the best catalytic activity.At 0.1 MPa and 470℃,the molar ratio of hydrogen to alkane at 4,and liquid hourly space velocity(LHSV)20 h^-1,the dodecane conversion is 10%,and the dodecene selectivity is about 70%.

Key words: SBA-15 catalyst, PtSn alloy, dodecane, dehydrogenation

摘要： A series of the Pt-Sn/SBA-15 catalysts were prepared and their properties characterized by using X-ray powder diffraction(XRD),N₂ adsorption-desorption,high resolution transmission electron microscope,X-ray photoelectron spectroscopy(XPS)and H₂-temperature programmed reduction.Their performances in long chain alkane dehydrogenation were evaluated in a fixed-bed microreactor with dodecane as a model alkane.The results indicated that SBA-15 maintained the well-order mesoporous structure during the reaction.The performance of the catalyst was found not dominated by its textural properties,but by the molar ratio of Sn to Pt which governed the degree of Sn reduction.Owing to the highest degree of Sn reduction,1%(by mass)Pt-1.8%(by mass)Sn/SBA-15 showed the best catalytic activity.At 0.1 MPa and 470℃,the molar ratio of hydrogen to alkane at 4,and liquid hourly space velocity(LHSV)20 h^-1,the dodecane conversion is 10%,and the dodecene selectivity is about 70%.

关键词: SBA-15 catalyst, PtSn alloy, dodecane, dehydrogenation

LU Zexiang, JI Shengfu, LIU Hui, LI Chengyue. Preparation and Characterization of Pt-Sn/SBA-15 Catalysts and Their Catalytic Performances for Long Chain Alkane Dehydrogenation[J]. , 2008, 16(5): 740-745.

卢泽湘, 季生福, 刘辉, 李成岳. Preparation and Characterization of Pt-Sn/SBA-15 Catalysts and Their Catalytic Performances for Long Chain Alkane Dehydrogenation[J]. , 2008, 16(5): 740-745.

References

1 Jin, L., “Platinum-tin complexing and its application to catalysis”, Appl. Catal., 72, 33-38 (1991).
2 Coleto, I., Roldan, R., Jimenez-Sanchidrian, C., Gomez, J.P., Romero-Salguero, F.J., “Transformation of α-olefins over Pt-M (M=Re, Sn, Ge) supported chlorinated alumina”, Fuel, 86, 1000-1007 (2007).
3 Barias, O.A., Holmen, A., Blekkan, E.A., “Propane dehydrogenation over supported platinum catalysts:Effect of tin as a promoter”, Catal. Today, 24, 361-364 (1995).
4 Rodríguez, D., Sánchez, J., Arteaga, G., “Effect of tin and potassium addition on the nature of platinum supported on silica”, J. Mol. Catal. A, 228, 309-317 (2005).
5 Qiu, A.D., Fan, Y., Ma, Y.F., Wu, P.C., Chen, Y., “Effects of alkali promoters on catalytic properties of alumina-supported Pt-Sn catalysts for long-chain paraffin dehydrogenation”, Chin. J. Catal., 22(4), 343-347 (2001). (in Chinese) .
6 Aguilar-Rfos, G., Valenzuela, M., Salas, P., Armendfiriz, H., Bosch, P., del Toro, G., Silva, R., Bertfn, V., Castillo, S., “Hydrogen interactions and catalytic properties of platinum-tin supported on zinc aluminate”, Appl. Catal. A, 127, 65-75 (1995).
7 Luo, G., Yan, S.R., Qiao, M.H., Fan, K.N., “RuB/Sn-SBA-15 catalysts:Preparation, characterization, and catalytic performance in ethyl lactate hydrogenation”, Appl. Catal. A, 332 (1), 79-88 (2007).
8 Du, J.M., Xu, H.L., Shen, J., Huang, J.J., Shen, W., Zhao, D.Y., “Catalytic dehydrogenation and cracking of industrial dipentene over M/SBA-15 (M=Al, Zn) catalysts”, Appl. Catal. A, 296 (2), 186-193 (2005).
9 Perathoner, S., Lanzafame, P., Passalacqua, R., Centi, G., Schl gl, R., Su, D.S., “Use of mesoporous SBA-15 for nanostructuring titania for photocatalytic applications”, Microporous and Mesoporous Materials, 90 (1-3), 347-361 (2006).
10 Gómez-Cazalilla, M., Mérida-Robles, J.M., Gurbani, A., Rodríguez-Castellón, E., Jiménez-López, A., “Characterization and acidic properties of Al-SBA-15 materials prepared by post-synthesis alumination of a low-cost ordered mesoporous silica”, J. Solid State Chem., 180 (3), 1130-1140 (2007).
11 Zhao, D.Y., Feng, J.L., Huo, Q.S., Melosh, N., Fredrickson, G.H., Chmelka, B.F., Stucky, G.D., “Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores”, Science, 279, 548-552 (1998).
12 Krawiec, P., Kockrick, E., Simon, P., Auffermann, G., Kaskel, S., “Platinum-catalyzed template removal for the in situ synthesis of MCM-41 supported catalysts”, Chem. Mater., 18, 2663-2669 (2006).
13 Neri, G., Rizzo, G., Arico, A.S., Crisafulli, C., de Luca, L., Donato, A., Musolino, M.G., Pietropaolo, R., “One-pot synthesis of naturanol from a-pinene oxide on bifunctional Pt-Sn/SiO₂ heterogeneous catalysts (I) The catalytic system”, Appl. Catal. A, 325, 15-24 (2007).
14 Kanda, Y., Aizawa, T., Kobayashi, T., Uemichi, Y., Namba, S., Sugioka, M., “Preparation of highly active AlSBA-15-supported platinum catalyst for thiophene hydrodesulfurization”, Appl. Cata. B, 77, 117-124 (2007).
15 Ruiz-Martínez, J., Sepúlveda-Escribano, A., Anderson, J.A., Rodríguez-Reinoso, F., “Influence of the preparation method on the catalytic behaviour of PtSn/TiO₂ catalysts”, Catal. Today, 123, 235-244 (2007).
16 Siri, G.J., Ramallo-L pez, J.M., Casella, L., Fierro, J.L.G., Requejo, F.G., Ferretti, O.A., “XPS and EXAFS study of supported PtSn catalysts obtained by surface organometallic chemistry on metals application to the isobutane dehydrogenation”, Appl. Catal. A, 278, 239-249 (2005).
17 Llorca, J., Homs, N., Fierro, J.G., Sales, J., Ramirez de la Piscina, P., “Platinum-tin catalysts supported on silica highly selective for n-hexane dehydrogenation”, J. Catal., 166, 44-52 (1997).
18 Lieseke, H., Volter, J., “State of tin in Pt-Sn/Al 2 O 3 reforming catalysts investigated by TPR and chemisorption”, J. Catal., 90 (1), 96-105 (1984).
19 Rodriguez, R., Pfaff, C., Melo, L., Betancourt, P., “Characterization and catalytic performance of a bimetallic Pt-Sn/HZSM-5 catalyst used in denitratation of drinking water”, Catal. Today, 107/108, 100-105 (2005).
20 Salmones, J., Wang, J.A., Galicia, J.A., Aguilar-Rios, G., “H₂ reduction behaviors and catalytic performance of bimetallic tin-modified platinum catalysts for propane dehydrogenation”, J. Mol. Catal. A, 184, 203-213 (2002).
21 Lin, L.W., Zhang, T., Zang, J.L., Xu, Z.S., “Dynamic process of carbon deposition on Pt and Pt-Sn catalysts for alkane dehydrogenation”, Appl. Catal., 67 (1), 11-23 (1990).

[1]	Junru Liu, Rui Hu, Xinlei Liu, Qunfeng Zhang, Guanghua Ye, Zhijun Sui, Xinggui Zhou. Modeling of propane dehydrogenation combined with chemical looping combustion of hydrogen in a fixed bed reactor [J]. Chinese Journal of Chemical Engineering, 2022, 47(7): 165-173.
[2]	Di Gao, Yibo Zhi, Liyuan Cao, Liang Zhao, Jinsen Gao, Chunming Xu, Mingzhi Ma, Pengfei Hao. Influence of zinc state on the catalyst properties of Zn/HZSM-5 zeolite in 1-hexene aromatization and cyclohexane dehydrogenation [J]. Chinese Journal of Chemical Engineering, 2022, 43(3): 124-134.
[3]	Bofeng Zhang, Mingxia Song, Hongwang Liu, Guozhu Li, Sibao Liu, Li Wang, Xiangwen Zhang, Guozhu Liu. Role of Ni species in ZnO supported on Silicalite-1 for efficient propane dehydrogenation [J]. Chinese Journal of Chemical Engineering, 2022, 43(3): 240-247.
[4]	Tianlei Wang, Zhikang Xu, Yuanyuan Yue, Tinghai Wang, Minggui Lin, Haibo Zhu. Bimetallic PtSn nanoparticles confined in hierarchical ZSM-5 for propane dehydrogenation [J]. Chinese Journal of Chemical Engineering, 2022, 41(1): 384-391.
[5]	Yanyong Li, Meng Ge, Jiameng Wang, Mengquan Guo, Fanji Liu, Mingxun Han, Yanhong Xu, Lihong Zhang. Dehydrogenation of isobutane to isobutene over a Pt-Cu bimetallic catalyst in the presence of LaAlO₃ perovskite [J]. Chinese Journal of Chemical Engineering, 2021, 32(4): 203-211.
[6]	Mohammad Reza Nabid, Yasamin Bide, Mahsa Jafari. One-step synthesis of Ni@Pd/NH₂-Fe₃O₄ nanoparticles as affordable catalyst for formic acid dehydrogenation [J]. Chinese Journal of Chemical Engineering, 2021, 32(4): 168-174.
[7]	Lei Miao, Jing Yan, Weiyan Wang, Yanping Huang, Wensong Li, Yunquan Yang. Dehydrogenation of methylcyclohexane over Pt supported on Mg-Al mixed oxides catalyst: The effect of promoter Ir [J]. Chinese Journal of Chemical Engineering, 2020, 28(9): 2337-2342.
[8]	Zhongfeng Geng, Hao Deng, Yonghui Li, Minhua Zhang. Numerical investigation of complex chemistry performing in Ptcatalyzed oxidative dehydrogenation of ethane fixed-bed reactors [J]. Chinese Journal of Chemical Engineering, 2020, 28(3): 793-807.
[9]	Yuxi Zhou, Yang Wang, Wenduo Lu, Bing Yan, Anhui Lu. A high propylene productivity over B₂O₃/SiO₂@honeycomb cordierite catalyst for oxidative dehydrogenation of propane [J]. Chinese Journal of Chemical Engineering, 2020, 28(11): 2778-2784.
[10]	Ali Darvishi, Razieh Davand, Farhad Khorasheh, Moslem Fattahi. Modeling-based optimization of a fixed-bed industrial reactor for oxidative dehydrogenation of propane [J]. Chin.J.Chem.Eng., 2016, 24(5): 612-622.
[11]	Masoud Hasany, Mohammad Malakootikhah, Vahid Rahmanian, Soheila Yaghmaei. Effect of hydrogen combustion reaction on the dehydrogenation of ethane in a fixed-bed catalytic membrane reactor [J]. Chin.J.Chem.Eng., 2015, 23(8): 1316-1325.
[12]	Jiang Yu, Xigang Yuan, Aiwu Zeng. A novel purification process for dodecanedioic acid by molecular distillation [J]. , 2015, 23(3): 499-504.
[13]	Jiangge Hao, Ying Wang, Guozhu Liu, Jingwen Zhang, Guozhu Li, Xuesong Ma. Synthesis of ITQ-2 Zeolites and Catalytic Performance in n-Dodecane Cracking [J]. Chin.J.Chem.Eng., 2014, 22(8): 869-874.
[14]	Jing Feng, Mingsen Zhang, Yuanyi Yang . Dehydrogenation of Propane on Pt or PtSn Catalysts with Al₂O₃ or SBA-15 Support [J]. , 2014, 22(11/12): 1232-1236.
[15]	Farnaz Tahriri Zangeneh, Saeed Sahebdelfar, Mohsen Bahmani. Propane Dehydrogenation over a Commercial Pt-Sn/Al₂O₃ Catalyst for Isobutane Dehydrogenation: Optimization of Reaction Conditions [J]. Chin.J.Chem.Eng., 2013, 21(7): 730-735.