Superparamagnetic Supported Catalyst H3PW12O40/γ-Fe2O3 for Alkylation of Thiophene with Olefine

doi:10.1016/S1004-9541(14)60053-7

Chinese Journal of Chemical Engineering ›› 2014, Vol. 22 ›› Issue (3): 305-311.DOI: 10.1016/S1004-9541(14)60053-7

• 催化、动力学与反应工程 • 上一篇下一篇

Superparamagnetic Supported Catalyst H₃PW₁₂O₄₀/γ-Fe₂O₃ for Alkylation of Thiophene with Olefine

许翠霞¹, 杨克迪¹, 刘自力^1,2, 秦祖赠¹, 何维³, 代倩雯², 张健杰², 张帆²

1 School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, China;
2 China Key Laboratory of Ministry of Education for Water Quality Security and Protection in Pearl River Delta, School of Chemistry & Chemical Engineering, Guangzhou University, Guangzhou 510006, China;
3 Key laboratory of Nonferrous Metal and New Processing Technology of Materials (Ministry of Education), Guangxi University, Nanning 530004, China

收稿日期:2012-10-11 修回日期:2013-04-30 出版日期:2014-03-28 发布日期:2014-03-05
通讯作者: LIU Zili
基金资助:
Supported by the National Natural Science Foundation of China (21076047).

Superparamagnetic Supported Catalyst H₃PW₁₂O₄₀/γ-Fe₂O₃ for Alkylation of Thiophene with Olefine

XU Cuixia¹, YANG Kedi¹, LIU Zili^1,2, QIN Zuzeng¹, HE Wei³, DAI Qianwen², ZHANG Jianjie², ZHANG Fan²

1 School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, China;
2 China Key Laboratory of Ministry of Education for Water Quality Security and Protection in Pearl River Delta, School of Chemistry & Chemical Engineering, Guangzhou University, Guangzhou 510006, China;
3 Key laboratory of Nonferrous Metal and New Processing Technology of Materials (Ministry of Education), Guangxi University, Nanning 530004, China

Received:2012-10-11 Revised:2013-04-30 Online:2014-03-28 Published:2014-03-05
Contact: LIU Zili
Supported by:
Supported by the National Natural Science Foundation of China (21076047).

摘要/Abstract

摘要： The alkylation of sulfur compounds with olefine is considered to be an attractive way to attain high level of sulfur removal by raising the boiling point of sulfur-containing compounds to ease their separation from light fractions by distillation. A series of superparamagnetic supported catalysts, used for alkylation of thiophene with 1-octene, were prepared by loading H₃PW₁₂O₄₀ (HPW) onto commercially available nanoparticles γ-Fe₂O₃ through incipient wet impregnation method. The catalysts were characterized by X-ray diffraction (XRD), Fourier transform infra-red (FT-IR), thermo gravimetric analysis (TG), N₂-adsorption and vibrating sample magnetometer (VSM). The physicochemical characterization reveals that γ-Fe₂O₃ could be accommodated to immobilize and disperse HPW. Moreover, possessing high magnetization of 26.1 A·m²·kg^-1 and with mesoporous structure with specific surface area of 35.9 m²·g^-1, the 40% (by mass) HPW loading catalyst is considered the proper catalyst for olefinic alkylation of thiophenic sulfur (OATS) and can be separated in an external magnetic field. The catalytic activity was investigated in the alkylation reaction of thiophene with 1-octene, and the conversion of thiophene is up to 46% at 160 ℃ in 3 h. The 40% (by mass) HPW/γ-Fe₂O₃ catalyst can be reused 6 times without too much loss of activity and keeps its property of superparamagnetism.

关键词: alkylation, heteropolyacid, thiophene, superparamagetism

Abstract: The alkylation of sulfur compounds with olefine is considered to be an attractive way to attain high level of sulfur removal by raising the boiling point of sulfur-containing compounds to ease their separation from light fractions by distillation. A series of superparamagnetic supported catalysts, used for alkylation of thiophene with 1-octene, were prepared by loading H₃PW₁₂O₄₀ (HPW) onto commercially available nanoparticles γ-Fe₂O₃ through incipient wet impregnation method. The catalysts were characterized by X-ray diffraction (XRD), Fourier transform infra-red (FT-IR), thermo gravimetric analysis (TG), N₂-adsorption and vibrating sample magnetometer (VSM). The physicochemical characterization reveals that γ-Fe₂O₃ could be accommodated to immobilize and disperse HPW. Moreover, possessing high magnetization of 26.1 A·m²·kg^-1 and with mesoporous structure with specific surface area of 35.9 m²·g^-1, the 40% (by mass) HPW loading catalyst is considered the proper catalyst for olefinic alkylation of thiophenic sulfur (OATS) and can be separated in an external magnetic field. The catalytic activity was investigated in the alkylation reaction of thiophene with 1-octene, and the conversion of thiophene is up to 46% at 160 ℃ in 3 h. The 40% (by mass) HPW/γ-Fe₂O₃ catalyst can be reused 6 times without too much loss of activity and keeps its property of superparamagnetism.

Key words: alkylation, heteropolyacid, thiophene, superparamagetism

许翠霞, 杨克迪, 刘自力, 秦祖赠, 何维, 代倩雯, 张健杰, 张帆. Superparamagnetic Supported Catalyst H₃PW₁₂O₄₀/γ-Fe₂O₃ for Alkylation of Thiophene with Olefine[J]. Chinese Journal of Chemical Engineering, 2014, 22(3): 305-311.

XU Cuixia, YANG Kedi, LIU Zili, QIN Zuzeng, HE Wei, DAI Qianwen, ZHANG Jianjie, ZHANG Fan. Superparamagnetic Supported Catalyst H₃PW₁₂O₄₀/γ-Fe₂O₃ for Alkylation of Thiophene with Olefine[J]. Chin.J.Chem.Eng., 2014, 22(3): 305-311.

参考文献

1 Bellière, V., Lorentz, C., Geantet, C., Yoshimura, Y., Laurenti, D., Vrinat, M., "Kinetics and mechanism of liquid-phase alkylation of 3-methylthiophene with 2-methyl-2-butene over a solid phosphoric acid", Appl. Catal. B Environ., 64, 254-261 (2006).

2 Takatsuka, T., Inoue, S., Wada, Y., "Deep hydrodesulfurization process for diesel oil", Catal. Today, 39, 69-75 (1997). 3 Jaimes, L., Badillo, M., de Lasa, H., "FCC gasoline desulfurization using a ZSM-5 catalyst interactive effects of sulfur containing species and gasoline components", Fuel, 90, 2016-2025 (2011).

4 Martínez-Magadán, J.M., Oviedo-Roa, R., García, P., Martínez-Palou, R., "DFT study of the interaction between ethanethiol and Fe-containing ionic liquids for desulfuration of natural gasoline", Fuel Process. Technol., 97, 24-29 (2012).

5 Huff, G.A., Owen, O.S., Alexander, B.D., Rundell, D.N., Reagan, W.J., Yoo, J.S., "Sulfur removal by catalytic distillation", US Pat., 5863419 (1999).

6 Brunet, S., Mey, D., Perot, G., Bouchy, C., Diehl, F., "On the hydrodesulfurization of FCC gasoline: A review", Appl. Catal. A Gen., 278, 143-150 (2005).

7 Zhang, Z.K., Jiang, H., Liu, S.L., Wang, Q.X., Xu, L.Y., "Alkylation performance of thiophene and derivatives during olefinic alkylation of thiophenic sulfur in gasoline", Chin. J. Catal., 27, 309-313 (2006).

8 Bellière, V., Geantet, C., Vrinat, M., Ben-Taarit, Y., Yoshimura, Y., "Alkylation of 3-methylthiophene with 2-methyl-2-butene over a zeolitic catalyst", Energy Fuels, 18, 1806-1813 (2004).

9 Hu, L., Zhang, Z., Xie, S., Liu,S., Xu,L., "Effect of grain size of zeolite Y on its catalytic performance in olefin alkylation thiophenic sulfur process", Catal. Commun., 10, 900-904 (2009).

10 Zhang, Z.K., Niu, X.L., Liu, S.L., Zhu, X.X., Yu, H.W., Xu, L.Y., "The performance of HMCM-22 zeolite catalyst on the olefin alkylation thiophenic sulfur in gasoline", Catal. Commun., 9, 60-64 (2008).

11 Zhang, Z.K., Liu, S.L., Zhu, X.X., Wang, Q., Xu, L.Y., "Modification of Hb zeolite by fluorine and its influence on olefin alkylation thiophenic sulfur in gasoline", Fuel Process. Technol., 89, 103-109 (2008).

12 Shi, R.G., Li, Y.H., Wang, R., Guo, B.S., "Alkylation of thiophenic compounds with olefine and its kinetics over MCM-41 supported phosphoric acid in FCC gasoline", Catal. Lett., 139, 114-122 (2010).

13 Guo, B.S., Wang, R., Li, Y.H., "The performance of solid phosphoric acid catalysts and macroporous sulfonic resins on gasoline alkylation desulfurization", Fuel Process. Technol., 91, 1731-1735 (2010).

14 Arias, M., Laurenti, D., Bellière, V., Geantet, C., Vrinat, M., Yoshimura, Y., "Preparation of supported H₃PW₁₂O₄₀·6H₂O for thiophenic compounds alkylation in FCC gasoline" Appl. Catal. A Gen., 348, 142-147 (2008).

15 Arias, M., Laurenti, D., Bellière, V., Geantet, C., Vrinat, M., Yoshimura, Y., "Gasoline desulfurization by catalytic alkylation over silica- supported heteropolyacids: From model reaction to real feed conversion", Catal. Today, 130, 190-194 (2008).

16 Guo, B.S., Wang, R., Li, Y.H., "Gasoline alkylation desulfurization over Amberlyst 35 resin: Influence of methanol and apparent reaction kinetics", Fuel, 90, 713-718 (2011).

17 Kozhevnikov, I.V., "Sustainable heterogeneous acid catalysis by heteropoly acids", J. Mol. Catal. A: Chem., 262, 86-92 (2007).

18 Kamiya, Y., Ooka, Y., Obara, C., Ohnishi, R., Fujita, T., Kurata, Y., Tsuji, K., Nakajyo, T., Okuhara, T., "Alkylation-acylation of p-xylene with butyrolactone or vinylacetic acid catalyzed by heteropolyacid supported on silica", J. Mol. Catal. A Chem., 262, 77-85 (2007).

19 Angelis, A., Amarilli, S., Berti, D., Montanari, L., Perego, C., "Alkylation of benzene catalysed by supported heteropolyacids", J. Mol. Catal. A Chem., 146, 37-44 (1999).

20 Yadav, G..D., Bokade, V.V., "Novelties of heteropoly acid supported on clay: Etherification of phenethyl alcohol with alkanols", Appl. Catal. A Gen., 147, 299-323 (1996).

21 Nandhini, K.U., Arabindoo, B., Palanichamy, M., Murugesan, V., "t-Butylation of phenol over mesoporous aluminophosphate and heteropolyacid supported aluminophosphate molecular sieves", J. Mol. Catal. A Chem., 223, 201-210 (2004).

22 Guo, P.M., Huang, F.H., Huang, Q.D., Zheng, C., "Biodiesel production using magnetically stabilized fluidized bed reactor", Renew. Energy, 38, 10-15 (2012).

23 Lei, Z.G., Li, C.Y., Li, J.W., Chen, B.H., "Suspension catalytic distillation of simultaneous alkylation and transalkylation for producing cumene", Sep. Purif. Technol., 34, 265-271 (2004).

24 Webb, C., Kang, H.K., Moffat, G., Williams, R.A., Estévez, A.M., Cuéllar, J., Jaraiz, E., Galán, M.A., "The magnetically stabilized fluidized bed bioreactor: A tool for improved mass transfer in immobilized enzyme systems?", Chem. Eng. J., 61, 241-246 (1996).

25 Li, W., Zong, B.N., X.F., Meng, X.K., Zhang, J.L., "Interphase mass transfer in G-L-S magnetically stabilized bed with amorphous alloy SRNA-4 catalyst", Chin. J. Chem. Eng., 14, 734-739 (2006).

26 Zhang, D.L., Zhang, Y.J., Zhang, J.L., Li,X.F., Lu, L.X., Meng, X.K., Mu,X.H., "Axial liquid dispersion characteristics in magnetically stabilized bed," Chin. J. Chem. Eng., 14, 532 -536 (2006).

27 Satish Kumar, G., Vishnuvarthan, M., Palanichamy, M., Murugesan, V., "SBA-15 supported HPW: Effective catalytic performance in the alkylation of phenol", J. Mol. Catal. A Chem., 260, 49-55 (2006).

28 Wang, J.Y., Wang, X.Q., Li, R., Wang, Q., Li, L., Liu, W.M., Wan, Z.F., Yang, L.Y., Sun, P., Ren, L.L., Li, M.L., Wu, H., Wang, J.F., Zhang, L., "Conjugation of biomolecules with magnetic protein microspheres for the assay of early biomarkers associated with acute myocardial infarction", Anal. Chem., 81, 6210-6217 (2009).

29 Izumi, Y., Ogawa, M., Urabe, K., "Alkali metal salts and ammonium salts of Keggin-type heteropolyacids as solid acid catalysts for liquid-phase Friedel-Crafts reactions", Appl. Catal. A Gen., 132, 127-140 (1995).

30 Zhang, J.X., Sun, W., Bergman, L., Rosenholm, J. M., Lindén, M., Wu, G.J., Xu, H., Gu, H.C., "Magnetic mesoporous silica nanospheres as DNA/drug carrier", Mater. Lett., 67, 379-382 (2012).

31 Kroll, E., Winnik, F.M., "In situ preparation of nanocrystalline γ-Fe₂O₃ in iron(II) cross-linked alginate gels", Chem. Mater., 8, 1594-1596 (1996).

32 Schmidt, L.D., The Engineering of Chemical Reactions, Oxford University Press, Oxford, 362-378 (2005).

33 Leng, Y., Wang, J., Zhu, D.R., Wu, Y.J., Zhao, P.P., "Sulfonated organic heteropolyacid salts: Recyclable green solid catalysts for esterifications", J. Mol. Catal. A Chem., 313, 1-6 (2009).

34 Soled, S., Miseo, S., McVicker, G., Gates, W.E., Gutierrez, A., Paes, J., "Preparation and catalytic properties of supported heteropolyacid salts", Chem. Eng. J., 64, 247-254 (1996).

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Superparamagnetic Supported Catalyst H₃PW₁₂O₄₀/γ-Fe₂O₃ for Alkylation of Thiophene with Olefine

Superparamagnetic Supported Catalyst H₃PW₁₂O₄₀/γ-Fe₂O₃ for Alkylation of Thiophene with Olefine

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