Conversion of Methanol to Propylene over a High Silica B-HZSM-5 Catalyst
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 32799
Conversion of Methanol to Propylene over a High Silica B-HZSM-5 Catalyst

Authors: Aina Xu, Hongfang Ma, Haitao Zhang, Weiyong Ying, Dingye Fang

Abstract:

Hydrothermally synthesized high silica borosilicates with the MFI structure was subjected to several characterization techniques. The effect of boron on the structure and acidity of HZSM-5 catalyst were studied by XRD, SEM, N2 adsorption, solid state NMR, NH3-TPD. It was confirmed that boron had entered the framework in the boron samples. The results also revealed that strong acidity was weakened and weak acidity was strengthened by the boron added zeolite framework compared with parent catalyst. The catalytic performance was carried out in a fixed bed at 460°C for methanol to propylene (MTP) reaction. The results of MTP reaction showed a great increment of the propylene selectivity and excellent stability for the B-HZSM-5. The catalyst exhibited about 81% selectivity to C2 = - C4 = olefins with 40% selectivity of propylene as major component at near 100% methanol conversion, and the stable performance in the studied period was 100h.

Keywords: Methanol to propylene, HZSM-5, boron.

Digital Object Identifier (DOI): doi.org/10.5281/zenodo.1333490

Procedia APA BibTeX Chicago EndNote Harvard JSON MLA RIS XML ISO 690 PDF Downloads 3521

References:


[1] M. Bj├©rgen, F. Joensen, M.S. Holm, U. Olsbye, K.-P. Lillerud, S. Svelle, "Methanol to gasoline over zeolite H-ZSM-5 Improved catalyst performance by treatment with NaOH", Appl. Catal. A, vol. 345, pp. 43-50, Apr. 2008.
[2] M. Stöcker, "Methanol-to-hydrocarbons: catalytic materials and their behavior Micropor", Micropor. Mesopor. Mater., vol. 29, pp. 3-48, Jun. 1999.
[3] J.Q. Chen, A. Bozzano, B. Glover, T. Fuglerud, S. Kvisle, "Recent advancements in ethylene and propylene production using the UOP/Hydro MTO process", Catal. Today, vol. 106, pp. 103-106, Oct. 2005.
[4] M. Hack, U. Koss, P. Konig, M. Rothaemel, H.D. Holtmann, US Patent 7015369 B2, 2006, to MG Technologies AG.
[5] C.S. Mei, P.Y. Wen, Z.C. Liu, H.X. Wang, W.M. Yang, Z.K. Xie, W.M. Hua, Z. Gao, "Selective production of propylene from methanol: Mesoporosity development in high silica HZSM-5", J. Catal., vol. 258, pp. 243-249, Aug. 2008.
[6] S. Svelle, F. Joensen, J. Nerlov, U. Olsbye, K.-P. Lillerud, S. Kolboe, M. Bj├©rgen, "Conversion of Methanol into Hydrocarbons over Zeolite H-ZSM-5: Ethene Formation Is Mechanistically Separated from the Formation of Higher Alkenes", J. Am. Chem. Soc., vol. 128, pp. 14770-14771, Oct. 2006.
[7] S. Svelle, U. Olsbye, F. Joensen, M. Bjorgen, "Conversion of Methanol to Alkenes over Medium- and Large-Pore Acidic Zeolites: Steric Manipulation of the Reaction Intermediates Governs the Ethene/Propene Product Selectivity", J. Phys. Chem. C, vol. 111, pp. 17981-17984, Nov. 2007.
[8] Y.-J. Lee, Y.-W. Kim, N. Viswanadham, K.-W. Jun, J.W. Bae, "Novel aluminophosphate (AlPO) bound ZSM-5 extrudates with improved catalytic properties for methanol to propylene (MTP) reaction", Appl. Catal. A, vol. 374, pp. 18-25, Feb. 2010.
[9] A.M. Al-Jarallah, U.A. El-Nafaty, M.M. Abdillahi, "Effects of metal impregnation on the activity, selectivity and deactivation of a high silica MFI zeolite when converting methanol to light alkenes", Appl. Catal. A, vol. 154, pp. 117-127, Jun. 1997.
[10] T. Blasco, A. Corma, J. Martínez-Triguero, "Hydrothermal stabilization of ZSM-5 catalytic-cracking additives by phosphorus addition", J. Catal., vol. 237, pp. 267-277, Jan. 2006.
[11] M.R. Klotz, Belg. Patent 859656 A1, 1978.
[12] E. Unneberg, S. Kolboe, "H-
[B]-ZSM-5 as catalyst for methanol reactions", Appl. Catal. A, vol. 124, pp. 345-354, Apr. 1995.
[13] S. Svelle, L. Sommer, K. Barbera, P.N.R. Vennestrm, U. Olsbye, K.P. Lillerud, S. Bordiga, Y.-H. Pan, P. Beato, "How defects and crystal morphology control the effects of desilication", Catalysis Today, vol. 168, pp. 38-47, Jun. 2011.
[14] L. Karwacki, M.H.F. Kox, D.A.M. de Winter, M.R. Drury, J.D. Meeldijk, E. Stavitski, W. Schmidt, M. Mertens, P. Cubillas, N. John, A. Chan, N. Kahn, S.R. Bare, M. Anderson, J. Kornatowski, B.M. Weckhuysen, "Morphology-dependent zeolite intergrowth structures leading to distinct internal and outer-surface molecular diffusion barriers", Nat. Mater., vol. 8, pp. 959-965, Sep. 2009.
[15] S.M. Cabral de Menezes, Y.L. Lam, K. Damodaran, M. Pruski, "Modification of H-ZSM-5 zeolites with phosphorus. 1. Identification of aluminum species by 27Al solid-state NMR and characterization of their catalytic properties", Micropor. Mesopor. Mater., vol. 95, pp. 286-295, Oct. 2006.
[16] A.P. Lee, B.L. Phillips, M.M. Olmstead, W.H. Casey, "Synthesis and characterization of the GeO4Al12(OH)(24)(OH2)(12)(8+) polyoxocation", Inorg. Chem., vol. 40, pp.4485-4487, Aug. 2001.
[17] R. de Ruiter, A.P.M. Kentgens, J. Grootendorst, J.C. Jansen, H. van Bekkum, "Calcination and deboronation of
[B]-MFI single crystals", Zeolites, vol. 13, pp. 128-138, Feb. 1993.
[18] W.Y. Dong, Y.J. Sun, H.Y. He, Y.C. Long, "Synthesis and structural characterization of B-Al-ZSM-5 zeolite from boron-silicon porous glass in the vapor phase", Micropor. Mesopor. Mater., vol. 32, pp. 93-100, Nov. 1999.
[19] V.R. Reddy Marthala, W. Wang, J. Jiao, Y.j. Jiang, J. Huang, M. Hunger, "Effect of probe molecules with different proton affinities on the coordination of boron atoms in dehydrated zeolite H-
[B]ZSM-5", Micropor. Mesopor. Mater., vol. 99, pp. 91-97, Feb. 2007.
[20] M. Firoozi, M. Baghalha, M. Asadi, "The effect of micro and nano particle sizes of H-ZSM-5 on the selectivity of MTP reaction", Catal. Comm., vol. 10, pp. 1582-1585, Jun. 2009.
[21] C.S. Mei, P.Y. Wen, Z.C Liu, H.X Liu, Y.D. Wang, W.M. Yang, Z.K. Xie, W.M. Hua, Z. Gao, "Selective production of propylene from methanol: Mesoporosity development in high silica HZSM-5", J. Catal., vol. 258, pp. 243-249, Aug. 2008.
[22] C.D. Chang, C.T-W. Chu, R.F. Socha, "Methanol conversion to olefins over ZSM-5: I. Effect of temperature and zeolite SiO2 / Al2O3", J. Catal., vol. 86, pp. 289-296, Apr. 1984.
[23] J. Liu, C.X. Zhang, Z.H. Shen, W.M. Hua, Y. Tang, W. Shen, Y.H. Yue, H.L. Xu, "Methanol to propylene: Effect of phosphorus on a high silica HZSM-5 catalyst", Catal. Comm., vol. 10, pp. 1506-1509, Jun. 2009.
[24] H. Mochizuki, T. Yokoi, H. Imai, R. Watanabe, S. Namba, J.N. Kondo, T. Tatsumi, "Facile control of crystallite size of ZSM-5 catalyst for cracking of hexane", Micropor. Mesopor. Mater., vol. 145, pp. 165-171, Nov. 2011.