Effect of Silica Base Catalyst on Transformation of Methanol to Hydrocarbon

Abstract:

Five different types of silica catalyst (SBA-15, SBA-15-PO₃H₂, and three different Si/Al ratio of commercial zeolites (30, 80 and 280) were used to study the transformation of methanol to hydrocarbon (MTH). The aim of this study was to investigate the effect of pore diameter and acidity in the structure of silica catalysts on the process performances in terms of methanol conversion and hydrocarbon selectivity. The mesoporous silica catalysts were prepared by co-condensation method. The catalysts samples were characterized by GC-MS, XRD, BET, and NH₃-TPD techniques. The catalytic performance of synthesized and commercial catalysts for MTH process was evaluated using a homemade fixed bed reactor at temperature (300°C). It was found that the liquid hydrocarbon product provided by zeolite catalysts is aromatic hydrocarbons-rich. High Si/Al zeolites with larger pore size lead to higher selectivity and yield to paraffins (C1-C7). In contrast to commercial zeolite catalyst, SBA-15 and its modification with phosphorus species showed no conversion under studied condition. These results indicate that both pore diameter and acidity influence the product distribution in methanol to hydrocarbon process.

• Periodical: Key Engineering Materials (Volume 751)
• Pages: 512-517
• DOI: https://doi.org/10.4028/www.scientific.net/KEM.751.512
• Online since: August 2017
• Authors: Supranee Lao-Ubol*, Phunthinee Somwongsa, Pracha Laoauyporn, Pasinee Panith, Siriporn Larpkiattaworn, Shih Yuan Chen
• Keywords: Mesoporous, Methanol to Hydrocarbon, Zeolite

References

[1] G. A. Olah, Towards oil independence through renewablemethanol chemistry, Angew Chem Int Ed. 52 (2013) 104–107.

DOI: 10.1002/anie.201204995

[2] M. Bjørgen, F. Joensen, K. -P. Lillerud, U. Olsbye, S. Svelle, The mechanisms of ethene and propene formation from methanol over high silica H-ZSM-5 and H-beta, Catal. Today. 142 (2009) 90– 97.

DOI: 10.1016/j.cattod.2009.01.015

[3] I. M. Dahl, S. Kolboe, On the reaction mechanism for propene formation in the MTO reaction over SAPO-34, Catal Lett. 20 (1993) 329 –333.

DOI: 10.1007/bf00769305

[4] S. Lopez-Orozco, A. Inayat, A. Schwab, T. Selvam, W. Schwieger, Zeolitic materials with hierarchical porous structures, Adv Mater. 23 (2011) 2602–2615.

DOI: 10.1002/adma.201100462

[5] A. Hagen, F. Roessner, Ethane to Aromatic Hydrocarbons: Past, Present, Future, Catal Rev. 42 (2000) 403–437.

DOI: 10.1081/cr-100101952

[6] O. Yoshio, A. Hiroshi, S. Yoko, Selective conversion of methanol into aromatic hydrocarbons over zinc exchanged ZSM-5 zeolites, J Chem Soc Faraday Trans, 1 (1988) 1091- 1099.

DOI: 10.1039/f19888401091

[7] M. Stöcker, Methanol-to-hydrocarbons: catalytic materials and their behavior, Micro porous Mesoporous Mater. 29 (1999) 3–48.

[8] Z. M. Cui, Q. Liu, S. W. Bain, Z. Ma, W. G. Song, The Role of Methoxy Groups in Methanol to Olefin Conversion, J Phys Chem C. 112 (2008) 2685–2688.

DOI: 10.1021/jp710491h

[9] M. Bjørgen, F. Joensen, K. P. Lillerud, U. Olsbye, S. Svelle, The mechanisms of ethene and propene formation from methanol over high silica H-ZSM-5 and H-beta, Catal Today. 142 (2009) 90–97.

DOI: 10.1016/j.cattod.2009.01.015

[10] D. Li, Y. Zheng, X.Y. Wang, Pt-loaded P-MCM-41 as a novel bifunctional catalyst for catalytic combustion of trichloroethylene, Catal Commun. 8 (2007) 1583–1587.

DOI: 10.1016/j.catcom.2007.01.004

[11] D. Li, Y. Zheng, X.Y. Wang, Effect of phosphoric acid on catalytic combustion of trichloroethylene over Pt/P-MCM-41, Appl. Catal. A: Gen. 340 (2008) 33–41.

DOI: 10.1016/j.apcata.2008.01.035

[12] Y. Wan, Y. Hai, Q.F. Zhao, M. Klingstedt, O. Terasaki, D.Y. Zhao, Ordered Mesoporous Pd/Silica−Carbon as a Highly Active Heterogeneous Catalyst for Coupling Reaction of Chlorobenzene in Aqueous Media, J Am Chem Soc. 131 (2009) 4541–4550.

DOI: 10.1021/ja808481g

[13] S. Kawi, S.C. Shen, P.L. Chew, Generation of Brønsted acid sites on Si-MCM-41 by grafting of phosphorus species, J Mater Chem. 12 (2007) 1582–1586.

DOI: 10.1039/b107795n

[14] S.Y. Chen, T. Yokoi, C.Y. Tang, L.Y. Jang, T. Tatsumi, J.C.C. Chan, S. Cheng, Sulfonic acid-functionalized platelet SBA-15 materials as efficient catalysts for biodiesel synthesis, Green Chem., 13 (2011) 2920–2930.

DOI: 10.1039/c1gc15299h

[15] J. K. Shon, X. Yuan, C, H. Ko, H. I. Lee, S. S. Thakur, M. Kang, M. S. Kang, D. Li, J. N. Kim, J. M. Ki, Design of mesoporous solid acid catalysts with controlled acid strength, J. Ind. Eng. Chem., 13 (2007) 1201-1207.

[16] B. Wu, Z. Tong, X. Yuan, Synthesis, characterization and catalytic application of mesoporous molecular sieves SBA-15 functionalized with phosphoric acid, J Porous Mater., 19 (2012) 641-647.

DOI: 10.1007/s10934-011-9515-4

[17] S. Lowell, J.E. Shields, M.A. Thomas, M. Thommes, Characterization of Porous Solids and Powders: Surface Area, Pore Size and Density, Particle Technol. Ser. 16 (2004).

DOI: 10.1007/978-1-4020-2303-3

[18] D. Macinaa, Z. Piwowarskaa, K. Taracha, K. Góra-Mareka, J. Ryczkowskib, L. Chmielarza Mesoporous silica materials modified with alumina polycations as catalysts for the synthesis of dimethyl ether from methanol, Mater Res Bull. 74 (2016) 425–435.

DOI: 10.1016/j.materresbull.2015.11.018

[19] M. Richter, J. Janchen, H. G. Jerschkewitz, B. Parlitz, E. Schreier, Specific modification of the external surface of ZSM-5 zeolites by 12-tungstosilicic acid, J Chem Soc Faraday Trans. 87 (1991) 1461-1466.

DOI: 10.1039/ft9918701461