Methylation of 2-Methylnaphthalene with Methanol over NH4F and Pt Modified HZSM-5 Catalysts

›› 2010, Vol. 18 ›› Issue (5): 742-749.

• CATALYSIS, KINETICS AND REACTORS • Previous Articles Next Articles

Methylation of 2-Methylnaphthalene with Methanol over NH₄F and Pt Modified HZSM-5 Catalysts

ZHAO Liang¹, GUO Xinwen¹, LIU Min¹, WANG Xiangsheng¹, SONG Chunshan^1,2

1. State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116012, China;
2. EMS Energy Institute and Department of Energy & Mineral Engineering, Pennsylvania State University Park, PA 16802, USA

Received:2009-12-07 Revised:2010-07-07 Online:2010-10-28 Published:2010-10-28
Supported by:
Supported by the Program for New Century Excellent Talents in University (NCET-04-0268);the Expertise-Introduction Project for Disciplinary Innovation of Universities

Methylation of 2-Methylnaphthalene with Methanol over NH₄F and Pt Modified HZSM-5 Catalysts

赵亮¹, 郭新闻¹, 刘民¹, 王祥生¹, 宋春山^1,2

1. State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116012, China;
2. EMS Energy Institute and Department of Energy & Mineral Engineering, Pennsylvania State University Park, PA 16802, USA

通讯作者: SONG Chunshan,E-mail:guoxw@dlut.edu.cn;csong@psu.edu
基金资助:
Supported by the Program for New Century Excellent Talents in University (NCET-04-0268);the Expertise-Introduction Project for Disciplinary Innovation of Universities

Abstract

Abstract: Shape-selective methylation of 2-methylnaphthalene (2-MN) was carried out over NH₄F and Pt modified HZSM-5 (SiO₂ /Al₂O₃=83) catalysts in a fixed-bed down-flow reactor using methanol as methylating agent and 1,3,5-trimethylbenzene (1,3,5-TMB) as a solvent. Pt promoted HZSM-5 catalysts showed low concentration of coke-like polycondensed aromatics, NH₄F modification decreased non-shape-selective acid sites. After Pt and NH₄F comodification, both conversion of 2-MN and selectivity tO2,6-DMN were improved. 6% NH₄F/0.5% Pt/HZSM-5 catalyst exhibited 13.8% of 2-MN conversion with 6.2% of 2,6-DMN yield after 7 h time on stream (TOS), and 2,6-/2,7-DMN ratio of 1.7 after 10 h of TOS.

Key words: 2-methylnaphthalene, methylation, HZSM-5,2,6-dimethylnaphthalene, NH₄F/Pt/HZSM-5

摘要： Shape-selective methylation of 2-methylnaphthalene (2-MN) was carried out over NH₄F and Pt modified HZSM-5 (SiO₂ /Al₂O₃=83) catalysts in a fixed-bed down-flow reactor using methanol as methylating agent and 1,3,5-trimethylbenzene (1,3,5-TMB) as a solvent. Pt promoted HZSM-5 catalysts showed low concentration of coke-like polycondensed aromatics, NH₄F modification decreased non-shape-selective acid sites. After Pt and NH₄F comodification, both conversion of 2-MN and selectivity tO2,6-DMN were improved. 6% NH₄F/0.5% Pt/HZSM-5 catalyst exhibited 13.8% of 2-MN conversion with 6.2% of 2,6-DMN yield after 7 h time on stream (TOS), and 2,6-/2,7-DMN ratio of 1.7 after 10 h of TOS.

关键词: 2-methylnaphthalene, methylation, HZSM-5,2,6-dimethylnaphthalene, NH₄F/Pt/HZSM-5

ZHAO Liang, GUO Xinwen, LIU Min, WANG Xiangsheng, SONG Chunshan. Methylation of 2-Methylnaphthalene with Methanol over NH₄F and Pt Modified HZSM-5 Catalysts[J]. , 2010, 18(5): 742-749.

赵亮, 郭新闻, 刘民, 王祥生, 宋春山. Methylation of 2-Methylnaphthalene with Methanol over NH₄F and Pt Modified HZSM-5 Catalysts[J]. , 2010, 18(5): 742-749.

References

1 Song, C.S., “Shape-selective isopropylation of naphthalene over H-mordenite catalysts for environmentally friendly synthesis of 2, 6-dialkylnaphthalene”, C. R. Acad. Sci. Paris IIc Chimie, 3, 477-496 (2000).
2 Song, C.S., Schobert, H.H., “Non-fuel uses of coals and synthesis of chemicals and materials”, Fuel, 75 (6), 724-736 (1996).
3 Inui, T., Pu, S.B., Kugai, J.I., “Selective neutralization of acid sites on the external surface of H-ZSM-5 crystallites by a mechanochemical method for methylation of methylnaphthalene”, Appl. Catal. A Gen., 146 (2), 285-296 (1996).
4 Song, C.S., “Recent advance in shape-selective catalysis over zeolites for synthesis of specialty chemicals”, Stud. Surf. Sci. Catal., 113, 163-186 (1998).
5 Song, C.S., Shen, J.P., Reddy, K.M., Sun, L., Lillwitz, L.D., “Shapeselective Fe-MFI catalyst for synthesis of 2, 6-dimethylnaphthalene by methylation with methanol”, Stud. Surf. Sci. Catal., 170, 1275-1282 (2007).
6 Lillwitz, L.D., “Production of dimethyl-2, 6-naphthalenedicarboxylate:Precursor to polyethylene naphthalate”, Appl. Catal. A Gen., 221 (1-2), 337-358 (2001).
7 Fraenkel, D., Cherniavsky, M., Ittah, B., Levy, M., “Shape-selective alkylation of naphthalene and methylnaphthalene with methanol over H-ZSM-5 zeolite catalysts”, J. Catal., 101 (2), 273-283 (1986).
8 Komatsu, T., Araki, Y., Namba, S., Yashima, T., “Selective formation of 2,6-dimethylnaphthalene from 2-methylnaphthalene on ZSM-5 and metallosilicates with MFI structure”, Stud. Surf. Sci. Catal., 84, 1821-1828 (1994).
9 Pu, S.B., Inui, T., “Synthesis of 2,6-dimethylnaphthalene by methylation of methylnaphthalene on various medium and large-pore zeolite catalysts”, Appl. Catal. A Gen., 146 (2), 305-316 (1996).
10 Park, J.N., Wang, J., Lee, C.W., Park, S.E., “Methylation of naphthlene with methanol over beta-Mordenite, ZSM-12 and MCM-22 zeolite catalysts”, Bull. Kor. Chem. Soc., 23 (7), 1011-1013 (2002).
11 Tsutsui, T., Ijichi, K., Inomata, T., Setiadi, T., Kojima, T., Sato, K., “Enhancement of conversion and selectivity by temperature-swing unsteady-state reaction method in shape-selective methylation of methylnaphthalene with ZSM-5”, Chem. Eng. Sci., 59 (19), 3993-3999 (2004).
12 Park, J.N., Wang, J., Hong, S.I., Lee, C.W., “Effect of dealumination of zeolite catalysts on methylation of 2-methylnaphthalene in a high-pressure fixed-bed flow reactor”, Appl. Catal. A Gen., 292, 68-75 (2005).
13 Song, C.S., Shen, J.P., Lillwitz, L.D., “Selective methylation catalyst, method of catalyst manufacture and methylation process”, US Pat., 7022637 (2006).
14 Jin, L.J., Fang, Y.M., Hu, H.Q., “Selective synthesis of 2, 6-dimethylnaphthalene by methylation of 2-methylnaphthalene with methanol Zr/(Al)ZSM-5”, Catal. Commun., 7 (5), 255-259 (2006).
15 Jin, L.J., Zhou, X.J., Hu, H.Q., Ma,B., “Synthesis of 2, 6-dimethylnaphthalene by methylation of 2-methylnaphthalene on mesoporous ZSM-5 by desilication”, Catal. Commun., 10 (3), 336-340 (2008).
16 Zhang, C., Guo, X.W., Wang, Y.N., Wang, X.S., Song, C.S., “Methylation of 2-methylnaphthalene with methanol to,6-dimethylnaphthalene over HZSM-5 modified by NH₄F and SrO”, Chin. Chem. Lett., 18 (10), 1281-1284 (2007).
17 Zhao, L., Wang, H.B., Liu, M., Guo, X.W., Wang, X.S., Song, C.S., Liu, H.M., “Shape-selective methylation of 2-methylnaphthalene with methanol over hydrothermal treated HZSM-5 zeolite catalysts”, Chem. Eng. Sci., 63 (21), 5298-5303 (2008).
18 Sánchez, N.A., Saniger, J.M., Caillerie, J.B., Blumenfeld, A.L., Fripiat, J.J., “Reaction of HY zeolite with molecular fluorine”, J. Catal., 201 (1), 80-88 (2001).
19 Li, Y.G., Huang, X.M., Liu, L., Liu, X.M., Shen, W.J., Bao, X.H., Xu, Y.D., “Dehydroaromatization of methane over Mo/HZSM-5 pretreated with NH 4 F:Further study on effect of pretreatment temperature”, Chin. J. Catal., 27 (2), 166-170 (2006). (in Chinese)
20 Todorova, S., Su, B.L., “Propane as alkylating agent for benzene alkylation on bimetal Ga and Pt modified H-ZSM-5 catalysts:FTIR Figure 9 IR spectra of modified catalysts after reaction ¹HZSM-5;2-0.5%Pt/HZSM-5;3-4%NH₄F/0.5%Pt/HZSM-5;4-6%NH₄F/0.5%Pt/HZSM-5;5-8%NH₄F/0.5%Pt/ HZSM-5study of effect of pre-treatment conditions and the benzene adsorption”, J. Mol. Catal. A Chem., 201 (1-2), 223-235 (2003).
21 Lukyanov, D.B., Vazhnova, T., “Highly selective and stable alkylation of benzene with ethane into ethylbenzene over bifunctional PtH-MFI catalysts”, J. Mol. Catal. A Chem., 279 (1), 128-132 (2008).
22 Lukyanov, D.B., Vazhnova, T., “A kinetic study of benzene alkylation with ethane into ethylbenzene over bifunctional PtH-MFI catalyst”, J. Catal., 257 (2), 382-389 (2008).
23 Wang, Y.N., Guo, X.W., Zhang, C., Song, F.L., Wang, X.S., Liu, H.O., Xu, X.C., Song, C.S., Zhang, W.P., Liu, X.M., Han, X.H., Bao, X.H., “Influence of calcination temperature on the stability of fluorinated nanosized HZSM-5 in the methylation of biphenyl”, Catal. Lett., 107 (3-4), 209-214 (2006).
24 Guisnet, M., Magnoux, P., “Coking and deactivation of zeolites:Influence of the pore structure”, Appl. Catal. A Gen., 54 (1), 1-27 (1989).
25 Saberi, M.A., Le Van Mao, R., Martin, M., Mak, A.W.H., “Effect of Zn loading of the Pt-Zn-HY trifunctional catalysts on the hydroisomerization of n-heptane”, Appl. Catal. A Gen., 214 (2), 229-236 (2001).
26 Yang, X.M., Ma, H.J., Xu, Z.S., Xu, Y.P., Tian, Z.J., Lin, L.W., “Hydroisomerization of n-dodecane over Pt/MeAPO-11(M=Mg, Mn, Co or Zn) catalysts”, Catal. Commn., 8 (8), 1232-1238 (2007).
27 Woltz, C., Jentys, A., Lercher, J.A., “Improving bifunctional zeolite catalysts for alkane hydroisomerization via gas phase sulfation”, J. Catal., 237 (2), 337-348 (2006).
28 Choudhary, V.R., Sivadinarayana, C., Devadas, P., Sansare, S.D., Magnoux, P., Guisnet, M., “Characterization of coke on H-gallosilicate (MFI) propane aromatization catalyst:Influence of coking conditions on nature and removal of coke”, Micropor. Mesopor. Mater., 21 (1-3), 91-101 (1998).
29 Karge, H.G., Nieβen, W., Bludau, H., “In-situ FTIR measurements of diffusion in coking zeolite catalysts”, Appl. Catal. A Gen., 146 (2), 339-349 (1996).

[1]	Wenpeng Li, Suohe Yang, Xiaoyan Guo, Guangxiang He, Haibo Jin. The effect of operating conditions on acylation of 2-methylnaphthalene in a microchannel reactor [J]. Chin.J.Chem.Eng., 2018, 26(6): 1307-1311.
[2]	Hao Sun, Saijian Shi, Zhenggui Gu. Isomerization of alkyl naphthalene and refining of 2-methylnaphthalene [J]. , 2017, 25(2): 149-152.
[3]	Wei Deng, Xuan He, Chao Zhang, Yunyi Gao, Xuedong Zhu, Kake Zhu, Qisheng Huo, Zhijie Zhou. Promoting Xylene Production in Benzene Methylation using Hierarchically Porous ZSM-5 Derived from a Modified Dry-gel Route [J]. Chin.J.Chem.Eng., 2014, 22(8): 921-929.
[4]	FANG Yanxiong, DENG Yunquan, REN Qinggang, HUANG Jingping, ZHANG Saidan, HUANG Baohua, ZHANG Kun. Blanc Reaction of Aromatic Compounds Catalyzed by Ionic Liquids [J]. , 2008, 16(3): 357-360.

Methylation of 2-Methylnaphthalene with Methanol over NH₄F and Pt Modified HZSM-5 Catalysts

Methylation of 2-Methylnaphthalene with Methanol over NH₄F and Pt Modified HZSM-5 Catalysts

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 4

Recommended Articles

Metrics

Comments