Non-oxidative methane aromatization by bimetallic (La, Co, Pd and Pt) M-Zn/HZSM-5: Impact of propane addition

Document Type : Article


1 Catalyst Research Group, Petrochemical Research and Technology Company, National Petrochemical Company

2 Chemical Engineering Department, Amirkabir University of Technology

3 Department of Civil and Environmental Engineering, University of Alberta, Edmonton


The non-oxidative aromatization of methane was studied over M-Zn/HZSM-5 (M=La, Co, Pd, and Pt) catalysts using propane as a co-reactant. The catalysts were characterized by BET, SEM, NH3-TPD and XRD techniques. Catalytic tests were performed in a fixed-bed reactor at 823 K, using a mixture of methane, propane, and nitrogen with ratio of 6/1/1.3, respectively. Propane conversion was above50% and remained stable in the first 12 hours on stream; however, the methane conversion rapidly dropped from a high of about 10% to zero within 4 hours, implying the absence of a stoichiometric reaction between the reactants. Both zinc and the second metal (M) had a beneficial effect on aromatic selectivity and Pt-Zn/HZSM-5 exhibited the highest aromatic yields and catalyst stability. The results of the present study showed that co-feeding of methane with propane cannot successfully induce methane to participate in aromatization reactions.


Main Subjects

1. Aboul-Gheit, A.K., Awadallah, A.E., El-Kossy, S.M.,
and Mahmoud, AL.H. \E ect of Pd or Ir on the
catalytic performance of Mo/H-ZSM-5 during the nonoxidative
conversion of natural gas to petrochemicals",
J. Nat. Gas Chem., 17, pp. 337-343 (2008).
2. Berndt, H., Lietz, G., Lucke, B., and Volter, J. \Zinc
promoted H-ZSM-5 catalysts for conversion of propane
to aromatics I. Acidity and activity", Appl. Catal. A:
Gen., 146, pp. 351-363 (1996).
3. Bhan, A., Hsu, S.H., Blau, G., Caruthers, J.M.,
Venkatasubramanian, V., and Delgass, W.N. \Microkinetic
modeling of propane aromatization over HZSM-
5", J. Catal., 235, pp. 35-51 (2005).
4. Moghimpour Bijani, P., Sohrabi, M., and Sahebdelfar,
S. \Thermodynamic analysis of nonoxidative dehydroaromatization
of methane", Chem. Eng. Technol.,
35, pp. 1825-1832 (2012).
5. Lukyanov, D.B. and Vazhnova, T. \Selective and
stable benzene alkylation with methane into toluene
over PtH-MFI bifunctional catalyst", J.Mol. Catal. A:
Chem., 305, pp. 95-99 (2009).
6. Choudhary,V.R., Kinage, A.K., and Choudhary, T.V.
\Low-temperature nonoxidative activation of methane
over H-galloaluminosilicate (MFI) zeolite", Science,
275, pp. 1286-1288 (1997).
7. Chu, W. and Qiu, F. \Remarkable promotion of benzene
formation in methane aromatization with ethane
addition", Top. Catal., 22, pp. 131-134 (2003).
8. Echevsky, G., Kodenev, E., Kikhtyanin, O., and
Parmon, V. \Direct insertion of methane into C3-
C4 parans over zeolite catalysts: a start to the
development of new one-step catalytic processes for the
gas-to-liquid transformation", Appl. Catal. A: Gen.,
258, pp. 159-171 (2004).
9. Guo, J., Lou, H., and Zheng, X. \Energy-Ecient
coaromatization of methane and propane", J. Nat. Gas
Chem., 18, pp. 260-272 (2009).
10. Asaftei, I.V., Bilba, N., Birsa, L.M., and Iofcea,
Gh. \Aromatization of industrial feedstock mainly
withbutanes and butenes over HZSM-5 and Zn/HZSM-
5catalysts", Acta. Chem. IASI, 17, pp. 5-34 (2009).
11. Naccache, C.M., Meriaudeau, P., Sapaly, G., Van
Tiep, L., and Ben Ta^arit, Y. \Assessment of the lowtemperature
nonoxidative activation of methane over
H-galloaluminosilicate (MFI) zeolite: A C-13 labelling
investigation", J.Catal., 205, pp. 217-220 (2002).
12. Bradford, M.C.J, Te, M., Konduru, M., and Fuentes,
D.X. \CH4-C2H6-CO2 conversion to aromatics over
Mo/SiO2/H-ZSM-5", Appl. Catal. A: Gen., 266, pp.
55-66 (2004).
13. Luzgin, M.V., Rogov, V.A., Arzumanov, S.S., Toktarev,
A.V., Stepanov, A.G., and Parmon, V.N.
\Methane aromatization on Zn-modi ed zeolite in the
presence of a co-reactant higher alkane: How does it
occur?", Catal. Today, 144, pp. 265-272 (2009).
14. Zhao, X., Wei, L., Cheng, S., Huang, Y., Yu, Y.,
and Julson, J. \Catalytic cracking of camelina oil for
hydrocarbon biofuel over ZSM-5-Zn catalyst", Fuel
Process Technol., 139, pp. 117-126 (2015).
15. Guo, J., Lou, H., Zhao, H., Zheng, L., and Zheng, X.
\Dehydrogenation and aromatization of propane over
rhenium-modi ed HZSM-5 catalyst", J. Mol. Catal. A:
Chem., 239, pp. 222-227 (2005).
16. Wang, D., Kan, Q., Xu, N.,Wu, P., andWu, T. \Study
on methane aromatization over MoO3/HMCM-49 catalyst",
Catal. Today, 93, pp. 75-80 (2004).
17. Xu, Y., Wang, J., Suzuki, Y., and Zhang, Z.G. \E ect
of transition metal additives on the catalytic stability
of Mo/HZSM-5 in the methane dehydroaromatization
under periodic CH4-H2 switch operation at 1073K",
Appl. Catal. A: Gen., 409-410, pp. 181-193 (2011).
18. Lubango, L.M. and Scurrell, M.S. \Light alkanes
aromatization to BTX over Zn-ZSM-5 catalysts: Enhancements
in BTX selectivity by means of a second
transition metal ion", Appl. Catal. A: Gen., 235(1),
pp. 265-272 (2002).
19. Kulkarni, S.S., Mauze, G.R., and Schwarz, J.A. \Concentration
pro les and the design of metal-supported
catalysts", J. Catal., 69(2), pp. 445-453 (1981).
20. Maggiore, R., Scire, S., Galvango, S., Crisafulli, C.,
and Toscano, T. \Hydrogenolysis reactions during
propane aromatization over Pt/ZSM-5", React. Kinet.
Catal. Lett., 46(2), pp. 255-261 (1992).
21. Sadegbeigi, R., Fluid Catalytic Cracking Handbook:
An Expert Guide to the Practical Operation, Design,
and Optimization of FCC Units, 3th Ed. Butterworth-
Heinemann, Netherlands (2012).
22. Caeiro, G., Carvalho, R., Wang, X., Lemos, M.,
Lemos, F., Guisnet, M., and Ram^oa Ribeiro, F. \Activation
of C2-C4 alkanes over acid and bifunctional
zeolite catalysts", J. Mol. Catal. A: Chem., 255, pp.
131-158 (2006).
23. Dong, X., Song, Y., and Lin, W. \A new way to
enhance the coke-resistance of Mo/HZSM-5 catalyst
for methane dehydroaromatization", Catal. Commun.,
8, pp. 539-542 (2007).
P. Moghimpour Bijani et al./Scientia Iranica, Transactions C: Chemistry and ... 25 (2018) 1423{1433 1433
24. Tessonnier, J.P., Louis, B., Rigolet, S., Ledoux, M.J.,
and Pham-Huu, C. \Methane dehydro-aromatization
on Mo/ZSM-5: about the hidden role of Brnsted acid
sites", Appl. Catal. A: Gen., 336, pp. 79-88 (2008).
25. Zheng, L., Xuan, D., Guo, J., Lou, H., and Zheng, X.
\Non-oxidative aromatization of CH4-C3H8 over Lapromoted
Zn/HZSM-5 catalysts", J. Nat. Gas. Chem.,
15, pp. 52-57 (2006).