skip to main content

Study of Catalytic Properties of the HoxMg1-xAl2O4 Modified HZSM-5 Zeolite in Conversion of Methanol to C2-C4 Alkenes and p-Xylene

1Department of Physical and Colloid Chemistry, Chemistry Faculty, Baku State University, Baku AZ1148, Azerbaijan

2Chemistry Faculty, Branch of Moscow State University, Baku, Azerbaijan, Baku AZ1142, Azerbaijan

Received: 14 Jul 2022; Revised: 29 Sep 2022; Accepted: 7 Oct 2022; Available online: 8 Oct 2022; Published: 25 Dec 2022.
Editor(s): Istadi Istadi
Open Access Copyright (c) 2022 by Authors, Published by BCREC Group
Creative Commons License This work is licensed under a Creative Commons Attribution-ShareAlike 4.0 International License.

Citation Format:
Cover Image
Abstract

Selective conversion of methanol to C2-C4 alkenes and p-xylene is one of the appealing chemical routes. Currently, there are no effective catalysts for the co-production of C2-C4 alkenes and p-xylene from methanol. To date, modified medium-pore ZSM-5 zeolites are considered one of the excellent candidates for the development of selective catalysts for the conversion of methanol to lower alkenes and aromatic hydrocarbons. In this paper, nanosized (30-33nm) powders of HoхMg1-хAl2O4 spinel structure were obtained by the method of combustion of nitrate solutions of aluminium, magnesium, holmium, diethylmalonate and hydrazine monohydrate with the further calcination of nanopowders at 1000 °C. Obtained nanopowders used in the preparation of a solid-phase catalytic composition of HoхMg1-хAl2O4-HZSM-5. Various physico-chemical properties of the catalytic composition were investigated using X-ray diffraction (XRD), pyridine adsorption (BİO-RAD FTS 3000 MX) and low-temperature nitrogen adsorption (BET) techniques. The textural properties and acidity of the catalysts were altered by adjusting the nanopowder concentration (1.0-5.0 wt.%) in the catalytic composition. The conversion of methanol in the presence of the catalytic compositions was carried out in flow-type fixed-bed catalytic reactor at 400 °C, in the presence of nitrogen carrier gas with 1.0 h-1 flow rate. A correlation between the selectivity to C2-C4 alkenes and p-xylene with a ratio of Lewis (L) and Brønsted (B) acid sites and the volume of the catalyst pore, the amount of the modifier in the catalytic system has been established. As the amount of HoхMg1-хAl2O4 nanopowder increases, the ratio of B/L acid sites and the volume of the catalyst pore decrease, which play a significant role in the increase of the selectivity to C2-C4 alkenes and p-xylene. Maximum yield of C2-C4 alkenes (31.6%) and selectivity to p-xylene (80.5%) is achieved on a catalytic composition containing 5.0 wt.% HoxMg1-xAl2O4. Copyright © 2022 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

 

Fulltext View|Download
Keywords: methanol; С2-С4 alkenes; p-xylene; НZSM-5; nanopowders HoxMg1-xAl2O4
Funding: Ministry of Education of Azerbaijan

Article Metrics:

  1. Normuminov, A., Ruziev, J., Fayzullaev, N. (2021). The Contact Time Effect Of Lower Alkane Pyrolysis Process On Target Product Yield In The Presence Of High-Silicon Zeolite Retaining Catalysts. Universum: Chemistry & Biology. 8(86), 90-96. DOI: 10.32743/Unichem.2021.86.8.12143
  2. Doronin, V.P.; Sorokina, T. P.; Lipin, P.V.; Potapenko, O.V.; Korotkova, N.V.; Gordenko, V.I. (2015). Development and introduction of zeolite containing catalysts for cracking with controlled contents of rare earth elements. Catalysis In Industry. 7(1), 12-16. DOI: 10.1134/S2070050415010043
  3. Kuzmina, R.I., Liventsev, V.T., Sevost’yanov, V.P., Dogadina, N.V. (2005). Modification of the Alumina-Supported Platinum Catalyst of Reforming. Russian Journal of Applied Chemistry. 78, 96–100. DOI: 10.1007/s11167-005-0238-7
  4. Song, W., Marcus D.M., Fu, H., Ehresmann, J.O., Haw J.F. (2002). An Oft-Studied Reaction That May Never Have Been: Direct Catalytic Conversion of Methanol or Dimethyl Ether to Hydrocarbons on the Solid Acids HZSM-5 or HSAPO-34. Journal of the American Chemical Society. 124(15), 3844-3845. DOI: 10.1021/ja016499u
  5. Dubois, D.R., Obrzut, D.L., Liu, J., Thundimadathil, J., Adekkanattu, P. M., Guin, J.A., Punnoose A., Seehra, M.S. (2003). Conversion of methanol to olefins over cobalt-, manganese- and nickel-incorporated SAPO-34 molecular sieves. Fuel Processing Technology. 83 (1-3), 203-218. DOI: 10.1016/S0378-3820(03)00069-9
  6. Liu, H., Kainfar, E. (2021). Investigation the Synthesis of Nano-SAPO-34 Catalyst Prepared by Different Templates for MTO Process. Catalysis Letter. 151, 787-802. DOI: 10.1007/s10562-020-03333-6
  7. Chakraborty, J.P., Singh, S., Maity, S.K. (2022). Chapter 6- Advances in the conversion of methanol to gasoline. Hydrocarbon Biorefinery. Sustainable Processing of Biomass for Hydrocarbon Biofuels, 177-200. DOI: 10.1016/B978-0-12-823306-1.00008-X
  8. Kianfar, E., Salimi, M., Pirouzfar, V., Koohestani, B. (2018). Synthesis of Modified Catalyst and Stabilization of CuO/NH4-ZSM-5 for Conversion of Methanol to Gasoline. International Journal of Applied Ceramic Technology. 15(3), 734-741. DOI: 10.1111/ijac.12830
  9. Teketel, Sh., Erichsen, M.W., Bleken, F.L., Svelle, S., Lillerud, K.P., Olsbye, U. (2014). Shape selectivity in zeolite catalysis. The Methanol to Hydrocarbons (MTH) reaction. Catalysis. 26, 179-217. DOI: 10.1039/9781782620037-00179
  10. Bjørgen, M., Svelle, S., Joensen, F.J.N., Kolboe, S., Bonino, F., Palumbo, L., Bordiga, S., Olsbye U. (2007). Conversion of methanol to hydrocarbons over zeolite H-ZSM-5: On the origin of the olefinic species. Journal of Catalysis. 249(2), 195-207. DOI: 10.1016/j.jcat.2007.04.006
  11. Palcic, A., Catizzone, E. (2021). Application of nanosized zeolites in methanol conversion processes: A short review. Current opinion in green and sustainable chemistry. 27, 100393-100397. DOI: 10.1016/j.cogsc.2020.100393
  12. Chen, Z., Hou, Y., Yang, Y., Cai, D., Song, W., Wang, N., Qian, W. (2019). Multi-Stage Fluidized Bed Strategy For The Enhanced Conversion Of Methanol Into Aromatics. Chemical Engineering Science. 204, 1-8. DOI: 10.1016/j.ces.2019.04.013
  13. Chen, Z., Wang H., Song, W., Hou, Y., Qian, W. (2020). Decentralized methanol feed in a two-stage fluidized bed for process intensification of methanol to aromatics. Chemical Engineering and Processing - Process Intensification. 154, 108049. DOI: 10.1016/j.cep.2020.108049
  14. Gao, P., Xu, J., Qi, G., Wang, C., Wang, Q., Zhao, Y., Zhang, Y., Feng, N., Zhao, X., Li, J., Deng, F. (2018). A Mechanistic Study of Methanol-to-Aromatics Reaction over Ga-Modified ZSM-5 Zeolites: Understanding the Dehydrogenation Process. ACS Catalysis. 8 (10), 9809-9820. DOI: 10.1021/acscatal.8b03076
  15. Chen, Z., Hou, Y., Song, W., Cai, D., Yang, Y., Cui, Y., Qian, W. (2019). High-yield production of aromatics from methanol using a temperature-shifting multi-stage fluidized bed reactor technology. Chemical Engineering Journal. 371, 639-646. DOI: 10.1016/j.cej.2019.04.024
  16. Tian, Sh.X., Ji, Sh.F., Sun, Q. (2014). Preparation of Phosphorus Modified HZSM-5 Zeolite Catalysts and their Catalytic Performances of Methanol to Olefins. Advanced Materials Research. 875-877, 295-299. DOI: 10.4028/www.scientific.net/AMR.875-877.295
  17. Sadeghi, S., Haghighi, M., Estifaee, P. (2015). Methanol to clean gasoline over nanostructured CuO–ZnO/HZSM-5 catalyst: Influence of conventional and ultrasound assisted co-impregnation synthesis on catalytic properties and performance. Journal of Natural Gas Science and Engineering. 24, 302-310. DOI: 10.1016/j.jngse.2015.03.04
  18. Zhang, C., Kwak, G., Lee, Y.-J., Jun, K.-W., Gao, R., Park, H.-G., Kim, S., Min, J.-E., Kang, S.C., Guan, G. (2019). Light hydrocarbons to BTEX aromatics over Zn-modified hierarchical ZSM-5 combined with enhanced catalytic activity and stability. Microporous and Mesoporous Materials. 284, 316-326. DOI: 10.1016/j.micromeso.2019.04.041
  19. Tian, H.F., Yang, X., Tian H.Z., Zha, F., Guo, X.J., Tang, X.H. (2021). Realization of rapid synthesis of H-ZSM-5 zeolite by seed-assisted method for aromatization reactions of methanol or methane. Canadian Journal of Chemistry. 99(11), 874-880. DOI: 10.1139/cjc-2021-0095
  20. Ponomareva, O.A., Moskovskaya, I.F; Romanovskii, B.V. (2004). Methanol conversion on pentasils: The order of product formation. Kinetics and Catalysis. 45(3), 400-405. DOI: 10.1023/B:KICA.0000032176.10430.7a
  21. Suganuma, S., Nakamura, K., Okuda, A., Katada, N. (2017). Enhancement of catalytic activity for toluene disproportionation by loading Lewis acidic nickel species on ZSM-5 zeolite. Molecular Catalysis. 435, 110-117. DOI: 10.1016/j.mcat.2017.03.029
  22. Albahar, M., Li, C., Zholobenko, V.L. Garforth, A.A. (2020). The effect of ZSM-5 zeolite crystal size on p-xylene selectivity in toluene disproportionation. Microporous and Mesoporous Materials. 302, 110221-11025. DOI: 10.1016/j.micromeso.2020.110221
  23. Kerimli, F.Sh., Ilyasli, T.M., Mammadov, S.E., Akhmedova, N.F., Mammadov, E.S., Makmudova, N.I., Akhmedov, E.I. (2021). Evaluation of the Properties of ZSM-5 Type Zeolites Modified with CexMg1–xAl2O4 Nanopowders in the Toluene Disproportionation Reaction. Petroleum Chemistry. 61, 895–900. DOI: 10.1134/S0965544121080041
  24. Ghosal, D., Basu, J.K., Sengupta, S. (2015). Application of La-ZSM-5 Coated Silicon Carbide Foam Catalyst for Toluene Methylation with Methanol. Bulletin of Chemical Reaction Engineering & Catalysis. 10(2), 201-209. DOI: 10.9767/bcrec.10.2.7872.201-209
  25. Yang, D.-H., Wang, X.-B., Shi. B.-B., Wu, Z.-H., Li, X.-F., Dou, T. (2014). Synthesis of ZSM-5/EU-1 Composite Zeolite and Its Application in Conversion of Methanol to Xylene. Journal of Inorganic Materials. 29(4), 357-363. DOI: 10.3724/SP.J.1077.2014.13377
  26. Zhang, J., Liang, W., Wu, Z., Wang, H., Wang, C., Han, S., Xiao, F.-S. (2019). Solvent-Free Synthesis of Core–Shell Zn/ZSM-5@Silicalite-1 Catalyst for Selective Conversion of Methanol to BTX Aromatics. Industrial & Engineering Chemistry Research. 58(34),15453–15458. DOI: 10.1021/acs.iecr.9b03357
  27. Mamedov, S.E., Gendzhalieva, I.Sh. (2010). A study of the properties of modified high-silica zeolites in the conversion of methanol to n-xylene. Russian Journal of Applied Chemistry. 83, 1099–1101. DOI: 10.1134/S1070427210060364
  28. Zhang, Y.K., Qu, Y.X., Wang, D.L., Zeng, X.C., Wang, J.D. (2017). Cadmium modified HZSM-5: A Highly Efficient Catalyst for Selective Transformation of Methanol to Aromatics. Industrial and Engineering Chemistry Research. 56, 12508-12519. DOI: 10.1021/acs.iecr.7b02908
  29. Zhang, J., Qian, W., Kong, C., Fei, W. (2015). Increasing para-xylene selectivity in making aromatics from methanol with a surface-modified Zn/P/ZSM-5 catalyst. ACS Catalysis. 5(5), 2982-2988. DOI: 10.1021/acscatal.5b00192
  30. Gong, T., Zhang, X., Bai, T., Zhang, Q., Tao, L., Qi, M., Duan, C., Zhang, L. (2012). Coupling Conversion of Methanol and C4 Hydrocarbon to Propylene on La-Modified HZSM-5 Zeolite Catalysts. Industrial & Engineering Chemistry Research. 51, 13589–13598. DOI: 10.1021/ie300515z
  31. Rostamizadeh, M., Taeb, A. (2015). Highly selective Me-ZSM-5 catalyst for methanol to propylene (MTP). Journal of Industrial and Engineering Chemistry. 27, 297-306. DOI: 10.1016/j.jiec.2015.01.004
  32. Makhmudova, N.I., Verdiyeva, L.R., Ilyasly, T.M., Babayeva, T.A., Mammadov, S.E. (2017). Synthesis of CexMg1-xAl2O4 Nano-Parts and the Study of Their Physico-Chemical and Catalytic Properties in Composition with Zeolite ZSM-5 in Conversion of Methanol into p-Xylol. Fundamental Research. 10(3), 483-491
  33. Zilkova, N., Bejblovа, М., Gil, В., Zones, S.I., Burton, A.W., Chen, C.Y., Musilová-Pavlсková, Z., Kosova, G., Cejka, J. (2009). The role of the zeolite channel architecture and acidity on the activity and selectivity in aromatic transformations: The effect of zeolite cages in SSZ-35 zeolite. Journal of Catalysis, 266, 79–91. DOI: 10.1016/j.jcat.2009.05.017
  34. Kazansky, V.B., Borovkov, V.Y., Serykh, A.I., Santen, R.A., Anderson, B.G. (2000). Nature of the sites of dissociative adsorption of dihydrogen and light paraffins in ZnHZSM-5 zeolite prepared by incipient wetness impregnation. Catalysis Letters. 66, 39–47. DOI: 10.1023/A:1019031119325

Last update:

No citation recorded.

Last update:

No citation recorded.