Skip to main content
Log in

Effects of the Type and Loading of Rare-Earth Metals (Pr, Yb, Ho) on the para-Selectivity of HTsVM Zeolite in Toluene Ethylation

  • Published:
Petroleum Chemistry Aims and scope Submit manuscript

Abstract

The study describes toluene ethylation using TsVM zeolite (SiO2/Al2O3 = 40) and a series of TsVM-based catalysts modified with rare-earth metals. To investigate the effects of the type and loading of rare-earth metals in the HTsVM catalyst on the selectivity towards total ethyltoluenes and p-ethyltoluene, the reaction was carried out in a continuous-flow fixed-bed reactor at atmospheric pressure and temperatures of 300–400°C. The HTsVM was modified with praseodymium, ytterbium, and holmium nitrates. The physicochemical and textural properties of the catalysts were characterized by XRD, FTIR spectroscopy, NH3-TPD, and low-temperature nitrogen adsorption. The specific surface area, acidity, total pore volume, and mesopore volume were found to decrease with an increase in the holmium loading of the catalyst. The zeolite catalysts loaded with 4.0–5.0 wt % Ho exhibited optimum stability and high p-ethyltoluene selectivity (79.5–81.4%) in combination with adequate toluene conversion (19.4–20.3%).

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1.
Fig. 2.
Fig. 3.
Fig. 4.
Fig. 5.
Fig. 6.
Fig. 7.

Similar content being viewed by others

REFERENCES

  1. Kaedinq, W.W., Barile, G.C., and Wu, M.M., Catal. Rev., 1984, vol. 26, nos. 3–4, pp. 597–602. https://doi.org/10.1080/01614948408064727

    Article  Google Scholar 

  2. Al-Khattaf, S., Ali, S.A., Aitani, A.M., Žilková, N., Kubicka, D., and Cejka, J., Catal. Rev. Sci. Eng., 2014, vol. 56, pp. 333–402. https://doi.org/10.1080/01614940.2014.946846

    Article  CAS  Google Scholar 

  3. Čejka, J. and Wichterlová, B., Catal. Rev. Sci. Eng., 2002, vol. 44, pp. 375–421. https://doi.org/10.1081/CR-120005741

    Article  Google Scholar 

  4. Wang, I., Ay, C.L., Lee, B.J., and Chen, M.H., Appl. Catal., 1989, vol. 54, pp. 257–262. https://doi.org/10.1016/S0166-9834(00)82368-4

    Article  CAS  Google Scholar 

  5. Cejka, J., Kapustin, G.A., and Wichterlova, B., Appl. Catal. A: General, 1994, vol. 108, no. 2, pp. 187–204. https://doi.org/10.1016/0926-860X(94)85070-4

    Article  CAS  Google Scholar 

  6. Manivannan, R. and Pandurangan, A., Kinet. Catal., 2010, vol. 51, no. 1, pp. 56–63. https://doi.org/10.1134/S0023158410010106

    Article  CAS  Google Scholar 

  7. Paparatto, G., Moretti, E., Leofanti, G., and Gatti, F., J. Catal., 1987, vol. 105, pp. 227–232. https://doi.org/10.1016/S0167-2991(09)61301-X

    Article  CAS  Google Scholar 

  8. Villareal, N.E., Kharisov, B.I., Ivanova, I.I., and Romanovskii, B.V., Appl. Catal. A: General, 2002, vol. 224, pp. 161–166. https://doi.org/10.1016/S0926-860X(01)00782-7

    Article  Google Scholar 

  9. Atanda, L.A., Aitani, A.M., and Al-Khattaf, S.S., Chem. Eng. Res. Des., 2015, vol. 95, pp. 34–46. https://doi.org/10.1016/j.cherd.2015.01.001

    Article  CAS  Google Scholar 

  10. Walendziewski, J. and Trawczyński, J., Ind. Eng. Chem. Res., 1996, vol. 35, no. 10, pp. 3356–3361. https://doi.org/10.1021/ie950659r

    Article  CAS  Google Scholar 

  11. Kaeding, W.W. and Barile, G.C., in New Monomers and Polymers, Culbertson, B.M. and Pittman, C.U., Eds., 1984, pp. 223–241. https://link.springer.com/chapter/10.1007/9781-4684-4619-7_14

  12. Canterino, P.J., Patent US 4230836A, 1979. https://patents.google.com/patent/US4230836A/en

  13. Innes, R.A. and Occelli, M.L., J. Mol. Catal., 1985, vol. 32, no. 2, pp. 259–271. https://doi.org/10.1016/0304-5102(85)80011-0

    Article  CAS  Google Scholar 

  14. Vasudevan, T.V. and Sharma, M.M., Ind. Eng. Chem. Res., 1983, vol. 22, no. 4, pp. 681–684. https://doi.org/10.1021/i200023a025

    Article  CAS  Google Scholar 

  15. Ponomareva, O.A., Moskovskaya, I.F., and Romanovskii, B.V., Neftekhim., 1998, vol. 38, no. 2, pp. 348–354.

    CAS  Google Scholar 

  16. Cejka, J., Wichterlová, B., and Bednárová, S., Appl. Catal. A: General, 1991, vol. 79, pp. 215–226. https://doi.org/10.1016/0926-860X(91)80007-L

    Article  CAS  Google Scholar 

  17. Wang, D., Wang, C.M., Yang, G., Du, Y.J., and Yang, W.M., J. Catal . , 2019, vol. 374, pp. 1–11. https://doi.org/10.1016/j.jcat.2019.04.021

    Article  CAS  Google Scholar 

  18. Kaeding, W.W., Young, L.B., and Chu, C.-C., J. Catal., 1984, vol. 96, no. 2, pp. 267–273. https://doi.org/10.1016/0021-9517(84)90304-X

    Article  Google Scholar 

  19. Ogunbadejo, B.A., Aitani, A., Cejka, J., Kubu, M., and Al-Khattaf, S.S., J. Chem. Eng., 2016, vol. 306, pp. 1071–1080. https://doi.org/10.1016/j.cej.2016.08.019

    Article  CAS  Google Scholar 

  20. Ogunbadejo, B.A., Osman, M.S., Arudra, P., Aitani, A.M., and Al-Khattaf, S.S., Catal. Today., 2015, vol. 243, pp. 109–117. https://doi.org/10.1016/j.cattod.2014.08.019

    Article  CAS  Google Scholar 

  21. Parikh, P.A., Subrahmanyam, N., Bhat, Y.S., and Halgeri, A.B., Ind. Eng. Chem. Res., 1992, vol. 31, no. 4, pp. 1012–1016. https://doi.org/10.1021/ie00004a005

    Article  CAS  Google Scholar 

  22. Galadima, A. and Muraza, O., J. Ind. Eng. Chem., 2015, vol. 31, pp. 1–14. https://doi.org/10.1016/j.jiec.2015.07.015

    Article  CAS  Google Scholar 

  23. Parikh, P.A., Ind. Eng. Chem. Res., 2008, vol. 47, pp. 1793–1797. https://doi.org/10.1021/ie071332g

    Article  CAS  Google Scholar 

  24. Mamedov, S.E., Iskenderova, A.A., Akhmedova, N.F., and Mamedov, E.S., Petrol. Chem., 2020, vol. 60, pp. 950–956. https://doi.org/10.1134/S0965544120080071

    Article  CAS  Google Scholar 

  25. Imyen, T., Wannapakdee, W., Ittisanronnachai, S., Witoon, T., and Wattanakit, C., Nanoscale Adv., 2020, vol. 2, pp. 4437–4449. https://doi.org/10.1039/D0NA00391C

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  26. Liu, J., Yang, Y., Wei, S., Shen, W., Rakovitis, N., and Li, J., Ind. Eng. Chem. Res., 2018, vol. 57, no. 38, pp. 12829–12841. https://doi.org/10.1021/acs.iecr.8b00681

    Article  CAS  Google Scholar 

  27. Parikh, P.A., Subrahmanyam, N., Bhat, Y.S., and Halgeri, A.B., Chem. Eng. J., 1994, vol. 54, pp. 79–85.

    CAS  Google Scholar 

  28. Abdullaeva, N.M., Voskressenskii, L.G., Akhmedova, N.F., and Mamedov, S.E., Petrol. Chem., 2021, vol. 61, pp. 190–197. https://doi.org/10.1134/S0965544121020018

    Article  CAS  Google Scholar 

  29. Wichterlová, B. and Čejka, J., J. Catal Lett., 1992, vol. 16, no. 4, pp. 421–429. https://doi.org/10.1007/BF00764900

    Article  Google Scholar 

  30. Janardhan, H.L., Shanbhag, G.V., and Halgeri, A.B., Appl. Catal. A: General, 2014, vol. 471, pp. 12–18. https://doi.org/10.1016/j.apcata.2013.11.029

    Article  CAS  Google Scholar 

  31. Blasco, T., Corma, A., and Martínez-Triguero, J., J. Catal . 2006, vol. 237, no. 2, pp. 267–277. https://doi.org/10.1016/j.jcat.2005.11.011

  32. Vinek, H., Rumplmayr, G., and Lercher, J.A., J. Catal., 1989, vol. 115, no. 2, pp. 291–300. https://doi.org/10.1016/0021-9517(89)90033-X

    Article  CAS  Google Scholar 

  33. Aliev, S.I., Akhmedov, E.I., Mamedov, E.S., and Gakhramanov, T.O., Russ. J. Appl. Chem., 2009, vol. 82, no. 3, pp. 512–514. https://doi.org/10.1134/S1070427209030318

    Article  CAS  Google Scholar 

  34. Parikh, P.A., Subrahmanyam, N., Bhat, Y.S., and Halgeri, A.B., Catal. Lett., 1992, vol. 14, pp. 107–113. https://doi.org/10.1007/BF00764224

    Article  CAS  Google Scholar 

  35. Lónyi, F., Engelhardt, J., and Kalló, D., Zeolites, 1991, vol. 11, pp. 169–177. https://doi.org/10.1016/0144-2449(91)80412-S

    Article  Google Scholar 

  36. Bhandarkar, B. and Bhatia, S., Zeolites, 1994, vol. 14, pp. 439–449. https://doi.org/10.1016/0144-2449(94)90170-8

    Article  CAS  Google Scholar 

  37. Aliev, I.A., Akhmedov, E.I., Mamedov, E.S., and Gakhramanov, T.O., Petrol. Chem., 2010, vol. 50, no. 5, pp. 373–375. https://doi.org/10.1134/S0965544110050099

    Article  Google Scholar 

  38. Mamedov, E.S., Gakhramanov, T.O., and Akhmedov, E.I., Vopros. Khim. Khim. Tekhnol., 2012, no. 1, pp. 35–37. https://udhtu.edu.ua/public/userfiles/file/VHHT/2012/1/Mamedov.pdf

    Google Scholar 

  39. Mahmudov, K.T., Karimli, F.Sh., Mamedov, E.S., Gurbanov, A.V., Akhmedova, N.F., and Mamedov S.E., Petrol. Chem., 2022. vol. 4, no. 2, рр. 122–129. https://doi.org/10.1134/S0965544122060147

  40. Zilkova, N., Bejblova, M., Gil, B., Zones, S.I., Burton, A.W., Chen, C.-Y., Musilová-Pavlačková, Z., Košová, G., and Čejka, J., J. Catal., 2009, vol. 266, no. 1, pp. 79–91. https://doi.org/10.1016/j.jcat.2009.05.017

    Article  CAS  Google Scholar 

  41. Mahmudova, N.I., Mаmmаdov, E.S., Kаrimli, F.Sh., Ilyasli, T.M., Akhmedova, N.F., and Mаmmаdov, S.E., Bull. Chem. React. Eng., 2022, vol. 17, no. 4, pp. 725–732. https://doi.org/10.9767/bcrec.17.4.15115.725-732

    Article  CAS  Google Scholar 

  42. Guan, X., Li, N., Wu, G., Chen, J., Zhang, F., and Guan, N., J. Mol. Catal. A: Chem., 2006, vol. 248, nos. 1–2, pp. 220–225. https://doi.org/10.1016/j.molcata.2005.12.032

    Article  CAS  Google Scholar 

  43. Zhang C, Xu, Z., Wan, K., Liu, Q., Appl. Catal. A: General, 2004, vol. 258, pp. 55–61. https://doi.org/10.1016/j.apcata.2003.08.012

    Article  CAS  Google Scholar 

  44. Sing, K.S.W., Pure Appl. Chem., 1985, vol. 57, no. 4, pp. 603–619. https://doi.org/10.1351/pac19855704

    Article  CAS  Google Scholar 

Download references

Funding

This work was supported by ongoing institutional funding. No additional grants to carry out or direct this particular research were obtained.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to N. F. Akhmedova.

Ethics declarations

The authors declare no conflict of interest requiring disclosure in this article.

Additional information

Publisher's Note. Pleiades Publishing remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Mammadov, E.S., Gahramanov, T.O., Akhmedova, N.F. et al. Effects of the Type and Loading of Rare-Earth Metals (Pr, Yb, Ho) on the para-Selectivity of HTsVM Zeolite in Toluene Ethylation. Pet. Chem. (2024). https://doi.org/10.1134/S0965544124010134

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1134/S0965544124010134

Keywords:

Navigation