Synthesis of Ziegler-Natta Catalyst using Malaysian Ilmenite Derived TiCl4 via Recrystallization Method: A Statistical Approach

Sanjith Udayakumar  -  School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia, Malaysia
Najwa Ibrahim  -  School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia, Malaysia
Chan Yong Chien  -  School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia, Malaysia
Shaikh Abdul Rahman Shaik Abdul Wahab  -  School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia, Malaysia
Ahmad Fauzi Mohd Noor  -  School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia, Malaysia
*Sivakumar Ramakrishnan  -  School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia, Malaysia
Received: 18 Jun 2020; Revised: 11 Aug 2020; Accepted: 13 Aug 2020; Published: 28 Dec 2020; Available online: 19 Sep 2020.
Open Access Copyright (c) 2020 Bulletin of Chemical Reaction Engineering & Catalysis
License URL:

Citation Format:
Cover Image

In the current study, Ziegler-Natta (Z-N) catalyst was synthesized via recrystallization method using MgCl2 as a support, AlCl3 as an activator and TiCl4 as a transition metal source. The TiCl4 used in the study was derived from Malaysian ilmenite through a sequential pyrometallurgical and hydrometallurgical process of ilmenite concentrate conversion to TiCl4. The recrystallization method of synthesis of the heterogeneous Z-N catalyst was studied by varying the synthesis parameters, such as the combined amount of MgCl2 and AlCl3, temperature, and amount of TiCl4, using statistical design of experiments. The investigation aimed at determining the best conditions for synthesizing the heterogeneous Z-N catalyst. The synthesis conditions posed a significant influence on the Ti content present in the catalyst product. The morphological and elemental analysis of SEM-EDX showed good spherical nature of the prepared catalysts. The XRD phase analysis detected the peaks of MgCl2, MgCl2-Ethanol, MgCl2/TiClx, and TiO2. The IR spectra confirmed the presence of the Mg-Cl bond at 1635 cm−1 and Ti-Cl bonds at 602 cm-1 and 498 cm-1. The produced catalyst contained a small amount of TiO2, which could be due to the seepage of moisture during the analysis or storage of the sample. The most favourable combination of the studied parameters was determined based on the Ti content in the catalyst product. Therefore, the best conditions for synthesizing the heterogeneous Z-N catalyst with high Ti content (181.1 mg/L) was at a combined amount of 2 g of MgCl2 for 6 g of AlCl3, crystallization temperature of 80 °C, and 2 mL dosage of TiCl4. Copyright © 2020 BCREC Group. All rights reserved

Keywords: Malaysian ilmenite; Ziegler-Natta catalyst; Recrystallization method; TiCl4; statistical design of experiments
Funding: Universiti Sains Malaysia (USM)

Article Metrics:

  1. Vaughan, A., Davis, D., Hagadorn, J., Salwani, M. (2017). Industrial catalysts for alkene polymerization. In Polymer Science: A Comprehensive Reference (Vol. 3, pp. 657-672): Elsevier.
  2. Galli, P., Vecellio, G. (2001). Technology: driving force behind innovation and growth of polyolefins. Progress in Polymer Science, 26(8), 1287-1336.
  3. Correa, A., Credendino, R., Pater, J.T., Morini, G., Cavallo, L. (2012). Theoretical Investigation of Active Sites at the Corners of MgCl2 Crystallites in Supported Ziegler–Natta Catalysts. Macromolecules, 45(9), 3695-3701.
  4. Chen, Y.-P., Fan, Z.-Q. (2006). Ethylene/1-hexene copolymerization with TiCl4/MgCl2/AlCl3 catalyst in the presence of hydrogen. European Polymer Journal, 42(10), 2441-2449.
  5. Parada, A., Rajmankina, T., Chirinos, J., Morillo, A. (2002). Influence of support recrystallization techniques on catalyst performance in olefin polymerization. European Polymer Journal, 38(10), 2093-2099.
  6. Pokasermsong, P., Praserthdam, P. (2009). Comparison of activity of Ziegler-Natta catalysts prepared by recrystallization and chemical reaction methods towards polymerization of ethylene. Engineering Journal, 13(1), 57-64.
  7. Tornqvist, E., Richardson, J., Wilchinsky, Z., Looney, R. (1967). Solid solution formation in the TiCl3-AlCl3 system. Journal of Catalysis, 8(2), 189-196.
  8. Ye, Z.Y., Wang, L., Feng, L.F., Gu, X.P., Chen, H.H., Zhang, P.Y., Pan, J., Jiang, S., Feng, L.X. (2002). Novel spherical Ziegler–Natta catalyst for polymerization and copolymerization. I. Spherical MgCl2 support. Journal of Polymer Science Part A: Polymer Chemistry, 40(18), 3112-3119.
  9. Sinthusai, L., Trakarnpruk, W., Strauss, R. (2017). Ziegler-Natta catalyst with high activity and good hydrogen response. Journal of Metals, Materials and Minerals, 19(2). 27-32.
  10. Almeida, L.A., Marques, M.d.F.V. (2012). Synthesis of a TiCl4 Ziegler‐Natta Catalyst Supported on Spherical MgCl2·nEtOH for the Polymerization of Ethylene and Propylene. Macromolecular Reaction Engineering, 6(1), 57-64.
  11. Redzic, E., Garoff, T., Mardare, C.C., List, M., Hesser, G., Mayrhofer, L., Hassel, A.W., Paulik, C. (2016). Heterogeneous Ziegler–Natta catalysts with various sizes of MgCl2 crystallites: synthesis and characterization. Iranian Polymer Journal, 25(4), 321-337.
  12. Huang, R., Malizia, F., Pennini, G., Koning, C.E., Chadwick, J.C. (2008). Effects of MgCl2 crystallographic structure on active centre formation in immobilized single‐centre and Ziegler–Natta catalysts for ethylene polymerization. Macromolecular Rapid Communications, 29(21), 1732-1738.
  13. Makwana, U., Naik, D.G., Singh, G., Patel, V., Patil, H.R., Gupta, V.K. (2009). Nature of phthalates as internal donors in high performance MgCl2 supported titanium catalysts. Catalysis letters, 131(3-4), 624-631.
  14. Thushara, K., Ajithkumar, T., Rajamohanan, P., Gopinath, C.S. (2014). Structural investigations of porous MgCl2–2-butanol molecular adduct as support for olefin polymerization. Applied Catalysis A: General, 469, 267-274.
  15. Thushara, K., Gnanakumar, E.S., Mathew, R., Jha, R.K., Ajithkumar, T., Rajamohanan, P., Sarma, K., Padmanabhan, S., Bhaduri, S., Gopinath, C.S. (2010). Toward an Understanding of the Molecular Level Properties of Ziegler−Natta Catalyst Support with and without the Internal Electron Donor. The Journal of Physical Chemistry C, 115(5), 1952-1960.
  16. Czaja, K., Bialek, M. (2000). The role of magnesium chloride as support for Ziegler-Natta catalysts. Polimery, 45(9), 608-613.
  17. Pirinen, S., Jayaratne, K., Denifl, P., Pakkanen, T.T. (2014). Ziegler–Natta catalysts supported on crystalline and amorphous MgCl2/THF complexes. Journal of Molecular Catalysis A: Chemical, 395, 434-439.
  18. Parada, A., Rajmankina, T., Chirinos, J. (1999). Study of the MgCl2 recrystallization conditions on Ziegler-Natta catalyst properties. Polymer Bulletin, 43(2-3), 231-238.
  19. Coutinho, F.M., Costa, M.A., Santos, A.L., Costa, T.H., Santa Maria, L.C.,
  20. Pereira, R.A. (1992). Characterization of Ziegler-Natta catalysts based on TiCl3 synthesized by different methods. Fresenius' Journal of Analytical Chemistry, 344(10-11), 514-516.
  21. Ahmadjo, S., Jamjah, R., Zohuri, G.H., Damavandi, S., Haghighi, M.N., Javaheri, M. (2007). Preparation of highly active heterogeneous Ziegler-Natta catalyst for polymerization of ethylene. Iranian Polymer Journal, 16(1), 31.
  22. Dil, E.J., Pourmahdian, S., Vatankhah, M., Taromi, F.A. (2010). Effect of dealcoholation of support in MgCl2-supported Ziegler–Natta catalysts on catalyst activity and polypropylene powder morphology. Polymer Bulletin, 64(5), 445-457.
  23. Hoff, R., Mathers, R.T. (2010). Handbook of Transition Metal Polymerization Catalysts: John Wiley & Sons.
  24. Kaminsky, W. (2013). Polyolefins: 50 years after Ziegler and Natta II (1 ed.): Springer-Verlag Berlin Heidelberg.
  25. Böhm, L.L. (2003). The ethylene polymerization with Ziegler catalysts: fifty years after the discovery. Angewandte Chemie International Edition, 42(41), 5010-5030.
  26. Klaue, A., Kruck, M., Friederichs, N., Bertola, F., Wu, H., Morbidelli, M. (2018). Insight into the synthesis process of an industrial Ziegler–Natta catalyst. Industrial & Engineering Chemistry Research, 58(2), 886-896.
  27. Ahmadi, E., Fauzi, A., Hussin, H., Baharun, N., Ariffin, K.S., Rezan, S.A. (2017). Synthesis of titanium oxycarbonitride by carbothermal reduction and nitridation of ilmenite with recycling of polyethylene terephthalate (PET). International Journal of Minerals, Metallurgy, and Materials, 24(4), 444-454.
  28. Ahmadi, E., Sereiratana, E., Rezan, S.A., Yeoh, F., Fauzi, A., Zhang, G. (2016). Assessment of titanium carbide chlorination by statistical design. Paper presented at the Materials Science Forum.
  29. Rezan, S.A., Zhang, G., Ostrovski, O. (2007). Synthesis of titanium oxycarbonitride by carbothermal reduction of titania in nitrogen containing gas mixtures. Paper presented at the The 11th World Conference on Titanium, Kyoto, Japan.
  30. Yaraghi, A., Sapri, M.H.A., Baharun, N., Rezan, S.A., Shoparwe, N.I., Ramakrishnan, S., Ariffin, K.S., Fauzi, M.A., Ismail, H., Seli, H.H. (2016). Aeration leaching of iron from nitrided Malaysian ilmenite reduced by polystyrene-coal reductant. Procedia Chemistry, 19, 715-720.
  31. Ahmadi, E., Shoparwe, N.I., Ibrahim, N., Hamid, S.A.R.S.A., Baharun, N., Ariffin, K.S., Hussin, H., Fauzi, M.A. (2018). The Effects of Experimental Variables on Iron Removal from Nitrided Malaysian Ilmenite by Becher Process. In Extraction 2018 (pp. 1383-1396): Springer.
  32. Ahmadi, E., Rezan, S.A., Baharun, N., Ramakrishnan, S., Fauzi, A., Zhang, G. (2017). Chlorination kinetics of titanium nitride for production of titanium tetrachloride from nitrided ilmenite. Metallurgical and Materials Transactions B, 48(5), 2354-2366.
  33. Ibrahim, N., Ahmadi, E., Rahman, S.A., Fauzi, M.A., Rezan, S.A. (2017). Extraction of titanium from low-iron nitrided Malaysian ilmenite by chlorination. Paper presented at the AIP Conference Proceedings.
  34. Ahmadi, E. (2018). Synthesis of titanium tetrachloride through arbothermal reduction and chlorination of ilmenite concentrate. (Doctor of Philosophy), Universiti Sains Malaysia, Malaysia. (875008031)
  35. Gnanakumar, E.S., Gowda, R.R., Kunjir, S., Ajithkumar, T., Rajamohanan, P., Chakraborty, D., Gopinath, C.S. (2013). MgCl2.6CH3OH: a simple molecular adduct and its influence as a porous support for olefin polymerization. ACS Catalysis, 3(3), 303-311.
  36. Thushara, K., Gnanakumar, E.S., Mathew, R., Ajithkumar, T., Rajamohanan, P., Bhaduri, S., Gopinath, C.S. (2012). MgCl2·4((CH3)2CHCH2OH): A new molecular adduct for the preparation of TiClx/MgCl2 catalyst for olefin polymerization. Dalton Transactions, 41(37), 11311-11318.
  37. Jamjah, R., Zohuri, G., Vaezi, J., Ahmadjo, S., Nekomanesh, M., Pouryari, M. (2006). Morphological study of spherical MgCl2.nEtOH supported TiCl4 Ziegler‐Natta catalyst for polymerization of ethylene. Journal of Applied Polymer Science, 101(6), 3829-3834.

Last update: 2021-01-18 20:43:06

No citation recorded.

Last update: 2021-01-18 20:43:07

No citation recorded.