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Improved Activation of Titanium Dioxide Catalyst for Isomerization of Alpha Pinene and Understanding into Effect of Isomerization Parameters

  • Research Article-Chemical Engineering
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Abstract

A series of acid-activated catalyst were prepared by activating TiO2 using different acids, and subsequent catalytic performance was evaluated for isomerization of alpha pinene. The prepared catalysts were also characterized using SEM, XRD, FTIR, TPD and BET methods to understand the effect of type of acid on the catalyst characteristics. It was demonstrated that catalyst surface area and total acidity increased with acid activation of the raw TiO2 catalyst. The influence of type of acid used for activation, operating temperature, catalyst amount and reaction time on the conversion of alpha pinene and selectivity of products was examined, also presenting kinetic and thermodynamic analysis. At optimized conditions, complete conversion of alpha pinene was observed with the higher selectivity towards products as camphene, carene and tricyclene, with higher commercial importance. The current work clearly demonstrated that activated catalyst gives highest conversion of alpha pinene and selectivity for bicyclic monoterpenes.

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References

  1. Rachwalik, R.; Hunger, M.; Sulikowski, B.: Transformations of monoterpene hydrocarbons on ferrierite type zeolites. Appl. Catal. A Gen. 427–428, 98–105 (2012)

    Article  Google Scholar 

  2. Frattini, L.; Isaacs, M.A.; Parlett, C.M.A.; Wilson, K.; Kyriakou, G.; Lee, A.F.: Support enhanced α-pinene isomerization over HPW/SBA-15. Appl. Catal. B Environ. 200, 10–18 (2017)

    Article  Google Scholar 

  3. Xiang, J.; Luo, Z.: Study on the pinene isomerization catalyzed by TiM. Chinese J. Chem. Eng. 26, 2537–2541 (2018)

    Article  Google Scholar 

  4. Zielińska, B.; Wróblewska, A.; Maślana, K.; Miądlicki, P.; Kiełbasa, K.; Rozmysłowska-Wojciechowska, A.; Petrus, M.; Woźniak, J.; Jastrzębska, A.M.; Michalkiewicz, B.; Mijowska, E.: High catalytic performance of 2D Ti3C2Tx MXene in α-pinene isomerization to camphene. Appl. Catal. A Gen. 604, 117765 (2020)

    Article  Google Scholar 

  5. A.Y. Sidorenko, A. Aho, J. Ganbaatar, D. Batsuren, D.B. Utenkova, G.M. Sen’kov, J. Wärnå, D.Y. Murzin, V.E. Agabekov, Catalytic isomerization of Α-pinene and 3-carene in the presence of modified layered aluminosilicates. Mol. Catal. 443 (2017) 193–202.

  6. Liu, Y.; Zheng, D.; Li, B.; Lyu, Y.; Wang, X.; Liu, X.; Li, L.; Yu, S.; Liu, X.; Yan, Z.: Isomerization of α-pinene with a hierarchical mordenite molecular sieve prepared by the microwave assisted alkaline treatment. Microporous Mesoporous Mater. 299, 110117 (2020)

    Article  Google Scholar 

  7. Wu, Y.; Tian, F.; He, M.; Cai, T.: Isomerization of α-pinene over immobilized AlCl3 catalysts. Cuihua Xuebao/Chinese J. Catal. 32, 1138–1142 (2011)

    Article  Google Scholar 

  8. Chimal-Valencia, O.; Robau-Sánchez, A.; Collins-Martínez, V.; Aguilar-Elguézabal, A.: Ion exchange resins as catalyst for the isomerization of α-pinene to camphene. Bioresour. Technol. 93, 119–123 (2004)

    Article  Google Scholar 

  9. Allahverdiev, A.I.: Kinetics of α -pinene isomerization. Ind. Eng. Chem. Res. 37, 2373–2377 (1998)

    Article  Google Scholar 

  10. Atalay, B.; Gündüz, G.: Isomerizaton of α-pinene over H3PW12O40 catalysts supported on natural zeolite. Chem. Eng. J. 168, 1311–1318 (2011)

    Article  Google Scholar 

  11. Comelli, N.A.; Ponzi, E.N.; Ponzi, M.I.: α-Pinene isomerization to camphene: effect of thermal treatment on sulfated zirconia. Chem. Eng. J. 117, 93–99 (2006)

    Article  Google Scholar 

  12. Wu, Y.; Tian, F.; Liu, J.; Song, D.; Jia, C.; Chen, Y.: Enhanced catalytic isomerization of α-pinene over mesoporous zeolite beta of low Si/Al ratio by NaOH treatment. Microporous Mesoporous Mater. 162, 168–174 (2012)

    Article  Google Scholar 

  13. Wijayati, N.; Kusumastuti, E.: Isomerization of α-pinene in the terpentin oil with TCA/Natural Zeolite using microwave irradiation. IOP Conf. Ser. Mater. Sci. Eng. 349, 012046 (2018)

    Article  Google Scholar 

  14. Ecormier, M.A.; Wilson, K.; Lee, A.F.: Structure-reactivity correlations in sulphated-zirconia catalysts for the isomerisation of α-pinene. J. Catal. 215, 57–65 (2003)

    Article  Google Scholar 

  15. L. Grzona, N. comelli, O. Masini, E. Ponzi, M. Ponzi liquid phase isomerization of alpha pinene study of the reaction on sulfated ZrO2. React. Kinet. Catal. Lett. 69, 271–276 (2000)

  16. Kelly, A.; Rocha, S.; Robles-dutenhefner, P.A.; Kozhevnikov, I.V.; Gusevskaya, E.V.: Phosphotungstic heteropoly acid as efficient heterogeneous catalyst for solvent-free isomerization of a -pinene and longifolene. Appl. Catal. A Gen. 352, 188–192 (2009)

    Article  Google Scholar 

  17. Alsalme, A.; Kozhevnikova, E.F.; Kozhevnikov, I.V.: α-Pinene isomerisation over heteropoly acid catalysts in the gas-phase. Appl. Catal. A Gen. 390, 219–224 (2010)

    Article  Google Scholar 

  18. Volzone, C.; Masini, O.; Comelli, N.A.; Grzona, L.M.; Ponzi, E.N.; Ponzi, M.I.: Production of camphene and limonene from pinene over acid di- and trioctahedral smectite clays. Appl. Catal. A Gen. 214, 213–218 (2001)

    Article  Google Scholar 

  19. Gündüz, G.; Murzin, D.Y.: Influence of catalyst pretreatment on α-pinene isomerization over natural clays. React. Kinet. Catal. Lett. 75, 231–237 (2002)

    Article  Google Scholar 

  20. Yadav, M.K.; Chudasama, C.D.; Jasra, R.V.: Isomerisation of α-pinene using modified montmorillonite clays. J. Mol. Catal. A Chem. 216, 51–59 (2004)

    Article  Google Scholar 

  21. Wróblewska, A.; Miądlicki, P.; Sreńscek-Nazzal, J.; Sadłowski, M.; Koren, Z.C.; Michalkiewicz, B.: Alpha-pinene isomerization over Ti-SBA-15 catalysts obtained by the direct method: the influence of titanium content, temperature, catalyst amount and reaction time. Microporous Mesoporous Mater. 258, 72–82 (2018)

    Article  Google Scholar 

  22. Severino, A.; Vital, J.; Lobo, L.S.: Isomerization of α-pinene over TiO2: Kinetics and catalyst optimization. Stud. Surf. Sci. Catal. 78, 685–692 (1993)

    Article  Google Scholar 

  23. Sidorenko, A.Y.; Senkov, G.M.; Agabekov, V.E.: Effect of acid treatment on the composition and structure of a natural aluminosilicate and on its catalytic properties in α-pinene isomerization. Catal. Ind. 6, 94–104 (2014)

    Article  Google Scholar 

  24. Agabekov, V.E.; Senkov, G.M.; Sidorenko, A.Y.; Tuyen, N.D.; Tuan, V.A.: New α-pinene isomerization catalysts. Catal. Ind. 3, 319–330 (2011)

    Article  Google Scholar 

  25. Bagheri, S.; Shameli, K.; Abd Hamid, S.B.: Synthesis and characterization of anatase titanium dioxide nanoparticles using egg white solution via Sol-Gel method. J. Chem. 2013, 6–11 (2013)

    Article  Google Scholar 

  26. He, Z.; Tang, J.; Shen, J.; Chen, J.; Song, S.: Enhancement of photocatalytic reduction of CO2 to CH4 over TiO2 nanosheets by modifying with sulfuric acid. Appl. Surf. Sci. 364, 416–427 (2016)

    Article  Google Scholar 

  27. P. Praveen, G. Viruthagiri, S. Mugundan, N. Shanmugam, Structural, optical and morphological analyses of pristine titanium di-oxide nanoparticles - Synthesized via sol-gel route. Spectrochim. Acta - Part A Mol. Biomol. Spectrosc. 117 (2014) 622–629.

  28. Gohari, G.; Mohammadi, A.; Akbari, A.; Panahirad, S.; Dadpour, M.R.; Fotopoulos, V.; Kimura, S.: Titanium dioxide nanoparticles (TiO2 NPs) promote growth and ameliorate salinity stress effects on essential oil profile and biochemical attributes of Dracocephalum moldavica. Sci. Rep. 10, 1–14 (2020)

    Article  Google Scholar 

  29. Nakamura, R.; Imanishi, A.; Murakoshi, K.; Nakato, Y.: In situ FTIR studies of pimary intermediates of photocatalytic reactions on nanocrystalline TiO2 films in contact with aqueous solutions. J. Am. Chem. Soc. 125, 7443–7450 (2003)

    Article  Google Scholar 

  30. Kumar, B.; Smita, K.; Angulo, Y.; Cumbal, L.: Valorization of rambutan peel for the synthesis of silver-doped titanium dioxide (Ag/TiO2) nanoparticles. Green Process. Synth. 5, 371–377 (2016)

    Google Scholar 

  31. Nishikiori, H.; Hayashibe, M.; Fujii, T.: Visible light-photocatalytic activity of sulfate-doped titanium dioxide prepared by the sol-gel method. Catalysts 3, 363–377 (2013)

    Article  Google Scholar 

  32. Park, S.K.; Shin, H.: Effect of HCl and H2SO4 treatment of TiO2 powder on the photosensitized degradation of aqueous rhodamine B under visible light. J. Nanosci. Nanotechnol. 14, 8122–8128 (2014)

    Article  MathSciNet  Google Scholar 

  33. Liao, L.F.; Lien, C.F.; Lin, J.L.: FTIR study of adsorption and photoreactions of acetic acid on TiO2. Phys. Chem. Chem. Phys. 3, 3831–3837 (2001)

    Article  Google Scholar 

  34. Akgül, M.; Özyaĝci, B.; Karabakan, A.: Evaluation of Fe- and Cr-containing clinoptilolite catalysts for the production of camphene from α-pinene. J. Ind. Eng. Chem. 19, 240–249 (2013)

    Article  Google Scholar 

  35. Solkina, Y.S.; Reshetnikov, S.I.; Estrada, M.; Simakov, A.; Murzin, D.Y.; Simakova, I.L.: Evaluation of gold on alumina catalyst deactivation dynamics during α-pinene isomerization. Chem. Eng. J. 176–177, 42–48 (2011)

    Article  Google Scholar 

  36. Allahverdiev, A.I.; Irandoust, S.; Murzin, D.Y.: Isomerization of α -Pinene over Clinoptilolite. J. Catal. 185, 352–362 (1999)

    Article  Google Scholar 

  37. López, C.M.; Machado, F.J.; Rodríguez, K.; Méndez, B.; Hasegawa, M.; Pekerar, S.: Selective liquid-phase transformation of α-pinene over dealuminated mordenites and Y-zeolites. Appl. Catal. A Gen. 173, 75–85 (1998)

    Article  Google Scholar 

  38. Wu, C.H.; Liu, H.Q.; Zhuang, C.F.; Ben Du, G.: Study on mesoporous PW/SBA-15 for isomerization of á-pinene. Appl. Mech. Mater. 483, 134–137 (2014)

    Article  Google Scholar 

  39. Dai, X.; Wu, C.: Study on α-pinene Isomerization over MCM-41 supported SO42-/TiO2. Adv. Mater. Res. 634–638, 632–637 (2013)

    Article  Google Scholar 

  40. Ünveren, E.; Günüz, G.; Cakicioǧlu-Özkan, F.: Isomerization of alpha-pinene over acid treated natural zeolite. Chem. Eng. Commun. 192, 386–404 (2005)

    Article  Google Scholar 

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Acknowledgements

Authors would like to acknowledge the support of M/s Mangalam Organics for supporting the PhD fellowship for PS

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Authors and Affiliations

  1. Department of Chemical Engineering, Institute of Chemical Technology, Matunga, Mumbai, 400019, India

    Pankaj S. Sinhmar & Parag R. Gogate

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  1. Pankaj S. Sinhmar
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Correspondence to Parag R. Gogate.

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Sinhmar, P.S., Gogate, P.R. Improved Activation of Titanium Dioxide Catalyst for Isomerization of Alpha Pinene and Understanding into Effect of Isomerization Parameters. Arab J Sci Eng 47, 5875–5893 (2022). https://doi.org/10.1007/s13369-021-05706-4

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  • DOI: https://doi.org/10.1007/s13369-021-05706-4

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