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One pot menthol synthesis via hydrogenations of citral and citronellal over montmorillonite-supported Pd/Ni-heteropoly acid bifunctional catalysts

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Abstract

Menthol synthesis is possible through citral and citronellal hydrogenations via following multistage chemical reactions such as hydrogenation and cyclization. This research mainly focuses on a design of selective, active and cost-effective metal-acid (bifunctional) catalysts for menthol production via citral and citronellal hydrogenations. More specifically, Pd and Ni metals were impregnated over acidic support (e.g., hetero-poly acid supported montmorillonite, HPA_MM). The prepared catalysts were characterized by BET, pyridine adsorption and amine titration methods. Some of the most important parameters such as metal type and loading; applied pressure and reaction time have been investigated throughout this work. The obtained results reveals that the 8 wt% Ni-HPA-MM catalyst (Cat-5) has produced 63% menthols (initial reaction rate 0.126 mmol/min) from citral hydrogenation (80 °C, 1.0 MPa) within 24 h. Similarly, during lower applied pressure (0.5 MPa), the production of menthol was significantly improved (approximately 98% of menthol, initial reaction rate ~ 0.138 mmol/min) with the application of 8 wt% Ni-HPA-MM catalyst (Cat-5) in citronellal hydrogenation. Higher menthol selectivity was achieved from both reactions (citral and citronellal hydrogenation) which might be due to the presence of strong Lewis and medium Brønsted acid sites.

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Abbreviations

MMT:

Montmorillonite

HPA:

Heteropoly acid (20% loading of Phosphotungstic acid)

MM:

Acid-treated montmorillonite

HPA-MM:

Heteropoly acid (20% loading of Phosphotungstic acid) supported acid-treated montmorillonite

Pd-HPA-MM:

Pd-loaded heteropoly acid supported acid-treated montmorillonite

Ni-HPA-MM:

Nickel loaded heteropoly acid supported acid-treated montmorillonite

Cat-1:

5 wt% Pd-MM

Cat-2:

2.5 wt% Pd-HPA-MM

Cat-3:

5 wt% Pd-HPA-MM

Cat-4:

5 wt% Ni-HPA-MM

Cat-5:

8 wt% Ni-HPA-MM

CIT:

Citronellal

IPOL:

Isopulegols

MOL:

Menthols

DHCIT:

Dihydrocitronellal

DMOL:

3, 7-Dimethyl-1-octanol

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Authors and Affiliations

  1. Fine Chemical Process Laboratory, Department of Chemical Engineering, Hanyang University, Ansan, South Korea

    Abdul Karim Shah & Yeung Ho Park

  2. Department of Chemical Engineering, Dawood University of Engineering and Technology, Karachi, Pakistan

    Abdul Karim Shah, Ghulamullah Maitlo, Abdul Qayoom Memon & Abdul Sattar Jatoi

  3. Department of Metallurgy Engineering, NED University of Engineering and Technology, Karachi, Sindh, Pakistan

    Aqeel Ahmed Shah & Iftekhar Ahmed Channa

  4. Department of Energy and Environment Engineering, Dawood University of Engineering and Technology, Karachi, Sindh, Pakistan

    Hubdar Ali Maitlo

  5. Department of Pharmaceutics, University of Sindh, Jamshoro, Sindh, Pakistan

    Ahmed Shah

  6. Greenhouse Gas Laboratory, Korea Institute of Energy Research, University of Science and Technology, Daejeon-34129, Republic of Korea

    Umair Hassan Bhatti

  7. Friedrich–Alexander University Erlangen–Nürnberg, Bavaria, Germany

    Iftekhar Ahmed Channa

  8. Department of Basic Science, Dawood University of Engineering and Technology, Karachi, Pakistan

    Ghulam Abbas Kandhro

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  1. Abdul Karim Shah
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Shah, A.K., Maitlo, G., Shah, A.A. et al. One pot menthol synthesis via hydrogenations of citral and citronellal over montmorillonite-supported Pd/Ni-heteropoly acid bifunctional catalysts. Reac Kinet Mech Cat 128, 917–934 (2019). https://doi.org/10.1007/s11144-019-01679-6

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