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Reaction Kinetics, Mechanisms and Catalysis

, Volume 128, Issue 2, pp 917–934 | Cite as

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

  • Abdul Karim ShahEmail author
  • Ghulamullah Maitlo
  • Aqeel Ahmed Shah
  • Iftekhar Ahmed Channa
  • Ghulam Abbas Kandhro
  • Hubdar Ali Maitlo
  • Umair Hassan Bhatti
  • Ahmed Shah
  • Abdul Qayoom Memon
  • Abdul Sattar Jatoi
  • Yeung Ho Park
Article
  • 111 Downloads

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.

Keywords

Citral Citronellal Isopulegol Menthol Bifunctional catalysts 

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

Notes

Supplementary material

11144_2019_1679_MOESM1_ESM.doc (276 kb)
Supplementary material 1 (DOC 275 kb)

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Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2019

Authors and Affiliations

  • Abdul Karim Shah
    • 1
    • 2
    Email author
  • Ghulamullah Maitlo
    • 2
  • Aqeel Ahmed Shah
    • 3
  • Iftekhar Ahmed Channa
    • 3
    • 7
  • Ghulam Abbas Kandhro
    • 8
  • Hubdar Ali Maitlo
    • 4
  • Umair Hassan Bhatti
    • 6
  • Ahmed Shah
    • 5
  • Abdul Qayoom Memon
    • 2
  • Abdul Sattar Jatoi
    • 2
  • Yeung Ho Park
    • 1
  1. 1.Fine Chemical Process Laboratory, Department of Chemical EngineeringHanyang UniversityAnsanSouth Korea
  2. 2.Department of Chemical EngineeringDawood University of Engineering and TechnologyKarachiPakistan
  3. 3.Department of Metallurgy EngineeringNED University of Engineering and TechnologyKarachiPakistan
  4. 4.Department of Energy and Environment EngineeringDawood University of Engineering and TechnologyKarachiPakistan
  5. 5.Department of PharmaceuticsUniversity of SindhJamshoroPakistan
  6. 6.Greenhouse Gas Laboratory, Korea Institute of Energy ResearchUniversity of Science and TechnologyDaejeon-34129Republic of Korea
  7. 7.Friedrich–Alexander University Erlangen–NürnbergBavariaGermany
  8. 8.Department of Basic ScienceDawood University of Engineering and TechnologyKarachiPakistan

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