Solvent Free Upgrading of 5-Hydroxymethylfurfural (HMF) with Levulinic Acid to HMF Levulinate Using Tin Exchanged Tungstophosphoric Acid Supported on K-10 Catalyst.

Manishkumar S Tiwari, Dipti Wagh, Jennifer Sarah Dicks, John Keogh, Michela Ansaldi, Vivek V Ranade, Haresh G Manyar
Author Information
  1. Manishkumar S Tiwari: Theoretical and Applied Catalysis Research Cluster, School of Chemistry and Chemical Engineering, Queen's University Belfast, David-Keir Building, Stranmillis Road, BelfastBT9 5AG, U.K. ORCID
  2. Dipti Wagh: Theoretical and Applied Catalysis Research Cluster, School of Chemistry and Chemical Engineering, Queen's University Belfast, David-Keir Building, Stranmillis Road, BelfastBT9 5AG, U.K.
  3. Jennifer Sarah Dicks: Theoretical and Applied Catalysis Research Cluster, School of Chemistry and Chemical Engineering, Queen's University Belfast, David-Keir Building, Stranmillis Road, BelfastBT9 5AG, U.K.
  4. John Keogh: Theoretical and Applied Catalysis Research Cluster, School of Chemistry and Chemical Engineering, Queen's University Belfast, David-Keir Building, Stranmillis Road, BelfastBT9 5AG, U.K.
  5. Michela Ansaldi: Theoretical and Applied Catalysis Research Cluster, School of Chemistry and Chemical Engineering, Queen's University Belfast, David-Keir Building, Stranmillis Road, BelfastBT9 5AG, U.K.
  6. Vivek V Ranade: Theoretical and Applied Catalysis Research Cluster, School of Chemistry and Chemical Engineering, Queen's University Belfast, David-Keir Building, Stranmillis Road, BelfastBT9 5AG, U.K. ORCID
  7. Haresh G Manyar: Theoretical and Applied Catalysis Research Cluster, School of Chemistry and Chemical Engineering, Queen's University Belfast, David-Keir Building, Stranmillis Road, BelfastBT9 5AG, U.K. ORCID

Abstract

The manufacture of high-value products from biomass derived platform chemicals is becoming an integral part of the biorefinery industry. In this study, we demonstrate a green catalytic process using solvent free conditions for the synthesis of hydroxymethylfurfural (HMF) levulinate from HMF and levulinic acid (LA) over tin exchanged tungstophosphoric acid (DTP) supported on K-10 (montmorillonite K-10 clay) as the catalyst. The structural properties of solid acid catalysts were characterized by using XRD, FT-IR, UV-vis, titration, and SEM techniques. Partial exchange of the H of DTP with Sn ( = 1) resulted in enhanced acidity of the catalyst and showed an increase in the catalytic activity as compared to the unsubstituted DTP/K-10 as the catalyst. The effects of different reaction parameters were studied and optimized to get high yields of HMF levulinate. The kinetic model was developed by considering the Langmuir-Hinshelwood-Hougen-Watson (LHHW) mechanism, and the activation energy was calculated to be 41.2 kJ mol. The prepared catalysts were easily recycled up to four times without any noticeable loss of activity, and hot filtration test indicated the heterogeneous nature of the catalytic activity. The overall process is environmentally benign and suitable for easy scale up.

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Word Cloud

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