Faculty Publications
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Item A straightforward preparation of levulinic esters from biorenewable levulinic acid using methanesulfonic acid supported on silica gel (MSA-SG) as an efficient heterogeneous catalyst(Elsevier Ltd, 2023) Vinod, N.; Bandibairanahalli Onkarappa, S.; Madhwaraj Girija, V.; Dutta, S.The present work reports methanesulfonic acid supported on silica gel (MSA-SG) as an inexpensive heterogeneous solid acid catalyst for the high-yielding production of various alkyl levulinates from biomass-derived levulinic acid. The catalyst was characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy with energy-dispersive X-ray analysis (SEM-EDX). The reactions were conducted in a batch-type glass pressure reactor under conventional heating. The esterification reaction was optimized on temperature, duration, and catalyst loading. The optimized reaction conditions (120 °C, 8 h, 8 wt% MSA-SG) afforded methyl- to butyl levulinate in excellent isolated yields (≥90 %). The catalyst was filtered, and the products were purified by simply evaporating the excess alcohol reagent. © 2022Item Recent Advances in the Value Addition of Biomass-Derived Levulinic Acid: A Review Focusing on its Chemical Reactivity Patterns(John Wiley and Sons Inc, 2021) Dutta, S.; Bhat, N.S.Levulinic acid (LA) is one of the most prominent biomass-derived chemical building blocks that can be transformed into specialty chemicals like fuels, solvents, monomers for polymers, plasticizers, surfactants, agrochemicals, and pharmaceuticals. Over the past three decades, an enormous amount of research data have been acquired on the preparation and downstream value addition of LA, and these works have been reviewed. However, considering the astonishing number of publications appearing every year on LA derivatives, the periodical review of recent works focusing on unique aspects of chemistry must be undertaken to critically evaluate the achievements to date, reassess the challenges, and recognize new opportunities. This review discusses the chemical-catalytic synthesis of various derivatives of LA by focusing on its functionalities and reactivity patterns. Recent literature on some crucial derivatives such as γ-valerolactone, 4,4’-diphenolic acid, and ethyl levulinate have been tabulated and discussed. The synthetic interconversion between various derivatives, mechanistic insights, critical analysis of the reaction parameters toward selective preparation of various derivatives, and their potential commercial applications have been elaborated using predominantly heterogeneous catalysts. A critical assessment of the relative advantages and shortcomings of the existing synthetic strategies for various derivatives of LA has been presented to enkindle fresh ideas. © 2021 Wiley-VCH GmbHItem Hydrogen-Economic Synthesis of Gasoline-like Hydrocarbons by Catalytic Hydrodecarboxylation of the Biomass-derived Angelica Lactone Dimer(Wiley Blackwell info@wiley.com, 2017) Chang, F.; Dutta, S.; Mascal, M.The biomass-derived platform molecule levulinic acid is converted into the angelica lactone dimer (ALD) in high overall yield using simple inorganic catalysts. Hydrodecarboxylation of ALD using a Pd/?-Al2O3 catalyst under moderate hydrogen gas pressure at high temperatures generates branched C8–C9 hydrocarbons in nearly quantitative yield consuming as little as a single equivalent of external hydrogen. These molecules are high-octane “drop-in” equivalents of isoalkanes used in commercial gasoline. Catalytic hydrodecarboxylation is presented as a highly effective means to reduce hydrogen demand in biomass-to-biofuel conversion technologies. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, WeinheimItem Upgrading of coconut shell-derived pyrolytic bio-oil by thermal and catalytic deoxygenation(Taylor and Francis Ltd., 2024) Dasari, K.K.; Gumtapure, V.; Dutta, S.The objective of this study is to upgrade the pyrolysis oil obtained from coconut shells via thermal deoxygenation and catalytic hydrodeoxygenation (HDO) and compare the elemental properties of the upgraded bio-oil samples. The crude coconut shell pyrolysis oil (cr-CSPO) was obtained in 33% yield by intermediate pyrolysis (575°C) of pre-dried coconut shells. The higher heating value (HHV) of cr-CSPO was found to be 16.46 MJ/Kg. The thermal and catalytic upgrading was done at 250°C, 30 bar of hydrogen pressure, a reaction time of 3 h, and a stirring speed of 350 rpm. In the case of catalytic upgrading, 10% Pd/C (10 wt% of cr-CSPO) was used as the catalyst. Thermally heating the cr-CSPO under identical conditions without the catalyst provided oil of HHV 25.94 MJ/kg. Catalytic HDO of the cr-PCSO showed a noticeable increase in the HHV value to 30.57 MJ/kg. The results indicate significant improvement in the combustion properties of cr-CSPO by thermal treatment and more so by the catalytic HDO chemistry. © 2020 Taylor & Francis Group, LLC.Item Efficient preparation of hybrid biofuels from biomass-derived 5-(acetoxymethyl)furfural and petroleum-derived aromatic hydrocarbons(Royal Society of Chemistry, 2024) Yadav, A.K.; Bhat, N.S.; Kaushik, S.; Seikh, A.H.; Dutta, S.Fuel candidates containing both petroleum-derived and biomass-derived molecules in their structural motifs ensure both feedstocks are used optimally and coherently. This work reports a straightforward and efficient preparation of 5-(arylmethyl)furfurals (AMFFs), 2-(arylmethyl)furans (AMFs), and 2-(arylmethyl)-5-methylfurans (AMMFs) as hybrid biofuels (or fuel oxygenates) starting from carbohydrate-derived 5-(acetoxymethyl)furfural (AcMF) and petroleum-derived aromatic hydrocarbons. The AMFFs were prepared by Friedel-Crafts reaction between AcMF and aromatic hydrocarbons (e.g., BTX, mesitylene) by employing anhydrous ZnCl2 as the catalyst. AMFs were prepared by decarbonylation of AMFFs over the Pd(OAc)2 catalyst under solvent-free conditions. In contrast, AMMFs were produced by hydrogenating AMFFs in methanol using gaseous hydrogen and the 10% Pd/C catalyst. The catalytic transformations were optimized on various parameters, and all the biofuel candidates were obtained in good to excellent isolated yields (>80%) under moderate conditions. © 2024 The Royal Society of Chemistry.