HPW anchored Meso‐HZ‐5, a novel catalyst for selective synthesis of ethyl levulinate biofuel by alcoholysis of biomass‐derived furfuryl alcohol

Abstract

Ethanolysis of biomass derived furfuryl alcohol (FA) produces ethyl levulinate (EL), a biofuel additive and precursor for γ‐valerolactone synthesis. The present study is devoted to develop an efficient and an environmentally benign catalytic system for one‐pot conversion of FA to EL biofuel, by revealing an insight of the catalytic mechanism. The catalytic activity of H‐ZSM‐5, Meso‐HZ‐5 (desilicated H‐ZSM‐5) and different percentage H3PW12O40(HPW) anchored to Meso‐HZ‐5 catalysts have been evaluated for the FA ethanolysis. As per our knowledge, this is the first research reporting the application of HPW anchored to Meso‐HZ‐5 catalysts for the conversion of FA into EL in biomass utilization. These catalysts were synthesized and characterized by Powder X‐ray diffraction (XRD), N2 physisorption and temperature programmed NH3 desorption (TPAD). Products of FA ethanolysis viz., 4,5,5‐triethoxypentan‐2‐one (TEP), ethoxy‐methyl‐ furan (EMF), diethyl ether (DEE), EL were identified by Gas Chromatography‐Mass Spectroscopy (GC‐MS) and quantified by flame ionization detector (GC‐FID). The physicochemical properties of catalysts were found to correlate to the product distribution matrix. Moreover, influences of several process parameters such as catalyst amount, reactant molar ratio, temperature and time on the extent of FA ethanolysis were systematically investigated. Under optimized conditions, 15% (w/w) HPW/Meso‐HZ‐5 exhibited a remarkable catalytic performance with complete FA conversion (100%) along with 97% yield of EL, these activity values are superior than the previously reported studies. The present study provides an insight of the catalytic mechanism along with a potential environmental benign and the economic catalyst for the efficient synthesis of EL biofuel from the biomass‐derived FA. © 2017 American Institute of Chemical Engineers Environ Prog, 37: 1736–1742, 2018

Versatile Coordination Polymer Catalyst for Acid Reactions Involving Biobased Heterocyclic Chemicals

“…Nano ZSM-5 led to 91% yield at 140 °C/1 h [173], while 1 required 24 h to reach a similar EL yield of 92%, using a similar FA concentration (0.33-0.39 M) but requiring a much lower catalyst/FA mass ratio (0.30 for 1 versus 1.02 for ZSM-5). Superior results were reported for HPW-MesoZSM-5 [193], Ti-HPA [183], Fe-USY [194] and magnetic sulfated zir-…”

“…Nano ZSM-5 led to 91% yield at 140 • C/1 h [173], while 1 required 24 h to reach a similar EL yield of 92%, using a similar FA concentration (0.33-0.39 M) but requiring a much lower catalyst/FA mass ratio (0.30 for 1 versus 1.02 for ZSM-5). Superior results were reported for HPW-MesoZSM-5 [193], Ti-HPA [183], Fe-USY [194] and magnetic sulfated zirconia (MSZ) [167], which led to 91-97% EL yield at 120-130 • C and 0.5-5 h (for 1: 72% EL at 140 • C/5 h). A higher FA initial concentration was used for HPW-MesoZSM-5 and MSZ (1.04-3.12 M versus 0.33 M for 1) [193], and a lower catalyst/FA mass ratio was used for HPW-MesoZSM5 [193], Ti-HPA [183], Fe-USY [194] and MSZ (0.02-0.07 versus 0.33 for 1) [167].…”

“…Superior results were reported for HPW-MesoZSM-5 [193], Ti-HPA [183], Fe-USY [194] and magnetic sulfated zirconia (MSZ) [167], which led to 91-97% EL yield at 120-130 • C and 0.5-5 h (for 1: 72% EL at 140 • C/5 h). A higher FA initial concentration was used for HPW-MesoZSM-5 and MSZ (1.04-3.12 M versus 0.33 M for 1) [193], and a lower catalyst/FA mass ratio was used for HPW-MesoZSM5 [193], Ti-HPA [183], Fe-USY [194] and MSZ (0.02-0.07 versus 0.33 for 1) [167]. However, MSZ requires catalyst regeneration at 500 • C to keep the catalytic performance steady, whereas 1 does not require thermal regeneration.…”

Synthesis of ethyl levulinate from cellulose over a double acid site catalyst

“…This occurred because, with the increased number of active sites, the amount of reactant species and the quantity of active sites reached an optimal level, beyond which the addition of more active groups hindered contact between the reactants and the substrate, thus reducing the yield. 54 Nandiwale et al 56 used the solid acid HPW/MESO-HZ-5 to catalyze the transformation of furfuryl alcohol to EL. When the HPW loading was increased from 5 to 15 wt%, the EL yield increased from 14.0 to 24.0 mol%, while a further loading increase to 20 wt% actually resulted in a slight decrease in yield.…”

Direct conversion of furfuryl alcohol to butyl levulinate using tin exchanged tungstophosphoric acid catalysts

“…In recent times, the rise in energy demand and depletion of fossil fuel reserves has led to an increased attention to biomass as the potential resource for alternative energy and biofuels [1]. Apart from sustainable energy, biomass is also a key feedstock for production of a variety of value-added chemicals, which makes the biomass-derived fuel processes more economic [2][3][4]. To reduce the dependency on non-renewable resources, European Union and US governments have set targets to utilize renewable resources to produce up to 20% of fuel and 25% of chemicals [5].…”