HPW Anchored Meso-HZ-5, a Novel Catalyst for Selective Synthesis of Ethyl Levulinate Biofuel by Alcoholysis of Biomass-Derived Furfuryl Alcohol Kakasaheb Y. Nandiwale , a,b Ashwini M. Pande, a and Vijay V. Bokade a a Catalysis and Inorganic Chemistry Division, CSIR - National Chemical Laboratory, Pune, 411008, India; vv.bokade@ncl.res.in (for correspondence) b Center for Environmentally Beneficial Catalysis, Department of Chemical and Petroleum Engineering, University of Kansas, 1501 Wakarusa Drive, Lawrence, Kansas, 66047, United States Published online 00 Month 2017 in Wiley Online Library (wileyonlinelibrary.com). DOI 10.1002/ep.12822 Ethanolysis of biomass derived furfuryl alcohol (FA) pro- duces ethyl levulinate (EL), a biofuel additive and precursor for g-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 reveal- ing an insight of the catalytic mechanism. The catalytic activity of H-ZSM-5, Meso-HZ-5 (desilicated H-ZSM-5) and different percentage H 3 PW 12 O 40 (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), N 2 physisorption and temperature pro- grammed NH 3 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 investi- gated. 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 bio- fuel from the biomass-derived FA. V C 2017 American Institute of Chemical Engineers Environ Prog, 00: 000–000, 2017 Keywords: ethanolysis, furfuryl alcohol, ethyl levulinate, meso-HZ-5, biofuel INTRODUCTION The over exploitation of petroleum resources causing a host of energy crisis and serious environmental concerns have drawn considerable attention of worldwide researchers to explore biomass as a sustainable alternative feedstock [1–3]. In this context, furfural alcohol (FA) obtained by hydrogenation of industrially produced (biomass derived) furfural is an important platform chemical having potential for upgrading into biochemicals and biofuel [4,5]. Further- more, catalytic alcoholysis of FA yields to alkyl levulinates, which are a versatile chemical feedstock having numerous applications as a blending compound viz; biofuel, solvents, plasticizing agent, as spices in fragrance and flavoring indus- try [6,7]. In particular, ethanolysis of FA produces ethyl levulinate (EL), one of the top 10 biomass-derived platform molecules recognized by the United States Department of Energy in 2004 [5,8,9]. Moreover, EL is a renewable oxygenate additive and used up to 5 wt. % as the diesel miscible biofuel (DMB) in regular car engines without any modifications [10–12]. One step transformation of FA to EL by acid catalyst has been reported as an atom-economical and an efficient pro- cess [5,13–16]. In this perspective, various heterogeneous cat- alysts including sulfated zirconium oxide-coated magnetic particles (SZF) [17], arylsulfonic acid functionalized hollow mesoporous carbon spheres (ArSO 3 H-HMCSs) [15], Al-TUD-1 [16], zeolites [18], ionic liquids [19], sulfonic acid- functionalized ionic liquid [20] and graphene oxide [21] have been evaluated for ethanolysis of FA. Our previous study has demonstrated that, the hierarchical-HZ-5 converts FA to EL, with stable catalytic activity for three cycles [5]. Furthermore, heteropolyacids, in particular dodecatung- stophosphoric acid (HPW) is a super acid having predomi- nantly Br€ onsted acidity and high thermal stability (573K– 623 K) [12,22]. Our previous studies on HPW anchored to desilicated H-ZSM-5 [12] and K10 [22,23] have revealed to be highly active catalysts for various acid catalyzed reactions. At the same time, it was also noticed that HPW anchored to Meso-HZ-5 catalyst has not been previously evaluated for ethanolysis of FA. These factors motivated us to further tune the properties of catalyst by anchoring HPW to Meso-HZ-5 (Hierarchical-HZ-5) support and investigate its catalytic per- formance for the one-pot conversion of FA to EL. We hypothesize that, the introduction of adequate active sites by HPW anchoring to Meso-HZ-5 having mesopores V C 2017 American Institute of Chemical Engineers Environmental Progress & Sustainable Energy (Vol.00, No.00) DOI 10.1002/ep Month 2017 1