@article { ISI:000226714000027, title = {Convenient synthesis of 5-methylene-4-substituted-2(5H)-furanones}, journal = {Tetrahedron Letters}, volume = {46}, number = {6}, year = {2005}, month = {FEB}, pages = {1009-1012}, publisher = {PERGAMON-ELSEVIER SCIENCE LTD}, type = {Article}, address = {THE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLAND}, abstract = {

A synthesis of novel 4-(substituted)benzyl-5-methylene-2(5H)-furanones involving Stobbe condensation of substituted aldehydes with ethyl levulinate followed by treatment with acetic anhydride in the presence of sodium acetate, has been developed. (C) 2004 Elsevier Ltd. All rights reserved.

}, keywords = {5-methylene-2(5H)-furanones, acetic anhydride, arylaldehydes, ethyl levulinate, sodium acetate}, issn = {0040-4039}, doi = {10.1016/j.tetlet.2004.12.040}, author = {Mahajan, Vishal A. and Shinde, Popat D. and Borate, Hanumant B. and Wakharkar, Radhika D.} } @article { ISI:000320976600013, title = {Catalytic upgrading of renewable levulinic acid to ethyl levulinate biodiesel using dodecatungstophosphoric acid supported on desilicated H-ZSM-5 as catalyst}, journal = {Applied Catalysis A-General}, volume = {460}, year = {2013}, month = {JUN}, pages = {90-98}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

Levulinic acid (LA) is considered as a renewable platform chemical and can be used for the synthesis of variety of important fuels and chemicals. In particular, its esterification with ethanol produces ethyl levulinate (EL) would be green process, as it can be used as diesel miscible biofuel (DMB), preventing global warming by decreasing atmospheric CO2. This study explores the use of modified H-ZSM-5 by desilication viz.; DH-ZSM-5 and dodecatungstophosphoric acid (DTPA) loaded on DH-ZSM-5 for esterification of LA with ethanol aiming to EL. Different degree of desilication of H-ZSM-5 was performed by using aq. NaOH (0.2-1.5 M) at 338 K for 30 min and then DTPA was loaded on these desilicated H-ZSM-5 (DH-ZSM-5) support. H-ZSM-5, DH-ZSM-5 and DTPA on these DH-ZSM-5 samples were characterized by powder x-ray diffraction (XRD), N-2 adsorption-desorption, pyridine chemisorbed IR spectroscopy, Temperature Programmed Ammonia Desorption (TPAD). The increase in conversion of levulinic acid was observed from 28\% to 94\% with increase of DTPA loading from 0\% to 15\%. The increased LA conversion may be due to increase in total acidity from 43.14\% to 84.31\%. The use of DH-ZSM-5 as support for deposition of DTPA may be reported for the first time. The present work also extended to optimize process parameters such as DTPA loading on DH-ZSM-5, catalyst to LA ratio, LA to ethanol molar ratio, speed of agitation, particle size reaction temperature and catalyst reusability. Kinetic study based on pseudo-homogeneous (P-H) model is also presented. The experimental results follow second order kinetics. (C) 2013 Elsevier B.V. All rights reserved.

}, keywords = {desilicated H-ZSM-5, DTPA on desilicated H-ZSM-5, Esterification, ethyl levulinate, levulinic acid}, issn = {0926-860X}, doi = {10.1016/j.apcata.2013.04.024}, author = {Nandiwale, Kakasaheb Y. and Sonar, Shilpa K. and Niphadkar, Prashant S. and Joshi, Praphulla N. and Deshpande, Shilpa S. and Patil, Vilas S. and Bokade, Vijay V.} } @article { ISI:000328527000041, title = {Esterification of levulinic acid to ethyl levulinate over bimodal micro-mesoporous H/BEA zeolite derivatives}, journal = {Catalysis Communications}, volume = {43}, year = {2014}, month = {JAN}, pages = {188-191}, publisher = {ELSEVIER SCIENCE BV}, address = {PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS}, abstract = {

A series of bimodal micro-mesoporous H/BEA zeolite derivatives were prepared by the post-synthesis modification of H/BEA zeolite by NaOH (0.05 M-1.2 M) treatment Samples were characterized by powder XRD, low temperature nitrogen adsorption/desorption, temperature programmed desorption of ammonia and ICP. The mesopore formation was found to play a crucial role in liquid phase esterification of levulinic acid with ethanol. The enhanced catalytic activity of a bimodal micro-mesoporous H/BEA zeolite derivative (H/BEA(0.10)) prepared by treatment with 0.1M NaOH can be mainly attributed to the high mesoporosity coupled with better preserved crystallinity and acidic properties. (C) 2013 Elsevier B.V. All rights reserved.

}, keywords = {Esterification, ethyl levulinate, H/BEA zeolite, Mesoporosity, Post-synthesis modification}, issn = {1566-7367}, doi = {10.1016/j.catcom.2013.10.006}, author = {Patil, C. R. and Niphadkar, P. S. and Bokade, Vijay V. and Joshi, P. N.} } @article { ISI:000341764500007, title = {Esterification of renewable levulinic acid to ethyl levulinate biodiesel catalyzed by highly active and reusable desilicated H-ZSM-5}, journal = {Journal of Chemical Technology and Biotechnology}, volume = {89}, number = {10}, year = {2014}, month = {OCT}, pages = {1507-1515}, publisher = {WILEY-BLACKWELL}, type = {Article}, address = {111 RIVER ST, HOBOKEN 07030-5774, NJ USA}, abstract = {

BACKGROUNDIn the near future, fossil fuel will have limitations in terms of availability and also great concerns over its environmental impact. New routes and related technologies based on renewable feedstocks can overcome most of these problems associated with fossil fuel. Among current biodiesel sources, ethyl levulinate (EL) biodiesel obtained from catalytic esterification of renewable levulinic acid (LA) with ethanol has received a great deal of attention. The use of desilicated H-ZSM-5 (DH-ZSM-5) as heterogeneous acid catalyst for EL biodiesel production in a closed system (under autogeneous pressure) was studied. RESULTSThe effect of reaction parameters such as ethanol to LA molar ratio (4:1 to 10:1), catalyst to LA ratio (0.10-0.25), speed of agitation (100-400rpm), particle size (53-355 mu m), reaction temperature (363-403K) and reaction time (7h) was investigated to maximize LA conversion. CONCLUSIONLevulinic acid conversion reached 95\% over DH-ZSM-5 and the catalyst was reusable for up to six cycles. This LA conversion and the catalyst reusability values are higher than others reported in the literature. A pseudo-homogeneous (P-H) kinetic model indicated that reaction rate constants increased with increasing molar ratio, catalyst to LA ratio and reaction temperature. The activation energy decreased from 73.14 to 21.08 kJ mol(-1) when increasing the catalyst to LA ratio from 0.10 to 0.25, which implies a kinetically controlled reaction. (c) 2013 Society of Chemical Industry

}, keywords = {desilicated H-ZSM-5, Esterification, ethyl levulinate, levulinic acid}, issn = {0268-2575}, doi = {10.1002/jctb.4228}, author = {Nandiwale, Kakasaheb Y. and Niphadkar, Prashant S. and Deshpande, Shilpa S. and Bokade, Vijay V.} } @article {46827, title = {Catalytic conversion of HMF into ethyl levulinate - a biofuel over hierarchical zeolites}, journal = {Catalysis Communications}, volume = {140}, year = {2020}, month = {JUN}, pages = {105998}, type = {Article}, abstract = {

Catalytic conversion of 5-hydroxymethyl-2-furfuraldehyde (HMF, a biomass-derived platform chemical) into ethyl levulinate (EL) is an attractive approach for producing renewable transport fuels for mitigating global warming. We report here the application of hierarchical zeolites (DZSM-5 and MZSM-5 synthesized by desilication and mesoporous templating approaches, respectively) as solid acid catalysts for this transformation. Hierarchical structure of these zeolites was confirmed by X-ray diffraction, nitrogen-physisorption and electron microscopy, and acidity was determined by temperature-programmed desorption of ammonia. HMF conversion of 94.2\% with EL selectivity of 90.8\% was achieved over the MZSM-5 catalyst. Acidity, pore size and surface properties affected the catalytic activity.

}, keywords = {5-Hydroxymethyl-2-furfuraldehyde (HMF), Biofuel, ethyl levulinate, Hierarchical zeolite, ZSM-5}, issn = {1566-7367}, doi = {10.1016/j.catcom.2020.105998}, author = {Chithra, P. A. and Darbha, Srinivas} } @article {46676, title = {Highly efficient micro-meso acidic H-USY catalyst for one step conversion of wheat straw to ethyl levulinate (biofuel additive)}, journal = {Microporous and Mesoporous Materials}, volume = {306}, year = {2020}, month = {OCT}, pages = {110474}, type = {Article}, abstract = {

Ethyl Levulinate (EL), biofuel additive can blend up to 20\% with biodiesel to improve its fuel properties. Till the date, there are reports on homogeneous catalysts (H2SO4, ionic liquid) for synthesis of EL from raw biomass like wheat straw. To best of our knowledge, there is no single report on heterogeneous catalyst for one step synthesis of EL directly from wheat straw. This work is a successful attempt to use heterogeneous micro-meso acidic H-USY (post dealumination and desilication) for direct one step conversion of wheat straw to EL with higher EL yield 24.5 wt\%, which is probably the highest so far.

}, keywords = {Acidity, ethyl levulinate, H-USY, Micro-meso, Wheat straw}, issn = {1387-1811}, doi = {10.1016/j.micromeso.2020.110474}, author = {Heda, Jidnyasa and Niphadkar, Prashant and Mudliar, Sandeep and Bokade, Vijay} } @article {47580, title = {Single-pot alcoholysis of furfuryl alcohol to alkyl levulinates using heterogenized p-TSA catalyst**}, journal = {ChemistrySelect}, volume = {6}, year = {2021}, month = {JUL }, pages = {6636-6643}, type = {Article}, abstract = {Synthesis of levulinate esters which are known to be excellent sustainable fuel additives, was achieved by alcoholysis of furfuryl alcohol over strong solid acid catalyst, prepared by copolymerization of p-toluenesulfonic acid with paraformaldehyde. Our catalyst possessed Bronsted acidity (3 mmol/g) with an excellent stability up to 220 degrees C. XPS, FT-IR and Pyridine-IR along with microanalysis studies confirmed the presence of terminal -SO3H functional groups responsible for Bronsted acidity in the catalyst. The catalyst was found to efficiently catalyze the alcoholysis of furfuryl alcohol to give alkyl levulinates under mild reaction conditions. The complete conversion of furfuryl alcohol with 96 \% and 97 \% selectivities to ethyl and butyl levulinates could be achieved using ethanol and butanol, respectively. Detailed study on effect of various reaction parameters like catalyst loading, reaction time and reaction temperature on conversion and product distribution was also carried out for the ethanolysis of furfuryl alcohol to ethyl levulinate. The catalyst could be easily recovered and recycled for five times successfully, with no loss in its original activity.}, keywords = {Biomass, ethyl levulinate, Fuel additive, Furfuryl alcohol, heterogeneous catalysis}, issn = {2365-6549}, doi = {10.1002/slct.202101392}, author = {Patil, Chetana R. and Kamble, Sanjay P. and Rode, Chandrashekhar V.} } @article {48257, title = {Effect of acidity and mesoporosity in H-USY on conversion of wheat straw to ethyl levulinate (Biofuel additive)}, journal = {Journal of the Indian Chemical Society}, volume = {100}, year = {2023}, month = {FEB}, pages = {100883}, type = {Article}, abstract = {

Cold flow properties of biodiesel can be improved by addition of additives especially ethyl levulinate (EL up to 20\%). There are very limited information on synthesis of EL from actual raw biomass like wheat straw over heterogeneous catalyst. The present article elaborated on optimization of Acidity to Mesoporosity ratio in H-USY, which is crucial for its application in conversion of raw wheat straw to selective formation of EL in one-step. The acidity and mesoporosity is monitor by systematic post treatment of desilication and dealumination. Optimum acidity/mesoporosity ratio of 3.6 in HUSY resulted in to maximum EL yield of 24.5\%, which is probably the highest so far.

}, keywords = {Acidity, Biofuel additive, Dealumination, Desilication, ethyl levulinate, H-USY, Mesoporosity, Wheat straw}, issn = {0019-4522}, doi = {10.1016/j.jics.2023.100883}, author = {Heda, Jidnyasa and Niphadkar, Prashant and Nandanwar, Sachin and Bokade, Vijay} }