01508nas a2200217 4500008004100000022001400041245011000055210006900165260007300234300001000307490000700317520070700324653003301031653000801064653001901072653001401091653002301105100001501128700002201143856012501165 2011 eng d a1003-995300aEsterification of levulinic acid to n-butyl levulinate over heteropolyacid supported on acid-treated clay0 aEsterification of levulinic acid to nbutyl levulinate over heter aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcJAN a18-240 v203 a

Levulinic acid has been identified as a promising green, biomass-derived platform chemical. n-Butyl levulinate is used as an important intermediate having diverse applications. The present work focuses on the synthesis of n-butyl levulinate by esterification of levulinic acid with n-butanol using heteropolyacid (HPA) supported on acid-treated clay montmorillonite (K10). 20% (w/w) dodecatungestophosphoric acid (DTPA) supported on K10 was found to be the most efficient catalyst with 97% levulinic acid conversion and 100% selectivity towards n-butyl levulinate. Effects of various process parameters were studied to examine the efficacy of 20% (w/w) DTPA/K10 for optimization of the activity.

10adodectungestophosphoric acid10aK1010alevulinic acid10an-butanol10an-Butyl levulinate1 aDharne, S.1 aBokade, Vijay, V. uhttps://library.ncl.res.in/content/esterification-levulinic-acid-n-butyl-levulinate-over-heteropolyacid-supported-acid-002723nas a2200277 4500008004100000022001400041245016200055210006900217260007300286300001000359490000800369520166100377653002402038653003202062653001902094653002102113653001902134100002902153700002202182700002802204700002502232700002602257700002102283700002202304856011902326 2013 eng d a0926-860X00aCatalytic upgrading of renewable levulinic acid to ethyl levulinate biodiesel using dodecatungstophosphoric acid supported on desilicated H-ZSM-5 as catalyst0 aCatalytic upgrading of renewable levulinic acid to ethyl levulin aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcJUN a90-980 v4603 a

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.

10adesilicated H-ZSM-510aDTPA on desilicated H-ZSM-510aEsterification10aethyl levulinate10alevulinic acid1 aNandiwale, Kakasaheb, Y.1 aSonar, Shilpa, K.1 aNiphadkar, Prashant, S.1 aJoshi, Praphulla, N.1 aDeshpande, Shilpa, S.1 aPatil, Vilas, S.1 aBokade, Vijay, V. uhttps://library.ncl.res.in/content/catalytic-upgrading-renewable-levulinic-acid-ethyl-levulinate-biodiesel-using-002418nas a2200229 4500008004100000022001400041245013700055210006900192260006700261300001400328490000700342520151900349653002401868653001901892653002101911653001901932100002901951700002801980700002602008700002202034856013202056 2014 eng d a0268-257500aEsterification of renewable levulinic acid to ethyl levulinate biodiesel catalyzed by highly active and reusable desilicated H-ZSM-50 aEsterification of renewable levulinic acid to ethyl levulinate b a111 RIVER ST, HOBOKEN 07030-5774, NJ USAbWILEY-BLACKWELLcOCT a1507-15150 v893 a

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

10adesilicated H-ZSM-510aEsterification10aethyl levulinate10alevulinic acid1 aNandiwale, Kakasaheb, Y.1 aNiphadkar, Prashant, S.1 aDeshpande, Shilpa, S.1 aBokade, Vijay, V. uhttps://library.ncl.res.in/content/esterification-renewable-levulinic-acid-ethyl-levulinate-biodiesel-catalyzed-highly-active-001826nas a2200241 4500008004100000022001400041245011600055210006900171260007300240300001200313490000700325520093200332653001701264653001901281653001201300653001901312653002101331653003301352100002901385700002201414700002201436856012601458 2014 eng d a2095-495600aProduction of octyl levulinate biolubricant over modified H-ZSM-5: Optimization by response surface methodology0 aProduction of octyl levulinate biolubricant over modified HZSM5  aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcJUL a535-5410 v233 a

The present study highlighted the use of modified H-ZSM-5 (Meso-HZ-5) as heterogeneous catalyst for the synthesis of octyl levulinate biolubricant by catalytic esterification of biomass derived renewable levulinic acid (LA) with n-octanol. The process variables such as catalyst loading (X-1), n-octanol to LA molar ratio (X-2) and reaction temperature (X-3) were optimized through response surface methodology (RSM), using Box-Behnken model. Analysis of variance was performed to determine the adequacy and significance of the quadratic model. The yield of octyl levulinate was obtained to be 99% at optimum process parameters. The developed quadratic model was found to be adequate and statistically accurate with correlation value (R-2) of 0.9971 to predict the yield of octyl levulinate biolubricant. The study was also extended on the validation of theoretical and experimental data, including catalyst reusability.

10abiolubricant10aEsterification10aH-ZSM-510alevulinic acid10aoctyl levulinate10aResponse surface methodology1 aNandiwale, Kakasaheb, Y.1 aYadava, Sunil, K.1 aBokade, Vijay, V. uhttps://library.ncl.res.in/content/production-octyl-levulinate-biolubricant-over-modified-h-zsm-5-optimization-response-002298nas a2200229 4500008004100000022001400041245013100055210006900186260006700255300001200322490000700334520145300341653001301794653001901807653001801826653001901844653001401863653001001877100002901887700002201916856013001938 2015 eng d a1944-744200aEnvironmentally benign catalytic process for esterification of renewable levulinic acid to various alkyl levulinates biodiesel0 aEnvironmentally benign catalytic process for esterification of r a111 RIVER ST, HOBOKEN 07030-5774, NJ USAbWILEY-BLACKWELLcSEP a795-8010 v343 a

This study explores, the use of modified zeolite (Micro/Meso-HZ-5) obtained by desilication post-treatment as heterogeneous catalyst for esterification of biomass derived renewable levulinic acid (LA) with different alkyl alcohols such as methanol, ethanol, n-butanol, and n-octanol aiming to produce corresponding alkyl levulinate. This method of production of alkyl levulinates would be sustainable process, as it can be used as novel miscible diesel biofuels preventing global warming by decreasing atmospheric CO2. The LA conversion obtained over Micro/Meso-HZ-5 was higher than H-ZSM-5, which is due to the combined effect of increase in Bronsted acid sites, total acidity, and other properties such as BET surface area and the generation of mesoporosity. The maximum LA conversion of 91, 95, 96, and 98% with 100% selectivity toward alkyl levulinate was obtained, when LA was being esterified over Micro/Meso-HZ-5 with methanol, ethanol, n-butanol, and n-octanol, respectively, at optimal process parameters. Micro/Meso-HZ-5 catalyst was found to be reusable for six cycles. Furthermore, pseudo homogeneous (P-H) kinetic model of the esterification of LA with the studied four alcohols were established with R-2>0.99, using the experimental data. A P-H kinetic model implies that, the esterification reaction follows second order reversible kinetics. (c) 2014 American Institute of Chemical Engineers Environ Prog, 34: 795-801, 2015

10abiofuels10aEsterification10akinetic model10alevulinic acid10ameso-HZ-510amicro1 aNandiwale, Kakasaheb, Y.1 aBokade, Vijay, V. uhttps://library.ncl.res.in/content/environmentally-benign-catalytic-process-esterification-renewable-levulinic-acid-various-001734nas a2200217 4500008004100000022001400041245009100055210006900146260007700215300001200292490000700304520093300311653001901244653001801263653001901281653002001300653002301320100002901343700002201372856012201394 2015 eng d a0930-751600aEsterification of renewable levulinic acid to n-butyl levulinate over modified H-ZSM-50 aEsterification of renewable levulinic acid to nbutyl levulinate  aBOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANYbWILEY-V C H VERLAG GMBHcFEB a246-2520 v383 a

The synthesis of n-butyl levulinate, one of the most important biodiesel additives, by catalytic esterification of biomass-derived levulinic acid (LA) with n-butanol over modified H-ZSM-5 (micro/meso-HZ-5) in a closed-batch system is reported for the first time. The optimization of the reaction conditions such as the reactant molar ratio, the catalyst loading, the reaction time and the temperature was performed in view to maximize the yield of n-butyl levulinate. Micro/meso-HZ-5 was found to be the most efficient catalyst, with 98% yield of n-butyl levulinate and a reusability for six cycles, which is higher than reported in the literature. A possible catalytic mechanism for the esterification reaction is also proposed. A second-order pseudo-homogeneous model with R-2 > 0.97 confirmed that the esterification reaction is performed in the kinetic regime due to the high activation energy of 23.84 kJ mol(-1).

10aEsterification10akinetic model10alevulinic acid10aMicro/meso-HZ-510an-Butyl levulinate1 aNandiwale, Kakasaheb, Y.1 aBokade, Vijay, V. uhttps://library.ncl.res.in/content/esterification-renewable-levulinic-acid-n-butyl-levulinate-over-modified-h-zsm-5-001656nas a2200205 4500008004100000022001400041245016300055210006900218260000800287300001400295490000800309520088300317653002401200653001801224653001901242653001301261100002001274700002501294856013101319 2020 eng d a1011-372X00aEfficient synthesis of gamma-valerolactone-a potential fuel from biomass derived levulinic acid using catalytic transfer hydrogenation over Hf@CCSO3H catalyst0 aEfficient synthesis of gammavalerolactonea potential fuel from b cJUL a2038-20440 v1503 a

A new hafnium based carbonaceous catalyst (Hf@CCSO3H) was prepared by simultaneous carbonization and sulfonation of readily available glucose, followed by incorporation of hafnium metal on the surface of catalyst. The catalyst was well characterized using FT-IR, PXRD, EDX, SEM, C-13 CPNMR, XPS and BET analysis. The catalytic activity of Hf@CCSO3H was evaluated for synthesis of gamma-valerolactone-a potential fuel and green solvent. gamma-valerolactone was synthesized from biomass derived levulinic acid by catalytic transfer hydrogenation using 150 wt% of catalyst at 200 celcius for 24 h in isopropanol solvent as a hydrogen donor. 100% conversion of levulinic acid was achieved with an excellent yield of 96% with more than 99% selectivity of gamma-valerolactone as evident from GC analysis. The method developed is simple, efficient and economical. [GRAPHICS] .

10agamma-Valerolactone10aHydrogenation10alevulinic acid10aTransfer1 aJori, Popat, K.1 aJadhav, Vrushali, H. uhttps://library.ncl.res.in/content/efficient-synthesis-gamma-valerolactone-potential-fuel-biomass-derived-levulinic-acid-using02121nas a2200277 4500008004100000022001400041245013400055210006900189260000800258300001100266490000700277520120900284653001501493653001501508653001101523653000801534653001901542653002301561653001001584100002401594700002801618700002601646700002001672700002201692856012901714 2021 eng d a1944-744200aMilder operating parameters for one-step conversion of fructose to levulinic acid over sulfonated H-beta zeolite in aqueous media0 aMilder operating parameters for onestep conversion of fructose t cJAN ae135300 v403 a

The sulfonated H-beta zeolite was successfully prepared and used for the synthesis of levulinic acid (LA) fromD-fructose. The catalyst was characterized by powder X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscope, N-2 physisorption, NH3-temperature programmed desorption and carbon-hydrogen-nitrogen-sulfur analysis. The total acid amount is increased with increase in sulfur loading, confirmed that the sulfonic acid group (SO3-H) is successfully grafted onto zeolite structure. The various parameters such as different amount of sulfur loading, reaction temperature, time, catalyst loading was studied for selective production of LA. The catalytic activity of sulfonated H-beta (S-beta) zeolite was found to be efficient for synthesis of LA from D-fructose in aqueous media. Maximum LA yield of 43.5 mol%, low HMF yield (<1%) with 98.15% fructose conversion was obtained with 3% S-beta catalyst at 160 degrees C for 7 hr. The catalyst was reusable for minimum three times by H2O2 regeneration. This study provides the new zeolitic catalyst for the efficient production of LA at shorter reaction time (7 hr) and low catalyst to substrate ratio (0.7:1).

10aconversion10aD-fructose10aH-beta10aHMF10alevulinic acid10asulfonated zeolite10ayield1 aBisen, Swapneel, K.1 aNiphadkar, Prashant, S.1 aNandanwar, Sachin, U.1 aSimakova, Irina1 aBokade, Vijay, V. uhttps://library.ncl.res.in/content/milder-operating-parameters-one-step-conversion-fructose-levulinic-acid-over-sulfonated-h02017nas a2200265 4500008004100000245013200041210006900173260000800242300001100250490000700261520119700268653001501465653001501480653000901495653000801504653001901512653002301531653001001554100002401564700002801588700002601616700002001642700002201662856006701684 2021 eng d00aMilder operating parameters for one-step conversion of fructose to levulinic acid over sulfonated H-β zeolite in aqueous media0 aMilder operating parameters for onestep conversion of fructose t cFEB ae135300 v403 aAbstract The sulfonated H-β zeolite was successfully prepared and used for the synthesis of levulinic acid (LA) from D-fructose. The catalyst was characterized by powder X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscope, N2 physisorption, NH3-temperature programmed desorption and carbon–hydrogen–nitrogen–sulfur analysis. The total acid amount is increased with increase in sulfur loading, confirmed that the sulfonic acid group (SO3-H) is successfully grafted onto zeolite structure. The various parameters such as different amount of sulfur loading, reaction temperature, time, catalyst loading was studied for selective production of LA. The catalytic activity of sulfonated H-β (S-β) zeolite was found to be efficient for synthesis of LA from D-fructose in aqueous media. Maximum LA yield of 43.5 mol%, low HMF yield (<1%) with 98.15% fructose conversion was obtained with 3% S-β catalyst at 160°C for 7 hr. The catalyst was reusable for minimum three times by H2O2 regeneration. This study provides the new zeolitic catalyst for the efficient production of LA at shorter reaction time (7 hr) and low catalyst to substrate ratio (0.7:1).10aconversion10aD-fructose10aH-β10aHMF10alevulinic acid10asulfonated zeolite10ayield1 aBisen, Swapneel, K.1 aNiphadkar, Prashant, S.1 aNandanwar, Sachin, U.1 aSimakova, Irina1 aBokade, Vijay, V. uhttps://aiche.onlinelibrary.wiley.com/doi/abs/10.1002/ep.1353001303nas a2200217 4500008004100000022001400041245010000055210006900155260000800224300001100232490000700243520058000250653001200830653002400842653001800866653001700884653001900901100002100920700002500941856011900966 2022 eng d a2452-223600aIonic liquids for the sustainable transformation of levulinic acid to gamma-valerolactone (GVL)0 aIonic liquids for the sustainable transformation of levulinic ac cJUN a1006070 v353 a

This short review is focused on recent findings on the role of ionic liquids (ILs) in catalysing the hydrogenation of levulinic acid (LA) to gamma valerolactone (GVL), which is a cascade reaction involving more than one type of reaction. A brief introduction on green aspects of IL as a catalyst followed by various types of ILs being used for hydrogenation of LA to GVL are discussed. The unique characteristics of ILs responsible for hydrogenation reaction are also explained along with the current and upcoming scenario of IL catalysed hydrogenation of LA to GVL.

10aBiomass10aGamma valerolactone10aHydrogenation10aIonic liquid10alevulinic acid1 aKondawar, Sharda1 aRode, Chandrashekhar uhttps://library.ncl.res.in/content/ionic-liquids-sustainable-transformation-levulinic-acid-gamma-valerolactone-gvl02117nas a2200265 4500008004100000022001400041245017000055210006900225260000800294300001100302490000800313520115400321653002801475653001101503653001601514653001901530653003301549653002201582100003101604700002101635700002101656700002301677700002101700856013001721 2022 eng d a0008-621500aSubcritical water hydrolysis of N-acetyl-D-glucosamine: hydrolysis mechanism, reaction pathways and optimization for selective production of 5-HMF and levulinic acid0 aSubcritical water hydrolysis of NacetylDglucosamine hydrolysis m cJUN a1085600 v5163 a

In this study, the subcritical water hydrolysis of N-acetyl-D-glucosamine (NAG), a monomer of abundant renewable marine biopolymer chitin, for production of value-added chemicals is investigated. The enhanced ionization of water at subcritical conditions (200 degrees C; 50-100 bar), provides enough acidity for deacetylation of NAG resulting in 80% yield of acetic acid along with traces of formic acid, lactic acid, glucose, fructose, 5hydroxymethylfurfural (5-HMF),etc. The significant humin formation indicates that the self-condensation and polymerisation of 5-HMF is favored in water at subcritical conditions. A catalyst p-toluenesulfonic acid (p-TsOH) was employed to selectively convert NAG to levulinic acid (LA) via ring opening of 5-HMF previously formed during hydrolysis. The maximum yield of 27.13 +/- 1% and 53.46 +/- 1% of 5-HMF and LA, respectively, was obtained at process conditions optimized using Box-Behnken design coupled with response surface methodology. Subcritical water enables greener conversion of NAG to platform chemicals wherein the selective production can be achieved by tuning the process conditions.

10a5-Hydroxymethylfurfural10achitin10aGlucosamine10alevulinic acid10aResponse surface methodology10aSubcritical water1 aKulkarni, Sphurti, Prakash1 aDure, Shital, N.1 aJoshi, Sunil, S.1 aPandare, Kiran, V.1 aMali, Nilesh, A. uhttps://library.ncl.res.in/content/subcritical-water-hydrolysis-n-acetyl-d-glucosamine-hydrolysis-mechanism-reaction-pathways