02723nas 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-002423nas a2200229 4500008004100000022001400041245012500055210006900180260007700249300001200326490000600338520156500344653001301909653001401922653001901936653001901955653001301974100002901987700002302016700002202039856013202061 2014 eng d a2194-428800aGlycerol etherification using n-butanol to produce oxygenated additives for biodiesel fuel over H-beta zeolite catalysts0 aGlycerol etherification using nbutanol to produce oxygenated add aBOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANYbWILEY-V C H VERLAG GMBHcMAY a446-4520 v23 a

The catalytic etherification of glycerol has been systematically studied in batch process by using n-butanol to produce oxygenated additives for biodiesel fuels over various solid-acid catalysts, such as H-beta zeolite, ZSM-5, K10, etc.. The present work includes a detailed study of the optimization of the etherification process parameters, such as catalyst loading (7-20 wt% of glycerol), molar ratio of glycerol/n-butanol (1: 6 to 1: 15), speed of agitation (100-400 rpm), reaction temperature (413-453 K), and reaction time (0.5-4 h) in view of maximizing the glycerol conversion and selectivity towards mono-butyl-glycerol ether (ME). The catalyst reusability was studied using the optimized process parameters. Amongst the studied catalysts, the H-beta zeolite was found to be the most promising for the etherification of glycerol with glycerol conversion of 55% and a 98% selectivity towards ME formation. The H-beta zeolite was found to be an active and stable catalyst for up to 4 cycles. The use of n-butanol as alkylating agent is presented for first time, to the authors knowledge. The reaction was performed at milder operating conditions (0.5 MPa) than previously reported (2 MPa). A kinetic model was developed for the etherification reaction and the data obtained at optimized process parameters was used to calculate the kinetic parameters. The reaction rate constants at different reaction temperatures, activation energies, and pre-exponential factors were obtained for the etherification reaction with an accuracy of R-2 > 0.989.

10abiofuels10acatalysis10aetherification10afuel additives10azeolites1 aNandiwale, Kakasaheb, Y.1 aPatil, Shivraj, E.1 aBokade, Vijay, V. uhttps://library.ncl.res.in/content/glycerol-etherification-using-n-butanol-produce-oxygenated-additives-biodiesel-fuel-over-h-001676nas a2200265 4500008004100000022001400041245013400055210006900189260007100258300001400329490000600343520068500349653002801034653001801062653001201080653001501092653003101107100002901138700002401167700002001191700002301211700002301234700002201257856013101279 2014 eng d a2168-048500aOne-pot synthesis of 5-hydroxymethylfurfural by cellulose hydrolysis over highly active bimodal micro/mesoporous H-ZSM-5 catalyst0 aOnepot synthesis of 5hydroxymethylfurfural by cellulose hydrolys a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcJUL a1928-19320 v23 a

Direct synthesis of 5-hydroxymethylfurfural (5-HMF), a useful renewable biofuel and biochemical, was systematically studied by hydrolysis of microcrystalline cellulose over Bimodal-HZ-5 zeolite. Bimodal-HZ-5 zeolite obtained by post-synthesis modification of H-ZSM-5 with desilication was found to be a potential heterogeneous catalyst with 67% cellulose conversion and 46% yield of 5-HMF. Bimodal-HZ-5 was observed to be reusable for four cycles, without any loss in activity. The detailed optimization of process parameters and catalyst reusability are also presented. The present study opens a new avenue for the renewable one-pot synthesis of 5-HMF, a valuable product.

10a5-Hydroxymethylfurfural10aBiomodal-HZ-510aglucose10aHydrolysis10aMicrocrystalline cellulose1 aNandiwale, Kakasaheb, Y.1 aGalande, Nitish, D.1 aThakur, Pratika1 aSawant, Sanjay, D.1 aZambre, Vishal, P.1 aBokade, Vijay, V. uhttps://library.ncl.res.in/content/one-pot-synthesis-5-hydroxymethylfurfural-cellulose-hydrolysis-over-highly-active-bimodal-001777nas a2200157 4500008004100000022001400041245016300055210006900218260007100287300001600358490000700374520105800381100002901439700002201468856012901490 2014 eng d a0888-588500aProcess optimization by response surface methodology and kinetic modeling for synthesis of methyl oleate biodiesel over H3PW12O40 anchored montmorillonite K100 aProcess optimization by response surface methodology and kinetic a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcDEC a18690-186980 v533 a

Heterogeneous acid catalysts comprised of 1030% (w/w) H3PW12O40 anchored to montmorillonite (K10) were used for synthesis of methyl oleate biodiesel by esterification of free fatty acid (oleic acid) with methanol in closed batch system. Response surface methodology (RSM) was employed to optimize esterification of oleic acid with methanol over 20% (w/w) H3PW12O40/K-10. The effects of various process parameters such as catalyst loading, molar ratio, and reaction temperature on oleic acid conversion were addressed by BoxBehnken experimental design (BBD). Coefficient of determination (R-2) of this model was 0.996. 20% (w/w) H3PW12O40/K-10 was proved to be potential catalyst with 100% oleic acid conversion at optimized process parameters and with reusability of four cycles. Moreover, a second-order pseudohomogeneous (PH) kinetic model has been proposed and validated (R-2 > 0.97) with experimental data. Kinetics confirmed that esterification reaction is performed in the kinetic regime due to high activation energy of 43.7 kJ mol(-1).

1 aNandiwale, Kakasaheb, Y.1 aBokade, Vijay, V. uhttps://library.ncl.res.in/content/process-optimization-response-surface-methodology-and-kinetic-modeling-synthesis-methyl-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-002353nas a2200229 4500008004100000022001400041245016000055210006900215260006700284300001200351490000700363520144500370653001601815653003301831653001901864653001801883653002401901100002401925700002901949700002201978856012302000 2014 eng d a0894-323000aPseudo-homogeneous kinetic model for esterification of acetic acid with propanol isomers over dodecatungstophosphoric acid supported on montmorillonite k100 aPseudohomogeneous kinetic model for esterification of acetic aci a111 RIVER ST, HOBOKEN 07030-5774, NJ USAbWILEY-BLACKWELLcFEB a121-1270 v273 a

Esterification of acetic acid with propanol isomers such as isopropanol and naEuropropanol was carried out over dodecatungstophosphoric acid (DTPA), dodecamolybdophosphoric acid ammonium salt hydrate, and sodium tungstate hydrated purified supported on montmorillonite K10, which were characterized by powder XaEuroray diffraction, BrunaueraEuro'EmmettaEuro'Teller, and temperature programmed ammonia desorption. A pseudoaEurohomogeneous (PaEuroH) kinetic model was established for esterification of acetic acid with propanol isomers over DTPA supported on montmorillonite K10. Effects of various parameters such as reaction time, speed of agitation, particle size, temperature, percent catalyst loading, molar ratio and mixture of propanol isomer were investigated in detail. The 20% (w/w) DTPA/K10 was found to be an optimum solid catalyst with 82% naEuropropanol and 53% isopropanol conversion with 100% selectivity toward propyl acetate. The 20% (w/w) DTPA/K10 catalyst was found to be reusable for three cycles. The reaction follows secondaEuroorder kinetics with activation energies of 25.53aEuro?kJaEuro?mol(a?'1) and 28.15aEuro?kJaEuro?mol(a?'1) for isopropanol and naEuropropanol, respectively. PseudoaEurohomogeneous kinetic model fitted with R-2 value of trend line 0.999. This implies that esterification reaction is kinetically controlled owing to high activation energy. Copyright a (c) 2013 John Wiley & Sons, Ltd.

10aAcetic acid10adodecatungstophosphoric acid10aEsterification10akinetic model10amontmorillonite K101 aGurav, Hanumant, R.1 aNandiwale, Kakasaheb, Y.1 aBokade, Vijay, V. uhttps://library.ncl.res.in/content/pseudo-homogeneous-kinetic-model-esterification-acetic-acid-propanol-isomers-over-002221nas a2200157 4500008004100000022001400041245014900055210006900204260011000273300001600383490000600399520148800405100002901893700002201922856011901944 2014 eng d a2046-206900aSelective synthesis of propofol (2,6-diisopropylphenol), an intravenous anesthetic drug, by isopropylation of phenol over H-beta and H-mordenite0 aSelective synthesis of propofol 26diisopropylphenol an intraveno aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcJUL a32467-324740 v43 a

Propofol (2,6-diisopropylphenol/DIPP) is the world's most widely used intravenous general anesthetic and is typically synthesized by isopropylation of phenol over an acid catalyst. It is highly difficult to stabilize bio-oil containing phenolic compounds. The isopropylation of this phenol (a model compound representing species in bio-oils) is one of the options to stabilize the bio-oil and convert it into valuable products. Probably for the first time, H-beta- and H-mordenite-catalysed vapour phase isopropylation of phenol with isopropyl alcohol (IPA) was studied to selectively synthesize DIPP. The optimization of various operating parameters such as molar ratio (phenol : IPA), weight hourly space velocity (WHSV), reaction temperature and time on stream were performed. H-beta (94% phenol conv. and 56% DIPP sel.) was found to be a potential and more active catalyst than H-mordenite (68% phenol conv. and 43% DIPP sel.) at optimized process parameters. A kinetic model is proposed to probe the intricate reaction kinetics and validated (R-2 > 0.98) by the experimental results. H-beta catalyst was observed to be stable for more than 25 h with 94% phenol conversion and 56% selectivity towards DIPP at optimized process parameters. The phenol conversion and DIPP selectivity obtained in the present study are higher than those reported so far. The activation energy obtained for isopropylation of phenol with IPA over H-beta is calculated to be 25.39 kJ mol(-1).

1 aNandiwale, Kakasaheb, Y.1 aBokade, Vijay, V. uhttps://library.ncl.res.in/content/selective-synthesis-propofol-26-diisopropylphenol-intravenous-anesthetic-drug-002167nas a2200253 4500008004100000022001400041245009900055210006900154260009500223300001200318490000700330520123800337653001601575653001901591653001901610653001601629653002201645653002201667100002901689700002401718700002001742700002201762856012901784 2015 eng d a0263-876200aBenzylation of acetic acid to benzyl acetate over highly active and reusable micro/meso-HZSM-50 aBenzylation of acetic acid to benzyl acetate over highly active  a165-189 RAILWAY TERRACE, DAVIS BLDG, RUGBY CV21 3HQ, ENGLANDbINST CHEMICAL ENGINEERScJAN a584-5900 v933 a

Catalytic benzylation of acetic acid (AA) with benzyl alcohol (BA) to benzyl acetate was studied over zeolites viz. H-ZSM-5 (microporous, medium pore), Micro/Meso-HZSM-5 (combination of micro- and meso pore), H-Beta (microporous, large pore) to investigate catalytic activity and selectivity towards benzyl acetate. Micro/Meso-HZSM-5 obtained by desilication post-treatment has been employed as a heterogeneous catalyst for benzylation reaction probably for the first time. Micro/Meso-HZSM-5 was found to be a promising catalyst for benzylation with AA conversion of 94%, selectivity towards benzyl acetate of 95%. The detailed optimization of process parameters such as molar ratio, catalyst loading, reaction temperature and time was also presented. Micro/Meso-HZSM-5 catalyst was observed to be stable for six cycles (1 fresh and 5 recycles). The first order reaction kinetics (R-2 >0.98) indicated that reaction rate constants increased with increasing reaction temperature. The activation energy for benzylation of AA with BA over Micro/Meso-HZSM-5 was obtained to be 15.07 kJ mol(-1), which is far less than the reported. (C) 2014 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

10aAcetic acid10aBenzyl acetate10aBenzyl alcohol10aBenzylation10aMicro/Meso-HZSM-510aReaction kinetics1 aNandiwale, Kakasaheb, Y.1 aGalande, Nitish, D.1 aRaut, Sunil, A.1 aBokade, Vijay, V. uhttps://library.ncl.res.in/content/benzylation-acetic-acid-benzyl-acetate-over-highly-active-and-reusable-micromeso-hzsm-5-002303nas a2200229 4500008004100000022001400041245013600055210006900191260009500260300001200355490000700367520140500374653001201779653001601791653002801807653001601835653002101851100002901872700001901901700002201920856013101942 2015 eng d a0263-876200aCatalytic upgrading of citric acid to environmental friendly tri-butyl citrate plasticizer over ultra stable phosphonated Y zeolite0 aCatalytic upgrading of citric acid to environmental friendly tri a165-189 RAILWAY TERRACE, DAVIS BLDG, RUGBY CV21 3HQ, ENGLANDbINST CHEMICAL ENGINEERScJUN a212-2190 v983 a

The catalytic synthesis of non-toxic/eco-friendly tributyl citrate (TBC) plasticizer by esterification of renewable citric acid (CA) with butanol would be completely sustainable route. In this context, catalytic performance of parent ultra stable Y (USY) and phosphonated USY catalysts were investigated for TBC synthesis. Parent USY and phosphonated USY catalysts were characterized by powder X-ray diffraction (XRD), N-2 adsorption-desorption, NH3 temperature programmed desorption (TPD), pyridine-Fourier Transform Infrared Spectroscopy (FTIR), FTIR, SEM, ICP. The influence of various process parameters such as phosphorous (P) loading (0 to 4 wt/%), catalyst loading (5-25%), molar ratio of CA to n-butanol (1:4 to 1:12), reaction temperature (383-423 K) and reaction time (1-5 h) have been investigated over USY catalyst with aim to maximize CA conversion and TBC yield. Amongst the studied catalysts, the 2% (w/w) P/USY was found to be highly potential catalyst with complete CA conversion (100%) and 93% TBC yield. The present method of using 2% (w/w) P/USY catalyst for the synthesis of TBC would be environmentally benign in the context of bio-renewable synthetic route, high catalytic activity, non-toxic product, long term stability and reusability of catalyst (five catalytic cycles). (c) 2015 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved,

10aButanol10aCitric acid10aheterogeneous catalysis10aPlasticizer10aTributyl citrate1 aNandiwale, Kakasaheb, Y.1 aGogoi, Pranjal1 aBokade, Vijay, V. uhttps://library.ncl.res.in/content/catalytic-upgrading-citric-acid-environmental-friendly-tri-butyl-citrate-plasticizer-over-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-5-002265nas a2200169 4500008004100000022001400041245013100055210006900186260011000255300001600365490000600381520150500387100002901892700002301921700002201944856012901966 2015 eng d a2046-206900aOne step synthesis of ethyl levulinate biofuel by ethanolysis of renewable furfuryl alcohol over hierarchical zeolite catalyst0 aOne step synthesis of ethyl levulinate biofuel by ethanolysis of aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcSEP a79224-792310 v53 a

Ethanolysis of renewable furfuryl alcohol (FAL) to ethyl levulinate (EL) biofuel over various zeolites viz. H-ZSM-5 (microporous, medium pore), Hierarchical-HZ-5 (combination of micro-and meso pore), H-Beta (microporous, large pore) and Ultra Stable Y (USY, microporous, large pore) was studied in detail. To the best of our knowledge, probably for the first time, Hierarchical-HZ-5 synthesized by desilication post-treatment has been employed as a heterogeneous catalyst for ethanolysis of FAL. The synthesized catalysts were characterized by powder X-ray diffraction (PXRD), temperature programmed NH3 desorption (TPAD), Energy dispersive X-ray analysis (EDAX), etc. Response surface methodology (RSM) with Box-Behnken experimental design (BBD) was used to investigate the influence of three crucial process variables of ethanolysis such as ethanol to FAL molar ratio, percent catalyst loading and reaction temperature on EL yield. The optimization tool of design expert software was employed to obtain the optimum reaction parameters for FAL ethanolysis over Hierarchical-HZ-5 catalyst. Three intermediates of FAL ethanolysis reaction such as, ethoxymethylfuran (EMF), 4,5,5-triethoxypentan-2-one and diethyl ether (DEE) have been identified and quantified from the product mixture with the aid of Gas Chromatography-Mass Spectroscopy (GC-MS). Hierarchical-HZ-5 was found to be a potential catalyst for ethanolysis of FAL with 73% EL yield and 26% EMF yield at optimized process parameters.

1 aNandiwale, Kakasaheb, Y.1 aPande, Ashwini, M.1 aBokade, Vijay, V. uhttps://library.ncl.res.in/content/one-step-synthesis-ethyl-levulinate-biofuel-ethanolysis-renewable-furfuryl-alcohol-over-002155nas a2200217 4500008004100000022001400041245012400055210006900179260007300248300001200321490000700333520131700340653001401657653001901671653002101690653002401711100002901735700002201764700002201786856012901808 2015 eng d a2095-495600aPhosphonated USY, a promising catalyst for the development of environmentally benign biodiesel (methyl acetate) process0 aPhosphonated USY a promising catalyst for the development of env aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcMAY a285-2900 v243 a

The present study focuses on the evaluation of the potential applicability of Ultra Stable Y (USY) and phosphonated USY (1 wt%-4 wt% phosphorous loading) as heterogeneous catalysts for biodiesel (methyl acetate) production. The synthesized catalysts were characterized by powder X-ray diffraction (XRD), Brunaer-Emmett-Teller (BET) surface area, total acidity by temperature-programmed desorption of ammonia (TPD-NH3) and Fourier Transform Infrared (FTIR) spectra. The performances of catalysts were evaluated for the transesterification of butyl acetate with methanol (a model reaction in biodiesel production). In view to obtain a maximum yield of methyl acetate, the optimization of process parameters such as reactant molar ratio, catalyst loading, reaction temperature and reaction time was performed. All the phosphonated USY catalysts showed higher catalytic activity than the parent USY, which can be attributed to the increase of total acidity due to phosphonation. 2 wt% P/USY (2% phosphorous loaded on USY) exhibited 92% methyl acetate yield with 100% selectivity, which was proved to be a potential catalyst for biodiesel production. The invented catalyst was found to be stable and reusable for five catalytic cycles, demonstrating that it might be a environmentally benign catalytic process.

10aBiodiesel10amethyl acetate10aphosphonated USY10atransesterification1 aNandiwale, Kakasaheb, Y.1 aGopal, Gahana, C.1 aBokade, Vijay, V. uhttps://library.ncl.res.in/content/phosphonated-usy-promising-catalyst-development-environmentally-benign-biodiesel-methyl-001875nas a2200169 4500008004100000022001400041245016700055210006900222260011000291300001600401490000600417520108000423100002901503700002401532700002201556856012701578 2015 eng d a2046-206900aProcess optimization by response surface methodology for transesterification of renewable ethyl acetate to butyl acetate biofuel additive over borated USY zeolite0 aProcess optimization by response surface methodology for transes aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcJAN a17109-171160 v53 a

Butyl acetate, a renewable biofuel additive was synthesized by transesterification of butanol with ethyl acetate via a renewable and sustainable route. Use of fermentation derived bio-butanol and bio-ethyl acetate for synthesis of butyl acetate would be a more advantageous route over conventional Fischer Esterification. For the first time, a heterogeneous zeolite catalyst such as Ultra Stable Y (USY) and its modified versions obtained by borating on parent USY were used for the synthesis of butyl acetate. Response surface methodology (RSM) was employed to optimize the process parameters for transesterification of butanol with ethyl acetate over a 4% (w/w) B-USY catalyst. The influence of three crucial process variables such as catalyst loading, molar ratio, and reaction temperature on yield of butyl acetate were addressed by Box-Behnken experimental design (BBD). 4% (w/w) B-USY was proved to be a potential catalyst with 96% yield of butyl acetate at optimum process parameters. The 4% (w/w) B-USY catalyst was found to be reusable for 6 catalytic cycles.

1 aNandiwale, Kakasaheb, Y.1 aGalande, Nitish, D.1 aBokade, Vijay, V. uhttps://library.ncl.res.in/content/process-optimization-response-surface-methodology-transesterification-renewable-ethyl-001387nas a2200229 4500008004100000022001400041245012200055210006900177260000800246300001200254490000700266520058600273653001300859653001400872653002000886653002900906653001600935100002900951700002400980700002201004856013101026 2015 eng d a1863-065000aSynthesis of non-toxic triethyl citrate plasticizer by esterification of renewable citric acid using modified zeolite0 aSynthesis of nontoxic triethyl citrate plasticizer by esterifica cJUN a927-9310 v433 a

Triethyl citrate (TEC), a non-toxic plasticizer, was synthesized by esterification of renewable citric acid (CA, from entire waste of oranges) with ethanol over modified H-ZSM-5 (HZ-5) zeolite. Different micro-meso composites (M-HZ-5) with varying crystallinities were prepared by alkaline treatment of HZ-5. M-HZ-5(0.6) (87% crystallinity) was observed to be a potential and environmentally benign catalyst with 96% CA conversion, 64% TEC selectivity (61.44% TEC yield), and a reusability of six cycles. The probable catalytic mechanism of esterification was also proposed.

10aBiowaste10aCatalysts10agreen chemistry10aMicro-mesopre composites10areusability1 aNandiwale, Kakasaheb, Y.1 aBorikar, Sanjay, P.1 aBokade, Vijay, V. uhttps://library.ncl.res.in/content/synthesis-non-toxic-triethyl-citrate-plasticizer-esterification-renewable-citric-acid-using02403nas a2200229 4500008004100000022001400041245017800055210006900233260009500302300001200397490000700409520142700416653003301843653001901876653002201895653002301917653001701940653003301957100002901990700002202019856013202041 2016 eng d a0957-582000aOptimization by box-behnken experimental design fur synthesis of n-hexyl levulinate biolubricant over hierarchical H-ZSM-5: an effort towards agricultural waste minimization0 aOptimization by boxbehnken experimental design fur synthesis of  a165-189 RAILWAY TERRACE, DAVIS BLDG, RUGBY CV21 3HQ, ENGLANDbINST CHEMICAL ENGINEERScJAN a159-1660 v993 a

The present study is devoted to develop efficient catalytic process for conversion of agricultural waste feedstock to value added chemicals. In this context, the n-hexyl levulinate, a renewable biolubricant was synthesized by esterification of biomass derived levulinic acid (LA) with n-hexanol in a closed batch system. Hierarchical-HZ-5 (modified H-ZSM-5) was used as a heterogeneous acid catalyst. There are no reports available on the synthesis of n-hexyl levulinate biolubricant using renewable levulinic acid. The process variables such as catalyst to LA ratio (X-1), n-hexanol to LA molar ratio (X-2), reaction time (X-3) and reaction temperature (X-4) were optimized by response surface methodology (RSM), using the Box-Behnken model. Analysis of variance was done to check the suitability and significance of the quadratic model. The yield of n-hexyl levulinate obtained was 97% with 100% selectivity at optimum process parameters. The RSM analysis predicted that catalyst to LA ratio is most significant (value of p < 0.0001) and n-hexanol to LA molar ratio is least significant (value of p = 0.0064) process parameter in esterification. The quadratic model established was revealed to be suitable and statistically precise with correlation value (R-2) of 0.9837 to predict the yield of n-hexyl levulinate. (C) 2015 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

10aAgricultural waste feedstock10aEsterification10aHierarchical-HZ-510an-Hexyl levulinate10aOptimization10aResponse surface methodology1 aNandiwale, Kakasaheb, Y.1 aBokade, Vijay, V. uhttps://library.ncl.res.in/content/optimization-box-behnken-experimental-design-fur-synthesis-n-hexyl-levulinate-biolubricant-002463nas a2200157 4500008004100000245014900041210006900190260000800259300001400267490000700281520182100288100002902109700002302138700002202161856012202183 2018 eng d00a HPW anchored Meso-HZ-5, a novel catalyst for selective synthesis of ethyl levulinate biofuel by alcoholysis of biomass-derived furfuryl alcohol0 aHPW anchored MesoHZ5 a novel catalyst for selective synthesis of cSEP a1736-17420 v373 aEthanolysis of biomass derived furfuryl alcohol (FA) produces ethyl levulinate (EL), a biofuel additive and precursor for -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), N-2 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 FA1 aNandiwale, Kakasaheb, Y.1 aPande, Ashwini, M.1 aBokade, Vijay, V. uhttps://library.ncl.res.in/content/hpw-anchored-meso-hz-5-novel-catalyst-selective-synthesis-ethyl-levulinate-biofuel02569nas a2200169 4500008004100000022001400041245015400055210007300209260000800282300001400290490000700304520187600311100002902187700002302216700002202239856013802261 2018 eng d a1944-745000aHPW anchored Meso‐HZ‐5, a novel catalyst for selective synthesis of ethyl levulinate biofuel by alcoholysis of biomass‐derived furfuryl alcohol0 aHPW anchored Meso‐HZ‐5 a novel catalyst for selective synthesis  cNOV a1736-17420 v373 athanolysis 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.1 aNandiwale, Kakasaheb, Y.1 aPande, Ashwini, M.1 aBokade, Vijay, V. uhttps://library.ncl.res.in/content/hpw-anchored-meso%E2%80%90hz%E2%80%905-novel-catalyst-selective-synthesis-ethyl-levulinate-biofuel02265nas a2200193 4500008004100000022001400041245014500055210006900200260000900269300001200278490000700290520153100297100002901828700002201857700001801879700002001897700002201917856013201939 2021 eng d a0887-062400aOne-pot cascade conversion of renewable furfural to levulinic acid over a bifunctional H3PW12O40SiO2 catalyst in the absence of external H-20 aOnepot cascade conversion of renewable furfural to levulinic aci cJAN  a539-5450 v353 a

The conversion of biomass-derived furfural (FUR) to levulinic acid (LA), a versatile platform chemical, involves catalytic hydrogenation of FUR followed by acid hydrolysis to LA. However, this two-step process demands expensive separation and purification of the furfuryl alcohol (FAL) intermediate. Herein, we demonstrate an ingenious catalytic strategy for the one-pot cascade conversion of FUR to LA over a bifunctional catalyst without using pure external H-2. Isopropyl alcohol (IPA) served a dual role as a hydrogen donor and solvent while inhibiting the side reactions. Catalysts with a tunable surface area and acidity were synthesized by impregnating different percentages of H3PW12O40 (heteropolyacid) over a SiO2 support. The bifunctionality of the H3PW12O40/SiO2 catalyst is ascribed to the mutual coexistence of Lewis and Brvinsted acid sites. The Lewis acid sites imparted by active W metal sites adsorb hydrogen proton for catalytic transfer hydrogenation of FUR to FAL, while the predominant Brvinsted acid sites catalyze the hydrolysis of FAL to LA. Consequently, H3PW12O40/SiO2 revealed to be a potential catalyst producing an similar to 51% LA yield under optimized reaction conditions. Moreover, the catalyst was found to be reusable for three catalytic cycles. This study paves the way to develop future biorefinery, particularly direct conversion of FUR to LA over a bifunctional catalyst with a liquid H-donor, in an environmentally benign manner and comply with the green chemistry principles.

1 aNandiwale, Kakasaheb, Y.1 aVishwakarma, Mona1 aRathod, Simmy1 aSimakova, Irina1 aBokade, Vijay, V. uhttps://library.ncl.res.in/content/one-pot-cascade-conversion-renewable-furfural-levulinic-acid-over-bifunctional-h3pw12o40sio2