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-001624nas a2200241 4500008004100000022001400041245011300055210006900168260007300237300001200310490000700322520073500329653001901064653002101083653001801104653001701122653003201139100001801171700002201189700002201211700001801233856013101251 2014 eng d a1566-736700aEsterification of levulinic acid to ethyl levulinate over bimodal micro-mesoporous H/BEA zeolite derivatives0 aEsterification of levulinic acid to ethyl levulinate over bimoda aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcJAN a188-1910 v433 a

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.

10aEsterification10aethyl levulinate10aH/BEA zeolite10aMesoporosity10aPost-synthesis modification1 aPatil, C., R.1 aNiphadkar, P., S.1 aBokade, Vijay, V.1 aJoshi, P., N. uhttps://library.ncl.res.in/content/esterification-levulinic-acid-ethyl-levulinate-over-bimodal-micro-mesoporous-hbea-zeolite-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-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-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-5-002403nas 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-0