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-002121nas 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.13530