@article {44418, title = {Acid modified H-USY zeolite for efficient catalytic transformation of fructose to 5-hydroxymethyl furfural (biofuel precursor) in methyl isobutyl ketone-water biphasic system}, journal = {Energy Fuels}, volume = {32}, year = {2018}, month = {FEB}, pages = {3783{\textendash}3791}, abstract = {Sustainable process and efficient heterogeneous acid catalyst for the preparation of platform chemicals like 5-hydroxymethyl furfural (5-HMF) from renewable source is much in demand in the context of heterogeneous catalysis. Commercially available solid acid catalyst, H-USY zeolite was modified by treating with aqueous solution of H3PO4 and H2SO4 (10{\textendash}30 wt \%). Modified H-USY was completely characterized by XRD, NH3-TPD, energy dispersive analysis X-ray (EDAX), FT-IR, pyridine-IR, and NMR. Its catalytic performance was evaluated for the fructose conversion to 5-HMF in methyl isobutyl ketone (MIBK){\textendash}water system. Modified H-USY zeolite was identified to have potential in enhancement of 5-HMF yield up to 65\% from 32\% (parent H-USY) with minimum formation of furfural (8\%). H-USY modified with 10 wt \% H3PO4 (10P{\textendash}Y) was found to be the best compared to other studied catalysts, namely, H-USY modified with 20 and 30 wt \% H3PO4 (20 and 30P{\textendash}Y) or 10{\textendash}30 wt \% H2SO4 (10- to 30S{\textendash}Y). Best performance of 10P{\textendash}Y is associated with the optimum combination of moderate acidity (both weak as well as strong), moderate dealumination of Al from extra-framework sites as well as from framework sites of H-USY, formation of new Al{\textendash}O{\textendash}P bonds between framework Al and elemental monomeric phosphorus, presence of Br{\o}nsted as well as Lewis acidity, and creation of mesopores. This gives new insight on a potential heterogeneous acid catalyst for the synthesis of 5-HMF.}, doi = {10.1021/acs.energyfuels.7b03684}, author = {Pande, Ashwini and Niphadkar, Prashant and Pandare, Kiran and Bokade, Vijay} } @article {46180, title = {Efficient synergetic combination of H-USY and SnO2 for direct conversion of glucose into ethyl levulinate (Biofuel Additive)}, journal = {Energy \& Fuels}, volume = {33}, year = {2019}, month = {MAR}, pages = {2319-2327}, type = {Article}, abstract = {

Ethyl levulinate (EL), a biofuel additive for petroleum and biodiesel can also be used as a 100\% fuel to replace petroleum diesel with the existing diesel engine. The major problem to make the EL process economical is the lack of a proper conversion technology to convert C-6 sugars such as glucose with higher yield of EL as well as process which can tolerate higher glucose concentration to increase productivity. The present study highlighted the catalytic synthesis of EL from glucose over synergetic combination of zeolite H-USY and Lewis acidic catalysts such as Sn-beta, TiO2, ZrO2, and SnO2. Because of the strong Lewis acidic nature and the subsequent enhancement in the isomerization rate from glucosides to fructosides, the synergetic combination of H-USY with SnO2 showed higher EL yield than the combination with other Lewis acidic catalysts. So far, the highest EL yield of 81\% from glucose (50 g/L) at 180 degrees C in 3 h was achieved over the optimal combination of 95\% H-USY and 5\% SnO2 having strong/weak acidity and B/L ratios of 1.30 and 0.75, respectively. The study was further extended for establishing the proposed reaction mechanism without the formation of 5-hydroxymethyl furfural, levulinic acid, and formic acid which makes the overall process clean and green.

}, issn = {0887-0624}, doi = {10.1021/acs.energyfuels.8b04395}, author = {Heda, Jidnyasa and Niphadkar, Prashant and Bokade, Vijay} } @article {47150, title = {Highly active Br{\o}nsted acidic silicon phosphate catalyst for direct conversion of glucose to levulinic acid in MIBK{\textendash}water biphasic system}, journal = {SN Applied Sciences}, volume = {2}, year = {2020}, month = {JAN}, pages = {Article number: 51}, type = {Article}, abstract = {

Due to depletion of fossil fuel reserves and environmental concerns demand the utilization of other renewable feedstocks such as biomass which is available abundantly in different quantities throughout the world. Catalytic transformation of this biomass or biomass-derived products such as glucose to valuable platform biochemicals viz: levulinic acid (LA) is academically as well as industrially important reaction. In the present work, Silicon phosphates (SixPO4) catalysts viz: Si10PO4, Si20PO4, Si30PO4, and Si40PO4 having solely Br{\o}nsted acidic properties were prepared by wet impregnation of H3PO4 (10{\textendash}40\ wt\%) on fumed silica followed by calcination at 550\ {\textdegree}C for 10\ h. The prepared catalysts were characterized by various techniques such as XRD; NH3-TPD; FTIR etc. Formation of silicon phosphate structure was found to depend on \% of P loading and its interaction with silica. The acidic property of SixPO4 catalyst was characterized by NH3-TPD and Pyridine-IR, confirmed that catalyst has exclusively strong Br{\o}nsted acidity. A high LA yield of 81\ mol\% over Si30PO4 has achieved at an optimized reaction condition of 140\ {\textdegree}C; 10\ h in MIBK{\textendash}water (9:1) biphasic system.

}, doi = {10.1007/s42452-019-1827-z}, author = {Bokade, Vijay and Moondra, Hitakshi and Niphadkar, Prashant} } @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 {46755, title = {Maximization of furanic compounds formation by dehydration and hydrogenation of xylose in one step over SO3-H functionalized H-beta catalyst in alcohol media}, journal = {Biomass \& Bioenergy}, volume = {139}, year = {2020}, month = {AUG}, pages = {105646}, type = {Article}, abstract = {

Furanic compounds such as furfural (FUR); furfuryl alcohol (F. Alc) are important renewable platform chemicals can be used as such or further convert for preparation of other value added products such as Levulinic acid (LA), Alkyl Levulinates, 2-Methyltetrahydrofuran (MTHF), and Tetrahydrofuran (THF) etc. Sulfonated H-beta zeolite was successfully prepared and used for the synthesis of furanic compounds especially FUR and F. Alc from c-xylose in one step using isopropanol as alcohol media. Prepared catalyst was well characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), BET, NH3-Temperature programmed desorption (TPD) and carbon-hydrogen-nitrogen-sulfur analysis (CHNS). It was found the total acid amount was increased with increase in sulfur loading which confirmed the sulfonic acid group (SO3-H) was successfully grafted onto zeolite structure. 3 wt\% H-beta-SO3-H catalyst with optimized reaction parameters of 150 degrees C, 7 h, 25 wt\% catalyst loading was tuned to get the highest furanic compound yield of 88.5\% (FUR 76.8\% + F.Alc 11.7\%).The reusability study confirmed that there was a marginal drop of similar to 25\% after 3 recycle runs.

}, keywords = {furfural, Furfuryl alcohol, H-beta, isopropanol, sulfonated zeolite, Xylose}, issn = {0961-9534}, doi = {10.1016/j.biombioe.2020.105646}, author = {Gupta, Anshita and Nandanwar, Sachin U. and Niphadkar, Prashant and Simakova, Irina and Bokade, Vijay} } @article {47071, title = {Effect of rice husk particle size on ZSM-5 physico-chemical properties for selective formation of 1,3,5-trimethyl-2-benzylbenzene (Pharmaceutical Intermediate)}, journal = {ChemistrySelect}, volume = {6}, year = {2021}, month = {FEB }, pages = {1255-1262}, type = {Article}, abstract = {

Rice husk, rich in silica and abundantly available as waste, is presently destroyed by burning, which creates environmental issues. Thus, it will be advantageous if this rice husk waste can be used for preparation of valuable products. One of the application is its use as silica source in the synthesis of zeolites like ZSM-5, which are silico-aluminates. Rice husk waste is available in wide range of particle sizes in agricultural farms. There is no study available in open literature on use of these wide particle ranges for its direct application. This paper is an attempt to use wide particle size rice husk, its effect on ZSM-5 synthesis and its physico-chemical properties. Further these prepared ZSM-5 catalyst was evaluated for benzylation of mesitylene reaction. The study found that, rice husk of 600 mu m particle size is optimum as far as ZSM-5 synthesis, its physicochemical properties and further its application in mesitylene benzylation reaction.

}, keywords = {Mesitylene, Particle size, rice husk, Silica Source, ZSM-5}, issn = {2365-6549}, doi = {10.1002/slct.202004802}, author = {Ghuge, Gorakh and Niphadkar, Prashant and Rathod, Simmy and Bokade, Vijay V.} } @article {47983, title = {Enhanced anisole hydroxylation over a hierarchical micro/mesoporous TS-1 catalyst}, journal = {New Journal of Chemistry}, volume = {46}, year = {2022}, month = {AUG}, pages = {14667-14675}, type = {Article}, abstract = {

Hierarchical TS-1 materials were synthesized using hydrothermal synthesis and a post modification technique through desilication. They were evaluated for hydroxylation of anisole to produce industrially important chemicals, o-methoxyphenol (OMP) and p-methoxyphenol (PMP). The detailed characterization of the prepared catalysts, such as morphology, structure, nature of Ti and surface area were obtained by SEM, HR-TEM, XRD, UV-VIS spectroscopy and the BET technique. The effects of various operational parameters such as substrate/H2O2 molar ratio, reaction temperature, catalyst concentration and solvent effect on the hydroxylation of anisole have been studied in detail. The microporous TS-1 catalyst showed 32\% anisole conversion with 34\% selectivity to PMP, while the micro/mesoporous DTS-1 catalyst showed enhanced activity for anisole hydroxylation, i.e. 54\% conversion with 55\% selectivity towards PMP. The increased framework Ti and improved accessibility of the active sites located in the channels of DTS-1, which permit the mass transfer of reactants, transition states and products from the mesopores of DTS-1, were responsible for the enhanced catalytic activity and selectivity towards p-methoxyphenol.

}, issn = {1144-0546}, doi = {10.1039/d2nj01556k}, author = {Patil, Chetana R. and Niphadkar, Prashant and Kamble, Sanjay P. and Rode, V. Chandrashekhar} } @article {48354, title = {Hierarchical TS-1 for epoxidation of non-edible Karanja (Millettia pinnata) oil methyl ester to methyl epoxioleate (biodiesel additive) in presence of H2O2 as oxidizing agent}, journal = {Environmental Progress \& Sustainable Energy}, volume = {41}, year = {2022}, month = {MAY}, pages = {e13766}, type = {Article}, abstract = {

Application of non-edible Karanja (Millettia pinnata) oil which is abundantly available in India is not explored so far. The present study is an attempt to convert fatty acid methyl ester (FAME) obtained from Karanja oil to methyl epoxioleate over hierarchical titanosilicate (TS-1) catalyst. Methyl epoxioleate, a biodiesel additive can blend up to 20\% with biodiesels to improve oxidative stability and cold flow properties of biodiesel. A series of hierarchical TS-1 were prepared by desilication of parent TS-1 with 0.1 N NaOH at 80 degrees C for 1, 3, 5, and 7 h, respectively. Samples were characterized by powder XRD, low temperature nitrogen adsorption/desorption, and TEM. Eighty percent FAME conversion with 70\% yield of methyl epoxioleate was obtained over 5H-TS-1 catalyst. The enhanced catalytic activity of a 5H-TS-1 compared to parent TS-1 mainly attributed to the high mesoporosity coupled with well-preserved crystallinity. 5H-TS-1 catalyst was found to be completely reusable after calcination at 500 degrees C for 12 h. Hierarchical 5H-TS-1 catalyst for effective conversion of non-edible Karanja oil methyl ester to methyl epoxioleate probably not reported so far.

}, keywords = {H2O2, hierarchical TS-1, Karanja oil methyl ester, methyl epoxioleate, TS-1}, issn = {1944-7442}, doi = {10.1002/ep.13766}, author = {Anil, Reshma and Niphadkar, Prashant and Bokade, Vijay} } @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} }