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ORIGINAL ARTICLE

Synthesis of Hydroxymethylfurfural from Fructose Om Prakash, Shailal Ahmad Siddiqui, Anugrah Shukla, Anju Yadav, Ashween Deepak Nannaware, Chandan Singh Chanotiya and Prasant Kumar Rout* Chemical Science Division, CSIR-Central Institute of Medicinal and Aromatic Plants, Lucknow, Uttar Pradesh 226015, India. Academy of Scientific and Innovative Research (AcSIR), Delhi 110025, India. *Corresponding Author: P. K. Rout Email: [email protected] Received: 22/12/2014 Revised: 11/02/2015 Accepted: 12/02/2015

Abstract Dehydration of fructose to 5-hydroxymethylfurfural (HMF) in ionic

liquids (ILs) is a greener approach for producing liquid bio-fuels and high value bio-chemicals from renewable resources. Screening of some commercial catalysts for synthesizing HMF in ILs has been carried out in CSIR-CIMAP. 1-Ethyl-3-methylimidazolium chloride ILs along with CrCl3.6H2O or heteropoly acid catalysts have resulted upto 90% yield of HMF from fructose in two-batch reaction process. HMF yield was estimated in the reaction mixture using HPLC-PDA. In addition, HMF has been isolated from the reaction mixture through solvent-solvent extraction using ethyl acetate and percentage composition was analyzed by GC-FID. The compound was identified by GC/MS, FT-IR and NMR analysis. Keywords: Fructose; Catalysts; Hydroxymethylfurfural, Bio-fuel; Bio-chemical.

1. Introduction Currently, the energy requirement in the world

is realised through exploration of petroleum sources, coal and natural gas. There has always been high energy demand in the industrialized world as well as in the domestic sectors. But pollution problem caused due to the widespread use of fossil fuels forced the researchers make it necessary to develop the renewable energy sources of limitless duration with lesser environmental impact than the conventional fuel (Rout et al., 2015; Rout et al., 2014). Environmental pollution is a major hazard, the world facing today and there is an increasing awareness towards the clean environment for smooth living and better health of human being. The fossil fuels are not eco-friendly and also contributing huge amount of CO2 on the process of combustion, which is one of the major concerns of global warming. Therefore, this has forced the scientists to find an alternative for replacing petroleum-based fuel. An alternative fuel must be technically feasible, environmentally acceptable and readily available. One possible alternative to fossil fuel is the fuels derived from the plant biomass or organic wastes. In order to meet the present energy demand, lignocellulosic biomass has come up as a prime candidate for the production of both conventional hydrocarbon based liquid transportation fuel and commodity chemicals to support industrialization

(Rout et al., 2014). Recently, we have developed an economical process for isolation of cellulose, hemicellulose and lignin from the agricultural residues (Rout et al., 2014). The depolymerization of cellulose through green catalytic process is produced glucose, and further isomerization of glucose to resulted fructose (Rout et al., 2014). Fructose or fruit sugar is a simple ketose-monosaccharide found in many food products. It was observed that at a high temperature, in the course of food preparation, hydroxymethylfurfural (HMF) was automatically formed as a chemical derivative. As reported in roast coffee, HMF contain was nearly 110-2480 mg of HMF/kg coffee (Rout et al., 2015). It was also reported that the high percentage of HMF consumption resulted into cytotoxic effect; hence high HMF percentage has not been recommended for consumption along with the food products.

HMF and 2,5-disubstituted furan derivatives have great potential in the field of intermediate chemicals from the re-growing resources as presented in Fig 1. Due to its various functionalities, it has been proposed that HMF could be utilized as a key platform chemical to produce a wide range of products such as polymers, solvents, surfactants, pharmaceuticals, and plant protection agents (Rosatella et al., 2011). HMF has potential for the production of clean liquid fuels through reduction or esterification reaction to

Prakash et al…Synthesis of Hydroxymethylfurfural from

Journal of Bioresource Engineering and Technology | © 2015 Jakraya Publications (P) Ltd

Fig 1: Importance of HMF in various industrial applications

ethoxymethylfurfural (EMF). The HMF has great potential in the field of bio-fuel after the chemical modification. Through reduction, HMF was converted to dimethylfuran (DMF), which wellbiofuel precursor molecule. The energy density (31.5 mJ/L) of DMF is 40% higher as compared to ethanol (23 mJ/L) and very closer to the gasoline (33 mJ/L).Thus, HMF has high demand for the production ofalternative high calorific value clean a potential intermediate molecule to support the chemical industries (Fig 1). HMF is a bio-precursor molecule in plastic industry, and its chemically modified furan dicarboxylic acid (FDCA) which successfully replaced PET-plastics (Rout et al., 2015).

Recently, synthesis of HMF from sugars using ionic liquid (ILs) has been received much attention due to its greener solvent approachal., 2005; Zhang and Zhao, 2009). ILs are new organic salts that exists as liquid at a relatively low temperature. They are non-flammable and recyclable solvents with very low volatility, high thermal stability and immeasurable low vapor pressure. In contrast to the traditional volatile organic compounds, they are called as ‘green’ solvents and have been widely used(Heinze et al., 2005). Some reported that fructose was dissolved in some hydrophilic such as 1-ethyl-3-methylimidazolium chloride (EMIMCl) and 1-butyl-3-methylimidazolium chloride (BMIMCl), etc (Chidambaram and Bell, 2010; Zhang and Zhao, 2009). The solubility of different species in

Prakash et al…Synthesis of Hydroxymethylfurfural from Fructose

Journal of Bioresource Engineering and Technology | Year-2015 | Volume 2 | Pages 01-0715 Jakraya Publications (P) Ltd

2

Importance of HMF in various industrial applications

The HMF has great fuel after the chemical

Through reduction, HMF was converted , which well-known as a

The energy density (31.5 mJ/L) of DMF is 40% higher as compared to ethanol (23 mJ/L) and very closer to the gasoline (33 mJ/L).

for the production of alternative high calorific value clean bio-fuel as well as a potential intermediate molecule to support the

HMF is well recognized as precursor molecule in plastic industry, and its

chemically modified furan dicarboxylic acid (FDCA) -plastics and PBT-

synthesis of HMF from the reducing sugars using ionic liquid (ILs) has been received much attention due to its greener solvent approach (Heinze et

. ILs are new group of as liquid at a relatively low

flammable and recyclable high thermal stability

and immeasurable low vapor pressure. In contrast to ic compounds, they are

solvents and have been widely used reported studies confirmed

s dissolved in some hydrophilic ILs methylimidazolium chloride

limidazolium chloride (Chidambaram and Bell, 2010; Zhang

of different species in

imidazolium ILs are mainly dependedas well as hydrogen bonding ability. Saturated compounds are generally veryand olefins shown somewhat greater solubilitywhereas reducing sugars (Rosatella et al., 2011). Furtherthe sugar solution was converted et al., 2011). Then, HMF was isolated from the reaction mixture through a suitable solventfor relatively easy separation of reacted substrates (Rout et al.,used in carbohydrate processing. The cation consists of a five-membered ring with two nitrogen and three carbon atoms, i.e. a derivative of and methyl groups substituted at the two nitrogen atoms. Its melting point is 7carrying the reaction at easily attainable temperatureThe structure and physical properties of very similar with BMIMCl Though, there have been some reports exist synthesis of HMF (Rout et al.,communication deals with synthesis of HMF from fructose with reasonable economical yield. 2. Materials and Methods

Al l the chemicals used in thereagent grade and solvents were laboratory before use. Fructose (EMIMCl and BMIMCl) were purchased from SigmaAldrich, Bengaluru, The catalysts selected

Fructose

7

are mainly depended on the polarity hydrogen bonding ability. Saturated aliphatic

very sparingly soluble in ILs n somewhat greater solubility,

are completely miscible Further using suitable catalysts

the sugar solution was converted into HMF (Rosatella HMF was isolated from the

reaction mixture through a suitable solvent, allowing for relatively easy separation of the products and/or un-

et al., 2014). EMIMCl is being ocessing. The cation consists of

membered ring with two nitrogen and three carbon atoms, i.e. a derivative of imidazole, with ethyl

groups substituted at the two nitrogen atoms. Its melting point is 77-79°C, which favor to

ying the reaction at easily attainable temperature. The structure and physical properties of EMIMCl is

BMIMCl (Heinze et al., 2005). Though, there have been some reports exist on

et al., 2015), but the present a simple procedure for

synthesis of HMF from fructose with reasonable

Materials and Methods

l the chemicals used in the experiments were solvents were distilled in the

ructose as well as ILs were purchased from Sigma-

The catalysts selected for the study



3

were CrCl2, CrCl3, CrCl3.6H2O, CuCl2 as metallic chlorides catalysts, Nb2O5, V2O5, NH4.VO3 as metallic oxides, P-toluene sulphonic acid (PTSA), PMA (phosphomolybdic acid), PTA (phosphotungstic acid) as a acid catalysts, H-ZSM-5 as molecular sieve and Dowex-type ion-exchange resin, Amberlyst 15-Dry as acidic polymeric resins. 2.1 Reaction Conditions

The reaction was carried out in a 15 mL pressure tubes procured from Sigma-Aldrich, Bengaluru. Fructose (50 mg) was dissolved in EMIMCl (500 mg) and kept for 30 minutes at a particular temperature. Then reaction mixture was cooled and catalyst was added. The reaction was further continued for synthesis of HMF. After completion of the reaction, the reaction mixture was cooled and HMF was isolated by solvent-solvent extraction. The solvent was concentrated in a rotary evaporator under vacuo. The product was kept in a refrigerator prior to the analysis. 2.2 Analysis of Chemicals

The analysis of the reaction mixture and products formed in these processes are very important for calculation of the yield and percentage composition of the final product in the extract. The extracted HMF was analyzed through TLC, HPLC, GC-FID, GC/MS and FT-IR and NMR experiments.

TLC analysis was carried out by using the solvent system of CH2Cl2/ THF/ CH3COOH (60: 20: 20). After development of the plate, it was sprayed in aniline phthalate solution and heated for 10 min.

All the extracts were analyzed on a Varian CP-3800 GC fitted a Carbowax fused silica capillary column (30 m × 0.25 mm i.d., 0.25 µm film thickness) equipped with a flame-ionization detector (FID). The temperature program was 40oC, 40-120oC (3oC/ min), 120oC (9 min), 120-140oC (2oC/min), 140oC (2 min), 140-250oC (5oC/ min), 250oC (5 min). Hydrogen was used as carrier gas with flow rate of 1.7 mL/min. The neat sample (0.04 µL) was injected to the capillary column through injection port of the GC. The injector and detector (FID) temperatures were 300 °C and 310 °C, respectively. The relative percentage of individual compound was determined on the basis of peak area normalisation method without using the correction factors.

GC/MS analysis was performed in a PerkinElmer Auto System XL GC interfaced with a Turbomass Quadrupole mass spectrometer fitted with the same capillary column. The injector, transfer line and source temperatures were 250 °C. The neat sample (0.03 µL) was injected with a split ratio of 1:30. The carrier gas was He at 10 psi constant pressure;

ionization energy 70 eV; mass scan range 40-450 amu. Finally, the compounds were identified by mass spectra library search (NIST/EPA/NIH version 2.1 and Wiley registry of mass spectral data, 7th edition).

The analysis of HMF was carried out in HPLC (Waters 996) fitted a RP18 column equipped with PDA detector. The mobile phase was water/acetonitrile (93:7) at a flow rate of 1.0 mL/min. The HMF was confirmed by co-elution method using pure HMF standard.

FT-IR analysis was carried out in PerkinElmer Spectrum BX FT-IR. The sample was dissolved in CCl4 and directly taken in KBr plates for analysis.

The compound was subjected to NMR analysis to determine its structure. The 1H-NMR spectrum was recorded on DPX-300 Brucker machine at 300 MHz in CDCl3 at 26oC with tetramethylsilane (TMS) as internal standard. The 13C-NMR spectrum was recorded on DPX-300 Brucker machine at 75 MHz in CDCl3 at 26oC with tetramethylsilane (TMS) as internal standard. 3. Results and Discussion 3.1 Selection of Solvent (ILs)

As per the experimental results, EMIMCl gave better yield as well as selectivity in comparison to the BMIMCl. Thus, further optimization of reaction temperature, type of catalyst, catalyst amounts and sugar to EMIMCl ratio has been carried out by taking only EMIMCl. 3.2 Selection of Catalyst

The synthesis of HMF is based on the mechanism of dehydration of fructose. The acid catalyzed dehydration leads to form HMF, then after there is a possibility to form various side products from HMF as presented in Fig 2. Therefore catalyst played a major role for synthesis of HMF.

In the present study, the catalyst has been divided into groups for better understanding. Among the catalyst, the metal chlorides including CrCl2, CrCl3, CrCl3.6H2O and CuCl2 were used. It was particularly, interesting that the Lewis acidic metal chloride such as CrCl2 and CrCl3 displayed better activity for fructose at 120˚C as presented in Table 1. CrCl3 was soluble in ILs, whereas CrCl2 was insoluble. Therefore, our observation was agreed with the findings of Zhang and Zhao (2009). On the other hand, the improved HMF yield was obtained from fructose (upto 90%) in CrCl3.6H2O catalyst. Therefore, CrCl3.6H2O is the most preferred catalyst used for the preparation of HMF in ILs among all the metal chlorides.



4

Fig 2: Chemical pathways of Synthesis of HMF from fructose

Heteropolyacids (HPA) are solid acids consisting of transition metal-oxygen anion clusters, and they are exploited for chemical transformations as recyclable catalysts. HPA are Keggin type acids with a general formula [XYxM(12-x)O40]

n- (X: heteroatom, M,Y: addendum atoms). HPA have received much research interest for synthesis of HMF due to their mesmerizing structural designs and admirable physicochemical properties such as Bronsted acidity, high proton mobility and good stability (Chidambaram and Bell, 2010). They dissolved in polar solvents to release H+ ion and it is acted as strong acid as mineral acids (Rout et al., 2015) However, the Keggin type acids could not use as heterogeneous catalysts in polar solvents. Moderately strong soluble catalysts investigated were H3PW12O40 (PTA) and H3PMo12O40

(PMA) and both catalysts displayed higher dehydration activity with reasonable higher yield (85-90%) of HMF.

Zeolites are chemically alumino-silicate belongs to the family of microporous solids known as "molecular sieves." The term molecular sieve refers to a particular property of these materials, i.e., the ability to selectively sort out the molecules based primarily on a size exclusion process. The H-ZSM-5 or Zeolite was used for the synthesis of HMF with appreciable yield (up to 65%). In ILs, the mechanism was explained as H-ZSM-5 in EMIMCl could produce [EMIM]+ that entered the inner channel of H-ZSM-5 and reacted with acidic sites to replace H+ ion. Then free H+ might be responsible for dehydration of fructose to resulted HMF (Cai et al., 2012).

Several metal oxides like Nb2O5, V2O5 and NH4VO3 are used for the catalytic dehydration of fructose into HMF. The Nb2O5 and V2O5 catalysts are

very effective for the dehydration of fructose into HMF as presented in Table 1. On the other hand, the yield of HMF from fructose was upto 60%. Similarly, the yield of HMF from fructose was around 65% in NH4VO3 catalyst.

Table 1: Yield of HMF from fructose using different

catalysts

Catalyst Solubility % Yield of HMF CrCl2 insoluble 60-65 CrCl3 soluble 60-65 CrCl3.6H2O soluble 85-90 CuCl2 soluble 35-40 ZnCl2 soluble not found FeCl3 soluble not found NH4VO3 soluble 60-65 V2O5 soluble 55-60 Nb2O5 soluble 80-85 ZSM-5 insoluble 60-65 PTA soluble 85-90 PMA soluble 85-90 Amberlyst@15 Insoluble 55-60

Results presented is the average of three experiments The acidic polymeric resin, which was very

much suitable as a catalyst for the conversion of fructose into HMF such as ion-exchange resin (Amberlyst 15-Dry). The solid Amberlyst 15-Dry was suitable for synthesis of HMF with yield up to 60%. The catalyst has one most important advantage for re-using (at least five times), without catalytic poisoning (Li et al., 2013).

Most of the catalyst gave better yield and selectivity when fructose was used as a substrate. Among these catalysts, CrCl3.6H2O, PMA and PTA gave comparatively better yield and selectivity. The

O

HO OH

HO OH

HO

glucose

HO

OH

HO OH

HOO

fructose

OHO

OH

OH

HO

HO

OHO

OH

OH

HO

OO

OH

5-hydroxymethyl furfural

OH

O

O

+H2

-

Levulinic acid



5

experimental findings were justified as per the reaction mechanism presented in Fig 2. The dehydration of fructose was occurred for HMF synthesis, thus most of the catalyst discussed above were effective for chemical conversion to HMF. From the above catalysts studied so far, the CrCl3.6H2O, PMA and PTA were found to be suitable for conversion to HMF (Table 1). The further process optimization reaction was carried out by taking the above three catalysts. 3.3 Reaction Condition

All the reactions were carried out in fructose and solvent ratio of 1: 10. The reaction time for all the experiments was 3 h. The other two main important parameters were reaction temperature and catalyst ratio, which determined the yield of the HMF. 3.3.1 Reaction Temperature

The reaction was carried out at different temperatures viz. 90oC, 100oC, 110oC, 120oC, 130oC and 140oC. The low temperature gave less yield of HMF and similar trend was observed at high temperature. It was concluded that, the low temperature was not sufficient for carrying out the reaction towards forward direction. On the other hand, at high temperature the products are degraded and polymerized to unwanted humin as presented in Fig 2. Therefore, the most ideal reaction temperature was 120˚C for the preparation of HMF from fructose.

3.3.2 Fructose to Catalyst Ratio

The ratio of fructose to catalyst was very important and affected the yield of HMF as presented in Table 2. For the maximum yield of HMF, the ratio of fructose to catalyst should be optimum. Introduction of high amount of catalyst during the reaction, decreased the yield of HMF and also its selectivity. The lower dose of catalyst was not efficient for conversion of whole substrate to product (HMF) and similarly the higher dose also leads to degradation of product (HMF) to unwanted humin polymers. 3.3.3 Isolation of the Product

The isolation of HMF from the reaction mixture was done by solvent-solvent extraction. The isolation of HMF was tried with various common organic solvents. The solvents tried for the isolation purpose such as ethyl acetate, chloroform, diethyl ether, acetone, dichloromethane, etc. But, ethyl acetate was the most suitable solvent for selectively extraction of HMF from the reaction mixture. It not only gave the improved yield but also favored because of its low cost, low toxicity, and agreeable odor. Ethyl acetate is very volatile and has a low boiling point of 78°C. Due to

these properties, it could be easily removed from solution through rotary evaporator under vacuo. Table 2: Catalysts and fructose ratio Fructose (mg)

Catalyst (mg)

Ratio Yield of HMF (mg) from fructose

50 5 1:10 27 (77.1%) 50 10 1:5 29 (82.8%) 50 15 1:3.33 32 (91.4%) 50 20 1:2.5 20 (57.1%) 50 25 1:2 15 (42.9%)

Results presented is the average of three experiments 3.3.4 Re-use of same ILs and Catalyst

In our experiment, we have re-used the ILs and catalyst upto five batches after vacuum drying the reaction mixture for an hour at 100oC. The yield and purity of HMF was very close with the first experiment. So economically, the same spent ILs can be re-used several times for the HMF synthesis.

3.4 Physical Properties and Chemical Analysis

HMF is reddish yellow low-melting solid (32-34oC) having high solubility in water. The molecule consists of a furan ring, containing both aldehyde and alcohol functional groups. The compounds were detected in TLC plate in Rf value 0.8.

FT-IR analysis gave the characteristic absorptions (υ; cm-1): 3382 (-OH), 1673 (-C=O), 1522 (furan oxygen). Thus the compound contained alcoholic functional group, aldehydic functional group and furan nucleus.

The GC chromatogram is presented in Fig 3a. The selectivity was above 96% as per the chromatogram. The quantitative HPLC chromatogram is presented in Fig 3b. The analysis indicated that the purity of the compound (HMF) in the ethyl acetate was above 95%.

The identification of structure of HMF was carried out in GC/MS analysis. The spectral data of HMF is given in Fig 4. The compound of interest (top one) was matched with HMF library mass spectra (bottom one). EIMS (70 eV) m/z: 41 (100%), 53 (55%), 69 (40%), 81 (10%), 97 (70%) [M+-CHO], 109 (25%) [M+-H2O], 124 (40%) [M+-H2], 126 (25%) [M+].

The identification of structure of HMF was done by NMR technique. 1H-NMR (300 MHz): δ 9.53 (1H), 7.26 (1H), 6.5 (1H), 4.69 (2H), 2.89 (1H) ppm. The spectral data of 13C-NMR was given for structural identification. 13C NMR (75 MHz): δ 178.0, 161.4, 152.0, 123.8, 110.0, 57.1 ppm (Table 3).



3.5 Significance Aspects From the above discussion, the HMF was

synthesized from fructose at the optimum reaction conditions with reasonable high yield using some specific catalysts as presented in Table 1. importance of this chemical is already discussed and briefed in Fig 1. Therefore, this chemical can be synthesized profitable from fructose to fulfill the today’s requirement through sustainable approach. 4. Conclusion

HMF is an important versatile biochemical produced from fructose. HMF has potential for the production of clean liquid fuels. In oxidation reaction, HMF led to commercially important chemicals such as


Journal of Bioresource Engineering and Technology | Year-2015 | Volume 2 | Pages 01-0715 Jakraya Publications (P) Ltd

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Fig 3a: GC chromatogram of HMF

Fig 3b: HPLC chromatogram of HMF

From the above discussion, the HMF was synthesized from fructose at the optimum reaction conditions with reasonable high yield using some specific catalysts as presented in Table 1. The importance of this chemical is already discussed and

Therefore, this chemical can be synthesized profitable from fructose to fulfill the today’s requirement through sustainable approach.

HMF is an important versatile biochemical produced from fructose. HMF has potential for the production of clean liquid fuels. In oxidation reaction, HMF led to commercially important chemicals such as

Table 3: Spectral data of

1H-NMR 13CProton No

δ (ppm) Carbon No

a 9.536 1 b 7.260 2 c 6.500 3 d 4.690 4 e 2.899 5 6

* structure of HMF is presented

OOHC C

H H

a

b c

1 23

4 5

Fructose

7

Table 3: Spectral data of 1H and 13C NMR*

C-NMR Carbon No δ (ppm)

178.00 161.44 152.07 123.86 110.05 57.17

is presented below

CH2 OHd e

6



diformylfuran and FDCA. Similarly, decarboxylation of HMF was originated bio-baviz. furfuryl alcohol and reduction of HMF produced pharmaceutical important chemical viz. furandimethanol. The various industrial these chemicals are already been discussed including biofuels, synthesis chemicals, biopolymers, electronics, food flavoring agents etc. Factors determining the catalytic effectiveness are Lewis and Bronsted acid sites, diffusion and dispersion behavior, hydrophobic / hydrophilic environment, solvent effect, etc. In commercial aspects, the of the catalyst along with the ILs issubsequent recycling reactions.

References Cai H, Li C, Wang A, Xu G and

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Li Y, Liu H, Song C, Gu X, Li H, Zhu W, Yin S (2013). The dehydration of fructose to 5hydroxymethylfurfural efficiently catalyzed by acidic ion-exchange resin in ionic liquid. Technology, 133: 347-353.


Journal of Bioresource Engineering and Technology | Year-2015 | Volume 2 | Pages 015 Jakraya Publications (P) Ltd

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Fig 4: Mass spectra of HMF

. Similarly, decarboxylation based valuable chemical

and reduction of HMF produced pharmaceutical important chemical viz. 2.5-

The various industrial importance of these chemicals are already been discussed including biofuels, synthesis chemicals, bio-pesticides, bio-polymers, electronics, food flavoring agents etc. Factors determining the catalytic effectiveness are

nsted acid sites, diffusion and dispersion behavior, hydrophobic / hydrophilic environment, solvent effect, etc. In commercial aspects, the recovery of the catalyst along with the ILs is most important for subsequent recycling reactions. Further bio-refinery

aspects, there is a need to integrate process operation, designing proficient reactor and synthesis of environment-friendly catalyst to improve the production of these precious chemicals. Acknowledgments

The authors are thankful to Prof. A.K. Tripathi, Director, CSIR-CIMAP for providing the laboratory facility for carrying out the experimental work. are also thankful to Mr. Shailal Ahmad Siddiqui for helping in laboratory experiments. grateful to CSIR, New Delhi for financial support in the form of supra-institutional (ChemBio; BSC 0203).

and Zhang T (2012). Zeolite-promoted hydrolysis of cellulose in ionic liquid, insight into the mutual behavior of zeolite, cellulose and ionic

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The authors are thankful to Prof. A.K. Tripathi,

CIMAP for providing the laboratory facility for carrying out the experimental work. Authors are also thankful to Mr. Shailal Ahmad Siddiqui for helping in laboratory experiments. The authors are grateful to CSIR, New Delhi for financial support in

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