BBy

Babasaheb M. Matsagar

Research Guide: Dr. Paresh L. Dhepe

Catalysis and Inorganic Chemistry Division

CSIR-National Chemical Laboratory, Pune 411008, India

Tel. 91-20-25902024, FAX. 91-20-25902633, E-mail: pl.dhepe@ncl.res.in

Group Website: http://academic.ncl.res.in/pl.dhepe

Applications of Applications of FurfuralFurfural

PreservativeOH

Low-calorie Sweetener

Fuel additives

HOOH OH

OH

Xylitol

+H2O -3H2O

Specialty chemicalsHemicellulose (xylan)

+H2

Low cost biodegradable

solvent

+H2

Excellent solvent in many pharmaceutical

reactions

Intermediate for pharmaceuticals,

insecticides Plasticizers

+H2+H2

2

Plasticizers,Ink and coatings

Applications Applications of 5of 5--hydroxymethyl furfural (HMF)hydroxymethyl furfural (HMF)

Polyesters & polyurethane foams

Poly(ethylene terephthalate) analogues

H +H2+H2

‐3H2o

(HMF)

+H2o

(HMF)

+H2

O2

Replace terephthalic acid

2

3Fuel additive

Dehydration of xyloseDehydration of xylose

BAIL

Water+Toluene, 170 °C

100Xylose Conversion Furfural Yield

Xylose Furfural

60

80

on/

d (%

)

20

40

60

Con

vers

iood

uct Y

iel

0

20CPr

o

CatalystsFig. Reaction condition: xylose 0.6 g, catalyst 0.08 g, Water+Toluene 1:5 (v/v) 60 mL, 170 °C, 4 h. 4

Optimization of reaction Optimization of reaction parametersparameters

Catalyst quantity (g) at 170 °C, 4 h Time (h) at 170 °C1 (f f l 56%)0.04 (furfural 71%)

0.08 (furfural 73%)

1 (furfural 56%)

3 (furfural 62%)

0.125 (furfural 59%) 4 (furfural 74%)

5 (furfural 71%)

Solvent (1:5 v/v)Water (furfural 37%)

Substrate concentration (g)0.3 (furfural 81%) Water (furfural 37%)

Water+MIBK (furfural 54%)

Water+Toluene (furfural 73%)

( )

0.45 (furfural 76%)

0 6 (furfural 73%) Water+Toluene (furfural 73%)0.6 (furfural 73%)

5

Recycle Recycle studystudy

100 Xylose Conversion Furfural Yield

80

eld

(%)

60

oduc

t Yie

40

rsio

n / P

ro

20

Con

ver

01 2 3 4

Run

Fig. Reaction condition: xylose 0.6 g, [C3SO3HMIM][HSO4] 0.08 g, Water+Toluene 1:5 (v/v), 170 °C, 4 h

6B. M. Matsagar, M. M. Munshi, A. A. Kelkar and P. L. Dhepe, Catal. Sci. Technol., 2015, DOI: 10.1039/C5CY00858A.

Dehydration of fDehydration of fructose ructose to HMFto HMF

Fr ctose con ersion HMF Yield Gl cose Yield

80

100

/ (%)

Fructose conversion HMF Yield Glucose Yield

40

60

nver

sion

/uc

t Yie

ld(

0

20Con

Prod

u

Fig. Reaction condition: fructose 0.5 g, Water+MIBK 1:5 (v/v) 30 mL, catalyst, 0.025 g, 150 °C, 30 min7

Catalysts

Optimization of reaction Optimization of reaction parametersparameters

Catalyst quantity (g) at 150 °C, 30 min Time (min) at 150 °C0.05 (HMF 71%)

0.025 (HMF 73%)

20 min (HMF 60%)

30 min (HMF 73%)

0.0125 (HMF 50%)

S l 30 L 50 C 30 iT t (°C) t 30 i

40 min (HMF 56%)

Solvent 30 mL at 50 °C, 30 minWater (HMF 17%)

Temperature (°C) at 30 min140 (HMF 54%)

Water+MIBK 1:5 (v/v) (HMF 73%)

Water+Toluene 1:5 (v/v) (HMF 39%)

150 (HMF 73%)

160 (HMF 69%)

8

Effect of fructose Effect of fructose concentration & concentration & Recycles studyRecycles studyRecycles studyRecycles study

Conversion HMF Yield Fructose conversion HMF Yield

80

100Conversion HMF Yield

80

100

)

Fructose conversion HMF Yield

60

ersi

on/

Yiel

d (%

)

60

ersi

on/

Yiel

d (%

)

20

40

Con

vePr

oduc

t Y

20

40

Con

vePr

oduc

t

05 10 20 40 40

1 h rea0

1 2 3 4 5 6

Fructose (wt%)

Fig. Reaction condition: [C3SO3HMIM][HSO4] 0.025

Run

Fig. Reaction condition: fructose 0.5 g, Water+MIBK

9

g, Water+MIBK 1:5 (v/v) 30 mL, 150 °C, 30 min. 1:5 (v/v), [C3SO3HMIM][HSO4] 0.025 g, 150 °C, 30 min

B. M. Matsagar, M. M. Munshi, A. A. Kelkar and P. L. Dhepe, Catal. Sci. Technol., 2015, DOI: 10.1039/C5CY00858A.

ConclusionsConclusions Use of Brønsted acidic ionic liquids (BAILs) in catalytic amount for below

reactions

OHOH

HO

O-3H2O

-3H2O

OHOH

xylose furfural fructose HMF

Property activity correlation study shows ion-dipole type of interaction,Hammett acidity, homogeneous nature of a catalyst plays important role inhigher selectivity and yield of furanshigher selectivity and yield of furans

B. M. Matsagar, M. M. Munshi, A. A. Kelkar and P. L. Dhepe, Catal. Sci. Technol., 2015, DOI: 10.1039/C5CY00858A.

10

B. M. Matsagar and P. L. Dhepe, Catal. Sci. Technol., 2015, 5, 531-539.

Thank youB. M. Matsagar, M. M. Munshi, A. A. Kelkar and P. L. Dhepe, Catal. Sci. Technol., 2015,B. M. Matsagar, M. M. Munshi, A. A. Kelkar and P. L. Dhepe, Catal. Sci. Technol., 2015, 

DOI: 10.1039/C5CY00858A.

http://pubs.rsc.org/en/content/articlelanding/2015/cy/c5cy00858a/unauth#!divAbstract

For other works on biomass conversion using ionic liquids

B. M. Matsagar and P. L. Dhepe, Catal. Sci. Technol., 2015, 5, 531‐539

http://pubs.rsc.org/en/content/articlelanding/2015/cy/c4cy01047g#!divAbstract

DOI: 10.1039/C4CY01047G

Group web‐page: http://academic.ncl.res.in/pl.dhepe