Conversion of Concentrated sugar solutions into HMF and furfural using BAILs

1. 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

2. Applications ofApplications of FurfuralFurfural
Preservative
OH
Low-calorie Sweetener
Fuel additives
HO
OH OH
OH
Xylitol
+H2O -3H2O
Specialty chemicals
Hemicellulose (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

3. ApplicationsApplications 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
3
Fuel additive

4. Dehydration of xyloseDehydration of xylose
BAIL
Water+Toluene, 170 °C
100
Xylose Conversion Furfural Yield
Xylose Furfural
60
80
on/
d(%)
20
40
60
Conversio
oductYiel
0
20
C
Pro
Catalysts
Fig. Reaction condition: xylose 0.6 g, catalyst 0.08 g, Water+Toluene 1:5 (v/v) 60 mL, 170 °C, 4 h. 4

5. Optimization of reactionOptimization of reaction parametersparameters
Catalyst quantity (g) at 170 °C, 4 h Time (h) at 170 °C
1 (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

6. RecycleRecycle studystudy
100 Xylose Conversion Furfural Yield
80
eld(%)
60
oductYie
40
rsion/Pro
20
Conver
0
1 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.

7. Dehydration of fDehydration of fructoseructose to HMFto HMF
Fr ctose con ersion HMF Yield Gl cose Yield
80
100
/
(%)
Fructose conversion HMF Yield Glucose Yield
40
60
nversion/
uctYield(
0
20
Con
Produ
Fig. Reaction condition: fructose 0.5 g, Water+MIBK 1:5 (v/v) 30 mL, catalyst, 0.025 g, 150 °C, 30 min7
Catalysts

8. Optimization of reactionOptimization of reaction parametersparameters
Catalyst quantity (g) at 150 °C, 30 min Time (min) at 150 °C
0.05 (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 min
Water (HMF 17%)
Temperature (°C) at 30 min
140 (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

9. Effect of fructoseEffect of fructose concentration &concentration &
Recycles studyRecycles studyRecycles studyRecycles study
Conversion HMF Yield Fructose conversion HMF Yield
80
100
Conversion HMF Yield
80
100
)
Fructose conversion HMF Yield
60
ersion/
Yield(%)
60
ersion/
Yield(%)
20
40
Conve
ProductY
20
40
Conve
Product
0
5 10 20 40 40
1 h rea
0
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.

10. ConclusionsConclusions
 Use of Brønsted acidic ionic liquids (BAILs) in catalytic amount for below
reactions
OH
OH
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 in
higher 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.

11. Thank you
B. 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