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.dhepe1

IntroductionIntroduction Advantages of utilization of biomass over fossil feedstock (A biorefinery concept)

1) Helps to solve the problem of shortage of fossil feedstock

2) Abundantly available. (Production of crops in India in MT; 2013: Sugarcane 3.41x108, Rice paddy, 1.59x108,

Wheat 9.31x107)1

3) Renewable, sustainable and inexpensive

OPEN CYCLE CLOSED CYCLE

) , p

4) Make carbon neutral process

CO2 CO2O2hν

Fossils Biomass

Multiple steps Multiple stepsMultiple steps p p

Bio-refinery Concept 2

1. FOOD AND AGRICULTURE ORGANIZATION OF THE UNITED NATIONS, 2013, http://faostat3.fao.org/browse/Q/QC/E

Lignocellulosic biomassLignocellulosic biomass

E i f j iExtraction of juicefrom sugarcane

CelluloseOther

40-50%09%

18-28%20-30%

18-28%

Components ofComponents of lignocellulosic biomass

Removing seedsCrop waste

O O

O

O

Removing seedsfrom wheat cob

O O

HO O

OH

O

HO OH

O O

O

Hemicellulose

3

OHO OH

OH

O

OArOH

OO

O

Lignin

HHemicellulose emicellulose →→ C5 sugarsC5 sugars

160 °C, 1h

C5 Sugar (X+A) Hemicellulose

,

Conversion of hemicellulose into C5 sugars (Xylose + Arabinose = X+A) using Brønsted  acidic ionic liquids (BAILs)

4B. M. Matsagar and P. L. Dhepe, Catal. Sci. Technol., 2015, 5, 531-539.

Catalyst evaluationCatalyst evaluation

100 N

N

Cl

80

(%)

Oligomer X+A

FurfuralHO3S

40

60

uct Y

ield

20

40

Prod

0

CatalystCatalystConversion of Hemicellulose (birchwood xylan) using different catalysts.

Reaction condition: birchwood xylan 0.6 g, catalyst 0.24 g, water 60 mL, 1 h, 160 °C.5

Hammett acidity function (Hammett acidity function (HHoo) of ) of catalystscatalystscatalystscatalysts

Catalyst Amax [I]% [IH+]% H

Hammett acidity function (Ho) data for different catalysts

Catalyst Amax [I]% [IH ]% HO

Blank 0.94 100 0.0 ‐

HUSY (Si/Al=15) 0 46 48 9 51 1 0 97HUSY (Si/Al=15) 0.46 48.9 51.1 0.97

HMOR (Si/Al=10) 0.64 68.0 32. 1.31

H2SO4 0.78 82.9 17.1 1.67

[C3SO3HMIM][HSO4] 0.87 92.5 7.5 2.08

[C3SO3HMIM][PTS] 0.90 95.7 4.3 2.33

[C3SO3HMIM][Cl] 0.91 96.8 3.2 2.473 3

[BMIM][Cl] 0.94 100 ‐ ‐HO = pK(I)aq + log([I]/[IH+])

6

Ho calculated using p-nitroaniline indicator, ILs 0.075 g in 50 mL

indicator solution (10 mg p-nitroaniline in 1000 mL water)

Correlation: catalyst Correlation: catalyst activity with activity with HHoo

3100 Oligomer X+A N

N

Cl

2.580

d %

Oligomer X+A

Furfural Ho HO3S

Cl

1.5

260

Ho

duct

yie

ld

0.5

1

20

40

Prod

0

0.5

0

Ctalysty

Conversion of Hemicellulose (birchwood xylan) using different catalysts.

Reaction condition: birchwood xylan 0.6 g, catalyst 0.24 g, water 60 mL, 1 h, 160 °C

Effect of acid concentrationEffect of acid concentrationCatalysts H+ (mmol) X+A yield (%) Furfural yield (%)

H2SO4 0.32 33 0

H2SO4 0.64 65 4

H2SO4 1.36 68 52 4

H2SO4 2.4 76 7

H2SO4 4 8 50 6H2SO4 4.8 50 6

[C3SO3HMIM][PTS] 0.64 76 10

[C SO HMIM][HSO ] 1 58 87 10[C3SO3HMIM][HSO4] 1.58 87 10HUSY 0.64 61 8HMOR 0 64 48 6HMOR 0.64 48 6

PTSA 0.64 44 5

HCl 0 64 40 5

8

HCl 0.64 40 5Reaction condition: birchwood xylan 0.6 g, water 60 mL, 1 h, 160 °C

IonIon--Dipole type of interactionDipole type of interaction

Ion-dipole type interactions of alkyl imidazolium groups

and hydrogen sulphate ions with hydroxyl groups of

hemicellulose.

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

IonIon--Dipole type of Dipole type of interaction: interaction: 11H H NMR NMR

10

Optimization of reaction parametersOptimization of reaction parameters

Catalyst quantity (g) at 160 °C, 1 h Time (h) at 160 °C1 (X A 76% f f l 11%)0.31 (X+A 76%, furfural 5%)

0.24 (X+A 76%, furfural 10%)

1 (X+A 76%, furfural 11%)

2 (X+A 68%, furfural 13%)

0.12 (X+A 59%)

0.06 (X+A 41%)

3 (X+A 65%, furfural 18%)

4 (X+A 53%, furfural 20%)

5 (X+A 56%, furfural 26%)

6 (X+A 50%, furfural 22%)Temperature (°C) at 1 h150 (X+A 20%, furfural 3%)

160 (X+A 76%, furfural 11%)

170 (X+A 28%, furfural 7%)

11

Effect of hemicellulose & its concentrationEffect of hemicellulose & its concentration

100 X+A Yield Furfural100 X+A Furfural

60

80

Yiel

d (%

)

60

80

Yiel

d (%

)

40

Prod

uct Y

40

Prod

uct Y

0

20

P

0

20

P

00.6 1.2 1.8 1.8

birchwood xylan (g)

0beechwood oat spelt birchwood

Hemicellulose

Reaction condition: Hemicellulose 0.6 g,[C3SO3HMIM][PTS] 0.24 g, water 60 mL, 1 h,160 °C

Reaction condition: [C3SO3HMIM][PTS] 0.24 g,water 60 mL, 1 h, 160 °C

BAIL is capable of converting almost all types of hemicellulose into sugar monomers. Also,

BAILs are capable for converting concentrated substrate into sugar monomers. 12

Thank youFurther Reading: 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/C4CY01047GDOI: 10.1039/C4CY01047G

For other works on biomass and ionic liquid

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

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