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By

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
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Introduction
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


p
4) Make carbon neutral process
OPEN CYCLE CLOSED CYCLE
CO2 O2 CO2
h

Fossils Biomass

Multiple steps
Multiplesteps Multiplesteps
p p

2
Bio-refinery Concept
1. FOOD AND AGRICULTURE ORGANIZATION OF THE UNITED NATIONS, 2013, http://faostat3.fao.org/browse/Q/QC/E
Lignocellulosic biomass

EExtractionofjuice
i fj i
fromsugarcane
Other Cellulose

09% 40-50%
18-28%
20-30%

Components of
lignocellulosic biomass
Crop waste O
O
Removingseeds
Removing seeds O O

fromwheatcob O
HO OH
HO O O
O O OH Hemicellulose
OH O
HO OH
O
O
O
O
OH
OAr
Lignin 3
Hemicellulose C5 sugars

160C,1h
,

Hemicellulose
C5Sugar(X+A)

ConversionofhemicelluloseintoC5sugars(Xylose +Arabinose =X+A)usingBrnsted


acidicionicliquids(BAILs)

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


Catalyst evaluation
N

100 N
Cl

Oligomer X+A
80 HO3S
Product Yield (%)

Furfural
60

40

20

Catalyst
Conversion of Hemicellulose (birchwood xylan) using different catalysts.
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Reaction condition: birchwood xylan 0.6 g, catalyst 0.24 g, water 60 mL, 1 h, 160 C.
Hammett acidity function (Ho) of
catalysts
Hammett acidity function (Ho) data for different catalysts

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

Blank 0.94 100 0.0

HUSY (Si/Al=15)
HUSY(Si/Al=15) 0 46
0.46 48 9
48.9 51 1
51.1 0 97
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 2.47


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

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


indicator solution (10 mg p-nitroaniline in 1000 mL water)
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Correlation: catalyst activity with Ho
N

100 N 3
Oligomer X+A Cl

2.5
80 Furfural Ho HO3S
d%
duct yield

2
60

Ho
1.5
Prod

40
1

20
0.5

0 0

Ctalyst
y
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 concentration
Catalysts H+(mmol) X+Ayield(%) Furfural yield(%)
H2SO4 0.32 33 0
H2SO4 0.64 65 4
H2SO4 1.36 68 5
H2SO4 2.4 76 7
H2SO4 48
4.8 50 6
[C3SO3HMIM][PTS] 0.64 76 10
[C3SO3HMIM][HSO4] 1 58
1.58 87 10
HUSY 0.64 61 8
HMOR 0 64
0.64 48 6
PTSA 0.64 44 5
HCl 0 64
0.64 40 5
Reaction condition: birchwood xylan 0.6 g, water 60 mL, 1 h, 160 C
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Ion-
Ion-Dipole 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.


-Dipole type of interaction: 1H NMR
Ion-
Ion

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Optimization of reaction parameters
Catalyst quantity (g) at 160 C, 1 h Time (h) at 160 C
0.31 (X+A 76%, furfural 5%) 1 (X+A
(X A 76%,
76% ffurfural
f l 11%)
0.24 (X+A 76%, furfural 10%) 2 (X+A 68%, furfural 13%)
0.12 (X+A 59%) 3 (X+A 65%, furfural 18%)
0.06 (X+A 41%) 4 (X+A 53%, furfural 20%)
5 (X+A 56%, furfural 26%)
Temperature (C) at 1 h 6 (X+A 50%, furfural 22%)
150 (X+A 20%, furfural 3%)
160 (X+A 76%, furfural 11%)
170 (X+A 28%, furfural 7%)

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Effect of hemicellulose & its concentration
100 X+A Furfural 100 X+A Yield Furfural

80
Yield (%)

80

Yield (%)
60 60
Product Y

Product Y
40 40
P

P
20 20

0 0
beechwood oat spelt birchwood 0.6 1.2 1.8 1.8
Hemicellulose birchwood xylan (g)
Reaction condition: Hemicellulose 0.6 g, Reaction condition: [C3SO3HMIM][PTS] 0.24 g,
[C3SO3HMIM][PTS] 0.24 g, water 60 mL, 1 h, water 60 mL, 1 h, 160 C
160 C

BAIL is capable of converting almost all types of hemicellulose into sugar monomers. Also,
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BAILs are capable for converting concentrated substrate into sugar monomers.
Thankyou
FurtherReading:B.M.MatsagarandP.L.Dhepe,Catal.Sci.Technol.,2015,5,531539

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

DOI 10 1039/C4CY01047G
DOI:10.1039/C4CY01047G

Forotherworksonbiomassandionicliquid

B. M. Matsagar, M. M. Munshi, A. A. Kelkar andP.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

Groupwebpage:http://academic.ncl.res.in/pl.dhepe