catalytic conversion of biomass using solid acid catalysts
DESCRIPTION
The processes for synthesis of several value-added chemicals from biomass (hemicellulose and ignin) using solid acid catalysts are documented in this presentation. Particularly, C5 sugars and furfural are synthesized from hemicellulose and various aromatic monomers are obtained from lignin.TRANSCRIPT
h hh h * h k* h kParesh L. DhepeParesh L. Dhepe,* P. Bhaumik, T. Kane, A. K. Deepa,* P. Bhaumik, T. Kane, A. K. DeepaNational Chemical LaboratoryNational Chemical Laboratory
Pune 411008Pune 411008Pune 411008Pune 411008Tel. 91Tel. 91‐‐2020‐‐2590202425902024
EE‐‐mail: [email protected]: [email protected] p d epe@ c esa p d epe@ c es
CSIR‐National Chemical LaboratoryCatalysis Division
Green Chem., 2010, 12, 2153–2156 ChemSusChem 2012, 5, 751 – 761
ACS Catal. 2013, 3, 2299−2303 RSC Adv., 2014, 4, 12625
SO3H HOOC
SO3H HOGreen Chem., 2010, 12, 2153–2156 ChemSusChem 2012, 5, 751 – 761
ACS Catal. 2013, 3, 2299−2303 RSC Adv., 2014, 4, 12625
Surface area Acid amount Catalyst Type of catalyst Surface area, m2/g
Acid amount, mmol/g
H‐USY (Si/Al=15) Micro 873 0.55
H‐ZSM ‐5 (Si/Al=11.5) Micro 423 0.97
H‐BEA (Si/Al=19) Micro 761 0.91
( )H‐MOR (Si/Al=10) Micro 528 1.18
Nb2O5 ‐‐ 115 0.30
SO 2‐/ZrO 84 ndSO42 /ZrO2 ‐‐ 84 nd
Clay (K10) Layered 246 0.42
Al pillared clay Layered nd ndAl pillared clay Layered nd nd
SiO2‐Al2O3 Amorphous 532 0.63
10%MoO3/SiO2 Nonporous nd nd3/ 2 p
Amberlyst‐15 ‐‐ nd 4.65
Cs2.5‐HPA ‐‐ nd 0.20
Nafion‐SAC‐13 ‐‐ 190 0.13
Green Chem., 2010, 12, 2153–2156 ChemSusChem 2012, 5, 751 – 761
ACS Catal. 2013, 3, 2299−2303 RSC Adv., 2014, 4, 12625
SorbitolBagasse
Cellulose Glucose
Sorbitol(Rs.50000/ton)
Glycols
BagasseRs.750/ton
Cellulose(Rs.17500/ton) Gluconic/
glucoronic acid
HMF FDCA
Hydrogen
HMFLevulinic acid(Rs.175000/ton)
FDCA
Hydrogen
HemicelluloseXylose Xylitol
(Rs 100000/ton)FurfurylalcoholHemicellulose (Rs.75000/ton)
Arabinose Furfural
(Rs.100000/ton)
Furoic acid
alcohol(Rs.100000/ton)
Furoic acid
Lignin Aromatic monomers
*All prices are approximate
Solid catalysts Acid catalysts
Green Chem., 2010, 12, 2153–2156 ChemSusChem 2012, 5, 751 – 761
ACS Catal. 2013, 3, 2299−2303 RSC Adv., 2014, 4, 12625
Lignocelluloses contains cellulose (40‐50%), hemicellulose (25‐35%) and lignin (15‐25%)
Green Chem., 2010, 12, 2153–2156 ChemSusChem 2012, 5, 751 – 761
ACS Catal. 2013, 3, 2299−2303 RSC Adv., 2014, 4, 12625
Solid acid catalyst
HemicelluloseSolid acid catalyst
H2O H2O + Org. solvent
OH+ Xylose
OO
OH+ Xylose+ +
Furfural FurfuralArabinose
Major productsArabinose Major product
Furfural
ca. 40% xylose+arabinose yield, >90% conversion ca. 60% furfural yield, >90% conversion
ChemSusChem 5 (2012) 751; Green Chem. 12 (2010) 2153;
Selective conversion of Selective conversion of hemicellulosehemicellulose from from bagassebagasse ((lignocellulosiclignocellulosic material) is possiblematerial) is possibleSelective conversion of Selective conversion of hemicellulosehemicellulose from from bagassebagasse ((lignocellulosiclignocellulosic material) is possiblematerial) is possible
Patents: India , PCT, US, AU, JP, BR, CN
Green Chem., 2010, 12, 2153–2156 ChemSusChem 2012, 5, 751 – 761
ACS Catal. 2013, 3, 2299−2303 RSC Adv., 2014, 4, 12625
CatalystHemicellulose Xylose + Glucose + Arabinose
Xylan: Model substrate
a) Softwood: Xylose ≥70%, glucose ~ 15%, arabinose ~ 10%)
b) Hardwood: Xylose ≥ 90%
( )
Xylose 90%
Catalyst : Solid acid (pre‐treatment, 550oC for 24 h)
Pressure: 1‐50 bar @ RT, N2
Time: 1 h – 96 h
Temperature: 100°C – 200°C
Analysis: HPLC
Green Chem., 2010, 12, 2153–2156 ChemSusChem 2012, 5, 751 – 761
ACS Catal. 2013, 3, 2299−2303 RSC Adv., 2014, 4, 12625
Hemicellulose [Xylan] (several nm length)Hemicellulose [Xylan] (several nm length)
Oligomers (few nm length) 1 41.6
4550
/g
Xylose yield Acid amount, mmol/g
Xylopentaose
g ( g )
0.811.21.4
2530354045
unt, mmol/
e yield, %
Xylotetraose 0.20.40.6
51015205
Acid am
ou
Xylose
Xylotriose
005
catalyst
oly ac
id
Al =40
)
Nb2
O5
K10
/Al =
15)
/Al= 19
)
/Al= 10
)
/Al=10)
Al =2.6)
A
XylobioseWith
out c
Heterop
o
HUSY (S
i/A
HUSY (S
i/
Hbe
ta (S
i/
ZSM‐5 (S
i/
HMOR (Si/
HY (Si/A
H
catalyst
P. L. Dhepe, R. Sahu, patents (India, PCT, US, BR, AU, CN)P. L. Dhepe, R. Sahu, Green Chem. (2010); ChemSusChem (2012)
It’s a catalytic reaction.It’s a catalytic reaction.It’s a catalytic reaction.It’s a catalytic reaction.
Green Chem., 2010, 12, 2153–2156 ChemSusChem 2012, 5, 751 – 761
ACS Catal. 2013, 3, 2299−2303 RSC Adv., 2014, 4, 12625
+ water + + water + hemicellulosehemicellulose
Oligomer Xylose+Arabinose Furfural
+ water + + water + hemicellulosehemicellulose
5060
%
Reaction at 170°C, 3h
30405
s Yield
Centrifuge
1020
oducts
Solution+Unreacted0
1 2 3 4 5 6 7
Pr+Unreacted
hemicellulose
3 4 5 7
Number of runsCalcination
550°C, 16hReaction
Catalyst is recyclable up to 6 cyclesCatalyst is recyclable up to 6 cycles46 5% 46 5% xylose+arabinosexylose+arabinose yield was obtainedyield was obtainedCatalyst is recyclable up to 6 cyclesCatalyst is recyclable up to 6 cycles46 5% 46 5% xylose+arabinosexylose+arabinose yield was obtainedyield was obtained
Green Chem., 2010, 12, 2153–2156 ChemSusChem 2012, 5, 751 – 761
ACS Catal. 2013, 3, 2299−2303 RSC Adv., 2014, 4, 12625
Bagasse: Cellulose (~43%), hemicellulose (~30%), lignin (~18%)
60
70
, %
agasse Ce u ose ( 43 ), e ce u ose ( 30 ), g ( 8 )
40
50
60
se Y
ield,
20
30+a
rabino
0
10
Xylose+
Catalyst
HUSY (Si/Al=15) catalyst, 170oC
Selective conversion of Selective conversion of hemicellulosehemicellulose from real substrate, from real substrate, bagassebagasse is also possible.is also possible.Selective conversion of Selective conversion of hemicellulosehemicellulose from real substrate, from real substrate, bagassebagasse is also possible.is also possible.
Green Chem., 2010, 12, 2153–2156 ChemSusChem 2012, 5, 751 – 761
ACS Catal. 2013, 3, 2299−2303 RSC Adv., 2014, 4, 12625
7080 Furfural Xylose+arabinose
285060
yield, %
58
3040
oduc
t y
38
102030
Pro
X X15
010
Water Water+furfuralate ate u u a
Solvent
HUSY (Si/Al=15), 170°C, 6 h
Change from aqueous system to biphasic system yields more furfuralChange from aqueous system to biphasic system yields more furfuralChange from aqueous system to biphasic system yields more furfuralChange from aqueous system to biphasic system yields more furfural
Green Chem., 2010, 12, 2153–2156 ChemSusChem 2012, 5, 751 – 761
ACS Catal. 2013, 3, 2299−2303 RSC Adv., 2014, 4, 12625
Lignocelluloses contains cellulose (40‐50%) hemicellulose (25‐35%) and lignin (15‐25%) Lignocelluloses contains cellulose (40‐50%), hemicellulose (25‐35%) and lignin (15‐25%)
Green Chem., 2010, 12, 2153–2156 ChemSusChem 2012, 5, 751 – 761
ACS Catal. 2013, 3, 2299−2303 RSC Adv., 2014, 4, 12625
Aromatic monomers with 60% yield could be obtained below 250Aromatic monomers with 60% yield could be obtained below 250ooC from ligninC from ligninAromatic monomers with 60% yield could be obtained below 250Aromatic monomers with 60% yield could be obtained below 250ooC from ligninC from lignin
Green Chem., 2010, 12, 2153–2156 ChemSusChem 2012, 5, 751 – 761
ACS Catal. 2013, 3, 2299−2303 RSC Adv., 2014, 4, 12625
TPD
XRD
TPD
(f)(f)HZSM‐5 (Si/Al=40)f e h
(e)(e)HUSY (Si/Al=40)‐fresh
‐fresh
(b)
(a.u
.) (b)
(a.u
.)
HUSY (Si/Al=15)‐fresh
(d)(d)Clay
Inte
nsity
In
tens
ity
(c)(c)HB (Si/Al=19)‐fresh
(a)(a)
HUSY (Si/Al=15)‐used
(a)
(b)
(a)
(b)
HUSY (Si/Al=15)
HUSY (Si/Al=15)‐fresh
fresh10 20 30 40 50 60 70 80 90
2 (°)10 20 30 40 50 60 70 80 90
2 (°)
Temperature, K 423 473 523 573 623 673 723 773 823 873
Temperature, K 423 473 523 573 623 673 723 773 823 873
‐used
Catalyst morphology changesCatalyst morphology changesCatalyst morphology changesCatalyst morphology changes
Green Chem., 2010, 12, 2153–2156 ChemSusChem 2012, 5, 751 – 761
ACS Catal. 2013, 3, 2299−2303 RSC Adv., 2014, 4, 12625
Characterization
CatalystHUSY (Si/Al=15)
F h S tCharacterization Fresh(mmol/g)
Spent(mmol/g)
Na K Total Na K Totala o a a o aICP‐AES 0.17 ‐ 0.17 0.14 0.14 0.28NH3‐TPD 0.55 0.21
M+
Zeolite with proton Zeolite with exchanged proton
Green Chem., 2010, 12, 2153–2156 ChemSusChem 2012, 5, 751 – 761
ACS Catal. 2013, 3, 2299−2303 RSC Adv., 2014, 4, 12625
Properties SAPO‐44 SAPO‐5 H‐MOR
Thermal Stability (C) in 1000 1000 ‐y ( )air[12]
Hydrothermal Stability (C) under 20% steam[12]
600 600 340[17]
(C) under 20% steam[12]
Surface Area (m2/g) 670[13] 184[14] 528[5]
Pore Size (nm) [12] 0.43 (small pore)
0.8 (large pore)
0.59[5]
P V l ( / ) [13] 6[15] [5]Pore Volume (cc/g) 0.29[13] 0.16[15] 0.22[5]
Total Acidity 0.93 0.09 1.2[5]ota c d ty(mmol/g)[16]
0 93 0 09
[5] Green Chem., 2010, 12, 2153–2156. ChemSusChem, 2012, 5, 751 – 761.[12] J. Am. Chem. Soc., 1984, 106, 6092-6093. [13] Colloids andSurfaces A, Physicochem. Eng. Aspects, 1999, 146, 375–386. [14] Microporous and mesoporous Mater., 1999, 31, 271-285. [15] J. Chem. Soc.Faraday Trans., 1992, 88. [16] Proc. Indian Acad. Sci. (Chem. Sci.), 1994,106, 3, 621-628. [17] Adsorption, 2005,11, 405–413,
Green Chem., 2010, 12, 2153–2156 ChemSusChem 2012, 5, 751 – 761
ACS Catal. 2013, 3, 2299−2303 RSC Adv., 2014, 4, 12625
Polysaccharide disaccharide glucose
Fructose HMF
100100
Glucose Yield (%) HMF Yield (%) Fructose Conv. (%)Fructose HMF
6374
60708090
60708090
ersion (%
)
ld (%
)
30405060
30405060
ose co
nve
oduc
t yie
0102030
0102030
Fruc
to
Pro
Non‐cat SiO2 g‐Al2O3 SAPO‐5 H‐MOR SAPO‐44
Catalyst
Reaction Condition: fructose, catalyst, water + MIBK = 1:5, 175C, 1 h
y
SAPOSAPO‐‐44 showed best selectivity (88%) for HMF formation from fructose44 showed best selectivity (88%) for HMF formation from fructoseSAPOSAPO‐‐44 showed best selectivity (88%) for HMF formation from fructose44 showed best selectivity (88%) for HMF formation from fructose
Green Chem., 2010, 12, 2153–2156 ChemSusChem 2012, 5, 751 – 761
ACS Catal. 2013, 3, 2299−2303 RSC Adv., 2014, 4, 12625
Catalyst + Catalyst + H2O (d=0.99 g/mL) + CCl4 (d=1.58 g/mL)
10 minutes
water
Catalyst Density
(g/mL)
CCl4
SAPO‐44 0.61
H‐MOR 0 35
Catalyst + H2O (d=0.99 g/mL) + MIBK (d=0.8 g/mL) H‐MOR 0.35
10 minutes
MIBK
10 minutes
water
HydrophilicityHydrophilicity: SAPO: SAPO‐‐44 > SAPO44 > SAPO‐‐5 > HMOR5 > HMORHydrophilicityHydrophilicity: SAPO: SAPO‐‐44 > SAPO44 > SAPO‐‐5 > HMOR5 > HMOR
Green Chem., 2010, 12, 2153–2156 ChemSusChem 2012, 5, 751 – 761
ACS Catal. 2013, 3, 2299−2303 RSC Adv., 2014, 4, 12625
MIBK
CatalystX XX XWater
SAPO‐44 H‐MOR
With HMOR in organic phase, higher degradation products could be obtainedWith HMOR in organic phase, higher degradation products could be obtainedWith HMOR in organic phase, higher degradation products could be obtainedWith HMOR in organic phase, higher degradation products could be obtained
Green Chem., 2010, 12, 2153–2156 ChemSusChem 2012, 5, 751 – 761
ACS Catal. 2013, 3, 2299−2303 RSC Adv., 2014, 4, 12625
+ + water + MIBK water + MIBK + + fructosefructose+ + water + MIBK water + MIBK + + fructosefructose
80
Reaction at 175°C, 1h
60
70
%)
Centrifuge
30
40
50
F Yield (%
Solution( hi & D i )( hi & D i )
10
20
30HM(washing & Drying)(washing & Drying)
0
10
1st 2nd 3rd 4th 5th
Calcination WO Calcination
Recycle RunReaction47% yield Catalyst could be recycledCatalyst could be recycledCatalyst could be recycledCatalyst could be recycled
Green Chem., 2010, 12, 2153–2156 ChemSusChem 2012, 5, 751 – 761
ACS Catal. 2013, 3, 2299−2303 RSC Adv., 2014, 4, 12625
Fructose Yield (%) HMF Yield (%) Glucose Conv. (%)
80
100
8090100
%)
Fructose Yield (%) HMF Yield (%) Glucose Conv. (%)
60
80
607080
version (%
Yield (%)
40304050
cose con
v
Prod
uct Y
0
20
01020
Glu
Non‐cat SiO2 SAPO‐5 H‐MOR SAPO‐44Catalyst
Glucose conversion to HMF via Glucose conversion to HMF via isomerizationisomerization to fructose is possibleto fructose is possibleGlucose conversion to HMF via Glucose conversion to HMF via isomerizationisomerization to fructose is possibleto fructose is possible
Green Chem., 2010, 12, 2153–2156 ChemSusChem 2012, 5, 751 – 761
ACS Catal. 2013, 3, 2299−2303 RSC Adv., 2014, 4, 12625
Spent SAPO-44.)
nsity
(a.u
Inte
n
Fresh SAPO-44
10 20 30 40
2 o2o
Structural changes happen during the course of reactionStructural changes happen during the course of reactionStructural changes happen during the course of reactionStructural changes happen during the course of reaction
Green Chem., 2010, 12, 2153–2156 ChemSusChem 2012, 5, 751 – 761
ACS Catal. 2013, 3, 2299−2303 RSC Adv., 2014, 4, 12625
Fresh SAPO‐44 Spent SAPO‐44
Green Chem., 2010, 12, 2153–2156 ChemSusChem 2012, 5, 751 – 761
ACS Catal. 2013, 3, 2299−2303 RSC Adv., 2014, 4, 12625
• Solid acids can,OHOH
OO
64% yield 58% yield64% yield 58% yield
60% yield
• Morphological changes happen in the catalyst structure74% yield
• Morphological changes happen in the catalyst structure
Green Chem., 2010, 12, 2153–2156 ChemSusChem 2012, 5, 751 – 761
ACS Catal. 2013, 3, 2299−2303 RSC Adv., 2014, 4, 12625
HMFFuran
Diformyl furanHMF 2,5‐dicarboxylic acidDiformyl furan
XylitolHemicellulose
HO H
OH
CH2OH
HMetal catalystMetal catalyst
y to
Glucose
HO H
H OH
H OH
CH2OH
yH2, H2O
Cellulose
yH2, H2O
2
Sorbitol
M+M+
Zeolite with proton Zeolite with exchanged proton
Green Chem., 2010, 12, 2153–2156 ChemSusChem 2012, 5, 751 – 761
ACS Catal. 2013, 3, 2299−2303 RSC Adv., 2014, 4, 12625
Funding agencies: DST In house research grantFunding agencies: DST, In‐house research grant
Deepa A K SRF Prasenjit Bhaumik SRF Anup Tathod SRF B. Matsagar, SRFDeepa A. K., SRF Prasenjit Bhaumik, SRF Anup Tathod, SRF B. Matsagar, SRF
Sandip Singh, JRF Sanil E. S., PATanushree Kane, PARicha Km, JRF
Green Chem., 2010, 12, 2153–2156 ChemSusChem 2012, 5, 751 – 761
ACS Catal. 2013, 3, 2299−2303 RSC Adv., 2014, 4, 12625