catalytic conversion of biomass using solid acid catalysts

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


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


ACS Catal. 2013, 3, 2299−2303 RSC Adv., 2014, 4, 12625

Lignocelluloses contains cellulose (40‐50%), hemicellulose (25‐35%) and lignin (15‐25%)


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


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


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.


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


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.


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


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%)


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


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


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


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,


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


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


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


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


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


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


ACS Catal. 2013, 3, 2299−2303 RSC Adv., 2014, 4, 12625

Fresh SAPO‐44 Spent SAPO‐44


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


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


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


ACS Catal. 2013, 3, 2299−2303 RSC Adv., 2014, 4, 12625

catalytic conversion of biomass using solid acid catalysts

Science

acs catal

furfural xylose

catalyst hemicellulose

ton arabinose furfural

ton cellulose rs

conversion chemsuschem

h hh h

cn green