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“Solid acid catalyzed Lignocellulosic Biomass conversion in Water or SC organic solvents”

Understanding and overcoming limitations

Nadine ESSAYEM

Institut de recherches sur la catalyse et l’environnement de Lyon,

IRCELYON-CNRS

VII BRAZILIAN SCHOOL OF GREEN CHEMISTRY MEETING

Novel processes for the renewable industry

9th and 10th – October 2017-INT-Rio de Janeiro - Brazil

Institut de Recherches sur la Catalyse et l ’Environnement

de Lyon

100 permanent staff ~150 non permanent staff (60 PhD-25-35 post-doc)

Team Sustainable Chemistry : from fundamental to applications

Design of nanomaterials-Molecular precursors, hybrids- acido-basic catalysts- metallic catalysts- Organometallic complexes

Sustainable chemistry:

- heterogeneous catalysis

metallic, acido-basic….

- catalysis in water

- Catalysis in SC organic media

Catalysis for lignocellulose

- Sugars, carboxylicacids, polyols- wood, cellulose, hemicellulose, lignin

Axe 2

Team : Sustainable Chemistry: from fundamental to applications

Thanks

Doctorants : Flora Chambon, Chuc Nguyen, Amar Dandach, Alexandre Demolis,Post-doc: Quynh Nguyen, Youssef SwessiColleagues: Franck Rataboul, Pascal Fongarland, Marion Eternot,

Catalysis for Lignocellulosic biomass

Lignocellulose

Hemicellulose

Cellulose

Lignine

GlucosePhénols,

biooils

Pentose

Propylène

Glycol

Levulinic(ate) acid

Sorbitol

Diols, lactone, 2 MTHF, 3 MTHF

(hemi)celluloses

functionalizedisosorbide diméthylisosorbide

Furfural

Diacides

FDCA

Plateform

molecules,

biooils

lactate

fructose

polyols

Lactic acid

Aconitic acid

HMF

Xylitol

WO2014096305

WO2004007560

WO2011 107712WO2012085362WO2014097040

WO2013030131

WO2012022853WO2012085362

WO2014023902

WO2012156479

WO2014122319

FR3008970

WO2011107712

Br

WO2014122319

The team Patent Porfolio

WO2013030132

Team : Sustainable Chemistry : from fundametal to applications

[email protected]

HMF FDCA

Hexoses

6

Lignocellulosicbiomass

Cellulose

Hemicelluloses

Lignin

Chemicals from raw biomass liquefaction assisted byheterogeneous catalysts

Biomass deconstruction

Fractions transformations Large variety of

valuable coumpounds

GlucoseHMF

FurfuralLevulinic acid

Etc …

Drawbacks:- modifications of the native components- Difficult isolation of hemicellulose- Low carbon efficiency and sustainability

Advantages:- Accessibility to isolated fractions - Pure component-> Se - Avoid possible catalysts poisoning with lignin or

hemicellulose fragments

Usual approach

7

Hemicelluloses

Lignin

Large variety of valuable coumpounds

GlucoseHMF

FurfuralLevulinic acid

Etc …

Lignocellulosicbiomass

Direct un-pretreated wood fractionation/conversion

Chemicals from raw biomass liquefaction assisted by heterogeneous catalysts

Our approach:

Liquid water // SC organic solvents

solid acid catalysts

Chemicals

Next Challenge ?

Outline

Cellulose vs wood in Water

• Understanding limitations and overcoming:

• Analytic tools development

• Uncatalyzed vs catalyzed cellulose liquefaction: kinetics

• Improvement of solid Lewis acid catalyst efficiency

• Cellulose vs wood conversion into Lactic acid: Kinetics, mechanism

SC organic solvents

• Potential of SC organic fluids

• Usual approaches

• New challenges

9

Direct conversion of wood components into chemicalsin organic solvents: recent advances

[1] C.Chesi, I.B.D. deCastro, M.T.Clough, P.Ferrini, R.Rinaldi ChemCatChem 8(2016) 2079-2088.

[2] M.V.Galkin, A.T.Smit, E.Subbotina, K.A.Artemenkon, J.Bergquist, W.J.J.Huijgen, J.S.M.Samec ChemSusChem9(2016)3280-3287.

[3] B.F.Sels et al. Green Chem 7(2015)5035.

Y.Wang, 2016 [5]Pt/NbP, cyC628% alkanes

[5] Y. Wang, Nature Communication 2016, DOI:10.1038

Reductive catalytic Fractionation, Lignin first

Phenolics Y~50% + Solvents, H2O, MeOH, EG, THF..

Bert Sels, 2015 [3]Pd/C, H2,

M.M.Abu-Omar, 2015 [4]Zn-Pd/C, H2,

R.Rinaldi,2016 [1]Ni Raney, isoPrOH

J.S.Samec,2016 [2]Pd/C, ethanol

Phenolics Y~40-50% +

Carbohydrate residue

[4] M.M.Abu-Omar et al. Green Chem 17(2015) 1492

Carbohydrate residue

10

Direct catalytic conversion of wood carbohydrates into chemicals in hot water: recent advances

Ethylene glycol

Propylene glycolT.Zhang, 2012 [1]

WC, H2,50% EG+PG

+

H.Kobayashi,A.Fukuoka,2016 [2]

Pyrolized wood +HCl~80 % G+X

[2] H.Kobayashi et al., Catal. Commun. 2014, 54, 22

[1] T. Zhang et al., Energy Environ. Sci. 2012, 5, 6383-6390.

[3] A. Fukuoka et al., Chem. Sci. 2016, 7, 692-696

Lactic acid 2017 [5]

ZrW

[5] N.Essayem et al, ChemCatChem 9 (2017) 1-7

SorbitolPt/C,H260% X+S

ZrP-Ru/C, H2

Xylitol

+

H.Kobayashi,A.Fukuoka2014 [3]

T.Zhang2017 [5]

[4] Q.Liu, T.Zhang, Y.Liao, C.Cai, J.Tan, T.Wang, S.Qiu, M.He, L.Ma ACS Sustainable

Chemistry &Engineering 5(2017)5940-5950

+ solid lignin as residue

Objectives: deeper understanding the phenomenon

the role of solid Lewis acid catalyst on the mechanism ofcellulose/wood hydrothermal liquefaction.

Solid Lewis acid

11

Solid Lewis acid catalyzed lactic acid formation from biomass :

Cellulose vs wood

A stepwise approach

Limitations understanding Cellulose vs wood into Lactic acid:- Analytic tools development - Kinetic studies of uncatalyzed and ZrW catalyzed celluloses liquefaction- Improvement of Solid Lewis acid catalyst efficiency: key parameters?

12

Homogeneous catalysts in water

Production of lactic acid from biomass (sugars, cellulose, lignocellulose)

Up to 91% lactic acid yield from cellulose with ErCl3

13

Heterogeneous catalysts in water

Up to 32% lactic acid yield from cellulose with Pb(OH)2/rGO, no direct conversion of wood

Production of lactic acid from biomass (sugars, cellulose, lignocellulose)

Rôle of water self protolysis:

2H2O OH- + H3O+ Ke= [H3O+][OH-]

[H+]=f(T)

Difficulties/advantages: Hot water = reactive solvent

OO

OH

HOO

O HO

OH

OH

OH

Cellulosen

H+

OO

OH

HOO

O HO

OH

OH

n

H+

(homogeneous

Bronsted acids)H2O

H+

- 3H2OO

CH2OH

O

+ 2 H2O

O

HO

Olevulinic acid

HO

O

HO OH

OH

OH

+ H OH

O

formic acidglucose5-HMF

HO

O

HO OH

OH

OH

glucose

0

10

20

30

40

50

150 155 160 165 170 175 180 185 190 195

0

10

20

30

40

50

150 155 160 165 170 175 180 185 190 195

Dis

solu

tion d

e la c

ellulo

se (%

)

Température °C

F.Chambon, F.Rataboul, A.Cabiac, C.Pinel, E.Guillon, N.Essayem, Green Chem 2009

M. Chaplin, Water Structure and Science, 2009

Promotion of cellulose liquefaction(24h)

Cellulose liquefaction in hydrothermal conditions

Lactic acid synthesis from cellulose

Cellulose hydrolysis in hot water

Conditions: 1.6g cellulose, 0.68g catalyst, 65g H2O, 190°C, 24h, 50 bar He

Lactic acid formation:Cooperation betwee H3O+ (water self protolysis) and solid Lewis acid sites.

N. Essayem, F.Chamcon, F.Rataboul, A.Cabiac, E.Guillon WO 2011 098683, WO2012 085361

0.00

5.00

10.00

15.00

20.00

25.00

30.00

35.00

40.00

45.00

50.00

H-U

SY

Cs2

.5H0.

5PW

12O

40

ss c

atal

yseu

r

Cs2

SnPW

12O

40

C-S

O3H ZrS

ZrWSnA

lAlW

% m

ol

OPS

Produits non identifiés

5-HMF

Acétol

Acide acétique

Acide lévulinique

Acide formique

Acide lactique

Glucose

Earlier objectives:LA yield increase via catalysts design and experimental conditions optimization

F.Chambon, F.Rataboul, A. Cabiac, C.Pinel, E.Guillon and N.Essayem Appl. Catal. B:Environnemental 105(1-2) (2011) 171-181

Conditions: 2 g cellulose, 60 mL water, 190 °C)

Celluloses DP CI (%) Particules sizes ()

microcrystalline 155 80 20

Sigmacell 560 70 fibers

Avicel 155 80 50

Liquefaction of celluloses of different featuresin hot water

Pathway for celluloses liquefaction

Celluloses features

Sigmacell: DP 560 , CI=70%

Avicel: DP 155, CI=80%

Kinetic constant (h-1)* Activation energy (kJ.mol-1)

Sigmacell Avicel Sigmacell Avicel

0.687 0.140 57.8 88.0

*T=200°C, Pseudo first order for each step

Kinetic Constant -Activation Energy

P.Fongarland, N.Essayem, F.Rataboul Ind.Eng.Chem.Res.56(2017) 126-134

Kinetic of uncatalyzed Cellulose liquefaction: influence of cellulose features

17

Analytical methods

Cellulose fibers

Solid phase(cellulose + catalyst+residue)

DRX/13C-NMR/

Solid catalyst

Oligosaccharides(IC-amperometric detector)

Soluble polymers

Organic acids/sugars/diolsOther products detected by HPLC

HPLC with RID

H2O

Liquid phase TOC (mgC/l)= solubility of cellulose

Rdti= 100 x (nCi/6) x (ni/nglucose unit)

Solubility (%)=100 x (mgCsolubility/mgCinitial)

Rdt OPS= solubility (%) – Ʃrdti

IR:cellulose conversion

Solid carbon residue (%)= conversion of cellulose - solubility

Appl. Catal. B:Environnemental 105 (2011) 171-181

ChemSusChem 6 (2013) 500 – 507

Appl. Catal. A:General, 504(2015), 664-671

F.Chambon, F.Rataboul, A. Cabiac, C.Pinel, E.Guillon and N.Essayem

Proposed mechanism

Efficient solid Lewis acid for Lactic acid formation from cellulose:….Identification of limiting parameters

Statement: saccharides conversion in water: high catalyst/substrate ratio are usual

0

10

20

30

40

50

60

70

80

90

100

5%NbOH 10%NbOH 15%NbOH 50%NbOH100%NbOH

Conversion

HMF yield

fructose yield

otehrs yield

Rodrigo Lopes de Souza, Franck Rataboul, Nadine Essayem

Challenges 3(2) (2012) 212-232 doi:10.3390/challe3020212

0

10

20

30

40

50

20% 42% 53%

Yie

ld o

f p

rod

uc

ts, %

catalyst / cellulose (%)

Conditions: T=190°C, t=24h, mcellulose MN 301= 1,6g, m

H2O=65g, Ar purge

LA

How to improve the control of the selectivity?

Outline





• Enhancement of solid Lewis acid catalyst efficiency


SC organic solvents



• New challenges

Bioresource Technology 149 (2013) 216–224

Acid catalyzed hydrolysis of lignocellulosic biomass to levulinic acid

Chemical Engineering Journal 217 (2013) 61–70

Acid-catalyzed hydrolysis of sugar cane bagasse

LvA + FA

21

Chain value:LCB Glucose HMF LvA + FA

Direct wood conversion into chemicals catalyzed by soluble Brnsted acids:

Kinetic models in literature:

Autoclave V = 100 ml

Masse de cellulose = 1,6 g Mass d'eau distille = 65 gMasse de catalyseur = 0,68 g

(cellulose MN 301(DP: 400-500; ∅ 2-20 μm))

Autoclave V = 2,5 L

Conditions:wood= 38.4gcatalyst = 16,3 gwater = 1,56 kgT = 190 ° CP = 11 atm

(∅<500 microns)

% H2O 8.70

% C 48.60

% Cellulose 37.20

% Hémicellulose 19.10

% Lignine 30.60

Direct solid Lewis acid catalyzed wood liquefaction into lactic acid: a kinetic approach

Cellulose Pine Wood sawdust

Substrate: cellulose MN301 Substrate: wood sawdust

0,00

0,50

1,00

1,50

2,00

2,50

3,00

3,50

Cellulosesubstrate

without ZrW

Cellulosesubstrate with

ZrW

woodsubstrate with

ZrW

Init

ial p

rod

uct

ion

rat

e (

g.L-1

.h-1

)

Lactic acid Formic acid Acetic acid

…..wood pretreatment would not be required

Modeling: comparison between wood and cellulose

Reaction rate equations were considered as pseudo-first-order kinetic (approach by Semans)

Good agreement between experimental and predicted data

High initial production rates of carboxylic acids using wood as substrate:

- Faster conversion of native cellulose- contribution of hemicellulose

- No negative effect of lignin on catalyst activity

Y.Swesi, C.Nguyen, T.T.H.Vu, F.Rataboul, M.Eternot, P.Fongarland, N.Essayem ChemCatChem 9 (2017) 1-7

solid lignin in the residue

Direct solid Lewis acid catalyzed wood liquefaction into lactic acid: a kinetic and

mechanism a approach

Two parallel pathways

Y.Swesi, C.Nguyen, T.T.H.Vu, F.Rataboul, M.Eternot, P.Fongarland, N.Essayem ChemCatChem 9 (2017) 1-7

Outline





• Improvement of solid Lewis acid catalyst efficiency


SC organic solvents



• New challenges – analytical tools development

Supercritical Fluid properties

Unique Phase

Principal physical properties

T>Tc: the increase of P can not liquefy the fluid

Clustering effect:

Clusters Formation:

- Local increase of the concentration solute /solvent

- Dependence with T and P

Tunable Dielectric Constant of FSC

Broad variations for the most polar SCFs:

NH3, H2O, CFC, N2O

solvents Tc(°C)

Pc(Bars)

solvent Tc(°C)

Pc(Bar)

water 374 220 2-butanol 263.0 41.0

CO2 31.1 73.9 n-butane 156.9 74.3

NH3 132.8 112.8 diethylether 192.6 36.1

acetone 235.5 47.6 n-pentane 196.6 33.7

methanol 240.0 79.5 ethylene 93.3 50.4

ethanol 243.0 63.8 N2O 36.5 72.4

1-propanol 263.6 51.7 CH3-NH2 156.9 74.3

Ligno Cellulosic Biomass (LCB) Liquefaction with SC organic solvents

Advantages of SC organic solvents :- Low critical coordinates- Large choice of SC solvents - Reactive solvent - Tunable solvent properties ….

Coupling Supercritical Organic Solvents and Catalysis in the frame of LCB valorization :

…..insolublein conventional solvents

LCB SC organic Fluids

Solubility issues

Catalysis

Selectivity

0100 501500100 50150 0100 50150

/ppm /ppm /ppm

(a) (b) (c)*

*

*

**

*

0100 501500100 50150 0100 50150

/ppm /ppm /ppm

(a) (b) (c)*

*

*

**

*

8

SC MeOH

SC MeOH 90%: 249 °C / 9.5 MPa

0

20

40

60

80

100

MeOH 100%

1 min2 hours

Solu

bili

sati

on

/ %

300 °C / 10 MPasuper-critical 240 °C / 6.5 MPa

sub-critical

MeOH 90%

2 hours

MeOH 90%

2 hours

1 min

250 °C / 8 MPanear-critical

MeOH 90%

2 hours

1 min

F.Ratabou, N.Essayem, Ind. Eng. Chem. Res. 2011, 50, 799-805

0

10

20

30

40

50

60

70

80

90

100

Liq

uéfa

ctio

n d

e la

cellu

lose

(%

) 300°C, 1 min50 bars 52 bars 60 bars

n-Butanol iso-Butanol sec-Butanol

SC BuOH isomers,

n-BuOH Tc=290°C, Pc=44bar

A.Demolis, M.Eternot, N.Essayem,F.Rataboul

New Journal of Chemistry 40 (2016) 3747-3754

Usual approach LCB liquefaction into bio-oils.

LCB liquefaction into bio-oils.

Liquefaction of LCB in SC ethanol: Mass balances

FeedstockP (bar)

solid residue(wt%)

light products yield (wt%)

Gasesyield(wt%)

Bio Oil yield(wt %)

Massbalance (wt%)

Pine wood 102 60 10 1.6 33 105

Lignin (CIMV) 111 48 5 2.7 40 96

Cellulose

(microcryst.)

111 44 13 2.0 50 109

Conditions: m solid biomass=2.5g, m ethanol=27.0g, T=280°C, Treatment time=1h

N. Q. Bui, P. Fongarland F. Rataboul, C. Dartiguelongue, N. Charon, , C. Vallée, N. EssayemFuel Processing Technology, 134 (2015) 378-386

Usual approach

Liquefaction of LCB in SC ethanol: Pine wood and models : lignin (CIMV), microcrystalline cellulose

32

0 5 10 15 20 25 30 35 40 45 50

Retention time (min)

EtOH after blank test

Absolute EtOH

Lignin

Cellulose

Pine

EtOH

EtOH – blank test

Lignin

Cellulose

Pine-wood

GC MS Analysis of liquid products

N. Q. Bui, P. Fongarland F. Rataboul, C. Dartiguelongue, N. Charon, , C. Vallée, N. EssayemFuel Processing Technology, 134 (2015) 378-386

33

GC

retention

time (min)

Identified compounds Yields

( %)

proposed origin

1.9 Diethyl ether - C4H10O 0.29 solvent

2.0 Ethyl vinyl ether - C4H8O 0.03 solvent

2.1 Acetaldehyde - C2H4O 0.97 carbohydrate/lignin

2.9 Ethyl formate - HCOOC2H5 0.03 carbohydrate/lignin

3.4 2-Methylfuran - C5H6O 0.02 carbohydrate

3.6 Ethyl Acetate - C4H8O2 3.31 hemicellulose/lignin

6.0 Ethyl acrylate - CH2=CHCOOC2H5 0.03 cellulose

7.2 2-Ethoxytetrahydrofuran - C6H12O2 0.17 carbohydrate

12.9 Ethyl orthoformate - C7H16O3 0.01 carbohydrate

13.3 2,5-Diethoxytetrahydrofuran - C8H16O3 0.05 cellulose

14.8 Acetol - CH3C(O)CH2OH 0.01 cellulose

15.2 Ethyl-lactate - C5H10O3 0.86 cellulose

16.2 1-Hydroxy-2-butanone – C4H8O2 0.08 carbohydrates

17.1 Butanoic acid, 2-hydroxy-, ethyl ester - C6H12O3 0.36 carbohydrate

17.7 Ethyl glycolate - C4H8O3 1.86 cellulose

18.8 1-Hydroxy-2-pentanone - C5H10O2 0.19 hemicelluloses

19.2 Furfural - C5H4O2 0.07 hemicelluloses

21.7 Tetrahydrofurfuryl alcool - C8H14O3 0.09 hemicelluloses

23.7 2-Hydroxy-3-methylsuccinic acid - C5H8O5 0.07 cellulose

25.2 Diethyl methylsuccinate - C9H16O4 0.04 carbohydrate

26.0 2-Furanmethanol - C5H6O2 0.28 cellulose

26.8 Succinic acid, diethyl ester - C8H14O4 0.06 carbohydrate

30.7 2-Propanol, 1-(2-methoxy-1-methylethoxy)- - C7H16O3 0.07

31.2 Ethyl hydrogen glutarate - C7H12O4 0.04

33.0 2-Cyclopenten-1-one, 2-hydroxy-3-methyl- C6H8O2 0.10

33.8 o-Guaiacol - C7H8O2 0.11 lignin

GC MSidentification and quantification of

of detected liquid products

Total yield lightliquid products < 15 wt%


LCB liquefaction into chemicals combining a reactive SC fluid and a solid catalyst

[1] F.Ratabou, N.Essayem, Ind. Eng. Chem. Res. 2011, 50, 799-805

[2] N.Essayem, G.Sapaly, M.Eternot, F.Rataboul WO 2014/001486

[3] L. Yang, X. Yang, E. Tian, H. Lin ChemSusChem 9 (2016) 36-41

An approach attracting more and more interest:

[1bis] A.Demolis, M.Eternot, N.Essayem,F.Rataboul

New Journal of Chemistry 40 (2016) 3747-3754

Methyl-levulinate yield (%)

0.3

12.5

17.5

19.5

16

20

350 mg cellulose, 150 mg catalyst

12

O

O

O

methyl-levulinate

MeOH 90%, 300 °C / 10 MPa / 1 minute

Catalyst

none

HZSM-5 (Si/Al = 28)

HY (Si/Al = 15)

Sulfated zirconia

Cs2.5H0.5PW12O40

Cs2HPW12O40

F.Ratabou, N.Essayem, Ind. Eng. Chem. Res. 2011, 50, 799-805

Cellulose reactivity in SC MeOH medium in the presence of solid acid catalysts :methyl-levulinate formation

Entry AcidTemp.

(°C)

Pressure

(MPa)

Mass of

recovered

liquid

(g)

Mass of

recovered

solid

(g)

Dissolution

(%)

Yield sec-

butyl

levulinate

(%)

1a None 175 10 0 2 0 0

2a H2SO4 150 10 0.8 0.94 53 10

3a H2SO4 175 10 1.1 0.94 53 13

4a H3PO4 175 10 0.22 1.35 32 0.6

5b H2SO4 175 10 1.25 0.7 65 13Pine wood

m= 2g cellulose ou épicéa

Cellulose

Trans-But-2-ene : T c=155,4 °C, Pc= 41,0 Bars

Cellulose and pine wood conversion in SC But-2-ene in semi-continuous reactor

[2] N.Essayem, G.Sapaly, M.Eternot, F.Rataboul WO 2014/001486


New objectives

…..insolublein conventional solvents

LCB SC organic Fluids

Solubility issues

Catalysis

Selectivity

Selective liquefaction of one wood fractionHemicellulose/cellulose/lignin, using adequatSC organic solvent

38

Bottleneck: compositional analysis of the solid residue

?Compositional analysis

Fresh Biomass:

- Acid hydrolysis and simplesugars analysis.

- lignin ~ insoluble

Problem:

Formation of chars,insoluble via acid hydrolyses

≠ lignin-

13C CP/ MAS NMR : cellulose and solid residues

unusual solvant


New objectives: selective liquefaction/fractionation of wood fractions into chemicals

39

“FTIR as a simple tool to quantify unconverted lignin from chars in biomass liquefaction process: application to SC ethanol liquefaction of Pinewood” N. Q. Bui, P. Fongarland F. Rataboul, C. Dartiguelongue, N. Charon, , C. Vallée, N. EssayemFuel Processing Technology, 134 (2015) 378-386

direct quantification of the lignin content by FTIR: quantification of C=C absorption band at 1514cm-1

Cellulose(wt %)

Hemi-Celluloses

(wt%)

Char*, ≠lignin:(wt%)

Lignin(wt%)

Analyticaltechnic

Compositional analysis by acid hydrolysis

Compositional analysis and

FT-IR

FT-IR

Pine wood 37 0.8 19 0.4 - 31 0.8

Solid residuefrom pinewood

52 1.1 10 0.2 26 1.0 8 0.2

1800 1700 1600 1500 1400 1300 1200 1100 1000 900 800

0.2

0.4

0.6

0.8

1.0

Ab

so

rba

nce

(a

.u.)

Wavenumber (cm-1)

Lignin

Lignin-280-1h

1514


Bottleneck: compositional analysis of the solid residue

New objectives: selective liquefaction/fractionation of wood fractions into chemicals

40 in SC ethanol : lignin and hemicellulose removal

0

10

20

30

40

50

60

70

80

90

Pine-280-1h Lignin-280-1h Cellulose-280-1h

Re

sid

ue

fra

ctio

n (

%)

Cellulose Hemicellulose Lignin

Residual fractions, batch conditions:

200 150 100 50 0

(ppm)

Pine wood

Pine wood treatment in SC ethanol

2000 1900 1800 1700 1600 1500 1400 1300 1200 1100 1000 900 800

1606

1238

1031

11261269

13291427

15141655

1720

1369

Ab

so

rba

nce

(a

.u.)

Wavenumber (cm-1)

Lignin

Lignin treatment in SC ethanol

1464

0.2

13C CP MAS NMRpine

FTIR lignin

Investigation of SC ethanol


New objectives: selective liquefaction/fractionation of wood components into chemicals

Réacteur

Capteur de pression

Manomètre

Réservoir

Manomètre

Thermocouple

41F.Rataboul, N;Essayem Industrial Engineering Chemistry Research 50(2) (2011) 799-805

SolventTc

(°C)Pc

(bar)Critical density

(kg/m3)EtOH 241 61 271

- Experimental conditions:T,P, density> critical values


Batch reactor: many disadvantages….

Potential of Semi-Continuous reactor

N.Essayem , G.Sapaly, M.Eternot, F.Rataboul WO 2014001486 “Levulinates from BLC in SC butene”


Conclusions:

LignoCellulosic Biomassinto Chemicals

Future developments will depend on

Development of analytic tools

Basic knowledge of Kinetic and mechanism

Understanding superficial properties/initial performances relationship….

Development of lab scale technics to probe solid / liquid interface

Design of robust solid catalyst

4th INTERNATIONAL CONGRESS ON CATALYSIS FOR BIOREFINERIES11-15 December 2017, Lyon, France

http://catbior2017.univ-lyon1.fr/en

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