WP No. 3: Advanced biochemical conversion of biomass · Project BIOSYNERGY ... from biotechnology to fine chemistry – Side event November 17, 2010, Reims ... WP No. 3: Advanced

Workshop ‘Development of multi-product lignocellulose biorefinery technology with focus on residues (pentoses, lignin) from cellulose ethanol production - Results of the Integrated Project BIOSYNERGY ’Biomass derived pentoses: from biotechnology to fine chemistry – Side eventNovember 17, 2010, Reims (France)

C. Aymard, C Boeriu, B. Clément, B. Houweling-Tan, T. Jing, A. Lopez Contreras, M.-L. Mattinen, R. Marchal, M. Penttilä, A. Rogut, J. Rogut, M. Ropars, T. Tamminen, A. Togtema, H. van der Wal, P. van Doeveren, M. Wiebe, F. Monot

WP No. 3: Advanced biochemical conversion of biomass

Background/Vision WP 3 activities (1)

Physicalchemical

pretreatment&

Fractionation

Ligno-cellulosicbiomass

Esp.STRAW

Lignin

Hemicellulose

Cellulose EnzymaticHydrolysis

Fermentation

ChemicalConversion

Ethanol

ABE

Xylonic acid

(HMF) > 2,5 FDA

Furfural

PentosideSurfactants

C5 sugars

SC Depolymeri-

sation

CatalyticPyrolysis

Fractionation &

(bio-)chemicalconversion

Phenolics

Poly-ethers

Resins / Thermosets

C6 sugars

CHP Heat & Power to process

B i o m a s s r e s i d u e s


Hemicellulose

C6 sugarsC5 sugars

Cellulose

C6 sugars

Lignin

Aromatic alcohols

Acetone + butanol

Sugar derivatives

Ethanol

Dispersants AdhesivesFuelChemical Building block

Separation processes

Biological conversion

Functional lignin derivatives


From microbiologyto fermentation ...

and separation


Main partners

• IFP Energies nouvelles: Scientific Research and industrialdevelopment center. Dvt of chemical (and biotechnological) processes.

• VTT - VTT Biotechnology: enzymology of lignocellulosic materials transformation, metabolic engineering and fermentation technology.

• WUR: Wageningen UR Food and Biobased Products. Separation, microbiology and fermentation.

• GIG: Glowny Instytut Gornictwa (Central Mining Institute). Separationprocesses.

WP3: Main results

3.1 Acetone-butanol fermentation (ABE). - ABE from wheat straw hemicellulose hydrolysates IFP EN

from DDGS WUR- Separation by pervaporation WUR

using Multiphase Rotating Contactors (MRCs) GIG

3.2 Sugar conversion to platform chemicals. VTT

3.3 Production of functional lignin derivatives. VTT

WP3: Acetone-butanol fermentation (ABE) (1)

Microbiology

• Clostridium acetobutylicum, beijerinckii, ...

• Anaerobic bacteria

• Solventogenesis coupled to sporulation

• Genome sequences available

WP3: Acetone-butanol fermentation (ABE) (2)

Fermentation

• Two-phases (acidogenesis-solventogenesis)

• Shift to solventogenesis related to pH

• Can use C5 and C6 sugars

• Toxicity of products limits solvent levels

ABE (3) – Screening of strains on glucose

12.00.234IFP T'110A

13.00.334IFP M410C

5.50.120DSMZ1739

3.00.416DSMZ6423

7.04.035DSMZ 1733

7.57.047DSMZ 792

9.07.026DSMZ 1731

8.57.548DSMZ 1732

Acids (g/L)Solvents (g/L)Glucose consumed(g/L)

Strain

6.015.553IFP903

6.017.559DSMZ 6422

4.510.540IFP904

5.514.557DSMZ 6228

2.51541DSMZ 923

5.515.560DSMZ 1738

5.01662DSMZ 4685

7.51863DSMZ 1737

Acids (g/L)Solvents (g/L)Glucose consumed(g/L)

Strain

Solvents

Acids

Solvents

& Acids

ABE (4) – Screening of strains on xylose

CaCO3 : 2 g/L

2.40.37DSMZ 6423

2.51.19IFP 9046.52.635DSMZ 4685

4,814,147DSMZ 17313.513.545IFP 903

3.715.751DSMZ 6422

8,52,730DSMZ 17337,63,826,4DSMZ 17378,23,824DSMZ 1738

3,614,551,9DSMZ 17322,714,749,1DSMZ 6228

Acids (g.L-1)Solvents (g.L-1)xylose consumed (g.L-1)Strain

ABE (5) – Production on wheat strawhemicellulose hydrolyzate 1

Lignocellulosic hydrolysate(IFP ref: 1019)

• Concentrated wash water from steam-exploded wheat straw

• Pretreatment conditions: 18.5 bars for 2 min (after soaking in 0.04 M H2SO4).

Composition :Cellobiose: 1.2 g/LGlucose : 6.5 g/LXylose : 43.5 g/LGalactose: 5.5 g/LArabinose: 5.5 g/LMannose : 0.7 g/LAcetate : 0.6 g/L5-HMF : 132 mg/LFurfural : 4 mg/L

• A preculture was performed in a fermentor (4-L of culture medium) on glucose with C. acetobutylicum NCIB 8052 (DSMZ 1732)

• The culture on hydrolysate rapidly stopped (probably because of the inhibitors in the hydrolysate).

ABE (6) – Effect of lignocellulose degradation products

0.04ferulic acid

Growth inhibitionCoumaric acid

0.10Syringic acid

0.20Vanilline

0.05p-hydroxybenzoic acid

0.48Catechol

0.18Furfural

0.045-hydroxymethylfurfural

Relative productionCompound added ( at 1 g/L)

Strain used: DSMZ 6228 ; substrate: xylose at 60 g/LABE production with no added compound : 14.7 g/L

ABE (7) – Production on hydrolyzate 2 (a)

� Fermentation using lime-pretreated H1121 added at variousconcentrations to a synthetic medium and using various strains

Solvent production

0,00

2,00

4,00

6,00

8,00

10,00

12,00

14,00

0% 20% 40% 60% 80% 100% 0% 20% 40% 60% 80% 100% 0% 20% 40% 60% 80% 100%

ATCC 39057 DSMZ 1732 NCIB 8052

So

lven

t (g

/l)

EthanolAcétoneButanolSolvants totaux

EtOHAcetoneBuOHtotal solvents

ABE (8) – Production on hydrolyzate 2 (b)

0

2

4

6

8

10

12

14

16

18

20

0 10 20 30 40 50 60 70

Time (h)

pH

or

gas

pro

du

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(L/L

)

5,70

5,80

5,90

6,00

6,10

6,20

6,30

6,40

6,50

6,60

Gas

flow

(mL

/min

)

Volume (L/L) Flow rate[mL/min] pH

05

10

1520253035

404550

0 10 20 30 40 50 60 70 80

Time (h)

Res

idua

l glu

cose

or x

ylo

se (

g/L)

0,002,004,00

6,008,0010,0012,0014,00

16,0018,0020,00

Aci

ds

or S

olve

nts

(g/L

)

Residual Glucose (g/L) Residual Xylose (g/L) Total solvents (g/L) Total acids (g/L)

C. beijerinckii NCIB 8052

Culture time (h)

Total acids(g/L)

Total solvents

(g/L)

Total sugarsconsumed

(g/L)

Yabe/sugars(g/g)

solvent productivityg/L.h

70.00 3.2 17.5 50 0.35 0.25

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ABE – Separation (1)

• Extraction of solvents from acetone-butanol fermentation brothwith membranes (WUR)� Suitability of PerVaporation membranes for Acetone-butanol extraction� Suitability of Reverse Osmosis membranes for Acetone-butanol extraction� Fermentation with on-line extraction

• Extraction of alcools using rotating disc contactors (GIG)

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(g/l)

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acid

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Separation using Rotating disc contactors

• Rotating disc contactors (GIG)� Principle

� Mixtures of alcools� Mass transfer for water solutions of single and multiple components

Background Model - Based on Zanfir and Gavriilidis (2007) work

Rotating disc contactors: principle (1)

Chemical Reaction Engineering • Mass transfer • Heat transfer • Chemical conversions • Separation – reaction • Energy consumption

Biotechnology Issues

• Conversions efficiencies • Product purity • Adaptability to Bio-Processes • Ability for control • Flexibility to raw materials

Emission Capture

Processes addressed: • Removal of volatile products of fermentation ( ethanol, ABE – as model processes ) • Esterification of organic acids ( ethyl lactate production in pressurized RDC …? )

Rotating Disc Concept – Reaction – Separation Tool for Bioprocesses

Rotating disc contactors: principle (2)

Integration of two rotating disks

Experimental Units in use in GIG

Materials and geometry : polycarbonate discs ( D = 0,27 m ), volumes for liquid phase : 0,5 L ( small unit ) , 10 L ( large unit )

Rotating disc contactors (3)

Butanol Transfer in Rotating Discs System

Acetone Transfer in Rotating Disc System

Zanfir, Gavrilidis (2007) – to compare

Ethanol Transfer in Rotating Disc System

• Demonstration of the suitability of the system for ABE separation

• Comparison with stripping favorable to RDC

• Elaboration of a model for broad applications underway

Separation using Rotating disc contactors -conclusions

Comparison of rates of direct ethanol recovery by natural stripping, forced stripping and in rotating disc systems

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WP No. 3: Advanced biochemical conversion of biomass · Project BIOSYNERGY ... from biotechnology to fine chemistry – Side event November 17, 2010, Reims ... WP No. 3: Advanced

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