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1/23

First European Lignocellulosic Ethanol Conference, 13 15/10 2010, Copenhagen

Development of ethanol based lignocellulose biorefinery technology

Overview & results of the IP BIOSYNERGY (FP6)

R.R. Bakker, J.H. Reith, R. van Ree, R. Capote

Campos, P.J. de Wild, F. Monot, B. Estrine, A.V.

Bridgwater, A. Agostini, et al.


2/23

Integrated Project BIOSYNERGY

BIOmass for the market competitive and environmentally friendlySYNthesis of bio-products

chemicals and/or materials

together with the

production of secondary enERGY carriers transportation fuels, powerand/or CHP through the biorefinery approach.

EU FP6 Program: Contract No. 038994 SES 6. EC Officer: Silvia Ferratini.

Duration: 01-01-2007 31-12-2010 (48 months). Budget: 13.4 M, EC grant 7M

Development multiproduct cellulose-ethanol based biorefinery technology

Focus on valorisation of residues from cellulose ethanol production

Both Bioprocessing and thermochemical pathways combined

Process development from lab-scale to pilot-scale


3/23

7 Industry, 8 R&D Institutes and 2 Universitiesfrom 10 EU countries


4/23

Physical/chemical

Fractionation

Ligno-

cellulosic

biomass

Lignin

Hemicellulose

Cellulose EnzymaticHydrolysis Fermentation

Chemical

conversion

Ethanol

HMF > 2,5 FDCA

Furfural

SurfactantsC5-sugars

SC-depolymeri-

sation

Catalytic

pyrolysis

Chemical

conversion

Enzymatic

conversion

Fractionation

Phenolics

Activated l ignins

Resins / Thermosets

Integration in

petrochemical

refineries

C6-sugars

Processes and Product lines in the IP BIOSYNERGY

CHPHeat & Power to

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

Multi-product biorefinery, focus on residues cellulose ethanol: C5 and l ignin valorisation

Aqua-

thermolysis

ABE

Xylonic acid

Pretreatment


5/23

Advanced physical/chemical fractionation Major cost factor in biorefinery

Model feedstocks: wheat straw, woods

Processes studied Mechanical/Alkaline Fractionation (MAF; A&F)

Ethanol/water Organosolv (ECN)

Organic acid organosolv (Avidel process; ARD)

Acid hydrolysis (Biorefinery.de) Reference technology: steam explosion (ABNT)

Ethanol/H2O Organosolv,ECN Mech/alk pretreatment FBR Acid organosolv ARD


6/23

Results Lignocellulosic biomass fractionation

All studied routes lead to significant fractionation of C5,C6 sugars and lignin from lignocellulose. Processes can be optimised toward a particular goal, forexample:

High enzymatic degradability of the cellulose fraction Hemicellulose hydrolysis for further processing of C5

Recovery of a high quality lignin stream

Review and results benchmark to be published

Lignin products from Organosolv Fractionation (ECN)


7/23


8/23

Fermentation routes: ABE

Results (IFP, WUR-FBR)

Final conc solvents (ABE) :

17,6 g/L

Continuous fermentation is

still a challenge

ABE separation from

fermentation broth wasdemonstrated

0

5

10

15

20

0 10 20 30 40 50

Time (h)

Conc(g/l)

SolventsAcetic acidButyric acid5-HMFFurfural

ABE

Acetone, Butanol, Ethanol

Aim

ABE production from hemicellulose hydrolyzates of wheat straw


9/23

Fermentation routes: Xylonic acid

Xylonic acid

Applications: Dispersant, esters, lactones (cyclic esters)

Aim

Xylonic acid production from fermentation of xylose (C5-sugar)

S

ources

Acid-hydrolyzed DDGS (dried distillers grains with solubles)

Wheat straw C5-sugar hydrolysates

Results

Successful fermentation results in batch and continuous cultures

(VTT)Toivari, M.H., Ruohonen, L., Richard, P., Penttil, M., Wiebe, M.G.

(2010) Saccharomyces cerevisiae engineered to produce D-xylonate.

Applied Microbiology and Biotechnology 88: 751-760.


10/23

Chemical conversion routes: HMF

2,5 FDCA

HMF (hydroxymethylfurfural)

Applications:

Potential building block for conversion to monomers (eg

2,5-FDCA) for bulk polyesters (eg PET) and polyamides

Aim

HMF production from glucose (C6) dehydration

Oxidation of HMF to 2,5-furandicarboxylic acid (2,5-FDCA)

Results

Substantial yield improvement of HMF by using ionic liquids (Bioref)

High yield (> 90%) conversion of HMF to 2,5-FDCA (Bioref/ WUR)

Application testing 2,5 FDCA-derived polymers promising results (DOW)
http://en.wikipedia.org/wiki/File:2,5-Furandicarboxylic_acid.png


11/23

Chemical conversion routes: furfural

Aim

Analysis kinetics furfural synthesis from xylose Modelling to improve furfural production process

Results

Yield improvement > 85% (TU Delft)

Chemical building

block

Route from

furfural

World production

(t/a)

Biobased world

production (t/a)

Furfural -See biobased

production200.000-300.000

Furfuryl alcoholHydrogenation of

furfural120.000-180.000 -

Tetrahydrofurfuryl

alcohol

Hydrogenation of

furfuryl alcohol-

Tetrahydrofuran

(THF)

Hydrogenation of

furfural1 200.000

2-

Maleic anhydrideRing cleavage offurfural

-

Maleic acidHydrolysis of

maleic anhydride-

Furfural

Applications

Chemical building blocks

Resins, adhesives

Marcotullio, G. and W. de Jong, Green Chemistry (2010)


12/23

Chemical conversion routes: surfactants

Aim

Production ofgreensurfactants atcompetitive price level (~1500 /ton)

Results

Short tail surfactants prepared from straw

derived unpurified pentose syrups (ARD)

Xylose

syrup AVIDEL

syrup ABNT PWS

Syrup

Decyl Pentosides

Isoamyl Pentosides

Butyl Pentosides

0,0

10,0

20,0

30,040,0

50,0

60,0

70,0

80,0

90,0

100,0

%

Yields

Yields of alkyl pentosides obtained for three

pentose syrups and for 3 types of alcohols.

C5-sugar based surfactants

Route:

C5-sugars + fatty alcohols (ROH) C:4 -

C:18


13/23

Lignin valorization

Lignin

Lignin contains numerous valuable aromatic (phenolic) structures Valorisation to products improves carbon footprint

and revenue

of

the biorefinery

Technologies

Combustion for heat and/or power (main application to date)

Gasification for syngas

Hydroliquefaction for transportation fuels (reformulated gasoline) Direct application of lignins in resins*

Enzymatic processing (laccases) to improve reactivity*

Pyrolysis for chemicals, performance products and fuels*


14/23

Absorbance(a.u.)

Time/min

Absorbance(a

.u.)

4 6 8 10 12 14

Time/min

4 6 8 10 12 14Time/min

30 32 34 36 38 40 42 44 46 48 50

30 32 34 36 38 40 42 44 46 48 50

Absorbanc

e

(a.u.)

Absorbance

(a.u.

)

Time/min

Column: Toyopearl HW-55F 500 (A&F)


Column:Hydrogel 2000 + 250 + 120 (VTT)


Solid

Liquid

Absorbance(a.u.)

Time/min

Absorbance(a

.u.)

4 6 8 10 12 14

Time/min

4 6 8 10 12 14Time/min

30 32 34 36 38 40 42 44 46 48 50

30 32 34 36 38 40 42 44 46 48 50

Absorbanc

e

(a.u.)

Absorbance

(a.u.

)

Time/min

Absorbance(a.u.)

Time/min

Absorbance(a

.u.)

4 6 8 10 12 144 6 8 10 12 14

Time/min

4 6 8 10 12 144 6 8 10 12 14Time/min

30 32 34 36 38 40 42 44 46 48 5030 32 34 36 38 40 42 44 46 48 50

30 32 34 36 38 40 42 44 46 48 5030 32 34 36 38 40 42 44 46 48 50

Absorbanc

e

(a.u.)

Absorbance

(a.u.

)

Time/min





Solid

Liquid

Lignin conversion

Supercritical depolymerisation (WUR-FBR)

Aim: Lignin depolymerisation

in supercritical CO

2Result:

Improved yields

Functional lignin derivatives: l ignin activation (VTT)

Aim: Improvement of reactivity to enhanceproduct options

Result: Successful enzymatic lignin modification

by Trametes hirsuta laccasesPhenol substitution (Chimar)

Aim: Phenol substitution in PF resins for particle board applications

Result:

25% substitution by (organosolv) lignins

ThL treated lignin

Raw l ignin

Control lignin


15/23

Pilot scale production of wood-based panels

Particleboards produced with PF resins where phenol

was replaced by ARD

lignin at various levels

PF std

PFL-15% Ph sub.

PFL-25% Ph sub.

PFL-35% Ph sub.

PFL-45% Ph sub

Step of plywood

panels production.

Testing of

plywood at

CHIMAR

premises

Plywood panels


16/23

Catalytic pyrolysis of biomass

Improve quality of fast pyrolysis

oil (filtration, dewatering)

Fractionation of bio-oil into enriched fractions suitable for resins and

wood preservatives

80-250 kg/hrrotating cone fast

pyrolysis

pilot plant at BTG


17/23

Biomass-to-products chain design

Aim

Identification of the most promising biorefinery chains for the EUResults

Modelling

tool with modular structure developed (Aston)

Process synthesis and simulation (on-going)

Preliminary results

Biorefinery processes (ethanol + chemicals) have better

economic perspective than cellulose ethanol (ethanol + lignincombustion)

Aston, ECN, IFP, CRES, JR, JRC, Cepsa, ABNT.


18/23

Module structure (Aston)

Feed

Economics

Product B

Product A

Solidwaste

Liquid waste

Recovered condensate

Waste water

Stillage stream

Air emissions

CO2

others

Steam H2

SO4 H2

O NaOH Enzymes Yeast

Auxiliary material

Others

Electricity Heat

Auxiliary

energy

Module

Organic processresidues


19/23

Integration results in conceptual design biorefinery plant

Basic design for integral lignocellulose biorefinery plant at existing

cellulose ethanol site: AB BCyL

demonstration plant, Salamanca.

ABNT, Aston, ECN

BCyL cellulose ethanol demo plant ABNT,

Salamanca (Spain)

5 Million L EtOH/yr from 25,000 ton straw.

Operational since Oct. 2009.


20/23

Conclusions and perspectives (1)

BioSynergy RTD provides solid basis for valorization of

C5 sugars and lignin.o This fits in a cellulose ethanol-based biorefinery concepto

Several processes demonstrated on pilot scale in 2010

Fractionation technologies need to be optimized towarda particular goalo An integrated approach feedstock-process-endproduct istherefore required!


21/23

Conclusions and perspectives (2)

Lignin valorization to chemicals is an important tool for

economic profitability of the biorefinery and for improvingthe ecological footprint.

o

Direct application of lignin in resins (up to 25 wt% phenol

substitution)o Catalytic thermochemical processing (pyrolysis) of ligninto phenolicso Enzymatic lignin conversion to improve reactivity

Biorefinery of lignocellulose to ethanol + chemicals +CHP shows better economic perspectives thanproduction of only cellulose ethanol + CHP.


22/23

Thank you for your attention!

More information: Hans Reith, coordinator IP BIOSYNERGY

+31-(0)224-564371, [email protected]

Public Workshop

Development of multi-product lignocellulose biorefinerytechnology - Results of the Integrated Project BIOSYNERGY -

Wednesday November 17th 2010, 13:00 17:30

Hotel de lUnivers, Reims, France

See program at website : www.biosynergy.eu(Side event of the Conference:

Biomass derived pentoses: from biotechnology to fine chemistry

14-16 November 2010; Reims, France (FR)
mailto:[email protected]://www.biosynergy.eu/http://www.biosynergy.eu/mailto:[email protected]


23/23

Potential applications of lignin-derived phenolics

Biobased plastics Fuel addit ives

BTX

Binders Bio-bitumen

Carbon Fiber (for CF

composites)

Specialty phenolics in

high-value applications

Fragrances

Pharmaceuticals

Wood-adhesives and resins

Epoxies

Polyolefins

Documents

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