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

Integrated Project BIOSYNERGY

BIOmass for the market competitive and environmentally friendly SYNthesis of bio-products chemicals and/or materials together with the production of secondary enERGY carriers transportation fuels, power and/or CHP through the biorefinery approach.

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

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

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

Processes and Product lines in the IP BIOSYNERGY

Multi-product biorefinery, focus on residues cellulose ethanol: C5 and lignin valorisation
Cellulose
Enzymatic Hydrolysis

C6-sugars

Fermentation

Ethanol ABE

Lignocellulosic biomass

Xylonic acid

Hemicellulose
Physical/chemical Fractionation

HMF > 2,5 FDCA

C5-sugars

Chemical conversion

Furfural Surfactants Phenolics

Pretreatment

Lignin
Aquathermolysis

SC-depolymerisation

Chemical conversion Enzymatic conversion

Activated lignins Resins / Thermosets Integration in petrochemical refineries Heat & Power to process

Catalytic pyrolysis

Fractionation

Biomass residues

CHP

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

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, for example:
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)

Thermo-chemical fractionation: Hybrid staged de-gasification

65 solid residue (dry) 100 WHEAT STRAW (dry) AQUATHERMOLYSIS 35 aquathermolysate (FAST) BFB PYROLYSIS 6 gas 20 char 39 bio-oil

58 FUELS

7 furfural 28 WASTE WATER (for anaerobic digestion)

28 diluted aqueous solution of acids, sugars, extractives, ash, etc.

14 CHEMICALS

7 levoglucosan
32 residual oil containing water, acids, C2-C4 oxygenates, anhydrosugars, phenolics, ash, etc.

Results (ECN, Aston, BTG) Proof of concept sequential thermal decomposition

Fermentation routes: ABE ABE

Acetone, Butanol, Ethanol Aim ABE production from hemicellulose hydrolyzates of wheat straw Results (IFP, WUR-FBR) Final conc solvents (ABE) : 17,6 g/L Continuous fermentation is still a challenge ABE separation from fermentation broth was demonstrated
20
Solvents Acetic acid Butyric acid 5-HMF Furfural

15 Conc (g/l)

10

0 0 10 20 Time (h) 30 40 50

Fermentation routes: Xylonic acid Xylonic acid

Applications: Dispersant, esters, lactones (cyclic esters) Aim Xylonic acid production from fermentation of xylose (C5-sugar) Sources 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.

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)

Chemical conversion routes: furfural Furfural

Applications Chemical building blocks Resins, adhesives
Chemical building block Furfural Route from furfural Hydrogenation of furfural Hydrogenation of furfuryl alcohol Hydrogenation of furfural1 Ring cleavage of furfural Hydrolysis of maleic anhydride 200.0002 World production (t/a) See biobased production 120.000-180.000 Biobased world production (t/a) 200.000-300.000

Furfuryl alcohol Tetrahydrofurfuryl alcohol Tetrahydrofuran (THF) Maleic anhydride

Maleic acid

Aim Analysis kinetics furfural synthesis from xylose Modelling to improve furfural production process Results Yield improvement > 85% (TU Delft)
Marcotullio, G. and W. de Jong, Green Chemistry (2010)

Chemical conversion routes: surfactants C5-sugar based surfactants

Route: C5-sugars + fatty alcohols (ROH) C:4 - C:18

% Yields

Aim Production of green surfactants at competitive price level (~1500 /ton) Results Short tail surfactants prepared from straw derived unpurified pentose syrups (ARD)

100,0 90,0 80,0 70,0 60,0 50,0 40,0 30,0 20,0 10,0 0,0 Xylose syrup AVIDEL syrup

Butyl Pentosides Isoamyl Pentosides

Decyl Pentosides ABNT PWS Syrup

Yields of alkyl pentosides obtained for three pentose syrups and for 3 types of alcohols.

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*

Lignin conversion
Supercritical depolymerisation (WUR-FBR) Aim: Lignin depolymerisation in supercritical CO2 Result: Improved yields Functional lignin derivatives: lignin activation (VTT) Aim: Improvement of reactivity to enhance product options Result: Successful enzymatic lignin modification by Trametes hirsuta laccases
Absorbance (a.u.)
Absorbance (a.u.)

ThL treated lignin Control lignin Raw lignin

Solid

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

8
Time/min

10

12

14

Column: Hydrogel 2000 + 250 + 120 (VTT) 44 46 48 50

30

32

34

36

38

40 42 Time/min

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

Absorbance (a.u.)

Absorbance (a.u.)

Liquid
4 6 8
Time/min

10

12

14

Column: Hydrogel 2000 + 250 + 120 (VTT)

Phenol substitution (Chimar) Aim: Phenol substitution in PF resins for particle board applications Result: 25% substitution by (organosolv) lignins
30 32 34 36 38 40 42 Time/min 44 46 48

50

Pilot scale production of wood-based panels

PF std PFL-15% Ph sub. PFL-25% Ph sub. PFL-35% Ph sub. PFL-45% Ph sub
Particleboards produced with PF resins where phenol was replaced by ARD lignin at various levels

Testing of plywood at CHIMAR premises

Step of plywood panels production.

Plywood panels

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/hr rotating cone fast pyrolysis pilot plant at BTG

Biomass-to-products chain design

Aim Identification of the most promising biorefinery chains for the EU Results 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 + lignin combustion)

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

Module structure (Aston)

Auxiliary material Steam H2SO4 H2O NaOH Enzymes Yeast Others

Feed Auxiliary energy

Liquid waste Recovered condensate Waste water Stillage stream

Product A

Module

Product B Economics

Solid waste

Air emissions CO2 others

Organic process residues Electricity Heat

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.

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 concept o Several processes demonstrated on pilot scale in 2010 Fractionation technologies need to be optimized toward a particular goal o An integrated approach feedstock-process-endproduct is therefore required!

Conclusions and perspectives (2) Lignin valorization to chemicals is an important tool for economic profitability of the biorefinery and for improving the ecological footprint. o Direct application of lignin in resins (up to 25 wt% phenol substitution) o Catalytic thermochemical processing (pyrolysis) of lignin to phenolics o Enzymatic lignin conversion to improve reactivity Biorefinery of lignocellulose to ethanol + chemicals + CHP shows better economic perspectives than production of only cellulose ethanol + CHP.

Thank you for your attention!

More information: Hans Reith, coordinator IP BIOSYNERGY +31-(0)224-564371, reith@ecn.nl

Public Workshop Development of multi-product lignocellulose biorefinery technology - 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)

Potential applications of lignin-derived phenolics

Biobased plastics Wood-adhesives and resins Fuel additives BTX Binders Bio-bitumen

Carbon Fiber (for CF composites) Epoxies Polyolefins Specialty phenolics in high-value applications Fragrances Pharmaceuticals