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7/28/2019 6 Biorefineries Bakker
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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.
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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
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7 Industry, 8 R&D Institutes and 2 Universitiesfrom 10 EU countries
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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
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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
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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)
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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
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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.
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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.png7/28/2019 6 Biorefineries Bakker
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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)
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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
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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*
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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: Toyopearl HW-55F 500 (A&F)
Column:Hydrogel 2000 + 250 + 120 (VTT)
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
Column: Toyopearl HW-55F 500 (A&F)
Column: Toyopearl HW-55F 500 (A&F)
Column:Hydrogel 2000 + 250 + 120 (VTT)
Column:Hydrogel 2000 + 250 + 120 (VTT)
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
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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
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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
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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.
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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
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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.
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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!
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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.
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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]7/28/2019 6 Biorefineries Bakker
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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