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LIGNOCELLULOSICS-DERIVED CARBOHYDRATES AS
PLATFORM MOLECULES FOR THE PRODUCTION OF
BIOFUELS AND BIOBASED PRODUCTS
Isabella De Bari
ENEA CR TRISAIA, ITALYItalian Representative Task IEA 42
Intertasks Workshop andItalian stakeholders meeting on biorefineries, Sassari, 5 May 2015
� Test fields of energy crops� Thermochemical processes� Advanced biofuels� Biorefineries and green
chemistry
Combustion technologies
� Microalgae growth, � Anaerobic processes
to CH4 and H2
� Energy crops
ENEA’s research centres working on bioenergy/biorefineries
LCA – Anaerobic digestion
ITALIAN BIOMASS AVAILABILITY
agricultural area was reduced by 28% in 40 years from 18 million hectares to 13 (abandonment and cementification)
The forest area has increased in 40 years of 100% from 5.5 to 11 million hectares
A recent analysis is detailed in the Sector Plan for Bioenergy (5 August 2014)
by the Permanent Conference for relations between the State, the Regions and
the Autonomous Provinces
The estimated annual potential of
residual biomass amounts to about
30 million tons (dry matter) ≈10
Mtoe.
The agricultural areas for dedicated
crops are less than 200,000 hectares
but could be increased by 5 times
without conflicting with food
production.
Dedicated crops for biofuels and biobased products
Giant reed(Arundo donax)
Lignocellulosic.residues fromCardoon
Glucan 34.75 35
Xylan 20.10 14
Galactan 0.27 1,7
Arabinan 2.12 2,2
Mannan 0 1,1
Lignin Klason 22.0 25
Ash 7.70 8,1
EtOH Extractives 10.22 4,1
BIOLYFE "Second BIOethanol process:
demonstration scale for the step of
LignocellulosichYdrolysis and Fermentation
SEEDS
VEGETABLE
OILS
METHODS TO DISSOLVE LIGNOCELLULOSICS
SUGARS PLATFORM� breakdown of the raw materials into sugars � fermentation,
dehydration, hydrogenation
METHODS to dissolve lignocellulosic feedstocks: acid hydrolysis, , and
liquefaction in ionic liquids.
IMPROVING THE PERFORMANCES
THE MAIN STEPS IN THE BIOCHEMICAL ROUTE
12
3
BIOMASS
HYDROLYZATE
1. Optimizazion of the pretreatment2. Development of high gravity bioprocesses3. Biomass derived sugars�fermentation, dehydration, hydrogenation….6
PRETREATMENT
ENZYMATIC
HYDROLYSIS
ENEA’S TECHNOLOGIES FOR THE BIOMASS PRETREATMENT
ENEA’ CONTINUOS PLANT (300 kg/hr)
ENEA’ BATCH PLANT
Few % of additives �catalyses the process at milder conditions / affects the biomass
fractionationsBIOMASS+ ACIDS Hemicellulose mostly
hydrolized to monomers
I.e. Monomer sugars for fermentation, or dehydration
BIOMASS + BASES Hemicellulose mostly
olygomeric
I.e. olygomeric sugars to
produce barrier films
BIOMASS PRETREATMENT AND FRACTIONATION
WOODWaste paper
STRAW
ARUNDO
DONAX
GRAPE STALKS
HEMICELLULOSE
LIGNIN (residual
sugars ≈ 2%)
CELLULOSE
(≈80%)
PRETREATMENT FRACTIONATIONATION
Plant size 300 kg/h
Lignocellulosic biomass
Process severity
CELLULOSE HYDROLYSIS YIELD
(LOW SOLIDS LOADING)
time
Temperature
PRETREATMENT OF WOODY BIOMASS (ASPEN CHIPS)
Before
After
ACID-CATALYZED STEAM PRETREATMENT OF ARUNDO
DONAX [1,4%WT]
C5
REC
OV
ER
Y:
70
%
T[°C], t(min)
Klason
lignin ARABINAN Galactan Glucan Xylan
% COMPOSITION OF THE WATER-INSOLUBLE FRACTION
196°C+acid 27.1 0.69 0.21 36.0 8.6
200°C+acid 25.7 0.50 0.20 35.1 6.0
205°C+acid 23.5 0.52 0.18 34.9 4.8
210°C+acid 23.0 0.40 0.120 33.7 3.5
% OF SOLUBLE CARBOHYDRATES
196°C+acid 0.55 0.31 1.70 6.0
200°C+acid 0.80 0.40 2.4 9.5
205°C+acid 0.63 0.36 2.5 5.2
210°C+acid 0.51 0.25 1.7 4.3
Level of microbial inhibitors
4-HBAa
(mg/kg)
SYRb
(mg/kg)
5-HMFb
(mg/kg)
2-FURd
(mg/kg)
CATe
(g/kg)
F. acidf
(g/kg)
A. acidg
(g/kg)
196°C+acid 64 77 86 538 2.9 4 8.5
200°C+acid 112 77 128 747 4.9 7 15.6
205°C+acid 98 47 86 700 5.3 7.1 18
210°C+acid 194 126 35 954 1.4 8.4 23.9
a 4-hydroxybenzaldehyde. b Syringaldehyde. c 5-(Hydroxymethyl)furfural. d 2-Furaldehyde. e catechol. f formic acid. g acetic acid
The effect of these degradation products on the hydrolizates
fermentability will depend on the microorganism and process
set-up(inoculum size, pH, and process strategy)
HIGH GRAVITY HYDROLYSIS
• Effect of the pretreatment on the biomass hydrolizability
• High gravity hydrolysis of biomass • Hybrid simultaneous saccharification and
fermentation
High gravity hydrolysis = process in which the solids content is above 20%
High gravity hydrolyis
30
50
70
90
0 10 20 30
s/L [%]
xylo
se y
ield
, %
%
20
40
60
80
100
0 10 20 30s/L [%]
glu
cose
yie
ld [
%] 144 hr 48 hr
The Challenges of high gravity hydrolysis: �High viscosities � mass transfer limitations� poor mixing
�Inhibition by end-products
The Challenges of high gravity hydrolysis: �High viscosities � mass transfer limitations� poor mixing
�Inhibition by end-products
The Challenges of high gravity fermentation: � High concentration of microbial inhibitors� Osmotic stress due to high solutes concentration� Toxic effect of ethanol (synergistic inhibition)
EFFECT OF HIGH SOLIDS CONTENT ON THE BIOMASS HYDROLYSIS
Research activities
1.Investigate bioreactor geometries suitable for the processing of concentrated slurries
2.Optimize the bioreactor feeding strategies (bach , fed-batch)
3.Optimize the use of enzymatic mixtures (dosage, effect of auxiliary components, effect of surfactants)
4.Find the optimal process strategy (SSF, SHF, hybrid process)
5.Reduce the hydrolyzates toxicity to the fermentation microrganisms and to grow resistant microrganisms
EFFECT OF THE MIXING
1 2
3
Mixing in shaken flasks and bioreactor (1 and 2)
Arundo fiber, 20% solids loading, 50° C.
pH 4.8 pH 5.5
MIXING GEOMETRY
0
20
40
60
80
100
120
0 25 50 75 100
Time [h]
Glu
cose
, [g
/L]
GRAVIMETRIC
MIXING STIRRED TANK
Gravimetric shaking in rotating drum system was much more effective (Arundo fiber)
Mixing in stirred bioreactor and gravimetric shaker (2 and 3)
HYBRID HYDROLYSIS AND FERMENTATION
SHF: separate hydrolysis and fermentation
SSF: simultaneous saccharification and fermentation
19
SSFbiomass
H-SSF : hybrid simultaneous
saccharification and fermentation
� Optimization depends on the subsequent
fermentation strategy (i.e. fermentation or
cofermentation, type of microrganism).
� the liquefaction time is an important variable.
Production of bioethanol through hybrid process
Enzyme dosage
[g/g biomass
DM] MicrorganismsProcess
TypeYeast
inoculation T [°C]
Ethanol
(%wt)
0,07 S. cerevisiae SHF B 32°C 3,5
0,07 S. cerevisiae SSF B 32°C 3,9
0,027 S. cerevisiae HSSF B 37°C 3,7
0,027 S. cerevisiae HSSF FB3 50-37°C 3,8
0,027 S. cerevisiae HSSF FB1 50-37°C 3,8
0,07 K. marxianus H SSF FB 2 50-32°C 4,7
0,07 K. marxianus H SSF B 32°C 4,4
0,07 S. cerevisiae HSSF FB1 50-37°C 4,2
0,07 S. cerevisiae HSSF B 37°C 4,2
0,07 S. cerevisiae H SSF B 32°C 4,6
0,07 S. cerevisiae H SSF FB 2 50-32°C 5,0
B=batch; FB= Fed-Batch
Inhibitor Conc.
(g/L)
Yeasts Strain
Reduction of
ethanol yield (%)
Reduction of of ethanol
productivity (%)
5-HMF 4 S.cerevisiaeTembec T1
12 45
5-HMF 4 S.cerevisiaeCBS 8066
40
5-HMF 4 S.cerevisiaeY-1528
11 40
Furfural 4 S.cerevisiaeCBS 8066
69
Furfural 1.6 S.cerevisiaeTembec T1
27
Furfural 1.6 S.cerevisiaeY-1528
25
Acetic acid
4.3 S.cerevisiae 50
Aceticacid
8 P.stipitis 98
Microorganisms inhibition thresholds
Value
added
product
Microrganism Inhibition
threshold
Butanol Clostridium
beijerinckii
Xylitol Candica
Tropicalis
Lactic acid Lactobacillus
acidophilus
Biosuccinic
acid
Actinobacillus
succinogenes
Tryacyl-
glycerides
Cryptococcus
curvatus
………………
…..
………………………
…….
………………
…
…………………….
Microorganisms resistance to the biomass degradation products is an important requirement
for the conversion of lign. cellulosic derived carbohydrates to biobased products
PRODUCTION OF CLEAN SUGARS
� ION-EXCHANGE RESINS
� OVERLIMING
� STEAM STRIPPING
� ……………….
Hydrolyzates detoxyfication is sometime necessary to increase the microbial conversion efficiency
ADAPTATION
Fermentation
Detoxification =rimoval of degradation by-products (i.e. organic acids, furan
compounds, phenols)
Pretreated biomass/hydrolyzates
22
� MICROBIAL ADAPTATION
� FERMENTATION AT HIGH CELLS CONCENTRATION (IMMOBILIZATION)
Microbial adaptation
23
FERMENTATION WITH CO-IMMOBILIZED CELLS OF S. Cerevisiae and P. stipitis
Yeast(s) conditions
Process scheme P/S
% xylose consumption at
maximum ethanol
% glucose consumption at ethanol maximum Y%
COF 4 16 100 68COF 4 16 100 66COF 0,25 16 100 64COF 0,25 16 100 63COF 20 97 68COF 17 100 60COF 17 93 56COF 33 100 61COF 31 100 53COF 34 100 51COF 67 100 49COF 4 34 100 72COF 4 42 100 80COF 0,25 41 100 64COF 0,25 33 100 71SEQ 10^9 [S] 1,36x10^9 [P] 4 73 100 61
SEQ 10^9 [S] 5x10^9[P] 4 39 100 69
P. and S. adapted +
EtOH
Beads uptake
1,25,E+09P. adapted up to 40%
WILD4,70E+08
6,80E+08
P. adapted up to 40% (repeated
cycles)
3,25E+06
3,70E+07
4
COF= cofermentation
SEQ= sequential fermentation 24
EUROPEAN PROJECTS ON 2G BIOETHANOL
Project Main Partners
5FP BIO-H2: Production of clean hydrogen for fuel
cells by reformation of bioethanol
CR FIAT, ECN, Un. Patrasso,
Queens, CNRS, Peugeot, Renault
BIOPAL “Algae as raw material for production of
bioplastics and biocomposites contributing to
sustainable development of european coastal
regions”
CEVA, FIAT, Un. Pisa,
DEMOKRITOS, OWS
TIME “Technological Improvement for ethanol
production from lignocellulose”
VTT, Un. Lund, Roal, Un. Budapest,
Nedalco,
7FP BIOLYFE "Second BIOethanol process:
demonstration scale for the step of
LignocellulosichYdrolysis and Fermentation"
Biochemtex, ENEA, Novozymes,
Lund University, IFEU, WIP
Running (7FP) GRAIL “Glycerol Biorefinery Approach for the
Production of High Quality Products of Industrial
Value”
IUCT, ENEA, In.Bio-Consorzio,
STUBA, Megara, Biozoon, CENTIV,
DBFZ, Universidad Valparaíso, PI,
SINTEF, Queen’s University Belfast,
Aalborg University
Italian projects on biofuels/biobased
productsFunding
Ministry
Project
acronymFULL TITLE
MIPAAF MULTISORGO Integrated production of bioethanol and biogas
from sweet sorghum: technological, economic, energy and
environmental aspects
FITOPROBIO Phytodepuration treatments using cellulosic biomass to obtain
second generation ethanol"
BIOSEGEN Innovative chain for the production of second generation
biofuels from agricultural and agro-industrial
residues and biomass crops.
MSE
INDUSTRIA
2015
PRIT Development of an Italian pretreatment technology for the
production of second generation bioethanol (COORDINATED BY
BIOChemtex)
MIUR BIT3G
REBIOCHEM
ALBE
research activities within the green chemistry cluster -spring
ENEA, University of Salerno, Department of Industrial Engin eering(A. Giuliano, D. Barletta)
Process Flowsheet Analysis and Synthesis
for a Lignocellulosic Biorefineryproducing ethanol and biobased
products
Lignocellulosic Biorefinery Flowsheet: base case
BIOMASS PROCESS PROCESS ENERGY PRODUCTS
BIOMASS STEAM
EXPLOSION
ENZYMATIC
HYDROLYSISETHANOL
FERMENTATION
ETHANOL
DISTILLATION AND
PURIFICATION
LIGNIN
COMBUSTION
WASTE WATER
TREATMENT
HEMICELLULOSE
UPGRADING AND
FERMENTATION
LIGNIN
WASTE
WATER BIOGASHEMICELLULOSE
RICH
0,00
0,20
0,40
0,60
0,80
1,00
1,20
1,40
1,60
1 2 3 4 5
*PSPEnzyme in situ
/PSPBaseProcess
Enzyme price (€/kg)
Sensitivity on enzyme price
Xylitol is a platform molecule
Scenario with xylitol co-production
BIOMASS PROCESS PROCESS ENERGY PRODUCTS
BIOMASS STEAM
EXPLOSION
ENZYMATIC
HYDROLYSISETHANOL
FERMENTATION
ETHANOL
DISTILLATION AND
PURIFICATION
LIGNIN
COMBUSTION
WASTE WATER
TREATMENT
LIGNIN
WASTE
WATER BIOGASHEMICELLULOSE
RICH WASTE
WATER
HEMICELLULOSE
UPGRADING AND
FERMENTATION
PRELIMINARY ESTIMATIONS FROM OUR EVALUATIONS
Furans are platform molecules
Source: ( Angew 2007)
O
O
H
O
OCH3
O
O
OH
O
HO
O
Polymer
Biofuel
Fine chemical
Furfural
O
O
HHO
5-Hydroxymethylfurfurfual
O
O
H
Furfural
Scenario with furfural co-production
BIOMASS PROCESS PROCESS ENERGY PRODUCTS
BIOMASS STEAM
EXPLOSION
ENZYMATIC
HYDROLYSISETHANOL
FERMENTATION
ETHANOL
DISTILLATION AND
PURIFICATION
LIGNIN
COMBUSTION
WASTE WATER
TREATMENT
LIGNIN
WASTE
WATER BIOGASHEMICELLULOSE
RICH WASTE
WATER
PRELIMINARY ESTIMATIONS FROM OUR EVALUATIONS
COMPARISONC5 XYLITOL/FURFURAL
SCENARIO 1 2
Main Product Ethanol Ethanol
Co-Product Xylitol Furfural
Payback selling price for the co-product through our simulation(€/kg)
2 3
Estimated market price (€/kg)* 3.5 0.9-1.3
Tot Yield (tPRODUCTS/tBIOMASS ) 25 % 24 %
Electricity balance(MWPROD – MWCONS)
8.1 -4.7 (heat integration is
necessary)
Required Steam (t/h) 84 122
Succinic Acid is a platform molecule
HEMICELLULOSE
UPGRADING AND
FERMENTATION
Scenario with succinic acid co-production
BIOMASS PROCESS PROCESS ENERGY PRODUCTS
BIOMASS STEAM
EXPLOSION
ENZYMATIC
HYDROLYSISETHANOL
FERMENTATION
ETHANOL
DISTILLATION AND
PURIFICATION
LIGNIN
COMBUSTION
WASTE WATER
TREATMENT
LIGNIN
WASTE
WATER BIOGASHEMICELLULOSE
RICH
SUCCINIC ACID
FERMENTATION
SUCCINIC ACID
PURIFICATION
SUCCINIC ACID
CO2
PRELIMINARY ESTIMATIONS FROM OUR EVALUATIONS
WASTE
WATER
Scenario with succinic acid and xylitol co-production
BIOMASS PROCESS PROCESS ENERGY PRODUCTS
BIOMASS STEAM
EXPLOSION
ENZYMATIC
HYDROLYSISETHANOL
FERMENTATION
ETHANOL
DISTILLATION AND
PURIFICATION
LIGNIN
COMBUSTION
WASTE WATER
TREATMENT
LIGNIN
WASTE
WATER BIOGASHEMICELLULOSE
RICH
SUCCINIC ACID
FERMENTATION
SUCCINIC ACID
PURIFICATION
SUCCINIC ACID
CO2
PRELIMINARY EVATUATIONS FROM OUR ESTIMATIONS
Scenario with succinic acid/furfural co-production
BIOMASS PROCESS PROCESS ENERGY PRODUCTS
BIOMASS STEAM
EXPLOSION
ENZYMATIC
HYDROLYSISETHANOL
FERMENTATION
ETHANOL
DISTILLATION AND
PURIFICATION
LIGNIN
COMBUSTION
WASTE WATER
TREATMENT
LIGNIN
WASTE
WATER BIOGASHEMICELLULOSE
RICH
SUCCINIC ACID
FERMENTATION
SUCCINIC ACID
PURIFICATION
SUCCINIC ACID
CO2
WASTE
WATER
PRELIMINARY ESTIMATIONS FROM OUR EVALUATIONS
Scenario with ethanol+succinic acid co-production:COMPARISON C5 ETHANOL/XYLITOL/FURFURAL
SCENARIO 1 2 3
Main Product Ethanol Ethanol Ethanol
Co-Products Succinic Acid Succinic Acid + Xylitol
Succinic Acid + Furfural
Payback selling price for the co-product (RED) through our simulation (€/kg)
5.4 2.6 3.5
Estimated market price (€/kg)*
2.7 3.5 0.9-1.3
Tot Yield (tPRODUCTS/tBIOMASS ) 23 % 24 % 24 %
Electricity balance(MWPROD – MWCONS)
-4.1 -5.2 -5.5
Required Steam (t/h) 129 129 159
The biorefinery is no longer self sufficient for the energy need. A detailed LCA is necessary
40
Concluding remarks
CHALLENGES
Capitalization of the knowledge developed in the sector of biofuels for
the maximum exploitation of the “biomass barrel”.
� Optimize multi-products biorefineries by improving the existing
pioneering technologies
� Develop new processes for the conversion of side streams from
lignocellulosic biorefineries
� Improve the process integration
ENEA’s FACILITIES FOR BIOREFINING
41
� Pretreatment and fractionation at pilot scale
(300 kg/h)
� Production of second generation sugars
� Process scale up/downstream processing
� Technological platforms for thermal valorization
of biomass residues (pyro-gasification
� Identification of new proteins and key enzymes
involved in specific substrate degradation
/biomass degradation (proteomics) RECENT ACTIVITIES
� Fully equipped analytical labs for materials
characterization and process analysis
THANKS FOR YOUR ATTENTION
isabella.debari@enea.it
+39 0835974313
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