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FORTH/ICE-HT
WP1: Optimisation of oil crops
agronomy and oil yield and
utilisation of by products
Leading partner: FORTH
24 April 2009, Foggia, Italy
Optimisation of oil crops agronomy and
oil yield and utilisation of by products
• Objectives
– how to increase the yield of appropriate crops and the
added value of the by products
– what novel technologies have been developed to
harvest/pre-treat/fractionate oil-rich crops
– what products can be derived from harvesting
byproducts and biorefinery schemes
– input to WP4 and WP5-6
• Partners: CETIOM, FERA, CJ Co , UYork,
FORTH, DTU, INPT, Biorefinery.de
Tasks
• Task1: how to improve yields of vegetable oil and total biomass
(FERA and CETIOM)
• Task2: Cost and impact of harvesting (CETIOM)
• Task3: What is the pelletisation impact on the cost and processing
(CJ & Co )
• Task 4: Extraction of high value chemicals (UYork)
• Task 5: Biomethane from oil-rich crops straws (FORTH)
• Task 6: Ethanol and biogas production (DTU)
• Task 7: Biomaterials production (INPT)
• Task 8: Levulinic acid production (Biorefinery.de)
Speakers
• F. Flénet, A. Quinsac – CETIOM: “Identification of most
promising strategies to increase oil and biomass yield of
sunflower in European Union”
• David Turley, Ruth Laybourn - FERA: “Improving the
production and yield of oilseed rape”
• Ray Marriott – Green Chemistry (Centre of Excellence), UYork:
“Extraction of High Value Chemicals”
• K. Stamatelatou, G. Antonopoulou, G. Lyberatos – FORTH
“Anaerobic digestion of residues from oil-rich crops”
• J. Woodley – DTU: “Methods of pretreatment, hydrolysis, and
fermentation of lignocellulosic fraction for ethanol production
and subsequent biological treatment of the remaining biomass
for methane production”
• A. Rouilly, C. Vaca-Garcia - INPT : “Biomaterials production”
• B. Kamm - Biorefinery.de : “Levulinic acid production”
Identification of most promising
strategies to increase oil and
biomass yield of sunflower in
European Union
F. Flénet, A. Quinsac
24 April 2009, Foggia
Introduction
• Sunflower is the second most important oilseed crop in
UE, but the area has decreased
• Sunflower is mainly cultivated in Southern Europe :
Romania (900 000 ha in 2007), Spain (613 000 ha), Bulgaria (540 000
ha), France (537 000 ha), Hungary (470 000 ha) and Italy (130 000 ha)
• The strategies to increase seed yield were investigated :
– To increase the seed yield potential
– To decrease the effect of water stress, diseases and other limiting
factors
• Little information was available about oil content, and very
little information about biomass yield
• In this presentation, the main strategies are discussed
Strategy 1 : to increase the potential seed yield
(1)
• Potential seed yield increased by 40 % from 1970 to 2000, due to :
– An increase in harvest index
Year of official
registration
Mirasol
1978
Primasol
1979
Albena
1988
Vidoc
1989
Santiago
1993
Prodisol
1995
Melody
1996
LG5660
1998
Heliasol
2000
150
Harvest index (in % of the
variety ALBENA)
Varieties
Montpellier (2001 - 2002)
Toulouse (2002)
125
100
75
50
25
0
1975
1980
1985
1990
1995
2000
2005
Year of offical registration of the variety
(Results from Debaeke et al., 2004)
– A greater efficiency to intercept solar radiation per unit of leaf area
• No obvious increase in seed oil content was observed
Strategy 1 : to increase the potential seed yield
(2)
• Further improvements in seed yield potential are possible
– The main physiological processes explaining seed yield potential
are, in order of importance : 1st biomass allocation and light
interception through the canopy architecture; 3rd phenology
– No cultivars optimize all the physiological processes, hence
improvement are still possible
– Quantitative genetic methods such as QTL can be used to evaluate
the variability of these physiological processes, and to increase the
efficiency of breeding programs
Strategy 2 : to decrease the effect of water stress (1)
• Water stress is a major limiting factor
– Under water stress, sunflower is able to produce greater seed yields
than most other crops
– However, plant available water is the most limiting factor of
dryland agriculture in semiarid regions
– Sunflower is mainly cultivated without irrigation (96 % of the area
in France…), or with a limited amount of irrigated water
Strategy 2 : to decrease the effect of water stress (2)
• Strategies to decrease the effect of water stress
– To increase the drought tolerance of varieties
Crop models can be useful to test varieties and to identify the best physiological
characteristics
– To better adapt crop management to water availability
To optimize the choice of variety, date of sowing, planting density and N fertilizer,
depending on climate and soil water holding capacity
– To increase the irrigation of sunflower
If less water is available for agriculture, this crop with a low water requirement
could replace current irrigated crops
– To convince farmers to follow recommendations, because better cultural
practices would improve yields
For instance, in South-West of France there is a tendency to reduce the cost of
inputs, resulting in plant population densities below the recommendations in half of
the area…
Strategy 3 : to decrease the effect of diseases
(1)
• Some diseases are major liming factors
Main
diseases
Main countries
affected
Effects of the disease
Downy
mildew
All countries in EU
If entire areas are affected, the decrease in yield ranges from 50 %
(late development) to 100 % (early development) in the infected areas
Broomrape
Bulgaria, Romania,
Spain
In case of severe infections, losses can reach up to 50 % and near
100 %.
White rot
Bulgaria, France,
Hungary, Romania
Almost 100 % of yield losses if infection occurs near anthesis, but on
a regional basis losses are generally from 1 to 5 %
Phomopsis
stem canker
Romania, Hungary,
France
The disease occurrence has lessened in the past years
Alternaria
blight
All countries in EU
Infestations can cause defoliation and yield losses as high as 60 to
80 %.
Phoma
black stem
France
At a regional scale, in France yield losses range from 0.2 to 0.5 t/ha
Strategy 3 : to decrease the effect of diseases
(2)
• Strategies to decrease the effect of diseases
Main
diseases
Strategies to control the diseases
Downy mildew
Genetic and chemical control, but adaptations of the pathogen give continuous challenge to scientists
Broomrape
Genetic resistance, but it is rapidly overcome by evolutions of the parasite.
To use CLEARFIELD sunflowers (resistant to imidazolinone herbicide family) and the application of
imidazolinone herbicide to control broomrape
To avoid dissemination by machinery movement along the different growing areas
White rot
The most effective control is an integrated program of cultural practices (no excessive N fertilization,
wide row spacing…), spatial isolation, genetic resistance and chemicals
Phomopsis stem
canker
Genetic resistance has been very efficient, because it is polygenic (difficult to overcome)
Chemical application
Cultural practices (density < 50000 plants/ha, N < 60 kg/ha and deep incorporation of stalks) and
spatial isolation
Alternaria blight
Resistance breeding
Phoma black
stem
Susceptibility of cultivars (there is a need to study the tolerance of hybrids)
One fungicide is effective, but it is not available for farmers (homologation is needed)
Cultural practices (limited N fertilization and irrigation help to control the disease)
Strategy 4 : to decrease the effect of other factors
• The main other limiting factors
– Some weeds are not controlled by pre-plant or pre-emergence herbicides
The recent introduction of herbicide-tolerant sunflowers (CLEARFIELD
and EXPRESS) make possible a post-emergent weed control option
– Insect damages are mainly a problem in eastern Europe (Bulgaria,
Hungary and Romania)
The use of chemical insecticides is a primary tool, but alternative pest
management strategies are possible (rotating crops, altering planting dates,
increasing natural ennemies, sex pheromones…)
– Slugs, birds and game animals : in France, the yield loss (0.3 to 0.4 t/ha in
some areas) is greater than that attributed to insects
The strategy should focus on seed treatments and sowing practices to
obtain a better seedling emergence, while a better understanding of the
biology of animals would be helpful
Conclusion
• A global strategy is needed to increase seed yield
– The best combination of decisions must be taken in order to obtain
high yields, at low costs and with little impact on environment :
Decisions to be taken are : the distribution of crops in the landscape, machinery
movements along the growing areas, crop rotation, the choice of variety, cultural
practices and chemical applications
The risks of drought, diseases and other limiting factors must be taken into account
– Studied are needed to design and to test these combinations of
decisions, but the conformation of farmers to adopt the recommended
practices is also a challenge
– Breeding will help to obtain better results (increased yield, lower costs
and lower impacts on environment)
Breeding should focus on seed yield potential, but also on drought tolerance, and on
resistance to diseases and insects
Improving the production and
yield of oilseed rape
David Turley, Ruth Laybourn
24 April 2009, Foggia, Italy
Oilseed rape
• EU largest producer
(18m tonnes)
• 70% of all oilseeds
• Ave EU yield 3-3.3 t/ha
China & Canada = 1.8 t/ha
India = 0.8 t/ha
Increasing Production
• 1) Increase area of land cropped
• 2) Increase yield of OSR/ha
Netherlands
Germany
Ireland
Denmark
Belgium
UK
Austria
Czech R
France
Poland
Sweden
Slovenia
Hungary
Slovakia
Bulgaria
Lithuania
Romania
Greece
Latvia
Spain
2
Italy
2.5
Estonia
Finland
EU average yields
4
3.5
3
0.8 m
tonnes
1.5
1
EU OSR average yield improvement
European increase in yield of wheat and rape
4.5
4
3.5
yield (t/ha)
3
2.5
rape
Wheat
2
1.5
1
0.5
0
1960
1965
1970
1975
1980
1985
1990
1995
2000
2005
2010
Potential yield
• Realistic potential = 6.5 t/ha
– (Berry & Spink 2006)
• 9.2 t/ha where water not restricting
• Doubling yield in countries currently
above EU average = extra 12.4 m
tonnes
Way forward
• Address Sulphur deficiency
• Maintaining rotational gaps (> 1 in 3)
• Develop improved cultivars
Way forward
• Increase seed number by optimising
resource capture
– Bring flowering forward
– Reduce light interception by flowering
canopy
– Increase leaf area (photosynthetic area)
Way forward
• Field yields of up to 5t/ha have been
achieved – 6.5 t/ha is not unrealistic !
• Increase in yield is not at the expense of
oil content
Extraction of High Value
Chemicals
Ray Marriott
24th April 2009, Foggia, Italy
Extraction Strategy
 Capture
high value molecules before
conversion of biomass to biofuel
 Use benign technologies where possible
 Use by-products of biofuel production to
provide resources
 Add value to biorefinery and provide
renewable and economic source of valuable
molecules
Extraction Strategy
Fermentation
CO2
Densification
Extraction
Sterols
Digestion
Alkanes
OH
HO
O
O
Fatty acids
O
Wax esters
OH
Fatty alcohols C29
C12
C18/
C18:1 C18:2
C31
C33
C28
unknown
C14 C16
C18:3 C22
C20 C24 C26
C24
Functional extracts
Integrated Corn Processing
Reproduced from WO2008/020865
Extraction Economic Factors
 Overall
extract yield (kg/kg raw material)
 Typically
 Extraction
1-3% for straw/husk/leaf
column loading (bulk density kg/m3)
 650kg/m3
 Extraction
should be achievable by pelleting
time (kg CO2/kg raw material)
 Typical
extraction time 2-3 hours
 Rapid load/unload mechanisms essential
 Plant
capacity
Effect of Bulk Density
Effect of Plant Scale
Electrical energy
14.7%
Water
1.1%
Loan interest
13.1%
Steam
4.0%
CO2
7.3%
Depreciation
26.9%
Spares
3.6%
Labour
29.4%
Brunner,G., Supercritical fluids: technology and
application to food processing. Journal of Food
Engineering, 2005, 67, 21–33
Typical breakdown of operating
costs for CO2 extraction
Potential Products
Sterols
Alkanes
OH
HO
O
O
Fatty acids
O
Wax esters
OH
Fatty alcohols C29
C12
C18/
C18:1 C18:2
C31
C33
C28
unknown
C14 C16
C18:3 C22
C20 C24 C26
C24
Summary
 Utilizes
proven technologies
 Selective extraction of valuable chemicals is
possible but yields will be low
 Densification of raw material is essential
 Economy of scale demonstrated with other
raw materials
 Continuous extraction would provide a
quantum shift in costs
FORTH/ICE-HT
Anaerobic digestion of residues
from oil-rich crops
K. Stamatelatou, G. Antonopoulou
and G. Lyberatos
24 April 2009, Foggia, Italy
FORTH/ICE-HT
Anaerobic digestion
• … is the breakdown of the organic matter by
micro-organisms in the absence of oxygen.
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FORTH/ICE-HT
AD of Solid Waste
Yield
(m3CH4/kgVS)
Yield
(m3 CH4/ton ww)
0.57
150
0.5-0.6
100-150
0.30-0.50
30-100
0.2-0.4
36-145
Pig manure
0.29-0.37
17-22
Cow manure
0.11-0.24
7-14
Feedstock
Slaughterhouse
waste (industrial
waste)
OFMSW
Energy crops
Straws, sugar beet
tops (crops
residues)
FORTH/ICE-HT
Biogas utilization
Biogas
Desulphurisation
Boiler
Heat
Desulphurisation
CHP
Electricity
Heat
Gas treatment
Gas treatment
Reforming
Compression
Fuel Cell
Pressure Tank
Electricity
Heat
Fuel
FORTH/ICE-HT
Anaerobic digesters
•
•
•
•
dry (>15% dw) – wet (<15% dw)
mesophilic (35 C) – thermophilic (55 C)
batches – continuous
One stage – two stages
FORTH/ICE-HT
AD of energy crops
Example Reidling, Austria
CHP operation (2005)
AD
Input energy crops
Wet, two-stage
11,000 t/y
Feedstock 30% pig manure
70% energy crops (maize)
and residues from
vegetable processing
Input manure+leachates 7,300 t/y
Example Güssing, Austria
CHP operation (2005-2006)
AD
Input maize crop
5,940 t/y
Input grass crop
2,181 t/y
Input clover crop
1,374 t/y
Sale electricity
4,153 MWh/y
Sale heat
1,697 MWh/y
Wet, two-stage
Feedstock energy crops (maize,
grass, clover)
Sale electricity
8,030 MWh/y
Sale heat
1,600 MWh/y
FORTH/ICE-HT
AD of energy crops
Dry
matter
(%)
(%)
30-33
47
20
18
Rye
30-40
15
Grass
15-30
4
Solid manure
20-35
15
Feedstock
Maize
Sunflower
average
29
(20-40)
100
Active digestate (6 parts)
Feedstock (1 part)
<10 mm
Mixer
pump
Biogas
Use
DRA
NCOFAR
M
Nüstedt,
Germany
Dranco –
farm
continuous,
thermophilic
3 CHP (250 kW each)
Intensive
fermentation
post
fermentation
Inactive
pump
digestate
Digestate
storage
FORTH/ICE-HT
Residues - Characteristics
Residues
rapeseed
sunflower
Dry matter (wt%)
91
87
Moisture (wt%)
9
13
Volatile Solids (wt% dry basis)
91
90
Ash (wt% dry basis)
9.4
10
Chemical Oxygen demand (g O2 /g dry basis)
1.07
1.04
Soluble carbohydrates (wt% dry basis)
3.66
3.45
Characteristics
FORTH/ICE-HT
BMP tests
Biogas
measurement
Methane
content
 No pretreatment
 Thermal pretreatment (1 h)
 Acid (H2SO4, 2% w/v) addition with or
without thermal treatment
 Alkali (NaOH, 2% w/v) addition with or
without thermal treatment
FORTH/ICE-HT
Performance of AD on residues
Methane yield (L methane / kg VS)
No thermal treatment
thermal treatment
Acid
Alkali
Acid
Alkali
Rapeseed
247
149
213
294
232
248
Sunflower
280
184
248
284
239
224
Biogas yield (m3 biogas / t feedstock)
No thermal treatment
thermal treatment
Acid
Alkali
Acid
Alkali
Rapeseed
273
151
264
279
246
308
Sunflower
313
200
273
308
250
234
FORTH/ICE-HT
Cost evaluation
– 1 m3 biogas yields:
• 5-7.5 kWh (total) energy
• 1.5-3 kWh (electrical) energy
– Investment: 2,000-5,000 €/kWel
– Operating: 2-4.5 € ct/kWhel
•
•
•
•
•
Maintenance CHP (10-40; 32)%
Maintenance and repair of biogas unit (10-15; 15) %
Labour costs (14-40; 30)%
Insurance 8%
Other utilities (10-15; 15)%
FORTH/ICE-HT
Profit evaluation
• Electricity production value
– 14.5 € ct/kWhel (Austrial tariff for CHP up to
500kWel)
• Thermal energy value
– 4 € ct/kWhheat
• Fertilizer value
FORTH/ICE-HT
Cost benefit analysis (on annual
basis)
residues
rapeseed
sunflower
quantity (t/y)
6,000
6,000
CHP (kWel)
458
536
cost
min
max
min
max
investment (€)
916,791 2,291,978 1,071,269 2,678,172
Electricity production (ΜWhel)
3686
4307
cost
min
max
min
max
operating (€)
73,710
165,848
86,130
193,793
maintenance CHP
23,587
53,071
27,562
62,014
maintenance & repair biogas
11,057
24,877
12,920
29,069
labour
22,113
49,754
25,839
58,138
insurance
5,897
13,268
6,890
15,503
other
11,057
24,877
12,920
29,069
sell electricity (€)
534,398
624,443
Heat production (ΜWh)
6,552
7,656
sell thermal (€)
262,080
306,240
Methods of pretreatment, hydrolysis, and
fermentation of the lignocellulosic fraction
for ethanol production and subsequent
biological treatment of the remaining
biomass for methane production.
by Merlin Alvarado Morales (DTU)
Pretreatment Methods (I)
• The selection of a pretreatment technology heavily
influences cost and performance in subsequent hydrolysis
and fermentation.
• The ideal pretreatment process must meet the following
requirements:
– (1) improve the formation of sugars or the ability to subsequently
form sugars by hydrolysis,
– (2) avoid the degradation or loss of carbohydrates,
– (3) avoid the formation of byproducts that are inhibitory to the
subsequent hydrolysis and fermentation processes, and
– (4) be cost-effective and environmentally friendly.
Pretreatment Methods (II)
• Of the promising pretreatment technologies, dilute acid is
the most developing.
• Xylose yields are 75-90 % which is much higher than
when using steam explosion (45-65%).
• Dilute acid pretreatment also produces fewer fermentation
inhibitors, and significantly increases the later cellulose
hydrolysis.
• However, acid consumption is an expensive part of the
method, the method produces a gypsum waste disposal
problem and it requires the use of expensive corrosion
materials.
Pretreatment Methods (III)
• One of the promising pretreatment technologies is
the LHW.
• However, the LHW process is still at the earliest
laboratory stage and could come commercially
available within 10 years, with yields projected
around 88-98%, higher than for dilute acid or
steam explosion.
• But the associated costs are uncertain (e.g. costs of
the considerable water recycling)
Pretreatment Methods (IV)
• Greater fundamental understanding of the chemical and
physical mechanisms that occur during the pretreatment,
along with an improved understanding of the relationship
between the chemical composition and physicochemical
structure of lignocellulosics and the enzymatic digestibility
of cellulose and hemicellulose are required for the
generation of effective pretreatment models.
• Predictive pretreatment models will enable the selection,
design, optimization, and process control for pretreatment
technologies that match the biomass feedstock composition
with the appropriate method and process configuration.
Cellulose Hydrolysis
• Acid hydrolysis has been practiced and well understood for
half a century and analysis of R&D driven improvements
projected only modest cost improvements.
• The enzymatic hydrolysis has currently high yields (7585%) and improvements are still projected (85-95%), as
the research field is only a decade young.
• Refraining from using acid may be better for the economy
of the process (cheaper construction materials, cutting
operational costs), and the environment (no gypsum
disposal).
Hydrolysis and Fermentation
Strategies (I)
• SSF configuration process consolidates hydrolysis of
cellulose with direct fermentation of the produced glucose.
This reduces the number of reactors involved by
eliminating the separate hydrolysis reactor and more
importantly, it avoids the problem of product inhibition
associated with enzymes: the presence of glucose inhibits
the hydrolysis.
• In SSF there is a trade-off between the cost of cellulase
production and the cost of hydrolysis/fermentation. Short
hydrolysis reaction times involve higher cellulase and
lower hydrolysis fermentation costs than longer reaction
times.
Hydrolysis and Fermentation
Strategies (II)
• The optimum retention time is constrained by the cost of
the cellulase, and is about 3-4 days.
• The SSCF which implies the co-fermentation of hexoses
and pentoses is being tested atpilot scale and the
microorganisms able to ferment both hexoses and pentoses
are under R&D.
Biological Treatment for
Methane production (I)
• The remaining wastewater can be considered as another
source of energy. Anaerobic digestion of wastewater
results in biogas, which contain 50-70% methane.
• The biogas can be sold as a by-product or burned to
generate steam and electricity, allowing the plant to be self
sufficient in energy.
• This approach results also in reduction of disposal costs of
the wastes and generates additional revenue through sales
of excess electricity.
Biological Treatment for
Methane production (II)
• Maxifuel concept involves the production of other biofuels
such as methane and hydrogen, and other valuable byproducts such as a solid fuel from the parts of the biomass
not suitable for ethanol production, adding full value to the
overall process.
• The Maxifuel concept exploits an environmentally friendly
way of producing bioethanol where recirculation and reuse
of all streams produced in the process are integrated into
the process.
Biomaterial Production
A. Rouilly, C. Vaca-Garcia
Potential of olaginous straw
• Huge ressource
– e.g. for sunflower: [Marechal, 1998]
• stem=25% of total dry matter
• Seeds=30% DM
– Potential resource: [Cetiom, 2007]
• European production of sunflower seeds in 2007: 5.6 Mt
• Potential ressource of sunflower straw≈ 4.7 Mt/year
– Soy or rapeseed straw are not rigid enough to be
harvested
– But no harvest!! Today straw is only used as soil
enrichment...
Structure and composition of sunflower straw
• Husk: 90% w/w
– 41% cellulose
– 32% hemicelluloses
– 17% lignin
• Pith: 10% w/w
– d=0.035
– 17-18% pectin
– 44-45% cellulose
Use of sunflower straw fiber
• Structural heterogeneity [Ince, 2005 + 2 references]
– Stronger on the lower part
– Outter part (90%): lignocellulosics
– Easy depithing
• Pulping of straw [Marechal, 1999 + 6 references]
– Pulp is good enough for cardboard
– Yield and pulping conditions have been optimized
• Particle boards [Guler, 2006 + 3 references]
– Better if depithed
– Better when mixed with wood particles
• Rapeseed straw: few work on fiber characterization
Use of sunflower pith
• Low density materials [Marechal, 1999]
– No additive or mold-drying process
– Properties related to water content
– Actually investigated for new insulating material
• Pectin extraction
– high anhydrogalacturonic acid content (77-85%)
– low acetyl content (2.3-2.6%)
– Firm gels with Ca but highly pH sensitive
Aqueous extraction of sunflower oil
• One stage twin-screw extrusion process
– Energy efficient
– Solvent free
– Emulsions with natural surfactant
Flow sheet of the aqueous extraction of
sunflower oil from whole sunflower plant
• Oil extraction
yield up to 70%
• Cake meal:
– High fiber
content
– Residual oil &
protein
Thermo-molding of cake meal
• High pressure hot pressing:
• Materials: [Evon, 2008]
– Characteristics:
• density≈1.1
• flexural modulus: up to 2.3 GPa
Conclusion
• High potentiality for sunflower stalk
especially
• Pith is an interesting natural low-density
material
• New aqueous oil extraction:
– Use of the whole plant
– Environmentally friendlier
– Fibrous cake meal as source of new agromaterials