WP1: Optimisation of oil crops agronomy and oil yield and utilisation of by products

Leading partner: FORTH

24 April 2009, Foggia, Italy

FORTH/ICE-HT

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

• Potential seed yield increased by 40 % from 1970 to 2000, due to :– An increase in harvest index

– A greater efficiency to intercept solar radiation per unit of leaf area

• No obvious increase in seed oil content was observed

0

25

50

75

100

125

150

1975 1980 1985 1990 1995 2000 2005

Year of offical registration of the variety

Har

vest

inde

x (i

n %

of

the

vari

ety

AL

BE

NA

)

Montpellier (2001 - 2002)

Toulouse (2002)Varieties

Year of official registration

Mirasol 1978

Primasol 1979

Albena 1988

Vidoc 1989

Santiago 1993

Prodisol 1995

Melody 1996

LG5660 1998

Heliasol 2000

Strategy 1 : to increase the potential seed yield (1)

(Results from Debaeke et al., 2004)

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 availabilityTo 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 EUIf entire areas are affected, the decrease in yield ranges from 50 % (late development) to 100 % (early development) in the infected areas

BroomrapeBulgaria, Romania, Spain

In case of severe infections, losses can reach up to 50 % and near100 %.

White rotBulgaria, 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 EUInfestations can cause defoliation and yield losses as high as 60 to80 %.

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 rotThe 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

• EU largest producer (18m tonnes)

• 70% of all oilseeds

• Ave EU yield 3-3.3 t/haChina & Canada = 1.8 t/ha

India = 0.8 t/ha

Oilseed rape

• 1) Increase area of land cropped

• 2) Increase yield of OSR/ha

Increasing Production

EU average yields

1

1.5

2

2.5

3

3.5

4

Fin

land

Est

onia

Italy

Spa

in

Latv

ia

Gre

ece

Rom

ania

Lith

uani

a

Bul

garia

Slo

vaki

a

Hun

gary

Slo

veni

a

Sw

eden

Pol

and

Fra

nce

Cze

ch R

Aus

tria

UK

Bel

gium

Den

mar

k

Irel

and

Ger

man

y

Net

herla

nds

0.8 m tonnes

European increase in yield of wheat and rape

0

0.5

1

1.5

2

2.5

3

3.5

4

4.5

1960 1965 1970 1975 1980 1985 1990 1995 2000 2005 2010

yie

ld (

t/h

a)

rape

Wheat

EU OSR average yield improvement

• 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

Potential yield

• 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

Way forward

Extraction of High Value Chemicals

Ray Marriott

24th April 2009, Foggia, Italy

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

Extraction Strategy

Densification

Extraction

Sterols

Alkanes

C31

C29

C33

Wax estersFatty acids

C12

C14 C16

C18/ C18:1

C28

C24 C26

C18:2

C18:3C20

C22

C24

unknown

OH

O

Fatty alcoholsOH

OHO

O

Digestion

Fermentation

CO2

Functional extracts

Integrated Corn Processing

Reproduced from WO2008/020865

Overall extract yield (kg/kg raw material) Typically 1-3% for straw/husk/leaf

Extraction column loading (bulk density kg/m3) 650kg/m3 should be achievable by pelleting

Extraction time (kg CO2/kg raw material) Typical extraction time 2-3 hours Rapid load/unload mechanisms essential

Plant capacity

Extraction Economic Factors

Effect of Bulk Density

Effect of Plant Scale

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

C31

C29

C33

Wax estersFatty acids

C12

C14 C16

C18/ C18:1

C28

C24 C26

C18:2

C18:3C20

C22

C24

unknown

OH

O

Fatty alcoholsOH

OHO

O

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

Summary

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.

FORTH/ICE-HT

AD of Solid Waste

FeedstockYield

(m3CH4/kgVS)Yield

(m3 CH4/ton ww)

Slaughterhouse waste (industrial waste)

0.57 150

OFMSW 0.5-0.6 100-150

Energy crops 0.30-0.50 30-100

Straws, sugar beet tops (crops residues)

0.2-0.4 36-145

Pig manure 0.29-0.37 17-22

Cow manure 0.11-0.24 7-14

FORTH/ICE-HT

Biogas utilizationBiogasBiogas

DesulphurisationDesulphurisation DesulphurisationDesulphurisation Gas treatmentGas treatment Gas treatmentGas treatment

ReformingReforming CompressionCompression

BoilerBoiler CHPCHP Fuel CellFuel Cell Pressure TankPressure Tank

ElectricityElectricity HeatHeatHeatHeat ElectricityElectricity HeatHeat FuelFuel

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 cropsExample Reidling, Austria

AD Wet, two-stage

Feedstock 30% pig manure70% energy crops (maize) and residues from vegetable processing

CHP operation (2005)

Input energy crops 11,000 t/y

Input manure+leachates 7,300 t/y

Sale electricity 8,030 MWh/y

Sale heat 1,600 MWh/y

Example Güssing, Austria

AD Wet, two-stage

Feedstock energy crops (maize, grass, clover)

CHP operation (2005-2006)

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

FORTH/ICE-HT

AD of energy crops

DRANCO-FAR

M

Intensive fermentation

post fermentation

pumpMixer

Feedstock (1 part)<10 mm

FeedstockDry matter (%)

(%)

Maize 30-33 47

Sunflower 20 18

Rye 30-40 15

Grass 15-30 4

Solid manure 20-35 15

average29

(20-40)100

Active digestate (6 parts)

pumpInactive digestate

Digestate storage

BiogasUse

Nüstedt, Germany

3 CHP (250 kW each)

Dranco –farmcontinuous, thermophilic

FORTH/ICE-HT

Residues - Characteristics

ResiduesCharacteristics

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

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 residuesMethane 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 sunflowerquantity (t/y) 6,000 6,000CHP (kWel) 458 536cost min max min maxinvestment (€) 916,791 2,291,978 1,071,269 2,678,172Electricity production (ΜWhel) 3686 4307cost min max min maxoperating (€) 73,710 165,848 86,130 193,793

maintenance CHP 23,587 53,071 27,562 62,014maintenance & repair biogas 11,057 24,877 12,920 29,069

labour 22,113 49,754 25,839 58,138insurance 5,897 13,268 6,890 15,503

other 11,057 24,877 12,920 29,069sell electricity (€) 534,398 624,443Heat production (ΜWh) 6,552 7,656sell thermal (€) 262,080 306,240

FORTH/ICE-HT

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 (75-85%) 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 by-products 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 agro-materials