1 J.M.Pujol
Jean-Marc Pujol
CROPS2INDUSTRY Bordeaux
Industrial Uses of Biobased FeedstocksFocus on Oleoproducts
2 J.M.Pujol
Rhodia Engaged in Chemistry
of Several Plant Feedstocks
eucalyptus spruce pine coconut palm soybean rapeseed peanut
corn rice
castor bean
guarsugarcane
Plants:
a source of
natural
molecules and
polymers
Plants:
a source of
natural
molecules and
polymers
fatty
acids
sugars
cellulose
wheat
alcohols
3 J.M.Pujol
Rhodia Engaged in Chemistry from Biomass
for Growing Applications
Natural molecules and polymers
for numerous applications
Natural molecules and polymers
for numerous applications
fatty acids
sucrose
cellulose
cables
for filters
solvents, monomers
for inks, paints, coatings
soaps, surfactants
for shampoos and body wash
plastics
for automotive
additives
for crop protection
Augeo® Sipomer® Rhovanil® Rhodiantal®
Mirataine® Alkamuls® Miranol® Rhodasurf® Rhodameen® Rhodapex® Geropon®
Acetol Jaguar® Rhodicare ® Rhodopol® Rheozan® Technyl® eXten
alcohols
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Refinery : carbon flow from oil, coal and gas to applications
Biorefinery : carbon flow from biomass (sugarcane, wood, rapeseed, wheat…) to applications
Rhodia : Downstream for Biorefineries
Oil Fields
����crude oil
Refineries
���� fuels
���� chemical intermediates
Chemical Processes
���� chemical
specialties
FormulationDownstream Industries
Agriculture Fields
����biomass
Biorefineries
���� food
�biofuels
� paper, chemical
intermediates
Chemical Processes
���� chemical
specialties
FormulationDownstream Industries
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Rhodia Biosourced Raw MaterialsWorldwide Feedstocks - Room for Growth at least in Europe
eucalyptuseucalyptus
eucalyptuseucalyptus
sprucespruce
pinepine
pinepine
pinepinerapeseedrapeseed
corn/wheatcorn/wheat
guarguar
coconutcoconut
palmpalm
sugarcanesugarcane
castor beancastor bean
ricericepinepine
sugarcanesugarcane
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• Current situation• many examples of products coming from biomass,
• for diverse applications including high performance.
• Europe• Europe a leader in agro production,
• Europe a leader in chemicals production,
• European raw materials from biomass still to develop for chemical use.
• The future• A positive trend,
• Drivers: economics, regulation, innovation,
• Opportunities to create.
Status : Successes and Potential
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Data to Consider :
• Today• stable or decreasing oil production : 4 billions tons / year
• chemical industry uses 12 % of oil production (half as raw materials)
• increasing agriculture production : 4 billions tons / year
• chemical industry uses 2 % of agriculture production
• cellulose is the most abundant organic feedstock:
• more than 50 % of biomass,
• quantity synthesized by plants is 50 to 100 billions tons per year
• paper industry uses 1 % of cellulose production
Oil
4 Gt
Agri
culture
4 Gt
Cellulose
> 50 Gt
Oil
for chemicals
Cellulose
for paper
300 Mt500 Mt
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Future Growth
Based on Biosourced Feedstocks• Rhodia
• 4 billions sales - 14 000 employees• France : 7 % sales, 30 % production, 33 % employees, 50 % R&D
• 2009 : 11 % raw materials coming from biosources• cellulose
• ethanol
• oleochemicals
• guars
• Growth Ambition : increase based on sustainable development
• Ambition • 2017 : 15 % raw materials coming from biosources
• 2020 : 20 %
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Future Growth should be based on Major Feedstocks
Most important opportunities for chemical industry came from feedstocks driven by
mass applications
• Oleo Feedstock (palm, soy, rapeseed…)• food applications developed the feedstock
• biodiesel derivatives generated glycerol as a interesting feedstock for chemical industry
• Sugar/Starch (cane, wheat, corn...)• food applications developed the feedstock
• biofuel gave an additional development and generated bioethanol interesting for polyethylene, polyoxyethylene,
• new fermentation biotechs may lead to new products
• Lignocellulose (pine, eucalyptus... bagasse)• paper applications developed the feedstock
• future bioethanol 2nd generation may create coproducts interesting for chemical industry.
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Rhodia one of the Founding Members of ACDV
Association Chimie du Végétal
Biosourced Chemistry Association
Biomass Chemicals
Leading Asset
of
Green Chemistry
Objective of our ACDV membership 2008:
Identify feedstock sector for strategic development
of future business growth
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Biosourced Chemicals :
Positive Trend for Sustainability
• Limited fossil resources
• mainly located in sensitive countries
• strong price variations with a trend to higher prices
• A societal request
• Financial support from governments
• development of local resources
• diversification of energy sources
• reduce global warming from CO2
• Chemical companies engaged in sustainable development
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ACDV for the Promotion of Biobased ChemicalsAssociation of chemicals and agricultural industries
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Natural Oils from Seeds and Fruits
Biomass Feedstocks for Derivatives
pressure extraction
triglycerides
coconut palm soybean rapeseed peanut
glycerol
fatty acids
lauric C12cetylic C16oleic C18stearic C18erucic C22
…
Augeo®
new
solvents
castor bean
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0
5
10
15
20
25
30
35
40
45
Palm
Palm kernel
Coconut
SoybeanRapeseed
Sunflower
Cottonseed
Peanut
Olive
Corn
Sesame
Tallow/grease
Lard
Butterfat
Tall Oil
LineseedCastor oil
Fish Oil
millio
ns t
on
s
15%85%
Vegetale oils
Animal fats
Oleochemical Feedstocks
A Dominant Vegetable Output
Source:Oil world 2009
Palm oils Vegetable edible oils Animal fats Industrial oils Fish
32.2 % 51.5 % 14.3 % 1.4 % 0.7 %
Total production: 155 millions tons5 distinctive segments
22%13%
7%
14%
16%
28%Palm
Soybean
Rapeseed
Sunflower
Animal fats
Others
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General Context
Battlefield and Rhodia’s Positioning
End users
Playground
Plantation
CompaniesOleochemicals
Battlefield
Crushers
Oil MillsOil Refiners Surfactants
Plastics
Soaps
12 %
Personal care
Food-Feed
Converters
6 % BiodieselFeed
Food76 %
Rhodia
Candles
12 %
Source APAG 2008, Oil world 2009, Berlin Icis Oléo Conférence Oct. 2009
16 J.M.Pujol Source Icis 2009
Vegetable Oils Usage Food & Industrial Markets
Vegetable Oils
155 kT
FOOD
104 kT
FEED
13 kT
INDUSTRIAL
38 kT
SOAPS
8 kT
OLEOCHEMs
11 kT
BIODIESEL
19 kT
⇒ Oleochems (not inc soap) are only 7% of the global vegetable oil market.
⇒ Food (76%) dictates market dynamics
⇒ Fuel / Biodiesel (12%) is becoming an increasingly important factor
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Biosourced Fatty AcidsFeedstocks for Many Surfactants
• Surfactants : molecules made of two distinct blocks: • one presenting a strong compatibility with oils,
• one presenting a strong compatibility with water.
fatty acids
lauric C12cetylic C16oleic C18stearic C18erucic C22
…
+
polar part
ions
hydrophilic blocks
surfactants
ionicsanionics
cationics
amphoterics
non-ionics
sourcing
coconut
palm kernelpalm
soybean
rapeseed
…
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Biosourced SurfactantsApplications in Fluid Formulations
• Due to their properties: foam control, surface modification, cleaning, emulsion, rheology : Miranol®, Rhodasurf®, Rhodameen®
• Surfactants are used as performance additives for fluid formulations in several industries : • personal care,
• home care,
• metal treatment, industrial cleaning,
• oil extraction,
• crop protection.
• The renewable source is a positive element for higher value added applications.
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• Betaines amphoteric surfactants : Mirataine®
• very soft and foamy surfactant, compatible with other surfactants and soluble in electrolyte solutions
• emulsifiers, thickeners, antistatics, foaming agents for :
• shampoos, body washes, liquid soaps, bubble bath gels, conditioners,detergents.
Amphoteric Biobased Surfactants :Well Suited for Personal Care
Fatty acid + DMAPAmine + choroacetate Na
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• Cocoylisethionate sodium Geropon®fatty acid +
• Surfactant for cleansing personal products• shower gels, shampoos, facial cleansers, liquid soaps,
• brings softness for skin cleansing care,
• foaming agent efficient with hard waters,
• forms a light foam, leaves the user with a cleanliness and soft care feeling with light moisturizing.
• The consumer is looking for a natural product for skin care and soft feeling.
• Miracare® Plaisant brings :• high softness,
• deep cleansing,
• soft and silk feeling after use.
A Natural Origin
Expected by the Consumers
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Natural Oils :A Feedstock as well for Plastics
• Sebacic acid C10 is synthesized from ricinoleic acid extracted from castor oil• Polyamide 6,10 is prepared from diamine C6 and sebacic acid C10• PA6,10 broadens polyamides application field to high tech applications with:
• strong mechanical and thermal performances similar to PA 6, with a high melting point (215°C)
• an exceptional chemical resistance, similar to polyamides 11 and 12
• Used to manufacture pipes and tubes for engine fuels in automotive applications • Engineering Plastics are often able to replace steel and aluminum, since they can bring significant weight savings.
�A high performance application for a biosourced product in a highly technical sector.
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Polyamide 6,10 From Industrial Yarns to Engineering Plastics
Butadiene
NH3 HMDAADN
Castor OilSebacid
Acid
Castor seeds
• PA 6.10 is produced from 60% of natural resources
• Current market PA 6.10 is about 25kT mainly in monofilaments and toothbrushes
• Global castor oil production > 500 kT, less than 1 % of global production of natural oils
• Primary uses are in soaps, paints, lubricants
• Sebacic acid global production 25 kT, 5% of castor oil consumption
64%
36%
PA 6.10215°C
73w%
30w%
21w%
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Polyamide 6,10 High Performance Biobased Polymer
Offers significant environmental footprint reduction
PA 6
PA 11
Price
PA 12
PA 6.6 Shorter carbon chainShorter carbon chainShorter carbon chainShorter carbon chain+ high barrier to fuels+ high temperature resistance
Oil-based
PA 10.10
Longer carbon chainLonger carbon chainLonger carbon chainLonger carbon chain+ chemical resistance+ low water uptake+ low density
PA 6.12
PA 6.10
3 €/Kg
5 €/Kg
7 €/Kg
10 €/Kg
Bio-sourced
PA 10T
Using carbon from natural origin, and with simple and direct
chemical processes: the synthesis of polyamide 6,10 is an
efficient chemistry for CO2 emission.
Based on HMDA and Sebacic Acid,
PA 6.10 is the most economic Bio PA polymer.
Compared to other high-performance polyamides, it
offers technical performance and cost-effective profile.
Its excellent chemical resistance to salts, as well as to
steam and hot water and its low humidity absorption
characteristics makes it an excellent alternative to longer
carbon chain polyamides.
0 1 2 3 4 5 6 7 8 9
PA 6.10
PA 6
PA 12
Climate change, kg CO2eq
- 3.5 kg CO2saved
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• Main market segment targets
• brake and clutch systems
• fuel lines, connectors
• water tanks for cold countries
• flexible hoses
• batteries gaskets
• Second generation bio based PA
• high temperature, low water sensitivity, dimensional stability
• fast growing markets such as electronics connectors, photovoltaic
Bio PA for Automotive and Industrial MarketsAdditional Markets in Electronics for High T 2nd Generation
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Sugar Feedstocks Combined with OleoproductsFor 100 % Biobased Products
corn
starch
enzymatic
hydrolysis
glucose
sorbitol
sorbitan
sorbitan
ester
oil
emulsifiers
100 %
biobased
100 %
biobased
RCOOH
Biosourced
fatty acid Alkamuls®
non ionic surfactant
wheat
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Sugar Feedstocks Combined with
OleoproductsFor 100 % Biobased Products
sugarcane saccharose
fermentation
ethanol
ethanol acetaldehydeacetic
acid
ethanol
ethyl
acetate
solvents
for inks,
coatings,
paints,
adhesives
CH3CH2OH
ethylene
ethylene oxide Rhodapex®ESB70NAT
SLES Sodium Lauryl Ether Sulfate+
RCOOH
Biosourced
fatty acid