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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Backup

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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