isosorbide

Isosorbide as sustainable diol from the C6 platform

BioPerspectives 2005 – BREW Symposium – Wiesbaden - May 11th 2005 - 1

AGENDA

I ROQUETTE PRESENTATION

II THE CONCEPT OF A STARCH BASED BIOREFINERY

III THE STARCH BASED BIOREFINERY TODAY

IV THE STARCH BASED BIOREFINERY TOMORROW

V CASE STUDY : ISOSORBIDE

VI CONCLUSION


ROQUETTE : MAIN FACTS

Employees : 6 000 Sales : 2 billion €uros

Agricultural raw materials : more than 5 mio.t/year

1133 plantsplants ::

Europe (8): France (4), Italy, Spain, Great Britain , RomaniaUnited States (2) Asia (3): China, South Korea


ROQUETTE MAIN FACTS

Family owned company created in 1933 and focusing on a long term and environmental respect strategy

First French manufacturer of starch and derivatives

Second European starch and starch derivatives manufacturer

Within the TOP 4 of global starch manufacturers

80 % of the French production dedicated to exportation

First worldwide manufacturer of sorbitol :

• 1 factory in France (Lestrem)

• 2 factories in the USA

• 3 factories in Asia (2 in China)

Based on reliable and well established financial structure, ROQUETTE support innovation and sustainable development into its strategic programme

ROQUETTE builds great hopes on Vegetal Based Chemistry


SUSTAINABLE DEVELOPMENT

SUSTAINABLE INDUSTRY

SUSTAINABLE CHEMISTRY

VEGETAL BASED CHEMISTRY

STARCH BASEDBIO-REFINERY

BIOETHANOL FOR BIOFUEL

BUILDING BLOCKS FOR COMMODITIES SPECIALTIES AND FINE CHEMICAL MARKETS

BIOPOLYMERS (BIOMATERIALS, BIOPLASTICS AND MODIFIED STARCHES)

THE STARCH BASED BIOREFINERYTHE CONCEPT

WheatMaize

PotatoPea

PROCESSES :• Fermentation• Enzymology• Vegetal based chemistry


THE STARCH BASED BIOREFINERY TODAYTYPICAL FLOW-SHEET

Renewable

Raw

Materials

Physical separation,

pre-treament

Chemical or bio. Catalysis process

Fermentation Products

Enzymatic process


THE STARCH BASED BIOREFINERY TODAYMAIN PRODUCTS

Isosorbide

Mechanical engineering

Enzyme engineering

Biochemical & Chemical engineering

Starch grain

Starch Modified starchesPre-cooked starches

Sodiumerythorbate

Maltitol SyrupsHydrogenated glucose syrups

Xylitol Sorbitol Gluconic acidand gluconate

Lactic acid and lactate

Glucose syrups Glucose Maltodextrins


THE STARCH BASED BIOREFINERY TODAYSTARCH VALUE CHAIN FOR CHEMICALS

Ascorbic acid

C = chemical process

B = biotechnological process

Renewable Raw Materials(maize, wheat, potatoe, …)

Vegetable Proteins

Starch

Glucose

Sorbitol

Isosorbide

PU

Other polyols (mainly for foodmarkets today)

MaltitolMannitolXylitol

ArabitolErythritol…

Cyclodextrins

Modified Starches

Organic acids

Erythorbic acid + salts

Oxalic acid + salts

Lactic acid + saltsLactate esters

PLA

Thermoplastic starches

Alkylpolyglucoside

Sorbitan esters

PolyetherpolyolsThermo setting

resins

Gluconic acid + salts

B

B

B

C

C

C

C

C

C

B

C

C

B

C

2 cetogulonic acid

Itaconic acid

Citric acid + salts

Glycerin Oil

Fatty Acids

B

B + C

C

C

Produced by the starch industry

Produced by the customers of the starch industry

Ethanol ETBE, fuel, C2 chemistry…

BB

C

C


THE STARCH BASED BIOREFINERY TODAYROQUETTE MAIN PLANT

THE MOST IMPORTANT BIOREFINERY IN EUROPE :

more than 150 hectares of surface,

more than 5000 t/day of grain worked,

2 800 employees


EUROPEAN NON FOOD USES OF MAIN AGRICULTURAL COMMODITIES (EU15/2002)

More than 50 % of these agricultural products are used for non-food applications.

Cellulose for paper and pulp production is the main resource (85 % of non-food uses).

Starch is the second resource significantly ahead of sucrose.

Annual non-food use : 42.6 mio.t

Starch & derivatives : 8%3.6 mio.t

(Total EU production : 8 mio.t)

Cellulose : 85%

36 mio.t (Total EU production : 37 mio.t)

Sucrose : 1%

0.4 mio.t (Total EU production : 17 mio.t)

Vegetable oil : 6% :

2.6 mio.t(Total EU production : 18.6 mio.t)


EUROPEAN STARCH AND DERIVATIVES MARKET BY SECTOR EU 15 / 2003

25%1%

29%

12% 4%29%

Confectionery & Drinks

Processed Food

Feed

Corrugating & PaperMakingPharma. & Chemicals

Other non-food

Total Starch & Derivatives Market = 8 mio tons(source AAC)

46% dedicated to the non-food sectors


CURRENT BIOCHEMICAL APPLICATIONSFOR STARCH AND DERIVATIVES

AMINO ACIDS

VITAMINS

ANTIBIOTICS

ENZYMES

POLYSACCHARIDES

Carbohydrate sourcesNitrogen sourcesTechnological auxiliaries

YEAST

Main properties


CURRENT CHEMICAL APPLICATIONSFOR STARCH AND DERIVATIVES

POLYURETHANE

SURFACTANTS

DETERGENTSMETAL SURFACE

TREATMENT

COLORANTS

Chemical intermediatesActive ingredients in formulated productsPlastic polymers

BIODEGRADABLE PLASTICS

Main properties


STARCH BASED BIOREFINERY TOMORROWSTARCH VALUE CHAIN FOR CHEMICALS

Ascorbic acid

C = chemical process

B = biotechnological process

Renewable Raw Materials(maize, wheat, potatoe, …)

Vegetable Proteins Proteins based plastics

Starch

Glucose

Sorbitol

Isosorbide

PU

PTT

Propane Diol

Other polyols (mainly for foodmarkets today)

MaltitolMannitolXylitol

ArabitolErythritol…

Cyclodextrines

Modified Starches

Organic acids

Erythorbic acid + salts

Oxalic acid + salts

Lactic acid + salts

Succinic acid

Fumaric acid

Lactate esters

PLA

Malic acid

Glucuronic and glucaric acid

Thermoplastic starches

Polyhydroxyalcanoates

Alkylpolyglucoside

Alkylmethylglucamide

Methylglucosideesters

Sorbitan esters

Polyether polyols

Isosorbide esters

Dimethyl isosorbide

Polyethylene Isosorbide Modified Terephtalate, other polymers

Thermo setting resins

POLYMERS

Current bulk productions

Productions on large pilote scale

Productions to be evaluated

Gluconic acid + salts

B

B

B

B

B

B

BC

C

C

C

C

C

C

C

C

B

C

C

C

B + C

EthanolC2 chemistry…

ETBE, fuel

B

C

B

C

2 cetogulonic acid

Itaconic acid

Citric acid + salts

Adipic acid

Aspartic acid

Acrylic and 3-Hydroxy propionic acid

Glycerin Oil

Fatty Acids

PBS C

Levulinic acid

Acetone Butanol B

B

C

C

C

Amino acids :Lysin

ThreoninSodium Glutamate

Tryptophan

MethioninLysteinLeucin

B


CGlycols

. Acid - catalysed reaction = protonation preferentially occurs on primary hydroxy

HOH2C C C CH2

OCH2

HO - C C OH

H+

CH2OH

-C- OH

HO - C -

- C - OH

- C - OH

CH2OH

+ H+ HO - C -

- C - OH

H2 C - O - H

H

+

- C - OH

- C - OH

CH2OH

- H2O HO - C -

- C - OH

H2 C+

- C - Ö - H

- C - OH

CH2OH

-H +

OH2 C

- C

-H2O

-H+OH O

HO

C C OH

C

¨

H

H

H

H

H

H

H

H H

H

H H

H

H

H

HH

PRINCIPLE OF ISOSORBIDE REACTION


ROQUETTE ISOSORBIDE

«« Molecular StructureMolecular Structure »»

«« CharacteristicsCharacteristics »»The main chemical and physical properties of crystalline isosorbide are listed below..

CAS No 652-67-5 Molecular formula C6H10O4 (Mw=146.14) Appearance White crystalline powder, very hygroscopic Melting point 61-64°C Boiling point 160°C (10 mm Hg) Flash point > 150°C Solubility Soluble in water, alcohols, dioxane, ketones

Almost insoluble in hydrocarbons, esters, ethers

Isosorbide content Min. 99 % Isomannide content Max. 0.5 % Water content Max. 1 %

Isosorbide is non-toxic. In addition, the molecule is very heat stable : decomposition only occurs at about 270°C.


ISOSORBIDEA SUSTAINABLE DIOL FOR CHEMICALS AND POLYMERS


(isosorbide)

(sorbitol)CH2 OH – (CHOH)4 – CH2OHCH3-CHOH-CH2OH (MPG)

CH2OH – CH2OH (EG)

COOH – (CH2)n – COOH Diacids

Isosorbide Diester« PVC-plasticizers »

(glucose)

H

CH2 OH – (CHOH)4 – C

O

H2, P

O

O O N O2

O N O2

Polyetherpolyols PU

Di Methyl Isosorbide« sustainable solvent »

Polyesters

PO

Sorbitan estersFatty acids

Isosorbide dinitrate

O

O

OCH3

OCH3

O

O

O CO

R

OCO

R

O

R-C

OHFatty acids

H2, P

PEIT

PolyurethanePolycarbonateOther polymers

ISOSORBIDE MODIFIED PET REACTIONISOSORBIDE MODIFIED PET REACTION

PTA EG Isosorbide

+ PEIT+

O OH

OH O

H O OHO

O

HO

OH=


ISOSORBIDE PET DEVELOPMENT PARTNERSHIPISOSORBIDE PET DEVELOPMENT PARTNERSHIP

Strong Intellectual Property Across the Value ChainStrong Intellectual Property Across the Value Chain&

Isosorbide

monomer

production

Converters“Make Articles”

MONOMER“PEIT”Polymer

Isosorbide

polymer

production

End-UseMarkets

e.g.,PET ContainersThermoplasticsFiber

Corn Glucose Sorbitol

The Value Proposition…Enhanced application-functionality from higher temperature performance for use in multiple markets


ISOSORBIDE VALUE CREATION FOR MULTIPLE MARKETS

Glass-Transition Temperature of PEIT

0 20 40 60 80 10040

60

80

100

120

140

160

180

200

Comonomer Effect on Glass Transition Temperature (Tg)

IsosorbideCHDMIsophthalic Acid (IPA)

Mole % (X)

Engineering Resins

CD’s

3GT4GT

PEN

Hot-fillContainers

ThickSheet

PETGPCHDM

IPA

g T(°

C)

First target = HOT-FILL CONTAINERS (THERMORESISTANT PET)


ISOSORBIDE VALUE CREATION FOR PET CONTAINERS

191.3 mm

159 mm

122 mm

102 mm

20 mm

Upper Bell

Lower Bell

Upper Bumper

Lower BumperHEEL

PANEL

WAIST

UPPER BELL

LOWER BELLCost savings options include

eliminating need for heat-set operation, provides faster cycle time and/or weight savings

Performance demonstrated by Plastics Technologies Inc.

PET Hot Fill ContainersHigher Tg performance creates new

opportunities for PET beyond today’s limitations


CONCLUSION :RENEWABLE CHEMICAL BUILDING BLOCKS FOR THE FUTURE

NEED ?

In-depth assessment by the scientific and political communauties on the real opportunity of the vegetal-based chemistry for the future. (Sustainable Chemistry platform for the 7th European R&D Framework Program)

Need to develop incentives to facilitate adoption of these processes by industry.


Isosorbide as sustainable diol from the C6 platform

THANK YOU FOR YOUR TIME

Questions & Answers


isosorbide

Documents

renewable

total eu production

lactate esters

food markets

c6 platform

ascorbic acid

sustainable

modified starches