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
BioPerspectives 2005 – BREW Symposium – Wiesbaden - May 11th 2005 - 2
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
BioPerspectives 2005 – BREW Symposium – Wiesbaden - May 11th 2005 - 3
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
BioPerspectives 2005 – BREW Symposium – Wiesbaden - May 11th 2005 - 4
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
BioPerspectives 2005 – BREW Symposium – Wiesbaden - May 11th 2005 - 5
THE STARCH BASED BIOREFINERY TODAYTYPICAL FLOW-SHEET
Renewable
Raw
Materials
Physical separation,
pre-treament
Chemical or bio. Catalysis process
Fermentation Products
Enzymatic process
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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
BioPerspectives 2005 – BREW Symposium – Wiesbaden - May 11th 2005 - 7
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
BioPerspectives 2005 – BREW Symposium – Wiesbaden - May 11th 2005 - 8
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
BioPerspectives 2005 – BREW Symposium – Wiesbaden - May 11th 2005 - 9
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)
BioPerspectives 2005 – BREW Symposium – Wiesbaden - May 11th 2005 - 10
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
BioPerspectives 2005 – BREW Symposium – Wiesbaden - May 11th 2005 - 11
CURRENT BIOCHEMICAL APPLICATIONSFOR STARCH AND DERIVATIVES
AMINO ACIDS
VITAMINS
ANTIBIOTICS
ENZYMES
POLYSACCHARIDES
Carbohydrate sourcesNitrogen sourcesTechnological auxiliaries
YEAST
Main properties
BioPerspectives 2005 – BREW Symposium – Wiesbaden - May 11th 2005 - 12
CURRENT CHEMICAL APPLICATIONSFOR STARCH AND DERIVATIVES
POLYURETHANE
SURFACTANTS
DETERGENTSMETAL SURFACE
TREATMENT
COLORANTS
Chemical intermediatesActive ingredients in formulated productsPlastic polymers
BIODEGRADABLE PLASTICS
Main properties
BioPerspectives 2005 – BREW Symposium – Wiesbaden - May 11th 2005 - 13
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
BioPerspectives 2005 – BREW Symposium – Wiesbaden - May 11th 2005 - 14
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
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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.
BioPerspectives 2005 – BREW Symposium – Wiesbaden - May 11th 2005 - 16
ISOSORBIDEA SUSTAINABLE DIOL FOR CHEMICALS AND POLYMERS
BioPerspectives 2005 – BREW Symposium – Wiesbaden - May 11th 2005 - 17
(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=
BioPerspectives 2005 – BREW Symposium – Wiesbaden - May 11th 2005 - 18
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
BioPerspectives 2005 – BREW Symposium – Wiesbaden - May 11th 2005 - 19
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)
BioPerspectives 2005 – BREW Symposium – Wiesbaden - May 11th 2005 - 20
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
BioPerspectives 2005 – BREW Symposium – Wiesbaden - May 11th 2005 - 21
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.
BioPerspectives 2005 – BREW Symposium – Wiesbaden - May 11th 2005 - 22
Isosorbide as sustainable diol from the C6 platform
THANK YOU FOR YOUR TIME
Questions & Answers
BioPerspectives 2005 – BREW Symposium – Wiesbaden - May 11th 2005 - 23