10 Arkema PDF

Glycerol as a co-product of oleochemicals /biodiesel and vegetable oil
derivatives from Castor oil for the production of fine chemicals in perfume and
pharmaceuticals
Jean-Luc DUBOIS
Scientific Advisor, Directeur Scientifique
Catalysis and Processes
Part of the work presented here has been carried out

within the Glyvalacr project sponsored by ADEME
Niche markets for specialty industrial crops September 2nd 2011 - Thessaloniki - no copy allowed without prior author consent
Arkema is a member of the European Biorefinery Projects
Acrolein and Acrylic Acid from Glycerol

Acrolein derivatives
Related to existing Network

(steamcrakers, pipes)
Fine Chemicals
Propylen
Methionine
Ubiquitous
HO
OH
OH
Glycerol
Acrolein
Esters
O
OH
Acrylic Acid
Fine Chemicals
3
Jean-Luc DUBOIS - / Niche markets for specialty industrial crops September 2nd 2011 - Thessaloniki - no
copy allowed without prior author consent
Polyacrylics
Dispersants for
Pigments or
CaCO3
Sources of Glycerin. (Worlwide).

103 Tons
2005
2006
2007
2008
2009
Soaps
160
150
155
130
110
Fatty Acids
410
450
470
470
490
130
160
180
190
200
Synthetic
20
Other
35
30
30
30
30
Biodiesel
368
550
635
853
1000
1123
1399
1470
1673
1830
Fatty Alcohols
TOTAL
4
Classical Acrolein and Acrylic acid processes

Standard Acrolein plant:
Methionine: 30 kt/yr
Pyridine: few kt/tr
Glutaraldehyde: few kt/yr
Fine chemicals: few 100t/yr
Standard Acrylic Acid

plant:
Superabsorbants,
Esters: 80 - 160 kt/yr
Techniques de lingnieur, 1995, J6055 and J6100

5
Environmentally Friendly Process:

Avoid scenarios of past accidents

Target: develop a new process for on-site Acrolein production (PROXIplants) to avoid storage and transportation of a highly toxic Chemical.
Pierre Bnite, France. July 10, 1976.
Taft, USA/ December 10, 1982.
Major contamination of
the Rhne River, during
clean-up of a train tank
367 Tons dead fish
Explosion of a Storage facility

17000 people evacuated
6
Cradle to gate analysis

CO2
Plant growth =
consumption of
atmospheric CO2

Acrolein ex propylene: 3190 kg CO2/t

Acrol. ex glycerol: Target 980 kg/t
Acrylic acid ex Propylene: 950 kg CO2 /t
Acrylic Ac. ex glycerol: target 0 kg/t
Methanol
Transesterification
Diesel Blend
Biodiesel
Vegetable Oil
Glycerine
Acrolein/
Acrylic Acid
Done within the Glyvalacr Project sponsored by Ademe
7
Historical prices: propylene and glycerol in

Europe
/t
Propylen contract Europe (/t)
Glycerin 80% crude Europe (/t)
1000
800
600
400
2009
2008
2007
2006
2005
2004
2003
2002
2001
2000
1999
1998
1997
1996
1995
200
8
Glycerol and
Propylene
historical
prices;
drivers are
not the
same
Basic Design of Industrial Plant

Glycerol
Storage
Acrolein or
acrylic unit
Glycerol
phase
Thermal
Oxidizer
reaction +
purification
Separation
unit
9
Acrolein
or Acrylic
Acid
storage
Reaction mechanism
O
HO
HO
HO
- H2O
OH
OH
- H2O
O
OH
H
1,3-dihydroxy-propene
OH
HO
O OH
formaldehyde
Ethenol
vinyl
alcohol
acetaldehyde
-H2O
OH
3-hydroxy-propanal
H
O
- H2O
OH
Acrolein
glycerol
Heavies
Hydrogen
transfer
H
HO
- H2O
O
H
2,3-dihydroxy-propene
H
O
Propanal
OH
+H*
OH
Prop-2-en-1-ol
O
O
OH
Acetals
HO
hydroxyacetone (acetol)
10 Jean-Luc DUBOIS - / Niche markets for specialty industrial crops September 2nd 2011 - Thessaloniki - no
H3C
CH3
acetone
Glycerol to Acrolein- Operating conditions

(Typical)
Operating Conditions.

Temperature: 300-320C
Pressure: 2 bara
GHSV: 2 250 Hr-1
Catalyst: WO3/ZrO2 (solid acid)

Ratio Glycerol/Water: 30/70 (w./w.)
Ratio O2/Glycerol: 0.42 (mole/mole)

Glycerol: 6.7 % vol.

Water: 79.9 % vol.
O2: 2.8 % vol.
N2: 10.6 % vol.
Acrolein purification
Example of product qualities
H2O
Acetone
2,3-butanedione
Propionaldehyde
Hydroxypropionaldehyde
Formaldehyde
Acetaldehyde
2-oxopropanal
Crotonaldehyde
Acrolein dimer
HydroQuinone (stabilizer)
Reference
12931
Reference
13948-crude
Reference
13948-purif
wt %
wt %
wt %
4.16
0.22%
0.11%
0.75%
0.00%
0.154%
12.2%
0.0496%
0.0998%
0.0019%
0.1879%
3.00
0.34%
0.08%
0.55%
0.00%
0.049%
0.74%
0.0201%
0.0240%
0.0011%
0.1325%
3.24
1.18%
0.05%
0.065%
10.5%
0.2165%
12 Principles of Green Chemistry

1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
Prevent waste We use a waste

Design safer Chemicals and Products Same products offer market
access
Design less hasardous chemical synthesis Process for on-site
production
Use Renewable feedstocks Glycerol
Use catalysts not stoichiometric reagents Heterogeneous Catalyst
Avoid Chemical derivatives Direct route
Maximize atom economy C3 to C3
Use safer solvents and reaction conditions no solvent, safer process
Increase Energy effciency Translated into CO2 balance
Design Chemicals and products to degrade after use return plantbased CO2 to the atmosphere
Analyse in Real time to prevent pollution Target = on-time
consumption
Minimize the potential for accidents Avoid transportation and storage
Industrial property : Arkema portfolio

5 granted patents
- EP1,848,681B1 US7,655,818
WO06/087084 (02/05) GlycerolAcrolein with highly acid solid catalysts (H0 -18 to -9)
- US7,396,962 WO06/087083 (02/05) GlycerolAcrolein in the presence of O2
- US7,531,699 WO07/090990 (02/06) Glycerol + propylene acrolein
- EP1,981,835B1, US7,880,034
WO07/090991 (02/06) Glycerol + propylene acrolein acrylic acid
- US7,910,771 WO06/114506 (04/05)
Glycerol Acrolein acrylic acid in the presence of O2 in a single reactor
And much more in a near future

32 published patent applications
- WO08/007002 (07/06) Glycerol acrylic acid with 2-layered catalyst (not extended)
- WO08/087315 (12/06) Glycerol acrylic acid with intermediate condensation of
water after dehydration step
- WO08/129208 (03/07) Vaporisation/purification of glycerol in fluidized bed
- WO09/044051 (09/07) Reactive vaporisation of glycerol in fluidized bed
- WO09/044081 (09/07) GlycerolAcrolein with modified iron phosphate catalysts
- WO09/081021 (12/07) GlycerolAcrolein through acetals from glycerol + acrolein
- WO09/136537 (04/08) Catalyst made of salt of heteropolyacid for glycerolAcrolein (with NK)
- WO09/127889 WO09/128555 (04/08) GlycerolAcrolein with salt of heteropolyacid
- WO09/156664 (06/08) Use of acidic gas in glycerol dehydration
- WO10/10291 WO10/10298 (07/08) Propionic acid and vinyl propionate from cristallisation
of glycerol-based acrylic acid
- WO10/031649 (09/08) Process for biobased glacial acryclic acid
- WO10/047905 (10/08) VPO catalyst for glycerolAcrolein (with NK)
- WO10/046227 (10/08) GlycerolAcrolein with VPO catalyst
- WO11/010035 (07/09) Process for glycerol based acrylic acid that comprises an azeotropic drying step
and a crystallisation step
- WO11/010036 (07/09) Process for glycerol based acrylic acid that comprises an absorption with
hydrophobic solvant and a crystallisation

32 published patent applications
- WO11/033689 (09/09) Catalyst & process: glycerol acrolein with metal supported on TiO2
- WO11/046232 (09/09) Catalyst & process glycerol acrolein with salt of heteropolyacid supported on a
support.
- WO11/073552 (12/09) Acrolein & acrylic acid process from glycerol with elimination of impurities in a water
loop by oxidation
- FR2953830(12/09) Acrolein & acrylic acid process from glycerol with elimination of impurities in a water
loop or by evaporation or condensation
- WO08/113927 (02/07) Glycerol Acrolein acrylonitrile
- WO09/153529 (06/08) Biosourced acrolein polymer
- WO10/010309 (07/08) Acrylate esters from glycerol
- WO10/058129 (11/08) Methylmercaptopropionaldehyde and methionine from glycerol
- FR 2,939,055 (12/08) Dispersing or grinding agent from glycerol-based acrylic acid (Coatex)
- WO10/106267 (03/09) Bio-based impact modifier
- FR 2,943,351 (03/09) Bio-based acrylic processing aid
- WO10125276 (04/09) Technical biobased acrylic acid acrylate ester Acrylate polymers
- WO10/130919 (05/09) Bio-based acrylic wood adhesive
- WO11/055051(11/09) Biobased glutaraldehyde
- WO11/055057(11/09) Biobased pyridine and picoline
And much more in a near future
Further applications of a Glycerol to acrolein

technology

Fine Chemicals
(perfumes/pharmaceuticals)
Antimicrobial polymer
Acrylic acid
Acrylonitrile
Acrylamide
Glutaraldehyde
Pyridine
Acrolein

Melting point: -88 C

Boiling point:

Solubility:

2.8 31 %
Vapor pressure:
234 C
Flash point: -26C cc

Flammability limits in Air:
20 g/100 ml water @ 20 C
6.8 g water / 100 g solution @ 20 C
Density: 0.84
Self ignition temperature:
53 C @ 760 mmHg
-11 C @ 50 mmHg
-36 C @ 10 mmHg
29 kPa @ 20 C
VLE: 0.25 mg/m3

LD50:

(rat): 46 mg/kg
(mouse): 40 mg/kg
Acrolein Uses
Acrolein: a platform molecule, for Bio-based

products
CH3
R1
R1
R1
R2
R2
R2
H3C
H3C
R3
R4
R4
H3C
R3
R3
O
O
R4
H3C
O
O
CH3
CH2
Mg
Cl
HO
R1
R1
R2
R2
R
O
NH2
CH2
CH2
H2C
N
H
O
O
NH
Br
Br
CH3
CH3
O
Cl
CH3
Cl
H3C
O
O
CH3
CH3
O
O
CH3
N
N
CH3
N
Some products made out of Acrolein

Cl
O
O
Cloquintocet-M
Ciba Geigys herbicide
Quinfamide
Winthrop antiprotozoan
O
CH3
N
Cl
O
CH3
Cl
CH3
OH
HN
Pentabromopseulidin
H
N
Br
Br
Br
Br
Intermediate to
ATORVASTATIN
Br
H3C
O
Cyclopentenone
(used in Jasmone industry)
Cl
OH
NH2
H
N
O
S
Cl
NH
CH3
CH3
Chlothenoxazine
(analgesic)
Dopaminergic
Some other products made from Acrolein

O
S
Chloroquin
H2C
S
NH
CH3
Cl
Letosteine
HN
H3C
Methional Methionine
CH3
CH3
H2C
OH
H3C
H3C
O
H3C
SH
S
H2N
Meticran
(diuretic)
CH3
S
O
O
H3C
NH
Melatonin
H3C
H3C
N
H
CH3
O
NH
N
H
H3C
N
Rizatriptan
Sumatriptan
CH3
N
H
CH3
Diels Alder Reactions

H2C
R1
R1
R2
R1
Myrcenol
R2
R2
and/or
R3
CH2
R3
O
CH2
H3C
CH2
R3
R4
R4
R4
H3C
Perfumes/ Fragances
O CH
3
CH3
OH
H3C
CH3
CH3
HO
H3C
H3C
CHO
H3C
O
CH3
Muguet Aldehyde
Ivyal
Trivertal
Lyral
Cl
Pharmaceutical
O
H
N
NH2
O
N
H
S
O
O
Norbornene carboxaldehyde
Cyclothiazide (diuretic)
Diels-Alder (Acrolein as 1,3 diene)

CH2
R1
R1
+
O
R2
R2
Acrolein dimer
3-Cyclohexene-1-carbaldehyde, forms a cyclic
acetal with pentaerythritol, used as stabilizer
against ozone in rubber.
Also used for the synthesis of cycloaliphatic
epoxides
hexanetriol
O
O
Hetero Diels-Alder
R
H2O
O
R
OH
Production of Glutaraldehyde
Oxidation / Ammoxidation
O
320 C
H2C
O2
MoVWXY cat
H2C
H2O
OH
Acrylic Acid
O
H2C
1/ 2 O 2
NH3
H2C
2H2O
Acrylonitrile
O
H2C
O
HO
OH
pH# 8
H2O
O
oxirane-2-carbaldehyde
Glycidaldehyde
Pyridine derivatives
O
CH3
H2C
O
400-500 C
NH3
Catalyst
H2C
2H2O
N
3-methylpyridine
Intermediate to nicotinic acid (niacin)
O
H2C
NH3
2H2O
H3C
O
Vinyl alcohols through Grignard reactions

R
H2C
H2C
Mg
Cl
OH
O
R
OH
CH3
CH2
Octene-1-ol-3
CH3
OH
Indanone precursors
H3C
CH3
CH2
CH3
OH
CH3
CH2
Terbinafin side chain
Vinyl Alcohol through reduction

O
HO
O
H2C
OH
CH3
H2C
H3C
H3C
CH3
Hydrogen transfer reaction (Meerwein-Ponndorf), in liquid phase

CH3
H3C
OH
or
H2C
O
CH3
400 C
MgO cat H2C
OH
H3C
OH
H3C
O
or
H3C
Gas phase reaction
Amine derivatives
(Skraup Reaction)
NH2
H2
+H2C
Quinoline
Tetrahydro
quinoline
N
H
Cl
O
O
Cloquintocet-M
Ciba Geigys herbicide
Quinfamide
Winthrop antiprotozoan
O
CH3
N
Cl
O
CH3
Cl
R1
R1
K2CO3
NH
R2
O
R1
R2
H2C
R2
CH3
NH
H3C
CH3
H3C
H3C
O
DBU
THF
H3C
NH2
H2/Pd
CH3
O
NH
H3C
H3C
O
CH3
Phthalimido compounds
O
O
NH
Phthalimido propanal
+H C
2
O
O
O
O
H2N
Ethylene acetal amino propionaldehyde

O
R1
H2N
R1
R2
R2
3-aminopropanes
O
O
CH3
CH3
O
Br
HN
H2N
F
O
F
O
Intermediate to
ATORVASTATIN
Acrolein and alcohols

O
Trialkoxypropane
3-alkoxypropanal
Controlled acidity
O
Acid
R
R
CH2
Acetal
(high yields when combined
with extraction)
R
O
Vinyl dioxan & dioxolan

(more easy to form)
n
CH2
H2C
OH
O
H2C
O
O
CH2
HO
H2C
HO
O
H2C
Monomer for spirane resins

H 2O
OH
CH3
3-phenylpropanal
Acrolein acetate is obtained
by acid catalyzed reaction of
acrolein and acetic anhydride
Lewis Acid
+ H2C
CH3
Acrolein diacetate
R
O
Reaction with HCN

OH
H2C
H2C
HC
mild alkaline catalyst
O
OH
H3C
H2C
O
O
H3C
N
O
acetic anhydride
H2C
CH3
N
1-cyanoprop-2-enyl acetate
Intermediate for pharmaceutically and biologically active substances
Propargyl
R
Mg
CH3
THF / CuBr
H2C
Cl
H2O / HCl
CH3
CH3
CH3
H2C
HC
Br
O
CH3
Propargyl aldehyde
DEA
Pyroles
O
CH3
2-Bromo diethoxypropene
2-methylene cyclopentanone
Halogen Propionaldehyde Acetals

Building blocks (acetals react with HX)
O
(dioxan)
BEDO
Br
BED
(dioxolan)
Br
CH3
Cl
Cl
CH3
CPDEA
CPDMA
O
CH3
CH3
Cl
OH
NH2
Cl
NH
CH3
CH3
Chlothenoxazine
(analgesic)
Mg
Mg
R
R
Acid Chloride
Aldehyde/ketone
Br
OH
BED
Hydrolysis
Hydrolysis
4-hydroxybutyraldehydes
4-oxobutyraldehydes
OH
O
Paal Knorr
H
N
Br
Pentabromopseulidin
Br
R
H3C
Br
N
H
Br
Br
Pyroles
H3C
Dieckmann
R
H
N
Dopaminergic
D3 Antagonist
WO 951674
Cyclopentenone
(used in Jasmone industry)
R1
R2
Br
Mg
THF
R2
H2SO 4
Benzothiophenes
O
R1
R1
O
R2
Br
R1
+
R3
THF
R2
Naphthalenes
Mg
H2SO 4
O
R3
Salts and the Wittig Reaction

BED and BEDO react easily with triphenylphosphine to form the correponding phosphonium salt
O
R
Br
Cis isomers
High value for perfumes
O
P
Hydrolysis
THF
O
Cis-isomerism
R
O
R
O
O
Traumatin
OH
R1
R1
H2C
P
R2
R2
H2C
Tryptamines
CH3
O
H3C
O
O
CH3
O
CH3
N
O
H2C
NH2
O
H3C
NH
N
H
H3C
CH3
OH
H3C
NH
O
O
N
H
Melatonin
H3C
H3C
N
H
CH3
O
NH
N
H
H3C
N
Rizatriptan
Sumatriptan
N
H
CH3
Thiols
O
O
R
SH
Base
S
S
CH2
Methional Methionine
H3C
3-alkylthiopropanal
O
S
CH3
HS
CH2
O
O
CH3
S
NH
Letosteine
O
O
OH
H2C
O
H3C
H3C
O
SH
H3C
S
H2N
S
O
Meticran
(diuretic)
CH3
Michael Condensation
CH3
O
O
H3 C
O
O
H3C
H3 C
CH2
H3C
O
O
Monoaddition
CH3
Diaddition
O
CH3
O
R
H3C
CH3
R
O
CH2
H3C
Cyclohexenone
O
H3C
O
NH
H3C
Aminoacid
H2N
O
O
CH3
ADB
HO
O
R=H, D,L Tryptofan

R=OH, D,L Oiytryptan
R
Acetamidodicarbethoxybutanal
NH2
R
(ADB)
NH
N
H
NH2
4-oxo heptanedial derivative

(perfumes, fragances)
CH2
R
O
R
O
O
2-furanylpropanal
Nitrated derivatives
O
O
N
N
R
CH2
4-nitro
butyraldehyde
O
R
CH2
4-nitro
valderaldehyde
Cl
NH2
H3C
Chloroquin
H2C
CH3
H3C
HN
N
CH3
CH3
CH3
Novoldiamine
CH3
O
O
N
O
Lactones
O
4-nitro
heptane-1,7-dial
H3C
OH
O
O
N
O
4-oxobutanals
4-oxobutyric acids
O
O
N
O
For more informations

Kirk-Othmer Encyclopedia
Ullmanns Encyclopedia of Industrial Chemistry
Fine Chemistry and Acrolein , B. Goyau,
Chimica OGGI/Chemistry todayNovember/December 1999
Info Chimie Magazine, N412, Oct 1999, p9098
Arkemas offer
Bio-based acrolein technology for licencing

PILOT scale (Several kg/hr) end 2011
Partnership on a case by case basis.
Design parameters:

Plant capacity
Product quality (acceptable impurities)
Location
Based on crude or refined glycerine
Valorization of Castor Oil for Polymer and Fine Chemicals

Applications in Arkemas Castor Biorefinery
Edible vs Non-edible Oils / Fatty acid types

Seeds
C16:0
C18:0
C18:1
C18:2
C18:3
Rape seed
(v. low erucic)
3-6
1-3
55-67
16-26
6-14
Safflower
(high linoleic)
3-6
1-4
11-21
73-79
tr
Safflower
(high oleic)
3-6
1-4
73-79
10-16
tr
12-17
5-10
37-63
19-41
1-2
1-2
3-4
5-6
Jatropha
Curcas
Castor
0.5-1
Other
Iodine Nr
96-117
0.2
140-150
90-110
1-2 C20
93-107
87-88
82-90
(C18:1, OH)
Pongamia
pinnata
3-8
Rubber seed
7-11
9-12
18-30
33-39
Sal
5-9
34-48
34-45
2-3
13-16
14-24
49-62
2-16
Neem Oil
2-9
44-71
10-18
15-20
80-96
(C20~C24)
20-26
121-148
6-12 C20
33-45
1-3 C20
65-80
Arkemas Castor Biorefinery

Marseille Saint-Menet, France
Hydrolysis
Bromination
Cracking
Methanolysis
Amonolysis
Crystallization
Flowsheet
Aminoundecanoic acid production
Castor
Castor is indigenous to the

Mediterranean Basin, Easter Africa
and India.Today it is widespread
throughout tropical regions.In
areas with a suitable climate
(tropical regions), castor
establishes easily and can often be
found on unused land.
Castor oil chemically unique

Castor Oil is the only vegetal oil containing an hydroxyl group in the
triglyceride structure.
TRIGLYCERIDE
OH
O O
OH
O O
OH
Castor Beans seeds contains 40 to 60 % of oil

wich is made of 80 to 85 % of ricinoleic acid.
This such particular structure is the key to
explain the result of this equation :
18 = 11 + 7 or 10 + 8
When 18 equals to 11 + 7
The behaviour of Castor Oil when heated to high temperature has intrigued
chemists since 1845. Since that time Castor Oil chemistry has evolved
significantly. The process in use at the Arkema Marseille plant is in fact
unique in the world. Castor Oil is a biodegradable and renewable resource for
a large range of raw materials.
Castor Oil
GLYCERINE
C3
C18
RICINOLEIC
C18
NON RICINOLEIC
Mixture of Fatty acids

triglycerides
C3
C18
RICINOLEIC
Methanolysis
C18
NON RICINOLEIC
GLYCERINE
GLYCERINE
C3
OH OH OH
C18
RICINOLEIC
O
O
Methyl ricinoleate
C18
NON RICINOLEIC
Valorisation of glycerine :
bio-resourced compounds such

as acrolein, propylene glycol
GLYCERINE
anti-freezing,
C3
Decantation
wetting and lubricating agent in

handcreams, suntan lotionsand
soaps hair care.
OH
OH OH OH
Steam Cracking
Steam Cracking (pyrolysis at elevated temperature) cleaves ricinoleic acid

ester into two parts: one part consisting of 7 carbon atoms and the other of
11 carbon atoms.
atoms The Marseille process equation is C18 = C11 + C7.
C7
A whole range of innovative chemistries and end use products are generated
from these base reaction products. These products are used in every-day
life, to improve our comfort and safety.
C7
Heptanal
C18
RICINOLEIC
Steam Cracking
OH
O
O
Methyl ricinoleate
C18
NON RICINOLEIC
OH
C11
Methyl undecylenate
O
Fatty esters
C7 derivatives
from perfumes to technical products
The C7 molecule has seven aligned carbon atoms
and is known for the olfactory qualities of
certain of its derivatives. In its natural state, it
is present in wine as oenanthol.
The low freezing point of this
chain makes it well suited for
lubricant applications.
applications
Aldehyde, alcohol and acid are the three main chemical derivatives of C7.
OH
red.
ox.
O
OH
Main characteristics :
100% linearity (compared to synthetic route)

high purity
100% bio-based raw material
Applications of heptanal
O
Synthesis intermediate for the fragrance and aroma industry.

industry
An perfume aromas related to C7 aldehyde is
JASMINE. This aroma is detectable in many
washing powders, soaps, candies and other jasmine
perfumed products.
natural odor : fresh, green, like vegetable

methyl-heptyne carboxylate : green and floral note
O
C
C
O
ACA : n-amyl cinnamic aldehyde : synthetic jasmine

CHO
Jasmonoids
Applications of heptanol
red.
OH
Synthesis intermediate in the fragrance and aroma industry (with fruit taste)
Trace quantities are used in perfumes to provide a peach-apricot aroma.
-decalactone :
coconut, vanilla flavour (dairy products, beverage)
O
Esters with fruit notes (heptyl butyrate, octanoate )
Synthesis intermediate for plasticizers for polymers.
Applications of heptanoic acid

ox.
OH
The diversity of applications of this acid is surprising :

Valorised in the form of esters as lubricant for military
aircraft jet engines, car engines and refrigerant.
compared to C6/C8/C10 analogues
better compromise in terms of low viscosity at low
temperature and low volatility at high temperature,
very low color
100% linear saturated acid,
lower pour point,
higher viscosity index.
High efficiency of C7 salts as corrosion inhibitor (water
based hydraulic fluids for automotive, additives in paints,
cutting oils, metalworking fluids).
Applications of heptanoic acid

ox.
OH
Chemical intermediates for Pharmaceuticals and cosmetics
emollient agent / surfactant in personal care (propylene
glycol diheptanoate, stearyl heptanoate ) and in

pharmaceutical gel (neopentylglycol diheptanoate)
Chemical intermediates for aromas and perfumes.
perfumes
natural, green grassy and fruity ester like odour in
banana flavours and in coffee, dairy products, passion
fruit
Synthesis intermediate for plasticizers for polymers.

Improves the properties of herbicides.
herbicides
C11 derivatives
Derivatives of methyl undecylenate have the rare property of being both
long and bi functional.
functional
They are versatile molecules for chemical synthesis.
O
+H O
methyl undecylenate
2
mthyl
undecylenate
- MeOH
undecylenic acid
Both are used for their natural bioactivity and fungi resistance.
resistance
OH
C11 derivatives
from pharmaceuticals
Bioactivity and fungi resistance.
In nature, trace quantities of C11 acid are found in
sweat, tears and hair fats. Under salt form (Zn/Ca), it is
used in pharmaceuticals for human skincare preparations.
ie :
- treatment of athletes foot

- effective against denture stomatitis
- herpes ...
combining surfactant as well as natural

bioresistance properties
Bacteriostatic action in baby diapers.
diapers
One of the safest, ecological, most economical and highly
effective natural bacteriostatic and antifungal agents
C11 derivatives
Cosmetics Personal Care
Hair care / anti-dandruff shampoos
Deodorant
Beauty creams
(antiseptic) Soaps
Bacteriostatic emulsifier for cosmetics
as surfactants, like
Betain C11 = Amphoram U (CECA)
O
R
NH
CH 3
(CH 2 )3 N + CH 2 COO -, NaCl
CH 3
undecylenamido propyl betaine

O
undecylenic acid diethanolamid
R C N(CH2Ch2OH)2
O
disodium undecylenamido MEA-sulfosuccinate
R'O C CH 2
R = CH2=CH(CH 2)8_
SO 3Na
C
COONa
R ' : U n d e c y le n a m id o M E A
safe and natural bacteriostatic agent compared to chemical biocides

(imidazoles, tolnaftates) used in cosmetics.
C11 derivatives
to Perfumes
Undecylenic Acid (fruity-rosy note)
Methyl Undecylenate (heavy citrus note) for lilac based
perfumes and anti-odors.
Chemical intermediates for perfumes.

perfumes
Undecenal for rose or jasmine based formulations, key component for
quality perfumes (fixing agent) and quality enhancer for large volume
products.
Undecenol (citrus, floral note), volume / natural freshness to floral

compositions, effect increasing, especially in soap formulations.
Macrocyclic musks
ie : Cyclopentadecanolid
(Exaltolide, Pentalide, Thibetolide)
O
O
In a second step,
step ricinoleic acid is cleaved to give capryl alcohol (2-octanol)
octanol
and sebacic acid (C10 ,-diacid).
C8
2-octanol
C18
OH
RICINOLEIC
O
Basic Cracking
C10
OH
HO
OH
Ricinoleic acid
OH
O
O
Sebacic acid O
HO
OH
O
OH
Properties and uses of 2-Octanol

The 2-octanol (capryl alcohol) is mainly used as a raw material for producing
intermediates in flavors and perfumes industry.
In cosmetics,
cosmetics it is an intermediate for the
preparation of caprylic/capric triglyceride (CCT)
use as emollient, excellent as a super-fatting oil in
soap-making and improves spreading of skincare
formulas.
Capryl alcohol can be used as a possible alternate for 2-ethylhexanol or
isooctyl alcohol in the preparation of diesters plasticizers : dicapryl esters
such as dioctyl phthalate (DOP),
(DOP) dioctyl adipate (DOA).
(DOA)
2-octanol is used as a solvent.
solvent It is also used as a mineral floatation agent
and for producing emulsifiers,
emulsifiers defoaming and anti-bubbling agents.
agents
Challenges in Chemistry from vegetable oils

Green Notes for Green Chemistry
Development of Green chemistry

from vegetable oils requires to set the
conditions to make money
Use all parts of vegetable oils:

Glycerol
Fatty acids
high concentration in targeted fatty acid
dedicated vegetable oils
Develop Safer processes

Renewable chemicals with improved
Life Cycle Analysis
Renewable (bio-based) # biodegradable # safe
Thank you for your attention
No waste, everything is valorised !!!
C18
NON RICINOLEIC
Esterol A is made up of saturated and unsaturated

natural fatty acid methylic esters like stearic, oleic or
linoleic acid.
Esterol A is mainly used as machining oils due to good lubricating properties

(oiliness, anti-wear properties). It finds a lot of applications in a large range
of domains :
Metal working fluids / Cutting oils (lubricity for
anti-wear additive when sulfurized),
Fat liquors for leather treatment,
Concrete mold release agents (biodegradable, fluid
oil, easy to emulsify),
Grease and lubrication formulations,
Anti-foaming agents.

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Glycerol as a co-product of oleochemicals /biodiesel and vegetable oil

Part of the work presented here has been carried out

Arkema is a member of the European Biorefinery Projects

Acrolein and Acrylic Acid from Glycerol

Related to existing Network

Sources of Glycerin. (Worlwide).

Classical Acrolein and Acrylic acid processes

Standard Acrylic Acid

Techniques de lingnieur, 1995, J6055 and J6100

Environmentally Friendly Process:

Explosion of a Storage facility

Cradle to gate analysis

Acrolein ex propylene: 3190 kg CO2/t

Historical prices: propylene and glycerol in

Propylen contract Europe (/t)

Glycerin 80% crude Europe (/t)

Basic Design of Industrial Plant

Glycerol to Acrolein- Operating conditions

Catalyst: WO3/ZrO2 (solid acid)

Glycerol: 6.7 % vol.

12 Principles of Green Chemistry

Prevent waste We use a waste

Industrial property : Arkema portfolio

And much more in a near future

Industrial property : Arkema portfolio

Industrial property : Arkema portfolio

Further applications of a Glycerol to acrolein

Melting point: -88 C

Flash point: -26C cc

VLE: 0.25 mg/m3

Acrolein: a platform molecule, for Bio-based

Some products made out of Acrolein

Some other products made from Acrolein

Diels Alder Reactions

Diels-Alder (Acrolein as 1,3 diene)

Intermediate to nicotinic acid (niacin)

Vinyl alcohols through Grignard reactions

Terbinafin side chain

Vinyl Alcohol through reduction

Hydrogen transfer reaction (Meerwein-Ponndorf), in liquid phase

Gas phase reaction

Ethylene acetal amino propionaldehyde

Acrolein and alcohols

Vinyl dioxan & dioxolan

Monomer for spirane resins

Reaction with HCN

mild alkaline catalyst

Intermediate for pharmaceutically and biologically active substances

Halogen Propionaldehyde Acetals

(used in Jasmone industry)

Salts and the Wittig Reaction

R=H, D,L Tryptofan

4-oxo heptanedial derivative

For more informations

Bio-based acrolein technology for licencing

PILOT scale (Several kg/hr) end 2011

Partnership on a case by case basis.

Valorization of Castor Oil for Polymer and Fine Chemicals

Edible vs Non-edible Oils / Fatty acid types

Arkemas Castor Biorefinery

Castor is indigenous to the

Castor oil chemically unique

Castor Beans seeds contains 40 to 60 % of oil

bio-resourced compounds such

wetting and lubricating agent in

100% linearity (compared to synthetic route)

natural odor : fresh, green, like vegetable

ACA : n-amyl cinnamic aldehyde : synthetic jasmine

Esters with fruit notes (heptyl butyrate, octanoate )

Chemical intermediates for Pharmaceuticals and cosmetics

emollient agent / surfactant in personal care (propylene

Synthesis intermediate for plasticizers for polymers.

undecylenic acid diethanolamid

disodium undecylenamido MEA-sulfosuccinate

Chemical intermediates for perfumes.

Undecenal for rose or jasmine based formulations, key component for

Undecenol (citrus, floral note), volume / natural freshness to floral