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1
Added value of Homogeneous,
Heterogenous and Enzymatic Catalysts in
Biorefineries
Jean-Luc DUBOIS
Scientific Director
Arkema is a member of the European Biorefinery / technology Projects
Arkema received the 2013 Award from the European BiomassIndustry Association for its merits in advanced biomass processing
OPTICO
OPTICO
2 Jean-Luc DUBOIS // Montreal, June 17th 2013, BIO World Congress
Arkema’s Existing Biorefineries
4 Vegetable Oil-based
1 Wood-based
11 % of Turnover (700 M€)
Arkema’s Renewable Products have technical advantages
2
Fatty Nitriles & Amines
Feuchy
Epoxidized Linseed& soybean Oils,
Terpenes
Blooming Prairie
Casda
Castor Oil-BasedPA MonomersSebacic Acid
Marseille St Menet
Castor Oil basedPolyamide Monomer
Coating Solutions
Wood-basedActivated Carbons
Parentis
Vegetable Oil based
3 Jean-Luc DUBOIS // Montreal, June 17th 2013, BIO World Congress
Fatty Acid ProfileSource: « Lexicon of Lipid Nutrition », Pure Appl. Chem., Vol 73, N°°°°4, PP 685-744, 2001 and Oleon datasheets + internal data
0% 20% 40% 60% 80% 100%
DH12C
Coconut
Palm Kernel
Babassu
CASTOR
Tallow
Olive
Palm
Lard
Honesty
Safflower (high oleic)
Crambe
Rapeseed HIGH erucic
Lesquerella fendleri
Groundnut
Rapeseed low erucic
Canola
Jatropha
Corn
Cotton seed
Camelina
Soya bean
Walnut
Sunflower
Linseed
Safflower (high linoleic)
Content (wt %)
Saturated
Monounsaturated
Polyunsaturated
Castor
4 Jean-Luc DUBOIS // Montreal, June 17th 2013, BIO World Congress
Ricinoleic Acid based
Renewable polymers
C7
C8
Amino
Acid
C11
DiAmine
DiAcid
C10
PA THT
PA HT
Bio-composites
2 Octanol derivatives
Castor
plants
Castor
seeds
Castor
oil
Glycerol
Casda’s Biorefinery
Marseille’s Biorefinery
O
HO
OH
85-90 %
PA 10.10PA 10.XPA X.10
PA11
5 Jean-Luc DUBOIS // Montreal, June 17th 2013, BIO World Congress
Value to the customer
● High flexibility
● Low water absorption
● Chemical resistance
● Impact resistance
● Low density
● Easy tube extrusion processing
Market opportunities & drivers
● Transportation
– Lightweight materials for metal replacement
● Energy (off shore)
– Non conventional oil recovery
● Consumer goods (sports, cosmetics)
– Increasing standard of living
Main end-markets
5
Specialty polyamides market
6 Jean-Luc DUBOIS // Montreal, June 17th 2013, BIO World Congress
Selective Enzymatic Extraction of Ricinoleic Acid
from Castor Oil
Collaboration with C. Bourlieu, B. Barea, E. Dubreucq, P. VilleneuveUMR IATE, Montpellier, France
Ingénierie des Agropolymères et Technologies Émergentes
7 Jean-Luc DUBOIS // Montreal, June 17th 2013, BIO World Congress
RRR : 71.0 % (p/p)
ROR : 7.2 % (p/p)91 %
1,3-diricinoleoyle-2-
oleoyle-sn-glycerol
RLR : 6.6 % (p/p)
95 % 1,3-diricinoleoyle-2-
lineleoyle-sn-glycerol
RPR : 1.6 % (p/p)
78 % 1,3-diricinoleoyle-2-
palmitoyle-sn-glycerol
RRLinolenic : 0.15 % (p/p)
RSR : 1.1 % (p/p)
96 % 1,3-diricinoleoyle-2-
steroyle-sn-glycerol
RRRR (estolide): 0.45 % (p/p)
RRLesquerolate :
0.67 % (p/p)
OH
O
O
O
C
O
(CH2)7
(CH2)7
(CH2)7
C
OC
O9
11 13
OH
OH
Triacylglycerols identified in Castor Oil
R: C18:1, OH – P: C16:0 - S: C18:0 – O: C18:1 – L: C18:2
(Lin & Arcinas, 2005; Lin et al., 2006; Weber et al., 2006 )
8 Jean-Luc DUBOIS // Montreal, June 17th 2013, BIO World Congress
0102030405060708090
100T
aux
de c
onve
rsio
n (%
)
0 0.5 2 4 6 8 24
Temps (Heure)
RA
LA
OA
MethRA
MethLA
MethOA
Test in methanolysis of Castor Oil
Methanol/Castor Oil : 1.5:1 in 3 methanol additions (3*1.5:1 at 0, 2 & 4 Hr)
Legend : RA = ricinoleic acid, LA = Linoleic acid, OA = Oleic acidMethRA = Methyl ricinoleate, MethLA =Methyl linoleate, MethOA = Methyl oleate
Results on Castor Oil
Time scale (Hr)
WO2010/100366 : Jean-Luc DUBOIS, Claire BOURLIEU- LACANAL, Jéröme LECOMTE, Eric DUBREUCQ, Pierre VILLENEUVE.
Very fast enzymaticReaction ���� 0.5 hr
Con
vers
ion
Rat
e
(%
, by
acid
type
initi
ally
in
trig
lyce
ride
“in-planta” Catalysis for the production of methyl ricinoleate
Reactive seed crushing on Castor Seeds
PROCESS INTENSIFICATION
Objective: Produce at the same time Castor Oil Methyl Ester, Glycerin
and a detoxified Castor Meal without ricin and allergens
Provide a technology for the seed producer, to deliver higher value
products (esters and seed meal)
Collaborative development with VALAGRO
Acknowledgement to ADEME for financial support
10 Jean-Luc DUBOIS // Montreal, June 17th 2013, BIO World Congress
Reactive seed crushing process
Crushing
Steam
Extraction
Refining
Methyl EsterFAME
Solvent (Methanol)
Glycerine
Crushing
Steam
Extraction
Refining
Methyl EsterFAME
Solvent (Methanol)
Glycerine
+ <catalyst>
11 Jean-Luc DUBOIS // Montreal, June 17th 2013, BIO World Congress
Product Analysis
< 12 wt %
<0.5
<0.2 wt %
<0.2 wt %
<0.8 wt %
-
Biodiesel
EN14214
0.8
1.2
3.5
3.5
90.6
0.3
99.6
nd
0.03
0.33
0.36
~90
0.6
Test 09E30-4
Seeds Acidity mg KOH/g
0.6
0.9
2.3
3.3
91.5
0.57
99.1
nd
0.1
0.7
0.8
Analysis of an ester from
conv. process
-Esters Yield
≥≥≥≥ 98.5Ratio [MR/(MR+ glycerides)]
-Triglycerides, %
-Monoglycerides, %
-Diglycerides, %
0.8 – 1.1Palmitic C16:0
0.7 - 1.0Stearic C18:0
4.1- 4.7Linoleic C18:2
2.0 – 3.3Oleic C18:1
85.0 – 89.0Ricinoleic C18:1, OH (MR)
Fatty Esters Profile
≤≤≤≤ 0.3Acidity Index, mg KOH/g
≤≤≤≤1.0Glycerides (%)
TARGET ARKEMA
12 Jean-Luc DUBOIS // Montreal, June 17th 2013, BIO World Congress
Detoxification. Ricin and Allergen (CB-1A)Special acknowledgement to Dr Xiaohua He, Western Regional Research Center, USDA,
Albany, USA for “blind” testing seed meals and confirming our results. JL Dubois, A Piccirilli, J
Magne, X. He, Industrial Crops and Products, 43 (2013) 194-199.
1,6 10-4
2,4 10-4
> 4 10-4*
> 4 10-4*
Active Ricin (%)
99.99%2.2 ××××10-4100°°°°C/4h120°°°°C / 4h100°°°°C / 16hContinuous fixed bed process
99.95%8.6 ××××10-4-120°°°°C / 4h100°°°°C / 16hContinuous fixed bed process
94.50%0.01-120°°°°C / 4h100°°°°C / 16hBatch process, agitated bed
-1.8---Defatted flakes (60°C, 10h)
Ricinereduction
(%)
Ricin (%)Final Drying
(T°C, h)
Solventremoval
T°C/(h)
Drying
T°C/(h)
Seed/Seed meal
Immunologic Assay + Mass spectrometry test done by CEA (Saclay)
Continuous fixed bed process
Continuous fixed bed process
Defatted flakes (60°°°°C, 10h)
Seed/Seed meal
non allergenic at 10%> 2000120°C, 4h
non allergenic at 10%> 2000150°C, 4h
Allergenic at 10%300< DL50 < 2000*
(*mortality 100%)
-
Cutaneous sensitvity test
(Local Lymph Node Assay)
Accute toxicity on rats (DL50, mg/kg)
Final Drying(T°C, h)
* Value above the saturation limit of the method** + additional drying at 100°C, 4 h
13 Jean-Luc DUBOIS // Montreal, June 17th 2013, BIO World Congress
The Triple Effect
� Reduce CAPEX� Smaller number of pieces of equipment
� Reduce OPEX�Reduce maintenance, labor and processing cost
� Detoxify�Reduced toxicity of the Seed Meal
Also contributed to this work
● ADEME financial support to project RICHARB
● Jacques BARBIER, Antoine PICCIRILLI, Julien MAGNE (Valagro)
WO2010/076527, Jean-Luc DUBOIS, Julien MAGNE, Jacqu es BARBIER, Antoine PICCIRILLIWO2010/084276, Jean-Luc DUBOIS, Antoine PICCIRILLI, Jacques BARBIER, Julien MAGNEWO2011/092430, (Jatropha seeds) Jean-Luc DUBOIS, Jul ine MAGNE, Anoine PICCIRILLI…
14
Metathesis of Vegetable Oils for
Aminoacids production
Xiaowei Miao, Raluca Malacea, Cedric Fischmeister, Christian Bruneau, Pierre Dixneuf
Jean-Luc Dubois, Jean-Luc Couturier
15 Jean-Luc DUBOIS // Montreal, June 17th 2013, BIO World Congress
Route selected: Cross metathesis
Mechanism described by Yves Chauvin
R1
R1
R2
R2
+
R2R1
+
R1 R2
[M=]
Ru
NMesMesN
Cl
Cl PPPPhhhhPPPPCCCCyyyy3333
Homogeneous Catalystex. Grubbs II
MR
MR2
R2R1
R1 R1
M
R1
MR2
MR2
R1R1
R1
RR1 R2
R1 R1
R2
R1
R2
R2
16 Jean-Luc DUBOIS // Montreal, June 17th 2013, BIO World Congress
Arkema’s Renewable Long Chain Polyamides
Butadiene
Polyamide-12
Lactame-12
CDT
Castor Oil
Polyamide-11
Amino-11
Undecenoic Acid
Polyamide-10.10
Diamine-10
Sebacic Acid Undecenoic ME
Polyamide-12
Amino-12
Undecenenitrile
Acrylonitrile
MethylAcrylate
17 Jean-Luc DUBOIS // Montreal, June 17th 2013, BIO World Congress
Oil
Unsaturated fatty acid derivatives as precursors
to polyamides through metathesis
ϖ-unsaturated fatty nitrile / ester
METATHESIS
HYDROGENATION
(CH2)8
N
O
O
N
N
(CH2)8
O
O
O
(CH2)8
N
O
+
+
NH2
(CH2)11
O
O
O O
(CH2)8
WO2010/055273, Jean-Luc DUBOIS & WO2010/089512, Jea n-Luc DUBOISX Miao, C Fischmeister, P Dixneuf, C Bruneau, JL Du bois, JL Couturier, Green Chemistry, 2012
High TurnOverNumbers
18
Glycerol conversion to Acrolein and Acrylic Acid
Collaborations with:
Pr Hölderich, RWTH Aachen
Pr Ueda, Hokkaido University
Pr Patience, Ecole Polytechnique de Montréal
WO06/087083 Jean-Luc DUBOIS, C DUQUENNE, W HOLDERIC HWO07/090990 Jean-Luc DUBOISWO07/090991 Jean-Luc DUBOISWO08/087315 Jean-Luc DUBOIS, Gregory PATIENCEAnd more than 30 other patent applications filed
19 Jean-Luc DUBOIS // Montreal, June 17th 2013, BIO World Congress
Acrolein/ Acrylic Acid: ARKEMA’s Project
Acrolein and Acrylic acid are currently produced from propylene (Petroleum).
Double internal dehydration of Glycerol leads to Acrolein which is further oxidized to Acrylic acid
Acrolein/AcrylicAcid Unit
Crude Glycerol
Thermal Oxidizer
Acrolein or Acrylic acid
Tank
Tank
Wastes: salts…
Separation
OH
OH
OHCH2
O
+ 2H2O CH2O
OH
Methionine
Fine Chemicals/Fragrances
Polyacrylate= dispersing agents for minerals Superabsorbants
20 Jean-Luc DUBOIS // Montreal, June 17th 2013, BIO World Congress
Environmentally Friendly Process:
Avoid scenarios of past accidentsTarget: develop a new process for on-site Acrolein production (PROXI-plants) to avoid storage and transportation of a highly toxic Chemical.
Pierre Bénite, France. July 10, 1976.
Taft, USA/ December 10, 1982.
Major contamination of the Rhône River, during clean-up of a train tank367 Tons dead fish
Explosion of a Storage facility17000 people evacuated
21 Jean-Luc DUBOIS // Montreal, June 17th 2013, BIO World Congress
Cradle to gate analysis
Acrolein ex propylene: 3190 kg CO2/t
Acrolein ex glycerol: Target 980 kg/t
Acrylic acid ex Propylene: 950 kg CO2/t
Acrylic Acid ex glycerol: target 0 kg/t
Diesel Blend
Vegetable Oil
MethanolTransesterification
MethanolTransesterification
BiodieselDiesel
CO2Plant growth = consumption of atmospheric CO2
GlycerineAcrolein/ Acrylic Acid
Done within the Glyvalacr Project sponsored by Ademe
22 Jean-Luc DUBOIS // Montreal, June 17th 2013, BIO World Congress
12 Principles of Green Chemistry
1. Prevent waste ���� We use a waste
2. Design safer Chemicals and Products ���� Drop in
3. Design less hasardous chemical synthesis ���� Process for on-site production
4. Use Renewable feedstocks ���� Glycerol
5. Use catalysts not stoichiometric reagents ����Heterogeneous Catalyst
6. Avoid Chemical derivatives ���� Direct route
7. Maximize atom economy ���� C3 to C3
8. Use safer solvents and reaction conditions ���� no solvent, safer process
9. Increase Energy effciency ���� Translated into CO2 balance
10. Design Chemicals and products to degrade after use ���� return plant-based CO2 to the atmosphere
11. Analyse in Real time to prevent pollution ���� Target = on-time consumption
12. Minimize the potential for accidents ���� Avoid transportation and storage
23
Thank you
for your attention
………………………………………………………………………………………….........
………………………………………………………………………………………….........24
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