(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 ...
Sustainable Castor Oil-based Production Through Reactive Seed Crushing “in-planta” Catalysis for the production of methyl ricinoleate Jean-Luc DUBOIS
Collaborative development with VALAGRO Acknowledgement to ADEME for financial support
Arkema’s Plant-Based factories 4 Vegetable Oil-based 1 Wood-based 11 % of Turnover (700 M€) Coating Solutions
Feuchy
Hengshui
Fatty Nitriles & Amines
Castor Oil-Based PA Monomers Sebacic Acid
Vegetable Oil based
Blooming Prairie
Epoxidized Linseed & soybean Oils, Terpenes
Parentis
Marseille St Menet
Wood-based Activated Carbons
Castor Oil based Polyamide Monomer
Arkema’s Renewable Products have technical advantages
Jean-Luc Dubois - AOCS - May 4-7, 2014, San Antonio, Texas, USA
Malaysia
BioMethionine Under construction
Fatty Acid Profile Source: « Lexicon of Lipid Nutrition », Pure Appl. Chem., Vol 73, N° °4, PP 685-744, 2001 and Oleon datasheets + internal data
Safflower (high linoleic) Linseed Sunflower Walnut Soya bean Camelina Cotton seed Corn Jatropha Canola Rapeseed low erucic Groundnut
Saturated Monounsaturated Polyunsaturated
Lesquerella fendleri Rapeseed HIGH erucic Crambe Safflower (high oleic) Honesty Lard Palm Olive Tallow
Castor
CASTOR Babassu Palm Kernel Coconut DH12C
0%
20%
40%
60% Content (wt %)
Jean-Luc Dubois - AOCS - May 4-7, 2014, San Antonio, Texas, USA
80%
100%
Castor Composition H3C
0.5 1.0 %
85.0 – 95.0 %
CH3
OH HO
HO
O
O
1.0 – 5.0 %
H3C
2.0 – 6.0 %
H3C
HO
HO
O
O OH
HO
CH3
0.3 0.7 %
0.5 1.0 %
CH3
HO
O
O
OH
CH3
HO
0.5 1.0 %
CH3
HO
O
O
Other minor fatty acid: lesquerolic acid, … Jean-Luc Dubois - AOCS - May 4-7, 2014, San Antonio, Texas, USA
0.3 %
Castor oil seed production Source: FAOStat, Data in tons for 2012 countries India China, mainland
2012 1 630 000 170 000
Mozambique
62 000
Brazil
25 989
Thailand
12 500
Paraguay
10 000
Ethiopia
7 000
South Africa
6 000
Viet Nam
6 000
Pakistan
4 200
Angola
4 000
Ecuador
3 000
Kenya
3 000
United Republic of Tanzania
3 000
Madagascar
2 650
Jean-Luc Dubois - AOCS - May 4-7, 2014, San Antonio, Texas, USA
Castor Oil Trade Export from India and major applications per region
Lubs Paints PU
PA-11 DC10 / DA10
Jean-Luc Dubois - AOCS - May 4-7, 2014, San Antonio, Texas, USA
Castor Seeds Composition ● Seeds are rich in Oil and Proteins: 40 to 60 % Oil, 15 to 20 % Proteins and contain a dangerous toxalbumine: Ricine, and Allergen (CB-1A)
Oil contains mainly ricinoleic acid. ● Used in lubricants, raw materials for polymers (Rilsan) and source of undecylenic acid and sebacic acid
Applications in ● Polymers Polyurethane, PolyAmides, Polyesters ● 1st generation Biodiesel acceptable only if diluted in other vegetable oil ● 2nd generation Biodiesel (full hydrogenation + isomerisation) acceptable as such ● Other industrial applications ● Non-ricinoleic part to Fuel. 15 % of the Castor Oil ends up as Esterol A (methylester of non ricinoleic acid sold as a solvent) in Arkema’s process.
Jean-Luc Dubois - AOCS - May 4-7, 2014, San Antonio, Texas, USA
Fears about Ricin Georgi Markov, a Bulgarian writer and BBC journalist, was assassinated in 1978 by a man yielding an umbrella. Markov, a dissident who broadcasted sarcastic comments of Communism in Bulgaria, had survived two previous assassination attempts when he was attacked at a bus stop by an unknown man who used a modified umbrella to shoot a ricin pellet into his leg. He soon developed a high fever, and after four days of agony, was dead.
Jean-Luc Dubois - AOCS - May 4-7, 2014, San Antonio, Texas, USA
Ricin and similar toxins
structure: A-S-S-B Jean-Luc Dubois - AOCS - May 4-7, 2014, San Antonio, Texas, USA
Essentials of Glycobiology Second Edition
Allergen In addition to the toxic Ricin, Castor beans also contain a powerful allergen CB-1A.
It is said that 8 to 20 % of the population is allergic to Castor, with in some cases anaphylactic shocks.
Structures of allergens from the prolamin superfamily. A: soybean hydrophobic seed protein (Gly m 1), B: peach nonspecific lipid transfer protein (Pru p 3), C: castor bean 2S albumin (Ric c 3), and D: wheat 0.19 α-amylase inhibitor (Tri a 28). In recent years, it has become clear that most allergens belong to a limited number of protein families.
Jean-Luc Dubois - AOCS - May 4-7, 2014, San Antonio, Texas, USA
Prices…
Jean-Luc Dubois - AOCS - May 4-7, 2014, San Antonio, Texas, USA
Castor Oil historical prices Castor Oil Market Value, FOB Kandla (India) 3000
Castor Oil Value (US$/t)
2500
2000
1500
1000
500
0 o-95
j-98
a-01
j-04
o-06 Date
Jean-Luc Dubois - AOCS - May 4-7, 2014, San Antonio, Texas, USA
j-09
a-12
d-14
Castor and Rapeseed meal Values in India (for export), US $/ton 300 Castor Meal (Bulk) ex Kandla - US $/ton
Annual Average price (US $/ton)
250
Rapeseed Meal Ext (Bulk)
200
150
100
50
0 2002
2004
2006
2008 Year
Jean-Luc Dubois - AOCS - May 4-7, 2014, San Antonio, Texas, USA
2010
2012
2014
New technology: Reactive Seed Crushing Process
Jean-Luc Dubois - AOCS - May 4-7, 2014, San Antonio, Texas, USA
Conventional process to produce Castor Oil and its Methyl ester
Solvent
Note: hexane phase-out probable COV emissions 800g/t seeds
To Transesterification unit Steam
Refining Crushing Extraction
Jean-Luc Dubois - AOCS - May 4-7, 2014, San Antonio, Texas, USA
Evolution
Solvent
Note: hexane phase-out probable COV emissions 800g/t seeds
To Transesterification unit Steam
Refining Trituration Extraction
Jean-Luc Dubois - AOCS - May 4-7, 2014, San Antonio, Texas, USA
Reactive seed crushing process Solvent (Methanol)
Refining Steam
Methyl Ester FAME Glycerine
Crushing Extraction
Jean-Luc Dubois - AOCS - May 4-7, 2014, San Antonio, Texas, USA
PRODUCTION OF FATTY ACIDS METHYL ESTERS BY REACTIVE CRUSHING PROCESS 1) Seeds conditioning 2) Drying
Castor flakes
Castor seeds
1) Methanol + basic catalyst 2) Methanol evaporation 3) Glycerin removing 4) Methyl esters purification
Defated castor flakes
Methyl ricinoleate Jean-Luc Dubois - AOCS - May 4-7, 2014, San Antonio, Texas, USA
Lab tests
Produce large samples (2.5 liters) for Thermal Cracking test Then move to demonstration stage
Jean-Luc Dubois - AOCS - May 4-7, 2014, San Antonio, Texas, USA
Amount of catalyst Criteria
Test 09E08
Test 09E11
Test 09E12
Castor flakes (g)
350
350
350
Methanol (g)
700
700
700
NaOH (g)
1.1
0.7
0.35
87.1
86.3
57.5
2.6
3.5
3.7
Esters losts (%)
10.3
10.2
38.8
Acidity index (mg KOH/g)
0.46
0.52
0.60
MeC16 (%)
0.85
0.75
0.50
MeC18:2 (%)
2.90
3.02
1.92
MeC18:1(%)
3.46
2.09
1.08
MeC18:0 (%)
0.96
0.71
0.73
MeC18:1,OH (%)
90.65
73.16
49.80
Monoglycerides (%)
1.19
16.14
12.22
Diglycerides (%)
nd
0.80
4.28
Triglycerides (%)
nd
0.38
28.77
Methyl ester yield (%) Fat remaining in meal (eq. Ester) (%)
Jean-Luc Dubois - AOCS - May 4-7, 2014, San Antonio, Texas, USA
Effect of reaction time Criteria
Test 09E26
Test 09E08
Castor flakes (g)
350
350
Methanol (g)
700
700
NaOH (g)
1.1
1.1
Duration of reaction (contact time) (min)
60
30
Methyl ester yield (%)
90.4
87.1
Fat remaining in meal (eq. Ester) (%)
4.5
2.6
Esters losts (%)
5.1
10.3
Acidity index (mg KOH/g)
0.29
0.46
MeC16 (%)
0.71
0.85
MeC18:2 (%)
3.31
2.90
MeC18:1(%)
2.90
3.46
MeC18:0 (%)
0.86
0.96
MeC18:1,OH (%)
90.34
90.65
Monoglycerides (%)
1.82
1.19
Diglycerides (%)
0.05
nd
Triglycerides (%)
0.00
nd
Jean-Luc Dubois - AOCS - May 4-7, 2014, San Antonio, Texas, USA
Product Analysis Biodiesel
TARGET ARKEMA
EN14214
Analysis of an ester from conv. process
Seeds Acidity mg KOH/g Esters Yield
-
Test 09E25
Test 09E26
Test 09E30-4
2.6
2.6
0.6
88.7
90.4
~90
-
≤1.0
0.8
1.82
1.87
0.36
Monoglycerides, %
2000
non allergenic at 10%
* Value above the saturation limit of the method ** + additional drying at 100°C, 4 h
Jean-Luc Dubois - AOCS - May 4-7, 2014, San Antonio, Texas, USA
Methyl esters
Methy Ricinoleate Conventional Process
Methy Ricinoleate Reactive Crushing Process
Jean-Luc Dubois - AOCS - May 4-7, 2014, San Antonio, Texas, USA
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, Jacques BARBIER, Antoine PICCIRILLI WO2010/084276, Jean-Luc DUBOIS, Antoine PICCIRILLI, Jacques BARBIER, Julien MAGNE WO2011/092430, (Jatropha seeds) Jean-Luc DUBOIS, Juline MAGNE, Anoine PICCIRILLI …
Jean-Luc Dubois - AOCS - May 4-7, 2014, San Antonio, Texas, USA
Aknowledgements
ADEME for financial support for the RICHARB project
Jacques BARBIER, Antoine PICCIRILLI, Julien MAGNE (Valagro) for active involvement in the project
Jean-Luc Dubois - AOCS - May 4-7, 2014, San Antonio, Texas, USA
Castor Oil : a vegetal refinery ! As a conclusion, a little summarize of all the applications of Castor Oil derivatives … Esterol A
Undecylenic acid
11-aminoundecanoic acid methyl undecylenate
Thank you all for your attention. heptanol
heptanoic acid heptanal Castor oil
Jean-Luc Dubois - AOCS - May 4-7, 2014, San Antonio, Texas, USA
2- octanol Sebacic acid
