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LipochemistryBioproducts for a
Sustainable UsePREFALC
Dr. Guadalupe VACA MEDINAUniversit de Toulouse
June 27th 2013 Riobamba, Ecuador
Outline
! Process in One-Pot! Substitution Molecules! New Technology Process! New Reaction Pathway
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Valorization of Native Fatty
Acids from Rapeseed via an
Integrated Process with ThreePhase Partitioning
Guadalupe VACA MEDINA, Zphirin MOULOUNGUI, Jean-Franois FABRE,Muriel CERNY & Eric LACROUX
6th Euro Fed Lipid Congress
Athens, September 7-10, 2008
Valorisation of Native Fatty
Acids from Rapeseed
Oilseed Fatty Acids Ester
IntegratedProcess
Three PhasePartitioning
Objective
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CHOCORCH2OCOR'
CH2OCOR'OH2 3 CHOH
CH2OH
CH2OHR'COOH+' +
ROH+RCOOH H2O+RCOOR
Hydrolyse
Esterification
Candidarugosa
Reactions Lipase
Au-kbc.org
Catalytic Transformation
Oilseed
Water
Crushing
Emulsion
AqueousPhase
PelletCentrifugationHydrolysis
Lipase
Z. Mouloungui & E. Mechling (2006)
Homogenization
LipidTransformation
MechanicalStrength
Particle SizeReduction
Particle SizeReduction
PhaseSeparation
Integrated Process
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Use renewable feedstockUse safer solvents and reactionconditions
Reduce number of steps in theprocess
Maximize atom economyIncrease energy efficiencyPrevent wasteUse catalysts
RapeseedBrassica napus
Colza Kosto
(MOMONT, France)
Protein Content 17 to 19 %
Oil Content 44 %
C16:0 ~5%
C18:0 ~2%
C18:1 60-62%
C18:2 20-21%
C18:3 8-10%
Release /
Transformation
Anastas & Warner (1998)
Integrated Process
Oleosomes have affinity
with water due to theamphiphilic character of
biomolecules thatsurround the oil droplet
Oleosome
Anastas & Warner (1998)
Use renewable feedstockUse safer solvents and reactionconditions
Reduce number of steps in theprocess
Maximize atom economyIncrease energy efficiencyPrevent wasteUse catalysts
Release /
Transformation
Integrated Process
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Anastas & Warner (1998)
Use renewable feedstockUse safer solvents and reactionconditions
Reduce number of steps in theprocess
Maximize atom economyIncrease energy efficiencyPrevent wasteUse catalysts
Release /
Transformation
Integrated Process
Pellet
Protein supply
Fibre supply
Second generation of biofuels
Emulsion
Aqueous
Phase
Pellet
Integrated Process
Aqueous Phase
Conducting Medium
Oligo-elements
Fertilization
Glycerol
Anastas & Warner (1998)
water and
enzyme
Recycling
Use renewable feedstockUse safer solvents and reactionconditions
Reduce number of steps in theprocess
Maximize atom economyIncrease energy efficiencyPrevent wasteUse catalysts
Release /
Transformation
Integrated Process
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Lipase
CHOCOR"
CH2
OCOR'''
CH2
OCOR'
CHOCOR"
CH2
OH
CH2
OCOR'Lipase
R'''COOH
OH2
OH2 CHOH
CH2
OH
CH2
OCOR'Lipase
R''COOH
OH2 CHOH
CH2
OH
CH2
OHLipase
R'COOH
Triglyceride Diglyceride Monoglyceride Glycerol
+ + +
Anastas & Warner (1998)
Use renewable feedstockUse safer solvents and reactionconditions
Reduce number of steps in theprocess
Maximize atom economyIncrease energy efficiencyPrevent wasteUse catalysts
Release /
Transformation
Integrated Process
Lipase LYPOLYVE CC
(LYVEN)from Candida Rugosa
Enzymatic Hydrolysis
40C
400 rpm
300 U/g seed
A lipase (triacylglycerol acylhydrolase, EC 3.1.1.3)which makes part of the family of hydrolases acts on
carboxylic ester bonds
-10
0
10
20
30
40
50
60
70
80
90
100
0 50 100 150 200 250 300 350
time, min
HydrolysisRate,
L ip oz ym e R M IM N o vo z ym 4 35 L p 2Y .I. L Y P O L IV E C C L Y P O L IV E C C R e cyc le
Hydrolysis Rate = [FFA] x 100
[FFA] + [MG] + 2[DG] + 3[TG]
Lipid Transformation
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t 0
t f
Lipase LYPOLYVE CC is ableto convert > 99 % of
triglycerides giving place to acomplex emulsion
40% Water
55% Fatty Acids
5% Proteins
20%Rapeseed
Lipid Transformation
Z. Mouloungui & E. Mechling (2002)
ProteinsVegetable Oils
Three Phase Partitioning
Free Fatty Acids Release
Ethanol ExtractionThree Phase partitioning
C. Dennison & R. Lovrien (1997)
R. Gaur et al. (2007)
?Free Fatty Acids
BackgroundBackgroundBackground
Break emulsion forfatty acids release
Fatty Acidsin Emulsion
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Experimental Conditions
5 g lipids and proteins / 20 mL water 30 % w/v ammonium sulphate 1:1 v/v alcohol 37 C for 1 hour Centrifugation 10 min at 5000 x g
1. Methanol2. Ethanol3. 1-propanol4. Butan-1-ol5. Iso-butanol6. Ter-butanol7. 1- octanol8. 2-ethylhexan-1-ol
Tested Alcohols
1 2 3 4 5 6 7 8
1 2 3 4 5 6 7 8
C1-C2 C3-C4 C8
Without (NH4)2SO4
With (NH4)2SO4
Three Phase Partitioning
CN Solvent% LIPID
EXTRACTION(NH4)2SO4
1 Methanol -
2 Ethanol 80
3 1-propanol 85
4 Butan-1-ol 88
4 Iso-butanol 95
4 Tert-butanol 86
8 1-octanol 97
8 2-ethylhexan-1-ol 90
Three Phase Partitioning
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Alcohol Catalyst Conditions Reference
Methanol 2%p-TSA3:1 alcohol/oleic acid, 500 rpm,
120 min,100CE. Lacroux (2006)
Ethanol 2%p-TSA3:1 alcohol/oleic acid, 500 rpm,
120 min,110CE. Lacroux (2006)
1-octanol0.20 mol
phosphoric acid0.23 mol oil, 1.2 mol alcohol, 7
h, 500 rpm, 130CC. Lacaze & Z.
Mouloungui (1999)
2-ethylhexan-1-ol2%p-TSA in
xilene50 mmol oleic acid, 50 mmol
alcohol, 300 rpm, 50 min, 140CC. Lacaze & Z.
Mouloungui (2000)
Chemical Catalysis
Chemical Catalysis
Enzymatic Catalysis
Fatty Acids
+
Alcohol
Esterification
CN AlcoholESTERIFICATION
DEGREE (%)
1 Methanol -
2 Ethanol 0
3 1-propanol 2
4 Butan-1-ol 18
4 Iso-butanol 30
4 Tert-butanol 0
8 1-octanol 58
8 2-ethylhexan-1-ol 85
Experimental Conditions
5 g lipids and proteins / 20 mL water 30 % w/v ammonium sulphate 1:1 v/v alcohol 37 C for 4 hour Centrifugation 10 min at 5000 x g
Enzymatic Catalysis
Fatty Acids
+
Alcohol
Chemical Synthesis
Enzymatic Synthesis
CN AlcoholESTERIFICATION
DEGREE (%)
1 Methanol -
2 Ethanol 0
3 1-propanol 2
4 Butan-1-ol 18
4 Iso-butanol 30
4 Tert-butanol 0
8 1-octanol 58
8 2-ethylhexan-1-ol 85
ED = [Ester] x 100
[Ester] + [Fatty Acid]
Esterification
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Summary
Substitution of ASA from
fossil origin by ASA from fattyacid esters of vegetable oils
Laure CANDY, Carlos VACA-GARCIA & Elisabeth BORREDON
5th International Conference on Renewable Resources & Biorefineries
Ghent, June 10-12, 2009
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Paper Production & Consumption in 2006
84,1
65,0
31,1
22,7
18,2
12,1
10,7
10,0
10,0
14,2
0,0 20,0 40,0 60,0 80,0 100,0
USA
China
Japan
Germany
Canada
Finland
Sweden
Korean Republic
Italy
France
Paper and Board Production (106
tons)
10th world Rank
301
49
247
253
213
268
176
201
179
330
0 100 200 300 400
USA
China
Japan
Germany
Canada
Finland
Sweden
Korean Republic
Italy
France
Paper and Board Annual Consumption (kg/inhabitant)
24th world Rank
Copacel Annual Report; 2007 ; http://internet.copacel.org/rapport_annuel.php
95 industries111 factories181 papermachines18,277 employees6,2 Billion Turnover
France
Laboratoire de Chimie Agro-Industrielle Study of Alkenyl Succinic Anhydrides from fatty acid esters of vegetable oils as paper sizing agents
French Paper & Board Production in 2006
Newsprint
11%
Corrugated
paper 34%
Flexible
packaging
3%
Paperboards
9%
Others 5%
Toiletries 7%
Printing
paper 32%
3,2 Mt
Copacel Annual Report; 2007 ; http://internet.copacel.org/rapport_annuel.php
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Laboratoire de Chimie Agro-Industrielle Study of Alkenyl Succinic Anhydrides from fatty acid esters of vegetable oils as paper sizing agents
Papersheet process
Chemical
Mechanical
Additives
Papermachine
Laboratoire de Chimie Agro-Industrielle Study of Alkenyl Succinic Anhydrides from fatty acid esters of vegetable oils as paper sizing agents
The different additives in paper process
Fillers
Calcium
carbonate
Clay
Talc
Additives : specialty chemicals
Polymer binders;
56%
Coating additives;
6%
Process chemicals;
11%
Others; 5%
Sizing agents;
12%
Colorants; 1,50%
Synth. dry strength
resins; 2%
Wet strength agents;
7%
M. Prinz & W.S. Schultz, Wochenblatt fr
Papierfabrikation, 2006, 22, 1329-1335
Sized paper Unsized paper
Sizing agents
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Laboratoire de Chimie Agro-Industrielle Study of Alkenyl Succinic Anhydrides from fatty acid esters of vegetable oils as paper sizing agents
Sizing agents
Sized paper Unsized paper
Sizing agents Cellulose
Alkenyl Succinic
Anhydride (ASA)O
O
O
HO
O
HO
OH
O
HO
O
HOHO
OH
O
HO OH
HO
O
HO HO
OH
OH
n
O
O
Rosin
COOH
O
O
OAlkyl Ketene
Dimer
()12
OO
()12Petrochemical -olefins
Isomerization
ASA
Maleinization
Laboratoire de Chimie Agro-Industrielle Study of Alkenyl Succinic Anhydrides from fatty acid esters of vegetable oils as paper sizing agents
Objectives
Petrochemical ASA
Substitution ?
Olo-ASA
Optimum C16-C20
Maximal hydrophobic character
O
O
O
O
O
O O
OR
Oleo-ASA
L. Neimo ; Papermaking Science & Technology,
1999, 4, 151-203 Fatty acid esters C18-C22
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Laboratoire de Chimie Agro-Industrielle Study of Alkenyl Succinic Anhydrides from fatty acid esters of vegetable oils as paper sizing agents
Objectives
Vegetal
Sizing Agent
Green labelMarket in
developement
Petrochemical ASA
Substitution
Agricultural resources
valorization
Oleo-ASA
O
O
R
Source=
Alkyl oleates
R = linear
-CH3-C2H5-C3H7-C4H9-C5H11-C6H13
R = branched
R = cyclicCH3
CH3
CH3CH3
CH3CH3
CH3CH3
O
OR
9
10
O
OR
OO O
9
10
11
O
OR
9
10
OO O
8
O
OR
9
10 8
OO O
OO O
11
O
OROO O
+
a b
ene-reactionallylic addition
910
F. Stefanoiu et al ; Eur. J. Lipid Sci. Technol., 2008, 110, 441-447 K. Holmberg & J.A. Johansson, Acta Chem. Scand., 1982, B36, 481-485
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Laboratoire de Chimie Agro-Industrielle Study of Alkenyl Succinic Anhydrides from fatty acid esters of vegetable oils as paper sizing agents
Oleo-ASA synthesis
Secondary reactions
maleic anhydride polymerizationanhydride/alkene copolymerizationretro-ene reaction
Purification : distillation under reduced pressure
Synthesis conditions
230 C8 hmolar ratio nANH/nC=C = 1,3N2 atmosphere without catalyst
RR'
H
OO O
RR
'
OO O
J. Quesada et al., J. Am. Oil Chem. Soc., 2003, 80, 281-286
Laboratoire de Chimie Agro-Industrielle Study of Alkenyl Succinic Anhydrides from fatty acid esters of vegetable oils as paper sizing agents
Optimization of the Oleo-ASA synthesis
Ene-reaction : ethylic, propylic and isopropylic oleates
Optimal
conditions
O OOO
O
R
+
Doehlert
experimental design
EsterEster Anhydridemalique
Anhydride
malique
Produits
secondairesProduits
secondairesOlo-ASAOlo-ASA
EsterEster Anhydridemalique
Maleic
Anhydride
Produits
secondairesSecondary
productsOlo-ASAOlo-ASA
Temprature (C)(220 ; 1,2)
(235 ; 0,7)
(235 ; 1,7)
(250 ; 1,2)(190 ; 1,2)
(205 ; 1,7)
(205 ; 0,7)
Temperature (C)(220 ; 1,2)
(235 ; 0,7)
(235 ; 1,7)
(250 ; 1,2)(190 ; 1,2)
(205 ; 1,7)
(205 ; 0,7)
Molar ratio
(220 ; 1,2)
(235 ; 0,7)
(235 ; 1,7)
(250 ; 1,2)(190 ; 1,2)
(205 ; 1,7)
(205 ; 0,7)
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Optimization of the Oleo-ASA synthesis
Consumption > YieldSecondary products
Topt = 220-235C
ratioopt = 1.3-1.5
190 220 250
0,7
1,2
1,790-100
80-90
70-80
60-70
50-60
40-50
30-40
20-30
10-20
0-10
Yield in ASA (%)
T (C)
R
190 220 250
0,7
1,2
1,719-22
16-19
13-16
10-13
7-10
4-7
1-4
190 220 250
0,7
1,2
1,790-100
80-90
70-80
60-70
50-60
40-50
30-40
20-30
10-20
0-10
Gardner Index Clarity index
T (C)
R
T (C)
R
190 220 250
0,7
1,2
1,790-100
80-90
70-80
60-70
50-60
40-50
30-40
20-30
10-20
0-10
Oleate Consumption (%)
T (C)
R
Laboratoire de Chimie Agro-Industrielle Study of Alkenyl Succinic Anhydrides from fatty acid esters of vegetable oils as paper sizing agents
Cobb Index
Cobb60
Water
Measurement of the increasein weight
60 s
Cobb60 (g/m)
0
20
40
60
80
100
120
140
Poor
Efficient
LowSizing
ISO 535, 1994, Determination of water absorptiveness Cobb Method
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Laboratoire de Chimie Agro-Industrielle Study of Alkenyl Succinic Anhydrides from fatty acid esters of vegetable oils as paper sizing agents
Linear Oleo-ASA R = n-CnH2n+1
C1 C2 C3 C4 C5 C6
30 2927
60
43
19 22
0
20
40
60
80
100
120
140
Sizing optimum forethylic & propylic ASA
Efficient fiber coveringEasier approach for cellulose hydroxyl groups
Cobb (g/m)
Laboratoire de Chimie Agro-Industrielle Study of Alkenyl Succinic Anhydrides from fatty acid esters of vegetable oils as paper sizing agents
Branched and cyclic oleo-ASA
29
43
22
3950
25
0
20
40
60
80
100
120
140
C3 C4 C6
CH3
CH3 CH3
CH3
CH3
CH3
100
Branched oleo-ASA less competitiveSterical hindrancea Reactivity more difficult with hydroxylsIsopropylic ASA really efficient
Cobb (g/m)
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Laboratoire de Chimie Agro-Industrielle Study of Alkenyl Succinic Anhydrides from fatty acid esters of vegetable oils as paper sizing agents
Optimum oleo-ASA for sizing application
ASAOE
O
O
OO
O
ASAOPrO
O
OO
O
ASAOIPrO
O
OO
O
Cobb60
2227
1925
0
20
40
60
80
100
120
140
ASAPAP
ASAAO
ASAOM
ASAOE70
ASAOE98
ASAOPr-e
ASAOPr-a
ASAOB
ASAOPe
ASAOH
ASAOIPr-e
ASAOIPr-a
ASAOMPr
ASAOMPe
ASAO2EH
ASAOCH
ASAEMT
ASAEMC
ASAOE802
ASAOB804
ASAO2EH808
ASAO2EH208
ASAEMCE
ASAEMTO
ASAEETO
ASAEPrTO
ASAEBTO
g/m
ASAOE
ASAOPr
ASAOIPr
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Other specifications for sizing agents
90,290,289,6
90,2
82
84
86
88
90
92
94
96
98
100
ASAPAP
ASAAO
ASAOM
ASAOE70
ASAOE98
ASAOPr-e
ASAOPr-a
ASAOB
ASAOPe
ASAOH
ASAOIPr-e
ASAOIPr-a
ASAOMPr
ASAOMPe
ASAO2EH
ASAOCH
ASAEMT
ASAEMC
ASAOE802
ASAOB804
ASAO2EH808
ASAO2EH208
ASAEMCE
ASAEMTO
ASAEETO
ASAEPrTO
ASAEBTO
ASAEPeTO
2227
1925
0
20
40
60
80
100
120
140
ASAPAP
ASAAO
ASAOM
ASAOE70
ASAOE98
ASAOPr-e
ASAOPr-a
ASAOB
ASAOPe
ASAOH
ASAOIPr-e
ASAOIPr-a
ASAOMPr
ASAOMPe
ASAO2EH
ASAOCH
ASAEMT
ASAEMC
ASAOE802
ASAOB804
ASAO2EH808
ASAO2EH208
ASAEMCE
ASAEMTO
ASAEETO
ASAEPrTO
ASAEBTO
Cobb60 (g/m) Total retention (%)
Surface tension (mN/m)Particles diameter (m)
31,130,5 30,8 30,2
20
22
24
26
28
30
32
34
36
38
40
ASAPAP
ASAAO
ASAOM
ASAOE70
ASAOE98
ASAOPr-e
ASAOPr-a
ASAOB
ASAOPe
ASAOH
ASAOIPr-e
ASAOIPr-a
ASAOMPr
ASAOMPe
ASAO2EH
ASAOCH
ASAEMT
ASAEMC
ASAOE802
ASAOB804
ASAO2EH808
ASAO2EH208
ASAEMCE
ASAEMTO
ASAEETO
ASAEPrTO
ASAEBTO
ASAEPeTO
0,5
1,3
0,7
0,2
0
0,2
0,4
0,6
0,8
1
1,2
1,4
1,6
1,8
2
ASAPAP
ASAAO
ASAOM
ASAOE70
ASAOE98
ASAOPr-e
ASAOPr-a
ASAOB
ASAOPe
ASAOH
ASAOIPr-e
ASAOIPr-a
ASAOMPr
ASAOMPe
ASAO2EH
ASAOCH
ASAEMT
ASAEMC
ASAOE802
ASAOB804
ASAO2EH808
ASAO2EH208
ASAEMCE
ASAEMTO
ASAEETO
ASAEPrTO
ASAEBTO
ASAEPeTO
Laboratoire de Chimie Agro-Industrielle Study of Alkenyl Succinic Anhydrides from fatty acid esters of vegetable oils as paper sizing agents
Emulsion stability
Same
granulometry
t0
t12h
ASAOPr
10 m
10 m
Stable
emulsion
10 cm
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Laboratoire de Chimie Agro-Industrielle Study of Alkenyl Succinic Anhydrides from fatty acid esters of vegetable oils as paper sizing agents
Strategy
Stripping Hydrolysis Reactivity
Comparison oleo-ASA vs petrochemical ASA
Oleo-ASA advantages
Equivalent sizing
Optimal oleo-ASA Petrochemical ASA
Laboratoire de Chimie Agro-Industrielle Study of Alkenyl Succinic Anhydrides from fatty acid esters of vegetable oils as paper sizing agents
Steam Stripping
ASA : 10% H2O : 90%
Vapor stripping
L/L Extraction
MTBE
Organic phase Aqueous phase
Solvant concentration
Dilution
HPLC analysis
Deposits (stickies):
In air-ductsOn presses
Heating
W.E. Scott, Principles of Wet End Chemistry, Tappi Press, 1996; 99-110
J. Lindfors et al.,Nord. Pulp Paper Res., 2005, 20, 453-458
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Laboratoire de Chimie Agro-Industrielle Study of Alkenyl Succinic Anhydrides from fatty acid esters of vegetable oils as paper sizing agents
Steam Stripping
M stripped ASA(g/kg ASA)
Oleo-ASA = deposits divided by factor 10
Volatility decreased by the ester function
0,08 0,06 0,04
0,57
1,46
0,64
0,0
0,4
0,8
1,2
1,6
ASAOE ASAOPr ASAOIPr ASAPAP1 ASAPAP2 ASAPAP3
Laboratoire de Chimie Agro-Industrielle Study of Alkenyl Succinic Anhydrides from fatty acid esters of vegetable oils as paper sizing agents
W.E. Scott, Principles of Wet End Chemistry, Tappi Press, 1996; 99-110
Kinetics of ASA hydrolysis
ASAcid drawbacks:
Decrease in the quantity of active ASACritical to sizingSalts formation with Ca2+ and Mg2+
The kinetics of this rapid reaction essentially depends on:
TemperaturepH
Emulsions prepared on site and impossible to store
ASA ASAcid
R CH2 CH
OO O
CH CH R' + R CH2 CH CH CH R'
OHOH
H2O
OO%A
SA
Time (h)
pH = 3.5
Time (h)
%A
SA
T = 25C
R.B. Wasser, J. Pulp Pap. Sci, 1987, 13, 29-32
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Laboratoire de Chimie Agro-Industrielle Study of Alkenyl Succinic Anhydrides from fatty acid esters of vegetable oils as paper sizing agents
Kinetics of ASA hydrolysis
Oleo-ASA = 2 times slower hydrolysis
Comparison at 50C
0
20
40
60
80
100
0 1 2 3 4 5 6 7 8 9 10 11 12
Hydrolysis time (h)
%A
SA
ASAOEASAOPrASAPAP1ASAPAP2ASAPAP3
Laboratoire de Chimie Agro-Industrielle Study of Alkenyl Succinic Anhydrides from fatty acid esters of vegetable oils as paper sizing agents
Kinetics of ASA hydrolysis
The ester function decreases
the anhydrides accessibility
Oleo-ASA two times more
resistant to hydrolysis
k (mn-1) tmax (mn)ASAOE -0,240 558ASAOPr -0,252 615
ASAPAP1 -0,461 222ASAPAP2 -0,496 249ASAPAP3 -0,639 278
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Laboratoire de Chimie Agro-Industrielle Study of Alkenyl Succinic Anhydrides from fatty acid esters of vegetable oils as paper sizing agents
Reaction with cellulose
Is there an ester linkage ?How much ASA reacts with cellulose ?
Cellulose+ ASA Bound ASA
ASAcid
Unbound ASA
ASARetained
ASA
Unretained ASA
R CH2 CH
OO O
CH CH R' + Cellulose R CH2 CH CH CH R'
O CelluloseOH
OH
O O
Laboratoire de Chimie Agro-Industrielle Study of Alkenyl Succinic Anhydrides from fatty acid esters of vegetable oils as paper sizing agents
Reaction with cellulose
Higher retention for Oleo-ASAMore bound Oleo-ASA
0%
20%
40%
60%
80%
100%
ASAPAP1 ASAOPr
%A
SA
Bound
ASA
Unretained
ASA
Unbound
ASA
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Development of Continuous
Processes for Vegetable Oil
Ethanolysis in MicrofluidicDevices
Sophie THIEBAUD-ROUX, R. Richard, B. Dubreuil, L. PratJournes Chevreul
June 2012
Context and Objectives
Vegetable oils
SunflowerRapeseed
Soybean
+
Palme
Fatty Acid Ethyl Esters
BioethanolCH3CH2OH
FAEE
FAEE : considered as 100% biosourcedFAEE used for applications principally in food and cosmetic industryTo open the application field to biofuels or biosolvents (as Methyl Esters), theprocess efficiency has to be developed to be economically profitable
Transfer of the batch or semi-batch transesterification into a continuous device
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Constant amount of monoglycerides at the end of the reaction (not negligiblecontrary to DG and TG) : stable equilibria
Numerous steps in the ethanolysis process in order to shift the reaction equilibria(in comparison to methanolysis processes) :
- Transesterification reaction
- Separation of ethyl esters from glycerol, by-product of the reaction :quite difficult
- Refill with ethanol and catalyst
- 2nd reaction
Limits of FAEE Production Processes
Expensive process
Continuous processBatch process
Transesterification
+ 3 C2H5OH
Homogeneous catalysis :EtONa
3 RCOOC2H5 +
1re tape : TG + R-OH DG + R-OOC-R
2me tape : DG + R-OH MG + R-
OOC-R
3me tape : MG + R-OH GL + R-
OOC-R
k1
k-1
ReactionsTriglyceridesethanolysis *
Secondary reactions **
Phase equilibrium changesTwo immiscible phases are present at the beginning of the reaction (oil and ethanolphases) and at the end of the reaction (ester and glycerol phases with ethanol in
excess in both phases)
Simultaneous presence of various phenomena : mixing, heat and mass transfers,principal and competitive reactions
OOCCH2
CH
R
OOC R
C OOC RH2
OCH2
CH O
C OH2
H
H
H
+ 3 Na+,OH-H2O
3 RCOO-,Na+ +TG GL
+ 3 Na+,OH- RCOO-,Na+ +RCOOH H2O
TG GL
k2
k-2k3
k-3
Saponification
Salification
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Continuous Process in Microreactors
Reactiongenerating
dropletsPDMS microreactor
PFA microreactorImplementation of small volumes(widths between 1 m and 1000 m)
safety is increased
Perfect control of the flows (between1 L/h and several L/h)
Very high surface/volume (S/V) ratiowhich increases heat and masstransfer
Control of the initial mixingtime which does not depend on the
feeding procedure
Access to low characteristic times
Parallelize the microreactors to produce (numbering-up vs scaling-up) : a faster extrapolation
ocurrent approach: scale-up laboratory
pilot Industrialscale
oplanned approach: smart numbering-up
Microstructuredreactor Moderate scale-up and
optimizationParallelization forproduction scale
Transposition to a continuous process in
microreactors
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Experimental Device
Reaction isquenched
by adding HCl
to neutralize the
basic catalyst
Each tube length corresponds to a reaction time : thetube was cut to obtain lower reaction times
Effect of temperature on the flow
From T = TL, no drops are observed :coflowing jet
c
cc
c
dU
=Re
d
dd
d
UCa
=
20
25
30
35
40
45
50
55
60
65
70
0 1 2 3 4 5 6 7 8 9
Reaction time (min)
T (C)
experimental points
limit diphasic/monophasic flow
limit jet/droplet
Jet flow
Droplet flow
Monophasic flow
TL
Cad(10
-3)
Red/Rec(10
-2)
0,321,47
1,25
1,05
0,89
0,75
0,44
0,59
0,80
1,09
Generation
Qtot = 1,5 mL.h-1
Molar ratio EtOH/huile = 45,4
Catalyst EtONa = 1%
Water content = 0,08%
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FAEE contents for different EtOH:oil molar ratios
1 m 2 m1,5 m0,5 m
Ltube
oilEtOH/EtONa
Fast reaction :around 7 min
Interfacial surface S/V increases
A new on-line method based on
Near Infrared spectroscopy and a
multivariate approach
Advantages:Fast Reliable Inexpensive Non-destructive No quench needed No sample preparation needed
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NIR Spectroscopy Analysis
Fiber-optic probe working bytransflectance
Material : NIR Spectrometer Antarix MX FT-NIRProcess Analyzer from Thermo Fisher Scientific, USA
Analysis parameters: Wavenumber range:
10000 4000cm-1 (800 - 2500 nm)
Optical beam path: 3 mm 32 scans Spectral resolution: 2 cm-1
Optical beam path
Mirror
Height-adjustablescrew
Light beam
Monitoring of the reactionthrough sequential scans and with GC
reference method
Study of a new environment
friendly catalytic system for
the oxidative scission of
unsaturated fatty acidsAnas Godard, Sophie Thiebaud-Roux, Emeline Vedrenne, Pascale
de Caro, Zphirin Mouloungui103rd AOCS Annual Meeting & Expo
Long Beach, California, USA
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OH
O
O
OH OH
O
OH
O
+
ozonolysis
! Shorter and odd hydrocarbon chains! Low availability at a natural state! Interesting raw materials forbiobased products
Cosmetics, synthesisof polymers/polyesters
Biosolvents, lubrificants,resines, plastificizers
Oleic acid(OA)
Pelargonic acid
(PA)
Azelaic acid
(AA)
Oxidative cleavageGreen oxidant
system
Oxidative scission reaction
! Green oxidant system : H2O2 / Q3{PO4[WO(O2)2]4}
! No extra organic solvent
OH
O
O
OH OH
O
OH
O
+
H2O2(oxidant)
Q3{PO4[WO(O2)2]4}
(catalyst/co-oxidant)
OA
Q+ : quaternary ammonium cation
Oxidative cleavage of oleic acid
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! In the presence of H2O2, the catalyst is converted into the peroxo form
! The peroxo form of the catalyst transfer the oxygen to the substrate
M : W
(tungsten)
H2O2 H2O
Oxo form Peroxo form
Peroxo form Oxo form
interface
Turnwald, SE. et al., Journal of Materials Science Letters, 1998Noyori, R. et al, Chemical Communications, 2003
Mechanism of the phase transfer catalyst
Hydrolysis of high oleic sunflower oil
Total
triglycerides
conversion:
100 min
O
O
O
ROC
ROC
ROC
R
OH
O
340 C , 5 h
WaterLipase Candida Cylindracea (1%)
aa
! Hydrolyse of high sunflower oil with the lipase Candida Cylindracea
0
20
40
60
80
100
0 50 100 150 200 250 300
Time (minutes)
Yields
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Hydrolysis of high oleic sunflower oil
O
O
O
ROC
ROC
ROC
R
OH
O
340 C , 5 h
WaterLipase Candida Cylindracea (1%)
aa
! Hydrolyse of high sunflower oil with the lipase Candida Cylindracea
Fatty acids Symbol Mass composition
Oleic acid C18 : 1 87.6 %
Linoleic acid C18 : 2 4.7 %
Palmitic acid C16 : 0 3.5 %
Stearic acid C18 : 0 3.1 %
Capric acid C10 : 0 0.2 %
Other acids -- 0.9 %
63/23Anas Godard - 103rdAOCS Annual Meeting & Expo
Q3{PO4[WO(O2)2]4}
Oleic acid
1. Q+,X- in water
2. H3PW12O40 with H2O2H2O2
5 eq.
1 eq.
In situ
formation
Protocole for the oxidative cleavage of OA
Catalyst/Co-oxidant
Oxidant
Substrate
Reactants
64/23
Treatment
! Temperature quenching! Extraction with AcOEtAnalysis! GC with internal standard! MS with ammonia chemical ionization! NMR 1H and 13C
Anas Godard - 103rdAOCS Annual Meeting & Expo
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! System : OA / H2O2 / Q3{PO4[WO(O2)2]4} (1/5/0.02)! 85 C, 5 h , 400 rpm! Four quaternary ammonium cations Q+ were tested
Effects of the type of catalyst/co-oxidant
Catalyst X- OA (%) YAA (%) YPA (%)-- - 38.1 1.8 2.2
[n-Bu4N]3{PO4[WO(O2)2]4} Cl- 100.0 77.6 80.9
[n-Bu4N]3{PO4[WO(O2)2]4} Br- 100.0 71.8 76.2
[C5H5N(n-C16H33)]3{PO4[WO(O2)2]4} Cl- 100.0 81.5 86.1
[MeN(n-C8H17)3]3{PO4[WO(O2)2]4} Cl- 100.0 75.7 80.7
[(n-C8H17)4N]3{PO4[WO(O2)2]4} Cl- 100.0 73.2 76.5
Best results were obtained with [C5H5N(n-C16H33)]3{PO4[WO(O2)2]4}
65/23
Experimental standard deviation(3 analyzed samples) between 0.1-3.9%
Anas Godard - 103rdAOCS Annual Meeting & Expo
Effects of the reaction temperature! System : OA / H2O2 / [C5H5N(n-C16H33)]3{PO4[WO(O2)2]4} (1/5/0.02)! 5 h, 400 rpm
30
40
50
60
70
80
90
60 65 70 75 80 85 90 95 100 105 110
Temperature (C)
Yield(%
)
Azelaic acid
Pelargonic acid
Optimal temperatures
85 C - 90 C
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Experimental standard deviation (3 analyzed samples) between0.3-2.2% Anas Godard - 103rdAOCS Annual Meeting & Expo
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Kinetic investigation! OA / H2O2 / [C5H5N(n-C16H33)]3{PO4[WO(O2)2]4} (1/5/0.02), 85C
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0 50 100 150 200 250 300
Time (min)
Ai /Atotal
Pelargonic acid
Azelaic acid
Epoxide
Diol
Aldehyde (AP)
Aldehyde (AA)
Mechanism : OA Epoxide Diol Aldehydes Acids (AA and PA)
67/23Anas Godard - 103rdAOCS Annual Meeting & Expo
! Extractions of AA and PA performed at low temperature! Catalyst recovery by filtration
Influence of the post-reaction treatment
Catalyst Treatment
temperature
YAA (%) YPA (%)
[n-Bu4N]3{PO4[WO(O2)2]4} R.T. 72.9 73.9
[n-Bu4N]3{PO4[WO(O2)2]4} Ice bath 77.6 80.9
[C5H5N(n-C16H33)]3{PO4[WO(O2)2]4}R.T.
71.8 70.9
[C5H5N(n-C16H33)]3{PO4[WO(O2)2]4} Ice bath 81.5 86.1
[MeN(n-C8H17)3]3{PO4[WO(O2)2]4} R.T. 71.3 77.2
[MeN(n-C8H17)3]3{PO4[WO(O2)2]4} Ice bath 75.7 80.7
! OA / H2O2 / [C5H5N(n-C16H33)]3{PO4[WO(O2)2]4} (1/5/0.02)! 85C, 5 h, 400 rpm! Two treatment temperatures were tested:at room temperature (R.T.) or cold in an ice bath ( T < 4C)
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Experimental standard deviation (3 analyzed samples) between0.1-3.9%
Anas Godard - 103rdAOCS Annual Meeting & Expo
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Solvant
recycling
1. Ice bath(T < 4C)
2. Filtration
Oleic acid
H2O2
Extractionwith AcOEt
Fatty acids
! In situ formation ofthe catalyst! 85 C, 5 h, 400 rpm
Organic
phase
Aqueous
phase
Solventevaporation
Solid catalyst
Free-solvent
(No waste)
Aqueous
phase
Conclusions : Development of a green process
Q3{PO4[WO(O2)2]4}
Organic
phase
69/23Anas Godard - 103rdAOCS Annual Meeting & Expo
Thank you for your attention
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