Bioproducts for a Sustainable Use

7/29/2019 Bioproducts for a Sustainable Use

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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





Release /

Transformation

Integrated Process


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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


water and

enzyme

Recycling




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

+ + +





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


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



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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


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


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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Papersheet process

Chemical

Mechanical

Additives

Papermachine


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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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


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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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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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


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


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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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)


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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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


Emulsion stability

Same

granulometry

t0

t12h

ASAOPr

10 m

10 m

Stable

emulsion

10 cm


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Strategy

Stripping Hydrolysis Reactivity

Comparison oleo-ASA vs petrochemical ASA

Oleo-ASA advantages

Equivalent sizing

Optimal oleo-ASA Petrochemical ASA


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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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


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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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



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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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


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}

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Experimental standard deviation(3 analyzed samples) between 0.1-3.9%


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)


! 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%



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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


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Thank you for your attention

Bioproducts for a Sustainable Use

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