vegetable lecithin production & industrial scale...

Vegetable Lecithin production Vegetable Lecithin production & Industrial Scale Modification& Industrial Scale Modification

W. van NieuwenhuyzenW. van Nieuwenhuyzen

Lecipro ConsultingLecipro Consulting

www.lecipro.nlwww.lecipro.nl

AOCS Lecithin SC AOCS Lecithin SC –– Montreal, April 27Montreal, April 27--28,201328,2013

1Lecipro – AOCS Lecithin SC Montreal 2013

Topics Topics

1.1. Lecithin Production Lecithin Production

2.2. Phospholipid PropertiesPhospholipid Properties

3.3. Plant Scale Modification Plant Scale Modification 3.3. Plant Scale Modification Plant Scale Modification

4.4. SpecificationsSpecifications


Production of Vegetable LecithinProduction of Vegetable Lecithin

•• Oil seeds are the primary source Oil seeds are the primary source

•• Lecithin occurs in oil seeds at 0.6 Lecithin occurs in oil seeds at 0.6 –– 1.5%1.5%

•• Crushing opens the cell wallsCrushing opens the cell walls

•• Lecithin recovery 0.3 Lecithin recovery 0.3 –– 0.6%0.6%

•• Beyond 280 million T oil seeds are crushedBeyond 280 million T oil seeds are crushed

•• Most oilMost oil--soluble phospholipids ”follow” the oil and soluble phospholipids ”follow” the oil and must be removedmust be removed


Different oil seed sources for Different oil seed sources for vegetable lecithinsvegetable lecithins

Soy Beans

Sunflower Kernels

4 Rape Seeds Lecipro – AOCS Lecithin SC Montreal 2013

Basic Soybean CompositionBasic Soybean Composition


(Phospho)Lipid Molecular structures(Phospho)Lipid Molecular structures•• FatsFats = Triglycerides= Triglycerides

R1, R2, R3:R1, R2, R3:

fatty acidsfatty acids

chain length C8 <chain length C8 <--> C22> C22chain : saturated,monochain : saturated,mono--poly unsat.poly unsat.

•• Emulsifier basis Emulsifier basis : Mono: Mono--DiglycerideDiglyceride

R3

R2

R1

•• Emulsifier basis Emulsifier basis : Mono: Mono--DiglycerideDiglyceride

•• LecithinLecithin

6

MonoglycerideMonoglyceride

Hydrolysed lecithinHydrolysed lecithin

CH2 OH CH2 OH

OHDiglycerideDiglyceride

CH2 O P

O

O

X

StandardStandardOH

CH2 O P

O

O

X

Lecipro – AOCS Lecithin SC Montreal 2013

Processing of Vegetable Lecithins

Cleaning

Dehulling

Water / Acid

Degumming

DryingHulls

Non Degummed

oil

Oil

Seed

7

Dehulling Drying

EXPELLING

Extraction

Desolven-

tizingStandardization

Storage

Cooling

Hulls

Protein Meal

Lecithin


Importance for good lecithinImportance for good lecithin

•• Expelling = pressing of sunflower Expelling = pressing of sunflower

or rapeseed oil (not for soya oil)or rapeseed oil (not for soya oil)

•• Good seed treatment & dehulling Good seed treatment & dehulling

benefit: colour, degummingbenefit: colour, degummingbenefit: colour, degummingbenefit: colour, degumming

•• Standard PL composition and Standard PL composition and

Quality standardsQuality standards

•• Convenience in useConvenience in use


Enzymatic activity during seed crushingEnzymatic activity during seed crushing

•• Critical process zone Critical process zone

– Pass Temperature range from 40 to 70 °C quickly:

Inactivate enzymes (PL-D) to avoid Non Hydratable

Phospholipid (NHP) formation

• Refinability of crude oil

– Low NHP, FFA, oxidized fatty acid chains– Lecithin quality - PL composition– Lecithin quality - PL composition

– Yields

• Higher oil loss and lower lecithin yield with poorer refinability

• Lecithin yields in water- degumming

– Crude Soya oil 1000 ppm P� 100 ppm P: 2.5% yield

– Crude RP /SF oil 800ppm� 300 ppm P: 1.5% yield


Removal of Lecithin: Removal of Lecithin: ”Degumming” in Lecithin production”Degumming” in Lecithin production

•• 11--2 % water is added to crude oil at 70 2 % water is added to crude oil at 70 °°C, C, hydrating phospholipids hydrating phospholipids ��”gums or sludge””gums or sludge”

•• Aqueous gums precipitate and can be centrifugedAqueous gums precipitate and can be centrifuged

•• Thin film vacuum drying reduces water from 40 % to <1 %Thin film vacuum drying reduces water from 40 % to <1 %

•• Drying time is 1Drying time is 1--2 minutes at 902 minutes at 90--100 100 °°C C ––> cooling to 50 > cooling to 50 °°CC 10

Rheology of lecithin gums during dryingRheology of lecithin gums during dryingFree after W. van Nieuwenhuyzen, Free after W. van Nieuwenhuyzen, JAOCSJAOCS, 53, 53,, 425425--427, 1976427, 1976

Viscosity of lecithin gums

during drying

700

800

900

1000Vis

cosity Pa.s

0

100

200

300

400

500

600

700

0 5 10 15 20 25

% Moisture

Vis

cosity Pa.s

Lecipro – AOCS Lecithin SC Montreal 2013 11

Lecithin processing conditionsLecithin processing conditions•• Lecithin as it isLbrown colourLecithin as it isLbrown colour

•• Lecithin with lighter colourLecithin with lighter colour

–– Bleaching with Hydrogen peroxide, Bleaching with Hydrogen peroxide,

POV max 10POV max 10

–– One step L”single bleached lecithin” One step L”single bleached lecithin” ––

US definition, not valid in EuropeUS definition, not valid in EuropeUS definition, not valid in EuropeUS definition, not valid in Europe

–– Two stepsL”double bleached lecithin” Two stepsL”double bleached lecithin”

•• nonnon--food, technical grade in Europefood, technical grade in Europe

•• Clear Transparent lecithinClear Transparent lecithin

–– nonnon--degummed oil filtrationdegummed oil filtration


Requirements for Clear Transparent LecithinRequirements for Clear Transparent Lecithin

•• Low HI Low HI -- impurity level for regulative and impurity level for regulative and

technological reasons technological reasons

•• Stable thin liquid lecithin Stable thin liquid lecithin –– oil systems need absence oil systems need absence

of turbid dry substancesof turbid dry substances

•• Low metal content, optimal taste and colorLow metal content, optimal taste and color•• Low metal content, optimal taste and colorLow metal content, optimal taste and color

•• Clear transparency occurs at Clear transparency occurs at HI << HI << 0.03 % (< 300 0.03 % (< 300

ppm)ppm)


Intensive Filtration of NonIntensive Filtration of Non--degummed Oildegummed Oil

•• Pressed oil with 3Pressed oil with 3--7 % d.s.: filter of decanter centrifuge7 % d.s.: filter of decanter centrifuge

–– Filtration without filter aid feasibleFiltration without filter aid feasible

•• Miscella filtration is possible but ExMiscella filtration is possible but Ex--proofproof

•• Extracted oils with 0,2 Extracted oils with 0,2 --0,4% d.s. more efficient with 0,4% d.s. more efficient with

special filter equipment with use of prespecial filter equipment with use of pre--coat & filter aidcoat & filter aidspecial filter equipment with use of prespecial filter equipment with use of pre--coat & filter aidcoat & filter aid

–– Soy need 0,1% bodySoy need 0,1% body--coatcoat

–– Filter aids: Dicalite, Celite 545, JRS EFCFilter aids: Dicalite, Celite 545, JRS EFC

•• Lecithin AI 60% is high viscous and cannot filtered Lecithin AI 60% is high viscous and cannot filtered

deeply on plant scale. deeply on plant scale.


Crude Oil filtrationCrude Oil filtration(chart (chart borrowed from Mahle borrowed from Mahle –– AMA Filter)AMA Filter)

15 Lecipro – AOCS Lecithin SC Montreal 2013

Topics Topics






Phospholipids in vegetable lecithinsPhospholipids in vegetable lecithins

9

10 14 10

43 4

6 4 4

60%

80%

100%

Other

PA

PI

15 16 17

10 89

0%

20%

40%

lecithin lecithin lecithin

Soy Sun Rape

PI

PE

PC


Fatty acid division in lecithinsFatty acid division in lecithins

55 63

25

7 06

1 4 5

60%

80%

100%

others

C18:3

C18:2

C18:1

1611 7

44

1

1718

56

0%

20%

40%

lecithin lecithin lecithin

Soy Sun Rape

C18:1

C18:0

C16:0


Exchange of vegetable lecithinsExchange of vegetable lecithins

•• Soy lecithinSoy lecithin–– Traditionally available in top quality standardsTraditionally available in top quality standards

•• Sunflower lecithinSunflower lecithin–– Need intensive oil filtration during processing (low TI)Need intensive oil filtration during processing (low TI)

–– Nutty pleasant tasteNutty pleasant taste

•• Rapeseed lecithinRapeseed lecithin•• Rapeseed lecithinRapeseed lecithin–– Need intensive oil filtration during processing (low TI)Need intensive oil filtration during processing (low TI)

–– Colour and taste criticalColour and taste critical

•• Exchange of typeExchange of type–– Evaluate functionality and recipeEvaluate functionality and recipe


Topics Topics






Lecithin Modification processesLecithin Modification processes

–– Enzymatic HydrolysisEnzymatic Hydrolysis

–– AcetylationAcetylation

–– HydroxylationHydroxylation–– HydroxylationHydroxylation

–– FractionationFractionation

–– DeDe--oilingoiling

–– Spray dryingSpray drying


Why Modification ?Why Modification ?OBJECTIVE :OBJECTIVE :

different hydrophilic different hydrophilic -- lipophilic character lipophilic character

‘HLB’ range 2‘HLB’ range 2--1212

reduced Calcium sensitivityreduced Calcium sensitivity

PRODUCT RANGE :PRODUCT RANGE :

deoiled lecithin powder / granules deoiled lecithin powder / granules -- 2% oil2% oildeoiled lecithin powder / granules deoiled lecithin powder / granules -- 2% oil2% oil

fractionsfractions -- PC enriched / isolatedPC enriched / isolated

-- PE enrichedPE enriched

enzymatic hydrolysedenzymatic hydrolysed

hydroxylated *hydroxylated *

acetylated*acetylated*

clear standard lecithins clear standard lecithins -- 35% oil35% oil

speciality mixesspeciality mixes

* No E* No E--number in Europenumber in Europe22Lecipro – AOCS Lecithin SC Montreal 2013

Fractionation techniques for Fractionation techniques for phospholipid separationphospholipid separation

•• Alcohol fractionationAlcohol fractionation

•• Chromatographic isolationChromatographic isolation


Reasons for FractionationReasons for Fractionation

•• Deoiled lecithins in powder and granule form Deoiled lecithins in powder and granule form

with bland tastewith bland taste

•• Specific surfaceSpecific surface--active properties, stabilizing active properties, stabilizing

emulsionsemulsions

•• Phosphatidylcholine (PC) forms liposomal Phosphatidylcholine (PC) forms liposomal

bilayers with encapsulation capacity bilayers with encapsulation capacity

•• PC has specific nutritional and pharmaceutical PC has specific nutritional and pharmaceutical

propertiesproperties


Lecithin fractionation processLecithin fractionation processCrude Crude

LecithinLecithin

AlcoholAlcoholFractionationFractionation

Alcohol Alcohol solublesoluble

fraction PCfraction PC--3535

Alcohol Alcohol insolubleinsoluble

fraction PI fraction PI --FF

ChromatographicChromatographic

25

ChromatographicChromatographicseparationseparation

PCPC--80 80

IsolateIsolate

Alcohol Alcohol solublesoluble

fraction PE fraction PE --FF

SpraySpray--drying on carrierdrying on carrier

PCPC--80 fraction 80 fraction on maltodextrinon maltodextrin

Mixing on carrierMixing on carrier

PCPC--80 fraction on oil80 fraction on oilLecipro – AOCS Lecithin SC Montreal 2013

PC/PE ratio in lecithin fractionsPC/PE ratio in lecithin fractions

PC PE PI PC/PE ratio

Standard Lecithin 16 13 10 1.2

Alcohol soluble PC-35 35 8 1 4.5

Alcohol insoluble PI-F 5 14 12 0.4

PC-80 Isolate 80 3 - 25

Egg Lecithin 70 16 1 4.5

PC = phosphatidylcholine PE = phosphatidylethanolamine26Lecipro – AOCS Lecithin SC Montreal 2013

Fractionation Plant up scaling Fractionation Plant up scaling issuesissues

•• Viscosity of alcoholViscosity of alcohol--lecithin mixture: lecithin mixture:

Ratio Ethanol: Lecithin = 3Ratio Ethanol: Lecithin = 3--4:14:1

•• Temperature controlTemperature control


•• Stability and shelf life of fractionsStability and shelf life of fractions

•• Management of coManagement of co--products (80%) products (80%)

essential for economic success.essential for economic success.

•• Continuous counter current extraction Continuous counter current extraction

processprocess

Fractionation techniques for oil Fractionation techniques for oil removalremoval

•• Acetone extractionAcetone extraction

•• Critical Carbon dioxide extractionCritical Carbon dioxide extraction

•• Membrane technologyMembrane technology•• Membrane technologyMembrane technology


Crude lecithin

Acetone Extraction

Belt drying

De-oiling of Lecithin

29

Belt drying

Sieving

Packaging

Deoiled lecithinPowder / Granules


Composition of soy lecithinComposition of soy lecithin

10

15

5

7.5

37

2.5

60%

80%

100%

Oil

Complex

Carbohydrates

Glycolipids

48

65

0%

20%

40%

Standard Lecithin Oil free Lecithin

Glycolipids

Phospholipids


Lecithin hydrolysis with enzymeLecithin hydrolysis with enzyme

Phospholipase APhospholipase A22

40 40 -- 70 70 °°CC

RR22 CC

OO

OO CHCH

CHCH22 OO CC

OO

RR11

HOHO CHCH

CHCH22 OO CC

OO

RR11

OO

HOHO CC

OO

RR22

+++ H+ H22OO

31

phospholipidphospholipid

Degree of hydrolysis : 20 Degree of hydrolysis : 20 -- 60 %, depending on requirement60 %, depending on requirementincreasing hydrophilicityincreasing hydrophilicity

CHCH22

OO PP

OO

OO--

OO XX CHCH22

OO PP

OO

OO

OO--

XX

+ water+ water lysophospholipidlysophospholipid + fatty acid+ fatty acid


Types of phospholipaseTypes of phospholipase

11

2

Phospholipase A1

Phospholipase A2

32

P X

2

3 4

2

3

4

Phospholipase A2

Phospholipase C

Phospholipase D


HydrolysisHydrolysis


Hydrolysis of Sunflower lecithinHydrolysis of Sunflower lecithinEP 1 607 003 [2001] UnileverEP 1 607 003 [2001] Unilever0.83 ml Lecitase 10L per kg lecithin0.83 ml Lecitase 10L per kg lecithin

30

40

50

Deg

ree o

f H

yd

roly

sis

%

DH-PE

0

10

20

30

0 0.5 1 1.5 2

Hydrolysis time in H

Deg

ree o

f H

yd

roly

sis

%

DH-PE

DH-PC

DH-PI


Benefits for hydrolysisBenefits for hydrolysis

•• Formation hydrophilic LysoFormation hydrophilic Lyso--PLsPLs

•• Transformation “inactive” PE Transformation “inactive” PE --�� functional LPEfunctional LPE

•• Improvement of Calcium Improvement of Calcium ––ResistanceResistance•• Improvement of Calcium Improvement of Calcium ––ResistanceResistance

•• Effective processing aid Effective processing aid –– Oil DegummingOil Degumming

•• LPL’s positive interactions:LPL’s positive interactions:

–– Starch antiStarch anti--staling breadstaling bread

–– Proteins Proteins –– emulsion stabilityemulsion stability

–– Heat stable W/O emulsionsHeat stable W/O emulsions


Hydrolysis Plant up scaling issuesHydrolysis Plant up scaling issues

•• Addition of PLAddition of PL--A to viscous Lecithin (gums)A to viscous Lecithin (gums)

•• Stirring in (semiStirring in (semi--) batch process) batch process

•• Constant reaction / residence time in continuous Constant reaction / residence time in continuous

hydrolysis processhydrolysis process

–– Material rheology changeMaterial rheology change

–– Ideal: 3Ideal: 3--4 stirred vessels, but expensive4 stirred vessels, but expensive


–– Ideal: 3Ideal: 3--4 stirred vessels, but expensive4 stirred vessels, but expensive

–– Plug flow reactor with good Length / Diameter Plug flow reactor with good Length / Diameter

ratioratio

•• Plant control of degree of hydrolysisPlant control of degree of hydrolysis

•• Relationship hydrolysis Relationship hydrolysis ↔↔ emulsifying propertiesemulsifying properties

Acetylation of LecithinAcetylation of LecithinAcetylation of LecithinAcetylation of Lecithin

R1

R2

CH2O P

O

O.

O CH2 CH2 N+H3 CH3 C

O

OCH3 C

O

R1

R2

N

H

H

C

O

CH3 CH3 C

O

OH++

37

O

PE + Aceticanhydrid

Acetyl PE + Acetic acid

Increased Hydrophilicity HLB 6• still weak O/W Emulsifier

R = Fatty acidLecipro – AOCS Lecithin SC Montreal 2013

Acetylated LecithinAcetylated Lecithin

•• Acetylating of PE with Acetic anhydrideAcetylating of PE with Acetic anhydride

•• Product has no E number in Europe because Product has no E number in Europe because

nobody has requested for registrationnobody has requested for registration

•• In NIn N--America use as food grade lecithin in America use as food grade lecithin in

e.g. baked good and pan release agente.g. baked good and pan release agent

•• In animal feed milk replacers use as O/W In animal feed milk replacers use as O/W

emulsifieremulsifier


Hydroxylation of LecithinHydroxylation of LecithinHydroxylation of LecithinHydroxylation of Lecithin

39

PL + Hydrogen peroxide Hydroxy-PL + Water

• strong hydrophilic O/W Emulsifier HLB 9-10• Easily dispersible in Water (white emulsion)

R = Fatty acid


Hydroxylated lecithinHydroxylated lecithin

•• Hydroxylation of double bonds in fatty Hydroxylation of double bonds in fatty

acid chains with Hydrogen peroxide at acid chains with Hydrogen peroxide at

low pHlow pH

•• Excellent water dispersible lecithin due Excellent water dispersible lecithin due •• Excellent water dispersible lecithin due Excellent water dispersible lecithin due

to enhanced hydrophilic propertiesto enhanced hydrophilic properties

•• No European E numberNo European E number

•• In NIn N--America use in baked goods, O/W America use in baked goods, O/W

emulsions and instant wetting productsemulsions and instant wetting products


Spray dried lecithin powdersSpray dried lecithin powders

•• Spray drying of liquid lecithinSpray drying of liquid lecithin

–– homogenized in whey protein solutionhomogenized in whey protein solution

–– convenient lecithin powder on carrier (50%)convenient lecithin powder on carrier (50%)

–– Casein level determines “encapsulation” and Casein level determines “encapsulation” and

“free fat content”“free fat content”

•• Spray cooling of liquid lecithinSpray cooling of liquid lecithin

–– on wheat flour, soy protein, dairy proteinon wheat flour, soy protein, dairy protein

–– Lecithin content 20Lecithin content 20--30%30%

•• Handling / Dosing ConvenienceHandling / Dosing Convenience


Topics Topics






Legal Lecithin SpecificationsLegal Lecithin Specifications

FAO/WHO

Codex

FCC

USA

EU

E322

Acetone Insoluble % >60 >50 >60 [56*]

Hexane / Toluene

Insoluble % <0.3 <0.3 <0.3

Moisture % <2.0 <1.5 <2.0

Acid Value mg KOH/g <36 <36 <35 [45*]

Peroxide Value meg/kg <10 <100 <10

* for enzymatic hydrolysed lecithin


Typical Chemical AnalysesTypical Chemical AnalysesStandard liquid lecithinsStandard liquid lecithins

Sunflower Sunflower

LecithinLecithin

Soya Soya

LecithinLecithin

Rape seedRape seed

LecithinLecithin

Acetone InsolubleAcetone Insoluble 6363 6262 6262

Acid ValueAcid Value 3434 3030 3131

MoistureMoisture 0.40.4 0.40.4 0.50.5

Hexane InsolubleHexane Insoluble 0.10.1 0.10.1 0.10.1

Gardner ColorGardner Color 99 1010 1212

POVPOV 22 22 11

Viscosity Pa.sViscosity Pa.s 88 88 88


Analytical tests lecithinsAnalytical tests lecithins

•• Lecithin contains phospholipids, byLecithin contains phospholipids, by--lipids, complex lipids, complex

sugars and embedded crude oilsugars and embedded crude oil

•• Phospholipids are the “powerful” portionPhospholipids are the “powerful” portion

•• Phospholipids insoluble in AcetonePhospholipids insoluble in Acetone

•• All components soluble in Toluene / HexaneAll components soluble in Toluene / Hexane•• All components soluble in Toluene / HexaneAll components soluble in Toluene / Hexane

•• The legal requirement for Lecithin E 322 are:The legal requirement for Lecithin E 322 are:

–– Acetone Insoluble AI min. 60 % (Active matter)Acetone Insoluble AI min. 60 % (Active matter)

–– Toluene Insoluble TI max. 0,3 % (impurities) Toluene Insoluble TI max. 0,3 % (impurities)


Summing upSumming up

•• Phospholipid composition of standard lecithin is Phospholipid composition of standard lecithin is

importantimportant

•• Source can be : soy, rapeseed, sunflowerSource can be : soy, rapeseed, sunflower

•• Often used modifications are enzymatic hydrolysis, Often used modifications are enzymatic hydrolysis,

fractionation and deoiling.fractionation and deoiling.fractionation and deoiling.fractionation and deoiling.

•• Modifications aim for specific emulsifying propertiesModifications aim for specific emulsifying properties

•• Emulsion tests: first screening of desired propertiesEmulsion tests: first screening of desired properties

•• Methods of analysis are important for legal, Methods of analysis are important for legal,

commercial and technological reasons.commercial and technological reasons.


Recommended LiteratureRecommended Literature

•• A A WendelWendel, Lecithin, Chapter in Kirk, Lecithin, Chapter in Kirk--OthmerOthmer Encyclopedia of Chemical Encyclopedia of Chemical

Technology, Technology, VolVol 15, 19215, 192--210, Wiley & Sons (1995)210, Wiley & Sons (1995)

•• Lecithin, AOCSLecithin, AOCS-- INFORM, INFORM, VolVol 7, Nr 11, 11577, Nr 11, 1157--1175 (1996)1175 (1996)

•• B. B. SzuhajSzuhaj, Lecithin, Chapter 13, Baileys Oils & Fats, , Lecithin, Chapter 13, Baileys Oils & Fats, VolVol 3, 3613, 361--456, Wiley 456, Wiley

(2001) (2001)

•• S.D. S.D. DoigDoig, R.M.M. , R.M.M. DiksDiks, Toolbox for modification of the lecithin head group, , Toolbox for modification of the lecithin head group,

Eur.J.LipidEur.J.Lipid Sci.Technol.105, part 1: 359Sci.Technol.105, part 1: 359--367, part 2: 368367, part 2: 368--376 (2003)376 (2003)


Eur.J.LipidEur.J.Lipid Sci.Technol.105, part 1: 359Sci.Technol.105, part 1: 359--367, part 2: 368367, part 2: 368--376 (2003)376 (2003)

•• W. van Nieuwenhuyzen & M Tomas W. van Nieuwenhuyzen & M Tomas --Update of vegetable lecithin Update of vegetable lecithin

technologies, EJLST 110, 472technologies, EJLST 110, 472--486 (2008)486 (2008)

•• Phospholipid Technology and Applications, Ed. F.D. Phospholipid Technology and Applications, Ed. F.D. GunstoneGunstone, The Oily , The Oily

Press (2008)Press (2008)

•• WvN: Lecithin and Other Phospholipids, Chapter 10 in Surfactants from WvN: Lecithin and Other Phospholipids, Chapter 10 in Surfactants from

Renewable Resources, Ed. M. Renewable Resources, Ed. M. KjellinKjellin, I. Johansson Wiley (2010), I. Johansson Wiley (2010)

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