Modification of Edible Fats and OilsModification of Edible Fats and Oils

Namal SenanayakeNamal SenanayakeMartek Biosciences CorporationMartek Biosciences Corporation

Winchester, Kentucky 40391, USAWinchester, Kentucky 40391, USA

Fereidoon ShahidiFereidoon ShahidiDepartment of BiochemistryDepartment of Biochemistry

Memorial University of NewfoundlandMemorial University of NewfoundlandSt. JohnSt. John’’s, NL, A1B 3X9, Canadas, NL, A1B 3X9, Canada

November 12,November 12, 20072007

▪▪ Improves Oxidative StabilityImproves Oxidative Stability

▪▪ Alter the Melting PropertiesAlter the Melting Properties

▪▪ Alter the Crystallization PropertiesAlter the Crystallization Properties

▪▪ Economic Advantages:Economic Advantages:Less Expensive Oil More Expensive OilLess Expensive Oil More Expensive Oil

Why Modified Lipids ?Why Modified Lipids ?

Modification MethodsModification Methods

1)1) HydrogenationHydrogenation

2)2) FractionationFractionation

3)3) InteresterificationInteresterification

4)4) Physical BlendingPhysical Blending

HydrogenationHydrogenation

▪▪ Treatment of Fats and Oils with HydrogenTreatment of Fats and Oils with Hydrogen▪▪ A Catalyst and Heat must be presentA Catalyst and Heat must be present▪▪ Exothermic ReactionExothermic Reaction▪▪ Converts Liquid Oils into Solid or Converts Liquid Oils into Solid or

SemiSemi-- Solid ProductsSolid Products▪▪ Improves Oxidative StabilityImproves Oxidative Stability▪▪ Imparts desired Physical Properties Imparts desired Physical Properties (melting point, SFC)(melting point, SFC)

Hydrogenation: PrincipleHydrogenation: Principle

Catalyst – CH = CH – + H2 – CH2 – CH2 –

Possible Reactions during HydrogenationPossible Reactions during Hydrogenation

▪▪ Complete Saturation: Complete Saturation: 18:318:3 18:218:2 18:118:1 18:018:0

▪▪ Partial HydrogenationPartial Hydrogenation

▪▪ Geometric Geometric IsomerizationIsomerization::ciscis transtrans

▪▪ Positional Positional IsomerizationIsomerization: : ciscis transtrans

HydrogenationHydrogenation

Oil Deaeration Heating Reaction

TerminationFiltration

Catalyst

Hydrogen

CoolingBleaching

Hydrogenation: Monitoring the ReactionHydrogenation: Monitoring the Reaction

▪▪ HH22 Consumption Consumption

▪▪ Refractive IndexRefractive Index

▪▪ Iodine ValueIodine Value

▪▪ Melting Properties:Melting Properties:

-- Melting PointMelting Point

-- SFCSFC

Hydrogenation VariablesHydrogenation Variables

▪▪ ReactionReaction Temperature Temperature

▪▪ PressurePressure

▪▪ AgitationAgitation

▪▪ Catalyst TypeCatalyst Type

▪▪ Catalyst ConcentrationCatalyst Concentration

▪▪ Reaction TimeReaction Time

Impact of Hydrogenation VariablesImpact of Hydrogenation Variables

DecreaseIncreasePressure

IncreaseDecreaseTemperature

DecreaseIncreaseAgitation Speed

IncreaseDecreaseCatalyst Dosage

Trans IsomerFormation

Saturate Formation

Increase of:

Hydrogenation Conditions Affecting SelectivityHydrogenation Conditions Affecting Selectivity

Shallow SFC CurveSteep SFC Curve

Low trans fatty acidsHigh trans fatty acids

High agitationLow agitation

Nonselective catalystSelective catalyst

Low catalyst (0.02% Ni)High catalyst (0.05% Ni)

High hydrogen pressure ( >3 Atm)Low hydrogen pressure ( 1 Atm)

Low temperature (120oC)High temperature (170oC)

Nonselective HydrogenationSelective Hydrogenation

Hydrogenation: Feedstock Oil QualityHydrogenation: Feedstock Oil Quality

< 2 ppmPhosphorus

< 25 ppmSoaps

< 0.05%Moisture

< 0.05%Free fatty acids

< 10p-Anisidine value

< 0.5 meq/kgPeroxide value

SpecificationParameter

Effect of Hydrogenation on Soybean Oil CompositionEffect of Hydrogenation on Soybean Oil Composition

3918:3

355418:2

492118:1

4418:0

91116:0

Partially Hydrogenated and Winterized oil

RBD oilFatty Acid (%)

Hydrogenated Oil End Products: ExamplesHydrogenated Oil End Products: Examples

▪▪ Liquid Oils Liquid Oils –– Brush HydrogenationBrush Hydrogenation

▪▪ Margarine Bases Margarine Bases –– Partial HydrogenationPartial Hydrogenation

▪▪ Shortening Bases Shortening Bases –– Partial HydrogenationPartial Hydrogenation

▪▪ StearinStearin -- Total HydrogenationTotal Hydrogenation

▪▪ Coating Fats Coating Fats –– Partial HydrogenationPartial Hydrogenation

FractionationFractionation▪▪ Separates Fats and Oils into Fractions with differentSeparates Fats and Oils into Fractions with differentMelting Points Melting Points ▪▪ Three Major Processes:Three Major Processes:

(a) Dry Fractionation(a) Dry Fractionation-- Gradual cooling of oil w/o solventGradual cooling of oil w/o solvent-- includes winterization and includes winterization and dewaxingdewaxing

(b) Solvent Fractionation(b) Solvent Fractionation-- Crystallization performed in diluted solutionsCrystallization performed in diluted solutions-- Solvents: Acetone, Hexane & IPASolvents: Acetone, Hexane & IPA

(c) Detergent Fractionation(c) Detergent Fractionation-- Addition of detergent solution into crystallized Addition of detergent solution into crystallized oiloil

-- An electrolyte is also addedAn electrolyte is also added

Fractionation PrincipleFractionation Principle

[ SSS-SSU-SUU-UUU ] [ SSS-SSU ] + [ SUU-UUU ]Crystallization

Filtration

Oil Crystallization Filtration

Liquid Olein

Solid Stearin

Fractionated Fats & OilsFractionated Fats & Oils

Palm oil crude / bleached / deodorizedPalm kernel oil crude / bleached / deodorizedSoybean oil bleached / deodorizedCottonseed oil bleached / deodorized

Fish oil- Native crude / bleached- Hydrogenated bleached / deodorized

Tallow crudeMilk fat crude / deodorized

OIL TYPE REFINING STATE

Fractionation: Analytical MethodsFractionation: Analytical Methods

Cc 13e-92Lovibond colorCe 16-89Fatty acid composition (GC)Cd 1-25Iodine value (Wijs method)Cd 8-53Peroxide valueCc 11-53Cold testCc 18-80Dropping pointCc 6-25Cloud pointCc 1-25Melting point

Cd 16b-93Solid fat content (SFC)AOCS Method NumberAnalytical Technique

Effect of Fractionation on Palm Oil CompositionEffect of Fractionation on Palm Oil Composition

744050SFC (%) at 10oC

51.022.036.0Melting Point (oC)405853Iodine Value6.011.010.018:2(%)32.043.039.018:1 (%)6.04.44.518:0 (%)54.040.044.016:0 (%)1.31.01.014:0 (%)

Palm Stearin

Palm Olein

Palm OilChemical Properties

InteresterificationInteresterification

▪▪ Rearrange and Randomize the Rearrange and Randomize the FAsFAs on the Glycerol on the Glycerol MoleculesMolecules

▪▪ Why Why InteresterifyInteresterify ??

-- Achieve Melting Properties that cannot be Achieve Melting Properties that cannot be achieved by Other Methodsachieved by Other Methods

-- Replace Hydrogenated FatsReplace Hydrogenated Fats

-- Change the Melting PropertiesChange the Melting Properties

Chemical Chemical InteresterificationInteresterification: Principle: Principle

R1R1R1 + R2R2R2

R1R1R1

R1R2R1 R2R1R1

R1R2R2 R2R1R2

R2R2R2

Catalyst

0

20

40

60

80

0 10 20 30 40 50 60

Temperature (C)

SFC

(%)

R1

R2

0

20

40

60

80

0 10 20 30 40 50 60

Temperature (C)

SFC

(%)

R1, R2

Chemical Chemical InteresterificationInteresterification: Feedstock Oil Quality: Feedstock Oil Quality

< 5 ppmPhosphorus

< 0.01%Moisture

< 0.05%Free fatty acids

< 1.0 meq/kgPeroxide value

SpecificationParameter

Chemical Chemical InteresterificationInteresterification: Process Steps: Process Steps

1)1) Pretreatment of Oil: Pretreatment of Oil: 120120ooC, < 50 mbar C, < 50 mbar HH22O < 0.01%O < 0.01%

2) Catalyst Addition:2) Catalyst Addition: 0.05 0.05 –– 0.1%0.1%

3) Reaction:3) Reaction: 9090--150150ooC; 15C; 15--60 min; < 50 mbar60 min; < 50 mbar

4) Catalyst Deactivation:4) Catalyst Deactivation: water; organic acid; water; organic acid; silicatesilicate

5) Centrifugation5) Centrifugation

InteresterificationInteresterification

▪▪ CHEMICAL: CHEMICAL: -- RandomRandom-- Preferred Catalysts: Preferred Catalysts:

CHCH33ONa; CHONa; CH33CHCH22ONaONa

▪▪ ENZYMATIC: ENZYMATIC: -- SelectiveSelective-- LipaseLipase--CatalyzedCatalyzed

InteresterificationInteresterification: Process Comparison: Process Comparison

Pretreatment of Oil

Catalyst:CH3ONa

CatalystDeactivation Bleaching Deodorization

Pretreatment of Oil

Catalyst:Lipase Deodorization

Chemical Chemical InteresterificationInteresterification::

Enzymatic Enzymatic InteresterificationInteresterification::

InteresterificationInteresterification: Monitoring the Reaction: Monitoring the Reaction

▪▪ SFC SFC

▪▪ Melting PointMelting Point

▪▪ Dropping PointDropping Point

▪▪ Cloud PointCloud Point

▪▪ TAG Profile (FTTAG Profile (FT--NIR)NIR)

InteresterificationInteresterification: Current Trends: Current Trends

▪▪ Increasing trends to reduce/ eliminate TFA in Increasing trends to reduce/ eliminate TFA in foodsfoods--LegislationLegislation

USA: FDA labeling USA: FDA labeling ononTransTrans fats fats –– January 2006January 2006Europe: max 2% in food fats (Denmark)Europe: max 2% in food fats (Denmark)

▪▪Major food processors are replacing TFA by Major food processors are replacing TFA by low/zero TFA alternativeslow/zero TFA alternatives▪▪ Increased demand for:Increased demand for:

Low trans products: < 5% in food fatsLow trans products: < 5% in food fatsZero trans products: < 0.5% in food fatsZero trans products: < 0.5% in food fats

▪▪ Alternative technology for partial hydrogenationAlternative technology for partial hydrogenation

InteresterificationInteresterification: Product Examples: Product Examples

▪▪ Low/No Trans Margarines and Spreads Low/No Trans Margarines and Spreads

▪▪ Low/No Trans ShorteningsLow/No Trans Shortenings

▪▪ Cocoa Butter Alternative FatsCocoa Butter Alternative Fats

▪▪ Reduced Calorie/ No Calorie FatsReduced Calorie/ No Calorie Fats

▪▪Milk FatsMilk Fats

Physical BlendingPhysical Blending

▪▪ Easiest and Most Economical Way to Modify FatEasiest and Most Economical Way to Modify Fat▪▪ Purpose:Purpose:

-- Increase StabilityIncrease Stability-- Alter the Color and FlavorAlter the Color and Flavor-- Alter the Melting PropertiesAlter the Melting Properties

▪▪ Blend Two Oils with different Melting Curves toBlend Two Oils with different Melting Curves toachieve Oil with a Specific Melting Propertiesachieve Oil with a Specific Melting Properties▪▪ Blends can be Calculated using the SFI Value andBlends can be Calculated using the SFI Value and

Linear AlgebraLinear Algebra

SummarySummary▪▪ ReasonsReasons for Modifying Fats & Oils:for Modifying Fats & Oils:

1) Alter Physical Properties 1) Alter Physical Properties 2) Improvement of Stability2) Improvement of Stability3) Economical Benefits3) Economical Benefits

▪▪ModificationModification Methods:Methods:1) Hydrogenation1) Hydrogenation2) Fractionation2) Fractionation3) 3) InteresterificationInteresterification4) Blending4) Blending5) Combinations of each of the above5) Combinations of each of the above