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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
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