Emulsifier: Department of Food Science and Technology - IPB/DIN/2011

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Emulsifier

Department of Food Science and Technology – IPB/DIN/2011


Emulsions
Liquid/liquid systems of 2 immiscible substances
Substances of particle size = 10-100 microns

oil oil H2O H2O


oil oil H2O H2O
oil H2O
water oil
Oil in water (O/W) Water in oil (W/O)

Department of Food Science and Technology – IPB/DIN/2011


Example :
W/O O/W
butter mayonnaise
margarine salad dressing
milk
cream

Department of Food Science and Technology – IPB/DIN/2011


Stability of Emulsion depends on :

• Droplet size /energy output

• Quality of the interfacial films

• Viscosity of outer phase

• Ratio of the two phases

• Specific density of the two phases

Department of Food Science and Technology – IPB/NAN/2011


Margarine
EMULSIFIER

Oil Emulsifier
Hydrophobic group
water

Hydrophilic group

Mayonnaise

Allow water and oils to


Water
remain mixed together in
Oil an emulsion

Department of Food Science and Technology – IPB/NAN/2011


DESTABILIZATION OF THE DISPERSION

Oil Oil
Oil Oil Oil Oil
Oil
Oil Oil Oil Oil Oil
Oil
Oil Oil
Oil
Water

Oil Oil Oil Oil Oil


Oil
Oil Oil Oil Oil
Aggregation
Water

Oil Oil separation


from water
Water

Department of Food Science and Technology – IPB/NAN/2011


FUNCTIONS
1. To assist stabilization and formation of emulsion
 the reduction of surface tension at the oil-water
interface (margarine & mayonnaise)
2. Alteration of the functional properties of other food
components (bakery products: crumb softener,
dough conditioner)
3. To modify the crystallization of fat (the reduction of
bloom in certain candy products)
4. Change food’s texture
Form the complex compounds with carbohydrate
(starches) and protein
 improve food’s texture
Department of Food Science and Technology – IPB/DIN/2011
SOME DESIRABLE CHARACTERISTICS OF FOOD
EMULSIFIERS

1. Ability to reduce interfacial tension below 10 dynes/cm


2. Ability to be rapidly absorbed at the interface
3. Ability to function effectively at low concentrations
4. Resistance to chemical change
5. Lack of odor, color, and toxicity
6. Economical

Department of Food Science and Technology – IPB/NAN/2011


Emulsifier selection :

• Final product characteristics


• Emulsion preparation methodology
• The amount of emulsifier added
• The chemical and physical characteristics of each
phase
• The presence of other functional components in
the emulsion
• Approval by government (legal emulsifier)
• Processing parameters
• Synergistic effect of other ingredients

Department of Food Science and Technology – IPB/DIN/2011


Most important functions of Emulsifiers
Stabilizations of emulsifiers

Starch complexing - baked goods

Protein interaction - bread

Fat crystallization - margarine, shortening

Viscosity control - chocolate

Foaming and aeration - desserts

Lubrication - extruded products


Department of Food Science and Technology – IPB/NAN/2011
Composition of Food Emulsifiers
OH-Component Acid-Component Others Emulsifier
Glycerol Phosphoric acid Amino component Lecithin's
Glycerol Phosphoric acid Ammonium Ammonium phosphatides
Glycerol - - Monoglycerides
Glycerol - Ethylene oxide Ethoxylated monoglyceride
Glycerol Acetic acid - ACETEM
Glycerol Lactic acid - LACTEM
Glycerol Citric acid - CITREM
Glycerol Acetic-/tartaric acid - DATEM
Glycerol Succinic acid - Succinic ester of monoglyc.
Sucrose - - Sucrose ester
Sorbitol - - Sorbitan ester
Sorbitol - Ethylene oxide Polysorbates
Polyglycerol - - Polyglycerol ester, PFPR
Propylene - - Prophyleneglycerol ester
Lactic Acid - Sodium, calcium SSl, CSL
Tartaric Acid - - Stearyl tartrate
Department of Food Science and Technology – IPB/NAN/2011
HLB concept

Hydrophillic-Lipophillic Balance
• A concept for choosing emulsifiers
• Based upon the relative percentage of
hydrophilic to lipophilic groups within the
emulsifier molecule
• The value of HLB range from 1-20

Lower HLB : a more lipophilic emulsifier


Higher HLB : a more hydrophilic emulsifier

Department of Food Science and Technology – IPB/DIN/2011


Function of Emulsifiers in Relation to the HLB-Value

HLB Application
1
2 Antifoaming agents

3
4 W/O-
emulsifies
5
6
7
8 Wetting agents

9
10
11
12 O/W-
13 emulsifiers
14
15
16 solubilizer

17
18
Department of Food Science and Technology – IPB/NAN/2011
HLB VALUES OF SOME FOOD EMULSIFIERS
• Acetylated monoglycerides (stearate) 3.8
• Sorbitan monooleate 4.3
• Propylene glycol monolaurate 4.5
• Sorbitan monostearate 4.7
• Calcium stearoxyl-2-lactylate 5.1
• Glycerol monolaurate 5.2
• Sorbitan monopalmitate 6.7
• Soy lecithin 8.0
• Diacetylated tartaric acid esters of monoglycerides 8.0
• Sodium Stearoyl lactylate 8.3
• Sorbitan monolaurate ) 8.6
• Polyoxyethylene (20) sorbitan tristearate 10.5
• Polyoxyethylene (20) sorbitan trioleate 11.0
• Polyoxyethylene (20) sorbitan monostearate 14.9
• Sucrose monolaurate 15.0
• Polyoxyethylene (20) sorbitan monooleate 15.0
• Polyoxyethylene (20) sorbitan monopalmitate 15.6
Department of Food Science and Technology – IPB/DIN/2011
Limitation of HLB system
• HLB system does not work well for ionic
emulsifiers  the charge varies with pH

• Commercial preparation usually contain two or


more emulsifier

• HLB system based upon the molecular structure


of emulsifier  does not take into account the
combined oil/aqueous phase/emulsifier system

Department of Food Science and Technology – IPB/DIN/2011


Limitation of HLB system
The inability to take into account :
i. The effect of temperature
ii. The presence of additives
iii.The concentration of emulsifying agents

Department of Food Science and Technology – IPB/DIN/2011


Lecithin
• Phosphatidylcholine and mixtures of phospholipids
• Source : soybeans, corn, sunflower, cottonseed,
rapeseed, eggs
• HLB 8.0
• Partially soluble in water
• Regulation/safety :
safe as food emulsifier
FDA – GRAS (Generally Recognize as Safe)
The EU – Food additive (E322)
Codex – INS No. 322

Department of Food Science and Technology – IPB/DIN/2011


The primary phospholipids reported in commercial lecithin,
where R1 and R2 are fatty acids
Department of Food Science and Technology – IPB/DIN/2011
Mono- & diglycerides of fatty acids
 Most commonly used as food emulsifier
 Synonyms :
 Glyceryl monostearate, glyceryl monopalmitate, glyceryl
monooleate, etc
 Monostearin, monopalmitin, monoolein, etc.
 GMS (for glyceryl monostearate)

• Formula weight
Glyceryl monostearate: 358.6 Two major components
Glyceryl distearate: 625.0 of commercial products

• White or cream colored hard fats of waxy appearance,


plastic products or viscous liquids
Department of Food Science and Technology – IPB/DIN/2011
Mono- & diglycerides of fatty acids

 Insoluble in water
soluble in ethanol, chloroform and benzene
 HLB values range 1-10
 Produced by transesterification of glycerol and
triacylglycerides
 Safety
FDA – GRAS (Generally Recognize as Safe)
The EU – Food additive (E471)
Codex – INS No. 471

 Used in bakery products, frozen desserts, icings,


toppings, and peanut butter
Department of Food Science and Technology – IPB/DIN/2011
Monoglyceride Diglyceride

Di-glycerides ( di-stearate)
O
Mono- Glycerides (mono-stearate) CH2 O C (CH2 )16 CH3
O O
CH O C (CH2 )16 CH3
CH2 O C (CH2 )16 CH3
HO CH2
HO CH Hydrophobic
HO CH2 Hydrophobic Hydrophilic
Hydrophilic

Department of Food Science and Technology – IPB/DIN/2011


Acid ester of mono- and diglycerides

Department of Food Science and Technology – IPB/DIN/2011


ACETEM (E472a)
Synonyms :
• Acetic acid esters of mono- and diglycerides
• Acetoglycerides
• Acetylated mono- and diglycerides
• Acetic- and fatty acid esters of glycerol
• Mono- and diglycerides of fatty acids esterified with
acetic acid

Solubility
Insoluble in strongly polar solvent (water, glycerol)
Dispersible to soluble in edible oil/fats and some alcohol
(ethanol, iso-propanol)
Department of Food Science and Technology – IPB/DIN/2011
LACTEM (E472b)
Synonyms :
• Lactic acid esters of mono- and diglycerides
• Lactoglycerides
• Lactic acid and fatty acid esters of glycerol
• Mono- and diglycerides of fatty acids esterified with lactic
acid
• Glycerol-lacto esters of fatty acids
• Lactated mono- and diglycerides

Solubility
Insoluble in hot water and 1,2-propylen-glycol
Soluble in some hot alcohol (ethanol, iso-propanol or xylol)
and fats (soybean oil/lard)
Department of Food Science and Technology – IPB/DIN/2011
CITREM (E472c)
Synonyms :
• Citric acid esters of mono- and diglycerides of edible fatty
acids
• Mono- and diglycerides of fatty acids esterified with citric
acid
• Monoglycerol citric acid esters
• Monoglycerol citrates
• Citric acid monoglycerides
• Citric acid monoglycerol esters
• Citric acids ester of glycerides
• Citric acid-fatty acid-glycerides
• Citric- and fatty acid esters of glycerol
• Citroglycerides
Department of Food Science and Technology – IPB/DIN/2011
DATEM (E472d)
Synonyms :
• Diacetyltartaric acid esters of mono- and diglycerides
• Diacetyltartaric and fatty acids ester of glycerol
• Mono- and diglycerides of fatty acids esterified with
diacetyltartaric acid

Solubility :
Dispersible in hot/cold water
Offer certain solubility in warm fats, oils, methanol/ethanol,
acetone
ADI 0-50 mg/kg bw (JECFA)
Interact with starch and flour protein in bread

Department of Food Science and Technology – IPB/DIN/2011


MATEM (E472f)
Synonyms :
• Diacetyltartaric-, acetic-, and fatty acids ester of glycerol,
mixed
• Mono- and diglycerides of fatty acids esterified with
acetic- and diacetylated tartaric acid

Solubility :
Dispersible in water
Soluble in methanol, ethanol, acetone

ADI 0-50 mg/kg bw (JECFA)

Department of Food Science and Technology – IPB/DIN/2011


Polysorbates
Polyoxyethylene esters of sorbitan monoesters

Department of Food Science and Technology – IPB/DIN/2011


Chemical structure of Polysorbates

where w + x + y + z = approx. 20 and RCO- is the fatty acid moiety

Department of Food Science and Technology – IPB/DIN/2011


Polysorbate 20

• Polyoxyethylene (20) sorbitan monolaurate

• Solubility
Soluble in water, ethanol, ethyl acetate, dioxane
Insoluble in mineral oil and petroleum ether

 Safety : FDA – CFR No. 172.515


Codex – INS No. 432
• ADI 0-25 mg/kg bw
• Lemon to amber colored oily liquid at 25oC, with
a faint characteristic odor
Department of Food Science and Technology – IPB/DIN/2011
Polysorbate 40
• Polyoxyethylene (20) sorbitan monopalmitate

• Solubility
 Soluble in water, ethanol, methanol, ethyl
acetate, and acetone
 Insoluble in mineral oil

 Lemon to orange colored, oily liquid or semi-gel


at 25o, with a faint characteristic odor
 Safety : FDA – CFR No. 172.515
Codex – INS No. 434
• ADI 0-25 mg/kg
Department of Food Science and Technology – IPB/DIN/2011
Polysorbate 60
• Polyoxyethylene (20) sorbitan monostearate (Tween 60)
• Soluble in water, ethyl acetate, anillin, and toluene
Insoluble in mineral oil and vegetable oil
 Safety : FDA – CFR No. 172.836
Codex – INS No. 435
• HLB = 14.9
• Lemon to orange colored oily liquid or semi-gel at 25o,
faint characteristic odor
• ADI 0-25 mg/kg
• Application
Oil toppings, cake mixes,
and cake icing
Department of Food Science and Technology – IPB/DIN/2011
Polysorbate 65

• Polyoxyethylene (20) sorbitan tristearate


• Dispersible in water
Soluble in mineral oil, vegetable oil, petroleum ether,
acetone, ether, dioxane, ethanol and methanol
 Safety
FDA – CFR No. 172.838
Codex – INS No. 436
• Tan coloured, waxy solid at 25oC,with a faint
characteristic odour
• Permitted in ice cream, frozen food, custard

Department of Food Science and Technology – IPB/DIN/2011


Polysorbate 80
• Polyoxyethylene (20) sorbitan monooleate
• Solubility
 Soluble in water, ethanol, methanol, ethyl
acetate and toluene
 Insoluble in mineral oil and petroleum ether

 Safety : FDA – CFR No. 172.840


Codex – INS No. 433
• Lemon to amber coloured oily liquid at 25o, with
a faint characteristic odour
• Application : Special dietetic foods
Fat soluble vitamine
Department of Food Science and Technology – IPB/DIN/2011
Sorbitan esters
Nomenclature and physical characteristic of sorbitan esters

Name E No. FDA Ref.


Sorbitan monolaurate E 493 -
Sorbitan monostearate E 491 CFR 172.842
Sorbitan monooleat E 494 -
Sorbitan tristearate E 492 Self-determined GRAS
Department of Food Science and Technology – IPB/DIN/2011
Sorbitan monostearate

• A mixture of the partial esters of sorbitol and its


mono- and dianhydrides with edible stearic acid
• Solubility
 Soluble at temperatures above its melting point
in toluene, dioxane, carbon tetrachloride, ether,
methanol, ethanol and aniline
 Insoluble in petroleum ether and acetone
 Insoluble in cold water but dispersible in warm
water
 Soluble with haze at temperatures above 50o in
mineral oil and ethyl acetate

Department of Food Science and Technology – IPB/DIN/2011


Sorbitan monostearate

• ADI 0-25 mg/kg as the sum of sorbitan esters of


lauric, oleic, palmitic and stearic acids
• HLB = 4.7
• Safety : FDA – CFR No. 172.842
Codex – INS No. 491
• Light cream to tan beads or flakes
or hard, waxy solid with a slight
characteristic
odor

Department of Food Science and Technology – IPB/DIN/2011


Stearoyl Lactylates

• An ionic, hydrophylic emulsifier


• Lactic acid ester of monoglyceride with sodium
or calcium
• Form strong complex with gluten in starch and
especially valuable in baked products

Department of Food Science and Technology – IPB/DIN/2011


Sodium stearoyl-2-lactylate
• Chemical names :
Sodium di-2-stearoyl lactate, major
Sodium di-(2-stearoyloxy) propionate component
• Synonyms :
Sodium stearoyl lactate
Sodium stearoyl lactylate
• Chemical formula
C21H39O4Na; C19H35O4Na
(major components)

where R is C17H35 or C15H31 and


the mean value of n is normally 2
Department of Food Science and Technology – IPB/DIN/2011
Sodium stearoyl-2-lactylate
• Solubility
Insoluble in water, soluble in ethanol
 Safety
FDA – CFR No. 172.846
Codex – INS No. 481
• ADI 0-20 mg/kg
• White or slightly yellowish powder or brittle solid
with a characteristic odour
• Application : waffles, cake icing and filling,
topping, non-dairy creamer, sauces and gravies
Department of Food Science and Technology – IPB/DIN/2011
Calcium stearoyl-2-lactylate
• Chemical names :
Calcium di-2-stearoyl lactate, major
Calcium di-(2-stearoyloxy) propionate component
• Synonyms :
Calcium stearoyl lactate
Calcium stearoyl lactylate
• Chemical formula
C42H78O8Ca; C38H70O8Ca
(major components)

where R is C17H35 or C15H31 and the mean value of


n dependent on the proportion of lactic acid present
Department of Food Science and Technology – IPB/DIN/2011
Calcium stearoyl-2-lactylate
• Solubility : Slightly soluble in hot water
 Safety
FDA – CFR No. 172.844
Codex – INS No. 482
• ADI 0-20 mg/kg
• White or slightly yellowish powder or brittle solid
with a characteristic odor
• Application : yeast-leavened bakery products,
whipped topping, dehydrated potatoes
Department of Food Science and Technology – IPB/DIN/2011
Polyglycerol Esters
• HLB 6-11  a versatile emulsifier for food applications

EU FDA
Polyglycerol No number No number
Polyglycerol ester E475 CFR 172.854

• Polyglycerol fatty acid esters, glycerin fatty acid ester


• Light yellow to amber, oily to very viscous liquids
Light tan to medium brown, plastic or soft solids
Light tan to brown, hard, waxy solids
• ADI 0-25 mg/kg bw

Department of Food Science and Technology – IPB/DIN/2011


Affirmed GRAS Emulsifiers

184.1101 Diacetyl tartaric acid esters of mono-


and diglycerides
184.1323 Glyceryl monooleate
184.1324 Glyceryl monostearate
184.1328 Glyceryl behenate
184.1400 Lecithin
184.1505 Mono- and diglycerides
184.1521 Monosodium phosphate derivatives
of mono- and diglycerides

Department of Food Science and Technology – IPB/DIN/2011


Department of Food Science and Technology – IPB/DIN/2011
Emulsifier usage in U.S.A
(millions of pounds)
Emulsifier Bread Cake mix M,SD,S* Total
Mono&Di 116 23 30.5 200
Lecithins - 1 10 42.5
MG 13.2 0.5 2.5 25
Polysorb 1.5 1 0.75 8
CSL/SSL 27 0.75 0.25 30
PG ester - 10 1.8 14.3
SorbMS - 0.1 2 -
*Margarine, salad dressings, shortenings

Department of Food Science and Technology – IPB/DIN/2011


Department of Food Science and Technology – IPB/DIN/2011

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