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Interesterification
Interesterification involves an exchange of acyl group among triglycerides. Acyl groups may exchange positions within a triglyceride or among triglyceride molecules.
Interesterification
S S S S
SSS
(SUS
SSU)
(SUU
USU)
UUU
Random Interesterification
A. S (Stearic acid 35%) O (Oleic acid 30%) L (Linoleic acid 35%) B. S (50%) O (40%) L (10%)
After random interesterification, the triglyceride compositions are: Sample A Triglyceride SSS OOO LLL SSO SSL OOS OOL LLS LLO SOL* % = 4.3 = 2.1 = 4.3 = 11.0 = 12.8 = 9.5 = 9.5 = 12.8 = 11.0 = 22.0 Sample B Triglyceride SSS OOO LLL SSO SSL OOS OOL LLS LLO SOL* % = 12.5 = 6.4 = 0.1 = 30.0 = 7.5 = 24.0 = 4.8 = 1.5 = 1.2 = 12.0
Catalysts
High temperature catalysts: KOH and NaOH Low temperature catalysts: Sodium Methoxide (NaOCH 3)
Reaction Mechanisms
1. The formation of enolate ion 2. The formation of Beta-Keto ester 3. Interesterification
H2O +
O CH3 C CH2
-
OCH3 C CH2
CH3
O C CH2
CH3OH
O O O O C
H C O C H2R2 C O C H2R3
O O O O C C H C O C H2R2 C O C H2R3 R1
O COCH2R3
II
O O O O C
H O C R1 C CH2 R2
_ O O O C H O C R1 C CH2R2
COCH2 R3 III
COCH2R3 IV
_
O
O C C H 2R
4
C O C H 2R 5
C O C H 2R 3
C O C H 2R 6
I
O O C H C O C O
VI _
VII
R 1 C H 2R 4 O O C O C H 2R 2 C O C H 2R 3 O O C O C H 2R 5 C O C H 2R 6
R4 R 2+ R3
R1 R5 R6
IX
R1 R2 + R3 R5 R4 R6
VIII
Random Esterification
Interesterification can be carried out to an equilibrium condition, at which point the fatty acids assume an almost random distribution among triglycerides.
S S S S
SSS
(SUS
SSU)
(SUU
USU)
UUU
Direct Interesterification
Interesterification can be directed away from its usually random end-point if the fat is allowed to crystallize during reactions. The trisaturated glycerides crystallize first.
S S S S
SSS
(SUS
SSU)
(SUU
USU)
UUU
Directed Interesterification
S O L
1. 2. 3. 4. 5.
33.3 mole % solid 8.3 mole % liquid 8.3 mole % liquid 24.9 mole % liquid 24.9 mole % liquid
S S S S
SSS
(SUS
SSU)
(SUU
USU)
UUU
Benefits of Interesterification
Lard may be given different properties by varying the method of interesterification. One set of conditions favors intramolecular interchange and results in a crystal-modified lard (CML). Conditions favoring random distribution can be controlled to yield a partially modified lard (PML). Conditions favoring directed interesterification can be used to control the GS3 content of direct interesterified lard (DIL).
Applications
Shortenings: The proportion of palmitic acid in the 2-position is reduced from about 64% to 24% on random interesterification. Natural lard Randomized lard beta beta
Randomization of lard improves its plastic range and thus makes it a better shortening than natural lard.
Confectionary Fats
Hydrogenated palm kernel oil is a hard butter melting at 46rC and produces a waxy feel in the mouth. On randomization, its melting point is reduced to 35rC. By blending hydrogenated palm kernel oil and its randomized product, a whole series of hard butters with highly desirable melting qualities (rapid melt in mouth) are obtained
Confectionary Fats from Blend of Hydrogenated and Interesterified Hydrogenated Palm Kernel Oil
SCI Fat Hydrogenated palm kernel oil (PKO) Int. hydrogenated PKO 50% hydrogenated 50% int. hydrogenated M.P.(rC) 46.8 10 74.2 20 67.0 35 15.4 38 11.7
35.0
65.0
49.9
1.4
1.1
41.7
70.0
57.4
8.7
5.2
Effect of Randomization on SCI of an 80:20 Mixture of Lightly Hydrogenated Soybean Oil and Palm Stearine
Alpha
Beta Prime
Beta
D D
Alpha
Beta-Prime
Beta
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