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FISHERIES AND MARINE SERVICE
Translation Series No. 3463
One-phase transesterification of two-component mixtures
of liquid oils and highly hydrogenized oils
by A. Katzer, Leopold Strecker, and Urszula Fal
Original title: Jednofazowe przeestryfikowanie dwuskladnikowych
• mieszanin olejow cieklych z wysokouwodornionymi
From: Tluszcze Jadalne
pp. 165-184,VroL V
NL)
4
1 191'4
Translated by the Translation Bureau( BSH)
Multilingual Services Division
Department of the Secretary of State of Canada
Department of the Environment
Fisheries and Marine Service
Halifax Laboratory
Halifax, N.S.
1975
27 pages typescript
^= t Nt
«•
3y- 6 3
DEPARTMENT OF THE SECRETARY OF STATE
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BUREAU DES TRADUCTIONS
ti
1^:.
MULTILINGUAL SERVICES •.._
^:•'^^nL éi.
DIVISION DES SERVICES
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CANADA
MULTILINGUES
DIVISION
INTO - EN
TRANSLATED FROM - TRADUCTION DE
English
Polish
AUTHOR -AU^EUXatZer
Leopold Strecker, and Ur.swula .Fa.l
TITLE IN ENGLISH - TITRE ANGLAIS
One-phase transesterification•of two-component, -mixtures
of liquid oils and highly hydrogenized oi1s.
TITLE IN FOREIGN LANGUAGE (TRANSLITERATE FOREIGN CHARACTERS)
TITRE EN LANGUE ETRANGERE ( TRANSCRIRE EN CARACTÉRES ROMAINS)
lednofazowe przeestryfilrowanie dwuskladni.kowych mieszanin oie jow cieklych z wysokouwodornior_ymi.
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DEPARTMENT OF THE SECRETARY OF STATE
SECRÉTARIAT D'ÉTAT
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TRADUCTION NON REVISEE
Information teulement
transOne-phaseAesterification of two-component mixtures of
liquid oils and highly hydrogenized oils.
by Leopold Strecker and Urszula Fal, Institute of the Fat
Industry, Warsaw
One aspect in the assessment of the food value of edible
fats is the presence of biologically valuable, indispensable
unsaturated fatty acids (I.U.F.A.) Thus there exists a growing
demand for dietetic margarines containing a high proportion of
these acids on fatty bases. However, the production of such
bases is directly connected with an increased liquid oil content.
Production of dietetic margarines can be achieved by using
traditional technology on the condition that the increased amount
of liquid oils will go together with the introduction into the
base of fat hydrogenized to a suitably higher melting temperature.
Thus a proper crystalline structure will be created, which will
ensure the proper consistency and softness of the product. This
method, while being most simple and most commonly used, is not
ideal sincd the product obtained possesses, besides the increased
SOS -WA -M -M
. 2 .
I.U.F.A. content, some unfavourable features, such as:
-- high melting temPerature of hardened fat which is one of the
components of margarine base;
-- high proportion of unsaturated acids with a "trans" configu-
ration in hardened fat;
-- instability of crystalline forms which can produce eutectelics.
The use of the product of one-phaseAesterification of mixtures of totally hydrogenated fats with liquid oils in the prod-
uction of dietetic margarines would create bases devoid of "trans"
isomers which, • at the same time, would possess a homogeneous
crystalline structure and a high I.U.F.A. content. Besides, trans esterification creates great possibilities of choosing components
for margarine bases, especially those bases which are used in the
form of fully hydrogenated fats. This fact can be of particular
significance should the country's market have a surfeit of animal
fats, which are currently not used for margarine production.by
traditional technology.
The Institute of the Fat Industry has been studying these
problems for several years. Studies were made, for example, of
Aesterification of hydrogenated beef suetl or hydrogenated lard 2 with soya oil or sunflower oil.
This article discusses the results of studies concerning
L-1- 7the influence of A esterification upon the changes in the properties
-
-
1
of physical-chemical mixtures of hydrogenated fats with liquid
oils. The above process is considered from the point of view of
_
using the esterified fats as bases of dietetic margarines. The
^ 3 w
I
_1. :1:
studies made consisted of experimental.-esterification of twocomponent mixtures containing such highly hydrogenated fats as
low-erucic rapeseed oil, palm oil (red) and cod-liver oil, as well
as a liquid component -- sunflower oil or soya oil. A total of
six types of mixtures were studied. They contained 20 - 35% of
solid component and correspondingly, $0 - 65% of sunflower oil
or soya oil.
Description of materials used in experiments:
:
The following fats were used in the experiments:
Hydrogenated low-erucic rapeseed oil: This oil was obtainéd as a
liquid after a full refining at the Fat Processing Factory named
after Gen. W. Wroblewski in Gdansk. It was subsequently hydrogenated in a laboratory (autoclave) in the following conditions:
Charge $ kg., hydrogen pressure 1 - 1.2 atmospheres, temperature
1$0 - 190°, RCH 55/10 catalyst produced by Hoechst, added at
0.3% nickel weight in relation to'oil weight. Catalyst applied
in two doses. Duration: approx. 5 hours. The hydrogenation process
was controlled by measuring the light refraction coefficient at
60°. Hydrogenated fat was stored at temperatures below +50 after
separation from metallic nickel.
Hydrogenated palip oil: Raw oil was received from the Fat Processing Factory named after the 15th of December in Warsaw. The oil
was deacidified in the laboratory and subsequently hydrogenated
in conditions similar to the above-described.
Hydrogenated cod-liver oil: It was received, after bleaching,
from the Silesian Fat Processing Factory in Trzebinia in a partly
-4-.
hydrogenated form with an iodic number 50.3. Further hydrogenation
was performed in the laboratory in conditions similar to those
mentioned above, except for the duration of the process, which in
this case, was 9 hours.
All hydrogenated fats were deacidified and bleached in the
laboratory before they were made into mixes ready for A esterification.
Liquid oils -- soya oil and sunflower oil -- came from the
Silesian Fat Processing Factory in Trzebinia where they had been
fully refined.
A detailed description of individual components of fatty
mixtures eserified is given in table I. It includes physical and
chemical properties of fatty acids and their composition.
Method:
Six types of two-component mixtures were made of fats
included in table I. These six types exhausted all possible
combinations of the above ingredients. Each mixture consisted of
one highly hardened fat and one of_the two liquid oils. At the
same time, each type of two-component mixture possessed a fourlevel proportion of liquid oil to hardened oil. All types of mixtures were grouped in four categories in which weight.proportions
of solid fat to liquid fat were as follows: 20:80, 25:75, 30:70,
and 35:65 (table II).
Individual experiments used the following procedure:
500 g. of a mixture of hardened fat and liquid oil (in appropriate
amounts) were made in a 1-litre three-necked glass flask. Subse-
(167)
I
-5quently, the mixture was de-aerated and dehydrated at a lowered
pressure at 900 temperature with a steady flow of nitrogen and
vigorous stirring. After 30 minutes of drying, half the contents
of the flask were poured into a jar. This sample was used for
- 4 7 ^-. o-N ÿ -
analytic determinations of fat before.testerification. The remaint•1 !' 4 'l
ing portion of the mixture wastesterified in standard conditions.
For this purpose, fat was heated to 1300 while the pressure in the
flask was lowered to approx 10 mm Hg. Nitrogen flow was small,
and stirring, intensive. When 130' was reached, the catalyst
9
powder trisodium glycerate was drawn into the flask using a
vacuum. The mixture was being stirred throughout this part of the
^.•.s-
experiment.,'Esterification with 0.5% of weight catalyst was
performed for 30 minutes after adding the catalyst with other
conditions remaining unchanged.
Table I - Components of fatty mixtures used in experiments.
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1. type of fat
2. physical and chemical properties
3. softening temperature
4. number
5. iodic
6. Lea
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7. acid
8. composition-of fatty acids (%)
9. sunflower oil
10. soya oil
11. low-erucic, hydrogenated rapeseed oil
12. hydrogenated palm oil (red)
13. hydrogenated cod-liver oil
0\
i
it
-7.-
(169)
Table II - Iodic number and linoleic acid content in esterified
fats.
lodown I.zas-lartoo6 lcwasu 11nolowogo
w .1;:luszcza.oh przaestrynkowanych
-
Kwas linolowy. /%,/
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types of fats in the mixture
iodic number
linoleic acid (%)
% of hardened fats and liquid
oils in the mixtures
—
f
I
46 ,5
- li
li
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Pi
h
43,0
—
5. hardened rapeseed oil
6. hardened palm oil
7. hardened cod-liver oil
8. sunflower oil
9. soya oil
After half an hour, the fat in the flask was cooled to
approx. 70 0 and the vacuum was liquidated with nitrogen. Subsee o
quently, the'esterified fat was rinsed, first with hot water
with citric acid, then with pure hot water (several times). After
the catalyst was deactivated and the products of its disintegration
II
H
- 8 washed away together with newly created soaps, the fat was dried
for 30 minutes at 90° temperature and 10 mm Hg pressure. Nitrogen
flow was constant, and stirring uninterrupted. The obtained -1.-esterified fat was subsequently analyzed.
The degree of:èàtèrification was determined on the basis
of temperature differences: of softening and of the drop point,
At the same time, micropenetratJ
ion and dilatation were also determined before and after esterifi-
before and after resterification.
cation in order to obtain a full picture of physical properties of
<
both the fatty mixtures and'estrified fats. Differential thermal
analysis was also performed. The latter method provides especially
valuable information concerning the two essential factors which
determine the fatts consistency: solid phase content and its
melting boundaries, and type of crystalline formation of a given
fat. Besides, determinations of iodic number, acid number, peroxide
number and the composition of fatty acids were made to obtain
a chemical characteristicsof both the components and the products.
In addition, the contents of "trans" isomers of fatty acids
were determined on an ad hoc basis. They were determined in mixtures
5
which contained 30% hardened fats afteresterification, and in
original hydrogenated fats. None of the fats analyzed contained
"trans" isomers. This is the result of the very low iodic numbers
of the hydrogenated fats used in this study. At the same time,
it proves that esterification is not aecompanied by geometric
isomerization.
The majority of the above analyses were made according to
the currently obligatory state-imposed norms. The exceptions were:
micropenetration, dilatation and diffèrential thermal analysis.
Micropenetration was determined by a process described previously
(4), while dilatation was performed according'to DGF - Einheitsmethoden - Abteilung C - Fette IV 3e. We have not applied
differential thermal analysis to determine physical and chemical
changes in esterified acids so far. The method of taking measurements together with the measuring apparatus, and its working
principle was discussed in detail by K. Danowski (3).
Results and Discussion:
Melting temperature is the basic indicator of changes
-f ,%- :... ,
caused by.'esterification in the studied fatty mixtures. Fig. 1
illustrates melting temperatures before and after the reaction
expressed by the drop point. The course of individual curves
_ ^. .
indicates that one-phase èstërification Iawers the drop point
from 8.5 0 to 20.40, depending on the mixture used. This decrease
is directly proportional to the amount of liquid component, but
at the same time, it depends also on the types of components.
The greatest differences between melting temperatures before and
.,,..^
after,',esterification can be observed in mixtures containing hardened low-erucic rapeseed oil, while mixtures based on hydrogenated
palm oil or cod-liver oil demonstrate smaller differences. Besides,
it is apparent that hardened fat is responsible for the melting
temperature of the mixture before=testerification. An increase in
liquid oil from 65% to 80% lowers the drop point only slightly.
-10-
(171)
. Fig. 1. Melting temperature of two-component fatty mixtures with
_ -^
.
a different ratio of components before and after;:ésterification.
I tmZV-15 mZtTszcZV uwoDOxrtzorr-^o AN
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65
80
75
70 75
70
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65
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TLUSZCZ PRZEESTRYSMosv,MY I
RYôU;1F'K J.
T.7,!P1:-2AT'J3Y TOPiiÏE,*iLi D°IITSRL1D:iIriOWXCH NI]^SZftl`J£Ir !rwSZCZJ!`l 0 RO211YCR no---PORCJACH. I"io^?PC3;t^.^*iiTbS9
PRZED I 7O 11i2t;s i7`RY^7^
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5. hydrogenated cod-liver oil
6. ratio of sunflower oil ( f)
7. ratio of soya oil (%)
$..mixture before esterification
g.`;^.esterified fat
1. ratio of hydrogenated fat
2, drop point (OC.)
3. hydrogenated rapeseed oil
4. hydrogenated palm oil
:xI-Fr.,_,_„_-,^ ,^^^ ,.-.^_ rn •
-
TM
-
11
-
On the other hand, the lowering.of the drop point corresponds to the increase of liquid oil in%esterified fats. From the
point of view of using these fats as margarine bases (bearing in
mind that the melting temperature of:dietetic margarine should
not exceed 35 ° ), the following mixtures qualify:
mixtures containing 20% hydrogenated low-erucic rapeseed oil,
20 - 25% hydrogenated palm oil (red), and correspondingly
80 - 75% sunflower oil, 20% hydrogenated palm oil (red) and
80% soya oil, 20% hydrogenated cod-liver oil and 80% of soya oil
or sunflower oil.
The studies of consistency at 20 0 , the results of which
are represented in fig. 2, have shown a very significant increase
in micropenetration of fats afteri.éterification. This is caused
chiefly by a smaller amount of solid phase in these fats.
Simultaneously, we observed how the type of component influences the hardness of the fat mixture and theAésterified prod-
ucts. The graphs in fig. 2 demonstrate that mixtures of sunflower
oil or soya oil and hardened palm fat are toughest. This is undoubtedly the result of the composition of fatty acids in palm oil
(which consists mainly of palmitic acid and stearic acid) (table
I),Awhich also appear:, in liquid oils. Therefore, mixtures contain-
ing palm fat have a more homogeneous glyceride structure than
mixtures containing hardened rapeseed oil or cod-liver oil, which
in turn contain large quantities of acids with 20 and 22 carbon
atoms in a molecule, besides acids of the 016 and 018 group. When
glyceride content is more varied, fat mixtures are less hard.
This is the result of a heterogeneous crystalline structure and
- 12 of the appearance of eutectics as a result of the mutual solubility of glycerides. A typical example is provided by mixtures
of hardened fat with liquid oils (fig. 2 E, F), which in three
cases, show a decrease in hardness when a larger amount of hardened fat is added.
e 5
Hardness of esterified fats decreases systematically as
the ratio of liquid oils increases. This is attested by increasing
micropenetration. At the same time, it is clear that the samples
of esterified fat from a mixture containing hardened palm oil
are harder than the other samples. This is caused by the more
homogeneous acid composition, discussed above.
In general, micropenetration of the'esterified fats under (174)
observation is several times greater than the micropenetration of
conventionally used margarine bases, which is of the order of
28 units at 20 0 temperature. In the light of the above, the consistency of the esterified fats which were studied differs
essentially from that of solid fats used as base components of
traditional block margarines. Thus they could not be used for this
purpose. On the other hand, they could be used in the production
of improved margarines packed in cups, tubes or other containers
of this type.
The results of our studies concerning the consistency of
fats are supported by the solid fat indices deterened by dilatometry, which are represented in figs..3 and 4. The position of
curves in individual graphs suggests that the solid fraction content in'esterified fats is much lower than that in the original
mixture, within the studied temperature zone. For example,
(cont'd)
-
13
(173)
-
Fig. 2. Micropenetration of two-componènt fatty mixtures with
varying ratios of components before and afteresterification.
1
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•
(Key on next page)
- 14 •
1. ratio of hydrogenated fat (%)
2. micropenetration in 20° C.
3. hydrogenated rapeseed oil
4. hydrogenated palm oil
5. hydrogenated dod-liver oil
6. ratio of sunflower oil (%)
7. ratio of soya oil (%)
8. mixture before",egterification
(eXsterified fat
(P. 174, conttd):
at 15 0 , the solid fat indicator in a mixture containing 20%
hardened low-erucic rapeseed oil and 80% of liquid soyq oil
(fig. 4) is 19.5 beforeAesterification and only 2.8 aftergÉér-
ification, while at the temperature of 35° it is 21.1 and 0.9
respectively. The figures are similar in the case of mixtures
containing hardened palm oil (red) or hardened cod-liver oil.
The discussed fatty mixtures and the products of their
te.le.P1 e
Aesterification differ also in the decrease in solid fraction
content with increased temperature. Solid fraction content in
-VrAt ,e
o
mixtures beforeAesterification does not change within the 15
0
to 35 temperature range. The total amount of solid glycerides
melt at 40 - 55 o . On the other hand,r, esterified fats ) especially
0
the mixtures with a drop point around 35 , begin to melt much
earlier, until solid phase disappears almost completely at 35 ° .
In the case of differential thermal analysis (DTA), the
situation is analogous. DTA is one of the most objective methods
of determining the basic factors affecting fatts consistency.
According‘to the principle governing DTA, the thermogram
curve reflects the melting process of a studied fat. A maximum
reached within a given temperature range means the melting of
the largest number of crystals, while a minimum implies polymorphic changes in the solid phase.
e
fr
(175)
- 15 Fig. 3. Dilatometric curves of two-component mixtures of fats
containing differeut ratios of sunflower oil to hydrogenated
fats before and after :esterification.
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- 16 Key for figures 3 and 4:
1. solid fat indicator (mm 3 /g.)
2. hydrogenated rapeseed oil
3. hydrogenated palm oil
4 hydrogenated cod-liver oil
,
5. temperature in ° C.
6. mixture before,esterification
t-ravls
-
7.esterified fat
- 17 -
17 6 )
(
Fig. 4. Dilatometric curves of two-component mixtures of fats
with different ratios of soya oil to hydrogenated fats before
Pi .5
and afterAesterification.
40
.,
S5/35
70/3 0
75/ 2 5
80/20
30
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6
(Key on preceding page)
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(177)
-1$-
The thermogram curve extends above the basic line when the
sample, completely solidified at approx. 1-70°. begins to melt.
When the temperature at which all glycerides become liquid is
reached, the curve returns to its initial level. Thus the surface
of a thermogram is proportional (approximately) to the amount
of heat absorbed or expelled by fat which allows us to draw conclusions about the solid glyceride content in the melting sample
at a given temperature.
Figures 5 and 6 represent thermograms of materials used for
making fatty mixtures. Figures 7 and $ demonstrate the DTA curves
in mixtures of each type (containing 25% hardened component and
75% liquid component), and in/,esterified fats obtained from these
mixtures.
As can be seen from the thermograms in fig. 5, glycerides
in soya oil and sunflower.oil melt almost completely at temperatures below zero, starting at approx. -40°. The melting range of
hardened fats, in sharp contrast to these glycerides, moves
definitely to the right and ends at about +65° (fig. 6).
Melting range is the smallest for palm oil (fig. 6), the
fat possessing the simplest chemical structure, since it consists
almost entirely of glycerides of palmitic and stearic acids
(table I), and highest for sunflower oil, soya oil and hardened
cod-liver oil, which all contain a relatively wide assortment of
fatty acids and consequently, possess.a more complex glyceride
pattern. The melting range of a given fat expressed by thermogram
thus indirectly reflects the fat's glyceride structure. Thermograms of fatty mixtures before and after,'esterification represented
in Rigures 7 and $ demonstrate essential differences in the scope
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- 19 -
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of the melting range and maximal values, as well as the number of
minimal values corresponding to successive transformations of
crystalline forms.
-^•^ Ft ^ i
Thermograms of mixtures before;kesterification point to a
considerable heterogeneity of the glyceride content and the crystalline structure of these fats. They possess two clearly differentiated maxima: one in the "minus" range, corresponding to the
liquid component of the mixture, and another, characteristic for
the hardened component, at about +500. When passing from one
maximum to another, the thermogram curve marks a deep, clearly
marked minimum which implies transformations of crystalline forms
,;^;%,
within the fatty mixture. Thermograms-of,^esterified fats show
a considerably narrower melting range.
(1$2)
The middle of the curve forms angradual maximum created
I
by the melting of the largest number of crystals. The gradual
course of the thermogram implies a homogeneous glyceride and
crystalline structure in,testerified fats, which is the result of
a statistical distribution within the glycerides, which had been
introduced with fatty acids' components.
The results of differential thermal analysis can be interpreted both descriptively and in terms of concrete figures.
•l^^ts
While studying the influence of<<esterification upon the change
in physical and chemical properties of the above-mentioned fatty
mixtures, we have calculated the surface of individual thermo-
grams above 3$0. These areas are cross-hatched in figures 7 and 8.
(cont'd)
ÿ.
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- 20
Fig. 5.
(178)
-
of liquid sunflower oil and soya oil.
Thermograms
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a 37 .-.F.Era 0 ()J.,
T.
1. sunflower oil
2. soya oil
3. temperature in ° C.
:0: 1* (fU i..t0
(179)
_ 21 Fig. 6. Thermograms of hydrogenated fats.
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OIcW RZ-EPAICOi^75C ViVO710RNIOPtY 3
1. hydrogenated cod-liver oil
2. hydrogenated palm oil
3. hydrogenated rapeseed oi1 4. temperature
(18o)
-22-
Fig. 7. Thermograms of two-component fatty mixtures with sunflower
oil ratio to hydrogenated fats of 75:25, before and after ti-a-,-15esterification.
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1. hydrogenated rapeseed oil
2. hydrogenated palm oil
3. hydrogenated cod-liver oil
4. temperature
5., mixture before Nesterification
6.','testerified fat
-
23
(181)
-
Fig. 8. Thermograms of two-component fatty mixtures with soya oil
ratio to hydrogenated fats of 75:25, before and afterAèstbrification.
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1. hydrogenated rapeseed oil
2. hydrogenated palm oil
3. hydrogenated cod-liver oil
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4. temperature
5. mixture before;esterification
6.,\'eSterified fat
- 24. (P. 182, conttd)
The surfaces of these graphs for rats before and after -1-'a-. 1-• correspond with the amount of solid phase at this
temperature. The boundary value 35 0 was established conventionally
on the assumption that fats containing glycerides which melt at
higher temperatures have a clearly waxy aftertaste. According to
this factor, calculated thermogram surfaces were called a "wax
index". They are represented as graphs in figure 9. As can be
seen from the shape of individual curves (fig. 9), the values of
the "wax index" foresterified fats are several times smaller
t,a,e
than they were in the mixtures beforeAesterification. Besides,
the "wax index" decreases systematically as the amount of liquid
tee, u5
component increases, which implies thatesterified fats are cap-
able of crystallizing the stable polymorphic form,P.
An exception to this rule are mixtures of hardened fats
with soya oil which have irregular "wax index" graphs. In some
cases, the "wax index" values increase regardless of the decreasing concentration of the solid component. This implies an unstable
crystalline structure of these mixtures and their polymorphic
transformations which occur during heating.
If we take the "wax index" tobbe the criteria for evaluating the studied samples according to how much glycerides melting
in high temperatures they contain, all esterified fats containing
80% liquid ail and 20% solid component are best. Fats containing
25% hydrogenated cod-liver oil and 75% sunflower oil or 25% hydrogenated rapeseed oil and 75% soya oil are also suitable.
(conttd)
estrifcaon
-
25
(183 )
-
Fig. 9. Wax (tallow) indices of two-component fatty mixtures with
different ratios of.components, before and afterA esterification.
•
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no1'0n-
(Key on next page)
-'26 Key for Figure 9:
1.
2.
3.
4.
ratio of hydrogenated fat
wax indices
hydrogenated rapeseed oil
hydrogenated palm oil
5. hydrogenated cod-liver oil
6. sunflower oil (%)
7. soya oil (%)
8. mixture before 'e&E'erification
9.esterified fat
On the basis of the studies conducted so far, we can make
an initial selection of the obtainede'stérified fats according to
their suitability for making margarine with a high I.U.F.A.
(indispensable unsaturated fatty acids) content.
On the basis of individual determinations, we should
(184)
disqualify for this purpose all the mixtures containing 30% and
35% of hardened fats. On the other hand l \esterified fats containing 20 - 25% highly hydrogenated fats are suitable for the production of dietetic margarines. We should stress the fact that the
above-mentioned fats contained 50.0 to 53.5% linoleic acid in the
case of sunflower oil, or 39.5 to 42.0% of this acid in the case
of soya oil (table II).
However, the final evaluation of these fats can be done
only in the experimental production of this type of margarine.
This is very important sinceeterified fats tend to be softer,
which will affect the consistency of margarines obtained.
Literature:
1. Fal, U. and Witkowski, S. Edible Fats. 14, 207 - 217, 1970.
2. Fal, U. and Witkowski, S. Edible Fats. 14, 233 - 242, 1970.
3. Danowski, K. Studies of the Food Industry Institute and Laboratory. 20, 323 - 337, 1970.
4. Kaganowicz, I. and Strecker, L. Edible Fats. 14, 201 - 206,
. 1970.
f
_27The authors would like to express their thanks to their
colleagues from the Fat Processing Technology Section of the
Department of Technology of Ready-made Foods, Institute of Fat
Processing in Gdansk, directed by Dr. K. Danowski, for making
determinations using differential thermal analysis.
L. Fal U., V`litkôwski S. - T1uszcze Jadalne9 1g, s.207-217 /1970/
2o Fal U., Witkowski S. - Tluszcze Jada1r,-,.jA,: s. 233-242 /1970/
3.
Daîia•^ski K. - Prace Inst. i :Gab.Bad.Pr:zem,Spoz.. 20, s. 323-337
/1970/.
- Txuszc: e, Jadalne, 14 's. 201-206
/1970/
4. I;aganotiv3.cz I., Strecker L.
._
.
.
.
.
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