Note: Descriptions are shown in the official language in which they were submitted.
; . . BACKGROUND OF~THE INVENTION . -
Field of the Invention
This invention relates to methods for preparing good hard
butters from palm oil, which may be used.as a replacement for .
. cacao butter to a large ex~ent in confectionary products such as
chocolates, chocolate-flavored coatings and the like, without the
~ occurrence of blooming even when the product is used without tem-
20 pering.
The Prior Art
Hard butters are very important in the chocolate-making in- .
dustry as a substitute for cacao butter, because while it is solid
at room ~emperature,.it melts evenly at body temperature, i.e.,
around 37G. Heretofore, most hard butters have been made from
. natural fats having fatty acid composi~ions and orientation
. . .
.
~ _ _
.
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.. ~ .~, . .
d
.. - '' .. ' :,
. . ~ '~ :. ,
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1093579
similar to those of cacao butter, such as shea butter or phulwara
butter. However, these vegetable bu~ters are relatively expensive
because of the comparatively poor yields from the raw starting
materials which grow wild and are not widely cultivated. ~ore-
over, the starting materials for these vegetable butters aredifficult to obtain because of unstable weather and political con-
ditions in the countries to which they are indigenous. As a re-
sult 3 there has been an increasing demand for cheaper and more
abundant substitutes for cacao butter other than the known vege-
table butters noted above.
Palm oil, which is obtained from the fruit of the palmaeanplant, Elaeis guineensis Jacq., is one of the most abundant and
cheap vegetable oils,because the plant is now being increasingly
cultivated in Malaysia and Indonesia. In the past, it has been
known to obtain hard butters from palm oil by fractionating the
palm oil with a suitable solvent such as acetone, methyl ethyl-
ketone or hexane, or by collecting the mid-fraction of a hardened
palm oil by solvent fractionation. Of these two known processes,
the former is unacceptable because the yield of desired product is
much too low when the fractionation is effected with sufficient
precision so as to obtain a suitable product. On the other hand,
if the fractionation is not carried out precisely enough, a large
amount of high~melting glycerides in the oil unavoidably becomes
mingled with the final product. When such a crude product is
used in confectionaries, the undesirable phenomenon known as
"blooming" occurs. The second of these two known processes îs
~093579
also unacceptable, because i~ the palm oil is preliminarily hydro-
genated according to conventional techniques (with a nickel cata-
lyst) and then subjected to a conventional solvent fractionation,
it will form, as a by-product, so large an amount of the high-
melting glycerides (which must be removed), that it becomes an
uneconomical process for industrial purposes. Likewise, the
hydrogenation of a highly unsaturated oil, such as cotton seed
oil or soybean oil using an ordinary nickel catalyst will also
give unsatisfactory results because of the high-melting glycerides
which are inevitably by-produced in such process.
On the other hand, it has also been known that hard butters
having a high trans-isomer content rarely cause blooming and thus
may be used as a replacement ~o:r cacao butter. However, since
the ordinary nickel catalyst is so lo~ in the ability to isomer-
ize the product, an oil having a high iodine value which is far
dif~erent from palm oil must be used as the raw starting material,
and even under special conditions, that is, under so~called
"selective conditions" (i.e., low hydrogenation pressure and high
catalyst concentration), it is impossible to avoid the by-
production of the high melting-glycerides. In addition, other
processes for bringing about the trans-isomerization o~ an oil
or fat are also known, which processes, however, do not seem
practical because deterioration of the treated oil occurs due to
the isomerization catalysts generally used, such as selenium.
In order to avoid the disadvantages of the above-described
prior art processes, there was developed a process which is
~9 3 ~ ~ ~
described in U.S. Patent 3,856,831 (owned by the unrecorded
assignee hereo~). Said U.S. patent describes a method ~or obtain-
ing good hard butters by hydrogenating a fat or oil including palm
oil having an iodine value within the range o~ 60 to 78 with the
total content o~ linoleic and linolenic acids being less than 17
weight percent with a nickel catalyst poisoned with sulfur (6 to
21 parts o~ sul~ur per 100 parts by weight of nickel). However,
it should be noted that although this process was satisfactory for
the most part at the time, there still remained some unresolved
problems, in particular, in controlling the degree o~ catalyst
poisoning. For di~ferent applications or uses, it is desirable
to prepare dif~erent kinds o~ poisoned catalysts, that is, cata-
lysts which are poisoned to di~.erent degrees. However, since the
catalyst poisoning according to the process o~ U.S. Patent
3,856,831 is effected by subjecting an active nickel metal cata-
lyst to the action of a toxic gaseous sul~ur compound (such as
H2S), it is practically impossible to e~ectively control the
degree of poisoning using that process. The present invention
provides improved processes ~or making hard butters, which over-
comes the disadvantages o~ the prior art sul~ur-poisoned catalyst
processes. The present process uses a novel poisoning agent,
namely methionine, as a result o~ which the above di~ficulties in
controlling the degree o~ catalyst poisoning are completely avoid
ed. Moreover, by using the present process, the danger inherent i
using H2S as a catalyst poison is avoided. Finally, by using the
present process, there is no danger o~ having a ~ood product con-
taminated with H2S.
~ 3 5 ~ ~ i
In addition to the foregoing, the following patents are
noted as being relevant prior art: U.S. Patents 3,~87,989;
2~972,541; 2,942,984; 2,468,799; ~ritish Patents 1,2i9,245;
~61,016; 859,769; and Japanese Patent Publication No. 135,103/75.
In view o~ the above-noted problems and disadvantages which
characterize the prior art processes, it is an object o~ this in-
vention to provide processes ~or making hard butters ~rom an in-
expensive raw material without the need ~or a tempering step,
which hard butters have remarkable resistance against fat bloom-
ing and which also have good melting properties tha~ make theproduct especially useful as a cacao butter substitute.
Another object of the present invention is to provide pro-
cesses or hydrogenating palm oil wherein the hydrogenation re-
action is easily controllable whereby to prevent over-absorption
of the hydrogen.
A further object of the invention is to provide means ~or
poisoning the catal~st used in hydrogenating the palm oil in a
manner that is safe, both for operators employed during the pro-
cessing as well as the ultimate consumers of the products having
the hard butters incorporated therein.
SU~Y OF T~ INVENTION
. _ . _ _ . . ..
In accordance with the foregoing objects, the present
invention provides processes for preparing hard butters from
palm oil which comprises hydrogenatiny a soft palm oil fraction
having an iodine value of at least 55 with a conventional
hydrogenation catalyst in the presence of a catalytically
effective amount of methionine so as to form at least 40%,
!,
~lg357~
. ~
based on the total glyceride cnntent, of trans-isomers (mostly con-
sisting of an elaidic acid moiety, calculated conveniently in term$
of trielai~ine~. The hydrogenated product is further fractionated
in the case where the starting palm oil has an iodine value from
55 to less th~n 60. When the starting palm oil has an iod~ne
value of 60 or ~ore, this further fractionation is optional.
The methionine as used in this invention includes the
following methionine compounds,namely l-methionine, d-methionine,
dl-methionine, methionine sulfoxide, methyl sulfonium
methionine, ~-methionine and functional derivatives thereof,
including salts, esters, ethers and N-acyl derivatives
thereofO
BRIEF DESCRIPTION OF THE DRAWING
Figure 1 and Figure 2 respectively, are Solid Fat
Content Index (SCI) curves for the hydrogenated products
prepared accordiny to Examples 1 and 3.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
As noted above, the invention provides processes for
` ~ preparing hard butters,`wherein a raw palm oil is first
fractionated with a suitable organic solvent, such as methyl
~ ethyl ketone, n-hexane or acetone, to provide a lower melting
`~ fraction (hereinafter referred to as "soft palm oil") having
an iodine value of at least 55. The thus obtained soft
palm oil is then subjected to hydrogenation with a conventional
hydrogenation catalyst of the type which has heretofore
been used for hydrogenating oils or fats, such as an activated
nickel catalyst, in the co-presence of methionine, so as to
increase the trans-isomer content ~calculated in terms of the
amount of trielaidine relative to the total glyceride content)
- 30 to over 40%. As the raw starting material there can be used
either a raw, deacidified or bleached palm oil. According
to the pro-
-- 6 --
1~)93579
cess, the starting oil is dissolved in a suitable organic solvent
and the resulting solution is cooled and allowed to stand in order
to precipi~ate out the undesirable higher melting f~action (con-
sisting mainly of a mixture of high melting glycerides). If the
iodine value of the soft palm oil is below 55, the oleic acid
content of the oil becomes so low, that after removal of the un-
desired higher melting fraction, the yield of the desired lower
melting fraction (i.e., the soft palm oil) becomes so low as to
be uneconomical. On the contrary, if the iodine value of the
starting soEt palm oil is between 55 and below 60, a pre-
ferred hard butter can be obtained through post-fractionation of
the hydrogenated product; moreover, the omission of this post-
fractionation step makes the resultant product unsui.table on
account of its considerable softness which results from its lower
SCI. Finally, if the iodine value of the starting soft palm oil
is 60 or more, hard butters having desirable properties can usuall~ Y
be obtained irrespective of whether or not the post-fractionation
step has been carried out. The following Table 1 gives the ex
perimental data obtained in the Cone Penetration Tes~;when several
hydrogenated products derived from three different soft palm oil
fractions as well as cacao butter (for comparison purposes) were
hydrogenated in accordance with the process of the invention, that
is, with a conventional nickel catalyst and methionine.
_ . ., _. ,
* Described in A.O.C.S. Official Method Cc 16-60 using the
apparatus described in ASTM Standard D-217-60T.
5~7g
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oo ~r~ oO ~: 5~ ~ 5U
I ~ . . . I ~ 0~ ~
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~ 1093579
As can be clearly seen ~rom the foregoing data, the hydro-
genated products derived ~rom so~t palm oils (a) and (b) having
an I.V. o~ 70 2 and 60.1, respectively, have similar hardness to
that of cacao butter.
~ccording to the process of the invention, the soft palm
oil having an iodine value of at least 55, and ~rom which the high
melting fraction has been removed, is then hydrogenated with a
conventional hydrogenation catalyst such as an activated nickel
in the presence of methionine so as to give a hydrogenated ~at or t
oil having a trans-isomer content of over 40%. The amount o~ the
methionine used is pre~erably from 0.003 to 0.03% by weight, based
on the soft palm oil. The methionine may be preliminarily admixed
with the nickel catalyst or it may be separately added to the so~t
palm oil together with the catalyst. Irrespective o~ how the
catalyst and methionine are added to the soft palm oil, the ex-
tent or degree o~ isomerization (to the trans-isomer) is remark-
ably enhanced by the joint use o~ such catalyst and methionine as
` compared with the extent of isomerization when the catalyst is
used alone. Thus, when a so~t palm oil of I.V. = 70 is hydrogena-
ted with catalyst + methionine, the ratlo ~ % trans-isomer/~I.V.
is about 5. That is, there is a dramatic increase in the trans
isomer content per ttnit decrease in I.V. On the contrary, when
the same soft palm oil is hydrogenated with catalyst alone, the
ratio is only 1, indicating a very modest increase in trans-isomer
content per unit decrease in I.V. Thus, conventional hydrogena
tion catalysts are not able to change so~t palm oils to hardened
~ ~ 35~7~
oils or fats having high trans-isomer contents. Moreover, even
though certain oils having high iodine values such as cotton seed
oil or soybean oil can be converted to hardened oils or fats
having high trans-isomer contents (about 30-50%), these products
invariably need to be further fractionated to remove the large
quantities of high-melting glycerides present therein, because if
such high melting glycerides are not removed, the melting points
of the hydrogenated products would be too high for confectionary
use. Theoretically, of course, such other oils (cotton seed,
soybean) could be used since a suitable middle melting fraction
; would be obtained after removing the high melting fraction. In
practice, however, those other oils cannot be used because the
high melting fraction accounts i-or such a large portion of the
total hardened oil that after removal thereof, the final yield of
;~ 15 the desired middle melting fraction would be so low as to be
economically un-feasible.
Notwithstanding the fact that cotton seed or soybean oil
per se are unsuitable for use in the process of the invention, it
should be noted that small amounts (less than about 20%) of such
highly unsaturated oils as rape seed oil or rice bran oil as well
as cotton seed oil or soybean oil can be present in the soft palm
oil which is to be hydrogenated, particularly if a slight deteri-
oration in the ability of the hardened product to melt in the
mouth, i.e~, to melt at about 37C. and a lowering of the hardness
of the product at higher temperatures can be tolerated. In fact,
a lowering of the hardness may even be advantageous for certain
, , 10-
93579
hard butt:ers which are to be used in frigid zones. Clearly, it
is difficult to state with precision exactly how much of these
unsaturated oils may be incorporated into the soft palm oil be-
cause the amount will vary with the nature and kind of the un-
saturated oils to be added, the iodine values of the soEt palm c
oil to be hydrogenated and the hydrogenation conditions. All
these factors being considered, it is believed that an amount of
less than 20% by weight based on the total soft palm oil is per-
missible. The data given below show the melting point and S.C.I.
values of a hardened product which was prepared by hydrogenating
a mixture consisting o:E 15% soybean oil (I.V. 130.4) and 85% soft
palm oil (I.V. = 67.4) at a hydrogen pressure of 1 kg./cm2 at
; 180-200C. for 240 minutes in the presence of 0.19% activated
nickel and 0.005% methionine.
Temp. S.C.I.
10C. 62.3
20C. 59-5
melting point of
hydrogenated product 30C. 28.7
36.9 C.
35C. 7.0
40C. o.o
Thus, a suitable product can be obtained from a soft palm oil
which contains 15% of a highly unsaturated soybean oil.
As described aboveg hydrogenation according to the process
of the invention is carried out by using a conventional hydrogena-
tion catalyst such as an activated nickel in the presence of
methionine at a temperature of 160-220C. and a hydrogen pressure
_.____,, . ,. ~ ~.
~ 35i7~3
(gauge) of 1-10 kg./cm2. The amounts of the nickel catalyst and
methionine to be used are respectivelyl 0.1-3.0% and 0.003-0.03%
by weight based on the weight of the soft palm oil. Moreover, one
l may use cystine or cysteine instead of the methionine, although
methionine is presently preferred. As used herein, the term
"methionine" is intended to include equivalents thereof such as
dl-methionine, d-methionine, methionine sulfoxide, methyl-
sulfonium methionine, ~-methionine and functional derivatives
thereof such as salts, esters, ethers and N-acyl derivatives as
well as the naturally occurring l-methionine.
The hydrogenation will stop automatically when the trans-
isomer content reaches a maximum level which is detenmined by the
ratio of the hydrogenation catalyst to the methionine. This is
a very important characteristic of the invention inasmuch as it
effectively prevents the over-hydrogenation which has been a
problem in prior oil or fat hardening processes.
The trans-isomer content of the hardened product should be
at least 40% and preferably 50% or more of the total glycerides
(calculated as trielaidine, measured according to "A.O.C.S. Tenta-
tive Method" Cd. 14-61). If the trans-isomer content is below
40%, the ultimate yield of hard butter after the further
fractionation step by which the desired hard butter is obtained
will be too low.
Alternatively, if the trans-isomer content is between 40%
and 50%, a good hard butter is obtained in satisfactory yield
afterthe fraction~ion. In particular, if the trans-isomer content
1~ 1093579
is over 45%, a superior hard butter (as shown in Figure 2) is
obtained in a yield of more than 50% based on the starting soft
palm oil.
The fractionation of the hydrogenated so~t palm oil whereby
to obtain the desired hard butter is ef~ected with a suitable
organic solvent such as methyl ethyl ketone~ acetone, hexane,
petroleum ether, ethyl acetate, and the like. The hardened
product is dissolved in the solvent, either warm or hot, and
cooled to precipitate out a first crystalline fraction (the high-
melting fraction). This high-melting ~raction is removed by
filtration or centrifugation and then the filtrate or supernatant
(as the case may be) is collected and further cooled to precipi-
tate out a second crystalline ~raction (the mid-raction). This
mid-~raction comprising the desired hard butter is then collected
and dried.
The fractionating temperatures will vary depending on the
kind of solvent used and the desired characteristics of the hard
butter. However3 generally, the two-step fractionation is
carried out first at a temperature of 15-25C. to precipitate out
the high melting fraction, and then at 5-10C. to precipitate out
the desired mid-fraction. The process according to the
invention has the following unexpected advantages as com-
pared with the process of U.S. Patent 3,856,831:
(1) Increased yield; good hard butters having more than 50%
of trans-isomer can be obtained in a yield of over 50% based on a
raw soft palm oil of I.V. 60.
9~ 35~9
(2) Improved workability; control of the extent of poison-
ing of the catalyst is much easier than in said patent since
methionine is not a gaseous substance but rather is a solid which
is stable and can be weighed precisely.
(3) Improvement from a hygienic aspect; methionine is a
harmless and stable substance and is quite different from the
toxic gaseous suflur compounds which are used in said patent.
This feature is important not only in terms of production person-
nel, but also the consuming public.
(4) Reproducibility of the product; in connection with (2)
above, a uniform product can be obtained regardless o~ fluctua-
tions in the quality of the starting palm oil because the balance
between the trans-isomer content and the saturated fatty acid
content in the hardened product can be readily controlled by ad-
justing the amount o~ methionine to be added relative to the cata-
lyst. Therefore, it is possible to prepare many kinds of cataLyst
which differ in the degree of poisoning; moreover, it is possible
to reduce the reaction time as compared with the previous catalyst
(5) Improved color of the products; the color of the
hardened product according to the invention is much better than
that o~ the prior art as Eollows:
ABLE 2
. _~ _. .~ . , ,.
Sam~les Color*
- ~ . -- _ ____.~ .
Example V of U.S. Patent 3,856,831 red 0.8
Example I of the present invention red 0.6
* Measured using a Lovibond chromometer
with a 5 1/4 inch cell
-- -- - ~ ,
I ~ !
~ 3S79
"
(6) Improved in taste and flavor; the generation of off
flavor and unpleasant taste can be prevented to a large extent by
the present invention as follows:
. TABLE 3
_ .. . .
Samples* Days required for generating off
flavor and unpleasant (un-
.~ palatable~ taste
Example V of U.S. Patent , 10
3,856,831
Example I of the present 13
invention .~ .
* Each sample was placed in a half-filled bottle,
: tightly closed and kept at 60C.
(7) Compatibility; other conventional hydrogenation cata-
lysts can be freely used in the present process. For example,
any known selective hydrogenation catalyst which has been used for
the reduction of polyenes to monoenes, such as copper or copper/
chrome may be used jointly with the catalyst according to the in-
vention.
.
,. . __ _ _ . __ , .,
~ 357~
,.
ESCRIPTION OF THE PREFERRED EMBODIMENTS
The process of the present invention will now be further
described by the following examples which are intended to merely
illustrate and not to limit the invention,
EXAMPLE
`: ' ,
A purified palm oil was dissolved in warm 95~/0 methyl ethyl-
ketone to form a 10% solution therein. This solution was then
cooled to -5C. to form a crystalline precipitate which was then
collected to yield a soft palm oil having an I.V. of 70.2. To
this soft palm oil, there were then added 0.3% by weight of a con-
ventional nickel catalyst(l) and 0.01% of dl-me~hionine. The soft
palm oil was then hydrogenated at 200C. under a hydrogen pressure
of 3 kg./cm2(gauge) until the trans-isomer content had reached
60% (this procedure took about 5 hoùrs). The resulting hardened
product was then refined according to conventional purification
techni-ques to give a hard butter having a Solid Fat Content Index
as shown in Figure 1.
EXAMPLE 2
. A different palm oil than that which was used in Example 1
was fractionated as in Example 1 to obtain a soft palm oil having
an I.V. of 60.1. This soft palm oil was then hydrogenated as in
(1) The nickel catalyst consisted of 18% by weight of nickel em-
bedded on diatomaceous earth. This catalyst was used in all
of the succeeding examples.
1~ ~L09357g
Example 1, except that 0.15% o the nickel catalyst and 0.003 %
of dl-methionine were used. After the fractionation, a good, hard
butter was obtained.
EXAMPLE 3
The same palm oil as was used in Example 1 was dissolved in
methyl ethyl ketone and cooled to -5C., after which it was fil-
tered to remove a high melting portion which precipitated out.
From the resulting ~iltrate, the solvent was distilled off to
give a soft palm oil having an I.V. of 70. To this soft palm oil,
there were added 0.3% of the nickel catalyst and 0.01% of dl
methionine. The mixture was then hydrogenated under a hydrogen
pressure 3 kg./cm2 (gauge) at 200C. for 1.5 hours to give a
hardened product having a trans--isomer content of 60%. This
product was then dissolved in 95% methyl ethylketone to form a
20% oil solution which was then cooled to 2]C, to precipitate
out a high-melting portion. The filtrate was then further cooled
to -8C. to form a crystalline precipitate which was then collec-
ted and dried whereby to obtain a mid-fraction having a melting
point of 35.4C`., the melting characteristics of this product
being shown in Figure 2. The yield was 70% based on the starting
soft palm oil.
EXAMPLE 4
The soft palm oil obtained according to the procedure of
Example 1 was hardened following the procedure of Example 1, ex-
cept that the amount of the nickel catalyst was 0.2% by weightand the amount of dl-methionine was 0.004% by weight. There was
r~ - ~
~35~7~
,
obtained a hardened oil containing 50% of the trans-isomer. This
hardened oil was then dissolved in 98% acetone to give a 20%
acetone solution thereof. Thereafter, the acetone solution was
cooled to 20Cv and the thus precipitated high-melting portion was
removed through filtration. The resulting filtrate was then
cooled to -6C., and the thereby precipitated desired mid-fraction
was collected. This was ~ollowed by evaporation of the solvent to
give a good hard butter possessing good melting properties. The
yield was 55% based on the weight o~ the starting soft palm oil.
EXAMPLE 5 (control)
A soybean oil was hardeped with 0.3% of the nickel catalyst
at a hydrogen pressure of 3 kg./cm2 (gauge) and 200C, For com-
parative purposes, an experiment: according to Example 3 was re-
peated, The properties of the raw (starting) oils and the respec-
~ive hardened and fractionated oils are given in tlle following
Table 4.
. ... _ .~
~9357~
_ _ _ . .
g ~ ~ oo
~rl . 00 ~ 1~ ~ L~
H ~) u~ D .
o _ _ ............... . 'I
0 ~ U~
~1 O ~ r-l C~
h . _ ~ ~ C~ l
. aJ
'¢
U~ O
~J .d ~
~;~. .~ ~O bO~ 1 ~ ~ X ~1
~1 O ~ ~ O ~ O ~
¢ 1~ _ .
s~ ~ ,~ c~l n
~1 ~ ,i
_
t~ H 00 t~
1~4 ...
~ 5~ . .
~H E~ .
'~ U~ ~ .~
E~ -~0
_ _ ~ . .
-~ ~ . ~ . ~
_~ 0~0 , ~rl ~
U~ O _ ~
-19-
3L~1~357~
As can be clearly seen from the data in the above Table, in
both hardened oils (before frac~ionation), the iodine value and
trans-isomer content are quite similar irrespective of the nature
of the original oil, but the rising points are quite different.
5 This difference in rising point accounts for the differences in
the yields of the respective middle melting fractions. Thus,
according to the present invention, a remarkably high yield can
be obtained from palm oil as compared wlth that from soybean oil
when both are subjected to ordinary hydrogenation.
EXAMPLE 6
A so~t palm oil having an I.V. of 6~.2 was hydrogenated at
a hydrogen pressure of 1 kg./cm2 with different amounts of catalys :
and dl-methionine, wherein the hydrogenation temperatures were
raised from 180C. at first to 200C. finally. The obtained data
are given in the following Table 5.
'
3~
.
,~
o ~ ~ o oo U~
- .. ,
,~ ~ U~ o oo
~ ~ S~ O O~
o ~ _,
4 ~ . _ .
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.U ~1 t~
tl~ ~ U~ O ~ `;t In 1~ ~ 1~ U~
bO~ ~
C~ ~ 0 00 ~ U~
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:C H
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.,1
E~
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o a)
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O 00 ~ 7 N ~ O
Ul ~ ~
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.~ ~: ~ U~
oO~ OOOOOOOO
~a)o oooooooo .
~.~.
~g .
~a~ u~u~oooooo
a)o ........
C) ~ 3 - O O O O O O O O
~; ~
~ ~ ~ ~
D Zi .. ~
-21-
~C39,35~
EXAMPLE 7
An industrial scale run was carried out with 8,042 liters of
a soft palm oil having an I.V. of 66.8 together with 10.5 kg. of
an activated nickel catalyst and 0.7 kg. of dl-methionine at a
hydrogen pressure of l kg./cm2 and a temperature of 200C. ~or
360 minutes. The catalyst and methionine were preliminarily dis
persed into a small portion o~ the raw palm oil to form a 7% sus-
pension which was then added into the remaining oil. The intro-
duction of hydrogen was started when the inner temperature of the
reaction vessel (7 ton capacity~ had reached 170C. The heating
was controlled so that the inner temperature did not exceed 200C.
During the course of the reaction, O.S kg. samples were taken at
30 minute intervals at first and then at 60 minutes for analysis.
The data obtained are given in l:he following Table 6.
~0~3157~
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cn ~ ~ cO ~ I ~ ul 0
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o
. cq ~ ~ D
E~
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~ _ ~ I~ I r` I ~ o ~ o
a) . ~ ~ Ln i~ oo C~
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. ~D 1~ 1~ ~ ~D Lr~ U)
H ~
_ _ .
. o~ . '
.
t~ o 00 oO CS~ O
~1 1~ o~:) CO oo o~ ~ o~
. ` ~ ~
_ _ - ' .
J
~ O O O O O O O O O
~ ~ o ~:
E ~ ~ ~ c~
E
.
_ _
-23-
109357~ ~
After the hydrogenation was complete ~at the end of the
reaction, the absorption of hydrogen almost completely stopped),
the reaction mixture was filtered and the filtrate was dissolved
in 95% methyl ethylketone to form a 20% oil solution therein.
This solution was then cooled to 21-22C, and allowed to stand for
60 min~tes with 510w stirring until the high-melting glycerides
had precipitated out. The filtrate from which the high-melting
glycerides had been removed was further cooled to -8C. and allowe
to stand for 90 minutes, whereby there was precipitated a mid-
fraction which was then collected. This mid-fraction was then
bleached and deodorized according to conventional techniques after
the solvent had been removed. The results of this fractionation
are given in the following Table 7.
TAB]E 7
1~ Fractions I.V. Yield (~/O) ~ Trans-isomer (%~
High- 38.2 14.5 _
melting
Mid- 52.6 63.5 36.5 67.0
melting
Low- 69.5 22.0 _ _
melting
. ... _ - .. -. .
EXAMPLE 8
Two milk chocolate samples were preparèd in accordance with
the following recipes.
i()93579
_ .
_ In~redient Reci~e_A Recipe B
Cocoa liquor 15 parts 15 parts
Whole milk powder 25 parts 25 parts
Pulverized sugar 38 parts 38 parts
Fa~ 22 parts (cacao19 parts (cacao
butter)butter)
3 parts (substitute)
Lecithin 0.5 part 0.5 part
* "Substitute" means a hydrogenated soft palm oil prepared
according to Example 1.
The ingredients of recipes A and B were separately admixed
with each other according to the conventional manner and the mix-
tures were further homogenized through refining rolls. After
conching for 5 hours, both mixtures were subjected to tempering
and molding processes, and then cooled. The thus obtained
chocolate samples were then allowed to stand for a week at 17-20C.
in order to allow the fats to change into a more stable crystallin
form for the subsequent test. Then the chocolate samplès were put
into a thermostatically controlled heating apparatus and subjected
to the following heat treatments:
31.0+0.3C for 10 hours temperature lowered withi~ 18.0tO.3C.for
2 hours 2 hours
temperature raised within 2 hours ~
This heat cycle was repeated until blooming could be seen.
In sample A, blooming occurred after 5-6 cycles o~ the heating
test, while sample ~ did not show any appreciable blooming or
1093579
decrease in gloss even after 15 cycles of the heating test.
Variations and modifications can, of course, be made without
departing Erom the spirit and scope of the invention.
Having thus described our invention what we desire to secure
by Letters Patent and hereby claim is:
