Vol.44. No.

7 (1995) 503

NOTE

Hydrogenation of Edible Oils and Fats

by Nickel Catalysts. VI.

Changes in Solid Fat Index with Hydrogenation Conditions

and Types of Fish Oils

Kazuaki SUZUKI and Yukinobu MURASE

Research and Development Division, Asahi Denka Kogyo K.K.

(8-4-1, Higashiogu, Arakawa-ku, Tokyo, •§116)

When refined mackerel oil hydrogenated with a commercial nickel catalyst, the acid value increased

considerably with hydrogenation temperature. Hydrogenation rate and trans isomer formation de-

creased above 235•Ž. With hydrogenated cod liver oils (mp 35•Ž, 39•Ž), steeper solid fat index (SFI)

curves were obtained by selective hydrogenation with the nickel catalyst and hydrogenation with the pal-

ladium catalyst compared with normal or trans promotive hydrogenation with the nickel catalyst. Three

fish oils, (cod liver oil, mackerel oil, and capelin oil) differing in fatty acid composition were selectively

and trans promotively hydrogenated with the nickel catalyst up to mp 35•Ž. Hydrogenated oils with

steeper SFI curves were obtained by the selective hydrogenation of cod liver and capelin oils containing

less saturated acids or less polyenoic acids than mackerel oil.

with nickel catalysts. Zachau4) reported the

1 Introduction
physical properties of hydrogenated Peru-
Hydrogenation of fish oils is an important vian fish oil with commercial nickel cata-
technology for the food industry in Japan lysts. In our previous paper5), we reported
and Europe; it is an established and ma- the oxidative stabilities of hydrogenated pol-
ture industry. The U.S. Food and Drug Ad- lack oil, mackerel oil, and cod liver oil. Shi-
ministration extended its affirmation of mamura et al.6) studied the hydrogenation
GRAS (generally recognized as safe) to hy- of turbot oil and saury pike oil with cop-
drogenated menhaden oil in 1989. Despite per-chrome- manganese (KW catalyst) in
these, there are insufficient data for full the presence of poly-dimethyl-siloxane in
utillization of the excellent physical proper- order to produce a stable hydrogenated oil
ties of hydrogenated fish oil, because of so with low melting point. However, little find-
many kinds of fish oils and their extremely ing has been obtained for production of a
complex fatty acid compositions. A few sharp melting hydrogenated oil (with steep-
studies have been reported about operating er solid fat index), correlating fish oil com-
conditions and hydrogenation processes of position and hydrogenation condition. The
fish oils. Morales et al.1) reported the stabil- aim of this study is to clarify effects of fatty
ity of hydrogenated anchovy oil, and Sebe- acid compositions and hydrogenation condi-
dio et al.2),3) reported the selectivities and tions on the solid fat index (SFI) of hydro-
the isomerizations during herring oil hydro- genated fish oils using mackerel oil, cod liv-
genation and menhaden oil hydrogenation er oil, and capelin oil. The examined condi-
tions were normal, selective, and trans pro-
Corresponding author: Kazuaki SUZUKI motive hydrogenations with a nickel cata-
*the previous paper: Yukagaku, 31, 533 (1982) lyst. Moreover the hydrogenation of mack-

19
 504 J. Jpn. Oil Chem. Soc. (YUKAGAKU)

erel oil with a palladium catalyst was also was conducted under a condition similar to
conducted as a comparison. selective hydrogenation, moreover a nickel
catalyst was poisoned with sulfur of methio-
2 Experimental
nine so as to promote greatly trans isomer
Refined and bleached cod liver oil, mack- formation in a first stage during hydro-
erel oil, and capelin oil were hydrogenated genation.
with a commercial nickel catalyst (SO-110 A flow of hydrogen gas was purged to
with Ni content 22% by weight: Sakai displace the air, and then the reactor was
Chemical Co., Japan), or palladium-carbon sealed. The oil containing a catalyst was
(Pb content 5% by weight: Nihon Engel- heated up with slow stirring, and then hy-
hald., Japan). Iodine value (IV), acid value drogen gas was introduced into the system
(AV) and fatty acid composition (FAC) at the respective temperatures. This mo-
were determined in accordance with the ment of hydrogen introduction and with vig-
standard methods7), respectively; IV, AV orous stirring (700rpm) was considered as
and FAC of fish oils are shown in Table-1. the initial point of the reaction. The samples
Melting point (mp), trans isomer content were taken from the reactor at the specified
and solid fat index (SFI) of hydrogenated time intervals during hydrogenation and fil-
fish oils were determined in accordance tered to remove the catalyst. In the case of
with the standard methods8), respectively; the trans promotive hydrogenation, the
IV and trans isomers of hydrogenated fish whole hydrogenated oil was filtered to re-
oils are shown in Table-4. move the deactivated catalyst with a di-
Hydrogenation of fish oils were carried atomaceous earth after hydrogenated for
out with an 1.5L autoclave and a charge of 180min, and a fresh nickel catalyst was
900g oil under the conditions as shown in added into the filtered oil for promoting hy-
Table-2. The normal hydrogenation with a drogenation.
nickel catalyst was conducted under a con-
3 Results an Discussion
dition with intermediate catalyst dose, at

common temperature, and with normal hy- 3・ 1 Optimum hydrogenation temperature

drogen concentration excepting hydrogena- for mackerel oil.
tion temperature of mackerel oil varied be- As shown in Table-1, fish oils contain
tween 180•Ž to 250•Ž. The selective hydro- larger amounts of polyunsaturated fatty

genation was conducted under a condition acids than vegetable oils such as soybean oil
with higher catalyst dose, at higher temper- and cotton seed oil, so that fish oils are very
ature, and with lower hydrogen concentra- sensitive to heat. It was reported that cy-
tion. The trans promotive hydrogenation clizations, polymerizations and decomposi-

Table-1 Characteristics of fish oils in this study.

20
 Vol.44. No.7 (1995) 505

tions of fish oil components, and sintering scants, the degrees of hydrolysis, and the

of metal in catalyst, which inactivated cata- trans isomer contents formed during the hy-

lyst to some extent, might occur during hy- drogenation with a nickel catalyst are shown

drogenation at high temperature9). So, in Table-3. The hydrogenation rate con-

mackerel oil was hydrogenated for 60min stants showed that it attained the maximum

at various temperatures from 180•Ž to 250•Ž about 220•Ž, and it decreased at higher tem-

under the normal conditions as shown in perature (235•Ž, 250•Ž). Moreover, the acid
Table-2 and the hydrogenation rate con- values by hydrolysis of triacylglycerol were

Table-2 Hydrogenation conditions of fish oils.

a) Hydrogenation temperatures were varied between 180 and 250•Ž.

b) Normal hydrogenation was continued with a fresh catalyst after removal of deactivated catalyst.

Table-3 Effects of hydrogenation temperature on hydrogenation rates, hydrolysis rates

and maximum trans isomer contents during hydrogenation of makerel oila).

a) Hydrogenation conditions: 0.066% catalyst based on Ni content. H2 pressure 3.0kgf cm-3.

b) Average value for a 60min after strating of hydrogenation.
c) Maximum trans isomer content during the course of hydrogenation.

21
 506 J. Jpn. Oil Chem. Soc. (YUKAGAKU)

found to increase during hydrogenation at

higher temperature. The maximum trans

isomer formation showed roughly the same

tendency as the hydrogenation rate con-

stants; the maximum formation was ob-

served at 200•Ž to 220•Ž, and it decreased

above 235•Ž. These data confirmed that the

catalyst was inactivated by the prescribed

sub-reactions during hydrogenation and by

sintering of metal in catalyst at higher tem-

perature. Therefore, we considered that hy-

drogenation temperature of fish oil was de-

sirable below 220•Ž regarding to produce ed-

ible hvdroaenated oils.

3・ 2 Effects of hydrogenation conditions
on SFI of hydrogenated cod liver oil.
From the mackerel oil hydrogenation da-

ta (Table-3), we selected the temperature of

Time (min)
215•Ž for the selective hydrogenation (Ni-
•« Fresh Ni catalyst was added after removal of
Sel) and the trans promotive hydrogenation
deactivated catalyst.
(Ni-Tpr) with a nickel catalyst, because a Fig. -1 Effects of hydrogenation conditions on
higher temperature gave a higher hydro- hydrogenation rates of cod liver oil.

genation selectivity and trans promotion

with a nickel catalyst10), and the tempera-
ture of 180•Ž for the normal hydrogenation

(Ni-Nor) with a nickel catalyst and for the

hydrogenation (Pd-Cat) with a palladium

catalyst. These hydrogenation conditions

are shown in Table-2 and the time courses

of these hydrogenations are shown in Fig. -

1. As results, hydrogenation rates were

large. Ni-Nor>Pd-Cat•âNi-Sel>>>Ni-Tpr

in the order. Where, the hydrogenation rate

of Ni-Tpr was the smallest after 30min of

hydrogenation, a fresh catalyst was added

at time of 180min so as to promote hydro-

genation.
The trnas isomer formations during these

hydrogenations are shown in Fig. -2. As ex-

pected, trans isomer formation decreased in

the order of Ni-Tpr>Pd-Cat>Ni-Sel>Ni-

Nor. In Fig. -2 a dotted line is the trans Iodine value

equilibrium line that cis/trans ratio is about
Fig. -2 Effects of hydrogenation conditions on
1/211). trans isomer formation during cod liver
We expected that the degree of steepness oil hydrogenation.
of SFI curve was large in the same order of

trans isomer formation. However their SFI steepness of SFI courses in order were Ni-
curves (mp 35•Ž, 39•Ž) as shown in Fig. -3 Sel=Pb-Cat>Ni-Tpr=Ni-Nor. On the other
were in a different order against the degree side, the degree of trans isomer formations
of trans isomer formations. The degree of were Ni-Tpr>Pb-Cat>Ni-Sel>Ni-Nor as
22
 Vol.44. No.7 (1995) 507

Temperature (•Ž) Temperature (•Ž)

Iodine value and trans isomer content of these hy- Iodine value and trans isomer content of these hy-
drogenated cod liver oils are shown in Table-4. drogenated fish oils are shown in Table-4.
Fig. -3 Effects of hydrogenation conditions on Fig. -4 SFI of fish oils (mp 35•Ž) hydrogenated
SFI of hydrogenated cod liver oil (mp 35, under the selective and the trans promo-
39•Ž). tive conditions.

above-mentioned (see Fig. -3). It was re- rate (S3) and disaturate-elaidate (S2E) con-
ported that SFI of the trans promotively hy- tributing to SFI above body temperature10).
drogenated vegetable oil was the steepest11) So, it is evident that SFI curve of the trans
and the values for selectivities during the promotively hydrogenated fish oil using
trans promotive hydrogenations of soybean nickel catalyst and methionine is less steep
oil and cottonseed oil were the same as than that of the selectively hydrogenated
those of the selective hydrogenation, except- fish oil.
ing those in an initial stage of soybean oil 3・ 3 Effects of hydrogenation conditions
hydrogenation12). In fish oil hydrogenation on SFI of hydrogenated mackerel oil
there may be existing the problem of diffu- and capelin oil.
sional transport of triacylglycerol molecules In order to investigate the effect of fatty

into and out of the pores of catalyst, which acid compositions of fish oil on SFI of hy-

are partially filled with catalytic poisons drogenated fish oil, mackerel oil and capelin

caused from decomposition of methionine, oil were hydrogenated up to melting point

since triacylglycerol molecules of fish oil 35•Ž under the selective and the traps pro-

are bigger than those of vegetable oil such motive hydrogenations. Fig. -4 shows that

as soybean oil and cottonseed oil. Therefore the SFI of the hydrogenated capelin oil are

we speculate that the effect of transport lim- similar to the SFI of the hydrogenated cod

itation for triacylglycerol molecules may liver oils in both the selective and the trans

give low values for selectivity, while it is im- promotive hydrogenations. The SFI curve of
possible to estimate finely the value for se- the hydrogenated oil obtained from capelin

lectivity by reason of the extremely compli- oil containing less saturated acid is steeper

cated triacylglycerol composition of partial- than that of the hydrogenated oil obtained

ly hydrogenated fish oil. from mackerel oil containing both saturated

Low values for selectivity may lead to the acid and polyunsaturated acid in rich.
formation of the undesirable high melting Therefore, we conclude that hydrogenated
triacylglycerols which are especially trisatu- fish oil with a steeper SFI curve is obtained

23
 508 J. Jpn. Oil Chem. Soc. (YUKAGAKU)

Table-4 Iodine values and trans isomer contents of hydrogenated fish oils

(mp 35•Ž, 39•Ž).

Hydrogenation conditions are shown in Table-2.

by hydrogenation of fish oil containing less 11) H.B.W. Patterson, •gHydrogenation of Fats

saturated acids and polyunsaturated acids and Oils: Theory and Practice•h, AOCS

under the selective condition with a nickel Press (1994) p. 43

12) K. Suzuki and Y. Murase, J. Jpn. Oil Chem.

catalyst or under the normal condition with
Soc. (YUKAGAKU), 31, 10 (1982)
a palladium catalyst, although the differ-

ence of their SFI is small.

(Received Dec. 28, 1994) ニ ッケ ル 触 媒 に よ る食 用 油 脂 の

水 素 添 加(第6報)
References

1) L.J. Morales and I.J. Sueyoshi, Arch. Lati-

no. Nutri., 27, 333 (1987) 水 素 添加 条 件 及 び魚 油 種 に よる

2) J.L. Sebedio, Rev. Franc. Corps Gras., 31, 固体 脂 指 数 の 変 化
3 (1984)

3) J.L. Sebedio, G. Finke, and R.G. Ackman,

鈴木 一 昭 ・村 瀬 行信
Chem. Phys. Lipids, 31, 215 (1984)

4) W. Zachau, Fette Seifen Anstrich., 83, 527

旭電化工 業株式会社研究開発本部
(1981)
(〒116東京都荒川区東尾久8-4-1)
5) K. Suzuki and Y. Murase, J. Jpn. Oil Chem.

Soc. (YUKAGAKU), 31, 533 (1982)

市 販 ニ ッケ ル触 媒 に よ る精 製 サバ 油 の水 素 添 加 にお い
6) M. Shimamura, T. Shimizu, K. Suzuki, and
て,酸 価 は水 素 添 加 温 度 の上 昇 と と も に大 き く増 加 し
T. Matsumoto, J. Jpn. Oil Chem. Soc. (YU-
た。 水 素 添 加 速 度 お よ び トラ ン ス異 性 体 生 成 は 温 度 が
KAGAKU), 31, 293 (1982)
235℃ 以 上 で減 少 した 。 ス ケ トウ ダ ラ肝 油 の水 素 添 加 油
7) •gStandard Methods for the Analysis of Oils,
脂(融 点35℃ と39℃)の 場 合,ニ ッケ ル 触 媒 に よ る 選
Fats and Derivatives•h, Japan Oil Chemists'
択 的水 素 添 加 とパ ラ ジ ウム触 媒 に よ る水 素 添 加 は ニ ッケ
Society 2.4.5.1-71; 2.4.1-83; 2.4.20-71;
ル 触 媒 に よ る通 常 水素 添加 およ び トラ ン ス促 進 的 水素 添
2.4.21-73
加 と比 べ て シ ャー プ な 固 体 脂 指 数(SFI)の 水素添加魚
8) •gStandard Methods for the Analysis of Oils,
油 が 得 られ た 。 さ らに,脂 肪 酸 組 成 が 幾 分 異 な る三 種 の
Fats and Derivatives•h, Japan Oil Chemists'
魚 油(ス ケ トウ ダ ラ 肝 油,サ バ 油,カ ラ フ トシ シ ャ モ
Society 2.3.4.2-90; 2.4.24.2-81; 2.4.19.1-81
油)を ニ ッケ ル触 媒 を用 い て選 択 的 お よび トラ ンス促 進
9) H.B.W. Patterson, •gHydrogenation of Fats
的 に融 点 が35℃ に な る よ う水 素 添 加 した 。 サ バ 油 に比
and Oils•h, Applied Science Publishers (1983)
べ て 飽 和 酸 ま た は 多価 不 飽 和 酸 が 少 な い ス ケ トウ ダ ラ肝
p. 48
油 お よ び カ ラ フ トシ シ ャモ油 か ら,よ りシ ャ ー プなSFI
10) J.W.E. Coenen, J. Am. Oil Chem. Soc., 53,
の 水 素 添 加 油脂 が得 られ た。
382 (1976)
(連絡 者:鈴 木一 昭)

24