Molecular Distillation of Sperm \Vhale Blubber Oil
Seiichi Ishikawa, Yoshimori. Ornate, Hideo Kanno
1. Introduction.
Tsujimoto and Koyanagi1> report that when sperm whale blubber oil
was distilled in vacuum, only 60.25% of distilled oil was obtained at a
reduced pressure of 2 mm. and distilled up to 295°C, and a greater part of
the glycerides remained as residue. The authors undertook this researchwith the presumption that it will be possible to distill a greater part of thesperm whale blubber oil by molecular distillation, and the relation betweentemperature and quantity of distillate was examined,. together with thegeneral characteristic of each fraction. Also, quantitative analysis of eachfraction was carried on. It was of great interest to find out to what extent
cholesterol, which is present in minute quantities in this whale blubber oil,is contained in each ~raction, which is related with analytical distillationof vitamin D.
2. Molecular Distillation with Pot Still.
At first, molecular distillation was carried out with pot still with theobject of observing the general conditions such as the extent glycerides will
distill over by molecular distillation. The result of this shows that 74. 7%
distilled over at 130-269°C. The characteristic and cholesterol content ofeach fraction is as shown in Table 1.
Experiment 1. Molecular Distillation with Pot Still.
The characteristic of the sperm whale blubber oil sample was asfollows: specific gravity dl7 0.8599, refractive index n'iJ 1.4673, acid value 1.46,
saponification value 158, iodine value 60.5, unsaponifiable matter 23.5%,cholesterol content 0.15% (0.12% in free state and 0.03% as ester).
40 g of sample was used each time and distilled in a vacuum of 10-:iTable 1. Molecular Distillation with Pot Still

I Tempera- Quantity

F raction ture Range of Distil(OC)late (g)--1234Residue

130-215215-225225-245245-269269

Qua~tity ;Refractive Acidof Distil- \ Index n 20late(%)
n
16.5
32.4
21.2
4.2
25.3

6.5
12.9
8.5
1.7
10.1
--

1.46451.4654
1.4674
1.46971.4735:saponifica-: Iodine
Value tion Value
Value

ICholesterol %

1

2.74
0.91
0.87
15.34
1.57

95.5
100.3
132.4
145.3
224.2

III1

52.4
54.7
63.8
77.0
64.4

III!

19.0
20.5
12.4
4.1
44.0

Molecular Distillation of Sperm Whale Blubber Oil

43mm. The average of each trial is shown in Table 1. The temperature
was measured in the still. Micro-colorimetric method using LiebermannBurchard color reaction was used for quantitative analysis of cholesterolin each fraction.
3. Molecular Distillation with Cyclic Still.
Next distillation was carried on with falling-film type cyclic still and 17
fractions were obtained between 195-295°C. Quantity of distillate was 90% of the sample, and a greater part of the distillate was obtained at 205°C,
about 60% of the sample and about 75% of the distillate. The characteristic and cholesterol content of each fraction are summarized in Table 2.
On examining the result indicated in Table 2, with reference to Toyama and Tsuchiya's2) report on the composition of sperm whale blubber oil,
it is concluded that higher alcohol ester was the principal component of thedistillate at a temperature below fraction 12, reached the maximum at 205cC
and glycerides distilled over at higher temperatures (See Fig. 1).
Furthermore, observations were made of fraction No. 5 as a representative of the 205°C fraction and it was shown that the fraction was a mixture of oleyl oleate and cetyl oleate, its mol-ratio being 3 : 2.
Also, the distillation of cholesterol was at the maximum from the first
distillate to the 205°C fraction, its concentration increasing again near theend of the distillation. (See Fig. 2). It is assumed that the former is cholesterol in the free state and the latter, cholesterol in ester form. The presenceof cholesterol in the free state and as an ester was also verified by quantitative separation analysis using digitonin.
Fig. 1.

Relation Between Temperature and Quantity of Distillate

44Seiich Ishikawa, Yoshimori Omote, Hideo Kanno

Experiment 2.. Molecular Distillation with Cyclic Still.
285 g of sample was used, vacuum of 10-" mm., temperature determination made at the central part of the heating oil bath within the evaporatingcolumn, and about 30 minutes were required for one cycle. Experimental
result is summarized in Table 2.
Table 2.

--._!___Number

Fraction T~rnptN1o.
23456789101112131415
16
17of

Molecular Distillation with Cyclic Still

Quantity ofDistillation

IR ft'l e rac iv~·

A .dc1·fi

S--I---d~-~ _apom ca- 1

o .me

121.8
123.5
136.1
lW.O
128.2
134.0
125.1 .
131.6
126.5
160.0
151.8
211.4
216.4
215.0
221.6
223.8

53.6
41.5
64.9
54.9
64.6
66.8
67.5
69.7
78.l
78.3
76.9
72.5
69.l
67.9
67.2
66.6

__ 1_ _ _ __Cholest-I (~S _ Cy:le ~--~~- _(~1~ !-~~~:~1 __ ::~~_:t~on 9::lue ::.l:e ___ erol %
205
205
205
205

1
12
222
22
l
1
1~05

205
205
215
225
235
245
255
265
275
285
295

15.2
31.8
35.3
:09.1
22.4
22.7
12.5
10.l
6.8
6.2
5.3
4.8
4.8
4.5
4.1
3.1

l
I

1
1
1

1

5.3
11.8
12.8
10.4
7.9
7.9
4.4
3.5
2.4
2.0
1.9
1.7
. 1.7

1.46781.46611.46681.4662
1.46661.40701.46701.46801.46801.46801.46801.47071.47101.47131.47241.4726

1.6
1.4
1.1

1.06
1.32
0.78
1.05
1.10
0.98
1.10
0.H
1.69
4.09
4.82
2.56
2.44
3.60
2.44
1.72

14.6
30.5
6.6
4.6
3.5
2.1
2.1
0.8
1.1
3.6
4.6
4.6
4.6
5.3
6.5
4.1

Fig. 2. Relation between Temperature and Quantityof Cholesterol Distillation
16-JA

9.

s=· 6;;,-'"" 4'Oc',

2195

205

215

225

235 245255

2b5275285

295

Temperature ( °C)

Experiment 3. Confirmation of Composition of Fraction No. 5.
5.4 g of Fraction No. 5 of Table 2 was used, unsaponifiable matter

Molecular Distillation of Sperm Whale Blubber Oil45extracted with ether after saponification, and from this a light yellow, semisolid vrns obtained. This substance had an iodine value of 56.4, and referring to the report of Koyanagi and Tsujimoto1), its ratio, assuming that
it is a mixture of cetyl alcohol and oleyl alcohol, was 2 : 3. Also an yellow
oil was obtained from the saponifiable matter by ether extraction after acidifiying with hydrochloric acid. The acid value of this oil was 187.8, iodine
value 92.0 (theoretical value of oleic acid, acid value 190, iodine value 90)
so it was confirmed that this oil was oleic acid.
4. Conclusion.
( 1) By using pot still, about 80% of distillate was obtained between 195-:--295cC by molecular distillation of sperm whale blubber oil. Its principal
component, about 75% of the entire distillate distilled over at 205°C andits components were confirmed as being oleyl oleate and cetyl oleate.
( 2) Quantitative analysis of cholesterol in each fraction was carried out
and it was possible to observe the presence of two maximum concentrations,which corresponds to the free state and ester state.
References
1) Mitsumaru Tsujimoto and Hanji Koyan:ag;, ]. Soc. Chem. Ind. (Japan) 40, 694 (1937).
2) Shushi Toyama and Chitaro Tsuchiya, ]. Soc. Chem. Ind. (Japan) 30, 519 (1927).