Studies on Utilization of Higher Fatty Alcoholfrom Sperm Whale Oil

BY
SHINICHI TOMIYAMA and MASAYASU TAKAO(Received June 00. 1952)
CONTENTS
Introduction ................................................................... 37
1. New synthetic method of alkyl aryl hydrocarbon .......................•. 37
2. Utilization as lubricating oil and hydraulic oil and their properties •..... 39
3. Utilization as vacuum pump oil and its property ......................... 42
4. Utilization as cutting oil and its property ................................ 43
5. Utilization as detergents and fat splitting agent and their properties .... 44

Introduction

Sperm whale oil has been used in Japan for limited purposes suchas wax, textile oil agent and detergent etc. So we studied utilizationof higher fatty alcohol from sperm whale oil. Alcohol fraction from
sperm whale oil was condensed with aromatic hydrocarbon to get alkyl
aryl hydrocarbon, from which superior lubricating oil, hydraulic oil
vacuum pump oil, cutting oil, detergent and fat splitting agent weremade on an industrial scale.
Process for them and their properties are described in the following paragraphs.
1.

New synthetic method of alkyl aryl hydrocarbon.

a.

Condensation between saturated alcohol from hydrogenated sperm
whale oil and naphthalene.
Hydrogenated sperm whale oil was used as sample, which wassaponified and distilled into saturated alcohol (A.V. 0.2, S.V. 2.8, Ac. V.
190.6 and I. V. 4.7). The reaction between this alcohol and refined;Daphthalene using active clay as catalyst, with incessant stirring, at
normal pressure let to dehydration at 160°C. There was a violent
dehydration at 180° to 190°C. Then alkylation at 200°C and came up
to its maximum in 30-90 minutes. The results of experiments showedthat this new reaction for industrial synthesis of alkylnaphthalene wassuperior in the following points to previous methods using sulphricacid 2 ), metals haloide 3) or boron trifluoride•) as catalyst.
1. More yield and easier operation in reaction process.

S. ToMIYAMA and M. TAKAO

2. No need of after-treatment except removal of clay.
3. Simple equipment without special material.
By the result of the experiments on various temperatures, reaction
hours, and amounts of active clay and naphthalene, the best condition
to get a condensed oil principally consisting of monoalkyl naphthalene
which is suitable for the diffusion pump oil, cutting oil and surface
active agent as described later, was: 100 parts of higher fatty alcohol(1 mol), 103 parts of naphthalene (2 mols) and 20-25 parts of active
clay, 180-200°C in reaction temperature, and 30-60 minutes in reaction
hours. In this case, the yield of monoalkyl naphthalene was 57-59%of theoretical value. After various experiments, was found the best
condition to obtain a condensed oil principally consisting of dialkylnaphthalene and polyalkylnaphthalene, which is used for high grade
lubricating oil. That is, 100 parts of higher fatty alcohol (1 mol), 30
parts of naphthalene (0.6 mol) and 30 part of active clay, 200-210°C
in reaction temperature and 90-120 minutes in reaction time. On thiscondition, the yield of dialkylnaphthalene and polyalkylnaphthalene was
45% of alcohol and that of monoalkylnaphthalene was 35% and thesmall amount of olefine dimer was obtained as by product. The above
mentioned monoalkylnaphthalene is considered to consist of /3 alkylnaphthalene, for in the ultraviolet ray absorption spectrum photographthe maximum absorption of monoalkylnaphthalene did not coincide withthat of a methyl naphthalene but with that of /3 methyl naphthalene.
Furthermore, judging from the significantly lower solidifying point
and the smaller viscosity index of monooctadecylnaphthalene than thoseof n-/3 monooctadecylnaphthalene, the alkyl in question should be notof normal chain but of isoparaffine base.
Condensation between olefine from saturated sperm alcohol and•naphthalene and benzol.
For the synthesis of alkylaryl hydrocarbon by condensation of olefine and aromatic hydrocarbon, sulphric acid6 ), metal haloide7), phosphoricacid or boron trifluoride 8) have been hitherto used. A condensation
method to use active clay as catalyst has been already patented also 9 ).
The following experiments were carried out to find the best conditionof the reaction, for of which details have never been reported yet.
The above mentioned higher fatty alcohol from sperm whale oil
was normally dehydrated with active almina at 300-350°C and distilled
into olefine fraction (260-310° in distilling temperature, N~0 1.4425,
I. V. 103.0 Mol. wt. 226) with a yield of 87 % of alcohol.
b.

Utilization of Higher Fatty Alcohol :!'rom Sperm Whale Oil

39

Olefine content in this distillate was calculated 92% from molecularweight and iodine value. In the process of condensing this olefine andnaphthalene in the presence of active clay, alkylation commenced at
140°C and came up to its maximum at 180-190°C. Olefine, even withhalf amount of active clay, led reaction easier and more sufficiently
than alcohol did. The best condition was: 100 parts of olefine (1 mol)104 parts of naphthalene (2 mols) and 11.8 parts of active clay 1801900C in reaction temperature, 60 minutes in reaction time. In thiscase, the yield of monoalkylnaphthalene was 66.2% of thoretical value,
showing better result than experiment (a), using alcohol.
It was also found that alkylbenzol could be more easily obtainedby the condensation of the above mentioned olefine and benzol than incase of experiment using naphthalene. Namely, in a rotative autoclave,
olefine and benzol began to alkylate at 120°C in the presence of active
clay. The reaction advanced with the ascent of temperature, amounting to 60-70% at 150-160°C, and to the maximum, over 90% at 210°C.
At higher temperature, decomposition was seen with the lapse of time,the yield of alkylbenzol decreasing. The best condition for monoalkylbenzol synthesis was: 100 parts of olefine (1 mol), 321 parts of benzol(10 mol) and 10 parts of active clay, at 200-210°C, 30 minutes inreaction time, at the pressure of 10-12 kgs/cm2 • In this case, the yieldof monoalkyl benzol was 81.2% of theoretical value and that of d.ialkylbenzol was 8.8% viz. 90% of olefine was alkylated.
2.

Utilization as lubricating oil and hydraulic oil and their properties.

Tomiyama demonstrated by his patent 10) that high grade lubricating
oil can be synthesized from higher alcohol and naphthalene. Among
many experimental manufacturing of lubricating oil from higher fatty
alcohol of sperm whale oil and naphthalene with use of active clay as
catalyst, the representative result is as follows. Condensation is madeon the following condition: 96 kg of alcohol, 29 kg of naphthalene and
29 kg of active clay to 205-210°C for 90 minutes in reaction time, inthe 200 L condensation kettle. Average yield of crude condensed oil
was 86.4 kg. The result of topping 100 kg of the above mentioned
condensed oil to 300°C in the oil temperature under the vacuum of 20 mg
Hg in the vacuum super steam kettle, is as shown in the fallowing
table 1.
The fqllowlng table 2 shows the comparison of properties among
lubricating oil from natural mineral oil and the other synthetic lubricating oil.

40

S. TOMIYAMA 'and .M. TAKAO

Table 1. Results of fractional distillation of crude condensed oil.
Distillates
Naphthalene I lst fract.
fractionI 2nd fract. I 3rd fract. I
N.F. No. 2 iN.F. No. 63

180-203;20 I 203-210120 I

Residum

6.2

-

14.6

43.5

Boiling point C/mmHg
Condenced water/distilled oil
Yield for condensed
oil in percentage

84-120/760

Appearance

yellow light yellowllight brown:reddish yellow
white solid faintliquidliquid
oily
I
oily

I

5.2
5.5

Viscosity at 100°F

u.s.s.

Table 2.

-120-180/20

I

0.9

2.9

14.2

21.0

57.0

169.5

I

294.0

I

1350

Properties of some lubricating oil.
JapaneseNavystandard

TexacoNo. 120

PhilipLubricat-J Lubricat- Lubricating oil
ing oiling oilpolyme-1 polyme- condensed
rized from rized from by ourparaffin fatty acid method

1
Acid value
under 0.1
0.08
0.06
0.02 /
0.02
0.03
Saponification value
under 1.5
0.10
0.12
1.41 I
0.38
0.28
Specific gravity D 425
under 0.9 D 430 0.8806D4BO 0.8972 D430 0.869 D 430 0.8504 D 430 0.8785
Flash point °C
over 200
251
246
245
261
248
1
Solidifying point 0°C
under -51
-14
-7.6
-13
-27
-5.6
Viscosity at 210°F U.S.S. 115-125
120.0
122.0
121
123
120.0
Viscosity index
over
90
95
77
107
117
111
0.56
0.70
0.97
0.980
Conradson test carbone % under 1.5
1.13
Stability
under 2.0
1.45
Viscosity ratio
1.06
1.90
1.15
1.37
under 2.51
1.64
1.71
1.59
1.49
Conradson test (%)
2.22
I

I
I

II

Engine test: The result of an engine test for 2180 kg of the above
mentioned lubricating oil with use of (EI) 1450 H.P. engine, was asfollows. After eighty hour running test it was judged that this oil
could be used sufficiently for the practical purpose. Thus, our lubricating oil has some properties superior to common mineral oils andpolymerized lubricating oils. It is not poorer in stability than higher
grade mineral oils.
The second fraction (B.P. 180-203°C under the vacuum of 20 mm) andthe third one (B.P. 203-210°C in the same vacuum) were dehydrated
and refined with clay into a refined oil with the following properties,
which was suitable for hydraulic -oil for machine tool.

Utilization of Higher Fatty Alcohol from Sperm Whale Oil

Table 3.

General properties of NF 20 and NF 63

I Sample NF No. 2 f

NF No. 63

I

0.88051.5030Specific gravity n 4 20
Index of refraction nn20
Flash point °C
Solidifying point °C
Viscosity at 100°F U.S.S.
Viscosity at 210°F
Viscosity index
Molecular weight (by freezing point method)
Acid value
Saponification value
Iodine value
Oxidation test:

41

0.88831.5092
152
-22
169.5
45.1
107.8

II
I

I
-16
294.0
54.0
115.0

420

590

0.03
0.15
4.69

0.04
0.21
4.69

at 100°C, for 12 hrs. air blown 6 L/min/40 gr

Viscosity at 100°F
Viscosity ratio
Acid value
Increases in acid value

171.8
1.01
0.37
0.34

300.5
1.02
0.41
0.37

The comparative test between previously used Tycol Heavy Medium
and the oil NF No. 2 was made about the effect on the velocity ofreciprocating table of T 81 automatic internal grinder No. 502, madeby the Toyo Kogyo Co. Ltd. During it, the pressure was 10 kg/cm 2and the temperature was kept at 40°, 60° and 80°C by electric heater.
The result is shown in the Tables 4 and 5.
Table

Flash point °C
Solidifying point °C
Viscosity at 30°C Red sec
50°C
"
80°C
"
//
m

4.

Tycol Heavy
MediumNF. No. 2

221
-12
380
140
61
3.85

152
-22
192
96.7
50.8
3.50

This result showed that the oil NF No. 2 had a smaller velocitychange by temperature change than Tycol Heavy Medium, which waspreviously of the highest grade. As shown by the result of the

42

S. ToMlYAMA and M. TAKAO

Table 5.

I

Tycol Heavy Medium,

NF No. 2jI

I40°C mm/min [60°C mm/min[80°C mm/min[ 40°C mm/min [60°C mm/min [80°C mm/min
1/8 I
218 I

1,708,188
4,376,898
3/81 7,024,392
4/8 ! 8,674,698
5/8 I 9,473,682
9,863,016
10,069,932
I
10,140,846
8/8

~::

1,746,708
4,298,508
6,889,950
8,275,860
9,056,604
9,350,652
9,473,682
9,536,424

1,531,915
4,298,507
5,760,000
7,600,002
7,756,908
8,056,908
8,000,016
8,111,730

533,333
2,796,117
5,647,059
8,228,572
9,290,323
10,000,000
10,359,703
10,866,668

I

620,6902,868,526
5,559,846
7,912,088
9,330,769
9,664,430
10,000,000
10,434,783

562,500
2,818,500
5,517,241
8,04.4,693
9,056,104
9,600,000
9,795,918
9,931,034

experiments, our condensation method made out a new lubricating oilwith a large yield from higher fatty alcohol from sperm whale oil.
This oil showing high viscosity index and a good stability for oxydation
is superior to previously used synthetic lubricating oils and is equal tonatural lubricating oils.
In addition, hydraulic oil for machine tool which is better thanhydraulic oil from natural mineral oils hitherto used, was obtained fromlower temperature fraction.
3.

Utilization as vacuum pump oil and its property.

The authors have already reported that alkylnaphthalene has a good
adaptability for a diffusion pump oil. Experiments were carried on by
the various kinds of distilling methods for the purpose of obtaining a
diffusion pump oil from the forementioned condensed oil. The result
showed that method to obtain monoalkylnaphthalene fraction by thefractional distillation under the vacuum of 1.0-0.01 mm Hg with use of arectifier, was the best one. After a distillation, the yield of the diffusion pump oil for the vacuum of 4x10- 5 mm Hg was 54.2% of alcohol.
After triplicate distillation, the yield of the diffusion pump oil for thevacuum of 6 x 10-1 mm Hg was 35.3%.
On the basis of these experiments, refined condensed oil was obtainedin the average yield of 55 kg, from 50 kg saturated sperm whale alcoholand 51.5 kg of naphthalene. These materials condensed with 12.5 kgof active clay at 180-190°C, for 60 minutes in a 200 L iron-made condenBy steam distillation of this condensed oil, excess
sation kettle.
naphthalene was distilled out. The average yield of the dehydrated andrefined condensed oil was 55 kg for these materials.

43

Utilization of Higher Fatty Alcohol from Sperm Whale Oil

25 kg of this refined condensed oil was rectified again in a 50 L
iron-made rectifier, 20 cm in diameter and 100 cm in height, which waspached with rectifying tower full of porcelain berl saddle in it. The
condition was as follows: vacuum was 0.2-0.4 mm Hg, reflex ratio
was 2 and distillating velocity was 1.5-20 L/hr. After rectification, theyield of the diffusion pump oil for 2-4x10- 6 mm Hg was 51-53% of thealcohol. After double rectification, superior diffusion pump oil was
obtained with the yield of 38-40% of the alcohol. Properties of thisoil was as follows.
Specific gravity D 43D

0.9038Index of refranction nD3D

1.5224

Viscosity

80°F U.S.S.

224

100°

130

130°
Solidifying point

"
n

74
-45°C

Molecular weight345
6xI0- 7 mmHg

Maximum vacuum

The results show there is a possibility that the excellent diffusion
pump oil is produced on the industrial scale from the saturated alcoholof sperm whale oil.
4.

Utilization as <JUtting oil and its property.

By distilling out naphthalene, 113 parts of refined condensed oil
was obtained from the above mentioned condenced oil which had been
made of 100 parts of saturated alcohol from sperm whale oil. For thisoil, friction coefficient between steel and steel with a load of 10 kg/mm2
at room temperature were measured with the pendulum oiliness tester.
The result is shown in the following table:
Crude condensed oil

Soya bean oil

Spindle oil

Specific gravity D,130

0.89780.91970.8940Index of refraction nD30

1.51381.4733

Viscosity 50°C centistokes

26.3

24.6

Acid value

0.04

0.9

0.08

Friction coeffieient

0.078

0.100

0.305

8.19

Thus the refined condensed oil, of•which the principal ingredient is
monoalkylnaphthalene, has an excellent oiliness. The fallowing tables
show the results of adaptability test of this condensed oil which isblended in turbine oil as oiliness accelerator, and the results of corn-

s. TOMIYAMA and M. TAKAO

44

parative test of utility among turbine oil, soya bean oil and this condensed oil.
No. of cutting oil

No. 3

No. 4

No. 8

100

80

80

Constituent of samples
Turbine oil
Soya bean oil

20
20

Condensed oil
Viscosity 30°C Redwood sec.

425

294

333

50°C
Acid valte

146

114

122

"

0.2

Saponification value
Friction Coefficient (1,)

0.7

0.1

39.2
0.167

0.131

0.136

Conditions in cutting
Machine used

Hobbing machine

Cutting material

Hard steel (0.55 C)

Hardness of cutting material

39-Lll 0 (shore's)

Cutting speed

17m/min.

Cutting depth

Rough cutting 10.'75 mm finish 0.4 mm

Cutting feed.

0.56 mm/rev.

Hobb

All ground hobb

Oiling capacity

6 l/min.

The result is shown in the following figure. The amount of friction,
when No. 8 oil was used, of hobb at two gear cutting, was 1/4 of thatwhen No. 3 oil was used and was 1/3 of that when No. 4 oil was used.
In case of No. 3 oil, hobb had to be repolished after only two gear
cutting. In case of No. 8, it was not so, even after 4 gear cutting.
It was thus found that our condensed oil shows a very good oilinessexactly suitable for gear cutting oil.
5.

Utilization as detergents and fat splitting agent and their properties.

Monoalkyl benzol was made of the above mentioned olefine which
was obtained from sperm whale oil. To 1 mol of this monoalkyl benzol,
3 mols of 20% fuming sulphric acid was dropped at 30°C. This sulfonicacid was dissolved into alcohol and neutralized with caustic soda, thenproduced sodium sulfate was removed by filteration. To this alcoholic
solution, petroleum ether was added so as to extract out the oil which
remained not reacted. By further distillation of alcohol, alkyl benzol
sodium sulfonate was obtained. Its yield and surface activity in
0.5% water solution are compared as follows, with those of sulphric45

Utilization of Higher Fatty Alcohol from Sperm Whale Oil

ester soda salt which is normally made from saturated alcohol from
sperm whale oil.
Yield for higher fatty alcohol

Monoalkylbenzol sulphonicacid soda salt

Alcoholic sulfuric acid
ester-soda salt

From sperm whale oil inpercentage

128

105

Sulphonation ratio inpercentage

9575

Forming (at 40°C)

1 min. 1655

1275

Loss & Milrs methods

10 min.

1205

1620

Surface tension dyn/cm 2

31.05

35.81

Interfacial tension

4.21

7.05

"

The above results show that monoalkyl benzol-sodium sulfonate
obtained by the method of condensing olefine and benzene, have thebetter foaming and better interfacial tension than those of sulfuric acidsoda salt of alcohol. In addition, to 100 parts of the above mentioned
refined condensed oil, 100 parts of 20% fuming sulpfric acid was dropped
at 30°C and then a little water was added. After standing to remove
the waste acid, fat splitting agent of which 80% was alkylnaphthalenesulphonic acid was obtained with a yield of 156% for alcohol, rawmaterial.
The comparative splitting test against palm oil was made between
this splitting agent and the previous one mainly consisting of dibutylnaphthalene sulphonic acid. A mixture of 100 parts of palm oil, 50 parts ofwater and 1.5 parts of fat splitting agent was splitted with stirring for
4 hours at 95°C. Neutralization value of fatty acid produced by our
fat splitting agent was 186.0 and that of fatty acid by the previous
one was 156.9. For the industrial products by this method the fat
splitting test with use of the above mentioned palm oil showed thatthey had so good a splitting power as 96-98%.
As the result of the above experiments showed, from saturated
alcohol from sperm whale we could produce with a large yield a powerful
agent, which mainly consists of alkylnaphthalene sulphonic acid and has
better splitting power than the previously used dibutylnaphtalene sulphonic acid.
Literatures
1)
2)
3)
4)

T. Kuwata, S. Tomiyama and M. Takao: Bull. Chem. Soc. Japan 22, 66 (1949).
U.S.P. 2, 237066.
I.P. Tsukeranik: J. Cen. Chem. (U.S.S.R.) 17, 1005 (1947).
G.F. Hennion and R.A. Toussaint: U.S.P. 2, 390, 835 (1947).

46

S. ToMrYAMA and M. TAKAO

5) Takao and Tomiyama: A lecture at Jap. Chem. Soc. 2nd Anniversary meeting.
6) V .N. Tpatieff: J .A.C.S. 58, 919 (1836).
Schild Wachter: Ang. Chem. 47, 677 (1934),
7) Naetelson: I.E.C. 25, 1391 (1933).
V.N. Ipatieff and Bross: J. Org. Chem. 1, 559 (1937).
8) Nilwland, Sowa, Slamia: J .A.C.S.· 57, 1547 (1935).
9) T. Kuwata: Jap. Patent No. 162, 258 (1944).
10) S. Tomiyama: Jap. Patent No. 164, 180 (1944).
11) Proc. Worlt. Petr. Cong. 2 448 (1933).
(These studies were made at Ressearch Dept., Lion Fat and Oil Co. Ltd.)