US2100146A - Manufacture of soap from marine oils - Google Patents

Description

Patented Nov. 23, 1931 UNITED STATES PATENT oFrici: I Masonic-rune 215g;- raoriimirmn I Sigval Schmidt-Nielsen, Trondhjem, and Arne .Flood, Larvik, Norway No Drawing. Application November 2,1936, Serial No. 108,900. In Norway June 20, 1933 4 Claims.

This invention relates to the manufacture of soap from marine oils and has for its object a process by means of which it is made possible from such oils to obtain soaps of good lathering 5 quality permanently free from the disagreeable fishy odors usually inherent .in soaps manufactured from marine oils. I

This application is a continuation-impart of of our copending application Serial No. 730,841

lessen their oxidizability. a

An important feature of thepresent invention consists therein, that the marine oils prior to the saponiflcation operation are subjected to a treatment by which the autooxidizability of the oils is eliminatedor reduced without the aid of added oxygen, hydrogen or other elements and without simultaneous polymerization to any substantial degree. According to the invention this change vin the character of the oils is the-result of an intramolecular saturation of the oil brought about by heating for several days in closed vessels under pressure at temperatures between about 250 C. and 300 C. A necessary condition to bring.

about the said interior saturation of the fat molecule is that the said heat treatment is extended over a period of considerably more han 48 hours, preferably about 72 hours or more.

It has been found that by maintaining a temperature not substantially above 250-260 during the main part of the heat treatment it is possible to-bring about the said intramolecular saturation without appreciable polymerization. When an oil obtained according to the invention is decom- 35 posed to obtain the fatty acids thereof in a free condition it will be found that these acids are capable of being distilled with water vapour. As well known this is not the case with fatty acids of polymerized oils. The fact that the decrease of the iodine number has been effected by intramolecular saturation and not principally by polymerization can also be ascertained by conventional molecular weight determination.

The heat treatment according to the invention will produce the results above referred to without the aide! any foreign additions. The treat.- ment takes place in closed vessels with consequent pressure and there is no loss of substance. A small quantity of water is formed as a consequence of the intramolecular saturation, and the percentage of free aclds in the oil is increased at the same time as the percentage of unsaponiflable matter increases owing to the formation of hydrocarbons.

As is well known,

'filedJune 15, 1934 for the Treatment of oils to the of oils and fats pro-- duced from marine animals (fishes, whales, seal and the like) is highly limited owing to the autooxidizability. This property of the oils is due to the fact that the molecules of the compounds, of which the oils are composed, comprise a great 5 number of'double bonds. If these double bonds are not eliminated, the marine oils will retain their high degree of 'autooxidizability and consequently their restricted field of use. In the manufacture of soaps the odor can be dis- 10 guised by the aid of perfumes, but sooner or later it reappears in the washed materials (laundry, etc.).

It is known that it is possible to add hydrogen, oxygen, sulphur and other elements or radicals .15 to the oils (or fats) and that in this-manner stable oils or fats may be obtained. A great number of patents have therefore been issued which deal with thetreatment of fatsor fatty acids respectivelywith hydrogen, the socalled 'oilhardening treatment as well as with the polymerization of fats or fatty acids by heating to elevated temperatures in the presence of air resulting in a powerful oxidation simultaneously with polymerization andanhydride formation.

It has also been suggested (U. S. A. Patent No. 1,151,002) to improve the quality of soaps made i from marine oils by subjecting the oils to a combined polymerization and hydrogenation treatment because it has been found that by inter- 3o posing the polymerizing treatment the produced soaps vwill be of a more satisfactory lathering quality than soaps produced from ordinary hydrogenated marine oils. 1

According to the present invention no hydrogenation treatment is required, the desired results being obtained solely by extending the heat treatment under pressure over a period of several days.

By thistreatment the desirable decrease of the 40 iodine number is attained neither by the addition of hydrogen or other foreign substances nor by polymerization but by an intramolecular saturation of the double bonds of the oil molecules.

The oils treated according to the invention will be found to have acquired a pleasant smell and taste as well as a lighter colour and are an excellent raw material for the manufacture of soaps of any kind.

The duration of the heat treatment required v to produce the effects aimed at will to some degree depend on the temperature employed, the character of the oils, the pressures employed as well as on the conditions of operations in general. But usually several days duration of the as heat treatment will be necessary when ordinary The temperature may be maintained constant during the entire reaction period, or the tem-' perature may be caused to rise or sink respectively in stages. And it may also sometimes be suitable to carry the heat treatment into efiect in several stages separated from one another by periods with lowered temperatures.

It is not required to subject the crude oils to I any .preparatory treatment with the object of removing water or protein-matter. And it is usually preferred to subject the oils or fats in a crude condition to the heat treatment according to the invention.

A possibly desired, refining of the oils ,for example to remove colouring matter may be carried out subsequent to the heat treatment herein referred to.

Example Ordinary medicinal cod liver oil was heated in a closed'co'ntainer (autoclave) under nitrogen for about 72 hours at 250 C. By this treatment the iodine number was lowered from 170 to 84. The resulting oil was of lighter colour than the initial material and had attained a slightly aromatic smell. The oil had lost every trace of the original taste and smell of cod liver oil. The hexabromide test gave a negative result. The saponification number was unaltered as also the average molecular weight (determined by the camphor meth- 0d). The oil reacted readily with lye and produced an entirely white soa Example 2 Crude whale oil No. 0-1 was heated in nitrogen atmosphere in a closed autoclave for about hours at 250 C. In the course of the treatment the iodine number fell from 112 to 76. The oil behaved as indicated in Example 1. The resulting oil was then subjected to the'conventional saponification treatment without any preparatory refining treatment.

Example 3 Whale oil No. 0-1 was heated in nitrogen atmosphere in a closed container to about 260 C. for about 72 hours. Owing to local overheating, the colour of the treated oil was somewhat darker than of the initial material. It reacted readily with saponification lye. By salting out a light, hard soap and a quite light under liquor suitable for glycerine production resulted. In spite of the fact that no additions were used, the finally obtained soap had a pleasant smell. It could be readily pressed to blocks as is the case with other grain soap. By the addition of small proportions of other fats, the soap could be made into prepared toilet soaps (pilierte Toiletten-Seifen).

Example 4 L Whale oil No. 4 was heated. in a closed vessel to about 260 C. for 72 hours.

In the course of this treatment, the iodine number fell from 102 to 65. The resulting oil was of a somewhat lighter colour than the initial oil and was slightly fluorescent. At room temperature it was of a butter-like semisolid consistency. It produced a dark coloured soap of agreeable smell. In manufacturing practice it would be advisable to subject an oil of the character obtained according to this example to a bleaching treatment before use as a raw material for fine soaps.

We claim:

1. Process for the manufacture of soaps from unoxidized and unhydrogenated marine oils comprising the step of heating the marine oils without adde'd catalysts and in the absence of oxygen marine oil is subjected to the heat treatment in a crude condition.

4. Process for the manufacture of soaps from unoxidized and unhydrogenated marine oils comprising the step of heating the marine oils without added catalysts and in the absence of oxygen to a temperature between about 250 C. and 260 C. in closed vessels, the said heating being continued for a period of time not less than 48 hours decrease of the so as to bring about a substantial decrease of the iodine number by intramolecular saturation of the glyceride molecules and subjecting the resulting product to saponification by the aid'of added alkali. v

SIGVAL SCHMIDT-NIELSEN. ARNE FLOOD.