US2382531A - Soap manufacture - Google Patents

Description

Patentea Aug. 14, 1945 SOAP MANUFACTURE Laszl Auer, South Orange, 'N. J.

No Drawing. Application August 17, 1942,

Serial No. 455,132

8 Claims. (01. 252-370) description of the process. However, before fully FIELD or INVENTION This invention relates to soap manufacture and is particularly concerned with improvements which are especially adapted to soap manufacture by the method herein referred to as the anhydrous saponification method.

Examples of the anhydrous method are disclosed in my issued Patent No. 1,957,437 May 8, 1934, and also in my copending applica 11, Serial No. 455,131, filed concurrently herewith.

Briefly, according to the anhydrous method, a fatty material, such as a fatty oil or a fat, is heated together with one or more alkali oxides and/or hydroxides and/or carbonates, the temperature being relatively high, for instance, from about 150 C. to about 350 C.

There are a number of basic or fundamental advantages in the anhydrous method generally considered, many of which are touched on in my patent and copending application above mentioned. For instance, the anhydrous method is of advantage since it may be used to produce a thermoplastic soap product. Moreover, the anhydrous method is especially well adapted to production of solid soaps from fatty oils.

Some of the general and more important objects of the present invention are: improvements in procedural steps of the anhydrous method, whereby not only to make the process more readily capable of commercial operation, but also to improve the product itself in many ways.

According to the invention, provision is made for introducing water into the anhydrous product, this feature being adaptable to introduction of water over a wide range of percentages, whereby to meet the requirements of soap products of different types.

In another aspect, the invention provides for production of a product of relatively light color even where the fatty material employed would otherwise normally produce a very dark product.

Still further, the invention contemplates the employment of certain steps and agents eifective to reduce objectionable odors, this phase of the invention being especially useful in the treatment of certain fatty materials, for instance, fish oil, which normally have a highly objectionable odor.

Still another object of the invention is to increase the rate of dissolution of the alkali agent in the fatty material.

The manner in which the foregoing general objects are achieved will be pointed out more fully hereinafter, along with others which can be understood to best advantage following a fuller analyzing the several steps of the process, reference is made just below to the fatty materials, alkali agents and treatment conditions which 1 preferably employ in carrying out the anhydrous saponification broadly considered.

FATTY MATERIAL The invention is applicable generally to fats and fatty oils, a. typical list of fatty oils being asfollows:

From the list it will be seen that not only drying. oils are suitable, but also semi-drying and non-drying oils. The fatty acids of these oils may also be used and the starting material may consist of a single oil or fatty acid or mixtures thereof.

Further, solid fats, such as tallow and lard, and acids thereof'may be used, either alone or in admixtures with oils, for instance, with those listed above. Still further, the invention is adapted to the treatment of other raw materials such as fatty waste materials, for instance, fatty acid distillation residues, foots, such as mucilaginous matter, and other by-products of fatty oil refining (sludges).

i It is here pointed out that the expression "fatty materials as used herein, including the claims appended hereto, comprehends various of the oil and fatty materials of the types mentioned above.

/ I Aunt: AGENT The alkali agentsused maybe either of the type disclosed in my patent above mentioned, or of the type disclosed in my copending application above mentioned. Thus, asdisclosed in the with each other.

plication, alkali metal carbonates or alkali metal bicarbonates, may be used.

With reference tothe metals, it may be men tioned that lithium, sodium and potassium are well suited to the process. Ammonium is also herein classed with these metals, since the action thereof is similar to the alkali metals. The oxides or ,carbonates of lithium will normally produce the hardest soap, other treatment conditions being equal. Oxides or carbonates of sodium, potassium and ammonium yield progressively softer soaps in the order listed, although all are capable of producing a solid soap product. The alkalies may be used separately or in admixture For most purposes hydroxides or carbonates of sodium are preferred, since they are not only readily available, but also capable of producing a soap of good texture and hardness. However, good quality potassium soaps are obtained by using potassium hydroxide or carbonates.

ANHYDROUS SAPONIFICATION In accordance withthe anhydrous method, the fattyfmaterial is mixed and heated with the alkali agent the temperature desirably being between about 150 C. and 350 0., preferably from 200 C. to 300 C. Most of the fatty oils give best results when, treated between 260 C. and 7:100" C. The time of treatment should be at least one half hour. In general, increase of temperature and/or time increases the hardness of the soap product. In any event for the production of solid soap as herein contemplated, the treatment temperature and time should be such as to drive ofl most or substantially all of the water present or formed during the saponiflcation step.

The quantity of alkali agent should preferably approximate that required for substantially complete saponification of the particular fatty material being treated. Some leeway may be permissible, as for-instance, when producing super+ fatted'or alkaline soaps, but in general, I prefer adhering fairly close to neutrality. The exact quantity of alkali required will vary, depending upon the particular fatty material being treated, since some fatty oils or fats require more reagent than others, to eifect complete saponification. The quantity may, of course, be determined by experimentation or may be calculated roughly from the saponification number of the particular fat or oil. In many cases, to obtain a certain degree of acidity or alkalinity of the soap, a slight excess of alkali is desirable in addition to that calculated.

, der vacuum. This is of advantage in many in-' stances inorder to reduce contact of the airwith the reaction mass. Other means may be employed for this purpose, for instance, as disclosed invention and these are, therefore, considered more fully hereinafter.

ILLUSTRATIVE PROCESS Although it may not be necessary or desirable in all cases to use all of the steps contemplated by the invention, certain of the steps being of advantage per se, conjoint use of the several major improvement steps is in many cases desirable, as will be clear from consideration of the following treatment which is'presented for illustrative p p A treatment highly effective for certain fatty materials, and especially for fatty materials, such as fish oil, is as follows:

Assume that the fatty material being treated is a fish oil-which would normally yield a very dark product with an objectionable odor. This oil is heated with a mixture of an alkali metal hydroxide and an alkali metal carbonate selected from 'the classes herein disclosed, the temperature preferably being from 200 C. to 300 C., so as to effect anhydrous saponification.

This treatment is desirably carried out in an autoclave and, according to the invention, from about 5% to about 25% of rosin is heated with the fish oil and the alkali agents.

The quantity of the alkali agents approximates that required to completely saponify the oil and rosin. The carbonate is preliminarily calcined to drive oif a portion of the CO2 and any water present, and both the carbonate and the hydroxide are added in ground form, the total quantity of the two agents being divided into a plurality of portions, for instance, l0, which are added at intervals, each one after the foamin the copending application above referred to,

the reaction may be carried out in a vessel having only a small outlet to atmosphere, CO2 released from the batch during heating being relied upon to exclude the air.

Still further, supplemental conditions and/ or treating agents may be employed during the anhydrous saponification, but many of these have direct bearing on the process steps of the present just below the boiling point of water.

ing of the preceding one has appreciably subsided.

After addition of the alkali agents, the pressure in the autoclave is reduced down to from 400 mm. to mm. of mercury, this condition being maintained for about /2 to 5 hours, for instance, 3 hours.

The temperature of the reaction mixture in the autoclave is now permitted to drop to a point Water is introduced at this temperature and the valves of the autoclave then closed, heat being again applied so as to raise the temperature appreciably above 100 C., the steam released at this time serving to develop pressure.

Simultaneously with introduction of water into the autoclave, as mentioned just above, from about of 1% to 2% of hydrogen peroxide is added.

After maintaining the increased pressure for a period of at least /2 hour. the pressure and heat are terminated and the soap is poured out to cool.

Y 1 FEATURES or IMPROVEMENT The eilect of various of the steps enumerated above is as follows:

With respect to the addition of rosin, this serves several important functions. In the first place, it promotes dissolution of the alkali agent in the oil. Secondly, the rosin aid in yielding a light colored product. Thirdly, and of considerable importance, the resin addition greatly diminishes the objectionable odor which the soap would otherwise have. a

, Calcining of the alkali carbonates, grinding of both the carbonate and the hydroxide, and ad- ;dition of the two agents in a plurality of portions, are all of importancein insuring etl'ective dispersion and dissolution of the alkali agents and in avoiding the tendency to foam. In many cases satisfactory products may be secured 'without these particular steps.

The addition of water belowthe boiling point thereof; followed by closure of the autoclave and reheating effectively distributes the water in the soap, yielding auniform arid homogeneous soap product. Employment of agitation at this stage is usually advantageous and often necessary to produce a uniform product.

The addition of hydrogen peroxide aids in obtaining a product of light color, usually not more than being required.

The foregoing and other features of improvement are more fully analyzed, individually just below:

, Reverting again to the rosin addition, it may be mentioned that the rosin mayibe any suitable gum or wood rosin, derived from trees, such as the known rosin producing trees of Greek, Spanish, French and American origin. When employing a rosin addition, the quantity thereof may be any where up to 100%, from about 5% to 50%, usually'being effective for the purposes above mentioned. In addition to the important advantages of the rosin above mentioned, it is also pointed out that the rosin is a relatively inexpensive ingredient as compared with various of the fatty materials, in view of which the cost of the soap is thereby reduced.

The addition of water is an important feature,

is being of especial advantage that by first employing the anhydrous saponification method, and thereafter adding water, any desired percentage of water may be incorporated in the anhydrous product, thereby permitting production of soaps of varying degrees of hardness, ranging all the way from extremely hard and brittle products,

. all the way to relatively soft or even liquid products. In the normal type of solid soap, the presence of water facilitates lathering and for this purpose the quantity should preferably be up to about 10%, 5% usually being sufficient. The

amount of water incorporated in the autoclave may be varied by altering the treatment, temperature, time of treatment, etc.

The water may alternatively be added by kneading the soap product with the quantity of water desired at a temperature appreciably above room temperature but not above 100 C. Still further, the Water addition may be effected after the anhydrous saponiflcations reaction is completed by introducing super-heated steam into the reaction mass and passing the steam therethrough, at a temperature and pressure providing for condensation of a portion of the same.

Addition of water ma not alwaysbe desired, or for some purposes, may be required in only very-small (even fractional) percentages. Products of this type may be quite hard and may advantageously be ground, thereby yielding an effective soap powder.

On the other hand, for some purposes the invention contemplates addition of relatively large amounts of water, even upwards of 10%, and in cases of this type where it is at the same time desired to retain considerable body or hardness in the soap, the invention contemplates the addition of sodium silicate up to about 30%, for instance, from about 3% to 5%.

It is to be noted that initial production of an anhydrous soap, followed by controlled additions of the desired quantity of water is a procedure in distinct contrast to the usual soap producing of the foregoing treatment conditions.

methods, wherein the soap initially contains water and is thereafter subjected to drying. Therefore, the process of the present invention is of advantage in eliminating the drying steps and the drying equipment; heretofore required.

Oxidizing or bleaching agents other than hydrogen peroxide may be employed, for instance, benzoyl peroxide, barium peroxide, sodium peroxide, hypochlorites, other chlorine containing bleaching agents, etc. In some cases it may be desirable to vary some For instance, it is contemplated that the water and peroxide treatments may be effected separately, although preferably they are both carried out after the anhydrous saponiflcation has been completed. EXAMPLES In addition to the illustrative process fully analyzed'above, there are presented hereinafter a number of examples which illustrate various individual steps of the process and also various combinations of the steps. For convenience in consideration of the examples, the parts and the several ingredients are listed in each instance. (All parts are by weight.)

Example 1 Harts Fishoil 440' Rosin s 66 Sodium carbonate 93 Sodium hydroxide 12 The original oil was of dark color. It was heated together with the rosin up to 300 C. be.-

fore addition of the alkali. The sodium carbonate and sodium hydroxide were added in small portions-andafter the addition of the alkali, the reaction mass was maintained between about 270 C. and 290 C. for about 4 to 5 hours.

The color of the product was quite light.

Example 2 v Parts Fish oil 375 Rosin 125 Sodium carbonate 93 Sodium hydroxide 10 Example 3 Parts Linseed oil 187 Sunflower oil 188 Rosin 125 Sodium carbonate 106 After about 1 hours heating 30% water was added and the mass was well kneaded, yielding a uniform soap product containing about 7.2% water.

Example 4 I I Parts Fish oil Sunflower oil 100 Rosin; 40 Sodium carbonate '45 Sodium hydroxide 5 I The reaction mass was heated for about 3% hours between about 290 C. and 300 C. Some gas evolution was observed at 300 C.

The product was quite hard and was free of fish oil odor.

Example 5 Parts Fish oil 30o Sodium carbonate 74 Eromple 6 Parts Fish oil fatty acids 300 Rosin 60 Sodium carbonate --l. 83

The reaction mass was treated in accordance with Example 5, the product, being somewhat harder than that of Example 5. Steam was again introduced in the manner of Example 5, yielding a soap of satisfactory consistency, with a water content oi l.t%.

Example 7 4 Parts Fish oil fatty acids 300 Rosin --L 60 Sodium carbonate 83 Example 11 Parts Cod liver oil bleached once 250 Rosin 100 Potassium carb ate 2 This experiment yielded a good potassium soap of light color, capable of forming a good lather.

The reaction temperature was about 260 C. and the time about 4 hours. After incorporation of water, the final product contained about 51% water and was still fairly hard and could have taken even more water.

Example 12 Parts Cod liver oil 300 Rosin 10% Sodium hydrm F16 The treatment temperature was from about 7 290 6. to 30 02, the time being about t hours. The product was somewhat dark and very hard.

Example 13 Parts Cod liver oil fatty acids bleached once 200 Rosin 10d Sunflower oil fatty acid 100 Sodium carbonate 82 Sodium hydroxide 10 The oil and rosin were heated to 180 C. and

the sodium carbonate was added at that temperature. The temperature was then raised to 250 C. and vacuum was applied, the temperature ris= me still further to about 275 C. Thereafter the temperature was again dropped to about 250 C. and steam was bubbled through the reaction mixture, the temperature dropping to about 2W C.

The product was fairly hard and contained 30.6% water.

Example 8 Parts Linseed oil 124 Sunflower oil 126 Rosin 84 4 Sodium carbonate 72 The temperature was taken up to about 300 C. and after a time the product was subjected to steam, by bubbling through the mass.

The product was of quite light color containing about .6% water.

Ezample 9 Parts Cod liver oil 300 Ros 90 Sodium carbonate Treatment temperature was about 250 C, the

I time being about 3 hours. The product was hard and after 3 months standing, the odor was still good.

Example 10 Parts Fish oil fatty acids bleached twice with Clarit (bleaching compound) 300 Ros 90 88 Example 14 Parts Fish oil fatty acids 300 Ros 90 Sodium carbonate ..L- 88 The sodium carbonate was first powderized to a fine powder and then dried in a porcelain dish on a flame, thereby driving ed a part of the C02.

The fatty materials and the rosin were preliminarily heated to C. and the alkalies were then added during temperature rise up to (3., the reaction mass being maintained under vacuurn. Thereafter the temperature was taken up to about 160 C. to 200 C.

Very little foaming occurred.

The product was a satisfactory soapy mass.

The fatty acid and rosin were heated together with the sodium carbonate in an autoclave to a temperature of about 230 C. for about 5 hours. The product was of good color, containing about .2% free alkali.

Water was incorporated in a batch of- 390 parts of this product, until th water equaled 18%. Thereafter 20 parts of water glass were added.

The final product had a good soap consistency.

Iclaim:

1. In the manufacture of solid soapsfrom fatty materials by the anhydrous saponification method, the process which comprises heating the fatty material, together with rosin and a dry saponitying agent selected from the class consisting of alkali metal oxides and hydroxides and alkali metal carbonates and bicarbonates, to a temperature or from to 350 C1, whereby to eilect amounts ranging fromv 15% to 40% based on the weight of the fatty material.

2. A process in accordance with claim 1 in which the rosin is present in amounts of about 3. A process in accordance with claim 1 in which the fatty material is a fish oil.

4. In the manufacture of hard solid soaps fro iatty materials, the process which comprises first producing an anhydrous soap product by heating to a temperature of from 150 C. to 350 C., a fatty oil and a rosin, the rosin being present inamounts ranging from to 40% based on'the weight of the fatty material, atintervals adding,

in anhydrous form small portions of a saponify- 15 ing agent selected from the class consisting of alkali metal oxides and hydroxides and alkali metal carbonates and bicarbonates, after addition of said agent, reducing the pressure on the batch while maintaining said temperature, the

temperature being maintained until a substantially anhydrous product is secured, and for about half an hour and thereafter addingwater to the anhydrous product by mixing the product with water under temperature and pressure conditions maintaining the water as liquid.

5. In the manufacture of solid soaps from fatty. materials by the anhydrous saponification method, the process which comprises heating the fatty material in a water free environment with rosin,

the rosin being present in amounts ranging from 15% to based on the weight of the fatty material, and with a saponifying agent selected from the class consisting of alkali metal oxides and hydroxides and alkali metal carbonates and as bicarbonates to a temperature between about 150 C. and 350 C., the time of treatment being sufficient to produce a substantially anhydrous product, the pressure being reduced below atmos heric pressure during at least a portion or said heating, 40

and thereafter admixing water with the anhy- Q drous product by heating the product with water at a temperature above C. but below the saponification temperature and at a pressure above atmospheric pressure.

6. A process in accordance with claim 1 in which the anhydrous soap is hydrated by the incorporation of water in amounts not to exceed 10% of the weight of the anhydrous soap, the water containing /2% to 2% of bleaching agent based on the weight of the anhydrous soap.

7. In a. process for making a hard soap having a predetermined water content the methodwhich comprises the steps: First, of, heating a mixture o1 fatty material, rosin, andan anhydrous saponifying agent selected from the class which consists of alkali metal oxides and hydroxides incorporating in such material a predetermined quantity of water and a bleaching agent selected from the classconsisting of peroxides and chlorine-containing bleaching agents, said water not to exceed 10% of the weight of the anhydrous soap.

8. A process in accordance with claim 'I and further comprisingas a part of the second step the addition of hydrogen peroxide, as the bleaching agent. a

LAszno 1mm.