US2385818A - Solidified normally liquid hydrocarbons - Google Patents

Description

Patented Oct. 22, 1M5

Albert Joseph Laliberte, Nau'gatuck, Com, as-

signor to Safety-Fuel, Inc., West Cheshlr Comm, a corporation of Connecticut 7 No Drawing. Application March 18, 1942,

Serial N0. 435,169

10 Claims.. (Cl. 44-7) This invention relates to new and useful improvements in solidified normally liquid hydrocarbons.

The normally liquid hydrocarbons in accordance with the invention are of the combustible type and preferably of the combustible fuel type,

One example is, for instance, a petroleum distillate. Another example is a mixture of hydrocarbons of the benzene series. Although such normally liquid hydrocarbons as used for fuel ordinarilfcontain numerous hydrocarbons, the term hydrocarbons as used herein includes the limiting case in which only one hydrocarbon is present. As a. normally liquid hydrocarbon, I may, for instance, use gasoline, although I prefer a petroleum distillate of closer boiling point. Also benzol or a light coal tar distillate consisting predominantly of benzol homologues may be used. The normally liquid hydrocarbons in accordance with my invention are preferably for ordinary use readily inflammable and preferentially then possess a flash point not substantially above normal temperature so that combustion may be started by means of a match or similar lighter while the fuel is at normal temperature.

In accordance with the invention a voluminous gel 'of a metallic soap substantially insoluble or limitedly soluble in the hydrocarbon to be solidified is created, in situ, in such hydrocarbon by reacting a hydrocarbon solution of a suitable organic compound, saponifiable to yield a voluminous metallic soap, with a suitable saponification agent suspended-in the hydrocarbon solution in substantially dry pulverul'ent form, under conditions substantiallyassuring finest comminution of the soap products formed.

The saponification reaction may be either one of acid neutralization or of double decomposition. The saponification agent should be maintained in suspension during the reaction, i. e., no appre ciable segregation of suspended particles should occur. This, as a rule, ma be accomplished by agitation or by the procurement of finest dispersion of saponification agent in the hydrocarbon to be solidified and preferably with the aid of a suitable dispersion device such as a colloid mill, ball mill or the like.

Comminution of the soap products formed during the reaction may be accomplished in accordance with the invention by agitation. The comrninution may be carried out or enhanced by the use of a suitable comminuting or dispersing device such as a colloid mill, baL mill or the like. When proceeding in this manner, the resulting products are of a heavily viscous to petrolatumlike consistency depending upon the amount of soap products present. The solidified hydrocarbon products of a consistency approaching or simulating that of pe'trolatum are, as a rule, preferred as they cannot be poured under normal conditions and are usually possessed of a high degree of homogeneity.

I have discovered that it is sometimes of advantage in the production of products of relatively high consistency, such as those approaching or simulating petrolatum consistency, to use dispersing or peptizing agents of a type substan- 'tially soluble in the hydrocarbon to be solidified.

In some cases, it is of advantage to initiate or expedite the saponification reaction by heating the hydrocarbon solution containing the reactants to a temperature ofabove normal or alternatively procure the mixing of the reactants at such temperature. Depending upon the reactants used, the temperature requirements may vary. In some cases, a temperature of about 40 C. may suflice, while in other cases, higher temperatures must be resorted to. In most cases, once the saponification reaction has been satisfactorily initiated, the heating may be discontinued. In some cases, it maybe of advantage to continue the heating until the substantial completion of the saponiflcation reaction.

The organic compound of the afore-mentioned type is preferably one of the aliphatic acid or acid salt series, carrying at least one carboxyl or carboxyl metal group in aliphatic chain linkage, the aliphatic chain in either case having preferably at least 12 carbon atoms in said chain. The organic compound in accordance with the invention may thus comprise either an organic acid salt or free organic acid of the above-memtioned type and nature. If the same is'an organic acid, the saponification reaction is one of neutralization of the acid with the sa'ppnification agent. 0n the other hand, if ,the organic compound is a salt, the saponificatlonreaction will be one of double decomposition between the organic acid salt and the saponification agent. Organic acids useful in accordance with the invention are, for instance, stearic acid, oleic acid,

almitic acid and the like. In many instances the commercial forms of these acids may be used, such as, for instance the products obtained by the splitting of fats and containing a mixture of palmitic, stearic and oleic acids in varying proportions. Commercial products of this type are, for instance, coconut oil fatty acids, peanut oil fatty acids, palm oil fatty acids and the like. For best results, I have found it of advantage to usestearic acid. Organic salts that may be used in the practice of my invention are, for instance, the metal salts of any of the herein enumerated organic acids or mixtures of organic acids in which the metal is capable of exchange with the metal of the saponlfication agent.

The saponiflcationagent of the type hereinabove referred to may be any agent which is capable of neutralizing the organic acid present in the hydrocarbon solution or reacting with a suit able salt ofsuch organic acid by way of double decomposition as the case may be. The saponification agent should in all cases be such as is capable of forming with the organic compound inaccordance with the invention a voluminous metallic soap gel insoluble or limitedly soluble in the liquid material to be solidified. Good results are preferably obtained with hydroxides and 2.100- holates andsuitable saponification agents of this type, useful in accordance with the invention are, for example, sodium hydroxide, sodium alcoholates and the like. It is sometimes of advantage and desirable to initiate or. expedite the saponiflcation reaction by passing the reaction mix containing both the organic compound and the saponiflcation agent through a suitable dispersion device. In accordance with the preferred practice of my invention, the saponlflcation agent is added to the hydrocarbon solution of the organic compound in the form of a fine suspension in a portion of the hydrocarbon to be solidified.

The alcoholates are preferably the salts of monohydric and polyhydric alcohols carrying the hydroxyl group in aliphatic chain linkage. Examples of such alcohols are, for instance, the simple alcohols of the aliphatic series, such as methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, and the like alcohols. Examples of suitable polyhydric alcohols, are, for instance, the glycols. The alcoholate formation may be accomplished by the dissolution of a suitable metal such as metallic sodium in the alcohol. Whenever possible, however, such as in the case of the simple aliphatic alcohols, as for instance, methyl alcohol, ethyl alcohol, and the like, I prefer to obtain alcoholate formation by adding to a strong and concentrated alcohol, a suitable solid anhydrous metal hydroxide, such as sodium hydroxide with subsequent evaporation of excess alcohol. When proceeding in this manner, I prefer to use an alcohol concentration of in excess of 90% and preferably in excess of 95% and preferably equimolecular proportions of alcohol and hydroxide.

The dispersing or peptizing agent that I may use may be any one or combination of agents and preferably organic agents of this type. well-known in the art, substantially soluble in the hydrocarbon to be solidified, such as petroleum mahogany sulphonate, triethanolamine, and products of like character and nature. The amount of dispersing or peptizing agent to be added dependsance with the invention should be taken that the alcohol content is 6011-.

sidered in calculating the required amount of saponiflcation agent. A satisfactory solidified product contains approximately 4 to 11% (calculated on the hydrocarbon present) of metallic soap gel. v

The following is a practical example in accordgiven by way of illus: tration butnot of limitation. f

Example I to a point where no stratification or segregation of saponiflcation agent occurred upon interruption of the agitation. The sodium methylate was added to the organic acid hydrocarbon solution in finely pulverized dry form and kept in fine suspension therein by means of agitation. Vigorous agitation was used throughout the f-reaction until the completion thereof. The resulting prod-n uct was a heavily viscous homogeneous mass of a sticky pourable nature. The same burned without increase in fluidity.

In certain instanceswhere the reaction seems to be delayed or to proceed with difficulty even though the mass is heated to the reaction temperature, a small amount of alcohol from 0.5%

to 1.5% will initiate or expedite the reaction.

- acterized by a firmer structure.

' ification agent in suspension.

inter alia upon the reactants used and the fineness of dispersion desired.

The amount of reagents used within the practical application of my invention should be preferably so adjusted that the organic compound and hydrocarbon are present in a ratio suflicient to solidify substantially all of the hydrocarbon present with the soap gel formed; As a general rule 4% to 10% of the organic compound will accomplish this result. The saponification agent should be present in amount suflicient to accomplish the saponification, which as a rule, requires in excess of stoichiometric amounts. When using alcoholates containing crystal alcohol, care This may be achieved, for instance, by preparing a suspension of the entire amount of saponiflcation agent required in a hydrocarbon solution of only a portion of the organic compound. The amount of such organic compound is then preferably so selected as to be just sufllcient to yield by saponiflcation, the gel formation necessary for the desired degree of viscosity. The solution obtained in this manner contains unreacted saponiflcation agent held in suspension. by the soap gel formed and further amounts of organic compounds may then be added to the solution at any subsequent time for further reaction and solidiflcation. It is however also possible and special circumstances may make it desirable, to use in this multiple step saponification procedure an initial amount of organic compound less than that required for soap gel formation to the point of desired viscosity.

When using this procedure of successively reacting portions of organic compounds, the organic compounds for each portion may be either the same compounds or different compounds as desired.

stantially as formed, and agitating the mix. throughout the saponiflcation reaction to assure finest comminution of soap gel formed, said organic acid carrying at least one carboxyl group in aliphatic chain linkage of at least twelve carbon atoms in such chain.

2. Method according to claim 1 in which from 4 to of fatty acid calculated upon the total amount of hydgocariion present is reacted with said saponiflcation agent.

3. Method for solidifying a normally liquid inflammable hydrocarbon which comprises reacting a, 4% to 10% solution, in said hydrocarbon, of stearic acid with sodium hydroxide suspended in said hydrocarbon in substantially dry pulverulent form and agitating the mix throughout the saponiflcation reaction to assure finest comminution of the sodium stearate gel formed.

4. Method for solidifying a normally liquid inflammable hydrocarbon which comprises preparing a suspension of sodium hydroxide in a first portion of said hydrocarbon, reacting said suspension with a stearic acid solution in a second portion of said hydrocarbon, said stearic acid being present from 4% to 10% of the total amount of hydrocarbon, and agitating the mix throughout the saponiflcation reaction to assure finest comminution of sodium stearate gel formed.

5. Method for solidifying a normally liquid inflammable hydrocarbon which comprises reacting, in the presence of an aliphatic alcohol of not more than 5 carbon atoms, an organic fatty acid solution in said hydrocarbon with sodium hydroxide, suspended in said hydrocarbon in substantially dry pulverulent form, and agitating the mix throughout the saponiflcation reaction to assure finest comminuation of soapgel formed, said alcohol being present in amount not substantially in excess of about 3% of the hydrocarbon, said organic acid being saponiflable to produce a voluminous metallic soap gel from limitedly soluble to insoluble in said hydrocarbon, carrying at least one carboxyl group in aliphtaic chain linkage, of at least 12 carbon atoms in such chain and being present in said solution from 4% to 10% of the total amount of hydrocarbon added.

6. Method for solidifying a normally liquid inflammable hydrocarbon which comprises reacting, in the presence of methyl alcohol, a stearic acid solution in said hydrocarbon with sodium hydroxide, suspended in said hydrocarbon in substantially dry pulverulent form, and agitating the mix throughout the saponiflcation reaction to assure finest comminution of sodium stearate gel formed, said methyl alcohol being present in amount not substantially in excess of 3% of the hydrocarbon present in the final product.

7. A solidified hydrocarbon material which comprises a hydrocarbon gel of from syrupy viscous to petrolatum like consistency predominantly composed of a normally liquid inflammable hydrocarbon and 4 to 11% of a voluminous sodium fatty acid soap from limitedly solubly to insoluble in said hydrocarbon, said soap having an organic acid radical carrying at least one carboxyl group in aliphatic chain linkage of at least 12 carbon atoms in such chain, said gel having a bulk specific gravity substantially equivalent to the total weight of the components divided by the total volume of the components, being characterized by substantial freedom from melting when burning and being prepared to include precipitation of hydrocarbon fatty acid soap gel by reaction of free fatty acid, dissolved in said hydrocar-bon, with solid, pulverulent saponiflcation agent of the group consisting of sodium hydroxide and sodium alcoholates at a temperature assuring precipitation of soap gel continuously as formed and agitation substantially throughout the saponiflcation reaction.

8. A solidified hydrocarbon material which comprises a hydrocarbon gel of substantially petrolatum like consistency predominantly composed of a normally liquid inflammable hydrocarbon and 4 to 11% of sodium stearate, said gel'having a bulk specific gravity substantially equivalent to the total weight of the components divided by the totalvolume of the components, being characterized by substantial freedom from melting when burning and being prepared to include precipitation of hydrocarbon sodium stearate gel by reaction of free stearic acid, dissolved in said hydrocarbon, with solid, pulverulent saponiflcation agent of the group consisting of sodium hydroxide and sodium alcoholates at a temperature assuring precipitation of stearate 'gel con tinuously as formed and agitation substantially throughout the saponiflcation reaction.

9. A solidified hydrocarbon material in accordance with claim 8 in which said hydrocarbon gel contains not in excess of 3% of methyl alcohol based on the hydrocarbon present.

10. A solidified hydrocarbon material in accordance with claim 8 in which said hydrocarbon gel' contains a pyrotechnical compound.

ALBERT Josm- H LAIJBER'I'E.

In the following exampleyan alternative pro- I cedureobtaining a stearic acid soap in accord ance with the invention is illustrated.

Example II magnesium powder exhibit a thermite effect when ignited. These products are as a rule character- A dispersion or substantially anhydrous NaOH in naphtha was preparedby flnely grinding three parts by weight of NaOH with 21 parts by weight of naphtha and adding the resulting dispersion including 28 parts by weight of naphtha washings to 91 parts by weight of naphtha. parts by weight of stearic acid were melted and added to 140 parts by weight of naphtha. The stearic' acid naphtha solution was added slowly to the well agitated dispersion of sodium hydroxide in naphtha. Reaction took place immediately and 'stirring was continued for approximately twenty minutes'at which time reaction was substantially complete. The reaction mass constituted a syrupy sticky mass that could be poured and which adhered tenaciously to any surface with which it lived by intermittent flaring. The products obtained in accordance with the invention are characterized by a high degree surfaces with which they come into contact.

was contacted or against which it was thrown.

The product burned without decrease in viscosity. In the following example an illustration is given of the preparation of a solidified hydrocarbon material in accordance with the invention using a dispersing or peptizing agent.

Example III The procedure in this example is the same as that utilized in Example II. In this case, three parts by weight of mahogany sulphonate were added to a suspension of 5 parts by weight of NaOH in 140 parts by weight'of gasoline. A solution of parts by weight of stearic acid in 140 parts by weight of gasoline was slowly added to the vigorously stirred NaOH dispersion and the agitation continued until completion of the reac: tion. The product formed in this case possessed a consistency similar to that of petrolatum'. The product could not be poured and when in contact with or thrown against a surface, adhered tenaciously thereto. The product upon heating or burning did not liquefy. V

The consistency of the products in accordance with my invention may be varied or modified by changes in the reactants used so as to procure lesser or greater soap formation. Thus, for instance, when using a stearate soap as solidification agent higher amounts of stearic acid and NaOH, as seen from Example III, will produce solidified products more nearly approaching petrolatum like consistency.

In accordance withmy invention and as a still further embodiment thereof, I have discovered that it is possible to incorporate pyrotechnical agents "and compositions into the solidified hydrocarbons substantially without materially ailecting the characteristics of these products particularly with respect to liqueficatlon when heating or burning. These products may comprise any one or more of the know pyrotechnical agents or compositions including incendiary agents or compositions well known in the art. In the preparation of these products, I find it of advantage to finely disperse the pyrotechnical or incendiary agent in the hydrocarbon suspension of the saponification agent. Care should be taken however that the incendiary or pyrotechnical agent is so selected that it will not react with either the organic compound or saponiflcation agent so as to impair the saponiiication reaction. Thus, for instance, dispersions of mixtures of chlorate with This is particularly true of the products of petrolatum like consistency. The products are further characterized by the fact that the normally liquid hydrocarbon material which they contain may be recovered in substantially unadulterated form by the application of pressure, centrifugal manipulation, distillation or the like. Altematively, the hydrocarbon material may be recovered from the products solidified in accordance with the invention by separation with the aid of suitable solvent extraction. In such case,,the extracting solvent is preferably one in which the metallic soap is substantially soluble and the hydrocarbon but limitedly soluble or substantially insoluble.

The products in accordance with the invention are characterized by a considerable density. The solidified products are thus substantially free from voids and have a buikspecific gravity, 1. e., specific gravity .of the entire product, equivalent to at least the specific gravity of the normally to liquid hydrocarbon component and preferably a bulk specific gravity approximately equivalent to the total weight of the components divided by the total volume of the components. By reason of their density and characteristics of structure, the solidified products contain a high volume .percentage of hydrocarbon material.

In the preparation of solidified products as hereinabove set forth, a particular organic compound or acid used in the saponiflcation reaction may sometimes yield a product of an undesirably low viscosity. This condition maybe for instance encountered when using oleic acid. Though the resulting products are satisfactory for most purposes and will not materially increase in fluidity or decrease in viscosity when heated, it is, as a general rule, particularly for shipping and handling purposes, desirable to obtain a morehighly viscous consistency of the compound. In most cases the lack in desired high consistency can be remedied by using the particular organic compound or acid in question together with an organic compound or acid of the type yielding solidified products of a more satisfactory degree of consistency. By a proper proportioning of such organic compound or acid mixture, desired intermediate consistencies can be procured. For example, wh'ere oleic acid is to be used in the saponincation reaction it is preferred to use a mixture of oleic acid with stearic acid,

Theforegoing description is by way of illustration and not of limitation and it is, therefore, my intention that the invention be limited only by the appe ded claims or their equivalents, in which I have endeavored to claim broadly all inherent novelty.

CERTIFICATE OF CORhECTION.

Patent No. 2,385,818, October 2,; 191

. smear JOSEPH LALIBERTE.

It is hereby certified that error appears in .the printed specification of the above numbered patent requiring correction as follows: Page 1;, first column, line 29, claim 5, after the word. "form" insert the temperature of reaction being Such t sodium stearate gel precipitates continuously substantilly as forum"; line 59, claim A, and second column, line 5, claim 6-, after the comma and before "and agitating" insert "the teinperature of reaction using such that sodium stearate "gel precipitates continuously substantially as formed,- same page, first column, line 1 8, elaim 5, after the comma and before "and agitating" insert ---the temperature of reaction being such that soap gel precipitates oontimiouslr substantially as formed -j and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 29th day of January; A, D. 191 6.

Leslie F ra zer- (Seal) I First Assistant Commissioner oi Patents,