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2,025,805 Patented Dec. 31, 1935 UNITED ?TATES PATENT OFFICE , 2,025,805 PROCESS FOR BREAKING PETROLEUMZ EMULSIONS Melvin De Groote, St. Louis, Bernhard Keiser, Webster Groves, and Arthur F. WirteL'Bich mond Heights, Mo., assignors to Tretolite Com pany, Webster Groves, Mo., a corporation of ouri No Drawing. Application December 31, 1934, Serial No. 760,033 6 Claims. (Cl. 196-4) broadly speaking, polyricinoleic acids are more‘ This invention relates to the treatment of e?ective demulsifying reagents than ricinoleic emulsions of mineral oil and water, such as pe acid. However, there are certain emulsions on troleum emulsions, for the purpose of separating which the unpolymerized keto fatty acid bodies, the oil from the water. which will be referred to more simply as “keto Petroleum emulsions are of the water-in-oil fatty acid bodies”, are more effective than the 5 type, and comprise ?ne droplets of naturally-oc polymerized keto fatty acid bodies. The present curring waters or brines, dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion. 10 They are obtained from producing wells and from the bottom of oil storage tanks, and are commonly referred to as “cut oil”, “roily oil”, “emulsi?ed oil” and “bottom settlings". The object of our invention is to provide a 15 novel and inexpensive process for separating emulsions of the character referred to into their component parts of oil and water or brine. Brie?y described, our process consists in sub jecting a petroleum emulsion of the water-in-oil' 20 type to the action of a treating agent or de mulsifying agent of the kind hereinafter de scribed, thereby causing the emulsion to break down and separate into its component parts of oil and water or brine, when the emulsion is permitted to remain ina quiescent state after treatment, or is subjected to other equivalent separatory procedures. The treating agent used in our process con sists of an unpolymerized keto fatty body or 30 bodies. It is well known that fatty acids or fatty bodies can be subjected to chemical treat ment so as to yield keto fatty acids, that is, fatty acids in which a ketonic group (a carbonyl group) is present. One example is the conversion of 35 ricinoleic acid into ketohydroxystearic acid. (See Lewkowitsch “Chemical Technology of Oils, Fats and Waxes”, Gthedition, volume 1, page 242.) In a general way, the manufacture of such ketonic acids is dependent upon the treatment of an un 40 saturated fatty bcdy or fatty acid, such as ricin oleic acid, oleic acid, or the like, with a halogen, such as bromine, so as to form a halogen addi tion product, for example, ricinoleic acid di bromide, which. is then converted into ricin Ricinstearolic acid, on treatment 45 stearolic acid. process is concerned with the use of keto fatty, acid bodies in an unpolymerized state, in those instances where they are the most .effective de 10 mulsifying agents. . As previously indicated, the method described in the Lewkowitsch reference forproducing keto hydroxystearic acid bodies may be applied to va rious unsaturated acids and the like. Such proc 15 ess can be applied to the hydroxylated unsaturat ed materials obtained in themanner described in co-pending application for patent of De Groote and Keiser, Serial No. 760,025, ?led December 31, 1934. Said aforementioned application for patent. 20 discloses the oxidation of highly unsaturated fatty - bodies having a relatively high iodine number, ‘ ' above 120, for example, so as to produce un- ' saturated, hydroxylated fatty bodies. In our co-pending application for patent Serial as No. 760,031, ?led December 31, 1934, we have de scribed a new composition of matter consisting of the poly keto fatty acid bodies. These poly keto fattyacid bodies may beobtained by the esteri?ca tion or polymerization or condensation of a keto 30' fatty acid with another fatty acid molecule, which. need not contain a ketone group. In said afore mentioned application for patent describing these new compositions of matter, there is also disclosed a method for producing poly keto fatty 35 acids directly without ?rst forming the‘ unpoly merized keto fatty acids. It would appear'at least theoretically possible to decompose‘ such poly keto fatty acid bodies and perhaps separate from the resultant mixture unpolymerized keto fatty acid 40 bodies. Thus far, however, we-have been unable to accomplish this hydrolysis and separation, ' but this is immaterial ‘because the keto fatty acids may be produced in the‘ manner previously ' described. 45 We are fully aware that migration may take with sulfuric acid, yields ketohydroxystearic acid. place in a fatty molecule. For instance, that the In our co-pending application for patent Serial ‘ formation of stearolactone from hydroxystearic' ' No. 760,031, ?led December 31, 1934, we have dis acid appears to depend on the migration of the ‘closed the use of poly keto fatty acids or the salts alcoholiform hydroxyL- We are also aware that. or esters thereof for breaking oil ?eld emulsions. 50 in the case of the-common non-fatty ketonic acid, In a general manner we have found that fre aceto-acetic acid, that certain reactions are‘ quently the poly keto fatty acid bodies are more known to take place which suggest that aceto effective for breaking the majority of emulsions ~ acetic acid may, a far as these reactions are con-‘ than the unpolymerized keto fatty acid bodies. 55 This is true to the same general extent that, cemed, react more as an aldehyde or as an alde 2 2,025,805 hyde acid than as a ketonic acid. Such wander ing of a hydrogen atom and change in position of a double bond, is referred to as keto-enolic tautomerism (Bernthsen “Textbook of Organic Chemistry”, 2nd edition, 1931, page 231). We believe that this or a comparable change may take place in these ketonic fatty acids or bodies previously described. Possibly in regard to some reactions employed in identi?cation, these keto 10 acids or salts or esters thereof act more as if they were aldehydic acids or esters or salts there of. In other words, if these ketonic acid bodies are to be used in a mixture where aldehydic acids would be incompatible, it is also likely that these 15 ketonic acids or their salts or their esters may be incompatible, for the reason that they really may be aldehydic acid bodies. It is to be noted that the reagents of the kind employed for de termining the presence of the carbonyl group in -20 ketones also usually detect the presence of the carbonyl group in aldehydes. It is to be under stood that in the claims where the products are characterized by the presence of ketonic radical, that such acids might ultimately prove to be alde hydic acids, or at least convertible under certain conditions of use, or else under certain conditions of identi?cation, possibly they become converted into aldehydic acids, and it is not intended that the word “ketonic” or “keto” be interpreted as 30 excluding the meaning of “aldehydic” in the sense previously described or discussed, i. e., that both have the carbonyl (CO) radical present, and their ultimate composition in carbon atoms, hydrogen atoms, and oxygen atoms, is identical. 35 It is understood, of course, that these keto fatty acids or their esters may be converted into salts or into esters in the manner generally employed for the manufacture of salts and esters. How ever, it should be borne in mind that saponi?ca 40 tion of the kind which would decompose or de stroy the carbonyl radical cannot be employed. may be employed, such as the methyl ester, ethyl ester, propyl ester, butyl ester, amyl ester, hexyl ester, cetyl ester, etc. Aromatic or cyclic esters may be employed. What has been said in regard to the use of conventional demulsifying agents 5 applies also to the materials employed as the de mulsifying agent of our process, with the limita tion that such materials are generally monobaslc, although it is probable that dibasic acids, such as , sulfoketostearic acid might be prepared, and w would prove to be a suitable demulsifying agent. Conventional demulsifying agents’ employed in the treatment of oil ?eld emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as 15 gasoline, kerosene, stove oil, a coal tar product, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particular ly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, 20 butyl alcohol, hexyl alcohol, octyl alcohol, etc. may be employed as diluents. Miscellaneous sol vents, such as pine oil, carbon tetrachloride, sul fur dioxide, extract obtained in the re?ning of petroleum, etc. may be employed as diluents. 35 Similarly, the material or materials employed as the demulsifying agent of our process may be ad mixed with one or moreof the solvents customarily used in connection with conventional demulsifying agents. Moreover, said material or materials may be used alone or in admixture with other suitable well known classes of demulsifying agents, such as demulsifying agents of the modi?ed fatty acid type, the petroleum sulfonate type, the alkylated sulfo-aromatic type, etc. It is well known that conventional demulsify ing agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oil and water solubility. Sometimes they may be used in a form which exhibits relatively 40 limited water-solubility and relatively limited oil In such instances where it is desirable to elimi nate the residual acidity, it is best accomplished by means of a relatively weak base, such as tri solubility. However, since such reagents are sometimes used in a ratio of 1 to 10,000, or 1 to 20,000, or 1 to 30,000, such an apparent insolu means of a stronger base, such as ammonium said reagents undoubtedly have solubility with 45 ethanolamine, or it may be accomplished by hydroxide or caustic soda, provided the neutrali zation is conducted with care. In some instances it is desirable to mix an alcohol, particularly a 50 polyhydric alcohol, such as glycerine or ethylene glycol with a keto fatty acid body and then heat so as to eliminate the carboxylic hydrogen. In any event, the ketonic bodies may be converted into any suitable form by means of conventional 55 reactions, provided that the material is not de composed to destroy the carbonyl radical. Our preferred reagent consists of unneutralized ketohydroxystearic acid obtained from ricinoleic acid in the manner previously described. For the 60 sake of convenience we prefer to dilute the keto bility in oil and water is not signi?cant, because 15 in the concentration employed. This same fact is true in regard to the material or materials em- , ployed as the demulsifying agent of our process. As stated previously, it has been so common to 50 use a conventional demulsifying agent derived from an acid in the form of the acid itself, or in the form of a salt, or in the form of an ester. that the expression “acid body” is frequently em ployed to mean' the acid itself, or an ester thereof, 56 or salt thereof. The word “body” is herein em ployed in this same sense in conformity with its prior usage in the trade, and particularly in va rious patents of the prior art. Half salts and half esters are considered as'salts, and esters, re hydroxystearic acid with 50%, by weight, of a spectively. solvent composed of equal volumes of methyl al In practising our process a treating agent or de cohol and solvent naphtha. The use of demulsifying agents consisting of' mulsifying agent of the kind above‘ described is 65 various sulfo acids, or carboxy acids, or com brought into contact with or caused to act upon pounds having both a sulfo group and a carboxyl the emulsion to be treated, in any of the various 65 ways or by any of the various apparatus now gen group, is well known in the treatment of water erally used to resolve or break petroleum emul in-oil emulsions. In the use of conventional de mulsifying agents it is the common practice to sions with a chemical reagent. 70 use them, not only in the form of acids, but also Having thus described our invention, what we in the form of salts or esters, or half salts, or half esters, or ester salts, in case of dibasic acids. The salts generally employed are the sodium salt, potassium salt, ammonium salt, ‘calcium, magne sium, the triethanolamine salt, etc. The esters claim as new and desire to secure by Letters Pat- 70 en 1s: 1. A process for breaking a petroleum emulsion of the water-in-oil type, which consists in sub jecting the emulsion to the action of a demulsify ing agent, comprising a keto fatty acid body. 2,025,805 2. A process for breaking a petroleum emulsion of the water-in-oil type, which consists in subject in; the emulsion to the action of a demulsifying agent, comprising a keto fatty acid body in the form of an acid. ’ 8. A process for breaking a petroleum emulsion of the water-in-oil type, which consists in subject ing the emulsion to the action of a demulsifying agent, comprising a'keto fatty acid body derived 10 from castor oil. 4. A process for breaking a petroleum emulsion of the water-in-oil type, which consists in subject ing the emulsion to the action of a demulsifying 3 ' agent, comprising a keto fatty acid body in the form of an acid and derived from castor oil. 5. A process for breaking a petroleum emulsion of the water-in-oil type, which consists in subject ing the emulsion to the action ' of ketohydroxy stearic acid. ' 6. A process for breaking a petroleum emulsion of» the water-in-oil type, which consists in sub jecting the emulsion to the action of ketohydroxy stearic acid with 50%, by weight, of a‘ solvent com- 10 posed of equal volumes of benzol and ethyl alcohol. MELVIN DE GROOTE.‘ BERNHARD KEISER. ARTHUR F. WIRTEL.