US2300103A - Process for breaking petroleum emulsions - Google Patents

Description

Patented Oct. 27, 1942 PROCESS FOR BREAKING PETROLEUM EMULSIONS Edwin E. Clayton, Long Be Petrolite Corporation, Ltd.,

ach, CaliL, amignor to Wilmington, DeL,

a corporation of Delaware No Drawing. Application June 19, 1941, Serial No. 398,814

8 Claims.

This invention relates to the resolution of petroleum emulsions.

The main object of my invention is to provide a novel process for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

Another object of my invention is to provide an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned is of significant value in removing impurities, particularly inorganic salts from pipe line oil.

In my improved process, hereinafter described in detail, derivatives of the water-soluble type of petroleum acid, commonly known as green acid or acids, are used as a demulsifier to resolve or break a petroleum emulsion of the water-inoil type.

Petroleum sulfonic acids,are produced from a Wide variety of petroleum distillates or petroleum fractions, and in some instances they are produced from the crude petroleum itself. When produced from crude petroleum itself it is customary to use crude oil of the naphthenic type, crude oil of the paraffin type, crude oil of the asphaltic type and mixtures of said three different types of crude oil.

The art of refining crude petroleum or various fractions, using sulfuric acid of various strengths, as well as monohydrate and fuming acid, is a well known procedure. In such conventional refining procedure, petroleum sulfonic acids have been produced asby-products. For instance, in removing the olefinic components, it has been common practice to use sulfuric acid so as to polymerize the olefines or convert them into sulfonic acids which are subsequently removed. Likewise, in the production of white oil, or highly refined lubricating 0115, it has been customary to treat with fuming sulfuric acid, so as to eliminate certain undesirable components.

In recent years, certain mineral oil fractions have been treated with sulfuric acid with the primary object of producing petroleum sulfonic will be herein referred to as water-soluble, without any efiort to indicate whether the solution is molecular or colloidalin nature. The green acids, as indicated by their name, frequently give an aqueous solution having a dark green or graygreen appearance. They generally appear as a component of the acid draw-off, and do not remain behind dissolved in the oil fraction which has been subjected to sulfuric acid treatment. The green acids are not soluble in oil, even when substantially anhydrous, and certainly are not soluble in oil when they contain as much as 15% of water. Similarly, their salts obtained by neutralizing the green acids with a strong solution of caustic sode, caustic potash, or ammonia, are not oil-soluble. For convenience of classification, the ammonium salt will be considered as an alkali salt.

In contradistinction to the hydrophile green acids, there occurs as in the manufacture of medicinal white oil, the oil-soluble type or the mahogany acids. These mahogany acids are characterized by being soluble in oil, especially acids, and in such procedure the petroleum sulfonic acids represented the primary products of reaction, rather than concomitant by-products.

when anhydrous, and being soluble in oil, even if they contain some dissolved water. Some of the mahogany acids also show limited hydrophilic properties to the extent that either some water can be dissolved in the acids, or they, in turn, may dissolve to some extent in water. In some instances their salts, such as the sodium, ammonium, or potassium salt, will dissolve in water to give a colloidal sol. However, regardless of the presence of any hydrophilic properties whatsoever, they always have a characteristic hydrophobe property, as indicated by the fact that the substantially anhydrous form, for instance, their alkali salts containing 512% water, will dissolve in oil. This clearly distinguishes them from the green acids previously referred to, because the green acids in similar form containing the same amount of water, for example, will not dissolve in oil. The green acids, as such, are essentially hydrophilic and non-hydrophobic in character.

The utility of the mahogany acids in various arts has been enhanced by increasing their water-solubility; for instance, converting the ,ma-

hogany acids into hydroxy alkylamine salts. On the other hand, as far as I am aware, no valuable product of commerce has resulted from decreasing the water solubility of the mahogany acids by the addition of some oil-soluble basic amine, such as, for example, triamylamine. The triamylamine salts of mahogany acids, for example, are completely devoid of any solubility in water which the alkali salts may have exhibited and show, as would be expected, an increased solubility in hydrophobe solvents.

Green acids are hydrophile in character, as previously stated. Their hydrophile character has been increased by neutralization with materials such as triethanolamine and the like. Such green acid salts, having enhanced water solubility, as compared with the ordinary alkali salts, havefound application incertain arts.

I have found that if green acids, of the oilinsoluble type, are neutralized with a heat-polymerized basic hydroxyamine of the kind hereinafter described, the resultant product has pronounced value as a demulsifier for oil field emulsions of the water-in-oil type, either when used alone, or when used in conjunction with other compatible and well-known demulsifiers. Heatpolymerized basic hydroxyamines are well known compounds and are described in detail, for example, in U. S. Patent No. 2,231,758, dated February 11, 1941, to De Groote, Keiser and Blair. For purposes of convenience, the subsequent description of such heat-polymerized basic hydroxyamines is substantially identical with that found in the aforementioned U. S. Patent No. 2,231,758.

It is well known that alkylol amines or similar basic hydroxy amines, i. e., amines characterized by the fact that there is no aryl radical directly attached to the amino nitrogen atom, can be polymerized by heating to elevated temperature, particularly in the presence ,of suitable catalysts. Generally speaking the catalysts are basic materials, or materials having a basic reaction, such as caustic soda, soap and the like. Polymerized amines contain two or more amino nitrogen atoms, but the most desirable form for my purpose is the form in which there are at least three nitrogen atoms present, and not more than five nitrogen atoms. Such amines may be polymer.- ized to the degree that the material shows surface activity, when dissolved in water, either in the form of the amine (forming a base with water, of course), or in the form of a salt, such as the acetate. For the sake of convenience, I will refer to the polymerized amines, broadly, as the polymerized product. I will refer to. the form containing two nitrogen atoms as thedimeric form, and the type containing three, four or five nitrogen atoms, as the polymeric form. When sufficiently polymerized, the product will be surface active. This means that a dilute solution, as such, or in the form of the acetate (for instance, one tenth of 1% to 1%) will foam. I will refer to such type as the highly polymerized surface active form. In actual practice, the amine that is available mostcheaply and which po ymerizes most readily and which gives the most desirable type of demulsifier, is triethanolamine, particularly commercial triethanolamine, which, as is known, contains a smallamount of monoethanolamine and an appreciable amount of diethanolamine. The composition of such polymerized amines is not definitely known, except that the polymerization takes place obviously by virtue of ether linkages. Examination of triethanolamine, for example, indicates that cyclic polymers could be formed or linear polymers could be formed, or polymers could be formed which involve both linear and cyclic formations.

Needlessto say, since polymerization involves ether linkages, one may include a polyhydric alcohol, such as a glycol or glycerol, recinoleyl alcohol, or one might include polyhydric alcohols containing ether inkages, such as diethylene glycol, diglycerol, triglycerol, tetraglycerol, and the like. Monohydric alcohols, of course, can be employed only to form ether linkages with a terminal hydroxyl group. Thus, one mole of triethanolamine, for example, and three moles of ethyl alcohol might not form a highly polymerized material. is readily understood, in view of the common theory of polyfunctionality in regard to resinous or subresinous materials derived from polyhydric alcohols and polybasic acids. 'To produce highly polymerized materials one must have retactants which are at least bifunctional. In polymerizations of the kind described the polyhydroxylated amines are bifunctional or polyfunctional intermolecularly. Monohydroxylated amines, such as ethanolamine, or a diethylethanolamine, are in the same class as monohydric alcohols, i. e., they are monofunctional, unless, as far as the material such as monoethanolamine is concerned, the hydrogen atoms attached to amino nitrogen atom could be removed with the formation of water, with the result that instead of an ether linkage, there is a direct carbon atom, nitogen atom bond. Thus, in the claims reference will be made to the polymerization of polyfunctional alkylol amines,

the intention being to emphasize this particular feature. As has been indicated, however, monofunctional compounds, such as monohydric alcohols, and certain monohydroxy amines are acceptable to form part of the polymerized compound or composition. Furthermore, polyhydric alcohols may be employed to produce the same polymeric structures as polyhydrated amines. The preferred type of compound, however, is prepared without the introduction of polyhydric alcohols, such as glycerols, glycols, and the like. If desired, such particular type of preferred polymer may be indicated as being free from polyhydric alcohol residues, or more broadly, free from alcohol residues, the word alcohol being used in the sense to refer to non-amino bodies, 1. e., the glycols and glycerols, and is not intended to refer to aminoalcohols as the term is sometimes used in the description of triethanolamine or the like.

The polymerization of the basic hydroxy amines is effected by heating same at elevated temperatures, generally in the neighborhood of 200 to 270 C., preferably, in the presence of catalysts, such as sodium hydroxide, potassium hydroxide, sodium ethylate, sodium glycerate, or catalysts of the kind commonly employed in the manufacture of superglycerinated fats and the like. The proportion of catalysts employed may vary from slightly less than one tenth of 1% in some instances, to slightly over 1% in other instances.-

Needless to say, in the event the alcohol amine is low boiling, customary precautions must be taken so as not to lose part of the reactants. On the other hand, conditions must be such as to permit the removal of water formed during the process. At times the process can be conducted most readily by permitting part of the volatile constituents to distill, and subsequently subject- Theprinciple involved, of course,

the xylene. The dried condensate is then returned to the reaction chamber for further use.

.In some instances, condensation can best be conducted in the presence of a high boiling solvent, which is permitted to distill in such a manner as to remove water of reaction. In any event, the speed of reaction and the character of the polymerized product depends not only upon the original reactants themselves, but also on the nature and amount of catalyst employed, on the temperature employed, time of reaction and speed of water removal, i. e., the effectiveness with which the water of reaction is removed from the combining mass. Polymerization can be effected without the use of catalysts in the majority of instances, but such procedure is generally undesirable, due to the fact that reaction takes a prolonged period of time and usually a significantly higher temperature. It is noted that in the subsequent examples the final compositions of matter which are contemplated, particularly for use as demulsifiers, are preferably derived by means of water-soluble polymerized hydroxy amines as one of the reactants. Thus, all the subsequent description of polymerized hydroxy amines has been limited largely to the type which is watersoluble, and is obviously the preferred type. How- 1 ever, it must be recognized that polymerized hydroxy amines, particularly if polymerized for a fairly long period of time, at a fairly high temperature, and in the presence of an active catalyst, may result in a polymerization reaction which ends in a product that is water-insoluble, or substantially water-insoluble. Obviously, such I water-insoluble material can be obtained more readily from a higher hydroxy amine than from a lower one. In other words, tributanolamine, triliexanolamine, trioctanolamine, etc., would yield such insoluble products much more readily than triethanolamine.

Incidentally, it also must be recognized that the speed of reaction and the degree of polymerization is effected by the nature of the vessel in which the reaction takes place. In the examples cited, it is intended that reaction take place in a metal vessel, such as iron. However, in order to obtain the same degree of polymerization, when conducting the reaction in a glass lined vessel, it is quite likely'that the period of reaction would have to be increased 150 to 400%.

Suitable hydroxy primary and secondary amines which may be employed to produce materials of the kind above described includes the following: diethanolamine, monoethanolamine, ethyl ethanolamine, methyl ethanolamine, propanolamine, dipropanolamine, propyl propanolamine, etc. Other examples include cyclohexanolamine, dicyclohexanolamine, cyclohexyl ethanolamine, cyclohexyl propanolamine, benzyl ethanola- 5 mine, benzyl propanolamine, pentanolamine, hexanolamine, octyl ethanolamine, octadecyl ethanolamine, cyclohexanol ethanolamine, etc.

Similarly, suitable hydroxy tertiary amines which may be employed include the following: triethanolamine, diethanolalkylamines, such as diethanol ethylamine, diethanol propylamine, etc. Other examples include diethanol propylamine, etc. Other examples include diethanol methylamine, tripropanolamine, dipropanol methylaoxygen of the aldehyde,

mine, cyclohexanol diethanolamine, dicyclohexanol ethanolamine, cyclohexyl diethanolamine, dicyclohexyl ethanolamine, dicyclohexanol ethylamine, benzyl diethanolamine, dibenzylethanolamine, benzyl dipropanolamine, tripentanolamine, trihexanolamine, ethyl hexyl ethanolamine, octadecyl'diethanolamine, polyethanolamine, etc.

It is also known that one may have amines of the type:

0111.0 CzH OH (anion cimon 0211.0 ciraon 0111.0 013.011

HN HN C2H40C2H40H CzHaOH such amines may serve as functional equivalents of the previously described amines.

Attention is directed to the fact that the alkylolamines are obtained in such a manner that they may be looked upon as being derivatives of dihydric alcohols, or of the chlorhydrins of the dihydric alcohols. For example, the alkylolamines may be prepared as follows:

It is not necessary to point out that the same types of reactidns will produce secondary or tertiary amines, and that the reaction is not limited to a combination with ammonia, but may take place with a combination of other primary or secondary amines, such as amylamine, diamylamine, cyclohexylamine, dicyclohexylamine, benzylamine, dibenzylamine, amyl cyclohexylamine, etc. I

This means that in the types of material previously described, there is a wide variety of material, such as mono-glycerylamine, diglycerylamine, monoglyceryl diethylamine, monoglyceryl dipropylamine, diglyceryl propylamirie, triglycerylamine, etc., which are functional equivalents of the various amines previously described. All that has' been said here in regard to functional equivalents will be perfectly obvious without further explanation to those skilled in the art. See U. S. Patent No. 2,091,704, dated August 31, 1937, to Duncan and McAllister, and also U. S. Patent No. 2,042,621, dated June 2, 1936, to Olin.

Attention is directed to co-pending application for patent Serial No. 273,221, filed May 12, 1939, by Melvin De Groote. Said aforementioned application describes, among other things, the formation of hydroxy diamines, particularly certain hydroxylated methylene diamines by reactions involving an aldehyde such as formaldehyde, and secondary amines, as,- for example, diethanolamine. In such reaction the amino hydrogen atoms are removed along with the for instance, the oxygen atom of formaldehyde. The resultant product is tetraethanolmethylene diamine. Such hydroxylated amines, or comparable types, such as polyethylene diamlnes, may be employed. In the polyglycerols, and

amine and a chlorhydrin, such as glycerine chlor-- hydrin, and the like. Examples of hydroxylated amines obtained by the procedure described in said aforementioned De Groote and Keiser application may be illustrated by the following ex Attention is also directed to the fact that suitable amines include tris(hydroxymethyl) aminomethane, and derivatives thereof, obtained in various manners, for instance, by reaction with chlorhydrins, alkyl chlorides, and the like, particularly ethylene glycol chlorhydrin, glyceryl monochlorhydrin, etc.

Ponymnmznn Hxpnoxr AMINE Example 1 One percent of caustic soda is added to commercial triethanolamine and the product heated for approximately three hours at 245260 C. The mass is stirred constantly, and any distillate is condensed and reserved for re-use after an intermediate running step. At the end of approxi: mately two and one-half to three and one-half hours, the molecular weight determination shows that the material is largely dimeric.

Pomruxmznn HYDBOXY Ammo Example 2 The same procedure is employed as in the previous example, except that heating is continued for approximately another hour. In this instance the reaction mass is largely a polymeric material with an average molecular weight range indicating the presence of approximately three to four nitrogen atoms in the polymerized mass.

PoLYMEmzEn Hrmzoxx Amm't Example 3 POLYMEBIZED HYDBOXY AMINE Example 4 'Iri-isopropanolamine is substituted for triethanolamine in Examples 1, 2 and 3.

POLYMERIZED HYDBOXY AMINE Example 5 Tripentanolamine is substituted for triethanolamine in Examples 1, 2 and 3.

of two parts of hydroxy amine and one-part of glycerol. One percent of caustic soda is added to the mixture and the same procedure employed as indicated in Examples 1, 2 and 3, although there may be some variation necessary to obtain the proper molecular weight range and surface activity. In any event, molecular weight determinations can be employed, as "well as a foam test of the kind previously described.

POLYMERIZED HYDBOXY AMINE Example 8 Diglycerylamine is substituted for triethanolamine, in Examples 1, 2 and 3, previously described.

As previously stated, the preferred polymerized hydroxy amines are water-soluble, but the wateriusoluble type, orsubstantially water-insoluble type, of the kind previously referred to, may also be employed. Furthermore, it must be remembered that the final criterion of degree of polymerization, especially in the initial stages, is dependent upon an actual molecular weight determination, rather than based on time of reaction.

The manufacture of the demulsifler employed in my process involves nothing more or less than neutralizing the selected petroleum sulfonic acid with a suitable poLvmerized amine so as to neutralize the sulfonic hydrogen atom. As a rule, one can employ any suitable indicator, for instance, methyl orange, litmus, or any other suitable means of determining the neutralization point. For purposes of convenience, I prefer that the selected petroleum sulfonic acid contain not over 15% of water. It is. of course. understood that the conventional procedure employing double decomposition instead of direct neutralization, can be employed in the manufacture of my new material or composition of matter.

It may be well to point out that the hydrophile, non-hydrophobe petroleum sulfonic acid or acids of the green acid type varies somewhat. For instance, the molecular weight may vary from the range of 350-500 or thereabouts. Naturally, these petroleum sulfonic acids may carry some polymerized olefins, free hydrocarbons, or the like, or may even carry a bit of naphthenic acids which represent carboxylated, non-sulfonated petroleum acids. As previously stated, these materials are well known commercial products and are available in the open market, either in the form of the acid itself, or in the form of a salt.

Attention is directed to the fact that some of the polymerized hydroxyamines herein contemplated produce oil-soluble, water-insoluble salts when employed to neutralize green acids. This is particularly true in regard to those amines which are surface-active per se; i. e., the solution of the amine in water or in the form of a simple salt, such as the acetate, shows surface activity, as exemplified by producing, foaming, etc. Whether or not a water-insoluble salt is produced depends, in part, on the molecular weight of the acid; and as has been previously indicated, this property may show variation. However, the surface-active, heat-polymerized hydroxyamines" almost invariably produce a water-insoluble product, or at least a product with very limited water solubility, compared with the sulfonic acid prior to neutralization.

Although it is believed, in view of what has been said previously, that no further description is required in regard to the manufacture of the new compounds herein contemplated, and particularly for use of demulsifiers, the following examples are added purely by way of illustration:

Example 1 The same procedure is followed as in Example 1, but instead, the green acids are obtained from Gulf Coast transformer oil extract in the manner described in U. S. Patent No. 2,203,443, dated June 4, 1940, to Ross and Mitchell.

Example 3 The same procedure is followed as in Example 2, except that California 65 Saybolt viscosity Edeleanu extract employed instead of Gulf Coast transformer Edeleanu extract employed in Example 2.

Ea'ample 4 The same procedure is followed as in Example 1, except that the product is made from a Gulf Coast naphthene type crude, preferably of the kind which has little or no low boiling fraction,

i. e., the kind which, on a straight run distillation, gives little or no gasoline.

Example 5 The same procedure is followed as in Examples 1-4, inclusive, except that an amine of the kind exemplified by Polymerized Hydroxyamine, Example 2, is employed instead of the polymerized hydroxyamine previously referred to.

Example 6 The same procedure is followed as in Example 5 preceding, except that the polymerized hydroxyamine employed is of the kind described in Polymerized Hydroxyamine, Example 3, preceding.

Ezrample 7 The same procedure is followed as in Example 5 preceding, except that the polymerized hydroxyamine employed is of the kind described in Polymerized Hydroxyamine, Example 6, preceding.

Example 10 The same procedure is followed as in Example 5 preceding, except that the polymerized hydroxyamine employed is of the kind described in Polymerized Hydroxyamine, Example '7, preceding.

Ea'ample 11 The same procedure is followed as in Example 5 preceding, except that the polymerized hydroxyamine employed is of the kind described in Polymerized Hydroxyamine, Example 8, preceding.

Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as gasoline, kerosene, stove oil, a coal tar product, such as benzene, toluene, xylene, tar acid oihcresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents, such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of my process may be admixed with one or more of 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.

It is well known that conventional demulsifying 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 limited oil solubility. However, since such reagents are sometimes used in a ratio of 1 to 10,000, or 1 to 20,000, or even 1 to 30,000, such an apparent insolubility in oil and water is not signiflcant, because said reagents undoubtedly have solubility within the concentration employed. This same fact is true in regard to the material or materials employed as the demulsifying agent of my process.

I desire to point out that the superiority of the reagent or demulsifying agent contemplated in my process is based upon its ability to treat certain emulsions more advantageously and at a somewhat lower cost than is possible with other available demulsifiers, or conventional mixtures thereof. It is believed that the particular demulsifying agent or treating agent herein described will find comparatively limited application, so far as the majority of oil field emulsions are concerned; but I have found that such a demulsifying agent has commercial value, as it will economically break or resolve oil field emulsions in a number of cases which cannot treated as easily or at so low a cost with the demulsiiying agents heretofore available.

In practising my process, a treating agent or demulsifying agent of the kind above described is brought into contact with or caused to act upon the emulsion to be treated, in any of the various ways, or by any of the various apparatus now -generally used to resolve or break petroleum emulsions with a chemical reagent, the above procedure being used either alone or in combination with other demulsifying procedure, such as the electrical dehydration process.

The demulsifier herein contemplated may be employed in connection with what is commonly known as down-the-hole procedure, i. e., bringing the 'demulsifier in contact with the fluids of the well at the bottom of the well, or at some point prior to their emergence. This particular type of application is decidedly feasible when the demulsifier is used in connection with acidification or calcareous oil-bearing strata, especially if suspended in or dissolved in the acid employed for acidification.

Having thus described my invention, what I 018g? as new and desire to secure by Letters Paten s:

1. A process for resolving petroleum emulsions of the water-in-oil type, characterized by sub- J'ecting the emulsion to the action of a demulsifier comprising a. chemical compound consisting of the salt of a basic amine; said amine salt being obtained from a watersoluble, non-hydrophobe petroleum sulfonic acid of the green acid type and a heat-polymerized basic hydroxyamine.

2. A process for resolving petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifler comprising a chemical compound consisting of the salt of abasic amine; said amine salt being obtained from a water-soluble, non-hydrophobe petroleum sulfonic acid of the green acid type and a non-acylated heat-polymerized basic hydroxyamine.

3. A process for resolving petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifler comprising a chemical compound consisting of the salt of a basic amine; said amine salt being obtained from a water-soluble, non-hydrophobe petroleum sulfonic acid of a green acid type and a non-acylated heat-polymerized basic hydroxyamine free from an ether radical derived from a monohydric alcohol.

4. A process for resolving petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising a chemical compound consisting of the salt of a basic amine; said amine salt being obtained from a water-soluble, non-hydrophobe petroleum sulfonic acid of the green acid ,type and a non-acylated heat-polymerized basic hydroxyamine free from an ether radical derived from an alcohol. 7

5. A process for resolving petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising a chemical compound consisting of the salt of a basic amine; said amine salt being obtained from a water-soluble, non-hydrophobe petroleum sulfonic acid of the green acid type and a water-soluble. non-acylated heat-polymerized basic hydroxyamine free from an ether radical derived from an alcohol.

6. A process for resolving petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifler comprising a chemical compound consisting of the salt of a basic amine; said amine salt being obtained from a water-soluble, non-hydrophobe petroleumsulfonic acid of the green acid type and a water-soluble non-acylated ,heat-polymerized basic hydroxyamine of the dimeric type, free from an ether linkage derived from an alcohol. I

7. A process for resolving petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising a chemical compound consisting of the salt of a basic amine; said amine salt being obtained from a water-soluble, non-hydrophobe petroleum sulfonic acid 01' the green acid type and a water-soluble non-acylated heat-polymerized basic hydroxyamine of the polymeric type, free from an ether linkage derived from an alcohol.

, EDWIN E. CLAYTOR.