US2372254A - Process for breaking petroleum emulsions - Google Patents

Description

chlorinated fatty acids.

acids, one might employ the hydrogenated resin Patented Mar. 27, 1945 r PROCESS FOR BREAKING PETROLEUM EMULSIONS Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Mo.,

assignors to Petrolite Corporation, Ltd, Wilmington, Del., a corporation of Delaware No Drawing. Application June 23, 1943, Serial No. 492,180

10 Claims.

This invention relates primarily to the resolution of petroleum emulsions, our presentapplication being a continuation in part of our copending application Serial No. 424,649, filed December 27, 1941, which subsequently matured as U. S. Patent No. 2,344,976, dated March 28, 1944.

One object of our present 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 our 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 demulsiiication under the conditions just mentioned is of significant value in removing impurities, particularly inorganic salts from pipeline oils.

The demulsifier or demulsifying agent employed in our process for breaking petroleum emulsions, consists of a sub-resinous or semi-resinous product obtained by reaction between a polybasic carboxy acid or its equivalent, such as the anhydride, and a hydroxylated esteramide of the kind hereinafter described.v Said hydroxylated esteramide is of the kind in which the amido acyl radical is derived from a hydroxlated monoca'rboxy acid having not over 5 carbon atoms, and

the acyloxy radical is characterized by being derived from a monocarboxy detergent-forming acid having at least 8 and not-more than 32 carbon atoms.

It is well known that certain monocarboxy or ganic acids containing eight carbon .atoms or more, and not more than 32 carbon atoms, are

characterized by the fact that they combine with alkalies to produce soap or-soap-like materials. These detergent-forming acids include fatty acids, resin acids, petroleum acids, etc. For the sake of convenience, these acids will be indicated by the formula RCOOH. Certain derivatives of detergent-forming acids react with alkali to produce soapor soap-like materials, and are the obvious equivalent of the unchanged or unmodified detergent-forming acids; for instance, instead of fatty acids, one might employ the Instead of the resin acids. Instead of naphthenic acids, one might employ brominated naphthenic acids, etc.

The fatty acids are of the type commonly referred to as higher fatty acids; and of course, this is also true in regard to derivatives of the kind indicated, insofar that such derivatives are obtained from higher fatty acids. The petroleum acids include not only naturally-occurring naphthenic acids, but also acids obtained by the oxidation of wax, paraffin, etc. Such acids may have as many as 32 carbon atoms. For instance, see U. S. Patent No. 2,242,837, dated May, 20, 1941; to Shields.

Although any of the high molal monoc'arboxy acids can be converted into esteramides of the kind described, by conventional procedure, it is our preference to employ hydroxylated esteramides derived from higher fatty acids, rather than petroleum acids, rosin acids, and the like. We have found that by far the most effective demulsifying agents are obtained from unsaturated fatty acids having 18 carbon atoms. such unsaturated fatty acids include the higher fatty acids, such as oleic acid, ricinoleic acid, linoleic acid, linolenic acid, etc. One may employ mixed fatty acids, as, for example, the fatty acids obtained by hydrolysis of cottonseed oil, soyabean oil, corn oil, etc. Our preferred demulsifler is obtained from unsaturated fatty acids, and more speciiically, unsaturated fatty acids containing a hydroxyl radical or unsaturated fatty acids which have been subjected to oxidation or oxyalkylation,

such as oxyethylation.

The esteramides of the kind herein .described may be obtained in any conventional manner. They are usually derived from the hydroxylated low molal acids themselves; but if desirable, the

functional equivalents, such as the anhydrides,

acyl chlorides, or other derivatives, may be em ployed. Suitable acids include hydroxyacetic acid (glycollic acid), hydroxypropioni'c acid (lactic acid), and others. It is not intended to include polybasic hydroxy acids. Not only may alphahydroxy acids be employed, but one may also employ the betahydroxy acids, for instance,

betahydroxy butyricacid, betahydroxy propionic I acid, etc. The objection to the use of such betahydroxy acids which contain a hydrogen atom on the alpha carbon atom, is that they are rather unstable. Thus, on heating, they lose the elements of water, forming unsaturated acids. This is illustrated by the formation of acrylic acid from betahydroxy propionic acid.- For all practical purposes, the two hydroxy acids most suitable are lactic acid-and hydroxy acetic acid. In some Harris instances, there are available derivatives of acids such as ethanolacetic acid, propanolacetic acid, and the like. See U. 5. Patent No. 2,238,928. dated April 22, 1941, to Cahn and Harris, and particularly Example 51 on page 3. Note particularly Examples 64-66 on page 4. If such acids be considered as derivatives of hydroxyacetic acid, and obtained hypothetically by an oxyalkylation reaction involving alcoholic hydroxyl radical of hydroxyacetic acid, and ethylene oxide, then it is apparent that analogous compounds would be derivable by the use of glycid. In this connection note Examples 69 and 70 of the aforementioned Cahn and Harris patent. In actual manufacture these particular types of acid are obtainable by other means.

The amide of such low molal hydroxy acid may be treated with an oxyalkylating agent, such as ethylene oxide, propylene oxide, butylcne oxide, or the like, so as to produce a compound of'the following type:

Actually, the alkylene radical might represent an equivalent divalent radical, in which the carbon atom chain is interrupted at leastonce by oxygen, as

Having obtained a bis(hydroxyalkyl)amide of the kind described, such compound can then be reacted in a conventional manner with a high molal acid or its equivalent, to give an esteramide, in other words, a compound of the following type:

alkylene.0H

0 alkylcnabOCR IJ R N alkylens.0H

A procedure that is frequently more readily adaptable is simply the reaction between a low molal acid, such as acetic acid, and a material of the kind exemplified by diethanolamine, dipropanolamine, or the like. For the sake of brevity, reference hereafter will be made largely to diethanolamine and hydroxyacetic' acid, although other suitable reactants have already been described. The method of manufacturing esteramides is sowell known that no further description is required; but for convenience, the following example is given in substantially verbatim form, as it appears in U. S. Patent-No. 2,238,928, dated April 22, 1941, to Cahn and Example 0 tion product was a reddish brown, water-soluble,

somewhat viscous material and comprised largely or essentially the lactic acid amide of diethanolamine.

(2) 37.3 grains of the lactic acid amide of dieued for 20 minutes at degrees C., for 20 minutes at degrees C., for 20 minutes at degrees C.,\and for 15 minutes at degrees C."

Previous reference has been made, however, to the fact that our preference is to use hydroxyacetic acid, due to its low cost and ready availability.

Illustrating somewhat similar types of reactions, see U. S. Patent No. 2,238,902, dated April 22, 1941, to Katzman and Harris; and also U. S. Patent No. 2,267,180, dated April 30, 1941, to Munz and Troskan.

In view of what has been said, it will be obvious that hydroxylated esteramides of the kind herein employed as reactants, may be obtained in various manners, including those described in the patents previously mentioned. As illustrating such hydroxylated esters, reference is made to the following formulas:

fl) CaHaOOCR'OH RON O CgHtO O C R" 0 CaHaOOOR'OH \RIII 0 CsHaOOCR'OH CsHaOH O CzHtOOCR'OH In the above formulas, RCO represents the acyl radical derived from a hydroxylated acid having 5 carbon atoms or less, such as hydroxyacetic, hydroxypropionic, hydroxybutyric, etc. OI-IIR'CO represents the acyl radical of a hy droxylated acid, such as ricinoleic acid, hydroxystearic acid, or similar acids obtained by oxidation, such as blown oleic, acid or acids obtained by the hydrolysis of blown olein. Such acyl radicals all contain at least 8 and not more than 32 carbon atoms and are apt to contain 18 car bon atoms. R"CO is the acyl radical derived from a non-hydroxylated monocarboxy detergent-forming acid, particularly an unsaturated acid, such as oleic acid, linolenic acid, etc. It is understood, of course, that a mixture of fatty acids might be employed instead of a single fatty acid. R"' is a hydrocarbon radical having 4 to 12 carbon atoms.

In examining the above formulas, it is to be noted that comparable products might be obtainable from monobutanolamine, dibutanolamine, monopropanolamine, dipropanolamine, monoglycerylamine, diglycerylamine, or the like, instead of being derived from monoethanolamine or diethanolamine. Similarly, the products shown in the last two formulas are derived from tris- (hydroxymethyl) aminomethane- Similar derivatives may be derived from 2-amino-2-ethyl-1,3- propanediol and 2-amino-2-methyl-1,3 propanediol.

The hydroxylated esteramides may, of course, be derived in any other suitable'way, such as reaction with ammonia, followed by oxyethylation, or some other suitable process. Thus, the low molal acids themselves, or, if desirable, the functional equivalents, such as the a'nhydrides, acyl chlorides, or other derivatives, may be reacted with ammonia, or a primary amine, such as any suitable alkylamine, or an alicyclic amine, or an aralkylamine. to give the amide'or substituted amide; in any event, a compound .containing at least one amino hydrogen atom. Suitable amines include butylamine, amylamine, octylamine, decylamine, cyclohexylamine, benzylamine, phenylamine, etc. Generally speaking, when an amine is used instead of ammonia for reaction with the low molal hydroxyl acid, one may employ a hydroxylated detergent-forming acid such as ricinoleic acid, in order to insure a plurality of available alcoholic hydroxyl groups for subsequent reaction with the polybasic carboxy acid or its equivalent. However, even if a non-hydroxylated detergent-forming acid, such as oleic acid, is employed, there still is available under any circumstances at least one alcoholic hydroxyl radical, to wit, the hydroxyl radical or radicals of the low molal acyl radical.

In this connection it may be well to point out the following: By considering the reaction involving hydroxyacetic acid and butylamine, the substituted amide so obtained can be reacted with a polybasic carboxyacid or its equivalent without further modification. However, the most desirable type of demulsifying agent, and for that matter, the most desirable type of compound for other purposes. is derived from such low molal amides as are characterizedby a plurality of alcoholic hydroxyl radicals." Thus, if the substituted amide obtained by reaction between butylamine and hydroxyacetic acid is treated with ethyleneoxide, glycid, or the like, and then reacted with oleic acid or some equivalent nonhydroxylated high molal acid, one still has availticularly as deinulsiflers, must present a rather peculiar structure when hydroxylated low molal acids are used, in light of the fact that either one, or possibly both, of the following structural arrangements may occur, to wit:

(a) A molecular arrangement whereby a phthalic acid radical or its equivalent is attached directly to the low molal acyl radical, as differentiated from being attached in an altogether different position to a ricinoleyl radical or an ethanol radical; or

(b) There would be present a terminal hydroxymethyl group, or its equivalent, as, for example, when derived from hydroxyacetic acid; and thus such a terminal radical would be distinctly hydrophile in character, as compared with the ordinary methyl radical appearing in acetic acid or the like.

Other procedures suggest themselves for preparation of compounds having a plurality of alcoholic hydroxyl radicals. For instance, in the case of compounds derived from butylamine, cyclohexylamine, benzylamine, or the like, one might use glycld or the like as an *oxyalkylating agent. Another procedure involves preparing the amide from ammonia and treating such amide with an oxyalkylating agent, such as ethylene oxide, propylene oxide, butylene oxide, glycid, or the like, to produce a compound of the following type:

0 alkylenc.OlI

,RCN

alkyleuc. 0 ll Actually, the alkylene radical might represent an equivalent divalent radical in which the carbon atom chain is interrupted at least once by oxygen;

' i.'e., the low molal amide, instead of being treated with two moles of ethylene oxide or the like, might be treated with four moles or six moles of ethylene oxide, or even more.

Previous reference has been made to the fact that the preferred compounds or demulsifiers are derived from hydroxyacetic acid, unsaturated fatty acids, particularly ricinoleic acid, etc. The type of amide which we prefer to employ for reaction with phthalic anhydride or the like, may be illustrated by the following:

Esteramide, Example 1 amine; and after the amide has been formed in able a plurality of alcoholic hydroxyl radicals. I

However, on treatment of such amide with ethylene oxide, glycid, or the like, at least under certain conditions, there is formed to a very minor degree amides of certain low molal-acids of the kind previously described; i. e., it is exemplified by ethanolacctic acid. As a matter of fact, however, it is our preference that even under such circumstances, i.- e.-, even where there is a plurality of alcoholic hydroxyl radicals present, the high molal acid also contain a hydroxyl group.

Thus, ricinoleic acid is the preferred reactant employed to supply the high molal acyloxy radical; and in such instance, the hydroxyl radical, which is part of the ricinoleyl radical. would serve as a reactive function for combination with phthalic anhydride or the like by esteriflcation.

In this connection, it may be pointed out that.

such compounds herein contemplated, and parsubstantial yield, the mass is then reacted with one pound mole of ricinoleic acid so as to form the ester.

Esteramide, Example 2 One pound'mole of diethanolamine is substituted for monoethanolamine in Example 1, preceding.

Esteramide, Example 3 methyl) aminomethane, bis(hydroxymethyl)aminomethane, and the like, are substituted in place of monoethanolamine and diethanolamine in Examples 1 and 2, preceding.

Esteramide, Example 4 Oleic acid is substituted for ricinoleic acid in Examples 1-3, preceding.

Esteramide, Example 5 owalkylation process with 1-2 moles of ethylene oxide, propylene oxide, butylene oxide, glycidyor the like.

Esteramtde, Example 6 Methyl lactate isemployed in the manner previously indicated to produce lactic acid derivatives instead of hydroxyacetic acid derivatives.

In any event, the reaction of the hydrmlated esteramide of the kind described with a polybasic carboxy acid or its functional equivalent,

such as the anhydride, is a well-known reaction and is nothing more or less than an esterification' reaction of the kind employed to produce phthalated castor oil, phthalated ricinoleoamide, etc. For instance, common comparable reactions are described in U. S. Patent No. 1,976,602, to De Groote, Kelser and Adams, dated October 9, 1934, and U. 8. Patent No. 2,078,652, to De Groote and Keiser, dated April 27, 1937.

Briefly stated, the molar combinations of the reactions selected depend upon the available number of hydroxyl groups and may be illustrated by the following examples:

Final product, Ezample 1 One pound mole ofa polyhydroxylated esteramide of the kind exemplified by Esteramide, Examples 1-5, preceding, is reacted with one pound mole of phthalic anhydride at approximately 145-165 C. until esteriflcation is complete, as indicated by the substantial elimination of one alcoholic hydroxyl radical. The product so obtained has one free carboni radical.

Final product, Example 2 The same procedure is followed as in the preceding Final product, Example 1, except that the esteramide' employed is the kind exemplified by Esteramide, Example 6, instead of Esteramide, Examples 1-5, inclusive.

Final product, Example 3 The same procedure is followed as in Final product, Examples 1 and 2, except that two moles of phthalic anhydride are employed instead of one mole; and the final product is characterized by the presence of two free carboxyl radicals.

Final product, Example 4 Insofar that some of the esteramides described in Esteramlde, Examples 1-6, inclusive, may have more than two alcoholic hydroxyl groups per molecule, one may employ the same type of reaction as described in the examples immediately preceding, except that the maximum amount of phthalic anhydride which can be employed from a stoichiometrical standpoint is employed; and thus the final product of reaction has a plurality of carboxyl groups and a substantial absence of hydroxyl groups. 1

Final product, Example 5 tinuously distilled under a reflux condenser, conhydride is employed, water may not be formed If desired, one may pass a dried, inert gas, such as dried nitrogen gas, through the mass to hasten esteriflcation. Esteriflcation is also hastened at times by the presence of a mere trace of a suitable acid, such as benzene sulfonic acid. In other instances, the reaction is most suitably conducted in the presence of an inert high boiling solvent, such as xylene. The xylene is condensed by such condenser, and returned to the reaction chamber through a trap. The xylene vapors carry off the water, which is removed after being condensed by the trap. This is a conventional procedure, commonly employed in this type or similar types of reaction.

Although we prefer to use phthalic anhydride as the most desirable source of the polybasic carboxy acid, one may use other polybasic carboxy acids or their anhydrides, such as succinic, malic, fumaric, citric, maleic, adipic, tartaric. glutaric, diphenic, naphthalic, oxalic, pimelic, suberic, azelaic, sebacic, etc. Naturally, a simple derivative of a polybasic acid, such as chlorophthalic acid, can be used as advantageously as phthalic acid itself, although there is no added advantage in the use of the more costly chemical compounds.

In view of the large number of reactants and types of materials described, it may be well to note those which we particularly prefer. It has been ointed out that we prefer to use unsaturated fattyacids as the source of the high molal acyloxy radical, and particularly the hydroxylated fatty acids commonly available, to wit, rici noleic acid. We prefer to use phthalic acid, maleic acid, or their anhydrides, or oxalic acid as the source of the polybasic carboxy acid. We prefer to use hydroxyacetic acid or its equivalent as the source of, the low molal acyl radical. We prefer to use monoethanolamine or diethanolamine as the reactant for formation of the substituted amide employed for subsequent reaction to produce the esteramide.

In view of what has been said, it is apparent that the hydroxylated esteramides of the kind described previously may be considered, for the sake of simplicity, as being in the class of an alcohol, i. e., a monohydric or polyhydric alcohol. If an alcohol is indicated by the formula Y'(OI-I)s, where 1: indicates the number 1 or more, and if a polybasic acid body be indicated by the formula X'(COOH) n, where n indicates the number 2 or more, then the reaction between a monohydric alcohol and a olybasic acid will result in a compound which may be indicated by the following formula: X'Y' (COOI-I) I, wherein 11 indicates the number 1 or more, and which is in reality a eontraction of a more elaborate structural formula, in which X and Y are joined by a carboxyl radical or residue. Assuming, however, as would be true in the majority of cases, that the alcohol actually would be a polyhydric alcohol, and that residual hydroxyl radicals, or might result in compounds in which there were residual hydroxyl radicals, and no residual carboxyl radicals, or compounds where there might be residual carboxyl radicals and no residual hydroxyl radicals;

' or there might be both. This is indlcatedby the following:

(Y.X) (OI-I)1v (YX) (((COOH) 1n (OHMMYX) q(COOH) m" in which q indicates a small whole number (one in the case of a monomer, and probably not over 20 and usually less than and m and n indicate the number 1 or more, and m" and n" indicate zero or a. small or moderately-sized whole number, such as zero, one or more, but in any event, probably a number not in excess of 10-15.

Naturally, each residual hydroxyl could combine with a phthalic acid body or its equivalent, or with asimilar compound derived from a tribasic acid, such as citric acid; and in such event, there would be a. large number of free or uncombinedcarboxyl radicals present, possibly 20- or more. Actually, the preferable type of reagent would be more apt to include less than 20,

and in fact, less than 10 free hydroxyl radicals. It is not necessary to remark that the residual carboxyl radicals can be permitted to remain as such, or can be neutralized in any suitable manner, such as conversion into salts, esters, amides, amino esters, or any other suitable form. Usually, such conversion into salt form would be by means of sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, ammonium hydroxide, amylamine, bu'tanolamine, ethanolamine, diethanolamine, triethanolamine, cyclohexanolamine, benzylamine, aniline, toluidine, etc. Conversion into the ester would be by means of a monohydric alcohol, such as 23 cresol, anthracene oil, etc.

4 employed as diluents. Mi

such as pine oil, carbon tetrachloride, sulfur diin which the characters have their previous significance, and 11 represents a small whole number not greater than 5, and :2 represents a small whole number not greater than 5; Z represents a hydrogen ion equivalent, suchas metallic atom,

organic radical, etc. v

It will be noted that compounds of the type just described having atleast one hydrophobe nucleus are designated as being polar" when there is presenteither an unesterified hydroxyl radical, or an unesterified carboxyl radical, or both. We have found that the polar type of material is by far the most effective for demulsiflcation, and it is our preference to use such type; Indeed, this particular type is so much more eflective for demulsification than th non-polar type, that it may be considered in essence anv invention within an invention. I

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 oil, Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl lcohol, etc., may be llaneous solvents,

oxide extract obtained in the refining of petromethyl alcohol, ethyl alcohol, propyl alcohol, Y

alcohol, hexyl alcohol, octyl alcohol, decyl alcohol, ethylene glycol, diethylene glycol, glycerol, diglycerol, triethylene glycol, or the like. One could employ an amino alcohol so as to produce an ester.

We have found, however, as suggested, that the butyl mostsuitable products are sub-resinous, semiresinous, or balsam-like products, and are preferably derived from polyhydroxylated reactants, i. e., polyhydroxylated esteramides. We have found that such productsare soluble to a fairly definite extent; forinstance, at least 5% in some solvent such as water, alcohol, benzene, dichlorethyl ether, acetone, cresylic acid, or the like. This is simply another way of stating that it is preferable, if the product be one Of the sub-resins, which are commonly referred to as an A resin, or

- B resin, as distinguished from a C resin, which is a highly infusible, insoluble resin (see Ellis,

Chemistry of Synthetic Resins, 1935, page 862,

et seq).

In recapitulating what has been said previously, the sub-resinous, semi-resinous, or balsamlike product herein contemplated may be indicated by the following formula: I

I coon)...

leum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of our 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 b used in'a water-soluble form, or in an oil-soluble form, or in a form exhibiting both 'oil and water solubility. However, since such reagents are sometimes used in a ratio of 1 to 10,000,or 1 to 20,000, or even l-to 30,000, such an apparent insolubility in oiland water is not sig-' nificant, 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 our process. v

' We desire to point out that the superiority of the reagent or demulsifying agent contemplated in 'our 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 themajority-of oil field emulsions are concerned; but we 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 be treated as easily or at so low'a cost with the' demulsifying agents heretofore available.

In practising our process for resolving petroleum emulsions of the water-in-oil type, 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 coon).

(OID-KYI'XM) in which 2' and u are small whole numbers not greater than 10 and m, 1:, and m are small whole numbers notover l0, and including zero; Z is an acidichydrogen atom equivalent; and X is a residue derived from a polybasic carboxy acid; and Y is a residue derived from a hydroxylated esteramide containing (a) one amido-linked acyl radical derived from a hydroxylated carboxy .acid

having not over 5 carbon atoms; and (b) at least one acyloxy radical derived from a monocarboxy detergent-forming acid having a least 8 and not more than 32 carbon atoms, and linked by a divalent aliphatic radical to the amido nitroen atom,

2. A process for breaking petroleum emulsions of the water-in-oil type, which consists in sub- 7 jecting the emulsion to the action of a demulsifier comprising a polar sub-resinous esteriilcation product of the following formula type:

coon).

( m-(Yam I 0002 in which 1: and y are small whole numbers not greaterthan l and m, n, and m' are small whole numbers not over 10, and including zero; Z is an acidic hydrogen atom equivalent; and X is a residue derived from a polybasic carboxy acid; and Y is a residue derived from a hydroxylated esteramide containing (a) one amide-linked acyl radical derived from a hydroxylated carboxy acid having not over carbon atoms; and (b) at least one acyloxy radical derived from a monoearboxy detergent-forming'acid having at least 8 and not more than 32 carbon atoms, and linked by a divalent aliphatic radical to the amido nitrogen atom.

3. A process for breaking petroleum emulsions of the water-in-oil type, which consists in subjecting the emulsion to the action of a demulsiiler comprising a polar sub-resinous esteriilcation product of the following formula type:

coon).

( m-OWL) (00oz)..- in which .1:' and u are small whole numbers not greater than 10 and 1n, n, and m are small whole numbers not over 10, and including zero; Z is an acidic hydrogen atom equivalent; and X is a residue derived from a hydroxylated esteramide containing (a) one amide-linked a yl radical derived from a hydroxylated carboxy acid having not over 5 carbon atoms; and (b) at least one acyloxy radical derived from a higher fatty acid having at least 8 and not more than 32 carbon atoms, and linked by a divalent aliphatic radical to the amido nitrogen atom.

4. A process for breaking petroleum emulsions of the water-in-oil type, which consists in subjecting the emulsion to the action of a demulsifier comprising a polar sub-resinous esteriilcation product of the following formula type:

in which 1:" and y are small whole numbers not reater than 10 and m, n, and m are small whole numbers not over 10, and including zero; Z is an acidic hydrogen atom equivalent; and X is, a residue derived froma polybasic carboxy acid; and Y is a residue derived from a hydroxylated esteramide containing (a) one amide-linked acyl radical derived from a hydroxylated carbon acid having not over 5 carbon atoms and (b) at least one acyloxy radical derived from a higher unsaturated fatty acid having at least 8 and not more than 32 carbon atoms, and linked by a divalent aliphatic radical to the amido nitrogen atom.

5. A process for breaking petroleum emulsions of the water-in-oii type, which consists in subiecting the emulsion to the action of a demulsifier comprising a polar sub-resinous esteriflcation product of the following formula type:

)n( s' Sc 0 0.2)

in which :0 and 1' are small whole numbers not greater than 10 and m, n, and m are small whole numbers not greater than 10, and including zero; Z is an acidic hydrogenatom equivalent; and X is a residue derived from a polybasic carbon acid; and Y is a residue derived from a hy- 00 0H) BA -Xvi in which 2: and 11 are small whole numbers not greater than 10 and m, n, and m are small whole numbers not over 10, and including zero; Z is an acidic hydrogen atom equivalent; and X is a residue derived from a polybasic cerboxy acid, and Y is a residue derived from a hydroiqrlated esteramide containing (a) one amide-linked acyl radical derived from a hydroxylated carboxy acid having not over 5 carbon atoms and (b) at least one ricinoleyl oxy radical, and linked by a divalent aliphaticradical to the amido nitrogen atom. 1

7. A process for breaking petroleum emulsiml of the water-in-oil type, which consists in sub- Jecting the emulsion to the action of a demulsi fler comprising a polar sub-resinous ester-incain which at and y are small whole numbers not. greater than 10 and m, n, and m. are'small whole numbers not over 10, and including zero; -Z is an acidic hydrogen atom equivalent; and X is a residue derived from a dibasic carboxy acid; and Y is a residue derived from a hydroxylated esteramide containing (a) one amido-linked acyl radical derived from a hydroxylate'd carboxy acid having not over carbon atoms and (b) at least one ricinoleyl oxy radical, and linked by a divalent aliphatic radical to the amido nitrogen atom.

8. A process for breaking petroleum emulsions of the water-in-oil type, which consists in subjecting the emulsion to the action of a demulsifier comprising a polar sub-resinous esteriflca- 4 tion product of thefollowing formula type:

I (coon).

(oH .(Y,'x.')

in which 1: and u are small whole numbers not greater than and m, n, and m are small whole numbers not over 10, and including zero; Z is an acidic hydrogen atom equivalent; and x is a residue derived from phthalic acid; and Y is a residue derived from a hydroxylated esteramide containing (a) one amido-linked acyl radical derived from a hydroxylated carboxy acid having not over 5 carbon atoms and (b) at least one ricinoleyl oxy radical, and linked by a divalent f aliphatic radical to the amido nitrogen atom.

9. A process for breaking petroleum emulsions of the water-in-oil type. which consists in subjecting the emulsion to the action of a deinulsiviier comprising a polar sub-resinous esteriflcation product of the following formula type:

(COOK),-

DK I' W) in which :0 and y are smallwhole numbers not greaterthan 10 and m, n, and m are small whole numbers not over 10, and including zero; Z is 10 an acidic hydrogen atom equivalent; and X is a residue derived from maleic-acid; and Y is a residue derived from a hydroxylated es teramidecontaining (a) one amido-linked acyl radical derived froma hyroxylated carboxy acid having not over 5 carbon atoms and (b) at least one derived from a ricinoleyl oxy radical, and linked by a divalent aliphatic radical to the amido nitrogen atom.

10. A process for breaking petroleum emulsions of the water-in-oil type, which consists in subjecting the emulsion to the action of a demulsitier comprising a polar sub-resinous esteriflc'ation product of the following formula type:

coon).

(Oman) 0 o o .z) w

in which x and u are small whole numbers not greater than 10 and m, n, and m are small whole numbers not over 10, and including zero; Z is anacidic hydrogen atom equivalent; and X is a residue derived from oxalic acid; and Y is a resi-- due derived from a hydroxylated esteramide containing (alone amido-linked acyl radical derived from a hydroxylated carboxy. acid having not over 5 carbon atoms; and (b) at least one ricinoleyl oxy radical, and linked by a divalent aliphatic radical to the amido nitrogen atom.

mmvm DE oaoo'rn BERNHARD xmsnn.