US2306329A - Process for breaking petroleum emulsions - Google Patents

Description

PROCESS FUR RE i G IPIETOLIE JESIIONS ware No Drawing. Application .lfune 2'], 19%,

- Seriai No. M21315 x t @lairns.

This invention relates primarily to the treatment of emulsions of mineral oil and water, such as petroleum emulsions, for the purpose of separating the oil from the water.

"One object of our 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 theoil 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 petroleum and relatively soft waters or weak brines.

Controlled emulsification and subsequent demul siflcation under the conditions just mentioned is of significant value in removing impurities, particularly inorganic salts, from pipelin oil.

The demulsifier or demulsifying agent em Ployed in our process consists of a compound or mixture of compounds that comprises the asy tion product of a high molecular weight carboxy acid and a polyamine of the kind hereinafter described. Said compound or mixture of compounds are characterized by the presence of a certain type of acyl radical in the acylated compound, as hereinafter described. The acid radical may be derived from any suitable high molecular weight carboxy acid. In order that our invention may be clearly understood, we will hereinafter give several examples of chemical compounds suitable for use in practising our process; and we will explain how said compounds can be produced or obtained.

The expression higher molecular weight carboxy acids is an expression frequently employed to refer to certain organic acids, particularly monocarboxy acids, having more than six carbon atoms, and generally less than 40 carbon atoms.

e commonest examples include the detergentf'orming acids, 1. e., those acids which combine with alkalles to produce soap or soap-like bodies. The detergent-forming acids, in turn, include naturally-occurring fatty acids, resin acids, such as abietic acid, naturally-occurring petroleum acids, such as naphthenic acids, and carboxy acids produced by the oxidation of petroleum. As will be subsequently indicated, there are other acids which have somewhat similar characteristics and are derived from some what diflerent sources and are erent in structure, but can be included in the broad generic term previously indicated.

Among sources of such acids may be mentioned straight chain and branched chain, saturated and unsaturated, carboxylic, aliphatic, alicyclic, fatty, aromatic, hydroaromatic, and aralkyl acids, including caprylic acid, butyric acid, heptylic acid, caproic acid, capric acid, pimelic acid, sebacic acid, erucic acid, saturated and unsaturated higher molecular weight aliphatic acids, such as the higher fatty acids containing at least eight carbon atoms, and including, in addition to those mentioned, melissic acid, stearic acid, oleic acid, ricinoleic acid, diricinoleic acid, triricinoleic acid polyricinoleic acid, ricinostearolic acid, ricinoleyl lactic acid, acetylricinoleic acid, chloracetyl-ricinoleic acid, linoleic acid, linolenic acid, lauric acid, myristic acid, undecylenic acid, palmitic acid, mixtures of any two or more of the above mentioned acids or other acids, mixed higher fatty acids palm kernel oil, palm oil, olive oil, corn oil, cottonseed oil, sardine oil, tallow, soyabean oil, peanut oil, castor oil, seal oils, whale oil, shark oil, and

other fish oils, teaseed oil, partially or completely hydrogenated animal and vegetable oils, such as those mentioned; hydroxy and alpha-hydroxy higher carboxylic, aliphatic and fatty acids, such as dihydroxystearic acid, dihydroxy palmitic acid, dihydrpxybehenic acid, alphahydroxy capric acid, alphahydroxystearic acid, alphahydroxy palmitic acid, alphahydroxy lauric acid, alphahydroxy myristic acid, alphahydroxy cocoanut oil mixed fatty acids, alphahydroxy margarlc acid, alphahydroxy arachidic acid, and the like; fatty and similar acids derived from various waxes, such as beeswax, spermacetti, montan wax, Japan wax, coccerin, and carnauba wax. Such acids include carnaubic acid, cerotic acid, laccerlc acid, montanic acid psyllastearic acid, etc. As suggested, one may also employ higher molecular weight carboxylic acids derived, by oxidation and other methods, from paraffin wax, petroleum and similar hydrocarbons; resinic and hydroaromatic acids, such as hexahydrobenzoic acid, hydrogenated naphthoic, dehydrogenated carboxy diphenyl, naphthenic, and abietic acid; aralkyl and aromatic acids, such as benzoic acid, Twitchell fatty acids, naphthoic acid, carboxydiphenyl pyridine carboxylic acid, hydroxybenzoic acid, and the like. e

Other suitable acids include phenylstearic acid, benzoylnonylic acid, campholic acid, fencholic acid, cetyloxybutyric acid, cetyloxyacetic acid, chlorstearic acid, etc.

Alkylene polyamines, characterized by the fact that two or more amino nitrogenatoms are joined by an alkylene radical, are well known. Such compounds may be either open chain compounds of the following general formula:

where a: is a whole number; or they may be ring compounds having the general formula:

. where :c is a whole number. The first group is exemplified by diethylene triamine,

(NHa.C2H4-NH.C2H4.NH2)

triethylene tetramine,

(NH:.C2H4.NH.C2H4.NH.C2H4.NH2)

and tetraethylene pentamine,

(NH2.C2H4.NH.C2H4.NH.C2H4.NH.C2H4.NH2) examples of the second group are diethylene di- In the above formulas the radical C2H4 is simply a divalent linking radical. Thus, preceding 3% formulas maybe rewritten as follows:

'I E NH )mr) 'r T 'r 'r NH.T.NH/

in which T represents any suitable divalent linking radical. O

We have discovered that if T is an oxygenated divalent linking radical of the kind to be described, and if such polyamines are acylated so as to introduce an acyl radical from a high molecular weight carboxy acid of the kind previously defined, one obtains a new composition of matter and a compound or a variety of compounds which are particularly effective as de- I mulsifiers for water-in-oil emulsions.

Generally speaking the oxygenated divalent linking radical is exemplified by three types: the keto type, in which the conventional carbonyl linkage appears; the ether type, in which the conventional ether linkage appears; and the hydroxylated type, in which the conventional alcoholic hydroxyl radical appears. One of the best known examples are compounds obtained from pW-diclfloralml ethers instead of alkylene dichlorides. Such compounds are characterized by "Hi asoaaaa the preceding formulas, if one adds the proviso that in such formulas T shall represent the divelent radical CHzCHzOCHzCI-Iz. As to the manufacture of such compounds, see U. S. Patent No. 1,919,301, dated July 25, 1933, to Morton. Said patent is concerned largely with compounds contalning an aryl radical; but of course the same procedure is equally effective in connection with ammonia or amines free from an aryl radical and containing at least one reactive hydrogen atom; i. e., the selected amines must be primary or secondary. Furthermore, one is not limited to the ethyl ether halogen derivative; but one may use the propyl ether halogen derivative or any other suitable compound. If derived from ammonia, such diamines may be alkylated in the manner commonly employed for alkylating ordinary amines, i. e., monoamines. Alkylation may result in products which are symmetrically or non-symmetrically alkylated. The symmetrically alkylated diamines are most readily obtainable. For instance, alkylated products may be derived by reaction between alkyl chlorides, such as propyl chloride, butyl chloride, amyl chloride, cetyl chloride, and the like. .Such reaction products result in the formation of hydrochloric acid, and the resultant product consists of an amine hydrochloride. The conventional method for conversion into the base is to treat with dilute caustic solution. Alkylation is not limited to the introduction ofen alkyl group; but as a matter of fact, a radical may be introduced characterized by the fact that the carbon atom chain is interrupted at least once by an oxygen atom. In other words, alkylation may be accomplished by compounds which are essentially alkyloxyalkyl chlorides, as, for example, the following:

As a matter of common knowledge, reactions involving ammonia and an alkyl ether dichloride probably go through an intermediate stage which involves the formation of aminoalkyl ether halide. As a result, one has another suitable procedure for manufacture of the diamines, i. e., a reaction involving aminoalkyl ether halides and a monoamine. See British Patent No. 292,615, to I. G. Farbenindustrie A.-G., application date in the United Kingdom June 22, 1928.

As has been previously stated, the reaction involving the alkyl ether dichlorides is not limited to ammonia, but may involve amines, such as ethylamine, propylamine, butylamine, octylamine, decylamine, cetylamine, dodecylamine, etc. Similarly, the reaction may involve the comparable secondary amines, in which various alkyl radicals previously mentioned appear twice and are types in which two dissimilar radicals appear, for instance, amyl butylamine, hexyl octylamine, etc. Furthermore, compounds may be derived by reactions involving alkylene dichlorides and a mixture of ammonia and amines, or a mixture of two different amines.

It is known that there are numerous other compounds which are akin to the dichloralkyl ethers, in that they are labile or reactive alphaomega-dichloro derivatives. Thus, well known reactants which supply a divalent linking radical of the kind indicated by T in previous formulas include: dichlorodiethyl ether (C1C2H4oC2H4C1); triglycol dichloride; tetraglycol dichloride; dichlorodiisopropyl ether. (C1C3H7OCsH7Cl); dichlorodiisobutyl ether (C1C4H9OC4HBC1); glycerol 01 550 0135C] CaHuO CaHuCl dicchlorhydrin; methyl glycerol dichlorhydrin;

(slei ht-013301) derived from acetone; dichlormethylpropyl ketone cmcl (are OCH/ cmoi etc.

Various other procedures may be employed producing polyamines of the kind described. For instance, reference is made to our co-pending application" for patent Serial No. 273,278, filed May 12, 1939. In said application there is described the conversion of triethanolamine into an alcoholate, such as a monoacoholate, by means of caustic soda and the like, and subsequently uniting two moles of such compound by means of a material such as glycerol dichlorhydrin. Similarly, th dialcoholate might be treated in the same manner. Incidentally, such alcoholates may be derived from hydroxyalkyl ethers of tertiaryamines, as well as materials of the kind exemplified by triethanolamine. See U. S. Patent No. 1,923,178, to Ulrich, Nuesslein, and Koerding, dated August 22, 1933.

Other suitable procedure involves hydroxyamines, such as diethanolamine, an aldehyde, particularly formaldehyde, and a ketone or polyketone having present alpha-hydrogen atoms. As to such general reactions, see U. S. Patent No. 1,071,007, to Merling, dated August 19, 1913.

In the manufacture of certain diamines and their obvious modifications, which can be made in many instances to yield higher polyamines, i. e., analogous or comparable products having at least three amino nitrogen atoms, generally speaking, if the amine or if ammonia is treated with a reactant having a divalent linking radical and two labile halogen atoms, such as chlorine atoms, one is apt to obtain varying amounts of such higher polyamines. For the sake of brevity, further indications will be'limited to procedures for making various suitable polyamines. Such suitable polyamines will be the following:

3 C 3 C H ah- 3 a)2 N H 1 1E;

C H (O H) Cfiz CH: (once- 5 i=(cm),

1 1B: NH: (See German Patent No. 96,657, March 1, 1898.) 50

ClHe v CHz-C H2-N O CHr-CHr-OH (A) CHrCHr-OH CRT-C Hr-N NH--CH2C H-C H3 H: H DH-O H 6B: OH Il IHCHr-( 3H-C Ht Th (See German Patent No. 635,904, to I. G. Farbenindustrie, A.-G., dated October 1, 1936.) H /H N-CHsCHOHCHz-N H rncnonomNm N- (2-hydrow-3-aminopropyl) -2-hydroxy propylene diamine-1,3.

n a N-omcrronom-N NmcmcHoaoH omononcumm N,N'-di(2-hydroxy-3-amino propyl) -2-hydroxy propylene diamine-1,3. (See U. S. Patent No; 2,046,720, to Bottoms, dated July 7, 1936.) See also U. S. Patent No. 2,132,074, to Kartaschoff and Aeschlimann, dated October 4, 1938.

Among products commercially available is 1,3- diamino-Z-propanol, which is an especially suitable reactant.

It has been pointed out that polyamines of the kind previously described may be produced or reacted in such a manner that the amino hydrogen atom is replaced by an alkyl radical, a hydroxyalkyl radical, a hydroxyalkyloxyalkyl radical, or the like. It is well known that certain other modifications can be obtained by conventional procedure. For instance, one may introduce acyl radicals derived from acids having six carbon atoms or less, such as acetic acid, butyric acid, and the like. Such products are obtained by treatment with acetic anhydride, acetyl chloride, or equivalent reactants. Furthermore, it is known that one can obtain derivatives of amines or the kind described by reactions with chlorhydrins derived from polyglycols, polyglycerols and the like, such as diglycerol chlorhydrin, the chlorhydrin derived from the dihydric alcohol obtained by etherizing two moles of diethylene glycol, etc. Similarly, amino hydrogens may be substituted by reaction with compounds of the kind typified by ethyl chloracetate, i. e., esters of carboxy acids in which an alpha hydrogen has been substituted by chlorine. Similarly, as has been suggested previously, aminoalkyl chlorides may be employed so as to introduce an aminoalkyl group. As an example of such aminoalkyl halide, reference is made to the description of certain examples found in U. S. Patent No. 2,014,077, dated September 10, 1935, to Wilson. As will be pointed out subsequently, the intention is to introduce an acyl radical derived from a higher molecular weight carboxy acid. In some ininstancis amides already containing such acyl radical may be treated with the reactant containing a linking radical of the kind described. Furthermore, in certain instances polyamines such as dlamines may be employed. Certain other compounds may be looked upon as instances in which one of the amino hydrogen atoms of a polyamine, particularly a diamine, has been replaced by an aminoalkyl group. For instance, one might react two moles of oleyldiethyl ethylenediamine with one mole oipfidichlorethyl ether. For the sake of brevity, in the hereto appended claims the expression alkyloxyalkyl is intended to include the type of oxyhydrocarbon radical where the hydrocarbon chain is interrupted more than once by an oxygen atom. Similarly, since materials such ethyl chloracetate are sometimes spoken of as alkylating agents, it is intended that the expression "alkyl will include the type of radical so introduced, i. e., a radical exemplifled by the following:

CHzCOOCzHs although strictly speaking. it is not, of course, an alkyl radical.

Summarizing what has been said thus far, it is apparent that one could readily obtain amines of the following type:

in which a: is a small whole number less than but including zero, T has its previous significance and D may be hydrogen, alkyl, alkylol, hydroxyalkyloxyalkyl, arninoalkyl, R'COB'CQOX, and R'C0.0K', in which R'CO is an acyl radical derived from a lower molecular weight carboxy acid having six carbon atoms or less; R'CODX is a radical in which OX represents a divalent radical obtained at least hypothetically by the removal of a hydroxyl hydrogen atom from an allwlol radical; and R'CODX denotes a radical in which OX represents a radical derived, at least hypothetically, by the removal of a hydroxyl hydrogen atom from a hydroxyalkyloxyalkyl radical.

If one adds the proviso that there must be a reactive hydrogen atom present in such polyamine, i. e., a hydrogen atom linked to a nitrogen atom or to an oxygen atom, one then has an acylation-reactive polyamine. In other words, such polyamine can be acylated so as to introduce a high molecular weight carboxy acid acyl group in the same manner that any other amine can be acylated, i. e., an ordinary monoamine or dlamine. Thus, the methods for acylating ordinary monoamines which are primary or secondary are well known. Likewise, a suitable procedure for acylating diamines, including hydroxylated diamines, is well known. In such instances one employs a suitable acid or any functional equivalent. For convenience, amines of the above type which can be acylated, i. e.,

have present a reactive hydrogen atom, will be 1 referred to as acylation-reactive amines. 'Such acylation products may be of the amide type; in other words, of a type in which the acyl group is directly attached to the amino nitrogen atom; or they may be of the ether type, where the acyl group replaces a hydroxyl hydrogen atom, and thus is linked to a nitrogen atom through a carbon chain; or the acylation derivative may exemplify both types, where the amine employed as a rawmaterial has present at least one amino hydrogen atom and at least one hydroxyl hydrogen atom. A's has been previously stated, it is unnecessary to describe to any length the method of producing the acylation products, except to indicate that the same means may be employed as in connection with the acylation of any ordinary amine, whether a monoamine or a diamine. Attention is also directed to the fact that after acylation of the polyamines herein described, the subsequent reaction product, i. e., the acylation reaction product, if it still contains a reactive hydrogen atom, may be reacted with an oxy-,

alkylating agent, such as ethylene oxide, propylene oxide, and the like, so as to introduce oxyalkyl radicals, for instance, with the result that an amino hydrogen atom is converted into a hydroxyethyl radical.

As to the conventional procedure for the acylation of polyamines, regardless of type, reference is made to the following U. S. patents: No. 1,924,698, to Neelmeler, Nocken, and Friedrich, dated August 29, 1933; No. 1,947,951, to Neelmeier,

Noclten and Friedrich, dated February 20, 1934;

aeoaeaa No. 2,075,109, to Friedrich, dated March 30, 1937; and No. 2,008,649, to Ulrich and Nuesslein, dated July 16, 1935.

It is understood that the new composition of matter herein contemplated and adapted particularly for use as a demulsifler, may be prepared in any suitable manner. It is not intended that the hereto attached claims be limited in any respect as to the method of manufacture, unless such method of manufacture is specifically recited. As has been stated, it is our preference to obtain an acylation-reactive amine of the type or kind just described, and react the same with a higher molecular weight carboxy acid or its functional equivalent. It is our preference to use the detergent-forming acid type, which includes fatty acids, resin acids, and petroleum acids. Such petroleum acids may be naturally-occurring. acids, such as naphthenic Example 1 One mole of 1,-3-diamino-2-propanol is acylated with one mole of riclnoleic acid, using a temperature of approximately C. The temperature is allowed to rise as acylation takes place.

Example 2 Oleic acid is substituted for ricinoleic acid in the above examples.

Example 3 A non-fatty, detergent-forming acid, such as purified naphthenic acid, abietic acid, or petroleum acids derived by the oxidation of paraffin, is substituted for ricinoleic acid in Example 1.

Example 4 One mole of N'-(2-hydroxy-3-amino propyl) 2-hydroxy propylene diamine-1,3 is acylated with three moles of ricinoleic acid. A higher temperature may be suitably employed, for instance, a temperature of approximately C.

Example 5 In the preceding example, other suitable detergent-forming acids of the kind referred to in Examples 2 and 3 preceding are substituted for ricinoleic acid in Example 4.

Example 6 N,l-l-di(2-hydroxy-3-amino propyl) -2-hydroxy propylene diamine-1,3 is substituted for N-(2- hydroxy-3-amino propyl)-2-hydroxy propylene (Hairline-1,3 in the two preceding examples, to wit, 4 and 5.

Example 7 asoaaao U. S. Patent No. 2,049,467, to Nookin, dated March i, 1936. Having obtained a mixture of such polyamines, no particular effort is made to obtain a separation, but the mixture is employed as such. It is to be noted that an equally efiective amine can be obtained from amylamine or from octylamine, as from ammonia. Based on the average molecular weight, a suitable proportion of such amines is acylated with one or more of the various detergent-fonning acids described in the previous examples, and particularly by use of ricinoleic acid. The temperature of acylation preferably starts at the boiling point of the lowest amine present; but in any instance, one need not employ a temperature of over 200 C.

Example 8 One mole of a material of the kind indicated by Formula B preceding and made according to directions found in German Patent No. 6353M, is acylated with two moles of ricinoleic acid. The diamine used as a raw material is indicated structurally by the following formula:

NHCHr-CHOHa m (|)H on-n cm on NHCH2CHCH3 Example 11 Triethanolamine is converted into the mono:

alcoholate by treatment with caustic soda. Two' moles of the sodium alcoholate so derived are reacted with one mole of glycerol dichlorhydrin so as to yield a product of the following structure:

OHCzHl melon Noznioouiuomoolnm OHCzH4 C2H4QH Such material is then acylated with two moles of ricinoleic acid in the manner previously described, i. e., by heating for approximately 2-6 hours at rec-175 C.

Example 12 Various other detergent-forming acids of the kind previously described, such as oleic acid, naphthenic acid, abietic acid, oxidized petroleum acids, and the like, are substituted for ricinoleic acid in the preceding example.

Example 13 Hydroxyethyl ethylene diamine is treated with fifl'dichloroethyl ether in approximately the some manner indicated in aforementioned U. 8. Patent No. 1,909,301 to Morton. The product so obtained is a mixture but contains a substantial proportion of a material of the following composition:

In place of ricinoleic acid, in Example 12, various other detergent-forming acids are used, such as oleic acid, naphthenic acid, etc.

It is to be noted that no edort is made in the preparation of the compositions of matter herein contemplated to obtain any specific isomer unless so indicated by the structural formula. As far as we are aware, one isomer is Just as suitable as another for the various purposes indicated, and particularly, for use in the production of ademulsifier. What is said of the isomers in unacylated forms applies with equal force and effect to the acylated forms.

As has been previously stated. no particular directions are required in regard to such acylation procedure. Generally speamng one must employ a temperature below the boiling point of the amine employed, although as acylation takes place, the temperature may be permitted to rise. Many of the amines have boiling points above C. Under such circumstances, one can use a higher temperature and hasten the reaction, for instance, may employ a. temperature of 180 C. If the amine is especially low boiling, the pressure might be suitably employed and the reaction preferably conducted in such a manner as to remove the water of reaction.

One can obtain the amide ester type by acylating an amine in such a manner that more acyl groups are introduced than there are available either amino hydrogen atoms considered by themselves or alcoholic hydroxyl radicals considered by themselves. One can produce the ester type in a number of ways, for instance, by acylatlon of an amine which contains no amino hydrogen atom. One can produce the amino type by employing an amine which does not. contain hydroxyl radicals, i. e., the keto type or the ether type; or even if a hydroxyl radical is present, acylation can be conducted by means of an amide such as ricinoleoamide with the formation of an amine in the substantialabsence of any'water.

Previous reference has been made'to the introduction of an aminoalkyl radical in-place of an amino hydrogen atom. The availability of a compound of the following types:

would permit the intrwuction of a hydroxyalkylamino radical. However, the introduction of such type radical is more feasible by introducing an aminoalkyl radical from a compound such as, for instance, chloramylamine The use of such halide permits the introduction of the aminoalkyl radical NH2.CsH1o. Such radical, after being introduced into the polyamine nucleus, whether prior to or after acylation, can of course, be treated with an oxyalkylating agent, such as ethylene oxide, or any similar afiallrylene oxide or with glycid, epichlorhydrin and other reagents, so' as to convert one or both of the amino hydrogen atoms in the above described aminoalkyl radical into a hydroxyalkyl radical, or, in the case of ethylene oxide, into a C2H4OH radical. Needless to say, such a radical, which is in essence an alkylolamine radical, or an alkylolamine residue, can be acylated by acids of either high molecular weight or low molecular weight, in the same manner that has been described pre-' viously in regard to any alcoholic hydroxyl or amino hydrogen atom which happens to 1% present.

Attention is directed to the fact that the word "amidiflcation has been applied to the reaction involving the replacement of an amino hydrogen atom by an acyl radical, without conventional limitation to a reaction involving ammonia. The replacement, of the amino hydrogen atom of a primary amine or a secondary amine by an acyl radical, has been considered as Ming amidiflcation, rather than the formation of a substituted amide, or the formation of an imide or substituted imide. Such obvious departure from comventional nomenclatures has been for purposes of simplicity and to show the similarity between certain reactions.

In summary, it is obvious that the acylated derivative, i. e., the acylated polyamine containing at least one acyl radical derived from a high molecular weight carboxy acid, can be characterized by the following formulas:

inwhich a: is a small whole nummr, including 0, but in any event, less than 10, and preferably, 1 to 4; T is an oxyhydrocarbon radical selected from the class consisting of the keto type, the ether type, and the alcohol type; and D may be hydrogen, alkyl, @kyl'ol, .hydroxyalkyloxyalkyl, aminoalkyl, hydroxyalkylamino, RCO, RCQOX, BCQOX', RC0.0 RC0.0 R'CO, RCQOX, R'C0.0X, R'C0.0 and R'CQOX', in which RC0 is an acyl radical derived from a highermolecular weight carborw acid having more than six carbon atoms; R'CO is an acyl radical derived from a lower molecular weight carboxy acid having six carbon atoms or less; ,OX represents a divalent radical obtained at least hypothetically by removal of a hydroxyl hydrogen atom from an alkylol radical; 0X

represents a radical derived at least hypothetically by removal of a hydroxyl hydrogen atom from a hydroxyalkyloxyalkyl radical; OX" represents a divalent radical derived least hypothetically by the removal of an amino hydrogen atom from an aminoalkyl radical; and O represents a radical derived at least hYDQthetically by removal of a hydroxy hydrogen atom from a hydroxyalkylamino radical; and RCO must occur at least once.

It is to be understood that the compound herein contemplated may be manufactured in any suit-- able manner; and one is not dependent upon following the exact procedure previously outlined.

In certain instances the other reactants mig t be employed, or else reactants of the kind previously 7 described might be combined in some other manner. It is not intended that the hereto ap ended claims be limited in any manner whatsoever as to the method of manufacture, unless such method is-specifically recited.

Conventional demulsifying agents employed in the treatment oi oil field emulsions are used as such, or after dilution with any suitable solvent,

such as water-petroleum hydrocarbons, such as mixed 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 lmown 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 significant, 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.

- It is to be noted that some of the compounds described are basic in character. due to the presence of an unacylated basic amino nitrogen atom, or due to the presence .of an esterified group of the kind described. In such instances the compound may be employed as such, or may be employed in basic form (that is, after combination with water), or may be employed in salt form by reaction with an acid such as acetic acid, lactic acid, hydrochloric acid, or any other suitable acid.

We desire to point out that the sup riority 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 de-' scribed will find comparatively limited applica tion, so far as the majority of oilfield 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 practicing our 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 wtroleum 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 demulsiiier herein contemplated may be employed in connection with what is commonly known as down-the-hole procedure, 1. e., bringing the demulsifler in contact with the fluids oi 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 demulsiiier is used in connection with acidification of calcareous oil-bearing strata, especially if suspended in or dissolved in the acid employed for acidification.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

. l. A process for breaking petroleum emulsions oi the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising compounds of the kind selected from the class consisting of the following type formulas:

NDLTAIHND) z-NDZ -(rnn ,rrnnanew-- in which a: is a. small whole number less than 10, but including T is an oxyhydrocarbon radical selected from the class consisting of the keto type, the ether type, and the alcohol type; and D is selected from the class consisting of hydrogen, alkyl, alkylol, hydroxyalkyloxyalkyl, aminoalkyl, hydroxyalkylamino, RCO, RCQOX, RCOQX, RCQOX", RCODX' R'CO, R'COOX, R'CODX', R'CODX", a. n d

R'C0.0 in which RC0 is an acyl radical derived from a higher molecular weight carboxy acid having more than 6 carbon atoms; R'CO is anacyl radical derived from a lower molecular weight carboxy acid having not over 6 carbon atoms; 0X represents a divalent radical obtained by removal of a hydroxyl hydrogen atom from an alkylol radical; OX represents a radical derived by removal of a hydroxyl hydrogen atom from a hydroxyalkyloxyalkyl radical; OX represents a divalent radical derived by the removal of an amino hydrogen atom from an aminoalkyl radical; and OX' represents a radical derived by removal of a hydroxy hydrogen atom from a hydroxyalkylamino radical; and with the added proviso that RCO must occur at least once.

2. A process for breaking petroleum emulsions oi the water-in-oil tym, characterized by subjecting the emulsion to the action of a demulsiiler comprising compounds of the kind selected from the class consisting of the following type formulas:

ND2.T. (T.ND) 2:.ND2

!-(T.ND),.I.ND.I.ND

in which a is a small whole number less than but including 0, T is an oxyhydrocarbon radical selected from the class consisting of the keto type, the ether type, and the alcohol type; and D is selected from the class consisting of hydrogen, alkyl, alkylol, hydroxyalkyloxyalkyl, aminoalkyl, hydroxyalkylamino, RCO, 'RC0.0X, RCODX, RG00 RC0.0X"', RCO, R'CODX, R'C0.0X', RC0.0X' and RCOOX, in which RED is an acyl radical derived from a detergent-forming acid; RCO is an acyl radical derived from a lower molecular weight car-boxy acid having not over 6 carbon atoms; OX represents a divalent radical obtained by removal of a hydroxyl hydrogen atom from an alkylol radical; OX represents a radical derived by removal of a hydroxyl hydrogen atom from a hydroxyalkyloxyalkvl radical; 0X represents a divalent radical derived by the removal of an amino hydrogen atom from an aminoalkyl radical; and OX' represents a radical derived by removal of a hydroxy hydrogen atom from ahydroxyalkylamino radical; and with the added proviso that RCO must occur at least once.

3. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifler comprising compounds of the kind selected from the class consisting of the following type formulas:

ND2.T.(T.ND) $.ND2

|(T.ND)=.T.ND.T.ND-|

in which :a is a small whole number less than 10 but including 0; T is an oxyhydrocarbon radical selected from the class consisting of the keto type, the ether type, and the alcohol type; and D is selected from the class consisting of hydrogen, alkyl, alkylol, hydroxyalkyloxyalkyl, aminoalkyl, hydroxyalkylamino, RCO, RCQOX, RCQOX', RCQOX", RC0.0X"', R'CO, R'C0.0X, R'CODX', RC0.0X", a n d from an aminoalkyl radical; and 0X represents a radical derived by removal of a hydroxy hydrogen atom from a hydroxyalkylamino radical; and with the added proviso that RCO must occur at least once.

4. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising compounds of the kind selected from the class consisting of the following type formulas:

ND2.T.(T.ND) :aNDz

in which .1: is a small whole number less than 10 but including 0; T is an oxyhydrocarbon radical selected from the class consisting of the keto type, the ether type, and the alcohol type; and D is selected from the class consisting of hydrogen, alkyl, alkylol, hydroxyalkyloxyalkyl, aminoalkyl, hydroxyalkylamino, RCO, RCODX, RCODX', RCQOX", RCQOX', R'CO, R'CODX, 'R'CO'OX', R'C0.0X", and

RCODX, in which RC0 is an acyl radical droxyallryloxyalkyl radical; X" represents a divalent radical derived by the removal of an amino hydrogen atom from an aminoalkyl radical; and QX' represents a radical derived by removal of a hydroxy hydrogen atom from a in which a: is a small whole number less than but including 0; T is an oxyhydrocarbon radical selected from the class consisting of the keto type, the ether type, and the alcohol type; and D is selected from the class consisting of hydrogen, alkyl, allrylol, hydroxyalkyloxyalkyl, aminoalkyl, hydroxyalkylamino, RCO, RCODX, RCQOX', RCODX, RC0.0X"", R'CO, R'CQOX, R'CODX, R'CQOX", and R'C0.0X"", in which RC0 is a ricinoleyl radical; 'R'CO is an acyl radical derived from a lower molecular weight carboxy acid having not over 6 carbon atoms; OX represents a divalent radical obtained by removal of ahydroxyl hydrogen atom from an 'alkylol radical; OX represents a radical derived by removal of a hydroxyl hydrogen atom from a hydroxyalkyloxyalkyl radical; OX" represents a divalent radical derived by the removal of an amino hydrogen atom from an aminoalkyl radical; and 0 represents a radical derived by removal of a hydroxy hydrogen atom from a hydroxyalkylamino radical; and with the added proviso that sifler comprising compounds of the kind selected from the class consisting of the following type formulas:

m which I is a small whole number less than 10 but including 0; T is an oxyhydrocarbon radical of the keto type; and D is selectedfrom the class consisting of hydrogen, alkyl, alkylol, hydroxyalkyloxyalkyl, aminoalkyl, hydrowalkylamino, RCO, RCQOX, RCODX', RCQOX". RCQOX', R'CO, R'C0.0 a ricinoleyl radical; R'CO is an acyl radical derived from a lower molecular weight carboxy acid having not over 6 carbon atoms; OX represents a divalent radical obtained by removal of a hydroxyl hydrogen atom from an alkylol radical; OX represents a radical derived by removal of a hydroxyl hydrogen atom from a hydroxyalkyloxyalkyl radical; O represents a divalent radical derived by the removal of an amino hydrogen atom from an aminoalkyl radical; and OX represents a radical derived by R'CODX, R'C0.0K',' and R'CQOX, in which RC0 is aaoaaaa removal of a hydroxy hydrogen atom from a hydroxyallrylamino radical; and with the added proviso that RCO must occur at least once.

7. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising compounds of the kind selected from the class consisting of the following type formulas:

ND2.T.(T.ND)1.ND2

in which a: is a small whole number less than 10 but including 0; T is an oxyhydrocarbon radical of the ether type; and D is selected from the class consisting of hydrogen, alkyl, alkylol,

hydroxyalkyloxyalkyl, aminoalkyl, hydroxyalkylamino, RCO, RC0.0X, RCODX, RCQOX, RCODX', R'CO, RCODX, R'CQOX', R'C0.0X", and R'COOX', in which RC0 is a ricinoleyl radical; R'CO is an acyl radical derived from a lower molecular weight carboxy acid having not over 6 carbon atoms; 0X represents a divalent radical obtained by removal of a hydroxyl'hydrogen atom from an allrylol radical; OX represents a radical derived by removal of a hydroxyl hydrogen atom from a hydroxyalkyloxyalkyl radical; OX" represents a divalent radical derived by the removal of an amino hydrogen atom from an aminoalkyl radical; and OX' represents a radicalderived by removal of a hydroxy hydrogen atom from a hydroxyalkylamino radical; and with the added proviso that RCO must occur at least once.

8. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising compounds of the kind selected from the class consisting of the following type formulas:

in which a: is a small whole number less than 10 but including 0; 'I' is an oxyhydrocarbon radical oi the alcohol type; and D is selected from' the class consisting of hydrogen, alkyl, alkylol, hydronyallryloxyallryl, amlnoalkyl, hydroxyalkyl- 'amino, RCO, RCQOX, RCODX', RCODX",

rived from a lower molecular weight carboxy acid having not over 6 carbon atoms; OX represents a divalent radical obtained by removal oi a hydroxyl hydrogen atom from an allrylol radical; OX represents a radical derived by removal of a hydroxyl hydrogen atom from a hy-