US2373102A - Process for breaking petroleum emulsions - Google Patents

Description

"Patented Apr. 10, 1945 l mocnss FOB namxme PETROLEUM muns rons I Melvin De Groote, University City, and Bernhard Keiser,

Webster Groves,

Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Did, a

corporation of Delaware No Drawing. Application March 9, 1943,

Serial No. 478,596

6 Claims. (Cl. 252-341) This invention relates primarily to the resolution of petroleum emulsions.

One object of our invention is to provide a novel process for resolving petroleum emulsions of the wa'ter-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 beenprepared under controlled conditions from mineral oil, such as crude petroleum, and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under conditions just mentioned, is of significant value in removing impurities, par,- ticularly inorganic salts, from pipelineoil.

- The deinulsifier r demulsifying agent employed in our process consists of the resultant products obtained by reaction involving polybasic carboxy acids, preferably and conveniently in the form of an ester, such as diethyl phthalate, and acylated ureas, and particularly acylated substituted ureas having in the most preferred. form, at least one, and more Such acylatedureas, or' substituted ureas, are of the kind in which the acyl radical which is introduced is derived from detergent-forming monocarboxy acids containing eight carbonatoms or more, and not more than 32 carbon atoms, and.

are characterized by the fact that they combine .with alkalis-toproduce soap or soap-like mate- -rials.- -These detergent-forming -acids include fatty acids, resin acids, petroleumacids, etc. For the sake of convenience, these acids will be indicated by the iormtila'RflOOH. Certain derivatives of detergent-forming acids react with alkali to produce soap or. soa'p like materials, and ,4 are the obvious equivalent-of the unchanged or unmodified detergent forming acids; for. in-. stancerinstead of fatty acids,one might employ preferably, at least two hydroxyl radi- Acids alsotrue in regard to primary amines, such as 9, 1943. Said co-pending applications describe new compositions of matter, for instance, the acylated derivatives of reaction products obtained by combination with diethanolamine and diethyl carbonate. This is illustrated in a very simple .aspect by the three following reactions:

ethyl ethanolamine, ethyl propanolamine, ethyl butanola'mine, propyl ethanolamine, propyl propanolamine, cyclohexyl ethanolamine, benzyl ethanolamine, phenyl ethanolamine, etc. This is monoethanolamine, monopropanolamine, monobutanolamine, monopentanolamine, monohexanolamine, etc.

Reconsidering the three reactions immediately preheding, it is obvious that they may be considagent having a reactive ethylene oxide ring, and

forni'ing acyl group into a molecule or compound of the kind previously described by the use of Reference is made to our co-pending applica- 7' tions Serial Nos. 478,595 and 478,594, filed March ered as substituted ureas, substituted urethanes, and carbonic acid esters; The-'uiethanes are, of course, esters'of carbamic acid. It is also obvious that the products of reaction above described, the

esters, urethanes, the substituted ureas, etc., can

be treated with ethylene oxideor some other resubsequently acylated'witba high molal monocarboxy acid.

-One may introduce ahigh molal detergentsuitable' reactants, such as ethyl oleate, ethyl naphthenate, ethyl resinate, etc., all of which isdescribed in detail in said aforementioned copending applications.

Attention is, directed to U. S. pate'ntto' De Cirootev No. 2,083,22L dated June 8, 1937, and'No.

2,059.27 3, dated November 3, 1936, to Piggott. It is :to be noted that said, aforementioned De Groote patent gives a more ,elaborate description of. the monocarboxy detergent-forming acids-herein contemplated as reactants. It is also believed, in the light of subsequent investigations, that in many instances reaction with a compound having a reactive ethylene oxide ring, such as ethylene oxide, propylene oxide, butylene oxide, glycid, or the like, may result in the complete elimination of an amino hydrogen atom; as shown in both of said aforementioned patents, i. e., the De Groote and Piggott patents.

It is also obvious that substituted ureas in considerable variety and suitable. for use as a reactant in preparing compounds of the kind herein contemplated, both for use as demulsifiers and for other uses, are readily obtainable from a variety of amines.

It may be well to point out that our preferred fatty acids, for instance, oleic, ricinoleic, linoleic, linolenic, stearic, lauric, etc. One need not employ a single higher fatty acid, but may employ the fatty acids, particularly in ester form, as derived from various natural sources. In other words, one may employ the fatty acids or esters of fatty acids as they occur in mixed form in cottonseed oil, corn oil, castor oil, soyabean oil, olive oil, cocoanut oil, teaseed oil, linseed oil, etc.

In many instances, one need not separate the acylated ureas, or substituted press, of the kind herein described from other members of a cogeneric mixture, such as esters of carbonic acids,

or 'urethanes. Previous reference in regard to this aspect has already been made in connection with our two co-pending applications Serial Nos.

The

478,594 and 478,595, flied March 9, 1943. use of such cogeneric mixtures as reactants will serve to yield a final product which containsa significant amount of the compositions ornew compounds herein contemplated.

Attention is further directed to the fact that in various examples, particularly those hereinafter described in detail, there is an intermediate step of oxyethylation prior to treatment with ethyl oleate or the like and diethyl phthalate or the like. It is to be noted that in some instances it is more advantageous to reverse the procedure and react with a compound such as diethyl phthalate first, and then follow with an acylation reaction or the kind in which there is introduced a high molal detergent-forming monocarboxy radical or acylated radical. I

It is also of interest to note that,v as previo pointed out, the acylation reactions herein con- .15 detergent-forming acid, as-a source'of the re- 'quired vacyl radical, is exemplified by: the higher piamylurea is prepared from amylamihe, and a cyanate. (See Berichte 12, 1331, Custer.) Other equally suitable methods may be employed.

Sussrrmzp Um Example 2 The same procedure is followed'as in the pie ceding example, except that cyclohexylamine is substituted for amylamine.

, Susanna-ran Um Example 3 'Ifhe same procedure-is followed as in Example 1, preceding, except that benzylamine is substituted for amylamine.

svssnrprrn URIA Efiomple '4 The same procedure is followed as in Example \1 preceding, except that aniline is substituted for amylamine. V

AMIDO-TYPI Ac'rmrsn sunsnrurxn Urns Example 1 Symmetrical diamyl urea is reacted with a low molal ester of a hydroxylated high molal detergent-forming acid, such as the ethyl ester of ricinoleic acid, the ethyl ester of hydroxystearic acid, the ethyl ester ,of dihydroxystearic acid, the ethyl ester ofhydroxylated acids obtained by the oxidation of petroleum .wax, etc. Equal molal ratios are employed. One amino hydrogen atom remains without entering into reaction.

Amino-TY" AcYum 8088mm Urns Example 2 The same procedureais followed as in the preceding example, except that instead oi employing the amylated urea, one employs instead,

tempiated, whether involving the introduction of 7 an acyl radical from a high molal detergent forming monocarboxy acid, or the acyl radical of a polybasic carboxy acid, need not be limited to the esteriflcaflon type of acylation, i. e., reaction involving an alcoholic hydroxyl radical, but includes reactions involving an amino hydrogen atom, i. e., amidiiication.

In other words, in some of the subsequently described examples, it

various substituted ur'eas described under the heading Substituted Examples 2-4."

- Oxntx'nxrstfbdssrrrum Urns 1 pound mole of four pound moles of ethylene oxide (see afore- -mentioned U. S. patent to De Groote No. 2,083,221,

isiobvious that if oxyethylation were, omitted, the

product would still be susceptible to"reactio ns of the kind described, i.-- e;, acylstion reactions. n It would appear that perhaps the simplest and most attractive reaction for the formation of compounds of the kind herein-contemplated, or

' rather, for. the formation of certain desirable intermediates, would be a reaction involving the amide of a high molal detergent-forming acid,

such as oleoamide, ricinoleoamide, etc., with diethyl carbonate, or the like, in the-ratio of-ctwo and U. S. patent to Pisgott No. 2,059,273) Oxmnmsrsn Sworn-mo Um Example 2 One pound mole of amylaied urea of the kind 'described'under the "Substituted ureas.

Example 1;".preced'in'g, is treated with two pound moles of ethylene oxide so as to yield the corresponding oxyetbtrlated derivative.

.moles ofthe amidefor 121018 91 diethyl-carbonate, particularly in theprcsence of a small amount or catalyst, such as sodium'bicarbonate.

. Oxxmrnm Suns-11mm Um Example 3 I Insteadofemployingamylatedumaasareactant, one instead various other substitutediureas of the kind described under the previous headings 2Bubstituted ureas, Examples 2-4, inclusive.

-urea. is' treated with at least Oxutmsrzo Um Example 4 The same procedure is followed as in the three preceding examples, except that some other reactant containing a reactive ethylene oxide ring, for instance, propylene oxide, butylene oxide, glycid, or the like, are employed instead of ethylene oxide.

ESTER-TYPE AcYLATan Su'esTITuTso UasAs Q Esample 1 Hydroxylated substituted ureas, preferably having at least two alcoholic functions, arereacted with low molal esters of high molal detergent-forming acids which may or may not be.

hydroxylated, for example, one pound mole of an oxyalkylated urea exemplified by Oxyalkylated Example 1, preceding, is reacted with one pound mole of ethyloleate.

EsTna-Trrn AcYLATeo SUesTITu'rEn UBEAS Example 2 Instead of using an oxyalkylated urea. of the kind exemplified by Example 2, preceding, one employs the type exemplified by Exampdes 3 or 4, preceding.

ESTER-TYPE AcYLAm SUBSTITUTED UREAS Example 3 Ethylricinoleate, or some other low molal ester, such as the methyl or propyl ester, is substituted for ethyloleate in the preceding example.

ESTER-TYPE AcYLATsn SussTITuTeo UasAs Example 4 Ethyl naphthenate is substituted for ethyloleate in Examples 1 or. 2, preceding.

ESTER-TYPE ACYLATED SussTITuTao UREAS Example 5 Ethyl resinate, prepared by the esterification of rosin with ethyl alcohol, is substituted for ethyloleate in Examples 1 and 2, preceding.

FINAL Como'sITroN or MATm Example 1 1 pound mole of an amido acylated substituted urea, as exemplified by the type of material described under Example 1, preceding, is'reacted with 1 pound mole of diethyl phthalate. The substituted urea is preferably reacted with 2 to 4 moles of an oiwalkylating agent, prior to re-.

action, with diethyl phthalate. is especially suitable.

FINAL ComrosrrroN or MATTER Example 2 The same procedure is followed as in Ester type acylated substituted ureas, Example 1, preceding, but there is employed as a reactant the type of material described under the heading Ethylene oxide -Amido-type acylated substituted ureas, Ex-

ample 2i 4 FINAL COIIPOSITION or MATTER Example 3 The same procedure is followed as in Examples 1 and 2, preceding, but instead of the previous reactants employed in conjunction with diethyl phthalate, there is employed instead a material of the kind described under the heading "Estertype acylated mibstituted ureas, Example 1.

FINAL ComosITIoN or Example 4 The same procedure is-followed as the pre- I ceding example, except that the reactant em ployed in conjunction with diethyl phthalate is a material of the kind typified by "Ester-type I acylated substituted ureas, Examples 2 to 5, in-

elusive."

FINAL COMPOSITION or MATTER Example 5 The same procedure is followed as in the preceding examples, except that where the reactant employed in conjunction with diethyl phthalate is polyfunctional, the molar proportion of di ethyl phthalate to the acylated intermediate (acyP having reference to thehigh molal detergent-forming monocarboxy acid. radical) is increased to a polymolecular proportion, for instance, 2 to 1 or 3 to 1.

FINAL COMlOSI'HON or MATTER Earample 6 I The same procedure is followed as in the preceding Examples 1 to 5, inclusive, except that the diethyl ester of some other suitable polybasic carboxy acid, such as diethyl maleate, diethylfumarate, diethyl, adipeate', diethyl succinate, di ethyl azaleate, diethyl citrate, diethyl citraconate, diethyl sebacate, diethyl tartrate, or the like, is employed;

' FINAL Como'sITIoN or M TTER Example 7 The same procedure is followed as in Examples 1 to 6, preceding, except that some other low molal alkyl ester, particularly a dialkyl ester, is employed instead of the diethyl ester. For instance, one might employ dimethylphthalate,

- 40 ethyl methyl phthalate, dipropyl phthalate,

methyl propyl phthalate, ethyl propyl phthalate, dibutyl phthalate, propyl butyl phthalate, ethyl butyl phthalate, etc. In various of the above instances, the acid itself or anhydride, such as phthalic anhydride, maleic anhydride, citraconic anhydride, or the acid, such as adipic acid, azaleic acid, or the like, may be used.

Reference is again made to the fact that'it has been previously noted that in some instances it is more-convenient and desirable to react a selected raw material or intermediate with a reactant such as diethyl phthalate, or the like, and

subsequently react with ethyl oleate, ethyl ricin-- oleate, or the like.

In the preceding examples, it is to be noted that the reactions, in part, involve conventional acylation, which generally-means the elimination of water, or an alcohol, or possibly, ammonia. In view of the employment of a reactant such as ethyl oleate, or ethyl ricinoleate, it is obvious that acylation will ,take'place with the eliminae tion of ethyl alcohol. Naturally, methyl oleate,

, methyl ricinoleate, propyl oleate, propyl ricinolestance, 2-12 hours. Completeness of reaction is generally indicated by the fact that substantially the theoretical amount of alcohol, after making allowance for impurities and mechanical loss, is evolved and may be condensed and measured. The same applies when the acylation reaction involves a reactant such as diethyl phthalate, or the like. This is also true in regard to reactions involving diethyl carbonate. The diethyl carbonate reactions are sometimes catalyzed by the addition of a small amount, for instance, approximately /i% to of sodium bicarbonate. 7

Conventional acylation reactions of the kind involved in the formation of oleoamide, or ricinoleoamide, are so well known that description is not required.

We have found that the most suitable products for various purposes, and particularly, for

demulsiflcation, are sub-resinous, semi-resinous, or balsamlike products, and are preferably derived from' polyfunctional acylated reactants, in which the acyl group is derived from a high molal detergent-forming monocarboxy acid. We have found that suohproducts are soluble to a in which q indicates a small whole number (one in the case of a monomer, and probably not over 10, and usually less than 5, and m and n indicate the number 1 oimore, and m" and n" indicate zeroor a small or moderately sized whole number, such as zero, one or more, but in any event, probably a number not in excess of 4-8.

fairly definite state, for' example, 5% in some solvent, such as water, alcohol, benzene, dichlo-- roethyl ether, acetone, .cresylic, acid, dilute acidic acid, dioxane, or the like. This is simply another way of stating that it is preferable, that the product be one of the sub-resins, which are commonly referred to as an A resin, or a 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.)

It is our preference that the roducts'be obtained from polyhydroxylated 'acylated products by reaction with diethyl phthalate, or the like. Indeed, it is our preference to employ polyhydroxylated acylated products. of the kind in which there is no amino hydrogen atom present, i. e., the kindv in which acylation is limited entirelyto the esterification type of reaction.

In view of what has been said as to the runner 0115 and varied aspects of the present invention, it is apparent that a monohydroxylated acylated product free from an amino hydrogen atom, can form only a monomer such as a complete ester or fractional ester. Thus, if the hydroxylated acylment with a reagent containing a reactive Actually, in view of what has been said as to the most desirable procedure of manufacture, in order to avoid decomposition, it is obvious that the free carboxyl atom above will not appear, but the ester radical, i. e., one where the carboxylic hydrogen atom has been replaced by a methyl, ethyl, propyl, or butyl group, will appear.

It is also obvious that the solubility oi the reagents herein described maybe enhanced by oxyalkylation, i. e., the final composition of matter-exemplified by Examples 1 to 7, preceding, may, in various instances, be subjected/to treatethylene oxide ring, for example, ethylene oxide, propylene oxide, butylene oxide, glycid, etc. In such instances, the ethylene oxide'or equivalent reactant reacts with any aminohydrogenatom present or any hydroxyl radical present, or may cause a rearrangement or re-esterification -by.replacing a low mole alkyl radical, such as an ethyl radical, by a hydroxy' ethyl radical, or an equivalent radical, in which the carbon atom chain is interrupted one or more times by an oxygen atom. Compare reactions involved when a glyceride such as a castor oil or olive oilais treated with ethylene oxide.

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,

ated products employed as reactants for combiwhere n indicates the number 2 or more, then the reaction between a monohydric alcohol and a polybasic acid will result in a compound which may be indicated by the following formula: YX(COOH)1u, wherein n indicates the number 1 or more, and which is in'reality a contraction of a more elaborate structural formula, in which X and Y are joined by a carboxyl radical or resi? due. Assuming, however, as would be true in the majority of cases, that the alcohol actually would be a poiyhydric alcohol, and 'that the'acid body would be polybasic in nature, for instance, if one employed a diphthalate of a polyhydroxylated ester diamide of thekind previously described, then examination reveals that the formula might result in acombination, in which therewere neither residual carboxyl radicals, nor residual such as benzene, toluene, xylene, tar acid oil,

cresol anthracene oil, etc. Alcohols, particularly aliphatic. alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl' alcohol, hexyl alcohol, octyl alcohol, etcL, 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 our process may be admixed with one or more of the solvents customarily used in connection with conventional 5 apparent insolubility in oil and water is not sigic acid, and the thereof, such as diethyl phthalate. For purpose of -clarity,"in the -hereto attached-claims, the

acids. 1 Y I xttentienhes been previously. directed t the fact'that theexpression alkanoli' includes the type of hydroxy'alipliatic radicals in which the" niflcant, because said reagents undoubtedly have solubility within the concentration employed.

"This Same fact 13 true in'regard to the material or materials employed as the demulsii'ying agent of our process.

We desire to point out that the superiority of the reagent or demulsifying agent contemplated oxide, propylene'oxide,butylene oxide and glyoide,

Patent is;

in our process isbased ,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 we have found that such a demulsiiy- .ing agent has commercial value, as it will economically break or resolve oil field emulsions in a, number of.-case which cannot be treated as easily 'or. at soilow a cost'with the agents heretofore available.

In practising our processior resolving petroleum emulsionsof the water-in-oil type, a-treating agent or demulsifyirig agent of the; kind above described is brought into contact with orcaused to act upon the emulsion to.be treated, in any of demulsifying paratus now generally used to resolve .or break petroleum emulsions with a chemical reagent, the

above procedure beingused either alone, or in combination with-other demulsifying procedure, such as'the electrical dehydration process. I Y The demulsifier herein contemplated-may be employed in connectionwith what iscommonly known as down-the-hole procedure.'i. e., bringing the demulsifle'r in contact with the fluids of the well at the bottom of the well, .or at some point prior to theemergence of said well fluids. This particular type of application is decidedly feasible when thedemulsifier is used in connection'with acidification of calcareous oil-bearing strata, especially if suspended in or dissolved in the acid employed for acidification.

The words "acidyP and "acyP and the-words acidylation and "acylation are usually used synonymously, Compounds of the type herein contemplated, and particularly for use as demulsiilers, are characterized by having two diflerent types of carboxylic acid radicals, or carboxylic la yl radicals present. One type is derived from high molal'detergeht-formingmonocarboxyacids, such as higher'fatty acids, and the. other. type;is

. derivedfrom polybasic acids, particularly phthal-=- 7 like, or other suitable derivatives of the words facyl, acylatedf' and facy1a'-' tion, is limited to-high .molal "monocarboxy detergent-forming acids,- whereas,- the expressions" acidyl, ffacidylated and acidylationi are molal oxyalkylated agents, such as ethylene has a distinctly functional significance.

Having thus described our invention, what we claim as-new and desire to secure by Letters 32 carbon atoms; said acidyl radical being a polybasic carboxy acid radical. 2. A'process for breaking petroleum emulsions or the water-in-oil type, whichconsists in subjecting the emulsion to the action of a demulsifier, comprising a sub-resinous acidylated derivative of an acylated substituted urea containing at least one nitrogen-linked alkanol radical havthe various'ways, orby any of the various aping at least 4 and not more than 18 ether linked oxygen atoms; theacyl radical being that of a detergent-forming monocarboxy acid having at least 8 and not more than 32 carbon atoms; said acidyl radical being a polybasic carboxy acid rad- 3. A process for breaking petroleum emulsions of the water-in-oil type, which consists in sub-i jecting the emulsion to the action of a demulsi- .fier, comprising a' sub-resinous acidylated der-lvative of an acylated substituted urea containing at least one nitrogen-linked alkan'ol radical havmg atleast 4 and not more than 18.ether linked oxygen atoms; the acyl radical being that of a detergent-forming monocarboxy acid having at least 8 and not more than 32 carbon atomsisaid' acidyl radical being a' dibasic carboxy acid radi- Call;

4. A process for breaking petroleum emulsions of the water-in-oil type, Which'consists in subjecting the emulsion to the action of ademulsifler, comprising a sub-resinous acidylated deriv- -ative of an'acylated substituted ureacontaining .at least one nitrogen-linked alkanol radical hav ing at least 4 and notmqre than 18 other linked oxygen atoms; the acyl radical. being that oi a higher fatty acid having at least 8 and not more radical being a than 32 carbon atoms said acidyl dibasic'carboxy acid radical.

-' SLQA process for breaking petroleum emulsio of the water-in-oil type, which consists in sub- .lecting the emulsion to the actiofiof a demul sifler, comprising asub-resinous acidylated deriv ative of an acylated substituted urea containing at least'one nitrogen-linked ,alkanol radical having atleast time not more than 18 ether linked connection with polybasic 'carboxy carbon atom chain is interrupted at least once -by an oxygen 'ai;0m, i; e., contains an ether linkage.

We have found the {type in which-the ether linkage recurs a fairly large number of most-desirable type of compoundi'or. other pur- I poses enumerated; Unquestionably, the recurring other linkage, particularly that'derived from low ox en .atoms; the any! radicalv being that'or a higher fatty acid having 18 carbon atoms; said acidyl radical'being a dibasic carboxy acid rad-j ical. e

. 6. A process tor. breaking petroleum emulsions 'of the water-in-oil typ which consists in subiecting the emulsionto'the action 01' a demulsiiler, comprising a sub-resinous acidylated deriva- .tive otan acylated'substitut'ed urea containing at -l east.one nitrogen-linked alka'nol radical having at least 4 and not more than 18 ether linked oxy- I times, for instanceni to .18 times-,1 represents the most. desirable type of demulsifiei' vand also the gen atoms; the acyl radical being that oia'highe'r unsaturated'fatty acid h ving 18 carbon atoms;

said acidyl; radical being a dibasic'carbom acid BERNHARD