Patented Nov. 11, 1941 2,262,743

UNITED STATES PATENT of FICE 2,262,743 PROCESS FOR BREAKING PETROLEUR EMUSIONS Melvin De Groote, University City, and Bernhard Keiser and Charles M. Blair, Jr., Webster Groves, Mo., assignors to Petroite Corporation, Ltd., Wilmington, Del, a corporation of Dela Ware No Drawing. Application May 12, 194i, Serial No. 393,128 4 Claims. (C1. 252-344) This invention relates primarily to the resolu ous chemical compounds adapted for use in tion of petroleum emulsions, our present appli breaking oil field emulsions, reference was made cation being a continuation, in part, of Our co to a type exemplified by the following formula: pending application Serial No. 342,716, filed June. N-CH 27, 1940. 2 One object of our invention is to provide a Ciuc, novel process for resolving petroleum emulsions NH-CI of the water-in-oil type that are commonly re In regard to such compounds, it is pointed out ferred to as 'cut oil,' 'roily oil,' 'emulsified oil,' in said co-pending application Serial No. 342,716, etc., and which comprise fine droplets of nat 10 that the oxyalkylated derivatives may be emi urally-occurring waters or brines dispersed in a ployed, This fact is stated in the following.lan more or less permanent state throughout the oil guage: which constitutes the continuous phase of the "Also, as is well known, any of the diamines emulsion. w of the kind previously described containing at Another object of our invention is to provide s least one amino hydrogen atom may be con a: economical and rapid process for separating verted into hydroxylated derivatives by reaction emulsions which have been prepared under con with an alkylene oxide, such as ethylene oxide, trolled conditions from mineral oil, such as crude propylene Oxide, glycidol, epichlorhydrin, and the petroleum and relatively soft waters or weak like. As to the general procedure employed, al brines. Controlled emulsification and subsequent 20 though not concerned particularly with cyclic demulsification under the conditions just men amines or the like, reference is made to U. S. tioned is of significant value in removing im Patent No. 2,046,720, dated. July 7, 1936, to Bot purities, particularly inorganic salts, from pipe tons.' line Oil. The compounds herein contemplated are chair Incidentally, a compound of the kind herein acterized by the presence of a five-membered contemplated may be used as a break-inducer heterocyclic ring with two atoms different from and for doctor treatment of the kind intended carbon. More specifically, they may be consid to Sweeten gasoline. See U. S. Patent No. 2,- ered as derivatives of imidazole, frequently re 157,223, dated May 9, 1939, to Sutton. ferred to as glyoxaline. Inidazole (glyoxaline) Such compounds may also find utility in re 30 is indicated by the following formula: covering oil from Subterranean oil-bearing strata. See U. S. Patent No. 2,223,381, dated February EC-N 25, 1941, to De Groote and Keiser. Compounds of the type herein contemplated a are of particular value in preventing water-in 85 Y?, - oil emulsions resulting from acidization of cal The imidazolines or glyoxalidines may be con careous oil-bearing strata. See U. S. Patent No. sidered as dihydro-derivatives of amidazole (gly 2,233,383, dated February 25, 1941, to De Groote oxaline); and thus the expressions "dihydrogly and Keiser. Such specific application of de oxalines' and "glyoxalidines' are often em mulsifiers of the kind herein contemplated is 40 ployed. The introduction of two hydrogen atoms disclosed in our co-pending application Serial at the 4-5 position results in the conversion of No. 393,129, filed May 12, 1941. imidazole into dihydroglyoxaline, which may be . The chemical compounds herein contemplated indicated by the following formula: as demulsifying agents, are oxyalkyl derivatives of imidazolines. These types of materials and 45 BC-N the method of preparing the same are Well known. EC5 2CH For instance, see U. S. Patent No. 2,211,001, N1/ dated August 13, 1940, to Chwala. In our aforementioned co-pending application Serial No. 342,716, which is concerned with vari 50 AS to the manufacture of imidazolines, refer 2 2,262,743 ence is made to the following patents: U. S. other acids, mixed higher fatty acids derived Patents Nos. 2,215,861, 2,215,862, 2,215,863 and from animal or vegetable sources, for example, 2,215,864, dated September 24, 1940, to Wald lard, cocoanut oil, rapeseed oil, sesame oil, palm mann and Chwala. ------kernel oil, palm oil, olive oil, corn oil, cottonseed Imidazolines or glyoxalidines may be regarded oil, Sardine oil, tallow, soyabean oil, peanut oil, as dehydration products of certain amides; and castor oil, seal oils, whale oil, shark oil and other they may be obtained by reacting polyamines. fish oils, teaseed oil, partially or completely hy and the higher carboxylic acids under certain drogenated animal and vegetable oils, such as conditions. The formation of these glyoxalidine these mentioned; hydroxy and alpha-hydroxy compounds, while forming no part of the pres O higher carboxylic, aliphatic and fatty acids, such ent invention, is indicated by the following as hydroxystearic acid, dihydroxypalmitic acid, Scheme: dihydroxystearic acid, dihydroxybehenic acid, O alphahydroxy , alphahydroxy stearic 2 -O acid, alphahydroxy , alpha hydroxy R.C-OH--H.N.C.H.C.H.R.N.H.R.X --> 5 , alphahydroxy , alpha Alkylene polyanine hydroxy Cocoanut oil mixed fatty acids, alpha O - hydroxy , alphahydroxy arachidic 2 r. f -HO acid, and the like; fatty and Similar acids derived R.C.H.N.C.H.CH.R.N.H.R.XHO - from various waxes, such as beeswax, sper Amide 20 maceti, montan wax, Japan wax, coccerin, and carnauba, Wax. Such acids include carnaubic R-c e's CH acid, , lacceric acid, , . . . . 2EO psyllastearic acid, etc. . As suggested, one may X-RN C.R. also employ higher molecular weight carboxylic 1,2-disubstituted glyoxalidine 25 acids derived, by oxidation and other methods, wherein R represents an alkyl or alkenyl group from paraffin wax, petroleum and similar hydro containing from 10 to 20 carbon atoms (the res carbons; resinic and hydroaromatic acids, such idue of a higher fatty acid); Ri represents hy as hexahydrobenzoic acid, hydrogenated naph drogen or a lower alkyl group; R2 represents an thoic, hydrogenated carboxy-diphenyl, naph alkylene group or a lower alkyl substituted al 30 thenic, and abietic acid; aralkyl and aromatic kylene group; and X represents a hydroxyl group, acids, Such as hexahydrobenzoic acid, hydrogen an amino group, or an aminoalkylene substituted ated naphthoic, hydrogenated poly carboxy imino group. See U. S. Patent No. 2,214,152, diphenyl, naphthenic, and abietic acid; aralkyl dated September 10, 1940, to Wilkes. and aromatic acids, such as benzoic acid, See also U. S. Patents Nos. 2,55,877 and 35 Twitchell fatty acids, naphthoic acid, carboxy 2,155,878, both dated April 25, 1939, to Waldmann diphenyl, pyridine carboxylic acid, hydroxy and Chwala. benzoic acid, and the like. The expression "higher molecular weight car Other suitable acids include phenylstearic acid, boxy, acids' is an expression frequently employed benzoylnonylic acid, campholic acid, fencholic to refer to certain organic acids, particularly 40 acid, cetyloxybutyric acid, cetyloxyacetic acid, monocarboxy acids, having more than six car chlorStearic acid, etc. bon atoms, and generally, less than 40 carbon Another source of suitable acids are those com atons. The commonest examples include the monly referred to as lac acids, such, for example, detergent-forming acids, i. e., those acids which as the acids derived from shellac. Such acids combine with alkalies to produce soap or soap 45 include various polyhydroxy acids, for example, like bodies. The detergent-forming acids, in aleuritic acid, shelloic acid, and kerrolic acid. turn, include naturally-occurring fatty acids, As is well known, one may use substituted resin acids, Such as abietic acid, naturally-occur acids in which some other non-functional con ring petroleum acids, such as naphthenic acids, stituent enters the structure of the fatty acid. and carboxy acids produced by the oxidation of 50 For instance, one may use aryl-, hydroxy-, petroleum. As will be subsequently indicated, alkoxy-, chlor-, keto-, and amino-derivatives. there are other acids which have somewhat simi Generally Speaking, however, it is always prefer lar characteristics and are derived from some able to use the unsubstituted acid, particularly What different sources, and are different in struc free from substituents which contain either ture, but can be included in the broad generic 55 Oxygen or nitrogen atoms. Generally speaking, term previously indicated. the introduction of hydrocarbon radicals, regard Among Sources of such acids may be men less of Source, has little effect, except in altering tioned straight chain and branched chain, satu the hydrophile-hydrophobe balance. rated and unsaturated, carboxylic, aliphatic, ali One may also employ the blown or oxidized Cyclic, fatty, aromatic, hydroarmoatic, and O acids, such as blown ricinoleic acid, blown oleic, aralkyl acids including , , etc., or estolides derived from blown oils, such heptylic acid, , capric acid, pimelic as blown castor oil, blown soyabean oil, etc. acid, Sebacic acid, , saturated and un Needless to say, the acids themselves need not Saturated higher molecular weight aliphatic be employed; but one may readily employ any acids, such as the higher fatty acids containing 65 functional equivalent, such as the anhydride, the at least eight carbon atoms, and including, in acyl chloride, or the like. In some instances, the addition to those mentioned, , stearic esters, especially in presence of a trace or a acid, , ricinoleic acid, diricinoleic acid, significant amount of water, act as the acid itself, triricinoleic acid, polyricinoleic acid, ricino in that the acid is liberated. Unless specific ref Stearolic acid, ricinoley lactic acid, acetylirici 70 erence is made to a particular isomer, one may noleic acid, chloracetyl-ricinoleic acid, linoleic employ any isomer or mixture of various isomers, acid, linolenic acid, lauric acid, myristic acid, un if the acid or acids are so available. We have decylenic acid, palmitic acid, mixtures of any produced demulsifiers, for use in our process, by two or more of the above mentioned acids or 75 the following procedures: 2,262,743 3 Eacample 1 within the scope of the claim. Similarly, where 1-aminoethyl-2-heptadecenyl glyoxalidine is the claims specify the presence of the group prepared by mixing one gram mole (282 grams) of oleic acid with two gram moles (206 grams) of i. e., the group introduced by oxyalkylation at diethylene triamine, and heating the mixture for the amino hydrogen position, it is understood a period of about 16 hours under a distilling that R includes groups derived from glycid or column. Water was continuously removed until the like. a temperature of about 245° C. was reached. The It is to be noted that the compounds herein quantity of Water thus removed amounted to 0 contemplated, being basic in character, maybe about i.7 moles. Unreacted diethylene triamine used as Such, or in the form of a base, i. e., in was distilled from the reaction mixture under combination with water, or in the form of a salt, Vacuum, and the residue then was purified by i. e., in combination with an organic or inor distillation at an absolute pressure of 1 mm. of ganic acid, such as hydrochloric acid, acetic acid, mercury, at which point it boiled within a tem 5 lactic acid, and the like. perature range of 225 to 250° C. About 220 Specific attention is directed to the fact that grams of the 1-aminoethyl-2-heptadecenyl gly One may use various Oxyalkylating agents in ad oxalidine was obtained as a pale yellow liquid. dition to those already indicated. For instance, The product also may be designated by refer note the oxyalkylating agents specifically ence to the reactants used in its preparation, as enumerated in aforementioned U. S. Patent No. oleyl diethylene triamine. 20 2,211,001, and also in U. S. Patent No. 2,208,581, thylene oxide is introduced into the above dated July 23, 1940, to Hoeffelmann. All the base at a temperature of about 120-140° C., un oxyalkylating agents mentioned in both of the til the increase in weight amounts to about 2A previously designated patents may be employed pound moles of ethylene oxide calculated upon as reactants for the manufacture of demulsifying one pound mole of the base. 25 agents contemplated in the present process. Conventional demulsifying agents employed Eacample 2 in the treatment of oil field emulsions are used as The base used in the preceding example is re such, or after dilution with any suitable solvent, placed by 1-(aminoethyl ethylamino)-2-hepta 30 Such as Water, petroleum hydrocarbons, such as decenyl glyoxalidine. This glyoxalidine was pre gasoline, kerosene, stove oil, a Coal tar product, pared by reacting 1 gram mole of Oleic acid. With such as benzene, toluene, xylene, tar acid oil, three gram moles (438 grams) of triethylene cresol, anthracene oil, etc. Alcohols, particu tetramine in a vessel equipped with a distilling larly aliphatic alcohols, such as methyl alcohol, column. The mixture was heated for a period 35 ethyl alcohol, denatured alcohol, propyl alcohol, of about six hours, and water was continuously butyl alcohol, hexyl alcohol, octyl alcohol, etc., removed until a temperature of about 300° C. may be employed as diluents. Miscellaneous was reached. Approximately 1.9 moles of water solvents, such as pine oil, carbon tetrachloride, were thus removed. The reaction mixture was sulfur dioxide extract obtained in the refining of then distilled under vacuum to remove excess 40 petroleum, etc., may be employed as diluents. triethylene tetramine. Ethylene oxide was em Similarly, the material or materials employed as ployed in the same manner as in Example 1, pre the demulsifying agent of our process may be ceding. admixed with one or more of the Solvents cus tomarily used in connection with conventional Eacample 3 45 denulsifying agents. Moreover, Said material or materials may be used alone, or in admixture Tetraethylenepentamine is substituted for tri with other suitable Well known classes of de ethylene tetramine as a reactant in the preced mulsifying agents. ing example. The glyoxalidine obtained was It is well known that conventional demulsify treated as before with ethylene oxide. 50 ing agents may be used in a water-soluble form, Eacaniple 4 or in an oil-soluble form, or in a form exhibit ing both oil and water solubility. Sometimes Lauric acid is substituted as a reactant for they may be used in a form which exhibits rela oleic acid in the three preceding examples. tively limited oil solubility. However, since such 55 reagents are Sometimes used in a ratio of 1 to Eacample 5 10,000, or 1 to 20,000, or even 1 to 30,000, such an apparent insolubility in oil and water is not Ricinoleic acid is substituted for oleic acid in significant, because said reagents undoubtedly Examples 1-3 preceding. have solubility within the concentration em Eacample 6 60 ployed. This same fact is true in regard to the material or materials employed as the demul Naphthenic acid is substituted for oleic acid sifying agent of Our process. in Examples 1-3 preceding. We desire to point out that the superiority of Eacample 7 the reagent or demulsifying agent contemplated 65 in our process is based upon its ability to treat An equivalent molal amount of propylene oxide certain emulsions more advantageously and at a is substituted for ethylene oxide in Examples 1-6 somewhat lower cost than is possible with other preceding. available demulsifiers, or conventional mixtures The preferred type of demulsifier is obtained thereof. It is believed that the particular de by the action of 2-10 moles of the oxalkylating 70 mulsifying agent Or treating agent herein de agent, for instance, ethylene oxide or propylene scribed will find comparatively limited applica oxide, on one mole of the imidazoline. tion, so far as the majority of oil field emulsions In the hereto appended claims, the addition are concerned; but we have found that such a products formed by reaction with acids or the demulsifying agent has commercial value, as it basic form by reaction with water, is included 75 Will economically break or resolve oil field emul 4 2,262,748 sions in a number of cases which cannot be consisting of allicyclic hydrocarbon radicals, ali treated as easily or at , so low a Cost with the phatic hydrocarbon radicals, and aliphatic hy demulsifying agents heretofore available. drocarbon radicals substituted by hydroxyl radi. In practising our process, a treating agent or calls; said oxyalkylated imidazolines containing demulsifier of the kind above described is brought the radical: into contact with or caused to act upon the emul sion to be treated, in any of the various ways, or by any of the various apparatus now generally wherein R. denotes an aliphatic radical and n is a , . . used to resolve or break petroleum emulsions whole number greater than 2 and less than 11; with a chemical reagent, the above procedure O Said radical substituted in the 2-position being being used either alone or in combination with derived from a higher fatty, acid. other demulsifying procedure, such as the elec 3. A process for breaking petroleum emulsions trical dehydration process. of the Water-in-oil type, characterized by sub The demulsifier herein contemplated may be jecting the emulsion to the action of a demulsi employed in connection with what is commonly fler comprising oxyalkylated inidazolines sub I known as down-the-hole procedure, i. e., bring stituted in 2-position by a radical containing sing the demulsifier in contact with the fluids of fron 11-22 carbonatoms selected from the group. the well at the botton of the well, or at some consisting of allicyclic hydrocarbon radicals, ali point prior to their emergence. This particular phatic hydrocarbon radicals, and aliphatic hy type of application is decidedly feasible when : drocarbon radicals substituted by hydroxyl radi the demulsifier is used in connection with acidif cals; Said oxyalkylated imidazolines containing cation of calcareOS oil-bearing strata, especially . . . the radical: ...... if suspended in or dissolved in the acid employed for acidification. What Wei claim as new and desire to secure. 25 wherein R. denotes an aliphatic radical and n is a . . . by Letters Patentis: whole number greater than 2 and less than 11; . . . . . A process for breaking petroleum emulsions said radical substituted in the 2-position being of the water-in-oil type, characterized by sub derived from naphthenic acid. jecting the emulsion to the action of a demulsi. 4. A process for breaking petroleum emulsions fier, comprising oxyalkylated inidazolines sub 30 of the water-in-oil type, characterized by sub stituted in 2-position, by a radical containing. jecting the emulsion to the action of a demulsi from 11-22 carbon atons selected from the group fier comprising oxyalkylated imidazolinies sub consisting of allicyclic hydrocarbon radicals, all stituted in 2-position by a radical containing phatic hydrocarbon radicals, and aliphatic hy from 11-22 carbon atoms selected from the group drocarbon radicals substituted by hydroxyl radia. consisting of allicyclic hydrocarbon radicals, ali. cals; said oxyalkylated inidazolines containin phatic hydrocarbon-- radicals, and aliphatic hy the radical: yalky . . . • ining drocarbon radicals substituted by hydroxy radi. cals; said oxyalkylated imidazolines containing -N-(R-O) nH; -NH-(R-O).H. the radical: . . wherein R. denotes an aliphatic radical and n is 40 is a whole number greater than 2 and less than 1. wherein R. denotes an aliphatic radical and n is a 2. A process for breaking petroleum emulsions whole number greater than 2 and less than 11; of the Water-in-oil type, characterized by sub said radical substituted in the 2-position being jecting the emulsion to the action of a demulsi derived from abieticacid. fier comprising oxyalkylated imidazolines sub MELVIN DE GROOTE. stituted in 2-position by a radical containing BERNHARD KEISER. from 11-22 carbon atoms selected from the group CHARLES M. BLAIR, JR