Patented May 14, 1946 2,400,394 UNITED STATES PATENT OFFICE 2,400,394 PROCESS FOR BREAKNG PETROLEUM EMULSIONS Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrollite Corporation, Ltd., Wilmington, Del, a corporation of Delaware No Drawing. Application December 14, 1944 Serial No. 568,228 8 Claims. (C. 252-344) This invention relates primarily to the resolu U. S. Patent No. 2,304,113, dated December 8, tion of petroleum emulsions, 1942, to Morgan, et al., and U. S. Patent No. The main object of Our invention is to provide 2,304,369, dated December 8, 1942, to Morgan, a novel and efficient process for resolving pe et al. troleum emulsions of the water-in-oil type, that As previously suggested, one type of raw mate are commonly referred to as "cut oil,' 'roily oil,' rial herein contemplated, consists of a cyclic com “enulsified oil,' etc., and which comprise fine pound having a 5-membered heterocyclic ring droplets of naturally-occurring waters or brines With two atoms different from carbon. More dispersed in a more or less permanent state specifically, they may be considered as deriva throughout the oil which constitutes the continu O tives of imidazole, frequently referred to as gly OuS phase of the emulsion. oxaline. Imidazole (glyoxaline) is indicated by Another object of our invention is to provide an the following formula: economical and rapid process for separating emulsions which have been prepared under con HC-N trolled conditions from mineral oil, Such as crude IS oil and relatively Soft Waters or weak brines. B s 2 B Controlled emulsification and SubSequent denul NBI sification, under the conditions just mentioned, The imidazolines or glyoxalidines may be con is of significant value in removing impurities, sidered as dihydro-derivatives of imidazole (gly particularly inorganic Salts from pipeline oil. 20 oxaline); and thus the expressions “dihydrogly Demulsification, as contemplated in the pres Oxalines' and "glyoxalidines' are often employed. ent application, includes the preventive step of The introduction of two hydrogen atoms at the Commingling the demulsifier with the aqueous 4-5 position results in the conversion of imidazole component which would or might subsequently into dihydroglyoxaline, which may be indicated become either phase of the emulsion, in absence 25 by the following formula: of Such precautionary measure. H, C-N The new chemical product, compound, or ma terial that is used as the demulsifier in the proc ess herein described, consists of the reaction H & 15 B -N product involving two moles of a 1,2-disubstituted 30 H glyoxalidine and one or more moles of urea or As to the manufacture of imidazolines, ref the equivalent thereof. The reaction involved erence is made to the following patents: U. S. Pat eliminates ammonia with the formation of the ents Nos. 2,215,861, 2,215,862, 2,215,863 and corresponding Substituted urea. Assuming the 2,215,864; dated September 24, 1940, to Wald reaction involves two terminal amino nitrogen 35 mann and Chwala. groups, it may be indicated, for the sake of brev Imidazolines or glyoxalidines may be regarded ity, in the following manner: as dehydration products of certain amides; and E they may be obtained by reacting polyamines -C-C-N and the higher carboxylic acids under certain conditions. The formation of these glyoxalidine Yi; BSE compounds, while forming no part of the present q=o invention, is indicated by the following scheme: --- or------a O - HO -C-C-NH. H. -Eli.H.NE H. H. N. 45 Ré–OHH.N.CH, CHRNH.R.x -8 Fatty Alkylene polyamine The linkage formed involves two amino nitro acid gen atoms connected by the divalent carbonyl O -IO radical. It is known, however, that two moles of urea may combine to give a mole of biuret, or, if 50 Rib-HNCHCH.R.NH.R.XH.0 - desired, biuret itself may be used to replace urea. Amide Other comparable compounds, as well as biuret, N may be used as the obvious equivalent of urea, for instance, thiou rea, or guanidine carbonate. R-ofich, - 2HO AS to the use of Such other reactants in some 55 --- 5 H.R. what analogous reactions, reference is made to 1,2-disubstituted glyoxalidine 2 2,400,394 wherein R represents an alkyl or alkenyl group, wax, petroleum and similar hydrocarbons; resinic such as one containing from 10 to 20 carbon and hydroaromatic acids, such as hexahydro atoms (the residue of a higher ); R1 benzoic acid, hydrogenated naphthoic, hydrogen represents hydrogen or a lower alkyl group; R2 ated carboxy-diphenyl, naphthenic, and abietic represents an alkylene group, or a lower alkyl acid; aralkyl and aromatic acids, such as hexa substituted alkylene group and X represents a hydrobenzoic acid, hydrogenated naphthoic, hy hydroxyl group, an amino group, or an annino drogenated polycarboxy-diphenyl, naphthenic, alkylene substituted amino group. (See U. S. and abietic acid; aralkyl and aromatic acids, Patent No. 2,214,152, dated September 10, 1940, such as benzoic acid, Twitchell fatty acids, naph to Wilkes. Also see U. S. Patents Nos. 2,155,877 O thoic acid, carboxy-diphenyl, pyridine carboxylic and 2,155,878, both dated April 25, 1939, to Wald acid, hydroxy-benzoic acid, and the like. mann and Chwala.) Other suitable acids include phenylstearic The expression "higher molecular weight car acid, benzoylnonylic acid, campholic acid, fen boxy acids' is an expression frequently employed cholic acid, cetyloxybutyric acid, cetyloxyacetic to refer to certain organic acids, particularly 15 acid, chlorstearic acid, etc. monocarboxy acids, having more than six car Ariother source of suitable acids are those com bon atoms, and generally, less than 40 carbon monly referred to as lac acids, such, for example, atoms. The commonest examples include the as the acids derived from shellac. Such acids detergent-forming acids, i. e., those acids which include various polyhydroxy acids, for example, combine with alkalies to produce soap or soap 20 aleuritic acid, shelloic acid, and kerrolic acid. like bodies. The detergent-forming acids, in The preferred aspect of our invention is con turn, include naturally-occurring fatty acids, cerned with the use of compounds derived from resin acids, such as abietic acid, naturally-oc detergent-forming monocarboxy acids, which in curring petroleum acids, Such as naphthenic clude those previously described having at least acids, and carboxy acids produced by the oxida 25 8 carbon atoms and not more than 32 carbon tion of petroleum. As will be subsequently in atoms. The preferred reagent in this particular dicated, there are other acids which have some CaSeconsists of the higher fatty acids, and more What similar characteristics and are derived especially, the unsaturated, higher fatty acids. from somewhat different sources, and are differ In order to illustrate the invention, the follow ent in structure, but can be included in the broad 30 ing examples are given of procedures that we generic term, previously indicated. have employed to produce the new compound or Among Sources of Such acids may be men material that is used as the demulsifier of our tioned straight chain and branched chain, sat process, although obvious varieties can be pre urated and unsaturated, carboxylic, aliphatic, pared in light of the class of reagents previously alicyclic, fatty, aromatic, hydroaromatic, and 35 enumerated. aralkyl acids, including , heptylic Eacample 1 acid, , , pimelic acid, Sebacic acid, , saturated and unsat l-aminoethyl-2-heptadecenyl glyoxalidine was urated higher molecular weight aliphatic acids, prepared by mixing i gram mole (282 grams) of Such as the higher fatty acids containing at least 40 , with 2 gram moles (206 grams) of di eight carbon atoms, and including, in addition ethylene triamine, and heating the mixture for to those mentioned, , , a period of about 16 hours, under a distilling col oleic acid, ricinoleic acid, diricinoleic acid, triric umn. Water was continuously removed until a inoleic acid, polyricinoleic acid, ricinostearolic temperature of about 245° C. was reached. The acid, ricinoleyl lactic acid, acetylricinoleic acid, 45 quantity of water thus removed amounted to chloracetyliricinoleic acid, , linolenic about 1.7 moles. Unreacted diethylene triamine acid, , , undecylenic acid, was distilled from the reaction mixture under , mixtures of any two or more of the vacuum, and the residue then was purified by above mentioned acids or other acids, mixed distillation at an absolute pressure of 1 mm. of higher fatty acids derived from animal or vege 50 mercury, at which point it boiled within a tem table sources, for example, lard, cocoanut oil, perature range of 225 to 250° C. About 220 rapeseed oil, sesame oil, palm kernel oil, palm grams of the 1-aminoethyl-2-heptadecyl gly oil, olive oil, corn oil, cottonseed oil, sardine oil, Oxalidine was obtained as a pale yellow liquid. tallow, soyabean oil, peanut oil, castor oil, seal 2 lbs. moles of the above product are mixed oils, whale oil, shark oil and other fish oils, tea with 1 lb. mole of urea and heated at a tempera Seed oil, partially or completely hydrogenated ture Within the range of 120° C. to approximately animal and vegetable oils, such as those men 160° C. until 2 moles of ammonia are eliminated. tioned; hydroxy and alphahydroxy higher car This requires approximately 20 minutes to 1 boxylic, aliphatic and fatty acids, such as hy droxystearic acid, dihydroxypalmitic acid, dihy 60 hour. The product so obtained is somewhat droxystearic acid, dihydroxybehenic acid, alpha darker in appearance, and much more viscous hydroxy capric acid, alpha-hydroxystearic acid, than the product prior to reaction with urea. alpha-hydroxy palmitic acid, alpha-hydroxy It is Soluble in water, dilute acids, etc. lauric acid, alpha-hydroxy myristic acid, alpha Eacample 2 hydroxy cocoanut oil mixed fatty acids, alpha hydroxy , alpha-hydroxy arachidic The same procedure is followed as in the pre acid, and the like, fatty and similar acids derived ceding example, except that a different disub from various waxes, such as beeswax, spermaceti, stituted glyoxalidine is employed, to wit, montan Wax, Japan wax, coccerin, and carnauba 1 - (aminoethyl ethylamino)-2-heptadecenyl wax. Such acids include carnaubic acid, cerotic 70 glyoxalidine. This glyoxalidine was prepared by acid, lacceric acid, , psyllastearic reacting 1 gram mole of oleic acid with 3 gram acid, etc. As suggested, one may also employ moles (438 grams) of triethylene tetramine. higher molecular weight carboxylic acids, derived The molal ratio of glyoxalidine to urea is left by oxidation and other methods, from paraffin is unchanged. 2,400,894 3 Erample 3 higher proportions of urea, or its equivalent is Tetraethylenepentannine is substituted for tri employed, due to the formation of a structure, as ethylene tetramine as a reactant in the preceding indicated in the following manner: example. B Eacample 4 -NCHCENE Lauric acid is substituted as a reactant for oleic d=0 acid in the three preceding examples. NCHCH. H Sample 5 O ExamplesRicinoleic 1-3, acid preceding. is substituted for oleic acid in Eacanple 6 Naphthenic acid is substituted for oleic acid in Examples 1-3, preceding. S Eacample 7 The same procedure is followed as in Examples -NCHCH.H 2 to 6, inclusive, except the molal ratio of urea AS far as we are aware, the reaction involving is doubled. 20 two moles of the glyoxalidine and 1 mole of the Eacomple 8 urea, involves the terminal primary amino rad The same procedure is followed as in Examples icals. When additional linkages are formed, as 2 to 6, inclusive, except that the molal ratio of indicated, provided that such linkages may take urea is tripled. 25 place in more than 1 position, we are unaware as Eacample 9 to the factors which determine the particular point of reaction. The same procedure is followed as in Examples In order to properly designate the herein con 1 to 6, inclusive, except that thiourea, biuret or templated compounds, we have referred to them guanidine carbonate is substituted for urea. as substituted carbamyl compounds containing at Attention is directed to the fact that products 30 least 2 radicals of the 1,2-disubstituted gly of the kind described show unusual resistance Oxalidine. to hydrolysis in strong acid solution, and thus, are particularly differentiated from somewhat similar compounds in which the high molal group derived, for example, from a fatty acid is present 35 in ester or amide form. This makes the con X-R-N-CH.R.. pounds herein contemplated particularly effec wherein R represents an alkyl or alkenyl group, tive for use as inhibitors in acid Solution, for the Such as one containing from 10 to 20 carbon formation of acid fluxes, and particularly for atoms (the residue of a higher fatty acid or its use in preventing emulsions in connection with 40 equivalent); R1 represents hydrogen or a lower the acidification of calcareous acid structure, as alkyl group; R2 represents an alkylene group or contemplated in our co-pending application a lower alkyl substituted alkylene group; and X Serial No. 568,229, filed December 14, 1944. represents a member of the class consisting of It has been previously pointed out that where amino groups and amino-alkylene, substituted urea is employed in the proportion of one mole of amino groupS, and having at least one occurrence urea for 2 of the glyoxalidine, that the structure of a divalent radical selected from the class con involves a linkage, such as the following: sisting of: -NCHCH-NH (-o: (-s; -Nh and (-o N H -NHCHCH-NH(-0 When, however, 2 moles of urea are employed for 2 moles of the glyoxalidine, a variety of other structures may enter into the combination, as, 55 radicals, and the aforementioned divalent radical for example, the formation of biuret, with the uniting the glyoxalidine radicals by being linked result that there appears a linkage such as the to nitrogen atoms. following: Compounds of the type herein described are basic in form, and it is understood that reference -N- in the claims includes the free base, i. e., the &=0 s 60 anhydro form, or the hydrated base formed by H combination with water or salts formed by com &=o bination with Organic or inorganic acids, such as citric acid, lactic acid, hydroxyacetic acid, -N- nitric acid, hydrochloric acid, etc. However, cyclic structures may be formed, due Attention is directed to U. S. Patent No. to the formation of 2 cross-linked structures, as 2,353,706, dated July 18, 1944, to De Groote & indicated by the following: Keiser. Said patent describes the Oxyalkylation, and particularly, the oxyethylation of 1,2-disub -N-CHCH-NHC=O C-O 70 stituted glyoxalidine of the type herein contem plated as reactants. It is understood that the -N-CHCH-NH products herein contemplated may be subjected It is entirely possible, however, and seems indi to oxyethylation under the same conditions, and cated by some of the thick, resinous products in the Sane manner, and in the same molal ratio formed, that polymerization occurs when the 73 as the simpler 1,2-disubstituted glyoxalidine de 4. 2,400,394 scribed in the aforementioned U. S. Patent No. Conventional demulsifying agents employed in 2,353,706. Furthermore, one may react the oxy the treatment of oil field emulsions are used as alkylated 1,2-disubstituted glyoxalidine with urea, such, or after dilution with any suitable solvent, thiourea, or other reactants of the kind herein such as water; petroleum hydrocarbons, such described, and obtain somewhat analogous con 5 as gasoline, kerosene, stove oil; a coal tar prod pounds, although the reactions appear to be con uct, Such as benzene, toluene, Xylene, tar acid plicated by the fact that reactions involving the oil, cresol, anthracene oil, etc. Alcohols, par following groups appear to take place to a greater ticularly aliphatic alcohols, such as methyl alco or lesser degree, particularly when both hydrogen hol, ethyl alcohol, denatured alcohol, propyl al atoms attached to the terminal amino nitrogen O cohol, butyl alcohol, hexyl alcohol, octyl alcohol, atoms have been subjected to oxyethylation, as etc., may be employed as diluents. Miscellane indicated in the following manner: ous Solvents, such as pine oil, carbon tetra chloride, sulfur dioxide extract obtained in the / CHO refining of petroleum, etc., may be employed as -N 5 diluents. Similarly, the material or materials Ycho:EEENii; employed as the demulsifying agent of our here ---. in described process for breaking petroletum (=0 emulsions, may be admixed with one or more of o:Ho:BiHSF: the Solvents customarily used in connection with 20 conventional demulsifying agents. Moreover, said material or materials may be used alone, The above product appears to form linkages Or in admixture with other suitable well-known which represent a particular type of carbonic classes of demulsifying agents. acid ester. It is well known that conventional demulsify However, when there is one hydrogen aton at 25 ing agentS may be used in a Water-soluble form, tached to an amino nitrogen atom available for or in an oil-soluble form, or in a form exhibiting reaction, the following reaction appears to both oil and water solubility. Sometimes they predominate: may be used in a form which exhibits relatively NC OH limited oil solubility. However, since such re 30 agents are Sometimes used in a ratio of 1 to 10,000, or 1 to 20,000, or even 1 to 30,000, or even 1 to 40,000, or 1 to 50,000, in desalting practice, such an apparent insolubility in oil and water is not significant, because said reagents undoubt edly have solubility within the concentration employed. This Same fact is true in regard to Nicho H the material or materials employed as the de In this instance the final product appears largely mulsifying agent of our process. to conform to that obtained by initial reaction We desire to point out that the superiority of with urea, followed by oxyethylation as a subse 40 the reagent or demulsifying agent contemplated quent step. Oxyalkylation, particularly Oxy in our process, is based upon its ability to treat ethylation, need not be limited to 2 annino radi certain emulsions more advantageously and at cals, but may be employed for the modification a Sonewhat lower cost than is possible with of a single amino radical, or for more than 2 other available demulsifiers, or conventional amino radicals. There must be a hydrogen atom 45 mixtures thereof. It is believed that the par attached to the amino radical, i. e., the amino ticular demulsifying agent or treating agent radical must be primary or secondary, in order to herein described will find comparatively limited be susceptible to oxyalkylation. application, so far as the majority of oil field In its broadest aspect, the present invention emulsions are concerned, but we have found that contemplates such variants in which the imidazo 50 such a demulsifying agent has commercial line radical contains a group selected from the value, as it will economically break or resolve class consisting of oil field emulsions in a number of cases which cannot be treated as easily or at so low a cost -N-(R3-O) H and -NH-(R3-O) inh with the demulsifying agents heretofore avail groups; wherein R3 denotes an aliphatic radical 55 able. and n is a small whole number greater than 2 In practising our process for resolving petro and less than 11; or the equivalent radicals pre leum emulsions of the water-in-oil type, a treat viously mentioned in connection with hydroxy ing agent or demulsifying agent of the kind ethylene derivatives, and which may be indicated above described is brought into contact with or in a broader aspect by the following structure: 60 caused to act upon the emulsion to be treated, in any of the various apparatus now generally used to resolve or to break petroleum emulsions With a chemical reagent, the above procedure being used either alone, or in combination. With 65 other demulsifying procedure, such as the elec trical dehydration process. The demulsifer herein contemplated may be employed in connection with what is commonly known as down-the-hole procedure, i. e., bring wherein R3 has its previous significance and in 70 ing the demulsifier into contact with the fluids is a small whole number less than 11. R3 par of the well at the bottom of the well, or at Some ticularly represents alkylene radicals having 2 point prior to the emergency of said fluids. This to 4 carbon atoms, such as the ethylene radical, particular type of application is decidedly feaS propyleneradical, butylene radical, glycide radical ible, when the demulsifier is used in connection and methyl glycide radical. 75 with acidification of calcareous oil-bearing 2,400,394 strata, especially if suspended in or dissolved in S the acid employed for acidification. 3. The process of claim 1, wherein R is the A somewhat analogous use of our demulsifying radical of higher fatty acid having 18 carbon agent is the removal of a residual mud sheath atons. which remains after drilling a well by the rotary 4. The process of claim 1, wherein R is the method. Sometimes the drilling mud contains radical of an unsaturated higher fatty acid added calcium carbonate, or the like, to render having 18 carbon atoms. the mud Susceptible to reaction with hydro 5. The process of claim 1, wherein R is the chloric acid, or the like, and thus expedite its radical of an unsaturated, higher fatty acid hav removal, O ing 18 carbon atoms, and the ratio of glyoxali The new composition of matter and method dine radicals to radicals selected from the class of making same herein described, constitutes the consisting of subject-matter of our divisional application Se rial No. 596,398, filed May 28, 1945, O Having thus described our invention, what we 15 8. d claimPatent asis: new and desire to secure by Letters o 1. A process for breaking petroleum emulsions radicals being 2 to 1. of the water-in-oil type, characterized by sub 6. The process of claim 1, wherein R is the jecting the emulsion to the action of a demulsi 20 radical of an unsaturated, higher fatty acid fier comprising a member of the class consist having 18 carbon atoms; the ratio of glyoxali ing of: (A) substituted carbamyl compounds dine radicals to radicals selected from the class containing at least 2 glyoxalidine radicals; said consisting of: glyoxalidine radicals being the radical of a 12 disubstituted glyoxalidine of the structure 25 and Od N E. 23N O 5 radicals being 2 to 1, and the number of nitrogeia X-R-N-CH.R. 30 atoms in each glyoxalidine radical being 3. wherein R is the radical of the detergent-form 7. The process of claim 1, wherein R is the ing monocarboxy acid having at least 8 and not radical of an unsaturated higher fatty acid having more than 32 carbon atoms; R1 is a member of 18 carbon atoms; the ratio of glyoxalidine radi the class consisting of hydrogen atoms and lower cals to radicals selected from the class consisting alkyl radicals; R2 is a member of the class con 35 Of sisting of alkylene radicals and lower alkyl sub stituted alkylene radicals; X is a member of the Pt class consisting of hydroxyl radicals, amino radi and O cals and amino alkylene-substituted amino radi cals; in said carbamyl compound the aforemen 40 O - tioned 1,2-disubstituted glyoxalidine radicals being united by a least one member selected radicals being 2 to 1, and the number of nitrogen from the class consisting of the divalent atoms in each glyoxalidine radical being 4. 8. The process of claim 1, wherein R is the radical of an unsaturated higher fatty acid hav ing 18 carbon atoms; the ratio of glyoxalidine -S; -Nh and NH sistingradicals of: to radicals selected from the class con

radicals; and the aforementioned divalent radi e cal uniting the glyoxalidine radicals by being and O linked to nitrogen atoms; and (B) oxyalkylated derivatives of the aforementioned carbamyl com O pounds in which there is at least one occurrence of the radical (RO), in which Rs represents 5 5 radicals being 2 to 1, and the number of nitrogen an alkylene radical having 2 to 4 carbon atoms atoms in each glyoxalidine radical being 5. and 7' is a small whole number less than 11. 2. The process of clan. 1, wherein R is the MELVIN DE GROOTE. radical of a higher fatty acid. BERNHARD KEISER. 80