United States Patent Office
Total Page：16
File Type：pdf, Size：1020Kb
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 fatty acid); 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 caprylic acid, heptylic Eacample 1 acid, Caproic acid, capric acid, pimelic acid, Sebacic acid, erucic 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 oleic acid, 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, melissic acid, stearic acid, 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, linoleic acid, linolenic about 1.7 moles. Unreacted diethylene triamine acid, lauric acid, myristic acid, undecylenic acid, was distilled from the reaction mixture under palmitic acid, 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.