US3158647A - Quaternary ammonium fatty, phenate and naphthenate salts - Google Patents

Quaternary ammonium fatty, phenate and naphthenate salts Download PDF

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US3158647A
US3158647A US14162061A US3158647A US 3158647 A US3158647 A US 3158647A US 14162061 A US14162061 A US 14162061A US 3158647 A US3158647 A US 3158647A
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quaternary ammonium
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Earl E Myers
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Gulf Research and Development Co
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/22Organic compounds containing nitrogen
    • C10L1/222Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/26Organic compounds containing phosphorus
    • C10L1/2633Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
    • C10L1/2658Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) amine salts

Description

United States Patent 3,158,647 QUATERNARY AMMONIUM FATTY, PHENATE AND NAPHTHENATE SALTS Earl E. Myers, Chcswiclr, Pa, assignor to Gulf Research 53; Development Company, a corporation of Delaware No Drawing. Original application Oct. 5, 1955, Ser. No. 538,799, new Patent No. 3,029,136, dated Apr. 10, 1962. Divided and this application Sept. 29, 196i, Ser. No. 141,620

Claims.

This invention relates to addition agents useful in the stabilization of distillate fuel oils. More particularly, the invention is concerned with certain novel quaternary ammonium salt addition agents disclosed hereinafter.

Uncompounded distillate fuel oil compositions are often troublesome with regard to sludge deposition during storage at normal atmospheric temperatures. Sludge deposits in distillate fuel oils are objectionable in that such deposits can cause clogging of burner filters, screens, nozzles, etc. and thereby lead to improper functioning of the combustion apparatus in which the fuel oil is consumed.

Although sludge deposition sometimes occurs in straight run distillate fuel oils, which oils contain mostly relatively stable parafiinic components, sludge deposition in these oils is normally considered to result from the presence of minor amounts of components that are not normally present and which impart instability to the otherwise stable oil, e.g., impurities added to and/or incompletely removed from the oil during refining, rather than from the inherent instability of the hydrocarbon components of the oil. The problem of sludge formation in such oils is considered essentially one involving oxidation and the formation of insoluble oxygenated products.

Catalytically cracked fuel oil distillates, on the other hand, are rich in olefinic, aromatic and mixed olefinicaromatic compounds. Sludging in such oils, when such occurs, is considered to involve primarily condensation and/ or polymerization type reactions which result in the formation of insoluble reaction products of relatively high molecular weight.

Sludge deposition in blends of straight run and catalytically cracked fuel oil distillates is an entirelydistinct problem from that for either component oil. While the sludge formed in such blended fuel oils very probably contains some sludge of the type formed in each component oil, the sludge formed in blended fuel oils is consistently greatly in excess of the amount that can be accounted for from the known sludging tendencies of the individual component oils, thus indicating the existence of a special problem.

I have found that sldge deposition in blended distillate fuel oils can be substantially diminished by incorporation therein of small amounts of the addition agents of this invention. The addition agents included by this invention are oil-soluble quaternary ammonium salts having two of the covalent N-bonds attached to aliphatic hydrocarbon radicals containing 8 to 22 carbon atoms, and having the remaining covalent N-bonds attached to saturated aliphatic hydrocarbon radicals containing 1 to 4 carbon atoms, and having the ionic N-bond attached to an anionic, salt-formingradical derived from a material selected from the group consisting of (a) oil-soluble organic monocarboxylic acids, and (b) oil-soluble monohydric phenols having attached to the aromatic nucleus at least one hydrocarbon substituent containing at least 4 carbon atoms, and having not more than one substituent in the ortho position that contains more than one carbon atom. The present invention includes the novel quaternary ammonium salts of the indicated class and methods of making these salts.

In what Way the quaternary ammonium salts described herein function to improve the characteristics of distillate fuel oils is not clear, and accordingly, the invention is not limited to any theory of operation. It would appear that they function as solubilizing agents for the sludge. However, in instances where other additive agents, considered to function similarly as the quaternary ammonium salts described herein, have been incorporated in blended distillate fuel oils in which some sludge has already formed, it has been noted that although the formation of additional sludge is inhibited, the already-formed sludge does not become dissolved. Nevertheless, in such instances it appears that although the already-formed sludge does not disappear, its characteristics are changed so as to prevent its deposition on burner screens, filters, or other burner parts.

The salts of this invention can be prepared in any suitable manner. For example, these salts can be prepared by reacting a suitable quaternary ammonium halide with silver hydroxide in a solvent and at conditions such as to form a silver halide precipitate, and a quaternary ammonium hydroxide. The latter can then be neutralized with a salt-forming, oil-soluble acidic material of the class included by this invention to form a quaternary ammonium salt of the desired type. However, I prefer to form the quaternary ammonium salts of this invention by reacting a suitable quaternary ammonium halide with an alkali metal hydroxide, e.g., potassium hydroxide, in alcoholic solution, thus forming a precipitate of an alkali metal halide and an alcoholic solution of a quaternary ammonium hydroxide. After separation of the alcoholic quaternary ammonium hydroxide from any excess, or unreacted, alkali metal hydroxide, the quaternary ammonium salt can be formed by neutralizing the quaternary ammonium hydroxide with the desired oil-soluble saltforming acidic material of the class included by this invention.

According to a preferred technique, any unreacted alkali metal hydroxide is separated from the alcoholic quaternary ammonium hydroxide by a procedure involving first, distilling the alcoholic solution containing quaternary ammonium hydroxide and unreacted alkali metal hydroxide, under reduced pressure sufiiciently low to permit distillation of the alcohol at a temperature below the decomposition point of the quaternary ammonium compound, e.g., F. or below, until a major portion of the alcohol has been removed. The alcohol removed by distillation is then replaced with an approximately equal volume of a non-polar solvent which is capable of forming an azeotropic mixture with alcohol and/ or Water, e.g., benzene. The addition of the non-polar solvent to the concentrated alcohol solution causes precipitation of excess alkali metal hydroxide. The thus precipitated alkali metal hydroxide can be removed by filtration. Since it is preferred to effect the neutralization of the quaternary ammonium hydroxide in a solvent other than alcohol, the above-described distillation, solvent addition and filtration can be repeated as many times as are necessary is to remove not only excess alkali metal hydroxide but also substantially all of the alcoholic solvent.

The reaction involving the liberation of the quaternary ammonium hydroxide from the corresponding halide takes place spontaneously at room temperature, and because of the formation of an insoluble reaction product, the reaction proceeds substantially to completion. Although equimolar proportions of the quaternary ammonium halide and the alkali metal hydroxide can be used, it is generally preferred to employ at least a small excess of the alkali metal hydroxide. The quaternary ammonium hydroxides formed by reaction of the quaternary ammonium halide with an alkali metal hydroxide are strong bases, comparable to alkali metal bases, and they react spontaneously at room temperature with about equimolar proportions of oil-soluble, salt-forming acidic materials of the class included by the invention, to form the desired substantially neutral quaternary ammonium salts.

Quaternary ammonium salts included by this invention can be graphically represented by the generic formula:

where R and R are similar or dissimilar aliphatic hydrocarbon radicals containing 8 to 22 carbon atoms, R and R are similar or dissimilar saturated aliphatic hydrocarbon radicals containing 1 to 4 carbon atoms, N is ni trogen, O is oxygen and where R is (a) the acyl residue 0 RJL of an oil-soluble organic monocarboxylic acid, C representing carbon and R representing a hydrocarbon radical of a size and configuration such as to impart oil-solubility to the parent acid, or (b) a substituted phenyl radical that has attached to the aromatic nucleus at least one hydrocarbon substituent containing at least 4, and preferably 4 to 15, carbon atoms and that has not more than one sub stituent in the ortho position containing more than one carbon atom.

In the foregoing formula, R, R R R and R; can be straight or branched chain radicals and can be substituted with substituents that do not adversely affect the oil-solubility of the ultimate salts and that do not react preferentially with oil-soluble acidic materials of the class included by the invention. For example, these substituents may contain halogen, nitrogen, phosphorus, oxygen and sulfur. Examples of substituents containing such elements are hydroxy, mercapto, chloro, bromo and like substituents.

Referring to the various N-substituents in greater detail the two long chain aliphatic hydrocarbon substituents are important as regards the performance characteristics of the class of salts of this invention, the latter being considered distinctly superior fuel oil sludge inhibitors as compared with similar salts containing other N-substituents or a lesser number of long chain N-substituents. Thus, the salts of this invention are particularly outstanding as regards water separation and susceptibility to Water-leaching. The long chain aliphatic hydrocarbon substituents can be, for example, alkyl, alkenyl or alkadienyl radicals containing 8 to 22 carbon atoms. Quaternary ammonium salts wherein the two long chain aliphatic hydrocarbon N-substituents are alkyl groups containing 12 to 18 carbon atoms are considered especially effective fuel oil addition agents. Examples of preferred long chain aliphatic hydrocarbon N-substituents are dodecyl (lauryl), tetradecyl (myristyl), hexadecyl, and octadecyl (stearyl) radical's. Examples of other suitable long chain aliphatic hydrocarbon N-substituents are octyl, dodecenyl, tetradecenyl, octadecenyl (oleyl), and octadecadienyl (linoleyl) radicals.

If desired, the two long chain aliphatic hydrocarbon N-substituents containing 8 to 22 carbon atoms can be derived from natural fats and oils, for example coconut oil, soybean oil, animal tallow and the like. In such instances the long chain aliphatic hydrocarbon N-substituents will consist essentially of mixed alkyl groups containing 8 to 22 carbon atoms.

The two short chain aliphatic hydrocarbon N-substituents can be any lower alkyl group. Although methyl and ethyl groups are preferred for the reason that they tend to minimize any hindrance to the addition of the long chain substituents to the nitrogen atom, isopropyl, propyl, and butyl groups can be present.

The nature of the ionic N-substituents of the salts of this invention is also important as regards the performance characteristics of these salts as sludge inhibitors in distillate fuel oils. Thus, it has been found that good results are obtained with quaternary ammonium salts having quaternary ammonium groups of the nature described above and whose ionic N-substituents are salt-forming radicals derived from materials selected from the group consisting of (a) oil-soluble organic monocarboxylic acids, and (b) oil-soluble monohydric phenols having attached to the aromatic nucleus at least one hydrocarbon substituent containing at least 4 carbon atoms, and having not more than one substituent in the ortho position that contains more than one carbon atom.

Oil-soluble organic monocarboxylic acids suitable for the purposes of this invention will normally contain 7 to 30 carbon atoms. Quaternary ammonium salts wherein the anionic substituent is a salt-forming radical derived from petroleum naphthenic acids form a preferred class of additives. As is known, such naphthenic acids are mixed alicyclic monocarboxylic acids recovered by alkali washing of petroleum distillates such as kerosene, naphtha, gas oil and lubricating distillates. The acids derived from these distillates are mixtures of alicyclic monocarboxylic acids containing about 7 to 30 carbon atoms per molecule, which mixtures have average molecular weights ranging from about 200 to about 450. Within the general class of petroleum naphthenic acids, the higher molecular weight acids derived from higher boiling distillates and containing 14 to 30 carbon atoms per molecule and having molecular weights of about 250 to 450 are considered to form especially effective quaternary ammonium salts for the purposes of this invention. Examples of other monocarboxylic acids that can be used to form quaternary ammonium salts included by this invention are oilsoluble, synthetic naphthenic acids such as cyclohexylacetic, cyclohexylpropionic, and cyclohexylstearic acids, and oil-soluble saturated or unsaturated fatty acids, such as caprylic, lauric, myristic, palmitic, stearic, oleic and linoleic acids. Mixtures of long chain fatty acids such as those derived from the saponification of natural fats and oils also can be used to form quaternary ammonium salts within the scope of this invention. Examples of such mixed fatty acids are coconut, soya and tallow fatty acids. In such instances, the acids will consist essentially of mixtures of oil-soluble straight chain monocarboxylic acids containing 8 to 22 carbon atoms.

As previously indicated, phenols that form salts with- I in the scope of this invention are oil-soluble monohydric phenols having attached to the aromatic nucleus at least one hydrocarbon substituent containing at least 4 carbon atoms and'having not more than one substituent in the ortho position that contains more than one carbon atom.-

st-ituent groups, e.g., nitro, amino, aryl, keto, or mercapto groups which do not affect the oil-solubility of the phenol and which do not react preferentially with the quaternary ammonium hydroxide. Phenols of the class described methylammonium chloride in isopropyl alcohol.

possess advantageous solubility and salt-forming characteristics.

Oil-soluble, monohydric phenols containing one aliphatic hydrocarbon substituent, having 4 to 15 carbon atoms, in the meta or para position to the hydroxyl group are considered to form especially eifective quaternary ammonium salts within the scope of this invention. For example, outstanding results have been obtained with quaternary ammonium salts of p-tert-octylphenol. Examples of other phenols that form suitable quaternary ammonium salts are p-tert-butylphenol, p-tert-amylphenol, p-sec-amylphenol, o-sec-amylphenol, o-tert-amylphenol, p-nonylphenol, cardanol, which consists essentially (approximately 90 percent) of a mixture of C straight chain meta-substituted phenols with difierent degrees of unsaturation in the side chains, hydrocardanol, i.e.; m pentadecylphenol, 2,6-dimethyl-4-tert-butylphenol, 2-tertamyl-4-methylphenol, 3 methyl 6 -tert-buty1phenol, 2- methyl 4,6 di tert butylphenol, and 2,4 di-tert-butylphenol.

Specific examples of preferred quaternary ammonium salts included by this invention are didodecyldimethylammonium naphthenate, dioctadecyldimethylammonium naphthenate, di-(hydrogenated tallow a1kyl-)dimethylammonium naphthenate, dicocoalkyldimethylammonium oleate, didodecyldimethylammonium oleate, dicocoalkyldimethylammonium naphthenate, di-(hydrogenated tallow alkyl-)dimethylammonium p tert octylohenate, the chief component or which is dioctadecyldimethylammonium p-tert-octylphenate. Examples of other salts included by the invention are the dioctyldimethylammonium, the didodecyldiethylammonium, the dihexadecyldipropylammonium, and the dioctadecenyldimethylammonium salts of naphthenic, oleic, stearic, caprylic, cyclohexylstearic acids, p-tert-amylphenol, p-sec-amylphenol, o-sec-amylphenol, o-tert-amylphenol, p-nonylphenol, cardanol, mpentadecylphenol, 2,6-dimethyl-4-tert-butylphenol, 2-tertamyl-4-methylphenol, 3 methyl 6 tert-butylphenol, 2- methyl 4,6 di-tert-butylphenol, and 2,4-di-tert-butylphenol.

The preparation of quaternary ammonium salts included by this invention is illustrated by the following specific examples.

EXAMPLE I An alcoholic solution of a quaternary ammonium halide was prepared by dissolving about 1380 grams of Arquad 2 HT in approximately 2 liters of absolute ethanol, the mixture being warmed to provide a reasonably clear solution, and this solution was then reacted as indicated below, Arquad 2 HT is manufactured by Armour & Company, Chicago, Illinois, and consists essentially of a 75 weight percent solution of di-(hydrogenated tallow alkyl-)c]l1ii T. e hydrogenated tallow alkyl radical consists essentially of a mixture of C H and C H radicals, with the latter predominating. The average molecular weight of the di- (hydrogenated tallow alkyl-)dimethylarmnonium chloride is about 570. An alcoholic solution of potassium hydroxide was then prepared by dissolving about 150 grams of potassium hydroxide in about 1600 m1. of absolute ethanol. Approximately 1200 ml. of the alcoholic potassium hydroxide were added slowly to the alcoholic Arquad 2 HT solution with stirring over a period of about to minutes. A precipitate of potassium chloride was formed immediately. Precipitated potassium chloride was separated from the mixture by filtration, and the remaining 400 ml. of alcoholic potassium hydroxide were then slowly added to the filtrate with stirring over a period of about 10 to 15 minutes. Further precipitation of potassium chloride was observed. The mixture was again filtered to remove precipitated potassium chloride and the filtrate was distilled under reduced pressure to remove about 75 percent of the alcohol solvent; Heat was applied to the stillpot through the medium of a water bath which was kept well below the boiling point, at an estimated temperature of not greater than about F. The reduction in pressure was achieved by the use of the laboratory vacuum line, which varies typically between about 25 and about 75 mm. Hg. The alcohol thus removed from the mixture was replaced with approximately an equal volume of benzene. The addition of benzene to the concentrated alcoholic solution caused precipitation of unreacted potassium hydroxide. After filtering the benzene:alcoholzdi-(hydrogenated tallow alkyl-) dimethylammonium hydroxide solution to remove precipitated postassium hydroxide, the mixture vwas again distilled as described above to remove approximately 75 percent of the solvent. The distilled solvent was again replaced with an approximately equal volume of benzene, and the mixture was again filtered. Approximately 3450 ml. of a benzene solution of di(hydrogenated tallow alkyl-) dimethylammonium hydroxide were obtained.

Approximately 2100 m1. of the foregoing solution were used to neutralize 200 ml. of a petroleum naphthenic acid cut boiling from about 145 to about C. at 3 mm. Hg, having a neutralization value of 213, and having an average molecular weight of about 381. The neutralization point was determined by the use of a litmus paper indicator. To the quaternary ammonium salt solution was then added a solvent-treated, Mid-Continent lubricating oil having a viscosity of about 450 Saybolt Universal seconds at 100 F. and an ASTM Union color of about 3, in an amount sufiicient to provide an ultimate, approximately 1:1 by weight solution of mineral lubricating oil and the quaternary ammonium salt. The thus obtained mixture was then distilled under vacuum as described above to remove benzene and water, and the remaining product was filtered. This product consisted essentially of an approximately 50 percent solution of di-(hydrogenated tallow alky1-)dimethylammonium naphthenate in a mineral lubricating oil. The principal component of the active portion of the solution was dioctadecyldimethylammonium naphthenate.

The 50 percent mineral oil solution produced in accordance with the above-described procedure had the following analysis:

Neutralization value 7.12 Oxide ash 0.10 Percent nitrogen 1.14

EXAMPLE ll the predominant component of the mixed alkyl radicals being the laurylradical, the balance of said mixed alkyl radicals being made up of smaller amounts of C C C C and C n-alkyl radicals. An alcoholic'solution of potassium hydroxide is prepared by dissolving about 75 grams of potassium hydroxide in about 800 ml. of absolute ethanol, and this solution is added slowly to the Arquad 2 C solution with stirring, until no additional precipitation of potassium chloride is observed. The mixture is filtered to separate potassium chloride, and the filtrate is distilled under vacuum as described in Example I to 1 remove about 75 percent of the alcoholic solvent. The volume of distilled alcohol is replaced with benzene, and the mixture is filtered to remove precipitated potassium hydroxide. The filtrate is again distilled under vacuum as described above to remove about 75 percent of the solvent, and the removed volume of solvent is again replaced with an equal volume of benzene. The mixture is again filtered to remove any precipitated potassium hydroxide. The filtrate comprises a benzene solution of dicocoalkyldimethylamrnonium hydroxide. This mixture is then neutralized using approximately 278 grams (the calculated stoichiometric quantity) of a commercial oleic acid (Emersol 233 LL Elaine, Emery Industries, Inc.) having an iodine value of 88:2, a free fatty acid content, calculated as oleic acid, of 101% i1%, and a saponification value of 203:2. The neutralized mixture is then diluted with about 682 grams of the lubricating oil diluent described in Example I. The benzene and water of neutralization are then distilled off at reduced pressure fol- I lowing the procedure described above. The remaining product is an approximately 50 percent mineral oil solution of dicocoalkyldimethylammoniurn oleate, the predominant component of the active portion of the solution being dilauryldimethylarnmonium oleate.

EXAMPLE III An alcoholic solution of a quaternary ammonium hydroxide was prepared by a procedure including first, dissolving about 690 grams of Arquad 2 HT in approximately 1 liter of absolute ethanol, the mixture being warmed to provide a reasonably clear solution, and then reacting the solution as indicated below. An alcoholic solution of potassium hydroxide was then prepared by dissolving about 75 grams of potassium hydroxide in about 800 ml. of absolute ethanol. Approximately 400 ml. of the alcoholic potassium hydroxide were added slowly to the alcoholic Arquad 2 HT solution with stirring over a period of about to minutes. A precipitate of potassium chloride was formed immediately. Precipitated potassium chloride was separated from the mixture by filtration, and the remaining 200 ml. of alcoholic potassium hydroxide were then slowly added to the filtrate with stirring over a period of about 10 to 15 minutes. Further precipitation of potassium chloride was observed. The mixture was again filtered to remove precipitated potassium chloride and the filtrate was distilled under reduced pressure to remove about 75 percent of the alcoholic sol vent. Heat was applied to the stillpot through the medium of a water bath which was kept well below the boiling point, at an estimated temperature of not greater than about 150 F. The reduction in pressure was achieved by the use of the laboratory vacuum line which varies typically between about 25 and about 75 mm. Hg. The alcohol thus removed from the mixture was replaced with approximately an equal volume of benzene.. The addition of the benzene to the concentrated alcoholic solution caused precipitation of unreacted potassium hydroxide. After filtering the benzene:alcoholzdi-(hydrogenated tallow alkyl)dimethylarnmoniurn hydroxide solution to remove precipitated potassium hydroxide, the mixture was again distilled as described above to remove approximately 75 percent of the solvent. The distilled solvent was again replaced with an approximately equal volume of benzene and the mixture was again filtered. Approximately 1650 ml. of a benzene solution of di-(hydrogenated tallow alkyl-)dimethylammonium hydroxide were obtained.

Approximately 488 ml. of the foregoing solution were neutralized with about 50 grams, the calculated stoichiometric quantity, of a' commercial (Rohm and Haas) p tert-octylphenol having a hydroxyl number of 270, a'

90 percent boiling point of 278308 C. at 760 mm. Hg, and a specific gravity (fused) of 0.941. To the quaternary ammonium salt solution was then added about 187 grams of a solvent-treated, Mid-Continent lubricating oil having a viscosity of about 450 Saybolt Universal seconds at 100 F. and an AST M Union color of about 3. The thus obtained mixture was then distilled under vacuum as described above to remove benzene and water of neutralization, and the remaining product was filtered. This product consisted essentially of an approximately 50 percent mineral oil solution of di-(hydrogenated tallow alkyl,)dimethylammonium p-tert-octylphenate. Dioctadecyldimethylammoniurn p-tert-octylphenate was the chief component of the active portion of the solution.

The 50 percent mineral oil solution produced in accordance with the above-described procedure had the following analysis:

Neutralization value 35.1

Oxide ash 0.09 Percent nitrogen 0.95

EXAMPLE IV A benzene solution of dicocoalkyldimethylammonium hydroxide is prepared from Arquad 2 C using the same quantities, materials and procedure described in Example II. This mixture is then neutralized using 164.2 grams, the calculated stoichiometric quantity, of a commercial p-tert-arnylphenol, having a melting point within the range 81 -91 C., a boiling point within the range 250- 260 C., a flash point (open cut) of about 230 F., and a phenol coefiicient of about 50-55. The neutralized mixture is then diluted with about 551 grams of the lubricating diluent described in Example I. The benzene and water of neutralization are then distilled off at reduced pressure, following the procedure described above. The remaining product is an approximately 50 percent mineral oil solution of dicocoalkyldimethylammonium ptert-amylphenate, the principal component of the active portion of this solution being dilauryldirnethylammonium p-tert-amylphenate.

The foregoing specific examples are illustrative of the salts of this invention and the preparation thereof. Other quaternary ammonium salts included by the invention can be similarly prepared by substituting, in equivalent proportions, other suitable quaternary ammonium halides, of the class herein indicated and other herein disclosed oil-soluble organic monocarboxylic acids and other oilsoluble hydrocarbon-substituted monohydric phenols for the corresponding reactants referred to in the foregoing embodiments.

The quaternary ammonium salts of this invention are useful when incorporated in blended distillate fuel oils in amounts suificient to inhibit sludge deposition therefrom. The quaternary ammonium salts of this invention are especially useful in mixtures of straight run and catalytically cracked fuel oil distillates wherein the ratio of straight run to catalytically cracked components is between about 9:1 and about 1:9, and preferably between about 4:1 and about 1:4, since such mixtures exhibit especially severe sludge depositing tendencies. A

poration therein of as little as about 0.001 to about 0.005 percent by weight of the composition of the salts of this invention. Excellent reductions in the sludging tendencies of mixed catalytically cracked and straight run fuel oil distillates have been obtained by incorporation therein of amounts between about 0.005 and about 0.1 percent by weight of the composition of the salts of this invention. Although in some instances it can be advantageous to employ still larger amounts, e.g., up to about 1.0 percent by weight of the composition, of the salts of this invention, no additional advantage will ordinarily be obtained by the use of more than this'arnount. It will be with the character of individual quaternary ammonium salts.

The quaternary ammonium salts of this invention can be incorporated in the blended distillate fuel oils in any suitable manner. For example, the desired quaternary ammonium salt can be added to either or both of the catalytica'lly cracked or straight run oils prior to mixing of the two, or it may be added to the mixed oil. When a quaternary ammonium salt of this invention is incorporated in a mixed oil, it is unnecessary to do this immediately after mixing the oil, as the compounds are effective even after some sludge has formed. It will usually be preferable to add the compound prior to any sludge formation as this will normally produce the greatest reduction in sludge deposition. The quaternary ammonium salts of this invention can be added to the blended fuel oils as such, but it is preferred to employ them in the form of concentrated solutions in an oil carrier. After addition, some circulation of the mixed oil is desirable to insure the early production of a uniform composition, but this is not absolutely necessary.

Specific examples of distillate fuel oils inhibited against sludge deposition by the quaternary ammonium salts of this invention are set forth below.

EXAMPLE V A blended No. 2 fuel oil having severe sludging tendeniies and consisting essentially of a 1:1:1 by volume mixture of a doctor sweetened West Texas straight run No. 2 fuel oil distillate, a South Louisiana straight run furnace oil boiling in the No. 2 range, and a fluid catalytically cracked light catalytic gas oil stock boiling in the No. 2 range was inhibited by incorporation therein of 0.02 weight percent of the 50 percent mineral oil solution of di- (hydrogenated tallow alkyl-)dimethylammonium naphthenate prepared according to Example I. The blended fuel used in this composition had the following characteristics:

Inspections- Gravity, API 33.5 Specific gravity 0.8576 Viscosity, SUS:

70 F. 37.9 100 F 34.5 Color, ASTM union 1 /2+ Pour point -15 Flash point, open cup, F 168 Carbon residue on bottoms, percent 0.38 Neutralization value 0.12 BS&W Trace Sulfur (lamp), percent 0.527 Bromine No 11.7 Olefins, percent 15.1 Aromatics, percent 21.9 Aniline point 129.0 Refractive index n 20 C 1.4832 Ash oxide, percent 0.01 Distillation, F.:

Initial 360 10% 416 50% 496 90% 580 End 630 EXAMPLE VI Another fuel oil composition having reduced sludging tendencies is obtained by admixture of the uninhibited fuel oil blend of Example V with 0.02 percent by weight of the composition of the mineral oil solution of dicocoalkyldimethylammonium oleate described in Example II.

EXAMPLE VII Another fuel oil composition having reduced sludging tendencies was obtained by admixture of the uninhibited fuel oil blend of Example V with 0.02 percent by weight of the composition of the mineral oil solution ofdi-(hydrogenated tallow alkyl-)dimethylammonium ptert-Octylphenate described in Example III.

10 EXAMPLE VIII Another fuel oil compocsition having reduced sludging tendencies was obtained by admixture of the uninhibited fuel oil blend of Example V with 0.02 percent by weight of the composition of the mineral oil solution of dicocoalkyldimethylammonium p-tert-amylphenate described in Example IV.

A No. 2 oil is defined in ASTM Standard on Petroleum Products and Lubricants, D 396-48 T. The No. 2 indicates a distillate oil for general purpose domestic heating for use in burners not requiring a No. 1 fuel oil and having the following properties: flash point, F. 100 or legal (min); pour point, F.-20 (max); water and sediment, percent by volume-0.1 (max); carbon residue, percent by weight--0.35 on 10% residuum; distillation temperature, F.-% point, 675 (max); viscosity, Saybolt Universal seconds at F.- 40 (max); gravity, API26 (min); and max. sulfur content-1%.

The properties upon which the sludge inhibiting characteristics of the salts of this invention depend appear to be shared by the entire class of salts disclosed herein. Accordingly, other suitable fuel oil compositions having reduced sludging tendencies can be obtained by substitution of other distillate fuel oils of the herein indicated kind and by substitution of other quaternary ammonium salts of this invention, in the same or equivalent proportions, for the corresponding components in the foregoing specific embodiments. For example, good results can be obtained by incorporating into blended distillate fuel oils 0.02 weight percent, or more, of the dioctyldimethylammonium, the didodecyldiethylammonium, the dihexadecyldipropylammonium, and the dioctadecenyldimethylammonium salts of naphthenic, oleic, stearic, caprylic, and cyclohexylstearic acids, p-tert-amylphenol, p-sec/amylphenol, o-sec-amylphenol, o-tert-amylphenol, p-nonylphenol, cardanol, m-pentadecylphenol, 2,6-dimethyl-4- tert-butylphenol, 2-tert-amyl-4-rnethylphenol, 3-methyl-6- tert-butylphenol, 2-methyl-4,6-di-tert-butylphenol, and 2,4- di-tert-butylphenol.

The usefulness of quaternary ammonium salts of this invention as fuel oil sludge inhibitors has been demonstrated by means of a standard accelerated sludging test which is carried out by heating 600 gram samples of the fuel oil composition being tested for periods varying from 16 to 64 hours at 210 F. in loosely stoppered, one-quart clear glass bottles. Following each heating period each test sample is cooled to room temperature and filtered by suction through tared, medium porosity fritted glass Gooch-type crucibles. The sludge in each crucible is washed with heptane. Complete removal of the sludge adhering to the inside of the bottles is obtained by means of a rubber policeman and heptane. The respective crucibles are then dried in an oven maintained at 210 F. for one hour, cooled in a desiccator, and reweighed.

the di-(hydrogenated tallow alkyl-)dimethylammonium chloride of Example I, di-(hydrogenated tallow a1kyl-) dimethylammonium hydroxide, di-(hydrogenated tallow a! kyl-)dimethylammoniu-m sulfon-ate, and a well-known commercial fuel oil sludge inhibitor that is considered to consist essentially of a 50 percent solution in mineral oil of the neutral and/ or basic barium salt of an alkylbenzene sulfonic acid 'wherein the (CH ):(CH ratio in the alkyl portion of the material is about 1:16.

Table Make-up: Percent by Wt.:

Blended Fuel Oil of Example V Di-(liydrogenated tallow alkyl-) dimethylammonium Naphtheuate of Example I (50% Mineral Oil Solution) Di-(hydrogenated tallow alky1-) dimethylammonium Phenate of Example 111 (50% Mineral Oil Solution) The results shown in column 1 of the table indicate the sludging characteristics of an uninhibited, blended No. 2 fuel oil. The results presented in columns 2 and 3 of the table show that a remarkable improvement in the sludge depositing characteristics of the fuel oil is obtained with quaternary ammonium salts of the kind included by this invention. The results presented in columns 4, 5, 6, and 7 of the table show the sludging properties of the fuel oil containing, respectively, the quaternary am monium chloride, hydroxide, and sulfonate, and the commercial fuel oil sludge inhibitor previously referred to. Comparison of the various results indicates the outstanding qualities of the quaternary ammonium salts of this invention.

It is to be emphasized that the remarkable properties of the additives of this invention are attributable to the characteristics of both the covalent N-substituents and the ionic N-substituent. Thus, comparison of the results obtained for compositions 2 and 3 with those obtained for compositions 4, 5, and 6 shows the importance of the nature of the ionic N-substituent.

Indicative of the importance of the character of the aliphatic hydrocarbon N-substituents of the quaternary ammonium salts included by the invention were the results of an experiment wherein 100 grams of a methanol solution containing 35 percent benzyltrirnethylammonium hydroxide were neutralized with about 43.2 grams of p tert octylphenol to form benzyltrimethylammonium p-tert-octylphenate, a compound outside the scope of this invention. Approximately 78.2 grams of a solvent-treated lubricating oil, derived from a Mid-Continent crude and having a viscosity of about 450 S.U.S./ 100 F., were added to the mixture, and methanol and water were removed by distillation under vacuum. The product was a 50 percent mineral oil solution of benzyltrimethylammonium p-tert-octylphenate. On cooling, the mixture solidified. Additional lubricating oil was added to make a 10 percent mineral oil-90 percent phenate mixture, but the phenate failed to dissolve. Ten grams of the lubrieating oil-phenate mixture were then added to 90 grams of benzene, but the phenate failed to dissolve. In view of its poor solubility, the benzyltrirnethylammonium p-tert-octylphenate was unsuited for use as a fuel oil additive.

In addition to the sludging test indicated in the table the Water separation properties of the various fuel oil compositions were determined according to Federal Specification VV-L-791d, Method FS 320.1.5 (modified), and were found to be relatively unimpaired for the fuel oil compositions of this invention.

If desired, the stable fuel oil compositions of this inven tion may contain, in addition to the additives disclosed herein, other improvement agents such as, for example, oxidation inhibitors, flash point control agents, corrosion inhibitors, anti-foam agents, ignition quality improvers, combustion improvers and other additives adapted to improve the oils in one or more respects.

it will be apparent to those skilled in the art that many modifications and variations of the herein-disclosed invention may be resorted to without departing from'the spirit thereof. Accordingly, only such limitations should be imposed as are indicated in the appended claims.

This is a division of my copending application Serial No. 538,799, filed October 5, 1955, and now US. Patent I claim:

1. A quaternary ammonium salt wherein two of the covalent N-bonds are attached to aliphatic hydrocarbon substituents containing 7 to 30 carbon atoms selected from the group consisting of alkyl, alkenyl and alkadienyl radicals containing 8 to 22 carbon atoms and the remaining covalent N-bonds are attached to open-chain saturated aliphatic hydrocarbon radicals containing 1 to 4 carbon atoms, and wherein the ionic N-bond is attached to an anionic salt-forming radical derived from a material selected from the group consisting of (a) oil-soluble organic monocarboxylic acids selected from the group consisting of fatty acids and naphthenic acids and (b) oil-soluble mono-, diand tri-substituted monohydric phenols whose substituents are open-chain aliphatic hydrocarbon radicals, said phenols having attached to the aromatic nucleusat least one hydrocarbon substituent containing at least 4 carbon atoms, and having not more than one substituent in the ortho position that contains more than one carbon atom.

2. Dioctadecyldimethylammoniurn naphthenate.

3. Di-(hydrogenated tallow alkyl-)dimethylammonium naphthenate.

4. Dioctadecyldimethylammonium p-tie -octylphenate.

5. Di-(hydrogenated tallow alkyl-)dimethylammonium p-tert-octylphenate.

References Cited in the file of this patent UNITED STATES PATENTS Great Britain Dec. 6, 1950 OTHER REFERENCES Ralston et al.: J. Org. Chem, vol. 13, pp. 186-190 Houben-Weyl: Methoden der organischen Chemie, v01. 11, part2, p. 624 (1958).

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,l58 647 November 24;, 1964 Earl E. Myers It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 12, line 31, strike out "containing 7 to 30 carbon atoms" and insert the same after "acids", in line 39 same column 12.

Signed and sealed this 13th day of April 1965,

(SEAL) Attest:

ERNEST W. SWIDER- EDWARD J. BRENNER Attesting Officer Commissioner of Patents

Claims (1)

1. A QUATERNARY AMMONIUM SALT WHEREIN TWO FO THE COVALENT N-BONDS ARE ATTACHED TO ALIPHATIC HYDROCARBON SUBSTITUENTS CONTAINING 7 TO 30 CARBON ATOMS SELECTED FROM THE GROUP CONSISTING 8 TO 22 CARBON ATOMS AND THE REMAINING COVALENT N-BONDS ARE ATTACHED TO OPEN-CHAIN SATURATED ALIPHATIC HYDROCARBON RADICALS CONTAINING 1 TO 4 CARBON ATOMS, AND WHEREIN THE IONIC N-BOND IS ATTACHED TO AN ANIONIC SALT-FORMING RADICAL DERIVED FROM A MATERIAL SELECTED FROM THE GROUP CONSISTING OF (A) OIL-SOLUBLE ORGANIC MONOCARBOXYLIC ACIDS SELECTED FROM THE GROUP CONSISTING OF FATTY ACIDS AND NAPHTHENIC ACIDS AND (B) OIL-SOLUBLE MONO-, DI- AND TRI-SUBSTITUTED MONOHYDRIC PHENOLS WHOSE SUBSTITUENTS ARE OPEN-CHAIN ALIPHATIC HYDROCARBON RADICALS, SAID PHENOLS HAVING ATTACHED TO THE AROMATIC NUCLEAUS AT LEAST ONE HYDROCARBON SUBSTITUENT CONTAINING AT LEAST 4 CARBON ATOMS, AND HAVING NOT MORE THAN ONE SUBSTITUENT IN THE ORTHO POSITION THAT CONTAINS MORE THAN ONE CARBON ATOM.
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Cited By (13)

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US3281458A (en) * 1961-03-15 1966-10-25 Nat Lead Co N-alkyl ammonium humates
US3632330A (en) * 1970-04-20 1972-01-04 Applied Biolog Sciences Lab In Combatting algae, bacteria and fungi with nitroso aryloxy quaternary ammonium compounds
US3883320A (en) * 1972-12-07 1975-05-13 Standard Oil Co Reducing deposits and smoke from jet fuels with additives incorporating an ammonium salt
US4365972A (en) * 1981-11-05 1982-12-28 Texaco Inc. Fuel composition
US4473377A (en) * 1982-06-30 1984-09-25 Mobil Oil Corporation Zwitterionic quaternary ammonium carboxylates, their metal salts and lubricants and fuels containing same
US4487698A (en) * 1982-05-03 1984-12-11 Bayer Aktiengesellschaft Extraction of onium salts from process waters and waste waters
EP0161082A2 (en) * 1984-04-26 1985-11-13 Mobil Oil Corporation Additives for improving low temperature characteristics of fuels, process of preparation and compositions and use thereof
EP0266193A1 (en) * 1986-10-31 1988-05-04 Exxon Research And Engineering Company Gasoline composition
EP0293192A1 (en) * 1987-05-27 1988-11-30 Exxon Chemical Patents Inc. Diesel fuel composition
US5348561A (en) * 1990-03-01 1994-09-20 Exxon Chemical Patents Inc. Fuel oil compositions
US6955761B2 (en) 2001-09-10 2005-10-18 Procter & Gamble Company Multifunctional filter
EP2033945A1 (en) * 2007-09-06 2009-03-11 Infineum International Limited Quaternary ammonium salts
WO2013043332A1 (en) * 2011-09-23 2013-03-28 The Lubrizol Corporation Quaternary ammonium salts in heating oils

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US2416309A (en) * 1941-08-29 1947-02-25 Dow Chemical Co Alkylamine salts of dinitrophenols
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Cited By (17)

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Publication number Priority date Publication date Assignee Title
US3281458A (en) * 1961-03-15 1966-10-25 Nat Lead Co N-alkyl ammonium humates
US3632330A (en) * 1970-04-20 1972-01-04 Applied Biolog Sciences Lab In Combatting algae, bacteria and fungi with nitroso aryloxy quaternary ammonium compounds
US3883320A (en) * 1972-12-07 1975-05-13 Standard Oil Co Reducing deposits and smoke from jet fuels with additives incorporating an ammonium salt
US4365972A (en) * 1981-11-05 1982-12-28 Texaco Inc. Fuel composition
US4487698A (en) * 1982-05-03 1984-12-11 Bayer Aktiengesellschaft Extraction of onium salts from process waters and waste waters
US4473377A (en) * 1982-06-30 1984-09-25 Mobil Oil Corporation Zwitterionic quaternary ammonium carboxylates, their metal salts and lubricants and fuels containing same
EP0161082A2 (en) * 1984-04-26 1985-11-13 Mobil Oil Corporation Additives for improving low temperature characteristics of fuels, process of preparation and compositions and use thereof
EP0161082A3 (en) * 1984-04-26 1986-08-13 Mobil Oil Corporation Additives for improving low temperature characteristics of fuels, process of preparation and compositions and use thereof
EP0266193A1 (en) * 1986-10-31 1988-05-04 Exxon Research And Engineering Company Gasoline composition
EP0293192A1 (en) * 1987-05-27 1988-11-30 Exxon Chemical Patents Inc. Diesel fuel composition
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US6955761B2 (en) 2001-09-10 2005-10-18 Procter & Gamble Company Multifunctional filter
EP2033945A1 (en) * 2007-09-06 2009-03-11 Infineum International Limited Quaternary ammonium salts
WO2013043332A1 (en) * 2011-09-23 2013-03-28 The Lubrizol Corporation Quaternary ammonium salts in heating oils

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