US2693448A - Demulsified antirust turbine oil - Google Patents

Demulsified antirust turbine oil Download PDF

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US2693448A
US2693448A US32871852A US2693448A US 2693448 A US2693448 A US 2693448A US 32871852 A US32871852 A US 32871852A US 2693448 A US2693448 A US 2693448A
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antirust
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Phillip S Landis
Henry D Norris
Ralph V White
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ExxonMobil Oil Corp
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    • CCHEMISTRY; METALLURGY
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    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M1/00Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
    • C10M1/08Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02Hydroxy compounds
    • C10M2207/023Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/026Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/04Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064Di- and triaryl amines
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064Di- and triaryl amines
    • C10M2215/065Phenyl-Naphthyl amines
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/26Amines
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/046Polyamines, i.e. macromoleculars obtained by condensation of more than eleven amine monomers
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/06Macromolecular compounds obtained by functionalisation op polymers with a nitrogen containing compound
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2210/00Nature of the metal present as such or in compounds, i.e. in salts
    • C10N2210/02Group II, e.g. Mg, Ca, Ba, Zn, Cd, Hg
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2210/00Nature of the metal present as such or in compounds, i.e. in salts
    • C10N2210/03Group III, e.g. Al, In, La
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2240/00Specified uses or applications of lubricating compositions
    • C10N2240/14Steam engines or turbines

Description

P Nov. 2, 1954 P, s. LANDls ETAL 2,693,448

DEMULSIFIED ANTIRUST TURBINE on.

Filed Dec. 50, 1952 INVENToRs f//u/ 5. Aw/5 5A/,2r a. Nam/5 BY mmv v. WH/rf 2,693,448 Patented Nov. 2, 1954 DEMULSIFIED ANTIRUST TURBINE OIL Phillip S. Landis, Mickleton, Henry D. Norris, Woodbury, and Ralph V. White, Pitman, N. J., assignors to Socony-Vacuum Oil Company, Incorporated, a corporation of New York Application December 30, 1952, Serial No. 328,718

7 Claims. (Cl. 252-33.4)

This invention relates to mineral lubricating oil formulations having reduced emulsion characteristics. It is more particularly concerned with the reduction of the emulsive tendencies of certain antirust turbine oil formulations.

In United States Letters Patent No. 2,568,876, issued on September 25, 1951, to the inventors named in the present application, there were disclosed, as antirust additives, reaction products produced by first reacting a polyalkylenepolyamine with a monocarboxylic acid to obtain an intermediate product and then reacting the intermediate product with an alkenyl succinic acid anhydride. It was found that some of these antirust additives imparted sufficient emulsive tendencies to some mineral oils` that the resultant blends failed to meet Navy specifications for turbine oils. It will be appreciated that it is desirable to reduce the emulsive characteristics of such blends, in order that the antirust agents will have a wider application in the eld of turbine lubrication.

It has now been found that the emulsive tendencies of certain mineral lubricating oils containing the more emulsive additives of Patent No. 2,568,876 can be sharply reduced. It has been discovered that the addition ,of small amounts of aryl sulfonic acids or their salts to blends of solvent-refined turbine oils containing the aforementioned antirust additives and antioxidants greatly reduces the emulsive characteristics of the blends.

Accordingly, it is an object of this invention to provide mineral lubricating oils having reduced emulsion characteristics. Another object is to provide turbine oil compositions having reduced tendencies to form lasting emulsions. A further object is to provide a method for reducing the emulsive tendencies of solvent-rened turbine oil compositions containing antirust additives produced by reacting a polyalkylenepolyamine with a monocarboxylic acid and then with an alkenyl succinic acid anhydride. A specific object is to provide a solvent-rened turbine oil containing the aforedescribed antirust additive, antioxidants, and a small amount of an arylsulfonic acid or of a salt thereof. Other objects and advantages of this invention will become apparent to those skillled in the art,

` from the following detailed description.

The present invention provides a solvent-refined turbine y oil having a viscosity of at least 350 seconds Saybolt at 100 F. containing an antioxidant and a small amount, suicient to prevent the rusting of ferrous metal surfaces, of an antirust agent produced by reacting oleic acid with a polyethylenepolyamine, having one more nitrogen atom than there are ethylene groups therein, in a molar proportion varying between about one to one, respectively,

` and about (sc-1) to one, respectively, x being the number of nitrogen atoms in the polyethylenepolyamine molecule to produce an intermediate product, and then reacting triisobutenyl succinic acid anhydride with the intermediate product, in a molar proportion of between about one to one respectively, and about (2c-,1) to one, respectively, the sum of the number of moles of oleic acid and of said triisobutenyl succinic acid anhydride so reacted with each mole of polyethylenepolyamine being no greater than x, and a small amount, suicient to reduce the emulsive tendencies of the blend of a petroleum sulfonic acid or of a salt thereof.

As is well known to those skilled in the art, one of the requirements of a turbine oil composition intended for use in marine turbines is that it must pass the Government Emulsion Test as dened in the Federal Stock heated to 130 F., and stirred with a specified paddle at 1500 R. P. M. for five minutes. Separation of the emulsion is observed while the cylinder is maintained at 130 F. The minutes required for the complete separation of the Water and oil phases are observed. If the separation of the emulsion is not complete, the number of cubic centimeters of emulsion remaining after 60 minutes is recorded. In order to be acceptable, the oil blend must demulsify in this test within 30 minutes. The test is also run using a one per cent NaCl solution as the emulsant.

In the specification of United States Letters Patent No. 2,568,876, it has been disclosed and demonstrated that some of the antirust agents claimed therein imparted unsatisfactory emulsion characteristics to oil blends containing them. This property renders such additives unsatisfactory for use in marine turbines, although the additives are excellent antirust agents. In mineral oils having viscosities of less than about 350 seconds Saybolt at F., no emulsion dificulties were observed. Of the heavier oils, i. e., those having a viscosity at 100 F. of more than 350 S. U. S., only the solvent-refined oils are improved in accordance with the present invention. Accordingly, the mineral oils which are utilizable in the compositions of this invention are solvent-refined turbine oils having a viscosity of at least 350 seconds Saybolt at 100 F. Such oils can be derived from any petroleum source, such as Far East, Mid-Continent, Coastal, etc., or they can be, a blend of solvent-refined turbine oils from various crude sources. The turbine oils contemplated herein are commonly known as heavy turbine oils and can have viscosities ranging as high as 950 seconds Saybolt at 100 F., and preferably between about 350 seconds and about 600 seconds at 100 F.

The antirust agents contemplated in the compositions of this invention are described fully in United States Letters Patent No. 2,568,876, issued in the names of the inventors herein. The disclosure of that patent should be referred to for detailed directions for preparing the antirust agent, and is considered part of this specification. In brief, the antirust agent is produced by a two step process. Initially, a monocarboxylic acid is reacted with a polyalkylenepolyamine, in a molar proportion of l between about 1:1 and about (x-1):1, respectively,

to produce an intermediate product. Then, the intermediate product is reacted with an alkenyl succinic acid anhydride, in a molar proportion of anhydride to intermediate of between about 1:1, respectively, and about (x-1) :1, respectively. In the molar proportions, x represents the number of nitrogen atoms in the polyalkylenepolyamine reactant. The total number of moles of monocarboxylic acid reactant and of alkenyl succinic acid anhydride reactant reacted per mole of polyalkylenepolyamne reactant must not be greater than x. The antirust agents particularly contemplated herein are those produced using oleic acid as the monocarboxylic acid reactant, a polyethylenepolyamine, and triisobutenyl succinic acid anhydride as the alkenyl succinic acid anhydride reactant. Non-limiting examples of the amine reactant are diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc. Named in the manner dened in column II of U. S. Patent No. 2,568,876, nonlimiting examples of the preferred antirust agents contemplated herein are: oleic acid (I) diethylenetriamine (I) -ltriisobutenyl succinic acid anhydride (I I); oleic 3 EXAMPLE 1 Single-distilled oleic acid (red oil) (2 moles) (564 grams) and triethylenetetramine (1.5 moles) (219 grams) were placed in a reaction Vessel which was provided with a stirrer, a thermometer, and a reflux takeoff trap. The reflux takeoff was filled with benzene and the stirred reactants were heated to 140 C. Then, 30 milliliters of benzene were added to the reaction mixture such that refluxing occurred with a pot temperature of l40-142 C. The reaction was continued for ten hours, during which time 57 milliliters of an aqueous layer (primarily water) was collected. The solvent was removed from the reaction mixture by distillation at a pot temperature of 145 C., and under about 20 millimeters pressure. This intermediate product had an N. N. of 5.5 and an average molecular Weight of about 484.

About 0.466 moles (225.7 grams) of this intermediate, 1.074 moles (285.7 grams) of triisobutenyl sucoinic acid anhydride (produced in accordance with U. S. Patent No. 2,380,699), and 500 grams of mineral oil B (defined hereinafter) were placed in a reaction vessel. The reaction vessel was equipped with a thermometer, a stirrer, and an outlet tube which, in turn, was connected to a manometer, a trap, and a vacuum pump. The reactants were heated, with stirring, to 100 C. and the pressure in the reaction vessel was reduced to 50 millimeters. The reaction was continued under these conditions for three hours. The reaction product had an N. N. of 53.7. This product contained about 50 per cent, by weight, of the active antirust agent.

In order to reduce the emulsive characteristics imparted to a turbine oil composition containing the aforedescribed antirust agents, any oil-soluble alkarylsulfonic acid, or a metal or ammonium salt thereof, can be utilized. The sulfonic acids can be those produced, by Well-known methods, from aromatic hydrocarbons or, more economically, from petroleum aromatic fractions, e. g., the mahogany sulfonates. In general, the metal portion of the alkaryl sulfonate salt is a metal of group I, Il, or III of the periodic chart of the elements. Especially preferred are sulfonates of sodium and potassium.

As indicated hereinbefore, the petroleum sulfonates are preferred. These are made by methods well-known in the art, by sulfonating aromatic petroleum fractions. In the specification and the claims, the terms petroleum sulfonic acid and petroleum sulfonates, denote any sulfonate or acid produced from petroleum fractions as aforedescribed. Non-limiting examples of the sulfonate reactant are petroleum sulfonic acid, ammonium petroleum sulfonate, sodium petroleum sulfonate, potassium petroleum sulfonate, barium petroleum sulfonate, strontium petroleum sulfonate, aluminum petroleum sulfonate, and zinc petroleum suifonate.

It has been found that greater reduction of the emulsion tendencies of an antirust mineral oil composition is effected by the sulfonic acid or sulfonate, when the cornposition also contains an antioxidant. The antioxidant does not appreciably affect the emulsion characteristics of a mineral oil blend, but unexpectedly, it enhances the effectiveness of a sulfonate or of a sulfonic acid. As is well known to those familiar with the art, most commercial turbine oils contain antioxidants. These are Well known in the art, and include substituted phenols, aryl amines, etc.; any of which are contemplated herein. Non-limiting examples of suitable antioxidants are 2,6- di-t-butyl-4-methylphenol; phenyl-a-naphthylamine; butyla-naphthylamine; octylated diphenylamine, etc. The antioxidants are added in concentrations sufficient to inhibit oxidation of the oil, usually between about 0.05 per cent and about 2 per cent, by weight. A preferred antioxidant is a combination of between about 0.05 per cent and about 1 per cent, by weight (preferably 0.2 per cent), of 2,6-di-t-butyl-4-methylphenol and between about 0.05 per cent and about 1 per cent, by weight (preferably 0.1 per cent), of phenyl-a-naphthylamine.

The concentration of the antirust agent in the lubricating oil compositions of this invention is between about 0.01 per cent, by weight, and about per cent, by weight. The amounts of emulsion-reducing additive, i. e., sulfonate or sulfonic acid, depend upon the particular additive and upon the concentration of antirust agent. In Figure 1 is set forth a curve showing the effect of concentration of a commercial petroleum sodium sulfonate (PB Emulsier) upon the emulsion characteristics of an fonate.

antirust blend. The curve is based upon emulsion data obtained from a series of runs involving a solvent-refined turbine oil (comprising a blend of solvent-refined Mid- Continent distillate stock and a solvent-refined Mid- Continent residual stock) having a Saybolt viscosity at F. of 400 seconds, containing 0.2 per cent, by Weight, of 2,6-di-t-butyl-4-methylphenol, 0.1 per cent, by weight, of phenyl-a-naphthylamine, 0.1 per cent, by weight, of the antirust agent of Example 1, and varying amounts of petroleum sodium sulfonate. It will be noted that the emulsion tendencies of the antirust turbine oil are satisfactorily reduced when the sodium sulfonate is added in amounts of between about 0.005 per cent and about 0.025 per cent. This range, however, applies when the antirust agent is used in a concentration of about 0.1 per cent. If the concentration of antirust agent is varied, the concentration of sulfonate varies directly therewith. For example, when the antirust agent is present at a weight concentration of 0.1 per cent, about 0.02 per cent of sodium sulfonate reduces the emulsion break time to about 15 minutes. When the concentration of antirust agent is doubled to 0.2 per cent, then the concentration of the sodium petroleum sulfonate must be doubled to 0.04 per cent, in order to achieve a break time of similar magnitude. Accordingly, the concentration of sodium sulfonate is best expressed as a function of the antirust agent concentration. Thus, based upon the weight concentration of antirust agent, the effective concentration of sodium sulfonate is between about 5 per cent and about 25 per cent.

In Figure 2 is presented a curve showing the effect of the concentration of a petroleum sulfonic acid upon the emulsion properties of an antirust turbine oil blend. The antirust oil blend used to obtain the data upon which the curve is based is the same as was used for Figure l; and the data were similarly obtained. It will be noted that, with a concentration of 0.1 per cent, by Weight, of antirust agent, the effective concentration of the petroleum sulfonic acid varied between about 0.005 per cent and about 0.08 per cent, by weight. Based upon the weight concentration of antirust agent, this amounts to a concentration of between about 5 per cent and about 80 per cent, by weight.

With respect to the polyvalent metal sulfonates, particularly those of groups II and III metals, and with ammonium sulfonates, it Was found that effective concentrations were between about 0.005 per cent and about 0.04 per cent, by weight, when using 0.1 per cent by weight of antirust agent. Based upon the weight concentration of antirust agent, therefore, the concentration of these salts will be between about 5 per cent and about 40 per cent.

ln addition to the antirust agent, antioxidant, and sulfonate or sulfonic acid, the mineral oil compositions of this invention can contain other substances to impart other desirable properties thereto. For example, there may be added pour point depressants, V. I. improvers, etc.

The following specific working examples are for the purpose of illustrating the compositions of this invention. lt is to be strictly understood that the invention is not to be limited by the specific additives utilized in the examples. As those skilled in the art will readily appreciate, a variety of other addition agents as set forth hereinbefore can be used.

Several demulsifying agents, i. e., sulfonates and sultonic acids, were used in the examples. A typical method of preparation is set forth in Example 2. It is to be understood, however, that this invention is not predicated upon the method of preparation used. Any arylsulfonic acid or salt is utilizable.

EXAMPLE 2 .designated hereafter as Demulsier A.

Demulsier B is a commercial sodium petroleum sul- It contains about 4.5 weight per cent sodium. Demulsier C is a sodium salt of the sulfonic acid obtained by sulfonating an aromatic stock containing which are set forth in Table I.

AVl-2O per cent aromatics and having a viscosityat 100 F. of 128-138 S. U. S. This sodium petroleum sulfonate Vcontains 3.8 Weight per cent sodium.

Demulsier D is a calcium salt of the sulfonic acid obtained by sulfonating an aromatic stock containing about 40 per cent aromatics and having a viscosity at 100 F. of 840 S. U. S. This calcium petroleum sulfonate contains 0.53 weight per cent calcium.

Demulsier E is a strontium salt of the sulfonic acid lobtained by sulfonating an aromatic stock containing vabout 35 per cent aromatics and having a viscosity at 210 F. of 80-83 S. U. S. This aluminum petroleum sulfonate contains 0.15 per cent aluminum, by weight.

Demulsifier H is an ammonium petroleum sulfonate, i. e., the ammonium salt of the sulfonic acid obtained by sulfonating an aromatic petroleum stock containing about 10420 per cent aromatics and having a viscosity at Demulsier I is a petroleum sulfonic acid produced by sulfonating an aromatic petroleum stock containing about 35 per cent aromatics and having a viscosity at 210 F. of 80-83 S. U. S. This petroleum sulfonic acid Yhas a neutralization number of 30.

EXAMPLES 3 THROUGH 5 A series of mineral lubricating oil blends were prepared each containing 0.1 weight per cent of the antirust agent of Example 1, and, respectively, none, 0.01 per cent, and 0.015 per cent of Demulsier B. Each blend Was subjected to the Emulsion Test, pertinent results of The mineral oil used was a blend of solvent-refined Mid-Continent distillate vand residual stocks having a Saybolt viscosity of 400 seconds.

EXAMPLES 6 THROUGH 19 To portions of blends comprising the mineral oil used in Examples 3-5 containing 0.25 per cent 2,6-di-t-buty1- 4-methylphenol, 0.1 per v cent phenyl-m-naphthylamine, and 0.1 per cent of antirust agent of Example l, were added various amounts of Demulsiiier B. Pertinent data and Emulsion Test results are set forth in Table I.

EXAMPLES 20 THROUGH 23 Blends were prepared in the mineral oil used in Examples 3-5 containing 0.1 per cent of the antirust agent of Example 2 and only one of the antioxidants of lthe preceding examples in each blend. Each blend was subjected to the Emulsion Test along with similar blends containing 0.01 per cent of Demulsitier B. Pertinent data and test results are set forth in Table I.

EXAMPLES 24 THROUGH 26 A series of blends were prepared in the base oil used in Examples 3`5, each containing 0.25 per cent 2,6di-t butyl-4-methylphenol, 0.1 per cent phenyl-a-naphthylamine, and varying amounts of the antirust agent of Example l and of Demulsiiier B. Each blend was subjected to the Emulsion Test. Pertinent data and results are set forth in Table I.

EXAMPLES 27 THROUGH 30 A series of blends similar to those described in Examples 24-26 were prepared, except that the concentrations of all of the additives were varied. Pertinent data for these blends and the Emulsion Test results therefor are set forth in Table I.

EXAMPLES 31 AND 32 Two blends were prepared in a solvent refined oil similar to that used in the preceding examples, except that the Saybolt viscosity thereof at 100 F. was 915 seconds, containing 0.25 per cent 2,6-di-t-butyl-4-methylphenol, 0.1 per cent phenyl-a-naphthylamine, and 0.1 perl cent of the antirust agent of Example l. To one blend was added Demulsier B. Then each blend was subjected to the Emulsion Test.` Pertinent data and results are set forth in Table I.

EXAMPLES 33 AND 34 Two blends similar to those of Examples 31 and 32, except that the base oil used had a Saybolt viscosity at F. of 600 seconds, were tested in the Emulsion Test. Pertinent data and results are set forth in Table I.

EXAMPLES 35 AND 36 Two blends similar to those of Examples 31 and 32, except that the base oil used had a Saybolt viscosity at 100 F. of 300 seconds, were subjected to the Emulsion Test. Pertlnent data and test results are set forth in Table I.

Table I Weight Percent Of- Government Emulsion Test at Base F.; Minutes Example Para Antiou for Break or nox PAN rust Demul- M1. Emulsion 441 Agent sier B at 60 Min.

of Ex. 1 Distilled Water S l 4 0. 1 S 1 34 0. 1 0 01 S 1 34 0.1 0 015 S 1 28 0. 1 O. 1 S 1 33 0. 1 0. 1 0.005 S 1 28 0. 1 0. 1 0. 01 S 1 20 0.1 0. 1 0.015 S 1 23 0.1 0. l 0.02 S 1 15 0.1 0. l 0.025 S 1 16 0.1 0.1 0.0275 S l 41 m1. 0. 1 0.1 0.03 S 1 27 m1. 0. l 0. 1 0.035 S 1 42 ml. 0. 1 0. 1 0.04 S 1 42 ml. 0. 1 0. 1 0.05 S 1 43 ml. 0. 1 0. 1 0.1 S 1 45 ml. 0. l 0. 1 0. 2 S 1 47 ml. 0. 1 0.1 0. 5 S 1 51 ml. 0. 1 0.1 S 1 38 2l 0.1 0.1 0 01 S 1 30 22. 0. l S 1 41 23- 0.1 0. 01 S 1 35 24 0.25 0.1 0.2 0.04 S 1 13 0. 25 0.1 0. 2 S 1 25 26". 0.25 0.1 0.2 S1 19 27 0. 5 0. 2 0. 1 S 1 35 28. 0.5 0. 2 0. 1 S 1 13 29 0. 2 0. 2 0. 2 S 1 35 30-.. 0.2 0.2 0.2 S1 25 31.. 0.25 0.1 0.1 T2 53 0. 25 0. l 0. 1 T 1 43 33.-. 0.25 0.1 0.1 U3 40 34.-. 0. 25 0.1 0.1 U3 33 35... 0.25 0.1 0.1 V1 26 36.-. 0. 25 0.1 0.1 V4 26 37.-- 0.25 0.1 0.1 W5 50 0. 25 0.1 0.1 W 5 58 0.25 0.1 0.1 W5 10 ml. 40..- 0. 25 0.1 0. l X t 55 4l. 0. 25 0.1 0. 1 X s 5 m1. 42.-- 0. 25 0.1 0.1 Y1 22 43 0. 25 0. 1 0. l Y 1 30 1 Biend of solvent-reiined Mid-Continent distillate and residual stocks of 400 S. U. S. at 100 F.

I Blend o solvent-refined Mid-Continent distillate and residual stocks 01915 S. U. S. at 100 F.

3 Blend of solvent-refined Mid-Continent distillate and residual stocks 600 S. U. S. atv100 F.

4 Blend of solvent-retined Mid-Continent distillate and residual stocks of 200 S. U. S. at100 F.

5 Acid-rened Stock of 110D-1200 S. U. S. at 100 F.

1 Acid-refined Stock of 600 S. U. S. at 100 F.

7 Acid-rened Stock of 140 S. U. S. at 100 F.

EXAMPLES 37 THROUGH 43 For comparison purposes, blends in acid-refined oils were prepared and tested in the Emulsion Test. Details of each blend are set forth in Table I, along with test relsults. See Table I for viscosity description of these o1 s.

From the data in Table I, it will be apparent that the addition of a petroleum sulfonate to a mineral oil containing antioxidants and antirust agent vastly improves the emulsion characteristics of the blend. It will be noted that little improvement is eiected when no antioxidants are used (Examples 3 and 4), but that addition of even one antioxidant enhances the effectiveness of the demulsifying agent. The antioxidants themselves, however, have no effect in demulsication (Examples 3 and 6). It will also be seen that this invention is not effective in acid-rened oils or in solvent-reiined oils having 'viscosities less than 300 seconds Saybolt at 100 F. The

EXAMPLES 44 THROUGH 51 To a series of blends of 0.25 per cent, 2,6-di-t-butyl- 4-methylphenol (Paranox 441), 0.1 per cent phenyl-vtnaphthylamine (PAN), and 0.1 per cent of the antirust agent of Example l in the base oil of Examples 3-5 (Base Oil S), were added various metal petroleum sulfonates and petroleum sulfonic acid in different amounts, as shown in Table II. These blends were subjected to the Emulsion Test. Pertinent data and results are set forth in Table II.

From the data in Table II, it will be appreciated that the present invention involves the use of any petroleum sulfonate of groups I, Il or III metals or of ammonia, and ofy petroleum sulfonic acids. The effective ranges of concentrations will also be apparent therefrom.

Although the present invention has been described in conjunction with preferred embodiments, it is to be understood that modications and variations may be resorted to, without departing from the spirit and scope of this invention, as those skilled in the art will readily understand. Such variations and modifications are considered to be within the purview and scope of the appended claims.

Table I I EMULSION TEST DATA FOR BLENDS OF BASE OIL S CON- TAINING 0.25% PARANOX 441, 0.1% PAN, 0.1% ANTIRUSI AGENT OF EXAMPLE 1 AND OIL-SOLUBLE PETROLEUM SULFONIC ACID OR SALT Government Emulsion gestvlat 130 1.' i inutes Example Sulfonic Acid or Salt lgvelcgeltt folrgrcak or rn mulsion at 60 Minutes,

Distilled Water 33 0.01 20 0. 02 17 4,4 Barmm Petroleum sulfonate (1.6% 0. 03 25 33)' 0. 04 29 0. 05 33 45 Ammonium Petroleum sulfonate.. 0. 05 16 46 Zic Petroleum sulionate (1.6% 0. O n 0.0 47 Strontium Petroleum sulfonate 0.015 17 (3.97% sr). o. o1 25 48 Calcium Petroleum sulfonate 0. 01 30 (0,53% oa). 0.14 11 49 Sollium petroleum sulfonate (3.8% 0.01 12 50 Aluminum petroleum sulfonate 0.02 23 (0.15% Al). g i) 0.01 20 0. 02 17 0. 03 20 51 Petroleum sulfvonic acid (N. N 30) g: 0.08 30 0. 1 37 0. 3 61 Inl. 0. 5 78 ml.

What is claimed is:

l. A solvent-refined turbine oil having a viscosity of between about 350 seconds and about 600 seconds Saybolt at 100 F. containing (l) between about 0.05 and about 2 per cent, by weight, of a phenolic antioxidant;

(2) between about 0.01 per cent and about 10 per cent, by weight, of an antirust agent which is the reaction product obtained by reacting oleic acid with triethylenetetramine, in a molar proportion of between about 3:1, respectively, and about 1:1, respectively, to produce an intermediate product and reacting an alkenyl succinic acid anhydride with said intermediate product, in a molar proportion of between about 1:1, respectively, and about 3:1, respectively, the number of moles of said oleic acid and of said alkenyl succinic acid anhydride reacted with each mole of said triethylenetetramine being no greater than 4; and (3) between about 5 per cent and about 25 per cent, by weight, based upon the weight concentration of said antirust agent, of a demulsier selected from the group consisting of petroleum sulfonic acids, ammonium salts of petroleum sulfonic acids and metal salts of petroleum sulfonic acids wherein the metal thereof is selected from groups I, II and III of the periodic table.

2. A solvent-reiined turbine oil having a viscosity of between about 350 seconds and about 600 seconds Saybolt at F. containing 1) about 0.25 per cent, by weight, of 2,6-di-t-butyl-4methylphenol; (2) about 0.1 per cent, by weight, of phenyl-alpha-naphthylamine; (3) about 0.1 per cent, by weight, of an antirust agent which is the reaction product obtained by reacting oleic acid with triethylenetetramine, in a molar proportion of about 1.3:l, respectively, to produce an intermediate product, and reacting triisobuteuyl succinic acid anhydride with said intermediate product, in a molar proportion of about 2.3:l, respectively; and (4) a demulsier consisting of about 0.02 per cent, by weight, of a sodium petroleum sulfonate.

3. The composition deiined in claim 2 wherein the demulsiiier is about 0.02 per cent, by weight, of barium petroleum sulfonate.

4. The composition dened in claim 2 wherein the demulsiier is about 0.05 per cent, by weight, of ammonium petroleum sulfonate.

5. The composition defined in claim 2 wherein the demulsier is about 0.02 per cent, by weight, of zinc petroleum sulfonate.

6. The composition defined in claim 2 wherein the demulsifier is about 0.02 per cent, by weight, of an alkaryl sulfonic acid.

7. A solvent-reiined turbine oil having a viscosity of between about 350 seconds and about 600 seconds Saybolt at 100 F. containing (l) between about 0.05 per cent and about 1 per cent, by weight, of 2,6-di-t-butyl- 4-methylphenol; (2) between about 0.05 per cent and about 1 per cent, by weight, of phenyl-alpha-naphthylamine; (3) between about 0.01 per cent and about 10 per cent, by weight, of an anti-rust agent which is the reaction product obtained by reacting oleic acid with triethylenetetramine, in a molar proportion of about l.3:l, respectively, to produce an intermediate product, and reacting triisobuteuyl succinic acid anhydride with said intermediate product, in a molar proportion of about 23:1, respectively; and (4) between about 5 per cent and about 25 per cent, by weight, based on the weight concentration of said anti-rust agent, of a sodium petroleum sulfonate demulsier.

References Cited in the le of this patent UNITED STATES PATENTS Number Name Date 2,482,517 Schiermeier Sept. 20, 1949 2,533,700 Wallace Dec. l2, 1950 2,568,876 White Sept. 25, 1951

Claims (1)

1. A SOLVENT-REFINED TURBINE OIL HAVING A VISCOSITY OF BETWEEN ABOUT 350 SECONDS AND ABOUT 600 SECONDS SAYBOLT AT 100* F. CONTAINING (U) BETWEEN ABOUT 0.05 AND ABOUT 2 PER CENT, BY WEIGHT, OF A PHENOLIC ANTIOXIDANT; (2) BETWEEN ABOUT 0.01 PER CENT AND ABOUT 10 PER CENT, BY WEIGHT, OF AN ANTIRUST AGENT WHICH IS THE REACTION PRODUCT OBTAINED BY REACTING OLEIC ACID WITH TRIETHYLENETETRAMINE, IN A MOLAR PROPORTION OF BETWEEN ABOUT 3:1, RESPECTIVELY, AND ABOUT 1:1 RESPECTIVELY TO PRODUCE AN INTERMEDIATE PRODUCT AND REACTING AN ALKENYL SUCCINIC ACID ANHYDRIDE WITH SAID INTERMEDIATE PRODUCE, IN A MOLAR PROPORTION OF BETWEEN ABOUT 1:1, RESPECTIVELY, AND ABOUT 3:1, RESPECTIVELY, THE NUMBER OF MOLES OF SAID OLEIC ACID AND OF SAID ALKENYL SUCCINIC ACID ANHYDRIDE REACTED WITH EACH MOLE OF SAID TRIETHYLENETETRAMINE BEING NO GREATER THAN 4; AND (3) BETWEEN ABOUT 5 PER CENT AND ABOUT 25 PER CENT, BY WEIGHT, BASED UPON THE WEIGHT CONCENTRATION OF SAID ANTIRUST AGENT, OF A DEMULSIFIER SELECTED FROM THE GROUP CONSISTING OF PETROLEUM SULFONIC ACIDS, AMMONIUM SALTS OF PETROLEUM SULFONIC ACIDS AND METAL SALTS OF PETROLEUM SULFONIC ACIDS WHERIN THE METAL THEREOF IS SELECTED FROM GROUPS I, II, AND III OF THE PERIODIC TABLE.
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1075255B (en) * 1957-12-16
US2794782A (en) * 1954-08-02 1957-06-04 Monsanto Chemicals Anti-rust emulsion resistant mineral oil composition
DE1042808B (en) * 1956-01-18 1958-11-06 Shell Res Ltd oil we
US2908649A (en) * 1956-10-01 1959-10-13 Monsanto Chemicals Anti-rust emulsion resistant mineral oil composition
US2954344A (en) * 1957-12-11 1960-09-27 Exxon Research Engineering Co Heavy duty lubricating oil
US3036969A (en) * 1957-11-26 1962-05-29 Exxon Research Engineering Co Oil containing rust inhibiting combination of two ingredients
DE1162964B (en) * 1959-03-05 1964-02-13 Monsanto Chemicals Hydraulic Liquid and lubricant
US20050272614A1 (en) * 2004-06-07 2005-12-08 Walker Johnny B Novel multi-purpose rust preventative and penetrant
US7888299B2 (en) 2003-01-15 2011-02-15 Afton Chemical Japan Corp. Extended drain, thermally stable, gear oil formulations

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2482517A (en) * 1945-03-13 1949-09-20 Shell Dev Corrosion inhibiting composition
US2533700A (en) * 1946-09-06 1950-12-12 Standard Oil Co Nonfoaming lubricant composition
US2568876A (en) * 1949-11-14 1951-09-25 Socony Vacuum Oil Co Inc Reaction products of n-acylated polyalkylene-polyamines with alkenyl succinic acid anhydrides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2482517A (en) * 1945-03-13 1949-09-20 Shell Dev Corrosion inhibiting composition
US2533700A (en) * 1946-09-06 1950-12-12 Standard Oil Co Nonfoaming lubricant composition
US2568876A (en) * 1949-11-14 1951-09-25 Socony Vacuum Oil Co Inc Reaction products of n-acylated polyalkylene-polyamines with alkenyl succinic acid anhydrides

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2794782A (en) * 1954-08-02 1957-06-04 Monsanto Chemicals Anti-rust emulsion resistant mineral oil composition
DE1042808B (en) * 1956-01-18 1958-11-06 Shell Res Ltd oil we
US2908649A (en) * 1956-10-01 1959-10-13 Monsanto Chemicals Anti-rust emulsion resistant mineral oil composition
US3036969A (en) * 1957-11-26 1962-05-29 Exxon Research Engineering Co Oil containing rust inhibiting combination of two ingredients
US2954344A (en) * 1957-12-11 1960-09-27 Exxon Research Engineering Co Heavy duty lubricating oil
DE1075255B (en) * 1957-12-16
DE1162964B (en) * 1959-03-05 1964-02-13 Monsanto Chemicals Hydraulic Liquid and lubricant
US7888299B2 (en) 2003-01-15 2011-02-15 Afton Chemical Japan Corp. Extended drain, thermally stable, gear oil formulations
US20050272614A1 (en) * 2004-06-07 2005-12-08 Walker Johnny B Novel multi-purpose rust preventative and penetrant
EP1605033A1 (en) 2004-06-07 2005-12-14 Afton Chemical Corporation Novel multi-purpose rust preventative and penetrant
CN100554515C (en) 2004-06-07 2009-10-28 雅富顿公司 Novel multi-purpose rust preventative and penetrant

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