US3080322A - Fire-resistant hydraulic fluids - Google Patents

Fire-resistant hydraulic fluids Download PDF

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US3080322A
US3080322A US115737A US11573761A US3080322A US 3080322 A US3080322 A US 3080322A US 115737 A US115737 A US 115737A US 11573761 A US11573761 A US 11573761A US 3080322 A US3080322 A US 3080322A
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oil
percent
water
weight
emulsion
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Rudolph J Holzinger
Hans F Waldmann
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ExxonMobil Oil Corp
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Socony Mobil Oil Co Inc
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Priority to DE19611444891 priority patent/DE1444891A1/de
Priority to FR885283A priority patent/FR1334956A/fr
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00—Lubricating compositions containing more than 10% water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/02—Water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102—Aliphatic fractions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/16—Naphthenic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/064—Di- and triaryl amines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/046—Overbased sulfonic acid salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01—Emulsions, colloids, or micelles

Definitions

  • Hydraulic systems are being employed more and more extensively in industry to operate machinery from remote locations and with comparative ease.
  • Various types of liquids have been employed as the operative uid in these hydraulic systems; however, for one reason or another, these liquids have been found to lack required properties.
  • Various oils, such as mineral oils have found much favor in the past; however, many applications of hydraulic systems cannot tolerate leaks with such a pressure transmitting medium since the oil, under high pressure, may then find its way to heat and llame where explosion or combustion occurs. Hydraulic systems are used in metalworking and treating plants and lea-ks in the system have caused serious accidents in the'past.
  • Water-in-oil emulsions have been tried in the prior art to provide a useful hydraulic oil that had the benefit of low ammability. As long as these emulsions remain unbroken with the water uniformly dispersed throughout the oil in the form of ne particles, the re resistance remains high. However, adequate stability and antiwear properties of the emulsion have not been present in prior formulations. The water particles tend to agglomerate in clusters and to settle to the lower part of the reservoir, thereby impairing the fire resistance of the uid remaining in the upper part. In some cases, an upper layer of clear oil possessing no -re resistance whatsoever will result.
  • the water may coalesce into larger droplets which eventually will settle out and form a layer of free water on the bottom.
  • free Water may enter the circulating system and may cause corrosion of lines and working parts and rapid wear of pump parts due to lack of lubrication.
  • the water particles be dispersed in the oil so that good lubricity is obtained.
  • the water particles be small and uniformly distributed throughout the oil to keep corrosion tendency to a minimum and provide the minimal amount of metal Wear.
  • Many prior art emulsions have employed commonly available surface active agents such as esters or partial 'esters of fatty acids and glycols or polyglycols.
  • esters of sorbitol and sorbitan sold under the tradenames Spans and Tweens the latter identifying ethylene oxide derivatives of such esters.
  • these agents cannot be employed in alkaline systems since under conditions of high temperature and pressure, the ester link age is broken and the emulsions become unstable. Consequently, they must be used in neutral or nearly neutral Systems. It is well known that in systems containing appreciable amounts of water, it is highly desirable to maintain a distinctly alkaline pH in order to minimize corrosion and corrosive wear.
  • a further object of this invention is to provide an im proved composition for use as an hydraulic iluid.
  • An additional object of this invention is to provide an proved composition having fire-resisting properties for use as an hydraulic fluid.
  • An additional object of this invention is to provide an improved stable Water-in-oil emulsion having nre-resisting properties for use as an hydraulic fluid.
  • An additional object of this invention is to provide an improved water-in-oil emulsion having anti-wear properties comparable to a mineral oil which is useful as a fireresistant hydraulic iluid.
  • Another object of this invention is to provide an improved method of preparing water-in-oil emulsions.
  • a stable, fire-resistant water-in-oil emulsion can be obtained by emulsifying up to 50 percent water with an oil, using a calcium sulfonate as the basic emulsier and further substantially improved by using selected sodium, potassium, ammonium, lithium, calcium, strontium or barium soaps of naphthenic acids having molecular weights of above about 275 as a stabilizing medium and anti-wear agent.
  • FIGURE 1 shows a plot of percent of oil separation versus potassium naphthenate content and percent of water separation versus naphthenic content after four days storage at 170 F. with 1 percent calcium sulfonate active) as the basic emulsiier.
  • FIGURE 2 shows a plot of percent of oil separation and percent of Water separation versus potassium naphthenate content after seven days storage at F. with 1 percent calcium sulfonate (100% active) as the basic emulsiiier.
  • FIGURE 3 shows a plot of percent of oil separation and percent of water separation versus potasium naphthenate content after seven days storage at 200 F. with 1 percent calcium sulfonate (100% active) as the basic emulsier.
  • FIGURE 4 shows a plot of percent of oil separation versus naphthenic acid content and percent of water separation versus naphthenic acid content after seven days storage at 175 F. (total emulsifier content being maintained at 1 percent of total composition).
  • FIGURE 5 shows a plot of percent of oil separation and water separation versus naphthenic acid content of total emulsier (total emulsifier content being maintained at 1 percent of total composition).
  • the oil used may -be any suitable hydrocarbon oil of viscosity range from about 504100 Saybolt Universal Seconds at 100 F. It has been found, however, that a White oil in that viscosity range provides unusually good results when using the ernulsifying and stabilizing agents disclosed hereinafter. This is a completely unexpected result since the rigorous refining required to produce white oils is generally conceded to remove natural inhibitors (see Kalichev-sky & Kobe, Petroleum Refining with Chemicals, Elsevier Publishing Company, 1956), reduce lubricity and greatly interfere' with emulsion sta- Ibiilty.
  • oil-soluble sulfonates are those obtained by sulfonation of mineral lubricating oil fractions which may be prepared by any of the well known and accepted methods in this art.
  • the calcium sulfonate used as the basic cmulsilier may be present in the lblend in the amount of 0.1-5.0 percent by weight of Ithe total blend but preferably about 0.25- 2.00 kpercent by weight can be used to provide entirely satisfactory results.
  • the calcium sulfonate While primanily an emulsifying agent, supplies a certain amount of anti-corrosive action and anti-wear protection.
  • Particularly useful calcium sulfonates are Calcium Petronate HMW or Basic Calcium yPetron-ate HMW supplied by Sonneborn and Sons, Inc.
  • the preferred naphthenic acids are those having molecular weights of about 315-500.
  • the concentration of the stabilizing agentgin the nished blend may vary from about 0.1-5.0 percent by weight but,y
  • the water may range from about -50 percent of the waterin-oil emulsion; however, a fully acceptable emulsion having excellent fire resisting properties is obtained when the water is about 25-45 percent of the water-inoil emulsion.
  • the water phase is added to they oil phase
  • a suitable method of4 li5 F. and the lime, after being added to the water, is kept in dispersion by mild agitation.
  • the water phase is then added to the oil phase under vigorous agitation, using a high-speed mixer, followed, if necessary, by further mechanical treatment such as passing the emulsion through a. colloid mill or homogenizer.
  • the amount of lime to be used in preparing these emulsions be sutiicient to form the basic soaps of the sulfonic and naphthenic acids and also, if a neutral calcium sulfonatev is used to convert the latter to the basic sulfona-te.
  • Another preferred method of preparing the'emulsions of this invention is the following.
  • This method is particularly preferred when using an [alkali of sufficiently high water solubility to form concentrated solutions such aspotassiurn or sodium hydroxide.
  • An [alkali of sufficiently high water solubility to form concentrated solutions such aspotassiurn or sodium hydroxide.
  • Two-thirds of the mineral oil and the required amount of naphthenic acid are heated to F. and the required amount of alkali, c g; potassium hydroxide,
  • ⁇ Rating of the emulsions formed may be done visually" either at room temperature or after storage at elevated temperature, e.g., F.
  • a convenient method consists of storing the emulsions in 100 ml. graduated cylin- ⁇ ders so that the volume of oil or water separated may beVv read directly as percent of total volume. Obviously, it is desirable to keep separation of oil and water to a minimum.
  • a measure of particle size may be had by electrical measurements, e.g., noting the voltage required toobtain ycurrent ow between submerged electrodes spaced 1/a apart.
  • electrical measurements e.g., noting the voltage required toobtain ycurrent ow between submerged electrodes spaced 1/a apart.
  • the voltage approaches zero.
  • the voltage required may exceed 500. Consequently, the higher the voltage readingobtained, the better the emulsion and vice versa.
  • the standard for good required that less than of the oil phase separated after seven days storage at 170 F. or less than 30% of the oil phase separated after seven days storage at 200 F.
  • the standard for good further required that less than 2% of the water phase separated after seven days storage at 170 F. or less than 10% of the Water phase separated after seven days storage at 200 F.
  • the standard for fair required that less than 35% of the oil phase separated after seven days storage Iat 170 F. or required more than tive days for complete separation at 200 F.
  • the standard for fair also required that less than 50% of the water phase separated after seven days storage at 170 F.
  • the standard for poor required that less than 75% of the oil phase separated after seven days storage at 170 F.
  • FIGURE 1 shows the water and oil separation of each naphthenate after storage for four days at 170 F.
  • FIGURE 2 shows the water and oil separation after seven days storage at 170 F.
  • FIG- URE 3 shows the amount of separation that occurred after seven days storage at 200 F.
  • the D curve is the 250 molecular weight naphthenic acid; the A curve is the 295 M.W. acid; the B curve is the 325 M.W. acid; and the C curve is the 415 M.W. acid.
  • the curves show that the A, B and C acids provide substantially better stability than the D acid.
  • the naphthenic acid of 325 M.W. provides major improvements in oil and water separation; moreover, the concentration of this acid is much less critical, covering an approximate range of from 25 to 85 percent in the case of oil separation, and an approximate range from 20 to 80 percent in the case of water separation. This is indicated by the areas below the broken lines, bounded by the respective curves. This acid is seen to be less sensitive to reduction of calcium sulfonate content.
  • Naphthenic acid of 415 M.W. effects similar improveyments with respect to oil separation, still greater improvements with respect to Water separation.
  • Oil separation is reduced from an original level of 30 percent toa level between 10 and 12 percent. Even more important, water separation is reduced :trom 50 percent to one percent or less.
  • the range of concentration in the latter case is especially broad, covering concentrations from 25 to 95 percent. The largeness of the area below the dotted line, bounded by the curve depicting water separation, is particularly noteworthy.
  • the improvement obtained by using the 415 M.W. naphthenic acid is clear, particularly when used in a concentration from 50 to 70 percent of total emulsier. For instance, oil separation at F. is reduced from about 60 to about 6 percent. Even more striking, however, is the improvement in storage stability at 200 P. In the absence of the 415 M.W. naphthenic acid, both oil and water separation amounted to 100 percent, the emulsion brokecompletely, Whereas in emulsions containing 60 ercent of 415 M.W. naphthenic -acid the oil separation was reduced to about 30 percent and the Water separation to about 36 percent.
  • the ratio between calcium sulfonate and the naphthenate' may vary from 5/95 to 95/5, depending upon the type and viscosity of the oil and the type and molecular weight of the sulfonate used.
  • Table Il gives stability results of a series of emulsions using different metals with 325 M.W. naph thenic acid as the naphthenate stabilizer, the amount being as indicated, and with 1 percent by weight of oilsoluble calcium petroleum sulfonate as the basic emulsifier, about 0.5 percent by Weight anti-oxidant, 41.5 percent by Weight of water and balance to 100 percent oil.
  • a sample of each emulsion was placed in a tall form 4 oz. oil sample bottle yielding a column height of 130 mm. and subjected toa seven day test at 170 F.
  • Various amounts of potassium soap prepared from naphthenic acid of molecular weight 415 and stoichiometric equivalents of potassium hydroxide were added to The resultant compositions were then evaluated as to their Wear characteristics.
  • a recognized test for lubricating capabilities, the socalled Vickers Pump Test may be achieved by circulating the fluid in a Vickers pump, such as Vickers Vane Type Pump, Model V-lll-ElO (rated Iat 2 gal. per. min), manufactured by Vickers Incorporated, of Detroit, Michigan. This is a positive displacement, vane-type hydraulic pump.
  • the rotor lwith twelve steel varies in contact with a steel ring, turns at 1200 r.p.m.
  • the twelve varies and the ring are weighed before and afterthe test, and the weight of metal worn olf during the .test is determined by diierence.
  • the pump test stand has a five gallon fluid reservoir and up to 2.5 gallons of fluid per minute are circulated at 1000 p.s.i. pressure. A convenient duration of test is hours, preferably run at a temperature of F. to simulate the severe operating conditions which hydraulic oils very frequently encounter in service. Wear in the Vickers pump occurs both on the vanes and on the ring. Vane wear is highly important and critical in the operation of the pump. Ring wear, although less important, still is of signicance. Since pumps of this general type are widely used in hydraulic systems, capability of a hydraulic iiuid, as a lubricant, to minimize such wear, is a necessity.
  • FIGURE 6 plotted against naphthenic acid concentration present in the form of potassium naphthenate.
  • ammonia to prepare ammonium naphthenate soaps may lead to' compositions which tend to lose alkali by volatization, especially under high temperature conditions. Such a loss can be counteracted by the use of alkali in excess over the stoichiometric equivalent Ias described above. Moreover, volatilization may provide additional benefits such as corrosion inhibition in the vapor phase.
  • a composition for use as hydraulic iluid consisting essentially of a water-in-oil emulsion containing 0.1-5.0 percent by Weight of oil-soluble calcium Ipetroleum sulfonate and 0.1-5.0 percent by Weight of a soap of naphthenic acids having a molecular weight greater than 275, the cation of the soap being selected fromV the group consisting of sodium, potassium, ammonium, lithium, calcium, strontium, and barium, the oil portion of Said emulsion being a hydrocarbon oil of from about 50-400.
  • the water con-tent ⁇ of said emulsion being about 10-50 percent by weight
  • the ratio be# tween the oil-soluble calcium petroleum sulfonate and the metal naphthenate being from about /95 to 95/ 5 by weight.
  • a composition for use as hydraulic fluid consisting essentially of a water-in-oil emulsion containing about 0.1-5.0 percent by weight of oil-soluble calcium petroleum sulfonate and about 0.1-5.0 percent by weight of soaps of naphthenic acids having molecular weights of about 275-1000, the cation of the soap being selected from the group consisting of sodium, potassium, ammonium, lithium, calcium and barium, the oil portion of said emulsion being a hydrocarbon oil of from about 50-400 S.U.S. viscosity at 100 F., the water content of said emulsion being about -50 percent by weight and the ratio between the oil-soluble calcium petroleum sulfonate and the metal naphthenate being from about 5/95 to 95/5 by weight.
  • a composition for use as hydraulic uid consisting essentially of a water-in-oil emulsion in which about 10- 50 percent by weight of the mixture is water uniformly distributed in ne-particle form and containing about 0.1- 5.0 percent by weight of oil-soluble calcium petroleum sulfonate as an emulsifying agent and vabout 0.1-5.0 percent by weight of soaps of naphthenic acids having molecular weights of about 315-500 as a stabilizing medium whereby the emulsion is retained with the water particles in tine-particle form and uniformly distributed throughout the mixture, the cation of the soap being selected from the group consisting of sodium, potassium, ammonium, lithium, calcium, strontium and barium, the oil portion of said emulsion being a hydrocarbon oil of from about 50-400 S.U.S. viscosity at 100 F. and the ratio between the oil-soluble calcium petroleum sulfon-ate and the metal naphthenate being from about 5/ 95 to 95/ 5 by weight
  • a composition for use as hydraulic uid consisting essentially of a water-in-oil emulsion in which about 25- 45 percent by weight of the mixture is wiater uniformly distributed in fine-particle form land containing about G25-2.00 percent by weight of oil-soluble ⁇ calcium petroleum sulfonate as an emulsifying agent and about 0.25- 3.0 percent by weight of soaps of naphthenic acids having molecular weights of about 315-500 as a stabilizing medium, the cation of the soap being Selected from the group consisting of sodium, potassium, ammonium, lithium, calcium, strontium and barium, whereby the emulsion is retained with the water particle-s in ne dispersion in the oil, the oil portion of said emulsion being a hydrocarbon oil of from about 50-400 S.U.S. viscosity at 100 F., and the ratio between the oil-soluble calcium petroleum sulfonate and the metal naphthenate being from about 5/ 95 to 95/5
  • a composition for use as hydraulic iiuid consisting essentially of a water-in-oil emulsion in which 25-45 percent by weight of the mixture is water uniformly distributed in fine-particle form, the oil is a white oil of about 50-400 S.U.S. viscosity at 100 F.
  • the mixture contains about 0.25-2.00 percent by weight of oil-soluble calcium petroleum sulfonate as an emulsifying agent and about 0.25-3.00 percent by weight of soaps of naphthenic acids having molecular weights of about 315-500 asa stabilizing medium, the cation of the soap being selected from the group consisting of sodium, lithium, potassium, ammonium, calcium, strontium and barium, whereby the emulsion is retained with the water particles in ine dispersion in the oil, the ratio between the oil-soluble calcium petroleum sulfonate and the metal naphthenate being from about 5/95 to 95/5 by weight.
  • a composition for use as hydraulic fluid consisting essentially of a water-in-oil emulsion in which about 25- 45 percent by weight of the mixture is water uniformly distributed in tine-particle form, the oil is a white oil of about 50-400 S.U.S. viscosity at 100 F.
  • the mixture contains about C25-2.00 percent by weight of oil-soluble calcium petroleum sulfonate as an emulsifying agent and about 0.25-3.00 percent by weight of soaps of a naphthenic acid having a molecular weight of 325 as a stabilizing medium, the cation of the soap being selected from the group consisting of sodium, potassium, lithium, ammonium, calcium, strontium and barium, Where-by the emulsion is retained with the water particles in line dispersion in the oil, the ratio between the oil-soluble calcium petroleum sulfonate and the metal naphthenate being from about 5/95 to 95/5 by weight.
  • a composition for use as hydraulic uid consisting es-sentially of a w-ater-in-oil emulsion in which about 25- 45 percent by weight of the mixture is water uniformly distributed in tine-particle for-m, the Ioil is a white oil of about 50-400 S.U.S. viscosity at 100 F.
  • the mixture contains about G25-2.00 percent by weight of oil-soluble calcium petroleum sulfonate as an emulsifying agent and about 0.25-3.00 percent by weight of soaps of naphthenic acid having a molecular weight of 415 as a stabilizing medium, the cation of the soap being selected from the group consisting of sodium, potassium, ammonium, lithium, calcium, strontium and barium, whereby the emulsion is retained with the water particles in ine dispersion in the oil, ythe ratio between the oil-soluble calcium petroleum sulfonate and the calcium naphthenate being from about 5/ 95 to 95/5 by weight.
  • a composition for use as hydraulic liuid consisting essentially of a Water-in-oil emulsion containing about G25-2.00 percent by weight of oil-soluble calcium petroleum sulfonate, about G25-3.00 percent by weight of naphthenic acids having a molecular weight of 315-500, an amount of calcium hydroxide substantially in excess of that required to produce the basic calcium sulfonate, an amount of an hydroxide substantially in excess of that required to produce the basic soaps of the naphthenic acids, the cation of the soap of said hydroxide being selected from the group consisting of sodium, potassium, ammonium, lithium, calcium, strontium and barium, the oil portion of said emulsion being a hydrocarbon oil of from about 50-400 S.U.S. viscosity at 100 F., the water content of said emulsion being about 150-50 percent by weight, and the ratio between the oil-soluble calcium petroleum sulfonate and the metal naphthenate being from about 5/95 to
  • composition of claim 8 further characterized in that the excess of calcium hydroxide is limited to about 1010 percent greater than that required to produce basic calcium sulfonate and the excess of metal lhydroxide is limited to about percent greater than that required to produce basic metal naphthenate.
  • composition of claim 8 further characterized in that the excess of calcium hydroxide is limited to about 50 percent greater than that required to produce basic calcium sulonate and the excess of metal hydroxide is limited to about 50 percent greater than that required to produce basic metal naphthenate.
  • Wat-er-in-oil emulsion which comprises the steps: dissolving naphthenic acids and oil-soluble calcium petroleum sulfonate in the base oil, the oil being a hydrocarbon oil of from about 50-400 S.U.S.
  • Visco-sity at 100 F. dispersing lime in the water, combining the oil phase with the aqueous phase in such a manner as to simultaneously effect both formation of basic calcium salts and emulsiiication, the amount of oil-soluble petroleum sulfonate being 0.1-5.0 percent by weight of the total blend, the amount of calcium naphthenate being 0.1-5 .0 percent by weight of the total blend, the ratio between the oil-soluble calcium petroleum sulfonate and the calcium naphthenate being from about 5/95 to 95/5 by weight and the molecular weight of the naphthenic acid used to form the calcium naphthenate having a molecular weight greater than 315.
  • a composition for use as hydraulic fluid consisting essentially of a water-in-oil emulsion containing about 0.1-5.0 percent by weight of oil-soluble calcium petroleum sulfonate and about 0.1-5.0 percent by Weight of the potassiumv soap of naphthenic acids havingrmolecular weights of about275-1000', the oil portion of said emula sion being a hydrocarbon ⁇ oil of from about 50-400 S.U.S. viscosity at 100 F., the water content of said emulsion being about 10-50 percent by Weight and the ratio between the oil-soluble calcium petroleum sulfonate and the potassium naphthenate being from about ⁇ /95 to 95/ 5 by weight.
  • a composition for use as hydraulic iluid consisting essentially of a water-in-oil emulsion in which about -50 percent by weight of the mixture is Water kuniformly distributed in fine-particle form and containing about ⁇ 0.1-5.0 percent by weight of oil-soluble calcium petroleum sulfonate as an emulsifying agent and about l0.1-5.0 percent by Weight of the 4 potassium soap of naphthenic acids having molecular weights of about 315-500 as a stabilizing medium whereby the emulsion is Yretained with the Water particles in ne-particle kform and uniformly distributed throughout the mixture, the oil portion of said emulsion being a hydrocarbon oil of from about 50-400 S.U.S. Visco-sity at 100 F. and the ratio between the oil-soluble calcium petroleum sulfonate and the potassium naphthenate being from about 5/95 to 95 5 by weight.
  • l oil-soluble calcium petroleum sulfonate
  • composition of claim 13 further characterized in that the molecular weight of the naphthenic acid is 325. 15. The composition of claim 13 further characterized in that the molecular weight of the naphthenic acid is 415.
  • the method of preparation of a Water-in-oil emulsion which comprises the steps: mixing a portion of the base oil' with naphthenic acid, heating the mixture to about F., adding with stirring a dilute solution of an alkali selected from the group consisting of sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonium hydroxide, calcium hydroxide, strontium hydroxide and 'barium hydroxide, raising the temperature of the mixture to about 190 F., adding with stirring oil-soluble calcium petroleum sulfonate, raising the temperature of the mixture to about 250 F.
  • an alkali selected from the group consisting of sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonium hydroxide, calcium hydroxide, strontium hydroxide and 'barium hydroxide

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
US115737A 1961-06-08 1961-06-08 Fire-resistant hydraulic fluids Expired - Lifetime US3080322A (en)

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BE611837D BE611837A (en)van) 1961-06-08
US115737A US3080322A (en) 1961-06-08 1961-06-08 Fire-resistant hydraulic fluids
DE19611444891 DE1444891A1 (de) 1961-06-08 1961-12-14 Hydraulische Fluessigkeit und Verfahren zu ihrer Herstellung
FR885283A FR1334956A (fr) 1961-06-08 1962-01-19 Fluides hydrauliques ininflammables

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3234143A (en) * 1962-05-21 1966-02-08 Socony Mobil Oil Co Inc Water-in-oil emulsion and method for the preparation thereof
US3472781A (en) * 1966-06-22 1969-10-14 Union Carbide Corp Hydraulic fluids
US4770798A (en) * 1984-04-13 1988-09-13 Labofina, S.A. Lubricating and anti-corrosion compositions
US4992185A (en) * 1988-05-11 1991-02-12 Mobil Oil Corporation Stability improver for water-in-oil emulsion
US6552090B1 (en) * 1997-09-15 2003-04-22 3M Innovative Properties Company Perfluoroalkyl haloalkyl ethers and compositions and applications thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2671758A (en) * 1949-09-27 1954-03-09 Shell Dev Colloidal compositions and derivatives thereof
US2744870A (en) * 1953-11-24 1956-05-08 Shell Dev Lubricating compositions
US2770597A (en) * 1952-11-13 1956-11-13 Sun Oil Co Soluble oil
US2802786A (en) * 1954-06-18 1957-08-13 Exxon Research Engineering Co Emulsifiable oil composition
US2820007A (en) * 1953-11-24 1958-01-14 Shell Dev Lubricating compositions
US2894910A (en) * 1956-07-23 1959-07-14 Shell Dev Water-in-oil emulsion lubricants

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2671758A (en) * 1949-09-27 1954-03-09 Shell Dev Colloidal compositions and derivatives thereof
US2770597A (en) * 1952-11-13 1956-11-13 Sun Oil Co Soluble oil
US2744870A (en) * 1953-11-24 1956-05-08 Shell Dev Lubricating compositions
US2820007A (en) * 1953-11-24 1958-01-14 Shell Dev Lubricating compositions
US2802786A (en) * 1954-06-18 1957-08-13 Exxon Research Engineering Co Emulsifiable oil composition
US2894910A (en) * 1956-07-23 1959-07-14 Shell Dev Water-in-oil emulsion lubricants

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3234143A (en) * 1962-05-21 1966-02-08 Socony Mobil Oil Co Inc Water-in-oil emulsion and method for the preparation thereof
US3472781A (en) * 1966-06-22 1969-10-14 Union Carbide Corp Hydraulic fluids
US4770798A (en) * 1984-04-13 1988-09-13 Labofina, S.A. Lubricating and anti-corrosion compositions
US4992185A (en) * 1988-05-11 1991-02-12 Mobil Oil Corporation Stability improver for water-in-oil emulsion
US6552090B1 (en) * 1997-09-15 2003-04-22 3M Innovative Properties Company Perfluoroalkyl haloalkyl ethers and compositions and applications thereof

Also Published As

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BE611837A (en)van)
DE1444891A1 (de) 1969-01-09

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