US2453690A - Process of producing polyvalentmetal hydrocarbon sulfonate - Google Patents

Process of producing polyvalentmetal hydrocarbon sulfonate Download PDF

Info

Publication number
US2453690A
US2453690A US560030A US56003044A US2453690A US 2453690 A US2453690 A US 2453690A US 560030 A US560030 A US 560030A US 56003044 A US56003044 A US 56003044A US 2453690 A US2453690 A US 2453690A
Authority
US
United States
Prior art keywords
oil
water
sulfonate
soluble
alcohol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US560030A
Inventor
Ulrie B Bray
Original Assignee
Ulrie B Bray
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ulrie B Bray filed Critical Ulrie B Bray
Priority to US560030A priority Critical patent/US2453690A/en
Application granted granted Critical
Publication of US2453690A publication Critical patent/US2453690A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G33/00Dewatering or demulsification of hydrocarbon oils
    • C10G33/04Dewatering or demulsification of hydrocarbon oils with chemical means
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01Sulfonic acids
    • C07C309/62Sulfonated fats, oils or waxes of undetermined constitution
    • 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
    • C10M135/00Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/08Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
    • C10M135/10Sulfonic acids or derivatives thereof
    • 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
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • 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
    • C10M2207/10Carboxylix acids; Neutral salts thereof
    • C10M2207/12Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/129Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
    • 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
    • C10M2219/02Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
    • 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
    • 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
    • C10M2219/08Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • 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
    • C10M2219/08Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/088Neutral salts
    • 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
    • C10M2219/08Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/089Overbased salts
    • 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
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04Phosphate esters
    • 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
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04Phosphate esters
    • C10M2223/042Metal salts thereof
    • 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
    • C10M2223/00Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04Phosphate esters
    • C10M2223/047Thioderivatives not containing metallic elements
    • 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
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/04Groups 2 or 12
    • 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
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/08Groups 4 or 14
    • 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
    • C10N2010/00Metal present as such or in compounds
    • C10N2010/14Group 7
    • 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
    • C10N2030/00Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • 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
    • C10N2050/00Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10Semi-solids; greasy

Description

Patented Nov. 16, 1948 CROSS REFERENCE PROCESS OF PRODUCING POLYVALENT- METAL HYDROCABBON SULFONATE Ulric B. Bray, Pasadena, Calif.

No Drawing. Application October 23, 1944. Serial No. 560,030

21 Claims. (Cl. 260-504) This invention relates to lubricating and rust preventing compositions, and also to processes for manufacture of such compositions.

Important objects of the invention are to produce compositions which are exceptionally efficient for lubrication purposes, especially in severe service engines, and for the prevention of rust under severe conditions of use. Another object is to provide methods for the easy manufacture of constituents employed in such compositions, particularly the production of oil-soluble, water-insoluble petroleum sulfonates substantially free from inorganic salts and water-soluble or kindred sulfonates which are generally conducive to rust formation, and to undue wear and corrosion in internal combustion enaines. 1n the preparation of some rust preventing compounds and lubricants, and in the preparation of some lubricants for severe service uses and for similar lubricating uses, it has been a practice for several years to employ various metal salts of sulfonic acids derived from petroleum fractions in connection with sulfuric acid treatment of such petroleum fractions. These sulfonic acids, and their salts are well known in the petroleum industry. Those most commonly used for the present purpose are the oil-soluble acids known as mahogany acids which are found in solution in a supernatant oil layer which accumulates above an acid sludge layer upon settling of a batch of petroleum lubricating oil following sulfuric acid treatment. The sulfuric acid treatment of petroleum lubricating all results also in the production of other sulfonic acids, known as "green acids, which are primarily water-soluble and are, therefore, found chiefly in the acid sludge layer. However, some of these watersoluble green acids are found in the presence of the oil-soluble mahogany acids in the oil layer and are objectionable for certain purposes. Possibly these vagrant water-soluble sulfonic acids pass into the oil layer because they are at the same time slightly oil-soluble, or because they are to that extent solubilized by the action of the mahogany acids. As a result, these objectionable water-soluble green acids are carried over as sulfonate into the oil-soluble sulfonate which is commonly placed upon themarket as the sodium salts of the mahogany acids. For the purpose of preparing rust preventing compounds and severe service lubricants, these sodium mahogan acid salts are commonly converted by metathesis into alkaline earth metal sulfonates, usually the calcium salts. The calcium salts of the true mahogany acids appear to be almost entirely insoluble in water although oil-soluble. But the resultant calcium salts of the green acids, which are readily water-soluble, are apparently also oilsoluble in the presence of mahogany acid salt. Because of their water-solubility, they are obiectionable in rust preventives and in lubricating oils where moisture may be encountered. because they appear to weaken the resistance to water of an oil mm on metal, possibly through favoring the formation of a water-continuous emulsion; whereas the water-insoluble, oil-soluble calcium salts of the true mahogany acids, when operating in the presence of water to form emulsions, resuit in emulsions where oil is the continuous phase. In the case of oil-continuous emulsions, the oil preferentially wets iron or steel surfaces with the result that the water present in the emulsion does not wet the metal and rusting is avoided. On the other hand. where the chemical environment producu water-continuous emulsions, the water phase displaces the oil from the metal surface, thereby reducing or destroying the rust inhibiting effect of the oil. Even though the oil-soluble, water-insoluble sulfonates greatly predominate, nevertheless, appreciable proportions of water-soluble sulfonates result in corresponding rusting eiiects, even a relatively small proportion of the water-soluble sulionate resulting in excessive water corrosion, to the extent that-products fail to give the full degree of protection required in severe service, such as in military and naval operation.

A primary object of the present invention is to eliminate the water-soluble sulfonates above-described. or at least to reduce them to such an insignificant Proportion that their presence is not detrimental. Another important object is to produce a finished sulfonate free from inorganic salts such as sodium chloride calcium chloride and sodium sulfate that may be formed by metathesis or be present as impurities.

I have discovered that the water-soluble sulfonates which ordinarily are present in commercial oil-soluble sulfonates of the mahogany acid type, such as those commonly placed on the marhot in the form of oil-soluble sodium sulfonates.

can be so completely eliminated from the alkaline earth metal product produced by metathesis as to be either not present at all or at least present in such reduced quantities that their presence and eflect are not detrimental. This purification of the oil-soluble sulfonatee is accomplished by diluting the batch of sulionates underlain: metathesis or purification with a smallpencentase.

example, around 2% or 3% or in the order of OR IN 252/33 SEARCH ROQN about 0.2% to of the total batch being treated, of a water-insoluble, oil-soluble aliphatic alcohol or other oxygen-bearing organic solvent havlngappropriate boiling point and sufiiciently low viscosity and preferably capable of producing viscosity reduction efi'ects. By suitable boiling point, it is intended to signify a material Whose boiling point is below the decomposition temperature of the sulfonate so that the diluent material may be eliminated from the product by vaporization. In general, this signifies a boiling point not materially in excess of 350 F., inasmuch as the initial decomposition temperature of a sulionate such as calcium sulfonate is in the neighborhood of 450' F. The object in using material of relatively low viscosity is to reduce the viscosity of the sulfonate so that it does not thicken or curd during the conversion operations.

This class of diiuents is best represented commonly by amyl alcohol (e. g. fusel-oil) and butyl alcohol. Both of these materials boil several degrees above the boiling point of water, and they are almost entirely insoluble in water. However. other alcohols that may be employed are the hexanols, the pentanols, and also the octanols (especially 2-ethylhexanol) In general, I may use any oxygen-containing organic compound possessing four or more carbon atoms, which is oil-soluble, water-insoluble and possesses a boiling point not appreciably above 350 F. and preferably not exceeding about 400 F. so far as is known, all aliphatic alcohols containing four or more carbon atoms and having a sufiicently low boiling point are usable. Some times it is desirable or permissible to leave the alcohol or a substantial proportion thereof in the finished sulfonate composition. In such a case, the boiling point oi the alcohol may not be a limiting factor in its use, as in the case of z-ethylhexanol.

In it broadest aspect, one phase of the invention resides in employing as a diluent in the purification or conversion of the sulfonates an oilsoluble, water-insoluble organic compound consisting only of carbon, hydrogen and oxygen, the diluent or solvent having a boiling point below the decomposition temperature of the sulfonates. In general, these materials contain at least four carbon atoms per molecule, and, in order to avoid too high a viscosity, they will ordinarily contain not more than about eight carbon atoms per molecule. More specifically, and primarily, the invention resides also in the definitely preferred class of oil-soluble, water-insoluble aliphatic alcohols whose boiling point is below the decomposition point of the sulfonates. These materials also contain at least four carbon atoms per molecule and ordinarily not to exceed eight carbon atoms per molecule in order to avoid excessive viscosity. The two members which constitute an outstanding preferred class are butyl alcohol and ethyl alcohol, these being especially preferred because of their relatively low boiling point, low viscosity and great effectiveness, and also because of their ready availability and relatively low cost. While aliphatic alcohols of four or five carbon atoms may be preferred, I may also use alcohols of the polymethylene series such as cyclohexanol and methyl cyclohexanol, and of the benzene se. ries such as phenol and cresol. Alcohols of the aliphati type containing ring constituents, such as benzy l alcohol and furfuryl alcohol, may be also used. These materials are normally liquid and are in general solvents for the mineral oils and oil-soluble sulfonates involved.

employed; that is, any sodium mahogany acid salt which characteristically contains a consid-.

erable proportion of mineral .oil commonly carried over into the commercial product from the mineral oil fraction which was originally treated in preparing the sulfonate. Such a commercial sulionate is ordinarily quite viscous or even semisolid at normal temperatures and contains varying amounts of mineral oil, for example, 15% to as much as 75% of the oil. This commercial concentrate is often further diluted with mineral oil as desired to reduce viscosity and facilitate han dling. It is sometimes desirable however. to employ no additional mineral oil or as small a proportion as possible in order to reduce the bulk be ing handled or; to produce a product of very vis-- cous or resinous consistency.

The sodium sulfonates in the oil carrier are all water-soluble or dispersible in water. In practicing my invention, one volume of sulfonate-oil mixture is dispersedin 1 to 5 or more volumes of water, preferably ator near the boiling point of water. This solution or-dispersion is thewatercontinuous type. For the purpose ofv conversion into an oil-soluble, water-insoluble metal suitonate, a water solution of an appropriate metal salt is then added and mixed, with the aqueous suli'onate-oil dispersion. at a temperature of about 210 F., agitationbeing employed to insure com- 'plete distribution. characteristically, a watersoluble calcium salt is used. such as calcium chloride in a, water solution of 40% concentration, a proportion of the solution being added sufllcient to provide at least a slight excess of calcium chloride. Other proportions oi. solution to afford a saitsfactory working volume of water and containing the salt in concentrations to yield any desired excess may be employed. The agitated heated mass usually quickly develops into a characteristic thick or doughy mass of oil-continuous emulsion as the water-insoluble calcium sulfonate forms. As a result subsequent settling produces relatively little separation, or at least very poor separation. Consequently, the water-soluble calcium sulfonates which are formed from the green acid salts during metathesis are mechanically retained in the massof oil-continuous emulsion. Also, the water phase dispersed as droplets throughout the oil-continuous mass contains the dissolved inorganic salts representing original impurities suci as sodium sulfate, sodium chloride produced by metathesis. and excess calcium chloride. It is extremely dimcult or practically impossible to wash out or settle out the briny water phase at this stage by the conventional method=. Heretofore, it has been the practice to evaporate the entire amount of water entrained in the oilcalcium sulfonate mass, and to remove as much as Possible of the inorganic salts and other impurities from the dehydrated oil-sulfonate mixture by mechanical means. such as centrifugin filtering in the presence of a filter aid such as II I...)

zoo-42a t'ROSS REFERENCE aasaeco diatomaceous earth. Naphthl. is sometimes addQ before, during or after the dehydration in order to iacilitate handling and removal of crystallized salts and other impurities. Such operations are laborious, expensive, and usually do not remove all inorganic salts from the finished product. Obviously, little or no rejection of watersoluble metal sulfonates is accomplished.

According to the improvement of this invention, a small quantity of the described oil-soluble, water-insoluble diluent alcohol or other indicated oxygen-bearing organic compound is added before, during or after the metathesis, with agitation so as to be thoroughly distributed throughout the mass being treated. Sufilcient organic compound is added to obtain good breaking of the emulsion, which seems to vary somewhat with the sulfonate, the amounts of oil and water present and amount of excess calcium chloride used. Ordinarily, 0.2% to 3.0% of commercial fusel-oil (iso-amyl alcohol) based on the volume of the kettle contents is employed. For somewhat faster operation, a greater proportion such as or even up to may be added, especial- 1y where the alcohol is to be recovered upon subsequent evaporation. Upon completing distribution of the alcohol in sumcient quantity through the mass, and stopping agitation, the phases quickly break, and separation by settling follows with comparative rapidity. The separation is so complete that a distinct line forms between the resultant supernatant oil phase in which most of the alcohol and all of the water-insoluble, oil-soluble calcium sulfonates have dissolved. and the lower water phase in which water-soluble calcium sulionate has dissolved along with excess calcium chloride and the resultant sodium chloride formed in the conversion, together with any other watersoluble impurities present. such as sodium sulfate and sodium sulflte. Separation of the phases may be accomplished, if desired, by centrifuging the mass after mixing in the alcohol, using for example a de Laval separator; but I have found settling in a. suitable vessel as described below to be satisfactory when the .proper alcohol is used in suitable amount.

After settling either the supernatant oil layer containing the diluent alcohol and the dissolved water-insoluble sulfonates may be decanted from the water layer, or the water layer may be withdrawn from the treating vessel leaving only the oil and alcohol layer. In either event, the oil layer is heated to expel any entrained water and the diluent alcohol, which alcohol may be passed to a recovery system if desired. Should an alcohol have been employed whose boiling point too close- 1y approximates the decomposition temperature of the sulfonate, the evaporation of the diluent may be-oonducted under appropriate vacuum.

The resultant solvent-free concentrate of calcium-sulfonate in oi. apparently contains little or no water-soluble sulfonate and no inorganic salts. In other words a mahogany acid soap concentrate comparatively free from green acid soaps and inorganic salts is produced. Or, in any event, the oil-containing concentrate possesses insufllcient objectionable sulfqnates or other impurities to interfere with the rust preventing and/or detergent properties of compounds produced therefrom.

If it should be that, in the heating of the oil layer to expel the diluent, a. product is yielded that requires clarification, it may be centrifuged, or a small amount or filter aid such as diatomaceous earth may be added and commingled with the 6 masathem'assbeingthenfilteredtoyieldaclear final product. For example, small amounts of crystallized salts, trapped in the oil-sulfonate solution following expulsion of solvent and of water that contained the salts and was entrained in the oil-sulfonate layer during settling, will be removed. So complete however is removal of such salts in the water layer, which separates upon the described alcohol treatment, that, in batches containing 900 lbs. of excess CaCh and other salts. less than 50 lbs. (sometimes as little as 10 lbs.) is trapped through the medium of entrained water, this being easily removed by centrifu-gation; whereas in the prior processes as much as 90% of the inorganic salts is commonly retained in the oil layer and must be removed as well as possible by mechanical means.

The employment of the described alcohol or other oil-soluble, water-insoluble oxygen-bearing compound described offers the further advantage that the oil-alcohol solution of the oil-soluble sulfonates may be readily water washed and rewashed without emulsification difilculties, should it appear desirable at any time so to treat the oil layer in order to remove the last traces of watersoluble sulfonate and inorganic salts from the oil solution. Additional quantities of the organic diluent compound are usually required at each wash as a greater'proportion of the electrolyte is removed, unless adequately large proportions of compound are initially used.

Another advantage in the employment of the alcohol or other described oxygen-bearing compound is that it may be added to a sulfonate concentrate before the addition of water, or either before or after dilution with additional oil when such is employed, whereby the organic solvent is present to take up the water-insoluble sulfonate as formed by metathesis, or at other stages, or

.portions may be added at various stages as required.

In general, the greater the excess of calcium chloride used or the higher the salts concentration in the water phase, the less the amount of alcohol required, but to take the fullest advantage of this in order to conserve alcohol presents the danger of excessive contamination in the event the settling or decanting operations are not perfect. I prefer to use a larger volume of water and a smaller excess of calcium chloride together with a larger proportion of alcohol when a product of maximum purity is desired, such as for use naval equipment.

As a specific example or one mode of practicing my invention, 4050 lbs. (477 gallons) sodium sulfonate of commerce, known as Grifiln Chemical Company's Gammanol L-100, containing approximately 64% sodium sulfonate, 26% lubricating oil and 10% water and inorganic salts, was charged into a steam heated kettle of 2200 gallons capacity. 1000 gallons of water was added and the kettle contents were heated to boiling and agitated to insure thorough dispersion or the commercial sodium sulfonate. Then 600 lbs. of commercial calcium chloride flakes (82% CaCh) dissolved in gallons of water was added to the kettle with agitation and continued boiling. Then four (4) gallons of commercial fused oil (about iso-amyl alcohol) was added with agitation to insure thorough mixing. Next, 500 gallons of refined mineral oil (500 seconds Saybolt Universal viscosity at F.) was added and the kettle contents again brought to boiling with agitation.

Soon after the contents again reached boiling SEARCH RODN temperature, both heating and agitation were stopped and the kettle contents were allowed to stand, 33212 hours. Two sharply defined layers developedd'uring standing, and the bottom layer consisting of water and dissolved impurities was drawn oil accurately and discarded. Heat was then applied to the kettle and the retained upper layer was heated with agitation to 275 F. to remove i'usel oil and water. Agitation with dry steam for a few minutes at 250 F. was employed. As the kettle contents were being heated, 50 lbs. powdered C9.(OH)2 were added to the kettle to insure a neutral or alkaline product. Ai'ter dehydration at about 275 1'. 1070 gallons oi the same oil as the 500 gallons added previously was added with agitation. The resulting blend was heated to 250 F. to 275 F. and passed through a Sharples Super-Centrifuge at the rate of 400 gallons per hour. The centrifuge bowl was cleaned three times while running the batch, first after 30 minutes. then after 2 hours, and at the end of the run. The total solids removed from the centrifuge bowl weighed 18.6 lbs. and consisted largely of excess Ca(H)z.

A yield of 1980 gallons 01' clear calcium sulfonate concentrate was obtained, containing approximately calcium sulfonate. Addition of 12 parts of this concentrate to 88 parts of a well refined mineral oil blend of 53 seconds Saybolt Universal viscosity at 100 F. gave a compounded oil meeting the requirements for rust preventive oil for small arms as given in U. 8. Army specification 2-120. The addition 01 12 to 18 parts of this concentrate to a number of different brands of heavy duty crankcase ofl conforming to U. 8. Army specification 2-104B gave in each case an interior engine preservative oil complying with U. S. Army Ordnance specification AXE-934. The addition of 20 parts oi this concentrate to 80 parts of refined mineral oil 01' 65 seconds viscosity at 210 F. gave a rust preventive oil complying with U. 8. Army Ordnance specification AXS-674, Revision 2. The addition 01' 5 parts of the concentrate along with 1 part tertiary amyl phenol sulfide to 94 parts 01' a well refined motor oil blend, having a viscosity 01' 62 seconds at 210 F. at :l a viscosity index of 78 gave a heavy duty crankcase oil complying with U. 8. Army specification 2-104B. The addition of 20 parts or the concentrate to 80 parts of petrolatum having a melting point of 138 F. and a penetration of 210 gave a resulting rust preventive compound complying with Army-Navy Aeronautical specification AN-C-124. The addition oi 10% to of the concentrate to sodium base greases used for automotive chassis lubrication not only imparted exceptional resistance to corrosion from moisture and salt water immersion, but also immaterial as a lubricant.

proved the resistance to disintegration by water to the point where such modified soda base greases compared satisfactorily in this respect with aluminum, barium, and lithium base greases. The addition of 5% to 20% of the concentrate to calcium, aluminum, barium, magnesium, zinc,

and lithium base greases. respectively, impTr'FFT both markedly improved anti-rusting properties and reduced tendency to bleed or separate on standing.

While my purified petroleum sulfonates or mahogany salts are usually the calcium products, the invention includes also the preparation or other alkaline earth metal suli'onates especially the barium salts and also the strontium salts. Such sulionates may be readily Pr pared by employing water-soluble barium or strontium salts instead 01' calcium chloride or other water-soluble calcium salt. The processgilcgnverting and puriapplicable to the production of water-insoluble, oil-soluble sulfonates oi metals other than the alkalne earth metals. Such metals include aluminum, zinc, magnesium lead, cobalt, nickel and the lik e. In brief. my process'inakes' it possible to manufacture efiiciently and economically the sulionates of any or the polyvalent metals.

For the purpose or production of rust preventives, as above indicated, the described waterinsoluble, oil soluble polyvalent. metal sulfonate concentrate in oil is diluted with such carriers as may be desired for the intended purpose. The diluent may be selected from any appropriate mineral oil lubricating fraction according to the ultimate use of the product. For example, the diluent may range anywhere from a very light petroleum fraction. such as one having a viscosity of 50 to 60 seconds Saybolt Universal at F. for low temperature work, up to one having a viscosity of 2000 seconds Saybolt Universal at 100 F. i corresponding generally with a lubricating oil oi an S. A. E. 70 grade) such as may be required for high temperature lubrication in aircraft engines and the like. In preparing such an oil, a quantity of the sulfonate product obtained by the above-described purification method will be employed to yield in the final product a proportion of the calcium sulfonate or other water-insoluble. oil-soluble metal suli'onate amounting to between about 0.5% and about 8% based on the blended product. Ordinarily, a satisfactory working proportion will be about 3%, or between about 2% and about 4%.

Inasmuch as lubricating properties are possessed by the petroleum fractions employed for solution therein of the sulfonates purified by the present improvement, the resultant rust-preventive products may be simultaneously employed as lubricants. In the case of aircraft and other engines as above mentioned, where heavier grades of lubricating oils are employed in producing the rust preventing composition, the engines may be subsequently operated with the rust preventive I! desired, other constituents may be incorporated in such oils to adapt them to special lubrication uses such as severe service conditions encountered in aircraft engines, Diesel engines, and the like. In those instances, other additives well known to thelubricating industry may be introduced, including (1) detergent soaps such as represented by oil-soluble calcium soaps and similar metal soaps of synthetic carboxylic acids produced by the oxidation oi parafiinic hydrocarbons. and (2) oxidation inhibitors such as sulfurized alcohols, sulfurized hydrocarbons, thiophosphates, phenolic thioethers, phosphites, suitable metal derivatives of these materials. and like materials known to th industry,

Similarly, purified sulfonates of the present in vcntion may be employed in the preparation of sulfonate-containing lubricating oil for severe service uses and the like which are not necessarily required for rust preventing purposes. Thus, typical lubricating oils may contain from about 0.5% to about 2%, for example 0.75%, of the purified alkaline earth metal sulfonate of this invention. together with from about'0.5% to 2% or 3%, for example about 1%. of oxidation inhibitors as above-described, or detergent soaps as above-described. or otherwise, to meet any given requirement. In many oi these instances,

Z lZU CROSS REFERENCE the gmplbyment of purified water-insoluble, oilsoiuhle alkaline earth metal sulfonates from pctroleum. as above-described, are especially valuable in counteracting tendencies toward undue corrosion in internal combustion engines, espe cially those of the severe service type such as the indicated aircraft and Diesel engines.

The purified sulfonates produced as described may be used in other compositions than those above disclosed. For example, they may be used as rust preventives in carriers which are normally solid and applied as films having appreciable thickness either by hot application or as solutions in readily volatilesolvents. Such sulfonates may be used also-in grease-like materials for rust preventing or lubricating purposes, or otherwise. For example, an appropriate quantity of the oil-sulfonate product may be added to petrolatum, and, if required, this composition thinned with petroleum lubricating fractions to whatever consistency desired. The petrolatum itself possesses lubricating properties.

When any of the products above-described are to be used under conditions where foaming is apt to be encountered, purified sulfonates may be produced, as above-described, by employing the indicated octyl alcohol and terminating the subsequent expulsion of the octyl alcohol so as to leave around 0.5% to 2% of octyl alcohol in the oil-sulfonate solution whereby to impart antiioaming charcteristics. The same will be true of any other organic solvent which is employed and possesses anti-foaming characteristics. I have also found that the prwence of 0.25% to 2% of octyl alcohol or other high molecular weight alcohol in the finished lubricant increases very greatly the effectiveness of the sulfonate addition in combating corrosion from hydrobromic acid. For example, the addition of 2.5% calcium sulfonate to a heavy duty motor oil containing 0.75% calcium soap of oxidized petroleum acids and 0.75% calcium salt of tertiary amyl phenol sulfide was sufiicient to protect the crankcase interior of engines against rusting from moisture condensation, but was insuillcient to protect against dilutes aqueous hydrobromic acid. The addition of 0.75% of octyl alcohol (z-ethylhexanal) to the foregoing oil containing 2.5% sulfonate, as described, gave perfect protection against hydrobromic acid corrosion as required in Army-Navy Aeronautical specification AN- VV-C-576 and Army Ordnance specification AXS-934. The addition of the octyl alcohol in any amount to the heavy duty oil described, without the addition of the sulfonate, failed to correct the corrosion from hydrobromic acid. Other alcohols, alcohol-esters such as CarbitoP' and Cellosolve (monoethyl ethers of diethylene and ethylene glycol respectively, made by Carbide and Carbon Chemical Corporation), and their alkylated derivatives, may be used to increase the effectiveness of the sulfonate addition in combating hydrobromic and hydrochloric acid corrosion of iron surfaces.

At present I have no theory regarding the operability of the indicated class of organic compounds which are useful for breaking the emulsion formed when sodium suli'onate is converted to alkaline earth or heavy metal sulfonates by metathesis, whereby good separation between the oil layer and water layer results. Obviously, it m not wholly a matter of viscosity reduction imparted by the low viscosity of the solvent diluent, because petroleum naphtha, which possesses low purifying sodium sulfonate.

is not effective. Nor are the water-soluble propyl alcohols effective, nor other lower molecular weight alcohols. conceivably, the results are derived as combined effects of the characteristics of low viscosity, oil-solubility, substantial waterimsolubility, and possibly even the effect of very slight water-solubility which appears to be a characteristic of the materials employed and defined as water-insoluble.

My process is not to be confused with the commonly used process of concentrating or purifying sodium sulfonate wherein crude sodium sulfonate is extracted with methyl, ethyl, or isopropyl alcohol containing carefully controlled proportions of water. In the latter process, the solvent is miscible with water and immiscible with oil, and is designed to extract the sodium sulfonates away from the oil. While both green acid and mahogany acid sodium soaps can be concentrated from the crude sodium sulfonates with water-iso-propyl alcohol mixtures, any tendency to separate green acid from mahogany acid soaps is in the wrong direction. Water-isopropyl (or ethyl or methyl) alcohol mixtures have a greater solvent power for the green acid soaps than for the mahogany acid soaps. The so-called purified sodium sulfonate produced in the conventional manner therefore usually has a higher ratio of green acid to mahogany acid soap than was present in the crude. sulfonate; whereas my process gives a purified sulfonate in which the ratio of green acid to mahogany acid soap is less than was present in the crude sulfonate. In the conventional process, a portion of the more desirable mahogany acid soaps is lost in the rejected oil phase, whereas in my process all of the more desirable mahogany acid soaps are recovered and the less desirable green acid soaps are expelled in the rejected water phase. The amount of alcohol containing four or more carbons used in my process is from only a few tenths of a percent to 5 percent as a maximum, usually, based on the volume being processed, as compared with from 50% to 200% of aqueous alcohol solvent in the conventional process for Also, judging from the small amount required of alcohol containing four or more carbons per molecule, it would appear that the function of the alcohol in my process is not to act so much as a selective solvent as it is to break an otherwise stable oil-continuous emulsion, and to permit water-soluble impurities to be expelled in an easily removed water phase.

While I have described my process as being applicable to petroleum sulfonates produced by sulfuric acid treatment of petroleum fractions, my process is also applicable to sulfonates produced synthetically by sulfonation of hydrocarbons or other compounds from coal tar products or any other source. Also mymis applicable to sulfates (often called sulfonates) produced by re acting sulfuric acid or sulfur trioxide with alcohols and/ or unsaturated compounds belonging to the classes of hydrocarbons acids, esters, ketones ethers, glycerides, waxes, etc.

It is to be understood that, in view of the above disclosures, other modifications will become apparent to those skilled in the art to which these improvements pertain. Therefore, all modifications within the scope of the appended claims are intended to be 'protected thereby.

viscosity and is water-insoluble and oil-soluble,

I claim as my invention:

1. In a process of producing water-insoluble, oil-soluble polyvalent-metal hydrocarbon suli'oacts, the steps which comprise: forming a mix- SUXKUH KUU ture containing water, said polyvalent metal sulfonate-iandan emulsion-breaking, oil-soluble liquid compound consisting of carbon, hydrogen and oxygen and containing four to about eight carbon atoms per molecule to facilitate separation of a water-insoluble sulfonate-containing phase from an aqueous phase; and recovering the sulfonate phase.

2. The process of claim 1 wherein the mixture containing said emulsion-breaking liquid is heated approximately to the boiling point of the mixture to facilitate said separation.

3. The process of claim 1 wherein said emulsion-breaking liquid is an aliphatic alcohol.

4. The process oi claim 1 wherein said emulsion-breaking liquid is abutyl alcohol.

5. The process of claim 1 wherein said emulsion-breaking liquid is an amyl alcohol.

6. The process of claim 1 wherein an alkaline earth metal hydroxide is heat d with said separated sulfonate-containing phase in the presence of said emulsion-breaking liquid to render said sulionate alkaline.

7. The process of claim 1 wherein said polyvalent-metal sulfonate is an alkaline earth metal sulionate.

8. The process of claim 1 wherein the quantity of emulsion-breaking liquid employed is about 0.2% to 10% of the mixture.

9. A process as in claim 1 wherein the separated sulfonate-containing phase is washed with water in the presence of said emulsion-breaking liquid.

10. In a process of producing water-insoluble, oil-soluble polyvalent-metal hydrocarbon sulfonate, the steps which comprise: forming a mixture containing water, said polyvalent-metal sulfonate, a petroleum oil of lubricating viscosity and anemulsion-breaking, oil-soluble liquid compound consisting of carbon, hydrogen and oxygen and containing four to about eight carbon atoms per molecule, said water, sulfonate and oil tending to form an oil continuous emulsion, and said emulsion-breaking liquid facilitatingseparation of a water-insoluble sulfonate and petroleum oil containing phase from an aqueous phase; and recovering the sulfonate and oil containing phase.

11. The process of claim 10 wherein the mixture containing said emulsion-breaking liquid is heated approximately to the boiling point of the mixture to facilitate said separation.

12. The process of claim 10 wherein said emulsion-breaking liquid is an aliphatic alcohol.

13. The process of claim 10 wherein said emulsion-breaking liquid is a butyl alcohol.

14. The process of claim 10 wherein said emulsion-breaking liquid is an amyl alcohol.

15. The process of claim 10 wherein an alkaline earth metal hydroxide is heated with said separated sulfonate 011 containing phase in the presence of said emulsion-breaking liquid to render said sulfonate alkaline.

16. The process of claim 10 wherein said polyvalent-metal suli'onate is an alkaline earth metal sulionate.

17. The process of claim 10 wherein the quantity of emulsion-breaking liquid employed is about 0.2% to 10% of the mixture.

18. A process as in claim 10 wherein the separated sulfonate oil containing phase is washed with water in the presence of said emulsionbreaking liquid.

19. A process of producing oil-soluble, waterinsoluble, polyvalent-metal petroleum type sulfonate, substantially free from water-soluble constituents, comprising: preparing a mixture in water of oil-soluble. water-soluble, alkali metal petroleum sulfonate containing petroleum oil; supplying to said mixture an oil-soluble, organic emulsion-breaking liquid compound consisting of carbon, hydrogen and oxygen and containing from four to about eight carbon atoms per molecule; also supplying to said mixture a water-soluble, polyvalent metal salt to convert said alkali metal sulfonate to said oil-soluble, water-insoluble polyvalent-metal sulfonate, whereby said liquid compound facilitates separation of an oil phase containing said polyvalentmetal sulfonate and oil from an aqueous phase containing said water and water-soluble constituents; and recovering the resultant polyvalentmetal sulfonate and oil phase.

20. A process in accordance with claim 19, in which the emulsion-breaking compound is introduced into said mixture prior to introducing said polyvalent metal salt.

21. A process in accordance with claim 19 in which the emulsion-breaking compound is introduced into said mixture after formation of said polyvalent-metal sulfonate.

ULRIC B. BRAY.

REFERENCES CITED The following references are of record in the the of this patent:

UNITED STATES PATENTS Number Name Date 2,140,263 Kessler et al Dec. 13, 1938 2,166,117 Blumer July 18, 1939 2,168,315 Blumer Aug. 8, 1939 2,246,374 Lohman et al. June 17, 1941 2,261,047 Assefl' Oct. 28, 1941 2,285,752 Van Ess June 9, 1942' 2,304,230 Archibald et a1 Dec. 8, 1942 2,307,953 Potter Jan. 12, 1943 2,316,719 Russell Apr. 13, 1943 2,361,476 Higbee et al. Oct. 31, 1944 2 6 U 4 2 9 cross REFEPENCE sum ROOM Certificate of Correction Patent No. 2,453,690. November 16, 1948.

ULRIO B. BRAY It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows:

Column 9, line 46, for the word dilutes read dilute; line 48, for hexanal read hezanol; line 57, for alcohol-esters read or alcohol-ethers;

and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Oflice.

Signed and sealed this 29th day of March, A. D. 1949.

THOMAS F. MURPHY,

Assistant Oonwm'asioner of Patents.

Ar Q Ma. a

US560030A 1944-10-23 1944-10-23 Process of producing polyvalentmetal hydrocarbon sulfonate Expired - Lifetime US2453690A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US560030A US2453690A (en) 1944-10-23 1944-10-23 Process of producing polyvalentmetal hydrocarbon sulfonate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US560030A US2453690A (en) 1944-10-23 1944-10-23 Process of producing polyvalentmetal hydrocarbon sulfonate

Publications (1)

Publication Number Publication Date
US2453690A true US2453690A (en) 1948-11-16

Family

ID=24236059

Family Applications (1)

Application Number Title Priority Date Filing Date
US560030A Expired - Lifetime US2453690A (en) 1944-10-23 1944-10-23 Process of producing polyvalentmetal hydrocarbon sulfonate

Country Status (1)

Country Link
US (1) US2453690A (en)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2532997A (en) * 1947-11-14 1950-12-05 Standard Oil Dev Co Production of alkaline earth sulfonates
US2533303A (en) * 1947-10-09 1950-12-12 Sinclair Refining Co Prevention of rust
US2689221A (en) * 1950-06-13 1954-09-14 Bray Oil Co Method of purifying, concentrating, and converting petroleum sulfonates
US2708182A (en) * 1952-04-21 1955-05-10 Shell Dev Preparation of oil-soluble organic sulfonates
US2732344A (en) * 1956-01-24 B bray
US2738326A (en) * 1952-10-04 1956-03-13 Shell Dev Preparation of oil solutions of basic alkaline earth metal petroleum sulfonates
US2746987A (en) * 1952-09-15 1956-05-22 Bray Oil Co Sulfonate manufacture
US2746980A (en) * 1952-10-27 1956-05-22 Bray Oil Co Production of mahogany sulfonates
US2798851A (en) * 1955-04-08 1957-07-09 Socony Mobil Oil Co Inc Emulsion drilling fluid for wells
US2824126A (en) * 1956-04-16 1958-02-18 Bray Oil Co Manufacture of sulfonates from petroleum oils
US2833716A (en) * 1953-08-07 1958-05-06 Exxon Research Engineering Co Process for purifying and increasing combined calcium of calcium sulfonates
US2899460A (en) * 1959-08-11 Purification of alkaryl sulfonic acids
US2902449A (en) * 1952-12-01 1959-09-01 Dehydag Gmbh Aqueous lubricant composition
US2945818A (en) * 1955-02-01 1960-07-19 Atlas Powder Co Process for preparing surface active compositions
US3041278A (en) * 1959-03-10 1962-06-26 Shell Oil Co Method of preparing polyvalent metal petroleum sulfonates and mineral lubricating oil containing same
US4738804A (en) * 1985-08-15 1988-04-19 Ashok Ramnaney Manufacture of oil soluble polyvalent metal sulfonates

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2140263A (en) * 1936-10-06 1938-12-13 Sonneborn Sons Inc L Method for the purification of petroleum mahogany sulphonates
US2166117A (en) * 1937-01-19 1939-07-18 Sonneborn Sons Inc L Method for the purification of petroleum mahogany sulphonates
US2168315A (en) * 1937-01-19 1939-08-08 Soneborn Sons Inc L Method for the purification of petroleum mahogany sulphonates
US2246374A (en) * 1939-09-22 1941-06-17 Emery Industries Inc Mineral oil sulphonates, their purification and fractionation
US2261047A (en) * 1941-07-28 1941-10-28 Lubri Zol Corp Lubricant
US2285752A (en) * 1940-11-18 1942-06-09 Shell Dev Anticorrosive
US2304230A (en) * 1939-12-19 1942-12-08 Standard Oil Dev Co Metallic salts of mahogany sulphonate and the process of making the same
US2307953A (en) * 1940-07-05 1943-01-12 Colgate Palmolive Peet Co Purification of organic compounds
US2316719A (en) * 1943-04-13 Purification of organic substances
US2361476A (en) * 1943-03-18 1944-10-31 Atlantic Refining Co Production of oil solutions of alkaline earth metal sulphonates

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2316719A (en) * 1943-04-13 Purification of organic substances
US2140263A (en) * 1936-10-06 1938-12-13 Sonneborn Sons Inc L Method for the purification of petroleum mahogany sulphonates
US2166117A (en) * 1937-01-19 1939-07-18 Sonneborn Sons Inc L Method for the purification of petroleum mahogany sulphonates
US2168315A (en) * 1937-01-19 1939-08-08 Soneborn Sons Inc L Method for the purification of petroleum mahogany sulphonates
US2246374A (en) * 1939-09-22 1941-06-17 Emery Industries Inc Mineral oil sulphonates, their purification and fractionation
US2304230A (en) * 1939-12-19 1942-12-08 Standard Oil Dev Co Metallic salts of mahogany sulphonate and the process of making the same
US2307953A (en) * 1940-07-05 1943-01-12 Colgate Palmolive Peet Co Purification of organic compounds
US2285752A (en) * 1940-11-18 1942-06-09 Shell Dev Anticorrosive
US2261047A (en) * 1941-07-28 1941-10-28 Lubri Zol Corp Lubricant
US2361476A (en) * 1943-03-18 1944-10-31 Atlantic Refining Co Production of oil solutions of alkaline earth metal sulphonates

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2732344A (en) * 1956-01-24 B bray
US2899460A (en) * 1959-08-11 Purification of alkaryl sulfonic acids
US2533303A (en) * 1947-10-09 1950-12-12 Sinclair Refining Co Prevention of rust
US2532997A (en) * 1947-11-14 1950-12-05 Standard Oil Dev Co Production of alkaline earth sulfonates
US2689221A (en) * 1950-06-13 1954-09-14 Bray Oil Co Method of purifying, concentrating, and converting petroleum sulfonates
US2708182A (en) * 1952-04-21 1955-05-10 Shell Dev Preparation of oil-soluble organic sulfonates
US2746987A (en) * 1952-09-15 1956-05-22 Bray Oil Co Sulfonate manufacture
US2738326A (en) * 1952-10-04 1956-03-13 Shell Dev Preparation of oil solutions of basic alkaline earth metal petroleum sulfonates
US2746980A (en) * 1952-10-27 1956-05-22 Bray Oil Co Production of mahogany sulfonates
US2902449A (en) * 1952-12-01 1959-09-01 Dehydag Gmbh Aqueous lubricant composition
US2833716A (en) * 1953-08-07 1958-05-06 Exxon Research Engineering Co Process for purifying and increasing combined calcium of calcium sulfonates
US2945818A (en) * 1955-02-01 1960-07-19 Atlas Powder Co Process for preparing surface active compositions
US2798851A (en) * 1955-04-08 1957-07-09 Socony Mobil Oil Co Inc Emulsion drilling fluid for wells
US2824126A (en) * 1956-04-16 1958-02-18 Bray Oil Co Manufacture of sulfonates from petroleum oils
US3041278A (en) * 1959-03-10 1962-06-26 Shell Oil Co Method of preparing polyvalent metal petroleum sulfonates and mineral lubricating oil containing same
US4738804A (en) * 1985-08-15 1988-04-19 Ashok Ramnaney Manufacture of oil soluble polyvalent metal sulfonates

Similar Documents

Publication Publication Date Title
US2270577A (en) Compounded lubricating oil
US3318809A (en) Counter current carbonation process
US2375222A (en) Aviation lubricating oil
US2485861A (en) Lubricating oil
US2316087A (en) Lubricant
US4073720A (en) Method for reclaiming waste lubricating oils
US2501731A (en) Modified lubricating oil
US4287049A (en) Reclaiming used lubricating oils with ammonium salts and polyhydroxy compounds
US2362289A (en) Lubricating compositions
US3150089A (en) Highly basic magnesium containing additive agent
US4073719A (en) Process for preparing lubricating oil from used waste lubricating oil
US2764548A (en) Dinonylnaphthalene sulfonates and process of producing same
US2081075A (en) Lubricating oil composition
RU2340652C2 (en) Method of demetallisation with recycling of hydrocarbon oil
US2413311A (en) Lubricant and process for preparing same
US6225267B1 (en) Sodium sulfonate blends as emulsifiers for petroleum oils
GB2142928A (en) Preparation of detergent-dispersant additives of very high alkalinity based on calcium
US2416281A (en) Mineral oil composition
US2760970A (en) Process for the preparation of substantially pure metal salts of organic sulfonic acids
US4147638A (en) Sulfonation of crude oils to produce petroleum sulfonates
US2216485A (en) Emulsion
US2406564A (en) Compounded lubricating oil
US2779784A (en) Basic alkaline earth metal sulfonates and method of making same
Wilson et al. Liquid propane use in dewaxing, deasphalting, and refining heavy oils
US3835035A (en) Method of purifying lubricating oils