US2724697A - Preparation of emulsifiers for producing soluble oil - Google Patents

Preparation of emulsifiers for producing soluble oil Download PDF

Info

Publication number
US2724697A
US2724697A US299597A US29959752A US2724697A US 2724697 A US2724697 A US 2724697A US 299597 A US299597 A US 299597A US 29959752 A US29959752 A US 29959752A US 2724697 A US2724697 A US 2724697A
Authority
US
United States
Prior art keywords
stock
oil
soluble oil
partial oxidation
sulfonated
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
US299597A
Inventor
Lipkin Moses Robert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sunoco Inc
Original Assignee
Sun Oil Co
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 Sun Oil Co filed Critical Sun Oil Co
Priority to US299597A priority Critical patent/US2724697A/en
Application granted granted Critical
Publication of US2724697A publication Critical patent/US2724697A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • 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
    • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
    • C10M135/08—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium containing a sulfur-to-oxygen bond
    • C10M135/10—Sulfonic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/62—Sulfonated fats, oils or waxes of undetermined constitution
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • 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
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
    • C10M2207/122—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms monocarboxylic
    • 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
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
    • Y10S516/03—Organic sulfoxy compound containing
    • Y10S516/04—Protein or carboxylic compound containing

Definitions

  • This invention relates to the preparation of acidic derivatives of petroleum hydrocarbons. More particularly the invention is directed to the preparation of products comprising both petroleum sulfonates and hydrocarbon derivatives formed by partial oxidation of the hydrocarbons. Products of the invention have special utility in the manufacture of soluble oils.
  • soluble oils are employed commercially in metal working operations, such as cutting and grinding, and as spray oils, rust-proofing compositions and the like.
  • a suitable mineral oil is compounded with emulsifying agents, and a minor amount of a solvent for both oil and water, generally referred to as a mutual solvent is usually added.
  • emulsifying agents petroleum naphthenates and mahogany sulfonates are often used in combination, the sulfonates also serving to enhance the rust-proofing characteristics of the composition.
  • suitable emulsifying agents for soluble oils can be prepared by liquid phase partial oxidation of petroleum stocks boiling in the lubricating oil or gas oil range.
  • An example of a partial oxidation process of this type is disclosed in Johnson et al. Pat. No. 2,395,627.
  • a disadvantage in producing emulsifiers in this manner arises, however, from the fact that the liquid phase partial oxidation reaction generally will not proceed properly if the charge stock contains the usual amount of aromatic constituents present in petroleum stocks.
  • Aromatics inhibit the oxidation reaction and have the effect either of preventing any substantial amount of oxidation being obtained or, if sufiiciently drastic conditions are used to force the oxidation reaction, of causing the formation of resinous acidic products which are unsuitable for soluble oil manufacture.
  • .various non-hydrocarbon constitu cuts of petroleum such as sulfur and nitrogen compounds, may tend to inhibit the oxidation reaction. For this reason it has been necessary heretofore to pretreat the charge stock in order to reduce its aromatic content to a low value and perhaps also remove non-hydrocarbon constituents in order to avoid the inhibitory effect of these materials. This adds considerably to the expense of the operation.
  • the present invention is directed to and provides an inexpensive process for producing, from a single charge stock, a material containing both the mahogany sulfonates and the partial oxidation product emulsifiers desired for soluble oil manufacture.
  • a charge stock containing a usual amount of aromatic constituents is first subjected to sulfonation to form mahogany sulfonic acids. After removal of sludge, the sulfonated stock is neutralized with an alkali and.the neutralized stock is then subjected to liquid phase partial oxidation to form carboxylic acid derivatives of the hydrocarbons.
  • the resulting product, after neutralization with an alkali is especially suitable for use in the preparation of soluble oil.
  • the first two steps of the present processsulfonation followed by neutralizationserve not only to produce mahogany sulfonates which are desired in the soluble oil composition, but also to convert aromatic constituents which would normally interfere with the partial oxidation reaction into a form in which no inhibitory effect is obtained. Furthermore, it has been found that the sulfonates formed upon neutralization of the sulfonated stock are stable under conditions employed in the oxidation step and do not therein undergo degradation affecting their quality. This would not be true, however, of the sulfonic acids before neutralization, as it has been found that they decompose rapidly under conditions used in the oxidation reaction. The neutralization step is accordingly essential.
  • Charge oil for the process may be a petroleum distillate fraction boiling mainly above 450 F. such as a gas oil or lubricating oil cut. Selection of the charge stock with respect to boiling range will depend mainly upon the molecular weight desired for the carboxylic acids produced in the subsequent partial oxidation reaction.
  • the charge stock may be a fraction as obtained directly from crude petroleum by distillation, or it may be an oil which has undergone treatment adapted to remove part of the aromatics, such as, for example, a rafiinate from a solvent extraction operation. In any event the charge stock should be a fraction which contains aromatic hydrocarbons in sufficient amount to yield the concentration of mahogany sulfonates desired in the product, such amount generally being in excess of 15% aromatics by weight.
  • the charge oil is introduced to a sulfonation zone 10 wherein it is treated with any suitable sulfonating agent such as concentrated or fuming sulfuric acid, sulfur trioxide, chlorosulfonic acid and the like, sulfur trioxide being the preferred agent.
  • suitable sulfonating agent such as concentrated or fuming sulfuric acid, sulfur trioxide, chlorosulfonic acid and the like, sulfur trioxide being the preferred agent.
  • the mixture is separated, as illustrated by separation zone 11, to remove the sludge comprising the so-called green sulfonic acids and any excess sulfonating agent. This may be done by allowing the mixture to settle in the same zone in which the sulfonation is efiected or in a separate zone, or it may be done in any other suitable manner such as by filtration or centrifuging.
  • the oil containing the mahogany acids is neutralized as illustrated at neutralization zone 12. This may be done simply by mixing the acid oil with caustic soda or any other suitable alkali such as sodium carbonate or potassium hydroxide. It is important that the amount of alkali used be at least sufficient to neutralize substantially all of the mahogany acids formed so that the mixture which is subsequently oxidized will not contain any free sulfonic acids. An excess of alkali may be employed, if desired, so that the material charged to the oxidation step will be in alkaline condition, in which case the carboxylic acids will react with the excess alkali immediately as they are formed during the subsequent oxidation reaction.
  • the neutralized stock is then subjected to partial oxidation in liquid phase by means of a free-oxygen containing gas, as illustrated by zone 12.
  • a free-oxygen containing gas as illustrated by zone 12.
  • Conditions heretofore employed for partially oxidizing petroleum stocks of low aromatic content are suitable for oxidizing the sulfonatecontaining stock in the present process.
  • a temperature of the order of 1l0165 C. generally should be employed and a preferred temperature range is l20150 C.
  • the oxidizing medium may be air or other gas comprising free oxygen; and for the present purpose ozone can be considered the equivalent of a free-oxygen containing gas.
  • the reaction can be efiected without a catalyst, but
  • a suitable catalyst such as a naphthenate, oleate or stearate salt of manganese, magnesium, cobalt, lead, copper or the like, in order to accelerate the. rate of reaction,
  • Theoperation can be conducted at atmospheric pressure or an elevated pressure maybe used-to increase the reaction rate.
  • the level to;which,the oxidation reactionshould be carried will depend upon the particularmanner in which it is desired toutilize the product in compounding the soluble oil.
  • the oxidation may be effected just to that degree corresponding to the desired carboxylic acid salt content of the soluble oil, soqthat the preparation of the soluble oil will comprise merely neutralizing the oxidation acidsand, if desired, blending the neutralized product with a mutual solvent.
  • the sulfonation reaction preceding the oxidation should also be eifected to a degree corresponding to the-desired sulfonate content of the soluble oil.
  • both the sulfonation and oxi dation reactions are carried to higher levels, in which case theproduct constitutes a concentrate of the two,
  • the degree to which the sulfonation is carried generally will correspond to a mahogany sulfonic acid content within the range of 225% by weight of the acid oil, while the degree of oxidation generally will fall within a range corresponding to a saponification value of 15l00 mg. KOH/gram of the oxidized product.
  • Charge stock for the process was a lubricating oil rafiinate obtained from. a furfural extraction operation and having the following characteristics:
  • the foregoing stock was sulfonated by contacting it at ordinary ambient temperature with S03 until the acid oil contained about 14% mahogany acids by weight. About 12% by weight of green acids was also formed and this material was separated from the reaction mixture as a sludge by centrifuging. Upon attempting to oxidize a portion of the acid oil, it was found that charring and coke. formation occurred rapidly, indicating serious decomposition of the mahogany acids.
  • A500 gram portion of the acid oil was exactly neutralized with caustic soda and then was mixed with 0.4% manganese oleate as an oxidation catalyst.
  • the mixture was partially oxidized in a 2" I. D. steel column at a temperature of about 138 C. by bubbling air upwardly through the column until the mixture had a saponification value of about 52 and an acid number of about 16.
  • the resulting product, upouneutralization with caustic soda, constituted an emulsifier concentrate suitable for blending With hydrocarbon oil'to produce a soluble oil:
  • Method of forming an acidic partial oxidation prodnot containing mahogany sulfonates and suitable for use in preparing soluble oil which comprises treating a petroleum oil boiling mainly above 450 F. with a sulfonating agent under sulfonating conditions, separatingsludge from the sulfonated stock, neutralizing. the sulfonated stock with an alkaline-reacting alkali metal compound, and treating the neutralized stock in liquid phase with'a freeoxygen containing gas under conditions, includinga temperature above C., effecting partial oxidation to carboxylic acids.
  • Method of forming a soluble oil which comprises treating a petroleum oil boiling mainly above. 450 F.
  • Method of forming an acidic partial oxidation prod not containing mahogany sulfonates and suitable for use in preparing soluble oil comprises treating. a petroleum lubricating oil stock with a sulfonating agent under sulfonating conditions until the stock, after separation of sludge, has a mahogany sulfonic acid content of 2-25% by weight, separating sludge from the sulfonated stock, neutralizing the sulfonated stock with an alkalinereacting alkali metal compound, and treating the neutralized stock in liquid phase at a temperature of 110-165 C. with a free-oxygen containing gas until the stock has a saponification value of 15-100 mg. KOH/ gram.

Description

Nov. 22, 1955 M. R. LlPKlN 2,724,697
PREPARATION OF EMULSIFIEIRS FOR PRODUCING SOLUBLE OIL Filed July 18, 1952 Charge Oil sulfomflng Sulfonatian a Agent .i r H Sludge Separation Sludge Alkflli Neutralization Free-Oxygen Partial Containing Gas Oxldatlon Product (to Soluble Oil Manufacture) INVENTOR. MOSES ROBERT LIPKIN mitt fitwdh ATTORNEY United States Patent PREPARATION OF EMULSIFIERS F011 PRODUCING SOLUBLE OIL Moses Robert Lipkin, Havertown, Pa., assignor to Sun gil Company, Philadelphia, Pa., a corporation of New ersey Application July 18, 1952, Serial No. 299,597 8 Claims. (Cl. 252-332) This invention relates to the preparation of acidic derivatives of petroleum hydrocarbons. More particularly the invention is directed to the preparation of products comprising both petroleum sulfonates and hydrocarbon derivatives formed by partial oxidation of the hydrocarbons. Products of the invention have special utility in the manufacture of soluble oils.
The so-called soluble oils are employed commercially in metal working operations, such as cutting and grinding, and as spray oils, rust-proofing compositions and the like. In the manufacture of soluble oils a suitable mineral oil is compounded with emulsifying agents, and a minor amount of a solvent for both oil and water, generally referred to as a mutual solvent is usually added. As the emulsifying agents, petroleum naphthenates and mahogany sulfonates are often used in combination, the sulfonates also serving to enhance the rust-proofing characteristics of the composition.
It is known that suitable emulsifying agents for soluble oils can be prepared by liquid phase partial oxidation of petroleum stocks boiling in the lubricating oil or gas oil range. An example of a partial oxidation process of this type is disclosed in Johnson et al. Pat. No. 2,395,627. A disadvantage in producing emulsifiers in this manner arises, however, from the fact that the liquid phase partial oxidation reaction generally will not proceed properly if the charge stock contains the usual amount of aromatic constituents present in petroleum stocks. Aromatics inhibit the oxidation reaction and have the effect either of preventing any substantial amount of oxidation being obtained or, if sufiiciently drastic conditions are used to force the oxidation reaction, of causing the formation of resinous acidic products which are unsuitable for soluble oil manufacture. Also .various non-hydrocarbon constitu cuts of petroleum, such as sulfur and nitrogen compounds, may tend to inhibit the oxidation reaction. For this reason it has been necessary heretofore to pretreat the charge stock in order to reduce its aromatic content to a low value and perhaps also remove non-hydrocarbon constituents in order to avoid the inhibitory effect of these materials. This adds considerably to the expense of the operation.
The present invention is directed to and provides an inexpensive process for producing, from a single charge stock, a material containing both the mahogany sulfonates and the partial oxidation product emulsifiers desired for soluble oil manufacture. According to the invention, a charge stock containing a usual amount of aromatic constituents is first subjected to sulfonation to form mahogany sulfonic acids. After removal of sludge, the sulfonated stock is neutralized with an alkali and.the neutralized stock is then subjected to liquid phase partial oxidation to form carboxylic acid derivatives of the hydrocarbons. The resulting product, after neutralization with an alkali, is especially suitable for use in the preparation of soluble oil.
The first two steps of the present processsulfonation followed by neutralizationserve not only to produce mahogany sulfonates which are desired in the soluble oil composition, but also to convert aromatic constituents which would normally interfere with the partial oxidation reaction into a form in which no inhibitory effect is obtained. Furthermore, it has been found that the sulfonates formed upon neutralization of the sulfonated stock are stable under conditions employed in the oxidation step and do not therein undergo degradation affecting their quality. This would not be true, however, of the sulfonic acids before neutralization, as it has been found that they decompose rapidly under conditions used in the oxidation reaction. The neutralization step is accordingly essential.
The accompanying drawing is a simplified diagrammatic illustration of the present process. Charge oil for the process may be a petroleum distillate fraction boiling mainly above 450 F. such as a gas oil or lubricating oil cut. Selection of the charge stock with respect to boiling range will depend mainly upon the molecular weight desired for the carboxylic acids produced in the subsequent partial oxidation reaction. The charge stock may be a fraction as obtained directly from crude petroleum by distillation, or it may be an oil which has undergone treatment adapted to remove part of the aromatics, such as, for example, a rafiinate from a solvent extraction operation. In any event the charge stock should be a fraction which contains aromatic hydrocarbons in sufficient amount to yield the concentration of mahogany sulfonates desired in the product, such amount generally being in excess of 15% aromatics by weight.
Referring to the accompanying drawing, the charge oil is introduced to a sulfonation zone 10 wherein it is treated with any suitable sulfonating agent such as concentrated or fuming sulfuric acid, sulfur trioxide, chlorosulfonic acid and the like, sulfur trioxide being the preferred agent. Conditions for effecting sulfonation are well known, and any suitable conditions and procedure may be employed,
' with the operation being conducted batchwise or in continuous manner. Following the sulfonation step, the mixture is separated, as illustrated by separation zone 11, to remove the sludge comprising the so-called green sulfonic acids and any excess sulfonating agent. This may be done by allowing the mixture to settle in the same zone in which the sulfonation is efiected or in a separate zone, or it may be done in any other suitable manner such as by filtration or centrifuging.
After removal of the sludge, the oil containing the mahogany acids is neutralized as illustrated at neutralization zone 12. This may be done simply by mixing the acid oil with caustic soda or any other suitable alkali such as sodium carbonate or potassium hydroxide. It is important that the amount of alkali used be at least sufficient to neutralize substantially all of the mahogany acids formed so that the mixture which is subsequently oxidized will not contain any free sulfonic acids. An excess of alkali may be employed, if desired, so that the material charged to the oxidation step will be in alkaline condition, in which case the carboxylic acids will react with the excess alkali immediately as they are formed during the subsequent oxidation reaction.
The neutralized stock is then subjected to partial oxidation in liquid phase by means of a free-oxygen containing gas, as illustrated by zone 12. Conditions heretofore employed for partially oxidizing petroleum stocks of low aromatic content are suitable for oxidizing the sulfonatecontaining stock in the present process. A temperature of the order of 1l0165 C. generally should be employed and a preferred temperature range is l20150 C. The oxidizing medium may be air or other gas comprising free oxygen; and for the present purpose ozone can be considered the equivalent of a free-oxygen containing gas. The reaction can be efiected without a catalyst, but
it is usually preferred to utilize a suitable catalyst, such as a naphthenate, oleate or stearate salt of manganese, magnesium, cobalt, lead, copper or the like, in order to accelerate the. rate of reaction, Theoperationcan be conducted at atmospheric pressure or an elevated pressure maybe used-to increase the reaction rate.
The level to;which,the oxidation reactionshould be carried will depend upon the particularmanner in which it is desired toutilize the product in compounding the soluble oil. In one. manner of operation the oxidation may be effected just to that degree corresponding to the desired carboxylic acid salt content of the soluble oil, soqthat the preparation of the soluble oil will comprise merely neutralizing the oxidation acidsand, if desired, blending the neutralized product with a mutual solvent. In such case the sulfonation reaction preceding the oxidation should also be eifected to a degree corresponding to the-desired sulfonate content of the soluble oil. In another mannerof operation both the sulfonation and oxi dation reactions are carried to higher levels, in which case theproduct constitutes a concentrate of the two,
emulsifying agentswhich is subsequently blended with oil to form soluble oil having the desired sulfonate and carboxylic acid salt contents. Regardless of which procedure is used, the degree to which the sulfonation is carried generally will correspond to a mahogany sulfonic acid content within the range of 225% by weight of the acid oil, while the degree of oxidation generally will fall within a range corresponding to a saponification value of 15l00 mg. KOH/gram of the oxidized product.
The following example specifically illustrates the process according to the invention:
Charge stock for the process was a lubricating oil rafiinate obtained from. a furfural extraction operation and having the following characteristics:
Viscosity 100 F., CS; 127 Viscosity @"210" F., CS 9.56 Refractive index, 20 C./D 1.4991 Density, 20 /4 C 0.9118 Viscosity-gravity constant 0.855 Viscosity index 35 Average molecular weight; 410 Aromatic content, Wt. per cent 27 It was found that this stock could not be oxidized substantiallyunder customary partial oxidation conditions due, to the inhibiting effect of the aromatics; and that when more severe oxidizing conditions were employed, resinous oxidation products not suitable for soluble oil manufacture were formed.
The foregoing stock was sulfonated by contacting it at ordinary ambient temperature with S03 until the acid oil contained about 14% mahogany acids by weight. About 12% by weight of green acids was also formed and this material was separated from the reaction mixture as a sludge by centrifuging. Upon attempting to oxidize a portion of the acid oil, it was found that charring and coke. formation occurred rapidly, indicating serious decomposition of the mahogany acids.
A500 gram portion of the acid oil was exactly neutralized with caustic soda and then was mixed with 0.4% manganese oleate as an oxidation catalyst. The mixture was partially oxidized in a 2" I. D. steel column at a temperature of about 138 C. by bubbling air upwardly through the column until the mixture had a saponification value of about 52 and an acid number of about 16. The resulting product, upouneutralization with caustic soda, constituted an emulsifier concentrate suitable for blending With hydrocarbon oil'to produce a soluble oil:
I claim:
1. Method of forming an acidic partial oxidation prodnot containing mahogany sulfonates and suitable for use in preparing soluble oil which comprises treating a petroleum oil boiling mainly above 450 F. with a sulfonating agent under sulfonating conditions, separatingsludge from the sulfonated stock, neutralizing. the sulfonated stock with an alkaline-reacting alkali metal compound, and treating the neutralized stock in liquid phase with'a freeoxygen containing gas under conditions, includinga temperature above C., effecting partial oxidation to carboxylic acids.
2. Method according to claim 1 wherein the sultonation is effected to a degree corresponding to a mahogany sulfonic acid content in said sulfonated stock of 225% by weight.
3. Method according to claim 2 wherein thepartial, oxidation is effected to a degree corresponding, to a.
saponification value of 15-100 mg. KOI-I/gram.v
4. Method according to claim 1 wherein the partial oxidation is effected to a degree corresponding to a saponification value of 15100 mg. KOH/gram.
5. Method of forming. a soluble oil which comprises treating a petroleum oil boiling mainly above. 450 F.
with a sulfonating agent under sulfonating conditions, separating a sludge from the sulfonated stock, neutralizing the sulfonated stock with an alkaline-reacting alkali metal compound, treating the neutralized stock in. liquid phase I with a free-oxygen containing gas underconditionstineluding a temperature above 110 C., effectingpartial oxidation to carboxylic acids, and neutralizing the partially oxidized stock with an alkaline-reacting alkali metal compound.
6. Method according to claim 5 wherein both the sulfonationand partial oxidation are effected to degrees.
corresponding, respectively, to the desired sulfonate and carboxylic acid salt contents of the soluble oil.
7. Method according to claim 5 wherein both the sulfonation and partial oxidation are effected to degrees in excess of those corresponding to the desired sulfonate and carboxylic acid salt contents of the soluble oil, and said soluble oil is formed by blending hydrocarbon oil with the partially oxidized stock.
8. Method of forming an acidic partial oxidation prod not containing mahogany sulfonates and suitable for use in preparing soluble oil which comprises treating. a petroleum lubricating oil stock with a sulfonating agent under sulfonating conditions until the stock, after separation of sludge, has a mahogany sulfonic acid content of 2-25% by weight, separating sludge from the sulfonated stock, neutralizing the sulfonated stock with an alkalinereacting alkali metal compound, and treating the neutralized stock in liquid phase at a temperature of 110-165 C. with a free-oxygen containing gas until the stock has a saponification value of 15-100 mg. KOH/ gram.
References Cited in the fileof this patent UNITED STATES PATENTS 1,436,214 Teichner Nov. 21, 1922 1,817,599 Adams Aug. 4, 1931 2,361,476 Higbee Oct. 31, 1944 2,454,826 Liberthson Nov. 30, 1948 2,454,827 Moscowitz Nov. 30, 1948

Claims (1)

1. METHOD OF FORMING AN ACIDIC PARTIAL OXIDATION PRODUCT CONTAINING MAHOGANY SULFONATES AND SUITABLE FOR USE IN PREPARING SOLUBLE OIL WHICH COMPRISES TREATING A PETROLEUM OIL BOILING MAINLY ABOVE 450*F. WITH A SULFONATING AGENT UNDER SULFONATING CONDITIONS, SEPARATING SLUDGE FROM THE SULFONATED STOCK, NEUTRALIZING THE SULFONATED STOCK WITH AN ALKALINE-REACTING ALKALI METAL COMPOUND, AND TREATING THE NEUTRALIZED STOCK IN LIQUID PHASE WITH A FREEOXYGEN CONTAINING GAS UNDER CONDITIONS, INCLUDING A TEMPERATURE ABOVE 110* C., EFFECTING PARTIAL OXIDATION TO CARBOXYLIC ACIDS.
US299597A 1952-07-18 1952-07-18 Preparation of emulsifiers for producing soluble oil Expired - Lifetime US2724697A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US299597A US2724697A (en) 1952-07-18 1952-07-18 Preparation of emulsifiers for producing soluble oil

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US299597A US2724697A (en) 1952-07-18 1952-07-18 Preparation of emulsifiers for producing soluble oil

Publications (1)

Publication Number Publication Date
US2724697A true US2724697A (en) 1955-11-22

Family

ID=23155471

Family Applications (1)

Application Number Title Priority Date Filing Date
US299597A Expired - Lifetime US2724697A (en) 1952-07-18 1952-07-18 Preparation of emulsifiers for producing soluble oil

Country Status (1)

Country Link
US (1) US2724697A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2933452A (en) * 1956-06-06 1960-04-19 Lignosol Chemicals Ltd Dispersant and method of making the same
US3277014A (en) * 1962-08-27 1966-10-04 Union Oil Co Emulsifier compositions

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1436214A (en) * 1920-09-29 1922-11-21 Teichner Gustav Process for oxidizing hydrocarbons and their oxidation products
US1817599A (en) * 1928-09-04 1931-08-04 Standard Oil Co Emulsifiable lubricant
US2361476A (en) * 1943-03-18 1944-10-31 Atlantic Refining Co Production of oil solutions of alkaline earth metal sulphonates
US2454827A (en) * 1947-02-21 1948-11-30 Sonneborn Sons Inc L Viscosity reduction of petroleum mahogany sulfonate hydrocarbon solutions
US2454826A (en) * 1948-11-30 Viscosity reduction of petroleum

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2454826A (en) * 1948-11-30 Viscosity reduction of petroleum
US1436214A (en) * 1920-09-29 1922-11-21 Teichner Gustav Process for oxidizing hydrocarbons and their oxidation products
US1817599A (en) * 1928-09-04 1931-08-04 Standard Oil Co Emulsifiable lubricant
US2361476A (en) * 1943-03-18 1944-10-31 Atlantic Refining Co Production of oil solutions of alkaline earth metal sulphonates
US2454827A (en) * 1947-02-21 1948-11-30 Sonneborn Sons Inc L Viscosity reduction of petroleum mahogany sulfonate hydrocarbon solutions

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2933452A (en) * 1956-06-06 1960-04-19 Lignosol Chemicals Ltd Dispersant and method of making the same
US3277014A (en) * 1962-08-27 1966-10-04 Union Oil Co Emulsifier compositions

Similar Documents

Publication Publication Date Title
US2865956A (en) Preparation of basic polyvalent metal salts of organic acids
US4147638A (en) Sulfonation of crude oils to produce petroleum sulfonates
US4165291A (en) Overbasing calcium petroleum sulfonates in lubricating oils employing monoalkylbenzene
US2514733A (en) Sulfonation method
US2523582A (en) Sulfonation process
US2815370A (en) Sulfonation of petroleum oils
US2724697A (en) Preparation of emulsifiers for producing soluble oil
US2168315A (en) Method for the purification of petroleum mahogany sulphonates
US3153087A (en) Process for producing alkali metal adducts of aromatic solvent extracts of petroleum fractions, the products thereof and carbonation of the products
US2738326A (en) Preparation of oil solutions of basic alkaline earth metal petroleum sulfonates
US2978416A (en) Concentrated aqueous detergent composition
US2274057A (en) Process for the oxidation of aliphatic hydrocarbons
US2220678A (en) Sulphonation products and process of manufacture
US2927076A (en) Stabilizing sulfonated petroleum with organic sulfoxides
US2218174A (en) Preparation of sulphonic acids
US3007868A (en) Light-color, oil-soluble alkaline earth metal sulfonates
US2465221A (en) A method of producing a mineral oil concentrate
US2881140A (en) Rust inhibiting composition
US2330163A (en) Process for the simultaneous pro
US2645656A (en) Production of surface active sulfates
US2713034A (en) Treatment of alkaline earth metal petroleum sulfonates
US2680716A (en) Making sulfonates suitable for use in soluble oil
US2578657A (en) Process for producing sulfonic acids and sulfonates
US2204903A (en) Process for desulphurizing mineral oils
US2843625A (en) Low temperature sulfonation process