US3852206A

US3852206A - Sulfur halogenated cutting oil and process of making

Info

Publication number: US3852206A
Application number: US00395742A
Authority: US
Inventors: R Dinsmore; H Ivey
Original assignee: Lubrication Co of America
Current assignee: Lubrication Co of America
Priority date: 1973-09-10
Filing date: 1973-09-10
Publication date: 1974-12-03
Anticipated expiration: 1991-12-03

Abstract

A naphthenic base mineral oil, useful as a cutting or lubricating oil, by itself or upon dilution, is formed by treating a naphtene base crude oil fraction with an amount of sulfuric acid less than the maximum amount required to react completely with the oil, and thereafter treating this unneutralized acid oil with a sulfur halide at ambient temperature to incorporate both sulfur and halogen into the oil whereby anti-weld properties are obtained.

Description

United States Patent [191 Dinsmore et al.

[111 3,852,20 [451 Dec.3, 1974 SULFUR HALOGENATED CUTTING OIL AND PROCESS OF MAKING Inventors: Robert L. Dinsmore, Long Beach;

Herbert D. Ivey, Pasadena, bothof Calif.

Lubrication Company of America, Los Angeles, Calif.

Filed: Sept. 10, 1973 Appl. No.: 395,742

Assignee:

U.S. CI 252/483, 252/45, 260/139 Int. Cl Cl0m l/38 Field of Search 252/488, 45; 260/139 I References Cited UNITED STATES PATENTS 6/1946 Signaigo 260/139 3/1967 Hanna et al. 252/42.4

OTHER PUBLICATIONS Gruse et a1. Chemical Technology of Petroleum, 2nd Edn. (1942), pages 6 & 7.

Primary Examiner W. Cannon Attorney, Agent, or Firm-Charles G. Lyonamount of sulfuric acid less than the maximum amount required to react completely with the oil, and thereafter treating this unneutralized acid oil with a sulfur halide at ambient temperature to incorporate both sulfur and halogen into the oil whereby anti-weld properties are obtained. 1

14 Claims, No Drawings SULFUR HALOGENATED CUTTING OIL AND PROCESS OF MAKING BACKGROUND OF THE INVENTION This invention generally relates to cutting and lubricating oils, and more particularly to a process of making sulfurchlorinated naphthenic oils having anti-weld properties. I

Cutting oils used in the machining of steel and like metals require anti-weld properties to prevent the binding up of the machining metal with the'workpiece. An anti-weld lubricant is especially required with soft metals for the making of deep cuts where the workpiece may approach its welding temperature. Ideally, a lubrieating oil having anti-weld properties reacts with the tool and work surfaces just below the weld temperature to prevent the two from welding together. Such antiweld lubricating oils are usually made up of sulfur compounds which form an iron sulfide with the tool and work surface below the weld temperature to prevent these surfaces from weldingtogether;

The effectiveness of a sulfur-containing anti-weld lubricating oil is often dependent upon the amount of sulfur which is available to react just below the weld temperature; Generally, sulfonated fats, esters and waxes have tightly bound sulfur atoms which will not readily react below the weld temperature unless also exposed to extreme pressure. Consequently, such materials as sulfonated fats and esters find their use as extreme pressure additives rather than anti-weld additives in lubricating oils. v i I On the other hand, incorporation of loosely bound sulfur atoms into a cutting oil, so that the sulfur atoms are active-at room temperature may result in corrosion of workpieces and tools. Also, free sulfurmay result in instability of the oil'itself. Thus, the ideal sulfurized cutting oil is one whichis inactive under ambient conditions, but which exhibits anti-weld properties at a temperature below the welding temperature of the workpiece.

-In US. Pat. No. 3,309,315 assigned to the same assignee as the present invention, it was discovered that by selection of a mildly or incompletely acid treated neutralized naphthenic mineral oil and preferably the lubricating oil fraction of such oil, a high concentration of sulfur useful to impart anti-weld properties could be introduced into the oil by reaction with a sulfur halide. Typically, a boiling fraction of naphthene base crude oil (also called asphalt base crude, California or Western crude, Gulf crude, Coastal crude, etc.) boiling between 300- 1 500F and preferably the lubricating fraction between 500 and 760F, is incompletely reacted with sulfuric acid to remove unwanted nitrogen, oxygen and sulfur bearing compounds, etc. which will form sludge upon reactionwith S Cl if not removed. The insoluble products of this sulfuric -acid reaction, commonly known as green acid, is removed by settling, filtering or other techniques. It'was also believed that soluble reaction products, generally in the form of sulfonic acid derivatives and commonly called red or mahogany acids, had to be removed or neutralized before the product could be utilized as a lubricating oil, since soluble red acids inthe final product may cause instability of the oil, corrosion of the workpiece and staining due to the extremely dark color.

Removal of the oil soluble red acids is generally accomplished by contacting it with a material such as filtering clay onto which the acid will be adsorbed. Alternately, the acid may be neutralized by treatment with a base. We have now discovered that neutralization or removal of the soluble red acids is not only unnecessary prior to sulfur halide treatment for the making of a stable, non-corrosive anti-weld lubricant, but in fact appears to catalyze or take part in the sulfur halide reaction to give a stable sulfurchlorinated oil which releases a large number of sulfur atoms just below the welding temperature of the metal so as to act as an improved anti-weld lubricant. Thus, the advantages of this cutting oil and the process of making it is not only a cost savingsby the elimination of a costly neutralization or separation step, but also an improved anti-weld lubricant is obtained.

. SUMMARY OF THE INVENTION A naphthenic base crude oil fraction, boiling between 350-1,500F. with a viscosity index below 50,

is treated with 0.1 percent w. to 10 percent w. of sulfuric acid to cause separation of unwantedimpurities, but yet leave the naphthene base derivatives substantially unreacted. The unneutralized, acid-treated oil is then further reacted with a normally liquid sulfur halide, such as sulfur monochloride atambient temperature for a time sufficient to give, after separation of any resulting precipitate and gaseous halide,,a stable and homogeneous oil characterized by lack of offensive odor and containing up to l8percent w. of total sulfur and up to 5 percent w. total halide. The final product has a substantial 18 percent w. of sulfur and halogen active below the weld temperature and is compatible with other lubricating oils.

PREFERRED EMBODIMENT crude oils which are considerably more paraffmic. For

many applications, a high naphthenic content isundesirable and is therefore extracted by well-known processes. Such extraction may be accomplished by treatment with furfurol duosol (phenylpropane), 'sulfur dioxide, or sulfuric acid. In the case of sulfuricv acid, if excess acid is used to completely react with all the reactive components of the oil, awhite or pale mineral oil will be obtained. Such an oil cannot be sulfurized, thereby prohibiting its use as an anti-weld cutting oil. On the other hand, it is desirable for many applications to have the major component of the oil a white oil, pale oil or paraffin oil. Thus, in the formulation of an antioxygen and sulfur containing compounds are removed.

Additionally, soluble sulfonic acid derivatives, commonly called red or mahogany acids are formed. After separation of the insoluble (green acid) reaction products of the sulfuric acid treatment, the oil is directly treated at ambient temperatures, with a sulfur halide.

The final product possesses some very unusual characteristics. Unexpectedly, there is little, if any, sulfonic red acid in the final product. The oil contains relatively small portions of active sulfur or chlorine at room temperature, but yet exhibits excellent anti-weld properties in the cutting of soft metals, indicating the release of both the sulfur and chlorine, analyzed to be present, below the weld temperature.

Although the reaction is not fully understood, it is believed that the S Cl when reacted in the presence of sulfonic acids at preferably ambient temperatures, forms a sulfur chlorinated oil of the general formula R- S-Cl or R-S-S-Cl. This is very different from other sulfur-chlorinated products such as fats or waxes which release sulfur or chlorine only under extreme pressure. The extreme pressure is necessary since the suflur and chlorine are tightly bound to the carbon backbone by, for example, the saturation of the double bonds. In the present process, sulfur chlorination is not accomplished by double bond saturation. On the other hand, by neutralization or removal of the sulfonic acids, it is very difficult to chlorinate the oil. Thus, upon reaction with sulfur monochloride, an oil of the general formula R-S-S-R is obtained, with the chlorine being released in the form of HCl, This oil will readily release sulfur at temperatures well below the weld temperature of even soft metals. This results in unnecessary corrosion and premature spending of the anti-weld ingredient, since the weld temperature may not be approached for many cutting applications.

In the process of this invention, a liquid crude oil fraction which possesses any useful lubricating qualities and generally boiling between 350l,500F (after removal of tar or gasoline and naptha portions) or, only the lubricating oil fraction, boiling between 500 and 760F, may be sulfurchlorinated. if the entire liquid crude oil is first sulfurchlorinated, it may be later separated into individual fractions in which the 500F to 760F fraction would give the most preferred cutting oil.

, Alternatively, the entire unfractionated sulfurchlorinated oil or a fractionated portion thereof may be blended with higher or lower boiling oils to give the most desired boiling range. Also, the sulfurized oils may be blended with other lubricating oils to give the desired viscosity and viscosity index. Since the product of this invention may be blended. with pale oils, white oils or paraffin oils, boiling range, viscosity and viscosity index may be tailored for'each application.

The unneutralized sulfuric acid-treated riaphthenic oil-is treated witha normally liquid sulfur halide to form the sulfurchlorinated cutting oil. Although sulfurchlorination is preferable, any sulfur halide capable of reacting with the oil to form a product having anti-weld properties may be used. These may include sulfur monochloride, sulfur dichloride, sulfur monobromide, thionyl chloride, sulfuryl chloride, or other sulfur halides which are liquid under ambient conditions and which will react with the naphthenic oil. We have generally found that up to 26 percent by weight of sulfur monochloride may be reacted with an unneutralized acidtreated naphthenic base oil fraction, boiling between 500 to 760F. The final product may contain up to 13 percent active sulfur and up to 18 percent total sulfur as well as up to chlorine after removal of all the hydrogen chloride. Despite the presence of chlorine and sulfur in the final product, the oil exhibits little staining or corrosion at room temperatures. However, when used as a cutting oil, it has been found to exhibit extremely effective anti-weld properties, indicating that the sulfur and chlorine compounds, which are relatively inactive at room temperature, will react below the welding temperature to prevent the welding of the tool surface with the workpiece.

Also, although it is believed that the sulfonic red acids catalyze the sulfur halide reaction, reaction in the presence of a metal such as iron filings or in an iron ket tle reaction vessel may be desired to further speed the reaction.

EXAMPLE I A naphthenic base, straight run, Western mineral oil having a distillation range of about 500 to about 760F, a viscosity index below 50, and a pour point below 30F is agitated with l 10 vol. concentrated sulfuric acid at room temperature for minutes and then allowed to settle for 4 hours, after which the precipitate is removed.

To 800 gms of this oil is reacted a total of 210 gms (26 percent by weight) of S Cl gms of S Cl is first added to the oil in an iron kettle reaction vessel at ambient temperature with agitation by bubbling air therethrough. The iron kettle and in addition, iron filings may be used to catalyze the reaction, although it is preferable not to catalyze the reaction so as to minimize the exotherm and permit the chlorine to react. It is believed that if the reaction is allowed to proceed well above ambient temperature, the chlorine will be driven off as HCl and will not react with the oil. The reaction is allowed to proceed overnight, and the second day, an additional 105 gms of S Cl is added with air agitation. The reaction is allowed to proceed to completion for a total reaction time of about 48 hours. The end of the reaction is indicated by the absence of sulfur monochloride odor in the effluent vapor.

The kettle is then heated to -200F with air blowing for about 10 hours to' remove unreacted chlorine in the form of HCl gas. The oil is let stand. overnight and filtered to remove any precipitate. The resultant product isa dark reddish colored, sulfurized and chlorinated mineral oil of pleasant odor, stably homogeneous, soluble in white oil and posessing the following characteristics:

Gravity APl 12.6 Lbs per gallon 8.18 Specific Gravity at 60F 0.9820 Density at l5F 0.98 [4 Viscosity SU at l00F 209 Viscosity CS at l00F 45.0

Pour Point degrees F +15 Flash Point COC degrees F 325 Copper Strip Corrosion at 77F g Positive Total Sulfur wt 8.76

ASTM D129 Active Sulfur wt 6.49

Ford Motor Co. Method ATl-l Total Chlorine wt 1.24

ASTM D808 Soluble in pale or paraffin oil EXAMPLE II A cutting oil was blended from 25 percent w. of the oil of Example I with 75 percent w. of a mineral oil t 100 SU at 100F). When used in threading steel pipe, bright shiny threads with smooth surfaces were obtained, with tool life 40 times longer than commercial mixtures of pale oil and sulfurized fatty oil.

Since the product of this invention has been found to exhibit equal or superior anti-weld properties as compared with a product made from neutralized sulfuric acid-treated naphthenic based oil, it would be understood that the product of this invention may be used for a wide variety of applications, such as those taught in U.S. Pat. No. 3,309,315 which discloses a neutralized sulfuric oil. Such applications may include use as a cutting oil, alone or as an additive. It may be used for threading steel pipe, as a gear oil, machining, and drilling, especially in the drilling of oil wells.

What is claimed is:

l. The process which comprises reacting a naphthenic-base mineral oil, boiling between 350- 1,500Fwith about 0.1 percent w. of sulfuric acid, such amount of sulfuric acid being less than the maximum amount required to react completely with the oil, removing the sludge formed thereby, reacting the unneutralized product with a normally liquid, sulfur halide, and separating the resulting precipitate and hydrogen halide therefrom, to leave a stable and homogeneous oil characterized by lack of offensive odor and containing up to about 18 percent w. of total sulfur and up to about 5 percent w. total halide in oil soluble organic compounds which have anti-weld properties.

2. The process of claim 1 wherein the sulfur halide is essentially sulfur monochloride.

3. The process which comprises reacting the lubricating oil fraction of a naphthenic base mineral oil with about 0.1 percent w. to about percent w. of sulfuric acid, such amount of sulfuric acid being less than the maximum amount required to react completely with the oil, removing the sludge formed thereby, reacting the unneutralized product with a normally liquid sulfur halide, separating the resulting precipitate and hydrogen halide therefrom to leave a stable and homogeneous oil characterized by lack of offensive odor and containing up to about 18 percent w. of total sulfur and up to 5 percent w. of total halide in oil soluble organic compounds which have anti-weld properties, whereby the bulk of said oil containing said soluble compounds may be used as a cutting oil by itself or upon dilution.

4. The process of claim 3 wherein said lubricating oil fraction boils between 500 and 760F and exhibits a viscosity index below 50.

5. The process which comprises reacting a naphthenic base mineral oil boiling between 350-1,500F and having a viscosity index below about 50 with about 0.1 percent w. to about 10 percent w. of sulfuric acid, such amount of sulfuric acid being less than the maximum amount required to react completely with the oil, removing the sludge formed thereby, reacting the unneutralized product with a normally liquid, sulfur halide at ambient room temperature, and separating the resulting precipitate and hydrogen halide therefrom to leave a stable and homogeneous oil characterized by lack of offensive odor and containing up to about 18 percent w. of total sulfur and 5 percent w. of halide in oil soluble organic compounds which have anti-weld properties.

6. The process of claim 5 wherein said sulfuric acid is about 0.5 percent w. to about 5 percent w. and said sulfur halide is added is fractional amounts during an extended period of time up to about 15 hours and said a reaction is effected principally at about ambient temperatures with agitation effected by passage of an air current through the reaction mixture until no odor of sulfur halide or hydrogen halide is evident, even upon heating to about 200F.

7. The process of claim 6 wherein the reaction proceeds for about 48 hours.

8. The process of claim 6 wherein said sulfur halide is essentially about 0.5 percent w. to about 26 percent w. of sulfur monochloride.

9. The process which comprises reacting the lubricating oil fraction of a naphthenic base mineral oil with about 0.5 percent w. to about 5 percent w. of sulfuric acid, such amount of sulfuric acid being less than the maximum amount required to react completely with the oil, removing the sludge formed thereby, reacting it at ambient temperature with up to about 26 percent w. of sulfur monochloride, and separating the resulting precipitate and volatile chlorides therefrom to leave a stable and homogeneous cutting oil or additivetherefor, characterized by lack of offensive odor and containing up to about 18 percent w. of total sulfur and up to about 5 percent total chlorine in oil soluble organic compounds which have anti-weld properties.

10. A mineral oil base, cutting fluid containing homogeneously and stably disbursed therein an anti-weld quantity of the organic oil soluble reaction product formed between a normally liquid, sulfur halide and a naphthenic base mineral oil boiling between 350l,500F and having a viscosity index below 50, said reaction product being formed by treating said mineral oil with about 0.1 percent w. to about l0 percent w. of sulfuric acid, such amount of sulfuric acid being less than the maximum amount required to react completely with the oil, removing the sludge formed by the sulfuric acid and then reacting the oil with said normally liquid sulfur halide and separating the resulting precipitate therefrom, thereby leaving an organic oil soluble reaction product containing up to about 18 percent w. total sulfur and up to 5 percent w. total halogen having anti-weld properties, said reaction product remaining dissolved in the mineral oil in which it.was formed, which oil forms the bulk of said cutting fluid.

thenic base mineral oil, prior to saidsulfuric acid treatment, consists essentially of a lubricating oil fraction of said mineral oil boiling between 500 and 760Ff 14. A fluid composition having lubricant and antiweld properties having uniformly disbursed therein a beneficialquantity of the reacted mineral oil of claim 10.

Claims

1. THE PROCESS WHICH COMPRISES A NAPHTHENIC-BASE MINERAL OIL, BOILING BETWEEN 350*- 1,500F WITH ABOUT 0.1 PERCENT W. OF SULFURIC ACID, SUCH AMOUNT OF SULFONIC ACID BEING LESS THAN THE MAXIMUM AMOUNT REQUIRED TO REACT COMPLETELY WITH THE OIL, REMOVING THE SLUDGE FORMED THEREBY, REACTING THE UNNEURALIZED PRODUCT WITH A NORMALLY LIQUID, SULFUR HALIDE, AND SEPARATING THE RESULTING PRECIPITATE AND HYDROGEN HALIDE THEREFROM, TO LEAVE A STABLE AND HOMOGENEOUS OIL CHARACTERIZED BY LACK OF OFFENSIVE ODOR AND CONTAINING UP TO ABOUT 18 PERCENT W. OF TOTAL SULFUR AND UP TO ABOUT 5 PERCENT W. TOTAL HALIDE IN OIL SOLUBLE ORGANIC COMPOUNDS WHICH HAVE ANTI-WELD PROPERTIES.

3. The process which comprises reacting the lubricating oil fraction of a naphthenic base mineral oil with about 0.1 percent w. to about 10 percent w. of sulfuric acid, such amount of sulfuric acid being less than the maximum amount required to react completely with the oil, removing the sludge formed thereby, reacting the unneutralized product with a normally liquid sulfur halide, separating the resulting precipitate and hydrogen halide therefrom to leave a stable and homogeneous oil characterized by lack of offensive odor and containing up to about 18 percent w. of total sulfur and up to 5 percent w. of total halide in oil soluble organic compounds which have anti-weld properties, whereby the bulk of said oil containing said soluble compounds may be used as a cutting oil by itself or upon dilution.

4. The process of claim 3 wherein said lubricating oil fraction boils between 500* and 760*F and exhibits a viscosity index below 50.

5. The process which comprises reacting a naphthenic base mineral oil boiling between 350*-1,500*F and having a viscosity index below about 50 with about 0.1 percent w. to about 10 percent w. of sulfuric acid, such amount of sulfuric acid being less than the maximum amount required to react completely with the oil, removing the sludge formed thereby, reacting the unneutralized product with a normally liquid, sulfur halide at ambient room temperature, and separating the resulting precipitate and hydrogen halide therefrom to leave a stable and homogeneous oil characterized by lack of offensive odor and containing up to about 18 percent w. of total sulfur and 5 percent w. of halide in oil soluble organic compounds which have anti-weld properties.

6. The process of claim 5 wherein said sulfuric acid is about 0.5 percent w. to about 5 percent w. and said sulfur halide is added is fractional amounts during an extended period of time up to about 15 hours and said reaction is effected principally at about ambient temperatures with agitation effected by passage of an air current through the reaction mixture until no odor of sulfur halide or hydrogen halide is evident, even upon heating to about 200*F.

7. The process of claim 6 wherein the reaction proceeds for about 48 hours.

9. The process which comprises reacting the lubricating oil fraction of a naphthenic base mineral oil with about 0.5 percent w. to about 5 percent w. of sulfuric acid, such amount of sulfuric acid being less than the maximum amount required to react completely with the oil, removing the sludge formed thereby, reacting it at ambient temperature with up to about 26 percent w. of sulfur monochloride, and separating the resulting precipitate and volatile chlorides therefrom to leave a stable and homogeneous cutting oil or additive therefor, characterized by lack of offensive odor and containing up to about 18 percent w. of total sulfur and up to about 5 percent total chlorine in oil soluble organic compounds which have anti-weld properties.

10. A mineral oil base, cutting fluid containing homogeneously and stably disbursed therein an anti-weld quantity of the organic oil soluble reaction product formed between a normally liquid, sulfur halide and a naphthenic base mineral oil boiling between 350*-1,500*F and having a viscosity index below 50, said reaction product being formed by treating said mineral oil with about 0.1 percent w. to about 10 percent w. of sulfuric acid, such amount of sulfuric acid being less than the Maximum amount required to react completely with the oil, removing the sludge formed by the sulfuric acid and then reacting the oil with said normally liquid sulfur halide and separating the resulting precipitate therefrom, thereby leaving an organic oil soluble reaction product containing up to about 18 percent w. total sulfur and up to 5 percent w. total halogen having anti-weld properties, said reaction product remaining dissolved in the mineral oil in which it was formed, which oil forms the bulk of said cutting fluid.

11. The cutting fluid of claim 10 wherein said normally liquid sulfur halide consists essentially of sulfur monochloride and said reaction product contains from about 4 percent w. up to about 18 percent w. of total sulfur and from about 0.5 percent w. to about 5 percent w. total chlorine.

12. The cutting fluid of claim 11 wherein said reaction product is formed essentially at ambient temperature.

13. The cutting fluid of claim 10 wherein said naphthenic base mineral oil, prior to said sulfuric acid treatment, consists essentially of a lubricating oil fraction of said mineral oil boiling between 500* and 760*F.

14. A fluid composition having lubricant and anti-weld properties having uniformly disbursed therein a beneficial quantity of the reacted mineral oil of claim 10.