US3309315A - Sulphurized cutting oil and process of making same - Google Patents
Sulphurized cutting oil and process of making same Download PDFInfo
- Publication number
- US3309315A US3309315A US3309315DA US3309315A US 3309315 A US3309315 A US 3309315A US 3309315D A US3309315D A US 3309315DA US 3309315 A US3309315 A US 3309315A
- Authority
- US
- United States
- Prior art keywords
- oil
- sulfur
- mineral oil
- sulfuric acid
- reaction product
- 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
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- 238000000034 method Methods 0.000 title description 50
- 239000010730 cutting oil Substances 0.000 title description 24
- 239000011593 sulfur Substances 0.000 claims description 144
- 229910052717 sulfur Inorganic materials 0.000 claims description 144
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 120
- 239000003921 oil Substances 0.000 claims description 110
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 104
- 239000002480 mineral oil Substances 0.000 claims description 98
- 235000010446 mineral oil Nutrition 0.000 claims description 96
- -1 SULFUR HALIDE Chemical class 0.000 claims description 50
- 239000007788 liquid Substances 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 48
- 239000000314 lubricant Substances 0.000 claims description 28
- 239000007795 chemical reaction product Substances 0.000 claims description 22
- 239000002173 cutting fluid Substances 0.000 claims description 22
- 239000012530 fluid Substances 0.000 claims description 20
- 239000010802 sludge Substances 0.000 claims description 20
- 239000002244 precipitate Substances 0.000 claims description 18
- 239000000344 soap Substances 0.000 claims description 14
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 12
- 239000012433 hydrogen halide Substances 0.000 claims description 12
- 230000003472 neutralizing Effects 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 description 36
- 239000003208 petroleum Substances 0.000 description 36
- NGDNCZPCIZNCQS-UHFFFAOYSA-N CTK3J8699 Chemical compound Cl=S NGDNCZPCIZNCQS-UHFFFAOYSA-N 0.000 description 22
- 239000000047 product Substances 0.000 description 22
- 239000003981 vehicle Substances 0.000 description 22
- 150000001875 compounds Chemical class 0.000 description 20
- 238000010306 acid treatment Methods 0.000 description 18
- 239000002253 acid Substances 0.000 description 16
- 239000010779 crude oil Substances 0.000 description 14
- 239000010687 lubricating oil Substances 0.000 description 14
- 239000008186 active pharmaceutical agent Substances 0.000 description 12
- 239000000654 additive Substances 0.000 description 12
- 239000003153 chemical reaction reagent Substances 0.000 description 12
- 230000005484 gravity Effects 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000002199 base oil Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000003925 fat Substances 0.000 description 10
- 239000012208 gear oil Substances 0.000 description 10
- 150000002894 organic compounds Chemical class 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000010790 dilution Methods 0.000 description 8
- 239000010685 fatty oil Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 238000005553 drilling Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 230000001050 lubricating Effects 0.000 description 6
- 238000003754 machining Methods 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 150000003464 sulfur compounds Chemical class 0.000 description 6
- 239000001117 sulphuric acid Substances 0.000 description 6
- 235000011149 sulphuric acid Nutrition 0.000 description 6
- 239000005069 Extreme pressure additive Substances 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N Furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- 210000001503 Joints Anatomy 0.000 description 4
- FWMUJAIKEJWSSY-UHFFFAOYSA-N Sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N Thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- 230000005591 charge neutralization Effects 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- GNVXPFBEZCSHQZ-UHFFFAOYSA-N iron(2+);sulfide Chemical compound [S-2].[Fe+2] GNVXPFBEZCSHQZ-UHFFFAOYSA-N 0.000 description 4
- 239000010699 lard oil Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000001264 neutralization Effects 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- HPSUPGAVFFFPMQ-UHFFFAOYSA-N 1,2,3,4,6,7,10-heptachlorododecane Chemical compound CCC(Cl)CCC(Cl)C(Cl)CC(Cl)C(Cl)C(Cl)CCl HPSUPGAVFFFPMQ-UHFFFAOYSA-N 0.000 description 2
- BZRNNFDADQGMGA-UHFFFAOYSA-N CTK5D9411 Chemical compound Br[S] BZRNNFDADQGMGA-UHFFFAOYSA-N 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- 241001397173 Kali <angiosperm> Species 0.000 description 2
- 101710009221 LD Proteins 0.000 description 2
- 241000158728 Meliaceae Species 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N Sulfuryl chloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- HWKQNAWCHQMZHK-UHFFFAOYSA-N Trolnitrate Chemical compound [O-][N+](=O)OCCN(CCO[N+]([O-])=O)CCO[N+]([O-])=O HWKQNAWCHQMZHK-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 230000000996 additive Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 231100000078 corrosive Toxicity 0.000 description 2
- 231100001010 corrosive Toxicity 0.000 description 2
- OJOJJFJFCMEQRM-UHFFFAOYSA-L cyclohexanecarboxylate;lead(2+) Chemical compound C1CCCCC1C(=O)O[Pb]OC(=O)C1CCCCC1 OJOJJFJFCMEQRM-UHFFFAOYSA-L 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000011068 load Methods 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000003129 oil well Substances 0.000 description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000010690 paraffinic oil Substances 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000035943 smell Effects 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
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
- C10M135/02—Sulfurised compounds
-
- 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
- C10M2207/16—Naphthenic acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/40—Fatty vegetable or animal oils
-
- 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
- C10M2207/40—Fatty vegetable or animal oils
- C10M2207/404—Fatty vegetable or animal oils obtained from genetically modified species
-
- 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
- C10M2211/00—Organic non-macromolecular compounds containing halogen as ingredients in lubricant compositions
- C10M2211/08—Halogenated waxes
-
- 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
- C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
- C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
-
- 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
- C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
- C10M2219/024—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of esters, e.g. fats
-
- 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
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/041—Triaryl phosphates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/08—Groups 4 or 14
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/22—Metal working with essential removal of material, e.g. cutting, grinding or drilling
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
-
- 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
Definitions
- This anti-weld property of the compounded lubricant is required especially with soft metals and in making deep cuts and working at slow cutting speeds.
- anti-weld properties are still needed but are associated with extreme pressure additives such as sulfurized or chlorinated fats and waxes which have both cooling and load-bearing properties. They also prevent the formation of too much iron sulfide such as would erode the edge or point of the cutting tool. Hence, a balance between these factors produces the optimum formula for a particular metal or a particular machining operation.
- various methods have been used to obtain beneficial sulfur by direct introduction of the element (or by injection of sulfur-containing reagents) into fatty oils as well as into (refined) mineral oils.
- fatty oils cool the workpiece more than does mineral oil, and hence are less applicable in cutting fluids as they generally lack anti-Weld properties and are unable to acquire anti-weld properties without the presence of extreme pressure qualities.
- sulphur has been incorporated into additives such as synthetic polymers, which are then dispersed in the lubricant base to build up a desired concentration of useful sulfur.
- additives such as synthetic polymers
- the direct reaction of sulfur with mineral oil has too often yielded a dark colored, malodorous low sulfur content oil from which the sulfur or sulfur-containing precipitate soon separates upon agitation and/or aging.
- the amount of useful sulfur permanently introduced by reaction with liquid petroleum lubricant (mineral oil) has been at best no more than about three and a half or four percent, and such procedure has been generally possible only by reacting lubricating fractions of paraffinic base stock with stron reagents at elevated temperature, and in some cases with pressure.
- a more strenuous or complete sulphuric acid extraction of naphthenic petroleum apparently leaves in it only saturated or unreactive components, which, similar to an originally parafiinic crude, subsequently do not react in the present manner to incorporate a high concentration of beneficial and solution-stable sulfur.
- a viscosity index below about 70 may be taken as an approximate boundary to distinguish the naphthem'c base crudes which may be treated by the present invention, as contrasted with the more parafiinic petroleums.
- sulphuric acid is commonly used to remove undesirable (especially unsaturated) components from crude oil (by their precipitation, followed by neutralization of the liquid).
- sulphuric acid treatment is applied to a parafiinic base oil, or is continued to the limit of possible reaction with a naphthenic base oil, it removes all of the unsaturated (and polymerizable) components. Consequently, subsequent introduction of sulfur into the refined petroleum is then possible only to a limited extent and by comparatively strenuous reaction; such practice (when at all effective) has been generally limited to reacting paraihnic type, crude oil following its acid treatment (or its refinement by other means).
- the neutralized liquid is then beneficially reacted with a normally liquid sulfur halide.
- a normally liquid sulfur halide Such reaction forms in situ, solution-stable, non-malodorous, sulfur-containing organic compounds which are especially beneficial in cutting oil (the entire liquid petroleum reaction-mixture after removal of sludge and volatile components being usable as cutting oil, when it is characterized by other required physical properties, such as viscosity, flash point, etc.).
- the initial incomplete sulfuric acid treatment itself apparently produces some useful compounds which remain in the oil and which possibly may be polymerized by the subsequent reaction with sulfur halide (at least in part).
- the sulfuric acid removes (as a sludge) various higher molecular weight, reactive compounds which would otherwise later react with the sulfur halide, but would not thereafter permanently remain in solution.
- the present process increases the yield from the subsequent sulfur halide treatmentin other words, less of the sulfur halide reaction product (as measured by the sulfur content) is lost in the subsequent sludge or precipitate.
- the entire liquid crude oil which possesses any usable lubricating qualities can be sulphurized generally after removal of tar or heavy residuum, and the topping of gasoline and naphtha portions) and if desired, this overall range which distills from about 300 F. to about 800 F., can be sulfurized following its sulfuric acid treatment, either before or after its fractionation. Or a lubricating oil fraction (e.g. distilling between about 500 F. and about 760 F.
- a fluid as light as a kerosene fraction can be used as a cutting oil and hence such a volatile portion can be sulfurized with such end use in mind.
- Such thinner oil has a greater heat transfer value and its comparatively low flash point is of no consequence under frigid operating conditions.
- a more viscous portion than desired for the ultimate cutting fluid can be sulfurized with the intention of diluting it later with more readily available (or cheaper) diluent -which need not be mineral oilsince a sulphur concentration as high as the obtainable 13% w.
- the sulfurized fraction can be diluted with less viscous fluid which in addition contains other desired additives such as extreme pressure agents, etc., or the additives can be added to the total vehicle after its dilution.
- the entire usable distillate range of mineral oil can be sulfurized as a unit and subsequently fractionated.
- the liquid petroleum can first be fractionated and (one or more) individual fractions then sulfurized.
- sulfur halide refers generically to sulfur halides which are liquid at ambient room temperature and atmospheric pressure, such as sulfur-monochloride, sulfur dichloride, sulfur monobromide, thionyl chloride, sulphuryl chloride, or other sulfur halides which are liquid under the conditions under which the reacting petroleum or mineral oil remains liquid.
- sulfur monochloride is the most convenient for the present use and the invention will be subsequently exemplified by employment of this reagent.
- reaction of the sulfur halide with the Western mineral oil evolves some heat and this may be taken as an indication of the petroleum to beneficially utilize the sulfur halide.
- the potential reactivity is reached with addition of a maximum of about 50% weight S Cl
- the amount of sulfur monochloride which will remain mixed with the petroleum may be taken as the practical limitation of quantity required.
- the petroleum has the required quantity of reactant dispersed therein.
- the body of the oil was then left to settle, and the oil was filtered.
- the resultant product is a dark mahogany color, sulfurized mineral oil, of pleasant odor,
- Example 4 700 gms. of the former acid treated oil was reacted with 300 g. (43% w.) of S Cl following the procedure of Example 1. The resulting product has the following analysis:
- Example 6 The procedures outlined in Examples 1, 2 and 3 were followed on a paraffinic base, mineral oil with a similar viscosity as the naphthenic base oil of Examples 1 through 4, as well as examples of higher and lower viscosity. In each instance the yield was an unstable sulfurized oil with a maximum active sulfur of 2.5% w., part of which precipitated out as elemental sulfur within about a week.
- compositions illustrate some of the uses of our sulphurized mineral oil when mixed with various additives and/ or diluents:
- Example 7 A cutting oil was blended from 23% w. of the product of Example 4, and 77% w. of mineral oil (100 SSU 100 F.). The blend contained about 3% w. of active sulfur. When used in threading steel pipe, bright shiny threads with smooth surfaces ensued, and the tool life was up to 40 times longer than when using a commercial mixture of pale oil and sulphurized fatty oil which was recommended for this purpose. In comparison, when using only the recommended commercial product, in addition to the shorter tool life there was produced shredded threads and torn surfaces of the metal which had only a dull finish or appearance.
- Example 8 A concentrate was formed by mixing the product of Example 4 with an equal volume of sulphurized fat (such as sulphurized sperm oil or sulphurized lard oil). One volume of this concentrate is then blended with two volumes of pale oil of the desired viscosity, at a bulk depot, and distributed to individual users, who then dilute it with from two to ten volumes of pale oil prior to its use on automatic screw machines employed in working various stainless steels. In comparison with a commercial blend of cutting oil recommended for this purpose, our composition produced both extended tool life and smooth finish of the workpiece.
- sulphurized fat such as sulphurized sperm oil or sulphurized lard oil
- Example 9 Percent volume Product of Example 4 20 Miscible oil having extreme pressure properties (such as sulphurized lard oil or other non-petroleum oil)- 10 Refined mineral oil of desired viscosity 70 This blend used on a gun drilling machine produced a smoother finish of'the workpiece and longer tool life than did a commercial blend of pale oil and sulphurized fatty oil previously used and recommended for this purpose.
- Miscible oil having extreme pressure properties such as sulphurized lard oil or other non-petroleum oil
- Example 10 1 Percent volume Product of Example 4 10 Refined mineral oil SAE 90 Using this blend as a gear oil: after running the motor less than three hours it was impossible to hold ones hand on the gear box due to the overheating produced when the mineral oil alone was used; after adding the 10% of our sulphurized petroleum, it was possible to run the motor indefinitely without overheating.
- Example 11 Another gear oil, which additionally had extreme pressure characteristics was produced by including 3% vol. lead naphthenate in the preceding formula (the mineral oil then being 87% volume).
- other suitable extreme pressure additives include chlorinated hydrocarbons and/or phosphorated hydrocarbons (e.g. tricresyl phosphate).
- chlorinated additives may be preferred;
- n f a kali Or alkaline-earth soaps (e.g. sodium, lithium or calcium W ns soaps). in either event, the presence of our sulphurized mineral 011 results in longer gear life and smoother performance.
- Example 12 Another extreme pressure gear oil was compounded of Percent volume Product of Example 4 15 Chlorinated paraffin wax 5 Refined mineral oil of desired viscosity 80
- a heavy duty petroleum-base gear oil may contain about w. to about w..of our sulphurized mineral oil, about 3% w. to about 20% w. of extreme pressure agents, and the remainder being an inert vehicle consisting essentially of refined mineral oil.
- Example 13 5% volume of the product of Example 4 was incorporated in a water-soluble mineral oil and the mixture then emulsified with volumes of water. This is sprayed onto the contact face of the iron mold in a glass factory in order to minimize sticking of the glass to the mold. In comparison with such a spray which lacked our sulphurized component, our formula produced a cleaner release operation and resulted in considerable time-saving in cleaning the molds before re-use. Apparently the active sulfur produced by our process, inhibits iron impurities in the glass from adhering to the iron mold. In general, about 1% W. to about 10% W.
- sulphurized petroleum can be mixed with the water-soluble oil, and the mixture is then emulsified with up to as much as about 150 volumes of water to form the sprayable fluid.
- the aqueous component then volatilizes from the mold surface to leave a thin film of oil.
- Example 14 In drilling an oil well, the threads of the temporary casing sections became frozen in 40% of the joints when using a commercial pipe thread lubricant recommended for this purpose. After 20% volume of the product of Example 4 was blended into the commercial lubricant, the project was completed without any galling or freezing of joints.
- a pipe thread lubricant may contain about 5% w. to about w. of our sulphurized petroleum, about 0.5 w. to about 10% w. of a metallic soap, and the remainder being an inert vehicle consisting essentially of refined mineral oil.
- the process which comprises reacting a naphthenicbase mineral oil, having a viscosity index below about 70, with about 0.1% w. to about 10% 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, neutralizing the oil, reacting it with a normally liquid, sulfur halide at ambient room temperature, and separating the resulting precipitate and hydrogen halide therefrom, thereby to leave a stable and homogeneous oil characterized by lack of offensive odor and containing up to about 13% w. of active sulfur in oil-soluble organic compounds which have anti-weld properties.
- composition of the preceding claim 13 wherein said vehicle includes water which is emulsified with said fluid whereby said composition is adapted to be sprayed onto a metallic mold and thus to serve as a mold release agent.
- composition of the preceding claim 13 wherein said vehicle comprises refined mineral oil and a greaseforming quantity of metallic soap.
- a pipe thread lubricant comprising about 5% w. to about w. of the fluid of claim 10, about 0.5% W. to about 10% w. of a metallic soap, and the remainder being an inert vehicle consisting essentially of refined mineral oil.
- a petroleum-base gear oil comprising about 10% w. to about 20% w. of the fluid of claim 10, about 3% w. to about 20% w. of extreme pressure agent, and the remainder being an inert vehicle consisting essentially of refined mineral oil.
- a sprayable mold-release fluid consisting essentially of a mixture of about 1% w. to about 10% w. of the fluid of claim 10 and about w. to about 99% w. of refined mineral oil, which mixture is emulsified with from about 40 to about volumes of water.
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Description
United tatcs atent O 3,309,315 SULPHUREZED CUTTENG H. AND PROCESS (3F MAKENG SAME John Hanna J. Tarazi and Herbert D. Ivey, In, Pasadena, Calif, assigns-rs to Lubrication Company of America, Los Angeles, Caiif. No Drawing. Filed Aug. 14, 1963, Ser. No. 301,986 21 Claims. (Cl. 252-42A) Cutting oils used in the machining of steel and the like, require an active sulfur compound in the oil; that is, a compound which at a temperature lower than the welding temperature of steel forms iron sulfide on the tool and work surface so as to prevent the two from welding together. This anti-weld property of the compounded lubricant is required especially with soft metals and in making deep cuts and working at slow cutting speeds. For harder metals, anti-weld properties are still needed but are associated with extreme pressure additives such as sulfurized or chlorinated fats and waxes which have both cooling and load-bearing properties. They also prevent the formation of too much iron sulfide such as would erode the edge or point of the cutting tool. Hence, a balance between these factors produces the optimum formula for a particular metal or a particular machining operation.
The art shows many types of extreme pressure compounds such as sulfurized fats and esters, chlorinated fats, esters, and waxes, and many other compounds of phosphorous as well as combinations of all these, but very few of the sulfur compounds have anti-weld rather than extreme pressure characteristics. Those that do show anti-weld characteristics are usually present in very small percentages. The total bound sulfur content of most cutting oils is only slightly informative, unless it is first broken down between active and inactive sulfur. inactive sulfur then should be broken down again between sulfurized fats and the like, which have extreme pressure characteristics and the sulfur naturally in the oil which seems to have neither.
While petroleum may often contain naturally occurring sulfur compounds, these generally lack beneficial proper 'es, may also be odorous and/Or corrosive, and ardusually removed in the early refining or treatment process. In contrast, various methods have been used to obtain beneficial sulfur by direct introduction of the element (or by injection of sulfur-containing reagents) into fatty oils as well as into (refined) mineral oils. However fatty oils cool the workpiece more than does mineral oil, and hence are less applicable in cutting fluids as they generally lack anti-Weld properties and are unable to acquire anti-weld properties without the presence of extreme pressure qualities.
Alternately, sulphur has been incorporated into additives such as synthetic polymers, which are then dispersed in the lubricant base to build up a desired concentration of useful sulfur. However, the direct reaction of sulfur with mineral oil has too often yielded a dark colored, malodorous low sulfur content oil from which the sulfur or sulfur-containing precipitate soon separates upon agitation and/or aging. In any event, the amount of useful sulfur permanently introduced by reaction with liquid petroleum lubricant (mineral oil) has been at best no more than about three and a half or four percent, and such procedure has been generally possible only by reacting lubricating fractions of paraffinic base stock with stron reagents at elevated temperature, and in some cases with pressure.
It has now been found however, that by selection of a mildly or incompletely acid-treated, naphthenic-base mineral oil (typically a lubricating oil fraction thereof), a high concentration of useful sulphur (cg. up to about 13% sulfur by weight) can be directly, easily and stably introduced into the petroleum so that the resulting liquid can then be used as a cutting oil per se, or can even be diluted with an equal volume or many volumes of cheaper (depending on the metal to be cut) or local lubricant vehicle and still retain a satisfactory percentage of useful (i.e. active) sulfur having anti-weld properties. Such reaction between the sulfur-containing reagent and the mineral oil can be effected without heating, that is, at ambient room temperature. Although elevated temperature would increase the reaction rate, it is obviously more economical not to heat it.
We have found that a moderate sulfuric acid treatment (i.e. with up to about 10% W. H 50 of naphthene base crude oil (also called asphalt base crude, California or Western crude, Gulf crude, coastal crude, etc.) appears to leave the remaining (dissolved) unsaturated components of the oil more susceptible to a subsequent reaction with certain sulphur compounds so as to form beneficial, solution-stable, sulfur-bearing, organic compounds in the oil. This is in marked contrast to attempted reaction of (the same) crude oil after initial treatment with other extractants such as furfurol, Duosol (phenol-propane), sulfur dioxide, etc. On the other hand, a more strenuous or complete sulphuric acid extraction of naphthenic petroleum apparently leaves in it only saturated or unreactive components, which, similar to an originally parafiinic crude, subsequently do not react in the present manner to incorporate a high concentration of beneficial and solution-stable sulfur. A viscosity index below about 70 may be taken as an approximate boundary to distinguish the naphthem'c base crudes which may be treated by the present invention, as contrasted with the more parafiinic petroleums.
Restated: sulphuric acid is commonly used to remove undesirable (especially unsaturated) components from crude oil (by their precipitation, followed by neutralization of the liquid). However, when sulphuric acid treatment is applied to a parafiinic base oil, or is continued to the limit of possible reaction with a naphthenic base oil, it removes all of the unsaturated (and polymerizable) components. Consequently, subsequent introduction of sulfur into the refined petroleum is then possible only to a limited extent and by comparatively strenuous reaction; such practice (when at all effective) has been generally limited to reacting paraihnic type, crude oil following its acid treatment (or its refinement by other means). Now however, by starting with a naphthenic-base crude oil and incompletely acid-treating it, the neutralized liquid is then beneficially reacted with a normally liquid sulfur halide. Such reaction forms in situ, solution-stable, non-malodorous, sulfur-containing organic compounds which are especially beneficial in cutting oil (the entire liquid petroleum reaction-mixture after removal of sludge and volatile components being usable as cutting oil, when it is characterized by other required physical properties, such as viscosity, flash point, etc.). In addition to the reaction compounds subsequently formed in situ by the sulfur halide, the initial incomplete sulfuric acid treatment itself apparently produces some useful compounds which remain in the oil and which possibly may be polymerized by the subsequent reaction with sulfur halide (at least in part). On the other hand, the sulfuric acid removes (as a sludge) various higher molecular weight, reactive compounds which would otherwise later react with the sulfur halide, but would not thereafter permanently remain in solution. Hence the present process increases the yield from the subsequent sulfur halide treatmentin other words, less of the sulfur halide reaction product (as measured by the sulfur content) is lost in the subsequent sludge or precipitate.
By our process, the entire liquid crude oil which possesses any usable lubricating qualities can be sulphurized generally after removal of tar or heavy residuum, and the topping of gasoline and naphtha portions) and if desired, this overall range which distills from about 300 F. to about 800 F., can be sulfurized following its sulfuric acid treatment, either before or after its fractionation. Or a lubricating oil fraction (e.g. distilling between about 500 F. and about 760 F. and having a viscosity index between about 35 and about 30) such as may be employed in its entirety as a cutting oil may be sulfurized; alternately, under low temperature (refrigerated) operation, a fluid as light as a kerosene fraction can be used as a cutting oil and hence such a volatile portion can be sulfurized with such end use in mind. Such thinner oil has a greater heat transfer value and its comparatively low flash point is of no consequence under frigid operating conditions. On the other hand, a more viscous portion than desired for the ultimate cutting fluid can be sulfurized with the intention of diluting it later with more readily available (or cheaper) diluent -which need not be mineral oilsince a sulphur concentration as high as the obtainable 13% w. is not need ed in many cutting liquids. Likewise, the sulfurized fraction can be diluted with less viscous fluid which in addition contains other desired additives such as extreme pressure agents, etc., or the additives can be added to the total vehicle after its dilution. To repeat: the entire usable distillate range of mineral oil can be sulfurized as a unit and subsequently fractionated. Or the liquid petroleum can first be fractionated and (one or more) individual fractions then sulfurized.
Normally liquid sulfur halide" refers generically to sulfur halides which are liquid at ambient room temperature and atmospheric pressure, such as sulfur-monochloride, sulfur dichloride, sulfur monobromide, thionyl chloride, sulphuryl chloride, or other sulfur halides which are liquid under the conditions under which the reacting petroleum or mineral oil remains liquid. However sulfur monochloride is the most convenient for the present use and the invention will be subsequently exemplified by employment of this reagent. In general, reaction of the sulfur halide with the Western mineral oil evolves some heat and this may be taken as an indication of the petroleum to beneficially utilize the sulfur halide. In general, the potential reactivity is reached with addition of a maximum of about 50% weight S Cl However we prefer to use a smaller quantity and to add this amount in successive fractions over a period of time in order to avoid rapid (temporary) temperature rise and to permit a slower, more stable and complete reaction. Alternately, if it is desired to add the entire quantity of reactant at the beginning, the amount of sulfur monochloride which will remain mixed with the petroleum may be taken as the practical limitation of quantity required. Hence when a permanent layer of the reagent remains separate from the mineral oil after mutual agitation, it may be considered that the petroleum has the required quantity of reactant dispersed therein. When adding the reagent in two or more fractional amounts so as not to effect a gross temperature rise (e.g. no more than about 10 to 20 F.), the reaction is completed in a maximum period of about 12 to 15 hours, or what might roughly be termed overnight. The odor of sulfur chloride can then no longer be detected upon stirring. Air is blown through the liquid until no odor of hydrogen chloride remains; it may be heated to about 150 F to about 200 F. to hasten removal of all traces of volatile halide. The small precipitate of insoluble compounds is removed, this is generally on the order of to 30% w. and even this does have the very offensive odor which characterized the in situ sulfurization processes of the prior art.
On the other hand, if the naphthenic crude is reacted first with more than about w. sulfuric acid, this stronger treatment will convert it substantially to.a paraffinic oil and will remove the compounds which later (by our process) form solution-stable, organic sulfur compounds. While any small amount of concentrated sulfuric acid will have some beneficial effect on the crude oil, treatment with about 0.1% W. may be taken as a practical minimum. About 0.5% W. to about 5% w. has been found quite adequate in most cases. While the present proportions are stated with reference to concentrated sulfuric acid (which is about 95% H 50 and about 5% water), it will be apparent that since the concentrations described for acid treatment are those of the final dilution of mineral oil and sulfuric acid, it is generally irrelevant whether the mixing step is initiated with concentrated or with more dilute sulfuric acid, as long as the final mixture of oil and acid has the designated ratio. Thus, treating petroleum with 1% w. concentrated sulfuric acid, signifies that one percent by weight of the final dilution consists of H it does not mean that a liquid which itself was 1% sulfuric acid was first added to the petroleum. However, since small difierences in said concentration are not minutely critical, and in addition since the final result also bears some relation to the time (and temperature) of treatment, it will be apparent that adjustments of the relevant factors will be made by a skilled chemist in applying the teaching of the present invention to particular reaction conditions.
In contrast, if the naphthenic crude (in place of sulfuric acid treatment) is refined by any of the various solvent extraction processes (e.g. furfurol, sulfur dioxide, propanephenol Duosol, etc.) a subsequent treatment with sulfur monochloride (with or without heating) will incorporate even less sulfur (e.g. 2.6% w.) than can be incorporated in a paralfinic base oil at elevated temperature, since apparently the extraction process has removed the compounds which would have later incorporated sulfur.
By way of further illustration of our process, a naphthenic base, straight run, Western mineral oil having a distillation range of about 500 F. to about 760 F. and a pour point below -30 F. was agitated with 1% vol. concentrated sulfuric acid at room temperature for min. and then allowed to settle for 4 hours. The acid sludge was separated and the oil neutralized by contact with filtering clay (1% bentonite by wt); after filtering, the oil had the following analysis:
Gravity API 60 F 20-225 Viscosity SSU F. 100-110 Aniline point, F -160 Neutralization number 0.1 NPA color 1-2 Pour point, F. 30 Active sulfur (ASTM Dl66259T) None Total sulfur (ASTM D12958), percent 0.2
Example 1 To 1 gallon (7.6 lbs.) of the acid-treated oil was added 0.3225 lb. of S Cl at room temperature and the mixture agitated by bubbling air therethrough for about 4 hours, then left in the reaction kettle without agitation overnight. The second day another equal portion of S Ci added (total of 0645/16 lbs.=8.5% w.), and agitated as before. The end of the reaction was indicated by the absence of sulfur monochloride smell in the effluent vapor. The kettle with its content was then heated to a temperature of 200 F. with air blowing through the body of the oil in order to clear it of all hydrogen chloride. Air continued to be blown through the oil at this temperature about 10 hours until HCl ceased to evolve. (However, there was no appreciable change of the active sulfur content of the oil during this period of heating.) The body of the oil was then left to settle, and the oil was filtered. The resultant product is a dark mahogany color, sulfurized mineral oil, of pleasant odor,
stably homogeneous, and possessing the following characteristics:
Gravity API 60 F. Viscosity SSU 100 F 130-150 Pour point, F -30 Active sulfur, percent 5.7
Total sulfur, percent 5.9
Yield of oil, percent 95 Example 2 900 gms. of acid treated oil was reacted with 200' gms. of S Cl added in two equal portions, following the procedure of Example 1 above. (Sulfur monochloride 200/900 g.=22% W.) The result was:
Gravity API 60 F 15.5 Viscosity SSU 100 F 200 Active sulfur, percent 8.1 Total sulfur, percent 8.3 Yield of oil, percent 93 Example 3 800 gms. of acid treated oil reacted with 210 gms. of S Cl (=26% w.) added in two equal portions following procedure of Example 1 above. The result was:
Gravity API 60 F 13.1 Viscosity SSU 100 F 245 Activesulfur, percent Total sulfur, percent 10.2 Pour point, F. -30
Yield of oil, percent 90 Example 4 700 gms. of the former acid treated oil was reacted with 300 g. (43% w.) of S Cl following the procedure of Example 1. The resulting product has the following analysis:
Gravity API 60 F 10.6 Viscosity SSU 100 F 255 Total sulfur, percent 13.0 Active sulfur, percent 12.8
Yield of oil, percent 70 Example 5 7.6 lbs. of the same cut of naphthenic base oil untreated with sulfuric acid, was reacted with 0.645 lb. of S 01 following the procedure in Example 1 above. The resulting product has following analysis:
Gravity API 60 F. 19.5 Viscosity SSU 100 F. 125 Active sulfur, percent 2.0 Total sulfur, percent 2.6 Yield of oil, percent 75 The untreated oil contained 0.6% natural sulfur.
Example 6 The procedures outlined in Examples 1, 2 and 3 were followed on a paraffinic base, mineral oil with a similar viscosity as the naphthenic base oil of Examples 1 through 4, as well as examples of higher and lower viscosity. In each instance the yield was an unstable sulfurized oil with a maximum active sulfur of 2.5% w., part of which precipitated out as elemental sulfur within about a week.
periods of time. In general, about 0.5% w. to about 25% w. sulfur halide is preferred; or expressed another way-enough to incorporate up to about 10% w. active sulfur so as to produce an economical concentrate which could be diluted, as needed, with up to four volumes of liquid and still provide a very satisfactory cutting fluid for many purposes, containing approximately 2% w. active sulfur.
The following compositions illustrate some of the uses of our sulphurized mineral oil when mixed with various additives and/ or diluents:
Example 7 A cutting oil was blended from 23% w. of the product of Example 4, and 77% w. of mineral oil (100 SSU 100 F.). The blend contained about 3% w. of active sulfur. When used in threading steel pipe, bright shiny threads with smooth surfaces ensued, and the tool life was up to 40 times longer than when using a commercial mixture of pale oil and sulphurized fatty oil which was recommended for this purpose. In comparison, when using only the recommended commercial product, in addition to the shorter tool life there was produced shredded threads and torn surfaces of the metal which had only a dull finish or appearance.
Example 8 A concentrate was formed by mixing the product of Example 4 with an equal volume of sulphurized fat (such as sulphurized sperm oil or sulphurized lard oil). One volume of this concentrate is then blended with two volumes of pale oil of the desired viscosity, at a bulk depot, and distributed to individual users, who then dilute it with from two to ten volumes of pale oil prior to its use on automatic screw machines employed in working various stainless steels. In comparison with a commercial blend of cutting oil recommended for this purpose, our composition produced both extended tool life and smooth finish of the workpiece.
Example 9 Percent volume Product of Example 4 20 Miscible oil having extreme pressure properties (such as sulphurized lard oil or other non-petroleum oil)- 10 Refined mineral oil of desired viscosity 70 This blend used on a gun drilling machine produced a smoother finish of'the workpiece and longer tool life than did a commercial blend of pale oil and sulphurized fatty oil previously used and recommended for this purpose.
Example 10 1 Percent volume Product of Example 4 10 Refined mineral oil SAE 90 Using this blend as a gear oil: after running the motor less than three hours it was impossible to hold ones hand on the gear box due to the overheating produced when the mineral oil alone was used; after adding the 10% of our sulphurized petroleum, it was possible to run the motor indefinitely without overheating.
Example 11 Another gear oil, which additionally had extreme pressure characteristics was produced by including 3% vol. lead naphthenate in the preceding formula (the mineral oil then being 87% volume). For drilling and machining metals, other suitable extreme pressure additives include chlorinated hydrocarbons and/or phosphorated hydrocarbons (e.g. tricresyl phosphate). In working Carbon steels and stainless steels, as with automatic screwmachines, chlorinated additives may be preferred; When used as a long-lasting lubricant, the consrstenQY- g ease can be obtained, when desired, by addit n f a kali Or alkaline-earth soaps (e.g. sodium, lithium or calcium W ns soaps). in either event, the presence of our sulphurized mineral 011 results in longer gear life and smoother performance.
Example 12 Another extreme pressure gear oil was compounded of Percent volume Product of Example 4 15 Chlorinated paraffin wax 5 Refined mineral oil of desired viscosity 80 In general, a heavy duty petroleum-base gear oil may contain about w. to about w..of our sulphurized mineral oil, about 3% w. to about 20% w. of extreme pressure agents, and the remainder being an inert vehicle consisting essentially of refined mineral oil.
Example 13 5% volume of the product of Example 4 was incorporated in a water-soluble mineral oil and the mixture then emulsified with volumes of water. This is sprayed onto the contact face of the iron mold in a glass factory in order to minimize sticking of the glass to the mold. In comparison with such a spray which lacked our sulphurized component, our formula produced a cleaner release operation and resulted in considerable time-saving in cleaning the molds before re-use. Apparently the active sulfur produced by our process, inhibits iron impurities in the glass from adhering to the iron mold. In general, about 1% W. to about 10% W. of our sulphurized petroleum can be mixed with the water-soluble oil, and the mixture is then emulsified with up to as much as about 150 volumes of water to form the sprayable fluid. The aqueous component then volatilizes from the mold surface to leave a thin film of oil.
Example 14 In drilling an oil well, the threads of the temporary casing sections became frozen in 40% of the joints when using a commercial pipe thread lubricant recommended for this purpose. After 20% volume of the product of Example 4 was blended into the commercial lubricant, the project was completed without any galling or freezing of joints. In general, such a pipe thread lubricant may contain about 5% w. to about w. of our sulphurized petroleum, about 0.5 w. to about 10% w. of a metallic soap, and the remainder being an inert vehicle consisting essentially of refined mineral oil.
Since such components as extreme pressure agents, mineral soaps used in grease-making, etc., are well known in the lubricant compounding art, they need not be described in detail here. Likewise the various specific proportions recited by way of example in particular formulae are not given by way of limitation but rather as illustrative examples. It is within the competence of a chemist skilled in the art to adopt the teaching and disclosure of our invention to the particular problem at hand; and the breadth of the claimed invention is to be evaluated by reference to the possible substitution of functional equivalents known to the prior art, which may be employed in association with our composition and process.
We claim:
1. The process which comprises reacting a naphthenicbase mineral oil, having a viscosity index below about 70, with about 0.1% w. to about 10% 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, neutralizing the oil, reactwith a normally liquid, sulfur halide, and separatsulting precipitate and hydrogen halide there A yrto leave a stable and homogeneous oil char- 3 ck of offensive odor and containing up to of active sulfur in oil-soluble organic comve anti-weld properties.
2. The process which comprises reacting the lubricating oil fraction of a naphthenic-base mineral oil, with about 0.1% w. to about 10% 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, neutralizing the oil, reacting it with a normally liquid, sulfur halide, and separating the resulting precipitate and hydrogen halide therefrom, thereby to leave a stable and homogeneous oil characterized by lack of offensive odor and containing up to about 13% w. of active sulfur in oil-soluble organic compounds which have anti-weld properties, whereby the bulk of said oil containing said soluble compounds is applicable as a cutting oil by itself or upon dilution.
3. The process of the preceding claim 1 wherein said sulfur halide is esentially sulfur monochloride.
4. The process of the preceding claim 2 wherein said lubricating oil fraction has a viscosity index between about 35 and about 30.
5. The process which comprises reacting a naphthenicbase mineral oil, having a viscosity index below about 70, with about 0.1% w. to about 10% 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, neutralizing the oil, reacting it with a normally liquid, sulfur halide at ambient room temperature, and separating the resulting precipitate and hydrogen halide therefrom, thereby to leave a stable and homogeneous oil characterized by lack of offensive odor and containing up to about 13% w. of active sulfur in oil-soluble organic compounds which have anti-weld properties.
6. The process of the preceding claim 5 wherein said sulfuric acid is about 0.5% w. to about 5% w. and said sulfur halide is added in fractional amounts during an extended period of time up to about 15 hours, and said reaction is effected principally at ambient room temperature with agitation effected by passage of an air current through the reaction mixture until no odor of sulfur halide or hydrogen halide is evident in the efferent air even upon heating to about 200 F. i
7. The process of the preceding claim 6 wherein said sulfur halide is essentially about 0.5% w. to about 25% w. of sulfur monochloride.
8. The process which comprises reacting the lubricating oil fraction of a naphthenic-base mineral oil, with about 0.5% w. to about 5% 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, neutralizing the oil, reacting it at ambient room temperature with up to about 50% w. of sulfur monochloride, and separating the resulting precipitate and all volatile chlorides therefrom, thereby to leave a stable and homogenous cutting oil or additive therefor, characterized by lack of offensive odor and containing up to about 13% w. of active sulfur in oil-soluble organic compounds which have anti-weld properties. 1
9. A mineral oil base, cutting fluid containing homogeneously and stably dispersed therein, an anti-weld quantity of the organic, oil-soluble reaction product formed between a normally liquid, sulfur halide and a naphthenicbase mineral oil having a viscosity index below about 70; said reaction product being formed by treating said mineral oil with about 0.1% W. to about 10% 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 with the sulfuric acid and neutralizing the remaining oil, and then reacting the neutralized oil with said normally liquid sulfur halide and separating the resulting precipitate and hydrogen halide therefrom, thereby leaving an organic, oil-soluble reaction product containing up to about 13% w. active sulfur and having consequent anti-Weld properties, said reac tion product remaining dissolved in the mineral oil in 9 which it was formed, which oil forms the bulk of said cutting fluid.
10. The cutting fluid of the preceding claim 9 wherein said normally liquid, sulfur halide consists essentially of sulfur monochloride, and said reaction product contains from about 4% w. up to about 13% w. of active sulfur based on the weight of said naphthenic base mineral oil.
11. The cutting fluid of the preceding claim 10 wherein said reaction product is formed essentially at ambient room temperature.
12. The cutting fluid of the preceding claim 9 wherein said naphthenic-base mineral oil, prior to said sulfuric acid treatment, consists essentially of a lubricating oil fraction of said mineral oil.
13. A fluid composition having lubricant and anti-weld properties and characterized by a beneficial quantity of the reacted mineral oil of claim 9 generally uniformly dispersed in a lubricant vehicle.
14. The cutting fluid of the preceding claim 9 wherein said naphthenic-base mineral oil, prior to said sulfuric acid treatment, consists essentially of a lubricating oil fraction of said mineral oil, and said normally liquid, sulfur halide consists essentially of sulfur monochloride which is reacted with the su1furic-acid-treated-oil essentially at ambient room temperature.
15. The composition of the preceding claim 13 wherein said vehicle includes water which is emulsified with said fluid whereby said composition is adapted to be sprayed onto a metallic mold and thus to serve as a mold release agent.
16. The composition of the preceding claim 13 wherein said vehicle includes an added amount of an extreme pressure agent.
17. The composition of the preceding claim 13 wherein said vehicle includes an added amount of miscible, sulphurized, non-petroleum oil having extreme pressure properties.
18. The composition of the preceding claim 13 wherein said vehicle comprises refined mineral oil and a greaseforming quantity of metallic soap.
19. A pipe thread lubricant comprising about 5% w. to about w. of the fluid of claim 10, about 0.5% W. to about 10% w. of a metallic soap, and the remainder being an inert vehicle consisting essentially of refined mineral oil.
20. A petroleum-base gear oil comprising about 10% w. to about 20% w. of the fluid of claim 10, about 3% w. to about 20% w. of extreme pressure agent, and the remainder being an inert vehicle consisting essentially of refined mineral oil.
21. A sprayable mold-release fluid consisting essentially of a mixture of about 1% w. to about 10% w. of the fluid of claim 10 and about w. to about 99% w. of refined mineral oil, which mixture is emulsified with from about 40 to about volumes of water.
References Cited by the Examiner UNITED STATES PATENTS 1,824,523 9/1931 Adams 25245 2,112,677 3/1938 Muskat 252-45 2,142,916 1/1939 Parkhurst 25245 2,246,282 6/1941 Zimmer et al. 252-45 2,303,853 12/1942 Lutz et -al. 252-45 2,378,803 6/1945 Smith 260139 2,380,072 7/1945 Reid 260-139 2,578,865 12/1951 Veatch et al 25249.5
OTHER REFERENCES Manufacture and Application of Lubricating Greases, C. J. Boner, Reinhold Publishing Corp.,.1954, pp. 152- 157.
DANIEL E. WYMAN, Primary Examiner.
L. G. XIARHOS, Assistant Examiner.
Claims (3)
- 9. A MINERAL OIL BASE, CUTTING FLUID CONTAINING HOMOGENEOUSLY AND STABLY DISPERSED THEREIN, AN ANIT-WELD QUANTITY OF ORGANIC, OIL-SOLUBLE REACTION PRODUCT FORMED BETWEEN A NORMALLY LIQUID, SULFUR HALIDE, AND A NAPHTHENICBASE MINERAL OIL HAVING A VISCOSITY INDEX BELOW ABOUT 70; SAID REACTION PRODUCT BEING FORMED BY TREATING SAID MINERAL OIL WITH ABOUT 0.1% W. TO ABOUT 10% 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 WITH THE SULFURIC ACID AND NEUTRALIZING THE REMAINING OIL, AND THEN REACTING THE NEUTRALIZED OIL WITH SAID NORMALLY LIQUID SULFUR HALIDE AND SEPARATING THE RESULTING PRECIPITATE AND HYDROGEN HALIDE THEREFROM, THEREBY LEAVING AN ORGANIC, OIL-SOLUBLE REACTION PRODUCT CONTAINING UP TO ABOUT 13% W. ACTIVE SULFUR AND HAVING CONSEQUENT 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.
- 13. A FLUID COMPOSITION HAVING LUBRICANT AND ANTI-WELD PROPERTIES AND CHARACTERIZED BY A BENEFICIAL QUANTITY OF THE REACTED MINERAL OIL OF CLAIM 9 GENERALLY UNIFORMLY DISPERSED IN A LUBRICANT VEHICLE.
- 18. THE COMPOSITION OF THE PRECEDING CLAIM 13 WHEREIN SAID VEHICLE COMPRISES REFINED MINERAL OIL AND A GREASEFORMING QUANTITY OF METALLIC SOAP.
Publications (1)
Publication Number | Publication Date |
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US3309315A true US3309315A (en) | 1967-03-14 |
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US3309315D Expired - Lifetime US3309315A (en) | Sulphurized cutting oil and process of making same |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3852206A (en) * | 1973-09-10 | 1974-12-03 | Lubrication Co Of America | Sulfur halogenated cutting oil and process of making |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1824523A (en) * | 1929-08-08 | 1931-09-22 | Standard Oil Co | Sulphurized oils |
US2112677A (en) * | 1938-03-29 | Sulphurized petroleum cutting oils | ||
US2142916A (en) * | 1939-01-03 | Treating lubricating oils | ||
US2246282A (en) * | 1941-06-17 | Sulphurized product and method for | ||
US2303853A (en) * | 1940-12-20 | 1942-12-01 | Gulf Research Development Co | Cutting oil |
US2378803A (en) * | 1945-06-19 | Lubricants | ||
US2380072A (en) * | 1942-03-06 | 1945-07-10 | Phillips Petroleum Co | Sulphurized hydrocarbon and method of preparation |
US2578865A (en) * | 1948-03-31 | 1951-12-18 | Standard Oil Co | Machining fluid |
-
0
- US US3309315D patent/US3309315A/en not_active Expired - Lifetime
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2112677A (en) * | 1938-03-29 | Sulphurized petroleum cutting oils | ||
US2142916A (en) * | 1939-01-03 | Treating lubricating oils | ||
US2246282A (en) * | 1941-06-17 | Sulphurized product and method for | ||
US2378803A (en) * | 1945-06-19 | Lubricants | ||
US1824523A (en) * | 1929-08-08 | 1931-09-22 | Standard Oil Co | Sulphurized oils |
US2303853A (en) * | 1940-12-20 | 1942-12-01 | Gulf Research Development Co | Cutting oil |
US2380072A (en) * | 1942-03-06 | 1945-07-10 | Phillips Petroleum Co | Sulphurized hydrocarbon and method of preparation |
US2578865A (en) * | 1948-03-31 | 1951-12-18 | Standard Oil Co | Machining fluid |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3852206A (en) * | 1973-09-10 | 1974-12-03 | Lubrication Co Of America | Sulfur halogenated cutting oil and process of making |
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