Патент USA US2404871код для вставки
Patented July 309 lgd? 4 UNITED STATES PATENT OFFICE I 2.404.811 LUBRICATING COMPOSITIONS Paul R. van Ess, Berkeley, Forrest J. Watson, Oakland, ‘and Gary M. Whitney, Piedmont, Calif., assignors to Shell Development Com pany, San Francisco, Calil’., a corporation of Delaware No Drawing. Application July 28, 1943, Serial No. 496,678 12 Claims. (Cl. 19.6-13) 1 This invention relates to sulfur-containing ad ditives used to produce improved lubricants and stabilized organic compositions, to methods of preparing concentrates of naturally-occurring sulfur-containing additives for lubricating oils and greases, and to improved methods of inhibit ing oxidative decomposition and lubricating in ternal combustion engines, particularly those containing corrosion~i5ensitive alloy bearings. , 2 is to obtain superior aviation and Diesel engine, heavy duty lubricating oils. A still further pur pose is to produce novel sulfur-containing petro leum fractions which contribute valuable anti corrosive, anti-oxidant, anti-wear, high ?lm strength and/or other advantageous properties to organic compositions in which they are incor porated. Other objects will be apparent from the following description. I It was quite generally; believed heretofore that 10 It has been determined that the anti-corrosive and anti-‘oxidant properties of the desirable nat relatively high boiling sulfur compounds natur ural petroleum sulfur compounds are associated ally occurring in petroleum crudes were good in vwith the availability or activity of the sulfur in hibitors for lubricating oils, imparting to them them.’ If the compounds or mixtures thereof, anti-corrosive properties and oxidation stability. As a result, several high sulfur-content lubricat 15 such as those obtained from petroleum by the hereinafter described methods have low sulfur ing oils have appeared on the marketfor which certain superiorities are claimed. However, in ' availabilities, they are themselves'substantially non-corrosive to bearing surfaces but may fail to many cases such claims cannot be veri?ed by inhibit other types of corrosion. If, however, laboratory and engine tests. Moreover, it was found that as a rule these high sulfur lubricating 20 their sulfur availability is above a certain mini mum, they will inhibit against both bearing cor oils have a very strong and dangerous tendency to form lacquer, sludge ‘and carbon on pistons and piston rings, particularly in high tempera ture operation. rosion and oxidative decomposition and may also contribute other valuable properties to the lubri eating oil to which they are added. Some of these It has now been discovered however that 25 additives may produce a brown or colored ?lm on metal bearing surfaces in engine operation. among the naturally-occurring sulfur com pounds in petroleum oils there are bene?cially active as well as inactive and even detrimental With others, (notably the hereafter described Utanol ra?lnates) this discoloration of copper‘ surfaces may be substantially absent, but the an varieties and that the bene?cially active com 30 ti-corrosive and anti-catalytic properties which pounds can be extracted from the oils in which the sulfur compounds contribute to the lubri they occur to produce concentrates of relatively eating oil are still prominent. Some of these sul high non-corrosive sulfur content, which, when furcompositions (e. g. the Utanol ra?inates) also added to well re?ned lubricating oils, impart to possess material anti-wear properties and/or the properties without materially increasing their 35 ability to enhance or prolong the anti-wear prop erties of other anti-wear agents. tendency to form lacquer, sludge and carbon. them good oxidation stability and anti-corrosive It is accordingly an object of this'invention to produce from crude petroleum, sulfur concen trates which, when added to refined lubricating 40 oils and the like, act as oxidation and corrosion inhibitors without materially increasing the lac-. quering and sludge depositing tendency of the base oil. A further purpose is to provide lubri cating compositions having decreased tendencies 45 to attack modern alloy bearings. Another object The reactivity or availability of the sulfur in various compounds is de?ned as the percent sul fur (calculated on the total sulfur content in the compound or mixture) which will react with me tallic copper under certain conditions. It is de termined by heating at various temperatures samples of the compositions with an excess (over the amount equivalent to the sulfur content) of ?nely divided metallic copper for a standard pe 2,404,871 riod of time, here taken at 16 hours. The cop 2,315,131, sulfuric acid treatment, solvent extrac per sul?de formed is then determined quantita tion, selective hydrogenation, etc., or a combina tively as by oxidizing the sul?de with bromine tion of such treatments, preferably under condi and precipitating the resultant sulfate with bar tions not to reduce the sulfur content of the con ium chloride. If the percent of sulfur reacted is centrate excessively, i, a. so that not more than plotted against the reaction temperatures for about 1/3 of the total sulfur content is lost. In various sulfur compounds or high sulfur content other Words. our concentrates are “rai?nates,” oils, a family of curves is obtained which at rel “raiilnates” as commonly understood in the petro atively low temperatures are quite close together. leum industry being relatively para?lnic petro However, at temperatures of say 300° C. the 10 leum fractions from which naturally associated curves separate widely and the availability of the aromatics have been removed. Whether the sulfur as determined at this temperature gives sludging tendency is the result of over-activity of a reasonable correlation for various petroleum certain sulfur compounds (as might well be) or derived sulfur compounds with their inhibiting is due to the presence of other associated com e?icacy when incorporated in re?ned lubricating 15 pounds, is not known at this time. However, this oils. At this particular temperature, compounds is immaterial, as it is sufficient that a treatment having sulfur availabilities below about 15% (for adapted to remove aromatics from hydrocarbon example those in West Texas high-sulfur lubri mixtures will achieve the desired result. cating oil extracts) are of little if any effect, In general, crudes which contain the active sul while certain other natural petroleum sulfur 20 fur compounds in concentration su?lclent to re compounds of higher availability, 1. e. above cover them in relatively concentrated form. are of about 15% and preferably above about 20% (for highly asphaltic nature such as certain California example, those in Utanol ra?inates) are highly (particularly Mount Rose, Coalinga, Santa Maria) effective. and Venezuelan crudes. The availability of these sulfur compounds has 25 Outstanding is an oil known to the trade as been correlated with their anti-corrosiveness in “Utanol" which is an asphaltic petroleum crude lubricating oils, for example by determining the obtained from snallow wells in the Great Salt comparative weight losses of copper-lead bearings Lake area and southern Idaho. The oily fraction subjected to the action of lubricating oils contain separated from this material is known as “Utah ing standard amounts of these sulfur additives 30 on.” Utanol varies in sulfur content from about plus a commonly used detergent, which, although 10% to 1.5%, has a spec?c gravity of about 1.0 to contributing other valuable properties, causes or 1.1, a saponi?cation number of around 10 to 20, increases corrosiveness of the lubricating oil. naphtha msoluoles of 10% to 15%. and contains Thus various blended oils have been tested and about 40% to ‘10% asphalt as determined by pre compared by a procedure known as the Thrust 35 clpitation with about 0' volumes of n-butane at 60° Bearing Corrosion test, which was described in to 11500" C. It has no appreciable content of phe the National Petroleum News, September 17, 1941, pp. R 294-296. Fractions or concentrates of active sulfur com.. no . Methods for obtaining an oil fraction having the desired concentration of active sulfur com pounds may be obtained by various methods from 40 pounds from crudes having a sulfur content above 5%, such as Utanol, are relatively simple. One tain them. In most crudes, the concentration of such method speci?cally applied to Utanol is as these compounds is quite low, and special methods follows: (which are described later) are required in order The crude is ?rst de-asphalted by any of the 45 to recover them in relatively high concentration, standard de-asphalting methods. This may be so that they may be added to re?ned lubricating achieved by asphalt precipitation or distillation, oils in eifective amounts without materially or both. The precipitation method is preferred changing the desirable properties of the latter. because of the extremely high asphalt content of As a rule, it is poor practice to add to a well re ?ned lubricating oil more than about 10% of any 50 ‘the Utanol which may interfere with the proper distillation and result in cracking of the asphalt addition agent. The effective amounts of sulfur and the inclusion of harmful cracked material in which must be added to various re?ned lubricat the distillate. ing oils in the form of active sulfur compounds various high sulfur petroleum crudes which con The precipitation may be carried out by mixing usually are on the order of 0.1% to 0.3% by ~ 55 the Utanol with several volumes of a liquid light weight of re?ned oil, although quantities of be tween 0.02% and 1% may be useful. In a semi plastic composition such as a grease, higher amounts may be employed. Therefore, it is de sirable, if not essential, that the. sulfur content of a concentrate of active compounds be at least 60 2% and preferably 5% or higher. As previously indicated, the indiscriminate ad dition of natural petroleum sulfur compounds tends to cause an increase in lacquering and sludge depositing tendencies of the blended oils. This however can be minimized by properly re ?ning either the oil from which the active high sulfur concentrates are produced or the concen hydrocarbon oil comprising predominantly or consisting of C: to C6 hydrocarbons, preferably at a temperature within about 75° to 100° C. of the critical temperature of the latter. Thus propane or propylenes at normal room temperature, bu tanes or butylenes at temperatures of 60° C. or above are well suited. Dissolving in benzene and precipitating with isopentane also proved suc cessful. If desired. the crude may be dissolved in a liquid 04 to Cu hydrocarbon, naphtha. light kerosene, etc., and gaseous methane. ethane, nat.. ural gas, propane, fuel gas. water gas, CO, CO: or other cases may be introduced at high pressures to effect or complete the asphalt precipitation. trates themselves before they are added to lubri cating oils. Such re?nement includes substantial 70 Moreover, selective so-called “naphthenlc” sol elimination of asphaltic materials and a treat vents may be present. such as liquid 80:. furtural, ment capable of separating aromatic from non nitrobenzene, beta,beta'-dichlor-diethyl ether. aromatic hydrocarbons, for example, by precipi phenol, cresylic acids. aniline, methylsulfolane, tation with gas, such as methane under high pres dimethylsulfolane. or a large number of others sure as described by Pilat in U. 8. Patent 75 or their mixtures. , 3,404,871 If the crude oil contains relativelyv low boiling components, as gasoline, kerosene, etc., they may be ?ashed from the crude prior to the precipita tion or else may be separated later by fractional distillation of the deasphalted ra?inate oil. Ability of Utanol raillnates to decrease wear . was determined on a. Multiple-Four Bali machine similar- in‘ principle to ‘the Boerlage apparatus described in themagazine vEngineering, volume ' » 136, July 14, 1933. This apparatus comprises four The supernatant liquid layer, 1. e. the ra?‘inate steel balls arranged in pyramid formation.‘ The phase resulting from asphalt precipitation and top ball is rotated by a spindle against the three containing the desired oil, is now separated from bottom balls which are clamped in avstationary the precipitated asphalt. This oil must be further ball holder. All balls are immersed in the oil to re?ned to reduce its lacquer-imparting tendenq 10 be tested. The tests are run for two hours at ,700 R.- P. M. under a '7 kg. loadfand at a controlled Depending on the conditions of the precipita temperature of 130°_ C. Diameters of the wear tion, the nature of the solvents employed and the scars worn on the three balls forming the base of nature of the crude itself, one of several ways may the pyramid are then measured, and the average cies. - ~ ' be followed. Obviously the more drastic the pre cipitation conditions are, the less ‘drastic need be the second treating step which involves (as previously indicated) a treatment adapted to re move aromatic hydrocarbons. Solvent extraction may be employed with any one of the well known selective “naphthenic" solvents previously men tioned. Treatment with strong, i. e. 93 to 100% sulfuric acid is usually desirable and effective. Amounts of sulfuric acid ranging anywhere from 5 to 100 pounds per barrel of the ra?inate oil may be employed. taken as the true indication of wear. Results were as follows: Scar Lubricant ' diameterin millimeters 1 Re?ned aviation lubricating oil,‘ PI gravity 2 Oil #1 containing clay treated Utanol. Pilat 3 Oil #1 containing clay treated Utanol Pilat ' about 26, S0 at 210° F. about 115-125 ________ __ 0.7 raiilnate, AS=0.10% ......................... ._ 0. 47 raii‘lnate, AS=0.30% __________________________ -_ 0.36 Oxidation tests were made with the same oil _ Several treatments may be combined and the second re?ning treatment may be carried out in, the presence or absence of the light hydrocarbon liquid employed in the precipitation; generally 30 its presence may be helpful in the second step. The undesirable components, if any (which may be in the form of sludge, extract, etc), produced in the second re?ning treatment, are now sepa to determine the time required for the absorption of 1800 cc. of oxygen by 100 g. of oil in the pres ence of 1 cm.2 of copper surface/gram of oil at 150° C. The following data are typical: Hours Oil No. 1 (as above) ____________________ __ 9.3 011 No. 2 (as above)? _____________ ...'- ____ -_ 48 1 rated. Solvent, if present, is removed in the usual " manner as by distillation or washing with water or wash solvent, and the recovered-‘high sulfur oil may be given a ?nishing treatment‘ with clay (such as fuller’s earth, acid activated clay, etc.), bauxite, zeolite, silica gel-or other adsorbents. The speci?c dispersion of the treated high sul fur rafiinate oil is often a fair indication of its lacquer imparting tendencies. ' It is desirable This Utanol rai?nate was also tested in the Thrust Bearing Corrosion test, referred to earlier, employing. a compounded heavy dutytruck and bus or Diesel lubricating oil. It contained ineach case 1 % of the magnesium salt of lauryl salicylate which has been a widely used lubricating oil de tergent. but which. although otherwise bene?cial, imparts corrosive properties to the lubricant. In 20 hour tests at 125 lbs. thrust and 2400 R. P. M. with this oil, the copper-lead bearings showed a weight loss at 130° C. of 15 mg./cm.2. When test that the specific dispersion be below about 160,v ed with this same oil, to which had'been added a more preferably below about 140 or 145. Also, 45 clay treated Utanol Pilat ra?inate, AS=0.10%, the bearings showed no weight loss at 160° C. the color may be an indication if taken together with the speci?c dispersion. Preferably, the color v Chevrolet engine tests using procedure L-4—243 ‘ of the Cooperative LubricantsTest Program were should be better than 6 (A. S. T. M. or National Petroleum Association Scale). also made using a corrosive S, A. E. reference oil. - . Samples of treated Utanol railinate oils from 50 Results were as follows: Varnish mung Used voil properties gang's: _ mgJcm.’ 1 Sail)‘. No. Neut. No. Sludge mung , Base oil _____________________________________ ._ 105 73 .' . ’ 106. 5 109. 5 70- 5 72 Base oil + Utanol rai?nate AS=0.30%.__ _ ___ 104. 5 i 73 Base oil + Utanol ra?lnate AS=0.10¢7. Base oil +. Utanol raf?nate AS=0.1 ,7. General range Gravity‘,o ........... .. Viscosity at 100° F... Viscosity at 210° F. 34-39 Viscosity index.._.. --. 40-55 . _ _ _ _ . _ _ _ __ 130-145 Color _______________________________ __ 4-7. 5 Saponi?cation number, mg.KOH/"_-- Ultimate analysis: __ Carbon ________ -_per cent weight“ I Hydrogen _________________ _.do__._ Sulfur ................. ..do.._. ‘ Nitrogen... ............... -_' .'.-_ 0-8 65 0. 9880 ' 1,018 ' 34. 7 53 132 i 1 4% 1 ° 0. 9 A‘ clay treated .Pilat ra?inair ‘ I f 33:4 2i. 7 ‘3. 2 mg. KOH/g. v _22. 2 91's 4- 6 4. 2v 2. 8 ' 25-1 ‘ 26.8 : 9. 98, salt of methylene bis p-i'sooctylphenol, may be seen from the following‘ data of piston ringweight loss _in a CFR-Diesel engine. _Test conditions:' 1400 P. M.;'load,v 68 155.1111? brake mean‘ effec ‘ tive pressure; jacket-temp.‘- 100° C.; voil tempera-J 70 compression ratio ‘1631;114'7 =ceta’ne" number commercial Dieselffuel;~ baseioilt','com-,-_ 76. 27 10. 90 12. 7- V 0.14 84. o ' OH/g. I the e?lciency of ananti-Wear agent, the calcium one acid treated Piiat railinate 0. 98-1. 0 950-1400 mg. The action of a Utanol-railina'te in increasing di?erent batches had the following properties: Speci?c dispersion . . . _ _ I - l" 11.9 ' 0.06 mercial Diesel. lubricating on s. AYE‘. amiss; length, 4, runs of lit-hours, 'resultsreported for: overall period. Megan 8 relatively high speci?c dispersion or content of aromatics, the former often being considerably above 160, unless the solvent extraction and ad P weigh-its‘ Additive loss, mg. ditional treatment preparatory to the solventex 13.4 31.6 radinate NJ ‘ The Utanol ra?lnates‘also possess other desir r able characteristics when incorporated in a lubri cating oil, such as anti-scu?ing and anti-scratch ing properties in Diesel engines. Their bene?cial activity may also be enhanced’ by utilization in the presence of small amounts of synthetic or ganic sulfur-containing ‘anti-oxidants, e. g. di benzyl sul?de or disul?de, wax disul?de, diphenyl sul?de, sulfurized sperm oil, sulfurized ole?n polymers, sulfurized wax ole?ns (obtained in the cracking, or by chlorination and dehydrochlori traction was very drastic. If the speci?c dis persion of the sulfur concentrate is above about 145, the concentrate may ‘ again be solvent-ex tracted or sulfuric acid treated, etc., to further reduce its 'aromaticity and speci?c dispersion to below about 140 in order to produce an addition agent for lubricating oils which has the least lacquer imparting tendencies. the oxidation‘ st‘ability (Domte type oxygen ab sorption apparatus at 150° C.) in the presence of 1 square‘ centimeter of copper per gram of oil of an S. A. E. 60 lubricating oil when added thereto in amounts to raise the sulfur content by 0.1%: Bpre?c. die; , Source of petroleum material > In the table below, ‘a comparison is made of the e?ect of the several sulfur concentrates on pc on o ' sulfur eon- Method of obtaining sulfur cone. Tim; fgm "mm" m 0’ M00 mxme 11 I. 011 Hours None Utanol ......................................................... __ ” " 0. 2 Asphalt precipitation-acid treating ........ ._ 132 47, 7 Mt. Poso lubricating distillate, furiural railinate, 55 V. I _______ -_ Mercurlc acetate in acetic acid ............ _. 120 52,0 SbClr-AlCln .............................. .. 143 32, 1 Mt. Peso lubricating distillate, iurfural ramnate, 65 V. I _______ __ Aluminum chloride ....................... .. West Texas distillate ‘ Acid treat-i-extractlon with HgAer in HA .. ‘17min lubricating distillate, acid treated iurtural railinate, 15B 19d 21, a 13 D0 * _____ Duosol extration followed by acid treat .... .- 200+ 0.8 The method of concentrating sulfur com nation, of para?ln wax), bis-(methylene aryl or 35 pounds with the aid of mercuric acetate in acetic alkaryl sul?des), etc. acid ‘is described below in greater detail: A sample of 50 V. 1. Mt. Poso furfural railinatc was ?rst extracted with glacial acetic acid to re terially below about 5%, such as California and Venezuelan oils, different methods for recovering 40 move nitrogen bases. Glacial acetic acid satu rated with mercuric acetate was then added to the active sulfur compounds must be employed the oil, with stirring, in the amounts shown in than that described for Utanol. Since oils hav-_ the table below. The mixture was allowed to ing a relatively low sulfur content may display As indicated before, when starting with crudes or fractions thereof having sulfur contents ma a ratio of aromatics to sulfur that is higher, for settle and the lower layer drawn off. This ex example, than with Utanols, it is necessary to 45 traction may be performed several times on a sample (as shown in the table) and the remain ?rst remove from these oils some of the aromatics, as by selective solvent extraction with a “naph ing oil then washed with acetic acid to remove the remaining mercury compounds. It is also thenic" solvent of the type described earlier, and advantageous to carryout the extraction in the if necessary augment this treatment with others such as sulfuric acid treatment. Likewise, crudes 50 presence of an inert, oxygen-excluding agent relatively low in asphalt and aromatic content . such as nitrogen or natural-gas which may be bubbled through the liquid to minimize oxida do not show the desired concentration of the tion. The extracts and acetic acid end-wash are sulfur compounds by the removal of their smaller then combined. The acetic acid may be distilled amounts of undesirable constituents. The sul fur components, however, can be concentrated 55 o? and the mercury then released from the oil, for example, by heating say to 100° C. with dilute ‘by methods such as the following: acid (e. g. 2 vols. of 15% HCl) or by saturating Extraction with aceticacid containing a soluble with Has, the oil then being diluted with iso mercury salt such as mercuric acetate, mercuric pentane or other suitable solvent, water-washed, chloride, etc. to form ‘a mercury complex extract which is then worked up to recover the extract 60 dried and clay-treated before removal of solvent. The variables for several such runs are shown oil and if necessary further re?ne the latter. in the following table: Extraction with a liquid mixture of SbCh and A101: to form a complex which may be separated Run number and decomposed to recover the oil. Extraction with AlCh at temperatures between I about 0 to 80° C. as described in U. S. Patent 2,309,337 to form a complex which may be de composed to recover the oil. . All three of these extraction methods yield rela tively dark' oils, even though the starting ramnate 70 may have been of light color. Moreover, the .SbCla-AICI: extraction, as well as the A101: ex traction, tend to cause accumulation in the sul fur concentrate of whatever aromatics have been left over from the preceding solvent extraction, and therefore result in auliur concentrates of 76 Weight of oil used, gms .... -_ No. of dumps of reagent ..-. Volume of acetic acid, mls... _.~ e20 3 ' i190 Volume of HgAc; plus acetic acid,‘ mls ............................. .- - II ' .' 111 901 738 3 216 3 150 , . 485 060 Temperature of treatment‘, ° 0. .-.. 30 18 Tot 00 136 treating time minutes ..... -- Wei ht per cent yield of extract (on,‘ Po“ “tnliii------------ "ll-lull"--er cen s urremaining o .---- ‘ l 60 106 ‘ OLI: 0 1446; . . Per cent sulfur in extract oil (average) ............................ .. 540 - 0.165.‘: ( 8.00 8.88 8. ll 2,404,871 10 Extract from Run No. II was incorporated in white oil to the extent of 3%. This increased the time required for 100 g. to absorb 1800 ml. of oxygen from less than 2 to 236 hours. Corre sponding extracts obtained at higher (e. g. re?ux) temperatures were considerably less effective. used in connection with other additives in lubri cating media, for example, detergents formed from the oil-soluble salts of various bases with detergent forming acids. Such bases include metallic as well as organic bases. Metallic bases ~ include those of the alkali metals, as well as Cu, It has been found that when this mercuric acetate extraction of the oil is carried out at Mg, Ca, Sr, Ba, Zn, Cd, Al, Sn, Pb, Cr, Mn, Fe, Ni, acetic acid) the content of desirable sulfur con Examples of detergent forming acids are the .1 various fatty acids of, say, 10 to 30 carbon atoms, ' Co, etc. Organic bases include various nitrogen bases as primary, secondary, tertiary and room temperature or lower (i. e. below about 20° C. and preferably near the melting point of 10 quaternary amines. stituents in the extract is greater than if the oil wool fat acids, paraffin wax acids (produced by is re?uxed or maintained at a higher tempera oxidation of paraf?n wax), chlorinated fatty ture while treating with the mercury salt. In general, any mercury salt, particularly the mer 15 acids, aromatic carboxylic acids including aryl fatty acids, aryl hydroxy fatty acids, paraffin wax curic salts soluble in acetic acid such as the mixtures, may be employed in like manner as benzoic acids, various alkyl salicyclic acids, phthalic acid mono esters, aromatic keto acids, the mercuric acetate, since these salts will give aromatic ether acids; diphenols as di-(alkyl oxalate, carbonate, chloride, sulfate, etc. or their mercuric acetate in the acetic acid solution. The 20 phenol) sul?des and disul?des, methylene bis alkylphenols; sulfonic acids such as may be pro solubility of the acetate is considerably greater duced by treatment of alkyl aromatic hydro than for the other salts, hence it is generally carbons or high boiling petroleum oils with sul- ' more advantageous to start with the mercuric furic acid; sulfuric acid mono esters; phosphoric acetate. As compared with salts of other metals, the mercury salts are de?nitely superior for this 25 acid mono and di-esters, including the corre sponding thiophosphoric acids; phosphonic and purpose as shown by the foregoing data. The herein described compositions possessing arsonic acids, etc. Non-metallic detergents include compounds the required amount of available or reactive sul fur may also be incorporated advantageously in such as the phosphatides (e. g. lecithin), certain extreme pressure lubricants, cutting oils, roll oils, 30 fatty oils as rapeseed oils, voltolized fatty or wire drawing lubricants, greases, hypoid gear 1 mineral oils. I Other detergents are the alkali earth phosphate lubricants, etc. They may also be used to impart anti-wear and/or anti-oxidant properties to di-esters. including the thiophosphate di-esters; lubricants not necessarily subject to high pres— the alkali earth diphenolates. speci?cally the cal sure, such as turbine oil, refrigerator oil, lubri cium and barium salts of diphenol mono and poly cants for bearings, in particular, modern alloy sul?des; etc. bearings comprising cadmium-silver, cadmium Our sulfur additives may also be used in asso nickel, copper-lead, “high lead” alloys, as Well as ciation with other anti-oxidants, for example alkyl phenols such as 2.4.6-trimethylphenol,v I Babbit metal, and the like. The lubricating media ' also need not be derived in whole or in part from mineral oil but may consist in whole or part of vegetable or animal lubricants such as palm oil, cottonseed oil, ?sh oil, animal wax, phosphatides, etc., as well as the so-called synthetic lubricants pentamethylphenol, 2.4 - dimethyl - 6 - tertiary butyluhenol,’ 2.4-dimethy1-G-octylphenol, 2.6-di tertiary-butyl-li-methylphenol, 2 4,6-tri-tertiary butylphenol, etc.; amino phenols as benzyl amino phenols; amines such as dibutylphen'ylene (e. g. polymers of ole?ns derived from cracked 45 diamine, diphenylamine, phenyl-alpha-naphthyl wax). In addition, by reason of their anti amine, phenyl-beta-naphthylamine, dinaphthyl oxidant properties, such additives may be in amines; etc. corporated advantageously in organic substances Other corrosion inhibitors may also be present not intended for use as lubricants at all, such as gasoline, kerosene, spray oil, medicinal oil, trans former or electrical insulating oil, cleaning ?uid, synthetic or natural rubber, Diesel fuel, photo graphic developers, etc. Particular reference may be made to the in such as dicarboxylic acids of 16 and more car bon atoms, alkali metal and alkali earth salts of , sulfonic acids and fatty acids, etc. Likewise, other additives may be present in a.‘ lubricating oil or grease such as blooming agents, anti-foaming agents, viscosity index improvers. clusion of the herein described anti-oxidants as 55 etc. additives for coating materials such as asphalt, Instead of ?rst producing the herein described‘ resins, oils, waxes, varnish, insulating or mois additive and then adding it to a lubricating oil, ture-protective substances such as oiled or a high sulfur asphaltic crude such as raw “waxed" paper, etc. Such plastic or semi-plastic Utanol may be added to a crude petroleum, for vehicles may also contain, for example, anti 60 example a topped crude suitable for the manu rusting agents and be applied to metal surfaces facture of lubricants, and the mixture then sub-a to provide a corrosion-resistant coating. Also jected to one or several treatments adapted to such oxidation inhibited adhesive coatings may remove substantially all asphaltenes and at least a portion of aromatic hydrocarbons such be applied to wood, paper, cardboard, felt, stone, laminated glass, fabric. concrete, plastic composi as previously described. Amounts of this high tions, Transite board, etc., by such methods as sulfur oil which may be added to the crude lu roller coating, dipping. brushing, spraying and the bricating stock vary with the amount and avail ability of the sulfur content of the former, as like.‘ When the sulfur compounds of this invention explained before. and may range preferably from are intended for addiiton to lubricating oils, they 7 0 about 2% to 15%. or the concentrates which contain them should We claim as our invention: have boiling temperatures above gas oil range 1. A process for obtaining a sulfur~containing and preferably within or above lubricating oil fraction possessing anti-oxidant and other val range. uable properties, which process comprises ex These compounds may also be advantageously tracting a substantially para?inic lubricating oil 9,404,”: 11 12 ra?lnate with a mercury salt under temperature para?lnic lubricating oil ramnate with a mer cury salt under temperature conditions to pro duce a mercury salt-sulfur compound complex and breaking the resulting mercury salt-sulfur compound complex to regenerate and recover conditions to produce a mercury salt-sulfur com pound complex and breaking the resulting mer cury salt-sulfur compound complex to regenerate and recover the extracted sulfur compounds. 2. A process for obtaining a sulfur-containing fraction possessing antioxidant and other valu able pronerties, which process comprises extract ing a substantially para?'inic lubricating oil rai ?nate with a mercury salt under conditions of atmosphere and ‘temperature to substantially avoid any oxidation and to produce a mercury therefrom the extracted compounds. - 9. An organic composition comprising a pre dominant amount oi.’ a mixture 01' hydrocarbons, which mixture is unstable-against oxidative de-. terioration and which is responsive to sulfur-con taining antioxidants. and an added antioxidant amount of a concentrate oi! natural-occurring sul fur containing compounds from petroleum oil pos salt-sulfur compound complex. and breaking the sessing antioxidant and other valuable prop resulting complex to regenerate and recover the 15 erties prepared by the process which comprises extracted compounds. extracting a substantially para?lnic lubricating 3. A process for obtaining a sulfur-contain oil ra?inate with a mercury salt under tempera ing fraction possessing antioxidant and other ' valuable properties, which process comprises ex tracting a substantially parai?nic lubricating oil ture conditions to produce a mercury salt-sul fur compound complex and breaking the result ra?lnate with a mercury salt at a temperature 20 ing complex to regenerate and recover the ex below about 20° C. and breaking the resulting sulfur complex to recover the extracted sulfur compounds. 4. A process for obtaining a sulfur-contain tracted compound. . 10. An oleaginous composition comprising a predominant amount of an oleaginous material which is unstable against oxidative deterioration ing fraction possessing antioxidant and other 25 and which is responsive to sulfur-containing an valuable properties. which process comprises ex tioxidants, and an added antioxidant amount of _ treating a substantially para?lnic lubricating oil a concentrate of natural-occurring sulfur-con raillnate with glacial acetic acid saturated with taining compounds from petroleum oil possessing mercuric acetate and breaking the resulting sul antioxidant and other valuable properties prefur complex to recover the extracted sulfur com 80 pared by the process which comprises extracting pounds. ~ a substantially paraii'inic lubricating oil raiiinate 5. A process for obtaining a sulfur-contain with a mercury salt under temperature conditions ing fraction possessing antioxidant and other to produce a mercury salt-sulfur compound com valuable properties, which process comprises ex plex and breaking the resulting complex to regen tracting a substantially paramnic lubricating oil 85 erate and recover the extracted compound. ra?lnate with a mercury salt at a temperature not 11. A lubricant comprising a predominant above about 50° 0.. thereby producing a mercury amount of a re?ned mineral oil, a small added salt-sulfur compound complex, and breaking the amount of a normally corrosive detergent, and resulting complex to regenerate and recover the an added small amount su?lcient to render the 40 extracted compounds. resultant mixture substantially non-corrosive of 6. A process for obtaining a composition pos sessing antioxidant and other valuable proper ties, which process comprises extracting a sub stantially para?lnic lubricating oil ra?lnate with a mercury salt at a temperature not above about 50° C., thereby producing a mercury salt addi tion compound. and breaking the resulting ad dition compound to regenerate and recover the extracted compounds. 7. A process for obtaining a composition pos sessing antioxidant and. other valuable proper ties, which process comprises treating a substan tially para?lnic lubricating oil ramnate with gla cial acetic acid saturated with'merouric acetate, thereby producing a mercuric acetate addition compound, and breaking the resulting addition compound to regenerate and recover the extract ed compounds. 8. An organic composition comprising a pre dominant amount of an organic substance which is unstable against oxidative deterioration and which is responsive to sulfur-containing anti oxidants. and an added bene?ciating amount of natural-occurring sulfur-containing compounds from petroleum oil possessing antioxidant and other valuable properties prepared by the proc ess which comprises extracting a substantially a concentrate of natural-occurring sulfur-con taining compounds from petroleum oil possessing antioxidant and other valuable properties pre pared by the process which com-prises extracting a substantially parai?nic lubricating oil raf?nate with a mercury salt under temperature conditions to produce a mercury salt-sulfur compound com ,plex and breaking the resulting complex to regen erate and recover the extracted compound. 12. A lubricant comprising a predominant amount of a re?ned mineral oil and character ized by a normal tendency to corrode metal bear ing surfaces, and an added corrosion-inhibiting amount or a concentrate of natural-occurring sulfur-containing compounds from petroleum oil possessing anticorrosive and other valuable prop erties prepared by the process which comprises extracting a substantially para?lnic lubricating oil ra?lnate with a mercury salt under tempera ture conditions to produce a mercury salt-sulfur compound complex and breaking the resulting complex to regenerate and recover the extracted compound. PAUL R. VAN ESS. FORREST J. WATSON. GARY M. WHITNEY.