US2982728A - whitney - Google Patents

Description

May 2, 1961 w. B. WHITNEY 2,982,728

LUBRICATING ADDITIVE Filed March 26, 1954 fsoLvENT INVENTOR. 1W. B. WHITNEY ATTORNEYS 2,982,728 Patented May 2, 1961 United States Patent Oice This inventionrelates to lubricating additives having detergent and/ orI dispersant properties. Inone of its more specific' aspects, 'this invention relates to petroleum lubricating oil compositions. In another of its more specific aspects; this invention relates to methods `of pro-- ducing these lubricant additives.

As the speed and output of internal combustion engines have increased to higher and higher values, the ability of oils Without additives to maintain an engine free from lacquer, sludge and carbon deposits has decreased. Under present day conditions, lubricating oils for use in autoomotive and diesel engines require the use of additive agents. Stop and go driving in cold weather also.- has a tendency to produce sludge in the lubricating system yand additives are necessary to combat this problem.

The requirements desirable in a satisfactoryY detergent additive are: (1) compatibility with lubricating oil and other types of additives which may be present; (2) maintenance of satisfactory cleanliness of engineparts, principally in the ring belt zone of the piston; and` (3) chemi cal inertness with respect to supplemental additives and metal engine parts. Additional desirable characteristics include: (l) ease of handling, either as such or as an oil concentrate;-(2) minimum effect on voil properties, such as viscosity, color and odor; (3) inexpensive overall cost; and (4) independence with respect to critically lirnited or expensive raw materials. Y

The use of additives in lubricating compositions as corrosion inhibitors, oxidation inhibitors, viscosity index improvers, dispersing agents, pour-point depressants, extreme pressure agents, lubricity improvers and ash forming detergents, is Well known. The need for additives to improve various specific properties of lubricating oils is all the more'acute and necessary, in view of the service conditions which lubricating oils undergo and must withstand. In internal combustion engines, it is desirable that the lubricating compositions be resistant to sludge and varnish for-mation and in the event of such formation to prevent the deposition of these materials on the metallicl parts of thevengines.

Each of the'l objects of vthis invention will be obtained by at least one of the aspects of this invention.

An object of this invention is to provide improved lubricant additives having detergent and/or dispersant properties.

Another object of this invention is to provide new` lubricating compositions containing the additives' of this invention.

Accompanying and forming a part of this specification is a drawing which illustrates apparatus which can be used in the practice of this invention.

I have now discovered that an additive for lubricating oils which is useful as a detergent or dispersant therein fcan be produced by subjecting a selected hydrocarbon fraction having at least 40 carbon atoms per molecule to oxidation in the presence of alkaline earth compounds or by oxidizing such a hydrocarbon fraction and thereafter treating the oxidized material with alkaline earth metal compounds.`

The additives prepared according to' this invention are readilyincorporated in lubricating oils to form compositions of improved performance characteristics. Lubricants containing these additives exhibit excellent resistance to deposition of sludge and varnish in internal combustion engines operating both under high performance conditions and under intermittent service. .They materially reduce ring-sticking, piston varnish, etc., in such engines ahdjmpart cleanliness to the engine.

AOne material'well suitedy for the production-of my 'i detergent is preferably one which is substantially satuof between 1.440 and 1.520. Hydrocarbon materials whichjc anj ,be satisfactorily used inthe preparation of my Vdetergent. include substantially saturated diene poly.

rated 'containing at least 40 carbon atoms per molecule,l

preferably. between 40 and 80 carbon atoms per molecule. The hydrocarbon material should have a refractive index mers, such 'as polybutadiene and polypentadiene, and polymers of'olens having from 2 to l2 carbon atoms, per

molecule, such as polypropylene, polyethylene, polyiso-y butylene, etc., preferably having a ratio ot carbon atoms to olefin bondsof at least 40 to 1 and not less thank 16 to l, copolymers such as styrene-olefin copolymers, alkylated polystyrene, and a petroleum lubricating oil fraction, which has substantiallyno asphalt, either in its natural state or 'when deasphalted, and which has beenv solvent extracted to reduced the content of aromatic-type hydrocarbons therein and preferably dewaxed.

` r.the detergent-type lubricating voil additives of this i.n' vennon'can be used alone or in combination with other` "additives infrared spectrograms of these materials reveal the presence of groups characteristic of substantially neutralcompletelyorganic, oxygen-containing compounds` such as alcohols, ethers, esters, lactones, anhydrides, ketones, and aldenydes. Examination of the oxidized materials by infrared spectroscopy discloses very marked changes in the absorption bands upon oxidation of the selected hydrocarbon fractions disclosed herein. Astrong carbonyl yband' Within the 5.75 to 5.87 micron region is producedin the initial oxidation of the hydrocarbon as is Another object of this invention is to provide a rneth-A I positions possessing excellent detergent properties.

Other and further objects of this invention will be,

apparent to.those skilled in the art upon studyingthe accompanying disclosure.

provide a methj a weak absorption band at 2.94 to about 3.0,microns which indicates the presence of a low concentration ofA hydroxyl groups. These bands are characteristic of a concentrated oxidized product but also appear. in the scanning of the total oxidized hydrocarbon fraction. The concentrated oxidized material also exhibits a broad absorption `band in the'lV to lO'micron region, this band being' much weaker for theunconcentrated material.

Petroleum fractions whichare suitable for production of the material of this invention, i.e., an excellent deter.

gent .lor use in ylubricating oils, include Pennsylvania, Mid-Continent, California, East Texas, Gulf Coast, Venezuela, Borneo, and Arabian .crudeSL The source of the crude from which the petroleum fraction is derived does not significantly vinfluence thepreparationor properties i ot the detergent material of this invention, rprovided the petroleum fraction hasbeen prepared by subjecting the crude to certain necessary treatments to exclude undesired materials therefrom. Y

In the preparation of the preferred petroleum Vfraction from which the detergent material of this invention is produced, a crude oil -is topped, i.e., distilled to remove therefrom the more volatile, lower molecular Weight hydrocarbons, such, as gasoline and light gasoil, and then vacuum reduced to remove heavy gas oil and light lubricating oil of the SAE and 20 viscosity grade. Thevacuum reduced crude is then propane fractionated to remove an overhead fraction of about l0() SUS at 210 F. viscosity and the residual material is subjected to a second propane fractionationto 'remove another overhead fraction of about 200 SUS at 210 F. viscosity. The residue from the second fractionation may be subjected to a third propane fractionation to remove still another overheadlfractiogn of' about 575 SUS at 210 F. viscosity. Propane fractionation maybe modiied by the presence of butane, ethane or methane to the extent desired.

Following the propane fractionation step, theoverhead oil fraction is solvent extracted withV a Vselective solvent which Will separate the parai'nic hydrocarbons from the moreV aromatic-type hydrocarbons. Suitable selective solvents for aromatichydrocarbons include among others, the various phenols, sulfur dioxide, furfural and /8,dichlorodiethyl ether. This solvent extraction step for the removal of the more highly aromatic compounds can be carried out in accordance withl the well-knownconcurrent or'countercurrent solvent extrac-v tion'techniques, aswell as by the Duo-Sol technique.

' The resulting solvent extracted material, before vor after theremoval of the more aromatic hydrocarbons,K4

is preferably devvaxed. D'ewaxing may be carried` ont by any conventional method,ve.g., by solvent dewaxing' using propane or solvent mixtures, such as methyl ethyl, ketone ormethy'l isobutyl ketone Awith benzene at a suitj` able temperature.

EachV fraction of lthe phenol extracted, dewaxed, propane-fractionated oil can be used in`preparing the detergent material Vofthisv invention with good results butv the oil fraction from the vsecond propane fractionation is preferred. It Will be recognized by those skilled in the art Vthat propane fractionated oils differing from those described may bev used or a single broad viscosity cut can be used. The residual material from the iinal propane fractionation contains therejected asphalt and more aromaticoils.

Although the preferred method for preparation' of feed y stock is as above described, other methods may be used to secure a similar type hydrocarbon fraction. Thus, a

vacuum'reduced crude which has essentially' no asphalt,l

such as a Pennsylvania oil, mayA be` used directly or after a light acidY treatment. Another method, Ywhile not feasible 'commercially at the present time, is ultra-high vacuum (molecular) dis'tillationto obtain the desired' fraction.

As pointed out above, a polydiene, such as'liquid`poly-- butadiene which is prepared by sodium-catalyzed 'polymerization of butadiene `and` which material is subsequently hydrogenated so as to reduce the oleti'nicv un-V carriedout `by Vmeans ofthe process set forthY in U.S;l

Patent No. 2,631,175; issued March 10, 1953, by W. W;

Crouch.

Another suitable feed -stock is a liquid` or semi-solid polybutadiene `which is prepared by conventional emulsion polymerization and coagulationY to form syntheticrubber, subsequently hydrogenating said material soV as to reduce the oleiinic unsaturation thereof to the desired amount and finally. thermally depolymerizing it. suffi- TABLE I f Property Broad range Preferred Y Rango Refractive Index m20 1. 440-1. 520 1. 4801. 515 Average Moec'ilar Weight above 550 SOO-10, 000- Minirnurn Molecular Weigh 4.50 Viscosity, SUS at 210 F; above50 above 100 Viscosity Index (when determinable) 1 50-125 80-120 Carbon Atom Content per Molecule above 40 50-720 present. Hence the viscosity is not decreased to anyv catalyst, as more `fully disclosed inl U.S. .application Seriall No. 333,576, tiled January 23, 19.53, now aban` cloned, by John P. Hogan and Robert L. Banks. Another suitable feed material is -a copolymer -of styrene with oleiins in which the olefin portion constitutes at least 50 percent of the total molecular Weight of the molecule. With any of these feed materials, it is desired to reduce the amount of olenic unsaturation to such an extent ythat the ratio of carbon atomsto oleiinic bonds ispreferably at leasty 40 :l and not less than 16 :1. The hydrocarbon stocks which are useful in the practice of this invention include those materials which are identiiable as having the following properties set forth in Table I.

lVscosty index notl determinable for non-Newtonian materials.

Lubricating oils which are suitable as feed stock my process have the properties set forth in` Table II.

DuringY oxidation, scission takes place Ain the large hydrocarbon molecules, the lighter products'r being col-- lected in traps. When nitrogen gas was passed through the untreated oil at 250 C. substantially no Volatile products were collected. Only a very small amount wasr collected when the temperature was raised.to300 C., thus demonstratingthat the major cause of the formation of the volatile products is oxidation and v.not thermal decomposition nor stripping of light ends,` originally presentv in the oil. With oils of moderate."molecular` Weight, scission cannot ytake placein anyposition but whatv one or Aall of the fragments is sufficiently' small that distillation takes place, thus preventing accumulation of` molecules appreciably smaller. than those originally great extent. Concomitant with the` oxidative scission reaction, there is a polymerization or condensationk reaction resulting in an increase in viscosity, The net change in viscosity is` apparently due Vto the relative magnitude of each reaction. In very high molecular Weight hydrocarbons, the oxidative scissionmore frequently results in fragments too large to be removed by-distillation and,

hence, the average molecular weight decreases, tendingl to cause a decrease in viscosity. As the oxidation reacf tion proceeds, the reactions Vcausing. increased molecular weight may overcome, more or. less, .thosecausingl a decrease in molecular Weight.

As ,a result, the molecular.v

lower range tend to increase and those in the higher range tend to` decrease during the initial oxidation period.

If desired, the' p'etroleumvoil fraction which has been highly refined, as described above, may be further subjected to additional refining treatments. For example, these petroleum fractions may be hydrogenated to' convert any aromatic compounds therein to the corresponding naphthenic -and saturated hydrocarbon', or if desired, these petroleum fractions may be subjected to contact with adsorbents such as silica gel for the preferential adsorption and removal of the more aromatic hydrocarbons therefrom. Generally, the petroleum fraction which is oxidized for the production of the detergent of this invention should contain' not more than 20 percent of the carbon atoms in aromatic' rings, as determined by the ring .analysis described in the book Aspects of the Constitution of Mineral Oils by K. Van Nes and H. A. Van Westen, Elsevier Press, New YorkY City, NewYork. Itis preferred that the aromatic content of the petroleum fraction lbe reduced to -an economically feasible extent by refining procedures sincevoxidation of aromatic-type hydrocarbons tends to result in the 'formation of oil-insoluble products not suitablev for the present invention. It also appears that aromatic vconstituents oxidize more readily than do the non-aromatic components. Thus, failure to remove materials containing a high percentage of carbon atoms in aromatic rings from the feed before oxidation results in formationrof considerable oil-insoluble materials. Usually, a suitable petroleum fraction, upon distillation under'reduced pressure, e.g., molecular distillation, will produce a first percent by weight fraction which has a viscosity of more than 50 SUS at 210 F., preferably more than 80 SUS at 210 F.

In one method of carrying out my invention, the hydrocarbon fraction is oxidized and then treated with the alkaf line earth compound. During the oxidation reaction, the

hydrocarbon fraction is modified, resulting in a product of increased dispersing activity which differs from the starting material in respect to the following four physical characteristics: (1) an increase in -the carbon to hydrogen weight ratio; '(2) usually an increase in molecular weight; (3) an increase in the oxygen content; and (4) a decreased solubility in propane under propane fractionating conditions.

All these changes are brought about by contacting an above-described selected hydrocarbon fraction under suitable conditions of temperature and pressure withan oxidizing agent, such as free-oxygen, sulfur trioxide, nitrogen dioxide, nitrogen trioxide, nitrogen pentoxide, acidied chromium oxides and chromates, permanganates, peroxides, such as hydrogen peroxide, sodium peroxide and ozone. Any oxygen-containing material capable of releasing free oxygen under the oxidizing conditions can be used. Nitric lacid can be used. Other suitable oxidizing agents include air,.relatively pure commercial grade oxygen, oxygen enriched air,'and a mixture of oxygen with an inert gas, such as carbon dioxide and nitrogen. Even oxygen admixed with natural Igas or methane is satisfactory. Air having less than the usual amount of oxygen may also be used. Air is economically a preferred oxidizing agent.

Generally, the oxidation reaction is carried out at a temperature in the rangeof from 40 F. to 800 F. When using an active oxidizing agent, such as sulfur trioxide, temperatures in the range of -40 F. to 400 F., preferably 70 F. to 200 F., are used. With less active oxidizing agents, such as. air, higher temperatures are used, such as 100 F. to 800 F., preferably 375 F. to 575 F. Higher oxidation temperatures result in a faster oxidation reaction. When the oxidizing agent is in the gaseous phase, another yvariable which affects the rate of the oxidation reaction is the partial pressure of the oxidizing agent. Accordingly, as the pressure at which the oxidation reaction is carried out is increased, other conassenza ditionsI remaining the same, the oxidation reaction pro ceeds at a faster rate. Therefore, depending upon the rate of oxidation desired, the oxidation reaction is carried out at sub-atmospheric, atmospheric or super-atmospheric pressures. Usually it is preferred to carrylout the oxidation lreaction' at arpressure between about 10 and 100 pounds per square inch absolute, depending upon the composition or oxygen content of Ithe oxidizing gas. Lower or higher absolute pressures may be satisfactorily used, if desired. Lower oxidation pressures are useful, in that they facilitate release and removal of the more volatile, and other undesirablematerials, eg., H2O, from the reaction mixture.

The rate of oxidation is also dependent upon, and influenced by, the distribution of the oxidizing gas within the reaction mixture and the rate of introduction of the oxidizing Igas thereto. The oxidizing agent is preferably introduced and present in the reaction mixture in a finely dispersed state,in order'to achieve better contact with the materials undergoing oxidation and better mixing therewith. An increase in the rate of introduction of the oxidizing gas, of course, increases the rate of oxidation, other conditions remaining unchanged. The conditions of temperature, pressure, oxygen content of the oxidizing gas, Arate of introduction of oxidizing gas, etc., are correlated, adjusted and controlled so as to carry out the oxidation reaction at -a sufficiently rapid rate so as to minimize reaction time while readily and easily controlling the reaction.

Conditions which have been found to be satisfactory .for producing the detergent of this invention from a selected hydrocarbon fraction, when using a moderate oxidizing agent, such as air, are set forth in Table III.

Exemplary of the inuence of various variables upon the oxidation reaction, it is pointed out that at a tempera-` ture of 482 F. and at an air introduction rate of about 0.32 s.c.f. per pound of oil per hour and at about atmospheric pressure, the oxidation reaction requires about 20 hours before the desired degree of completion is reached (as measured by increase in viscosity). When the air rate was increased to 1.44 s.c.f. per pound of oil per hour, only 16 hours were required to convert the oil to an oxidized product of similar viscosity. Increasing thereaction temperature to 572 F. decreasedthe time required for oxidation appreciably. Reducing the reaction temperature to below 390 F. increased the reaction time under these conditions.

It has been found that the time required for the reac-` tion mixture .to reach the desired degree of oxidation can be decreased or increased by the -use of catalysts. Positive (promoters) or negative (inhibitors) catalysts can be used to modify the reaction rate and time.

Catalysts which have been found to promote the oxidation reaction andl to decrease the time required for oxidation reaction include the various well known oxidation catalysts, such as the oil soluble salts and compounds containing such metals as copper, iron, cobalt, lead, zinc, cadmium, silver, manganese, chromium, vanadium, and the like, having an atomic number between 5l and 113, inclusive. The naphthenates of these metals are particularly useful. Especially useful and outstanding as a catalyst are those compounds which are obtained by reacting a compound containing both phosphorus and sulfur, such as P285, with a terpene, either monocyclic or dicyclic or. a mixture :thereof, such as pinene, as disclosed in my copending U.S. application, Serial No. 264,839, filed January 3, 1952, now U.S. Patent No. 2,758,069. A particularlyl effective catalyst of this type is widely used as a corrosion inhibitor for petroleum lubricating oils and is sold under the trade name Santolube 395-X, and is a P2S5- terpene reaction product. This reaction product exhibits a'marked catalytic effect, resulting in a decrease of several hours in the time normally required for the oxidation reaction to reach the desired degree of completion. Also, it is pointed out that the above-mentioned metal naphthenates, especially the copper and iron naphthenates, effectively catalyze the oxidation reaction at a'temperature in the range of 300 to k500 F. Usually, however, the catalytic effeet of these'metal naphthenates is pronounced for only a few hours and then becomes ineffective, the addition of more naphthenates being required in order to maintain a catalytic effect upon the oxidation reaction.

`Negative catalysts or inhibitors, i.e.,materials which tend to increase the time required for the oxidation reaction, are usually high molecular weight aliphatic alcohols, such as the C to C24 highly branched, non-straight chain and normal aliphatic alcohols. Typical material useful as an anti-catalyst or inhibitor is a highly branched octadecyl alcohol, such as 2,2,4,5,810,10-heptamethyl5 undecanol and n-octadecyl alcohol.

These catalysts can be added in catalytic amounts, usually in the range of 0.1 percent to 4.0 percent by Weight of the oil undergoing oxidation, depending upon the catalytic promoting or inhibiting effect desired. An amount of one of these types of catalyst, such as about 1.0 per-V cent by weight of the oil, is sufficient for most purposes. It is pointed out that the employment of catalysts is beneficial, in that they decrease or increase the time required for oxidation (for better control) and, in some cases, even improve the quality of the detergent recovered as a product from the oxidation reaction. However, the presence of a catalyst, positive or negative,'is not essential' to the practice of this invention.

More active oxidizing agents, such as sulfur trioxide, may also be used in the oxidation step, as pointed out above. When liquid sulfur trioxide is utilized as the oxidizing agent, the reaction is most readily carried out when both the oil and sulfur trioxide are separately diluted with a modifying solvent. Solvents which maybe utilized in this operation under suitable temperature conditions include liquid sulfur dioxide, hexane, tetrachloroethylene, ethylene dichloride, pyridine, nitrobenzene and dioxane.

Liquid sulfur trioxide is an extremely reactive compound and, if added directly to the oil, will cause excessive charring and violent splattering. `It is necessary to moderate this excessive reactivity by dilution with a solvent, such as those disclosed above. A molar ratio of solvent to sulfur trioxide of at least about 1:1 appears to be necessary, and it is preferred to use a ratio of 2:1 or greater. Dilution of the oil is also very desirable for the reduction of viscosity and` to facilitate mixing, but such dilution is not required. Dilution of the oil may be obtained with some non-reactive solvent other than that utilized for the dilution of the sulfur trioxide. Use of the same diluent, however, simplifies the recovery problem. Gaseous S03 maybe introduced into the oil directly or mixed with a carrier gas, such as air, nitrogen or other inert gas. In the case of gaseous S03, an elevated temperature, eg., 200 to 300 C., is frequently used.

The extent of oxidation is determined by the ratio of oil to sulfur trioxide. The weight ratio may be varied from 1:1 to 30:1, but is preferably maintained within the range of between 3:1 to 18:1. Ratios from 3:1 to 8:1 are the most desirable. Very low ratios resultv in the use of excessive amounts of sulfur trioxide without obtaining a corresponding increase in useful product. Very highfratiosfail to obtain sufficient oxidation to, becco-` nomic'al.

TheV initial reaction of the sulfurtrioxide with oil is almost instantaneous -at room temperature' .or above, but the reaction continues for extended periods of'time, ,e.g.,` up to as much as 144 hours or more. At highertem-y peratures the time of the slower secondary reactions is shortened to less than 24 hours. vThe evolution of sul; fur dioxide and other gases causes muchyfoaming and the rate of reaction must be controlled 'sufficiently toI per-v mit the capacity of the apparatus to lhandle the foaming reaction mixture. The time required for Vreaction may be shortened to as little asY three minutes, in which case, secondary reactions do not take place to,any great extent. The quality of the :product is notmaterially affected bythe length of reaction `time or by the absence or occurrence of they secondary reactions. v

The temperatures which may generally be utilizedin the oxidation reaction, wherein sulfur trioxide `is used as the oxidizing agent, range from 40 to 400 F.,A preferably from 70 P. to' 200 lF. Avery short period of time, usually less than three hours, is required for the initial reaction. 'I'his time is sometimes ask short as three minutes.

After the reaction, the product is treated,k for the removal of acid and other impurities. Acid is conveniently removed from the product by water washing. The product is concentrated in the manner discussed later in connection with the product obtained ina process utilizing a less active oxidizing agent.

The detergent produced by sulfur `trioxide oxidation is somewhat improved in color by reduction. This is preferablyv accomplished by treatment in alcoholwith lithium hydride or with zinc and hydrochloric acid. Catalytic hydrogenation or chemical reduction can also be used.

kThe extent to which the oxidation reaction is carried out is dependent upon the selected oil fraction being oxidized and the yield of detergent material desired. I have found that if the oil being oxidizedcontains a relatively low concentration of lower molecular weight hydrocarbons, the oil may be oxidized toa considerable extent, up to as high as percent-by weight of the oil charged, without any deleterious effects upon the reaction itself or the detergent product. Also, I havev observed that when the aromatic content of the charge stock is low, such as below about 5 percent by weight oflcarbon atoms in aromatic rings and especially below about 2 percent by weight, the charge stock can be oxidized to a greater extent without any undesirable effects or adversely affecting the yield, such as may happen when there is an appreciable amount, above about 5 percent by weight of aromatic carbon atoms, presentjtherein. In general, the oxidation reactionis carried out until the oxidized oil has increased in'viscos'ity, when Vexpressed in Saybolt Universal Seconds (SUS) at210 FQ, from 1.5 to 50 fold, preferably from 1.5 to 10 fold, over that of the originally charged unoxidized oil. The range 1.5 to 2 fold has been found especially valuable Vwith some stocks. When the oxidation reactionris carried'out to a 3 to 10 fold increase in viscosity, the yield of active detergent recovered from theroxidized oil amounts to about l5 to 50 percent by weight of the original unoxidized oil. Continued, oxidation, especially to yields above about'60 percent, tends to produce a certainamount of 'oil-insoluble oxidized materials which,` although they do not adversely affect the effectiveness Y,of the'oil-soluble detergent, do adversely effect the yield of the desired product. VAlso, since it is often necessary to remove these oil-insoluble oxidized materials, it is desirable, therefore, not `to continue the oxidation reaction beyond that ,point at' which the oil-insoluble materials are produced. l

In generaLrhowever, the extent to which the selected oil fraction is oxidized in the practice of thisinvention is primarily a. matter of convenience,l based on. the lease iication assegna of handling of reactants and reacted (oxidized)materials,

the' productl recovered (as by propane fractionation o-f the oxidationreactionmixture), if the recovered product is again oxidized to a hard, brittle mass, the reoxidized n'iaterial has a detergent power or activity, when tested as alubricatingoil additive, by a hereinafter defined test, in a Lauson engine which simulates the well-known, widely accepted L-l diesel engine ftest, only slightly less than the product recovered from the initial and'rst oxidation reaction. v f l While the viscosity increase measured at SUS at 210 F. has been stated as one way of determining and measuring the extent of the oxidation reaction, it is not the only way. Another way is toi' measure the amount vof 'water produced during the oxidation reaction. Another method of determining the extent of the reaction isto measure the detergent activity of the oxidation reaction mixturfelby' a spot plate test.. Still-another method is to determine the amount of propane insoluble material presen tjin-'the oxidation reaction mixture.` V"When the oxidation reaetion is completed tothe'extent'desired, the propane insoluble, oil soluble material in the reaction ,mixture amounts to between about S'and about 60 percent by .Weight of the reaction mixture, more often between about and about 40 percent by weight;

The oxidation reactionvmixturc, .after oxidation, can be, used directly without additional 'concentration or puri- However, if a product-of improved quality, purityand greaterL concentration andeifectiveness per unit weight is desired, the active detergent oil-additive material is preferably'removed and. recovered from thev oxidation reaction mixture. When the hydrocarbon feed'tothe oxidation reaction is a liquid, `the recovery and concentration of the active additive material is preferably 'obtained by propane fractionation, 'such as 'is disclosed by J. ML Whitely and G.' A. Beiswenger in U.S. Patent 2,110,845. l f l# 'Following propane fractionation thematerial is a iirm, plastic or slightly brittle -mass soluble in pentane, benzene,

have anvacid number belowabout 50 and asaponitication number ybelowlabout 100.- r

Following-the oxidation, an alkaline earth material, such vas the oxides, hydroxides and carbonates of calcium,.strontium or-barium, is added. Representative cornpounds include lcalcium oxide, calcium hydroxide, calcium carbonate, barium oxide, barium hydroxide, strontium hydroxide, and strontium carbonate. This is preferably doneby dissolvingl the oxidized material in a suitable solvent, suchas an SAE -10` oil, and adding the alkaline earth compound. Other solvents include aromatics, such as `benzene and toluene. Frequently it is advantageous to add a small amount of a non-solvent, such 'as isopropyl alcohol, in order to obtain better contacting. This is especially true when an aqueous solution of the alkaline earth material is used. When the alkaline earth hydroxide is used, the hydrate maylikewise be used, .e., when barium hydroxide is used, the anhydrous material, the monohydrat'e, or the octahydrate, can be used. The alkaline material is added as an aqueous solution or as iinely powdered material, irlV a concentration of 0.1 to 20 weight percent, and preferably from 0.5 to l0 weighty percent of the hydrocarbon material. Following addition,the mixture is preferably stirred for a sufhcient length lof time to insure adequate reaction. The' resulting solution is .filtered to -remove excess alkaline metal material and any other-*insoluble material. Temperatures for this reaction usually range from around 50 F. to around 500 F., although the preferred temperature range is 200 to 300 F. A reaction time of 5 minutes to 5' hours is usually required. The resulting product, after filtration, is au oil concentrate containing the additive,

diethyl ether and the other usual liquid hydrocarbon solvents. It is also soluble in `all petroleum lubricating oils, as well as in polymers and polyester synthetic oils. The additive leaves a dark red color, when rubbed on a white surface and when dissolved in a lubricating oil, such as a motor oil, gives the oil a black appearance by reflected light. The oxidized material has a strong tinting power when dissolved in lubricating oil. It has a low acid num-l ber below about 50, expressedas the number of milli grams of KOH per gram, and a saponil'lcation number between 0 and, about 100. The oxygen content of these materials ranges from about 2 percent up to about 10 percent by weight, usually from 3 percent to 8 percent, although in some cases the oxygen content maybe as high as 15 percent or as low as lpercentby weight.

While these solid oxygen-containing materials v appear to have a supercial resemblance to reSiIlS, asphaltenes and sludges heretofore reported inthe literature,'there l which can be added to any desired lubricating oil base stock direct, orthe additive may be separated from the oil'concentrate. f

1 Another method of preparing these additives is to add the alkaline earthcompound to the hydrocarbon fraction prior to the oxidation step. 'In this manner, the additive can be prepared in one step. The physical conditions of temperature and pressure set forth above for the oxidation are used for the reactionin this case.

This active solid detergent material can be recovered directly from the reaction mixture by solvent extraction with a solventi which is selective for the relatively unoxidized, essentially hydrocarbon material therein, and which solvent is at the same time essentially a non-solvent forthe active detergent material in the reaction mixture.y Suitable solvents for thel'recovery of the solid active detergent material from the oxidized reaction mixture include propane, isopropyl alcohol, a solvent mixture of propane with modifying amounts (up to about 50 percent by weight) of other low boiling hydrocarbons, such as methane, ethane, and butane. Other selective solvents, such as methyl ethyl ketone, methyl isobutyl ketone, tertiary butyl alcohol, isobutyl alcohol, ethyl acetate, dioxane, morpholine, dimethyl formarnide and phenol, are also useful. In general, those polar compounds containing" only carbon, hydrogen, and oxygen atoms, such as aliphatic alcohols, aliphatic ketones, and esters having from` 3to 8 carbon atoms per molecule, are useful as treating materials in the practice of thisv invention. `Mixtures of these various materials may be used.

' One step-wise processfor concentrating the detergent material comprises 4extracting the partially `oxidized oil with methyl isobutyl ketone, methyl ethyl ketone, or mixt'uresof thetwo, at appropriate temperatures so as to dissolve onlyV the oil and lower molecular weight additive material. The proper temperature will depend'upon the ratio of solvents `and the percentage of productrto be dissolved. The undissolved material is thereafter mechanically separated from the dissolved material.

' -When these materials are used in obtaining the active detergent material from the oxidized reaction mixture, the active solid detergent is recovered as a propane insoluble, oil soluble, solid phase (rainate), the ineffective,

ll substantially hydrocarbon material of the reaction mixture being dissolved in the treating material as an extract. rl"he'propane soluble phase, from which the active detergent material is separated, has a viscosity index much higher than that of the unoxidized oil. This propane soluble phase may beA used toblend with an oil for the purpose of improvingthe viscosity index of that oil. Y

Inythe recovery of t-he active detergent material, it is preferred in the practice offthis invention to employ propane as a selective solvent, the solid active detergent being recovered as a separate Vpropane insoluble phase under propane fractionating conditions of temperature, pressure and ratio of solvent to material being treated (usually :1 to 25:1 by volume). The solvent extraction operation for the recovery of the active detergent material is usually carried on at a temperature in the range 50 F. to 250 F., especially'inthe rangeL 100 F. to 160 F., and a pressure of between 200 p.s.i.g. to 500 p.s.i.g. Countercurrent solvent extraction techniques are usefully employed, as well as multiple, solvent extraction steps of separately contacting and recovery of the undissolved active detergent.

VIn many instances, the activity of the detergent material is considerably increased by additionally treating thisrecovered solid detergent material with an aliphatic alcohol, in the C3 to C8 range, such as isopropyl alcohol, and recovering apuried and more active detergent therefrom as a solid, `alcohol insoluble phase. The alcohol treatment has a two-fold purpose. Traces of peroxides,

aldehydes, and the like, which may be oxidation promotors, are removed thereby. In addition thereto, it appears that a beneficial chemical change takes place during stripping of residual alcohol solvent from the additive material.

The above-described sequence of recovery and purification steps does not in some instances greatly inuence the quality and effectiveness of the solid, final detergent product.v It is preferred to employ a propane fractionation step prior to the organic polar compound treating -step to avoid emulsions which are difficult to break and which present operational difculties when the alcohol or ketone treating step precedesthe propane solvent extrac-V tion step.

The method by 'Whichthe additives of the present invention are formed., is notfully understood, since the amount of alkalineV earth metal compound reacting often exceeds by a large factor that corresponding to the neutralization number. The reaction appears to be quite rapid, indicating the saponilication of ester groups is not the fullexplanation. While not wishing to be bound by any possible theory set forth, I believe that it may be that chelates or other coordination complexes play an important part. The material preparedfrom the oxidation of the oil in the presence of an alkaline earth metal compound, such yas barium hydroxide, has excellent detergent properties, as measured by the spot plate test, even when very little viscosity increase has taken place.` Measurement of the olf-gas indicates that oxidation is taking place during the reaction even though the viscosity of the oil isy not increasing rapidly.

The oxidation step disclosed herein is similar to that disclosed in my copending application Serial No. 304,659, filed OctoberlS, 1952, now abandoned, and reference is made thereto for further details and illustrative examples. The additives of this invention show improvements over the additives produced according to the method of Serial No. 304,659 in certain respects when tested ina paraflinic oil in anengine using a dirty fuel. p The oil to which the solid active detergent material of this invention is added can be any oil of lubricating viscosity and, preferably, is a lubricating oil commonly used in internal combustion engines, such as in the crankcase thereof. The additive is usually added to the base lubricating oil in effective detergent amounts and gen- Gravity, API

erally comprises between 0.1 -percent to 10 percentV by.

weight of the total lubricating oil composition, but may be as high as 25 percent Vfor lextreme service conditions. Usually, however, an amount in the yrange 0.3 percent to 10.0 percent by Weight of the total lubricating oil composition is sufficient. A

The' modified diesel L-l test referredl to in the following` examples was carried out for a shorter period of time than the 480 hou-rs prescribed by the full scale diesel L-l test set forth in C.R.C. Handbook 1946 by the Cof ordinating Research Council, Inc., at pages 347 and following. The procedure outlined in the C.R.C. Handbook was modified as to the specific fuel. In its distillation characteristics, the fuel utilized in the tests set forth in the following examplesv had a percent distillationY of 600 F. to 640 F., a minimum 50 percentdistillation of 500 F., andan endpoint of 650 YF. to 690 F. The sulfur content in the fuel utilized4 had a minimum of .35 percent natural sulfur and a cetane number of between 40 and 45. The simulated L-l Lauson engine test, used in connection with the following examples, is described in Motor Oils and Engine Lubrication by Carl W. Georgi at page 83 and following. TheV operating conditions which were utilized in the tests of the following exampleshave been modified and are asfollows.

The lubricating oil employed as a base oil in these tests was a solvent-refined Mid-Continent oil of lubricating viscosity and having the following characteristics I K `30.3 Viscosity at 210 F. 61.8 Viscosity index 98 Neutralization number 0.01

The detergent in selected amounts was added to the base oil and tested in a standard Lauson engine. The test consisted in placing920 `grams of .the base oilc0n taining this detergent in the crankcase of a single cylinder Lauson gasoline engine. der a 1.2 horsepower` load at 16001-20 r.p.m.,'maintain ing a cooling jacket temperature of 300 F., an oil temperature of 225 F., an air-to-fuel ratio of 13.5 :1, carburetor air at roomv temperature, spark advancefof 25 before top of dead center, andcrankcase vacuum of 1.0 inchof mercury'. Atthe' end vof 60 hours engineV operation under these conditions, the engine Wasstopped, disassembled, and the piston, crankcase and bearingszwere examined. The piston varnish was rated on an arbitrary scale of 0 to 10 with representing a clean or perfect condition and 0 representing the dirtiest condition.

Example I A Mid-Continent oil, solvent refined, and dewaxed,

having a Viscosity of 208 SUS at 210 F'.` Was oxidized.

by passing air into 3440 grams of the oil containing barium hydroxide octahydrate, equivalent to 2.0 percent barium hydroxide.V The airwas dried, metered and introduced through a porous plate located near the bottom of the oil. The oil containing the barium hydroxide was heated to 482 F. and treated for 20.4 hours with approximately 0.95 cc. of air per gram of oil per minute. The viscosity of the oil after oxidation wasl 648 SUS at 210 F. The oxidized oil containing barium was extracted with liquid propane at 123 F. and 250 p.s.i.g., using a propane to oil ratio of 6:1. The propane insoluble portion represented 36 percent by weight of the oil.

Example Il EVALUATION 0F ADDITIVES The modified diesel L-l test referred to in this and other examples was car-riedV out for a period of 60 or hours, as indicated, instead of thev 480 hours prescribed by the' full scale diesel L-l test set forth in C.R.C.

The engine was operated un-V tained'in the 60 hour dies'eltest:

v"itove insolubles.

13 Handbook 1946 by the Coordinating Research Council, Inc., at pages 347 and following, and as givenin application Serial No. 304,659, page 25. 'In the 60-hour tests, a 1.0 percent sulfur fuel was used instead of the 0.4 percent used in the 120 hour test.v y A 5 percent blend was `made of barium detergent (prepared as described in Example I) in the base oildescribed in the above paragraphs. 1.25 percent of Lubrizol 309, a commercial antioxidant containing zinc dithiophosphate, was also added to the `base oil. The following results werel obtained in the diesel tests:

120 Hour 60 lour Diesel Test Diesel Test 9o. 1 l sa. 7 95. o

Example III PREPARATION OF ADDITIVES To a 50-gallon horizontal still was lcharged 340 pounds of a Mid-Continent oil, solvent refined and dewaxed, having a viscosity of 208 SUS at 210 F. This direct red, batch still was equipped with 'a 1A" stainless steel tubing containing M6" holes at 3 inch intervals-for air distribution. The oil Awas heated to 482"v .at atmospheric pressure and then oxidized bypassing air through the mass at 14 standard cubic feet per minute for: a total of 7 hours. The viscosity of the resulting oxidized'oil Was 650 SUSat 210 F. v`

yThe resulting oxidized oil (305 pounds) was transferred to an open top. steam jacketed tank, heated to 170"l F. and 9.25 pounds of nely ground (in a hammer mill) barium hydroxideY octohydrate wasaddd while the oxidized oilwas being agitated. Two hours were allowedfor .the reaction. The barium treatedoxidized oil was filtered .using a horizontal plate Sparkler Filtermaintained at about 325 F. The total vfiltrate weighed 293 pounds. The viscosity-of the ltratewas 2740 SUS at 210 F. IThefbarium treated oxidized oil-was extracted by the batch method Vwith l lvolumes of isobutane for' l volume of the treated oil at 123 F. A yieldv of 30 percent insoluble material was obtained. This material was difcultly soluble in oill and had a sulfated ash equivalent to '6.8 perf cent barium hydroxide.

Example 1V EVALUATION OF ADDITIVE A 5 percent blend was made of the isobutane-insoluble fraction of thebarium treated oxidized oil (prepared as described in 'Example III) in the base oil described in Example II. v1.25 percentof Lubrizol 309', a commercial anti-oxidant containing zinc dithiophosphate, was also added t'o the'base oil. The' following results were job- Overall rating `86.8 Lacquer :rating Y 78.9 Carbon 'rating 93 -EJamplaV 820 grams of an ashless'. detergent,vprepared by air oxidation at 482v F. and '25 p.s.i.g., followed by propane fractionation, as described in application Serial No. 304,659, was placed in'a container and dissolved in 1400 ml. of benzene and 120 ml. of isopropyl alcohol.- Thirtyeight grams of barium hydroxide octohydrate was added, which is 2.5 weight percent of the additive calculated as Ba(OH)2. The mixture was warmed just below boiling for one hour and then heated to azeotrope oi the water and alcohol. Fresh portions of benzene were added to Ikeep the material in solution. After the complete removal of the water, the solution was centrifuged to' re- A weighed amount of oil was added to fan sludge formation, etc.

14 the solution and the benzeneflashed olf. This product gave the following results in the L-l 60 hour high sulfur fuel test using 1.25 percent Lubrizol 309 inhibitor, a commercial, antioxidant containing zinc dithiophosphate. For comparisomthevalue for the untreated ashless detergent is'also presented.

r Treated Piston `Rating Percent ywith Concentration B a(OH)z ,i Overall Lacquer Carbon 5.0 Nn 89. 3 83. 3 93. 0 2 s l l YM 89.0 s3. 9 91. 4 5.0 Yes 92.0 91.2 89.0

' These results indicate that a 2.5 percent concentration of the bariumhydroxidevtreated detergent is 'as effective as a 5.0 percent blend ofthe ashless detergent. A5 percent blend of the treated detergent showed a very sub- Vstantially improved lacquer rating. The ash content of the additive is about 2.8 percent, which amounts to only 0.14 percent ash in a 5 percent blend.

Example Vl A quantity of ashless detergent was prepared according to the method of application Serial No. 304,65'9 by oxidizing a finished 250 stock having a viscosity of 205 SUS at 210 F., using a temperature of 485 F. to 500 F.anda pressure of approximately 25 p.s.i.g. for 7 to 14 hours with airas the oxidant. This fshless detergent was .dissolvedfin arnixture of benzene and a small amount of isopropyl'alcohol, and a calculated amount of the barium hydroxide dissolved in Water was added to the solution. The mixture was heated at"l40f to 160 F. for an hour. The water and alcohol were then removed as an razeotrope and the benzene solution centrifuged to remove the insoluble material. The solution wasi then lmixed with oil and thebenzene evaporated.V

The results'of modiiied EX-2 tests, described below, with these additives, are found inthe following table. All tests were made'using 1.25 percent Lubrizol 309, `a commercial antioxidant containing zinc dithiophosphate and-SAE 30 oil with 'l0 percent concentration of the additive, with the exception Athat the additive treated with 2.5 percent Ba(OH)2 was usedk in a l1 percent concentration.; i..

The one digit ratings are from 0 to l0 and the two digit ratings are-0-to 50, the higher numbers being perfect. The -fuel used was a thermally cracked dirty-type test fuel.

The 'EX-2 testv is designed to give accelerated low temperature'- s'ludge'conditions ofa type-found in city delivery service. The piston rings of the Chevrolet engine were slotted -rto allow a large vamount ofblow-by'products to enter the oil and a dirty fuel is used. The testis of 96 hours duration and, at the end of this period, the engine is rated'for Acleanliness and the oil for viscosity increase,

Under these conditions, the ashlessy detergent without further treatment consistently caused an excessive thickening of the crankcase oil.

The product' obtained by treating the ashless detergent with 2.5 percent Ba(OH)2 showed a great improvement over the ashless detergent. Unlike the other samples tested, this additive, in a paraiiinic Ioil and with a dirty fuel, produced no crackcase ,geL

Example V11 800 grams of the ashless detergent prepared as described in Example VI was dissolved in'1200 ml. of benzene and 100 ml. of isopropyl alcohol. To this mixture was added amounts of various bases equivalent to 2.5 weight percent of barium hydroxide inA about 70 ml. of Water. The mixture was heated belowthe boiling point for 1.5 hours and then the alcohol and water were removed as an azeotrope. The solution was centrifuged to remove the insolubles. The solution was diluted with SAE 20 oil. The benzene was evaporated, leavingthe product.

The results of the L-l 60 hour thigh sul'fur'fuelV engine tests are presented in the following table. All of the materials were tested at percent-.concentration with 1.25 percent Lubrizolf309.

Piston Rating l Average of four tests.

2 Equal to 2.5 percent Ba(OH)2 on a gram-equivalent basis. Y

The data in this example show that treating with alkali metal hydroxides does not result in the improvement shown when using alkaline earth metal hydroxides.

Example VIII Solvent refined 250 lubricating oil was'agitated withan equal volume of 32 to 34 percent nitric acid at a temperature of 140 to 160-F. for 4 to 12 hours. The oil was separated, washed with cold water, andthendissolved in pentane. The emulsion was broken by the addition of isop ropyl alcohol.' Pentane was evaporated and a dark red `oil recovered.. 150 grams of this material was heated lto 212 F., 3375 grams of Ba(OH)2-I-I2O were added and the mixturev heated forjone hour at this temperature. Thereafter, the :temperature was raised to 300 F. for an additional hour. The material, when cooled, was dissolved-in pentane, centrifuged, and the solvent evaporated. The results of a Lauson engine test made with 1.75 percent concentration of the additive and 0.82 percent Santolube-395-X inhibitor, a commercial inhibitor containing P285 reacted terpene with a control comprising the base oil appears in the following table.

Material tested: Piston varnish Base oil 6.3 Base oil with above additive 8.0

In the above examples, the mixtures were agitated in order to keep the alkaline earth compounds in suspension, since these materials, which are powders, tend to settle out of the solution instead of remainingum'formly dispersed and in good contact with the oil.- In the drawing which accompanies and forms a part of this disclosure, I have illustrated apparatus for preparingthe detergents of this invention, this apparatus taking advantage of the fact thatrau oxidized oil percolating'over an alkaline earth metal hydroxide reacts with'the material `to form the additive. l j

This apparatus comprises an elongated vessel providedwith an o'il inlet 11 and a gaseous material outlet 12 in the upper end portion thereof. Vessel 10 is iilled with an inert granular support 13,7; such as bauxite, on which has been deposited the desired basic material, such as an alkaline earth metal hydroxide, oxide, or carbonate. Heat exchangers 14, 16 and 17 are positionedwithin this bed in order to maintain `the temperature desired for treatment. Means for introducing gaseous material f. is provided in a lower pontion of vesselr 10, thisbeing intror'16 duced through line18 to a perforated plate'19, or other equivalent gas distribution means.

Conduit 21 communicates with the lower portion of vessel 10 and extends to the central or upper portion of liquidliquid extraction zone 22. From the lower end portion of zone 22, conduit 23 extends to fractionator-Z, this fractionatorfbeing provided with conduit 26 extending from the lower portion thereof. Extending from the upper end portion ofk zone 22 there is provided conduit `27 which communicates with fractionator 28, this fractionator 28 being provided with conduit 29 extending from the lower end portion thereof. Conduit 31 extends from the upper portion of fractionator 24to the lower end portion of extraction zone 22 and conduit 32 extends from the upper portion of fractionator 28 to conduit 31. Make-up sol: vent can be added throughrconduit 33.*V n n In the operation of this apparatus, the oil to be oxidized is introduced through conduit 11 into the upper portion of vessel 10, this vessel beinglilled with the treating material: The oil passes downwardly over this granular treating material 13 countercurrent to the flow of oxidant introduced throughdistribution means 19. The oil is added at such a" rate that it is oxidized to the desired extent by the time `it leaves Vessel 10, it being removed through conduitk 21. The use of this apparatus provides continuous movement downwardly over the treating material with a minimum of mixing of the various portions of the oil, a situation that is 'dicult to avoid when batch-wise operation is utilized.v Since. the specic ,gravity of the oxidized maferial is higher than that of the' charge oil, the tendency of these materials to mixis minimized. For instance, with one particular .oil, the oxidized material had a specific gravity of 0.93 compared to 0.87 for the charge oil.

The apparatus shown in this drawing includes the propane fractionation step which is preferred in the recovery of the additive. The treated oil is introduced by conduit 21` intoliquid-liquid extraction zone 22 and conduit 31 supplies 'solvent thereto. Although the treated oil and solvent'canbe introduced at a common point I prefer to operate by introducing `the oil into the central or upper portion of zone 22 and by supplying the solvent to the lower portion, as shown, in order to provide countercurrent extraction. Temperatures for the'` oxidation have been previously recited. Temperatures inthe extraction zone can vary widely. below the critical temperature with liquid phase conditions. Using propane as the solvent, a suitable range for the bottom of the zone isV to 150 F., preferably about F., and the range of 125 to 200 F., preferably about l50 F., for the top of the zone. The nonsoluble portion of the treated stock, being heavier, is' re-v moved from the lower portion of zone 22, conveyed by line 23 to frctionator 24, where the solvent dissolved therein is returned to the process Vthrough overhead' conduit 31 and the additive is recovered as a bottomproductin conduit 26. The rpropane soluble portion, the upper layer found in the zone- 22, is passed to fractionator 28 through'conduit 27,- where the propane isrecovered and returned1 to the system through line 32 and the unoxidized portion is recovered in conduit 29. This portion can be returned to the treating column 10, as desired, or'usedfor other purposes.

As many possible embodiments may be made 'of' this invention without departing-from `the spirit and scope thereof, it is to be understood that all matter herein set forth or shown in the accompanying drawing is to be interpreted as illustrative and not in a limiting sense.

I claim:

l. A process for producing a material having detergent and dispersant properties which comprises subjecting a hydrocarbon fraction, having a. refractive index m32 of between 1.440 and 1,520, a minimum'molecular weight of 450, a viscosity of at leastl 50 SUS at 210 F., a viscosity index (when deetrminable) at at least 50, and an average It' is preferred to operate' carbon atom content per molecule of at least 40, to oxidation with air at a temperature of 100 F. to 800 F. for a time of 3 to 75 hours and at a pressure of 10 to 200 p.s.i.a., said air being supplied at a rate of 0.01 to 3.0 cf. per hour per pound of said hydrocarbon, recovering the oxidized fraction of said hydrocarbon by solvent extraction, adding to said oxidized portion 0.1 to 20 percent by Weight of at least one compound selected from the group consisting of alkaline earth hydroxides, oxides, and carbonates, heating said mixture at a temperature in the range of 50 to 500 F. for a time of 5 minutes to 5 hours, and recovering the resulting treated material, said material having detergent and dispersant properties in lubricating oil compositions.

2. The process of claim 1 in which said alkaline earth material is barium hydroxide.

3. The process of claim 1 in which said alkaline earth material is calcium hydroxide.

4. The process of claim 1 in which said alkaline earth material is barium oxide.

5. The process of claim 1 in which said alkaline earth material is calcium oxide.

6. A process for producing a material having detergent and dispersant properties which comprises subjecting a hydrocarbon fraction, having a refractive index m32 of between 1.440 and 1.520, a minimum molecular Weight of 45o, s viscosity of st least 5o sUs at 210 F., s viscosity index (when determinable) of at least 50, and an average carbon atom content per molecule of at least 40, to oxidation in the presence of an oxidizing agent under oxidizing conditions and at least one compound selected from the group consisting of alkaline earth hydroxides, oxides, and carbonatos, said oxidation being suicient to provide at least a 1.5 fold increase in viscosity, and recovering a resulting material having detergent and dispersant properties when used in a lubricating oil.

7. A lubricant composition comprising a major portion of lubricating oil and at least 0.1 percent by weight of an oil soluble materialhaving detergent and dispersant properties, said material produced by oxidation and treatment with at least one compound selected from the group consisting of alkaline earth hydroxides, oxides and carbonates, of a hydrocarbon fraction having a refractive index nD20 of between 1.440 and 1.520, an' average molecular weight of at least 550 and no appreciable portion thereof having a molecular weight below 450, a viscosity of at least 50 SUS at 210 F., a viscosity index (when `18 determinable) of at least 50, and an average carbon atom content per molecule of at least 40, the solid oxidation product having an acid number below 50, a saponication number in the range of 0 to 100, and an oxygen content in the range of 1 tok 15 percent by weight.

8. The composition of claim 7 in which said material having detergent and dispersant properties is present in an amount from'0.3 to 10.0 parts by weight.

9. A lubricant composition comprising a major portion of lubricating oil and at least 0.1 percent by weight of an oil-soluble material having detergent and dispersant properties, said material produced by oxidation and treatment With at least one compound selected from the group consisting of alkaline earth hydroxides, oxides, and carbonates, of a hydrocarbon fraction having a refractive index 111,20 of between 1.480 and 1.515, an average molecular weight of at least 600 and no appreciable proportion thereof having a molecular weight below 400, a viscosity of at least SUS at 210 F., a viscosity index (when determinable) of at least 80, and an average carbon content per molecule of at least 50, the solid oxidation product having an acid number below 50, a saponication number in the range of 0 to 100, and an oxygen content in the range of 1 to 15 percent by weight.

10. The composition of claim 9 wherein said alkaline earth material is barium hydroxide.

References Cited in the le of this patent UNITED STATES PATENTS pag'es 87, 91 and 92.

Performance of Lublicating Oils, Zuidema, Reinhold Pub. Co., 1952, page 123.

Claims (3)

1. A PROCESS FOR PRODUCING A MATERIAL HAVING DETERGENT AND DISPERSANT PROPERTIES WHICH COMPRISES SUBJECTING A HYDROCARBON FRACTION, HAVING A REFRACTIVE INDEX ND20 OF BETWEEN 1.440 AND 1.520, A MINIMUM MOLECULAR WEIGHT OF 450, A VISCOSITY OF AT LEAST 50 SUS AT 210*F., A VISCOSITY INDEX (WHEN DEETRIMINABLE) AT AT LEAST 50, AND AN AVERAGE CARBON ATOM CONTENT PER MOLECULE OF AT LEAST 40, TO OXIDATION WITH AIR AT A TEMPERATURE OF 100*F. TO 800*F. FOR A TIME OF 3 TO 75 HOURS AND AT A PRESSURE OF 10 TO 200 P.S.I.A., SAID AIR BEING SUPPLIED AT A RATE OF 0.01 TO 3.0 CF. PER HOUR PER POUND OF SAID HYDROCARBON, RECOVERING THE OXIDIZED FRACTION OF SAID HYDROCARBON BY SOLVENT EXTRACTION, ADDING TO SAID OXIDIZED PORTION 0.1 TO 20 PERCENT BY WEIGHT OF AT LEAST ONE COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALKALINE EARTH HYDROXIDES, OXIDES, AND CARBONATES, HEATING SAID MIXTURE AT A TEMPERATURE IN THE RANGE OF 50 TO 500*F. FOR A TIME OF 5 MINUTES TO 5 HOURS, AND RECOVERING THE RESULTING TREATED MATERIAL, SAID MATERIAL HAVING DETERGENT AND DISPERSANT PROPERTIES IN LUBRICATING OIL COMPOSITIONS.

6. A PROCESS FOR PRODUCING A MATERIAL HAVING DETERGENT AND DISPERSANT PROPERTIES WHICH COMPRISES SUBJECTING A HYDROCARBON FRACTION, HAVING A REFRACTIVE INDEX ND20 OF BETWEEN 1.440 AND 1.520, A MINIMUM MOLECULE WEIGHT OF 450, A VISCOSITY OF AT LEAST 50 SUS AT 210*F., A VISCOSITY INDEX (WHEN DETERMINABLE) OF AT LEAST 50, AND AN AVERAGE CARBON ATOM CONTENT PER MOLECULE OF AT LEAST 40, TO OXIDATION IN THE PRESENCE OF AN OXIDIZING AGENT UNDER OXIDIZING CONDITIONS AND AT LEAST ONE COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALKALINE EARTH HYDROXIDES, OXIDES, AND CARBONATES, SAID OXIDATION BEING SUFFICIENT TO PROVIDE AT LEAST A 1.5 FOLD INCREASE IN VISCOSITY, AND RECOVERING A RESULTING MATERIAL HAVING DETERGENT AND DISPERSANT PROPERTIES WHEN USED IN A LUBRICATING OIL.

7. A LUBRICANT COMPOSITION COMPRISING A MAJOR PORTION OF LUBRICATING OIL AND AT LEAST 0.1 PERCENT BY WEIGHT OF AN OIL SOLUBLE MATERIAL HAVING DETERGENT AND DISPERSANT PROPERTIES, SAID MATERIAL PRODUCED BY OXIDATION AND TREATMENT WITH AT LEAST ONE COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALKALINE EARTH HYDROXIDES, OXIDES AND CARBONATES, OF A HYDROCARBON FRACTION HAVING A REFRACTIVE INDEX ND20 OF BETWEEN 1.440 AND 1.520, AN AVERAGE MOLECULAR WEIGHT OF AT LEAST 550 AND NO APPRECIABLE PORTION THEREOF HAVING A MOLECULAR WEIGHT BELOW 450, A VISCOSITY OF AT LEAST 50 SUS AT 210*F., A VISCOSITY INDEX (WHEN DETERMINABLE) OF AT LEAST 50, AND AN AVERAGE CARBON ATOM CONTENT PER MOLECULE OF AT LEAST 40, THE SOLID OXIDATION PRODUCT HAVING AN ACID NUMBER BELOW 50, A SAPONIFICATION NUMBER IN THE RANGE OF 0 TO 100, AND AN OXYGEN CONTENT IN THE RANGE OF 1 TO 15 PERCENT BY WEIGHT.

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