US2830949A

US2830949A - Phosphorus- and sulfur-containing complex metal salts of oxidized hydrocarbons and oil compositions thereof

Info

Publication number: US2830949A
Application number: US554930A
Authority: US
Inventors: Henry G Berger; Ferdinand P Otto; John W Schick
Original assignee: Socony Mobil Oil Co Inc
Current assignee: ExxonMobil Oil Corp
Priority date: 1955-12-23
Filing date: 1955-12-23
Publication date: 1958-04-15
Anticipated expiration: 1975-04-15

Description

United States Henry G. Berger, Glen Rock, Ferdinand P. Otto, Woodbury, and John W. Schick, Camden, N. J., assignors to gocillny Mobil Oil Company, Inc., a corporation of New No Drawing. Application December 23, 1955 Serial No. 554,930

22 Claims. (Cl. 252-32.7)

The invention relates to a new class of phosphorus-, sulfurand metal-containing oxidized hydrocarbon products and to a method for the preparation of these products. It also contemplates the use of these new products as addition agents for mineral lubricating oils, particularly oils designed for use in internal combustion engines.

It is well known that hydrocarbon lubricating oils tend to oxidize in use in an engine with attendant formation of oxidation products which are acidic in character and which exert a corrosive action on the engine parts, such as the hard metal alloy bearings. Furthermore, it is well known that the gradual deterioration of the oil in use due to oxidation, etc. is attended by formation of carbonaceous sludge and lacquer which adheres to the engine parts, particularly the piston ring grooves and skirts, thereby lowering the efiiciency of the engine and frequently causing the rings to stick. To counteract these conditions, the art has developed chemical agents which when added in small amounts to engine lubricating oils have the ability to greatly retard the oxidation of the oil in use. Agents have also been developed which have the ability to prevent deposition of sludge materials on the engine parts, thereby keeping the engine clean and free from the clogging and sticking effects normally encountered. These two types of chemical agents are known in the art as antioxidants and detergents, respectively. The present invention provides a new class of chemical products which exhibit both antioxidant and detergent properties.

In a copending application, Serial No. 441,626, filed July 6, 1954, there is disclosed and claimed a method for oxidizing hydrocarbon oils in the presence of metal hydroxides to produce complex metal salts of the oxidized oils which are effective detergents for mineral lubricating oils.

It has now been found, in accordance with the present invention, that by reacting a hydrocarbon, such as a petroleum oil, which has been oxidized in the presence of a metal hydroxide, with a phosphorus sulfide, and then subjecting the resulting product to reaction with additional metal hydroxide in the presence of water, under the conditions hereinafter defined, a new class of reaction products are produced. These new products have high metal contents. They also contain substantial amounts of phosphorus and sulfur and they exhibit exceptional detergent properties, as well as being effective antioxidants for mineral lubricating oils.

Due to the complex nature of the products provided by the invention, no exact chemical formula can be ascribed to them at this time and they are, therefore, best described by the process of producing them. As far as atent P 2,830,949 Patented Apr. 15, 1958 is known, the products of the character provided by the invention have not been known heretofore. They are, therefore, believed to be new compositions of matter.

It is, therefore, the primary object of the invention to provide a new class of phosphorus-, sulfurand metalcontaining oxidized hydrocarbon products. It is also an object to provide mineral lubricating oils containing minor amounts of these new products, said oils having improved antioxidant and detergent properties. Other and further objects will be apparent from the following description.

It will be seen that broadly stated the present invention provides a method for the preparation of oil-soluble, phosphorus-, sulfurand metal-containing reaction products which involves the steps of (1) forming a mixture of a hydrocarbon material, such as a petroleum oil, and a metal hydroxide, (2) contacting said mixture with an oxidizing gas at a temperature of from about C. to about 325 C. to provide a metal-containing oxidized hydrocarbon product, (3) reacting the metal-containing oxidized hydrocarbon product with a phosphorus sulfide to provide a metal-, phosphorusand sulfur-containing oxidized hydrocarbon product, (4) forming a mixture of the product produced in step 3 with water and a metal hydroxide at a temperature below the boiling point of water, (5) substantially completely dehydrating the mixture formed in step 4 and (6) filtering the dehydrated mixture from step 5 to remove insolubles therefrom.

As aforesaid, the exact nature of the products produced by the process of the invention is not known, however, analytical data indicate that these products are comprised principally of complex salts, i. e., salts containing more equivalents of metal than so-called normal salts. Thus, it has been found that products produced by the oxidation step of the process contain about two equivalents of metal per equivalent of acid-hydrogen formed in the course of the oxidation. For example, when such an oxidation product, prepared by oxidizing a petroleum oil and containing 1.50% calcium, was de-metallized by means of strong hydrochloric acid, the resulting acidic product had a neutralization number (N. N.) of 21 and a saponification number of 18. This neutralization number would account for only 50% of the calcium, assuming the formation of normal salts. This indicated that the remaining 50% of the calcium is present in the product as some type of complexed or coordination compound.

When the products produced in the oxidation step are reacted with phosphorus sulfide and the resulting products reacted with additional metal hydroxide in accordance with the subsequent steps of the invention, the metal contents thereof are substantially increased. The manner in which this further amount of metal is incorporated into the ultimate products is not fully understood. However, without intending to limit the invention in any way by theoretical considerations, it would appear that the phosphorus sulfide reacts with oxygenated groups contained in the oxidized hydrocarbon molecules, such as aldehyde, ketone or alcohol groups, to form cross-linked molecules. As shown in the examples presented hereinafter, the phosphorus sulfide reaction with the oxidized hydrocarbon intermediate is often attended by substantial gel formation, particularly where the hydrocarbon reactant has been subjected to relatively strong oxidation. This gel is broken by the water which is always added to the reaction at this point in the process. It appears, therefore, that in the presence of water, the cross-linked molecules are hydrolyzed to form new acids which react with additional 'me'tal hydroxide to produce the ultimate complex salt products of the invention. As in the case of the oxidized oil intermediate products, de-metallization of the final products indicates that their metal contents are greater on an equivalent basis than the metal contents of normal salts. Thus, such a product, containing 3.07% calcium, upon de-metallization with hydrochloric acid showed a neutralization number (N. N.) of 15. This acid number would account-for only 054% calcium, assuming the formation of normal salts. This product, therefore, had a calcium content amounting to 500% excess or approximately 5 equivalents of calcium over that which would be expected in a normal salt product.

THE REACTANTS The hydrocarbons utilizable as starting materials in the process of the invention may comprise any hydrocarbon or mixture of hydrocarbons capable of providing a product which is soluble in lubricating oil. In general, this solubility requirement is satisfied by hydrocarbons havingmo'lecular weights of from about 200 to about I000, with those having molecular weights of from about 600 to about 1000 being particularly suitable. The hydrocarbons may be aliphatic hydrocarbons of either the straight-chained, branch-chained or cyclic type. Also, aromatic hydrocarbons which have aliphatic substituent groups of sufficiently high melocular Weight to provide an oil-solubilizing character to the final products can be used. Thus, alkaryl type hydrocarbons containing at least one aliphatic substituent of at least about 8 carbon atoms, or several such substituents totaling at least about 8 carbon atoms per molecule are suitable. Examples of these would be octyl benzene, dodecyl benzene, wax benzene, etc.

Petroleum oils and petroleum oil fractions, such as petrolaturns, waxes, etc., are a preferred class of hydrocarbon reactants, while refined oils, such as Bright Stocks are especially preferred. In terms of viscosity, oils having viscosities ranging from 2 to about 65 centistokes at 210 F. may be used, with those having viscosities of from about to 45 centistokes at 210 F. being preferred. The characteristics of several different types of suitable oil stocks are-shown in Table I.

Table I Gravity K. V. Av 011 API' 210 F., m

Solvent-refined Mid-Continent idlisttllate stock came MION U100 The metal hydroxides utilizable as reagents in the invention are those of the metals of Groups I and II of Mendeleefis Periodic Table of the Elements. Specifically, the hydroxides of calcium, sodium, barium, cobalt, strontium, zinc and magnesium are highly suitable, with calcium hydroxide being particularly preferred. Various grades of calcium oxide, calcium hydroxide and barium hydroxide may be used in the invention. However, grease-makers lime (96% CaOH) is preferred because of its high purity, small particle size and its property of'being wetted by-oil.

The phosphorus sulfide reactant used in the process may be either P 8 P S 'or P 8 with phosphorus penta- '4 sulfide being preferred. Mixtures of the sulfides can also be used.

PROCESS CONDITIONS in conducting the oxidation step of the process, the hydrocarbon reactant and the metal hydroxide reagent are charged to a reactor having means for the introduction of an oxidizing gas, such as air or oxygen. The amount of metal hydroxide charged to the hydrocarbon can range from about 0.5% up to about 25%, based on the weight of the hydrocarbon reactant. The reactants are mixed together and heated at a temperature of from about C. to about 325 C., preferably C. to 225 C., and maintained at this temperature while the oxidizing gas is passed through the mixture to effect oxidation of the hydrocarbon and reaction of the oxidized hydrocarbon with the metal hydroxide. The oxidation is continued until the hydrocarbon has attained a metal content of from about 0.05% to about 3%, by weight. It has been found that superior oil detergents are provided by the process of the invention when a relatively mild oxidation is used, i. e., an oxidation which provides an oxidation product which has a metal content of from about 0.05 to about 0.5 and preferably about 0.1%. Furthermore, the products obtained using a mildly oxidized intermediate are better from the standpoint of antioxidant ability.

It should be noted that the amount of metal hydroxide charged to the hydrocarbon prior to the oxidation reaction should, in all instances, be in excess of that eventually utilized in the oxidation. Thus, we have found that at least about 15% of the metal hydroxide charged should remain unreacted at the end of the oxidation. It has been found that the metal hydroxide when present in such amounts serves to prevent undesirable side reactions, such as oxidative polymerization, which are detrimental to the provision of products of the nature and quality herein-contemplated, particularly from the standpoint of color and solubility in lubricating oil. Also, with respect to the amount of metal hydroxide charged, although as much as 25% may be used, large excess arnounts provide no particular advantage. Furthermore, the use of large excess amounts of the metal hydroxide reduces the fluidity of the reaction mass so that stirring of the reaction mixture and eventual filtration are made more difficult. In instances where these latter difficulties are encountered, however, theycan be overcome by the-addition of adiluent solvent, such as benzene, toluene or the like, which is subsequently distilled from the final product.

The'oxidation time required 'to'incorporate the desired amount of metal into the hydrocarbon reactant will, of course, vary depending upon the conditions employed, such as 'the equipment used, the rate of oxygen or air introduction, the temperature, the amount of metal hydroxide charged, the type of hydrocarbon bei'ng oxidized, etc. As will be seen from the examples which follow, the oxidation times used varied from about 3 hours up to about 85 hours. From a practical standpoint, it is, of course, desirable to use oxidation equipment and conditions which are conducive to etfecting the oxidation to the desired extent in as short a time as possible. Accordingly, it is considered that modifications designed to increase the efficiency of the oxidation procedure, such as the use of oxidation catalysts and special reactors calculated to give a more efiicient disbursal of the oxidizing gas in the hydrocarbon, etc., come within the broad purview of this invention.

Upon completion of the oxidation step the oxidized hydrocarbon product mixture may be filtered to remove the excess (unreacted) metal hydroxide and the phosphorus sulfide reagent added, or the phosphorus sulfide may be added directly to the oxidized hydrocarbonmetal hydroxide reaction mixture. In conducting the reaction, from about 5% to about 20%, by weight (based on the weight of the hydrocarbon charge), of phosphorus sulfide is added to the oxidized hydrocarbon product and the two mixed together. The mixture is then heated to a temperature of from about 75 C. to about 150 C. for a suificient time to complete the reaction. The reaction is usually complete in from about 10 minutes to about 10 hours. Although the temperature may be 'varied within the aforesaid range without significantly effecting the final product, the higher temperatures, i. e., from about 125 C. to about 150 C. give products which are usually dark in color and which, therefore, tend to darken the color of the oils in which they are used. The lower temperatures, however, i. e., from about 75 C. to about 110 C., give lighter colored products which provide better colored oil blends.

As will be seen from the examples, the metal contents of the ultimate complex salt products, on an undiluted basis, were increased from 1.94% for a charge of P 8 to 6.04% for a 15% charge on batches of the same oxidized oil product. However, the sharpest rise in metal content occurs with the first 7.5% of the P 8 with only relatively slight increases above'that amount. The use of about of the phosphorus sulfide in the reaction is, therefore, considered to be the preferred amount to use.

The phosphorus contents of the finished products indicate that from about 70% to 100% of the phosphorus sulfide charged is reacted. However, the P/S ratio in the products ranges from 0.4 to 0.8 and for the most part averages about 0.6. This ratio is higher than 0.39 which is the P/S ratio in phosphorus pentasulfide, for example. It would appear then that some sulfur is lost in the reaction either as hydrogen sulfide or it is removed as an oil-insoluble salt during the filtration step.

As mentioned previously, gelation of the reaction mixture is apt to occur in the phosphorus sulfide reaction. This is paticularly so where the oxidized oil intermediate contains a relatively high percentage of metal, i. e., more than about 0.5%, and about 10%, or more of phosphorus sulfide is added. Gelation does not usually occur when the reaction is conducted on the more mildly oxidized hydrocarbons, i. e., those containing 0.5%, or less of metal. The gel formation, however, is in no Way harmful, and as afore-indicated, the gel is quickly broken by the addition of water, which is added in all instances at this stage of the process.

In general with respect to the phosphorus sulfide reaction it can be said that the use of a 10% charge of the phosphorus sulfide and conduction of the reaction at a temperature of from about 75 C. to about 125 C. for about 1 hour using P 5 as the phosphorus sulfide reactant are the preferred reaction conditions. It should be noted that somewhat longer reaction times, i. e., 5 to 6 hours, are required for best results where P 8 is used as the sulfide reactant.

In this connection it has been found that both the phosphorus heptasulfide and the phosphorus trisulfide are not as reactive as the phosphorus pentasulfide under comparable conditions, the trisulfide giving salt products having the lowest metal contents. However, the use of a triggering compound, such as sulfur, in conjunction with these reagents substantially increases their reactivity and also increases the metal content of the ultimate products. The produt obtained using the P4S7S combination, for example, approaches that of the P 8 products in metal content. Also, in the case of the P 8 .by extending the reaction time to 5 or 6 hours, products may be obtained which are comparable to the P 5 products without the use of sulfur. The amount of sulfur used in conjunction with the P 5 or P 8 should be about 10% to 25% based on the phosphorus sulfide used.

In conducting the reaction of the phosphorus sulfidetoxidized hydrocarbon intermediate with the additional metal hydroxide in the presence of water, the metal ghydroxide reagent can be either that which is already present in thereaction mixture (if the mixture was not filtered pior to the phosphorus sulfide reaction) or it can be a fresh charge of metal hydroxide. In any case, the amount of metal hydroxide present in the reaction mixture at this stage should be from about 2% to about 25 (based on the original hydrocarbon charge) the usual amount being about 10%. The amount of water necessary is small, generally from about 2% to about 10% being suificient, although higher amounts may be used. The water is preferably added after cooling the reaction mixture to a temperature below the boiling point of water, preferably to about C. Dehydration is then accomplished by heating the reaction mixture above the boiling point of water while passing a stream of nitrogen therethrough. The mixture is preferably heated to a temperature of from about 150 C. to about 200 C. and maintained at this temperature level until all of the water is driven off. The product is generally filtered at or near this latter temperature level in order to obtain relatively rapid filtration. Obviously, the dehydration may be accomplished in other ways, such as by adding a solvent, such as benzene, which may be subsequently distilled oif as an azeotropic mixture.

The metal hydroxides used in the water-treating and dehydration steps of the invention are the same as those utilized in the oxidation step, i. e., the hydroxides of the metals of groups I and II of the periodic table of the elements. However, the mixed metal salt products, i. e., salt products containing more than one metal can be produced in the invention by the use of one metal hydroxide in the oxidation step and a difierent metal hydroxide in the water-treating and dehydration steps, as is illustrated in the examples which follow.

A full understanding of the nature of the products of the invention and the manner of their preparation may be had by reference to the following specific examples.

The oxidation step of the process is illustrated by Examples A to I.

EXAMPLE A a rate of 1.7 liters per hour per grams of oil for 85 hours. The introduction of air was then stopped and the reaction mixture stirred with 48 grams (4%) of Hyilo (a diatomaceous earth filter aid), filtered and cooled. The filtered product contained 1.49% calcium.

EXAMPLE B Two thousand grams of a percolated, solvent-refined, Mid-Continent type bright stock and 218 grams (11 weight percent) of calcium hydroxide were charged to an electrically heated column reactor, 60 inches long by 3 inches in diameter, having a fritted glass piece sealed in the bottom. Sixty liters of air per hour were passed up through the oil, maintained at 204 C., for 24 hours. A portion of the reaction mixture was contacted with 4 weight percent of Hyflo and filtered. Analysis showed the filtrate to contain 1.94% calcium. This example illustrates the use of a column type reactor which provides a much more eflicient use of the oxidizing gas than the flask type reactor used in Example A. Consequently, the oxidation time in this example is considerably shorter.

Additional oxidations were conducted (Examples C to J) following the same general procedure employed in Example B, but varying the oxidation conditions. The pertinent data with respect to the several oxidation examples are summarized in Table II.

.Tqble .II

- Percent Temper- Air-rate, -xida- Percent Example Hydrocarbon Stock ,llrne ature, l./hr./ tlon Ca in charged C. 100 g. time, filtered 1 011 hr. product A SOltvenKt-refinedMid-Continent type bright 7.2 190 1.7 85 1. 49

.s 00 B- do 11 204 3.0 24 1. 94 0. do. 1 21 218 5. 0' '27 2.84 D. do 10 218 3.0 3 05-16 E- do 218 3. 0 7 0.57 F. do 10 218 3. 0 3 0.12 G- .do 3. 7 190 2. 5 50 2. 23 H. Foots oi 7. 2 204 2.0 48 2. 14 I Slack wax 7.2 190 1.7 50' 1.05 J Conventional 100 sec. at 100 F. paraflin oil- 10 204 3. 0 .3 i 0. 1

; 521(011): was-charged instead of lime.

The following examples illustrate the reactionof oxidized hydrocarbon products, prepared in the manner illustrated by Examples A to K, with phosphorus sulfide and also the reaction of the products thus produced with additional metal hydroxide in the presence of water to produce the products of the invention. The amount of EXAMPLE 1 Three hundred grams of filtered, oxidized solventrefined, Mid-Continent type residual oil product containing 1.49% soluble calcium (Example A, Table II), diluted with 100 milliliters of xylene were charged into a 4-necked, round-bottomed flask equipped with a stirrer, thermometer and a gas inlet tube. This mixture was reacted with grams of P 8 (10%, by weight, of the oxidized oil product) at 130 *F..to 145 C. for A'hour in an atmosphere of nitrogen. .The mixture gelled. Two hundred milliliters of toluene were added to reduce the viscosity. Seventy-five milliliters of water and 100 grams of limeuwere-added. The mixture was dehydrated to a temperature of 200 C. Five weight percent of Hyflo (filter aid) was added and the product filtered. The solvents were removed by distillation.

Analyses:

Calcium percent 6.03 Phosphorus do 2.44 Sulfur do 3.79 Calcium increase do 305 P 8 consumed do 88 13-10 stability No. 170

The percentage of additive, multiplied by 100, that reduces theN. N .-of the reference oil-t0 a value of.2. Thus, thelower the stability number, the more eifective the additive as an antioxidant.

EXAMPLE 2 One hundred and sixty-seven grams of a filtered, oxidized, solvent-refined, Mid Continent type residual oil product containing 1.49% soluble calcium (Example A, Table-ll) were diluted with 100 milliliters of xylene. This was reacted directly with 17 grams of P 8 (10%) and 50 grams of lime at 140 C. to 150C. for 5 minutes. Thernixture became gelatinous. Another 200 milliliters of xylene-were added and the mixture stirred for about 6 hours. After cooling to about 80 C. to 90 C., 50 milliliters of water were carefully added. The gelatinous mixture became very fluid. The water was stripped up to 195 C. About 5%, by weight of Hyfio (filter aid) was added and the product filtered. The solvents were removed by distillation.

Analyses: Percent Calcium 6.5 Phosphorus 2.40 Sulfur 3.81 Calcium increase 329 'P S ;consumed 86 Comparing Examples 1 and 2, it is seen that the use of 6 hours reaction time and the addition of the lime along with the P 8 inExample Z, as compared to the A-hour reaction time used in Example 1 did not. significantly affect the product in any way.

EXAMPLE 3 Analyses: Percent Calcium 1 2.25 Phosphorus 0.75 Sulfur 1.49 Calcium increase 132 P 8 consumed 1 4.50% on undiluted basis.

EXAMPLE 4 This example is the same as Example 3 with the exception that 15 grams ofl S (7.5%, by weight, of the calcium oxidized residual oil product) were used.

Analyses: Percent Calcium 1 2.78 Phosphorus 1.02 Sulfur 1.90 Calcium increase 187 P 8 consumed 98 1 5.56% on undiluted basis.

EXAMPLE 5 This example is the same as Example 3 with the exception the 20 grams of P S 10%, by weight, of the calcium oxidized residual oil product) were used.

This example is the same as described in Example 3 with the exception that 30 grams of P S (15%, by weight, of calcium oxidized residual oil product) were used. A gel formed after 12 minutes reaction time. A small amount of water (about 2% by weight) broke the gel and restored the original fluidity.

Analyses: Percent Calcium 1 3.02 Phosphorus 1.84 Sulfur 3.04 Calcium increase 211 P 5 consumed 88 1 6.04% on undiluted basis.

Examples 3 to 6 show the increase in metal content of the complex salt product attained by increasing the amount of P 5 used from 5% to 7.5% to and to respectively. The sharpest rise, however, occurs with the first 7.5% of P 8 with more gradual increases being obtained with 10% and 15% of the P S EXAMPLE 7 Two hundred and seventy-seven grams of an unfiltered, oxidized, solvent-refined, Mid-Continent residual oil product-lime mixture containing 1.27% calcium (prepared after the fashion of Example B, Table II) and 125 grams of conventional parafiin oil (300 seconds of 100 F.) were reacted with 25 grams of P 8 (about 10%, by weight, of the calcium oxidized residual oil product) at 100 C. to 110 C. for 3 hours in an atmosphere of nitrogen. Twenty-five milliliters of water (10%) were slowly added at 80 C. No additional lime was added over and above that which was present in the original mixture. ture of 190 C. Four weight percent of Hyfio (filter aid) was added and the product filtered.

1 3.81% on undiluted basis.

EXAMPLE 8 Two hundred grams of a filtered, oxidized, solventrefined Mid-Continent type residual oil product containing 2.84% barium (Example C, Table II) were diluted with 200 grams of 100 seconds Mid-Continent oil. This was reacted with grams of P 8 (10%) at 140 C. to 150 C. for 1 hour in an atmosphere of nitrogen. Twenty milliliters of water were carefully added at 90 C. followed by the addition of 85 grams of barium hydroxide (dry). The total mixture was dehydrated up to a temperature of 190 C. Eight weight percent of Hyfio (filter aid) was added and the product filtered.

Analyses: Percent Barium 1 7.9 Phosphorus 1.30 Sulfur 2.14 Barium increase 460 P 3 consumed 97 1 15.8% on undiluted basis.

The mixture was dehydrated up to a tempera- 10' This example illustrates the application of the process to a barium-oxidized oil using barium hydroxide as the water-complexing reagent.

EXAMPLE 9 Four hundred grams of an unfiltered, oxidized, Mid- Continent residual oil product (0.16% calicum)-lirne mixture (Example D, Table II) and 40 grams of P 8 were reacted in equipment described in Example 1 at 140 C. to 150 C. for 1 hour in an atmosphere of nitrogen. After cooling to 80 C. to C., 40 milliliters of H 0 and 80 grams of lime were added. The mixture was slowly dehydrated to 190 C. Eight weight percent of Hyfio (filter aid) was added and the product filtered immediately.

Analyses Percent Calcium 3 .87 Phosphorus 2.14 Sulfur 3.38 P 8 consumed 85 Calcium increase 2,300

This example shows the applicability of the process of the invention to a mildly oxidized oil (0.16% calcium)- EXAMPLE 10 Example 9 was duplicated with an unfiltered, oxidized, residual oil product containing 0.12% calcium (Example F, Table II).

Analyses:

Calcium percent 2.83 Phosphorus do 1.97 Sulfur do 3.00 3-10 stability No. 190

EXAMPLE Example 10 was duplicated except that the batch size was increased five-fold.

Analyses:

Calcium percent 2.78 Phosphorus do 1.89 Sulfur do 2.88 13-10 stability No 185 EXAMPLE 10b Example 10a was duplicated.

Analyses: Percent Calcium 2.79 Phosphorus 1.86 Sulfur 2.85

Examples 10, 10a and 10b show the reproduceability of the products of the process.

EXAMPLE 106 Analyses:

Calcium percent 0.1 1 Barium do 10.30 Phosphorus do. 2.09 Sulfur do 2.24 B-10 stability No Ca P 8 consumed percent 85 This example illustrates the production of a mixed metal salt of calcium and barium by the use of calcium.

woe-

11 hydroxide in the oxidation step and barium hydroxide ie'i hs a -e m ains st p- EXAMPLE 11 Four hundred grams of an unfiltered, oxidized, residual oil product containing 0.16% calcium (prepared in the manner of Example F, Table II) and 30 grams of P 8 were reacted for 1 hour at 140 C. to 150 C. Twenty grams of lime were added in the absence of water. The temperature was raised to 190C. Four weight percent of Hyflo (filter aid) was added and the product filtered immediately.

Analyses: Percent Calcium 0.06 Phosphorus 0.98 Sulfur 3.45

The poor metal content of this product shows the necessity for having water present in the reaction of the oxidized oil-P 8 product with the additional metal hydroxide.

EXAMPLE 12 Four hundred grams of an unfiltered, calcium oxidized residual oil mixture containing 0.57% calcium (Example E, Table II) and 40 grains of P S were reacted in equipment described in Example 1 at 140 C. to 150 C. for 1 hour in an atmosphere of nitrogen. After cooling to 80 C. to 90 C., 40 milliliters of water and 40 grams of lime were added. The mixture was slowly dehydrated to 190 C. Four weight percent of Hyflo (filter aid) was added and the product filtered.

Analyses: Percent Calcium 4.64 Phosphorus 2.47 Sulfur 4.29 P S consumed 90 EXAMPLE 13 One hundred grams of a filtered, calcium-oxidized residual oil product containing 2.76% calcium (same as Example B, Table II, except oxidization time was 30 hours) were diluted with 150 grams of conventional paraffin oil (100 seconds at 100 F.). This was reacted with 10 grams (10%) of lime and 10 grams of P 8 in equipment described in Example 1 at 140 C. to 155 C. for 1% hours in an atmosphere of nitrogen. A heavy geT-formed when the mixture was cooled to 80 C. The

gel broke when 20 milliliters of water and 20 grams of lime were added. The mixture was slowly dehydrated to 190 C. Eight weight percent of -Hyfio (filter aid) was added and the product filtered.

Analyses Percent Calcium 1 2.24 Phosphorus 1.15 Sulfur 1.98

1 5.6% on undiluted basis.

EXAMPLE 14 Analyses 7 Percent Calcium 2.72 Phosphorus 1.61 Sulfur 1.76

1 on undiluted basis.

EXAMPLE 15 Two hundred grams of a filtered, oxidized, solvent-refined, Mid-Continent type distillate oil product containing 2.23% soluble calcium (Example G, Table II) were dilutedwith 200 grams of conventional paraflin oil (100 seconds at 100 'F.). This was charged to equipment described in Example 1 and reacted with 20 grams of P 5 (10%, by Weight, of the calcium oxidized distillate oil product) at 140 C. to 150 C. in an atmosphere of nitrogen. A gel formed after 5 minutes reaction time. Twenty milliliters of water were carefully added at C. followed by the addition of 20 grams of lime. The mixture was dehydrated up to a temperature of 190 C. Four weight percent of Hyfio (filter aid) was added and the product filtered.

Analyses Percent Calcium 1 2.43

Phosphorus 1.22 Sulfur 1.78

Calcium increase 118 P 5 consumed 91 1 4.86% on undiluted basis.

EXAMPLE 16 Two hundred grams of a filtered, oxidized, foots oil product containing 2.14% soluble calcium (Example H, Table II) were diluted with 200 grams of conventional parafiin oil (100 seconds at 100 F.). This was charged to equipment described in Example 1 and reacted with 20 grams of P 8 (10%, by weight, of the calcium-oxidized distillate wax product) at 140 C. to 150 C. for /2 hour in an atmosphere of nitrogen. Twenty milliliters of water were carefully added followed by the addition of 20 grams of lime. The mixture was dehydrated up to a temperature of 190 C. Four weight percent of Hyflo (filter aid) was added and the product filtered.

Analyses: Percent Calcium 1 2.68 Phosphorus 1.26 Sulfur 1.84 Calcium increase 150 P 5 consumed 95 1 5.36% on undiluted basis.

EXAMPLE 17 Two hundred grams of a filtered, oxidized, slack wax product containing 1.08% soluble calcium (Example I, Table II) were diluted with 300 grams of conventional paratfin oil seconds at 100 F.) This was charged to equipment described in Example 1 and reacted with 20 grams of P 5 (10%, by Weight, of the calcium oxidized residual wax product) at C. to C. for 1V2 hours in an atmosphere of nitrogen. Twenty milliliters of water were carefully added followed by the addition of 40 grams of lime. The mixture was dehydrated up to a temperature of C. Four weight percent of Hyflo (filter aid) was added and the product filtered.

Analyses: Percent Calcium 1 1.71 Phosphorus 1.06 Sulfur 1.36 Calcium increase 138 P 5 consumed 98 1 2.57% on undiluted basis.

EXAMPLE 18 Twenty-one hundred and fifty grams of an unfiltered, calcium-oxidized wax benzene (2-12) product containing 0.12% oil-soluble calcium metal (prepared under the conditions of Example F, Table II) were reacted with For preparation see U. s. Patent No. 2,476,972.

Analyses:

Calcium percent 2.53 Phosphorus do 1.37 Sulfur d 2.17 B-10 stability No 175 EXAMPLE 19 Four hundred and forty grams of an unfiltered mixture of calcium-oxidized dodecylbenzene residue 1 containing This is the high boiling residue from dodecylbenzene manufacture.

0.13% oil-soluble calcium metal (prepared after the fashion of Example K, Table II) were reacted with 40 grams of phosphorus pentasulfide (10%, by weight, of oil) under an atmosphere of nitrogen at 140 C. to 145 C. for 3 hours (equipment used is described in Example 1). The mixture was cooled to 80 C. to 90 C. Forty milliliters of water were carefully added. The mixture was dehydrated up to a temperature of 190 C. Twenty grams (5 by weight) of Hyfio (filter aid) were EXAMPLE 20 Four hundred and forty grams of anunfiltered, calcium-oxidized white oil product (Nujol) containing 0.21% oil-soluble calcium metal and 1.46% oxygen (prepared under the conditions of Example F, Table II) were reacted with 40 grams of phosphorus pentasulfide by weight, of oil) for 3 hours at 150 C. in an atmosphere of nitrogen. The mixture was cooled to 80 C. to 90 C. Fourty milliliters of water were carefully added followed by 40 grams of lime. The mixture was dehydrated up to 150 C. Twenty grams (5%, by weight) of Hyflo (filter aid) were added and the mixture filtered hot.

Analyses Percent Calcium 3.51 Phosphorus 2.13 Sulfur 3.52

Examples to show the use of several difierent types of hydrocarbon reactants in the process of the invention.

EXAMPLE 21 Analyses:

Calcium percent 1.99 Phosphorus do- 1.98 Sulfur do 2.25 B-10 stability No B-10A stability No. 24 hours 500 EXAMPLE 22 Example 21 was duplicated except that after the phosphorus heptasulfide was rapidly added, 5 grams of sulfur were slowly added over about 1 hour. The mixture was heated at 150 C. for an additional 2 hours. The final steps were the same as in Example 21.

Analyses:

Calcium percent. 2.76 Phosphorus o 2.28 Sulfur d 2.75 B-10A stability No., 24 hours 430 EXAMPLE 23 Example 21 was duplicated with the exception that 40 grams of phosphorus trisulfide (P 5 were used.

Analyses: Percent Calcium 0.70 Phosphorus 0.62 Sulfur 1.18

EXAMPLE 24:

Example 22 was duplicated except that 40 grams of phosphorus trisulfide were substituted for phosphorus heptasulfide.

EXAMPLE 25 A mixture of pounds of Mid-Continent type bright stock and 10 pounds of lime were air oxidized (1.5 cu. ft./min.) in a conical shaped steel container at 400 F. for 5 hours. The oxygen content of a filtered sample of oxidized oil was 2.08%.

The unfiltered oxidized oil-lime mixture was transferred to a 30-gallon glass-lined Pfaudler kettle and treated with 7.5 pounds of P 8, (7.5%, by weight, of oxidized oil) at 220 F. for 6 hours in a nitrogen atmosphere. The mixture was cooled to 160 F. to 170 F. Ten pounds of water (10%) were added portionwise over 1 hour. After an additional 10 pounds of lime (10%) were added to complete the final neutralization, the water was removed over a 3-hour period up to a temperature of 150 C. Ten pounds of Hyde (filter aid) were added to facilitate filtration through a conventional plate and frame filter press.

Examples 21 to 26 illustrate the use of phosphorus heptasulfide and phosphorus trisulfide in the process of the invention. It will be seen that these sulfides provide products having metal contents somewhat lower than products prepared using phosphorus pentasulfide (compare Examples 21 and 23 with Example 9). However, the use of sulfur as a triggering agent in conjunction with, with the P 8 and P 8 increased the metal contents of the ultimate products (compare Examples 22 and 24 with Examples 21 and 23, respectively). Example 25- shows that by extending the reaction time from 3 hours (Example 21) to six hours, the metal content of the P 5 product was greatly increased.

EXAMPLE 26 Four hundred grams of a filtered, calcium-oxidized, Mid-Continent residual oil product containing 0.16% oilsoluble calcium metal (prepared under the conditions of Example D, Table II) were reacted with 40 grams of phosphorus pentasulfide for one hour at C. to C. in an atmosphere of nitrogen. The mixture was cooled- (4%, by weight), of Hyflo (filter aid) were added and the mixture filtered hot.

EXAMPLE 27 Four hundred grams of a filtered, calcium-oxidized, Mid-Continent residual oil product containing 0.12% oilsoluble calcium metal (for oxidation conditions see Example F, Table II) were reacted with 30 grams of phosphd ruspentasulfide (7.5%)for 3 hours at 170 C. in an atmosphere of nitrogen. One-half of the mixture was filtered.

An l e Neutralization No 16 (1st break). 24 (1st break). Phosphorus 2.07 percent. Sulfur 4.13 percent. B-10 stability No 47.

Analyses:

Zinc percent 1.20 Phosphorus do 1.77 Sulfur do 3.22 B-lO stability No 175 EXAMPLE 28 Four hundred grams of a filtered, Mid-Continent type,

calcium-oxidized residual oil product containing 0.25% 7 oil-soluble calcium metal and 1.20% oxygen (for oxidation conditions see Example F, Table II) were reacted with 40 grams of phosphorus pentasulfide (10%, by weight, of oil) for 3 hours at 150 C. in an atmosphere of nitrogen. The mixture was cooled to 80 C. to 90 C. Twenty milliliters of water were carefully added followed by a solution containing 16 grams of NaOH in 20 milliliters of water. The mixture was dehydrated up to 150 C. One hundred grams of this product were removed and filtered.

Analyses:

Calcium percent 0.20 Sodium ..do 2.30 Phosphorus do 2.50 Sulfur do 3.63 BaseNumber 8.9 B-10A stability No 200 EXAMPLE 29 To the remainder of the product from Example 28, a solution containing 27 grams of ZnCl in 60 milliliters of water was added. The mixture was dehydrated up to 160 C. Fifteen grams (5%, by weight,) of Hyflo (filter aid) were added and the product filtered hot.

Analyses: Zinc i percent 3.34 Calcium do.. 0.20 Sodium do 2.02 Phosphorus do 2.24 Sulfur do 2.99 Chlorine do 3.84 B-10A stability No 600 Examples 26 to 28 illustrate the use of zinc carbonate,

zinc oxide and sodium hydroxide, respectively, as metal salt reagents in the water-complexing step, while Example 29 shows the further complexing of the sodium hydroxide-complexed product with zinc chloride. It will be seen from the latter example that the reaction which occurs is a complexing of the zinc chloride with the sodium salt, rather than a metathetical exchange which would ordinarily occur by a reaction of a sodium salt with zinc chloride.

EXAMPLE so A mixture of two thousand grams of a Mid-Continent type residual oil and 100 grams of zinc oxide (5%, by weight,) were air oxidized at 420 F. for 3 /2 hours with an air rate equivalent to 3 l./ 100 grams of oil/hour.

Four hundred and twenty grams of this mixture containing 0.09% oil-soluble zinc metal and 0.70% oxygen were reacted with 40 grams of phosphorus pentasulfide at 150 C. for 3 hours in an atmosphere of nitrogen. The mixture was cooled to C. to C. and forty milliliters of water were carefully added. The mixture was dehydrated up to 150 C. Twenty grams of Hyflo (filter aid) were added and the mixture filtered hot.

(a) A sodium-oxidized residual oil intermediate was made by oxidizing a 3.5% caustic soda in oil mixture at 218 C. with an air rate equivalent to 5 l./hr./ grams of oil. The oxygen and oil-soluble sodium contents of the oxidized product were 1.42% and 0.7%, respectively.

(b) Four hundred grams of the unfiltered sodium-oxidized residual oil-caustic soda mixture (a) were reacted with 30 grams of P487 (7.5 weight percent) for six hours at C. in a nitrogen atmosphere. After cooling the mixture to 80 C., 40 milliliters of water were carefully added followed by 40 grams of lime. The mixture was dehydrated to a temperature of 150 C. Five percent of Hyflo (filter aid) was added and the mixture filtered.

31(a), with the exception that 40 grams of P S (10 weight percent) were substituted for the P 8 and reacted for three hours.

Analyses:

Calcium percent 2.62 Sodium do i 0.7 Phosphorus do 2.30 Sulfur 7 o 2.68 B-10 stability No.

17 EXAMPLE 33 Four hundred grams of an unfiltered sodium-oxidized residual oil-caustic soda mixture containing 0.87% oxygen and 0.5% oil-soluble sodium were reacted with 40 grams of P 8 weight percent) for 4 hours at 105 C. in a nitrogen atmosphere. After cooling the mixture to 80 C., 20 milliliters of water were carefully added followed by a solution of 40 grams of caustic soda in 60 milliliters of water. The mixture was dehydrated to a temperature of 200 C. Five percent of Standard Super Cel (filter aid) was added and the mixture filtered.

Analyses: Percent Sodium 3.70 Phosphorus 1.82 Sulfur 2.2.0

Example 30 illustrates the use of zinc oxide in the oxidation and water-complexing steps of the invention. Examples 31 and 32, on the other hand, show the use of sodium hydroxide in the oxidation step with P 3 as the phosphorus sulfide reactant in one case (Example 31) and P 5 in another (Example 32), the water-complexing salt being calcium hydroxide. Example 33 shows the use of sodium hydroxide in both the oxidation and watercomplexing steps.

EVALUATION OF PRODUCTS Table IV Calcium L-l caterpillar test Prod- Gone, in oil uct percent blend, 5 added percent Test Piston Lacquer Percent tune, hr rating demerits TGI N 0ne 120 61. 9 28. 2 6 Do 120 57.4 =31.0 7 120 98. 8 e 0.7 0 10 X 4. 0 0.11 240 97. 6 a 1.4 1 480 94.3 B g 120 99. X 1 4. 0 0.11 2 1 3 1 0 Y 2.8 0.11 240 3% i i 240 9 Y 2 088 i 480 93. 9 a. 9 5 120 99. 3 I 0.0 4 Z 2. 9 0. 088 240 98. 3 f 0. 1 13 480 97.1 1 0. 8 120 99. 7 B 0. 1 1 Z 2. 9 0.088 240 99. 0 B 0. 4 6 480 93. 2 s 4. 2 12 X-A product similar to that described in Ex. 10a; ca1cium=2.79%; phosphorus=1.86%; sulfur=2.85%.

YA product similar to that described in Ex. 12, except 15% P255 was used; calciu1n=4.02; phosphorus=2.56%; sulfur=2.62%.

Z-A pilot plant batch of a product similar to X. Calc1um=3.07%; phosphorus=1.93%; suliu.r=3.58%.

Ba.se oil is an SAE grade solvent-refined Mid-Oontment 011, K. V. at 210 F.=11.08 05., K. V. at 100 F.=101.4 cs.

B1end also contained 0.5% of a commercial antioxidant (a pmene-PzS reaction product).

Blend also contained 0.25% of a commercial antioxidant as m footnote Blend also contained 0.5% of a commercial antioxidant (a suliurized ter ene -Blend also contained 0.5% of a commercial antioxidant (zinc di- 30 hexyldith iophosphate). The ability of the reaction products of the invention TGILDOP Grove Packmg' as detergents and antioxidants for engine lubricating oils LAUSON ENGINE D-4A TEST has been demoflfitrated y subjecting Oil blends of 01656 This test determines the effectiveness of the lubricatproducts to engme tests. The detergent tests used were i il i preventing piston fouling a measured by the the Lauson (116931 13-21, R diesel 13-23 cleanliness of the rings, lands, grooves and piston skirts. and caterplllar ellglne tests- The antlOXldaIlt ieSiS Cleanliness ratings are assigned at the end of the test were the Lauson D4{& and 08-2 tests. The several tes on a le f f m 100 to O, a 100 rating signifying procedures are described below. The results obtained a perfectly clean condition and a zero rating represent- III a representatlve numbfif of tests are 5 1n Tablfis ing the worst possible deposit condition. Bearing weight III and IV. From these test results it is apparent that 40 l i l o measured as supplemental data. A single the products of the invention are outstanding detergents cylinder, 4-cyc1e, liquid-cooled Lauson engine with splash for engine lubricating oils when used either alone or in l bri ation and having a copper-lead bearing is employed combination with known antioxidants. Also, it is seen i the test. The operating conditions are as follows: that the products prepared from the mildly oxidized oils, Sample "gallon" 1 1. e., those having less than 0.5% metal contents, are Oil temperature 225 the best detergents (see Examples 9 and 10a, Table III). J ket temperature P 275 The data in Table III also show that the products of the Speed R. P. M 1825 invention are efl'ective antioxidants, particularly those Brake load H P 1.6 produced from the mildly oxidized oil intermediates. One-half throttle air-fuel ratio 13-1 Table III Lauson D4A engine B CFR D-21 OFR D-23 Lauson OS2 engine B diesel b diesel b Percent Product Metal, Percent Percent Inetalin added percent phossulfur oxidized phorus Percent Avg.% Percent Percent Percent AvgJA oil interproduct Rating brg. wt. product Rating product Rating product Rating brg. wt. mediate loss, mg. loss, mg.

None None. Ex. 2 Ex. 8---- Ex. 9..-. Ex. 10a.- Ex. 1%.. Ex. l0c Ex. 12-.. Ex. 15 Ex. 16... 1. 26 2.14 Ex. 17..- Oa1.71 1.06 1.08

e The base oil was an SAE oil blend equivalent to 0.3% Ba (0.088% Ca), except where noted 20 grade solvent-refined, Pennsylvania oil (kin. vis. at F.=63 es.; kin. vls. at 210 F.=8.3 05.). Metal content of b The base oil was an SAE 30 grade solvent-refined, Mid-Continent oil (kin. vis. at 100 F.==121 cs.; kin. vis. at 210 F.=l2.2 03.). Metal content of oil blend equivalent to 0.3% Ba (0.088% Ca).

0 The oil blend also contained 0.5% of a commercial antioxidant (pinene-PrSi product),

P1 The oil contained 1.0% of the commercial antioxidant as in 12357,, more additive was used.

19 Oil was added every 20 hours. The duration of the test is 100 hours. The piston cleanliness rating and the bearing Weight loss obtained with the test oil is compared to that obtained with the reference oil.

CFR DIESEL DETERGENCY TEST D21 This test determines the effectiveness of the lubricating oil in preventing piston deposits and top ring wear. A single cylinder, CFR 4-cycle, supercharged diesel engine is used. The operating conditions are as follows:

Oil temperature F 175 Jacket temperature F 212 Speed R. P. M 1800 Brake load "H. P 7.5

I A one and one-half gallon sample of oil is used with addition of oil every 8 hours starting at 4 hours. The duration of the test is 60 hours. The diesel fuel used contained 1% sulfur. The results of the test are reported in terms of piston cleanliness ratings as in the D-4A test.

CFR DIESEL DETERGENCY TEST D23 This test determines the effectiveness of an oil in preventing piston deposits and top ring wear. The operating conditions are as follows:

Oil temperature F 175 Jacket temperature F 212 Speed R. P. M 1800 Brake load H. P 4.5

A one and one-half gallon sample of oil is used at the start and oil is added every 8 hours starting at 4 hours. The duration of the test is 60 hours. The diesel fuel used contained 0.4% sulfur. The results are given in terms of piston cleanliness ratings using the same rating system as in the Lauson D-4A and diesel D-2l test.

CRC CATERPILLAR ENGINE TEST L-l This is a specification engine test to determine the ability of an oil to prevent engine deposits including the piston and crankcase deposits. A single cylinder, 4-cycle caterpillar engine is used. The operating conditions are as follows:

011 temperature F 150 Jacket temperature F 180 Speed -R. P. M 1000 Brake load H. P 19.8

Twenty gallons of oil is used in the engine at the start of the test and the oil is changed at 120-hour intervals. The duration of the test is 480 hours. The diesel fuel used contained 0.4% sulfur. The condition of the engine at the end of the test is expressed by an engine cleanliness rating based on a scale from to 100, 100 being a perfectly clean engine.

It will be appreciated that the products of this invention are actually oil solutions of the phosphorus-, sulfurand metal-containing oxidized oil products, and although the products shown in the examples presented herein vary with respect to the concentration of the products in the oil, it will be understood that these differences can be eliminated by standardization of process proce- 20 sants, viscosity index improvers, defoamants, rust preventives, etc.

Although the invention has been described herein by means of certain specific embodiments and illustrative examples, it is not intended that it be limited in any way thereby, but only as indicated in the accompanying claims.

What is claimed is:

1. An oil-soluble, phosphorus-, sulfurand metal-eontaining oxidized hydrocarbon reaction product produced by the method which comprises the steps of (1) forming a mixture comprising (a) a hydrocarbon having a molecular weight of from about 200 to 1000 and which is selected from the group consisting of aliphatic hydrocarbons and aromatic hydrocarbons having at least one nuclear hydrogen atom substituted by an aliphatic radical to provide a total of at least 8 aliphatic carbon atoms per molecule therein, and mixtures thereof, and (b) from about 0.5% to about 25%, based on the weight of said hydrocanbon, of a metal hydroxide, the metal constituent of which is selected from Groups I and II of Mendeleeffs Periodic Table of the Elements, (2) contacting said mixture with an oxidizing gas at a temperature of from about 125 C. to about 325 C. to effect oxidation of said hydrocarbon and reaction of said metal hydroxide with the oxidized hydrocarbon, (3) continuing the oxidation for a time suflicient to incorporate from about 0.05% to about 3.0%, by weight, of metal into the oxidized hydrocarbon, (4) reacting the product from step 3 with from about 5% to about 20%, by weight, based on the weight of hydrocarbon charged in step 1, of a phosphorus sulfide, at a temperature of from about C. to about 150 C., to form a phosphorus, sulfurand metal-containing product, (5) providing a mixture of the reaction product from step 4 with from about 2% to about 25 by weight, based on the hydrocarbon charged in step 1, of a metal hydroxide, the metal constituent of which is selected from Groups I and II of Mendeleetts Periodic Table of the Elements, and water, at a temperature below the boiling point of water, (6) substantially completely dehydrating the mixture formed in step 5 and (7) subjecting the dehydrated mixture to filtration to remove insolubles therefrom.

2. An oil-soluble, phosphorus, sulfurand metal-containing oxidized oil reaction product produced by the method which comprises the steps of (1) forming a mixture comprising (a) a petroleum oil having a molecular weight of from about 200 to about 1000 and (b) from about 0.5 to about 25%, based on the weight of said oil, of a metal hydroxide, the metal constituent of which is selected from Group II of Mendeleetfs Periodic Table of the Elements, (2) contacting said mixture with an oxidizing gas at a temperature of from about C. to about 325 C. to effect oxidation of said oil and reaction of said metal hydroxide with the oxidized oil, (3) continuing the oxidation for a time sufiieient to incorporate from about 0.05 to about 3.0%, by weight, of metal into the oxidized oil, (4) reacting the product of step 3 with from about 5% to about 20%, by weight, based on the oil charged in step 1, of a phosphorus sulfide, at a temperature of from about 75 C. to about dure and also when required by distillation of a portion 7 C., to form a phosphorus-, sulfurand metal-containing product, (5) providing a mixture of the reaction product from step 4 with from about 2% to about 25 I by weight, based on the oil charged in step 1, of a hydroxide of a metal selected from Group II of Mendeleeffs .Periodic Table of the Elements, and water, at a temperature below the boiling point of water, (6) substantially completely dehydrating the mixture formed in step 5 and (7) subjecting the dehydrated mixture to filtration to remove insolubles therefrom.

3. An oil-soluble, phosphorus-, sulfurand calciumcontaining oxidized oil reaction product produced by the method which comprises the steps of (1) forming a mixture comprising (a) a petroleum oil having a molecular weight of from about 600 to about 1000 and (b) from about 0.5% to about 25% of calcium hydroxide, (2) contacting said mixture with an oxidizing gas at a temperature of from about 125 C. to about 325 C. to effect oxidation of said oil and reaction of said calcium hydroxide with the oxidized oil, (3) continuing the oxidation for a time sufficient to incorporate from about 0.05 to about 3.0%, by weight, of calcium into the oxidized oil, (4) reacting the product from step 3 with from about to about by weight, based on the hydrocarbon charged in step 1, of a phosphorus sulfide, at a temperature of from about 75 C. to about 150 C., to form a phosphorus-, sulfurand calcium-containing product, (5) providing a mixture of the reaction product from step 4 with from about 2% to about by Weight, based on the weight of the oil charged in step 1, of calcium hydroxide, and water, at a temperature below the boiling point of water, (6) substantially completely dehydrating the mixture formed in step 5 and (7) subjecting the dehydrated mixture to filtration to remove insolubles therefrom.

4. An oil-soluble, phosphorus-, sulfurand calciiuncontaining oxidized oil reaction product produced by the method which comprises the steps of (1) forming a mixture comprising (a) a petroleum oil having a molecular weight of from about 600 to about 1000 and (b) from about 0.5 to about 25 based on the weight of said oil, of calcium hydroxide, (2) contacting said mixture with an oxidizing gas, at a temperature of from about 125 C. to about 325 C., to effect oxidation of said oil and reaction of said calcium hydroxide with the oxidized oil, (3) continuing the oxidation for a time sufiicient to incorporate from about 0.05% to about 0.5%, by weight, of calcium into the oxidized oil, (4) reacting the product from step 3 with from about 5% to about 20%, by weight, based on the weight of oil charged in step 1, of phosphorus pentasulfide, at a temperature of from about 75 C. to about 150 C. to form a phosphorus-, sulfurand calcium-containing product, (5 providing a mixture of the reaction product from step 4 with from about 2% to about 25%, by weight, based on the weight of oil charged in step- 1 of calcium hydroxide, and water, at a temperature below the boiling point of water, (6) substantially completely dehydrating the mixture formed in step 5 and (7) subjecting the dehydrated mixture to filtration to remove insolubles therefrom.

5. An oil-soluble, phosphorus-, sulfurand bariumcontaining oxidized oil reaction product produced by the method which comprises the steps of (1) forming a mixture comprising (a) a petroleum oil having a molecular weight of from about 600 to about 1000 and (b) from about 0.5 to about 25 based on the weight of said oil, of barium hydroxide, (2) contacting said mixture with an oxidizing gas, at a temperature of from about 125 C. to about 325 C., to efiect oxidation of said oil and reaction of said barium hydroxide with the oxidized oil, (3) continuing the oxidation for a time sufiicient to incorporate from about 0.05% to about 3.0%, by weight, of barium into the oxidized oil, (41) reacting the product from step 3 with from about 5% to about 20%, by weight, based on the weight of the oil charged in step 1, of a phosphorus sulfide, at a temperature of from about 75 C. to about 150 C., to form a phosphorus-, sulfurand barium-containing product, (5) providing a mixture of the reaction product from step 4 with from about 2% to about 25%, by weight, based on the weight of the oil charged in step 1, of barium hydroxide, and water, at a temperature below the boiling point of water, (6) substantially completely dehydrating the mixture formed in step 5 and (7) subjecting the dehydrated mixture to filtration to remove insolubles therefrom.

6. An oil-soluble, phosphorus-, sulfurand barium-com taining oxidized oil reaction product produced by the method which comprises the steps of (1) forming a mix ture comprising (a) a petroleum oil having a molecular weight of from about 600 to about 1000 and (b) from about 0.5 to about 25 based on the weight of said oil, of barium hydroxide, (2) contacting said mixture with an oxidizing gas, at a temperature of from about 125 C. to about 325 C., to effect oxidation of said oil and reaction of said barium hydroxide With the oxidized oil, (3) continuing the oxidation for a time sufficient to incorporate from about 0.05% to 0.5%, by weight, of barium into the oxidized oil, (4) reacting the product from step 3 with from about 5% to about 20%, by weight, based on the Weight of the oil charged in step 1, of phosphorus pentasulfide, at a temperature of from about C. to about 150 C., to form a phosphorus-, sulfurand barium-containing product, (5) providing a mixture of the reaction product from step 4 with from about 2% to about 25%, by weight, based on the weight of oil charged in step 1, of barium hydroxide, and water, at a temperature below the boiling point of water, (6) substantially completely dehydrating the mixture formed in step 5 and (7) subjecting the dehydrated mixture to filtration to remove insolubles therefrom.

7. An oil-soluble, phosphorus-, sulfur-, calciumand zinc-containing oxidized oil reaction product produced by the method which comprises the steps of (l) forming a mixture comprising (a) a petroleum oil having a molecular weight of from about 600 to about 1000 and (b) from about 0.5% to about 25%, based on the weight of said oil, of calcium hydroxide, (2) contacting said mixture with an oxidizing gas at a temperature of from about 125 C. to about 325 C. to effect oxidation of said oil and reaction of said calcium hydroxide with the oxidized oil, (3) continuing the oxidation for a time sufficient to incorporate from about 0.05% to about 3.0%, by weight, of calcium into the oxidized oil, (4) reacting the product from step 3 with from about 5% to about 20%, by weight, based on the weight of oil charged in step 1, of a phosphorus sulfide at a temperature of from about C. to about 150 C. to form a phosphorus-, sulfurand calcium-containing product, (5) providing a mixture of the reaction product from step 4 with zinc hydroxide and water at a temperature below the boiling point of water, (6) substantially completely dehydrating the mixture formed in step 5 and (7) subjecting the dehydrated mixture to filtration to remove insolubles therefrom.

8. An oil-soluble, phosphorus-, sulfur-, calciumand zinc-containing oxidized oil reaction product produced by the method which comprises the steps of (l) forming a mixture comprising (a) a petroleum oii having a molecular weight of from about 600 to about 1000 and (b) from about 0.5% to about 25 based on the weight of said oil, of calcium hydroxide, (2) contacting said mixture with an oxidizing gas, at a temperature of from about C. to about 325 C., to efiect oxidation of said oil and reaction of said calcium hydroxide with the oxidized oil, (3) continuing the oxidation for a time sufiicient to incorporate from about 0.05% to 0.5%, by Weight, of metal into the oxidized oil, (4) reacting the product from step 3 with from about 5% to about 20%, by weight, based on the weight of oil charged in step 1, of phosphorus pentasulfide, at a temperature of from about 75 C. to about C., to form a phosphorus-, sulfurand calcium-containing product, (5) providing a mixture of the reaction product from step 4 with from about 2% to about 25%, based on the weight of the oil charged in step 1, of zinc hydroxide, and water, at a temperature below the boiling point of water, (6) substantially completely dehydrating the mixture formed in step 5 and (7) subjecting the dehydrated mixture to filtration to remove insolubles therefrom.

9. An oil-soluble, phosphorus, sulfurand calciumcontaining oxidized oil reaction product produced by the method which comprises the steps of (1) forming a mix- 23 ture comprising (a) a petroleum oil having a molecular weight of from about 600 to about 1000 and (b) from about 0.5% to about 25% of calcium hydroxide, (2) contacting said mixture with an oxidizing gas, at a temperature of from about 125 C. to about 325 C., to effect oxidation of said oil and reaction of said calcium hydroxide with the oxidized oil, (3) continuing the oxidation for a time sufiicient to incorporate from about 0.05% to about 0.5 by weight, of calcium into the oxidized oil. (4) reacting the product from step 3 with from about to about by weight, based on the weight of oil charged in step 1, of phosphorus heptasulfide, at a temperature of from about 75 C. to about 150 C., to form a phosphorus, sulfurand calcium-containing product, (5) providing a mixture of the reaction product from step 4 with from about 2% to about by weight, based on the weight of oil charged in step 1, of calcium hydroxide, and water, at a temperature below the boiling point of water, (6) substantially completely dehydrating the mixture formed in step 5 and (7) subjecting the dehydrated mixture to filtration to remove insolubles therefrom.

10. An oil-soluble, phosphorus-, sulfurand calciumcontaining oxidized oil reaction product produced by the method which comprises the steps of (1) forming a mixture comprising (a) a petroleum oil having a molecular weight of from about 600 to about 1000 and (b) from about 0.5 to about 25 of calcium hydroxide, (2) contacting said mixture with an oxidizing gas, at a temperature of from about 125 C. to about 325 C., to effect oxidation of said oil and reaction of said calcium hydroxide with the oxidized oil, (3) continuing the oxidation for a time sufficient to incorporate from about 0.05 to about 0.5 by weight, of calcium into the oxidized oil, (4) reacting the product of step 3 with from about 5% to about 20%, by weight, based on the weight of the oil charged in step 1, of phosphorus trisulfide, at a temperature of from about 75 C. to about 125 C., to form a phosphorus-, sulfurand calcium-containing product, (5) providing a mixture of the reaction product from step 4 with from about 2% to about 25%, based on the Weight of the oil charged in step 1, of calcium hydroxide, and water, at a temperature below the boiling point of water, (6) substantially completely dehydrating the mixture formed in step 5 and (7) subjecting the dehydrated mixture to filtration to remove insolubles therefrom.

11. An oil-soluble, phosphorus-, sulfur, and calciumcontaining reaction product produced by the method which comprises the steps of (1) forming a mixture comprising (a) a petroleum oil having a molecular weight of from about 600 to about 1000 and (b) from about 0.5% to about 25% of calcium hydroxide, (2) contacting said mixture with an oxidizing gas, at a temperature of from about 125 C. to about 325 C., to effect oxidation of said oil and reaction of said calcium hydroxide with the oxidized oil, (3) continuing the oxidation for a time sufiicient to incorporate from about 0.05% to about 0.5%, by weight, of calcium into the oxidized oil, (4) reacting the product of step 3 with from about 5% to about 20%, by weight, of phosphorus trisulfide and from about ,05% to about 2% of sulfur, both percentages being based on the weight of oil charged in step 1, at a temperature of from about 75 C. to about 150 C., to form a phosphorus-, sulfurand calcium-containing product, (5) providing a mixture of the reaction product from step 4 with from about 2% to about 25 based on the weight of oil charged in step 1, of calcium hydroxide, and water, at

" F; .id hydrocarbon, of a metal hydroxide, the metal constituent of which is selected from Groups I and II of Mendeleeffs Periodic Table of the Elements, (2) contacting said mixture with an oxidizing gas at a temperature of from about 125 C. to about 325 C. to effect oxidation of: said hydrocarbon and reaction of said metal hydroxide with the oxidized hydrocarbon, (3) continuing the oxidation for a time sufiicient to incorporate from about 0.05 to about 3.0%, by weight, of metal into the oxidized hydrocarbon, (4) reacting the product from step 3 with from about 5% to about 20%, by weight, based on the weight of hydrocarbon charged in step 1, of a phosphorus sulfide, at a temperature of from about C. to about 150 C., to form a phosphorus-, sulfurand metal-containing product, (5 providing a mixture of the reaction product from step 4 with from about 2% to about 25%, by weight, based on the hydrocarbon charged in step 1, of a metal hydroxide, the metal constituent of which is selected from Groups I and II Mendeleetls Feriodic Table of the Elements, and water, at a temperature below the boiling point of water, (6) substantially completely dehydrating the mixture formed in step 5 and (7) subjecting the dehydrated mixture to filtration to remove insolubles therefrom.

13. A mineral lubricating oil containing a minor amount, sufficient to improve the detergent character thereof, of an oil-soluble, phosphorus-, sulfurand metalcontaining oxidized oil reaction product produced by the method which comprises the steps of (1) forming a mixture comprising (a) a petroleum oil having a molecular weight of from about 200 to about 1000 and (b) from about 0.5 to about 25 based on the weight of said oil, of a metal hydroxide, the metal constituent of which is selected from Group II of Mendeleeffs Periodic Table of the Elements, (2) contacting said mixture with an oxidizing gas at a temperature of from about C. to about 325 C. to eflfect oxidation of said oil and reaction of said metal hydroxide with the oxidized oil, (3) continuing the oxidation for a time sufiicient to incorporate from about 0.05% to about 3.0%, by weight, of metal into the oxidized oil, (4) reacting the product of step 3 with from about 5% to about 20%, by weight, based on the oil charged in step 1, of a phosphorus sulfide, at a temperature of from about 75 C. to about C., to form a phosphorus-, sulfurand metal-containing product, (5) providing a mixture of the reaction product from step 4 with from about 2% to about 25%, by weight, based on the oil charged in step 1, of a hydroxide of a metal selected from Group II of Mendeleefis Periodic Table of the Elements, and water, at a temperature below the boiling point of water, (6) substantially completely dehydrating the mixture formed in step 5 and (7) subjecting the dehydrated mixture to filtration to remove insolubles therefrom.

14. A mineral lubricating oil containing a minor amount, sufiicient to improve the detergent character thereof, of an oil-soluble, phosphorus-, sulfurand calcium containing oxidized oil reaction product produced by the method which comprises the steps of (1) forming a mixture comprising (a) a petroleum oil having a molecular weight of from about 600 to about 1000 and (b) from about 0.5 to about 25% of calcium hydroxide, (2) contacting said mixture with an oxidizing gas at a temperature of from about 125 C. to about 325 C. to effect-oxidation of said oil and reaction of said calcium hydroxide with the oxidized oil, (3) continuing the oxidation for a time suflicient to incorporate from about 0.05% to about 3.0%, by weight, of calcium into the oxidized oil, (4) reacting the product from step 3 with from about to about 20%, by weight, based on the hydrocarbon charged in step 1, of a phosphorus sulfide, at a temperature of from about 75 C. to about 150 C., to form a phosphorus-, sulfurand calcium-containing product, (5 providing a mixture of the reaction product from step 4 with from about 2% to about 25%, by weight, based on the Weight of the oil charged in step 1, of calcium hydroxide, and water, at a temperature be low the boiling point of Water, (6) substantially completely dehydrating the mixture formed in step 5 and (7) subjecting the dehydrated mixture to filtration to remove insolubles therefrom.

15. A mineral lubricating oil containing a minor amount, sufiicient to improve the detergent character thereof, of an oil-soluble, phosphorus-, sulfurand calcium-containing oxidized oil reaction product produced by the method which comprises the steps of (1) forming a mixture comprising (a) a petroleum oil having a molecular weight of from about 600 to about 1000 and (b) from about 0.5% to about 25%, based on the Weight of said oil, of calcium hydroxide, (2) contacting said mixture with an oxidizing gas, at a temperature of from about 125 C. to about 325 C., to effect oxidation of said oil and reaction of said calcium hydroxide with the oxidized oil, (3) continuing the oxidation for a time sufiicient to incorporate from about 0.05% to about 0.5%, by weight, of calcium into the oxidized oil, (4) reacting the product from step 3 with from about 5% to about 20%, by Weight, based on the weight of oil charged in step 1, of phosphorus pentasulfide, at a temperature of from about 75 C. to about 150 C. to form a phosphorus-, sulfurand calcium-containing product, (5) providing a mixture of the reaction product from step 4 with from about 2% to about 25%, by Weight, based on the weight of oil charged in step 1 of calcium hydroxide, and water, at a temperature below the boiling point of water, (6) substantially completely dehydrating the mixture formed in step 5 and (7) subjecting the dehydrated mixture to filtration to remove insolubles therefrom.

16. A mineral lubricating oil containing a minor amount, suflicient to improve the detergent character thereof, of an oil-soluble, phosphorus-, sulfurand barium-containing oxidized oil reaction product produced by the method which comprises the steps (1) forming a mixture comprising (a) a petroleum oil having a molecular weight of from about 600 to about 1000 and (b) from about 0.5% to about 25%, based on the Weight of said oil, of barium hydroxide, (2) contacting said mixture with an oxidizing gas, at a temperature of from about 125 C. to about 325 C., to effect oxidation of said oil and reaction of said barium hydroxide with the oxidized oil, (3) continuing the oxidation for a time sufiicient to incorporate from about 0.05% to about 3.0%, by weight, of barium into the oxidized oi}, (4) reacting the product from step 3 with from about 5% to about 20%, by weight, based on the weight of the oil charged in step 1, of a phosphorus sulfide, at a temperature of from about 75 C. to about 150 C., to form a phosphorus-, sulfurand barium-containing product, (5) providing a mixture of the reaction product from step 4 with from about 2% to about 25%, by Weight, based on the weight of the oil charged in step 1, of barium hydroxide, and Water, at a temperature below the boiling point of Water, (6) substantially completely dehydrating the" mixture formed in step 5 and (7) subjecting the dehydrated mixture to filtration to remove insolubles therefrom.

17. A mineral lubricating oil containing a minor amount, sufficient to improve the detergent character thereof, of an oil-soluble, phosphorus-, sulfurand barium-containing oxidized oil reaction product produced by the method which comprises the steps of (1) forming a mixture comprising (a) a petroleum oil having a molecular weight of from about 600 to about 1000 and (b) from about 0.5 to about 25%, based on the weight of said oil, of barium hydroxide, (2) contacting said mixture with an oxidizing gas, at a temperature of from about 125 C. to about 325 C., to efiect oxidation of said oil and reaction of said barium hydroxide with the oxidized oil, (3) continuing the oxidation for a time sufficient to incorporate from about 0.05% to 0.5%, by weight, of barium into the oxidized oil, (4) reacting the product from step 3 with from about 5% to about 20%, by weight, based on the weight of the oil charged in step 1, of phosphorus pentasulfide, at a temperature of from about 75 C. to about 150 C., to form a phosphorus-, sulfurand barium-containing product, (5) providing a mixture of the reaction product from step 4 with from about 2% to about 25% by Weight, based on the Weight of oil charged in step 1, of barium hydroxide, and water, at a temperature below the boiling point of water, (6) substantially completely dehydrating the mixture formed in step 5 and (7) subjecting the dehydrated mixture to filtration to remove insolubles therefrom.

18. A mineral lubricating oil containing a minor amount, sufficient to improve the detergent character thereof, of an oil-soluble, phosphorus-, sulfur-, calciumand zinc-containing oxidized oil reaction product produced by the method which comprises the steps of (1) forming a mixture comprising (a) a petroleum oil having a molecular weight of from about 600 to about 1000 and (b) from about 0.5% to about 25%, based on the weight of said oil, of calcium hydroxide, (2) contacting said mixture with an oxidizing gas at a temperature of from about 125 C. to about 325 C. to efi'ect oxidation of said oil and reaction of said calcium hydroxide with the oxidized oil, (3) continuing the oxidation for a time sufficient to incorporate from about 0.05% to about 3.0%, by weight, of calcium into the oxidized oil, ('4) reacting the product from step 3 with from about 5% to about 20%, by weight, based on the weight of oil charged in step 1, of a phosphorus sulfide at a temperature of from about C. to about 150 C. to form a phosphorus-, sulfurand calcium-containing product, (5) providing a mixture of the reaction product from step 4 with zinc hydroxide and water at a temperature below the boiling point of water, (6) substantially completely dehydrating the mixture formed in step 5 and (7) subjecting the dehydrated mixture to filtration to remove insolubles therefrom.

19. A mineral lubricating oil containing a minor amount, suificient to improve the detergent character thereof, of an oil-soluble, phosphorus-, sulfun, calciumand zinc-containing oxidized oil reaction product produced by the method which comprises the steps of (1) forming a mixture comprising (a) a petroleum oil having a molecular weight of from about 600 to about 1000 and (b) from about 0.5% to about 25 based on the weight of said oil, of calcium hydroxide, (2) contacting said mixture with an oxidizing gas, at a temperature of from about C. to about 325 C., to effect oxidation of said oil and reaction of said calcium hydroxide with the oxidized oil, (3) continuing the oxidation for a time suflicient to incorporate from about 0.05% to 0.5 by weight, of metal into the oxidized oil, (4) reacting the product from step 3 with from about 5% to about 20%, by weight, based on the weight of oil charged in step 1, of phosphorus pentasulfide, at a temperature of from about 75 C. to about C., to form a phosphorus-, sulfurand calcium-containing product, (5 providing a mixture of the reaction product from step 4 with from about 2% to about 25%, based on the Weight of the oil charged in step 1, of zinc hydroxide, and water, at a temperature below the boiling point of Water, (6) substantially completely dehydrating the mixture formed in step 5 and (7) subjecting the dehydrated mixture to filtration to remove insolubles therefrom.

20. A mineral lubricating oil containing a minor amount, sufiicient to improve the detergent'character thereof, of an oil-soluble, phosphorus-, sulfurand calcium-containing oxidized oil reaction product produced by the method which comprises the steps of (1) forming a mixture comprising (a) a petroleum oil having a molecular weight of from about 600 to about 1000 and (b) from about 0.5% to about 25% of calcium hydroxide, (2) contacting said mixture with an oxidizing gas, at a temperature of from about 125 C. to about 325 C., to effect oxidation of said oil and reaction of said calcium hydroxide with the oxidized oil, (3) continuing the oxidation for a time sufiicient to incorporate from about 0.05% to about 0.5%, by weight, of calcium into the oxidized oil, (4) reacting the product from step 3 with from about 5% to about by weight, based on the weight of oil charged in step 1, of phosphorus heptas'ulfide, at a temperature of from about 75 C. to about 150 C., to form a phosphorus-, sulfurand calcium-containing product, (5) providing a mixtureof the reaction product from step 4 with from about 2% to about by weight, based on the weight of oil charged in step 1, of calcium hydroxide, and water, at a temperature below the boiling point of water, (6) substantially completely dehydrating the mixture formed in step 5 and (7) subjecting the dehydrated mixture to filtration to remove insolubles therefrom.

21. A mineral lubricating oil containing a minor amount, sufiicient to improve the detergent character thereof, of an oil-soluble, phosphorus-,sulfurand calciumcontaining oxidized oil reaction product produced by the method which comprises the steps of (1) forming a mixture comprising (a) a petroleum oil having a molecular weight of from about 600 to about 1000 and (b) from about 0.5% to about 25% of calcium hydroxide, (2) contacting said mixture with an oxidizing gas, at a tempera ture of from about 125 C. to about 325 C., to effect oxidation of said oil and reaction of said calcium hydroxide With the oxidized oil, (3) continuing the oxidation for a time sufficient to incorporate from about 0.05% to about 0.5%, by weight, of calcium into the oxidized oil, (4) reacting the product of step 3 with from about 5% to about 20%, by weight, based on the weight of the oil charged in step 1, of phosphorus trisulfide, at a temperature of from about C. to about C., to form a phosphorus-, sulfurand calcium-containing product, (5) providing a mixture of the reaction product from step 4 with from about 2% to' about 25 based onthe weight of the oil charged in step 1, of calcium hydroxide and water, at a temperature below the boiling point of water, (6) substantially completely dehydrating the mixture formed in step 5 and (7) subjecting the dehydrated mixture to filtration to remove insolubles therefrom.

22. A mineral lubricating oil containing a minor amount, sufficient to improve the detergent character thereof, of an oil-soluble, phosphorus-, sulfurand calcium-containing reaction product produced by the method which comprises the steps of (1) forming a mixture comprising (a) a petroleum oil having a molecular weight of from about 600 to about 1000 and (b) from about 0.5% to about 25 of calcium hydroxide, (2) contacting said mixture with an oxidizing gas, at a temperature of from about 125 C. to about 325 C., to effect oxidation of said oil and reaction of said calcium hydroxide with the oxidized oil, (3) continuing the oxidation for a. time sulficient to incorporate from about 0.05% to about 0.5%, by weight, of calcium into the oxidized oil, (4) reacting the product of step 3 with from about 5% to about 20%, by weight, of phosphorus trisulfide and from about .05 to about 2% of sulfur, both percentages being based on the weight of oil charged in step 1, at a temperature of from about 75 C. to about C., to form a phosphorus-, sulfurand calcium-containing product, (5 providing a mixture of the reaction product from step 4 with from about 2% to about 25 based on the weight of oil charged in step 1, of calcium hydroxide, and water, at a temperature below the boiling point of water, (6) substantially completely dehydrating the mixture formed in step 5 and (7) subjecting the dehydrated mixture to filtration to remove insolubles therefrom.

References Cited in the file of this patent UNITED STATES PATENTS Musselman Apr. 22, 1947

Claims

1. AN OIL-SOLUBLE, PHOSPHORUS-, SULFUR- AND METAL-CONTAINING OXIDIZED HYDROCARBON REACTION PRODUCT PRODUCED BY THE METHOD WHICH COMPRISES THE STEP OF (1) FORMING A MIXING COMPRISING (A) A HYDROCARBON HAVING A MOLECULAR WEIGHTS OF FROM ABOUT 200 TO 1000 AND WHICH IS SELECTED FROM THE GROUP CONSISTING OF ALIPHATIC HYDROCARBONS AND AROMATIC HYDROCARBON HAVING AT LEAST ONE NUCLEAR HYDROGEN ATOM SUBSTITUTED BY AN ALIPHATIC RADICAL TO PROVIDE A TOTAL OF AT LEAST 8 ALIPHATIC RADICAL PER MOLE THEREIN, AND MIXTURES THEREOF, AND (B) FROM ABOUT 0.5% TO ABOUT 25%, BASED ON THE WEIGHT OF SAID HYDROCARBON OF A METAL HYDROXIDE, THE METAL CONSTITUENT OF WHICH IS SELECTED FROM GROUPS I AND II OF MENDELEEFF''S PERIODIC TABLE OF THE ELEMENTS (2) CONTACTING SAID MIXTURE WITH AN OXIDIZING GAS AT A TEMPERATURE OF FROM ABOPUT 125* C. TO ABOUT 325* C. TO EFFECT OXIDATION OF SAID HYDROCARBON AND REACTION OF SAID METAL HYDROXIDE WITH THE OXIDIZED HYDROCARBON, (3) CONTINUING THE OXIDATION FOR A TIME SUFFICIENT TO INCORPORATE FROM ABOUT 0.05% TO ABOUT 3.0% BY WEIGHT, OF METAL, INTO THE OXIDIZED HYDROCARBON (4) REACTING THE PRODUCT FROM STEP 3 WITH FROM ABOUT 5% TO ABOUT 20%, BY WEIGHT, BASED ON THE WEIGHT OF HYDROCARBON CHARGED IN STEP 1, OF A PHOSPHORUS SULFIDE, AT A TEMPERATURE OF FROM ABOUT 75* C. TO ABOUT 150* C., TO FORM A PHOSPHORUS-, SULFUR, AND METAL-CONTAINING PRODUCT, (5) PROVIDING A MIXTURE OF THE REACTION PRODUCT FROM STEP 4 WITH FROM ABOUT 2% TO ABOUT 25% BY WEIGHT BASED ON THE HYDROCARBON CHARGED IN STEP 1, OF A METAL HYDROXIDE, THE METAL CONSTITUENT OF WHICH IS SELECTED FROM GROUPS I AND II OF MENDELEEF''S PERIODIC TABLE OF THE ELEMENTS, AND WATER, AT A TEMPERATURE BELOW THE BOILING POINT OF WATER, (6) SUBSTANTIALLY COMPLETELY DEHYDRATING THE MIXTURE FORMED IN STEP 5 AND (7) SUBJECTING THE DEHYDRATED MIXTURE OF FILTRATION TO REMOVE INSOLUBLES THEREFROM.