US2738344A - Stabilization of sulfurized hydrocarbons - Google Patents

Description

March 13, 1956 D, T. ROGERS ET AL 2,738,344

STABILIZATION OF SULFURIZED HYDROCARBONS Filed Sept. 22, 1951 LOT OF COPPER Vs. I-IospI-Iozus CloNTEN-rs F'oa dumzous Oxma- TREATED Suwumzan HYDIZOCAIZbONS oppaw. In IzoDuc-r, WEIGHT "/0 r- !\7 (P o o 0 I l l l l l 0 L0 2.0 5.0 4.0 HQfiPl-KQRLJS m szooucr, WEIGHT 7:

13 Zw rib. T. 20 QIQEQ 1 ms zawgfgi fln-vmbors filbbornag United States Patent STABILIZATION 0F SULFURIZED HYDROCARBONS Dilworth T. Rogers, Summit, and John P. McDermott,

Roselle, N. J., assignors to Esso Research and Eng:- neering Company, a corporation of Delaware Application September 22, 1951, Serial No. 247,808

7 Claims. (Cl. 260-139) The present invention is related to an improved method for preparing sulfurized hydrocarbons. More specifically, it is concerned with a treating process for preparing sulfurcontaining hydrocarbons having improved product quality.

Sulfurized hydrocarbons prepared, for example, by treatment of hydrocarbons with elemental sulfur or reactive sulfur compounds, such as sulfur halides, sulfides of phosphorus, and the like, are extremely valuable additives for various hydrocarbon products. They are particularly useful as anti-oxidants, detergents, and corrosion inhibitors for various types of lubricants. The sulfurization step, however, frequently results in the formation of products that are unstable with respect to HzS evolution on storage, that may be corrosive to certain types of metals, or that have poor color. It is known to neutralize the acidity in the sulfurized materials bytreatment with certain basic reagents, particularly metal-containing reagents, resulting in the formation of compounds containing a metal component. Such treatment does not always achieve the desired stabilization and, in addition, is undesirable when the finished product is to be ashless in nature.

It is a principal object of the present invention to disclose a novel, inexpensive process for treating unstable and corrosive sulfurized hydrocarbons whereby substantial improvements in product quality are obtained. This invention also teaches a method for treating such hydrocarbons with a metal compound whereby the amount of metal constituent introduced into the finished product is controlled.

In accordance with the present invention, the reaction product of sulfur or of a reactive sulfur compound with an essentially hydrocarbon material is treated with a minor amount of cuprous oxide at an elevated temperature under conditions whereby the product is stabilized. The treating process is preferably carried out with a sulfurized hydrocarbon containing no or only a relatively small amount of phosphorus since it has been found that the substantially phosphorus-free sulfurized hydrocarbons do not retain chemically-combined copper as a result of the treatment.

The mechanism whereby the reaction products are improved by treatment with cuprous oxide is not entirely understood, particularly since cupric oxide is substantially inefiective for producing the desired results. Possibly since cuprous oxide is a reducing agent and cupric oxide is an oxidizing agent, only the former compound will effect reaction with or conversion of the types of unstable compounds present.

The cuprous oxide is preferably added to the material to be treated as a finely divided solid, such as powder, pellets, or the like. The oxide and sulfurized hydrocarbon are preferably stirred during thecontacting step at an elevated temperature for a time sufiicient to effect the improvements desired. The treating temperature should be above about 150 F. and below about 450 F. to 500 F. in order to eifect substantial improvements and yetprevent substantial decomposition of the sulfurized hydrocarbons. A preferable temperature range is about 200 to 400 F.

The amount of cuprous oxide employed will vary depending on the contact time and treating temperature. Amounts below about 0.5 wt. percent, based on the material being treated, will generally require rather severe treating conditions, whereas it is generally uneconomical to use amounts much higher than about 20 to 25 wt. percent. Preferred amounts are in the range of about 1 to 15% by weight. Treating times are generally not critical and will depend to a large extent on the type of stock being treated, the amount of cuprous oxide employed, and the treating temperature. Contact times may vary from about five minutes up to about ten hours or more, preferably in the range of about 0.5 to 5 hours.

After the treatment has been carried out for the desired length of time, the solid material is removed by filtration of the hydrocarbon derivative through a diatomaceous earth such as Hy-Flo or through other equivalent filtering or separation means to recover a substantially solid-free material. The resulting stabilized product is then ready for use as such or may be further reacted with various materials to produce derivatives having certain desired characteristics.

The term sulfurized hydrocarbon as used herein refers to materials prepared by reaction of an essentially hydrocarbon material with a reactive sulfur-containing material including elemental sulfur, elemental sulfur and phosphorus mixtures, a sulfide of phosphorus such as P285, P453, P487, ormixtures thereof, or with sulfur halides such as sulfur monochloride, sulfur dichloride, mixtures of these materials and the like. If desired, the material may be reacted with sulfur in a first step and subsequently reacted with a sulfide of phosphorus before the treatment with cuprous oxide is carried out. The sulfurized hydrocarbon preferably comprises at least 1.0 weight percent of chemically combined sulfur.

The essentially hydrocarbon materials used in preparing the sulfurized hydrocarbon may be paraflins, olefins or olefin polymers, diolefins, acetylenes, aromatics or alkyl aromatics, cyclic aliphatics, petroleum fractions such as lubricating oil fractions, petrolatums, waxes, cracked cycle stocks, condensation products of petroleum fractions, solvent extracts of petroleum fractions, and the like. Bright stock residuums and lubricating oil distillates are particularly desirable hydrocarbons to be employed. The foregoing hydrocarbons may be condensed, usually through first halogenating the hydrocarbon, with aromatic hydrocarbons in the presence of anhydrous inorganic halides such as aluminum chloride, zinc chloride, etc.

As examples of mono-olefins may be mentioned isobutylene, decene, dodecene, cetene (C16), octadecene (C18), cerotene (C26), melene (C30), olefinic extracts from gasoline or gasoline itself, cracked cycle stocks and polymers thereof, cracked waxes, dehydrohalogenated chlorinated waxes, and any mixed high molecular weight alkenes obtained by cracking petroleum oils. A preferred class of olefins are those having at least 20 carbon atoms per molecule, of which from about 12 to about 18 carbon atoms, and preferably at least 15 carbon atoms, are in a long chain. Such olefins may be obtained by the dehydrogenation of paraffin waxes, by the dehydrohalogenation of long chain alkyl halides, by the synthesis of hydro carbons from C0 and H2, by the dehydration of alcohols, etc.

Another class of suitable olefinic materials are the terpenes such as dipentene and the like. The monoolefin polymers, in which the molecular weight ranges from to 50,000, preferably from about 250 to about 10,000 may also be used. These polymers may be obtained by the polymerization of low molecular weight mono-olefinic hydrocarbons, such as ethylene, propylene, butylene, isobutylene, normal and isoamylenes, or hexenes, or by the copolymerization of any combination of the above mono-olefinic materials.

Diolefins which may be employed include well known materials such as butadiene, isoprene, chloroprene, cyclopentadiene, 2,3-dimethylbutadiene, pentadiene-1,3, hexadiene-2,4, terpenes and the like. Acetylene and substituted acetylenes may similarly be employed.

Another class of unsaturated hydrocarbon materials which may be advantageously employed in the preparation of the additives of this invention are high molecular weight copolymers of low molecular weight mono-olefins and diolefins. The copolymer is prepared by controlled copolymerization of a low molecular weight olefin and a non-aromatic hydrocarbon having the general formula CnHZn-z, in which x is 2 or a multiple of 2, in the presence of a catalyst of the Friedel-Crafts or peroxide type. The low molecular weight olefin is preferably an isoolefin or a tertiary olefin, preferably one having less than 7 carbon atoms per molecule. Examples of such olefins are isobutylene, Z-methyIbutcne-l, Z-ethylbutene-l, secondary and tertiary base amylenes, hexylenes, and the like. Examples of the non-aromatic hydrocarbons of the above formula which may be used are the conjugated diolefins listed in the preceding paragraph, diolefins such as 1,4-hexadiene, in which the double bond is not conjugated, as well as the acetylcnes. The copolymerization is preferably carried out in the presence of aluminum chloride, boron fluoride, or benzoyl peroxide, and the copolymer is preferably one having a molecular weight of about 1,000 to 30,000. Specifically preferred limits are between about 1,500 and 20,000 molecular weight.

Another class of hydrocarbons which may be employed in a similar manner are aromatic hydrocarbons, such as benzene, naphthalene, anthracene, toluene, xylene, diphenyl, and the like, as well as aromatic hydrocarbons having alkyl substituents and aliphatic hydrocarbons having aryl substitutents.

A still further class of hydrocarbons which may be employed in the reaction are condensation products of halogenated aliphatic hydrocarbons with an aromatic compound, produced by condensation in the presence of aluminum chloride or other Friedel-Crafts type catalyst. The halogenated aliphatic hydrocarbon is preferably a halogenated long chain paraffin hydrocarbon having more than 8 carbon atoms, such as parafiin wax, petrolatum, ozocerite wax, etc. High viscosity parafiin oils, particularly heavy residual oil which has been treated with chemicals or extracted with propane or other solvents for the removal of asphalts, may be employed. The aromatic constituent may be naphthalene, fluorene, phenanthrene, anthracene, coal tar residues, and the like.

Another type of hydrocarbon material which may be similarly employed is a resin-like oil which has a molecular weight of from about 1,000 to 2,000 or higher, obtained preferably from a parafiinic oil which has been dewaxed and which is then treated with a liquified normally gaseous hydrocarbon, e. g. propane, to precipitate a heavy propane-insoluble fraction. The latter is a substantially wax-free and asphalt-free product having a Saybolt viscosity at 210 F. of about 1,000 to about 4,000 seconds or more.

The reaction of the hydrocarbon material with sulfur or reactive sulfur-containing materials may be conducted by procedures well known in the art. For example, the hydrocarbon may be treated with from about 1 to by weight of free sulfur or of compounds of sulfur and phosphorus for 2 to 15 hours or more at a temperature above 200 F. and up to about 500 F. The resulting product, which will usually contain above 1 to 2 weight percent of chemically combined sulfur, may then be filtered and blown with nitrogen or otherwise treated to remove hydrogen sulfide or other reaction gases. The

CLK

4 material may then be treated with cuprous oxide in accordance with the procedure outlined above.

A particularly desirable procedure is to react hydrocarbons, particularly unsaturated hydrocarbons, with a sulfur halide followed preferably by a dehydrohalogenation step, which may be accomplished by treating the sulfurized and halogenated hydrocarbon product with phenol or other hydroxy compound. Such a method is described in the Winning and Rogers U. S. Patent 2,422,275. It is preferred that the sulfurized hydrocarbon be substantially free of halogen before conducting the cuprous oxide treating step.

The hydrocarbon material or one of the sulfurized hydrocarbons prepared by the above procedures may be sulfurized by treatment with a sulfide of phosphorous at an elevated temperature such as in the range of about 300 to 550 F., generally using about 1 to 3 molecular proportions of hydrocarbon to at least /3 molecular proportion of phosphorus sulfide. Usually the reaction is carried out in a non-oxidizing atmosphere, such as an atmosphere of nitrogen above the reaction mixture. An amount of phosphorus sulfide is usually used that will completely react with the hydrocarbon under the conditions used. Reaction times in the range of about 2 to 10 hours will generally be required, although the reaction time is not critical. The resulting reaction product may be further treated by blowing with steam, alcohol, or the like to improve odor before treatment with the cuprous oxide, although treatment with the oxide will generally be sufficient to improve odor without this intermediate step. Other sulfurization procedures known to the art may be used.

Cuprous oxide treatment effects substantial improvements in sulfurized hydrocarbons obtained by various sulfurization methods. However, phospho-sulfurization introduces acidic compounds that are quite reactive with the cuprous oxide, resulting in the formation of organocopper compounds which are ash-forming in nature. It has been found on the other hand that sulfurized hydrocarbons containing less than about 1 wt. percent phosphorus, preferably below 0.5 Wt. percent phosphorus. will have extremely low copper contents such as below 0.5 to 0.2 wt. percent copper. In addition, improvements with respect to stability, odor, color, and the like are sometimes greater in the case of materials containing relatively small amounts of phosphorus. sulfurized hydrocarbons containing no phosphorus have been found to be substantially entirely free of copper, even after treatment under rather severe conditions with cuprous oxide. Therefore, cuprous oxide treatment of substantially phosphorus-free materials or those containing only a limited amount of phosphorus is preferred, particularly when an ashless detergent is desired.

The additives of the present invention are particularly suitable for use in lubricating oils, and when used for such purpose must be sufiiciently soluble to accomplish the desired improvements in the finished composition. Proportions of about 0.001 to about 20.0 wt. percent, generally not above about 10%, of the treated sulfurized hydrocarbon will generally be used in the lubricating oil. Obviously the proportions will vary depending somewhat on the nature of the additive and the specific purpose which the lubricant is to serve in a given case. For commercial purposes it is convenient to prepare concentrated oil solutions in which the amount of additive in the composition ranges from about 20 to 50% by weight, and thus transport and store them in such form. Since the concentrates may be stored for extended periods of time, the treating step of the present invention is quite beneficial from the standpoint of preparing a stable and more saleable product.

Below are given detailed descriptions of preparations of sulfurized hydrocarbons prepared and treated in accordance with the present invention. It is to be understood that the examples are given as illustrations only and are not to be construed as limiting the scope of the invention in any way.

Example 1 Product A was prepared by combining and heating a mixture of 1000 g. of a Mid-Continent lubricating oil having a Saybolt viscosity at 210 F. of 56 seconds and 150 g. (15.0 weight percent) of sulfur at a temperature of about 420 F. The sulfurization step was continued for 6 hours with rapid stirring and nitrogen blowing. After cooling to about 212 F. the product was filtered through Hy-Flo and a dark, viscous concentrate was obtained which contained 3.7 weight percent sulfur.

Product B was prepared by treating 270 g. of Product A with 30 g. 11.1 weight percent) of powdered cuprous oxide for 3 hours at a temperature of about 390 F. The mixture was stirred rapidly and blown with nitrogen during the reaction period. Solids were removed from the product by filtration through Hy-Flo. The product contained about 0.04 weight percent copper.

Product C was prepared in the same way as Product B except that 30 g. (11.1 weight percent) of cupric oxide were employed in place of cuprous oxide. The filtered product contained 0.02 weight percent copper.

Each of the Products B and C was blended in a lubricating oil base consisting of a solvent extracted Mid- Continent distillate of SAE 10 grade. Each blend contained 1.0 weight percent of the active ingredient in the oil.

modification of the C. R. C. method 11-16-445. This method comprises immersing a polished metallic copper strip in the oil blend to be tested for 3 hours at 212 F. and noting the extent of staining. Numerical ratings from 1 to 10 denote discoloration ranging from no stain to a black surface film, respectively. The results of the tests are given below:

Product Used in Oil: Copper strip rating A (no treatment) 10 B (CuaO treatment) 2 4 These blends and a sample of the unblended base. oil were submitted to a copper, strip test which was a C (CuO treatment) 10 It is noted that cupric oxide is inelfective as a treating agent for reducing the corrosiveness of the sulfurized hydrocarbon whereas cuprous oxide under the conditions used was extremely effective.

Example ll Product D was prepared as follows: 56 pounds of sulfur, 1.87 pounds of mercaptobenzothiazole and 0.93 pound of diphenyl guanidine were placed in a glass lined reactor with reflux condenser and heated to 300 F. 131 pounds of commercial dipentene were added gradually over a period of about one hour at 300 F. The temperature was then raised to 350 F. and held at this point for 6 hours, after which the product was cooled. Upon analysis it was found to contain 23.0 Weight percent chemically combined sulfur. Three portions of the resulting sulfurized dipentene were treated respectively, with 0.5, 1.0, and 2.0 weight percent, based on the material being treated, of cuprous oxide. Each treatment was carried out at a temperature of about 185 to 200 F. for 10 minutes, following Which'the products were filtered through Hy-Flo. The storage stability of the untreated sulfurized dipentene and of each of the treated products was determined as follows:

Four-ounce bottles were filled about /1. full with the product, stoppered with tin foil-covered corks, and stored for 20 hours at a temperature of 140 F. The stoppers were then removed, and a filter paper that had been dipped in saturated lead acetate solution just prior to the test was immediately placed over the bottle opening being held in place by means of a watch glass. After five minutes the test papers were removed and allowed to dry, followed by rating against a set of standards in which zero represents no stain and 10 represents a heavy Iblack metallic stain. The results of this test are shown elow:

C1120 Treatment of Sulfurized Dipentene, Weight Percent H25 Rating H ONOQO Substantial improvements in odor and storage stability were obtained by treatment with small amounts of cuprous oxide. 0.5 weight percent cuprous oxide was not suflicient to produce an entirely stable product under the temperature and time conditions employed.

Example III Product E, consisting of sulfurized di-isobutylene, was prepared as follows:

To 2520 g. of di-isobutylene contained in a 4-necked, 5 liter flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel, were added 1050 g. of sulfur monochloride over a period of about 1% hours. The initial temperature was 78 F., but upon completion of the sulfur halide addition the reaction temperature had risen to F. The reaction mixture was then heated at this temperature for an additional 30 minutes. 138 g. of phenol were then added, and after the phenol dissolved, the flask was equipped with a downward condenser and the temperature raised to 220 F. Vacuum was gradually applied, and the temperature maintained at 220 F. for 6 hours, after which distillation had practically ceased. The resulting product was dissolved in an equal volume of oil, which concentrate contained 13.0 percent S and essentially no chlorine.

Product F was prepared by treating 500 g. of Product E with 25 g. (5 weight percent) of cuprous oxide at 212 F. with stirring. The material was then soaked at a temperature of about 212 F.-230 F. for 2% hours, followed by filtration through Hy-Flo. The final product was a clear, light red concentrate. Products E and F were subjected to various laboratory tests. Sunlight stability was determined by storing products in clear glass bottles under conditions whereby they were contacted by sunlight. Copper strip ratings were determined by the method described in Example I. The results of these tests are shown as follows:

Product E F Sulfur Content, Weight Percent 13.0 12. 9 Copper Content, Weight Percent--- 0 0. 01 Sunlight Stability, Days to Form 11:17 4 35+ Color, Robinson 1% 7 Copper Strip Rating 10 2 Product G was prepared as follows: A 500 g. charge of Product E contained in a 3 necked, 1 liter flask equipped with a stirrer, thermometer, and reflux condenser was heated to 203 F., followed by the addition of 50 g. of P483. The temperature was then maintained at 203212 F. for 2 hours with rapid stirring. At this stage, a practically clear, reddish liquid was obtained with only a very small amount of insoluble residue. The product was then steam distilled for one hour, after which it was poured into a separatory funnel. The organic layer was withdrawn, blown with nitrogen for 20 minutes at 212-221 F. to remove water, after which it was dissolved in an equal volume of light mineral oil to give a 50% concentrate.

Product H was prepared as follows: 300 g. of Product G was heated to about 176 F., after which 6.0 g. (2 weight percent) of cuprous oxide were added with rapid stirring. After stirring for 2 hours at 221 F., 2% of acid-treated contact clay was added, followed by filtration through Hy-Flo. A dark red, practically odorless product was obtained, which upon analysis was found to contain 0.54% copper, 1.4% phosphorus, and 13.4% sulfur.

Product I was prepared in the same manner as described in the preparation of Product G using 500 g. of Product E and 50 g. of P255.

Product K was prepared in the same manner as described in connection with the preparation of Product H using 300 g. of Product I and 6.0 g. (2 weight percent) of cuprous oxide. A very dark red, practically odorless material was obtained which, upon analysis, was found to contain 0.08% copper, 0.33% phosphorus, and 14.7% sulfur.

Product L was prepared in the following manner: A lubricating oil bright stock derived from a Mid- Coutincnt crude, prepared by deasphalting, dewaxing, acid and clay treating the residuum, and having about 252 seconds viscosity (Saybolt) at 210 F. was treated with 17.5 weight percent of P255 for 7 hours at a ternperature of 400 F. The product was then filtered.

Product M was prepared by treating a portion of roduct L with weight percent of commercial dipentene for l hour at 380 F. temperature in order to obtain the dipentene derivative thereof. The resulting derivative was then heated to about 360 F. with 5 weight percent CuzO for 2 /2 hours with rapid stirring. The filtered product was clear, dark red, and viscous, and, upon analysis, was found to contain 2.7 weight percent phosphorus, 4.6 weight percent sulfur, and 5.7 weight percent copper.

Product N was prepared by treating a portion of Product L with 5 weight percent of cuprous oxide at about 360 F. for 2 hours with rapid stirring. The filtered product contained 2.9 weight percent phosphorus, 5.2 weight percent sulfur, and 2.9 weight percent copper.

H ratings were determined on the above products in accordance with the procedure of Example Hi. The results are shown below:

H25 rating Product tested:

Exam 1 1.2 V

The corrosion and detergcncy characteristics of the products prepared as described in the above examples were tested by laboratory bearing corrosion and Lauson engine tests on the blends of the products in various oils. The tests were conducted substantially in accordance with those described in Examples 12 and 13 of U. S. 2,529,303 to Mcfiermott. The bearing corrosion test was carried out using a blend containing 0.25 weight percent of the additive in a solvent extracted, Mid-Continent paraflinic lubricating oil of SAE 20 grade, the test being carried out on the base oil as such also. 0.5 weight percent of the products were blended in a solvent extracted Mid- Continent SAEl0 grade oil and tested along with the base oil per se in 20 hour Lauson engine runs, the engine being operated at 290 F. jacket temperature and 300 F. oil temperature. hc results of these tests are shown below:

Some improvement in bearing corrosion and detergency characteristics were obtained by the cuprous oxide treatment.

Example VI The copper and phosphorus contents of the various CuzO-treated products prepared as shown above are plotted in Figure 1. Chemically combined copper was not present in the treated products derived from substantially phosphorus-free sulfurized hydrocarbons containing up to about 15 weight per cent sulfur whereas the copper content showed a sharp increase when the material treated contained above 0.15-1.0 weight per cent phosphorus. The substantially copper-free materials are particularly useful as ashless detergents in aviation engine lubricating oils and the like.

The products of the present invention may be employed in ordinary hydrocarbon lubricating oils, the heavy duty type of lubricants along with other additives of the conventional type, and with various synthetic lubricants such as those prepared by polymerization of olefins, by the reaction of oxides of carbon with hydrogen, or by other means. The conventional synthetic oils of the ester, poly-ester and poly-ether types may also be used alone or in combination with mineral lubricants as base oils. The lubricating oils may vary considerably in viscosity and other properties, depending on the use for which they are desired, but they usually range from about 40 to seconds viscosity (Saybolt) at 210 F.

Other agents such as dyes, pour depressors, organometallic compounds, sludge disperser, viscosity index improvers, and the like may be used along with the additives of the present invention in compounding lubricants. In addition to being employed in lubricants, the additives of the present invention may also be used in motor fuels, hydraulic fluids, cutting oils, turbine oils, fuel oils, transformer oils, and in other petroleum products susceptible to oxidation. They may also be used in gear lubricants and greases.

What is claimed is:

1. A method for preparing improved sulfur-containing hydrocarbon products which comprises reacting a hydrocarbon material with at least one agent selected from the group consisting of sulfur, sulfides of phosphorus and sulfur halides to form a sulfurized hydrocarbon containing at least 1.0 weight percent of chemically combined sulfur and less than about 1.0 weight percent phosphorus, treating said sulfurized hydrocarbon with cuprous oxide in an amount in the range of about 0.5 to 25% by weight, based on the sulfurized hydrocarbon, at a temperature in the range of about 150 to 500 F. for a period of time in the range of about 5 minutes to 10 hours, removing solids from the cuprous oxide-treated sulfurized hydrocarbon, and recovering a substantially copper-free, sulfurcontaining hydrocarbon product.

2. The method as in claim 1 wherein said product is formed by reacting a mineral lubricant base stock with sulfur.

3. The method as in claim 1 wherein said product is formed by reacting a mineral lubricant base stock with a sulfide of'phosphorus.

4. The method as in claim 1 wherein said product is formed by reacting a terpene with sulfur.

5. The method as in claim 1 wherein said product is a substantially halogen-free reaction product of an unsaturated hydrocarbon and a sulfur halide.

6. The method as in claim 5 wherein said dehalogenated reaction prodct is further reacted with a sulfide of phosphorus before treating with said oxide.

7. A method for preparing improved sulfur-containing hydrocarbon products which comprises reacting a hydrocarbon material with at least one agent selected from the group consisting of sulfur, sulfides of phosphorus and sulfur halides to form a sulfurized hydrocarbon containing at least 1.0 weight percent of chemically combined sulfur and less than about 0.5 weight percent phosphorus, treating said sulfurized hydrocarbon with cuprous oxide in an amount in the range of about 1 to 15% by weight, based on the sulfurized hydrocarbon, at a temperature in the range of about 200 to 400 F. for a period of time in the range of about 0.5 to 5 hours, removing solids from the cuprous oxide-treated sulfurized hydrocarbon, and recovering a substantially copper-free, sulfur-containing hydrocarbon product.

References Cited in the file of this patent UNITED STATES PATENTS 2,080,365 von Fuchs May 11, 1937 2,174,810 von Fuchs Oct. 3, 1939 2,422,275 Winning et a1. June 17, 1947 2,489,249 Adelson Nov. 29, 1949 2,560,547 Bartleson July 17, 1951

Claims (1)

1. A METHOD FOR PREPARING IMPROVED SULFUR-CONTAINING HYDROCARBON PRODUCTS WHICH COMPRISES REACTING A HYDROCARBON MATERIAL WITH AT LEAST ONE AGENT SELECTED FROM THE GROUP CONSISTING OF SULFUR, SULFIDES OF PHOSPHOROUS AND SULFUR HALIDES TO FORM A SULFURIZED HYDROCARBON CONTAINING AT LEAST 1.0 WEIGHT PERCENT OF CHEMICALLY COMBINED SULFUR AND LESS THAN ABOUT 1.0 WEIGHT PERCENT PHOSPHOROUS, TREATING SAID SULFURIZED HYDROCARBON WITH CUPROUS OXIDE IN AN AMOUNT IN THE RANGE OF ABOUT 0.5 TO 25% BY WEIGHT, BASED ON THE SULFURIZED HYDROCARBON WITH CUPROUS OXIDE THE RANGE OF ABOUT 150* TO 500* F. FOR A PERIOD OF TIME IN THE RANGE OF ABOUT 5 MINUTES TO 10 HOURS, REMOVING SOLIDS FROM THE CUPROUS OXIDE-TREATED SULFURIZED HYDROCARBON, AND RECOVERING A SUBSTANTIALLY COPPER-FREE, SULFURCONTAINING HYDROCARBON PRODUCT.

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