US2611766A - Process for the formation of a sulfurized halogenated aliphatic hydrocarbon - Google Patents

Description

p 1952 N. M. SCHNEIDER ETAL 2,611,766

PROCESS FOR THE FORMATION OF A SULFURIZED HALOGENATED ALIPHATIC HYDROCARBON Filed Dec. 28, 1949 ,QEAcT/o/v VESSEL 8 T SEPARATION VESSEL 8 M/X/NG VESSEL SEPARATION VESSEL. gg zf FILTER- Patented Sept. 23,1952 2:11:

rnocEss FOR THE FORMATION or A son- .-FURIZED. HALO'GENATED ALIPHATIC H-,

DROCARBON NicholasM. Schneider, Bayonne, andR-aymond M. Dean, Westfield,. N. J.,, assignors toStand 1 ard-Oil Development Company,-.a corporation of Delaware Applicationllecember 28, 1-949, Serial N0.: I35:1 16

' 4 Claims. (01. 260-439") "T i DV I HO 1 M .0 lubricatin O l d-'7 ditives. Particularlygit relates to an improved process for the manufacture of lubricating oil additives which have the characteristic of .imparting desirable qualities to lubricating oils with which they are blended. More particularly, the invention relates to animproved process forthe preparation of ,sulfurized halogenated aliphatic materials.

In U. S. Patent 2,124,598 issued July 26, 1938, there is disclosed a lubricating oil additive which is made by incorporating sulfur into halogenated aliphatic compounds. The additive materials disclosed in this patent have the desirable characteristics of imparting .to a lubricating oil blend containing them resistance to extreme pressures under high rates of shear.

These lubricating oil additive materials have been made heretofore by combining with the desired halogenated aliphatic material, such as high molecular weight hydrocarbons, sulfur in the form of sodium hydrosulflde, elemental .sulfurand the like. lngeneralrthe process has involved dissolving the halogenated material in a solvent such as an alcohol and admixing the sulfur-containing material therewith. After the de-' sired period of time has elapsed and the sulfurization hasreached the desired stage, the mixture is allowed to separate into its component layers by gravity separation. The top layer, being composed of the major proportion of the solvent,is withdrawn and recycled for reuse in the process. The bottom, or brine, layenfis withdrawn and may be discarded, or approximately of the alcoholis recovered by distillation.

The middle or productlayerwhich contains the sulfurized halogenated hydrocarbon material also contains entrained-or dissolved therein a minor proportion of the solvent along with extraneous matter such as reaction sludge, sediment and so forth. This entrained or dissolved solvent has normally been removed by a process of vacuum stripping. Temperatures in the neighborhood of 200 F. to 255 .F. are used at a-va'cuum of about 18 to-26 inches of mercury." .3

After the stripping step is cormial'eted andthe entrained solvent has been removed the product is then passed through a filtering medium for re- 7 for an extended period of time deteriorates slightly in its ability to impart the above Vmentioned desirable characteristics to the lubricating oil.

Also the vacuum stripping has been done in the reactor vessel itself, thus tying up the-vessel for an undesirably long period soiJiume.

In the improved process which is the subiect of this invention the above mentioned disadvantages are eliminated. The vacuum distilla f tion stepis completely done awavw'ith and sub-j stituted thereforis a process for the separation of the entrained or entrapped solvent by a si-m-' ple selective solvationprocess. In'thisnew p1 ce'dure the productlayer referred to above',f that is, that layer containing the sulfurizedihalogen ated hydrocarbon along with a minor amount of entrained solvent isa'dmixed with a'liquidin which the solvent used is solublelbut in which the product is not soluble. It is to be understood, of course, that the particular liquid chosen will depend upon the particular. solvent'used in the reaction stage ofthe process; When thfesolventusedis an alcohol such as isopropyl alcohol the solubilizing liquid may be .water. i

The mixture of the product layer iandjtheladded liquid is agitated, for a period of time .suflicient to completely dissolve the solvent in .theliquid and the mixture is then allowed: to separateusing a simple gravity separation. The top-layer, which ordinarily will contain the dissolved sol; vent, is withdrawn and .the bottom layer which contains the product, .freeirom all but traces of entrained solvent, .is airblown toremove traces of ,solubilizing liquid and solvent and is then passed through afilter medium for-theremoval of extraneous material s. v If desired, va,filtering agent such as diatomaceous earthmay-be. added prior to the-filtering step. :2 ,1

In the drawing there is illustratedan apparatus suit-ablefor carrying out one embodimentrof the invention. .It is to be realized, of course, hat the-apparatus as. shown is not limiting, in any respect since other -:means .ofcarrying outnthe process of this. invention will beevidentsto .those skilled in the art. In this particulanembodiment a-mixture of chlorinated; wax andchlorine ated kerosene is sulfurized using elementalsulfur and sodium hydrosulfide. .Isopropyl-alcohol is used as a solvent for thewax-kerosenesmixture. The amounts of these constituents usedwilldepend uponthe product desired. I

Referring now to the drawing, numeral 2'represents ,a reaction vessel suitable for carryingout the-sulfurization of the halogenated thydrocare bon material. Through an openingsuch aspcrt 4 the, halogenatedv chlorowax chloro; kerosene mixture is added. .Howevenany of the various chlorinated hydrocarbons such as chlorinated Wax, chlorinated petrolatum, chlorinated .kero: sene, or mixtures of the above in .any desired proportion maybe added to the reaction vessel at this point. Also through port 4 the sulfurizing agent,,-elemental, sulfur and sodium hydrosulfide is added. -Sodium isulfide,q.or,,;any :rofythe polysulfidesmay be; added. to .athexreaction. yes: i

r se1;at-this-pointwhen:itsisdesiredz togusethese;in-

Any of the lower alcohols, v,

isopropyl alcohol usually being preferred, may

be used. 7 l

The mixture in the reaction vessel is agitated for the desired period of time, usually 2 to 6 hours at reflux temperature, by meansoi an agitation device such as propeller 8 which is driven by shaft l and an electric motor I2. Suitable heating means such as a steam coil, not shown, may be used to raise the temperature of the ingredients in the reaction vessel to the desired level. Preferred temperatures will be within a range of from 160 F. to 180 F. When the reaction between the sulfur compound and the halogenated hydrocarbon has proceeded to the desired point, the agitation is suspended and the contents of the reaction vessel are withdrawn through valved line l4' into a separation vessel 16. Here the mixture is allowed to separate by gravity separation. This usually requires from 15 minutes to 2 hours depending upon the constituents of the mixture; In the preferred embodiment, this separation will occur within from 15 minutes to 1 hour.

Three layers are formed on standing in separation vessel l6. The bottom layer which contains any of the excess sodium salt and any unused sulfur is withdrawn from vessel [6 through valved lines I8 and 20. Ordinarily this material is discarded. The middle or product layer which contains the sulfurized halogenated hydrocarbon material and a certain amount of the alcohol entrapped or dissolved is withdrawn through valved line l8 and introduced through valved line 22 into mixing vessel 24. The top layer, which contains the major proportion of the alcohol used is withdrawn through valved as propeller driven by shaft 32 and electric 7' motor 34, the desired amount of agitation is obtained. The temperature desired in mixing vessel may be obtained by means of a suitable heating device, such as a steam coil, not shown. Preferred temperatures are those between 70 F. and 150 F.

The mixture of water and product is agitated to insure complete solubilization of the alcohol which ordinarily will take from 15 minutes to 3 hours, depending upon type of agitation.

After the mixing is completed the contents of mixing vessel 24 are withdrawn through valved line 3-6 into separation vessel 38. Here gravity separation is allowed to occur again. The product layer freed from substantially all of the entrained solvent is removed through valved lines 40 and 42 and introduced into aeration vessel 46. The water layer containing dissolved therein substantially all of the alcohol which was entrapped by the product layer is removed through valved lines 40 and 48. I In aeration vessel 46 the product, which may contain a minor amount of entrapped water alcohol mixture is blown with air which is 'in-, troduced into the bottom of the aeration "vessel aenyec Tb... 5; f xiii '4 through valved lines 58. The blowing with the air removes any of the entrapped liquid leaving the product free and clear except for minor amounts of extraneous materials such as reaction sludge, sediments, and the like.

The product is then withdrawn from aeration vessel 46 through valved line 52 and introduced into a filtering device as shown at 54. This filtering device may be any of the various filters known to the art such as a plate and frame press, and the like. If it is desired a filter aid such as diatomaceous earth may be added to the product in the aeration vessel to aid in the filtering operation. 7 I This invention will be more completely described and moreclearly explained by'a reference to the following examples. I

A mixture of 60 parts of chlorinated kerosene (41.0% chlorine) and 40 parts of chlorinated wax (34% chlorine based on pts.) was-reacted with 3.2 parts of elemental sulfur and58.5 parts of 25% aqueous sodium hydrosulfidein the presence of parts of isopropyl alcohol as a solvent. After 3 hours at 176 F. the re-' action mixture was allowed to separate into three layers.

Four 500 milliliter portions of the middle or product layer were taken. One portion wassubjected to a vacuum distillation step. The (3113 tillation was carried out at a temperature between 215 F. and 220 F. for one half hour at 26 inches of mercury. An inspection of the product after the distillation was completed showed that it was free of alcohol. This sample was labeled Example IV.

The remaining three portions of the product', Examples I, II and III, were each agitated with milliliters of water until the alcohol was completely dissolved. The mixtures were then allowed to separate and the product layers withdrawn from the water layers. The separated product layers were then blown with air to remove any residual water-alcohol solution.

The temperatures of the water washing and air blowing steps with the settling time and-the blowing time are given in Table I belowzl TABLE I Water Washing Air Blowing Example Temp. as Temp. .Time

F. I hrs. F. hrs.

70 3 7O 2% II 100 3 100 2% m 125 s 125 2 The four examples treated as detailed' above were then tested for. per cent chlorine; per cent sulfur and viscosity at 210 F. Results are shown in Table II below?" TABLE II Inspection test data Percent Percent Percent Viscosity Example Chlorine Sulfur Gravity (S' 30.5 5.9 17.9 61.0 30.6 5.9 17.9 .61.2 30.6 an 18.0 61.2 33.5 5.8 17.8 -e1.:'

1 This sample of product was vacuum distilled at a temperature of 2l5220 F. for 0118 11811 under-g6 inches of mercury to remove excess isopropyl alcohol. J p 4.15;. j (I The data in Table II above shows that there is no differentiation in the final products of the two processes as regards to the per cent chlorine, per cent sulfur, and viscosity at 210 F., all tests agreeing within experimental error.

The materials of Examples I through IV were then tested as to their solubility in different base Oil A=a paraflinic aviation oil having a viscosity at 210 F of 76-84 S. U. S. and a viscosity index of 100.

1 Oil B=50% of a propane deasphalted phenol treated residuum from Panhandle Crude having a viscosity of 210 F. of 160-170 S. U. S. and a viscosity index of 90 with 50% of a treated and filtered paraflinic distillate having a viscosity at 100 F. of 285-295 S. U. S. and a viscosity index of 72.

1 This sample of product was vacuum distilled at a temperature of 215220.F. for one-half hour under 20 inches of mercury to remove excess isopropyl alcohol.

That the additive material manufactured according to the process of this invention is equally potent with that material made by the old process is conclusively pointed out by the data given in Table IV.

by weight of the product was blended with test Oil C and was subjected to the tests as reported below:

1 Oil C=69% of a steam refined cylinder stock from a Pennsylvania Crude having a viscosity at 210 F. of 210-225 S. U. S. with 31% of a treated paraflin distillate having a viscosity at 210 F. of 285-295 S. U. S. and a viscosity index of 72. I

I This sample of product was vacuum distilled at a temperature of 2l5220 F. for one-ha1i hour under 26 inches of mercury to remove excess isopropyl alcohol.

To summarize briefly, this invention involves an improved process for the formation of sulfurized halogenated hydrocarbon materials. In the process an expensive time-consuming vacuum stripping step is eliminated and substituted therefor is a simple procedure for accomplishing the same end, that is, removing any entrained solvent by dissolving the entrained solvent with a liquid in which it is soluble, separating the liquid-solvent mixture, and removing any minor amount of the liquid from the product by blowing with air.

What is claimed is:

1. A process for the formation of a sulfurlzed halogenated aliphatic hydrocarbon which comprises subjecting a mixture of chlorinated wax and chlorinated kerosene to the action of elemental sulfur and sodium hydrosulfide in the presence of an alcohol as a solvent in a reaction zone, allowing the reaction to proceed for the desired period of time, permitting the reaction mixture to separate into three layers, discarding the bottom brine layer, recycling the top alcohol layer to the reaction, removing the middle product layer to a mixing zone and adding thereto water, mixing said product and said added water for until the alcohol entrained with said product is dissolved, allowing said mixture to separate into two layers, a top layer and a bottom product layer, removing the top layer from said mixing zone, removing the bottom product layer to a second mixing zone, blowing the removed product layer with a gas to remove any residual solubilizing agent and solvent, removing the blown product to a filtering zone, and filtering said product to remove extraneous material.

2. A process according to claim '1 wherein the solvent used is isopropyl alcohol.

3. A process according to claim 1 where the gas used is air.

4. A process for the formation of a sulfurized halogenated aliphatic hydrocarbon having the. characteristic of imparting desirable extreme pressure resisting properties to a lubricating oil with which it is blended which comprises subjecting a mixture of chlorinated wax and chlorinated kerosene to the action of elemental sulfur and sodium hydrosulfide for from 2 to 6 hours in a reaction zone heated to a temperature of from F. to F. in the presence of isopropyl alcohol as a solvent, withdrawing the product into a settling zone, allowing the product to separate into three layers, discarding the bottom brine layer, recycling the top alcohol layer to the reaction zone, removing the middle product layer to a mixing zone and adding thereto 5 to 25 parts of Water, raising the temperature of said mixing zone to one within the range of from 70 F. to 150 F., agitating the product in said mixing zone for from A to 3 hours, withdrawing the mixture into a second separation zone, allowing the mixture to separate into two layers, a top wateralcohol layer and a bottom product layer, withdrawing said top water-alcohol layer from said separation zone, introducing said bottom product layer into a separate mixing zone, blowing said product in said second mixing zone with air heated to a temperature Within a range of from room temperature to 200 F. for from 1 to -5 hours in said second mixing zone to remove any residualwater, removing the blown product to a filtering zone, and filtering said blown product to remove extraneous material.

NICHOLAS M. SCHNEIDER. RAYMOND M. DEAN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,124,598 Turner July 26, 1938 2,192,700 Turner Jul 26, 1938

Claims (1)

1. A PROCESS FOR THE FORMATION OF A SULFURIZED HALOGENATED ALIPHATIC HYDROCARBON WHICH COMPRISES SUBJECTING A MIXTURE OF CHLORINATED WAX AND CHLORINATED KEROSENE TO THE ACTION OF ELEMENTAL SULFUR AND SODIUM HYDROSULFIDE IN THE PRESENCE OF AN ALCOHOL AS A SOLVENT IN A REACTION ZONE, ALLOWING THE REACTION TO PROCEED FOR THE DESIRED PERIOD OF TIME, PERMITTING THE REACTION MIXTURE TO SEPARATE INTO THREE LAYERS, DISCARDING THE BOTTOM BRINE LAYER, RECYCLING THE TOP ALCOHOL LAYER TO THE REACTION, REMOVING THE MIDDLE PRODDUCT LAYER TO A MIXING ZONE AND ADDING THERETO WATER, MIXING SAID PRODUCT AND SAID ADDED WATER FOR UNTIL THE ALCOHOL ENTRAINED WITH SAID PRODUCT IS DISSOLVED, ALLOWING SAID MIXTURE TO SEPARATE INTO TWO LAYERS, A TOP LAYER AND A BOTTOM PRODUCT LAYER, REMOVING THE TOP LAYER FROM SAID MIXING ZONE, REMOVING THE BOTTOM PRODUCT LAYER TO A SECOND MIXING ZONE, BLOWING THE REMOVED PRODUCT LAYER WITH A GAS TO REMOVE ANY RESIDUAL SOLUBILIZING AGENT AND SOLVENT, REMOVING THE BLOWN PRODUCT TO A FILTERING ZONE, AND FILTERING SAID PRODUCT TO REMOVE EXTRANEOUS MATERIAL.

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