US2082204A - Method of making high viscosity index lubricating oils - Google Patents

Description

June 1, 1937. E. w. GARDINER E-r AL 2,082,204

I METHOD OF vMAKING HIGH VISCOSITY INDEX LUBRICATING OILS original Filed June 11', 1934 O ,JoH/v w GREENE ARTHUR L. LVM/4N Patented June l, 1937.

UNITED STATES PATENT oFFlcE METHOD F MAKING HIGH VISCOSITY INDEX LUBRICATING OILS Elmslie W. Gardiner, Berkeley, John W. Greene,

Richmond, and Arthur L. Lyman, Berkeley,V Calif., assignors to Standard Oil Company of California, San Francisco, Calif., a corporation of Delaware' Original application June 11, 1934, Serial No. 730.064. Divided and this application March 11., 1935, Serial No. 10,478

11 Claims.

This invention relates to hydrocarbon lubricating oils which have extremely :dat viscosity-temperature curves,-that` is, whose viscosity indices (as defined, for example, by Dean and Davis in Chemical and Metallurgical Engineering,

l1929, vol. 36, page 618) are extremely high. 'I'he invention also relates to processes for producing hydrocarbon lubricating oils which possess this desired property.

This application is a division of our co-pendlng application Serial No. 730,064, iiled June 11, 1934, which .related more particularly tothe production of high viscosity index 'oils of substantially'the same molecular weight range as `that of the initial hydrocarbons from which they are prepared; the present divisional application relates most particularly to the production of high viscosity index oils of substantially higher molecular weight range than that ofthe hydro- Yably 'higher viscosity indices than those of the most superior naturally occurring oils, and to provide suitable methods of producing them. It is another purpose of the invention to provide lubricating oils of such high viscosity indices that very considerable amounts of low viscosity index oils may be blended or mixed therewith without lowering the viscosity index of the blendor mix l below those of the most superior naturallyoccur- Aring oils.

We have found that the viscosity indexof the hydrocarbons or series of hydrocarbons in the lubricating oil range of boiling points increases as the structure of the hydrocarbon molecules dices far higher than those of the most superior parailine base lubricating oils known.

It is a purpose of the invention to provide hydrocarbon lubricating oils whose molecular structure approaches that of the normal straight chain paraiiines and whose viscosity indices approach those of the normal straight chain parafnes themselves, but whose uidity is retained to relatively low temperatures and whose Viscosity and boiling points may be of any desired range.

The oils of our invention are produced, generally, by dehydrogenating essentially saturated hydrocarbons of the normal straight chain series,

for example, the parafline waxes, to form olenes and dioleflnes, and, if-desirable, polymerizing the produced olenes and dioleflnes, wholly or in part, to form higher average molecular weight hydrocarbons of any desiredvolatility or viscosity range. 'I'he dehydrogenated parailines (oleiines and diolenes) have the same molecular structure, so far as length of chain is concerned, as the saturated hydrocarbons from which they are obtained, and moreover, the product-is liquid at ordinary temperatures. wholly or in part, branched chains may b e introduced, but, due to the length of chain in the hydrocarbons polymerized, all such branched v'chains in the product are of great length, however far polymerization may be allowed to progress. The produced oils are liquid relatively low temperatures, and possess extremely high viscosity indices, as is exemplified below.

Dehydrogenation of the saturated straight chain hydrocarbons may suitably bebrought about by chlorination, followed-by dechlorination and the evolution of hydrochloric acid, the latter step taking place in the presence of a dechlorination catalyst which may also be a polymerizationL catalyst, if products of high viscosity are desired.

Although the process as described below is exemplied by the use of paramne waxes as saturated straight chain hydrocarbons, it will be apparent that the benets of the invention may be obtained by the use of other hydrocarbon materials, and that the more nearly the original saturated material approaches the single, normal straight chain in molecular structure the greater will be the benefits obtained in the practice of the process.

In the practice of the process:

-Paramne wax (for example, crude scale wax, match wax, Parawax, etc.)` is chlorinated by direct contact with'chlorine at temperatures of 130 to 210 F. or slightly above. Between these Upon polymerization,

temperatures the rapidity and degree of chlorination of the wax increases with increasing temperature; at temperatures of 250 F. or higher, however, decomposition of part of the chlorparaffines takes place, and hence are to be avoided. chlorination catalysts, such as traces of iodine,v may be used, but are generally not necessary. Emcient contacting of gas and liquid obviously vincreases the rate of chlorination.

In the chlorination step, chlorination of all of the parafllne hydrocarbons in one operation is impractical, and even undesirable. Thus it has been found that as the degree of chlorination increases, the proportions of diand tri-chlor parafnes increase, with respect to monochlorl paraines; moreover, as the proportions of diand higher chl'or derivatives increase, the viscosity oi' the dechlorinated product increases, probably by reason of the greater ease of polymerization of the di-, tri, etc., oleflnes produced.

Further than this, the viscosity index of the dechlorinated product, whether polymerized to a high or low degree is lower by reason of the formation of di-, tri, etc., chlorparaflines, for, as stated above, the length of chain of the dehydrogenatedhydrocarbons has been found to determine in large part the viscosity index of the oil,

and it is apparent that the dechlorination of monochlorparamnes will produce hydrocarbons with the longest and most nearly normal straight n chains. f

The eiect of increasing degree of chlorination upon the relative proportions of mono, diand vtri-chlorparailines is brought out in the table From a consideration of these data it is apparent that 4when a product of low viscosity. or a product of high viscosity index (whether of low or high viscosity) is desired, the degree of chlorination should not be high, in any single chlorinating operation. Low degree of chlorination may be combined with convenience and high mciency of wax utilization b'y chlorinating for a brief period, say to a point when 3-6% by weight of chlorine has been absorbed, on the basis of waxl treated, and cooling the partially chlorinated mixture tov70 F. or below. The chlorparamnes, whatever their.

degree of. chlorination, are light mobile liquids at very low temperatures, whereas, as is well known, the paraihne waxes are solid below about 110 F. It has been found that the chlorinated Vparaflines are excellent crystallizing agents for the unchlorinated waxes, and that the' waxes are essentially insoluble in them. By cooling the chlorination mixture to` '70 F. or below, very good 1 separation of chlorinated and unchlorinated hydrocarbons may be effected by the use of a bull: centrifuge without the use o f a lter aid, as is invariably necessary in the removal of solid waxes from crude petroleum distillates or residue. In this manner unchlorinated wax, inert;y in the remaining steps in the process, is prevented from becoming an ingredient of the nal oily product ;v

, moreover; by return of the wax to the chlorinating step in the process, its utilization is made substantially complete.

For the several reasons advanced above, we prefer that chlorparaillnes be produced containing from 1323% chlorine, on a wax-free basis, 5 and that unchlorinated wax be removed by simple bulk centrifugation and returned for use in a subsequent chlorinating operation. Hereinafter, the terms chlorinated paraiilnes" and chlorparafilnes are to be interpreted on a waxl0 free basis, that is, after removal of unchlorinated wax.

In effecting chlorination of this type of hydrocarbons, the use of iron reaction vessels, or of ferrous alloy vessels in general, has been found to l5 produce inferior products, especially as concerns the color of the ilnished dechlorinated oils. Lead or porcelain lined vessels, ttings, etc., are found to have no deleterious effect of this character, f and hence are preferred in the construction of 20 the chlorinating apparatus.

'I'he wax-free chlorparafdnes are dechlorinated at elevated temperatures with the aid of a dechlorinating catalyst. Hydrochloric acid is evolved, and oleflnes, dioleiines, etc., depending 25 upon the degree of chlorination (as brought out above), are produced. In -the absence of polymerization these hydrocarbonsy have the same molecular structure as that of the original wax, namely, 'single normal straight chains. Whether 30 polymerization is or is not allowed to take place; the produced dechlorinated hydrocarbons are entirely of the unsaturated series,-oleflnes, diolefines, etc., and/or their polymers. v

4'I'he dechlorination catalyst may also be a poly- 35 merization catalyst, if products of high viscosity are desired, and there are given hereinbelow examples descriptive of the use of both non-polymerizing and polymerizing dechlorination catalysts. 'Iypical of the first class of catalyst (de- 40 chlorinating, non-polymerizing) are various of the adsorbent earths,-clays of both the fullers earth and bentonite types-and silica gel. Typical oi' the second class of catalyst (dechlorinating,

polymerizingl are metallic :aluminum and alu- 45 minumamalgam. Anhydrous aluminum chloride occupies a position intermediate between these two types, so far as polymerization is concerned:

When using the clay or adsorbent earth 'type 50 of catalyst, the chlorparaiiines'and clay are heatmoval the mixture is allowed to cool somewhat and the clay separated by filtration. 'I'he result- 60 ing oils are very light in color and possess a green bloom or fluorescence; they arey relatively low in viscosity.

, The figure exempliiles the lines of ilow of a system well adapted to carry out the processes 65 of the invention. In the gure:

"I'he vwaxy hydrocarbon feed stockfenters wax feed tank P through line I and is there held above the melting point of the wax but not above about 250 F. Thence it flows through line 3 to chlorin- 70 ator A, in which partial chlorination takes place. Liquid chlorine from storage vessel N passes through line 6 and vsuitable pressure reducing and regulating valves (not shown) to vaporizer D,

thence through line 1 and into chlorinating ves- 75 aosaaos sel A, where it is allowed to bubble up from a suitable distributor through the wax hydrocarbons. Unabsorbed chlorine passes from the chlo rinator A through line and may be recovered by absorption in a solvent therefor, as in the vessel M, as shown.

Upon the formation of chlorparamnes desired extent, the reaction mixture is pumped to chlorinated wax storage Q, whence it passes through line il to chiller B for the crystallization of unchlorinated waxes and thus, through line 8:. to bulk centrifuge C. Liquid chlorparamnes pass to storage vessel R, as shown, and unchlo'rinated waxesare returned to wax feed tank P, diagrammatically represented as through the line 2.

From vessel R the chlorparamnes are pumpedv through heater E and dechlorinating vessel D, either by-passing the catalyst chamber S, in the line lll, or passing therethrough as shown. vCirculation into and out of the heater E maintains the temperature at the desired point', and disposition of the dechlorinating, polymerizing type of catalyst in vessel S and of the de'chlorinating, non-polymerizing type of catalyst inthe vessel D, fed as desired through the entry l l, suitably in the form of a slurry in oil, allows the simultaneous use of both types of catalyst, or ofveither, alone,

solvent as that employed in the absorption of the y chlorine passed from the chlorinator A. p

Upon complete dechlorination, the entirely oleflnic, largely mono-olenic oil, of extremely high viscosity index and of viscosity regulable in ac;-

cordance with the invention, may be cooled as by passage through the cooler U, and all traces.l

Example 1.-A yellow crude scale Wax was` chlorinated to a chlorine content of 18.6% by weight, on a wax-free basis, and the chlorparaffines separated from unchlorinated wax by bulk centrifuging at 35 F. The fluid chlorparanes were mixed with 10% by weight of 30-60 mesh Florida clay, such as is useclfor decolorizing pe# troleum lubricating oils, and the mixture heated, with agitation, to 500 F. during a period of about 2 hours'; the temperature of the mixture was held at 500 F. for 2 hours, by which time HC1 evolution had ceased. The dechlorinated mixture was cooled and filtered free from clay. There was no oil-insoluble sludge formed, nor did there ppear to be any loss of hydrocarbon material except that held up on the clay. A red oil with a green bloom. having the following characteristics, was obtained:

Viscosity at F 173 Secs. Saybolt Universal Viscosity at 210 F-- 48 Secs. Saybolt Universal Viscosity index (Dean 8i Davis) 137 Pour 50 F. Solid 45F.

Example 2.-A chlorinated parailine, dewaxed and containing 18.6% chlorine by weight, on a wax-free basis, made b y the chlorination of yellow crude scale wax, was mixed with 10% by weight of an acid-treated 200 mesh decolorizing clay of the montmorillonite type and heated to 525 F. as rapidly las HC1 evolution permitted;

lto the y were as follows:

Viscosity at 100 F 144 Secs. Saybolt -Universal Viscosity at 210 F-- 44 Secs. Saybolt Universal Viscosity index---" 122 Pour 60 F. Solid 55 F.

This oil was dewaxed using four volumes of liqueed butane to one volume of oil, at 40 F. The dewaxed oil had the following characteristics: i

Viscosity at 10.0 F-- 151 Secs. Saybolt Universal Viscosity at 210 F-- 44 Secs. Saybolt Universal Viscosity index 113 Pour 0-F. Solid 5 F.

creases rapidly with temperature rise. The reaction is'continued until HC1 evolution is complete,

after which the catalystis separated and the oil v clarified, as before. By reason of the considerable increase in viscosity attending the use of this type of catalyst, an inert .diluent, such as Apurifled (inert) kerosene, may in extreme cases be desirable as a diluent to .facilitate handling; theA diluent may later be removed, as by ordinary or steam distillation. The resulting oils are darker in color than those prepared with the clay type dechlorinating catalysts; they are of relatively high viscosity, by reason of the polymerization taking place simultaneously with dechlorination.

Example 4.-Substantially wax-free chlorparamnes containing 21,7% chlorine by weight, made from yellow crude scale wax, was heated with v0.5% by weight o f aluminum amalgam, with,

agitation. Evolution of HC1 Vbegan at about 200 F. lThetemperature was raised vto about 300 F. as rapidly, as HC1 evolution would permit, and hem at 300 F. for about 3 hours, by which time deohlorination was complete. No sludge, such as is characteristic of the use of anhydrous aluminum chloride, was formed with the use of.

the aluminum amalgam. The oil was filtered free from aluminum hydroxide, after steaming to remove traces of hydrochloric acid The resulting oil had the following characteristics:

Viscosity at 100 F-- 690 Secs. Saybolt Universal Viscosity at 210 F-- 88 Secs. Saybolt Universal Viscosity index 137 Pour 65 F. Solid 60 F.

mercury, by weight; it is washed free of .hy--

droxide by means of alcohol, and, because'of its great reactivity, is added immediately to the chlorparaiiine in the reaction vessel. f

Example 5.--Wax-free chlorparaillnes containing `18.6% chlorine cwere heated with 0.5% by weight of clean aluminum turnings. As the temperature rose, dry AHC1 gas was bubbled in small amount through the liquid. At about 200 F. dechlorination commenced, and the introduction of dry HC1 was thereupon discontinued. The temperature was increased to 300 F. and held at that point for about 2 hours, by which time dechlorination was complete. As was noted above, with the use of aluminum amalgam, no sludge was formed with the use of metallic aluminum as catalyst. The resulting oil, after separation from the aluminum catalyst and steaming, etc., to remove traces of HC1, had the following properties:

Viscosity at 100 F-- 445 Secs. Saybolt Universal Viscosity at 210 F 68 Secs. Saybolt Universal Viscosity index 122 Pour 65 F.

Solid 60 F.

Example 6.-Metallic aluminum may be used as dechlorinating and polymerlzing catalyst without the introduction of HC1 to initiate the reaction, as was exemplified above (Example 5). I n this event, however, higher temperatures must be used and a longer time of heating is required to give equivalent results. Thus, the dechlorination reaction does not begin below about 300 yF., and, if the dechlorination is to be completed within 4-5 hours, the reaction temperature should be brought to 400 to 450 F. At these higher temperatures, however, excellent results are obtained, and the following oil, obtained in this manner from a Wax-free chlorparamne containing 15.2% chlorine'with the use of 1% of aluminum by weight, is typical:

Viscosity at 100 F-; 918 Secs. Saybolt Universal Viscosity at 130 F..- 432 Secs. Saybolt Universal Viscosity at 210 F 109 Secs. Saybolt Universal Viscosity index 126 Pour 65 F. x Solid 60 F. i

Anhydrous aluminum chloride is in wide use as a dechlorinating agent, and also as a polymerization catalyst. It functions in the present dechlorination-polymerization reaction to produce satisfactory high viscosity index oils, but we have found it less desirable than aluminum amalgam or metallic aluminum, whether or not the dechlorination reaction is initiated, in the latter case, with anhydrous HC1. As is well known, anhydrous aluminum chloride invariably forms an oil-insoluble sludge which contains a very considerable amount of hydrocarbon material held in rather loose chemical combination. The formation of this sludge decreases considerably the yield of oil that may be obtained in a reaction such as that here discussed, for, as is well recognized, the hydrocarbons which may be obtained from the` sludge itself, for example, by decomposition with water, are of inferior quality and represent an utter loss except for use as a fuel or the like purpose.

In addition to loss in yield of high quality oil through the'formation of the typical aluminum chloride sludge, this catalyst is less desirable than aluminum or aluminum amalgam by reason of its cost and because oi' the relatively large quantity required. Thus for dechlorination alone Viscosity at 100 F 97 Secs. Saybolt Universal Viscosity at 130"F 65 Secs. Saybolt Universal Viscosity at 210 F--- 39 Secs. Saybolt Universal Viscosity index 87 Pour 55 F. Solid F.

It will be noted that there has been in this instance no appreciable polymerization; to obtain appreciable polymerization, aluminum chloride approaching 10% in amount must be employed, with consequent increase in amount of sludge formed. In the above example, the yield of oil from original wax was 65 per cent by weight; in the preceding examples (Examples 1-6) the yields in each case were above 90%. From the above it will be clear that although anhydrous aluminum chloride may be used as dechlorination and polymerization catalyst (especially the former), the use of aluminum amalgam or of metallic aluminum, the latter either with or without the introduction of HC1 to initiate Ithe reaction, is much preferred.

The simultaneous use of both polymerizing (aluminum) and non-polymerizing (clay) type catalysts hasbeen found of advantage, for in this manner the viscosity of the finished oil may be controlled. In the use of the two types of catalysts, aluminum or polymerizing type is allowed to function at relatively low temperatures, for example, 300 F. or thereabouts, until the reaction has proceeded sufficiently to produce oil ofthe desired viscosity; thereafter, the temperature is raised to a higher point, for example 500 F. or thereabouts, and the non-polymerizing type catalyst allowed to function until dechlorination is complete. The following is an example of this method of operation.

Example 7.-Ch1orinated paramne containing 15.6% chlorine by weight, on a wax-free basis, was heated with 10% by weight of the acidtreated clay of the montmorillonite type and 0.5 by weight of aluminum, for 1% hours at 300 F. The temperature was then raised to 500 F. and held there for about 30 minutes, by which time dechlorination was complete. ture was cooled and ltered free of clay and of aluminum. A light yellow oil with a green bloom was obtained; it had the following characteristics:

Viscosity at 100 F 423 Secs. Saybolt Universal Viscosity at 210 F.- 70 Secs. Saybolt Universal Viscosity index 130 Pour 60 F. Solid F.

The reaction mixalone, until the reaction has proceeded suiiiclently to produce an oil of the desiredviscosity; without removing any of the reaction products produced by the aluminum or aluminum amalgam reaction, other than the produced hydrogen chloride, we then add a non-polymerizing catalyst, continuing the heatinguntil dechlorination is complete. The results obtained in using such a sequence of steps are similar yto those of Example 7, above, with the advantage that control of the character of the desired end product is in many cases facilitated.

We have found, in general, that the viscosity of the finished oil can be controlled by the correct selection of the chlorine content of the chlorinated paramne, the time of reaction and the temperature of reaction. The following tabulation will make clear'how the practice of our invention may be varied to produce oils, varying viscosity 20 and varying viscosity index:

1n these experiments, aluminum amalgam was 35 used as dechlorinating catalyst.l

From the results above tabulated it appears that:

1. The viscosity and viscosity index of the synthetic oil are almost wholly dependent on the chlorine content of the chlorinated paramne. e higher the chlorine content, the higher the viscosity and the lower the viscosity index.

2.. The reaction time and reaction temperature, within the limits shown above, have relatively little effect onthe viscosity of the synthetic oils. These two factors control the degree of removal oi the chlorine. The temperature must be at least 250 F. for complete dechlorination in a reasonable time. Also the higher the chlorine content, the longer the reaction time must be for the reaction to go to completion.

In blending the high viscosity index oils herein described with oils'of low viscosity index,-for example, to improve in this respect the naph- 55 thenic or mixed-base naturally occurring oils,-

it is to be pointed out that the viscosity index (as dened by Dean and Davis, supra) is not the arithmetic mean of the viscosity indices of the blended oils, but is in all cases considerably 50 higher. For example. the oil whose preparation was described above in Example 4 was blended with an equal volume of a naphthenic-type lubricating oil whose viscosity index was 25, by the Dean and Davis method of calculation. Ihe

65 characteristics of the ons and of this 50-50 mend follows: y

Synthetic Naphthenii 50--50 v oil oil blend 70 Viscosity at 100 F 690 687 643 Viscosity at 130 324 259 274 .viscosity as 210 F. ss so 7o viscosity index.. 124 25 94 It will be observed that the pour points of several of the oils whose production is described above are higher than is desirable for some lubricating purposes. The pour points of these oils may be lowered by a dewaxing process, as mentioned above in connection with Examples 2 and 4, or, if preferable, by adding small amounts of a specially prepared pour point lowering compound, such as is described, for example in U. S. Patent 1,815,022, issued July 14, 1931, to Garland H. B. Davis. Representative of the results obtained with the use of the Davis compound, identied in the trade as Paraow, are the following: f

While we have described in detail the character of our invention and given numerous illustrative examples of the preparation of synthetic hydrocarbon oils of high Viscosity index, we have done so by way of illustration and with the intention that no limitation should be imposed upon the invention thereby.

We claim:

1. The process of producing a liquid olenic hydrocarbon oil consisting of mono-oleilnes in major part and possessing a regulable viscosity and a viscosity'index of above 105, comprising passing chlorine gas into a straight chain parafine wax at a temperature above its melting point but not above about 250 F., to produce chlorparaines containing not above about 25% chlorine on a hydrocarbon-free basis, cooling the mixture containing unchlorinated wax hydrocarbons and produced chlorparaflines to a temperature below the crystallizing temperature of the unchlorinated wax hydrocarbons, removing the crystallized unchlorinated wax hydrocarbons, completely dechlorinating the chlorparaihnes and simultaneously partially polymerizing the resulting straight chain olem'c hydrocarbons by heating the chlorparaines in the presence of two catalysts, one of which is a dechlorinating and polymerizing catalystand .is selected from the group consisting of metallic aluminum and aluminum amalgam and the other of which is a dechlorinating and non-polymerizng'catalyst and is selected from the group consisting of fullers earth and montmorillonite clay, and separating the said catalysts from the produced entirely dechlorinated entirely olefinic and largely mono-oleflnic high viscosity index hydrocarbon oil.

2. The process of producing a liquid oleflnic hydrocarbon oil consisting of mono-olenes in .f major part and possessing a regulable viscosity partial dechlorination of the chlorparaines and to cause polymerization of the resulting oleflnic hydrocarbons, removing the said catalyst from the resulting mixture of chlorparaiiines and ole- `ilniox: hydrocarbons, and heating the said mixture of chlorparaiilnes and olenic hydrocarbons with a second catalyst, selected from the group consisting of fullers earth and montmorillonite clay, to cause complete dechlorination of the remaining chlorparaillnes without the polymerization of the resulting olenic and largely mono-olenic high viscosity index hydrocarbons, and removing the second catalyst from 'the produced entirely dechlorinated entirely oleilnic hydrocarbon oil.

3. The process of producing a liquid oleiinic hydrocarbon oil consisting of mono-oleflnes in major part and possessing a viscosity index of above 105, comprising passing chlorine gas into a straight chain parailine wax at a temperature above its meltingpoint but not above about 250 F., to produce chlorparatnes containing not above about 25% chlorine on a hydrocarbonfree basis, cooling the mixture containing unchlorinated wax hydrocarbons and produced chlorparanes to a temperature below the crystalllzingtemperature of the unchlorinated wax hydrocarbons, removing the crystallized unchlorinated paraine wax hydrocarbons, adding metallic aluminum to the remaining liquid chlorparaillnes, passing dry hydrochloric acid gas into the admixture of chlorparaffines and -metallic aluminum at -a superatmospheric temperature until active dechlorination of the chlorparafnnes is initiated, discontinuing the, introduction oi, the hydrochloric acid while continuing the heating of the reaction mixture, whereby the chlorparafdnes are completely dechlorinated and the resulting oleflnes are simultaneously polymerized, and removing the metallic aluminum from the produced entirely dechlorinated en-l tirely oleiinic and largely mono-olenic high viscosity index hydrocarbon oil;

4. The process of producing a liquid olenic hydrocarbon oil of viscosity index above 105 con sisting entirely of olenes and of mono-olenes in major part, comprising passing chlorine gas into a straight chain paralne wax at a temperature above its melting point but not above about 250 F., to produce Chlor-paraffinescontaining not above about 25% chlorine on a hydrocarboniree basis, removing unchlorinated wax hydrocarbons from the produced chlorparailnes, completely dechlorinating the chlorparamnes and simultaneously polymerizing the resulting olenic hydrocarbons by heating the chlorparafilnes in the presence of aluminum amalgam, and separating the said dechlorinating and polymerizing catalyst from the produced entirely dechlorinated entirely oleflnic and largely mono-oleflnic high viscosity index hydrocarbon oil.

5. 'I'he process of producing a liquid' olenic hydrocarbon oil consisting of mono-olenes in major part and possessing a viscosity 'index of above 105, comprising passing chlorine gas into a straight chain parafline wax at a temperature above its melting point but not above about 250 F., to produce chlorparailines containing not above about 25% chlorine on a hydrocarbonv.free basis, cooling the mixture containing unchlorinated wax hydrocarbons and' produced chlorparamnes to a temperature below the crystallizing temperature of the unchlorinated wax hydrocarbons, removing the crystallized unchlorinated wax hydrocarbonazcompletely dechlorinating the chlorparafnes and simultaneously polymerizing the resulting straight chain olefinic hydrocarbons by heating the chlorparafnes in the presence of aluminum amalgam, and

,separating the said dechlorinating and polymerizing catalyst from the produced entirely dechlorinated entirely oleilnic hydrocarbon oil.

6. The process of producing a liquid olenic hydrocarbon oil consisting of mono-oleiines in major part and possessing a regulable viscosity and a viscosity index of above 105, comprising passing chlorine gas into a straight chain parafilne wax at a temperature above its melting point point but not above ab0ut250 F.,to produce chlorparaiines containing not above about 25% chlorine on a hydrocarbon-free basis, cooling the mixture containing unchlorinated wax hydrocarbons and produced chlorparaiiines to a temperature below the crystallizing temperature of the unchlorinated wax hydrocarbons, removing the crystallized unchlorinated wax hydrocarbons, completely dechlorinating the chlorparaiilnes and simultaneously partially polymerizing the resulting straight chain olefinichydrocarbons by heating the chlorparaiilnes in the presence of two catalysts, one of which is a dechlorinating and polymerizing catalyst and is aluminum amalgam and the other of which is a dechlorinating and nonpolymerizing catalyst and is selected fromv the group consisting of fullers earth and montmorillonite clay, and separating 'the said catalysts from the produced entirely dechlorinated entire- 7. 'Ilie process of producing a liquid oleiinic hydrocarbon oil consisting .of mono-oleiines in major part and possessing a regulable viscosity and aviscosity index of above 105, comprising passing chlorine gas into a, straight chain paraffine waxat a temperature above its melting point but not above about 250 F., to produce chlorparaiilnes containing not above about 25% chiorine on a hydrocarbon-free basis, cooling the mixture containing unchlorinated wax hydrocarbons and produced chlorparaillnes to a temperature below the crystallizing temperature of the unchlorinated wax hydrocarbons, removing the crystallized unchlorinated wax hydrocarbons, heating the chlorparaiiines with aluminum amal- Ygam to cause only partial dechlorination of the chlorparaiilnes and to cause polymerization of the resulting oleinic hydrocarbons, removing the said catalyst from the resulting mixture of chlorparamnes and oleflnic hydrocarbons, and heating the said mixture of chlorparamnes and oleiinic hydrocarbons with a second catalyst, selected from the group consisting of fullers earth and montmorillonite clay, to cause complete dechlorination of the remaining chlorparaiilnes without the polymerization of the resulting oleilnic hydrocarbons, and removing the second catalyst from the produced entirely dechlorlnated entirely oleiinic and largely mono-oleinic high viscosity index hydrocarbon oil.

8. A process of producing a high viscosity index i the other of which is a dechlorinating and non- Y polymerizing catalyst and is selected from the ,75

aosaaoc group consisting of fuilers earth and montmorillonite clay, at elevated temperatures, and separating the catalysts from the dechlorinated hydrocarbon oil.

9. A process of producing a high viscosity index lubricating oil which comprises chlorinating straight chain paraiine hydrocarbons to a chlorine content of between 10 and 25% on a hydrocarbon-free basis, removing unchlorinated hydrocarbons, heating the chlorparafnes with a catalyst selected from the group consisting of metallic aluminum and aluminum amalgam to cause only partial dechlorination of the chlorparaiilnes and to cause polymerization of the resulting dechlorinated chlorparaflines, removing the said catalyst from the resulting mixture of vchlorparaines and hydrocarbon polymers, heating the said mixture of chlorparafflnes and hydro.-

carbon polymers with a second catalyst, selected from the group consisting of fuilers earth and montmorillonite clay to cause complete dechlorination of the remaining chlorparanes without the polymerization of the resulting dechlorinated hydrocarbons, and removing the second catalyst from the dechlorinated hydrocarbon oil.

10. A process of producing a high vviscosity index lubricating oil which comprises chlorinating straight chain paraine hydrocarbons to a chlorine content of between 10 and 25% on a hydrocarbon-free basis, removing unchlorinated hydrocarbons, adding metallic aluminum to the liquid chlorparamnes, passing dry hydrochloric acid gas into the'admixture of chlorparafiines and metallic aluminum at a super-atmospheric temperature until active dechlorination of the chlorparalnes is initiated, discontinuing the introduction of -the hydrochloric acid while continuing the heating of the reaction mixture to eiect a complete dechiorination of the chlorparafiines, and removing the metallic aluminum from the dechlorinated hydrocarbon oil.

11. A process. of producing a, high viscosity index lubrlcating oil which comprises chlorinating straight chain paraiiine hydrocarbons to a chlorine content of between 10 and 25% on a hydrocarbon-free basis, removing unchlorinated hydrocarbons, completely dechlorinating the chlorparafdnes and simultaneously polymerizing the resulting hydrocarbons by heating the chlorparaiilnes in the presence of aluminum amalgam, and separating the aluminum amalgam from the dechlorinated hydrocarbon oil.

ELMSLIE W. GARDINER. JOHN W. GREENE. VR'I'I-IIUR L. LYMAN.

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