US2296511A - Process for producing paraffinic oils - Google Patents

Description

p 1942- F. E. FREY EI'AL 2,296,511

PROCESS FOR PRODUCING PARAFFINIC OILS Original Filed June 27, 19 36 2 Sheets- Sheet 1 gwue/wtoo FREDERICK E. FREY PAUL V. MCKINNEY WILLIAM H. WOOD P 1942- F. E. FREY ETAL 2,296,511

PROCESS FOR PRODUCING PARAFFINIC OILS Original Filed June 27, 1936 2 SheetsSheet 2 O n no n m Til-E1 Yi K Err-:1

f T Q an grwc/wboc FREDERICK E. FREY PAUL V. MCKINNEY WILLIAM H, WOOD @TM M gh J flvw Patented Sept. 22, 1942 PROCESS FOR PR?) DUCING PARAFFINIO ILS Frederick E. Frey, Bartlesville, kla., Paul V. Mc-

Kinney, Pittsburgh, Pa., and William H. Wood, Cleveland, Ohio, assignors to Phillips Petroleum Company, a corporation of Delaware Original application June 27, 1936, Serial No. 87,790. Divided and this application Septem her 5, 1940, Serial No. 355,528

13 Claims. (Cl. 196-10) This invention relates to the manufacture of parafflnic and saturated hydrocarbon oils, and more specifically to the production of paraffinic oils suitable for motor fuel by catalytic synthesis from hydrocarbons of lower molecular weight.

This application is a division of our copending application, Serial No. 87,790, filed June 27, 1936, entitled Process for producing parafiinic oils, now Patent 2,233,363, issued February 25, 1941.

The conversion of normally gaseous olefins into valuable hydrocarbons of higher molecular Weight, suitable for motor fuels, has been efi'ected by heat and pressure, and the use of elevated pressures efiecting rapid reaction and nearly complete conversion at temperatures below the pyrolysis range. The polymerization may also be effected with the aid of suitable catalysts at temperatures lower than those required for the pure- 1y thermal conversion. The hydrocarbons of higher molecular weight which result, are, in either case, composed of varying proportions of hydrocarbons of several types, a large proportion being olefinic or unsaturated. Such olefinic polymers may be converted into oils of saturated type by means of hydrogenation preferably of the non-destructive type.

The present invention is an improvement of the invention set forth in Freys application Serial No. 731,920, filed June 22, 1934, which issued May 21, 1935, as Patent 2,002,394, and also is an improvement of the invention set forth in Freys application Serial No. 12,981 filed March 25, 1935, which was copending with said application of which this is a division, which is a continuationin-part of the aforesaid application and which issued January 4, 1938, as Patent No. 2,104,296.

It is an object of the present invention to effect a process for the formation of predominantly saturated oils at relatively low temperatures, below those required for producing such oils by thermal means, or at appreciably lower pressures, with resultant saving in plant construction and operating expense, by effecting catalytically the polymerization reactions which involve the direct union of parafiins and olefins of lower molecular weight than the oils to be produced.

A further object of this invention is to provide a process for the production of oils of essentially saturated type without the step of hydrogenating partly olefinic polymer oils.

A still further object is to provide a process for the conversion of parafiins of low molecular weight into oils of higher molecular weight without the intermediate conversion into simple olefinic hydrocarbons prior to efiecting conversion into oils.

Other objects will be apparent upon a further consideration of the following description of this invention.

The normally gaseous olefins, ethylene, propylene, and the butylenes may be converted in the process, constituting our invention, together with propane and butane which are normally gaseous, and pentanes. The conversion of pentanes, and parafilns of somewhat higher molecular weight, is desirable in circumstances in which their volatility is undesirably high. It will be understood that by parafllns of low melecular weight is meant those which may yield by union with olefins, oils boiling within the gasoline range.

We have found that the union of parafflns with olefins to produce saturated hydrocarbons of higher molecular weight can :be effected with known polymerization catalysts under new and appropriate conditions and in novel processes which will be presently described. Catalysts efiective for the reaction are aluminum chloride chemically combined with an equimolar quantity, more or less, of lithium, sodium, calcium, or potassium chloride, and the corresponding double compounds in which chlorine is replaced by bromine. Other modifying agents added to aluminum chloride or bromide may also be employed. Zinc chloride, zinc bromide, hydrous alumina, and hydrous alumina deposited on or combined with hydrous silica, are likewise effective for catalyzing the reaction. The catalyst is conveniently used in granular form or disposed on an inert granular support. We have found that oils of a saturated type may be produced by reacting together a mixture of parafiins with olefins, provided the ratio of olefins to paraflin is low in the mixture subjected to the action of the catalyst, and our process provides means whereby extensive and practical conversion may 'be obtained by passing the hydrocarbon stream into contact with the catalyst while maintaining a reaction temperature and while adding olefin in small proportion a plurality of times in the course of the reaction, addition of olefin taking place prior to contact with the catalyst in each addition, whereby added olefin is consumed prior to each subsequent addition of additional olefin. The concentration of olefin present throughout the reaction is in this way maintained at a low value, and the parafllnic reactants at a high value. The temperature ofthe reaction is somewhat higher than the optimum for the familiar i in most cases.

with olefin, and will vary from.100 to about 400 C., the lower temperatures being most fav- Iorable for the utilization of the modified aluminum halide catalysts, and the higher temperatures more favorable for zinc halide, and alumina associated with silica and hydrated phosphorus pentoxide. We have found that elevated pressures are required for obtaining efilcient reaction in which paraflin takes part, and pressures in excess of 100 pounds per square inch are employed, the reaction proceeding more efflciently in most cases as the pressure increases up to about 3000 pounds per square inch, though higher pressures may usually be used without adverse effect on the reaction. Pressures of 400 to 2500 pounds per square inch are, preferable With high olefin contents, exceeding 30%, the parafllns enter into reaction to only a limited degree, and the oils produced are largely of the familiar unsaturated type. Accordingly, we maintain olefin concentration below 20%, and preferably below 10%, in order to obtain eillcient cooperative reaction of paraflins and olefins. Olefin concentration in the parafllnic reactants as low as 0.5% may be maintained economically in the presence of the catalyst by making small olefin additions a sumcientiy great number of times in the course of the reaction. The time of residence in thecatalyst zone will vary with the manner of disposing catalyst in the reaction chamber and with the particular catalyst employed as will also the temperature of reaction, and both can be readily determined by experiment. The oils produced by this process are predominantly parafiinic, containing 20% or les of unsaturated hydrocarbons and distilled almost wholly in th gasoline range, that is, below 225 C. Figure 1 illustrates diagrammatically one form of apparatus for effecting the present process, and, Figure 2 illustrates diagrammatically a modified form of apparatus for effecting the process.

The operation of the process constituting this present invention will be readily understood from a consideration of Figure l of the attached drawings, and the following description relative thereto.

A stream of paraffinic hydrocarbons of low molecular weight is charged to the apparatus illustrated diagrammatically in Figure 1 by introducing the same by way of conduit l0 through which the hydrocarbons pass to the pump ii and are thereby forced tothe heater l2 wherein they are brought to a reaction temperature. The desired degree of heat may be maintained in the heater |2 by any suitable heating means, such as heating coils which may be provided with a feed pipe i3 and an outlet pipe M.

From the heater I2 the stream of paraflinic hydrocarbons flows through the conduit i5 to the. plurality of catalyst chambers i6, i1, |8, I9, 20, and 2| which are arranged in series. Portions of the catalyst chambers iBand l1, l8 and i9, and 20-:falnd 2| are connected by the conduits 22, 23, and 24 respectively; while other portions of the catalyst chambers i1 and I8, and i9 and 20 are connected by the conduits and 26 respectively. A' conduit 21 connects conduit 24 with 'conduit l5 adjacent the chamber l6, and also "connected to the conduit 21 are the conduits 28,

29 and which connect with conduits 22, 23 and v 24 respectively, and the conduits 3| and32 which connect with the conduits 25 and 26 respectively.

Normally gaseous olefins are introduced into the system through conduit 33 and are forced by the pump 34 to the conduit 21 through which the normally gaseous olefins flow to the conduits 28, 29 and 30 to be introduced by conduits 22, 23 and 24 into the catalytic chambers l1, l9, and 2| respectively. From conduit 21 the olefins also flow through conduits 3|, and 32 into the conduits 25 and 26 to be introduced into the catalyst chambers l8 and 20. Conduit 21 also conduits olefins directly to conduit l5, from which they flow into the catalyst chamber i6.

Thus it will be appreciated that a reaction between the parailinic hydrocarbons introduced into the process by way of conduit I0, and the olefinic hydrocarbons introduced byway of conduit 33, takes place in the several catalyst chambers IS, IT, i8, i9, 20 and 2| through which the reacting parafilnic and olefinic hydrocarbons flow in series. The reacting paraflinic and olefinic hydrocarbons after reaching the last catalyst chamber 2| pass therefrom through the conduit 35 into a separator 36 wherein oils of a higher molecular weight are separated and dis charged from the process through the conduit 31 controlled by the valve 38.

Unreacted parafflns of low molecular weight and containing a small amount of olefin will pass from the separator 36 through the conduit 39, and will be forced by the pump 40 into the conduit l5 to be passed'to the first catalyst chamber i6 and the succeeding ones as described.

The parafiins of low molecular weight most suitable for the process, namely propane, butane, pentanes and somewhat heavier paraffins may contain paraffins of lower molecular weight, and may be derived from petroleum, natural gas, or cracking still gases and other sources. Olefins may be derived from cracking still gases, from pyrolysis of petroleum distillates and gases, and from dehydrogenation of ethane, propane, and butane. The product of catalytic partial dehydrogenation, containing unconverted paramn together with the corresponding olefin is particularly suitable for conversion in our process, since both parafiln and olefin are present. Such a mixture of parafiln and olefin may be introduced through conduit 33 of Figure 1 as olefinic stock. The olefin depleted paramn recovered in separator 36 may be returned through conduit 39 to serve as the parafilnic reactant, and unconverted paraflins in excess are discharged through conduit Si by opening valve 42 and thereafter may be subjected to partial dehydrogenation and returned once more to the process by any suitable manner not shown. This process is most advantageously applied to the conversion of propane and butane. The reacting of an individual paraflin with an individual olefin yields an oil of relatively simple composition predominating in saturated hydrocarbons whose molecular weight is the sum of that of the paraflln and the olefin.

Example duced into the catalyst tube at four equidistant points, the rate of flow of the hydrocarbon being such that the time of passage through the catalyst zone occupied minutes. the following composition:

The efliuents had As the analysis shows, the quantity of isobutane consumed was approximately equal to the isobutylene consumed. The oils formed were almost wholly paraflinic in character and predominated in material distilling in the heptaneoctane range.

Figure 2 illustrates diagrammatically a modified apparatus for effecting the present invention, and herein hydrocarbons, consisting of olefins and parafiins, which are to be reacted, enter the process together with each other through the conduit 50 and are forced by the pump 55 through the conduit 52 to the reaction chamber 53 wherein the hydrocarbons, comprising paraffins and oleflns, are brought into contact with a catalyst suitable for effecting the desired polymerization reaction.

The reacted hydrocarbons are discharged from the chamber 53 into the conduit 54 and are divided into two streams, one of which flows through valve 55A into conduit 55 and is forced by pump 56 through valve 553 backinto conduit 52 to be reintroduced into the reaction chamber 53. The other stream of reacted hydrocarbons flows through valve 51A and into conduit 51 passing into the separator 52 wherein the hydro carbons of higher molecular weight produced by of low molecular weight with normally gaseous the reaction are separated from the lighter hydrocarbons and discharged through conduit 59 controlled by valve 60.

Any unreacted gases will be predominantly parafiinic and may be discharged through conduit 6i, and may be reacted with additional olefin or put to any other desired use.

However, it is to be understood that it may not always be desirable, or necessary, to recycle the reacted hydrocarbons from chamber 53 back through conduits 55 and 52 for reprocessing in the reaction chamber, so therefore when desired, or conditions demand, the valves 55A and 55B, which are interposed in conduit 55, may be closed.

Or it may be desirable, or necessary, to recycle the reacted hydrocarbons from chamber 53 back through the conduits 55 and 52 to the chamber again with only a minimum amount of the reacted hydrocarbons passing directly from the chamber 53 through conduits 54 and 51 to the separator 58, in such a case the valve 51A may be set at any desired partially closed position to limit the flow of the reacted hydrocarbons directly from chamber 53 to separator 58.

From the foregoing it should appear obvious that by control of valves 55A and 55B, and valve 51A the flow of the reacted hydrocarbons from the chamber 53 to the separator 58, or the recycling of these hydrocarbons back through the chamber 53 can be readily controlled and regulated.

We claim:

1. A continuous process for reacting paraflins olefins to produce predominantly paraflinic oils in the motor fuel boiling range and of higher molecular weight, which comprises bringing the parafiins into contact with a polymerization catalyst of the group consisting of aluminum chloride combined with a substantial proportion of an alkali halide and aluminum bromide combined with a substantial proportion of an alkali halide in a reaction zone for a suitable reaction period while maintaining a reaction temperature between and 400 C. and a pressure of at least 100 pounds per square inch, introducing normally gaseous olefins to the reaction zone a plurality of times during the reaction period while maintaining the concentration of added olefin present in the reacting hydrocarbons below 20 per cent, withdrawing the reacted hydrocarbons from the reaction zone and separating therefrom a hydrocarbon fraction containing the predominantly parafiinc oils in the motor fuel boiling range so produced.

2. A continuous process for reacting paraflins of low molecular weight with normally gaseous olefin hydrocarbons to produce predominantly paraillnic oils of high molecular weight in the motor fuel boiling range, which comprises passing a stream of hydrocarbons comprised of parafiins of low molecular weight in which normally gaseous olefin hydrocarbons are dispersed through a reaction zone at a temperature between 100 and 00" C. and a pressure greater than 100 pounds per square inch, and in the presence of a polymerization catalyst of the group consisting of aluminum chloride combined with a substantial proportion of an alkali halide and aluminum bromide combined with a substantial proportion of an alkali halide, for a period of time such that reaction takes place consuming paraflin hydrocarbons and said olefin hydrocarbons and dispersing normally gaseous olefin hydrocarbons in said stream of hydrocarbons during said period of time in such a manner that the concentration of unreactedunsaturated hydrocarbons present in the mixture does not exceed 20 per cent by weight of the total hydrocarbon stream and separating from at least a portion of the eiiluent of said reaction zone a hydrocarbon fraction comprising paraflinic oils in the motor fuel boiling range.

3. A continuous process for reacting paraffins of low molecular'weight with normally gaseous olefin hydrocarbons to produce predominantly paraflinic oils of higher molecular weight in the motor fuel boiling range which comprises passing a stream of hydrocarbons comprised of paraflins of low molecular weight in which normally gaseous olefin hydrocarbons are dispersed, while at a reaction temperature between 100 and 400 C. and a pressure greater than 100 pounds per square inch, through a reaction zone in the presence of a polymerization catalyst of the group consisting of aluminum chloride combined with a substantial proportion of an alkali halide and aluminum bromide combined with a substantial proportion of an alkali halide, for a period of time such that reaction takes place consuming paraffin hydrocarbons and said olefin hydrocarbons, passing a portion of the eflluents of said reaction zone to be mixed with the hydrocarbon stream entering said zone and separating from another portion of said eflluents predominantly paraflinic oils of higher molecular weight in the motor fuel boiling range so produced.

4. In a continuous process for producing predominantly paraflinic hydrocarbons or high molecular weight from paraifins and olefins of lower molecular weight, the steps which comprise maintaining a stream of predominantly paramnic hydrocarbons in independent cyclic circulation through a reaction zone containing a polymerization catalyst of the group consisting of aluminum chloride combined with a substantial proportion of an alkali halide and aluminum bromide combined with a substantial proportion of an alkali halide, and wherein a reaction temperature between l and 400 C. and a pressure between 100 and 3000 pounds per square inch are maintained and wherein a catalyzed reaction takes place consuming parafiin and added olefin hydrocarbons, introducing into said stream an olefin-containing hydrocarbon mixture such that the cone tration of added, unreacted olefins does not xceed 20 per cent by weight of the total mixture local to the point 0! introduction,

withdrawing from the said stream a portionthereof and separating therefrom predominantly parafiinic hydrocarbons of higher molecular Weight.

5. In a continuous process for producing predominantly pc hydrocarbons of higher molecular weight from ns and olefins of lower molecular weight the steps which comprise maintaining a predominantly paraflinic hydrocarbon mixture in continuous circulation in an endless circulatory cycle which contains a reaction zone containing a polymerization catalyst of the group consisting of aluminum chloride combined with' a substantial proportion of an alkali halide and aluminum bromide combined witha substantial proportion of an alkali halide, and a zone of hydrocarbon introduction, adding a hydrocarbon mixture containing paraifins of low molecular weight having at least three carbon atoms per molecule and olefin hydrocarbons at the zone of hydrocarbon introduction thereby producing a hydrocarbon mixture such that the concentration of unreacted added olefin is between 0.5 and 20 percent by weight of the total hydrocarbon mixture, passing the mixture to said reaction zone wherein a catalyzed reaction takes place consuming paramns and olefins and forming paraflin hydrocarbons and maintaining therein a reaction temperature between 100 and 400 C. and a'pressure in excess of 100 pounds per square inch, passing the reacted mixture back to the zone of hydrocarbon introduction thus completing the endless circulatory cycle, withdrawing at some point in the cycle a portion 01! the mixture and separating therefrom predominantly parafiinic hydrocarbons of higher molecular weight.

6. A continuous process for reacting parafilns of low molecular weight with normally gaseous olefin hydrocarbons to produce predominantly parafilnic oils of high molecular weight in the motor fuel boiling range, which comprises passing a. stream of hydrocarbons comprised of parafiins of low molecular weight in which normally gaseous olefin hydrocarbons are dispersed through a reaction zone at a temperature between 100 and 400 C. and a pressure greater than 100 pounds per square inch, and in the presence of aluminum chloride combined with a substantial proportion of an alkali halide, for a period of time suchIthat reaction takes place consuming parafiin hydrocarbons and said olefin hydrocarbonsv and dispersing normally gaseous olefin hydrocarbons in said stream of hydrocarbons during said" period of time in such a manner that the concentration of unreacted unsaturated hydrocarbons present in the mixture does not exceed 20 per cent by weight'oi the total hydrocarbon stream and separating from at least a portion'of the efiluent of said reaction zone a hydrocarbon fraction comprising parafilnic oils in the motor fuel boiling range.

7. A continuous process for reacting parafiins of low molecular weight with normally gaseous olefin hydrocarbons to produce predominantly paraiflnic oils of high molecular weight in the motor fuel boiling range, which comprises passing a stream of hydrocarbons comprised of paraflins of low molecular weight in which normally gaseous olefin hydrocarbons are dispersed through a reaction zone at a temperature between and 400 C. and a pressure greater than 100 pounds per square inch, and in the presence of aluminum bromide combined with a substantial proportion of an alkali halide, for a period of time such that reaction takes place consuming parafiin hydrocarbons and said olefin hydrocarbons and'dispersing normally gaseous olefin hydrocarbons in said stream of hydrocarbons during said period of time in such a manner that the concentration of unreacted unsaturated hydrocarbons present in the mixture does not exceed 20 per cent by weight of the total hydrocarbon stream and separating from at least a portion of the eiiluent of said reaction zone a hydrocarbon fraction comprising parafiinic oils in the motor fuel boiling range.

8. A continuous process for reacting paraffins of low molecular weight with normally gaseous olefin hydrocarbons to produce predom nantly paraifinic oils of high molecular weight in the motor fuel boiling range, which comprises passing a stream of hydrocarbons comprised of paraflins of low molecular weight in which normally gaseous olefin hydrocarbons are dispersed through a reaction zone at a temperature be-- tween 100 and 400 C. and a pressure greater than 100 pounds per square inch, and in the presence of aluminum chloride combined with a substantial proportion of an alkali chloride, for a period of time such that reaction takes place consuming paraflin hydrocarbons and said olefin hydrocarbons and dispersing normally gaseous olefin hydrocarbons in said stream of hydrocarbons during said period of time in such a manner that the concentration of unreacted unsaturated hydrocarbons present in the mixture does not exceed 20 per cent by weight of the total hydrocarbon stream and separating from at least a portion of the eiiluent of said reaction zone a hydrocarbon fraction comprising parafiinic oils in the motor fuel boiling range.

9. A continuous process for reacting parafiins of low molecular weight with normally gaseous olefin hydrocarbons to produce predominantly paraflinic oils of high molecular weight in the motor fuel boiling range, which comprises passing a stream of hydrocarbons comprised of paramns of low molecular weight in which normally gaseous olefin hydrocarbons are dispersed through a reaction zone at a temperature between 100 and 400 C. and a pressure greater than 100 pounds per square inch, and in the presence of aluminum bromide combined with a substantial proportion of an alkali bromide, for a period of time such that reaction takes place consuming parafiin hydrocarbons and said olefin hydrocarbons and dispersing normally gaseous olefin hydrocarbons in said stream of hydrocarbons during said period of time in such a manner that the concentration oi unreacted unsaturated hydrocarbons present in the mixture does not exceed 20 per cent by weight of the total hydrocarbon stream and separating from at least a portion of the emuent of said reaction zone a hydrocarbon fraction comprising parafilnic oils in the motor fuel boiling range.

10. A continuous process for reacting paramns of low molecular weight with normally gaseous olefin hydrocarbons to produce predominantly parafilnic oils of high molecular weight in the motor fuel boiling range, which comprises passing a stream of hydrocarbons comprised of parafilns of low molecular weight in which normally gaseous olefin hydrocarbons are dispersed through a reaction zone at a temperature between 100 and 400 C. and a pressure greater than 100 pounds per square inch, and in the presence of aluminum chloride combined with a substantial proportion of sodium chloride, for

a period of time such that reactiontakes place consuming parafiln hydrocarbons and said olefin hydrocarbons and dispersing normally gaseous olefin hydrocarbons in said stream of hydrocarbons during said period of time in such a manner that the concentration of unreacted unsaturated hydrocarbons present in the mixture does not exceed 20 per cent by weight of the total hydrocarbon stream and separating from at least a portion of the efliuent of said reaction zone a hydrocarbon fraction comprising paramnic oils in the motor fuel boiling range.

11. A continuous process for reacting parafflns of low molecular weight with normally gaseous olefin hydrocarbons to produce predominantly parafilnic oils of high molecular weight in the motor fuel boiling range, which comprises passing a stream of hydrocarbons comprised of paraflins of low molecular weight in which normally gaseous olefin hydrocarbons are dispersed through a reaction zone at a temperature between 100 and-400 C. and a pressure greater than 100 pounds per square inch, and in the presence of a polymerization catalyst of the group consisting of aluminum chloride combined with a substantial proportion of an alkali halide and aluminum bromide combined with a substantial proportion 01' an alkali halide, tor a period of time such that reaction takes place consuming parafiin hydrocarbons and said olefin hydrocarbons and dispersing normally gaseous olefin hydrocarbons in said stream of hydrocarbons during said period of time in such a manner that'the concentration of unreacted unsaturated hydrocarbons present in the mixture is between 0.5 and 10 per cent by weight of the total hydrocarbon stream and separating from at least a portion oi the eiiluent of said reaction zone a hydrocarbon fraction comprising parafllnic oils in the motor fuel boiling range.

12. A continuous process for reacting parafiins 01 low molecular weight with normally gaseous olefin hydrocarbons to produce predominantly paraflinic oils oi high molecular weight in the motor fuel boiling range, which comprises passing a stream of hydrocarbons comprised of parafllns 01' low molecular weight in which normally gaseous olefin hydrocarbons are dispersed through a reaction zone at a temperature between and 400 C. and a pressure greater than 100 pounds per square inch, and in the presence of a polymerization catalyst of the groupconsisting of aluminum chloride combined with a substantial proportion of an alkali halide and aluminum bromide combined with a substantial proportion of an alkali halide, for a period of time such that reaction takes place consuming paraflin hydrocarbons and said olefin hydrocarbons and dispersing normally gaseous olefin hydrocarbons in said stream of hydrocarbons during said period of time in such a manner that the concentration of unreacted unsaturated hydrocarbons present in the mixture is about 0.5 per cent by weight of the total hydrocarbon stream and separating from at least a portion of the efliuent oi. said reaction zone a hydrocarbon fraction comprising parafiinic oils in the motor fuel boiling range. I

13. A continuous process for reacting parafiins- 01' low molecular weight with normally gaseous olefin hydrocarbons to produce predominantly paraifinic oils of high molecular weight in the motor fuel boiling range, which comprises passing a stream of-hydrocarbons comprised of parafllns of low molecular weight in which normally gaseous olefin hydrocarbons are dispersed through a reaction zone at a temperature between 100 and 400 C. and a pressuregreater than 100 pounds per square inch, and in the presence 01' aluminum chloride combined with a substantial proportion 01' an alkali chloride, for a period of time such that reaction takes place consuming paramn hydrocarbonsand said olefin hydrocarbons and dispersing normally gaseous olefin hydrocarbons in said stream of hydrocarbons during said period of time in such a man-'- her that the concentration 01' umeacted unsaturated hydrocarbons present in the mixture is about 0.5 per cent by weight of the total hydrocarbon stream and separating from at least a FREDERICK E. FREY. PAUDQT. MCKINNEY wnmm H. WOOD.-

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