US2245733A - Process for reforming and polymerizing hydrocarbons - Google Patents

Description

June '17, 1941. P, SUBKQW y2,245,733 PROCESS FOR EFRMING AND POLYMERIZING HYDROCARBONS Original Filed Aug. 12, 1935 2 SheetS-Sheet 1 Separa for 7 3 f frnace June 17, 1941.

P. suBKow ffRocEss FOR REFoRMING-AND POLYMERIZING'HYDRocAR-BONS Original Filed Augf 12, 1935 2 Sheets-Sheet 2 [Nl/ENTOR isomeriration properties.

Patented June 17, 1941 UNITED STATES PATENT oI-FicE 2,245,733 I I PROCESS FOR REFORMING AND POLYMER- IZING HYDROCARBONS Philip Subkow, West Los Angeles, Calif., assignor to Union Oil Company of Califo rnia, Los Angeles, Calif., a corporation of California Original application August 12, 1935, Serial No. 35,702. Divided and this application July 12, 1938, Serial No. 218,775

(ci. iss-9) 4 Claims.

This invention relates to a process and apparatus for the formation of high anti-knock gaso-` vmolecular weight into lower molecular Weight hydrocarbons, known as cracking, "dehydrogenating and reforming, with processes' for building hydrocarbons of lhigh anti-knock quality from low molecular weight hydrocarbons, particularly those which are normally gaseous at atmospheric temperatures and pressures, and known as polymerization or synthesis and processes for obtaining improved anti-knock qualities by molecular rearrangement, known as The conventional process for reforming gasoline consists in subjecting hydrocarbons in the gasoline range, preferably in vaporous form, to high temperatures, under which conditions the gasoline is converted from one having low antiknock properties to one having high anti-knock The gasoline is then separated from the xed gases and normally gaseous hydrocar bons to form a stabilized and reformed gasoline. This process for the formation of high iso-octane number material is visualized as proceeding through cracking, dehydrogenating and isomermonoor dioleiins are polymerized to higher molecular weight polymers. Isomerization, lalthough not strictly a polymerization reaction in the sense that higher molecular weight'bodies are formed, is included within this term since it.

occurs along with such polymerization reactions.

The term polymerization as here used is intended toy embrace these types vof reactions for building higher .molecular weight bodies by reaction of lowermolecular Weight hydrocarbons.A

The gasoline produced by this process is termed polymergasoline, and when produced as a mixture with reformed gasoline it is here termed reformed and polymer, gasoline.

The term reforming is intended to embrace v the reactions of cracking ord'ecomposition, de-

hydrogcnation and isomerization by which low octane material of lgasoline -or higher boiling range is converted into gasoline fractions of high anti-knock properties.- i .l

'I'he object of this invention is to reform gasoline under such conditions that along with the cracking, dehydrogenating, and isomerizing operations there is a parallel, subsequent, or conjoint polymerizing reaction where the gasesformed Vor added to a reforming operation vare formed directly in the process. Broadly stated,

izing reactions which yield as an intermediate or by-product, low molecular weight oleiinic -fractions-and chemical radicals with unsatised vii.-v lences called residuals. In conventional reforming operations there is no attempt to control the subsequent polymerization of these materials to retain and conserve those desirable anti-knock characteristics and to polymerize Vthe gaseous residuals to liquid hydrocarbons of high anti-knock value.. 'Ihe process of this invention provides.`4 for controlled polymerization and conservation of these residuals and olens, particularly those of the ethylenic type, in the reaction zones, thus favoring continued decomposition of the petro-l leum hydrocarbons and increased yield of high octane material over that resulting from a simple reforming operation. A reformed gasoline con-l taining increased percentages of polymer gasoline of high octane valueresults.

The reactions here generically" termed polymerization include alkylation reactions wherein l saturated hydrocarbons combinewith' .unsaturated hydrocarbons to form high molecular weight branched chain hydrocarbons or alkylaethylene, propene or butenepor straight vpolymerization reactions wherein olens such as the-invention consists in reforming'liquid hydrocarbons, and particularly hydrocarbons in the gasoline range, to produce hydrocarbons having boiling points in thegasolin range and vapors containing. hydrocarbons of ilve or less carbon atoms, which vapors are polymerized, separately if desired, but preferably in the presence of the gasoline fractions produced by the reforming operation.

The -inventionalso contemplates the addition of hydrocarbons having ilve or less carbon atoms .to the gasoline being polymerized to increase theconcentration of these hydrocarbons. I l Normally gaseous hydrocarbons suchas Propane, butane, propylene or butylene may be polymerized. Instead of using the hydrocarbons having four or less carbon atoms, stabilized natural gasoline containing these fractions may be employed. It is preferred, however, touse hy'- drocarbons of the unsaturated type. Sources of such gases areprocesses in which ga's oil and/or fuel oil arecrackedat temperatures below 1000 F.,that is, in the neighborhood of 850950 F.

The reforming operation, which is-at least partially a combined cracking, dehydrogenating and isomerizing'operatlon.- may be aided by choice of conditions of temperature and pressure and rate of feed and by selection of catalysts. In general, high temperatures, short time, and moderate pressures are desirable.- Temperatures may range from 650-18509 F., but the range from 850- nesium,

1200 F. is preferred. Pressures ranging from atmospheric to 1500 lbs. may be used, but low prestungsten;

Ormea-Alkali metals such as calcium, magbarium, aluminum, chromium, zinc, manganese, silica;

Hydroides.-Chromium, alkali metal; Acids.--Molybdid'` tungstic, chromic, phosphoric, arsenious, silica, boric;

Salta-illuminates, chromates, tungstates, vanadates, uranates, phosphates, of the alkali earth metals such as calcium;. and the phosphates, chromates and vanadates of aluminum, `chromium or zinc; phosphates of molybdenum, tungsten, ammonium molybdate, aluminum sulfate; adsorbents like fullers earth, bentonite Adsorbcnt charcoal or other adsorbent carbons;

Halides such as aluminum chloride, iron chloride, aluminum bromide and iron bromide.

When hydrocarbon fractions having a boiling range up to-about 60G-650 F. are-passed over these catalysts at .temperatures from 662-1832 gasoline containing oleinic materials temperatures of about 850-1050 F. may be employed. Higher temperatures in the neighborhood of 1380-1830", F. favor aromatic formation. The salts and oxides of .the difcultly reducilble metals, as for instance, the alkali metals such as calcium, magnesium, barium, require in general higher temperatures for thel formation of oleflns, i. e. temperatures in the neighborhood of 1020- 1380 F. The gases resulting may then be reacted in Athe, rprsence of a polymeri'zing catalyst.

Catalysts which have been found to aid polymerization are termed polymerizing catalysts. Such catalysts are fullers earth, absorbent carbon, phosphorous acidsV such as orthophosphorous aicid, and phosphoric acid such as orthol phosphoric acid.- In solid form, aluminum oxsilicon,- lead oralloys of these metals.

In using the reforming and polymerizing cata.-

clays such as Ibentonite and fullers earth are best used in their activated states, thus fullers earth is used in the acid treated state, inwhich state their adsorptive activity is best brought out. Methods of increasing the adsorptive activity of clays and' adsorbent carbon are Well known in the adsorption art.

In using catalysts to be carried in the stream of gases, the catalyst, if it is boron fluoride, may be fed as a gas to this stream or mixed in the liquid state at low temperature. If the catalysts are solid they are best ground fine and carried in suspension by mixing with the liquid feed and carried along bythe high velocity of the vapors. The solid catalyst may also be positioned as a contact mass in the reaction zone and the vapors passed through the body of catalyst.

The reactions which have been termed polymerization reaction, and reforming reaction are parallel reactions. These reactions are generaly reversible, the reaction in one direction being a polymerization reaction, and the reaction in the other direction being a reforming reaction. Consequently, in the polymerization operation and in the reforming operation, all reactions may occur. In general, the polymerization reactions are favored by lower temperatures, While the reforming reactions are favored by higher temperatures, the temperatures chosen should be those at which the desired reaction predomina'tes. The temperature will also vary with the feed stock, particularly upon its boiling lysts, one skilled in the art will understand that the` conventional methods of preparing catalysts of this nature are to be followed. Thus, the

metals are best usedwhen in finely divided form,

and better when supported on carriers. For example, the metal might be formed by reducing the oxide of metal absorbed upon a carrier such as charcoal orsilica gel in a stream of hydrogen.

'Ihese methods arewellknown and conventional formed'when precipitated on a. carrier or fused ,V75

range and the chemical type of the feed stock and with the pressure. An additional factor is time. The polymerization reactions and decomposition reactions may proceed further by allowing a longer time of contact with the catalyst.

Care must be taken to prevent the reforming reactiony from'going too far, thus forming light,

undesirable fractions, or from allowing the polyfavor polymerization reactions in the temperature range between 350 and 700 F. Nickel favors the reaction' in the lower of the saldi range, that is, around 350-355 F. These materials favor the reforming operation at highertemperatures. Iron and nickel favor the reforming operation above about 390 F. and in general, iron, nickel,l coppercob alt, zinc, aluminum, chromium favor the reforming operation at temperature ranges above 932 F. y l

It will, be seen that certain of the materials here recited, for example, both vzinc and nickel catalyze both reactions, ibut at lower tempera-A tures, zinc in the range between' 350-'700 F., and nickel in the range between S55-390 F. favor the polymerization reaction, while the reforming reaction ls favored at temperatures above 930 F. In choosing temperatures for polymerization and reforming, vusing metall catalysts 4of the nature shown above, it is preferable that polymerization `reactions be carried out at lower temperatures here indicated, and the reforming operations at the higher temperatures. However, by applying higher pressures as hereinafter described, the vreaction temperatures are broughtv ing at temperatures in the neighborhood of choose catalysts whichare.

silica in the form of aluminum silicates, for instance, oridin or fullers earth, favor polymerization in the temperature range between 570 and 750 l'. Preferably, aluminum oxide should be used in the neighborhood of from 640 to 700 F. Lime and other alkali earths 'or oxides or carbonates favor. polymerization in the range .between 660 F. and 840 F. Magnesium and beryllium oxides favor polymerization reactions in the upper part of said rangearound 840 F.

to 930 F. Aluminum chloride and boron trifluoride are very active at temperatures from 32 F. to 300 or 390 F. Magnesium oxide, lime and silica, such as silica gel, can be used in reforming reactions in temperature ranges above-930 1290 F. Aluminum oxide or aluminum silicate such as fullers earth or floridin or other forms will favor reforming above 750. F. Thus in using aluminum oxide, either alone or in the form-of silicate, the temperature ranges should be adjusted depending on the form of thereaction which is to Ibe favored. In operating inthe upreforming -operation, and the temperature at. which they accelerate the polymerization operation, .do not lie far' apart, instance, one may choose catalysts which are active, i. e. promote or accelerate; in reformactivein, i. e. promote or accelerate, the polymerization reactiony attemperatures 4ranging from about 570-840 F. at pressures ranging as low as atmospheric.

The liquid gases may be washed with alkali to free them of hydrogen sulfide vand( they can then be charged. The charging stocks to the reforming operation maycontain organic sulfur bodies which will poison the catalyst. One may either remove these bodies or use' a'catalyst which will not be poisoned in these bodies.

The following of the above .referred to catalysts' are not easily poisoned by the sulfur and sulfur bodies present in the charging stocks here used. Metals: Cobalt, iron, zinc; suldesof oo balt, iron, zinc, nickel, manganese, tungsten; ox-

ides of chromium, zinc, manganese; aluminum;

` chromium hydroxide; molybdic, tungstic, chromper ranges around '750 F. aluminum oxide will have a favorable inuence on both reactions, aiding in the decomposition in the higher molecular weight liquid hydrocarbons, and aiding in the lower molecular weight gaseous hydrocarbons. The temperature range should be chosen to form a balance between thetwo.

Of. theA salts or adsorbents which accelerate polymerization reaction, the alkali metal carbonates, phosphates and borates are active in the neighborhood of 750930 F.; bentonite is active ic, phosphoric, arsenious, silicio, boric acids; phosphates of alkali metals, molybdenum, tungsten; ammonium molybdate, aluminum silicate,

fullers earth'.

Water and oxygen and traces fof' alkali Vpoison valuminum oxide and full'ers earth catalysts.

Small percentages of moisture in such catalysts as hereinafter described may be tolerated. Oxyfrom G-840 F.: phosphoric acid is active from 35o-475 F. Absorbent charcoals and carbons fa- .vor the polymerization reaction at around '750 F; Y Above these, temperatures, and particularly at substantially higher temperatures reforming is favored by these catalysts. `Calcium aluminate, ammonium molybdate favor the reforming operations at temperatures of 930-1290" F. and higher. Aluminum sulfate and phosphoric acid are active in reforming reactions above 660 F. and very active above 930'* F.

Mixed catalysts composed of mixtures of any from water, dehydrated by heating, although a gen also poisons aluminum oxide, fullers earth, and the metal catalysts. Air should be excluded.

A good catalyst for the polymerization reaction is aluminum oxide preferablyin the form of. fullers earth or artificial fullers earth formed by co-precipitating silica and aluminum oxide from a mixture of sodium silicate and aluminum sulfate. The aluminum silicate is` washed neutral and dehydrated. It is preferred that the mixture be neutral or acid, and fr ee of alkaline material. It is best that the catalyst be substantially free small percentage, up to 5 or 6% of moisture is not detrimental. In using this catalyst it has '1 been found that a -small amount of hydrochloric acid introduced as alkyl chloride, as for instance,

isopropyl chloride may be introduced to aidthe polymerization reaction. Apparently, the isoone or more of the above reforming catalysts, and

any one or 'more ofthe above polymerizing cata.-

lysts, which are active, i. e. promote and accelerate the reforming and -polymerizing operation in the neighborhood of 700-930 F. will permit of the joint andfavorable reactions of reforming and polymerization when operated at temperatures between about I700` 930 F. at pressures of about '75-1500-lbs.

Higher pressures favor the polymerization re-'l Aaction vand therefore, by the amplification of pressure, the tolerable temperature for polymerization vis increased. At the same time pressure tends to decrease the reforming operation, and the two operations may be brought closer together by the application .of pressure. By choosing a temperature intermediate the preferred reforming and polymerization reaction temperature at atmospheric pressure, and applying high pressure *inthe-neighborhood ofv 1000-5000 lbs. the samev catalyst may be used for both reactions. It may be chosen to use a catalyst or vcatalyst mixtures propyl chloride is decomposed ln'the reaction- 5 v,zone and forms free 5 hydrochloric acid. Ithas been found conveniently formed bypassing a mixture of .un-

' saturated hydrocarbons such as butylene and propylene over the above fullers earth type catalyts as previously disclosed at ordinary temperatures from about 20G-400 F. The alkyl chloride may be introduced either in vapor form as pro- "duced by the chlorinating reaction, or first condens'ed, `and then introduced in liquid form. The

amount of alkyl chloride required varies from one-tenth to one percent, preferably to about one-half percentof the reaction vapors.

.y 'I'he catalysts here employed'may be the reforming or polymerizing processes either as a catalystbody or as a mixture with incoming feed. In using the catalyst as a catalyst body, the reaction zone Ain the tubelor chamber Ais chargedwith the solid catalyst and thereaction vapors are passed through the body of the catalyst. It is possible,;however, to use the catalyst as a slurry with"the"incomiug feed, 'in which case Thus, forv that the alkyl chloridesare used-in the reaction zones are empty except for the reaction mixture. When the vaporized hydrocarbons carrying the catalyst ground fine in suspension pass through the reaction zone, the high velocity of thevapors and the ne particle size of the catalyst prevent sedimentation of the catalyst in the tubes or chambers.

In carrying out the process of this 4invention the following principles may act as a guide. The' feed of liquid fractions is 'one preferably having an end point not in excess of 650 F. Usually a heavy gasoline fraction boiling between 30G-500 .F. will prove satisfactory. The reforming, cracking or dehydrogenation is best carried out at a temperature plane higher than that at which the polymerization reaction is carried out. It is desirable also to control these reactions so that they do not proceed to the ultimate stage of vcarbon, hydrogen and methane formation or to the production of high boiling fractions in the fuel oil range; It therefore will be desirable .in one form of this invention to use relatively high temperatures and short times of contact in the reforming zone, and to cool ,the reaction products produced by the dehydrogenating and cracking reactions before passing them to the polymerization reaction zone. The yield of polymerizai gaseous hydrocarbons are introduced into the tion products may be increased by adding to the reaction mixture from an extraneous source hydrocarbon materials of live or less carbon atoms. The polymerizing reaction including addition of unsaturates to unsaturates and alkylation in polymolecular reaction'is favorablyiniiuenced by increasing the concentration of the reactants. 4This may be accomplished by increasing the pressure, and also by adding materials undergo` ing polymerizing reaction to the reformed vapors. These may be cracking still gases, or liquid gas from a gasoline stabilizer tower.

It is desirable to have present unsaturated hydrocarbons such as butenes, propenes and ethylene. The gases may be lobtanedfrom the cracking of gas oil or fuel oil at temperatures from 850-1000 F. and preferably, from SOO-950 F. The gases are those produced after the cracked gasoline has'been removed. Other processes for producing these unsaturates may be employedtoj produce the unsaturated normally gaseous hydrocarbons here addedto the polymerization and y reforming operations, as herein described. The

saturated normally gaseous hydrocarbons undergo dehydrogenation and polymerization during the reforming operation. The decomposing reactions occur best at low pressures, the polymerization at higher pressures. It therefore may be desirable to increase the pressure in passing through the polymerization stage. The diniculty of compressing hot vapors makes this step practically diflicult. It is, therefore, desirable to compress only the cold feed and to operate the whole system Aunder the desired high pressure' for the polymerizing reaction. The use of catalysts permits the use of lower pressures-for the polymerizing reaction and lower temperatures forthe reforming reaction than would be possible without the catalyst.

I Whilethe processes 'of reforming and polymerization are two distinct processes which may 'be separated the one from the otherby careful choice of conditions and catalysts by control of conditions, as previously described, processes may be interwoven. g.

In operating a combination of reforming and polymerization such as, for example, those shown in Figures 1, 2,l 3, and 5, Where saturated normally the two reforming zone, this reforming may be operated at a relatively high temperature to form larger amounts of unsaturated normally gaseous hydrocarbons in the vapor mixture passing to the polymerization stage.` In such a. process an active dehydrogenating or reforming catalyst may be employed. The temperatures to be employed may be in the upper portion of the range suggested for the reforming catalyst. Another procedure to be followed in this connection is to carry thereforming on at relatively high temperatures'to produce large amounts of gas by extensive cracking of the feedstock, Thus, for instance, in operating on a charging stock com- .posed of crude gasoline of from 15G-500 F. end

point, the cracking maybe carried on to produce large gas yields Vin excess of400-500 cu. ft. per barrel of charging stock. These gases, together with any added gas may bepassed to the polymerization stage. In this Yconnection the gaso line fractions may befirst removed and the lighter gases polymerized or the polymerization may be carried on in the presence of the reformed gasoline fractions.

The cracking and dehydrogenating processes of reforming are reversible reactions, and concomitant with them occur polymerizing and hydrogenating reactions. The unsaturated bodies formed as a result of the cracking and dehydrogenation are extremely active and tend to combine with each other. The light unsaturated gases tend to polymerize with themselves and with the unsaturated higher molecular weight l carbons and an increased .yield of high octane.

material over that resulting from a simple reforming operation. The lower molecular weight unsaturated hydrocarbons, particularly those of five carbon .atoms and less are polymerized with themselves and are also polymerized by addition of the higher molecular weight liquid Ahydrocarbons of six carbon atoms and more formed in the reforming reaction, or present in the hydrocarbon material forming the charge 'to the opermay be placed in reaction zones of If desired, instead of using a mixture of catalysts, the catalytic zones may be separated and the reaction mixture passed separately or alternately over a dhydrogenation and polymerization catalyst. This may be accomplished by passing the mixture through a series of tubes of the nature of cracking tubes connected together by return bends and the tubes filled alternately with a dehydrogenation and a polymerization/catalyst e is rein a number of runs so that the mix formed and polymerized in repea passages over the catalyst. The tubes may be placed in The reaction mixture is then heated and cooled, first heated to the reforming temperature in the reforming tubes, then cooled to a lowerl polymerizing temperature in the polymerization zone. If desired, temperature alone may be used to produce the desired reforming and polymerization without using catalysts in the tubes.

While catalytic operations are preferred, certain of the advantages of this-operation are preserved in non-catalytic processes thus either the reforming or polymerizing reaction or both may be operated without the aid of catalysts to ob- Itain a greatnumber of the `advantages of the operation. l

Another 'arrangement which may be used is to carry out the process in ,a heated chamber throughv which are passed cooling tubes. Cracking and dehydrogenating catalysts may be deposited on the warm walls of the chamber andV polymerizing catalysts .on the cooler tubes.

If ldesired,'air may be passed with the vapors through the cracking anddehydrogenating zone in such .cases where thel oxygen or water vapors will not have a poisoning action on the catalyst,

in order to removeundesirable gum-forming con..

stituents such as diolefin. Olens other than those that react readily with free oxygen are not objectionable constituents in gasoline. and their.

conservation is desirable. Retention of these d esirable unsaturated. compounds maybe accomplished by a controlled polymerizing action which only affects those unsaturates which are most` readily polymerized and leaves the others to contribute their high anti-detonatingcharacteristics to the fuel. i

The process of polymerization andalso of ref fractions to a reforming and polymerization reacforming results in a product which is composed of a polymer vandreformed gasoline fraction of highv octane and having an end point of from o-400 F. depending' onyoperations, a heavy gasoline-kerosene fraction having anend point of about 50G-550 F. and a vheavy portion. The heavier fraction called heavy gasoline-kerosene is recycled, While the gures describe the total return, it will be understood that only a portion merization reaction in which tion in the presence of Aa reforming `and polymerization catalyst under such high pressure conditions and such conditions of temperature that the polymerization and reforming operations are both aided by the presence of the polymerization and reforming catalysts.

It is arfurther object of this invention to sub: ject gasoline and kerosene and heavier petroleum fractions to a reforming .operation and subsequently to a polymerization operation under such conditions of temperature and pressure that the reforming operation is carried out at a higher temperature than the polymerization operation wherein the reformed gasoline composed of gaso-y line and kerosene fractions, and-containing normally gaseous hydrocarbons are subject to a lower polymeriztemperature for polymerization of the able hydrocarbons at that temperature and pressure.

This erence to the sub-joined n gnres in which: Figure l'is a ow sheet showing the polymerization and reforming reactions and providing for withdrawal and the addition of a catalyst at an intermediate point in the reaction;

Figure 2 shows la stage reforming and polya promoter is added to the reaction undergoing polymerization;

' Figure 3 shows a stage polymerization and re- Y forming reaction wherein provision is made'for may be returned and the remaining portion -sent v to storage or re-run on blending Istock with the polymer and reformed gasoline. f

It is therefore an object of this. invention to subject kerosene and gasoline and heavier petroleum fractions to a reforming operation in Athe presence of a reforming catalyst. A

It is a further lobject of this invention to form a reformed and polymer'gasoline by subjecting gasoline, kerosene and heavier hydrocarbons-to a reforming process and to subject light hydro-A carbons to a polymerzing reaction to form a poly.. mer gasoline, and to combine and rectify the two to produce a. reformed and polymer gasoline.

It is another object of this. inventio'nto subject gasoline and kerosene and heavier petroleum fractions toa reforming operation in the presence of a catalyst' which will aid the polymerization of the lighter hydrocarbon fractions, and4 particularly, those which are normally gaseous in the reforming operation.v

It is a furtherv object of this invention to subject gasoline and kerosene and heavier petroleum fractions vin the presence of agnormally gaseous hydrocarbon to a `reformingV and' polymerization reaction, preferably in the presence of catalysts which will accelerate and. aid the reforming and polymerization reactions.

It is a. further object of this invention to subject gasoline and kerosene and heavier petroleum l 2 through valve 3 and line tion and the control of temperature in reaction; i

Flgure`.4 shows a combined polymerization and reforming operation;

Figure 5 shows a design and iiow sheet of a combined polymerization and-reforming opera-.x

a 'furnace structure for the controleof temperature in the various coils of the` furnace;

Figure 6'shows a simultaneous polymerization and reforming operation tion and reforming operations are carried on separately, and the products are combined and treated together.

Figure 1 represents a A combined reforming and polymerization process in which the reforming is prim y conducted in one zone at relatively higher temperature and polymerization in another zone of relatively lower temperature. .In Figure 1 gasoline, kerosene. or gas oil fractions having end points under 60o-'650 to be reformed are I into the reforming coil 1 in furnace 8. The reforming catalyst may be added before passage to the heating coil through line 5 controlled by valve The mechanism for the addition of the solid catalyst to the oil stream is shownschematically .as indicated. Mechanisms for the addition of solid materialrvto liquid being well known in the chemical en- 'gineering art. The reforming catalyst may be one ofthe previously mentioned catalysts or may invention will be betr understood by refthe polymerization schematic flow sheet of a l fed through line I by pump wherein the polymerizabe a mixture of reforming and polymerization closing valve I4 and opening valves I0 and I6.'

The streaml of catalyst and oil vapor is then passed through line 9 and meets oil residuum such as fuel oil entering at I I to act as a dousing medium to wash out entrained catalysts and separate the vapors from the dousing medium in the separator I2. The temperature maintained in the separator is about `500'F. to insure the vaporization of the gasoline fractions. The

mixture of oil and catalyst is removed through valve controlled line I3, and the vapors of gasoline and lighter fractions includingthe hydrocarbons of four and less carbon atoms, pass through line I and valve I6 into line 9'. ever, if it is desired that the catalyst present in the reforming lcoil 1 and catalysts entrained in v the vapors passing vtherethrough be also present in the polymerization zone, valves I0 and I6 remain closed and valve I4 is open. In the event the operation in' chamber I2 is carried out, additional catalysts may be added through line I1 or provided as catalytic mass in the reactor chamber 29. It vmay be found desirable to add fresh Acatalysts to the reaction mixture. Also, in the event that the operation in chamber I2 is not carried out, the reaction mixture passes through line 9' in order to increase the concentration of active catalysts in the reaction mixture.

The reforming operation may be carried out with the omission of catalyst introduction through 5, and the entire reformed. mixture` may be passed either through I4 or by-passed to I2A and the'separated gasoline sent to reactor chamber 29 in the same manner as previously described. The catalyst added through I1 is preferably chosen from amongv the polymerization catalysts herein previously disclosed. In order to increase the concentration of light hydrocarbons there may be added throughline I3 liquid gases produced in the stabilizer 46 as will be Howly by adjusting the valves 28a in lines 28 and valved line 29 and valves Sla and 32a in line 3I so that the flow will be downward through the reactor and into fractionator 33. If the catalyst contact mass is used; it may be'desirable to flow the vapors upwardly through the reactor and in which case by proper manipulation of the valves 29a, 28a, 3Ia and 32a, the flow may be properly directed. Gasoline thus formed will result from the reforming reactions operating on the charge to coils 1 and on polymerization of the reformed vapors and gases.`

The reformed and polymer gasoline then passes through fractionator 33 containing the usual reflux cooler 42 which may be either internal or.

external. The heavy fraction, containing the suspended catalyst if this is combined in the vapors is removed from the tower through line 34 controlled vby'valve 35. The heavy gasoline fraction is removed through line 36, pump 31 for recycling to the reforming Aoperation via line I9 or is removed from the system partially or totally. The reformed and polymer gasoline is removed through side stream take-off 38 `into tank 39, passed by pump 40 through heater 4I and line 45 into the stabilizer 45. Uncondensed gas from the fractionator passes through line 43, compressor 43a and line 44 into the stabilizer 46.

The gasolines and gas are separatedinto a stabilized gasoline removed through line 5I, valve 52, and cooler v53 and the liquid gas fraction containing butanes, butylenes, propanes, propylenes, some ethane and ethylenes in liquid form pass into tank 56 and circulate by pump 51 through line 20 as previously described. Heat is supplied to the bottom of the tower by circulation from a lower tray through line 41, heater 49, and returned through line 50. 'I'he uncondensed and fixed gases are removed through line 54,-conhereinafter described. There'may be also added v at this point liquid gases from an extraneous source throughy line 2| and pump 22. These gases are preferably propenes, butenes, ethylene, or mixtures of these hydrocarbons with the saturated hydrocarbons of four or less carbon atoms. The mixture is formed in line 9. Inv the event that the cooling operation in chamber I2 and the cooling effected by the addition of the liquid material through line I8 and vaporization'of this material has reduced the temperaturebelow the chosen reaction temperature, the mixture may be by-passed through line 23 and reheating coil 25 in furnace '8 by the proper manipulation of valves 9a, 24 and 21a. This control heater will .then adjust the temperature in line 284to the proper reaction temperature to be -maintainedsin mixture; `In operating the reactor without the catalyst mass it would be advisable to direct the flow of vapors-and entrained catalyst downwardtrolle by valve 55.

The. conditions to be maintained in heater 1 and in the reactor 29 are those previously described and must be adjusted for the stock and catalyst employed as will be well understood in the art.

In carrying out the process shown in Figure 1, any one of the catalysts here described may be employed, but the now will be explained using one of the catalysts merely to illustrate the principle of carrying out the reaction.

It will be understood that the "other catalysts may be used with the proper control of temperature and pressure according to the principles hereinabove fully described.

A kerosene fraction having an end polntvof about 550 F. is passed through line 3 and is intimately incorporated to form a slurry with molybdic acid, molybdenum sulfide, or calcium aluminate, and is heated to a temperature of about 930 to 1290 F. in coil 1. The mixture is then passed through line 9 into chamber I2 in which the catalyst and the oil are withdrawn and the vapors at a temperature of about 450 F. are withdrawn through line' I5. Material is -added through line I8 and the mixture at a temperature of about 350 to 400 F. is introduced into chamber 29 which is charged with a phosphoric acid cata- V lyst in the form of orthophosph'oric acid deposited ing improved characteristics inthe iinal product. As previously described `the catalysts may be either added to the material entering the reforming operation or present in the reforming tubes polymerization and reforming catalysts of the v adsorbent clay,type, suchas fullers earth or on using base catalysts like aluminum oxide, hy-

Mdrochloricacidfgasgoralkyl'chlorides which-react at the temperature reaction in the presence of y lthese catalysts activate these catalysts. It has been found additionally, that these alkyl chlorides are themselves quite readily polymerized into higher molecular Weight hydrocarbons or chlorinated hydrocarbons. While this polymerization is shown as occurring in a catalyzed reaction, the alkyl chloride with or without mixture with the hydrocarbon feed as' here shown, may be polymerized in tubes 1 in an uncatalyzed reaction. The action in reactor 29 if desired may be catalytic or the end product of the uncatalyzed polymerization in 1 may be digested to aid polymerization in chamber 29 free of catalyst.

In carrying out the process shown in Figure 2 v thefeed is described as being made up of gasoline fractions to which maybe added the alkyl chlo-v rides. It is of course possible that the feed may be composed of alkyl chlorides alone. However, it is preferred to operate the process in Figure 2 whereby the alkyl chlorides are added to the gasoline and in the event the alkyl chlorides are used as a promoter in the catalytic polymerization reaction they will be added to the reaction mixture entering the polymerization zone. Heavy gasoline or kerosene passes through line l, pump 2, to be passed with stock added through valve 3 and pass then into line 4 and valve 3 into reforming coils 1 in furnace 8. Alkyl halides may be fed through line 60 and valve 60a, into reaction coil 1, or in the event' that the feed is composed entirely of these halides, material is not introduced in line-I. If it is desired instead of feeding halides through line 60, valve 60a may be closed andthe halides may be introduced into line 9. Polymerization catalyst is introduced into the stream passed into line 4 as previously described` by any well known solid feeding mechanism. The point of introduction should be prior to the introduction of the stream into coil 1 unless the catalyst is contained inside the coils. Reformed material passes through line 9. Before entering line 9 it. meets liquid gas introduced through line I8. These liquid gases may be introduced from stabilizer 46 as later described or may come from an extraneous sourceor may be both.' The reactor 29 may be used either as an additional contact catalytic zone in which case the catalyst is maintained in the reactor as a :ontact mass or the reactor may be empty and merely provide reaction time. The material passes through line 9'controlled by valve 9a and through the reactor 29, passes through line 32 l drawn through line 36 and pump 31 to act as urecycle stock as previously described.v The reformed and polymer gasoline iswithdrawn through line 38 into tank 39 and passed through pump 40 and heater 4I to stabilizer 46. The gases uncondensed by cooler 42 pass through line 43, compressor 43a into stabilizer 46. In stabilizer 46 the gasoline and gases are separated into a stabilized, reformed and polymerized gasoline which is withdrawn throughv line I and cooler A53. Bottoms are circulated through line 41, heat- -er -49 and 'line 50 to provide heat in the base of the clumml Liquid,A frac'tiapns composed of butane, butylene, propane, propylene, ethane and ethylene are withdrawn in liquid form into tank j 56 and passed .to line 20 into. line 6I as will be hereinafter described. The Q-uncondensed and xed gases'are withdrawn through line 54 controlled by valve4 55, cooledl and condensed to prov ide a refluxA to 'column-4 6. Thellqueed gases I"a'i'ewithdrawn 'through line 20 to which may be added from an extraneous source, preferably4 unsaturated normally gaseous hydrocarbons or mixtures ofsaid hydrocarbons and saturated normally gaseous hydrocarbons. The gases may be separated in the following fashion: A portion may be introduced through line I8 and valve la Aas previously described. Another portion may be passed through line 6I controlled by valve 6Ia to the reaction chamber 62 for conversion into the halide. It has been found that unsaturated hydrocarbons in .the nature of propylene, butylene,

I"=-amylene will react with hydrochloric acid in the presence of activated fullers earth or aluminum oxide at' temperatures from 32-390" F. to form alkyl halide. Propylene will add in the presence of hydrochloric acid at temperatures from 32- 390 F. to hydrochloric acid very smoothly.' The alkyl chloride thus formed may be introduced into the reaction stream by passing through line 63, valve 64 and line 65. In passing through 65 it passes as a vapor and may be introduced into line 9 to activate the 4polymerization in reactor 29. It has been found that as much as from onetenth to five-tenths percent of isopropyl chloride when added to the gases entering the polymerizer reactor chamber 29 accelerates polymerization reaction markedly. The chloride may be passed via line and valve 60a into coils 1. Instead of .y passing the isopropyl chloride as a .gas the and valve 32al to fractionator 33. In the event l that reaction' is completed in coils 1, the reactor may be by-passed by closing valves 9a and 32a and the vapors passed through line `3 l controlled by valve 3|a directly into fractionator 33. In fractionator33 materialA is separated into a heavy residual fraction and is Withdrawn through line 34. The bottoms are reheated by circulation through lines 23, pump 23a, heater 25 and line 21. Incompletely converted gasoline is withisopropyl may be condensed by passing through line 63a, valve'64 remaining clo-sed to cooler 66, collector 61 and uncondense'd gases may be removed through valved line 68; the condensate is fed by pump 69through valved line 10 as previously described. The hydrochloric-acid may be added oxide formed'by the co-precipitation of alumina l and silica by the interaction of sodium silicate and aluminum sulfate, as previously described. Reaction chamber 62 is charged with activated fullers earth or aluminum oxide as previously described. The temperature maintained in reactor 62 is as described, under 390." F. Dry hydrochloric acid gas is fed through 1I and alkyl chlo- 'ride isintroduced into line I8. The material entering line 4 is a slurry of the fullers earth or aluminum oxide and oil. The temperature maintained in coil 'I is in the neighborhood of S30-10.20 F. and the temperature in reactor 29 is 5 from G40-'730 F. This temperature' is maintained by the introductionof material through 29 or through cooling the gases entering through 9 by an interchanger, as will be understood although not shownint-heirawings, or by the conl trolin the reactor 29uas-sh`own in Figure 3. Cooling in line 9 maybe provided as shown in Figures 3, 4 and 6. Pressure maintained in coil 'I and reactor 29 is in the neighborhood of 500-1500 A Figure 3 showsjschematicallya combined process of reforming and polymerization process in which separate reforming and .polymerizationzones are provided. A'reforming zone is provided iri coill in which coil 'polymerization may also 20 to rise, and it is desirable to control the temperature to prevent excessive increases in temperature.

Feed oil is introduced under pressure through line I and may pass either through line Ia and valve 2a or through line Ib and valve Ic, or 3c -heated by passing through; valves 84 and 86 and through both to the reformingcoils 1. It is preferred, in the event that the feed is a mixed feed containing a wide range vof boiling fractions such as gasoline; kerosene and gas-oil, to rectify the feed by introducing it through line Ib and valve Ic into the fractionating chamber 33. In this chamber it meets the hot vapors from the reaction zones and aids in the fractionation of these vapors to form a heavy residual fraction 28 composed of the heavy ends of the charging stock and the heavy ends of the polymerized and reformed gasoline. A side out of intermediate boiling fractions is removed through line I9b and circulated through line I9 to meet any portion of material by-passed through line Ia if any such isbypassed. If desired, a portion of the liquid gases which are to be polymerized are introduced through line 80 and the mixture is then passed through line I a, heat exchange coil 3a, line 4 into the reforming coils 'I positioned in furnace 8. 50

At the outlet of coil 1 the reformed gasoline is doused by contact with relatively cold heavy oil such as fuel oil entering through line II and the partially cooled gases are then passed through heat exchanger 3b from which point they may be 55 passed directly to the polymerizing chamber 29 via line 9', or first passed through the separator I2. In separator I2 the heavy ends arc removed through line I3 and the vapors -Withdrawn from line I5. IIhe stripping of the bottoms to insure the removal of the gasoline fractions is aided by, the introduction of xed gases such as hydrogen, methane, carbon' dioxide or liquid gases used in the polymerization reaction in `chamber I2. With some catalyst where steam is either an aid or is not a detriment to the polymerization reaction, steam may be used at this point. A spray of wash oil I2a. is passed over'the mist extraction and fractionatng elements I2b to insure separation of entrained materials Yand heavy ends of the vapors. Instead of passing the vapors through this chamber, the chamber may be by-passed by; proper control of valve I0 in line 9 and valve 9a in line 9 to pass the vapors around the separator. rThe vapors are then passed to the poly- 7 5 merizing zone 29. Instead of passing the gases through the reforming zone, or in addition to passing the gases through the reforming zone. they may be added to lthe vapor in line 9 through by-pass line` I8`by proper control of valve Ia and valve a. The mixed gases and vapors are then passed through line 9 into the reaction zone 29. 1

In order to control the temperature in the reaction zone 2 9,` the liquid gases may be expanded through spray 8I by .proper control ofvalves` 82 4and also by circulation of cooling `fluidthrough the cooler 83 via lines 83a and 83b. In operat- `ing the separator I2 in such'manner that only the light fractions of gasoline are separated, the temperature of the outlet vapors may sometimes be below the desired temperature in the polymerization chamber 29. Thus for instance, the

vapors issuing Athrough line I5 may be in the neighborhood of 400-450 F. While the reaction 'zone may be of a temperature of 600 F. and above.

Under those circumstances it may be desirable to heat the reaction chamber 29 instead of cooling it. To do this the cooler 83 may be converted to a\heater by circulating a heating fluid through the coils of the cooler 83. This cooler may be of the closed tube sheet type, the cooling fluid circulating out of contact of material in the reaction chamber 29. The gases entering through valves 82 and spray 8| maybe heater by the proper manipulation of valve 91j. Any desired proportion of the gases to be added for polymerization may be added in this way. Such gases thus added are not subject to the reactions occurring in the reforming coils 1. If it is desired to polymerize these gases Without subjecting them to the reformingoperation all the gases may be introduced in this' manner.

The heavy polymers formed in the reaction zone and which are not volatile at the temperature in chamber 29 .are withdrawn through 34a and the vapors are Withdrawn through line 34 to be passed to fractionator 33. There they pass countercurrent to the feed Ib and the reflux formed by cooling coils 42. In addition to the heavy cut I9b, a reformed and polymer gasoline- A s and cooler 53. 'I'he bottoms are reboiled by cirg-l culation through line 41, heater 49 and return line 50. `A liquid light hydrocarbon fraction withdrawn through line 56a into chamber 56 and composed of the fractions 'containing four or A l lower carbon atoms, both of. the saturated andv unsaturated types. Fixed gases are withdrawn through line 54, condenser 54h and recycldas a reflux through line 54a. The liquid gas is circulated through line 20 by pump`51 and meets additional gases throughvalve 81 coming from storage 89. These liquid gases 'are similar to those in 20 and are lderived from 'other refinery sources. I These gases may be sent through line 88 or 80 as previously described.

In operating the process according to this flow sheet the temperature in coil 1 may be fromv 600-1000 F. Thus, for instance, it may be operated at about 980 F., cooled by the dousing medium to about 650 F. and further cooled to .about 500 F. and separated in I2. Vapor withdrawn through line I5 may be in the neighborhood of 425 F. and the chamber 29 maintained at about 600 F. In employing a catalyst requirlng a polymerization temperature of 350-450 F. the reaction chamber is cooled. Catalyst may be omitted in the reform g operation and the temperature then empio ed mayl be from 950- in chamber 29. 'I'he temperatures and pressures ydiscussed with relation to Figure 2 may be 'applied to the process of-Flgure 3.

The catalyst tobe used in the reforming operationl may be either introduced into line lq by a feeder as previously described or may be y vapors' exit.

positioned in the coils of reforming coils 1. The

reaction chamber!!v may be charged with con-A tact mass `catalysts or theV catalysts may be introduced into line to pass with the vapors through line 'il'. It is preferred, however, in the structure shown in Figure 3, to charge reaction chamber with catalysts. v

In the operation according to the flow sheet shown in Figure 4, the polymerization and the reforming operation are carried out in one zone. The feed .which consists of kerosene andI gasoline fractions containing added thereto propane, butane, propene, butene.' ethane, and ethylene produced as previously described, ls passed under pressure together with the catalyst, if an entrained catalyst be used. through lines IV and 20 and through heater exchange la, line 4,' coil 'l positioned in chamber l. Instead of using an entrained catalyst I may use coils charged with catalytic mass. Polymerized and reformed gasoline is 'then doused by contact with heavy fuel oil entering through Il passed into the heat exchange 3b and through separator I2. The heavyv fractions are withdrawn through line I3 and the vapors are passed through mist extractor and fractionator elements |2b and Washed with oil introduced through l2a to separate the heavy ends of the vapors. 'I'he vapors then pass through line I to the fractionator 33 in which the heavy o il is 'withdrawn through line 28 and vapors reuxed by reflux produced by cooler 42. The polymer and reformed gasoline are withdrawn into side stream receiver 39, and passed by pump d0 through the heater 4l and introduced into the stabilizer 46. The unconden'sed vapors through line 43 are also introduced into stabilizer 46 by compressor 43a. In the stabilizer thevapors are separated into a stabilized gasoline,- withdrawn through 5| and cooler` 53. The bottoms are heated by circulating through line' 41, heater 49 and line 50. Reflux is obtained by the condensation of the vapors, withdrawn through by-pass 5d, valve 55, condenser 54h and condensate collected in 54' returned through lilla as amrefiux. Liquid fraction withdrawn through 56a contains the hydrocarbons ranging from butanes and butylenes,i propane and propylenes to .ethane and ethylene. These Vare recirculated through line to be sent to reformer coils l.

The temperature chosen in Figure 4 inoperating with fullers earth may be in the neighborhood ofA 840l020 F.; the pressure in the neighborhood of 500-5000 lbs. 'I'he other conditions Willfoilow those described-With regard to Figure 3.

In view of the fact that the polymerization reaction using certain catalysts as previously de'- scribed, operates best at temperatures lower than the reforming operation, the form of heater *shownvin Figure 5 provides for reaction zones of alternatively high and low temperatures in Vwhich the reaction mass is first passed through high temperature and then low temperature zones. The reforming catalysts may be positioned in the high temperature zone and polymerizing catalysts in the low.. temperature zone orthe mixed catalysts may be used in both zones. The

"furnace 3- is divided by vertical partition walls VI0!) to form chambers '8a and 8b. :Ihe coils 1 are positioned in both zones, the flow being iirst passed through the coils in zone 0a and then zone 8b,l and then zone 8a, etc.. as shown until the 'I'he furnace is heated by burner I0l in combustion tunnel lllafand the gases escape through conduit |02. The combustion gases maybe split by'propermanipulatinof dampers |03 and IM'. A portion maybe through conduit` |05 passing into the'ilue Ill leading to the stack. -Combustlon air which is also used fr cooling thev chamber l0b `is circulated through conduits lII and III by fan Illpa'ssed through low temperature zone 0b and conduit l il.4 A portion ofthe thus preheated air is split byproper manipulationof-dampers lll and Ill; and passes through conduit U0 toprvide combustion air for burner I0 l. In this fashion cold air, and if desired, lflue gases recycled by ythe circulation of the portion of combustion stream lfrom `conduit I02,.-is.circulated over the coils in chamber 8. Chamber 8b is therefore maintained at consider- |00 is preferably made of heat insulating material which is suitable for high temperature operation such as fire brick or diatornace'ous earth bricks. By proper circulation of air any desired difference in temperature may be maintained. It is understood that instead of passing the' reaction material first; through'the coils in chambers 8a, then through chamber 8b and then through chamber 8a,\ etc., the vapors may be passed in any'number of passes through the coils in chamber-8a,and then to chamber 8b to pass in the chosen number'of passes. Thus,.the vapors may be passed to chamber 8a to carry on the reforming reaction, and then passed through chamber Bbjfor polymerization.. The gases after exiting from' chamber 8b are then treated as Ashown in Figure 4. It Will lbe understood that the furnace construction and flow yshown in Fig- 'ure 5 may also be used in place of the furnaces shown in Figures 1, 2 and 3.

In operating the reaction in Figure 5, the coils in chamber 8a shall be maintained from 930- l020 F. while the coils in chamber 8b shall be at about G40-'720 F. In this case the catalyst may be fullers earth or activated fullers earth, or aluminum oxide,L or the precipitated oxide previously described.

While the descriptions oi. the preferred operation in Figs; 4 and 5 are given with relation to catalyzed reactions, the process there described Yj In the foregoing process of alternately reforming and polymerizing the products from the reforming operation, the heating of the initial gasoline stock to a reforming temperature, for extion operation on thes'tock, a product maybe eventually produced containing a relatively large amount of aromatic hydrocarbons which are beneficial in'4 a motor fuel. p Figure 6 shows almodication wherein thereforming and polymerizationfreaction is separated,

and the polymeriz'ed'fand reformed materials are combined for treatment tof-produce'- a=-'blended, stabilized,l polymerized and 'i reformed-l gasoline. .Feed composed lof petroleum" fractions," for' instance kero'sene" and" gasolinegf-isj"introduced th'rough'lir'ie'.v into fractionator 33." Asidef'cut having 'anA intermediatelfboiling :ra-nge is 'withvdrawn through line-| @by pump 2 *andsent through heat yexchange 3a -into'ref'rming chamber v1' posi- Vtion-ed -in furnae 8': Reformedgasolin'e is-then 'contacted'withthe dousing' 'oil `composed -of fuel oir-.introduced through '||',r Where it' is partially cooled andv theripassed through heatA exchange lco'il 3b; It'r'neetsiin1=liriei9. polymerized material introducedthroughflineWSlL" The lmixture 'of polymer-ized and f -'1'e'forrned--fgasoline passes into separatorei-Zf 'and' through' mist extractor* |2b. -T-he heavy ends are withdrawnthrough I3 and the 'uncondensed vapors of a temperature from 425450 F. are'removed` through line l5, then passed into the stripperand fractionator 33.

where, by the aid of the feedA I and the reboiler 33a and reflux coil 42 in fractionating chamber 33h, it is fractionated into heavy ends 2'8, recycle stock la and the side cut of reformed and polymerized gasoline withdrawn through line 39a. Reiiux is provided by coil 42. The uncondensed vapors are Withdrawn through line 43. The side cut 39a. is passed by pump 40 into heater 4| and into the stabilizer 46. The uncondensed vapors are passed by pump 43a, linen, into the stabilizer 4,6. In this stabilizer the gasoline is stabilized by the aid of reboilerABa and reux provided by the condensation of gases withdrawn through valve 55, lines 54 and 54a and'condenser 54h. Stabilized gasoline is withdrawn through 5|, and liquefled gases containing the butanes, propanes, butylenes, propylenes, ethane and ethylenes pass through line 56a into collecting chamber 56 for recycling by pump 51 through line 20 into line 80. In this line it meets additional like materials through line 81. The commingled gases are then passed-into heat. exchanger 9| a into polymerization coil 9| positioned in furnace 92. 'I'he hot gases are doused by mixing with a dousing medium'such as gas oil, fuel oil, or kerosene, or gasoline introduced through 93 and passed through heat exchanger 9| brand through 90 as previously described. I

The reaction in coil 1 may be uncatalyzed or catalyzed. If catalyzed, the catalyst may be any one of thereforming catalysts hereinabove indicated. The temperature may be regulated indebe independently controlled. by regulating valve 90a. The temperature in coil 1 may, depending upon the catalyst, beffrom 8501050 F. and the pressures from about 15G-500 lbs. If uncatalyzed, the temperature may be between 900-1250 `F., while in coil 9|, the pressures may be around 500-5000 lbs., and the temperatures from 230- 750 F., depending upon the catalyst employed. Any of the polymerizing catalysts previously described may be employed. `Mixed catalyst slurry is removed through'chamber Al2'. 'This will de` pend on the catalyst and stockv chosen as will be understood --from'what-h'as been said previously. Ify thefareactions in vcoil 9| are uncatalyzed, the temperaturemay range'from 850;950"F.

- yThe y'foregoiiig 'description 'of the' several 'modi-z 'cations of'my invention described above are not to becon'sidered as limitingsince' many variations may lbe'rnade within the s'copef-of .the following claims by those skilled'in'the art Without depart'-I ingfrom the lspirit thereof. A 'v The present application'is-a division of my co- I -pending application, 4Serial No. 35,702, led August12, 1935.'H I

, -1. -A processsforlthe production of reformed and polymergasoline. comprising passing hydrocarbons boiling yWithinthe'gasoline range in a restrictedstreamthrough a heated zone to'heatsaid f mixture to a gasoline-reforming temperature and reformingv -said gasoline hydrocarbons therein,

subsequently passingV the resultant gaseous and vaporous mixture through a polymerization zone maintained at. ya polymerizing. temperature lower than said reforming `temperature and polymerizing the normally gaseous hydrocarbons present in said mixture is said polymerization zone and then passing. saidl 'mixture in a restricted stream through a heating zone where said mixture is reheated to a gasoline reforming temperature and reformed therein.

2. A process according to claim 1 wherein the reforming and polymerization are accomplished in the Vapor phase over a series of reforming and polymerizing catalysts.

3. A process for the production of reformed polymer gasoline comprising passing hydrocarbons boiling within the gasoline range in a restricted stream through a heated zone to heat said mixture to a gasoline reforming temperature and reforming said gasoline hydrocarbons therein, subsequently passing the resultant gaseous and vaporous mixture through a polymerization zone maintained at a polymerizing temperature lowerthan said reforming temperature and polymerizing the normally gaseous hydrocarbons present in said mixture in' said polymerization zone, then passing said mixture in a restricted stream through a heating zone where said mixture is reheated to a gasoline reforming temperature-and reformed therein, and then passing said reheated and reformed gasoline through apolymerization zone maintained at a polymerizing temperature lower than said reforming temperature.

4. A process according to claim 3 wherein the reforming and polymerization are accomplished in the vapor phase over a series of reforming am:1 polymerizing catalysts.

l PHILIP SUBKOW.

pendently of coil 9|. The pressure in coil 9| may'

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