US2342123A - Alkylation of hydrocarbons - Google Patents

Description

Feb; 22, 1944.

J. DJYDANFORTH ALKYLATIQN OF HYDROCARBONS Filed Jan. 10, 1 941 moEzo u E ATTQRNEY INVENTOR IIIIL. In I" I MHhs IIIIL H T R O A D U H P E S O .J

uaiui 2 .5553

Fatented Feb. 22, 1944 ALKYLATEON @F RYDROCABBONS Q Joseph lit. Daniorth, @hicago, ML, assignor to Universal cu Products Qompany, Ghicago, 11L, a

corporation of Delaware Application January it, ianfseun No. 373,960

cams. (e1. ace-asap This application is a. continuation-in-part of my co=pending application Serial Number 370,323, flied December 16, 1940.,

This invention relates to the treatment of isoparamnic hydrocarbons to produce higher molecular weight alkyl derivatives thereof. More specifically the process is concerned with a method for alkylating isoparaflinic hydrocarbons and other branched chain paramnic hydrocarbons with oleflns in the presence of a volatile catalyst introduced by means of a substantially inert carrying fluid comprising essentially one or more of the reactants charged to a reaction zone containing a packing material.

Alkylation of isoparaffinic hydrocarbons with oleflns may be effected in the presence of easily volatilized catalysts including aluminum chloride-hydrogen chloride mixtures, boron fluoride hydrogen fluoride mixtures, hydrogen fluoride, etc. When an alkylation reaction is carried out in the presence of a catalyst introduced as vapor it is necessary for a substantial proportion of the catalyst to be present in the allwlating reactor and consequently it is necessary to recycle large amounts of the catalyst. Similar recycling of catalyst is necessary when the usual type of alkylation is carried out in liauidphase or in mixed phase as near the critical conditions where both gases and liquids may be present in the reaction system. Iii order to substantially avoid the recycling of large amounts of catalyst, the reaction chamber employed in the present process is filled with a granular packing material upon which a substantial proportion of the catalyst, carried thereto by a fluid, is deposited and retained within the reaction zone. In this way a relatively high concentration of a catalyst is kept in the reaction Zone whileintroducing the catalyst in relatively small amounts with the hydrocarbons or other fluids being charged to the akylation process, rather than. in the largeramount required to catalyze the reaction.

In one specific embodiment the present invention comprises a process for producing higher boiling hydrocarbons which comprises subject- According to the present invention isoparaffinic hydrocarbons including isobutane and its homologs may be alkylated. The conditions of operation, however, may not necessarily be the same when alkylating isoparaflins and other branched chain paramn hydrocarbons of difierent reactivities. AlLoLthese alkylatable paraffins may be referred to broadly by the term isoparaffins. The olefins employed as alkylating agents are either normally gaseous or liquid and include e thyene, propene, butcnes, pentenes, hexenes, and higher olefins, the latter boiling generally within the approximate range of gasoline. The normally gaseous oleflns generally combine directly with an isoparaifln during alkylation, while hexenes and higher liquid olefins usually undergo depolymerization prior to or during alkylation with the result that two molecular proportions of a substantially saturated alkylate are formed from two molecular proportions of an isoparamn and one molecular proportion of a hexene, while some 'still higher boiling olefinsmay depolymerize or split to a greater extent and form more than 2 molecular proportions of alkylation products. 1 I

The alkylation of an isoparaiflnic hydrocarbon with an olefin in the presence of a volatile catalyst such as aluminum chloride or boron fluoride is generally aided by the presence of a hydrogen halide. Thus hydrogen chloride generally is beneficial to the eflicient utilization of aluminum chloride as catalyst and similarly the action of boron fluoride is improved by the presence of hydrogen fluoride. However, hydrogen fluoride alone may be utilized as a hydrocarbon alkylating catalyst and mixtures of aluminum chloride and boron fluoride may be employed similarly. The addition of a substantially inert gas as hydrogen to a hydrocarbon mixture being subjected to alkylation may improve the operation of the process and increase the time during which the catalyst remains active.

By the process of this invention volatile atalytic materials as aluminum chloride, boron fluoride hydrogen fluoride, etc; may be introduced to a packed reaction zone by means of one or more of the fluids being charged thereto. Thus in an alkylation in the presence of aluminum chloride, the aluminum chloride is picked up by a carrier fluid, which may be hydrogen,

hydrogen chloride, a parafiinic hydrocarbon or a mixture of any two or all of these substances, from an aluminum chloride charging vessel which is maintained under a temperature necessary to introduce into the carrier fluid the desired amount of aluminum chloride. The aluminum chloride may be present in the charging vessel as a solid, a liquid, a binary or ternary mixture with other metal halides, or as an adsorbed layer on an adsorbent material such as firebrick, charcoal, silica, etc. The mixture of aluminum chloride and isoparafilnic hydrocarbon with or without hydrogen and/or hydrogen chloride, is admixed with an olefin or an olefin-containing hydrocarbon fraction and the resultant mixture is charged to a reaction zone containing a granular packing material which may or may not have been impregnated by aluminum chloride. While an olefin or an olefin-containing hydrocarbon is the preferred alkylating agent, other substances as alkylhalides, alcohols, ethers, and esters may be employed similarly for alkylating hydrocarbons.

The aluminum chloride catalyst is charged continuously with the other reactants or inter mittently so that as the catalyst remaining upon the packing material within the reaction zone becomes spent during use, a further quantity of fresh aluminum chloride is introduced to the reaction zone containing the granular packing material which includes such substances as porcelain, pumice, firebrick, quartz, activated charcoal, other activated carbons, diatomaceous earth, kaolin, raw and acid-treated clays, silica gel, alumina, magnesia, zirconia, titania, composites of silica with alumina and/or zirconia and metals possessing considerable surface as spongy iron. Halides of the Friedel-Crafts type as those of aluminum, zinc, iron and copper may also be incorporated with any of the supporting materialsprior to being packed in the reaction zone, when such compositing is physically or chemically feasible.

The alternative reactor filling materials are not necessarily equivalent in their-action and the particular granular filling material employed in any given alkylation reaction is dependent upon the hydrocarbons being treated, the temperature and pressure employed, the nature of the catalyst charged, and other factors.

When relatively large reactors are employed it may also be desirable to introduce aluminum chloride and the carrying fluid to a reactor at various points between the inlet and exit thereof so that the aluminum chloride is present in exactly the optimum concentration at all points throughout the bed of granular filling material and also that no excess of aluminum chloride is present at the point of its introduction with a resulting deficiency of aluminum chloride at other points throughout the length of the bed of reactor filling material.

It is proposed to carry out the alkylation of isoparaflins with olefins in the presence of a volatilizable catalyst carried by one or more of the reactants into a packed reaction zone. When such alkylation is catalyzed by aluminum chloride, the fluid material entering the catalyst pickup chamber is heated to a temperature between about 150 and about 350 F. and the subsequent alkylation reaction zone is preferably maintained at a temperature between about 30 F. and about 300 F. under a pressure of from substantially atmospheric to approximately 500 pounds per square inch. The preferred operating temperature for the allwlation reactor is generally between about and 200 F. and a preferred pressure about 100 and 300 pounds per square inch.

In such a process where a reactant is substantially saturated with a volatile or soluble catalyst at one temperature and is then caused to react with a second substance at a relatively lower temperature, it is advantageous to divide the stream of the first reactant into two parts, to saturate one part with the catalyst at the higher temperature, and then'to combine the heated and unheated partsof the first reactant with the second reactant to form a mixture of desired temperature for subsequent catalytic treatment.

In the hydrocarbon mixture subjected to alkylation it is preferable to have a relatively high molecular ratio of isoparafiln to olefin, with an olefin concentration generally between about 1 and 25 mole per cent, in order to substantially avoid olefin polymerization and to favor alkylation. Hydrogen chloride is preferably present in the alkylation mixture generally to the extent of up to about 5 mole per cent of the total hydrocarbon mixture' subjected to contact with the alkylating catalyst. It is also recommendedto add hydrogen to the reaction mixture, generally in a quantity of not more than about 20 mole per cent of the total hydrocarbons.

The hydrogen and/or hydrogen chloride charged to alkylation may also be used for carrying thereto the aluminum chloride as it is generally desirable to carry the aluminum chloride by means of a fluid having a relatively low reactivity therewith. The paraflinic hydrocarbon may also be employed as a carrier but the olefin is less desirable for this purpose because of its ,tendency to undergo polymerization in the presence of aluminum chloride especially if hydrogen chloride or water vapor is present.

Other types of hydrocarbons as aromatics and naphthenes may be alkylated similarly with oleflns and the other above mentioned alkylating agents in the presence of a volatilizable or soluble catalyst introduced continuously by means of a fluid to a reaction zone containing a substantially inert packing material.

While a gas is preferably used as the fluid for carrying the catalyst to the packed reaction zone, a liquid may be employed similarly, although not necessarily under the same operating conditions. In the latter case the catalyst as aluminum chloride is dissolved and/or dispersed in one or more of the liquid reactants and the resulting solution and/or dispersion is thereafter charged to a reaction zone containing a packing material which retains in said reaction zone a substantial proportion of the catalytic material charged thereto. In this way it is also possible to maintain a relatively high concentration of catalytic material in a reactor to which more catalyst is introduced with the charge to replenish the loss of catalyst by sublimation and/or by solution in the reaction mixture.

The alternative means which may be used for introducing a catalyst to a packed reaction zone by a fluid carrying medium are not necessarily equivalent and the particular means employed in any specific case depend upon the properties of the hydrocarbons undergoing treatment, the nature of the catalyst, the conditions of operation, and other factors. 7

For the purpose of illustrating the combination of steps characteristic of the present invention,

the accompanying drawing shows diagrammatically one form of apparatus suitable for use in producing a more valuable hydrocarbon product by alkylating an isoparaflin with an olefin in a packed reaction zone in the presence of a volatile catalyst carried thereto by one or more of the charged reactants. It is understood that other types of apparatus may also be used for carrying out the process and that there are other methods of introducing a catalyst as by mechanically adding catalyst powder or by extruding into the system a paste-like material containing aluminum chloride. Also variations in the order oil-mixing the reacting components may be employed in the process.

Referring to the drawing, a hydrocarbon fraction containing isoparaflins is admitted through line I and valve 2 topump 3 which discharges through line 4 containing valve 5. At least a portion of the isoparaihn-containing fraction is directed from line 4 through line 6, valve I, and coil 8 which receives heat from heater 9 and thence through line ID to catalyst pick-up chamber H containing aluminum chloride as a solid, liquid, an adsorbed layer on an adsorbent such as firebrick, or as a binary or ternary mixture with other metal halides. In chamber II the temperature, pressure, and amount of isopara'ffin-containing hydrocarbon fraction passing therethrough are controlled so as to pick up aluminum chloride in an amount desired for use as catalyst in a subsequent alkylation treatment as hereinafter set forth. I

Although only one catalyst pick-up chamber is shown in the attached diagrammatic drawand the picked-up aluminum chloride is directed through line H containing valve 13 and is commingled in line it, by means hereinafter set forth, with an olefin-containing hydrocarbon fraction, fresh and recycled hydrogen and hydrogen chloride, a recycled fraction containing unconverted isoparafiin hydrocarbons, arid, when desired, a portion of the isoparaflin-containing hydrocarbon fraction charged to the process.

Hydrogen and/or hydrogen chloride are introduced to line I l containing valve l under a suitable pressure by a pump, compressor, or other means, not shown; an olefin or an olefin-containing hydrocarbon fraction is admitted through line it and valve H to pump or compressor it which discharges through line l9 and valve 2@ into line I4; and a recycled mixture of hydrogen and hydrogen chloride is directed through line 65 containing valve 66 to the line M from which the mixture contained therein is directed through line i2 and thence to reactor 2| containing a granular packing material. Chamber Ii may also be heated by any other suitable means and reactor 2| may be fitted with a meansof cooling if this is necessary to maintain the temperature needed for the alkylation reaction. I Also, the mixture containing isoparafiins, aluminum chloride, olefins, hydrogen, and hydrogen chloride being directed to reactor 2| by way of line i2 is therein commingled with a fraction conline l2 to reactor 2| containing a granular filling material which may consist of any one'or a number of materials as aforementioned.

When desired, paraffins, isoparamns, hydrogen, and/or hydrogen chloride may be used singly or in any combination to carry aluminum chloride from catalyst pick-up chamber throu h line i2 to reactor 2|- containing a suitable packin material. When hydrogen chloride is charged to catalyst pick-up chamber ll simultaneously with a paraflin fraction containing normal and/or mildly branched chain parafilns, a substantial amount of paraifin isomerization may occur in the cataiyst pick-up chamber in the presence of 1 aluminum chloride to form mildly branched chain paraflins from normal parafiins, and more-highly branched chain paraflins from the mildly branched chain parafilns. When such preliminary isomerization'occurs, the resulting branched chain parafllns may be alkylated with oleflns in reactor 2| simultaneously with the alkylatlon of the branched chain parailins and other alkylatable hydrocarbons present in the fraction charged to the process.

Such alternative means of carrying and introducing aluminum chloride to a packed alkylating reactor are not necessarily equivalent and the particular aluminum chloride carrying means chosen in any given case are dependent upon the reacting hydrocarbons, the amount of catalyst employed, the conditions of operation, and other factors.

The products from reactor 2| are directed through line 22 and valve 23 to separator 24 in which some relatively heavy residue or sludge containing partially spent aluminum chloride is separated and withdrawn through line 25 and valve 26. The products passing through line 22 may be cooled, by means not shown, and/or treated to remove aluminum chloride, as by scrubbing with a molten salt as a mixture of another metal halide and aluminum chloride or by passage through a vessel containing a granular adsorbent, prior to admission to separator 26. Although separator 24 is shown diagrammatically as one vessel, two may be employed so as to have one in use while the other is being cleaned.

When desired, the relatively heavy residue or sludge containing partially spent aluminum chloride may be subjected to contact, by means notparafiins comprising both normal and branched chain isomers, and substantially free from olefinic hydrocarbons, may thereafter be subjected to con tact with aluminum chloride to pickup and carry to the packed reaction zone the desired amount of aluminum chloride. The aluminum chloridecontaining sludge may alternatively berecycled The mixture of products containing a substantlally saturated alkylate formed from olefins and from a portion of the isoparaffln hydrocarbons as well as the excess of the isoparaflin-containing fraction, hydrogen, and hydrogen chloride employed in the alkylation step is passed through line 21 and valve 28 to fractionator 29 of conventional design in which a light fraction containing hydrogen and hydrogen chloride is substantially separated from higher boiling hydrocarbons. When it is desirable to operate fractionator 29 under a pressure above that employed in alkylation reactor 2| in order to assist in the separation of the reactants and products and to facilitate recycling of said light fraction and of unconverted paramns, valve 28 is closed and the mixture of hydrocarbons, hydrogen, and hydrogen chloride is passed from line 21 through line 30 and valve 3| to pump 32 which discharges through line 33 and valve 34 into fractionator 29.

From fractionator 29 a light fraction containing hydrogen, hydrogen chloride, and relatively small amounts of normally gaseous parailins, as methane, ethane, propane, and butanes, is taken overhead through line 35 and valve 38 to condenser 31 and thence through run-down line 38 and valve 39 to receiver 40 equipped with conventional gas release line 4| containing valve 42 and with liquiddraw-ofi line 43 containing valve 44. At least a portion of a normally gaseous mixture comprising essentially hydrogen, hydrogen chloride and some methane is directed from near the top of receiver 40 through line 45 and valve 46 to line l4, already mentioned, in which fresh hydrogen and hydrogen chloride are commingled with other reactants later conducted through line l2 to alkylation reactor 2 I. 1

Although the isoparaflin-contaimng fraction contained in line 4 is indicated in the attached diagrammatic drawing as the carrying fluid for the aluminum chloride catalyst, it may also be desirable to introduce to the fraction in line 4 by way of line 41 and valve 48 a portion of the mixture containing hydrogen and hydrogen chloride being recycled through line 45, aforementioned. A portion of the material present as liquid in receiver 40 is directed therefrom through line 49 and valve 50 to pump which discharges through line 52 and valve 53 into the upper portion of fractionator 29 to assist in controlling the temperatures therein.

From the bottom of fractionator 29 a normally liquid mixture comprising essentially a substantially saturated alkylate and an unconverted isoparaflln-containing hydrocarbon fraction is directed through line 54 and valve 515 to fractionator 56 of conventional design in which the unconverted isoparafllnecontaining fraction is separated from a substantially saturated alkylate-containing fraction of gasoline motor fuel boiling range, the latter being withdrawn to storage through line 51 and valve 58.

The unconverted isoparaflin-containing hydrocarbon fraction is passed overhead through line 59, valve 60, condenser 6|, and run-down line 52 containing valve 63 to receiver 64 equipped with conventional gas release line 65 containing valve 66. A portion of the condensab in receiver .54 is withdrawn therefrom through line 61 and valve 68 by pump 69 which discharges through line and valve II into the top of fractionator 56 to assist in controlling'the temperatures therein. The remainder of the condensate contained in receiver 64 and comprising essentially the excess of isoparailln-containing fraction unconverted in the alkylation, is recycled through line '12 and valve 13 to line =l2,-already mentioned. A

' portion of the freshly charged isoparaflin-containing fraction may be introduced to line 12 from line 4, thus by-passing the catalyst pick-up chamber l I.

The following examples are introduced as characteristic of the practical operation of the process. although they are presented with no intention of limiting the scope of the invention in exact correspondence with the numerical data since some latitude is possible in the choice of the type of reactor packing material, the amount of catalyst, the conditions of operation, etc.

EXAMPLE I 110 parts by weight (200 volumes) of a hydrocarbon fraction containing 3.8 mole per cent propane, 74.7% isobutane, and 21.5% normal butane, and 2 parts by weight of hydrogen chloride was passed downwardly per hour through a chamber containing 113 parts by weight of aluminum chloride granules maintained at 200 F. and-under a pressure of 200 pounds per square inch in order to pick-up in the fluid hydrocarbons a desired amount of aluminum chloride. The resulting mixture of hydrocarbons, hydrogen chloride, and aluminum chloride was passed downwardly through a subsequent reaction zone containing volumes of formed pieces of porcelain packing material and maintained at 150 F. After charging the iso-butane-containing fraction for onehalf hour, ethylene was also introduced to the reaction zone at an hourly rate sufllcient to give a reaction mixture containing approximately 10 mole per cent of ethylene.

A runfor a total of 45 hours yielded a total of 527 parts by weight (722 volumes) of a substantially saturated alkylate containing 169 volumes of pentanes, 472 volumes of hexanes with 91 cctane number, and 81 volumes of higher boiling grams (200 cc.) of the paraflin hydrocarbon fraction charged in Example I was passed per hour upwardly through a steel reactor containing 200 grams (173 volumes) of 4-20 mesh aluminum chloride maintained at 205 F. under a pressure of 250 pounds per square inch. The resulting mixture of hydrocarbons and aluminum chloride was directed from the top of the first chamber containing aluminum chloride to a reaction zone containing 100 volumes of porcelain packing material as used in Example I maintained at a temperature between about and about 180 F. as indicated in Table I. At

thebeginning of a run the isobutane-containing fraction was charged for from about 4 to 8 hours the solid aluminum chloride.

presence of aluminum chloride Team: I

introduced by the isobutane to a packed reaction zone Period No.

1 2 a 4 t 1 s 1 Dunflon 110111! 48 27 a 24 17 25 24 18 Temp. 0! packed reactor JR. 1 0 150 A150 160 100 170 170 180 0 stock, mole per cent: ghyjgnn 9. 0 n. a 13. 1 18.0 19.9 19. V20. 7 11. 7 Bntanes, mainlg iso- 3 83- 1 81-9 77. l 75. 0 70. 3 75. 1 78. 1 Hydrogen ch10 do 1- 8 L 3 L 2 1. 2 1. 2 1. 2 1. 2 1. 1 Hydrogen 0. 0 c 0 0.1 0.7 0.0 0. 0 0. 0 0. 0 w Pi l-2 :3 d 3. 6 3. 2 3. 0 3.0 3.0 3. 0 8. 0 3. 1

e nee, grams charge 0,011 3,450 3,410 0,001 2,244 2,900 3,079 2, 421 Butanee- 710 245 250 2. 0 2, 000 2, 650 2, 730 2, 190 Ethylene- 307 211 226 281 244 316 349 231. Liquid product: V

Total grams. 413 499 600 651 300 481 310 279 Weight per cent ethylene charged 1 237 221 204 14B 152 86 121 't'ireig l i t per cent ethylene reacted 237 237 m1 190 176 168 102 215 Dist t on, vol. per cent- 70-105" F.- 18 10 10 0 0 12 7 lot-150 F.- 00 02 06 74 00 50 66 03 Above 160 F 22 19 34 28 31 32 32 30 Oleflns in exit gas, moi per cent: After 4 hours 7.9 0 0; 8 6. 6 3. 8 16. o 13 The above table shows how the completeness 5 renewedamount of freshly volatilized aluminum oi the alkylation reaction is affected by the proportion of ethylene present in the reaction mixture charged together with aluminum chloride and hydrogen chloride to a packed reaction zone. Thus after a short time on test, an olefin-free exit gas was obtained in period 1 and the ethyl- 4 one removal continued to be complete until period 4 when the olefin concentration in the charge reached 18%. when the total charge contained. more than 18% of ethylene, part of this olefin appeared in the exit gas at all times.

The chief diflerence in the nature of the liquid product obtained as the concentration of ethylene in the charge was increased consisted in an increase in the percentages of alkylation products boiling higher than hexanes at the expense oithe pentane production, while the yield of hexanes remained fairly constant. The alkylation products boiling higher than hexanes contained a substantial proportion of octanes probably formed by the alkylation of hexanes with ethylene. The hexane fractions obtained in the different periods of ths run had zero bromine number and contained between about 0.02 and about 0.05 per cent of chlorine.

In previous runs, hydrogen chloride was introduced into the aluminum chloride pick-up chamber or vaporizer along with the isobutane. Such a. procedure caused the iormation of some sticky, lower-layer material upon the surface of In the present run, hydrogen chloride was not introduced into the vaporizer but only into the reactor with the result that aluminum chloride recovered from the vaporizer was free from sticky material and as bright in color as that of the fresh aluminum chloride.

At the end of the run when mea was taken apart, considerable lower-layer material was found distributed throughout the packed reaction zone and the remainder of the system. This material was in the form of a dark brown sludge which flowedreadily until it was exposed to air, and when treated with water it reacted violently thus indicating that it was still active.

EXAMPLE m A number of runs were made on the allrylation of isobutane with isobutene in the presence 01 aluminum chloride, in the form of a constantly chloride continuously deposited upon a ceramic packing material contained in a reaction zone. The results obtained, which are shown in more detail in Table 11, indicated that the lower temperatures gave the greater yields of lower boiling materials'havlng low bromine numbers than did higher temperatures. Good results were obtained when isobutane was pumped upwardly through a tube containing 150 grams of 4-20 mesh aluminum chloride maintained at 200 F.- and the resulting mixture was thereafter intro duoed to a packed reaction zone maintained at F. to which lsobutene and hydrogen chloride were also admitted.

Tears II Alkylotion of isobutane with. isobutene Period N0.

Duration ..hours.. 96 24 24 24 24 48 Temperature of packed reactor .F.. 150 130 100 ressuret of packed reac or 200 220 220 220 250 250 Charging stock, composiposition, mole per cent:

Isobutanc 70. 9 70. 0 71. 0 70.9 69. 7 70. 0 n-Butaue l6. 6 16. 4 16. 6 '16. 5 16. 7 l6. 7 P10138112 2.0 2.0 1.9 2.0 2. 5 2. 4 Pentancs 0. 0 0. 0 0. 0 0. 0 0. 5 0. 5 Isobutene 8. 4 9. 0 8. 5 8. 5 9. 0 8. 9 Hydrogen chloride 2. 2 2.0 2. 0 2. l 1. 6 1. 5 Charging rates:

Peraifln Iced- ..cc.lhr 198 203 201 195 203 206 Isobutene feed ec.lhr- 19. 5 21. 3 20. 0 19. 2 21. 4 21. 6 Hydrogen chloride .l l.- 1. 75 1. 60 1. 60 1. 60 1. 35 1. 35 Mole ratio, isobutane/ isobutenc 8.4 7. 0 8. 4 8.4 7. 8 7.8 Mole ratio, total buta eslisobute e 10.4 9.7 10:3 10.3 9.6 9.7 Liquid products, pentanes and higher hydrocarbogs:

rams; 1,517 384 313 275 309 l, 24 Yield, based on iso- 0 butane charged weight per cent" 157 144 126 115 116 Bromine number 21 10 28 36 42 7 Thus in period 6 with an hourly charge consisting of approximately 112 grams of a subst: :1- tially isobutane fraction, 1.35 grams of hydrogen chloride, and sumcient isobutene to provide approximately 8.9 mole per cent of this hydrocarbon in the total hydrocarbon mixture charged,

only 0.02% chlorine, and had a bromine number The novelty and utility of the process of this invention are evident from the preceding specification and examples given, although neither section is intended to unduly limit its generally broad scope. v

I claim as my invention: 1. In the alkylation of hydrocarbons, the method which comprises reacting an alkylatable hydrocarbon with an alkylating agent in a reaction zone containing a solid packing material, dissolving an alkylating catalyst in a liquid which is substantially unreactive with the catalyst, introducing the resultant solution of said liquid and catalyst to said zone and collecting a substantial portion of the catalyst on said packing material. 2. In the alkylation of hydrocarbons wherein an isoparaflin is reacted with an olefin in a reaction zone containing a solid packing material, the method which comprises contacting at least a portion of said isoparafiin, in Qiquid phase, with a metal halide catalyst of the Friedel-Craits type under conditions such as to form a solution of metal halide catalyst in the liquid isoparaiiin, the

This liquid product contained 73% latter being substantially unreactive with the catalyst under said conditions, introducing said solution of liquid isoparafiin and catalyst to the reaction zone, and depositing a substantial portion of the catalyst on said packing material.

3. An alkylation process which comprises contacting a liquid with a body of metal halide catalyst of the Friedel-Crafts type under conditions such as to dissolve a portion of said body in the liquid, said liquid being substantially unreactive with the metal halide catalyst under said conditions, introducing the resultant solution to a reaction zone containing a solid packing material and depositing a substantial portion of the catalyst on said packing material, simultaneously introducing an alkylatable hydrocarbon and an alkylating agent to said zone and therein reacting the same in the presence of the catalyst.

4. The process as defined in claim 3 further characterized in that said liquid comprises at least a portion of said alkylatable hydrocarbon.

5. An alkylation process which comprises contacting an isoparaflin, in liquid phase, with aluminum chloride under conditions such as to dissolve aluminum chloride in the isoparaflinic liquid without any appreciablechemical reaction between the isoparaflin and the aluminum chloride, introducing the resultant solution into a reaction zone containing a solid packing material and depositing aluminum chloride from the solution onto the packing material, simultaneously introducing an olefin to the reaction zone and therein reacting the same with at least a portion of the isoparaflin in the presence of the deposited aluminum chloride.

JOSEPH D. DANFORTH.

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