US2358011A - Treatment of hydrocarbons - Google Patents

Description

'- Patented Sept.f12, 1944 hydrocarbons.

TREATMENT OF HYDROCARBONS Vladimir N. Ipatiefl' and Louis Schmerling, Chicago, 111., a'ssignors to Universal Oil Products Company, Chicago, 111.;

. ware a corporation of-Dela- No Drawing. Application October I, 1942,

Serial No. 461,204

23 Claims... (01. zen-683.4)

This is a continuation-in-part of our co-pend- 'ing application Serial No. 443,008, filed May 14;

This invention relates to the treatment of hydrocarbons in the presence oi! a particular type or catalyst to produce branched chain hydrocarbons. fers more particularly may involve the alkylation of isoparaflihic, naphthenic, and aromatic hydrocarbons by olefinic hydrocarbons and olefin-act- .ing compounds; the isomerization of paraflins and naphthenes; or the polymerization of oleflnic hydrocarbons,

In its broadest aspects the present invention relates to a process for producing organic compounds, particularly hydrocarbons and phenols, of branched structure by reacting convertible organic compounds in the presence of a'particular type of catalyst. The production of branced hydrocarbons may involve the isomerization of lessbranched into more-branched hydrocarbons, as the isomerization of n-butane into isobutane, the

-. 6 a Isobutane is the isoparailin commonly subjected The reactions to which the invention reinto branched and more-highly branched chain hydrocarbons according to the process of the present invention are hereinafter referred to more completely. a

to alkylation although higher molecular weight isoparaflins also react with oleflnic hydrocarbons under similar or modified conditions oi. operation to produce branched chain paraiiinic hydrocarbons of higher boiling point than the isoparaflinic hydrocarbons charged to the process. However, as the higher molecular weight isoparafllns, such as-isopentane, isohexane, etc., arethemselves val uable constituents of gasoline, they .are conseisoinerization of m o r e-b r a n c h e d into less-' fins and aromatics in different crude petroleums.

referred to as cycloparaiilns, the cyclopentane,'

ture than the charged hydrocarbon starting ma-' terial which comprises contacting said hydrocarbon material under reaction conditions with a catalyst formed by interacting a phosphoric ac@ and a metal halide of the Friedel-Crafts type, separating from the reaction products the more: highly branched chain hydrocarbon and the unconverted hydrocarbon starting material, and recycling said unconverted material toiurther contact with the catalyst. 3

The hydrocarbons utilized as starting materials for the process of the presentinvention comprise paraiiinic, olefinic, naphthenic, and aromatic The paraflins and oleflns include both normal and branched-chain isomers, while the naphthenes and aromatics comprise cyclic and alkylated cyclic hydrocarbons. The difl'erent types oi-hydrocarbons which may be converted 50 and P y-81kt! a m y oc bo s which may quently used less commonly than isobutane as charging stocks for the alkylation process. Normal paraiiinic hydrocarbons which may be converted' into isoparaflinic. hydrocarbons by the present process comprise normal butane and higher' boiling paraflinic hydrocarbons of straightchain structure. Similarly, mildly branched liquid paraflins may beisomerized-into more-highly branched chain paraiiinic hydrocarbons with substantially higher antiknock value than the, less branched compounds charged to the process.

Naphthenic hydrocarbons which may be alkylated or isomerized according to the present process occur generally in admixture with parat- Of the diflerent naphthenidhydrocarbons, also cyclohexane, alkyl cyclopentane and alkyl cyclohexane hydrocarbons are generally those which are isomerized or alkylated in the presence 0! a catalyst of the type herein described to produce naphthenic h y d r o c a r b o n s of more-highly branched chain structures which are utilizable as constituents of high antiknock gasoline or for other p es.

Aromat c hydrocarbons, such as benzene, toluene, other alkyl benzenes, naphthalene, alkyl naphthalenes, other poly-nuclear aromatics, etc. which are alkylated by oleflnic' hydrocarbons as hereinafter set forth, may be obtained from any source such as by distillation of coal, by the dehydrogenation of naphthenic hydrocarbons, by the dehydrogenation and cycl'ization oi aliphatic hydrocarbons, etc. 'Alkyl aromatic hydrocarbons to which we herein refer include both mono -alkyl be converted into more highly alkylated aromatic mally liquid and include ethylene, propylene, butylenes, amylenes, and higher normally liquid oleflns, the. latter including various polymers of normally gaseous oleflns. Cyclic oleflns, such as cyclohexene, may also be utilized but generally not under the same conditions of operation as those employed with non-cyclic oleflns. oleflnic hydrocarbons utilizable in the present process include conjugated diolefins such as butadiene and isoprene and also non-conjugated dioleflns and other poly-oleflnic hydrocarbons containing more than 2 double bonds per molecule.

Alkylation of saturated hydrocarbons, including isoparaiflnic, naphthenic and aromatic hydrocarbons may also be effected in the presence of thecatalyst hereinafter described by reacting with the saturated hydrocarbons a substance capable of producing olefinic hydrocarbons under the conditions of operation chosen for the process. Such olefin-producing substances include alcohols, ethers, and esters capable of undergoing dehydration or splitting to form oleflnic hydrocarbons containing at least 2 carbon atoms per molecule, which may be considered to be present in the re-j action mixture even though possibly only as transient intermediate unsaturates which react further with the saturated hydrocarbons to produce desired reaction products. Oleflnic hydrocarbons and the above mentioned olefin-producing sub-' stances are herein referred to as olefin-acting compounds. Alkyl halides are also olefin-acting compounds and may be considered as esters of halogen acids.

moting the formation of more-highly branched hydrocarbons from less-highly branched hydrocarbons may be made by interacting a phosphoric acid with a metal halide" oi. the Friedel-Crafts type under such conditions that limited amounts of hydrogen halide are evolved which are generally from about 0.5 to about 2.0 molecular equivalents based upon the metal halide. It is apparent that since there are several phosphoric acids and a number of Friedel Crafts type metal halides which may be interacted, a considerable number of alternative catalystsma be made although 'such catalysts will not necessarily be equivalent in their action in any particular hydrocarbon conversion reaction to produce more-branched chain hydrocarbons.

The phosphoric acids which may be employed in th manufacture of the present types of catalysts include orthophosphoric acid, pyrophosphoric acid, and metaphosphoric acid. While any of these three acids may be used in the production of the catalysts, the activity of various catalysts" thus prepared will not necessarily be equivalent in any reaction in' which they may be employed.

Friedel-Crafts type metal halides which are reacted' with phosphoric acids to form catalysts Other anhydrous aluminum chloride is the Eriedel- Crafts type catalyst: usually used in hydrocarbon conversion reactions of the types mentioned herein because aluminum chloride is usually higher in catalytic activity under a given set oi conditions than another Friedel-Crafts type'metal halides. However, disadvantages accompany i use, in some instances on account of its high egree of activity. Thus, it mustbe handled in the substantial absence of water since it hydrolyzes readily and ultimately loses its catalytic activity when hydrolysis proceeds beyond a certain point. 'Alu:

' minum chloride catalyst alsohas a tendency to form undesirable complexes with unsaturated and aromatic hydrocarbons. However, by reacting proportioned mixtures of an aluminum halide, such as aluminum chloride, and a phosphoric acid,

in accordance with the present invention, cata-- a temperature of about 80 C. at which point place and a pale yellowish powder-like com-' We have found that catalysts useful in pro-'- a vigorous evolution of hydrogen chloride takes posite results with a composition corresponding approximatelyto that of a compound having the formula C1zA1OPO(OH)2 in admixture with unreacted aluminum chloride. definite activity as catalyst for the isomerization and alkylation of saturated hydrocarbons.

When a mixture of phosphoric acid and aluminum chlorideis heated, hydrogen chloride is evolved as hereinabove set forth and a solid catalytic material is produced, the activity of which depends upon the original proportions of phosphoric acid and aluminum chloride and also upon the amount of hydrogen chloride expelled during 'the mixing and heating. Active solid catalysts are formed when about 0.5 molecular proportion of hydrogen chloride is evolved per molecular proportion of aluminum chloride originally mixed with phosphoric acid. Active catalysts are also formed when even less hydrogen chloride is evolved but such catalysts are generally not solid and therefore are less suitable for use as reactor ,fllling materials. In general, the preferred catalyst is formed by mixing equal proportions of phosphoric acid and aluminum chloride and I thereafter heating the mixture at about 80 C.

useful in the present process include aluminum chloride, aluminum bromide, zinc chloride, zirconium chloride, ferric chloride, antimony chloride, bismuth chloride, and others. Substantially I until 1 molecular proportion of hydrogen chloride This composite has phosphoric acid and ther eafter heated as herein described, composites having generally higher,

catalytic activities may be produced which may owe their increased activities to the presence of uncombined aluminum chloride.

. Composite catalytic materials analogous to those formed by combining orthophosphoric acid and aluminum chloride can be made by reacting other phosphoric acids with aluminum chloride or with other Friedel-Crafts type metal halides such as those already mentioned. The activities of these alternative catalyticmaterials may vary considerably from those of higher activities made from aluminum chloride or aluminum bromide and phosphoric acids to those having catalytic activities ofa lower order and thus more suitable for uses requiring catalysts of relatively lower activities. Furthermore, some of these composite materials may be active as catalysts for certain hydrocarbon conversion reactions and less active for others..

The preferred catalysts which :are granular solids at ordinary temperatures may be used as such or b mixed with carrying or spacing materials of a relatively inert character such as various prepared forms of alumina, various silicas,

activating carbons or chars, silicate minerals, synthetic silica-alumina type composites and acid-treated kaolin group minerals, such as, for example, the acid-treated montmorillonites of commerce some of which are known as Filtrol, Tonsil," etc. The preferred catalytic composites may be prepared in the presence of these carriers in relatively finely divided condition so that an intimate mixture of catalyst and carrier is produced, or they may be prepared separately and used to surface prepared granules, or mixed with finely divided carriers and formed into particles by pelleting or extrusion Procedures.

In contrast to, aluminum halide catalysts, the catalysts of the present invention do not form substantial amounts of complexes with unsaturated and aromatic hydrocarbons and, accordingly, they may b used in continuous processes over long periods of time with relatively little contamination by such complexes so that in many instances the catalyst life is considerably longer than the life of the corresponding aluminum halide in similar types of hydrocarbon conversion reactions.

According to the process of the present invention, a naphthenic, oleflnic, or parafli'nic hydrocarbon, or a mixture of an olefinic hydrocarbon with a saturated hydrocarbon selected from the isoparaflinic, naphthenic, and aromatic hydrocarbons, may be reacted in the presence of the above indicated catalyst at a temperature of from about --20 to about 150 C. to produce hydrocarbons of more-highly branched chain structure and of either substantially the same or higher molecular weight than that of the hydrocarbons chain structure while similar treatment of olefinic' hydrocarbons, and particularly gaseous olefinic hydrocarbons, results in the formation of branched chain polymers. The reaction of an olefinic hydrocarbon with an aromatic, isoparafllnic, or naphthenic hydrocarbon produces an alkylated hydrocarbon more-branched in structure than the hydrocarbon tion. Y

In isomerizing paraillnic hydrocarbons with the type of catalysts herein described, either batch or continuous operations may be employed. In a simple batch procedure proportioned amounts of a parafllnic hydrocarbon and catalyst and minor amounts of hydrogen halide may be added to a vessel capable of withstandingmoderately superatmospheric pressure and the contents heated for a time adequate to cause a desired degree of conversion. In some instances, especially where normally liquid paramn hydrocarbons are treated, undesirable decomposition reactions may be minimized by introducing hydrogen. After a period of heating the reaction vessel may be cooled, the gaseous contents discharged, and the liquid hydrocarbon layer separated from the partly spent catalyst and' fractionated to recover desired isomers and insufll-- ciently isomerized hydrocarbons, the latter suitable i'or returning to further treatment. In continuous operations the granular catalyst, either alone or on carriers, may be placed in reaction chambers and preheated mixtures of hydrocarbon along with hydrogen chloride may be hydrocarbons being recycled to the reaction zone for further treatment while the desired isomeric fractions are recovered.

-In isomerizing paraflinic and naphthenic hydrocarbons with the types of catalysts which characterize the present invention, the temperatures employed are from about 20 to about 150 C. but preferably from about 20 to C. With some of the less active but possibly more selective catalysts, still higher temperatures may be found suitable. Superatmospheric pressures may also be employed, particularly when using hydrogen and in some instances; pressures as high as 100 atmospheres may be utilized. The reaction time employed in batch operations and the space velocities of the reactants passed through a bed of catalyst in continuous operations may be varied as desired depending upon the values found to be optimum for producing high yields of desired products.

Alkylations of saturated hydrocarbons, including isoparafllnic, naphthenic, and aromatic hydrocarbons by oleflnic hydrocarbons and olefinacting compounds in the presence of a composite catalyst herein described, are carried out at temperatures of from about 20 to about C.

and under a pressure of from substantially at-' mospheric to approximately 100 atmospheres. In the hydrocarbon mixture subjected to alkylation, it is preferable-to have present. from about 2 to about 40 molecular proportions of saturated hydrocarbon per one molecular proportion of olefinic hydrocarbon introduced thereto. In general a'higher molecular proportion of saturated hydrocarbon to oleflnic hydrocarbon is employed when a normally liquid olefinic hydrocarbon is utilized than when alkylatlng with a normally gaseous olefin because of the fact that higher mo-. lecular weight oleflns, particularly those boiling subjected to' alkylaalkylation product.

able to introduce to the reaction mixture a relacarbon and produce a substantially saturated It is frequently also desirtively small amount of a hydrogen halide such as hydrogen chloride or hydrogen bromide and sometimes alsoto have hydrogen present in the reaction mixture but generally in a quantity not greater than about mole per cent based upon the total hydrocarbons present.

The alkylation of a saturated hydrocarbon by an oleflnic hydrocarbon or other olefin-acting compound may be carried out using either batch or continuous operation. Thus, in batch types operation, a finely divided catalyst formed by interacting aluminum chloride and a phosphoric acid is charged to a reactor containing a saturated 'hydrocarbon such as an isoparaflin, and the resultant mixture is then agitated while an olefinic fraction, or a hydrocarbon fraction containing both oleflns and alkylatable saturated hydrocarbons, is added thereto in order to effect the formation of higher boiling more-highly branched chain hydrocarbons of gasoline boiling range and high antiknock value. After the reaction, the hydrocarbon layer is separated from the catalyst and the former is then fractionally distilled into unconverted hydrocarbon and alkylation product. The unconverted hydrocarbon and used catalyst may then be employed in another alkylation run.

Continuous type of alkylation treatment may be carried out by introducing a mixture of alkylatable saturated hydrocarbons and an olefin to "a reactor containing'a fixed bed of granular catalytic material formed by interacting substantially anhydrous aluminum chloride and a phosphoric acid as herein described. The olefin charged to alkylation may thus be introduced with a saturated alkylatable hydrocarbon or it may be directed to contact with said saturated hydrocarbon at a number or points intermediate the inlet and outlet of the alkylation zone. The conditions of temperature and pressure maintained in such an alkylation zone are generally between the approximate limit hereinabove set forth, but

the exact, conditions employed in any particular alkylation generally vary with the molecular weights and reactivities of the saturated and oletinic hydrocarbons reacting, the composition of the catalyst, and other factors.

It is generally advantageous to dilute the oleflnic hydrocarbon or olefin-acting compound with a portion of the saturated hydrocarbon and to introduce the olefin-containing mixture at a plurality of points throughout the reaction zone rather than to add the undiluted olefinic hydrocarbon directly to the catalytic alkylation zone. In this way, a relatively high ratio of saturated hydrocarbon to oleflnic hydrocarbon is readily maintained throughout the entire reaction so that alkylation is thereby favored and polymerization of the olefinic hydrocarbon is kept relatively low. The recovered mixture obtained from a continuous alkylation treatment is then conducted to a separating or fractionating zone in which unconverted alkylatable saturated hydrocarbons are separated from the alkylation product and said unconverted hydrocarbons are then recycled to further treatment in the alkylation zone of the process. v

The iollowing examples'aregiven toillustrate isomerizing normal butane were obtained with the character or results obtainedby the use of. the present process, although the data presented are not introduced with the intention of unduly restricting'the generally broad scope of themvention. I I

A catalystwas made by heating equimolecular proportions of aluminum chloride and orthophoswas placed in a rotatable steel autoclave along with amounts of normal butane shown inTable 1 and the autoclave was then closed, heated, and rotated at 100 C. for a period or four hours.

Team: 1

Isomerization of normal butane in the presence of a catalyst made by interacting aluminum chloride and a phosphoric acid Run No.

Catalyst made from A101: and- Orthophos- Pyrophos horic phoric acid aci Tern reture, "C 100 100 100 100 M mum pressure, atmospheres... 12 16 l8 l7 l3 Reactants, parts by weight:

n-Butane 52 52 51 52 50 Hydrogen chloride 0 2 0 2 0 Catalyst 5 5 (i 6 6 Products, parts by weight:

Cond d 52 49 51 50 49 0 0 0 0 0 ys 5 5. '5 6 6 7 Hydrogen chloride 0 l. 5 0 0. 5 0 Loss, uncondensed gas, etc..." 0 3 0 3 0 Analysis of condensed gas:

Isobutane 28. 6 27. 4 10. 2 21. 5 3. n-Butane 71. 2 71. 6 88. 0 77. 6 96. Pentanes 2. 2 1. 0 0. 8 0. 9 0.

From the above data it is noted that under the reaction conditions used the best results in the catalyst made from aluminum chloride and orthophosphoric acid, since the production of isobutane was 26.6% by weight in Run 1 and 25.8% (assuming the loss to be normal butane) in Run 2. In these two runs, there Was no change in weight 01' the catalyst in Run 1 and a slight increasein weight in Run 2. The fact that the catalyst did not increase appreciably in weight during use is evidence that only small amounts of organic [complexes were formed by the interaction of the hydrocarbons and the catalyst. It is worth noting that there was only a very small formation of hydrocarbons heavier than butane, and accordingly substantially all of the hydrocarbons other than isobutane could be recycled.

Runs '3, 4, and 5 in which normal butane was isomerized in contact with the catalyst made by interacting aluminum chloride and pyrophosphoric acid, showed somewhat lower yields, particularly in the absence ofadded hydrogen chloride in Runs 3 and 5. The low yield 01' isobutane izing action was selective as shown by the rela-- tively small amounts of products higher boiling than butanes; Again, the catalyst showed no ap- Ohia,sse,oi1

, chloride. During the addition oi the P pylene,

preciable weight increases indicating substantially no formation 01' hydrocarbon complexes.

EXAMPLE'II Portions of the catalystsprepared as described in Example I were contacted with normal hep-- tane in a rotatable steel autoclave under the conditions shown in Table 2.

" p Tan: 2 1o Isomeflzatlon of normal heptone in thcpresence of catalysts made by interacting aluminum chloride and a phosphoric acid Catalyst made from 4101:

Orthophos- Pyrophosphoric acid phorio aoid Temperature, C .Q 100- 27 50 100 Duration, hours 4 4 4 umpressuraatmosph m 4 4 Reactants, parts by weight:

n-Heptane 50 s 50 -50 50 Hydrogenchioride. 0 2 3 2 Ca ya 4... l0 8 4 6 Products parts by weight:

' Con ensed gas"..- 0 0 0 0 Liquid 41 45 50 47 Catalyst 13 11 6 6 Hydrogen chloride 0 l 0 Loss uncondensed gas, etc... 6 4 l 5 Distillation of liquid products,

volume r cent:

04 an lighter paramns l0 Grand 05 parafiins... 6 26 0 0 i-HeptanelL. 20 16 10 8 n-Heptane 55 23 80 86 0 and higher hydrocarbona. 2 21 3 I 4- In run 6 on n-heptane, a higher yield of iso heptane (branched chain heptanes) was obtained at 100 C. in the absence of added hydrogen chloride than was obtained in run '7 at 27 C. in the presence of 2 parts by weight of hydrogen chloride. However, the reaction was obviously more selective in run 6 since there was less iormation of products boiling above and below the heptanes and a considerably larger amount of unconverted normal heptane which could be recycled for further treatment. 7

In runs 8 and 9, the catalysts, made by interacting aluminum chloride and pyrophosphoric acid, showed a high degree of selectivity in that there 'was only small production of hydrocarbons boiling lower than isoheptanes and a large amount of normal heptane was recovered'which could be recycled to further isomerizing treatment.

40 parts by weight of aluminum chloride were added with stirring to 29 parts by weight of 100% phosphoric acid. The temperature oi. the wellstirred mixture rose from 20 to 70 0., the mixture first became putty-like in appearance. and then yielded 59 parts by weight of yellow powder. This final weight corresponded to a loss of approximately 1 molecular equivalent of hydrogen chloride. On further heating at 85 0., more hydrogen chloride was evolved and 58.6 parts by weight of finely dividedyellow powder was produced.

Alkylation oi isobutane was then carried out by introducing 40 parts by weight of propylene during a period of 4 hours to an autoclave containing a stirred mixture of 168 parts by weight of isobutane, 25 parts by .weight or. the-catalyst composite, and 5 parts by .weight of hydrogen 7;;

the autoclave and contents were maintained at a constant reaction temperature. Three allrylation runs thus made at temperature of 35, 60, and 74 C. gavetheresultsshownin'rable 3.

Turn 3 Allcylation of ieobutane with propylene Run No.

case i anes was relatively high while octanes were pres ent in larger amount than the heptanes. The relatively high proportion of propane iormed indicated that some of the liquid product, possibly that boiling in the octane range, was produced by hydrogen transfer reaction in which propylene reacted withisobutane to produce propane and isobutylene. the latter being then utilized in alkylating isobutane to iso-octane.

EXADEPLE IV 53 parts by weight 01 powdered aluminum chloride were added with stirring to 71 parts by weight of pyro-phosphoric acid at C. The resultant mixture which at first was paste-like in consistency soon had the appearance of putty and then hydrogen chloride was evolved while the mixture increased in volume due to roaming and finally yielded a porous cream-colored solid whichwas easily crushed to a powder. The yield of this powder indicated the loss of about 0.55 molecular proportion of hydrogen chloride per 0.4 molecular proportion of aluminum chloride and 0.4 molecular proportion of pyrmphosphoric acid so composited.

8 parts by weight of the catalyst powder so prepared, 81 parts by weight or isobutane and 20 parts by weight of propylene were charged to a rotatable steel autoclave and rotated therein at ,60 C. for 4 hours under a maximum pressure isobutane. 3% of hydrocarbons boiling below 75 C., 12% of a fraction boiling between 75 C. and C. corresponding to heptanes, 10% of a fraction boiling between 95 .and C. consisting largely of octanes, 8% boiling between 125 and H a sense a:

* 150 7% boiling between 150 and 200 0..

above 200 C.

The preparation of the catalyst was similar to that shown in Example IV with the exception and 42 boiling afssaon the presence of a catalyst comprisingjthereaethat the .pyrophosphoric acid was initially at I room temperature and no attention was paid to the temperature developed by addition thereto The resultant reaction mixture yielded 16 parts by weight of liquid hydrocarbons containing 19% by volume of dissolved isobutane, 31% or pentanes and hexanes boiling below 75 C., of a heptane fraction boiling between 75 and 95 C., 16% of an octane fraction boiling be-, tween 95 and 125 C.; 8% of a fraction boiling between 125 and 150 C. and 11% of higher boiling material.

EXAMPLE VI 1 Alkylation of benzene was carried out by gradually introducing 21 parts by weight of propylene during a period of 4 hours to an autoclave maintained at 25 C. and containing a stirred mixture of 80 parts by weight of benzene and 5 parts by weight of the catalyst composite described in Example III. After this treatment, the reaction mixture was removed from the autoclave, sepa- 1 rated from the used catalyst, and'tractionally distilled into 57% by volume of unconverted ben-' zene, 25% of mono-isopropyl benzene, and 18% of higher boiling alkylated benzenes.

The novelty and utility or the process of the present invention are evident from the preceding specification and examples, although neither section is intended to unduly limit its generally broad scope.

We claim as our invention:

1. A process for producing organic compounds of branched carbon structure which comprises contacting a reactive organic compound under conversion conditions with a catalyst comprising the reaction product formed by interacting a phosphoric acid and a metal halide of the Friedel-Crafts type and liberating hydrogen halide in an amount not in excess 01 2 mols for each mol of metal halide present, whereby said reaction product contains at least one halogen atom per mol.

2. A process for producing hydrocarbons of branched carbon structure which comprises contacting a hydrocarbon material under reaction conditions with a catalyst comprising the reaction product formed by interacting a phosphoric acid and a metal halide of the Friedel-Craits type and liberating hydrogen halide in an amount not in excess of 2 mols for each mol of metal 'halide present, whereby said reaction product contains. at least one halogen atom per mol.

3. A process for producing hydrocarbons of more-highly branched structure than that of a hydrocarbon starting material which comprises reacting said hydrocarbon material at a temperature oi! irom about -20 to about 150 C. in

The autoclave so tion product formed by interacting a phosphoric acid and a metal halide of the Friedel-Crafts type and liberating hydrogen halide in an amount not in excess 01 2 mols for each mol of metal halide present, whereby said reaction product contains at least one "halogen vatom per mol. 1 If 4. A process for producing substantially saturated hydrocarbons of more-highly branched structure than that of a hydrocarbon starting material which comprises reacting said hydrocarbon material at a temperature of from about -20 to about 150 C. in the presence of a catalyst formed by interacting a phosphoric acid and a metal halide of the Friedel-Crafts type.

' 5. A process for producing substantially saturated hydrocarbons ot more-highly branched structure than that'of a substantially saturated hydrocarbon starting material which comprises reacting said hydrocarbon material at a tem-1..

' perature of from about 20 to about 150 C. in

the presence of a catalyst formed by interacting a phosphoric acid and a metal halide or the 1 Friedel-Craits type.

reacting said hydrocarbon material at a temperature of from about -20 to about 150 C. in the presence of a catalyst comprising the reaction product formed by mixing a phosphoric .acid and a tri-valent metal halide oi the Friedel-Crafts type andheating the resultant mixture 'to cause interaction of the acid and metal halide so as to evolve from about 0.5 to about 2.0 molecular pro portions oi! hydrogen halide per molecular proportion of metal halide interacted with said phosphoric acid, whereby said reaction product contains at least one halogen atom per mol.

8. A process for producing substantially saturated hydrocarbons ot more-highly branched structure than that of a substantially saturated hydrocarbon starting material which comprises reacting said hydrocarbon material at a temperature of from about -'20 to about C. in the presence of a catalyst formedby interacting a phosphoric acid and a'metal halide of the Friedel-Craits type and heating the 'resultant mixture to cause interaction of the acid and metal halide so as to evolve from about 0.5 4:0 about 2.0 molecular proportions of hydrogen halide per molecular proportion of metal'halide interacted with said phosphoric acid.

9. A process for producing substantially saturated hydrocarbons of more-highly, branched structure than that of a substantially saturated hydrocarbonstarting material which comprises reacting said hydrocarbon material and an olefinic hydrocarbon at a temperature oi from about -20 to about 150 C. in the presence of a catalyst formed by interacting a phosphoric acid and a metal-halide of the Friedel-Crafts typeand heating the resultant mixture to cause interaction of the acid and metal halide so as to evolve from about 0.5 to about 2.0 molecular proportions of hydrogen halide per molecular proportion of oi branched carbon structure whic metal halide interacted with said phosphoric acid.

10. The process of claim 8 further characterized in that said metal halide comprises substantially anhydrous aluminum chloride.

11. The process of claim 8 further characterized in "that said phosphoric acid,- comprises orthophosphoric acid.

12. The process oi! claim 8 further characterized in that said substantially saturated hydrocarbon. starting material comprises a paraiiinic hydrocarbon isomerlzable to a more-highly branched paraflinic hydrocarbon.

13. An alkylation process which comprises reacting an alkylatable hydrocarbon with an oleilnic hydrocarbon at atemperature of from about -20 to about-150 C. in the presence 01' a catalyst formed by interacting a phosphoric acid and aluminum chloride and heating the resultant mixture to cause interaction 01' the acid and alu-. minum chloride to as to evolve from about 0.5 to about 2.0 molecular proportions of hydrogen chloride per molecular proportion of aluminum chloride interacted with said phosphoric acid.

14. The process of claim 13 further characterized in that said aikylatable hydrocarbon comprises an isoparamnic hydrocarbon.

15. The process of claim 13 i'urther characterized in that said alkylatable hydrocarbon comprises an alkylatable naphthenic hydrocarbon.

16. The process of claim 13 further characterized in that said alkylatable hydrocarbon compises an alkylatable aromatic hydocarbon.

17. The process of claim 3 further characterized in that said hydrocarbon starting material comprises essentially oleilnic hydrocarbons.

18. The process of claim 4 further characterized in that his carried out under a pressure of from about to 1 to about 100 atmospheres.

19. A process for producing organic compounds comprises contacting a reactive organic compound under conversion conditions with a catalyst comprising the reaction product formed by interacting 'a phosphoric acid and aluminum chloride and liberating hydrogen chloride in an amount not in excess of 2 mols for each moi 01 aluminum chloride present, whereby said reaction product contains at least one chlorine atom per mo].

20. A process for producing hydrocarbons of branched carbon structure which comprises conconditions with a catalyst comprising the reaction product formed by interacting a phosphoric acid and aluminum chloride and liberating hydrogen chloride in an amount not in excess of 2 mols for each mol of aluminum chloride present, whereby said reaction product contains at least one chlorine atom per mo].

21. A process for producing substantially saturated hydrocarbons, oi more-highly branched structure than that of a hydrocarbon starting material which comprises reacting said hydrocarbon material at a temperature 01' from about 20 to about 150 C. in the presence 01' a catalyst comprising the reaction product formed by interacting a phosphoric acid and aluminum chloride and liberating hydrogen chloride in an amount not in excess of 2 mols for each mol of aluminum chloride present, whereby'said reaction product contains at least onechlorine atom per mol.

i one chlorine atom per mol.

23. A process for producing substantially saturated hydrocarbons of more-highly branched structure than that of a hydrocarbon starting material which comprises reacting said hydro-' carbon material at a temperature of from about --20 toabout C. in the presence of hydrogen and a catalyst comprising the reaction product formed by interacting a phosphoric acid and aluminum chloride and liberating hydrogen chloride in amount not in excess of 2 mols for each mol of aluminum chloride present, whereby said reaction product contains at least one chlorine atom per mol.

Y VLADIMIR. N. IPATIEFF.

LOUIS SCHMERLING.