Патент USA US2403649код для вставки
Patented July 1946 2,403,649 ` UNITED STATI-:sf PATENT OFFICE; f HYDROCARBON RECONSTRUCTION Frederick E. Frey, Bartlesville, Okla., vassigner to . Phillips Petroleum Company, a corporationof Delaware . Application January 13, v1942, Serial No. 426,627 18 Claims.v (Cl. 260-683.5)- 2 1 compounds; (6) conversion of noncyclic hydro vThis invention relates to the conversion of hyv drocarbons. More particularly, Y ity relates fto' chemical reconstruction of hydrocarbons-in the carbons to cyclic compounds. When the initial material has a considerable proportion of naph presence of hydrofluoric acid as a catalyst. This thenes,disproportionationofV these to paraflins application is a continuation in part of my co 5 and aromatics appears to occur, especially at rela pending application Serial No. 323,443, filed March 11, 1940, now Patent 2,317,901, issued April 27, tively drastic conditions oi 'time and 'tempera 1943. ture. The y production . of these effects indicates> , that several different types of Vchemical reactions may beiin'volved vin-the present 'process'.ffor; recon struction of hydrocarbons. v Y The `predominating I have discovered that, in the presence of `sub stantial proportions _of khydroi‘luoric «acid andv 10 under suitable conditions of time and/or'temper Iature, hydrocarbons cany be catalytically recon structed to hydrocarbons of differentA lcarbon vskeleton arrangement and/or., different vboiling point, thereby effecting an improvement in yprop t reaction types, as deduced `from 'a consideration „ of reactants, products, operating conditions,fand theoretical aspects relating to the invention, may be exemplified as follows: Y " Y erties and in usefulness for specific purposes. Parañinic hydrocarbons boiling in the motor ,<0 . fuel range, for example, undergo conversioni-,o isomers and to hydrocarbons of both lower and y ' higher molecular> weights and correspondingly 20'(2) y . Y suitable reaction temperature and pressure and ' . ’ , j ,HF 30 .. Y ' `- 2C1H1ß ` HF ' ,_> (heptanevs) -l-_> 2041110 (cyclohexane) ' 06H12 06H12 (butanes) ' H -_->« (cyclohexane)_ , for a time suflicient to eii’ect the desired extent '(octanes) - y(b) :_1-butano- --> Isobutane Í (4) hydrocarbons to the action of a substantial'pro vportion ofconcentrated- hydrofluoric'acid at a HF (a) n-heptane 1_» branched heptanes , ’, higher-boiling products. Accordingly, the pres 25 (3) ent invention comprises subjecting hydrocarbon material consistingk predominantly of saturated Y (hexanes) ‘ lower and higher boiling temperatures. Similarly, motor-fuel fractions containing minor propor tions of unsaturates are converted into complete ly saturated materials containing some lower-and (heptanes) . t CHaCtHa (methyl cyclopentane) The ñrst two reactions, namely, reconstruction to produce both higher-and lower-boiling parafñns, of conversion. Recycling of unreacted hydrocar 'and isomerization, respectively, predominate un bons and/or of selected fractions of the product der relatively mild treating conditions. "The may be practiced. By the term “saturated” l yields of cyclics, exemplified' in thethird equation intend to exclude unsaturated hydrocarbons such 35 by cyclohexane, is increased by increasing theV as oleiins, dioleiins, acetylenes, and the like. temperature and/or the timeofu reaction. A In general, this invention may be Íused to con vfourth ytype. of reaction' is believed to account for vert or improve hydrocarbon materials compris the increase in saturation and stability that oc ing substantially entirely saturated hydrocar curs when motor fuel comprising some unsatu bons; although minor proportions of unsaturated 40 rated material is treated. By this reaction, ole ñns arey converted to cycloparañins such as cyclo heXane and its derivatives. _This reaction may hydrocarbons initially present can be tolerated, it is not intended that my invention Ashall include a process'only for the alkylation- of saturated hydrocarbons by reaction with unsaturated hy, be exempliñed as follows: l ‘ drocarbons. The specific effect-„produced in any 45 particular case is usually one or more of the fol lowing: (1)' increased octane number of motor fuel range hydrocarbon materials; (2)V enhanced susceptibility to antiknock improvement by the addition of tetraethyl lead to hydrocarbon ma __) (heptylene) " C eHuC Ha ‘ (methyl cyclohexane) Several other types of reactions undoubtedly oc 50 cur in the reconstruction process; however, the terials; k(3) ' conversion of hydrocarbons to hydro above-mentioned kñve types appear to accountl for carbons of higher and/or lower molecular most of the effects which are produced. The gen eral term “reconstruction” is used herein to de weights; (4) decreased content of unsaturates in noteV the production of one or more of the above- „ hydrocarbon materials; (5) conversion of hydro carbons to relatively highly branched isomerio 55 mentioned effects and/or of other inherent ad- ' U 2,403,649 3 4 vantageous effects which result from the practice production capacity of equipment of any given size; however, proportions outside of the pre of my invention. Insofar as I have been able to determine, .the actual catalyst which promotes the reconstruc tion reaction, or reactions, is concentrated hydro ñuoric acid. Other materials may be present which will exert a slight promoting effect, such as compounds fortuitously formed in minor amounts by reaction of hydroñuoric acid with Walls of reaction vessels, but the presence of such compounds does not alter the fact that hy drofluoric acid is the catalyst. Agents which ferred range should not be excluded from the scope of this invention. Mixing of the hydro fluoric acid and the hydrocarbon material may be effected by any of a number of methods, as by the use of a special mixer or emulsiñer, or by maintaining high linear velocities in conduit I3; devices such as sharp bendsI or constrictions in conduit I3 are advantageous in some instances. ` The resulting mixture is passed to heater I?, wherein it is heated to a suitable reaction tem perature. Heater I1 preferably consists of a tube cOil surrounded by hot gases or liquids. In some promote the action of the hydrofluoric acid may be added in many instances without changing the character of the reaction nor exceeding the 15 instances, as When the desired reaction tempera ture is atmospheric, or only slightly above, heater scope of the spirit of the invention and of the I'I is unnecessary and may be ‘oy-passed or. re disclosure. The> reaction may take place in the presence of relatively or essentially inert solids moved from the system. Depending somewhat .upon the character of the of large surface area such as activated charcoal, initial hydrocarbon material, the reaction tenu bauxite, etc. which will tend to adsorb and con perature may vary from about 50 to about 1090o centrate hydrofluoric acid in an active state. F.; a temperature in the range of 250 to 800D F. is ’When it is desired to maintain hydroñuoric acid usually preferred. The pressure may vary from in a liquid phase at higher reaction tempera about atmospheric to 5000 pounds »per square tures, this effect may be aided by incorporating with the hydrofluoric acid inorganic salts which 25 inch, or more. The reaction time may vary from about one minute to twenty hours or more, high are soluble in hydro?luoric acid, especially the values applying to relatively low reaction tem iiuorides of alkaline materials and of alkali-earth peratures or to highly refractory reactants, and metals. i low values applying to relatively high operating ' An object of this invention is to provide a new process for catalytically reconstructing hydro 30 temperatures or to highly reactive reactants. De pending upon the particular hydrocarbon mate carbon material. rial being treated and upon the region of tem lA further object is to produce hydrocarbons perature and pressure under which the recon of -loWer and/or higher molecular weight and of structing reaction is conducted, the mixture of correspondingly lower and/or higher boiling hydrocarbons and catalyst may be in a wholly points than those of the material treated. gaseous phase, in a partially liqueñed condition, A specific object is to treat motor fuel so as to or in a Virtually wholly condensed condition. The enhance its susceptibility to improvement of its extent of conversion increases with increase in antiknock rating by the addition of tetraethyl temperature, time, and/or catalyst concentration. lead. Another speciiic object is the production of sat 40 Changes in pressure appear to affect the nature of the reaction appreciably, particularly at high urated hydrocarbons boiling in the motor-fuel temperatures. In general, an increase in pressure range and having increased unleaded and leaded retards the formationof lower-boiling hydrocar~ octane numbers as compared with the original 4bons and increases the formation of higher-boil material or corresponding fractions thereof. Another specific object is to improve hydrocar- -» ing- hydrocarbons; also, increase in pressure tends to increase the rate of conversion, particularly bons, such as those obtained by petroleum reñnery under gas-phase operating conditions. Over-re operations, and especially those boiling in the acting may lead to the formation of some heavy motor-fuel range, by increasing the degree of oils, usually of relatively low value, and of some saturation and, consequently, the stability, when a small but undesirable proportion of unsaturates 50 organic iiuorine-containing compounds of high molecular weight, which usually remain mostly are originally present. dissolved in the hydroñuoric acid when the pro Another specific object is to convert normal or portion of acid is large enough for a separate slightly branched aliphatic hydrocarbons to more liquid acid phase to be produced upon cooling highly branched aliphatic hydrocarbons. the reaction mixture. A further object is to convert normal paraffins The optimum operating conditions in any into corresponding isoparafñns. specific case are dependent upon the nature of Other objects and advantages of my invention the feed material aswell as upon the extent of will be apparent from the accompanying disclo reconstruction desired. For example, in treating sure and discussion. An understanding of some of the many aspects 60 a lube oil to decrease unsaturation or to modify such properties as the pour point, the viscosity, of the invention may be aided by the accompany or the like, relatively mild reconstructing condi ing drawing, which is a flow-diagram illustrating tions are used. By contrast, in reconstructing a preferred arrangement for practicing the in relatively refractory materials, such as normal vention. ~ butane or normal pentane, to produce isomers A suitable hydrocarbon material, admitted tov the system through inlet I0, pump II, and valve I2, is mixed in conduit I3 with concentrated, prei erably anhydrous, hydrofluoric acid, which is ad mitted through inlet I4, pump I5, and valve I6. The proportion of hydro?luoric acid is preferablyy in the range from 0.2 to ‘l times by weight of the total l hydrocarbon fluids. Proportions much smaller than this are sometimes insuiiicient to >effect the desired degree of conversion, whereas much larger proportions vdecrease undesirably the and higher-and/or lower-boiling hydrocarbons, relatively drastic conditions are required. For re constructing normal butane to produce isobutanc, the preferred conditions are a temperature in the range of 400 to 800° F., a pressure in the range of 250 to 2500 pounds per square inch, and a re action time in the range of 1 to 100 minutes; but ` conditions outside of these ranges may at times œ used, in accordance with the principles of the invention. The reconstructing reactions to im ‘2,403,649 . ‘ 5 V6 prove the rantikno'ck"characteristics of' motorffuel i'acid phase, wherein most of the reaction takes what less drastic conditions than those preferred upper layer _from the acid, from which it maybe withdrawn. Acid passing out of solution on cool place;V Converted hydrocarbonseparates as 'an . hydrocarbons are usually carried-out under some for the reconstruction of normal butane. For any rparticular case, the optimum;k conditions are read ing may be allowed to return to the column of ily determinable’by trial "by one skilled in the art in the light ofthe present disclosure and dis cussion. ' ' - acid. l f Y ' ' ' The eliiuent mixture from reactor 23 is passed l Vthrough conduit 28 havingvalve 29 to separator f 20 Ywherein it is separated into two liquidphases, ` When the requisitereaction time is relatively as lby ‘cooling and gravitation or centrifugal 10 short, such as about one to about ten minutes, the means. The lighter' 'or hydrocarbon phase is reaction may be carried out preferably wholly in passed vthrough conduit 30 Vhaving valve 3| to tu-be heater I1, from which the reaction mixture fractionator32. The heavier or hydrofluoricacid is conducted via pipe I8 and vvalve I9 directly to phase ’ may be recycled via conduit`33 _having cooler and 'separator 20. -When the requisite re`~ >action time is relatively long, it is advantageous 15 valve 34 to pump> I5; however, preferably at least part of it is passed through valve 35 and con >to pass the heated, mixture from heater rI'l duit 36'to acid fractionator 31, wherein it is puri through valve> 2| and conduit 22A >to reactor 23, ñedbefore being reused. wherein the mixture isdigested at the reaction From -fractionator 32 is passed a comparatively temperature and pressure for a time sufficient to minor overhead fraction, which comprises free effect the desired conversion. Such digestion may hydrogen fluoride and relatively low-boiling- hy need AtoA be accompanied by vigorous agitation drocarbons, through valve 38 and conduit 39‘ to when relatively immiscible liquid phases are pres separator 4ll.V The rremaining or major portion ent. When liquid-phase or mixedfpha'seroperat of material, which comprises substantially pure ing conditionsl are used, means for effecting agi hydrocarbons with very small proportions of or tation or miXingrin reactor 23 are usually desir 25 ganic fluorine compounds, is passed through valve able, Y because liquid hydrocarbon-hydrofluoric 4| -and conduit 42 to deñuorinator or i'luorine re acid'mixtures tend to separate into two layers. mover 43. Mixing may be effected by any well-known means, ` Fluoriner remover 43 comprises a chamber con- , such as mechanical stirrers, relatively constricted taining a contact mass having hydrogenation ' .30 orifices or zones` through which the mixture is and/ or dehydrogenation properties, such as baux passed at high linear velocity, or the like; it may ite, alumina, or other similar material. Usually be aided by recirculation, las through circuit 24, suitable operating conditions are a temperature pump 25, and valves 26 and 21. If all components in the range of 75‘to 250° F. and a space velocity of the reaction mixture are in a single phase, Yin the range of 1 to 50 volumes of liquid hy. no means of agitation willgenerally be required. drocarbon material per volume of contact mass Usually the heat of reaction is relatively small per hour. Under such conditions, which may. be particularly selected in accordance with a trial, organically combined ñuorine is substantially and does not markedly affect the temperature of . the reacting mixture. Preferably, reactor 23 is ,operated adiabatically; but, if desired, auxiliary completely removed from the hydrocarbon ma heating or cooling devices may be incorporated in 40 terial, which then is `passed through valve 44 reactor '23,. although control of the temperature 4and conduit 45 to fractionator 46. Such deflu therein is more suitably effected by controlling orination'is more completely disclosed, and is the heat input in heater l1. , ì claimed, in my copending application Serial No. YI have found that the solubility of saturated 398,361, filed June 16, 1941. This is now Patent hydrocarbons in hydrogen fluoride, and the solu 2,347,945, issued May 2, 1944. When organic flu bility of _hydrogen ñuoride in 'such hydrocarbons increases with elevation in temperature. At tem peratures near but below the critical for hydro gen fluoride, under supercritical pressures Ihave found it convenient to operate with a liquid hy- ~ drogen iluoride phase containing a _high content vof dissolved hydrocarbon. ~ rIn such instances ag1 tating means are sometimes unnecessary, during the digestion period in which the reaction is ef-` fected, a's discussed. Similarly, I may operate in the sub-critica1 temperature region with respect >to a hydrocarbon phase carrying in solution a high proportion pf hydrogen fluoride or acid. Reaction may be effected in acid rich liquid phase by contacting the hydrocarbon to be converted with liquid hydrogen fluoride at elevated tem perature, thereafter separating the acid phase, now containing the reactant hydrocarbon in so lution, and then subjecting the solution to reac tion conditions. The acid rich effluent from such a step may be distilled to recover the volatilizable hydrocarbons together with a part of the acid, orine compounds are not present or harmful, ory are to be removed by treating only a part of the material present, the hydrocarbon material can . 'be passed directly to fractionator 46, entirely or vin,pa.r1'.,fiîrom conduit 42 through conduit 69 and valve 1K0, valves 4I and 44 being partially or com pletely closed. ' ' ‘ ' ' Fractionator 46 effects'a separation of the hy drocarbon mixture into the desired products, by products, and recycle fractions. For exam-ple, if ' the principal product is motorfueljthe follow ing four fractions may be obtained: (l) a >by product fraction comprising chiefly isoparañ‘ins 60 boiling below the motor-fuel range, whichis with drawn through outlet 4l having valve 48, and which may be used as conversion stock in an al kylation process; (2‘) a motor-fuel fraction, which is withdrawn‘through outlet 49 having valve 50; (3) a fraction vboiling above the motor fuelrange, which may be recycled by way of valve 5I and conduit 52’ to pump Il; and (4) a bottom fraction comprising a high-boiling hydrocarbon residue, which may be Withdrawn through outlet may be used again in the conversion Step. In an other modiñcation hydrocarbon material may be 70 53 having valve 54. If desired, the motor-fuel fraction withdrawn may be limited to a relatively .introduced into the lower end of a column'of y narrow-boiling range in order to obtain relatively liquid acid maintained at reaction temperature concentrated specific materials, such as, for ex through which the hydrocarbon ascends by vir ample, highly-branched octanes, while‘other hy tue of its lower density, undergoing as it ascends While the residue of hydrocarbon-depleted acid y -partitionwith the hydrocarbon dissolved in the drocarbons boiling in the motor fuel range are 2,403,649 7 vseparately-recovered, by means *not shown '_or thereaction mixture in th'efliquid phase. The through 53, and/or passed tothe conversion zone reaction> mixture was then cooled to 32° F. and through' conduit 52. was allowed to stand for a few minutes, Where upon two liquid phases separated out. The upper or hydrocarbon phase was equivalent to»93 per .- . . . » The overhead effluent from fractionator 32'is separated into two phases in separator 40, as by cooling and centrifugal or gravitational means. »The lighter or hydrocarbon phase is withdrawn through outlet 55 having valve VV55; and theheavier or hydroiiuoric acid phase is recycled cent by weight ofA theV Aoriginal hydrocarbon charge. 'I'h‘ishydrocarbon product'was found to have approximately the following composition, in per cent by weight: propane, 1,2; isobutane, 4.1; through conduit 1l and valve 51 to conduit 33 10 pentane, 2.3;v hexanes, 1.2; highly branched >hep and to pump I5. f Part> or all of the light hy drocarbon material passed through conduit 55 may be returned to fractionato-r 32 through con duit 61 controlled >by valveI 58 in which case light hydrocarbons . mayv be through conduity 41. completely discharged Such an operation is more ’ fully disclosed, and is claimed, in’my copending application Serial No. 315,063, Filed March 11, 1940, now Patent 2,322,800, issued June 29, 1943. Fractionator 31 separates the acid eiiiuent from , separator 20 into an overhead fraction compris ing anhydrous hydrogen fluoride and small pro portions of hydrocarbons, which is passed by way of valve 58 and conduit 50 to separator 60, and into a bottom or sludge fraction comprising flu 25 oro-organic material, tar, etc., which is with drawn through outlet 5! having valve 52. tanes, 18.4; hydrocarbons boiling in the range of 93.5 to 100° C., 43.0, which appeared to be com posed of normal heptane, isooctane, and cyclics; hydrocarbons boiling above 100°’ C., 11.4. This product was found to havev an ASTM- octane num ber of 54.6 and a lead susceptibility of 12.5; it contained virtually no oleñnic unsaturation (by bromine titration). ~ ,» , Material of thefcharacter produced in this'ex ample is suitable for blending in ordinary motor fuel.. Preferably, however, an aviation-gasoline cut, such as an isooctane fraction, is separated out, and part of the remainder is recycled to the treatment with‘vhydrogen ñuoride, and/or, 'op tionally, part is used for conversion stock in other hydrocarbon-conversion processes. For example, the isobutane fraction is particularly advanta In separator 60, the overhead effluent from geous for use in alkylation processes; thefrac tions boiling above the aviation-gasoline range las by cooling and centrifugal or gravitational 30 are suitable for cracking stock to produce cracked means; a hydrocarbon phase which is withdrawn gasoline; and the relatively low-octane fractions through outlet 63 havingvalve 04, and a con boiling within the gasoline range are suitable for centrated hydroiiuoric acid phase which is re recycling to my process. ' ’ cycled by way of va1ve55 and conduit `(it to Example II acid fractionator 31 is separated into two phases pump I5. Any hydrocarbon -phase may, if de 35 A substantially pure isooctane fraction was ag sired, be passed from conduit 63 through conduit itated for one hour at a temperature of 70° F. r‘l2 and valve 'F3 to conduit I8 and separator 20. with an equal volume of concentrated hydroflu If desired, the sludge formed at the bottom of fractionator 31 may be subjected to thermal de oric acid. The reaction mixture was Withdrawn and was separated, by settling and decanting, in composition, whereby free hydrogen fluoride is to an acid phase and a hydrocarbon phase. The liberated, and the resulting recovered hydrogen fluoride may be recycled to pump I5. The ther mal decomposition may be effected in fractionator 31 itself, if a-suitably high bottom temperature is emp1oyed,ror it may be effected in a separate means, not shown. The process of this invention is applicable to hydrocarbon phase wasequivalent by Weight to 94.1 per cent of the original hydrocarbon charge. It had the following composition in mol per cent; isobutane, 29.2'; Pentanes, 9.1;'hexanes 4.8; hep tanes, 4.5; hydrocarbons boiling higher than hep tanes, 52.4. The composition of the normally liq many different specific hydrocarbon feed mate uid portion of the product, in per cent by weight, rials, and it may be employed to produce several was as follows: pentanes and h'exanes, 15.5; hep-k desirable effects. For example, in the produc tanes, 6.8; octanes, 34.2; nonanes, 9.3;` decanes, tion of isoparaffins of five toten carbon atoms 50 10.9; undecanes and dodecanes, 15.0; hydrocar per molecule, suitable for use in aviation gasoline, bons boiling higher than dodecanes, ,8.3. fractions of straight-run gasoline or natural gas This example illustrates the formation of hy drocarbons having higher and lower boiling points oline are suitable; these fractions may be ob tained by many known means, such as fractional and correspondingly higher and lower molecular distillation, selective extraction, and the like. lsopentane, when reconstructed by hydrogen `flu weights than those of the original material. " The lower boiling compounds, particularly isobutane, oride, yields, besides some isobutane, considerable amounts of `hexanes and heptanes, mainly of rather highly branched structure, that are suit are suitable for conversion stocks in alkylation processes for producing aviation gasoline; the higher-boiling compounds, such as undecanes and 60 higher, may be advantageously recycled within able for inclusion in aviation fuel. A few of the many aspects of my invention my process, or they may be used, for examplaas are illustrated in the following examples, which conversion stock in cracking processes to produce are purely illustrative and not necessarily limi aviation gasoline. The middle-range hydrocar tative of the invention. Example I A fraction fromV natural gasoline that boiled in the methylhexane range was found to have- a clear ASTM octane number of 46.9 and a lead susceptibility of 11.7 octane numbers for 1 cc. of tetraethyl lead per gallon. A portion of this ma terial was agitated with one third of its volumne of concentrated hydrogen fluoride for 26 hours at an average temperature of 270° F. anf‘ under pressure suñìcient to maintain all components of bon material, such'as pentanes t0 decanes, in clusive, is suitable’ for use- as aviation motor fuel. Example III In a process for'manufacturing-aviation gaso line, a by-product motor-fuel-range hydrocarbon mixture is produced that has an octane number of about 63 and a tetraethyl‘lead response of '7.5 octane numbers for 1 cc. of tetraethyl lead per gallon. This material is treated, in accordance with’ the principles of my invention, with an equal volume of concentrated hydrofluoric acid. The 2,403,649; 10 conditions are: temperature 350° F.; pressure, shaken 4continuously by a Ymechanical rocker., equivalent to the vapor pressure of the reaction The reaction mixture -was then withdrawn, and a _» mixture; time, 40 minutes; and rapid agitation. The reaction mixture isV partly in the vapor, phase. On being cooled, as to about V40 to 80° F., there hydrocarbon phase was recovered by decanting.` It V_was found by fractional analysis to have the followingl composition in per cent by liquid sulting Ymixture is separated into . two ,liquidV volume. phases. From the hydrocarbon' phase, which is` equivalent by weight to about 86 percent of ythe* . .Y Y. ~ ~ Lower-boiling _`_____________v_____________ Tracel original charge, is separated an aviation-gasoline f Butanes _ ______________________________ __ 8.5 70.2 fraction having an octane number of 85 and a 10 Isopentane lead lresponse of 12.5. e A relatively low-boiling _ N-.Pentane ______ __ ____________________ __ fraction comprising mostly isobutane is used as feed to an alkylation process for producing avia tion gasoline, and a relatively high-boiling frac Hexanes ' High bniling ____ ___ tion is subjected to a cracking process for produca 15 ing cracked gasoline. Y 100.0 Example VII anhydrous l hydrofluoric acid. ` Toa steel bomb of 400 cc. capacity were charged 84 grams of anhydrous hydroñuoric acid and43> Asteel bomb was almost ñlled with' 28 grams of C. P. normal butane and 60 grams of substan grams of C. P. normal pentane. The'bomb was heated to` 572° F. »and was maintained at that temperature for A30 minutes. vIt >was then cooled, and the products were withdrawn. It was found Suitable means for heating the bomb, maintaining the contents in intimatemixture, and for measuring the internal temperatureand `the pressure were by fractional'analysis that approximately 10l per centofiv the >normal pentane had reacted to give the following products in the proportions shown: provided. The temperature was raised to 350°F., and the pressure rose to 3700 pounds per square inch. 0.6 AY small proportion of .l tarry residue is withdrawn fromthe system. El‘ample IV tially , 8.3 12.4 After 3 hours th'e heatv was turnedroiî, and , the bomb was rapidly cooled.y The products were wtihdrawn and separated by decantation. The recovered hydrocarbon layer weighed 20.3 grams; , it was treated with alkaline solution to'remo've. Mol ' 30 Product:> Y '~ Lower boiling ______ _____ _______ __ ____ __.'I‘race Propane ` I_ 17.3 hydrogen fluoride. The resulting hydrocarbon Isobutane product was found by fractional analysis to have Normal lontane 31.5 ‘ the following composition, in per cent by weight: 35 Isopentane `Propane ___________ __ _________________ __ Isobutane > Normal butane Hexane 3.2 4.3 ì 6.0 Higher-boiling _.-_____ _______________.___'___ _3.0 n 2.5 40 Y 19.7 _ 22.5" 90.0 Isopentane ________ __ __________________ __ ' percent 100.0 Example VIII- ' 100.0 Ezramplel V To a steel bomb were charged 92.4 grams of In- an> experiment similar to that of `Example ` concentratedhydroiluoric acid‘and 50.6 grams of IV, 64y grams'of C. _P." normal butane and 188 45 normal pentane. The bomb was surrounded byV an electrical heating jacket, and was heated to grams of substantially pure hydroiluoric acid 570° F. in 70 minutes, as follows: up to 356° F, in were chargedto a steel bomb having a capacity 30 minutes, from 356 to 453° F. in> 17 minutes, and of 400 cc. During aperiod of two hours and from 453 to 570° F. in 23 minutes. At 570° F. a twenty minutes, the temperature was gradually raised to 520° F., at which temperature the pres 50 pressure gage attached to the bomb registered 4,240 pounds per square inch. The bomb was sure was 3400 pounds per square inch. The maintained at this temperature for 4 hours; and bomb was then cooled rapidly, and the contents was then cooled to 212° F. in 14 minutes. 'I'he were removed for examination. The resulting hydrocarbon material recovered from kthe bomb hydrocarbon material was. found by fractional analysis to have the following composition, in per 55 cent by weight: ` hadA the following analysis. Lower-¿boiling Methane __ 0.6 Propane 10.1 v Norma1 butano ì-Cï4Hio 50.8 60 Isopentane _____ ______ __________ __ _____ __ 8.1 __________________ __ ________ ____ _ ' ____________ __ _________ __ Trace ---__ ________________ __dO...... __ n-C4H1n " ` ~ i-CsHiz f __ n-C5H12 Norma1pentane_ _______________________ __ _2.0 Hexanes ~ CsHa _________ __»____ __Per cent by weight...` V2.7 Isobutane ___________ __T _______________ __, 25.9 Heptanes ' ' 06H14 2.0 ' ~ Higher-boiling l ` 4-.6 d0 3.0 do 10.5 do 76.6 dn ______________ __do ...... __ 1.7 0.9 0.5 65 100.0 The fextent of isomerization of normal butane to isobutane was considerably more than that ob tained in Example IV, as was also the conver-> sion to _isopentane and lhigher-boiling parañ‘ìns. v 'Approximately equal proportions by volumeof` isopentane andv yanhydrous hydrogen fluoride were charged to a steel bomb. For a period of 28 y ,y VExample IX Y . 100.0 l To arsteel bomb were charged 165.0 grams of concentrated hydrofluoricacidand 74.4 grams Yof normal butano, the bomb being agitated by ‘a platformV shaker. The ‘bomb VIwas heated from 145° F..up toV 302° F.; in"1_l"1our,iand,maintainedv daysl the ‘boint'ßv was maintained 'at atemperaturef '15 at 302° F. for vv2 hours. ’ »After.this,Y theìboinb was? cooled to >140°!F.fin 15 minutesz: YThe hydroc‘zar-'YV of 175° F. by'v an electric heating coil and‘wasï 2,403,649 1i* position. ' by weight ____ __ ___________________ __ i tion in the liquid-phase-‘while intimately mixed Per cent Lower-boiling 12 , bon material recovered had the following com 0.0 í-C4H1o _______________________________ __ 13. n-C4H1o _______________________________ __ 82.4 05H12 (and4 heavier) ____________________ __' 4.2. with 0.2 to 4 times by weight of coneízentratedr liquid hydroi’iucri'c acid as the eiTecti-ve vcatalyst at a reaction temperature ofvat `least-59" F. for a time sufficient to effect alteration of the struc~ ture of saturated hydrocarbons present tol form other saturatedY> hydrocarbons, and subsequently recovering from eiiluents of said treatment satu-V rated 'hydrocarbons' boilingin-the motorîfuel 100.0 10 ` 4. A process of `converting a saturated hydroIt Will 'be understood that Various parts Of the carbon material of" at least four carbon* atoms eflluent from theprocess may -be recycled. For per molecule into other saturated hydrocarbons, example', any ofthe fractions obtained from frac which comprises subjecting such a ¿material- to tionator 46, preferably the light-isoparafñn frac 15 reaction at an elevated temperature and pressure tion boiling below the motor-fuel range, may be while Vintimately mixed with 0.2'to-4 times ïby advantageously recycled to coil I3 and/ or reactor range so produced.j 23 by means not shown that can be readily sup plied by those skilled- in the art; thereby the yield of hydrocarbons of adesired boiling range or of a v ' ` ' ’ weight of concentrated hydroiluoric acidasthe effective catalyst for a time >such as to eiTect a material alteration in the structure of saturated 20 hydrocarbons in said hydrocarbon material into desired carbon-skeleton structure is increased. other saturated hydrocarbons, passing eiiluents of It valsowill -be understood that the equipment said treatment to a separating Zone wherein a hy used for this process may be of corrosion-resist drocarbon phase is separated from a liquid hy ant> steels, Monel metal, nickel alloys, aluminum drofluoric acid phase, subjecting said hydrocar and/or magnesium alloys, copper, copper alloys, bon phase to fractional distillation to remove orthe like, Since hydro?luoric Yacid is relatively residual amounts of hydrofluoric acid contained inert to metals in the absence of moisture, corro in said hydrocarbon phase, and >recovering from sion may be minimized by using substantially remaining hydrocarbons a fraction containing completely anhydrous hydroñuoric acid and by saturated hydrocarbons of atleast four carbon drying `the hydrocarbon material fed to the proc atoms per molecule and of altered structure Vs0 ess.-` ’ ~ My invention provides a new catalytic process for » reconstructing hydrocarbon materials. It provides a new process for improving the anti knock characteristicsnand the degree of satura tion of motor-fuel hydrocarbons, It further pro vides a novel process for producing lhydrocarbons of higher and/or lower molecular weight than produced. 5. A process of converting a saturated hydro carbon material of at least four carbon atoms per molecule, which comprises subjecting such a 35 material to reaction at an elevated temperature and pressure whileintimately mixed with 0.2 to 4, times by weight of concentrated hydroiluoric acid as the _effective catalyst for a time such as that of the original material. Still further, it to effect a material` alteration in the structure of . provides a process wherein normal and slightly branched aliphatic hydrocarbons may be con 40 saturated hydrocarbons in said hydrocarbon ma terial, passing effluents of said treatment to a verted t0 relatively highly branched aliphatic separating Zone wherein a hydrocarbon phase is hydrocarbons. separated from a liquid hydroiluoric acid phase, My process is especially advantageously ap subjecting said hydrocarbon phase to -fractional plicable' to treatment of all hydrocarbon mate distillation to remove residual amounts of hydro rials which comprise predominantly saturated fluoric acid contained in said hydrocarbon phase, hydrocarbons having four or more carbon atoms separating low-boilingk material so ,removed into per molecule. Because of the variety of mate a hydrocarbon phase and a hydroñuoric acid rials and the plurality of vpurposes to which my phase, returning said hydrofluoric acid to said re invention is applicable, there -are a large number of modifications and variations of my invention, 50 action, returning said hydrocarbon phase to said distillation, removing as a high ‘boiling product of which only a very few are specifically described of said distillation a hydrocarbon material essen in this speciñcation. Additional equipment such tially free of hydro?luoric acid but containing as pumps, valves, coolers, fractionators or the minor amounts of organic iluorine compounds, like, such as are well-known to those skilled in passing said hydrocarbon material to the action the art, may be used in my process wherever of granular bauxite to remove said organic fluo needed or convenient. It is not intended that rine compounds and. to. produce a substantially mention herein of specific apparatus, materials, liuorine-free eiiluent, and recovering from the hy conditions, theories, reactions, or purposes should drocarbon material so purified a normally liquid unnecessarily limit the scope of my invention. What I claim is: , l. A process of isomerizing a normal parañin 60 hydrocarbon .fraction boiling _in the: motor-fuel range. „ l 6. AY processY for converting hydrocarbons by having at least four carbon atoms per molecule, reactions -comprising isomerization and dispro which comprises subjecting said normal parañ‘ìn portionation,A which comprises subjecting a nor to the catalytic action of 0.2 to 4 times by Weight of Vconcentrated hydroiiuoric acid as the effective 05 mally liquid parañin hydrocarbon to a reaction temperature in the presence and intimately ad catalyst at an elevated temperature in the range miXed with 0.2 to 4 times by weight of liquid con of about 50 to 1000? F. for a time Suñicient to ef fect a substantial extent of isomerization of said normal paraiiin. v ~ 2.l The process of olai l, in which .said normal ` paraflin isnormal butane. 3. A process for improving the antiknock char acteristics of a saturated hydrocarbon material boiling in the motor ¿fuelrange which comprisesv subjecting such a hydrocarbonmaterial to reac-Vr centrated hydro?luoric acid as the sole catalyst `for a time su?icient to convert saidparafün hy drocarbon in part to isomeric paraffin hydrocar bons of Vthe same molecular weight and in part to parailins of higher and of lower molecular weights. M Y K Y 'LA process »for converting hydrocarbons ¿by reactions comprising isomeriaation . and dispro 2,403,649 13 14 ly recovering from eilluents of said reaction a fraction comprising at least one of said paraffin hydrocarbons so produced. l carbons of the same molecular Weight and in part to parañìns of higher and of lower molecular - i 13. A process for isomerizingl normal pentane to produce isopentane, which comprises subject ing normal pentane to isomerization under isom hydrocarbon in part to isomeric paraffin hydro Weights. „ forming paraffin hydrocarbons having fewer and morecarbon atoms per molecule, and subsequent portionation, which comprises subjecting a nor mally liquid paraífln hydrocarbon to a reaction temperature in the presence and intimately ad mixed with 0.2 to 4 times by Weight of liquid con centrated hydrofluoric acid as the effective cata lyst for a time suii'icient to convert said'parafjn erization conditions in the presence of liquid 10 concentrated hydrofluoric acid as the essential 8. A process for converting saturated hydro carbons contained in a saturated hydrocarbon isomerization catalyst to form isopentane, and recovering from eiiiuents of said isomerization material by reactions comprising isomerization and disproportionation, which comprises subject >isopentane so produced. ing a saturated hydrocarbon material to the cata lytic action of 0.2 to 4 times by Weight of inti f 14. A process for isomerizing a saturated hy 15 `drocarloon having at least four carbon atoms per molecule, which comprises subjecting such a sat urated hydrocarbon to isomerization under isom mately admixed liquid concentrated hydrofluoric erization conditions in the presence of 0.2 to 4 acid as the effective catalyst at a conversion tem-4 times by weight of intimatelyïadmixed liquid con perature for a time sufficient to effect a> substan tial conversion of saturated hydrocarbons con 20 centrated hydrofluoric acid as the essential isom erization catalyst to form a saturated hydro carbon isomeric with the ñrst said saturated hy drocarbon, and recovering from eiliuents of said tained in said material into other saturated hy drocarbons including at least one isomer of a saturated hydrocarbon so converted. f 9. A process for converting saturated hydro carbons contained in a saturated hydrocarbon isomerization a saturated hydrocarbon fraction material by reactions comprising isomerizationA and disproportionation, which comprises subject so produced. l5. A process of isomerizing a paraiîin having at least four carbon atoms per molecule, which comprising said isomeric saturated hydrocarbon ing a saturated hydrocarbon material to a con Version temperature in the presence vof 0.2 to 4 y comprises subjecting said paraiiin to the catalytic times lby-Weight of intimately admixed concen trated liquid hydroñuoric acid as the sole cata action of 0.2 to 4 times by weight of concentrated hydro?luoric acid as the effective catalyst at an lytic material for a time sufficient to elîect a con-Y elevated temperature in the range of about 50 to version of saturated hydrocarbons into other 'sat urated hydrocarbons including at least one iso tial extent of isomerization of said paraffin. mer of a saturated hydrocarbon so converted. 10. A process for converting a _paraffin hydro carbon contained in a saturated hydrocarbon ma 1000° F. for a time sufficient to effect a substan 35 16. A process of isomerizing a saturated hydro carbon having at least four carbon atoms per molecule, which comprises subjecting said satu- f terial, -Which comprises subjecting a liquidsatu rated hydrocarbon material containing at least rated hydrocarbon to the catalytic action of 0.2 to 4 times by Weight .of concentrated Vhydroiluoric one paraffin hydrocarbon of atleast four carbon atoms per molecule to a conversion temperature in the presence of 0.2 to 4 times by weight of in acid as the eifective catalyst at an elevated tem perature in the range of about 50 to 1000a F. for a time suñîlcient to effect a substantial extent of isomerizationV of said saturated hydrocarbon. 17. A process of isomerizing a cycloparaflin hy oric acid as the essential catalyst for a time suffi cient to convert said parañin hydrocarbon into an 45 drocarbon having at leastsix carbon atoms per timately admixed liquid concentrated hydroflu >isomeric parafûn hydrocarbon. molecule, which comprises subjecting said cyclo paraffin hydrocarbon to the catalytic action of 11. A process for converting normal pentane 0.2 to 4 times by weight of concentrated hydro into isobutane, isopentane, and isohexanes, which ñuoric acid as the effective catalyst at an ele comprises subjecting liquid normal pentane at a conversion temperature to the catalytic action of 50 vated temperature in the range of about 50 to about 1000o F, for a time sufñcientto eiïect Ia liquid hydrogen fluoride as the essential catalyst substantial extent of isomerization of said cyclo for a time sufficient to effect ra substantial con paraíi‘in hydrocarbon. version of normal pentane to isobutane, isopen 18. A process for isomerizing a cycloparaiìn tane and isohexane, and subsequently recovering from eñiuents of said conversion a fraction com 55 hydrocarbon having at least six carbon atoms per molecule, which comprises subjecting such a prising at least one of said isoparaflins so pro cycloparañln hydrocarbon to isomerization under » isomerization conditions in the presence of 0.2 to 12. |A process for effecting disproportionation 4 times by Weight of intimately admixed liquid of a paraffin hydrocarbon having at least ñve carbon atoms per molecule, which comprises sub 60 concentrated hydroñuorie acid as the essential isomerization catalyst to form a cycloparafûn hy- ' jecting a liquid saturated hydrocarbon material drocarbon isomeric with the ñrst said cyclo comprising such a paraffin hydrocarbon at a re parañin hydrocarbon, and recovering from eillu action temperature to the catalytic action of 0.2 `ents of said isomerization a hydrocarbon frac to 4 times by weight of intimately admixed liquid tion comprising said isomeric cycloparaflin hydro hydrofluoric acid as the essential catalytic mate duced. rial for a time sufficient to eiïect a substantial disproportionation of said parañ‘in hydrocarbon, 65 carbon so produced. ` FREDERICK E. FREY.