Патент USA US2408188код для вставки
Sept. 24, 1946. H. v. ATwELL cmnALYsT~ MANUFAGTURE Filed May 18, 1944 ON Il HAROLD v. ATwELL . ' I 'm Hrs AT’rd N'EY VE NTOR Patented Sept. 24, 1946 2,408,187 ' * UNITÈD „STAT PATENT‘ÍoFFIcE > ' _ Íaiosnsi CATALYST MANUFACTURE ~ - vliîlvarold ' ì ’ ' Atwell,- Beacon, N. Y., assignor to‘The Texas Company, New York, N; Y,-,;a corporation of Delaware. ,y d ` 1 @Application May 1_8, 1,944, seriam- .SSGßSQ-g, „ is claims. (ci. 252-254) ' . ~ ` ' ' ' ' vessel and subjecting the entire mixture to vheat‘ ing :and stirring in a batch type of> operation..- The present invention relates to catalyst manu- ` facture, and particularly'to ay .complex liquid'V catalystformed’by'reacting a solid metal halide, ' The present' invention .involves 'a' substantial improvement’ over the prior vart since it provides such as aluminum chloride,- with a normally liquid hydrocarbon in the presence of a promoter 5 for effecting solution of solid metal halidelin'äa such as hydrogen halide. > '- - .= r Í f ' solvent hydrocarbon under’conditions suchtthat ~ substantially :no complex. formation»Y occurs -fand then effecting reaction Abetween ».thefzdissolved Complex .compounds 'formedf by 1. reacting a metal halide with ar petroleum hydrocarbon in the presence of a promoter are usefulas catalysts halide» and Areacta'nt'"hydrocarbons ina separate for elïecting catalytic conversion of'hydrocarbons 10 zone. `f @The invention* thus ¿permits segregating the v‘conriple'x substantially las rapidly'.it is such as conversion processes involving valkyla. formed-and also permits" effecting contact be tion and isomerization. >The metal halide ‘may be> reacted with varioustypes of hydrocarbons tween rthe" solvent f hydrocarbon' land> the solid including oleñns,»paraflins, naphthenes, and aro matics.' A mixture of reactant hydrocarbons metal halidev _in the substantial absence» of complex. may be employed, as for~example,'kerosine or some other fraction of petroleum. _ ¢ ‘ . ' . An advantage ofthe process of the present in vention is thatfit avoids pumping and circula ` ' In accordance with ìthe invention ytheA solid metal halideï'is maintained’ in vay contact -zone in lump or granular form. ' A stream of saturated 27o C4 hydrocarbon in liquid phase is Vpassed through the contact zone in‘contactvwith the'V solid metal halide underconditions such as to effect solution of a small amount ofthe'vmetal halide in" the liquid stream. The ellluent stream from the con.lv tact zone containing~ dissolvedmetal halideis tioni‘of complex, Whichis particularlyv advantaá geòus 'iromrvthe standpoint of reducing corrosion arìd‘ei'osion of equipment'gf for example,` one serious ‘difliculty'experien‘ced in pumping' 'com-Ly 'plex- withv a reciprpcatingitypeof pump isfth‘at - theïcomplex penetratesA> thef'packingv glands; and solidiñes therein ultimately causing" substantial leakage'aswell as injury'to the pump. ’ ' `lidvoreover, theu‘avoid‘ance 'of the presence of complex'in the solution zone permits more ef fective contact between _the solvent hydrocarbon subjected to elevated temperature in the presence of hydrogen halide‘and also in the presence of the normally liquidireactant hydrocarbon in a 3.0 and `the solid metal" halide so that a uniform second zone so as to effect complex formation: betweenl the metal halide and the normally liquid reactant hydrocarbon. ' ' ' 'I‘he reactant hydrocarbon may lbe commingled - rate of solution is realized. \ ‘ u The invention also> involves a further advan tage as regards'the preparation of complex from a metal halide such as ~_ aluminum chloride. with the C4 hydrocarbon stream prior- to, -_or 35 Aluminum chloride is relatively more _solublefin subsequent to, its passage through the contact butane than it is vin higher molecular Weight hydrocarbons'. ' Thus' at a" temperature of about zone, 'although the latter _is advantageous, as will 200° F. normalv butane dissolves about 1.75% be explained later.V ` ~ Y ' aluminum chloride by >Weight ofthe butane While normal hexane at the same temperature dissolves only about 0.33%. lNormal butane at a temper ature ofl40° F. dissolves about 0.55% by Weight of aluminum chloride YWhile normal hexane vat The mixture of metal halide and reactant hy drocarbons remain inthe second zone for suil‘i cient time to permit.complexjfcrrnation.` The resultingr __ mixturefofv hydrocarbons con taininglcomple'x also undergoessettling so. as to effect phase separation between complex andun the sarnetemperature dissolves'only about 0.16%. reacted hydrocarbons.; The hydrocarbon phase comprising mainly C4 4hydrocarbons is*v drawn off in.A acontinuous streamzand recycled through y _ Consequently,reither normal or isobutane or a mixture' of both is'used in the present invention operation .isl conducted to effect substantial to eiïectf'solution ofthe solid metal halide and to transfer the dissoivedìmetal hande into the "reactionl zone fory reaction with kerosirle4 in which the halide is'much less‘soluble. ` „ l y L fThe invention also contemplates iortifying the formation of complex».y complex by subjecting it to‘contact with a stream u theïcontact zone to dissolved additional metal halide after which it-.again passes through the ' reactionand phase separation zones. The cyclic 50 . . . f Y . of.„`bu.ta`ne ,containing dissolved metal halide, .. Complex compounds `have been prepared Áhere tofore by chargingk aV quantity of hydrocarbon oil, ¿metal halide,l andA promoter`fto a.. reaction . 5.5 contact being continued until the complex has extracted metalhalide Afrom the solvent hydro 2,408,187 4 3 carbon to the extent desired, as will be described later. The resulting complex settles out and accumu lates in the bottom of the vessel 3, while the bu In order to describe the invention in more de tail, reference Will now `be made to the accom tane and unreacted kerosine accumulate as a panying drawing which comprises a diagram of vessel 3. hydrocarbon layer in the upper portion of the « The butane may undergo isomerization so that iiow useful in preparing a complex of aluminum ultimately the C4 hydrocarbons in the circulat chloride and kerosine hydrocarbons. ing mixture will compriseganequilibrium'mixture In the drawing the numeral- I rdesignates „a pair of vessels packed with solidaluminum ,chloe ride in the form of particles or lumps rangingl from about 1A to 1%; inch in diameter. Two ves of iso and normalbutane. The reaction condi tions of time and temperature are such ‘that only a very limited amount of the |butane enters into sels are provided so that when one is onstream complex formation with the aluminum chloride. the other is offstream for recharging with fresh The hydrocarbon phase separating in the ves ` sel 3 isl«continuously¿'drawn oiî through the pipe aluminum chloride. ' j ‘ 2 ' ‘ ` 9 and forcedï'byigthe pump I0 ‘through the pipe The numeral 2 designates allieating zone which may comprise a tubular heater wherein the mix I I to the-heatiexchanger 4 wherein the tempera ture of hydrocarbonsk and dissolved aluminun‘ry tureI _of the; hydrocarbons may be reduced if de chloride is raised to the temperature required _for effecting complex formation. i f ' f 1 On the other hand, the heat exchanger 4 may 20 be bypassed as indicated. . ` YIt is contemplated maintaining a. relatively The numeral 3 designates a reaction and set tling vessel. _ sired to a temperature in the range 150 to 200° F. ` . The numeral 4 designates a heat exchanger; through which the unreacted hydrocarbons are recycled from the vessel 3 Vto either of the vessels I. . short time.l of contact between hydrocarbons and solid aluminum chloride in aluminum chlo ride vessels t so that' the action taking place therein is essentially that of solution rather than complex formation. Reducing' the‘ltemperature An operation in which a butane: stream con, taining kerosine is' circulatedithrough'the system of the. recycled» hydrocarbons-in the exchanger 4 will be >described, ñrs't. is a further means of'- inhibiting complex forma f ~ , ~ 1 ' At the outset and’assuming'that'the-vessels»-I tion in the-'vessel'|.. ’ ~ . > . are packed with solid aluminum chloride‘,'thesys-- 3.0.' 1 The circulation of hydrocarbons through the. system is continued until substantially all ofthe tem is filled wit-h a mixture -of butane-and kero' kerosine present is converted to> complex. The sine, the pressure being _suflicient to maintain the compleximay‘be retained in the vessel 3 until the butane in liquid phase. The> kerosine may entire batch of kerosine charged is reacted. 0n amount. to about l0 to 15% by volumeV of the the other hand, the complex may «be drawn oiî. butane. The butane and kerosine are drawn continuously or intermittently if desired. . from sources not shown through pipes 5 and 6 A modified form'of operation involves charg respectively anddischarged into> pipe 'I vwhich ing the system first withbutane a-ndthen adding leads to the heater 2. The heater 2 is operated the kerosine inl small amounts to thecirculating so as to heat the hydrocarbon streamto a, tem»l butane stream. In vthis type of operation theperature in the range 200 to 300o F. _ The> heated. kerosine addition to the circulating stream. _may stream passes through pipe B into» the *vessel` 3.. be regulated, so as‘to _provide approximately the When the vessel 3 becomes filled with liquid, the amount of kerosine required to; react withY the overflow is conducted through- pipe S-by pump dissolved aluminum chloride in thepstream. pass I0 which discharges into pipe l-I .. The pipe Il. communicates with the> heat ex-Í `~'45 ing rto the heater 2. Thismethod of operation avoids- circulating unreacted- kerosine through changer 4 which in turn discharges into pipe I2. the aluminum chloride vessels I or at least-re The. pipe I2 communicates with branch pipes I3 and I4 leading to the vessels l. Y ' duces the amount so circulated to a minimum. By circulating the» hydrocarbon stream in the In this way the hydrocarbon stream is. vintro duced to the top of either of: the. aluminum chlo `5`0 foregoing manner through the solution vessels complex> formation therein can be substantially ride vessels and ñows: downwardly therethrough entirely avoided since under the conditions pre discharging through pipes. I5 and i6 as the case vailing therein butane- does- not enter into com may be».y which in turn communicatewith thepre viously mentioned pipe 1. ' ‘ ` plex readily. Once the system. has. become ñlled with> hw 55 i The complex formed.. in the. vessel 3 may be drawn off through a, pipey I1 to atower I8 for the drocarbon liquid, the introduction of further purpose of fortifying it with additional aluminum hydrocarbons may be discontinued. Under such chloride. The complex is advantageously dis conditions the butane and unreacted kerosine are posed as a static column of liquid in the tower I8. continuously recirculated through the. system un til substantially all. of the kerosine present: is 60 A stream of butane containing` dissolved alumi num chloride isvdrawn oiiv from the Vessels I` and converted to complex. In actual operation it is vconducted through pipe I9 which terminates in contemplated that the effluent stream from the a suitable distributor 20 positioned within the aluminum chloride. vessels l will contain a small bottom of the tower. ` , ` amount of dissolvedvalurninum chloride and will be substantially free from complex.- Any required < 65 The butane stream is thusv dispersed within the static column of liquid and rises upwardly there makeup promoter is added toYL this stream either through. In doing so thecomplex extracts alu prior to or subsequent to its passage to the heater minum chloride from the butane stream until the 2. The heating temperature. and the amount of complexv becomes saturated. promoter are correlated to eiîect substantially complete reaction between the dissolved alumi- ` num chloride and kerosine hydrocarbons. The reaction to` form complex takes place substan tially entirely in the. vessel 3 Whichis. of suffi; In this way a complex suitable’as an isomeriza tion catalyst may be prepared: For'example, -a complex catalyst effective for isomerizing normal butaneY is characterized' by havingl a heat of hy drolysis of about 300- tol 330 small calories per .cient capacity to permit a substantial reaction T5 gram of complex. The complex leaving the-»ves time, namely, about 30 to 60 minutes. 2,408,187 5 ' 6 Y sel 3 may have a heat of hydrolysis of only about 200 to 280 calories. Consequently, its heat of ` recyclingv said hydrocarbon phase to the contact zone, and >continuing the cyclic operation to eiîect substantial conversion of kerosine hydrocarbons to aluminum chloride-hydrocarbon complex. hydrolysis may be raised by fortifying in the tower I6 as already described. >This fortifying action 2. A method of preparing a complex catalyst is advantageously carried out at a temperature . of about 200° F. formed byreacting aluminum chloride with kero Y sine in the presence of hydrogen halide which During the fortifying action the effiuentstream comprises maintaining in a contact zone alumi of butane may be discharged from the tower I8 through a pipe 2| and passed all or in part to num chloride in solid granular form, circulating pipe 22 communicating with the previously men 10 through said contact zone in contact with the solid halide a stream of liquid hydrocarbons com tioned pipe H. prising a major portion of saturated aliphatic C4 'I'he fortifying stream of butane and dissolved hydrocarbon vand a minor portion of kerosine, aluminum chloride may be passed through the eiîecting contact between solid halide and hydro heater 2 prior to introduction to the tower I8 in order to maintain the required temperature con 15 carbons under conditions of time and tempera ditions in the tower I8. ture such that solution of a small amount of ' The collecting and fortifying of the complex may, if desired, be carried out in a single chamber ' aluminum chloride in C4 hydrocarbonsk occurs` without substantial complex formation, passing said stream of solution to a reaction zone, sub While specific mention has lbeen made of form 20 jecting it therein to elevated temperature in the or vessel. . Vrange of about 200 to 300ov F. and in the presence , 'ing a complex from aluminum chloride, it is con of hydrogen halide such that dissolved aluminum templated that other solid metal halides of the Friedel-Crafts type, such as aluminum lbromide and zirconium chloride,.may be used. Likewise, other hydrocarbons or hydrocarbon mixtures than chloride reacts with kerosine hydrocarbons to .form complex, separating resulting complex fromV the unreacted hydrocarbons including C4 hydro carbons, recycling the hydrocarbons from which complex has been separated to the contact zone; and continuing the circulation of hydrocarbons ` kerosine may be used. However, from the stand point of making a complex catalyst effectivelfor isomerizing normal parañins such as normal bu to effect substantial conversion of said kerosine K 1 tane, it is desirable to employ a non-aromatic hydrocarbon. `\ 30 Obviously many modifications and variations of the invention as above set forth may be made without departing from the spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in the ap pended claims. I claim: f f» 1. A method of preparing a complex catalys formed by reacting aluminum chloride with kero sine hydrocarbons in the presence of hydrogen halide which comprises maintaining aluminum chloride in solid granular form in a contact zone, passing a saturated aliphatic C4 hydrocarbon in hydrocarbons to complex. 3. A method of preparing a complex catalyst formed by reacting aluminum chloride with Akero sine in the presence of hydrogen halide which comprises maintaining in a contact zone alumi num chloride in solid granular form,r circulating through said contact zone in contact with thev solid halide `a stream of saturated aliphatic C4 hydrocarbons in liquid phase, effecting contact between'solid halide and C4 hydrocarbons under conditions of time and temperature such that solution of a small amount of aluminum chloride in C4 hydrocarbons occurs without substantial complex formation, thereafter vpassing the circu liquid phase through- the contact zone in contact lating stream containing dissolved aluminum with said chloride, eiîecting solution of a small amount of chloride at a temperature below about 200° F. in the C4 hydrocarbon under conditions such that substantially no complex formation 0c curs, passing the resultant solution to a reaction chloride to a reaction zone, adding to the stream, passing to said reaction zone a small amount of kerosine, subjecting the dissolved chloride to con tact with the kerosine in the presence of hydrogen hydrocarbons removing from the reaction zone carbons to complex. halide at elevated temperature Vsuch that dis zone, subjecting the dissolved chloride to contact 50 solved aluminum chloride reacts With kerosine to form complex, separating resulting complex from in said reaction zone with said kerosine hydrocar the unreacted hydrocarbons including C4 hydro bons in the presence of hydrogen chloride at a> carbons, recycling the hydrocarbons from which temperature in the range about 200 to 3009 F. complex has been separated to the contact zone, such that dissolved chloride enters into complex formation with kerosine hydrocarbons, separating 55 and continuing the circulation of hydrocarbons to effect substantial conversion of kerosine hydro resulting complex from C4 and unreacted kerosine a hydrocarbon phase consisting mainly of C4 hy drocarbons and substantially free from complex, ‘ HAROLD V. ATWELL.