Jan. 4, 1955 2,698,829 V. HAENSEL, ‘TWO-STAGE PROCESS FOR THE CATALYTIC CONVERSION OF GASOLINE Filed Deo, 29, 1960 43 REFORMED GASOLINE Lich stratcnT — RUN é 3 INVENTOR: ; ig VLADIMIR HAENSEL 5 Bl gf hiulane é = f SEG Gina, ATTORNEYS:United States Patent Office 2,698,829 Patented Jan. 4, 1955 1 2,698,829 TWO-STAGE PROCESS FOR THE CATALYTIC CONVERSION OF GASOLINE Viadinir Hacasel, Hinsdale, ML, assignor to Universal Oil Products Campany, Chicago, Il, a corporation of Delaware Application December 29, 1950, Serial No, 203,474 2 Claims, (Cl. 196—50) » This application is_a continuation in-patt of, my ¢o- pending “application ‘Serial No, 92,866, fled’ May 12, 1549, now U. 8. Patent 2,664,386, “This invention relates 10 the extalytic conversion of hydrocarbon fractions” It is. more. particularly con Soined with a specie method of reforming straight run Seeolies and the like in the presence of catalyst com- finn atimon containing 'mlnorproprtons of om- nod halogen anda member of the plainim group. tlt comprising alumina, member ofthe plat num group, perdeslery platinum, and combined halogen, Particularly combined itoring and. combined chlorine, Be copeiallytoefal in the reforming of hydrocarbons Hydrosrackiag of parafine and dehydrogenation of naph {nce ate armong the. principal reactions that. are pro- Ihoted by these estalyst, which are capable of jneressing {he octane number of staight ron gasolines and naphifas fo yalucs dat gre substantially Higher than those that Stalanvly ‘can ‘be reached. by. thermal reforming. In Gidlton: the yielz-octane ‘number relationships realized Stith these catalysts are mich better than are the corre sponding ations obtained in thermal reforming and iPhost of the prior eatayite reforming processes, By th appropriate ssletion of operating conuition, these Sctaljes can be used for-e number of weeks and even Shonths without regeneration. These catalysis also are UHective in promoting the isomerization of hydrocarbons fericularly poratini hydrocarbons. T have invented an Faproved brocegs for teforming sagt ron gasolines and the like inthe Presence of these catalysis, t's an object of the present invention to increase the gclag sunber of low" octane. soles end Hass theres fis another object ofthe present invention to produce Ijgher yolds of reformed gasolines having lower volati- TES'ign ns are prodded in eormipg browses employing catalysts comprising platinum, alumina, en combined halogen one embodtinent my invention relates te an improve- ment in the reforming of hydrocarbon fraction co Thining naphthenes and. parafins and boiling approxi- aaelswikin the pusoline ange in the presence of Wyro- fon and cofaget comprising platini, alumina, and Combined. halogen, said improvement comprising, sab- fenting std traction fo the aetion of fist body of said EXaget maistained ar reforming conditions ineluding a pressure of at least about $00 p. stg» and thereater Ribjecting the thustrented fraction to 4 second body of Seid ceiver tnsintsined. af reforming ‘conditions in- Gluing & Pressure Tess thon about 300 p. i @ the pressure of said second body of catalyst eing at Teast 6° Bpout 200 psy i less than the pressure om said first body of exif, i anti embodiment my invention eae oa prec ess which comprises passing hydrogen wid a hydrocarbon SFaction contalning paratias and naphthenes and boiling Approximately within the gasoline rango through # frst #28 of platioum-aluminn combined atogen catalyst st @ Temperature of from atout 780° F. to about 1000" F. nda presure greater then about $00 pu. iy passing the bulk of the hydrocarbons ta the effluent fom said fist catalyst body topsther with hydrogen throvgh a Second. body "of platinum-slumina-combined halogen Shrayat ata temperature of from about 730° F. to aboot $000" Fe and a pressre less than about 500 p 8. Bo ihe presure on said second body of calalyst being at 30 6 50 80 2 Jett tot 29 pt thn te person id it seg treat Fe sodment my intention rele t 0 CE er rect nati pe fein 3. Hp Kaci a he en By fos one and hg ey et rt a Sain aS cia at a ce Dad Oa cet Mae Rae Se ee ae eae ee Basa mca SSG WRU eae Sram eaten tas Ease SSS fs Hoan a rect ta a aaah MR See ns ee weer ihoeg anes ne anos oe eee eee ee a See al aS te, Rec cee ee a ee yn ae pola: have 2 fa oe a Tn ce point within the range of from about 325° to about 425° ee ee ea Tine UL \iise hate’ dea lta SN ATER eat APOE TeEE Saal lash oo ah 3m F, to cya 425° by a ma os Ua ay ewe in poss cmos ana sme ely aes Sas uate tat an ean Hat te See faa oes go Sa Sse Pa a, Set a AP af Siac lac, Saray aS arta ees cn Sau! oa 2 Be hi fe age oa she Ot Bessa eau hat See et ty Shoo Rea eo hear ser sea en ne uy aR Abate Paoee ba adits ene cee eee ee Sa cate Se ioe eal ee eae Ey el in ny pres enue me re tl ay cami i St, ne Serer ann sl, asm ae api ghee oni See i teas eh ae See RS, wn me Se a cee heat apa orm og cede aes ra eerie ea al aya my feo anergy See ae a eae ee sate ream commana eas Soh oi er alec Ber Se aL nan ite eter seo an 20, Tt eB ecm id pis ca tet ae SEF Raagl alfoPlenbind er See eae ete ta age Se ne a eee Pee sept a hate Beas ra lore tol Pans amt sau fot ah and fe, oe a Peat pe ee Cate ay Ace aie oo2,698,829 3 from about 750° F, to about 1000" F; pressure—preater than about $00 p. si, and usually not greater thaw about 1000-1200 p. s,s: ydrogen-hydrocarbon moat ratio— greater than aboot 0.3 and usualy betveen about 2 and Sand weight hourly space velocity, defied as the weight cof hydrocarbon charge. per hour per Weight of catalyst {nthe reaction zone ffom sbout 0.5 to about 40, snd Usually Between about 2 and 4. ‘Under the conditions of operation outlined above, low etane number straight ran gasoline and the {ike will be Substantially up-araded wid very litle loss of charge Stock, and the operation will be essentially nonregenet= ative. “The nonregenerative characteristic of this oper. ation is due tothe presence of sm apprecinble amount of fiydrogen in the reaction zone and to the relatively high pressure; i.e», greater than about 500 ps. ig. Ie pres- Sures gubsianialy below this value were employed: the Tate of deposit of carbonaceous material on the catalyst would be greatly increased and the tsefl life of the catalyst would be appreciably. shortened, necessitating replacement or regeneration thereof. Regeneration Undesirable because of the greatly increased capital cost of the plant when regeneration facies ars provided, because" of the frequent of stream periods that are ne” cesstated, and because inadequately controlled Tegen- eration may harm the catalyst “Although operation at pressures of about S00 p. si. cor higher is desirable from the standpoint of catalyst life {tis disadvantageous from the standpoint of conversion of naphthenes to aromatics. At higher pressures, the equilibrium of the reaction, naphihenes to aromatics, 13 appreciably fess favorable than itis at lower pressures onseauenty, at high pressure operations, ful lization ‘of the naphthenes isnot obtained ‘This results in a poten tal loss of octane number, since the conversion of magi thenes to atomaties incresses the octane number of ihe product. In order fo oblain a. given premitm octane hhumber, itis necessary fo, hydrocrack ton somewhat greater extent than would be necessary if all of the po- tential aromatics ware produced. tydrocratking a very efficient way of increasing the yield as well 4s the octane number providing itis carried out t0 only & lim: ited degree, since at higher hydrocracking conversions the eld fails of rapidly. The mcressed hydrocracking that Is necessary to compensate for the les thon quantitative conversion of naphihenes rests in & lower vist of gaso- line’ product having. a relatively" high volatile higher than is desired by some refiners who have natural sasoline or butanes and peatanes with which to blend Into the reformate, {avoid many of the disadvantages enumerated in the foregoing paragraph, by charping st lest the bulk oF ts hydrocarbon effluent from the first sage to 2. second slage which is maintained af 4 presse less than about 500 ps. i. g, the pressure in the second stage being at ieast'300 p. 5, lower than the pressure inthe fist stage Tn my second stage, the bulk ofthe remaining unconverted naphithenes' are. dehydrogenated. to the ‘corresponding aromatic hydrocarbons. Vary file hyérocrackiny takes place in this zone. As a rest, my twa stage process Eapable of yielding «higher octane number product with very litle foss in yield, or, by adjusting the: operating gonditions inthe fist stage to give a smailer amount of hydrocracking, there can result larger yield of the samme eetane number product. In other words, the increased onversion of nphthenes to aromatics redces the amot of hydrocracking necessary to produce a refornate ef © fiven oetaine namber. Tn general the reforming conditions maintained in my sega siae are substaniiy the same ay those mete tained fa the first stage. However, one principal excop- tion is in the pressure which, as hereinbefore sated, wi bo less than about 500 pounds, and will be atleast bout 200 pounds lower than the pressure maintained in the fir Stage. As hereinbefore stated, the lower pressures favor the naphhene: dehydrogenation equilibrim, and reduce the tendency towards hydrocracking. Arf exception ‘is the temperature. In general T maintain essentially the same temperatore of a higher tempera. {ure fn the second stage than I doin the fst stage. This is for the reason that increased temperature also favors the naphihene dehydrogenation eauiibrium, Because of the flower pressure, the fnerensed| temperature hs Tess tendency ta promote hydrocracking. In some types of operation, T maintain a lower hydrogen-hydrocarvon 12+ 0 20 io 10 % 80 85 4 the second stage than in the first to further decrease the hydrocracking tendency. ‘Hydrocarbons may be reformed in accordance with my process using fluidized, fluidized-fixed bed, suspensoid, ‘and moving bed types of processes. However, I preler to use fixed bed operation primarily because processes of this type tend to minimize attrition losses of the relatively expensive catalyst. One fixed bed method of condvcting my invention comprises preheating hydrogen and the hy- drocarbon charging stock to a conversion temperate, and passing the same through 2 plurality of substan: tially adiabatic reaction zones containing a catalyst eom- prising alumina containing minor amounts of combined hhalogen and a member of the platinum group. In the initial stages the reaction is endothermic, hence the te actant stream passing between said zones is reheaied to the desired temperature, ‘The effluent from my fist, or hhigh pressure, stage may be passed directly to my see ‘ond, or low pressure, stage. "Alternatively, the eftent from my first stage may be cooled t0 condense the ol ‘mally liquid hydrocarbons, the hydrogen separated there. from and recycled to the first zone, and the condense hydrocarbons passed to the second zone together with hydrogen. Another type of fixed bed process that is suitable for certain types of operations comprises passing the hyciro- carbon charging stock together with hydrogen through fubes containing catalyst, said tubes being subjected io radiant heat from a radiant flame and the resulting hot products of combustion. Ordinarily, this type of opera tion would be suitable for my first stage Which is more highly endothermic than the second stage. In any event, the reformate is recovered and the hydrogen is separated therefrom and recycled to the stages, Further features and advantages ‘of my process will become apparent from the description of the flow diagram shown in the figure. In the figure, a full boiling straight run gasoline is passed through line 1, js picked up by Pump 2 and is discharged into line 3. "If it is desiree to charge the entire full boiling gasoline to the first stage of my reforming process, the gasoline is passed throuat line 4 containing valve § and into heater 6 wherein the tem erature is raised to a value within the range of from about 750° F. to about 100° F. Just before the stream centers heater 6 itis joined by a stream of recycle hydro en, prepared as hereinafter described, which enters line 4 through line 7. ‘The hydrogen is reeyeled at a rate such that the mola ratio of hydrogen to hydrocarbon joe. Ths head mix of hydrocarbons aad hydrozan ey ing heater 6 pass farough line 8 and into retcfor 9. Ht tip desired to process only the heavier portion of the straight run gasoline in reactor 8, the full. boiling jpraight ron guioline passing tarough ‘ing 3. pased through valve 10 and into fractionator 11, The Tight fraction, which may have an end boiling point of about 200° 'F., is removed ovethead from fractionator i through ‘tine 12, "If this light fraction is not to be f ther processed, it may be passed through line £3 contain- ing valve 14 and sent to storage or blended with the re formed heavy fraction. If it is desired to process this light straight run fraction, it will be directed through line 15 containing valve 16 and passed into heater 6 whercin it will be heated to. a reaction temperature withi Tange of from about 750° F. to about 1000" F. The 's heated light fraction will be passed through Jine 17 and into reactor 18. It may be necessary to increase the Pressure on this light fraction if the pressure in reactor 48 is higher than itis in fractionator 11. For purposes of simplicity, reflux condensers, recel pomps,and the like are omitted from the drawing A itis to'be understood that they are to be employed in con- jimetion with fractionator 11 if necessary. ‘A heavy fraction having a boiling range of from about 200° F. to about £00" F. is removed from fractionator 11 through Tine 48 containing valve 19 and is dirzcied through line 4, heater 6, and line § into retetor 5. This heavy fraction is joined by a stream of rezyele hydrogen Passing through line 7. A single adiabatic ‘reactor is. shown although ordinarily 2, 3 or 4 adiabatic resctors with hes fers between the reactors will be employed. Reacior 9 contains a ded of 14” x 14" pellets of platinum-aluming- combined halogen catalyst having a platinum content of 0.3% and a fluorine content of 0.3%... ‘The pressure fa the reactor is maintained at 700 p. 5. i. g.5 ‘The following reactions take place in reactor 9: A sub- stantial portion of the cyclohexanes are dehydrogenated to the corresponding aromatic hydrocarbons; alkyloyclo- Pentanes are isomerized to cyclohexanes which are then Schydrogensted to the corresponding aromatic hydrocar- ‘bons; ish boiling paraffins ere hydrocracked to lower boiling paraffins of higher octane number; and straight chain and. mildly branched. paraffins are isomerized to more highly branched parafins. Because of the relatively high pressure that is maintained in reactor 9 to prevent excessive carbon deposition on the catalyst and thereby insure nonregenerative operation, a number of the reac- tions, particularly the conversion of naphthenes to. aro- matics, do net go to completion, Therefore, the effluent from reactor 9 contains hydrocarbons that can be con- yerted to higher octane number hydrocarbons by process- Ing over the same type of catalyst, but at a lower pressure. "The effluent from reactor 9 may be. passed,, without appreciable change in the temperature thereof, through line 20 containing valve 21 and introduced into reactor 18. “Alternatively, the effiuent from reactor 9 may be passed through line 20 and then directed through Tine 22, Sontaining valve 23, through condenser 24, and line 28 into separator 26, wherein a separation is effected between the hydrogen, which is in the gaseous phase, and the liquid hydrocarbons, ‘The hydrogen may then ‘be withdrawn through line 27 and introduced into line 28, where it is picked up by compressor 29 and recycled via line 7 ‘hzough ester 6 and into reactor 9." Make-up hydrogen ‘may be added through line 30 containing valve. 31, or excess hydrogen may be withdrawn through said Tine. ‘Also, excess hydrogen may be bled from line 27 through, tine 32 containing Valve 8 into line 34, which is part of a separate hydrogen recycle system for the low pressure a iauid hydrocarbons may be withdrawn from separator 26 tivough line 38, passed through heater 36, wherein they are heated fa rection temperature within the range Ot from about 150°. to sbont 1000" F. and thence Gsssed through line 37, fine 20, and into reactor 18,” The figuid hydrocarbons, withdrawn from separator 36 are Joined by a stream of reeyele hydrogen, prepared as here- Inatter described, passing throigh fine 34, before they are passed through Rater 36. Reactor 18 conisins one or more beds of platinam- siuming-combined. helogen setalyst having’ a platintim Sontent of 03% and a fivorine content of O34. The fressre in this reactor fs msintained a¢ 300 pos, kg. An Spprectabie Proportion of the remaining aligieyclopen” {ics and exGiotexanes ere converted to the cortespond- tng scotadehyroctoone inh veacor TEU dee Sed lant straight ran fraction passing through line so nay be charged fo reactor 18. Many of the parafis ‘his light fraction will be fsomerized Yo higher boiling ‘tomers, and. the methyleyclopentane and cyclohexane eet ithe fection wl be converted tlre part fo benzene, “Tre iyétogen and hydrocarbon effixent from reactor 18, is pased through line 38, condenser 38, line 40 and into Separator 4i._ Liguid hydrocecbons are withdrawn from Separator 41 through lines 42 containing valve 43 and are Sent fo storage or Blending fies, -ydcogen is wilh- cinwn from separetor 41 throvgh fine 44, i picked Up {fy compressor 48, and is discharged foto line 28 from whence itis recysted to reaclor 9 and/or reactor 18 “Te following example is eiven to further ilustate my jon, but it not given for the porpose of unduly 2 the generally broad scope of the same EXAMPLE A full boiling straight run gasoline having an F-1 clear ‘octane number of 42 was passed through a bed of plati- ‘num-alumina-combined halogen catalyst comprising alu ‘mina containing 0.3% platinum and 0.3% combined fuorine. This slep was designated as stage 1. The efluent from stage 1 was condensed, the hydrogen was separated from the liguified hydrocarbons, and the yield, octane umber, and vapor pressure of the reformate determined. Thereafter, the effent from stage 1 was passed directly into stage 2 with only a slight heating thereof. The cat- lyst in stage 2 was of the same composition as that em- ployed in stage 1. The operating conditions and results of the two stages are shown in the following table: 30 40 0 60 0 80 8 Stag. ‘Liga dun ope loa. ‘pega ol fal "es, Vo, Parent of Charge to me Plltyce PBL Get Ne a3 fied Vigor Passa, a It can be seen that there was a very appreciable gain in the octane number of the product and only a very small loss in yield brought about by passing the effluent from stage 1 through stage 2. The beneficial resulls of my two stage process are fur- ther evidenced by the following data which show the effect Of pressure on the conversion of methyleyclopentane and cyclohexane to benzene at normal reforming conditions Pressure, p. tg, Poreont Bongo. rom Methyleylopentan Fon ana? 8 Tecan be seen that if the fraction contining methyleyelo- Penfane and cyclohexane is processed at 700 p. si By the Inajor portion vill remain unconverted. These can Be converted hy further processing at 190 p-3, Alterna: threly, this fraction need only be charged to the second Sy fy Poors ad \¢ principal operating, conditions and re amy two stages ae fisted below retstage Pressre, ‘Above about 600 | Below about 00 pee nat lane Bea ele a tho ‘Tomperatare Ta-,000"F. sow F., but at last tenet the et apn ent age be a8 Hig a in syed, Hata...| Fae hgh topo Saatbontar | “ists Principal Resets... Hydtoctacking | Debydropmation of na a sree: | ite aomenstl ot ee ener | cag tok natn | EF Eling eonmad ul boing range "Ronse Tevet ‘ter wihoue daproe: | eee = ‘As hereefore sed a elavely high rset a a ie ioe SRA ee salts ig HSN cues ete Tat dean fale Eeraee ans ge melts as Tore oe ae tak st Fite temper alo ish Pe sa ace ib erenee tian to trond ant PE eee ere sete Gant sPia he taae eae emrcs 2 gin nas gan Wn Reel WA ere Ee ano eat yal of cre aes Tar er of Prt te ee sees Freel ny te ofa fe an rae yo ea yh hae es amas oF igh inden Svs et a pied by Si ino age operation fo ordre ssalne of ier By cy a eat Peas, es AS Paseo mel Nonale toernatoe in he ele alt en a eects Bushes her cane Matec eae caclng Ethers aie prot of Sencate le itig cay ncaa one ehogen de tent netic other ea ae ee reece eso tides Tay unnuiso sot roe eae ae2,608,829 7 for the high pressure stage and one for the low pressure stage, Telaim as my invention: 1. A process which comprises fractionating a straight run gasoline to separate therefrom a light fraction boiling 5 below about 200" F. and a heavy fraction boiling above about 200° E., passing hydrogen and the heavy fraction through a frst Body of catalyst comprising alumina con faining’ @.15-1.9%. platioum ond 0.130% combined hhalogen maintained at paraffin hydrocracking condition including a temperature’ of from about 750" F. 10 about 1000" F. and a pressure greater than about 500 p. s. ig supplying substantially all of the normally liquid hydro: carbons in the effluent from said ‘first catalyst body to. gether with hydrogen and said light fraction to a second body of catalyst comprising alumina containing. 0.05- 1.5% platinum and 0.1-3.08 combined halogen main- 0 8 tained at a temperature of from about 750° F. to about 1000" F. and a pressure less than about 500 p. &. k gy the pressure’ on said second body of catalyst being at least About 200 p. si, less than the pressure on said first body of catalyst 2. The process of claim 1 further characterized in that said light fraction contains the major portion of the meth yleyclopentane and cyclohexane originally present in said Straight run gasoline References Cited in the file of this patent UNITED STATES PATENTS 392,749 Lewis eta. _ Jan. 8, 1946 2/417/308 Mar. 11, 1947 21463,741 Mar. 8, 1949 2,479,110 “Aug. 16, 1949