Патент USA US2403714код для вставки
July 9, 1946. l F. E. FREY PRocEss FOR THE `'JJREATNIEM' 4011'.l-I'unmocARßoNs Filed July 11, 1942 NN 2,403,714 Patented July 9, 1,946 . uNflsTEofl-STATES PATENT: , - _ 2,403,714- j . PROCESS FOR'rHE Tit’lgnjlïl’yiENT'oir'-Y Y ' `HYDROCAR-BONSy I ` Frederick E. Frey,Bartlesville;l Ókla.; assigner-ato:l » Phillips VPetroleum Company, a= corporation of», 3 l ,Y §- K Delaware' Applieationculy 11, l1942-,"l varial No; «teaser _' Y 1a claims.vv (ol. ¿Q01-_1683.49 alkyiating,?elativelylmwáf Y 4process for This' invention relates' ,tothe treatment; Of by: ` ca‘ftio'nf> inla alkylatableY hydrocarbons in tlfieï'presenceÈ drocarbon»materials.l More particularly’ it V,ree ' *boiling> of ñuorin'e‘. compounds;` ‘a selected'ipartl or`r all bof' lates-:to the conversion, vley-'an alkylation reaction ' ‘ the hydrocarbon. effluent from ranïalky'latin'g 'zone may: be f advantageously ysubjected toïthegaction in the presence of a iiuorine-containing catalyst, of> relatively lowl-vboilingvv Yhydrocarbons to motor of. a s'olid porous- c‘ontact: material `toirern’ove‘.o'rV->> fuel hydrocarbons.` _Still morefparticularly, it re- ' lates to the removal of organically combined fluo lrine from the product vof such'fconversion. This` application is ’acontinuation-in-part of my` co pendingapplication,,Serial No. 398,361A,vñled June »ganic‘ ?luorine'coinpounds‘. pounds. asvr impurities.` 16,.1941, now U. S. Patent 2,3‘l7,945,issued May 2,1944-i . ' »f ` " » ' ' " Y An'lobject'of this invention isito efîect’substan- ' tiallyfcomplete removal of .'ñuorine; fromuhydro-f 10 carbon~ >liuids' containing organic ‘fluorine ` .come , Al further: :object :of ¿this-ï invention is ank »imi , l proved'lpr'ocesssfor’obtaining. a substantially fluo-->> y In'the manufacture; of rhydrocarbons by proc rime-free A»a'lkylate ëfrom" the' alkylationi of hydro# esses in which»Viiuorine-containinglcatalysts are 15 Vcarbons .in the >presence-tof al catalyst ’_coxm'irlsingV - Y ,y a iluori'ne compound. taining byfproducts‘are formed.V t These vprocesses used, small proportions of organic'fluorine-.con `other objentsfand advantagfsfwiu .begabnarent - may involve reactionsisuch aspolymerízation and fromy ythe ‘followingfdescrìptionçitne accompanying alkylation of relatively low-boilinghydrocarbons drawing, andî/o'rfthe appendedaclaimse». » .Y » to produce motor-fuelhydrocarbonsin the pres encerof catalysts lcomprising one or more of such 20 iluorinacompoundsI asf¿h'ydrofluoric acid, boronY trifluoride, and the like. AIn ¿accordance with' »the A‘present .inventio'rrgf‘fl have now found that the undesirable organic Vflu-f orinœcompounds ¿differ among". themselves-with respect >~to .the ease‘withlwhi'ch the lorganic' »ñuo‘nv Although the exactna-r , ture or composition of. the organic fluorine-con rine can'be removed. » For example, when th‘eltoe taining by-¿products which _may bekvformed has tal- hydrocarbon eiliuenti ,fromj a- hydroñuoric. acid alkylation process ris treated to remove iiuorin’e,~ as by\.contacting Withbauxite, and subsequently not been deñnítely establishedythey are believed tobepredominantly alkyl and/tor aryl. fluorides. They are not .completely removed by vwashing the hydrocarbons -with alkali solutions, They tend to ‘decompose Yat ‘eleva'taiV temperatures; 'suon as those employed in fractional distilïaticncf' the' - is .separated intoffracti'ons of. different boilingv ranges; the residual organic iluorine, whichfhas not been'-4 removed. byi the defluorinating treat*l Which‘is corrosive",Y especially :in the Y‘presenceof Y ingvi‘ractions;y ,Althoughëiti is possible bythe ment, is concentrated in therlrelatively>higl'reboilè» hydrocarbons, rtherebyj'forming"hydrofluoric acid, ì n moisture. " process of the-aforementioned c'open‘ding applica>-~` 'Inggases theyima'y thus'fcause'corro- Y tion to remove substantiallyî'all'lfluorine in asin# gle treatment by- .fusing suili'cìentlydrastic oper-. sion‘of handling‘equipment; inliquid motorffuel ' hydrocarbons‘they“ areV undesirable forreasons l. thatlare obvious.` 'f Y . _ ating conditions;~.I have found it is 4advantageous ~ to` treat; the xalkylationeiiluent under such .condif A According toy the* aforementioned“ co-pendin'g tions thatrtheïloiv-boilingxorganic fluorine'. is' re-r` application,V organic ñuorine compounds'may ' be removedv 'from hydrocarbonmaterials containing them by 'contacting' such hydrocarbonniaterials 40 withj solid porous Contactk materials. Contact~ materials which have been found-suitableginclude moved, then to‘sep'arate from the eíiluent at leastv one; relatively ¿high-¿boiling fraction'yand- ñnally .to treat this relatively high-_boiling fraction tome-f rnove'the high-boiling:organic-fluorine. Thereby ' the .most advantageousconditions for the removalof each type of organic ñuorinezcan .be usedr-andV genatíon or dehydrogenationreactions, such as alumina gel, activated aluminagidehydrated baux 45 equipment of' a givenA size or> capacity can'be- uti-' those vknown to. be catalyti‘cally active for hydro- , n ite, chromium oxide,r‘rnixturesy ofi~ alumina»` and chromium. oXide,ïmetals-"of the iron group,»-»es-peci'ally ñnely divided` nickel deposited onr an'- in@ ” lizedto the fullestadvantage.: » Y Understandingcofamyinvention maybe aided y c >by reference ltothe;accompany-ingdrawing; whichA erh-support, andïtlielikegl Such'contact mate- ' isf a schematic ilowediagram Yof one arrangementl of apparatus-for practicingthe inventionl; rialsfappear to adsorb preferentially the organic> fluorine- compounds;y althoughthe exact mecha- Y agent,A for example >an -.isoparafûn ' such as isobu-= ni‘smilnvolved is’ not ful-ly known.atapi'esegui'.Y.n . The ` tane or isopentanerandian oleñn’such as propyl' hydrocarbon material: being 'treated'.may. be. in". eitherfthe liquid ort'the.:vapor1ïphase.‘ Also,. ac-,_ cordin’g‘rto the~ aforementionedcof-pending appli-1` - Y »Analkylatable hydrocarbon and an'alkylating f ene or one orgmorejlof; the butylenes, respectively,` 55 Vai:efadmitted-preferably«through a number of _in 2,403,714 3 lets, such as that represented by inlet I0, and/or through conduit II and pump I2 to alkylator I3, in which' they are agitated under alkylating con ditions with concentrated or substantially anhy drous hydrofluoric acid, which may be admitted through inlet I4 and/or conduit I5 and pump I6. In the feeds to alkylator I3 the mol ratio of iso parañin‘to olefin, or other alkylating agent, such as the corresponding alcohol or halide or the like, masses which have been found suitable are alumina gel, activated alumina, dehydrated bauxite, chromium oxide, mixtures of alumina and chromium oxide, metals of the iron group, especially finely divided nickel deposited on an inert support, floridin, diatomaceous earth, and the like. Such contact lmaterials appear to adsorb preferentially the organic iluorine compounds, although the exact mechanism involved is not preferably having three to five carbon atoms in 10 fully known, The hydrocarbon material being the alkyl group, is preferably in the range of 2:,1 treated may be in either the liquid or the vapor to 20:1 or more, and the Weight ratio of hydroñu phase; -since the volume is relatively small in the oric acid to total hydrocarbons is preferably in liquid phase condition, and since all the mate the range of about 0.211 toj`4:1.-v_ The’ feed, or at rialsinvolved in this process are easily maintained least the portion of the feed which 'contains the 15 in the liquid V_state under the preferred operating alkylating agent, is preferably introduced into conditions, it is preferably treated in the liquid th'e reaction mixture under conditionsfof’high state. In general, theconditions of temperature turbulence and/or in multipointwise fashion, so and contact time in dei‘luorinator 28 should be that the alkylating agent is rapidly mixed 'and reacted with the isobutane or other alkylatable hydrocarbon'.~ Thisv procedure is advantageous. in Well below those which would induce deteriora tion or alteration of the hydrocarbon material. Temperatures‘between about 50 and 4:00"` F. may orderto: favor the. desired .olefin-‘isoparaflin j unc be employed. ’ The optimum temperature ’in any tures, or» alkylation reactions, and to hinder un particular instance Will depend upon the nature desirable olefin-olefin junctures,. or polymeriza of the contact mass, the nature of the material tion reactions. Preferred'operating conditions in 25 being treated, and the desired degree of removal alkylator I3,v as vfor example `for alkylating iso of fluorine. The `preferred temperature, particubutane with’ butylenes, to which for the sake of larly when bauxite is used, is approximately `simplicity this description maybe primarily de voted, 'are a temperature in >therange of 30°> to equal to or somewhat‘lower than the kettle tem perature of column 2 I , and is usually in the range l5.0°-.F., a pressure suiñcient to maintain all com 30 of about 150 to 350° F. By using such a tempera ponents in the liquid phase, and a contact‘time ture, the necessity for heating or cooling in de or time of residence in the alkylator. of about l ñuorinator 28 is avoided, and the removal of to 30 or more minutes; however, conditions out iluorine, especially offthat fluorine which upon sidelof> these ranges may be used Without passing distillation of the vfluorine~containing material beyondthe scope of this invention. _The opti 35 appears in the low-'boiling distillate fractions, mum alkylating conditions _vary with different such as 'the isobutane and butano fractions, is reactants;v 'for example,fin alkylating benzene with ethylene, or‘normal butane with oleñns, in sufhciently complete that corrosion of equipment by fiuorine compounds in the hydrocarbon mate the presence.` of .hydroiluoric acid as a catalyst, the-preferred Vtemperature is in the :range of 200° 40 rial is substantially Completely eliminated. While the same type of contact material may be utilized to 350° F. ~ = ~ ' . vAfter a suitable contact or reaction time, the resulting mixture passes through conduit I'I to separator I8, wherein >it is separated into two liquid phases, as by cooling and/or gravitational or.`centrifugal means. The heavier or hydroä fluoric acid. phase preferably is recycled', as through conduit I5, to alkylator I3; part of it may Abe withdrawn, as through valved outlet I9, and passed topurification or acid-recovery steps, not 50 in both steps, different »materials of the class de scribed may be usedin each-defluorinating step. At relatively high temperatures, Yvery high space velocities, such as about 2000 or 3000 vol umes of vapor (or an equivalent number `of vol umes of liquidrper volume of contact material .per hour, are'satisfactory; at relatively low tem peratures, the space velocity should be compara tively low, such as perhaps 1 or 2 volumes of liquid per' hour. In general the optimum space velocity depends not only upon the temperature but also Y The lighter. or hydrocarbon phase is passed upon such factors as the content >of fluorine, the through conduit 20.to azeotrope column 2|, in pressure used, the desired extent of iluorine re which it is'v separated vby fractional distillation into two fractions.. vThe overhead fractioncon 55 moval, and the particular Acontact material in use'. A suitable space velocity >for any particular sists of an 'azeotropiemixture .of hydrogen fluo application may be readily found by trial by one rideY and low-boiling paraffin hydrocarbons, such shownin the drawing. as ¿propane and isobutane. ` . . This fraction is passed throughconduit 22, condenser 23, and conduit 24. tosep-arator 25, wherein it is separated into 'two- liquid rphases, as by> cooling and/or vgravitational or. centrifugal means. . All of the lighter. or hydrocarbon phase is returned through éondu'itZGvas vreflux to azeotrope column 2l; thefheavier or> hydrofluoric. acid phase- may be recycled, as through «conduit I5,..to. alkylatorA I3. @The :bottom fraction from.. columnr 2|, which consists> of. hydrocarbons that are substantially free' from .dissolved hydrogen fluoride but that skilled in the. art. v ` ` ‘ The partially deñuorinated hydrocarbon vmate rial passes from defluorinator 28 through con duit 29 to deisobutanizer 30, whereby it is sepa rated into two fractions. The overhead fraction, which contains isobutane, may be recycled through valve 3| and conduit II tohydrocarbon inlet I0, or. 4part or all of it maybe withdrawn through valvedY outlet 32 to a kc_iesiredadditional processing step, not shown, such .as a dehydro genation step to produce oleñns for use in alkyla tor I3. If a substantial proportion of. 10W-.boiling comprise organically combinedA ?luorine, is passed 70 material other thanv isobutane„. such> as propane. and lighter, is present in this fraction, preferably through! conduit 2‘I.to defluorinatorv 28. Deflu~ orinator -28 may consist of -any suitable closed chamber', containing »a .dehydrogenation-'hydro genation-type .contact mass, through which the hydrocarbons . may; Abe' passed. ' - Specific- -contact at least. part offitv is passed through conduit 33 ,having valvel 34 ’to depropanizer 35, wherefrom undesired low-boilingv material is withdrawn as an `overheadifraction. through valved outlet 36, . 2,403,714 fraction containing about .003 per cent by weight of fluorine may be obtained. This fraction was 'contacted with an additional quantity of bauxite at 300° F. and a space velocity of 2.3 liquid vol umes of hydrocarbon per volume of bauxite per hour and at a pressure of '75 pounds per square inch.' The fluorine >content 'o'i‘ the eiiiuent'was found to be .0003 per cent', indicating " almost complete removal of fluorine. ' ' ' Instead of bauxite, the other contact materials " described, such as alumina, chromium oxide, etc., may be used in a' manner similar’to 'that de ' >scribed above. .. Because the invention may be .practiced other ‘Wise than as specifically described or illustrated nherein,` and >because many _modiñcations and vari ationswithin the spirit and scope of it will be obvious to thoseskilled. in the art, the invention should not be unduly restricted by the foregoing specification and examples, butI it should be re stricted only in accordance with the appended n claims. I claim: 1. The process of removing organically com bined ñuorine from mixtures of normally gaseous and normally liquid hydrocarbons containing said `fluorine, which comprises subjecting such a mix a solid, porous metal’ oxide-catalytically active for hydrogenation and dehydrogenation reac tions, for the further removal of organically com bined'fluorine from said fraction. Y 6. The process of claim .f5 in which the second defiuorinating zone is at a» higher temperature thanthe ñrst. , » 7. The process of claim 5 wherein said metal oxide isalumina in theform of bauxite and in which the temperature in the iirst deiluorinat ying zoneis between about 150 and 350°- F. and in the second defluorinating zone isfhigher than the temperature in said iirst deñuorinating zone and is between about 200 and 400° F. f „ 8.: Ak process for producing normally liquid hy drocarbons substantially free from fiuorine-con taining compoundsVwhich comprises alkylating a low-boiling alkylatable hydrocarbonwith `an alkylation agent in an alkylation zone in the Apresence of va Aconcentrated hydroñuoric acid al kylation catalyst, removingfromeiliuents of said alkylation zone a liquid.y hydrocarbon material containing hydroñuoric acid in solution, passing said liquid hydrocarbon material to a fractional distillation zone, fractionally distilling said mate rial in said zone at a kettle temperature between about 150 and 350° F. to remove hydrofluoric acid ture to the action of a solid, porous metal oxide as a low-boiling fraction, passing as a high-boil fraction and a normally liquid fraction, andI sub jecting the normally liquid fraction to the action drogenation reactionsk for `altime such that exten ing kettle product of said distillation zone an catalytically active for hydrogenation and dehy drogenation reactions, at a-reaction temperature 30 essentially hydro?luoric acid-free ñuorine-con >taining hydrocarbon mixture to a ñrst defluo '_ and for a time suiiicient to effect substantial re rinating zone without-substantially cooling or moval of said nuorine from said mixture and such heating saidfraction and contacting same, at that extensive chemical changes in the hydrocar about the kettle temperature used in said distil bons of said mixture are not effected,v separating ' the eilluent therefrom into a normally gaseous , lation zone, withla solid„vp_orous metal oxide .cat ' of: a second solid, porous metal oxide catalytically active for hydrogenation and dehydrogenation re actions, at an elevated temperature to effect fur- \ ther removal of fluorine from said fraction. 2. The process of claim 1 in which the solid, porous metal oxide comprises aluminum oxide. 3. The process of claim 1 in which said metal `oxide is alumina in the form of bauxite. 4. The process of claim 1 in which the temper ature of the ñrst vcontacting step is in the range of about 150° to 350° F., and the temperature in the second contacting step is higher than tha't‘of 'said first contacting step and is in the range of about 200° to 400° F. ` ' Y alytically active for hydrogenation Vand dehy sive chemical changes in the hydrocarbons pres ent in said mixture are 'not effected and such as to effect a substantial removal of fluorine from said mixture, passing eiiiuents of _said first defluo rinating zone> to .a separating means, separating a low-boiling hydrocarbon fraction comprising an unreacted lalkylatable hydrocarbon, separat ing further a higher-boiling hydrocarbon frac tion containing hydrocarbons produced by-said alkylation, passing the last said fraction to a second defluorinating ¿zone and contacting same therein at a `temperature between about 200 and ,400° F. and higher than that used in saidV first defluorinating zonewith asolid, po highly branched, saturated-type hydrocarbons which comprises subjecting a low-boiling alkyl yatable paraffin hydrocarbon to the action of an alkylating agent selected from the group which consists of oleñns, alcohols, and alkyl halides Vhav ing three to ñve carbon atoms per molecule, in rous metal oxide catalytically active for hydro genation and dehydrogenation reactions for a time Sufñcient to eil’ectl no substantial chemical conversion of the hydrocarbons present and such that the total eiiluent from said `treatment is essentially fluorine-free, and recovering from said second defluorinating zone a ñuorine-free hydro the presence of substantially anhydrous hydro carbon alkylate so produced._ fluoric acid as a catalyst in an alkylation zone 9. In a process for producing normally liquid hydrocarbons substantially free Yfrom fluorine containing compounds by alkylation of a low-boil ing alkylatable hydrocarbon in the presence of Ya 5. The process for producing normally liquid, under alkylating conditions, separating the eiîlu ent from said alkylation zone into a hydrofluoric acid phase and a hydrocarbon phase, `returning atv least part of the acid phase to ther alkylation zone, passing the hydrocarbon phase to av frac tionation step for removing free hydrogen fluo ride, passing the hydrogen fluoride-free hydro carbon material to a first defluorinating zone con taining a solid, porous metal oxide catalytically ._ . concentrated hydrofluoric» acid ,alkylation cata lyst, the improvement which comprises passing a liquid hydrocarbon material, separated from eflluents ofsuch an 'alkylation zone and contain ing hydrofluoric acid in solution, to a fractionalV distillation zone, `removing vfrom said material in active for hydrogenation and dehydrogenation re- ì . saidzone hydrofluoric acid as a low-.boiling frac tion, Yand passing _' from said distillation zone as actions, for the removal of a substantial propor tion of organically combined fluorine therefrom, debutanizing the eiñuent from said first defluori nating zone, and passing the remaining hydrocar bons .to a second defluorinating zone containing Y a high-boiling fraction an essentially hydroñuoric .acid-free i fluorine-containing hvdrocarbon mix ^ture to- a defluorinating , zone without;- substan tially »heating or coolingsaid ¿high-'boiling frac 2,403,714. 9 . I tion and contacting same, at about the kettle carbon mixture to a first deiiuorinating zone temperature used in said distillation zone, with a solid, porous metal oxide catalytically active for hydrogenation and dehydrogenation reactions for without substantially cooling or heating said frac tion and contacting same, at about the kettle temperature used in said distillation zone, with a solid porous contact mass comprising alumina for a time such that extensive chemical changes in a time such that extensive chemical changes in the hydrocarbons present in said mixture are not effected and such as to effect a substantial re-v moval of iiuorine from said mixture. the hydrocarbons present in said mixture are not effected and such as to effect a substantial re-` moval of tluorine from said mixture, passing ef iluents of said first defluorinating zone to a sec ond, fractional distillation zone, -fractionally dis tilling said material in said second zone at a ket tle temperature not greater than about 400° F. and higher than that used in Asaid ñrst distilla _tion zone to remove low-boiling paraiiins leaving a liquid alkylate fraction, passing as a high-boil ing kettle product of said distillation zone a sub 10. A process forproducing normally liquid hy drocarbons substantially free fromV iiuorine-con taining compounds, which comprises alkylating a 10W-boiling alkylatable hydrocarbon with an alkylation agent in an alkylation zone in 'the presence of a concentrated hydroiiuoric acid al kylation catalyst, removing from etliuents of said alkylation zone a liquid hydrocarbon material containing hydroiiuoric acid in solution, passing said liquid hydrocarbon material to a fractional stantially butane-free iiuorine-containing alkyl distillation zone, fractionally distillingsaid mate ate fraction to a second defluorinating zone with out substantially cooling or heating said fraction and contacting same, at about the kettle tem perature used in said second distillation zone and at a temperature higher than that used in said rial in said zone at a kettle temperature between about 150 and 350° F. to remove hydroñuoric acid as a low-boiling fraction, passing as a high-boil ing kettle product of said distillation zone an iirst deiiuorinating zone, with a solid porous con taining hydrocarbon mixture to a ydefluorinating 25 tact material comprising alumina for a time sui' zone without substantially cooling or heating said f iicient to eifect no substantial chemical conver -sion of the hydrocarbons present and such that fraction and contacting same, at about kettle the total effluent from said treatment is substan temperature used in said distillation zone, with a tially tluorine-free, and recovering from said sec solid, porous metal oxide catalytically active for hydrogenation and dehydrogenation reactions 30 ond deiiuorinating zone a substantially ñuorine essentially hydrofluoric acid-free fluorine-co'n for a time such that extensive chemical changes ‘ free paramnic hydrocarbon alkylate so produced. 13. The process or claim 12 in whichsaid con in the hydrocarbons present in said mixture are> tact masses comprise bauxite. not effected and such as to eiïect a substantial - 14. The process of claim 9 in which said solid, removal of ñuorine from said mixture. 11. The process of claim 8 in which bauxite is 35 porous metal oxide comprises aluminum oxide. 15. The process of claim 10 in which said solid, the solid,l porous material used in each said de porous metal oxide comprises aluminum oxide. iiuorinating zone. 16. The process of claim >9 in which said metal 12. A process for producing normally liquid oxide is alumina in the form of bauxite. paraiiin hydrocarbons substantially free from 17. The process of claim 10 in which said metal iiuorine-containing compounds. which comprises 40 oxide is alumina in the form of bauxite. 18. The process of claim 5 in which said metal alkylating isobutane with an olefln in an alkyla tion zone in the presence of a concentrated hy oxide y in each of said defiuorinating zones is droiiuoric acid alkylation catalyst, removing from aluminum oxide and in which the temperature in the ñrst deiluorinating zone is between about 150 eiiiuents of said alkylation zone a, liquid hydro carbon material containing hydrotluoric acid in and 350° F. and in the vsecond deiluorinating zone is higher than the temperature in said ñrst de fluorinating zone and is between about 200 and` solution, »passing said liquid hydrocarbon mate rial to a iirst fractional distillation zone and therein fractionally distilling said material at a kettle temperature not greater than about 350° F. to remove hydrofluoric acid in a low-boiling over head fraction, passing as a high-boiling kettle product of. said distillation zone an essentially hydrofluoric acid-free ilumine-_containing hydro 400° F. 50 19. The process of claim 8 in whichsaid metal oxide in each of said defluorlnatingl zones com prises aluminum oxide. FREDERICK E. FREY.