Патент USA US2404628код для вставки
July 23, 1946. 2,404,628 " J. D. GRENKO Erm. POLYMERIZATION 0F HYDROCARBONS Filed June 1e, 1943 ' 525ML Ä u „NJ *I m6 G5 9 . Qi>><I AI: _ _ _ ¿il JOHN o. GRENKO ’ LYNN _ _ IN ENToRs 2,404,628 Patented July 23, 1946 UNITED STATES PATENT OFFICE POLYMERIZATION OF HYDRO CARBONS John D. Grenko and Lynn R. Strawn, Port Arthur, Tex., assignors vto The Texas Company, New York, N. Y., a corporation of Delaware Application June 18, 1943, Serial No. 491,320 `4 Claims. (Cl. :E60-.666) 1 Y This invention relates to the polymerization of 2 ~ « . tion such as is necessary during take-off. In other Words, during take-off it is desirable to em hydrocarbons such as normally gaseous oleñns` to produce nap'ntha hydrocarbons useful in the ploy a rich mixture and for this purpose a naph tha having a high content of aromatic constitu ents is preferable to one having a high content manufacture of motor fuel. »The invention involves polymerizing normally gaseous oleñns such as propylene and butylene by contact with a solid polymerizing catalyst of th'e alumina-silica gel type and more particularly With a catalyst consisting essentially of a mix ture of silica, alumina and zirconia such as de of parafñnic constituents, the latter being useful Where a lean mixture is employed as in cruising operations. . . A modification ofthe present invention in pressure in the -range atmospheric .to 300 pounds volves subjecting feed oleñns to contact with a fresh, or freshly regenerated silica-alumina gel polymerization catalyst at a moderate tempera vture not in excessof about 560° F. underwhich conditions the resulting polymer naphtha has a relatively high content of saturatedv hydrocar bons. The used catalyst preferably after being in contact with oleñn feed hydrocarbons for not more than about 5 hours under-the> aforesaid moderate temperature‘conditions is then em, ployed in a separate operation to effect'polymeri' ization of feed olefins under more elevatedv tem per square inch gauge.` It has been found that ' f by effecting the polymerization reaction with this perature conditions so` as to obtain a polymer ' naphtha which is relatively rich in aromatic con scribed in U. S. Patent No. 2,249,583. . More spe ciñcally the invention involves eifecting the poly merization with this type of catalyst under 4con ditions such that a polymer naphtha relatively rich in aromatic constituents is obtained. ' In accordance With the invention the feed olefin is subjected to contact with an alumina-silica type catalyst- at a temperature Within th‘e range about 580> to 700° F. and under apressure of about 150 pounds per squareA inch gauge o1' under a type of catalyst within the temperature range in stituents. question the resulting polymer is unexpectedly rich in aromatic constituents. 'I'he above mentioned patent broadly discloses subjecting oleñns to-contact with a catalyst of the type in question at temperatures ranging from 200 to 650° E'. and under pressuresranging The naphtha products obtained from ' eachoperation may be separately disposed of‘or . may be blended all or in part for th'e purpose .of producing’motor fuelY of predetermined charac teristics. l _ , Co-pending application, Serial No. 493,186, for Polymerization of hydrocarbons, filed on July 2, from 400 to 4000 poundsper square inch gauge. , 1943, by Nelson B. Haskell and Charles J. Ran Polymerization of oleñns such as propylene with naturally occurring and synthetic aluminum ' dolph, Jr., describes more specifically the poly merization of normally gaseous ole?ins under silicates has also been described by Frederick H. moderate temperature conditions with an alumi na-silica gel type of catalyst so as to obtain poly mer gasoline characterized by having a relatively . Gayer in an article entitled “The catalytic poly merization of propylene,” published in Industrial and Engineering Chemistry, October,.1933, pages high content of unsaturated hydrocarbons. ~ 'I'he 1122 to 1127. According to this author activated Floridin and especially a synthetic alumina-on co-pending application discloses effecting> the-re silica catalyst are active in the polymerization of . action at a temperature in the range about 425 to 560° F. during passage of the feed hydrocar propylene to a liquid hydrocarbon mixture of bons in gas ph‘ase through a contact mass of the very high unsaturation. Elsewhere th'e author points out that the polymer so obtained is pre ‘ about 0.25 to 0.55 pound of hydrocarbon ‘feed _per dominantly composed of olefin hydrocarbons. The present invention has to do, however, with the discovery that by employing a reaction tem perature about 580 to'600° F. and( above,Y the ’re sulting polymer naphtha, mayA contain as much catalyst employing a mass,y velocity in‘the’ra'nge pound of catalyst per hour. i. As there disclosed Lil the catalyst remains in contact with the hydro carbons undergoing treatment for notlonger than about 5 hours between catalyst- regenerations. The present invention vinvolves a distinction as 40 to 50% or more by‘weight of aromatic hy since it’has to do with employment of a reac drocarbons. tion temperature substantially above 560° F. for . . The production of naphtha rich in aromatic constituents is advantageous from the standpoint the purpose of producing polymer vnaphtha of diiferent character, namely, rich in. aromatic con of manufacturing aviation motor fuel useful stituents. However,. it is Within the scope Vof this invention to employ a two-stage operation, `Where a high superchargingfrate is employed so asto obtain a large power output Without detona 55 the >first stage involving the aforementioned 2,404,628 ¿i 3 `moderate temperature reaction while the sec alumina gel catalyst in the form of small gran ;ond stage involves the higher temperature reac ules, particles, pellets or pills, etc. The catalyst is continually fed into the upper portion of the reactor ¿l through a conduit 5. Provision may be made within the reactor ä for maintaining the catalyst in the form of one or more beds of desired depth. The catalyst moves slowly and downwardly through the reactor from the bottom of which it is removed through a conduit 6. `tion using partially spent catalyst from the mod ` erate temperature stage; In the higher _tem ` perature stage the used catalyst may be main tained onstream for a substantial period of time lof about five to eight `hours or ranging from a lfew hours up to two or three days, thereafter the catalyst is regenerated in the conventional manner and re-employed in the moderate tem Thus, as indicated, the feed hydrocarbon in `this instance ñows countercurrently to the down , perature reaction. In practicing the process of this invention a `catalyst may be maintained in a fixed bed, or wardly moving body of catalyst. The polymer "case the- feed olefin heated to the desired tern ized hydrocarbons including unreacted hydro carbons are continuously drawn off from the up perature is continuously passed through the con Ètact mass maintained at the reaction tempera per portion of the reactor li through a pipe 'l leading to a fractionator or fractionating unit 6. lture, and the iiow of hydrocarbons continued therethrough until the catalyst has become spent. Thereupon the catalyst may be regenerated in arate the product into a plurality of fractions beds, within a reaction zone or zones. In such f Fractionation may be carried out so as to sep including a gas fraction removed through a pipe 9, a polymer naphtha fraction through a pipe lo and a heavy hydrocarbon fraction through a pipe l l. The gas rfraction will comprise unre ` situ by the passage therethrough 0f oxygen-bear ing gas so as to remove carbonaceous deposits "upon the catalyst by combustion. Advantageous acted olefin hydrocarbons which may be recycled ly a plurality of reaction zones are employed ' Ã particularly Where the aforementioned two-stage 25 all or in part to the heater 2 or to the reactor 4. A separate stream of feed olefin which may be operation is employed. In this way when the of the same character as that previously men tioned is conducted fromY a source not shown catalyst inthe low temperature stage has been ` onstream for 5 hours the feedstream may then ‘be diverted to an adjoining> reactor containing through a pipe lâ'to a heater IB wherein it is `fresh or freshly regenerated catalyst.A `During ' this period the offstream contact mass is em i ployed for the higher temperature reaction until l such time as it has become substantially spent, heatedv to a temperaturein the range 560l to '700° F. The resulting heated hydrocarbons under a pressure of „about 1'50 pounds are passed through a pipe Il to the lower portion of a re when the feed stream is then diverted to another actor !8 operating on the same principle as the ` low temperature reaction. i The completely spent previously mentioned reactor t. The used catalyst passing through the pipe 6 ¿catalyst is then regenerated and thus placed in to which reference has already been made passes v ` contact mass which may be partially spent in the into the upper portion of the reactor lll and reaction. The several reaction Zones are thus `40 provides the moving bedV or beds of catalyst con-V tained within the reactor Ill. `manifolded together by suitable pipe connec ‘ condition for employment inthe low temperature The feed hydrocarbons likewise rise 'counter- Y tions so that any one or more of the reactors Y currently through the downwardly moving cata i may be taken offstream either for use under dif lyst maintained at the reaction temperature. -The polymerized and unreacted hydrocarbons are continuously drawn off through a pipe I9 to a fractionator or fractionating unit 26. This fractionator also may be operated to separate the l ferent temperature conditions or for regeneration I ofthe catalyst. ' Instead of a fixed bed type of operation a mov ;able bed type of operation may be employed wherein a body of catalyst movesV gradually previously described three fractions. `through the reaction zone either counter-cur ` The polymer naphtha issuing from the frac rently to or concurrently with a stream of feed hydrocarbons undergoing-treatment. For exam tionator 8 will be poor in aromatics or substan ple, two reaction zones may be employed, the ñrst being used for the low temperature reac Ition, while the second is used for the higher tially free'from aromatics, but relatively rich in , temperature reaction. saturated hydrocarbons, whereas the polymer f naphtha issuing from the fractionator 2@ will be relatively rich in aromatic vconstituents and may be substantially free from saturated hydro A body'of catalyst moves I through the low temperature reaction Zone and i the catalyst issuing therefrom is conducted to carbon constituents. the higher temperature zone. The spent catalyst l issuing from this higher temperature zone is then subjected to regeneration after which it is re l turned for use in the low temperature reaction 1 zone." 60 The polymer naphtha may be drawn olf through a pipe 272 while the heavier hydrocarbons are re . Y The >latter type of operation is illustrated by means of a iiow diagram` shown in the accom 1 panying drawing to which reference will now be ' made for the purpose of further description of theY invention. A gas yfraction may be re moved from the fractionator 2i) through a pipe 2l and the olefinic constituents thereof recycled yall or in part to the polymerization reaction. - moved through a pipe 2S. » If desired the polymer naphtha products ob- ` tained from the two fractionating units may _be drawn off all or in part toa receiver 2@ for the purpose of blending to produce motor fuel of As indicated in the drawing a stream of feed v olefin such as propylene is .conducted from a » I source not shown through a pipe I to a heater 2 `. wherein it is. raised to a temperature inthe range ,predetermined characteristics'. Spent catalyst is drawn yoff continuously from the bottom of the reactor lli through a 'conduit V¢l25to 560° F. and under a pressure of abouty 150 ‘ pounds; YThe 'heated hydrocarbon vapor,l is then unit 3l from which it can be recycled through a n >conduitt? to the reactor ii. ' `1 conducted through a pipe 3 to the lower portion of a vertical reactor 4 containing'a mass of silica 3o and may be passed to a catalyst regeneration In' the'reactor >i8 the charging rate’ may be maintained so that the massY velocity is within V2,404,623 5 Y. . , 6 This example'likewise indicates that tempera _ the range about .20 to 1.0 pound'of hydrocarbon feed per pound of catalyst per hour. While a moving bed catalytic operation is de ' tures of 423° F. and below are productive of poly >mer naphtha products free or substantially free scribed in connection with the drawing, never- ¿, theless it is also contemplated that other means " from aromatic constituents although such prod-, uçts have a relatively high content of saturated hydrocarbons. By increasing the temperature of employing the catalyst may be utilized, as, ' for example, a catalyst in powdered form may be injected into a body of the vaporized hydro carbons undergoing treatment within the reac polymer product is increased to 53%. amount to from a fraction of a per cent to sev tane number of about 78 to 80. 'I‘he addition of 3 ccs. of TEL raises the octane number to about to 652° F., however, the aromatic content of the ' The polymer gasoline rich in aromatic con 10 stituents which is obtained by employing a re tion zone. action temperature ranging from about 560 to The catalyst may be used in the presence of a 700° F. is characterized by having a CFRM oc small amount of moisture. For example, it may eral per cent by weight of the feed. In a fixed bed type of operation it may be 87. Mention has been made of treating propylene, but it will be understood îthat the feed to the advantageous to condition the catalyst following regeneration and this may be accomplished by passing a stream of feed oleñn through the process may comprise a mixture of olefin and contact mass or bed at a temperature substan non-olefin hydrocarbons such as obtained from refinery sources, Obviously many modifications and variations of the invention, as hereinbefore set forth may be made without departing from the spirit and tially below the reaction temperature for a pe riod of about 40 to 60 minutes. For example, the catalyst employed in the low temperature reaction may be conditioned by passing feed ole scope thereof, and therefore onlysuch limita iins at a temperature in the range 75 to 300° F. through the contact mass for a period of about 25 tions should be imposed as are indicated in the appended claims. 1 hour. We claim: In the following examples propylenewas sub jected to polymerization by the action of the catalyst of the character described in U. S. Pat ent No. 2,249,583. Such a catalyst consists es sentially of a calcined mixture of a major pro 1. A process for polymerizing propylene which comprises passing propylene through a mass of 30 polymerization catalyst consisting essentially of a calcined mixture of precipitated silica, alumina and zirconia having approximately the compo sition 100Si02í 2Al203: 12Zr02, said catalyst hav ing been previously exposed for a short time to mately the following composition: 100Si02, 35 feed olefin under polymerizing conditions at a 2A1203 and 12Z1'O2. temperature of at least about 340° F. and not The reactionwas carried out by continuously in excess of about 560° F. maintaining a velocity passing a stream of the propylene in gas phase of flow through the contact mass such that the through a contact mass of Ithe catalyst main mass velocity through the catalyst is in the range tained at a predetermined reaction temperature. 40 about .2 to .3 and effecting contact between pro Example A pylene vapor and catalyst at a temperature of portion of precipitated silica and minor propor tions of alumina and zirconia having approxi T‘Èlìfp" Thiële’ MV Yield Olefins Aromatics about 580 to 650° F., under a pressure of about X saturates 415..." 0.5 0.549 31.4 22 580. _ _ ._ 3. 5 . 526 37. 3 35 37 28 580 ..._ 6.0 . 530 4.1.4 32 28 40 150 to 300 pounds thereby obtaining a polymer naphtha' containing 40 to 50% and more by weight of aromatic hydrocarbons. 2. A process for Í.polymerizing propylene .to Vproduce naphtha rich in aromatics which com prises passing propylene in a continuous stream 7 In the foregoing tabulation the temperature represents the average reaction temperature of the contact mass; time refers to the length of through a mass of polymerization catalyst con sisting essentially of. a calcined mixture of pre time in hours that the contact mass has been onstream; MV represents the mass velocity in pounds of charge per pound of catalyst per hour; yield represents the weight per cent of the poly- i mer product, basis propylene feed; and oleiins, aromatics and saturates represent the per cent by weight of these constituents in the polymer product. As indicated by the tabulated data the product obtained at a reaction temperature of 415° F. Vhas. a relatively low aromatic content, namely, 7%, and a relatively high saturated hydrocarbon con tent, namely, 71%. By effecting the reaction at a temperature of 580° F., however, the aromatic content is materially increased to a value rang ing from 28 to 37%. 34o___-_ jected to contact for a short time with a stream of propylene gas under polymerizing conditions at a temperature below about 560° F., main taining the catalyst mass at a temperature of about 580 to 650" F., and under a pressure of about 150 to 300 pounds and maintaining a ve locity of flow through the contact mass such that the mass velocity through the catalyst is in the range about 0.2 to 1.0 pound of hydrocarbon feed per pound of catalyst per hour. 3. A continuous process for polymerizing pro pylene which comprises passing a stream of hot propylene vapor through a reaction zone main v tained at about 425 to 560° F., subjecting said' vapor to contact therein with a catalyst consist ing essentially of a calcined mixture of precipi Example B Teâlbïl’" Thlïlëf’" Mv Yield cipitated silica, alumina and zirconia having the approximate composition 100Si02: 2Al203: 12Zr02, said catalyst having been previously sub tated* silica, alumina and zirconia having the ap proximate composition liOOSiOz: 2Alz03: 12Zr02, oiefius Aromatics saturates y, .505 39.2 47 c 5a 423- _ 1 .841 43. s 51 o 49 652- _ .__ a . 31s 7o. 1 4s 53 1 removing from the reaction zone an eñluent hy drocarbon stream comprising polymer naphtha rich `in saturated hydrocarbons, removing >used 75 catalyst from said reaction zone, passing re .movedoatalystto a separate reaction zone, pass ing lthrough said .separate reaction zone a. >sepa. matics, and blending polymer naphthaJ from both said reaction zones to yform- motor fuel. raf'terîstream .o_f v hotl propylene vapor, eñ‘ectîng Contact between used catalyst and lseid Vseparate ¿stream .of propylene vapor at a temperature of 4. The method4 according .togclaim 3 in which used catalyst is removed from seidA separate zone, regenerated, and returned to said. lfirst about 580 »to .650° F., removing from said sepa. Arate reaction zone an eñìuent hydrocarbon stream comprising polymer nalohtlnal rich ín aro mentioned reaction zone. JOHN D. GRENKO. LYNN R. S’I‘RAWN.