Патент USA US2406081код для вставки
2,406,081 Patented Aug. 20, 1946 ’ UNITED; STATES " PATENT] IPOLYMERIZATIONIdF owns, HYDROCARBONS); L, _, ' ‘ William A. La Lande, .Tr., andrllfeinz‘llleinemanm?Upper tion, Philadelphia, Darby, Pa., assignorsrtorPorocel Pa, a,-,corporation~ (iorporaof.;Dela ware" ' No Drawing. ,_ a . , , . ' , ~ ~r» , ~~ . ' -' ‘W ~ I » r Application‘Novemberi'lglfi?, , Serial No. 562,405‘ , _ ‘ " Y" 9 Claims. (01. 260-68315) Theipresent invention relates tothe polymeri zation. of ole?ns, and more particularly to, the polymerization ofv normally gaseous ole?ns to liq uid' hydrocarbons comprising essentially aliphatic 1%»onless by weight. In'order to“ obtainrvthe' most (ef?cient polymerization, the ole?ns; under-,; going ‘conversion _ should: beisubstantially ifree: of; moisture, ‘and thisvlmayljbe; accomplished byfdeér hydrating ‘the olefins- in a conventional'manneri polymers of copolymers suitable for use in the 5; with ‘dry-ing- agents? such as Activated Alumina; manufacture of motor fuel‘. ' ' V ’ silica-gel», calcium‘ chloride and‘the like; 'While‘.‘ An» object of, this invention is the polymeriza tion, of ole?ns'or of gaseous mixtures containing ole?ns in the presence of a catalystv comprising activatedbauxite to produce polymers boiling for: 1 the. most, part within, the gasoline’ boiling range.‘ A further object of this inventionl‘is the: poly merization of- dehydrated gaseous ole?ns, partic ularly the butylenes, at temperatures below 350 degrees F; in the presence of ' a'catalyst. compris-~ 15: ing bauxite which hasbeen actiyatedby heating, at, atempe'rature between ‘700, degrees and¢>180'0, degreesR, and preferably between._1200 degrees our-process is particularly, applicable to‘ the poly-v merization of the: butylenes', especially isobutyl-r ene, such process‘may also bejuti-lized in the con-' version of'gaseous ‘mixtures including other. ole-'1 - ?ns-r such as ‘propylene, or- mixtures- of gases in-- cluding ethane, ethylenapropane, propylene, the' butanes, ‘and the butylenes: Howevenrthe'presa ence-of substantial quantities of gaseous: hydro carbons other than‘v the :butylenesappearsto'havei an adverseie?ect uponthe catalyst, and'thecon-f version e?iciency ofvthe catalyst is substantially decreased from that attainable“ with: the butyl=~ F. and. 1800 degrees Fl to a-Hresidual‘ moisture, enes or isobutylene, .per se." jWhen, the gaseous;v content ofnot more than 2% by weight, and; 20‘ mixture comprises the butylenes, or the butylenesi' preferably 1% or less by weight. . with;variousproportions of other gaseous‘ hydro’ It has been proposed heretofore to crack or_ carbons, itis preferred to-ca-rry out the polymer‘ polymerize- hydrocarbon gases in thepresence of ‘3 ization under substantial superatmospheric pres-' various adsorbent catalysts such‘ as fuller’s earth, sure, for example, from 100 to~2~,000=pounds:'per1 acid activatede-bentonite, silica-- gel, activatedcan; 25 square,‘ inch. However, ' in- the polymerization of" bon, alumina, and alumina» supported on’ silica. 'I-‘hesematerials, with the-exceptionof- alumina, i$9buty1¢ne 01' copqlymerization? of isobutylene? possess in varying degrees the ability‘to‘ catalyze Willa-bummed’ or'butene‘2i the Operation may be‘ thepolymerization of ole?nsi, the, Catalytic e1?_ carriedrout at substantially atmospheric pressure,‘ ciency and catalyst life differing as between the 30' 01' higher pressuresrif desired- materials. Alumina, however, was found toliave" ' ' ' ‘ In carrying out our‘ process‘ We bring the gait“T little or no-activity in ole?n-polymerization, even: sous‘ ole?n‘ 01'‘ mixture‘ containing gaseous Ole?n“ , when employed under the most. favorable Com into contact with thethermallyvactivated bauxite; ' ditions_ at temperatures not in excess of 350'degrees F.: We have found that bauxite, when activated 35 #01‘ fliperiod of, time suf?cient' to‘e?ect polymer under certain conditionais superior» to. the cata129301011 With>~ the production of liquid'hydrocar lysts above mentioned, particularly with respect bans comprising for the most part alipha'?op‘?y‘ , torrate of. decrease in efficiency, and totaluseful mers‘boiling Within‘the motor'f‘uel‘range 01' hav life. More speci?cally, we have found'that bauxing an” assay‘ distillation end‘ point not’ substan", ite, when heated to a temperature between 700' 4° ?atly above 400‘ degrees’? The polymerization degreeSR and 1300' degrees F‘ for Suf?cient time of. isobutylene in the' presence of bauxitel‘of low, to reduce its moisture content or “Volatile mat_ moisture content is initiated at ordinary tempera ter" 150.6% by weight or less, exhibits to a marked degree,,the ability, to catalyze the polymerization; ature‘ ('70 degrees F. or lower) andsince the'reac ‘61011 is: exethermic; it may be necessary to‘ pro vide cooling. of the catalyst to prevent‘the reac or copolymerization of ole?ns to liquidwhydrocar- 45 tion temperature from reaching depolymeriza bons; Even better results‘ are. obtained: in the‘ tion or decomposition levels- Ordinarily, a high polymerization or copolymerization; . using‘ baux degree of conversion may be obtained with cata ite which has-been activated? at, 1200- degrees" F.. lyst temperatures of from-100' degrees 150-300 to 1,800, degrees F. to a residualimoisture content. of not more than 2% by weight; andipref'erablyiwx degreesiF; precaution being taken to avoidw tem- 2' =' ~ ~, I ‘ R 2,406,081 'peratures much in excess of 350 degrees F. The bauxite may be employed in the form of granular peratures, the polymerizationreactions being car ried out at various temperatures to obtain liquid hydrocarbon products. The length of time of particles or pellets of desired size, or may be utilized in ?nely divided condition wherein it is suspended or'dispersed in the ole?ns. during the conversion reaction and is removed from the re each run was two hours, and the results obtained are shown in the following table, the yields being , expressed in weight percent of the isobutylene action product upon completion of the reaction. charged. It is preferred, however, to utilize the bauxite in the form of granules disposed as a bed through ' which the ‘ole?ns may be passed in order to‘e?ect polymerization; which bed may be heated or cooled as required to maintain it at the desired conversion temperature. When, after prolonged? 11:; 7 Reaction‘ Percent conversion; bauxite activated at , '1 ' mp., ' 600° F. ' 7002?‘. 8.57 6.0 g v. M". v. M’. de rees F. use, the polymerizing e?iciency of the. bauxite has decreased to a commercially uneconomical level, the bauxite may be regeneratedby various m‘ethQ - ‘ . v.1vi’. . ' ' 146M571‘; 188%;1‘. . _ . ' v. if. v. M’, V ods, the most simple and" inexpensive Tof which'is ' -- " ' heating in the presence of air; 'V'In‘lieuof thermal regeneration per se, the spe t’ bauxite may be, treated with steam or solvents and thereafter subjected to heating at temperatures up to_-1800; - The l% V. M. comprehends volatile matter or moisture in the bauxite. plishes degrees complete F. The reactivation regenerationof usually the bauxite accom-j; to. 100% of its original e?iciency. " ' . » per hour through‘ a 200 gram bed of bauxite acti'-' vated by heating at a temperature of 1200 de velocity (volume of- gas pervolume of catalyst per hour) employed -is not; particularly important,- ‘ grees F. The. conversion temperature Wasmain tained, at 300 vdegrees and 100%. conversion of the isobutylene to liquid products was obtained‘ version is obtained regardless of'the space ve for a period of 300 minutes! at which timethe run was stopped, theve?iclency still being 100%.; The stabilized product. contained 93% by volume, of hydrocarbons boiling below'400 degrees F.,‘ and ‘ I locity. In the polymerization ofisobutylene, for example, at 300 degrees‘ F. ' in the presence '1 of bauxite catalyst,'100% conversion of the isobutyl ene to liquid hydrocarbons is obtained with space velocities up to 375 volumes of gaseous isobutylene this productwhen hydrogenated at atmospheric, pressure in theipresence of avcatalyst consisting of nickel supported on kieselguhr at, a tempera ture of 450 degrees F., had an octane number per-[volume of bauxite per hour; . With increase ~ in space velocity’ from 375 r0440, the conversion decreases progressively fromj100% to 90%,’v and (motor method) ‘of 104, and with 2 cc. of tetra with even‘ higher space velocities, the percentage conversion vdecreases further. I V I ethyl lead added, had an octane‘number of 109. ' Our invention may be further illustrated by the ‘following examples, which, however, are not to . product produced according to the present inven Characteristic, ‘boiling data or the stabilized: be construed as limiting the scope thereof. tion are'shown in the following table. While most of the product is suitable for hydrogenation to an’ .1. Isobuty1ene‘of‘_95% purity was passed at a l' space velocity of 250 vols. per vol. of catalyst per‘ aviation gasoline’ blending stock, the small high 7 ’ h‘our through a bed of 200 grams of 6-14 mesh " bauxite which ‘had been activated by heatingat 1200vdegrees F.‘ to a, moisture content of 1.18% by weight. Y The polymerization'reaction terhpera- _. ture was maintained at 275 degrees F. and total‘; " condensation to liquid hydrocarbon products was obtained; with no decline in catalyst activity durél ing the run which produced 6 grams of liquid = - In carrying out the polymerization, the space I since within certain limits a high degree of con ; ' -. ‘Y 4. lsobutylene Was passed at a. rate of 43 liters products per gram of catalyst. . Distillation of the > 1 unstabilized'product' yie1ded'67% by volume of hydrocarbons boiling between 72 degrees F. and 1 375. degrees F.,‘ 70%‘ of which distillate boiled : _ 1 between 200 degrees F. and 250 degrees F. and 1 comprised mainly diisobutylene ’ § amounts of tri-isobutylene. and minor boiling end may be depolymerizeddover‘bauxite. fuller’s earth, *or the like at’ elevated tempera-H‘ tures above about'800 degreesFi and recycled to’ the polymerization operation‘. v ' , Initial boiling point ________ __' _______ _i_°F_-_ 1180» 10% _ > y. - - _, _ _. 213 30% _______-i ________ __-_ _____ _.;____‘___.-.___._ 221 50% '_’_____'_ __________ _1_~_>_ _________ __'___.'__ 226V 70% ___L»_______ __. _______ __>___,___'_____ __V-_.- 233 80% ____r ____ -1 ____ _V____V__'_____; ______ __ 241 90% _________ _; ______ _-___-_ ____________ _‘__288» End point ______________________________ __ 370 Per cent dist; __________________________ .__ 97 Per cent res ____________________________ _._ 2 Spec. gravity__~____» ___________________ __ 0 7335 We claim: ' 1. The method of polymerizing normally gase ous ole?ns to liquidhydrocarbons, which com prises contacting saidiole?ns at a polymerizing‘ temperature below 350v degrees F. with bauxite which'hasv been activated by heating at a tem perature between-700 degrees F.‘ and 1‘800'deg'rees F. to a residual moisture content of not more 1 isobutylene polymers and isobutylene-butene-l than 6% by weight. _‘ '2; The method of polymerizing normally gase 1 copolymers, as‘ contrasted with 49 grams of poly ous‘ ole?ns to liquid hydrocarbons, which com §mers when isobutylene ‘alone was polymerized prises contacting said ole?ns at a polymerizing" temperature below 350 'degrees'F; with bauxite which'has been activated by heating at a tem? perature between 1200 degrees F. and 1800 ae-q .grees 'F'. to a 'residual‘moisture content of not’ I under the same conditions. " ‘ ' .3. Isobutylene was passed‘ at a rate of 43 liters ‘per hourzthrough 200 gram beds of bauxite which ' ' had been activated by heating at various tem-. -'-more*tlian.2% by weight. ~ " ‘ '> ‘ ~ 2,406,081 ~ 3. The method of polymerizing a normallygas eous ole?n mixture consisting essentially of bu tylenes to liquid hydrocarbons, which comprises contacting said ole?n mixture at'a polymerizing temperature below 350 degrees F. with bauxite which has been activated by heating at a tem-' perature between 700 degrees F. and 1800 degrees 1200 degrees F. and 1800 degrees ‘F. to-a residual moisture content of not more than 2%“ by weight. 7. The method of polymerizing isobutylene to liquid hydrocarbons, which comprises contacting‘ said isobutylene at a polymerizing temperature below 350 degrees F. with bauxite which has been activated by heating at a temperature of about 1200 degrees F. to a residual moisture content of F. to a residual moisture content of not more than 6% by weight. 4. The method of polymerizing a normally gas eous ole?n mixture consisting essentially of bu tylenes to liquid hydrocarbons, which comprises contacting said ole?n mixture at a polymerizing temperature below 350 degrees F. with bauxite which has been activated by heating at a tem perature between 1200 degrees F. and 1800 de not more than 1% by weight. 10 , 8. The method of copolymerizing a mixture of isobutylene and normal butylene to liquid hydro carbons, which comprises contacting said mixture of isobutylene ‘and normal butylene at a poly merizing temperature below 350 degrees F. with 15 bauxite which has been activated by heating at a temperature between 700 degrees F. and 1800 degrees F. to a residual moisture content of not grees F. to a residual moisture content of not more than 2% by weight.. more than 6% by weight. 9. The method of copolymerizing a mixture of said isobutylene at a polymerizing temperature 20 isobutylene and normal butylene to liquid hydro below 350 degrees F. with bauxite which has been I carbons, which comprises contacting said mix ture of isobutylene and normal vbutylene at a activated by heating at a temperature between 5. The method of polymerizing isobutylene to liquid hydrocarbons, which comprises contacting polymerizing temperature below 350 degrees F. 700 degrees F. and 1800 degrees F. to a residual with bauxite which has been activated by heating moisture content of not more than 62% by weight. 6. The method of polymerizing isobutylene to 25 at a temperature between 1200 degrees F. and 1800 degrees F. to a residual moisture content liquid hydrocarbons, which comprises contacting of not more than 2% by weight. said isobutylene at a polymerizing temperature below 350 degrees F. with bauxite which has been WILLIAM A. LA LANDE, JR. activated by heating at a temperature between 30 HEINZ HEINEMANN. '