Патент USA US2404661код для вставки
July 23, 1946. R. T. sANDERsoN 2,404,661 MANUFACTURE OF MOTOR FUEL Filed Aug. 15, i 1942 Om PIL? I Il' »/mm ROBERT THOMAS SANDERsoN /N VENTO/e A TTORNE Y Patented July 23, -1946 t 2,404,661 il 1 ~ UNITED STATES PATENT OFFICE` 2,404,661 MANUFACTURE oF Moron FUEL `Robert Thomas Sanderson, Beacon, N. Y., assign or to The Texas Company, New York, N. Y., a corporation of Delaware Application August 15, 1942, Serial No. 454,970 i 5 Claims. (Cl. 260-676) 1 Z This invention relates to the manufacture of motor fuel and particularly to motor fuel rich. in branched chain hydrocarbons. The invention has to do With obtaining 2,2,3 trimethylbutane from a mixture comprising the _ » 2,4-dimethylpentane may be obtained by various methods of organo metallic synthesis. They may be obtained in processes of isomerization and alkylation and by cross polymerization with sub sequent hydrogenation and synthesis through trimethylbutane and its isomer 2,4-dimetloyl-` 5 organo metallic compounds. pentane by a process involving treating the mix- i y . One procedure for the catalytic preparation of ture with sulfuric acid under conditions such 2,2,3-trimethylbutane involves reacting a methyl that 2,4-dimethylpentane undergoes conversion' aluminum halide with an alkyl halide as de into 2,3-dimethy1pentane, and distilling a. frac- 10 scribed in my pending application, Serial No. tion rich in 2,2,3-trimethylbutane from the treated hydrocarbon mixture. Advantageously, the treatment of the hydrocarbon mixture is ef- 452,698, iiled July 29, 1942, for improvements in Organic synthesis. ` I As therein disclosed methyl aluminum chlo fected with concentrated sulfuric acid at a temride or other alkyl aluminum halide is placed perature in the range about 70 to 125° `F. The 15 or formed in a suitable reaction vessel, and an acid treated mixture is subsequently treated with aliphatic halide such as 2-chloro-2,3-dimethylalkali prior to distillation for the purpose _of butane is introduced slowly, advantageouslyV in removing traces of acid remaining in the hydrothe form of a solution in 2,3-dimethy1butane. carbons. i This solution containing about 12 to 15% of the . The hydrocarbon 2,2,3-trimethylbutane boils 20 chlorodimethylbutane is added over a period of at a temperature of about 178° F. while the isomer 2,4-dimethylpentane boils at a temperature of about 177° F. In the catalytic prepara- about-,3 hours, while maintaining areaction tem perature in the range about minus 58° to 32° F. The total solution added amounts to about 15 to tion of 2,2,3-trimethylbutane relatively large 2o parts by weight per part of methyl aluminum amounts of the isomer may be present. The 25 chloride. I isomer 2,4-dimethylpentane has a C. F. R. M. As previously intimated other methods of pre octane value of about 82 or thereabouts, whereas paring branched chain hydrocarbon mixtures 2,2,3-trimethylbutane has a materially higher containing 2,2,3-trimethylbutane and 2,4-di methylpentane may be employed. octane value. For this reason it is frequently desirable to produce the trimethylbutane in as 30 In any case, the synthetic hydrocarbon mix concentrated form as possible for the purpose ture is subsequently treated with concentrated of making high octane motor fuel. Due to the acid and thereafter distilled in accordance with similarity in boiling temperatures, however, this the method of this invention so as to obtain a` separation cannot be effected by conventional hydrocarbon product rich in 2,2,3-trimethyl 35 butane. fractional distillation methods. It has been found that concentrated sulfuric acid at temperatures in the range about 70 to125° F. exerts no substantial effect upon 2,2,3- Reference will now be made to the accompany ing drawing illustrating one method of iiow which may be employed in practicing the invention. trimethylbutane, but under the same condi- i In the drawing methyl aluminum chloride from tions does effect substantial conversion of 2,4- 40 a source not shown is introduced through a pipe dimethylpentane into 2,3-dimethylpentane which I to an alkylation unit 2. A solution of 2-chloro has a materially higher boiling point, namely, 2,3-dimethylbutane is introduced from a source about 194° F. Consequently, the acid treated not; shown through a pipe 3 to the unit 2. The hydrocarbon mixture can be subjected to charge materials are thus subjected to reaction fractional distillation and thereby effect re- 45 in the unit 2 so as to produce a hydrocarbon prod-. moval of the more volatile hydrocarbons from uct vcontaining 2,2,3-trimethylbutane and 2,4-di the higher boiling and less valuable hydrocarbon. methylpentane. For example, by subjecting 2,4-dimethylpentane to the action of 95% H2504 at a temperature of The hydrocarbon mixture is accumulated in a tank 4 from which it may be conducted through ' - about 120° F. for a period of 2 hours some 15%` 5o a pipe 5 to a mixer B wherein it is brought into contact with concentrated sulfuric acid intro or more of the hydrocarbon is converted to 2,3 duced through a pipe 1. This acid may have a dimethylpentane. The - acid treatment appar concentration of about 94% to 100% or more `of ently causes isomerization of the afl-dimethyl pentane. n > HzSO4, and preferably a concentration'of about \ Mixtures of the trimethylbutane and its isomer 55 97% H2SO4. , 2,404,661 3 The mixture of acid and hydrocarbons is sub jected to thorough agitation in the mixer 6 While maintained at a temperature of about 7_0 to 125° F. over a period of about 20 minutes to 3 hours. Th‘e products of reaction are drawn off through a pipe 8 to a settler 9 wherein separation into - hydrocarbon and acid phases respectively occurs. The acid phase; is drawn off fromzthe bottom ofv the settler through aI pipe I 0 and may be dis charged all or in part from the system as spent acid. On the other hand at least a portion of it may be passed through a pipe l l communicating with' the previously mentioned pipe 1 whereby it is recycled to the mixer 6 for use-in. treatingifur ther'feed hydrocarbon. The hydrocarbon phase is drawn oiî from the settler through a pipe I2 to a neutralizing‘vessel; I3 wherein it may be treatedwith alkali for the> purpose of removing remaining acid therefrom; The 'neutralized hydrocarbons are then passed ~ through a pipe' I4 to-afracti’onator l5». The frac, tionator t5 is“ operated sozaszto separate from. the hydrocarbon mixture. a> distillatev fraction. con'. taining.Y 2',2,3-»trimethylbut‘ane and unreactedl 2,4» dímethylpenta'ne; This distillate fraction isr dis'.- \ charged from the fractionator. through a, pipe |162. The., residual fractionY removedl from: the. bottom on.' theifractiorrat‘or through apipe- l1 comprises. 4 pentane drawn oir from the fractionator 29 through a pipe 32 may be conducted together y with th‘e hydrocarbon drawn off through the pipe l1 to a tank 33. Y The liquid fraction comprising 2,3-dimethyl pentane drawn 01T from .the fractionator 29 through a pipe 32 may be conducted together with the hydrocarbon drawnoiî throughthe, pipe I1 to a tank 33. The above described method of flow comprises a two-stage operation. However, it is contem platedA that anyÁ number of stages Vmay be used or instead a single stage may be used as al ready' intimated. Moreover, the conditions of 1 acid treatment may'vary from stage to stage with respect’ to acid" concentration, temperature and time» of contact. Obviously many modifications and variations of the' invention, as hereinbefore set forth, may be made without departing from the spirit and scope. thereof', andi therefore only’ such limita tions shoul‘d: be: imposed: as arezindicatedi the'.i appended claims; I'claim: . , ‘ - ` 1. 'Iïlrrev method ofev removing. 23s-dimethylpen..-x ` tane from. amixture: comprising 2.4i- dimethylpena tane: and;r 21,2 ¿3-trimethylbutane»,. which conrprises 2-,3‘-dimethylpentane. subjecting; saidî mixture~ tof the- actionao?' concert..-y `are;` 2Q' which' passedïthrough'. may b'e'simiiar' the. pipe.-toi k6.’ the: to a1 mixer second'.AßA andU hydrocarbons comprising 2,3%-dimethylpentane..-V . substantiall'yJ similar conditions so: as. to‘ effect isomer ZA-dimethylpentane, treatingï the: hydro@V tratedsulfuríc acid ata .temperature in the range:l The: distillate fraction removed through the; 30. about 'Z0 to 125°: F..for a period; ofy time lessi than. pipe I6: may“ still contain a relatively larga about 3; hours,r such" that. 2;,42-dimethylpentanec amount of 2,4-dimethylpentane. and further; con undergoessubstantial conversionl into12=,3 edimethzf: version.` of this' material into the. higl‘i'er` boiling ylpentane: while 2«,2~,`3;~trim'ethylbutane». remains; 2`,'3r-dîmethy1pentane may; be“ effected by recycling substantially unchanged. removing; acidv fromatheí to. the: mixer: lì.4 Insteadi ofîrecyc'lingto thev mixer , treated’ hydrocarbon.- mixture;V and ldistillingK a. 6~itî i'sadvantageousïto pass the hydrocarbon mixe» fraction enriched ilrl 2»,2-„3"-trimethylbutane- from ture- toraseparate. stage. Thus; the hydrocarbons the treated-g hydrocarbon, mixture, the:- remaimng 2. In the manufacture of 2,2,3-trimethylbutane.. wherein». the; hydrocarbons; are; again brought into. 40, t-he steps: comprising.I forming au’ hydrocarbon contact witlrconcentrated; sulfuric: acid under` mixture.: containing. 2 ;2;3.-trimethylb11tanel and: its:l further conversion. of; the, ZA-dimethyipentane; into; 2,3;-dimethylpentane The reaction mixture is subsequently passed through a pipe, 2|v to a: settler 22 wherein the hydrocarbon' phaseI is separated from the. acid-Y phase. . . The acid phasesis‘- drawn-l o?f. through a pipe.- 23' and; may bel discharged all' or: in part from the system. Advantageously, however,> this acid is. carbon. mix-ture'.r with, sulfuric' acid. atv a: tempera.-« ture.l in the.~ range ab'out;7S0-t'o;125“ for aperio‘d: of: time. lessi than;`about 3Ã hours. such; that.' 2,45» dímethylpentane. undergoes substantial. com/.eir-4 sion'. int-o, 2,3.--dimethylpentanez while 2;2,3f.-t1:i:-- methylbutane: remains substantially unchanged.. removing acid from; the vtreated;hydrocarbon miie.v ture;_ and. distilli'ng4 ai fraction; enriched ini 2,2;35-r trimethylbutane from: the treated; hydrocarbon.Y conducted; through a pipe 241 communicating Withî mixturer the remaining ' hydrocarbons” comprising.' the.Í previously mentioned pipe.` l; wherein.y itis.Y re Zß-dimethylpentane. ' cycled~ tothe mixer Bfor the primary stage;> In 3; inthe manufacture of zgaßttnmethymutana this type of operation fresh acid may be intro 55 the steps comprising: reacting; aemethylï aluminum.y duced- tothe secondary stage> through the» pipe>~ 25 halide.: Witlr alkyl halide in. solutionV in‘: :an: a/lkane Whilevused acidi removed from- the secondary~ corresponding to. the`> alkyl radical ofi said. alkyl: stage» settler 22'A is- used-.solely or largely as, the-re.-` halide such» that.. a branched` chain hydrocarbon agent in the prima-ry~ stage mixer 6.. In» th'isëway product comprising 2,2.',3-tri`methylbutane and: aâcountercurrent treatment betweenA acid and hy-Z-Afdimethylpentane is.t obtained,y treating said-l' drocarbons> is.- utilized. v Where theV usedV acid is not so recycled; from the secondary stage or onlyy returned in‘ part,. fresh producirl with. sulfuric acid at. a temperature» the: range about 70:: to'. 1525.“ F2. for' aiperi'od’: of. time.l acidfmay be passedv directly from. a pipe 26 tothe less than about'l 3b hours; such. that Zyl-dimethylLA primary stage mixer 6. 2«,3'-dimethylpentane while 2,2,Bî-trimethy-llïJu-tan'eÄ remains substantially unchanged-f, removing' acidf . The hydrocarbon phase- isf drawn 01T. fromf the settler 22 through a pipe 21 to a neutralizer'28 wherein the: remaining acid is removed'` from the hydrocarbons.. The? neutralized hydrocarbons are thennpassedi 1 ‘ to: a. fractionator 29goperatedz irr aA similar? manner to thezfi‘actionator F55. Thev distillate fraction ri‘clr in 2;2,3‘-trimethyl;butarre is-y drawnoiî‘ througnapipe 30mg; tank' 3.15.. The liquid fraction comprising ¿lì-dimethyl; p‘entane> undergoes substantial; conversion: into-A from the treated? hydrocarbon mixture, and dis-l tillingi a. traction enriched» in 2=,2\;3f-trimetliylbul--tane> from'. theV treated` hydrocarbon mixture', the remaining- hydrocarbons; comprising. 2,3i-diimeth‘-~ yl‘pentane'; . - ' » - 41:. In; the manu-iî'acture1'y of 2,2,3 -triinet'hylbutane»; the. steps; comprising reacting a methyl atlumi--` num halide with alkyl halide in solution iwan-'aale kan'ef. corresponding. to thek alkyl-radical'. oiî said 2,404,661 5 alkyl halide at a temperature in the range about minus 58 to 32° F. such that a branched chain hydrocarbon product comprising 2,2,3-trimeth t 6 num chloride with 2-chloro-2,3-dimethylbutane in solution in 2,3-dimethylbutane at a tempera ture in the range about minus 58 to 32° F. such ylbutane and 2,4-dimethylpentane is obtained, that a. branched chain hydrocarbon product com treating said product with sulfuric acid at a tem perature in the range about 70 to 125° F. for a period of time less than about 3 hours, such that 2,4-dimethy1pentane undergoes substantial con prising 2,2,3-trimethy1butane and 2,4-dimethyl pentane is obtained, treating said product with removing acid from the treated hydrocarbon mix ture, and distilling a fraction enriched in 2,2,3 trimethylbutane from the treated hydrocarbon while 2,2,3-trimethy1butane remains substantial ly unchanged, removing acid from the treated hydrocarbon mixture, and distilling a fraction enriched in 2,2,3-trim`ethy1butane from the treat sulfuric acid at a temperature in the range about '70 to 125° F. for a period of time less than about 3 hours such that 2,4-dimethy1pentane undergoes version into 2,3-dimethylpentane While 2,2,3-tri methylbutane remains substantially unchanged, 10 substantial conversion into 2,3-dimethylpentane mixture, the remaining hydrocarbons comprising 2,3-dimethylpentane. 5. In the manufacture of 2,2,3-trimethylbu tane, the steps comprising reacting methyl alumi ed hydrocarbon mixture, the remaining hydro carbons comprising 2,3-dimethy1pentane. ROBEERT THOMAS SANDERSON.