Document Z4YZejkq7jQnQ0BG61gEBpEXO

May 9. 1933. J. N. CAROTHERS . PROCESS FOR PRODUCING DIARYL BYDK0CARB0NS 1,907,498 Plld Hoy. 11, 1930 g Sheata-Shaet 1 TOWOLDMONOQ57410 May 9. 1933. J. N. CAROTHERS ntociss ROR PRODUCING DIARYL HYDROCARBONS 1,907,498 Pllxl Hoy. 11. 1930 2 Shaoto-Shaot 2 MVENTOR J^AT. Carothera TOWOLDMONOQ57411 Patented May 9, 1933 1,907,498 :-i ;v.* l/it'.'j',-; v .j .ij 'j f>'. *it* !;j'j it--.ij ju *r..; J, .<-Ui-J m yu %* kill *> Ic\r < r:-i . \v V . ,; ^^NITED STATES r / nt * ' ik t m ..:- rii.jCTU* j. >. PATENT (OFFICE ' . '** 1 : 4 161V ft. CA&OTBXBS, 49 AWIVIOV, AL&1AXA, A88IOVO& SO fWAW MBttABCB. *" *'* <* ' ' f nrOOKPOBATZD. A OO&PO&ATZOY 07 AZASAJIA A .;jI i;: . -i . . . . s - ... ; -- u .. is ). - . . faocbas worn yaopocnro piaan, kydbocsRBpyg ... * , ,, J' " ' ' Application Had Vrember 11, WO. Mai fco. 4K65. ' ~ ^, VhR invention related to a process and to barfly account for the relatively small apparatus for theproduction pf diphenyl or yields obtained, and also accounts for the (gther diaryIs, particularly to ft' process in net that these described processes remained which the vapors ol benzol or 'other Aro- mere laboratory methods. g matic hydrocarbon are heated in a tube to In iny application, Serial Number 268,096, t>5 a temperature at which the molecular struc- filed April 7th, 1926, there is shown, de- ,ture thereof is broken down and diphenyl or scribed and claimed a prooesB for producing .other diaryl formed; and has for its Object diphenyl by passing a stream of benzol va- (provision of conditions and means *por over electrically heated screens. In io whereby formation of carbon is greatly de- carrying out the invention aforesaid, I found eo creased and larger yields of the desired that it was highly important that the ben- 'piaryl obtained. ' - . zol vapors be passed over the screens, heat- ,A further specific object of my invention ed to diphenyl forming temperatures, at a ,)j? to provide a process for the production relatively high velocity, in order to pre mia .of diphenyl by thermal synthesis, wherein vent the total decomposition of a part of the as diphenyl may De readily obtained for com- benzol into carbon and hydrogen or bitu- .merciaJ purposes. . rninous bodies. , ; Previous methods for producing diphenyl 1 While the process described in my prior tfcave been described by M. Berthelot in Ann. application has proved to be successful, I to. 142 251 ,(1867), /Schultz, Ann. 174 201 have found that satisfactory operation may 70 vil874), Berthelot, Pull. 80c. Chem. (2) 22 be obtained by the simpler process herein 137 (1874), Luddens Per. 8 870 f1875^, described. In accordance with my present jSchnndt and Schultz Ann. 203 118 (1880), invention, I pass benzol vapors through an ',Biibner-Ann. 209 839 (1881), La Coste and exteriorly heated tube and have devised v. p6,Sorger Ann, 230 1 (1685), and McKee, J. such a process and -apparatus whereby 76 ;Cheat. -Soc. j April 30, 1904, page 403. In greater yields than any heretofore reported ' Abe.methods described by these investigators Have been obtained and have overcome the -tf fies been,the practice to boil benzene un- necessity for frequent shut downs of the ap- fdjer practically atmospheric pressure. (Ber- paratus due to carbon and tar formation. aofWot, La paste) in * fiask connected with Ml carrying out my process, T have dis-.eo .the decomposition tube or to drpp the liq- covered that m order to reduce carbon for . Wd benzol directly into tbe~tiibe (Schultz: 'roation to a minimum it is necessary to nkalnalao Schmidt and Schultz) or into, a heated tAin the velocity of the gases above the critiyglass.flask. (McKee).* ^uddens and Hub- cal value in passing through the tube,`and -;4# err. recognized theoesirabilifcyof obtaining .'preferably at a uniform rate. I have fur-05 ,a uniform stream of benzol vapor and em- thermore discovered that this critical veloc- (Joyed A,stream of CO, po every the benzol ity of the gases should preferably be main- ftrapof AhfOQgb the tape. 7,./ *. * , . `. plained throughout the length of the tube, at v\ ` In mpst of^the worg described ly the here- `least throughout 'that Action of the tube (&#*.epbefqie mentioned `investigators, in ' within which the beqzdl vapors are heated o oj(Qinptihig:^hs projection -or /iiphepyl by above the diphenyl Conning temperature. ' % ^tpasring benzol vap9^s through an exterior- Obstructions in the tube'through Which the ly heated tube, considerable difficulty ^as .'gases are' Vowing art highly undesirable, .^xpeyieno^d idue to tlm. total, idocpmpasUion i nce they are responsible for the formation fcsfft'jnTa Urge part of the bepzol employed, into ; 6f local areas in which'the Velocity of the p .UaibonVnd hydiwp qr bitiiminiou- ^ -la*:-* (?fhidi tended to rtw up.Jtpe tut^a) p5S^sai^to^nSrrcJ^be^merimfeiTSitU ^ich1 the benzol vapor is admitted to the oH l/> c ON TOWOLDMONOQ57412 ,4 ,;v 1^,703,1 1,907,498 tU'I vr.v: ing on the rate of carbon formation, and obtained while employing a ye" diameter ''that When the vapor stream fluctuates in pipe and velocities above 0 ft. per seoond. velocity, as when benzol is vaporized by A marked decrease in the amount of carbon dropping it directly into a heated tube nr deposited may also be obtained by employ * into a heated .flflsk&onnpcted {herewith. or ing a strictly uniform flow of benzol vapor 70 even Jrtjplj filing it Tp^ |ask *> feck as miy db ebtaiaefl by partly throttling stantially under atmospheric ^pressure, the stream or by passing it through a suit marked fluctuations in the gas stream occur able'orifice. wtfch *ft'-flbddeive to' carbon furrasUoa, / The accompanying dfwviaga, forming * W As a practical means' of ffajxanmijr the ist- mart .of ibis application, illustrate an em- 76 ter objection, 1 have found that by introduc oodiment of my invention, in which: ing a restricted drifice, We^by 4eati6 -of a ' iFig. 1 ki diagrammatic view of an ap throttling valve in the yapor conduit, be paratus suitable for carrying out the pro tween the benzol vaporizer and the heated feeds j and - - u ftybe, ead thereby vaporizing benzol under (uFig- 2 is a graphical representation show- 80 .^OMBaewW above /atmospheric, it leg the influence of temperature and rate of as -pOmihle -to obtain a uniform .vapor veloc treatment of {he benzol vapors. ity through the heated section of the tube, .Referring to the drawings; I thaw in .(mpr means vfor obtaining uniform gas Trig. 1 a boiler 10 for Vaporizing the benzol. * Jew friU occur ip those skilled in the art. jfhB boiler js provided with an electric heat- win 'ideteifDiiung the. fffect of velocity of .ing coil 11, though any other suitable beat benzol vapors on the rate of carbon forma ing means may be employed. At 12 is an tion, I performed the /following simple ex- inlet for benzol to be vaporized and at 18 is *perianent. Benzol was volatilized by slowly a conduit through which the vaporized ben dropping it into the lower end of a vertical zol is discharged. The boiler 10 is prefer- t- heated tube, 1" in diameter, in which was ably provided with a safety valve 'if. At ripusppidod an iron spiral which could be re- 46 is shown a conduit which connects to the Xttoved and weighed before, and after each conduit 18, and through which a non-Com- . ^aperiment The difference in weight gave .bustible gas, such as carbon dioxide is passed *o the amount of carbon deposited. The ex- to purge the apparatus of air before start- tj -periment was run at 830 C. plus or minus ing the process. li#0 C. for thirty minutes with the following .The ponduit 13 is provided with a restrict jresulto; : r- -. - . ed /orifice at 17, the area of which may be " iV.'y.-iJ r :< J(i 'A ', v/n i[. H<hibceartbeodn 00*77*0' on.otr* varied by means of a valve 18. A gauge 19 .shows the pressure in the boiler 10, while a. gauge 21 shows the pressure immediately ' beyond -the valve 18. fl^rv9ii mt\ 6T - ?f 1 *i>i:h'n`rr *nr.>or4 ><at ill ophrrrvvn *>) a4ni ,qr :*) lo as i At 22 T show a furnace provided with a vl' suitable beating means, such as an electric beating element 23, and in which is disposed tf coiled tube 24, The tube 24 is connected to the conduit 13 so that Vapors from the feoiler fO pass through the tube in the fur ... _.'iA#trikjng incnaae.in the carbon foama- nace 22, in which they are raised to diphenyl tlie vfpqT yelocilyjs de- `farming temperature. Suitable tempera- -U 'from .96 to 1A3 cm. per second. (ure recording devices 26 and 27 are dis .`A? esfianM* 'Wed on the T%por ireJocHy tad posed within the furnace whereby the tewij^haraeterigties'of the apparatus in these pr- "perature of the furnace may be observed. ct .^periments indicates thta irheh (be yapor _ .At the bottom of the tube 24 is preferably *.*eloci * __from' LS3 -to--2.86 cm. per '^disposed a carbon trap 28 and connected to 't:r ./mmnd. the nature of theflowchs^iges Irom .the carbon4rap is a conduit 29 leading to a (Stream -lirMv *ptarbub#Adu, other words ^the rondenser 81 rr6tn 4rWcb the condensed va ofritieal aplo^j.'in * >pe of ^..diameter pors pass to a receive^'32. The reeefrrer 82 j**vjpg* gwal, arranged tafrao .as above provided With 4 hydrogen vent 88. `It is Preferable Ap tO 'pro^de a temperature i-820 ritKftljWeftj^t.ooWef Wjn vary WJth the dicaibr means'*34'pi'the "point of -dweharge 1--*" #1-W ponwut.ihipjgh .Whicti the, ' bf Vapors' from toU 24 into the oarbon Wf W,tration ,4p t^icondult. ' ' " ** ` small ': In #pbrtiob`, 'I vnportze pi^feraMy Ory, . yiigai/ljKTMdl ttaler, 10 nntil a pres- *** dr'betw^n fl mnd 10 ponnfls above/at- `ftosp.beric is "registered by the gaUg T9. j.Tbe itobajiitus wing purged crf aw by lpte- f. :jgge or `therethrough, the lurnace.^s `beated W)' a temperature Of from ^7* TOWOLDMONOQ57413 InotnS iameter second. 'carbon amploy1 vapor W MUiog a suitmiqg a i- w ` start- 13 ntrictley be uge IS while liately W0 C. and the valve IB k _ benxol, varies with its temperature, the passage Of vapors through the >' The drop in pressure through the ive indicated the amount of oondensate 'minute passing through the tube rather - Orifice forntod by ra iralve i thetelocfty in<** psf Seeobd. - Ail of ' a aroond < pound* to the square ini ales indicated ate tofth to be effect a to be noted by the fiance SI. The vapors then otVapta- through the tube it a velocity f___o__w__t_h_r_o_ug__h__t_h_e._tu__b_e__S,t,,b__e_in,,g h__e_a_t_e_d__t_o______ antially fa excess of the critical and ,' .diphenyl forming temperature, and profit dsuehas prevent the deposition of earbon. ' `thence through the oondenser 81 to the receiy- Tor example the vhpor velocity, with Mtc. to er 82, which is at substantially atmospheric tohdehsate per minute, at 800 C. furnace to pressure. The cross sectional area of the tube "wsnperatnrej Was found to be 82 feet per 24 is such that the vapors in passing there- seeond; it .810 C., 86 feet per second; and, -through flow at a turbulent rate, sufficiently, to'-BWVC_ '88 feet per second. ; .............................. ^ r \Tfrom fig. 8, it will be observed that, with V vapor veMStty'sufficimftly high to prevent to ______________________ ____ apparatus snob 'fine formation of earbon, the hifiher yields as I have illustrated, I have employed a pipe at a given temperature are obtained at the of %" inside diameter 86 feet long, with [ridstivriy lower velocities. This is for the , good results. In place of a throttle valve 'reason that a longer contact period is ob- to such as 18,1 have found that a fixed orifice thined and the vapors are more thoroughly to may be need equally as well, or a simple eon- heated to diphenyl forming temperatures, stnction in the conduit will also serve the `"In- this specification the term "critical re purpose. -lority", is used in its common engineering A relation exists between the maximum sense, as Indicating the velocity at which as temperature to which the tube 24 is heated stream line flow changes to turbulent flow, -to and the velocity of the vapors within the -As may be seen from toe foregoing, the rate tube so that the higher the temperature of bf flow of the vapsrs through a heated pipe, tube 24, the higher must the velocity of the in order to prevent carbon formation, should vapors be. I have operated successfully be turbulent and considerably above the so with tubes of %" diameter steel tubing critical velocity. to heated to 800 C. when the vapor velocity ' Other diaryls such as ditolyls, dixylyls or was as low as 29 feet per second and lower, 'dinaphthyls may also be made in accordance without forming a troublesome amount of with my improved process. I do not wish carbon. By operating in this manner with therefore to be limited merely to the produc ts a tube 86 feet long, one obtains approxi- tion of diphenyl. These compounds are-too mately 7.45% diphenyl in the condensate. formed by the pyrolytic decomposition of By increasing the furnace temperature to the corresponding hydrocarbon in an analo- 860 C- and employing a heated tube 100 gouS manner to the formation of diphenyl, feet long, with a vapor velocity of 91 feet I have also determined that it is desirable 40 per second through the tube, I have obtained -to employ dry hydrocarbons for this pur--too a yield of over 20% diphenyl, without any pose since the presence of moisture causes evidence of carbon in the trap 26 or in the oarbon formation during pyrolysis. - - condensate. I have found it preferable to ' ' While I have described my invention in employ e relatively long tube in order to %>ut hue farm,' it will he obvious to those s maintain a sufficiently high velocity to avoid billed in the art that it is not so limfad,"tio the formation of carbon, oouplra with a but is sosoeptible of various changes and sufficiently long period of contact f the fabdjffidatSone,' without departing from the i vapors with the heated tube to insure their..-Spirit thereof, and I desire, therefore, that thorough heating to diphenyl forming teas- fjSdy snCh'limitations shall be placed there- M peratures. In the example just' given the upon as are imposed by the prior art or asiie . - period of contact of the vapors in. the heated *ry ^Specifically set forth in the appended ;>.U -tube was U0 seconds. `The JoMer.oontadt iglfima. -ly. t 7 ii.- .L . V*' period provided by a tube 100 feet lqng a* ../What I dawn n: " ii. - .. compared with a tube 86 feet ktog also per-' 1. Inthe process of producing diaryls the 4^5 to mite the furnace, to'he epe^atedpt wrei -steps comprising vaponamgthe oorrespond-Hso ' epondingly lower temperatures for the same mg aromatic hydrocarbon, effecting an unob- b-*-. heating of the. vapors, thereby^avoiding toructed flow of the vapor at a velocity K, . - ' damage to the tube of tubed dpa fo excee- above the critical, -then heating said vapor % J'' mvely high temperatures. v & I'zjO-.'* while at said,,velocity, to. diaryl forming * ra* to ' .graphical form an intended lL4n the prooam of-(adducing diaryls the Converter Ipifelorixfe '* atepa comprising vaponcing the correspond- tong.- .Ituide.. tic hydrocarbon, effecting an sn- 1 turbulent rate of flow of the 1 l thin hating said vapor while at said"too f*r -VS.v TOWOLDMONOQ57414 * rat* of PpVitp fiml ' tefMlf Jfin^q o; ; : dTiir* :. -. * - WPPfratbrtt, i.r. `.A.Jb the PTPW Jl* mUh it*rr >'? i . '* i.flj nn^', neo.oa'*vr#m ing dry *r*c bj4row#o% m Sd`i-Jfltorfe r ) erdI r ; 9;it W> l.tv.r' . ' mj h'in d n ftl'r1 . i"''; ' ! i frtoMvilpWl nt 8* twraW mtiif f^T .1 '' 4-wtoeity they* twn Pne^oji,) <W l^.'of.*- .tt* Wv' ; i_n__*_ mi,f T^wr " ' rtp.'.'s jt.-.i. ,n.:u ti-'iM.; j,.: . i jdiiharrfri lfeotrming; _ V! <WI O) If. K'.iwt .: -Ij! ' -: ' fl* . ,4, lb the procf*s of pi., *>r/'r'q*om*:! vM.'!:.) - ^ (> the steps comprising yapori, ,........... .'.t - -.: ,. footing an unobstructed .>.# t#d ISjpor at any rate aboyaibe pritinal, then h^ytijm vit!* - ffi -IH. :* );''! i..; , ' r !. . hnid WM< repot while at, tid Yfawfv hr-nif.: f 7 | , " ' : 'l . # diphenyl fobbing temperatuff*, ,. . <;} .iMti'iqu;' y;jri ].: -r;;- ' d>. Ins patioatB of producing Vllp; * -T ; ateps comprising vaporising ibyjwm W: Tf I: dieting * uniform -turtmlepf epoMryqted I:'7f How of the sapor, then bearing said hansel fr? i/ > M Hi Vapor while *t said uniform rate t>f w>W to , diphenyl fpraing temperatures. . . The prooose ofproducing diphenylnpm- , rising vaporiung benzol under pressure, 'i-lfl* : 4- !. t ' ' >;*.! - : ;. ' ir- . > partly throttlingtbe yapor to form y etrram H* thereof et a uniform velocity ephstutiylly in excess of the critical velocity, then beating raid vapor to dipbseyl forming temperatures While nt said velocity, and. oeedonfung fbe iTtpots. /! ; ' - i.\. };> ir--"., :. y 7 &> 7. In process of producing dWhpuyl by . .pausing benSol vapors fa unn&fruqted flow through pipe heated to diphenyl forming bemperaturos, the step which consist* 14 pee- ting * turbulent rate of How of.said vapors fl* through.raid pipe. ,, i . In a process elf producing dip1 using benzol vepors in onobstrno,., through t pipe hrated to .diphenyl fermipg stdmpemtureb, the step,Which constats 40 ap- \ - .d*velerating the rate of flow of mid vapors through said pipe to e velocity substantially in excess of thenrifickl Ve)pQity., . n. ! , : 8. In proeasa of prodnwig <flphe7) by <M .`.i 1 r :r. - .: .'-a ' : * , - passing benzol irapott in *n<*otruoted flow Ol 'JOi* Mr fi . -I . * /* f-..' ' r, ,.v , ji# through a pipe betted to diphenyl WfPISg Kkv;- ai vtj .r , ,i`_ ; - ) Ihempenatutes, the.etep wbiehpoo*iU;in.ot- B }>*!<><;. , rif (*; j , ../: ; `Oeleratihg the npte of flow Ot eMd iMftWs {.(!? 'in 'lu fri.jiu.: !: 1 through raid pipeto ia,,turilapt uniform livfl ^Tltr'ff] r, j brfj'- i i1 j ! . .. rat* dubsthpMlfy..d MKM* :*f itpejcdfistl -UmI Iv- >: v. , * fT* rdodty. 1 ;; l^v i f .ft?"1!* -1' ; : Mi;/ ef. ' - --d ! f: -n:- Jj;7 0 !l : ! > , J*i Jit *!-*>. 'o! M?7` ;I ! r . ' ' , 1. t,;jH fltuih I fef Jiftj! J-/* r, 73 i*;;,':v< ' -`h ^,-fj rJ -.1 1*KJ r.;i Jv.i .ill V::)7s .'.U "l ' fc 4 i.r) ^iij aj <:T(jiUo. Ky*ii- -yri . ji t-iin - j wl o? toi--r-i tidi^niikM.ll9>hochxyiF,(>iI iin.mils ^ni 9inr.-r n* io* it -o it>qfl srb kv tu; i. Winr & jyi:bro7/! .1: rnor;r &;!' V> * ii'u< yniiui'id.wiyM .ItwJpiVdffJ Wjf'k '^V;. yv" hl. 'i,iff t i!n!v oJ `mil *jJi J to *d: j e.!: *>' X : ;||] :} I'-b^ V.;. Mf* `V.'/ u-; Ujwu*ei*flqini*3` -fcSfc ;9vtfjT l Mi;: b ~ > nl ... lo 4J6 tt;j <#ho5 It n *ti !-..\ni:i; * ** . >,.'; -fx i lo voft tflodsJOtfTb'tii ^iiuiKha &Fiirrokiwift ifti/mfvi ___ ."C,-` bttottlmi -rt^v <l< Vs ry>tvr'*f! ' l.riir-i- -&4i ^Wq[- It %i Jmioiiifi 0265313 . k *V : V' \ i /? TOWOLDMONOQ57415