April 12, 1955 JH. DUNN ETAL 2,706,172 MANUFACTURE OF BENZENE HEXACHLORIDE Filed Sept. 23, 1952United States Patent Office 2,706,172 Patented Apr. 12, 1955 1 2,106,172 MANUFACTURE OF BENZENE HEXACHLORIDE James H. Duna, Stephen N. Hall, Leo A. Miller, and ‘Clarence ML. ‘Neher, Baton Rotge, Lan” assignors Eths! Corporation, New Work, S. Yo a corporation Application September 23, 1952, Serial No, 311,034 2 Claims, (C1. 204-163) 7 ing so i ag of ee ERS he eae ee ote eats eerie Uns Ae sereette geet ee vey se eats enone ema Sipe ete baceetnar Gaahe eaten tte Be ci ieee ad She a gn et aeiaea ana cine Renata ered ss ati os pce cn se echare race Sic cin tit pr pepe fc es arte luke teenie: carter Foams eh a eee men cer tee hacia Me ey ease ie ny Steak ete emer ects fy etetng vaporization of te Bennet a SL/ove see ites uth Goat Benzene is vaporized to remove the major auantitics of disoived chlorine and hytiogen corde. "Ths vapor {ion ie pteerably ontalled to. proguse an essentially Saturated solution of benzene hexachlorce In Senzzne at the temperature of taporisation. Iti not desied (0 =. oe bn sep wl tly of ensne fo pe Epitate appreciabe quantities of BHC in ihe conten {rlted reactor solution. "The eo-conceniated Solon fs then pass ito a second vaporizer wherein the remain. {ng qanites of the benzene are vaporized "The benzene. reactor solution i= normally esientilly saturated with benzene hexachlorde under the conditions 2 fof the reaction, i. ¢» 10-25 per cent by weight BHC In benzene. This reactor solution is then passed into the vaporizer or concentrator Wherein the temperature Of the reactor solution (generally above about 100" F-) is Talsed (0 2 temperature between 170° and 225° F. (16 10)° C)), preferably between 170" and. 190" F. (76 88° C.).” These temperatives can be somewhat iower if reauess presures ate employed ‘The solution dn this ‘operation is concentrated, for sxample, from approx mately 2.15 per cent by weight BHC solution to beuween 830 fo 50 per cent by weight BHC solution, preferably "bout 40 pet cent by weight he cao sluion normallycontaips fom 0.25 to 3 per cent chlorine, less than | pec cent HCI, and about 1 jr cent of water. “These volatile impurities are removed fom the recor solution during the later vaporization ot concentration operation, and theve vapors can then, be Tecovered by, Sny suitable recovery equipment. How wo ver, a very desirable method is disclosed heretnafter for Selectively dissolving the valuable chlorine from the hy ‘drogen chloride ea. ‘the concent hencen solution is then passod into 30" sporizer operated at a temperature betwcen (60281305 and preterably between F, (U76°-188° (C) whetein the rematning ‘benzene is shed from the BH. “The solvent-free BHC. fn & molten condition at tese temperatures, then slid. fied and recovered. "The latter recovery of the BHC can sonvenienly be accomplished by use of dram Maer ot Simier appara, 'A wile varety of proces equipment can be employed fot eter the concertation operation or the Anal fash vaporization operation. For example, cther unt can be simply’ ‘conventional heat exchanger in combination ia) fooetou drm oe sitar eset” Beta ot ¢ ihly desirable process and apparatus forthe nal vap. oriret is dselosed in U, 8 Patent No, 2364406, ‘For a beter undersianding of the Operation of the invention, one modification of x suitable process flow de gram and apparatus i ilestrated in the drawings The Iain units of equipment for the benzene. vaporization operation are the concentrator 10, a concentrator knock. ur drum 20, hash vaporizer including & knockout {drum 32 and‘a drum faker or easter 40. "THE main vapor ‘covey ums ate a concentrator condenser 80, « beniene Feed’ drum 60, a vent semubber 70 and a vapors con: denser 80 ‘Atenzine-BHC reactor solution, obtained by any suite able proces, is pasted Into the Bottom of the Yonsei {or 10, hroigh the line 12 "The concentrator, 2s chown, isa tube bundle heat exchanger. "The benzeae solution flows upwardly through the plurality of tes 1a.” Seam on other heat transfer mesiim enters the jacket of the oncenttator 10 through line 16-and leaves through the line Ih. The misture of vapors and concentetcd BITC clusion is then pasted hough ine 23 Into the concen: trator knockout drum 20 where the phases re separated. ‘The concentrated BHC solution 24 then flows to he Bash vaporizer 30, through he line 34, wherein the Temata: ing benzene i fsshed, ‘This vaporizer i aso show a2 tube bundle heat exchanger In'which the BHC solution flows through a plurality of tubes (not shown). “A'heat fer medium, preferably high pressure elem, mers jacket of the fash vaporizer through the line 36 aad denves de Sire through the line 38, “Molen BHC sep Sates ftora the benzene vapors in the vaporizer knock: ‘ut drum’? and fs solidifed and faked! by the drum ‘ster 40, In the latter operation, molten BHC: in the Pan 42 freezes on the cooled roier and is faked ff therefrom by a knife or similar scraper, The vapors formed in the consentrstor 10 and sep- arated from the lguid pass ‘n the knockout dram 40 are passed to the concentrator condenser $0; through the line"$2.~ This condenser i shown in the drawing 25°3 tube bundle heat exchanger, and Is cooled by an Suit 430% cooling medium, flowidg through the lites 34 and 456. Condensed vapors, primarily benzene, are returned ‘60, through the line G2. "The uncondensed Vapors ate passed rom the concentrator ‘9 condenser $0 to the vent serubber 79, thro 30 eo “0 02,700,172 3 chlorine with fresh benzene. The fresh benzene enters the vont scrubber 70 through the line 74 from the benzene {sed drum 60.” The benzene solution containing the un teat chlorine i eared tothe benene fed drum 60 throu the ine 64, The so-crubbed gaoes, primarily drogen chords, ro ten recovered ox doped of BY a ‘ltable means The benzene vaporized in the flash vaporizer and se arated from the molten BHC in the Enackout dram {s passed into the vaporizer condenser 80 through Ii ‘The condensed benzene vapors are Teturned through ‘6640 the benzene feed drut ‘The following isa working example of a commerciat scale recovery ‘operation. A benzene eactor solution ontalaing 17 weight per cent BHIC is fed to the concen ‘ator 10 through the line 12, at a rate of 23,590 parts by Welght/hour. “The solution’ also ‘contains about 3 pet ‘cent by weight of chlorine and traces of water and Hcl St 2” Of wale pressure. This reactor solution has a tem perature of 90°F in the concentiator 10, the temperature of the solu tion is raised to 187" F," The mixture of concentrated Solution and vapor formed therein is then separated in the BHC concentrator knockout drum 20. The concentrated feed, 40 per cent by weight BHIC in benzene, is passed t0 the flash vaporizer 30 through the line 34 st the rate of 59,300 parts by welght/hour and is essentially free of chlo- fine, HICL of water. In the fash vaporizer 30. the tem perature of the solution is raised to about 360" F. At {his temperature, the benzene and molten BHC sre sep- arated in the knockout drum 32, and the BHC is recov fred as a White, laky product from the drum caster 40 at the rate of $428 patts by welgh/hour. The valuable Unreacted chlorine, about 100_parts by weight/hour, Is recovered inthe vent scrubber 70,” The vapor phase {rom fed at the rate of 2 2. the concentrator knoskout drum 20 is Z returned through the I t ‘The temperature of this condensation ig 176" F. The un condensed phase containing the chlorine se then. passed {rouge the line 72 to the vent scrbber whercit cool (Hoo F.)enzene from the Beane fot dram 0 fused fo serib the vapors. This benzene passes through the line 74.” The benzene containing the chlorine is then re: {rned to the benzene feed drum through the line 64 "As is believed apparent from the foregoing, the present invention provides an improved process for the economt- cal recovery of BHC from solutions thereof in benzene hereby a white, Maky BHC product can be obtained ‘This proces, In conzat to pion provi, petits the recovery of tnreacted gaseous chlorine from ® BHC reac {or solution, eliminates corrosive conditions during the 0 40 “5 50 4 final flash vaporization of benzene from the BHC and permits the use of low temperature steam for vaporiza- 1 of large quantities of the benzene solvent, ‘We claim: ESA process for the manufacture of crude benzene hexichloride comprising chiorinating benzene in the Bre {hee of actin ight to produce a preduct containing ben- ‘zene hexachloride, hydrogen ehlotide and unreacted chio Tine dissolved in benzene, thereafter vaporizing a frst por- lion of the benzene, the hydrogen chloride and the unre- fcted chlorine at a temperature between about 170" to 235" F, to concentrate the benzene hexachloride in ben. ene collin, heating the s-concentrated solution 10,8 ‘emperature between about 350"-370" F. to remove t remaining benzene and recover the erude benzene hex fhloride, cooling the vapors containing the first portion Of benzéne, the hydrogen chloride aad chlorine to con~ Udense and separate the benzene from the unreacted chlo. ne and hydrogen chloride, scrubbing te uncondensed Vapors with coal benzene t9 selectively dissolve the n= reacted chlorine from the chloride, and recy Gling the benzene used in the serubbing operation and tontsining the unreacted chlorine for further chlorina- "2 A process for the manufacture of crude benzene hexachiotide comprising choraaing benzene ithe prs. nce of actinic lat to preduce a product containing ben Sone fexachlorde, hydrogen chiorde and unreacted cho fine dissolved. in’ benzene, thereafter vaporizing a frst postion of the benzene, the hydrogen chloride and the Ua Feacted chlorine ats sificiently high temperature to con Centrate the benzene hexachloride in benzene. solution, heating the so-conceatrated solution toa. substantial higher temperature sufficient to remove the remaini0g benzene and recover the crude benzene hexschlorid, cooling the vapors containing the frst portion of benzene, the hydrogen ehloride and chlorine tov condense and sep farate the bonzene from the unteacted chlorine aad hydro: fen chloride, serabbing the uncondensed vapors with cool onzene to ‘selectively ‘disalve the “unreacted chlorine the benzene from the hydrogen chloride, and recy {hed in the sordbbing operation and co reacted chlorine for further chlorination. References Cited in the fle ofthis patent UNITED STATES PATENTS 2,628,260 Britton et al. Feb. 10, 1983 FOREIGN PATENTS 646917 Great Britain - — Nov. 29, 1950 6585686 Great Briain — Aue. 1, 1951