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Irfifil'icf-E Patented Nov. 15, 1949 2,488,479 er I PT, n irFiFil'iCf-E ' 2,488,479 ‘SEPARATION 9F PHENGLS ,FROIVI THIOPHENOLS Hans ‘Schindler, Pet-rolia, Pa., iassignor ‘to T'Ehe Pure iOil ‘ Company, Chieagoglll, a ‘corporation of Ohio No Drawing. Applicationseptember 2%,..1948, Serial No. 51,123 19 Claims. (01. 260-609) "1 2 This invention relates to a method of separat ring sulfur, wherein: the oxygen and‘sulfur are ‘at ' ing phenols from thiophenols and, in particular, it ‘:tached rclirectly 1‘ to: the nucleus. relates to an adsorption process of separating “In accordance :with- my invention, EI prefer to phenols from thiophenols whichhave' closely re ‘filter the'mixture of a “phenol and thiophenol lated ‘structures. 5 :through aibed of-silicagel until analysis: of the This application is a-continuation-in-ipart of e?luent‘liquid or '?ltratesshows that phenol‘ isl-no my'application Serial Number 547,989, now aban longer being iadsorbed zaon‘the-silica gel as indi doned, filed August “3, 1944. vcated lby-lthe ‘fact that'the- effluent has substan Phenols recovered ‘from 'coaltars ‘and petro tially thesamercomposition as thezcharge. The leum oils are frequently admixed with thiophe 10 asijlicargel-bed isitheniwashed with "a suitable-‘sol nols which occur naturally in the same media and vent, preferably 'a1.low'-'boiling hydrocarbon sol because of the chemical similarity .of the two =.vent, such as hexane?benzene or hydrocarbons types of compounds, separation is very dimcult fbo'iling :in the-gasoline range, ‘capable-of ‘remov when purely chemical means are used. This in 1mg unadsorbed :materiali held ‘in “the :?lter vbed, particular is "true when phenols are extracted 15111115 incapable of rextractingthe adsorbed con virom , their.naturallmedialbylmeans of caustical :istituents :from :the :silica gel; Following ithis vkali solution. A common source of mixtures of washing, the adsorbed phenols a-raextracted from phenols and thiophenols is the alkaline prewash the silica gel by means ofasuitable solvent, pref used in re?ning cracked gasolines. Quitegener erably a low-boiling 'ketone, such as acetone, sally ‘in such operations, ;an ;acid oil fraction is 20 butanone, or pentanone. Any hydrocarbon sol ‘sprung .from the :alkaline > was-h solution, which vent boiling up to approximately 200°,C.,is suita jfraction-hassa boiling :range ::from about 359° to ble-Ior the‘preliminary washing of the silica gel about 450311, land-1a desirable cresol content. ‘and any "aliphatic sketone 'boiling "up ‘to - approxi However, the economic’ valuev of the ‘ material --is mately 200°C. is suitable for the extraction of the seriouslyrreducedbecause it contains thiophenols 25 phenols from the silica gel. ‘ Zin ‘substantial :amounts. To apply the process to a speci?c-mixture-of Accordingly,__itnis :a ‘fundamental 1 object of ‘ the >_ phenols anclthiophenols, consideration should'be :instant invention toprovide .armethod which can given to the possibility that the phenol to be re ‘serve as abasisforla-processcfor separating;phe covered may be substituted'to such an-extent that nols. from thiophenols and serve totconcentrate a 30;it .will not be adsorbed preferentially. I have :mixture :of :the compounds ;into fractions rela .zfound that if .thesphenol to berecovered'from ad tively :richer ‘:in phenol and thiophenol, respect ;mixture with1anthiophenol is soluble in sodium ively. lhydroxidezsolution .of :a concentration about :10 ;It is :asecond :object of ,the:invention to pro per . cent‘ :.by ‘weight, it will “be preferentially ad ~_vide an adsorption'process-jfor the separation of .vsorbed from admixture with very closely related aphenols ‘from ;thiopheno1s. athiophenols. :fIlhezsolubilitynof ‘the phenol in any alt isianother-gobject of vtheinvention to provide zalk'altmetal hydroxidesolutioncan be used, for \a-cmethod of'recovering a useful;phenol fraction iexamplejsodium, ipotassium, lithium, rubidium, :Irom .acid zoiil. , ' ,iforitiistheccapacity of the phenol-t0 form phe Ii'have discovereclsthatrelatively pure phenols ‘19 enolatewhichgis beingrrtested, :becauselit is those can be separated from :mixtures :of-pheno-ls :and :y‘vhich xform 531K811 zphenolates which are readily "thiophen'ols ;by;contactir.g ;the jnixtures with adsorbed. In general, .imsu-bstitutedphenols v‘will zsilica ‘gel aatordinarytemperatures. Mixtures "-of be adsorbed from admixture with unsubstituted phenol and thiop'henol- :which :are zrathericlosely thiophenols; 'likewisa'sub'stituted phenols will be related in‘structurebyyirtue ofrhavingesubstam adsorbedzfrom admixture with substitute'rlthio "tially similar 'substituents > onithe» respective ben -,phenols. 2 It iswhen atsubstituted phenol is to be recovered from admixture with unsubstituted ‘ ' zene rings are readily-separated,'=for the'phenols thiophenol that the degree of substitution of the are preferentially“adsorbed onisilica gel'andloan phenol or ‘the degree of di?erence'between‘the ‘be extracted therefrom‘by using, a-suitable solvent . ,structuresof the compounds should be consid ‘from which ‘theycan‘ibe recovered. "'Thel- process ered. If the phenol is soluble in sodium hydrox~ is applicable generally 'to mixtures ‘toil-aromatic ide ‘solution .of about “10 percent concentration, compounds-of carbon,fhydrogennoxygenwand sul itwill be‘preferentially adsorbed by silica‘gel. vfur, the onrelgroup-offcompounds:containing oxy~ 'As an "example 'of the above procedure, ‘the ‘gen and thelother group invthe mixture :contain- ’ 55 eseparationrof thiop'hen'o'l vfrom 2,4,‘G-tertiarybutyl 2,488,479 3 4 phenol might be attempted. Because the hy cent by weight of cresols and 2.4 per cent by droxyl group on the 2,4,6-tertiary butyl phenol is weight of thiocresols. Measured in terms of so hindered by alkyl groups, the thiophenol would barrels of cresols per ton of silica gel, the yield be preferentially adsorbed. The 2,4,6-tertiary was 1.6 barrels per ton. The cresols obtained butyl phenol has no signi?cant solubility in 10 were slightly better in quality than commercial per cent sodium hydroxide solution. However, cresols marketed by a well-known company. 2,4-tertiary butyl phenol can be preferentially ad Commercial cresols, with which a sample pre- sorbed from a mixture thereof with thiophenol pared in accordance with my invention was com and it is found to be readily soluble in 10 per pared, contained 2.6 per cent of thiocresols. cent sodium hydroxide solution. 10 The cresols from the ?rst extraction were Thus, the application of the process to the again percolated through the silica gel and four recovery of phenols from thiophenols as they cuts of ?ltrate were taken and analyzed for occur in admixture, is well exempli?ed in the thiocresols. The data on these four cuts are rendering of acid oils. These oils as they are given in Table III: sprung from spent caustic, may contain very low TABLE III boiling aliphatic acids, but will include phenolic and thiophenolic compounds of closely related Per Cent by Per Cent by Per Cent by structures in the fraction boiling from about 300° Cut No. W gt. of Wgt. of W gt. of to 450° F. The phenolic bodies are easily recov Charge Thiocresol Crcsol ered by successive adsorptive fractionations car 20 ried out with silica gel in accordance with the instant invention as illustrated by the following asap-q examples in which the separation of mixtures Hwww I-‘CRHD-l caDcow otocozo FIST‘? representing typical acid oil cuts is illustrated. In order to demonstrate the invention, 125 The silica gel was then washed with 200 milli grams of silica gel having a mesh size of approxi liters of hexane to wash it free of unadsorbed mately 8 to 14 was packed in a glass tube. The material and thereafter washed with 150 milli silica gel occupied a volume of 200 milliliters. liters ci acetone to extract the adsorbed ma Two hundred (200) grams of a mixture, con terial. The data on the extracts obtained are taining 25 per cent by weight of meta-thlocresols 30 given in Table IV: and 75 per cent by weight of mixed meta- and TABLE IV para-cresols was percolated by gravity at room temperature through the bed of silica gel at the rate of 1.3 barrels per ton per hour. The ?ltrate i91 o vent P $36113.“'_ 1 Pcrvcentfbygt. 0 Pervcentfbygt. 0 was divided into seven separate equal cuts and solvggtugtree Thiocrcsol Cresol each was analyzed for thiocresols. The data are given in the following table: Hexane ____ __ 41.0 2.3 97.7 TABLE I Acetone...“ 11.0 1.4 98.6 Per Cent by Per Cent by Per Cent by It will be seen from the table that 11 per cent Cut No. Wgt. of Wgt. of Wgt. of of the initial charge of 35 grams containing 97.6 Charge Thiocresol Cresols per cent of cresols and 2.4 per cent by weight of thiocresols was obtained as cresols having a 5. 2 5B. 1 41. 9 5. 2 32. 5 67.5 purity of 98.6 per cent by weight. 5. 2 27.0 73.0 It will be apparent that larger yields of cre 5. 2 25. 6 74. 4 7. 7 25. 9 71. 1 sols may be obtained by recontacting any or all l2. 9 25. 8 74. 2 of the ?ltrate cuts with silica gel. For example, 7. 7 24. 6 75. 4 the process can be carried out in series with the ?ltrate from one ?lter bed passing through After 98.4 grams of the mixture had drained 50 successive ?lter beds followed by separate ex from the silica gel bed, hexane was admitted in traction of each bed with hydrocarbon solvent order to remove all non-adsorbed material. The and ketone. In this manner it is possible to amount of hexane used in the washing step was obtain a series of fractions of cresols of gradu approximately 200 milliliters. After the unad .. ally decreasing purity from each bed and these sorbed material was removed from the silica gel fractions can be again treated in a series of con by hexane washing, the silica gel was washed tact steps with silica gel to increase the purity with approximately 150 milliliters of acetone to thereof.
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