Patented Dec. 24, 1946 2,413,255 . ' > , UNITED ‘STATE s“ PATENT OFFICE 2,413,255 - . . - PROCESS FOR REFINING STYRENE AND METHYL STYRENE , ' Frank J. Soday, Baton Ronge,;La., assignor to The United Gas Improvement Company, a cor poration of Pennsylvania ‘ - No Drawing. Application May 1"],v 1943, Serial No. 487,345 7 Claims. . 1 (01. 260-669) ‘ 2 alkaline earth metals. _ . . Examples of such metals are lithium, sodium, potassium, rubidium, caesium, barium, strontium removal of impurities from styrene and substi- _‘ tuted styrene by the application thereto of one or and calcium. Due to the availability and low cost ' of sodium and potassium, however, these metals more metals of group Ia andv group 11a of the pe riodic table, as well as certain active alloys there- ‘ are preferred for the use set forth herein. . , Alloys of these metals, such as'NaPbio, NaHg‘r, . NaCa5, NaZnm, KNa and the like,- also may be ‘ An object'of the present invention is the re I moval of certain impurities from styrene and sub stituted styrene by treatment with one or more! ?nely divided'alkali or alkaline earth metals, or and y \ ‘ More particularly, this invention pertains to the of. , obtained by the use of ?nely divided alkali This invention relates to the re?ning of styrene type compounds. i w employed for the removal of undesired impurities from styrene and substituted styrene. In general, 10 the alloys of the respective metals react with the impurities present in styrene and substituted styrene fractions at a slower rate than-the corre active alloys thereof. Another object of the in vention is the provision of certain methods where- ' sponding metals. by styrene and substituted styrene and particu larly light oil styrene and substituted styrene ' In general, therefore, it may be said that very‘ ?nely divided metals in groups Ia and 11a of the, ' periodic system, and their\ reactive alloys, may be fractions, maybe puri?ed in a continuous manner by the application of alkali or alkaline earth met als without undue loss of unsaturated hydrocar bons in the ‘form of soluble or insoluble polymers. Other objects and. advantages of the‘ invention will be apparent to those skilled in the art upon an, inspection of the following description and used to re?ne styrene and substituted styrene. The styrene and substituted styrene which may be re?ned by this method may-be obtained from any desired ‘source such as synthetically, for ‘example by the removal of the elements-of chlo rine or. hydrogen chloride from chlorinated ethyl . benzene or'substituted ethyl b'en'zenesfby the . Styrene and substituted styrene fractions, par 25 partialv hydrogenation of certain phenyl or sub ticularly light oil fractions, frequently contain ' s‘tituted-phenyl acetylenes; by the dehydrogena substantial quantities of impurities, such as acet ‘tion of ethyl benzene or substituted ethyl ben claims. ylenic hydrocarbons and compounds; ' oxygenated ' zenes; by the dehydration of’ phenyl ethyl alcohol compounds such as aldehydes and peroxides; sul 30 or methyl phenyl carbinol, or substituents there fur compounds; and other impurities, which in of ;- and by the pyrolysis of petroleum or petro terfere with the use of suchmaterials in most, if , leum hydrocarbons in‘the gaseous phase at tem .peratures above 1000° F., and more particularly not all, industrial applications. Thus, for example, a 60% light oil styrene frac above 1300° F., followed by condensation and ‘ tion obtained by the pyrolysis of petroleum in the 35 fractionation; and by the pyrolysis of other car gas phase at temperatures substantially above procedures also may _ bonaceous materials. Other ’ 1300° F., followed by'condensation and fractiona be employed for the production of styrene or sub tion', was found to contain,0.2% phenyl acetylene, stituted styrene which may be ‘ re?ned by the 0.1% sulfur, and 0.02% aldehydes, as well as cer methods to be more particularly described herein. tain other oxygenated impurities. This ‘styrene 40 The styrene fractions which may be re?ned by , styrene obtained therefrom‘ by the use of suitable concentrating methods‘, such as a 98% styrene my process may have any ‘desired, boiling point, although I generally prefer to employ fractions ‘ boiling mainly in the range of 125 to 160° 0., and concentrate, is unsuited for the production of more particularly from 140 to 150° C. 1 Excellent - resins of good quality due to the inhibiting action, results are obtained by the ‘use of styrene frac tlons boiling mainly in the range of l43eto148° C. fraction, as well as the more highly concentrated ~ and other undesirable properties, of the impuri ties contained therein. As a result of extensive experimentation, I have discovered that styrene and substituted styrene, particularly light oil styrene and substituted The substituted styrenes which may be re?ned by my process may be‘ represented by the follow " ing formula 50 styrene fractions, may be re?ned by the applica tion in ?nely divided form'ofat least'one metal - of group In and group 11a of the periodic table, as well as certain active alloys thereof, in a continu- ous operation. Particularly desirable results are (d) 1| 3 in which at least one of the group a, ‘b, and d is an alkyl group, such as methyl, ethyl, propyl, butyl, or amyl, the remaining groups being‘hy drogen, and n denotes that from up to five of such substituents may be present on the benzene ring. , adherence to certain operating conditions such ‘as temperature, reaction time, concentration, and so forth, which will be discussed in consider able detail. V In addition, the use of polymerization in Examples of such substituted styrenes are the _ -, hibitors, as well as the method employed for con methyl styrenes, and particularly the nuclear~ ductingthe re?ningoperations, also has a very substituted ‘methyl styrenes. _ considerable in?uence upon the results‘obtained. Of particular interest is the mixture. of nu ' While the re?ning operations maybe carried clear-substituted methyl styrenes obtained 10 .out in the absence of any added polymerization among other ways, by the pyrolysis of petroleum ' inhibitors, I prefer to employ‘ one or more poly at temperatures above 1300“ F. These fractions merization inhibitors in order to reduce the loss may have any desired boiling range, although I of styrene-type compound in the form of poly generally prefer to ' employ fractions boiling mers, as well as to broaden the permissible limits mainly in the range of 160 to 180°_ 0., and more. of certain of the reaction variables. .particularly in the range of 165 to 175° C. Ex; 1,5, Inhibitors which are particularly effective cellent results are obtained by the use of frac-v agents for retarding the rate of polymerization of tions boiling mainly in the range of 167 to 173° C. ‘.- stynene-typ'e compounds ' when re?ned with A preferred embodiment ‘of this invention is ‘ ‘very ?nely divided metals in groups Ia and 11a the continuous re?ning of a mixture, of styrene 20 of the periodic system, their reactive alloys. and and methyl styrene, such as a light oil fraction reactive derivatives, may be classi?ed in the fol boiling mainly in the range of 125.to 180° 0., lowing groups. 1 I followed by the separation of the styrene and l. Amines and nitrogen-containing inhibitors, methyl styrene, if desired, and/or the concen particularly aryl amines such as: tration of the styrene and/or methyl styrene. 25 Alpha-naphthylamine, For convenience in the speci?cation and claims, Thiodlaryl amines, the term “styrene-type compound" will be used p-Phenylene diamine, to denote styrene, substituted styrene, and mix o-Phenylene diamine, .2,4-diamino diphenylamine tures thereof. 1 The. fractions containing styrene-type com-' 30 Phenyl hydrazine, ' I pounds also may be initially concentrated to any Benzamide, V desired extent prior to re?ning, and such con Cyclohexyl naphth’yl amine, and centration ,may be carried out by any desired Polybutyl amines. method.- This ay include concentration by fractionation, azeotropic distillation, solvent ex I'articularly desirable results may be obtained traction, a combination of solvent extraction and by the use of secondary aryl amines having the fractionation methods, and the formation-of ' complexes between the diole?ne and some active ' following general formula ' compound, followed by the removal of the un reactedportion of the fraction and the decom- ' 40 position of the complex. Other concentrating ' methods also may be amp loyed if desired. In addition, other re?ning methods also may in which R1 is a substituted or an unsubstituted aryl such as phenyl or naphthyl, aralkyl such as tolyl or methyl phenyl, cyclopara?lnic such as be applied to styrene-type compounds and frac- ' cyclobutyl, cyclopentyl, or cyclohexyl, cyclo ‘tions thereof to remove at least a portion of one‘ 45 ole?nic such as cyclobutenyl, cyclopentyl, or cy or more impurities present prior to re?ning by methods to be more particularly described here in. Thus, such fractions may be contacted with acids or acidic solutions or materials to remove clohexenyl, .hydroaromatic such as ,dihydro phenyl, or tetrahydrophenyl, or naphthenic such as methyl cyclohexyl, ring or group, and in which materials present. aralkyl, cyclopara?lnlc, cycloole?nic, hydroarop R is a substituted or an unsubstituted alkyLesuch a portionv of certain impurities or undesirable ' 50 as, ‘methyl, ethyl, propyl, butyl or amyl, aryl, ' Such concentrating and/or partial re?ning operations also may be applied to styrene-type ~ ‘compounds subsequent to the re?ning operations matic, or naphthenic ring or group such as given in the case of R1. Included ‘are secondary amines such as for examples ' to be more particularly described herein. . v I ?nd that a solution of sodium, or a suspension or emulsion of "very ?nely divided. sodium, or a solution,‘ suspension, or emulsion of one or more ?nely divided sodium alloys, is a particularly desirable agent for the continuous removal of certain undesirable impurities from styrene type 'compounda- Excellent results are obtained by the use ,of a suspension of very finely divided sodium. ' _ - \ in which R and R1 have the same meaning as be fore. . . Secondary amines containing'one or more aryl - The alkali metals, particularly sodium and 65 or substituted aryl groups are preferred, such as: ' potassium, are very active catalysts for the poly 1 Diphenyl-p-phenylene diamine, merization of styrene-type compounds. Con sequently, the use‘ of such an active catalyst, particularly in ?nely_-divided (and hence most . active) v~forin, for the re?ning of styrene-type compounds would be expected to result in the ‘ converslonof the greater portion, if not all, of such compounds present to polymers. _ - It s ould be emphasized that the success of the re Phenyl-beta-naphthylamine, Isopropoxydiphenyl amine, Aldoll-alpha-naphthyl' amine (and polymers thereof), _ . , Symmetrical di beta naphthyl-p-phenylenedh amine, . Trimethyl‘ ~dihydroquinol1ne (and polymers thereof), and Hg operations'is dependent upon rigid 75~- Ditolylamines, and mixtures thereof. , ' ‘ . acraaes ' a metal of group Ia or group IIa, or an active 2. Phenolic compounds, such as: alloy of such metals, in ?nely divided or solution I p-Tertiary butyl ca'techol, , ' Dihydroxybenzenes (and substitution prod ucts thereof) , Pyrogallol . \ (and , ' of one or more polymerization inhibitors. By the products 5 use of a continuous system, particularly in con junction with the use of an inhibitor, the lossJof substitution thereof), _ form ina continuous system and in the presence ' styrene-type compound due to side reactions ‘or > < Pyrocatechol, to ‘polymerization is very markedly reduced, or Resorcinol, almost completely eliminated. Xylenols, ~ - As pointed out previously, this is of particula Catechol, Y Trihydroxybenzene thereof), Nitrosophenol, (and importance in the case of styrene-type compounds which are quite susceptible to polymerization when placed in contact with certain active metals, as well as active alloys thereof. Thus, sodium 15 isv a very active catalyst for the polymerization of substituents " ‘ ' Diaminophenoi, Alpha-naphthol, , Dihydroxynaphthalene, Hydroxy quinollne,_ ‘ styrene-type compounds,~ and has been suggested as a catalyst for the conversion of styrene to resinous polymers in numerous references. The use of this material in very ?nely divided form in 20 a continuous system for the re?ning of styrene ' Hydroxy tetrahydroquinoline, Polyhydric phenols, Polyhydroxy'phenanthrene, and typ'e compounds, therefore, ‘must be carried out within well defined limits in order to prevent 4-nitroso-2-methyl phenol. 3. Compound inhibitors, such as: Acyl-substituted amino phenols, - undue loss of styrene-type coinpounds due to polymerization. or other active metals, or alloys, must be attrib uted largely to the continuoous nature of opera tion, resulting in‘ a minimum contact time be tween the styrene-type compound and the re actant. Although the process may-be carried out in any o-Amino phenol, and 5-amino-2-hydroxytoluene. 4. Miscellaneous inhibitors, such as: Hydroquinone, > The success of the preferred re?ning method employing ?nely divided sodium, 25 4-cyclohexyl amino phenol, p-Amino phenol, Quinol, . 5 ‘ » desired manner, I prefer to conduct it in a ver tical vessel or tower in which a certain height V Nitroso naphthols, of a liquid suspension or solution of the active Quinhydrone, ' Reaction product of an aldehyde and an 35 re?ning agent is maintained.‘ The material to be re?ned then is passed upward in the vapor and/ or ‘amine, liquid phase‘ through this column of reagent at 1 p-Amino acetophenone, Dihydroxy anthraquinone, andv a ratesu?icient to insure the remova1 of the de— sired quantity and type of impurities present at Reaction product of a ketone' with an amine. the temperature employed. The re?ned mate- 1 _ rial preferably is taken off at the top in. the vapor I phase, temperature and pressure conditions being Excellent results maybe obtained when one or more inhibitors selected from a list comprising . adjusted for this purpose. ‘ Other methods of contacting the material to be (1) secondary aryl amines such as phenyl beta- - naphthylamine, diphenyl-p-phenylene diamine, 45 treated and the re?ning agent also may be em} isopropoxydiphenyl amine, aldol-alpha-naphthyl amine (and polymers. thereof)‘, symm. di-beta- ployed if desired. Thus, the unsaturated 'hydro- _ carbon may be passed through a horizontal treat naphthyl-p-phenylene diamine, trimethyl dihy in: unit, such as a pipe or bank of pipes, partially or completely ?lled with a suspension of the de-_ droquinoline (and polymers thereof), and the di tolylamines; (2) phenolic compounds, such as p 50 sired re?ning agent, or otherwise. . - _ Phenols; and (3) reaction produ'cts‘of a ketone, The suspending liquid employed for the re ?ning agent may be'of any desired‘type. Pref- ' such as acetone, 'and/ or an aldehyde,suchasform erabLv, it does not react with the reagent or the ' .7 tertiary butyl catechol and alkylated polyhydroxy material to be treated to any substantial extent,‘ aldehyde and acetaldehyde, with an amine, such as aniline, are employed in the re?ning process 55 and preferably it does- not introduce ‘any addi described. . .tional impurities into the material to be treated. _ I ?nd that hydrocarbons and hydrocarbon frac- > In general, I prefer to employ less than 10% , by weight, of polymerization inhibitor, based on the tions are particularly desirable materials for use. as suspending mediums for re?ning agents of treating system at any one time in the continuous co the type described herein. Excellent 'resultshaye been obtained by the use of aromatic hydrocar treating system. Good results also have been ob bons and aromatic hydrocarbon fractions for this tained by the use of less than 5% inhibitor, and maximum total volume of suspending liquid in the purpose, particularlythose having initial boiling~ . even less than 2% inhibitor, in certain cases, par~ ticularly when one or more of the inhibitors listed in the preceding paragraph are employed. points above 180° Q.‘ and more preferably above _ I 65 200° C.‘ . . ' As pointed out previously, the ‘refining opera tions are carried out in a continuous or semi continuous system in order to reduce the propor tion of styrene-type compound lost in the form of polymers, as well as to secure greater economy in 70 pending medium actually employed in the opera tion of the process usually 'comprises a mixture of / the use of the reagent. the material to be treated and~the suspending ' ‘ ' The re?ning method disclosed herein di?ers fundamentally from all methods described here ‘It is to be-understood, of course, that the ma terial to be treated may dissolve to ‘some extent in the suspending medium,/c0nsequent1y the sus medium initially introduced into the system. _ The material being treatedalso may serve as ‘ tofore for the re?ning of styrene-type compounds a suspending ‘medium for the re?ning agent with in that the material in question is treated with a 75 out the addition of any other material, if desired. r 2,413,255 Thus, a light oil styrene fraction may be intro include extrusion through ?ne ori?ces, and the. generation of an arcbetween sodium electrodes duced into the desired tower or vessel, together in an inert liquid. ‘ with the ?nely divided re?ning agent, after which the styrene fraction is passed into the suspension Although almost any desired concentration of 4 of the re?ning agent in the said styrene fraction 5 treating agent in the suspending medium may, at the desired temperature, the charging rate be employed. depending upon the type and con and more particularly the operating pressure be centration of the styrene-type compound, or ing adjusted to maintain the treating agent at the desired level in the vessel. ' fraction thereof, to be re?ned, the temperature, tion of the material to be treated which has been dissolved in the suspending mediumor which has less than 30%, and more particularly less than 20%, by weight of the treating agent. Excellent been employed as the suspending medium in‘ the - results are obtained when less than 15% by weight of the treating agent is suspended in the the depth of reagent employed, and the like, 'I It is to be understood. of course, that the por 10 generally prefer to employ a reagent containing substantial absence of other liquid materials, does not necessarily remain in the treating zone throughout the entire treating cycle. Rather, suspending medium. this material is in a state of dynamic equilibrium It is to be understood, of course, that the term vsuspending medium refers to the actual sus vwith the material being treated, a portion of .it pending agent employed during the treating op volatilizing continuously and being removed from the system, the material volatilized in this man ner being replaced by the solution of a corre eration, and . includes any of ,material being‘ 20 treated which may dissolve in such agent. The concentration of the styrene-type‘ com sponding quantity of freshly added material to be treated. The major portion of the material - pound to~~be treated also has a considerable in ?uence upon the method of operating the proc ess. Thus, with a highly concentrated styrene type compound, such as 98% styrene, the reagent should preferably contain a fairly low concentra tion of active agent to minimize losses due to to be treated, of course, passes upward through the suspending medium without dissolving therein. I ~ The thickness of the layer of reagent through which the material to be treated is preferably polymerization. ‘ . I generally preferato'employ a fraction of such ' passed depends upon a number of factors, such concentration, and with such proportion of sus as the quantity and type of impurities present, pending r'nediumythat the actual concentration the extent to which such'impurities 'are to be removed, the type and degree of dispersion of ‘ of styrene-type compound in the reaction zone is less than 80%, and more preferably, less than the treating agent employed, the reaction tem - 70%] Excellent results are obtained when the perature, the concentration of the treating agent in the suspending medium, and the like. In gen 35 actual concentration of styrene-type compound in the reaction zone is lessthan 65%. eral, however, I prefer to employ a layer of re The concentration of styrene-type compound agent at ‘least one foot thick and, more prefer also may be reduced by the addition thereto of ably, at least two feet thick. Excellent results a suitable solvent, such as a hydrocarbon ‘or hy .40 drocarbon fraction, prior to introduction into the - are obtained by the use of a layer of reagent at a least four feet thick. , It will be recognized that, .other things being equal, the depth of reagent employed in the treating vessel controls the contact time be tween the material to be re?ned and the re?ning reagent. . re?ning The degree of dispersion of the treating agent ,also has a very profound effect upon the degree of re?ning obtained. In the case of sodium, I prefer to employ a subdivided mass in which at 7 _ L pressure, such as atmospheric, subatmospheric, and superatmospheric pressures. 45 _ system. The processamay be carried out at any desired , ‘ ' In. many cases, particularly when a styrene type compound in a'fairly highly concentrated form is refined with a suspension or solution of a finely divided active metal, or alloy, of the type ' _ described herein in a higher-boiling solvent, it least the majority of the particles present have 50 'isihighly advantageous to conduct such opera tions at subatmospheric pressures, thereby reduc a diameter of not more than 0.05" and, more ing the concentration of styrene-type compound ‘ present in the re?ning system at a given reac tion temperature. This serves to reduce the - 55 quantity of styrene-type compound converted to than 0.02". . I polymers in the process, consequently it is a pre~ This subdivision may be carried out in any de ferred embodiment of this invention. _ sired manner. Thus, in the case of sodium, a ' The temperature at which the process is con solution of this material in; liquid amomnia may ducted also has a very considerable bearing upon be introduced into an inert liquid, such as xylene, at room temperature or at elevated temperatures. 60 vthe degree to which the styrene-type compound preferably, not more than 0.03". Excellent re sults are obtained when at least the majority of the particles present have a diameter of not more The almost instantaneous volatilization of the ammonia present results in the dispersion of the sodium present in the xylene in an extremely finely divided state. Another‘method comprises is refined and the lossesincured due to polymer ization. Although the optimum reaction tern-r perature vto - be employed is dependent largely upon other factors, such as theconcentration of _ spraying molten sodium into an inert liquid such 65 both'thé styrene-type. compound and the re?n as'xylene or solvent naphtha. By suitable vari- . _ing agent in the reaction zone, I generally prefer . ations in the type and degree of ?neness and/or to conduct the re?ning operations at tempera dispersing ability of the spray nozzle employed, sodium of almost any desired degree of ?neness may be obtained at will. ‘ , Another satisfactory’method comprises melt ‘ - ing the sodium under the surface of a suitable liquid, such as xylene, followed by violent agita tion, such as with a turbo-mixer, and cooling with tures below 100°C. and more particularlykbelow - 85° C. Excellent results are obtained by conduct 70 ing the re?ning operations at temperatures below‘ '75? C. ' ' The rate at which the material to be re?ned is passed through the reagent has a very consid-' erable effect upon the degree to which the im agitation. Other methods which may be used 75puritiesl present are removed, although this is 2,418,255 .9. i0 . ‘dependent to some extent upon other variables such as the concentration of re?ning agent in‘ ' the suspending medium and .the'temperature at Y which the re?ning operations are being con you?’ - in the gaseous ‘state upward-through the column ' was found to maintain the'system in the desired _' degree of agitation. ‘ - The re?ning agent. particularly‘ when ?nely ducted. While it is di?icult to establish exact 5 divided sodium is employed for this purpose. limits for optimum throughputs under all condi- > usually actsboth as a reactant and as a poly tions, 1 generally prefer not to exceed a through- merizing'l agent for the" removal of undesired im put of material to bevtreated on an ‘hourly basis purities. Thus, in the ‘case of light ‘oil styrene of more than four times the weight of suspend- 1 fractions containing acetylenes, aldehydes, and lag medium employed and more preferably not 10 other impurities, the sodium usually will react . more than twice the weight of the, suspending with at least a portion of the acetylenes present medium. Excellent results are obtained when to form the corresponding sodium'acetyildes, and not more than equal quantities of material to be .may react with certain of the oxygenated deriva Vtreated. upon an hourly-basis. are passed through tlves to form corresponding metallic derivatives. _ the suspending medium. _ 15 At least a portion of the acetylenic hydrocarbons ' _ It will be recognized that the contact time 116present also are polymerized to form polymers, ' tween the material to be treated and the reagent 1 I or copolynrers with other unsaturated hydro is determined both by the thickness of the layer carbons present, which frequently are insoluble of reagent employed and by the rate at which in nature. Certain of the omgenated derivatives, the material to be treated is passed through the 20 such as aldehydes, also may be polymerized to reagent. ' , form polymers which may be insoluble in type.’ ' The method employed for introducingthe material to be re?ned into the re?ning agent also has some in?uence upon the extent to which the styrene-type compound is re?ned. _ As a result, the re?ning or styrene-type com - pounds witha suspension of ?nely divided sodium is characterized by the gradual accumulation In general, 25 of insoluble polymers in the re?ning medium. .it may be said that a ?ne stream or jet of the liquid or gaseous material to be re?ned is do- This may be removed in any desired manner, such as by ?ltration, which may be carried out ‘ continuously during the. re?ning - operation, or siredv This may be accomplished by introducing the material to be treated into. the reagent by may be carried out in a batchwise manner after means of suitable ori?ces, jets, nozzles, or other 30' the termination of the re?ning step, _ , subdividing means. Porous objects or materials As the removal of the insoluble polymers also also may be employed for this Purpose, Such as is attended by some loss of re?ning agent, even ' porous ceramic or glass diffusing blooksor units when the latter is in a/ very ?ne‘ state of sub; , As the re?ning agent may show some tendency division, it isadvisable in many cases to continue to settle out in the bottom of the treating vessel 35 the re?nmg operations 'until the re?ning agent or unit, the jets or nozzles by means of which has been largely or completely exhausted before the material to 'be treated is introduced into the » unit may be so arranged as to prevent any undue , ?ltering. ’ ' . ' . - The solidor semi-solid ?ltered products may settling of this material, In vertical vessels, this be treated to recover any desired materials or , may 'be accomplished bylocating these units in 40 they may be disposed of in any suitable manner. such away as to impinge the inlet stream or Thus, any unchanged re?ning agent,‘ such ‘as streams upon the bottom of the treating vessel. sodium, may be recovered by melting and coalesc The inlet jets also may be, aranged tangentially ing operations, or by amalgamation with mercury, to impart a swirling or circular motion to the treating reagent, if desired. or otherwise. - Certain of vthe reaction products, Another method _ 45 such as sodium acetylide‘s, may be decomposed ' comprises locating the inlet jet or jets directly with water to regenerate the corresponding in the bottom of the reactor, or tangentially in the sides of the reactor, or both, to prevent any acetylenes or they ‘may be reacted with carbon ' ' dioxide to form unsaturated acids, or otherwise. ‘ settling in the .bottom of the reacting vessel A convenient method for the disposal of the ‘and/or to impart any desired circular or other 50 insoluble polymers ' comprises treatment with .‘ ' motion to the treating medium. carbon dioxide, suitably in the presence of traces Any desired combination of these methods also of moisture, iollowed by ?ltration. may be employed, such as the use of a jet or jets As the cost of the treating process is largely .- directly impinging upon the bottom of the reactor a function of the quantity ‘or the reactive agent in conjunction with the use of a tangential jet or 55 employed in the re?ning operations, the e?icient jets to prevent‘ the active agent from settling out‘ utilization of such agent is-of considerable im _ and depositing on the walls of the 'eactor and/or to maintain the reaction medium 11 any desired portance. _A desirable method for insuring optimum utilization oi.’ the treating agent is to state of‘ agitation. , i I carry out the operations in a continuous counter The reaction medium also-may be maintained 60 current manner, the reagent moving through the‘ in the desired degree of agitation by the use of system in a manner countercurrent to that of 7 suitable stirring or mixing devices, or by the use the material tobe treated. . ' ' ‘ ' of circulating pumps, or by a .combination of This may be illustratedby means of a consider these methods, or otherwise. One or more of ation of a simple continuousicountercurrent sys these methods also may be used in conjunction 65 _ tom comprising two treating towers or vessels. , " v.with one or more of-the methods discussed pre- - viously to maintain the system in‘ the desired degree of dispersion.‘ _ , v _> The material to be treated is passed into the ?rst tower, ‘which contains a partially exhausted re - agent. This serves to remove a substantial por tion of the impurities present, after which the of suchngitationomethods is notlrequired in most ' 70 partially re?ned material passes into the second .It should be pointed out, however,'that-the use cases.v Thus, excellent results have been secured by conducting the re?ning operations in a tower. thematerial to be treated being introduced into tower, whichcontains a iresh,~or more highly concentrated; reagent. This serves to remove the impurities present to the desired extent. ,The the bottom of the tower by means of a small process is continued until the reagent in the ?rst I ‘ori?ce! The passage of the fraction being treated 75_'tower is ‘almost, ‘or completely exhausted, after ‘ 9,418,205 11 » 12 ' ' passed‘ continuously into the bottomofa 2" steel column containing very ?nely divided- sodium which it is discarded and the partially exhausted - reagent from the second column substituted for it. Fresh reagent then is added to the second column. suspended in a mixture of amyl-substituted naphthalenes at a temperature of 60° C. The In this manner the material to be treatedand the treating agent pass through the system operation was carried out under reduced pressure, countercurrent to each other, the ?rst continu-__ which was adjusted ‘to maintain the treatins mixture at the desired level. The re?ned styrene fraction obtained as a result of such operations ously and the second in a discontinuous manner. This may be modi?ed such as by the continuous addition of fresh reagent to the second tower, the . was water-white and was substantially free of to the ?rst tower, and the continuous withdrawal phenylacetylene, aldehydes, and other impurities. The impurities'present, particularly the acet of more completely exhausted, vor exhausted' ylenes and the aldehydes, were converted both to continuous transfer of partially exhausted reagent reagent from the ?rst tower. A completely con tinuous countercurrent treating system thus is achieved. sodium derivatives and to insoluble polymers. In the speci?cation and in the claims, the fol 15' lowing terms have the indicated meanings. ‘ Any desired modi?cation of these methods may be employed, and any number of treating. towers The term "metals of group Ia and group 11:: of the periodic system” is intended to mean lith or‘ units may be used. It will be observed that in each of the cases discussed, the incoming ma terial to be re?ned is contacted with ‘partially. ium, sodium, potassium, rubidium, caesium, bar 2.0 exhausted reagent (maximum concentration of impuritiesq-min‘imum concentration of reagent), ium, strontium, and calcium, as well'as active ' alloys containing one or more of ‘such metals as an essential ingredient. _ . The term “?nely divided" is intended to' mean while the outgoing material to be re?ned ‘is con a material reduced ‘to such a state of ?neness that the 'preponderating part is composed of par tacted with fresh or more highly concentrated - reagent (minimum concentration of impurities--, 25 ticles having a diameter of less than 0.05". as well as‘materials in the colloidal or dissolved maximum concentration'of reagent). Thus the two objectives to be sought, namely, practically While reagents and procedures of a particular complete, or complete, utilization of the ‘reagent and substantial, or practically complete, removal - nature have been speci?cally described, it_ is to of impurities from the material to be re?ned, are 30 be understood that ‘these are given by way of illustration. JTherefore, changes, omissions. ad As the limiting factor a?ecting the utilization ditions, substitutions, and/or modi?cations may of the reagent is theproportion of insoluble poly be made within the scope of the claims without form. achieved. ' - . - ~ , Y ’ ‘departing from the spirit of the'invention, which mers and/or residues which can be contained therein without seriously impairing its ?owing ' is intended‘ to be limited only \as. required by the properties, or the passage of the gaseous mate prior art. rial to be treated 'therethrough, it frequently happens that the quantity of insoluble material present is-insuf?cient to interfere seriously with I claim: . ‘ _ l. A process for re?ning a hydrocarbon selected from the grouplconsisting of styrene and methyl the operation of the process when the re?ning 40 styrene and contained in a hydrocarbon mixture which alsoicontains impurity including acetylenic agent present has been almost completely ex hausted. In this case, the operation of the unit material, comprising passing said mixture at a temperature below 100° 0. through a dispersion may be continued by the addition thereto of an additional quantity of the re?ning agent, and of a ?nely. divided metal selected from’the group this process may be continued until the concen ‘5 consisting'of metals'orgroupla and group 11a of the periodic system, said dispersion‘ being at tration of insoluble material inv the reagent ren dersit too viscous to be used further in the proc es in a satisfactory manner. ‘ least .one foot. in thickness in the direction of .?ow of said mixture andcontaining less than " 30% by weight of said ?nely divided metal, main In this connection, itis well to point out that ' the insoluble products-formed during the reaction 5° taining the concentration of said selected hydrohave a tendency to stabilize the sodium suspen carbon in_the reaction zone less than 80% by weight of the total material present, while main sion and act to reduce the rate. of settling of the taining the rate of ?ow per hour of said mixture ' ?nely divided sodium in certain cases. As this is _ desirable; the incomplete removal of insoluble ' through said dispersion less than four'times the ' products from the reagent may be indicated, or 55 weight of, dispersion 'medium’employed, and re moving said mixture‘less contaminated with-im even the addition of a certain quantity of, such lpurityincluding acetylenic material from said materials to a fresh reagent. _ ‘ , reaction zone sumciently' rapidly to prevent a Soluble polymers also usually are f‘rmed in small amounts .during ‘the. re?ning operations, - .largekloss of said selected hydrocarbon due to the . As certain of these soluble and/or~ liquid polymers 60polymerization thereof. . ' may be converted on prolonged contact with the ‘ re?ning agent to viscous and/or insoluble prod ucts, their removal from the suspending medium‘, suitably at the end of a re?ning cycle and prior to the return of the suspending‘agent to the sys tem, may be indicated. On the other hand, cer tain of these soluble polymers are su?lciently stable to act as a suspending medium for the re?ning agent. - . - . I _‘ low 75° C. througha dispersion of a ?nely divided _ alkali metal, said- dispersion containing‘ less than 20% by weight thereof of said ?nely divided metal and being at least two feet in thickness in the di rection of?ow' of said fraction, maintaining the 70 concentration of said styrene in the reaction zone The process may be more completely‘ illustrate by means of the following example. _ 2. IA‘PX'OOGSS for re?ning styrene contained in admixture with- impurity including acetylenic ma terial in a light oil styrene fraction‘, which com prises passing said fraction at a temperature be _ (Example A 60% light oil styrene fraction containing’ less ‘than 65% by weight of the total material pres ent, while maintaining a rate of now perhour of . said fraction through said dispersion of less than four times the weight of dispersion medium em 0.2% phenyiacetylene and,0.02% aldehydes, ‘was 76 ployed, and removing 'saidstyrene fraction less / - 2,418,255 . l3 14 . ' . ‘ contaminated with impurity including acetylenic one foot inthlckness in the direction of flow of material from said reaction zone su?lciently rap idly to prevent a large loss of said styrene due to said mixture, maintaining the concentration of polymerization thereof. 65% by weight of the total material present, said methyl styrene in the reaction zone less than while maintaining the rate ,of ?ow per hour of said 3. A process for re?ning methyl styrene con mixture through said dispersion at less than four times the weight of dispersion medium employed, ylenic material in a light oil methyl styrene frac and removing said methyl styrene in vapor phase tion, which comprises passing said fraction at a ‘less contaminated with impurity including acet temperature below 75° C. through a dispersion of a ?nely divided alkali metal, said dispersion con 10 ylenic material from said reaction zone su?lciently rapidly to prevent a large loss of said methyl taining less than 20% by weight thereof of said styrene due to polymerization thereof. ‘ ?nely divided metal and being at least two feet tained in admixture with impurity including acet-, 6. A process for the puri?cation of styrene con in thickness in the direction of ?ow of said frac tained in admixture with impurity including acet tion, maintaining the concentration of said methyl styrene in the reaction" zone less than 65% by 15 ylenic material, which comprises passing said ad mixture at a temperature below 85° 0. through a weight of the total material present, while main dispersion of ?nely divided sodium, said dispersion taining a rate of flow per hour of said fraction being at least one foot in thickness in thedirec through said dispersion of less than four times tion of ?ow of said admixture and containing less the weight of’ dispersion medium employed, and removing said methyl styrene fraction less con 20 than_30% by weight thereof of said ?nely divided sodium, maintaining the concentration of said taminated with impurity including acetylenic ma styrene in the reaction zone less than 65% by terialv from said reaction zone sumciently rapidly weight of the total material present, while main; ~ to prevent a large loss of said methyl styrene due to polymerization thereof. ‘ , . 4. A process for re?ning styrene contained in a hydrocarbon mixture contaminated with impurity including acetylenic‘ material, which comprises taining the rate of flow per hour of said admix- ' ture through said dispersion at less than four times the weight of dispersion medium employed, - and removing styrene less contaminated with im purity including acetylenic material from said re action zone ,su?iciently rapidly to prevent a large loss of said styrene due to polymerization thereof. divided alkali metal, said dispersion conta 30' 7. A process for the puri?cation of methyl less than 30% by weight thereof of said ?nely di styrene contained in admixture with impurity in vided metal and being at least one vfoot in thick cluding acetylenic material, which comprises ness in the direction of flow of said mixture, main passing said admixture at a temperature below taining the concentration of said styrene in the reaction zone less than 65% by weight of the total 35 85° C. through a dispersion of ?nely divided so dium, said dispersion being at least one foot in material present, while maintaining the rate of thickness in the direction of ?ow of said admix ?ow per hour of said mixture through said dis ture and containing less. than 30% by weight persion'at' less than four times the weight of dis thereof of said ?nely divided sodium, maintaining persion medium employed, and removing said styrene in vapor phase less contaminated with im 40 the concentration of said methyl styrene in the reaction zone less than 65% by weight of the total purity including acetylenic material from said re-~ material present, while maintaining the rate of action zone sumciently rapidly to prevent a large ?owper hour of said admixture through said dis loss of said styrene due to polymerization thereof. ‘ persion at less than four times the weight of dis 5. A process for re?ning methyl styrene con tained in a hydrocarbon mixture contated 45 persion medium employed, and removing methyl styrene less contaminated with impurity includ» with impurity including acetylenic material, ing acetylenic material from said reaction zone which comprises passing said mixture under tem suf?ciently rapidly to prevent a large loss of said perature conditions below 100° C. through a, dis methyl styrene due to polymerization thereof. persion of a ?nely divided alkali metal, said dis passing said mixture under temperature condi tions below 100° (2.‘. through a dispersion of a ?nely persion containing less than 30% by weight vthere ' of of said ly divided metal being at least "1 J. sonar. .