vPatented 1946 -‘ . 2,413,254 umrso fsrarss PATENT 'QFFHCQE A . 2,413,254 ' I ' . HYDROGARBON MATERIAL WITH AN AL KALI 0R EARTH METAL Frank J. Soday, Swarthmore, Pa, assignor to The United Gas Improvement Company, a cor poration of Pennsylvania No Drawing. Application ' 24, 1942, ‘ Serial No. 470,078 ' . was... (crate-.611) _. v 1 2 v This invention relates to the puri?cation of unsaturated hydrocarbons. More particularly, this invention is concerned . . may be re?ned by the application in ?nely di vided form‘of at least one metal or group Ia and group no of the periodic table, as well as certain active alloys thereof. Particularly desirable re with the removal of certain impurities from un saturated hydrocarbons, or mixtures thereof. An object of. the present invention is the re sults are obtained by the use of ?nely divided al kali and alkaline earth metals. moval of certain impurities from unsaturated hy-~ drocarbons by ‘the application of at least one Examples’ of such metals are lithium, sodium,‘ potassium, rubidium, caesium, barium, strontium , v?nely divided metal of groups In and 11a of the and calcium- Due to the availability and low cost -' of sodium and potassium, however, these metals periodic system, or active alloys thereof. Another object of the invention is the re?ning of oleilnes, or fractions or mixtures containing at least one ole?ne, under conditions designed to. reduce the losses incurred in such operations. Other objects and advantages of the invention will be apparent to those skilled in the art upon an inspection 0 the speci?cation and claims. . are preferred for the use set forth herein. Alloys of these metals, such as,NaPb1o,‘NaI-lg4, NaCas, NaZmz, Ella, and th‘eiike, also maybe employed-for the removal of undesired impurities fromunsaturated hydrocarbons. Ingeneral, the alloys of the respective metals react with the im purities present in such materials at a slower rate ' Unsaturated hydrocarbons and unsaturated hydrocarbon fractions,- particularly those ob 4 than the corresponding metals. Mind that a solution of sodium, or a suspension or emulsion of very finely divided sodium, or a solution, suspension, or emulsion of one or more tained by the pyrolysis of petroleum or of petrol eum hydrocarbons, frequently contain substan tial proportions of impurities which interfere with their use in most, if not all, industrial applica t ons. sodium alloys or active compounds, is a particu larly desirable agent for the removal of certain undesirable impurities iromunsaturated hydro . Thus, unsaturated hydrocarbons obtained by carbons. Excellent'results are obtained by the .use of a" suspension of very finely divided sodium. the pyrolysis of petroleum may contain impurities The alkali metals, particularly sodium and po tassium. are very active catalysts for the poly _ such as acetylenes, aldehydes, peroxides, phenolic - compounds, other oxygen-containing compounds, sulfur-containing compounds, such as disul?des merization of ' unsaturatedhydrocarbons, Thus, and mercaptans, nitrogen-containing com 30 practically all of the early work on the prepara tion of synthetic rubber from isoprene, both‘in pounds, and thellike. These compounds may be present in proportions ranging from traces to this country and abroad, was based on the use‘ of several percent depending, among other things, sodium and/or potassium as the catalyst. Con-Y sequently, the use of such an active catalyst, par upon the boiling range of the particular fraction or mixture in question, the characteristics of the 35 ticularly in ?nely divided (and hence most active) form, for the re?ning of unsaturated hydrocar petroleum or petroleum fraction from which it was obtained, and the cracking ‘temperature, as bons would be expected to result in the‘conversi‘on of the greater portion, if not all, of the unsatur well as other pyrolysis conditions, employed. . The removal of one or more impurities from . ated hydrocarbon to polymers. . v. - _ unsaturated hydrocarbons or unsaturated hydro 40 It should be emphasized that the success of the re?ning operations is dependent upon rigid ad carbon vfractions is complicated generally by the ease with which such materials may be polymer Y herence to certain operating conditions such as ized. The application of the re?n'ing techniques‘ customarilyemployed for the removal of impuri temperature, reaction time, concentration, and so forth, which (will be discussed in considerable‘ ties from hydrocarbons or hydrocarbon fractions 45 detail. , ' Unsaturated hydrocarbons which may be re which are preponderantly saturated and/or aro'-_ ?ned by methods to be more particularly de-_ matic in character, such as gasoline, kerosene, scribed herein ‘include hydrocarbons containing light petroleum distillates, coal tar fractions, and ' at least one double bond such as ole?nes, for ex the like, to unsaturated hydrocarbons or unsatur ated hydrocarbon ‘fractions frequently leads to 50 ample, aliphatic, cyclic, and aromatic ole?nes; dioleilnes such as aliphatic, ‘cyclic and aromatic the conversion of a substantial proportion, or all. diole?nes; and mixtures containing one or more of such materials to inferior types of polymers. of the foregoing, classes of'hydrocarbons. As a result of extensive experimentation, I have The process is particularly applicable to the re discovered that unsaturated hydrocarbons and unsaturated hydrocarbon fractions and mixtures % ?ning of ole?nes, such as aliphatic-de?nes. a . ‘ I - amazes . . 3 be re?ned then is passed‘ upward A desirable source of ole?nes. to be re?ned by methods to be more particularly described herein ._._ column of liquid at a rate suilicient to insure the is the by-product obtained upon the concentra- ~ a removal of the desired quantity and type of- im purities present at the temperature employed. tion of diole?nes, such as butadiene. Thus. they Other methods of contacting _-the material to ole?ne fraction obtained upon the concentration ' 'be treated and the re?ning agent also may be of a butadiene fraction usually contains substan employed if desired. Thus, the unsaturated-hy tial, and generally contains predominating. Pro - drocarbonv may be passed through a horizontal 7 portions of‘ isob'utylene. Such fractions may be ‘ re?ned readily by the process disclosed herein. treating unit, such as a pipe or bank of pipes, A preferred embodiment of this-invention is 10. containing a suspension of the desired're?nins agent, or otherwise. The suspending liquid employed for the re- ' the re?ning of isobutylene or of unsaturated hy drocarbon fractions in which isobutylene is the. ?ning agent may be of any desired type, pro vided that it does not reactwith the reagent or prepondering unsaturated hydrocarbon present. Buchfractions also may contain minor.proportions of one or more diole?nes. ' the material to be treated to any substantial . extent, and provided that it does not introduce any additional impurities into the material to _ be treated. I ?nd . that hydrocarbons and hy , drocarbon fractions‘ are particularly desirable. While the re?ning operations may be rrigged‘ ‘ f added ' out m the absence 0 em any 10 inhibitors’ I prefer to p y e polym _ on . 1 one or more p0ly- of the unsaturated hydrocarbons in the form of ‘polymers, as well as to increase the limits of the _> merization inhibitors in order to reduce the loss permissible reaction variables. materials for use as suspending mediums for refining agents of the type described herein. Excellent results have been obtained by the use . of aromatic hydrocarbons and aromatic hydro Excellent results may be obtained when one or carbon fractions for ‘this purpose. ' more inhibitors selected from a list comprising (1). secondary aryl amines such as phenyl beta 25 It is to be understood, of course, that the ma-‘ terial to be treated may dissolve to some extent naphthylamine, diphenyl-p-phenylene dlamine, isopropoxydiphenyl amine, aldol-alpha-naph- ' . in the suspending medium, consequently the ' suspending medium actually employed in the op thylamine (and polymers thereof), symm. di beta-naphthylhp-phenylene diamine, trimethyl dihydroquinoline (and polymers thereof),'and eration of the process usually comprises a mix 30 ture of the material to be treated and the sus pending medium initially introducedv into the the ditolylamines;' (2) phenolic compounds, such as p-tertiary but? catechol and alkylated poly system. ketone, such" as I cetone‘,‘ n _ , . ‘ - The unsaturated hydrocarbon being treated - droxy phenols; a d (3) reaction products of a also may serve as a suspending medium for the . and/or an aldehyde,‘ such as formaldehyde vand acetaldehyde. with an 35 re?ning agent without the addition of any other ' amine, such as aniline, are used in the re?ning ‘ material, if desired. Thus, the unsaturated hy drocarbon or unsaturated hydrocarbon fraction operations disclosed ‘herein. In general, I prefer to employ less than 10% .. may (be introduced into the desired tower or vessel, together with the ?nely divided. re?ning by weight, of polymerization inhibitor, based on agent, after which the material to be treated‘is the unsaturated hydrocarbon ‘or unsaturated hy-v passed ‘into the suspension of the re?ning agent drocarbon fraction in batch treating ‘processes, and the maximum total volume of suspending I in the unsaturated hydrocarbon at the desired temperature, the. charging rate and more par-. liquid in the treating system at any one time in ticularly the operating pressure being adjusted to the casezof continuous treating processes. Good results also have been obtained by the use of less 45 ‘maintain the treating agent at the desired level in the vessel. _ than 5% inhibitor and even 2% inhibitor in cer-q tain cases, particularly when one or more of the It is to be understood, of course, that the por-‘ inhibitors listed in the preceding paragraph are tion of the‘ material to be treated which has ‘been dissolved in the suspending medium or which employed. - While the re?ning operations ‘may be carried 50 has been employed as the suspending medium in out in a satisfactory manner in a batchwise . the substantial absence of other liquid materials, manner, I prefer to conduct such operations in a does not necessarily remain in the treating zone continuous or semi-continuous system in order throughout the entire treating cycle. Rather, to reduce the proportion of unsaturated hydro this material is in a state of‘ dynamic equilibrium carbon lost in the form of polymers, as well as to with the‘material being treated, a portion of it secure greater economy in the use of the reagent. volatilizing continuously and being removed from 'The preferred re?ning method disclosed herein the system, the material volatilized in this man ‘ differs fundamentally from all methods described ner being replaced by the solution ‘of a corre spondingquantity of freshly added material to drocarbons in that the material in question is 60 be treated. The major portion of the material treated with a metal of group IA or group'IIA, to be treated, of course, bubbles up through the _or an active alloy of such metals, in ?nely di suspending medium without dissolving therein. vided or solution form in a continuous system ' The thickness of the layer of reagent through preferably in the presence of one or more poly which the material to be treated is preferably merization inhibitors. By the use of a continu 65 passed depends upon a number of factors, such ous system, particularly in conjunction with the heretofore for'the re?ning of unsaturated hy . as thequantity and type of impurities present, . ‘ use of an‘ inhibitor, the loss of unsaturated by drocarbons due toside reactions or to polymeri- , zation is very markedly reduced, or almost com pletely'eliminated. 70 Although the process may be carried outin any-desiredmannerHI prefer. to conduct it in a vertical vessel or tower in which a certain height of a liquid suspension or solution of the active re?ning agent is maintained. The material to 75 the extent to which such impurities are to be re- I moved, the type and degree of dispersion of the treating agent employed,‘ the reaction tempera ture, the concentration of the treating agent in the suspending medium. and the like. In gen eral,'however, I prefer to employ a layer of re agent at least one foot thick and, more prefer ably, at least two feet thick. ‘ Excellent. results , ‘ 2,413,954 are obtained by the use of a layer of reagent at ,at subatmo'spheric pressures, thereby reducing least four feet thick. the concentration of the unsaturated hydrocars _ It will be recognized that, other things being equal, the depthoi‘ reagent employed in the treat ing vessel controls the contact time between the material to be re?ned and the re?ning reagent. The degree of dispersion of the treating agent bon ‘present in the re?ning system at a given reaction temperature. This serves to reduce the quantity of unsaturated hydrocarbonlconverted to polymers in the process, consequently, it is a preferred embodiment of this invention. The temperature at which the process is con also has a very profound effect upon the degree ducted also has a very considerable bearing up of re?ning obtained. In thecase'of sodium, I prefer to employ a subdivided mass in which at 10 on the degree to which the unsaturated hydro least the maJority of the particles present .have carbon is re?ned and the, losses incurred due to polymerization. Although the optimum reaction a diameter of not more than 0.05’; and, more temperature to be employed is dependent large-l preferably, not more than 0.03"; Excellent re 1y upon other factors, such as the concentration sults are obtained when at least the majority of the particles present‘ have a diameter of not more 15 of both the unsaturated hydrocarbon and the re ?ning agent in the reaction zone, I generally pre than 0.02". '_ fer to conduct the re?ning operations at temper This subdivision may be carried out in any atures below 100° C. and. more particularly, be desired manner. Thus. in the case of sodium, a low 80° C. ,Excellent results are obtained by consolution of this material in liquid ammonia may be introduced into an inert liquid, such as xylene, 20 ducting the re?ning operations at temperatures below 70° C. -' at room temperature or at elevated temperatures. The rate at which the material to be re?ned is ~ The almost instantaneous volatilization of the passed through the reagent has a very consider ammonia present results in the dispersion of the able e?ect upon the degree to which the impuri sodium present in the xylene in an extremely ?nely divided state. Another method comprises 25 ties present are removed, although this is de pendent to some extent upon other variables spraying molten sodium into an inert liquid such such as the concentration of re?ning agent in the as xylene or solvent naphtha. By suitable varis suspending medium and the temperature, at ations in the type and degree of ?neness or in the . dispersing ability of the spray nomle employed, . . which the re?ning operations are being conduct or both, sodium of almost any desired degree of 30 ed. While it is dif?cult to establish exa'ct'limits for optimum throughputs under all conditions, ?neness may be obtained at will. ' Anothersatisfactory method comprises melting ~ I generally prefer not to exceed a throughput of the sodium under the surface of a suitable liquid, such as xylene, followed by violent agitation, such material to be treated on an hourly basis of more than four times the weight of'suspendirm inert liquid treated, upon'an hourly basis, are passed through as with a turbo-mixer, and cooling with agita 35 medium ‘employed and more preferably, not more than twice the weight of the suspending tion. Other methods which may be used include medium. Excellent results are obtained when extrusion through ?ne ori?ces, and the genera not more than equal quantities of material to be tion of ‘an are between sodium electrodes in an ' _ _ . Although almost any desired concentration of 40 the suspending medium. It will be recognized that the contact time be treating agent in the suspending medium may be tween the material to be treated and the reagent employed, depending upon the type and concen is determined both by the thickness of'the layer tration of the unsaturated“ hydrocarbon in the . of reagent employed and by the rate at which the diluted fraction to be re?ned, the temperature, the depth of reagent employed, and the like, I 45 material to be treated is passed through the re-, generally prefer to employ a reagent containing agent. - _ - 20% by weight of the treating agent. Excellent The method employed 'for introducing the ma terial to be re?ned into the re?ning agent also results are obtained when less than 15 % by weight ' has some in?uence upon the extent to which the less than 30% and more particularly less than of the treating agent is‘ suspended in the sus 50 unsaturated hydrocarbon or unsaturated hydro carbon -fraction is re?ned. In general, it may be (pending medium. ' ’ said that a ?ne stream or jet of the liquid or gas It is to be understood, ofvc'ourse, that the term eous material to be re?ned is desired. This may suspending medium refers to the actual-suspend; be accomplished by introducing the material to ing agent employed during the treating opera tion, and includes any of the material being 55 be treated into the reagent by ‘means of suitable ori?ces, jets, nozzles, or other subdividing means. treated which may dissolve in such agent. Porous objects or materials also may be employed The concentration vof the unsaturated hydro for this purpose, such as porous ceramic or glass carbon to be treated also has a considerable in diffusing blocks or units‘., ' ?uence upon the method of operating the process. I generally prefer to employ such proportion of do As the re?ning agent may show some tendency _ to settle out in the bottom of the treating vessel suspending medium that the actual concentra or_unit, the jets or nozzles by means of which the tion of the unsaturated hydrocarbon in the re material to be treated is introduced into the unit action zone is less than 80% and, more prefer ' may be so arranged as to prevent any undue setably, less than 70%. Excellent results are ob‘ - tained when the actual concentration of unsat 65 tling of this material. In vertical vessels, this may be accomplished by locating these units in urated hydrocarbon in the reaction zone ‘is less than 60%. » » ' ' . such a way as to impinge the inlet stream or streams upon the bottom of the treating vessel. The inlet Jets also may be arranged tangentially and-superatmospheric pressures. ‘ 70 to'impart a swirling or circular motion to the In many cases, particularly when a fairly high treating reagent, if desired. Another method The process may be carried out‘ at any desired pressure, such as atmospheric, subatmospheric, ly concentrated fraction is re?ned with a sus pension or ~ solution of a ?nely divided active comprises locating the inlet jet or jets directly 7 in the bottom of the reactor, or ‘tangentially in the sides of the reactor, or both, to prevent any metal. or alloy of the type described herein; it is highly advantageous to conduct such operations 75 settling in the bottom of the reacting vessel and I 2,418,954 7 . to impart any desired circular or other motion to the treating medium. Any desired combination of these methods also may be employed, such as the use of a jet or jets directly impinging upon the bottom of the reac-' tor in conjunction with the'use of a tangential jet or jets to prevent the active agent from a 8 carbon dioxide to form unsaturated acids, oi‘ otherwise. ' A convenient method for the disposal of the insoluble polymers comprises treatment with carbon dioxide, suitably in the presence of traces of moisture, followed by ?ltration. As the cost of the treating process is largely a - function ‘of the quantity of the reactive agent reactor and to maintain the reaction medium in . employed in the re?ning operations, the efficient 10 utilization of such agent is of considerable im any desiredstate of agitation. ‘ . settling out and depositing on the walls of the The reaction medium also may be maintained in the desired. degree of agitation by the use of suitable stirring or mixing devices, or by the use portance. A desirable method for insuring op timum utilization of the treating agent is to carry methods also may be used in conjunction with one or more of the methods discussed previously to maintain the system in the desired degree of material to be treated. ' out the operations in a continuous countercur rent manner, the reagent moving through the of circulating pumps, or by a combination of these methods, or otherwise. One or more of these 15 system in a manner countercurrent to that of the dispersion. This may be illustrated by means of a consider ation of a simple continuous countercurrent sys tem comprising two treating towers or 'vessels. It should be pointed out, howeventhat the use 20 The material to be treated is passed into the ?rst tower, which contains a partially exhaustedre of such agitation methods is not required in most agent. This serves‘to remove a substantial por cases. Thus, excellent results have been secured by conducting the re?ning operations in a tower, - tion of the impurities present, after which the partially re?ned material passes into the second the material to be treated being introduced into the bottom of the tower by means of a small ori 25 tower, which contains a fresh, or more highly concentrated, reagent. This serves ‘to remove the ?ce. The passage of the fraction being treated impurities present to the desired extent. The > in the gaseous state upward through the column process is continued until the reagent in the ?rst usually is su?lcient to maintain the system in the tower is almost, or completely, exhausted, after desired degree of agitation. . The re?ning agent, particularly when ?nely di 30 which it is discarded and the partially exhausted reagent from the second column substituted for vided sodium is employed for this purpose, usu it. Fresh reagent then is added to the second ally acts both as a reactant and as a polymeriz column. , ing agent for the removal of undesired impuri In this manner the material to-be treated and ties. Thus, in the case of unsaturated hydrocar the treating agent pass through the system bon fractions containing acetylenes, aldehydes, countercurrent to each other, the ?rst continu and other impurities, the sodium usually will re ously and the second in a discontinuous manner. act with at least a portion of the acetylenes‘ pres This may be modi?ed such as by the continuous ent to form sodium acetylides, and may react addition of fresh reagent to the second tower, the with certain of the oxygenated derivatives to At 40 continuous transfer of partially exhausted re- ‘ _ form corresponding metallic derivatives. agent to the ?rsttower, and the continuous with least a portion of‘ the acetylenic hydrocarbons drawal of more completely exhausted, or ex- ‘ present also are polymerized to form polymers, hausted, reagent ‘from the ?rst tower. A com or copolymers with other unsaturated hydrocar-' pletely continuous countercurrent treating sys- ' bons present, which polymers frequently are in soluble in nature. Certain of the oxygenated de 45 tem thus is achieved. _ Any desired modi?cation of these methods may rivatives, such as aldehydes, also may be poly be employed, and any number of treating towers merized to form polymers which may be insolu ble in type. ~ . As a result, the re?ning of unsaturated hydro carbons with a suspension of ?nely divided so dium usually is characterized by the gradual ac cumulation-of insoluble polymers in the re?ning ' medium, This may be removed in any desired manner, such as by ?ltration, which may be car ried out continuously during the re?ning opera tion, or may be carried out in a batchwise man ner after the termination of the re?ning step. or units may be used. It will be observed that ,in each of the cases discussed, the incoming 50 material to be re?ned is contacted with partially exhausted reagent (maximum concentration of - impurities-minimum concentration of reagent), while theoutgoing material to be re?ned is con tacted with fresh or morehighly concentrated reagent (minimum concentration of impurities maximum concentration ‘of reagent). Thus the two objectives to be sought, namely, practically As the removal of the insoluble polymers also - complete, or complete, utilization of the reagent and substantial, or practically complete, removal is attended by some loss or re?ning agent, even when the latter is in a very ?ne state of subdivi 60 of impurities from the material to be re?ned, are achieved. ' 1 sion, it is advisable in many cases to continue As the limiting factor affecting the utilization the re?ning operations until the re?ning agent has been largely ‘or. completely exhausted before. of the reagent is' the proportion of insoluble polymers and/or residues which can be con ?ltering. I 65 tained therein without seriously impairing its The solid or semi-solid ?ltered products ‘may ?owing properties, or thepassage of the gaseous be treated to_-recover any desired materials or material to be treated therethrough, it frequently they may be?disposed of in any suitable manner. happens that the quantity of insoluble material , Thusf‘any‘ unchanged re?ning agent, such as present is insu?lcient to interfere seriously with the operation of the process when the re?ning may be recovered by melting'and coa agent present has been almost completely, ex lescing?‘ operations, or by amalgamation with hausted. In this case, the operation of the unit ni'er'curyj‘or otherwise. Certain of the reaction may be continued by the addition thereto of an prfdtii'icts, such ‘as sodium acetylides, may be de additional quantity of the re?ning agent, and composedl'with water to ‘regenerate the corre sponding'i'acids or they may be reacted with 75 this process may be continued until the concen ’ ' $418,254 tration or insoluble niai'erial ‘in the reagent Iclaim: renders it too viscous to be used further- in the _ ' process in a satisfactory manner. " ' _. . ing acetylenic and-aldehyde material, comprising I have a tendency to stabilize the sodium suspen- ?nely divided sodium in certain cases. _ As this ' l _ - 1. A process for re?ning unsaturated hydrocar-v bon material having from one to two double bonds terial being contaminated with impurity includ ' sion andact to reduce the rate of settling of the ' materials to a fresh reagent. @ permolecule, said unsaturated hydrocarbon ma In this connection, it is well to point out that _ the insoluble products ‘formed during the reaction is desirable, the incomplete removal of insoluble products from the reagent may be indicated, or even the addition of a certain quantity of such 10 , passing said unsaturated hydrocarbon material at a temperature below 100° C. through a disper > sion 'of a ?nely divided material selected from the 10 group consisting of metals of group IA and group _ ‘ _ HA of the periodic system and alloys thereof, said dispersion being at, least one foot in thickness in Soluble polymers also usually .are formed in > the direction'of flow of said unsaturated hydro carbon material and containing less than 30% by small amounts during the re?ning operations. As weight of said ?nely divided material, maintain-_ certain. of these soluble polymers are converted ing the concentration of said unsaturated hydro- on prolonged contact with‘the re?ning agent to carbon material in the reaction zone below 80% viscous or insoluble products, their removal from. , by weight of the total material present, while the suspending medium, suitable at the end; maintaining the rate of ?ow per hour of said un of a re?ning cycle and prior to'the return of the suspendingv agent to ‘the system, maybe -indi-. 20 saturated hydrocarbon material through said dis-, persion at less than fourv times the weight of dis cated. On the other hand, certain of these persion medium employed, and removing said un soluble polymers are sufficiently stable to actas a I suspending medium for the refining agent. An example of procedure which may be con saturated hydrocarbon material less contami- ' nated with impurity including acetylenic and aldehy'dematerial from said reaction zone, suffi ciently rapidly to prevent a large loss of said on ‘ saturated hydrocarbonimaterial due to the poly 1 venientiy followed ‘in the practice of my inven tion is as follows: Example 1 meriz‘ation thereof. , , _ 2._A process for re?ning unsaturated hydro A light oil fraction containing approximately carbon material having from one to’ two double 25% isobutylene, as well as approximately 1% 30 bonds per molecule, said unsaturated hydrocar- ' acetylenic hydrocarbons, 0.05% aldehydes, and other impurities} was passed continuously in the gaseous stateinto a xylene suspension of ?nely divided sodium contained in a’steel column 2" in diameter at a temperature of 50° 0. Under the operating conditions chosen, the re?ning agent comprised a. 10% suspension of, ?nely divided sodium in a suspending. medium bon material being contaminated with impurity ‘including acetylenic ‘material, which comprises continuously passing said unsaturated hydrocar-' bon material ‘at a temperature below 80? 0. through a dispersion of a ?nely divided material ‘selected from the group consisting of metals of group IA and group 115 of the periodic system and alloys thereof. said dispersion containing less than ' containing ‘approximately 90% xyleneand 10%: ' 20% by ‘weight thereof of said ?nely divided ma- ’ ' isobutylene fraction. The height of re?ning terialland being atleast two feet in thickness in agentemployed was approximately 6 feet. the direction of ?ow of said unsaturated hydro The re?ning operation was continued for a carbon material, maintaining the concentration period of 30 hours, the isobutylene-fraction being ' of said unsaturated hydrocarbon material in the charged at; the rate of approximately 1000 grams 45 reaction zone less than I10% by weight of the total material present, while maintaining a rate of The product obtained was water-white in color ?ow per hour, of said unsaturated hydrocarbon and contained only 0.002% acetylenes. ~The alde - material through said dispersion of less than hydes present had been removed completely. twice the weight of dispersion medium employed, The product was in a high state of purity and and continuously'removing said unsaturated .hy 50 could be used for the production of polybutene or drocarbon material less contaminated with impur synthetic rubber, suitably by copolymerization ity including acetylenic material from said reac with relatively small proportions of one or more tion zone suf?ciently rapidly to prevent a large diole?nes. , loss of said unsaturated hydrocarbon material due In the speci?cation and in the claims, the fol to polymerization thereof. . lowing terms have the indicated meanings. -3._ A process for re?ning unsaturated hydrocar The term "a metal of group IA and group 11A material having from one to two double bonds of‘ the periodic system” is intended to mean one > bon per molecule, 'said unsaturated hydrocarbon ma of a gr'oup consisting of lithium, sodium, potas terial being contaminated with impurity includ sium, rubidium, caesium, barium, strontium. and 60 ing aldehyde material, whichcomprises continu-' ‘ ously passing said unsaturated hydrocarbon ma ’ The term “alkali metal” is employed as ‘de?ne ' terialat a temperature below 80° C- through a itive of the group of metals consisting of lithium, dispersion of ,a ?nely divided material selected . I per hour. calcium. v , ' _ 1 I - sodium, potassium, rubidium,- and caesium. The term “?nely divided” is intended to mean a material reduced to such a state of ?neness that from the group consisting of metals of group'IA and group 11A of the periodic system and alloys the preponderatingpart is composed of particles thereof, said dispersion containing less than ‘20%. tions, substitutions, and/or modi?cations may be material present,- while maintaining a rate of ?ow per hour of said‘unsaturated hydrocarbon mate 75 rial througb said dispersion of less than twice the by weight thereof of said ?nely divided material having a diameter of less than 0.05", as well as and being at least two feetin thickness in the materials in the colloidal or dissolved form. direction of ?ow of said unsaturated hydrocarbon While reagents and procedures of a particular nature have been speci?cally described, it is to 70 material, maintaining the concentration of said unsaturated hydrocarbon material in ,the' reac-_. be understood that these are given by way of tion zone less than 70% by weight of the total illustration. Therefore, changes, omissionaaddi made within the scope of the claims without de parting from the spiirtof the invention. / 8,418,854 11 . . weight of dispersion medium employed, and con tinuously removing said unsaturated hydrocarbon material less contaminated with impurity includ za'tion thereof. "1. A process for the puri?cation of isobutylene contained in admixture with impurity including acetylenic material. which comprises continuously ing aldehyde material from said reaction zone sumciently rapidly to prevent a large loss ofsaid unsaturated hydrocarbon material due to poly nierization thereof. 12 _ loss of aliphatic ole?ne material due to polymeri passing said admixture in vapor phase at a tem perature. below 100° C. through a dispersion of ‘ 4. A process for re?ning ole?ne material con ?nely divided sodium,_ said dispersion being at tained in a mixture including‘acetylenic mate-' least one foot in thickness in the direction of ?ow rial, which comprises continuouslypassing said 10 of said admixture and containing less than 30% mixture ‘in vapor phase under temperature con by weight thereof of said ?nely divided sodium, _ ditlons below 100° 0. through a dispersion of a maintaining the concentration of said‘isobutylene ?nely divided alkali metal, said dispersion con taining less than 30% by weight thereof of said v?nely divided alkali metal and being at least one foot in thickness in the the direction of ?ow of in the‘reaction zone‘ less than 80% by‘ weight of the total material present, while maintaining the rate of ?ow per hour ofsaid admixture through , said mixture, maintaining the concentration of of dispersion medium employed, and continuously said dispersion at less than four times the weight - said ole?ne material in the reaction zone less removingisobutylene in vapor phase less con than 80% by weight of the total material present, taminated with said impurity including acetylenic while maintaining the 'rate of ?ow per hour of said mixture through said dispersion at less than ‘four times the weight of dispersion medium em-. material from said reaction zone su?iciently rapidly to- prevent a large loss of said isobutylene due to polymerization thereof. 8. A process for the recovery of isobutylene from a mixture containing the same and contain ployed, and continuously removing said ole?ne material less contaminated with impurityinclud ing acetylenic material from said reaction zone su?iciently rapidly to prevent a large loss of said, ole?ne material due to polymerization thereof. 5. A process for the recovery of aliphatic ole?ne ‘material from a mixture containing the same and ing impurity including acetylenic material. which comprises continuously passing said mixture in vapor phase at a temperature below ‘10° vC. through a reaction zone containing a dispersion - of ?nely dividedsodium at least the majority of containing impurity including acetylenic mate 30 the particles of which have a- diameter, of not rial, which comprises continuously passing said ' more than 0.05", said dispersion containing less than 30% by weight thereof of said'?nely divided _mixture in vapor phaseunder temperature cori-v ditions below 80° 0. through a dispersion of finely ' soduim ‘and being at least one vfoot in thickness divided sodium, said dispersion containing less . in the direction of ?ow of said mixture. maintain than 20% by weight thereof of said ?nely divided. as ing the concentration ofsaid isobutylene in said sodium and being at least two feet in thickness reaction zone less than 80% by-weight of the total in the direction of ?ow of said mixture, maln material present. while maintaining a rateof ?ow talning the concentration of aliphatic ole?ne " per hour of said mixture through said dispersion material in the reaction zone less than 70% by of less than four times the weight of dispersion weight of the total material present, while main (0 medium employed. and continuously removing taining a rate of flow per hour of said mixture ' isobutylene in vapor phase and less contaminated through said dispersion of less .than twice the with said impurity including acetylenic' material weight of dispersion medium employed, and con from said reaction zone ‘su?lciently rapidly to tinuously removing said aliphatic ole?ne material prevent a, large loss of said isobutylene due to‘ in vapor phase less contaminated with impurity 45 polymerization thereof. including acetylenic material from said reaction 9. A process for the puri?cation of a light oil zone su?lciently rapidly to prevent a large loss of isobutylene fraction containing isobutylene to said aliphatic ole?ne material due to polymeriza gether with impurity at least a portion of which tion thereof. is in the form of acetylenic material, which com 6. A process for the puri?cation of aliphatic 50 prises continuously passingsald fraction in vapor ole?ne material contained in admixture with im phase at a temperature below 80° ‘C. upwardly purity including aldehyde material, which com through‘ a reaction zone containing a dispersion prises continuously passing said admixture in ‘ of ?nely divided sodium at least the majority of vapor phase at a temperature below 80° 0. through I the particles of which have a diameter of not a reaction zone containing a dispersion of ?nely 55 more than 0.03", said dispersion containing less divided sodium, said dispersion containing less than 20% by weight thereof of said ?nely divided than 20% by weight thereof of said ?nely divided sodium and being at least two feet in thickness in sodium and being at least two feet in thickness the direction of flow of said fraction, maintaining in the direction of ?ow of _said admixture, main the concentration of said isobutylene in said re taining the concentration of aliphatic ole?ne 60 action zone less than 70% by weight of the total material present while maintaining a rate of ?ow material in said reaction zone less than 70% ‘by weight of the total material present, while per hour of said, fraction .throughsaid dispersion maintaining _a rate of ?ow per hour of said ad mixture through said dispersion of less than twice dium' employed: and continuously removing said of less than twice the weight of dispersion me the ‘weight of dispersion medium employed, and 65 fraction in vapor phase from the top of said continuously removing said aliphatic ole?ne ma reaction zone less ‘contaminated with impurity terial in vapor phase less contaminated with im- - including acetylenic material suiliciently rapidly purity including aldehyde material from said re action zone su?iciently rapidly to prevent a large to prevent a large loss of said isobutylene due to polymerization thereof. 70 ' FRANK J. SODAY.