Jan. 7, 1947. 2,413,791 R. w. SHAFOR FRACTIONATION 0F SOLUTES Filed May 9, 1942 I'OYAQ L 2 Sheets-Sheet l NC “I X Ii INVENTOR RALPH W. SHAFOR BY ’ ‘I mmdkm ATTORNEY Jan. 7, 1947. 2,413,791 R. w. SHAFOR FI‘RACTIONATION OF SOLUTES Filed May 9, 1942 2 Sheet>-Sheet 2 IN'VENTOR RALPH W. SHAFOR BY ATTORNEY 2,413,791 Patented Jan. 7, 1947 UNITED STATES PATENT. OFFICE 2,413,191‘ ' FRACTIONATION, 0F SOLUTES Ralph W. Shai'or, New York, N. Y" assignor to The Don‘ Company, a corporation or Dela» , ware Application May 9, 1942, Serial No. 442,385 5 Claims. (GE. 23-1) 3 portion of the effluent solution ?owing from the This invention relates to the puri?cation of» sugar-bearing solutions or sugar juices by treat bed; ment with ion exchange materials whereby the solution is subjected sequentially to treatment in sent an improvement upon or_ a re?nement over a cation and an anion exchanger bed, and more speci?cally this relates to a method of operation coupled with such ion exchange treatment, whereby certain non-sugar solutes in the juice ' The present invention may be said to repre the substance of the‘ Rawlings invention above outlined, such re?nement residing in the use of spent 'regenerant solution as an auxiliary solu tion for displacing the organic constituents from the bed in a manner to be hereinafter further ex can be isolated and recovered. This invention is based on the discovery that 10 plained. An ionic exchanger is usually represented in ion exchange material for example the synthetic ' the form of a unit or cell containing a bed of the resinous kind, will selectively take up from the exchanger material proper which is usually gran sugar-bearing solution certain non-sugar con . ular. An exchanger has the ability to absorb stituents in accordance with certain affinities ex isting between respective constituents and the 15 from the solution an ion of an ionized solute and to give off into the solution in exchange an ion exchange material. More speci?cally with re of another kind even though of like electric spect to a?inities such exchange material dis charge. Therefore, cation exchangers as‘ a class criminates ‘between inorganic non-sugar ions and exchange positively charged ions, whereas anion organic non-sugar constituents, as has been set forth in the co-pending patent application of 20 exchangers as a class exchange negatively Rawlings Ser. No. 479,093. ' ‘charged ions. . As the solution is passed through and contacted with the ion exchanger bed, the direct exchange and recovery of organic non-sugar constituents of respective ions between the solution and they and more particularly of nitrogenous constitu ents, asmore speci?cally exempli?ed by betaine, 25 exchanger continues until the exchanger is satu The Rawlings invention proposes the isolation from the solution. The isolation and eventual recovery is effected by utilizing the preference of the exchange material for the inorganic ions over the organic constituents. Accordingly there re rated with absorbed ions and its exchange ca pacity thus exhausted. The exchange capacity can then be restored by treatment of the ex changer with a suitable regenerant solution. sults a stratification or zoning in the exhausted 30 The saturation on the one hand, and the regen eration on the other hand, represent the main exchanger bed of respective heterogeneous non phases of the operating cycle of an exchanger, sugar constituents, that is inorganic as against ' whereby the exchanger may be used over and over the organic constituents. The Rawlings inven again.- The chemical reactions involved in the tion proposes to pass, for instance, sugar juice through an ion exchange bed until the in?uent 35 operating cycle are reversible equilibrium reac tions. end portion thereof has__become saturated with The treatment method for attaining the fore inorganic ions and the e?iuent end portion with organic constituents, and to discontinue the pas sage of the solution thus being treated before any going objects involves broadly the passing through an active ion exchanger bed of a solu appreciable portion of the organic constituents is 40 tion having ionized matter desired to be isolated therefrom for collecting in that bed the ions‘ of displaced from the eiliuent zone. That is a con such material, then removing such ions from the tinued ?ow of the solution through the exchanger exchanger bed in the form of a salt or a mixture .bed would cause a corresponding growth in depth of salts. ‘ of the zone of inorganic ions in the bed, at the The objects proper of this invention are at expense of the zone containing the organic con 45 tained by treating a solution containing a mix stituents in the e?iuent portion of the bed. With ture of solutes with ionic exchangers and utiliz the bed thus retaining substantially a relative ing in a special manner certain selective or pref maximum of the desired organic compounds from erential exchange characteristics thereof, in or the solution, the organic constituents are then displaced from the bed by means of another so 50 der to e?ect the desired isolation or fractionation of certain ionic constituents of the solutes in the lution containing ions having greater a?nity to form of ‘salts or otherwise. the exchange material than is possessed by the Such a fractionation problem occurs for in organic constituents, with the result that these stance in connection with the puri?cation treat— displaced constituents can be intercepted in rela tively high concentration in the corresponding 55 ment of sugar bearing solutions, or sugar juices . 2,418,791, 4 3 such as obtained from beet or cane, when it is de sirable to isolate, for instance, such values as po tassium, aconitic acid, betaine and others' from the bulk of impurities dissolved in the juice, and constituent may move up or downin the order of a?‘inities with respect to the exchanger. Thus the order or af?nity of two constituents with re which may also include Ca, Mg, Na and others. The invention is therefore herein illustrated by‘ referring to the ionic exchange treatment of sugar juice, and such exempli?cation is herein not to be taken in any limiting sense. change of their relative concentrations. The apparent growth of the various strata is, spect to an exchanger may be reversed by a in reality, a ‘sequence or chain of successive ionic displacement actions, inasmuch as the growing - top stratum displaces a portion of the subsequent Ionic exchange materials have inherent. tothem 1 a natural order of exchange a?inity with respect to various ionic substances contained in the solu tion. For instance, they have a preferential ac tion for the alkaline earths, such as Ca and Mg over the alkali metals such as represented by K and Na, all of which may be contained in vary ing degrees as so-called impurities in sugar juices. Hence, from sugar juices the alkali metals with potassium as a value may be recovered separate from the alkaline earths. Acom'tic acid and be taine may also be recovered from sugar juice. More generally speaking, and in view of what stratum of ions of another constituent, which in turn passes the displacement on to the next stratum that is inferior with regard to its af?nity to the exchanger, and ‘so on down to the bottom stratum of the bed. In this way, as the respec tive strata or bands of the various ionic constitu ents widen, they also appear to be shifting down wardly through the bed until even the bottom stratum of the bed will have been saturated with the constituent of lowest a?lnity, at which time the basic exchange capacity of the exchanger will be considered as exhausted. - Just as there manifests itself a scale or order of a?inity between various ions and the exchanger during the saturation phase, so does the ex characteristics, the progress of exhaustion of the bed can perhaps best be visualized,‘ as follows: 25 changer conversely exhibit a correspondingse lective reluctance or discrimination in releasing The exhaustion or saturation of a fresh ex di?erent ions under the pressure of ions of greater changer bed with the solution ?OWiIlg downward has just been said with respect to the preferential ly therethrough proceeds in continuous fashion from the top to the bottom of the exchanger body. Hence, there exists, approximately speak a?lnity during the regeneration phase. That is to say, if an exchanger bed has been saturated 30 with a variety of ionic constituents taken up by ing, a dividing line or relatively narrow zone of the exchanger in a corresponding sequence of transition between the upper exhausted or satu strata of the bed, when regenerant solution is started through the exchanger bed the ?rst part or fraction of the spent regenerant solution will contain predominantly those ions for which the exchanger has the lowest a?inity, and sequen tially thereafter will contain theions for which, the exchanger has greater ai?nity. Again, this sequential discharge of various kinds of ions rated portion of the exchanger body and the lower non=exhausted or non-saturated portion of that body. This dividing line or zone keeps shifting downwardly through the exchanger body as the continuously ~through-flowing ‘solution leaves an increasing exhausted exchanger portion behind as it advances through a correspondingly decreas ing portion of non-exhausted or still active ex 40 is due to a chain or sequence of ionic displacement actions, all in equilibrium with each other, where changer. However, as the dividing line is not by the regenerant solution displaces ?rst the ions necessarily a sharp one, there will be noticed a in the top strata, which have the highest a?inity slowing down of the exchange intensity as the to the exchanger. The displaced ions of the top "break-throng " point of the exchanger is being approached. This is a warning that the fresh or 45 strata in turn displace a molar equivalent of the ions of the subsequent strata, that have a lower regenerated exchanger should be substituted for degree of a?inity to the exchanger, and so on the one nearing saturation. The regeneration of through the bed until again equilibrium is reached a bed proceeds in a similar manner through the as the ions available for exchange in the regen bed. solution will then all have been taken up Now, after theexhaustion of the exchanger 50 erant by the exchanger. has proceeded part way down the bed, there will Considering these preferential displacement or have been formed in the exhausted portion a equilibrium conditions, it is possible according number of strata corresponding to various ionic to this invention to cause the discharge and isola constituents that are being collected in the ex tion of ions present in a bottom strata of an ex changer, the sequence of the strata correspond hausted exchanger bed, by sending through the ing to the order of a?inities of the constituents bed a solution containing ions adapted to displace with respect to the'exchanger. That is to say, any of the ions in the strata above, that is'to say, the constituent having the greatest a?inity will by causing a displacement from the upper strata be found to be substantially represented in the top strata, with the other constituents following 60 of the molar equivalent of the bottom strata ions to be isolated. Thus, if a solution is passed in subsequent lower strata in the order of their through the exhausted exchanger bed, containing a?inity. As the solution continues to ?ow and a suitable concentration of cations having a the exhaustion proceeds accordingly, the various greater a?inity to the exchanger than the ions strata will appear to grow in depth until their aggregate depth will occupy the total e?’ective 65 ‘already present in the top strata, there will take place a corresponding molar displacement down depth of the bed, at which time the exchange wardly of the top strata ions, which displacement capacity of the bed is to be considered exhausted. _will be passed‘on through the strata further be The depth of the individual strata is substan low and, as a result, a corresponding molar tially proportional to the degree of concentration of the respective constituents in the solution. 70 equivalent of ions from the bottom strata will eventually be discharged in the spent solution The sequence depends upon the a?inity of the constituents with respect to the exchanger, but and recoverable therein as the desired fraction. More speci?cally, let it be assumed the total such sequence may vary with the concentration. ' That is to say, as the concentration of a constitu ent in the solution is increased or decreased, that depth of an exhausted cation exchanger bed con sisted of three strata or bands of equal depth, the 2,418,701 upper one representing ions of greatest ailinity to the exchanger, the medium one representing ions or medium a?lnity, and the lower or bottom strata representing ions or relatively lowest af ?nity. It a solution were then sent downward through the exchanger bed, the solution contain ing solely cations or the type of the ?rst strata and containing them in a suitable concentration contacted with an anion exchanger bed or cell that operates in the hydroxyl cycle. In passing through the anion bed, the negatively charged ions of the dissolved salts or the juice (called anions) are exchanged for the hydroxyl ions of the bed until the anion bed becomes saturated with sulphates, chlorides and the like anions. Thereupon the saturated anion bed must be re generated by contact with some ionized alkali ‘and in a quantity representing the molar equiva lent of the cations already present in the upper 10 hydroxide or carbonate, especially sodium hy droxide or carbonate. During regeneration, the strata, then the cations of that solution would reverse equilibrium process takes place, namely, have no e?‘ect upon the ions of the same kind or the residual chloride and sulphate anions in the a?lnity order in the top strata. But they would bed exchange with hydroxyl ions or the basic re displace the intermediate strata of lower ai?nity, generant so that the collected negative ions or which in turn would displace the ions of the lower anions ?ow from the bed until the anion bed is or bottom strata of lowest a?inity, and then the substantially re-charged with hydroxyl ions. In molar equivalent of the ions displaced from the passing through the anion bed. the juice is sub bottom strata would be found in the spent solu stantially rid of its negative or acid forming an tion as an isolated. fraction. In this way, by sending a predetermined solution through the 20 ions since they have been left in the exchanger. Thus, the basic or positive ions of the juice are exhausted bed, a desired bottom fraction or removed from it while passing through a. cation the ions in the exchanger bed can be dis exchanger bed and the negative or acid forming placed therefrom and intercepted or isolated ions are removed from it while passing through a for the possible recovery of the isolated ions as salts or otherwise. In principle then, it is only 25 subsequent anion exchanger bed. In other words, the cations of the salts are replaced by H-ions (in necessary that the solution to cause this displace the hydrogen ion cycle) while the anions of the ment have ions of greater a?inity to the ex salts are replaced by OH-ions (in the hydroxyl changer than the ions to be isolated, and have ion cycle), with the net result that the salts are them in a quantity corresponding at least to the , molar equivalent of the ions to be displaced. 30 replaced with HOH (or H2O‘), that is the molar equivalent in pure and evaporable water. Other This invention has also ,to do with beds that substances are also removed from the juice by make use of granular ion exchange material that this particular treatment, that surprisingly are is of organic nature and is of that type now new non-ionic, such as color imparting constituents ly called organolites in distinction from the in organic base exchangers heretoiore known as 35 and colloids. In a particular embodiment the invention also zeolites. Organolites are being proposed cur comprises a system of countercurrent regener rently, for instance, in sugar making, a use that ation whereby an unexpected economy can be will now be described as an example by which to realized with regard to the operation of the frac convey an understanding of the ionic environ ment of this invention, and of‘ the chemical ex 40 tionation steps proper of .this invention. The principle of countercurrent regeneration per se change mechanism involved in the use of the ex changers. In extracting non-sugars and espe cially dissolved salts from sugar making juice or syrup, two main types of ion-exchange beds are ’ used. has been disclosed in the patent application of F. N. Rawlings Ser. No. 383,087, ?led March 13, 1941. Countercurrent regeneration permits of One that is called the cation exchanger 45 far-reaching utilization or conversion of the re bed is characterized by its use of ionic exchanger material that operates on the hydrogen ion cycle and is adapted to collect from the juice positively generant solution, and in other words, makes possible a high e?iciency of regeneration. A spent regenerant solution that is well converted will in turn make possible certain economies in charged ions (called cations) represented gen erally by-calcium, magnesium, sodium and po 50 conjunction with the fractionation of solutes ac tassium. ' That is, as juice is supplied to the ca tion' exchanger bed (or cell that contains the bed) so as to pass through it and out therefrom,,ca cording to this‘inventlon, as will be further ex plained. Because of this importance an outline of countercurrent regeneration is given as fol lows: , _.tlons Of dissolved salts of the juice exchange This countercurrent regeneration procedure es themselves'for hydrogen .ions of the exchanger 55 sentially means that, in order to regenerate an until the exchanger bed becomes exhausted of its exhausted exchanger, the exchanger is ?rst con exchange capacity and is so saturated with ca tacted with a largely, but not entirely, spent so tions that it ceases substantially to exercise fur lution obtained from a previous exchanger treat ther- exchange activity. Thereupon the cation bedv must be regenerated by contact with a regen 60 ment. This solution would contain on the one , erant-in the form of an ionized strong acid such vas hydrochloric or sulphuric acids. During re hand some of the salt, base or acid used for re generation, and on the other hand some of'the resultant products of regeneration. This solu tion contains the unused regenerant chemical in up by the exchanger with hydrogen ions of the 65 a relatively low molar concentration which, how ever, is high enough to initiate the regeneration acid regenerant so that the cations ?ow from the of, or to partially regenerate, the exhausted ex bed until the bed is substantially completely re changer. Because this partly spent solution is charged with hydrogen ions. the ?rst one to be applied to the exchanger, it Juice that passes from the cation bed has had its impurity content of cations substantially re 70 shall herein be called the ?rst stage regenerat ing solution. ~ When this partly spent or ?rst stage moved and replaced by a molar equivalent of hy drogen ions, but it .yet contains sulphates, chlo- ‘ regenerating solution is passed through the ex changer the remainder of the unused regenerant rides and other such negative ionic impurities. chemical in the solution will have been largely So the .juice substantially ridof its positive ionic converted to the products resulting from regen _ or cation impurities that have been left behind, is generation, the reverse equilibrium process takes place in the exchanger, namely, the cation taken 2,413,791 7 . eration. An exchanger so treated will be per tially regenerated. I 8 organic' matter, or as it were, nitrogenous matter and-notably betaine may collect in the e?luent end portion of the cation exchanger bed in ap_ . After the ?rst stage regenerating solution has been contacted with the exchanger bed, the bed preciable quantity. Subsequently therefore, such matter will be found in relatively high concen is given a. second treatment with a fresh regener ating solution to complete the regeneration. The tration in the initial portion of spent regenerant liquor ?owing from the bed. Intercepting that solution resulting from this completion of the regeneration becomes the partly spent or ?rst . portion of the e?luent represents a way of iso stage regenerating solution to be used as such in lating and recovering in relatively high concen the treatment of the next exchanger bed to be 10 tration such organic or nitrogenous matter. regenerated. More in particular, such by-product values as What has just been desribed may be called a betaine are thus recoverable from a cation ex two-stage process, but correspondingly three or changer bed through which the sugar juice is more stages can be used. Accordingly, there may passed. , be used successively a second and third stage 15 The objects of this invention are attained by sending or recirculating spent regenerant solution partially used regenerating solution of consecu tively greater strength, having been subjected to corresponding smaller degrees of conversion. The through exhausted exchangers from which ions tion of suitable strength. which are to be isolated or fractionated. or the lower strata of the bed are to be isolated. solution used in the last stage of regeneration This spent solution herein also termed the auxil of this exchanger is strong enough to effectively 20 iary solution, contains a proportion of ions the complete the regeneration of the exchanger, and a?im'ty of which to the exchanger is greater than this solution may be in the form of fresh solu the affinity of the ions in the bottom strata, and The essence of the There countercurrent regeneration is that the strong fore, the ion in the auxiliary solution passing regenerant solution is re-used by passing it in ef 25 through the bed will cause the displacement of fect through a succession of exchanger beds in various stages of regeneration. That is to say, the strongest regenerant solution contacts the least exhausted bed, while the weakest regener ant solution contacts the most exhausted bed. 30 The regenerant chemical in the solution is ac a molar equivalent of ion from the bottom strata of the bed, which displaced molar equivalent rep resents the fraction of the ions to be isolated. This fraction can be further treated as by con centration, or otherwise, in order to e?ect re covery of desirable values therein. cordingly stage-wise converted while the total molar concentration in the solution remains sub Some features of the invention relate to the conditioning or chemical adjusting of the spent stantially constant. regenerant solution, for the purpose of obtaining It is desirable that the exchanger bed be sub 35 a suitable auxiliary regenerant solution to effect merged in liquid at all times, so that no air will the chemical exchange displacement desired in become entrapped in the voids of the bed. There the exchanger bed to result in a desired fraction fore, the regeneration is conducted in such a man ation or isolation of ions therefrom. This in ner that one fraction of the regenerant solution volves neutralizing or partially neutralizing re is displaced from the bed by the next stronger 40 sidual or unconverted acid or alkali in the spent fraction. After the fully regenerated condition regenerant solution and also adjusting the dilu of the exchanger has been reached, the exchanger tion prior to applying this auxiliary solution to must be washed free of the regenerant solution the exhausted exchanger for the purpose of frac in it, that is to say, the remaining volume of tionation. strong regenerant solution that still ?lls the voids According -to another feature the fractionation in the exchanger, must be displaced by wash wa of ions from an exhaustion exchanger bed, is ter, whereupon the exchanger is again ready for functionally coupled with a countercurrent re use. generation system such as above referred to, by While the exchanger material takes up from means of which spent regenerant required as aux the sugar juice inorganic ions by way of ionic 50 iliary solution is obtained in a condition in which exchange, it also takes up dissolved organic mat ter or impurities including nitrogenous matter. In that instance and when using for instance such exchanger materials as organic synthetic resins, the exchanger material is found to have 55 an a?inity or preference for the inorganic ions over the organic matter. This order of a?inity manifests itself in that an exhausted exchanger bed will have accumulated inorganic matter at the in?uent end portion, whereas organic mat it is so well utilized or converted as to require a relatively small, if any, amount of neutralizing agent to condition it as auxiliary solution to be applied to the exhausted exchanger bed for the purpose of fractionation. Still other features relate to the fractionation or isolation and recovery of by-product values in connection with a puri?cation treatment by means of ionic exchangers of sugar bearing juices 60 or syrups. Some of the potential values recover able from sugar juice as a source, are potassium, ter will have accumulated at the e?iuent end por betaine, aconitic acid and various nitrogen-bear tion, under the condition that the flow of juice through the bed should have been maintained for ing matter. . As illustrative of a form of construction by a period of time adequate to produce that phe nomenon. That is to say, the exhausted condi 65 which the invention hereof may be realized, ref erence is made to the accompanying drawings tion of the bed as herein considered is that con constituting a part of this speci?cation, and in dition which results when the period of juice ?ow which drawings: from the bed has been long enough to have caused Fig. 1 is a diagrammatic example of the prin a desired quantity of the organic matter to be accumulated in the e?luent portion of the bed 70 ciple of ionic displacement induced in the ex changer bed, to effect fractionation of constitu but not so long as to have caused the thus ac cumulated organic matter to be again displaced ents therefrom; from the bed and into the spent liquor owing to Fig. 2 illustrates the invention more fully as applied to the regeneration phase of organolite the excessive growth of the strata of inorganic matter accumulating in the bed. In this way, 75 cation exchanger bed that has been saturated 2,413,791 9 . 10 - with non-sucrose impurities in the process of invention, are substantially stable in the presence sugar juice puri?cation treatment. So that the underlying principle of this inven tion may more readily understood, there is ‘shown in Fig. a general diagrammatic example of acids and alkalis. of how a variety of ions, for instance of the ca tion class, range themselves'in strata in the ex- , changer bed, in the order of their aiiinity of theirexchanger, and how subsequently they can be fractionated or isolated by controlled ionic displacement whereby the ions of lower affinity are displaced by ions having greater amnity to the exchanger. ‘ a ‘ » Other suitable organolite exchangers are: The I cation exchanger produced by the Resinous Prod ucts Corp. of Philadelphia under the name or identi?cation of Amberlite 1R.1, and the anion exchanger Amberlite 1R.4 from the same source. The invention is represented in Figure 2 in connection with the regeneration phase of a ca tion exchanger of the organolite class,‘ the ex changer bed being designated as B. However, it is to be understood that the invention can be applied as well to an anion operating cycle, and Referring to Fig. 1, let 50% of the capacity of Y also in connection with the use of zeolites. A solution such as sugar juice containing a a fully exhausted exchanger bed \be saturated 15 with Na-plus Ca-ions, corresponding to half the mixture of solutes or non-sucrose impurities is assumed to have passed through the exchanger bed B leaving the bed in the exhausted condition a. Let the lower half of the bed X be saturated indicating in Figure 2 that various ionic constitu with K- and with NHa-iOns so strati?ed that K occupies a stratum or band b of 25% of the depth 20 ents have been taken‘up by the exchanger in con secutive strata in the order of their a?lnity to the of the bed, and NH: occupies the remaining 25% exchanger. By way of example, the exchanger below. ‘ _ bed is herein shown to have the top stratum satu Let'it further be assumed that another ex rated with Na and Ca ions, and to have potassium changer bed Y of equal capacity be saturated and exhausted throughout with Na-plus Ca-ions from 25 (K), ammonia (NHs), and betaine, respectively, in the strata below. The aggregate depth of these a previous operation. If this bed Y is then re strata represents the total depth of the exchanger generated with _HCl solution design‘ ted as S, bed. then the spent regenerant liquor ?o ing from depth of the bed represented by the top stratum The constituents K, NHa, and betaine, present the bed may be considered as ti?ztliary solu tion since it contains all theNa p/s Ca which 30 in the respective three lower strata arethe ones to be fractionated or isolated eitherin bulk or it has displaced from the bed i/ change for H each of them individually. That is to say, de ion. If 50% total Na-plus Ca-ions removed from pending upon how the fraction of fractions are the exchanger bed Y and present in the spent to be intercepted in the spent liquor ?owing from regenerant solution R is then sent downwardly the exchanger bed, one may visualize either a sing 35 through the exhausted exchanger bed X, it will gle fraction being intercepted that contains all pass substantially inertly through the upper three constituents, K, NHa, and betaine, or each stratum a because ‘of the presence therein of the of these constituents as being intercepted as an Na and Ca. But in passing through the further individual fraction. Other possible variations are strata b and cit displaces therefrom the K- and to-have the betaine isolated in the ?rst fraction, NHfi-iOHS because of the greater a?‘inity of the 40 and the NH: and K together in a following frac Na and Ca to the exchanger. The displaced K tion, or vice versa, the betaine and the NH: might and NHs-iOl’l will then be found present in the be'isolated together in a ?rst fraction, with the spent solution flowing from the exchanger bed _ K alone to follow in the subsequent fraction. X: as the bed X is left fully saturated with Na If the betaine, which is substantially present and Ca and thus in a condition to be regenerated in the bottom strata of the exchanger bed, is the with HCl solution and utilized in the manner of sole value sought to be isolated and recovered, bed Y in a subsequent operating cycle. The dis then a corresponding ionic displacement must be placed K- and NHa-ion are represented as volume effected for recovering just that constituent in F in terms of spent solution, and that volume 50 a corresponding fraction of intercepted spent represents a fraction comprising the K- and NH; ion desired to be isolated. The ?ow-sheet of Fig. 2 illustrates the inven tion as applied to the problem of fractionation or by-product recovery incident to the ionic puri? cation treatment of sugar juice by means of or ganolites, that is the isolation of values from the impurities removable from the juice by the ionic exchange treatment. - ‘ liquor. , Since the isolation of‘ the three constituents each individually-K, NH:;, and betaine—is here in taken as an example, there are consequently provided three interceptor or fractionation tanks III, II, and I2, to receive the respective fractions of spent liquor. Furthermore, there are provided tanks l3, l4, l5, I6, for receiving regenerant solution in various One of a variety of organic cation exchangers 60 stages of conversion,- such as occur in the prac considered suitable for the present purpose is of tice of counter-current regeneration aforemen the resinous type such as exempli?ed in the tioned. In this system, tank l3, for example, re-v United States pa nt to Holmes No. 2,191,853, ceives a 5% fresh regenerant HCl solution, tank where the excha ger is described as a synthetic I 4 a partially converted or once-used regenerant resin of the polyhydric phenol formaldehyde type 65 ‘solution obtained from a‘ previous regeneration which is sulphited to a degree such that its sul phur content is not less than 2.4%. An'organic anion exchanger considered suitable for the pres cycle, tank IS a still further converted or twice used regenerant solution from a previous regen eration cycle, and tank IS the spent regenerant ent purpose is also of the resinous type and is solution containing residual unconverted chemi exempli?ed in the United States patent to Adams 70 cal too dilute for use in a. further regeneration and Holmes No. 2,151,883, describing the ex cycle. For example, in counter-current regen changer as an insoluble resin-like product ob eration a 5% HCl regenerant solution may be tained by the reaction of formaldehyde with an convertedto about 1 to 1.5% HCl content with aromatic amine. Exchangers of the type con regeneration of the bed proceeding effectively. templated for use in connection with the present 75 whereas straight regeneration (that is regenera 2,418,791 12 iion of an exhausted exchanger bed directly with fresh or strong 5% regenerant solution) could by tion serves as auxiliary regenerant solution in the fractionation steps, the balance to be discharged comparison be carried only to about 2 to 2.5% H01 content in the spent liquor. The spent re generant solution, according to this invention, from the system through line 44. Valves 45, 48, 41, also connected with the header 40a admit spent liquor fractions containing K, NHz, and serves as an auxiliary regenerant solution for ef betaine respectively into the interceptor tanks l0, fecting the ionic displacement from the exhausted II, and I2 respectively, which tanks in turn are exchanger bed B of one or more fractions repre provided with bottom discharge valves 5|, 52, 53, and with corresponding discharge connections senting di?erent ionic constituents. This dis placement is e?’ected due to the contents in the 10 51a. 52a and 5311. There is also provided a tank 54 to receive used wash‘water from the exchanger spent or auxiliary regenerant solution of a pro bed, through the header 40a and a valve 55. The portion of ions of a higher order of a?inity to the tank has a. discharge valve 56 and discharge con exchanger than is possessed by the ionic constitu nection 51. A goose-neck G through which the ents to be fractionated from the exchanger. The liquid discharging from the exchanger bed B must interceptor tanks III, II, and I2 may be oper pass, is so designed as to normally insure sub ated to receive the spent liquor fractions contain~ mersion of the exchanger material at all times. lllg the K, NH3, and betaine respectively. The goose-neck G has a vent 58 to break the There is further provided a tank 20 to which syphoning effect thereof. the spent regenerant solution from tank Hi can be transferred after the residual regenerant 20 Operation chemical (HCl) has been neutralized, and other Inasmuch as the principle of ionic displacement wise conditioned as with respect to its dilution, so herein employed will be clear from what has been as to serve more effectively as the auxiliary re said in the foregoing with respect to Fig. 1, it will generant solution. Hence, there is also shown suffice to describe the operation on the basis of a measuring tank 2i for dosing a neutralizing the ?owsheet in Fig. 2 pertaining speci?cally to agentsuch as an acid or an alkali as the case an example in which an organolite cation ex may be, and a measuring tank 22 for diluting changer is exhausted incident to the puri?cation water. A measuring tank 23 supplies the required treatment of sugar juice, whereby dissolved non dose of fresh regenerant acid (HCl) to make up the fresh regenerant solution in tank l3. 30 sucrose impurities or salts are removed from the juice, that is to say, sugar juice has been passed A header 24 supplies regenerant solution in downwardly through the cation exchanger, consecutive stages from the various tanks I3, l4, whereby the exchanger has become saturated with l5, and 20, by means of a pump 24a to the top a variety of cations in strata corresponding to of and onto the exchanger bed B, connections the ailinity of the respective cations to the ex being provided between the header and the re changer. In this example Na- and Ca-ions are spective tank bottoms. A discharge control valve found largely in a top stratum of appreciable 25 is provided for the fresh solution tank l3, a depth, while the strata below are represented by valve 26 for discharging once-used solution from K, NHa, and betaine respectively. At this point tank l4, and a valve 21 for discharging twice-used solution from tank l5. A valve 28 is provided for 40 of the operating cycle the tank 13 should be assumed to have been ?lled with the required vol discharging neutralized spent liquor (that is ume of fresh acid (HCl) regenerant solution of. auxiliary regenerant solution) from tank 20 to say, 5% concentration. At the same time, tank the exchanger bed. Wash water for the ex14 is assumed to be ?lled with what is herein changer bed can be admitted into the header 24 45 called once-used regenerant solution such as has through a valve 21A. been obtained from a previous operating cycle. Provision is made for the spent liquor solution and tank I 5 should be‘ ?lled at this time with from tank I6 to be transferred through a con twice-used regenerant solution, also obtained as trol valve 29, a pump 30, pipe connections 3| and such from a previous operating cycle. Tank [8 is 32 and another control valve 33 to the tank 20. A portion of the spent regenerant solution from 50 emptied at this time, but tank 20 is ?lled with spent regenerant solution from a previous cycle, the cyclic system is sent to waste through a dis which spent solution according to the invention, charge connection 34. The admission of a regu should have had its residual or unconverted acid lating dose of alkali into the measuring tank 2i (HCl) neutralized and its dilution adjusted so is controlled by a valve 35, and into tank 20 by a valve 36. The admission of diluting water into 55 that it represents auxiliary regenerant solution suited to the exchange characteristics of the ex the measuring tank 22 is controlled by a valve 31, changer and for the present purpose of fractiona and into the tank 20 by a valve 38. The admis— tion which is the object of this invention. sion of fresh make-up acid (HCl) .into the meas At this time the voids in the exchanger bed B uring tank 23 is controlled by a valve 39, and into the tank 13 by a valve 40. 60 are assumed to be ?lled with residual wash water which now must be displaced downwardly from Furthermore, there is provided a supply header the bed incident to the passage therethrough of 40a for admitting regenerant solution in various the neutralized spent regenerant solution. The stages of conversion, leading from the bottom of displaced wash water may be intercepted in tank the exchanger bed to the respective tanks I3, [4, l5, and I 6. The admission of strong solution into 65 54 into which it can be admitted through the valve 55. At the proper time the ?ow of liquid tank I 3 is controlled-through a valve 4|, and the discharging from the exchanger bed is switched exact source of this strong solution or of por to and through the valve 45 into the ?rst inter tions thereof will herein be further explained. ceptor tank It], that is, when the residual wash Once-used solution from the exchanger bed is supplied to the tank I! through a valve 42, to be 70 water has been displaced and the spent liquor further utilized in a subsequent exchange cycle. ' fraction containing the betaine begins to flow from the bed. In this way, the betaine-contain Twice-used solution is supplied into tank I5 through a valve 43, also for use in a subsequent ing fraction of the discharging spent liquor is in cycle. Spent regenerant solution is supplied to tercepted in tank III until the content of the dis tank l6 .through a valve 44, part of which solu 75 charging liquor begins to change from betaine to ‘2,413,791 solution ' as ‘auxiliary ' the discharging spent liquor is switchedthrough solution for ' pump 30 through lines 3| and .32 and through valve 33 into tank 20 where the residual uncon verted acid (HCl) inv it is neutralized with a suit able alkali from the measuring tank ii, and the solution diluted,‘ if desired, from the measuring 'now the out?owi'ng“ NHaécontaining "fraction ac cumulates. In a vsimilar manner the. flowis then again switched throughva-lve '4], into thethird interceptor tank l2 in which to accumulate the tank 22. The balance of the spent regenerant K-containing fraction of the spent liquor. When . 10 solution coming from the tank [6, andnot needed, this latter fraction has been substantially inter ’cepted, the flow from tank 20 of auxiliary re -' regenerant effecting the fractionation as above described, is ' - sent through discharge-valve 29 by means'or the '- ’ valve“ into the second interceptor tank H where > - 14 ' '- Nmwmtnls the next constituent to be inter_ 1 vcepted- and isolated. . Consequently, at this point . begins to discharge from the system as indicated by the line“, The discharge line 34 is formed with a gooseneck J through which spent regen generant solution through-the bed is stopped, as > the exchanger bed 'will now have ‘been saturated 1_..substantially through its entire depth with Na erant solution from tank I6 begins to ?ow when ? - and Ca-ions assumed to have been present in suf - ' i‘lcient quantity in the auxiliary regenerant solu 15 the valve 33 is closed while the pump 30 ‘continues tion-to effect the displacement and fractionation running. The goose-neck J has a vent 34a to break the syphoning 'e?ect thereof. The spent ofthe-K, NHs, andjbetaine as-just described. ' regenerant, solution that has been conditioned ‘ ._ , -,From what has beenusaid‘ before about the ‘ into neutralized spent solution in tank 20 is then ' J im'e'chanism of successive displacement ,e?ects in 20 ready‘to be used over again as auxiliary regen erantsolution in a new ‘cation exchanger oper - ' the exchanger bed B, ‘it will be understood why , ating cycle. ~ ‘ - thefractions representing the various constituents Since through dilution (note the regulating vdischarge from thefbed in the‘ order described. That is tosay, the Na- and Ca-ions su?iciently ; water valve 31) one may vary the relative a?‘inity ' of the ions in the auxiliary regenerant solution with respect to the exchanger, it can be visualized that by such control the ions in the auxiliary ‘regenerant solution may be assigned a desired‘ ' -'juice puri?cation treatment, but in continuing '_ place in the order of a?im'ty. Consequently, such’ ' ' 1 downward through the bed, they ?rst displace the control or vamnity adjustment should make it -’ _ K-ions which in turn displace the NHv-ions in the ‘ v:rmss‘ible to leave una?ected any desirable dept ., . next stratum,.passing the displacement further of the exchanger, and to havev the chemical dis - '1 ontothe-betaine in the bottom stratum, causing present in the auxiliary solution pass inertly through the upper strata of the exchanger, al ready saturated with 'Na"-- and 021,- from the placement action take?place, for instance, only » ' the betaine eventually to emerge from the bed as _ when the auxiliary regenerant solution substan- > the'?rst‘fraction'to be intercepted in tank i0. tially reaches the particular strata containing. '_ ‘By virtue of the same displacement mechanism, .the fraction of ions or moleculesto be displaced. . l J the'next spent liquor fraction containing the NHs, 'It is thus visuaiizedithat the auxiliary regenerant ‘ , and thethird spent liquor fraction containing the solution should ?ow substantially'inertly (that is, -> - K, are successively intercepted in tanks II and v_ [2 respectively. Finally, when all'three frac . ‘' tions'have been displacedand intercepted, sub ~10 v _' :stantially the entire depth of the bed will be ,'_ found. to have become saturated with Na and Ca. The'intercepted fractions in the tanks III, II and without exerting displacement or exchange func tion) through that depth or strata of- the bed; that overlies that strata containing the ions or molecules to be displaced as a recovered fraction. In other words, in this way one may control or . predetermine the point of depth in the bed, at .i2 can' .be, individually concentrated for the re " ‘covery of the respective values or salts. 45 which or fro-m which on, a desired displacement action by the auxiliary regenerant solution should vvIf the molar equivalent needed for displacing '_ \thefthre‘e fractions K, NH; and betaine, is known, '_ be effected. ' > . ,- , ' . The twice-used or largely converted regenerant ' ' then it is possible to predetermine the volume and .‘char'a'cter' of the auxiliary regenerant solution, [that is, the neutralized spent regenerant solution solution from tank I5 passing through the bed have caused the initial regeneration of the exchanger bed with I-I-ion. Any of the residual 50. will (‘which must be sufficient to effect the desired dis placement and fractionation. Following directly .iupon this auxiliary solution e?ecting fractiona tion, there is then passed through the exchanger second-used solution in the bed is then followed up with and. displaced by once-used, that is, less converted, regenerantv solution from tank H, in Ijfbed the twicesused ' (that is. largely converted)” 55' order to furtheradvance the regeneration of the, exchanger bed. Consequently, there will now ?ow 1-regenerant'solution from tankv l5 from which it , is‘drawn thru the valve 21 by the pump 24a. » from the. bed a solution equivalent in HCl strength This twice-used solution will displace from the to twice-used-solution and as such it is discharged through valve 43 into the now emptytank l5. ' .3. bed ‘any of the'aforer'nentione'd spent liquor frac The residual solution from. thisregeneration '' ,tions or else any excess or residual unconverted 60 ~ strong regenerant solution from tank l3>to ?nish.‘ ; : '- emergesirom the bed as'true spent regenerant , ‘solution which as such will containv largely Ca and ~ ~Naas chlorides due to initial regeneration now taking place inthe bed to the extentJthat the ~_H—'ion's ‘of the regenerant acid '(HCl). ‘are avail ‘ ablein-the twice-used regenerant solution; This bre'ak 'or-‘interception means that: what new ?owingfrom the bed when this final regen-v' 6,5 now crant solution emerges with the HCl content reduced to what is, equivalent to once-used solution, . ' ' 1 and as such, it is sent to the new empty tank _' it for use in a subsequent operating cycle, while being followed up with and displaced by wash twater?from the header 24. _ However, when the - ‘ regeneration of the exchanger bed from'top to -' .valve 44 into the-empty spent regenerant solution tank .l6. . 'interception’is the regeneration made of the with bed. respect-to Again the the break solution.‘ or - '~' . ~_ _ ~_-Y_lemerges from .the bed as'true spent-‘regenerant solution is'sent through the header Mia-and the ' ._ v .. v _ ‘:"I'he portion needed of this spent. regenerant , step is then displaced from the bed by .‘fresh or “ ' auxiliary regenerant solution. Again the break or interception is made with ‘respect to the liquid " discharging from the bed, when'the ‘spent liquor bottom is thus-completed in this last step, the voids of the‘ .bed will still be. ?lled to some ex ‘tent with trailing unconverted HCl solution which, 9,418,791 15 - with the wash water, forms a weak solution. By continuing to pump wash water this weak solu tion is displaced from the bed and supplied through the header 40a, and valve 4| to the fresh solution tank I3 until the tank is filled to its predetermined mark. _Fresh make-up acid is then added from the measuring tank 23 to bring it up to the strength required for the fresh regen erant solution. ' 16 lution containing dissolved nitrogenous along with ionized inorganic non-sugar constituents to e?'ect the isolation of nitrogenous constituents, which comprises passing the solution through a quan tity of granular hydrogen ion exchange material substantially saturated with H-ions so that in organic constituents are retained in the in?uent zone while nitrogenous constituents are retained in the eilluent zone of the material approximate The use of counter-current regeneration in con 10 ly until nitrogenous~ constituents start to pass from said eilluent zone, then passing through said nection with this invention makes it possible to eiiluent zone an auxiliary solution of substantially conduct the step of neutralizing the spent regen the same composition as the regenerant solution erant solution with a high degree oi! economy. later produced to displace nitrogenous constitu That is to say, since the regenerant chemical (HCl) has been converted to a particularly large 15 ents in said eiiluent zone by inorganic cations, extent by counter-current operation, the small residual unconverted HCl portion in the spent regenerant solution requires a corresponding but small quantity of neutralizing agent. However, isolating a resulting eiiiuent portion containing the displaced nitrogenous constituents for the recovery of such constituents, and regenerating the exchange material to restore its H-ion ex -it is within the scope of this invention that the 20 changecapacity by passing therethrough as acid neutralizing or conditioning step be dispensed with, and the true regenerant solution from tank l6 be used-as such, that is substantially without regenerant solution, whereby therev is produced an eilluent of substantially spent regenerant solu tion substantially in the nature of said auxiliary solution. chemical adjustments, to serve as the auxiliary 2. The process according to claim 1, in which regenerant solution either with or without addi 25 the organic constituents isolated are derived irom tional controlled dilution thereof. the cation exchange material and comprise sub While the invention so far has been described stantially betaine. substantially on the basis of the chemical mech 3. The process according to claim 1, with the anism that controls straight ionic vexchange or ion displacement effects taking place in the ex 30 additional steps of neutralizing unconverted acid regenerant chemical in ‘said auxiliary solution changer, it is to be understood that the displace prior to contacting the solution with the exchange ment or fractionation, to be effective according material. to this invention with the aid of spent regenerant 4. The method according to claim 1, with the solution as an auxiliary, may also include con stituents which do not exactly follow the law 35 additional step of diluting said auxiliary solution to effect a desired degree of concentration of the herein set forth of selective or preferential ionic solutes therein prior to contacting it with the exchange. That is to say, some values to be exchange material. fractionated from the exchanger may be found 5. The method according to claim 1, in which to have been absorbed directly, that is, in their molecular state, by certain strata of the exchang 40 the regeneration is effected by ?rst passing through the exhausted material partially spent er, and it is observed that somehow these con regenerant solution obtained from previous re stituents have a place in the order of a?inity generation whereby largely spent e?luent liquor is obtained, and then passing through it stronger their place at the end of the line, namely, after 45 regenerant solution, in which said auxiliary so lution comprises a quantity of said largely spent all true ionic exchange has taken place in the liquor, with the additional step or neutralizing exchanger, and consequently such constituents any unconverted acid regenerant chemical in said may be found in the bottom portion or strata of auxiliary solution prior to contacting the solution the exchanger bed whence they may be most . readily removed or displaced by the treatment 50 with the exchange material. with respect to the exchanger. In some cases, such molecular constituents will appear to take method according to this invention. ‘ I claim: 1. The process of treating a sugar-bearing so RALPH w. SHAFOR.