claimed is: 1. A process of purifyin.- an isomerized com type conversion syrup of above about 70 D.E. and at least about 15% ketose of which at least 10% is fructose, comprising the steps of passing the isomerized syrup through a decolorizing resin of the strong base, anion exchange type. in chloride form with color absorbing properties; passing syrup from the resin through an electrodialysis chamber and removing ash from the syrup, said electrodialysis treatment including a dilution-concentration type unit of multi-membrane cells of alternate anion-cation type, separated by a spacer, an electrode stream of Na2,SO4 and a concentrating stream of 0.05 N NaCl, said treatinent bein.- at a current density of 4 to 12, a terrperature of 80-140' and a rate of 0.2 to 0.8 gal./hr./ft.2: passing the clectrodialyzed syrup through a decolorizing resin of the strong base, anion exchange type in chloride form with color absorbing properties; treating the syrup with activated carbon; and recovering a decolorized com convesion syup of less than about 0.5% ash, a D.E. of above about 70 and containing about 15% ketose of which at least about 10% is fructose; and coicentrating the syrup to about 70- 83 % sojids. 2. A pro cess of puri fyin g an iso mer ized com type conversion syrup of above about 70 D.E., and at least about 15% ketose of which at least about 10% is fructose, comprising the steps of passing said syrup throu,@ll an electrodialysis chamber and removin-g ash from,the syrup, said electrodialysis treatment being at a current density of 4 to 12, a temperature of 80-140' F. and a rate of 0.2 to 0.8 gal./hr. ft.2, said electrodialysis treatment including a dilution-concentration type unit of multi-membrane TABLEII Solids, Ash, D.E., Ketose, Fructose, Psicose, Dextrose, Percent Transinission Processing Description Percent Percent Percent Percent Percent Percent Percent 450 mA 550 mA 620 niu Feed ----------------------------------------- 41.8 0.91 75.3 24.6 20.0 5.0 44.3 None 6.0 31.0 A. Electrodialysis ---------------------------- 41.6 0.098 77.5 26. 6 ------------------ ---- 45.9 None 12.0 27.0 (B) (1) Resin treatment ---------------------- 39.4 0.099 78.0 26.0 20.1 4.1 46.1 20.0 81.5 90.0 (2) 2-2% carbon treatment ------------------ 40.0 ----------- 79.3 27.0 20.1 4.1 46.3 73.0 90.0 93.0 TABLE III Solids, Ash, D.E., Ketose, Dextrose, Pereciit Transmission Processing Description Percent Percent Percent Percent Percent 450 mg 550 niA 620 mA Feed --------------------------- --------- same as Feed of Table I---------------------------- None 6.0 31.0 Electrodialyzed liquor ------------------- 41. 6 0.098 77. 5 26. 6 45.9 None 12.0 27.0 Graliular carbon composite effluent ------ 39.3- ----------- 78.9 29.4 47.6 56.0 85.0 9010 As can be -een from the foregoing examples, the dextrose level increases slightly during purifi@,ation because of removal of traces of high molecular weight sugars by the electrodialysis membranes, the resins, and particu60 larly the carbon. While it is preferred to hold the final dextrose content below about 45% to insure that the final product is non-crystallizing, syrups of sli,-htly hi,@her dextrose are useflil if tised in a short time, and the presence of th.- fructose in the final syrups has been 6zi noted to incrcase the solubility of the dextrose so that 1--vels of destrose higher than precisely 45% are better tolerated. The decolorized product from all four examples is concentrated under vacuum to 80% solids to form a decolo70 rized, deashed very sweet corn syrlp. Thus it is seen that the present invention achieves all of the objects and advantages sotght therefor. T'bis invention is intended to cover all changes and modificatioiis of the examples of the invention herein 75 cells of altemate anion-cation type separated by a spacer, an electrode strea@m of Na2SO4 and a concentratin- stream of 0.05 N NaCl, treating the syrup with carbon and removing color from the syrup, and recovering a corn conversion syrup of less than about 0.5% ash, a D.E. of above aboti,t 70, and at least about 151 ketose of which at least about 10% is fructose. 3. A process of purifyin.- an isomerized cor@l type conversion syrup of about 70-85 D.E. and having about 10-23% ftuctose and a total of about 15-33% ketose sugars, comprising the steps of passing the syrup through an electro-dialysis chamber and removing ash from the syrup, passin.- the syrup through a decolorizing resin in the chloride form to remove color from the syrup, treating the syrup with carbon to remove color from the syrup, and recovering a com conversion syrup of less than about 0.5% ash, a D.E. of about 70-85 and having about 10-23% fructose and a total of about 15-33% ketose sugars.

7 4. The process of claim 3 wherein the electrodialyzed syrup is passed through an activated carbon bed at 0.1-5 bed/voluiiie I hr. and 70-140' F. S. The process of claim 4 includin,@,the steps of filterin-. the syrup from the carbon treatment and concentrating the syr-up from the said ftlter to 70-83% solids. References Cited UNITED STATES PATENTS 318832245 8 2,487,121 11/1949 Fetzer et al - --------- 127-36 ?,688,572 9/1954 Warshaw ----------- 127-54 2,860,091 11/1958 Rosenberg -------- 204-180 X 2,892,737 6/1959 Rohwer et al - -------- 127-- 40 5 3,276,908 10/1966 Idaszak ------------- 127- 40 MORRIS 0. WOLK, Pi-imary Examinet-. A. LOUIS MONACELL, MICHAEL E. ROGERS, Exaininers. 2,354,664 8/1944 Cantor et al - -------- 127-36 10 D. G. CONLIN, Assistaizt Exattiiiier.

United States Patent Office 31383,245 3,383,245 PR@,OCESS OF PURIFYING HIGH D.E.-VERY SWEET SYRUPS Barrett L. Scallet, C@.ayton, and Irvin.- Ehrentnal, University City, Mo., as-gi,-nors to Anheuser-Busch, I.rcor- 5 porated, St. Louis, Alo., a corporation of rviissol:ri Continuation-in-p,irt cf application Ser. No. 268,267, Mar. 27, 1963, now @-eent No. 3,305,395, dated Feb. 21, 1967, i,,hich is a continuation-in-part of appli,-ation Ser. No. 184,506, Apr. 2, 1962. This 10 application Nov. 8, 1966, Ser. No. 592,797 5 Claims. (Cl. 127-53) ABSTRACT OF TH-h DISCLOSURE 15 A process for purifying an isomerized corn type conv,-rsion syrup of above 70 D.E. in which ash is r--m. oved by -Iectrodialysis, cole@.- is removed by an ion exchanae resin in the chloride form and the syrup is treated with carbon. 20 This application is a continuation-in-part of olar copending application S.N. 268,267, filed Mar. 27, 1963, now U.S. Patent 3,305,395, issued Feb. 21, 1967, v@ ,hich 95 in turn is a contiiluation-in-part of our application S.N. - 184,506, filed Apr. 2, 1962, now U.S. Patent 3,285,776, issued Nov. 15, 1966. The present invention principally relates to process improvements concerr@ir@g the purification of isomerized 30 iiquor. Patent application Ser. No. 184,506 coi7ers the making of a high D.E. syrup by means of hydrolysis of starch with inineral acids at high temperatures and under pressure and enzyme conversion of the hydrolysate to a 70-85 @5 D.E. high gILloose liquor. The high glucose-high D.E. ' liquor is then isomerized with alkali to produce a very sweet liquor of about 70-85 D.E., 10-23% fructose an a total of about 15-3 3 % ketose sugars. The isomerized liquor having 40% solids generally also contains 0.5- 40 1.0% ash (based on the total weight of the liquor) and a high level of color bodies and de.-radation products. Ion exclusion and ion exchange a,ve then used to deash and decolorize the isomerized liquor to purify it for use as a commercial food product. 45 The purification of isomerized liqugr is the greatest obstacle to commercial development of a hi-h D.E. very sweet syrup from both an economic and technical standpoint. The purification procedures of ion exclusion and "On 50 exchange in application Ser. No. 184,506 results in yield losses higlier than are economically practical under present circumstances. Also, ur@der certain circumstances molecular exclusion occurs during ion exclusion causing some hi---her molectilar weight sugars to be retained with 55 the waste and tllus increase the dextrose and fructose level of the effluent product. These yield losses of mainly Y@igh molecular weight sugars si.-nificantly add to the cost of producing a product. Accordi-@igly, the principal purpose of the present inven- Go tion is to provide process improvements i-,l the purification of the isonerized liquor of Ser. No. 184,506 whereby the yield losses are decreased and the overall process is made more economically practical. These and otber objects and advantages will become 6,5 apparent hereinafter. The fi-,Ure shows a bloc"- flow diagram of the present process. Briefly, the process irnprovements of the present invention involving purification of isomerized liquor are as 70 follows: (1) Decolorizing Resin.-Isoinerized hi.-h D.E. liquor Patented May 14, 1968 2 (0.5-1.0% ash o-@l a 50% solids basis) is passed through a bed of strong base highly porous anion exchange decolorizing resin in the chloride form at a flow rate range of 0,5-5.0 -al./min. ft.2 and a temperature range of 60140' F. A number of stron.- base resins in the chloride form which have colcyr absorbin@ properties are satisfactory _for this purpose and includes: (a) Rohm & Haas IRA 401-S which is a hi.-hly porous strong base gel type quaternary ammonium ion exchange resin. (b) Rohm & Haas IRA 900 which is a highly porous stroiig base quatemary ammonium macroreticular ion exchange resin. (c) Duolite ES III which is a highly porous strong base quaternary ammoiium polystyrene matrix ion exchaii,-e resin, 16- 50 mesh. . A preliminary decoloi-ization is done at this stage to improve electrodialysis stack membrane life and stack efficiency in tie next step of the process. 2. Electrodialysis.-Electrodialysis is a process which involves the transfer of ions from one solution throu.-h a membrane into another solution by imposing a direct electrical current. The dilution-coicentratioii mul@timembrane c-Ils used in this process consist of membranes @ach of Nv @-@ich contains io-7i exchange groups and so gives each a positive or negative fixed electrical charge. Positive charced membranes (anionic membranes) will pass . 0 anions and repel cations. The negatively char.-ed membranes (cation membranes) will pass cations and repel anions. The membranes are separated by spacers and placed so that no two lik6 charged n-lembranes are adjacent to each other in the cell pair dilution coricentration system (i.e., membranes arra-.iged anion, cation, anion, cation, etc.). The system basically consists of an electrode and electrode membrane at each end, and a stack of charged membranes, which are basically a series of oppositely charged cell pairs, each consisting of an anion membrane, a plastic spacer and a cation membrane. The three streams in the process are the electrode st.eam (a recirculating dilute solution of Na2SO4), the dilutir@g stream (the isomerized liquor stream to be deashed), and the concentrating stream (this is the stream to which the ash is transferred consisting of 0.05 N NaCl at the stait of the run). When a current is imposed between the two electrodes, positive ions (part of the ash) will pass from the diluting stream (the syrup liquor) tbrough the cation membrane to the concentrating stream and further travel will be blocked by the anion rnembrane. Negative ions (part of the ash in the syrup) will pass from the diluting stream through an anion membrane into the concentrating stream where further lateral travel is blocked by a cation membrane. Ash removal is affected by type and number of niembrane cell pairs, current density, temperature, flow rate, numberof Dasses, etc. The liquor effl,@ent from the decolorizing column is then pumped into an electrodialysis stack assembly for renioval of 50- 95% of the ash content. Electrodialysis is conducted at a current density range ie,,@4 to 12, temperature ran,-e of 80-140' F. and a production rate range of 0.20-0.80 gal./hr. ft.2 area using 61 CZL and 1 1 1 EZL Ionics, Inc. type inembranes. These systems are described in Bulletin L-2 (Second Edition) @1963 by Ionics Iticorporated of Cambridge, Mass. Product from the electrodialysis process has now had 50%-95% of the ash removed with no appreciable change in color or sugar distribution and a minimal yield loss. 3. Decolorizing resin.-The electrodialyzed liquor is now ready for further color removal and can be passed throu.-h a bed of decolorizing resin as per step No. 1. This procedure is an altemative treatment that can be

3)383)245 3 used before carbon treatment to lower carbon consumption requirements. 4. Carbon treatment.-Liquor effluent directly from theelectrodialysis or from the decolorizing treatment after electrodialysis (Step No. 3) is now treated as follows: 5 (a) with activated powdered carbon and filtered; (b) or passed throu.-h a bed of granular carbon consisting of Pitt. Chem. CPG granular or equivalent and then filtered. Flow rate ran.-e is 0.1-5.0 bed volumes per hour at a temperature range of 70-140' F. 10 5. Concentration.-The carbon treated liquor is tlaen concentrated to a range of 70-83 % solids. Detailed process specifications: 1. Resin decolorization.-Isomerized liquor is produced 15 as per application Ser. No. 184,506. The isomerized liquor is first passed through a strong base quaternary ainmonium decolorizing anion exchange resin in the chloride form. Preferred flow rate is I g.p.m./ft.3 bed volume and a preferred temperature ran.-e of 90-120' F. I-ligher tem20 peratures within allowable resin limits permit better resin decolorizing efficiency but also risk further degradation of isomerized liquor. Therefore, an upper limit in the 120' F. area is preferred. This decolorizing step is necessary to remove some of the or.-anic de.-radation products and 25 color bodies so as to improve electrodialysis stack efficiency and maximize stack membrane life in the next step of the subject process. 2. Electrodialysis.-The liquor from Step No. I is passed throu.-h an electrodialysis stack system to rernove 30 most of the ash preseiit in the isomerized liquor. The desired final ash in the prodlict is less than 0.5% and preferably less than 0.25% of a syrup which is about 80% solids. Assuming an intial ash of 0.75% on 40% solids, 83% of the ash must be removed to yield 0.25% 35 ash at 80% solids and 67% of the ash must be removed to yield 0.5% ash in the j'inal product. The level of ash can be controlled primarily by the number of passes made through the electrodialysis system at a given set of conditions. The prcferred current density is ie,=4 to 6 and the 40 preferred temperature is 110'-140' F. Production rate for 90% ash removal of 0.91% ash from 40% solids liquor is 0.33 gal./hr. ft.2 at 110' F. and ieo@4 and 0.53 gal./hr. ft.2 at ie,,=4 and T=140' F. Yields are better than 97% and energy constimption for 90% asli renioval 45 of 0.91% ash from 40% solids feed liquor at ie,,@4 is 0.035 kwh./gal. liquor. The electrodialysis step has deashed the liquor, removed traces of color and yields as effluent of essentially the same sugar composition as the feed. 50 3. Resin decolorizing.-The electrodialysis effluent liqSolids, Ash, D.E., Processing Description Percent Percent Percent Feed (isonierized liquor) --------------------- 41.8 0.91 75.3 A. Resin Decolorizing ------------------------ 41.0 0.87 75.2 B. Electrodialys'@ ----------------------------- 41.3 0.095 77.4 C. Resin Decolor,zing ------------------------ 38.9 0.098 77.6 D. C@,rb.. Treatment (2-2% carbon treatments) ------------------------------------- 40.1 ----------- 78.2 uor can now be passed through the same - decolorizing process as in Step No. 1 to remove further color bodies 65 and reduce carbon requirements. This ste@n is optional and if omitted will only involve a higher carbon consumption requirement in the next step of the process. 4. Carbon treatment.-The liquor either from the second decolorizing step or direct from the electrodialysis 70 process can be treated with activated carbon in one of the following two ways: (a) Activated powdered carbon-batch treatment. The liquor can be treated with powdered activated carbon and filtered to remove remaining color bodies. 75 (b) Granular carboti colui-@in. A granular carbon colv@mn containin- PiLt Chem. CPG 44 x 40 mesh or equivalent is used to decolorize liquor from steps 2 or 3. Liqiior flow rate is preferably 0.5-2.0 bed volumes per hour at a temderature oi. 100- 140' F. The effluciit is then filtered. 5. Evaporation.-The carbon treated liquor is concentrated to a very sweet high fermen'Lable rion-crystallizing syrup. Examples The following examples all utilize an isomerized feed liquor with the following a@ialysis: D.E - --------------------------------------- 75.3 Ketose ------------------------------------- 24.6 Dextrose ----------------------------------- 44.3 Fructose ------------------------------------ 20.0 Psicose ------------------------------------- 5.0 Solids -------------------------------------- 41.8 Ash ---------------------------------------- 0.91 Color, percent traismission: 450 rniz -------------------------------- None 550 ml-& -------------------------------- 6.0 620 mA -------------------------------- 31.0 All colors mcasured in 6" x 3/4" optically matched colorimeter ttibes with a Bausch and Lomb Spectronic 20 Colorimeter. The flow diagram shows the @process steps used in m@iking the prodlict used in the exampl,-s. Also the specification of Ser. No. 184,506 gives the details of making such a product. Example I (A) A volume of 4000 cc. isomerized liquor having the foregoing specifications is passed throua,h a 100 cc. bed volume of Rohm & Haas IRA 401-S in the chloride form at a rate of I gal./min. ft.3 at ambient ternp-@rature. (B) Tlle liquor effluent from the resin is passed through an clectrodialysis stack pack assembly at ieo=4 at 110' F. The stack pack coiisists of 10 cell pairs of Ionics Inc. 61 CZL and III EZL 9" x 10" membranes with 0.040" spacers. The electrodes are plat,.niim-tatalum and Hastelloy C. Th-- elec,rode stream is 0.1 N Na2l '04 and the stprting conceiitration (waste) stream is 0.05 N i\TaCl. Starting liquor resistivity is 220 chmlcm. at I! O' F. and fitipl liquor re,.;istivity is 3050 obm-cm. at 110' F. (C) The clectrodial@yzed liquor is pas@.ed through a 100 cc. bed of IRA 401-S as pcr step A. (D) The liquor is then carbon treated as a final decolorizin.- step. An analysis of product properties at the end of each processin.- step is as follows: TABLEI Ketose, Fructose, Psicose, Dextrose, Color, Percent Transmission Percent Percent Percent Percent --- - - 450 ml, 650 ing 620 mg 24.6 20.0 5. 0 44.3 None 6.0 31.0 24.8 ------ -------- I ------ 44.4 Non(3 57.0 83.0 26.6 19.4 3.9 45.3 3.0 30.0 46.0 27.4 ---------------------- 45.6 33.5 87.0 93.0 27.7 20.6 3. 7 46. 5 79.5 93.0 95.0 Example II The steps here are identical to Example I except that step C, the second resin decolorizing st-.p, is omitted. Aiialvsis for feed, steps A and B, are identical to those of Table I of Exanple 1. The liquor, carbon treated (22% carbon treatments) right from the electrodialysis system has the following color levels: Color, p@@reent transmission: 450 rntk --------------------------------- 38.5 550 mg --------------------------------- 79.0 620 miL --------------------------------- 88.5

5 3)3832245 Sugar contents of final product are similar to step D, Table L Example 1. Example III (A) Isomerized feed liquor is electrodialyzed in electrodialysis stack pack assembly consisting of 10 cell pairs 5 of Ionics Inc. 61 DZL & 111 EZL 9" x 10" membranes with 0.040" spacers, at ieo=4 and 110' F. Electrodes are platinum-tantalum and Hastelloy C and the electrode stream is a solution of 0.1 N Na2SO4- Starting concentration of the concentration (waste) stream is 0.05 N 10 NaCl. Resistivity of liquor is 220 ohm-cm. at 110' F ' at the start and the final resistivity of deashed liquor is 3000 ohm-cm. at 1 10' F. (B) (1) The electrodialyzed liquor is carbon tre-ated to yield an analysis similar to Table I-D and the fol15 lowing color level: Color, percent transmission (2-2% carbon - treatments): 450 mp --------------------------------- 12.0 550 m@k --------------------------------- 49.0 20 620 mtk --------------------------------- 65.0 (2) The electrodialyzed liquor is passed through a collimn of IRA 401-S at the same conditions of step A, Example I. The effjuent from the resin column is then carbon treated. 25 Analysis at th-- end of the processing stages is as follows: Exampl@e IV 40 Isomerized feed liquor is electrodialyzed as per part A of Example III. The feed liquor (4000 cc.) is then passed throu.-h a 500 cc. bed (320 g.) of Pitt. Chem. CPG 14 x 40 mesh @.ranuiar carbon at a rate of 4.2 cc./min. (.5 bed vol./hr.) at 110-1151 F. The composite 4,5 is collected with the following analysis: chosen for purposes of the disclosure, which do not constitute departures from the spirit and scope of the invention. What is