4,008,285 United States Patent ,,o; ay Melaja et al. (4s) Feb. 15, 1977 St] PROCESS FOR MAKING XYLITOL 3.558.725 1/1971 Kolo 2601695 ¢ et be Aner ane 3Sieae0 Sort Paes 2e0re3 c [76] Inventors: Asko J. Melaja, Niittypolku 6, 3,784,408 1/1974 Jaffe 260/635 C Kantsik; Lauri Hiimliinen, 319300970 5/1973 vers 1276 A Baal C, 02460 Kan both of OER PUBLICATIONS ile ©. Samuelson et al, Actd. Chem. Scand, 22, [22] Filed: June 18, 1975 55 rose C1B68) [21] Appl. No.: 588,022 Primary Examiner—Morris O. Wolk Related U.S. Application Data Assistant Examiner—Sidney Marantz [60] Division of Ser. No. 463,037, April 22, 1974, Attorney, Agent, or Firm—Brumbaugh, Graves, fhandoned, which is continuation in-pat of. No. Donohue & Raymond 354/391, Apt 25,1973, abandoned [52] US. CL. ceseseee 260/635 C; 127/37; (57) ABSTRACT 137/46'A; 127/46 Bi, 2607637 R;S36/i A method for recovering xplitol from pentosan-, prefer- [51] Int. CL? CO7C 31/183 C13K 13/00 ably xylan-containing raw materials including the steps [58] Field of Search .. 127/37, 46 R, 46 A, of hydrolyzing the raw material, purifying the hydroly- 127/46 B; 260/635 C, 635 R, 637 R by ion exclusion and color removal, and then sub = jeeting the purified solution to chromatographic frac- a ) References Cited . tionation to provide a solution containing a high level UNITED STATES PATENTS of xylose. The xylose solution is hydrogenated and a 281885111958 Khym 127/85 Sylitohrich solution is recovered by chromatographic 2890972 6/1939 Wheaton até factionation using ion exchange resins. 2917390 12/1959 Apel 260/635 ¢ 33051395 2/1967 Salle 1276 B . ‘ne Fi 3,420,709 1/1969 Barrett 127/53 ‘16 Claims, 15 Drawing Figures PRODUCTION OF XYLITOL AND. XYLOSE i i 1 I i | i 1 I | i ewe i i spo} solution” i I roo | | Monto 'U.S. Patent Feb. 15, 1977 Sheet 1 of 14 4,008,285 pentose molasses FIG./ PRODUCTION OF XYLITOL AND XYLOSE Hydrolysis of Pentosan- containing raw materials pentose sugar material ——__1 Jon exclusion -------4 i i \ Finot purification ond | color removal | I purified pentose solution | , =] Hydrogenation i | i | i polyol solution it 1 Fractionation ond] | [Frastonaton ond crystaliztion i crystallization I Po , v XYLOSE XYLITOL polyol molassesSheet 2 of 14 4,008,285 Feb. 15, 1977 USS. Patent , 1 t 1w0qu09 Poyoaioy Peq pax f ‘yoquo3 — pajonnoy eq pexw Peq paxiw 4. t t 7 xt 1894 Bus21s01009 eats pq pax u1s91 burz120}099g faeae F ¥ f ef ; , Jabuoyoxe ous yom, I ‘se6upyoxe wo109 6uos, yos sobs esojuad TWAOW3Y YOI09 GNY NOILVOISINd TWNIS NOILMI0S YVONS 3SOLN3d YOd S3uNGIIONd YNOI 2 OldUS. Patent — Feb. 15, 1977 Sheet 3 of 14 4,008,285 CHROMATOGRAPHIC FRACTIONATION AND CRYSTALLIZATION OF XYLITOL purified pentose solution ¥ Hydrogenation polyol solution Chromatographic ‘octionation | f-—® Belvo! molasses Xylitol-rich fraction + i XYLITOL <———|__ Crystallization i ' 1 1 1 ! al 1 i 1 | 1 1 i recirculation of xylitol~ rich fraction syrup ¥ XYLITOL Chromatographic SOLUTION fractionation | polyol molassesU.S. Patent Feb. 15, 1977 Sheet 4 of 14 4,008,285 FIG.4 XYLITOL PRODUCTION, MATERIAL BALANCE SCHEME wood D.S. 10009 rites Hydrolysis Pulp X 2559 x Sig NooH rf X nylon, sylose oF sylitol Neviroiizea ORG = organic. material except X hyve, MIN = minerals ‘inorganic material } 9 8 9 DS. = dry substan ORG 110g MIN 67g 7 ee T-Evoporation Je CH COOK 18g CHs COOH I2g Ds. 1,5- 35 jactecieemeredieces (| ‘Salt fraction IL Evaporation xX 14g ORG 649 ;-—» DS. 4-55 -— 1 MIN 629 _D.S, 1425 water removed 32929 Solt removal 0.5, “3819 Sugar Fraction TH - Evaporation X 190g ORG 46g }—+| 08. 8-60 MIN 59 0S 2419 water removed 26I1g) fication demineralization colour removal Ds 24lg Hydrogenation x Ielg ORG 405 Crystativzation J] Drying X_181+123 = 3049 x 182g i JORG 40+20= 60g [-———*|_ ong 1g «= [4] Packing Dis. 221+ 143 = 3649 BIS 1859 syrup Polyol molasses TZ Eveporation % 239 oss Te ORG 389: water removed 126 Fractionation o_O. 689 —! Xx 1529 ors 59 DS. 2ilg Xylitol = rich fraction Y Evaporation = XK 1239 ts |_J bro 20, Fs. 4-70 DS 1430 jwater removed 8179]4,008,285 Sheet 5 of 14 U.S. Patent Feb. 15, 1977 uwol x ew O¢-B1 suoyo014 se_oe ve ze for oz 92 wz zz bz sonundwr umouyun puo suoBns payouabospayun = --— u/t 21 peed 2 6b duo wo g'Zz 9x wo0SE : pea WWZE'O 9zIS 9ID1}J0d “WuOJ- 99 :uISey G OldSheet 6 of 14 4,008,285 Feb. 15, 1977 U.S. Patent vworx eu fb _— zg-1¢ suonooug oc_ oc ve| aco o¢ oe ve zz oe [or os ie Tt sarjiundu_umouyun uo suv6ns pejpuaboipAyun = -—— pup suv6ns poji yun U/L GI pad Delg dway g2zexus0se¢ :paa wiwZe'0 9218 81914400 ‘uy, 4S :uIsey 9 OldU.S. Patent — Feb. 15, 1977 Sheet 7 of 14 4,008,285 FIG. 7 SEPARATION OF SORBITOL AND XYLITOL Resin in Ai***- form ¢(g/100m!) —— Dry Substance xylitol Sorbitol 20 FractionU.S. Patent Feb. 15, 1977 Sheet 8 of 14 4,008,285 FIG. SEPARATION OF POLYOLS Resin in Fe***~form (rate 3.2 mi /min) —— Dry Substance ¢(9/100m!) Xylitol Mannitol Sorbitol ek Galactitol Arabinitot FractionU.S. Patent Feb. 15, 1977 Sheet 9 of 14 4,008,285 FIG. 9 SEPARATION OF POLYOLS Resin in Al ***+- form (rate 3.2 mi /min) —— Dry Substance --= Xylitol Mannitol Sorbitol Galactitol Arabinitol ¢(g/100 mI) FractionUSS. Patent Feb. 15, 1977 Sheet 10 of 14 4,008,285 FIG. 10 SEPARATION OF POLYOLS Resin in Al***= form (rate 2.2 mi /min) ¢(g/100 mi) —— Dry Substance Xylitol - Sorbitol + Golactitol Mannitol + Arabinitol 22 20 FractionUS. Patent — Feb. 15, 1977 Sheet 11 of 14 4,008,285 FIG. I SINGLE FRACTIONATION Feed (polyol syrup) v xylitol FIG. 12 DOUBLE FRACTIONATION (Me) Froct. (I) om) se" Tmo OX) | x2) (We) Fract. (4 +Xe) (1) Fe*4 t (s) Cryst. (polyol syrup) xylitolU.S. Patent Feb. 15, 1977 Sheet 12 of 14 4,008,285 FIG. 13 FRACTIONATION (I) ¢(9/10om) Resin in Sr**~ form —— Dry Substance Xylitol Mannitol Sorbitol —-— Goaloctito! - Arabinitol Fractions TIM MX Mx Ww My x Time (min)U.S. Patent Feb. 15, 1977 Sheet 13 of 14 4,008,285 FIG. 14 FRACTIONATION (I) Resin in Fe***-form ¢(g/100 ml) Dry Substance Xylitol x= Mannitol —- Sorbitol —-— Galactitol vrmeee Arabinitol Fractions 150 Time (min)USS. Patent — Feb. 15, 1977 Sheet 14 of 14 4,008,285 FIG. 15 SEPARATION OF POLYOLS Resin in Alt**~ form (rate 82 I/h) c 9/100 mi —— Dry substance == Xylitol Sorbitol —-— Galactitol Mannitol Arabinitol Fraction4,008,285 1 PROCESS FOR MAKING XYLITOL ‘This is a division, of application Ser. No. 463,037, filed Apr. 22, 1974, now abandoned, which is a con- tinuation-in-part of application Ser. No. 354,391, filed Apr. 25, 1973, now abandoned. ‘This invention relates to a process for obtaining xyli- tol from pentosan-containing materials, preferably xy- Jan-containing materials by acid hydrolysis of the mate- rials followed by purifying and chromatographic sepa- ration techniques, ‘The prior artis replete with processes described as being suitable for obtaining xylose and/or xylitol from natural products such as birch wood, corn cobs, cotton seed hulls and the like. The Russian article by Leihin, E.R. and Soboleva, G. D., Proizvostro Ksilita (Produc- tion of Xylitol) Moscow, 1962 gives a review of the processes known at that time. Recent United States patents dealing with the subject, include U.S. Pat. Nos. 3,212,932 and 3,558,725. Brit- ish Patent No. 1,209,960 and Russian Patent No. 167,845, 1965, contain related disclosure. The prior art processes have not been employed to any great extent on a commercial scale because they fre economically unsound. For example, where the xyloserich solutions are obtained from wood chips fol- lowing the prior art processes, the solutions have been so impure that several costly process steps, are required before xylose can be recovered or before’ solution of| appropriate purity is obtained that can be hydroge- nated to form xylit In accordance with the present invention, an im- proved method for the production of xylitol from pen- tosan-containing, specifically xylan-containing raw mi terials has now been developed in which a pentose-rich solution obtained by acid hydrolysis of a pentosan con- taining raw material is purified by mechanical filtration and ion exclusion techniques for color removal and desalting. This solution is then subjected to chromato- graphic fractionation to obtain a highly purified solu- tion of xylose. The xylose solution of high purity may be used as a source of xylose in aqueous solution form, ‘or xylose may be crystallized therefrom. The next step in the process is hydrogenating the solution to produce xylitol. Pure xylitol is then recovered from the reaction mixture by chromatographic fractionation. In both this stage of the process, a preferred way of ing the chromatographic fractionation step is by passing the solution through a column of an alka- line earth metal salt of a polystyrene sulfonate cation exchange resin cross-coupled with di-vinyl benzene, the column having a height of from about 2,5 to about 5 meters. In another preferred manner of separating the polyols and recovering pure xylitol, trivalent metal salts, such as Fe*** and Al***, of a polystyrene sulfo- nate cation exchange resin cross-coupled with di-viny! benzene are used in the chomatographic fractionation step. One of the advantages of the process of this invention is that it provides a solution of xylose of sufficiently high purity to warrant hydrogenation thereof to xylitol ona commercial scale if desired. Materials used as the raw materials from which the pentosan-rich solutions are obtained are preferably ignocellulose materials including wood of various spe- cies of trees, such as birch and beach, Also useful are cat hulls, com cobs and stalks, coconut shells, almond shells, straw, bagasse and cotton seed hulls, Where 5 2s 40 45 35 oo 6s 2 wood is used, it is preferably subdivided into wood chips, shavings, saw dust and the like. DESCRIPTION OF THE DRAWINGS ‘The invention will be further described with refer- ence to the drawings, in which FIG. 1 is a flow diagram showing generally the pro- cesses of the present invention; FIG. 2 isa flow diagram showing four possible proce- dures for purifying pentose sugar solutions in accor- dance with the invention; FIG. 3 is a flow diagram disclosing the procedure whereby xylitol is recovered from a hydrogenated pen- tose solution; FIG. 4 is a flow diagram with material balance scheme for a process of preparing xylitol from wood chips; FIG. § is a graph showing distribution of various polyols in successive fractions taken during chromato- graphic separation of a solution of polyols in accor- dance with Example VII, supra; FIG, 6 is a graph showing distribution of various polyols in successive fractions taken during chromato- graphic separation of a solution of polyols in accor- dance with Example Vill, supra; FIG. 7 is a graph showing distribution or sorbitol and xylitol in successive fractions taken during chromato- graphic separation of a solution containing a mixture of the two polyols on an Al*** form of the resin in accor- dance with Example X; FIG. 8 is a graph showing distribution of five polyols in successive fractions obtained after chromatographic separation of a mixture thereof in accordance with the process described in Example FIG. 9 is a graph showing distribution of various polyols in successive fractions taken during the chro- matographic separation of a solution thereof in accor- dance with Example XM; FIG. 10 is 2 graph showing distribution of various polyols in successive fractions taken during chromato- graphic separation of a solution of polyols in accor- dance with Example XIE; FIG. 11 is a flow diagram describing the single frac- tionation procedure described in Example XIV; FIG. 12 is a flow diagram describing a double frac- tionation scheme described in Example XI; FIG. 13 is graph showing distribution of various poly- ols in successive fractions taken during the first frac- tionation of Example XIV, using the Sr°** form of resin; FIG. 14 is a graph showing distribution of various polyols in successive fractions taken during the second fractionation of the solution of polyols described in Example XIV, using the Fe*** form of resin; and FIG. 15 is a graph showing the results of the polyol separation described in Example XV. Referring to FIG. 1, the raw materials may be hydro- lyzed in the first stage of the present invention by fol- lowing any of the well known procedures in the art. Suitable procedures described in the literature include those given in U.S. Pat. Nos. 2,734,836; 2,759,856; 2,801,939; 2,974,067 and 3,212,932. The important the appropriate method of hydrolysis is that a maximimum yield of pentoses be ‘obtained and that the resulting pentose-rich solution be neutralized using materials which do not cause serious deterioration of sugars, such as sodium hydroxide. Where the pentose material is obtained by methods4,008,285 3 other than acid hydrolysis, the step of desalting by ion exclusion described below may not be required. The next stage in the process where a hydrolysis product is used is that of the purification of the hydro- lysis product. The purification stage comprises. two main steps, one is removal of the salt, sodium sulfate, and the major part of organic impurities and coloring bodies by ion-exclusion techniques, while the second step accomplishes final color removal. The ion exclu- sion technique removes salt from the solution and simi- lar processes have been used in the sugar industry for the purification of molasses. Suitable processes are described for example in U.S. Pat. Nos. 2,890,972 and 2,937,959. ‘Upon completion of the salt removal step the solu- tion still contains some organic and inorganic impuri- ties. These are removed by the color removal step by treating the impure solutions with ion exchange sys- tems consisting of a strong cation exchanger followed by a weak anion exchanger and then followed by a step of passing the solution through an adsorbant or acti- vated carbon bed. These methods are also known in the sugar industry. One such procedure is described for example in USS. Pat. No. 3,558,725. Other pertinent disclosures of this feature include J. Stamberg and V. Valter: Entfarbungsharze, Akademie Verlag Berlin 1970; P. Smit: lonenaustauscher und Adsorber bei der Herstellung und Reinigung von Zuckern, Pektinen und verwandten Stoffen. Akademie Verlag Berlin 1969; 3. Hassler: Activated carbon; Leonard Hill London 1967. As shown in FIG. 2 the purification step may be further improved where necessary by the addition of a step which uses a synthetic macroreticular adsorbant such as Amberlite XAD 2 to remove organic impuri- ties. The macroreticular adsorbant can be used in the purification stage immediately following the ion exclu- sion step but prior to the cation exchanger as shown in FIG. 2. Altenatively, it can be the final step of the purification stage. FIG. 2 shows four alternate schemes for accomplish ing the purification stage of the process of the present invention. Selection of one of these alternate schemes will depend upon the nature and level of the impurities present in the solution and upon the composition of the solution undergoing purification ‘The purified pentose solution obtained in the purifi- cation stage may then be used for the recovery of xy- lose as shown in FIG. 1 by chromatographic fraction- ation to obtain a solution with a high purity with re- spect to xylose, followed by crystallization. The pen- tose molasses, made up of unselected fractions, may be subjected to’ further chromatographic fractionation procedures to recover one or more of the other sugars present therein, Alternatively, it can be used as a source of carbohydrate in fermentation processes. Alternatively, where xylitol is desired, the purified pentose solution is hydrogenated and treated according to the procedure outlined in FIG. 3. The hydrogenation process is conducted in a manner similar to the hydro- genation of glucose to sorbitol. A suitable process is found in an article by W. Schnyder entitled “The Hy- drogenation of Glucose to Sorbitol with Raney Nickel Catalyst," Dissertation at the Polytechnical Institute of Brooklyn, 1962. It has additionally been found that unhydrogenated sugars present in the hydrogenated pentose solution are easily separated from the mixture of polyols by follow- ing ion-exchange chromatographic techniques. The 20 as 30 3s 40 4s so 35 60 6s 4 unhydrogenated sugars are eluted from the column ahead of the polyols. The fractions shown in FIGS. 5 and 6 as “unknown impurities” were found to contain substantial quantities of unhydrogenated sugars. Thus, the process of the present invention provides a method of obtaining pure polyols, even though hydrogenation is incomplete and permits the use of continuous hydro- ‘genation method, if desired. ‘The ion exchange resins used in separating the poly- ols in accordance with this invention are of the type described as sulfonated polystyrene cation exchange resins cross coupled with di-vinyl benzene. The alkaline earth metal salts of these resins, such as the calcium, barium and strontium form provide acceptable results and of these the strontium form gives the best separa- tion of the polyols. A significant improvement in the separation of certain polyols is obtained where the trivalent metal forms such as the Al*** and Fe*** are used. Ithas been found for example that the AI*** and Fe*** forms of the resin provide at least three advan- tages over the use of the alkaline earth metal forms by themselves. In the first place, it has been found that the polyols are eluted from the Al*** and Fe**" in a differ- tent order. This was surprising and is important because separation of the major impurity, sorbitol, is thus im- proved In the second place, in the recovery of xylitol itis possible to avoid the accumulation of sorbitol caused by recycling by either carrying out the fractionation initially on a resin of either AI"** or Fe*** form or by using a double fractionation process where a first frac- tionation is conducted on a resin in alkaline earth metal form followed by a second fractionation on a resin in AL or Fe*¥ form. ‘Asa third advantage, it is possible to advantageously separate any desired polyol from a mixture of polyols resulting from the hydrogenation of wood hydrolysates. EXAMPLE I As an example of the hydrogenation step conducted in accordance with the process of the present inven- tion, a suitable feed solution obtained by purification of a bitch wood hydrosylate is subjected to catalytic hy- drogenation to form a xylitol-tch solution. The feed solution in the amount of 1,500 grams having a concen- tration of solids of 50% by weight and the solids com- prising 75% xylose and 25% other sugars is hydroge- nated in a batch autoclave using a Raney nickel catalyst ata temperature of 135°C for 2% hours, at a hydrogen pressure of 40 atmospheres. At the end of this time the catalyst is removed by filtration and and residual amount of nickel remaining in the solution is removed by ion exchange treatment, ‘The next step in the process of the present invention is the fractionation of the solution of the polyols ob- tained by hydrogenation into a xylitol-rich fraction and a polyol molasses. The hydrogenated solution prepared as described above contains a mixture of polyols; a typical composition of a hydrogenated birch wood hydrosalate as follows: Percent, Dry Potyol Solis Bass Xpiitoh 7 Arebinitol 7 Manat & Gstactot 44,008,285 5 6 -continued Table I-continued Percent, Dry Frac 8 of Paty! Sole fais ‘ion “Aan! “Maral! Galatta! —ylial —SorbRor Sorbitol 4 58 ais os —— ‘0 oa 02 ‘The mixture of polyols is separated by ion exchange chromatography and fractions are selected which pro- vide a solution which is rich in xylitol. The purified solution thus obtained is readily processed to provide crystallized xylitol therefrom. Other polyols present in the solution, that is the arabinitol, mannitol, galactitol and sorbitol, may either be recovered from other se- lected fractions or collected into a polyol molasses. ‘While the hydrogenated polyol solution may be suy plied directly to the fractionation column, it is techni- cally sometimes advantageous to first crystallize a por- tion of xylitol from the impure solution, to separate the crystals, and to then fractionate the’ sugar alcohols remaining in the solution chromatographically. In addi- tion, the solution remaining after the crystallizaton and separation of the crystals therefrom may be recircu- lated to a subsequent crystallization step in in order to improve the yield of crystals. This procedure is ilus- trated in FIG. 3. EXAMPLE I ‘As an example of the application of a chromato ‘graphic fractionation step to the polyol solution, a col- tumn of ion exchange resin, specifically, a sulfonated polystyrene cation exchange resin, cross-coupled with 23.5% divinyl benzene, in strontium form, is provided in a column one meter in depth and 9.4 centimeters in diameter. The column is prepared for use by submerg- ing it in water. Means are provided to insure uniform introduction of the feed solution across the column. The feed solution has a solids concentration of 25% and a polyol analysis, by gas-liquid chromatographic analysis, as follows: Percent, Dry Sole Bans 755 29 ‘Monnior 3 Gasset 33 Sorbo! 3 ‘The feed solution is fed to the column at a temperature of 50°C and at a feed rate of 27 ml per minute. The total amount of solution fed is 58.5 grams and the solids concentration thereof was 25%. Table I below shows the distribution of polyols in successive fractions col- lected during the chromatographic fractionation. Be- fore collection of fractions commenced, 216 ml of solution, mostly comprised of the water originally in the column, was collected and discarded. Table 1 Resend Kal Sorbiar Toss : = 2 tas = = 5 iss = = a oto if 5 a ws é 14303, 5 = Tor bas a = a8 08S -rich fraction is obtained by combining a part of fraction 5 with fractions 6 and 7. The solution thus ‘obtained, 430 ml in amount, has the following analysis: Poljol Gram 15 “Arabia 0s ‘Sanmior % Gatacutot 035 Xylitol 2965 (95%) Serbitot 095 20 Crystalline xylitol is obtained from xylitolrich solu tions of the type described above by simple evaporation of the water contained therein. For example, 2,000 grams of a xylitol solution having a solids concentration of 80% and xylitol purity of 95% of the solids, when held at 60° C for 12 hours, provides 1,200 grams of crystalline xylitol having a purity of over 99.5%. EXAMPLE Ill A xylose-tich solution obtained as shown in FIG. 1 may be purified advantageously by chromatographic fractionation and subsequent crystallization. The put fied pentose solutions contains several sugars in addi- tion to xylose and the solution can be greatly enriched with respect to xylose by utilizing chromatographic fractionation techniques. In carrying out this example, a chromatographic column comprising a strongly acid ‘cation exchanger in the form of a sulfonated polysty- rene, cross-coupled with 3.5% of di-vinyl benzene, in 25 30 35 *° strontium form, is contained in a column 1.0 meter high and 9.4 centimeters in diameter. The resin is sub- ‘merged with water. A pentose solution containing 25% solids and having the following composition was used 4s 2 the feed solution: Poreant, Dey Sugar Sole Bet yose 7 a 35 ‘The solution was uniformly fed across the top of the column at the rate of 27 mi per minute until a total of {60 grams of solids are fed to the column. The first 108 ri of material through the column comprising mostly the water originally in the column, are discarded. An 60 analysis of the fractions obtained thereafter is given in ‘Table It below. Table I Fae of 65, _00n_“Uisie Kise Manone Calaiane ADOT 1 02 = = = 2 Os = = = 3009s on = = 2 Pe S = =4,008,285 7 Table H-continued Free “areca ayes We Cane — mre 5 4400S S é 03 on = 5 0 03 8 18 os 5 13. 03. = 0 ros os. os t 03 O85 88 a O33 Os i a bos Os on a Ss S os i S S = = on By combining fractions 6,7 and 8, applicants ob- tained a solution having a xylose purity of 89%. ‘This xylose-rich fraction can be used in the produc- tion of a pure crystalline xylose. Altematively the xylose-rich solution obtained by combining fractions 6, 7 and 8 may be hydrogenated as shown in FIG. 1 to obtain a relatively pure xylitol solution. It is addition- ally possible to crystallize the xylose from the solution, such as the feed solution used above in this example, and to thereafter fractionate the sugars which remain in the syrup by chromatographic procedures using ion exchanger resins. The xylose-rich fraction is recirculated to the crystallization step. It is also possi- ble to obtain other pentoses and hexoses from corre- sponding fractions or the balance of the fractions may bbe combined into a pentose molasses. EXAMPLE IV Birch wood in the form of chips is used to prepare xylitol in accordance with the process of the present invention. A material balance scheme for this example is given in FIG. 4 of the drawings. In accordance with the process of this example, suffi- cient birch wood chips to provide 1,000 grams of dry substance are hydrolyzed with sulfuric acid to provide a mixture of hydrolysate and pulp which contains to- tally 225 grams of xylose. The pulp, containing 51 grams of xylan is removed from the hydrolysate and either discarded or used for some other purpose. The balance of the hydrolysate containing 204 grams of xylose is neutralized with sodium hydroxide to provide a hydrolysate containing 204 grams of xylose, 110 grams of organic material exclusive of xylose and 67 grams of inorganic material. The hydrolysate is then heated to drive off unwanted acidic acid and water, and then subjected to a step of salt removal by ion exclusion and purification by passing the solution through succes- sive beds of strong cation exchanger and weak anion exchanger. As shown in the drawing, 14 grams of xy lose together with a major portion ‘of the inorganic material and some of the organic material are removed and discarded in the salt fraction. The sugar fraction, ‘containing most of the xylose together with a portion of the organic impurities and a small amount of inorganic impurities are again subjected to an evaporation step to remove additional quantities of water. The concentrated sugar solution thus obtained as passed through a color removal step and activated carbon bed. The thus purified solution, containing 181 ‘grams of xylose together with 40 grams of organic ma- terial, is hydrogenated. After hydrogenation, the solu- tion is heated to evaporate a portion of the water, and from the concentrated solution xylitol is crystallized. The mother liquor remaining after removal of the crys- 5 20 25 30 40 4s 50 60 6s 8 talline xylitol is passed through a chromatographic ion exchange column, certain fractions being selected to provide a xylitol-tich fraction and the balance going into the polyol and molasses fraction. The xylitorl-rich fraction is concentrated by removal of water and re- tured to earlier crystallization stage where the xylitol is recovered. As can be seen ftom FIG. 4 of the draw- ings, the yield in terms of xylitol obtained from a given of raw material is high; approximately 60% of the original xylan content of the raw material is recov- ered as xylitol. EXAMPLE V A xylose-rich solution obtained by hydrolysis of birch wood, followed by salt removal and color removal pro- cedures as described above, was further purified by chromatographic fractionation on an ion exchange resin column in accordance with the procedure de- scribed below. The composition of the solids content of the xylose-rich solution as determined by gas chro- matographic analysis, was: Sugar Pereent ‘Arabinore 6 Xyose ” Mannose "75 Galactose Shucone as The resin employed was a strongly acid cation ex- changer, sulfonated polystyrene cross-coupled with 43.5% of di-vinyl benzene, the resin being in calcium form. The resin had a mean particle size of 0.32 mm. ‘The Separation was conducted at a temperature of 49° €. The column was 350 cm in height and had a diame- ter of 22.5 em. The column was submerged in water. ‘The xylose-rich solution was fed uniformly across the column at a rate of 17 liters per hour. The total amount fed to the column was four kilograms of solids, as a solution having a solids content of 26' ‘The first effluent from the column, in the amount of 88 liters and mostly comprising water, was discarded. Thereafter, successive fractions were collected and analyzed, With the following results: Frac. lon _“Glueow — Xylene Mannate Galactose Arabia 1 6a = S = 2 of gs = = 54s ast = 278 308 sot to % 6 = So 8 5 les a i 3 9 * 0 es Fractions 3 through 6 were combined to provide 35 liters of a xylose-rich solution which had the following analysis: ‘Sugar ‘Grams ‘Arabinose = Sytose, 2883. (=855%) Mannose 240 Galactose to4,008,285 9 -continued Sugar Grams, Glucose 3 EXAMPLE VI A xylose-rich solution obtained by hydrolysis of birch ‘wood followed by salt removal and color removal pro- cedures as described above was further purified by chromatographic fractionation on an ion exchange resin column as described below. The composition of the solids content of the xylose-rich solution, as deter- mined by gas chromatographic analysis, was: Sugar____‘Percont Anitinos 65 Xsiowe 7 Mannose |S Gatzctore Giucore as ‘The resin employed was a strongly acid cation ex- ‘changer, sulfonated polystyrene cross-coupled with 3.5% of di-vinyl benzene, the resin being in strontium form. The resin had 2 mean particle size of 0.32 mm, ‘The separation was conducted at a temperature of 51° . The column was 350 cm in height and had a diame- ter of 22.5 cm. The column was submerged in water. ‘The xylose-rich solution was fed uniformly across the column at the rate of 15 liters per hour and the total amount of solids supplied to the column was four kilo- grams, in the form of a solution having a solids content of 28%. ‘The first effluent from the column, in the amount of 88 liters and comprising mostly water, was discarded. Thereafter, successive fractions were collected and analyzed, with the following results: Dry substance, Grams Fraction Glucose _Xylote Mannose Galactose Arabinose 1 a1 = = 2 157 = = 3 aw = = 4 62S = = 5 oe 8 = 6 5601 “0 = i 3a 108 3s 3s a i 66 3 3 5 a7 1 99 0 oo Ss a Fractions 3 through 6 were combined to provide 35 liters of a xylose-rich solution which had the following analysis: ‘ua ‘Grams Xylose 2385 (90%) Mannose ie Galactore 3 Glucose 2 0 20 2s 45 50 35 6 6s 10 EXAMPLE VIL ‘This example illustrates the separation of sugar aleo- hols by chromatographic fractionation on an ion ex- change resin column. The resin used was 2 strongly acid cation exchanger, sulfonated polystryene cross- coupled with 3.5% di-vinyl benzene, the resin being in calcium form. The resin had a mean particle size of 0.32 mm. The separation was conducted at 49° C. The column was 350 cm in height and had a diameter of 22.5 cm. The column of resin was submerged in water. ‘The polyol solution was fed uniformly across the col- umn at a feed rate of 17 liters per hour, and the total ‘amount of solids fed to the column was four kilograms in the form of a solution having @ solids concentration cof 26%, The composition of the polyot solution, as determined by gas chromatographic analysis, was Percent 3 5 4 5 Poly ‘Arainital sitet Menno Galatta. Sorbitol Unknown ‘The degree of separation of the sugar alcohols ob- tained in accordance with this example is shown in FIG. S of the drawings. A number of fractions were taken. A Useful xylitol-rich fraction was recovered by combinin fractions 18 through 30. In this manner, a solution in, the amount of 34 liters was obtained having the follow- ing analysis: Palyol Gams ‘Arabia = Xyttot 1810 (2965) Mannitol = Gatsettot a Serbivt 80 EXAMPLE VIII ‘This example illustrates the separation of sugar alco- hols by chromatographic fractionation on an ion ex- change resin column. The resin used was a strongly acid cation exchanger, sulfonated polystyrene cross- coupled with 3.5% di-vinyl benzene, the resin being in strontium form. The resin had a mean particle size of 0.32 mm. The separation was conducted at 51° C. The column was 350 cm in height and had a diameter of 22.5 cm. The column of resin was submerged in water. ‘The polyol solution was fed uniformly across the col- umn at a feed rate of 15 liters per hour and the total amount of solids fed to the column was four kilograms in the form of a solution having a solids concentration ‘of 28%. The composition of the polyol feed solution, as, determined by gas chromatographic analysis, was: Pavel Percent “Anbinitol 10 Xyitl 6s onsite! Galetto! 5 Sorbitol 54,008, li -continued Polyol Unknown ‘The degree of separation of the sugar alcohols ob- tained in accordance with this example is shown in FIG. 6 of the drawings. A number of fractions were taken. A useful xylitol-rich fraction was recovered by combining 10 fractions 31 through 57. In this manner, a solution in the amount of 40 liters was obtained having the follow- ing analysis: 285 12 EXAMPLE X This example illustrates the separation of hexitol from pentitols using a synthetic mixture of sorbitol and xylitol, and using sulfonated polystyrene cation ex- change resins cross-coupled with 3.5% di-vinyl ben- zene. A series of resins were evaluated, including each of the following catio forms: H*, Li*, Nit*, Mg**, Fett, NH,*, Al***, Cut*. Of these cations, Fe"** and Al**give the best results. The results of the experi- ‘ments are shown in the following table: Fractionation of Xylitol and Sorbitol — = 1s FORE sotto SO wy ———_ — 1 0.84 0.79 0.10 0.30 HY Nant mom 3 Gas OS Oak NE th 3 oa Oak Ol Gas Fetes ‘This example illustrates the separation of ushy- 25 Grogenated sugars and polyols from a hydrogenated ‘The distribution coefficients, HETP values and the pentote solution by chromatograph fractionation om radon value forte separations wore called an ly acid catic ‘These values are the parameters normally used for the jStamuster: ut bel resin used Aas] a Lenore Lec enon evaluation of column separations, and are calculated exchanger, sulfonated polystyrene cross-coupled with 30 according to the following P formulae: 3.5% di-vinyl benzene, the resin being in calcium form. 1g 1g a arson wae condusted at 30°C and the feed rate ats wer0.90 hour The food sock comprised a hycrope nated mixture with 57 g. of solids as a 28% aqueous 35 ‘nere =" winlon The compostifn ofthe sis was flows — = f o ee ‘Assbineet i Ky = distribution coefficient as i ETP hehe of those plate cae # = heat Kyeee™ meeriss 35 45 elution volume for the peak ‘A number of fractions were collected and analyzed by gas-chromatography, with the following results: Dry Substance, Grams N= number of theoretical plates Fraction Xylose Unknown Mannitol Arabinital Galacttol” Xylitol Sorbitol ross = = = = = 2 06502 = = = = = 5 ts = = = = = 4 5 os on = = = = 5 = os 18 03 = cos 6 5 OR se oos k= 5S 08 was 4 " S15 on 3 03 90 O6 0 = a1 oS i" = = 6s 2 Ss a = = ses 03 3 = = = = 13s ons By combining fractions 6-13, a polyol solution com- pletely free from unhydrogenated sugars and unidenti- fied impurities was obtained. M-=band width of eluted peak, measured on volume (or time) axis in volume (or time) units4,008 13 From the examination of the table above, itis evident that sorbitol is eluted before xylitol and that Fe*** and AI" give the best separation. "The conditi is used in this example were as follows: 5 Column ight. 84 em; diameter, 44 em Tempertue 50°C Feed Rate 3.2 niin ao Resin {polyestene sulfonate, coseinked sith 3-4 vino benscee) Ihetn bead sine O18 mm, Al***-fomm Feed ‘Teynthete mixute of sorbitol and Zyitol (1-1). Total amount 25 g {substances concentration 38% (weight) 1s ‘The results obtained in accordance with this example are shown in FIG. 7 in graph form. 285, 14 EXAMPLE XII ‘This example describes the separation of five polyols present in hydrogenated wood hydrolysates on the cation exchange resin described in Example X, using the Al*** form. The conditions of the separation were as follows: ‘Separation of polyor Column eight, #2 em: diameter, 44 em Temperature SINC. Feed Rate 32 nia Resin [Ar in Example X, AI***-form Feed Potyo solution, tial amount 235 g ry ubnance, congentition 34 9%, comp- ‘ton given in Example Xt above ‘The results obtained are summarized in the following tables: ‘Separation of Polyal on Resin in AI"*7-Form Fraction Mannitol AtabinitolGalecttol Xyfitl Sorbitol @om) ’ a g 8 Tab 00 oo —- —- — — — — 002 oo 2 ols 027 — os aos = aa 020 3 027 034 007 007 0.13 0.18 002 Oa2 0.3.86 ‘ 039° 093 «O18 0.28 023 O41 023 © 025056 1.10 5 043 136 027 051027 068 (052077065 LT6 6 034 170 039 «O91 «023-091 192269 0868 232 7 023 193 043 134 O16 107 3085740. 2.66 8 O11 204 039-173 009116 329903, ot 2.87 9 00s 209 029 202 003 121 305 1208 Ott 2.98 10 SA ots 2s S203 at ons 303 n for SP LL om um a ee Tout 2.09 215 121 15.03 303 59% oi 5% 64.0% 129% Distribution of polyols when the fractions are com- jo bined a) 1-6 / 7-12 or b) 1-7 / 8-12. Polyols, as % of EXAMPLE XI CEN ‘This example shows the separation of each of five polyols from hydrogenated wood hydrolysates on the tation exchange resin described in Example X, using the Fe++* form. The results are shown graphically in FIG. 8. The conditions for this example were as follows: Separation of Pobol a) Column ‘eight 4 om; diameter, 44 em empernure SPC" Feed Rate 33 min Resin Fotytyene sulfonate with 3-4% DVB, tnean fead siz 0.18 nm, Fee? form Feed Foil soliton, total amouat 25g dry 5s ‘ubetanee, concentation 33%. ‘The composition of the feed solution was as follow: 23.5 g total dry substance; concentration: 35 g/100 ml Percent Manniot 88 Abinto 31 Gatactto! SI Spite oo 6 Sorbitol 123 ‘Arabnitot Galsttt Xoltat Sorbo! In addition, FIG. 9 of the Drawings is a graph illus- trating the results obtained in accordance with the process of this example. EXAMPLE XIII ‘This example illustrates a process similar to that of Example XII above and differs therefrom only in the feed rate used. The column dimensions and resins used were the same as those in Example XII. The tempera- ture used was 50° C and the feed rate was 2.2 ml per minute. The feed solution was a polyol solution, 25 ‘grams in total amount containing 35% of dry substance. ‘The results obtained in this example are shown in FIG. 10. EXAMPLE XIV The following example describes a double fraction- ation procedure which is useful in the production of4,008,285 15 xylitol in accordance with the process of the present invention. In the first stage of the procedure, a hydrogenated ‘wood hydrolysate is fractionated on a resin in alkaline arth metal form and three fractions are collected from 5 the effluent, namely, a xylitol-rich fraction, a polyol fraction and a waste fraction, Xylitol is crystallized from the xylitol-rich fraction and the xylitol crystals are separated from the mother syrup by centrifuging. The ‘mother syrup which remains from the centrifugation is combined with the polyol fraction obtained from the first fractionation above and the resulting combined polyol solution is then subjected to a second fraction- ation on a resin in Al*** or Fe** form. ‘Three fractions are again collected from the effluent of the second fractionation namely, a xylitol-rich frac- tion, a polyol fraction and a waste fraction. The xylitol- rich fraction from this second fractionation is com- bined with the xylitol-rich fraction from the first frac- tionation and from the combined solution, xylitol recovered by concentration and crystallization. The polyol fraction from the second fractionation is added to the next batch of feed solution to the first fraction- ation and the combined sol fractionated on the 0 5 16 graph showing the results of this fractionation, in terms Of the polyol distribution in successive fractions, is shown in FIG. 13. Referring to FIG. 11, the fractions are combined into a xylitol-rich fraction (X) and a -d polyol fraction (M). From the x; Xylitol is recovered by concentration and crystalliza- tion, The mother syrup from the crystallization may be partly recirculated to the process. Double fractionation —Referring to FIG. 12, the polyols are first fractionated as in the method with a single fractionation which is described above (resin in Sr**-form). From the first fractionation, 3 fractions are recovered: a xylitol-rich fraction (X,), a polyol fraction (M,) and a waste fraction (W,). From the waste frac- tion, xylitol cannot be recovered, but it still contains valuable carbohydrates. From the X,, fraction, xylitol is recovered by concentration and crystallization. The polyol-syrup which is separated from the crystals is Combined with the polyol fraction (M,) from the first fractionation to provide a polyol solution (S) w! contains large amounts of xylitol. This solution (S) is fractionated on a resin in Fe***-form and again 3 frac- tions are collected: a xylital-rich fraction (X,),a polyol fraction (M,) and a waste fraction (W,). The second column of alkaline earth metal form resin as described 25 xylitol fraction (X,) is combined with the first xylitol for the first fractionation. fraction (X,) and from the combined solution xylitol is ‘The process was carried out in detail as follows: recovered by concentration and crystallization. The second polyol fraction (Mz) is combined with the next batch of feed solution. Produotion of Xyol 30 A graph showing the result of the double fraction- Feedsouton—Aabiniol 338 of @ytwance ation (Fractionation 11) is shown in FIG. 14. Site! H solutions an Riel 20 8 ‘Composition of the solutions and fractions: Fractionation f Feed, 100% S05 Mi, 398 Ambionol $28 ofds 02% ofda Gis ofds Syitot 7708 $298 Sa Mannitol "873 38 153 iS O98 es Ss 53% 408, Wy, Waste fraction 9%. Fractionation i Xy 248 Mia Sie) ‘se 709% 11% cd a8 atscto! 43g f xylitol in the crystallization step was Soret 38 65% of the xylitol present in the solution. The total recovery by double fractionation was 85-90% xylitol, which had a purity of over 99%. This is to be compared Fractionaione ri 7 Polystyrene sulfonate Polystyrene sulfonate with Sua DVB mean dla meter 039 mm Sr*-form em, diameter 228 em Ieter 0.24 mm Fess" 525'em, diameter 22. em im i Concentration 25.2% ‘omponition above Column Feed Rate Feed Sih SR DVD me da Single fractionation —Reference is made to the scheme in FIG. 11, Resin used was in Sr**-form. A with a recovery of 50-55% of xylitol by the single frac-4,008,285 17 tionation procedure. At the same time, the double fractionation procedure avoids precipitation of signi cant quantities of galactitol with the xylitol crystals Depending on the composition of the feed solution it might sometimes be advantageous to collect only two $ fractions: a xylitol-rich fraction and a waste fraction from both fractionation steps. Reference is made to FIG. 7 and to the tables of Example XI By way of explanation, where fractionations are car- ried out on resins in alkaline earth metal form and 10 polyol fractions or portions thereof are recirculated to recover xylitol values therein, sorbitol tends to accu- ‘ulate in the process. The reason for this can be seen from an examination of FIG. 13. The curves for xylitol and sorbitol show that no significant separation of these two polyols occurs on the Sr*** resin form. Thus, if xylitol were removed from the xylitol-rich fraction and the balance of the fraction was returned to the syst a build-up of sorbitol would occur. Use of the resin in Alt+* or Fet** resin form permits effective separation Of sorbitol; it will be removed from a double fraction- ation system such as that shown in FIGS. 12 and 14 in the W, fraction in sufficient quantities to prevent its build-up within the system. With regard to the galactitol, this substance has @ very low solubility and it is thus important that it be separated from the xylitol before crystallization thereof because it tends to crystallize with the xylitol crystals. ‘The double fractionation scheme shown in FIGS. 12 and 14 substantially reduces the galactitol impurity level in the xylitol crystals. It will be noted that a major part of the galactitol during fractionation I is found in the M, fraction, In fractionation II, however, the major part of the galactitol is separated into the Ws fraction and thus removed from the system. EXAMPLE XV This example shows a good separation of xylitol from ther polyols on a resin in Al*** form. The results of the test are shown in FIG. 15. The conditions of this example were as follows: 2s 3 40 Rein Polyatyrene-divinybenzene in AI"**-form ‘Mean particle siz 0.21 mm sre a2 im 4s Temperatre Feed rate ‘The composition of the feed solution was as follows: 1 kg of dry substance, concentration of 25.2 ‘The polyol syrup had the following composition: Sugar Percent of Dry Substance Xiat Sorbiot Maraitol We claim: 1. A method for the production of xylitol on a com- mercial scale from a pentose-rich solution obtained by acid hydrolysis of a pentosan-containing raw material which comprises the steps of ‘a removing suspended solids from the solution by mechanical filtration; 6s 18 ', removing inorganic salts and the major portion of organic impurities and color from the solution by ion exclusion; ce. removing the balance of color and other organic ‘impurities by treating the solution with a material selected from the group consisting of an ion ex- change resin and activated carbon 4. fractionating the solution thus obtained by ion exchange chromatographic techniques to provide a xylose solution of high purity; e. catalytically hydrogenating the xylose solution; and {. subjecting the xylitol solution thus produced to ion exchange chromatographic. fractionation to re cover a xylitol fraction of high purity. 2. The process of claim 1 wherein step (d) is accom- plished by: a. providing a column of a salt of a polystyrene sulfo- nate cation exchange resin cross-coupled with di- vinyl benzene; b. submerging the column of resin in water; cc. feeding the pentose-rich solution having a dry material content of 25 to 55% by weight in uniform supply to the resin surface in the column at a flow rate of 0.2 to 1.5 cubic meters per hour per square ‘meter of the cross-section of the resin column; and d. recovering successively from the downstream side of the resin bed 1. an inital fraction containing mostly water but also containing other pentoses and a low concen tration of xylose, 2. an intermediate fraction having a high concen- tration of xylose and small amounts of other pentoses, and 3. a final fraction containing other pentoses and a minor amount of xylose. 3. The process of claim 1, wherein step (£) is accom vinyl benzene; ». submerging the column of resin in water; c. feeding the xylitol-rich solution having a dry mate- rial content of 25 to 55% by weight in uniform supply to the resin surface in the column at a flow rate of 0.2 to 1.5 cubic meters per hour per square ‘meter of the cross-section of the resin column; and 4. recovering successively from the downstream side of the resin bed 1. an initial fraction containing mostly water but also containing other polyols and a low concen- tration of xylitol, 2. an intermediate fraction containing a high con- centration of xylitol, together with small amounts of other polyols; and 3. a final fraction containing other polyols and minor amount of xylitol. 4. The process of claim 3, wherein the salt of the resin is selected from the group consisting of alkaline earth metal salts, Fe*** salts and Al*** salts. 'S. The process of claim 3, wherein the column of cation-exchanger, wherein used, is from 2.5 to 5 meters in depth, 6. The process of claim 3 wherein the resin used in step (a) is an alkaline earth metal salt 7, A method for the production of a mixture of poly- ols on a commercial scale from a pentose-rich solution4,008,285 19 obtained by acid hydrolysis of a pentosan-containing raw material which comprises the steps of a. removing suspended solids from the solution by ‘mechanical filtration, b, removing inorganic salts and the major portion of color and other organic impurities by ion exclu- c. removing the balance color and other organic impurities by treating the solution with a material selected from the group consisting of an ion ex- changer resin and activated carbon; 4. fractionating the solution thus obtained by ion ‘exchange chromatographic techniques to provide a pentose solution of high purity, and having a high concentration of pentoses. ¢. catalytically hydrogenating the pentose solution to produce a mixture of polyols, and £. subjecting the polyol mixture to ion exchange chro- ‘matographic fractionation to recover a polyol frac- tion of high purity, free of unhydrogenated sugars and other impuriti 8. The process of claim 7, wherein step (f) is accom- plished by: a. providing a column of a salt of a polystyrene sulfo- nate cation exchange resin cross-coupled with vinyl benzene; », submerging the column in water, c. feeding the polyol solution in uniform supply to the resin surface in the column, and 4d. recovering successively from the downstream side of the resin bed 1. a first fraction comprising unhydrogenated sug- ‘ars and other impurities, and 2. a second fraction comprising substantially pure polyols. 9. The process of claim 8, wherein the second frac- tion comprising a mixture of polyols at (d) (2) is fur- ther separated by ion exchange chromatographic frac- tionation to recover the individual polyols in substan- tially pure form. 10. The process of claim 8, wherein the salt of the resin is selected from the group consisting of alkaline earth metal salts, Fe'** salts and AI** salts 11, The process of claim 8 wherein the salt of the resin is an alkaline earth metal salt. 12, The process of claim 8, wherein the salt of the resin is an Fe*** or Al*"* salt, and wherein the second fraction comprising a mixture of polyols at (d) (2) is further separated by ion exchange chromatograph fractionation to recover the individual polyols in sul stantially pure form. 13. In a method for recovering xylitol on a commer- cial scale from an aqueous mixture of polyols which employs chromatographic techniques on a bed of poly- styrene sulfonate cation exchange resin cross-coupled with di-vinyl benzene, the improvement comprising 2 two-stage fractionation procedure, one stage of the procedure comprising: I. fractionation of the polyol mixture by passing it through a bed of said resin in an alkaline earth metal salt form to recovers a. a waste fraction having a low concentration of aylitol, and b. a xylitobrich fraction; 2. crystallizing xylitol from the xylitol-rich fraction to obtain xylitol erystals and a polyol molas 3. subjecting the polyol molasses remaining after crystallization of the xylitol to a second stage frac- 20 tionation procedure which comprises passing the ‘molasses through a column of said resin in the AI“ or Fe*** form to recover; ‘a, a waste fraction containing a low level of xylitol, 5 and b. a xylitobrich fraction; 4. recovering xylitol crystals from said xylitol-ich fraction, leaving a residual polyol molasses; and 5. returning the residual polyol molasses to the first stage of the separation procedure in admixture with new polyol mixture. 14, In a method for recovering xylitol on a commer- cial scale from an aqueous mixture of polyols which employs chromatographic techniques on a bed of poly- styrene sulfonate cation exchange resin cross-coupled with di-vinyl benzene, the improvement comprising a two-stage fractionation procedure, one stage of the procedure comprising: I. fractionation of the polyol mixture by passing it through a bed of said resin in an alkaline earth ‘metal salt form to recover; a. a waste fraction having a low concentration of xylitol, ». an intermediate polyol molasses fraction, and ¢. a xylitol-rich fraction; 2. erystallizing xylitol from the xylitol-tich fraction to obtain xylitol crystals and a polyol molasses; 3. combining the intermediate fraction in (1) (b) above with the polyol molasses obtained in (2) above to provide a polyol molasses feed for the next stage in the process; 4, subjecting the polyol molasses feed to a second stage fractionation procedure which comprises passing the molasses through a column of said resin 1s 20 2s 30 35 in the AI*** or Fe*** form to recover; a. a waste fraction containing a low level of xylitol, . an intermediate polyol molasses fraction, and ich fraction; 0 itol crystals from said xylitol-rich leaving a residual polyol molasses; 6. combining the residual polyol molasses from (5) above with the intermediate polyol molasses frac- tion from (4) (b); 7. returning the said combined polyol molasses frac- tions to the first stage of the separation procedure in admixture with new polyol mixture. 18. A method for the production of xylitol on a com- mercial scale from a pentose-rich solution obtained by acid hydrolysis of a pentosan-containing raw material which comprises the steps of ‘a. removing suspended solids from the solution by mechanical filtration; . removing inorganic salts and the major portion of, ‘organic impurities and color from the solution by ion exclusion; . removing the balance of color and other organic impurities by treating the solution with a material selected from the group consisting of an ion ex- change resin and activated carbon; d. fractionating the solution thus obtained by ion exchange chromatographic techniques to provide a xylose solution of high purity; ¢. catalytically hydrogenating the xylose solution; f. providing a column of Fe*t* or AI** salt of a polystyrene sulfonate cation exchange resin cross- coupled with di-vinyl benzene; g. submerging the column of resin in water; 45 50 ss 60 654,008,285 2 hh, feeding the pentose-rich solution having a dry material content of 25 to 55% by weight in uniform supply to the resin surface in the column at a flow rate of 0.2 to 1.5 cubic meters per hour per square 5 meter of the cross-section of the resin column; and. recovering successively from the downstream side of the resin bed 1. an initial fraction containing mostly water but 10 also containing other polyols and a low concen- of xylitol, 2. an intermediate fraction cont: centration of xylitol, together with small amounts 15 of other polyols; and 3. a final fraction containing other polyols and a minor amount of xylitol. 16, A method for the production of a mixture of 29 polyols from a pentose-rich solution obtained by acid hydrolysis of a pentosan-containing raw material which comprises the steps of ‘a. removing suspended solids from the solution by 25 mechanical filtration, 30 35 45 50 3s 6s 22 ’. removing inorganic salts and the major portion of ‘color and other organic impurities by ion exclu- sion; . removing the balance of color and other organic, impurities by treating the solution with a material selected from the group consisting of an ion ex- changer resin and activated carbon; 4, fractionating the solution thus obtained by ion ‘exchange chromatographic techniques to provide a pentose solution of high purity, and having a high concentration of xylose, e. hydrogenating the pentose solu mixture of polyols, f. providing a column of an Fe*** or AI*** salt of a polystyrene sulfonate cation exchange resin cross- coupled with di-vinyl benzene; g. submerging the column in water; h. feeding the polyol solution in uniform supply to the resin surface in the column, and i. recovering successively from the downstream side of the resin bed 1, a fraction comprising unhydrogenated sugars ‘and other impurities, and 2..a second fraction comprising substantially pure polyols. mn to produce aUNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 4,008,285 DATED February 15, 1977 INVENTOR(S): Melaja et al. It ts certified that error appears in the above-identified patent and thal said Letters Patent ate hereby corrected as shown below First page, Col. 2, line 4, "3,830,770" should be --3,730,770--; Col. I, line 26, “xyloserich" should read --xylose-rich-~; iI, last line, after "hulls" change the comma to a period; Col. 2, Tine 26, "or" should read --of--; 3, Tine 38, "Altenatively" should read --Alternatively--; » Tine“7, after "of" insert --a--; 4, line 44, “hydrosylate" should read --hydrolysate--; Col. 4, Tine 52, "and and" should read --and any--; 4, line 56, delete "the" (third occurrence) ; 4, line 61, “hydrosalate" should read --hydrolysate--; 5, line 31, after "specifically", delete the comma; , line 33, delete "a"; Col. 7, Tine 6I, “as" should read --is--; Col. 8, Tine 4, "the polyol and" should read --a polyol-- and "xylitorl" should read --xylitol--; Col. 10, line 6, “polystryene" should read --polystyrene--; Col. 12, Tine 8, “catio" should read --cation: Col. 13, line I, “the” (first occurrence) should read --an--; Col. 16, Tine 16, delete the comma after "Xi"; and Col. 19, Tine 8, after “balance” insert --of. Signed and Sealed this Twenty-eighth Day of Sune 1977 [SEAL] Attest: RUTH C. MASON C. MARSHALL DANN Attesting Officer Commissioner of Patents and Trademarks