United States Patent (19) 11, 3,708,396 Mitsuhashi Et Al
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United States Patent (19) 11, 3,708,396 Mitsuhashi et al. (45) Jan. 2, 1973 54 PROCESS FOR PRODUCING 3,492,203 1/1970 Mitsuhashi............................. 195/31 MALTTOL 3,565,765 2/1971 Heady et al.................. .......... 195/31 75) Inventors: Masakazu Mitsuhashi, Okayama-shi, 3,535,123 10/1970 Heady.................................... 195/31 Okayama; Mamoru Hirao, Akaiwa 2,004,135 6/1935 Rothrock.......................... 260/635 C gun, Okayama; Kaname Sugimoto, OTHER PUBLICATIONS Okayama-shi, Okayama, all of Japan Abdullah et al., Mechanism of Carbohydrase Action, Vol.43, 1966. 73) : Assignee: Hayashibara Company, Okayama, Hou, E. F., Chem. Abs., Vol. 69, 1968, 53049d. Japan Kjolberg et al., Biochem. J. p. 258-262, Vol. 86, 1963. 22 Filed: Jan. 8, 1969 Lee et al., Arch Biochem. Biophys, Vol. 1 16, p. (21) Appl. No.:789,912 162-167, 1966. Payur, J. H., Starch, Chem. and Tech., Vol. 1, p. 166, 30 Foreign Application Priority Data 1965. Jan. 23, 1968 Japan.................................. 43/3862 Primary Examiner-A. Louis Monacell July 1, 1968 Japan................................. 43148921 Assistant Examiner-Gary M. Nath July 1 1, 1968 Japan................................. 43148922 Attorney-Browdy and Neimark 52 U.S. Cl.............. 195/31 R, 260/635 C, 99/141 R 5 Int. Cl................................................ C13d 1100 57 ABSTRACT 58) Field of Search............. 195/31; 99/141; 127/37; A process for producing maltitol from a starch slurry 260/635 C which comprises hydrolyzing the starch slurry with beta-amylase and alpha-1,6-glucosidase to produce a 56 References Cited high maltose containing product and catalytically hydrogenating the maltose with Raney nickel after ad UNITED STATES PATENTS justing the pH of the maltose product with calcium 2,868,847 111959 Boyers.................................. 260/635 carbonate. 3,137,639 6/1964 Hurst et al.............................. 195/31 3,490,922 11970 Hurst...................................... 195/31 24 Claims, 1 Drawing Figure PATENTEDJAN 2 1973 3,708, 396 p INVENTORS 4eta24 ATTORNEYS 3,708,396 1. 2 PROCESS FOR PRODUCING MALTTOL is decreased to about 90 percent with the production of about 8 percent sorbitol. In the experiments, therefore, DETAILED EXPLANATION OF THE INVENTION the pH of the solution was adjusted midway in an effort This invention relates to a process for producing 4 to improve the yield. However, the yield was only (o-D-glucopyranosyl)-D-sorbitol, or maltitol, which is 5 slightly increased to 93 percent. Then, calcium car a high-pressure hydrogen reduction product from bonate was added as a moderate neutralizing agent to maltose. the starting material maltose in an amount of 0.06 to Maltitol has heretofore been made by a know 0.3 percent on the basis of the latter amount. This process which consists of removing dextrin as by al resulted in an increase of sorbitol production to 1.6 cohol fractionation from maltose having a purity of 10 percent, thus indicating that the decomposition of more than 60 percent that is obtained by decomposi maltose came to an end, and also an increase of mal tion of starch by malt amylase, repeating recrystalliza titol yield to more than 96 percent. The result was tion of the dextrin-free maltose several times to attain a satisfactory in both purity and yield. purity of about 90 percent, and then reducing the high Thus, in accordance with the process of the inven purity maltose by hydrogenation under high pressure. 15 tion, 100 kg. of dehydrated starch in the form of a 3 This conventional process is disadvantageous in that percent aqueous solution was decomposed with heat, the means to attain the end are not adapted for com and the branched structure of dextrin was decomposed mercial production with poor yield and high produc into a straight-chain structure by the addition of cy-1,6- tion cost. glucosidase, and then saccharification was effected The purpose of this invention is to eliminate these 20 with 6-amylase. The starch was thus completely disadvantages and produce maltitol on an industrial decomposed into maltose, giving 103 kg. of maltose scale at low cost. with a purity of 95 percent. Briefly stated, the present invention is directed to The maltose upon hydrogenation yielded 103.5 kg. quantity production of maltitol on a commercial basis 25 of maltitol with a purity of 95 percent. by decomposing branched structures of starches into When the saccharification was effected without the amylosic straight-chain structures by the use of o-1,6- addition of o-1,6-glucosidase but solely with 3 glucosidases (isoamylase and pullulanase), the en amylase, the maltose in the saccharified solution was zymes obtained, for example, by culturing strains of decomposed leaving ov- and 6-limit dextrins behind. Aerobacter aerogenes and which have specific activi 30 Fractional estimation of various saccharides by paper ties in cutting off the a-1,6-glucoside bonds in starch chromatography showed that the product contained 50 amylopectin, thereby aiding the amylolytic activity of percent maltose, 30 percent dextrin and 20 percent g-amylase to obtain maltose with a purity of nearly 100 oligo-saccharide. percent, and thereafter reducing the maltose by In this case, if this saccharified solution is hydrogenation under high pressure. 35 hydrogenated, it affords 102 kg. of a reduction product By way of illustration, in one experiment (A), a 10 which is a mixture of sugar alcohols of 50 percent mal percent sweet potato starch slurry was liquefied by ov titol, oligo-saccharide and dextrin. To obtain high-puri amylase to D.E. 2.7 percent, and 25 units of g-amylase ty maltitol from this reduction product is difficult was added per gram of the starch and then the mixture because of industrial problems involved. was saccharified at 55C. for 16 hours, while, in 40 In order to produce high-purity maltitol without the another experiment (B), similar saccharification was use of o-1,6-glucosidase, maltose must be taken out of carried out with the addition of 25 units of 3-amylase the saccharified solution by alcohol fractionation and and 10 units of oz-1,6-glucosidase per gram of starch. must be recrystallized. When the procedure was re The compositions of the saccharified solutions that peated several times to obtain maltose with the same resulted were as tabled below. It was thus noted that 45 purity of 95 percent as by the process of the invention, when the 6-amylase was used singly (A) the only 3 kg. of 95 percent maltose was produced. The saccharified solution had a maltose content of 69.6 per product upon hydrogenation yielded 3 kg. of 95 per cent but when the g-amylase was used in combination cent maltitol. Thus, the yield is too low, the production with the a-1,6-glucosidase (B) the maltose content of means are not adapted for commercial production, and the resulting solution exceeded 90 percent. 50. the product is costly. As described above, the present invention permits Saccharified Composition production of high-purity maltitol with good yield in solution Maltose Glucose Malttriose Dextrin A 69.6% 1.1% -3.5% 25.7% commercial operation and hence provision of the B 90.4% 0.4% 1.3% 7.9% product at cheap price, which has never been possible 55 with the conventional process. In hydrogenating maltose, the maltose was dissolved The process of producing maltose will now be more in water to prepare a 40 to 60 percent aqueous solution fully described hereunder. It has been known that and Raney nickel ("N154,' trademark of Nikki maltose is manufactured from starches by liquefying a Kagaku's product) was used as a catalyst in an amount starch and saccharifying the liquid with the addition of of 8 to 10 percent of the amount of the aqueous solu 60 malt (i.e., a mixture of o- and (3-amylases). According tion. Hydrogen was forced in the solution with a pres to this known process, the maltose contents of the sure of 20 to 100 kg/cm' while the temperature was saccharified products are at most 50 to 60 percent. The gradually increased to 80° to 150°C., and thus products usually contain large percentages of proteins hydrogenation was carried out. In such a case it some and limit dextrins. Thus, because of the low maltose times occurs that the pH of the solution drops and the 65 contents and high impurity contents, the products in reaction slows down. If such is the case a decomposi volve great difficulties in being purified merely by sim tion of maltose will take place and the yield of maltitol ple recrystallization procedures. 3,708,396 3 4. The factor which makes it impossible to effect ing the starch slurry at 80 to 180° C., or by adding cy complete amylolysis of a starch into maltose in ac amylase and liquefying the mixture with the application cordance with the conventional process is the produc of heat ranging from 70 to 95 C, or weakly acidifying tion of limit dextrins including a-1,6-glucoside bonds. the slurry and then liquefying the starch with heat. In The present invention has been perfected with this in any case, the liquefaction or thermal dissolution of view. More particularly, the present invention is starch decomposes the starch molecules into finer ones directed to the manufacture of highly pure maltose at and therefore, even when the starch has been high yields from starches by selectively decomposing completely amylolyzed by G-amylase, the molecules the ox-l,6-glucoside bonds contained in amylopectin, a formed of an even number of glucose units are decom constituent of starch, that is, the o-1,6-glucoside bonds O posed into maltose molecules of two glucose units that form the branches of amylopectin having a each, and thus leave maltotriose or glucose per branched molecular structure, by taking advantage of molecule of the liquefied starch.