United States Patent 19 Rohrbach et al. (54 0s) 173) Ri) 2} [63] bi [52] (58) (56) PRODUCTION OF HIGH SUGAR SYRUPS. Inventors: Ronald P. Rohrbach, Forest Lake, Til; Mary J. Maliarik, Ann Arbor, Mich.; Thomas P. Malloy, Lake Zurich, Ml Assignee: UOP Ine., Des Plaines, I Appl. Now: 499,652 Filed: May 31, 1983 Related US. Application Data Continuation-in-part of Ser. No. 360,120, Mar. 19, 1982, abandoned. Int. CL (C12P 19/22; C12P 19/20; Ci2N 11/14 us. cL. +» 435/98; 127/55; 210/651; 2107654, 435/96; 435/176 Field of Search 210/653, 654, 655, 500.2, 210/651; 127/54, 55; 435/95, 96, $9, 105; 735/176 References Cited US. PATENT DOCUMENTS 3.331,772 1/1967 Brownscombe et al. 210/683 31720583. 3/1974 Fisher .. 435/95 531783,100 1/1974 Larson eta. 435/96 3.857.782 12/1974 Crowley «0 “ n1076a6 4039440 8/1977 Cadotte “31075002 4338398 7/1982. Yoneyama 435/96 (11) Patent Number: 4,511,654 {45} Date of Patent: Apr. 16, 1985 4.316707. 3/1983. Lehmann 210/679 $429,122. 1/1984 Zapancie 536/128 FOREIGN PATENT DOCUMENTS SS-41171 11/1980. Japan 210/683 Primary Examiner-—Peter Heuskoci Attorney, Agent, or Firm—James R. Hoatson, Jt Raymond H. Nelson; William H. Page, I 7) ABSTRACT ‘The preparation of syrups which contain a high glucose for maltose content may be effected in a two-step pro- cess. In the first step, 2 feedstock such as starch which hhas been pretreated with alpha-amylase to adjust the dextrose equivalent is contacted with an enzyme such as amyloglucosidase or beta-amylase immobilized on @ solid support. The contact time is adjusted by correlat- ing the residence time and the liquid hourly space ve- locity so as to provide a conversion percentage of starch in the range of from about 50% to 85%, thus avoiding the formation of undesired conversion prod- ucts. The partially hydrolyzed reaction mixture from the enzyme treatment is then passed through an ultrafil- tration membrane whereby the permeate comprising the high glucose or maltose content is recovered, while the retentate is recycled for admixture with the partially hydrolyzed reaction mixture or for further treatment with the immobilized enzyme. 9 Claims, No Drawings4,511,654 1 PRODUCTION OF HIGH SUGAR SYRUPS CROSS-REFERENCE TO RELATED ‘APPLICATION ‘This application is a continuation-in-part of our co- pending U.S. application Ser. No, 360,120 filed Mar. 19, 1982 and now abandoned, all teachings of which are incorporated herein by reference thereto. BACKGROUND OF THE INVENTION In many commercial enterprises, sugar is utilized to a great extent for its sweetening properties. It is used in the sweetening of foods, for the manufacture of syrups and confectionery items, in preserves and jams, as a chemical intermediate ‘for detergents, emulsifying agents and other sucrose derivatives such as plasticiz= ers, resins, glues, etc. The usual derivation of sugar is from cane sugar and sugar beets. It is obtained by crush- ing and extracting the sugar from the cane with water or extracting the sugar from the sugar beet with water followed by evaporation and purifying with lime, absor- bent carbon and/or various liquids. The chief compo- nent of this type of sugar is sucrose, while other sugars may contain other polysaccharides such as dextrose and levulose (fructose). Other polysaccharides which pos- sess sweetening properties include glucose, maltose, ete ‘The various polysaccharides possess varying degrees of sweetness, especially when in pure form and not con- taminated by an reversion products. One source of glucose which possesses a relatively high degree of sweetness and which, in turn, may be converted to fructose, the latter possessing an even greater degree of sweetness, is a starch. As is well known, starch is present in many naturally occurring plants including corn, potatoes, rice, tapioca, wheat, ete. Heretofore, it has been known to treat starch with an enzyme such as amyloglucosidase to obtain glucose. However, the treatment heretofore provided entailed a relatively long residence time in order to obtain a glu- cose syrup which contained about 94% glucose. The relatively long residence time which has heretofore been required restricts the throughput of glucose and results in the appearance of reversion products which impart a bitter taste to the glucose, thus negating the sweetening property of the compound as well as requir- ing further treatment in order to remove the offending product. One such reversion product which imparts & bitter taste comprises isomaltose. ‘Many methods involving the use of an enzyme such as amyloglucosidase to convert starch into sugar have been tried. However, each of these methods has some disadvantages attached thereto. For example, when using a free enzyme, it is necessary to continuously replace the enzyme which is lost during the production Of the desired saccharide. Likewise, when using an immobilized enzyme, the heretofore relatively long residence time has resulted in the appearance of un- wanted side products. As will hereinafter be shown in greater detail, we have now discovered that the feedstream comprising @ starch which possesses a low dextrose equivalent may be subjected to a partial hydrolysis to provide a prede- termined degree of conversion due to a correlation of residence time and liquid hourly space velocity, and to 2 degree wherein the reversion products which consti- 5 2 2 30 6 2 tute an undesired side reaction are extremely low or, in some instances, non-existent. BRIEF SUMMARY OF THE INVENTION This invention relates to a process for obtaining high glucose or maltose content syrup. More specifi cally, the invention is concerned with a process for the production of a high glucose or maltose content syrup by treating a feedstock comprising starch with an im- mobilized enzyme followed by passage of the partially hydrolyzed reaction mixture through an ultrafiltration membrane whereby the permeate which is recovered comprises syrup having a high glucose of maltose content, ‘Syrups which are high in glucose or maltose concen- tration comprise désirable chemical entities. By utilizing these syrups which are high in glucose or maltose con- tent for sweetening processes such as in baking goods, ‘candies or in the case of maltose, in culture media or even as a sweetener of nutrient, itis possible to utilize lesser amounts of these syrups, thereby concomitantly reducing the overall cost of the finished product. In addition, as will hereinafter be set forth in greater detail, the syrups which are high in glucose or maltose content will aso contain a relatively small amount or no amount atall of reversion products which impart a bitter taste to the syrup, thereby reducing the efficiency of the glu- ‘cose or maltose to act as a sweetening agent. It is therefore an object of this invention to provide a process for producing syrups which possess a high glu- cose or maltose content. ‘A further object of this invention is to provide a process for producing syrups which possess a high glu- ‘cose or maltose content with little or no reversion prod- ucts present in said syrups. In one aspect, an embodiment of this invention re- sides in a process for the production of a high glucose ot maltose syrup which comprises treating feedstock having a low dextrose equivalent with an immobilized ‘enzyme selected from the group consisting of amyloglu- cosidase and beta-amylase in a conversion zone at con- version conditions adapted to effect a conversion of said feedstock to glucose or maltose in a range of from about 50% to about 85%, passing the resultant partially hy- Grolyzed reaction mixture through an ultrafiltration ‘membrane to form a retentate and a permeate, recycling the retentate for further conversion, and recovering the permeate comprising a high glucose or maltose content syrup. A specific embodiment of this invention is found in the process for the production of a high glucose syrup which comprises treating a feedstock comprising starch which has been pretreated with alpha-amylase to pro- vide a dextrose equivalent in the range of from about 5 to about 25 with an amyloglucosidase enzyme compos- ited on a solid support at a temperature in the range of from about 45° to about 70° C., a pressure in the range ‘of from about I to about 1000 pounds per square inch, a liguid hourly space velocity in the range of from about 2 to about 50 and for a residence time in a range of from about 4 minutes to about 1.6 hours, passing the resultant partially hydrolyzed reaction mixture through an ultra- filtration membrane comprising polystyrenesulfonate at temperature in the range of from about ambient to about 70° C. and a pressure in the range of from about 25 to about 1500 pounds per square inch, recycling the ‘etentate material for further conversion and recover-4,511,654 3 ing the permeate comprising a syrup possessing a high glucose content. Other objects and embodiments will be found in the following further detailed description of the present invention. 5 DETAILED DESCRIPTION OF THE INVENTION ‘As hereinbefore set forth, the present invention is concemed with a two-step process for the production ‘of syrups which possess a high glucose or maltose con- tent. The process is effected by treating a feedstock, comprising a liquified starch which itself has been pre- treated to adjust the dextrose equivalent, with an appro- priate enzyme Which is in an immobilized state followed by passage of partially hydrolyzed reaction mixture over a membrane, the latter or second step of the pro- cess permitting the permeation of the desired sugar through the membrane while concurrently rejecting the higher oligosaccharides which, in the form of the reten- tate, may be recycled for further treatment with the enzyme. Heretofore, in order to achieve a syrup which would contain about 94% glucose or maltose by treating starch with an enzyme, it was necessary that the starch be in contact with the enzyme for a relatively long residence time. A disadvantage in allowing the starch to be in contact with the enzyme restricted the throughput of the desired sugar such as glucose or maltose and, ‘when utilizing an immobilized enzyme, the amount of 30 undesired reversion products which possessed a bitter taste would be promoted. For example, isomaltose which possesses a disagreeable taste would be present in the reaction mixture to such an extent as to seriously impair the use of the desired product as a sweetening agent. ‘As will hereinafter be shown in greater detail, by uiilzing the process of the present invention, itis possi- ble to obtain a syrup which contains a high glucose or maltose content, that is, in excess of 94% with little or no reversion products imparting a disagreeable taste to the finished product. “The present process involves the treatment of a feed- stock comprising aliquified starch which has been pre- treated with an enzyme such as alpha-amylase whereby the dextrose equivalent is increased to a range of from about 5 to about 25. The treatment of the pretreated Tiquified starch with an immobilized enzyme such as amyloglucosidase or beta-amylase is effected under conversion conditions which will permit a conversion of the feedstock to glucose or maltose ina range of from about 50% to about 85%. The conversion conditions include a temperature in the range of from about 45° to about 70° C. and a pressure in the range of from about 1 to about 1000 pounds per square inch (psi). The resi- dence time during which the starch is in contact with the immobilized enzyme is relatively short, that is in a range of from about 4 minutes to about 1.6 hours and is in correlation with liquid hourly space velocities which ‘may range from about 2 to about 50. The space velocity and residence time are correlated in such a manner, i, short residence time and high space velocity within the ranges hereinbefore set forth $0 as to provide a conversion rate within the desired range. Conversely, itis also contemplated that long 6 residence times and low space velocities withthe afore- said range may also be employed to effect the desired result. 10 15 20 2s 3s 0 45 50 33 4 ‘The correlation of the space velocity and the rela- tively short residence time will permit a sufficient con- version of the starch to glucose or maltose within the desired range while preventing the formation of the undesired reversion products to a degree wherein they are extremely low or even in some cases nonexistent. In addition, the relationship between the residence time and the conversion will result in a bimodal reaction product, that is, the molecule sizes will be greatly differ- ‘ent. As will hereinafter be shown in greater detail, there is a relatively large difference in size between the glu- ‘cose or maltose molecules and the remaining oligosac- ccharides. This difference will permit the use of ultrafil- tration membranes to readily separate the permeate from the retentate. ‘The partially hydrolyzed reaction mixture which is obtained from the conversion step is then subjected to an ultrafiltration step wherein said reaction mixture is passed over a membrane which possesses an appropriate molecular weight and pore sizes whereby the higher glucose syrup will pass through the membrane as per- ‘meate while the retentate material containing unhydro- lyzed oligosaccharides may be recycled for additional treatment. The ultrafiltration step in the present process may be effected under conditions which will include a temperature in the range of from about ambient (20"-25" C.) up to about 70° C. and a pressure in the range of from about 25 to about 1500 psi. ‘AS heretofore set forth, the enzymes which are uti- lized in the process of this invention comprise amylo- ‘glucosidase or betaamylase which are composited on a solid support. By utilizing enzymes which are immobi- lized on the support, itis possible to stabilize the enzyme ina relative manner and therefore to permit the reaction Of the enzyme which otherwise may be lost in the reac- tion medium. Such immobilized or insolubilized en- zymes may be employed in various reactor systems such as in packed columns, stirring tank reactors, etc., de- pending upon the nature of the substrate which is uti- lized therein. By permitting the reuse of the enzymes which are in a relatively stable condition and thus may be utilized for a relatively lengthly period of time, it is possible to operate the process in a commercially attrac- five and economical manner. The particular enzyme may be immobilized on a solid support in any manner known in the art. One such method of immobilizing the enzyme which may be used as an illustration of a method for immobilizing the en- ‘zyme comprises treating an inorganic porous support ‘material including, but not limited thereto, metal oxides such as alumina, and particularly gamma-alumina, silica, zirconia, silica-magnesia, silica-zirconia-alumina, etc., ‘gamma-alumina containing other inorganic compounds such as boron phosphate, etc., ceramic bodies, ceramic fibers, ceramic monoliths which may be coated with a porous inorganic oxide, as well as compositions of the aforementioned materials, one of said materials which ‘may serve as a coating for another material comprising the solid support. The service area of the particular porous support may vary over a relatively wide range, said range being from about 1 to about 500 or more m?/g. In addition, the configuration of the support ma terial may vary depending upon the particular type of support which is utilized. For example, the support may be in the form of spheres, particulates, monoliths, pel- lets, fibers, etc. Its to be understood that the aforemen- tioned types of porous supports and configurations