CRYSTALLINE FRUCTOSE PREPARATION

Abstract: This invention relates to the crystallization of fructose from aqueous fructose-containing dispersions through the addition of at least two alcohols, such as ethanol and iso­ propanol. The resultant crystalline fructose is obtained in good yields and purity.

Description: CRYSTALLINE FRUCTOSE PREPARATION BACKGROUND OF THE INVENTION 1. Field Of The Invention This invention relates to a process for preparing crystalline fructose, in particular to a process for obtaining fructose in high yields with a high degree of purity. 2. Description Of The Art Practices Fructose may be viewed as one-half of a sucrose molecule with the other half being dextrose (glucose). Sucrose is, of course, known commonly as tabie sugar and is widely used as a sweetener and structurant in many products from cake mixes to soft drinks. It has been determined that the fructose por tion of the sucrose molecule has greater sweetening power on an equal weight basis than sucrose or dextrose. Therefore, if fructose is substituted into formulations, the overall. cost may be lowered when compared to using sucrose. The use of fructose provides a higher degree of sweetening at a given weight level than sucrose. Thus, fewer calories are present in a fructose-sweetened product at equal sweetening levels than when sucrose is used. Several routes have been utilized to isolate and separate fructose as a crystalline component. For the most part, fructose is prepared by isomerizing dextrose which is obtained through the refining of corn syrup. The isomerization of dextrose is generally not a 100% conversion and therefore the fructose must be separated from the remaining saccharides, e.g. dextrose, and crystallized from the aqueous dispersion. The separation of fructose from the syrup is complicated by the high degree of solubility of the fructose in water. Therefore, the separation of fructose at acceptable purity and yield from an aqueous syrup is yet to be accomplished in a practical manner. U. S. Patent 3,607,392, issued September 21, 1971, to Lauer, describes a process and apparatus for obtaining crystalline fructose through the use of methanol. Methanol has limits on its usage in food products which is the major market for crystalline fructose in the first instance. U.S. Patent 3,883,365, issued to Forsberg et al on May 13, 1975, describes a separation of fructose from glucose within a narrowly constrained pH range by lowering the temperature of the reaction mixture. The disadvantage in this process Is that it Is not economical to refrigerate a syrup In a plant setting. That is, the syrup will be at least at an ambient temperature during processing and the mechanics of cooling require the substantial expenditure of energy. Vamauchi U.S. Patent 3,928,062, issued December 23, 1975, discloses recovering fructose by seeding anhydrous fructose crystals into a supersaturated solution of fructose. U.S. Patent 4,371,402, issued February 1, 1983, to Kubota, describes the dehydration of fructose utilizing an organic solvent having azeotropic behavior with respect to water. The teachings of Dwivedi et al in U.S. Patent 4,199,373, issued April 22, 1980, relate to anhydrous free-flowing crystalline fructose obtained by allowing a seeded syrup to stand at low temperature and high relative humidity. United States Patent 4,199,374, issued April 22, 1980 also to Dwivedi et al suggests seeding a syrup containing fructose and allowing it to stand followed by recovery of the fructose. U. S. Patent 3,513,023 to Kush, issued May 19, 1970, discloses the recovery of crystalline fructose over a broad pH range, through concentration and cooling, following seeding of the mixture. It therefore remains to effectively separate fructose from an aqueous syrup in a high degree of purity and with a high yield. It is an objective of the present invention to provide a process that permits crystalline fructose to be obtained from an aqueous fructose mixture with good yield and purity. Throughout the specification and claims, percentages, parts and ratios are by weight, temperatues are degress Celsius, and pressures are in KPa over ambient unless otherwise indicated. The present invention thus provides a process for preparing crystalline fructose from an aqueous fructos.e-containing dispersion by crystallization, characterized in that said process compr-ises-adding at least two alcohols to an aqueous dispersion containing, on a dry solids basis, at least about 85% fructose, the quantity of alcohols added being such that the weight ratio of fructose to alcohols in the resultant mixture is from about 4:1 to 1:4. In .a preferred embodiment, the process of the invention includes the steps of: (a) obtaining an aqueous dispersion containing on a dry solids basis at least about 858 by weight fructose; (b) adding to the aqueous dispersion a mixture of at least two alcohols; (c) mixing the aqueous dispersion and the alcohols until the weight ratio of the fructose to the alcohols is from about 4:1 to 1:4 (d) allowing crystallization to occur; and, recovering the fructose. In a particularly preferred embodiment, the process of the invention includes the steps of: (a) obtaining an aqueous dispersion containing on a dry solids basis at least about 85% by weight fructose; (b) adding to the aqueous dispersion ethanol and isopropanol in a re spective weight ratio of the alco hols of 250:1 to 1:250; (c) mixing the aqueous dispersion and the alcohols until the weight ratio of the fructose to the alcohols is from about 4:1 to 1:4; (d) allowing crystallization to occur; and, recovering the fructose. The first component of the present invention is the aqueous- -dispersion (syrup) from which the fructose is to be crystallized. While the aqueous dispersion could consist essentially of fructose and water, it is more likely that other saccharides and various materials obtained in the processing of corn syrups will be present. Namely, dextrose is typically present at from 38 to 10% by weight in the syrup. The foregoing is stated as it may be desirable in some circumstances, where highly pure fructose is desired, that crystalline fructose be redissolved in water and recrystallized according to the present invention. In any event, the amount of fructose in the syrup is preferably from about 88% to about 97% by weight fructose and most preferably from about 93% to about 96% by weight on a dry solids basis (dsb). The preferred fructose source is from corn syrup, however, any source of fructose such as from inulin or other sources such as cane or beet may be employed. The conditions for the aqueous dispersion prior to the addition of the later described alcohols are such that he pfl is conveniently from about 3.0 to about 5.0, preferably from about 3.5 to about 4.8. The temperature of the syrup and alcohol mixture prior to the crystallization step is conveniently from about 40"C to about 800C, preferably from about 50 C to about 700C. The alcohols utilized herein are preferably obtained in their anhydrous state. This condition is imposed as any additional water in the system will decrease the yield of fructose due to its solubility in water. The two alcohols (minimum) used to obtain crystalline fructose are conveniently selected from methanol, methanol n-propano3., isopropanol, n-butanol, and sec-butanol. The alcohols are desirably monohydric. The alcohols preferably employed herein are ethanol and isopropanol. The weight ratio of one alcohol to each other alcohol is conveniently from 250:1 to 1:250; more preferably 200:1 to 1:200. It is preferred that ethanol be the predominant alcohol in the mixture of the alcohols. It is also preferred that isopropanol also be present in the mixture of alcohols. The weight ratio of the ethanol to the isopropanol is desirably from about 80:20 to about 98:2; preferably from about 85:15 to about 97:3 and most preferably from about 90:10 to about 96:4. It has been determined that within the forego ing ranges that the mixture of ethanol and isopropanol gives a higher yield and purity of the fructose obtained when compared to either of the alcohols utilized alone. The alcohols may be added to the syrup separately or by premixing of the alcohols. The ethanol, as it is a regulated material, may be denatured with a suitable denaturant such as methanol. Methanol is conveniently used to denature ethanol at from 1% to 10%, particularly at 58 as in 3A alcohol. Thus ternary and higher mix tures of alcohols are contemplated herein. The weight ratio of the fructose in the resultant aqueous dispersion to the alcohols is from about 4:1 to about 1:4; preferably from about 3:1 to about 1:3. The alcohol ratio to the fructose in the aqueous dispersion is important in that an insufficient amount of alcohol does not allow the fructose to be effectively separated. The aqueous dispersion and the alcohols are preferably mixed as near to ideally as possible. The mixing conveniently is also continued during the crystallization step which is preferably induced by using a seeding material, conveniently a suitable food-grade seeding material. The preferred seeding material- is crystalline fructose which may be initially obtained from a commercial source. Any other suitable sugar or saccharide may be employed, however, as the goal is to obtain a high fructose content with as high a degree of purity as possible, it is desirable to use pure fructose for the seeding. Of course, after the process is started, a portion of the product which has been crystallized as fructose may be recovered and utilized for further initiation of seeding. The mixing of the aqueous dispersion as previously noted allows an intimate mixing'of the alcohols thereby selectively extracting the fructose such that the solution structure of the water, fructose and alcohol molecules bring about favorable conditions for crystallization. Thus, when the seeding is initiated, crystallization of the dispersed fructose is extremely rapid. The use of two alcohols also reduces the viscosity of the syrup thereby facilitating mixing. The present process may be run on a continuous basis by introducing a fresh feed stream into the mixing tank, seeding, and removing crystalline fructose slurry from the bottom of the tank. The crystallized -fructose can then be drawn off, filtered, recovered as o semi-solid, and dried. Other suitable methods of r covering the fructose from the slurry can also be employed. The present invention as described above allows for the recovery of crystalline fructose particles which average between 100 and 1,000; preferably 150 and 500 microns. Larger granules are also possible if desired. The product is of high purity when seeded with fructose and is generally suitable for all applications in which crystalline fructose is desired. The present invention will now be further illustrated by means of the following non-limitin Examples: EXAMPLE I Corn syrup containing 96.8% fructose on a dry solids basis is adjusted to a pH of 4.5 and evaporated under vacuum to a solids content 91.6% by weight. The remaining components in the mixture include dextrose and water. The evaporated product in an amount of 208 parts is dissolved in 89.6 parts of an alcohol mixture which is 95:5 by weight ethanol to isopropanol. Both alcohols were essentially anhydrous prior to introduction into the system. The alcohol is added incrementally to the aqueous mixture. The resulting combination of the aqueous mixture and the alcohols is mixed vigorously at 550C to obtain a clear solution. 1.905 parts of crystalline fructose is then mixed with the solution and stirring continued while the mixture is cooled to 220C over a period of 4 hours. The seeded mixture is then filtered and washed with three separate, 24 part aliquots of the previously described alcohol mixture at OOC. The fructose product so recovered is air-dried to obtain 147 parts of the product which is a white crystalline powder having a purity of 99.4to by weight. Substantially similar results are obtained by varying the alcohol mixture used above within the range -described above. The pH of the aqueous dispersion may be varied between about 3 and about 5 with substantially similar results. EXAMPLE II Several comparative tests of various alcohols and alcohol mixtures are conducted according to the process described in Example I. The results are reported in Table I below. TABLE I Alcohol Product Purity 8 Yield2 1008 IPA3 94.6 (gummy) 90 1008 ETOH4 98.9 - 99.8 73 1008 MEOH5 99.5 55 5% MEOH/95% ETOH 99.7 63 10% MEOHI908 ETOH 99.3 51 15% MEOH/85% ETOH 99.5 64 5% IPA/95% ETOH 99.4 81 7% IPA/93% ETOH 98.9 88 108 IPA/90% ETOH 98.9 91 15% IPA/85% ETOH 98.3 87 1. % fructose in product. 2. Yields of fructose. 3. IPA is isopropanol. 4, ETOH is ethanol. 5. MEOH is methanol. The tests conducted show the mixtures of IF and ETOH are most effective in increasing the purity and yield of crystalline fructose. A similar run using 1 part isopropanol to 99 parts ethanol increased the yield of crystalline fructose by greater than 14% by weight over a comparative run using ethanol alone.

Claims: CLAIMS 1. A process for preparing crystalline fructose from an aqueous fructose-containing dispersion by crystallization, characterized in that said process comprises adding at least two alcohols to an aqueous dispersion containing, on a dry solids basis, at least about 85% fructose, the quantity of alcohols added being such that the weight ratio of fructose to alcohols in the resultant mixture is from about 4:1 to 1:4. 2. A process as claimed in claim 1 including the steps of: (a) obtaining an aqueous dispersion containing on a dry solids basis at least about 85% by weight fructose; (b) adding to the aqueous dispersion a mixture of at least two alcohols; (c) mixing the aqueous dispersion and the alcohols until the weight ratio of the fructose to the alcohols is from about 4:1 to 1:4; (d) allowing crystallization to occur; and, recovering the fructose. 3. A process as claimed in either of claims 1 and 2 wherein said at least..two alcohols are monohydric lower alkanols. 4. A process as claimed in any one of claims 1 to 3 wherein said at least two alcohols are selected from: ethanol, methanol, n-propaflol, iso-propanol, n-butanol and sec-butanol. 5. A process as claimed in any one of claims 1 to 4 wherein said at least two alcohols are used in a weight ratio of one alcohol to each other alcohol of from about 250:1 to 1:250. 6. A process as claimed in any one of claims 1 to 5 wherein said at least two alcohols comprises methanol and isopropanol. 7. A process as claimed in claim 6 wherein ethanol and isopropanol are used in a weight ratio relative to each other of from- about 80:20 to about 98:2. 8. A process as claimed in claim 6 wherein ethanol and isopropanol are used in weight ratio relative to each other of from about 85:15 to about 97:3. 9. A process as claimed in any one of claims 6 to 8 wherein said at least two alcohols additionally comprises methanol. 10. A process as claimed in any one of claims 1 to 9 wherein the aqueous dispersion to which said at.leasttwo alcohols are added- contains from about 5% to about 15% water. 11. A process as claimed in any one of claims I to 10 wherein the aqueous dispersion to which said at least two alcohols are added contains from about 88% to about 97% by weight fructose on a dry solids basis. 12. A process as claimed in any one of claims 1 to 11 wherein the aqeuous dispersion also contains dextrose. 13. A process as claimed in any one of claims 1 to 12 wherein the recovery of the crystalline fructose is enhanced by seeding the dispersion. 14. A process as claimed in claim 13 wherein the seeding is accomplished using a seeding material selected from saccharides and crystalline fructose. 15. Aprocess as. claimed in any one of claims 1 to 14 wherein the quantity of alcohols added is such that the weight ratio of fructose to alcove in the resultant mixture is from about 3:1 to about 1:3. 16. A process as claimed in any one of claims 1 to 15 wherein mixing is continued during crystallization. 17. A process as claimed in any one of claims 1 to 16 wherein the temperature of the dispersion is maintained at from about 400C to 8.00C prior to the crystallization. 18. A process as claimed in any one of claims 1 to 17 wherein the pH of the aqueous dispersion is from about 3.C to about 5.0.

Inventors: DAY, GARY ALLEN
Applicants: A.E. STALEY MANUFACTURING COMPANY
Application year: 1985
Main classification: C13K11
IPC codes: C13K11