Methods of making solid sweeteners and solid sweetener blends

Abstract

The technology disclosed in this specification pertains to a dry sweetener composition and methods of making the sweetener. The sweetener can by a single sweetener, for example allulose, or can be a blend of sweeteners. The method comprises providing a concentrated syrup comprising a sweetener and a seed solid comprising a carbohydrate and contacting the syrup with the seed solid to form a composite composition; and drying the composite composition under conditions to obtain the solid sweetener composition wherein at least a portion of the solid sweetener reintroduced into the process to act as a seed solid.

Description

METHODS OF MAKING SOLID SWEETENERS AND SOLID SWEETENER BLENDS100011 The technology disclosed in this specification pertains to a drying technology useful for making a solid sweetener composition. The technology may be applied to a variety of monosaccharides, disaccharides, polyols, and high intensity sweeteners to obtain a solid sweetener composition comprised essentially of single sweetener or a blend of sweeteners.

[0002] Substances such as monosaccharides, disaccharides, polyols, and high intensity sweeteners commonly are handled in the solid state (rather than in the liquid state) because the solid state has greater physicochemical and microbiological stability, longer shelf life, and lower water activity.(0003] But the manufacture and the use of a solid sweetener composition, whether consisting essentially of a single sweetener or comprising a blend of sweeteners, can have various limitations. As to manufacturing, for example, crystallization process (cooling of seeded supersaturated syrups) provides a pure crystalline product but requires long crystallization times. Other problems associated with crystallization include handling the non-crystallizable residues and losses of material during separation of impurities. As another example in the manufacturing space, solidification via spray drying or other evaporative process or freeze drying are energy intensive processes. As to use, making consistent solid blends of different material is challenging because, commonly, different ingredients have particle size materials leading to ingredient separation during processing.(0004] The technology disclosed in this specification avoids the discussed problems providing an alternate method for forming a solid sweetener composition wherein a solid sweetener composition is formed by contacting a syrup comprising a sweetener with a seed solid comprising a carbohydrate so that the seed solid absorbs or adsorbs the syrup.BRIEF DESCRIPTION OF THE FIGURES

[0005] The technology disclosed in this specification can be better understood with reference to the following figures which are for illustrative purposes and are not intended to limit the full scope of the disclosed technology.

[0006] Figure 1 is a flow diagram illustrating an embodiment of the disclosed methods for making a solid sweetener composition.

[0007] Figure 2 graphs the results of differential scanning calorimetry analysis of the solid sweetener composition (comprising allulose) according to one embodiment of the present technology as compared to crystalline allulose.

[0008] Figure 3 graphs the results of differential scanning calorimetry analysis comparing two embodiments of the solid sweetener composition (comprising allulose).

[0009] Figure 4 graphs the results of thermal gravimetric analysis of the solid sweetener composition (comprising allulose) according to one embodiment of the present technology as compared to crystalline allulose.

[0010] Figure 5 graphs the results of thermal gravimetric analysis of two embodiments of the solid sweetener composition (comprising allulose).

[0011] Figure 6 is a light microscopy image (lOx) of allulose crystals.

[0012] Figure 7 is a light microscopy image (lOx) of the solid sweetener composition (comprising allulose) described in this specification.

[0013] Figure 8 is a light microscopy image (lOx) of another embodiment of the solid sweetener composition (comprising allulose) according to one embodiment of the present technology.

[0014] In various aspects, this specification discloses a method for making a solid sweetener composition that contacts a syrup comprising a sweetener with a seed solid comprising a carbohydrate so that the seed solid absorbs or adsorbs the syrup.

[0015] In any embodiment, this specification describes a method for making a solid sweetener composition, the method comprising: (a) providing a concentrated syrup comprising a sweetener; (b) providing a seed solid comprising a carbohydrate; (c) contacting the syrup with the seed solid to form a composite composition; and (d) drying the composite composition under conditions to obtain the solid sweetener composition wherein at least a portion of the solid sweetener composition is introduced at step b) as the seed solid.[0016 In any embodiment of the methods described in this specification each of the sweetener in the syrup and the carbohydrate in the seed solid is independently selected from the groupconsisting of monosaccharides, di saccharides, polyols, rare sugars, high intensity sweeteners, and mixtures thereof. In various embodiments of the method described in this specification each of the sweetener in the syrup and the carbohydrate in the seed solid is independently selected from the group consisting of allulose, tagatose, sorbose, apiose, allose, altrose, melezitose, dextrose, fructose, mannose, galactose, idose, gulose, sorbitol, maltitol, xylitol, lactitol, galactitol, allitol, altritol, talitol, glucitol / 1-gulitol, mannitol, iditol, ribose, fucose, arabinose, turanose, leucrose, rebaudioside A, rebaudioside C, rebaudioside D, rebaudioside F, rebaudioside H, rebaudioside N, rebaudioside K, rebaudioside J, rebaudioside O, rebaudioside M, rubusside, dulcoside A, dulcoside B, thaumatin, a mogroside, brazzein, monellin, mabinlin, pentadin, curculin and miraculin and mixtures thereof.(0017] In at least some embodiments of the methods described in this specification, the sweetener in the syrup is selected from the group consisting of allulose, sorbitol, xylose and dextrose. In at least some other embodiments of the methods described in this specification, the carbohydrate in the seed solid is selected from the group consisting of allulose, sorbitol, xylose and dextrose.

[0018] In still other embodiments of the methods described in this specification, the sweetener in the syrup and the carbohydrate in the seed solid are the same and are selected from the group consisting of allulose, sorbitol, xylose and dextrose, wherein, preferably, the sweetener and the carbohydrate are allulose. In these embodiments, the solid sweetener composition consists essentially of a single sweetener. For example, the solid sweetener compositions consists essentially of allulose, or consists essentially of dextrose, or consists essentially of xylose, or consists essentially of sorbitol. In these embodiments, the sweetener in the syrup is a single sweetener consisting essentially of allulose, sorbitol, xylose, and dextrose, and the seed solids consists essentially of the carbohydrate, which is selected from the group consisting of allulose, sorbitol, xylose, and dextrose (and excludes mixtures thereof). The transition consists essentially as applied to the foregoing solid sweetener compositions means that the compositions is (respectively) at least 95% allulose, or at least 95% dextrose, or at least 95% sorbitol, or at least 95% xylose. The remainder of the composition may be moisture and / or a mixture of other carbohydrates. For example, for a solid sweetener composition that is allulose, the remainder ofthe composition may include less than 5% of some mixture of fructose, dextrose, or higher degree polysaccharides comprise of allulose, fructose or dextrose.[00.1.9] In yet other embodiments, the sweetener of the syrup may be different than the carbohydrate of the solid seed. In these cases, the solid seed may be thought of as a carrier or a bulking agent. The solid seed may be any suitable carrier, for example a sweetener as described above, or soluble fiber, such as polydextrose or inulin, etc. In at least some embodiments where the solid sweetener composition is a blended sweetener composition, the carbohydrate of the seed solid is a sweetener such as dextrose or fructose or allulose or other suitable monosaccharide or disaccharide. For purposes of making a reduced calorie sweetener allulose is a useful seed solid. In at least some embodiments of the methods described in this specification, the sweetener in the syrup is selected from the group consisting of rebaudioside A, rebaudioside C, rebaudioside D, rebaudioside F, rebaudioside H, rebaudioside N, rebaudioside K, rebaudioside J, rebaudioside O, rebaudioside M, other steviol glycosides and mixtures thereof, and the carbohydrate in the seed solid is allulose. In yet other embodiment of the method described in this specification, preferably, the sweetener in the syrups is a mixture of rebaudioside, A, rebaudioside D, rebaudioside M and the carbohydrate in the seed solid is allulose. In at least some embodiments where the sweetener composition comprises mixtures, the sweetener in the syrup is a sweet protein, such as thaumatin, instead of a carbohydrate. In such cases, allulose is still a useful seed solid.

[0020] The foregoing paragraph focuses on rebaudioside and thaumatin. These are high intensity sweeteners. Although the method may be used to form solid high intensity sweeteners, in other embodiments, and the described methods are useful for making sweetener compositions that blend any high intensity sweetener with another carbohydrate such as allulose. Advantageously, when the methods are used to make a sweetener of blended materials, the blended sweetener can protect the high intensity sweetener against oxidation because the high intensity sweetener is absorbed or adsorbed into the seed solid (which protects the high intensity sweetener from oxidation). Also, advantageously, as a single composition because the high intensity sweetener is adsorbed or absorbed by the seed solid, the solid sweetener composition is more uniform and consistent than mixed powders and does not separate in the solid state.

[0021] In any embodiment, the method of contacting the syrup and the crystalline seed solid comprises adding the syrup to the seed solid at a temperature from 10 °C to a temperature less thanthe melting temperature of the seed solid, or from about 10 °C to about 90 °C or from about 20 °C or from about 30 °C or from about 40 °C or from about 50 °C, or from about 60 °C or to about 90 °C temperature. In some embodiments the seed solid and syrup are heated separately to matching temperature and then combined. In other embodiments the seed solid and syrup are mixed and heated together to a desired temperature.

[0022] In any embodiment, described in this specification the method of contacting the syrup and the seed solid comprises adding the syrup to the seed solid in a weight ratio of the syrup to the seed solid in a range from about 1 : 100 to about 2: 1, or from about 1 : 100 to about 1 : 1, or to about 1 :2, or to about 1 :3, or to about 1 :4, or to about 1 :5, or to about 1 :6, or to about 1 :7, or to about 1 :8, or to about 1 :9, or to about 1 : 10, or from about 1 : 1 to about 1 : 10, or to about 1 :9, or to about 1 :8, or to about 1 :7, or from about 1 :2, or from about 1:3, or from about 1 :4, or from about 1 :5 to about 1 : 10. Preferred ranges are from about 1 :2 to about 1 : 10, and from about 1 :5 to about 1 :9.|0023] In any embodiment of the methods described in this specification the seed solid has a purity of about 90% to about 99%. Here purity refers to the percent (wt.%) of the seed solid of a single carbohydrate in the seed solid. For example, a seed solid may include from about 90% to about 99% by weight allulose, or sorbitol, or xylose, or dextrose, or other suitable carbohydrate carrier. In any embodiment, the particle size of the seed solid ranges about 0.0001 mm to about 2 cm.|0024| In any embodiment, the concentrated syrup used in the method has a dry solids content of about 80% to about 95 by % (wt.% of the syrup). The concentrated syrup may be provided as a concentrated syrup, or the method may further comprises obtaining the concentrated syrup by concentrating a base syrup. In any embodiment, the concentrated syrup is prepared by concentrating a base syrup having a dry solids content of about 60% to about 80%, or from about 60% to about 75%, or from about 65% to about 80%, or from about 65% to about 75% (wt.% of the syrup). The concentrating may be performed in any suitable manner. In at least some embodiments, a base syrup may be concentrated using evaporative concentration at a temperature of about 40 °C to about 60 °C. In at least some embodiments, a base syrup may be concentrated using vacuum concentration under a pressure less than about 100 mBar, less than about 60 mBar, or from about 10 mBar to about 60 mBar.

[0025] In any embodiment, the composite composition is dried at a temperature of from about from 30 °C, or from about 35 °C to about 80 °C. Although any drying method may be suitable, in at least some embodiments the composite composition is dried in a fluidized bed dryer.

[0026] In any embodiment, the method further comprises reducing the particle size of the solid sweetener composition. Preferably, although not necessarily, the reduced size solid sweetener can be used as the seed solids. Particle size reduction of the solid sweetener composition can be done by milling, sieving, or both. It is expected that while some of the solid sweetener composition will be recycled back into the process to create a continuous process, most of the solid sweetener composition is packaged for sale or other uses. Prior to packaging, the solid sweetener composition can be subjected to a second drying step to further reduce moisture content in the sweetener.

[0027] In any embodiment, the methods include recycling at least part of the solid sweetener composition as the solid seed comprising a carbohydrate which allows the process to run continuously, without the need to introduce solid seed from outside of the system. The continuous process at least comprises the steps of (a) providing a concentrated syrup comprising a sweetener; (b) providing a seed solid comprising a carbohydrate; (c) contacting the syrup with the seed solid to form a composite composition; and (d) drying the composite composition under conditions to obtain the solid sweetener composition. Additionally, the process may further comprise the steps of (e) reducing the particle size of the solid sweetener composition and optionally (f) sieving the solid sweetener composition. The continuous process further comprises recycling at least a fraction of the solid sweetener composition from one or more of steps (d), (e) and (f) to step (b). As a continuous method, embodiments of the methods can run for any number of cycles, for example more than 2 cycles, or more than 5 cycles, or more than 10 cycles, or more than 15 cycles. Here a cycle means that a sweetener composition has run through n cycles. In other words, during a continuous process an original seed solid is added during process start-up, but the seed forms a composite composition that can be recovered at the end of the drying process (a sweetener composition) with at least a portion of the recovered sweetener composition being recycled (the recycled material being the seed solid in the next cycle of the process). Commonly the portion of the recovered composition that is packaged as the sweetener composition will be subjected to further refining steps, whereas the recycle material will not. However, the recovered composite composition can be recycled as after any number of refining steps or may be part of the finalsweetener material. As shown in the examples, the structure of the sweetener composition recovered from drying (part of which is recycled) changes compared to the original seed, although the structure of the sweetener composition will reach essentially a steady state (not change further in meaningful ways) after the sweetener composition has been recycled for around 10 to 15 cycles.

[0028] In optimized methods the syrup and seed solid are mixed continuously to maximize the surface area of solids presented to the syrup. This increases adsorption or absorption rate. The mixing also prevents agglomeration of separate seed solid particles which reduces the presented surface area of the seed solids available to the syrup. Accordingly, in any embodiment of the methods does not lead to the agglomeration of separated solid particles. Additionally, advantageously, there is essentially no yield loss of solid material as all solids are adsorbed or absorbed into the seed material.

[0029] The present technology further provides a solid sweetener compositions made by the methods described herein. The product obtained by the process of the present technology can be distinguished from other materials as not being crystalline or not being an agglomeration of separate solids. The product by process is a quasi-angular material or an amorphous material as subsequent layers of syrup are adsorbed or absorbed by the recycled sweetener composition, in Figure 6 (crystalline seed), Figure 7 (3-cycles), and Figure 8 (15-cycles) are images of this material and it migrates away from a crystalline solid as solidification cycles increase. The product of the present technology can further be distinguished from crystalline material by a reduced onset melting temperature relative to the crystalline form of the solid sweetener or peak melting temperature relative to the crystalline form of the solid sweetener, or a combination thereof.

[0030] In another aspect of the present technology, the solid sweetener composition is an allulose composition. In any embodiment, the solid sweetener composition is an allulose composition having a solids content of greater than 90%, or greater than 95% or greater than 97% (wt.% of the composition) and allulose content greater than 95% (wt.% of the solids) and an onset melting temperature less than 120 °C or less than about 117 °C, or less than about 115 °C. The allulose composition can be further described by having a peak melting temperature of less than 130 °C, or less than 128 °C, or less than about 125° C. The allulose composition can be further described by having a heat of melting is less than 213 J / g or from 210 to 213 J / g.

[0031] In any embodiment, of an allulose composition, the composition has a degradation peak (as measured by thermal gravitation analysis) at temperature between 200° and 250° C, or has having a degradation peak measured (as measured by thermal gravitation analysis) in one more of a range selected from the group consisting of: a. from about 200° to about 230° C, or from about 200° to about 230° C, or from about 200° to about 220° C b. and about 235° to about 260° C, or from about 235° to about 255° C, or from 235° to 250° C.

[0032] In any embodiment of an allulose composition, the composition has a particle size distribution having a median particle size (d0.5) from 400 to 800 microns or from 500 to 800 microns or from 600 to 800 microns.

[0033] Use of “about” to modify a number is meant to include the number recited plus or minus 10%. Where legally permissible recitation of a value in a claim means about the value. Use of about in a claim or in the specification is not intended to limit the full scope of covered equivalents.

[0034] Recitation of the indefinite article “a” or the definite article “the” is meant to mean one or more unless the context clearly dictates otherwise.|0035| While certain embodiments have been illustrated and described, a person with ordinary skill in the art, after reading the foregoing specification, can effect changes, substitutions of equivalents and other types of alterations to the methods, and of the present technology. Each aspect and embodiment described above can also have included or incorporated therewith such variations or aspects as disclosed regarding any or all the other aspects and embodiments.

[0036] The present technology is also not to be limited in terms of the aspects described herein, which are intended as single illustrations of individual aspects of the present technology. Many modifications and variations of this present technology can be made without departing from its spirit and scope, as will be apparent to those skilled in the art. Functionally equivalent methods within the scope of the present technology, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing descriptions. Such modifications and variations are intended to fall within the scope of the appended claims. It is to be understood that this present technology is not limited to methods, conjugates, reagents, compounds, compositions, labeled compounds or biological systems, which can, of course, vary. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearlycontradicted by context. It is also to be understood that the terminology used herein is for the purpose of describing aspects only and is not intended to be limiting. Thus, it is intended that the specification be considered as exemplary only with the breadth, scope and spirit of the present technology indicated only by the appended claims, definitions therein and any equivalents thereof. No language in the specification should be construed as indicating any non-claimed element as essential.

[0037] The embodiments illustratively described herein may suitably be practiced in the absence of any element or elements, limitation or limitations, not specifically disclosed herein. Thus, for example, the terms “comprising,” “including,” “containing,” etc. shall be read expansively and without limitation. Additionally, the terms and expressions employed herein have been used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the claimed technology. Additionally, the phrase “consisting essentially of’ will be understood to include those elements specifically recited and those additional elements that do not materially affect the basic and novel characteristics of the claimed technology. The phrase “consisting of’ excludes any element not specified.

[0038] In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group. Each of the narrower species and subgeneric groupings falling within the generic disclosure also form part of the technology. This includes the generic description of the technology with a proviso or negative limitation removing any subject matter from the genus, regardless of whether the excised material is specifically recited herein.

[0039] As will be understood by one skilled in the art, for any and all purposes, particularly in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc. Recitationof ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. As will also be understood by one skilled in the art all language such as “up to,” “at least,” “greater than,” “less than,” and the like, include the number recited and refer to ranges which can be subsequently broken down into subranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member, and each separate value is incorporated into the specification as if it were individually recited herein.

[0040] The technology disclosed in this specification can be further understood with reference to the following aspects that are provided for illustrative purposes and are not intended to limit the full scope of the disclosed technology.

[0041] 1. A method for producing a solid sweetener composition, the method comprising: (a) providing a concentrated syrup comprising a sweetener; (b) providing a seed solid comprising a carbohydrate; (c) contacting the syrup with the seed solid to form a composite composition; and (d) drying the composite composition under conditions to obtain the solid sweetener composition wherein at least a portion of the solid sweetener is introduced at step b) as the seed solid.

[0042] 2. The method of claim 1, wherein each of the sweetener in the syrup and the carbohydrate in the seed solid is independently selected from the group consisting of monosaccharides, di saccharides, polyols, rare sugars, high intensity sweeteners, and mixtures thereof.

[0043] 3. The method of claim 1 or 2, wherein each of the sweetener in the syrup and the carbohydrate in the seed solid is independently selected from the group consisting of allulose, tagatose, sorbose, apiose, allose, altrose, melezitose, dextrose, fructose, mannose, galactose, idose, gulose, sorbitol, maltitol, xylitol, lactitol, galactitol, allitol, altritol, talitol, glucitol / 1-gulitol, mannitol, iditol, ribose, fucose, arabinose, turanose, leucrose, rebaudioside A, rebaudioside C, rebaudioside D, rebaudioside F, rebaudioside H, rebaudioside N, rebaudioside K, rebaudioside J, rebaudioside O, rebaudioside M, rubusside, dulcoside A, dulcoside B, thaumatin, a mogroside, brazzein, monellin, mabinlin, pentadin, curculin and miraculin and mixtures thereof.

[0044] 4. The method of any one of claims 1 to 3, wherein the sweetener in the syrup is selected from the group consisting of allulose, sorbitol, xylose and dextrose.

[0045] 5. The method of any one of claims 1 to 4, wherein the carbohydrate in the seed solid is selected from the group consisting of allulose, sorbitol, xylose and dextrose.[0046| 6. The method of any one of claims 1 to 5, wherein the sweetener in the syrup and the carbohydrate in the seed solid are the same and are selected from the group consisting of allulose, sorbitol, xylose and dextrose, wherein, preferably, the sweetener and the carbohydrate are allulose.

[0047] 7. The method of any one of claims 1 to 5, wherein the sweetener in the syrup is selected from the group consisting of rebaudioside A, rebaudioside C, rebaudioside D, rebaudioside F, rebaudioside H, rebaudioside N, rebaudioside K, rebaudioside J, rebaudioside O, rebaudioside M and mixtures thereof, and the carbohydrate in the seed solid is allulose, wherein, preferably the sweetener in the syrups is a mixture of rebaudioside, A, rebaudioside D, rebaudioside M.| 0048| 8. The method of any one of claims 1 to 7, wherein the concentrated syrup has a dry solids content of about 80% to about 95%.

[0049] 9. The method of any one of claims 1 to 8, wherein the concentrated syrup is prepared by concentrating a base syrup having a dry solids content of about 60% to about 80%, or from about 60% to about 75%, or from about 65% to about 80%, or from about 65% to about 75%, wherein optionally the concentrating is conducted as an evaporative concentration at a temperature of about 40 °C to about 60 °C or as a vacuum concentration under a pressure less than about 100 mBar, less than about 60 mBar, or from about 10 mBar to about 60 mBar.

[0050] 10. The method of any one of claims 1 to 9, wherein contacting the syrup and the crystalline seed solid comprises adding the syrup to the seed solid at a temperature from 10 °C to a temperature less than the melting temperature of the seed solid, or from about 10 °C to about 90 °C or from about 20 °C or from about 30 °C or from about 40 °C or from about 50 °C, or from about 60 °C to about 90 °C temperature.

[0051] 11. The method of any one of claims 1 to 10, wherein the weight ratio of the syrup to the crystalline seed solid ranges from about 1 : 100 to about 2:1, or from about 1 : 100 to about 1: 1, or to about 1 :2, or to about 1 :3, or to about 1 :4, or to about 1 :5, or to about 1 :6, or to about 1 :7, or to about 1 :8, or to about 1 :9, or to about 1 : 10, or from about 1 : 1 to about 1 : 10, or to about 1 :9, or to about 1 :8, or to about 1:7, or from about 1 :2, or from about 1 :3, or from about 1 :4, or from about 1 :5 to about 1 : 10, wherein optionally, the weight ratio is from about 1 :2 to about 1 : 10, wherein, optionally, the weight ratio is from about 1 :5 to about 1 :9.

[0052] 12. The method of any one of claims 1 to 11, wherein the seed solid has a purity of about 90 % to about 99 %.

[0053] 13. The method of any one of claims 1 to 12, wherein the composite composition is dried at a temperature of from about 30 °C, or from about 35 °C to about 80 °C.

[0054] 14. The method of any one of claims 1 to 13, wherein the drying is conducted using a fluidized bed dryer.|0055] 15. The method of any one of claims 1 to 14, further comprising: (e) reducing the particle size of the solid sweetener composition; (f) optionally sieving the solid sweetener composition; and (g) optionally subjecting the solid sweetener composition to a drying step.

[0056] 16. The method of claim 15, wherein reducing the particle size comprises dry milling the solid sweetener composition product to a desired particle size.

[0057] 17. The method of any one of claims 1 to 16, wherein steps a) to d), optionally, steps a) to e), optionally steps a) to f) are repeated for more than 2 cycles or more than 5 cycles, or more than 10 cycles or more than 15 cycles.[0058| 18. The method of any one of claims 1 to 17, wherein the particle size of the seed solid ranges about 0.0001 mm to about 2 cm.

[0059] 19. The method of any one of claims 1 to 18, wherein the syrup is absorbed or adsorbed by the seed solid.

[0060] 20. The method of any one of claims 1 to 19, wherein during the step c) the syrup and seed solid are mixed continuously.

[0061] 21. The method of any one of claims 1 to 20, wherein the method does not agglomerate the separate solid particles.

[0062] 22. A solid sweetener composition product obtained by the method of any one of claims 1 to 21.

[0063] 23. The solid sweetener composition of claim 22, wherein the composition comprises allulose.

[0064] 24. The solid sweetener composition of claim 22, wherein the sweetener in the syrup and the carbohydrate in the seed solid are the same or different and are selected from the group consisting of allulose, sorbitol, xylose and dextrose, wherein, preferably, the sweetener and the carbohydrate are allulose.

[0065] 25. The solid sweetener composition of claim 22, where the sweetener in the syrup and the carbohydrate in the seed solid are selected from the group consisting of rebaudioside A, rebaudioside C, rebaudioside D, rebaudioside F, rebaudioside H, rebaudioside N, rebaudioside K, rebaudioside J, rebaudioside O, rebaudioside M and mixtures thereof, and the carbohydrate in the seed solid is allulose, wherein, preferably the sweetener in the syrups is a mixture of rebaudioside, A, rebaudioside D, rebaudioside M.

[0066] 26. An allulose composition having a dry solids content of greater than 90%, or greater than 95% or greater than 97% (wt.% of the composition) and allulose content greater than 95% (wt.% of the solids) and an onset melting temperature (as measured by differential scanning calorimetry) less than 120 °C or less than about 117 °C, or less than about 115 °C.

[0067] 27. The allulose composition of claim 26 having a peak melting temperature (as measured by differential scanning calorimetry) of less than 130 °C, or less than 128 °C, or less than about 125° C.

[0068] 28. The allulose composition of claim 26 or 27, wherein a heat of melting (as measured by differential scanning calorimetry) is less than 213 J / g or from 210 to 213 J / g.

[0069] 29. The allulose composition of any one of claims 26 to 28 consisting essentially of allulose.

[0070] 30. The allulose composition of any one of claims 26 to 29 having a particle size distribution with a median particle size (d0.5) from about 400 to 800 microns or from about 500 to 800 microns or from about 600 to 800 microns.100711 31. The allulose composition of any one of claims 26 to 30 have a degradation peak (as measured by thermal gravitation analysis) at a temperature between 200° and 250° C, or having a degradation peak measured (as measured by thermal gravitation analysis) in one more of a range selected from the group consisting of: a. from about 200° to about 230° C, or from about 200° to about 230° C, or from about 200° to about 220° C b. and about 235° to about 260° C, or from about 235° to about 255° C, or from 235° to 250° C.

[0072] The technology disclosed in this specification can be further understood with reference to the following examples that are provided for illustrative purposes and are not intended to limit the full scope of the disclosed technology.EXAMPLE 1 - METHODS

[0073] Differential scanning calorimetry (“DSC”) (for all samples reported except for dextrose) and thermal gravimetric analysis (“TGA”) (of all samples reported) was done using a TA Instruments model DSC Q200 using the following conditions. Nitrogen gas flow of 100 mL / min. Temperature ramp of 10° C per minute from 0° C to 350° C. Samples were enclosed in aluminum using Tzero" sample press kit (TA Instruments). Calorimeter was calibrated using an indium metal standard according to standard testing method E 794, “Melting Crystallization Temperature by Thermal Analysis.”

[0074] DSC for dextrose was done using a PerkinElmer thermal analysis instruments Model PYRIS 1, conditions: Nitrogen gas flow of 20 mL / min. Temperature ramp of 20° C per minute from 25° C to 210° C.

[0075] Particle size distribution was measured using a Malvern, Mastersizer 2000 using the following optical parameters:• Refractive Index: 1 .52 (default) for both sample types (Allulose & dextrose);• Absorption: 0.1;• Model: General purpose-normal sensitivity;and the following measurement parameters:• Sample Measurement Time: 10s• Background Measurement Time: 10s• Time between Measurements: Os• Air pressure: 2 Bar for allulose and dextrose• Feeding: 70% for allulose and 50% for dextrose• Odds: 1• Measurements: 3 (Average reported)

[0076] Dissolution rate was measured by adding 3.5 grams of powdered allulose to 96.5 grams of room temperature (about 21° C) deionized water. The solution was stirred and observed (visually). Dissolution rate is the time for all powdered allulose to dissolve.

[0077] Within this specification theoretical relative sweetness refers to a comparative theoretical relative sweetness calculated by taking the weighted sum (by usage) of the relative sweetness of each component. Sweetness rating for each sweetener is relative to sucrose, where sucrose is defined to have a linearly increasing sweetness of 1 for a 1% solution (wt.%) of sucrose in water and 2 for a 2% solution (wt.%) of sucrose in water, etc. Within this specification, the sweetness value of Allulose is 0.7 (or 70% of sweetness of sucrose for a given usage level). The sweetness the Rebaudioside A, D, M blend is 350. The sweetness of Thanumatin is 2500.EXAMPLE 2 - EFFECT OF SYRUP CONCENTRATION ON SOLID ALLULOSE PRODUCT

[0078] Allulose syrups of varying concentration were made as follows. Allulose syrup having 74% solids (wt.% of the syrup) and allulose content of 96.87% (wt.% of dry solids) was used as a base. The syrup was concentrated at reduced pressure (20 mBar) in a vacuum evaporator, for up to 40 min to obtain allulose syrups having different solids concentration. Concentrated syrups had solids content ranging from 82 to 93% (wt.%) dry solids. Solids product was obtained using syrup- to-seed ratio of 1:4 As shown in Table 1, syrups with higher solids concentration produced a solid product that was more stable against hygroscopicity.Table 1.Effect of syrup concentration on the final productEXAMPLE 3 - EFFECT OF SYRUP TO SEED RATIO ON ALLULOSE PRODUCT

[0079] Non-hygroscopic allulose syrups (at least 88% solids, wt.% dry basis, at least 95% allulose, wt.% solids) were mixed with seed solids (solid allulose) (200g). The syrup addition to the powder was done at a constant temperature with temperature of the seed solid and syruped matched (65 °C). Syrup and seed solid were mixed at a ratio (syrup-to-seed) of 1 :5, 1 :4, or 1 :3. Syrup was absorbed and / or adsorbed by the seed solid to obtain a solid product.

[0080] The obtained solid sweetener composition was dried (convection furnace) at a temperature of 50° C for 24h. The dry product was then ground in a mill and sieved to a fine particle size (undefined). This sieved product was used again as a seed solid to start a next mixing cycle with the same concentrated allulose syrup. This cycle was repeated 3 times and 15 times. Select properties of allulose solid sweetener composition (3 cycles) as compared to crystallized allulose are reported in Table 2.Table 2.Comparison between reference crystalline Allulose and solid Allulose.

[0081] Figure 2 compares differential scanning calorimetry endothermal plots of crystallized allulose and allulose solid sweetener composition (3-cycle). Figure 3 compares differential scanning calorimetry endothermal plots of allulose solid sweetener composition (3-cycle) and allulose solid sweetener composition (15-cycle). Figure 2 shows a shift to lower onset, peak and final melting temperatures from the crystallized allulose to the solid allulose (3-cycle) . Similarly, Figure 3 shows a shift to lower onset, peak and final melting temperature from solid allulose (3-cycle) to the solid allulose (15-cycle). Differences in onset, and peak melting temperature, and heat of melting of crystallized allulose and allulose solid sweetener composition (15-cycle) are reported in Table 3.Table 3DSC Values Crystallized vs Solid (15-cycle) Allulose

[0082] Figure 4 compares crystallized allulose and allulose solid sweetener composition (3- cycle) using thermal gravimetric analysis (measuring the change in the weight of samples versus change in temperature) and the derivative of the change in weight of the samples versus temperature change. Figure 5 compares allulose solid sweetener composition (3-cycle) and allulose solid sweetener composition (15-cycle) using thermal gravimetric analysis (measuring the change in the weight of samples versus change in temperature) and the derivative of the change in weight of the samples versus temperature change. While the crystalized allulose and allulose solid sweetener composition (3-cycle) had similar profiles, the allulose solid sweetener composition (15-cycle) differs significantly. The allulose solid sweetener composition (15-cycles) had substantial thermal decompositions (graphed peak) at 212.65° C, and 241.88° C, whereas the allulose solid sweetener composition (3-cycles) had a substantial thermal decomposition (graphed peak) at 270.01° C.EXAMPLE 4 - ALTERNATE ALLULOSE SOLIDIFICATION PROCESS(0083] In this example, allulose syrup with a solids range of 82-88% wt.% dry solids was used for the solidification process with allulose seed solid (200g). The during addition the syrup had a temperature between 40° C - 45° C and the temperature of seed solid was around 25° - 28° C. Constant stirring of the seed solid during the addition of the syrup was maintained, at a syrup to seed solid ratio from 1:5 to 1 :8 in different cycles.(0084] The resulting allulose solid sweetener composition from each cycle was dried using a fluidized bed dryer, at 40°C for 30 min. Allulose solid sweetener composition was then milled and sieved to a fine particle size and dried again at 40°C for 30 min. Afterwards, the composition was allowed to cool for 24 h at room temperature (about 23° C). The cooled Allulose solid sweetener composition was recycled to start a next mixing cycle. This process was repeated 15 times (described in Table 4). Final solid product had 99.33% total solids (dry basis; moisture content 0.67%) and allulose content of 96.14% (wt.% of dry solids).Table 4 Solidification Process.EXAMPLE 5 - DEXTROSE SOLIDIFICATION PROCESS

[0085] Dextrose syrup was concentrated from a base syrup with 72 % wt.% dry solids. Base dextrose syrup was concentrated in a vacuum evaporator (50mBar), obtaining a saturated syruphaving from 82 to 86% wt.% dry solids. Increase nucleation (solids formation) was observed in higher concentrated syrups. For the process, syrups with reduced nucleation were preferred.

[0086] The concentrated dextrose syrup was mixed with anhydrous dextrose powder (seed solid) (200g). Both dextrose syrup and dextrose powder were heated to between 70° and 75° C and maintained at a constant temperature during the mixing. Dextrose syrup and dextrose powder were stirred constantly to improve the contact area and impregnation in the solid phase. Dextrose syrup and dextrose powder were mixed at different ratios syrup to powder (seed). Details of the process are reported in Table 5.Table 5.Syrup / seed Ratio in Dextrose Solidification

[0087] The resulting dextrose solid sweetener composition was dried using a fluidized bed dryer, at different temperatures from 50°C to 80°C for 10 min. The dry product was ground and sieved to a fine particle size (see Table 6, compared to crystalline dextrose) and showing a composition of a-D-Glucose. Table 6 also reports the DSC profile of obtained dextrose solid sweetener composition compared to commercial crystalline dextrose products.Table 6Comparison Between Reference Commercials Dextrose and Solid Dextrose.[0088| DSC analysis confirmed that the dextrose solid sweetener composition is distinguishable from crystalline dextrose.EXAMPLE 6 - SORBITOL SOLIDIFICATION PROCESS

[0089] Solid sorbitol was obtained by concentrating a base syrup 65-70% wt.% dry solids and a minimum purity of 96% D-Sorbitol (wt.% of solids dry basis). The base sorbitol was concentrated using a vacuum evaporator (50 mmHg) to a moisture content of less than 0.5% (99.5% dry solids). Concentrated syrup was added to crystalline sorbitol (seed solid) in a ratio of 1:3, 1 :4 and 1 :5 (syrup-to-seed) at a maintained mixture temperature of 85 °C with constant stirring to favor mixing. The product was made to pass through dry air at different temperatures from 75°C, 70°C, 60°C, 50°C, 40°C, 30°C, 20°C, by time intervals. Under the conditions used, it was possible to obtain a sorbitol solid sweetener composition with a suitable hardness for grinding in a mill. The sorbitol solid sweetener composition had the following parameters (Table 7).Table 7Typical analysis of solid sorbitolEXAMPLE 7 - SOLIDIFICATION OF XYLOSE

[0090] Syrup preparation: Xylose with 99.5% purity was used to prepare a 65% solution in water. This solution was concentrated at reduced pressure (30 mBar) in a vacuum evaporator brand to obtain a saturated syrup at 76% dry solids. The concentrated xylose syrup was added to 200g of xylose seed solid. The addition of the syrup to the seed solid was done at a constant temperature in both phases, between 74-87°C. Xylose seed solid and xylose syrup were constantly stirred at syrup:seed ratio of 1 / 1.9. The xylose solid sweetener composition was dried using a convection furnace at a temperature of 50° C for 24h. The moisture of the xylose solid sweetener composition compared to crystalline xylose is shown in Table 8.Table 8Comparison between reference commercials xylose and solid xylose:EXAMPLE 8 - HIGH INTENSITY SWEETENER WITH A RARE SUGAR SOLIDIFICATION PROCESS

[0091] Syrup preparation: mixture of 2% rebaudioside A, 2% rebaudioside D and 2% rebaudioside M were dissolved in 94% of water at temperature of 82°C to obtain a transparent solution. The mixed rebaudioside solution (100g) was added to 300g of an allulose syrup (85% wt.% solids content). The mixed rebaudioside / allulose syrup had 66% wt.% dry solids and formed a base syrup that was concentrated at reduced pressure (20 mBar) in a vacuum evaporator until a saturated syrup with 92% dry solids was obtained.

[0092] The concentrated syrup was added to 200g of allulose seed solids. The syrup and allulose powder both had a temperature between 60° - 65° C when mixed. Mixture of syrup and allulose seed solids was maintained at temperature and constantly mixed. The syrup:seed ratio was 1 :2.6.The obtained solid sweetener composition was dried using a convection furnace at a temperature of 50° C for 24h. The solid sweetener composition was then ground in a mill and sieved to a fine particle size. This final solid sweetener composition was 99.06% (wt .%) allulose and 0.94% (wt.%) rebaudiosides (A, D, M). The theoretical calculated relative sweetness of this solid product is 3.98 times sweeter compared to sugar.EXAMPLE 9 - SWEETENED PROTEIN IN A RARE SUGAR PROCESS OF SOLIDIFICATION

[0093] Syrup preparation: 18 g of thaumatin powder with a purity of 95% was added and mixed (282g) in with an allulose syrup (71% wt. dry solids) to form a base syrup having 85% (wt.% dry solids). This base syrup was concentrated in a vacuum evaporator (20 mBar) until a saturated syrup with 92% ds was obtained. The allulose-thaumatin concentrated syrup was mixed with 200g allulose seed solid. Both syrup and seed solid were heated to between 60° - 65° C. The mixture was maintained at temperature and mixed constantly. The syrup:seed ratio was 1 :2.74. The solid product was dried using a convection furnace at a temperature of 50° C for 24h. Subsequently, the dry product was ground in a mill and sieved to a fine particle size. This final solid product had 97.18% allulose and 2.82% thaumatin. The theoretical relative sweetness of this solid product is 71.

Claims

CLAIMSWhat is claimed is:

1. A method for producing a solid sweetener composition, the method comprising:(a) providing a concentrated syrup comprising a sweetener;(b) providing a seed solid comprising a carbohydrate;(c) contacting the syrup with the seed solid to form a composite composition; and(d) drying the composite composition under conditions to obtain the solid sweetener composition wherein at least a portion of the solid sweetener is introduced at step b) as the seed solid.

2. The method of claim 1, wherein each of the sweetener in the syrup and the carbohydrate in the seed solid is independently selected from the group consisting of monosaccharides, di saccharides, polyols, rare sugars, high intensity sweeteners, and mixtures thereof.

3. The method of claim 1 or 2, wherein each of the sweetener in the syrup and the carbohydrate in the seed solid is independently selected from the group consisting of allulose, tagatose, sorbose, apiose, allose, altrose, melezitose, dextrose, fructose, mannose, galactose, idose, gulose, sorbitol, maltitol, xylitol, lactitol, galactitol, allitol, altritol, talitol, glucitol / 1- gulitol, mannitol, iditol, ribose, fucose, arabinose, turanose, leucrose, rebaudioside A, rebaudioside C, rebaudioside D, rebaudioside F, rebaudioside H, rebaudioside N, rebaudioside K, rebaudioside J, rebaudioside O, rebaudioside M, rubusside, dulcoside A, dulcoside B, thaumatin, a mogroside, brazzein, monellin, mabinlin, pentadin, curculin and miraculin and mixtures thereof.

4. The method of any one of claims 1 to 3, wherein the sweetener in the syrup is selected from the group consisting of allulose, sorbitol, xylose and dextrose.

5. The method of any one of claims 1 to 4, wherein the carbohydrate in the seed solid is selected from the group consisting of allulose, sorbitol, xylose and dextrose.

6. The method of any one of claims 1 to 5, wherein the sweetener in the syrup and the carbohydrate in the seed solid are the same and are selected from the group consisting of allulose, sorbitol, xylose and dextrose, wherein, preferably, the sweetener and the carbohydrate are allulose.

7. The method of any one of claims 1 to 5, wherein the sweetener in the syrup is selected from the group consisting of rebaudioside A, rebaudioside C, rebaudioside D, rebaudioside F, rebaudioside H, rebaudioside N, rebaudioside K, rebaudioside J, rebaudioside O, rebaudioside M and mixtures thereof, and the carbohydrate in the seed solid is allulose, wherein, preferably the sweetener in the syrups is a mixture of rebaudioside, A, rebaudioside D, rebaudioside M.

8. The method of any one of claims 1 to 7, wherein the concentrated syrup has a dry solids content of about 80% to about 95%.

9. The method of any one of claims 1 to 8, wherein the concentrated syrup is prepared by concentrating a base syrup having a dry solids content of about 60% to about 80%, or from about 60% to about 75%, or from about 65% to about 80%, or from about 65% to about 75%, wherein optionally the concentrating is conducted as an evaporative concentration at a temperature of about 40 °C to about 60 °C or as a vacuum concentration under a pressure less than about 100 mBar, less than about 60 mBar, or from about 10 mBar to about 60 mBar.

10. The method of any one of claims 1 to 9, wherein contacting the syrup and the crystalline seed solid comprises adding the syrup to the seed solid at a temperature from 10 °C to a temperature less than the melting temperature of the seed solid, or from about 10 °C to about 90 °C or from about 20 °C or from about 30 °C or from about 40 °C or from about 50 °C, or from about 60 °C to about 90 °C temperature.

11. The method of any one of claims 1 to 10, wherein the weight ratio of the syrup to the crystalline seed solid ranges from about 1 : 100 to about 2: 1, or from about 1 : 100 to about 1 : 1, or to about 1 :2, or to about 1:3, or to about 1 :4, or to about 1 :5, or to about 1 :6, or to about 1 :7, or to about 1 :8, or to about 1 :9, or to about 1 :10, or from about 1 : 1 to about 1 : 10, or to about 1 :9, or to about 1 :8, or to about 1 :7, or from about 1 :2, or from about 1 :3, or from about 1 :4, or from about1 : 5 to about 1 : 10, wherein optionally, the weight ratio is from about 1 :2 to about 1 : 10, wherein, optionally, the weight ratio is from about 1 :5 to about 1 :9.

12. The method of any one of claims 1 to 11, wherein the seed solid has a purity of about 90 % to about 99 %.

13. The method of any one of claims 1 to 12, wherein the composite composition is dried at a temperature of from about 30 °C, or from about 35 °C to about 80 °C.

14. The method of any one of claims 1 to 13, wherein the drying is conducted using a fluidized bed dryer.

15. The method of any one of claims 1 to 14, further comprising:(e) reducing the particle size of the solid sweetener composition;(f) optionally sieving the solid sweetener composition; and(g) optionally subjecting the solid sweetener composition to a drying step.

16. The method of claim 15, wherein reducing the particle size comprises dry milling the solid sweetener composition product to a desired particle size.

17. The method of any one of claims 1 to 16, wherein steps a) to d), optionally, steps a) to e), optionally steps a) to f) are repeated for more than 2 cycles or more than 5 cycles, or more than 10 cycles or more than 15 cycles.

18. The method of any one of claims 1 to 17, wherein the particle size of the seed solid ranges about 0.0001 mm to about 2 cm.

19. The method of any one of claims 1 to 18, wherein the syrup is absorbed or adsorbed by the seed solid.

20. The method of any one of claims 1 to 19, wherein during the step c) the syrup and seed solid are mixed continuously.21 . The method of any one of claims 1 to 20, wherein the method does not agglomerate the separate solid particles.

22. A solid sweetener composition product obtained by the method of any one of claims 1 to 21.

23. The solid sweetener composition of claim 22, wherein the composition comprises allulose.

24. The solid sweetener composition of claim 22, wherein the sweetener in the syrup and the carbohydrate in the seed solid are the same or different and are selected from the group consisting of allulose, sorbitol, xylose and dextrose, wherein, preferably, the sweetener and the carbohydrate are allulose.

25. The solid sweetener composition of claim 22, where the sweetener in the syrup and the carbohydrate in the seed solid are selected from the group consisting of rebaudioside A, rebaudioside C, rebaudioside D, rebaudioside F, rebaudioside H, rebaudioside N, rebaudioside K, rebaudioside J, rebaudioside O, rebaudioside M and mixtures thereof, and the carbohydrate in the seed solid is allulose, wherein, preferably the sweetener in the syrups is a mixture of rebaudioside, A, rebaudioside D, rebaudioside M.

26. An allulose composition having a dry solids content of greater than 90%, or greater than 95% or greater than 97% (wt.% of the composition) and allulose content greater than 95% (wt.% of the solids) and an onset melting temperature (as measured by differential scanning calorimetry) less than 120 °C or less than about 117 °C, or less than about 115 °C.

27. The allulose composition of claim 26 having a peak melting temperature (as measured by differential scanning calorimetry) of less than 130 °C, or less than 128 °C, or less than about 125° C.

28. The allulose composition of claim 26 or 27, wherein a heat of melting (as measured by differential scanning calorimetry) is less than 213 J / g or from 210 to 213 J / g.

29. The allulose composition of any one of claims 26 to 28 consisting essentially of allulose.

30. The allulose composition of any one of claims 25 to 29 having a particle size distribution with a median particle size (d0.5) from about 400 to 800 microns or from about 500 to 800 microns or from about 600 to 800 microns.

31. The allulose composition of any one of claims 25 to 30 have a degradation peak (as measured by thermal gravitation analysis) at a temperature between 200° and 250° C, or having a degradation peak measured (as measured by thermal gravitation analysis) in one more of a range selected from the group consisting of: a. from about 200° to about 230° C, or from about 200° to about 230° C, or from about 200° to about 220° C b. and about 235° to about 260° C, or from about 235° to about 255° C, or from 235° to 250° C.

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