AU2015202392B2 - Natural crystalline colorant and process for production - Google Patents

Abstract

[0097] A crystalline pigment or colorant composition having high color intensity and/or low sugar content, and methods and processes of preparation. The composition may comprise purified fruit and/or vegetable color juices. The unique dried colorants obtained from natural sources including plants, such as fruits and vegetables, and algae. The colorants may be obtained from red grape juice and/or purple carrot juice. The process of producing the dried colorant includes, purifying the color pigments using various purification technologies and subsequently removing water using low temperature drying methods. This combination of purification technologies and low temperature drying produces a unique natural colorant that is high in color and/or low in sugar. The colorants exhibit superior storage stability and/or handling characteristics including, but not limited to density, flowability, water dispersion and/or hygroscopicity.

Description

NATURAL CRYSTALLINE COLORANT AND PROCESS FOR PRODUCTION

CROSS-REFERENCE TO RELATED APPLiCATiGNS 10001] The present application claims the benefit of and priority to U,8. Provisional Patent Application No..;81/503,557 entitled “NATURAL CRYSTALLINE COLGRANF AND PROCESS FOR PRODUCTION" fled on June 30, 2011 . which is hereby incorporated fey reference.

FIELD OF TECHNOLOGY

[0002] The present disclosure relates In general Id purified natural color pigments and colorants and processes for preparing and processing the pigments and colorants.

BACKGROUND 10003] Natural colors and dyes are pnmaniy derived from pigments that are found In plants including fruits, flowers and vegetables. Based on their chemical composition, natural plant-sourced pigments can be classified into structural groups including, Out not limited to, anthocyanins, feetalains, carotenoids, curcumln, carminic acid end derivatives, chlorophylls aridTheir derivatives, etc, Carotenoids include, but are net limited to, jTcarotene, a-carotene, apoearPienal, lycopene, biximnorbixim canthaxanthln, and zeaxanthln, Chlorophyll and chiorophyilin derivatives include, but are not limited to* copper complexes. In another non-limitlhg embodiment, the pigment may be pomplexed with a metei ionsuch;am Μ,ηοΐ limited: to, copper, [0004] One objective of the manufacturing industry is to concentrate the pigmented portion of plants to provide a more concentrated natural colorant that can be added to various food, drug, add cosmetic products. These concentrate colorants are produce by removing other compounds through separation processes.

[0003] Natural colorants are often recovered from frail and vegetable juices which are high in sugar relative to the fraction of pigmented compounds. These sugar-based colors are typically concentrated to remove water and are used as a concentrate with greater than €D percent sugar on a dry weight basis and low pigment levels; St will fee appr©dai®a"thst'fe0&' concentrate may have higher or lower percentage sugar on a dry weight basis depending on the fruit or vegetable. Low color content liquids are expensive to store (often requiring refrigeration), are subject to degradation over time, have a high calorie to color contribution ratio in food or beverage applications due to high sugar content, aodfof may impart uhdesireci sensory characteristics. (0008] The industry has provided two d ifferent forms of these natural colorants from fruit and vegetable juices, namely liquids and powders. Sugar-based colors are often difficult to dry and typical%.:^ggife a fsadhehsuchi&s· malted extrin or micro-crystalline: cellulose to compensate for the hygroscopic character of the sugar. (0007] Further, since the liquids that are subjected: to drying are typically at about S0% w/w to 00%: w/w water content, there are very few technologies1 ava liable to efficiently dry such products. The most common technology available for drying liquids that have a low concentration of soluble solids is spray drying, (0008] Unfertunately,:Spray drying has some disadvantages when it comes to handling of the dried product. Typical problems include, but are not limited to, significant deterioration of the product quality due to the high temperature and pressure that the liquid is subjected to during drying, the formation of amorphous particles with low bulk density due to the rapid rate of drying in micron ixed droplets, and poor water dissolution or wettability characteristics as well as hygroscopic tendencies due to the presence of sugars in an amorphous rather than crystalline state, making the powOers prone to lumping or baking. Furthermore, successful spray drying of a fruit or vegetable concentrate with high sugar contenttypicaliy requires the presence of a carrier, thereby weakening the color concentration arid dosage efficiency of the finished product. (0009] Another objective of the manufacturing industry is to substantially reduce the sugar fraction of the standard fruit- and vegetable-based color concentrates to produce a more concentrated natural color with lower caloric density that can also be dried to yield a product with Improved storage and handling oharacteristics. Purified colors are typically produced by removing the non-pigment components of fruit and vegetable juices and extracts, thereby significantly enriching the material in the color compounds. .Purified colors, containing low coneentrations of sugar, can be dded using a bread range of drying processes Including spray, drum , refractive window, and freeze driers.

The present process provides combinations of purification end drying technology to produce concentrated natural color that can be dried without carriers. The concentrated natural colors described herein have a high color intensity and/or improved sensory, stability:, and handling characteristics relative to other dry colors known to the industry, P0i0] The foregoing related therewith are intended to. be Illustrative and hot exclusive, Other limitations of the related art will become apparent to those of skill sn the art upon a reading of the specification and a study of the drawings,

SUMMARY pOIIJ The/following aspects and embodiments thereof described and illustrated below are meant to be exemplary and illustrative, not limiting in scope. ρδ12] The present disclosure relates to unique dried colorants obtained from natural sources including plants, such as fruits end vegetables, and aigae. In embodiments, the colorants are obtained from fruit and/or vegetable Juices or Juice concentrates and/or extracts, in further embodiments, the colorants are obtained from red grape juice and/or purple carrot juice- The process of producing the dried coiorant includes, briefly, purifying the cofor pigments;using various purification technologies and subsequently removing water using low temperature.drying methods. This novel combination of purification technologies and low temperature1 drying produces a unique natural coiorant that is high in color and/pf low: in sugar, In empod imehis, the colorants described herein exhibit Superior storage stabiiify'and/or handling characteristics including, but pot limited to density, fiowabiiity, water dispersion and/or hygroscopiclty.

[00131 In one aspect, a natural colorant composition comprising a Crystalline pigment or mixture of pigments derived from plants :and/br algae are contemplated, id an embodiment, the composition has a color intensify that is: higher than the color intensity of raw juice or an unpurified pigment or composition, in a further embodiment, the composition of the above aspect and/or embodiment has decreased sugar on a dry weight basis as compared to raw Juice or an unpuriiied pigment composition, in another embodiment, the composition of the above aspect and/or embodiments contains less than about S-20% sugar on a dry weight basis, in a further embodiment, the composition of the above aspect and/or embodiments Pas a total sugar crontent of less than about 20% of dry weight. In yet another embodiment, the composition of the above aspect and/or embodiments has acolor intensity greater than about 40,000 color units, in another embodiment, the pigment of the above aspect and/or embodiments is a red grope anihocyanin and thecomposition has a color intensity of about 40,000- SS,000 cplof units, in a further embodiment, the pigment of the above aspect and/or embodiments is a purple carrot anthocyanin and the cornposition has a coior intensity of about 9D,QQCM25,000 color units, in an additional embodiment, the pigment of the above aspect and/or embodimehts is selected from the group consisting of anthocyanins, carotenoids, bsfa|aihs;, curcumin, camiinic acid, carminic acid derivatives, chlorophyll, and chlordphyil benvatiyes. |P014| In another aspect, a process for producing a purified, crystalline natural pigment is contemplated , the process comprises (a) pu rifying a j uice or extract containing pigments by removing at least a portion of non^igmem compounds to produce a purified pigment; and (b) drying the purified pigment in an embodiment, the purified pigment is crystalline and has an increased color intensity andior decreased sugar content on a dry weight basis compared to raw Juice, in another embodiment, the pigment Of the above aspect and/or embodiment is selected from the group consisting of anthocyanins, carotenoids, betalains, curcumin, carminic acid, carminic acid derivatives, chlorophyii, and/or chlorophyll denvatives. in a further embodiment, the step of purifying in the process of the above aspect and/or embodiments comprises uitrafiitration and dlafiltration across a pelymerie membmne system, in yet another embodiraent, the polymeric membfarie system of the above aspect and/or embodiments comprises potyethersuifone (RES) spiral uitratiltration mombranes. In a further embodiment, the RES spiral uitrafiitration membranes of theabove aspect and/or embodiments have a nominal moiecuiar weight cutoff of about 5000 daltons. in yet another embodiment, tiie step of purifying of the above aspect and/or embodiments comprises circulating the Juice or extract through a membrane system comprising (a) filtering the Juice or extract through:a membrane system; ip) recovering a reteniate; (c) reoonstifuting the rotentafe; and |d) repeating steps (a) to fb) until the retentate reaches a desired coior strength on a dry weight basis. In an additional embodiment;, step of purifying of the above aspect and/or embodiments comprises sdsorption/desorpiion chromatography, in another embodiment, purifying of the above aspect and/or embodiments comprises a fermentation process In a further embodiment, purifying of the above aspect and/or embodiments comprises a subcnticai or a supercritioai fluid extraction process. in yet another ern hodimen t, the step of drying of the above aspect and/or embodiments is accomplished with a refractive window drier, in a further embodimeni, the step of drying of the above aspect an^ior embodiments comprises freezS'-drying. in another embodiment, the process of the above aspect and/or embodiments fudher comprises 'milling the dried product.

[0015] In a further embodiment a composition formed by the process of any of the above aspect or embodiments, alone or in any combination is contemplated.

[00103 Additional embodiments of the present methods and compositions, and the like, will be apparent from the following description, drawings, examples, and claims. As can be appreciated from the foregoing and following desenpfion, each and every feature described herein, and each and every combination of two or more of such features, is included within the scope of the present disclosure provided that the features included in such a combination are not mutualiy inconsistent, in addition* any feature or combination of featu res may be specifically excluded from any embodiment of the present Invention. Additional aspects and advantages of tie present invention are set forth in the tbllowing descfiption and claims,. particularly when considered in cor^unction with the accompanying eprnples end drawings:.

BRIEF DESCRIPTION OF THE FIGURES

[001T] Figure 1 Is allow chart illustrating ah exemplary process for purifying and drying natural fruit and vegetable based pigments, according to one embodiment £0018¾ Figure 2 is a low chart illustrating an exemplary process for purifying a colorant using ultraiSfration and diaflitration, according to one embodiment.

[0019] Figure 3 Is a flow chart illustrating an exemplary process for concentrating purified color liquid, drying, and milling, according to one embodiment.

[00203 Figure 4A is a side view illustration of a refractive window drier, according to one embodiment.

[00213 Figure 48 is a cross-sectional view illustrating a refractive window drier, according to one embodiment; [0022| Figure 5 is a flow ehartillustrating an: exemplary process for purifying color using adsorption resin separation technology,: according to one embodiment, [0O23| Figure 8 is a flow chart: illustrating an exemplaiy process for purifying color using fermentation technology, according to one eoibodlment.

[00243 Figure 7 is a fiow chart illustrating an exemplary process for purifying color using solvent extraction technology, according to one embodiment.

[Q02S1 Figure 0 is a flow chert illustrating an exemplary process for drying purified color using frae^e-dry technology, according to one embodiment, [00281 Figures 9A-9D are microscopy images at 5x magnification of purified;grape pigments that are refractive window dried (Figure 9A), freeze-dried (Figure SB), spray dried (Figure9D3,,::and drum dried (Figure SO), [00273 Piguras 10A~ 1 DO are microscopy images of Figures 9A-9D at 20x magnification,

DETAILED DESCRIPTION

[0028] Various aspects now will be described more fully hereinafter. Such aspects may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey its scope to those skilled in the art.

[O0293 It will be appreciated that for simplicity and clarity of Illustration, where Considered appropriate;, reference numerals may be repeated among the figures to indicate corresponding or analogous elements, in addition, numerous specific details are set forth in:ofder to provide a thorough understanding of the example embodiments described herein. However, if· will be understood by those of ordinary skill in the art that the example embodiments described heroin may he practiced without these specific details.

[0030] The terms “colorant” and “pigment” as used herein refer to any substa nce used to modify the color of an oblect by changing its spectral transmittance of Its spectral reflectance. “Colorant" and “pigment" as used herein generally refer id colorants and pigments obtained from nature! sources including, but not limited to plants and algae. “Coioranf and “pigment” are used interchangeably herein.

[8031j A “concentrate” as used herein refers to a juice or extract that has had at least some of the water removed, |$β323 “Juice” as used herein refers to the liquid obtained from a fruit, vegetable or other plant, Juice may also refer to iiquid obtained from algae, As used herein, “juice" includes concentra te and extract* “Raw juice” as used herein refers to juice that has not been purified, [0033] “Increased color intensity” refers to ah increase in color intensity as compared to the color intensity of raw juice and/or unpurified pigment compositions, [8034j “Decreased sugar content* refers to a decrease In sugar content on a dry weight basis as compared to raw juice and/or unpurified pigment, [0035] Concentrations, amounts, pH values, etc., are often presented herein in a range format. The description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention. Accordingly , the description of a range should be considered to have specifically disclosed ail the possible subranges as well as individual numerical values within that range. For example, description of a range such as 10-15% should be considered to have specifically disclosed subranges such as 10-1 i%, 10-1:2%, 1043%, 10-14%,11-12%, 1143%, etc,

Method of Preparing Colorants 100383 fe one aspect, a method of preparing a colorant is described. It will he appreciated that the present method may be used to prepare a pigment or colorant and the terms are used interchangeably herein. Briefly, the process includes (I) opiionai feconstitution and pasteurization of a juice concentrate or extract, (ii) purification of the juice concentrate or extract such as by iJtrafsttnation and diaflliratfen, 011} concentration of the purified juice eoneentrate or extract such as by failing film evaporation, Civ) drying, and |vj rniing. While prior dry colorants in the food industry are spray-dried powders, the present dry colorants use Sow temperature drying, such as with refractive window drying technology or freeze drying, to produce crystalline solid color additives that are 100% natural, high in antioxidants, extremely concentrated In'color, and/or completely water soluble.

[O03?| Figure 1 illustrates exemplary·process steps to produce the unique crystalline product described above. Fruit and/or vegetable juice and/or extract 100 is typically, but not always, reconstituted fdiiuted} before purification., in one non-limiting embodiment, concentrate at about 68° Brlx is reconstituted to about. 18-22* Brix. In an embodiment, concentrate is reconstituted with approximately 3 parts water to one part concentrate. Once reconstituted, the juice may be more susceptible to fermentation tom any yeast cells that might be present in the starting material, Since the juice will remain at a low solids level throughout all of the subsequent liquid processing, it may optionally be pasteurized immediately to enhance microbial stability from the start of the process.

The juice or extract may be pasteurized according to methods known in the ah. According to one non-limiting embodiment , the juice or extract is pasteurized by heating to about i 85* F for about 30 seconds and then immedlateiy cooling to about §5* F. The juice of extract is typically, but not always, pasteurized into a jacketed tank that becomes the feed tank for subsequent membrane filtration. All tanks used in the process may be jacketed and/or temperature controlled using, forexample, food-grade propylene glycol aside refrigerant. p}38j The juIce/extract Is then purified 200, ;8y increasing the concentration Of pigment relative to sugar end organic acids, the color-enriched liquid, under the proper drying;conditions, can be converted efficiently into a crystalline form with superior properties, such as handlihg properties. j0039| The juice/extmct may be purified according tp any suitable methods known In the aft. in one preferred embodiment, purification 2001s achieved through thb use of ulfrafiitratiori and diafiitration across polymeric membranes. yitrafiltratiPh (and subsequent iterations of dsaiilfratsOh} produces a reteotriie that is enriched in pigments such as anthocyanln pigments or carotenoid pigmentswhile·simultaneously depleted in the sugars and acids that more easily permeate through the membrane. Removal of sugar increases the color concentration or color intensity on a dry weight basis while also creating a product with superior storage and handling properties relative to other colorants known to the industry. Alternative methods of color purification include, but are not limited Ή column chromatography w^h adsorbent resias/farmentaiioo, sod extraction including, but not limited to, subaiticai fluid extraction, supercritical fluid extraction, and/or solvent extraction, [8848| In the case of pigment purification using membrane separation, purified pigments, iow in sugar and organic acids, are concentrated 308 by removing water using evaporation. Depending on the membrane proeess, it may be possible to dry the purified product directly without concentration. Once a liquid of suitabie composition and solids content has been prepared, tbe liquid is dried 400 under proper conditions effective to create a product with the described format and properties. These conditions allow suitable rates of water removal to achieve crystallization of the soiids while avoiding significantfoermai damage lo the color compounds. |8841| Figure 2 illustrates an exemplary process for purifying color pigments using uitrafiltration and dlafiitration to remove natural sugars and other low molecular weight dissolved soiids such as organic acids tom the retentate, according to one embodiment. In this embodiment, the feed 188 to the membrane system is preferably a fruit or vegetable juice/extraetof less than about 4CP Brlx, and preferably between about 12-22° Bnx, In one embodiment, the membrane system 203 comprises polymeric membranes as known in the art, The membrane system 283 used in one embodiment is composed of poiyethersultone (PESJ with a molecularwelght cutoff in the range of about 5,000-10,000 Daltons, such as those manufactured by Koch Membrane Systems Of HydranaUtics. Membranes of this type provide rejection characteristics suitable lor creating a permeate stream SOS that is enriched in sugar and acids and a retentate stream 204 increasingly enriched: in pigment compounds such as anthocyanins and polyphenols relative to the concentration of sugar and acid, in another exemplary embodiment, a system of PES spiral ultrafiltrdtion membranes with a nominal molecular weight cutoff of about 5,000; Daltons is used.., Oitofiltrailon 282 may be performed over any operating temperature and pressure ranges that avoid damage to the membranes and provide sufficient cross flow as specified by the membrane manufacturer.

However, in the present embodiment, maintaining temperatures below about ?d®F or more preferably below about 40°F, maintains product quality by stowing pigment color degradation kinetics, Retentate 284 from the membrane system 203 is returned to the feed lank SOI arid eireyiaied back through Ihe ultrafiltration membranes 202 until a limiting viscosity and flux Is reached, typically at a retentate solids concentration of about 20-25% by weight. Further purification may then continue by adding water to the retbritate 208 and concentrating again by circulating through trie membrane 203 up to a limiting soilds concentration. Diarlltration 206 sequences are repeated until the desired pigment purity is achieved in the retentate The retentate, according to one embodiment, contains: pigment concentrations greater than about 45,000 coior units on a dry weight basis compared to the base extract/juice of about 3,000 color units on a dry weight basis. (0042] Tft# disTiitratlesn stop may be modified by adding water '200 at a; rate approximately equal to the rate of permeate 20S leaving the system, thereby performing a continuous dlafiitration until the desired retentate composition is achieved. (0043] - After each concentration, retentate samples may foe analyzed lor residual sugar and color strength on a dry weight basis (color strength as liquid -e percent solids by weight). Once the retentate reaches a color strength on a dry basis that produces the product within the desired specifications, the product is concentrated 300. Due to the natural variation in the composition of the feed material for this process, the amount of diafiltration required can vary, typically from about 2-4 diaflitrations. (0044] As a non limiting example of a batch size, a feed tank of 5,SOD gallons of reconstituted , pasteurized pee at about 18-2¾° Brix will be circulated through the memfomne system with the retentate recycled back to the feed tank until the tank reaches a soilds level of about 30* Brix (at which point tie decrease in flux usually prohibits: further concentration). This results in approximately a fourfold reduction in volume of the feed liquid, leaving about 1,500 gallons of retentate. Because this Initial concentration may not increase the ratio of pigments such as anthocyanin pigment molecules to sugar enough to achieve a targeted color strength, the retentate may undergo several diafiitFatlons to reach a sufficient dissolved solids composition. According to one embodiment, for each dlafiitration, the retentate Is reconstituted with a 1:1 volumetric ratio of water to concentrate and the about 3.000 gallons of reconstituted material is circulated through the membrane system and concentrated back to the original retentate volume of about 1,500 gallons. £0845| ίπ a non-limiting embodiment, throughout the ultraltratlon and diafiltration process, the permeate may pass through a small surge tanlt attached to the membrane skid and be pumped out to a SOKigallon permeate accumulation tank in the plant cellar where it is concentrated and used in concentrate blends, £0046] After achieving the desired color Intensity oh a dry weight basis by adjusting the ratio of pigment to sugars, membrane processing ends and the retentate liquid may be further concentrated in solids without adjusting the solids composition, £Q847| Pigment purification can also be achieved using adsorption resin separation technology. jh this embodiment, shown in Figure §, a water-based toil or vegetable juicefe:)<tract:100 is passed; (feed ilquld :581) through a packed bed of adsorbent resins 502. the pigment compounds are prefbrehtiaily adsorbed on the resins relative to other dissolved solids such as sugar and acids §03. The adsorbed pigments are subsequently recovered torn the resin using an ethanoi/water eiyerrt 808 of varying composition. The purified, pigment rich eiluate 584 is distilled 585 to recover ethanol 507. The alcohol-free., high purity pigment 588 Is concentrated according to the processes noted In £88481 In another embodiment, pigment purification can be achieved using fermentation to convert the free sugar to alcohol, and subsequently recovering the alcohol using conventional bsatiation processes, in this embodiment, shown in Figure 6, the fruifrvegetable Sugar from the fruit/vegetable juice/eMmctiOO (feed liquid 681} is fermehted to alcohol using active yeast 683 at appropriate temperature (about 50° to 100° F) in a suitable fermenter 682. It wiii be appreciated that other temperature ranges may be suitable for fermentation as known to those of skill in the art. The fermented byproduct; 804, comprised of about 8 to 25 percent alcohol, is distilled 885 ίο recover the ethanol 887 leavinl purified color pigments 688. The alcohol-free liquid is subsequently concentrated by removing water according to the methods outlined in Figure 6, £00491 ^ yet another embodiment, pigment purification is achieved using supercritical fluid or solvent-solvent extraction processes^ in this embodiment, shown in Figure 7, water-based fruit/vegetable juicefe;xtract 188 (feed liquid 701} is contacted with a nonpolar, non-water miscible extract liquid (such as hexane) or solvent 702 which; preferentially absorbs the color compounds. The absorption process is repeated to yield an extract fraction rich in color compounds 70S and a fraction rich in carbohydrates andter other non-colored components 704. A batch or continuous extractor 703 may fee used to recover and 'Concentrate, the color. The extract solvent 70$ is subsequently distilled 700 to recover the solvent for re use 708. yielding a solvent-free, pigment-rich water-based liquid 707, which is subsequently concentrated by removing wafer according to thetmethOderoutlinedrin Figure 3, IO0SOJ Figure 3 illustrates an exemplary process of concentrating 300 and drying 400 a purified color liquid using a, refractive window dryer In an exemplary embodiment, The dried crystalline material is then milled §00 to produce a powder form with a consistent particle size range. Purified liquid: can be produced using membrane filtration such as uitrafiltration/dlafiltration, adsorption resin, fermentation, solvent extraction and/or superi critical· fluid extraction technologies. Depending on the solids content in the purified liquid, If may fee necessary to concentrate the solids to 20-35% by weight prior to drying, |S0§i] Concentration 300 of the purified liquid color may fee performed by feeding the final reientate from the previous step to a falling film evaporator, in one embodiment. Other types of evaporators, such as a forced circulation evaporator or plate evaporator may also fee used (0&amp;S2f in one non-limiting embodiment, the retentate Is concentrated with a failing film evaporator prior to drying. One exemplary failing film evaporator is a small (single effect) foiling film ./evaporator, in one embodiment using a falling film evaporator, a final solids content of about 16-20% fey weight and about 26-30ft 8rix, the retentate is circulated through the evaporator until the solids concentration of the feed tank reaches :about 25-30% solids fey weight Or about ASMS* Srix, This degree Of concentration results in a volume reduction of approximately 45% and takes approximately 12 hours, according to one embodiment The resulting liquid is then ready as feed material for dryfng./euohfoS'Wiih'dtrefedilve/wihdow dryer. The liquid may additionally be pasteurized and packaged into mobile metal drums so that it can bo stored without spoilage and can be transported in small units as needed, [00§3l Because the final concentrated liquid fed to the dryer still may not be at a shelf-stable solids concentration of concentrate (which could require concentration up to 68+i: Brix), and Is fed to the dryer at a .rate of about 9-12 gallons per hour with some drying embodiments , an optional additional pasteurization step may be warra nted tat the end ot liquid processing. This pasteurization step may kit! any yeast ooils tHat may have been introduced during processing before the liquid is stored and/or gradually fed to the dryer. Any method of pasteurization known In the art may be used An exemplary method # pasteurizatjon inoiudes heating the liquid about 185° F for about 30 seconds and cooling the liquid to about 55* F into a"Surge tank. From this surge tank, the liquid may be immediately pumped to a barrel filler where it is injected, without exposure to air, laid bags that line:the barrels (e.g., 54-galion metal barrels). According to one embodiment,/barrels of finished liquid feed: material are stored at approximately 40-0015 F. The barrels may be brought to the dryer in groups (up to tour for one pallet}, where they are gradually depleted one at a time. P0S4| Purifying natural pigmenis ensures that the final dried product exhibits superior shelf stability and handling characteristics including density* flowabiltty, water dispersion, and bygrosoopicity, Purified color extracts, have Improved: drying characteristics, and hence can be dried using a variety of standard drying techniques including spray, drum, belt, and aimosphene/vacuum tray drying. These techniques can subject the pigments to excessive high temperatures or residence time, resulting in color deterioration and/or adverse sensory impact. These drying techniques may also produce varying crystalline morphology with associated differences in quality or material handling characteristics:, Toprepare a crystalline product with superior quality, handling, and/or dissolution characteristics, the ooior concentrate must be dried slowly, as is the case for refractive and freeze drying, to allow formation of targe crystal lattices, including crystallization of any residual sugar, in one embodiment, the present process uses a refractive window dryer that significantly reduces tbe temperature requirements lor effective drying and the time of exposure to elevated temperatures. Spray drying and drum drying, In contrast, operate at higher temperatures to accomplish drying over a very short time and leaves components in an amorphous state. Freeze drying can also be used to produce large crystal lattices provided the base material is purified prior to drying, [ftCSSSJ After concentration, the liquid is dried to produce a crystalline solid pigment, in one embodiment, as shown in Figure 3, the liquid may then be applied te a refractive •window'dryer 400 to remove most of the remaining water and produce a crystalline solid Of less than about 8% moisture. The dryer 400 comprises a long tunnel, typically formed from stainless steel. Liquid product passes through tunnel as a tliln layer spread across the top surface of a thin plastic conveyor belt 403, In the drying process, :hot water circulates through shallow heating trays underneath the conveyor belt and heats the liquid tayer; according to one embodiment.: Thermal energy from the hot1 water is transmitted through the; conveyor belt by means of conduction and radiation, in one embodiment, the hot Water is at a temperature of up to about 210* F. It will be appreciated: that the water may be any temperature editable to heat the liquid layer to a desired temperature. Air blowers continuously sweep water vapor away from the thin' layersurface to.maximize the fate of water evaporation. The combination of evaporative cooling and limited heat conductivity of the plastic bait keep thethin liquid layer from reaching the temperatures of the hot water In the heating trays, which could negatively impact product quality. The product leaves the tunnel as a dried solid product layer which may be removed by a sharp plastic edge placed in contact with the belt at the end of the dryer. Contact with this edge causes the layer of dried product to break off into thin crystalline pieces of varying size.

[0050] The solid product exits the dryer in forms that can be described as sheets, flakes, or granules of varying particle,size, These particles may then be milled through a screening mil! 500, or other sultabie particle Size reduction equipment such as an impact mill, to produce particles irra desired size range. The desired particle size range may be determined by specific i ndystry app! icatiohs. In the embodiment where the pigments are prepared as a food colorant, the desired particle Size consists of no less than about 90% of total particle size betweeh about 50-425 pm for purposes of optimizing handling characteristics and standardizing bulk density, in other embodiments, about 90% of total particle size is less than about 100-200 pm, less than about 100-250 pm, less than about 100-300 pm,Jess than about: 100-400 pm, less than about £00-250 pm, less than about 200-300 pm,Jess than about 250-300 pm, less than about 200-400 pm, or less than about 250-400 urn.

[00571 In one embodiment, the concentrated 1 iqyId feed material 300 passes through a dryer such as a. refractive window dryer to remove water and produce a crystalline solid of less than about moisture by weight. In other embodiments, the crystalline solid has less than about 5-10% moisture by weight jjtf058J In one non-limiting embodiment, the:present disclosure concerns unique dry colors made: from fed grape Juice concentrate and purple carrot juice concentrate. A particular embodiment Is a crystalline red colorant from grapes1 with alleast about 40,000: oolor units, lit other embodimehtSi the crystaliirie red colorant has about 40,900- 55.000 dolor 001^: 0500^42,000^55,000 dolor units,, abeui 45,000-55,000 color units,, about 40,000-50,000 color units, about 42,000-50,000 color units, about 45,000-50,000 color units. 1« further embodiments, the crystalline fed colorant has greater than about 40.000 color Units,. greater than about 42,000 color units, greater than about 45,000 color units, greater than about 50,000 color units, or greater than about 55,000 color units. Another particular embodiment Is a crystalline purple oolorani from carrots with at least about00,000 color units, in ether embodiments,, the crystalline purple colorant has about 85,000-130^000 color units, about 85,000-125,000 color units,, about 90,000- 130.000 color units, abeut 90,000-125,000 color units, about 95,000-130,000 color units, about 95,000-125,000 color units: about 100,000-130,000 color units, and about 100,000-126,000 dolor units, in further embodiments, the crystalline purple colorant has greater than about 35.000 color units, greater than about 90,000 color units, greater than about 95,000 color units, greater than about 100,090 colorunits, greater than about 125,000 color units, and greater than about 130,000 color units.

[00!i9j Figure 4A and Figure 4B illustrates the side vieyv and cross-sectional view of an exemplary refractive window dryer 400 respectively. The dryer 400 comprises a long tunnel 401, typleaily formed from stainless steei, suitable for rapid water evaporation. Liquid product passes through tunnel 401 as a thin layer 402 spread across the top surface of a thin plastic conveyor belt 403. fMOOJ in one non limiting erhtedihient, liquid colorant is applied to the belt using an air pump with a suction hose inserted into a feed barrel, which pumps liquid from the barrel through a filter, such as a 75 micron in-line filter, and into a small feed balance tank. The air pump Is typically controlled by the level in the feed balance tank. Valves on feed spout(s> drain produetonto an applicator tray, forming a thin layer on the moving surface of the belt. £0061J Hot water circulates through shallow heating trays 404 underneath the conveyer belt 403 and heats the liquid layer 402, according to one 'embodiment Thermal energy from the hot water is transmitted through the conveyor Celt 403 by meant of conduction and radiation, in one embodiment, the hot water is at a temperature of eg to about 210* F. It will be appreciated that the water may be any temperature suitable to heat tie liquid layer 402 to a desired temperature.

[0002] Air blowers continuously sweep water vapor away from the thin layer surface 402 to maximize the rate of water evaporation. The combination of evaporative dpbllng and limited heat conductivity of the plastic beit keep the thin liquid layer surface 402 fr<^:^chidgthe-;t^pere^r^:'M;;^e hot water in the heating trays 404, which could negatively impact; product quality. pmi The product leaves the tunnel 401 as a dried solid product layer 405 which may be removed by a sharp plastic edge 480 placed in contact with the belt 403 at the bulinose end of the dryer. Contact with this edge causes the layer of dried product to break oft Into thin crystalline pieces of varying size, in one embodiment, the crystalline product fails off the end of the beit for collection . In an embodiment, plastic bags placed Inside plastic barrels and supported by a mobile stainless steel frame are pieced to ooilect the crystal line produce from the belt. |00€4| Soft water may be used for the water in the heating trays under the belt to avoid staining and deposits on the stainless steel. The water is typically held in tanks underneath the belt. In one embodiment, each: tank is connected to and circulated through a heat exchanger that uses steam to reach and maintain an adjustable setpoint temperature, [0065] in another embodiment, the purified, liquid concentrate is dried using vacuum, freeze-drying processes to produce a dry powder with large crystalline Structure exhibiting superior cpior stability, andter color handling Characteristics, in this embodiment, illustrated in Figure 8, the purified liquid is placed in a freeze dryer 801 vacuum chamber. Air and water vapor is removed from the chamber under vacuum until the liquid in the trays is frozen, fee frozen frays are then indirectly heated using an externa! source (i.e. steam, hot water, electricity) with the trays maintained under •vacuum. Residual water is sublimed from the frozen material until moisture levels are below about 7 percent. The water sublimation step is performed at plate temperatures ranging from about 40° C to 100° € for a period of about 8 to 24 hours depending oh the water content and composition of the pigment. Once the water is sublimed, the trays are removed from the vacuum chamber and the dry crystals are recovered as graholes of varying size. The granules are milled through a sproeniog ml 802, or other size reduction equipment such as Impact milts as known in the art, to produce pedicles le a desired size range S8S< The milling process produces a more consistent particle size and a higher packing density for better storage and/or shipping efficiency.

Crystalline Colorants/Pigments f0088| In another aspect, a crystaiiine'pigmenf or colorant is described. Preferably, the crystalline pigment or colorant is derived from natural pia/it or algae sources, The novel combination of purification technologies and drying produces a unique natural colorant, high in color and/or low in sugar that exhlbib superior shelf stability and/or handling characteristics, including density, flowabilify, water dispersion and/or less hygroscopic character. As such, the present crystalline pigment or colorant overcomes some of the basic problems that the Industry has been dealing with when using dry natural colorants. ($087! In embodiments, derivatives and/or modifications of the crystalline pigment are contemplated. Modifications include, but are not limited to, co-pigmentation, saponification, complexing, ahd/Of flaking. The pigments may be modified and then formulated info a colorant composition.

[88881 As seen in Figures 9A-9D, the present crystaitihe pigments are crystalline rather than amorphous. The present natural dry colorant is slot spray dried and therefore is not amorphous in nature with low bulk density and does not require additives to enable drying or to make It less hygroscopic. Instead, the present natural dry poloradt Is dried using a milder drying technique, including, but not limited to drying with a refractive window dryer, or freeze-dryer.

[8089] The crystalline colorant or pigment may be produced from any suitable plant or algae producing desired pigments. In embodiments,; the pigments consist of anthocyanlns, carotenoids, curcumin, betaiains, earnlinic acid and derivatives, and/or chlorophyll and derivatives. Carotenoids include, but are not limited to, β-caroiene, a-carotene, apocarotenais lycopene, blxin, norblxin, canthaxanthSm and zeaxaetiwu Chlorophyll and chlorophyliin derivatives include, but are not limited to, copper complexes. In another non-limiting embodiment, the pigment may be completed with a metal bn such as, but not limited to, copper. In non-limiting embodiments, the crystalline colorant or pigment is obtained from grapes or carrots, it wi be appreciated that pigment compositions may include one or more crystalline pigments.

[§0703 The present purified natyral dry colorant is produced using a m iicier drying technique thiat yields a crystailine color that is non-hygroscopic. This purified Crystalline color has exdellent dispersability and dissolution characteristics due to its non-hygrosoopic nature and does not require agglomeration and granulation to improve dissolution characteristics, [00713 When purifying fruit and vegetable pigment juice and extracts, the composition of the sugar component is reduced from about 70% to 95% on a dry weight basis to about 10 to 20% on dry basis,.according to one embodiment, in other embodiments, the sugar component is reduced to less than 10%, to less than 15%, to less than 20%, to 16-20%, to 10-16% on a dry basis. In further embodiments, crystalline pigments described herein have about 5-20% total sugar on a dry basis. In other embodiments*, crystailine pigments have about 5-10% total sugar on a dry basis, about 5-15% total sugar on a dry basis, about 10-20% total sugar on a dry basts/SbsuH&amp;i 5$r:totai sugar on a dry basis, or about 15-20% total sugar on a dty basis. Reducing the concentration of sugar miatfve to total dried solids also concentrates the pigmented portion to about ? to 15 times the original concentration on a dry weight basis, according to one embodiment, in embodiments, the pigmented portion is concentrated to about 7-10 times or 10-15 times the Original concentratidn oh a dry weight basis. There are several techniques for purifying the colorants, including yltraftitration/diafiltraiion, addorptioh resin, solvent extraction, fermentation;, and super critical or sub critlcaj fluid extractions, [00723 As noted above, the crystailine colorant or pigments are high in color. Table 1 contrasts the color intensity of purified grape and carrot pigments to standard sugar-based natural colors. Color strength measurement for Table 1 is: 520 yl

Grmns S^mplepm-100 w^u^fierSoh^Wa ξρΗ 3.2) ‘v pr&amp;jj As shewn, the typical color intensity of unpurified fruit end vegetable Juice concentrates is 2,000 to 12,000 color units. Purified pigments exhibited a color intensity of about 40,000 to §5,000 color unitsfor grape anthocyanins, and about 90,000 to 125,000 cbior units for purple carrot anthocyanins, In an embodiment,: the purified pigments have s coior intensity of greater than about 40,000 color units for grape anthocyansnk in another embodiment, tbe purified pigments have a coior intensity of greater than about 90,000 color units for purple carrot anthocyanins. in an embodiment, the coior value is equal io:

.Λc:> fM 520 smfl -t:w «i.C) ‘?OOQ dmoms of Sample per 100 ml Muiffer Soltitimi (pH 3.2) [0§74| In a further embodiment, the purified pigments exhibit an increased coior intensity as compered to raw juice and/or to unpurified pigments or pigment compositions, in non-limiting embodiments, increased color intensity refers to at least about 5-200% increase sh color Intensity, In further embodiments, increased color intensity refers to at least about 5%, 10%, 20%, 25%, 50%, 75%, 100%, 150%, 200% increase in color intensity or more.

[O075| The ranges of values for residual sugar and color intensity are provided for Illustration purposes only and represent nominal purification levels achievable using membrane purification processes. Lower residual sugar levels (down to less than 1 percent) are possible using additional or different membrane filtration andfor different purification processes including fermentation, adsorption resins, and solvent extraction. [0070| Table 1: Purified Pigment Color intensity for Extracts, Purified Concentrate, and Purified Powder

Ρδ?7] As seen from Table i , the punfied:pigment powder had significantly Increased color as compared to the raw fruit exiracticoncentraie, iM also seen, from Table 1, the purified pigment powder had reduced sugar content as compared to tile raw fruit exfracfrconcenirete. The grape pigment had at least 4 times less sugar than· the raw fruit extraci/ooficentrate and the carrot pigment had at least 2.8 times less sugar. The purified crystal red grape pigment had 13-17 times stronger color strength on a dry basis than the unpunfled grape juice concentrate. The purified crystal purple carrot pigment had 6~9 times stronger color strength on a dry basis than the unpurified purple carrot juice concentrate. In embodiments, the purified crystal pigment has 5-20 times stronger color strength on a dry basis as compared to an unpurified juice concentrate.

Id fudher embodiments, the purified crystai pigment has 5-10 times, 5-15 times, 10-15 times, or 10-20 times stronger color strength on a dry basis as compared to an unpurified juice concentrate. {0078J The data shown in Table 1 reflects the use of membrane filtration to purity the natural pigment, inherent in membrane filtration Is a practical lower limit for sugar content based on the amount of diafiltration required and the decreasing yield of purified color with increased diafiltration. Other purification methods, such as fermentation or adsorption resins, can potentially achieve lower sugar content and hence higher relative purification, it wilt be appreciated that lower sugar content and higher color purity may be obtained with other purification methods. f$Q7d| Table 2 summarizes the differences In physical' characteristics among refractive window, freeze, end spray dried powders produced from the same purified grape anthocyanin pigment As shown, the refractive window and freeze dried crystals exhibit markedly different photomieroscopy, particle size distribution, and particle density compared To spray dried powder. '$$001 Table 2: Physical Characteristics for Purified Grape Pigments

5 0.5 bar dispersion pressure 2 The terms DIO, 050, and D90 refer to the particle sizes at which 10%, 50%, and 90% of the sample is smaller.

Motes: The moisture content of the refractive window end spray dried products were 3.0% and 3.5%, respectively.

[0081| As seen from Figs. 9A-9B and 10A-10B, refractive window and freeze dried powders exhibit a giassy and angular crystal, reflecting relatively slow crystal growth compared to spray dried powders. Refractive window crystals further exhibit micfopoms within the base crystal structure (Fig, 10A). The angular, glassy morphology of the refractive window and freeze-dried crystals provide the superior physical and flowabillty characteristics as Idrther discussed below. £00823 Spray dried powder, in contrast is spherical and glassy (Figs. 90 and i00)-. [0083| The crystal size for refractive window or freeze dried powder is approximately 7 times larger than spray dried powder produced from the same purified grape pigments. Ninety percent of the refractive window and freeze dried powder crystals were less than 277-287 pm whereas 90 percent of the spray dried particles are less than .38 pm in diameter. As a result of their larger average particle size, the crystalline powders produced by refractive window and freeze drying exhibit less dust in handling when compared to an equivalent spray dried powder, which results in Jess airborne produet loss and cleaner and safer use in a manufacturing environment. £8084] The particle density for refractive window and freeze dried powder is SO percent greater than the value for spray dried powder: 1.5 versus 0.9 grams/cnr\ [0085] Table 3 summarizes the powder flovvability characteristics for purified grape anthocyanin pigments dried using refractive window and spray drying processes. As shown, purified powder produced using refractive window drying is less cohesive and exhibits iower wall friction and higher air permeability compared to the spray dried version. These properties result in smaller hopper outlet requirements, less steep hopper angle requirements, and higher steady state discharge flow rates respectively. £0085] Table 3: Fldwability Characteristics for Purified Crape Pigments 1 Cohesive archisthe

in a mass flow bib,

Smaller arch sizes afibw higher throughput aithe same outlet size and more design flexibility.

Wall friction is the maximum mass flow angle needed to maintain steady flew. Larger angles allow more design flexibility, 3 Permeability measures the critical mass flow fate that can be sustained without plugging. £5087] Cohesive strength measures a powder’s tendency to form faf holes and cohesive arches. Cohesive arch measurements determine the smallest hopper outlet size required to sustain steady-state flow without plugging, A smaller minimum outlet diameter is preferred since if requires smaller transfer pipe and mixing equipment •Purified grape pigment powder produced using refractive window drying can sustain steady flow in a cone-shaped outlet as email as § ore M':diameter. The same purified pigment produced using a spray dryer requires a cone diameter as large as 55 cm to sustain steady-state fiow, nearly 8 times larger.

[0088J Waii friction angle is another measure of a powder's resistance to hopper dlseha:rge or pipe flow and susceptibility to plugging. Larger angles indicate superior flowabilify because mass flow can occur with hopper wails farther from vertical orientation, thereby reducing the space footprint required to achieve a given flow rate. Purified powder produced using ref active window drying has a conical hopper wail fiction angle of 18 degrees compared to 1 i degrees for purified powder produced using Spray:drying and subject to the seme outlet size, wall material [0089] Powder permeability correlates with steady-state flow characteristics, with higher permeability able to sustain steady fiow. Powders with high air permeability retain their ferm and sustain high low rates through confined openings while powders with low permeability experience discharge rate limitations due to interaction with air. Flowabiiity characteristics are quantified by determining the steady-state flow of a powder through a fixed opening. Purified powder produced using refractive window drying can sustain steady state flow close to 700 kg/min through a t-foot diameter conical opening compared to only S kg/min tor purified powder produced using spray drying. Similar enhanced fiowability characteristics as described above for purified grape pigments are expected to hold true for other purified natural pigments purified using the same purification process and dried using freeze drying; [0090] in embodiments, the pigment of colorant are formulated as a composition. The pigments or colorant may be formulated as an aqueous solution, emulsion, suspension, and/or dispersion. The pigments or pigment compositions are contemplated for any suitable situation of adding or enhancing color. In embodiments, the pigment or pigment compositions are used In food, dmgs, and/or cosmetic applications.

EXAMPLES

[0991] The following example is illustrative in nature and is. in no way intended to be limiting.

Example 1

Crystalline CoKorantEormatlo« [0092j Ά red grape juice concentrate and a purple carrot: juice concentrate were separately reconstituted to about 18-22° Brix |O0i3j The red grape juice concentrate and purple carrot juice concentrate wore separately purified through ultrafiltration and diafiltratlon across a RES membrane system, P0l4j Purified rod grape juice concentrate and purple carrot juice concentrate were separately concertrated Using a failing film evaporator and then dried using a .refractive window dryer. Purification data was measured: and tbs results are showmln Table 5, Table 5: Crystal Purification Data

P0963 White a number of exemplary aspects and embodiments have been discussed above, those of sfbii in the art will recognize certain modifications:, permutations, additions and sub-combinations thereof. It is therefore intended that the Mowing appended claims and claims: hereafter introduced, are interpreted: to include allsuoh rood ideations, permutations, additions end sub-combinations as areWithih their true spirit and scope.

Claims (7)

1. CLAIMS What is claimed is:

   1. A natural colorant composition comprising: a crystalline pigment or mixture of pigments derived from plants or algae, wherein the composition has a color intensity that is higher than raw juice, and wherein the composition has decreased sugar on a dry weight basis than raw juice, and wherein the composition has a bulk density of 0.62 g/cm3 or greater.
2. 2. The composition of claim 1, containing less than about 5-20% sugar on a dry weight basis.
3. 3. The composition of claim 1, having a color intensity greater than about 40,000 color units.
4. 4. The composition of claim 1, wherein the pigment is a red grape anthocyanin and the composition has a color intensity of about 40,000-55,000 color units.
5. 5. The composition of claim 1, wherein the pigment is a purple carrot anthocyanin and the composition has a color intensity of about 90,000-125,000 color units.
6. 6. The composition of claim 1, further comprising a total sugar content of less than about 20% of dry weight.
7. 7. The composition of claim 1, wherein the pigment is selected from the group consisting of anthocyanins, carotenoids, betalains, curcumin, carminic acid, carminic acid derivatives, chlorophyll, and chlorophyll derivatives.