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    • 专利摘要:
    METHOD FOR PREPARING AN INHIBITED NON PREGELATINIZED GRANULAR STARCH. The present invention relates to an inhibited non-pregelatinized granular starch suitable for use in a food ingredient in place of a chemically modified starch, which can be prepared by heating a non-pregelatinized granular starch in an alcoholic medium in the presence of a the base and / or a salt. Steam treatment can be used to intensify the extent of inhibition.
    公开号:BR112014028425B1
    申请号:R112014028425-3
    申请日:2013-05-09
    公开日:2020-12-22
    发明作者:Xian-Zhong Han；Thomas K. Hutton
    申请人:Tate & Lyle Ingredients Americas Llc；
    IPC主号:
    专利说明:

    Field of the Invention
    [0001] The present invention relates to the production of inhibited non-pregelatinized granular starches that are useful as ingredients in food compositions. Background of the Related Art
    [0002] A recent trend in the food industry has been the growing consumer demand for so-called "clean labeling" or non-chemically modified ingredients. In applications where it is desired to thicken a food product, such as soup or sauce, which must be subjected to strong acid and / or heat and / or shear conditions during its processing or terminal use, chemically modified starches have traditionally been used , since such starches are notably tolerant of such extreme conditions. These chemically modified starches are produced by various crosslinking techniques in which a chemical reagent is used to form crosslinks in the starch and thereby alter its viscosity and stability characteristics at elevated temperatures. However, it would be desirable to develop substitutions for such chemically modified starches, which exhibit similar performance and are not yet viewed or classified as chemically modified for labeling purposes. Summary of the Invention
    [0003] The invention provides a method for preparing an inhibited non-pregelatinized granular starch, wherein the method comprises heating a non-pregelatinized granular starch in an alcoholic medium in the presence of at least one treatment agent selected from the group consisting of bases and salts at a temperature of at least 35 ° C.
    [0004] In another aspect, the invention provides a method for preparing an inhibited non-pregelatinized granular starch, wherein the method comprises: heating a non-pregelatinized granular starch in an alcoholic medium in the presence of a base at a temperature of at least 35 ° C; neutralize the base with an acid; separating the inhibited non-pregelatinized granular starch from the alcoholic medium; and removing the alcohol solvent from the non-pregelatinized granular starch inhibited by heating.
    [0005] The alcoholic medium can be comprised of a C1-C4 alcohol (for example, ethanol). In another embodiment, the alcoholic medium is comprised from 0 to 20 weight percent of water. In one embodiment, the alcoholic environment is basic. In another modality, the alcoholic environment is neutral. The temperature in step a) can, in one embodiment, be at least 120 ° C. The heating in step a) can, for example, be carried out for a period of time from 5 minutes to 20 hours. The treatment agent can, for example, be a base selected from the group consisting of alkali metal hydroxides, alkali metal carbonates (in particular, sodium carbonate), alkali metal phosphate, ammonium phosphates, alkaline earth carbonates and alkali hydroxides earthy. The treatment agent can include a polycarboxylic acid salt. The polycarboxylic acid salt can, for example, be a sodium or potassium salt of a polycarboxylic acid. The treatment agent in one embodiment includes one or more sodium salts of citric acid. The treatment agent can be present in an amount of not more than 10 weight percent based on the weight of the non-gelatinized granular starch and / or it can be present in an amount of at least 0.2 weight percent, based on the weight of the non-gelatinized granular starch. The method may comprise an additional step of removing the solvent alcohol from the inhibited non-pregelatinized granular starch. The method may comprise an additional step of separating the inhibited non-pregelatinized granular starch from the alcoholic medium and heating the separated inhibited non-pregelatinized granular starch. Heating of the separated inhibited non-pregelatinized granular starch, in one embodiment, is conducted at a temperature of at least 120 ° C. The method may comprise an additional step of treating the steam-inhibited nonpregelatinized granular starch. The non-gelatinized granular starch used as a starting material can, for example, be selected from the group consisting of corn starch, pea starch, potato starch, sweet potato starch, banana starch, barley starch, starch wheat, rice starch, sago starch, amaranth starch, tapioca starch, sorghum starch, waxy corn starch, waxy pea starch, waxy wheat starch, waxy tapioca starch, waxy rice starch , waxy potato, waxy sorghum, starches having an amylose content of 40% or more, and combinations thereof. In particular, the non-pregelatinized granular starch can be corn starch or a waxy starch. In one embodiment of the method, the non-pregelatinized granular starch is in the form of a slurry in the alcoholic medium and the pH of the slurry is at least 6. In another embodiment, the at least one treatment agent includes a base and the The method comprises an additional step of neutralizing the base in the non-pregelatinized granular starch inhibited with an acid. The acid can, for example, be selected from the group consisting of acids containing phosphorus, carboxylic acids, uric acid and mixtures thereof. For example, the acid can be selected from the group consisting of citric acid, oxalic acid, malic acid, lactic acid, acetic acid and mixtures thereof. The acid can be a polycarboxylic acid. After neutralization, an additional step of heating the non-pregelatinized granular starch inhibited in the alcoholic medium can be performed. For example, additional heating of the inhibited non-pregelatinized granular starch in the alcoholic medium can be carried out at a temperature of about 120 ° C to about 200 ° C.
    [0006] In yet another aspect, the invention provides a method for preparing an inhibited non-pregelatinized granular starch, wherein the method comprises: heating a slurry of a non-pregelatinized granular starch in an aqueous ethanol medium in the presence of a base at a temperature of 120 ° C to 200 ° C; neutralize a base with an acid; separating the inhibited non-pregelatinized granular starch from the aqueous ethanol medium; and contacting the inhibited non-pregelatinized granular starch separated with steam at a temperature of 100 ° C to 200 ° C to remove ethanol.
    [0007] After step b) and before step c), the neutralized slurry can be heated again, for example, at a temperature of 120 ° C to 200 ° C.
    [0008] Also provided by the present invention is a method for preparing an inhibited non-pregelatinized granular starch, wherein the method comprises: heating a non-pregelatinized granular starch in an alcoholic medium in the presence of a base at a hair temperature minus 35 ° C; neutralize the base with an acid to provide a neutralized slurry; heating the neutralized slurry to a temperature of at least 35 ° C; separating the inhibited non-pregelatinized granular starch from the alcoholic medium; and removing the solvent alcohol from the non-pregelatinized granular starch inhibited by heating.
    [0009] Another aspect of the present invention provides a method for preparing an inhibited non-pregelatinized granular starch, wherein the method comprises: heating a non-pregelatinized granular starch in an alcoholic medium in the presence of a carboxylic acid salt to a temperature of at least 35 ° C; separating the inhibited non-pregelatinized granular starch from the alcoholic medium; and removing the solvent alcohol from the non-pregelatinized granular starch inhibited by heating.
    [00010] The alcoholic medium may comprise a C1-C4 alcohol, such as ethanol. The alcoholic medium may comprise 0 to 20 weight percent water. In one embodiment, the temperature in step a) is at least 120 ° C. The carboxylic acid salt can, for example, be present in an amount of no more than 10 weight percent, based on the weight of the non-gelatinized granular starch. The carboxylic acid salt can, for example, be present in an amount of at least 0.2 weight percent, based on the weight of the non-gelatinized granular starch. In one embodiment, heating of the inhibited non-gelatinized separated granular starch in step c) is conducted at a temperature of at least 120 ° C. The method mentioned above may comprise a step of treating the vapor-inhibited, non-gelatinized granular starch. The non-pregelatinized granular starch can, for example, be selected from the group consisting of corn starch, pea starch, potato starch, sweet potato starch, banana starch, barley starch, wheat starch, rice starch, starch sago, amaranth starch, tapioca starch, sorghum starch, waxy corn starch, waxy pea starch, waxy wheat starch, waxy tapioca starch, waxy rice starch, waxy barley, waxy potato, waxy sorghum having an amylose content of 40% or more, and combinations thereof. In particular embodiments, the non-pregelatinized granular starch is corn starch or a waxy starch. The non-gelatinized granular starch can be in the form of a slurry in the alcoholic medium, and the pH of the slurry can be 5 to 8, in certain embodiments of the invention. The heating in step a) can, for example, be carried out for a period of time from 5 minutes to 20 hours. The at least one carboxylic acid salt can include a polycarboxylic acid salt, such as a sodium or potassium salt of a polycarboxylic acid. In one aspect of the invention, the at least one carboxylic acid salt includes one or more sodium salts of citric acid. The at least one carboxylic acid salt can be formed in situ, prior to step a) by combining at least one carboxylic acid with at least one base.
    [00011] Yet another aspect of the invention provides inhibited non-pregelatinized granular starch obtained according to any of the methods mentioned above.
    [00012] The present invention thus allows the preparation of inhibited starches, without the use of harmful chemicals, using only food-grade ingredients. In addition, no harmful chemicals are produced during such preparation. Starches produced according to the invention can be inhibited to levels comparable to highly chemically cross-linked starches, and can be used in the same applications in which chemically modified starches are conventionally used. For example, inhibited starches obtained according to the methods of the invention, can be used as alternatives or substitutes for chemically modified starches, where strong acid and / or heat and / or shear conditions exist or are applied. Brief Description of the Figures
    [00013] The Figures are explained in more detail in the Examples.
    [00014] Figure 1 shows the profiles of the Rapid Visco-Analyzer (RVA) (Cooking) of different starch samples measured at a concentration of 5% at a pH of 6.5 of aqueous medium.
    [00015] Figure 2 shows micrographs of starch pastes after RVA at pH 6.5 (200X magnification).
    [00016] Figure 3 shows the RVA (Cooking) profiles of different starch samples measured at a concentration of 5% at a pH of 3.5 in aqueous medium.
    [00017] Figure 4 shows micrographs of starch pastes after RVA at pH 3.5 (200X magnification).
    [00018] Figure 5 shows micrographs of various starch pastes after retort simulation.
    [00019] Figure 6 shows micrographs of various starch samples, some of which have been treated in accordance with the present invention.
    [00020] Figure 7 shows the RVA (Cooking) profiles of several starch samples measured at a concentration of 5% at a pH of 6.5 in aqueous medium.
    [00021] Figures 8 and 9 show the RVA profiles of various starch samples, including samples prepared according to the invention, as well as a chemically modified waxy starch with high cross-linking commercially available from Tate & Lyle.
    [00022] Figures 10 and 11 show the RVA profiles of various starch samples, measured at 6.65% in a buffer having a pH of 3.5.
    [00023] Figures 12 to 15 show micrographs of starch granules, in several samples of starch paste after RVA and retort simulation.
    [00024] Figures 16, 17 and 24 show the RVA profiles at different pHs of starch samples treated before and after desolventization.
    [00025] Figures 18, 20 and 25 show micrographs of cooked starch samples treated with 1% NaCl.
    [00026] Figures 19, 21 and 26 show micrographs of cooked starch samples treated with 1% NaCl and then cut using a blender.
    [00027] Figures 22, 23 and 27 show micrographs of treated starch samples illuminated with polarized light. Detailed Description of the Invention
    [00028] As used herein, the term "inhibited starch" means a starch that has the characteristics of a chemically cross-linked starch. Inhibited starches can vary with respect to their degrees of inhibition, as characterized by their observed viscosities and other characteristics, when 5% to 6.3% of dry starch in water having a pH of 3 is heated to 92 ° C to 95 ° C . A starch that is substantially completely inhibited will resist swelling. A starch that is highly inhibited will swell to a limited extent and show a continuous rise in viscosity, but it will not reach a peak viscosity. A starch that is moderately inhibited will exhibit a lower peak viscosity and a lower percentage of interruption in viscosity compared to the same starch that is not inhibited. A starch that is slightly inhibited will show a slight increase, an increase in peak viscosity, and a lower percentage of interruption in viscosity compared to the control starch (not inhibited).
    [00029] All starches (including starch flours) are suitable for use in the present invention. Starches can be derived from any native source. A "native" starch or flour is one as found in nature, in unmodified form. Typical sources for starches are cereals, tubers, roots, vegetables and fruits. The native source can be corn, peas, potatoes, sweet potatoes, bananas, barley, wheat, rice, sago, amaranth, tapioca, sorghum, waxy corn, waxy peas, waxy wheat, waxy tapioca, waxy rice, waxy barley , waxy sorghum, starches having an amylose content of 40% or more, and the like. In one embodiment, corn starch (in particular, waxy corn starch) is used. Mixtures of different starches can be used. The starch can be subjected to one or more purifications and / or modification treatments, before being heated with the alcoholic medium and treatment agent. For example, starch can be treated to reduce the amount of lipids and / or proteins present in the starch. Starch can contain some amount of moisture, for example, up to about 15% by weight of water.
    [00030] The alcoholic medium generally comprises at least one alcohol, particularly a C1-C4 monoalcohol such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butyl alcohol and the like. One or more other substances may also be present in the alcoholic medium, such as a non-alcoholic organic solvent (particularly those that are miscible with alcohol) and / or water. However, in one embodiment of the invention the alcoholic medium does not contain any solvent other than alcohol and, optionally, water. Aqueous alcohols, for example, can be used to advantage in the process of the invention. The alcoholic medium can comprise, for example, 30% to 100% by weight of alcohol (for example, ethanol) and from 0% to 70% by weight of water. In one embodiment, the alcoholic medium contains 80% to 96% by weight of alcohol (eg, ethanol) and 4% to 20% by weight of water, the total amount of alcohol and water equalizing 100%. In another modality, the alcoholic medium contains 90% to 100% by weight of alcohol (for example, ethanol) and from 0% to 10% by weight of water, the total amount of alcohol and water equalizing 100%. In other embodiments, no more than 10% or no more than 15% by weight of water is present in the alcoholic medium. The amount of alcoholic medium in relation to the starch is not considered to be critical, but typically, for the sake of convenience and sufficient processing ease, the alcoholic medium is present to provide a slurry that is agitated and / or pumpable. For example, the weight ratio of starch: alcohol may be from about 1: 2 to about 1: 6.
    [00031] In one aspect of the invention, at least some amount of the treatment agent (base and / or salt) is present when the non-pregelatinized granular starch is heated in the alcoholic medium. However, an advantage of this embodiment of the present invention is that large amounts of treatment agents (in relation to starch) do not need to be used in order to effect effective starch inhibition, unlike the previously known starch modification processes. This simplifies the subsequent processing of the inhibited starch and lowers potential production costs.
    [00032] Typically, at least 0.5% by weight of the treatment agent (based on the dry weight of the starch used) is employed, although in other embodiments of the invention at least 1%, at least 2%, at least 3% at least 4% or at least 5% by weight of the treatment agent is present. For economic reasons, generally no more than 10% or 15% by weight of the treatment agent is present.
    [00033] Typically, the mixture of starch, alcoholic medium and treatment agent is in the form of a slurry. In certain embodiments of the invention, it may be desirable to adjust the pH of the slurry to a particular value. It may be difficult to measure the pH of such a slurry due to the presence of alcohol. In an embodiment where it is desired to make the basic slurry by adding a base, an appropriate amount of base can be determined as if the slurry were a starch slurry in deionized water only and then scaled up to the current amount, while maintaining the same proportion of base and starch.
    [00034] The slurry can, for example, be neutral (pH 6 to 8) or basic (pH greater than 8). In one embodiment, the pH of the slurry is at least 6. In another embodiment, the pH of the slurry is at least 7. The pH of the slurry in another embodiment is no more than 12. In other embodiments, the pH of the slurry slurry is 6-10, 7.5-10.5 or 810. In still other embodiments, the pH of the slurry is 5-8 or 6-7.
    [00035] The treatment of the starch alcohol treatment agent can be carried out by first placing the starch in the alcoholic medium and then adding the treatment agent (for example, base and / or salt). Alternatively, the treatment agent can first be combined with the alcoholic medium and then contacted with the starch. The treatment agent can be formed in situ, such as by separately adding a base and an acid that reacts to form the salt that functions as the treatment agent.
    [00036] Bases suitable for use in the process of the invention include, but are not limited to, alkali metal and alkaline earth metal hydroxides, such as potassium hydroxide, calcium hydroxide, and sodium hydroxide, alkali metal carbonates and alkali metal earthy soda such as sodium carbonate, potassium carbonate, sodium bicarbonate, and calcium carbonate, alkali metal and ammonium salts of phosphorus-containing acids such as tetrasodium pyrophosphate, ammonium orthophosphate, disodium orthophosphate, and trisodium phosphate, and any other bases approved for use under applicable regulatory laws. Strong bases as well as weak bases can be used.
    [00037] Salts suitable for use in the process of the invention include water-soluble substances, which ionize in aqueous solution to provide a substantially neutral solution (i.e., a solution having a pH of 6 to 8). Alkali metal-containing salts are particularly useful in the present invention, as are salts of organic carboxylic acids. In one embodiment of the invention, the treatment agent includes a salt (in particular, a sodium or potassium salt) of a polycarboxylic acid such as citric acid or the like. Other suitable carboxylic acid salts include, but are not limited to, acetic acid salts, adipic acid, itaconic acid, malonic acid, lactic acid, tartaric acid, oxalic acid, fumaric acid, aconitic acid, succinic acid, oxalosuccinic acid, glutaric, ketoglutaric acid, malic acid, fatty acids and combinations thereof. Sodium citrates (monosodium citrate, disodium citrate, trisodium citrate and combinations thereof) are used in one aspect of the present invention. Other illustrative examples of suitable carboxylic acid salts include, but are not limited to, potassium citrates, calcium citrates, sodium malate, sodium fumarate, sodium oxalate and the like and combinations thereof. In one embodiment of the invention, one or more salts capable of functioning as buffering agents are employed.
    [00038] Mixtures of different treatment agents can be used in the present invention. For example, starch can be heated in the alcoholic medium in the presence of both, at least one base and at least one salt.
    [00039] The starch, alcoholic medium and treatment agent are heated for a while and at a temperature effective to inhibit the starch to the desired point. Generally speaking, temperatures in excess of the ambient temperature (ie 35 ° C or more) will be required. At the same time, extremely high temperatures should be avoided. The heating temperature can be, for example, 35 ° C to 200 ° C. Typically, temperatures of 100 ° C to 190 ° C, 120 ° C to 180 ° C, or 130 ° C to 160 ° C, or 140 ° C to 150 ° C will be sufficient. The warm-up time is usually at least 5 minutes, but not more than 20 hours and typically 40 minutes to two hours. In general, a desired level of starch inhibition can be achieved more quickly, if the heating temperature is increased.
    [00040] The specific conditions of treatment time, treatment temperature, and proportions of the components of the mixture of starch, alcoholic medium and treatment agent, are generally selected in such a way that the starch is not gelatinized to a significant extent. That is, the starch remains non-gelatinized. Thus, in various embodiments of the invention, no more than 30% or no more than 20% or no more than 10% of the starch granules lose birefringence as a result of such processing.
    [00041] When the temperature selected for the heating step exceeds the boiling point of one or more components of the alcoholic medium, it will be advantageous to carry out the heating step in a flask or other device capable of being pressurized. Treatment can be carried out within a confined zone in order to maintain the alcoholic medium in a liquid state. Additional positive pressure may be used, but it is generally not necessary. The starch can be fluidized in the alcoholic medium, together with the treatment agent under conditions of elevated temperature and pressure, and treated for a time sufficient to change the viscosity characteristics of the starch. Such treatment can be conducted in a batch reactor on a batch basis, or in a tubular reactor on a continuous basis, although other appropriate processing techniques are evident to those skilled in the art. In another embodiment, the starch may be in the form of a bed within a tubular reactor and a mixture of the alcoholic medium and treatment agent passed through that bed (optionally, on a continuous basis), with the bed being maintained at the desired temperature for the purpose of inhibiting starch.
    [00042] In embodiments of the invention in which the base was used as a treatment agent, the mixture of starch, the alcoholic medium and the base can be combined with one or more acids, once the heating step is complete, to purposes of neutralizing the base.
    [00043] Acids suitable for use in such a neutralization step include, but are not limited to, phosphorus-containing acids such as phosphoric acid, carboxylic acids such as acetic acid, adipic acid, itaconic acid, malonic acid, lactic acid, tartaric acid, oxalic acid, fumaric acid, aconitic acid, succinic acid, oxalosuccinic acid, glutaric acid, ketoglutaric acid, malic acid, fatty acids and combinations thereof, as well as other types of acids, such as uric acid. If the inhibited starch is intended for use as a food ingredient, the acid should generally be selected to be one that is permitted for such use under applicable regulations. Typically, sufficient acid is added to decrease the pH of the mixture to about neutral to significantly acidic, for example, a pH of about 5 to about 7 or about 6 to about 6.5.
    [00044] Acid neutralization can be performed at any appropriate temperature. In one embodiment, the starch slurry, base medium and alcohol are cooled from the used heating temperature to approximately room temperature (for example, about 15 ° C to about 30 ° C) before being combined with the acid to be used for neutralization. The neutralized mixture can then be further processed, as described below, to separate the inhibited starch from the alcoholic medium. In another embodiment of the invention, however, neutralization of the base is followed by additional heating of the starch slurry. Such additional heating was found to be able to modify the rheological properties of the obtained inhibited starch, when compared to the viscosity characteristics of an analogously prepared starch, which was not subjected to heating after neutralization of the base.
    [00045] Generally speaking, such an additional heating step is advantageously carried out at temperatures in excess of the ambient temperature (i.e., 35 ° C or more). At the same time, extremely high temperatures should be avoided. The heating temperature can be, for example, 35 ° C to 200 ° C. Typically, temperatures of 100 ° C to 190 ° C, 120 ° C to 180 ° C, or 130 ° C to 160 ° C, or 140 ° C to 150 ° C will be sufficient. The warm-up time is usually at least 5 minutes, but not more than 20 hours and typically 40 minutes to two hours.
    [00046] In embodiments of the invention in which a salt (such as a citric acid sodium salt) has been employed as the treatment agent, it may be advantageous to cool the starch / treatment agent / alcoholic medium moderately rapidly to approximately temperature after the mixture has been heated for the desired period of time. It has been found that, under at least some conditions, such rapid cooling can provide a more highly inhibited starch when compared to a starch obtained by decreasing the cooling of the starch / treatment agent / alcoholic mixture following the heat treatment step.
    [00047] The mixture of starch and alcoholic medium can be processed in order to separate the starch from the alcoholic medium. Conventional methods for recovering solid particles from liquids, such as filtration, settling, sedimentation or centrifugation, can be adapted for this purpose. The separated starch can optionally be washed with additional alcoholic and / or alcohol and / or water to remove any undesirable soluble impurities. In one embodiment, neutralization of residual base is carried out by washing, the starch recovered with an acidified liquid medium. Drying of the separated starch will provide an inhibited non-pregelatinized granular starch according to the invention. For example, drying can be carried out at a moderately high temperature (for example, 30 ° C to 60 ° C) in a suitable apparatus such as an oven or fluidized bed reactor or dryer or mixer. Vacuum and / or a gas purge (eg, a nitrogen sweep) can be applied to facilitate the removal of volatile substances (eg, water, alcohol) from starch. The resulting dry inhibited non-pregelatinized granular starch can be milled, crushed, laminated, screened, sieved or subjected to any of these techniques to achieve a particular desired particle size. In one embodiment, the inhibited starch is in the form of a free flowing granular material.
    [00048] In an embodiment of the invention, however, the starch undergoes a desolventization step at a significantly higher temperature (for example, greater than 80 ° C or more than 100 ° C or more than 120 ° C ). Excessively high temperatures should be avoided, however, as they can result in starch degradation or discoloration. Such a step not only reduces the amount of residual solvent (alcohol) in the product, but also provides the unexpected additional benefit of enhancing the degree of inhibition exhibited by the starch. The temperature desolventization can, for example, be about 100 ° C to about 200 ° C. Typical temperatures are 120 ° C to 180 ° C or 150 ° C to 170 ° C. Desolventization can be carried out in the presence or absence of steam. It has been found that steam treatment is advantageous in that it helps to minimize the extent of starch discoloration, which can otherwise occur at such an elevated temperature. In one embodiment of the invention, the steam is passed through a bed or cake of the inhibited starch. The starch desolventization methods of United States Patent No. 3,578,498, incorporated herein by reference in their entirety for all purposes, can be adapted for use in the present invention. Following steam treatment, the inhibited starch can be dried to reduce the residual moisture content (for example, heating in an oven at a temperature of about 30 ° C to about 70 ° C or in a fluidized bed reactor ).
    [00049] In one embodiment, the treated starch, which has been recovered from the alcoholic medium, is first brought to a total volatile content of no more than about 35% by weight or no more than about 15% by weight. This can be accomplished, for example, by first air or by drying in the oven the starch recovered at moderate temperature (for example, 20 ° C to 70 ° C) to the desired initial volatile content. Live steam is then passed through the dry starch, the system being maintained at a temperature above the steam dew point. A fluid bed apparatus can be used to carry out such a step of vapor desolventization.
    [00050] In general, it will be desirable to perform desolventization under effective conditions to result in a residual alcohol content in the inhibited starch of less than 1% by weight or less than 0.5% by weight or less than 0.1% by weight.
    [00051] Following desolventization, the inhibited starch can be washed with water and then re-dried to further improve color and / or taste and / or reduce the moisture content.
    [00052] The resulting starches are functionally similar to chemically cross-linked starches in that they can have a non-cohesive, soft texture when cooked out (for example, to maximize their functionality or performance in a selected application) or gelatinized (for example, starch no longer exhibits birefringence or Maltese hybridizations when illuminated using polarized light), and / or excellent tolerance to processing variables such as heat, shear and pH extremes, particularly for a significant time under such conditions . Also, the viscosity in cooking starts (starts to prepare) at a later time or substantially the same as the same starch that has not been inhibited according to the present invention. Such inhibited starches can also provide a desirable soft texture for the processed food product, and maintain its ability to thicken throughout processing operations. In addition, the inhibited starch will have less viscosity decomposition than the same starch that was not treated using the process of the present invention.
    [00053] The inhibited non-pregelatinized granular starch, obtained by the practice of this invention, can be mixed with other unmodified or modified starches, or with other food ingredients before use in a food product. Inhibited starches can be used in place of the chemically modified or crosslinked starches currently used in food, and still maintain a clean label (unmodified label).
    [00054] Food products in which inhibited starches are useful include thermally processed foods, acidic foods, dry mixtures, refrigerated foods, frozen foods, extruded foods, oven-prepared foods, cooked foods cooked on the stove, foods that can be prepared in micro -waves, totally fatty or reduced fat foods, and foods having a low activity in water. Food products in which inhibited starches are particularly useful are foods that require a thermal processing step such as pasteurization, retort, or ultra high temperature (UHT) processing. Inhibited starches are particularly useful in food applications, where stability is required through all processing temperatures including cooling, freezing and heating.
    [00055] Inhibited starches are also useful in food products where the non-chemically cross-linked starch thickening agent, viscosifier, gelling agent, or extender is required or desirable. Based on the processed food formulations, the practitioner can readily select the amount and type of inhibited non-pregelatinized starch, starch required to provide the required thickness and gelled viscosity in the finished food product, as well as the desired texture. Typically, starch is used in an amount of 0.1-35%, for example, 2-6% by weight of the food product.
    [00056] Among the food products that can be improved by using the inhibited non-pregelatinized granular starch are high acid foods (pH <3.7) such as fruit-based pie fillings, baby foods, and the like; acidic foods (pH 3.7 to 4.5) such as tomato-based products; low acid foods (pH> 4.5) such as gravies, sauces, and soups; top-cooked foods on the stove such as sauces, gravies, and puddings; instant foods such as puddings; salad dressings in spoonfuls or pourable; refrigerated foods such as dairy or imitation dairy products (for example, yogurt, sour cream, and cheese); frozen foods such as frozen desserts and dinners; microwave foods such as frozen dinners; liquid products such as diet products and hospital foods; dry mixes for preparing baked goods, gravies, sauces, puddings, baby foods, hot cereals, and the like; and dry mixes for coating foods before cooking the dough and frying. Inhibited starches are also useful in the preparation of food ingredients such as flavors and encapsulated mists.
    [00057] Inhibited starches prepared in accordance with the present invention may also be useful in various non-food end-use applications, in which chemically modified (crosslinked) inhibited starches have been conventionally used, such as cosmetics and personal care products, paper, packaging, pharmaceutical formulations, adhesives, and the like. EXAMPLES Starch Treatment Method A
    [00058] In this example, the starch is first heated in an alcoholic medium in the presence of base (sodium carbonate), followed by neutralization at a lower temperature. After separating the alcohol mass from the inhibited starch, the inhibited starch is subjected to drying / desolventization. Summary of the treatment procedure:
    [00059] Weigh 3A ethanol (94% by weight) 1177 g.
    [00060] Add 308 g of waxy starch (89% dry starch or d.s.) to the ethanol while stirring.
    [00061] Add sodium carbonate (0.7%, 1.4%, 2.8% or 5.53% by weight, based on dry starch).
    [00062] Transfer the mixture of starch, alcohol and sodium carbonate in a 2 liter high pressure stainless steel reactor equipped with stirring and controlled steam heating through its wrap.
    [00063] Heat the slurry in the reactor to a projected temperature (143 ° C) and keep it at that temperature for 60 minutes.
    [00064] Cool the reactor to 35 ° C.
    [00065] Open the respirator to equalize the pressure.
    [00066] Neutralize the slurry to about pH 6 using 50% citric acid solution (0.843%, 1.685%, 3.37% or 6.75% by weight of dry starch-based citric acid) using a syringe through of a respirator.
    [00067] Shake for 30 minutes.
    [00068] Open the lid.
    [00069] Remove the slurry from the reactor.
    [00070] Filter the slurry using a filter paper in a Buchner funnel.
    [00071] Remove and crumble the wet cake on a tray and leave it for several hours / or overnight before placing it in the oven. This allows more of the 3A alcohol to evaporate.
    [00072] Starch dried at 50 ° C in a convection oven overnight.
    [00073] Crush and pass the starch through a 100 mesh sieve and label.
    [00074] Starch dried at 125 or 160 ° C in a convection oven for 4 hours for desolventization.
    [00075] Steam desolventization:
    [00076] 1. Weigh 3.5 kg of DI water in a steel container (7.2 "in diameter, 8.5" in height).
    [00077] 2. Place the steel container with water in an oven (Yamato DKN 600 mechanical convection oven, Fisher Scientific Inc.) at 160 ° C for one hour.
    [00078] 3. Weigh and spread 50 g of alcohol-treated starch (alcohol-treated starch from procedure step 15 above) on a 500 mesh sieve and place on a shelf directly on top of the water container. De-solvent the starch at 160 ° C for 4 hours.
    [00079] Starch dried at 50 ° C overnight in an oven.
    [00080] Rapid starch measurement by visco-analyzer:
    [00081] A visco rapid analyzer (RVA) (Newport Scientific Pty. Ltd., Warriewood, Australia) was used to analyze profiles of starch pastes. Starch concentrations were varied to give a peak paste viscosity of about 1000 centipoises (cP). In this study, starch concentrations of 5% and 6.65% were used. Heating and RPM profiles are indicated on each graph. PH 6.5 RVA solution (Cat. No. 6654-5, RICCA Chemical Company, Arlington, Texas, USA) and the pH 3.5 solution of certified buffer (Key Laboratory Services, 2363 Federal Drive, Decatur, IL) they've been used. The Cooking RVA profile is designed to measure the RVA viscosity of cooked waxy starch. The starch was weighed in a cup of RVA and solutions of pH 6.5 or pH 3.5 of RVA were added to a total weight of 28 g. The current RVA profile was designed to analyze instant starches. The starch was weighed in the RVA cup and 4.5 g of propylene glycol were added to disperse the starch. The mixture was stirred with a spatula to make sure that complete dispersion was carried out. The pH 6.5 RVA solution was added for a total weight of 32 g. The starch slurry was mixed at 35 ° C for 20 minutes in the initial stage to develop paste viscosity from the current starches. Microscopy of starch paste:
    [00082] The starch paste was diluted with distilled water to about 1% starch. A drop of the starch solution was added to a microscopic cursor and stained with iodine tincture (2% O.S.P.) or solution containing 0.2% I2 and 2% KI. A slide cover was added to the top of each sample. The slide cover with stained starch sample was observed using a Leica Microscope DM4000 M (Buffalo Grove, IL 60089 United States). A 20x objective and 10x binocular lens under transmitted light were used. Starch granules stained with a solution containing 0.2% I2 and 2% KI and illuminated with polarized light, were also observed using this microscope. Specific sedimentation volume of starch after baking RVA:
    [00083] The specific sedimentation volume (SSV) is defined as the volume of the mass occupied by the enlarged starch granules per unit mass of dry starch (mL / g). Each starch was cooked using a Visco Rapid (RVA) analyzer under the following conditions: percentage of dry solids (DS%) = 2.5% dry starch in the slurry; 38 g of the entire slurry; Cookup RVA profile (160 rpm, 20 minutes at 95 ° C, refrigerated to 50 ° C, total run 35 minutes); pH 6.5 phosphate buffer. The loss of water during the RVA was due to weighing before and after cooking. The paste was then transferred to a 30-mL cluttered tube without dilution, weighed, and centrifuged at 4000 rpm for 15 minutes on a Sorvall Legend T + bench top. The sediment volume was read after the supernatant was decanted. SSV (mL / g) = (mL of pellet after 15 minutes at 4000 rpm) / (g of paste in 30 mL * dry starch% paste content). Starch with SSV between 20 ml / g to 40 ml / g is considered to have low shear stability or low crosslinking in chemically crosslinked starch. Starch with SSV between 16 ml / g to 20 ml / g has medium shear stability, and starch with SSV <16 ml / g has high shear stability. Starch color measurement:
    [00084] Color was measured using a Hunter Colorflex reflective spectrophotometer (Hunterlabs, Reston, VA). Retort simulation using Physica MCR 301 Rheometer with pressure cell:
    [00085] A Physica MCR 301 Rheometer (Anton Paar Germany GmbH, Ostfildern, Germany) was used to simulate retort processing. The starch was weighed in a cup and the pH 6.5 RVA solution (Cat. No. 6654-5, RICCA Chemical Company, Arlington, Texas, USA) was added for a total weight of 25 g of slurry. The percentage of starch should be high enough for a viscosity of above about 1000 mPa.s at 120 ° C. A higher concentration of starch is required for more highly inhibited starch. 20 g of slurry was loaded into the pressure cell using a syringe. A two-blade stirrer (ST24 / PR-2W-A1) was used. There is an initial heating to 60 ° C, then the sample is maintained at 60 ° C to record the viscosity, followed by slow heating to 120 ° C (typical retort temperature) with a 5-minute hold. The starch slurry is then cooled in two stages by double recording of viscosity stability at hot (70 ° C) and cold (25 ° C) temperatures. The system is under a "high" shear at a shear rate of 177 min-1 during the heating and cooling phases, in order to guarantee product homogeneity and a "low" shear at a shear rate of 29.3 min-1 during the high temperature maintenance step (120 ° C) to maximize the viscosity reading and intensify differences between batches. The viscosity curve during the maintenance time of 5 minutes at 120 ° C, is important for retort stability. A line or curve upstream at 120 ° C maintenance time indicates expansion of starch granules and highly inhibited starch. A downstream curve or line indicates decomposition of pastes. The pastes after measurement were examined under a microscope. Results and Discussion (Starch Treatment Method A)
    [00086] As previously described, waxy starch was treated in alcohol with sodium carbonate (1.4% based on dry starch) at 143 ° C for one hour and then neutralized with citric acid. The treated waxy starch was collected by filtration. Additional alcohol was removed by evaporation in the hood overnight, dried in a forced air oven at 50 ° C and then at 160 ° C with or without steam (desolventization) for 4 hours.
    [00087] Figure 1 shows the RVA (Cookup) profiles (5% and pH 6.5) of waxy starch (Sample 1-D), waxy starch after alcohol-based treatment at 143 ° C for one hour (Sample 1-A), and waxy starch after treatment of basic alcohol at 143 ° C for one hour and desolventization at 160 ° C with (Sample 1-C) or without (Sample 1-B) steam for 4 hours. Alcohol-based treatment alone reduced decomposition of RVA (peak or maximum viscosity minus depression or minimum viscosity after peak) by about 50% and increased final viscosity by about 43%. The micrographs of the pastes, after RVA analysis, show that the waxy starch paste was dispersed while the waxy starch paste, after the alkaline alcohol treatment, contained remaining dilated granules (broken dilated granules) (Figure 2), which indicate that the alcohol-based treatment helped to maintain remaining dilated granules, but was not sufficient to maintain the structure of the dilated granule. De-solventization with or without steam after alcohol-based treatment, eliminated RVA decompositions (Figure 1). Waxy starch treated with unsolventized alcohol base without steam, has a final RVA viscosity lower than that desolventized with steam. The paste micrographs, after RVA analysis, showed that the alkaline alcohol starch pastes treated with desolventized waxy starch with or without steam, both maintained the starch granule structure. Measurements of specific sedimentation volume (SSV) indicated a greater inhibition of waxy starch treated with non-vaporized alkaline alcohol compared to that with steam (Table 1), probably caused by less swelling of starch granules than the previous one during RVA. However, dry starch (less than 1% moisture) at a high temperature is a harmful explosion; in this way, steam desolventization is considered a safe process on an industrial scale. In addition, desolventization at 160 ° C with steam produced less color in the product than that desolventized without steam (Table 2). Table 1.
    Table 2.

    [00088] Positive slopes were maintained (without decomposition in paste viscosity) in alcohol-based waxy starches after desolventization with and without steam during RVA analysis using 5% sample concentration in pH 3.5 buffer (Figure 3), indicating that the pastes were stable in acidic conditions. Micrographs of pastes after RVA using pH 3.5 buffer, showed granular structure but desolventized samples (Figure 4).
    [00089] Retort simulation using a rheometer was used to simulate retort processing at 120 ° C, in soup production, to test the stability of starch pastes under high temperature conditions. In this test, starches with slightly negative, zero or positive slopes at 120 ° C residence time are potentially acceptable for soup and other high temperature applications. Native waxy starch is not suitable for soup and foods that require high temperature processing, by this criterion. Waxy starch treated with alcohol without desolventization is not an ideal candidate. Desolventized alcohol-based waxy starches, with and without steam at 160 ° C, are potentially suitable for soup foods that require high temperature processing. Micrographs of the pastes after retort simulation are shown in Figure 5. Waxy starch pastes treated with desolventized alcohol, with and without steam, both maintained the starch granule structure, which provided structural evidence that they were of stable retort.
    [00090] Samples of non-pregelatinized granular starches, after alcohol-based treatment followed by desolventization, which were illuminated with polarized light, displayed the microscopic images shown in Figure 6; their RVA profiles are shown in Figure 7. Beads show birefringence or a typical standard Maltese cross when viewed in polarized light. This property (display of a Maltese cross) is produced because the starch molecules are radially oriented within the granule. When the starch is heated in water, birefringence (Maltese cross pattern) in polarized light is lost by the end of the starch gelatinization. Figure 6 shows that the Maltese cross patterns of starch granules are virtually unchanged, when waxy starch is processed with alcohol-based treatment, followed by desolventization with or without steam, which indicates that starches are not pre- gelatinized. The pregelatinized starch develops viscosity in RVA using the instant profile in the initial 20 minutes at 35 ° C before further heating. Instant pre-gelatinized waxy starch (commercial product XPAND'R SC, a Tate & Lyle) developed viscosity immediately at 35 ° C, while native waxy starch and waxy starches after treatment with alkaline alcohol followed by desolventization did not develop discernible viscosity until heated to a higher temperature, which suggested that they are not pregelatinized starches.
    [00091] Waxy starch was treated in alcohol with various amounts of sodium carbonate (0.7%, 1.4%, 2.8% and 5.53% based on dry starch) at 143 ° C for one hour and then neutralized with citric acid. Desolventization was carried out at 125 or 160 ° C for 4 hours. Table 3 shows that increasing amounts of sodium carbonate and citric acid for neutralization tend to result in decreased values of SSV (higher inhibition) of the products. The same alcohol-treated starch desolventized at a high temperature (160 ° C), gave more inhibited products (lower SSV values) than when desolventized at a lower temperature (125 ° C). The product treated using 5.53% sodium carbonate and desolventization at 160 ° C was inhibited more than AC Starches, which were commercially available inhibited or modified starches. Table 3.

    [00092] Figure 8 shows the profiles of waxy starch rva after being treated in alcohol with various amounts of sodium carbonate and desolventized at 160 ° c for 4 hours, and a chemically modified commercial waxy starch with high crosslinking . All samples did not show rva decomposition after alcohol treatment. The viscosities of the waxy starches treated decreased with increasing amounts of sodium carbonate, in the treatment based on alcohol and citric acid in the neutralization thereafter. The samples treated with alcohol behaved like chemically crosslinked starches in the analysis of rva.
    [00093] These same alcohol-treated samples were desolventized at a low temperature (125 ° C) and their RVA profiles are shown in Figure 9. Significantly less inhibition was exhibited by the samples dissolved at a low temperature (Figure 9). The decomposition of RVA increased with reduced amounts of sodium carbonate (from 5.53% to 0.7%).
    [00094] The acid stability of samples treated with alcohol, which were desolventized at 160 ° C, were tested using RVA in a pH 3.5 buffer (Figure 10). No decomposition of RVA was observed in the RVA profiles, indicating that these treated starches were stable acids. Significant RVA decompositions were exhibited by the samples desolventized at 125 ° C with the decomposition increasing with decreasing amounts of sodium carbonate (from 5.53% to 0.7%) (Figure 11).
    [00095] The high temperature stability of starches was tested using a Physica MCR 301 Rheometer. The viscosities of samples treated with alcohol, prepared using 2.8%, 1.4% and 0.7% sodium carbonate, in treatment with alcohol followed by desolventization at 160 ° C, showed increases in 5 minutes of time permanence at 120 ° C, which indicated no paste decomposition and paste stability at a high temperature.
    [00096] Figures 12, 13, 14 and 15 show micrographs of starch granules in pastes after RVA and retort simulation using a Physica MCR 301 Rheometer. When alcohol-treated starches were desolventized at 160 ° C, intact dissolved starch granules were clearly visible. The intact swollen starch granules, after RVA and retort simulation, clearly demonstrated the inhibition of the starch granules after the treatment according to the invention. When samples treated with alcohol were desolventized at 125 ° C, the starch granules swelled more than the starches desolventized at 160 ° C and some dilated starches were decomposed. The extent of decomposition of starch granules was inversely related to the amounts of sodium carbonate, and the amounts of citric acid used during neutralization thereafter. Starch Treatment Method B
    [00097] In this example, the starch is treated using a procedure involving two heat cycles, in which the starch was first heated on the basis of an alcoholic medium and then further heated after the addition of citric acid to neutralize the base (providing a pH of about 6).
    [00098] Waxy starch (308 g, 11% moisture) was added to 3A ethanol (1177 g; 7.18% water) while stirring. Anhydrous sodium carbonate (7.585 g; 2.77% by weight based on dry starch) was then added. The resulting slurry was transferred to a two-liter high-pressure stainless steel reactor equipped with agitation and steam heating, controlled through its casing. The slurry was heated in the reactor with stirring at 143 ° C and maintained at this temperature for 60 minutes. After cooling the reactor contents to 25 ° C, the slurry was neutralized using 18.5 g of a 50% citric acid solution (3.37% by weight based on dry starch). The reactor contents were again heated to 143 ° C with agitation and maintained at that temperature for 60 minutes. After cooling to 25 ° C, the slurry was filtered through filter paper in a Buechner funnel to provide a moist starch cake. The wet cake was crumbled on a tray and left for several hours in a hood before being placed in an oven, to allow more 3A alcohol to evaporate. The starch (hereinafter referred to as "7629-68") was thereafter dried at 50 ° C in a convection oven overnight and then crushed and passed through a 100 mesh sieve.
    [00099] Steam starch desolventization was carried out by placing 3.5 kg of deionized water in a steel container (7.2 "in diameter, 8.5" in height), heating the steel container in an oven at 125 ° C for one hour, spreading 50 g of the treated starch in a 500 mesh sieve and placing it on a shelf directly on top of the steel container, and de-solvent the starch at 125 ° C for 4 hours. The starch was then dried overnight in a 50 ° C oven. Rapid Measurement of Starch by Mistletoe Analyzer
    [000100] A Rapid Visco-Analyzer (RVA) (Newport Scientific Pty. Ltd., Warriewood, Australia) was used to analyze starch paste profiles. A starch concentration of 5% was used in the RVA slurry. RPM heating profiles are indicated on each graph. A pH 6.5 buffer solution of RVA (Cat. No. 6654-5, RICCA Chemical Company, Arlington, Texas, USA) and a pH 3.5 solution of certified buffer (Key Laboratory Services, 2363 Federal Drive, Decatur, IL) were used. The Viswaxy RVA profile, with a 20-minute stay at 95 ° C, is intended to measure the RVA viscosity of cooked waxy starches. The starch was weighed in a cup of RVA and RVA solutions of pH 6.5 or pH 3.5 were added to a total weight of 28 g. Method to measure sedimentation volumes with and without shear
    [000101] Measure the moisture content of the starch.
    [000102] Weigh 5% of starch in a 250 ml wide-mouthed glass jug and add DI water or 1% NaCl solution to 100 g.
    [000103] Record the weight of the jug (optional).
    [000104] Place the jar in a 95 ° C water bath and stir the contents using a glass rod for 3 minutes while heating.
    [000105] Remove the glass jar and secure it with a lid.
    [000106] Place the jug in another 95 ° C water bath mixer (Boekel Shaker hot tub).
    [000107] Cook the sample at 95 ° C for 20 minutes with an orbital mixer at 120 rpm.
    [000108] After 20 minutes, take the sample from the mixer and place it in another water bath at room temperature and refrigerate the starch paste.
    [000109] Record the weight of the jug (optional).
    [000110] 10. Add ~ 40-50 mL of DI water or 1% NaCl solution to a graduated cylinder and add 20.0 g of cooked starch paste. Fill the rest of the volume (100 mL mark) with DI water or 1% NaCl solution.
    [000111] Seal the graduated cylinder with paraffin and shake the contents a to form a uniformly distributed suspension of starch (1% ds).
    [000112] Set aside the graduated cylinder without any disturbance.
    [000113] 13. Record the sediment volume after 24 hours.
    [000114] To measure the sedimentation volume, after shearing, add 50 g of the starch paste in the water or 1% NaCl solution in the mixer. Shear at 35 V ready for starch in water and 25 V ready for starch in 1% NaCl solution for 20 seconds. Then the procedure for settling the starch paste with shear. Microscopy of starch paste:
    [000115] Place 20 μL of starch paste, as it is (5%), on a microscope glass slide.
    [000116] Apply 20 μL of 0.02 N of iodine stock solution over the paste.
    [000117] Use a toothpick to mix the paste and iodine evenly on the glass slide.
    [000118] Apply a piece on the slide in the mixture and examine the sample using a 5x and 10x binocular objective lens under light transmitted in the Leica DM4000 optical microscope.
    [000119] Go over the entire sample area under the glass cover and take images with granule concentration, which is representative of the entire sample.
    [000120] For starch paste sample without shear, the number of intact granules is counted as the total number of intact waxy granules in the 50x magnification image.
    [000121] For sample of sheared starch paste, the number of intact granules is counted manually, since the microscope image has to be magnified to tell the waxy granules apart from the fragments.
    [000122] Fragmentation percentage = (number of intact waxy granules in non-sheared sample number of intact waxy granules in sheared sample) / number of intact waxy granules in non-sheared sample. Starch microscopy under polarized light:
    [000123] Starch (10 mg) was placed on a microscope slide. A drop of distilled water was added and mixed with starch. A sliding cover was added on top of a sample. The lid slide with starch sample was observed using the Leica Microscope DM4000 M (Buffalo Grove, IL 60089 United States) illuminated with polarized light using a 20x objective and 10x binocular lens. Results and Discussion (Starch Treatment Method B)
    [000124] Table 4 shows the sedimentation volumes in 1% NaCl of the starch treated with alkaline alcohol before and after desolventization at 125 ° C and 160 ° C. Table 4.

    [000125] Table 5 shows the sedimentation volumes of samples treated with alkaline alcohol of 7629-68, before and after desolventization at 125 ° C and 160 ° C in water, which exhibited higher sedimentation volumes than those observed in 1% NaCI solution. Table 5.


    [000126] The RVA profiles of samples treated with 7629-68 alkaline alcohol before and after desolventization at 125 ° C and 160 ° C are shown in Figure 16 (RVA pH 6.5) and Figure 17 (RVA pH 3.5 ).
    [000127] Figures 18 and 20 are micrographs of starch cooked in 1% NaCl as prepared to measure the volumes of non-shear sedimentation. Figures 19 and 21 are micrographs of starch cooked in 1% NaCl and after shear using a mixer as prepared to measure the shear sediment volumes. No significant fragmentation of the granules was observed.
    [000128] Granules of native starch showed birefringence or a typical Maltese cross when viewed in polarized light. When the starch is heated in water, the birefringence or Maltese cross in polarized light is lost by the end of the starch gelatinization. Figures 22 and 23 show that the Maltese crosses of starch granules are preserved when the waxy starch was processed using an alkaline alcohol treatment with two heating cycles and desolventized at 125 ° C and 160 ° C, which indicates that the starch is not pre-gelatinized.
    [000129] Sedimentation volumes are used to measure the extent of starch inhibition in the study described above. A lower settling volume without less shear indicates less dilation of the cooked starch granules and greater inhibition. A smaller change in shear sediment volumes, when compared to sediment volumes without shear, indicates a higher shear stability. By these standards, it was shown that samples treated with 7629-68 alkaline alcohol before and after desolventization were very highly inhibited, and shear stable. RVA profiles also showed that samples 7629-68 before and after desolventization were highly inhibited.
    [000130] Micrographs of starch cooked in 1% NaCl before (Figures 18 and 20) and after shear using a mixer (Figures 19 to 21) at 25 Volts for 20 seconds did not show significant fragmentation of gelatinized granules.
    [000131] Maltese crosses of starch granules are preserved when waxy starch is processed using alkaline alcohol treatment with two heating and desolventization cycles, which indicate that the starch is not pre-gelatinized. Starch Treatment Method C
    [000132] In this method, the starch is heated in an alcoholic medium in which sodium carbonate and citric acid were introduced, in which sodium carbonate is essentially neutralized by citric acid (thereby forming citric acid sodium salts in situ) .
    [000133] Waxy starch (307 g, 10.7% moisture) was added to 3A ethanol (1177 g; 7.18% water) while stirring. Anhydrous sodium carbonate (7.585 g; 2.77 wt% based on dry starch) and 18.5 g 50% citric acid solution (3.37 wt% based on dry starch) were then added. The resulting slurry was transferred to a two-liter high-pressure stainless steel reactor, equipped with stirring and controlled steam heating through its casing. The slurry was heated in the reactor with stirring to 143 ° C and maintained at that temperature for 60 minutes. After cooling to 25 ° C, the slurry was filtered through filter paper in a Buechner funnel to provide a moist starch cake. The wet cake was crumbled on a tray and left for several hours in a hood for several hours before being placed in an oven, to allow more 3A alcohol to evaporate. The starch (hereinafter referred to as "7629-70") was thereafter dried at 50 ° C in a convection oven overnight, and then crushed and passed through a 100 mesh sieve.
    [000134] Steam starch desolventization was carried out by placing 3.5 kg of deionized water in a steel container (7.2 "in diameter, 8.5" in height), heating the steel container in an oven at 125 ° C for one hour, spreading 50 g of the treated starch through a 500 mesh sieve and placing on a shelf directly on top of the steel container, and de-solvent the starch at 125 ° C for 4 hours. The starch was then dried overnight in a 50 ° C oven.
    [000135] The obtained starch was characterized using the same procedures described previously for the starch produced using Starch Treatment Method B. Results and Discussion (Starch Treatment Method C)
    [000136] Table 6 shows the sedimentation volumes in 1% NaCl of inhibited starch, made using a heating cycle with sodium carbonate and citric acid and alcohol, before and after desolventization. Table 6.

    [000137] Table 7 shows the sedimentation volumes in water of inhibited starch made using a heating cycle with sodium carbonate and citric acid in alcohol, before and after desolventization. The sedimentation volumes were higher than those observed in 1% NaCl solution. Table 7.

    [000138] The RVA profiles at pH 3.5 and 6.5 of inhibited starch, made using a heating cycle with sodium carbonate and citric acid in alcohol before and after desolventization, are shown in Figure 24.
    [000139] Figure 25 is a micrograph of starch cooked in 1% NaCl as prepared to measure the non-sheared sedimentation volumes. Figure 26 is a micrograph of starch cooked in 1% NaCl and after shear using a mixer, as prepared to measure shear sediment volumes.
    [000140] Granules of native starch show birefringence or a typical Maltese cross when viewed in polarized light. The Cruz de Malta property is produced because the starch molecules are radially oriented inside the granule. When the starch is heated in water, birefringence or the Maltese Cross in polarized light is lost by the end of the starch gelatinization. Figure 27 shows that the Maltese cross property of starch granules is preserved when waxy starch has been processed using a heating cycle with sodium carbonate and citric acid in alcohol and desolventization, which indicates that the starch is not pre- gelatinized. Sedimentation volumes are used to measure the extent of starch inhibition in this study. A smaller settling volume without shear indicates less swelling of cooked starch granules and greater inhibition. A smaller change in sediment volumes with shear, compared to sediment volumes without shear, indicates a higher shear stability. This example shows that the inhibited starch made using a heating cycle with sodium carbonate and citric acid in alcohol is highly inhibited and stable in shear. The micrographs of starch cooked in 1% NaCl before (Figure 25) and after shear (Figure 26), using a mixer at 25 Volts for 20 seconds, did not show significant fragmentation of the cooked granules. The starch after processing shows birefringence or a typical Maltese Cross, when seen in polarized light, which indicates that the starch is not pregelatinized.
    权利要求:
    Claims (17)
    [0001]
    1. Method for preparing an inhibited non-pregelatinized granular starch, characterized by the fact that the method comprises heating a non-pregelatinized granular starch in an alcoholic medium comprised between 80% to 96% by weight of alcohol and 4% to 20% % by weight of water, the total amount of alcohol and water equalizing 100%, in the presence of at least one treatment agent selected from the group consisting of bases and salts, at a temperature of at least 35 ° C.
    [0002]
    2. Method according to claim 1, characterized by the fact that the temperature is at least 120 ° C.
    [0003]
    Method according to claim 1, characterized in that it comprises an additional step of removing the solvent alcohol from the inhibited non-pregelatinized granular starch.
    [0004]
    Method according to claim 1, characterized in that it comprises an additional step of separating the inhibited non-pregelatinized granular starch from the alcoholic medium and heating the separated non-pregelatinized granular starch.
    [0005]
    Method according to claim 4, characterized in that the heating of the inhibited nonpregelatinized separated granular starch is carried out at a temperature of at least 120 ° C.
    [0006]
    Method according to claim 1, characterized in that it comprises an additional step of treating the vapor-inhibited non-pregelatinized granular starch.
    [0007]
    Method according to claim 1, characterized in that the non-pregelatinized granular starch is in the form of a slurry in the alcoholic medium and the pH of the slurry is at least 6.
    [0008]
    Method according to claim 1, characterized in that the at least one treatment agent includes a base and the method comprises an additional step of neutralizing the base in the non-pregelatinized granular starch inhibited with an acid.
    [0009]
    Method according to claim 8, characterized in that it comprises an additional step after the heating neutralization of the non-pregelatinized granular starch inhibited in the alcoholic medium.
    [0010]
    Method according to claim 1, characterized in that the at least one treatment agent includes a salt of carboxylic acid.
    [0011]
    Method according to claim 1, characterized in that the at least one treatment agent includes a polycarboxylic acid salt.
    [0012]
    Method according to claim 1, characterized in that the at least one treatment agent includes one or more sodium salts of citric acid.
    [0013]
    13. Method according to claim 1, characterized by the fact that the alcoholic medium is basic or neutral.
    [0014]
    14. Method according to claim 1, characterized in that the method comprises: a) heating the non-pregelatinized granular starch in the alcoholic medium, in the presence of a base at a temperature of at least 35 ° C; b) neutralize the base with an acid; c) separating the inhibited non-pregelatinized granular starch from the alcoholic medium; and d) removing the solvent alcohol from the non-pregelatinized granular starch inhibited by heating.
    [0015]
    15. Method according to claim 14, characterized by the fact that: the alcoholic medium is an aqueous ethanol medium; the non-gelatinized granular starch is in the form of a slurry in the alcoholic medium; the non-pregelatinized granular starch in the aqueous ethanol medium is heated in the presence of a base at a temperature of 120 ° C to 200 ° C; and wherein the inhibited non-pregelatinized separated granular starch is contacted with steam at a temperature of 100 ° C to 200 ° C to remove residual ethanol.
    [0016]
    16. Method according to claim 14, characterized by the fact that: in step b) the base is neutralized to provide a neutralized slurry; and after step b) and before step c), the method further comprises heating the neutralized slurry to a temperature of at least 35 ° C.
    [0017]
    17. Method according to claim 1, characterized in that the at least one treatment agent is selected from at least one carboxylic acid salt; and wherein the method further comprises the steps of: b) separating the inhibited non-pregelatinized granular starch from the alcoholic medium; and c) removing the solvent alcohol from the non-pregelatinized granular starch inhibited by heating.
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    同族专利:
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    IN2014DN09370A|2015-07-17|
    JP2018109192A|2018-07-12|
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    US11166483B2|2021-11-09|
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    WO2013173161A1|2013-11-21|
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    US20130309386A1|2013-11-21|
    CN104411727A|2015-03-11|
    MX2014013679A|2015-02-04|
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    AU2013263191A1|2014-11-27|
    JP6863917B2|2021-04-21|
    US10463066B2|2019-11-05|
    AU2013263191B2|2018-03-01|
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    法律状态:
    2018-05-08| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-11-05| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-10-13| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-12-22| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 09/05/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201261647146P| true| 2012-05-15|2012-05-15|
    US61/647,146|2012-05-15|
    US201361810545P| true| 2013-04-10|2013-04-10|
    US61/810,545|2013-04-10|
    PCT/US2013/040311|WO2013173161A1|2012-05-15|2013-05-09|Process for preparing inhibited non-pregelatinized granular starches|
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