Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
  • C08B30/00—Preparation of starch, degraded or non-chemically modified starch, amylose, or amylopectin
  • C08B30/12—Degraded, destructured or non-chemically modified starch, e.g. mechanically, enzymatically or by irradiation; Bleaching of starch
• • A23L1/0522—
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
  • A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
  • A23L29/20—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
  • A23L29/206—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin
  • A23L29/212—Starch; Modified starch; Starch derivatives, e.g. esters or ethers
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
  • A23L7/00—Cereal-derived products; Malt products; Preparation or treatment thereof
  • A23L7/10—Cereal-derived products
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
  • C08B30/00—Preparation of starch, degraded or non-chemically modified starch, amylose, or amylopectin
  • C08B30/06—Drying; Forming
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
  • C08B30/00—Preparation of starch, degraded or non-chemically modified starch, amylose, or amylopectin
  • C08B30/12—Degraded, destructured or non-chemically modified starch, e.g. mechanically, enzymatically or by irradiation; Bleaching of starch
  • C08B30/14—Cold water dispersible or pregelatinised starch
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
  • C08B30/00—Preparation of starch, degraded or non-chemically modified starch, amylose, or amylopectin
  • C08B30/12—Degraded, destructured or non-chemically modified starch, e.g. mechanically, enzymatically or by irradiation; Bleaching of starch
  • C08B30/16—Apparatus therefor
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
  • C08B30/00—Preparation of starch, degraded or non-chemically modified starch, amylose, or amylopectin
  • C08B30/20—Amylose or amylopectin
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
  • C08B31/00—Preparation of derivatives of starch
  • C08B31/18—Oxidised starch
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
  • C08H99/00—Subject matter not provided for in other groups of this subclass, e.g. flours, kernels

Definitions

• the present invention relates to thermally inhibited starches and starchy flours produced by heat treatment of native starch that has been pre-dried where necessary to a dry matter content greater than or equal to 95% by weight, preferably 98% by weight, more preferably 99% by weight.
• Native starch grains are insoluble in cold water. However, if native grains are dispersed in water and heated, they undergo hydration and swell. With continued heating, under conditions of shear or an extreme pH, the swollen grains disintegrate and the starch molecules are dispersed in the water, i.e. solubilized.
• Pre-gelatinized starches i.e. starches that dissolve or swell in cold water
• the present invention applies equally to native and pre-gelatinized starches and starchy flours.
• starches may be heated for various purposes, e.g. for drying, vaporizing off-flavors, imparting a smoky taste and for sterilization or dextrination purposes.
• U.S. Pat. No. 3,977,897 B describes a non-chemically inhibited starch that is produced by controlled heating, at a specific pH, of an aqueous solution of an amylose-containing starch in intact granular form and an inorganic salt, thereby leading to an increase in the starch's gelatinization temperature.
• U.S. Pat. No. 4,303,451 B discloses the heating of waxy corn starch at a temperature in the range from 120 to 200° C., at the starch's naturally occurring pH, in order to eliminate woody aromas and modify the texture during pre-gelatinization.
• JP 61-254602 discloses the heating of waxy corn starch and waxy corn starch derivatives at a temperature of 100 to 200° C. in order to provide a starch with emulsifying properties as a substitute for gum arabic.
• the starch is heated in the presence of moisture, preferably under acidic conditions at a pH of 4.0 to 5.0, in order to hydrolyse the starch and obtain the emulsifying properties.
• U.S. Pat. No. 4,303,452 B discloses a smoke treatment of waxy corn starch in order to improve the gel strength and generate a smoky taste.
• the starch's pH Prior to smoking, the starch's pH is raised to a value ranging from 9 to 11 so as to counteract the smoke's acidic reaction and obtain a starch end product with a pH of 4 to 7.
• the preferred water content of the starch during the smoking process is 10 to 20%.
• native starch grains are dispersed in water and heated, they undergo hydration as from approx. 60° C. and swell, reaching their maximum viscosity in the range from 65 to 95° C. This rise in viscosity, which results from the physical force of friction between the strongly swollen grains, is a desirable property in many food and industrial applications.
• swollen, hydrated starch grains are rather fragile. If the starch slurry is held at temperatures of 92 to 95° C., the starch grains begin to fragment and the viscosity collapses. Shear forces or extreme pH conditions also tend to promote breaking open and fragmentation of the grains, causing the starch polymers to dissociate and solubilize and the originally high viscosity to collapse rapidly.
• WO 96/04315 A1 and WO 96/04316 A1 disclose thermally inhibited, pre-gelatinized or non-pregelatinized granular starches or thermally inhibited, non-pregelatinized granular flour produced by (a) dehydrating a granular starch or a granular flour to a moisture level of less than 1% by weight in order to render the starch substantially anhydrous; and (b) heat-treating the substantially anhydrous starch or the substantially anhydrous flour at a temperature of 100° C. or thereabove for a length of time sufficient to inhibit the starch or flour, the dehydration steps and heat treatment being carried out in a fluidized-bed reactor or dryer.
• fluidized-bed reactors and fluidized-bed dryers are also known to have considerable drawbacks, for example residence time distribution of fluid by dispersion, residence time distribution of solids by back-mixing, abrasion of the vessel and attrition of the solid particles and apparatus walls, difficult scaling-up and modeling, costly explosion protection and very high energy consumption.
• gas-solid separators e.g. cyclones
• the maximum flow rate is frequently limited due to the risk of particle discharge.
• the inhomogeneities that frequently occur in fluidized beds can complicate operation insofar as highly non-uniform residence time distributions of the reaction mixture must be anticipated.
• the upward speed of the largely solid-free bubbles is highly non-uniform.
• a spiral vibratory conveyor or spiral dryer usually consists of a closed tubular system made of stainless steel.
• the tube is fixed to a frame that is set into vibratory motion by a motor.
• the speed at which the particles are transported through the tube depends on the angle of the motor and the vibratory speed, enabling the desired flow rate for the product to be set via these parameters.
• the atmosphere inside the tube can be controlled as specified; for example, temperatures of up to 650° C. can be generated by electrical heating of the tube wall.
• Product is introduced into the spiral tube via a gravimetrically controlled feed metering unit or, alternatively, by manual means, and then, depending on the product density and the set flow rate, has a defined residence time in the spiral vibratory conveyor or spiral dryer.
• the particle residence time is indirectly proportional to the speed of the motor, that is, the faster the motor runs, the stronger is the vibration and the shorter the residence time of the product in the tube.
• U.S. Pat. No. 2,818,357 B discloses a method of producing transformation or degradation products of high-molecular hydrocarbons by heating, as well as a device for carrying out a method of such kind.
• this device is a spiral vibratory conveyor.
• chemical reactions between solid substances can be carried out in the disclosed device according to the disclosed process.
• ethers of cellulose or starch can be obtained by heating a mixture of cellulose or starch with alkali and chloroacetic acid according to the process described.
• the reaction must be carried out in the absence of air. Complete exclusion of air is of great importance because undesired degradation of cellulose or starch is thereby prevented.
• the object of the present invention is to overcome the drawbacks of the processes described in the prior art and to provide thermally inhibited starches and starchy flours produced according to an alternative method and/or in an alternative device.
• thermally inhibited starches and/or starchy flours are produced by heat treatment of native starch and/or starchy flours that has/have been pre-dried where necessary to a dry matter content greater than or equal to 95% by weight, preferably 98% by weight, more preferably 99% by weight, wherein said native starch and/or starchy flours, pre-dried where necessary, is/are heat-treated in a spiral vibratory conveyor in the presence of at least 0.1% by volume oxygen at a starch and/or starchy flour temperature, referred to hereinafter as the product temperature, in excess of 100° C.
• thermally inhibited starches and flours may come from an arbitrary source, for instance bananas, corn, peas, potatoes, sweet potatoes, barley, wheat, rice, sago, amaranth, tapioca and sorghum, and may be starches with a high or low amylose content, and the like.
• references to starch in this description are to be understood as including their corresponding flours.
• starch is intended to also include starch that contains protein, either endogenous protein or added protein of animal or plant origin, e.g. zein, albumin and soybean protein.
• native starch refers to naturally occurring starch.
• the starches may be native starches or, alternatively, starches modified by enzymes, heat or acid conversion, oxidation, phosphorylation, etherification (in particular hydroxyalkylation), esterification and chemical cross-linking.
• the starting products are pre-dried where necessary because if starches are subjected to heat in the presence of water, they may undergo acid hydrolysis or acid degradation. Hydrolysis or degradation will impair or prevent inhibition; conditions for dehydrating the starch must therefore be selected such as to favor inhibition rather than hydrolysis or degradation.
• suitable conditions consist in dehydrating at low temperatures or increasing the pH of the starch prior to dehydration.
• the preferred conditions consist in a combination of low temperature and a neutral-to-basic pH.
• Starch dehydration temperatures are preferably kept at 125° C. or lower, and more preferably at temperatures or a temperature range between 100° C. and 120° C. It is possible to use a dehydration temperature below 100° C. but a temperature of at least 100° C. will eliminate moisture more efficiently.
• the preferred pH is at least 7, with pH ranges of 7.5 to 10.5, preferably 8 to 9.5 and, best of all, a pH above 8 being typical.
• a pH in excess of 12 is very apt to cause gelatinization; a pH of less than 12 is therefore more effective.
• the starch is slurried in water or another aqueous medium, typically in a ratio of 1.5 to 2.0 parts by weight of water to 1.0 part by weight of starch, and the pH adjusted by addition of a suitable base. Buffers such as sodium phosphate may be used where necessary in order to keep the pH stable.
• the starch slurry is then either dehydrated and dried, or dried directly, to the starch's equilibrium moisture content, preferably, however, to a moisture content of 2 to 6%. These drying procedures are to be distinguished from the steps in the thermal inhibition process, in which the starch is dewatered until it is anhydrous.
• a solution of a base may be sprayed onto the powdered starch until the starch reaches the desired pH, an alkaline gas such as NH 3 may be diffused into the starch or use may be made of dry mixtures of starch/flour and alkali.
• heat treatment of the starch is performed in the spiral vibratory conveyor in the presence of at least 0.5% by volume oxygen, preferably in the presence of at least 5% by volume oxygen, more preferably in the presence of at least 10% by volume oxygen or, best of all, in the presence of atmospheric oxygen.
• Comparative experiments performed within the context of the present invention show that, although the presence of oxygen cannot be ruled out for technical reasons, no undesired degradation of starch products takes place under the process conditions according to the invention. Contrary to what is disclosed in the prior art, heat treatment can even be conducted in the presence of atmospheric oxygen, thereby making the method of producing thermally inhibited starch and/or starchy flours according to the invention fast, easy and cheap to carry out.
• the starch according to the invention is characterised in that it is heat treated at a product temperature of between 150 and 200° C., preferably of between 155 and 175° C.
• the heat treatment ranges are temperatures or a temperature range in excess of 150° C.
• the maximum heat-treatment temperature is usually in the vicinity of 200° C., at which temperature strongly inhibited starches can be obtained.
• Heat treatment is typically carried out at 155 to 175° C., with time and temperature profiles depending on the desired degree of inhibition.
• the starch is in granular form, preferably in the form of native starch, that is, in the form of starch as it occurs in nature.
• the starch according to the invention advantageously has an amylose content of less than 5% by weight, preferably less than 2% by weight.
• Amylopectin is the major constituent (usually 70 to 80%) of natural vegetable starch, e.g. corn or potato starch, and the polysaccharide amylose the second major constituent, usually making up 20 to 30%.
• Starches rich in amylopectin that is, starches with an amylopectin content of at least 95% by weight, are generally referred to as waxy starches or amylopectin-rich starches.
• starch according to the invention having an amylose content of less than 5% by weight, preferably less than 2% by weight, is a corn starch (waxy corn starch being the term generally used for starches of this kind).
• the viscosity of starch and starchy flours is measured as a function of time and temperature and is compared with the starting, or reference, material.
• the viscosity is measured in a Brabender Viscograph-E (manufactured by Brabender TECH KG) and is expressed in Brabender units. It is the resistance of the solution, measured as torque.
• the starch/water suspension is heated and cooled, at a constant rate of temperature increase and decrease, respectively, in a Brabender bowl rotating at a constant rotational speed.
• the temperature and the viscosity, in Brabender units are recorded simultaneously.
• a graph is obtained by plotting temperature and Brabender units against time.
• Thermally non-inhibited starches usually gelatinize in a range between 60-70° C., reaching their maximum in the range from 65-95° C. If the temperature is held there for a certain period of time, the viscosity decreases (by what is known as the breakdown) from its peak value and then, on cooling, increases again to its end value.
• the spiral vibratory conveyor used is of pilot-plant scale and is dimensioned as follows:
• the two tube openings are opened with each spiral revolution. This enables the water to vaporize and prevents it from condensing on the tube wall. Plus, a constant O 2 level is also guaranteed.
• the starch from Example 1 was conveyed through the spiral at a product flow rate of 50 kg/h and a product temperature of 130° C. Metering was performed gravimetrically via the automatic metering station. After a cycle, a sample was withdrawn and analysed. As is evident from Table 2, the sample does not undergo a viscosity shift in the direction of a thermally inhibited starch but retains the viscosity profile of the non-modified starch.
• the two tube ends were connected with a hose so as to enable recirculation of the product. All the openings at each turn of the spiral were open.
• the starch from Example 1 was added at a flow rate of 100 kg/h. After drying at 130° C. for 6 minutes, the heating temperature was raised in order to reach a product temperature of 190° C. and the product recirculated until it was seen to turn intensely brown and take on a different aroma. After each cycle (approx. 6 min), the hose was removed briefly by hand and a sample withdrawn.
• Time GT PM BD EV Name [° C.] [min] [° C.] [BE] [BE] [BE] 1 190 12 66.8 1117 741 631 2 190 18 66.5 1039 480 834 3 190 24 65.3 669 19 1016 4 190 30 63.3 419 0 634 5 190 36 62.0 207 0 371 Non-modified control — — 67.3 1066 777 546 Modified control — — 65.6 668 32 1020 Novation ® 2300 — — 65.2 506 1 771 Novation ® 2600 — — 66.4 682 41 1011
• thermostable samples were obtained which have a strongly reduced breakdown and have the properties of chemically modified starches.
• Time GT PM BD EV Name [° C.] [min] [° C.] [BE] [BE] [BE] 1 170 18 67.0 1125 717 667 2 170 30 66.4 933 193 1224 3 170 36 66.2 842 101 1166 4 170 42 66.0 722 14 1103 5 170 48 65.9 653 3 1035 6 170 54 65.6 564 0 853
• Modified control — — 65.6 668 32 1020 Novation ® 2300 — — 65.2 506 1 771 Novation ® 2600 — — 66.4 682 41 1011
• Example 2 The samples were treated in the same way as in Example 2 except that heat treatment was carried out at a product temperature of 150° C. In this case, there was only a low level of thermal inhibition and the starch obtained was only slightly more stable than a non-modified starch.
• Time GT PM BD EV Name [° C.] [min] [° C.] [BE] [BE] [BE] 1 150 30 66.9 1146 653 743 2 150 36 66.8 1063 439 868 3 150 42 66.8 1208 561 923 4 150 48 66.7 968 227 1118 5 150 54 66.7 968 211 1204 6 150 60 66.9 936 205 1318 7 150 66 67.0 923 203 1320 8 150 72 66.6 915 166 1222 Non-modified control — — 67.3 1066 777 546 Modified control — — 65.6 668 32 1020 Novation ® 2300 — — 65.2 506 1 771 Novation ® 2600 — — 66.4 682 41 1011
• Table 6 below shows the formulation for the 40° Brix cherry fruit preparation used for application-related testing of the starch profiles produced.
• the Brabender viscosities of the samples according to the invention, produced in the spiral vibratory conveyor, are comparable with the quality of the Novation starches known from the prior art. In addition, they are able to substitute for chemically modified starches.
• the sample treated for 54 minutes at 170° C. has a viscosity curve similar to that of Novation 2300 and has a slightly higher viscosity.
• Both the sample treated for 42 minutes at 170° C. and the sample treated for 24 minutes at 190° C. show a viscosity profile that corresponds to that of Novation 2600 and thus to a commercially available thermally inhibited starch.

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• Dispersion Chemistry (AREA)
• Polysaccharides And Polysaccharide Derivatives (AREA)
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• 2012
  • 2012-06-29 RU RU2015102793/13A patent/RU2602282C2/ru active
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