WO2007111524A1 - Biopolymer hydrating method - Google Patents

Abstract

The inventive method for hydrating biopolymers of agricultural and natural vegetable and animal raw materials in the biopolymer mass moisturing processes makes it possible to decontaminate used water and biomass, to bind a maximum quantity of water in polymer solvate shells with no risk of the thermal or chemical denaturation and chemical and microbiological contamination thereof. The inventive method consists in treating water, prior to mixing in with a biomass, in a cavitation reactor at a sound pressure amplitude generating an acoustic wave cavitation which is at least by 5.5 times greater than a hydrostatic pressure inside the cavitation reactor, wherein the water runs through the cavitation reactor at a flow rate which is equal or less than 450 cavitation reactor volumes per hour.

Description

 METHOD FOR HYDRATION OF BIOPOLYMERS

Technical field

The invention relates to the field of production, storage and processing of agricultural raw materials, as well as the storage and processing of natural raw materials of plant and animal origin, and is intended for use in hydration processes of biopolymer materials, including disinfection of the water used for this and the biomass itself.

The invention can be used, for example, for:

- processing of grain, seeds, fruits and other biomass before laying them for storage;

- presowing treatment of grain and seeds;

- conditioning of grain during its processing into flour;

- moistening and disinfection of raw materials in the process of preparing dry feed for farm animals and poultry;

- obtaining aqueous suspensions from products of grinding grain, seeds and fruits, for example, baking dough or liquid feed;

- processing products of grinding grain, seeds and fruits, or other biomass in the process of extraction of soluble and emulsifiable substances, for example, in the production of drinks, including alcoholic, liquid spices or medicines.

It is possible to use the invention for hydration of biopolymers of animal origin, for example:

- in the processes of cooling, freezing, thawing and processing meat;

- restoration of milk from dried milk and the preparation of substitutes for whole milk, including the use of vegetable proteins.

The invention also extends to cases where an aqueous solution is used to hydrate biopolymers instead of water.

State of the art

A known method of wetting grain when processing it into flour with water with a temperature of 15 ... 204C and subsequent isothermal aging [Egorov G. A., Martynenko Ya. F., Petrenko TP Technology and equipment for milling, groats and combines feed industry.- M .: Publishing complex MGUPP, 1996]. During exposure, moisture is distributed over the anatomical parts of the grain and the formation of its bonds with biopolymers.

A disadvantage of the known method is that water having a cluster structure at room temperature, which is formed by the hydrogen bonds of its molecules with each other, weakly enters the hydration reaction of biopolymers.

In addition, room temperature water does not have a bactericidal or bacteriostatic effect on microorganisms living in it itself, as well as on the surface of the grain and capable of causing its microbiological damage.

Known methods for hot wetting of grain [Aizikovich L.E. Physico-chemical fundamentals of flour production technology.-M .: Kolos, 1975], carried out by pre-heated water or steam with a pressure close to atmospheric.

The disadvantage of these methods is the irreversible thermal denaturation of proteins, which further leads to a deterioration in the consumer qualities of the produced product.

Known methods:

- pre-sowing seed treatment [RU N ° 2170499, 1999];

- grain processing [Egorov G., Kochetkova A., Sushenkova O. Intensification of hydrothermal grain processing // Flour-and-elevator and animal feed industry, 1986, N ° 5.- p. 46-47];

- feed disinfection [RU N ° 2164747, 1999];

- bookmarks silo [RU JY22168910, 1999];

- manufacture of a preparation for processing raw meat [RU 2130267, 1999];

- meat salting [Borisenko A.A. Thermogravimetric analysis of moisture bond forms in salted beef // Meat Industry, 2001, N ° 7.- p. 45-46], during which water is subjected to electrochemical activation in the electrolyzer. Factors affecting the intensity of hydration are not thermal in nature, therefore, there are no drawbacks associated with the effect of temperature on biopolymers. However, the described methods have a common disadvantage, which is the need for preliminary chemical treatment of water. Otherwise, the processed biopolymer mass is contaminated by the products of electrode reactions. Known methods: - processing of grain in which water is sprayed into the grain using ultrasound [RU N22122311, 1998];

- salting of meat products, during which the brine is affected by ultrasound at a pressure below atmospheric [SU 1717063, 1992];

- preparation of the test based on a fat-water-flour suspension subjected to ultrasound [RUN ° 2151783, 2000];

- preparation using ultrasound flour suspension for activation of baker's yeast [RU Ne2184145, 2000].

The reason that prevents the use of these methods for hydration and disinfection is that there is no true cavitation in the water during its ultrasonic atomization, ultrasonic treatment with hydrostatic pressure below atmospheric pressure or in the presence of a phase with a developed surface area. Therefore, the process of destruction of hydrogen bonds proceeds under these conditions extremely slowly. It can be shown that under reduced static pressure in water or in a thin layer of water, where the thermal mechanism of dispersion of the energy of acoustic vibrations acts, even if all the potential energy of ultrasound with a density:

w = ^ A ^r t, (1)

where: A is the pressure amplitude in the acoustic wave; D is the adiabatic compressibility of water; t is the duration of exposure to ultrasound; T is the duration of the ultrasonic wave period, spent on useful work, then tens of hours will be required to break hydrogen bonds, whose heat under thermodynamically equilibrium conditions is ~ 25 kJ per mole of water (18 g). Known methods:

- the production of bread, in which the dough is carried out using water that has passed cavitation treatment [RU N22151782, 2000];

- processing of grain before laying it for storage or processing into flour, in which water is preliminarily treated in a cavitation mode [RU N ° 2171568, 2000]. In the implementation of these methods, water is also pre-subjected to aeration.

Closest to the claimed is the method described in the patent [RU N ° 2171568, 2000]. As you know, grain consists mainly of hydrophilic biopolymers: gluten proteins and starch polysaccharides. The effect of improving milling grain properties is achieved due to the intensification of microcracking of grains under the influence of heat and mass transfer phenomena accompanying the hydration of these biopolymers and the decomposition of hydrogen peroxide synthesized during cavitation treatment of water into enzymes. As a result of the latter, oxygen is also formed, which inhibits the activity of microflora. That is, such treatment of grain with water is a process of hydration of biopolymers, accompanied by the effect of reducing the microbiological contamination of the processed biomass.

It is known that the most effective cavitation process is carried out in a cavitation reactor - an apparatus in which cavitation is formed in the form of regions located in the antinodes of the pressure of an acoustic wave [US N ° 4618263, 1986; RU JVs2209112, 2002; RU N22226428, 2003; RU 3422228217, 2003].

It is also known that the level of energy dissipated by the cavitation phenomenon is described by the differential equation of motion of the wall of the cavitation bubble [Кпарр RT, Дайуу JW, Nammitt FG Cavitatiop.-Неw Yоrk: McGraw HiIl Vook Сomrapu, 1970]. By integrating this equation, it can be shown that when the amplitude of wave A in water is, for example, 0.8 at rest pressure inside the cavitation bubble P ₀ , the instantaneous pressure value P on the surface of the bubble will change, as shown in FIG. 1. Then, the average pressure over time t generated by the oscillations of the cavitation bubble, calculated depending on the phase of the harmonic wave D by the formula:

будет изменяться, удовлетворяя принципу сохранения импульса давления, как показано на Фиг. 2 кривой под номером 1.

will vary, satisfying the principle of preserving the pressure pulse, as shown in FIG. 2 curves at number 1.

In the theory of a cavitation reactor, which is applicable to cases where the A-dependent collapse of cavitation bubbles (the length of time over which their instantaneous radius is smaller than the rest radius) is negligible compared to the period of the cavitation-causing ultrasonic wave, the expression is true:

где в квадратных скобках обозначена целая часть числа (Фиг. 2 ломаная линия под номером 2). Среднее за период волны T значение плотности потенциальной энергии кавитации w, трансформируемой одной кавитационной областью в произвольной точке пространства реактора, вычисляется путем интегрирования:

where in square brackets the integer part of the number is indicated (Fig. 2 broken line at number 2). The average over the wave period T value of the density of potential cavitation energy w, transformed by one cavitation region at an arbitrary point in the reactor space, is calculated by integrating:

w = n - ^C P f n2

2T K ^d <£> (4) where: n is the number of cavitation bubbles involved in the process; C is the attenuation coefficient of the pressure pulse in space, m ¹ . Moreover, the time t in (2) or (3), through which P _tιf is expressed, is understood as the average time of arrival of the pressure perturbation from the bubbles that make up the cavitation region to the point in space for which the calculation is performed.

Using expression (4), it can be shown, for example, that in a round-shaped reactor with a radius of 50 mm with a standing half-wave equal to 35 mm, the average density of potential energy released over the same volume of the reactor for the same periods of time for the cases shown in FIG. 2 graphs 1 and 2, differ almost 20 times.

Within this range is a threshold energy below which water disinfection does not occur, and accelerated development of bacterial colonies is observed, associated with the mechanical separation of their clusters without the death of individual microorganisms [Bergman JI. Ultrasound and its application in science and technology. - M: IIL, 1956]. Therefore, the disinfection of the water used in the prototype does not occur. The enhancement of the bacteriostatic effect with respect to grain microflora during the implementation of the prototype is achieved by aeration of water in order to increase the yield of hydrogen peroxide by involving air oxygen in its synthesis. However, aeration leads to a decrease in PQ, which is equivalent to a decrease in hydrostatic pressure and, accordingly, the efficiency of the destruction of hydrogen and covalent bonds in water.

All this does not allow to achieve the technical result of the invention formulated below when using the prototype.

Disclosure of invention

The technical result of the invention is to reduce the microbiological contamination of hydratable biopolymers by intensifying the disinfection of hydrating their water and increasing the content of the bactericidal agent hydrogen peroxide synthesized as a result of cavitation, as well as intensifying hydration reactions, which results in an increase in the mass of biopolymers due to an increase in water of the most active reagent - its unstructured phase, by epithermal destruction in de own structure formed by hydrogen bonds of its molecules with each other.

The invention consists in the following.

It is known that the resting pressure P ₀ in a cavitation bubble depends on the radius of rest of this bubble RQ, the surface tension of the liquid, the vapor density of the liquid, and the hydrostatic pressure Pj ₁ in it. The real threshold for cavitation in water and aqueous solutions is for cavitation bubbles with a diameter of more than 10 ^" m ~ 0.5-10 ⁵ Pa at a hydrostatic pressure of 10 ⁵ Pa, which is explained by the low density of water vapor in comparison with the hydrostatic pressure in it at equilibrium. Taking this into account, using the equation of equilibrium embryo cavitation bubble in liquid, it can be shown that the different variations of parameters, the pressure in the bubble rest in an equilibrium state, since RQ> 10 ^'5 m, negligibly little different from the hydrostatic one P _11. Supporting this conclusion is the dependence of the pressure P ₀ in bubble radius from its RQ at a different initial equilibrium conditions, obtained by computational experiments with model Ka- a gravitational vial shown in FIG. 3. Thus, it is possible hydrostatic pressure P _h in water accept as a constant, with respect to which A. is established

It is also known that, by virtue of the law of conservation of the pressure pulse, the pause between collapses of an individual bubble is even or odd for the period of the acoustic wave, provided that the pause is longer than the period, the average pressure generated by the cavitation region for a large number of periods is zero. Therefore, for each P _h there exists a value A, above which the density of the potential energy released in the cavitation reactor is constant. This value corresponds to the condition that the oscillation period of the cavitation bubble is equal to the period of the acoustic wave causing cavitation. That is, the choice of the pressure amplitude from the region in which the desired value A is located and all values exceeding it is a necessary and sufficient condition for achieving the formulated technical result.

This value was found by a numerical experiment to establish the dependence of P _tιСШ = max P _t on A at atmospheric pressure. The experimental results are shown graphically in FIG. 4, where the dashed line marks the maximum value of the average pressure when the collapse coincides with the end of the period of the acoustic wave causing cavitation. It is seen that the desired value of A is 5.5Pj ₁ . The optimal duration of the process of cavitation treatment of water was established experimentally by studying the dependence of the content of unstructured component in water on the time of cavitation exposure. In this case, water was considered a dispersed system, the environment of which is an unstructured component, the phase is structured. It was also believed that at the temperature of vaporization under adiabatic conditions, the entire volume of water is degraded, and in the temperature range 0 ⁰ C ... +4 ⁰ C water contains a maximum of the structured phase. Then, if the dependence of the viscosity of water on the ratio of the volumes of the phase and the medium obeys the Einstein-Smoluchowski equation, then by measuring the viscosity it is possible to establish the percentage of unstructured water in the total mass of water subjected to cavitation.

For the study, a cavitation reactor was used, in which the condition A> 5.5Pb was ensured, and the rheometer Vkookfield LVD V-III (Br. Eng. Lab., USA) was provided. The experimental results are shown in FIG. 5. The asymptotic nature of the dependence is explained by the equilibrium state, established during prolonged cavitation exposure.

Taking into account the instrumental and methodological error of the experiment (shaded area), it is possible to accept the necessary and sufficient processing time of 8 seconds.

Thus, in the general case, the maximum productivity of the process under the condition A≥5.5P _h can be defined as 450 ¹ Y m ³ / h, where V is the reactor volume in m ³ .

The technical result when using the invention is achieved by the fact that in the known method of hydration of biopolymers, it is characteristic that they process water in a cavitation mode and mix it with a biopolymer mass, wherein the water treatment is carried out in a cavitation reactor with an amplitude causing cavitation of the acoustic wave of not less than 5.5 Fj ₁ , where P _h is the hydrostatic pressure inside the cavitation reactor and with a capacity of not more than 450 U m / h, where V is the volume of the cavitation reactor in m

Brief Description of the Drawings

In FIG. Figure 1 shows the change in time, expressed in units of the period of the acoustic wave T of pressure P on the surface of a single cavitation bubble located in the antinode of the wave pressure. In FIG. _Figure 2 shows the functions of the pressure _averaged over time t / T P _tιf generated by oscillations of a single cavitation bubble with the initial phase O = 0.75G. Curve 1 is COOTBeTCTByCTA = O ₅ SPi ₁ , and broken line 2 is A = 5.5P _h .

In FIG. Figure 3 shows the dependence of the pressure inside the bubble on its radius under various initial conditions. The upper group of curves for P _h = IO ⁵ Pa, the average P _h = 5-10 ⁵ Pa, the lower P _h = IO-IO ⁵ Pa. In groups from top to bottom - surface tension 0.10 N / m; 0.05 N / m; 0.02 N / m.

In FIG. _Figure 4 shows the dependence of P _tιfPax on A at atmospheric pressure. The dashed line marks the maximum value of the average pressure when the collapse of the cavitation bubble coincides with the end of the period of the forcing oscillator.

In FIG. Figure 5 shows the empirical dependence of the content of the unstructured phase in water subjected to cavitation treatment at A = 5.5P ₁₁ and atmospheric pressure in a cavitation reactor. The area corresponding to the hardware error in measuring the viscosity of water is hatched.

In FIG. 6 is a perspective view, combined with a sectional view, showing the construction of a cavitation reactor with a radius of 35 mm and a height of 215 mm, intended for treating water in the process of hydration of biopolymers. The drawing of the reactor is an illustration of the following embodiments of the invention.

An embodiment of the invention

The proposed method can be implemented, as shown in the following examples of hydration of biopolymers of raw materials of plant and animal origin.

Inside a cavitation reactor, for example, with an internal volume diameter of 70 mm and a height of 215 mm (Fig. B) using an acoustic oscillation source consisting of an electro-acoustic transducer 1, an acoustic waveguide transformer 2 and a reflector-resonator 3, inside the reactor vessel 4 in water, passed through the reactor under pressure, for example, l, 0-10 ⁵ Pa, establish a plane standing acoustic wave, causing cavitation. The reactor through the flanges 5 is built into the water supply, through which water is supplied for mixing with biomass. The pressure amplitude of the acoustic wave is set by selecting the electric power of the transducer depending on the average volumetric density of the potential cavitation energy dissipated during the wave established upon receipt of the dependence depicted in FIG. 5, which is equal to 4.2 Doιs / m ³ . If the electro-acoustic efficiency of the process is 0.8 (taking into account internal friction losses in the electro-acoustic transducer 1, waveguide transformer 2 and reflector-resonator 3), then the power of the transducer should be 3.9 kW. For this purpose, for example, the BRANSON co-model 502 / 932R is suitable. At the selected sizes, the volume of the internal space of the reactor is 8.4-10 ^"4 m ^3. Since the productivity should not exceed 450" VM ³ / h, where V is the volume of the cavitation reactor in m ³ , the maximum process capacity is 377 l / h .

Water is supplied to the internal volume of the reactor through one of the nozzles 6, connected by means of a flange 5 to the water supply, and exits through the other. Cavitation occurs in the reactor under the influence of the dissipated power of an acoustic wave in water. The potential energy of cavitation destroys the shells of microorganisms living in it. The same energy, realizing the transformation mechanism inherent in high-energy chemistry, by the suprathermal path directly affects hydrogen bonds inside water clusters, destroying them. Water molecules not interconnected by hydrogen bonds when mixed with a biopolymer mass hydrate its macromolecules.

Cavitation exposure also increases the chemical activity of water due to its dissociation, accompanied by the formation of ions / J ₃ O ⁺ and OET. These ions also take part in the synthesis of hydrogen peroxide. The resulting hydrogen peroxide, decomposing, including on enzymes and metabolites of microorganisms with the formation of oxygen and the release of energy, helps to accelerate the interaction of water with the biopolymer mass and inhibits the activity of bacteria.

Example 1. Activation and disinfection of water and wheat grain during the wetting process of processing grain into flour, accompanied by hydration of its gluten proteins and starch polysaccharides, in order to improve the structural and mechanical properties of grain, increase gluten content and reduce microbiological contamination.

It was necessary to moisten a grain of type IV wheat, containing 18.1% crude gluten and having a moisture content of 13.7%. Moistening of the grain was carried out with water at a temperature of 35 ⁰ C, processed according to the method described in the prototype, and claimed. The isothermal exposure time after wetting was 8 hours. The results are shown in table 1.

Table 1

Example 2. Activation and disinfection of water and powder of mustard seeds during the extraction of water-soluble and emulsifiable substances from it in the manufacture of mayonnaise in order to increase the yield of the extract and increase the microbiological purity of the intermediate product - a suspension of mustard powder.

The powder of mustard seeds was mixed at a temperature of 40 ⁰ C with water that was processed in accordance with the prototype and the claimed invention. The results of the study of the environment of the resulting suspension are shown in table 2.

table 2

Example 3. Activation and disinfection of water in the process of restoring milk used in the manufacture of a substitute for whole milk, to give the product natural properties, increase the mass of "chemical substance" and ensure its microbiological purity.

It was required to obtain synthetic milk with a protein content of 4.5% from skimmed milk powder (38.5% protein), water and whole uncooled milk with a protein content of 3.0%. A concentrate was prepared containing 23.3% skimmed milk powder and 76.7% treated water. Then concentrate diluted with whole milk. Water for the preparation of the concentrate was subjected to cavitation treatment in accordance with the prototype and the claimed method. The comparison results are shown in table 3.

Table 3

Example 4. Activation and disinfection of water for the preparation of curing brine in the manufacturing process of meat minced molded semi-finished products to give them juiciness, reduce weight loss during heat treatment and reduce microbiological parameters.

Stuffing was prepared from beef and pork meat in a ratio of 1: 1 and a saturated solution of salt in water, which was processed in accordance with the prototype and the claimed method. When salting, the minced meat was mixed with brine in a ratio of 1000: 76 by weight. The results are summarized in table 4.

Table 4

From the presented examples it can be seen that the processing of water by the claimed method can improve the microbiological purity of the final product.

Claims

 CLAIM A method of hydration of biopolymers, including the treatment of water in a cavitation mode and the interaction of the biopolymer mass with water treated in a cavitation mode, characterized in that the water treatment is carried out in a cavitation reactor with an amplitude causing cavitation of the acoustic wave of at least 5,5P _h, where P _h - cavitation hydrostatic pressure inside the reactor and with a capacity of no more than 450-V ^m / h, where V- cavitation reactor internal volume, in m ^3.