RU2286204C1 - Method of preparation of the water solutions of electrolytes under action of the ultrasonic cavitation - Google Patents

Abstract

FIELD: chemical industry; electrotechnical industry; food-processing industry; methods of preparation of the water solutions of electrolytes under action of the ultrasonic cavitation.

SUBSTANCE: the invention is pertaining to the methods based on utilization of the energy of the ultrasonic cavitation used for intensification of the dissolution and dissociation processes, for example, in chemical, electrotechnical and the food-processing industries. The method of preparation of the water solution of the electrolyte containing as the components the dissociated, hydrated, non-dissociated and non-hydrated substances provides, that the cavitation effects on the water before dissolution in it of the dissociated component. The ultrasonic cavitation energy using the epithermal action on the water realizes in it the gearings peculiar to the high energy chemistry and destroys the intermolecular hydrogen bonds forming in the conditions of the thermodynamic equilibrium the cluster structure of the water. It considerably boosts its diluting and dissociating capability. At that there is no need to use the cavitational reactor, which is proof against the aggressive mediums, that allows to simplifies its design and reduces the cost without lowering the effect from utilization of the ultrasonic cavitation.

EFFECT: the invention ensures, that the ultrasonic cavitation energy considerably increases the diluting and dissociating capability of the water solution of the electrolyte making unnecessary the usage of the cavitational reactor, that allows to simplifies its design and to reduce the cost without lowering the effect from utilization of the ultrasonic cavitation.

Description

The invention relates to dissolution methods based on the use of ultrasonic cavitation energy to intensify the processes of dissolution and dissociation of electrolytes in water, for example, in the chemical, electrical and food industries.

In the chemical industry, the invention can be used to accelerate liquid-phase reactions in aqueous solutions of electrolytes in the implementation of various technological processes. In the electrical industry, using the invention, it is possible to manufacture electrolyte solutions for chemical current sources. In the food industry, the invention can be used in the preparation of brines and in the salting of food raw materials in the production of fish, meat and vegetable products, as well as canned food from animal and / or vegetable raw materials.

A known method of manufacturing an electrolyte solution for a manganese-zinc chemical current source [application No. 93016666 RU, 1993], in which an organic corrosion inhibitor, which is a non-dissociable component, is mixed with a polymer or oligomeric component and dispersed in water or an aqueous electrolyte solution with heating to a temperature not exceeding the temperature of the onset of decomposition of any of the components. As a result, the preservation of the element increases and the consumption of an inhibitor having poor solubility in an aqueous medium decreases.

Obligatory heating of the prepared electrolyte solution, on which the technical effect directly depends on the temperature, prevents the technical result formulated below, for example, in the food industry, where the thresholds for thermal denaturation of proteins or vitamins have low temperature values. In addition, this method is impractical to intensify by using the effect of cavitation disintegration, since the cavitation threshold, and, accordingly, the resulting effect decreases with increasing temperature [1].

A known method of preparing an electrolyte solution [RU 1729025, 1990], intended for use in the chemical, metallurgical and food industries, which can be used in the implementation of physicochemical processes occurring between a solid and a liquid and accompanied by the transfer of all or part of this substance into a solution . The method includes dissolving salts and minerals while stirring or circulating the suspension through the dissolution zone. In this case, the suspension is subjected to continuous hydrodynamic treatment with solution jets introduced into the dissolution zone.

Even if cavitation occurs in the jets of the solution due to the presence of pressure gradients, it has a hydrodynamic nature. It is known that hydrodynamic cavitation is much less effective than ultrasonic (acoustic), which occurs in elastic waves in a liquid under the influence of variable sound pressure [2]. But hydrodynamic cavitation in an electrolyte solution, which in itself is an aggressive medium, will require the adoption of measures to ensure the erosion and corrosion resistance of the equipment in which the process is carried out. All this impedes the achievement of the technical result formulated below.

A known method of preparing solutions of electrolytes intended to obtain composite coatings used in electroplating [RU 2088689, 1996]. The prepared solution contains a dispersed phase in the form of solid metal microparticles, which provides increased sedimentation stability and improved physical and mechanical characteristics of the coatings due to the high degree of dispersion of the phase particles. The method includes introducing into the solution this dispersed phase and its further dispersion to the state of a stable colloid by the action of ultrasonic vibrations.

Since here the dispersing factor is cavitation, which is excited by ultrasound in an electrolyte solution - a chemically aggressive environment, erosion and corrosion protection of the equipment in which the process is carried out is required, which makes it more complicated and more expensive. This prevents the achievement of the technical result of the present invention.

The closest technical solution to the claimed is a method for the preparation of brine in the meat processing industry, containing as a dissociable component NaCl and salting them chopped meat raw materials. The method includes activating the brine by treatment in a cavitation reactor and mixing the activated brine with meat raw materials, which are poorly soluble and slightly dissociable component containing polyelectrolytes [RU 2245624, 2004]. The increase under the action of cavitation of the dissolving and dissociating abilities of water allows the product to provide the required content of sodium and chlorine ions immobilized by water molecules in the solvate shells of meat biopolymers while reducing the total NaCl content [4]. This method is adopted as a prototype.

With regard to achieving the technical result of the invention, the method has the same drawback as discussed above, namely, cavitation, enhancing the chemical aggressiveness of the electrolyte, will destroy the cavitation reactor in which the activation process is carried out [5]. Therefore, the developer takes special measures to prevent such damage, which complicates and increases the cost of equipment for the preparation of this electrolyte solution [6, 7]. This does not allow to obtain the technical result formulated below.

The invention is aimed at creating a method for preparing aqueous solutions of electrolytes using ultrasonic cavitation to intensify the process and improve the result, which does not require taking measures of corrosion and erosion protection of equipment in which cavitation is carried out.

The invention consists in the following.

As is known, the energy of ultrasonic cavitation can have a direct dissociating effect on water-soluble chemical compounds with ionic and covalent types of bonds [8, 9]. This action turns out to be through the implementation of high-energy chemistry mechanisms and has a suprathermal character [2, 4]. The restoration of the equilibrium thermodynamic state of the solution after this kind of cavitation exposure occurs in a short period of time. In the equilibrium state, the degree of dissociation of the electrolyte becomes appropriate if its ions are not immobilized by polar molecules of water. As can be seen from [4], the relaxation of the unsteady state of NaCl dissociation in water has an exponential dependence on time with a negative coefficient in front of the argument. However, there is another significant factor of cavitation effects that affects the degree of dissociation of electrolytes - this is cavitation declustering of water [10], in which they dissolve. By epithermal cavitation effects on water, it is possible to break intermolecular hydrogen bonds in it, which form its cluster structure in a stationary state. This significantly increases its dissolving and dissociating ability. Therefore, aqueous electrolyte solutions can be prepared in this order. First, treat the water in a cavitation reactor, then dissolve or dilute the electrolyte phase with it, regardless of whether it is a solid, concentrated solution or dispersed system, including insoluble components. In this case, it is not necessary to use a cavitation apparatus resistant to aggressive environments. During research it was experimentally established that the degree of dissociation of type A ⁺ B ^- electrolytes, to which NaCl belongs, after dissolving in water previously subjected to cavitation treatment and when processing the finished NaCl solution of the same concentration, 5 seconds after completion of the dissolution process and processing, respectively, practically do not differ. This suggests that the ions of the dissociable electrolyte in the treated water acquire dense solvation shells of free water molecules, that is, are immobilized by them, which prevents their association.

The technical result of the invention is to reduce the requirements for erosion protection of equipment for the implementation of the process of preparing aqueous solutions of electrolytes under the influence of ultrasonic cavitation, and therefore, the simplification of this equipment without reducing the effect of the use of cavitation.

The specified technical result when using the invention is achieved due to the fact that in the method of preparing an aqueous electrolyte solution containing other dissociable as well as non-dissociable, hydratable and non-hydratable substances, including ultrasonic cavitation treatment, the difference is that they are subjected to ultrasonic cavitation treatment water, after which it is mixed with the remaining components of the solution.

When analyzing the distinguishing features of the described method, no known similar technical solutions in the field of the subject invention and related fields of technology were revealed.

The method is as follows.

Water is exposed to ultrasonic cavitation, for example, in a cavitation reactor, after which it acquires a dissolving and dissociating ability increased in relation to the conditions of thermodynamic equilibrium. Then, from the water treated in a cavitation reactor, an electrolyte solution is prepared. For this, it is mixed with a dissociable component, for which, for example, NaCl can be used, as well as non-dissociable, hydratable and non-hydratable substances, for example hydrophilic and hydrophobic polymers, in the form of powders, colloidal and true solutions or suspensions.

The following are examples of specific uses of the invention in accordance with its features.

The invention was used for the preparation of brines used in the salting of raw meat in the production of cooked sausages and the preparation of minced sausage products themselves [11, 12]. As a device for cavitation processing, a device of the SIRINX 4000 type was used [13]. The water used in food production was processed, on the basis of which an electrolyte solution was prepared - a mixture of water and salt with meat raw materials containing non-dissociable, non-hydratable and hydratable components, which in this case are all biopolymers: fats and proteins, respectively, introduced into solution in the form of chopped meat. For comparison, a pre-prepared brine was processed - a concentrated solution of sodium chloride - and mixed with meat raw materials in accordance with RU 2245624, 2004. In both cases, grinding lump meat and mixing it with salt and water activated in an ultrasonic cavitation reactor or, respectively , NaCl solution was carried out in an Karl Schell FD 2/70 emulsifier, followed by treatment with the rest of the formulation components in a K 324 Seydelmann cutter. The amount of water constituting the electrolyte medium was calculated as the ratio of the salt content in the mixture of components to the weight of the salt, saturating 1 kg of water at a temperature of +8 ... + 10 ° С. Heat treatment was carried out in a Fessmann heat chamber. The tests were carried out in the manufacture of cooked sausages in accordance with GOST 23670-79. The average values of the residual NaCl content for 10 batches of sausages, measured by the concentration of Cl ions ^, using the standard method, were 2.20 ± 0.03% in both cases, that is, the degree of dissociation of the main electrolyte was the same. Moreover, in the case of the implementation of the claimed method in the apparatus "SIRINX 4000" was treated with water, rather than a concentrated solution of NaCl, so it is clear that chemical corrosion was excluded in it.

The next example is the preparation by the claimed method (and for comparison by the method selected as a prototype) of an electrolyte solution used as a paste for polishing and finishing metal products [14], for example, in jewelry. It consisted of: liquid glass - a surface-active component (electrolyte), finely dispersed electrocorundum - abrasive material (non-dissociable and non-hydratable component), dried walnut shell powder - dispersed filler (a mixture of hydratable weakly dissociable components). As a device for cavitation treatment, a laboratory apparatus of the SIRINX 250 type was used. Using it, in an open glass container of 200 ml in the first case, distilled water was subjected to cavitation for 90 s. Then, dry electrolyte was dissolved in the treated water, and the resulting solution was mixed with other components. That is, all the signs of the claimed method were implemented. In the second case, an aqueous electrolyte solution with the same content as in the first case was subjected to cavitation treatment under the same conditions. Then it was also mixed with the remaining components: abrasive and filler. The ratio of dry matter and water in the paste by weight in both cases was 2: 1. After the preparation of these paste samples, part of each of them was mixed with water in a proportion of 1:50. The degree of dissociation of the electrolyte in the solution was established by measuring the electrical conductivity with the conductivity sensor of the Anion 7051 device (INFRASPAK, Novosibirsk). In both cases, the electrical conductivity of the solution within the measurement error of the device turned out to be the same. That is, the effect of cavitation treatment on the degree of dissolution and dissociation of the electrolyte is also the same in both cases. During the cavitation treatment of water in the first case and the salt solution in the second, the same strips of aluminum foil were placed in the same zone of the container in which the treatment was carried out — samples. Thus, the well-known Knepp method [15] was applied, which is used to study the intensity of cavitation erosion. Before and after treatment, the mass of the samples was measured and its decrease was calculated, which characterizes the degree of erosion. In the first case, the sample lost only 3.2% of the mass, while in the second - 8.3%. That is, as a result, the same parameters of the prepared solution were obtained, characterizing it as an electrolyte solution, and the erosive effect on the metal sample inside the device, and therefore on the structure of the device itself, for example, on an acoustic transformer made of a titanium alloy and serving as an ultrasound emitter , in the first case it was less.

Thus, the above information indicates the possibility of carrying out the claimed invention using the means and methods described in the application or previously known, as well as the possibility of achieving the above technical result when implementing the totality of the features of the invention.

Literature

1. Shestakov S.D. Fundamentals of cavitation disintegration technology. Theory of cavitation reactor. - M .: EVA-press, 2001.

2. Rogov I.A., Shestakov S.D. Suprathermal change in the thermodynamic equilibrium of water and aqueous solutions: misconceptions and reality. Part 1 // Storage and processing of agricultural raw materials, 2004. 7, - P.24-28.

3. The Great Soviet Encyclopedia. - M.: Publishing. Soviet Encyclopedia, t.30, Art. "Electrolytes", 1972.

4. Rogov I.A., Shestakov S.D. Suprathermal change in the thermodynamic equilibrium of water and aqueous solutions: misconceptions and reality. Part 2 // Storage and processing of agricultural raw materials, 2004. 10. - S.9-13.

5. A study of the phenomenon of intensification of the physicochemical processes of “wet” meat salting in meal with a solution of sodium chloride subjected to cavitation disintegration, and the development of specialized equipment // Research Report. VNITTS, state registration number 0120.0 405099, 2004

6. The decision to grant a patent of the Russian Federation for a utility model by application No. 2004120738, 2004.

7. Certificate of official registration of the computer program No. 2004611996, 2004.

8. Elpiner I.E. Ultrasound. Physico-chemical and biological effects. - M .: IF-ML, 1963 .-- 420 p.

9. Bergman L. Ultrasound and its application in science and technology. - M .: IIL, 1956.

10. Shestakov S.D. The energy state of water and its binding by biopolymers of food raw materials: New opportunities // Storage and processing of agricultural raw materials, 2003. 4, - P.35-37.

11. Shestakov S.D. The technology of cavitation disintegration of liquid food media and its application in the meat industry // Transactions of the international forum "Meat Industry". - M: Publ. Asti Group, 2002, p. 95-96.

12. Shestakov S. D., Sokolov V. B., Chestnov S. M., Dzhafarova N. A., Podhomutov N. V., Bardonova E. F. Equipment and technology for the activation of solutions of curing agents for wet salting of meat // Materials of the international scientific and technical conference "Modern technologies for processing livestock raw materials in providing healthy nutrition: science, education and production". - Voronezh .: Ed. VGTA, 2003 .-- S.326-333.

13. The device “Syrinx 4000” for cavitation disintegration of liquid food media, SITB.443146.002TU, 2002.

14. The Great Soviet Encyclopedia. - M.: Publishing. Soviet Encyclopedia, Vol. 20, Art. "Polishing", 1972.

15. Knapp R., Daily J., Hammitt F. Cavitation. - New York: McGraw Book Company, 1970.

Claims (1)

A method of preparing an aqueous electrolyte solution containing dissociable as well as non-dissociable, hydratable and non-hydratable substances as solution components, including ultrasonic cavitation treatment, characterized in that water is subjected to ultrasonic cavitation treatment, after which the solution components are dissolved in water.