RU2383489C2 - Method of producing cold oxygen gas and device for realising said method - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: oxygen generator can be used as a more efficient compact standalone source of oxygen gas for enabling people to breath, mainly during accidents and emergency situations. The generator has a housing which has one or more outlet openings, a solid charge of oxygen-generating material which is placed in a combustion chamber lying in the housing and having one or more outlet openings. Between the outer surface of the combustion chamber and the housing of the generator there is a multifunctional active element which has a porous gas-permeable structure and whose material is selected from a group of peroxides and superoxides of alkali and alkali-earth metals. The generator has a device for igniting the charge and a filter for removing particles from the obtained oxygen.

EFFECT: increased specific output of oxygen with simultaneous reduction of temperature and increase in purity of the generated oxygen, reduction of temperature of the housing during and after operation of the generator, longer operation time of the generator and increased safety during its operation.

12 cl, 6 dwg, 1 tbl

Description

The present invention relates to applied chemistry, and in particular to methods and devices for producing gaseous oxygen.

Autonomous, small-sized, high-speed, with a large specific gas output, sources of gaseous oxygen with high purity and normal temperature are necessary in many areas of human life and, as a rule, are especially necessary in emergency cases and emergency situations. For example, such sources of gaseous oxygen are necessary for many categories of sick people (for asthma attacks, heart attacks, and a number of other diseases), for equipping ambulances, for the life support of rescue workers of various categories in accidents at mines, chemical and other hazardous enterprises, for life support of firefighters during fire extinguishing, for emergency supply of oxygen to people on airplanes during emergency depressurization, for emergency supply of oxygen to personnel in submarines in case of ode down other emergency systems provide oxygen or air, and in many other areas.

It has long been and until now widely used in practice as sources of gaseous oxygen for this purpose gas-balloon systems (GBS). However, along with well-known advantages, such systems have a number of significant drawbacks: they have significant mass and dimensions, give a relatively low oxygen yield from units of mass and volume, and are constantly exposed to high pressure (100-200 kgf / cm ² ) of oxygen, which creates the danger of rupture or leakage of oxygen and the threat to human life in the event of the ignition or explosion of substances or materials in contact with escaping oxygen, the difficulty of refueling or refueling with oxygen when there is no station near ary oxygen filling stations, non-autonomous, relatively long time of actuation, the need for the organization of special storage areas and a constant pressure control in the cylinders.

Chemical oxygen generators (HCH) on solid pyrotechnic compositions (oxygen-generating solid materials) do not have most of these disadvantages of GBS. Relatively small size and mass, relatively large specific yield per unit mass (K _m ) and volume (K _V ) of oxygen, lack of oxygen pressure in the housing during storage, autonomy, constant readiness for work for many years without routine checks, speed and ease of starting from low-power autonomous sources of electricity, reliability, ease of re-equipment in the absence of stationary workshops and a number of other advantages make them significantly more suitable for use as a source oxygen gas in the above applications.

The first, and relatively long ago (from the 40s-50s of the last century), began to be developed and applied in practice of the KHG of the "classical type", that is, based on the traditional method of burning solid charges from oxygen-generating materials in a regime where the front of self-sustaining combustion extends deep into the charge, and the gaseous products emitted in this process flow from the combustion front in the opposite direction (Chemical Encyclopedia. Volume 2 / ed. Sov. Encyclopedia // M., 1990, patents: No. 3,868,225 (US); No. 2052283 (RU), No. 6.264. 896 (US), No. 6.352.652 (US) No. 6,464.787 (US)). Such HKG are quite simple in design. They consist of a casing made of metal, preferably steel, having one or more outlet openings, elements for attaching the casing to the equipment, a solid charge of oxygen-generating material (moreover, the charge is capable of initiating self-sustaining combustion with the release of oxygen in this process and the formation of high-temperature slags ), a device for ignition (initiation) of a charge installed at the end of the charge and providing at a given moment ignition of the surface of the charge, adjacent heat-protective layers or elements made of inert materials that can be installed between the charge and the inner surface of the housing, and on the outer surface of the housing, to protect the housing from heating and one or more inert filters for cooling the generated oxygen, for cleaning the generated oxygen from impurities of harmful gases and for cleaning generated oxygen from impurities of particles.

As oxygen generating components of oxygen generating materials (CHM) for the charge of such HCH, substances from the group of alkali metal chlorates or perchlorates are used, more specifically, lithium, sodium and potassium perchlorates and chlorates, and preferably sodium chlorate, sometimes they are used together with substances from the group of peroxides and alkali metal superoxides; as combustible substances from the group of metals are used in them: aluminum, magnesium, zinc, molybdenum, iron, manganese, cobalt, nickel and, preferably, iron; as additives for various purposes, substances from the group of oxides are used: oxides of copper, iron, silicon, zinc, manganese, cobalt, chromium and, preferably, oxides of manganese and cobalt; barium peroxide, sodium and potassium silicates, glass.

However, HCG of this type have a significant drawback. It lies in the unacceptably high temperature of the released oxygen at the outlet of the gas generator. For example, patent No. 3868225 (US) teaches oxygen temperatures in a gas generator up to 370 ° C. Obviously, if oxygen is used after exiting the generator directly for respiration, it must be further cooled in the HCH. Usually, cooling is carried out using inert filters with high heat capacity (heat exchangers) in the KHC. This method of lowering the temperature of oxygen generated by HCH leads to an increase in the mass and dimensions of HCH and a decrease in the specific yield of oxygen, and often makes the use of HCH in many applications ineffective or impossible.

More recently, a new method was proposed for producing cold gases in gas generators (patent No. 2108282 (RU) dated November 28, 1996, publ. Bulletin No. 10, 04/10/98.). This method allows you to get cold (with a temperature close to normal) oxygen in the main time of operation of the HKG and thus practically eliminate the drawback inherent in the HKG of the classical type. Based on this method, a chemical oxygen generator was proposed with a temperature of released oxygen less than 50 ° C and preferably less than 30 ° C (only at the end of the work the temperature of the generated oxygen can increase significantly) (application No. 2001121023 (RU) dated July 26, 2001 , published bulletin No. 18, 06/27/2003, application PCT / NL / 02/00506 of July 25, 2002, published WO 03/009899, February 6, 2003).

HCH of this type, in principle, consist of the same basic elements as HCH of the classical type:

1) a casing made of metal, preferably steel, or a composite material, having one or more outlet openings and fastenings, which allow carrying, transporting, mounting the casing in devices and attaching to equipment or walls. The housing through the outlet may be connected to the buffer or cylinder;

2) a solid porous charge, which is placed inside the body of the generator. Moreover, the charge is made of oxygen-generating material, which, after initiation, is capable of self-sustaining combustion and oxygen evolution in this process and the formation of high-temperature slag. The porous charge is placed in the housing in such a way that the oxygen produced during its combustion passes through the pressure drop through the unburned part of the charge body from the combustion front in the direction of its movement to the outlet of the housing. At the same time, the porous charge during combustion provides the possibility of the passage of the obtained oxygen through its body without violating the integrity and creating volumetric combustion.

The porous charge is made of granular material bound by a binder and having a porosity ranging from 41 to 61%.

As the main components of oxygen-generating materials for charges to HCH of this type, almost all of the same substances are used as for charges to HCH of the classical type. Additionally, as a binder, they include in small quantities substances: from the group of inorganic binders, in particular silicates of sodium and potassium and mixtures thereof, and from the group of organic varnishes and binders, preferably the sodium salt of polyvinyltetrazole, and, in addition, the sodium salt of carboxycellulose, polyvinyl acetate, nitrocellulose, a mixture of pentaphthalic anhydride and pentaerythritol, epoxy resin and water-soluble proteins (application No. 2001121023 (RU), application PCT / NL / 02/00506);

3) a device for igniting a charge installed at the end of the charge and providing at a given moment the initiation of ignition of the surface of the charge adjacent to this device;

4) inert filter-heat exchanger for oxygen cooling;

5) a filter for cleaning the produced oxygen from harmful gases and a filter for cleaning the produced oxygen from particles. Two or three filters can be combined;

6) a heat-protective layer of an inert heat-insulating material (for example, fiberglass or silicone fiber, impregnated with the same binder that is used in the charge), placed between the charge and the housing, or from the outer layer of the charge.

The specified device for producing cold oxygen and the method of generating oxygen realized during its operation are the closest in combination of essential features to the claimed technical solution and therefore have been adopted as a "prototype" of the invention.

However, the prototype has a number of significant disadvantages:

1) The HKG prototype has a relatively low specific yield of oxygen per unit mass (K _m - at the level of 40-50 l / kg) and unit volume (K _v - at the level of 55-70 l / dm ³ ). Obviously, the low level of K _m and K _v causes, in general, a small amount of oxygen released by HCH and, accordingly, makes the probability of saving people using HCH in emergency and extreme situations in the above areas of application low.

МеСlO₃→MeCl+3/2O₂, но, в зависимости от условий, иногда и по пути: 2МеСlO₃→Mе2O+Сl₂+5/2O₂. Термическое разложение перхлоратов щелочных металлов (которые тоже могут использоваться в качестве основного компонента кислородгенерирующего материала) проходит через стадию образования хлоратов с соответствующим возможным выделением хлора. В присутствии избытка кислорода и при высоких температурах смеси хлора с кислородом могут образовывать различные оксиды хлора. Появление других вредных газов в выделяемом кислороде в большинстве случаев вызвано примесями различных элементов и соединений в исходных компонентах.2) Oxygen generated by the HKG prototype has a relatively low purity: O ₂ - 95.35-95.4%; CO ₂ - 0.92-0.93%; N ₂ - 2.1-2.12%; H ₂ O - 1.58-1.60% (application No. 2001121023 (RU), PCT / NL / 02/00506). The possibility of the presence of impurities of chlorine and its oxides in the oxygen generated by HCH is noted. The reason for the appearance of chlorine in oxygen generated by HCH is due to the fact that the decomposition reaction of alkali metal chlorates (the main component of the oxygen-generating material) can proceed not only along the main path:

МеСlO ₃ → MeCl + 3 / 2O ₂ , but, depending on the conditions, sometimes along the way: 2МеСlO ₃ → Ме2O + Сl ₂ + 5 / 2O ₂ . The thermal decomposition of alkali metal perchlorates (which can also be used as the main component of the oxygen-generating material) passes through the stage of formation of chlorates with the corresponding possible evolution of chlorine. In the presence of excess oxygen and at high temperatures, mixtures of chlorine with oxygen can form various chlorine oxides. The appearance of other harmful gases in the released oxygen is in most cases caused by impurities of various elements and compounds in the starting components.

To eliminate impurities of harmful gases in the oxygen generated by the HCH, a "chemical" filter is installed in the output part of the generator. This method of eliminating harmful impurities is relatively effective, but requires that the filter has a sufficiently large mass and dimensions. In order to reduce the mass and dimensions, this filter is additionally given the function of purifying oxygen from particles. However, this technical solution leads to a complication of the design of the generator, to an increase in its mass and dimensions, a decrease in the specific yield of oxygen, and does not provide a complete purification of oxygen from impurities of harmful gases.

3) The HKG prototype, when triggered and after operation in the absence of a heat-protective layer, has an unacceptably high body temperature. In this case, it can be at the level of slag temperature (800-1200 K), and sometimes higher. This is due to the fact that oxygen-generating materials during combustion produce oxygen and high temperature slags. To reduce the heating of the HKG case during and after operation, a relatively thick layer of inert heat-absorbing material is placed between the charge and the case or a non-combustible outer layer of charge is used, which leads to an increase in mass and dimensions, complicating the design and reducing the specific oxygen output.

4) The HKG prototype has a relatively short run time. This indicator is at the level of 12-15 minutes. Obviously, the longer the HKG operating time at a sufficient rate of oxygen evolution and an acceptable level of other characteristics, the more reliably can the viability of oxygen consumers be ensured in the above areas of application and especially in extreme and emergency situations.

To increase the operating time of HKG, it is necessary to reduce the rate of burning of the charge. However, the oxygen-generating pyrotechnic materials used in the prototype already have very low combustion rates (0.1-0.7 mm / s) and are at the limit of sustainable combustion. With a further decrease in their burning rate depending on the composition and conditions, it is possible to stop the charge burning during the operation of the HKG, which can lead to the death of oxygen consumers from the generator.

5) In the prototype, the last portions of oxygen (about 1-3% of the total amount of oxygen emitted) emitted during the combustion of the final small layer of oxygen-generating material at the rear end of the charge have a high temperature (usually at the level of 800-1000 K). To a certain extent, this oxygen in the wall layers is cooled by heat transfer to the walls of the body, but the temperature in the core of the flow can remain high. Obviously, such oxygen cannot be used after exiting the generator directly for human breathing. To cool these portions of oxygen in the HKG prototype, a method is used, which consists in passing oxygen through an inert filter-heat exchanger installed in the output part of the HKG and transferring part of the heat from oxygen to this filter. In special cases, this filter is combined with a filter to purify oxygen from impurities of harmful gases and particles. However, this method leads to a complication of the design of the generator, to an increase in its mass and dimensions and a decrease in the specific yield of oxygen.

6) The HKG prototype has insufficient safety for the consumer in the process. The generator operates at oxygen pressures in the housing at the level of 3-5 kgf / cm ² (sometimes higher). Given this pressure level, the material and wall thickness of the generator housing are calculated and selected. However, due to various kinds of accidents (violation of the integrity of the charge during equipment, storage or transportation, technological defects in the manufacture of the charge, deviations in the characteristics of the ignition device due to technological defects, integrity violations during the equipment, storage and transportation, etc.) during the operation of the HKG possibly an unauthorized significant increase in the gas intake from the charge and the ignition device and, as a result, a sharp increase in pressure in the housing. An accidental increase in pressure in the generator housing during operation can also be caused by a violation of the gas permeability of charges and filters (due to clogging of pores by slags or particles, deformation of filters and charges during equipment or transportation) and other reasons. Raising the gas pressure above the maximum possible in the housing can lead to its rupture, personal injury and the ignition of certain materials in contact with high-temperature oxygen and slag ejected from the exploding generator. To improve the security of HKG, they choose a more durable material for the case, increase the thickness of the case. In this case, the problem is not completely solved, since the pressure rise in the housing for the indicated random reasons may exceed the limit value that is provided by both more durable material and thicker walls. This circumstance necessitates the creation of new, effective ways to increase the safety of HCG.

The objective of the present invention is to provide a method for producing cold gaseous oxygen and a chemical oxygen generator for its implementation, which can increase the specific yield of oxygen while lowering the temperature and increasing the purity of the generated oxygen, lowering the temperature of the body during and after the generator, increasing its operating time and increasing its safety in the process.

The problem is solved by the proposed method for producing cold gaseous oxygen in a chemical oxygen generator based on self-sustaining charge burning from an oxygen-generating material, including the generation of oxygen with the formation of high-temperature slags during combustion of a charge placed in the combustion chamber, the evolution of additional oxygen, cooling the generator’s body, cooling and cleaning from impurities of various gases generated during combustion of an oxygen charge due to the transmission of e о through a multifunctional active element (MAE) located in the space between the outer surface of the combustion chamber and the generator housing, having a porous gas-permeable structure and whose material is capable, under the influence of heat released during combustion, to thermal decomposition with heat absorption and oxygen evolution without other gases and interaction both the MAE itself and the condensed products of its decomposition with acid-forming gases with the formation of condensed substances, purification of the obtained oxygen and from particles at the exit of the generator.

In particular, the upper limit of the oxygen pressure in the combustion chamber is limited to a certain predetermined value using an automatic safety valve (APC) by dumping excess oxygen from the combustion chamber through the APC in the MAE.

In particular, they organize the passage of the obtained oxygen through the MAE in the direction of motion of the charge combustion front.

In particular, they organize the passage of the obtained oxygen through the MAE in the direction opposite to the direction of motion of the charge combustion front.

The method of producing cold gaseous oxygen is carried out using a chemical oxygen generator with a temperature close to normal, containing a body made of metal, preferably steel, or a composite material having one or more outlet openings, a solid charge of oxygen-generating material capable of self-sustaining after initiation combustion with the evolution of oxygen and the formation of high-temperature slag, placed in a combustion chamber located in the housing and having one or several outlet openings, while in the space between the outer surface of the combustion chamber and the generator housing there is a multifunctional active element (MAE) having a porous gas-permeable structure and the material of which is capable, under the influence of heat released during combustion, to thermal decomposition with heat absorption and oxygen evolution without other gases and the interaction of both MAE itself and the condensed products of its decomposition with acid-forming gases to form condensed substances, a device for igniting a charge, installed at the end of the charge and providing at a given moment the initiation of ignition of the surface of the charge adjacent to this device, a filter for cleaning the produced oxygen from particles, placed at the outlet of the generator.

In particular, the combustion chamber is equipped with an automatic safety valve.

In particular, the combustion chamber is arranged in such a way that the produced oxygen is discharged in the direction of movement of the charge combustion front.

In particular, the combustion chamber is arranged in such a way that the produced oxygen is discharged in a direction opposite to the direction of motion of the charge combustion front.

In particular, the MAE is made in the form of a powder, preferably with a particle size of from 0.05 to 0.5 mm, or in the form of granules, preferably with a size of from 0.5 to 1.5 mm, or in the form of a solid porous body, preferably with porosity (æ = V _pore / V _MAE , where V _pore and V _MAE , respectively, the pore volume in the MAE and the volume of the MAE itself) ranging from 15 to 30%, or in the form of combinations thereof.

In particular, the MAE material is selected from the group of chlorates and perchlorates of alkali and alkaline earth metals in combination with substances from the group of peroxides and superoxides of alkali and alkaline earth metals, preferably from the group of peroxides and superoxides of alkali and alkaline earth metals, in particular sodium superoxide.

In particular, as a binder material MAE, made in the form of granules or in the form of a solid porous body, choose substances, preferably from the group of inorganic compounds, in particular cements.

In particular, the MAE material includes additives that reduce the temperature of the onset of decomposition and accelerate the thermal decomposition of the substances used in this material, which are selected from the group of oxides and hydroxides of transition metals and simple and complex metal salts containing one or more metal cations and one or more anions type Mt _x O _y (where Mt is a transition metal, O is oxygen, x is 1 or 2, y is 1 to 7), preferably potassium permanganate.

In particular, the housing has a mount or mounts, providing the ability to mount the housing in devices or attach to equipment or walls.

In particular, the housing has an attachment or attachments that enable it to be transported and transported.

In particular, the housing is connected to a buffer or balloon through an outlet or holes.

The proposed chemical oxygen generator is illustrated by graphic images:

Figure 1. - a longitudinal section of the generator in the initial state using a combustion chamber equipped with an AIC and having several outlet openings that are directed towards the outlet of the generator;

Figure 2 is a longitudinal section of the generator shown in figure 1, in the process;

Figure 3 is a longitudinal section of a generator in its initial state using a combustion chamber without an AIC and having several outlet openings that are directed toward the outlet of the generator;

Figure 4 is a longitudinal section of the generator shown in Figure 3, during operation;

Figure 5. - a longitudinal section of the generator in the initial state using a combustion chamber equipped with an AIC and having one outlet, which is directed to the side opposite to the outlet of the generator;

6. - a longitudinal section of the generator shown in Fig.5, in the process.

The proposed embodiment of the HKG device based on the method described in the application have a number of fundamental differences from the prototype:

- they introduced a new, of fundamental importance multifunctional active element, the material, the placement and functions of which are described above;

- they introduced a new element - a combustion chamber, in which a charge from the KGM is placed and which is placed inside the HKG case. KS is a thin-walled cylindrical shell made of metal, preferably alloy steel, with one or more outlet openings for oxygen. CS is necessary for isolating the charge and the ignition device from the MAE material during storage (to protect against chemical interaction) and in the process of ignition and combustion of the charge (in order to ensure the required modes of combustion), to create the necessary directions of motion of the combustion front and the flow of oxygen the charge and motion of the front of thermal decomposition and oxygen filtration in the MAE (with the aim of obtaining the greatest oxygen output and the most effective purification of oxygen from impurities and cooling it and the body), as well as for the suit li ne output high slag during combustion of charge in any place in the housing wall and CCG MAE by the decomposition;

- they do not have heat exchanger filters for cooling oxygen;

- they do not have inert chemical filters for purifying oxygen from impurities of harmful gases;

- they can be equipped with an automatic safety valve, which is installed on the compressor station and is designed to limit the upper limit of oxygen pressure in the HKG during operation and increase the safety of the HKG;

- they do not have inert heat-shielding layers, elements or coatings both inside the HKG case and outside.

The chemical oxygen generator contains a housing 1, a charge 2 of KGM, located in the combustion chamber 3, having one or more outlet openings 4. In the space between the outer surface of the combustion chamber 3 and the housing 1 there is a multifunctional active element 5. At the end of the charge 2 there is a device 6 for ignition of a charge 2. At the exit 7 from the generator, a filter 8 is placed to clean the resulting oxygen from particles. In some embodiments of the invention, the combustion chamber 3 is equipped with an automatic safety valve 9.

Figure 2, 4, 6 shows the front 10 of the combustion of charge 2, the direction 11 of the movement of the front 10, the slag 12 remaining in the combustion chamber, the front 13 of the thermal decomposition reaction of the MAE 5, the direction of movement 14 of the front 13, the condensed products 15 of the decomposition of the MAE 5, direction 16 of the movement of oxygen in the HCH.

The proposed chemical oxygen generator in various embodiments based on the proposed method works as follows.

The charge 2 of the KGM from the end is ignited using the ignition device 6. Oxygen emitted during the combustion of charge 2 flows through one or several outlet openings 4 from the combustion chamber 3 and is filtered through MAE 5 due to the differential pressure and then goes to the consumer through the particle filter 8. High-temperature slag 12 formed during the combustion of charge 2, in the form of cake remain in the combustion chamber 3.

In the embodiment of the HCH shown in FIGS. 1, 2, oxygen released from the COP 3 in the main time of burning of the charge 2 in the combustion mode used has a low temperature (less than 50 ° C and preferably less than 30 ° C) and basically requires removal of impurities of harmful gases and only minor additional cooling. Oxygen passing through MAE 5 in the direction of exit 7 from the generator is purified from impurities of harmful gases due to the chemical interaction of the components of the material MAE 5 and their decomposition products with such gases with the formation of condensed substances. The formed condensed substances are retained by the MAE 5 material and further by the filter 8 and remain in the HCH body 1, not being released together with the generated oxygen. In this case, due to heat transfer to the material MAE 5, oxygen is cooled to normal temperature.

In the embodiments of the HCH shown in Figs. 3, 4 and 5, 6, the temperature of the oxygen discharged through one or more of the outlet openings 4 of the KC 3 during the combustion of the charge 2 during the combustion mode used is very high (at the level of 800-1200 K). In the embodiment of the HCH shown in FIGS. 1, 2, the same temperature level has a portion of oxygen (1-3% of the total generated oxygen volume) discharged from KS 3 upon combustion of the last small portion of charge 2. High-temperature oxygen discharged from KS 3, passing through the porous material MAE 5, due to expansion, convective heat exchange with the material MAE 5 and the cost of heat for its thermal decomposition is cooled to ambient temperature. Moreover, due to the ability of the substances that make up the MAE 5 material and their decomposition products to chemically interact with harmful gases present as impurities in oxygen, with the formation of condensed products, oxygen is purified from these impurities. In addition, oxygen is partially purified from impurities of slag particles due to the delay of these particles by the finely porous structure of MAE 5. The MAE material, heated to the temperature of the onset of decomposition due to heat transfer from high-temperature oxygen discharged from KS 3, decomposes into oxygen and condensed products. This additionally obtained oxygen, together with the oxygen coming from the combustion chamber 3, is filtered through the remaining part of the MAE 5 and the filter 8 for cleaning particles from impurities to the outlet 7 of the generator. The condensed products 15 of thermal decomposition of the material MAE 5 and the products of its interaction and these products 15 of its decomposition with impurities of harmful gases are delayed both by the material MAE 5 and filter 8 and remain inside the casing 1 of the HCH.

Thus, oxygen purified from harmful impurities and cooled to normal temperature enters through the 7th HCH output 7 to the consumer. In addition, due to the allocation of an additional amount of oxygen to the charge 2 obtained during combustion, the overall oxygen output from the presented embodiments of HCH is increased on the basis of the proposed method in comparison with the HCH prototype. As a result, the specific characteristics also increase significantly: the oxygen output per unit volume and unit mass of HCH.

When the charge 2 is burned in KS 3, a significant amount of high-temperature slag 12 is formed, constituting 45-55% of the mass of the charge and having a temperature at the level of 1000-1500K. The heat flow from these slag due to heat transfer heats the material MAE 5 adjacent to the walls of the COP 3 in the area of the slag 12. In this case, the slag 12 itself is cooled. Absorbing the heat, the material MAE 5 decomposes with the formation of oxygen (its direction of motion is 16) and condensed products 15. Condensed products 15 of the decomposition of MAE remain in the zone of their formation. Thus, through the use of this heat, additional oxygen is released from the MAE material.

When the charge 2 is burning (FIG. 2), heat from the slag 12 of the surface of the COP 3 heated to the temperature of the slag 12 formed during the charge is transferred to the adjacent MAE 5 material layer. In this case, the MAE material heated to the decomposition onset temperature begins to decompose into oxygen and condensed products. The front 13 of the reaction of thermal decomposition of the MAE material propagates along the MAE near the heated surface of KS 3 in the direction of its end in accordance with the direction of motion 11 of the front 10 of the charge 2 at a speed close to the speed of the front 10 in charge. In the direction perpendicular to the HCH body 1, the front 13 of the thermal decomposition reaction of the MAE 5 material propagates at a speed significantly less. By the time the charge 2 ends, part of the MAE material remains undecomposed. The thermal decomposition of this part of the MAE with the evolution of oxygen continues until all the slags 12 in KS 3 are cooled to a temperature below the temperature at which the decomposition of the MAE material begins. Thus, the operating time of the considered embodiments of HCH, including MAE, increases compared to the HCH prototype, in which there is no MAE. The magnitude of the increase in operating time depends on the thickness, porosity and nature of the MAE material and the temperature of the slag in the combustion chamber.

As you move away from the surface of the combustion chamber 3 heated by the heat transferred from the slag 12 towards the HKG body 1, the temperature of the MAE 5 material decreases due to heat absorption by the previous layers to heat and decompose the material. At a certain MAE thickness, which depends on the temperature of the slag, the thermal decomposition parameters, the thermophysical characteristics and porosity of the MAE material, and a number of other factors, the ambient temperature is realized on the surface of the HCH body 1. In this case, a thin layer of MAE material adjacent to the surface of the generator housing may remain underdeveloped.

The agro-industrial complex used in the implementation of the HKG consists of the following main elements (not shown conventionally in the graphic images): a valve, a spring, a housing with several holes, and a pressure regulator for the spring on the valve. AIC 9 is mounted with its body on the outer surface of the combustion chamber 3 in such a way that in the initial state its valve closes the hole made in the COP. In this case, the valve is pressed to this hole by a spring with an elastic force corresponding to a given pressure. This implementation of the agro-industrial complex does not cover all its possible structural embodiments.

During the operation of the HCH, in the case of an abnormal increase in the oxygen pressure in the combustion chamber 3 above a predetermined maximum permissible value (due to an accidental increase in the gas intake from the charge due to technological defects, or due to a violation of the integrity during storage and transportation, or due to technological variations of the burning rate or in case of accidental blockage of the outlet (or part of the outlet) of the combustion chamber or pores in the charge by slags or other products, or due to other reasons), under the influence of oxygen pressure The valve compresses the spring and opens a hole in the COP. In this case, the high-temperature oxygen from it under the influence of a pressure drop is not discharged into the atmosphere, but into the MAE 5 and is filtered through its porous body, where it is mixed with the oxygen released during the thermal decomposition of the MAE material and with the oxygen released from one or several KS outlet openings, it is cooled by heat transfer to the MAE material to ambient temperature, it is cleaned of particles and impurities of harmful gases (due to interaction with the MAE material and its decomposition products) and follows in the direction of the filter 8 and exit 7 from KHG. After reducing the oxygen pressure in the COP to a predetermined value, the valve automatically returns to its original state under the action of a spring and the HKG continues to work in normal mode. Thus, by introducing into the KHG an agro-industrial complex in combination with other technical solutions proposed in the application: introducing an MAE, enclosing a charge in a separate shell — a combustion chamber, a certain relative position of the elements in the KHG, and optimized organization of the gas-dynamic path of oxygen movement in the MAE, the operation is stable and increased safety during the operation of the generator compared to the HKG prototype.

To ensure the movement of oxygen, increase the rate of heat transfer from it to the MAE material, increase the rate of oxygen evolution and the rate of neutralization of harmful gas impurities in oxygen, the MAE must have a porous structure with a developed surface. Therefore, the MAE material is made either in the form of a solid porous body, preferably with a porosity coefficient (æ) in the range of 15 to 30%, or in the form of a powder, preferably with a particle size of 0.05 to 0.5 mm, or in the form of granules, preferably with a size of from 0.5 to 1.5 mm (which approximately corresponds to the above величины limits), or - in the form of combinations thereof. At æ less than 15%, oxygen due to gas-dynamic resistance does not pass well through the body of MAE (which can lead to abnormalities in HCH), and at æ more than 30%, heat transfer through MAE material sharply worsens and, due to this factor and a decrease in the mass of MAE, the effectiveness of the method can be significantly reduced in terms of increasing the yield of oxygen from HCH. Thus, the specified limits of the coefficient of porosity are preferred.

In accordance with the claimed method, they best satisfy the set of requirements for substances for the manufacture of MAE material from the group of peroxides and superoxides of alkali and alkaline earth metals, and in particular sodium and calcium superoxides. Peroxides and superoxides of alkali and alkaline earth metals are capable of thermal decomposition with significant heat absorption and the evolution of oxygen and the formation of oxides of the corresponding metals without the release of any other gases or gaseous compounds. Moreover, they have a relatively low temperature of the onset of decomposition (T _n.d. ) (from 100 to 540 ° C) and therefore are capable of decomposition under the influence of temperatures that are realized in the released oxygen and slags during charge combustion in HCH. At the same time, they have a fairly significant heat of decomposition (from minus 5.2 to minus 16.2 kcal / mol), therefore they are capable of absorbing a large amount of heat during thermal decomposition.

It is most preferable to use sodium superoxide as a material of MAE, which has a relatively high content of active oxygen and the best operational and technological properties of all peroxides and superoxides of alkali and alkaline earth metals.

Oxides of alkali and alkaline earth metals have high boiling or sublimation temperatures: Li ₂ O - 2600 ° С, Na ₂ O - 1275 ° С, К ₂ O - 300 ° С, CaО - 2850 ° С, BaO - 2900 ° С, MgO - 3000 ° C. Therefore, these decomposition products of the above peroxides and superoxides are condensed products in the entire temperature range sold in the MAE, and remain within the volume of this element during and after the operation of HKG.

Peroxides and superoxides of alkali and alkaline earth metals and the condensed products of their thermal decomposition - oxides of the same metals - are capable of interacting with many acid-forming gases present as impurities in the oxygen obtained during the combustion of a charge, with the formation of condensed substances. In particular, when they interact with CO and CO ₂ , carbonates of the corresponding metals and oxygen are formed, when they interact with SO ₂ and SO ₃ , sulfates of the corresponding metals and oxygen are formed, when they interact with Cl ₂ and with various chlorine compounds with oxygen (for example, ClO, ClO ₂ and others), chlorides of the corresponding metals and oxygen are formed, when they interact with nitrogen oxides (for example, NO, NO ₂ ), nitrates of the corresponding metals and oxygen are formed, when they interact with COСl ₂ , chlorides and carbonates of the corresponding meta llov and oxygen. Carbonates, sulfates and chlorides of alkali and alkaline earth metals have higher boiling or sublimation temperatures (at the level of 1200 - 2000 ° С and higher) in comparison with the temperature of slags and oxygen formed during the combustion of a charge from oxygen-generating materials. Therefore, these substances are condensed products in the entire temperature range sold in the MAE, and also remain within the volume of this element during and after the operation of the HCH. The nitrates of these metals have a slightly lower temperature at the beginning of decomposition (at the level of 300-600 ° C). In the area of the MAE outlet part, during the operation of the HKG, the temperature is below this level. Therefore, these compounds in this area will also be in condensed form and also remain there during the entire period of operation of the HKG and after it.

Perchlorates and chlorates of alkali and alkaline earth metals have low decomposition temperatures (at the level of the above peroxides and superoxides), a sufficient level of heat of decomposition and decompose when heated, mainly to chloride of the corresponding metal and oxygen. Chlorides of these metals are high-boiling products and, therefore, during operation, HKG remain in the housing without polluting the released oxygen. Many of them have acceptable operational and technological properties. But perchlorates and chlorates of alkali and alkaline earth metals in the MAE material alone cannot be used, since under certain conditions that have not been studied at the present time, they can decompose in a different way: with the formation of the oxide of the corresponding metal, oxygen and toxic gas - chlorine. Therefore, to neutralize chlorine in the oxygen released by them, they must be used in the MAE material in combination with peroxides and superoxides of alkali and alkaline earth metals.

To increase the rate of oxygen evolution, the MAE material may further include additives that catalyze the thermal decomposition of the substances used in this material. For this purpose, additives from the group of oxides and hydroxides of transition metals and simple and complex salts containing one or more metal cations and one or more anions of the form MT _x O _y (where MT is a transition metal, O is oxygen, x - takes the values 1 or 2, y - takes values from 1 to 7). Most preferred is the use of potassium permanganate as a catalyst.

An analysis of the current level of technology has shown that to date, a multifunctional active element (MAE) with its inherent structure, properties and functions has not been described in the well-known patent and scientific literature, and the use of its or its close analogues in any devices and HCH is unknown.

In addition, it is known that in the prototype and in all analogues, the heat generated by oxygen and slags during the combustion of the charge from the KGM plays a negative role. Due to it, the temperature of the generated HCH oxygen rises to an unacceptable level. This heat is uncontrollable and significantly warms up the generator body during and after operation and requires special measures for thermal insulation, leading to a deterioration in the main indicators of HCH: increasing the size and mass of the generator, reducing the oxygen output per unit mass and volume.

In the claimed method, the heat generated by oxygen and slags during the combustion of the KGM charge, on the contrary, plays a positive role, since it is purposefully used for thermal decomposition of the MAE material and acceleration of the reactions of the interaction of the MAE material with gases present as impurities in the oxygen generated during combustion of the charge , and due to this, obtaining additional oxygen in the HCH, increasing the working time of the HCH and increasing the purity of the oxygen generated by it.

Peroxides and superosides of alkali and alkaline earth metals (the main substances used in MAE) are used in household chemicals: in fabric bleaches, in disinfectants, in hygienic and cosmetic preparations, as components of detergents; in chemical industries: as starting materials for the synthesis of other chemical compounds (hydrogen peroxide and peroxide compounds / edited by ME Pozin. // L-d, M .: GITIHL, 1951); in compositions for air regeneration in breathing apparatus (RF patents: No. 2209647, 2225241, 2210417, 2210416, 2219982, RF application No. 2002131658); in oxygen-generating materials for KHG charges (RF application No. 2001121023, application No. PCT / NL / 02/00596).

However, the properties of these substances, manifested when used in household chemicals and in the synthesis of other chemical compounds from them (solubility, acidity, reaction rate parameters with various substances in solutions, etc.), are in no way related to the properties that they should have as components MAE material (thermal decomposition products and parameters of these reactions, thermophysical characteristics of substances and their decomposition products, etc.) to ensure the operability of the method and device of HCH proposed in the application based on it.

In air regeneration compositions, these substances are used in combination with various other substances (with alkali metal hydroxides, or with hydrogen peroxide and metal hydroxide, or with potassium hydroxide, water and potassium carbonate, or with aluminum hydroxide and aluminum, or with potassium hydroxide, water, potassium carbonate and peroxides of calcium, barium and magnesium, or with oxides, hydroxides and chlorides of potassium, sodium, lithium and magnesium). They are not used in such combinations in the MAE material. Moreover, the known combinations of substances in the compositions for air regeneration exhibit only one property - the purification of exhaled air from human impurities of carbon dioxide and the release of oxygen.

In the well-known KGM for alkaline and alkaline earth metal peroxides and peroxides, the peroxides and superoxides are used in different combinations with various other substances, for example, from the group of metals, and in particular aluminum, magnesium, zinc, molybdenum, iron, manganese, cobalt, nickel; from the group of oxides, and in particular oxides of copper, iron, silicon, zinc, manganese, cobalt, chromium; other types of compounds: sodium and potassium silicates, glass and a number of other substances and with some of the substances proposed in this application: with perchlorates and chlorates of alkali and alkaline earth metals. But KGM with such combinations of components have the obligatory property - the ability to self-combustion with the release of heat. For MAE material, this property is unacceptable, as it leads to a sharp deterioration of the whole complex of basic indicators of HCH. In the MAE material, the proposed substances in those combinations in which they are used in KGM are not used. The MAE material not only does not burn with the release of heat during the operation of the HCH, but, moreover, it absorbs heat in this process. In addition, it possesses properties that are absent in the material known from KGM: the ability to react both itself and the condensed products of its decomposition with harmful gases present as an impurity in the oxygen obtained during the combustion of a charge with the formation of condensed substances.

The use of peroxides and superoxides of alkali and alkaline earth metals and their combinations with other substances proposed in the application for MAE material, as gas coolers, including as chillers of oxygen generated by HCH, or as materials or components of materials for heat-insulating shells or coatings of - either devices, including HKG, either as means for cleaning oxygen generated in HKG from impurities of harmful gases, or as means to increase the operating time of HKG at present The burden is not known.

The device of the agro-industrial complex and its use are known in the art, for example, for limiting the vapor pressure in various devices (Technical Encyclopedia. Vol. 10 / under the editorship of L.K. Martens // "Soviet Encyclopedia", Moscow, 1930). However, in chemical oxygen generators, APCs were not used and could not be used, because when the pressure increases during operation above a predetermined value, high-temperature oxygen with hot particles through an open valve will be released into the environment and may cause burns to the user and also cause a fire, which is unacceptable for safety reasons.

Only in the inventive oxygen generator, the use of the agro-industrial complex in combination with other essential features of the invention gives a new positive quality during the operation of the HCH - improving safety.

Experiments have been verified indicators of preferred embodiments of HCH according to the invention and made their comparison with the performance of the HCH prototype.

Moreover, the compared generators according to the prototype and according to the invention have the same dimensions, materials and weight of the housing and attachment points; dimensions, mass, composition of KGM and charge characteristics, a device for igniting a charge and a filter for purifying oxygen from particles. Sodium superoxide powders with particle sizes ranging from 0.05 to 0.5 mm were used for all types of MAE material. The granular MAE material in all cases had granule sizes ranging from 0.5 to 1.5 mm. The porosity coefficient (æ) of the MAE material in different experiments varied and had values ranging from 14 to 31%. For granular and solid types of MAE material, sodium superoxide was used in a mixture with 5% potassium permanganate, as a catalytic additive, and 5 and 7% cement, as a binder. For the AIC in the generator according to the invention, the set value of the minimum pressure in the compressor was 1.5 and 2 kgf / cm ² . The results of the checks are presented in the table, where: T _to ^m is the maximum oxygen temperature at the outlet of the HCH; T ^m _armature - CCG maximum case temperature during and after operation; τ _p is the HKG operating time; P _ass - set in the agro-industrial complex maximum pressure in the combustion chamber; P _to ^m - the maximum pressure in the HCH during operation.

Table No.
p / p Type HKG Composition, type and parameters of MAE The presence of agribusiness (P _ass ,
kgf / cm ² ) Key indicators of HKG T _to ^m
° C τ _p
min T _cor ^m
° C P _to ^m
kg / cm ² Purity of oxygen generated,
% _(vol) K _v
l / dm ³ K _m
l / kg one Prototype Lack of MAE Lack of agribusiness fifty 12.0 230 7 O ₂ - 97.0%;
CO ₂ - 0.92%;
N ₂ - 0.5%;
H ₂ O - 1.58%; Chlorine + chlorine compounds - 0.0004%. 70 48 2 HCH according to the proposed method based on the prototype according to the scheme in figures 1, 2 NaO ₂ .
Powdery.
æ = 14% AIC, P _back = 2 kgf / cm ² The abnormal work of HCH due to the high resistance of the MAE material (at æ = 14%) to the flow of oxygen in it. 3 Also NaO ₂ .
Powdery.
æ = 15% Agribusiness, P _ass = 2
kgf / cm ² 21 19.0 45 2 O ₂ - 99.3%;
N ₂ - 0.7%; 120 81 four Also NaO ₂ .
Powdered, æ = 22.5%. APK, P _ass = 1.5
kgf / cm ² 25 18.5 48 1,5 O ₂ - 99.3%;
N ₂ - 0.7%; 106 69

5 Also NaO ₂ .
Powdered, æ = 30%. APK, P _ass =
1.5 kgf / cm ² 27 16,4 65 1,5 O ₂ - 99.3%;
N ₂ - 0.7%; 89 62 6 Also NaO ₂ .
Powdery. æ = 31%. APK, P _ass = 1.5
kgf / cm ² 33 15.6 64 1,5 O ₂ - 99.2%;
N ₂ - 0.8%; 75 54 7 Also NaO ₂ + 5% KMnO ₄ . Powdery. æ = 22.5% APK, P _ass =
1,5
kgf / cm ² 19 eighteen 35 1,5 O ₂ - 99.3%;
N ₂ - 0.7%; 117 79 8 Also NaO ₂ + 5% cement. Granules; æ = 22.5%. APK, P _ass = 1.5
kgf / cm ² 26 16.6 59 1,5 O ₂ - 99.3%;
N ₂ - 0.7%; 97 60 9 Also NaO ₂ + 7% cement. Solid,
æ = 22.5%. APK, P _ass = 1.5
kgf / cm ² 28 15.8 47 1,5 O ₂ - 99.2%;
N ₂ - 0.8%; 93 59

The data presented in the table show the following:

- when using MAE material with æ less than 15%, the HCH according to the invention works abnormally, and when using MAE material with большим greater than 30%, the effectiveness of the method proposed in the application is significantly reduced;

- the introduction of an additive of potassium permanganate in the MAE material significantly increases the specific yield of oxygen from HCH (K _v 1.1 times; K _m 1.14 times);

- the considered preferred embodiments of HCH according to the invention, when using MAE material with a value of æ from 15 to 30%, have a significantly higher oxygen yield per unit volume and unit mass of HCH (K _v - 1.3-1.7 times; K _m - 1.1-1.7 times compared with the prototype) at the same time significantly lower body temperature (3.5-6.6 times compared with the prototype), significantly higher purity of oxygen (impurities of harmful gases generated by them) oxygen are absent unlike the prototype), significantly larger operating time (1.3-1.6 times compared with the prototype), a significantly lower temperature of the generated oxygen (1.5-2.6 times compared with the prototype) and a significantly lower level of oxygen pressure in the HCH (in 3.5-4.7 times compared with the prototype).

In general, all the data in the table show that when using the method proposed in the application for invention in HCH, a new positive quality is achieved, consisting in a simultaneous substantial improvement of the whole complex of the main characteristics of HCH.

Technological and hardware design of the proposed method and generator for its implementation are practically feasible, the materials and chemicals used are currently manufactured by industry. The claimed technical solution, in comparison with all the known analogues and prototype, has significantly better basic indicators, allows you to satisfy the long-standing need to ensure a greater likelihood of saving people who are forced to use an autonomous oxygen source for breathing in emergency and extreme situations, and can also be used for technical goals.

Claims (12)

1. A method of producing cold gaseous oxygen in a chemical oxygen generator based on self-sustaining charge burning from an oxygen-generating solid material, including generating oxygen with the formation of high-temperature slags during combustion of a charge placed in the combustion chamber, the evolution of additional oxygen, cooling the generator body, cooling and cleaning impurities at the outlet of the oxygen generator generated by the combustion of the charge, by passing it through placed in the transference between the outer surface of the combustion chamber and the generator case, a multifunctional active element having a porous gas-permeable structure, the material of which is selected from the group of peroxides and superoxides of alkali and alkaline-earth metals, is thermally decomposed under the influence of heat generated during combustion with heat absorption and oxygen evolution, this multifunctional active element and condensed products of its decomposition interact with acid-forming gases with the formation of cond sensitized substances. 2. The method according to claim 1, characterized in that the upper limit of the oxygen pressure in the combustion chamber is limited to a predetermined value using an automatic safety valve by dumping excess oxygen from the combustion chamber through the valve into a multifunctional active element. 3. The method according to claim 1, characterized in that the obtained oxygen is passed through the multifunctional active element in the direction of movement of the charge combustion front. 4. The method according to claim 1, characterized in that the obtained oxygen is passed through the multifunctional active element in the direction opposite to the direction of movement of the charge combustion front. 5. Chemical oxygen generator for producing gaseous oxygen with a temperature close to normal, containing a housing made of metal, preferably steel, or a composite material having one or more outlet openings, a solid charge of oxygen-generating material capable of self-sustaining combustion after initiation with the evolution of oxygen and the formation of high-temperature slag, placed in a combustion chamber located in the housing and having one or more outlet openings rst, while in the space between the outer surface of the combustion chamber and the generator housing there is a multifunctional active element having a porous gas-permeable structure, and the material of which is selected from the group of peroxides and superoxides of alkali and alkaline-earth metals, is thermally decomposed by the heat generated during combustion with heat absorption and oxygen evolution, while the multifunctional active element and the condensed products of its decomposition interact with acid gases with the formation of condensed substances, while the generator also contains a device for igniting the charge, installed at the end of the charge and providing at a given moment the initiation of ignition of the surface of the charge adjacent to this device, and a filter for cleaning the produced oxygen from particles located at the outlet of the generator . 6. The chemical oxygen generator according to claim 5, characterized in that the combustion chamber is equipped with an automatic safety valve. 7. The chemical oxygen generator according to claim 5, characterized in that the combustion chamber is arranged in such a way that the produced oxygen is discharged in the direction of movement of the charge combustion front. 8. The chemical oxygen generator according to claim 5, characterized in that the combustion chamber is arranged in such a way that the produced oxygen is discharged in a direction opposite to the direction of motion of the charge combustion front. 9. The chemical oxygen generator according to claim 5, characterized in that the housing has a mount or mounts that enable the housing to be mounted in devices or attached to equipment or walls. 10. The chemical oxygen generator according to claim 5, characterized in that the housing has a mount or mountings, providing the ability to carry and transport the housing. 11. The chemical oxygen generator according to claim 5, characterized in that the casing is connected to a buffer or balloon through an outlet or holes. 12. The chemical oxygen generator according to claim 5, characterized in that the multifunctional active element is made in the form of a powder, preferably with a particle size of from 0.05 to 0.5 mm, or in the form of granules, preferably with a size of from 0.5 to 1.5 mm, or in the form of a solid porous body, preferably with a porosity ranging from 15 to 30%, or in the form of combinations thereof.

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