EP0952958A2

EP0952958A2 - Devices and methods for producing and using ozone

Info

Publication number: EP0952958A2
Application number: EP97947714A
Authority: EP
Inventors: Rainer W. Sieke
Original assignee: EHMER KARIN
Current assignee: EHMER KARIN
Priority date: 1996-11-02
Filing date: 1997-11-03
Publication date: 1999-11-03
Also published as: AU5398098A; WO1998019961A2; WO1998019961A3; DE19781244D2

Abstract

The invention generally relates to devices and methods for producing and using ozone. More specifically, the invention deals with a device and a process to produce activated ozone structures. According to the invention, the device for producing ozone comprises a high voltage power source, at least two electrodes placed at a distance from each other and a dielectric located between them, whereby said dielectric forms at least one path of flow along the electrodes for the dissociation of incoming oxygen and at least one of the electrodes has holes. In the device the holes connect the path of flow to the path of discharge where no high voltage is available. According to the corresponding method gas is directed from the path of flow through the holes of the electrode into a path of discharge where no high voltage is specifically available. The invention also relates to devices and methods for pollutant and pest control, including cleansing, rendering harmless, neutralization or treatment of poisonous liquids or residues in, for instance, emptied containers and conduits.

Description

Devices and methods for producing and using ozone

description

The invention relates generally to devices and methods for generating ozone, and more particularly to a device and method for generating activated ozone structures. The invention further relates to devices and methods for controlling pollutants and pests, including for cleaning, rendering harmless, neutralizing or treating toxic fluids and residues thereof, for example in emptied containers and lines, and the use of ozone and in particular activated ozone structures for the aforementioned purposes. Basically, the invention is concerned, inter alia, with with a device for generating ozone, which has a high-voltage source and at least two electrodes arranged at a distance from one another, between which a dielectric is arranged which forms at least one flow path along the electrodes used for the dissociation of oxygen, at least one of the electrodes having holes. Such devices are e.g. known from DE 41 41 025 AI and EP 0 571 592 B1. A dielectric arranged between the electrodes serves to generate the so-called silent discharge.

The principle of ozone generation is based on the dissociation of molecular oxygen (O) initially to atomic oxygen (O), which leads to the formation of ozone (O ₃ ) through subsequent attachment to oxygen molecules (O ₂ ). In the simplest case, the chemical reactions are described as follows, taking into account the necessary reaction energies:

O ₂ - »2 0 - 5.1 16 eV

O + O ₂ - = O ₃ + 1.084 eV

From this follows the overall reaction:

3/2 O ₂ -> O ₃ - 1.474 eV This results in a specific minimum energy expenditure of 0.82 kWh / kg, which leads to a maximum theoretical ozone yield of 1,220 g / kWh. Under the most favorable conditions, commercial ozone plants only achieve an energy utilization of 14% in relation to the theoretically possible ozone yield.

In the ozone generators which have become known to date, the target was the ozone generation to use the ozone, although it was known that ozone is highly toxic and has a half-life of more than 5 hours. Many applications use the toxic area (killing germs, viruses, etc.), others use the oxidative area (bleaching processes, industrial oxidation, etc.). So the technical improvements mainly aimed at increasing the ozone yield. The main problem here is that the energy consumption is relatively high, since most of the energy fed into the discharge is lost for the ozone synthesis and is ultimately converted into heat. Since the use of ozone has become uneconomical in many areas of application because of these losses, the long half-life for obtaining the O radicals necessary for oxidation processes and the subsequent destruction of the residual ozone, this medium is little used today relative to its possible uses.

Since 1987, ozone production has been described in two mechanisms:

• Decay of the molecular oxygen to the ground state O ₂ ( ³ Σ ^" g) • Activation of the molecular oxygen [0 ₂ ('Δg), O ₂ (' ∑ ⁺ g), O ₂ (Σ ^" g, v)]

Activated ozone structures can be produced:

Basic state [O ₃ (Αι)],

• excited state [0 ₃ ( ³ B ₂ ), 0 (Αι, v) and O ₃ ('B ₂ )]

• Ionized state 0 ^~ and O ₃ ⁺ From a schematic point of view, as described above, the process can be contracted from the basic state:

3/2 O ₂ - »O ₂ + O -» O ₃ or O ₃ *

3/2 O ₂ - »0 ₂ * + O -> O ₃ or O ₃ * where O ₃ * the activated ozone structures [0 ₃ ( ³ B ₂ ), O ₃ (Αι, v) and O ₃ ('B ₂ ), 0 ₃ ^" and 0 ₃ ⁺ ].

The half-life of these activated ozone structures is described as between 70 ms and 70 s, i.e. there are significantly more radicals available for oxidation purposes in a shorter time.

A plasma, which is characterized by a high electron temperature and a low gas temperature, is fundamentally necessary for the ozone synthesis in an electrical discharge.

The production of activated ozone structures is achieved by removing the molecular oxygen (O ₂ ) from atomic oxygen (O) and the subsequent formation of ozone (O ₃ ) from the discharge gap as quickly as possible. This prevents, among other things, the decay from being caused again by electron impact in the discharge gap. An object of the invention is to provide an apparatus and a method which

Production of ozone with increased ozone-equivalent oxidation ability is made possible.

This goal is achieved in a device for generating ozone, with a high-voltage source and at least two electrodes arranged at a distance from one another, with a dielectric arranged between them, which forms at least one flow path along the electrodes used for dissociation of oxygen, in that at least egg- ne of the electrodes has holes through which the flow path communicates with at least one discharge path.

In other words, a device for generating ozone is created, having a high-voltage source and at least two electrodes arranged at a distance from one another with a dielectric arranged in between, which forms at least one flow path along the electrodes used for dissociation of oxygen, wherein at least one of the electrodes has holes . This device for generating ozone is characterized in that the holes connect the flow path with a discharge path in which there are no high voltages. This design has an astonishing number of advantages:

Through the holes, gas from the flow path, which is sometimes also referred to as a discharge gap, enters the at least one discharge path, namely both the gas introduced and also dissociated oxygen and already formed ozone.

The gas in the discharge path is in a protected room. This is because it is not exposed to any further shock discharges generated by externally applied voltages. Ozone that has already formed cannot therefore be destroyed by induced impacts. It follows that the proportion or the yield of ozone generated is achieved significantly higher than with the known ozonizers with the device according to the invention.

It follows from this that with the device according to the invention, as well as with the method based thereon, the proportion or the yield of ozone generated is substantially higher than in the known ozonizers.

In the discharge path, further oxygen atoms will combine with oxygen molecules to form ozone. This ozone, too, can no longer be destroyed by induced impacts. In addition, there is the further, significant effect that molecules and atoms in the discharge path are electrically charged when they touch the electrodes. Depending on the type of wall charge, neutral oxygen atoms are charged positively or negatively when they are touched. Together with oxygen molecules, these electrically charged oxygen atoms form activated ozone structures. This means ozone at different energy levels and ionized ozone. Electrically neutral ozone molecules can also come into contact with an electrode and be electrically charged in the process, as a result of which further activated ozone structures are formed.

If electrically charged oxygen atoms come into contact with the electrode wall, they can be recharged electrically. This is not a problem because both positively charged and negatively charged oxygen atoms form activated ozone structures together with oxygen molecules.

The fact that a very high proportion of activated ozone is formed is of considerable importance. The decay time of activated ozone is in the range of seconds. In contrast, the decay time of neutral ozone, as it is generated with the known ozonizers, is in the range of hours to days. The invention therefore makes it possible to provide significantly more radicals at the same time, which is crucial for oxidation processes. So that is Ozone-equivalent oxidation ability with the same energy expenditure is about a factor of 10 ³ greater than in the known devices and methods.

Finally, there is also the advantage that the device according to the invention and the corresponding method can be operated with significantly less or even completely without external cooling of the electrodes. This is because the gas emerging through the first holes in the discharge path, as seen in the direction of flow, is only slightly heated. It thus contributes to cooling the electrode in the discharge path both through direct contact with the electrode and by swirling the gas in the discharge path.

The passage through the gas-permeable electrode fulfills the plasma-physical conditions that are important for the optimal reaction phases, that the electron temperature must be higher than the temperature of the ions, atoms and molecules present in the gas.

The formation of the excited states O ( ³ B ₂ ), O (Αι, v) and O ₃ ('ß ₂ ) and O ₃ ^" and O ₃ ⁺ is also due to the collisions with the electrode wall or the electrically conductive filler Electrode, where the exchange of electrons takes place significantly, The generated ozone structures are led into a use room or container or treatment room.

For example, both electrodes can also have holes for discharge paths, which increases the yield.

The outer boundary wall of the discharge paths can be arranged essentially parallel to the electrode (s) having the holes. As a result, the same conditions can be maintained in the flow path forming the discharge channel and in the discharge paths.

According to another embodiment of the construction of the invention, the outer boundary wall of the discharge paths, viewed in the direction of the flow path, has a variable distance from the electrode having the holes. The cross section can be larger or smaller in the longitudinal direction or larger and smaller like a wave. Due to the variable cross-section of the discharge paths, the pressure and surge flow conditions can be influenced in the desired manner.

The electrodes are preferably coated with electrically conductive material. In this way, more stable material can be used under pressure loads.

Each discharge path can be closed on the side facing the entrance of the flow path and open at its opposite end. This further training serves to design the flow guidance.

The flow path can be closed at its end opposite the input end. Through this development of the invention, all gas in the flow path is forcibly directed into and through the discharge path (s). According to another development of the invention, the electrode or the electrodes are divided in such a way that they each form a discharge path, the part facing the flow path having holes and the other part being closed. This training brings a better use of the wall effects. In a further development, both parts of the divided electrode can be electrically connected to one another. However, they can also be optionally connected electrically with different potentials. This enables the potential differences to be used to support the kinetics of the ionization.

The gas passage openings of the holes in the electrodes can be designed to be adjustable, preferably either uniformly or variably over the length of the flow path. This training offers the advantage of the possible regulation of the pressure conditions between the flow path and the discharge path and thus also the possible heat influence.

Each exhaust route can contain a gas permeable material. The material contained reduces the available flow volume and thereby increases the molecular or body impact for O ₃ formation. According to another embodiment of the invention, the gas-permeable material is an electrically conductive material. The gas-permeable material can be designed as a layer or layers and be coated with electrically conductive material.

The discharge path (s) is preferably connected to gas supply lines. This makes it possible to selectively supply desired gases, for example to support the formation of molecules or to reduce NO _x formation.

Furthermore, the flow path can be connected to a pressure control unit, which enables the operation with either constant pressure, positive pressure or negative pressure. By setting the pressure conditions, the power of the generator, the load on the electrodes and higher voltages and thus the sequence and the efficiency of the process can be controlled. The electrodes can be connected to a power supply unit, which can be operated either with direct current, alternating current or steep-edged pulse current. The O ₃ yield can be increased in g / nr by optimal setting.

A plurality of device or ozone generation units described above can be interconnected to form a unit group, which can increase the power throughput. The units of a group can be communicatively connected to a common gas distribution unit. Such an embodiment can also be used to increase the throughput performance and to adapt to room conditions.

Aluminum, titanium or other suitable material can be used as the material for the electrodes. The plasma-physical conditions also include the pressure in the discharge channel, which is called the flow path in the present documents. It affects the time over which nem non-thermal plasma, the condition must be maintained that the electron temperature must be higher than the temperature of the ions, atoms and molecules present in the gas.

The above The object of the invention is also achieved with a method for generating ozone using a high-voltage source and at least two electrodes arranged at a distance from one another with a flow path along the dielectric forming at least one oxygen used for dissociation, in which method gas is led out of the flow path through holes in the electrode or electrodes into a discharge path in which, in particular, no high voltages are present. Another object of the invention is to provide an apparatus and a method for

Combating pollutants and / or pests, i.e. at least essentially rendering them harmless or neutralizing them.

One way to achieve this is by means of a device with ozone generation devices, e.g. an ozone generator, and a treatment room that is open to or contains material with pollutants and / or pests, wherein ozone generated by the ozone generator can be introduced into the treatment room for contact with the pollutants and / or pests. According to the invention, it is provided that the ozone generator is designed to generate activated ozone structures.

In particular, the treatment room can additionally be assigned at least one heat or heat radiation source for the action of heat on the material to be treated in order to mobilize the pollutants and pests, i.e. from solids, solids accumulations or liquids on their surface, where they can be treated by the activated ozone structures.

The ozone generation devices preferably contain at least one device for generating ozone, as stated above. However, the invention is related to one

Device and a method for controlling pollutants and / or pests are not limited to such an ozone generator. Such or the same purpose serving ozone generator is part of a device for controlling pollutants and / or pests. Combating pollutants and pests in the inventive sense means destroying and / or neutralizing these pollutants and pests. In general, a device according to the invention accordingly contains devices for generating activated ozone structures. The activated ozone structures are produced in an analogous manner in accordance with the method based on the above-described ozone generator.

The above aim can also be achieved with a device that has ozone generation devices, such as an ozone generator, and a treatment room that is open to or contains material with pollutants and / or pests, wherein ozone generated by the ozone generator for contact with the Pollutants and / or pests can be introduced into the treatment room. According to the invention, the treatment room is additionally provided with at least one heat or assigned a heat radiation source for the action of heat on the material to be treated. The pollutants and / or pests can thus be mobilized, ie brought to the surface from solids, solid accumulations or liquids where they can be treated by the ozone. In a method according to the invention, pollutants and / or pests with activated ozone structures and possibly ozone are treated. The pollutants and / or pests are preferably also mobilized by the action of heat, so that they emerge or come out of the material to be treated or assume a state in which they can be attacked by the ozone. The ozone generators for the device and the method for combating

In principle, all types known from the prior art are available for pollutants and / or pests, such as, in addition to the device for generating ozone specified above in the context of this invention, also devices such as those e.g. the publications DE 41 41 025 AI, EP 0 571 592 B, DE 31 08 563 AI, DE 26 44 978 AI and DE 28 53 436 AI are specified, the disclosure contents of which are hereby incorporated in full by the reference made in the present documents are.

Microwave devices are given here only as a preferred example of a heat or heat radiation source. The at least one heat or heat radiation source is connected upstream of the generation devices for ozone and / or possibly activated ozone structures and / or partially or possibly completely combined therewith. Possibly. However, an ozone treatment device can also be provided in front of the heat or heat radiation sources in order to treat surface loads before combating pollutants and / or pests emitted by heating.

In terms of the method, in the context of the invention for combating pollutants and pests, heating of the medium to be treated is carried out, if necessary by further measures, and simultaneously or subsequently ozone and / or activated ozone structures are used in order to combat pollutants and / or pests. To treat surface loads at the beginning of the method, however, it is also possible to apply ozone and / or activated ozone structures to the surface before the heating for mobilizing the pollutants and / or pests.

The mobilization causes pollutants to evaporate, so that they come from, for example, the soil or other accumulations of solids, from solids such as e.g. Wood, or leak from a liquid. Then they can be treated with ozone and / or activated ozone structures for destruction and / or neutralization. It is also possible for gas mixtures which contain ozone and / or activated ozone structures to be used which are coordinated with the pollutants and / or their mobilization.

In the case of pests, mobilization also causes them to be made available for ozone treatment. On the one hand, this can be done by the heating come to the surface of a solid or a liquid, so that they are exposed to the toxic and / or oxidizing effect of ozone and / or the activated ozone structures. On the other hand, there are pests, such as the tobacco beetle, which can put themselves in a state in which they are not accessible to the toxic and / or oxidizing effect of ozone and / or the activated ozone structures, for example by "switching off" or ceasing metabolic functions . By heating these pests are forced to resume their metabolism, so that the ozone and / or the activated ozone structures attack and develop their toxic and / or oxidizing effect, which leads to the destruction of these pests. The sources of heat or heat radiation that are used in the sense of the invention are not limited to the microwave devices specified. Depending on the type and structure of the substances to be treated, which are to be freed from pollutants and / or pests, and the pollutants and / or pests themselves, suitable sources of heat or heat radiation can be selected. It is important, however, that the heat or heat radiation sources are only designed and used for the pollutants and / or

Mobilize pests, but not to eliminate the latter. This means that the pollutants or pests are not destroyed or neutralized by means of temperature. This prevents temperature damage to the treated material.

With regard to the basic design and arrangement and the use of heat or heat radiation sources, reference is also made to EP 0 287 549 AI, DE 35 05 571 AI and

EP 0 136 453 A1, whose full disclosure contents are incorporated into the present documents by this reference.

In terms of the device, the components will include heat or heat radiation sources and ozone generation devices, which are not limited to those, as already stated above, which can only provide ozone, but also include those which are also or only activated

Generate ozone structures, used according to a variant of the invention on a self-propelled or towed vehicle for soil treatment on the spot. The heat radiation that may be used can be directed at the soil forming the base and its pollutants evaporated thereby or the pests resulting therefrom can then be exposed to the ozone and / or the activated ozone structures, which are fundamentally particularly suitable, as described in detail above become. The previous or possibly simultaneous heating of the floor, as already mentioned, may be optional. With regard to further developments of these configurations, reference is also made to US Pat. No. 5,566,627, the disclosure content of which is fully incorporated into the present documents by the present reference. Possibly the soil can also be removed to a certain depth by suitable means and transported on a conveyor belt or the like by the device according to the invention installed on the vehicle and then put down again. For this purpose, the vehicle can have a treatment tunnel as a treatment room, which can also contain suitable safety devices, such as radiation and gas shields or locks, so that for example, microwave devices for mobilizing the pollutants and / or pests and other neutralizing or toxic substances can be used.

In order to extend the effective time for the ozone and / or the activated ozone structures, according to a further development it is provided that at the end of the vehicle a carpet is drawn up, which covers the floor, which may have been removed and in any case treated, so that the ozone and / or the activated ozone structures cannot evaporate so easily.

However, the aforementioned tunnels on a vehicle cannot only be used on them. Stationary versions that can have the same equipment are e.g. for the treatment of contaminated and / or pest contaminated wood both in the raw form, as well as in processed or processed form, i.e. for example as boards, but also as entire furniture, encompassed by the invention. For example, panels, boards and furniture contaminated with formaldehyde can be disinfected.

In this respect, however, the invention is not limited to the treatment of wood, but can be used for any suitable materials and objects, both in connection with a tunnel through which the materials or objects to be treated are transported and in the form of stationary chambers in which the materials or objects to be treated are placed during treatment.

Further embodiments of the device of the invention are, for example, hand-held devices with an ozone generator and possibly a heat source or the like, which can be used in places that are difficult to access or locally restricted contaminations. Medium-sized devices, for example for treating parquet or other floors in the form of a vacuum cleaner, for example, can also be used.

If a microwave device is used as the heat radiation source, appropriate safety precautions may have to be taken in accordance with national regulations. Care must be taken to ensure that during operation of the device which is appropriately equipped in accordance with the invention, no micro-wave radiation in the area of personnel and other devices of the device can get outside the latter, except where appropriate in the treatment area if the treatment room is open to the material to be treated . Depending on the other design, suitable measures are, for example, the installation of protective blankets or suitable locks and / or shields. As stated at the beginning, the invention further relates to a device, a method and a substance and their use for cleaning, rendering harmless, neutralizing or treating toxic fluids and residues thereof in emptied containers and lines.

Et al there is a problem with, for example, earthbound missile and rocket fuel tanks and lines, cleaning the latter after use so that they are free of toxic substances which are contained in the fuels and fuels used.

A particularly toxic and difficult to remove or neutralize constituent of such toxic substances is, for example, hydrazine, which is also referred to as diazane or diamide and has the chemical formula H ₂ N-NH ₂ with a molecular weight of 32.05. It is about a colorless, oily, toxic air with a strong ammonia-like odor. In addition to water (cf. hydrazine hydrate), hydrazine can also be mixed with alcohols. Hydrazine forms an azeotrope with water at 120.5 ° with a hydrazine content of 58.5%. Since hydrazine has been shown to be carcinogenic in animal experiments, the previous MAK value was converted into a TRK value (0.13 mg / m ³ ) in 1980 and hydrazine was included in List III A2 of carcinogenic agents with a weak carcinogenic effect. A carcinogenic effect in humans has not yet been demonstrated. Hydrazine and its aqueous solutions are toxic. In liquid form or as a vapor, hydrazine has a strong irritant effect on the skin and mucous membranes, and local skin sensitization is also possible. As an exothermic compound, hydrazine decomposes into nitrogen and ammonia at temperatures above 250 ° - possibly explosively.

Concentrated aqueous solutions have a pH of 12-13 and are very aggressive against rubber and cork; with exposure to glass for several years, even glass is attacked. Like liquefied ammonia, hydrazine dissolves many inorganic salts and, as a strong reducing agent, shows great reactivity to many chemicals; so it reduces e.g. ammoniacal silver salt u. Fehling's solutions already in the cold to metallic silver or copper (I) oxide. As a divalent base, hydrazine reacts with acids to form two rows of hydrazinium salts, combines with metals or metal amides and hydrides to form hydrazides and forms hydrazones with aldehydes and ketones. The alkyl and aryl hydrazines, azines and the hydrazo compounds are also derived from hydrazine. Test tubes and the Compur 4100 S Monitox gas trace warning system are suitable for detecting hydrazine vapors.

Anhydrous hydrazine and its derivatives (especially methylhydrazines) are used as rocket fuel due to their high heat of combustion (e.g. the Apollo lunar vehicle was made with a 1: 1 mixture of H ₃ C-NH-NH ₂ and (H ₃ C) ₂ N-NH ₂ operated; nitrous oxide N ₂ O ₄ ) was used as the oxidant. Hydrazine can also be used as an energy source in fuel cells. Hydrazine and its derivatives are base products for plastics, dyes and adhesives,

Plant protection agents, pharmaceuticals, etc. Aqueous hydrazine solutions are versatile reducing agents, e.g. in the production of silver and copper mirrors, in the deposition of colloidal platinum deposits or in chemical analysis. Their use as a corrosion inhibitor for water-steam cycles is important. Hydrazine acts as a passivation layer, oxygen-binding and alkalizing. The hydrazine determination in the boiler feed water can be carried out electrochemically or colorimetrically using 4-dimethylaminobenzaldehyde as a reagent. Hydrogen peroxide in the presence of Pd-doped ion exchangers is particularly suitable for removing hydrazine residues in waste water; Another option is oxidation using sodium hypochlorite. In organic chemistry, hydrazine is used to reduce the carbonyl group to the methylene group (Wolff-Kishner and Huang-Minlon reduction). Versatile

Hydrazine and its derivatives are also used in the synthesis of heterocycles or as antioxidants for the stabilization of aromatic amines, phenols, oils, fats and rubber. The areas of application of crop protection agents, foam blowing agents and corrosion inhibition have achieved the greatest economic importance. With regard to further details on hydrazine, reference is made to "CD Römpp Chemie Lexikon - Version 1.0", Stuttgart / New York: Georg Thieme Verlag 1995, and the content of the disclosure thereof is hereby incorporated in its entirety into the present documents by reference. The already mentioned importance of hydrazine as a fuel and fuel leads to the fact that hydrazine is used in large quantities and in many different ways, so that complex cleaning work for the containers and lines is required on the operating facilities so that the latter can be safely maintained and repaired, such as, for example is required for tanks and lines that are used in the area of launch ramps. In connection with the use of hydrazine as a rocket fuel, the containers and lines that were used and were empty after the takeoffs were completed or possibly canceled were rinsed with plenty of water. In addition to the large water consumption, this has the disadvantage that a large amount of contaminated water is produced, which must be disposed of. Furthermore, such a method, for which appropriate devices are known and used in practice from the prior art, requires a great deal of time until adequate cleaning of the containers and lines has been achieved by rinsing with water.

The aforementioned problems exist not only with hydrazine, but with almost all toxic fluids, such as pastes, inter alia, liquids and gases, which are to be understood as fluids in the context of the invention. Another source of poison is, for example, fluids that contain cyanides. These are salts of hydrocyanic acid (hydrocyanic acid, HCN). These contain the colorless, toxic anion NC. The compounds derived from the tautomeric form ( ^~ NC) are called isocyanides. Due to formal parallels, the cyanides are sometimes combined with cyanates etc. as pseudohalogenides. The alkali cyanides (e.g. potassium cyanide, KCN or sodium cyanide, NaCN) and the alkaline earth cyanides (e.g. calcium cyanide, Ca (CN) ₂ ) are water-soluble, very toxic (MAK 5 mg / m ³ , calculated as CN, cf. hydrocyanic acid) , react strongly alkaline due to hydrolysis and smell of hydrocyanic acid. The simple, normal heavy metal cyanides are mostly insoluble (example: silver cyanide, AgCN), whereas mercury (II) cyanide (Hg (CN) ₂ ) is soluble.

Cyanides are used as an intermediate in organic syntheses of carboxylic acids, pharmaceuticals, dyes and pesticides. Larger amounts of cyanides are also required as so-called pushers for flotation, surface treatment of metals, electroplating and cyanide leaching. In waste water from such processing plants, cyanides represent a considerable environmental problem. For detoxification, cyanides, as is practiced in the prior art, can be destroyed oxidatively (using hypochlorite, hydrogen peroxide and peroxo compounds), but these processes are all very complex and lengthy, and involve great risks for the staff. Processes for the regeneration of old salts containing cyanide have been developed for hardening technology, which is also only possible with considerable effort and risk. Teaching about the handling of hydrogen cyanide / cyanides the leaflet for hazardous substances in BG Chemie M002, edition 4/85; Guidelines of the BMA (1963) are available for the operation of cyanide hardening shops.

With regard to further details on cyanides, reference is also made to "CD Römpp Chemie Lexikon - Version 1.0", Stuttgart / New York: Georg Thieme Verlag 1995, and the disclosure content thereof is included in full in the present documents by the reference thus made.

The present invention further aims to solve the above problems in detoxifying liquids and cleaning containers and pipes.

This is achieved according to the invention with a device for cleaning, rendering harmless, neutralizing or treating toxic fluids and residues thereof in emptied containers and lines, with connection devices for introducing treatment fluids into the toxic fluids or the containers or lines. This includes devices for generating ozone and / or activated ozone structures which can be connected to the connection devices, so that ozone and / or activated ozone structures can be / are introduced as a treatment fluid into the toxic fluids or the emptied containers or lines.

The toxic fluids can either be treated from their surface, or discharges into the toxic fluids are included, so that ozone and / or activated ozone structures are pressed into the toxic fluids. Another alternative in terms of device and method is to vaporize the toxic fluids and to mix this vapor with ozone and / or activated ozone structures.

In principle, the invention provides the possibility of providing ozone and supplying or using it in the containers or lines. However, due to its half-life, normal ozone still requires a period of around 3 to 5 hours in order to have a sufficient effect to neutralize or neutralize the toxic substances. If the activated ozone structures preferred according to the invention are used instead of normal ozone, the desired effect can e.g. can be reached after about 10 minutes. Both normal ozone and activated ozone structures have the advantage that there are no substances that ultimately have to be disposed of.

In particular, the containers or lines are those for holding fuels. The latter can contain hydrazine. For the purposes of the invention, however, a toxic fluid is also to be understood, for example, to be one with cyanide fractions without being restricted to certain substances, i.e. toxic fluids is sought.

To generate activated ozone structures, the devices for generating ozone contain an ozone generator according to the above-mentioned device for generating ozone. The activated ozone structures are produced in an analogous manner in accordance with the method based on the above-described ozone generator.

However, other devices for providing ozone can also be part of the device specified here, such as those ozone generators that are specified above Prior art publications can be found, such as DE 41 41 025 AI, EP 0 571 592 B, DE 31 08 563 AI, DE 26 44 978 AI and DE 28 53 436 AI.

In addition, control devices can be provided which are designed to generate and / or supply ozone and / or activated ozone structures into the toxic fluids or the containers and lines depending on operating parameters of the devices for generating ozone and / or activated ozone structures, from To control the state of the toxic fluids or the containers or lines, in particular their filling state, temperature, internal pressure, degree of contamination etc., and / or the type and composition of the toxic fluids.

This embodiment can be further developed in that detection devices assigned to the control devices are provided, which are designed to determine the operating parameters of the devices for generating ozone and / or activated ozone structures, the condition of the toxic fluids or the containers or lines, in particular their Fill level, temperature, internal pressure, degree of contamination, etc., and / or to record the type and composition of the toxic fluids and to forward them to the control devices as control variables. As an alternative to the above-mentioned further training measures in the invention, the connection devices for introducing treatment fluids into the toxic fluids or the containers or lines can be designed for various treatment fluids and / or at least one treatment fluid at a plurality of locations in the toxic fluids or the containers or initiate lines. A further development within the scope of the invention provides that the connection devices and / or possibly the control devices are designed to control the treatment fluid introduction in terms of quantity and / or time.

In a method according to the invention for cleaning, neutralizing, neutralizing or treating toxic fluids and residues thereof in emptied containers and lines, treatment fluids in the toxic fluids or the containers or via connecting devices

Lines are introduced, at least one treatment fluid is introduced, which contains ozone and / or activated ozone structures.

This can be accomplished, in particular, by using one of the devices which are given above in various embodiments and possibilities for realizing the device according to the invention.

Finally, the use of ozone and / or activated ozone structures for cleaning, rendering harmless, neutralizing or treating emptied containers and lines for toxic fluids and for these toxic fluids or generally toxic substances is directly created and claimed within the scope of the invention. According to preferred embodiments, the toxic liquids are fuels or fuels, which may contain hydrazine in particular, or those with at least cyanide components. Finally, the invention also includes a substance for cleaning, rendering harmless, neutralizing or treating toxic fluids and residues thereof in emptied containers and lines, the substance containing ozone. Alternatively or additionally, the substance can contain activated ozone structures and / or can be a treatment fluid. The invention is not limited to certain applications of hydrazine or cyanides or to hydrazine or cyanides, but can generally be used in connection with toxic fluids.

Further advantages and features of the invention result from the independent and dependent claims and their combinations. The design options of the devices and methods explained above are readily clear to a person skilled in the relevant art on the basis of the above written representations, so that a more detailed list of implementation examples and their graphic representation can be omitted without thereby restricting the disclosure content of the present documents and to complicate the understanding of the expert. The preferred configurations given above already provide sufficiently concrete information about the preferred and best ways of carrying out the invention, so that a repetition thereof is not necessary in the context of a description of preferred exemplary embodiments.

However, as far as the device according to the invention for generating ozone and the method based thereon and the effects of ozone and activated ozone structures are concerned, details are given below on the basis of concrete examples with reference to the accompanying drawings, from which further features and advantages of the invention can be found are. The drawings show:

1 shows a schematic sectional view of an ozonizer according to the invention, FIG. 2 shows a number of ozone generators connected in parallel,

3 shows an ozone generator with gas-permeable material in the discharge paths, and

4 to 7 the effect of activated ozone structures in connection with the degradation of hydrazine on the basis of test results shown in a log or graph.

FIG. 1 shows a schematic sectional view of an apparatus according to the invention for generating ozone, such as an ozonizer or ozone generator. Two divided electrodes 10 are each fastened in a holder 12 at an approximately parallel distance from one another. A dielectric 17 is arranged between the two electrodes 10. A discharge channel is formed between each electrode 10 and the dielectric 17 and is referred to as flow path 14 in the present description. The dielectric 17 is held at its right end in the figure by parts 18 which at the same time close off the end of the flow paths 14 facing them. The side 10a of each electrode 10 facing the flow path 14 has holes 20 through which gas can flow from the flow path into the discharge paths 16. The other side 10b of each electrode is closed.

The electrodes 10 are electrically connected to a power supply 22. The discharge paths 16 are connected via valves 24 to lines 26, via which optionally desired gas can be introduced into the discharge paths 16.

In operation, the desired gas, for example air or oxygen, is introduced into the flow paths 14 in the direction of the arrow while the electrodes 10 are supplied with the desired voltage. The so-called silent discharge takes place in the flow paths 14, in which atomic oxygen and, by combining atomic oxygen with molecular oxygen 0 ₂ , also ozone are formed.

The oxygen atoms and ozone molecules that enter one of the discharge paths 16 through one of the holes 20 are located in a safe zone in which there are no high voltages. The ozone located there is discharged through the outlet of the discharge paths 16 and is available for use e.g. in a treatment room (not shown), as specified above in connection with design options for a device and a method for controlling pollutants and / or pests.

It is pointed out that in the known ozonizers all ozone formed must flow through the entire length of the ionization gap in the form of the flow paths 14. A considerable part of the ozone already formed is destroyed there again on its way through the ionization gap, inter alia by means of electrically induced impacts. This significantly reduces the efficiency of the known ozonizers.

Due to the inflow of gases through the various holes 20 of the electrodes 10 into the discharge paths 16, there is considerable swirling. This promotes the desired wall contacts of the gases. This ensures two advantages. On the one hand, oxygen atoms and ozone molecules are electrically charged or recharged, which is desirable. On the other hand, excessive heating of the electrodes 10 delimiting the flow path 14 is prevented.

FIG. 2 shows a number of ozone generation devices or generators which are connected together in parallel to form a unit group. Such an ozone generator battery enables a correspondingly increased generation of ozone and radicals. The

FIG. 3 shows an ozone generator unit in which gas-permeable material is contained in the discharge paths 16, the effect of which was described above.

The effect of activated ozone structures has been tested in connection with the degradation of hydrazine. The test results are shown in protocols or graphs in FIGS. 4 to 7. In a first trial, 50 mg of hydrazine with activated ozone structure was treated. Fig. 4 shows the measurement protocol and Fig. 5 is a graphical representation of the amount of hydrazine present over time.

In a second trial, 125 mg of hydrazine with activated ozone structures was treated. Fig. 6 shows the measurement protocol and Fig. 7 is a graphical representation of the amount of hydrazine present over time.

As the tests show, in both cases examined, the hydrazine present at the start of the test was completely degraded after about 10 minutes. The invention thus enables efficient, quick and safe cleaning of containers and lines contaminated with toxic substances by filling or flushing the latter with ozone and / or activated ozone structures, and for this purpose creates the devices and methods and gives the corresponding novel use of ozone and activated ozone structures.

In addition to the technical areas specified in the introduction to this description, in which the device, the method and substance and their use according to the invention can be used, the latter also includes all other possible uses, in particular within the scope of the associated claims. By referring in places to fuel and fuel technology as well as missile and missile applications or cyanides, the invention is not restricted to this, but is only explained by way of example on the basis of this information. Likewise, the exemplary representation of an embodiment of the invention in connection with tests with hydrazine is not intended to limit the invention, which is used for cleaning or neutralizing or generally treating containers and lines, which are filled with various other toxic or toxic fluids which are viscous, liquid or gaseous be filled, or such and other toxic fluids can be applied directly. In particular, the solutions according to the invention can render any toxic fluids, such as liquids, which are used in technical processes or for cleaning, including pest control, harmless after their use.

The invention is not restricted to specific exemplary embodiments or preferred configurations, but relates to the entire disclosure of the present documents and in particular also to the information in the claims. Furthermore, reference is made to the following documents, the contents of which, individually and in combination, also belong to the disclosure content of the present documents: DE 41 41 025 AI, EP 0 571 592 B, DE 31 08 563 AI, DE 26 44 978 AI, DE 28 53 436 AI, DE 35 05 571 AI, EP 0 287 549 AI and EP 0 136 453 AI and US-5,566,627. In addition to the content of the abovementioned documents, this also includes the disclosure content of the present documents, which the person skilled in the art, including his specialist knowledge, includes the present documents, including the older publications mentioned and theirs

Combinations can take. Insofar as the type of generation of ozone or activated ozone structures is not essential in the context of the invention, the invention is also independent of which ozone generators will be available in the future.

Claims

Expectations

1. Device for generating ozone, with a high voltage source and at least two electrodes (10) arranged at a distance from one another with a dielectric (17) arranged between them, which forms at least one flow path (14) used for dissociation along the electrodes, at least one of the electrodes (10) having holes (20), characterized in that a discharge path (16) is connected to the flow path (14) via the holes (20) in the at least one electrode (10).

2. Device according to claim 1, characterized in that two electrodes (10) are provided, both of which have drainage paths (16) towards holes (20).

3. Device according to one of the preceding claims, characterized in that the outer boundary wall of the at least one discharge path (16) is arranged substantially parallel to the or the holes (20) having electrode (s) (10).

4. Device according to one of the preceding claims, characterized in that the outer boundary wall of the at least one discharge path (16) in the direction of the flow path (14) seen an uneven or variable distance to the or the holes (20) having electrode (s) (10) has.

5. Device according to one of the preceding claims, characterized in that the electrodes (10) are coated with electrically conductive material.

6. Device according to one of the preceding claims, characterized in that the discharge path (s) (16) on the side facing the input of the flow path (14) is closed and is / are open at its / its opposite end.

7. Device according to one of the preceding claims, characterized in that the flow path (14) is closed at its end opposite the input end.

8. Device according to one of the preceding claims, characterized in that the

The electrode or electrodes (10) is / are divided in such a way that they each form a discharge path (16), the part (10a) facing the flow path (14) having holes (20) and the other part (10b) being closed .

9. Device according to one of the preceding claims, characterized in that both parts (la, 10b) of a divided electrode (10) are electrically connected to one another.

10. Device according to one of the preceding claims, characterized in that both parts of a divided electrode (10) are optionally electrically connected to different potential applied.

11. Device according to one of the preceding claims, characterized in that the gas passage openings of the holes (20) of the electrode (s) (10) are optionally adjustable.

12. Device according to one of the preceding claims, characterized in that the discharge electrodes (10) are plate-shaped or tubular.

13. Device according to one of the preceding claims, characterized in that the or the discharge path (s) (16) contain a gas-permeable material.

14. The apparatus according to claim 13, characterized in that the gas-permeable material is an electrically conductive material.

15. The device according to one of claims 13 or 14, characterized in that the gas-permeable material is formed as a layer and is coated with electrically conductive material.

16. Device according to one of the preceding claims, characterized in that the discharge path (s) (16) are connected to gas supply lines (26).

17. Device according to one of the preceding claims, characterized in that the flow path (14) is connected on the input side to a pressure control unit which allows the operation either with the same pressure, positive pressure or negative pressure.

18. Device according to one of the preceding claims, characterized in that the electrodes (10) are connected to a power supply unit (22) which allows the operation either with direct current, alternating current or steep-edged pulse current.

19. Device according to one of the preceding claims, characterized in that a plurality of units for generating ozone according to one of the preceding claims are interconnected to form a unit group.

20. Device according to one of the preceding claims, characterized in that the units of a group are communicatively connected to a common gas distribution unit.

21. Method for generating ozone using a high-voltage source and at least two electrodes (10) arranged at a distance from one another with a flow path (14) arranged therebetween and forming at least one oxygen (17) arriving for dissociation along the dielectric (17) ), at least one of the electrodes (10) having holes (20), characterized in that gas from the flow path (14) is guided through the holes (20) in the at least one electrode (10) into a discharge path (16).

22. The method according to claim 21, characterized in that the discharge path (16) is optionally supplied with gases.

23. The method according to claim 22, characterized in that gas in the discharge path (16) is passed through a gas-permeable material.

24. The method according to any one of claims 21 to 23, characterized in that the gas from the flow path (14) through the holes (20) in the at least one electrode (10) in the a discharge path (16) forming the electrode (10) becomes.

25. Device for combating pollutants and / or pests with ozone generating devices and at least one treatment room, in which ozone can be introduced by means of the ozone generating devices, characterized in that the ozone generating devices are designed for generating activated ozone structures.

26. The apparatus according to claim 25, characterized in that the ozone generating devices upstream and / or effectively combined with these heat treatment devices are provided.

27. Device for combating pollutants and / or pests with ozone generating devices and a treatment room into which ozone can be introduced by means of the ozone generating devices, characterized in that heat treatment devices are provided upstream and / or effectively combined with these.

28. The apparatus according to claim 25 or 26, characterized in that the ozone generating devices contain at least one device for generating ozone according to one of claims 1 to 20.

29. Device according to one of claims 25 to 28, characterized in that the treatment room is stationary, mobile, displaceable or transportable, and that the treatment room is preferably designed for carrying out the ozone treatment and possibly the heat treatment and in particular is at least essentially lockable.

30. The device according to claim 29, characterized in that cover devices are provided in a mobile or displaceable treatment room, which are connected downstream in the direction of travel or displacement and to cover the treated and / or dispensed material for an after-effect time of the ozone and / or the activated ozone structures and possibly other gases.

31. The device according to one of claims 25 to 30, characterized in that the

Heat treatment devices contain microwave devices and are possibly assigned to the treatment room, and that, in particular, safety devices are included for operating the microwave devices, which prevent microwave radiation from escaping from the treatment room at undesired locations.

32. Device according to one of claims 25 to 31, characterized in that the

Ozone generation devices, the treatment room and possibly the heat treatment devices are accommodated in a hand-held device or a device similar to a vacuum cleaner.

33. Device according to one of claims 25 to 31, characterized in that the ozone generation devices, the treatment room and possibly the heat treatment devices are housed in, on or on a self-propelled device and / or a trailer.

34. Device according to one of claims 25 to 33, characterized in that the treatment room means for in particular semi-automatic or fully automatic Carrying out the material to be treated has that preferably devices are provided for in particular semi-automatic or fully automatic loading of the treatment room, and that the treatment room is preferably a treatment tunnel.

35. Device according to one of claims 25 to 33, characterized in that the treatment room is open on one side. and that the open treatment room side lies against the material to be treated.

36. Device according to one of claims 25 to 35, characterized in that further gas supply and / or radiation devices are assigned to the treatment room, so that further treatment gases and / or radiation can act on the material to be treated.

37. Device according to one of claims 25 to 36, characterized in that a

A plurality of treatment rooms is provided, and preferably devices for an in particular automatic transport of the material to be treated from one to the next treatment room are included,

38. Device according to one of claims 25 to 37, characterized in that a first ozone treatment can be carried out before a heat treatment, and that a second ozone treatment can be carried out during or after the heat treatment.

39. Process for combating pollutants and / or pests, characterized in that activated ozone structures are generated and passed onto a surface to be treated or into a material to be treated.

40. The method according to claim 39, characterized in that the to be treated

Surface, or the material to be treated, before, during and / or after the ozone treatment, is subjected to a heat treatment which is designed to mobilize the pollutants and / or pests to be controlled, and in particular a microwave treatment is provided as the heat treatment.

41. A method for combating pollutants and / or pests, wherein ozone is generated and passed onto a surface to be treated or into a material to be treated, characterized in that the surface to be treated or the material to be treated before, during and / or after the ozone treatment is subjected to a heat treatment which is designed to mobilize the pollutants and / or pests to be controlled, and in particular a microwave treatment is provided as the heat treatment.

42. The method according to any one of claims 39 to 41, characterized in that the material to be treated is wholly or partially introduced for treatment in a preferably at least substantially closed or lockable space, such as wood in a treatment room, and / or is conveyed through it, such as soil through a particularly mobile tunnel.

43. The method according to any one of claims 39 to 42, characterized in that for ozone treatment and possibly heat treatment, ozone generation devices and possibly heat treatment devices are moved in particular closely over a surface to be treated.

44. The method according to any one of claims 39 to 43, characterized in that a device according to one of claims 1 to 20 is used and / or a method according to one of claims 21 to 24 is used.

45. Use according to one of claims 1 to 20 or a method according to one of claims 21 to 24 for combating pollutants and / or pests.

46. Apparatus for cleaning, rendering harmless, neutralizing or treating toxic fluids and residues thereof in emptied containers and lines, with connecting devices for introducing treatment fluids into the toxic fluids or the containers or lines, characterized in that devices for generating ozone and / or activated ozone structures are contained which can be connected to the connection devices, so that ozone and / or activated ozone structures can be introduced as a treatment fluid into the toxic fluids or into the emptied containers or lines.

47. Apparatus according to claim 46, characterized in that it is fuels, in particular those which contain hydrazine, and / or that the toxic fluids contain cyanides in the case of toxic fluids.

48. Device according to claim 46 or 47, characterized in that ozone generating devices according to one of claims 1 to 20 are included.

49. Device according to one of claims 46 to 48, characterized in that control devices are provided which are designed to generate and / or supply ozone and / or activated ozone structures in the toxic fluids or the emptied containers and lines depending on Control the operating parameters of the devices for generating ozone and / or activated ozone structures, the state of the toxic fluids or the containers or lines, in particular their fill level, temperature, internal pressure, degree of contamination etc., and / or the type and composition of the toxic fluids.

50. Apparatus according to claim 49, characterized in that the control devices are assigned detection devices which are designed to determine the operating parameters of the devices for generating ozone and / or activated ozone structures, the condition of the toxic fluids or the containers or lines, in particular to record their fill level, temperature, internal pressure, degree of contamination etc., and / or the type and composition of the toxic fluids and to transmit them to the control devices as control variables.

51. Device according to one of claims 46 to 50, characterized in that the connection devices for introducing treatment fluids into the toxic fluids or the containers or lines are designed to various treatment fluids and / or at least one treatment fluid at a plurality of locations in the discharge toxic fluids or the containers or lines.

52. Device according to one of claims 46 to 51, characterized in that the connection devices and / or possibly the control devices are designed to control the treatment fluid introduction in terms of quantity and / or timing.

53. A method for cleaning, rendering harmless, neutralizing or treating toxic fluids and residues thereof in emptied containers and lines, wherein treatment fluids are introduced into the toxic fluids or the containers or lines via connecting devices, characterized in that at least one treatment fluid is introduced, which contains ozone and / or activated ozone structures.

54. The method according to claim 53, characterized in that a device according to one of claims 1 to 20 is used and / or a method according to one of claims 21 to

24 will be applied.

55. Use of ozone and / or activated ozone structures for cleaning, rendering harmless, neutralizing or treating toxic fluids and residues thereof in emptied containers and lines.

56. Use of ozone and / or activated ozone structures according to claim 55. characterized in that the toxic fluids are fuels, in particular those which contain hydrazine and / or fluids which contain cyanides.

57. Substance for cleaning, rendering harmless, neutralizing or treating toxic fluids and residues thereof in emptied containers and lines, characterized in that the substance contains ozone and / or activated ozone structures.

58. Substance according to claim 57, characterized in that it is a treatment fluid.