FR2765322A1 - MODULAR MOBILE DISPOSAL SYSTEM - Google Patents

Abstract

The present invention relates to a mobile modular disposal system by which materials containing toxic and / or explosive substances, in particular weapons, can be disposed of. After dismantling the weapons, toxic substances are removed in individual modules, for example, via a high-pressure plasma installation to which a gas cleaning system is connected. In a particularly advantageous manner, the disposal system according to the invention can be brought to a determined site of use and, after disposal on the site, it can be disassembled into modules and brought to the next site.

Description

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  The present invention relates to a method of disposing of materials, in particular weapons, containing toxic and / or explosive substances, according to which the weapons are dismantled and the separate sub-units of the weapons, obtained during dismantling, are routed respectively a specific module for each sub-unit; the sub-units which are not contaminated by toxic substances and which contain explosive substances are sent to a module in which the explosive substances are thermally converted in a controlled manner and any solids present are separated; and the subunits, which contain the toxic substances, after separation of their envelopes, are routed at least to a plasma module which contains a plasma produced by induction or by discharge from a hot cathode, which is charged with at least one reactive gas, the toxic substances being broken down in the plasma into less toxic products or

1.5 non-toxic.

  The present invention also relates to a mobile modular elimination installation for implementing this method, comprising: at least one module for dismantling weapons containing toxic substances and / or explosive substances, in which the weapons are broken down into separate sub-units; at least one explosive substances elimination module for the controlled thermal conversion of explosive substances contained in weapons; and at least one plasma module, which comprises at least one device for producing a plasma at high temperature by discharge at high

  frequencies or discharge of a hot cathode.

  The elimination of dangerous and toxic substances has been playing an increasingly important role in recent times. This is due, on the one hand, to the fact that, for example, toxic chemical waste and by-products have to be disposed of. But, on the other hand, there are still huge amounts of old military warheads, largely from the First World War, of chemical weapons used at the time. Likewise, there are amply overstocked weapons depots in the Russian Federation

  with toxic substances, which will have to be eliminated soon.

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  As toxic substances, the following products may be mentioned, for example: l tC1 tCl 1 z ci D-0L'AC 1.As ,, '", w, C! I As1" ", C 1 phosgene Lewisite 1 Lewisite 2 Lewisite 3 f., / C-,

VS! CE..N

  Clark I Clark II Satin Soman CCH] 151-H1 \ e ci c

H. C C

  o Tabun mustard gas But it is also necessary to eliminate other substances such as, for

  example, organic esters of thiophosphoric acid, in particular S-

  o-ethyl diisopropylaminoethyl-methylthiophosphonate (VX) or the

  phenarsazine, all of which are toxic.

  Hitherto in the state of the art, attempts have been made to eliminate the abovementioned substances by combustion at high temperature. However, the combustion of these materials in high temperature central installations generally presents a corresponding potential danger and is unsuitable for

  disposal of small quantities.

  A first promising approach for the elimination of toxic materials is described in German patent DE44 28 418 of the present Applicant. There is disclosed a method and a device for rendering toxic gases or toxic gasifiable substances inert. In this process, a gas to be eliminated is directed into a low-pressure plasma gallery, which is placed on a vehicle, and decomposes therein into less products.

  3 5 toxic more energetically interesting.

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  This process has certainly proven itself in practice, but the conversion of toxic substances is quantitatively too low per unit

of time.

  Starting from this state of the art, an object of the present invention has been to provide a method as well as a mobile device which make it possible to eliminate materials containing toxic substances and also explosive substances, in a reliable and respectful of the environment. This object is achieved, in accordance with the invention, by a process of the type o mentioned in the introduction, which is characterized in that the envelopes contaminated by the toxic substances are decontaminated hot in another plasma module; and in that all the burnt gases produced are

  routed to a central module for purifying burnt gases.

  The installation of the type mentioned in the introduction, which is used for the implementation of this process, is characterized in that it comprises at least one other plasma module for the thermal decontamination of envelopes, which are contaminated with toxic substances , as well as at least one module

purification of burnt gases.

  The implementation of the mobile modular system for eliminating chemical weapons starts from the fact that the chemical weapons to be eliminated can be extremely different in terms of the chemical structure of toxic compounds and the state of the actuation mechanisms, devices and equipment; the state of the actuation mechanisms, devices and equipment prohibits transport, and disposal on site is an absolute necessity; the quantities of chemical weapons to be eliminated on the various storage sites and places of discovery determine the choice of the method of elimination and, consequently, the composition of the modular system to be implemented; disposal operations are controlled and monitored

  by complete and automatic monitoring.

  The legal provisions in force in the respective country of intervention for the protection of people and the environment can be respected, the modular system, of different composition depending on the chemical weapons to be eliminated, can be brought, at determinable time intervals , at the place of storage to destroy weapons containing toxic substances and the system can also be used to

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  elimination of other highly toxic substances, including in cases

damage and disaster.

  The mobile modular system according to the present invention comprises at least part of the modules described below according to the materials to be eliminated: There is a module for dismantling old and recent chemical weapons, separated according to the different actuation mechanisms . The modules allow the respective dismantling of grenades, mines, missiles and chemical bombs. The necessary adaptable tools and systems (eg, underwater saws, waterjet cutting devices, mechanical decay systems) are determined based on the weapon system to be eliminated. For buried chemical ammunition or old chemical ammunition, devices are available to identify the ammunition and its contents. There is a direct connection with the modules in which the elimination of toxic substances, explosive substances and parts of mechanisms

contaminated actuator.

  According to the present invention, a module is also provided for the thermal decontamination of dismantled actuation mechanisms. Decontamination of dismantled mechanisms is done using a plasma

  produced by induction or gas oven.

  An explosive thermal elimination module is also planned. Explosive substances are burnt directly at the disposal site using a gas oven or a mobile rotary tube oven or

  2 5 are eliminated, after transport, in a fixed combustion installation.

  In this case, elimination by means of a rotary tube oven has proven to be optimal in practice. For further details concerning the elimination of explosive substances by means of a rotary tube furnace, reference is entirely made to German patent application 196 17 617.4, of May 2, 1996, prior, but not yet published, of the present Applicant. According to the present invention, residual substances remaining after the wet chemical treatment of toxic substances can optionally be treated by combustion at high temperature. Toxic substances are destroyed in a temperature plasma installation

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  high, using plasma produced by induction or discharge of a

hot cathode.

  By plasma is meant the dissociation of a gas into ions and electrons.

  Depending on the nature of the gas and the intensity of the energy applied, the gas will be dissociated to a different extent. A distinction is made, depending on the gas pressure, between low pressure plasma and high pressure plasma. In high pressure plasmas, ions, electrons and gas molecules are in thermodynamic equilibrium, so high powers are required to reach temperatures

  necessary for plasmachemical reactions.

  According to the present invention, there is also a module for the chemical elimination in the wet state of toxic substances. The installed apparatus allows chemical transformation of toxic substances into relatively non-toxic compounds, which are subject to subsequent disposal. The reaction chosen (for example, hydrolysis, oxidation, a specific catalytic process) depends on the nature of the chemical compounds

  to eliminate and their physicochemical properties.

  The module can be used to dissolve toxic substances insoluble in water in order to prepare them for elimination by a process

  thermal, in particular by plasma combustion.

  The present invention provides a module for the purification of burnt gases. The central flue gas cleaning system includes all

  the necessary devices (quenching, alkaline and / or oxidative washing against)

  current, filtration systems) to maintain emissions that respect

the environment.

  For other details concerning the purification of the burnt gases which are released for example during the elimination of explosive substances in a rotary tube furnace, reference will be made completely to German patent application 196 17 617.4 of May 2, 1996, earlier but not yet published, of

The present Applicant.

  There is judiciously provided a module intended to house the central analysis apparatus and equipment and to carry out a permanent recording of the current elimination operations and of the emissions. The necessary devices will be installed for the live recording of ongoing disposal operations. Systems for monitoring possible emissions

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  guarantee environmental protection. An automatic shutdown of the thermal elimination installation (plasma installation) occurs when

  limit values are exceeded.

  Modules are also provided for securing the necessary fuels and energy supply systems. The equipment and the routing mode are determined according to the process

respective disposal chosen.

  We can also provide a module to house the staff of

  service. The layout is done on the basis of sanitary standards.

  In addition, a safety module can be provided for occupational health interventions. The equipment of the module allows to carry out the necessary medical examinations and to provide first aid

  medical in case of poisoning or accidents.

  The following toxic substances can be eliminated, for example, by the process according to the invention: Sarin (o-isopropyl methylfluorophosphonate), Soman (o-1,2,2-trimethylpropyl methylfluorophosphonate), Tabun (N, N-dimethylamidocyanophosphate), VX (S-2-diisopropylaminoethyl-methylthiophosphonate), S-yperite (bis (2-chloroethyl sulfide), Lewisite 1 (2-chlorethenyl-dichlorarsine), Lewisite 2 (bis- (2-chlorethenyl) -chlorarsine), Lewisite 3 (tris- (2-chlorethenyl) -arsine), phosgene (carbonyl dichloride), 2 5 Clark I (diphenylchlorarsine), Clark II (diphenylcyanarsine), and

  Adamsite (diphenylaminarsine chloride).

  The following ammunition (indicated by their current designation) from old military charges can, for example, be disposed of on the spot by the process of the present invention, since such overstocked material is no longer transportable: First World War (Germany): grenades 7.7 cm short (green cross / yellow cross); 7.7 cm long grenades (green cross); 7,7 cm long grenades with cylinder (blue cross); 10 cm grenades, 1915 model (green cross, yellow cross); 10.5 cm long grenades (green cross, cross

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  green 3, yellow cross 1); 12 n / A grenades of 15 cm green cross, cm grenades, model 1912, semi-explosive, reinforced; 15 cm grenades with yellow cross, shattering effect; 17 cm grenades with liquid cap (yellow cross);

  18 cm smooth gas mines (green cross / blue cross).

  World War II (Germany): L.F.H. of, 5 cm and S.F.H. 15 cm (white ring, blue ring, green ring, yellow ring); 15 cm throwing grenades for rocket launchers (green ring,

  green ring 1, green ring 3, yellow ring); hand grenades with green ring.

  In addition to the safety technique described for the plasma installation, we will install, for all modules in which there could be release of toxic substances (thermal decontamination module of the dismantled actuation mechanisms, dismantling modules, elimination module chemical in the wet state of toxic substances, thermal elimination module for toxic substances), safety systems that prevent the release of toxic substances into the atmosphere. Consequently, these modules are equipped with an airlock system and a filter ventilation system, which allow forced ventilation to the outside only through a filter of harmful substances (carbon catalyst) and produce a depression in the hermetically sealed space. The monitoring of the ambient air using an automatic analysis device for the analysis of toxic substances to be eliminated (ion mobility spectrometer) signals by optical and acoustic signals a possible overshooting of the

  limit concentrations of toxic substances in indoor ambient air.

  In the case of contamination, water is sprayed into the module through an annular water pipe, so that there is a deposit of the toxic substance and a dilution effect. Contaminated water ends up in a receiving tank filled with a specific detoxification agent and can then be re-routed to the disposal process. The walls of the module will be decontaminated by a detoxification agent by the service personnel, who will have entered the space, equipped with corresponding protective masks and suitable protective clothing, passing through the

airlock system.

  The entire system is monitored and controlled in real time by means of a redundant error-protected process control. Sensors and live spectroscopy provide

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  continuous monitoring of the process. All safety-related components are provided in duplicate in intrinsically safe mode. The reactor is provided with an envelope which is permanently kept under vacuum during operation. In the event of an incident (for example, rupture of the plasma module reaction tube), the system pressure is reduced and, depending on the pressure conditions, gases, including leaks, are sucked up

  by means of the gas cleaning system.

  Substances not burnt during a general breakdown of the installation, due to a drop in the supply voltage or to a network failure, are sent to the process, after restarting the installation, by means of

  an appropriate recycling system.

  Other advantages and characteristics of the present invention

  will emerge from the description of exemplary embodiments made below in

  reference to the accompanying drawings, in which: FIG. 1 is a general diagram of the modular structure of the device according to the invention, FIG. 2 represents a plasma module, as a constituent part of the device according to the invention, in which the toxic substances are destroyed, and Figure 3 is a block diagram for purifying gases from the

plasma module.

  The principle structure of the plasma module according to the process

  Figure 5 shows the plasma concentration.

  Examples for the wet chemical removal of toxic substances which are carried out are given in Table 1 below.

in the corresponding module.

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Table 1

  Toxic substances Detoxification agent S-Yperite Lime chloride paste (lime chloride: water 1: 1); % chloramine T in water; % dichloramine in dichloroethane; saturated solution of sodium hypochlorite by introduction of chlorine in NaOH under cooling; % of hexachloromelamine in l _ __ __ __ __ __ _ dichloroethane; Lewisite 10% dichloramine in dichloroethane; % NaOH in water, optionally with the addition of 10% alcohol; alkaline hydrogen peroxide solution at%; saturated sodium hypochlorite solution; Clark 1, II and Adamsite 3% potassium permanganate solution; 10% hydrogen peroxide solution; % sodium sulfide in water (with the addition of alcohol); Lime chloride paste (lime chloride: water 1: 1); 10% phosphoric acid ester of NaOH in methanol or alcohol and 30% acid ester; phosphonic 20% NaOH in water; % ammonia in water; saturated sodium hypochlorite solution; 3% alkaline hydrogen peroxide solution; % of sodium cresolate or phenolate in methanol or 50% alcohol;

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  The toxic product to be removed is brought into the reactor via a metering device. The process gases required for treatment are

  obtained by precise gas supply.

  The reactor consists, in the case of inductive coupling, of a non-conductive material allowing the HF rays to pass, which is surrounded by a coil. The coil is connected to a high frequency generator. A network

  Adaptation serves to optimize the coupling of real power in the plasma.

  In a capacitively coupled reactor, the power is supplied by

  electrodes that operate with direct current.

  The reactor is equipped with a combined cooling system

  air / water. The cooling air system is connected to a suction blower.

  In the event of breakdowns (reactor leakage), the substances that leave are sucked through the entire gas cleaning system depending on the

pressure conditions.

  Quenching makes it possible to cool the reaction products.

  The residual substances are collected, downstream of a water-cooled separator, in a suitable container which is followed by a device

evacuation of burnt gases.

  Quenching The hot reaction gas from the plasma reactor is quenched with water, ammonia and air. This allows, in the high temperature range, the reaction of halogens, such as fluorine or chlorine, with hydrogen so that it is possible to continue the reaction with ammonia to obtain ammonium salts

readily volatile.

  Heat exchange By heat exchange with pure gas, the gas is further cooled after quenching and the pure gas is heated significantly above its dew point temperature around around 470 K, to avoid corrosion and reach a sufficient go temperature of the activated carbon bed

  (to avoid overshooting the dew point).

  Spray drying In the spray dryer, the washing solution from the washer is sprayed with its alkaline fractions containing 1165 acid or ammonia compounds from the flue gases. The solids separating in the form of granules are largely extracted by means of a

cell wheel lock.

  Filire In the flue gases, after the spray dryer, fractions of the dust formed remain. These are separated in the dust filter to a range well below 5 mg / m3 and are extracted

  also by means of a cell wheel lock.

  Denox A Denox installation for catalytic denitriding of flue gases is installed downstream of the dust filter, after intermediate heating. Preferably, ammonia is added in the gaseous form as a reducing agent. The catalytic decomposition of dioxins and

  furans, which may still appear, occur simultaneously.

  Alkaline washing Alkaline washing is carried out at a pH value of approximately 9. An aqueous solution of NaOH is supplied as a base to the system so as to adjust the pH, which has the effect of washing away the harmful acidic components present in the flue gas stream. Concentrated wastewater discharged

  20 are introduced into the spray dryer to be removed.

  Activated charcoal bed The activated charcoal bed is used to absorb harmful substances in the event of damage and must be considered as a safety device. After the activated carbon bed, there is the suction blower, by means of which

  the installation can operate in the low pressure range.

  The modular device according to the invention is entirely designed so as to be assembled on the site of the intervention, for example on the land of a landfill, so that the materials therein can be disposed of in a manner optimal, this design including 3 o more particularly the possibility of changing or completing modules

individual as needed.

  At the end of the elimination works, the installation is again dismantled in individual modules and brought to the most

  close to where it is re-assembled as needed.

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Claims (21)

  1. Process for the elimination of weapons containing highly toxic and / or explosive substances, in which the weapons are dismantled and the separate sub-units of the weapons, obtained during dismantling, are routed respectively to a specific module for each sub- unit, the sub-units not contaminated with highly toxic substances and which contain explosive substances are sent to a module in which the explosive substances are thermally converted in a controlled manner and any solids present are separated; and the subunits, which contain the toxic substances, after separation of their envelopes, are routed at least to a plasma module which contains a plasma produced by induction or by discharge from a hot cathode, which is charged with at least one reactive gas, the toxic substances being broken down in the plasma into less toxic or non-toxic products, characterized in that the envelopes contaminated by the toxic substances are decontaminated hot in another plasma module; and all the burnt gases produced are sent to a central module purification of burnt gases.   2. Method according to claim 1, characterized in that the weapons are chosen from bombs, bullets, grenades, mines and containers. 3. The method according to claim 1 or 2, characterized in that the toxic substances are chosen from the group comprising: organic esters of phosphoric and phosphonic acids, in particular: o-isopropyl methylfluorophosphonate, methylfluorophosphonate d 'o-1,2,2-trimethylpropyl, 13 2765322   o-ethyl N, N-dimethylamidocyanophosphate, organic esters of thiophosphoric acid, in particular: o-ethyl S-2-diisopropylaminoethylmethylthiophosphonate, organic sulphides, in particular: bis (2-chloroethyl) sulphide ) organic arsenic compounds, in particular: 2-chlorethenyl-dichlorarsine, bis (chlorethenyl) -chlorarsine, tris- (2-chlorethenyl) -arsine, o diphenylchlorarsine, diphenylcyanarsine, diphenylaminarsine chloride, and carbonyl dichloride.   4. Method according to any one of claims 1 to 3,   characterized in that the toxic substances are conveyed, either in the plasma module for treatment at high temperature, or in a chemical treatment module, in which the toxic substances are chemically converted in the wet state or thermally according to their 2 o physical and chemical characteristics, and the products obtained are   sent to the module for another thermal elimination.   5. Method according to any one of claims 1 to 4,   characterized in that, in the chemical treatment module in the wet state, inerting reactions are carried out which are chosen from the group comprising: hydrolysis; oxidation; the reduction; a specific catalytic process; and the introduction of toxic substances into: a mixture of lime chloride and water, chloramine T in water, dichloramine in dichloroethane, a saturated solution of sodium hypochlorite, hexachloromelamine in dichloroethane, sodium hydroxide in water, optionally with the addition of ethanol, a solution of hydrogen peroxide, in particular an alkaline solution of hydrogen peroxide, a solution of potassium permanganate, sodium sulfide in water, optionally with the addition of ethanol, sodium hydroxide in 14 2765322   methanol or alcohol, ammonia, sodium cresolate in methanol or alcohol, sodium phenolate in methanol or alcohol.   6. Method according to any one of claims 1 to 5,   characterized in that the hot reaction gases, which leave the module at   plasma, are soaked, preferably with water.   7. Method according to any one of claims 1 to 6,   characterized in that, after the toxic substances have passed through the plasma module, the solid residuals are separated from the gaseous products in a separator, preferably cooled with water, and are   collected in an appropriate container.   8. Mobile modular disposal facility for disposal   work of the method according to any one of claims 1 to 7 and   comprising: at least one weapon dismantling module containing toxic and / or explosive substances, in which the weapons are broken down into separate sub-units; at least one explosive substances elimination module for the controlled thermal conversion of explosive substances contained in weapons; at least one plasma module, which comprises at least one device for producing a plasma at high temperature by high frequency discharge or discharge from a hot cathode; characterized in that: the disposal installation comprises at least one other plasma module for the thermal decontamination of envelopes, which are contaminated with toxic substances, as well as at least one module purification of burnt gases.   9. Disposal installation according to claim 8, characterized in that the dismantling module comprises robots and / or tools 1S * 2765322   remote controlled screwing, sawing, drilling, sectioning and suction. 10. Disposal installation according to claim 9, characterized in that the tools are underwater saws, underwater drills and   water jet cutting devices.   11. Disposal installation according to any one of   Claims 8 to 10, characterized in that the module for eliminating   o explosive substances includes a rotary tube furnace.   12. Disposal installation according to any one of   Claims 8 to 11, characterized in that the plasma module comprises a   metering device by which toxic solid, liquid and   1 5 gaseous are brought into contact with the plasma.   13. Disposal installation according to claim 12, characterized   in that the plasma module produces a high pressure plasma.   14. Disposal installation according to claim 12 or 13, characterized in that the plasma chamber, in the case of inductive coupling, consists of a non-conductive material permeable to high frequencies or, in the case of a hot cathode discharge from a reactor in heat resistant fine steel.   15. Disposal installation according to claim 14, characterized in that the plasma chamber, in the case of an inductive coupling, is surrounded by a coil, which is connected to a high frequency generator, and, in the case of a capacitive coupling, is supplied by electrodes 3 o receiving direct current.   16. Disposal installation according to claim 14 or 15, characterized in that the plasma chamber is surrounded by an envelope of   security which is depressed. 16 2765322   17. Disposal installation according to any one of   Claims 1 to 16, characterized in that the plasma modules have   a process gas metering device.   18. Disposal installation according to any one of   Claims 1 to 17, characterized in that the plasma modules have   a combined air / water cooling system.   19. Disposal installation according to any one of   Claims 1 to 18, characterized in that the plasma modules have   a safety cooling and suction device with filters   adsorption, in particular activated carbon filters.   20. Disposal installation according to any one of   Claims 1 to 19, characterized in that the plasma modules have   a quench gas delivery system.   21. Disposal installation according to any one of   Claims 1 to 20, characterized in that an analysis module is provided   live which, by means of sensors, assists, on the one hand, the process control by spectroscopic processes and realizes, on the other hand, the leakage control.