Activated vapor treatment for neutralizing warfare agents
Abstract
A method to deactivate a pathogenic chemical agent characterized by: subjecting the pathogenic chemical agent to a gaseous mixture of a peroxide in the form of steam and nitrogen-containing compound in the form of gas, the ratio of peroxide to the compound containing nitrogen between 1: 1 and 1: 0.0001, the general formula of the nitrogen-containing compound being: ** (See formula) ** in which R1, R2 and R3 are independently selected between H and an alkyl group .

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27 claims: 9 independent, 18 dependent
- 1ES 2 341 010 T3 REIVINDICACIONES 1. Un método para desactivar un agente químico patógeno que se caracteriza por:someter el agente químico patógeno a una mezcla gaseosa de un peróxido en forma de vapor y compuesto que contiene nitrógeno en forma de gas, siendo la relación de peróxido con respecto a compuesto que contiene nitrógeno de entre 1:1 y 1:0,0001, siendo la fórmula general del compuesto que contiene nitrógeno: Rl-N-R 2 I r 3 en la que R 1 , R 2 y R 3 se escogen de manera independiente entre H y un grupo alquilo.
- 2El método de la reivindicación 1, que además se caracteriza porque:el peróxido incluye agua oxigenada.
- 3El método de la reivindicación 1 ó 2, que además se caracteriza porque:el peróxido se encuentra en forma de vapor.
- 4El método de la reivindicación 3, que además se caracteriza por:vaporizar el compuesto líquido de peróxido para formar un vapor de peróxido.
- 5El método de la reivindicación 1, que además se caracteriza porque:el compuesto que contiene nitrógeno incluye amoniaco.
- 6El método de la reivindicación 1, que además se caracteriza porque:el compuesto que contiene nitrógeno incluye una alquilamina.
- 7El método de una cualquiera de las reivindicaciones 1-6, que además se caracteriza porque:el gas de amoniaco y el vapor de agua oxigenada están presentes en una relación de entre 1:1 y 0,0001:1,0.
- 8El método de la reivindicación 1, que además se caracteriza porque:el compuesto que contiene nitrógeno se encuentra en una concentración de al menos 1 ppm en la mezcla gaseosa.
- 9El método de la reivindicación 8, que además se caracteriza porque:la concentración del compuesto que contiene nitrógeno es menor que 100 ppm.
- 10El método de la reivindicación 9, que además se caracteriza porque:la concentración del compuesto que contiene nitrógeno es de al menos 3 ppm en la mezcla gaseosa y menor que 20 ppm. ES 2 341 010 T3
- 11El método de la reivindicación 10, que además se caracteriza porque:el compuesto que contiene nitrógeno incluye amoniaco en una concentración de 8 ppm.
- 12El método de una cualquiera de las reivindicaciones 1 y 8 a 11, que además se caracteriza porque:la concentración de peróxido es de al menos 50 ppm en la mezcla gaseosa.
- 13El método de una cualquiera de las reivindicaciones 1 y 8 a 12, que además se caracteriza porque:la concentración de peróxido es menor que 1000 ppm en la mezcla gaseosa.
- 14El método de la reivindicación 12, que además se caracteriza porque:la concentración de peróxido es de al menos 400-800 ppm en la mezcla gaseosa.
- 15El método de la reivindicación 14, que además se caracteriza porque:el compuesto que contiene nitrógeno incluye amoniaco en una concentración de 3-20 ppm.
- 16El método de la reivindicación 15, que además se caracteriza porque:la temperatura es de 23-25°C.
- 17El método de la reivindicación 15 ó 16, que además se caracteriza porque:el peróxido incluye agua oxigenada en una concentración de 600 ppm en la mezcla gaseosa.
- 18El método de la reivindicación 17, que además se caracteriza porque:el compuesto que contiene nitrógeno incluye amoniaco en una concentración de 8 ppm en la mezcla gaseosa.
- 19El método de una cualquiera de las reivindicaciones 12 a 18, que además se caracteriza porque:la concentración de peróxido es de al menos 200 ppm en la mezcla gaseosa.
- 20El método de una cualquiera de las reivindicaciones 1 y 8 a 19, que además se caracteriza porque:la mezcla gaseosa además incluye un gas portador.
- 21El método de la reivindicación 20, que además se caracteriza porque:el gas portador incluye aire.
- 22El método de una cualquiera de las reivindicaciones 1-21, que además se caracteriza porque:el agente químico incluye al menos uno de los agentes químicos de tipo G, tipo V y tipo H y sus combinaciones.
- 23El método de la reivindicación 22, que además se caracteriza porque:el agente químico incluye un agente químico de tipo G y el método incluye poner en contacto el agente químico patógeno con el compuesto que contiene nitrógeno y el peróxido durante el tiempo suficiente para reducir el agente de tipo G hasta un nivel menor que 1% de su concentración original. ES 2 341 010 T3
- 24El método de la reivindicación 22 ó 23, que además se caracteriza porque:el tiempo de contacto es de hasta seis horas.
- 25El método de una cualquiera de las reivindicaciones 1-24, que además se caracteriza por:mantener la temperatura durante la etapa de puesta en contacto a alrededor de 15°C a 30°C.
- 26El método de una cualquiera de las reivindicaciones 1-25, que además se caracteriza porque:el compuesto que contienen nitrógeno es un líquido y el método además incluye vaporizar el líquido en un vaporizador.
- 27El método de la reivindicación 1, en el que el agente químico incluye éster 1,2,2-trimetilpropílico de ácido metilfosfonofluorídico (agente GD) y el compuesto que contiene nitrógeno incluye amoniaco y un objeto se encuentra contaminado con GD, caracterizándose dicho método por:poner en contacto el objeto en el interior de una caja (10) con vapor que contiene un peróxido y amoniaco, durante el tiempo suficiente para reducir la concentración de GD a menos que 1% de su concentración inicial, siendo el tiempo requerido para que la concentración alcance 1% de su valor inicial inferior a 6 horas.
Independent claims27
86 paragraphs in 6 sections, as filed
ES 2 341 010 T3
DESCRIPTION
Activated steam treatment to neutralize weapons agents.
Background of the invention
The present invention relates to the technique of deactivating biological and chemical weaponry agents. It finds particular application with type G, V and H neurotoxic agents, as well as with biological agents.
Chemical weaponry agents include type G, V, and H type agents. Type G agents contain phosphorus and are clear, colorless, and tasteless liquids that are miscible in water and most solvents. Examples include ethyl-N, N-dimethyl phosphoaminocyanidate (Taburn or agent GA), phosphonofluoridate esters, such as isopropyl methyl phosphonofluoridate (Sarin or agent GB), and methylphosphonofluoridic acid 1,2,2-trimethylpropylester (Soman or agent GD). GB is odorless, is the most volatile nerve agent, and evaporates about as fast as water. GA has a slight fruity odor and GD has a slight camphor odor. H-type agents include di (2-chloroethyl) sulfide (mustard gas or HD agent) and dichloro (2-chlorovinyl) arsine (Lewisite).
Type V neurotoxic agents contain a substituted amine group and include methyl phosphonothiolates that have an internal amino group. Examples include o-ethyl-s- (2-diisopropylaminoethyl) methylphosphonothiolate (agent VX), o-isobutyl-s- (2-diethyl) methylphosphonothiolate and o, s-diethyl methylphosphonothiolate. Phosphonothiolates from toxic hydrolysis products include phosphonothioic acids. VX is a clear, amber-colored, odorless, and oily liquid. It is miscible with water and soluble in all solvents. It is the least volatile nerve agent.
Liquid oxidants have been developed that can deactivate biological weapons agents. See, for example, US-A-6,245,957 to Wagner et al. In the Wagner paper, the spraying of an oxidizing liquid solution on field equipment that presents actual or potential contamination with chemical or biological weaponry agents is discussed. After treatment, the solution is rinsed from the equipment with water that is allowed to flow over the ground as a non-toxic residue. Although effective, Wagner's liquid solution has drawbacks. First of all, it is difficult for liquids to penetrate the crevices, small fissures, ducts and partially protected or overlapping parts. Second, in confined spaces such as the interior of airplanes, tanks, and buildings, cleaning and removing the liquid solution can be problematic. Third, liquids can damage some equipment, such as electrical and electronic equipment.
Blistering agents, such as HD (sulfur mustard) undergo oxidation to non-vesicle-forming products (sulfur becomes sulfoxide). By the correct choice of agents, subsequent oxidation to the sulfone product is avoided. This is preferable since both the sulfide and the sulfone exhibit vesicle-forming properties; at the same time, the sulfoxide is non-vesicle-forming.
Peroxide causes a perhydrolysis reaction that neutralizes type V neurotoxic agents, such as VX neurotoxic agent. In the perhydrolysis reaction, the peroxide moiety replaces one of the groups around the phosphorous atom in the active position of the neurotoxic agent molecule. Perhydrolysis is more effective with type V neurotoxic agents than base-catalyzed hydrolysis. In the presence of water, such as water and ammonia wash solution, the base catalyzed hydrolysis reaction can form EA2192 which is also highly toxic. EA2192 is a phosphonothioic acid that has the same basic structure as VX with the exception that the terminal ethoxy group is substituted by OH.
On the other hand, G agents, such as GD tend to be quite stable in the presence of hydrogen peroxide. GD does not undergo autocatalytic perhydrolysis which neutralizes the reaction with hydrogen peroxide. In contrast, type G agents typically undergo deactivation with liquid hydrogen peroxide via basic catalysis reaction. Specifically, ammonia has been used to facilitate base catalyzed hydrolysis of agents with liquid hydrogen peroxide, or perhydrolysis. Molybdate ions have also been used in combination with liquid hydrogen peroxide. The permolybdate ions formed have been shown to deactivate agents G, V and H.
US-A-5,998,691 describes the destruction of chemical weapons agents (CWA) by means of a nitrogen base, which can be ammonia or amines, followed by oxidation by hydrogen peroxide or other oxidants. It is also disclosed that the destruction of CWA by this method does not require active metal in combination with the nitrogenous base. It describes that the ammonia or amines should be in a liquid state and that hydrogen peroxide is added after evaporation of the ammonia.
The present application provides a vapor phase deactivator that is effective against type G, V and H agents, as well as against biological agents.
ES 2 341 010 T3
Summary of the invention
The present invention relates to a method for deactivating a pathogenic chemical agent characterized by:
subjecting the pathogenic chemical agent to a gaseous mixture of peroxide in vapor form and nitrogen-containing compound in gas form, the ratio of peroxide to nitrogen-containing compound being between 1: 1 and 1: 0.0001, presenting the nitrogen-containing compound the general formula:
r<sub>1</sub>-nr<sub>2</sub>
Ra in which R<sub>1</sub>, R<sub>2</sub> and R<sub>3</sub> they are independently chosen from H and alkyl group.
Furthermore, the present invention relates to an apparatus for deactivating a pathogenic chemical agent characterized by:
a vaporizer to vaporize the hydrogen peroxide liquid;
a means for injecting the hydrogen peroxide liquid into the vaporizer with a flow rate of 0.4-0.5 grams / minute to form hydrogen peroxide vapor;
a tank of compressed gaseous ammonia (32) or an atomizer (50) that atomizes a liquid compound containing nitrogen inside a mist of the general formula:
Ri-N-Rz
Go<sub>3</sub> in which R<sub>1</sub>, R<sub>2</sub> and R<sub>3</sub> they are independently chosen from H and alkyl group;
a box;
a means for mixing hydrogen peroxide vapor and gaseous ammonia or mist to form a gaseous mixture, the ratio of hydrogen peroxide to nitrogen-containing compound being between 1: 1 and 1: 0.0001 and supplying said mixture soda to the box.
In accordance with a preferred aspect of the present invention, there is provided a method for decontamination of an object contaminated with GD. The method includes contacting the object in a box with a vapor containing a peroxide and ammonia, for long enough to reduce the concentration of GD to less than 1% of its initial concentration, the time being for the concentration to reach 1 % of initial concentration less than 6 hours.
In accordance with a preferred aspect of the present invention, a method of inactivating a pathogenic chemical agent is provided. The method includes forming a peroxide vapor, increasing the pH of the vapor with a pH raising compound, and subjecting the pathogenic chemical agent to the peroxide at the elevated pH value for a time sufficient to deactivate the chemical agent.
According to a preferred aspect of the present invention, there is provided a method of deactivating the biologically active substance. The method includes subjecting the biologically active substance to a mixture of strong oxidizing compound and alkaline compound, both in gaseous form.
ES 2 341 010 T3
In accordance with more limited aspects of the present invention, the surfaces are optionally treated with a combination of an oxidizing vapor and a basic vapor, mist, or mist, preferably ammonia or a short chain aquilamine.
An advantage of at least one embodiment of the present invention resides in its efficacy against a wide variety of chemical weaponry agents, including type V and G agents, as well as biological weaponry agents.
Another advantage of at least one embodiment of the present invention resides in its effectiveness against chemical and biological weaponry agents.
Another advantage of at least one embodiment of the present invention resides in its ease of cleaning.
Another advantage of at least one embodiment of the present invention resides in its compatibility with electrical equipment.
Other advantages of the present invention will become apparent to those of ordinary skill in the art upon reading and considering the following detailed description of the preferred embodiments.
Brief description of the drawings
The invention may take the form of several components and component configuration, as well as multi-stage and stage configuration. The drawings are only intended to illustrate a preferred embodiment and are not intended to limit the invention.
Figure 1 is a diagrammatic illustration of a steam treatment system in accordance with the present invention;
Figure 2 is an alternative embodiment of the treatment system of Figure 1;
Figure 3 is another alternative embodiment of the steam treatment system;
Figure 4 is a proposed reaction scheme for the conversion of HD agent to HDO and HDO reaction products<sub>2</sub> in the presence of hydrogen peroxide;
Figure 5 is a proposed reaction scheme for the conversion of the VX agent to VX-Pyro, EMPA and other reaction products in the presence of hydrogen peroxide;
Figure 6 is a proposed reaction scheme for the conversion of the GD agent to PPMA in the presence of hydrogen peroxide and ammonia or amine;
Figure 7 is a plot of percent HD and HDO versus time, in the presence of hydrogen peroxide and ammonia;
Figure 8 is a plot of percent VX, VX-Pyro, and EMPA versus time, in the presence of oxygenated water vapor without ammonia;
Figure 9 is a plot of percent VX, VX-Pyro, and EMPA versus time in the presence of ammonia hydrogen peroxide;
Figure 10 is a graph of the percentage of GD and PMPA versus time, in the presence of hydrogen peroxide with ammonia; Y
Figure 11 is a graph of percent GD and PMPA versus time, in the presence of ammonia-oxygenated water vapor, under controlled water conditions.
Detailed description of the preferred embodiments
With respect to Figure 1, the treatment box 10 receives or constitutes in itself a structure potentially contaminated with biologically active substances, in particular biological or chemical weapons agents. Typically, biologically active substances include pathogens, biotoxins, prions, spores, chemical agents, and the like. Typical chemical agents include type H vesiculating agents such as mustard gas and type V and G neurotoxic agents.
The treatment chamber or box 10, in one embodiment, is a specific chamber that is adapted to receive the objects to be treated and then sealed. Objects to be decontaminated can include equipment, weapons, clothing, medical instrumentation, and the like. The camera can be a fixed structure, a tent that is mounted around
ES 2 341 010 T3 of the object to be treated, a mobile camera or the like. In another embodiment, the box includes the interior of a warehouse, room, airplane, ship, tank, or other vehicle whose interior surfaces or objects are subject to treatment.
Fan or blower 12 releases ambient gas, typically air, from box 10 through chemical or biohazard filter 10. A catalytic destruction device 16 causes the breakdown of the hydrogen peroxide to give rise to the formation of water vapor. The drying device 18 removes the water vapor from the recirculated gas in order to control the humidity of the carrier gas.
Filtered, dry air or other carrier gas is supplied to vaporizer 20, which vaporizes the liquid oxidant, preferably a hydrogen peroxide solution, from a source 22 of liquid hydrogen peroxide. In particular, the vaporizer provides heat to the liquid oxidant to convert it to vapor form. The heat applied is sufficient to vaporize hydrogen peroxide and water without leading to premature decomposition of hydrogen peroxide.
While particular reference is made to peroxides, in particular hydrogen peroxide, other strong oxidants such as hypochlorites, ozone solutions and peracids, such as peracetic acid, are also contemplated. Optionally, a cosolvent, such as an alcohol, is mixed with the liquid oxidant. Valve 24 or other appropriate control means regulates the rate at which liquid hydrogen peroxide vaporizes.
The oxygenated water vapor is fed into a chamber or mixing region 30 in which the homogenization of the oxygenated water vapor and the mixture of air with a basic gas, fog or mist (all of them referred to in the present memory as gaseous states, unless otherwise indicated), preferably ammonia gas. However, other nitrogen-containing compounds capable of increasing the rate of degradation of at least one biologically active substance and / or of reducing the concentration of at least one pathogenic product of degradation of the biologically active substance, such as alkylamines, are also contemplated. short chain, e.g. Ci-C alkylamines<sub>8</sub>. The nitrogen-containing active compound can be described below by means of the general formula:
R! -NR<sub>2</sub> r<sub>3</sub> where R<sub>1</sub>, R<sub>2</sub> and R are independently chosen from H and an alkyl group. The alkyl group may or may not be substituted. Suitable substituents are those that do not adversely affect the catalytic activity of the nitrogen-containing compound. Preferably, the nitrogen-containing compound is one capable of persisting in the oxygenated water vapor phase or in contact with the biologically active substance long enough to act as an accelerator in the peroxide degradation process of the agent. Suitable alkylamines include methylamine, ethylamine, propylamine, butylamine, dimethylamine, methylethylamine, diethylamine, combinations thereof, and the like.
In the embodiment shown in the illustration, ammonia gas (or other nitrogen-containing compound) is supplied from a source or reservoir 32, such as a high pressure tank containing compressed ammonia gas. A control or regulating valve 34 controls the amount of ammonia vapor supplied to mixing zone 30. Immediately, the mixture of ammonia and hydrogen peroxide is continuously supplied to treatment chamber 10. Optionally, a biological or chemical contaminant filter 36 is mounted at the inlet of the chamber.
In one embodiment, hydrogen peroxide and ammonia are mixed just before or at the time they enter box 10. In a specific embodiment, they are introduced into the box along separate fluid lines and mixed within the box. box.
Controller 40 is connected to one or more monitors 42 arranged in treatment chamber 10 to record environmental conditions. Based on the recorded environmental conditions, the controller regulates one or more control valves 24 and 34 in order to establish one or more of the relative concentrations of hydrogen peroxide and ammonia vapor, the pusher 12 to control the amount of air flow, chamber fans 44 to distribute treatment gas around the chamber, and the like. Preferably, controller 40 regulates valves 24, 34 so that the mixture of peroxide vapor and ammonia in mixing zone 30 reaches an ammonia concentration within the range of 1 to 0.0001 times the nominal concentration of peroxide vapor. .
In one embodiment, the ammonia concentration in treatment chamber 10 is at least 1 ppm by weight. The ammonia concentration in treatment chamber 10 can be up to about 100 ppm, by weight. In a specific embodiment, the ammonia concentration in treatment chamber 10 is within the range of 3-200 ppm, by weight. In one embodiment, the hydrogen peroxide concentration is at least 50 ppm by weight (0.67 mg / L). The hydrogen peroxide concentration in treatment chamber 10 can be up to about 3600 ppm, by weight
ES 2 341 010 T3 (5 mg / l), or higher. In a specific embodiment, the concentration of hydrogen peroxide in treatment chamber 10 is within the range of 200-1000 ppm, by weight. For example, the concentration of ammonia can be around 8 ppm and that of hydrogen peroxide around 600 ppm. To achieve such concentrations in the small box of around 0.1-0.2 m<sup>3</sup>, a flow rate of around 0.03-0.05 m is required<sup>3</sup>/ minute of hydrogen peroxide vapor and carrier gas. NH can be entered<sub>3</sub> into the VHP stream at about 0.18 ml / min just prior to its entry into the box. For larger boxes, higher flow rates may be appropriate.
In one embodiment, the hydrogen peroxide is replenished intermittently or continuously in order to maintain a desired range of concentration within the box 10. In another embodiment, the box is sealed once the hydrogen peroxide concentration and / or ammonia has reached the desired level, or a short time later. The concentration is allowed to decrease naturally over time due to decomposition. For example, hydrogen peroxide and ammonia can be introduced into the box for an initial period of around four to six hours and then the box is sealed, thus allowing the destruction of residual amounts of chemicals and their pathogenic reaction products. , for a later period of about ten to twenty hours. The vaporizer can be unplugged after the initial period and used to decontaminate another box.
By means of a heating device 46, the box 10 can be kept at room temperature or around room temperature (around 15-30 ° C), preferably around 23-25 ° C.
In the embodiment of Figure 1, a closed loop system is shown in which the carrier gas is recirculated and used again. Alternatively, an open loop system can be used, through which clean atmospheric air is supplied to the vaporizer, preferably filtered and dry, and the air leaving the chamber is filtered to prevent biological or chemical contaminants from escaping. or are released into the atmosphere.
With reference to Figure 2, an open loop system is shown. The blowing device 12 passes the air through the filter 14 and optionally through a dehumidifier before pushing it through the vaporizer 20. A source 22 of peroxide vapor and a source 34 of active nitrogen-containing compound They provide the liquid peroxide and the nitrogen-containing compound to the vaporizer. Alternatively, when the nitrogen-containing compound is liquid, separate vaporizers can be provided for each. It is possible to inject the peroxide and the nitrogen-containing compound separately, making use of the carrier gas, into the mixing region. Another possibility is to supply the vaporizer with the nitrogen-containing compound and the peroxide separately in the form of liquids. The outlet of the vaporizer is connected to an interior region whose surfaces it is desired to decontaminate.
Referring to Figure 3, the carrier gas is filtered 14, the peroxide 16 is destroyed, and 18 is dried. The blower device 12 conducts the dry gas to the vaporizer 20, which vaporizes the liquid peroxide from the source 22. Peroxide vapor is supplied directly to treatment region 10. An atomizer 50 receives the liquid alkaline solution from reservoir 52, atomizes it into a mist, and introduces it into chamber 10. Optionally, a part of the carrier gas flows through the nebulizer in order to conduct and transport the mist throughout the entire chamber. Alternatively, the alkaline solution can be vaporized. Suitable alkaline solutions include aqueous solutions of potassium and other carbonates, molybdates, ammonium salts, and the like.
In another embodiment, hydrogen peroxide and ammonia are introduced sequentially. For example, ammonia is added first. After a sufficient period of time for the ammonia to circulate through the box 10, the hydrogen peroxide is allowed to flow into the box.
In another embodiment, at least one of oxygenated water vapor and ammonia is generated in situ, inside the box.
Hydrogen peroxide is only relatively effective against vesiculating agents, HD, and against neurotoxic agents, such as VX, which show selective oxidation and selective perhydrolysis. By adding ammonia to the steam system, hydrolysis-based deactivation of GD can also be carried out. Improvements have also been found in the deactivation rates of vesiculating agents and neurotoxic agents.
Without intending to limit the scope of the invention, it is believed that, under exposure to hydrogen peroxide vapor, selective oxidation of HD occurs to give rise to a non-vesicle-forming sulfoxide, HDO (Figure 4), avoiding the generation of a sulfone vesicle-forming (HDO2). This reaction with vaporized hydrogen peroxide takes place rapidly, more rapidly with steam than with liquid hydrogen peroxide solutions. The mass transfer of hydrogen peroxide between the vapor and the liquid agent results in the accumulation of hydrogen peroxide in the liquid phase, which causes oxidation to take place rapidly. The excess of dissolved oxidant ensures that the oxidation process takes place completely.
In neutral liquid peroxide solutions, VX is understood to undergo partial autocatalytic perhydrolysis due to the basicity of its amine group. VX acts to self-activate peroxide through protonation of the amine group. In the presence of activators that change the pH of the peroxide to basic values, perhydrolysis proceeds until complete destruction occurs.
ES 2 341 010 T3
When exposure to hydrogen peroxide vapor occurs, it is understood that VX undergoes similar perhydrolysis, causing the basicity of the amine group of the VX molecule to occur autocatalytic perhydrolysis (Figure 5). Various reaction intermediates can be formed, with different toxicities, including ethyl methyl phosphonate (EMPA) and VX-pyro, a toxic intermediate. However, hydrogen peroxide is constantly replenished by mass transfer between the liquid agent and the vapor flowing over it, maintaining adequate supply of peroxyl anion for the reaction. Acidic products that are generated by perhydrolysis are volatile, and are transported by flowing steam. Unlike stagnant liquids, this removal of acidic products prevents them from building up and reducing the pH value to a point where the reaction stops.
The additional presence of ammonia has been shown to increase the rate of degradation of VX due to hydrogen peroxide, as well as reduce the concentration of toxic by-products. The reaction is selective for non-toxic EMPA. Little or no EA-2192 is formed. VX-pyro tends to be detected only as a non-persistent intermediate. It is suggested that the nitrogen-containing compound provides a pH that is more basic than that of hydrogen peroxide alone, thus promoting the course of the reaction until EMPA is obtained.
GD does not tend to undergo significant autocatalytic perhydrolysis with either liquid or vaporized hydrogen peroxide. However, GD is susceptible to deactivation via base-catalyzed hydrolysis and perhydrolysis. In solution, perhydrolysis is about four times faster than base-catalyzed hydrolysis. Both hydrolysis and perhydrolysis result in the formation of the same non-toxic inactivation products. GD exposed to hydrogen peroxide and ammonia or short chain alkylamines that increase pH undergoes rapid perhydrolysis and / or hydrolysis, as long as the pH remains high (Figure 6). For the most part, the reaction product is pinacolylmethylphosphonic acid (PMPA). Single exposure to hydrogen peroxide does not cause perhydrolysis. However, when ammonia is added to hydrogen peroxide, hydrolysis occurs to form non-toxic inactivation products. Because G-agents are hygroscopic, ammonia tends to be easily absorbed into the moisture retained by the G-agent from hydrogen peroxide. The hydrolysis reaction is the result of the basicity of ammonia and the presence of water that is absorbed in the hygroscopic GD liquid.
It can be appreciated that other chemical weapons agents susceptible to oxidation and / or perhydrolysis are also destroyed during the hydrogen peroxide / ammonia treatment, including, but not limited to, cyanogen chloride, hydrocyanic acid, 3-quinuclinidyl benzilate ( Agent BZ).
While referring to the destruction of chemical weapons agents, the method is also suitable for the destruction of biological weapons agents, such as bacterial spores, vegetative bacteria, viruses, molds and fungi capable of killing or seriously injuring people. mammals, particularly humans. Among them are viruses, such as equine encephalomyelitis and smallpox; bacteria, such as those caused by plague (Yersina pestis), anthrax (Bacillus anthracis) and tularemia (Francisella tularensis); and fungi, such as coccidioidomycosis; as well as toxic products expressed by microorganisms; for example, the botulism toxin expressed by Clostridium botulinium bacterium.
It has been found that it is possible to deactivate a wide spectrum of biological and chemical agents (i.e. reduce their original concentration to less than 1% by weight and preferably reduce to non-detectable levels) using the mixture in the form of oxygenated water vapor and ammonia, for a relatively short period of time, preferably no longer than ten hours, and more preferably no longer than six hours. It is possible to deactivate some chemical agents, such as HD, in shorter periods of time, for example, 2 to 6 hours. Preferably, the concentration of pathogenic intermediates, eg, VX-pyro, is reduced to less than about 5% of the original weight of the chemical agent in a period of no more than about 24 hours.
Without intending to limit the scope of the invention, the following examples demonstrate the effectiveness of the combination of hydrogen peroxide and ammonia in deactivating chemical weaponry agents.
Examples
The chemical agents VX, GC and HD are deposited separately on glass filter paper (5 µl of the agent). The sample is placed in a chamber 10 of 0.15 m<sup>3</sup> that is connected to a STERIS M-100 VHP® vaporizer. The vaporizer generates hydrogen peroxide from a solution comprising 35% hydrogen peroxide in water. Chamber air is used as the carrier gas. A flow rate of around 0.3 m is used<sup>3</sup>/minute. Hydrogen peroxide is injected into the carrier gas at a flow rate of 0.4-0.5 g / minute, resulting in a concentration of hydrogen peroxide measured within the chamber of around 600 ppm. Ammonia gas is introduced into the hydrogen peroxide and the carrier gas stream just prior to its entry into the chamber, at a concentration of 0.18 ml / min, resulting in a calculated ammonia concentration of about 8 ppm. The sample is exposed to hydrogen peroxide and ammonia in the chamber for a chosen period of time of about 0.5 to about 4 hours at a temperature of about 23 ° C to about 25 ° C.
The exposed and unexposed samples are subjected to solvent extraction and the content of residual agent and reaction products in the extract is analyzed by means of NMR.
Similar experiments to the one described above were carried out, but without ammonia.
ES 2 341 010 T3
Figure 7 is a plot of the percentage, by weight, of detected initial HD and percentage of HDO reaction product (expressed as percentage of initial HD), versus time, in the presence of both hydrogen peroxide and ammonia. It can be seen that HD is not detectable after a period of two hours. An important part (around 45%) is converted into HDO.
Figure 8 shows the result for VX in the presence of hydrogen peroxide without ammonia, as well as for the reaction products VX-pyro and EMPA. Although the initial decline in VX is relatively rapid, VX levels decline completely after approximately 24 hours. At this time, the product is EMPA. VX-pyro is detected as an intermediate product, which reaches a peak concentration after about six hours and then decreases.
Figure 9 shows the comparable results for VX in the presence of both hydrogen peroxide and ammonia. In this case, the decomposition rate of VX is much higher than without ammonia, decreasing to non-detectable levels after about 6 hours. After 24 hours, all reaction products are in the form of EMPA.
Figure 10 shows the results for GD in the presence of hydrogen peroxide and ammonia. The GD concentration decreases to non-detectable levels after about 4 hours. No PPMA is detected. This may be due to evaporation of the reaction product from the sample.
Figure 11 shows comparable results for GD in the presence of ammonia and water vapor as a control.
Contents6
7 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7
24 members in 11 offices
Priority claims2
| Document | Office | Kind | Date |
|---|---|---|---|
| 42247203 | United States of America | A | |
| 51986803 | United States of America | P |
Members24
| Document | Office | Kind | |
|---|---|---|---|
| US2004215046A1 | United States of America | A1 | |
| AU2004279294A1 | Australia | A1 | |
| CA2523604A1 | Canada | A1 | |
| WO2005035067A2 | World Intellectual Property Organization (WIPO) | A2 | |
| WO2005035067A3 | World Intellectual Property Organization (WIPO) | A3 | |
| EP1615703A2 | European Patent Office (EPO) | A2 | |
| KR20060017758A | Republic of Korea | A | |
| CN1791442A | China | A | |
| US7102052B2 | United States of America | B2 | |
| US2006205991A1 | United States of America | A1 | |
| JP2006524551A | Japan | A | |
| AU2004279294B2 | Australia | B2 | |
| US7629500B2 | United States of America | B2 | |
| US2009311152A1 | United States of America | A1 | |
| US7651667B2 | United States of America | B2 | |
| US2010074804A1 | United States of America | A1 | |
| EP1615703B1 | European Patent Office (EPO) | B1 | |
| AT465787T | Austria | T | |
| ATE465787T1 | Austria | T1 | |
| DE602004026852D1 | Germany | D1 | |
| ES2341010T3This record | Spain | T3 | |
| JP4538452B2 | Japan | B2 | |
| US8025848B2 | United States of America | B2 | |
| CA2523604C | Canada | C |
Numbers
- Application
- 4809340
Titles2
- English
- STEAM TREATMENT ACTIVATED TO NEUTRALIZE ARMAMENT AGENTS.
- Spanish
- TRATAMIENTO CON VAPOR ACTIVADO PARA NEUTRALIZAR AGENTES DE ARMAMENTO.
Classification
- CPC, 7
- A62D3/38
- A62D3/30
- A61L2/20
- A61L2/208
- A62D2101/02
- A61L2103/23
- A62D3/36
- IPC, 5
- A61L2 20
- A62D3 00
- A62D3 38
- A62D3 115
- A62D101 02