JP2019181182A - Decontamination method of chemical agent, and decontamination method of biological agent - Google Patents

Abstract

To provide a decontamination method of a chemical agent capable of decontaminating a chemical weapon agent or the like scattered over a wide range and efficiently making it harmless.SOLUTION: A decontamination method of a chemical agent makes a chemical agent such as a chemical weapon agent harmless using molecule-hydrated ozone water prepared by dissolving ozone in raw water. The method includes a step for forming the molecule-hydrated ozone water having a lower hydrogen bond ratio than the hydrogen bond ratio of the raw water, a step for storing the formed molecule-hydrated ozone water in a storage tank at an atmospheric pressure, and a step for making the chemical weapon harmless with an oxidative effect of an ozone molecule by bringing the molecule-hydrated ozone water taken out of the storage tank into contact with the chemical weapon.SELECTED DRAWING: None

Description

  The present invention relates to a chemical agent decontamination method for detoxifying chemical warfare agents and the like by utilizing a high oxidizing effect of molecular hydrated ozone water, and a bioagent for detoxifying biological agents contained in biological weapons. Relates to the decontamination method.

  For decontamination of chemical warfare agents and biological weapons, methods using detergents are generally used, and alkaline water solvents, or substances having an oxidizing action such as sodium hypochlorite and sodium peroxide are effective as decontamination agents. Is known to be.

As a method for performing decontamination using a detergent having an oxidizing action, for example, Patent Document 1 (Japanese Patent Laid-Open No. 2012-24385) describes a method using ozone and hydrogen peroxide. The document includes a decontamination apparatus for a toxic substance that decontaminates a contaminated substance contaminated with a toxic substance in a reactive oxidizing agent atmosphere, a decontamination chamber that contains the contaminated substance, and the decontamination chamber. An oxidant supply device for supplying hydrogen peroxide to the chamber in a vapor atmosphere, an additive supply device for supplying ozone to improve the oxidizing power to the decontamination chamber, and a vapor in the decontamination chamber to the oxidant supply device A decontamination device having a circulation device for circulation and an exhaust device for exhausting the decontamination chamber is disclosed.
JP 2012-24385 A

  However, in the decontamination method described in Patent Document 1, it is necessary to supply ozone or hydrogen peroxide to a dedicated space such as a decontamination chamber, and decontamination of chemical warfare agents and the like dispersed over a wide area. There is a problem that it is not suitable for use in the above.

  The present invention solves the above-described problems, and the chemical agent decontamination method according to the present invention uses, for example, molecular hydrated ozone water generated by dissolving ozone in raw water, A decontamination method for detoxifying chemical warfare agents as chemical agents, a step of generating molecular hydrated ozone water in which the hydrogen bond rate in ozone water is smaller than the hydrogen bond rate of raw water, and the generated molecular hydrated ozone Storing water in a storage tank at atmospheric pressure, contacting the molecular hydrated ozone water taken out from the storage tank with a chemical warfare agent, and detoxifying the chemical warfare agent by oxidizing the ozone molecules; , Can be included.

  Moreover, the chemical agent decontamination method according to the present invention can contain, for example, ozone having a bubble diameter of less than 50 nm in molecular hydrated ozone water.

  In addition, the chemical agent decontamination method according to the present invention is, for example, a peak intensity maximum value of hydrogen bond energy of molecular hydrated ozone water is −0. It can be smaller than 0021.

  In the chemical agent decontamination method according to the present invention, for example, the molecular hydrated ozone water may be 20 ° C. or lower in the storage tank.

  Further, the chemical agent decontamination method according to the present invention includes, for example, the temperature of the molecular hydrated ozone water after the molecular hydrated ozone water is taken out of the storage tank and before contact with the chemical warfare agent. , 30 ° C. or more and less than 45 ° C. can be included.

  The biological agent decontamination method according to the present invention is, for example, a decontamination method for detoxifying a biological agent using molecular hydrated ozone water generated by dissolving ozone in raw water, A step of generating molecular hydrated ozone water in which the hydrogen bond rate is smaller than the hydrogen bond rate of raw water, a step of storing the generated molecular hydrated ozone water in a storage tank at atmospheric pressure, and from the storage tank A step of bringing the extracted molecular hydrated ozone water into contact with the biological agent and detoxifying the biological agent by the oxidizing action of the ozone molecules.

  Moreover, the decontamination method of the biological agent which concerns on this invention can contain ozone whose bubble diameter is less than 50 nm in molecular hydration ozone water, for example.

  In addition, the biological agent decontamination method according to the present invention is, for example, a peak intensity maximum value of hydrogen bond energy of molecular hydrated ozone water measured by using an infrared spectrophotometer in comparison with that of raw water is −0. It can be smaller than 0021.

  In addition, in the biological agent decontamination method according to the present invention, for example, molecular hydrated ozone water can be set to 20 ° C. or lower in the storage tank.

  Moreover, the decontamination method of the biological agent according to the present invention includes, for example, the temperature of the molecular hydrated ozone water after the molecular hydrated ozone water is taken out of the storage tank and before contacting with the biological agent, A temperature raising step of 30 ° C. or higher and lower than 45 ° C. can be included.

  According to the chemical agent decontamination method of the present invention, chemical warfare agents and the like dispersed over a wide range can be efficiently detoxified and decontaminated.

  Moreover, according to the biological agent decontamination method of the present invention, bacteria such as anthrax spores can be killed, and biological weapons can be made harmless efficiently.

It is a schematic diagram which shows the state in which the other gas molecule entered between water molecules. (A) is a schematic diagram which shows the state of the water molecule in normal water, (b) is a schematic diagram which shows the state in which the gas molecule entered between water molecules. It is a conceptual diagram of super cavitation. It is a schematic block diagram of a gas liquid mixture production | generation apparatus. It is a perspective view of the gas-liquid mixing apparatus in a gas liquid mixture production | generation apparatus. It is a conceptual diagram which shows the process which the spreading | diffusion of a gas molecule arises from a gas bubble by super cavitation. (A) is a perspective view of a general-purpose Fourier transform infrared spectroscopic analyzer, and (b) is a perspective view of a Fourier transform infrared spectroscopic analyzer for observing molecular hydrated ozone water of the present invention. It is measurement data which shows the observation result of the infrared analysis of raw | natural water. It is measurement data which shows the observation result of the infrared analysis of raw | natural water (average) and UFB ozone water (average). It is a graph which shows the value which deducted the measurement data of raw | natural water (average) from UFB ozone water (average). It is a graph which shows the value which deducted measurement data of raw water (average) from ozone water (average) of sample name L. It is a figure which shows the measurement data of the bubble diameter distribution of UFB ozone water. It is a figure which shows the measurement data of the bubble diameter distribution of the ozone water of the sample name L. (A) is a schematic diagram which shows the state of the water cluster in normal water, (b) is a schematic diagram which shows the state of the water cluster in the molecular hydration ozone water of this invention. The result of a liquid chromatography mass spectrometry (LC-MS) is shown. The result of a liquid chromatography mass spectrometry (LC-MS) is shown. The result of a liquid chromatography mass spectrometry (LC-MS) is shown. It is a figure which shows the experimental result of the bactericidal effect of the molecular hydration ozone water with respect to anthrax spore. It is a figure which shows the result of the microscopic inspection of the anthrax vegetative type. It is a figure which shows the result of the microscopic inspection of the anthrax spore lot 1. It is a figure which shows the result of the microscopic inspection of the anthrax spore lot 2. It is a figure which shows the result of the microscopic examination of a Bacillus subtilis spore. It is a figure which shows the result of the microscopic inspection of the centrifugally concentrated Bacillus anthracis spore lot 2. It is a figure which shows the experimental result of the bactericidal effect of the molecular hydration ozone water with respect to enterohemorrhagic Escherichia coli. It is a figure which shows the experimental result of the bactericidal effect of the molecular hydration ozone water with respect to a Bacillus subtilis spore.

  Hereinafter, the present invention will be specifically described.

  The present invention provides a method for decontaminating chemical agents such as chemical warfare agents using molecularly hydrated ozone water produced by dissolving ozone molecules in raw water. Ozone water molecules hydrated here means that ozone molecules exist at a high density between water molecules at least in the raw water, and the ozone water density is so high that the hydrogen bond rate becomes smaller than the hydrogen bond rate of the raw water. It refers to molecularly hydrated ozone water in which molecules are dissolved and held. From another point of view, it refers to molecularly hydrated ozone water in which ozone molecules are dissolved and held at such a high density that the hydrogen bond energy of the raw water decreases. Although ozone is known for its strong oxidizing ability, it is hardly soluble in water and liquids and cannot stably exist in combination with water molecules. When present as bubbles, the bubbles are easily lifted and degassed from the liquid surface in a short time because the mass is lower than that of the liquid. Therefore, “molecularly hydrated ozone water” used in the present invention includes the phrase “ozone water”, but is generated by the dissolution of ozone microbubbles in water like conventional ozone water. Is completely different.

The molecularly hydrated ozone water in the present invention is observed when the ozone molecules are dissipated in the water molecules and the hydrogen bond ratio is averaged, and a part of the hydrogen bonds between the water molecules is inhibited and the energy decrease is observed. It means a state where ozone is present in molecular units, not bubbles, and is maintained at an extremely high density. That is, the H ₂ O molecule group that repeats the bond separation of hydrogen bonds in nanoseconds always shows the bond energy at a constant rate (if the water temperature and pressure conditions are the same), and the rate is observable. When it decreases significantly, it proves that ozone molecules are dispersed in the H ₂ O group molecular group at an unusually high density. Of course, in the case of a gas that can be dissolved in water, such as oxygen, since it dissolves by hydrogen bonding, the action of reducing the binding energy does not occur in a dissolved state below the saturation concentration. Water repeats the movement that changes in a very short time without interruption, and structurally consists of a space that forms a gap with the water molecule group, but with molecularly hydrated ozone water, ozone exists in a high ratio in the gap. Expected to be. Unlike air bubbles, ozone present in molecular units is not affected by buoyancy, and can be stably held in the liquid. In addition, ozone self-decomposition by ultraviolet rays can be suppressed by generating it in a tank that blocks sunlight. Furthermore, the self-decomposition of ozone due to the temperature explained by the Henry constant can be suppressed by cooling the raw water to a certain degree or holding it in the ozone water generation process. At this time, the ozone water should be 15 ° C. or lower, preferably 10 ° C. or lower, and more preferably around 4 ° C. where the movement of water molecules is the slowest and most stable in order to increase the production efficiency. It becomes effective. In any case, based on the fact that it is ozone water that has been stabilized to the extent that it can be said to be molecularly hydrated ozone water, a method that suppresses the decrease in concentration, that is, the decomposition of ozone into oxygen, is combined with this purpose. It is important to adapt.

  Oxidation properties of ozone are closely related to water molecules. For example, when ozone gas and organic gas (for example, odor) are contact-reacted in a dry gas phase environment, a relatively long working time is required although there is an oxidation reaction. However, when it is humidified under the same conditions and given the condition of floating / contacting water molecules, it immediately acts and finishes the oxidation reaction. In molecularly hydrated ozone water, ozone molecules are always present next to water molecules in high density, and when the ozone comes into contact with a chemical agent such as a chemical warfare agent under the most reactive conditions, it is surprisingly unique. Increase the effect.

  Next, molecular hydrated ozone water containing ozone molecules used in the present invention will be described. In the present invention, molecular hydrated ozone water generated by dissolving ozone molecules in raw water is used. However, in the following explanation, a considerably large amount of gas is dissolved in raw water, and further stabilized gas-liquid mixed water. The gas hydration water molecules are explained, and the types of gas molecules are not limited. The gas molecule hydrated water in which the type of gas molecules is limited to ozone molecules corresponds to the molecular hydrated ozone water described above.

  First, the general concept of clathrate and hydrate will be described. A clathrate is a substance that exists in a stable state regardless of bonds such as covalent bonds because other substance atoms and molecules enter the space created by the crystal lattice of a given compound. Are known. It is also called an inclusion compound (also referred to as “inclusion”, “embracing”, etc.). For example, in the case of a silicon clathrate, a guest atom such as an alkali metal is present in a predetermined crystal structure (various types) of silicon.

  Hydrate (gas hydrate), also called water clathrate compound, is a substance that exists in a state where other gas molecules enter the gaps of a three-dimensional network structure composed of water molecules by hydrogen bonds. Commonly known as Methane hydrate, which is particularly well-known, is a substance like ice and sherbet that looks like methane molecules formed by entering methane molecules into the gaps of a three-dimensional network structure composed of water molecules. Since it is a natural resource that exists in large quantities in the near sea, its effective use is expected.

  As it is known that methane hydrate is present in solid form in the seabed and frozen soil, substances such as clathrate and hydrate can be used under conditions of high pressure environment, freezing temperature range or lower temperature. It is generally recognized that it exists in the form of a solid material having a predetermined crystal structure.

  On the other hand, when describing the concept of the present invention, terms such as “hydrate” and “clathrate” can also be used. “Hydrate” and “clathrate” in the case of meaning a product according to the present invention are It does not have the generally recognized solid / crystal lattice structure and properties described above.

  That is, as already explained, water as a base material in the present invention is only a liquid, not a structure in which interstitial bonds such as a solid / crystal lattice are combined, and differs from conventional clathrates and hydrates in this respect. In addition, the substance of the present invention can also be called gas molecule hydrated water or liquid hydrate. Although there is a fundamental difference between the conventional solid-phase gas-containing substance that is a crystallized icy solid and the matrix state of the flowing liquid phase according to the present invention, the gas is dispersed in water in molecular units. In this respect, they are common, and are therefore expressed as gas molecule hydrated water or liquid hydrate.

In 2005, RJDMiller et al. Reported that structural changes caused by laser pulse irradiation of water are lost within 50 femtoseconds. (Ultrafast memory loss and energy redistribution in the hydrogen bond network of liquid H ₂ O; Nature 434, 199-202, published March 10, 2005). In other words, the movement change of water is an extremely short-time movement, and it is difficult to perform reliable observation even in the limit range that can be measured in time. Even if there is no change in the pressure conditions surrounding the water to be observed, the kinetic energy may fluctuate greatly due to changes in the water temperature, making it impossible to measure quantitatively. Has hindered the elucidation of research.

A conceptual diagram of gas molecule hydrated water, which is a product of the present invention, is shown in FIG. This is a model showing the molecular state at the moment when water moves continuously. In FIG. 1, H atom in water molecule H ₂ O is bonded to O atom having a large electronegativity by a covalent bond (solid line in the figure) and has a positive (+) charge (hydrogen ion). . This H atom is also bonded to a negative (−) charged O atom in another H ₂ O molecule by a hydrogen bond (dotted line in the figure). In non-impurity water, the area other than each molecule in the figure is a non-material space, and water and hydrated substances such as alcohol can enter this non-material space. In this case, the total amount is reduced by a certain amount from the simple sum of both volumes. In addition, in the molecular motion of water, positively charged hydrogen ions pass between the oxygen atoms of two negatively charged water molecules (catch balls) where hydrogen bonds are present. Is known to have occurred.

When the gas is dissolved in water, it is expressed as dissolution that molecules of the gas, which is another substance that is not H ₂ O, are allowed to be dissolved in the non-material space like alcohol. Although the concentration of dissolved gas varies depending on the conditions of the environmental pressure acting on water and the water temperature, it is known that the amount of a specific gas dissolved in water under a certain condition is a certain amount. On the other hand, it has not been observed that the kinetic energy between water molecules, that is, the hydrogen bond rate changes in the dissolution phenomenon below the saturation concentration. This means that the conventionally known gas dissolving action does not change the hydrogen bonding rate of water.

  The inventor has first produced a process in which water treatment by gas-liquid mixing under a certain condition brings about a clear change in the hydrogen bond rate of water, and a substance in which such a change is recognized. Was revealed. That is, in the liquid hydrate that is the substance, the gas enters at high density between water molecules in molecular units and spreads the non-substance region, so the ratio of hydrogen bonds between water molecules is established (hydrogen bond rate ), However, it is reduced to a measurable level compared to the hydrogen bond rate of water that does not contain gas molecules.

  This arrangement relationship (the arrangement relationship in which gas molecules affect the hydrogen bond between water molecules) fluctuates by repeating disintegration and bonding in units of a few tens of femtoseconds to picoseconds due to molecular motion, It is difficult to observe. However, in the gas molecule hydrated water of the present invention, the arrangement relationship is stable and maintained so that measurement comparison is possible even in a sample after several hours. Since gas molecules are diffused throughout the water and dispersed at high density, the decrease in hydrogen bonding rate based on the arrangement relationship can be measured so that it can be observed as a total amount, and is maintained for a long time. It is thought that. As will be described later, the hydrogen bonding rate is also caused by a phenomenon in which a mass of water molecules called a water cluster collapses due to the emission and interposition of gas molecules in the process of gas-liquid mixing. It is estimated that a decrease in In the gas molecule hydrated water of the present invention, even when the dissolved gas concentration is equal to or lower than the saturated concentration, a phenomenon in which the hydrogen bond rate is clearly reduced as compared with undissolved water can be confirmed.

  The gas molecule hydrated water of the present invention is generated by dissolving gas molecules in water, and is also grasped as a “water clathrate”. Here, the original water before the gas molecules are dissolved is defined as “raw water”. Raw water includes everything that is conceptualized as water, such as general drinking water, industrial water, and pure water, and also includes water that contains some impurities. Furthermore, water containing organic matter and microorganisms as will be described later is also included, but water including such intentionally mixed water is also understood as a “stock solution”.

  Gas molecule hydrated water is generated as a result of the gas molecules dissolved in the raw water, but the hydrogen bond rate of the gas molecule hydrated water is smaller than the hydrogen bond rate of the raw water before the gas molecules are dissolved. ing. That is, the rate at which the hydrogen bond rate is established between water molecules in the gas molecule hydrated water is lower than the rate at which the hydrogen bond rate is established in the raw water. In the gas molecule hydrated water of the present invention, the liquid state is maintained in a state where the gas molecules are dissolved in water (raw water). Therefore, the gas molecule hydrated water of the present invention can also be called a gas molecule dissolved liquid. is there.

  From another point of view, in the gas molecule hydrated water of the present invention, the number of gas molecules existing in the non-material space between water molecules in the water (the space that originally has nothing other than elementary particles such as electrons and neutrons) increases. By doing so, it is grasped by the phenomenon that the non-material space is expanded and hydrogen bonds between water molecules are eliminated. Gas molecules enter between the water molecules, hindering the catching of hydrogen ions between them. In that phenomenon, the gas molecules extend the distance between water molecules to a distance larger than the distance at which water molecules can be connected by hydrogen bond energy, and the total amount decreases when the hydrogen bond energy between water molecules is measured. Has reached.

  Further, in the gas molecule hydrated water of the present invention, due to the action of the gas molecules, the hydrogen bond energy due to hydrogen bonds not only between the water molecules but also between the hydrogen ions and other contaminants is greater than the hydrogen bond energy of the raw water. It can be said that it is decreasing.

  As another reason, as will be described later, gas bubbles and gas molecule groups explode in the process of enclosing gas in a liquid using a high-speed and high-strength phenomenon such as cavitation, as will be described later. Is radiated. As will be described later, it is considered that the water cluster on the orbit where the gas molecules move is partly divided, and as a total amount, the phenomenon occurs as the hydrogen bonding rate decreases. Furthermore, the gas molecules that have been radiated and traveled stop due to the resistance of water, and are scattered at a very high density throughout the water. The phenomenon in which hydrogen bonds generated in this series of processes are disconnected (mainly the disappearance of hydrogen bonds between water clusters) and the phenomenon in which hydrogen bonds are difficult to form due to the aforementioned gas molecules (mainly between hydrogen molecules) It is considered that the phenomenon of change in water properties disclosed this time is brought about by the action of both phenomena of disappearance of hydrogen bonds. It is considered that the phenomenon that the water cluster is collapsed leads to the result that the hydrogen bond rate is remarkably reduced even under the condition of the saturation concentration or less.

  As described later, these functions described above are performed at a high density and a high concentration so that the hydrogen bonding rate can be clearly observed by infrared spectroscopy compared to the original water which is the original water. It occurs in the liquid (i.e., gas molecules are scattered in the water at high density and high concentration) and imparts a remarkable property change to the raw water. In addition, although concepts such as hydrogen bond rate and hydrogen bond energy are presented as factors to be compared with raw water and gas molecule hydrated water, comparisons under the same conditions are necessary. For example, a comparison is required between raw water and gas molecule hydrated water having equivalent components other than gas molecules. Furthermore, it is necessary to keep the water temperature constant. Furthermore, since the water kinetic energy becomes intense as the water temperature rises and the difficulty of measurement increases, it is important to keep the measurement at a low water temperature, preferably 4 ° C., which is said to be the most stable molecular density of water. In addition, in order to observe the degree of change without errors, it is necessary to measure the target liquid sample for both raw water and gas-dissolved water, average the data, and compare the averaged data together to capture clear differences. Can do. Under such conditions, for the hydrogen bond rate, hydrogen bond energy, etc. described above, observation between the raw water and gas molecule hydrated water is meaningful, and there is a difference that can be captured between the two. It happens.

  The movement of individual water molecules and gas molecules, the state of the intermolecular network is a story of the microworld, and is constantly changing in motion at the picosecond level, so it cannot be observed directly. However, by capturing the hydrogen bond energy of the entire water, the behavior of gas molecules in the hydrated water can be observed. Even in normal water, hydrogen bonds between water molecules repeatedly occur and disappear due to molecular motion, but in the gas molecule hydrated water of the present invention, gas molecules enter between water molecules, so Hydrogen bonds disappear at a higher frequency than water (number of times hydrogen bonds disappear per unit time).

  FIG. 2 (a) is a schematic diagram showing the behavior of water molecules in normal water, and FIG. 2 (b) is a schematic diagram showing the behavior of water molecules and gas molecules in the gas molecule hydrated water of the present invention. This corresponds to a view of FIG. FIG. 2B shows an example in which the gas molecules are ozone molecules, but the gas molecules are not limited to ozone molecules. As shown in FIG. 2A, in normal water, water molecules are in a state of repeating hydrogen bonding and breaking at intervals of nanoseconds or less. On the other hand, as shown in FIG. 2 (b), the gas molecules in the gas molecule hydrated water explode radially and diffuse according to the method described later, proceed through the water clusters as shown in FIG. Maintained in the ocean space of water molecules where it stopped due to resistance. Here, the gas molecules annihilate part of the bonds by refining the water cluster part having a higher hydrogen bond rate than the surroundings, and prevent the hydrogen bond formation condition by the above-mentioned mechanism of hydrogen bonds. It works to reduce some. The water cluster will be explained later.

  Moreover, the method for determining whether a predetermined liquid corresponds to the gas molecule hydration water of this invention is not limited to a specific method, All methods can be employ | adopted. An example of a simple method is a method of taking out gas from a liquid by reducing pressure. The liquid (molecules) whose hydrogen bonding rate or the like has been measured in advance is placed under a decompression condition sufficient for degassing using a known apparatus, whereby the dissolved gas (molecules) can be forcibly degassed. It is possible to determine whether or not the determination target liquid is gas molecule hydrated water by measuring the hydrogen bond rate and the like of the liquid (raw water) remaining as a result of the process and comparing it with the original liquid.

  Next, the concept of supercavitation adopted this time for the generation of hydrated water of gas molecules according to the present invention will be described. General cavitation is also called a cavitation phenomenon, where a low-pressure part of a fluid (such as water) flowing at high speed evaporates, creating a pocket of steam in a very short time, and crushing in a very short time A phenomenon that disappears. It is possible to intentionally perform high intensity mixing by mixing gas in a place where the cavitation phenomenon occurs. Super cavitation is a method for generating a large amount of general cavitation more actively and reducing friction between an object and surrounding fluid. That is, super cavitation is a phenomenon in which an effect of reducing frictional drag with a substance in contact with a fluid is developed in the downstream region in the fluid flow direction by causing cavitation at a high density. This is because the liquid around the object is vaporized by cavitation, but the drag is reduced because the density of the gas is much smaller than the fluid liquid. In this example, the resistance in the mixing device is further reduced to increase the flow rate of the liquid containing gas, and the strength of the cavitation action is increased to increase the gas bubble fragmentation effect and cause gas molecules to explode. It was used for the purpose of giving the effect of being emitted as molecular particles.

  FIG. 3 is a conceptual diagram showing a state in which super cavitation occurs. Super cavitation SC occurs behind the object (black) placed in the liquid flowing at high speed (the part shown in gray).

  Next, the structure of the gas mixture generation apparatus for generating molecularly hydrated ozone water according to the present invention will be described with reference to FIG. The gas mixture generation apparatus 201 includes a storage tank 202, a gas supply device 203, a circulation system device 204 that returns the liquid to be treated taken out from the storage tank 202 to the storage tank 202, and a gas provided in the middle of the circulation system device 204. A liquid mixing device (gas molecule hydrated water generating device) 205, a dissolution promoting tank 206, and a temperature holding device 207 attached to the storage tank 202 are included.

  As shown in FIG. 4, raw water as a liquid to be treated can be injected into the storage tank 202 via a water intake valve 202v. The storage tank 202 is for storing the raw water taken and a gas mixture circulated through the circulation system 204 described later, that is, gas molecule hydrated water (molecular hydrated ozone water). The liquid stored in the storage tank 202 is held in the range of, for example, 1 to 20 ° C. by the temperature holding device 207. By setting the temperature within this range, for example, when the gas molecule is an ozone molecule, the ozone self-decomposition phenomenon associated with the temperature rise explained by the Henry constant is suppressed, and ozone dissolution and concentration increase are efficiently performed and dissolved. It is possible not to reduce the concentration of ozone. Gases other than ozone hardly have the property of decomposition due to temperature rise, but by keeping the water temperature at a high temperature, it is possible to maintain a certain degree of stability of water molecule motion and maintain high processing efficiency as a result. The temperature holding device 207 can be omitted depending on conditions. Also, the temperature setting range can be set in consideration of the type and properties of the liquid to be treated (raw water and / or gas molecule hydrated water) and gas (gas group), and the presence or absence of additives. it can. The temperature holding device 207 includes a pump 211 for taking out the liquid to be treated from the storage tank 202 and a cooler 212 for cooling the taken out liquid to be treated. Between the storage tank 202, the pump 211 and the cooler 212. Are connected by a pipe 213 through which the liquid to be processed passes.

  A pipe 190 for taking out molecular hydrated ozone water stored in the storage tank 202 is provided, and a pump 191 and a valve 195 are provided in the pipe 190. In order to prevent the ozone gas dissolved in the raw water from being degassed, it is originally desirable to keep the inside of the storage tank 202 at a positive pressure. However, in the present invention, the inside of the storage tank 202 is intentionally maintained at atmospheric pressure. Yes. By keeping the inside of the storage tank 202 at atmospheric pressure in this way, the concentration of molecularly hydrated ozone water taken out for use from the pipe 190 is reduced too much even if the length of the pipe 190 is about 20 m. Therefore, it can be said that the molecular hydrated ozone water obtained by the gas mixture generation apparatus 201 is suitable for decontamination of chemical warfare agents.

  With the above configuration, the liquid to be treated stored in the storage tank 202 is taken out of the storage tank 202 by the action of the pump 211 and sent to the cooler 212. The cooler 212 cools the liquid to be processed sent to a temperature within a predetermined range and returns it to the storage tank 202. The pump 211 is operated only when the temperature of the liquid to be treated in the storage tank 202 measured by a thermometer outside the figure exceeds a predetermined range and needs to be cooled. By providing the storage tank 202, the above-described cooling can be performed by temporarily storing the liquid to be processed, and the liquid to be processed is put in a stable state. For example, when the gas molecules are ozone molecules, While maintaining the state of ozone, dissolution can be promoted by an action similar to aging. In addition, when there exists a possibility that a to-be-processed liquid may freeze in a cold district etc., it can also comprise so that a to-be-processed liquid may be heated using a heater apparatus with the said cooler instead of the said cooler. .

  The gas supply device 203 in the present embodiment is a device for generating and supplying a predetermined gas. Basically, the gas-liquid mixing device 205 generates a vacuum phenomenon due to the occurrence of cavitation, and the supply gas is sucked from the gas supply device 203 at a negative pressure, but may be supplied after squeezing or the like as necessary. Is possible. As long as the necessary amount of gas can be supplied, there is no limitation on the generation principle of the gas that the gas supply device 203 acts on.

  An ozonizer is used as the gas supply device 203 according to the present embodiment. Oxygen is supplied from the oxygen gas cylinder 181 and nitrogen is supplied from the nitrogen gas cylinder 182 to the gas supply apparatus 203 which is an ozonizer. The gas supply apparatus 203 has a mixing ratio of 99.5% oxygen and 0.5% nitrogen to 50 kPa. After the pressure is set to ˜200 kPa, ozone is generated by electric discharge.

  The ozone gas generated by the gas supply device 203 is supplied to the gas-liquid mixing device 205 via a needle valve 218 and a check valve 219 provided in the middle of the gas supply pipe 217. Further, the gas supply pipe 217 is provided with a first gas pressure gauge 223 on the gas supply device 203 side and a second gas pressure gauge 224 on the gas-liquid mixing device 205 side, before and after the needle valve valve 218. The pressure of ozone gas can be monitored.

  In addition, if the gas mixed with a to-be-processed liquid is air | atmosphere, for example, a compressed air apparatus (compressor) etc. will become the main components of this gas supply apparatus. In the case of mixing plural kinds of gases, an apparatus for generating or collecting each gas is used.

  Next, details of the gas-liquid mixing device (gas molecule hydrated water generating device) 205 will be described with reference to FIGS. 4 and 5. The gas-liquid mixing device 205 is also called an ejector, and has a configuration obtained by adjusting the process in the process of the inventor aiming to obtain finer bubbles in water, as described above. The gas-liquid mixing device 205 includes a venturi tube 231 and a gas supply pipe 239 as a gas supply unit that supplies gas.

  The gas-liquid mixing device 205 of this embodiment further includes a magnetic circuit 243. The venturi tube 231 and the gas supply pipe 239 are integrally formed of a magnetically permeable synthetic resin material. The Venturi tube 231 has a pipe-like appearance for passing the liquid to be processed sent from the upstream side (arrow A1 side in FIG. 5) to the downstream side (arrow A2 side in FIG. 5). It flows in the axial direction (longitudinal direction) along arrows A1 to A2. In the hollow portion defined inside the venturi tube 231 so as to penetrate the venturi tube 231 in the longitudinal direction, an upstream large path 232, a throttle ramp 233, a small diameter path 234, and an open ramp 235 from the upstream side toward the downstream side. And the downstream large path 236 is formed in a state of communicating in this order.

  The upstream large path 232 is a throttle ramp that inclines in the throttle direction at a predetermined first angle (for example, 50 degrees) with respect to the axial direction of the gas supply pipe 239 (the direction perpendicular to the axial direction of the venturi tube 231). It is connected to the small-diameter path 234 via 233, and then opened with a predetermined second angle (for example, 30 degrees) with respect to the axial direction by the open inclined path 235. The open inclined path 235 is connected to the downstream large path 236 having the same outer diameter as the upstream large path 232. In other words, the sectional area (channel area) of the throttle ramp 233 decreases toward the small path 234, and the sectional area (channel area) of the open ramp 235 increases as the distance from the small path 234 increases. That is, the cross-sectional area (flow path area) of the small diameter path 234 is the smallest in the Venturi tube 231. In general, the first angle is set to be greater than the second angle, and the inclination of the stop ramp 233 is steeper than that of the open ramp 235.

  A gas supply pipe 239 is connected to the small-diameter path 234 perpendicularly to the axial direction thereof, and an open end of the gas supply pipe 239 opens to the small-diameter path 234 at the central portion of the small-diameter path 234 in the axial direction. A gas supply pipe 217 (FIG. 4) communicating with the gas supply device 203 is connected to the supply end of the gas supply pipe 239 (the opposite side of the opening end opened to the small path 234).

  The cross-sectional area (flow path area) of the small diameter path (orifice portion) 234 is the smallest in the venturi tube 231, and the liquid to be treated sent from the throttle inclined path 233 to the small path 234 has a sudden decrease in the flow path area. Exposed to extremely high pressures. After passing through the small path 234, the liquid to be treated enters the open inclined path 235 having a cross-sectional area that increases as it moves away from the small path 234, and is released from the high pressure. Therefore, the central portion in the axial direction of the small path 234 or downstream thereof. The vicinity of the side becomes a vacuum or a state close to vacuum due to a change in pressure of the liquid to be processed. The gas that reaches the supply end of the gas supply pipe 239 is sucked (suction pressure action of the liquid to be processed) and diffused into the turbulent liquid to be processed. This phenomenon is cavitation. The speed of the water flow at the time of passing through the small path (orifice portion) 234 is about 23 m per second, but is a high speed of 20 nm when converted per nanosecond.

  A magnetic circuit 243 is fixed to the venturi tube 231 with screws (not shown). The magnetic circuit 243 connects one magnet piece 245 and the other magnet piece 246 facing each other with the venturi tube 231 interposed therebetween, and connects the one magnet piece 245 and the other magnet piece 246 to each other, and the magnet piece to the venturi tube 231. And a connecting member 248 having a U-shaped cross section having a mounting function. By constructing a magnetic circuit, the magnetic field is prevented from being emitted unnecessarily toward the periphery of the mixing device that is not the ejector. The magnet piece 245 and the magnet piece 246 are composed of the small-diameter path 234 and / or the vicinity thereof (particularly the downstream side of the small-diameter path 234) in the entire flowing water area in the ejector section pipe with the magnetic field lines (magnetic fields) as much as possible. It is preferable that it is arranged so as to pass through most. This is because it is considered that the gas can be most efficiently dissolved in the liquid to be processed by applying a magnetic force to both the liquid to be processed (water) and the gas.

  Although the magnet piece 245 and the magnet piece 246 are comprised with a neodymium magnet etc., the kind of magnet is not specifically limited. The connecting member 248 is configured by a member (for example, iron) having a high magnetic permeability (μ) so that magnetic flux action is concentrated as much as possible on the liquid to be processed and the like, while suppressing magnetic flux leakage.

  The molecularly hydrated ozone water generated by the gas-liquid mixing device 205 is sent to the dissolution promoting tank 206 via the pipe 274. The dissolution accelerating tank 206 has a cylindrical shape and promotes dissolution of gas in water. The molecularly hydrated ozone water that has passed through the dissolution accelerating tank 206 is sent to the gas-liquid separator 265. The gas-liquid separator 265 functions as a degassing structure for separating and discharging the liquid to be processed and the gas degassed from the liquid to be processed. The gas separated by the gas-liquid separation device 265 is decomposed and rendered harmless by the gas decomposition device 267 and then released to the outside of the device.

  The circulation system device 204 has a function of circulating the gas molecule hydrated water that has passed through the gas-liquid mixing device 205 and allowing the gas-liquid mixing device 205 to pass again. The reason why the gas-liquid mixing device 205 is passed again is to further increase the solubility and concentration of the gas by reinjecting the gas into the liquid to be treated (gas molecule hydrated water) in which the gas has already been dissolved. The circulation system device 204 uses a pump 271 as a drive source, and a storage tank 202 and a dissolution promoting tank 206 as main components. That is, the pump 271 pressure-feeds the liquid to be processed taken out from the storage tank 202 via the pipe 270 to the gas-liquid mixing device 205 via the check valve 272 and the pipe 273. The liquid to be processed that has passed through the gas-liquid mixing device 205 by pressure feeding passes through the pipe 274 and the dissolution promoting tank 206 and is returned to the storage tank 202 through the pipe 275. The circulatory system 204 is configured such that the above-described steps can be repeated as necessary. The number of circulations can be freely set in order to obtain the gas solubility, gas concentration, and the like of the gas molecule hydrated water to be generated. A valve 276 is provided in the middle of the pipe 275, and is used to control the water pressure of the liquid to be processed that passes through the small-diameter path 234 of the gas-liquid mixing device 205 by opening and closing the valve 276.

  In the upstream pipe of the gas-liquid mixing device 205, a flow meter 220 for detecting the flow rate of the liquid to be processed, a first pressure gauge 221 for detecting the pressure in the pipe, and a target to be sent to the gas-liquid mixing device 205. And an electromagnetic valve 225 for controlling the flow rate of the processing liquid. A second pressure gauge 222 that detects the flow rate of the liquid to be processed and the pressure in the pipe 274 is provided in the pipe 274 at the rear stage of the gas-liquid mixing apparatus 205.

  Next, the gas-liquid mixing apparatus 205 that functions as a main part that generates super cavitation will be described again with reference to FIGS. 5 and 6. The gas-liquid mixing device 205 is also referred to as an ejector, and has a configuration obtained by adjusting the in-process in which the inventor aims to obtain finer bubbles in water.

  Next, the action that has been found to be obtained by the gas-liquid mixing device 205 of this time, that is, the mechanism for generating super cavitation will be described with reference to FIGS. As shown by an arrow A1 in FIG. 5, the liquid to be processed (hereinafter referred to as “water”) that has passed through the upstream large path 232 is compressed when passing through the throttle ramp 233, and the water pressure increases rapidly. A shock wave is applied to the liquid and gas bubbles and gas molecules contained in the liquid. At the same time, the water passage speed increases rapidly. The pressure and speed of water reach a peak when passing through the small path (orifice portion) 234.

  The water passing through the small path (orifice portion) 234 passes through the small path 234 at high speed and high pressure. After passing through the small path 234, the water is sent to the open ramp 235. However, even after being sent to the open ramp 235, the water still moves at a high speed due to the law of inertia. However, since the volume of the path through which the water moves (the channel area of the open ramp 235) rapidly increases (small path 234 → open ramp 235), a high vacuum environment is realized in the water together with the decompression phenomenon. . Due to this phenomenon, water generates a suction pressure that sucks (pulls in) the gas in the gas supply pipe 239 connected to the small diameter path 234 into the small path 234, and the suction pressure causes the small pressure from the gas supply pipe 239. Gas bubbles are supplied to the water through the path 234, and a gas-liquid mixed solution is generated (FIG. 6A).

  Then, as shown in FIG. 6B, due to the high pressure shock wave of the small path (orifice portion) 234, the bubbles are compressed and cavitation occurs, and as shown in FIG. Is divided and refined.

  FIG. 6E is a schematic diagram showing an image of the flow velocity. Since the phenomenon from the explosion pulverization to the diffusion and stopping is performed in a strong magnetic field, the generation efficiency is high. In addition, the higher the speed of water passing through the small path 234, the higher the density of cavitation, that is, the super cavitation density.

  In addition to the generation process described above, bubbles that have undergone the super cavitation process and do not float in the tank are finely sized to several tens of μm or less, and then enter the super cavitation process again and again. Subject to super cavitation.

  The substances conventionally known as hydrates and clathrates are substances that exist in a state where other gas molecules have entered into the gaps of the three-dimensional network structure composed of water molecules. And it is the ice which the interstitial bond has produced between water molecules, or the sherbet-like solid, The production | generation process is performed under very high pressure and low temperature, Comprising: It does not express in a liquid layer. On the other hand, the hydrated water of gas molecules according to the present invention can be produced, for example, at 20 ° C. and atmospheric pressure, so-called normal temperature and normal pressure. In a liquid phase in which no interstitial bond is generated, gas molecules enter between water molecules. Thus, the gas molecule hydrated water of the present invention is considered to be completely different from the conventional hydrate and clathrate from the viewpoint of its form and properties as a product and the production process.

  In addition, in the production | generation of this gas molecule hydrated water, the apparatus which employ | adopted the concept of supercavitation was used, but this concept and apparatus are an example of the production | generation method to the last. The gas molecule hydrated water of the present invention is not limited to the liquid produced by these apparatuses, and is not limited to the liquid produced by the concept of supercavitation. The generation technique is not particularly limited as long as the water can be divided at a molecular level so that the gas molecules can be dissolved between the water molecules of the raw water, and the gas can be dissolved by radiation in molecular units.

  Since several types of ozone water were produced | generated by the gas liquid mixture production | generation apparatus 201 which has the above structures, it demonstrates.

  Using an oxygen gas cylinder 181 and a nitrogen gas cylinder 182, pure oxygen gas 3.95 L / min and pure nitrogen gas 0.05 L / min are flowed into an ozonizer OZC-2 manufactured by Ebara Corporation, which is a gas supply device 203. Supply at 0.75 MPa.

In the ozonizer (gas supply device 203), oxygen is changed into high-concentration ozone gas (210 g / Nm ³ ) by discharge. Thereafter, the first gas pressure gauge 223 upstream of the valve is adjusted to 0.75 MPa by the needle valve valve 218, and the downstream to the gas-liquid mixing device 205 is reduced by referring to the second gas pressure gauge 224. The necessary high-concentration ozone gas flow rate is narrowed down to the desired negative pressure.

  Next, the flow on the liquid to be processed will be described. The pure water (18 MΩ / cm) introduced into the storage tank 202 is supplied to the gas-liquid mixing device 205 by the pump 271, and after the ultra-high-concentration ozone gas is mixed in the gas-liquid mixing device 205, the storage tank 202 (water volume 50 L) is supplied. Return to).

  The gas-liquid mixing device 205 is selected so that the orifice diameter of the small path 234 is 2.1 mm, and the pump 271 is controlled by an inverter so that an appropriate flow rate is obtained. When the flow rate / water pressure is increased by the pump 271, the gas suction force in the small path (orifice portion) 234 increases, and the gas pressure downstream from the needle valve valve 218 for adjusting the flow rate of the high-concentration ozone gas approaches the vacuum pressure. The mixing immediately downstream of the small path (orifice portion) 234 of the gas-liquid mixing device 205 becomes intense, and the high-concentration ozone gas is vigorously mixed in pure water.

  The gas-liquid mixing device 205 has a structure in which a magnetic path 243 irradiates a small path (orifice portion) 234 with a magnetic field strength of 4300 gauss (central magnetic field) in a magnetic direction perpendicular to the flow path of water. A structure in which the concentration ozone gas is finely dispersed in pure water is adopted.

  In the ultra high-concentration ozone gas flow path, the first gas pressure gauge 223 can be measured upstream (on the ozonizer side), and the second gas pressure gauge 224 (negative pressure and positive pressure) can also be measured downstream (gas-liquid mixing device 205 side). The high-concentration ozone gas is sucked at a desired degree of vacuum by opening and closing the needle valve valve 218.

  The flow rate of water passing through the gas-liquid mixing device 205 was adjusted by a pump 271 and an electromagnetic valve 225 by arranging a flow meter 220 (electromagnetic induction fluid sensor manufactured by Effector Co.). The circulating flow rate of the raw water (pure water) on the side where ozone is dissolved is measured by the flow meter 220.

  Sample collection of ozone water was carried out 10 minutes after the start of generation of ozone molecular water by the gas mixture generator 201 (total amount of ultrahigh-concentration ozone gas supply 40 L: pure water 50 L). Table 1 shows various parameters when ozone water is generated by the gas mixture generation apparatus 201. The ozone water generated by the gas mixture generation apparatus 201 includes 12 types of sample names A to L including the molecularly hydrated ozone water used in the present invention. In Table 1, the primary pressure [kPa] is the reading value of the first pressure gauge 221, the secondary pressure [kPa] is the reading value of the second pressure gauge 222, and the flow rate [L / min] is the flow rate. The gas pressure [mmHg] is the reading value of the second gas pressure gauge 224, and the gas flow rate [L / min] is the sum of the flow rates set in the oxygen gas cylinder 181 and the nitrogen gas cylinder 182. is there.

  As a comparative example, ultrafine bubble ozone water was similarly prepared by a 10-minute treatment (total amount of ultrahigh-concentration ozone gas supply 40 L: pure water 50 L). UltrafineGaLF FZ1N-05S manufactured by IDEC was used for the generation of ozone water, and the same high-concentration ozone gas as the gas mixture generation apparatus 201 used in the present invention was supplied to generate ultrafine bubble ozone water. At this time, the amount of water was set to 50 L, and 4 L of ozone gas was mixed per minute to obtain sample water, which was measured. The sample name of ultra fine bubble ozone water is “UFB”.

  Next, an analysis experiment by infrared irradiation performed to investigate the actual state of molecularly hydrated ozone water in the present invention will be described. In general, for analysis and identification of a substance, an ordinary microscope, X-ray irradiation, Raman spectroscopic irradiation, laser light irradiation is performed, and observation of a scattered light peak shift in this is used. With respect to the ozone water obtained by the apparatus shown in FIGS. 4 and 5, various observation methods have been used to observe the actual state, particularly the ozone gas bubbles in the water.

  In order to observe the state where ozone gas is dissolved in water at the molecular level as in the present invention, the hydrogen bond rate in water is changed compared to the original water (raw water) (hydrogen bond). A drop in rate) must be observed. Although the X-ray irradiation method is suitable for the measurement of the crystal, it is not suitable for the measurement of the fluid liquid, and the state of hydrogen bonding cannot be observed. In the case of Raman spectroscopic irradiation, the characteristics of the light beam were not optimal for water measurement, and there was a lack of accuracy (resolution), and a measurement result related to a clear difference could not be obtained. Therefore, the molecular hydrated ozone water of the present invention was observed by an analysis experiment using infrared irradiation.

  The contents of the analysis experiment using infrared irradiation will be described below. This experiment is the so-called infrared spectroscopy, which irradiates the substance to be measured with infrared rays and separates the transmitted (or reflected) light to obtain a spectrum (spectrum peak). A method of knowing the characteristics of an object.

  In carrying out the infrared analysis experiment, a Fourier transform infrared spectroscopic analyzer (also referred to as “infrared spectrophotometer”) Spctrum-one system B manufactured by Perkinelmer was used. As shown in FIG. 7A, this apparatus as a general-purpose product passes infrared rays emitted from a light source through a mirror and a prism, irradiates a liquid (molecular hydrated ozone water) as a specimen, and reflects by the liquid. Infrared light passed through the prism and mirror is introduced into the light receiving section, and the change is measured.

  That is, the Fourier transform infrared spectroscopic analyzer 300 includes a mirror 301 bent in an L shape, a prism 302, and a specimen placement base 303. A specimen filling hole 303a is provided at the center of the upper surface of the specimen placement pedestal 303, and the liquid L fills the specimen filling hole 303a by dropping the liquid L, which is a specimen, onto the top face of the specimen placement pedestal 303 with a spoid or the like.

  In the observation, the infrared ray IR1 emitted from the light source is reflected by the first surface of the L-shaped mirror 301 and guided to the prism 302. The infrared ray IR1 that has entered the prism 302 is guided to the specimen filling hole 303a of the specimen placement base 303, transitions to the infrared ray IR2 having different characteristics depending on the liquid L in the specimen filling hole 303a, and is reflected by the liquid L. The light travels inward and is emitted from the prism 302. The infrared ray IR2 emitted from the prism 302 reaches the second surface of the L-shaped mirror 301, is reflected by the second surface, and is guided to a light receiving surface (not shown). The actual state of the liquid L can be observed by analyzing the difference in characteristics between the infrared rays IR1 and IR2.

  However, in the configuration of such a general-purpose product, the observation is performed in a state where the liquid L as the specimen is dropped into the specimen filling hole 303a formed in a concave shape in a circular mortar shape having a diameter of about 10 mm. It communicates with the part exposed to the outside world on the upper surface. Since the volume of this part is not large (drop volume of several drops), the entire temperature of the dropped liquid L including the part in the specimen filling hole 303a is instantaneously synchronized with the temperature around the apparatus (room temperature), The temperature rose to room temperature (about 28 ° C.). In the measurement under this environment, the molecular motion of water was too intense, and it was difficult to evaluate the test results with the analytical performance of infrared analysis.

  Therefore, the inventor, when observing the liquid of the present invention, keeps the liquid at a temperature near 3.98 ° C. at which the water temperature is lowered to the highest density and increases the amount of the liquid so that the target liquid contacts the detection device. Considering that it is important to avoid changes due to contact with the parts, a holder 304 was prepared as shown in FIG. 7B and placed on the upper surface of the specimen placement base 303. That is, the generated liquid (gas molecule hydration water) was cooled before observation. The specimen placement base 303 and the holder 304 of the Fourier transform infrared spectroscopic analyzer 300 were cooled to near 0 ° C. before observation using an ice bag. In addition, the liquid can be held on the upper surface of the specimen placement base 303 using the holder 304 in order to prevent the water temperature from rising as much as possible due to room temperature (the room where the apparatus is located was 28 ° C.). At the same time, the sample solution produced at room temperature of 20 ° C. was cooled in a sealed container at one end and cooled to near 0 ° C. The amount of sample liquid injected into the holder 304 was increased to 10 ml so that an instantaneous increase in water temperature did not occur during the observation time.

  In the configuration of FIG. 7B, the temperature rise of the clathrate being observed is suppressed, the temperature range from about 1 to 2 ° C. to less than 10 ° C., that is, the water molecule motion is suppressed, and the change in hydrogen bonding rate can be analyzed. Observations that maintain a certain level (suppression of water molecular motion and observation without fluctuation of conditions due to changes in water temperature) became possible.

Next, the details and results of the analysis will be described. In actual analysis, each sample was measured for absorbance of infrared rays every time the temperature was increased by 1 ° C. from around 0 ° C. at the start of observation, and was measured up to 10 ° C. FIG. 8 is measurement data showing observation results of infrared analysis of raw water. The value measured at the top is when the water temperature is 10 ° C., and the one with the temperature lowered by 1 ° C. is described below. The data at the water temperature at the start of measurement is the lowest data, and the measured value is recorded every time it rises by 1 ° C. from the bottom, and all measured data are displayed. The unit of the horizontal axis is Kaiser (cm ⁻¹ ), which corresponds to the infrared frequency. The vertical axis corresponds to the relative intensity between each data of infrared absorbance, and there is no unit.

  In general, a typical absorbance peak of water by infrared analysis (hereinafter referred to as “peak”) is obtained in the vicinity of 3400 Kaiser (specifically, 3200 Kaiser and 3600 Kaiser) and is also a unique peak in the vicinity of 1600 Kaiser. Is obtained. The peak near 3200 Kaiser corresponds to the hydrogen bond state. The peak near 3600 Kaiser corresponds to the expansion and contraction of the bond (covalent bond) between the oxygen atom and hydrogen atom in the water molecule, and the peak near 3200 Kaiser is between the hydrogen bond between water molecules and other molecules (gas molecules). Corresponds to the amount of coupling between.

  Next, all the samples are averaged, and the measurement data is averaged in a temperature region where the water molecule motion is relatively stable from 0 ° C. to 10 ° C. FIG. 9 illustrates the average (upper) of the raw water measurement data thus obtained and the average (lower) of the UFB water measurement data.

  As described above, all the samples are averaged and the measurement data is averaged in a temperature range where the water molecule motion is relatively stable from 0 ° C. to 10 ° C., and the data of the raw water and the dissolved gas is compared. The difference was confirmed by subtracting the raw water used as a control in which no gas was dissolved from the gas dissolved solution to be analyzed. For example, FIG. 10 is a graph showing a value obtained by subtracting measurement data of raw water (average) from UFB ozone water (average). FIG. 11 is a graph showing a value obtained by subtracting measurement data of raw water (average) from ozone water (average) of sample name L.

  Table 2 shows the results of infrared analysis of sample names UFB and A to L.

  Calculation of the decrease value of hydrogen bond energy is as follows. First, an average value from 4000 Kaiser to 3700 Kaiser (baseline 1 (absorbance average of 4000 to 3700 in the table)) is obtained from infrared spectroscopic analyzer data, and then an average value from 2800 Kaiser to 2000 Kaiser (Baseline 2). (Absorbance average in table 2800-2000)) was determined and averaged to obtain “absorbance average” in the table. In addition, the maximum (maximum value on the minus side) between 3700 Kaiser and 2800 Kaiser was grasped (“maximum height” in the table). Then, the average value of raw water was subtracted from each sample, and the maximum value (decrease rate) of peak intensity was grasped.

  The extent to which the hydrogen bond energy is reduced is signified as the generation of a large amount of fine bubbles determined by a dynamic light scattering photometer measured with a sample having the same properties.

In general, the definition of the maximum absorption peak intensity may be considered as follows.
Calculate the maximum absorption peak intensity (Pa1) in the range from 2843 Kaiser to 2853 Kaiser.
-The average value (Pa2) of the absorption intensity of 3050 Kaiser and 2600 Kaiser is calculated.
The maximum absorption peak intensity Pa in the range from 2843 Kaiser to 2853 Kaiser is calculated from Pa1-Pa2.

  The molecular hydrated ozone water produced by dissolving ozone gas molecules in water gave a gas molecule hydrated water in which the hydrogen bond peak between water molecules measured by infrared spectroscopy was smaller than that of water. It was confirmed. In other words, in the molecularly hydrated ozone water of the present invention, the ozone gas molecules are denser in the whole water so that the peak of hydrogen bonds between water molecules is smaller than that of water as observed by infrared spectroscopy. Is distributed.

  Here, among the ozone waters in Table 2, the maximum hydrogen bond energy peak intensity value of ozone water is smaller than −0.0021 compared to the raw water (the absolute value of the difference is larger than | −0.0021 |). ) The ozone water of Samples D to L could be suitably used as ozone water for decontamination.

  In the above observation method, the specimen placement base 303 and the holder 304 are used for cooling the ozone water. However, if there is a cooling device that cools and keeps the ozone water below a predetermined temperature suitable for observation, The form is not particularly limited. As long as the conditions are suitable for observation, various conditions such as the cooling temperature and the amount of sample liquid to be observed are not particularly limited to those in the embodiment.

  Furthermore, as described above, the inventor has found that as a result of the gas molecules being dispersed in the raw water and the raw solution, the state of the raw water and the cluster of water molecules (water cluster portion) in the raw solution are changed. RIKEN Research Institute Press Release “Discovering non-uniform microstructure in liquid water that was thought to be uniform” (http://www.riken.go.jp/r-world/research/results/2009 /090811/index.html), it is known that there is a fine structure (non-uniformity) in water that has long been considered to be a uniform liquid. As a result of analysis by X-ray beam line IBL45XU small-angle scattering and high-precision Raman light analyzer of large synchrotron radiation facility Spring-8, water density non-uniformity is derived from two kinds of fine structures in water. I understood it. In other words, the non-uniformity of density occurs because the “microstructure very similar to ice” has a microscopic structure like a polka dot used in the sea of “water molecules with distorted hydrogen bonds”. ing.

  Here, the “fine structure similar to ice” is a state in which water molecules are gathered at a higher density than the surroundings, and forms a kind of cluster structure. This is observed by measuring water molecules in femtosecond units, and it is understood that the cluster structure repeats generation and disappearance in a very short time. It can be said that the state of the water molecule group gathered at a high density, that is, the water ball part, has a higher hydrogen bond rate than the water region where other molecules exist at a low density.

FIG. 14A is a schematic diagram showing the state of a water cluster in normal water (raw water), and about several tens of water molecules continue to change their configuration at a speed of nanoseconds or less. In FIG. 14A, the water cluster portion is schematically represented by an annular cluster region. In the case where a cyclic cluster is represented by (H ₂ O) n, studies have been made on the case where n, which is the number of water molecules H ₂ O, is 3 to 60, for example, but the range of n is not particularly limited. There is also a single movement of each water molecule, but a cluster in which water molecules are gathered in a bunch of cocoons (hereinafter referred to as “water cluster part”) is also generated in water. Show your own movement.

  On the other hand, FIG.14 (b) is a schematic diagram which shows the state of the water cluster in the molecular hydration ozone water of this invention. As described above, in the present invention, a large amount of gas molecules pass through the sea of water molecules of raw water during the explosion and diffusion of gas molecules, and the water clusters shown in FIG. The part is divided and subdivided. In FIG. 14B, the subdivided water cluster portion (fine water cluster portion) is schematically represented by an elliptical annular cluster region. After that, gas molecules exist between water molecules. That is, in the molecularly hydrated ozone water of FIG. 14B, by dissolving gas molecules in the raw water, the water cluster portion in the raw water in which water molecules are gathered at a higher density than the surroundings is crushed. Compared with the raw water of (a), the water cluster part is refined | miniaturized. As a result, in the molecularly hydrated ozone water of the present invention, the average number of water molecules in the water cluster portion is smaller than the average number of water molecules in the water cluster portion in the raw water. Further, gas molecules are densely intervened in water clusters that change in nanosecond units, thereby maintaining a state in which it is difficult to form a large water cluster portion and maintaining a fine water cluster portion. As a result, in the molecularly hydrated ozone water of the present invention, it is possible to maintain a small state of the water cluster part on average for a long time as compared with untreated raw water.

  The retention of fine water clusters in the molecularly hydrated ozone water of the present invention means that the area where water molecules are present at a higher density than the raw water is reduced. This means that the distance between water molecules is increased on average, and as a result, the hydrogen bond rate of molecularly hydrated ozone water is lower than the hydrogen bond rate of raw water. That is, in the present invention, the action of gas molecules that cause a decrease in the hydrogen bond rate is not only an action that exists between water molecules and weakens the hydrogen bonds between the water molecules (lowers the hydrogen bond energy). . The gas molecules also bring about the effect of lowering the hydrogen bond rate by exerting the action of destroying and refining the water cluster part of the raw water and holding the refined water cluster part. Therefore, it is not necessary for the amount of dissolved gas to reach the saturation concentration as a condition for generating the molecular hydrated ozone water of the present invention. Below, molecular hydrated ozone water can be generated even when the amount of gas is below the saturation concentration.

  Next, since the particle diameter measurement of the bubble was performed about the ozone water of sample name UFB and A thru | or L, this is demonstrated. ELSZ-2000ZS manufactured by Otsuka Electronics Co., Ltd. was used for the measurement, and the bubble particle size was measured by the dynamic light scattering method. As an example of the measurement result, FIG. 12 shows measurement data of bubble diameter distribution of UFB ozone water, and FIG. 13 shows measurement data of bubble diameter distribution of ozone water of sample name L. Table 3 shows the bubble diameter at which the number distribution peaks for each sample.

  From the results of particle size measurement, raw water is excluded because it is pure water that does not contain fine bubbles. In addition, the UFB ozone water had a bubble diameter peak (bubble diameter at which the number distribution had a peak) of 1128 nm, and bubbles smaller than 50 nm could not be measured.

  In the molecularly hydrated ozone water of the present invention, the bubble diameter at which the number distribution takes a peak is preferably 50 nm. When the second gas pressure gauge 224 of the ozone gas supply path in the gas mixture generation apparatus 201 is a sample (A to C) in the range of 35 mmHg to −80 mmHg, the bubble diameter peak is 1319.1 to 66.8 nm, which is 50 nm or less. Data could not be measured.

  In the samples (D, E) in which the gas pressure of the second gas pressure gauge 224 was in the range of −200 mmHg to −370 mmHg, the bubble diameter peak was 47.4 to 39.6 nm. Furthermore, in the samples (F, G) in the range of −480 mmHg to −640 mmHg, the bubble diameter peak was 24.8 to 24.6 nm, and it was confirmed that a lot of finer fine bubbles were generated.

  In the sample (H to L) in which the gas pressure of the second gas pressure gauge 224 is in the range of −760 mmHg, the bubble diameter peak is 12.2 to 11.3 nm, and it is confirmed that almost the entire amount is generated with ultrafine bubbles. It was done.

  From the above, when generating ozone water with the gas mixture generator 201, the pressure of the ozone gas supplied to the gas-liquid mixer 205 is a negative pressure, and more preferably, the pressure of the ozone gas is -200 mmHg or less. Even more desirably, it was confirmed that the pressure of the ozone gas was −760 mmHg or less.

  There is a correlation between the reduction effect of hydrogen bond energy obtained by measurement with an infrared spectrometer and the state of generation of ultrafine bubbles due to dynamic light scattering. It can be seen that the substance is dissolved in water in such a large amount that it can be recognized as a decrease in the hydrogen bond energy of water after high-density dispersion.

  In the molecularly hydrated ozone water of the present invention, when ozone water is generated by the gas mixture generator 201, the ozone gas or ozone molecule can be efficiently produced when the pressure of the ozone gas supplied to the gas / liquid mixer 205 is −760 mmHg or less. However, it is dissolved in large quantities with ultrafine bubbles below 20 nm. It can be presumed that the molecularly hydrated ozone water generated under such conditions is very effective for detoxifying chemical warfare agents and killing biological weapons.

  In addition, it is known that ozone molecules exert the maximum oxidation effect when they come into contact with an object at the same time as water molecules. In this sense, the molecular hydrated ozone water of the present invention makes chemical warfare agents harmless. It can also be expected to be very effective in killing biological weapons.

  Chemical weapons such as nerve agents such as VX gas, erosion agents such as mustard gas, and biological weapons using biological harmful substances such as Bacillus anthracis and Vibrio cholerae are inactivated or harmless by various oxidizing agents. It is known that it will be decontaminated.

  The chemical agent decontamination method according to the present invention proposes decontamination of a chemical warfare agent using the molecularly hydrated ozone water having a very strong oxidizing ability as described above. In the following embodiment, this decontamination will be described using a chemical warfare agent as an example, but it has been confirmed that molecular hydrated ozone water can also perform decontamination on the above biological weapons.

  In the chemical agent decontamination method according to the present invention, the molecular hydrated ozone water described so far is stored in the storage tank 202, and the molecular hydrated ozone water taken out from the storage tank 202 is brought into contact with the chemical warfare agent. , Including the step of detoxifying chemical warfare agents by the oxidizing action of ozone molecules.

  We have not verified the decontamination of chemical warfare agents that are vulnerable to alkalis like sarin as chemical warfare agents, but are stable to oxidizing ability. If the sprayed chemical warfare agent cannot be identified, it is possible that the chemical warfare agent is a weak chemical warfare agent such as sarin. After contacting the decontaminating agent with the chemical warfare agent, it is preferable to further perform decontamination by contacting with the molecularly hydrated ozone water according to the present invention having a large oxidizing effect.

  Moreover, in the chemical agent decontamination method according to the present invention, it is preferable that the molecular hydrated ozone water is 20 ° C. or less in the storage tank 202. By such temperature setting, in the storage tank 202, it is possible to suppress the self-decomposition phenomenon of ozone molecules accompanying the temperature rise and perform effective decontamination without reducing the ozone concentration.

  On the other hand, in the chemical agent decontamination method according to the present invention, after the molecular hydrated ozone water is taken out of the storage tank 202, the molecular hydrated ozone water is heated at a stage before contacting with the chemical warfare agent. It is preferable to employ a temperature raising step of 30 ° C. or higher and lower than 45 ° C. Further, after the molecular hydrated ozone water is taken out from the storage tank 202, a temperature raising step for bringing the temperature of the molecular hydrated ozone water to 45 ° C. or more and less than 90 ° C. before contacting with the chemical warfare agent is performed. It is more preferable to adopt.

  In normal ozone water, ozone gas is degassed instantly and cannot be brought into contact with chemical warfare agents at a high dissolved concentration, but the molecular hydrated ozone water according to the present invention greatly increases its oxidation effect by instantaneous heating. And a further decontamination effect can be expected.

  In addition, as described above, after the molecular hydrated ozone water is taken out from the storage tank 202, a temperature raising step for raising the temperature of the molecularly hydrated ozone water is adopted at a stage before contacting with the chemical warfare agent. In this case, it is desirable that the time required for the temperature raising step is 60 seconds or less.

[Example 1]
Hereinafter, the detoxification of chemical warfare agents by molecular hydrated ozone water will be described with reference to examples.
In this example, VX which is a nerve agent, HD (Mustard gas) and HN1 (Nitrogen Mustard) which are erosants were used as chemical agents. The structural formulas of VX, HD, and HN1 are shown below.

  The chemical warfare agent referred to in this specification is a chemical agent that can cause fatal damage to humans and can be used as a weapon. The chemical warfare agent is a chemical weapon prohibition treaty (chemical Chemical substances specified in the Convention on the Prohibition of Development, Production, Storage and Use of Weapons, and Disposal) shall be included.

(Preparation of chemical warfare agent sample solution)
A VX sample solution in which 1% by volume of VX was dissolved in normal hexane (hexane 300 manufactured by Kanto Chemical Co., Inc.) was prepared. In addition, an HD sample solution in which 1% by volume of HD was dissolved in normal hexane (Kanto Chemicals hexane 300) was prepared. An HN1 sample solution in which 1% by volume of HN1 was dissolved in normal hexane (hexane 300 manufactured by Kanto Chemical Co., Inc.) was prepared.

(Preparation of molecular hydrated ozone water)
Three types of molecular water with different ozone concentrations: a stock solution of molecular hydrated ozone water generated by the gas mixture generation device 201 described so far, a stock solution diluted three times, and a stock solution diluted ten times. Japanese ozone water was prepared. The ozone concentration of the stock solution of molecular hydrated ozone water generated by the gas mixture generation device 201 differs depending on the lot when it is generated. In this embodiment, the ozone concentration of the stock solution is 66 [ppm] to 80 [ppm]. Met. In this example, tap water provided by the Chiba Prefectural Waterworks Bureau was used as the raw water into which ozone was dissolved.

(Reproduction of contact between chemical warfare agent sample solution and molecular hydrated ozone water)
A chemical warfare agent sample solution of 30 μL of either VX, HD, or HN1 and 5 mL of any of three types of molecular hydrated ozone water having different concentrations were prepared in a capped test tube. The prepared capped test tube was shaken in a shaking thermostat kept at 25 ° C. (manufactured by TAITEC Corporation, temperature control part model number: SH-10N, shaking part model number: personal H-10). The shaking time was 2 minutes, 10 minutes, 30 minutes, and 150 minutes.

1. Measurement of residual ratio of chemical warfare agent by gas chromatography mass spectrometry (GC-MS) After shaking for 10 minutes, 30 minutes and 150 minutes, the remaining chemical warfare agent was dichloromethane (Wako Pure Chemical Industries, Ltd.) Preparation to extract to the company). Here, 1 mL of dichloromethane is dropped into the capped test tube containing the chemical weapon agent sample solution of HD, and 1 mL of dichloromethane and 1 M are added to the vial containing the chemical weapon agent sample solution of either VX or HN1. 200 μL of tris solution was added dropwise. As the tris solution, an aqueous solution of tris (hydroxymethyl) aminomethane for biochemistry manufactured by Wako Pure Chemical Industries, Ltd. was used.

  All the test tubes with caps were vibrated with a test tube mixer (HM-10 model manufactured by ASONE), and then the dichloromethane layer and other layers were measured with a micro high-speed cooling centrifuge (MX-301 model manufactured by Tommy Seiko Co., Ltd.). Was centrifuged.

Next, only the dichloromethane layer was transferred to a GC-MS dedicated vial, and gas chromatography mass spectrometry was performed. The apparatus and conditions used for gas chromatography / mass spectrometry are shown below. As for the gas chromatograph / mass spectrometer, two apparatuses were used for the convenience of analysis time.
(Condition 1)
・ Gas chromatography (GC)
Apparatus: 6890N manufactured by Agilent Technologies, Inc.
Column model number: DB-5MS (manufactured by Agilent Technologies, Inc., 30 m × 0.25 mm ID, 0.25 μm in thickness)
Injection method: split ratio 30: 1
Inlet temperature: 250 ° C
Ion source temperature: 230 ° C
Column temperature: 40 ° C. (1 minute) → 20 ° C./min→290° C. (5 minutes)
Helium flow rate: 0.7 mL / min
Injection volume: 1 μL
・ Mass spectrometry (MS)
Apparatus: 5975B insert MSD manufactured by Agilent Technologies, Inc.
Ionization voltage: 70 eV
(Condition 2)
・ Gas chromatography (GC)
Apparatus: 7890B manufactured by Agilent Technologies, Inc.
Column model number: DB-5MS (manufactured by Agilent Technologies, Inc., 30 m × 0.25 mm ID, 0.25 μm in thickness)
Injection method: split ratio 50: 1 or 20: 1
Inlet temperature: 250 ° C
Ion source temperature: 230 ° C
Column temperature: 40 ° C. (0.5 minutes) → 100 ° C./min→290° C. (1.5 minutes)
Helium flow rate: 2.5 mL / min
Injection volume: 1 μL
・ Mass spectrometry (MS)
Equipment: 5977A MSD manufactured by Agilent Technologies
Ionization voltage: 70 eV
Next, Table 4 shows the results of gas chromatography mass spectrometry.

(ND in the table is an abbreviation for Not Detected)
Under the condition of constant shaking time of 10 minutes, the residual rate decreases in the order of 10-fold dilution-> 3-fold dilution-> stock solution in any chemical warfare agent, and the higher the ozone concentration, the more effective the chemical It was confirmed that the molecular structure of weapon agents could be destroyed and detoxified.

  In addition, by using the stock solution of molecular hydrated ozone water generated by the gas mixture generation apparatus 201 as it is and setting the shaking time to 10 minutes or more, for any chemical warfare agent, the molecule of the original chemical warfare agent The chemical agent decontamination method according to the present invention was confirmed to be effective.

  Next, in order to estimate the decomposition product of the chemical warfare agent produced by contact with molecular hydrated ozone water, confirmation was performed by liquid chromatography mass spectrometry (LC-MS) method.

  200M of 0.1M sodium thiosulfate solution (0.1 mol / L sodium thiosulfate solution manufactured by Wako Pure Chemical Industries, Ltd.) is added to the chemical warfare agent sample solution mixed with molecular hydrated ozone water and shaken for a predetermined time. By adding, the remaining ozone was deactivated.

2. Measurement of chemical warfare agent decomposition product by liquid chromatography mass spectrometry (LC-MS) method The apparatus and conditions used for liquid chromatography mass spectrometry are shown below. LC-MS analysis was performed on the hydrolyzate of VX, and it was confirmed that the retention time and mass spectrum of the standard product and LC matched. Other decomposition products were detected by direct introduction into a mass spectrometer (infusion, ESI-TOF MS).
(About analysis of hydrolyzate of VX)
・ Liquid chromatography (LC)
Apparatus: Nexera X2 HPLC manufactured by Shimadzu Corporation
Column model number: L-column2 ODS (CERI, 1.5 × 150 nm, 5 μm)
Column temperature: 40 ° C
Flow rate: 0.2mL / min
Injection volume: 10 μL
・ Mass spectrometry (MS)
Equipment: impact HD Q-TOF mass spectrometer manufactured by Bruker Daltonics
The Pos. Ionization voltage during ionization: 4.5 kV
Neg. By ESI method. Ionization voltage during ionization: 4.0 kV
(For analysis of VX, HD and HN1 sample solutions)
・ Mass spectrometry (MS) (infusion)
Equipment: impact HD Q-TOF mass spectrometer manufactured by Bruker Daltonics
The Pos. Ionization voltage during ionization: 4.5 kV
Neg. By ESI method. Ionization voltage during ionization: 4.0 kV
Next, the results of liquid chromatography mass spectrometry (LC-MS) or analysis by direct introduction (ESI-TOF MS) are shown in FIG. 15, FIG. 16, and FIG. 15 and 16 are diagrams showing analysis results based on the VX sample solution, and FIG. 17 is a diagram showing analysis results based on the HD sample solution.

  In the box of FIG. 15, the molecular structure of the standard product (VX hydrolyzate) corresponding to the spectrum is shown. In the box of FIG. 16, the molecular structure of the molecule estimated corresponding to the spectrum is shown. In the box of FIG. 17, the molecular structure of the molecule estimated corresponding to the spectrum is shown.

  From the analysis results of FIGS. 15 to 17, it can be confirmed that the chemical warfare agent is damaged by contact with molecular hydrated ozone water to the extent that a decomposition product is generated, and as a result, the chemical warfare agent is rendered harmless. It was. In particular, according to FIG. 16, a decomposition product in which PS bond in VX is cut can be confirmed, and according to FIG. 17, a decomposition product in which oxygen is bonded to S in HD can be confirmed. It can be estimated that significant detoxification could be achieved by the effect of water.

  As described above, according to the chemical agent decontamination method of the present invention, chemical warfare agents and the like spread over a wide range can be detoxified and decontaminated efficiently.

  Next, an embodiment of the present invention for decontamination of biological weapons using molecular hydrated ozone water will be described. The term “biological weapon” as used herein can be defined based on the “Act on the Implementation of Conventions on the Prohibition, Disposal, and Disposal of Bacterial Weapons (Toxic Weapons) and Toxic Weapons”.

  That is, the “biological weapon” in this specification is filled with “biological agents or organisms that possess and mediate biological agents”, and the “biological agents” are “microorganisms, "When they grow in vivo in animals or plants, they cause disease, death or death, or produce toxins".

  Typically, “biological agents” in “biological weapons” include anthrax, smallpox virus, plague, botulinum, cholera, hemorrhagic fever virus, botulinum toxin, Staphylococcus aureus enterotoxin B, ricin toxin, etc. Can be mentioned. The present invention relates to a decontamination method for detoxifying such a biological agent using the molecularly hydrated ozone water described so far.

  More specifically, in the biological agent decontamination method according to the present invention, ozone molecules are present at a high density between water molecules at least in the raw water, and the ozone molecules are so dense that the hydrogen bond rate is smaller than the hydrogen bond rate of the raw water. The step includes contacting the biological agent with molecular hydrated ozone water in which is dissolved and held, and detoxifying the biological agent by the oxidizing action of ozone molecules.

  In the biological agent decontamination method according to the present invention, the molecular hydrated ozone water contains ozone having a bubble diameter of less than 50 nm. Moreover, compared with raw | natural water, the peak intensity maximum value of the hydrogen bond energy of the said molecular hydration ozone water is smaller than -0.0021 by the measurement using an infrared spectrophotometer.

  In the bioagent decontamination method according to the present invention, the molecular hydrated ozone water described so far is stored in the storage tank 202, the molecular hydrated ozone water taken out from the storage tank 202 is brought into contact with the biological agent, It includes a step of detoxifying the biological agent by the oxidizing action of ozone molecules.

  Moreover, in the biological agent decontamination method according to the present invention, it is preferable that the molecular hydrated ozone water is set to 20 ° C. or less in the storage tank 202. Such temperature setting suppresses the self-decomposition phenomenon of ozone molecules accompanying the temperature rise in the storage tank 202, and enables effective decontamination without reducing the ozone concentration.

  On the other hand, in the biological agent decontamination method according to the present invention, after the molecular hydrated ozone water is taken out of the storage tank 202, the molecular hydrated ozone water is heated at a stage before contacting with the biological agent. It is preferable to employ a temperature raising step of 30 ° C. or higher and lower than 45 ° C. Furthermore, after the molecular hydrated ozone water is taken out of the storage tank 202 and before contacting with the biological agent, a temperature raising step is adopted in which the temperature of the molecularly hydrated ozone water is 45 ° C. or higher and lower than 90 ° C. More preferably.

  In normal ozone water, ozone gas is degassed instantly and cannot be brought into contact with the biological agent at a high dissolved concentration. However, the molecular hydrated ozone water according to the present invention greatly increases its oxidation effect by instantaneous heating. And a further decontamination effect can be expected.

  As described above, after the molecular hydrated ozone water is taken out from the storage tank 202, a temperature raising step for raising the temperature of the molecularly hydrated ozone water is adopted at a stage before contacting with the biological agent. In some cases, it is desirable that the time required for the temperature raising step be within 60 seconds.

[Example 2]
Hereinafter, an example is shown and sterilization processing of a biological agent by molecular hydration ozone water is explained.
In this example, Bacillus anthracis was used as the target biological agent. Two forms of anthrax were used, both anthrax spores and anthrax trophozoites. Of these anthrax, anthrax spores having a spore shell are known to be difficult to kill.

  Further, in this example, although not defined as the biological agent as described above, it has a thicker spore shell than the spore shell of anthrax spore and is more difficult to sterilize and is easier to handle than the anthrax experimentally. Experiments were also conducted on the bactericidal treatment of Bacillus subtilis spores. Such Bacillus subtilis spores are considered to be one of the most difficult to kill. Therefore, if it can be confirmed experimentally that Bacillus subtilis spores are killed, theoretically, It can be estimated that the molecularly hydrated ozone water according to the present invention is effective against bacteria that are not defined.

  In this example, an experiment was also conducted on the bactericidal effect on enterohemorrhagic Escherichia coli, which is generally recognized more widely than Bacillus anthracis. Through such experiments, it was confirmed that the molecularly hydrated ozone water according to the present invention is effective against bacteria that are found in daily life and have high social interest.

Experiment 1
(Preparation of molecular hydrated ozone water)
A stock solution of molecular hydrated ozone water generated by the gas mixture generation apparatus 201 described so far was prepared. The ozone concentration of the stock solution of molecularly hydrated ozone water produced by the gas mixture production device 201 was 120 ppm to 130 ppm, although it varied depending on the lot when produced. Industrial raw water (industrial purified water manufactured by Sanei Chemical Co., Ltd.) was used as raw water into which ozone was dissolved.
(Preparation of experimental suspension)
The experimental bacteria used in this experiment are anthrax spores. As a suspension of the bacteria to be tested, a suspension of 10 ⁸ CFU / mL or more was prepared. Specifically, a purified spore suspension (7.85 × 10 ⁸ CFU / mL) of B. anthracis Pastur II No. 30 strain was prepared.
(Preparation of mixed reaction solution)
In order to obtain a desired ozone concentration, a suspension of the test bacteria, molecular hydrated ozone water, and sterilized ultrapure water are mixed in a 50 mL polypropylene centrifuge tube, and 40 mL of the mixed reaction solution is placed in a 25 ° C. water bath. It was adjusted. At the time of mixing, molecular hydrated ozone water was added last. For mixing, Drummond Pipette Aid was used. In addition, the concentration of the test target bacteria was adjusted to be about 1 × 10 ⁷ CFU / mL in any mixed solution. Prior to the experiment, the polypropylene centrifuge tube was washed three times with molecular hydrated ozone water three times. As the sterilized ultrapure water for dilution, tap water supplied by the Chiba Prefectural Waterworks Bureau was converted to ultrapure water using an ultrapure water preparation device, and sterilized at 121 ° C. for 20 minutes using an autoclave. As the ozone concentration of the mixed reaction solution, 117 ppm, 50 ppm, 10 ppm, and 1 ppm were prepared.
(Collecting reaction mixture)
After adjusting the mixing reaction solution as described above, after a predetermined time, 0.1 mL of the mixing reaction solution was collected and added dropwise to 10 mL of the medium. Moreover, as a culture medium, Nutrient Broth (trademark, manufactured by Nissui Pharmaceutical Co., Ltd.) was used. The predetermined time was 5 seconds, 10 seconds, 30 seconds, 1 minute, 3 minutes, 5 minutes, and 30 minutes. A 15 mL polypropylene centrifuge tube (manufactured by Nunc) was used as a medium storage container (culture container). Here, four culture medium storage containers (culture containers) having the same conditions were prepared. That is, n = 4.
(Cultivation method of test target bacteria after reaction and verification method of bactericidal effect by molecular hydrated ozone water)
The medium to which the mixed reaction solution was dropped was stirred at the maximum output of the vortex mixer and then aerobically cultured at 37 ° C., and the presence or absence of growth of the test target bacteria was observed for 10 days.
(Result / Examination)
The experimental results are shown in FIG. FIG. 18 (A) shows the results after 2 days, (B) shows after 3 days, (C) shows after 4 days, (D) shows after 7 days, and (E) shows The experimental results after 10 days are shown. In the table of FIG. 18, (+) indicates a positive case in which the growth of the experiment target bacterium was confirmed, and (−) indicates a negative in which the growth of the experiment bacterium was not confirmed and the kill of the experiment target bacterium was confirmed. Shows the case. In the left column of each table, the concentration in parentheses indicates the ozone concentration during sampling.

  In general, since the bactericidal effect of spores was observed for more than 7 days, in this experiment, the presence or absence of growth for 10 days was confirmed. Although the judgment and the judgment result changed, the result after the fourth day did not change.

When the presence or absence of growth was determined from the results after 7 days of culture, the molecular hydrated ozone water was exposed to an ozone concentration of 117 ppm in anthrax spores for 10 seconds (0.16 minutes) or longer (CT value = 19.5). 1 × 10 ⁷ (6 log or more) bactericidal action. In addition, 1 × 10 ⁷ (6 log or more) bactericidal action was exhibited at an ozone concentration of 50 ppm under conditions of 1 minute or longer (CT value = 50) and at 10 ppm under conditions of 5 minutes or longer (CT value = 50).

  On the other hand, at 1 ppm, the bactericidal effect could not be confirmed within 30 minutes. Thus, the CT value at each ozone concentration was calculated, and the necessary sterilization time at each concentration was clarified, which is very important in the actual decontamination using the molecular hydrated ozone water according to the present invention. This is a reference data.

With respect to anthrax spores, the molecularly hydrated ozone water according to the present invention can achieve a sterility assurance level (Sterility Assurance Level, SAL) of 10 ⁶ or less, which is an internationally common standard in a very short time. It has become possible. Moreover, since it was effective in the spore which has the strongest physicochemical resistance in microbial species, it is thought that it is more effective than anthrax spore for almost all microbial species. Although ozone sterilization has been known to have an effective sterilizing effect, ozone has low solubility in water and it has been difficult to maintain a high concentration. However, since the molecularly hydrated ozone water according to the present invention can maintain a high concentration for a long time, it can be expected to be effective for decontamination of various microbial species including anthrax spores in the future.

Experiment 2
(Preparation of molecular hydrated ozone water)
A stock solution of molecular hydrated ozone water generated by the gas mixture generation apparatus 201 described so far was prepared. The ozone concentration of the stock solution of molecular hydrated ozone water generated by the gas mixture generation apparatus 201 was 118 ppm. Industrial raw water (industrial purified water manufactured by Sanei Chemical Co., Ltd.) was used as raw water into which ozone was dissolved.
(Preparation of experimental suspension)
The test target bacteria used in this experiment are anthrax vegetative, anthrax spore lot 1, anthrax spore lot 2, and Bacillus subtilis spore. As suspensions of the bacteria to be tested, 10 ⁸ CFU / mL or more were prepared. The details of the suspension of the test target bacteria are as follows.
Anthrax vegetative type: B. anthracis Pastur II No.30 strain: 2.7 × 10 ⁸ CFU / mL
Anthrax spore lot 1: B. anthracis Pastur II No.30 strain: 2.6 × 10 ⁸ CFU / mL
Anthrax spore lot 2: B. anthracis Pastur II No.30 strain: 5.7 × 10 ⁸ CFU / mL
Bacillus subtilis spore: B. subtilis IAM12118T strain: 1.4 × 10 ⁸ CFU / mL
(Preparation of mixed reaction solution)
In a 50 mL polypropylene centrifuge tube, 40 mL of the mixed reaction solution was adjusted in a 25 ° C. water bath by mixing the suspension of the test subject bacteria, molecular hydrated ozone water, and sterilized ultrapure water in a 50 mL polypropylene centrifuge tube so that the ozone concentration was 107 ppm. . At the time of mixing, molecular hydrated ozone water was added last. For mixing, Drummond Pipette Aid was used. In addition, the concentration of the test target bacteria was adjusted to be about 1 × 10 ⁷ CFU / mL in any mixed solution. Prior to the experiment, the polypropylene centrifuge tube was washed three times with molecular hydrated ozone water three times. As the sterilized ultrapure water for dilution, tap water supplied by the Chiba Prefectural Waterworks Bureau was converted to ultrapure water using an ultrapure water preparation device, and sterilized at 121 ° C. for 20 minutes using an autoclave.
(Collecting reaction mixture)
After 30 minutes from the preparation of the above mixed reaction solution, 0.1 mL of the mixed reaction solution was collected and added dropwise to 10 mL of the medium. In addition, Nutrient Broth (trademark, manufactured by Nissui Pharmaceutical Co., Ltd.) was used as the medium. A 15 mL polypropylene centrifuge tube (manufactured by Nunc) was used as a medium storage container (culture container). Here, four culture medium storage containers (culture containers) having the same conditions were prepared. That is, n = 4.
(Cultivation method of test target bacteria after reaction and verification method of bactericidal effect by molecular hydrated ozone water)
The medium to which the mixed reaction solution was dropped was stirred at the maximum output of the vortex mixer and then aerobically cultured at 37 ° C., and the presence or absence of growth of the test target bacteria was observed for 7 days.
(Result / Examination)
In general, since the bactericidal effect of spores was observed for 7 days or longer, the presence or absence of growth for 7 days was confirmed. The molecularly hydrated ozone water according to the present invention has an ozone concentration of not less than 107 ppm and an ozone concentration of 1 × 10 for 30 minutes in any of anthrax vegetative type, anthrax spore lot 1, anthrax spore lot 2, and Bacillus subtilis spore. ⁷ or more (6 log or more) bactericidal action was shown.
(Microscopic inspection)
In the microscopic examination, 10 μL of the mixed reaction solution was placed on a slide glass, air-dried in a safety cabinet, and fixed with a flame. FluoroSave (trademark, manufactured by Calbiochem) was used as an encapsulant, and a cover glass was applied to dry out the encapsulant. A phase contrast image was observed with a biological microscope Axioskop2 plus (trademark, manufactured by Carl Zeiss) at 1000 times the objective lens 100 times and eyepiece 10 times. In photographing, a phase contrast microscope image was taken with AxioCam HRc (trademark, Carl Zeiss).

  The results of the microscopic examination are shown in FIGS. FIG. 19 shows a photograph of a positive control of the anthrax vegetative type and a photograph after 30 minutes of mixing reaction solution preparation. Moreover, FIG. 20 shows a photograph of a positive control of anthrax spore lot 1 and a photograph after 30 minutes of mixing reaction solution adjustment. FIG. 21 shows a photograph of a positive control of anthrax spore lot 2 and a photograph after 30 minutes of adjustment of the mixing reaction solution. FIG. 22 shows a photograph of a positive control of Bacillus subtilis spores and a photograph after 30 minutes of mixing reaction solution preparation. Further, FIG. 23 shows a photograph of the mixture obtained by further centrifugal concentration after 30 minutes of mixing with the anthrax spore lot 2 was adjusted.

  In the phase-contrast microscope image, the influence by the reaction of the ozone molecule with respect to a test object microbe was observed. When compared with the positive control, the anthrax vegetative form was observed as if the lightness in the fungus body had increased and the contents of the fungus body had escaped. In anthrax spore lot 1 and anthrax spore lot 2, only a few of the spores were observed, and a large amount of organic substances that seemed to be decomposed were confirmed (FIGS. 20 and 21). For confirmation, the Bacillus anthracis spore lot 2 was observed by centrifuging and increasing the pellet concentration, and the results were similar (FIG. 23). Many Bacillus subtilis spores were observed that maintained the morphology of the spores, but darkening had occurred and the surface structure was expected to be denatured (FIG. 22).

Experiment 3
(Preparation of molecular hydrated ozone water)
A stock solution of molecular hydrated ozone water generated by the gas mixture generation apparatus 201 described so far was prepared. The ozone concentration of the stock solution of molecular hydrated ozone water generated by the gas mixture generation apparatus 201 was 113 ppm. The tap water supplied by the Chiba Prefectural Waterworks Bureau was used as the raw water to dissolve ozone.
(Preparation of experimental suspension)
The experimental bacteria used in this experiment is enterohemorrhagic Escherichia coli. As a suspension of the bacteria to be tested, a suspension of 10 ⁸ CFU / mL or more was prepared. Specifically, a suspension of Escherichia coli (O157: H7) RIMD 05091896 (1.43 × 10 ⁸ CFU / mL) was prepared.
(Preparation of mixed reaction solution)
In order to obtain a desired ozone concentration, a suspension of the test bacteria, molecular hydrated ozone water, and sterilized ultrapure water are mixed in a 50 mL polypropylene centrifuge tube, and 40 mL of the mixed reaction solution is placed in a 25 ° C. water bath. It was adjusted. At the time of mixing, molecular hydrated ozone water was added last. For mixing, Drummond Pipette Aid was used. In addition, the concentration of the test target bacteria was adjusted to be about 1 × 10 ⁷ CFU / mL in any mixed solution. Prior to the experiment, the polypropylene centrifuge tube was washed three times with molecular hydrated ozone water three times. As the sterilized ultrapure water for dilution, tap water supplied by the Chiba Prefectural Waterworks Bureau was converted to ultrapure water using an ultrapure water preparation device, and sterilized at 121 ° C. for 20 minutes using an autoclave. As the ozone concentration of the mixed reaction solution, those having 102 ppm, 50 ppm, 10 ppm and 1 ppm were prepared.
(Collecting reaction mixture)
After adjusting the mixing reaction solution as described above, after a predetermined time, 0.1 mL of the mixing reaction solution was collected and added dropwise to 10 mL of the medium. In addition, Nutrient Broth (trademark, manufactured by Nissui Pharmaceutical Co., Ltd.) was used as the medium. The predetermined time was 5 seconds, 10 seconds, 30 seconds, 1 minute, 3 minutes, 5 minutes, and 30 minutes. A 15 mL polypropylene centrifuge tube (manufactured by Nunc) was used as a medium storage container (culture container). Here, four culture medium storage containers (culture containers) having the same conditions were prepared. That is, n = 4.
(Cultivation method of test target bacteria after reaction and verification method of bactericidal effect by molecular hydrated ozone water)
The medium to which the mixed reaction solution was dropped was stirred at the maximum output of the vortex mixer and then aerobically cultured at 37 ° C., and the presence or absence of growth of the test target bacteria was observed for 7 days.
(Result / Examination)
The experimental results are shown in FIG. In the table of FIG. 24, (+) indicates a positive case in which the growth of the test target bacteria was confirmed, and (−) indicates a negative in which the growth of the test target bacteria was not confirmed and the kill of the test target bacteria was confirmed. Shows the case.

As a result of confirmation of the presence or absence of proliferation, the molecularly hydrated ozone water according to the present invention was 1 × 10 ⁷ (6 log or more) in the enterohemorrhagic Escherichia coli at a concentration of 1 ppm or more and a condition of 5 seconds or more (CT value = 0.08). ) Showed a bactericidal action. Thus, it was confirmed that the molecularly hydrated ozone water according to the present invention is extremely effective against socially affecting bacteria such as enterohemorrhagic Escherichia coli O157. In particular, a very low value of CT value was calculated, and it was proved that the molecular hydrated ozone water according to the present invention has a great effect on sterilization against such bacteria.

Experiment 4
(Preparation of molecular hydrated ozone water)
A stock solution of molecular hydrated ozone water generated by the gas mixture generation apparatus 201 described so far was prepared. The ozone concentration of the stock solution of molecular hydrated ozone water generated by the gas mixture generation apparatus 201 was 100 ppm. The tap water supplied by the Chiba Prefectural Waterworks Bureau was used as the raw water to dissolve ozone.
(Preparation of experimental suspension)
The experimental bacteria used in this experiment are Bacillus subtilis spores. As a suspension of the bacteria to be tested, a suspension of 10 ⁸ CFU / mL or more was prepared. Specifically, a suspension of B. subtilis IAM12118T strain (1.95 × 10 ⁸ CFU / mL) was prepared.
(Preparation of mixed reaction solution)
In order to obtain a desired ozone concentration, a suspension of the test bacteria, molecular hydrated ozone water, and sterilized ultrapure water are mixed in a 50 mL polypropylene centrifuge tube, and 40 mL of the mixed reaction solution is placed in a 25 ° C. water bath. It was adjusted. At the time of mixing, molecular hydrated ozone water was added last. For mixing, Drummond Pipette Aid was used. In addition, the concentration of the test target bacteria was adjusted to be about 1 × 10 ⁷ CFU / mL in any mixed solution. Prior to the experiment, the polypropylene centrifuge tube was washed three times with molecular hydrated ozone water three times. As the sterilized ultrapure water for dilution, tap water supplied by the Chiba Prefectural Waterworks Bureau was converted to ultrapure water using an ultrapure water preparation device, and sterilized at 121 ° C. for 20 minutes using an autoclave. As the ozone concentration of the mixed reaction solution, 50 ppm, 10 ppm, and 1 ppm were prepared.
(Collecting reaction mixture)
After adjusting the mixing reaction solution as described above, after a predetermined time, 0.1 mL of the mixing reaction solution was collected and added dropwise to 10 mL of the medium. In addition, Nutrient Broth (trademark, manufactured by Nissui Pharmaceutical Co., Ltd.) was used as the medium. The predetermined time was 5 seconds, 10 seconds, 30 seconds, 1 minute, 3 minutes, 5 minutes, and 30 minutes. A 15 mL polypropylene centrifuge tube (manufactured by Nunc) was used as a medium storage container (culture container). Here, four culture medium storage containers (culture containers) having the same conditions were prepared. That is, n = 4.
(Cultivation method of test target bacteria after reaction and verification method of bactericidal effect by molecular hydrated ozone water)
The medium in which the mixed reaction solution was dropped was stirred at the maximum output of the vortex mixer, and then aerobically cultured at 37 ° C., and the presence or absence of growth of the test target bacteria was observed for 15 days.
(Result / Examination)
The experimental results are shown in FIG. FIG. 25 (A) shows the experimental results after 1 day, (B) shows the results after 2 days, and (C) shows the results after 7 days. In the table of FIG. 25, (+) indicates a positive case in which the growth of the test target bacteria was confirmed, and (−) indicates a negative in which the growth of the test target bacteria was not confirmed and the kill of the test target bacteria was confirmed. Shows the case.

In general, since the bactericidal effect of spores was observed for 7 days or longer, the presence or absence of growth for 15 days was confirmed. As a result, there was a difference between the results after 1 day and 2 days, but the results after 2 days did not change. The molecularly hydrated ozone water according to the present invention exhibited a bactericidal action of 1 × 10 ⁷ (6 log or more) in Bacillus subtilis spores at a concentration of 10 ppm or more and conditions of 5 minutes or more (CT value = 50).

  In this experiment, it was suggested that the bactericidal effect of ozone may reach a peak at 10 ppm. However, the ozone concentration decays quickly, and in the actual usage environment, other organic substances may be contained. Therefore, in order to maintain the ozone concentration with respect to the target fungus at 10 ppm or more, it is considered necessary to have a higher ozone concentration. . In general, Bacillus subtilis spores are known to be more resistant to disinfection by disinfectants than Bacillus anthracis spores, so that anthrax spores can be reliably removed if used under conditions that kill Bacillus subtilis spores. Dyeing is possible.

  As described above, according to the biological agent decontamination method of the present invention, bacteria such as anthrax spores can be killed, and biological weapons can be made harmless efficiently.

181 ... Oxygen gas cylinder 182 ... Nitrogen gas cylinder 190 ... Pipe 191 ... Pump 195 ... Valve 201 ... Gas mixture generator 202 ... Storage tank 202v ... Water intake valve 203- ..Gas supply device 204 ... circulation system device 205 ... gas-liquid mixing device (liquid clathrate production device)
206 ... Dissolution promotion tank 202 ... Storage tank 207 ... Temperature holding device 211 ... Pump 212 ... Cooling machine 213 ... Pipe 217 ... Gas supply pipe 218 ... Needle valve valve 219 ... Check valve 220 ... Flow meter 221 ... First pressure gauge 222 ... Second pressure gauge 223 ... First gas pressure gauge 224 ... Second gas pressure gauge 225 ... Electromagnetic valve 231 ... Venturi tube 232 ... upstream large path 233 ... throttle ramp 234 ... small path 235 ... open ramp 236 ... downstream large path 239 ... gas Supply pipe 243 ... Magnetic circuit 245 ... One magnet piece 246 ... The other magnet piece 248 ... Connection member 265 ... Gas-liquid separation device 267 ... Gas decomposition device 270 ... Piping 271 ... Pump 272 Check valve 273 ... Pipe 274 ... Pipe 275 ... Pipe 276 ... Valve 300 ... Fourier transform infrared spectroscopy 301 ... Mirror 302 ... Prism 303 ... Sample Placement base 303a ... Sample filling hole 304 ... Retainer

Claims (10)

A decontamination method that detoxifies chemical warfare agents as chemical agents using molecularly hydrated ozone water generated by dissolving ozone in raw water,
A step of generating molecularly hydrated ozone water in which the hydrogen bond rate in ozone water is smaller than the hydrogen bond rate of raw water;
Storing the generated molecular hydrated ozone water in a storage tank at atmospheric pressure;
A method of decontaminating a chemical agent, comprising: bringing the molecular hydrated ozone water taken out of the storage tank into contact with a chemical warfare agent and detoxifying the chemical warfare agent by an oxidizing action of ozone molecules. . 2. The chemical agent decontamination method according to claim 1, wherein the molecular hydrated ozone water contains ozone having a bubble diameter of less than 50 nm. The peak value of the peak intensity of hydrogen bond energy of molecular hydrated ozone water is smaller than -0.0021 as measured with an infrared spectrophotometer as compared with the raw water. The decontamination method of the chemical agent described. 4. The chemical agent decontamination method according to claim 1, wherein molecular hydrated ozone water is set to 20 ° C. or lower in the storage tank. 5. A step of raising the temperature of the molecular hydrated ozone water from 30 ° C. to less than 45 ° C. after the molecular hydrated ozone water is taken out of the storage tank and before contacting with the chemical warfare agent; 5. The chemical agent decontamination method according to claim 1, wherein the chemical agent is decontaminated. A decontamination method for detoxifying biological agents using molecular hydrated ozone water generated by dissolving ozone in raw water,
A step of generating molecularly hydrated ozone water in which the hydrogen bond rate in ozone water is smaller than the hydrogen bond rate of raw water;
Storing the generated molecular hydrated ozone water in a storage tank at atmospheric pressure;
A method for decontaminating a biological agent, comprising: bringing a molecular hydrated ozone water taken out from the storage tank into contact with a biological agent and detoxifying the biological agent by an oxidizing action of ozone molecules. The biological agent decontamination method according to claim 6, wherein the molecular hydrated ozone water contains ozone having a bubble diameter of less than 50 nm. The maximum peak intensity of hydrogen bond energy of molecular hydrated ozone water is smaller than -0.0021 as measured with an infrared spectrophotometer as compared with raw water. The decontamination method of the biological agent as described. The biological agent decontamination method according to any one of claims 6 to 8, wherein molecular hydrated ozone water is set to 20 ° C or lower in the storage tank. After the molecular hydrated ozone water is taken out from the storage tank and before being brought into contact with the biological agent, the method includes a temperature raising step for setting the temperature of the molecularly hydrated ozone water to 30 ° C. or higher and lower than 45 ° C. The biological agent decontamination method according to any one of claims 6 to 9.