WO2017138743A1 - Appareil et procédé de stérilisation du type à pulvérisation de fluide désinfectant complexe - Google Patents

Appareil et procédé de stérilisation du type à pulvérisation de fluide désinfectant complexe Download PDF

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WO2017138743A1
WO2017138743A1 PCT/KR2017/001365 KR2017001365W WO2017138743A1 WO 2017138743 A1 WO2017138743 A1 WO 2017138743A1 KR 2017001365 W KR2017001365 W KR 2017001365W WO 2017138743 A1 WO2017138743 A1 WO 2017138743A1
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ozone
liquid
plasma
disinfectant
carrier gas
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Korean (ko)
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손희식
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(주)에프티넷
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/02—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using physical phenomena
    • A61L2/08—Radiation
    • A61L2/10—Ultraviolet radiation
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/02—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using physical phenomena
    • A61L2/14—Plasma, i.e. ionised gases
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • A61L2/18—Liquid substances or solutions comprising solids or dissolved gases
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • A61L2/20—Gaseous substances, e.g. vapours
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/24—Apparatus using programmed or automatic operation

Definitions

  • the present invention relates to a sterilization apparatus and method, and more particularly, to a sterilization apparatus and method for enhancing the efficiency of sterilization by enhancing the generation of OH radicals by using a reaction of drugs such as hydrogen peroxide and ozone.
  • the antiseptics are used in the form of liquid (liquid) microparticles, not in the form of gases, and in combination with ozone and plasma as necessary.
  • Disinfection or sterilization has traditionally been a method using high temperature steam, a method of using Ethylene Oxide (ETO) gas, a method using ozone and water, a method using hydrogen peroxide vapor, a method using hydrogen peroxide and plasma.
  • ETO Ethylene Oxide
  • ozone and water a method using ozone and water
  • hydrogen peroxide vapor a method using hydrogen peroxide and plasma.
  • the chemical supply method is largely supplied in the form of vapor, gas bubbler, liquid (liquid) mist.
  • High concentration hydrogen peroxide water is a toxic substance in handling, and direct contact between the sterilized object and the plasma may cause electrostatic damage by electric fields and surface damage by plasma.
  • Ozone is disadvantageous in that it only takes part in the decomposition process of limited organic bonds, or is consumed in the oxidation reaction of metal, which takes a long time for sterilization.
  • Ozone has the next highest redox level (2.07 eV) after fluorine (F, 2.87 eV) and hydroxyl (OH, 2.85 eV), and is known to be more powerful than hydrogen peroxide (H 2 O 2, 1.77 eV).
  • Literatures using ozone include Korean Patent Registration No. 10-0737210, US 2004 / 0161361A1, JP 2005-211095A, JP 2008-104488A, JP 2005-211095A JP 2008-104488A, and the like.
  • ozone has the disadvantages of slow sterilization reaction time and large variation in speed during decomposition depending on the type of organic material.
  • US Pat. No. 4,643,876 describes a method of using plasma, and discloses a method of generating and sterilizing plasma as a whole in an airtight container.
  • a disadvantage that the surface of the sterilized object is damaged by the direct contact of the plasma.
  • Literature for improving this is U.S. Patent 6,458,321 and Republic of Korea Patent 10-0458112.
  • Korean Patent Laid-Open Publication No. 10-2012-0028413 discloses a method of activating hydrogen peroxide by a low-temperature plasma by maintaining a closed container at a pressure below atmospheric pressure and using hydrogen peroxide as a gas state, and additionally injecting ozone at a separate inlet.
  • this method has a disadvantage in that gaseous hydrogen peroxide is decomposed as it passes through the plasma, thereby reducing disinfection performance.
  • the gas circulation system is characterized in that the gas is circulated through the inside of the medical device. At this time, the plasma is involved in only a part of the gas circulating in the container to generate a small amount of ozone, there is a limit to the sterilization efficiency by activating and moving hydrogen peroxide.
  • the technique described above is essentially a method of using a hermetically sealed container, most of which is characterized by sterilization under reduced pressure below atmospheric pressure.
  • the method of activating the liquid microparticles of the disinfectant with radicals, etc. is a state of practical use only to generate a high voltage electric arc between two pointed electrodes to pass the sprayed liquid microparticles.
  • the method of using ultraviolet rays is also effective, but it is judged that the energy of ultraviolet rays is insufficient to activate the sprayed fine particles in a short time.
  • This method also forms OH radicals as the microparticles pass through the arc discharge, but have a short survival life of the OH radicals and tend to be exhausted before reaching the surface of the sterilized object. Therefore, there is a disadvantage that the sterilization effect can be generated only when the injection speed is fast and sustained.
  • a method of using a disinfectant, ozone, and plasma in combination with a relatively simple apparatus for spraying or spraying a disinfectant to sterilize the surface or space exposed to the outside as a basic process and to further increase sterilization efficiency I would like to propose. More specifically, the liquid microparticles and ozone of the disinfectant are used at the same time, and the disinfecting fluid is characterized by causing an activation reaction after reaching the surface of the sterilization object. At this time, the ozone is supplied by gas phase ozone, liquid phase ozone, or ozone generated when the plasma passes.
  • the present invention has been made to solve the problems of the prior art described above, the object of the present invention is to provide a disinfection and sterilization apparatus and sterilization method excellent in sterilization power and simple apparatus.
  • T3 Means for generating ozone
  • the final sprayed composite disinfecting fluid is achieved by a composite disinfecting fluid spray sterilizer characterized in that it comprises a liquid disinfectant microparticles, ozone (gas, liquid or a combination thereof) and a carrier gas.
  • the final sprayed composite disinfecting fluid is also achieved by a composite disinfecting fluid spray sterilization device comprising liquid disinfectant microparticles, ozone (gas, liquid or a combination thereof) and a carrier gas.
  • T3 Means for generating ozone
  • the final sprayed composite disinfecting fluid is achieved by a composite disinfecting fluid spray sterilizer characterized in that it comprises a liquid disinfectant microparticles, ozone (gas, liquid or a combination thereof) and a carrier gas.
  • the liquid disinfectant may be any one of hydrogen peroxide water, ozone water, peracetic acid, hypochlorous acid, sodium percarbonate, glutaraldehyde, ethylenediamine-tetracetate, isopropyl alcohol, citric acid, lactic acid, hydroxyl, or a combination thereof.
  • the hydrogen peroxide concentration of the hydrogen peroxide solution may be 50% or less, 35% or less, 15% or less, 7.5% or less, 6% or less or 3% or less.
  • the carrier gas may be any one of air, oxygen, argon, nitrogen, helium, or a combination thereof.
  • the mixing of the ozone may be any one of a method of adding to a liquid disinfectant in the form of gaseous ozone, a method of mixing in a carrier gas, a method of mixing in a particulate generation site, a method of mixing during spraying, or a combination thereof.
  • the ozone may be mixed with the liquid disinfectant in the form of liquid ozone water or ozone microbubbles.
  • the ozone concentration in the final disinfecting fluid to be sprayed may be an ozone concentration of 15% or less based on the gas except liquid.
  • the liquid fine particles may be generated by an injection nozzle or an ultrasonic particle generator.
  • An ultraviolet (UV) irradiation device may be further provided to irradiate ultraviolet (UV) to any one of liquid disinfectant, sprayed liquid disinfectant fine particles, sterilized object, or a combination thereof.
  • the atmospheric pressure plasma generates an atmospheric pressure plasma by applying electricity to the plasma generating electrode, and passes the carrier gas through the plasma generating region to at least one or more plasma jets from which the plasma is ejected into the free space (outer space).
  • the atmospheric plasma may be generated by at least one dielectric barrier discharge (DBD) plasma electrode having a through hole for fluid flow in a pair of plate-shaped electrodes perpendicular to the plate.
  • DBD dielectric barrier discharge
  • the dielectric barrier discharge plasma electrode may be any one of a through gap DBD method, a through surface DBD method, a through side DBD method, or a combination thereof.
  • the plasma electrode may be formed of any one of a water repellent layer, a waterproof layer, a photocatalytic layer, a catalyst layer, a hydrophilic layer, an insulating layer, a dielectric layer, a protective layer, or a combination thereof. Can be formed.
  • the plasma electrode may further have a temperature control function for adjusting the temperature of the electrode.
  • a fluid guide tube for guiding the inflow and outflow of the fluid may be introduced into the through hole inlet, the outlet, or both.
  • the applied electricity may be a voltage in the range of 0.2-25 kV and a frequency in the range of 0.5-50 kHz in the form of a pulse or alternating current.
  • the atmospheric plasma may be generated by an arc discharge or a plasma torch method.
  • the composite disinfection fluid is flying to reach a sterilized object (S7);
  • the final sprayed composite disinfection fluid is achieved by a composite disinfection fluid spray sterilization method comprising liquid disinfectant microparticles, ozone (gas, liquid or combinations thereof) and a carrier gas.
  • the object of the present invention is also;
  • the sprayed liquid fine particles and the carrier gas pass through the atmospheric plasma to activate the liquid disinfectant microparticles, and at the same time gaseous ozone is generated to form a composite disinfecting fluid (S6);
  • the composite disinfection fluid is flying to reach a sterilized object (S7);
  • the final sprayed composite disinfection fluid is also achieved by a composite disinfection fluid spray sterilization method comprising liquid disinfectant microparticles, ozone (gas, liquid or combinations thereof) and carrier gas.
  • the object of the present invention is also;
  • the sprayed liquid fine particles and the carrier gas pass through the atmospheric plasma to activate the liquid disinfectant microparticles, and at the same time gaseous ozone is generated to form a composite disinfecting fluid (S6);
  • the composite disinfection fluid is flying to reach a sterilized object (S7);
  • the final sprayed composite disinfection fluid is also achieved by a composite disinfection fluid spray sterilization method comprising liquid disinfectant microparticles, ozone (gas, liquid or combinations thereof) and carrier gas.
  • the liquid disinfectant may be any one of hydrogen peroxide water, ozone water, peracetic acid, hypochlorous acid, sodium percarbonate, glutaraldehyde, ethylenediamine-tetracetate, isopropyl alcohol, citric acid, lactic acid, hydroxyl, or a combination thereof.
  • the hydrogen peroxide concentration of the hydrogen peroxide solution may be 50% or less, 35% or less, 15% or less, 7.5% or less, 6% or less or 3% or less.
  • the carrier gas may be any one of air, oxygen, argon, nitrogen, helium, or a combination thereof.
  • the mixing of the ozone may be any one of a method of adding to a liquid disinfectant in the form of gaseous ozone, a method of mixing in a carrier gas, a method of mixing in a particulate generation site, a method of mixing during spraying, or a combination thereof.
  • the ozone may be mixed with the liquid disinfectant in the form of liquid ozone water or ozone microbubbles.
  • the ozone concentration in the final sprayed mixed disinfection fluid may be an ozone concentration of 15% or less based on gas except liquid.
  • the liquid fine particles may be to be generated by the injection nozzle or ultrasonic particle generator.
  • An ultraviolet (UV) irradiation apparatus may be further provided to irradiate ultraviolet (UV) to any one of liquid disinfectant, sprayed liquid disinfectant fine particles, sterilized object, or a combination thereof.
  • the atmospheric pressure plasma generates an atmospheric pressure plasma by applying electricity to the plasma generating electrode, and passes the carrier gas through the plasma generating region to at least one or more plasma jets from which the plasma is ejected into the free space (outer space).
  • the atmospheric plasma may be generated by at least one dielectric barrier discharge (DBD) plasma electrode having a through hole for fluid flow in a pair of plate-shaped electrodes perpendicular to the plate.
  • DBD dielectric barrier discharge
  • the dielectric barrier discharge plasma electrode may be any one of a through gap DBD method, a through surface DBD method, a through side DBD method, or a combination thereof.
  • the plasma electrode may be formed of any one of a water repellent layer, a waterproof layer, a photocatalytic layer, a catalyst layer, a hydrophilic layer, an insulating layer, a dielectric layer, a protective layer, or a combination thereof. Can be formed.
  • the plasma electrode may be further equipped with a temperature control function for controlling the temperature of the electrode.
  • a fluid guide tube for guiding the inflow and outflow of the fluid may be introduced into the through hole inlet, the outlet, or both.
  • the applied electricity may be in the form of a pulse or alternating current with a voltage in the range of 0.2 to 25 kV and a frequency in the range of 0.5 to 50 kHz.
  • the atmospheric pressure plasma may be generated by an arc discharge or a plasma torch method.
  • the sterilization apparatus and method described above are simple in apparatus and excellent in sterilization efficiency as a result of the combined reaction of disinfectant, ozone, and plasma.
  • the device can be simplified by omitting the decompression system for sterilization, and the sterilization efficiency can be increased by generating active species on the surface of the sterilized object, rather than after moving the active species.
  • the sterilization apparatus and method of the present invention can be easily applied to sterilized objects exposed to indoors and outdoors, and can also be applied to the inside of a sealed container and can be easily applied to sterilization of medical instruments.
  • 1 is a conceptual diagram showing the sterilization process of the disinfectant (hydrogen peroxide) and ozone according to the present invention.
  • FIG. 2 is a conceptual diagram illustrating an activation process by plasma according to the present invention.
  • FIG 3 is a conceptual diagram showing an activation scheme according to the present invention (in particular (a) shows an existing scheme and (b) shows a scheme according to the invention).
  • Figure 4 shows the structure of the device of the sterilization compound and gaseous ozone complex sterilization method.
  • Figure 5 shows the structure of the device of the sterilization compound and the combined sterilization method of micro bubble ozone.
  • Figure 6 shows the structure of the device of the sterilization compound and the compound sterilization method of plasma (plasma jet method).
  • FIG. 7 is an embodiment of a plasma jet structure diagram.
  • FIG 8 shows several types of DBD plasma electrode structures according to the present invention.
  • Figure 9 shows the device structure of the compound sterilization method of disinfectant and plasma (through side DBD method).
  • 10 is an embodiment of a structure of a through-side DBD plasma electrode.
  • FIG. 11 shows a device structure diagram of a compound sterilization method of a disinfectant, ozone and plasma (through surface DBD method).
  • FIG. 12 is a flowchart showing the steps of the sterilization method.
  • the present invention was intended to efficiently use a combined reaction with a disinfectant (such as hydrogen peroxide), ozone and water.
  • a disinfectant such as hydrogen peroxide
  • the main purpose of using plasma is also to produce ozone and liquid activation of liquid particulates.
  • Liquid disinfectant, ozone, and activated liquid constituting the complex disinfecting fluid has a relatively long lifespan, so that even after the spraying process, the compound reaches a sterilized object without the consumption of components to cause a complex reaction to form radicals and the like.
  • the present invention is based on spraying disinfectant such as hydrogen peroxide solution into liquid fine particles, and further adopts two methods as an additional method for increasing efficiency.
  • ozone is condensed by spraying disinfectant and ozone before spraying disinfectant.
  • the liquid fine particles and the carrier gas that are sprayed during the spraying of the disinfectant pass through the plasma to convert oxygen in the carrier gas into ozone, and the liquid fine particles to activate the liquid.
  • both methods may be applied simultaneously.
  • Disinfectants include hydrogen peroxide, peracetic acid, hypochlorous acid, and the like, which are known techniques.
  • the method of disinfecting the disinfectant drug also takes a long time to sterilize, and in particular, hydrogen peroxide has less sterilization effect on Gram-negative bacteria having a defensive enzyme such as superoxide dismutase.
  • Ozone In the case of ozone, ozone alone sterilization method or sterilization method with ozone and water vapor is also a known technique. Ozone has a disadvantage in that it is only involved in the decomposition process of limited organic bonds, or is consumed in the oxidation reaction of metal, which takes a long time for sterilization. Therefore, the present invention induces a complex reaction of disinfectant such as hydrogen peroxide, ozone and water to improve efficiency.
  • disinfectant such as hydrogen peroxide
  • ozone may be gaseous ozone or liquid ozone. The half-life of ozone varies by temperature, but it is about 12 hours, and it is 20-30 minutes in water, and the remaining time after generation is sufficient for practical application.
  • This reaction may be initiated even when sprayed, but hydrogen peroxide and ozone have a relatively long lifespan, and since hydrogen peroxide is liquid and a sufficient amount of ozone is supplied, it is easy to reach the sterilization target and react on the sterilization target until the components are exhausted. Will continue.
  • the present invention uses hydrogen peroxide solution and the like, water is already included in the disinfectant.
  • the hydrolysis reaction of ozone occurs through several reaction pathways.
  • the OH radical, hydrogen peroxide and the like are produced using the HO 2 radical as an initiator.
  • ozone is gaseous or liquid, and water is also present in the liquid phase, so that the components are continuously supplied by vaporizing from the object, so that the sterilization reaction is continued even after the spraying time, thereby being effective for sterilization.
  • the liquid fine particles of the disinfectant as the main component of the disinfection fluid for sterilization, and if necessary, a complex disinfection fluid is formed using ozone (gas or liquid) or plasma, Reaction to increase sterilization efficiency.
  • ozone gas or liquid
  • plasma Reaction to increase sterilization efficiency.
  • ozone may be a gas generated by an ozone generator, or ozone water dissolved in water.
  • the sprayed liquid and gaseous mixed disinfection fluid flies to atmospheric pressure as ozone (gas or liquid fine particles), hydrogen peroxide (liquid fine particles), water (liquid fine particles), air and carrier gas coexist.
  • ozone gas or liquid fine particles
  • hydrogen peroxide liquid fine particles
  • water liquid fine particles
  • air and carrier gas coexist.
  • ozone gas or liquid fine particles
  • some reactions of ozone and hydrogen peroxide, ozone and steam described above occur, but most disinfection fluids reach the surface of the sterilized object. Therefore, hydrogen peroxide, ozone, and water on the surface of the sterilized object causes a complex reaction to actively generate OH radicals and the like, resulting in a sterilization reaction.
  • hydrogen peroxide has been described as an example for convenience, but in addition, hydrogen peroxide, ozone water, peracetic acid, hypochlorous acid, sodium peroxocarbonate, glutaraldehyde, ethylenediaminetetraacetate, isopropyl alcohol , Citric acid, lactic acid, oxalic acid, or a combination thereof may be used.
  • the concentration of hydrogen peroxide may be subdivided into 50%, 35%, 15%, 7.5%, 6% or 3%, depending on the purpose and purpose. Do.
  • the carrier gas used for spraying, the carrier gas used for ozone generation, and the carrier gas used for plasma generation are preferably one of air, oxygen, argon, nitrogen, helium or a combination thereof.
  • Means for spraying the liquid disinfectant with liquid carrier particles and spraying gas may be used as a spray nozzle, ultrasonic particle generator, etc., the size of the atomized particles are preferably 1 to 50 microns.
  • an ozone generator using air or oxygen may be used, and in order to use liquid ozone, an ozone water generator may be used.
  • gaseous ozone there is a method of mixing with a carrier gas for spraying.
  • a more efficient way is to add gaseous ozone to the liquid disinfectant as a bubble so that some of it is dissolved in the disinfectant and the other is sprayed with the carrier gas.
  • Microbubbles can also be used because fine bubbles are more efficient in dissolving ozone.
  • Liquid ozone can be mixed and sprayed with liquid disinfectant.
  • Another method of the present invention is a method using a plasma, in which, as described above, spraying an appropriate concentration of disinfecting chemical under atmospheric pressure is used as a basic process.
  • the difference is that the mixing of ozone through the ozone generator is omitted and the disinfecting fluid sprayed passes through the plasma.
  • the carrier gas (including oxygen) present in the disinfecting fluid is converted into gaseous ozone by the plasma, and the liquid disinfectant fine particles are activated by the plasma.
  • Activation of the liquid forms liquid ozone, OH radicals, and the like in the liquid.
  • Table 1 shows the types and characteristics of plasma apparatuses used in the sterilization field and the amount of ozone and free radicals generated in the presence of oxygen. According to Table 1, it can be seen that when the space discharge is generated under low pressure (Low pressure discharge), mainly active oxygen is formed.
  • the traditional arc discharge or plasma torch is a high temperature plasma that generates a high temperature by applying a high voltage, and it can be seen that a large amount of active oxygen is mainly generated.
  • Dielectric Barrier Discharge Dielectric Barrier Discharge
  • plasma jet Dielectric Barrier Discharge
  • DBD plasmas are mainly used for ozone generation because a large amount of ozone is generated.
  • it is used for ozone generation, decomposition and activation of hydrogen peroxide when supplying hydrogen peroxide, activation of circulating gas in a closed container, or decomposition for prevention of contamination of hydrogen peroxide and radical components during exhaust.
  • liquid particulates other than gas pass through the DBD plasma, electric disturbance occurs, which makes it difficult to apply.
  • DBD discharge plasma or plasma jet is suitable for using ozone by plasma. Therefore, the present invention mainly uses a DBD plasma and a plasma jet. However, if ozone is sufficient by providing a separate ozone generator, an arc discharge or a plasma torch that generates a large amount of active species may be used.
  • Plasma jets generate ozone and free radicals to the same extent, and can generate plasma remotely, so that electrical disturbances do not occur when the liquid fine particles pass through the plasma, so that the application in the present invention is unreasonable.
  • the gaseous hydrogen peroxide When the gaseous hydrogen peroxide is exposed to the plasma, it is decomposed into water, oxygen, and hydrogen. Therefore, the effectiveness of the sterilization method for supplying hydrogen peroxide vapor through the plasma is questionable.
  • the disinfectant such as hydrogen peroxide is used in the form of liquid fine particles, it is possible to prevent decomposition of hydrogen peroxide and the liquid disinfectant can easily reach the target.
  • the liquid disinfectant microparticles and the carrier gas is passed through the plasma to generate gaseous ozone and to activate the liquid microparticles to form a complex disinfection fluid.
  • the complex disinfecting fluid is a relatively stable disinfectant, ozone, radicals, etc. are mixed, and after reaching the sterilized object, the compound is sterilized by a complex reaction.
  • the final disinfecting fluid of the liquid fine particles and ozone finally sprayed in the present invention preferably has a concentration of ozone of 15% or less based on the gas except liquid.
  • the compound disinfecting fluid may be sterilized by spraying the sterilization object indoors or outdoors, or further provided with a sealed space for isolating the sterilized object from the outside, and the disinfecting fluid may be sprayed into the sealed space to sterilize the internal object.
  • Korean Patent Laid-Open Publication No. 10-2012-0028413 is a document for improving sterilization efficiency using hydrogen peroxide, ozone, and plasma.
  • a closed pressure vessel is used, and hydrogen peroxide (20-60%) is made into a gas and the gas is passed through a plasma into the vessel.
  • ozone is generated in a separate ozone generator and the ozone is heated and activated to flow into the container.
  • plasma consumes, decomposes and activates gaseous hydrogen peroxide as a raw material.
  • Ozone is also consumed by heating to decompose and activate. Therefore, high concentrations of hydrogen peroxide and a large amount of ozone are required.
  • the present invention does not require a closed pressure reduction state, it uses liquid fine particles as a disinfectant, the plasma is efficient by simultaneously performing both functions of ozone generation and activating the liquid, and because the liquid fine particles, the plasma is a gas It does not decompose hydrogen peroxide.
  • the main difference from this patent is that liquid microparticles and ozone are sprayed straight onto the surface of the sterilized object to reach the surface of the object to generate OH radicals through the reaction of hydrogen peroxide with ozone and the reaction between ozone and water.
  • ozone optimized for sterilization can be introduced by actively converting and discharging inlet air or oxygen into ozone, plasma does not decompose and activate hydrogen peroxide, liquid disinfectant microparticles and ozone to the surface of the sterilization target.
  • the main difference from this patent is that OH radicals are generated by the reaction of hydrogen peroxide and ozone and the reaction of ozone and water after reaching the surface of the object.
  • the method of activating the liquid microparticles of the disinfectant with radicals, etc. is a state of practical use only to generate a high voltage electric arc between two pointed electrodes to pass the sprayed liquid microparticles.
  • ozone is generated after the passage of the plasma is the main object of the present invention
  • DBD dielectric barrier
  • the use of ozone, the plasma jet that can be remotely generated from the electrode of the plasma, the balance of the complex disinfection fluid can be balanced by the electrical indirect prevention of liquid particles and the simultaneous generation of ozone and free radical species as described above It is the difference of the present invention.
  • the present invention is chemically stable to allow long-lived ozone to reach sterilized objects and at the same time to reach liquid disinfectant particulates. Then, by inducing an active complex radical formation reaction on the surface of the sterilization object can be maximized sterilization efficiency.
  • a conceptual diagram thereof is shown in FIG. 3. That is, the present invention is not the method of FIG. 3 (a), which is a transfer method after generation of active species, which is a conventional method, but belongs to the method of FIG. 3 (b) to generate active species in a sterilized object after transfer of disinfecting components to the object. .
  • the plasma was electrically stabilized by preventing electric disturbance of the plasma electrode or introducing a remote plasma.
  • the complex disinfecting fluid passes through the plasma, a large amount of gaseous ozone is generated, and a part of the generated ozone is dissolved in the liquid fine particles.
  • liquid activation of the liquid fine particles occurs by the plasma action to generate liquid ozone in the fine particles, thereby further increasing sterilization efficiency.
  • the present invention can be judged that the difference from the conventional technology in that it uses a liquid disinfectant spray device and ozone or plasma is not great, but the present invention has a principle differentiation and technical progress through a deep understanding of the sterilization process I think that. That is, the principle differentiation in the present invention is not a transfer method after generation of active species such as OH radicals, but a method of generating OH radicals by inducing activation by a complex reaction after disinfectant and ozone reaches a sterilization target, That is, it is a method of generating active species after migration.
  • the technical difference is that plasma is applied to the liquid fine particles, and the plasma of the liquid fine particles is directly applied, and for this purpose, an electric disturbance prevention technology and a through hole are applied.
  • FIG. 4 An apparatus configuration example 1 according to the present invention is shown in FIG. 4.
  • the disinfectant storage container (T1) and the carrier gas supply device (T2) is provided.
  • an ozone generator (T3) for generating ozone using air or oxygen is provided.
  • the disinfectant storage container (T1) is supplied with a liquid disinfectant (such as hydrogen peroxide) is provided with a particulate generation and spraying device for spraying the liquid disinfectant with the carrier gas (air, etc.).
  • the apparatus may be a particulate generator T5 using spray nozzles or ultrasonic waves.
  • Ozone generated from the ozone generator is supplied to the liquid disinfectant in the form of bubbles (R1), supplied to the carrier gas for mixing (R2), mixed with the particulate generator (R3), and supplied after the particulate generator (R4). You can select and use the method according to your needs.
  • the size of the liquid fine particles is preferably in the range of 1 micron to 50 microns, so that the spray rate and amount of the fine particles can be adjusted according to the application.
  • the ozone water is preferably mixed with the disinfectant (R1), and the mixed ozone water and the disinfectant are simultaneously converted into fine particles and sprayed to the outside.
  • Device Configuration Example 2 relates to another way of mixing ozone with a disinfectant.
  • This example describes how to mix ozone into microbubbles.
  • ozone is mixed in the form of micro bubbles, ozone is dissolved in the disinfectant, and the ozone remaining as a gas is sprayed in a gaseous state together with the carrier gas. Therefore, the effect of spraying the liquid ozone and the gaseous ozone simultaneously. That is, the two effects of the gaseous ozone mixing system and the ozone water mixing system described in the device configuration example 1 simultaneously appear.
  • the microbubble generating function is applied to the ozone mixer T4 and the R1 direction (see FIG. 4) is applied.
  • the ozone mixer (micro bubble generator) supplies the micro bubble in the R1 direction (see FIG. 4).
  • the ozone mixer with a microbubble function may be supplied with a liquid other than the disinfectant storage container (T1), or may be supplied with a different liquid.
  • FIG. 5 One embodiment of the microbubble mixing mode of ozone is shown in FIG. 5.
  • Device configuration example 3 is shown in FIG.
  • the configuration of the apparatus is the same as that of the apparatus configuration example 1 except that the ozone generator and the ozone mixer are omitted.
  • At least one plasma jet device is additionally connected to the plasma power supply.
  • 7 shows one embodiment of a plasma jet structure.
  • the plasma jet is a plasma generator that generates electricity by reducing electricity to the plasma generating electrode, and passes the carrier gas through the plasma generating region to eject the plasma from the generating portion into a free space (outer space).
  • Plasma jets are placed in front of the sprayed disinfecting fluid so that the sprayed disinfecting fluid passes through the plasma discharged from the plasma jet.
  • the plasma jet since the plasma jet has a high airflow, it is preferable to arrange the plasma jet so as not to interfere with the flow of the liquid fine particles to be sprayed.
  • the plasma jets may be arranged so that each plasma airflow is centered.
  • the structure and generation principle of the plasma jet can be found in many literatures.
  • the power source for driving the plasma jet is preferably a voltage in the range of 0.2-25 kV and a frequency in the range of 0.5-50 kHz in the form of pulse or alternating current.
  • the function of the plasma jet in the present invention is to generate a large amount of gaseous ozone and free radicals as the complex disinfecting fluid passes through the plasma and to liquid-activate liquid fine particles.
  • Configuration Example 4 replaces the plasma jet apparatus in Device Configuration Example 3 and includes another plasma generating apparatus.
  • the plasma generator applies a DBD plasma electrode having a through hole for fluid flow in a direction perpendicular to the plate to a pair of plate-shaped electrodes.
  • the method of the DBD plasma electrode may use three methods. These three types are shown in FIG. 8.
  • (A) is a through space
  • Spacing DBD electrodes have a dielectric layer between a pair of plate-shaped electrodes and a gap between the two electrodes
  • surface DBD electrodes have a dielectric layer between a pair of electrodes and one electrode has a linear pattern (pattern). It has a surface discharge along the pattern.
  • the side DBD electrode has a dielectric layer between a pair of electrodes, and there is no gap between the electrodes, so that plasma is generated at the side of the electrode.
  • FIG. 9. 10 shows an embodiment of the through-side DBD plasma electrode structure.
  • Device Configuration Example 4 is similar to Device Configuration Example 3 in that ozone is generated and the liquid fine particles passing through the plasma are activated.
  • DBD plasma electrodes may apply more than one of the same type or may be combined with other types. You can also extend each type in series or in parallel.
  • the power source for driving the plasma is preferably in the form of a pulse or alternating voltage with a voltage in the range of 0.2-25 kV and a frequency in the range of 5-50 kHz.
  • water repellent layer, waterproof layer, photocatalyst layer, catalyst layer, hydrophilic layer, insulation layer, dielectric layer, protective layer, etc. are formed on metal electrodes, dielectrics, and external exposed parts of the plasma generating electrode structure to prevent electrical disturbance by liquid fine particles and improve activation efficiency. It can be increased further.
  • the plasma can be more stably maintained.
  • the DBD plasma electrode according to the present invention has a through hole formed in the flow direction of the composite disinfecting fluid, so when introducing a fluid induction pipe to guide the inflow and outflow of the fluid through the inlet, outlet or both of the through hole of the complex disinfection fluid The flow can be made more smoothly.
  • Combining one or more selected configurations of the device configuration examples 1 to 4 can realize the advantages and disadvantages of each configuration example in combination to ensure optimal sterilization performance in an optimal combination.
  • the structural example which combined the apparatus structural example 2 and the structural example 4 is shown in FIG.
  • the atmospheric pressure plasma generating apparatus may apply an arc method or a plasma torch method which is advantageous in the active longitudinal plane.
  • any one of the configuration of the above 1 to 5 further comprising a device for supplying ultraviolet light to any one of the disinfectant storage container, the sprayed disinfecting complex disinfection fluid, the surface of the sterilization object and combinations thereof to further increase sterilization efficiency Can be.
  • Sterilization method in the present invention is subjected to the following steps.
  • the sprayed liquid fine particles and the carrier gas pass through the atmospheric plasma to activate the liquid disinfectant microparticles, and at the same time ozone and active species are generated to form a complex disinfecting fluid (S6);
  • the composite disinfection fluid is flying to arrive at the sterilization target (S7);
  • the complex disinfecting fluid causes a complex reaction to sterilize (S8);
  • one of the steps S3 / S4 and S6 may be omitted according to the configuration of the device.
  • Sterilization apparatus was configured according to the device configuration example 1 and device configuration examples 3 to 5, the process parameters used in each device configuration example is as follows.
  • aqueous solution of 10% hydrogen peroxide was used, and the size of the liquid fine particles to be sprayed was in the range of 10 to 30 ⁇ m, and the spraying amount was 500 cm 3 / hr.
  • Ozone was generated at 10 g / hr in an ozone generator and mixed in the carrier gas before spraying the liquid fine particles.
  • the plasma jet was applied with AC power of 10 kV and 30 kHz, and the pressure of the carrier gas was adjusted so that the plasma was extended to 1.5 cm from the plasma discharge port.
  • two jet generators were installed to maintain the symmetry so that the jetting directions of the jets were opposed to each other at a 45 ° angle.
  • the DBD plasma generator uses a through-spaced DBD electrode, which forms a through hole in a disk electrode and generates a plasma at a constant distance from the electrode as an application form of the DBD.
  • the size of the electrode was 3mm in diameter, and eight through holes were uniformly distributed.
  • interval between electrodes was 1 mm.
  • a frequency of 15 kHz and a voltage of 4 kV were applied, and the mounting position was positioned 3 cm before the liquid fine particle spray outlet and passed through the liquid fine particles.
  • water-repellent coating was performed to minimize the electrical interference effect of the liquid fine particles, and the temperature of the electrode was maintained at 150 ° C. by using a temperature controller to maintain the plasma stably.
  • the microbial samples used in the sterilization test was performed using a BI (Biological Indicator), BI is positioned at 30cm distance that the commercially Geobacillus Stearothermophillus bacteria to stainless steel to be sold from the injection discharge opening 10 6 inoculum of disinfectants. Thereafter, the sterilization apparatus was operated and sterilization tests were performed to spray up to 30 seconds in units of 2 seconds. Table 2 shows the spraying time when there was no reaction by incubating the BI for 1 hour after spraying.
  • BI Biological Indicator
  • Example 1 is a case where hydrogen peroxide and ozone are applied as the case of apparatus structure example 1
  • Example 2 and 3 are the case of apparatus structure examples 3 and 4, respectively.
  • Example 2 and 3 hydrogen peroxide and plasma are applied, and the method of applying plasma is different.
  • Example 4 is the case of the apparatus structure example 5 when hydrogen peroxide, ozone, and a plasma are simultaneously applied.
  • Comparative Example 5 only hydrogen peroxide water was injected, and in Comparative Example 6, only gaseous ozone was injected through an ozone generator.
  • Comparative Example 7 is a case where plasma is applied after only gaseous ozone is injected.
  • Example 4 showed the best efficiency, and in Comparative Examples 6 and 7, it was not sterilized even with a spraying time of 30 seconds.
  • T5 means for generating particles and spraying
  • T6 means for generating plasma
  • R1 mixes ozone in liquid disinfectant
  • R2 mixes ozone in carrier gas

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  • Life Sciences & Earth Sciences (AREA)
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  • General Health & Medical Sciences (AREA)
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Abstract

La présente invention concerne un appareil de stérilisation et un procédé de stérilisation qui favorisent la génération de radicaux OH au moyen de la réaction de produits chimiques, tels que du peroxyde d'hydrogène, avec de l'ozone et permettant d'augmenter l'efficacité de stérilisation. L'appareil comprend : un moyen de stockage (T1) destiné à un produit chimique désinfectant liquide; un moyen d'alimentation en gaz vecteur (T2) destiné au transfert du produit chimique désinfectant; un moyen (T3) destiné à générer de l'ozone; un moyen (T4) destiné au mélange de l'ozone généré avec le produit chimique désinfectant; un moyen (T5) destiné à atomiser le produit chimique désinfectant liquide en particules liquides et à pulvériser les particules liquides conjointement avec le gaz vecteur; un moyen de génération de plasma à pression atmosphérique (T6) destiné à générer de l'ozone gazeux lorsque les particules de liquide et le gaz vecteur pulvérisés le traversent et à activer les particules liquides. Si besoin, (T3/T4) ou (T6) peuvent être omis, le fluide désinfectant complexe finalement pulvérisé comprend les particules de produit chimique désinfectant liquide, de l'ozone (gazeux, liquide ou une combinaison des deux) et le gaz vecteur.
PCT/KR2017/001365 2016-02-12 2017-02-08 Appareil et procédé de stérilisation du type à pulvérisation de fluide désinfectant complexe WO2017138743A1 (fr)

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