• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    the present invention relates to a method of treating a product (214, 314) or surface with a reactive gas (210, 408) which comprises producing the reactive gas (210, 408) forming a high voltage cold plasma (hvcp ) from a working gas; transport the reactive gas (210, 408) at least 5 cm away from the hvcp; followed by contact of the product (214, 314) or surface with the reactive gas (210, 408). hvcp does not contact the product (214, 314) or surface.
    公开号:BR112018007350B1
    申请号:R112018007350-4
    申请日:2016-10-19
    公开日:2021-03-30
    发明作者:Kevin M. Keener；Mark A. Hochwalt
    申请人:NanoGuard Technologies, LLC；
    IPC主号:
    专利说明:

    FUNDAMENTALS
    [001] Biological decontamination and sterilization have a wide range of applications including medical equipment and device sterilization, food production and preservation and consumer goods preparation. Chemical systems, heat systems, high-energy electronic beams and X-ray or gamma-ray irradiation are currently used for sterilization. Each of these systems has disadvantages due to cost, efficiency, immobility, electrical power requirements, toxic waste, personal risk and the time required for sterilization or decontamination.
    [002] Plasmas have been used for decontamination and sterilization. Plasma, a fourth state of matter other than gas, liquid and solid, can be produced through electrical discharge, for example, electrical discharge through a gas. Although all plasmas contain electrons, ions and neutral species, they will have different properties depending on the composition of the gas used to prepare the plasma, as well as the electrical and structural configuration of the device used to produce the plasma.
    [001] One type of plasma is cold high voltage plasma (HVCP), which can be prepared using dielectric barrier discharge (DBD) systems. HVCP can be prepared using chemical decomposition without equilibrium of a gas, using voltages preferably from 30 kV to 500 kV, typically at a frequency of 50 or 60 Hz with a DBD system. HVCP has no studies, as well as other types of plasmas, such as thermal plasma or RF plasmas. Consequently, there is currently no theory to explain the properties of these plasmas, nor the various excited and reactive species produced in such a plasma. Over the past decade, the HVCP experimental exam has been performed to study this plasma.
    [002] Direct exposure of materials to HVCP has been studied. Of particular relevance are studies exposing biological products and contaminants to HVCP, where biological products are sealed within packages and HVCP is produced within the package. In such studies, packaged foods such as fruits and other materials were sterilized in a short period of time. The product inside the packages comes in direct contact with the plasma. Since the packages are sealed, the reactive gas produced in the plasma remains in contact with the product indefinitely, is not diluted or dispersed and the packaged product is protected against new contamination, dramatically extending the shelf life of products, such as fruits and vegetables. vegetable. See, for example, Pub. De Pat. U.S., Nos. Pub. 2013/0189156 and 2014/0044595, both for Keener and others. SUMMARY
    [003] In a first aspect, the present invention is a method of treating a product with a reactive gas, comprising producing the reactive gas by forming a cold high voltage plasma (HVCP) from a working gas; transport the reactive gas at least 5 cm away from the HVCP; followed by contact of the product with the reactive gas. HVCP does not contact the product.
    [004] In a second aspect, the present invention is a method for reducing mycotoxins in the grain, comprising producing a reactive gas by forming a cold high voltage plasma (HVCP) from a working gas; transport the reactive gas at least 3 meters away from the HVCP; followed by the contact of the grain with the reactive gas.
    [005] In a third aspect, the present invention is a method of medical sterilization of a surface, comprising producing the reactive gas by forming a cold high voltage plasma (HVCP) from a working gas and contacting the surface with reactive gas. HVCP does not contact the surface and the surface is the surface of an enclosed space, or equipment in an enclosed space, where the enclosed space has a volume of at least 8 cubic meters.
    [006] In a fourth aspect, the present invention is a method of treating a product or surface with a reactive gas, comprising providing a container having stored reactive gas produced by the formation of a cold high voltage plasma (HVCP) from a working gas and contact the product or the surface with the reactive gas. The reactive gas comprises at least one reactive or excited species other than ozone.
    [007] In a fifth aspect, the present invention is a system for treating a product or surface with a reactive gas, comprising (1) a dielectric barrier discharge (DBD) system and (2) a treatment chamber, connected fluid way with the DBD system. The treatment chamber has a volume of at least 1 cubic meter. DEFINITIONS
    [008] All current described here is alternating current, specified as volts (V) and kilovolts (kV) of effective current. Percent gas compositions (%) are percentages of volume.
    [009] A cold plasma refers to plasma that has a temperature of a maximum of 40 ° C above the temperature of the gas used to prepare the plasma (ie, the working gas), more preferably a temperature of a maximum of 20 ° C above the temperature of the gas used to prepare the plasma.
    [0010] Cold high voltage plasma (HVCP) means cold plasma prepared using a dielectric barrier discharge (DBD) system, using voltages of up to 500 kV, with a frequency of up to 1000 Hz, prepared from a gas having a pressure of 10 to 50,000 Torr, such as 760 Torr (atmospheric pressure). HVCP is not a thermal plasma, it is not a microwave plasma and it is not a radio frequency (RF) plasma. HVCP plasmas are prepared under unbalanced chemical decomposition conditions.
    [0011] Reactive gas means gas produced by an HVCP, including excited and chemically reactive species, but not those species that dissipate in 0.2 seconds or less. The composition of a reactive gas will change over time, as excited species dissipate and chemical reactions within the reactive gas take place. Reactive gas is gas that can be moved away from the DBD system that is producing an HVCP. A reactive species or excited species is considered to be present in a reactive gas if it can be detected using spectroscopy.
    [0012] Dielectric barrier (DBD) discharge, or a DBD system, means a system having at least two electrodes separated by a dielectric barrier, and may have more electrodes, where a dielectric barrier is present between each electrode, to prevent that the charge generated in the gas by a discharge reaches an electrode. The shortest distance between adjacent electrodes in a DBD system is preferably at most 30 cm (or 12 inches) and is preferably at least 0.5 cm (or 0.25 inches). Preferably, DBD systems are configured to operate under conditions to produce an HVCP. Examples of DBD systems are illustrated in figures 1A, 1B, 1C, 1D, 1E and 1F; preferably, the electrodes are separated by a gap or a filled space directly between the electrodes as shown in figures 1a, 1B, 1C and 1F.
    [0013] Working gas and working gas mixture refer to the gas that is used to form a plasma.
    [0014] Package means a container having a maximum volume of 22, 7 liters (or 6 gallons).
    [0015] Sealed or substantially sealed means that the gases inside the package or container remain inside and do not flow or diffuse out of the package or container for at least 24 hours, if left unchanged.
    [0016] Sterilization or sterilized means medical sterilization or medically sterilized, which means subjecting (or having undergone) sufficient treatment to reduce the number of viable spores of Bacillus atrophaeus on or within a product or surface by up to 1 x 10-6 of the amount present before treatment, if such spores were present.
    [0017] Sterilization of potting or sterile potting means undergoing (or having been subjected to) sufficient treatment to reduce the number of viable spores of Clostridium botulinum on or within a product or surface by up to 1 x 10-12 of the amount present before of treatment, if such spores were present.
    [0018] Pasteurized E. coli means undergoing (or having undergone) sufficient treatment to reduce the number of viable Escherichia coli O157: H7 on or within a product or surface by up to 1 x 10-5 of the amount present before treatment, if such a bacterium was present.
    [0019] Pasteurized Listeria means to undergo (or have undergone) a treatment sufficient to reduce the number of viable Listeria monocytogenes on or within a product or surface by up to 1 x 10-5 of the amount present before treatment, if such bacteria I was present.
    [0020] Pasteurized Salmonella means to undergo (or have undergone) sufficient treatment to reduce the number of Salmonella enterica subsp. enterica serovar enteritidis viable on or inside a product or surface for up to 1 x 10-5 of the amount present before treatment, if such a bacterium was present.
    [0021] The phrase “contains a lot of mycotoxin for use as a human food under US standards” means that the referenced product contains more than 20 parts per billion (ppb) of aflatoxins, more than 1000 ppb of deoxynivalenol and / or more than that 200 ppb of fumonisins, while the phrase "is suitable for use as a human food by US standards" means that the referenced product contains a maximum of 20 ppb of aflatoxins, a maximum of 1000 ppb of deoxynivalenol and a maximum of 200 ppb of fumonisins.
    [0022] The phrase “contains a lot of mycotoxin for use as a human food under US standards” means that the referenced product contains more than 2 ppb of aflatoxin B1, more than 4 ppb of total aflatoxins, more than 750 ppb of deoxynivalenol , more than 1000 ppb of fumonisins and / or more than 75 ppb of zearalenone, while the phrase “is suitable for use as a human food by US standards” means that the referenced product contains a maximum of 2 ppb of aflatoxins B1, in maximum 4 ppb of total aflatoxins, maximum 750 ppb of deoxynivalenol, maximum 1000 ppb of fumonisins and maximum 75 ppb of zearalenone.
    [0023] The phrase "contains a lot of mycotoxin for use as animal feed by US standards" means that the referenced product contains more than 20 ppb of aflatoxins, more than 5000 ppb of deoxynivalenol, more than 5000 ppb of fumonisins and / or more than 1000 ppb of zearalenone, while the phrase "is suitable for use as animal feed by US standards" means that the referenced product contains a maximum of 20 ppb of aflatoxins, a maximum of 5000 ppb of deoxynivalenol, a maximum of 5000 ppb of fumonisins and a maximum of 1000 ppb of zearalenone.
    [0024] The phrase “contains a lot of mycotoxin for use as animal feed by US standards” means that the referenced product contains more than 10 ppb of aflatoxins, more than 1750 ppb of deoxynivalenol, more than 4000 ppb of fumonisins and / or more than 100 ppb of zearalenone, while the phrase "is suitable for use as animal feed by US standards" means that the referenced product contains a maximum of 10 ppb of aflatoxins, a maximum of 1750 ppb of deoxynivalenol, a maximum of 4000 ppb of fumonisins and a maximum of 100 ppb of zearalenone. BRIEF DESCRIPTION OF THE DRAWINGS
    [0025] The following figures are provided to help illustrate the products, devices and methods of the application, but other variations and configurations are possible. Figures are not drawn to scale, with the size of some parts increased or decreased for clarity.
    [0026] Figures 1A, 1B, 1C, 1D, 1E and 1F are schematic illustrations of a variety of DBD systems.
    [0027] Figure 2 is a schematic illustration of a reactive gas treatment system for continuous treatment of a product or a surface with a reactive gas.
    [0028] Figure 3 is a schematic illustration of a reactive gas treatment system for batch treatment of a product or a surface with a reactive gas.
    [0029] Figure 4 is a schematic illustration of a reactive gas treatment system for treating equipment and / or surfaces with an enclosed space. DETAILED DESCRIPTION
    [0030] The present invention makes use of the reactive gas produced by HVCP. The reactive gas is capable of sterilizing or pasteurizing surfaces even when transported a significant distance from the DBD system where the plasma is produced, for example, 3 to 30 meters (or 10 to 100 feet). In addition, the reactive gas is able to decompose some organic and biological materials, such as mycotoxins. This is very surprising, because unlike the HVCP produced in a package, there is no direct exposure of the product to HVCP, the contact time of the reactive gas with the product is limited, for example, for 1 second, 1 minute, 30 minutes or an hour. In addition, due to the fact that the reactive gas is transported away from the DBD system where HVCP is produced, it is diluted by both diffusion into the surrounding gas and mixed with the surrounding gas and / or the working gas. Since the reactive gas is transported away from the DBD system, much larger volumes of product can be exposed to the reactive gas, in batch or continuous processes. In addition, large-scale disinfection, such as disinfection of a surgical set, can also be performed.
    [0031] Figures 1A, 1B, 1C, 1D, 1E and 1F are schematic illustrations of a variety of DBD systems that can be used to produce the HVCP that produces a reactive gas. A DBD system includes a high voltage source 10, having a ground that generates alternating current, a first electrode 20, a second electrode 30 and an intermediate dielectric, 40. One or more additional intermediate dielectrics, 60, may also be present between the first and the second electrode. In some configurations, the dielectric can surround the first and / or the second electrode. In some configurations, the charge accumulation on the electrodes, used in conjunction with the voltage waveform, can be used to estimate the power consumption of the DBD system, and can be measured by determining the voltage developed through a conventional capacitor or another sensor, 70. Preferably, a full space, 50, is present, which defines a space between the electrodes where the HVCP and the reactive gas are produced, as shown in figures 1A, 1B, 1C and 1F. However, HVCP and reactive gas can also be produced in the vicinity of dielectrics even when a clear, full space is not present in the DBD system, as illustrated in figures 1D and 1E. In some configurations, multiple electrodes, such as 3 to 10 electrodes, 4 to 8 electrodes or 5 to 7 electrodes, with one or more intermediate dielectrics between each pair of adjacent electrodes, and optionally forming multiple full spaces, can be used, such as the one illustrated in figure 1F (where a frame, 80, can be used to hold each electrode and dielectric assembly (such as 40, 20 and 40) to define each full space (50)); such an arrangement allows the production of a greater amount of HVCP and, therefore, the production of the reactive gas, while maintaining the appropriate distance between the electrodes and keeping the system compact. The configuration of the DBD system results in the current limitation of any filament discharge that is formed between the electrodes, in order to prevent the formation of a high current arc. In a preferred arrangement, a first electrode is fully enclosed in a dielectric and a second electrode is grounded.
    [0032] The electrodes can be formed from any conductive material, such as a metal. Dielectrics can be formed from any insulating material (dielectric material), such as ceramics, glass, organic or plastic materials, including multiple layers of various compositions. The thickness of the dielectric, or layers other than the dielectric, must be selected to limit the current of any filamentary discharge that may form between the electrodes. The selection of materials for the dielectric layers can have an effect on the composition of the reactive gas.
    [0033] The distance between adjacent electrodes when the electrodes are parallel, or the shortest distance between adjacent electrodes when the electrodes are not parallel, is preferably at most 30 cm (or 12 inches) and is preferably at least 0.5 cm (or 0.25 inches), such as 1 to 10 cm or 2.5 to 6 cm (or 1 to 2 inches), including 2, 3, 4, 5, 6, 7, 8 and 9 cm. The high voltage source produces a maximum voltage of 500 kV, more preferably 30 kV to 150 kV, including 40, 50, 60, 70, 80, 90, 95, 100, 110, 120, 130 and 140 kV; having a frequency of at most 1000 Hz, more preferably 10 to 100 Hz, such as 50 to 60 Hz. The time-varying DC force (i.e., pulsed) can also be used. Although the frequency is chosen primarily for convenience (for example, 50 or 60 Hz AC power is available from the municipal power grid), the voltage is selected to ensure HVCP output.
    [0034] The different selection of working gases and mixtures of working gas will affect the species present in the reactive gas produced by HVCP. Examples of gases that can be used to prepare HVCP include oxygen (O2); nitrogen (N2); water vapor (H2O); inert and noble gases, such as helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe) and sulfur hexafluoride (SF6); hydrogen (H2); carbon dioxide (CO2) and carbon monoxide (CO); halogens and pseudohalogens, such as fluorine (F2), chlorine (Cl2), bromine (Br2) and cyanogen ((CN) 2); acidic gases, such as hydrogen sulfide (H2S), hydrogen fluoride (HF), hydrogen chloride (HCl) and carbonyl sulfide (COS); ammonia (NH3); hydrazine (H4N2); nitrogen trifluoride (NF3); chlorine dioxide (ClO2); hydrocarbons, such as methane (CH4), ethane (C2H6) and acetylene (H2C2); alcohols, such as methanol (CH3OH) and ethanol (C2H5OH) and mixtures thereof. Preferred gases include air and MA65 (a mixture of 65% O2, 30% CO2 and 5% N2). Increasing the amount of water vapor in the gas can be used to reduce the ozone present in the reactive gas. Increasing the amount of noble gas, such as helium, can be used to reduce the stress required to produce HVCP. The gas pressure used to prepare the HVCP is conveniently selected as ambient or atmospheric pressure, but other pressures can be used, such as 10 to 50,000 Torr, more preferably 100 to 1000 Torr, such as 760 Torr (atmospheric pressure).
    [0035] The reactive gas contains a variety of reactive and excited species and the reactive gas always contains at least one (and typically more than one) reactive and / or excited species that is not present in the working gas. When the working gas contains oxygen (for example, O2, CO2 and / or H2O) ozone can form; however, the properties and reactions of the reactive gas are not explained by the presence of ozone alone, and the reactive gas always contains other reactive and excited species in addition to any ozone (which may or may not be present in the reactive gas). In addition to ozone, other reactive and excited species that may be present in the reactive gas include: singlet oxygen (1O2) and other excited molecular species (both molecules excited by vibration and atoms and / or electronically excited molecules, such as O2, H2, N2 , CO, CO2, H2O, He, Ne, Ar, Kr and Xe), hydroxyl radical (HO •), nitrogen oxides (such as N2O, NO, NO2, NO3, N2O3, N2O4 and N2O5), hydrogen peroxide (H2O2), hydroperoxyl (HO2), HNOx species (such as HNO4, HNO3 and HNO), atomic radicals (such as O, F, Cl, N and H) and molecular radicals (such as hydrocarbon radicals, which may also contain one or more of oxygen, nitrogen, fluorine and chlorine). Preferably, the reactive gas has at least one additional reactive and / or excited species in addition to ozone and NO2 (or N2O4) (which may or may not be present). Unlike HVCP, the reactive gas is not a plasma and does not contain free electrons. Preferably, the reactive gas contains at least 2 different reactive and / or excited species listed above, more preferably at least 3 different reactive and / or excited species listed above, even more preferably at least 4 different reactive and / or excited species listed above and most preferably still at least 5 different reactive and / or excited species listed above, including 2 to 10 or 3 to 8 or 4 to 6 different reactive and / or excited species listed above.
    [0036] It is also possible to capture and store the reactive gas in a container for later use. Preferably, the stored reactive gas is used to treat a product or surface within 24 hours after it is produced, but preferably within 12 hours, more preferably within 6 hours, even more preferably within 3 hours. hours.
    [0037] Reactive gas can also be captured and stored by cooling to extremely low temperatures, for example, using liquid nitrogen as a refrigerant or using liquid helium as a refrigerant. When captured and stored at such low temperatures, the reactive gas can be stored for extended periods of time, for example, 1 day to 6 weeks and possibly longer. Containers, such as glass or metal containers used to store other liquefied or solidified gases, can be used.
    [0038] A reactive gas treatment system includes a stored DBD or reactive gas system, and a treatment chamber. The reactive gas treatment system also includes a device, mechanism or configuration to move the reactive gas away from the DBD system (which produces an HVCP, which in turn produces the reactive gas) or a container having a gas stored reagent and into or across the treatment chamber; this can be a fluid connection between the DBD system and the treatment chamber. Preferably, the treatment chamber is not sealed; such an unsealed chamber would include a treatment chamber with a gas outlet. Preferably, the treatment chamber has a volume of at least 28 liters (or 1 cubic foot), more preferably a volume of at least 1 cubic meter and even more preferably at least 8 cubic meters. Examples of treatment chambers include rooms, receptacles, grain dryers, silos, tanks and shipping containers.
    [0039] The reactive gas system can be used to perform a method of treating a product and / or a surface, supplying the reactive gas (from the stored reactive gas or by generating an HVCP using a DBD system) and distributing the reactive gas into or across the treatment chamber. Examples of a device, mechanism or configuration for moving the reactive gas include convection, a gas path or gas line, a fan and supplying the pressurized or fluent working gas to the DBD system. Preferably, the product or surface treated by the reactive gas is not heated (that is, its temperature is not increased) by the treatment method by more than 40 ° C, more preferably by no more than 20 ° C, even more preferably not more than 10 ° C and most preferably not more than 5 ° C, such as no heating of the product or surface. Reactive gas treatment is a non-thermal processing method. Preferably, products or surfaces are not exposed to the radiation (such as UV light) produced by an HVCP during the method. Optionally, air, a working gas or other gas (such as a noble gas or nitrogen) can be used to flush the reactive gas out of the treatment chamber, or the treatment chamber can be evacuated. The method can be optionally repeated 1, 2, 3 or more times, to provide multiple treatments for products or surfaces. Optionally, the product can be sealed in a container and / or refrigerated after treatment with a reactive gas. Preferably, the product to be treated is not closed in a sealed or substantially sealed container, such as a container that has a maximum volume of 10 gallons or a maximum of 6 gallons, during treatment. Preferably, HVCP is not produced in a sealed container, such as a container that has a maximum volume of 10 gallons or a maximum of 6 gallons.
    [0040] The reactive gas produced by HVCP is transported away from the production site of the HVCP (to avoid direct exposure of the product or surface to the HVCP), by diffusion or transfer of gas. Preferably, the distance between the plasma and the product or surface to be treated is at least a distance of 5 cm, such as at least 10 cm, at least 50 cm and at least 1 meter (or 3.28 feet), more preferably at least 3 meters, for example, 3 to 300 meters, including 5, 10, 20, 30, 40 and 50 meters. In most configurations, the reactive gas can flow while it is in contact with a product or surface to be treated, although it is also possible to produce the reactive gas and transfer it to a location to treat the product or surface and confine the gas in the treatment location for a period of time. Examples of flow rates for transferring reactive gas to a location for contact with a product or surface include 10 to 3000 meters / minute, 30 to 2500 meters per minute and 1000 to 2000 meters / minute, such as 50, 100, 200, 300, 400, 500, 750 and 1500 meters / minute. The reactive gas can contact the product or surface for at least 1 second, for example, at least 2 seconds, at least 10 seconds, at least 30 seconds, at least 1 minute, at least 10 minutes, at least 30 minutes, at least 35 minutes, at least 1 hour, at least 6 hours or at least 12 hours. Examples of contact times include 1 second to 12 hours, 10 seconds to 1 hour, 1 minute to 35 minutes, including 5 seconds, 15 seconds, 2 minutes, 5 minutes, 20 minutes, 35 minutes, 40 minutes, 2 hours, 3 hours, 4 hours and 5 hours.
    [0041] Figure 2 is a schematic illustration of a reactive gas treatment system 200, for continuous treatment of a product or a surface with a reactive gas. The system includes a DBD system, 206, to generate an HVCP to produce a reactive gas, 210. The reactive gas flows along a gas path, 208, into a treatment chamber, 216, and then out of a gas outlet, 222. The product, 214, to be treated or which has a surface to be treated, can be stored in a feeder tank, 212, when it is fed into the treatment chamber, and on a conveyor , 218, which moves the product through the treatment chamber and into a receiving compartment, 220, to hold the product after it has come into contact with the reactive gas. Also shown is a gas source, 202, such as a gas tank, which supplies a working gas from which the HVCP is formed, and a gas line, 204, which supplies the DBD system with the working gas. The reactive gas can be diluted with the additional working gas when it flows through the system. The transport of reactive gas from the DBD system to the treatment chamber is by means of a pressure differential between the DBD system (at higher pressure from the introduction of the working gas) and the treatment chamber (at lower pressure due to at the gas outlet). Optionally, the gas outlet can be connected back to the DBD system by a second gas line, allowing recycling of the working gas and any remaining reactive gas. Optionally, the DBD system can be located inside the treatment chamber, avoiding the need for a gas path. In one variation, the working gas can be air and the transport of the reactive gas can be caused by a fan located in the gas path (blowing the reactive gas into the treatment chamber) or at the rear of the DBD system (blowing the air through the DBD system). Optionally, the carrier can transport the product on a screen to ensure that the reactive gas contacts all surfaces of the product. In addition, the product can be moved through the treatment chamber on a plurality of conveyors, where the product is moved when it moves from a first conveyor to a second conveyor, ensuring that the reactive gas contacts all surfaces of product. In another variation, the DBD system can be eliminated, using a stored reactive gas as the gas source and transporting the reactive gas directly to the treatment chamber. A variety of different conveyors can be used, such as a permeable belt conveyor, a propeller, a tunnel dryer, a grain dryer or a cylindrical dryer.
    [0042] Figure 3 is a schematic illustration of a reactive gas treatment system 300, for batch treatment of a product or a surface with a reactive gas. The system includes a DBD system, 306, to generate an HVCP to produce a reactive gas. Reactive gas flows along gas paths, 308 and 312, into a treatment chamber, 302, and then out through a gas path, 316, through an optional product recovery trap, 318, along a gas path, 320, and out through a gas outlet, 324. Some or all of the reactive gas and working gas can be recycled back to the DBD system via an optional gas path , 304. Reactive gas and working gas are propelled through the system by fans, 310 and 322. The product, 314, to be treated or which has a surface to be treated, is present in the treatment chamber, as illustrated, the reactive gas is fed in through the bottom of the treatment chamber to create a fluidized bed of the reactive gas and the product to guarantee the treatment of all surfaces of the product. The product recovery trap can be used to capture any product that leaves the treatment chamber and into the gas path, and return it to the treatment chamber. The treatment chamber can be a silo in the illustrated system; other treatment chambers include a fluid bed, a mechanical fluid bed and a compartment. The reactive gas can be diluted with the addition of the working gas when it flows through the system. As illustrated, the working gas can be air, but optionally the gas path, 304, can be connected with a gas source to supply a working gas to the DBD system. In another variation, the DBD system can be eliminated and replaced with stored reactive gas.
    [0043] Any product or surface can be treated with reactive gas, to sterilize (medical sterilization or packaging sterilization) or pasteurize (pasteurized Salmonella, pasteurized Listeria or pasteurized E. coli) and / or remove contaminants , such as toxins. Examples of products include fresh foods (such as fruits, vegetables, grains, beans, seeds, meats, dairy products, eggs and spices or condiments), seafood (fish and shellfish and their parts), prepared foods, frozen foods, processed foods before packaging (water, beverages, baby food, liquid eggs, fruit juice, flour, oil, nutritional product, vitamins, nutraceutical and cooked foods), packaged products (to treat the outside of the packaging), animal feed, cans , bottles, plastic containers, food containers, kitchenware and utensils; pills, capsules, unit dosage forms and powders; medical devices and medical equipment, both before use and after use; glass and laboratory plastic items; ceramic products; metal products and leather and wood products.
    [0044] If a sufficient reduction in viable microorganisms (or microorganism spores) is not achieved by treatment with the reactive gas, successive treatments can be conducted until the desired reduction is achieved, for example, sufficient to obtain the medical sterilization or sterilization of potting. For example, 1 to 10 treatments can be performed or 2 to 9 treatments, including 3, 4, 5, 6, 7 or 8 treatments can be performed. Similarly, the treatment time can also be extended. Preferably, the reactive gas treatment is repeated until medical sterilization or potting sterilization is achieved or Salmonella pasteurization, Listeria pasteurization or E. coli pasteurization is achieved.
    [0045] As with sterilization or pasteurization, if a sufficient reduction in the toxin (such as mycotoxin or aflatoxin) is not achieved by treatment with the reactive gas, successive treatments can be conducted until the desired reduction is achieved. For example, treatment can be repeated until a reduction is achieved of at least a 50% reduction, at least a 90% reduction, a reduction of up to 1 x 10-1 of the amount present before treatment, a reduction of up to 1 x 10-2 of the amount present before treatment or even a reduction of up to 1 x 10-3 of the amount present before treatment.
    [0046] Surfaces of products, rooms and containers can be treated with reactive gas, to deodorize, remove pests and insects, remove or kill fungi, sterilize, pasteurize, bleach and destroy toxins, such as biological toxins and pesticides. Reactive gas can also be used to treat waste water, exhaust gases (such as car exhaust), chemically modify oils and denature enzymes.
    [0047] Fruits (such as parts of fruit and dried fruit) and seeds (eg parts of seed; grains, such as wheat, rice and corn; vegetables, such as peas, beans, lentils, soybeans and peanuts, and nuts, such as cashews, macadamia nuts, hazelnuts, chestnuts, acorns, almonds, pecans, pistachios, walnuts and Brazilian nuts), in particular those contaminated with mycotoxins, such as aflatoxins, are preferred products because reactive gas it is capable of destroying such toxins, making such products that were previously unsuitable for human or animal consumption, useful for such purposes. Examples of toxins that can be eliminated or reduced with contact with reactive gas include: aflatoxin (such as aflatoxin B1, B2, G1 and G2), deoxynivalenol (such as 15-acetyl deoxynivalenol and 3-acetyl deoxynivalenol), ochratoxin A, T2 toxin, HT-2 toxin, zearalenone and fumonisin (such as fumonisins B1, B2 and B3). The table below indicates the number of various mycotoxins above which a product is not suitable for use as human food or animal feed, both in the United States (US) and Europe (EU). Reactive gas treatment, including repeated reactive gas treatment, can be used to remove enough mycotoxins to transform a product that is not suitable for use as a human food or animal feed into a product that is suitable for use as a human food or animal food. TABLE 1. Recommendations and regulations for safe limits on mycotoxin concentrations in grains in the United States and the European Union, as of 2008.
    a Munkvold, 2003a b Commission regulation (EC) No 1126/2007 cVariation between specific food items dVariation between livestock species
    [0048] Figure 4 is a schematic illustration of a reactive gas treatment system for treating equipment and / or surfaces with an enclosed space, such as a room, a shipping container, a trailer or a refrigerated truck. Inside the treatment chamber, 400, which here is the closed space, is a DBD system, 406, to generate an HVCP to produce a reactive gas, 408. A fan, 410, is used to distribute the reactive gas throughout the closed space. Also included are products or surfaces to be treated, which include the interior walls or surfaces of the enclosed space, optional equipment, 414, such as medical equipment (for example, surgical instruments, masks, forced breathing equipment and vital sign monitors) and / or optional surfaces, 412, such as a surgical table, to be treated with reactive gas. Optionally, supports, 402, could be used to mount the DBD system on top or on the sides of the enclosed space or the DBD system could be placed on the floor of the enclosed space. Optionally, a supply of working gas could be supplied by a gas line, 404, connected to a gas supply (not shown). Alternatively, the enclosed space could be filled with a working gas. In another configuration, the DBD system could be replaced with stored reactive gas. EXAMPLES
    [0049] The following examples are test systems to show the effects and properties of the reactive gas, where an HVCP was used to produce the reactive gas. In a typical system, the scale would be increased to achieve the treatment of commercially significant product quantities. All HVCP was produced using force at 60 Hz. Example 1: treatment of whole corn to reduce microbial load simulating exposure to short-lived reactive gas
    [0050] 100 g of whole corn were placed in an ArtBin® polypropylene (PP) container (model 9100AB) - size 37.0 cm x 35.5 cm x 5.2 cm (L x W x H). ArtBin® was placed in a second bag composed of Cryovac® B2630 high barrier film - size 40.0 cm x 47.0 cm (L x W). Each bag was washed for 3 minutes (37 L / min) with MA65 (65% O2, 30% CO2, 5% N2) as the filling gas and then sealed. The bag was then placed inside a DBD system, between two sets of 4 electrodes (each electrode: aluminum, 15.24 cm diameter, 8 total electrodes - 4 at the top, 4 at the bottom) to produce an HVCP inside the bag , but not in contact with whole corn in ArtBin®. The treatment times were 5 minutes and 15 minutes for samples of whole corn with 280 to 290 watts of power consumption. The height (span) was 5.2 cm between the electrodes. HVCPs were formed at 95 kV with an amperage of 1.0 to 1.5 mA. The dielectric barriers were used to regulate the field characteristics of the plasma inside the bags: (1) cutting plates (IKEA® brand, 37 cm x 29 cm x 2 cm); (2) plexiglass barrier positioned on the upper electrode assembly and (3) charge caps (Bella ™ brand) of 114 L and / or 151 L of charges (two above and one below each bag) for further extension of the barrier capacity surface. These dielectric barriers allowed an optimal generation of reactive gas from the HVCP.
    [0051] Ozone and nitrogen oxides were measured using Drager® short-term detector tubes (Draeger Safety AG & Co. KGaA, Luebeck, Germany). Immediately after treatment was complete, the bags were opened and the samples were washed with fresh gas to remove any remaining reactive gas with the exception of one sample that was treated for 5 minutes and the reactive gas was allowed to remain in the sealed bag for 24 hours before opening.
    [0052] Colony forming units of total aerobic bacteria (CFU / g) were determined by standard expansion plate methodology using tryptic soy agar for aerobic bacteria (TSA, Difco brand, Becton, Dickinson and Company (BD), Sparks, MD). Standard TSA plates for aerobic recovery were incorporated at 37 ° C for 24 hours. After 24 hours post-reactive gas treatment and storage at room temperature (22 ° C), microbial populations were recovered from the respective food product (s) using a sterile rinse (0.1% peptone) by stirring for 1 minute in sterile filter stomach bags to remove microorganisms from product surfaces. The shaking rinse (manual and vortex shaking) allowed external recoveries only, with no potential for additional bactericidal interference that can be produced by the internal meat as a result of stomach upset. The recoveries of the diluents were obtained by performing serial dilutions and plate enumeration. Microbial colonies were enumerated after the plates were infused at 37 ° C for 24 hours. All microbiological methods were performed in accordance with the U.S. Food and Drug Administration, Bacteriological Analytical Manual (BAM: Bacteriological Analytical Manual, 8th edition, final review: January 25, 2001). The whole corn samples were collected from the same whole corn sample by subdividing the sample and analyzing the samples before and after treatment to obtain the differential reduction in the microbial load in the corn.
    [0053] The table below summarizes the results of this experiment. "Temp." in the table refers to the temperature of the electrodes. The additional reduction, using successive treatments, could be used to achieve as large a reduction as desired. TABLE 1: HVCP process parameters: configuration of multiple electrodes with 95 kV, type of MA65 gas, quantity of the sample with 100 g of whole corn seeds
    Example 2: treatment of whole wheat to reduce microbial load by simulating short exposure to reactive gas
    [0054] 100 g of whole wheat instead of whole corn and the experiments and measurements performed in example 1 were repeated. The table below summarizes the results of this experiment. "Temp." in the table refers to the temperature of the electrodes. The additional reduction, using successive treatments, could be used to achieve as large a reduction as desired. TABLE 2: HVCP process parameters: configuration of multiple electrodes with 95 kV, type of gas MA65, sample with 100 g of whole wheat seeds
    Example 3: treatment of a known reference sample containing mycotoxins to show a reduction
    [0055] 50 grams of a naturally contaminated multiple toxin corn product supplied by Trilogy Analytical Laboratory, Washington, MO (Trilogy® Reference Material, Product #: TR-MT500, Lot #: MTC-9999E) with known concentrations of mycotoxins was placed in an ArtBin® polypropylene (PP) container (model 9100AB) - size 37.0 cm x 35.5 cm x 5.2 cm (L x W x H). ArtBin® was placed in a second bag composed of Cryovac® B2630 high barrier film - size 40.0 cm x 47.0 cm (L x W). Each bag was washed for 3 minutes (37 L / min) with air (22% O2, 78% N2) or MA65 (65% O2, 30% CO2, 5% N2) as a filling gas and then tight. Humidification of the gas used in some of the experiments was carried out using a bubble (resulting in approximately 60% humidity). The bag was then placed inside a DBD system, between two sets of 4 electrodes (each electrode: aluminum, 15.24 cm diameter, 8 total electrodes - 4 at the top, 4 at the bottom) to produce an HVCP inside the bag , but not in contact with the product on ArtBin®. The HVCP was formed at 100 kV with an amperage of 0.6 to 1.8 mA across all samples. The dielectric barriers were used to regulate the field characteristics of the plasma inside the bags: (1) cutting plates (IKEA® brand, 37 cm x 29 cm x 2 cm); (2) plexiglass barrier positioned on the upper electrode assembly and (3) charge caps (Bella ™ brand) of 114 L and / or 151 L of charges (two above and one below each bag) for further extension of the barrier capacity surface. All product samples were treated for treatment times of 30 minutes and then stored for 24 hours after treatment under ambient temperature conditions (22 ° C). After 24 hours of storage, all test samples and controls were sent to the Trilogy Analytical Laboratory, Washington, MO for a complete mycotoxin panel (# 6).
    [0056] The following two tables show the results of these experiments. In the table, “ND” means “not detected”. In table 3, the total toxin in the reference was 40.67 ppm, while after treatment the total was only 13.00 ppm, resulting in a total reduction of 68%. In table 4, the total toxin in the reference was 45.97 ppm, while after treatment the total was only 23.75 ppm, resulting in a total reduction of 48%. An additional reduction, using successive treatments, could be used to achieve as large a reduction as desired. TABLE 3: Mycotoxin reduction results using MA65 and 100 kV working gas for 30 minutes

    TABLE 4: Mycotoxin reduction results using 100 kV air working gas for 30 minutes

    Example 4: generation and transport of reactive gas

    [0057] A polypropylene tube of 0.6 cm (% ”) in diameter with an internal diameter of 0.3 cm (1/8”) was assembled with two insulated wires measuring 20, separated by 180 degrees. The wires were 152.4 cm (five feet) in overall length. One leg of each wire was attached to the polypropylene tube using a contractile polyvinyl chloride tubing. The device was placed on a platform with two vertical supports to suspend it from the floor. The tubing was connected to a compressed gas tank that had a flow meter to measure the flow of the gas that was being passed through the tube. A sampling valve and valve were installed in the discharge of this DBD system to measure the amount of ozone that was being generated as a substitute for other reactive and excited species that were being generated in addition to ozone. The amount of ozone generated was measured using Draeger® short-term detector tubes (Draeger Safety AG & Co. KGaA, Luebeck, Germany). The working gas used in this experiment was compressed air. Two different flow rates were used to determine whether the flow rate would affect the generation rate of reactive and excited species. Gas flow rates were measured using the rotameter and also measured by the time required to fill a 100 mL syringe that was attached to the sampling valve. Three different measurements were taken over a period of 30 minutes to determine the average ozone generation rate. The conditions for generating the HVCP were the same for both experiments (30 kV) using 7 watts of power. The table below summarizes the results of this experiment. TABLE 5: generation and transport of reactive gas
    权利要求:
    Claims (15)
    [0001]
    1. Method of reducing mycotoxins in fruits or seeds, characterized by the fact that it comprises: producing a reactive gas by the formation of a cold high voltage plasma (HVCP) from a working gas; transport the reactive gas at least 3 meters away from the HVCP; followed by contact of the fruit or seeds with the reactive gas; the reactive gas being the gas produced by an HVCP, including excited and chemically reactive species, except for those species that dissipate in 0.2 seconds or less.
    [0002]
    2. Method of treating a product or surface with a reactive gas, characterized by the fact that it comprises: producing the reactive gas by forming a cold high voltage plasma (HVCP) from a working gas; transport the reactive gas at least 3 meters away from the HVCP; followed by contact of the product or surface with the reactive gas; where HVCP does not contact the product or surface, and the product or surface is pasteurized from Salmonella, Listeria and / or E. coli by contact; and being that the reactive gas is the gas produced by an HVCP, including excited and chemically reactive species, except for those species that dissipate in 0.2 seconds or less.
    [0003]
    3. Method according to claim 1 or 2, characterized by the fact that the reactive gas is stored in a container.
    [0004]
    Method according to any one of claims 1 to 3, characterized by the fact that the product, fruit or seeds, or surface, is not sealed or substantially sealed within a package or container during contact, being sealed or substantially sealed means that the gases inside the package or container remain inside and do not flow or diffuse out of the package or container for at least 24 hours, if left unchanged; where the product, fruit or seed, or surface is medically sterilized by contact, and medical sterilization means that the contact is sufficient to reduce the number of viable spores of Bacillus atrophaeus on or within the product, fruit or seed , or surface for up to 1 x 10-6 of the amount present before contact, if such spores were present; and the product, fruit or seed, or surface, comprises grain.
    [0005]
    Method according to any one of claims 1 to 4, characterized by the fact that it further comprises removing the reactive gas from contact with the product, fruit or seeds, or surface, after 1 second to 12 hours; and / or where the working gas comprises MA65; and / or where the product, fruit or seed, or surface, is whole corn or whole wheat; and / or where contact is made with the product, fruit or seeds, or surface, in a fluidized bed.
    [0006]
    Method according to any one of claims 1 to 5, characterized in that the reactive gas comprises at least one reactive or excited species other than ozone.
    [0007]
    Method according to any one of claims 1 to 6, characterized in that it further comprises removing the reactive gas from contact with the product, fruit or seeds, or surface, after 35 minutes to 12 hours.
    [0008]
    8. Method according to any one of claims 1 to 7, characterized by the fact that before the method, the product, fruit or seeds, or surface, contains a lot of mycotoxin for use as human food by US standards and, after the contact, the product, the fruit or seeds, or surface are suitable for use as a human food under US standards; and / or where contact is made with the product, fruit or seeds, or surface, moving on a conveyor; and / or the contact being made in a treatment chamber having a volume of at least 1 cubic meter; and / or where the amount of mycotoxin present in the product, fruit or seeds, or surface is reduced by at least 50% or at least 90%; and / or where at least a portion of the product, fruit or seeds, or surface is at least 3 meters away from the HVCP; and / or where the product, fruit or seed, or surface, is the internal surface of a room in a hospital.
    [0009]
    9. Method according to any one of claims 1 to 8, characterized by the fact that the product, fruit or seeds, or surface, is sterilized in the potting, being sterilized in the potting means that the contact is sufficient to reduce the number of viable spores of Clostridium botulinum on or inside the product, fruit or seeds, or surface for up to 1 x 10-12 of the amount present before contact, if such spores are present.
    [0010]
    10. Method according to any one of claims 1 and 3 to 9, characterized by the fact that the product, fruit or seeds, or surface is pasteurized from Salmonella, Listeria and / or E. coli by contact.
    [0011]
    11. Method according to any one of claims 1 to 10, characterized by the fact that before the method, the product, fruit or seeds, or surface, contains a lot of mycotoxin for use as human food by US standards and, after the contact, the product, the fruit or seeds, or surface are suitable for use as a human food under US standards.
    [0012]
    12. System (200, 300, 400) for treating a product or surface with a reactive gas, characterized by the fact that it comprises: (1) a dielectric barrier discharge system (DBD) (206, 306, 406) and ( 2) a treatment chamber (216, 302, 400), fluidly connected with the DBD system (206, 306, 406), with the treatment chamber (216, 302, 400) having a volume of at least 1 cubic meter; the distance between the DBD system (206, 306, 406) and the treatment chamber (216, 302, 400) being at least 3 meters; and the reactive gas (210, 408) is the gas produced by an HVCP, including excited and chemically reactive species, except for those species that dissipate in 0.2 seconds or less.
    [0013]
    13. System according to claim 12, characterized by the fact that the DBD system (206, 306, 406) comprises: (i) a first electrode (20) totally surrounded by a dielectric (40, 60), and (ii) a second electrode (30), electrically grounded, and (iii) an alternating current voltage source (AC) (10), with a full space (50) being present between the first (20) and the second (30) electrodes; and / or the DBD system (206, 306, 406) comprises: (a) a plurality of first electrodes (20), and (b) a plurality of second electrodes (30), each between two first electrodes ( 20), with the same number of first electrodes (20) as the second electrodes (30), or one more of the first electrodes (20) than the second electrodes (30), and (c) at least one barrier dielectric between each first adjacent electrode (20) and second electrode (30), each adjacent first electrode (20) and second electrode (30) forming a full space (50).
    [0014]
    14. System according to claim 12 or 13, characterized by the fact that it further comprises a conveyor (218) inside the treatment chamber (216, 302, 400); and / or further comprises a fan (310, 322, 410), for transporting a reactive gas from the DBD system (206, 306, 406) to the treatment chamber (216, 302, 400).
    [0015]
    15. System according to any one of claims 12 to 14, characterized by the fact that the treatment chamber (216, 302, 400) has a volume of at least 8 cubic meters.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112018007350B1|2021-03-30|METHODS OF TREATING PRODUCT OR SURFACE WITH REACTIVE GAS, REDUCING MYCOTOXINS IN FRUITS OR SEEDS AND SYSTEM FOR TREATING PRODUCT OR SURFACE WITH REACTIVE GAS
    US9363880B2|2016-06-07|Method and system for treating packaged products
    US9539352B2|2017-01-10|Method and system for treating packaged products
    Schlüter et al.2013|Opinion on the use of plasma processes for treatment of foods
    JP2018533405A5|2019-07-18|
    CN105711965B|2018-07-27|Using control gas composition within a package portion generate fungicide
    KR101384565B1|2014-04-11|Apparatus for food sterilization by non-thermal
    BR112013015500B1|2018-09-11|Method d preserving the color of meat or seafood
    Rothrock et al.2017|In-package inactivation of pathogenic and spoilage bacteria associated with poultry using dielectric barrier discharge-cold plasma treatments
    Kronn et al.2015|Nonthermal plasma system for extending shelf life of raw broiler breast fillets
    Ehlbeck et al.2015|Plasma treatment of food
    Moon et al.2016|Feasibility study of atmospheric-pressure plasma treated air gas package for grape's shelf-life improvement
    Cheng et al.2019|Modified atmosphere packaging pre-storage treatment for thermal control of E. coli ATCC 25922 in almond kernels assisted by radio frequency energy
    Yepez et al.2020|Nonthermal plasma technology
    Nur et al.2015|Development of ozone technology rice storage systems | for quality improvement of rice production
    EP3146983A1|2017-03-29|Combination method for cleaning, decontamination, disinfection and sterilization of objects
    Moon et al.2019|Decontamination Effects of Ozone Generated in an Atmospheric-pressure Air Plasma on Packaged Fruits
    Butscher2016|Non-thermal plasma inactivation of microorganisms on granular food products
    RU2766600C1|2022-03-15|Method and device for treatment of cooled meat with low-temperature gas plasma of atmospheric pressure
    KR890001888B1|1989-05-30|Apparatus for liquid sterilization
    Potts et al.2011|Plasma decontamination of sealed packages
    CN111066871A|2020-04-28|Continuous low-temperature plasma sterilization device for fish surface
    Sen0|KLM
    同族专利:
    公开号 | 公开日
    EP3247412B1|2019-03-20|
    EP3247412A1|2017-11-29|
    WO2017070240A1|2017-04-27|
    RU2724046C2|2020-06-19|
    MX2018004893A|2018-08-14|
    RU2018118775A|2019-11-25|
    US11000045B2|2021-05-11|
    MX2019012614A|2020-01-30|
    CA3039902C|2019-09-17|
    US10194672B2|2019-02-05|
    EP3581209A3|2020-03-25|
    US20210267225A1|2021-09-02|
    US20170112157A1|2017-04-27|
    US20190159471A1|2019-05-30|
    CN207253505U|2018-04-20|
    HUE043743T2|2019-09-30|
    AR106421A1|2018-01-10|
    ES2730803T3|2019-11-12|
    KR20180073589A|2018-07-02|
    PL3247412T3|2019-09-30|
    EP3581209A2|2019-12-18|
    BR112018007350A2|2018-10-23|
    JP6654238B2|2020-02-26|
    MX369186B|2019-10-31|
    KR20200056477A|2020-05-22|
    JP2018533405A|2018-11-15|
    PT3247412T|2019-06-14|
    RU2018118775A3|2019-12-09|
    CN111602710A|2020-09-01|
    TR201908191T4|2019-06-21|
    CN106962471B|2020-05-01|
    KR102113202B1|2020-05-20|
    CA3039902A1|2017-04-27|
    CN106962471A|2017-07-21|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3891561A|1967-01-04|1975-06-24|Purification Sciences Inc|Corona generator apparatus|
    JPH0153026B2|1982-06-16|1989-11-10|House Food Industrial Co|
    US4643876A|1985-06-21|1987-02-17|Surgikos, Inc.|Hydrogen peroxide plasma sterilization system|
    US5184046A|1990-09-28|1993-02-02|Abtox, Inc.|Circular waveguide plasma microwave sterilizer apparatus|
    RU2102084C1|1993-04-06|1998-01-20|Евгений Петрович Бельков|Method for sterilizing objects|
    US5482684A|1994-05-03|1996-01-09|Abtox, Inc.|Vessel useful for monitoring plasma sterilizing processes|
    US5656238A|1994-10-11|1997-08-12|Johnson & Johnson Medical, Inc.|Plasma-enhanced vacuum drying|
    IL115130A|1995-09-01|1999-09-22|Israel State|Method and device for ozone sterilization of objects|
    EP0862663A1|1995-11-13|1998-09-09|IST Instant Surface Technology S.A.|Method and device for sterilising, deodorising and protecting the inner surfaces of containers and tubes|
    RU2067003C1|1995-12-15|1996-09-27|Общество с ограниченной ответственностью Научно-производственная фирма "Плайн"|Object treating method and apparatus|
    US5896587A|1996-01-11|1999-04-27|Gentry; Debra|Sun shield helmet assembly for bicyclist|
    US5895587A|1997-01-21|1999-04-20|Cryovac, Inc.|Cook-in package and method of making same|
    AU7027098A|1997-05-12|1998-12-08|Ist Instant Surface Technology S.A.|Method and device for surface treatment|
    DE19719911A1|1997-05-13|1998-11-19|Max Kettner Gmbh & Co Kg I K|Device for treating beverage containers|
    US6406759B1|1998-01-08|2002-06-18|The University Of Tennessee Research Corporation|Remote exposure of workpieces using a recirculated plasma|
    DE19814865C2|1998-04-02|2000-09-07|Fraunhofer Ges Forschung|Process for plasma treatment in hollow bodies|
    US6093432A|1998-08-13|2000-07-25|University Of Guelph|Method and apparatus for electrically treating foodstuffs for preservation|
    FR2790962B1|1999-03-16|2003-10-10|Absys|PLASMA STERILIZATION PROCESS AND DEVICES|
    US6455014B1|1999-05-14|2002-09-24|Mesosystems Technology, Inc.|Decontamination of fluids or objects contaminated with chemical or biological agents using a distributed plasma reactor|
    WO2000070117A1|1999-05-14|2000-11-23|The Regents Of The University Of California|Low-temperature compatible wide-pressure-range plasma flow device|
    US6096564A|1999-05-25|2000-08-01|Wisconsin Alumni Research Foundation|Plasma-aided treatment of surfaces against bacterial attachment and biofilm deposition|
    WO2000078123A1|1999-06-24|2000-12-28|Wisconsin Alumni Research Foundation|Cold-plasma treatment of seeds to remove surface materials|
    US6403029B1|2000-01-12|2002-06-11|The Trustees Of Princeton University|System and method of applying energetic ions for sterilization|
    KR20000053747A|2000-03-23|2000-09-05|고중석|Vaporizer fitted Minute Quantitative Liquid Injection Device|
    DE10045585A1|2000-09-15|2002-03-28|Ruediger Haaga Gmbh|Process for sterilizing and depyrogenizing washed containers|
    FR2814079B1|2000-09-15|2005-05-13|Absys|PLASMA STERILIZATION SYSTEM|
    US6638475B1|2000-11-08|2003-10-28|The Regents Of The University Of California|Method for inhibiting pathogenic and spoilage activity in products|
    KR100430345B1|2000-11-28|2004-05-04|에스이 플라즈마|Apparatus for generating low temperature plasama at atmospheric pressure|
    US20040050682A1|2000-12-27|2004-03-18|George Paskalov|Activated water apparatus and methods and products|
    US7163664B2|2000-12-27|2007-01-16|Hydro Enterprises, Inc.|Methods and devices for dispensing a potable product liquid|
    DE10108717C1|2001-02-23|2002-07-11|Bosch Gmbh Robert|Apparatus for removing electric charge from a plastic sheet, paper web or polymer fibers, comprises a plasma generator producing plasma containing charged particles and rollers which feed sheet through the region containing plasma|
    US20020182101A1|2001-03-27|2002-12-05|Pavel Koulik|Process and device for plasma surface treatment|
    WO2002078749A2|2001-03-28|2002-10-10|The Regents Of The University Of California|Atmospheric pressure rf plasma source using ambient air and complex molecular gases|
    US6811757B2|2001-04-04|2004-11-02|Ecozone Technologies Ltd.|Dielectric barrier discharge fluid purification system|
    RU2199349C2|2001-04-12|2003-02-27|ГП "Красная Звезда" НПЦ "ИНТЕКО"|Method and device for carrying out dry sterilization of medical products|
    US6562386B2|2001-05-07|2003-05-13|Regents Of The University Of Minnesota|Method and apparatus for non-thermal pasteurization|
    US20030030374A1|2001-08-03|2003-02-13|Deepak Pai|Dielectric barrier discharge plasma reactor cell|
    DE10138938A1|2001-08-08|2003-02-20|Bosch Gmbh Robert|Method for sterilizing containers in a plasma treatment chamber, involves movement of the containers and/or the plasma excitation units so that a plasma is produced in required container regions|
    KR100437095B1|2001-08-14|2004-06-23|네오포텍|A Waste Water Treatment System with Photocatalyst and Non-thermal Plasma|
    US20030039726A1|2001-08-24|2003-02-27|American Air Liquide Inc.|Method of treating food products using irradiation and a modified atmoshpere|
    WO2003018176A1|2001-08-25|2003-03-06|Accentus Plc|Non-thermal plasma reactor|
    US6822250B2|2002-03-04|2004-11-23|Steris Inc.|Mobile radiant energy sterilizer|
    FR2836772B1|2002-03-04|2004-07-09|Absys|GAS GENERATOR FOR A STERILIZATION SYSTEM|
    US20030168009A1|2002-03-08|2003-09-11|Denes Ferencz S.|Plasma processing within low-dimension cavities|
    US20040076543A1|2002-03-18|2004-04-22|Sokolowski Asaf Zeev|System and method for decontamination and sterilization of harmful chemical and biological materials|
    DE10211976A1|2002-03-19|2003-10-02|Bosch Gmbh Robert|Method and device at least for the sterilization of containers and / or their closing elements|
    AU2003219434A1|2002-04-24|2003-11-10|Apit Corp. S.A.|Device for treating surfaces of containers with plasma|
    AUPS220302A0|2002-05-08|2002-06-06|Chang, Chak Man Thomas|A plasma formed within bubbles in an aqueous medium and uses therefore|
    JP4599023B2|2002-06-21|2010-12-15|大日本印刷株式会社|Method and apparatus for sterilizing packaging material using high voltage pulse power supply|
    US20060027539A1|2003-05-02|2006-02-09|Czeslaw Golkowski|Non-thermal plasma generator device|
    US20040216845A1|2003-05-02|2004-11-04|Czeslaw Golkowski|Non-thermal plasma generator device|
    US7307243B2|2003-05-09|2007-12-11|North Carolina State University|Dynamic radiant food preparation methods and systems|
    US8475723B2|2003-07-28|2013-07-02|Iono2X Engineering, L.L.C.|Dielectric barrier discharge cell with hermetically sealed electrodes and automatic washing of electrodes during operation of the cell|
    US7767167B2|2003-07-28|2010-08-03|Iono2X Engineering, L.L.C.|Dielectric barrier discharge cell with hermetically sealed electrodes, apparatus and method for the treatment of odor and volatile organic compound contaminants in air emissions, and for purifying gases and sterilizing surfaces|
    US6991768B2|2003-07-28|2006-01-31|Iono2X Engineering L.L.C.|Apparatus and method for the treatment of odor and volatile organic compound contaminants in air emissions|
    RU2254143C2|2003-09-08|2005-06-20|ФГУП - Российский федеральный ядерный центр - Всероссийский научно-исследовательский институт экспериментальной физики - ФГУП-РФЯЦ-ВНИИЭФ|Method for sterilizing objects|
    CA2553806A1|2004-01-22|2005-08-04|Plasmasol Corporation|Modular sterilization system|
    US7367196B2|2004-02-23|2008-05-06|Princeton Biomeditech Corporation|Spinning cold plasma apparatus and methods relating thereto|
    NL1026532C2|2004-06-30|2006-01-02|Tno|Method and means for generating a plasma at atmospheric pressure.|
    DE102004049783B4|2004-10-12|2009-03-19|Je Plasmaconsult Gmbh|Apparatus for processing goods with the aid of an electrical discharge|
    FR2880105B1|2004-12-23|2007-04-20|Cie Financiere Alcatel Sa|DEVICE AND METHOD FOR CONTROLLING THE DEHYDRATION OPERATION DURING A LYOPHILIZATION TREATMENT|
    DE102005002142A1|2005-01-12|2006-07-20|Forschungsverbund Berlin E.V.|Microplasma array|
    GB0501460D0|2005-01-25|2005-03-02|Univ Edinburgh|Improved plasma cleaning method|
    US7719200B2|2005-03-07|2010-05-18|Old Dominion University|Plasma generator|
    RU2415680C2|2005-04-29|2011-04-10|Вламсе Инстеллинг Вор Технологис Ондерзук|Device and method for cleaning and disinfection of liquids, solids and gases|
    KR101433955B1|2005-07-20|2014-08-25|알파테크 인터내셔널 리미티드|Apparatus for air purification and disinfection|
    CN101227929B|2005-07-28|2012-07-18|国立大学法人佐贺大学|Free radical disinfecting device|
    WO2007031934A2|2005-09-15|2007-03-22|Philips Intellectual Property & Standards Gmbh|Adaptive driver for dielectric barrier discharge lamp|
    US20070104610A1|2005-11-01|2007-05-10|Houston Edward J|Plasma sterilization system having improved plasma generator|
    WO2007067924A2|2005-12-07|2007-06-14|Stryker Corporation|Sterilizing system with a plasma generator, the plasma generator having an electrode assembly having an array of capillaries in which the plasma is generated and into which fluid is introduced to generate sterilant|
    US7967820B2|2006-02-07|2011-06-28|P Tech, Llc.|Methods and devices for trauma welding|
    DE102006019664B4|2006-04-27|2017-01-05|Leibniz-Institut für Plasmaforschung und Technologie e.V.|Cold plasma hand-held device for the plasma treatment of surfaces|
    DE102006020483A1|2006-04-28|2007-11-08|Fachhochschule Hildesheim/Holzminden/Göttingen|Method and device for treating seed with a physical plasma at atmospheric pressure|
    US7384456B2|2006-05-15|2008-06-10|Airinspace B.V.|Modular frame for air purification devices|
    US20080006536A1|2006-05-18|2008-01-10|North Carolina State University|Processing cellulosic material utilizing atmospheric-pressure plasma|
    DE102006036536B3|2006-07-31|2008-02-28|Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.|Process for plasma treating a surface|
    EP1884248A1|2006-08-01|2008-02-06|L'AIR LIQUIDE, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude|Continuous process for functionalisation and sterilisation of flat food packaging elements by atmospheric plasma|
    KR100775124B1|2006-09-07|2007-11-08|삼성전자주식회사|System for maintaining freshness including flexible conducting polymer electrode|
    US20080063559A1|2006-09-13|2008-03-13|Joseph Alexander|Fan forced electric unit that incorporates a low power cold plasma generator and method of making same|
    FR2907351B1|2006-10-18|2009-02-06|Sidel Participations|PLASMA CONTAINER TREATMENT MACHINE, COMPRISING DECAL DEPRESSURIZATION AND PRESSURIZATION CIRCUITS|
    US7931811B2|2006-10-27|2011-04-26|Regents Of The University Of Minnesota|Dielectric barrier reactor having concentrated electric field|
    WO2008072170A2|2006-12-15|2008-06-19|Philips Intellectual Property & Standards Gmbh|Dielectric barrier discharge lamp|
    KR100707730B1|2007-01-29|2007-04-16|씨맥스|Atmospheric plasma reactor of slot type|
    WO2008096292A1|2007-02-07|2008-08-14|Philips Intellectual Property & Standards Gmbh|Dielectric barrier discharge lamp|
    US20080193330A1|2007-02-09|2008-08-14|Tokyo Institute Of Technology|surface treatment apparatus|
    WO2008126068A1|2007-04-11|2008-10-23|University Of Limerick|A plasma system|
    KR101179691B1|2007-04-11|2012-09-04|바실리 파볼로비치 바하르|Method for treating water and aqueous solutions by means of a gas-discharge plasma and a device for carrying out said method|
    DK1982734T3|2007-04-19|2011-10-17|Akos Advanced Technology Ltd|Liquid purification method and apparatus|
    WO2008138901A1|2007-05-11|2008-11-20|Force Technology|Enhancing plasma surface modification using high intensity and high power ultrasonic acoustic waves|
    WO2008144499A1|2007-05-16|2008-11-27|Old Dominion Univesity Research Foundation|System and methods for pasteurizing food using ultrashort electrical pulses|
    US8097217B2|2007-07-06|2012-01-17|Uion Co., Ltd|Atmospheric pressure plasma generating apparatus by induction electrode|
    DE102007037406A1|2007-08-08|2009-06-04|Neoplas Gmbh|Method and device for plasma assisted surface treatment|
    WO2009041861A1|2007-09-25|2009-04-02|Sik Institutet För Livsmedel Och Bioteknik Ab|Device and method for lifting and handling of objects|
    JP4408957B2|2007-09-27|2010-02-03|聡 井川|Sterilization method and apparatus|
    WO2009040130A1|2007-09-28|2009-04-02|Danmarks Tekniske Universitet|Method for sterilization of objects|
    JP2011504404A|2007-11-21|2011-02-10|ユニバーシティオブフロリダリサーチファウンデーション，インク．|Self-sterilization device using plasma field|
    US8268136B2|2007-12-20|2012-09-18|McCutchen, Co.|Electrohydraulic and shear cavitation radial counterflow liquid processor|
    WO2009098662A1|2008-02-08|2009-08-13|Ecole Polytechnique Federale De Lausanne |Long lifetime system for the generation of surface plasmas|
    US8115135B2|2008-02-14|2012-02-14|Adventix Technologies Inc.|Plasma assisted oxygen decontaminant generator and sprayer|
    SE0800771L|2008-04-07|2009-08-04|Paer H Henriksson|Arrangement and method for damaging microorganisms with an electric field and uses of the arrangement|
    WO2009134663A1|2008-05-01|2009-11-05|Airinspace B.V.|Plasma-based air purification device including carbon pre-filter and/or self-cleaning electrodes|
    US7621985B1|2008-05-24|2009-11-24|Adventix Technologies Inc.|Plasma torch implemented air purifier|
    US20090297409A1|2008-05-30|2009-12-03|Buchanan Walter R|Discharge plasma reactor|
    CA2733163C|2008-08-08|2013-11-19|Chokichi Sato|Water vapor plasma generating apparatus, sterilization and disinfection method, and method for antioxidative treatment using water vapor plasma|
    WO2010022160A2|2008-08-19|2010-02-25|Drexel University|Nano discharges in liquids|
    ITMI20081993A1|2008-11-11|2010-05-12|Francesco Mazzariello|METHOD AND PLANT FOR SANITIZING FOOD PRODUCTS CONTAMINATED BY MYCOTOSSINS|
    US9363880B2|2009-03-24|2016-06-07|Purdue Research Foundation|Method and system for treating packaged products|
    US9539352B2|2009-03-24|2017-01-10|Purdue Research Foundation|Method and system for treating packaged products|
    GB0906091D0|2009-04-07|2009-05-20|Snowball Malcolm R|None invasive disinfector|
    US8372460B2|2009-07-10|2013-02-12|L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude|System and method for non-thermal plasma treatment of foodstuffs|
    EP2474352A4|2009-09-03|2015-05-06|Univ Osaka|Method and device for supplying ions to liquid, and method and device for sterilizing|
    GB0919274D0|2009-11-03|2009-12-16|Univ The Glasgow|Plasma generation apparatus and use of plasma generation apparatus|
    US20110115415A1|2009-11-16|2011-05-19|Kun-Liang Hong|Low ozone ratio, high-performance dielectric barrier discharge reactor|
    WO2011110191A1|2010-03-10|2011-09-15|Max-Planck-Gesellschaft zur Förderung der Wissenschaften e. V.|Method and arrangement for treating an object with a low- temperature plasma|
    DE102010003284A1|2010-03-25|2011-09-29|Dot Gmbh|Process for the chemical activation of working gases in closed volumes|
    WO2011123512A1|2010-03-31|2011-10-06|Drexel University|Plasma system for air sterilization|
    FR2958187B1|2010-04-01|2012-06-15|Centre Nat Rech Scient|DEVICE FOR PRODUCING A CHEMICAL SPECIES FROM A FLUID BY USING A MICROWAVE RESONANT STRUCTURE|
    US20110268850A1|2010-04-30|2011-11-03|Vashui Rasanayagam|Modified atmosphere packaging gas, method for non-thermal plasma treatment of article, and article of manufacture for use therein|
    CN101912761B|2010-07-05|2014-02-19|洪昆喨|Dielectric discharge reactor of uniform electric field|
    DE102010026104B3|2010-07-05|2011-12-01|Fresenius Medical Care Deutschland Gmbh|Method for sterilizing at least one article, sterilization device and use thereof|
    FR2965179B1|2010-09-24|2013-04-26|C R I T T Materiaux Depots Et Traitement De Surface|DEVICE FOR COLD PLASMA STERILIZATION OF AN OBJECT, SUCH AS A MEDICAL DEVICE, AN IMPLANT OR OTHER AND METHOD USING THE SAME|
    DE102010062874A1|2010-12-13|2012-06-14|Hilti Aktiengesellschaft|Hand tool|
    US8551546B2|2010-12-20|2013-10-08|American Air Liquide, Inc.|Plasma generation of CO for modified atmosphere packaging|
    US20120156340A1|2010-12-20|2012-06-21|Vasuhi Rasanayagam|Plasma Generation of CO for Modified Atmosphere Packaging|
    DE102011009056B4|2011-01-20|2016-04-07|Schott Ag|Apparatus for the plasma treatment of hollow bodies|
    JP6317927B2|2012-01-09|2018-04-25|ムー・メディカル・デバイスズ・エルエルシーＭｏｅ Ｍｅｄｉｃａｌ Ｄｅｖｉｃｅｓ Ｌｌｃ|Plasma assisted skin treatment|
    DE102011003782A1|2011-02-08|2012-08-09|Meiko Maschinenbau Gmbh & Co. Kg|Cleaning device for cleaning items to be cleaned|
    NL2006212C2|2011-02-16|2012-08-20|Synthesis B V|Device and method for disinfecting plant seeds.|
    WO2012113568A1|2011-02-25|2012-08-30|MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V.|Disinfection appliance, container, use of a container and disinfection method for disinfecting a container, in particular for a food container|
    US9220162B2|2011-03-09|2015-12-22|Samsung Electronics Co., Ltd.|Plasma generating apparatus and plasma generating method|
    AU2012229363B2|2011-03-11|2015-08-27|Purdue Research Foundation|Generation of microbiocide inside a package utilizing a controlled gas composition|
    DE102011016448A1|2011-03-29|2012-10-04|Khs Corpoplast Gmbh|Method for sterilizing and device for blow molding of containers|
    GB201107692D0|2011-05-09|2011-06-22|Snowball Malcolm R|Sterilisation of packed articles|
    US20130164173A1|2011-06-24|2013-06-27|Elwood G. Norris|Plasma emitter|
    TWI461113B|2011-08-24|2014-11-11|Nat Univ Tsing Hua|Atmospheric pressure plasma jet device|
    WO2013067003A1|2011-11-01|2013-05-10|Pepsico, Inc.|Cold plasma sanitization for a dispensing machine|
    EP2779803B1|2011-11-11|2020-01-08|Saga University|Plasma generation device for suppressing localised discharges|
    EP2782869A1|2011-11-22|2014-10-01|Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V.|Method and device for generating a non-thermal plasma having a predetermined ozone concentration|
    GB2496879A|2011-11-24|2013-05-29|Creo Medical Ltd|Gas plasma disinfection and sterilisation|
    WO2013090418A1|2011-12-12|2013-06-20|Applied Quantum Energy Llc|Sterilization using plasma generated nox|
    US8747972B2|2012-01-31|2014-06-10|Dai Nippon Printing Co., Ltd.|Packaging material for boil/retort treatment and pouch|
    KR101391708B1|2012-06-07|2014-05-07|한국식품연구원|Method for sterilizing of packaged food using atmospheric plasma and packaged food made by the same|
    US8834803B2|2012-10-19|2014-09-16|Hussmann Corporation|Electro hydrodynamic thruster for decontaminating a display case|
    US9067788B1|2012-11-01|2015-06-30|Rick B. Spielman|Apparatus for highly efficient cold-plasma ozone production|
    CN103039151B|2012-12-07|2015-09-02|常州中科常泰等离子体科技有限公司|Cold plasma seed-treating apparatus|
    WO2014093513A1|2012-12-11|2014-06-19|Cold Plasma Medical Technologies, Inc.|Method and apparatus for cold plasma food contact surface sanitation|
    DE102013003865B4|2013-03-06|2018-09-13|Al-Ko Therm Gmbh|Method and device for cleaning an article|
    CA2903100C|2013-03-15|2021-05-25|Archer Daniels Midland Company|Improved methods for treating grain with ozone|
    DE102014107805A1|2013-07-17|2015-01-22|Vorwerk & Co. Interholding Gmbh|Arrangement for filtering air and method for air purification|
    CN105992519A|2013-09-16|2016-10-05|马斯公司|Food sanitization|
    NL2013151C2|2013-10-30|2015-05-04|Johannes Adrianus Maria Hoefnagels|Process for the treatment of fruits and vegetables.|
    EP3166413B1|2014-07-08|2020-05-13|Johannes Adrianus Maria Hoefnagels|Process for the treatment of biological material|
    GB201322387D0|2013-12-18|2014-02-05|Dublin Inst Of Technology|A method for reducing the oil content of snacks by increasing spreadsheet|
    WO2015175867A2|2014-05-15|2015-11-19|Tim Zwijack|Apparatus and method for decontaminating grain|
    US20150373923A1|2014-06-27|2015-12-31|EP Technologies LLC|Treated sprout plants with decreased bacterial viability and methods and apparatuses for making the same|
    WO2016140447A1|2015-03-03|2016-09-09|Plasmapp Co., Ltd.|Plasma treatment method for processed meat product and plasma treatment apparatus for processed meat product|
    LU92784B1|2015-07-22|2017-01-31|Luxembourg Inst Of Science And Tech |Negatively charged self-assembling supported lipid bilayer on mesoporous silica nanoparticles, method of synthesis and use as a nanovector|
    WO2017019621A1|2015-07-24|2017-02-02|The Board Of Regents For Aklahoma State University|Cold plasma devices for decontamination of foodborne human pathogens|
    US10194672B2|2015-10-23|2019-02-05|NanoGuard Technologies, LLC|Reactive gas, reactive gas generation system and product treatment using reactive gas|
    DE102015119369A1|2015-11-10|2017-05-11|INP Leipniz-Institut für Plalsmaforschung und Technologie e.V.|Apparatus, system and method for treating an object with plasma|
    JP6649754B2|2015-11-24|2020-02-19|日本特殊陶業株式会社|Plasma reactor|
    KR20190039445A|2016-09-02|2019-04-11|솜니오 글로벌 홀딩스, 엘엘씨|Free radical generator and its manufacturing method|US10194672B2|2015-10-23|2019-02-05|NanoGuard Technologies, LLC|Reactive gas, reactive gas generation system and product treatment using reactive gas|
    DE102018115300A1|2018-06-26|2020-01-02|Relyon Plasma Gmbh|Arrangement and method for decontamination of objects|
    DE102018120269A1|2018-08-21|2020-02-27|Relyon Plasma Gmbh|Arrangement and method for handling objects|
    KR102345998B1|2018-10-24|2022-01-04|가천대학교 산학협력단|Method and system for reducing harmful generated-substances including benzopyrene of argricultural processed goods using cold plasma|
    CN109089372A|2018-11-12|2018-12-25|北京赛特超润界面科技有限公司|A kind of device for the corona zone cooling and energization making plasma generator|
    KR20200076811A|2018-12-19|2020-06-30|가천대학교 산학협력단|Method for reducing acrylamide of processed food using plasma|
    IL264463D0|2019-01-24|2020-07-30|Nova Plasma Ltd|Device and method for herbs disinfection by plasma|
    DE102019106767A1|2019-03-18|2020-09-24|Relyon Plasma Gmbh|Arrangement for decontaminating a surface of objects and method for decontaminating a surface of objects|
    US10925144B2|2019-06-14|2021-02-16|NanoGuard Technologies, LLC|Electrode assembly, dielectric barrier discharge system and use thereof|
    US11166481B2|2019-10-28|2021-11-09|Clean Crop Technologies, Inc.|Systems and methods for reactive gas-based product treatment|
    CN110897077A|2019-11-14|2020-03-24|华南理工大学|Plasma active water vacuum packaging red meat preservation system and method|
    US20210308309A1|2020-04-03|2021-10-07|NanoGuard Technologies, LLC|Methods of disarming viruses using reactive gas|
    WO2021221675A1|2020-04-30|2021-11-04|Hzo, Inc.|Atmospheric plasma systems, apparatuses and processes|
    WO2021252403A1|2020-06-07|2021-12-16|Comestaag Llc|Barrier coating compositions for perishables and methods, kits and coated items relating thereto|
    WO2021252369A1|2020-06-07|2021-12-16|Comestaag Llc|Selectively treating plant items|
    法律状态:
    2019-11-05| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-01-21| B12F| Appeal: other appeals|
    2021-02-17| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-03-30| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/10/2016, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US14/921,910|2015-10-23|
    US14/921,910|US10194672B2|2015-10-23|2015-10-23|Reactive gas, reactive gas generation system and product treatment using reactive gas|
    PCT/US2016/057753|WO2017070240A1|2015-10-23|2016-10-19|Reactive gas generation system and method of treatment using reactive gas|
    [返回顶部]