Method and apparatus for producing a treatment liquid and for providing said treatment liquid to a biological system - Patents.com

Abstract

The apparatus and method for obtaining a treatment liquid (6) containing reactive oxygen species (ROS) includes the steps of generating and supplying an aqueous ozone solution (5) at a predetermined pressure (P) to a first opening (73) of two openings (73, 74) of a container (71), in which a passage body (72) containing a plurality of passages (77) having a predetermined passage cross-sectional size is disposed, whereby the aqueous ozone solution (5) flows through the passage body (72) to generate a treatment liquid (6) in which ozone is converted into reactive oxygen species such as O2 ions, which then flows through a nebulizer device (80) immediately after generation and is released in the form of small droplets, so that after interaction of the reactive oxygen species with the biological system, for example by spraying the treatment liquid (6) into the biological system, the reactive oxygen species can decay into molecular oxygen O2 or can be incorporated into a gel to stabilize the ROS. The transverse bodies (72) may be selected from among hollow fibers (78) or bundles of whole fibers (75), preferably having a transverse passage size (77), a porous body having a permeable open-cell lattice, for example obtained by sintering or in the form of a sponge, or a bed of free inorganic granular material. The aqueous ozone solution (5) is preferably obtained by conventionally producing an ozone-containing gas and contacting it with preferably non-deionized water in a static tank or mixer, preferably in the presence of hydrogen peroxide.

Description

[Technical field]

[0001] The present invention relates to a method for producing aqueous solutions containing reactive oxygen species (ROS) and delivering the treatment solutions with little or acceptable degradation of the reactive oxygen species, and further relates to an apparatus for producing such treatment solutions and delivering the treatment solutions to biological systems with little or acceptable degradation of the reactive oxygen species. [Background technology]

[0002] Reactive oxygen species (ROS) are oxygen compounds that have one or more unpaired electrons and are therefore highly reactive. Examples include the superoxide anion O2 - , the hydroxyl radical OH, etc.

[0003] As is well known, reactive oxygen species are involved in various cellular processes and in particular promote the cellular metabolism of plants and animals, as described, for example, in Italian patent application no. 102018000009939.

[0004] Italian Patent Application No. 102018000009939 describes the synthesis of ozone decomposition products, in particular the superoxide anion O2 - The paper describes an apparatus for obtaining a solution of ozone. The apparatus includes a tubular ozone generator for obtaining an ozone-containing gas from air or oxygen, a spiral ionizer for passing the ozone-containing gas through a strong alternating electric field, and a device for ionizing the superoxide anion O2 present in the gas. - Singlet oxygen (O) 1 2, a heat exchanger for cooling the gas exiting the magnetic separator, and a micronizer for absorbing the gas into water in the form of microbubbles.

[0005] The above mentioned equipment is complex and expensive, contains energy intensive components such as ion generators and magnetic separators, and also requires extensive cooling of the superoxide anion containing stream. Furthermore, in the resulting solution or dispersion, the superoxide anion is present only in low concentrations and decays rapidly to molecular oxygen.

[0006] EP 3804844 A1 discloses a generator of nanobubbles in water. A gas, which may be ozone, is fed together with water to a superfine bubble generator, which can generate water containing nanobubbles, and the water containing nanobubbles is then added to the main water flow at the confluence. The main water flow and the water containing nanobubbles are then sprayed onto a recipient, such as a plant. In this way, water containing nanobubbles of gas is sprayed onto the recipient. If ozone is used as the gas, water containing nanobubbles of ozone is sprayed onto the recipient. To generate nanobubbles, the bubble generator is provided with a through hole.

[0007] China Patent Publication No. 111643700 discloses a mobile ready-to-use ozone germicidal sprayer, which includes an ozone-water synthesis device and an ozone-water dissolving system. Ozone generated by a generator is dissolved in water by the ozone-water dissolving system to obtain high-concentration ozone water that can kill bacteria and viruses. Because the ozone-water synthesis device only requires water, the mobile ready-to-use ozone germicidal sprayer only needs to add water to the tank. The ozone-water dissolving system includes a water-ozone dissolving tube that mixes ozone and water before spraying by a nozzle.

[0008] JP 0240289 A discloses an ozonizer that generates ozone that is fed into water. The use of such water improves the storage stability of fresh produce and increases the lifespan of fish in such water. A passage in the water pipe 26 receives ozone from a nozzle that is fed through a tube. A gas-liquid mixer is provided downstream of the nozzle to mix the ozone into the water, the mixer comprising a mesh body including a plurality of ceramic porous members. Bubbles of ozone in the water that flow out of the passage pass through the member and dissolve in the water.

[0009] DE 2938517 A1 discloses a device for enriching water with O3 to produce a disinfecting solution for medical and dental care. A line has a mixing nozzle into which gaseous O3 is injected. The nozzle has a mesh insert that serves to mix the water and the gas. In particular, a head is connected to the front end of the mixing nozzle, which includes a housing with an inlet for receiving running water (arrow) and a further inlet to which a line through which ozone (arrow) coming from an ozonizer or an ozone reservoir can be connected. Between the ozone inlet and the outlet of the mixing nozzle, there are a number of individual screens, which are stacked next to each other and act as a multi-stage mixing screen for intimately mixing the ozone and the water and thus producing a highly enriched ozone / water mixture. Plates and fine mesh grids can be provided. The mesh divides the flow and provides an intimate mix between the gas and the liquid. It is possible to integrate the device into a dentist's drill. Summary of the Invention

[0010] It is therefore an object of the present invention to provide methods and devices for making ROS-containing products, particularly superoxide anion-containing products, that can deliver the products before unacceptable amounts of ROS decay back into molecular oxygen.

[0011] It is a particular object of the present invention to provide such a method and apparatus, wherein the ROS-containing product is an aqueous solution that can be delivered to a biological system immediately after ROS generation.

[0012] It is a further object of the present invention to provide such a method and apparatus for achieving higher superoxide anion concentrations in a product or solution.

[0013] It is further an object of the present invention to provide such a method and apparatus, which obtains said product with less energy consumption than the prior art.

[0014] It is another object of the present invention to provide such an apparatus which is simpler and cheaper to manufacture than prior art apparatus.

[0015] It is a further object of the present invention to provide such a device which is small in size and easily transportable.

[0016] The above object is achieved by a method and an apparatus for producing a treatment liquid containing active oxygen species capable of treating biological systems from an aqueous ozone solution according to claim 1 and an apparatus for producing such a treatment liquid and for treating biological systems with the aqueous treatment liquid according to claim 12. Advantageous variants and embodiments of the method and apparatus are defined in the dependent claims.

[0017] For simplicity, in the following description, the term "aqueous ozone solution" is used to refer to an aqueous ozone solution, and the term "treatment solution" is used to refer to an aqueous treatment solution containing reactive oxygen species.

[0018] According to one aspect of the invention, the method comprises the steps of: pre-positioning a container having a first opening and a second opening, the container having a passage body therein between the first opening and the second opening; the passage body including a plurality of passages having a predetermined passage cross-sectional size; pre-positioning a nebulizer device in fluid connection with the second opening; generating an aqueous ozone solution; directing an aqueous ozone solution at a first predetermined pressure into a first opening of the container; an aqueous ozone solution is flowed through a plurality of passages in the passage body, the predetermined passage cross-sectional size being selected to convert ozone in the aqueous ozone solution to active oxygen species to produce a treatment liquid at a second pressure lower than the first pressure; Immediately thereafter, the treatment liquid is flowed through a nebulizer device and then atomized into sub-millimeter particles that can be directly deposited on biological systems and can interact with biological systems without breaking down into molecular oxygen O2 or can be stored. and providing the Including, the passage body is configured to reduce the pressure from a first pressure value of the aqueous ozone solution to a second pressure value of the treatment liquid passing through the passage body; and a bundle of hollow fibers, wherein passages for the aqueous ozone solution and the treatment liquid are defined within the hollow fibers; a bundle of intact fibers, the pathway through which the aqueous ozone solution that is converted into a treatment liquid flows including empty spaces between the intact fibers; a porous body, the passageways for the aqueous ozone solution to be converted into a treatment liquid being defined by a permeable open-cell lattice having a predetermined cell size; a body (76') including free inorganic particulate material having a particle size selected such that a leachable open-cell lattice is formed, again having a predetermined cell size; and Combination of the above passage bodies is selected from the group consisting of:

[0019] According to another aspect of the invention, the apparatus comprises: An ozone aqueous solution generating device; a container disposed in fluid communication with the aqueous ozone solution generator, the container having a first opening and a second opening; a passage body disposed inside the container between the first opening and the second opening of the container; Equipped with The passage body includes a plurality of passages having a predetermined passage cross-sectional size. In particular, the treatment liquid generating device is for generating an ROS aqueous solution containing superoxide anion; a nebulizer device fluidly connected to the second container opening of the container and configured to emit the treatment liquid in the form of sub-millimeter particles outside of the treatment liquid generating device; directing an aqueous ozone solution at a first predetermined pressure into a first opening of the container; the aqueous ozone solution flows through a passage body to form a treatment liquid at a second pressure lower than the first pressure; The treatment liquid at the second pressure then flows through a nebulizer and is discharged outside the treatment liquid generating device. a supply pump configured to supply Equipped with the plurality of passages of the passage body exhibit a predetermined passage cross-sectional size selected to convert ozone of the aqueous ozone solution into the treatment liquid such that the active oxygen species dissolve in the treatment liquid and can be directly dispersed by the nebulizer device without being decomposed into molecular oxygen O2; the passage body is configured to reduce the pressure from a first pressure value of the aqueous ozone solution to a second pressure value of the treatment liquid passing through the passage body; and a bundle of hollow fibers, wherein passages for the aqueous ozone solution and the treatment liquid are defined within the hollow fibers; a bundle of intact fibers, the passageways being defined by the open spaces between the intact fibers; a porous body, the passageways being defined by a permeable open-cell lattice having a predetermined cell size; and Combination of the above passage bodies is selected from the group consisting of:

[0020] The flow of pressurized aqueous ozone solution through a passageway having narrow passage dimensions aids in the conversion of the inherently unstable O3 molecules into reactive oxygen species. Indeed, the combined effect of the pressure set between the first and second pressures and the narrow passage cross-section of the passageway body through which the aqueous solution flows induces mechanical stresses on the O3 molecules, which in turn induces the aforementioned ionic species O2 - and O + This results in the splitting of O3 into , a heterolytic cleavage reaction.

[0021] [ka]

[0022] "Biological systems" can include plants, seeds, human cells, and animal cells. By administering the treatment solution to such biological systems, either directly or immediately or in gel-stabilized form, at ROS concentrations enabled by the manufacturing method and device and / or possible ROS gel-stabilization, reactive oxygen species can accelerate cellular metabolic processes. This can result in beneficial effects such as, for example, enhanced plant growth, increased size of the plant itself and its fruit, rapid regeneration of human or animal tissues, especially skin tissues, reactivation of hair bulbs, and other effects discovered by the inventors of the present invention.

[0023] In particular, the hollow fiber bundle may be made of a material selected from among polysulfone, cellulose triacetate, and polyvinyl chloride.

[0024] In particular, the porous body may comprise a sintered ceramic or metallic material, or an open-cell sponge.

[0025] For example, the free inorganic particulate material may include appropriately screened sand or ultrafiltration aid.

[0026] Any of the above described embodiments of the passage body are simple and relatively inexpensive to manufacture, thus reducing the manufacturing costs of the device.

[0027] Advantageously, the cross-sectional size of the passages in the passage body is set in a range suitable for obtaining an ultrafiltration step of the fluid flowing through the passages. For example, the walls of the hollow fibers can have submicrometer porosity, for example one of the types of hollow fibers used for hemodialysis. In this case, advantageously, the porosity of the walls of the hollow fibers can be configured as part of the passages through which the aqueous solution containing ozone and the ROS formed flows.

[0028] In particular, the cross-sectional size of the passage is set between 0.001 μm and 0.2 μm, preferably between 0.005 μm and 0.015 μm. The above size range is determined by the O2 - and O + The forced flow of the aqueous ozone solution through the passageway determines a pressure drop from a first pressure to a second pressure.

[0029] The feed pump is selected so that the aqueous ozone solution reaches the container of the treatment liquid generator at a first predetermined pressure P1, preferably set between 7 and 15 bar g, in particular between 10 and 12 bar g. Furthermore, the passage body is configured to discharge the just-formed treatment liquid to the nebulizer device at a second pressure P2, preferably set between 4 and 7 bar g.

[0030] Conveniently, before or after passing through the passage, each of the ozone aqueous solution or the ROS-containing treatment liquid can be made to flow through duct parts provided in the passage body. These duct parts can have a cross-sectional size set between 10 μm and 1 mm, preferably between 50 μm and 500 μm, more preferably between 100 μm and 300 μm. The above duct parts make the flow of the aqueous solution easier.

[0031] Specifically, the step of generating an ozone aqueous solution includes: - generating ozone from oxygen, in particular from an air stream, to obtain an ozone-containing gas stream; contacting the ozone-containing gas stream with water in a mixer apparatus to dissolve the ozone in the water to form an aqueous ozone solution; Includes.

[0032] For this purpose, the ozone aqueous solution generator is a water and ozone mixer; an ozone generator gas-coupled to the mixer apparatus and configured to receive an air flow and transform the air flow into an ozone-containing gas flow; an ozone supply unit for supplying the ozone to the mixer device; may include The supply unit is configured to contact an ozone-containing gas stream with water contained within a mixer apparatus such that the ozone dissolves in the water to form an aqueous ozone solution.

[0033] In one embodiment, the mixer device comprises a reservoir configured to accommodate a predetermined amount of water. In this case, the ozone supply unit and the reservoir are mutually arranged to supply a flow of ozone-containing gas to the reservoir below a level corresponding to the amount of water in the reservoir. In this embodiment, the aqueous ozone solution is produced in the reservoir in batches, which allows for more precise control of the ozone concentration in the aqueous ozone solution and therefore more precise control of the concentration of active oxygen species in the treatment liquid.

[0034] In another embodiment, the mixer device comprises a mixing duct with a static mixer disposed therein. In this way, the aqueous ozone solution is formed during the continuous flow through the mixing duct as in the subsequent step of producing the treatment liquid. Thus, no storage container for the aqueous ozone solution is required, and thus the size and weight of the device can be reduced. For this reason, the transportation and use of the device is simplified. Furthermore, in this embodiment, the aqueous ozone solution is used to produce the treatment liquid immediately after it is produced, and the ozone in the aqueous solution is immediately converted into ROS. Therefore, only a small amount of ozone will return to diatomic oxygen O2 due to its instability before being converted into ROS. This improves the overall ROS yield in the process of producing ROS from oxygen.

[0035] Conveniently, the water used to dissolve the ozone and form the aqueous ozone solution contains a quantity of hydrogen peroxide, and therefore the step of contacting and dissolving the ozone in water is carried out in the presence of hydrogen peroxide.

[0036] Preferably, the amount of hydrogen peroxide corresponds to an amount of 35% aqueous hydrogen peroxide solution set between 1 / 500 and 1 / 5000 of the amount of water.

[0037] Preferably, the water used to prepare the aqueous ozone solution contains a certain amount of dissolved salts. Specifically, the dissolved salts consist of at least one pair of anions and one cation selected from the group consisting of sodium, potassium, calcium, magnesium, iron, chloride, sulfate, bicarbonate, fluoride, and nitrate, each of which exists at a concentration set between 50 and 500 mg / L.

[0038] Preferably, the container of the treatment liquid generating device has an elongated shape, and the first and second openings are located at both ends of the container. In particular, the passage body or the container has a tubular shape with a length set between 3 and 5 times the diameter.

[0039] Superoxide anion O2 in the treatment solution prepared as described above - Also within the scope of the invention is a method for stabilizing reactive oxygen species, including by incorporating submillimeter particles of the treatment solution into the gel.

[0040] In particular, the incorporation of such submillimeter particles of aqueous ROS into the gel is Pre-placing a quantity of gel in a gel-forming turbo mixer, i.e., equipment commonly used for making gels; maintaining said gel under agitation in a gel forming turbo mixer; During the step of stirring the gel, feeding the treatment liquid discharged by the nebulizer device into a gel-forming turbomixer. Includes.

[0041] In particular, a gel can be generated in situ, i.e., in the gel-forming turbo-mixer, by pre-positioning a quantity of gelling agent in the gel-forming turbo-mixer and, during the above step of agitating the gel, feeding a predetermined amount of water (8) into said gel-forming turbo-mixer (90), i.e., immediately before or during the incorporation of the aqueous ROS solution into the already-formed or forming gel.

[0042] For this purpose, the device comprises such a gel-forming turbo-mixer in fluid connection with the output of the nebulizer device so as to be supplied with the treatment liquid discharged by the nebulizer device, which may further be associated with a gelling agent supply means and a water supply means for preparing said gel in said gel-forming turbo-mixer or for compensating for viscosity changes of preformed gels due to addition of water with ROS in the treatment liquid. [Brief description of the drawings]

[0043] Further features and / or advantages of the invention will become more apparent from the following description of embodiment variants and forms, given by way of example and not of limitation, with reference to the attached drawings, in which:

[0044] [Figure 1] FIG. 1 is a flow diagram of an apparatus for producing a treatment liquid containing active oxygen species according to the present invention. [Diagram 2] 1 shows diagrammatically a longitudinal section of a treatment liquid generating device in which the channel body is made entirely of fibres; [Diagram 3] 1 shows diagrammatically a longitudinal section of a treatment liquid generating device in which the passage bodies are made of hollow fibers. [Figure 4] FIG. 5 is a detailed view of the fibers of the passage body of FIG. 4 in a variant in which microporous fibers are used. [Diagram 5] 1 shows a schematic longitudinal sectional view of a treatment liquid generating device in which a passage body has a porous structure. [Figure 6] 1 shows diagrammatically a perspective view of a rolled porous membrane, for example for use in hemodialysis. [Figure 7] 6 shows diagrammatically a longitudinal section of a treatment liquid generating device in which the passage body is made of the rolled porous membrane of FIG. 5; [Figure 8] 1 shows diagrammatically a longitudinal section of a treatment liquid generating device in which the passage bodies have a granular structure and are formed from free inorganic granular material; [Figure 9]FIG. 2 is a diagram showing how the pressure of the aqueous ozone / ROS solution changes along the path between the aqueous ozone solution generator and the nebulizer of FIG. 1. [Figure 10] FIG. 2 is a flow diagram of an apparatus according to an embodiment of the present invention in which the mixer apparatus includes a reservoir. [Figure 11] FIG. 11 is a flow diagram of an apparatus according to a variation of the embodiment of FIG. 10, in which a hydrogen peroxide supply is provided for supplying H2O2 to the water-ozone mixer apparatus. [Figure 12] FIG. 2 is a flow diagram of an apparatus according to an embodiment of the present invention in which the mixer apparatus comprises a mixing duct surrounding a static mixer. [Figure 13] FIG. 12 is a flow diagram of an apparatus according to a modification of the embodiment of FIG. 11, in which a hydrogen peroxide supply is provided for supplying H2O2 to the water-ozone mixer apparatus. [Figure 14] FIG. 11 is a flow diagram of an apparatus according to a modification of the embodiment of FIG. 10, in which compensation and / or recycle ducts are provided between the treatment liquid generator according to an embodiment and the reservoir of the aqueous ozone solution generator. [Figure 15] FIG. 1 is a flow diagram of an apparatus for making a treatment solution containing reactive oxygen species and stabilizing the reactive oxygen species by incorporating the solution into a gel. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0045] Referring to Figure 1, reactive oxygen species (ROS), especially superoxide anion O2 - An apparatus 100 for obtaining a treatment liquid 6 containing the above will now be described.

[0046] The apparatus 100 comprises an aqueous ozone solution generator 10, which will be described in further detail below with reference to Figures 2 to 8, and a treatment liquid generator 70 arranged in fluid connection with the aqueous ozone solution generator 10. The treatment liquid generator 70 is configured to convert the aqueous ozone solution 5 obtained by the aqueous ozone solution generator 10 into a treatment liquid 6 containing active oxygen species.

[0047] In the treatment liquid generating apparatus 70, a container 71 has a first opening 73 and a second opening 74 and surrounds a passage body 72. The first opening 73 is arranged to be fluidly connected to an outlet of the aqueous ozone solution generating apparatus 10 such that the aqueous ozone solution 5 generated by the aqueous ozone solution generating apparatus 10 can be supplied to the first opening 73 of the treatment liquid generating apparatus 70. As will be described in further detail below, a supply pump 60 can be provided for supplying the aqueous ozone solution 5 to the treatment liquid generating apparatus 70.

[0048] As shown in Figures 2-8, the passage body 72 includes a plurality of passages 77 having a predetermined passage cross-sectional size, and the ozone aqueous solution 5 is transformed into the treatment liquid 6 as it flows through the passages 77, i.e., as the ozone aqueous solution 5 progresses through the passage body 72, ozone is converted into ROS.

[0049] As explained below, ROS, especially O2 - and O + To enable ozone conversion into ions, the passage cross-sectional size of the passage 77 is set to 0.001 μm to 0.2 μm, preferably 0.005 μm to 0.015 μm.

[0050] In particular, in the embodiments shown in Figures 2 to 8, the container 71 has an elongated shape extending along a longitudinal axis 71'. Advantageously, but not exclusively, the container 71 can have a cylindrical shape. In these embodiments, the first opening 73, i.e. the inlet opening for the aqueous ozone solution 5, and the second opening 74, i.e. the outlet opening for the treatment liquid 6, are located at both ends of the elongated container 71.

[0051] In the embodiment of Fig. 2, the passage body 72 comprises a bundle 75 of complete fibres 76 arranged in the direction of the longitudinal axis 71' of the vessel 71. The complete fibres 76 are packed together so as to define between one solid fibre 76 and the other a passage 77 for the aqueous ozone solution 5 and the treatment liquid 6 formed. Between the first opening 73 and the fibre bundle 75 an empty space 73' is advantageously provided so as to obtain a uniform distribution over the entire cross section of the fibre bundle 75 for the incoming aqueous ozone solution 5.

[0052] In the embodiment of FIG. 3, the passage body 72 comprises a bundle 75 of hollow fibers 78 also arranged in the direction of the longitudinal axis 71′. The hollow fibers 78 define within themselves respective passages 77 for the aqueous ozone solution 5 and the treatment liquid 6 to be formed. In this case, the passage cross-sectional size corresponds to the internal cross-section of the hollow fibers 78. Again, in order to promote a uniform distribution of the aqueous ozone solution 5 in the passage body 72, it is preferred to provide an empty space 73′ between the first opening 73 and the bundle of fibers 75. The hollow fibers 78 are densely packed so as to maximize the number of passages 77 in the passage body 72. Preferably, the bundle of hollow fibers 78 is mounted between two end plates in the same way as the tubes of a shell-and-tube heat exchanger.

[0053] Figure 4 shows a variation of the embodiment of Figure 3, where, similar to the shell side of a shell-and-tube heat exchanger, the walls of the hollow fibers 78 have sub-micrometer porosity 77 that fluidly connects the inner conduits of the hollow fibers 78 to the outside of the hollow fibers 78 themselves inside the vessel 71. In this case, the passages 77 through which the aqueous solutions 5, 6 containing ozone and the ROS that are formed flow can include or be the porosity 77 in the walls of the hollow fibers 78.

[0054] In this configuration, the first opening 73 and the second opening 74 are preferably positioned such that the aqueous ozone solution 5, which is converted into treatment liquid 6, flows from the shell side 79 of the bundle 75 through the perforations 77 to the tube side, i.e., the first opening 73 is made through the wall of the shell portion of the vessel 71, while the second opening 74 is made through the wall of the bonnet portion of the vessel 71.

[0055] In particular, the hollow fibers 78 of the passage body 72 may be of the same type as those used in dialysis machines.

[0056] Specifically, the hollow fibers 78 of the passage body 72 may be of the same type as those used to perform ultrafiltration of a liquid passing therethrough, i.e., through the porosity in the walls of the hollow fibers 78, typically from the outside to the inside of the hollow fibers 78.

[0057] The passage body 72, i.e., the full fibers 76 and hollow fibers 78 shown in Figures 2-4, can be made from a variety of materials, specifically polysulfone, cellulose triacetate, and polyvinyl chloride, as well as polypropylene and polyethersulfone, which are well known to those skilled in the art of ultrafiltration.

[0058] In the embodiment of Fig. 5, the passage body 72 is a porous shaped body that does not include a structure of tubes or tube bundles. In this case, the passages 77 for the aqueous ozone solution 5 that is transformed into the ROS-containing treatment liquid 6 are defined by a permeable open-cell lattice, the passage cross-sectional size of which corresponds to the cell size of the lattice. For example, the porous shaped body passage body 72 can be obtained in a known manner by sintering metal or ceramic powders. In a variant of this embodiment, the porous structure passage body 72 can be an open-cell sponge.

[0059] 6 and 7 relate to an embodiment in which the passage body 72 is a porous body consisting of a rolled porous membrane 78' wound around an axis 78" to form a substantially cylindrical structure suitable for insertion into a container 71 having a cylindrical shape.

[0060] Again, specifically, the porous membrane 78' of the passage body 72 may be the same type as that used in dialysis machines.

[0061] Again, specifically, the porous membrane 78' of the passage body 72 may be of the same type as that used to perform ultrafiltration of the liquid flowing therethrough, i.e., typically through the pores 77 of the membrane 78' toward the axis 78".

[0062] The passage body 72, i.e., porous membrane 78', shown in Figures 6 and 7, can be made from a variety of materials, with polysulfone, cellulose triacetate, polylactic acid, and polyvinyl chloride being preferred, as known to those skilled in the art of ultrafiltration.

[0063] In the embodiment of Figure 8, the passage body 72 is formed from a loose inorganic particulate material 72' whose particle size is selected so that, again, a permeable open-cell lattice is formed, the cells having a predetermined size as provided by the present method. For example, the loose inorganic particulate material 72' may be sand of controlled particle size, i.e., sand that has been appropriately sieved to obtain the desired passage cross-sectional size. Alternatively, the loose inorganic particulate material may be a mineral known in the art as an ultrafiltration aid.

[0064] A plurality of passage bodies 72, preferably arranged in series, may be provided along the flow path of the aqueous ozone solution 5 of the type described above.

[0065] Advantageously, before or after passing through the passage 77, the aqueous ozone solution 5 or the ROS-containing treatment liquid 6, respectively, can flow through a duct portion 77' (FIG. 4) provided in the passage body 72. The duct portion 77' can have a cross-sectional size set between 10 μm and 1 mm, preferably between 50 μm and 500 μm, more preferably between 100 μm and 300 μm.

[0066] Downstream of the treatment liquid generator 70 is a nebulizer 80, which is fluidly connected to the second opening 74 and is preferably configured to divide the flow of liquid available at a predetermined second pressure P2 into sub-millimeter particles, more preferably micron-sized particles, and then arranged to emit the treatment liquid 6 in the form of such particles outside the generator 70.

[0067] The feed pump 60 is selected so that the aqueous ozone solution 5 reaches the container 71 at a first predetermined pressure P1, preferably set between 7 and 15 bar g, in particular between 10 and 12 bar g. The pressure profile of the aqueous solution along the device 100 is shown diagrammatically in FIG.

[0068] Furthermore, the passage body 72 is configured to discharge the treatment liquid 6 to the nebulizer device 80 at a second pressure P2 set between 4 bar g and 7 bar g.

[0069] In this way, the aqueous ozone solution 5 can flow through the passages 77 of the passage body 72, for example the inner conduit of the hollow fiber 78 in FIG. 3, or the pores 77 in the wall of the hollow fiber 78 in FIG. 3, or the permeable lattice of the porous or granular body 72 as in FIGS. 5-8. During this passage, the combined effect of the pressure and the interaction with the inner wall of the passage 77 enhances the instability of the ozone molecules O3 contained in the aqueous ozone solution 5, so that the ozone is at least partially converted into ROS, e.g., heterogeneous cleavage reactions of ozone occur, resulting in the anions O2 and O3 being decomposed into ROS. - and cation O + is formed.

[0070] [ka] Therefore, the second opening 74 produces the treatment liquid 6 containing active oxygen species.

[0071] The treatment liquid 6 produced in the passage body 72 then flows through the nebulizer 80 and is available for dispersal into a biological system or for further ROS stabilization, as described below.

[0072] In the first case, reactive oxygen species from the treatment liquid can be directly attached to the biological system and allowed to interact with it before naturally decaying into molecular oxygen, O2.

[0073] Referring to FIG. 10, water 1 and an oxygen-containing gas 3, specifically air, are mixed to form a reactive oxygen species, specifically O2 - An apparatus 101 according to one embodiment of the present invention for generating and dispensing a treatment liquid 6 containing anions is described. For simplicity, the following description refers to air 3 drawn from the environment as the oxygen-containing gas. However, in embodiments not shown in the drawings, the oxygen-containing gas may be a gas separate from atmospheric air, such as substantially pure oxygen or compressed air drawn from a portable pressure vessel.

[0074] The device 101 is configured to at least partially convert the oxygen contained in the air 3 into ozone, from which the superoxide anions of the treatment liquid 6 are then obtained, as will be described below.

[0075] The device 101 comprises a conventional ozone generator 40 configured to convert at least a portion of the oxygen contained in the air 3 into ozone O3. Associated with the ozone generator 40 is a fan 30 configured to convey an air flow 3 taken from the environment through the generator 40 at a predetermined flow rate. In the embodiment of Fig. 10, the fan 30 is arranged upstream of the ozone generator 40, but in other embodiments it may be arranged downstream of the ozone generator 40.

[0076] Thus, ozone generator 40 produces a gas 4 that contains ozone in addition to nitrogen and any remaining unconverted oxygen, as well as smaller amounts of other gases normally contained in air.

[0077] The apparatus 101 further comprises a mixer device 50 configured to contact a quantity of water 1 or a stream of water 1 with an ozone-containing gas 4 in order to dissolve ozone in the water 1 to obtain an aqueous ozone solution 5.

[0078] In the embodiment of Fig. 10, the mixer device 50 comprises a reservoir 51 for receiving a predetermined amount of water 1. For this purpose, water supply means 21 are associated with the mixer device 50, such as for example a supply line 21 from a water supply network as shown in Fig. 10. In a variant not shown, the water supply means 21 can comprise a hopper arranged to receive the water 1 and selectively put it in communication with the reservoir 51, in order to transfer the water 1 to the reservoir 51 by gravity.

[0079] The device 101 further comprises a supply line 22 for an ozone-containing gas stream 4 in which the fan 30 and the ozone generator 40 are arranged as described above. The supply line 22 and the reservoir 51 are preferably arranged to supply the ozone-containing gas stream 4 below the level of the liquids 1, 5 contained in the reservoir 51 corresponding to the amount of water 1, so as to bring the ozone-containing gas 4 into contact with the water 1. In the embodiment shown in FIG. 10, the reservoir 51 is provided with a dip tube 52 fluidly connected to the supply line 22 for the ozone-containing gas 4. In some variants of this embodiment not shown, the mixer device 50 comprises conventional gas-liquid diffusion means for finely dispersing the ozone-containing gas 4 in the water 1 contained in the reservoir 51. Such diffusion means can be arranged at the submerged end, i.e. at the outlet of the dip tube 52.

[0080] The device 101 further comprises an exhaust duct 23 for the aqueous ozone solution 5, along which a pump 60 is arranged, thus defining a suction portion 25 and a delivery portion 26 of the exhaust duct 23. The delivery portion 26 of the exhaust duct 23 is connected to a treatment liquid generator 70.

[0081] 11 shows an apparatus 102 according to an embodiment of the present invention that differs from the apparatus 101 of FIG. 10 in that it includes a hydrogen peroxide supply 35 for supplying hydrogen peroxide H2O22 to the reservoir 51 of the mixer apparatus 50. The hydrogen peroxide supply 35 may include a supply line 36 and a pump 37, such as a metering pump, configured to transfer a predetermined amount of hydrogen peroxide 2 from a hydrogen peroxide container 38. The hydrogen peroxide container 38 may be a container of hydrogen peroxide purchased from a supplier or a fixed tank 38 of the apparatus 102.

[0082] The supply means or supplies 21, 22, 35 of the water 1, ozone-containing gas 4 and hydrogen peroxide 2 can comprise respective mass or flow rate predetermining means provided for supplying a predefined amount of water, ozone and hydrogen peroxide to the mixer device 50, in particular to the reservoir 51. In the case of the water supply line 1 and hydrogen peroxide 2 as supply means, such predetermining means can be a flow meter arranged to emit an electric signal when a predefined amount of liquid is reached to be supplied to the mixer device 50, in order to close the shutoff valve 24 of the water supply line 21 of the water 1 or to stop the hydrogen peroxide supply pump 37. In the case of a loading hopper as supply means, the predetermining means can comprise a metering device or a level indicator. The aforementioned predetermining means are not described in detail or shown in the drawings, since they are of conventional type and therefore can be easily implemented by a person skilled in the art.

[0083] FIG. 12 relates to an apparatus 103 according to a further embodiment of the invention which differs from the apparatus 101 of FIG. 10 in that the mixer apparatus 50 comprises, instead of the mixing tank 51, a mixing duct 55 which is a tubular element inside which in this case a conventional static mixer 56 is arranged.

[0084] Again, the device 103 comprises water supply means 21 and an ozone-containing gas supply device 22. The water supply means 21 comprises a supply tank 54 and a supply pump 60, and may preferably comprise a water flow control valve 29 for setting the correct flow rate to the mixing duct 55. The pump 60 and the regulating valve 29 are selected to supply the water 1 to the mixing duct 55 at the pressure required by the static mixer 56. Alternatively, as shown by the dotted line, it is also possible to draw the water 1 directly from a distribution network, where it is available at a pressure at least equal to the pressure required by the static mixer 56, without the need for a supply tank 54 and a pump 60 to convey the water 1 to the mixing duct 55.

[0085] Figure 13 shows an apparatus 104 according to one embodiment of the present invention which differs from the apparatus 103 of Figure 12 in that it includes a hydrogen peroxide supply device 35 for supplying hydrogen peroxide 2 to the mixer tank 54, similar to the apparatus 102 of Figure 11. In this case, a suitable hydrogen peroxide / water ratio is conveniently set in the supply tank 54.

[0086] Referring again to Figures 9 to 12, the container 71 of the treatment liquid generator 70 has a first opening 73 fluidly connected to the outlet duct 23 of the aqueous ozone solution 5, while the second opening 74 of the superoxide anion generator 70 is preferably directly connected to a nebulizer 80.

[0087] Figure 14 shows a device 105 which differs from the device 101 of Figure 10 in that the vessel 71 of the treatment liquid generator 70, in particular the space 79 defined between the shell of the vessel 71 and the hollow fibres 78, is fluidly connected to an opening of the reservoir 51 via a compensation and recycle duct 57 in order to maintain the pressure inside the vessel below a predetermined safety value. As an alternative to the embodiment of Figure 14, a suitably set safety valve can also be provided in one wall of the vessel.

[0088] 15 diagrammatically shows an apparatus 106 according to a further embodiment of the invention, comprising a gel-forming turbo-mixer 90 fluidly connected to the output 81 of the nebulizer device 80 so as to be supplied with the treatment liquid 6 emitted by the nebulizer device 80. Furthermore, the gel-forming turbo-mixer 90 can be associated with a supply means 82 of a gelling agent 7 and a further supply means 83 of water 8 in order to prepare a gel 9 in the gel-forming turbo-mixer 90 or to compensate for viscosity changes of the pre-formed gel 9 due to the addition of water with ROS in the treatment liquid 6. EXAMPLES

[0089] A production test of the ROS-containing treatment solution 6 was carried out using a prototype apparatus according to the diagram of apparatus 105 in FIG. · The fan 30 is a fan capable of delivering an air flow rate of 0.3mc / hr at a delivery pressure of 2.4mbar; Ozone Generator 40 is an 80W generator; The tank 51 of the mixer device 50 has a volume of 30 liters; The supply pump 60 is a rotary pump capable of delivering a water flow rate of 20 liters / min at a delivery pressure of 1.8 bar; The treatment liquid generating device 70 is provided with a vessel having a diameter of φ3.2×27 mm as shown in FIG. 4, in which a bundle 75 of hollow polysulfone fibers having a diameter of 200 μm is used, more specifically, a dialysis device of the model F5HPs type of Fresenius company is used; · The Nebulizer 80 is a type of brass atomizer that is typically used for irrigation.

[0090] The tests were carried out under the following operating conditions: aqueous ozone solution throughput: 30 liters; · Time for ozone aqueous solution generation step (operation time of ozone generator 40): about 1 minute; · Feed rate to treatment liquid generator 70: 20 liters / min; In the tests of Examples 2 and 4, 35% hydrogen peroxide 2 was added to water 1 at a concentration of 0.2 ml / l for the water in reservoir 51 to prepare an aqueous ozone solution 5 .

[0091] Electrical conductivity measurements were performed on the freshly produced treated solution 6 using a Hanna EDGE instrument capable of converting measurements into ion concentration values, after preliminary calibration to eliminate the contribution of ions commonly present in water.

[0092] The results are shown in the table below, together with comparative examples of processing solutions obtained with a prior art device described in Italian patent application no. 102018000009939.

[0093] [Table 1]

[0094] The above results show significantly higher concentrations of reactive oxygen species compared to those possible with prior art devices, a significant effect of hydrogen peroxide, especially important in combination with the dissolved salts in the water, and a significant effect of the dissolved salts by themselves.

[0095] Tests carried out with different amounts of hydrogen peroxide at various concentrations of dissolved salts in the water confirmed the significant effect of these factors on the concentration of ROS ions in the resulting treated solutions, starting from low values ​​as shown in the first row of the table, up to higher values ​​as shown in the other rows, above which saturation effects tend to occur.

[0096] The above description of certain specific embodiments, as well as the examples presented, can illustrate the present invention from a conceptual point of view, so that others can use known techniques to modify and / or adjust the specific embodiments in various applications without departing from the concept of the present invention without the need for further study, and therefore, it is understood that such adjustments and modifications are considered equivalents of the specific embodiments. The means and materials for achieving the various functions described may be of various types without departing from the scope of the present invention. It is understood that the expressions or terms used are purely descriptive and therefore not limiting.

Claims

1. 1. A method for obtaining a treatment liquid (6) containing reactive oxygen species (ROS) capable of treating a biological system, comprising: a step of pre-arranging a container (71) having a first opening (73) and a second opening (74), the container (71) having a passage body (72) therein between the first opening (73) and the second opening (74), the passage body (72) including a plurality of passages (77) having a predetermined passage cross-sectional size; pre-positioning a nebulizer device (80) in fluid connection with said second opening (74); generating an aqueous ozone solution (5); The aqueous ozone solution (5) is introduced into the first opening (73) of the container (71) at a predetermined first pressure (P1), the aqueous ozone solution (5) is caused to flow through the plurality of passages of the passage body (72), and the predetermined passage cross-sectional size is selected to convert ozone in the aqueous ozone solution (5) into active oxygen species to generate a treatment liquid at a second pressure (P2) lower than the first pressure (P1); Immediately thereafter, the treatment liquid (6) is caused to flow through the nebulizer device (80) and then atomized into sub-millimeter particles; The submillimeter particles can be directly deposited in the biological system, and the ROS are molecular oxygen O ２ or the submillimeter particles can be stored. and supplying the Including, the passage body (72) is configured to reduce the pressure from the first pressure (P1) of the aqueous ozone solution (5) to the second pressure (P2) of the treatment liquid (6) passing through the passage body (72); and a bundle (75) of hollow fibers (78), wherein the passages (77) for the aqueous ozone solution (5) and the treatment liquid (6) are defined within the hollow fibers (78); a bundle (75) of whole fibers (76), wherein said passages (77) comprise empty spaces between said whole fibers (76); a porous body (76) in which the passages (77) are defined by a permeable open-cell lattice having a predetermined cell size; a body (76') containing loose inorganic particulate material; and Combination of the above-mentioned passage body (72) is selected from the group consisting of A method for obtaining a treatment liquid (6), wherein the cross-sectional size of the passages (77) in the passage body (72) is selected between 0.001 μm and 0.2 μm.

2. The step of generating the aqueous ozone solution (5) comprises: generating ozone (30) from oxygen to obtain an ozone-containing gas stream (4); The ozone-containing gas stream (4) is contacted (22) with water in a mixer device (40) to dissolve the ozone in the water, resulting in ozone O ３ forming an aqueous solution (5); Including, The water contains a predetermined amount of hydrogen peroxide (2), and the step of contacting and dissolving ozone in water is carried out in the presence of the hydrogen peroxide; 2. The method for obtaining a treatment liquid (6) according to claim 1, wherein the amount of the hydrogen peroxide (2) corresponds to an amount of a 35% aqueous hydrogen peroxide solution set between 1 / 500 and 1 / 5000 of the amount of the water (1).

3. The porous body is Sintered ceramic or metal bodies, and Open-cell sponge 3. A method for obtaining a treatment liquid (6) according to claim 1 or 2, selected from the group consisting of:

4. 3. A method for obtaining a treatment liquid (6) according to claim 1 or 2, wherein the loose inorganic particulate material is selected from among sand and ultrafiltration aid, the loose inorganic particulate material having a particle size selected to form a permeable open-cell lattice having a predetermined cell size.

5. 3. The method for obtaining a treatment liquid (6) according to claim 1 or 2, wherein the passage cross-sectional size of the passage (77) in the passage body (72) is configured to perform an ultrafiltration step of a fluid flowing through the passage (77).

6. A method for obtaining the treatment liquid (6) described in claim 2, wherein the water contains ions selected from the group consisting of Na + , K + , Ca 2+ , Mg 2+ , Fe 2+ , Cl - , SO 4 = , HCO 3 - , F - , and NO 3 - , each of which is present at a concentration set between 50 and 500 mg / liter.

7. A method for stabilizing reactive oxygen species including superoxide anion O 2 − in a treatment liquid (6) obtained by the method for obtaining the treatment liquid (6) according to claim 1 or 2, comprising the steps of producing the treatment liquid (6): The method for stabilization of reactive oxygen species further comprises incorporating the submillimeter particles of the treatment liquid (6) into a gel (9).

8. The step of incorporating the submillimeter particles into a gel (9) comprising: pre-placing a quantity of said gel (9) in a gel-forming turbo mixer (90); maintaining said gel (9) under agitation in said gel-forming turbomixer (90); feeding the treatment liquid (6) emitted by the nebulizer device into the gel-forming turbomixer (90) during the step of maintaining the gel (9) under agitation; 8. The method for stabilizing reactive oxygen species of claim 7, comprising:

9. An apparatus for producing a treatment solution (6) containing reactive oxygen species (ROS) and treating a biological system with said treatment solution (6), comprising: An ozone aqueous solution generator (10), A treatment liquid generating device (70), comprising: a water-ozone solution generator (10) in fluid communication with the water-ozone solution generator (10); a container (71) having a first opening (73) and a second opening (74); a passage body (72) disposed inside the container (71) between the first opening (73) and the second opening (74); It is equipped with a treatment liquid generating device (70) in which the passage body (72) includes a plurality of passages (77) having a predetermined passage cross-sectional size; a nebulizer device (80) fluidly connected to the second opening (74) of the container (71) and configured to emit the treatment liquid (6) in the form of submillimeter particles to the outside of the treatment liquid generator (70); An aqueous ozone solution (5) is introduced into the first opening (73) of the container (71) at a predetermined first pressure (P1), The aqueous ozone solution (5) flows through the passage body (72) to form a treatment liquid (6) at a second pressure (P2) lower than the first pressure (P1); Thereafter, the treatment liquid (6) at the second pressure (P2) flows through the nebulizer device (80) and is discharged to the outside of the treatment liquid generating device (70). a supply pump (60) configured to supply Equipped with the plurality of passages of the passage body (72) exhibit the predetermined passage cross-sectional size selected to convert ozone from the aqueous ozone solution (5) into the treatment liquid so that active oxygen species dissolve in the treatment liquid and can be directly dispersed by the nebulizer device (80) without being decomposed into molecular oxygen O2; the passage body (72) is configured to reduce the pressure from the first pressure (P1) of the aqueous ozone solution (5) to the second pressure (P2) of the treatment liquid (6) passing through the passage body (72); and a bundle (75) of hollow fibers (78), wherein the passages (77) for the aqueous ozone solution (5) and the treatment liquid are defined within the hollow fibers (78); a bundle (75) of whole fibers (76), said passages (77) being defined by open spaces between said whole fibers (76); a porous body, the passages (77) being defined by a permeable open-cell lattice having a predetermined cell size; and Combination of the above-mentioned passage body (72) is selected from the group consisting of The device wherein the cross-sectional size of the passage (77) in the passage body (72) is selected between 0.001 μm and 0.2 μm.

10. The apparatus further comprises a gel-forming turbomixer (90) configured to contain a quantity of gel (9) and to maintain said gel (9) under agitation; 10. The apparatus according to claim 9, wherein the gel-forming turbomixer (90) is fluidly connected to an output port (81) of the nebulizer device (80) so as to be supplied with the treatment liquid (6) emitted by the nebulizer device (80).

11. The hollow fibers (78) are made of a material selected from the group consisting of polysulfone, cellulose triacetate, and polyvinyl chloride; or The porous body is Sintered ceramic or metal bodies, and Open-cell sponge or 11. The apparatus of claim 9 or 10, wherein the loose inorganic particulate material is selected from among sand and ultrafiltration aid, said loose inorganic particulate material having a particle size selected to form a permeable open-cell lattice having a predetermined cell size.

12. The apparatus of claim 9 or 10, wherein the supply pump (60) is configured to supply the aqueous ozone solution (5) to the first opening (73) of the container (71) at the predetermined first pressure (P1) set between 7 barg and 15 barg, in particular between 10 barg and 12 barg.

13. An apparatus as described in claim 9 or 10, wherein the container (71) has an elongated shape, the first opening (73) and the second opening (74) which function as an inlet opening for the aqueous ozone solution (5) and an outlet opening for the treatment liquid (6), respectively, are arranged at both ends of the container (71), and specifically, the container (71) has a tubular shape with a length (L) set between 3 and 5 times its diameter (D).

14. The ozone aqueous solution generating device (10), a water and ozone mixer device (50); an ozone generator (40) gaseously connected to the mixer device (50) and configured to receive an atmospheric air flow (3) and transform the atmospheric air flow (3) into an ozone-containing gas flow (4); an ozone supply unit (22) for supplying the ozone to the mixer device (50), the ozone supply unit (22) being configured to contact the ozone-containing gas stream (4) with the water contained in the mixer device (50) so that the ozone dissolves in the water to form the aqueous ozone solution (5) O3; Equipped with The water and ozone mixer device (50) a mixer device (50) comprising a reservoir (51) configured to contain a predetermined amount of water (1), wherein the ozone supply unit (22) and the reservoir (51) are configured to supply the ozone-containing gas stream (4) below a level corresponding to the amount of water (1) in the reservoir (51); and A mixer (50) comprising a mixing duct (55) in which a static mixer (56) is arranged.

11. The device of claim 9 or 10, selected from the group consisting of:

15. The gel-forming turbo mixer (90) is provided with: a gelling agent supply means (82), and Water supply means (83) The apparatus of claim 10 , wherein:

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