Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
  • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
  • B01F23/20—Mixing gases with liquids
  • B01F23/23—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids
  • B01F23/232—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids using flow-mixing means for introducing the gases, e.g. baffles
  • B01F23/2323—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids using flow-mixing means for introducing the gases, e.g. baffles by circulating the flow in guiding constructions or conduits
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K9/00—Medicinal preparations characterised by special physical form
  • A61K9/08—Solutions
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K33/00—Medicinal preparations containing inorganic active ingredients
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K33/00—Medicinal preparations containing inorganic active ingredients
  • A61K33/40—Peroxides
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
  • A61K47/02—Inorganic compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
  • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
  • B01F23/20—Mixing gases with liquids
  • B01F23/23—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids
  • B01F23/231—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids by bubbling
  • B01F23/23105—Arrangement or manipulation of the gas bubbling devices
  • B01F23/2312—Diffusers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
  • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
  • B01F23/20—Mixing gases with liquids
  • B01F23/23—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids
  • B01F23/232—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids using flow-mixing means for introducing the gases, e.g. baffles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
  • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
  • B01F23/20—Mixing gases with liquids
  • B01F23/23—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids
  • B01F23/237—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids characterised by the physical or chemical properties of gases or vapours introduced in the liquid media
  • B01F23/2376—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids characterised by the physical or chemical properties of gases or vapours introduced in the liquid media characterised by the gas being introduced
  • B01F23/23761—Aerating, i.e. introducing oxygen containing gas in liquids
  • B01F23/237613—Ozone
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
  • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
  • B01F23/20—Mixing gases with liquids
  • B01F23/29—Mixing systems, i.e. flow charts or diagrams
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
  • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
  • B01F25/40—Static mixers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
  • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
  • B01F25/40—Static mixers
  • B01F25/45—Mixers in which the materials to be mixed are pressed together through orifices or interstitial spaces, e.g. between beads
  • B01F25/452—Mixers in which the materials to be mixed are pressed together through orifices or interstitial spaces, e.g. between beads characterised by elements provided with orifices or interstitial spaces
  • B01F25/4522—Mixers in which the materials to be mixed are pressed together through orifices or interstitial spaces, e.g. between beads characterised by elements provided with orifices or interstitial spaces the components being pressed through porous bodies, e.g. flat plates, blocks or cylinders, which obstruct the whole diameter of the tube
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
  • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
  • B01F25/40—Static mixers
  • B01F25/45—Mixers in which the materials to be mixed are pressed together through orifices or interstitial spaces, e.g. between beads
  • B01F25/452—Mixers in which the materials to be mixed are pressed together through orifices or interstitial spaces, e.g. between beads characterised by elements provided with orifices or interstitial spaces
  • B01F25/4523—Mixers in which the materials to be mixed are pressed together through orifices or interstitial spaces, e.g. between beads characterised by elements provided with orifices or interstitial spaces the components being pressed through sieves, screens or meshes which obstruct the whole diameter of the tube
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
  • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
  • B01F25/40—Static mixers
  • B01F25/45—Mixers in which the materials to be mixed are pressed together through orifices or interstitial spaces, e.g. between beads
  • B01F25/452—Mixers in which the materials to be mixed are pressed together through orifices or interstitial spaces, e.g. between beads characterised by elements provided with orifices or interstitial spaces
  • B01F25/4524—Mixers in which the materials to be mixed are pressed together through orifices or interstitial spaces, e.g. between beads characterised by elements provided with orifices or interstitial spaces the components being pressed through foam-like inserts or through a bed of loose bodies, e.g. balls
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
  • B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
  • B01F35/181—Preventing generation of dust or dirt; Sieves; Filters
  • B01F35/187—Preventing generation of dust or dirt; Sieves; Filters using filters in mixers, e.g. during venting
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
  • B01J13/0052—Preparation of gels
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
  • C01B13/10—Preparation of ozone
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
  • B01F2101/00—Mixing characterised by the nature of the mixed materials or by the application field
  • B01F2101/04—Mixing biocidal, pesticidal or herbicidal ingredients used in agriculture or horticulture, e.g. for spraying
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
  • B01F2101/00—Mixing characterised by the nature of the mixed materials or by the application field
  • B01F2101/2202—Mixing compositions or mixers in the medical or veterinary field
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
  • B01F2101/00—Mixing characterised by the nature of the mixed materials or by the application field
  • B01F2101/305—Treatment of water, waste water or sewage

Definitions

• the present invention relates to a method for making a water solution containing reactive oxygen species (ROS) and for delivering the treatment solution with negligible or acceptable decay of the reactive oxygen species.
• the invention also relates to an apparatus for making such a treatment solution and for delivering the treatment solution to a biological system with negligible or acceptable decay of the reactive oxygen species.
• ROS reactive oxygen species
• ROS Reactive oxygen species
• IT 102018000009939 describes an apparatus for obtaining a solution of ozone splitting products, in particular superoxide anions 02’.
• the apparatus includes a tubular ozone generator for obtaining an ozone-containing gas from air or oxygen; a helical-tube ion generator, in which the ozone-containing gas flows through a strong alternating electric field; a magnetic ion separator where superoxide anions 02’ present in the gas are separated from singlet oxygen O 1 2 ; a heat exchanger to cool down the gas leaving the magnetic separator; and a micronizer to absorb this gas into water in the form of microbubbles.
• the above equipment is complicated and expensive, includes such energy-intensive components as the ion generator and the magnetic separator, and also requires vigorous cooling of the superoxide anions-containing stream. Moreover, in the obtained solution or dispersion, the superoxide anions are present at a low concentration, and rapidly decay to molecular oxygen.
• EP3804844A1 discloses a generator of nanobubbles in water.
• a gas that can be also ozone, is supplied along with a water supply to a ultrafine bubble generating apparatus, which is capable of generating water containing nanobubbles, which in turn is added to a water main stream at a junction point.
• the water main stream and the water containing nanobubbles then are sprayed on an acceptor like a plant. In this way, the water containing nanobubbles of the gas is sprayed on the acceptor.
• ozone is used as gas, then on the acceptor a water containing nanobubbles of ozone is prayed on the acceptor. Passage holes are provided in bubble generating apparatus for generating the nanobubbles.
• CN11 1643700A discloses a movable ready-to-use ozone disinfection sprayer, comprising an ozone-water synthesis device and an ozone-water dissolving system.
• the ozone generated by generator is dissolved in water through the ozone water dissolving system, obtaining a high-concentration ozone water capable of killing bacteria and virus. Since the ozone-water synthesis device only requires water, the movable ready-to-use ozone disinfection sprayer only requires adding water into a tank.
• the ozone-water dissolving system comprises a water-ozone dissolution tube where ozone and water mix before being sprayed by a nozzle.
• JPH0240289A discloses an ozonizer which generates ozone that is fed into water. By using such water a shelf stability of perishables is increased and life of fishes in such water is increased.
• a passage of a water pipe 26 receives ozone from a nozzle supplied through a tube.
• a gas-liquid mixing part is provided downstream of the nozzle, comprising a meshy body containing plural porous members of ceramic. Bubbles of ozone in water flowing out of a passage are dissolved in water by passing through members.
• DE2938517A1 discloses a device for enriching water with O3 to produce a sterilizing solution for medical and dental practice.
• the line has a mixing nozzle to which gaseous O3 is injected.
• the nozzle has a mesh insert which serves to mix the water and gas.
• a head is connected to the front end of a mixing nozzle containing a housing having an inlet for receiving flowing water (arrow) and a further inlet to which a line can be connected, through which ozone can flow (arrow), coming from an ozonizing device or from an ozone store.
• a plurality of individual screens that are stacked next to one another and which serve as a multistage mixing screen for intimately mixing ozone and water and thus for producing an ozone/water mixture which is enriched in high concentration.
• Plates and fine-mesh grids can be provided. The mesh divides the flow and provides an intimate mixture between the gas and the liquid.
• the device can be incorporated into a dentist’s drill.
• ROS-containing product is a water solution that can be supplied to the biological system immediately after the ROS production.
• the method comprises the steps of: prearranging a container with a first opening and a second opening and a passage body within the container, between the first opening and the second opening, wherein the passage body includes a plurality of passageways having a predetermined passage-section size; prearranging a nebulizer device in hydraulic connection with the second opening; generating an ozone water solution; feeding the ozone water solution into the first opening of the container at a predetermined first pressure, in such a way that the ozone water solution is caused to flow through the plurality of passageways of the passage body, wherein said predetermined passage-section size is selected to convert the ozone in the ozone water solution is converted to reactive oxygen species, generating a treatment solution at a second pressure lower than the first pressure; the treatment solution is immediately thereafter caused to flow through the nebulizer device and is then nebulized into submillimetric particles which can be directly deposited on the biological system and can interact with it without decaying into molecular oxygen O
• the apparatus comprises: an ozone water solution generator device; a treatment solution generator device for generating a ROS water solution including, in particular superoxide anions, wherein the treatment solution generator device is arranged in hydraulic connection with the ozone water solution generator device, wherein the treatment solution generator device comprises: a container with a first opening and a second opening, and a passage body arranged within the container between the first opening and the second opening of the container, wherein the passage body includes a plurality of passageways having a predetermined passage-section size; a nebulizer device in hydraulic connection with the second container opening of the container, the nebulizer device arranged to release the treatment solution outside of the treatment solution generating device in the form of submillimetric particles; a supply pump arranged to supply the ozone water solution into the first opening of the container at a predetermined first pressure, in such a way that said ozone water solution flows through the passage body, forming the treatment solution at a second pressure lower than the first pressure
• the pressurised flow of the ozone water solution through passageways with a narrow passage dimension assists the conversion of the intrinsically unstable O3 molecules into reactive oxygen species.
• the combined action of the pressure, set between the first pressure and the second pressure, and the narrow passage section of the passage body passageways, through which the water solution flows induces a mechanical stress on the O3 molecules that leads to the Os-splitting towards the aforementioned ionic species 02’ and O + , i.e. to the heterolytic cleavage reaction:
• the “biological system” can include plants, seeds, human cells and animal cells.
• the bundle of hollow fibres may be made of a material selected among a polysulphone, cellulose triacetate and polyvinyl chloride.
• the porous body may comprise a sintered, ceramic or metallic material, or an open cell sponge.
• the loose mineral particulate material may comprise an appropriately screened sand or an ultrafiltration aid.
• the passage-section size of the passageways in the passage body is set in a range appropriate to obtain an ultrafiltration step of a fluid flowing therethrough.
• the walls of the hollow fibres can have a submicrometric porosity, for example they can be hollow fibres of one of the types used in haemodialysis.
• the porosities of the wall of the hollow fibres can be configured as a part of the passageways through which the water solution containing ozone and the ROS being formed flows.
• the passage-section size of the passageways is set between 0,001 pm and 0,2 pm, preferably between 0,005 pm and 0,015 pm.
• the aforementioned size ranges make it possible to increase, or maximize the 02’ and O + concentrations in the treatment solution.
• the forced flow of the ozone water solution through the passageways determines the pressure drop from the first pressure to the second pressure.
• the supply pump is selected in such a way that the ozone water solution reaches the container of treatment solution generator device at a predetermined first pressure Pi, preferably set between 7 and 15 bar g, in particular between 10 and 12 bar g.
• the passage body is arranged to release the freshly formed treatment solution to nebulizer device at second pressure P2 set between 4 bar g and 7 bar g.
• the ozone water solution, or the ROS-containing treatment solution can flow through duct portions that are provided in the passage body.
• Said duct portions can have a section size set between 10 pm and 1 mm, preferably between 50 pm and 500 pm, more preferably between 100 pm and 300 pm. The above duct portios make easier the flow of the water solutions.
• the step of generating an ozone water solution comprises the steps of: generating ozone from oxygen, in particular from oxygen of an air stream, obtaining an ozone-containing gas stream; contacting the ozone-containing gas stream with water in a mixer device and dissolving the ozone into the water, so as to form the ozone water solution.
• the ozone water solution generator device may include: a water-ozone mixer device; an ozone generator pneumatically connected to the mixer device and arranged to receive an atmospheric air stream and to change the latter into a stream of ozone-containing gas; an ozone supply unit for supplying said ozone to the mixer device, the supply unit arranged to bring the ozone-containing gas stream into contact with water contained in the mixer device, so that the ozone dissolves into the water, forming an ozone water solution.
• the mixer device comprises a reservoir configured to contain a predetermined amount of water.
• the ozone supply unit and reservoir are mutually arranged to supply the stream of ozone-containing gas into the reservoir below a level corresponding to the amount of water therein.
• the ozone water solution is generated batchwise in the reservoir, which allows for more accurate control of the ozone concentration in the ozone water solution and the concentration of the reactive oxygen species in the treatment solution can be more accurately controlled as well.
• the mixer device comprises a mixing duct within which a static mixer is arranged.
• a static mixer is arranged.
• the ozone water solution is formed while flowing through the mixing duct, in a continuous way like the subsequent step of generating the treatment solution. Therefore, no storage container for the ozone water solution is required, so the size and the weight of the apparatus can be contained. For this reason, the transport and the use of the apparatus are simplified.
• the ozone water solution is used to generate the treatment solution immediately after being produced and the ozone of the water solution is immediately converted into ROS. Therefore, only a small amount of ozone is turned back to diatomic oxygen O2, due to its instability, before being converted into ROS. This increases the overall ROS yield in the ROS generation process from oxygen.
• the water used to dissolve the ozone and to form the ozone water solution includes a predetermined amount of hydrogen peroxide, therefore the step of contacting and dissolving the ozone into the water takes place in the presence of hydrogen peroxide.
• the hydrogen peroxide amount is equivalent to a 35% hydrogen peroxide water solution amount set between 1/500 and 1/5000 of the amount of said water.
• the water used to make the ozone water solution contains a certain amount of dissolved salts.
• the dissolved salts consist of at least one pair of an anion and one cation selected from the group consisting of Sodium, Potassium, Calcium, Magnesium, Iron, Chloride, Sulphate, Bicarbonate, Fluoride, Nitrate, each present at a concentration set between 50 and 500 mg/litre.
• the container of the treatment solution generating device has an elongated shape and the first and second openings are arranged at opposite end portions of the container.
• the passage body or the container has a tubular shape of length set between 3 and 5 times the diameter.
• such incorporation of ROS water solution submillimetric particles into a gel includes the steps of: prearranging an amount of a gel in a gel-forming turbomixer, i.e., in an equipment commonly used to make a gel; maintaining the gel under agitation in the gel-forming turbomixer; supplying the treatment solution, as released by the nebulizer device, into the gel-forming turbomixer during the above step of agitation of the gel.
• the gel can be produced in situ, i.e. in the gel-forming turbomixer just before or even during the incorporation of the ROS water solution in the gel formed or being formed, by prearranging an amount of a gelling agent in the gel-forming turbomixer and by supplying a predetermined amount of water (8) to said gel-forming turbomixer (90), during the above step of agitation of the gel
• the apparatus comprises such a gel-forming turbomixer hydraulically connected to an output mouth of the nebulizer device so as to be supplied by the treatment solution as released thereby.
• the gelforming turbomixer can be associated with a gelling agent supply means and by a water supply means so as to prepare said gel within said gel-forming turbomixer, or to compensate for the viscosity change of a preformed gel due to the addition of water accompanying the ROS in the treatment solution.
• Fig. 1 is a flow diagram of an apparatus for making a treatment solution containing reactive oxygen species according to the present invention
• Fig. 2 diagrammatically shows a longitudinal cross section view of a treatment solution generator device in which the passage body is made of full fibres;
• Fig. 3 diagrammatically shows a longitudinal cross section view of a treatment solution generator device in which the passage body is made of hollow fibres;
• Fig. 4 is a detail of the fibres of passage body of Fig. 4, in a modification in which microporous fibres are used;
• Fig. 5 diagrammatically shows a longitudinal cross section view of a treatment solution generating device in which the passage body has a porous structure
• Fig. 6 diagrammatically shows a perspective view of a rolled porous membrane, e.g., for use in haemodialysis;
• Fig. 7 diagrammatically shows a longitudinal cross section view of a treatment solution generator device in which the passage body is made of the rolled porous membrane of Fig. 5;
• Fig. 8 diagrammatically shows a longitudinal cross section view of a treatment solution generating device in which the passage body has a granular structure and is formed from a loose mineral particulate material
• Fig. 9 is a diagram showing how the pressure of the ozone/ROS water solution changes along a path between the ozone water solution generator device and the nebulizer of Fig. 1 ;
• Fig. 10 is a flow diagram of an apparatus according to an embodiment of the present invention, in which the mixer device comprises a reservoir;
• Fig. 1 1 is a flow diagram of an apparatus according to a modification of the embodiment of Fig. 10, in which a hydrogen peroxide supply device is provided to supply H2O2 to the water-ozone mixer device;
• Fig. 12 is a flow diagram of an apparatus according to an embodiment of the present invention, in which mixer device comprises a mixing duct enclosing a static mixer;
• Fig. 13 is a flow diagram of an apparatus according to a modification of the embodiment of Fig. 11 , in which a hydrogen peroxide supply device is provided to supply H2O2 to the water-ozone mixer device;
• Fig. 14 is a flow diagram of an apparatus according to a modification of the embodiment of Fig. 10, wherein a compensation and/or recycle duct is provided between the treatment solution generator device according to one embodiment and the reservoir of the ozone water solution generator device;
• Fig. 15 is a flow diagram of an apparatus for making a treatment solution containing reactive oxygen species and for stabilizing the reactive oxygen species by incorporation of the solution into a gel.
• Apparatus 100 comprises an ozone water solution generator device 10, described more in detail hereinafter with reference to Figs. 2-8, and a treatment solution generator device 70 arranged in hydraulic connection with the ozone water solution generator device 10.
• Treatment solution generator device 70 is configured to turn an ozone water solution 5 obtained by ozone water solution generator device 10 into treatment solution 6 containing reactive oxygen species.
• a container 71 has a first opening 73 and a second opening 74, and encloses a passage body 72.
• First opening 73 is arranged in hydraulic connection with an outlet of ozone water solution generator device 10, so that ozone water solution 5 generated by ozone water solution generator device 10 can be supplied to first opening 73 of treatment solution generator device 70.
• a supply pump 60 can be provided to supply ozone water solution 5 to generating treatment solution generator device 70.
• passage body 72 includes a plurality of passageways 77 having a predetermined passage-section size, in which ozone water solution 5 is turned into treatment solution 6 while flowing therethrough, i.e., in which ozone is converted into ROS as ozone water solution 5 advances within passage body 72.
• passage-section size of passageways 77 is set between 0,001 pm and 0,2 pm, preferably between 0,005 pm and 0,015 pm, in order to allow and possibly ozone conversion to ROS, in particular to 02’ and O + ions, as described hereinafter.
• container 71 has an elongated shape extending along a longitudinal axis 71'.
• container 71 can have a cylindrical shape.
• first opening 73 i.e., the inlet opening of ozone water solution 5
• second opening 74 i.e. the outlet opening of treatment solution 6 are located at opposite end portions of elongated container 71 .
• passage body 72 comprises a bundle 75 of full fibres 76 arranged in the direction of longitudinal axis 71 ’ of container 71 .
• Full fibres 76 are packed together in such a way as to define, between one solid fibre 76 and the other, passageways 77 for ozone water solution 5 and for treatment solution 6 being formed.
• An empty space 73’ is advantageously provided between first opening 73 and fibre bundle 75 to obtain a uniform distribution of incoming ozone water solution 5 over the cross section of fibre bundle 75.
• passage body 72 comprises a bundle 75 of hollow fibres 78 also arranged in the direction of longitudinal axis 71 ’.
• Hollow fibres 78 define within themselves respective passageways 77 for ozone water solution 5 and for treatment solution 6 being formed.
• the passage-section size corresponds to the internal cross section of hollow fibres 78.
• empty space 73’ is preferably provided between first opening 73 and fibre bundle 75 to promote uniform distribution of ozone water solution 5 in passage body 72.
• Hollow fibres 78 are tightly packed to maximise the number of passageways 77 of passage body 72.
• fibre bundle 75 of hollow fibres 78 is mounted between two end plates, in the same manner as the tubes of a shell-and-tube heat exchanger.
• FIG. 4 shows a modification of the embodiment of Fig. 3, in which the wall of hollow fibres 78 has submicrometric porosities 77 that place the inner lumen of hollow fibres 78 into hydraulic communication with the outside of hollow fibres 78 themselves, within container 71 , similar to the shell-side of a shell-and- tube heat exchanger.
• passageways 77 through which water solution 5,6 containing ozone and the ROS being formed flows, can include or be the porosities 77 of the wall of hollow fibres 78.
• first and second openings 73,74 are preferably arranged such that ozone water solution 5 turning into treatment solution 6 flows from shell side 79 into the tube-side of bundle 75 through porosities 77, i.e, first opening 73 is made through a wall of the shell portion of container 71 , whereas second opening 74 is made through the wall of the bonnet portion of container 71 .
• hollow fibres 78 of passage body 72 can be of the same type used in a dialyzer.
• hollow fibres 78 of passage body 72 can be of the same type used to perform an ultrafiltration of a liquid flowing therethrough, i.e., through the porosities of the wall of hollow fibres 78, typically from outside to inside hollow fibres 78.
• Passage bodies 72 shown in Figs. 2 to 4 i.e., full fibres 76 and hollow fibres 78, can be made of various materials.
• polysulfone, cellulose triacetate and polyvinyl chloride are preferred, as well as polypropylene, polyethersulfone, well known to a person skilled in the art of ultrafiltration.
• passage body 72 is a porous compact body, not including a tube or tube bundle structure.
• passageways 77 for ozone water solution 5 being turned into ROS-containing treatment solution 6 are defined by a percolable open-cell lattice, and the passage-section size corresponds to the cell size of the lattice.
• porous compact passage body 72 can be obtained in a known manner by sintering metal or ceramic powders.
• passage body 72 with porous structure may be an open-cell sponge.
• Figures 6 and 7 relates to an embodiment in which passage body 72 is a porous body consisting of a rolled porous membrane 78’, folded about an axis 78” thereby forming a substantially cylindric structure suitable for insertion into container 71 having a cylinder shape.
• porous membrane 78’ of passage body 72 can be of the same type as used in a dialyzer.
• porous membrane 78’ of passage body 72 can be of the same type as used to perform an ultrafiltration of a liquid flowing therethrough, i.e., through porosities 77 of membrane 78’, typically towards axis 78”.
• Passage bodies 72 shown in Figs. 6 and 7, i.e., porous membrane 78’ can be made of various materials.
• polysulphone, cellulose triacetate, polylactic acid and polyvinyl chloride are preferred, as well known to a person skilled in the art of ultrafiltration.
• passage body 72 is formed of a loose mineral particulate material 72’ whose grain size is selected in such a way to form also in this case a percolable open-cell lattice in which the cells have a predetermined size, as provided by the method.
• loose mineral particulate material 72’ can be a sand of a controlled grain size, i.e. a screened sand appropriately to obtain the desired passage-section size.
• the loose mineral particulate material may be a mineral known in the technique as an ultrafiltration aid.
• a plurality of preferably serially arranged passage bodies 72 can be provided along the flowpath of ozone water solution 5 of the types described above.
• ozone water solution 5, or ROS-containing treatment solution 6, respectively can flow through duct portions 77’ (Fig. 4) that are provided in the passage body 72.
• Duct portions 77’ can have a section size set between 10 pm and 1 mm, preferably between 50 pm and 500 pm, more preferably between 100 pm and 300 pm.
• a nebulizer 80 Downstream of treatment solution generator device 70, in hydraulic connection with second opening 74, there is provided a nebulizer 80, preferably configured to split a liquid flow available at a predetermined second pressure P2 into submillimetric particles, more preferably micron-sized particles, and arranged then to release treatment solution 6 outside of the generating device 70, in such a particle form.
• Supply pump 60 is selected in such a way that ozone water solution
• a predetermined first pressure Pi preferably set between 7 and 15 bar g, in particular between 10 and 12 bar g.
• the water solution pressure profile along apparatus 100 is schematically shown in Fig. 9.
• passage body 72 is arranged to release treatment solution
• ozone water solution 5 can flow through passageways 77 of passage body 72, for example the inner lumen of hollow fibres 78 of Fig. 3 or the porosities 77 of the wall of hollow fibres 78 of Fig. 3, or the percolable lattice of a porous or granular body 72, as in Figs 5 to 8.
• Treatment solution 6 generated in passage body 72 then flows through nebulizer 80 and is available for sprinkling a biological system, or for further ROS stabilization, as described hereinafter.
• reactive oxygen species from the treatment solution can be deposited directly onto the biological system, with which they can interact before spontaneously decaying to molecular oxygen O2.
• an apparatus 101 for producing and administering a treatment solution 6 containing reactive oxygen species, in particular 02’ anions, from water 1 and an oxygen-containing gas 3, in particular air.
• a treatment solution 6 containing reactive oxygen species in particular 02’ anions
• air 3 taken from the environment as an oxygen-containing gas.
• the oxygen-containing gas may be a gas distinct from atmospheric air, for example substantially pure oxygen, or compressed air taken from a portable pressure vessel.
• Apparatus 101 is configured to at least in part transform the oxygen contained in air 3 into ozone, from which the superoxide anions of treatment solution 6 are then obtained, as described below.
• Apparatus 101 comprises a conventional ozone generator 40 configured to convert at least one portion of the oxygen contained in air 3 into ozone O3. Associated with the ozone generator 40 there is a fan 30 arranged to convey a air stream 3 taken from the environment, at a predetermined flow rate, through the generator 40. In the embodiment of Fig. 10, fan 30 is arranged upstream of the ozone generator 40, but in other embodiments it may be arranged downstream of it.
• the ozone generator 40 thus produces a gas 4 containing ozone in addition to nitrogen and any unconverted oxygen, and smaller quantities of other gases normally contained in the air.
• Apparatus 101 further comprises a mixer device 50 configured to bring an amount or a stream of water 1 into contact with ozone-containing gas 4, so as to dissolve the ozone into water 1 and obtain ozone water solution 5.
• mixer device 50 comprises a reservoir 51 for receiving a predetermined amount of water 1.
• mixer device 50 is associated with a water supply means 21 , for example, as shown in Fig. 10, a supply line 21 from a water supply network.
• water supply means 21 can comprise a hopper arranged to receive water 1 and to selectively put it into communication with reservoir 51 , so as to transfer water 1 into reservoir 51 by gravity.
• Apparatus 101 further comprises a supply line 22 of ozonecontaining gas stream 4, along which fan 30 and the ozone generator 40 are arranged as described above.
• Supply line 22 and reservoir 51 are preferably arranged to supply ozone-containing gas stream 4 below the level of the liquid 1 ,5 contained in reservoir 51 , corresponding to the amount of water 1 , so as to bring ozone-containing gas 4 into contact with water 1.
• reservoir 51 is provided with a submerged tube 52 in hydraulic connection with supply line 22 of ozone-containing gas 4.
• mixer device 50 comprises a conventional gas-to-liquid diffuser means for finely dispersing ozone-containing gas 4 into water 1 contained in reservoir 51.
• Such diffuser means can be arranged at the submerged end, i.e., at the outlet of submerged tube 52.
• Apparatus 101 further comprises a discharge duct 23 of ozone water solution 5, along which pump 60 is arranged, thus defining a suction portion 25 and a delivery portion 26 of discharge duct 23. Delivery portion 26 of discharge duct 23 is connected to treatment solution generator device 70.
• Fig. 1 1 shows an apparatus 102, according to an embodiment of the invention, which differs from apparatus 101 of Fig. 10 in that it comprises a hydrogen peroxide supply device 35 for supplying hydrogen peroxide H2O2 2 to reservoir 51 of mixer device 50.
• Hydrogen peroxide supply device 35 may comprise a feed line 36 and a pump 37, such as a metering pump, arranged to transfer a predetermined amount of hydrogen peroxide 2 from an hydrogen peroxide container 38.
• Hydrogen peroxide container 38 can be a container of hydrogen peroxide as purchased from a supplier, or a fixed tank 38 of apparatus 102.
• Supply means or devices 21 , 22, 35 of water 1 , ozone-containing gas 4 and hydrogen peroxide 2 can be equipped with respective mass or flow rate predetermination means fed to supply predetermined amounts of water, ozone and hydrogen peroxide to mixer device 50, in particular to reservoir 51 .
• predetermination means may be flow meters configured to emit electrical signals upon reaching a predetermined amount of the liquid to be fed to mixer device 50, in order to close a shut-off valve 24 of the water supply line 21 of water 1 or to stop the hydrogen peroxide supply pump 37.
• the predetermination means may comprise weighing devices or level indicators.
• the aforementioned predetermination means are of a conventional type and therefore easily implemented by a technician in the branch, hence they are not described in detail, nor are they shown in the drawings.
• Fig. 12 relates to an apparatus 103 according to a further embodiment of the invention, which differs from apparatus 101 of Fig. 10 in that mixer device 50 comprises, instead of the mixing tank 51 , a mixing duct 55, in this case a tubular element within which a conventional static mixer 56 is arranged.
• apparatus 103 comprises a water supply means 21 and an ozone-containing gas supply device 22.
• Water supply means 21 may comprise a feed tank 54, a supply pump 60 and, preferably, a water flow rate control valve 29 for setting the correct flow rate to mixing duct 55.
• Pump 60 and the regulating valve 29 are selected in such a way to supply water 1 to mixing duct 55 at the pressure required by static mixer 56.
• water 1 can be directly withdrawn from a distribution network in which water 1 is available at a pressure at least equal to the pressure required by static mixer 56, without requiring feed tank 54 and pump 60 to convey water 1 to mixing duct 55.
• FIG. 13 shows an apparatus 104 according to an embodiment of the invention, which differs from apparatus 103 of Fig. 12 in that it comprises hydrogen peroxide supply means 35 for supplying hydrogen peroxide 2 to the mixer tank 54 similarly to apparatus 102 of Fig. 1 1.
• the correct hydrogen peroxide/water proportion is advantageously set in feed tank 54.
• container 71 of treatment solution generator device 70 has first opening 73 hydraulically connected to outlet duct 23 of ozone water solution 5, while second opening 74 of the superoxide anion generator 70 is preferably directly connected to nebulizer 80.
• Fig. 14 shows an apparatus 105 which differs from apparatus 101 of Fig 10 in that container 71 of treatment solution generator device 70, in particular, a space 79 defined between the shell of container 71 and hollow fibres 78, is hydraulically connected with an opening of reservoir 51 via a compensation and recycling duct 57, in order to maintain the pressure within container below a predetermined safety value.
• an appropriately set safety valve can be provided on one wall of container.
• Fig. 15 diagrammatically shows an apparatus 106 according to a further embodiment of the invention, comprising such a gel-forming turbomixer 90 hydraulically connected to an output mouth 81 of nebulizer device 80 so as to be supplied by treatment solution 6 as released by nebulizer device 80.
• gelforming turbomixer 90 can be associated to a gelling agent 7 supply means 82 and to a water 8 further supply means 83 so as to prepare gel 9 within gel-forming turbomixer 90, or to compensate for the viscosity change of a preformed gel 9 due to the addition of the water accompanying the ROS in treatment solution 6.
• Tests were conducted under the following operating conditions: ozone water solution throughput: 30 litres; duration of the ozone water solution generation step (uptime of ozone generator 40): approx. 1 minute; feed rate to treatment solution generator 70: 20 litres/minute;

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• 2021
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