WO2016021465A1 - 流体流通器および光化学反応器 - Google Patents
流体流通器および光化学反応器 Download PDFInfo
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- WO2016021465A1 WO2016021465A1 PCT/JP2015/071520 JP2015071520W WO2016021465A1 WO 2016021465 A1 WO2016021465 A1 WO 2016021465A1 JP 2015071520 W JP2015071520 W JP 2015071520W WO 2016021465 A1 WO2016021465 A1 WO 2016021465A1
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- outer tube
- tube
- inner tube
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- photochemical reactor
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- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Definitions
- the present invention uses a fluid flow channel for use in continuous feed, product recovery, concentration and purification steps of a microchannel reactor, or a photochemical reactor, and uses a photocatalyst to process the fluid. It relates to a photochemical reactor.
- the scale-up of a photoreactor can be facilitated by arranging a plurality of glass tubes provided with porous glass therein in parallel. Furthermore, the processing capacity of the photoreactor can be easily increased by arranging a plurality of glass tubes provided with porous glass therein in series. Further, by using quartz glass as the glass material, the wavelength band of light used in the photoreactor can be widened.
- a flow channel structure including a flow channel substrate having a flow channel groove and a lid substrate that closes the flow channel groove is known as a prior art (see, for example, Patent Document 2).
- Photocatalyst fine particles are arranged on the wall surface of the flow path of the flow path structure. Thereby, it can suppress that a flow path is blocked.
- a microreactor including a substrate provided with a groove for forming a reaction channel and a top plate that closes the opening of the groove is known as a prior art (see, for example, Patent Document 3).
- a catalyst layer is formed in the reaction channel. Thereby, a catalytic reaction can be advanced with respect to the solution etc. which distribute
- the present invention has been made under such circumstances, and an object of the present invention is to provide a fluid circulation device and a photochemical reactor that have a large fluid flow rate, a low manufacturing cost, and easy maintenance.
- the present inventors have arranged an inner tube inside the outer tube, and formed a fluid flow path on the inner surface of the outer tube and the outer surface of the inner tube, so that the amount of fluid flow is large, the manufacturing cost is low, and maintenance is performed.
- the present inventors have found that a fluid flow device and a photochemical reactor that can be easily manufactured can be manufactured. That is, the present invention provides the following inventions [1] to [21].
- An outer tube having an outer surface and an inner surface, an inner tube having an outer surface and an inner surface, disposed inside the outer tube, and forming a fluid flow path on the inner surface and the outer surface of the outer tube, or an outer surface,
- the inner surface of the outer tube and a rod-shaped body that forms a fluid flow path on the outer surface, and between the inner surface of the outer tube and the outer surface of the inner tube or the rod-shaped body in the thickness direction of the outer tube Fluid distributor with a distance of 100 nm to 5 mm.
- the fluid distributor according to the above [1], wherein the distance between the inner surface of the outer tube and the outer surface of the inner tube or the rod-shaped body in the thickness direction of the outer tube is 1 ⁇ m to 1 mm.
- the ring further includes a magnet that forms an NS pair with the arranged magnet and is disposed inside the ring-shaped jig so as to face each other, and a rotating device that rotates the ring-shaped jig in the circumferential direction.
- the fluid flow passage according to any one of [1] to [4], wherein the inner tube rotates in the circumferential direction when the shaped jig is rotated in the circumferential direction.
- the fluid distributor according to any one of the above [1] to [5], wherein at least a part of the outer tube, the inner tube, or the rod-shaped body is made of a porous material.
- porous material is a porous ceramic material, a porous glass material, a porous metal material, or a porous resin material.
- Porous materials are polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinylidene chloride, polyvinyl chloride, Nafion (R), polyfluoroethylene propene copolymer, perfluoroalkoxyalkane, ethylene tetra Fluoroethylene copolymer, tetrafluoroethylene-perfluorodioxole copolymer, polyetherketone, polyimide, polybutylene naphthalate, polyethersulfone, aromatic polyester, polyamide, nylon, polyvinylpyrrolidone, polyallylamine, polystyrene and substituted products thereof , A copolymer containing at least one selected from the group consisting of polyethylene, polyvinyl alcohol
- the porous material includes a metal porous material, a metal fine powder sintered porous body, a metal coil filter, a porous structure in which an organic surface treatment agent is applied to the surface of these porous metal materials,
- the porous structure having a polymer thin film formed on the surface of the porous metal material, or a porous structure having an inorganic compound surface coating layer formed on the surface of the porous metal material. Fluid distributor.
- the cross-sectional shape of the inner surface of the outer tube in a direction perpendicular to the axial direction of the outer tube is a circle or an ellipse
- the cross-sectional shape of the outer surface of the inner tube in the direction perpendicular to the axial direction of the inner tube, or a rod-shaped body is a circle or an ellipse
- the cross-sectional shape of the inner surface of the outer tube in the direction perpendicular to the axial direction of the outer tube is a polygon, and the cross-sectional shape of the outer surface of the inner tube in the direction perpendicular to the axial direction of the inner tube, or The fluid distributor according to any one of the above [1] to [4], wherein a cross-sectional shape in a direction perpendicular to the axial direction is a polygon.
- the above [1] further comprising a spacer arranged on at least one surface on the inner surface of the outer tube and on the outer surface of the inner tube or the rod-like body, for narrowing the width of the flow path in the thickness direction of the outer tube.
- a photochemical reactor comprising the fluid distributor according to any one of [1] to [12] above and a photocatalyst disposed on at least one of the inner surface of the outer tube and the outer surface of the inner tube or rod-shaped body .
- the photochemical reactor according to [13] further including a light source that is disposed inside the inner tube and emits light that passes through the inner tube and excites the photocatalyst.
- the photochemical reactor according to [13] further including a light source that is disposed outside the outer tube and emits light that passes through the outer tube and excites the photocatalyst.
- the fluid circulation device according to any one of [1] to [12] described above and a light source outside the outer tube, and the outer tube can transmit light or a light source inside the inner tube
- FIG. 1 is a perspective view of a fluid distributor in one embodiment of the present invention.
- FIG. 2 is a perspective view of a modification of the fluid distributor in one embodiment of the present invention.
- FIG. 3 is a perspective view of a modification of the fluid distributor in one embodiment of the present invention.
- FIG. 4 is a perspective view of a modification of the fluid distributor in one embodiment of the present invention.
- FIG. 5 is a perspective view of a modification of the fluid distributor in one embodiment of the present invention.
- FIG. 6 is a cross-sectional view of a modification of the fluid distributor in one embodiment of the present invention.
- FIG. 7 is a cross-sectional view of a modification of the photochemical reactor in one embodiment of the present invention.
- the photochemical reactor in one embodiment of the present invention includes the fluid distributor and the photocatalyst in one embodiment of the present invention.
- the fluid circulation device 1 in one embodiment of the present invention has an outer tube 2 having an outer surface 21 and an inner surface 22, an outer surface 31 and an inner surface 32, and is disposed inside the outer tube 2. And an inner tube 3 that forms a solution flow path 4 on the inner surface 22 and the outer surface 31 of the outer tube 2.
- an inner tube 3 that forms a solution flow path 4 on the inner surface 22 and the outer surface 31 of the outer tube 2.
- the flow channel 4 having a small width in the thickness direction of the outer tube 2 can be formed. Manufacturing cost can be reduced. Furthermore, when removing the block
- the pressure loss increases as the flow path length increases.
- the fluid circulation device 1 since the solution is in contact with the side wall in addition to the top and bottom surfaces of the flow path, the pressure loss increases as the flow path length increases.
- the pressure loss is at least 1/2 that of a conventional microchannel reactor having the same flow path length.
- the contact with the upper surface (the inner surface 22 of the outer tube 2) or the bottom surface (the outer surface 31 of the inner tube 3) is good, and the light transmittance described below or the porous tube described in the later-described modification is used. When used, the gas permeability can be increased.
- the outer tube 2 is preferably a material that transmits light that excites the photocatalyst.
- the material of the outer tube 2 include glass such as quartz glass, silica glass, soda lime glass, borosilicate glass, and aluminosilicate glass, and polymethyl methacrylate, polycarbonate, cycloolefin polymer, and alicyclic acrylic resin.
- Fluorine resin Polyimide, epoxy resin, unsaturated polyester, vinyl ester resin, styrene polymer, polyethylene terephthalate, polyethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinylidene chloride, polyvinyl chloride, Nafion (R), polyfluoro Ethylene propene copolymer, perfluoroalkoxyalkane, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-perfluorodioxole copolymer, polyether keto Or polybutylene naphthalate, polyethersulfone, aromatic polyester, polyamide, nylon, polyvinylpyrrolidone, polyallylamine, polystyrene and substituted products thereof, polyethylene, polyvinyl alcohol, polypropylene and polycarbonate, or Examples thereof include resins such as copolymers containing a part of these.
- a more preferable material of the outer tube 2 is quartz glass.
- the inner tube 3 may not transmit light that excites the photocatalyst.
- the material of the inner tube 3 include glass, metal, resin, ceramics, wood, and composite materials thereof.
- the material of the inner tube 3 may be the same as the material of the outer tube 2.
- the material of the inner tube 3 is more preferably a resin.
- the inner tube 3 is preferably a material that transmits light that excites the photocatalyst.
- the material of the inner tube 3 include quartz glass, silica glass, soda lime glass, borosilicate glass, and aluminosilicate glass, and polymethyl methacrylate, polycarbonate, cycloolefin polymer, and alicyclic acrylic resin.
- Fluorine resin Polyimide, epoxy resin, unsaturated polyester, vinyl ester resin, styrene polymer, polyethylene terephthalate, polyethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinylidene chloride, polyvinyl chloride, Nafion (R), polyfluoro Ethylene propene copolymer, perfluoroalkoxyalkane, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-perfluorodioxole copolymer, polyether keto Or polybutylene naphthalate, polyethersulfone, aromatic polyester, polyamide, nylon, polyvinylpyrrolidone, polyallylamine, polystyrene and substituted products thereof, polyethylene, polyvinyl alcohol, polypropylene and polycarbonate, or Examples thereof include resins such as copolymers containing a part of these.
- a preferred material for the inner tube 3 is quartz glass because the wavelength band of the transmitted light is wide.
- the outer tube 2 may not transmit light that excites the photocatalyst.
- the material of the outer tube 2 include glass, metal, resin, ceramics, and wood.
- the material of the outer tube 2 may be the same as the material of the inner tube 3.
- the material of the outer tube 2 is more preferably a resin.
- the distance between the inner surface 22 of the outer tube 2 and the outer surface 31 of the inner tube 3 in the thickness direction of the outer tube depends on the application of the fluid distributor, the application of the photochemical reactor, the wavelength of the selected light, and the light transmission of the reaction liquid. Although it varies depending on the nature and the like, it is 100 nm to 5 mm, preferably 1 ⁇ m to 1 mm, more preferably 10 ⁇ m to 0.5 mm. If the distance between the inner surface 22 of the outer tube 2 and the outer surface 31 of the inner tube 3 in the thickness direction of the outer tube is smaller than 100 nm, it may be difficult for the solution to flow through the flow path 4.
- the light for exciting the photocatalyst does not pass through the solution flowing through the flow path 4.
- the photocatalyst disposed on at least one of the inner surface 22 of the outer tube 2 and the outer surface 31 of the inner tube 3 described later is excited by the light. It can be difficult. According to the fluid distributor in one embodiment of the present invention, such a flow path 4 having a small width in the thickness direction of the outer tube 2 can be easily formed.
- a fine concavo-convex of 10 to 100 ⁇ m or a porous glass layer having a thickness of 10 to 100 ⁇ m may be formed on the inner surface 22 of the outer tube 2 or the outer surface 31 of the inner tube 3. Since these irregularities or the porous glass layer are cut off from the opposing surface when the inner tube 3 is taken out from the inside of the outer tube 2, removal of the obstruction that blocks the channel 4 or contamination of the channel surface Cleaning for removing the substance can be easily performed. Therefore, the fluid circulation device 1 in one embodiment of the present invention has both novelty and inventive step as compared with the photoreactor described in Patent Document 1 described above.
- the cross-sectional shape of the inner surface 22 of the outer tube 2 in the direction perpendicular to the axial direction of the outer tube 2 is preferably a circle, and the cross-sectional shape of the outer surface 31 of the inner tube 3 in the direction perpendicular to the axial direction of the inner tube 3 is Preferably it is a circle.
- the flow of the solution flowing in the axial direction of the outer tube 2 and the inner tube 3 through the flow path 4 formed by the inner surface 22 of the outer tube 2 and the outer surface 31 of the inner tube 3 can be made uniform.
- the cross-sectional shape of the inner surface of the outer tube 2 in the direction perpendicular to the axial direction of the outer tube 2 is an ellipse
- the cross-sectional shape of the outer surface of the inner tube in the direction perpendicular to the axial direction of the inner tube 3 is an ellipse. May be.
- the photocatalyst is disposed on at least one of the inner surface 22 of the outer tube 2 and the outer surface 31 of the inner tube 3. Thereby, the solution which flows through the flow path 4 formed by the inner surface 22 of the outer tube 2 and the outer surface 31 of the inner tube 3 can be treated with the photocatalyst.
- the solution is water
- the water can be purified.
- Examples of the photocatalyst disposed on at least one of the inner surface 22 of the outer tube 2 and the outer surface 31 of the inner tube 3 include a titanium oxide photocatalyst and a tungsten oxide photocatalyst.
- Examples of the titanium oxide photocatalyst include TiO 2 , TiO (N) 2 Pt / TiO 2 , copper compound modified titanium oxide, iron compound modified titanium oxide, metal modified titanium oxide, copper compound modified tungsten oxide, metal modification. Examples include tungsten oxide and tantalum oxynitride.
- Tungsten oxide photocatalyst is, for example, a Pt / WO 3.
- the photocatalyst may be disposed on at least one of the inner surface 22 of the outer tube 2 and the outer surface 31 of the inner tube 3 by being supported on at least one of the inner surface 22 of the outer tube 2 and the outer surface 31 of the inner tube 3. Good. Further, by forming a photocatalyst layer on at least one surface of the inner surface 22 of the outer tube 2 and the outer surface 31 of the inner tube 3, at least one surface of the inner surface 22 of the outer tube 2 and the outer surface 31 of the inner tube 3 is formed. You may arrange. Specifically, the photocatalyst can be disposed on the inner surface 22 of the outer tube 2 as follows, for example.
- the outer tube 2 is filled with a colloidal dispersion fluid of titanium oxide and allowed to stand for a while to allow the colloidal particles of titanium oxide to adhere to the inner surface 22 of the outer tube 2. Then, the colloidal dispersion solution of titanium oxide is discharged from the outer tube 2. Next, after drying the outer tube 2 having colloidal particles of titanium oxide adhered to the inner surface 22, the outer tube 2 is heated to form a titanium oxide layer on the inner surface 22 of the outer tube 2. In this way, the photocatalyst can be disposed on the inner surface 22 of the outer tube 2.
- the photocatalyst is preferably formed from colloidal particles.
- the colloidal particle-like titanium oxide is preferably titanium oxide containing brookite type titanium oxide as a main component. Brookite-type titanium oxide is known to be a particle having good water dispersibility, and is advantageous when processing for disposing titanium oxide on the surface of the photochemical reactor in one embodiment of the present invention. . Whether the colloidal particle titanium oxide is brookite-type titanium oxide should be confirmed by the presence of a peak attributed to the brookite type by pulverizing the colloidal particles after drying and performing X-ray diffraction measurement. Can be determined.
- brookite-type titanium oxide is the main component in the titanium oxide of the produced colloidal particles.
- a known method such as Rietveld analysis, for example, the composition of brookite-type titanium oxide: anatase-type titanium oxide: rutile-type titanium oxide This can be determined by calculating the ratio. If the proportion of brookite-type titanium oxide calculated from the composition ratio of titanium oxide is 50% or more, it can be said that the titanium oxide is titanium oxide mainly composed of brookite-type titanium oxide.
- the titanium oxide is preferably manufactured by a vapor phase method. Thereby, the titanium oxide particle which is very fine and has high crystallinity can be obtained.
- titanium oxide can be synthesized by heating a titanium chloride or oxychloride vapor to 500 ° C. or higher (preferably 800 ° C. or higher) and oxidizing it in oxygen or water vapor. Since titanium oxide obtained by such a vapor phase method is instantaneously synthesized in a high temperature atmosphere, it is fine but has high crystallinity and few lattice defects. For this reason, it can be said that the titanium oxide obtained by the vapor phase method is a suitable material as a photocatalyst used for the photochemical reactor of one embodiment of the present invention.
- a light source for exciting the photocatalyst for example, a low-pressure mercury lamp, black light, LED (light emitting diode), or the like is used.
- sunlight may be used as a light source, and sunlight may be used as a light source in combination with a light source such as a low-pressure mercury lamp, a black light, and an LED (light emitting diode).
- a cut-off filter, a bandpass filter, a fluid filter, a monochromator, and the like may be used.
- the photochemical reactor in one embodiment of the present invention is preferably used for water purification.
- various environmental hormones, dioxins, trihalomethanes, bacteria, and other harmful substances in water flowing through the flow path 4 are decomposed or inactivated by the photocatalytic reaction of the photocatalyst.
- the fluid distributor in one embodiment of the present invention and the photochemical reactor in one embodiment of the present invention can be modified as follows.
- At least a part of the outer tube or the inner tube may be made of a porous material.
- the gas required for the photocatalytic reaction by the photocatalyst is supplied from the portion made of the porous material of the outer tube or the inner tube, or the gas generated by the photocatalytic reaction by the photocatalyst is recovered from the flow path.
- the porous material is not particularly limited as long as it is a porous material that can separate liquid and gas. Examples of the porous material include a porous ceramic material, a porous glass material, a porous metal material, and a porous resin material.
- a preferred porous material is a porous resin material.
- Preferred porous resin materials include, for example, polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinylidene chloride, polyvinyl chloride, Nafion (R), polyfluoroethylene propene copolymer, perfluoroalkoxyalkane, ethylene Tetrafluoroethylene copolymer, tetrafluoroethylene-perfluorodioxole copolymer, polyetherketone, polyimide, polybutylene naphthalate, polyethersulfone, aromatic polyester, polyamide, nylon, polyvinylpyrrolidone, polyallylamine, polystyrene and their substitution Or at least one selected from the group consisting of polyethylene, polyvinyl alcohol, polypropylene and polycarbonate A copolymer containing a part.
- a more preferred porous resin material is polytetrafluoroethylene.
- the gas supplied to the solution through the porous material include oxygen, carbon dioxide, nitrogen, and argon.
- the average pore diameter, pore diameter distribution, and porosity of the porous material are not particularly limited as long as the average pore diameter, pore diameter distribution, and porosity that can separate a gas and a liquid are sufficient.
- the porous material includes a metal porous material, a metal fine powder sintered porous body, a metal coil filter, a porous structure in which an organic surface treatment agent is applied to the surface of these porous metal materials, It may be a porous structure in which a polymer thin film is formed on the surface of a porous metal material, or a porous structure in which a surface coating layer of an inorganic compound is formed on the surface of these porous metal materials.
- the outer tube When at least a part of the outer tube is made of a porous material, supply nitrogen, oxygen gas, carbon dioxide gas, etc. contained in the environment of the fluid circulation device to the solution flowing through the flow path through the porous material of the outer tube. Can do. Further, if a tube surrounding the outer tube is further installed outside the outer tube, the gas is circulated through the flow path formed by the gap between the tube and the outer tube, so that the space between the outer tube and the inner tube is reduced. The gas can be supplied to the solution flowing through the flow path. Further, by making the flow path formed by the gap between the pipe surrounding the outer pipe and the outer pipe negative pressure, the gas generated from the solution flowing through the flow path between the outer pipe and the inner pipe is changed to the outer pipe.
- This gas can include vapors of evaporated solvent, which allows for concentration of the solution.
- the structure of the tube surrounding the outer tube, the outer tube, and the inner tube makes it possible to reduce the concentration of the solution particularly when the solution or gas flowing through the flow path between the outer tube and the inner tube is reacted under chemical equilibrium conditions. It is possible to appropriately control the total elapsed time of the reaction, and the processing efficiency of the solution can be increased. Furthermore, by reducing the pressure outside the outer tube, it is possible to partially distill off the solvent from the solution flowing through the flow path, and thus the solution flowing through the flow path can be concentrated.
- the photocatalytic reaction of the photocatalyst can be controlled more finely by independently controlling the flow rate of the solution, the flow rate of the gas, and the amount of light irradiation.
- the outer tube when light is irradiated from the inside of the inner tube of the fluid circulation device to excite the photocatalyst of the photochemical reactor, the outer tube may not transmit light that excites the photocatalyst.
- at least a part of the outer tube may be a porous material.
- the inner tube when light is irradiated from the outside of the outer tube of the fluid circulation device to excite the photocatalyst of the photochemical reactor, the inner tube may not transmit light that excites the photocatalyst.
- at least a part of the inner tube may be a porous material.
- gas can be supplied to the solution or the gas generated from the solution can be recovered through the inner tube.
- the inner tube since the inner tube itself forms a flow path for supplying or recovering the gas, a flow for supplying or recovering the gas is used as in the case where at least a part of the outer tube is a porous material.
- another pipe such as a pipe surrounding the outer pipe may not be installed.
- the cross-sectional shape of the inner surface 21 of the outer tube 2 in the direction perpendicular to the axial direction of the outer tube 2 in the fluid distributor 1 described above is a circle or an ellipse.
- the cross-sectional shape of the outer surface 31 of the tube 3 was a circle or an ellipse.
- the cross-sectional shape of the inner surface of the outer tube in the direction perpendicular to the axial direction of the outer tube in the fluid distributor 1 is a polygon
- the cross-sectional shape of the outer surface of the inner tube in the direction perpendicular to the axial direction of the inner tube is It may be a polygon.
- the cross-sectional shape of the inner surface 22A of the outer tube 2A in the direction perpendicular to the axial direction of the outer tube 2A is a quadrangle, and is perpendicular to the axial direction of the inner tube 3A.
- the cross-sectional shape of the outer surface 31A of the inner tube 3A in the direction may be a quadrangle.
- reference numeral 21A indicates the outer surface of the outer tube 2A
- reference numeral 32A indicates the inner surface of the inner tube 3A.
- reference numeral 4A denotes a flow path formed by the inner surface 22A of the outer tube 2A and the outer surface 31A of the inner tube 3A.
- the shape may not be the same.
- the cross-sectional shape of the inner surface 22B of the outer tube 2B in a direction perpendicular to the axial direction of the outer tube 2B is a circle, and is perpendicular to the axial direction of the inner tube 3B.
- the cross-sectional shape of the outer surface 31B of the inner tube 3B in the direction may be an ellipse. In FIG.
- reference numeral 21B indicates the outer surface of the outer tube 2B
- reference numeral 32B indicates the inner surface of the inner tube 3B
- reference numeral 4B indicates a flow path formed by the inner surface 22B of the outer tube 2B and the outer surface 31B of the inner tube 3B.
- the cross-sectional shape of the inner surface 22C of the outer tube 2C in the direction perpendicular to the axial direction of the outer tube 2C is a circle, and is perpendicular to the axial direction of the inner tube 3C.
- the cross-sectional shape of the outer surface 31C of the inner tube 3C in the direction may be a hexagon.
- reference numeral 21C indicates the outer surface of the outer tube 2C
- reference numeral 32C indicates the inner surface of the inner tube 3C.
- reference numeral 4C denotes a flow path formed by the inner surface 22C of the outer tube 2C and the outer surface 31C of the inner tube 3C.
- the cross-sectional shape of the inner surface 22D of the outer tube 2D in the direction perpendicular to the axial direction of the outer tube 2D is an octagon, and the axial direction of the inner tube 3D
- the cross-sectional shape of the outer surface 31D of the inner tube 3D in the vertical direction may be a quadrangle.
- reference numeral 21D indicates the outer surface of the outer tube 2D
- reference numeral 32D indicates the inner surface of the inner tube 3D
- reference numeral 4D indicates a flow path formed by the inner surface 22D of the outer tube 2D and the outer surface 31D of the inner tube 3D.
- the fluid distributor is disposed on at least one surface on the inner surface of the outer tube and the outer surface of the inner tube, and includes a spacer for narrowing the width of the flow path in the thickness direction of the outer tube. Further, it may be included. Thereby, finer control of the width
- the spacer 5 is disposed on the outer surface 31E of the inner tube 3E, and the flow path 4E formed by the inner surface 22E of the outer tube 2E and the outer surface 31E of the inner tube 3E.
- the width of the outer tube 2E in the thickness direction 41E may be narrowed.
- a resin film, a woven fabric, a non-woven fabric, or the like can be used as the spacer.
- the fluid circulation device according to the embodiment of the present invention and the modified examples 1 to 4 of the fluid circulation device are used in the photochemical reactor, but the fluid circulation device according to the embodiment of the present invention and the modification of the fluid circulation device are used.
- the uses of Examples 1 to 3 are not limited to photochemical reactors.
- the fluid circulation system according to the embodiment of the present invention and the fluid circulation examples 1 to 3 are used for continuous raw material supply, product recovery, concentration, and purification processes of a microchannel reactor. Can be used as a container.
- the outer tube or the inner tube is made of a porous material
- a hydrophilic and / or ion-exchangeable porous membrane of a fluorine-based polymer material as the porous material, an ionic substance It is possible to control the concentration, supply, recovery and separation of hydrophilic raw materials and products.
- the fluid component modified example 1 of the embodiment of the present invention can be used to carry out the vacuum concentration step of the solvent component to recover the concentrated product solution.
- a rod-shaped body may be disposed instead of the inner pipe.
- the flow path can be formed by the inner surface of the outer tube and the outer surface of the rod-shaped body.
- the rod-shaped body include a cylinder and a prism.
- the material of the rod-shaped body for example, the same material as that of the inner tube 3 described above when irradiating light from the outside of the outer tube 2 of the fluid circulation device 1 to excite the photocatalyst of the photochemical reactor is used. May be used.
- at least a part of the rod-shaped body may be made of a porous material.
- the gas required for the photocatalytic reaction by a photocatalyst can be supplied, or the gas produced
- phase of the substance flowing in the flow path of the fluid flow path has been described by taking the liquid as a solution as an example.
- the phase of the substance flowing in the flow path of the fluid flow path is not limited to the liquid as long as it is a fluid.
- gas may flow through the flow path of the fluid flow path.
- the inner tube may be rotated in the circumferential direction.
- a catalyst is applied to the outer surface of the inner tube, this can promote contact between the photocatalyst and the fluid.
- the inner tube can be rotated as follows. A magnet is placed inside the inner tube and fixed to the inner tube.
- a ring-shaped jig is arranged outside the outer tube so that the center coincides with the central axis of the outer tube.
- a magnet having an opposite magnetic pole is arranged inside the ring-shaped jig.
- the magnet of the ring-shaped jig is arranged so as to form an NS pair with the magnet arranged inside the inner tube and to face each other.
- the magnet installed in the inner tube is also rotated by the magnetic force of the magnet provided in the ring-shaped jig. Since the magnet installed inside the inner tube is fixed to the inner tube, the inner tube also rotates together. Thereby, an inner pipe can be rotated without contact.
- the magnet is preferably a magnet having a strong magnetic force, for example, a rare earth magnet.
- the rotational force of the inner tube that can be applied by the rotation of the ring-shaped jig is changed by the magnetic force between the magnet provided in the ring-shaped jig and the magnet installed in the inner tube. For this reason, you may make it change the number of the magnets installed in the inside of an inner tube and / or the magnet provided in the ring-shaped jig
- the rotation direction of the inner tube may be periodically reversed.
- the outer tube may be rotated in the circumferential direction.
- the rotation direction of the outer pipe may be periodically reversed.
- both the outer tube and the inner tube may be rotated in the circumferential direction.
- the rotation direction of the outer tube is preferably opposite to the rotation direction of the inner tube.
- the photochemical reactor according to an embodiment of the present invention may further include a light source that is disposed inside the inner tube and emits light that passes through the inner tube and excites the photocatalyst.
- the light source 6 may be arranged inside the inner tube 3F.
- the light source 6 is not limited as long as it emits light that passes through the inner tube 3F and excites the photocatalyst.
- the light source 6 is a low-pressure mercury lamp, black light, or LED (light emitting diode).
- symbol 2F shows an outer tube
- the photocatalyst is disposed on at least one of the inner surface of the outer tube and the outer surface of the inner tube.
- a photocatalyst need not be arranged in the photochemical reactor.
- the photochemical reactor in this case is, for example, a photochemical reactor that has a fluid distributor in one embodiment of the present invention and a light source outside the outer tube, and the outer tube can transmit light, or the present invention.
- Modification 2 of the photochemical reactor includes a fluid circulation device according to an embodiment of the present invention, a light source outside the outer tube, and a light source inside the inner tube, and the outer tube and the inner tube emit light. It may be a photochemical reactor capable of transmitting.
- the photochemical reactor in which the liquid flows in the flow path of the fluid flow passage has been described.
- the fluid flowing in the fluid flow path of the photochemical reactor is not limited to the liquid as long as it is a fluid.
- gas may flow through the flow path of the fluid flow path of the photochemical reactor.
- the photochemical reactor can decompose nitrogen oxides, VOCs (volatile organic compounds), odor components and the like contained in the gas.
- this coating solution is filled in a quartz glass tube (model number: # 4, manufactured by Fujiwara Seisakusho Co., Ltd.) having an outer diameter of 5.9 mm, an inner diameter of 4.5 mm, and a length of 650 mm, and the excess solution is discharged. Thereafter, air was blown in a blower to dry, followed by baking at 450 ° C. for 2 hours to form a coating layer of brookite-type titanium oxide nanoparticles on the inner surface of the outer tube.
- the coating strength of the titanium oxide nanoparticle thin film formed on the surface of the flat Pyrex (registered trademark) substrate by the same procedure is 6H, and the photocatalyst layer has sufficient strength. I confirmed that
- the quartz glass tube having a coating layer of brookite-type titanium oxide nanoparticles formed on the inner surface is used as an outer tube, and a quartz glass tube having an outer diameter of 3.9 mm, an inner diameter of 2.5 mm and a length of 650 mm (Fujiwara Corporation) Glass structures in which both ends of Seisakusho, model number: # 2) were sealed were placed, and joints made of fluororesin were attached to both ends.
- 1 / 16-inch Teflon (registered trademark) piping is connected to each joint, one Teflon (registered trademark) piping is connected to the feed pump, and the other Teflon (registered trademark) piping is used to collect the product solution.
- Each was connected to a container.
- the average distance between the inner surface of the outer tube and the outer surface of the inner tube of this fluid distributor is about 500 ⁇ m, and the total volume of the flow path formed by the inner surface of the outer tube and the outer surface of the inner tube is 3.
- the area of the light receiving window of the outer tube that receives light from the light source was 82 cm 2 , and the light receiving window area / flow channel volume ratio was 2290 m ⁇ 1 .
- the area of the light receiving window of the outer tube was larger than that of the microchannel reactor.
- the light receiving part of the existing microchannel reactor receives light from one side of the flow channel sealed in the glass plate, but the light incident on the glass part between the flow channels is transmitted as it is.
- all the light incident from the surface of the outer tube is irradiated to the container flowing through the channel, so that at least the light receiving area per unit structure is doubled.
- the light receiving area of the photochemical reactor is small because the thickness of the Teflon (registered trademark) tube is small. About twice as much.
- a photochemical reactor of Comparative Example 1 was produced in the same manner as the photochemical reactor of Example 1 except that the titanium oxide nanoparticle coating layer was not formed on the inner surface of the outer tube.
- a photochemical reactor of Comparative Example 2 was produced in the same manner as the photochemical reactor of Example 1 except that the inner tube was not provided.
- the photochemical reactor was evaluated by purifying water using the photochemical reactor produced as described above.
- Water that is subject to purification includes 4-chlorophenol, a typical water-soluble pollutant (water quality standards for water supply and standards (51 items) of the Ministry of Health, Labor and Welfare). .005 mg / L or less) was added.
- As a light source for exciting the photocatalyst six 20 W black lamps (manufactured by Toshiba Corporation, model number: FL20S BLB) were used. Six black lamps were arranged so as to surround the glass tube and to be parallel to the glass tube. After turning on the six black lamps, water having a 4-chlorophenol concentration of 100 ⁇ M was circulated through the flow path of the photochemical reactor. The water was treated using a photochemical reactor with the flow rate of water flowing through the channel changed to 10 mL / min, 5 mL / min and 1 mL / min.
- the water treated by the photochemical reactor is collected, and the concentration of 4-chlorophenol is measured using a high-performance liquid chromatograph (manufactured by JASCO Corporation, model number: 875-UV). The conversion of was investigated. Note that 4-chlorophenol is converted into carbon dioxide when completely decomposed, but it is expected that phenol, catechol, hydroquinone, and the like are generated as intermediates while 4-chlorophenol is decomposed into carbon dioxide. Some amounts of phenol, catechol and hydroquinone were detected from the water treated by the photochemical reactor. From this, it is presumed that 4-chlorophenol was decomposed stepwise into carbon dioxide through a dechlorination process by a photocatalytic reaction.
- the conversion rate of 4-chlorophenol in the photochemical reactor of Comparative Example 2 in which no inner pipe was provided was 18% when the flow rate of water was 1 mL / min, which is the longest residence time. .
- the volume of the photochemical reactor of Comparative Example 2 was 10.3 mL, and the time that water stayed in the flow path was 2.8 times that of the photoreactor having the inner tube. Since the time during which water stays in the photoreactor corresponds to the time during which the water is irradiated with light, the amount of light received by the photochemical reactor of Comparative Example 2 is 2.8 times. Comparing the reaction efficiency per unit amount of light received, it was found that the reaction efficiency is increased about 5 times by forming the flow path by providing the inner tube inside the outer tube.
- the conversion rate of 4-chlorophenol in the photochemical reactor of Example 1 is such that when water having a 4-chlorophenol concentration of 1 mM is circulated through the flow path of the photochemical reactor at a flow rate of 1 mL / min, 7%. This is because the decomposition amount of 4-chlorophenol is about twice that of the case where water having a 4-chlorophenol concentration of 100 ⁇ M is circulated through the flow path of the photochemical reactor at a flow rate of 1 mL / min. It corresponds to the amount.
- a quartz glass tube having an outer diameter of 6.0 mm, an inner diameter of 4.4 mm and a length of 650 mm (manufactured by Fujiwara Manufacturing Co., Ltd., model number: # 4) has a transparent quartz glass tube having an outer diameter of 3.8 mm and a length of 650 mm (( Structures in which both ends of Sansho Co., Ltd., model number: IQ-2) were sealed were placed, and joints made of fluororesin were attached to both ends.
- This reactor is not provided with a photocatalyst layer because photoreactive molecules in the solution are directly photoexcited and activated.
- Teflon (registered trademark) piping 1 / 16-inch Teflon (registered trademark) piping is connected to each joint, and one Teflon (registered trademark) piping is connected to a syringe pump (Fusion 100 type, manufactured by Isis Co., Ltd.) and a gas tight syringe (SGE, The other Teflon (registered trademark) pipes were connected to the product solution collection containers.
- the distance between the inner surface of the outer tube of this fluid distributor and the outer surface of the glass rod is about 300 ⁇ m on average, and the total volume of the flow path formed by the inner surface of the outer tube and the outer surface of the glass rod is measured by 2.
- the area of the light receiving window of the outer tube that receives light from the light source is 109 cm 2 as an actual measurement value of the region irradiated by the lamp, and the light receiving window area / flow channel volume ratio is 4950 m ⁇ 1. It was.
- the area of the light receiving window of the outer tube was larger than that of the microchannel reactor.
- a photochemical reactor of Comparative Example 3 was fabricated in the same manner as the photochemical reactor fabrication method of Example 2 except that a structure in which both ends of the transparent quartz glass tube were sealed was not provided.
- the reactor volume of this reactor is 8.8 mL, and the area of the light receiving window of the outer tube that receives light from the light source is 109 cm 2 as an actual measurement value of the region irradiated with the lamp, and the light receiving window area
- the flow channel volume ratio was 1240 m ⁇ 1 , which was reduced to about 1 ⁇ 4 compared with the reactor provided with the glass rod.
- Reactivity activity evaluation 2 The photochemical reactor was evaluated using a 1 M isophorone-methanol solution using the photochemical reactor prepared as described above.
- a 1M isophorone-methanol solution was prepared by adding isophorone (manufactured by Wako Pure Chemical Industries, Ltd., model number: 095-01796) to methanol (manufactured by Wako Pure Chemical Industries, Ltd., model: 136-01837).
- Six 20 W germicidal lamps (manufactured by Toshiba Corporation, model number: GL20F) were used as light sources for exciting the photocatalyst. The six germicidal lamps were arranged so as to surround the glass tube and to be parallel to the glass tube.
- FIG. 1M isophorone-methanol solution was circulated through the flow path of the photochemical reactor of Example 2 at a flow rate of 0.5 cm 3 / min. Under these conditions, the flow rate was 13 cm / min, and the residence time of the 1 M isophorone-methanol solution in the photochemical reactor of Example 2 was 4.4 minutes.
- an inner tube (a glass tube having an outer diameter of 14.0 mm) having both ends fused and sealed was inserted into the outer tube. Since the difference between the inner diameter of the outer tube and the outer diameter of the inner tube is 500 ⁇ m, the gap formed between the inner surface of the outer tube and the outer surface of the inner tube is 250 ⁇ m.
- a ring-shaped Teflon (registered trademark) jig was disposed outside the outer tube so that the center axis of the outer tube substantially coincided with the center.
- Teflon (registered trademark) jig On the inner wall of the ring-shaped Teflon (registered trademark) jig, two rare earth magnets are arranged so as to form an NS pair with the rare earth magnet bonded to the inside of the inner tube and to face each other. .
- Teflon (registered trademark) jig is rotated using a motor, the inner tube rotates without contact.
- a 1/16 inch Teflon (registered trademark) pipe is connected to the lower and upper parts of the outer tube, and a 20 W black lamp (manufactured by Hitachi, Ltd., model number: FL20S BL-B) is attached to both sides of the outer tube.
- the photochemical reactor of Example 3 was produced by arranging them one by one. The distance between the lamp surface and the outer tube surface was 22 mm.
- the conversion rate when the inner tube was rotated at a rotation speed of 27 rotations / minute was 70%, and the conversion rate when the inner tube was rotated at a rotation speed of 80 rotations / minute was 69%. . From this, it was found that the conversion rate can be increased by rotating the inner tube, and the effect is almost saturated at the rotation speed of the reactor of 27 rotations / minute. This is presumed to be because the stirring of the solution flowing through the fluid flow passage was promoted by the rotation of the inner tube.
- the fluid distributor according to the present invention can be widely used as a fluid distributor through which a thin fluid layer flows.
- the fluid circulation device according to the present invention can be used for a micro-channel reactor, a photochemical reactor, and the like that are significantly scaled up.
- the photochemical reactor of the present invention can be used for fluid treatment devices such as gas purification devices, drinking water purification devices, and high-concentration sewage treatment device devices.
Abstract
Description
[1]外面および内面を有する外管と、外面および内面を有し、外管の内側に配置され、外管の内面および外面で流体の流路を形成する内管、または外面を有し、外管の内側に配置され、外管の内面および外面で流体の流路を形成する棒状体とを含み、外管の肉厚方向における外管の内面と内管または棒状体の外面との間の距離が100nm~5mmである流体流通器。
[2]外管の肉厚方向における外管の内面と内管または棒状体の外面との間の距離が1μm~1mmである上記[1]に記載の流体流通器。
[3]外管または内管もしくは棒状体が円周方向に回転するか、または、外管および内管もしくは棒状体の両方が円周方向に、および相互に反対方向に回転する上記[1]または[2]に記載の流体流通路。
[4]外管または内管もしくは棒状体の回転方向が周期的に反転する上記[3]に記載の流体流通路。
[5]中心が外管の中心軸と一致するように外管の外側に配置されたリング状治具と、内管と固定され、内管の内部に配置され磁石と、内管の内部に配置された磁石とN-S対を形成し、かつ対向するようにリング状治具の内側に配置された磁石と、リング状治具を円周方向に回転させる回転装置とをさらに含み、リング状治具を円周方向に回転させると、内管が円周方向に回転する上記[1]~[4]のいずれかに記載の流体流通路。
[6]外管または内管もしくは棒状体の少なくとも一部が多孔質材料で構成される上記[1]~[5]のいずれかに記載の流体流通器。
[7]多孔質材料は、多孔質セラミック材料、多孔質ガラス材料、多孔質金属材料または多孔質樹脂材料である上記[6]に記載の流体流通器。
[8]多孔質材料は、ポリテトラフルオロエチレン、ポリクロロトリフルオロエチレン、ポリフッ化ビニリデン、ポリ塩化ビニリデン、ポリ塩化ビニル、ナフィオン(R)、ポリフルオロエチレンプロペンコポリマー、パーフルオロアルコキシアルカン、エチレン・テトラフルオロエチレンコポリマー、テトラフルオロエチレン-パーフルオロジオキソールコポリマー、ポリエーテルケトン、ポリイミド、ポリブチレンナフタレート、ポリエーテルサルフォン、芳香族ポリエステル、ポリアミド、ナイロン、ポリビニルピロリドン、ポリアリルアミン、ポリスチレンおよびその置換体、ポリエチレン、ポリビニルアルコール、ポリプロピレンおよびポリカーボネートからなる群から選択される少なくとも一種またはこれらの一部を含む共重合体である多孔性樹脂材料からなる上記[7]に記載の流体流通器。
[9]多孔質材料は、金属製多孔質材料、金属微粉末焼結多孔質体、金属コイルフィルタ、これらの多孔質金属材料の表面に有機表面処理剤を塗布した多孔質構造体、これらの多孔質金属材料の表面に高分子薄膜を形成した多孔質構造体、またはこれらの多孔質金属材料の表面に無機化合物の表面被覆層を形成した多孔質構造体である上記[7]に記載の流体流通器。
[10]外管の軸方向に対して垂直方向における外管の内面の断面形状が円または楕円であり、内管の軸方向に対して垂直方向における内管の外面の断面形状、または棒状体の軸方向に対して垂直方向における断面形状が円または楕円である上記[1]~[4]のいずれかに記載の流体流通器。
[11]外管の軸方向に対して垂直方向における外管の内面の断面形状が多角形であり、内管の軸方向に対して垂直方向における内管の外面の断面形状、または棒状体の軸方向に対して垂直方向における断面形状が多角形である上記[1]~[4]のいずれかに記載の流体流通器。
[12]外管の内面上および内管もしくは棒状体の外面上の少なくとも一方の面上に配置され、外管の肉厚方向における流路の幅を狭めるためのスペーサをさらに含む上記[1]~[11]のいずれかに記載の流体流通器。
[13]上記[1]~[12]のいずれかに記載の流体流通器と、外管の内面および内管もしくは棒状体の外面の少なくとも一方の面に配置された光触媒とを含む光化学反応器。
[14]内管の内側に配置され、内管を透過し光触媒を励起する光を放射する光源をさらに含む上記[13]に記載の光化学反応器。
[15]外管の外側に配置され、外管を透過し光触媒を励起する光を放射する光源をさらに含む上記[13]に記載の光化学反応器。
[16]光触媒は酸化チタンである上記[13]~[15]のいずれかに記載の光化学反応器。
[17]光触媒は、ブルッカイト型酸化チタンを50%以上含む酸化チタンである上記[13]~[16]のいずれかに記載の光化学反応器。
[18]光触媒は気相法で製造された酸化チタンである上記[13]~[16]のいずれかに記載の光化学反応器。
[19]上記[1]~[12]のいずれかに記載の流体流通器と、外管の外側に光源を有し、外管が光を透過することができるか、内管の内側に光源を有し、内管が光を透過することができるか、または、外管の外側および内管の内側に光源を有し、外管および内管が光を透過することができる光化学反応器。
[20]外管の材料または内管もしくは棒状体の材料は石英ガラスである上記[19]に記載の光化学反応器。
[21]外管の外側に光源を有し、外管が光を透過することができるか、内管の内側に光源を有し、内管が光を透過することができるか、または、外管の外側および内管の内側に光源を有し、外管および内管が光を透過することができる上記[1]~[18]のいずれかに記載の光化学反応器。
本発明の一実施形態における光化学反応器は、本発明の一実施形態における流体流通器と光触媒とを含む。
図1に示すように、本発明の一実施形態における流体流通器1は、外面21および内面22を有する外管2と、外面31および内面32を有し、外管2の内側に配置され、外管2の内面22および外面31で溶液の流路4を形成する内管3とを含む。これにより、外管2の内面22および内管3の外面31により形成される空間の広い範囲にわたって、流体を流通させることができるので、流体の流通量を大きくすることができる。なお、流体は、流路4の中を、外管2および内管3の軸方向に流れる。また、所定の内径を有する外管2と所定の外径を有する内管3とを作製すれば、外管2の肉厚方向における幅が小さい流路4を形成できるので、流体流通器1の製造コストを低くすることができる。さらに、光化学反応器のメンテナンスで、流体流通器1の流路4の閉塞した部分を取り除く場合、外管2の内側に配置された内管3を外管2から外して、外管2および内管3を洗浄すれば、流路4の閉塞した部分を容易に取り除くことができる。また、上述したように、流体流通器1の製造コストは安いため、光化学反応器のメンテナンスで、外管2および/または内管3を取り換える場合でも、交換費用を安くすることができる。
光触媒は、外管2の内面22および内管3の外面31の少なくとも一方の面に配置される。これにより、外管2の内面22および内管3の外面31により形成される流路4を流れる溶液を光触媒により処理することができる。たとえば、溶液が水である場合、水を浄化することができる。
本発明の一実施形態における流体流通器および本発明の一実施形態における光化学反応器を次のように変形することができる。
外管または内管の少なくとも一部が多孔質材料で構成されるようにしてもよい。これにより、外管または内管の多孔質材料から構成されている部分から、光触媒による光触媒反応に必要な気体を供給したり、光触媒による光触媒反応により生成した気体を流路から回収したりすることができる。上記多孔質材料は、液体と気体とを分離することができる多孔質材料であればとくに限定されない。上記多孔質材料には、たとえば、多孔質セラミック材料、多孔質ガラス材料、多孔質金属材料および多孔質樹脂材料などが挙げられる。好ましい多孔質材料は、多孔質樹脂材料である。好ましい多孔質樹脂材料は、たとえば、ポリテトラフルオロエチレン、ポリクロロトリフルオロエチレン、ポリフッ化ビニリデン、ポリ塩化ビニリデン、ポリ塩化ビニル、ナフィオン(R)、ポリフルオロエチレンプロペンコポリマー、パーフルオロアルコキシアルカン、エチレン・テトラフルオロエチレンコポリマー、テトラフルオロエチレン-パーフルオロジオキソールコポリマー、ポリエーテルケトン、ポリイミド、ポリブチレンナフタレート、ポリエーテルサルフォン、芳香族ポリエステル、ポリアミド、ナイロン、ポリビニルピロリドン、ポリアリルアミン、ポリスチレンおよびその置換体、ポリエチレン、ポリビニルアルコール、ポリプロピレンおよびポリカーボネートからなる群から選択される少なくとも一種またはこれらの一部を含む共重合体などである。より好ましい多孔質樹脂材料はポリテトラフルオロエチレンである。多孔質材料を通じて溶液に供給する気体には、たとえば、酸素、二酸化炭素、窒素およびアルゴンなどが挙げられる。多孔質材料の平均細孔径、細孔径分布および気孔率は、気体と液体とを分離することができる平均細孔径、細孔径分布および気孔率であればとくに限定されない。また、多孔質材料は、金属製多孔質材料、金属微粉末焼結多孔質体、金属コイルフィルタ、これらの多孔質金属材料の表面に有機表面処理剤を塗布した多孔質構造体、これらの多孔質金属材料の表面に高分子薄膜を形成した多孔質構造体、またはこれらの多孔質金属材料の表面に無機化合物の表面被覆層を形成した多孔質構造体であってもよい。
以上、説明した流体流通器1における外管2の軸方向に対して垂直方向における外管2の内面21の断面形状が円または楕円であり、内管3の軸方向に対して垂直方向における内管3の外面31の断面形状が円または楕円であった。しかし、流体流通器1における外管の軸方向に対して垂直方向における外管の内面の断面形状が多角形であり、内管の軸方向に対して垂直方向における内管の外面の断面形状が多角形であってもよい。たとえば、図2に示す流体流通器1Aのように、外管2Aの軸方向に対して垂直方向における外管2Aの内面22Aの断面形状が四角形であり、内管3Aの軸方向に対して垂直方向における内管3Aの外面31Aの断面形状が四角形であってもよい。なお、図2において、符号21Aは外管2Aの外面を示し、符号32Aは内管3Aの内面を示す。さらに、符号4Aは、外管2Aの内面22Aおよび内管3Aの外面31Aにより形成される流路を示す。
本発明の一実施形態における流体流通器は、外管の内面上および内管の外面上の少なくとも一方の面上に配置され、外管の肉厚方向における流路の幅を狭めるためのスペーサをさらに含んでもよい。これにより、外管の肉厚方向における流路の幅のより細かい制御が可能になる。たとえば、図6に示す流体流通器1Eに示すように、内管3Eの外面31E上にスペーサ5を配置して、外管2Eの内面22Eおよび内管3Eの外面31Eにより形成される流路4Eの外管2Eの肉厚方向41Eにおける幅を狭めるようにしてもよい。たとえば、樹脂フィルム、織布および不織布などをスペーサとして使用することができる。
以上、本発明の一実施形態の流体流通器および上記流体流通器の変形例1~4を、光化学反応器に用いたが、本発明の一実施形態の流体流通器および上記流体流通器の変形例1~3の用途は光化学反応器に限定されない。たとえば、本発明の一実施形態の流体流通器および上記流体流通器の変形例1~3を、マイクロチャネル型反応器の連続的な原料供給、生成物回収、濃縮および精製工程に使用する流体流通器として使用することができる。
以上の一実施形態の流体流通路の内側に配置されるものは内管であったが、内管の代わりに、棒状体を配置してもよい。この場合も、外管の内面および棒状体の外面により流路を形成することができる。棒状体には、たとえば、円柱および角柱などが挙げられる。棒状体の材料として、たとえば、上に記載された、流体流通器1の外管2の外側から光を照射して、光化学反応器の光触媒を励起させる場合の内管3の材料と同じものを使用してもよい。また、棒状体の少なくとも一部が多孔質材料で構成されるようにしてもよい。これにより、棒状体の多孔質材料から構成されている部分から、光触媒による光触媒反応に必要な気体を供給したり、光触媒による光触媒反応により生成した気体を流路から回収したりすることができる。
以上、流体流通路の流路を流れる物質の相について、溶液である液体を例に挙げて説明したが、流体流通路の流路を流れる物質の相は流体であれば、液体に限定されない。たとえば、流体流通路の流路に気体が流れてもよい。
流体流通路の流路を流れる流体の撹拌を促進するため、内管を円周方向に回転させてもよい。とくに、内管の外面に触媒を塗布した場合、これにより光触媒と流体との間の接触を促進することができる。たとえば、次のようにして内管を回転させることができる。内管の内部に磁石を配置し、内管と固定する。また、中心が外管の中心軸と一致するように外管の外側にリング状治具を配置する。リング状治具の内側に反対の磁極を持つ磁石を配置する。具体的には、内管の内部に配置された磁石とN-S対を形成し、かつ対向するように、リング状治具の磁石を配置する。リング状治具を、モーターなどの回転装置を使用して円周方向に回転させると、リング状の治具に設けられた磁石の磁力によって、内管の内部に設置された磁石も回転する。内管の内部に設置された磁石は内管と固定されているので、内管も一緒に回転する。これにより、非接触で内管を回転させることができる。なお、磁石は、磁力が強い磁石であることが好ましくは、たとえば、希土類磁石である。
本発明の一実施形態の光化学反応器は、内管の内側に配置され、内管を透過し光触媒を励起する光を放射する光源をさらに含んでもよい。たとえば、図7に示す光化学反応器10Fのように、内管3Fの内側に光源6を配置してもよい。光源6は、内管3Fを透過し光触媒を励起する光を放射するものであれば限定されない。たとえば、光源6は、低圧水銀灯、ブラックライトまたはLED(発光ダイオード)である。なお、符号2Fは外管を示し、符号4Fは流路を示す。
以上の一実施形態における光化学反応器では、光触媒が外管の内面および内管の外面の少なくとも一方の面に配置されていた。しかし、光感応性原料などの原料自体が光の照射により反応する原料を処理する光化学反応器の場合、光化学反応器に光触媒を配置しなくてもよい。この場合の光化学反応器は、たとえば、本発明の一実施形態における流体流通器と、外管の外側に光源とを有し、外管が光を透過することができる光化学反応器、または、本発明の一実施形態における流体流通器と、内管の内側に光源とを有し、内管が光を透過することができる光化学反応器である。このとき、流体流通器の外管の外側から光を照射して、流体中の原料を励起させるか、または、流体流通器の内管の内側から光を照射して、流体中の原料を励起させる。さらに、光化学反応器の変形例2は、本発明の一実施形態における流体流通器と、外管の外側に光源と、内管の内側に光源とを有し、外管および内管が光を透過することができる光化学反応器であってもよい。
以上、流体流通路の流路に液体が流れる光化学反応器について説明したが、光化学反応器の流体流通路に流れるものは流体であれば、液体に限定されない。たとえば、光化学反応器の流体流通路の流路に気体が流れてもよい。流体が気体の場合、光化学反応器は、気体に含まれる窒素酸化物、VOC(揮発性有機化合物)および臭気成分などを分解することができる。
(外管の内面の光触媒層の形成)
昭和電工セラミックス(株)製のNTB1コロイド分散液(ブルッカイト型酸化チタンナノ粒子の分散液)6.66g、ポリエチレングリコール(和光純薬工業(株)製、平均分子量300)2.42g、アセチルアセトン(和光純薬工業(株)製、型番:)1.01gおよびエタノール(和光純薬工業(株)社製、型番:320-00017)2.0gをジルコニア製の遊星ボールミル((株)伊藤製作所製、型番:LP-1)にて400rpm、30分間の粉砕工程を経て、塗布溶液を調整した。次に、外径5.9mm、内径4.5mmおよび長さ650mmの石英ガラス管((株)藤原製作所製、型番:#4)の中に、この塗布溶液を充填し、過剰の溶液を排出後、ブロワーで空気を流して乾燥し、450℃で2時間焼成することにより、外管の内面にブルッカイト型酸化チタンナノ粒子のコーティング層を形成した。なお、別途、同じ手順にて平板状のパイレックス(登録商標)基板の表面に形成した酸化チタンナノ粒子薄膜の鉛筆引っ掻き試験機による塗膜強度は6Hであり、光触媒層をして十分な強度を有していることを確認した。
内面にブルッカイト型酸化チタンナノ粒子のコーティング層を形成した上記石英ガラス管を外管とし、この内部に、外径3.9mm、内径2.5 mmおよび長さ650mmの石英ガラス管((株)藤原製作所製、型番:#2)の両端を溶封したガラス構造物を配置し、それらの両端にフッ素樹脂で作製した継手をそれぞれ取り付けた。それぞれの継手に1/16インチのテフロン(登録商標)製配管を接続し、一方のテフロン(登録商標)製配管を送液ポンプに、他方のテフロン(登録商標)製配管を生成物溶液の回収容器にそれぞれ接続した。この流体流通器の外管の内面と内管の外面との間の距離は平均約500μmであり、外管の内面と内管の外面とで形成される流路の全体積は実測で3.6mLであり、光源からの光を受光する外管の受光窓の面積は82cm2であり、受光窓面積/流路体積比は2290m-1であった。この外管の受光窓の面積は、マイクロチャネル反応器よりも広い受光面積であった。
外管の内面に酸化チタンナノ粒子のコーティング層を形成しなかったことを除いて、実施例1の光化学反応器の作製方法と同様の方法で比較例1の光化学反応器を作製した。
内管を設けなかったことを除いて、実施例1の光化学反応器の作製方法と同様の方法で比較例2の光化学反応器を作製した。
上述のように作製した光化学反応器を使用して水を浄化することにより光化学反応器を評価した。浄化の対象となる水には、典型的な水溶性汚染物質である4-クロロフェノール(厚生労働省の上水道の水質基準項目と基準値(51項目)のフェノール類(フェノールの量に換算して0.005mg/L以下)に対応する)を添加した。光触媒を励起させる光源として、6本の20Wのブラックランプ((株)東芝製、型番:FL20S BLB)を使用した。上記ガラス管を取り囲み、上記ガラス管と平行になるように、6本の上記ブラックランプを配置した。6本のブラックランプを点灯した後、4-クロロフェノールの濃度100μMである水を、光化学反応器の流路に流通させた。流路を流れる水の流量を10mL/分、5mL/分および1mL/分と変えて、光化学反応器を使用して水を処理した。
実施例1の光化学反応器の4-クロロフェノールの転化率は、水の流量が10mL/分のとき、6%であり、水の流量が5mL/分のとき、9%であり、水の流量が1mL/分のとき、32%であった。一方、光を照射しない条件下での比較例1の光化学反応器の4-クロロフェノールの転化率は、水の流量が10mL/分のとき、1%であり、水の流量が5mL/分のとき、1%であり、水の流量が1mL/分のとき、1%であった。これより、比較例1の光化学反応器では吸着がほとんど起こらないことを確認された。また、内管が設けられていない比較例2の光化学反応器の4-クロロフェノールの転化率は、最も滞留時間が長い条件である、水の流量が1mL/分のとき、18%であった。比較例2の光化学反応器の体積は10.3mLであり、内管を有する光反応器と比較して、水が流路内に滞留する時間は2.8倍となった。光反応器に水が滞留する時間は水に光が照射される時間に相当するため、比較例2の光化学反応器が受光する光量は2.8倍となる。受光する単位光量当たりの反応効率で比較すると、外管の内側に内管を設けて流路を形成することによって、反応効率が約5倍になることがわかった。これより、本発明の光化学反応器を使用することによって、多くの水溶性汚染物質を水から除去できることがわかった。また、実施例1の光化学反応器の4-クロロフェノールの転化率は、4-クロロフェノールの濃度が1mMである水を、1mL/分の流量で光化学反応器の流路に流通させた場合、7%であった。これは、4-クロロフェノールの分解量としては、4-クロロフェノールの濃度が100μMである水を、1mL/分の流量で光化学反応器の流路に流通させた場合に比べて約2倍の量に相当する。
外径6.0mm、内径4.4mmよび長さ650mmの石英ガラス管((株)藤原製作所製、型番:#4)の内部に外径3.8mmおよび長さ650mmの透明石英ガラス管((株)三商製、型番:IQ-2)の両端を溶封した構造体を配置し、それらの両端にフッ素樹脂で作製した継手をそれぞれ取り付けた。この反応器は、溶液中の光反応性分子を直接光励起して活性化するため、光触媒層を設けていない。それぞれの継手に1/16インチのテフロン(登録商標)製配管を接続し、一方のテフロン(登録商標)製配管をシリンジポンプ(アイシス(株)製、Fusion 100型)およびガスタイトシリンジ(SGE、50mL)に、他方のテフロン(登録商標)製配管を生成物溶液の回収容器にそれぞれ接続した。この流体流通器の外管の内面とガラス棒の外面との間の距離は平均約300μmであり、外管の内面とガラス棒の外面とで形成される流路の全体積は実測で2.2mLであり、光源からの光を受光する外管の受光窓の面積は、ランプで照射している領域の実測値として109cm2であり、受光窓面積/流路体積比は4950m-1であった。この外管の受光窓の面積は、マイクロチャネル反応器よりも広い受光面積であった。
透明石英ガラス管の両端を溶封した構造体を設けなかったことを除いて、実施例2の光化学反応器の作製方法と同様の方法で比較例3の光化学反応器を作製した。この反応器の反応器体積は、8.8mLであり、光源からの光を受光する外管の受光窓の面積は、ランプで照射している領域の実測値として109cm2であり、受光窓面積/流路体積比は1240m-1であり、ガラス棒を設けた反応器と比較して約1/4に減少した。
上述のように作製した光化学反応器を使用して1Mイソホロン-メタノール溶液を使用して光化学反応器を評価した。1Mイソホロン-メタノール溶液は、メタノール(和光純薬工業(株)製、型番:136-01837)にイソホロン(和光純薬工業(株)製、型番:095-01796)を添加することにより作製した。光触媒を励起させる光源として、6本の20Wの殺菌灯((株)東芝製、型番:GL20F)を使用した。上記ガラス管を取り囲み、上記ガラス管と平行になるように、6本の上記殺菌灯を配置した。そして、上記殺菌灯を使用して、実施例2の光化学反応器の外管の中央の580mmの領域に光を照射した。実施例2の光化学反応器では、6本の殺菌灯を点灯した後、1Mイソホロン-メタノール溶液を、0.5cm3/分の流量で実施例2の光化学反応器の流路に流通させた。この条件では流速は13cm/分となり、1Mイソホロン-メタノール溶液の実施例2の光化学反応器における滞留時間は4.4分であった。また、比較例3の光反応器においては、実施例2の反応器と同じ流速で比較するため、流量を2.0cm3/分とし、実施例2と同じ流速(13cm/分)および反応器滞留時間(4.4分)の条件で、1Mイソホロン-メタノール溶液を流路に流通させた。
実施例2の光化学反応器では、イソホロンのHT型二量体の濃度は2.2mMであり、HH型二量体の濃度は12.5mMであり、転化率は約3%となった。一方、比較例3の光化学反応器では、イソホロンのHT型二量体の濃度は0.9mMであり、HH型二量体の濃度は4.0mMであり、転化率は約1%であった。これより、実施例2の光化学反応器の転化率は、比較例3の光化学反応器の転化率の約3倍に向上した。実施例2の光化学反応器のHH/HT比は5.6であったのに対し、比較例3の光化学反応器のHH/HTは4.4であり、概ね同等の選択性を持つことがわかった。
実施例2の光化学反応器の外管(内径14.5mmのガラス管)の内壁にアナターゼ型酸化チタンの分散液(アナターゼ型酸化チタン(日揮触媒化成(株)製、型番:PST18NR)の20%エタノール溶液)をディップコートし、外管の内壁にアナターゼ型酸化チタンのコーティングを形成した。そして、そのコーティングを450℃で2時間焼成することにより、外管の内壁にアナターゼ型酸化チタン層を形成した。次に、内部に2つの希土類磁石を接着した後、両端を融着封止した内管(外形14.0mmのガラス管)を外管の内部に挿入した。外管の内径と内管の外径との差が500μmであるため、外管の内面と内管の外面とで形成さえる間隙は250μmとなった。外管の中心軸と中心が略一致するように、この外管の外側にリング状のテフロン(登録商標)治具を配置した。リング状のテフロン(登録商標)治具の内壁には、内管の内部に接着されている希土類磁石とN-S対を形成し、かつ対向するように、2個の希土類磁石をそれぞれ配置した。これにより、モーターを利用してテフロン(登録商標)治具を回転させると内管が非接触で回転するようになった。
シリンジポンプを使用して、外管と内管との間の流体流通路に4-クロロフェノール水溶液(50μM)を流速1mL/分にて送液し、流体流通路から排出された溶液中の4-クロロフェノールの濃度を測定し、転化率を求めた。内管を回転させない場合の転化率は39%であった。一方、8.6回転/分の回転速度で内管を回転させた場合の転化率は60%であった。これは、内管を回転させない場合の転化率の約1.5倍の値であった。さらに、27回転/分の回転速度で内管を回転させた場合の転化率は70%であり、80回転/分の回転速度で内管を回転させた場合の転化率は69%であった。これより、内管を回転させることによって、転化率を増加させることができ、その効果は反応器の回転数が27回転/分で概ね飽和することがわかった。これは、内管の回転により、流体流通路を流れる溶液の撹拌が促進されたためであると予測される。
2,2A~2F 外管
3,3A~3F 内管
4 流路
5 スペーサ
6 光源
10F 光化学反応器
Claims (21)
- 外面および内面を有する外管と、
外面および内面を有し、該外管の内側に配置され、該外管の内面および該外面で流体の流路を形成する内管、または外面を有し、該外管の内側に配置され、該外管の内面および該外面で流体の流路を形成する棒状体とを含み、
前記外管の肉厚方向における前記外管の内面と前記内管または前記棒状体の外面との間の距離が100nm~5mmである流体流通器。 - 前記外管の肉厚方向における前記外管の内面と前記内管または前記棒状体の外面との間の距離が1μm~1mmである請求項1に記載の流体流通器。
- 前記外管または前記内管もしくは前記棒状体が円周方向に回転するか、または、前記外管および前記内管もしくは前記棒状体の両方が円周方向に、および相互に反対方向に回転する請求項1または2に記載の流体流通路。
- 前記外管または前記内管もしくは前記棒状体の回転方向が周期的に反転する請求項3に記載の流体流通路。
- 中心が前記外管の中心軸と一致するように前記外管の外側に配置されたリング状治具と、
前記内管と固定され、前記内管の内部に配置され磁石と、
前記内管の内部に配置された前記磁石とN-S対を形成し、かつ対向するように前記リング状治具の内側に配置された磁石と、
前記リング状治具を円周方向に回転させる回転装置とをさらに含み、
前記リング状治具を円周方向に回転させると、前記内管が円周方向に回転する請求項1~4のいずれか1項に記載の流体流通路。 - 前記外管または前記内管もしくは前記棒状体の少なくとも一部が多孔質材料で構成される請求項1~5のいずれか1項に記載の流体流通器。
- 前記多孔質材料は、多孔質セラミック材料、多孔質ガラス材料、多孔質金属材料または多孔質樹脂材料である請求項6に記載の流体流通器。
- 前記多孔質材料は、ポリテトラフルオロエチレン、ポリクロロトリフルオロエチレン、ポリフッ化ビニリデン、ポリ塩化ビニリデン、ポリ塩化ビニル、ナフィオン(R)、ポリフルオロエチレンプロペンコポリマー、パーフルオロアルコキシアルカン、エチレン・テトラフルオロエチレンコポリマー、テトラフルオロエチレン-パーフルオロジオキソールコポリマー、ポリエーテルケトン、ポリイミド、ポリブチレンナフタレート、ポリエーテルサルフォン、芳香族ポリエステル、ポリアミド、ナイロン、ポリビニルピロリドン、ポリアリルアミン、ポリスチレンおよびその置換体、ポリエチレン、ポリビニルアルコール、ポリプロピレンおよびポリカーボネートからなる群から選択される少なくとも一種またはこれらの一部を含む共重合体である多孔性樹脂材料からなる請求項7に記載の流体流通器。
- 前記多孔質材料は、金属製多孔質材料、金属微粉末焼結多孔質体、金属コイルフィルタ、これらの多孔質金属材料の表面に有機表面処理剤を塗布した多孔質構造体、これらの多孔質金属材料の表面に高分子薄膜を形成した多孔質構造体、またはこれらの多孔質金属材料の表面に無機化合物の表面被覆層を形成した多孔質構造体である請求項7に記載の流体流通器。
- 前記外管の軸方向に対して垂直方向における前記外管の内面の断面形状が円または楕円であり、
前記内管の軸方向に対して垂直方向における前記内管の外面の断面形状、または前記棒状体の軸方向に対して垂直方向における断面形状が円または楕円である請求項1~4のいずれか1項に記載の流体流通器。 - 前記外管の軸方向に対して垂直方向における前記外管の内面の断面形状が多角形であり、
前記内管の軸方向に対して垂直方向における前記内管の外面の断面形状、または前記棒状体の軸方向に対して垂直方向における断面形状が多角形である請求項1~4のいずれか1項に記載の流体流通器。 - 前記外管の内面上および前記内管または前記棒状体の外面上の少なくとも一方の面上に配置され、前記外管の肉厚方向における前記流路の幅を狭めるためのスペーサをさらに含む請求項1~11のいずれか1項に記載の流体流通器。
- 請求項1~12のいずれか1項に記載の流体流通器と、
前記外管の内面および前記内管もしくは前記棒状体の外面の少なくとも一方の面に配置された光触媒とを含む光化学反応器。 - 前記内管の内側に配置され、前記内管を透過し前記光触媒を励起する光を放射する光源をさらに含む請求項13に記載の光化学反応器。
- 前記外管の外側に配置され、前記外管を透過し前記光触媒を励起する光を放射する光源をさらに含む請求項13に記載の光化学反応器。
- 前記光触媒は酸化チタンである請求項13~15のいずれか1項に記載の光化学反応器。
- 前記光触媒は、ブルッカイト型酸化チタンを50%以上含む酸化チタンである請求項13~16のいずれか1項に記載の光化学反応器。
- 前記光触媒は気相法で製造された酸化チタンである請求項13~16のいずれか1項に記載の光化学反応器。
- 請求項1~12のいずれか1項に記載の流体流通器と、
前記外管の外側に光源を有し、該外管が光を透過することができるか、前記内管の内側に光源を有し、該内管が光を透過することができるか、または、前記外管の外側および前記内管の内側に光源を有し、該外管および該内管が光を透過することができる光化学反応器。 - 前記外管の材料または前記内管もしくは前記棒状体の材料は石英ガラスである請求項19に記載の光化学反応器。
- 前記外管の外側に光源を有し、該外管が光を透過することができるか、前記内管の内側に光源を有し、該内管が光を透過することができるか、または、前記外管の外側および前記内管の内側に光源を有し、該外管および該内管が光を透過することができる請求項13~18のいずれか1項に記載の光化学反応器。
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JP2017221896A (ja) * | 2016-06-15 | 2017-12-21 | 東芝ライテック株式会社 | 光触媒装置 |
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JP2021501040A (ja) * | 2017-09-14 | 2021-01-14 | ルプニク, カルロRUPNIK, Carlo | 薄い流動床における電磁波の近位および垂直放射のための反応器 |
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KR102436940B1 (ko) * | 2017-07-12 | 2022-08-29 | 서울바이오시스 주식회사 | 유체 처리 장치 |
CN113731327A (zh) * | 2021-09-14 | 2021-12-03 | 南通海晴医药科技有限公司 | 一种涡旋流动光化学反应器 |
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