JP6490952B2 - Reactor and water treatment device - Google Patents

Description

  The present invention relates to a reactant container for filling a reactant, a reactor in which the reactant container is filled with a reactant, and a water treatment apparatus using the same, and more particularly, a monolithic ion exchanger filling structure About.

  A monolithic ion exchanger is known as one of the ion exchangers (Patent Documents 1 and 2). The monolithic ion exchanger is a porous ion exchanger having a continuous pore structure. The monolithic ion exchanger can control the pore diameter from several μm to several tens of μm, and has a shorter ion exchange zone length than the granular ion exchange resin. Therefore, ions can be adsorbed quickly and uniformly, and processing at a high flow rate is possible. The ion exchange zone length refers to the length of the portion (ion exchanger) in which the reaction is actively performed in the steady state of the ion exchange reaction. Various catalysts can be supported on the monolithic ion exchanger. A monolithic ion exchanger carrying a platinum group metal catalyst is suitable for hydrogen peroxide decomposition treatment (Patent Documents 3 to 4).

Japanese Patent No. 523299 Japanese Patent No. 5231300 JP 2010-240641 A JP 2010-240642 A

  Monolithic ion exchangers have superior processing performance compared to granular ion exchangers, and can be processed at high flow rates. However, the higher the flow rate, the higher the differential pressure, affecting the overall performance of the system including the monolithic ion exchanger. Similar problems generally exist not only in monolithic ion exchangers but also in reactants that can be processed at high flow rates, but the differential pressure increases with higher flow rates.

An object of the present invention is to provide a reactor in which an increase in differential pressure is suppressed even under high flow rate conditions.

The reactor of the present invention includes a reactant container and a plurality of reactants that are monolithic ion exchangers filled in the reactant container. Reactants container comprises a reaction body holding portion having a plurality of through holes in which a plurality of reactants are filled respectively, are connected to the upper periphery of the reactants holding portion, the inlet portion treated water is supplied An upper lid and a bottom lid that is connected to the lower peripheral edge of the reactant holding portion and has an outlet for discharging the water to be treated. Each top lid and the bottom lid is provided with a flange for holding the reactants holding portion, and is connected to the pipe at the inlet portion or outlet portion. In the cross section of the through hole orthogonal to the through hole, D / H ≧ 1, where D is the diameter of the smallest virtual circle containing at least one through hole, and H is the axial length of the through hole. A value obtained by dividing the area of the filling region of the reactant in at least one through hole by the area of the virtual circle is 0.3 or more.

  The through hole has a shape satisfying D / H ≧ 1. As described above, the reactant can be subjected to a water flow treatment under a high flow rate condition. However, if the reactant filling height is high, the water flow differential pressure increases. Since the filling height of the reactants can be suppressed by satisfying D / H ≧ 1, water flow treatment under a high flow rate condition can be performed while suppressing the water flow differential pressure.

According to the present invention, it is possible to provide a reactor in which an increase in differential pressure is suppressed even under a high flow rate condition.

It is a schematic block diagram of the ultrapure water manufacturing apparatus which concerns on 1st Embodiment. It is the schematic of the ion exchange apparatus which concerns on 1st Embodiment. It is a top view of a support plate. It is a conceptual diagram which shows the other filling pattern of a monolithic ion exchanger. It is the schematic of embodiment provided with the several ion exchanger accommodating body. It is a schematic block diagram of the ultrapure water manufacturing apparatus which concerns on 2nd Embodiment. It is the schematic of the cartridge polisher in which the ion exchanger accommodating body was accommodated. It is a conceptual diagram of a monolithic ion exchanger.

(First embodiment)
First, the ultrapure water manufacturing apparatus according to the first embodiment of the present invention will be described. The ultrapure water production apparatus is used, for example, in the semiconductor manufacturing industry to clean silicon wafers using ultrapure water from which impurities are highly removed. Ultrapure water generally removes part of suspended matter and organic matter contained in raw water (river water, groundwater, industrial water, etc.) in the pretreatment process, and then treats the treated water with the primary pure water system and secondary pure water. Manufactured by sequential processing in an aqueous system (subsystem) and supplied to a use point for wafer cleaning. In a primary pure water system, for example, salts and impurities are removed from water by a reverse osmosis membrane separation device, and dissolved oxygen is removed by a deaeration device, thereby producing pure water. In the secondary pure water system, the purity of water is further increased and ultrapure water is produced.

  FIG. 1 shows a schematic configuration of an ultrapure water production apparatus 1 according to an embodiment of the present invention. The ultrapure water production apparatus 1 is the above-described secondary pure water system (subsystem). However, the apparatus that is the subject of the present invention may be in a primary pure water system or other water treatment system. It can be applied to all processing systems. The present invention can also be applied to processing (purification) of fluids other than water, for example, chemicals such as alcohol, and processing systems for gases such as the atmosphere. The ultrapure water production apparatus 1 includes a tank (T) 2 for storing pure water (treated water) produced by a primary pure water system (not shown), and a pump (P) for delivering treated water from the tank 2 (P ) 3, a heat exchanger (Hx) 4, an ultraviolet oxidation device (UVox) 5, a hydrogen peroxide removing device 6 composed of a monolithic ion exchanger carrying palladium (Pd), and a cartridge polisher ( A non-regenerative ion exchange device (CP) 7, a membrane deaeration device (MD) 8, and an ultrafiltration device (UF) 9 are disposed on the mother pipe 10 in this order. .

  The tank 2 stores water to be treated containing a TOC component. The treated water stored in the tank 2 is pumped by the pump 3 and sent to the ultraviolet oxidizer 5. The temperature of the water to be treated is adjusted by the heat exchanger 4 in advance. In the ultraviolet irradiation device 5, ultraviolet rays including a wavelength of 254 nm and a wavelength of 185 nm are irradiated to the water to be treated to generate OH radicals. The generated OH radical decomposes TOC contained in the water to be treated into carbon dioxide and organic acid.

  The generated carbon dioxide and organic acid are removed by the cartridge polisher 7. The cartridge polisher 7 is a non-regenerative ion exchange device in which an ion exchange resin filled in a cylinder removes ions in the water to be treated. When the ion exchange function of the resin is lowered, the resin chemical regeneration is not performed and the resin is replaced with a new resin. For this reason, three cartridge polishers (CP1, CP2, CP3) 7a, 7b, 7c each having 50% capacity are provided, and the resin can be exchanged even during operation of the ultrapure water production apparatus 1. . The treated water that has passed through the ultraviolet irradiation device 5 contains an oxidizing substance such as hydrogen peroxide generated by the ultraviolet rays irradiated by the ultraviolet irradiation device 5. For this reason, a hydrogen peroxide removing device 6 is provided between the ultraviolet irradiation device 5 and the cartridge polisher 7, and the hydrogen peroxide is decomposed into water and oxygen.

  As the hydrogen peroxide removing device 6, it is preferable to use a catalyst metal carrier on which a platinum group metal such as Pd is supported. Hydrogen peroxide in the water to be treated can be contacted with a platinum group metal catalyst, and hydrogen peroxide can be removed by catalytic decomposition. The platinum group metal catalyst is supported on, for example, an anion exchanger. The anion exchanger may be a granular anion exchange resin, but a monolithic organic porous anion exchanger formed by integrating the anion exchange resin is preferably used. By supporting the platinum group metal catalyst on the anion exchanger, a high catalytic ability is exhibited, and the effluent from the catalyst is reduced. The platinum group metal supported catalyst can remove dissolved oxygen in the presence of hydrogen and can also be used as a deoxygenation apparatus.

  The water to be treated that has passed through the cartridge polisher 7 is sent to the membrane deaerator 8 to remove dissolved oxygen. The dissolved oxygen contained in the ultrapure water forms a natural oxide film on the surface of a silicon wafer or the like. When a natural oxide film is formed on the wafer surface, it prevents growth of epitaxial silicon thin films at low temperatures, hinders precise control of the gate oxide film thickness and film quality, and increases the contact resistance of contact holes. It becomes. Therefore, it is necessary to prevent the formation of a natural oxide film on the wafer surface as much as possible, and it is necessary to suppress the amount of dissolved oxygen in the ultrapure water. Fine particles are removed by the ultrafiltration device 9. In this way, the water to be treated becomes ultrapure water from which impurities are highly removed, and is sent to the use point. The ultrapure water that has not been used is returned to the tank 2 by a return pipe 11 from a branch point between the ultrafiltration device 9 and the use point.

Next, the configuration of the hydrogen peroxide removing device 6 will be described in more detail with reference to FIG. In this embodiment, the hydrogen peroxide removing device 6 is provided as an independent reactor 21. 2 (a) is a side sectional view of the reactor 21, FIG. 2 (b) is at the level of the reactor 21 along the line 2b-2b of FIG. 2 (a), and more specifically at the level of the reactant holding part 24. FIG. 2C is a cross-sectional view of the reactor 21, and FIG. 2C is a side cross-sectional view of the reactant container 22 taken along line 2c-2c in FIG. The reactant container 22 means a container filled with the reactant, and the reactor 21 means the reactant container 22 filled with the reactant. The reactant container 22 is made of stainless steel. The reactant container 22 has a flow path or through hole 34 having an inlet opening 37 and an outlet opening 38 through which water to be treated can communicate. The reactant container 22 is generally in the shape of a rotating body because of ease of manufacture, cost, pressure resistance, and the like, and more specifically, a cylindrical shape having a reactant filling region 23 filled with the reactant. A reactant lid 24, an upper lid 26 connected to the upper peripheral edge 25 of the reactant holder 24, and a bottom lid 28 connected to the lower peripheral edge 27 of the reactant holder 24. Yes. The top lid 26, the reactant holding portion 24, and the bottom lid 28 have flanges 26a, 24a, and 28a, respectively, and are fastened to each other by fastening means 43 that includes bolts and nuts (not shown). As will be described later, the reactant holder 24 is thin, and the reactant container 22 has a disk-like shape as a whole. The reactant container 22 is installed so that the center line CL extends substantially in the vertical direction, and the water to be treated flows into the reactant container 22 from the upper inlet 32 and passes through the inlet opening 37 to the reactant holder 24. It flows in, flows out from the reactant holding part 24 through the outlet opening 38, and flows out from the reactant container 22 through the lower outlet 33. Here, the reactant means a substance that treats a specific substance in the water to be treated by a physicochemical reaction such as an ion exchange reaction, an adsorption reaction, an oxidation-reduction reaction, or a catalytic reaction. The reactant includes an ion exchanger, a monolithic ion exchanger, a monolithic ion exchanger carrying a platinum group metal catalyst, an ion exchange resin carrying a platinum group metal catalyst, and the like. The reactant filling region 23 is filled with at least one, in this embodiment, a monolithic ion exchanger (hereinafter sometimes referred to as “Pd monolith”) M carrying a plurality of Pd.

  Referring to FIG. 2B, seven Pd monoliths M1 to M7 are accommodated in the reactant accommodating body 22, more specifically, the reactant holding portion 24. The reactant container 22 has seven flow paths or through-holes 34, and one Pd monolith M1 to M7 is accommodated in each flow path or through-hole 34, respectively. Each Pd monolith M has a circular cross section in the flow path cross section of the reactant container 22 (cross section orthogonal to the central axis CL or cross section orthogonal to the flow path 34 of the reactant container 22), and is generally cylindrical. It has a shape. The Pd monolith M is arranged point-symmetrically with respect to the central axis CL of the reactant container 22. Specifically, one Pd monolith M1 is installed coaxially with the central axis CL of the reactant container 22, and six Pd monoliths M2 are arranged around the Pd monolith M1 along a virtual circle 40 coaxial with the Pd monolith M1. To M7 are arranged at equal intervals of α = 60 °. Since the Pd monolith M is cylindrical, the cylindrical flow path 34 can be easily filled, and the arrangement efficiency and use efficiency of the Pd monolith M are improved. A hole 24 b through which a bolt passes is formed along the outer periphery of the ion exchanger housing 22.

  The reactant container 22 has a support plate 31 for supporting the Pd monolith M therein. Seven support plates 31 are provided, and each support the Pd monolith M. The reactant container 22 has a ring-shaped protrusion 35 protruding toward the center of the flow path 34 at the bottom of each flow path 34, and the support plate 31 is placed on the protrusion 35. The support plate 31 is made of stainless steel. FIG. 3 is a plan view of the support plate 31. The support plate 31 has a number of holes 31a through which water to be treated passes. The diameter of the flow path or the through hole 34 is the same as or the same as the diameter of the Pd monolith M. The Pd monolith M is inserted into the flow path or through-hole 34 and supported by the reactant container 22.

  Seven upper holding plates 29 are provided above the flow path or the through hole 34. The upper holding plate 29 restrains the movement of the Pd monolith M in the vertical direction so that the Pd monolith M is firmly held in the flow path or the through hole 34 when water flows into the reactant container 22. The upper holding plate 29 can be omitted. However, it is preferable to provide the upper holding plate 29 when the reactant container 22 is filled with a granular reactant. The upper holding plate 29 can prevent scattering of the granular reactant. The upper holding plate 29 can have the same structure as the support plate 31, and similarly to the support plate 31, a large number of holes through which water to be treated passes are formed. A ring-shaped groove 36 extends circumferentially along the side surface of the flow path 34 just above the upper holding plate 29. A snap ring 30 is fitted in the groove 36 to restrain the upper holding plate 29. The snap ring 30 is an open ring-shaped member made of stainless steel. The snap ring 30 has an outer diameter larger than the diameter of the flow path 34. By elastically deforming the facing end portions toward each other, the outer diameter becomes smaller than the diameter of the flow path 34 and can be inserted into the flow path 34 from the inlet opening 37. When the deformation is released, the snap ring 30 returns to its original shape and fits into the groove 36 to restrain the movement of the upper holding plate 29 and the Pd monolith M. The reactant is filled in the space between the support plate 31 and the upper holding plate 29. The reactant filling area 23 is an area in the space where the reactant is actually filled. Therefore, the reactant filling region 23 is a part or all of the space between the support plate 31 and the upper holding plate 29.

  FIG. 4 shows another embodiment in which the filling pattern of the Pd monolith M is different. In FIG. 4A, the Pd monolith M having a circular cross section is provided in triplicate. In this way, the number of Pd monoliths can be increased or decreased according to the amount of water to be treated and the concentration of the substance to be treated. The cross-sectional shape of the Pd monolith M is not limited to a circle, but may be a quadrilateral or other polygon.

  In FIG. 4B, a Pd monolith M having a regular hexagonal cross section is provided. A Pd monolith having a regular hexagonal cross section is arranged at the center in the cross section perpendicular to the central axis CL of the reactant container 22, and a regular hexagonal Pd monolith M is further adjacent to the outer peripheral part so as to adhere to each other in a honeycomb shape And cut so as to have one circular cross section that fits in the reactant container 22. By doing so, it is not necessary to provide the individual flow paths 34 as shown in FIG. 2, and a single flow path can be filled with a plurality of Pd monoliths M, and the Pd monoliths M are arranged with high arrangement efficiency. be able to. The number of Pd monoliths can be increased as shown in FIG. 4C according to the amount of water to be treated and the concentration of the substance to be treated.

  FIG. 5 shows an example in which a plurality of reactors 21 are provided. Referring to FIG. 5A, three reactors 21a, 21b, and 21c are provided in parallel in two mother pipes 10 extending in the vertical direction. Referring to FIG. 5B, three reactors 21a, 21b, and 21c are provided in parallel in two mother pipes 10 extending in the horizontal direction. When a plurality of reactors 21 are provided, a part of them can be used as a spare unit. In the illustrated reactors 21a, 21b, and 21c, each reactor 21a, 21b, and 21c has a capacity of 50% of the flow rate, and one reactor 21a (or 21b or 21c) can be stopped. For this reason, the Pd monolith M whose performance has deteriorated can be sequentially replaced while the operation of the ultrapure water production apparatus 1 is continued. Each reactor 21a, 21b, 21c is connected by a pipe 12 branched from the mother pipe 10. The reactors 21a, 21b, 21c and the pipe 12 are connected by a flange 13, and the upper lid 26 is moved upward D1 and the bottom lid 28 is moved downward D2 by releasing the fastening force of a nut (not shown). , And can be separated from the reactant holder 24. For this reason, the reactant holding part 24 filled with the Pd monolith M can be pulled out in the horizontal direction D3 from between the upper lid 26 and the bottom lid 28, and maintenance can be easily performed.

  In the first embodiment, since the Pd monolith M is separated from the ion exchange resin (hereinafter referred to as CP resin) filled in the cartridge polisher 7, the replacement frequency of the Pd monolith M can be increased. For example, when an ion exchange resin resin carrying palladium (hereinafter referred to as Pd resin) is laminated on top of the CP resin, the CP resin has an earlier replacement time than the Pd resin, so that the catalytic activity still remains when the CP resin is replaced. Pd resin must be exchanged together. On the other hand, in this embodiment, the CP resin can be exchanged independently of the Pd monolith M. When the Pd resin is installed in a different tower from the CP resin, the same effect can be obtained when the CP resin is replaced, but the Pd resin requires a larger capacity than the Pd monolith. Since the Pd monolith has a smaller capacity than the Pd resin, a small reactant container 22 can be used. Therefore, the enlargement of the ultrapure water production apparatus 1 can be suppressed.

(Second Embodiment)
The reactant container 22 of the present embodiment is provided inside a container or piping. Hereinafter, the cartridge polisher 7 as a container will be described as an example, but the same can be applied to the inside of a pipe. A container will not be limited if it comprises a water treatment system and the to-be-processed water can distribute | circulate. The internal pressure of the container is not particularly limited, but a greater effect can be expected when the container is subjected to a pressure exceeding atmospheric pressure during use of the water treatment system. Further, the present embodiment can also be applied to a processing system (purification) of a fluid other than water, for example, a chemical solution such as alcohol, and a gas processing system such as the atmosphere.

  FIG. 6 shows a schematic configuration of an ultrapure water production apparatus 101 according to the second embodiment of the present invention. In this embodiment, the hydrogen peroxide removing device 6 or the reactor 21 is built in the upper space of the cartridge polisher 7 filled with the non-regenerative ion exchanger. Specifically, the reactant accommodating bodies 22a, 22b, and 22c are provided inside the three cartridge polishers 7a, 7b, and 7c, respectively. The reactant containers 22a, 22b, and 22c all have the same configuration. Other configurations of the ultrapure water production apparatus 101 are the same as those of the ultrapure water production apparatus 1 of the first embodiment shown in FIG.

  7A is a cross-sectional view of the cartridge polisher 7 in which the reactor 21 is accommodated, and FIG. 7B is an enlarged view of a portion A in FIG. 7A. The cartridge polisher 7 has a substantially cylindrical shape, and water to be treated flows from an inlet or opening 71 at the upper end and flows out from an outlet 74 near the lower end. The cylindrical portion at the center of the cartridge polisher 7 is provided with a mixed bed type ion exchange resin filling portion 73 in which a cation exchange resin and an anion exchange resin are mixed and filled. An ion exchange resin outlet 75 is provided at the lower end of the cartridge polisher 7. The reactor 21 is provided at the inlet 71 of the water to be treated of the cartridge polisher 7.

  The reactant container 22 has a reactant holding part 24 having a reactant filling region 23. The reactant holding unit 24 and the internal configuration thereof are the same as the reactant holding unit 24 and the internal configuration of the first embodiment. On the other hand, the reactant container 22 of the present embodiment does not have the upper lid 26 and the bottom lid 28 in the first embodiment. Refer to the description of the first embodiment for the configuration of the reactant container 22 not described below.

  The reactant container 22 has a flow path or through hole 34 having an inlet opening 37 and an outlet opening 38 through which water to be treated can communicate. The cartridge polisher 7 has a second flange 72 at the inlet 71 of the water to be treated, and the reactant container 22 includes the third flange 14 and the second flange 72 connected to the inlet pipe 10 of the water to be treated. The first flange 39 is located between the two. The second flange 72 is connected to the tip of the inlet nozzle wall 76 that rises from the main body of the cartridge polisher 7. A cylindrical wall 42 is provided between the inlet nozzle wall 76 and the reactant holder 24, and the first flange 39 is connected to the tip of the cylindrical wall 42. The first flange 39 and the cylindrical wall 42 may be integrally formed, or may be formed by joining separate members. Moreover, the cylindrical wall 42 and the reactant holding part 24 may be integrally formed, or may be formed by joining separate members. The third flange 14 is a part of the manhole 15 of the cartridge polisher 7, but may be a flange of the inlet pipe 10 itself. The first flange 39 is fastened together with the second and third flanges 72 and 14 by fastening means 29 such as bolts and nuts. The reactant container 22 (reactor 21) is suspended inside the cartridge polisher 7 in the vicinity of the inlet of the cartridge polisher 7 by the first flange 39 being supported on the second flange 72. Although the differential pressure is applied between the inlet opening 37 and the outlet opening 38, the reactant container 22 does not receive the system pressure of the ultrapure water production apparatus 101, and thus can have a very thin structure. Although the reactant container 22 of this embodiment is formed of stainless steel, it can also be formed of resin.

The reactant container 22 is filled with Pd monolith M. In this embodiment, since the reactant container 22 is provided in the upper space of the cartridge polisher 7, a dedicated installation area is not required. For this reason, the installation area and cost of the whole ultrapure water production apparatus 101 can be reduced. In particular, according to the present embodiment, the existing cartridge polisher 7 can be modified to provide the reactant container 22. In the cartridge polisher 7 before the reactant container 22 is provided, the second flange 72 and the third flange 14 are directly fastened by the fastening means 43 . Since the first flange 39 of the reactant container 22 is provided with bolt holes at the same positions as the second and third flanges 72 and 14, it is only necessary to replace the first flange 39 with a longer bolt if necessary. Since the reactant container 22 has a cylindrical shape, it can be easily accommodated in the cylindrical cartridge polisher 7, and the first flange 39 is the same as the second and third flanges 72 and 14. It is also easy to have a ring shape.

(Monolith filling method)
Next, a monolith filling method characteristic of the present invention will be described. The monolith filling method described below is common to the first embodiment and the second embodiment. As shown in FIG. 2, in these embodiments, the diameter of the virtual circle 411 having the smallest radius including the reactant filling region 23 around the central axis CL of the reactant container 22 is D1, and the reactant filling region When the filling height of the Pd monolith in the flow path direction filled in 23 is H1, D1 / H1 ≧ 1. Further, D / H ≧ 1 when D is the diameter of the virtual circle 41 having the smallest radius including all the through holes 34 and H is the height of the through hole 34 in the flow path direction or the axial direction. . Usually, the diameter D of the imaginary circle 41 matches or is approximately equal to the diameter D1 of the imaginary circle 411, while the filling height H1 of the Pd monolith is smaller than the height H of the through-hole 34, so that D / H ≧ 1 is satisfied. If so, D1 / H1 ≧ 1 is satisfied. In this embodiment, the diameter D of the virtual circle 41 matches the diameter D1 of the virtual circle 411.

  As described above, the monolithic ion exchanger can be processed at a higher flow rate than the granular ion exchanger. However, a differential pressure corresponding to the flow velocity is generated, and the differential pressure is larger than that of the granular ion exchanger. In order to effectively use the characteristics of the monolithic ion exchanger, it is desirable that the reactant filling region 23 has a flat shape that satisfies the condition of D1 / H1 ≧ 1, and for this purpose, the reactant holding unit 24 has the D / H A flat shape satisfying the condition of ≧ 1 is desirable. That is, it is desirable that the filling height H1 of the monolithic ion exchanger be as low (thin) as possible within a range where a predetermined treatment can be performed to suppress the differential pressure. On the other hand, in order to ensure SV (space velocity: the value obtained by dividing the flow rate by the cross-sectional area of the flow path), it is desirable to increase the plane area of the reactant filling region 23. For this reason, when there is much processing amount (water flow volume), it is desirable to enlarge the diameter of the reactant filling area | region 23 and to increase an internal water flow cross-sectional area. In that case, as shown in FIG. 5, it is also preferable to provide a plurality of reactant containers 22 in parallel.

  In the present invention, a monolithic ion exchanger carrying a platinum group metal such as Pd is preferably used, but a granular ion exchanger carrying a platinum group metal such as Pd can also be used. The granular ion exchanger has a longer ion exchange zone length than the monolithic ion exchanger. Since the hydrogen peroxide removal performance equivalent to that of Pd monolith can be obtained by increasing the layer thickness of Pd resin, for example, it is possible to use a granular ion exchanger in the second embodiment. However, there is a limit to increasing the layer thickness due to problems such as installation space of the apparatus.

  Since the reactant container 22 has a circular cross section, the diameters D and D1 are used in the above description, but the shape of the reactant container 22 is not limited to this, and may be any shape. Can be taken. When the reactant container 22 has a cross section other than a circle, for example, an equivalent circle diameter D having the same area as the inner space of the reactant holder 24 can be used.

  In order to obtain the desired hydrogen peroxide removal performance, it is desirable that the filling height H1 of the Pd monolith is at least 10 mm. The height of the reactant holding part 24 (height H of the through hole) may be the same as the filling height H1 of the Pd monolith, but the height of the reactant holding part 24 may be larger. The height of the reactant holder 24 is 10 to 1000 mm, preferably 50 to 500 mm, and more preferably 100 to 300 mm. When the height of the reactant holding part 24 becomes larger than the filling height H1 of the Pd monolith, the reactant container 22 becomes larger and the material cost increases. Furthermore, since it becomes a large-sized heavy article, handling property falls. The outer diameter of the reactant holder 24 is 50 to 1100 mm, preferably 100 to 900 mm.

The arrangement pattern of the Pd monolith M is not limited to that shown in FIGS. 2 and 4, but the value (packing rate) obtained by dividing the area of the reactant filling region 23 by the area of the virtual circle 41 in the above-described channel cross section is 0.3. The above is desirable. As the filling rate is higher, the reactant container 22 can be reduced in size and weight. In the example of FIG. 2B, the outer shape of the Pd monolith M is about 140 mm, and the diameter of the virtual circle 41 is about 450 mm. Therefore, the area of the ion exchanger filling region 23 is 7 × π × 70 ² = about 107760 mm ² , the area of the virtual circle 41 is π × 225 ² = about 159040 mm ² , and the filling rate is about 68%.

(About monolithic ion exchangers)
Next, the monolithic ion exchanger commonly used in the first and second embodiments will be described in more detail. As described above, the monolithic ion exchanger is a porous ion exchanger having a continuous pore structure. FIG. 8 shows a conceptual diagram thereof. As the monolithic ion exchanger, a monolith anion exchanger is preferably used, and in particular, A-type and B-type monolith anion exchangers described below are preferably used. In particular, a Pd monolith carrying Pd can decompose hydrogen peroxide in water, and can also decompose dissolved oxygen under the coexistence conditions with hydrogen. Pd monolith has higher hydrogen peroxide decomposition performance than granular Pd resin. Since Pd is a catalyst, the Pd monolith has a catalytic function rather than an ion exchange function, and can be used for a long time.

(A type monolith anion exchanger)
The A-type monolith anion exchanger is obtained by introducing an anion exchange group into the monolith, and the macropores in the form of bubbles overlap each other, and the overlapping portion has an average diameter of 30 to 300 μm, preferably 30 when wet. A continuous macropore structure having an opening (mesopore) of ˜200 μm, particularly preferably 40˜100 μm. The average diameter of the A-type monolith anion exchanger opening is larger than the average diameter of the monolith opening because the entire monolith swells when an anion exchange group is introduced into the monolith. If the average diameter of the openings in the water-wet state is less than 30 μm, the pressure loss during water flow increases, which is not preferable. If the average diameter of the openings in the water-wet state is too large, the water to be treated and A The contact between the monolith anion exchanger of the type and the supported platinum group metal nanoparticles becomes insufficient, and as a result, the hydrogen peroxide decomposition property is lowered, which is not preferable. The average diameter of the openings of the A-type monolith anion exchanger in the water wet state is a value calculated by multiplying the average diameter of the openings of the A-type monolith in the dry state or the monolith anion exchanger by the swelling ratio. The average diameter of the openings of the dried monolith anion exchanger is measured by the mercury intrusion method. The mercury intrusion method is a method for obtaining a specific surface area and pore distribution from the pressure and the amount of injected mercury by applying pressure to intrude mercury into pores by utilizing the high surface tension of mercury. The swelling rate is 1.4 to 1.9. In the A-type monolith anion exchanger, in the SEM image of the cut surface of the continuous macropore structure, the skeleton part area appearing in the cross section is 25 to 50%, preferably 25 to 45% in the image region. When the area of the skeletal part appearing in the cross section is less than 25% in the image region, the skeleton becomes a thin skeleton, the mechanical strength is lowered, and the monolith anion exchanger is greatly deformed particularly when water is passed at a high flow rate. Therefore, it is not preferable. Furthermore, the contact efficiency between the water to be treated and the A-type monolith anion exchanger and the platinum group metal nanoparticles supported thereon is lowered, and the catalytic effect is lowered, which is not preferable. If it exceeds 50%, the skeleton becomes thick. This is not preferable because the pressure loss during water passage increases.

  The total pore volume of the A type monolith anion exchanger is 0.5 to 5 ml / g, preferably 0.8 to 4 ml / g. If the total pore volume is less than 0.5 ml / g, the pressure loss during water flow will increase, which is not preferable. Furthermore, the amount of permeated fluid per unit cross-sectional area decreases, and the processing capacity decreases. Therefore, it is not preferable. On the other hand, if the total pore volume exceeds 5 ml / g, the mechanical strength is lowered, and the A-type monolith anion exchanger is greatly deformed particularly when water is passed at a high flow rate. Furthermore, the contact efficiency between the water to be treated, the A-type monolith anion exchanger and the platinum group metal nanoparticles supported thereon is lowered, and the catalytic effect is also lowered, which is not preferable.

  The pressure loss when water is permeated through the A-type monolith anion exchanger is expressed as the pressure loss when water is passed through a column packed with 1 m at a water flow velocity (LV) of 1 m / h. A range of 0.001 to 0.1 MPa / m · LV, particularly 0.005 to 0.05 MPa / m · LV is preferable.

(B type monolith anion exchanger)
The B type monolith anion exchanger has an average thickness composed of an aromatic vinyl polymer containing 0.3 to 5.0 mol% of a cross-linking structural unit in all the structural units into which an anion exchange group has been introduced. A co-continuous structure comprising a three-dimensionally continuous skeleton of 1 to 60 μm and three-dimensionally continuous pores having an average diameter of 10 to 100 μm in a wet state between the skeletons. The volume is 0.5 to 5 ml / g, the ion exchange capacity per volume under water wet condition is 0.3 to 1.0 mg equivalent / ml, and the anion exchange group is uniform in the porous ion exchanger. Is distributed.

  The B-type monolith anion exchanger has a three-dimensional continuous skeleton having an average thickness of 1 to 60 μm, preferably 3 to 58 μm in an wet state in which an anion exchange group is introduced, and an average diameter between the skeletons. A co-continuous structure composed of three-dimensionally continuous pores of 10 to 100 μm, preferably 15 to 90 μm, particularly preferably 20 to 80 μm in a wet state. That is, the co-continuous structure is a structure in which a continuous skeleton phase and a continuous vacancy phase are intertwined and both are three-dimensionally continuous. These continuous vacancies have higher continuity of the vacancies than the conventional open-cell monolith and particle aggregation monolith, and the size of the vacancies is not biased, so that extremely uniform ion adsorption behavior can be achieved. Moreover, since the skeleton is thick, the mechanical strength is high.

  The average diameter of the pores of the continuous structure in the water-wet state is a value calculated by multiplying the average diameter of the pores of the dry monolith or monolith anion exchanger measured by the mercury intrusion method and the swelling ratio. is there. The swelling rate is 1.4 to 1.9. The average thickness of the skeleton of the continuous structure in the wet state is determined by performing SEM observation of a dry B-type monolith or monolith anion exchanger at least three times, and measuring the thickness of the skeleton in the obtained image. The average value is calculated by multiplying the swelling ratio. The skeleton has a rod-like shape and a circular cross-sectional shape, but may have a cross-section with a different diameter such as an elliptical cross-sectional shape.

  The total pore volume of the B type monolith anion exchanger is 0.5 to 5 ml / g. If the total pore volume is less than 0.5 ml / g, the pressure loss at the time of water flow is increased, which is not preferable. Further, the amount of permeated water per unit cross-sectional area is decreased, and the amount of treated water is decreased. Therefore, it is not preferable. On the other hand, if the total pore volume exceeds 5 ml / g, the anion exchange capacity per volume decreases, the amount of platinum group metal nanoparticles supported decreases, and the catalytic effect decreases. Further, the mechanical strength is lowered, and the B-type monolith anion exchanger is greatly deformed particularly when water is passed at a high flow rate, which is not preferable. Furthermore, the contact efficiency between the water to be treated and the B-type monolith anion exchanger decreases, and the hydrogen peroxide decomposition effect also decreases, which is not preferable. If the three-dimensional continuous pore size and total pore volume are within the above ranges, the contact with the water to be treated is extremely uniform, the contact area is large, and water can flow through under low pressure loss. Become. Note that the total pore volume of the monolith (monolith intermediate, monolith, monolith anion exchanger) is the same in both the dry state and the water wet state.

  The pressure loss when water is allowed to permeate through the B-type monolith anion exchanger is indicated by the pressure loss when water is passed through a column filled with 1 m of a porous body at a water flow rate (LV) of 1 m / h. And a range of 0.001 to 0.5 MPa / m · LV, particularly 0.005 to 0.1 MPa / m · LV.

(Catalyst metal carrier)
The catalyst metal carrier is formed by carrying a platinum group metal on a monolith anion exchanger, and is preferably a catalyst metal carrier having platinum group metal nanoparticles supported on the monolith anion exchanger.

  As the monolith anion exchanger, the above-described A and B type monolith anion exchangers are preferable.

  The platinum group metal is ruthenium, rhodium, palladium, osmium, iridium, or platinum. These platinum group metals may be used alone or in combination of two or more metals, and more than one metal may be used as an alloy. Among these, platinum, palladium, and platinum / palladium alloys have high catalytic activity and are preferably used.

  The average particle diameter of the platinum group metal nanoparticles is 1 to 100 nm, preferably 1 to 50 nm, and more preferably 1 to 20 nm. If the average particle size is less than 1 nm, the possibility that the nanoparticles are detached from the carrier increases, which is not preferable. On the other hand, if the average particle size exceeds 100 nm, the surface area per unit mass of the metal decreases and the catalytic effect. Is not preferred because it cannot be obtained efficiently. When the average particle diameter of the nanoparticles is within the above range, the nanoparticles are strongly colored by surface plasmon resonance and can be confirmed by visual observation.

  The amount of platinum group metal nanoparticles supported in the catalyst metal support in the dry state ((platinum group metal nanoparticles / dry platinum group metal supported catalyst) × 100) is 0.004 to 20% by weight, preferably 0. 0.005 to 15% by weight. If the supported amount of platinum group metal nanoparticles is less than 0.004% by weight, the effect of decomposing hydrogen peroxide is insufficient, which is not preferable.

  In the catalyst metal carrier, the ionic form of the monolith anion exchanger, which is the carrier of the platinum group metal nanoparticles, is usually a salt form such as a chloride form after the platinum group metal nanoparticles are supported. Such a salt form may be used as a catalyst for decomposing hydrogen peroxide. Further, the catalyst metal carrier may be one obtained by regenerating the ionic form of the monolith anion exchanger into the OH form. Of these, the ionic form of the monolith anion exchanger is preferably the OH form because a high catalytic effect is obtained. The method for regenerating the monolith anion exchanger after supporting the platinum group metal nanoparticles to the OH form is not particularly limited, and a known method such as passing a sodium hydroxide aqueous solution may be used.

DESCRIPTION OF SYMBOLS 1 Ultrapure water production apparatus 5 Ultraviolet oxidation apparatus 6 Hydrogen peroxide removal apparatus 7 Cartridge polisher 14 3rd flange 21 Reactor 22 Reactor container 23 Reactant filling area 24 Reactor holding part 26 Top cover 28 Bottom cover 29 Upper part holding Plate 30 Snap ring 31 Support plate 34 Flow path, through hole 37 Inlet opening 38 Outlet opening 39 First flange 41,411 Virtual circle 72 Second flange 73 Ion exchange resin filling portion CL Center line
M Monolithic ion exchanger D Diameter of virtual circle with minimum radius including all through holes D1 Diameter of virtual circle with minimum radius including reactant filling region H Height of through hole in flow direction or axial direction H1 Monolith filling height

Claims (3)

And a plurality of reactants that are monolithic ion exchangers filled in the reactant receptacle,
The reactant container is connected to a reactant holding portion having a plurality of through holes filled with the plurality of reactants, respectively, and an inlet connected to the upper peripheral edge of the reactant holding portion, to which treated water is supplied. An upper lid provided with a portion, and a bottom lid connected to a lower peripheral edge portion of the reactant holding portion, and having an outlet portion through which the water to be treated is discharged, each of the upper lid and the bottom lid being each A flange for sandwiching the reactant holding part, and connected to the pipe at the inlet part or the outlet part,
In the cross-section of the through-hole orthogonal to the through-hole, D / H ≧ 1 where D is the diameter of the smallest virtual circle containing the at least one through-hole and H is the length in the axial direction of the through-hole. And the value obtained by dividing the area of the filling region of the reactant in the at least one through hole by the area of the virtual circle is 0.3 or more. The reactants are monolithic ion exchanger platinum group metal catalyst is supported, the reactor according to claim 1. A water treatment apparatus comprising: the reactor according to claim 2; an ultraviolet oxidation apparatus positioned upstream of the reactor; and a non-regenerative ion exchange apparatus positioned downstream of the reactor.