JP6529793B2 - Method of treating liquid to be treated and treatment apparatus of liquid to be treated - Google Patents

Description

  The present invention relates to a catalyst-supporting porous body in which a catalyst is supported on a porous body, an object to be treated comprising water to be treated containing hydrogen peroxide, water to be treated containing dissolved oxygen, or an organic solvent such as isopropyl alcohol. The present invention relates to a method for treating a liquid to be treated that passes a liquid to be treated such as a treatment liquid, and a device for treating a liquid to be used for the method.

  The catalyst-supporting porous body, in which the catalyst is supported on the porous body, has a much larger specific surface area than a general particulate or planar catalyst support, and therefore, efficient contact with the process fluid is possible. It is. Therefore, it is used in various fields such as water treatment, exhaust gas treatment, and production of chemical substances.

  In the method of bringing the catalyst-supporting porous body, in which the catalyst is supported on the porous body, into contact with the fluid to be treated, generally, only the catalyst-supporting porous body is filled in the treatment container, and the catalyst-supporting porous body is formed. A method has been proposed in which the fluid to be treated is supplied to the body layer and allowed to pass through the catalyst-supporting porous body layer.

  For example, in Patent Document 1, there is a method in which a catalyst-supporting porous body in which a catalyst metal is supported on a pellet-like carrier made of porous fluorocarbon resin is filled in a treatment container, and the treatment liquid and the catalyst-supporting porous body are in contact. Proposed.

  Further, Patent Document 2 proposes a method in which a catalyst-supporting porous body in which a metal catalyst is plated on a porous body such as urethane foam is filled in a processing container, and a gas to be treated is brought into contact with the catalyst-supporting porous body. ing.

  Further, in Patent Document 3, a catalyst-supporting porous body in which an active metal and an organic carboxylic acid are supported on a porous support such as alumina or silica is filled in a container, and the gasoline to be treated is brought into contact with the catalyst-supporting porous body. A method has been proposed.

  Further, in Patent Document 4, a platinum group metal catalyst-supporting porous body in which a platinum group metal is supported on a monolith-like organic porous body or a monolith-like organic porous ion exchanger is cut out in the form of a packed column and treated in a processing vessel. A method has been proposed in which the water to be treated and the platinum group metal-supporting porous body are brought into contact with each other.

  In addition, as a method of removing hydrogen peroxide in ultrapure water, for example, Patent Document 5 discloses a particulate catalyst-supporting anion exchange resin formed by supporting a catalyst using an anion exchange resin as a carrier, and an anion exchange resin, A method is disclosed for relatively efficiently removing hydrogen peroxide by passing water to be treated containing hydrogen peroxide in a catalyst mixing tower having the

JP 7-8805 A JP-A-6-110162 Unexamined-Japanese-Patent No. 2003-286493 JP 2012-61455 A Patent No. 5649520 gazette

  In Patent Documents 1 to 3, only the catalyst-supporting porous body is filled in the treatment vessel, but when the gap between the catalyst-supporting porous bodies filled in the treatment vessel is wide, the fluid to be treated is There is a problem in that the processing efficiency is lowered because a short pass is made through the gap.

  In addition, as in Patent Document 4, when a monolithic organic porous body or monolithic organic porous ion exchanger on which a catalyst is supported is cut out in the shape of a packed column and inserted into the packed column, a short path is obtained. It can be prevented. However, it takes time and, in the case where the diameter of the packed column is very large, there is a problem that it is difficult to produce a monolithic organic porous body or monolithic organic porous ion exchanger having a suitable size. was there.

Further, as described in Patent Document 5, a catalyst mixing tower having a particulate catalyst-supporting anion exchange resin in which a catalyst is supported with an anion exchange resin as a carrier, and an anion exchange resin, to be treated with hydrogen peroxide By passing water through it, hydrogen peroxide can be removed relatively efficiently, but the particulate catalyst-supported anion exchange resin has a small specific surface area, so the processing capacity per unit flow rate is small, and impurities can also be removed. The amount of anion exchange resin is also large, so it is necessary to increase the amount of anion exchange resin to remove the eluate. Therefore, it is necessary to mix a catalyst-supported anion exchange resin at a ratio of 3 to 20% by weight with respect to the anion exchange resin, and there is a problem that the water flow rate needs to be SV = 10 to 200 h ^−1. there were.

  Therefore, the present invention provides a method for treating a liquid to be treated that can efficiently pass the liquid to be treated to the catalyst-supporting porous body in which the catalyst is supported on the porous body, and used therein It is providing the processing apparatus of a to-be-processed liquid.

Such problems as described above are solved by the present invention described below.
That is, the present invention (1) is a catalyst-supporting porous body comprising a catalyst-supporting porous body having a catalyst supported on a porous body, and a particulate ion exchange resin filling the space between the catalyst-supporting porous body. A method for treating a liquid to be treated, wherein the liquid to be treated is supplied to the packed bed, and the liquid to be treated is allowed to pass through the catalyst-supporting porous material packed bed,
The catalyst-supporting porous body is a platinum group metal-supporting monolithic organic porous body in which a platinum group metal catalyst is supported on a monolithic organic porous body, or a platinum group metal catalyst as a monolithic organic porous ion exchanger Being a supported platinum group metal supported monolithic organic porous ion exchanger;
In the catalyst-supported porous body packed bed, the ratio of the packed volume of the catalyst-supported porous body to the total of the packed volume of the catalyst-supported porous body and the packed volume of the particulate ion exchange resin is 25 to 67% by volume To be
The present invention provides a method of treating a liquid to be treated characterized by

Further, the present invention (2) has a treatment tower or a treatment vessel through which the liquid to be treated flows.
A catalyst-supporting porous body comprising a catalyst-supporting porous body in which a catalyst is supported on a porous body, and a particulate ion exchange resin filling the space between the catalyst-supporting porous body in the treatment tower or treatment vessel A packed bed is formed,
The catalyst-supporting porous body is a platinum group metal-supporting monolithic organic porous body in which a platinum group metal catalyst is supported on a monolithic organic porous body, or a platinum group metal catalyst as a monolithic organic porous ion exchanger Being a supported platinum group metal supported monolithic organic porous ion exchanger;
In the catalyst-supported porous body packed bed, the ratio of the packed volume of the catalyst-supported porous body to the total of the packed volume of the catalyst-supported porous body and the packed volume of the particulate ion exchange resin is 25 to 67% by volume To be
An apparatus for treating a liquid to be treated is provided.

  According to the present invention, it is possible to provide a method for treating water to be treated which can efficiently pass the water to be treated, wherein the catalyst-supporting porous material having a catalyst supported on the porous body can be used efficiently. An apparatus for treating water to be treated can be provided.

It is a typical end elevation of an embodiment of a processing device of a processed liquid of the present invention. It is a typical end elevation of an embodiment of a processing device of a processed liquid of the present invention. It is a typical end elevation of an embodiment of a processing device of a processed liquid of the present invention. It is a typical end elevation of an embodiment of a processing device of a processed liquid of the present invention. FIG. 2 is a conceptual view of a processing device used in Example 1; FIG. 14 is a conceptual view of a processing device used in Example 3; FIG. 16 is a conceptual view of a processing device used in Example 4;

  The processing method of the to-be-processed liquid of this invention and the processing apparatus of the to-be-processed liquid of this invention are demonstrated with reference to FIGS. 1 to 4 are schematic end views of embodiments of the apparatus for treating a liquid to be treated according to the present invention.

  In FIG. 1, the treatment apparatus 1a for the liquid to be treated has a catalyst-supporting porous body 6 in which a catalyst is supported on a porous body in a treatment vessel 2, and a particulate ion exchange resin 7. A porous body packed bed 3 is formed. The catalyst-supporting porous material packed bed 3 is formed by being filled in the processing container 2 so as to form a mixed layer with a large number of cubic catalyst-supporting porous materials 6 and particulate ion exchange resins 7. There is. Then, in the catalyst-supporting porous material packed bed 3, a large number of catalyst-supporting porous materials 6 cut out in a cubic shape are packed in the flowing direction and the lateral direction, and between the catalyst-supporting porous materials 6 and the catalyst A granular ion exchange resin 7 is filled so as to fill the gap between the carrier porous body 6 and the processing vessel 2. In addition, a treatment liquid introduction pipe 10 for supplying a treatment liquid 21 into the treatment container 2 is attached to the inlet side, and the treatment support 2 has passed through the catalyst-supporting porous material filling layer 3. A treatment liquid discharge pipe 11 for discharging the treatment liquid, that is, the treatment liquid 22 to the outside of the container is attached. The catalyst-supporting porous material-containing layer 3 is formed at a predetermined position in the processing container 2 by the lower side being supported and held in position by the eye plates 12 disposed below the processing container 2. Be done.

  In FIG. 2, in the treatment apparatus 1b for the liquid to be treated, a catalyst-supporting porous material packed bed 3 composed of the catalyst-supporting porous body 6 and the granular ion exchange resin 7 is formed in the treatment container 2. And, the inflow side granular ion exchange resin layer 4 made of granular ion exchange resin 7 is provided on the inflow side of the liquid to be treated of the catalyst-supporting porous material packed bed 3. The catalyst-supporting porous material packed bed 3 in the treatment apparatus 1b for treated liquid is the same as the catalyst-supported porous body packed layer 3 in the treatment apparatus 1a for treated liquid. The inflow side granular ion exchange resin layer 4 is formed by being filled in the processing container 2 so that the granular ion exchange resin 7 becomes a layer.

  In FIG. 3, in the treatment apparatus 1c for the liquid to be treated, a catalyst-supporting porous material filled layer 3 composed of the catalyst-supporting porous body 6 and the particulate ion exchange resin 7 is formed in the treatment container 2. And, on the outflow side of the liquid to be treated of the catalyst-supporting porous material packed bed 3, an outflow side granular ion exchange resin layer 5 composed of granular ion exchange resin 7 is provided. The catalyst-supporting porous material packed bed 3 in the treatment apparatus 1c for the treatment liquid is the catalyst-supporting porous material packed bed 3 in the treatment apparatus 1a for the treatment liquid and the catalyst-supporting porous material in the treatment apparatus 1b for the treatment liquid It is similar to the body packed bed 3.

  In FIG. 4, in the treatment apparatus 1 d for the liquid to be treated, a catalyst-supporting porous material filled layer 3 composed of the catalyst-supporting porous body 6 and the particulate ion exchange resin 7 is formed in the treatment container 2. And, the inflow side granular ion exchange resin layer 4 consisting of granular ion exchange resin 7 is provided on the inflow side of the liquid to be treated of the catalyst support porous body packed layer 3, and the catalyst support porous body filled On the outflow side of the liquid to be treated of the layer 3, an outflow side granular ion exchange resin layer 5 composed of granular ion exchange resin 7 is provided. The catalyst-supporting porous material packed bed 3 in the treatment apparatus 1 d for treated liquid is the catalyst-supported porous body packed bed 3 in the treatment apparatus 1 a for treated fluid, the catalyst-supporting porous material in the treatment apparatus 1 b for treated liquid It is the same as the catalyst loading porous body filling layer 3 in the body filling layer 3 and the treatment apparatus 1c of the treatment liquid, and the inflow side granular ion exchange resin layer 4 in the treatment apparatus 1d of the treatment liquid is the treatment subject It is the same as the inflow side granular ion exchange resin layer 4 in the treatment apparatus 1b of the treatment liquid, and the outflow side granular ion exchange resin layer 5 in the treatment apparatus 1d of the treatment liquid is in the treatment apparatus 1c of the treatment liquid. Is the same as the outflow side granular ion exchange resin layer 5 of

  In the catalyst-supporting porous body 6 and the particulate ion exchange resin 7, the particulate ion exchange resin 7 has a larger pressure loss. Therefore, in the treatment apparatus 1a, 1b, 1c, 1d of the liquid to be treated, the portion of the catalyst-supporting porous material packed bed 3 where the catalyst-supporting porous body 6 is present and the particulate ion exchange resin 7 are filled. As compared with the portion being treated, the liquid to be treated hardly flows to the portion filled with the particulate ion exchange resin 7, and most of the liquid to be treated flows inside the catalyst-supporting porous body 6. As a result, in the apparatus for treating liquid to be treated 1a, 1b, 1c and 1d, most of the liquid to be treated flows in the catalyst-supporting porous body 6 on which the catalyst is supported. Since a short pass in which the liquid to be treated flows is unlikely to occur, the liquid to be treated can be treated efficiently.

In the method for treating a liquid to be treated according to the present invention, a catalyst-supporting porous body comprising a catalyst-supporting porous body having a catalyst supported on a porous body, and a particulate ion exchange resin filling the space between the catalyst-supporting porous body. A method for treating a liquid to be treated, wherein the liquid to be treated is supplied to the porous material-packed layer, and the liquid to be treated is allowed to pass through the catalyst-supporting porous material-filled layer
The catalyst-supporting porous body is a platinum group metal-supporting monolithic organic porous body in which a platinum group metal catalyst is supported on a monolithic organic porous body, or a platinum group metal catalyst as a monolithic organic porous ion exchanger Being a supported platinum group metal supported monolithic organic porous ion exchanger;
A method of treating a liquid to be treated characterized by

  The catalyst-supporting porous material packed bed according to the method for treating a liquid to be treated of the present invention comprises two or more catalyst-supporting porous materials in which a catalyst is supported on a porous material, and a particulate ion exchange resin. The catalyst-supporting porous material packed bed comprises two or more catalyst-supporting porous bodies and particulate ion exchange resins, and in many cases, a large number of catalyst-supporting porous bodies and particulate ion exchange resins as mixed layers. As such, it is formed by being packed in a processing tower or a processing vessel. And, in the catalyst-supporting porous material packed bed, the catalyst-supporting porous material is packed in the liquid passing direction and the lateral direction, and between the catalyst-supporting porous materials, the catalyst-supporting porous material and the treatment tower or treatment vessel. Granular ion exchange resin is filled so as to fill gaps between the catalyst-supporting porous bodies and between the catalyst-supporting porous bodies and the processing tower or the processing vessel.

  The catalyst-supported porous body according to the method for treating a liquid to be treated of the present invention is a platinum group metal-supported monolithic organic porous body or a platinum group metal-supported monolithic organic porous ion exchanger. In particular, for the removal of hydrogen peroxide and dissolved oxygen contained in water produced in various processes in the production process of ultrapure water and pure water for cleaning the surface of electronic parts for semiconductors and equipment for manufacturing semiconductor electronic parts A platinum group metal supported monolithic organic porous body and a platinum group metal supported monolithic organic porous ion exchanger, wherein a platinum group metal catalyst is supported on a monolithic organic porous body or a monolithic organic porous ion exchanger It is suitable. The platinum group metal-supported monolithic organic porous material and the platinum group metal-supported monolithic organic porous ion exchanger will be described below.

<Platinum Group Metal-Supported Monolith-Like Organic Porous Body, Platinum Group Metal-Supported Monolith-Like Organic Porous Ion Exchanger>
The platinum group metal-supported monolithic organic porous material is a platinum group metal-supported catalyst in which fine particles of platinum group metal having an average particle diameter of 1 to 1000 nm are supported on the monolithic organic porous material. In addition, the platinum group metal-supported monolithic organic porous ion exchanger is a platinum group metal-supported catalyst in which fine particles of platinum group metal having an average particle diameter of 1 to 1000 nm are supported on the monolithic organic porous ion exchanger. .

  The monolithic organic porous body is a porous body having a skeleton formed of an organic polymer and having a large number of communicating holes serving as a flow path of water to be treated between the skeletons. In addition, the monolithic organic porous ion exchanger is a porous body in which ion exchange groups are introduced into the monolithic organic porous body.

  As a platinum group metal supported monolithic organic porous body in which a platinum group metal is supported on a monolithic organic porous body, fine particles of platinum group metal having an average particle diameter of 1 to 1000 nm are supported on a monolithic organic porous body The monolithic organic porous body is composed of a continuous framework phase and a continuous pore phase, the thickness of the continuous framework is 1 to 100 μm, the average diameter of the continuous pores is 1 to 1000 μm, and the total pore volume is 0. The platinum group metal-supported monolithic organic porous body, which has a loading amount of platinum group metal of 0.004 to 20% by weight in a dry state, can be mentioned.

  In addition, as a platinum group metal-supported monolithic organic porous ion exchanger in which a platinum group metal is supported on a monolithic organic porous ion exchanger, the monolithic organic porous ion exchanger has an average particle diameter of 1 to 1000 nm. The fine particles of platinum group metals are supported, and the monolithic organic porous ion exchanger is composed of a continuous framework phase and a continuous pore phase, the thickness of the continuous framework is 1 to 100 μm, and the average diameter of the continuous pores is 1 The total pore volume is 0.5 to 50 mL / g, the ion exchange capacity per weight in dry condition is 1 to 6 mg equivalent / g, and the ion exchange group is in the organic porous ion exchanger A uniformly distributed, platinum group metal-supported monolithic organic porous ion exchanger can be mentioned, wherein the supported amount of platinum group metal is 0.004 to 20% by weight in a dry state.

  The average diameter of the pores of the platinum group metal-supported monolithic organic porous material or the platinum group metal-supported monolithic organic porous ion exchanger is measured by mercury porosimetry, and a pore distribution curve obtained by mercury porosimetry Points to the maximum value of The structure of the platinum group metal-supported monolithic organic porous material or the platinum group metal-supported monolithic organic porous ion exchanger and the thickness of the continuous skeleton can be determined by SEM observation. The particle diameter of the platinum group metal particles supported by the platinum group metal-supported monolithic organic porous material or the platinum group metal-supported monolithic organic porous ion exchanger can be determined by TEM observation.

  Hereinafter, in the present specification, “monolith-like organic porous body” is simply referred to as “monolith”, and “monolith-like organic porous ion exchanger” is simply referred to as “monolith ion exchanger”, and an intermediate in the production of monolith The body (precursor) "monolith like organic porous intermediate" is also referred to simply as "monolith intermediate".

  Examples of the structure of the monolith or monolith ion exchanger as described above include the open cell structure disclosed in JP-A-2002-306976 and JP-A-2009-62512, and JP-A-2009-67982. Examples of the co-continuous structure that has been described, the particle aggregation type structure disclosed in JP 2009-7550 A, and the particle composite type structure disclosed in JP 2009-108294 A, and the like.

  The thickness of the continuous framework in the dry state of the monolith or monolithic ion exchanger on which the platinum group metal is supported is 1 to 100 μm. If the thickness of the continuous framework of the monolith or monolith ion exchanger is less than 1 μm, the mechanical strength is lowered, and the monolith or monolith ion exchanger will be largely deformed particularly when passing at a high flow rate, which is preferable. Absent. Furthermore, the contact efficiency between the liquid to be treated and the monolith or monolith ion exchanger is lowered, and the catalyst activity is unfavorably lowered. On the other hand, when the thickness of the continuous framework of the monolith or monolithic ion exchanger exceeds 100 μm, the framework becomes too thick, which is not preferable because the pressure loss at the time of passing the solution increases.

  The average diameter of the continuous pores in the dry state of the monolith or monolithic ion exchanger on which the platinum group metal is supported is 1 to 1000 μm. If the average diameter of the continuous pores of the monolith or monolith ion exchanger is less than 1 μm, the pressure loss at the time of flow becomes large, which is not preferable. On the other hand, when the average diameter of the continuous pores of the monolith or monolith ion exchanger exceeds 1000 μm, the contact between the liquid to be treated and the monolith or monolith ion exchanger becomes insufficient and the catalyst activity is unfavorably reduced.

  The ion exchange group introduced into the monolithic ion exchanger on which the platinum group metal is supported is a cation exchange group or an anion exchange group. As a cation exchange group, a carboxyl group, an iminodiacetic acid group, a sulfonic acid group, a phosphoric acid group, a phosphoric acid ester group etc. are mentioned. As an anion exchange group, quaternary ammonium groups such as trimethyl ammonium group, triethyl ammonium group, tributyl ammonium group, dimethyl hydroxyethyl ammonium group, dimethyl hydroxypropyl ammonium group, methyl dihydroxyethyl ammonium group, etc., tertiary sulfonium group, phosphonium group Etc.

  The above monolith, that is, an example of the monolith form supporting the platinum group metal particles (hereinafter, also described as monolith (1)) and the above monolith ion exchanger, that is, the monolith ion exchange member serving as the support of platinum group metal particles Examples of the form of (hereinafter, also described as monolith ion exchanger (1)) include monoliths and monolith ion exchangers having a co-continuous structure disclosed in JP-A-2009-67982. That is, the monolith (1) to be a carrier of the platinum group metal particles is a monolith before the ion exchange group is introduced, and an aroma containing 0.1 to 5.0% by mole of a crosslinking structural unit in all the structural units. Consisting of a three-dimensionally continuous framework with an average thickness of 1 to 60 μm in a dry state and an average diameter of 10 to 200 μm in a dry condition between the frameworks. It is a monolith which is a co-continuous structure and is an organic porous body having a total pore volume in a dry state of 0.5 to 10 mL / g. In addition, the monolithic ion exchanger (1) serving as a support for platinum group metal particles has a dry average thickness of an aromatic vinyl polymer containing 0.1 to 5.0 mol% of crosslinking structural units in all constituent units. A co-continuous structure consisting of a three-dimensionally continuous framework of 1 to 60 μm in the state and three-dimensionally continuous pores of 10 to 200 μm in the dry state in average diameter between the skeletons, the dry state Total pore volume at 0.5 to 10 mL / g, having ion exchange groups, and having a dry ion exchange capacity per weight of 1 to 6 mg equivalent / g; A monolithic ion exchanger uniformly distributed in the organic porous ion exchanger.

  The monolith (1) or monolith ion exchanger (1) to be a carrier of platinum group metal particles has a three-dimensionally continuous skeleton having an average thickness of 1 to 60 μm, preferably 3 to 58 μm in a dry state, and its skeleton In the meanwhile, it is a co-continuous structure composed of three-dimensionally continuous pores having an average diameter of 10 to 200 μm, preferably 15 to 180 μm, and particularly preferably 20 to 150 μm in a dry state. The co-continuous structure is a structure in which a continuous framework phase and a continuous vacancy phase are intertwined and each is continuous in three dimensions. The continuous pores have high continuity of pores and no deviation in size as compared with the conventional open cell monolith and particle aggregation monolith. In addition, the mechanical strength is high because the skeleton is thick.

  The average diameter of the opening of the monolith (1) in the dry state, the average diameter of the opening of the monolith ion exchanger (1) and the empty state of the monolith intermediate (1) in the dry state obtained by the treatment I of the preparation of the monolith described below The mean diameter of the pores is measured by mercury porosimetry and refers to the maximum value of the pore distribution curve obtained by mercury porosimetry. In addition, the average thickness of the monolith (1) or the monolithic ion exchanger (1) in the dried state can be determined by SEM observation of the dried monolith (1) or the monolithic ion exchanger (1). Specifically, SEM observation of dry monolith (1) or monolith ion exchanger (1) is performed at least three times, and the thickness of the skeleton in the obtained image is measured, and their average value is averaged. I assume. In addition, although frame | skeleton is rod-shaped and is circular cross-sectional shape, you may include the thing of different diameter cross sections, such as elliptical cross-sectional shape. The thickness in this case is the average of the minor axis and the major axis.

  In addition, the total pore volume per weight of the monolith (1) or the monolith ion exchanger (1) as a carrier of platinum group metal particles in a dry state is 0.5 to 10 mL / g. If the total pore volume is less than 0.5 mL / g, the pressure loss at the time of passing will be large, which is not preferable, and furthermore, the amount of permeation per unit cross-sectional area will be small, and the throughput will be lowered. Unfavorable. On the other hand, when the total pore volume exceeds 10 mL / g, the mechanical strength is lowered, and the monolith or the monolith ion exchanger is largely deformed particularly when passing at a high flow rate, which is not preferable. Further, the contact efficiency between the reaction solution and the monolith (1) or the monolith ion exchanger (1) is lowered, and the catalyst efficiency is also lowered. When the three-dimensionally continuous pore size and total pore volume are in the above range, the contact with the reaction solution is extremely uniform, the contact area is large, and liquid passage is possible under low pressure loss. .

  In the monolith (1) or the monolith ion exchanger (1) serving as a carrier of platinum group metal particles, the material constituting the skeleton is 0.1 to 5 mol%, preferably 0.5 to 3.% of the total structural units. It is an aromatic vinyl polymer containing 0 mol% of crosslinking structural units and is hydrophobic. If the crosslinking structural unit is less than 0.1 mol%, mechanical strength is insufficient, which is not preferable. If it exceeds 5 mol%, the structure of the porous body tends to deviate from the co-continuous structure. The type of the aromatic vinyl polymer is not particularly limited, and examples thereof include polystyrene, poly (α-methylstyrene), polyvinyltoluene, polyvinylbenzyl chloride, polyvinylbiphenyl, polyvinylnaphthalene and the like. The polymer may be a polymer obtained by copolymerizing a single vinyl monomer and a crosslinking agent, or a polymer obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, and a blend of two or more polymers. It may be done. Among these organic polymer materials, styrene-divinylbenzene co-weights from the ease of formation of co-continuous structure, the ease of ion exchange group introduction and the high mechanical strength, and the high stability to acid or alkali. Preferred is coalescence or a vinylbenzyl chloride-divinylbenzene copolymer.

  In the monolithic ion exchanger (1) serving as a carrier of platinum group metal particles, the introduced ion exchange groups are uniformly distributed not only on the surface of the monolith but also inside the skeleton of the monolith. As used herein, "the ion exchange groups are uniformly distributed" means that the distribution of ion exchange groups is uniformly distributed on the surface and inside the skeleton at least on the order of μm. The distribution of ion exchange groups is easily confirmed using EPMA. In addition, when the ion exchange groups are uniformly distributed not only on the surface of the monolith but also inside the skeleton of the monolith, the physical and chemical properties of the surface and the interior can be made uniform, so that the durability against swelling and shrinkage is obtained. Improves the quality.

  The ion exchange group introduced into the monolithic ion exchanger (1) serving as a carrier of platinum group metal particles is a cation exchange group or an anion exchange group. As a cation exchange group, a carboxyl group, an iminodiacetic acid group, a sulfonic acid group, a phosphoric acid group, a phosphoric acid ester group etc. are mentioned. As an anion exchange group, quaternary ammonium groups such as trimethyl ammonium group, triethyl ammonium group, tributyl ammonium group, dimethyl hydroxyethyl ammonium group, dimethyl hydroxypropyl ammonium group, methyl dihydroxyethyl ammonium group, etc., tertiary sulfonium group, phosphonium group Etc.

  The monolithic ion exchanger (1) serving as a carrier for platinum group metal particles has an ion exchange capacity per dry weight of 1 to 6 mg equivalent / g of ion exchange capacity. Since the monolithic ion exchanger (1) has high continuity and uniformity of three-dimensionally continuous pores, the pressure loss does not increase so much even if the total pore volume is reduced. Therefore, the ion exchange capacity per volume can be dramatically increased while keeping the pressure loss low. When the ion exchange capacity per weight is in the above range, the environment around the catalyst active point, such as pH inside the catalyst, can be changed, thereby increasing the catalyst activity. When the monolithic ion exchanger (1) is a monolithic anion exchanger, an anion exchange group is introduced into the monolithic anion exchanger (1), and the anion exchange capacity per weight in the dry state is 1 to 6 mg. It is equivalent / g. When the monolithic ion exchanger (1) is a monolithic cation exchanger, a cation exchange group is introduced into the monolithic cation exchanger (1), and the cation exchange capacity per weight in dry state is 1 ~ 6 mg equivalent / g.

  Monolith (1) used as a support | carrier of platinum group metal particle is obtained by performing the manufacturing method of the monolith-like organic porous body currently disclosed by Unexamined-Japanese-Patent No. 2009-67982. That is, in the method, a water-in-oil emulsion is prepared by stirring a mixture of an oil-soluble monomer containing no ion exchange group, a surfactant and water, and then the water-in-oil emulsion is polymerized to obtain all pores. I. Treatment to obtain a monolithic organic porous intermediate of continuous macropore structure (hereinafter also referred to as monolith intermediate (1)) having a volume of more than 16 mL / g and not more than 30 mL / g, aromatic vinyl monomer, 0.3-5 mol% of a crosslinking agent, an aromatic vinyl monomer or a crosslinking agent is dissolved in an oil-soluble monomer having at least two or more vinyl groups in the molecule, but an aromatic vinyl monomer is polymerized and formed. Monoliths obtained by treatment II in which the mixture obtained in the treatment II is prepared, and the mixture obtained in treatment II is prepared by preparing a mixture consisting of an organic solvent and a polymerization initiator in which the polymer is not dissolved. Performed in the presence in the polymerization between body (1), comprising a III treatment, to obtain a monolith (1) is an organic porous material is a co-continuous structure.

  A platinum group metal is supported on the platinum group metal-supported monolithic organic porous material or the platinum group metal-supported monolithic organic porous ion exchanger. The platinum group metals are ruthenium, rhodium, palladium, osmium, iridium and platinum. One of these platinum group metals may be used alone, or two or more metals may be used in combination, and two or more metals 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 particles supported by the platinum group metal-supported monolithic organic porous material or the platinum group metal-supported monolithic organic porous ion exchanger is 1 to 1000 nm, preferably 1 to 200 nm, More preferably, it is 1 to 20 nm. If the average particle size is less than 1 nm, the platinum group metal particles are not likely to be detached from the carrier, which is not preferable. On the other hand, when the average particle size exceeds 200 nm, the surface area per unit mass of metal decreases, and the catalytic effect can not be obtained efficiently, which is not preferable. The average particle size of the platinum group metal particles can be determined by image analysis of a TEM image obtained by transmission electron microscopy (TEM) analysis.

  Supported amount of platinum group metal particles in platinum group metal supported monolithic organic porous body or platinum group metal supported monolithic organic porous ion exchanger ((platinum group metal particle / platinum group supported metal catalyst in dry state) × 100 ) Is 0.004 to 20% by weight, preferably 0.005 to 15% by weight. If the loading amount of the platinum group metal particles is less than 0.004% by weight, the catalytic activity becomes insufficient, which is not preferable. On the other hand, when the loading amount of platinum group metal particles exceeds 20% by weight, metal elution in water is observed, which is not preferable.

  There are no particular restrictions on the method for producing the platinum group metal-supported monolithic organic porous material or the platinum group metal-supported monolithic organic porous ion exchanger. By supporting fine particles of a platinum group metal on a monolith or monolithic ion exchanger by a known method, a platinum group metal-supported monolithic organic porous body or a platinum group metal-supported monolithic organic porous ion exchanger can be obtained . As a method for supporting a platinum group metal on a monolithic organic porous body or a monolithic organic porous ion exchanger, for example, the method disclosed in JP-A-2010-240641 can be mentioned. For example, the monolith ion exchanger in a dry state is immersed in a methanol solution of a platinum group metal compound such as palladium acetate, palladium ion is adsorbed to the monolith ion exchanger by ion exchange, and then it is contacted with a reducing agent to make palladium metal microparticles Is supported on a monolithic ion exchanger. Alternatively, the monolith ion exchanger is immersed in an aqueous solution of a platinum group metal compound such as a tetraamminepalladium complex, palladium ion is adsorbed to the monolith ion exchanger by ion exchange, and then the palladium metal particles are contacted with a reducing agent to make the palladium metal particles monolith ion It is a method of carrying on an exchange body.

  After the platinum group metal is supported on the monolithic organic porous body or monolithic organic porous ion exchanger, the resulting platinum group metal supported monolithic organic porous body or platinum group metal supported monolithic organic porous ion exchange is obtained The body can be cut into a predetermined shape and size to form a platinum group metal-supported monolithic organic porous body or a platinum group metal-supported monolithic organic porous ion exchanger for packing in a treatment tower or a treatment vessel. .

  The size of the catalyst-supporting porous body according to the method for treating a liquid to be treated of the present invention is not particularly limited, but the average apparent volume per one catalyst-supporting porous body is preferably 1 to 8000 μL, particularly preferably 1 1000 μL. When the average apparent volume per one catalyst-supporting porous body is in the above range, the effect of preventing a short pass is enhanced, and the treatment efficiency of the liquid to be treated is enhanced. The average apparent volume per one catalyst-supporting porous body is the apparent volume in a water-wet state, and is the apparent volume including the volume of pores in the catalyst-supporting porous body, that is, the catalyst The average apparent volume per supported porous body is one of the total volume of the volume of the skeleton forming the catalyst supported porous body at the time of loading and the volume of the pores formed in the catalyst supported porous body. It is an average value per piece.

  The shape of the catalyst-supporting porous body is not particularly limited, and examples thereof include a cube, a rectangular solid, and a sphere.

  The particulate ion exchange resin according to the method for treating a liquid to be treated according to the present invention is a particulate ion exchanger in which the substrate is a resin and a cation exchange group or anion exchange group is introduced into the resin. It is a gel type or MR type ion exchange resin. In the particulate ion exchange resin, a styrene-divinylbenzene copolymer is preferable as the resin in which the ion exchange group is introduced. The ion exchange group introduced into the particulate ion exchange resin is a cation exchange group or an anion exchange group. As a cation exchange group, a carboxyl group, an iminodiacetic acid group, a sulfonic acid group, a phosphoric acid group, a phosphoric acid ester group etc. are mentioned. As an anion exchange group, quaternary ammonium groups such as trimethyl ammonium group, triethyl ammonium group, tributyl ammonium group, dimethyl hydroxyethyl ammonium group, dimethyl hydroxypropyl ammonium group, methyl dihydroxyethyl ammonium group, etc., tertiary sulfonium group, phosphonium group Etc.

  As a particulate anion exchange resin, it has a quaternary ammonium group as a functional group, and a group bonded to the nitrogen atom of the ammonium group has strongly basic type I of only an alkyl group, and a quaternary ammonium group as a functional group. Examples thereof include strongly basic type II groups in which the group bonded to the nitrogen atom of the ammonium group is an alkyl group and an alkanol group, and weak basicity having the first to third amino groups as functional groups.

  The average particle size of the particulate ion exchange resin is preferably 0.2 to 1.0 mm, particularly preferably 0.4 to 0.8 mm. Also, the average apparent volume per particulate ion exchange resin is preferably 0.004 to 0.5 μL, particularly preferably 0.03 to 0.25 μL. The average apparent volume per granular ion exchange resin is the apparent volume in a water-wet state, and is an average value per volume of the skeleton forming the granular ion exchange resin at the time of filling. is there.

  Ratio of average apparent volume per particle of ion exchange resin to average apparent volume per particle of catalyst-supporting porous material (average apparent volume per particle of ion exchange resin of particulate / catalyst-supporting porous material) The average apparent volume per unit) is preferably 0.5 or less, particularly preferably 0.000001 to 0.1, and more preferably 0.00001 to 0.01. When the ratio of the average apparent volume per particle of the particulate ion exchange resin to the average apparent volume per particle of the catalyst-supporting porous body is in the above range, the effect of preventing the short path of the liquid to be treated is enhanced. .

  Even if the catalyst-supporting porous body is manufactured so that the average apparent volume is a predetermined volume, a large one is first manufactured, and it is cut or crushed so as to have a predetermined average apparent volume. It may be a

  In the catalyst-supporting porous body and the particulate ion exchange resin, the particulate ion exchange resin has a larger pressure loss. That is, when the catalyst-supporting porous body and the particulate ion exchange resin are respectively filled in the same treatment volume in the same treatment vessel and the treatment liquid is passed through the treatment vessel, the particulate ion exchange resin is filled. The pressure loss is larger in the case where the catalyst is loaded than in the case where the catalyst-supporting porous body is filled. The ratio of the pressure loss of the particulate ion exchange resin to the pressure loss of the catalyst-supporting porous body when water is passed is preferably 1.5 to 10, and particularly preferably 2 to 5. When the ratio of the pressure loss of the particulate ion exchange resin to the pressure loss of the catalyst-supporting porous body when water is passed is in the above range, the effect of preventing a short pass is enhanced. Even when a liquid other than water is passed, the pressure loss ratio is the same as when water is passed unless the viscosity is a very large liquid, so even when a liquid other than water is passed. The ratio of the pressure loss of the particulate ion exchange resin to the pressure loss of the catalyst-supporting porous material is preferably 1.5 to 10, particularly preferably 2 to 5.

  In the catalyst-supporting porous material packed bed, the ratio of the loading volume of the catalyst-supporting porous material to the total of the loading volume of the catalyst-supporting porous material and the loading volume of the particulate ion exchange resin (Packed volume of catalyst-supporting porous body + packed volume of particulate ion exchange resin)) × 100) is preferably 25 to 67% by volume, particularly preferably 50 to 67% by volume. In the case of a mixed layer of a particulate catalyst-supporting ion exchange resin in which a particulate ion exchange resin is used as a carrier and a particulate ion exchange resin as in Patent Document 5, a particulate catalyst-supporting ion exchange resin is used. If the ratio is too large, the elution amount of the substance eluted from the particulate catalyst-supporting ion exchange resin itself increases, so the amount of catalyst-supporting ion exchange resin can not be increased. On the other hand, when using a platinum group metal-supported monolithic organic porous body or a platinum group metal-supported monolithic organic porous ion exchanger as the catalyst-supporting porous body, the SV can be flowed largely, so the catalyst Even if the mixing ratio of the support porous body is large, it is possible to keep the amount of the substance eluted from the catalyst support porous body itself low. Therefore, in the catalyst-supporting porous material packed bed, the ratio of the loading volume of the catalyst-supporting porous body to the total of the loading volume of the catalyst-supporting porous body and the loading volume of the particulate ion exchange resin is 25 to 67% by volume, or 50 Even when the amount is up to 67% by volume, the amount of the substance eluted from the catalyst-supporting porous body itself is small, and the catalyst-supporting porous relative to the total of the packed volume of the catalyst-supporting porous body and the packed volume of the particulate ion exchange resin When the proportion of the filling volume of the matrix is preferably 25 to 67% by volume, particularly preferably 50 to 67% by volume, excellent processing performance is exhibited. Also, the ratio of the packed volume of the catalyst-supporting porous body to the total of the packed volume of the catalyst-supporting porous body and the packed volume of the particulate ion exchange resin does not have to be less than 25% by volume. Demonstrate excellent processing capacity. When the ratio of the filling volume of the catalyst-supporting porous body to the total of the filling volume of the catalyst-supporting porous body and the filling volume of the particulate ion exchange resin exceeds 67% by volume, the gaps between the catalyst-supporting porous bodies Since the amount of particulate ion exchange resin to be filled is insufficient, a short pass is likely to occur. The packed volume of the catalyst-supporting porous body is the total volume of the apparent volume of the catalyst-supporting porous body in the catalyst-supported porous body packed bed at the time of packing (water wet state). The packed volume of the catalyst-supported porous body is the sum of the apparent volumes of the catalyst-supported porous body before mixed and packed. Further, the filling volume of the particulate ion exchange resin means the total volume of the apparent volume of the particulate ion exchange resin and the particulate ion exchange resin in the catalyst-supporting porous material loading layer at the time of loading (water wet state) The sum of the total volume of The filling volume of the particulate ion exchange resin is a tapping volume measured by the tapping method of the particulate ion exchange resin before mixed loading. The measuring method of tapping volume of granular ion exchange resin by tapping method is as follows. Using a measuring cylinder whose volume is larger than the volume of the sample ion exchange resin, transfer the sample ion exchange resin to the measuring cylinder together with water, and add water sufficiently so that the sample ion exchange resin is below the water surface. Attach a rubber stopper about 30 mm in diameter to the end of the glass rod and tap the side of the measuring cylinder with the rubber stopper. This operation is repeated until the height of the sample ion exchange resin layer does not change, and the height of the sample ion exchange resin is read in units of ml. After shaking the sample ion exchange resin, again tap the side of the measuring cylinder with the rubber plug to read the height of the sample ion exchange resin layer in the unit of ml. This operation is repeated three times, and an average value is determined to be a tapping volume of the sample ion exchange resin.

  The thickness of the catalyst-supporting porous material packed bed is appropriately selected depending on the size and diameter of the treatment tower or treatment vessel, the type of liquid to be treated, the concentration of the treatment object, etc., preferably 10 mm or more, particularly preferably 30 mm. It is above. When the thickness of the catalyst-supporting porous material packed layer is too thin, there is a possibility that the liquid to be treated does not flow uniformly or a short pass may occur.

  The catalyst-supported porous material packed bed is formed in the treatment tower or treatment vessel. That is, the catalyst-supporting porous body and the particulate ion exchange resin are packed in the treatment tower or treatment container. In the treatment tower or treatment vessel, a supply pipe for the treatment liquid for supplying the treatment liquid into the treatment tower or treatment vessel, and a treatment liquid discharge pipe for discharging the treatment liquid to the outside of the treatment tower or treatment vessel It is attached.

  In the method of treating a liquid to be treated according to the present invention, the liquid to be treated is supplied to the catalyst-supporting porous body packed bed, and the liquid to be treated is allowed to pass through the catalyst-supporting porous body packed bed.

  Examples of the liquid to be treated include water to be treated containing hydrogen peroxide, water to be treated containing dissolved oxygen, and a liquid to be treated containing an organic solvent such as isopropyl alcohol. In particular, in the method for treating a liquid to be treated according to the present invention, various steps in the process of producing ultrapure water or pure water for cleaning the surface of electronic parts for semiconductors and tools for producing semiconductor electronic parts as the liquid to be treated Water containing hydrogen peroxide and water containing dissolved oxygen produced in the above can be mentioned, and the method of treating a liquid to be treated according to the present invention exhibits excellent effects in the treatment of these ultrapure water or pure water.

Although the supply rate of the liquid to be treated to the catalyst-supporting porous material packed bed is appropriately selected, the liquid to be treated contains hydrogen peroxide generated in various steps in the production process of ultrapure water and pure water. a water containing water or dissolved oxygen, to remove hydrogen peroxide or dissolved oxygen in the water to be treated, the space velocity of the water to be treated for the catalyst-carrying porous material packed layer, preferably a space velocity SV2000～20000h ^{- 1} , and more preferably SV 2000 to 10000 h ⁻¹ . The platinum group metal-supported monolithic organic porous material and the platinum group metal-supported monolithic organic porous ion exchanger intentionally have a water flow rate of less than SV 2000 h ⁻¹ because their ability to remove hydrogen peroxide and dissolved oxygen is extremely high. Although not required, it may be a water flow rate of less than SV2000h ^-1, even when the water flow rate less than SV2000h ^-1, exhibits excellent hydrogen peroxide and dissolved oxygen removability. On the other hand, when SV exceeds 20000 h ⁻¹ , the water flow differential pressure tends to be too large. In the present invention, the space velocity SV is the space velocity relative to the total packed volume of the catalyst support porous body packed in the catalyst support porous body packed bed.

  Then, in the method for treating a liquid to be treated according to the present invention, the liquid to be treated is supplied to the catalyst-supporting porous body packed bed, and the liquid to be treated is allowed to pass through the catalyst-supporting porous body packed bed. A treatment liquid is obtained by discharging the treatment liquid treated in the body packed bed.

The apparatus for treating water to be treated according to the present invention has a treatment tower or a treatment vessel through which the liquid to be treated flows.
A catalyst-supporting porous body comprising a catalyst-supporting porous body in which a catalyst is supported on a porous body, and a particulate ion exchange resin filling the space between the catalyst-supporting porous body in the treatment tower or treatment vessel A packed bed is formed,
The catalyst-supporting porous body is a platinum group metal-supporting monolithic organic porous body in which a platinum group metal catalyst is supported on a monolithic organic porous body, or a platinum group metal catalyst as a monolithic organic porous ion exchanger Being a supported platinum group metal supported monolithic organic porous ion exchanger;
It is a processing apparatus of the processed liquid characterized by the above.

  The treatment tower, the treatment vessel, the catalyst-supporting porous body, the particulate ion exchange resin, the catalyst-supporting porous body-packed layer, the treatment liquid, and the treatment liquid according to the treatment liquid of the present invention It is the same as the treatment tower, the treatment vessel, the catalyst-supporting porous body, the particulate ion exchange resin, the catalyst-supporting porous body packed bed, and the liquid to be treated according to the method.

  The catalyst-supporting porous body according to the method for treating a liquid to be treated of the present invention and the apparatus for treating a liquid to be treated according to the present invention is a platinum group metal supported monolithic organic porous body or a platinum group metal supported monolithic organic porous ion exchange Since it is a body, particulate ion exchange resin has a larger pressure loss than a catalyst-supporting porous body. Therefore, in the method for treating a liquid to be treated according to the present invention and the apparatus for treating a liquid to be treated according to the present invention, particulate ion exchange is carried out with the portion of the catalyst-support porous body packed layer where the catalyst-supporting porous body is present. In comparison with the part filled with resin, the part to be treated hardly flows in the part filled with the particulate ion exchange resin, so most of the part to be treated flows in the catalyst-supporting porous body. . As a result, in the method of treating a liquid to be treated according to the present invention and the apparatus for treating a liquid to be treated according to the present invention, most of the liquid to be treated flows in the catalyst-supporting porous body to form gaps between the catalyst-supporting porous bodies. Since the short pass through which the liquid to be treated flows is unlikely to occur, the liquid to be treated can be treated efficiently.

On the other hand, as in Patent Document 5, when a particulate catalyst-supported anion exchanger carrying a catalyst is used with a particulate anion exchange resin as a carrier, and a particulate anion exchange resin mixed, the particulate catalyst-carrying anion exchange resin And, in the particulate anion exchange resin, there is almost no difference in pressure drop when passing through. Therefore, the improvement in the treatment performance of the particulate catalyst-supported anion exchanger itself for the liquid to be treated by mixing the two can not be expected very much. However, it is known that the anion exchange resin can remove hydrogen peroxide if it is in the range of SV1 to 500 h ⁻¹ .

  Further, in the method of treating a liquid to be treated according to the present invention and the apparatus for treating a liquid to be treated according to the present invention, a particulate ion exchange resin is present between the catalyst-supporting porous bodies. Even if impurities such as ion components are eluted from the processing container or the like, the ion exchange function of the granular ion exchange resin can reduce the outflow of the impurities out of the system.

  In addition, when using a platinum group metal-supported monolithic organic porous body or a platinum group metal-supported monolithic organic porous ion exchanger as the catalyst-supporting porous body, the method for treating the liquid to be treated of the present invention and the present invention In the treatment apparatus for the liquid to be treated, even if the diameter of the treatment tower or treatment vessel is large, it is not necessary to produce a catalyst-supporting porous body of a size that fits the diameter, and an efficient size or a size that can suppress the production cost low. Since it is sufficient to produce the catalyst-supporting porous material of the present invention and cut it into a predetermined size, there arises a problem that it becomes difficult to produce a catalyst-supporting porous material of a size suitable for the diameter of a large treatment tower or treatment vessel. Absent.

  In the method of treating a liquid to be treated according to the present invention and the apparatus for treating a liquid to be treated according to the present invention, as in the embodiment shown in FIG. 2 and FIG. The provision of the inflow side granular ion exchange resin layer made of granular ion exchange resin makes it easier to uniformly supply the liquid to be treated to the catalyst-supporting porous material packed bed, thereby enhancing the treatment efficiency. Preferred.

  The particulate ion exchange resin according to the inflow side particulate ion exchange resin layer is the same as the particulate ion exchange resin according to the catalyst-supporting porous material packed bed. Further, as the particulate ion exchange resin according to the inflow side particulate ion exchange resin layer, the same particulate ion exchange resin as the particulate ion exchange resin according to the catalyst-supporting porous material packed bed may be used, or different particulate ion exchange resin Exchange resins may be used.

  In the method of treating a liquid to be treated according to the present invention and the apparatus for treating a liquid to be treated according to the present invention, as in the embodiment shown in FIG. 3 and FIG. It is provided that an outflow side granular ion exchange resin layer made of granular ion exchange resin is provided, and the outflow side granular ion exchange resin layer and the catalyst-supporting porous material packed layer are in contact with each other. It is preferable in that the prevention effect is enhanced, and thereby the processing efficiency is enhanced.

  The particulate ion exchange resin according to the outflow side particulate ion exchange resin layer is the same as the particulate ion exchange resin according to the catalyst-supporting porous material packed bed. Further, as the particulate ion exchange resin according to the outflow side particulate ion exchange resin layer, the same particulate ion exchange resin as the particulate ion exchange resin according to the catalyst-supporting porous material packed bed may be used, or different particulate ion exchange resin is used. Exchange resins may be used.

  Further, in the method for treating a liquid to be treated according to the present invention and the apparatus for treating a liquid to be treated according to the present invention, it is an object to remove impurity ions of water generated in various steps in the process of producing ultrapure water and pure water. By providing the catalyst-supporting porous material packed bed in the ion exchange resin column, it is possible to remove hydrogen peroxide and dissolved oxygen simultaneously with impurity ions. Further, as described above, it is more preferable that the catalyst-supporting porous material-containing layer be sandwiched between the particulate ion exchange resin layers on the inflow side and the outflow side of the liquid to be treated. In addition, since the catalyst-supporting porous body is a platinum group metal-supporting monolithic organic porous body and a platinum group metal-supporting monolithic-organic porous ion exchanger, the ability to remove hydrogen peroxide and dissolved oxygen is extremely high, and ion exchange The filling ratio of the catalyst-supporting porous body to the total packed amount of the resin tower may be much smaller than in the case of using a particulate catalyst-supporting ion exchange resin having a particulate ion exchange resin as a carrier and supporting the catalyst. Specifically, 1 to 5% by volume is preferable, and 2 to 4% by volume is particularly preferable as the packed volume of the catalyst-supporting porous body with respect to the total packed volume of the ion exchange resin tower.

  Hereinafter, the present invention will be described in detail based on examples. However, the present invention is not limited to the following examples.

<Production of platinum group metal (palladium) -supported monolithic organic porous ion exchanger A>
(Production of monolith intermediate (I treatment))
9.28 g of styrene, 0.19 g of divinylbenzene, 0.50 g of sorbitan monooleate (hereinafter abbreviated as SMO) and 0.25 g of 2,2'-azobis (isobutyronitrile) were mixed and uniformly dissolved. Next, the mixture of styrene / divinylbenzene / SMO / 2,2′-azobis (isobutyronitrile) is added to 180 g of pure water, and a vacuum stirring defoaming mixer (manufactured by EM Co., Ltd.) is a planetary stirring device. The mixture was stirred under reduced pressure using to give a water-in-oil emulsion. The emulsion was immediately transferred to a reaction vessel, sealed, and allowed to polymerize at 60 ° C. for 24 hours under standing conditions. After the polymerization was completed, the contents were taken out, extracted with methanol, and then dried under reduced pressure to produce a monolithic intermediate having a continuous macropore structure. The internal structure of the monolith intermediate (dry matter) thus obtained was observed by SEM. From the SEM image, although the wall part partitioning two adjacent macropores is very thin rod-like, it has an open cell structure, and the average of the openings (mesopores) in the portions where the macropores and the macropores overlap measured by mercury porosimetry The diameter was 40 μm and the total pore volume was 18.2 mL / g.

(Manufacture of monolith)
Next, 216.6 g of styrene, 4.4 g of divinylbenzene, 220 g of 1-decanol, and 0.8 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were mixed and uniformly dissolved (II treatment). Next, the monolith intermediate is placed in a reaction vessel, immersed in the mixture of styrene / divinylbenzene / 1-decanol / 2,2′-azobis (2,4-dimethylvaleronitrile), and defoamed in a vacuum chamber. The reaction vessel was sealed and allowed to stand still at 50 ° C. for 24 hours for polymerization. After completion of the polymerization, the contents were taken out, Soxhlet extracted with acetone, and then dried under reduced pressure (III treatment).
The internal structure of the monolith (dry matter) containing 1.2 mol% of the crosslinking component consisting of the styrene / divinylbenzene copolymer thus obtained was observed by SEM. From the SEM observation, it was found that the monolith was a three-dimensionally continuous skeleton and pore, and had a bicontinuous structure in which both phases were intertwined. Moreover, the average thickness of the skeleton measured from the SEM image was 20 μm. The average diameter of three-dimensionally continuous pores of the monolith measured by mercury porosimetry was 70 μm, and the total pore volume was 4.4 mL / g. The average diameter of the pores was determined from the maximum value of the pore distribution curve obtained by mercury porosimetry.

(Production of Monolith Anion Exchanger)
The monolith prepared by the above method is placed in a column-like reactor, and a solution consisting of 1600 g of chlorosulfonic acid, 400 g of tin tetrachloride and 2500 mL of dimethoxymethane is circulated and allowed to react for 5 hours at 30 ° C. Introduced. After completion of the reaction, the chloromethylated monolith was washed with a mixed solvent of THF / water = 2/1 and further washed with THF. To this chloromethylated monolith, 1600 mL of THF and 1400 mL of a 30% aqueous solution of trimethylamine were added, and reacted at 60 ° C. for 6 hours. After completion of the reaction, the product was washed with methanol and then with pure water to obtain a monolithic anion exchanger.
The anion exchange capacity of the obtained monolithic anion exchanger was 4.2 mg equivalent / g in a dry state, and it was confirmed that a quaternary ammonium group was quantitatively introduced. In addition, the thickness of the skeleton in the dry state measured from the SEM image is 20 μm, and the average diameter in the dry state of three-dimensionally continuous pores of the monolith anion exchanger is determined from the measurement by the mercury penetration method. Of 70 μm, and the total pore volume in the dry state was 4.4 mL / g.
Next, in order to confirm the distribution of quaternary ammonium groups in the monolithic anion exchanger, the monolithic anion exchanger was treated with an aqueous solution of hydrochloric acid to form a chloride type, and then the distribution of chloride ions was observed by EPMA. . As a result, the chloride ion is uniformly distributed not only on the skeleton surface of the monolithic anion exchanger but also on the inside of the skeleton, and it can be confirmed that the quaternary ammonium group is uniformly introduced into the monolithic anion exchanger. The

(Supporting platinum group metals)
The above monolith anion exchanger was ion-exchanged to the Cl form, then cut out in a cylindrical form in a dry state and dried under reduced pressure. The weight of the monolithic anion exchanger after drying was 2.1 g. The dried monolith anion exchanger was immersed in dilute hydrochloric acid in which 160 mg of palladium chloride was dissolved for 24 hours to ion-exchange into the form of palladium chloride. After completion of the immersion, the monolithic anion exchanger was washed with pure water several times, and immersed in a hydrazine aqueous solution for 24 hours to perform reduction treatment, whereby a palladium-supported monolithic anion exchanger A was obtained. While the palladium chloride type monolith anion exchanger was brown, the monolith anion exchanger after completion of the reduction treatment was colored black, suggesting the formation of palladium microparticles. The sample after reduction was washed with pure water several times and then dried under reduced pressure. The obtained dried palladium-loaded monolithic anion exchanger A was packed in a column, and an aqueous solution of sodium hydroxide was passed through to make the carrier, the carrier monolithic anion exchanger, in the form of OH.
The amount of palladium supported was determined by ICP emission spectrometry, and the amount of palladium supported was 3.9% by weight. In order to confirm the distribution of palladium supported on the monolithic anion exchanger, the distribution of palladium was observed by EPMA. It was confirmed that palladium was distributed not only on the framework surface of the monolithic anion exchanger but also on the inside of the framework, and although the concentration was slightly higher inside, it was relatively uniformly distributed. In addition, in order to measure the average particle diameter of the supported palladium particles, transmission electron microscope (TEM) observation was performed. The average particle size of the palladium fine particles was 8 nm.

The obtained palladium-supported monolithic anion exchanger was cut out and packed in a catalyst-packed column with an inner diameter of 57 mm. At this time, it cut out so that a volume might be set to 85 mL (water wet state). Next, ultrapure water was passed through so as to be SV 5000 h ⁻¹ , and the differential pressure was measured. The pressure loss was 20 kPa.

<Particulate ion exchange resin mixture A>
Granular cation exchange resin (AMBERJET 1024H, Rohm and Haas Japan Ltd., average diameter 0.6 to 0.7 mm, average apparent volume per water wet condition 0.113 to 0.180 μL), and granular anion exchange resin (AMBERJET 4002 Cl, Rohm and Haas Japan Ltd., average diameter 0.5 to 0.7 mm, average apparent volume per water-wet state 0.065 to 0.180 μL) regenerated with NaOH, 1 : It mixed by the volume ratio of 2, and prepared granular ion exchange resin mixture A.
The apparent density of the particulate ion exchange resin mixture A at this time was 0.71 (g / cm ³ -R).

85 mL of particulate ion exchange resin mixture A (water wet packed volume (tapping volume)) was packed into a catalyst packed column with an inner diameter of 57 mm. Next, ultrapure water was passed through so as to be SV 5000 h ⁻¹ , and the differential pressure was measured. The pressure loss was 43 kPa.

<Water to be treated>
As the water to be treated, water to be treated containing hydrogen peroxide was prepared. The properties are shown in Table 1.

Example 1
The test was conducted using the processing apparatus of the embodiment shown in FIG.
First, 85 mL (corresponding to the filling volume) of the platinum group metal (palladium) -supporting monolithic anion exchanger A obtained above are cut out in a water-wet state, and a 5 mm square cube (apparent volume per piece is 125 μL) The platinum group metal-supported monolithic anion exchanger A was placed in a catalyst-filled column with an inner diameter of 57 mm on which the screen 12 was installed. Next, 85 mL of particulate ion exchange resin mixture A (water wet packed volume (tapping volume)) is placed in a catalyst packed column and tapped to separate the particulate ion exchange resin mixture between platinum group metal-supported monolithic anion exchanger A. A was charged to form a catalyst-supporting porous body layer composed of a platinum group metal-supported monolithic anion exchanger A and a particulate ion exchange resin mixture A filling in between them. At this time, the thickness of the catalyst-supporting porous material layer was 70 mm. Also, in the packed volume of the platinum group metal-supported monolithic anion exchanger A and the packed volume of the particulate ion exchange resin mixture A in the catalyst-supported porous material packed bed, the packed volume of the platinum group metal-supported monolithic anion exchanger A The proportion was 50% by volume.
Next, ultrapure water containing 15 μg / L of hydrogen peroxide was passed through a catalyst-packed column at SV 5000 h ⁻¹ , and the concentration of hydrogen peroxide in the obtained treated water was quantified. The results are shown in Table 2.

(Example 2)
The test was conducted using the processing apparatus of the embodiment shown in FIG.
First, 85 mL (corresponding to the filling volume) of the platinum group metal (palladium) -supporting monolithic anion exchanger A obtained above are cut out in a water-wet state, and a 5 mm square cube (apparent volume per piece is 125 μL) The platinum group metal-supported monolithic anion exchanger A was placed in a catalyst-filled column with an inner diameter of 57 mm on which the screen 12 was installed. Next, 85 mL of particulate ion exchange resin mixture A (water wet packed volume (tapping volume)) is placed in a catalyst packed column and tapped to separate the particulate ion exchange resin mixture between platinum group metal-supported monolithic anion exchanger A. A was charged to form a catalyst-supporting porous body layer composed of a platinum group metal-supported monolithic anion exchanger A and a particulate ion exchange resin mixture A filling in between them. Next, 85 mL of particulate ion exchange resin mixture A (filled volume in water wet state (tapping volume)) was packed in a catalyst packed column to form an inflow side particulate ion exchange resin layer on the catalyst-supporting porous material layer. At this time, the thickness of the catalyst-supporting porous material packed bed was 70 mm, and the thickness of the inflow side granular ion exchange resin layer was 50 mm. Also, in the packed volume of the platinum group metal-supported monolithic anion exchanger A and the packed volume of the particulate ion exchange resin mixture A in the catalyst-supported porous material packed bed, the packed volume of the platinum group metal-supported monolithic anion exchanger A The proportion was 50% by volume.
Next, ultrapure water containing 15 μg / L of hydrogen peroxide was passed through a catalyst-packed column at SV 5000 h ⁻¹ , and the concentration of hydrogen peroxide in the obtained treated water was quantified. The results are shown in Table 2.

(Example 3)
The test was performed using the processing apparatus of the embodiment shown in FIG.
First, the particulate ion exchange resin mixture A is placed in a catalyst packed column having an inner diameter of 57 mm, in which 85 mL (filled volume in water wet condition (tapping volume)) and the gauze 12 is installed, to form an outflow side particulate ion exchange resin layer. The Then, 85 mL (corresponding to the filling volume) of the platinum group metal (palladium) -supporting monolithic anion exchanger A obtained above is cut out in a water-wet state, and further a cube of 5 mm square (apparent volume per piece is 125 μL) The platinum group metal-supported monolithic anion exchanger A was placed in a catalyst-filled column with an inner diameter of 57 mm on which the screen 12 was installed. Next, 85 mL of particulate ion exchange resin mixture A (water wet packed volume (tapping volume)) is placed in a catalyst packed column and tapped to separate the particulate ion exchange resin mixture between platinum group metal-supported monolithic anion exchanger A. A: A catalyst-supporting porous material layer consisting of a platinum group metal-supporting monolithic anion exchanger A and a particulate ion exchange resin mixture A filling the space between them is placed on the outflow-side particulate ion exchange resin layer. It was formed. Next, 85 mL of particulate ion exchange resin mixture A (filled volume in water wet state (tapping volume)) was packed in a catalyst packed column to form an inflow side particulate ion exchange resin layer on the catalyst-supporting porous material layer. At this time, the thickness of the catalyst-supporting porous material layer was 70 mm, the thickness of the inflow side particulate ion exchange resin layer was 50 mm, and the thickness of the outflow side particulate ion exchange resin layer was 50 mm. Also, in the packed volume of the platinum group metal-supported monolithic anion exchanger A and the packed volume of the particulate ion exchange resin mixture A in the catalyst-supported porous material packed bed, the packed volume of the platinum group metal-supported monolithic anion exchanger A The proportion was 50% by volume.
Next, ultrapure water containing 15 μg / L of hydrogen peroxide was passed through a catalyst-packed column at SV 5000 h ⁻¹ , and the concentration of hydrogen peroxide in the obtained treated water was quantified. The results are shown in Table 2.

(Example 4)
1 mm square, 2.5 mm square, 10 mm square, 20 mm square (apparent volume per unit is 1 μL, 16 μL, 1000 μL, respectively) with 85 mL of platinum group metal (palladium) -supported monolithic anion exchanger A in water-wet state , 8000 .mu.L) was used, in the same manner as in Example 2. The results are shown in Table 3.
Further, ^2000h -1 and ^SV, 3000h -1, was performed by changing the 10000h ^-1. The results are shown in Table 3.

(Example 5)
The procedure was carried out in the same manner as Example 1 except that the mixing amount of the particulate ion exchange resin mixture A was different. That is, first, 85 mL (corresponding to the filling volume) of the platinum group metal (palladium) -supporting monolithic anion exchanger A obtained above is cut out in a water wet state, and a cube of 5 mm square (apparent volume per piece is 125 μL) The platinum group metal-supported monolithic anion exchanger A and 595 mL of particulate ion exchange resin mixture A (fill volume (tapping volume in water wet state)) are cut to an inner diameter of 57 mm at which the plate 12 is installed. A catalyst-loaded porous body layer was formed, which was packed in a catalyst-packed column and composed of a platinum group metal-supported monolithic anion exchanger A and a particulate ion exchange resin mixture A filling in between them.
Next, ultrapure water containing 15 μg / L of hydrogen peroxide was passed through a catalyst-packed column at SV 5000 h ⁻¹ , and the concentration of hydrogen peroxide in the obtained treated water was quantified. The results are shown in Table 4.
Moreover, it carried out in the same manner as described above except that the mixing amount of the particulate ion exchange resin mixture A (filled volume in water wet state (tapping volume)) was 255 mL, 85 mL, 43 mL, and 28 mL, respectively. The results are shown in Table 4.

(Comparative example 1)
The procedure of Example 1 was repeated except that the particulate ion exchange resin mixture A was not used. That is, first, 85 mL of the platinum group metal (palladium) -supporting monolithic anion exchanger A obtained above is cut out in a water-wet state, and further cut into cubes of 5 mm square (apparent volume per piece is 125 μL) The platinum group metal supported monolithic anion exchanger A is packed in a catalyst-filled column having an inner diameter of 57 mm on which the plate 12 is installed to form a catalyst supported porous body layer consisting only of the platinum group metal supported monolithic anion exchanger A I did. At this time, the thickness of the platinum group metal-supported monolithic anion exchanger A layer was 70 mm.
Next, ultrapure water containing 15 μg / L of hydrogen peroxide was passed through a catalyst packed column, and the concentration of hydrogen peroxide in the obtained treated water was quantified. The results are shown in Table 4.
In addition, 85 mL of platinum group metal-supported monolithic anion exchanger A is cut into 1 mm square, 2.5 mm square, 10 mm square and 20 mm square (apparent volume per piece is 1 μL, 16 μL, 1000 μL, 8000 μL, respectively) The same procedure as described above was carried out except using the above. The results are shown in Table 5.

<Manufacture of palladium-supported particulate anion exchange resin A>
Palladium-supported particulate anion exchange wherein palladium nanoparticles are supported by a known method on particulate strong base anion exchange resin (type I) having a water retention ability of 60 to 70% based on OH form and in gel form Resin A was obtained. The particulate anion exchange resin of the Cl form was immersed in a hydrochloric acid aqueous solution of palladium chloride, washed with water, and then immersed in a hydrazine aqueous solution to conduct reduction treatment to obtain a palladium-supported particulate anion exchange resin A. At this time, the supported amount of palladium nanoparticles was 910 mg in terms of the supported amount of palladium nanoparticles with respect to 1 L of palladium-loaded particulate anion exchange resin in a water-wet state.

(Comparative example 2)
85 mL of the palladium-supported particulate anion exchange resin A obtained above (filled volume in water wet state (tapping volume)) and 765 mL of particulate ion exchange resin mixture A (filled volume in water wet state (tapping volume)) The mixture was packed and packed in a catalyst-filled column with an inner diameter of 57 mm in which 12 was installed.
Next, ultrapure water containing 15 μg / L of hydrogen peroxide was passed through a catalyst-packed column at SV 5000 h ⁻¹ , and the concentration of hydrogen peroxide in the obtained treated water was quantified. The results are shown in Table 6.

(Example 6)
The test was conducted using the processing apparatus of the embodiment shown in FIG.
First, 85 mL (corresponding to the filling volume) of the platinum group metal (palladium) -supporting monolithic anion exchanger A obtained above are cut out in a water-wet state, and a 5 mm square cube (apparent volume per piece is 125 μL) The platinum group metal-supported monolithic anion exchanger A was placed in a catalyst-filled column with an inner diameter of 57 mm on which the screen 12 was installed. Next, 85 mL of particulate ion exchange resin mixture A (water wet packed volume (tapping volume)) is placed in a catalyst packed column and tapped to separate the particulate ion exchange resin mixture between platinum group metal-supported monolithic anion exchanger A. A was charged to form a catalyst-supporting porous body layer composed of a platinum group metal-supported monolithic anion exchanger A and a particulate ion exchange resin mixture A filling in between them. Next, 85 mL of particulate ion exchange resin mixture A (filled volume in water wet state (tapping volume)) was packed in a catalyst packed column to form an inflow side particulate ion exchange resin layer on the catalyst-supporting porous material layer. At this time, the thickness of the catalyst-supporting porous material packed bed was 70 mm, and the thickness of the inflow side granular ion exchange resin layer was 50 mm. Also, in the packed volume of the platinum group metal-supported monolithic anion exchanger A and the packed volume of the particulate ion exchange resin mixture A in the catalyst-supported porous material packed bed, the packed volume of the platinum group metal-supported monolithic anion exchanger A The proportion was 50% by volume.
Next, hydrogen gas is dissolved in ultrapure water containing 30 μg / L of dissolved oxygen using a hydrogen dissolving film to make the water to be treated containing 50 μg / L of dissolved hydrogen, and this water to be treated is passed through the catalyst packed column. The water was drained, and the dissolved oxygen concentration in the obtained treated water was quantified. The results are shown in Table 7.

(Comparative example 3)
Example 5 was carried out in the same manner as Example 5, except that the particulate ion exchange resin mixture A was not used. That is, first, 85 mL (corresponding to the filling volume) of the platinum group metal (palladium) -supporting monolithic anion exchanger A obtained above is cut out in a water wet state, and a cube of 5 mm square (apparent volume per piece is 125 μL) The platinum group metal-supported monolithic anion exchanger A is packed into a catalyst-filled column with an inner diameter of 57 mm on which the plate 12 is installed, and the catalyst-supported monolith anion exchanger A alone is loaded. A porous layer was formed.
Next, hydrogen gas is dissolved in ultrapure water containing 30 μg / L of dissolved oxygen using a hydrogen dissolving film to make the water to be treated containing 50 μg / L of dissolved hydrogen, and this water to be treated is passed through the catalyst packed column. The water was drained, and the dissolved oxygen concentration in the obtained treated water was quantified. The results are shown in Table 7.

1, 31 treatment apparatus for liquid to be treated 2, 32 treatment vessel 3, 23 catalyst-supporting porous material packed bed 4, 24 inflow side granular ion exchange resin layer 5, 25 outflow side granular ion exchange resin layer 6 catalyst supporting porous body 7 Particulate ion exchange resin 10 treated liquid supply pipe 11 treated liquid discharge pipe 21 treated liquid 22 treated liquid 26 palladium supported monolithic anion exchanger A
27 Particulate ion exchange resin mixture A

Claims (9)

The liquid to be treated is supplied to a catalyst-supported porous body packed bed comprising a catalyst-supporting porous body in which a catalyst is supported on a porous body and a particulate ion exchange resin filling the space between the catalyst-supporting porous bodies. And a method of treating the treatment liquid in which the treatment liquid is allowed to pass through the catalyst-supporting porous material packed bed,
The catalyst-supporting porous body is a platinum group metal-supporting monolithic organic porous body in which a platinum group metal catalyst is supported on a monolithic organic porous body, or a platinum group metal catalyst as a monolithic organic porous ion exchanger Being a supported platinum group metal supported monolithic organic porous ion exchanger;
In the catalyst-supported porous body packed bed, the ratio of the packed volume of the catalyst-supported porous body to the total of the packed volume of the catalyst-supported porous body and the packed volume of the particulate ion exchange resin is 25 to 67% by volume To be
The processing method of the to-be-processed liquid characterized by the above.   The method for treating a liquid to be treated according to claim 1, wherein an average apparent volume per one of the catalyst-supporting porous bodies is 1 to 8000 μL.   The particulate ion exchange resin layer which consists of particulate ion exchange resin is further provided in the inflow side of the to-be-treated liquid of the said catalyst support porous body packed bed, The claim 1 or 2 characterized by the above-mentioned. Method of treating liquid to be treated.   The particulate ion exchange resin layer which consists of particulate ion exchange resin is further provided in the outflow side of the to-be-treated liquid of the said catalyst support porous body packed bed, The particulate ion exchange resin layer characterized by the any one of Claims 1-3 characterized by the above-mentioned. Method of treating liquid to be treated. The method for treating a liquid to be treated according to any one of claims 1 to 4 , wherein the liquid to be treated contains at least one of hydrogen peroxide and dissolved oxygen. It has a treatment tower or treatment vessel through which the liquid to be treated flows.
A catalyst-supporting porous body comprising a catalyst-supporting porous body in which a catalyst is supported on a porous body, and a particulate ion exchange resin filling the space between the catalyst-supporting porous body in the treatment tower or treatment vessel A packed bed is formed,
The catalyst-supporting porous body is a platinum group metal-supporting monolithic organic porous body in which a platinum group metal catalyst is supported on a monolithic organic porous body, or a platinum group metal catalyst as a monolithic organic porous ion exchanger Being a supported platinum group metal supported monolithic organic porous ion exchanger;
In the catalyst-supported porous body packed bed, the ratio of the packed volume of the catalyst-supported porous body to the total of the packed volume of the catalyst-supported porous body and the packed volume of the particulate ion exchange resin is 25 to 67% by volume To be
An apparatus for treating a liquid to be treated. 7. The apparatus for treating a liquid to be treated according to claim 6, wherein the average apparent volume per one of the catalyst-supporting porous bodies is 1 to 8000 μL. The liquid to be treated according to claim 6 or 7, further comprising a particulate ion exchange resin layer made of particulate ion exchange resin on the inflow side of the liquid to be treated of the catalyst-supporting porous material packed layer. Processing unit. The outflow side of the liquid to be treated of the catalyst-carrying porous packed bed, claims 6 to 8, wherein any one of claims, characterized in that the granular ion exchange resin layer having a granular ion-exchange resin is further provided Treatment equipment for liquid treatment.