WO2012056666A1

WO2012056666A1 - Adsorption structure, adsorption module, and method for producing same

Info

Publication number: WO2012056666A1
Application number: PCT/JP2011/005916
Authority: WO
Inventors: 牛房　信之; 敬子中野; 泰子山田
Original assignee: 株式会社日立製作所
Priority date: 2010-10-29
Filing date: 2011-10-24
Publication date: 2012-05-03
Also published as: JP2012091151A

Abstract

In water treatment plants there is a problem where organic matter dissolved in water adsorbs onto the surface of a reverse osmosis membrane used in high-performance treatment, thus causing membrane performance to deteriorate and necessitating frequent replacement of the reverse osmosis membrane module. In order to solve this problem, an adsorption structure is provided that adsorbs organic matter in treated water, wherein the adsorption structure comprises an outer wall, a plurality of flow paths provided on the inner side of the outer wall, and partition walls for partitioning the plurality of flow paths. The adsorption structure is characterized in that the partition walls are smaller than the diameter of the flow path and have communication holes through which the flow path and other flow paths communicate, and an adsorptive material to which the organic matter adsorbs. As a result, the organic matter in water to be treated can be selectively removed and the replacement frequency of a reverse osmosis membrane can be reduced.

Description

Adsorption structure, adsorption module and manufacturing method thereof

The present invention relates to a reverse osmosis membrane pretreatment technique for separating and removing dissolved organic substances and electrolytes used in advanced treatment in water treatment processes such as wastewater regeneration treatment and seawater desalination.

A reverse osmosis membrane is used in advanced treatment of water purification. A semi-permeable membrane is used on the surface of the reverse osmosis membrane, and the material of the semi-permeable membrane is roughly classified into cellulose acetate type and aromatic polyamide type. Among these, aromatic polyamide-based reverse osmosis membranes are widely used for industrial use because of their high water permeability and electrolyte removal performance. As the structure, a structure of a composite semipermeable membrane in which an aromatic polyamide membrane is formed on a microporous support is often used, and the thickness of the aromatic polyamide portion is 1 μm or less.

Reverse osmosis membranes are used to remove organic substances and electrolytes that are dissolved in water during seawater desalination, pure water production used in the manufacture of precision electronics such as semiconductors, advanced water treatment, and final treatment of sewage and wastewater.

Of these uses, when used for the final treatment of sewage, water is generally supplied to the reverse osmosis membrane through the following treatment process. First, coarse impurities, waste, etc. contained in sewage are removed through a sieve called a screen. Next, a fine suspension such as sand is added to the flocculant if necessary, and then submerged in a sedimentation basin for separation. The supernatant water still contains suspended solids, dissolved organic matter, etc., and is decomposed using microorganisms. Microbial metabolites are generated as sludge, and sludge and water are separated by settling in a sedimentation basin or passing through a microfiltration membrane. The sewage primary treated water treated in this way contains almost no suspended solids. At this stage, the quality of water can be disinfected and released into rivers, or reused depending on the application, such as greening spray water. It has been purified. In Japan, at this stage, it is discharged into rivers and water is recycled using natural purification. However, because there are not enough rivers and lakes necessary for natural purification in the Middle East, inland areas, islands without rivers, etc., there is an increasing demand for further purification of sewage primary treated water and reuse it as drinking water or industrial water. Yes. The reverse osmosis membrane is used to remove dissolved organic substances and electrolytes in the sewage primary treated water in this final treatment.

The sewage primary treated water varies depending on the treatment up to the previous stage, but the electrolyte is 1% or less and the dissolved organic matter is contained in 3-20 mg / L in terms of TOC (total organic carbon content). When these are separated by a reverse osmosis membrane, it is possible to reduce the electrolyte to 1 ppm or less and the dissolved organic matter to 1 mg / L or less.

Many reverse osmosis membranes used for final sewage treatment are folded into a shape called a spiral in order to increase the membrane surface area in the module. A bag-like reverse osmosis membrane is fixed to the center core, and it is rolled up like an umbrella and stored in a cylinder. The main module is a cylindrical shape with a diameter of 4 inches, 8 inches, etc. and a length of 1 m.

Reverse osmosis membranes are a type of separation membrane, but there are two methods for water filtration using separation membranes. One is a total filtration system, in which all the supplied water is passed through the membrane, and components that cannot pass through the membrane are deposited on the membrane surface. The other is a cross-flow filtration method, in which water flows parallel to the membrane surface, part of it permeates through the membrane to permeate, and the rest is taken out from the module as concentrated water with the concentration of dissolved matter increased. . The latter cross-flow filtration method is used for filtration through reverse osmosis membranes. This method reduces the increase in operating load due to the deposition of dissolved material on the membrane surface and the increase in concentration. However, even with the cross-flow filtration method, there is a problem that the dissolved matter is adsorbed on the membrane surface and the amount of permeated water deteriorates with time.

The adsorbed material on the membrane surface includes organic fouling that adsorbs organic matter in addition to the scale in which the electrolyte is deposited at a high concentration near the membrane surface, biofouling in which microorganisms in the water grow on the membrane surface. Clean water is periodically flowed over the membrane surface, and the adsorbate is removed by shearing force. However, when organic matter is adsorbed, it cannot be completely removed by shearing force, and gradually accumulates and the amount of water permeated. Decreases. The power (pressure) is increased to obtain a constant permeation amount, but this leads to an increase in the power cost of the pump. In addition, since the reverse osmosis membrane gradually deteriorates due to the cleaning liquid, the ion rejection rate decreases. As these progress, it is necessary to replace the reverse osmosis membrane module. When replacing the reverse osmosis membrane module, it is necessary to stop the operation for a long time, and since the reverse osmosis membrane module cannot be recycled, it is necessary to replace it with a new reverse osmosis membrane module. This increases the running cost per unit of water, such as product costs and waste disposal costs.

Japanese Patent No. 3864817 JP 2005-111407 A JP 2008-136919 A

For this reason, there is a method of extending the life until the replacement of the reverse osmosis membrane by adding a pretreatment step for removing organic substances in advance before the reverse osmosis membrane. As a pretreatment method, there are a method of decomposing an organic substance, a method of removing an organic substance by adsorption or aggregation, and the method of adsorbing the latter organic substance is disclosed in Patent Document 1 from the same material as a reverse osmosis membrane. A method using an adsorbing material is disclosed.

活性炭 Activated carbon is widely used as an organic material adsorption material. However, in the method using activated carbon, most of the organic matter contained in the sewage primary treated water is adsorbed, so the activated carbon quickly reaches adsorption saturation, the frequency of replacement of the activated carbon increases, and the frequency of replacement of the reverse osmosis membrane is reduced. No cost merit is obtained even if it is reduced.

The structure of the adsorbing material is required to obtain a sufficient amount of permeated water when sewage primary treated water is permeated. On the other hand, it is necessary to increase the surface area in contact with water in order to perform adsorption efficiently. As a method for expanding the surface area, activated carbon is in the form of powder, crushed pieces, and granular materials. However, when used in water, the flow path of water becomes narrow, and it is difficult to obtain a sufficient flow rate. If the adsorbing material other than activated carbon is granular, the same problem occurs. Furthermore, activated carbon has pores to increase the surface area, but the substance trapped in the pores is difficult to desorb and it is practically impossible to recover the adsorption capacity by washing.

Patent Document 2 discloses a method of using an adsorbent material to remove organic substances dissolved in water when water treatment is performed using a reverse osmosis membrane. The adsorbing material has a problem that a large amount of adsorbing material is required because the surface area is insufficient.

When the reverse osmosis membrane is contaminated and clogged, the pressure (power) is increased to obtain a certain amount of permeation, leading to an increase in the power cost of the pump. In addition, the reverse osmosis membrane is washed to remove contamination, but the reverse osmosis membrane gradually deteriorates due to the chemical solution, and the ion rejection rate decreases. As these progress, reverse osmosis membrane exchange is required. When replacing the reverse osmosis membrane, it is necessary to stop the operation for a long time, making it difficult to stably supply reclaimed water. In particular, in sewage regeneration treatment, clogging with dissolved organic matter is a major issue because the water supplied to the reverse osmosis membrane contains a large amount of organic matter.

There are two main mechanisms of reverse osmosis clogging caused by dissolved organic matter. First, organic substances are adsorbed on the reverse osmosis membrane surface, blocking the surface state of the membrane and pores at the molecular level, thereby degrading the membrane performance. The second is largely related to the reverse osmosis membrane module and occurs because dissolved organic substances are insolubilized and deposited between the membrane surface and between the membrane and the spacer, and block the flow path. In particular, in the case of the second module structure, it occurs on the inlet side of the module, and the permeated water amount is reduced in spite of the absence of membrane deterioration at the back of the module. As a conventional method for removing dissolved organic matter, Patent Document 1 discloses a method using an adsorbent material made of the same material as a reverse osmosis membrane. Moreover, in order to enlarge the contact area of a treated water and a reverse osmosis membrane, the patent document 2 using a fibrous polymer and a ceramic porous body is disclosed.

When treating with a reverse osmosis membrane after bioactive sludge treatment in the sewage reclamation process, persistent water-degraded organic substances adsorbed on the reverse osmosis membrane surface and the water permeability deteriorates over time, resulting in stable permeation. Problems arise in the water supply. Although the performance of the reverse osmosis membrane is restored by cleaning it with clean water, it is difficult to fully recover the function, and the quality of the permeated water deteriorates due to the membrane being deteriorated by the cleaning solution. For this reason, it is necessary to replace the reverse osmosis membrane when it deteriorates to some extent. If the lifetime of the reverse osmosis membrane is short, the running cost of water treatment increases. In particular, sewage reclamation is a major issue because the amount of organic matter contained in the water supplied to the reverse osmosis membrane is large.

There is a method of removing organic substances in the pretreatment process, but it is difficult to obtain an effect at low cost. This is because a large amount of adsorbent material is necessary and it is difficult to recycle the adsorbent material.

The object of the present invention is to solve the above-mentioned problems, add a low-cost pretreatment process to extend the life of the reverse osmosis membrane, and reduce the running cost for the regeneration treatment of sewage.

In order to solve the above-described problems, the present invention provides, for example, an adsorption structure that adsorbs organic matter in water to be treated, an outer wall, a plurality of channels provided inside the outer wall, and a plurality of channels. A partition wall that separates each of the partition walls, the partition wall having a communication hole that is smaller than the diameter of the channel and that communicates the channel with another channel, and an adsorbent that adsorbs the organic matter. An adsorption structure is provided.

According to the present invention, it is possible to reduce the running cost of the sewage regeneration process by adding a low-cost pretreatment process to extend the life of the reverse osmosis membrane.

It is a water treatment flowchart using an adsorption module. It is a schematic diagram of a structure when an adsorption module is assembled. It is the schematic diagram which looked at the ceramic honeycomb structure from the treated water supply direction. It is the schematic diagram which looked at the ceramic honeycomb structure from the side. It is an example of sectional drawing of a ceramic honeycomb structure. It is the molecular structure of the adsorption material concerning one Example of this invention.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.

FIG. 1 shows a water treatment facility according to an embodiment of the present invention. The water treatment facility includes an adsorption module 1, a water storage tank 5, a water supply pump 6, and a reverse osmosis membrane module 4.

In the embodiment according to the present invention, the sewage temporarily treated water supplied to the adsorption module 1 is a process for removing dust and the like through a screen, a process for adding fine flocculant such as sand to settle and removing it, a microorganism It is water that has been subjected to a series of treatments for decomposing organic matter using. The sewage primary treated water contains salts and dissolved organic matter. The sewage primary treated water thus treated contained 248 mg / L of dissolved organic matter in terms of TOC (total organic carbon content).

In the present invention, this sewage primary treated water is passed through the adsorption module 1 and passed through the reverse osmosis membrane 3 while being pressurized by the water absorption pump 6, thereby removing organic substances and salts in the treated water and completing the water regeneration. The sewage primary treated water is treated by passing through the ceramic honeycomb structure 2 in which the polymer material is modified by the adsorption module 1 and stored in the water storage tank 5. Water is supplied to the reverse osmosis membrane 3 from a water storage tank 5 by a water supply pump 6.

First, the problem and its solution will be described for the case of treating with the reverse osmosis membrane module 4 after microbial treatment in sewage regeneration treatment, but other uses of the reverse osmosis membrane, that is, precision electronic such as seawater desalination, semiconductors, etc. It is also effective in removing dissolved organic substances in water in the production of pure water used in equipment manufacturing, advanced treatment of clean water, and regeneration treatment of sewage and wastewater (including those that do not involve microbial treatment).

In the sewage regeneration treatment, the primary treated sewage water supplied to the reverse osmosis membrane is water after organic matter decomposition treatment by microorganisms, and contains 3-20 mg / L of refractory organic matter in terms of TOC (total organic carbon content). It is. The kind of persistent organic substance cannot be specified as one. In the cross-flow filtration method, the components separated by the reverse osmosis membrane are discharged together with the concentrated water, so that the organic matter that can be discharged is not a cause of deterioration of the reverse osmosis membrane and does not need to be positively removed. In the present invention, the water treatment flow shown in FIG. 1 solves the problem by using an adsorbent material in a pretreatment process that selectively and efficiently removes only organic substances adsorbed on the reverse osmosis membrane surface. By using such an adsorbing material, the amount of adsorbing material can be reduced, and low-cost pretreatment can be realized.

First, organic substances adsorbed on the surface of the reverse osmosis membrane were analyzed. Since multiple components are included, the components cannot be specified, but it was found that organic substances containing carbonyl groups and carboxyl groups are likely to be adsorbed. In addition, components including siloxanes containing amino groups and Si are also included in the adsorbing components.

In addition, when the amount of adsorption of the hardly decomposable organic substance to the reverse osmosis membrane was investigated, among the hardly decomposable organic substances dissolved in water, the amount adsorbed to the reverse osmosis membrane was about 5% in terms of TOC. It was found that the organic matter in the water does not adsorb on the reverse osmosis membrane even if it exists in the water and does not cause deterioration of the water permeability.

It is said that there are two major mechanisms by which reverse osmosis membranes adsorb organic substances. One is intermolecular interaction, and affinity works between materials with similar molecular structures. From the analysis of the adsorbed material, it is considered that a material containing a carbonyl group, an amino group, etc. has a higher affinity with a reverse osmosis membrane-causing substance, and therefore a polymer containing a carbonyl group or an amino group as a repeating unit is preferable. Examples include polyamide, polyimide, polyester, polycarbonate, polyurethane, acrylic resin, urea resin, polyethylene terephthalate, and the like. In order to increase the contact angle to 40 ° or more, it is preferable that the main chain or the side chain contains a hydrocarbon having 4 or more carbon atoms or an aromatic ring. Moreover, the thing containing a siloxane structure in a principal chain or a side chain is good for affinity with siloxanes. Furthermore, the structure contained in the main chain and the side chain is not limited to one type, and the adsorption efficiency can be improved by including a plurality of structures.

When there is a pretreatment process adsorbent with an adsorption surface equivalent to the reverse osmosis membrane surface, contact the pretreatment process adsorbent with the same surface area or more as the reverse osmosis membrane before putting it into the reverse osmosis membrane It is possible to double the life of the reverse osmosis membrane by removing the organic substances that cause deterioration.
In order to increase the surface area of the adsorbing material, the shape of the adsorbing material may be particles, meshes, fibers, filters, etc., but is not limited thereto.

Especially, the surface area becomes large in the case of a porous body such as a filter. If the surface area of the adsorbing material is increased, the volume of equipment added to the pretreatment process can be reduced, or the adsorbing material can be installed in the tank of the existing equipment.

Used for the process of adsorbing and removing dissolved organic substances in water for sewage reclamation, seawater desalination, pure water production used in the production of precision electronics such as semiconductors, and advanced water treatment.

In such a water treatment step, the treated water containing organic matter dissolved in water can be adsorbed through a ceramic honeycomb structure having a number of flow paths partitioned by partition walls.

The adsorption module of this example will be described with reference to the drawings. FIG. 2 is a side view of an example of the adsorption module 1 used in the sewage treatment apparatus. The adsorption module 1 is a structure having a filter (porous ceramic honeycomb structure 2) having a ceramic honeycomb structure. A ceramic honeycomb structure 2 on which an adsorbing material 13 such as polyamide is supported is accommodated by a filter support 8 in a housing 7 (acrylic container) via a gripping member. The support 8 allows water to pass without resistance, and when water is permeated at 0.1 MPa, the position change at the center of the major axis is within 5% of the length of the major axis in the fixed end. It is only necessary to use a material that has sufficient strength, thickness, and retention method and that does not have elution into water. For example, resin-based mesh spacers such as polyethylene, polypropylene, polyethylene terephthalate, and polystyrene, and metal-based materials. Stainless steel, titanium mesh or punching metal can be used. In this example, a punching metal having a thickness of 1 mm was used as the support 8.

As shown in FIGS. 3 to 5, the ceramic honeycomb structure 2 of the present example includes an outer peripheral wall 9, a plurality of flow paths 12 provided inside the outer peripheral wall 9, and a partition wall 10 that separates the flow paths 12. And a polymer material 13 provided on the partition wall 10. The flow paths 12 are arranged side by side in a direction intersecting the longitudinal direction, and are formed by plugging through holes penetrating from the inflow side surface to the outflow side surface. Specifically, the inflow side surface of the treated water is opened, the first outflow side is plugged by the plugging portion 11 on the opposite outflow side, and the outflow side of the treated water is opened, The opposite inflow side has a second flow path 12 b plugged by the plugging portion 11. On the plane intersecting the longitudinal direction, the first flow path 12a and the second flow path 12b are alternately arranged both vertically and horizontally. In addition, in the outer peripheral wall 9 and the partition wall 10 formed of the ceramic honeycomb, there are innumerable communication holes (not shown) thinner than the diameter of the flow path.

As shown in FIG. 5, to-be-processed water flows in into the 1st flow path 12a opened to the inflow side in the ceramic structure 2 in the adsorption | suction module 4. As shown in FIG. The treated water that has flowed in flows through the fine communication hole in the partition wall 10 into the second flow path 12b. A polymer material 13 as an organic material adsorbing material is provided on the surface of the partition wall 10 or on the uppermost layer of the fine communication hole surface in the partition wall 10. The material 13 adsorbs and removes organic substances in the water to be treated.
The water to be treated that has flowed into the second flow path 12b flows out from the outflow side of the ceramic structure 2 in which the flow path 12b is opened.

As shown in FIGS. 3 to 5, the partition 10 has a lattice shape having a thickness of 0.1 mm to 1 mm. When the partition wall 10 is thicker than 0.1 mm, it is easy to ensure the strength of the partition wall 10 and maintain the shape. Moreover, when the thickness of the partition wall 10 is less than 1 mm, the pressure necessary to permeate the treated water does not become excessive, which is practical. Further, the partition wall 10 is characterized by having fine communication holes with an average diameter of 0.005 mm to 0.05 mm. With fine communication holes having an average diameter of 0.005 mm or more, resistance during water permeation is not increased and the amount of treated water is easily obtained, and clogging due to components other than adsorbed components is difficult to occur. In addition, when the average pore diameter is less than 0.050 mm, the effect of expanding the surface area due to the porous ceramic honeycomb structure 2 is great, and the contribution to the volume control of the pretreatment process equipment is great.

Furthermore, the flow path 12 has a square shape with one side of 0.5 mm to 8 mm. When the flow path 12 has a side of 0.5 mm or more, the treated water having organic matter dissolved in water adsorbs the organic matter near the entrance of the ceramic honeycomb structure 2 and blocks the flow path 12 near the entrance. Therefore, the ceramic honeycomb structure 2 can be effectively used up to the end on the back side. On the other hand, if one side of the flow path 12 is smaller than 8 mm, the partition wall 10 of the ceramic honeycomb structure 2 can be thickened, and sufficient mechanical strength can be secured, and there is a possibility of breakage when pressure is applied to the treated water. Since it can be made low, it is preferable. Further, the shape of the flow path 12 is not limited to the square shape.

The end of the ceramic honeycomb structure 2 is plugged with an end of a desired flow path 12, and the flow path 12 has a shape with a plugged portion 11 at either end. The water to be treated was dissolved in the treated water by the partition wall 10 by being inserted from the first channel 12a without the plugging portion 11 on the inflow side in the channel 12 and passing through the fine communication holes of the partition wall 10. The organic matter is reliably adsorbed. The water to be treated that has passed through the partition wall 10 flows out of the ceramic structure 2 through the second flow path 12b without the plugging portion 11 on the outflow side. In the porous ceramic honeycomb structure 2, plugged portions 11 are formed at positions away from the end faces of a number of flow paths 12 partitioned by a porous partition wall 10 formed in a honeycomb shape. The plugging portion 11 in the ceramic honeycomb structure 2 can be made of the same material as the porous ceramic honeycomb structure 2 or a material that does not dissolve in the treated water, such as an organic material or an inorganic material. The plugging portion 11 as a stopper is pushed and fixed with a stick or syringe. Further, as shown in FIGS. 3 to 5, if the plugging portions 11 are alternately introduced into the end face of the flow path 12, they are in contact with both the first flow path 12a and the second flow path 12b and inside thereof. The partition wall 10 through which the water to be treated permeates increases and the efficiency is improved.

The porosity of the material used for the partition wall 10 is preferably 45% to 70%. When the porosity of the material used for the partition wall 10 is larger than 45%, the fine holes formed in the partition wall 10 are less likely to be blocked and become communication holes, and the amount of communication holes can be sufficiently secured. Moreover, it is preferable that the porosity of the material used for the partition wall 10 is less than 70% because the mechanical strength of the partition wall 10 is ensured and the possibility of breakage is reduced when pressure is applied to the treated water.

Further, the porosity of the material used for the plugging portion 11 is smaller than the porosity of the material used for the partition wall 10 and is 0% to 40%, and the plugging portion 11 is larger than the thickness of the partition wall 10. It is desirable that the thickness of the When the porosity of the material used for the plugged portion 11 is less than 40%, it is preferable because the possibility that the treated water that permeates the partition wall 10 will permeate the plugged portion 11 is reduced. By making the porosity of the material used for the plugging portion 11 smaller than the porosity of the material used for the partition wall 10, the treated water can surely pass through the partition wall 10.

It is desirable that the material constituting the partition wall 10 contains alumina or a composite oxide containing alumina. It was confirmed by experiments that the alumina group is exposed on the surface, so that a part of the dissolved organic matter in the treated water can be adsorbed, and the high-degradability dissolved organic matter in the polymer can be decomposed to reduce the molecular weight. . In particular, at least one of aluminosilicate, silimanite, mullite, spinel, cordierite, aluminum titanate, and lithium aluminum silicate is used as the alumina or composite oxide containing alumina contained in the material constituting the partition wall 10. It is preferable that there is.

Further, the same effect can be obtained by forming a film containing alumina on the surface of the partition wall 10 or on at least a part or the entire surface of the fine communication hole in the partition wall 10.

Furthermore, as long as it is insoluble in the treated water, the material constituting the partition wall 10 and the material constituting the plugging portion 11 may be different. Since heat resistance is not required because it is used for water treatment, at least one of glass, polyimide, polyamide, polyimide amide, polyurethane, acrylic, epoxy, polypropylene, and Teflon (registered trademark) is used as the material constituting the plugging portion 11. It may contain one or more materials. Therefore, the temperature at which the plugging portion 11 is formed may be lower than the temperature at which the partition wall 10 is formed.

Further, the material constituting the plugging portion 11 may be a composite material made of ceramic particles and an organic polymer material. As the ceramic particles used for the material constituting the plugging portion 11, at least one of alumina, silica, magnesia, titania, zirconia, zircon, cordierite, spinel, aluminum titanate, and lithium aluminum silicate is preferable.

As a method for forming the plugging portion 11, a printing mask having an opening at a position corresponding to the flow path 12 of the ceramic structure 2 is used, and the paste used for the plugging portion 11 is formed by the partition wall 10 by a screen printing method. The plugging portion 11 can be formed at a desired position of the flow path 12.

Further, as a method of forming the plugging portion 11, a dispenser having a plurality of nozzles arranged at positions corresponding to the flow paths 12 of the ceramic structure 2 is used, and paste used for the plugging portion 11 is ejected from the paste. The plugging portion 11 can be formed at a predetermined position in the flow path 12 formed by the partition wall 10 by the method. For example, in polymer coating, an ultrafine needle having a needle tip of micrometer order used for medical use or the like is used. First, it is possible to adopt a method in which the needle is inserted to the vicinity of the sealing portion, and the needle is pulled out while spraying.

In order to prevent contamination of the reverse osmosis membrane 3 used in the post-process of the adsorption module 1, the surface of the partition wall 10 of the porous ceramic honeycomb structure 2 used in the adsorption module 1 or fine communication holes in the partition wall 10 A polymer material 13 is modified on the uppermost layer of the surface. The polymer material 13 is applied to all or a part of the partition walls 10 of the porous ceramic honeycomb structure 2, only the inner wall of the partition wall 10 in the first half and the latter part, only the inner wall of the partition wall 10 in the second half part. , Any combination can be taken. It is effective that the polymer material 13 is modified with a material containing at least one polymer containing 2 equivalents or more of amino groups relative to the repeating unit. It has been confirmed by experiments that these polymer materials 13 have a characteristic of adsorbing organic substances that contaminate the reverse osmosis membrane 3 used in the subsequent process of the adsorption module 1.

The method of applying the polymer material 13 to the porous ceramic honeycomb structure 2 is the same as a part of the method used when forming the plugged portions 11, and a plurality of nozzles arranged at desired positions. The polymer material 13 used as the adsorbing material 13 is formed by applying the polymer material 13 as the adsorbing material to a predetermined position in the flow path 12 formed by the partition wall 10 by a discharge method. it can. For example, in polymer coating, an ultrafine needle having a needle tip of micrometer order used for medical use or the like is used. First, it is possible to adopt a method in which the needle is inserted near the end of the plugging portion 11 and the needle is pulled out while spraying. The polymer material 13 that adsorbs and removes the organic matter is thick enough not to fill the pores in the partition wall 10 over the entire surface or part of the surface of the partition wall 10 and the inside of the 0.005-0.050 mm hole. In this case, water penetrates the partition wall 10 with almost no resistance, and the applied polymer material 13 adsorbs and removes organic substances dissolved in water.

Intermolecular interaction affects the mechanism by which the polymer material 13 adsorbs dissolved organic matter in water. From the analysis of the adsorbed organic matter, a polymer containing a —NH— bond having a high affinity with a carbonyl group, a carboxyl group, or an aromatic ring is preferably used as the adsorbing polymer material 13. Examples of the polymer repeating unit containing —NH— bond include polyamide, polyimide, polyurethane, urea resin, polypeptide (protein), polyethyleneimine, polybenzimidazole, polybenzoxazole and the like. As other materials, those containing —NH— bonds in the side chain or main chain can also be used. FIG. 6 shows the chemical structure of the polymer. For example, there are polyallylamine and polyvinylamine. In addition, those having a carbonyl group or a siloxane structure in the main chain or side chain may be used because of the affinity for —NH— bonds and siloxanes. Furthermore, the structure contained in the main chain and the side chain is not limited to one type, and by including a plurality of structures, a wide variety of mixtures contained in water can be adsorbed and the adsorption efficiency can be improved. .

As the adsorbing polymer material 13, commonly used polyamide and cellulose acetate can be used, but are not limited thereto.

Further, a photocatalyst may be supported on the porous ceramic honeycomb structure 2 or the polymer material 13 in order to decompose organic substances. As the photocatalyst, titanium oxide, strontium titanate, zinc oxide, iron oxide, tungsten oxide and the like can be used, but are not limited thereto.

By purifying the water to be treated using the porous ceramic honeycomb structure 2 modified with such an adsorbing polymer material 13, organic substances can be efficiently removed with a large surface area, and the adsorption module 1 Since the flow path 12 is wide, clogging is less likely to occur, and the frequency of cleaning and replacement of the adsorption module 1 and the reverse osmosis membrane 3 in the subsequent process can be reduced, and the running cost can be reduced.

By performing the reverse osmosis membrane 3 pretreatment step with such an adsorbent material 13, it is possible to selectively adsorb only the organic matter causing the performance deterioration of the reverse osmosis membrane 3 in advance and remove it from the water. Since the amount of organic matter accumulated in the material 13 is small, the replacement frequency of the adsorbing material 13 is low, and a low-cost pretreatment method can be obtained by limiting the adsorbing function only to the outermost surface.

Hereinafter, a method for manufacturing the ceramic structure 2 will be described.

The ceramic honeycomb structure 2 on which the adsorbing material 13 is supported is manufactured as follows. Kaolin, talc, silica, were prepared powders such as alumina, SiO ₂ in a weight _{_{ratio: 48 ~ 52%, Al 2}} O 3: 33 ~ 37%, MgO: 12 ~ 15% become so cordierite Prepare a raw material powder, add a binder such as methylcellulose and hydroxypropylmethylcellulose, and a lubricant to this powder, mix thoroughly by dry process, add a specified amount of water, and thoroughly knead and plasticize ceramic clay. Create Next, the clay is extruded using an extrusion mold, cut, and dried to obtain a dried body having a honeycomb structure. Next, the outer peripheral portion of the dried body is removed by processing, and the flow path 12 located on the outermost periphery does not have the partition wall 10 with the outside, so that a honeycomb structure having a groove that opens to the outside and extends in the axial direction. It was set as the dry body which has. Further, as a typical example, after firing at 1400 ° C., a coating agent containing cordierite particles and colloidal silica is applied to the flow path 12 which opens to the outside and is fired. The cordierite-type ceramic honeycomb structure 2 is formed with a large number of flow paths 12 having a rectangular section.

In order to manufacture the ceramic honeycomb structure 2 by changing the thickness of the partition wall 10 to 0.05 mm to 2.0 mm, various extrusion molds were prepared and prototyped. When the thickness of the partition wall 10 was greater than 0.1 mm, the strength of the partition wall 10 was sufficient and it was easy to maintain the shape. On the other hand, when the thickness of the partition wall 10 is smaller than 1.0 mm, it is not necessary to apply excessive pressure to permeate the treated water, which is practical. Therefore, it was found that the thickness of the partition wall 10 was 0.1 mm to 1.0 mm.

Further, a ceramic honeycomb structure 2 having fine communication holes with an average diameter of 0.003 mm to 0.1 mm was manufactured in the partition wall 10. In the communication holes having an average diameter of 0.005 mm or more, the resistance during water permeation was small and a sufficient amount of treated water was obtained. In addition, clogging due to components other than adsorbed components does not occur. On the other hand, when the average pore diameter is less than 0.050 mm, the effect of increasing the surface area due to the porous ceramic honeycomb structure 2 is great, which contributes to the volume control of the pretreatment process equipment.

Furthermore, the channel 12 was made to have a quadrangular shape with sides of 0.3 mm to 10 mm. When the flow path 12 has a side of 0.5 mm or more, the treated water having organic matter dissolved in water adsorbs the organic matter near the entrance of the ceramic honeycomb structure 2 and blocks the flow path 12 near the entrance. Therefore, the ceramic honeycomb structure 2 can be effectively used up to the end on the back side. On the other hand, when one side of the flow path 12 is smaller than 8 mm, the partition wall 10 of the ceramic honeycomb structure 2 can be thickened, the mechanical strength is sufficient, and it is difficult to break when pressure is applied to the treated water by the pump 6. .

The composition of the ceramic honeycomb structure 2 and the firing temperature were changed so that the porosity of the material used for the partition wall 10 was 30% to 85%. When the porosity of the material used for the partition wall 10 is greater than 45%, the fine holes formed in the partition wall 10 can easily become communication holes, and the holes can be used effectively. In addition, a sufficient amount of communication holes can be secured, and no excessive pressure is required to permeate the treated water. On the other hand, if the porosity of the material used for the partition wall 10 is less than 70%, it is considered that the mechanical strength of the partition wall 10 can be sufficiently secured and is not easily damaged when pressure is applied to the treated water by the pump 6.

Further, the porosity of the material used for the plugging portion 11 was also produced by changing its composition and firing temperature. In the case where the porosity of the material used for the plugging portion 11 exceeds 40%, some of the treated water that permeates the partition wall 10 permeates the plugging portion 11. Therefore, the porosity of the material used for the plugging portion 11 is preferably smaller than the porosity of the material used for the partition wall 10 and is preferably 0% to 40%, and the plugging portion 11 is thicker than the thickness of the partition wall 10. By increasing the thickness of the stopper 11 in the longitudinal direction of the flow path, the treated water can surely pass through the partition wall 10. Thus, by making the porosity of the material used for the plugging portion 11 smaller than the porosity of the material used for the partition wall 10, the treated water can surely pass through the partition wall 10. .

Therefore, in the present invention, as an example of the structure of the ceramic honeycomb structure 2, the outer diameter (diameter) is 5.66 inches, the total length is 6 inches, the partition wall thickness is 0.32 mm, the partition wall pitch is 1.57 mm, The adsorption module 1 was produced using a pressure loss of 0.85 mmAq (at 7.5 Nm ³ / min).

As an example of a method for manufacturing such a ceramic honeycomb structure 2, there is Patent Document 3.
This patent document relates to a method for manufacturing a ceramic honeycomb structure 2 for purifying particulate matter contained in exhaust gas of a diesel engine.

Another example of the method for manufacturing the ceramic honeycomb structure 2 will be described. In this embodiment, the manufacturing method of the ceramic honeycomb is the same as that of Embodiment 2, but the manufacturing method of the plugging portion 11 is different.

The material used for the plugging portion 11 is a ceramic honeycomb structure having a composition containing the ceramic honeycomb structure 2 containing a solvent and a dispenser having a plurality of nozzles arranged at desired positions. An amount effective for plugging was discharged to predetermined predetermined positions on the inlet side and outlet side of the second channel 12. Thereafter, the plugged portion 11 was produced by drying and firing.

In addition to the dispenser, a screen printing method can be used to form the plugging portion 11. In the case of using the screen printing method, a printing mask having an opening at a predetermined position was aligned with a predetermined position of the ceramic honeycomb structure 2, and a high-viscosity slurry was discharged through the opening of the printing mask. Thereafter, the plugged portion 11 was produced by drying and firing. As in the case of using a dispenser, a good plugged portion 11 could be created.

Further, the porosity of the material used for the plugging portion 11 was also produced by changing its composition and firing temperature. In the case where the porosity of the material used for the plugging portion 11 exceeds 40%, some of the treated water that permeates the partition wall 10 permeates the plugging portion 11. For this reason, the porosity of the material used for the plugging portion 11 needs to be smaller than the porosity of the material used for the partition wall 10 and should be 0% to 40%, and the plugging portion 11 is thicker than the thickness of the partition wall 10. By increasing the thickness of the stopper 11, the treated water can surely pass through the partition wall 10. Thus, by making the porosity of the material used for the plugging portion 11 smaller than the porosity of the material used for the partition wall 10, the treated water can surely pass through the partition wall 10. .

The ceramic honeycomb structure 2 can be made of the same material, organic material, inorganic material, and the like as the porous ceramic honeycomb structure 2 in the partially plugged portion 11, and the stopper can be a stick or syringe. And fixed by pushing. Further, as shown in FIGS. 3 to 5, the sealing material was alternately introduced into the end face of the flow path 12 so that water could permeate through the partition wall 10.

Thus, as an example of the structure of the ceramic honeycomb structure 2 of the present invention, the outer diameter (diameter) is 5.66 inches, the total length is 6 inches, the partition wall thickness is 0.32 mm, the partition wall pitch is 1. A 57 mm initial pressure loss of 0.85 mmAq (at 7.5 Nm ³ / min) could be produced.

A ceramic honeycomb structure 2 was produced in the same manner as in Example 2 except that the following contents were applied.

As the material constituting the partition walls 10, alumina or a material containing a composite oxide containing alumina was used. It was confirmed by experiments that the alumina group is exposed on the surface, so that a part of the dissolved organic matter in the treated water can be adsorbed, and the low-molecular-weight dissolved organic matter can be decomposed to reduce the molecular weight. In particular, alumina or a composite oxide containing alumina contained in the material constituting the partition wall 10 is made of at least one material selected from aluminosilicate, silimanite, mullite, spinel, cordierite, aluminum titanate, and lithium aluminum silicate. If it was, good results were obtained.

Further, the same effect was obtained even when a film containing alumina was formed on the surface of the partition wall 10 or on at least a part or the entire surface of the fine communication hole in the partition wall 10.

Furthermore, a material in which the material constituting the partition wall 10 and the material constituting the plugging portion 11 are different was applied. However, it is insoluble in treated water. Since heat resistance is not required because it is used for water treatment, at least one of glass, polyimide, polyamide, polyimide amide, polyurethane, acrylic, epoxy, polypropylene, and Teflon is used as the material constituting the plugging portion 11. The one containing the material was used.

Also, a composite material composed of ceramic particles and an organic polymer material was used as the material constituting the plugging portion 11. As the ceramic particles used for the material constituting the plugging portion 11, at least one of alumina, silica, magnesia, titania, zirconia, zircon, cordierite, spinel, aluminum titanate, and lithium aluminum silicate was used. .

As the organic polymer material used for the material constituting the plugged portion 11, at least one of polyimide, polyamide, polyimide amide, polyurethane, acrylic, epoxy, polypropylene, and Teflon was used.

In the case of using an organic polymer material, the temperature for forming the plugging portion 11 was made lower than the temperature for forming the partition wall 10.

As a method of forming the plugging portion 11, a printing mask having an opening at a desired position is used, and a paste used for the plugging portion 11 is placed at a desired position of the flow path 12 formed by the partition wall 10 by a screen printing method. The sealing part 11 was formed.

Further, as a method of forming the plugging portion 11, a flow path formed by the partition wall 10 by using a dispenser having a plurality of nozzles arranged at desired positions and using paste for the plugging portion 11 by a paste discharge method. The plugging portion 11 could be formed at a predetermined position in 12. For example, for polymer coating, an ultra fine needle having a micrometer order is used for medical purposes. First, the needle was inserted to the vicinity of the sealing portion, and the needle was pulled out while spraying.

Thus, as in Example 1, the outer diameter (diameter) is 5.66 inches, the total length is 6 inches, the partition wall thickness is 0.32 mm, the partition wall pitch is 1.57 mm, and the initial pressure loss is 0. A structure of the ceramic honeycomb structure 2 of 85 mmAq (at 7.5 Nm ³ / min) could be produced.

An adsorbent was produced by the following method on the ceramic honeycomb structure 2 produced in Example 2 or the like.

As the polymer material 13 used for the adsorbing material, a material containing at least one polymer containing 2 equivalents or more of amino groups with respect to the repeating unit was modified. It has been experimentally confirmed that these polymer materials 13 have a feature of adsorbing organic substances that contaminate the reverse osmosis membrane 3 used in the subsequent process of the adsorption module 1.

As an example of the adsorbing material 13, polyamide was dissolved in N-methylpyrrolidone (NMP) to prepare a 0.5% polyamide NMP solution. The polyamide used was a polymerized 4,4'-oxydianiline and isophthaloyl dichloride as monomers.

In order to prevent contamination of the reverse osmosis membrane 3 used in the post-process of the adsorption module 1, the surface of the partition wall 10 of the porous ceramic honeycomb structure 2 used in the adsorption module 1 or fine communication holes in the partition wall 10 A polymer material 13 was modified on the uppermost layer of the surface. The polymer material 13 is applied to all or a part of the partition walls 10 of the porous ceramic honeycomb structure 2, only the inner wall of the partition wall 10 in the first half and the latter part, only the inner wall of the partition wall 10 in the second half part. Any combination was produced.

The method of applying the polymer material 13 to the porous ceramic honeycomb structure 2 is the same as a part of the method used when forming the plugged portions 11, and a plurality of nozzles arranged at desired positions. The polymer material 13 used as the adsorbing material is sprayed and applied to a predetermined position in the flow path 12 formed by the partition walls 10 of the ceramic honeycomb structure 2 by a discharge method using a dispenser having did.

For example, for the application of the polymer material, an ultrafine needle having a micrometer order needle tip used for medical use or the like was used. First, it is possible to adopt a method in which the needle is inserted near the end of the plugging portion 11 and the needle is pulled out while spraying. The polymer material 13 that adsorbs and removes the organic matter is thick enough not to fill the pores in the partition wall 10 over the entire surface or part of the surface of the partition wall 10 and the inside of the 0.005-0.050 mm hole. Was applied to 100 nm or less. After the polymer material 13 (polyamide) used as the adsorbing material was applied in the desired flow path 12 of the ceramic honeycomb structure 2, the ceramic honeycomb structure 2 was dried in an oven at 130 ° C. for 24 hours.

In this case, water permeated through the partition wall 10 almost without resistance, and the applied polymer material 13 was able to adsorb and remove organic substances dissolved in water.

Intermolecular interaction affects the mechanism by which the polymer material 13 adsorbs dissolved organic matter in water. From the analysis of the adsorbed organic matter, a polymer containing a —NH— bond having a high affinity with a carbonyl group, a carboxyl group, or an aromatic ring is preferably used as the adsorbing polymer material 13. Examples of the polymer repeating unit containing —NH— bond include polyamide, polyimide, polyurethane, urea resin, polypeptide (protein), polyethyleneimine, polybenzimidazole, polybenzoxazole and the like. As other materials, those containing —NH— bonds in the side chain or main chain can also be used. FIG. 6 shows the chemical structure of the polymer. For example, there are polyallylamine and polyvinylamine. In addition, those having a carbonyl group or a siloxane structure in the main chain or side chain may be used because of the affinity for —NH— bonds and siloxanes. Furthermore, the structure contained in the main chain and the side chain is not limited to one type, and by including a plurality of structures, a wide variety of mixtures contained in water can be adsorbed, and the adsorption efficiency can be improved. It was.

By purifying the water to be treated using the porous ceramic honeycomb structure 2 modified with such an adsorbing polymer material 13, organic substances can be efficiently removed with a large surface area, and the adsorption module 1 Since the flow path 12 is wide, clogging is less likely to occur, and the running frequency can be reduced by reducing the frequency of cleaning and replacement of the adsorption module 1 and the reverse osmosis membrane 3 in the subsequent process.

By performing the reverse osmosis membrane 3 pretreatment step with such an adsorbent material 13, it is possible to selectively adsorb only the organic matter causing the performance deterioration of the reverse osmosis membrane 3 in advance and remove it from the water. Since the amount of organic matter accumulated in the material 13 is small, the replacement frequency of the adsorbing material 13 is low, and a low-cost pretreatment method is obtained by limiting the adsorbing function only to the outermost surface.

In this example, a demonstration experiment of the capacity of the adsorption structure was performed. Temporary treated sewage water supplied to the adsorption module 1 is a process of removing dust etc. through a screen, a process of removing fine suspension such as sand by adding a flocculant, and a process of decomposing organic matter using microorganisms. A series of processes are applied. The sewage primary treated water contains salts and dissolved organic matter. The sewage primary treated water thus treated contained 248 mg / L of dissolved organic matter in terms of TOC (total organic carbon content).

The demonstration experiment was performed as follows, and the water to be treated was treated by using an experimental device simulating the water treatment device of FIG. 1 and applying a polyamide as the polymer material 13 to the surface of the ceramic honeycomb as the adsorption module. And it processed with the reverse osmosis membrane module, and the organic substance adsorption amount to the reverse osmosis membrane 3 was measured using size exclusion chromatography (GPC). For comparison, an adsorption module 1 not coated with the polymer material 13 was prepared and subjected to the same treatment, and the amount of organic matter adsorbed on the reverse osmosis membrane 3 was compared using GPC. The GPC conditions are as follows. The column is manufactured by Hitachi Chemical Co., Ltd., model number: GL-W550, column temperature: 41 ° C., sample volume: 20 μL, eluent: pure water, flow rate: 1.0 mL / min, detector (detection wavelength): UV ( 220 nm). As a result, the dissolved organic matter was reduced to 12 mg / L in terms of TOC (total organic carbon content) after the treatment with the adsorption module 1 than before the treatment with the adsorption module 1.

In addition, it was also confirmed that the polyamide modification can remove organic substances in the low-molecular region compared with the polyamide unmodified. That is, it is considered that different types of dissolved organic substances are adsorbed between the polyamide-modified and the polyamide-unmodified.

In addition, in the polyamide unmodified adsorption module 1 (the adsorbent material 13 on the ceramic honeycomb structure 2 is not modified), the dissolved organic matter is 226 mg / L in terms of TOC (total organic carbon content), and the ceramic honeycomb structure 2 The alumina group in the constituent material formed on the surface of the partition wall 10 can adsorb dissolved organic matter in the sewage primary treated water, and was confirmed to be effective as an adsorption module.

Therefore, the partition wall 10 of the ceramic honeycomb structure 2 used in the adsorption module 1 does not need to modify the adsorption material 13 on the entire surface of the partition wall 10 and the inner surface of the fine through hole, and is partially unmodified. It was found that the dissolved organic matter having a wide range of molecular weight can be adsorbed by the presence of the part.

DESCRIPTION OF SYMBOLS 1 ... Adsorption module, 2 ... Ceramic honeycomb structure, 3 ... Reverse osmosis membrane, 4 ... Module, 5 ... Water storage tank, 6 ... Pump, 7 ... Housing, 8 ... support, 9 ... outer peripheral wall, 10 ... partition wall, 11 ... plugging portion, 12 ... flow path, 13 ... polymer material (adsorption material).

Claims

In the adsorption structure that adsorbs organic matter in the treated water,
The outer wall,
A plurality of flow paths provided inside the outer wall;
A partition that separates each of the plurality of flow paths,
The said partition is smaller than the diameter of the said flow path, has a communicating hole which connects the said flow path and another flow path, and adsorb | sucks the said organic substance, The adsorption structure characterized by the above-mentioned.
In claim 1,
The adsorption structure has a first surface and a second surface facing each other,
The plurality of flow paths are provided side by side in a direction intersecting the longitudinal direction, and a first flow path that opens to the first surface, and a second flow path that opens to the second surface, An adsorbing structure characterized by comprising:
In claim 2,
The adsorption structure according to claim 1, wherein the first channel does not open to the second surface, and the second channel does not open to the first surface.
In claim 2 or claim 3,
The adsorption structure, wherein the first flow path and the second flow path are alternately provided in a direction crossing the longitudinal direction.
In any one of Claims 1 thru | or 4,
The said partition is formed with ceramics, The adsorption structure characterized by the above-mentioned.
In claim 5,
The adsorption structure according to claim 1, wherein the outer wall and the partition wall are formed of a ceramic honeycomb.
In claim 5 or claim 6,
An adsorption structure, wherein a polymer material that adsorbs the organic substance is formed on the ceramic.
In any one of Claims 2 thru | or 7,
The first flow path is formed by sealing a hole communicating the first surface and the second surface with a plugging portion on the second surface side,
The second flow path is formed by sealing a hole connecting the first surface and the second surface with a plugging portion on the first surface side. Characteristic adsorption structure.
In claim 8,
The adsorption structure according to claim 1, wherein the communication hole of the partition wall has a larger porosity than the hole of the plugging portion.
In claim 5,
An adsorption structure, wherein the material constituting the partition wall contains alumina or a composite oxide containing alumina.
In claim 10,
Alumina contained in the material constituting the partition or a composite oxide containing alumina is at least one of aluminosilicate, silimanite, mullite, spinel, cordierite, aluminum titanate, and lithium aluminum silicate. Characteristic adsorption structure.
In claim 10,
An adsorption structure comprising an alumina-containing coating formed on at least a part or the entire surface of the partition wall or the communication hole surface in the partition wall.
In claim 7,
The uppermost layer of the surface of the partition wall or the surface of the communication hole in the partition wall includes at least one or more kinds of polymers containing at least a part or the entire surface of the polymer material containing 2 equivalents or more of amino groups as the polymer material. An adsorption structure characterized by modifying a contained material.
In claim 8,
An adsorption structure, wherein a material constituting the partition is different from a material constituting the plugging portion.
In claim 14,
An adsorbing structure comprising at least one material selected from the group consisting of glass, polyimide, polyamide, polyimide amide, polyurethane, acrylic, epoxy, polypropylene, and Teflon as a material constituting the plugged portion.
In claim 14,
An adsorption structure characterized in that the material constituting the plugged portion is a composite material made of ceramic particles and an organic polymer material.
In claim 16,
The ceramic particles used for the material constituting the plugged portion are at least one of alumina, silica, magnesia, titania, zirconia, zircon, cordierite, spinel, aluminum titanate, and lithium aluminum silicate. An adsorption structure characterized by that.
In claim 16,
The organic polymer material used for the material constituting the plugged portion is at least one of polyimide, polyamide, polyimide amide, polyurethane, acrylic, epoxy, polypropylene, and Teflon. Adsorption structure.
In claim 7,
The porosity of the material used for the partition wall is 45% to 70%, and the porosity of the material used for the plugging is smaller than the porosity of the material used for the partition wall, 0% to 40%. Further, the adsorption structure is characterized in that the thickness of the plugging is larger than the thickness of the partition wall.
An adsorption structure according to any one of claims 1 to 19,
A housing,
A support member for supporting the adsorption structure within the housing;
An inlet for taking up the water to be treated;
A discharge port for discharging the treated water,
The intake port is connected to the first flow path;
The suction module, wherein the discharge port is connected to the second flow path.
In the manufacturing method of the adsorption structure that adsorbs organic matter in the water to be treated,
The first surface facing the second surface communicates with the second surface and has a plurality of through holes separated from each other by the partition walls, the partition walls communicating with the through holes, and an adsorbing material that adsorbs organic matter Forming an adsorbent structure body having:
Plugging the through hole with a plugging portion on the first surface side to form a second flow path opened on the second surface side; and
Plugging the through-holes not plugged on the first surface side with a plugging portion on the second surface side to form a first flow path opened on the first surface side;
A method for producing an adsorption structure comprising
In claim 21,
A method for manufacturing an adsorption structure, wherein a temperature for forming the plugged portion is lower than a temperature for forming the partition wall.
In claim 21,
As a method of forming the plugging portion, a printing mask having an opening at a desired position is used, and the paste used for the plugging is placed at a desired position in the flow path formed by the partition by the screen printing method. A method for producing an adsorption structure, comprising forming a seal.
In claim 21,
As a method for forming the plugged portion, a dispenser having a plurality of nozzles arranged at desired positions is used, and a paste used for the plugging is formed in the flow path formed by the partition by a paste discharge method. A method for manufacturing an adsorption structure, wherein the plugging is formed at a predetermined position.
In claim 21,
A method for producing an adsorption structure, comprising: forming a polymer material that adsorbs organic molecules on the partition wall.