JP6164366B2 - Adsorption member - Google Patents

Description

  The present invention relates to an adsorption member.

  As background arts in this technical field, there are Japanese Patent No. 3864817 (Patent Document 1), Japanese Patent Application Laid-Open No. 2005-518272 (Patent Document 2) and Japanese Patent Application Laid-Open No. 2012-091151 (Patent Document 3).

  In Japanese Patent No. 3864817 (Patent Document 1), prior to supplying water to be treated to a reverse osmosis membrane device, water treatment is performed by an adsorption cylinder using an adsorbent containing a constituent material of the reverse osmosis membrane. Methods and apparatus are described.

  JP-T-2005-518272 (Patent Document 2) has a flat flexible support having a large number of openings, and a coating existing on or in the support, and is used for a battery. Membranes are described that can be used as separators or as microfiltration membranes. The material of the support is selected from polymer transition nonwovens, the porosity of which is higher than 50% and the coating is a porous ceramic coating, the support having a thickness of 10 to 200 μm. Have.

  JP 2012-091151 A (Patent Document 3) includes an outer wall, a plurality of flow paths provided inside the outer wall, and a partition that separates each of the plurality of flow paths. An adsorbing structure that has a communication hole that is smaller than the diameter and that communicates a channel with another channel and an adsorbing substance that adsorbs organic matter is described.

Japanese Patent No. 3864817 JP 2005-518272 A JP 2012-091151A

  The water treatment system includes a module having a separation membrane that removes a substance to be separated from raw water. However, when fouling (clogging) occurs in the separation membrane, the separation performance for removing the substance to be separated from the raw water deteriorates. Therefore, fouling does not occur in the state where fouling has occurred in the separation membrane. In order to produce the same amount of water as the state, it is necessary to increase the operating capacity of the water treatment system.

  Further, when fouling occurs in the separation membrane, it is necessary to clean the membrane surface of the separation membrane. Furthermore, when the membrane surface of the separation membrane does not recover the filtration capability of the separation membrane in which fouling has occurred, the element needs to be replaced. At the time of element replacement, it is necessary to stop the water treatment system for a long time, and the part cost and replacement work cost are added to the running cost. For this reason, the occurrence of fouling in the separation membrane increases the water treatment cost of the water treatment system.

  Then, this invention provides the technique which can reduce the water treatment cost of a water treatment system by reducing the adsorbate to the membrane surface of a separation membrane.

  In order to solve the above problems, an adsorbing member that is an example of the present invention includes an outer wall and a flow path provided inside the outer wall, and inputs treated water containing a hydrophilic substance and a hydrophobic substance. The flow path has an adsorbing portion having a member that adsorbs a hydrophilic substance and a member that adsorbs a hydrophobic substance, and the member that adsorbs the hydrophilic substance or the hydrophobic substance. The adsorbing member is formed in a particle shape.

  An adsorbing member that is an example of the present invention is an adsorbing member that includes an outer wall and a flow path provided inside the outer wall, and into which treated water containing a hydrophilic substance and a hydrophobic substance is introduced. The adsorbing member has a hollow structure and has a plurality of hollow fibers in which one of the two ends is closed, and the hollow fiber has a space outside and an inside of the hollow fiber. A partition wall that separates the space from each other, and a partition wall that includes a communication hole that is connected from the space inside the hollow fiber to the outside space, and a flow path is formed inside the hollow fiber, and communicates with the channel. The hole is formed with an adsorbing part for adsorbing a hydrophilic substance or a hydrophobic substance, and the adsorbing part of one hollow fiber of the hollow fibers is composed of a member adsorbing the hydrophobic substance, and the other of the hollow fibers. The hollow fiber adsorbing part is constituted by a member adsorbing a hydrophilic substance.

  An adsorbing member that is an example of the present invention includes an outer wall, a plurality of flow paths provided inside the outer wall, and a partition that separates one of the plurality of flow paths from the other flow path. An adsorbing member into which water to be treated containing a hydrophilic substance and a hydrophobic substance is charged, and the partition wall has a communication hole that connects one channel to another channel In addition, it has a relationship of d / l ≧ 0.23 with respect to the thickness d of the partition wall and the width l of the flow path.

ADVANTAGE OF THE INVENTION According to this invention, the adsorbate to the membrane surface of a separation membrane can be reduced, and the water treatment cost of a water treatment system can be reduced.
Problems, configurations, and effects other than those described above will be clarified by the following description of embodiments.

It is the schematic which shows an example of a structure of the seawater desalination system by a present Example. It is a side view which shows an example of the adsorption | suction module which has the porous ceramic honeycomb adsorbent by a present Example. It is an end view of the inflow side which shows an example of the porous ceramic honeycomb adsorbent by a present Example. (A) is an end view when the cross section of the flow path in a direction orthogonal to the direction in which water flows is a square, and (b) is an end face in the case where the cross section of the flow path in a direction orthogonal to the direction in which water flows is a triangle. FIG. It is sectional drawing along the direction through which the water flows which shows an example of the porous ceramic honeycomb adsorbent by a present Example. It is a schematic diagram which shows a part of surface of the partition of the porous ceramic honeycomb adsorbent by a present Example. It is a schematic diagram which expands and shows a part of surface of the partition of the porous ceramic honeycomb adsorbent by a present Example. (A) is a schematic diagram of an adsorbing material in which hydrophobic particles and hydrophilic particles are fixed using a binder, and (b) is a schematic diagram of an adsorbing material in which hydrophobic particles are fixed using a hydrophilic binder. (C) is a schematic diagram of an adsorbent material in which hydrophilic particles are fixed using a hydrophobic binder. It is a schematic diagram which expands and shows a part of surface of the partition of the porous ceramic honeycomb adsorbent by a present Example. (A) is a schematic diagram illustrating the performance recovery mechanism of an adsorbent material in which hydrophobic particles and hydrophilic particles are fixed using a binder, and (b) is a diagram in which hydrophobic particles are fixed using a hydrophilic binder. (C) is a schematic diagram illustrating the performance recovery mechanism of the adsorbing material in which hydrophilic particles are fixed using a hydrophobic binder. It is sectional drawing which expands and shows a part of flow path of the porous ceramic honeycomb adsorbent by a present Example. (A) is a cross-sectional view when the cross section of the flow path in the direction orthogonal to the direction in which water flows is a quadrangle, (b) is a cross section in the case where the cross section of the flow path in the direction orthogonal to the direction through which water flows is a triangle FIG. It is a graph explaining the relationship between the passage time coefficient of water and the ratio of the partition wall thickness to the channel width in the porous ceramic honeycomb adsorbent according to this example. (A) is a graph in the case where the cross section of the flow path in the direction orthogonal to the direction in which water flows is a square, and (b) is a graph in the case where the cross section of the flow path in the direction orthogonal to the direction in which water flows is a triangle. FIG. It is a figure which shows the structure of the other adsorption | suction member in a present Example. It is a schematic diagram of the Example of the structure of the other adsorption | suction member in a present Example. It is a schematic diagram of the cross section of the structure of the other adsorption member in a present Example. It is a schematic diagram of the cross section of the structure of the other adsorption member in a present Example.

  In the following embodiments, when necessary for the sake of convenience, the description will be divided into a plurality of sections or embodiments. However, unless otherwise specified, they are not irrelevant to each other, and one is the other. There are some or all of the modifications, details, supplementary explanations, and the like.

  Further, in the following embodiments, when referring to the number of elements (including the number, numerical value, quantity, range, etc.), especially when clearly indicated and when clearly limited to a specific number in principle, etc. Except, it is not limited to the specific number, and may be more or less than the specific number.

  Further, in the following embodiments, the constituent elements (including element steps) are not necessarily indispensable unless otherwise specified and clearly considered essential in principle. Needless to say.

  In addition, when referring to “consisting of A”, “consisting of A”, “having A”, and “including A”, other elements are excluded unless specifically indicated that only that element is included. It goes without saying that it is not what you do. Similarly, in the following embodiments, when referring to the shapes, positional relationships, etc. of the components, etc., the shapes are substantially the same unless otherwise specified, or otherwise apparent in principle. And the like are included. The same applies to the above numerical values and ranges.

  Further, in the drawings used in the following embodiments, hatching may be added to make the drawings easy to see even if they are plan views. In all the drawings for explaining the following embodiments, components having the same function are denoted by the same reference numerals in principle, and repeated description thereof is omitted. Hereinafter, the present embodiment will be described in detail with reference to the drawings.

  First, since it seems that the water treatment system by this Embodiment becomes clear, the problem which it is going to solve in the background art and the water treatment system discovered by the present inventors is demonstrated in detail.

  In advanced treatment for water purification, a reverse osmosis membrane (hereinafter referred to as RO (Reverse Osmosis) membrane) is used as a separation membrane for removing substances to be separated from raw water. A semipermeable membrane is used for the RO membrane, and the material of the semipermeable membrane is roughly divided into cellulose acetate type and aromatic polyamide type. Among these, aromatic polyamide RO membranes are widely used for industrial use because of their high water permeation performance and electrolyte removal performance. The structure is often a composite membrane structure in which an aromatic polyamide film is formed on the surface of a microporous porous support, and the thickness of the aromatic polyamide film is, for example, 0.1 μm or less.

  RO membranes are used for the production of pure water used in the manufacture of precision electronic equipment such as semiconductors, the removal of organic substances dissolved in water in advanced treatment of water and final treatment of sewage and wastewater, or the removal of electrolytes in seawater desalination. .

  Among these uses, when the RO membrane is used for seawater desalination, for example, water is supplied to the RO membrane through the following treatment process. First, a fine suspension such as sand is separated by filtering through an ultrafiltration membrane (hereinafter referred to as UF (Ultrafiltration) membrane), subsiding in a sedimentation basin, or a combination of both. At this time, a floc may be formed by adding a flocculant or the like to the suspension as necessary. When the water obtained in this way (hereinafter referred to as pretreated water) is supplied to the surface of the RO membrane while being pressurized, it is suitable for drinking because it contains almost no electrolytes and organic substances from the back surface on the opposite side of the RO membrane. Water (hereinafter referred to as permeate) is obtained. Seawater contains 20 to 40 g / L of sodium chloride as an electrolyte. When this is separated by the RO membrane, the electrolyte can be reduced to 1 mg / L or less.

  By the way, the pretreated water contains organic substances and the like, and a part of the pretreated water is adsorbed on the surface of the RO membrane and inhibits the osmotic action. The adsorbate adsorbed on the surface of the RO membrane includes organic matter fouling that adsorbs organic matter, scales in which electrolyte is deposited at a high concentration near the surface of the RO membrane, and microorganisms contained in the pretreatment water. Biofouling that grows on the surface. In the case of scale and biofouling, the adsorbate can be removed by shearing force by periodically flowing clean water over the surface of the RO membrane.

  However, in the case of organic matter fouling, the organic matter is remarkably smaller than the boundary layer of the flow velocity on the surface of the RO membrane, so the adsorbate cannot be completely removed by shearing force and gradually adsorbs on the surface of the RO membrane. Objects accumulate and impede water permeability. As a result, when operating at a constant pressure, the permeated water amount decreases, and when feedback is applied to power (for example, pressure) to obtain a constant permeated water amount, the operating pressure increases. In either case, the power cost of the pump per unit permeate increases.

  Further, since the adsorbate cannot be completely removed by the shearing force, the RO membrane gradually deteriorates when the RO membrane is chemically cleaned with the cleaning liquid. For this reason, the ion rejection is reduced. Further, as these progress, it becomes necessary to replace the RO membrane module. When replacing the RO membrane module, it is necessary to stop the operation of the water treatment system for a long time, and since the RO membrane module cannot be recycled, it is necessary to replace it with a new RO membrane module. For this reason, the running cost per unit amount of water further increases due to a decrease in the operation rate of the water treatment system, the cost of consumables for the RO membrane, the waste treatment cost, and the like.

  For this reason, before supplying pretreatment water to the RO membrane, there is a method of adding a pretreatment step for removing organic substances in advance and extending the life until the replacement of the RO membrane module. The pretreatment method includes a method of decomposing organic matter, a method of collecting and removing organic matter by adsorbing it on an adsorbent fixed in a pipe, or a method of adding a flocculant to collect organic matter as coarse particles. There is a method to remove it.

  Patent Document 1 discloses a method using an adsorbent made of the same material as the RO membrane as a method for adsorbing organic matter. However, as described above, since the RO membrane cannot be recycled, there is a problem that it is difficult to reuse the adsorbent made of the same material as the RO membrane. Therefore, it is necessary to replace the adsorbent made of the same material as the RO membrane at a frequency equivalent to the replacement frequency of the RO membrane when the adsorbent made of the same material as the RO membrane is not used for the pretreatment.

  Patent Document 2 discloses a technique of using an adsorbent having a large contact area with treated water using a fibrous polymer and a ceramic porous body as a method for removing organic substances. However, the method of Patent Document 2 has a problem that the diameter of the flow path is about 200 nm and is easily blocked.

  Patent Document 3 discloses a technique using an adsorbent using a porous ceramic honeycomb structure as a method for removing organic substances. However, according to the study by the present inventors, the method of Patent Document 3 has a problem that the adsorption performance varies greatly depending on the water quality of the sea area used. The water quality here refers specifically to the concentrations and ratios of the following four types of organic substances. That is, in seawater, (1) a substance whose adsorptivity to a hydrophobic surface described later exceeds the adsorptivity to a hydrophilic surface described later (hereinafter referred to as a hydrophobic organic substance), and (2) a hydrophilic surface described later. The adsorbing property of this material is higher than the adsorbing property on the hydrophobic surface described later, and is positively charged in seawater (hereinafter referred to as a cationic organic substance). (3) Adsorbing property on the hydrophilic surface described later However, a substance that exceeds the adsorptivity to the hydrophobic surface described later and is negatively charged in seawater (hereinafter referred to as an anionic organic substance), (4) the adsorptivity to the hydrophilic surface described later is There are four types of substances that exceed the adsorptivity to the hydrophobic surface to be described and that are not charged in seawater (hereinafter referred to as neutral hydrophilic organic substances). Moreover, the high adsorbability here means that the adsorption equilibrium constant is large (exceeds). Since the ratio of these four kinds of substances varies depending on the water quality of the sea area used, it has been clarified by the inventors that the adsorption performance varies greatly depending on the sea area used in the method of Patent Document 3. As a result of such a feature, the amount of adsorbent required depending on the sea area to be used becomes enormous, and the running cost for seawater desalination treatment increases.

  A present Example demonstrates the seawater desalination system which desalinates seawater using an RO membrane as an example of a water treatment system. The water treatment system according to the present embodiment is not limited to a seawater desalination system using an RO membrane. For example, seawater freshwater using a microfiltration membrane (hereinafter referred to as NF (Microfiltration) membrane) or an ion exchange membrane. Needless to say, the present invention can also be applied to a purification system, a reused water production system that purifies wastewater to produce reused water, and a pure water / ultrapure water production system that produces pure water or ultrapure water.

The configuration of the seawater desalination system, the water treatment method in the seawater desalination system, the RO membrane module filtration method, the porous ceramic honeycomb adsorbent (adsorption structure, porous ceramic honeycomb structure, ceramic structure or ceramic honeycomb) The structure of the adsorption module having a structure and the like and the function of the porous ceramic honeycomb adsorbent will be described.
<Configuration of seawater desalination system>

  The structure of the seawater desalination system according to the present embodiment will be described with reference to FIG. FIG. 1 is a schematic diagram illustrating an example of the configuration of a seawater desalination system according to the present embodiment.

  As shown in FIG. 1, the seawater desalination system 1 according to this embodiment removes salt, organic matter, microorganisms (including fungi), boron, solid suspended matters, and the like contained in seawater as substances to be separated for desalination. It is a water treatment system, and is mainly composed of three parts in the order of the seawater intake part 10, the pretreatment part 20, and the desalination part 30 from the upstream side.

  The seawater intake unit 10 includes an intake pipe 11, an intake pump 12, and a raw water tank 13. The intake pipe 11 may be configured to be installed in the sea and suck up seawater as raw water, or may be configured to extend to the offshore and suck deep water as raw water, or buried in the seabed and filtered with seabed sand. The structure which sucks up the seawater used as raw water later may be sufficient. The intake pump 12 may be configured to be installed in the sea as well as configured to be installed on land.

  Further, in order to prevent organisms such as microorganisms, algae and shellfish from growing in the intake pipe 11 and blocking the intake pipe 11, chemicals (for example, bactericides, etc.) that prevent the growth of these organisms are contained in the intake pipe 11. It is good also as a structure inject | poured into.

  The pretreatment unit 20 includes, for example, a sand filtration tank 21, a porous ceramic honeycomb adsorbent 22, a water feed pump 22a, and an RO membrane supply water tank 23, and performs pretreatment for sterilizing microorganisms and removing other suspended components. . Furthermore, the pretreatment unit 20 includes a chemical injection system 24 that injects a plurality of types of chemicals into raw water. The medicinal injection system 24 is configured according to the type of chemical injected into the raw water. The suspended component is often an organic substance. Moreover, it may have an inorganic substance.

  FIG. 1 shows a bactericide injecting unit 24a, a pH adjusting agent injecting unit 24b, a flocculant injecting unit 24c, and a neutralizing / reducing agent injecting unit 24d. The sterilizing agent injection unit 24a injects a sterilizing agent that sterilizes microorganisms. The pH adjuster injection unit 24b injects a pH adjuster for preventing the generation of scale due to multivalent ions and improving the aggregation efficiency. The flocculant injection part 24c injects the flocculant for efficiently removing organic substances in the sand filtration tank 21. The neutralizing / reducing agent injection unit 24d injects a neutralizing agent and a reducing agent.

  From the sterilizing agent injecting section 24a, hypochlorous acid or chlorine is injected into the raw water as a sterilizing agent for sterilizing microorganisms. The killing rate or survival rate of microorganisms in the raw water varies depending on the interval and concentration of intermittent injection of the bactericide injected from the bactericide injection unit 24a.

  Hypochlorous acid or chlorine injected as a disinfectant reduces the function of the RO membrane provided in the RO membrane module 32 of the desalting unit 30, so that the raw water is reduced before being sent to the RO membrane module 32. The structure which does is preferable. For this reason, it is preferable to avoid excessive injection of the bactericidal agent, and the bactericidal agent injection portion 24a is provided with an adjustment valve VL1 for adjusting the injection amount of the bactericidal agent.

  Moreover, you may inject | pour a disinfectant into the intake pipe 11 from the disinfectant injection | pouring part 24a. In this case, it is preferable that an adjustment valve VL1 for adjusting the injection amount is also provided in a pipe line for injecting the bactericide into the water intake pipe 11.

  Moreover, in order to prevent generation | occurrence | production of the scale by a multivalent ion and to improve agglomeration efficiency, it is preferable that the raw | natural water processed with the seawater desalination system 1 is adjusted to acidity (pH 3-5). Therefore, a pH adjuster such as sulfuric acid is injected into the raw water from the pH adjuster injecting section 24b, and the pH is adjusted appropriately. The pH adjuster injection part 24b is provided with an adjustment valve VL2 for adjusting the injection amount of the pH adjuster.

  Further, a coagulant such as polyaluminum chloride or ferric chloride is injected into the raw water from the coagulant injection part 24c. Since the organic matter contained in the raw water is promoted by the flocculant, the organic fine particles having a size of 0.1 μm or more are grown into organic flocs having a size of 1 μm or more by the injection of the flocculant. Thereby, the removal efficiency of the organic substance in the sand filtration tank 21 improves.

  When the amount of the flocculant injected is too small, flocs do not grow properly, and organic matter may pass through the sand filtration tank 21. Further, when the amount of the flocculant injected is excessive, surplus that is not used for floc growth gives a load to the RO membrane provided in the RO membrane module 32 of the desalting unit 30. Accordingly, the flocculant injection portion 24c is provided with an adjustment valve VL3 for adjusting the injection amount of the flocculant.

  From the neutralizing / reducing agent injection unit 24d, a neutralizing agent for neutralizing the raw water adjusted to acidic pH 3-5 and a reducing agent for mainly reducing the bactericidal agent are injected into the raw water. The neutralizing / reducing agent injection part 24d is provided with an adjusting valve VL4 for adjusting the injection amounts of the neutralizing agent and the reducing agent.

  As described above, in the pretreatment process in the pretreatment unit 20, a process of sterilizing microorganisms by injecting a bactericide, a process of injecting a flocculant to grow organic flocs, and removing organic substances in the sand filtration tank 21. And done.

  The desalination unit 30 includes a main line LM composed of a high-pressure pump 31, an RO membrane module 32, and a fresh water tank 33, and a sub-line LS composed of an RO membrane module 32, an energy recovery device 34, and a concentrated water tank 35. Prepare. Further, the desalting unit 30 includes a waste water tank 36, a measuring unit, and a chemical injection system 39 for injecting a plurality of types of chemical solutions into the raw water.

  A semipermeable membrane is used for the RO membrane provided in the RO membrane module 32. A semipermeable membrane is a membrane that allows only water molecules to permeate due to the difference between the interaction between the semipermeable membrane and water molecules and the interaction between the semipermeable membrane and the substance to be separated. Some are polyamide-based. In this embodiment, an RO membrane made of an aromatic polyamide-based semipermeable membrane is used, but an RO membrane made of a cellulose acetate-based semipermeable membrane may be used.

  The configuration of the RO membrane module 32 is not limited. For example, a composite membrane in which a polyamide membrane (for example, an aromatic polyamide-based semipermeable membrane) having a thickness of 0.1 μm or less is formed on the surface of a microporous support having a thickness of about several hundreds μm in a shape called a spiral. The RO membrane module 32 can be configured by a folded element or an element in which hollow fiber membranes are bundled. In this case, the element has a diameter of 4 inches (about 10 cm), 8 inches (about 20 cm), or 16 inches (about 40 cm), and a cylindrical shape having a length of about 1 m is often used. The RO membrane module 32 arranged in series in the pressure vessel is used.

  In an element in which the RO membrane is folded in a spiral shape, for example, a polyethylene spacer is sandwiched between the membranes in order to prevent the RO membranes from sticking to each other. However, the gap between the spacer and the RO membrane is as narrow as about 0.5 μm. Therefore, a safety filter may be attached on the upstream side of the RO membrane module 32.

  The chemical injection system 39 is configured according to the type of chemical used for cleaning the RO membrane module 32. FIG. 1 shows an antibacterial agent injection part 39a for injecting an antibacterial agent that suppresses the growth of microorganisms, an acid injection part 39b for removing scales, and an alkali injection part 39c for removing organic substances.

  2,2-Dibromo-3-nitrilopropionamide (hereinafter referred to as DBNPA) or the like is injected into the raw water as an antibacterial agent that suppresses the growth of microorganisms from the antibacterial agent injection unit 39a. The killing rate or survival rate of microorganisms in the raw water varies depending on the interval and concentration of intermittent injection of the antibacterial agent injected from the antibacterial agent injection unit 39a. It should be noted that excessive injection of DBNPA or the like injected as a bacteriostatic agent is preferably avoided, and the bactericidal agent injection part 39a is provided with a control valve VL5 for adjusting the injection amount of the bactericidal agent.

  In addition, in order to periodically remove the generated scale from the acid injection part 39b, an acid such as sulfuric acid is injected into the raw water. The acid injection part 39b is provided with a control valve VL6 for adjusting the amount of acid injected.

Further, alkali such as caustic soda is injected into the raw water from the alkali injection part 39c. The alkali injection part 39c is provided with an adjustment valve VL7 for adjusting the injection amount of alkali.
<Water treatment method in seawater desalination system>

  In the seawater desalination system 1 according to the present embodiment, the raw water taken from the sea through the intake pipe 11 by the intake pump 12 of the seawater intake unit 10 is temporarily stored in the raw water tank 13, and the separated substances contained in the raw water After a part of the precipitate is removed, it is sent to the pretreatment unit 20.

  In the pretreatment unit 20, the raw water subjected to the bactericide injection from the bactericide injection unit 24a, the pH adjustment agent injection from the pH adjustment agent injection unit 24b, and the flocculant injection from the flocculant injection unit 24c is sand. It flows into the filtration tank 21. In the sand filtration tank 21, organic flocs grown to a size of 1 μm or more are mainly filtered and removed by the flocculant, and the raw water that has passed through the sand filtration tank 21 is transferred to the porous ceramic honeycomb adsorbent 22 by the water pump 22a. Sent. In the raw water that has passed through the sand filtration tank 21, organic substances that could not form flocs by the flocculant are dissolved, but are adsorbed and separated from the raw water by interaction with the surface of the porous ceramic honeycomb adsorbent 22. The

  The raw water is pressurized to about 0.1 to 0.5 MPa by a pressurizing means such as a water pump 22a, and is fed to the porous ceramic honeycomb adsorbent 22 (pressure feed). The raw water sent to the porous ceramic honeycomb adsorbent 22 has a higher rate of permeation through the porous ceramic honeycomb adsorbent 22 as the pressure increases, but the ability to separate the substance to be separated from the raw water (so-called separation performance) is reduced. To do.

  The raw water that has passed through the porous ceramic honeycomb adsorbent 22 is injected with a neutralizing agent and a reducing agent from the neutralizing / reducing agent injection part 24d, and the raw water adjusted to be acidic with a pH adjuster is neutralized, The injected germicide is reduced. The raw water is stored in the RO membrane supply water tank 23.

  The raw water stored in the RO membrane supply water tank 23 is pressurized by the high-pressure pump 31 of the desalting unit 30, sent to the RO membrane module 32 (pressure feed), and filtered by the RO membrane module 32. The raw water that has passed through the RO membrane provided in the RO membrane module 32 and from which suspended components have been removed is stored in the fresh water tank 33 as fresh water. On the other hand, the raw water that does not pass through the RO membrane provided in the RO membrane module 32 becomes concentrated water containing suspended components in a state pressurized by the high-pressure pump 31 and is stored in the concentrated water tank 35.

  In some cases, a drainage system for returning the concentrated water stored in the concentrated water tank 35 to the sea, for example, may be provided. In this case, in the drainage system, a process of reducing the salinity concentration and a process of taking out a substance that can be a raw material for the salinity and chemicals are performed.

In addition, the energy recovery device 34 provided in the desalinization unit 30 is, for example, a turbine that rotates with energy when high-pressure concentrated water (high-pressure water) stored in the concentrated water tank 35 is drained, and power is generated by the rotation of the turbine. The generated power can be used as drive power for the high-pressure pump 31 and the like.
<RO membrane module filtration method>

  In the seawater desalination system 1 according to the present embodiment, the RO membrane module 32 includes an RO membrane as a separation membrane. There are the following two methods for filtering raw water with an RO membrane.

  One of the filtration methods is a “total amount filtration method”, which is a method in which the entire amount of raw water is passed through the RO membrane. In this method, a substance to be separated that does not pass through the RO membrane is deposited on the membrane surface of the RO membrane. And since the micropores of the RO membrane are blocked by the deposition of substances to be separated, a phenomenon that the amount of permeated water decreases with operating time, that is, fouling occurs.

  Another one of the filtration methods is a “cross flow filtration method”, which is a method in which raw water flows along the membrane surface of the RO membrane, and a part thereof passes through the RO membrane. In this method, the substance to be separated that does not pass through the RO membrane is discharged together with the raw water and is not deposited on the membrane surface of the RO membrane. However, even in the cross-flow filtration method, the substance to be separated contained in the raw water is gradually adsorbed on the RO membrane due to long-time operation, the micropores are blocked, and the amount of permeated water of the RO membrane gradually decreases, that is, fouling occurs. To do. In this embodiment, the cross-flow filtration method is used, but the whole-volume filtration method may be used.

  The substances to be separated adsorbed on the RO membrane include scales in which the electrolyte is deposited at a high concentration near the membrane surface of the RO membrane, biofouling in which microorganisms contained in the raw water grow on the membrane surface of the RO membrane, and raw water Organic matter fouling that adsorbs organic matter is included.

  For example, with respect to the scale that deposits when the electrolyte concentration increases, the scale should not be deposited even when the electrolyte concentration increases by injection of a scale inhibitor or pH adjuster, or the RO membrane surface periodically It is possible to cope with this by flowing clean water through and removing with shearing force.

  However, organic matter fouling cannot be removed by shearing force and gradually accumulates over a long period of operation. For example, in the case of the seawater desalination system 1, the TOC (Total Organic Carbon) varies depending on the configuration and performance of the pretreatment unit 20, the quality of seawater, and the type of chemicals injected by the chemical injection system 24. In terms of amount), about 0.1 to 10 mg / L of organic matter is contained in the raw water sent to the desalting unit 30.

  In addition, when the organic matter scale is adsorbed and accumulated on the RO membrane, microorganisms grow using the organic matter as a medium to form a biofilm, which causes biofouling.

  In the case of the seawater desalination system 1, the microorganisms contained in the raw water are killed by the bactericide injected from the bactericide injection part 24a. However, RO membranes (especially aromatic polyamide-based RO membranes) decompose and degrade little by little with hypochlorous acid or chlorine, which is a bactericidal agent, so that the bactericidal agent is reduced by the reducing agent and the bactericidal component The raw water in a state not containing water is sent to the desalting unit 30.

  The members such as pipes constituting the desalination unit 30 are sufficiently cleaned after construction, and further regularly cleaned with chemicals after the start of use, but it is impossible to completely eliminate microorganisms from the members such as pipes. is there.

  In addition, microorganisms that cannot be sterilized by the sterilizing agent injected from the sterilizing agent injecting unit 24a may flow into the desalting unit 30 and enter the desalting unit 30 (more specifically, downstream of the RO membrane supply water tank 23). Microorganisms may be present. In this case, since the raw water sent to the desalting unit 30 does not contain a bactericidal component (bactericidal agent having bactericidal power), microorganisms present in the desalting unit 30 cannot be removed, Biofilms are formed by the microorganisms present.

  As described above, when organic matter fouling or bio-fouling occurs in the RO membrane module 32, the filtering ability of the raw water in the RO membrane is reduced, so that the RO membrane needs to be replaced. In the seawater desalination system 1, the elements of the RO membrane module 32 are cleaned or the RO membrane module 32 is replaced.

When the element of the RO membrane module 32 is washed or the RO membrane module 32 is replaced, the seawater desalination system 1 is stopped for a long time, so that the operating rate of the seawater desalination system 1 is lowered. In addition, since the component cost of the element and the replacement work cost are added to the running cost, the running cost of the seawater desalination system 1 increases.
Therefore, it is desirable to remove the organic matter from the raw water as much as possible in the pretreatment unit 20.
<Adsorption module structure>

  The structure of the porous ceramic honeycomb adsorbent according to the present embodiment and the structure of the adsorption module having the porous ceramic honeycomb adsorbent will be described with reference to FIGS.

  FIG. 2 is a side view showing an example of an adsorption module having a porous ceramic honeycomb adsorbent according to the present embodiment.

  As shown in FIG. 2, the adsorption module M is composed of a porous ceramic honeycomb adsorbent 22, a housing (resinous storage container) 201, and a filter support 202. The porous ceramic honeycomb adsorbent 22 is interposed via a gripping member. The filter support 202 in the housing 201 is housed.

  The filter support 202 is fixed to one end into which water before treatment flows and the other end from which water after treatment flows out. The filter support 202 allows water to pass through without resistance, and when water is permeated at 0.1 MPa, the position change at the center of the long axis is 5 with respect to the length of the fixed end in the long axis direction. The material, the thickness, and the holding method are set so that the strength is within%. The filter support 202 may be made of any material that does not have an eluate into water. For example, a resin-based mesh spacer made of polyethylene, polypropylene, polyethylene terephthalate, polystyrene, or the like, and a metal-based material made of stainless steel, titanium, or the like. A mesh or punching metal can be used. In this embodiment, a punching metal having a thickness of about 1 mm is used as the filter support 202, for example.

  FIG. 3 is an end view on the inflow side showing an example of the porous ceramic honeycomb adsorbent according to the present embodiment. FIGS. 3 (a) and 3 (b) are flow paths in a direction orthogonal to the direction in which water flows. It is an end view when the cross section is a quadrangle, and an end view when the cross section of the flow path in the direction orthogonal to the direction in which water flows is a triangle. The direction in which water flows refers to the direction from the inlet to the outlet on the inflow side of the porous ceramic honeycomb adsorbent. The orthogonal direction means an angle formed substantially perpendicular to the direction in which water flows, and does not indicate only 90 degrees. Here, the end surface refers to a contact surface of the porous ceramic honeycomb adsorbent 22 with the filter support 202, facing the direction in which the treated water flows, and a first surface into which the water before treatment flows, There is a second surface through which the subsequent water flows out. 3A shows a channel having a square cross section, and FIG. 3B shows a channel having a regular triangle cross section, but the present invention is not limited to this. For example, it may be a rectangle or an isosceles triangle.

  As shown in FIGS. 3A and 3B, the porous ceramic honeycomb adsorbent 22 includes an outer peripheral wall 209, a plurality of channels 212 provided inside the outer peripheral wall 209, and an adjacent channel 212. And a partition wall 210 to be spaced apart from each other. The partition wall 210 is made of, for example, ceramic.

  The plurality of flow paths 212 are arranged side by side in the first direction and the second direction that are not parallel to each other on the end surface, and the through holes penetrating from the inflow side surface to the outflow side surface are connected to the inflow side end surface or It is formed by plugging the end face on the outflow side. Specifically, the first flow path 212a in which the inflow side of water before treatment is opened and the outflow side of water after treatment on the opposite side is plugged by the plugging portion 211, and the outflow of water after treatment The second flow path 212b is opened on the side, and the inflow side of the water before treatment on the opposite side is plugged with the plugging portion 211. The first channel 212a and the second channel 212b are alternately arranged in the first direction and the second direction, respectively. The diameter of the channel 212 is, for example, about 0.5 to 5 mm.

  In addition, the communication holes formed in the outer peripheral wall 209 and the partition wall 210 are configured with an average pore diameter (for example, about 20 μm) that is a hole structure thinner than the diameter of the flow path 212, and between the adjacent flow paths 212 (for example, the first channel A large number of communication holes (not shown) are formed to communicate between the second flow path 212a and the second flow path 212b.

  FIG. 4 is a cross-sectional view along the direction in which water flows showing an example of the porous ceramic honeycomb adsorbent according to the present embodiment.

As shown in FIG. 4, the pre-treatment water flows into the porous ceramic honeycomb adsorbent 22 into the first flow path 212a having an open inflow side. The pre-treatment water that has flowed into the first flow path 212a flows through a large number of communication holes formed in the partition wall 210 to the second flow path 212b adjacent to the first flow path 212a. An adsorbing material (not shown) is formed on the surface of the partition wall 210 or on the inner surface of the communication hole formed in the partition wall 210, and when the water passes through the partition wall 210, the adsorbing material adsorbs organic substances contained in the water. And remove. Thereafter, the water that has flowed into the second flow path 212b flows out from the opened outflow side of the second flow path 212b.
<Function of porous ceramic honeycomb adsorbent>

  The mechanism of organic matter removal using the porous ceramic honeycomb adsorbent according to the present embodiment will be described with reference to FIG. FIG. 5 is a schematic view showing a part of the surface of the partition wall of the porous ceramic honeycomb adsorbent according to the present example.

  Seawater desalinated by the seawater desalination system contains many types of organic matter and cannot be specified in several types. Due to the difference in the molecular structure of organic matter, it is electrically polarized and has a high affinity with water, ions or polarized solid surfaces, and it has a small electrical polarization with water, ions or polarized solid surfaces. Some have low affinity. Furthermore, there are electrical polarizations that are positively charged and those that are negatively charged. Of the RO membranes used for seawater desalination, the aromatic polyamide membrane used in this example contains an aromatic ring, a carbonyl group, an amino group, and the like, so that it has a hydrophilic region (mainly formed by an aromatic ring. Regions) and hydrophobic regions (regions formed mainly by carbonyl groups and amino groups). Moreover, since the polarization of the amino group is stronger than that of the carbonyl group, a part of the hydrophilic region is positively charged by attracting hydrogen ions in water. For this reason, the substances that adsorb on the aromatic polyamide membrane and inhibit the water generation performance are neutral or negatively charged hydrophilic organic substances (neutral hydrophilic organic substances or anionic organic substances) and hydrophobic organic substances. In order to remove such substances that are easily adsorbed to the RO membrane from the raw water, a hydrophilic region that is neutrally or positively charged and a hydrophobic region are required.

  Here, hydrophobicity and hydrophilicity will be briefly described. Hydrophilic means spontaneously spreading when pure water is dropped on the solid surface, and hydrophobic means not spontaneously spreading when pure water is dropped on the solid surface. To do. As a result of the study by the present inventors, when a contact angle formed by the tangent line of the liquid surface and the solid / liquid interface is used, the contact angle is 40 degrees or less in a hydrophilic state, and the contact angle exceeds 40 degrees. Considering the case as hydrophobic, it became clear that the observed phenomenon could be well explained.

  As shown in FIG. 5, a hydrophilic region and a hydrophobic region are formed on the surface of the partition wall 210 (including the inner surface of the communication hole) of the porous ceramic honeycomb adsorbent 22 according to the present embodiment. It is desirable to form a hydrophilic region and a hydrophobic region on both the surface of the partition wall 210 and the inner surface of the communication hole. This is because the area contributing to adsorption increases by forming a hydrophilic region and a hydrophobic region in both.

The surface of the partition wall 210 does not simply mean a physical boundary surface where the raw water and the partition wall 210 are in contact with each other, but a hydrophilic region formed in a layer on the porous ceramic honeycomb adsorbent and a hydrophobic property. The layer structure of the region is defined as the surface. Moreover, the thing which formed the hydrophilic area | region and the hydrophobic area | region in the shape of a particle | grain, and apply | coated what was mixed with the binder is also included. That is, a coated binder structure having a thickness is also referred to as the surface of the partition wall 210.
In addition, the inner surface of the communication hole has a thickness similar to the surface of the partition wall 210.

  Note that the hydrophilic region and the hydrophobic region formed on the surface of the partition wall 210 and the inner surface of the communication hole are not essential, and only one of them can be implemented. However, it is clear that a higher water treatment capacity can be obtained by forming a hydrophilic region and a hydrophobic region.

  Moreover, water treatment capability will improve if the structural ratio of a hydrophilic region and a hydrophobic region is changed according to the ratio of the hydrophilic organic substance and hydrophobic organic substance which are contained in raw | natural water. For example, when the hydrophilic organic substance: hydrophobic organic substance contained in the raw water is present at a ratio of about 3: 7, it is desirable to form the hydrophilic area: hydrophobic area at a ratio of about 7: 3. Moreover, when hydrophilic organic substance: hydrophobic organic substance exists in the ratio of about 6: 4, it is desirable to form a hydrophilic area | region: hydrophobic area | region in the ratio of about 4: 6.

  Therefore, the hydrophilic organic substance and the hydrophobic organic substance contained in the raw water are efficiently removed by the porous ceramic honeycomb adsorbent 22 before reaching the RO membrane module 32 (see FIG. 1). Here, it is desirable that the hydrophilic region formed on the surface of the partition wall 210 (including the inner surface of the communication hole) of the porous ceramic honeycomb adsorbent 22 is neutrally or positively charged.

  Here, when the porous ceramic honeycomb adsorbent 22 is manufactured using cordierite, the porous ceramic honeycomb adsorbent 22 having only a hydrophilic region is obtained. However, the porous ceramic honeycomb adsorbent 22 is formed using alumina. Is produced, a surface where a moderately hydrophilic region and a hydrophobic region are mixed is formed. These ratios cannot be defined unconditionally depending on the manufacturing conditions of the porous ceramic honeycomb adsorbent 22. Therefore, although the trapping performance of organic substances contained in seawater cannot be defined in general, for example, when seawater collected at Yokohama Port is circulated through the porous ceramic honeycomb adsorbent 22 at a space velocity of 120 (1 / h), cordierite. The product removal rate was 3-7%, while the product made of alumina was 10-60%.

Furthermore, when it is desired to improve the removal rate of organic substances in seawater, a hydrophilic region and a hydrophobic region can be formed by the method described below. A method for forming the hydrophilic region and the hydrophobic region of the adsorbent material formed on the surface of the partition wall and the inner surface of the communication hole of the porous ceramic honeycomb adsorbent according to the present embodiment will be described with reference to FIG. FIG. 6 is a schematic view showing a part of the surface of the partition wall of the porous ceramic honeycomb adsorbent according to the present embodiment in an enlarged manner, and FIGS. 6 (a), (b) and (c) are respectively hydrophobic particles. Schematic diagram of adsorbent material in which hydrophobic particles are fixed using a binder, schematic diagram of adsorbent material in which hydrophobic particles are fixed using a hydrophilic binder, and hydrophilic particles fixed using a hydrophobic binder It is a schematic diagram of the made adsorption material.
A first forming method of the adsorbing material shown in FIG.

  First, a porous ceramic honeycomb adsorbent is prepared. The pore diameter of the porous ceramic honeycomb adsorbent is not particularly limited. Generally, the smaller the pore diameter, the larger the surface area (specific surface area) per unit volume and the larger the adsorption capacity. Desirable. On the other hand, according to the Hagen Poiseuille's equation, the smaller the pore diameter, the greater the permeation resistance. Therefore, power is required to pass water through the porous ceramic honeycomb adsorbent. Also, the smaller the pore diameter, the more likely the blockage occurs due to fine suspended components. For this reason, there is a lower limit for the optimum pore diameter for the porous ceramic honeycomb adsorbent. In the study by the present inventors, the thickness of the partition wall 210 is 0.5 mm and the average pore diameter is 20 μm, the thickness of the partition wall 210 is 1 mm and the average pore diameter is 10 μm, and the thickness of the partition wall 210 is 1 mm. Those having an average pore diameter of 1 μm were mainly used. When the differential pressure generated when seawater was passed through the porous ceramic honeycomb adsorbent at a space velocity of 120 (1 / h) was measured, the maximum was 4 kPa in any porous ceramic honeycomb adsorbent. Small enough compared to the capacity of the water pump. That is, an average pore diameter of 1 μm or more is suitable as a porous ceramic honeycomb adsorbent.

  Subsequently, particles (for example, about 10 nm) smaller than the pore diameter (for example, about 20 μm) of the communication hole for communicating the flow path formed in the partition wall 210 of the porous ceramic honeycomb adsorbent with other flow paths, and having hydrophilicity The hydrophilic fine particles having a hydrophobic property and the hydrophobic fine particles having a hydrophobic property are fixed to the surface of the partition wall 210 of the porous ceramic honeycomb adsorbent and the inner surface of the communication hole using an appropriate binder. The suitable binder is, for example, an acrylic polymer or methyl cellulose. A plurality of layers composed of a plurality of hydrophilic fine particles and a plurality of hydrophobic fine particles are deposited. Thereafter, by drying the porous ceramic honeycomb adsorbent and, if necessary, heat treatment, a hydrophilic region and a hydrophobic region are formed on the surface of the partition wall 210 and the inner surface of the communication hole of the porous ceramic honeycomb adsorbent. An adsorbing material having a thickness of, for example, about 1 μm is formed. In this case, it can apply | coat with fixed thickness and it becomes easy to take a layer structure. By repeating the application a plurality of times and adopting such a layer structure, when the layer in contact with the raw water deteriorates, it becomes easy to peel off the outermost layer. By removing one layer, the non-deteriorated surface comes into contact with the raw water, and the treatment capacity of the water treatment system can be recovered.

Here, examples of the hydrophilic fine particles include silica (silicon dioxide), alumina (aluminum oxide), titania (titanium oxide), zirconia (zirconium oxide), and magnesia (magnesium oxide). Examples of the hydrophobic fine particles include silicon carbide (silicon carbide), graphite, diamond, polystyrene, polyolefin such as polyethylene or polypropylene.
A second forming method of the adsorbing material shown in FIG.

  First, a porous ceramic honeycomb adsorbent is prepared. Subsequently, particles (for example, about 10 nm) smaller than the diameter of the communication hole (for example, about 20 μm) that communicates the flow path formed in the partition wall 210 of the porous ceramic honeycomb adsorbent with other flow paths, and are hydrophobic Is fixed to the surface of the partition wall 210 of the porous ceramic honeycomb adsorbent and the inner surface of the communication hole using a hydrophilic binder. Thereafter, by drying the porous ceramic honeycomb adsorbent and, if necessary, heat treatment, a hydrophilic region and a hydrophobic region are formed on the surface of the partition wall 210 and the inner surface of the communication hole of the porous ceramic honeycomb adsorbent. An adsorbent material having a thickness of, for example, about 1 μm is formed.

Here, the hydrophobic fine particles exemplified in the first forming method can be used as the hydrophobic fine particles, and the inorganic sol binder such as alumina sol or silica sol can be used as the hydrophilic binder.
A third method for forming the adsorbent material shown in FIG.

  First, a porous ceramic honeycomb adsorbent is prepared. Subsequently, particles (for example, about 10 nm) smaller than the diameter of the communication hole (for example, about 20 μm) that communicates the flow path formed in the partition wall 210 of the porous ceramic honeycomb adsorbent with other flow paths, and are hydrophilic. Is fixed to the surface of the partition wall 210 of the porous ceramic honeycomb adsorbent and the inner surface of the communication hole using a hydrophobic binder. Thereafter, by drying the porous ceramic honeycomb adsorbent and, if necessary, heat treatment, a hydrophilic region and a hydrophobic region are formed on the surface of the partition wall 210 and the inner surface of the communication hole of the porous ceramic honeycomb adsorbent. An adsorbent material having a thickness of, for example, about 1 μm is formed.

  Here, the hydrophilic fine particles exemplified in the first forming method can be used as the hydrophilic fine particles, and a mixed solution of an aromatic carboxylic acid and an aromatic amine can be used as the hydrophobic binder. it can.

  Next, a mechanism for recovering the adsorption performance of the porous ceramic honeycomb adsorbent according to the present embodiment will be described with reference to FIG. FIG. 7 is an enlarged schematic view showing a part of the surface of the partition wall of the porous ceramic honeycomb adsorbent according to the present example. (A), (b) and (c) are respectively a hydrophobic particle and a hydrophilic particle. Schematic diagram of the adsorbent material fixed with the binder using a binder, Schematic diagram of the adsorbent material with the hydrophobic particle fixed using a hydrophilic binder, and the hydrophilic particle fixed using a hydrophobic binder It is a schematic diagram of adsorption material.

  As shown in FIG. 7A, the hydrophilic region and the hydrophobic region formed by the first forming method are washed with a solution that dissolves the particles constituting each of the upper region, The particles dissolve and new particles underneath are exposed on the surface.

  As shown in FIG. 7B, for the hydrophilic region and the hydrophobic region formed by the second forming method, a solution for dissolving the hydrophilic binder (for example, an alkaline solution having a pH of 10 or more, hydroxylation) By washing with a sodium aqueous solution or the like, the surface layer of the hydrophilic binder is dissolved. Along with this, the hydrophobic particles contained in the surface layer fall off, and the lower hydrophobic particles are newly exposed on the surface.

  As shown in FIG. 7C, for the hydrophilic region and the hydrophobic region formed by the third forming method, a solution for dissolving the hydrophobic binder (for example, an alkaline solution having a pH of 10 or more, hydroxylation) By washing with a sodium aqueous solution or the like, the surface layer of the hydrophobic binder is dissolved. Along with this, the hydrophilic particles contained in the surface layer fall off, and the hydrophilic particles in the lower layer are newly exposed on the surface.

  Next, replacement of the porous ceramic honeycomb adsorbent will be described. In any of the first, second, and third forming methods, a surface layer of, for example, about 0.1 to 100 nm is dissolved by a single cleaning process, and the amount of dissolution can be known in advance. Therefore, it is possible to calculate the remaining thickness of the adsorbing material from the thickness of the adsorbing material and the number of cleaning processes, and to determine the replacement timing of the adsorption module. As a result, the adsorption module can be replaced before all the adsorption material is removed.

  The water treatment system has a calculation unit, and the calculation by this calculation unit compares the processing capacity at the start of operation of the adsorption module with the processing capacity at the time of measurement, and the processing capacity is lower than at the start of operation. Is confirmed or determined. That is, the usage time of the adsorption module is measured.

  When the water treatment performance of the adsorption module is lower than that at the beginning of operation, for example, it is displayed on the display unit provided in the water treatment system so as to be replaced. Further, the determination result may be notified by e-mail or the like to the administrator of the water treatment system or a service maker that performs maintenance, so that the adsorption module is replaced. In this case, it is possible to know the replacement time of the adsorption module (time when replacement is recommended) from other than the water treatment system.

  Further, the replacement timing of the adsorption module is managed by, for example, a calculation unit provided in the water treatment system, and an appropriate replacement time may be notified to the user from the calculation unit. Moreover, the replacement timing of the adsorption module is managed by, for example, a porous ceramic honeycomb adsorbent manufacturer, and the user may be notified of an appropriate replacement timing from the porous ceramic honeycomb adsorbent manufacturer.

  In the calculation of the replacement time, the time from the start of operation of the previously used adsorption module to the replacement, that is, the usage time is stored. Also, measure the operation time of the adsorption module currently in use, determine the difference from the replacement time of the adsorption module used earlier, calculate the recommended time until replacement, and obtain appropriate water treatment performance. You may notify the remaining time of the useful life of the state to be prepared. Appropriate water treatment performance is appropriately set depending on the water treatment system used. Moreover, you may obtain | require and notify the replacement frequency corresponding to the water treatment system by measuring and memorize | storing the replacement | exchange period of an adsorption | suction module. In this case, it is possible to propose a more suitable replacement time based not only on the performance deterioration of the adsorption module itself but also on the relationship with the treated water from the relationship between the treated water to be treated by the water treatment system and the durability performance of the adsorption module. it can.

  In addition to these notification methods, the above-described notification method by a user, a system administrator, or mail may be used. In this case, the replacement time can be notified in advance before the processing capacity of the adsorption module decreases. Therefore, it is useful for making a maintenance plan for the entire water treatment system together with maintenance of other configurations.

  Also, a plurality of notification methods may be provided, for example, not only informing the manager of the water treatment system, but also informing the manufacturer of selling or supplying the adsorption module in advance so that the time for replacing the adsorption module can be determined in advance. I can inform you. In this case, when the user of the water treatment system desires to replace the adsorption module having a reduced processing capacity, the manufacturer can prepare an adsorption module for replacement corresponding to the water treatment system in advance.

These notification methods can be similarly applied to other embodiments, and it is desirable to implement them in consideration of efficient operation of the water treatment system.
In addition, these notification methods are not essential components, but are an example of an embodiment of a water treatment system.

  In addition, in the above-mentioned notification, when the performance of the adsorption module can be recovered not only by replacing the adsorption module but also by cleaning, the cleaning time (time when cleaning is recommended) is notified. May be. In this case, it can be used for a long time by washing the adsorption module.

  Further, the cleaning frequency and the replacement frequency may be notified together, and in this case, it is possible to contribute to the extension of the life of the adsorption module by the cleaning, the appropriate proposal of the replacement time, and the preparation of the maintenance plan. In addition, it is possible to prevent a reduction in water treatment performance of the water treatment system as a whole.

  In addition, information on the thickness of the hydrophilic region or hydrophobic region formed in the adsorption module, information on the amount of decrease in the thickness of the hydrophilic region or hydrophobic region due to the cleaning process of the adsorption module, and after the reduction The information on the thickness of the adsorption module and the information on the cleaning frequency or replacement frequency of the adsorption module may be measured. Moreover, you may calculate the information estimated with reference to each measured information.

  It is also possible to calculate the replacement frequency or cleaning frequency of the adsorption module using at least one of these pieces of information and notify the user. Furthermore, the exchange frequency or the like can be obtained statistically or empirically with reference to each measured information.

  The adsorption modules M shown in FIG. 2 can be arranged in parallel and in series as necessary, and valves are provided at the inlet and outlet of each adsorption module M (not shown). Further, a pressure release port is provided at the inlet or outlet of each adsorption module M (not shown). When replacing the adsorption module M, the inlet and outlet valves of the adsorption module M to be replaced are closed, then the pressure release port is opened to release the pressure of the housing 201, and the porous ceramic honeycomb is removed from the housing 201. The adsorbent 22 is taken out. Thereafter, a new porous ceramic honeycomb adsorbent 22 is loaded into the housing 201, the housing 201 is assembled, the pressure release port of the adsorption module M is closed, and then the outlet side valve and the inlet side valve of the adsorption module M are opened. Start water.

  Thus, the porous ceramic honeycomb adsorbent according to the present example can maintain the permeation performance over a long period of time by performing an appropriate cleaning process.

  In any of the first, second, and third forming methods, the porous ceramic honeycomb adsorbent is immediately subjected to seawater desalination treatment after forming a new hydrophilic region or hydrophobic region by the above-described treatment. It is also possible to use it. However, after forming a new hydrophilic region or hydrophobic region by the above-described treatment, it is desirable to further wash the surface layer and then use the porous ceramic honeycomb adsorbent for seawater desalination treatment. This is because immediately after the formation of a new hydrophilic region or hydrophobic region by the treatment described above, the binder often covers the surface of the fine particles of the hydrophilic region and the hydrophobic region, This is because the hydrophobic region may not be formed.

  Next, the design of the partition walls and flow paths of the porous ceramic honeycomb adsorbent according to the present embodiment will be described with reference to FIGS. FIG. 8 is an enlarged cross-sectional view showing a part of the flow path of the porous ceramic honeycomb adsorbent according to the present embodiment, in which (a) and (b) are flows in a direction perpendicular to the direction in which water flows. It is sectional drawing in case the cross section of a path is a rectangle, and sectional drawing in case the cross section of the flow path of the direction orthogonal to the direction through which water flows is a triangle. FIG. 9 is a graph for explaining the relationship between the water passage time coefficient and the ratio of the partition wall thickness to the flow path width in the porous ceramic honeycomb adsorbent according to the present embodiment. ) Are graphs in the case where the cross section of the flow path in the direction orthogonal to the direction in which water flows is a quadrangle, and the graph in the case where the cross section of the flow path in the direction orthogonal to the direction in which water flows is triangular.

  The dimensions of the partition 210 and the channel 212 shown in FIGS. 8A and 8B are factors that determine the time for water to pass through the partition 210 between the adjacent channels 212.

  When the cross section of the flow channel 212 shown in FIG. 8A is a square, the thickness of the partition wall 210 is d, the width of the flow channel 212 is l, the length of the flow channel 212 is L, and the porous ceramic honeycomb adsorbent is made of When the area of the end face is A and the total flow rate is Q, the time t for water to pass through the partition wall 210 is expressed as follows. Here, the channel 212 having a square cross section is illustrated.

  Here, a value obtained by dividing the passage time t by (the end face area A × the flow path length L / the total flow rate Q) is defined as a passage time coefficient, and is illustrated in FIG. When the thickness d of the partition wall 210 and the width l of the channel 212 are equal, the maximum transit time coefficient is obtained. The maximum passage time coefficient indicates that the time allowed for interaction with the adsorbing material is the maximum, and that a larger amount of adsorption can be obtained even when the water flow rate is the same. According to the study by the present inventors, good adsorption performance is obtained when the passage time coefficient ≧ 0.3, and the condition for realizing the passage time coefficient ≧ 0.3 is d / l ≧ from FIG. 0.23.

  8B, when the cross section of the channel 212 is a triangle, the partition 210 is defined as d, where the thickness of the partition 210 is d and the width of the channel 212 (height from the bottom of the triangle) is l. The time t during which water passes is expressed as follows. Here, the flow path 212 whose cross section is an equilateral triangle is illustrated.

  Similarly, a value obtained by dividing the passage time t by (the end face area A × the flow path length L / the total flow rate Q) is defined as a passage time coefficient and is shown in FIG. 9B. When the ratio 1 / d between the width l of the channel 212 and the thickness d of the partition wall 210 is 2/3 (about 0.67), the maximum transit time coefficient is obtained. The maximum passage time coefficient indicates that the time allowed for interaction with the adsorbing material is the maximum, and that a larger amount of adsorption can be obtained even when the water flow rate is the same. According to the study by the present inventors, good adsorption performance is obtained when the passage time coefficient ≧ 0.3, and the condition for realizing the passage time coefficient ≧ 0.3 is d / l ≧ 3 from FIG. 0.06.

  Here, the porosity and average pore diameter of the partition walls in this example will be described. The porosity and average pore diameter of the partition walls were measured using a mercury intrusion porosimeter manufactured by Micromeritics. An average pore diameter means the hole diameter of a communicating hole.

Mercury intrusion porosimeters inject mercury into a vacuum septum sample and determine the relationship between the indentation pressure and the volume of mercury injected into the pores of the septum sample. This is a method for obtaining the relationship (pore size distribution). The porosity P was calculated from the total pore volume V and the true specific gravity ρ of the partition wall material using the following formula.
P = {V / (V + 1 / ρ)} × 100
When the partition wall is cordierite, ρ = 2.52 g / cm ³ .

  The average pore diameter is a pore diameter corresponding to 50% of the total pore volume in the pore diameter distribution, and may be expressed as a median pore diameter.

  Next, the structure of another adsorbing member in the present embodiment will be described with reference to FIG. A side view showing an example of a suction module having another suction member 22x according to the present embodiment is the same as that shown in FIG.

  FIGS. 10A and 10B are respectively an end view and a side view on the inflow side showing an example of the adsorbing member according to the present embodiment. Here, the end face refers to the contact surface with the filter support 202 shown in FIG. 2 when the porous ceramic honeycomb adsorbent 22 shown in FIG. 2 is replaced with the adsorbing member 22x, and is opposed to the direction in which the treated water flows. Thus, there are a first surface into which water before treatment flows and a second surface from which water after treatment flows out.

  As shown in FIGS. 10A and 10B, the adsorbing member 22 x has a structure in which the particles 501 are filled in the outer peripheral wall 209.

  The particles 501 are made of ceramic, for example, and the surface thereof constitutes an adsorbing part. For example, as shown in FIG. 10C, the particles 501 can be further improved in adsorbability by using a configuration including particles 511 having a hydrophilic surface and particles 512 having a hydrophobic surface. Here, the adsorption part in this embodiment is a part having particles 511 having a hydrophilic surface or particles 512 having a hydrophobic surface provided on the ceramic surface. The diameter of the particles 501 is, for example, about 10 μm to 5 mm. The particle size does not need to be the same, and varies among particles. In consideration of securing the gap 502 between the particles 501 which becomes a flow path, it is desirable that the particle size is as close as possible.

  The particles 511 having a hydrophilic surface are easy to adsorb a hydrophilic substance, that is, a member that adsorbs a hydrophilic substance. The particle 512 having a hydrophobic surface is a member that easily adsorbs a hydrophobic substance, that is, a member that adsorbs a hydrophobic substance. In addition, even if it is the particle | grains 511 which have a hydrophilic surface, a part of hydrophobic substance is a member which can adsorb | suck. Further, even a particle 512 having a hydrophobic surface is a member that can adsorb a part of a hydrophilic substance.

  FIG.10 (d) is sectional drawing along the direction through which the water flows which shows an example of the other adsorption member by a present Example. Here, an example in which spheres having different particle diameters are configured is shown.

  The water to be treated passes through the void 502 existing between the particles 501 of the adsorbing member 22x as a flow path.

  Here, in FIGS. 10A to 10C, the shape of the particle 501 is described as a spherical shape. However, the shape is not limited to this, and for example, a substantially spheroid (rugby ball shape) or a substantially rectangular parallelepiped. The shape may be a substantially cubic shape, a substantially triangular pyramid shape, or a shape having protrusions such as confetti. The particle 501 may have a shape in which, for example, a particle having a size of several tens of nanometers is bonded to the surface of the particle having a size of, for example, about 10 μm to 5 mm. At this time, for example, hydrophilic particles or hydrophobic particles as shown in FIGS. 5 to 7 may be used as the particles having a size of several tens of nanometers.

  Next, as another embodiment of the present invention, the structure of the suction member will be described with reference to FIG. In particular, an example using a member having a hollow fiber structure will be described.

  FIGS. 11A and 11B are an end view on the inflow side showing an example of the adsorbing member according to this embodiment and a cross-sectional view cut in the direction of the hollow fiber.

  Here, the end face refers to a contact surface with the filter supports 202a and 202b shown in FIG. 12 when the porous ceramic honeycomb adsorbent 22 shown in FIG. 2 is replaced with the adsorbent 22y, and the direction in which the treated water flows. There are a first surface through which water before treatment flows and a second surface through which water after treatment flows out.

  As shown in FIGS. 11A and 11B, the adsorbing member 22y has a structure in which a plurality of hollow fibers 601 are arranged side by side and a gap formed between them is sealed by a fixing portion 602. doing.

  The fixing part 602 fixes the vicinity of the first end of the hollow fiber, the first fixing part 602 a that does not seal the hollow part 603, and the second fixing part that fixes the second end part and seals the hollow part 603. It consists of at least two of the two fixed parts 602b.

  In the partition wall 605 that separates the hollow portion 603 and the outside 604 of the hollow fiber 601, a large number of communication holes that communicate the hollow portion 603 and the outside 604 are formed. The communication hole formed in the partition wall 605 has an average pore diameter (for example, about 1 μm) that is a pore structure smaller than the diameter of the hollow portion 603. The hollow fiber 601 is made of, for example, ceramic. That is, even if the member is made of ceramic, in the present invention, this structure is called a hollow fiber.

  The adsorbing member 22y is also formed by combining, for example, a hollow fiber 611 having a surface that adsorbs a hydrophilic substance and a hollow fiber 612 having a surface adsorbing a hydrophobic substance. The diameter of the hollow fiber 601 is, for example, about 1 to 5 mm. Each hollow fiber can be made of the material constituting the hydrophilic particles and the hydrophobic particles described above.

  12 and 13 are cross-sectional views showing an example of a suction module having the suction member shown in FIG.

  As shown in FIG. 12, the adsorption module M includes an adsorption member 22y, a housing 201, and filter supports 202a and 202b. The adsorption member 22y is accommodated by the filter support 202 in the housing 201 via a gripping member. ing.

  The filter support 202 includes a first filter support 202a located on one opening 203a side of the two openings of the housing 201 and a second filter support 202b located on the other opening 203b side. It consists of two.

  Of the two filter supports, the first filter support 202a is in contact with the first fixed part 602a of the two fixed parts 602 of the adsorption member 22y, and between the first fixed part 602a and the housing 201. It is installed to fill without gaps.

  Further, the second filter support 202b is in contact with the second fixing portion 602b of the two fixing portions 602 of the adsorption member 22y, and a gap 700 is formed between the second fixing portion 602b and the housing 201. Is installed.

  12B is an AA cross section in FIG. 12A, FIG. 12C is a BB cross section in FIG. 12A, and FIG. 12D is a C cross section in FIG. -C cross-sections are shown respectively. FIG. 12C shows an example in which the filter support 202b connects the housing 201 and the second fixing portion 602b at three locations. However, the filter supporting body 202b is not limited to three locations, and the second fixing portion 602b and A gap 700 may be formed between the housing 201 and the housing 201.

  The filter supports 202a and 202b are made of a material that does not pass water and does not elute into water. For example, fluorine rubber, silicon rubber, styrene-butadiene rubber, isoprene rubber, or the like can be used.

  FIGS. 13A and 13B both show the XX cross-section of FIG. 12 and are cross-sectional views along the direction in which water flows showing an example of the adsorbing member according to the present embodiment. FIG. 13A shows an example of flowing water from the first opening 203a side, and FIG. 13B shows an example of flowing water from the second opening 203b side.

  As shown to Fig.13 (a), the water before the process which flowed in from the opening part 203a flows in into the adsorption | suction member 22y into the hollow part 603 of the open hollow fiber. The untreated water that has flowed into the hollow portion 603 flows to the outside 604 of the hollow fiber through a large number of communication holes formed in the partition wall 605.

  An adsorbing material (not shown) is formed on the surface of the partition wall 605 or the inner surface of the communication hole formed in the partition wall 605, and when the water passes through the partition wall 605, the adsorbing material adsorbs organic substances contained in the water. And remove.

  Thereafter, the water flowing into the outside 604 of the hollow fiber flows out from the opening 203b of the housing 201 through the gap 700 between the housing 201 and the second fixing portion 602b.

  Moreover, as shown in FIG.13 (b), the water before the process which flowed into the adsorption member 22y from the opening part 203b side does not flow into the hollow part 603 of the hollow fiber which is not open, It reaches the outside 604 of the hollow fiber via the gap 700 between the filter support 202b and the second fixing portion 602b.

  The water before treatment that reaches the outside 604 of the hollow fiber flows into the hollow portion 603 of the hollow fiber through a large number of communication holes formed in the partition wall 605. An adsorbing material (not shown) is formed on the surface of the partition wall 605 or the inner surface of the communication hole formed in the partition wall 605, and when the water passes through the partition wall 605, the adsorbing material is a hydrophilic substance contained in water. Alternatively, a hydrophobic substance is adsorbed and removed. In particular, it adsorbs hydrophilic or hydrophobic organic substances.

  Thereafter, the water that has flowed into the hollow portion 603 of the hollow fiber flows out from the opening 203a of the housing 201 via the open end of the hollow fiber.

  Here, in the Example of this invention, it adds additionally about the magnitude | size of the hydrophilic particle and hydrophobic particle which were described in FIG.5 and FIG.6. Since the shape of the particles is not necessarily spherical, and there are various measurement methods, there are various definitions for the particle size.

  For example, in Japanese Industrial Standard (JIS Z 8901), the particle size of the test particles is expressed as “the size of the test sieve measured by the sieving method, the Stokes equivalent diameter by the sedimentation method, the circle by the microscope method” “Equivalent diameter”, “Equivalent sphere diameter by light scattering method, and Sphere equivalent value by electrical resistance test method”.

  Among these, the light scattering method includes a laser diffraction method, a dynamic light scattering method, and the like, and in particular, the latter can measure the particle diameter of fine particles of several nm. In the present invention, the term “particle diameter” refers to a sphere equivalent diameter using this dynamic light scattering method.

  In the case of a ceramic honeycomb filter, the particle diameters of the hydrophilic particles and the hydrophobic particles used in the present invention may be sufficiently smaller than the average pore diameter of the communication holes formed in the partition walls. For example, the ceramic honeycomb filter having an average pore diameter of 20 μm In contrast, particles having a particle size of 2 μm or less, for example, alumina particles having an average particle size of 31 nm sold under the trade name of NanoTek (registered trademark) from CI Kasei Co., Ltd. can be used.

  In addition, particles, such as hydrophobic particle | grains and hydrophilic particle | grains as used in the field of this invention, are the concept also including above-mentioned fine particle.

  In addition, as described above, the particle diameter of the particulate ceramic adsorbent particle 501 shown in FIG. 10 can be about 10 μm to 5 mm.

  Moreover, the case where the base material of the hollow fiber adsorbent of the adsorbing member 22x shown in FIG. For the hollow fiber ceramic adsorbent composed of this ceramic, it is sufficient that it is sufficiently smaller than the average pore diameter of the communication holes opened in the hollow fiber wall. For example, for hollow fibers having communication holes with an average pore diameter of 1 μm. For example, particles having a particle diameter of 100 nm or less, such as alumina particles having an average particle diameter of 31 nm as described above, can be used. First, the surface of the hollow fiber ceramic adsorbent is constituted by a hydrophobic material, a hydrophilic material, a material that adsorbs a hydrophobic substance, or a material that adsorbs a hydrophilic substance, as in the examples of FIGS. You can also.

  6 and 10 show an example in which the particle diameter is single for the sake of simplicity, the particle diameter of the particles constituting the powder is not single but has a distribution. When the dynamic light scattering method is used, the particle size distribution can be measured together with the particle size. Although the particle size distribution of the hydrophilic particles and the hydrophobic particles used in the present invention is preferably as small as possible, even when the standard deviation σ when the volume-based frequency distribution with respect to the logarithm of the particle size is approximated by a normal distribution is about 1 There is no practical problem.

  Here, when there is a sample having an average value m and a standard deviation s, it is known that the ratio of elements having a value not less than (ms) and not more than (m + s) is 68.3% of the whole.

  In the case of the above-mentioned particle diameter, since the average value when the logarithm of the particle diameter is approximated by a normal distribution is m, m = log (μ) when the average particle diameter is μ.

  Further, when s = log (α) is set, an element having a logarithm of particle diameter of (m−s) or more and (m + s) or less means that the logarithm of particle diameter is log (μ) −log (α) = log (μ / α) or more and (log (μ) + log (α) = log (μ · α)) or less, that is, particles having a particle size of (μ / α) or more and (μ · α) or less It turns out that.

  The standard deviation σ when the volume-based frequency distribution with respect to the logarithm of the particle diameter is approximated by a normal distribution is about 1 means that the particle diameter is 0.1 μm or more and 10 μm or less. This means that particles account for 68.3% of the total particles on a volume basis, with particles having particle sizes above and below 31.7% of the total.

  By purifying the water to be treated using the porous ceramic honeycomb adsorbing member 22 or the adsorbing member 22x, a hydrophilic material or a hydrophobic material typified by a hydrophilic organic material or a hydrophobic organic material can be efficiently obtained with a large surface area. Substances can be adsorbed and removed.

  In addition, since the cross section of the flow path 212 can be widened, clogging is unlikely to occur, so the frequency of cleaning and replacement of the adsorption module is reduced, and the running cost can be reduced.

  Moreover, the organic substance contained in the to-be-processed water thrown into the adsorption | suction member 22x has a hydrophilic organic substance and a hydrophobic organic substance, and it becomes possible to adsorb these efficiently.

  For example, the particles 511 having a hydrophilic surface shown in FIG. 10C are likely to adsorb hydrophilic organic substances, and the particles 512 having a hydrophobic surface adsorb hydrophobic organic substances. These particles are collectively called an adsorbing part.

  5, 6, and 7, the description has been made using expressions such as hydrophilic particles, hydrophilic binders, hydrophobic particles, and hydrophobic binders. The former two are members that adsorb hydrophilic substances, and the latter two Is a member that adsorbs a hydrophobic substance.

  FIG. 5 shows an example in which hydrophilic particles and hydrophobic particles are formed as a single layer, but this is a schematic illustration of the outermost surface, and as described above, the adsorption performance is recovered. For this purpose, it is desirable to form them by laminating. In addition, this 1 layer does not comprise clearly as a layer structure at the time of manufacture, but includes the concept which uses the thickness removed with the chemical | medical agent etc. as a layer. That is, by removing the layer that appears on the surface, a different layer from the removed layer appears on the surface, thereby restoring the adsorption force.

  Further, although the porous ceramic honeycomb adsorbent 22 has been described in FIG. 2, the present invention is not limited to this, and a particle-filled filter (adsorbing member 22x) as shown in FIG. A hollow fiber filter (adsorption member 22y) as shown in FIG. 13 may be used.

  The porous ceramic honeycomb adsorbent is superior to the particle-filled filter and the hollow fiber filter in that the area of the adsorbing portion that comes into contact with the water to be treated is secured and the resistance when the water to be treated passes is small. Has a point.

Moreover, it has a thin wall comprised by a hole with an average diameter of 5-40 micrometers required for adsorption | suction, and can ensure sufficient flow path on the entrance side and exit side.
Further, the inlet side and the outlet side have a plane-symmetric structure, and the reverse cleaning can be performed with a small resistance.

  In the particle-filling type filter using the adsorbing member 22x shown in FIG. 10, since the inside of the particle does not contribute to the adsorption function, it is necessary to secure the area of the adsorption part by reducing the volume of the particle. When the width of the flow path is also reduced at the same time, the passage resistance of the water to be treated is increased.

  In the hollow fiber filter, in the manufacturing process, the hollow fibers are prepared and then aligned and then fixed. Therefore, in order to secure the strength of the individual hollow fibers, the partition walls tend to be thicker than other structures.

  Since the water to be treated passes through the communication hole provided in the partition wall, the passage resistance increases when the partition wall is thick. Therefore, the partition wall is preferably thin.

  Therefore, in the porous ceramic honeycomb structure, it is easier to secure the width of the flow path by making the partition wall thinner than other particle-filled filters and hollow fiber filters.

  Here, when a porous ceramic honeycomb adsorbent suitable for purification of water to be treated is used, it can be roughly defined as follows depending on the quality of water to be treated.

  That is, the cross-sectional shape of the channel is a square or a triangle, the porosity of the partition walls is 40% to 80%, and the average pore diameter of the communication holes is 5 μm to 20 μm. The ratio of the width of the channel and the partition is as described above.

  In the porous ceramic honeycomb adsorbent, when the shape of the flow path is a square or a triangle, the diameter of the flow path means the width of the flow path shown in FIG.

  When the cross section of the flow path is rectangular instead of square, a suitable range of d / l is defined by setting the arithmetic average of the long side and short side of the rectangle to l. When the thicknesses of the partition walls constituting the two sides of the channel quadrangle that are in contact with each other are different, the arithmetic average thereof is set to d, thereby defining a suitable range of d / l.

  When the cross section of the channel is a triangle and is not a regular triangle, the arithmetic average of the lengths of the three sides is set to l to define a suitable range of d / l. When the thicknesses of the partition walls constituting the two sides of the channel quadrangle that are in contact with each other are different, the arithmetic average thereof is set to d, thereby defining a suitable range of d / l.

  The lower limit value of d / l is as described above, but the upper limit value of d / l can also be obtained as a condition satisfying the passage time coefficient ≧ 0.3, and the cross section of the flow path is square and triangular respectively. From Equation 1 and Equation 2, they are 4.4 and 7.4.

  In FIG. 10 (c), by removing the surface of the adsorbing portion with a chemical or the like, the particles 512 having a hydrophobic surface and the 511 having a hydrophilic surface that did not appear before the removal are exposed, and a new interface is obtained. Appears as That is, after the removal, a new surface of the adsorbing portion having the particles 512 having a hydrophobic surface and the particles 511 having a hydrophilic surface appears.

  When a hydrophobic solid binder having hydrophobic properties is used among the particles, the surface of the solid binder is removed, and particles 512 having a new hydrophobic surface are exposed and appear at the interface.

Therefore, since the organic substance is not adsorbed in the adsorbing portion appearing at the new interface, the adsorbing performance can be recovered. Thereby, it is possible to reduce the number of times of exchanging the adsorption member. Furthermore, the water treatment cost of the whole water treatment system can be reduced.
The above-described removal of the interface is applicable not only to this embodiment but also to other embodiments.

  In addition, the hollow fiber 611 having a surface that adsorbs a hydrophilic substance and the hollow fiber 612 having a surface that adsorbs a hydrophobic substance shown in FIG. 11C are removed by removing the surface with a chemical or the like, respectively. The surface that has not appeared before is exposed as a new interface, so that the attractive force can be recovered.

  As described above, according to the present embodiment, in the pretreatment unit, the organic matter that causes the performance of the RO membrane to deteriorate in advance can be selectively removed from the raw water by the porous ceramic honeycomb adsorbent. Thereby, the replacement frequency of the RO membrane module is reduced, and the running cost of the seawater desalination system can be reduced. That is, the water treatment cost of the water treatment system can be reduced.

  As mentioned above, the invention made by the present inventor has been specifically described based on the embodiment. However, the present invention is not limited to the embodiment, and various modifications can be made without departing from the scope of the invention. Needless to say.

DESCRIPTION OF SYMBOLS 1 Seawater desalination system 10 Seawater intake part 11 Intake pipe 12 Intake pump 13 Raw water tank 20 Pretreatment part 21 Sand filtration tank 22 Porous ceramic honeycomb adsorbent 22a Water pump 22x Adsorption member 22y Adsorption member 23 RO membrane supply water tank 24 Medicine Injection system 24a Disinfectant injection unit 24b pH adjuster injection unit 24c Coagulant injection unit 24d Neutralization reducing agent injection unit 30 Desalination unit 31 High pressure pump 32 RO membrane module 33 Fresh water tank 34 Energy recovery device 35 Concentrated water tank 36 Waste water tank 39 Chemical Injection System 39a Antibacterial Injection Unit 39b Acid Injection Unit 39c Alkali Injection Unit 201 Housing (Resin Container)
202 filter support 202a first filter support 202b second filter support 203a first opening 203b second opening 209 outer peripheral wall 210 partition wall 211 plugging portion 212 flow path 212a first flow path 212b Second flow path 501 Particle 502 Void 511 Particle 512 having hydrophilic surface Particle 601 having hydrophobic surface Hollow fiber 602 Fixed portion 602a First fixed portion 602b Second fixed portion 603 Hollow portion 604 External 605 Partition 611 Hydrophilic Hollow fiber 612 having a surface that adsorbs a hydrophobic substance Hollow fiber 700 having a surface that adsorbs a hydrophobic substance Gap LM Main line LS Subline M Adsorption module VL1, VL2, VL3, VL4, VL5, VL6, VL7 Control valve

Claims (11)

An adsorbing member comprising an outer wall and a flow path provided inside the outer wall, into which water to be treated containing a hydrophilic substance and a hydrophobic substance is charged,
The flow path has an adsorbing portion composed of a first member that adsorbs the hydrophilic substance and a second member that adsorbs the hydrophobic substance,
The first member is formed of particles, silica, alumina, titania, zirconia or magnesia,
The adsorbing member, wherein the first member is held by the second member synthesized using an aromatic carboxylic acid and an aromatic amine. An adsorbing member comprising an outer wall and a flow path provided inside the outer wall, into which water to be treated containing a hydrophilic substance and a hydrophobic substance is charged,
The flow path has an adsorbing portion composed of a first member that adsorbs the hydrophilic substance and a second member that adsorbs the hydrophobic substance,
The second member is formed of particles, silicon carbide, graphite, diamond, polystyrene, or polyolefin,
The adsorbing member, wherein the second member is held by the first member containing alumina or silica. The adsorption member according to claim 1 or 2 ,
By removing the surface of the adsorbing portion, the first member and the second member that have appeared on the surface are peeled off, and the first member and the second member different from the peeled first member and the second member The suction member, wherein the second member appears on a new surface of the suction portion. The adsorption member according to claim 1 or 2 ,
Of the surface of the adsorbing part, the area ratio between the first member and the second member is determined by the composition ratio of the hydrophilic substance and the hydrophobic substance contained in the water to be treated that is put into the adsorbing member. An adsorbing member characterized by being made. An outer wall, a plurality of flow paths provided inside the outer wall, and a partition wall that separates one of the plurality of flow paths from the other flow path, and includes a hydrophilic substance and a hydrophobic substance. An adsorbing member into which water to be treated containing water is charged,
The partition has a communication hole for connecting the one channel and the other channel,
An inner surface of the flow path and the communication hole is provided with an adsorbing portion composed of a first member that adsorbs the hydrophilic substance and a second member that adsorbs the hydrophobic substance,
A relationship of d / l ≧ 0.23 with respect to the thickness d of the partition wall and the width l of the flow path;
The first member is formed of particles, silica, alumina, titania, zirconia or magnesia,
The first member is held by the second member synthesized using an aromatic carboxylic acid and an aromatic amine,
The adsorption member according to claim 1, wherein the second member has a thickness larger than a diameter of the first member. An outer wall, a plurality of flow paths provided inside the outer wall, and a partition wall that separates one of the plurality of flow paths from the other flow path, and includes a hydrophilic substance and a hydrophobic substance. An adsorbing member into which water to be treated containing water is charged,
The partition has a communication hole for connecting the one channel and the other channel,
An inner surface of the flow path and the communication hole is provided with an adsorbing portion composed of a first member that adsorbs the hydrophilic substance and a second member that adsorbs the hydrophobic substance,
A relationship of d / l ≧ 0.23 with respect to the thickness d of the partition wall and the width l of the flow path;
The second member is formed of particles, silicon carbide, graphite, diamond, polystyrene, or polyolefin,
The second member is held by the first member containing alumina or silica,
The adsorption member according to claim 1, wherein the first member has a thickness larger than a diameter of the second member. The adsorption member according to claim 5 or 6 ,
By removing the surface of the adsorbing portion, the first member and the second member that have appeared on the surface are peeled off, and the first member and the second member different from the peeled first member and the second member The suction member, wherein the second member appears on a new surface of the suction portion. The adsorption member according to claim 5 or 6 ,
Having one surface facing the direction in which the water to be treated flows and the other surface;
The one flow path is provided side by side in a direction orthogonal to the direction in which the water to be treated flows, and is configured to open to the one surface and not to the other surface.
The other channel is configured to open to the other surface and not open to the one surface,
The adsorbing member, wherein the one channel and the other channel are alternately arranged in a direction different from a direction from the inlet to the outlet of the adsorbing member. An adsorbing member comprising an outer wall and a flow path provided inside the outer wall, into which water to be treated containing a hydrophilic substance and a hydrophobic substance is charged,
The adsorbing member has a hollow structure, and has a plurality of hollow fibers in which one end of two ends is closed,
The hollow fiber includes a partition that separates an external space and an internal space of the hollow fiber from each other, and a communication hole that is connected to the external space from the space inside the hollow fiber in the partition,
The flow path is configured inside the hollow fiber,
An adsorbing part for adsorbing the hydrophilic substance or the hydrophobic substance is formed in the flow path and the communication hole,
Of the hollow fibers, one hollow fiber adsorbing part is constituted by a second member adsorbing the hydrophobic substance, and the other hollow fiber adsorbing part of the hollow fibers is a first member adsorbing the hydrophilic substance. Consists of
The first member is formed of particles, silica, alumina, titania, zirconia or magnesia,
The first member is held by the second member synthesized using an aromatic carboxylic acid and an aromatic amine,
The adsorption member according to claim 1, wherein the second member has a thickness larger than a diameter of the first member. An adsorbing member comprising an outer wall and a flow path provided inside the outer wall, into which water to be treated containing a hydrophilic substance and a hydrophobic substance is charged,
The adsorbing member has a hollow structure, and has a plurality of hollow fibers in which one end of two ends is closed,
The hollow fiber includes a partition that separates an external space and an internal space of the hollow fiber from each other, and a communication hole that is connected to the external space from the space inside the hollow fiber in the partition,
The flow path is configured inside the hollow fiber,
An adsorbing part for adsorbing the hydrophilic substance or the hydrophobic substance is formed in the flow path and the communication hole,
Of the hollow fibers, one hollow fiber adsorbing part is constituted by a second member adsorbing the hydrophobic substance, and the other hollow fiber adsorbing part of the hollow fibers is a first member adsorbing the hydrophilic substance. Consists of
The second member is formed of particles, silicon carbide, graphite, diamond, polystyrene, or polyolefin,
The second member is held by the first member containing alumina or silica,
The adsorption member according to claim 1, wherein the first member has a thickness larger than a diameter of the second member. The adsorption member according to claim 9 or 10 ,
By removing the surface of the adsorbing portion, the first member and the second member that have appeared on the surface are peeled off, and the first member and the second member different from the peeled first member and the second member The suction member, wherein the second member appears on a new surface of the suction portion.

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