JP5062970B2 - Waste water treatment apparatus and method - Google Patents

Description

  The present invention relates to a wastewater treatment apparatus and a wastewater treatment method for treating organic wastewater generated from food factories, chemical factories, homes, and the like. Furthermore, the present invention relates to a wastewater treatment apparatus and method that generates less excess sludge and has a low phosphorus concentration in treated water.

  Known methods for treating organic wastewater include the activated sludge method, the biofilm method, and the stabilization pond method. In any of these methods, a large amount of excess sludge is generated in the treatment apparatus, and thus a sludge treatment apparatus such as a dehydrator, a dryer, and an incinerator is required. In addition, when the phosphorus concentration in the wastewater is high, problems such as eutrophication of the closed water area occur, so the concentration of phosphorus in the wastewater is regulated with COD and nitrogen.

In recent years, many wastewater treatment methods with less generation of excess sludge have been proposed, including lysis-latent growth method, maintenance metabolism method, uncoupling metabolism method, maintenance metabolism method, and bacteria predation method. The lysis-latent growth method is a method for dissolving sludge and promoting latent growth. To dissolve sludge, the ozone method described in Patent Document 1 (Japanese Patent Laid-Open No. 07-116665), Patent Document 2 (Japanese Patent Laid-Open Publication No. 11). In addition to the thermophilic bacteria method described in JP-A-235598), there are a chlorine method, a bead mill method, a high-speed rotating disk method, an ultrasonic method, a hydrothermal method, a chemical addition method, and the like. As the maintenance metabolic method, there is a membrane separation activated sludge method described in Patent Document 3 (Japanese Patent Laid-Open No. 2005-46748). As an uncoupling metabolic method, there is a method using a chemical uncoupling agent. In addition, the bacteria predation method includes a two-stage system.
Japanese Patent Laid-Open No. 07-116687 JP 11-235598 A JP 2005-66595 A Y. Wei et al., “Minimization of excess sludge production for biological wastewater treatment”, Water Research 37 (18) 4453-4467 (2003)

Each of the wastewater treatment methods has advantages and disadvantages, but both have a problem that the concentration of phosphorus in the treated water is higher than when excessive sludge is generated.
An object of the present invention is to provide a wastewater treatment apparatus and a wastewater treatment method for treating organic wastewater, which generate less excess sludge and have a low phosphorus concentration in treated water.

In order to solve the above-mentioned problems, the present inventor has found a wastewater treatment apparatus and method newly composed of a biological treatment means, a sludge separation means, and an ion adsorption means filled with a porous molded body, and has made the present invention.
That is, the present invention is as follows.
1. A wastewater treatment apparatus comprising a biological treatment means, a sludge separation means and an ion adsorption means filled with a porous molded body, wherein the porous molded body comprises an organic polymer resin and an inorganic ion adsorbent. fibrils is to form a three-dimensional network structure, a porous molded body having a communication hole that opens to the outer surface, Tei gap between fibrils to form a communication hole, and said fibrils have voids therein In addition , a wastewater treatment apparatus characterized in that at least a part of the voids are open at the surface of the fibril, and an inorganic ion adsorbent is supported on the outer surface of the fibril and the inner void surface.
2. The wastewater treatment apparatus according to 1., wherein the communication hole has a maximum pore diameter layer near the surface of the molded body.
3. Porous material in which the organic polymer resin includes one or more selected from the group consisting of ethylene vinyl alcohol copolymer (EVOH), polyacrylonitrile (PAN), polysulfone (PS), and polyvinylidene fluoride (PVDF). The waste water treatment apparatus according to 1 or 2 which is a molded body.

4). 1. The inorganic ion adsorbent contains at least one metal oxide represented by the following formula (I). ~ 3. The waste water treatment apparatus in any one of.
_{MN x O n · mH 2 O} (I)
(Wherein x is 0 to 3, n is 1 to 4, m is 0 to 6, and M and N are Ti, Zr, Sn, Sc, Y, La, Ce, Pr, Nd, Sm, Eu. Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Si, Cr, Co, Ga, Fe, Mn, Ni, V, Ge, Nb and Ta are metal elements selected from the group Are different from each other.)

5. 3. The metal oxide represented by the formula (I) is one or a mixture of two or more selected from any of the following groups (a) to (c). The wastewater treatment apparatus described in 1.
(A) hydrated titanium oxide, hydrated zirconium oxide, hydrated tin oxide, hydrated cerium oxide, hydrated lanthanum oxide, and hydrated yttrium oxide (b) consisting of titanium, zirconium, tin, cerium, lanthanum, and yttrium A composite metal oxide of a metal element selected from the group and a metal element selected from the group consisting of aluminum, silicon, and iron (c) activated alumina

6). The biological treatment means includes two or more aeration tanks. ~ 5. The waste water treatment apparatus in any one of.
7). The biological treatment means includes an aeration tank in which the contact material is immersed. ~ 6. The waste water treatment apparatus in any one of.
8). 6. The contact material is composed of a core material and a fibrous material partially fixed to the core material, and the fibrous material is densely formed around the core material. The wastewater treatment apparatus as described.
9. 7. The core material has a spiral shape. The wastewater treatment apparatus as described.

10. 7. The fibrous material is polyvinylidene chloride. Or 9. The wastewater treatment apparatus described in 1.
11. 1. The sludge separation means is a sedimentation tank and / or a membrane separator. -10. The waste water treatment apparatus in any one of.
12 11. The separation membrane of the membrane separation device comprises one or more selected from the group consisting of polyacrylonitrile (PAN), polysulfone (PS), polyvinylidene fluoride (PVDF), polyethylene (PE), and polypropylene (PP). The wastewater treatment apparatus as described.
13. 10. The separation membrane is a hollow fiber. Or 12. The wastewater treatment apparatus described in 1.

14 The separation membrane is a membrane cartridge in which both ends of a plurality of hollow fibers arranged in the vertical direction are bonded and fixed, and a cartridge head that is liquid-tightly bonded and fixed to the outer periphery of one end, and fixed to the outer periphery of the other end The cartridge head and the skirt are separated, the cartridge head side hollow fiber end is open, the skirt side hollow fiber end hollow is sealed, and the skirt side adhesive fixing layer Are provided with a plurality of through holes. -13. The wastewater treatment apparatus according to any one of the above.

15. Biological treatment process, a waste water treatment method for sludge separation step and porous molded body comprising a packed ion adsorption step, the fibrils porous molded body, comprising an organic polymer resin and an inorganic ion adsorbent it forms a three-dimensional network structure, a porous molded body having a communication hole that opens to the outer surface, the gap between the fibrils to form a communication hole, and said fibrils have voids therein, A wastewater treatment method characterized in that at least a part of the voids are open at the surface of the fibril, and an inorganic ion adsorbent is supported on the outer surface of the fibril and the surface of the void inside.

  The wastewater treatment apparatus and the wastewater treatment method of the present invention are a wastewater treatment apparatus and a wastewater treatment method for treating organic wastewater, and have an effect that the generation of excess sludge is small and the phosphorus concentration in the treated water is low.

The present invention will be specifically described below.
The present invention relates to a wastewater treatment apparatus comprising a biological treatment means, a sludge separation means, and an ion adsorption means filled with a porous molded body, and a method thereof.
The biological treatment means of the present invention is not particularly limited, but the standard activated sludge method, standard aeration method, long-time aeration method, oxidation ditch method, batch method, activated sludge method such as membrane separation activated sludge method, contact oxidation method Anaerobic, such as water filter method, submerged filter method, rotating disk method, fluidized bed method, biofiltration method such as biofiltration method, and stabilization pond method such as high-speed oxidation pond method and facultative oxidation pond method Process. Also, anaerobic nitrification method, anaerobic treatment such as lagoon method, septic tank method, anaerobic filter bed method, etc., treatment with specific organisms such as photosynthetic bacteria, yeast, chlorella, biological devagination, If necessary, at least one of treatment of nutrients such as biological dephosphorization and treatment utilizing natural purification functions such as lakes, waterways, and soils can be used in combination.

  As the biological treatment means of the present invention, the number of aeration tanks may be one or more. However, the generation of surplus sludge is reduced, so two or more tanks are preferable. A tank is more preferred.

  As the biological treatment means of the present invention, the catalytic oxidation method is preferred because the generation of excess sludge is reduced. The contact oxidation method is a method in which a contact material, which is a carrier for growing and acclimatizing microorganisms, is immersed in an aeration tank and aerated. The contact material is not particularly limited, but examples of the shape include a honeycomb shape, a spiral shape, a hollow shape, a sponge shape, a mesh shape, a rod shape, and a linear shape. Is preferred. Also preferred is a contact material comprising a core material and a fibrous material partially fixed to the core material, and the fibrous material is densely formed around the core material. The shape of the core material is not limited, but a contact material in which the core material has a helical shape is preferable.

  For the core material, soft iron, aluminum, copper or other metals, or soft vinyl chloride or other plastics can be used. The metal core can be waterproofed or plastic coated to prevent corrosion. Although the diameter of a core material changes with materials, 1 mm or more and 7 mm or less are preferable. Furthermore, the material of the fibrous material is not particularly limited, and examples thereof include polyethylene, polypropylene, polyester, polyamide, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, and polyurethane. Polyvinylidene chloride has good adhesion to microorganisms. Therefore, it is preferable.

As the contact material, a contact material block in which a plurality of contact materials are held on a frame made of an appropriate corrosion-resistant material and immersed in an aeration tank can be used. The height of the contact material block may be a height suitable for the water depth of the aeration tank, but is preferably from 0.5 m to 6 m, and more preferably from 2 m to 4 m.
As for the usage amount of the contact material, the surface area of the contact material per 1 m ² of the projected floor area of the contact material block is preferably 100 m ² or more and 3000 m ² or less. If it is 100 m ² or more, the installation area efficiency of the apparatus is good, and if it is 500 m ² or less, the air lift effect by aeration is exhibited and a uniform swirling flow is obtained, and an environment in which microorganisms are easy to grow is obtained. More preferably, it is 250 m ² or more and 350 m ² or less.

Although it does not specifically limit as a sludge separation means of this invention, Membrane separation apparatuses, such as a sludge settling tank, a screen, a microfiltration membrane, and an ultrafiltration membrane, can be used. These can also be used together. Since the membrane separation apparatus can remove even a minute amount of SS, it is preferable because clogging of the ion adsorption means can be prevented.
Furthermore, the membrane separation activated sludge method using a submerged membrane is more preferable because it has the effect of using both biological treatment means and sludge separation means.

The membrane separation activated sludge apparatus performs biological treatment by introducing raw water into an aeration tank, introduces a biological treatment liquid containing the sludge of the aeration tank into a separation membrane immersed in the tank, and supplies permeated water of the separation membrane. It is a device to take out as treated water.
The separation membrane used in the membrane separation activated sludge apparatus of the present invention is not particularly limited, but MF (microfiltration) membrane and UF (ultrafiltration) are preferable in terms of excellent balance between filtration accuracy and permeated water amount.
The form of the membrane is not limited to flat membranes, hollow fibers, pleats, spirals, tubes, and the like, but hollow fibers are particularly preferable in that the membrane area in a unit volume can be widened.

  The material of the membrane is polysulfone polymer, polyvinylidene fluoride polymer, polyvinylidene chloride polymer, polyolefin polymer, acrylonitrile polymer, polymethyl methacrylate polymer, polyamide polymer, polyimide polymer, cellulose polymer, ethylene vinyl There are many types such as alcohol copolymer polymers. In particular, it consists of polyacrylonitrile (PAN), polysulfone (PS), polyvinylidene fluoride (PVDF), polyethylene (PE), and polypropylene (PP) because of its non-swelling property and biodegradability in water and ease of production. It is preferable to include one or more selected from the group.

The membrane-separated activated sludge method is likely to be clogged because it filters a biological treatment liquid having a high MLSS (Mixed Liquid Suspended Solid) concentration. In order to obtain stable permeated water, it is necessary to effectively clean the membrane surface with air.
In order to effectively perform cleaning with air, a membrane cartridge having the following structure is particularly preferable.

The example of embodiment of the hollow fiber cartridge concerning this invention is demonstrated using FIG.
In FIG. 2, the hollow fiber cartridge 201 includes a large number of hollow fibers 202, an upper adhesive fixing layer 206, a lower adhesive fixing layer 207, a cartridge head 205, and a skirt 204. At one end of the bundled hollow fibers 202, the hollow fibers are integrally bonded together by an adhesive and are also integrally bonded in the cartridge head 205 to constitute an upper adhesive fixing layer 206. The end of the hollow fiber 202 on the cartridge head 205 side is opened. At the other end of the hollow fiber 202, the hollow fibers are integrally bonded by an adhesive, and are integrally bonded in the skirt 204 to form the lower adhesive fixing layer 207. The part is sealed. The lower adhesive fixing layer 207 is formed with a plurality of through-holes 203 for introducing raw water and cleaning gas into the hollow fiber bundle to effectively contact the outer peripheral surface of the hollow fiber.

The biological treatment liquid in the aeration tank is filtered from the outer surface of the hollow fiber, passes through the hollow portion inside the hollow fiber, passes through the treated water outlet 208, and is sent to the ion adsorption means as the next step.
The material of the adhesive is preferably a polymer material such as an epoxy resin, a urethane resin, an epoxy acrylate resin, or a silicon resin.
The material of the cartridge head 205 and the skirt 204 is not particularly limited, but a thermoplastic resin or stainless steel is preferable.
The size of the through hole is preferably in the range of 2 mm to 35 mm in diameter.
The skirt 204 protrudes downward from the end face of the hollow fiber and is fixed. The protruding length is preferably 5 to 500 mm although it depends on the diameter of the cartridge and the amount of air. The hollow fiber 202 preferably has an inner diameter of 50 μm to 3000 μm and an inner / outer diameter ratio of 0.3 to 0.8.

The ion adsorption means filled with the porous molded body of the present invention is mainly means for reducing the phosphorus concentration in the treated water. Furthermore, phosphorus useful as a resource can be recovered.
A wastewater treatment method according to the present invention is a wastewater treatment apparatus including a biological treatment process, a sludge separation process, and an ion adsorption process filled with a porous molded body, wherein the porous molded body includes an organic polymer resin and an inorganic A porous molded body having a communicating hole that opens to the outer surface, comprising an ion adsorbent, having a void inside the fibril forming the communicating hole, and at least a part of the void is the surface of the fibril And is a porous molded body in which an inorganic ion adsorbent is supported on the outer surface of the fibril and the inner void surface. The ion adsorption step is preferably provided after the biological treatment step and the sludge separation step from the viewpoint of efficiency of ion adsorption.

The porous molded body of the present invention will be described in detail below.
First, the structure of the molded body of the present invention will be described.
The molded body of the present invention has a communication structure and a porous structure. Furthermore, there is no skin layer on the outer surface, and the surface has excellent opening properties. Further, there is a void inside the fibril forming the communication hole, and at least a part of the void is opened on the fibril surface.

  The outer surface aperture ratio of the molded article of the present invention refers to the ratio of the sum of the aperture areas of all the holes in the area of the field of view when the surface is observed with a scanning electron microscope. In the present invention, the surface of the molded body was observed at a magnification of 10,000 to actually measure the outer surface opening ratio. The range of the surface opening ratio is preferably 10 to 90%, and particularly preferably 15 to 80%. If it is less than 10%, the diffusion rate of the substance to be adsorbed such as phosphorus is slowed down inside the molded body. It is. The outer surface opening diameter of the molded body of the present invention is determined by observing the surface with a scanning electron microscope. When the hole is circular, the diameter is used. When the hole is not circular, the equivalent circle diameter of a circle having the same area is used. A preferable range of the surface opening diameter is O.005 μm to 100 μm, and particularly preferably O.01 μm to 50 μm. If it is less than O.005 μm, the diffusion rate of the substance to be adsorbed such as phosphorus into the molded body tends to be slow, whereas if it exceeds 100 μm, the strength of the molded body tends to be insufficient.

  The molded body of the present invention has voids in the fibrils forming the communication holes, and at least a part of the voids are opened on the surface of the fibrils. The inorganic ion adsorbent is supported on the outer surface of the fibril and the void surface inside the fibril. Since the fibril itself is also porous, an inorganic ion adsorbent that is an adsorption substrate embedded inside can also come into contact with an adsorption target substance called phosphorus, and can effectively function as an adsorbent. In the porous molded body of the present invention, since the portion where the adsorption substrate is supported is also porous, the fineness of the adsorption substrate, which was a disadvantage of the conventional method of kneading the adsorption substrate and the binder, The adsorption site is rarely clogged with a binder, and the adsorption substrate can be used effectively.

  Here, the fibril means a fibrous structure formed of an organic polymer resin and forming a three-dimensional continuous network structure on the outer surface and inside of the molded body. The void inside the fibril and the opening of the fibril surface are determined by observing the cut section of the molded body with a scanning electron microscope. It is observed that there are voids in the cross-section of the fibril and that the surface of the fibril is open. Furthermore, it is observed that the inorganic ion adsorbent powder is supported on the outer surface of the fibril and the inner void surface. The thickness of the fibril is preferably O.01 μm to 50 μm. The pore diameter on the fibril surface is preferably O.001 μm to 5 μm.

  In the porous molded body of the present invention, the communicating holes preferably have a maximum pore diameter layer in the vicinity of the surface of the molded body. Here, the maximum pore diameter layer means the largest portion in the pore diameter distribution of the communication holes extending from the surface of the molded body to the inside. In the case where there is a large circular or oval (finger-like) void called a void, the layer in which the void exists is called the maximum pore diameter layer. The vicinity of the surface means the inner side up to 25% of the cleaved diameter of the molded body from the outer surface toward the center. By having the maximum pore diameter layer in the vicinity of the surface of the molded body, it has the effect of accelerating the diffusion of the substance to be adsorbed into the interior. Therefore, the adsorption target substance such as phosphorus can be quickly taken into the molded body and removed from the treated water.

  The positions of the maximum pore diameter and the maximum pore diameter layer are determined by observing the surface and the cut surface of the molded body with a scanning electron microscope. As the hole diameter, when the hole is circular, the diameter thereof is used. When the hole is not circular, the equivalent circle diameter of a circle having the same area is used. The form of the molded body can take any form such as a particulate form, a thread form, a sheet form, a hollow fiber form, a cylindrical form, and a hollow cylindrical form. In particular, when the molded body is used as an adsorbent in the water treatment field, the particle shape is reduced in terms of pressure loss, effectiveness of the contact area and ease of handling when packed in a column or the like and passed through. Spherical particles (not only true spheres but also oval spheres) are particularly preferable.

  The average particle diameter of the spherical molded body of the present invention is a mode diameter (most frequent particle diameter) of a sphere equivalent diameter obtained from the angular distribution of scattered light intensity of diffraction by laser light, assuming that the particles are spherical. A preferable range of the average particle diameter is 100 to 2500 μm, particularly 200 to 2000 μm. If the average particle size is smaller than 100 μm, the pressure loss tends to increase when the column or tank is filled, and if the average particle size is larger than 2500 μm, the surface area when packed in the column or tank is reduced. Processing efficiency tends to decrease.

The porosity Pr (%) of the molded body of the present invention is the weight W1 (g) of the molded body when it contains water, the weight W0 (g) after drying, and the specific gravity of the molded body as ρ. The value represented by
Pr = (W1-WO) / (W1-WO + W0 / ρ) × 100
The wet weight may be determined by spreading a molded product sufficiently wet with water on dry filter paper and taking excess water before measuring the wet weight. Drying may be performed under vacuum at room temperature in order to eliminate moisture. The specific gravity of the molded body can be easily measured using a specific gravity bottle.
A preferable range of the porosity Pr (%) is 50% to 90%, and particularly preferably 60 to 85%. If it is less than 50%, the contact frequency between the adsorption target substance such as phosphorus and the inorganic ion adsorbent as the adsorption substrate tends to be insufficient. If it exceeds 90%, the strength of the molded product tends to be insufficient.

The supported amount of the inorganic ion adsorbent in the molded product of the present invention is a value represented by the following formula when the weight Wd (g) when the molded product is dried and the weight Wa (g) of the ash content.
Load (%) = Wa / Wd × 100
Here, the ash content is the residue when the molded product of the present invention is baked at 800 ° C. for 2 hours.
A preferable loading range is 30 to 95%, more preferably 40 to 90%, and particularly preferably 65 to 90%. If it is less than 30%, the contact frequency between the adsorption target substance such as phosphorus and the inorganic ion adsorbent as the adsorption substrate tends to be insufficient, and if it exceeds 95%, the strength of the molded product tends to be insufficient.

According to the method of the present invention, unlike the conventional attaching method, since the adsorbing substrate and the organic polymer resin are kneaded and molded, it is possible to obtain a molded body having a large carrying amount and strong strength.
The specific surface area of the molded product of the present invention is defined by the following formula.
Specific surface area (m ² / cm ³ ) = S _BET × Bulk specific gravity (g / cm ³ )
Here, S _BET is a specific surface area (m ² / g) per unit weight of the molded body.
The specific surface area is measured using the BET method after vacuum drying the molded body at room temperature.
The bulk specific gravity is measured by measuring the apparent volume of a short shaped product such as a particle, a column, or a hollow column using a wet compact and a graduated cylinder. Then, it vacuum-drys at room temperature and calculates | requires a weight.

For a long fiber-like, hollow fiber-like, or sheet-like shape, the cross-sectional area and length when wet are measured, and the volume is calculated from the product of both. Then, it vacuum-drys at room temperature and calculates | requires a weight.
The preferred range of the specific surface area is ^{5m 2 / cm 3 ~500m 2 /} cm 3. If it is less than 5 m ² / cm ³ , the amount of the adsorbed substrate and the adsorption performance tend to be insufficient, and if it exceeds 500 m ² / cm ³ , the strength of the molded product tends to be insufficient.

In general, the adsorption performance (adsorption capacity) of an inorganic ion adsorbent that is an adsorption substrate is often proportional to the specific surface area. If the surface area per unit volume is small, the adsorption capacity and adsorption performance when packed in a column or tank are small, making it difficult to achieve high-speed processing.
The molded body of the present invention has a three-dimensional network structure that is porous and intricately intertwined with fibrils. Furthermore, since the fibril itself has voids, it has a feature that the surface area is large. Since this has an adsorption substrate (inorganic ion adsorbent) having a larger specific surface area, the surface area per unit volume is also increased.

Next, the manufacturing method of the porous molded object of this invention is demonstrated.
The method for producing a porous molded body of the present invention is characterized in that an organic polymer resin, a good solvent thereof, an inorganic ion adsorbent, and a water-soluble polymer are mixed and then molded and solidified in a poor solvent. .

  The organic polymer resin used in the present invention is not particularly limited, but is preferably one that can be made porous by wet phase separation. For example, polysulfone polymer, polyvinylidene fluoride polymer, polyvinylidene chloride polymer, acrylonitrile polymer, polymethyl methacrylate polymer, polyamide polymer, polyimide polymer, cellulose polymer, ethylene vinyl alcohol copolymer polymer, etc. There are many types. In particular, ethylene vinyl alcohol copolymer (EVOH), polyacrylonitrile (PAN), polysulfone (PS), and polyvinylidene fluoride (PVDF) are preferable from the viewpoint of non-swelling property and biodegradability in water and ease of production. Furthermore, an ethylene vinyl alcohol copolymer (EVOH) is preferable because it has both hydrophilicity and chemical resistance.

  In addition, the good solvent used in the present invention may be any as long as it dissolves both the organic polymer resin and the water-soluble polymer. For example, dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAC), dimethylformamide (DMF) and the like. These good solvents may be used alone or as a mixed solvent. The content of the organic polymer resin in the good solvent is not particularly limited, but is preferably 5 to 40% by weight, and more preferably 7 to 30% by weight. If it is less than 5% by weight, it is difficult to obtain a strong molded product. When it exceeds 40% by weight, it is difficult to obtain a porous molded body having a high porosity. The water-soluble polymer used in the present invention is not particularly limited as long as it is compatible with the organic polymer resin.

  Examples of natural polymers include guar gum, locust bean gum, carrageenan, gum arabic, tragacanth, pectin, starch, dextrin, gelatin, casein, collagen and the like. Examples of the semisynthetic polymer include methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl starch, and methyl starch. Furthermore, examples of the synthetic polymer include polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, carboxyvinyl polymer, sodium polyacrylate, and polyethylene glycols such as tetraethylene glycol and triethylene glycol. Among these water-soluble polymers, a synthetic polymer is preferable in that it has biodegradability resistance.

  In particular, it is particularly preferable to use polyvinylpyrrolidone as the water-soluble polymer because it has a high effect of developing a structure having voids inside the fibrils forming the communication holes as in the molded article of the present invention. The weight average molecular weight of polyvinylpyrrolidone is preferably in the range of 2,000 to 2,000,000, more preferably in the range of 2,000 to 1,000,000, and still more preferably in the range of 2,000 to 100,000. If the weight average molecular weight is less than 2,000, the effect of developing a structure having voids inside the fibril tends to be low. If the weight average molecular weight exceeds 2,000,000, the viscosity at the time of molding increases, and molding is difficult. It tends to be difficult.

The content of the water-soluble polymer in the molded product of the present invention is expressed by the following equation when the weight of the molded product when dried is Wd (g) and the weight of the water-soluble polymer extracted from the molded product is Ws (g). The value represented.
Content (%) = Ws / Wd × 100
The content of the water-soluble polymer depends on the type and molecular weight of the water-soluble polymer, but is preferably 0.001 to 10%, and more preferably 0.01 to 1%. If it is less than 0.001%, the effect is not necessarily sufficient to open the surface of the molded body, and if it exceeds 10%, the polymer concentration becomes relatively thin and the strength may not be sufficient.

  Here, the weight Ws of the water-soluble polymer in the molded body is measured as follows. First, after the dried molded body is pulverized in a mortar or the like, the water-soluble polymer is extracted from the pulverized product using a good solvent for the water-soluble polymer, and then the extract is evaporated to dryness, The weight of the conducting polymer is determined. Furthermore, identification of the extracted evaporated and dried product and confirmation of the presence or absence of the water-soluble polymer remaining in the fibril and not extracted can be measured by infrared absorption spectrum (IR) or the like. Furthermore, when there is a water-soluble polymer that remains in the fibrils and is not extracted, the porous molded body of the present invention is dissolved in a good solvent for both the organic polymer resin and the water-soluble polymer, and then the inorganic ions are dissolved. A liquid obtained by removing the adsorbent by filtration can be prepared, and then the liquid can be analyzed using GPC or the like to quantify the content of the water-soluble polymer.

The content of the water-soluble polymer can be appropriately adjusted depending on the molecular weight of the water-soluble polymer and the combination of the organic polymer resin and the good solvent. For example, when a water-soluble polymer having a high molecular weight is used, the entanglement of the molecular chain with the organic polymer resin becomes strong, and it becomes difficult to move to the poor solvent side during molding, and the content can be increased.
The inorganic ion adsorbent used in the present invention refers to an inorganic substance exhibiting an ion adsorption phenomenon.
For example, natural products include zeolite, montmorillonite, and various mineral substances, and synthetic products include metal oxides. The former is represented by aluminosilicate kaolin mineral with a single layer lattice, bilayer latticed muscovite, sea chlorite, kanuma earth, pyrophyllite, talc, three-dimensional framework feldspar, zeolite and the like. The latter mainly includes polyvalent metal salts, metal oxides, insoluble heteropolyacid salts, insoluble hexacyanoferrates, and the like.

Examples of the polyvalent metal salt include hydrotalcite compounds represented by the following formula (II).
M ²⁺ _(1-X) M ³⁺ _x (OH ⁻ ) _{(2 + xy)} (A ⁿ⁻ ) y / n (II)
[ ^Wherein M ²⁺ represents at least one divalent metal ion selected from the group consisting of Mg ²⁺ , Ni ²⁺ , Zn ²⁺ , Fe ²⁺ , Ca ²⁺ and Cu ²⁺ ; ³⁺ represents at least one trivalent metal ion selected from the group consisting of Al ³⁺ and Fe ^3+, a ^n-represents an n-valent anion, be 0.1 ≦ x ≦ 0.5 0.1 ≦ y ≦ 0.5, and n is 1 or 2. ]

The metal oxide can be represented by the following formula (I).
_{MN x O n · mH 2 O} (I)
(Wherein x is 0 to 3, n is 1 to 4, m is 0 to 6, and M and N are Ti, Zr, Sn, Sc, Y, La, Ce, Pr, Nd, Sm, Eu. Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Si, Cr, Co, Ga, Fe, Mn, Ni, V, Ge, Nb and Ta are metal elements selected from the group Are different from each other.)
The metal oxide referred to in the present invention may be an unhydrated (non-hydrated) metal oxide in which m in the formula (I) can be represented by 0, or a hydrate (m can be represented by a numerical value other than 0). It may be a hydrous metal oxide.

The metal oxide in the case where x in formula (I) is a numerical value other than 0 is such that each contained metal element has regularity and is uniformly distributed throughout the oxide, for example, a perovskite structure, spinel It forms a structure and the like, and is contained in metal oxides such as nickel ferrite (NiFe ₂ O ₄ ) and zirconium hydrous ferrite (Zr · Fe ₂ O ₄ · mH ₂ O m is 0.5 to 6). It is a complex metal oxide represented by a chemical formula in which the composition ratio of each metal element is fixed.

The inorganic ion adsorbent supported on the porous molded body of the present invention is represented by the above formula (I) and has the following (a) to (a) to (a) to (a) to (a) to (a) It is preferable that it is a 1 type, or 2 or more types of mixture of the metal oxide chosen from the group in any one of c).
(A) hydrated titanium oxide, hydrated zirconium oxide, hydrated tin oxide, hydrated cerium oxide, hydrated lanthanum oxide, and hydrated yttrium oxide (b) consisting of titanium, zirconium, tin, cerium, lanthanum, and yttrium A composite metal oxide of a metal element selected from the group and a metal element selected from the group consisting of aluminum, silicon, and iron (c) activated alumina In addition, activated alumina loaded with aluminum sulfate, activated carbon loaded with aluminum sulfate, and the like are also preferred.

The metal oxide represented by the formula (I) used in the present invention may be a solid solution of metal elements other than M and N. For example, the hydrated zirconium oxide represented by the formula ZrO ₂ · mH ₂ O according to the formula (I) may be hydrated zirconium oxide in which iron is dissolved.
The inorganic ion adsorbent used in the present invention may contain a plurality of metal oxides represented by the formula (I). There are no particular restrictions on the distribution state of each metal oxide, but in order to obtain an inorganic ion adsorbent that has better cost performance by effectively utilizing the characteristics of each metal oxide, the surroundings of a specific metal oxide Is preferably a mixed structure covered with another metal oxide. An example of such a structure is a structure in which hydrated zirconium oxide covers the periphery of triiron tetroxide.

In addition, since the metal oxide referred to in the present invention includes a metal oxide in which other elements are dissolved, the hydrated zirconium oxide in which iron is dissolved in the surrounding area of triiron tetroxide in which zirconium is in solid solution. A covered structure can also be exemplified as a preferred example.
In the above example, hydrated zirconium oxide has high adsorption performance for ions such as phosphorus, boron, fluorine, arsenic and durability for repeated use, but is expensive. On the other hand, triiron tetroxide has a low adsorption performance for ions such as phosphorus, boron, fluorine, and arsenic and a durability performance for repeated use, but is very inexpensive.

  Therefore, when the structure around iron tetroxide is covered with hydrated zirconium oxide, the surface of the inorganic ion adsorbent that is involved in the adsorption of ions becomes hydrated zirconium oxide with high adsorption performance and durability. Since the inside which does not participate in adsorption becomes inexpensive iron trioxide, a porous molded body which can be used as an adsorbent having high adsorption performance, high durability performance and low cost, that is, excellent in cost performance is obtained.

In addition, for adsorption and removal of ions harmful to the environment and health of phosphorus, boron, fluorine, arsenic,
From the viewpoint of obtaining an adsorbent excellent in cost performance, the inorganic ion adsorbent used in the present invention is a metal element in which at least one of M and N in the formula (I) is selected from the group consisting of aluminum, silicon, and iron. A structure in which at least one of M and N in the formula (I) is covered with a metal oxide that is a metal element selected from the group consisting of titanium, zirconium, tin, cerium, lanthanum, and yttrium. It is preferable to be configured.

  In this case, the content ratio of the metal element selected from the group consisting of aluminum, silicon, and iron in the inorganic ion adsorbent is a metal element selected from the group consisting of aluminum, silicon, and iron, and titanium, zirconium, tin, cerium, The total number of moles of the metal element selected from the group consisting of lanthanum and yttrium is T, the number of moles of the metal element selected from the group consisting of aluminum, silicon, and iron is F, and F / T (molar ratio) is 0.00. The range is preferably from 01 to 0.95, more preferably from 0.1 to 0.90, still more preferably from 0.2 to 0.85, and from 0.3 to 0.80. It is particularly preferred that When the value of F / T (molar ratio) is excessively increased, the adsorption performance and durability performance tend to be lowered.

Also, depending on the metal, there are a plurality of forms of metal oxides with different oxidation numbers of the metal elements, but the form is not limited as long as it can exist stably in the inorganic ion adsorbent. For example, in the case of an iron oxide, hydrated ferric oxide (FeO _1.5 · mH ₂ O) or hydrated iron trioxide (FeO _1.33 · mH ₂ O) is preferred.
In addition, the inorganic ion adsorbent of the present invention may contain an impurity element mixed due to its production method or the like within a range not departing from the achievement of the object of the present invention. Possible impurity elements to be mixed include nitrogen (nitrate, nitrite, ammonium), sodium, magnesium, sulfur, chlorine, potassium, calcium, copper, zinc, bromine, barium, hafnium, and the like.

In addition, since the specific surface area of the inorganic ion adsorbent affects the adsorption performance and durability, the specific surface area is preferably within a certain range. Specifically, it is preferable that a BET specific surface area determined by nitrogen adsorption method is 20~1000m ² / g, more preferably 30~800m ² / g, it is 50 to 600 m ² / g More preferably, it is 60-500 m < ² > / g. If the BET specific surface area is too small, the adsorption performance is lowered, and if it is too large, the solubility in acids and alkalis is increased.

  Although the manufacturing method of the metal oxide represented by the formula (I) used in the present invention is not particularly limited, for example, it is manufactured by the following method. A precipitate obtained by adding an alkaline solution to an aqueous salt solution of the metal chloride, sulfate, nitrate or the like is filtered, washed, and dried. The drying is performed by air drying or at about 150 ° C. or less, preferably about 90 ° C. or less for about 1 to 20 hours.

  Next, around at least one of M and N in the formula (I) around the metal oxide in which at least one of M and N in the formula (I) is a metal element selected from the group consisting of aluminum, silicon and iron A method for producing an inorganic ion adsorbent comprising a metal oxide that is a metal element selected from the group consisting of titanium, zirconium, tin, cerium, lanthanum, and yttrium. An example of manufacturing an inorganic ion adsorbent having a structure covered with zirconium oxide will be described.

  First, salts obtained by mixing a salt such as zirconium chloride, nitrate or sulfate with a salt such as iron chloride, nitrate or sulfate so that the above-mentioned F / T (molar ratio) is a desired value. Make an aqueous solution. Thereafter, an aqueous alkaline solution is added to adjust the pH to 8 to 9.5, preferably 8.5 to 9 to form a precipitate. Thereafter, the temperature of the aqueous solution is set to 50 ° C., air is blown in while maintaining the pH at 8 to 9.5, preferably 8.5 to 9, and oxidation is performed until ferrous ions cannot be detected in the liquid phase. The resulting precipitate is filtered off, washed with water and dried. The drying is performed by air drying or at about 150 ° C. or less, preferably about 90 ° C. or less for about 1 to 20 hours. The moisture content after drying is preferably in the range of about 6 to 30% by weight.

Zirconium oxychloride (ZrOC1 ₂ ), zirconium tetrachloride (ZrC1 ₄ ), zirconium nitrate (Zr (NO ₃ ) ₄ ), zirconium sulfate (Zr (SO ₄ ) ₂ ) Etc. These may be hydrated salts such as Zr (SO ₄ ) ₂ .4H ₂ O. These metal salts are usually used in the form of a solution of about 0.05 to 2.O moles per liter.
Examples of the iron salt used in the above-described production method include ferrous salts such as ferrous sulfate (FeSO ₄ ), ferrous nitrate (Fe (NO ₃ ) ₂ ), and ferrous chloride (FeC1 ₂ ). Can be mentioned. These may also be hydrated salts such as FeSO ₄ .7H ₂ O.

  These ferrous salts are usually added as solids, but may be added in the form of a solution. Examples of the alkali include sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia, sodium carbonate and the like. These are preferably used in an aqueous solution of about 5-20% by weight. When the oxidizing gas is blown, the time varies depending on the kind of the oxidizing gas, but is usually about 1 to 10 hours. As the oxidizing agent, for example, hydrogen peroxide, sodium hypochlorite, potassium hypochlorite and the like are used.

The inorganic ion adsorbent of the present invention is preferably as fine as possible, and its particle size is in the range of 0.01 to 100 μm, preferably 0.01 to 50 μm, more preferably 0.01 to 30 μm. .
If the particle size is smaller than 0.01 μm, the viscosity of the slurry at the time of production tends to increase and it tends to be difficult to mold. If it exceeds 100 μm, the specific surface area tends to be small, and the adsorption performance tends to be lowered.
The particle diameter here refers to the particle diameter of both the primary particles and the secondary particles in which the primary particles are aggregated or a mixture. The particle diameter of the inorganic ion adsorbent of the present invention is a sphere equivalent diameter (most frequent particle diameter) obtained from the angular distribution of scattered light intensity of diffraction by laser light.

  As the poor solvent of the method of the present invention, for example, water, alcohols such as methanol, ethanol, organic polymer resins such as industrial hydrocarbons, aliphatic hydrocarbons such as n-hexane and n-heptane are dissolved. Liquid is used, but water is preferred. It is also possible to control the coagulation rate by adding a little good solvent of the organic polymer resin in the poor solvent. The mixing ratio of the good solvent of the polymer resin and water is preferably O to 40%, and more preferably 0 to 30%. When the mixing ratio exceeds 40%, the coagulation rate becomes slow, so the polymer solution formed into droplets etc. enters between the poor solvent and the molded body between the poor solvent and the molded body. The shape tends to be distorted by the influence of friction resistance.

  The temperature of the poor solvent is not particularly limited, but is preferably −30 ° C. to 90 ° C., more preferably O ° C. to 90 ° C., and further preferably 0 ° C. to 80 ° C. If the temperature of the poor solvent exceeds 90 ° C or is less than -30 ° C, the state of the molded body in the poor solvent is difficult to stabilize.

Next, an ion processing method using the porous molded body of the present invention as an adsorbent will be described.
The porous molded body of the present invention is suitable for use as an adsorbent for adsorbing and removing ions in water by contacting with a liquid.
The ions to be adsorbed by the porous molded body of the present invention are not particularly limited to anions and cations. For example, with anions, phosphorus (phosphate ions), fluorine (fluoride ions), arsenic (arsenate ions, arsenite ions), boron (borate ions), iodine ions, chlorine ions, sulfate ions, nitrate ions , Nitrite ions, and ions of various organic acids such as acetic acid. Examples of the cation include sodium, potassium, calcium, cadmium, lead, chromium, cobalt, strontium, and cesium.

In particular, inorganic ion adsorbents have the characteristic of specific selectivity for certain ions, so that ions such as phosphorus are removed from the presence of miscellaneous ions such as sewage and industrial wastewater. Suitable for doing.
Specifically, for removal of phosphorus, boron, fluorine and arsenic ions, hydrated titanium oxide, hydrated zirconium oxide, hydrated tin oxide, hydrated cerium oxide, hydrated lanthanum oxide, hydrate Yttrium oxide; a composite metal oxide of a metal element selected from the group consisting of titanium, zirconium, tin, cerium, lanthanum, and yttrium and a metal element selected from the group consisting of aluminum, silicon, and iron; activated alumina; It is preferable to select at least one metal oxide selected from the group consisting of activated alumina; and aluminum sulfate impregnated activated carbon.

When the porous molded body of the present invention is used as an adsorbent for water treatment, the porous molded body is usually used by being filled in a container, but the shape of the container and the shape of the packed layer of the porous molded body There is no particular limitation as long as the porous molded body can be brought into contact with water to be treated, and examples thereof include cylindrical, columnar, polygonal columnar, and box-shaped containers. Preferably, packing in a column or adsorption tower and allowing the water to be treated to flow through and contact with each other can sufficiently bring out the high contact efficiency that is characteristic of the porous molded body.
These containers are preferably provided with a solid-liquid separation mechanism that prevents the porous molded body from flowing out of the container, for example, a pan and a mesh.
The material of the container is not particularly limited, and examples include stainless steel, FRP (reinforced plastic with glass fiber), glass, and various plastics. In consideration of acid resistance, the inner surface may be made of rubber or fluororesin lining.

  The contact method between the porous molded body and the water to be treated is not particularly limited as long as the porous molded body and the water to be treated can be brought into contact with each other. When the porous molded body is used as a fixed bed, a method of passing water in an upward or downward flow through a cylindrical, polygonal, or box-shaped porous molded body, or cylindrical porous molding Examples include an external pressure system that allows water to flow from the outer circumferential side to the inner cylinder, an internal pressure system that allows water to flow in the opposite direction, and a system that allows water to flow horizontally to the box-shaped packed bed. The packed bed of the porous molded body may be a fluidized bed system.

  The ion adsorbing means of the present invention is not particularly limited, but can adopt a merry-go-round system. With the merry-go-round method, a plurality of ion adsorbing means are arranged in series to conduct water, and when the adsorption capacity of the ion adsorbing means in the previous stage is reduced, the water passing through the ion adsorbing means is stopped and located in the subsequent stage This is a method of obtaining treated water with a stable water quality by sequentially passing water through the ion adsorbing means with a time difference from the previous stage, such as passing the ion adsorbing means as the front stage.

  In the ion adsorption means and the ion processing method of the present invention, the desorption operation and the activation operation described later are generally performed at the same site where the adsorption operation is performed. However, if there is not enough space at the site or the frequency of desorption is low, only the column can be removed from the apparatus and replaced with a new column separately. The removed column can be separately processed and reused in a factory equipped with a desorption and activation facility.

  When the porous molded body of the present invention is used as an adsorbent in water treatment applications, it is preferable to provide means for solid-liquid separation of suspended substances in water as a pretreatment. By removing suspended substances in water in advance, the surface of the porous molded body can be prevented from being blocked, and the adsorption performance of the porous molded body of the present invention can be sufficiently exhibited. Preferable solid-liquid separation means includes coagulation sedimentation, sedimentation separation, sand filtration, and membrane separation. In particular, a membrane separation technique that has a small installation area and that provides clear filtrate water is preferable. Preferred membrane separation techniques include reverse osmosis membrane (RO), ultrafiltration membrane (UF), microfiltration membrane (MF) and the like. The form of the membrane is not limited to flat membranes, hollow fibers, pleats, spirals, tubes and the like.

In the adsorption step of the present invention, it is preferable to adsorb the ions to be adsorbed after adjusting the pH of the liquid to a suitable pH by a combination of ions to be adsorbed and the inorganic ion adsorbent.
For example, the pH adjustment range when using an inorganic ion adsorbent having a structure in which phosphorus in a liquid is to be adsorbed and hydrated zirconium oxide or iron tetroxide is covered with hydrated zirconium oxide is pH 1.5 to 10. It is a range, More preferably, it is pH 2-7.

In addition, the pH adjustment range when using an inorganic ion adsorbent with a structure in which boron in the liquid is to be adsorbed and hydrated cerium oxide or iron tetroxide is covered with hydrated cerium oxide is in the range of pH 3 to 10. Yes, more preferably pH 5-8.
In addition, the pH adjustment range when using an inorganic ion adsorbent with a structure in which fluorine in the liquid is to be adsorbed and hydrated cerium oxide or iron trioxide is covered with hydrated zirconium oxide is in the range of pH 1-7. Yes, more preferably pH 2-5.
Also, the pH adjustment range when using an inorganic ion adsorbent with a structure in which arsenic in the liquid is the target of adsorption and hydrated cerium oxide or iron tetroxide is covered with hydrated cerium oxide is in the range of pH 3-12. Yes, more preferably pH 5-9.

  The porous molded body of the present invention can adsorb the anions again by contacting the alkaline aqueous solution to desorb the adsorbed anions and then treating the adsorbent with an acidic aqueous solution (re-applying). Use). By reusing the porous molded body, not only the cost can be reduced, but also the waste can be reduced. In particular, since the porous molded body of the present invention is excellent in durability, it is suitable for repeated use.

An anion can be eliminated when the pH of the alkaline solution is at least pH 10, but is preferably at least pH 12, more preferably at least pH 13. The alkali concentration is in the range of O.1 wt% to 30 wt%, more preferably in the range of 0.5 to 20 wt%. If it is thinner than O.1 wt%, the desorption efficiency is low, and if it is thicker than 30 wt%, the cost of alkali chemicals tends to increase.
The flow rate of the alkaline aqueous solution is not particularly limited, but is usually preferably in the range of SV0.5 to 15 (hr ⁻¹ ). When it is lower than SVO.5, the desorption time tends to be long and tends to be inefficient, and when it is larger than SV15, the contact time between the porous molded body and the alkaline aqueous solution is shortened, and the desorption efficiency tends to decrease. The kind of the alkaline aqueous solution is not particularly limited, but usually an inorganic alkali such as sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, ammonium hydroxide, and organic amines are used. Of these, sodium hydroxide and potassium hydroxide are particularly preferred because of their high desorption efficiency.

  In the desorption alkali recycling step and desorption ion recovery step in the present invention, an alkaline aqueous solution is brought into contact with the porous molded body of the present invention that has adsorbed ions, ions are desorbed in the alkaline solution, By adding a crystallization agent that generates ions and a precipitate and removing the precipitate, the alkali can be reused, and the ions can be recovered as a precipitate.

  Examples of the crystallization agent include metal hydroxides. In the metal hydroxide, a metal salt combines with anions such as phosphorus, boron, fluorine, and arsenic to form a precipitate. Further, since the hydroxide becomes an alkali source of the desorption liquid, a closed system can be obtained by collecting and recycling the regenerated liquid. Specific examples include sodium hydroxide, aluminum hydroxide, magnesium hydroxide, and calcium hydroxide.

From the viewpoint of obtaining a hardly soluble precipitate, that is, a precipitate having low solubility, a polyvalent metal hydroxide is preferable, and specifically, aluminum hydroxide, magnesium hydroxide, and calcium hydroxide are particularly preferable. In particular, calcium hydroxide is preferable in terms of cost.
For example, when it exists as sodium phosphate, the alkali can be recovered according to the following reaction formula. Furthermore, the crystallized calcium phosphate can be recycled into fertilizers and the like.
6Na ₃ PO ₄ + 10Ca (OH) ₂ → 18NaOH + Ca10 (OH) ₂ (PO ₄ ) ₆ ↓
The addition amount of the metal hydroxide is not particularly limited, but is 1 to 4 times equivalent to the target ion. When the addition amount is equal to or less than the equimolar amount, the precipitation removal efficiency is low, and when it exceeds 4 times the equivalent, the removal efficiency hardly changes and tends to be economically disadvantageous.

  When removing the precipitate, the pH is preferably 6 or more. Further, considering that the aqueous alkaline solution is recovered and reused, it is preferably maintained at pH 12 or more, preferably pH 13 or more. If the pH during the precipitation process is lower than 6, the solubility of the precipitate increases and the precipitation efficiency decreases. When removing the precipitate, an inorganic flocculant such as aluminum sulfate or polyaluminum chloride or a polymer flocculant can be used in combination with the metal hydroxide.

Further, the preferred desorbed ion recovery step in the present invention is to cool the desorbed liquid from which ions have been desorbed and to crystallize and remove the precipitate, thereby making it possible to reuse the alkali, Is to collect as.
This recovery process of desorbed ions by cooling can be suitably applied particularly when a porous molded body that has adsorbed phosphate ions is desorbed using sodium hydroxide.

The cooling means and method are not particularly limited, but can be cooled using a normal chiller, heat exchanger or the like.
The cooling temperature is not particularly limited as long as it is a temperature at which desorbed ions can be crystallized, but is preferably in the range of 5 to 25 ° C, more preferably in the range of 5 to 10 ° C. If the temperature is less than 5 ° C, a large amount of cooling energy is required and tends to be economically disadvantageous. If the temperature is higher than 10 ° C, the effect of crystallizing the precipitate tends to be low.
In order to effectively crystallize sodium phosphate by cooling, sodium hydroxide can be newly added to increase the concentration of sodium hydroxide in the desorption liquid.

The method for solid-liquid separation of the precipitate in the desorption solution of the present invention is not particularly limited, but usually, sedimentation separation, centrifugal separation, belt press machine, screw press machine, membrane separation method and the like can be used.
In particular, the membrane separation method is preferable in that the installation area is small and clear filtered water can be obtained.
The membrane separation method is not particularly limited, and examples thereof include an ultrafiltration membrane (UF), a microfiltration membrane (MF), and a dialysis membrane. The form of the membrane is not limited to a flat membrane, a hollow fiber, a pleat, a tube shape or the like. As a preferable membrane separation method, an ultrafiltration membrane (UF), a microfiltration membrane (MF) and the like are preferable in terms of filtration speed and filtration accuracy.

The porous molded body in the column after the desorption step is alkaline, and as it is, the ability to adsorb ions in the raw water again is low. Therefore, an operation of returning the pH in the column to a predetermined value using an acidic aqueous solution, that is, an activation treatment is performed.
The acidic aqueous solution is not particularly limited, but an aqueous solution such as sulfuric acid and hydrochloric acid is used. The concentration may be about O.001 to 10 wt%. If it is thinner than O.001 wt%, a large amount of water volume is required by the end of activation, and if it is thicker than 10 wt%, there is a possibility that a problem may occur in terms of danger in handling an acidic aqueous solution.

The liquid passing speed is not particularly limited, but is usually preferably in the range of SV 0.5 to 30 (hr ⁻¹ ). If it is lower than SV0.5, the activation time tends to be long and inefficient, and if it is larger than SV30, the contact time between the porous molded body and the acidic aqueous solution becomes short, and the activation efficiency tends to decrease. is there.
A more preferable method in the activation method is to circulate the active solution between the column and the pH adjusting tank.
By adopting this configuration, the pH of the porous molded body in the column shifted to the alkali side by the desorption operation can be slowly returned to a predetermined pH in consideration of the acid resistance of the inorganic ion adsorbent.

  For example, it is known that iron oxide is remarkably dissolved by acid at pH 3 or lower. When such iron oxide is supported on a porous molded body, the conventional activation method has a problem of dissolution of iron, and therefore, there is only a method of treating with a thin acid having a pH of 3 or more. However, this method requires a large volume of water and is not economically acceptable.

In contrast to such a conventional technique, the activation method of the present invention is provided with a column and a pH adjusting tank and circulates the activation liquid. The volume of water used for conversion can be reduced, and the apparatus can be made compact.
The liquid passing speed at this time is usually selected in the range of SV1 to 200 (hr ⁻¹ ). More preferably, it is in the range of SV1O-100. If it is lower than SV1, the activation time tends to be long and tends to be inefficient, and if it is larger than SV200, a large pump movement is required and tends to be inefficient.

This series of desorption and activation operations can be performed while the column is filled with the adsorbent. That is, regeneration can be easily performed by passing an alkaline aqueous solution and an acidic aqueous solution sequentially through the column after the adsorption operation is completed in the column packed with the adsorbent. In this case, the liquid flow direction may be either an upward flow or a downward flow.
Since the porous molded article of the present invention is excellent in chemical resistance and strength, the ion adsorption performance is hardly lowered even if this regeneration treatment is repeated several tens to several hundreds of times.

The present invention will be described based on examples.
[Production Example 1] Production of inorganic ion adsorbent One liter of an O.15 molar aqueous solution of zirconium oxychloride (ZrOC1 ₂ ) was prepared. This solution contained 13.7 g of metal ions as zirconium. In this aqueous solution, 84.Og of ferrous sulfate crystals (FeSO ₄ · 7H ₂ O) was added and dissolved while stirring. This amount corresponds to 0.3 mol of iron ion (F / T (molar ratio) 0.67).

  Next, a 15% by weight sodium hydroxide solution was added dropwise to this aqueous solution while stirring until the pH of the solution reached 9, resulting in a blue-green precipitate. Next, air was blown in at a flow rate of 10 liters / hour while the aqueous solution was heated to 50 ° C. When the air blowing was continued, the pH of the aqueous solution was lowered. In this case, a 15 wt% sodium hydroxide solution was dropped to maintain the pH at 8.5-9. When the blowing of air was continued until no ferrous ions could be detected in the liquid phase by spectrophotometric analysis, a black precipitate was formed. The black precipitate was then filtered off with suction, washed with deionized water until the filtrate was neutral, and dried at 70 ° C. or lower. This was pulverized with a ball mill for 7 hours to obtain an inorganic ion adsorbent powder having an average particle size of 2.8 μm.

The BET specific surface area of this powder was 170 m ² / g. The structure of the obtained inorganic ion adsorbent powder is based on the results of observation and analysis with a transmission electron microscope equipped with X-ray diffraction analysis and elemental analysis equipment. ) Was covered with hydrated zirconium oxide (possibly with solid solution of iron).

[Production Example 2] Production method of porous molded body Ethylene vinyl alcohol copolymer (EVOH, Nippon Synthetic Chemical Industry Co., Ltd., Soarnol E3803 (trade name)) 10 g, Polyvinylpyrrolidone (PVP, BASF Japan Co., Ltd., Luvitec) 10 g of K30 Powder (trade name) and 80 g of dimethyl sulfoxide (DMSO, Kanto Chemical Co., Inc.) were dissolved by heating at 60 ° C. in a Separa flask to obtain a uniform polymer solution. To 100 g of this polymer solution, 92 g of the inorganic ion adsorbent powder prepared in Production Example 1 was added and mixed well to obtain a slurry.

The obtained composite polymer slurry was heated to 40 ° C., and supplied to the inside of a cylindrical rotating container having a nozzle with a diameter of 5 mm on the side surface. The container was rotated, and droplets were discharged from the nozzle by centrifugal force (15G). Was discharged into a coagulation bath made of water at 60 ° C. to coagulate the composite polymer slurry. Further, washing and classification were performed to obtain a spherical molded body having an average particle size of 623 μm.
Furthermore, when the surface and fractured surface of the obtained porous molded body were observed using a scanning electron microscope (SEM), the presence of a skin layer was not observed. In addition, a maximum pore diameter layer (void layer) was observed near the surface, and voids inside the fibril and pores on the fibril surface were also confirmed. Furthermore, it was observed that the inorganic ion adsorbent powder was supported on the outer surface of the fibril and the void surface inside the fibril.

[Production Example 3] Production of hollow fiber cartridge A hollow hollow fiber cartridge having a membrane area of 0.15 m ² and having a skirt portion at the bottom of the adhesive resin portion was prepared by bonding and fixing both ends of the hollow fiber with resin. The hollow fiber was a microfiltration membrane made of polyvinylidene fluoride and having a pore diameter of 0.1 μm, and had an outer diameter of 1.4 mm and an inner diameter of 0.8 mm.
In the lower adhesive fixing layer, five through holes having a diameter of 5 mm are opened along the hollow fiber.

[Example 1]
An embodiment of the water treatment apparatus of the present invention is shown in FIG.

In FIG. 1, the adsorption process will be described first.
The wastewater from the food factory was received into the aeration tank 2 through the raw water supply channel 1, and air was supplied into the aeration tank through the air diffuser 4 using the blower 3 for biological treatment.
The quality of raw water remained almost stable at COD of 100 to 500 mg / liter and phosphate ion concentration of 5 mg-P / liter.
The MLSS concentration in the aeration tank changed at 10,000 mg / liter.
Next, using the suction pump 6, the liquid in the aeration tank was operated using the hollow fiber cartridge 5 of Production Example 3 with a permeated water amount of 0.7 m ³ / m ² / day. The filtered treated water was stored in the pH adjustment tank 8 through the flow path 7.

The water quality after membrane filtration was purified to turbidity <0.1 and turbidity, and COD was 15 mg / liter and phosphate ion concentration was 1.5 mg-P / liter.
In the pH adjusting tank 8, the pH adjusting agent addition mechanism 9 was used to adjust the pH to 3 by adding sulfuric acid.
The pH-adjusted raw water was sent to the column 12 via the pipe 10 and the pump 11. The column 12 was filled with 0.1 L of the porous molded body of Production Example 2 and passed with water at 1 liter / hr (SV 1 O).
The wastewater on which phosphate ions were adsorbed and purified was temporarily stored in the treated water tank 14 via the flow path 13, and discharged by the pH adjuster addition mechanism 15 after neutralization using sodium hydroxide.
The phosphate ion concentration of treated water was less than O.1 mg-P / liter.

Next, the backwash process will be described.
When the phosphate ion concentration of the treated water exceeded 0.5 mg-P / liter, valve c and valve h were closed to stop the feed of raw water. Next, the valve g and the valve b are opened, and the treated water in the treated water tank 14 is fed at 3 liter / hr (SV30) from the lower side of the column 12 through the flow path 16 and the pump 17, The adsorbent was developed and washed. The cleaning liquid was returned to the pH adjusting tank 8 through the flow path 18.

Next, the desorption process will be described.
The 5 wt% sodium hydroxide aqueous solution stored in the desorption liquid tank 19 is sent to the column 12 at 0.1 liter / hr (SV1) for 6 hours via the flow path 20 and the pump 21 to obtain the adsorbent and The adsorbed phosphate ion was desorbed into the aqueous sodium hydroxide solution and stored in the crystallization tank 23 via the flow path 22.
At this time, the phosphate ion concentration in the crystallization tank 23 was 570 mg-P / liter.

Next, the crystallization process will be described.
The aqueous solution of sodium phosphate stored in the crystallization tank 23 and the calcium hydroxide slurry stored in the crystallization drug tank 24 are converted to 3 g / liter in terms of calcium hydroxide via the passage 25 and the pump 26, and the crystallization tank 23 The mixture was stirred for 20 hours using a stirrer 27, and a crystallization reaction was performed to form calcium phosphate crystals. After the completion of the crystallization reaction, the clouded liquid containing the crystallized calcium phosphate is passed through the flow path 28, the pump 29, and the membrane separation device 30 (Asahi Kasei Chemicals Co., Ltd., ultrafiltration membrane, nominal molecular weight cut off 6, 000) and separated into solid and liquid. The aqueous sodium hydroxide solution after the solid-liquid separation had a phosphate ion concentration of 10 mg-P / liter and a calcium ion concentration of 1 mg-Ca / liter.
The calcium phosphate slurry concentrated by solid-liquid separation is circulated to the crystallization tank 23 via the flow path 31. The calcium phosphate slurry concentrated in the crystallization tank 23 was discharged from the valve i.

Next, the activation process will be described.
One liter of an activation solution adjusted to pH 3 with sulfuric acid was prepared in the pH adjustment tank 33. The liquid was fed to the column 12 through the flow path 34 and the pump 35 at 6 liter / hr (SV60), contacted with the adsorbent in the column, and circulated through the pH adjustment tank 33 through the flow path 36. Since the activation liquid comes into contact with the adsorbent in the column 12 and becomes alkaline, the pump 40 linked to the pH controller 37 installed in the pH adjustment tank 33 is used to store 50 wt% stored in the activation liquid storage tank 38. The sulfuric acid aqueous solution was fed to the pH storage tank 33 via the flow path 39 and controlled in the pH range of 3-5. This operation was repeated for 9 hours to stabilize the pH in the column 12 at 5. In order to increase the accuracy of pH control, the activation liquid was stirred using a stirrer 41.

The above adsorption process, backwash process, desorption process, crystallization process, and activation process were sequentially repeated, and the system could be stably operated for 3 months.
In addition, the amount of sludge generated in the operation period of 3 months is 0.60 kg / kg-SS, which is lower than the amount of sludge generated in the standard activated sludge method, 0.7 kg / kg-SS. It was confirmed that the amount of surplus sludge generated, which is a feature of the membrane separation activated sludge process, can be reduced.
Thus, if the waste water treatment apparatus of this invention is used, the generation amount of excess sludge can be decreased and the phosphorus density | concentration in treated water can be made low stably.

[Example 2] Wastewater treatment apparatus and method A wastewater treatment apparatus comprises an aeration tank 301 composed of a tank filled with a contact material as a biological treatment means, a sludge precipitation tank 302 as a sludge separation means, and a porous molded body as an ion adsorption means. Used was an apparatus in which the column 303 packed with was connected as shown in FIG. The volume of the aeration tank was 18 L in total, that is, 6 L for the first tank and 3 L from the second tank to the fifth tank. The contact material 304 and the air diffuser 305 were installed in all the tanks. The contact material is a 1.5-cm long loop of polyvinylidene chloride fiber, and a part of it is fixed to a plastic-coated copper core material of 50 cm in length. It is a helical shape with a length of 40 cm and an outer diameter of 8 cm. I made it. The capacity of the sludge settling tank was 5L. The column was filled with 0.1 L of the porous molded body produced in Production Example 2.

  The waste water 306 (BOD 700 mg / l, n-hexane value 50 mg / l) which diluted the liquid food with water was supplied 12 L / day. The first tank to the fifth tank were all aerated at an air amount of 1 to 1.5 L / min and adjusted so that DO was 4 to 5 mg / l. At this time, HRT was 36 hours, MLSS was 3000 to 5000 mg / l, and it was observed that oil worms and earthworms adhered to the contact material. The sludge precipitated in the sludge settling tank was returned to the first tank by a pump at 20 L / day. Wastewater treatment was continued for 3 months, but sludge was never extracted. At this time, the supernatant of the sludge settling tank was BOD 20 mg / l, TP 5 mg / l, and the treated water 307 that passed through the column was BOD 3 mg / l, TP 0.1 mg / l or less. It can be seen that if this wastewater treatment apparatus is used, surplus sludge is hardly generated and the phosphorus concentration in the treated water can be made extremely low.

  The wastewater treatment apparatus and method of the present invention can be suitably used in the field of organic wastewater treatment.

The schematic diagram of the wastewater treatment apparatus of this invention. The schematic diagram of the hollow fiber cartridge of this invention. The schematic diagram of the wastewater treatment apparatus of this invention.

Explanation of symbols

1: Raw water supply path 2: Aeration tank 3: Blower 4: Aeration pipe 5: Filtration membrane 6: Suction pump 7: Channel 8: pH adjustment tank 9: pH adjuster addition device 10: Channel 11: Pump 12: Column 13: Channel 14: Treated water tank 15: pH adjuster addition mechanism 16: Channel 17: Pump 18: Channel 19: Desorption liquid tank 20: Channel 21: Pump 22: Channel 23: Crystallization tank 24: Crystal Analysis chemical tank 25: flow path 26: pump 27: stirrer 28: flow path 29: pump 30: membrane separation device 31: flow path 32: flow path 33: pH adjustment tank 34: flow path 35: pump 36: flow path 37 : PH controller 38: Activation liquid storage tank 39: Flow path 40: Pump 41: Stirrer 42: Sludge extraction pipe
a, b, c, d, e, f, g, h, i: valve 201: hollow fiber cartridge 202: hollow fiber 203: through hole 204: skirt 205: cartridge head 206: upper adhesive fixing layer 207: lower adhesive fixing Layer 208: treated water outlet 301: aeration tank 302: sludge settling tank 303: column 304: contact material 305: air diffuser 306: waste water 307: treated water

Claims (15)

Biological treatment means, a wastewater treatment system sludge separation means and porous molded body is made of ion adsorption means filling, the fibrils porous molded body, comprising an organic polymer resin and an inorganic ion adsorbent it forms a three-dimensional network structure, a porous molded body having a communication hole that opens to the outer surface, the gap between the fibrils to form a communication hole, and said fibrils have voids therein, A wastewater treatment apparatus characterized in that at least a part of the voids are perforated on the surface of the fibril, and an inorganic ion adsorbent is supported on the outer surface of the fibril and the surface of the inner void.   2. The wastewater treatment apparatus according to claim 1, wherein the communication hole has a maximum pore diameter layer near the surface of the molded body.   Porous molded body, wherein the organic polymer resin comprises one or more selected from the group consisting of ethylene vinyl alcohol copolymer (EVOH), polyacrylonitrile (PAN), polysulfone (PS), and polyvinylidene fluoride (PVDF). The wastewater treatment apparatus according to claim 1 or 2. The wastewater treatment apparatus according to any one of claims 1 to 3, wherein the inorganic ion adsorbent contains at least one metal oxide represented by the following formula (I).
_{MN x O n · mH 2 O} (I)
(Wherein x is 0 to 3, n is 1 to 4, m is 0 to 6, and M and N are Ti, Zr, Sn, Sc, Y, La, Ce, Pr, Nd, Sm, Eu. Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Si, Cr, Co, Ga, Fe, Mn, Ni, V, Ge, Nb and Ta are metal elements selected from the group Are different from each other.) 5. The metal oxide represented by the formula (I) is one or a mixture of two or more selected from any of the following groups (a) to (c): The wastewater treatment apparatus as described.
(A) hydrated titanium oxide, hydrated zirconium oxide, hydrated tin oxide, hydrated cerium oxide, hydrated lanthanum oxide, and hydrated yttrium oxide (b) consisting of titanium, zirconium, tin, cerium, lanthanum, and yttrium A composite metal oxide of a metal element selected from the group and a metal element selected from the group consisting of aluminum, silicon, and iron (c) activated alumina   The wastewater treatment apparatus according to any one of claims 1 to 5, wherein the biological treatment means includes two or more aeration tanks.   The wastewater treatment apparatus according to any one of claims 1 to 6, wherein the biological treatment means includes an aeration tank in which the contact material is immersed.   The waste water treatment apparatus according to claim 7, wherein the contact material is composed of a core material and a fibrous material partially fixed to the core material, and the fibrous material is densely formed around the core material.   The wastewater treatment apparatus according to claim 8, wherein the core material has a spiral shape.   The wastewater treatment apparatus according to claim 8 or 9, wherein the fibrous material is polyvinylidene chloride.   The wastewater treatment apparatus according to any one of claims 1 to 10, wherein the sludge separation means is a sedimentation tank and / or a membrane separation apparatus.   The separation membrane of the membrane separator comprises one or more selected from the group consisting of polyacrylonitrile (PAN), polysulfone (PS), polyvinylidene fluoride (PVDF), polyethylene (PE), and polypropylene (PP). 11. A wastewater treatment apparatus according to 11.   The wastewater treatment apparatus according to claim 11 or 12, wherein the separation membrane is a hollow fiber.   The separation membrane is a membrane cartridge in which both ends of a plurality of hollow fibers arranged in the vertical direction are bonded and fixed, and a cartridge head that is liquid-tightly bonded and fixed to the outer periphery of one end, and fixed to the outer periphery of the other end The cartridge head and the skirt are separated, the cartridge head side hollow fiber end is open, the skirt side hollow fiber end hollow is sealed, and the skirt side adhesive fixing layer The wastewater treatment apparatus according to any one of claims 11 to 13, wherein a plurality of through holes are provided in the body. Biological treatment process, a waste water treatment method for sludge separation step and porous molded body comprising a packed ion adsorption step, the fibrils porous molded body, comprising an organic polymer resin and an inorganic ion adsorbent it forms a three-dimensional network structure, a porous molded body having a communication hole that opens to the outer surface, the gap between the fibrils to form a communication hole, and said fibrils have voids therein, A wastewater treatment method characterized in that at least a part of the voids are open at the surface of the fibril, and an inorganic ion adsorbent is supported on the outer surface of the fibril and the surface of the void inside.

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