JP2005296928A - Purifying material for waste water treatment, method of purifying waste water using the same and waste water treatment apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a low cost, environmentally friendly purifying material for waste water treatment which is excellent in anion adsorption, a method of purifying waste water using the same and a waste water treatment apparatus. <P>SOLUTION: The purifying material for waste water treatment is composed of a carbon material 9S having anion adsorption characteristic by bringing a carbonized material 9 obtained by carbonizing a raw material of plant origin 5 into contact with an acid solution 12 or contains the carbon material 9S. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a wastewater treatment purification material that adsorbs anions such as nitrate ions, nitrite ions, and fluoride ions, a wastewater purification method using the same, and a wastewater treatment apparatus.

  Water and soil contamination by heavy metals, pesticides and organochlorine compounds are problematic as they destroy the environment. These harmful substances can be adsorbed and removed by adsorbents such as activated carbon and zeolite, but nitrate nitrogen or nitrite nitrogen, fluorine, arsenic, cyanide, etc. present in the form of anions are difficult to treat with adsorbents. is the current situation.

  For example, nitrate nitrogen and nitrite nitrogen are serious problems due to groundwater contamination due to fertilization contained in plant culture wastewater such as tea plantations and golf course turf. Is not found. Nitrate ions contained in wastewater from chemical factories, petroleum refining factories, steel and steel manufacturing factories, paper mills, semiconductor factories, industrial waste storage, spinning factories in textile manufacturing, food factories, and domestic wastewater And nitrite ions are negatively charged and do not form a sparingly soluble salt when combined with other substances, so they are most easily leached from negatively charged soils, and water pollution such as groundwater is currently a major problem. In addition, recently it has been suspected of being an environmental hormone.

  Although a method using denitrifying bacteria is also considered as a method for removing nitrate nitrogen components from wastewater, in order to remove nitrate nitrogen by denitrifying bacteria, it is a hydrogen donor while keeping anaerobic conditions. There is a problem that it is necessary to grow denitrifying bacteria while reducing nitrate nitrogen in the presence of organic substances such as methanol to perform denitrification, and the operation operation is complicated, and maintenance and management are troublesome and expensive.

  In recent years, a large number of pharmaceuticals, agricultural chemicals, functional chemicals, polymers, and the like containing fluorine are produced due to their characteristics, and they tend to be used more and more in the future. For this reason, when these compounds are synthesized or used, fluorine is contained in factory wastewater, households, combined septic tanks, and household wastewater in village units. In addition, fluorine is contained in industrial wastewater from the glass, plating industry, metal refining, metal surface treatment, ceramic industry, electronics industry such as semiconductor, and chemical industry. However, since fluoride ions are harmful ion species, it is necessary to discharge the fluoride ions by performing some kind of treatment on waste water for environmental protection.

  Therefore, a method has been adopted in which a calcium compound is added to fluorine in various wastewaters and removed as calcium fluoride. However, it is necessary to install an adsorption tower with activated alumina or an anion exchange resin for fluorine. There is a cost. Further, if the environmental standard is 0.8 mg / L or less, an expensive dedicated anion exchange resin is required. In addition, arsenic and cyanide require expensive anion exchange resins for the treatment of industrial wastewater and groundwater contamination.

  On the other hand, in order to remove fluorine from waste water, as a method of using an adsorbent, a resin matrix carrying a metal hydrate or a metal adsorbed on an ion exchange resin, a cation exchange resin Fluoride ion adsorbents in which metal ions such as thorium, zirconium, and titanium are adsorbed are considered. However, these adsorbents have a problem that the adsorption speed is slow.

As described above, there is no inexpensive material that adsorbs the anions including nitrate ions at present, and therefore, contamination by these anions tends to spread and is once contaminated by the anions. And the restoration requires a great cost.
JP-A 61-287443 JP-A-5-115777 JP-A-6-126298 JP-A-6-57476 JP-A-7-265864 Japanese Patent Laid-Open No. 10-249393 JP 2002-186972 A Japanese Patent Laid-Open No. 2003-126885 Japanese Patent Laid-Open No. 10-165824

  Therefore, there is a need for an anion adsorption material that is inexpensive and environmentally friendly. Charcoal, which is a typical porous carbon material together with activated carbon, is widely used as a humidity control material, river purification material, soil improvement material, etc. For example, for removing chlorine-based gas and sulfur oxide in exhaust gas It's being used. This, like activated carbon, only uses the adsorption characteristics due to the fine pores inside the porous carbon material, and nitrate nitrogen or nitrite nitrogen or fluorine, arsenic, and cyanide that exist in the form of anions. Almost no adsorption.

  The present invention has been made in consideration of the above-mentioned matters, and an object of the present invention is to provide a wastewater treatment purification material that is inexpensive, environmentally friendly and excellent in anion adsorption, and a wastewater purification method using the same. In addition, the present invention is to provide a waste water treatment apparatus.

  As a result of studying the anion adsorption performance of the material obtained by bringing the acid solution into contact with the carbide, the present inventors have found that the carbonization treatment temperature and acid for the raw material plant (raw material consisting of plants) such as natural fiber and woody material. It was found that the obtained material has excellent anion adsorption performance, although it depends on the concentration of the anion.

That is, for example, if an acid solution such as hydrochloric acid (HCl) or sulfuric acid (H ₂ SO ₄ ) is brought into contact (acid treatment) with charcoal obtained by carbonizing wood as a raw material plant, the ability to adsorb anions can be obtained. The inventors have found that it is expressed. This is because an anion that can be ion-exchanged with the anion to be adsorbed is bonded to the functional group present on the microporous wall surface of the raw material plant. In addition, as a method of bringing the acid solution into contact with the carbide, the acid solution can be dropped, applied, sprayed, sprayed, etc., but it is most effective to immerse the carbide in the acid solution.

Furthermore, before carbonizing the raw material plant, the raw material plant contains a calcium-containing solution (desirably containing mainly calcium ions as cations), for example, a saturated aqueous solution of calcium hydroxide (Ca (OH) ₂ ) ( Lime water) or suspension (lime milk) is contacted to introduce Ca into the raw material plant, and then the Ca-introduced material is carbonized, and the resulting Ca-introduced charcoal is HCl, H ₂ SO _4, etc. The present inventors have found that better anion adsorption characteristics can be obtained by treatment with an acid.

  Therefore, the purification material for wastewater treatment of the first invention is made of a carbon material having anion adsorption characteristics by contacting an acid solution with a carbide obtained by carbonizing a raw material plant, or the carbon material (Claim 1).

In addition, the purification material for waste water treatment of the second invention is made of a carbon material having anion adsorption characteristics by bringing an acid solution into contact with a carbide obtained by carbonizing a calcium-treated raw material plant, Alternatively, the carbon material is included (claim 2). The calcium introduction treatment is preferably performed by bringing a solution containing calcium ions into contact with the raw material plant (claim 3).
Examples of the solution containing calcium ions include calcium acetate solution and calcium chloride solution in addition to lime water and lime milk. The calcium content is 0.03 to 30% by weight, more preferably 0.1 to 7.0% by weight. Those included are preferred.

The acid solution used for the contact treatment of the raw material plant after the carbonization treatment is preferably an acid solution such as HCl or H ₂ SO ₄ that does not interfere with the waste water treatment during the production of the waste water treatment purification material. The concentration of the acid solution is preferably 0.01 mol / L or more (Claim 4). This is because sufficient adsorption characteristics cannot be obtained when the acid solution concentration is less than 0.01 mol / L. In more detail, the acid solution concentration is 0.01 mol / L to 20 mol / L, preferably 0.1 mol / L to 10 mol / L.

Further, the present invention intensively studied, before carbonizing a raw material consisting of plants, a solution containing a pre-metal chlorides in the raw materials, for example the CaCl ₂ in the raw material by contacting a solution containing CaCl ₂ If the raw material into which the CaCl ₂ was introduced was carbonized after introduction, the carbonized material obtained thereby was found to have excellent anion adsorption performance.

  Therefore, the purification material for waste water treatment according to the third aspect of the present invention comprises a carbon material obtained by carbonizing a raw material plant into which a metal chloride has been introduced to give the carbide an anion adsorption property, or the carbon material. (Claim 5). Since the chloride ion of the metal chloride contained in the carbide expresses the anion exchange ability, the carbide functions as a purification material for waste water treatment. In addition, the introduction treatment of the metal chloride to the raw material plant can be performed by bringing the solution containing the metal chloride into contact with the raw material plant. Examples of the contact method include dropping, coating, spraying, spraying, and the like of the solution. Although it is possible, it is most efficient to immerse the raw plant in the solution.

In discharging wastewater treatment for purification material of the third invention, the raw material plant is immersed in a solution containing CaCl ₂ as a metal chloride, introducing handle and Ca ions and Cl ions in the raw material, then the CaCl ₂ introduced The CaCl ₂ -introduced carbon obtained by carbonizing the material shows excellent anion adsorption performance.

That is, for example, as shown in FIG. 25 (A), the wood chip 5 as a raw material is immersed in CaCl ₂ solution 100 is contacted to the CaCl ₂ solution 100, the Ca ions and Cl ions in CaCl ₂ solution 100 When introduced into the wood chip 5, a CaCl ₂ introduction chip 101 is obtained as shown in FIG. This is because the CaCl ₂ solution 100 soaks into the tissue in the wood chip 5, particularly the passage tissue, as shown in FIG. As the concentration of the CaCl ₂ solution 100 used in the pretreatment of the raw material (contact treatment), CaCl ₂ 0.1 wt% to 50 wt% by weight, and cost more preferably 1 wt% to 20 wt%. If the amount is less than 0.1% by weight, a high anion adsorption ability is not expressed, and if it exceeds 50% by weight, the anion adsorption ability is not improved.

Subsequently, when the CaCl ₂ introduction chip 101 is carbonized as shown in FIG. 26A, the purification material 1 is obtained as shown in FIG. In this carbonization process, organic substances in the CaCl ₂ introduction chip 101 are decomposed by heat, and at the same time, Cl ions and Ca ions are deposited on the surface of the fine pore wall of the CaCl ₂ introduction chip 101. At this time, as shown in FIG. 5B, Cl ions and Ca ions are deposited in a fine and highly dispersed state on the surface of the fine pore wall of the CaCl ₂ introduction chip 101, and many functional groups are formed at every corner of the fine pore wall. Pull out from. As a result, as shown in FIG. 6C, it is considered that Cl ions are bonded to a large number of functional groups extracted on the surface of the microporous wall via metal ions (in this case, Ca ions) or directly. It is done.

  In addition, as content of the said metal chloride, it is preferable to contain 2 to 25% of the metal chloride couple | bonded in the said carbide | carbonized_material as ash (Claim 6). The metal chloride bonded in the carbide is a metal chloride except for the metal chloride that is simply adhered in the carbide. Since it is bonded in the carbide, it does not dissolve after washing with water or acid. The metal chloride remaining in If it is less than 2%, the anion adsorption ability is inferior, and even if it exceeds 25%, the anion adsorption ability tends not to be improved.

  Furthermore, in the invention according to claims 5 and 6, it is preferable that the carbide is in contact with water and / or an acid (invention 7). In addition, as a method of bringing water and / or acid into contact with the carbide, water and / or acid can be dropped, applied, sprayed, sprayed, etc., but the carbide is immersed in water and / or acid. Is the most efficient.

Here, the reason why it is preferable to contact the carbide with water and / or an acid is considered as follows. That is, the purification material (CaCl ₂ charcoal) 1 obtained as shown in FIGS. 25 and 26 is immersed (contacted) in an acid such as hydrochloric acid 102 or sulfuric acid, as shown in FIG. 27A. Then, excess metal chloride crystals adhering to the purification material 1 are removed. In addition, when hydrochloric acid 102 is used as the acid, Cl ions bonded to the functional group of the purification material 1 are newly increased, and the state changes from the state (B) to the state (C). From the above, the produced anion adsorption ability is preferably increased. Even when the carbide is brought into contact with water instead of an acid such as hydrochloric acid 102, excess metal chloride crystals adhering to the purification material 1 are removed, and the anion adsorption ability can be enhanced.

Specifically, examples of the metal chloride include CaCl _{2 and} BaCl ₂ .

The raw material plant in the wastewater treatment purification material may be anything as long as it is a plant body, but is preferably composed of one or more of natural fibers and woody materials, and a carbide having fine pores. Examples include all woody materials such as felled trees and waste wood, and natural fibers such as hemp. Specifically, it is preferable to use a wood chip in which conifers such as birch and cedar having high water absorption are chipped to a size of, for example, 50 mm or less (preferably 10 mm or less). Further, in addition to the wood chips, agricultural waste such as bamboo, sawdust, rice husk, coconut, areca, jute, straw, mandarin orange, apple skin, and pomace may be used. Moreover, the part which has a passage tissue (a canal, a temporary canal, or a master tube) in a plant body is especially preferable.
In the case of using a solution (for example, lime water or lime milk) that contains almost no anion (for example, chloride ion) ion-exchangeable with the anion to be adsorbed as the solution in contact with the material (for example, lime water or lime milk), Preferably, when carbon is introduced and then carbonized, countless Ca compounds having a particle size of 100 nm or less are formed in the fine pores of the carbide.
Moreover, when using the solution (for example, calcium chloride solution etc.) which contains both the anion (for example, chloride ion etc.) and calcium ion which can be ion-exchanged with an adsorption object anion, when immersing in a solution as said raw material, It is desirable for the material to easily penetrate.

  Moreover, in the waste water purification method of 2nd invention, before carbonizing a raw material plant, it is made to introduce | transduce calcium to a raw material plant, for example by making the solution containing a calcium ion contact the said raw material plant. Yes. As a method of bringing a solution containing calcium ions into contact with the raw material plant, the solution can be dropped, applied, sprayed, sprayed, etc., but it is most effective to immerse the raw material plant in the solution.

That is, when the raw material is immersed in a solution containing calcium ions, a Ca-introduced chip can be obtained by the solution soaking into the raw material. In particular, when an alkaline solution is used as a solution containing calcium ions, as shown in FIG. 11A, for example, when the wood chip 5 is immersed in the lime water 18, the lime water 18 is brought into contact with the wood chip 5. Then, Ca in the lime water 18 is introduced into the wood chip 5, and the Ca introduction chip 16 is obtained as shown in FIG. This is presumably because, as shown in FIG. 11 (B), the organic matter in the wood chip 5 is dissolved by alkali and Ca ions react with the components of the wood chip 5. And as a density | concentration of the lime water (or lime milk) used for the contact process as a pretreatment for a raw material plant, Ca (OH) ₂ 0.1 weight%-50 weight% are preferable, More preferably, 0.2 weight% -10% by weight.

  When the Ca-introduced chip 16 is carbonized as shown in FIG. 12 (A), a Ca-introduced carbonized chip (Ca-introduced carbon) 21 as shown in FIG. 12 (C) is obtained. 16 (see FIG. 12B) is decomposed by heat, and at the same time, Ca ions are deposited on the surface of the fine pore wall of the Ca introduction chip 16 [see FIG. In this case, as shown in FIG. 12 (B), Ca ions are precipitated on the surface of the fine pore wall of the Ca-introduced chip 16, so that a fine and highly dispersed state results in the addition of many functional groups to the fine pore wall. It is thought to be drawn from every corner.

  In the first invention, after carbonizing the raw material plant, an acid solution is brought into contact with the carbide, and in the second invention, the raw material plant subjected to calcium introduction treatment by contacting a solution containing calcium ions is carbonized. Then, by contacting the carbide with an acid solution, an anion capable of ion exchange with an anion to be adsorbed is bonded directly or via a calcium ion to the functional group extracted from the microporous wall of the carbide, respectively. I am letting.

  The inventors have also found that more functional groups of carbides can be generated by controlling the temperature and time during the carbonization process. That is, as in the first invention, when Ca is not introduced into the raw material plant, there is little difference in the generation amount of the functional group of the carbide depending on the heating temperature during the carbonization treatment. On the other hand, when Ca is previously introduced into the raw material plant as in the second invention, the carbonization temperature of 650 to 750 ° C. is maintained for, for example, 1 hour, and then the natural cooling is about 600 ° C. The present inventors have confirmed that more functional groups can be formed as compared with the case where the carbonization temperature of about 800 ° C. is maintained for 1 hour and then the mixture is naturally cooled.

  In particular, when Ca is introduced, when observed with an electron microscope, in a carbide carbonized at a carbonization temperature of 650 to 750 ° C., fine particles of the Ca compound are half-deposited on the fine pore wall surface of the carbide and are uniformly dispersed. The situation was observed. On the other hand, at the carbonization temperature of about 600 ° C., it was observed that the Ca compound fine particles were not sufficiently deposited on the fine pore walls. Further, at the carbonization temperature of about 800 ° C., although the precipitation of Ca compound fine particles on the fine pore walls was observed, it was observed that the number of missing portions increased. Thus, about 650-750 degreeC (optimally 700 degreeC) can be mentioned as a carbonization process temperature required in order for Ca to draw out as many functional groups as possible from the fine pore wall of a carbide | carbonized_material.

In particular, in the second invention, as a raw material plant to be carbonized, a plant into which Ca is introduced using a solution containing calcium ions is used, and this is carbonized to obtain a Ca-introduced coal 21. For example, as shown in FIG. 13 (A), when Ca-introduced charcoal 21 is immersed in HCl solution 12, it binds to the functional group on the surface of Ca-introduced charcoal 21 as shown in FIGS. calcium ion and the functional group to the chloride ions (Cl ^-) is attached, as shown in FIG. (D), Cl to the functional group ^- via calcium ions or a direct bond to which acid treatment It is considered that Ca-introduced charcoal 21S is obtained. In addition, although the said acid treatment only needs to immerse the Ca introduction | transduction charcoal 21 in the acid solution 12, it is preferable to carry out under reduced pressure and it is preferable to carry out in the pressure range of 1330Pa-13.3Pa.

  And it is preferable that the carbonization process of a raw material plant is performed in the temperature range of 400 to 1000 degreeC (Claim 9). This is because if the carbonization temperature is lower than 400 ° C., the pores do not develop and the performance as an adsorbent is inferior, and if the temperature exceeds 1000 ° C., adsorption characteristics cannot be obtained due to excessive carbonization. It is. The carbonization temperature is more preferably 500 ° C to 900 ° C, and most preferably 650 ° C to 750 ° C.

  The wastewater treatment purification material having the above-described configuration has excellent anion adsorption performance. The purification material for waste water treatment does not cause any problems in waste water treatment at the time of production, and is extremely environmentally friendly and can be produced at low cost. Furthermore, the adsorbed anion is removed from the purification material for waste water treatment that adsorbs the anion to be adsorbed, and the anion that can exchange ions with the next anion to be adsorbed is replaced with the removed anion. (Claim 10), the waste water treatment purification material can be repeatedly recycled. The anion that can be adsorbed by the purification material for wastewater treatment of the present invention can be ion-exchanged with an anion previously bonded to a functional group on the surface of the fine pore wall of the carbide directly or via calcium ion. Naturally, it is an anion other than an anion previously bonded directly or via a calcium ion to a functional group on the surface of the microporous wall of the carbide.

  And the waste-water purification method of 4th invention is characterized by purifying waste-water using the waste-water-treatment purification material in any one of Claims 1-10 (Claim 11). The waste water treatment purification material can be used as it is, but can be processed into a granular form or a powder form. Therefore, for example, the granular wastewater treatment purification material is stored in a mesh bag or mesh bag having an appropriate mesh to form a wastewater treatment purification body, and this wastewater treatment purification body is used as wastewater. The anion contained in the sewage is surely adsorbed by being installed in a state where it can be sufficiently in contact with. Moreover, when powdered, it may be used as a waste water treatment purifier by attaching it to a nonwoven fabric. Furthermore, a drainage prevention mesh may be provided in the drainage wastewater passage, and the wastewater treatment purification material may be accommodated in the passageway by containing the wastewater treatment purification material.

  A waste water treatment apparatus according to a fifth aspect of the present invention is characterized in that the waste waste water treatment purification material according to any one of claims 1 to 11 is provided in a waste waste water flow path to purify waste waste water. (Claim 12). This wastewater treatment equipment is used from semiconductor factories, oil refining factories, various chemical factories such as pharmaceuticals, agricultural chemicals and functional chemicals, steel and steel manufacturing factories, metal refining factories, paper mills, textile factories, plant factories, and food factories. It can be adsorbed reliably to anions in wastewater by applying it to domestic wastewater and domestic wastewater in each household, combined septic tank, and village unit.

  In addition, it is preferable to have a regeneration unit for regenerating the adsorption capacity of the waste water treatment purification material and a purification material take-out mechanism for moving the waste water treatment purification material to the regeneration unit. In other words, by periodically regenerating the waste water treatment purification material in the regeneration unit, it is possible to effectively adsorb the anions contained in the waste water without reducing the adsorption capacity.

  The purification material for wastewater treatment of the present invention has a desired anion adsorption performance, and is composed of a carbon material obtained by carbonizing a raw material plant so as to have anion adsorption characteristics. Since it contains a carbon material, it is environmentally friendly and can be manufactured at low cost.

  And, in the above purification material for wastewater treatment, when the raw material plant is carbonized after calcium introduction treatment, anion adsorption carbon having anion adsorption characteristics equivalent to or better than anion exchange resin Material can be obtained.

  In addition, anions in the wastewater are reliably adsorbed by the wastewater purification method and the wastewater treatment apparatus using the wastewater treatment purification material. Moreover, you may use together the purification material conventionally used, such as a mere charcoal, in the purification material for waste water treatment.

  1 to 3 show a first embodiment of the present invention. First, FIG. 1A shows an example of a waste water treatment purification material (hereinafter simply referred to as a purification material) 1 of the present invention. In this embodiment, the purification material is formed in a chip shape having a length of about 10 mm. ing. FIG. 1 (B) shows an example in which the chip-shaped purification material 1 is formed into particles (pellets) 1a having an appropriate diameter.

  An apparatus and a method for manufacturing the purification material 1 will be described with reference to FIGS. 2 and 3. FIG. 2 schematically shows an example of an apparatus for producing the purification material 1. In this figure, 5 is a raw material plant, and in this embodiment is a wood chip. The wood chip 5 is formed by chipping coniferous trees such as birch and cedar having high water absorption into an appropriate size of 50 mm or less (preferably 10 mm or less). Reference numeral 6 denotes a carbonization furnace for carbonizing the wood chip 5, and a carbonization furnace body 8 heated by an appropriate heat source 7 is accommodated therein. The wood chip 5 supplied from the introduction part 8 a of the carbonization furnace main body 8 is carbonized by heating at an appropriate temperature (described later) and for an appropriate time (described later), and discharged as a carbonized chip (carbide) 9. Discharged from.

  In FIG. 2, reference numeral 10 denotes an apparatus for acid-treating the carbonized chip 9. For example, HCl having an appropriate concentration is accommodated in the treatment tank 11 as an acid solution 12. Reference numeral 13 denotes an agitation blade 13 provided in the treatment tank 11, which is rotationally driven by a motor (not shown) and agitates so that the concentration of the acid solution 12 in the treatment tank 11 becomes uniform. .

  In FIG. 2, 14 is a dryer for drying the carbonized chips (acid-treated carbonized chips) 9S after the acid treatment, neutralization treatment, and post-neutralization water washing treatment (hereinafter referred to as acid treatment). 14 is supplied with exhaust heat discharged from the carbonization furnace 6.

  An example of a procedure for obtaining the purification material 1 from the raw material plant 5 using the above apparatus will be described with reference to FIG. 3 as well. First, a woody material in which conifers such as birch and cedar are chipped into an appropriate size of 10 mm or less. The chip 5 is prepared (step S11).

  The wood chip 5 is supplied to the carbonization furnace body 8 of the carbonization treatment furnace 6 and heated and carbonized in a temperature range of 400 ° C. to 1000 ° C. for about 1 hour (step S12). Thereby, the carbonized chip 9 is obtained.

  The carbonized chip 9 is supplied to the acid treatment apparatus 10 and immersed in the acid solution 12 adjusted to 0.01 mol / L to 20 mol / L in the treatment tank 11 to be subjected to acid treatment (step S13). The immersion treatment of the carbonized chip 9 in the acid solution 12 is an example of a process of bringing the acid solution 12 into contact with the carbonized chip 9. Spraying, spraying, etc. are possible.

  The acid-treated carbonized chip 9S after the acid treatment is generally dried in the dryer 14 (step S14). In this case, the acid-treated carbonized chips 9S may be sent to the dryer 14 as they are, but may be neutralized by immersing them in an appropriate alkaline solution, or may be washed with water after the neutralization. . When the acid-treated carbonized chip 9S is used in a wet state, the drying process may not be performed.

  The acid-treated carbonized chip 9S after the drying treatment can be used as it is without being processed, but with an appropriate processing machine, the particle (pellet) 1a having an appropriate diameter or finer is used. It is formed on the powder 1b (step S15). Then, for example, by storing a large number of the pellet-shaped purification materials 1a in a net made of a wire mesh, a waste water treatment purification body is obtained (step S16).

  In the first embodiment described above, the raw material plant (for example, wood chips) 5 is carbonized, and the carbide (for example, carbonized chips) 9 obtained by this carbonization treatment is immersed in the acid solution 12 and the carbide 9 is negatively affected. The ion-adsorbing property has been provided, but as the raw material plant 5, a calcium-introduced plant may be used. Hereinafter, this will be described as a second embodiment with reference to FIGS. 4 and 5. FIG.

  First, FIG. 4 schematically shows another example of an apparatus for producing the purification material 1. In this figure, the same reference numerals as those shown in FIG. 2 are the same. Explaining that the apparatus in this embodiment is greatly different from the apparatus in the first embodiment shown in FIG. 2, 15 is an apparatus for introducing Ca into the wood chip 5 to form a Ca introduction chip 16. A solution 18 containing calcium ions is accommodated in the treatment tank 17. In this embodiment, the solution 18 containing calcium ions is lime water (or lime milk) having an appropriate concentration. Reference numeral 19 denotes a stirring blade provided in the processing tank 17, which is rotationally driven by a motor (not shown) and stirs the solution 18 containing calcium ions in the processing tank 17 so that the concentration is uniform. It is.

  In FIG. 4, reference numeral 20 denotes a dryer that dries the Ca introduction chip 16 obtained in the Ca introduction treatment device 15. The dryer 20 is supplied with exhaust heat discharged from the carbonization furnace 6. It is.

  An example of a procedure for obtaining the purification material 1 from the raw material plant 5 using the above apparatus will be described with reference to FIG. 5. First, a woody material in which coniferous trees such as birch and cedar are chipped into an appropriate size of 10 mm or less. The chip 5 is prepared (step S21).

  The wood chip 5 is immersed in a solution 18 containing calcium ions adjusted to 5 wt% in the treatment tank 17 of the Ca introduction treatment device 15 for 3 hours or more, for example. In this case, it is preferable to rotate the stirring blade 19 during the dipping of the wood chip 5 in order to sufficiently soak the solution 18 into the wood chip 5 or to sufficiently react calcium ions with the components of the wood chip 5. Thereby, Ca ion can fully react with the component of the wood chip | tip 5, and the Ca introduction | transduction chip | tip 16 by which Ca was introduce | transduced into the wood chip | tip 5 is obtained (step S22). In addition, the Ca introductory process has better processing efficiency when using lime milk. Moreover, the immersion treatment of the wood chip 5 in the solution 18 containing calcium ions is an example of the treatment in which the wood chip 5 is brought into contact with the solution 18 containing calcium ions. The solution 18 containing can be dropped, applied, sprayed, sprayed, and the like. And as the solution 18, it can replace with lime water and lime milk, and can also use a calcium chloride solution and a calcium acetate solution.

  The Ca introduction chip 16 after the Ca introduction processing is sent to the dryer 20 and dried (Step S23).

  The dried Ca-introduced chip 16 is supplied to the carbonization furnace main body 8 of the carbonization furnace 6 and heated at a processing temperature of 700 ° C. for about 1 hour to be carbonized (step S24). Thereby, a Ca-introduced carbonized chip (Ca-introduced charcoal) 21 is obtained.

The Ca introduction chip 21 is supplied to the acid treatment apparatus 10 and immersed in the acid solution 12 adjusted to, for example, 5 mol / L in the treatment tank 11 and subjected to acid treatment (step S25). In this case, it is preferable to rotate the stirring blade 13, thereby promoting the dissolution of CaCO _{3 on the} surface of the fine pore wall of the Ca introduction tip 21 by the acid, and the chloride ion and the calcium ion to the Ca introduction tip 21. It is possible to sufficiently react with the functional group on the surface of the fine pore wall, and a desired Ca-introduced acid-treated carbonized chip 21S is obtained. The immersion treatment of the Ca introduction chip 21 in the acid solution 12 shows an example of the treatment for bringing the Ca introduction chip 21 into contact with the acid solution 12. Application, spraying, spraying, etc. are possible.

  The Ca-introduced acid-treated carbonized chip 21S after the acid treatment is generally dried in the dryer 14 (step S26). In this case, the Ca-introduced acid-treated carbonized chip 21S may be sent to the dryer 14 as it is. However, the Ca-introduced acid-treated carbonized chip 21S may be neutralized by immersing it in an appropriate alkaline solution, or washed with water after the neutralization. It goes without saying.

  Then, the Ca-introduced acid-treated carbonized chip 21S after the drying treatment can be used as it is without being processed, but it can be used as it is by using an appropriate processing machine. (Step S27). Then, for example, by storing a large number of pellet-shaped purification materials 1a in a net made of a wire mesh, a waste water treatment purification body is obtained (step S28).

  FIG. 6 shows a chip-shaped purification material 1 shown in FIG. 1 or a pellet-shaped purification material 1 shown in FIG. 2 or FIG. In this example, the waste water treatment purifier 26 is accommodated in the net cage 25. Here, the net cage 25 is made of a chemically stable material such as plastic or stainless steel which is not easily affected by chemical substances or easily eluted, and the granular purification material 1a can easily escape from the mesh to the outside. It has a fine scale that does not go away. In the figure, reference numeral 25a denotes a reinforcing wire. In addition, although not shown in detail, the net fence 25 is formed with an opening having a door that can be opened and closed and locked so that the purification material 1a can be replaced or supplemented. .

  The waste water treatment purifier 25 is not limited to the one illustrated in FIG. 6. For example, as shown in FIG. 7, the purifier 25 is disposed in a net bag 27 made of a corrosion resistant material such as polyethylene. The mat-shaped waste water treatment purification body 28 may be configured by accommodating a number of the chip-shaped purification material 1 shown in FIG. 1 and the pellet-shaped purification material 1a shown in FIG. 2 or FIG. In this case, it is desirable that the opening (not shown) of the net bag 27 can be freely opened and closed so that the purification material 1 or 1a can be easily filled and removed.

  FIG. 8 schematically shows another example of the purification body 30 for waste water treatment. A waste water treatment purification body 30 shown in FIG. 8 (A) is a water-permeable sheet (for example, configured to carry the chip-shaped purification material 1 (formed into pellets 1a or powder 1b having an appropriate diameter) (for example, , Non-woven fabric sheet) 31 and a high-strength net 32 that is polymerized to the non-woven fabric sheet 31 so as to reinforce the non-woven fabric sheet 31. Moreover, the purification body 30 for waste water treatment of a present Example is a elongate strip | belt shape, for example, is comprised so that an annular strip | belt may be formed (it mentions later for details). When carrying the purification material pellets 1a or powder 1b on the nonwoven fabric sheet 31, the wastewater treatment purification body 30 is prepared by mixing the purification material pellets 1a or powder 1b into the raw material of the nonwoven fabric sheet 31. Can be configured. Moreover, you may fix the purification material 1 to the nonwoven fabric sheet 31 using the below-mentioned adhesive agent.

  The waste water treatment purification body 30 shown in FIG. 8 (B) uses the appropriate adhesive 33 to apply the chip-shaped purification material 1 (for example, the pellet-shaped purification material 1 a) to one entire surface of the nonwoven fabric sheet 31. Hold to stick. As shown in FIG. 8C, the chip-shaped purification material 1 (pellet-shaped purification material 1 a) may be adhered to both the front and back surfaces of the nonwoven fabric sheet 31.

  Here, the adsorption performance of nitrate nitrogen, nitrite nitrogen and fluorine of the purification material 1 will be described. First, the test method and test results for the adsorption performance of nitrate nitrogen and nitrite nitrogen will be described as follows.

[Adsorption performance of nitrate nitrogen and nitrite nitrogen]
〔Test method〕
Prepare 5 nitric acid solutions and 50 mL (standard solution) of nitric acid solution with 50 mg / L (50 ppm) concentration of nitrate nitrogen and nitrite nitrogen,
(1) 200 mg of charcoal 9 used in a comparative example in which the wood chip 5 is carbonized at 700 ° C.
(2) 200 mg of iron chloride charcoal used for the comparative example washed with water after the charcoal obtained by carbonizing the wood chip 5 at 700 ° C. was immersed in a 1 mol / L FeCl ₃ solution,
(3) After immersing the charcoal obtained by carbonizing the wood chip 5 at 700 ° C. in a 5 mol / L HCl solution, 200 mg of acid-treated charcoal 9S washed with water,
(4) 200 mg of Ca-introduced acid-treated charcoal 21S obtained by immersing the wood chip 5 in 5% by weight lime water 18 and then carbonizing it at 700 ° C. in a 5 mol / L HCl solution,
(5) Five samples of 200 mg of an anion exchange resin used in the comparative example were put in the corresponding standard solutions, respectively, shaken for 10 hours under the conditions of, for example, 200 rpm and 20 ° C., and then in a nitric acid solution and a nitrous acid solution. The concentration of nitrate nitrogen and the concentration of nitrite nitrogen were measured, and the amount of adsorption was calculated.

〔result〕
FIG. 9 shows a comparison of the nitrate nitrogen and nitrite nitrogen adsorption capacities of the above samples.
The charcoal 9 carbonized at 700 ° C. of (1) hardly adsorbs nitrate nitrogen and nitrite nitrogen, whereas the iron chloride charcoal of (2) absorbs nitrate nitrogen and nitrite nitrogen respectively. Adsorbed at 75 mg / g and 2.35 mg / g. The acid-treated charcoal 9S (3) adsorbed 2.50 mg / g and 2.20 mg / g of nitrate nitrogen and nitrite nitrogen, respectively. The anion exchange resin (5) adsorbed nitrate nitrogen and nitrite nitrogen at 10.80 mg / g and 10.00 mg / g, respectively. On the other hand, the Ca-introduced acid-treated charcoal 21S of (4) obtained by immersing the wood chip 5 in the lime water 18 and then carbonizing and subsequently immersing it in the HCl solution is 10. It adsorbed 75 mg / g and 9.80 mg / g, and showed an adsorption capacity equivalent to or better than the anion exchange resin of (5).

  The mechanism by which the Ca-introduced acid-treated charcoal 21S adsorbs nitrate ions, for example, is considered as follows. As shown in FIG. 14 (A), when Ca-introduced acid-treated charcoal 21S is dipped in nitric acid solution 35, chlorides bonded to the functional groups on the surface of Ca-introduced acid-treated charcoal 21S via calcium ions or directly to the functional groups. The ions (see (B) in the figure) and the nitrate ions in the nitric acid solution 35 are exchanged (see (C) in the figure), and the nitrate ions are adsorbed on the Ca-introduced acid-treated charcoal 21S (see (D) in the figure). . FIG. 5E shows a change when the Ca-introduced acid-treated charcoal 21S shown in FIG. 4D is immersed in a concentrated KCl (or NaCl) solution, for example. That is, the adsorbed nitrate ions can be regenerated by exchanging chloride ions and nitrate ions again with a KCl (or NaCl) solution. Hereinafter, this reproduction will be described.

《Regeneration test》
〔Test method〕
A sample of acid-treated charcoal 9S or Ca-introduced acid-treated charcoal 21S after the nitrate nitrogen adsorption test was washed with a 1 mol / L KCl (or NaCl) solution, and further washed with water. Subsequently, the standard solution was changed to prepare 50 mL of a nitric acid solution having a nitrate nitrogen concentration of 50 mg / L, and a first regeneration test of 200 mg of the sample washed with water was performed. That is, the sample is put in a nitric acid solution, shaken for 10 hours under conditions of, for example, 200 rpm and 20 ° C., then the concentration of nitrate nitrogen in the nitric acid solution is measured, and the first regeneration test for calculating the adsorption amount is performed. This was performed using the sample.

  Next, the sample used in the first regeneration test was washed with a 1 mol / L KCl (or NaCl) solution and further washed with water. Subsequently, the standard solution was replaced to prepare 50 mL of a nitric acid solution having a nitrate nitrogen concentration of 50 mg / L, and a regeneration test of the washed 200 mg of the sample was performed. That is, the sample is put in 50 mL of a nitric acid solution, shaken for 10 hours, for example, under conditions of 200 rpm and 20 ° C., then the concentration of nitrate nitrogen in the nitric acid solution is measured and the amount of adsorption is calculated. The test was performed using the sample. This process was repeated two more times.

〔result〕
Amount of nitrate nitrogen adsorbed by acid-treated charcoal 9S First time: 2.5 mg / g
The first reproduction ... 2.5mg / g
Second playback: 2.4 mg / g
3rd regeneration ... 2.5mg / g
Adsorption amount of nitrate nitrogen by Ca-introduced acid-treated charcoal 21S, first time ... 10.8mg / g
The first reproduction ... 10.6mg / g
Second playback: 10.9mg / g
3rd regeneration ... 10.7mg / g

From the above, it was found that the acid-treated charcoal 9S and the Ca-introduced acid-treated charcoal 21S used were regenerated by washing with a concentrated KCl (or NaCl) solution and further with water. That is, the acid-treated charcoal 9S and the Ca-introduced acid-treated charcoal 21S adsorbing nitrate nitrogen (anions) in the nitrate nitrogen adsorption test were each washed with a KCl (or NaCl) solution, and further washed with water, so Nitrate nitrogen (anion) adsorbed in the nitrogen adsorption test is removed, and Cl ⁻ is combined in place of the removed nitrate nitrogen (anion), whereby acid-treated charcoal 9S and Ca-introduced acid-treated charcoal 21S. Was found to be regenerated. That is, it was confirmed that the acid-treated charcoal 9S and the Ca-introduced acid-treated charcoal 21S that have been used once can be used a plurality of times by performing washing and washing each time after use. Even when nitrite nitrogen is adsorbed, the principle of regeneration is the same even if acid-treated charcoal 9S and Ca-introduced acid-treated charcoal 21S are used as anion adsorbing carbon materials, respectively.

[Fluorine adsorption performance]
〔Test method〕
Prepare 50 mL (standard solution) of a solution having a fluoride ion concentration of 50 mg / L,
(1) 100 mg of charcoal 9S used in a comparative example in which the wood chip 5 is carbonized at 700 ° C.
(2) Iron chloride charcoal 100 mg used in the comparative example washed with water after the charcoal obtained by carbonizing the wood chip 5 at 700 ° C. was immersed in a 1 mol / L FeCl ₃ solution,
(3) After immersing charcoal obtained by carbonizing the wood chip 5 at 700 ° C. in a 5 mol / L HCl solution, 100 mg of acid-treated charcoal 9S washed with water,
(4) 100 mg of Ca-introduced acid-treated charcoal 21S obtained by immersing the wood chip 5 in 5% by weight of lime water and carbonized at 700 ° C. in a 5 mol / L HCl solution,
(5) Five samples of 100 mg of the anion exchange resin used in the comparative example are placed in the corresponding standard solutions, and after shaking for 10 hours under the conditions of, for example, 200 rpm and 20 ° C., the fluoride ion concentration in the solution Was measured, and the amount of adsorption was calculated.

〔result〕
FIG. 10 shows a comparison of fluoride ion adsorption capacities of the above samples.
The 700 ° C. charcoal (1) hardly adsorbs fluoride ions, whereas the iron chloride charcoal (2) adsorbs 7.50 mg / g fluoride ions. Moreover, the acid-treated charcoal 9S of (3) adsorbed 5.00 mg / g fluoride ions. The anion exchange resin of (5) adsorbed 8.50 mg / g fluoride ion. On the other hand, the Ca-introduced acid-treated charcoal 21S of (4) obtained by immersing the wood chip 5 in lime water and then carbonizing and subsequently immersing it in the HCl solution adsorbs 19.00 mg / g fluoride ions, The adsorption capacity greatly exceeded the anion exchange resin of (5).

《Regeneration test》
〔Test method〕
Next, a sample of acid-treated charcoal 9S or Ca-introduced acid-treated charcoal 21S after the fluorine adsorption test was washed with 1 mol / L hydrochloric acid (or sulfuric acid), and further washed with water. Subsequently, the standard solution was changed to prepare 50 mL of a solution having a fluoride ion concentration of 50 mg / L, and a first regeneration test of the washed 200 mg of the sample was performed. That is, the sample is put into the solution and shaken for 10 hours under the conditions of, for example, 200 rpm and 20 ° C., then the fluoride ion concentration in the solution is measured and the first regeneration test for calculating the adsorption amount is performed. A sample was used.

  Next, the sample used in the first regeneration test was washed with 1 mol / L hydrochloric acid (or sulfuric acid) and further washed with water. Subsequently, the standard solution was exchanged to prepare 50 mL of the solution having a fluoride ion concentration of 50 mg / L, and a regeneration test of the washed 200 mg of the sample was performed. That is, the second regeneration test in which the sample is placed in 50 mL of the solution and shaken for 10 hours under the conditions of, for example, 200 rpm and 20 ° C., and then the fluoride ion concentration in the solution is measured and the adsorption amount is calculated. Was performed using the sample. This process was repeated two more times.

〔result〕
Adsorption amount of fluoride ion by acid-treated charcoal 9S First time ... 2.5mg / g
The first reproduction ... 2.5mg / g
Second playback: 2.4 mg / g
3rd regeneration ... 2.5mg / g
Adsorption amount of fluoride ion by Ca-introduced acid-treated charcoal 21S First time… 18.7 mg / g
The first reproduction ... 18.2mg / g
Second playback: 18.9 mg / g
3rd regeneration ... 18.6mg / g

From the above, it was found that the acid-treated charcoal 9S and the Ca-introduced acid-treated charcoal 21S used were regenerated by washing with concentrated hydrochloric acid (or sulfuric acid) and washing with water. That is, the acid-treated charcoal 9S and Ca-introduced acid-treated charcoal 21S adsorbing fluoride ions (anions) in the fluorine adsorption test are washed with hydrochloric acid (or sulfuric acid) and then washed with water, respectively. and fluoride ions (anions) are removed, Cl instead removed fluoride ions (anions) - ^(or SO ₄ ^2-) by coupling, acid treatment charcoal 9S and Ca introducing acid treatment It was found that charcoal 21S (anion adsorbing carbon material) was regenerated. That is, it was confirmed that the acid-treated charcoal 9S and the Ca-introduced acid-treated charcoal 21S that have been used once can be used a plurality of times by performing washing and washing each time after use.

  As described above, the purification material 1 of the present invention is excellent in the adsorption performance of anions such as nitrate nitrogen, nitrite nitrogen and fluorine. Further, the adsorbed anion is removed from the used purification material 1 (1a, 1b) that adsorbs the anion to be adsorbed, and an anion capable of ion exchange with the next anion to be adsorbed. The purification material 1 (1a, 1b) can be regenerated by combining with the removed anions, and the regenerated purification material 1 (1a, 1b) can be used repeatedly. An example in which such a purification material 1 is applied to an actual wastewater treatment apparatus such as a purification apparatus for treating wastewater formed in the middle of a wastewater distribution pipe will be described below.

  15 and 16 show a third embodiment of the present invention. FIG. 15 schematically shows an example of the waste water treatment apparatus 40.

  In FIG. 15, reference numeral 41 denotes, for example, a semiconductor factory, an oil refining factory, various chemical factories such as pharmaceuticals, agricultural chemicals, and functional chemicals, a steel / steel manufacturing factory, a metal refining factory, a paper mill, a textile factory, a plant factory, and a food factory. Waste water flow paths such as domestic waste water in each household / merged septic tanks / village units, 42 is a bottomed cylindrical adsorption tower (hereinafter referred to as a bottomed cylindrical adsorption tower configured to be able to introduce waste water flowing through the waste water flow path 41) , 43 is a mesh plate constituting the bottom of the suction portion 42. The adsorbing portion 42 accommodates the chip-shaped purification material 1 shown in FIG. 1 and the pellet-shaped purification material 1a shown in FIG. 2 or FIG.

  In the present embodiment, the waste water channel 41 is connected to the upstream channel 41 a for supplying waste water to the upper end of the adsorbing unit 42 and the lower end of the adsorbing unit 42, and the waste water flowing in the adsorbing unit 42 is purified by the purification material 1 ( And a downstream channel 41b that is discharged as sewage after being purified by 1a). The adsorbing portion 42 and the mesh plate 43 are made of a chemically stable material such as plastic or stainless steel that is not easily corroded by chemical substances or eluting any components, and the mesh of the mesh plate 43 has a chip shape. The purification material 1a has such a fine degree that it does not easily escape to the outside. That is, in the waste water treatment apparatus 40 of this example, the adsorption | suction part 42 which is a tank (drain waste water tank) which stores waste waste water between the waste waste water flow paths 41a and 41b is provided, and the purification material 1 ( An example is shown in which wastewater is purified by accommodating 1a).

  44 is a bottomed tubular regeneration tower (hereinafter referred to as a regeneration section) configured to accommodate the regeneration liquid 45, 46 is a discharge flow path configured to be capable of discharging the regeneration liquid 45 in the regeneration section 44, 47 A communication channel 48 that communicates and connects the lower portion of the adsorption unit 42 and the regeneration unit 44, and an open / close valve 48 is provided in the communication channel 47. Then, when the purification material 1 (1a) accommodated in the adsorbing part 42 sufficiently adsorbs the anion and its adsorbing capacity is lowered, the opening / closing valve 48 is opened to flow into the regenerating part that has been emptied in advance. Let That is, the waste water treatment apparatus 40 of the present embodiment includes a purification material take-out mechanism 49 including a discharge channel 46 and an opening / closing valve 48 for moving the purification material 1 (1a) in the adsorption unit 42 to the regeneration unit 45. ing. Note that the purification material 1 (1a) to be flowed to the regenerating unit 44 using the purification material take-out mechanism 49 is appropriately determined as to whether the purification material 1 (1a) accommodated in the adsorption unit 42 is the entire amount or a part thereof. be able to.

  For example, potassium chloride (KCl) can be used as the regenerating liquid 45 when the adsorption target by the purification material 1 (1a) is nitrate ions. Further, when the adsorption target by the purification material 1 (1a) is fluorine, hydrochloric acid (HCl) or the like is used as the regenerating liquid 45. That is, the regenerating liquid 45 stored in the regenerating part 44 is appropriately selected according to the adsorption target. Then, the purification material 1 (1a) that has been completely regenerated can be washed with water as necessary and returned to the adsorbing portion 42.

On the other hand, the regenerated liquid 45 after the regeneration process is recovered by opening the lower valve 46a provided in the discharge channel 46, and this is separately processed. The treatment of the regenerated liquid 45 after use is carried out by reacting with calcium carbonate (CaCO ₃ ) to form calcium fluoride (CaF ₂ ) when the object to be adsorbed by the purification material 1 (1a) is fluorine, and using a sedimentation tank, CaF. ₂ ) Precipitate is removed and disposed. Fluoride ions that could not be removed in the sedimentation tank are adsorbed by another purification material 1 (1a), and can be disposed as calcium fluoride by burning the purification material 1 (1a) without regenerating it. it can. Naturally, when the purification material 1 (1a) having adsorbed fluorine is moved from the adsorption unit 42 to the regeneration unit 45, the purification material 1 (1a) is taken out without being regenerated, incinerated, and disposed as calcium fluoride. You can also When the adsorption target is fluorine, it is desirable that a sedimentation tank is placed in front of the adsorption unit 42 and calcium carbonate is added in the sedimentation tank in advance to cause a reaction, so that most fluoride ions are precipitated and removed as calcium fluoride. Fluoride ions that cannot be removed in the sedimentation tank are adsorbed by the adsorbing portion 42, and waste water that satisfies the fluorine emission standard can be discharged.

  FIG. 16 is a view for explaining a processing method of the regenerating liquid 45. As shown in FIG. 16, when the adsorption target by the purification material 1 (1a) is nitrate ions, the used regenerated liquid 45 can be decomposed and disposed of by electrolysis.

In FIG. 16, 50 is a decomposition treatment tank configured to be able to contain the regenerating solution 45, 51 is an anode accommodated in the decomposition treatment tank 50, 52 is a cathode, 53 is power necessary for decomposition in both electrodes 51 and 52. It is a power supply to supply. That is, the spent regeneration solution 45 is accommodated in the decomposition treatment tank 50, and a voltage is applied between the electrodes 51 and 52, whereby chloride ions (Cl ⁻ ) in the vicinity of the anode 51 have a high oxidative power. ClO ^- converted to) nitrate in the vicinity of the cathode 52 (NO ₃ ^-) is reduced to ammonia (NH _3), then, hypochlorite (ClO generated at the anode ^-) with ammonia and a cathode in the regenerated liquid 45 Ammonia (NH ₃ ) generated in 52 reacts and is converted into harmless nitrogen gas (N ₂ ).

  FIG. 17 schematically shows an example of the waste water treatment apparatus 60 according to the fourth embodiment of the present invention.

  In FIG. 17, reference numeral 61 denotes, for example, a semiconductor factory, an oil refining factory, various chemical factories such as pharmaceuticals, agricultural chemicals, and functional chemicals, a steel / steel manufacturing factory, a metal refining factory, a paper mill, a textile factory, a plant factory, and a food factory. , Wastewater flow paths for domestic wastewater, etc. in each household / merged septic tank / village unit, 62 is a pipe (hereinafter referred to as an adsorbing part) formed in a horizontal cross section that communicates with the wastewater flow path 61, 63 A regenerating unit having two liquid reservoirs 63a and 63b arranged adjacent to the adsorbing unit 62, 64 and 65 are discharge channels provided at the lower ends of the respective liquid reservoirs 63a and 63b, and 66 is an adsorbing unit 62. A plurality of rollers arranged inside, 67 is a pair of rollers arranged at a position separating the inside and outside of the adsorption unit 62, and 68 is a plurality of rollers arranged at various locations in the reproducing unit 63.

  Then, the waste water treatment purification body 30 is rotated by rotating the rollers 66 to 68 in one direction while the belt-like waste water treatment purification body 30 described with reference to FIG. The purifying material 1 (1a, 1b) contained in is circulated in a switchable manner between the state accommodated in the adsorbing part 62 and the state accommodated in the regenerating part 63. That is, the purification material take-out mechanism in the present embodiment is each of the rollers 66-68.

  Further, in the waste water treatment apparatus 60 of the present embodiment, water and KCl solutions are accommodated in the liquid reservoirs 63a and 63b, respectively, and nitrate ions adsorbed by the waste water treatment purifier 30 in the adsorption part 62 are collected. A series of operations of regenerating with KCl, washing with water and returning to the adsorption unit 62 again can be performed continuously. In addition, when the adsorption target by the purification material 1 (1a, 1b) is fluorine, HCl is accommodated in the liquid reservoir 63b.

  FIG. 18 schematically shows an example of the waste water treatment apparatus 70 according to the fifth embodiment of the present invention. In FIG. 18 (A), for example, 71 is a wastewater flow path for domestic wastewater, etc. in each household, a combined septic tank, and a village unit, and 72 is between an upstream wastewater flow path 71a and a downstream wastewater flow path 71b. Disposed waste water reservoirs (hereinafter referred to as adsorption units) 73 are floats attached to the waste water treatment purifier 26 shown in FIG. By configuring as in the present embodiment, all of the purifying material 1a in the net 25 is positioned below and in contact with the surface of the waste water.

  The waste water treatment purifier 26 can be installed in various forms. For example, as shown in FIG. 18B, a support member 74 may be erected in the waste water reservoir 72, and the waste water treatment purifier 26 may be fixed horizontally to the support member 74. Furthermore, although not shown in the drawings, the size of the waste wastewater treatment purification body 26 may be formed large enough to occupy the entire interior of the wastewater drainage reservoir 72. In any case, the waste water reservoir 72 constitutes a waste water tank formed between the waste water channels 71a and 71b, and functions as a processing unit that accommodates the purification material 1 (1a). Waste water can be purified.

  In addition, as shown in FIG. 19, the waste water treatment purifier 26 may be inserted and installed in the waste water channel 71. In this case, it is preferable that the waste water treatment purifier 26 is fixed so as not to easily move in the waste water channel 71. In this case, the waste water channel 71 functions as a processing unit that contains the purification material 1 (1a) to purify the waste water.

  FIG. 20 shows another modification of the waste water treatment apparatus 70 of the present invention. A waste water treatment apparatus 75 shown in FIG. 20 puts a large number of chip-shaped purification materials 1 shown in FIG. 1 into a waste water reservoir 72 that communicates with the waste water flow channel 71, and migrates this by a water flow. Also good. In this case, it is necessary to provide a net 76 for preventing the purifying material 1 from flowing out at the outlet to the waste water channel 71 on the downstream side of the waste water reservoir 72.

  Further, as shown in FIG. 21, a plurality of pellet-shaped purification materials 1a shown in FIG. 3 or FIG. 5 are contained in a bag 77 made of a water-permeable nonwoven fabric through which waste water 36 can be passed for comparison. As shown in FIG. 20, the waste water treatment purification body 78 may be put into the waste waste water reservoir 72. In FIG. 21, reference numeral 79 denotes the waste waste water treatment purification body 78. In order to prevent the outflow, it is a net provided at the outlet to the waste water channel 71 on the downstream side of the waste water reservoir 72.

  Then, as shown in FIG. 22, the sheet-shaped wastewater treatment purification body 30 shown in FIG. 8 is laminated in an appropriate case 79 to form a wastewater treatment purification body 80. You may make it provide in the exit to the waste water flow path 71 of the downstream in the waste water reservoir 72. FIG. That is, also in the present embodiment shown in FIGS. 20 to 22, the waste water reservoir 72 constitutes a waste water tank formed between the waste water channels 71 a and 71 b, and the waste water tank 72 is the purification material 1. It functions as a processing unit that accommodates (1a, 1b) and purifies waste water.

  In addition, although the wastewater treatment apparatus 70 shown in FIGS. 18-22 has shown the example arrange | positioned in the wastewater drainage flow paths 71, such as domestic wastewater in each household, a combined septic tank, and a village unit, this same structure is shown, for example in a semiconductor Wastewater flow channels for wastewater from factories, oil refineries, various chemical factories such as pharmaceuticals, agricultural chemicals, and functional chemicals, steel and steel manufacturing factories, metal refining factories, paper mills, textile factories, plant factories, and food factories Needless to say, it can also be provided.

  In the second embodiment described above, the material plant 5 that has been subjected to calcium introduction treatment is used, but the material plant 5 that has been subjected to metal chloride introduction treatment may be used. Hereinafter, this will be described as a sixth embodiment with reference to FIGS. 23 and 24. FIG.

First, FIG. 23 schematically shows still another example of an apparatus for producing the purification material 1. In this figure, the same reference numerals as those shown in FIG. 4 are the same. Then, as shown in FIG. 23, the wood chip 5 is sent to a treatment tank 92 containing a metal chloride solution (CaCl ₂ solution in this embodiment) 91 having an appropriate concentration. Metal chloride (in this embodiment, CaCl ₂ ) is introduced into the chip 5 to form a metal chloride introduction chip 93. Reference numeral 94 denotes a stirring blade provided in the processing tank 92, which is rotationally driven by a motor (not shown), and is used when stirring the liquid or the like in the processing tank 92. Here, in order to improve the anion adsorption ability, it is preferable to add Ca (OH) ₂ slightly to the metal chloride solution.

  The metal chloride introduction chip 93 obtained as described above is dried by the dryer 20 and then sent to the carbonization furnace 6 to be carbonized. In addition, the said dryer 20 is comprised so that the waste heat discharged | emitted from the carbonization processing furnace 6 may be utilized for the said drying process.

  The metal chloride introduction chip 93 is supplied into the carbonization furnace main body 8 through the introduction portion 8a, and is carbonized by heating at an appropriate temperature (described later) and an appropriate time (described later). It is discharged out of the main body 8 from the discharge portion 8b.

  Thereafter, the purification material 1 is sent to a treatment tank 97 containing water or an HCl solution (hydrochloric acid) 96, and the contact (immersion) treatment of the purification material 1 with respect to the water or the HCl solution 96 is performed in the treatment tank 97. . Reference numeral 98 denotes a stirring blade provided in the processing tank 97, which is rotationally driven by a motor (not shown) and is used when stirring the liquid or the like in the processing tank 97. After the contact treatment with the acid, the contact treatment with water may be performed, and vice versa.

  Subsequently, the purification material 1 is sent to a dryer 14 and dried, and then formed into granules (pellets) 1a having a proper diameter or finer powder 1b. In addition, the said dryer 14 is comprised so that the waste heat discharged | emitted from the carbonization processing furnace 6 may be utilized for the said drying process.

  Next, an example of a procedure for obtaining the purification material 1 from the raw material plant 5 using the apparatus shown in FIG. 23 will be described in detail with reference to FIG. 23 and FIG. First, a wood chip 5 in which conifers such as straw and cedar are chipped to an appropriate size of 10 mm or less is prepared (step T1).

Subsequently, the wood chip 5 is immersed in a CaCl ₂ solution 91 adjusted to 1 to 20% by weight in the treatment tank 92 for 3 hours or more, for example. It is preferable to rotate the stirring blade 94 during the immersion of the wood chip 5. As a result, the CaCl ₂ solution 91 can permeate into the wood chip 5, and a metal chloride introduction chip 93 in which Ca ions and Cl ions are introduced into the wood chip 5 is obtained (step T2).

  Then, the metal chloride introduction chip 93 is sent to the dryer 20 to be dried (step T3).

  Thereafter, the metal chloride introduction chip 93 is supplied to the carbonization furnace body 8 of the carbonization furnace 6 and heated and carbonized for about 1 hour in a temperature range of 400 ° C. to 1000 ° C. (700 ° C. in this embodiment). (Step T4). Thereby, the purification material 1 is obtained.

The said purification material 1 is supplied to the processing tank 97, and is immersed in the HCl solution 96 adjusted to 0.01 mol / L-11 mol / L (for example, 5 mol / L) in the processing tank 97 (step T5). In this case, it is preferable to rotate the stirring blade 98, whereby it is possible to remove excess metal chloride (CaCl ₂ ) crystals remaining in the purification material 1 and to further add chloride ions. The desired purification material 1 can be obtained.

  And the purification | cleaning material 1 after the said immersion process is generally dried in the dryer 14 (step T6). In this case, the purification material 1 may be sent to the dryer 14 as it is, but may be neutralized by immersing it in an appropriate alkaline solution, or may be washed with water after the neutralization. In addition, when using the purification material 1 in a wet state, a drying process may not be performed.

  And although the purification material 1 after the said drying process can also be used with a chip shape, in this Example, the particle | grain (pellet) 1a of an appropriate diameter and finer powder 1b using an appropriate processing machine. (Step T7).

  In addition, the said purification material 1 is not restricted to what is manufactured by performing all from the said step T1 to step T7 in the same factory. For example, when it is manufactured up to a certain step among the steps T1 to T7 in other factories or the like, the purification material 1 may be manufactured starting from an intermediate step.

In the sixth embodiment, as the metal chloride, CaCl _{2 from} which the highest-performance anion-adsorbing carbon material is obtained is exemplified, but BaCl ₂ , MnCl ₂ or the like may be used.

  Further, in the sixth embodiment, the contact treatment with the HCl solution 96 of the purification material 1 is performed in the treatment tank 97, but water may be used instead of the HCl solution 96. In this case, addition of chloride ions is not performed, and only the excess metal chloride crystals remaining in the purification material 1 are removed.

  Furthermore, in the above embodiment, the metal chloride introduction chip 93 is carbonized in the carbonization furnace 6 to obtain the purification material 1 and then sent to the treatment tank 97, but not sent to the treatment tank 97. May be. In this case, since it is not necessary to send the purification material 1 to the dryer 14, the manufacturing method of the purification material 1 is one in which the steps T5 and T6 are omitted. Moreover, in this case, as a manufacturing method of the purification material 1, you may complete | finish by step T1-T4, and you may perform step T7 after that.

  Next, a test conducted for examining the adsorption performance of nitrate nitrogen and nitrite nitrogen of the purification material 1 of the sixth embodiment will be described. The test method and test results for the adsorption performance of nitrate nitrogen and nitrite nitrogen will be described as follows.

First, two sets of 200 mg each were prepared for a total of seven samples (1) to (7) shown below. That is,
(1) Charcoal obtained by heating and carbonizing the wood chip 5 at 700 ° C. for 1 hour (2) Heating and carbonizing the wood chip 5 at 700 ° C. for 1 hour, and then immersing it in a 1 mol / L FeCl ₃ solution. Iron chloride charcoal obtained by washing with water (3) Anion exchange resin (4) BaCl ₂ charcoal obtained by dipping the wood chip 5 in a 10% by weight BaCl ₂ solution, followed by heating at 700 ° C. for 1 hour for carbonization (5) The wood chip 5 is immersed in a 10 wt% BaCl ₂ solution, heated at 700 ° C. for 1 hour to be carbonized, and then immersed in a 5 mol / L HCl solution to obtain an HCl-treated BaCl ₂ charcoal ( 6) CaCl ₂ charcoal obtained by dipping the wood chip 5 in a 10 wt% CaCl ₂ solution and then carbonizing by heating at 700 ° C. for 1 hour. (7) The wood chip 5 was dipped in a 10 wt% CaCl ₂ solution. After 1 hour at 700 ° C Two sets of a total of seven samples of HCl-treated CaCl ₂ charcoal obtained by heating and carbonizing and then dipping in a 5 mol / L HCl solution were prepared. The samples (4) to (7) correspond to the purification material 1, and the samples (1) to (3) are for comparison with the purification material 1.

  Then, each sample of one set is individually put into 50 mL (first standard solution) of a nitrate nitrogen solution having a nitrate nitrogen concentration of 50 mg / L (50 ppm), and each sample of the other set is The nitrite nitrogen concentration was individually added to 50 mL (second standard solution) of nitrite nitrogen solution having a concentration of 50 mg / L (50 ppm). Then, after shaking for 10 hours under the conditions of 200 rpm and 20 ° C., the concentration of nitrate nitrogen in the first standard solution and the concentration of nitrite nitrogen in the second standard solution were measured, respectively. The amount of adsorbed nitrogen and nitrite nitrogen was calculated.

FIG. 29 shows a comparison result of nitrate nitrogen adsorption ability and nitrite nitrogen adsorption ability of each sample obtained by the above test. In this figure, the amount of nitrate nitrogen and nitrite nitrogen adsorption of each sample is shown as a pair of bar graphs. The left bar graph shows the nitrate nitrogen adsorption amount, and the right bar graph shows the nitrite nitrogen adsorption amount. ing. From the results shown in this figure, it can be seen that all the samples of the present invention have high nitrate nitrogen adsorption ability and nitrite nitrogen adsorption ability. Further, the adsorption amounts of nitrate nitrogen and nitrite nitrogen of (4) BaCl ₂ charcoal and (5) HCl-treated BaCl ₂ charcoal were compared, and (6) CaCl ₂ charcoal and (7) HCl adsorbed. In order to further enhance the nitrate nitrogen / nitrite nitrogen adsorption capacity of the purification material 1 by comparing the adsorption amounts of nitrate nitrogen and nitrite nitrogen of the treated CaCl ₂ charcoal, the purification material 1 is added to the HCl solution. It can be seen that it is better to perform a dipping treatment (HCl treatment). However, the purification material 1 having sufficiently high nitrate nitrogen / nitrite nitrogen adsorption ability can be obtained without performing the HCl treatment. In this case, the cost is low because the contact treatment of the HCl solution is not performed. The purification material 1 can be manufactured.

Here, the purification material 1 adsorbs, for example, nitrate ions when the purification material (CaCl ₂ charcoal) 1 is immersed in a nitric acid solution 99 as shown in FIG. Cl ions (see (B) in the same figure) directly bonded to the group via Ca ions or NO ₃ ions in the nitric acid solution 99 are exchanged (see (C) in the same figure), and the NO ₃ ions are converted into the purification material 1. It is thought that this is because it is adsorbed on the surface (see FIG. 4D).

FIG. 28E shows a purification material 1 that has adsorbed NO ₃ ions and has reached the state shown in FIG. 28D. A high-concentration chloride solution (for example, a metal chloride solution of KCl or NaCl, or The state after being immersed in HCl solution) is shown. That is, the NO ₃ ions adsorbed on the purification material 1 are exchanged with Cl ions by the chloride solution, whereby the purification material 1 is regenerated and becomes capable of adsorbing anions such as NO ₃ ions. That is, the purification material 1 of the sixth embodiment is not limited to a material that is always newly obtained by the above production method, but is obtained by the production method and is adsorbed from the purification material 1 that adsorbs anions (for example, NO ₃ ions). Anion (NO ₃ ion) is removed, and an anion (in this embodiment, Cl ion) capable of ion exchange with the next anion (for example, NO ₃ ion) to be adsorbed is removed. What was obtained by combining instead of (NO ₃ ion) (that is, regenerated) may be used. When sulfuric acid is used instead of the chloride solution, NO ₃ ions are ion-exchanged with SO ₄ ions instead of the Cl ions.

Next, the concentration of metal chloride solution (CaCl ₂ solution) 91 soaking the wood chips 5 in step T2 is described test conducted to examine the effect on the anion adsorbing ability of the purification material 1 after manufacturing . In the above test, the purification material 1 obtained by immersing the wood chip 5 in the CaCl ₂ solution 91, carbonizing by heating at 700 ° C. for 1 hour, and washing with water was used. The concentration of nitrate nitrogen was 50 mg / L (50 ppm). Was added to 50 mL (standard solution) of nitrate nitrogen solution, and the adsorption ability of nitrate nitrogen of the purification material 1 was examined. As the CaCl ₂ solution 61, the concentration was 1% by weight, 3% by weight, 5% by weight. %, 7%, 10%, 12%, 14%, 17% and 20% by weight were used. For comparison, adsorption of nitrate nitrogen of the purification material 1 obtained by immersing the wood chip 5 in a 10% by weight CaCl ₂ solution 91, carbonizing by heating at 700 ° C. for 1 hour, and treating with HCl. I also examined Noh. The results of the above test are shown in FIG.

As is clear from the results shown in FIG. 30, the anion adsorption capacity of the purification material 1 does not increase in proportion to the concentration of the CaCl ₂ solution. Most preferred. In addition, the results shown in FIG. 30 also show that the purification material 1 should be treated with HCl in order to further increase the anion adsorption capacity of the purification material 1.

  Next, the purification material 1 of the sixth example used for the adsorption of nitrate nitrogen was regenerated with a KCl (or NaCl) solution, and the regeneration performed to examine the nitrate nitrogen adsorption capacity of the regenerated purification material 1 The test will be described.

First, 200 mg of CaCl ₂ charcoal obtained by immersing the wood chip 5 in a 10 wt% CaCl ₂ solution and heating and carbonizing at 700 ° C. for 1 hour was prepared as the purification material 1. Then, this CaCl ₂ charcoal was put into 50 mL (standard solution) of a nitrate nitrogen solution having a nitrate nitrogen concentration of 50 mg / L (50 ppm), shaken at 200 rpm and 20 ° C. for 10 hours, The concentration of nitrate nitrogen in the standard solution was measured, and the amount of nitrate nitrogen adsorbed by the CaCl ₂ charcoal was calculated (first time).

Subsequently, the CaCl ₂ charcoal was washed with a 1 mol / L KCl (or NaCl) solution and further regenerated by washing with water. Thereafter, the regenerated CaCl ₂ charcoal is added to a newly prepared standard solution (that is, a nitrate nitrogen solution 50 mL having a nitrate nitrogen concentration of 50 mg / L) and shaken for 10 hours under the conditions of 200 rpm and 20 ° C. Thereafter, the concentration of nitrate nitrogen in the standard solution was measured, and the amount of nitrate nitrogen adsorbed by the CaCl ₂ charcoal was calculated. Then, the process from the reproduction of the CaCl ₂ charcoal up to the calculation of the amount of adsorbed nitrate nitrogen was carried out three times (reproducing first time - third time).

As a result of the regeneration test, that is, the adsorption amount of nitrate nitrogen by CaCl ₂ charcoal is
First time: 9.5mg / g
The first regeneration ... 9.0mg / g
Second regeneration: 9.1 mg / g
The third regeneration ... 8.8mg / g
Met. From the above, it was confirmed that the purification material 1 (CaCl ₂ charcoal) used for the adsorption of nitrate nitrogen was regenerated by washing with a concentrated KCl (or NaCl) solution and further with water. This is because the nitrate nitrogen is removed from the CaCl ₂ charcoal by washing the CaCl ₂ charcoal adsorbing the nitrate nitrogen with a KCl (or NaCl) solution and then washing with water. This is thought to be because Cl ^- is bonded to a functional group. Moreover, from the result of the regeneration test, the purification material 1 (CaCl ₂ charcoal) can be used multiple times for adsorption of nitrate nitrogen if it is regenerated by washing with KCl (or NaCl) solution and washing with water. It was also confirmed that it could be done. Even when the purification material 1 (CaCl ₂ charcoal) is used for adsorption of nitrite nitrogen, the principle of regeneration is the same.

Next, as the purification material 1 of the sixth embodiment, the wood chip 5 is immersed in a 10 wt% CaCl ₂ solution, heated at 700 ° C. for 1 hour to be carbonized, and then immersed in a 5 mol / L HCl solution. using HCl treatment CaCl ₂ charcoal was collected using, for the HCl process CaCl ₂ charcoal shows the results of similarly regeneration test as described above.

As a result of the regeneration test, that is, the adsorption amount of nitrate nitrogen by the HCl-treated CaCl ₂ charcoal,
First time ... 11.0mg / g
The first regeneration ... 11.0mg / g
Second regeneration: 10.8mg / g
The third regeneration ... 10.8mg / g
Met. From the above, purifying material 1 (HCl-treated CaCl ₂ charcoal) obtained by immersing in HCl solution after carbonization is also washed with concentrated KCl (or NaCl) solution after use for adsorption of nitrate nitrogen, Regeneration was confirmed by washing with water. Further, the nitrate nitrogen adsorption ability of the HCl-treated CaCl ₂ charcoal improved by the immersion treatment in the HCl solution is obtained by repeatedly regenerating the HCl-treated CaCl ₂ charcoal by washing with KCl (or NaCl) solution and washing with water. Has also been confirmed to remain (still improved).

  Next, a test conducted for examining the fluoride ion adsorption performance of the purification material 1 of the sixth embodiment will be described. First, in order to perform this test, 50 mg each of a total of seven samples (1) to (7) used in the above-described adsorption performance test for nitrate nitrogen and nitrite nitrogen were prepared. Each sample was individually added to 50 mL (standard solution) of a solution having a fluoride ion concentration of 50 mg / L (50 ppm), shaken at 200 rpm and 20 ° C. for 10 hours, and then subjected to the fluoride in the standard solution. The concentration of fluoride ion was measured, and the amount of fluoride ion adsorption by each sample was calculated.

FIG. 31 shows a comparison result of fluoride ion adsorption ability of each sample obtained by the above test. From the results shown in this figure, it can be seen that all the samples of the present invention have high fluoride ion adsorption ability. Furthermore, the adsorption amounts of fluoride ions of (4) BaCl ₂ charcoal and (5) HCl-treated BaCl ₂ charcoal were compared, and (6) CaCl ₂ charcoal and (7) HCl-treated CaCl ₂ charcoal were compared. By comparing the adsorption amount of fluoride ions, it is understood that it is better to perform a treatment (HCl treatment) in which the purification material 1 is immersed in an HCl solution in order to further enhance the fluoride ion adsorption ability of the purification material 1. . However, the purification material 1 having a sufficiently high fluoride ion adsorption ability can be obtained without performing the HCl treatment. In this case, the purification material 1 is produced at a low cost because the contact treatment of the HCl solution is not performed. can do.

  Next, a regeneration test performed to regenerate the purification material 1 used for adsorption of fluoride ions with hydrochloric acid (or sulfuric acid) and examine the fluoride ion adsorption ability of the regenerated purification material 1 will be described.

First, 200 mg of CaCl ₂ charcoal obtained by immersing the wood chip 5 in a 10 wt% CaCl ₂ solution and heating and carbonizing at 700 ° C. for 1 hour was prepared as the purification material 1. Then, this CaCl ₂ charcoal was put into 50 mL (standard solution) of a solution having a fluoride ion concentration of 50 mg / L (50 ppm), shaken at 200 rpm and 20 ° C. for 10 hours, and then in the standard solution. The concentration of fluoride ions was measured, and the amount of fluoride ions adsorbed by the CaCl ₂ charcoal was calculated (first time).

Subsequently, the CaCl ₂ charcoal was washed with 1 mol / L hydrochloric acid (or sulfuric acid) and further regenerated by washing with water. Thereafter, the regenerated CaCl ₂ charcoal was added to a newly prepared standard solution (that is, 50 mL of a solution having a fluoride ion concentration of 50 mg / L), shaken at 200 rpm and 20 ° C. for 10 hours, The concentration of fluoride ions in the standard solution was measured, and the adsorption amount of fluoride ions by the CaCl ₂ charcoal was calculated. Then, the processing up to the calculation of the adsorption amount of fluoride ions from the reproduction of the CaCl ₂ charcoal was carried out three times (reproducing first time - third time).

As a result of the regeneration test, that is, the adsorption amount of fluoride ions by CaCl ₂ charcoal,
First time ... 22.5mg / g
The first reproduction… 22.4mg / g
Second regeneration: 21.7 mg / g
The third regeneration ... 21.9mg / g
Met. From the above, it was confirmed that the purification material 1 (CaCl ₂ charcoal) used for the adsorption of fluoride ions was regenerated by washing with concentrated hydrochloric acid (or sulfuric acid) and further with water. This is because the fluoride ions are removed from the CaCl ₂ charcoal by washing the CaCl ₂ charcoal on which the fluoride ions have been adsorbed with hydrochloric acid (or sulfuric acid) and then washing with water, and instead of the removed fluoride ions, Cl ^- (Or SO ₄ ^2- ) is considered to be bonded to the functional group. Further, from the result of the regeneration test, the purification material 1 (CaCl ₂ charcoal) is used for adsorption of fluoride ions multiple times if it is regenerated by washing with hydrochloric acid (or sulfuric acid) and washing with water. It was also confirmed that it was possible.

Next, as the purification material 1 of the sixth embodiment, the wood chip 5 is immersed in a 10 wt% CaCl ₂ solution, heated at 700 ° C. for 1 hour to be carbonized, and then immersed in a 5 mol / L HCl solution. using HCl treatment CaCl ₂ charcoal was collected using, for the HCl process CaCl ₂ charcoal shows the results of similarly regeneration test as described above.

As a result of the regeneration test, that is, the adsorption amount of fluoride ions by the HCl-treated CaCl ₂ charcoal,
First time… 32.0mg / g
First reproduction: 31.5mg / g
Second regeneration: 31.4mg / g
The third regeneration ... 31.2mg / g
Met. From the above, purifying material 1 (HCl-treated CaCl ₂ charcoal) obtained by immersion treatment in HCl solution after carbonization is also used for adsorption of fluoride ions, then washed with hydrochloric acid (or sulfuric acid) solution, and further washed with water. By doing so, it was confirmed that it was reproduced. Further, the fluoride ion adsorption ability of the HCl-treated CaCl ₂ charcoal improved by the immersion treatment in the HCl solution can be obtained by repeatedly regenerating the HCl-treated CaCl ₂ charcoal by washing with hydrochloric acid (or sulfuric acid) and washing with water. It was confirmed that it persisted (it remained improved).

(A) is a figure which shows an example of the purification material for wastewater treatment of this invention, (B) is a figure which shows the example of a process of the purification material for wastewater treatment. It is a figure which shows roughly an example of the apparatus which manufactures the said purification material for waste water treatment. It is a figure which shows an example of the process of manufacturing the purification material for waste water treatment using the said manufacturing apparatus. It is a figure which shows roughly the other example of the apparatus which manufactures the said purification material for waste water treatment. It is a figure which shows an example of the process of manufacturing the purification material for waste water treatment using the said manufacturing apparatus. It is a figure which shows an example of the purification body for waste-water-treatment which used the said purification material for waste-water-treatment. It is a figure which shows the other example of the purification body for wastewater treatment. It is a figure which shows the further another example of the purification body for wastewater treatment. It is a figure which shows each adsorption amount in the adsorption test of nitrate nitrogen and nitrite nitrogen of the purification material for wastewater treatment of this invention. It is a figure which shows each adsorption amount in the adsorption test of the fluoride ion of the said purification material for wastewater treatment. It is a figure for demonstrating a lime water immersion process. It is a figure for demonstrating the carbonization process after the said lime water immersion process. It is a figure which shows the acid solution immersion process after the carbonization process. It is a figure for demonstrating the mechanism of nitrate ion adsorption | suction. It is a figure which shows roughly an example of the waste water treatment apparatus of this invention. It is a figure which shows the example of the processing apparatus relevant to the said waste water treatment apparatus. It is a figure for demonstrating the example according to waste water treatment apparatus. It is a figure for demonstrating another modification of a waste water treatment apparatus. It is a figure for demonstrating another modification of a waste water treatment apparatus. It is a figure for demonstrating another modification of a waste water treatment apparatus. It is a figure for demonstrating another modification of a waste water treatment apparatus. It is a figure for demonstrating another modification of a waste water treatment apparatus. It is explanatory drawing which shows roughly the structure of the apparatus which manufactures the purification material for waste-water-drain processing which concerns on 6th Example of this invention. It is a figure which shows an example of the process of manufacturing the said carbon material using the said manufacturing apparatus. (A)-(C) are the figures which show the detail of the process of step T2 in FIG. (A)-(C) are the figures which show the detail of the process of step T4 in FIG. (A)-(C) are the figures which show the detail of the process of step T5 in FIG. (A)-(D) is a figure which shows the detail of nitrate ion adsorption | suction in 6th Example, (E) is a figure which shows the carbon material after reproduction | regeneration. It is a graph which shows the comparison result of the adsorption amount of nitrate nitrogen and nitrite nitrogen of the purification material of 6th Example, and a comparison material. It is a graph showing the adsorption amount of nitrate nitrogen of the carbon material obtained by CaCl ₂ solution carbon materials and HCl treatment were prepared by varying the concentration of the step T2. It is a graph which shows the comparison result of the adsorption amount of the fluoride ion of the purification material of 6th Example, and a comparison material.

Explanation of symbols

1 (1a, 1b) Waste water treatment purification material 5 Raw material plant 9, 21 Carbide 9S, 21S Carbon material 12 Acid solution 40, 60, 70 Waste water treatment device 44, 63 Regeneration part 49, 66-68 Purification material take-out mechanism

Claims (13)

  A purification material for waste water treatment comprising a carbon material having an anion adsorption property by contacting an acid solution with a carbide obtained by carbonizing a raw material plant, or comprising the carbon material.   Waste water treatment characterized by comprising a carbon material having anion adsorption characteristics by contacting an acid solution with a carbide obtained by carbonizing a calcium-treated raw material plant, or containing the carbon material Purifying material.   The purification material for wastewater treatment according to claim 2, wherein the calcium introduction treatment is performed by bringing a solution containing calcium ions into contact with a raw material plant.   The purification material for wastewater treatment according to any one of claims 1 to 3, wherein the concentration of the acid solution is 0.01 mol / L or more.   A purification material for waste water treatment, comprising a carbon material in which a raw material plant into which a metal chloride has been introduced is carbonized so that the carbide has anion adsorption characteristics or contains the carbon material.   The purification material for waste water treatment according to claim 5, wherein the metal chloride bound in the carbide is contained in an amount of 2% to 25% as ash.   The purification material for wastewater treatment according to claim 5 or 6, wherein the carbide is in contact with water and / or acid. Discharging wastewater treatment for purification material according to any of claims 5-7 wherein the metal chloride is CaCl ₂ or BaCl _2.   The purification material for waste water treatment according to any one of claims 1 to 8, wherein the carbonization temperature of the raw material plant is 400 ° C to 1000 ° C.   The adsorbed anion is removed from the purification material for waste water treatment according to any one of claims 1 to 9, which adsorbs the anion to be adsorbed, and ion exchange with the next anion to be adsorbed is possible. A purification material for wastewater treatment, wherein anions are combined in place of the removed anions.   A method for purifying waste water, comprising purifying waste water using the purification material for waste water treatment according to any one of claims 1 to 10.   A wastewater treatment apparatus, wherein the wastewater treatment channel is provided with the purification material for wastewater treatment according to any one of claims 1 to 10 to purify wastewater.   The waste water treatment apparatus according to claim 12, further comprising: a regeneration unit for regenerating the adsorption capacity of the waste water treatment purification material; and a purification material take-out mechanism that moves the waste water treatment purification material to the regeneration unit.

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