JP2005296930A5 - - Google Patents

Description

Purifier for water purifier, water purification method using the same, and water purifier

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

  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.

  Therefore, when using rivers or groundwater as a water source, it is necessary to remove nitrate nitrogen components from the collected water. A method using denitrifying bacteria is also considered as the method, but in order to remove nitrate nitrogen by denitrifying bacteria, while maintaining anaerobic conditions, nitric acid in the presence of an organic substance such as methanol as a hydrogen donor. There is a problem that it is necessary to grow denitrifying bacteria while reducing nitrogen and to perform denitrification, and the operation is complicated, and maintenance and labor are troublesome and expensive. For this reason, removal of nitrate nitrogen components could only be done by installing large-scale facilities such as water purification plants.

  Patent document 1 has shown the water purifier which removes nitrate nitrogen from drinking water safely by combining an anion exchange resin and calcium carbonate. However, since this anion exchange resin is an expensive material and is a dedicated synthetic resin that acts only on specific anions, there is a problem that the manufacturing cost of the water purifier is increased.

  Also, rivers and groundwater may contain fluorine, and fluoride ions are harmful ionic species. It is necessary to discharge fluoride ions from the water.

  Therefore, it is possible to add a calcium compound to fluorine contained in water obtained from a water source and remove it as calcium fluoride. However, it is necessary to install an adsorption tower using activated alumina or an anion exchange resin for fluorine. Because of this, they needed large and expensive equipment and facilities. In particular, there is a problem that an expensive dedicated anion exchange resin is required.

  On the other hand, in order to remove fluorine from the collected water, an adsorbent is used as a method in which a metal hydrate is supported on a resin matrix, or a metal is adsorbed on an ion exchange resin, or cation exchange. A fluoride ion adsorbing material in which metal ions such as thorium, zirconium and titanium are adsorbed on a resin is considered. However, these adsorbents have a problem that the adsorption speed is slow.

As described above, an inexpensive material that adsorbs the anions including nitrate ions is not presently available, and can be manufactured at low cost, but easily and effectively from drinking water used for drinking water in each household. Therefore, an environmentally friendly water purifier that can remove anions was desired.
Japanese Patent Laid-Open No. 10-80682 Japanese Patent Laid-Open No. 10-165824

  By the way, charcoal is a typical porous carbon material together with activated carbon, and this charcoal is widely used as an extremely inexpensive humidity control material, river purification material, soil improvement material, etc. It is also used to remove gases and sulfur oxides. 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 water purifier purification material that is inexpensive, environmentally friendly and excellent in anion adsorption, a water purification method using the same, and water purification Is to provide a vessel.

The purification material for water purifier according to the first aspect of the present invention provides an anion adsorption property by combining an anion capable of ion exchange with an anion to be adsorbed by bringing an acid solution into contact with a carbide obtained by carbonizing a raw material plant. Or a carbon material containing the carbon material (claim 1).

Moreover, the purification material for water purifiers of the second invention combines an anion capable of ion exchange with an anion to be adsorbed by bringing an acid solution into contact with a carbide obtained by carbonizing a calcium-treated raw material plant. It is made of a carbon material having anion adsorption characteristics, or contains the carbon material (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).

  That is, as a result of examining the anion adsorption performance of the material obtained by bringing the acid solution into contact with the carbide, the present inventors have determined that the carbonization temperature for the raw material plant (raw material made of plants) such as natural fiber and woody material. Depending on the acid concentration, the inventors have found that the obtained material has excellent anion adsorption performance.

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, anion adsorption ability is expressed. The present inventors have found that. This is because an anion capable of ion exchange with the anion to be adsorbed is bonded to the functional group formed on the fine pore wall surface of the carbide. 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 solution containing calcium ions (desirably containing mainly calcium ions as a cation), 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. The present inventors have found that better anion adsorption properties can be obtained by treatment with an acid such as. In addition, as a method of bringing the 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.
Examples of the solution containing calcium 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. Are preferred.

The acid solution used for the contact treatment of the raw material plant after carbonization 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 water purifier 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. The acid solution preferably contains an anion that can exchange ions with the anion to be adsorbed, but the anion that can exchange ions with the anion to be adsorbed in the solution in contact with the plant material before carbonization. This is not the case when ions are included.

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, water purifier purifying material of the third invention, Ri by the carbonizing process the raw material plants by introducing treating metal chloride, bind anion and an ion-exchange capable chloride ions to be adsorbed to the carbide of their It is made of a carbon material having anion adsorption characteristics, or contains 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 the water purifier. 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 possible, it is most efficient to immerse the raw plant in the solution.

In water purifier purifying material of the third invention, the raw material plant is immersed in a solution containing CaCl ₂ as a metal chloride, a raw material to introduce processes and Ca ions and Cl ions, after which the CaCl ₂ introduction member The CaCl ₂ -introduced coal obtained by carbonization has excellent anion adsorption performance.

That is, for example, as shown in FIG. 18 (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. 19A, 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. 18 and 19 is immersed (contacted) in an acid such as hydrochloric acid 102 or sulfuric acid as shown in FIG. 20 (A). 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 purification material for water purifier 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 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.
In addition, when using a solution (for example, calcium chloride solution or calcium acetate solution) containing both an anion (for example, chloride ion) ion-exchangeable with the anion to be adsorbed and calcium ion, it is immersed in the solution as the raw material. In this case, it is desirable that the solution easily penetrates.

In the second invention, for example, before the carbonization treatment of the raw material plant, a solution containing calcium ions (for example, lime water or lime milk) is brought into contact with the raw material plant to introduce calcium into the raw material plant. Yes. 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 (for example, lime water) is used as the solution containing calcium ions, for example, when the wood chip 5 is immersed in the lime water 18 as shown in FIG. The water 18 can be brought into contact, and 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. 8C. This is presumably because the organic matter in the wood chip 5 is dissolved by alkali and Ca ions react with the components of the wood chip 5 as shown in FIG. 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. 9A, a Ca-introduced carbonized chip (Ca-introduced carbon) 21 as shown in FIG. 9C is obtained. 16 (see FIG. 9B) is decomposed by heat, and at the same time, Ca ions are precipitated on the surface of the fine pore wall of the Ca introduction chip 16 [see FIG. 9C]. In this case, since calcium ions are deposited on the surface of the fine pore wall of the Ca-introduced chip 16 (see FIG. 9B), a fine and highly dispersed state results in many functional groups at the corners of the fine pore wall. It is thought that it is drawn from people.

  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. After the treatment, by contacting the carbide with an acid solution, an anion capable of ion exchange with an anion to be adsorbed is directly or via a calcium ion on the functional group extracted from the microporous wall of the carbide, respectively. Combined.

  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 the second invention, as a raw material plant to be carbonized, for example, 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. 10 (A), when the HCl solution 12 is brought into contact with the Ca-introduced charcoal 21, as shown in FIGS. 10 (B) and (C), the surface of the fine pore wall of the Ca-introduced charcoal 21 is functionalized. (Cl ^-) chloride ions in the calcium ion and the functional group bonded to the base by bonding, as shown in FIG. 10 (D), the functional group Cl ^- is bonded or directly via calcium ions It is considered that the acid-treated Ca-introduced charcoal 21S is obtained. Moreover, although the said acid treatment should just 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 water purifier purification material having the above-described configuration has excellent anion adsorption performance. And this purification material for water purifiers does not cause any problem in the waste water treatment at the time of manufacture, and can be manufactured extremely environmentally and inexpensively. Further, in the present invention, the adsorbed anion is removed from the purifier for the water purifier adsorbing the anion to be adsorbed, and the anion capable of ion exchange with the next anion to be adsorbed is removed. By combining instead of (claim 10), the purifier for the water purifier can be repeatedly recycled. The anion that can be adsorbed by the water purifier purification material of the present invention is an anion that 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. Of course, it is an anion other than the anion previously bonded to the functional group on the surface of the fine pore wall of the carbide directly or via a calcium ion.

  According to a fourth aspect of the present invention, there is provided a water purification method for purifying water using the water purifier purification material according to any one of claims 1 to 10 (claim 11). The water purifier purification material can be processed into a granular form or a powder form. Therefore, for example, a granular water purifier purification material is stored in a mesh bag or mesh bag body having an appropriate mesh to form a water purifier purifying body, and the water purifier purifying body is in sufficient contact with clean water. By installing in a moist state, the anion contained in the tap water is reliably adsorbed. Moreover, when powdered, it is good also as a purifier for water purifiers by attaching this to a nonwoven fabric. Furthermore, it is good also as providing the purification | cleaning body for water purifiers by providing the flow-through prevention mesh in the water flow path, and accommodating the water purifier purification material in this water flow path.

  A water purifier according to a fifth aspect of the present invention is characterized in that the water purifier is provided with the water purifier purifying material according to any one of claims 1 to 10 to purify clean water (claim 12). ). Since this water purifier can be manufactured at a low cost, it is possible to reliably adsorb anions in clean water by installing it in each home.

  Conventionally used purification materials such as activated carbon may be used in combination with the purification material for the water purifier.

  Is the water purifier purifying material of the present invention made of a carbon material that has not only specific anions but also a desired anion adsorption performance, and a carbonized material obtained by carbonizing a raw material plant that has anion adsorption properties? Or the carbon material, it is environmentally friendly and can be manufactured at low cost.

  In the purifier for the water purifier, when the raw material plant is carbonized after the calcium introduction treatment, an anion adsorbing carbon material having an anion adsorption property equivalent to or superior to that of the anion exchange resin is used. Can be obtained.

  Moreover, the anion in clean water is reliably adsorb | sucked by the clean water purification method and water purifier which use the said purification material for water purifiers.

  1 to 3 show a first embodiment of the present invention. First, FIG. 1 (A) shows an example of the water purifier purifying material (hereinafter simply referred to as purifying material) 1 of the present invention, and in this embodiment, it is formed in a chip shape having a length of about 10 mm. . FIG. 1B 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, a sewage treatment purification body is obtained by accommodating a large number of the pellet-shaped purification materials 1a in a net made of a wire mesh (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-introduced chip 16 after the Ca-introducing treatment acid treatment 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). For example, a water purifier purifier is obtained by accommodating a large number of pellet-shaped purifiers 1a in a net made of a wire net (step S28).

  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. 6 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. 11 (A), when the Ca-introduced acid-treated charcoal 21S is dipped in the nitric acid solution 25, the chloride is bonded to the functional group on the surface of the Ca-introduced acid-treated charcoal 21S via calcium ions or directly. The product ions (see FIG. 11B) and the nitrate ions in the nitric acid solution 25 are exchanged (see FIG. 11C), and the nitrate ions are adsorbed to the Ca-introduced acid-treated charcoal 21S (see FIG. 11D). ). FIG. 11E shows a change when the Ca-introduced acid-treated charcoal 21S shown in FIG. 11D is dipped in, for example, a concentrated KCl (or NaCl) solution. 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. 7 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. The example which applied such a purification material 1 to the actual water purifier of the tap water formed in the middle of a water pipe, for example is demonstrated below.

  FIG. 12 is a cross-sectional view showing the configuration of the water purifier 30 of the third embodiment. In FIG. 12, 31 is a main body made of a substantially cylindrical bottomed cylinder, and 32 is removably screwed to the upper end of the main body 31. A lid body 33 to be connected and connected, 33 is a water supply port for the water guide W formed on the lower side surface of the main body 31, and 34 is a water outlet port protruding from the center of the lid body 32. Reference numeral 35 denotes two cylinders 35a and 35b arranged concentrically so as to be accommodated in the main body 31, and filters 35c and 35d which are positioned above and below the cylinders 35a and 35b and hold the mineral 36 inside. The container 37 is composed of a cylinder 37a made of a scientifically stable material such as plastic or stainless steel having an outer diameter substantially the same as or slightly smaller than the inner diameter of the container 35b, and first and second purification materials 38, for example. , 39 is a container comprising filters 37b to 37d that hold them in a separated state.

The mineral 36 includes, for example, calcium carbonate as a main component, thereby forming a mineral layer (hereinafter also referred to as a mineral layer 36). Therefore, as raw water (tap water) W such as tap water passes through the mineral layer 36 as shown by arrows F ₁ and F ₂ , calcium content beneficial to the human body is eluted in the top water W.

The first purification material 38 is obtained by forming the chip-shaped purification material 1 shown in FIG. 1 or the pellet-shaped purification material 1 shown in FIG. 2 or 4 into granules (pellets) 1a having an appropriate diameter. Thus, an anion removal layer (hereinafter also referred to as anion removal layer 38) is formed. That is, while the tap water W passes through the anion removal layer 38 as indicated by the arrow F ₃ , the tap water W contains anions such as nitrate ions, nitrite ions, fluoride ions and arsenic. Even if this is the case, it can be removed by adsorbing it to the purification material 38.

  The second purification material 39 is activated carbon, and a layer of this activated carbon (hereinafter also referred to as activated carbon layer 39) is formed downstream of the purification material 38. This activated carbon can remove residual chlorine that degrades the taste of water. That is, chloride ions and the like generated by ion exchange when nitrate ions and nitrite ions contained in the tap water W are adsorbed on the purification material 38 can be physically adsorbed and removed by the activated carbon layer 39.

  The filters 35c, 35d, 37b to 37d are made of a scientifically stable material such as plastic or stainless steel, and have a fine mesh that does not allow the contents 36, 38, 39 to escape to the outside. Use the body to hold the contents. In addition, a non-woven fabric having finer meshes is arranged on the filter 37b provided in the most downstream part, so that the purifier 1 (1a) and fine fragments of activated carbon can be captured by the filter 37b. Is desirable.

  Further, by removing the lid 32 from the main body 31, it is possible to take out the containers 35 and 37, respectively. If the mineral layer 36, the anion removal layer 38, and the activated carbon layer 39 are deteriorated, these can be easily removed. It is configured to be exchangeable. As already described in detail, the purification material 1 (1a) constituting the anion removing layer 38 can be recovered in the fluoride ion adsorption ability by being immersed in the HCl solution, and is thus immersed in the KCl solution. Thus, it is possible to recover the nitrate nitrogen adsorption ability, so that these can be recycled and used.

  The present invention is not limited to the detailed structure described above. That is, the purifying material 1 (1 a) may be accommodated in a net basket or a net bag without using the container 37, and this may be used as the anion removal layer 38. Furthermore, the purifying material 1 (1a, 1b) may be held by weaving or adhering to a water permeable sheet such as a nonwoven fabric, and the water permeable sheet may be used as the filters 35c, 35d, 37b to 37d. In addition, a filter medium such as a hollow fiber filter, barley stone, or tourmaline may be combined.

  Furthermore, the water purifier 30 is not limited to the stationary type shown in FIG. 12, but even if the water purifier 30 is formed small enough to be attached to the faucet spout, the raw water W is collected from the spout and is used as a stationary type. Various modifications such as attaching an attachment that can remove anions from the raw water W by the water purifier 30 are conceivable.

Hereinafter, some examples of the purifier for the water purifier formed using the plurality of purification materials 1 will be described.
FIG. 13 shows a chip-shaped purification material 1 shown in FIG. 1 or a pellet-shaped purification material 1 shown in FIG. 2 or FIG. This shows an example of a water purifier purifying body 41 housed in a net cage 40. Here, the mesh basket 40 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 40a denotes a reinforcing wire.

  In addition, although not shown in detail, the net fence 40 is formed with an opening provided with a door that can be opened and closed and locked so that the purifier 1a can be replaced or replenished. . The purifier 41 for the water purifier having the above-described configuration can be disposed at the position instead of the anion removing layer 38 by making the shape of the reed 40 into a cylindrical shape, for example.

  The purifier 41 for the water purifier is not limited to that illustrated in FIG. 13. For example, as shown in FIG. 14, the purifier 41 for water purifier is formed in a net bag 42 made of a corrosion-resistant material such as polyethylene. The mat-shaped water purifier purification body 43 may be configured by accommodating a large number of the chip-shaped purification material 1 shown in FIG. 2 and the pellet-shaped purification material 1a shown in FIG. In this case, it is desirable that the opening (not shown) of the mesh bag 42 can be freely opened and closed so that the purification material 1 or 1a can be easily filled and removed. It is also possible to arrange the purifier 43 for the water purifier instead of the anion removing layer 38 by adjusting the shape of the bag 42 filled with the purifying material 1 (1a) to a substantially cylindrical shape.

  FIG. 15 schematically shows an example of another purifier 50 for water purifier. A water purifier purification body 50 shown in FIG. 15A is a water-permeable sheet (for example, a nonwoven fabric) configured to carry the chip-shaped purification material 1 (formed in pellets 1a or powder 1b having an appropriate diameter). Sheet) 51. When carrying the pellets 1a or powder 1b of the purification material on the nonwoven fabric sheet 51, the purification body 50 for the water purifier is configured so that the pellets 1a or powder 1b of the purification material are mixed into the raw material of the nonwoven fabric sheet 51. be able to. Moreover, you may fix the purification material 1 to the nonwoven fabric sheet 51 using the below-mentioned adhesive agent.

  In the purifier 50 for water purifier shown in FIG. 15B, the chip-shaped purification material 1 (for example, the pellet-shaped purification material 1 a) is attached to the entire surface of the nonwoven fabric sheet 51 using an appropriate adhesive 52. Hold on. As shown in FIG. 15C, 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 51. By using these purification bodies 50 for water purifiers as the filters 35c, 35d, 37b to 37d shown in FIG. 12, it is possible to provide the filters 35c, 35d, 37b to 37d with an anion adsorption function. Moreover, when using this purification body 50 for water purifiers as a filter, the nonwoven fabric sheet 51 is made to follow along the plate-shaped net body which consists of chemically stable materials, such as a plastic and stainless steel, and the mechanical strength is raised. You may do it.

  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 fourth embodiment with reference to FIGS. 16 and 17.

First, FIG. 16 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. 16, 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. 16 will be described in detail with reference to FIGS. 16 and 17. 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 fourth embodiment, CaCl _{2 from} which the highest performance anion-adsorbing carbon material can be obtained is used as the metal chloride, but BaCl ₂ , MnCl ₂ or the like may be used.

  In the fourth embodiment, the contact treatment of the purification material 1 with the HCl solution 96 is performed in the treatment tank 97, but water may be used in place 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 fourth 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. 22 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 the 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. 21E shows a purification material 1 that has adsorbed NO ₃ ions and is in the state shown in FIG. 21D. A highly concentrated 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 according to the fourth 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. 23, 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. 23 also show that the purification material 1 should be treated with HCl in order to further increase the anion adsorption ability of the purification material 1.

  Next, the purification material 1 of the fourth 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 fourth 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 fourth 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. 24 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 fourth 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 water purifiers of this invention, (B) is a figure which shows the processing example of the purification material for water purifiers. It is a figure which shows roughly an example of the apparatus which manufactures the said purification material for water purifiers. It is a figure which shows an example of the process of manufacturing the purification material for water purifiers 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 water purifiers. It is a figure which shows an example of the process of manufacturing the purification material for water purifiers using the said manufacturing apparatus. It is a figure which shows each adsorption amount in the adsorption test of nitrate nitrogen and nitrite nitrogen of the purification material for water purifiers 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 water purifiers. 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 an example of the water purifier of this invention. It is a figure which shows an example of the purification body for water purifiers using the said purification material for water purifiers. It is a figure which shows the other example of the purification body for water purifiers. It is a figure which shows the further another example of the purification body for water purifiers. It is explanatory drawing which shows roughly the structure of the apparatus which manufactures the purification material for water purifiers concerning 4th 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 4th 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 | cleaning material of 4th 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 4th Example, and a comparison material.

Explanation of symbols

1 (1a, 1b) Purifier for water purifier 5 Raw material plant 9,21 Carbide 9S, 21S Carbon material 30 Water purifier 39 Activated carbon layer

Claims (12)

It is made of a carbon material having anion adsorption characteristics by combining an anion capable of ion exchange with an anion to be adsorbed by contacting an acid solution with a carbide obtained by carbonizing a raw material plant, Or the purification material for water purifiers characterized by including the said carbon material. Carbon material that has anion adsorption properties by binding anions that can be exchanged with anions to be adsorbed by contacting an acid solution with the carbide obtained by carbonizing the raw material plant treated with calcium. Or a water purifier purification material comprising the carbon material.   The purification material for water purifiers 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 water purifiers according to any one of claims 1 to 3, wherein the concentration of the acid solution is 0.01 mol / L or more. The raw material plants by introducing treating metal chloride Ri by the carbonizing process, the carbon material anion ion exchange adsorption target carbides its cause is bound chloride ions as possible gave an anion adsorbing properties Or a water purifier purification material comprising the carbon material.   The purification material for water purifiers of Claim 5 which contains 2-25% of metal chloride couple | bonded in the said carbide | carbonized_material as ash.   The purifier for a water purifier according to claim 5 or 6, wherein the carbide is in contact with water and / or an acid. Water purifier purifying material according to any one of claims 5-7 wherein the metal chloride is CaCl ₂ or BaCl _2.   The carbonization temperature of a raw material plant is 400 to 1000 degreeC, The purification material for water purifiers in any one of Claims 1-8.   The anion which adsorb | sucked the anion of the next adsorption object while removing the adsorbed anion from the purification material for water purifiers in any one of Claims 1-9 which adsorb | sucked the anion of adsorption object A purifier for a water purifier, which is bonded in place of the removed anion.   A clean water purification method, wherein clean water is purified using the purifier for water purifier according to claim 1.   A water purifier, wherein the water purifier purifying material according to any one of claims 1 to 10 is provided in a water purifier to purify clean water.