TW201223881A - Method for treating fluorine-containing water - Google Patents

Abstract

Calcium carbonate particles having a small particle diameter and having excellent reactivity and flowability are used and fluorine-containing water is passed upward through a reaction tower by a once-through operation to thereby effectively remove and recover the fluorine. Disclosed is a method for treating fluorine-containing water which comprises passing the fluorine-containing water upward from a lower part of a reaction tower (1), converting the fluorine contained in the fluorine-containing water into calcium fluoride through reaction with calcium carbonate particles present in the reaction tower (1), thereby removing the fluorine, and taking out the treated water from which the fluorine has been removed, from an upper part of the reaction tower (1), wherein calcium carbonate particles are introduced from an upper part of the reaction tower (1) into the reaction tower (1); through which the fluorine-containing water is being passed. Thus, use is made of not a method in which the fluorine-containing water is passed after calcium carbonate particles having a small particle diameter are packed into the reaction tower (1) to form a packing layer but a method in which calcium carbonate particles having a small particle diameter are introduced from above the reaction tower (1) when the fluorine-containing water is being passed upward through the reaction tower (1). As a result, the calcium carbonate particles can be efficiently reacted with the fluorine contained in the fluorine-containing water.

Description

201223881 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for treating water containing fluorine, and more specifically, the reaction tower is circulated upward into the water containing fluorine to make it in the reaction tower with calcium carbonate. Particle contact points, and fluorine can be efficiently removed as a method of removing calcium fluoride. [Prior Art] Fluoride-containing wastewater is hanged in the field of semiconductor manufacturing or related fields, solar cell manufacturing, various metal materials, single crystal materials, and optical materials. Conventionally, a method of treating fluorine-containing water has been generally proposed in which fluorine-containing water is poured into a calcium carbonate crucible column, and fluorine is converted into calcium fluoride having good crystallinity to be removed and recovered. Further, in these methods, a calcium carbonate ruthenium tower in which two or more columns are connected in series, and calcium fluoride which is introduced into the first column in sequence can be reacted with fluorine in the fluorine-containing water. When it is completely calcium fluoride, when the calcium carbonate in the first tower can completely become calcium fluoride, the calcium fluoride in the first column is extracted and then the new calcium carbonate is added, and the tower is used as the last The tower is provided with water, and the method of treating the fluorine-containing water in a so-called wheel-rotating manner to recover high-purity calcium fluoride is known (for example, Patent Documents 1 to 3). In the conventional calcium carbonate crucible for the treatment of the fluorine-containing water, the calcium carbonate particles which are filled with the calcium carbonate particles are excessively small in water content, and are dissolved in the fluorine-containing water to be sufficiently supplied for the reaction. Use a particle size of -5 - 201223881 Ο . 3 mm or so. [PRIOR ART DOCUMENT] [Patent Document] Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. The problem to be solved by the invention is that the calcium carbonate particles having a particle diameter of about 0.3 mm have the following disadvantages (1) and (2). (1) It is difficult to flow in the charging tower due to the large particle size, and it is easy to adhere to the inside of the tower. (2) Compared with the smaller particles, the specific surface area is small and the reaction rate with fluorine is slow. In order to solve these problems, in the past, the fluorine-containing water flowing upward was introduced into the charging tower, and a part of the treated water taken out from the upper part of the tower was circulated to the lower part of the tower to become a circulation mode to increase the linear velocity inside the tower, so that the tower was The calcium carbonate particles inside can flow to prevent their adhesion, and the reaction can be sufficiently carried out by circulating water. However, the circulation water supply method must have the power to make it circulate, and the reaction tower volume must be large for circulating water, which is unfavorable in industry. In view of this, as long as it is a small-sized calcium carbonate particle having a particle diameter of 0.05 mm or less, the fluidity is high, it is difficult to fix the viscosity, and since the specific surface area is large, the reaction speed with fluorine is also fast, so it is not necessary to recycle. In one pass

• 6- S 201223881 Water. However, calcium carbonate having a small particle size still has the following problems (i) and (ii). (i) It is easily soluble in water, and for this reason, the ratio of contribution to the reaction with fluorine is lowered. (Π) When the water velocity in the tower is small, the flow rate of the calcium carbonate particles will be shifted to the side. As a result, a dead space will be formed at the bottom of the tower, and the calcium carbonate particles in this part cannot react. Or solid. In the present invention, by using a small-sized calcium carbonate particle having excellent reactivity and fluidity, the fluorine-containing water can be used to efficiently remove the fluorine and recycle it by using an upward flow of water to the reaction column. In order to solve the above problems, the present inventors have found that the small-diameter calcium carbonate particles do not pass into the fluorine-containing water after being immersed in the reaction tower. When the water-containing fluorine-containing water is supplied to the reaction tower, calcium carbonate particles having a small particle diameter are introduced from above the reaction tower to efficiently react with fluorine in the fluorine-containing water. The present invention is finally achieved by the present invention. The gist of the person is as follows. The fluorine-containing water in the first aspect is treated by flowing water from the lower portion of the reaction column into the fluorine-containing water, and reacting the calcium carbonate particles in the reaction column with fluorine in the fluorine-containing water to form the fluorine. In the treatment method of removing the fluorine-containing water from the upper portion of the reaction tower, the fluorine-containing water is removed from the upper portion of the reaction tower, and the reaction tower is introduced with the fluorine-containing water from the upper portion of the reaction tower. Calcium particles are characteristic. 201223881 The second aspect of the method for treating fluorine-containing water is characterized in that in the first aspect, the calcium carbonate particles are introduced into the reaction column as a powder. In the first aspect or the second aspect of the method for treating fluorine-containing water in the third aspect, the amount of calcium carbonate particles in the reaction column is fluorine in the water containing fluorine which is passed into the reaction column. The reaction equivalent is 0.9 to 1.1 equivalents as a characteristic. In the method of treating the fluorine-containing water of the fourth aspect, in any one of the first to third aspects, the amount of the calcium carbonate particles in the reaction column is controlled to be the treated water taken out from the reaction tower. Below pH 値6 is characteristic. In the fourth aspect of the method for treating fluorine-containing water in the fifth aspect, the amount of calcium carbonate particles in the reaction column is controlled so that the pH of the treated water taken out from the reaction column can be 4.5 to 5 For the feature. In the method of treating the fluorine-containing water of the sixth aspect, in any one of the first to fifth aspects, the particle diameter of the calcium carbonate particles is preferably 0.05 mm or less. In the sixth aspect, the method for treating fluorine-containing water in the seventh aspect is characterized in that the average particle diameter of the calcium carbonate particles is 0.01 to 0.0 3 mm. The treatment method of the fluorine-containing water of the eighth aspect is in any one of the first to seventh aspects, wherein the calcium carbonate particles are introduced into the cylinder of the tubular calcium carbonate particle-input member provided in the upper portion of the reaction column. In the method, the upper end of the tubular carbonate-calcium particle input member protrudes upward from the upper surface of the reaction tower, and the lower end is located at a position 30 cm or more lower than the water level of the treated water extraction portion of the reaction tower. Feature. In the eighth aspect of the method for treating fluorine-containing water according to the ninth aspect, the lower end of the calcium carbonate particle-input member and the treated water of the reaction tower are taken out.

-8 - S The distance between 201223881 is Li 25~100cm, which is characterized by 1/20~1/5 of the total effective tower height L2 of the above reaction tower. In the eighth or ninth aspect, in the eighth or ninth aspect, in the reaction column having a bottomed cylindrical shape, the cylindrical calcium carbonate particle input member is set to be concentric. (relative to the diameter (inner diameter) of the reaction column) The diameter (inner diameter) of the calcium carbonate particle-input member is 1/5 to 1/10 as a feature of the fluorine-containing water of the first aspect In any one of the eighth to tenth aspects, the diameter of the reaction column having a bottomed cylindrical shape is 300 to 150 mm, and the upward flow rate of the fluorine-containing water is 150 to 5000 L/h. The input amount of the above calcium carbonate particles is 3 to 100 L/h. The method for treating fluorine-containing water in the first aspect is a method of any one of the eighth to tenth aspects, wherein the reaction column having a bottomed cylindrical shape is directly 1500 to 3000 mm, and the fluorine-containing water is The upward flow rate is 5000 to 20000 L/h, and the input amount of the above calcium carbonate particles is 1 to 400 L/h. The method for treating fluorine-containing water in the thirteenth aspect is any one of the eighth to tenth aspects, wherein the diameter of the reaction column having a bottomed cylindrical shape is 3,000 to 50,000 mm, and the above-mentioned fluorine-containing water is upward. The flow rate is 2000 to 60000 L/h, and the input amount of the above calcium carbonate particles is 400 to 1 200 L/h. In the method of treating the fluorine-containing water of the fourteenth aspect, in any one of the first to thirteenth aspects, the fluorine-containing water is passed through the reaction column as a feature. The method for treating fluorine-containing water in the first aspect is a reaction column in which two or more columns are connected in series, and the above-mentioned reaction tower is sequentially connected from the first column of 201223881. The water of fluorine is introduced into each reaction tower. When the water quality of the inflow water of the first reaction tower is about the same as the water quality of the effluent water, the water passing through the first reaction tower is stopped, and the reaction is changed to the second stage. The water passing through the tower is taken out, and the particles of the calcium fluoride containing in the first reaction tower are taken out, and the reaction tower of the first stage is used as the last reaction tower of the reaction tower above the two towers, and the water is repeatedly passed through. The project is a water-passing method for the rotation of the wheel, and the calcium carbonate particles are introduced into the last reaction column in which the fluorine-containing water is introduced into the water. The treatment method of the fluorine-containing water of the sixteenth aspect is the 15th aspect, wherein the last-stage reaction tower to which the calcium carbonate particles are charged is not pre-formed with calcium carbonate before the water containing the fluorine-containing water passes through the water. The layer is characterized in that water of the above-mentioned fluorine-containing water is supplied and calcium carbonate particles are introduced. The treatment method of the fluorine-containing water of the 17th aspect is in the 15th or 16th aspect, and in the reaction tower of the last stage, there is a fluorine concentration of the treated water of the reaction tower of the preceding stage of 1 000 to 30000 mg/L. In the present invention, a small particle diameter excellent in reactivity and fluidity, for example, a particle diameter of 〇.〇5 mm or less can be used as the feature of the present invention. The calcium carbonate particles are not preliminarily charged in the reaction tower to form a sputum layer, and then the fluorine-containing water is introduced, but when the fluorine-containing water is circulated upward, the upper portion of the reaction tower is used as a powder. In addition, it is possible to prevent the formation of a dead water region due to the flow of the calcium carbonate particles in the reaction tower.

-10- S 201223881 The small-sized calcium carbonate particles are easily dissolved. However, it is also possible to prevent the dissolution of calcium carbonate by controlling the calcium carbonate particles charged according to the pH. That is, the reaction between calcium carbonate and fluorine, for example, with hydrogen fluoride is as shown in the following reaction formula (I). Under acidic pH conditions, the carbonic acid formed by the reaction is not immediately used as the carbonic acid gas according to the following formula (II). It is dissolved in water and discharged to the outside of the system, so it does not affect calcium carbonate. However, under conditions of pH neutrality or higher, it becomes a bicarbonate ion according to the following formula (III). The produced heavy carbon acid ions act as an acid and dissolve calcium carbonate.

CaC03+2HF^CaF2+H2C〇3 ··· ( I ) pH with: H2CO H20 + C02 (generating gas) -.-(11) Ρ Η Neutral or above: h2co3 — h + + hco3- . . III) Therefore, in the present invention, the amount of calcium carbonate particles to be injected into the reaction column is preferably controlled so that the pH of the treated water taken out from the reaction column is 6 or less, thereby preventing dissolution of calcium carbonate. When the reaction amount of the calcium carbonate particles in the reaction column is 〇·9 to 1.1 times the equivalent amount of fluorine which is passed through the water in the fluorine-containing water of the reaction column, the fluorine in the fluorine-containing water is highly removed. Better words. Further, in the present invention, the calcium carbonate particles are supplied from the cylindrical calcium carbonate particle input member provided in the upper portion of the reaction column, and the upper end protrudes above the upper surface of the reaction tower, and the lower end is taken out through the treated water of the reaction tower. The in-cylinder injection of the carbonic acid #5 particle input member provided at a position lower than the water level of 30 cm or more is preferable. That is, when the calcium carbonate particles having a small particle diameter are directly maintained in a state of being put into a powder, the powder also contains a part of the fine powder.

The calcium carbonate will be directly injected from the overflow port of the reaction tower, and the treated water will flow out from the reaction tower from S -11-201223881, and it may not be used in the reaction. When such a calcium carbonate particle having a small particle size is to be used, when the calcium carbonate particle-inputting member is used as described above, calcium carbonate-like calcium carbonate is retained inside the cylinder of the calcium carbonate particle-injecting member, and the water in the tower is retained. In sufficient contact, the reaction can have a greater contribution. The present invention specifically connects the reaction towers of two or more towers in series, and is preferably applied to the water-containing fluorine when the water containing fluorine is passed through in a rotating manner. In the last stage of the water reaction tower, before the reaction tower of the last stage of the injection of the calcium carbonate particles is passed through the water containing fluorine, the calcium carbonate filling layer is not formed in advance to carry out the water supply and the carbonation of the fluorine-containing water. Calcium particles are best used to prevent drift in the tower and to prevent the formation of dead water areas. [Mode for Carrying Out the Invention] Hereinafter, an embodiment of a method for treating water containing fluorine according to the present invention will be described in detail with reference to the drawings. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an example of a reaction column 1 which is applied to the present invention. The reaction column 1 is an open-bottomed bottomed cylindrical shape, and fluorine-containing water is introduced from the bottom to be constructed from the upper portion. The overflow port 2 takes out the treated water. 3 is a member into which calcium carbonate particles are introduced, and in FIG. 1, the calcium carbonate particle-input member 3 is fixed to the upper portion of the reaction tower 1 concentrically with the reaction tower 1, and the upper end 3A is protruded from the water surface of the reaction tower 1, and the lower end The 3B system is disposed under the water surface of the reaction tower 1, and is installed in a vertical direction which can be lower than the water level of the overflow port 2 of the reaction tower 1. The fluorine-containing water is introduced from the bottom of the reaction column 1, and then overflows from the above

-12- S 201223881 Flow port 2 outflow. In the present invention, when the water is distributed to the water containing fluorine, in the upper portion of the reaction column 1, the calcium carbonate particles are introduced into the cylinder of the member 3 via the calcium carbonate particles. The fluorine in the fluorine-containing water reacts with the calcium carbonate particles to be charged, and calcium fluoride is precipitated and removed from the fluorine-containing water. When the particle size of the calcium carbonate particles introduced from the upper portion of the reaction column 1 is too large, the reaction rate with fluorine is slow, and the object of the present invention in which calcium carbonate having a small particle diameter is used to increase the reaction rate cannot be achieved. Therefore, the particle size of the calcium carbonate particles used in the present invention is 0. 5 mm or less, preferably 0.03 mm or less, and the average particle diameter is about 〜1 to 0.03 mm, especially 0.02 to 0.03 mm. suitable. Further, when the amount of the calcium carbonate particles to be supplied is too small, the fluorine in the fluorine-containing water cannot be sufficiently removed, and when too much, the amount of the calcium carbonate particles used is not increased, and it is not economical, and if unreacted calcium carbonate remains, There is also the problem that it cannot be converted into calcium fluoride, and there is no possibility of obtaining high-purity calcium fluoride. Therefore, the amount of calcium carbonate particles is the reaction equivalent of fluorine in the fluorine-containing water that passes through the reaction tower 1 0.9 to 1.1 equivalent times, particularly preferably 0.95 to 1.05 equivalents. Further, in the present invention, the calcium carbonate particles are maintained in the reaction column under the powder. If the calcium carbonate particles are put into the cement slurry, the capacity of the reaction tower must be added as the amount of water to be added to the cement. The transfer must have a cylinder, and in the case of calcium carbonate particles and fluorine-containing water. In terms of fluorine reaction efficiency, it is also preferable to use it as a powder. The input of the calcium carbonate particles may be continuously input, and may be carried out at intervals, for example, every 5 to 300 minutes. When continuously put in

The amount of calcium carbonate particles input per time for S-13-201223881 or the amount of calcium carbonate particles charged per fraction of time is based on the ratio of the reaction equivalent of fluorine to the fluorine-containing water, or the following The suitable pH in the column is determined. As described above, the small-sized calcium carbonate particles used in the present invention have the disadvantage of being easily dissolved in water, but the calcium carbonate particles can be controlled according to the pH, that is, the carbonic acid can be prevented. Calcium dissolution. In the present invention, in order to prevent the dissolution of calcium carbonate, the pH of the reaction liquid in the reaction column is controlled to be 6 or less, and particularly preferably 5 or less. In general, the addition of calcium carbonate to the fluorine-containing water increases the pH enthalpy and makes it easier to dissolve the calcium carbonate particles. For this reason, it is preferable to introduce a small amount of calcium carbonate particles in a state where the pH is low, and it is preferable from the viewpoint of preventing dissolution of the calcium carbonate particles. Therefore, in the present invention, the pH of the treated water flowing from the reaction column 1 or the water in the upper portion of the reaction column is measured, and it is preferable to control the pH to be 6 or less, particularly 5 or less to control the amount of calcium carbonate to be supplied. In addition, this pH system is preferably used to prevent the dissolution of calcium carbonate particles, and the amount of calcium carbonate particles required to ensure the reaction with fluorine is usually 4.5 or more. When the reaction column in which the fluorine-containing water flows upward is directly carried out, a part of the calcium carbonate particles to be injected will flow out from the reaction tower together with the treated water, and the reaction cannot be performed, and not only will the water quality of the treated water be reduced. The reason. That is, as described above, when the calcium carbonate particles having a small particle diameter are maintained under the powder, a part of the powdery powder is also contained therein, and the fine powdery calcium carbonate will overflow. The vent and the treated water are immediately after the input from -14-

S 201223881 The reaction tower flows out, and it is feared that it will not contribute to the reaction. Therefore, in the present invention, as shown in Fig. 1, it is preferable to provide a cylindrical calcium carbonate particle-input member 3 in the reaction column 1, and to introduce calcium carbonate particles into the reaction column 1 through the inside of the calcium carbonate particle-input member 3. Most suitable. As described above, the calcium carbonate particle-input member 3 is fixed to the upper portion of the reaction column 1 concentrically with the reaction column 1, and the upper end 3A protrudes from the water surface of the reaction column 1, and the lower end 3B is provided on the water surface of the reaction column 1. Next, it is set to a vertical direction at a position lower than the water level of the overflow port 2 of the reaction column 1. By using the calcium carbonate particle-input member 3, the fine powdery calcium carbonate is retained in the inside of the cylinder of the calcium carbonate particle-input member 3, and is sufficiently contacted with the water in the column to obtain such fine powdery calcium carbonate particles. React more smoothly. When the distance between the lower end 3B of the calcium carbonate particle input portion material 3 and the water level of the overflow port 2 of the reaction column 1 is too short, the above-described effects which are obtained by providing such a calcium carbonate particle input member 3 cannot be obtained. The contact efficiency with the upward flow of the fluorine-containing water may be deteriorated in an excessively long period of time. Therefore, the distance Li is preferably from 25 to 100 cm, for example, about 50 cm, and is preferably about 1/20 to 1/5 of the total effective column height L2 of the reaction column. Further, for example, when the cylindrical calcium carbonate particle input member 3 is provided in the reaction column 1 having a bottomed cylindrical shape as shown in Fig. 1, the calcium carbonate particles are supplied to the member 3 by the diameter (inner diameter) of the reaction column 1. The diameter (inner diameter) is about 1/5 to 1/10, and the calcium carbonate particle input member 3 is disposed concentrically with the reaction column 1, so as to prevent the flow of the fine powdery calcium carbonate particles. The contact efficiency is preferred. The upward flow rate of the fluorine-containing water to the reaction column 1 is such that the contact efficiency with the calcium carbonate particles charged from the upper portion of the reaction column 1 -15 - 201223881 can be sufficiently ensured, for the diameter of the reaction column or the calcium carbonate particles The correlation between the input amounts is preferably adjusted as appropriate, and for example, the conditions shown below are preferred. (i) The diameter of the reaction tower: 300~1 500mm, the flow rate of the fluorine-containing water: 150~500 OL/h The input amount of the calcium carbonate particles: 3~100L/h (Π) The diameter of the reaction tower: 1 500~ Flow rate of fluorine-containing water at 3000mm: 5000~2000L/h Input of calcium carbonate particles: 100~400L/h (iii) Diameter of reaction tower: Flow rate of fluorine-containing water above 3000~5000mm: 2000~60000L /h Calcium carbonate particles input: 400~120 OL/h Further, it is suitable for the reaction tower of the present invention, although it can also be a water-passing water or a circulating water, but it is not necessary to use small When the calcium carbonate particles having a particle diameter are circulated through the water, the effect of the present invention which exhibits high reaction efficiency can be exhibited, and it is also preferable to pass the water in one pass. By continuing this treatment, particles which become calcium fluoride due to the reaction with fluorine are accumulated in the reaction tower, and the water can be appropriately stopped to take out the calcium fluoride particles. In the present invention, in order to reduce the drift in the reaction tower, to prevent the formation of dead water in the bottom of the tower, and to prevent the dissolution of the calcium carbonate particles, the calcium carbonate particles are put into a reaction tower previously filled with calcium carbonate particles. It is preferable to use a small amount of a reaction column in which a calcium carbonate particle-filled layer is not formed. Therefore, the present invention in particular connects the reaction towers of 2 or more columns in series to follow -16-

S 201223881 When the wheel is rotated to pass the water containing fluorine water, the last reaction tower for water can be applied without carbonation. That is, in general, the processing system according to the wheel rotation mode discharges the particles of calcium fluoride in the fluorine-containing water in the reaction column of the foremost stage, and then adds a new layer in the tower to form a filling layer. In the reaction column of the last stage, a reaction column in which no calcium carbonate particles are formed is formed in the reaction column, and the fluorine having a fluorine concentration of 1000 to 15 in the reaction tower of the reaction column in which the calcium carbonate is not formed is not formed. It is preferable that the water is made into an upward flow of water into the calcium carbonate particles in one pass. In addition, such a method of turning the water in accordance with the rotation mode of the wheel can be carried out, for example, as follows. Namely, a fluorine concentration meter or a pH meter is provided at the inlet and outlet of a plurality of counter towers such as a patent or a column connecting two or more columns, for example, 2 to 4 columns. Further, in addition to the column, the reaction tower which is formed as a layer of calcium carbonate particles sequentially feeds the fluorine-containing water into the reaction column of the passage section to introduce calcium carbonate particles. The fluorine concentration meter or the pH meter up to the first mouth, and the number of the first reaction concentration meter or the p Η meter can be treated as about the same water, and after the same number, the water is changed. The water is exchanged for the second reaction column, and the calcium fluoride particles in the column are taken out, and it is not necessary to add the fluorine reaction in the previous cycle of the fluorinated layer of the fluorine-containing particles. The calcium carbonate particles to be formed, but the middle layer of the present invention is used as the last stage reaction tower of the last stage, -30000 mg/L, and the system itself can be exchanged from the upper part according to [3, the straight column, in each reaction In addition to the reverse layer of the last stage, from the first water, while continuing to pass the reaction column of the last stage of the reaction tower into the tower, the passage of the reaction tower will stop the reversed calcium carbonate particles. -17- 201223881 'This is used as the last stage of the reaction tower to be connected, and the reaction tower from the second stage is sequentially supplied with water into the fluorine-containing water. In the following order, the replacement of the first-stage reaction tower to the last stage of the rotation of the wheel is performed in the same order. As described above, when the present invention is applied to a reaction tower in which a calcium carbonate particle-containing layer is not formed, the effects of the present invention can be effectively exhibited. EXAMPLES Hereinafter, the present invention will be more specifically described by way of examples and comparative examples. [Example 1] Using the reaction column 1 shown in Fig. 1, at a flow rate of 50 L/h, a fluorine-containing water having a fluorine concentration of 1 过 mg/L was passed over at a flow rate of more than one passage, while passing through the upper portion of the reaction column 1 The calcium carbonate particle-input member 3 is placed in an amount of 1/3 L at a time of 10 minutes, and calcium carbonate particles having an average particle diameter of 〇3 mm are introduced so that the pH of the treated water can be 5 or less. Specifically, it can be 4. 5 to 5.0. The amount of calcium carbonate particles charged is 1.02 times the equivalent of the fluorine reaction equivalent of the fluorine-containing water passing through the water. Further, the reaction column 1 has a bottomed cylindrical shape having a diameter of 300 mm' and a height of 300 cm (i.e., L2 = 300 cm), and can be taken out from the overflow port 2 at the upper end of the column so that the treated water can be taken out. The calcium carbonate particle input member 3 provided in the reaction column 1 has a cylindrical shape having a diameter of 10 mm and a length of 400 mm, and is provided so as to be concentric with respect to the reaction column 1. The lower end 3B of the input calcium carbonate particle input member 3 is located 3 sec (i.e., 1^=300111) lower than the overflow port of the reaction tower. -18 -

S 201223881 After 30 hours of continuous water flow, the reaction column 1 is 1 (the carbonic acid particles which are at least partially converted into calcium fluoride are pulled out from the bottom of the reaction tower, and no particles are observed at all. The fluorine concentration of the treated water was highly removed. [Comparative Example 1] In Example 1, 60 L of calcium carbonate particles (particle size and used in Example 1) were used before the water for the calcium carbonate particles was introduced. The same is the same as the reaction tower layer, except that the others are all flowed upwards continuously for 20 hours, and the relationship between the particles in the reaction tower is reduced to 48 L. Further, the fluorine concentration of the treated water obtained by this treatment is not good for the removal efficiency of fluorine. As described above, the specific use of the specific aspect will be clearly understood by the present applicant, as long as it does not deviate from the present invention. In addition, the application of this case is based on the July 28, 2010 patent (licensed 2010-169378), all of which are listed.

Ting to leave 60L particles of calcium particles). This phenomenon is fixed. 100 ~ 300mg / L, in the fluorine-containing average particle size and solid, to form a water-filled water into the fluorine-containing water system due to calcium carbonate is dissolved in the 5L system is fixed in the reaction 呑 8 00 ~ 1 500mg /L Ming, as long as it is the intention and scope of the company, it is very clear that the application in Japan is cited in this article -19- 201223881 [Simple description of the diagram] Figure 1: shows the reaction applied in the present invention Schematic diagram of a tower example [Description of main components] 1 : Reaction tower 2 : Overflow port 3 : Calcium carbonate particle input member 3 A : Upper end 3B : Lower end L!: Distance of water level L2 : Full effective tower height

-20- S

Claims (1)

201223881 VII. Patent application scope: 1. A method for treating fluorine-containing water, characterized in that water is introduced into the lower part of the reaction tower to pass water into the fluorine-containing water, so that the calcium carbonate particles in the reaction tower and the fluorine-containing one The fluorine reaction in the water is carried out by removing the fluorine as calcium fluoride, and in the treatment method of removing the fluorine-containing water from the fluorine-treated water from the upper portion of the reaction tower, the reaction is carried out by the water passing through the fluorine-containing water. The tower is a person who inputs calcium carbonate particles from the upper part of the reaction tower. 2. The method for treating a fluorine-containing water according to the first aspect of the invention, wherein the calcium carbonate particles are introduced into the reaction column as a powder. 3. The method for treating water containing fluorine in the first or second aspect of the patent application, wherein the amount of calcium carbonate particles charged into the reaction column is for the water to be passed into the fluorine-containing water of the reaction column. The fluorine reaction equivalent is 0.9 to 1.1 times the equivalent. 4. The method for treating fluorine-containing water according to any one of claims 1 to 3, wherein the amount of calcium carbonate particles charged into the reaction column is controlled to be taken out from the reaction column. The pH of the treated water is below 値6. 5. The method for treating fluorine-containing water according to claim 4, wherein the amount of calcium carbonate particles charged into the reaction column is controlled so that the pH of the treated water taken out from the reaction column can be 4.5 to 5 By. 6. The method for treating fluorine-containing water according to any one of claims 1 to 5, wherein the calcium carbonate particles have a particle diameter of 0.05 mm or less. 7. The method for treating fluorine-containing water according to item 6 of the patent application, wherein the average particle diameter of the calcium carbonate particles in -21 - 201223881 is o. oi to 0.03 mm. The method for treating fluorine-containing water according to any one of the first to seventh aspects of the present invention, wherein the carbonic acid is introduced into a cylinder of a tubular calcium carbonate particle-receiving member provided in an upper portion of the reaction column The method of the calcium particles, wherein the upper end of the cylindrical calcium carbonate particle input member protrudes upward from the upper surface of the reaction tower, and the lower end is located more than 30 cm below the water level of the treated water extraction portion of the reaction tower. 9. The method of treating fluorine-containing water according to claim 8 wherein the distance between the lower end of the calcium carbonate particle input member and the water level of the treated water extraction portion of the reaction tower is 25 to 100 cm. It is 1/20~1/5 of the total effective tower height L2 of the above reaction tower. 10. The method for treating a fluorine-containing water in the eighth or ninth aspect of the patent application, wherein the cylindrical calcium carbonate particle-input member is set to be concentric for the reaction column having a bottomed cylindrical shape. The shape is 1/5 to 1/10 of the diameter (inner diameter) of the above reaction column. 1 1 The method for treating a fluorine-containing water according to any one of the items 8 to 10 of the patent application, wherein the diameter of the reaction column having a bottomed cylindrical shape is 300 to 15 〇 Omm. The upward flow rate of the fluorine water is 150 to 5000 L/h. The input amount of the above calcium carbonate particles is 3 to 1 〇〇L/h. The method for treating fluorine-containing water according to any one of claims 8 to 10, wherein the reaction column having a bottomed cylindrical shape has a diameter of 1500 to 3000 mm. The flow rate is 5 〇〇〇 to 20000 L/h, and the input amount of the above calcium carbonate particles is 1 〇〇 to 400 L/h. The method for treating water containing fluorine-22-S 201223881 according to any one of claims 8 to 10, wherein the reaction column having a bottomed cylindrical shape has a diameter of 3000 to 50000 mm, and the above-mentioned The upward flow rate of the fluorine water is 2000 to 60000 L/h, and the input amount of the calcium carbonate particles is 400 to 1 200 L/h. 14. The method for treating fluorine-containing water according to any one of claims 1 to 13, wherein the fluorine-containing water is passed through the reaction column in a one-pass manner. [15] The method for treating fluorine-containing water according to any one of claims 1 to 14, wherein the reaction column of two or more columns is connected in series, and the fluorine is sequentially supplied from the reaction column of the first stage. The water is passed into each reaction tower. When the water quality of the inflow water of the first reaction tower is about the same as the water quality of the effluent water, the water flowing to the first reaction tower is suspended, and the second reaction tower is replaced. The water passing through the first stage of the reaction tower removes the particles of calcium fluoride, and the reaction tower of the first stage is used as the last reaction tower of the reaction tower above the two towers, and the engineering of repeating the water sequentially It is a water-passing method for the rotation of the wheel, and the calcium carbonate particles are put into the last reaction column in which the fluorine-containing water is introduced into the water. 16. The method for treating fluorine-containing water according to claim 15 wherein the last stage of the reaction of the calcium carbonate particles is before the water of the fluorine-containing water is passed, and the calcium carbonate filling layer is not formed in advance. , the water passing through the fluorine-containing water and the calcium carbonate particles are introduced. 17. The method for treating fluorine-containing water according to claim 15 or 16, wherein in the reaction column of the last stage, the fluorine concentration of the treated water containing the preceding reaction column is from 1 300 to 30000 m g /L of the fluorine-containing water, which is circulated into the water in one pass. -twenty three-