JPS6090089A - Removal of fluorine ion in water - Google Patents

Abstract

PURPOSE:To efficiently remove a fluorine iron, by roughly removing the fluorine ion in water by using a roughly removing adsorbent and, thereafter, treating water by using an aminoalkylene phosphate type chelate resin having a metal ion adsorbed therewith. CONSTITUTION:Water is treated with a roughly removing adsorbent selected from an inorg. adsorbent such as diatomaceous earth, zeolite or a silica gel and an org. adsorbent based on a resin such as a phenol formaline resin, an epoxy resin or an acrylic resin to roughly remove the fluorine ion in water. Subsequently, water is treated by using a metal ion adsorbed aminoalkylene phosphate type chelate resin to remove the fluorine ion in water to a low concn. As the aforementioned chelate resin, there is one having an aminoaklylene group therein as a functional group and an iron ion or an aluminum ion adsorbed with said group.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention improves the efficiency of fluorine ions in water <n'r=1,
Regarding how to. Saego details (Masui Ill's), A
: Use the suction 1'+ agent for roughening the ions, and then use the cleaning agent 1' to absorb the metal ions.
This method uses resin to remove fluorine to a low concentration.

Currently, the ability to remove elemental ions (which are currently liberated in water) can be achieved by adding slaked lime (↓ slaked lime) to water and precipitating fluorine as fluorine and other calcium; The third method is to adsorb metal ions (e.g., iron ions, aluminum ions, etc.) to iminodiacetic acid type KIRE-1 resin and remove fluorine ions (Japanese Patent Application Laid-Open No. 1983-1983). -44649, JP-A-51-115058) Fourthly, a method of adsorbing and removing fluorine ions using an aminoalkylene phosphate chelate resin adsorbing metal ions (JP-A-57-1072).
87) Nato is known. However, in the first method, the solubility of fluoridated calcium is approximately 15 mg/l.
Therefore, it has the disadvantage that it cannot remove fluorine ions to low concentrations. In the second method, 1;3 ion exchange resin 0)
4r>C,04'->H2PO4->C1-F-, the selectivity for fluorine ions is very low, and there is a drawback that it is easily influenced by coexisting salts. In the third method, fluorine ions can be removed to a low concentration, but the total amount of adsorption is small and the regeneration time is short, making it extremely impractical. The fourth method is a method previously reported by the present inventors to improve the shortcomings of these conventional methods, and it has a good removal limit for fluoride ions, and also has a large total adsorption. However, it cannot be said that the performance of low power is fully utilized.

Therefore, the inventors of the present invention have carried out an intensive investigation to solve these drawbacks.1. , 1, and found that fluoride ions in water can be efficiently removed to a low concentration by treatment with an aminoalkylene phosphate chelate resin that has adsorbed fluoride ions in water.

Examples of inorganic adsorbents containing fluorine ions used in the present invention include diatomaceous earth, magnenoir, bauxite, zeolite, silica gel, activated alumina, bone char, and magne-aralumina and titanium-based adsorbents. Composite materials such as organic adsorbents include styrene-divinylbenzene copolymer, phenol-formalin resin, resol-formalin resin, epoxy resin, acrylic resin, vinyl chloride resin, and have rubamic acid groups and thiol. group, oxidium group, amide ocytum group, aminoalkyle/phosphoric acid group, and its functional JA
Examples include resins that have adsorbed a small amount of iron ions, aluminum ions, lanthanide ions, etc.

The aminoalkylene phosphate type chelate resin as used in the present invention is one that has an aminoalkylene phosphate group as a functional group in the resin, and has iron ions, aluminum ions, nitride ions, etc. adsorbed thereto.

In addition, the base material of the resin used here includes styrene-divinylbenzene copolymer, phenol-formalin resin,
Resolne-Formalin 11 Resin, epoxy resin, acrylic resin, vinyl chloride resin, etc. are used.

The method for removing the 72/72/7 acid type "'-11 Uji 4 5 1 2' chestnut ions can be applied to either a column method or a batch method, but is not particularly limited to these methods. It's not a thing.

The present invention will be explained below with reference to Examples.

Example -) The physical properties shown in Table 1 were obtained as an adsorbent for distributing elementary ions (by combining active aluminum and chelate resin with styrene and novinylbenzene. , a phosphomethylamino group (NHCH2
This chelate tree 11i was treated with a sulfuric acid r-luminium aqueous solution to obtain A/3'
We prepared an aminomethylene phosphate type chelate resin that adsorbed .

Column (inner diameter 40 mm) with 100 ml of activated alumina
Two columns, in which 100 ml of aminomethylene phosphate type chelate resin adsorbed Als' was packed into another column, were connected so that water could be passed in series.

Next, as raw water, F-: 25 ppm (dissolved as NaF), Ca'': 10 ppm (dissolved as CaC7,), NaCl!=196, Na2SO4:, 1
96, pH 6' (7) Aqueous solution passing rate SV 10 (
l! /Hr), the liquid was passed in a downward flow.

The results of the liquid passage are shown in Figure 1.

Table-1 Fluorine ions or 2 ppm started to leak from around 1st column, 11 TE, liquid passage magnification 1001/l-R, liquid passage magnification 30
01/l-R, fluorine ions leaked by 151)2m.

However, at the outlet of the second column, the liquid flow rate is 600 ///
The amount of fluorine ions was Q, 5 ppm or less up to around -R.

Example 2 As an adsorbent for fluoride ions, an adsorbent whose resin base is a styrene-divinylbenzene copolymer and has an iminodiacetic acid group as a functional group, and in which this resin is adsorbed with lanthanum iodine, was also used. As a chelate resin that adsorbs metal, it is a resin matrix or phenol-formalin resin, and has a functional,
Bosphomethylaminos was used as the base, and a resin in which aluminum ions were adsorbed was used.

7,y elemental 7100 ppm and Na Cl
Raw water containing 5000 ppm, pH 6 100
To 1, 1'1' of the above-mentioned lanthanum iodine for roughening was added, and the mixture was stirred in a container for 5 hours to adsorb and remove fluorine. As a result, the residual R'4 of fluorine ions
The temperature was 2.8 J)pm.

Next, the treated water obtained by solid-liquid separation was passed through a column filled with 100 ml of the above-mentioned chelate resin adsorbing aluminum ions at a flow rate of SV 15 (1/Hr) in a downward flow. When the fluorine ion concentration of the LAE effluent was measured, it was found to be 0.1 ppm or less.

Next, apply the same treatment to the above raw water 9 times (
jl 9001! ) The fluorine ion concentration was 0.191) m or more in all cases.

[Brief explanation of drawings]

Patent applicant Miyoshi Yushi Co., Ltd.

Claims (1)

[Claims] A method for removing fluorine ions from water is as follows: First, fluorine A'7 was roughened using a roughening adsorbent, and then metal ions were adsorbed.・How to treat I or 1 fat with III uV.