JPS6010521B2 - Chelate resin deodorization method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for deodorizing a chelate resin, which removes impurities such as solvents and unreacted monomers remaining inside the resin during the chelate resin manufacturing process.

When producing a chelate resin, it is inevitable that impurities such as the solvent and reactive monomer used in the production process remain inside the produced chelate resin. Chelate resins containing such impurities not only have an odor due to residual solvent, etc., but also these impurities impede the adsorption of heavy metal ions, so it is necessary to remove these impurities before commercialization. For this reason, these impurities have conventionally been removed during the manufacturing process of chelate resin, but methods for removing them include, for example, hot air drying by simply blowing air after producing chelate resin, reduced pressure vacuum drying by heating under vacuum, or Hot water washing method etc. However, such hot air drying methods and reduced pressure vacuum heating drying methods apply heat to the chelate resin to make it easier for the medium and monomers inside the resin to come out, while at the same time quickly removing the medium and monomers outside the resin, reducing the external concentration of the resin. Since the removal is carried out by moving the medium based on the difference between the concentration of the impurities and the internal concentration of the impurities, the rate of removal of impurities is determined by the rate of diffusion of the impurities within the resin, and the deodorizing process takes a long time.

On the other hand, the hot water cleaning method increases the diffusion rate within the resin by keeping the resin itself moist and allowing the resin to swell. After the deodorization, the hot water, medium, and monomer are replaced, so the deodorizing treatment time is shortened compared to the above two methods. However, since all of these known deodorizing treatment methods involve exposing the chelate resin to a heated state for a long period of time, the functional groups of the chelate resin, which are relatively unstable to heat, are destroyed and the performance of the chelate resin is significantly reduced. As a result of intensive research to solve the drawbacks of the current deodorizing methods for chelate resins, the present inventor found that when heavy metal ions are adsorbed to the chelate functional groups of chelate resins, the functional groups are significantly stabilized against heat, and the heavy metal ions The present invention was completed based on the discovery that impurities such as the solvent and unreacted monomers remaining in the chelate resin even when it is adsorbed can be easily removed by heating.

That is, the present invention is a deodorizing method for a chelate resin, which comprises exchanging and adsorbing heavy metal ions onto the chelate resin, and then immersing the resin in a hot bulb to wash and remove impurities such as solvents and monomers remaining inside the resin.

Chelate resins to which the present invention is applied include, for example, styrene divinylbenzeso copolymer, phenol-aldehyde condensate, and other base resins with functional groups such as jethylenetriamiso, triethylenetetramine, tetraethylenebentamine, and bentamate. Amines such as ethylenehexamine,
Examples of the method of the present invention include aminocarboxylic acids obtained by reacting the above amines with halogenated acetic acid, alcohol amines such as jetanolamine and dibropanolamine, and ureas such as urea and thiourea. This can be applied to cleaning when solvents and unreacted monomers remain inside the resin during the manufacturing process of such chelate resins, and when solvents adhere to the chelate resins during use.

The method of the present invention involves treating the chelate resin containing the solvent used in the manufacturing process and unreacted monomers with an aqueous solution containing heavy metal ions, such as zinc, copper, aluminum, nickel, and calcium, to convert the functional groups of the chelate resin into A chelate resin that adsorbs heavy metal ions and then protects its functional groups by adsorbing heavy metals, preferably 8000 or more,
Particularly preferably, the chelate resin is washed by immersion in hot water of 9 to 0 or more.

At this time, there is a method of cleaning the chelate resin by soaking the chelate resin in hot water and cleaning it mechanically, but there is also a method called "method of blowing air into the hot water or blowing heated steam to make the hot water deplete." is preferable because no damage to the resin occurs.The chelate resin deodorized by the method of the present invention can be easily regenerated by desorption treatment with a normal mineral acid aqueous solution.
This treatment hardly reduces the chelate forming ability of the chelate resin. However, if similar hot water treatment is performed without adsorbing heavy metal ions, the higher the hot water used, the lower the performance of the chelate resin after deodorizing treatment, and in severe cases, more than 30% of the chelate formation chamber may be destroyed. There is also. Next, the present invention will be explained in more detail with reference to Examples.

Note that parts in the examples represent parts by weight. Example 1 To 10 parts (0.37 mol) of chloromethylated styrene-divinylbenzene resin, 33 parts of methylene chloride was added,
Next, 150 parts of water, 320 parts of methanol, and 8.3 parts (0.137 mol) of dimethyl sulfide were added to this mixture.
was added and kept at room temperature for 9 hours.

The chelate resin thus obtained was isolated and washed with water, and the resin was further immersed in a solution containing 20Q blood magnesium to convert the chelate functional group terminal into a magnesium type.
1 part of this magnesium type chelate resin and 5 parts of ion exchange water
One part was placed in a three-loaf flask equipped with a condenser tube, and air was blown at 90 qo for 5 hours while adding replacement water to reduce the volume.

The isolated chelate resin had no solvent odor, and when its chelating performance was measured, there was almost no difference from before treatment. On the other hand, when a chelate resin was subjected to a similar deodorizing treatment without being treated with a magnesium-containing solution, the chelating performance decreased by about 23%.

Example 2 Phenolic chelate resin UNISEREC UR-10 [The resin base is a phenol condensate, has iminodiacetic acid as a functional group, and has an Na type at its terminal.

[manufactured by Unitika ■] was soaked in an aqueous solution containing 20-gold copper to make the end of the chelate functional group into a copper type. When 1 part of this chelate resin and 5 parts of ion-exchanged water were deodorized in the same manner as in Example 1, almost no decrease in the chelating performance of the treated resin was observed. On the other hand, when the same UNICEREC UR-10 as above and the chelate resin which was treated with an aqueous sulfuric acid solution to make the chelate functional group terminal H-type were deodorized in the same manner as in Example 1, it was found that the Na-type chelate resin The decrease in chelating performance was about 50%, and that of the H-type chelate resin was about 20%.

Claims (1)

[Claims] 1. A method for deodorizing a chelate resin, which comprises exchanging and adsorbing heavy metal ions onto the chelate resin, and then immersing the resin in hot water to wash and remove impurities such as solvents and monomers remaining inside the resin. . 2 Claim 1 in which the hot water is of 80°C or higher
Deodorization method described in section. 3. The deodorizing method according to claim 1 or 2, wherein the cleaning and removal of impurities is carried out by blowing air through hot water. 4. Claim 1 or 2, in which impurities are washed and removed by blowing heated steam into hot water.
Deodorization method described in section.