JPS59123540A - Regenerating method of chelate resin - Google Patents

Abstract

PURPOSE:To control the elution and decomposition of an easily hydrolyzable functional group by bringing a chelate resin having an easily hydrolyzable group into contact with an eluent and a regenerating agent at a prescribed temp. CONSTITUTION:A chelate resin having an easily hydrolyzable group, wherein >=1 kind of metallic ions among III group metals U, V, Cd, Pb, Ni, Cu, Co and Mo are absorbed, is brought into contact with an eluent at <=15 deg.C. The above- mentioned chelate resin has a functional group consisting of an amidoxime or an ester coupling, and the resin is further brought into contact with a regenerating agent at <=15 deg.C when needed. Thus, the decomposition of the easily hydrolyzable functional group is suppressed when the chelate resin having the easily hydrolyzable functional group wherein the metallic ions are absorbed is eluted and regenerated.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for regenerating a chelate resin having an easily hydrolyzable group that has adsorbed metal ions.

As a method for regenerating a chelate resin in which metal ions have been adsorbed to -F, the adsorbed metal ions are eluted by contacting the chelate resin with an eluent such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, or acetic acid at room temperature; Furthermore, a method is known in which the regenerating agent is brought into contact with a regenerating agent such as sodium hydroxide, potassium hydroxide, 7F calcium oxide, magnesium hydroxide, or ammonia, if necessary. However, in chelate resins having easily hydrolyzable groups, the metal ion trapping ability of the resin decreases significantly due to repeated adsorption and regeneration of metal ions, compared to chelate resins having other functional groups. This poses a major hindrance to the industrial use of chelate resins having easily hydrolyzable groups.

In view of these circumstances, the present inventors have made extensive studies to investigate the cause of the decrease in metal ion-trapping ability of chelate resins having easily hydrolyzable groups, and as a result, have arrived at the present invention.

That is, in the present invention, a chelate resin having an easily hydrolyzable group to which a metal ion has been adsorbed is brought into contact with an eluent at a temperature of 15° C. or lower, and the present invention will be explained in further detail as necessary.

The chelate resin having an easily hydrolyzable group used in the present invention is not particularly limited as long as it has a functional group that gradually undergoes hydrolysis under normal elution and regeneration conditions.

Such a chelate resin generally includes a chelate resin having a functional group such as an amidoxime group, an amidino group, or a group consisting of an ester bond such as a sulfuric acid ester, a phosphoric acid ester, or a carboxylic acid ester.

Specifically, (1) polymers of vinyl cyanide monomers such as acroni-1-lyl, α-chloroacrylonitrile, vinylidene cyanide, methacrylonitrile, or copolymerization with vinyl cyanide monomers are possible. A resin containing an amidoxime group by reacting a copolymer with another ethylenically unsaturated monomer with hydroxylamine or a derivative of hydroxylamine; (2) Acryliconi-1-lyl, α-chloroacrylonitrile, vinylidene cyanide , by reacting a vinyl cyanide monomer such as methacrylonitrile with hydroxylamine or a hydroxylamine derivative, and then copolymerizing the vinyl cyanide derivative with other ethylenically unsaturated monomers that can be homopolymerized or copolymerized. y, = resin; (3) chloromethyl group, sulfonyl chloride group, carbonyl chloride group, isocyanate group, epoxy group,
Polymers with amine-reactive groups such as aldehyde groups such as styrene-divinylbenzene copolymers, phenol resins, polyethylene, polypropylene, and polyvinyl chloride (hereinafter referred to as resins with amine-reactive groups) Aminoacetonitrile, aminomalonitrile, diaminomaleonitrile.

Dicyandiamide, iminodiacetonitrile, ■-amino-2-cyanoethane, 4-aminobenzonitrile, l
- A resin obtained by reacting a nitrile compound having an amino group or an imino group such as amino-8-cyanopropane, and then reacting it with hydroxylamine or a hydroxylamine derivative; (4) The nitrile compound having an amino group or an imino group as described above; and hydroxylamine or a hydroxylamine derivative is reacted with the resin having the amine-reactive group; (5) a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a dithiocarboxylic acid group; , styrene-divinylbenzene copolymer having alkylamino groups, etc., phenol resin, and other resins are treated with halogenation.
A resin is obtained by reacting the product obtained by reacting the nitrile compound having an amino group or imino group with hydroxylamine or a hydroxyl derivative;
(6) Benzamidoxime, benzylamino-N-methanediamide dioxime, benzylamino-N-ethanediamide dioxime, (2-benzimidazolylthio)acetone amidoxime, (2-benzimidazolylthio)
Ethylamidoxime, (-2-penzimidazolylthio)propylamidoxime, 1,2-benzisoxazole-3-acetamidoxime, 5-fluoro-1,2-
Compounds having at least one amidoxime group in the molecule, such as benzisoxazole-3-acetamidoxime, phenylsulfinylacetamidoxime, (3-chlorophenylsulfinyl)-acetamidoxime, mixtures of the above compounds, or compounds specified separately and aniline , resorcinol, 3-aminopyridine, 4-aminopyridine, 4-aminobenzenesulfonic acid, a mixture of 4-aminocarboxylic acid and formalin, epichlorohydrin, epibromhydrin, etc., and a resin having an amidoxime group, such as a condensation reaction resin (7) A resin having an amidino group by reacting a resin having a nitrile group with N,N-dimethylaminopropylamine, N,N-dimethylaminoethylamine, or N,N-diethylaminoethylamine; (8) A resin having a phosphoric acid ester group by reacting a resin having a chloromethyl group with triphenyl phosphite, triethyl phosphite, tributyl phosphite, etc.; (9) Resin having a hydroxyl group such as polyvinyl alcohol, cellulose, phenol resin, etc. Resins containing groups consisting of ester bonds by reacting phosphoric acid, sulfuric acid, acetic acid, bromoacetic acid, chloroacetic acid, phenyl phosphate, diphenyl phosphate, diphenylphosphinic acid, phenylphosphonic acid, etc., and Na, K, Ca% of these resins.
Examples include metal salts such as Ml.

The resin used in the present invention that adsorbs metal ions and is used in the present invention is
It doesn't matter if it's small.

Examples of metals include uranium, gallium, indium, vanadium, cadmium, lead, nickel, copper,
Examples include cobalt, molybdenum, etc., but are not limited to these.

In carrying out the method of the present invention, the chelate resin that has adsorbed metal ions is eluted with an eluent to elute the adsorbed metal ions. The contact between the chelate resin that has adsorbed metal ions and the eluent is carried out while maintaining the temperature of the zone where the chelate resin is present at no higher than about 15°C, preferably below 10°C. However, if the temperature of the zone where the chelate resin exists becomes higher than 15° C. due to contact between the chelate resin adsorbing metal ions and the eluent, the content of functional groups will decrease, which is not preferable. In particular, it is preferably carried out at -10 to 10°C.

% & sometimes the temperature of the zone where the chelate resin is present is about 15%
One way to maintain the temperature below ℃ is to adsorb metal ions and cool the resin or eluent, or both, to a level where the temperature of the system does not exceed 15℃ even if heat is generated before contact. Alternatively, the packed bed of chelate resin is cooled by either external or internal cooling, or a combination of both, and the temperature of the system is controlled so as not to exceed 15°C, or a combination of the above methods is adopted. .

Examples of elution methods include passing an eluent through a packed bed of chelate resin that has adsorbed metal ions, or charging the chelate resin into an elution tank and stirring it before adding an eluent to elute. . As the eluent, a water bath solution such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, etc. can be used.

The eluent used is generally 005 to 2N, preferably 0.1 to 1N.

The contact time varies depending on the type of metal to be adsorbed, but it is usually sufficient to contact for several seconds or more. By carrying out electrolysis etc. after one summer,
Metals can be recovered.

In this way, the metal ions are eluted and the chelate resin is prepared as is or as needed in water and/or a water bath solution such as sodium hydroxide, potassium hydroxide, calcium oxide, magnesium hydroxide, ammonia, etc. After treatment with a regenerating agent consisting of the following, it can be used repeatedly as a metal ion adsorption/trapping agent.

When treatment with a regenerant is accompanied by heat generation, as in the case of elution, the contact between the regenerant and the T-Kokire-1/U fat that adsorbs metal ions is controlled at the temperature of the zone where the chelate resin exists. The process is carried out while maintaining L7 at a temperature not higher than about 15°C, preferably below 10°C. Particularly preferably one
It is carried out at 0 to 10°C.

As a regenerating agent, sodium hydroxide, potassium hydroxide,
Aqueous solutions of calcium hydroxide, magnesium hydroxide, ammonia, etc. can be used. The concentration of the regenerant is generally 0.05 to 2N, preferably O1 to 2N.
1 standard is used.

This makes it possible to suppress the decomposition of easily hydrolyzable functional groups during the elution and regeneration of the rate resin, making it possible to do so, and its industrial significance is extremely great.

Hereinafter, the present invention will be explained in more detail with reference to examples, but it is needless to say that the present invention is not limited to the following examples unless it exceeds the gist thereof.

Examples 1 to 3 and Comparative Example 1 A commercially available chelate resin Duolite C8-846 (manufactured by Diamond Jamrock Co., Ltd., hereinafter referred to as chelate resin A) having an amidoxime group was packed into a column with an inner diameter of 20 g, and the uranium concentration was 8.1 I) Pb seawater was passed in an upward flow at a space velocity of 50 hr for 120 hours to adsorb uranium.Next, a 1N sulfuric acid aqueous solution cooled to the temperature shown in Table 1 was passed in a downward flow. The mixture was passed for 8 hours at a space velocity of 10 hr to elute 1 uranium adsorbed by the gyrate m fat.Next, 0.5N sodium hydroxide/water solution at 2°C was passed in an upward flow at a space velocity of 10 hr to elute 1 uranium. The chelate resin was regenerated over time.The temperature of the column during regeneration was maintained at 2-5°C.

When the adsorption amount of the chelate resin was examined after repeating the passage of seawater and elution and regeneration 20 times using the above method, it was found that the adsorption performance was shown in Table 1.

Table 1 Example 4 Vinylamide oxime polymer obtained by reaction of polyacrylonitrile fiber, hydroxylamine hydrochloride, and aqueous sodium hydroxide solution (hereinafter referred to as chelate resin B) 1
05' was allowed to flow inside for 3 hours to adsorb gallium. Next, after 100% of water was allowed to flow down, it was cooled to 0°C.
A 100% normal aqueous solution of hydrochloric acid was poured down for 1 hour, and then heated to 0°C.
The mixture was cooled to 100 tnl in a normal hydrochloric acid water bath for 1 hour to elute the gallium adsorbed to the chelate resin.

The temperature of the column was maintained at 0-2°C. Next, it was cooled to 5°C in A, and 100ml of water was poured down. After that, it was cooled to 0°C, and 400ml of 0.1N sodium hydroxide aqueous solution was poured into 1
It was played over time. Column temperature is 0-2℃
It is held in 1 piece.

Passing, eluating, and regenerating the gallium-containing liquid using the above method.
Repeat 0 times and set the first gallium adsorption rate to 10
When the temperature is 0, the adsorption rate for the 20th time is 93 flames and 1 flame.

Comparative Example 2 A gallium-containing solution was passed through and elution regenerated in the same manner as above using an eluent, a herbal medicine, and water at room temperature. If the potassium adsorption rate is 100, it is 24% of that of 1.

Example 5 300ml of the same chelate resin A used in Example 1 was
After running for an hour, 100 ml of water was flushed. Next, 200 liters of 1N aqueous hydrochloric acid solution cooled to 0 DEG C. was poured over a period of 1 hour to elute the gallium adsorbed on the chelate resin.

Next, 100 ml of water was poured over 30 minutes, and then 50 ml of 0.5 N aqueous sodium hydroxide solution cooled to 0° C. was poured over 30 minutes to regenerate the resin.

Passing, elution, and regeneration of the gallium-containing solution are carried out in the above manner.
When repeated 0 times, the gallium adsorption rate for the first time was 100.
The adsorption rate for the 20th time was 91.

Comparative Example 8 A gallium-containing solution was passed through, eluted, and regenerated using a 1N aqueous solution of hydrochloric acid and a 0.5N aqueous sodium hydroxide solution at room temperature in the same manner as above except for one exception.20
The adsorption rate for the first time was 18* when the potassium adsorption rate for the first time was 100.

Examples 6 to 13 Tests were conducted under the same conditions as in Example 5 except for the metal-containing solution shown in Table 2, and the adsorption rates for the first and 20th tests were compared. . The results are shown in Table 2.

Table 2 Example 14 A polymer having an amidoxime group, an imino group, and a hydrazino group (hereinafter referred to as thochelate resin C) obtained by the reaction of an acrylonitrile-dihinylbenzene copolymer, hydroxylamine sulfate, and an aqueous hydrazine solution was prepared. Inner diameter 2
01 column packed with indium concentrated K 205 ppm
pr=t a, liquid 8I of a! was run in 1.5 hours. Next, the mixture was cooled to 0° C., and 0.75 N hydrochloric acid (41) dissolved in water was flowed over a period of 2 hours to elute the indium adsorbed on the chelate resin C and regenerate the resin. Pass and elute the indium-containing liquid using the above method.
When repeated several times, the indium adsorption rate for the first time was 10
When I set it to 0, I got 87 Hayabusa and 1 piece.

Comparative Example 4 The adsorption rate of the 20th indium roller on which the indium-containing liquid was passed and eluted in the same manner as above except that a 0.75N hydrochloric acid aqueous solution at 20°C was used as the eluent was the same as that of the first indium roller. The adsorption rate was 100, and the number of plows was 28 at this time.

Claims (8)

[Claims] (1) A chelate resin having an easily hydrolyzable group on which metal ions have been adsorbed is brought into contact with an eluent at a temperature of 15°C or less,
A method for regenerating a chelate resin, which further comprises bringing the chelate resin into contact with a regenerant at a temperature of 15° C. or lower, if necessary. (2) The method according to claim 1, wherein the chelate resin having an easily hydrolyzable group has a functional group consisting of an amidoxime group or an ester bond. (3) Claim 1, wherein the metal ion is one or more metal ions selected from the group consisting of Group III metals, uranium, vanadium, cadmium, lead, nickel, copper, cobalt, and molybdenum; Or the method described in Section 2. (4) The chelate resin having an easily hydrolyzable group to which metal ions have been adsorbed is brought into contact with Bayer's liquid and has one core crystal.Claim No. 1.2. Or the method described in Section 3. (5) Contact between the chelate resin and the eluent at -10 to
Claim 1.2.3 or 4 carried out at a temperature of 10°C
The method described in section. (6) The eluent is 0.1 to 1N hydrochloric acid, sulfuric acid, phosphoric acid,
Claim 1.2, which is an aqueous solution of nitric acid or acetic acid
．． 3.4 or the method described in 5. (7) Claims @1.2. The chelate resin brought into contact with the eluent and the regenerant are brought into contact at -10-10°C.
8.4.5 or 6. (8) Pressure ulcer agent or 0.1 to 1N sodium hydroxide,
7. The method according to claim 1.2.3.4.5.6 or 7, wherein the aqueous solution is potassium chloride, calcium hydroxide, magnesium hydroxide, and ammonia.