JPS6092431A - Method for extracting metallic ion with solvent - Google Patents

Abstract

PURPOSE:To increase remarkably the rate of extraction by adding alkylbenzenesulfonic acid, dialkylnaphthalenesulfonic acid or a metallic salt thereof to acidic phosphoric ester, carboxylic acid or a chelating reagent as a cation exchange type extracting reagent. CONSTITUTION:Metallic ions are extracted from an acidic aqueous soln. with an org. solvent contg. acidic phosphoric ester, carboxylic acid or a chelating reagent. At this time, alkylbenzenesulfonic acid, dialkylnaphthalenesulfonic acid or a metallic salt thereof is added to the org. solvent or the acidic aqueous soln. This extracting method is especially effective in extracting Al<3+>, Ga<3+> and Fe<3+>.

Description

[Detailed description of the invention] Plates” JL The present invention relates to a method for solvent extraction of metal ions.

Prior Art There is a known method for concentrating and separating metals by extracting metal ions from an aqueous solution containing metal ions using an organic solvent containing a cation-exchange extractant such as an acidic phosphate ester, a carboxylic acid, or a chelating reagent. be.

In this metal ion solvent extraction method, when the metal ion-containing aqueous solution is an acidic aqueous solution, A i 3+
, G a s ÷ , F 63+ , T i 4+ , c
The extraction rate of 034, V2+, ■3+, C"3+, Ni2+, etc. is low, and in order to obtain the desired extraction rate, it is necessary to lengthen the extraction time, enlarge the extraction container, or accelerate extraction by heating. It was necessary.

Furthermore, the metal ions extracted into the extractant-containing organic solvent are normally recovered by back extraction (stripping) into an aqueous solution, but metals with low extraction rates such as the above-mentioned A jj 3+, Ga3+, and Fe3+ Another problem was that the back extraction speed was low.

It is also known that the monoester contained as an impurity in the acidic diester phosphoric acid, which is a type of cation exchange extractant, improves the speed of extraction of metal ions from an aqueous solution containing metal ions. It is also possible to use acidic phosphoric acid diester without removing the impurity monoester as an extractant, but the extraction speed in this case is also the same as that when acidic phosphoric acid diester viscous product is used as an extractant. (Chemical Engineering Vol. 44, No. 5, 1980, No. 300-308)
(see especially Table 2 on page 304).

Alkylbenzene sulfonic acid and dialkylnaphthalene sulfonic acid are also known to have the ability to extract metal ions, but since these are also strong surfactants, when added to an organic solvent, the organic Since a system consisting of a solvent and a metal ion-containing aqueous solution is emulsified and τ phase separation is not possible, it can only be used at extremely low concentrations, and it has not been possible to increase the extraction capacity of metal ions.

The purpose of the present invention is to improve the extraction rate of metal ions in the conventional solvent extraction method of extracting metal ions from an aqueous solution containing metal ions using a solvent containing a cation exchange extractant. It is a wonderful improvement.

The above object of the present invention is to add alkylbenzenesulfonic acid, sialic 4-renophthalenesulfonic acid or a metal salt thereof to a cation exchange type extractant selected from the group consisting of acidic phosphoric acid esters, carboxylic acids and chelating reagents. The problem was solved by using both methods.

That is, the gist of the present invention is to provide a solvent extraction method for extracting metal ions from an acidic aqueous solution using an organic solvent containing a cation-exchange extractant selected from the group consisting of acidic phosphate esters, carboxylic acids, and chelating reagents. The present invention provides a method for solvent extraction of metal ions, which comprises adding alkylbenzenesulfonic acid, dialkylnaphthalenesulfonic acid, or a metal salt thereof to the organic solvent or acidic aqueous solution to extract metal ions.

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the acidic phosphorus @ Mention may be made of mono-2-ethylhexyl ester and di-2-ethylhexyl phosphoric acid. The carboxylic acid preferably has 6 to 20 carbon atoms, and specific examples thereof include naphthenic acid represented by the general formula J: and carboxylic acid represented by the general formula J:.

Moreover, the following are mentioned as specific examples of the Kire-1 to reagents.

The organic solvent for dissolving the cation-exchange extractant may be of any type as long as it is insoluble or poorly soluble in water; specific examples include paraffinic solvents, aromatic solvents, naphthenic solvents, Examples include halogenated hydrocarbon solvents, higher alcohols, phenols, phenols, etc. For the metal ions extracted by the present invention, the extraction rate is usually considered to be the key, for example A13+, Ga3
+ , Fe 34 , -1- i 44 , C03
+, V2+, ys+, Cr3+, Ni2+, etc., but the present invention is particularly applicable to A131, G
Suitable for aa+ and p 6 a+ (7) extraction.

In the present invention, the alkylbenzenesulfonic acids, dialkylnaphthalenesulfonic acids, or metal salts thereof used in combination with the cation-exchanged extractant in the present invention are preferably those having 8 to 40 carbon atoms, and specific examples thereof include carbon atoms. i!
Examples include silbenzenesulfonic acid and its nonorkali metal salt, dinonylnaphthalenesulfonic acid and its alkali metal salt. The amount of alkylbenzenesulfonic acid, sialgylnaphthalenesulfonic acid or their metal salts for the above cation exchange extractant is 1
1Ilol/j! The latter is 0.1 mol/Jl
More preferably 0.02 mol/j! Particularly preferably 0. O15mol/J! It is as follows.

Since alkylbenzene sulfonic acids, dialkylnaphthalene sulfonic acids, or their metal salts dissolve in aqueous solutions in the form of molecules or are dispersed in the form of colloids or millelles, they may be added to the aqueous solution to extract metal ions; Afterwards, it is extracted into an organic solvent. Therefore, it is preferable to add it to an organic solvent from the beginning.

In the present invention, when a polar organic solvent such as a higher alcohol, ether, ester, phosphorus, or neutral organic phosphorus compound is further added, the phase separation characteristics in the extraction operation are improved.

Hereinafter, some examples will be given to further explain the present invention, but the present invention is not limited to these examples.

Example 1 Extraction example '1 of A (31) To 2-cotylhexyl phosphate-2-ethyl phosphate, which is a cation exchange extractant, to a paraffinic solvent, which is an organic solvent, 4:
Add syl ester to obtain an extractant concentration of 0.5 mol/
j! A paraffinic solution was obtained.

U, A using the extractant-containing paraffin solution obtained above.
When 8 (31) was extracted from a hydrochloric acid aqueous solution containing βG (3·61120 with 0.002 m01/β), it took approximately 80 hours (at 25° C.) to reach equilibrium.

On the other hand, 0.01 mol/β of dodecylbenzenesulfonic acid, which is a type of alkylbenzenesulfonic acid, and 1 mof/1 of 2-ethyl l\gisanol, which is a phase separation improver, were added to the paraffinic solution containing the extraction agent. When the above AβC (3.6
The extraction was completed at 5°C), and the extraction rate was 480 times faster.

Example 2 Extraction example 2 of A13+ Di-2-delhexyl phosphoric acid, a cation exchange type extractant, was added to a paraffinic solvent, which is an organic solvent, and the extractant mW was 0.5 iol/J! of paraffinic solution
It was.

Using the extractant-containing paraffin solution obtained above, A
fCJ! When 8(34) was extracted from a hydrochloric acid aqueous solution of about 0.9 IIH containing 0.002 mol/R of a.6H20, it took about 40 hours (at 25° C.) to reach equilibrium.

On the other hand, 0.01 mol/f! of dodecylbenzenesulfonic acid, which is a type of alkylbenzenesulfonic acid, was added to the extractant-containing paraffin solution described in step 1. , 1 mol/j of 2-ethylhexanol, a phase separation improver! The above AjIC4! When 8β3+ was extracted from an aqueous hydrochloric acid solution containing a.61-120, the extraction was completed in about 15 minutes (25°C), and the extraction rate was 160 times faster.

Example 3 Extraction example of Ga'a4 Di-2-ethylhexyl phosphoric acid, which is a cation exchange type extractant, was added to a paraffinic solvent, which is an organic solvent, and the extractant yA degree was 1. Q mol/j! Paraffinic solution of 1? is.

Equilibrium was reached when Gaa+ was extracted from a sulfuric acid aqueous solution containing 0.003 mol/J of gallium with a volume of about 1 using the paraffinic solvent containing the extractant obtained above: Equilibrium was reached in about 90 minutes at L. I counted.

On the other hand, 0.01 mol/j of dodecylbenzenesulfonic acid, which is one of the alkylbenzenesulfonic acids, was added to the above extractant-containing paraffinic solution. When Ga3+ was extracted from the above Qa3)-containing sulfuric acid aqueous solution using a phase separation improver 1)-decanol added at loVOI%, the extraction was completed in about 3 minutes, and the extraction rate was 30 times faster. Ta.

Example 4 Extraction example of Fe3+ Di-2-ethylhexyl phosphoric acid, which is a cation exchange extractant, was added to a paraffinic solvent, which is an organic solvent, until the extractant concentration was 1. Q mol/j! A paraffinic solution was obtained.

Using the extractant-containing paraffinic solution obtained above, F
e 2 (804) 3 ・16f-120 0, 01
From an aqueous solution containing mol/J of DH approximately 1(7) RA
When ea+ was extracted, it took about 2" to reach equilibrium.
Counted for 40 minutes.

On the other hand, 0.01 mol/jl of dodecylbenzenesulfonic acid, which is a type of alkylbenzenesulfonic acid, and 10 VO 1% of n-decanol, which is a phase separation improver, were added to the extractant-containing paraffin solution. When Fe3+ was extracted from the aqueous sulfuric acid solution containing Fe2(SO4)3.16120, the extraction was completed in about 5 minutes, and the extraction rate was 48 times faster.

As detailed above, by adding a small amount of gold nm of alkylbenpine sulfonic acid and sial-4-nylnaphthalene sulfone to an organic solvent containing a conventional cation-exchange extractant, the extraction rate of metal ions can be significantly improved. It happened.

Agent Hao Asahi

Claims (1)

[Claims] (1) In a solvent extraction method in which metal ions are extracted from an overlying acidic aqueous solution containing metal ions using an organic solvent containing a cation-exchange extractant selected from the group consisting of II-based phosphate esters, carboxylic acids, and chelating reagents. , alkylberzenesulfonic acid, dialkylnaphthalenesulfonic acid, or a metal salt thereof to the organic solvent or acidic aqueous solution to extract metal ions.