JPS6077936A - Metallic ion extractant, its manufacture, and extractive separation - Google Patents

Abstract

PURPOSE:To manufacture an extractant having high extractability for metallic ions even in high-concn. mineral acids by allowing secondary amine shown by the specified formula to react with formaldehyde and phosphorous acid in the presence of a mineral acid. CONSTITUTION:The secondary amine shown by formula I (di-n-octyl amine, etc.) and phosphorous acid (triethyl phosphite, etc.) in a specified molecular ratio are dispersed in an about 4-8-normal sulfuric or hydrochloric acid soln., and the temp. of the liquid is kept at about 90-100 deg.C. Then the specified amt. of formaline is slowly dropped while stirring, and the liquid is allowed to react for about 2-20hr while stirring by keeping the temp. at about 95-100 deg.C to form the metallic ion extractant shown by formula II. The charge ratio of the raw material is preferably regulated to 1:(1.2-1.4):(2.0-2.4) of secondary amine:phosphorous acid:formaldehyde. The metallic ion extractant usable even in >= about 1-normal high-concn. mineral acid can be manufactured in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel metal ion extractant, a method for producing the same, and a method for extracting and separating the same.

Conventionally, in the field of hydrometallurgical smelting of nonferrous metals, a liquid in which a metal ion extractant is dissolved in a water-insoluble solvent is brought into contact with an aqueous solution containing metal ions.

By extracting only specific metal ions to the solvent side,
Attempt to separate and recover metal ions. So-called solvent extraction methods are practiced industrially. Among the metal ion extractants used in such solvent extraction methods, monoheptadecyl phosphate, di(2-ethylhexyl) phosphate, 1-hydroxy-ethylhexyl phosphate, 2-ethylhexyl-
Phosphorus-containing compounds such as 2-ethylhexylbosphate and 2-ethylhexylphenylphosbonate are known, but these extractants contain mineral acids with a high concentration of 1N or more, such as sulfuric acid, phosphoric acid, hydrochloric acid, Metal ions, especially uranium, in hydrofluorosilicic acid and nitric acid.

There was a problem with the ability to extract and separate metal ions such as antimony, bismuth, and indium.

In view of the above-mentioned circumstances, the present inventors have conducted intensive studies on extractants that have a high extraction ability for the above-mentioned metal ions even in high-concentration mineral acids exceeding the specified specifications. The present invention was achieved based on the discovery that this compound, dissolved in a water-insoluble solvent, has the ability to selectively extract and separate valuable metals dissolved in highly concentrated mineral acids.

That is, the present invention has the general formula (1) (wherein R1 and R2 represent a hydrocarbon group having 4 to 20 carbon atoms, and may be the same or different.

) and the metal ion extractant represented by the general formula (II) 8">
It is characterized by reacting a secondary amine represented by NII (II) 2 (in the formula, RI+R2 is the same as the group described above), polymaldehyde, and phosphorous acid in the presence of a mineral acid. A method for producing a metal ion extractant represented by the general formula (1) (wherein RI+R2 is the same as the group described above) and a liquid-liquid method using an organic phase consisting of the metal ion extractant and a water-insoluble organic solvent. This is an extraction separation method characterized by extracting and separating metal ions contained in an aqueous solution.

To obtain the metal ion extractant of the present invention, 1, for example, the general formula (
The secondary amine represented by II), formaldehyde, and phosphorous acid may be reacted by heating in a mineral acid. At this time, first, the secondary amine represented by the general formula (II) and phosphoric acid in a predetermined molar ratio are dispersed and charged in a sulfuric acid or hydrochloric acid solution of about 4 to 8N, and then the liquid temperature is adjusted to 90 to 90%. 10
While keeping the temperature at 0°C, slowly add a predetermined amount of Polmarin dropwise while stirring, then raise the reaction temperature to 95-11°C while continuing to stir.
It is sufficient to maintain the temperature at 0"C and allow the reaction to occur for 2 to 20 hours. In addition, phosphorous acid can be prepared by adding phosphorous acid derivatives 1, such as triethyl phosphite and dibutyl phosphite, which form phosphorous acid during the reaction. Furthermore, the reaction may be carried out by adding a solvent such as dimethylbormamide or N-methylpyrrolidone to the mineral acid aqueous solution as a reaction solvent.

Uta 1: 0.8-1.
6:13 (secondary amine: phosphorous acid: formaldehyde)
is preferable, especially 171.2-1.4: 2.0-2.
4 is preferred.

Preferred specific examples of the secondary amine represented by the general formula (11) used in the present invention include diro-octylamine,
Bis(2-ethylhexyl)amine.

Dilaurylamine 5 N-benzyl-1(3-ethylpentyl)-4-ethyloctylamine, bis(1-isobutyl-3,5-dimethylhexyl)amine, di(tridecyl)amine, anhalide LA-1 (Roam Andhas secondary amine mixture).

Examples include anhalides 1 and A-2 (secondary amine mixture manufactured by Rohm and Haas).

The metal ion extractant of the present invention is produced by dissolving the metal ion extractant in a water-insoluble organic solvent and bringing it into contact with an aqueous mineral acid solution containing metal ions, thereby extracting only specific metal ions into the solvent. It can be used in a method of separating and collecting ions, that is, a solvent extraction method. At this time, the concentration of the extractant of the present invention in a water-insoluble organic solvent is 1 to 1.
30-t% is preferred. Also, as a water-insoluble organic solvent.

tJM, which has been conventionally used in solvent extraction methods.
i medium, e.g. t hahensen, toluene, xylene.

Examples include, but are not limited to, kerosene, light oil, chloroporum, carbon tetrachloride, and tetrachloroethylene. The temperature during solvent extraction is preferably 220°C to 80°C. The liquefaction of the organic phase and aqueous phase is preferably about 0.1 to 10. The extraction time is preferably 1 minute to 1 hour.

When using the metal ion extractant of the present invention dissolved in a water-insoluble organic solvent, isodecanol, 2-ethylhexanol, P-
Compounds such as nonylphenol and triptylphosphate-1. can be used.

Although the metal ion extractant of the present invention can be used to extract any metal ion, it is particularly effective in extracting metal ions such as uranium, antimony, bismuth, indium, and gallium dissolved in highly concentrated mineral acids. be able to.

Examples of highly concentrated mineral acid aqueous solutions targeted by the present invention include 1N or higher sulfuric acid, phosphoric acid, hydrochloric acid, fluorosilicic acid, and nitric acid aqueous solutions.2 As a specific extraction example, about 5M mineral acid containing uranium Extraction and separation of uranium from aqueous phosphoric acid solution,
Also copper, antimony.

It is used for the selective separation of andrimone and bismuth from an approximately 2M sulfuric acid aqueous solution containing bismuth, but is not limited thereto.

The metal ions extracted by the extractant of the present invention are as follows.

The extractant can be regenerated and metal ions can be recovered by back-extracting using an appropriate back-extracting agent in the same way as in the normal solvent extraction process, and the extractant can be used repeatedly. be.

The present invention will be explained in more detail below using Examples.

Example 1 Di(2-ethylhexyl)amine 24g, flax #9g
, 15 g of hydrochloric acid and 15 g of water were charged into a Mitsuro flask equipped with a stirrer, a dropping funnel, and a reflux condenser.

Subsequently, the liquid temperature was heated to 90°C while stirring.

Next, in this state, 18 g of formalin was gradually added dropwise over 1 hour, and reflux was continued for an additional 5 hours. After heating was completed, the mixture was cooled to room temperature. After that.

After adding methylene chloride to the reaction solution and extracting the product into methylene chloride, the methylene chloride was distilled off to obtain oily di(2-ethylhexyl)amine-N-methylenebosonic acid (this compound into an extractant.)32
I got g.

Next, a solution of 5 g of Ttll extractant A and 10 g of p-nonylphenol dissolved in 85 g of tetrachlorethylene was added. l
50ml of I and 100mg of hexavalent uranium/7! Contains 5M phosphoric acid? 87 & 50 ml were mixed, stirred at room temperature for 15 minutes, allowed to stand, and separated into an oil layer and an aqueous layer.
When the uranium concentration in the water layer was measured, the uranium concentration was 4.
2 mg/R, and the extraction rate was 95.8%.

Next, after washing the oil Ji1150m+ from which uranium was extracted with water,
．． After stirring with 50 ml of 4M soda carbonate solution for 5 minutes and allowing it to stand, the oil layer and water layer were separated and the uranium concentration in the ice layer was measured, and the uranium concentration was 92 mg/jl! Therefore, quantitative back extraction was performed and uranium was recovered.

Example 2 A reaction was carried out in the same manner as in Example 1 using Anharai 1-LA-2 manufactured by 01 M&HAS Co., Ltd. as a raw material to obtain an N-methyleneposponic acid derivative of ■-2 (this compound was extracted Agent B
shall be. ).

Next, 35g of extractant, 5g of l-butyl phosphate
, 50 ml of a solution obtained by dissolving 90 g of kerosene into 8/8, and 50 ml of a 2M sulfuric acid solution containing 400 mg/β of antimony, 200 mg/β of hismuth, and 40 g/β of copper.
were mixed, stirred for 15 minutes, and allowed to stand.

After that, the oil layer and water layer were separated and the concentrations of antimony, hismuth, and copper in the water layer were measured.

60mg/R, 20mg/β, 40g/j respectively! Therefore, it was possible to selectively extract and separate antimony and hismuth.

Next, 1i250ml of oil extracted from antimony and bismuth.
After washing with water, the mixture was stirred with 50+nI of 6M hydrochloric acid/8 solution for 5 minutes.

After standing still, the oil layer and the water layer were separated and the bismuth and antimony concentrations in the water layer were measured and found to be 310 mg of antimony.
/ j! , bismuth 150 mg/12, and back extraction was performed efficiently.

Comparative Example 1 Di(2-ethylhexyl)phosphorus #i, 5g to toluene 9
50ml of solution dissolved in 5g and 100ml of hexavalent uranium
g/j! Mix 50 ml of a 5M phosphoric acid solution containing.

As in Example 1, the mixture was stirred at room temperature for 15 minutes, left to stand, and separated into an oil layer and an aqueous layer.The uranium concentration in the aqueous layer was measured.5 The uranium concentration was 45.6 mg/β, and the extraction rate was 5. The value was 54.45, which was insufficient.

Patent applicant: Unikorikiki Co., Ltd.

Claims (1)

[Claims] Tl) Represented by the general formula (1) (wherein RI+ represents a hydrocarbon group having 4 to 20 carbon atoms, and may be the same or different) Zenku Ioyu/Extractant. (2) A secondary amine represented by the general formula (II) 2")NI+ (■) 2 (in the formula, RI+R2 is the same as the group described above), formaldehyde, and phosphorous acid in the presence of a mineral acid. A method for producing a metal ion extractant represented by the general formula (1) (in the formula, RI+R2 is the same as the group described above), which is characterized by reacting. (3) General formula (■) (in the formula, R+, Ih is the same as the group described above.) Metal ions contained in an aqueous solution are extracted and separated by a liquid-liquid extraction method using an organic phase consisting of a metal ion extractant represented by (Ih is the same as the group described above) and a water-insoluble organic solvent. extraction separation method.