JPS58177420A - Method for recovering valuable metal - Google Patents

Abstract

PURPOSE:To recover efficiently a valuable metal such as In from an acidic aqueous soln. by bringing the soln. into contact with an aminomethylenephosphonic acid deriv. to form a water insoluble solid complex contg. the metal in the soln. CONSTITUTION:An acidic aqueous soln. contg. a valuable metal such as In is brought into contact with an aminomethylenephosphonic acid deriv. such as n- butylamino-N,N-bis(methylenephosphonic acid). At this time, the deriv. is preferably dissolved in an aqueous alkali soln. and added to said acidic aqueous soln. The concn. of the deriv. is adjusted to 0.1-30wt%, and 0.1-5 N aqueous soln. of NaOH or the like is used as the aqueous alkali soln. By the contact treatment a water insoluble complex is precipitated, and the valuable metal is recovered by filtration.

Description

[Detailed description of the invention] The present invention relates to a method for recovering valuable metals.

Currently, valuable metals, especially idium, are recovered from mineral acid aqueous solutions as by-products of the zinc smelting industry, and the main recovery method is solvent extraction using alkyl phosphates or alkyl carboxylic acids. ing. However, this solvent extraction method relies on migration of the solvent in an aqueous solution.

It cannot be said to be a highly productive method due to the large loss of solvent, the difficulty in removing extracted valuable metals such as idium, and the complicated process, and it is difficult to recover them efficiently. Have difficulty.

In view of these circumstances, the inventors of the present invention conducted intensive studies on a method for recovering valuable metals from acidic aqueous solutions, and as a result, they brought the metals into contact with aminomethylenephosphonic acid derivatives.

It was discovered that an aminomethylene phosphonic acid derivative forms a strong solid complex insoluble in water with a valuable metal such as idium in an acidic aqueous solution, and the valuable metal in the acidic aqueous solution is recovered extremely efficiently. 2. Achieved the present invention. did.

That is, one aspect of the present invention is a method for recovering valuable metals, which is characterized by bringing an acidic aqueous solution containing valuable metals into contact with an aminomethylenephosphonic acid derivative.

Preferred examples of the aminomethylene phosphonic acid derivatives used in the present invention include 1, for example, the general formula ([) (wherein R, -R, are each a hydrogen atom and a carbon number of 1 to 5
0 aliphatic hydrocarbon group, an aromatic hydrocarbon group having 1 to 5 carbon atoms, or some of the hydrogen atoms in these hydrocarbon groups are halogens or carboxyl groups.

Represents a hydrocarbon group substituted with a group selected from the group consisting of a hydroxyl group, a thiol group, an amino group, a phosphonic acid group, and an aminomethylene phosphonic acid group. ), a compound represented by the general formula (U) 5- (wherein R and -R6 are each a hydrogen atom and a carbon number of 1 to 5
0 aliphatic hydrocarbon group, an aromatic hydrocarbon group having 1 to 50 carbon atoms, or some of the hydrogen atoms in these hydrocarbon groups are halogens or carboxyl groups.

Represents a hydrocarbon group substituted with a group selected from the group consisting of a hydroxyl group, a thiol group, an amino group, a phosphonic acid group, and an aminomethylenephosphonic acid group, where n represents an integer from 1 to 20. Compound, general formula (III) R, R10R,.

(In the formula, R5 to R72 are each a hydrogen atom and a carbon number 1
~50 aliphatic hydrocarbon groups, C1-50 aromatic hydrocarbon groups, or some of the hydrogen atoms in these hydrocarbon groups are halogens or carboxyl groups.

n and m represent a hydrocarbon group substituted with a group selected from the group consisting of a hydroxyl group, a thiol group, an amino group, a phospho-6-phonic acid group, and an aminomethylenephosphonic acid group;
Each represents an integer from 1 to 20. ). Specific examples of these compounds include the following.

(lln-butylamine-N,N-bis(methylenephosphonic acid), (21n-nonylamine-N,N-bis(methylenephosphonic acid), (31hexamethylenediamine-N,N,N'N'-tetrakis( methylenephosphonic acid), (412-ethylhexylamine-N,N-
Bis(methylenephosphonic acid), (51benzylamine-N,N-bis(methylenephosphonic acid), (61m-
Xylene diamine = N, N, N', N'-tetrakis(methylenephosphonic acid) i7) (P-nonylbendi!L/)amine-N,N-bis(methylenephosphonic acid)
, (81dibenzylamine-N-methylenephosphonic acid, (QIN-carboxymethylnonylamine-N~methylenephosphonic acid, 0ON-carboxymethylamine-
N-methylenephosphonic acid, 0ON-methylcaptomethylnonylamine-N-methylenephosphonic acid, 0δN, N-
Bis(O-hydroxybenzyl)amine-N-methylenephosphonic acid, 031 Tyrosine-N,N-bis(methylenephosphonic acid), Q41 (3,5-dichloro-4-
Hydroxyphenyl)glycine-N,N-(methylene91) To obtain the aminomethylenephosphonic acid derivative used in the present invention, for example, a compound containing a - or secondary amino group (for example, P-aminomethylphenol) ) with chloromethylenephosphonic acid, or a compound containing a -class or secondary amino group with formalin and phosphorous acid in an aqueous mineral acid solution. Specific conditions at this time include, for example, a compound containing a -class or secondary amino group and phosphorous acid in a molar ratio of 1:0.8n to 2n (n is 0.8n to 2n).

It represents the number of hydrogen atoms directly connected to the nitrogen atom of a compound containing a -class or secondary amino group. ) and add 1 to this.
After adding ~36N mineral acid aqueous solution to make a homogeneous solution, 9
Heat to 0°C to 130°C.

Reflux and add formalin 0.8 n to 6 in this state.
n moles are added dropwise over 1 to 2 hours. Next, after completing the dripping,
Heating and refluxing may be continued for an additional 1 to 5 hours, after which water may be distilled off or the product may be passed through the mouth. In addition, when a compound containing a -class or secondary amino group also contains a phenolic hydroxyl group, when this compound is treated with phosphorous acid and formalin, the methylene of the amino group is At the same time as the phosphonication, the 0-position or P-position of the phenolic hydroxyl group also reacts with formalin, and the above-mentioned as, am, and as compounds can also be obtained.

In the present invention, any method may be used to bring the acidic aqueous solution containing a valuable metal into contact with the aminomethylene phosphonic acid derivative, but the aminomethylene phosphonic acid derivative is dissolved in an alkaline aqueous solution and the acidic aqueous solution containing the valuable metal is Preferably, it is added to an aqueous solution. The concentration of the aminomethylenephosphonic acid derivative at this time is 1, for example, 0.
1 to 30% by weight is suitable, and 1 to 10% by weight is particularly preferred.

As the alkaline aqueous solution, an aqueous solution of, for example, 0.1 to 5N sodium hydroxide, potassium hydroxide, ammonium hydroxide, etc. is preferable. In addition, the amount to be added is 1, for example, 0.0 IX by weight per valuable metal.
x-”-fold amount (W is aminomethyl αb
The molecular weight of the phosphonic acid derivative, n represents the number of phosphonic acid groups contained in one molecule. ) is appropriate.

0.02x ffi~0,05x-! ! L times the amount is preferred. Furthermore, the temperature when adding the additive η7 is suitably 1, for example, 10 to 70'C, particularly preferably 40 to 60'C, and 2 for 1 hour.
For example, within one hour is appropriate.

By doing so, a water-insoluble complex (a complex of a valuable metal and an aminomethyleneposboxylic acid derivative) is precipitated, and by carrying this precipitate to the mouth side, the valuable metal is recovered. Any method may be used to recover valuable metals from the separated complex, but it is preferable to add the alkali aqueous solution described above to this complex. The hydroxide is precipitated, and the valuable metal and the alkaline aqueous solution containing the aminomethylenephosphonic acid derivative can be separately separated and recovered by transporting this precipitate to the outlet side. Alternatively, the complex can be incinerated to recover the valuable metal as a valuable metal oxide.

Since the aminomethylenephosphonic acid derivative decomposes, it becomes impossible to reuse the aminomethylenephosphonic acid derivative, so it is not very preferable.

As the acidic aqueous solution containing the valuable metal targeted by the present invention, for example, an acidic aqueous solution containing indium is effective. Contains acid (concentration is approximately 0.1-0.5 N). In particular, an acidic aqueous solution containing indium may contain metal ions as coexisting metal ions.
nJt.

It is particularly effective when containing Cu, Pb, Cd, etc., and these metal ions hardly form a complex with the 1-amino methylene phosphonic acid derivative in the above mineral acid aqueous solution.

According to the present invention, valuable metals in an acidic aqueous solution can be recovered extremely efficiently.

Next, the present invention will be specifically explained using examples.

Reference Example 1 (Synthesis of aminomethylenephosphonic acid derivative) 1 mole of p-aminomethylphenol, 2 moles of phosphorous acid, and 6 moles of formalin were reacted in 6N salt 11 at 13-120°C for 6 hours (p- A formalin condensate of hydroxybenzyl)amine-N,N-bis(methylenephosphonic acid) was obtained.

Reference Example 2 (Synthesis of aminomethylenephosphonic acid derivative) After reacting 1 mole of diethylenetriamine, 1 mole of 2.6 dimethylphenol, and 1 mole of formalin at 70°C for 2 hours, 6N hydrochloric acid was added to make an acidic solution. , further added 2 moles of phosphorous acid and 4 moles of formalin, and heated to 4 at 120°C.
The reaction was carried out for a period of time to obtain the compound represented by (II).

Reference Example 3 (Synthesis of aminomethylenephosphonic acid derivative) 1 mole of n-nonylamine, 1 mole of phosphorous acid, and 2 moles of formalin were reacted in 6N hydrochloric acid at 120°C for 2 hours to form n-nonylamine-N,N. -bismethylenephosphonic acid) was obtained.

Example 1 Reference example 1. 2. Obtained in 3. Mix 10 g of each aminomethylene phosphonic acid derivative and 4 g of caustic soda,
Three types of aminomethylenephosphonic acid-containing aqueous solutions were prepared by adding water to make 100 cc.

This aqueous solution was added to A (Reference Example 1), B (Reference Example 2), and C.
(Reference Example 3)

Next, if 1100PP of In is contained and other coexisting metal ions, T, Zn50 g/j! , Cd 1
0 g/j! .

Pb, 0.1g/j', CuO, 2g/
Contains I, FeO, 5g/1, and H,
Aqueous solutions containing 10 g/l of SO were prepared from the respective metal sulfates and concentrated sulfuric acid.

This aqueous solution is designated as D.

Next, 10cc of each of the above A, B, and C solutions were added separately to this D solution IIl. A pale yellow precipitate formed the moment it was added, and in this state it was heated to 60℃ for 30 minutes with gentle stirring.
Processed for minutes. After that, the precipitate was separated by passing through 9 mouths.
The In concentration of the oral fluid was measured by atomic absorption spectrometry.

As a result, in the case of liquid A, it was 2.5 ppI+l, in the case of liquid B, it was 5 ppm, and in the case of liquid C, it was 6.3 ppm.

It is clear that In is efficiently separated from liquid C.

On the other hand, the separated precipitate was washed with water and air-dried, and then 10 cc of IN sodium hydroxide solution was added thereto, and a precipitate of indium hydroxide was formed. By separating this precipitate by filtration, it was possible to separately recover In and solutions A, B, and C (aqueous solutions of aminomethylenephosphonic acid derivatives).

In the case of A, the amount of In recovered at this time was 9711 g.

In the case of B, 95mg, in the case of C, 93g, which is 10
The recovery rate was close to 0%. One more recovered A, B,
Liquid C was recyclable.

Example 2 Contains 50 ppm of In and 100 g/j of Zn as other coexisting metal ions! , Cu 1
A solution containing 5 g/l of HCl and 5 g/l of HCI was prepared from the hydrochloride of each metal and concentrated hydrochloric acid.

This aqueous solution is designated as E.

Next, A and B containing the aminomethylenephosphonic acid derivative obtained in Example 1 are added to this E solution 11.

5 cc of Solution C was added to each separately. Thereafter, the same operation as in Example 1 was carried out, and the In concentration of the first sip was measured by atomic absorption spectrometry.

As a result, for liquid A, it was 1.2 ppm, for liquid B, it was 2 ppsI, and for liquid C, it was 3 ppm.
It is clear that <In is efficiently separated from both liquids and C.

On the other hand, the two separated precipitates were subjected to the same operation as in Example 1, and In and liquids A, B, and C could be recovered separately.

In the case of A, the In recovered at this time was 48B.

In the case of B, 48 mg, in the case of C, 47 mg, which is about 10
The recovery rate was close to 0%. In addition, 8 recovered A, B,
Liquid C was recyclable.

Patent applicant Unitika Co., Ltd. 17- Procedural amendment (method) % formula % 1. Indication of the case Japanese Patent Application No. 1983-61619 2. Name of the invention Law for the recovery of valuable metals 3. Person making the amendment Related Patent Applicant Address 1-5o Higashihonmachi, Amagasaki City Address 541 Address 4-68 Kitakuobe-cho, Higashi-ku, Osaka Name
Unitika Co., Ltd. Patent Department Telephone: Di281 + 5258 (Dial-in)
4. Date of amendment order: July 9, 1982 (Shipping date: July 27, 1982) 5
, Detailed Description of the Invention of the Specification Subject to Amendment II (Pages 8 and 9 of the Specification) 6, Contents of the Amendment Pages 8 and 9 of the Specification [Engraving of the Specification (no change in content) ] is attached as attached.

Claims (1)

[Claims] (11. A method for recovering valuable metals, which comprises bringing an acidic aqueous solution containing a valuable metal into contact with an aminomethylene sulfonic acid rust conductor. (2) Scope of Claims, in which the valuable metal is indium. Collection method described in paragraph 1., 3) A32. 76 oxic acid derivatives 3 general. (1) (In the formula, R5 to R4 are each a hydrogen atom and a carbon number of 1 to 5
0 aliphatic hydrocarbon group, aromatic hydrocarbon group having 1 to 5 carbon atoms, or some of the hydrogen atoms in these hydrocarbon groups are halogen, carboxyl group, hydroxyl group, thiol group,
Represents a hydrocarbon group substituted with a group selected from the group consisting of an amino group, a phosphonic acid group, and an aminomethylenephosphonic acid group. ) Claim 1 or 2 is a compound represented by
Collection method described in section. (4) The aminomethylene phosphonic acid derivative has the general formula () (wherein R6 to R6 are each a hydrogen atom and a carbon number of 1 to 5
0 aliphatic hydrocarbon group, aromatic hydrocarbon group having 1 to 50 carbon atoms, or a portion of water 11M molecules in these hydrocarbon groups is halogen, carboxyl group, hydroxyl group, thiol group, amino group, phosphonic acid and n represents an integer of 1 to 20. ) The recovery method according to claim 1 or 2, which is a compound represented by: (5) The aminomethylene phosphonic acid derivative has the general formula (I
II) R9R7OR+2 (In the formula, R1 to R52 are each a hydrogen atom and a carbon number of 1 to
50 aliphatic hydrocarbon groups, aromatic hydrocarbon groups having 1 to 50 carbon atoms, or some of the hydrogen atoms in these hydrocarbon groups are halogens, carboxyl groups, hydroxyl groups, thiol groups, amino groups, phosphonic acid groups , represents a hydrocarbon group substituted with a group selected from the group consisting of aminomethylenephosphonic acid groups, and n and product each represent an integer from 1 to 20. ) Claim 1 or 2 is a compound represented by
Collection method described in section.