JPS60128279A - Method for producing metallic copper and chlorine from cuprous chloride - Google Patents

Abstract

PURPOSE:To recover easily metallic copper and chlorine having high purity with high efficiency by supplying hydrochloric acid or an aq. slon. of metallic chloride to an anode chamber, supplying cuprous chloride (chlorinated complex) to a cathode chamber and electrodepositing metallic copper on the cathode. CONSTITUTION:Cuprous chloride is supplied to a cell 12 for forming chlorinated complex. The cuprous chloride is made into the chlorinated complex soln. of the cuprous chloride by hydrochloric acid or an aq. soln. of metallic chloride of univalent and bivalent ions in the catholyte from a route 13 or the similar aq. soln. supplied freshly from a route 15. Hydrochloric acid or the aq. soln. of metallic chloride is supplied to an anode chamber 2 and electrolysis is accomplished. The chlorinated complex of the cuprous chloride in a cathode chamber 3 is reduced by conduction of electricity and is electrodeposited in the form of metallic copper on the surface of a cathode 6. The hydrochloric acid and a part of metallic chloride formed in the chamber 3 is conducted to the chamber 2 and the balance is supplied to the cell 12. The chlorine ion generated in the chamber 2 is removed of electron and is discharged in the form of gaseous chlorine to the outside of the system.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing metallic copper and chlorine from cuprous chloride.

Conventionally, as a method for depositing electrolytic copper, metal is reduced and deposited on a cathode by electrolysis from a copper sulfate solution or a copper nitrate solution.

In conventional electrowinning methods such as this, the target product is limited to copper that is deposited on the cathode. ), and the anodic reaction cannot be used for anything of value, despite using a large amount of power. As a chemical method, there is a substitution method that utilizes ionization tendency, but the purity of the precipitated copper is poor and a purification process is necessary.As a result of repeated research and tests, the present invention was completed.

That is, in the present invention, an aqueous solution of hydrochloric acid or a metal chloride is supplied to the anode chamber of an electrolytic cell which is divided into an anode chamber and a cathode chamber via a cation exchange membrane, and cuprous chloride is previously added to the cathode chamber. Supplying a chlorinated complex of cuprous chloride obtained by reacting with ions, or/and chlorinating in a state where chlorine ions are present in the cathode chamber at a concentration sufficient to at least form a cuprous chloride chlorinated complex. This is a method for producing metallic copper and chlorine from cuprous chloride, which is characterized by supplying cuprous chloride, generating chlorine gas from the anode by electrolysis, and electrodepositing metallic copper on the cathode. An example will be described in detail by quoting.

FIG. 1 is an explanatory diagram showing an example of the method of the present invention.

In this figure, 1 is an electrolytic cell main body composed of unit electrolytic cells, 2 is an anode chamber, 3 is a cathode chamber, and the anode chamber has an anode 5.
However, a cathode 6 is provided in the cathode chamber, and these two electrode chambers are partitioned by a cation exchange membrane 4.

In the Kameru electrolytic cell, cuprous chloride is supplied to the cuprous chloride chlorination complex generation tank 12 through path 14, and through path 13.
Hydrochloric acid or an aqueous solution of monovalent or divalent ions of metal chloride in the catholyte supplied via route 15 or/and hydrochloric acid or an aqueous solution of monovalent or divalent ion of metal chloride supplied separately via route 15 It is sent to the cathode chamber 3 via route 7 as a chlorinated copper complex solution. Further, hydrochloric acid or a metal chloride aqueous solution is supplied to the anode chamber 2 through a circulation path 9 (the role of this circulation path will be described later) and electrolyzed.

That is, the cuprous chloride chlorinated complex in the cathode chamber 3 is reduced by energization in the electrolytic cell, and is electrodeposited on the surface of the cathode 6 as metallic copper.

On the other hand, in the anode chamber 2, cations (hydrogen ions or metal ions of the corresponding metal chloride) are present due to dissociation of hydrochloric acid or an aqueous metal chloride solution, and these pass through the cation exchange membrane and enter the cathode chamber 3 together with coordinated water. , and generates hydrochloric acid or metal chloride with chlorine ions in the cathode chamber.

A portion of the hydrochloric acid or metal chloride thus generated is introduced into the anode chamber 2 through the circulation path 9, as described above, together with free hydrochloric acid, etc. contained in the chlorinated complex solution of cuprous chloride. , are reused as feedstock for the anode chamber, and the remainder is supplied to the production tank 12 via the route 13 for preparing a chlorinated complex of cuprous chloride. Further, the path 16 is a water supply port for concentration adjustment.

Anode chamber? In this case, the generated chlorine ions are electrophilic and are discharged to the outside of the yarn from the path 10 as chlorine gas.

The chlorinated complex of cuprous chloride supplied to the cathode chamber 3 is 0.0
A concentration of 1 mol/l to 2.2 mol/l is sufficient, but is not particularly limited in the present invention.

When the concentration of monovalent copper ions in the cathode chamber is low, one or more of hydrochloric acid or metal chlorides may be added as an electrolyte to reduce electrolyte resistance.

In this case, the hydrogen ion concentration (pH) is preferably 4 or less. The amount of cations transferred from the anode chamber to the cathode chamber through the cation exchange membrane is determined by the passing current together with coordinated water.

The concentration of hydrochloric acid or metal chloride aqueous solution supplied to the anode chamber is 0.
．． A range of 5 moI/l to 5 moI/l is preferable, and these raw materials are most preferably hydrochloric acid or metal chloride after copper removal in the cathode chamber as described above, but the present invention is not necessarily limited to this. Alternatively, part or all of the liquid may be freshly drawn and supplied.

In the present invention, instead of supplying the cuprous chloride chlorinated complex to one cathode chamber, a slurry liquid of raw material cuprous chloride may be directly supplied to the cathode chamber. However, in this case, it is necessary that the cuprous chloride solution supplied has at least a sufficient concentration of chlorine ions to form a chlorinated complex of cuprous chloride in the cathode chamber. This can be achieved by adding the ions directly to the cathode compartment concurrently with the cuprous chloride feed, or by adding them into the cuprous chloride slurry liquid prior to feeding to the cathode compartment.

Furthermore, in the method of the present invention, the means for supplying the previously prepared chlorinated complex of cuprous chloride to the cathode chamber and the means for directly supplying the cuprous chloride solution to the cathode chamber may be used in combination. .

The cationic species of hydrochloric acid and metal chlorides supplied to the anode chamber, the cathode chamber, and the complex formation of cuprous chloride outside the electrolytic cell are H'',
I, i'', Na'', K'', Mg, Ca, Sr.

Ba, specifically HCt, NaCL, 'KCL
.

MgC1-2, CaCl2, 5rcL2. BaC62, etc. can be mentioned, and the concentration of all of them is 0 as mentioned above.
．． A range of 5 mol/l to 5 mol/t is preferred.

The waxy acid or salt water discharged from the anode chamber is 0.5 mo
1/ or more is sufficient, and economically it is preferable to increase the decomposition rate.

The current density of the electrolytic cell is 1 A/dm' to 30 A/d.
The range of m2 is preferable, but if considering the electrolytic cell capacity, electrolysis time, copper precipitation form, etc., it is 5A/dm2 to 20A/d.
m2 is particularly desirable.

Regarding the cation exchange membrane used in the electrolytic reaction, ordinary cation exchange membranes such as carboxylic acid membranes and sulfonic acid membranes can be used. An exchange membrane with a

If a weak acid type cation exchange membrane is used, the resistance of the membrane increases and the sliding voltage tends to increase, which is not very preferable.

Even if there is a mixture, the damage to the exchange membrane is small. However, as polyvalent cations, metal ions having a deposition potential nobler than copper are not very preferable for the purpose of obtaining pure copper.

Regarding the material of the anode, graphite, magnetite, peroxide, or a dimensionally stable insoluble metal anode coated with a platinum group metal on titanium is used.

Regarding the material of the cathode, since copper is deposited at a higher potential than hydrogen generation, it is possible to perform electrolysis at room temperature even in an acidic solution. Corrosion of the cathode is not a problem.

According to the method of the present invention described above, high purity metallic copper and chlorine can be easily recovered with high efficiency by electrolytically treating a solution mainly containing cuprous chloride in an electrolytic cell using a cation exchange membrane. It is something.

Furthermore, by carrying out the present invention, not only can the same amount of metallic copper be produced with half the power of conventional copper electrowinning using divalent copper salts, but also the amount of metal copper produced from the anode can be reduced compared to copper sulfate or copper nitrate electrowinning. It is a very efficient and economical method as it produces useful chlorine instead of oxygen generation or copper dissolution.

The present invention will be explained below with reference to Examples.

Example 1 Electrolysis was carried out as follows using the electrolytic cell structure and attached piping system shown in FIG.

That is, a cuprous chloride slurry liquid is fed into the chlorinated complex generation tank 12 of cuprous chloride through the route 14, and is reacted with hydrochloric acid to obtain a liquid mainly containing a chlorinated complex of cuprous chloride. It was supplied to the cathode chamber 3 of the electrolytic cell through path 7. The hydrochloric acid used in the generation tank 12 is the hydrochloric acid from the route 13 and the newly supplied amount from the route 15.

Hydrochloric acid was supplied to the anode chamber through path 9, and a liquid containing unreacted hydrochloric acid was discharged through path 11.

In this case, the specifications for feeding and discharging each part, operating conditions, etc. were as shown in Table 1.

Table 1 Meikosai's engraving (Contents 1ζ No changes) The results are shown in Table 2 below.

Second table 1! ij lli book a-(no change in content) Example 2 In Example 1, the chlorinated complex generation tank 12 was not newly replenished with hydrochloric acid, and sodium chloride from the cathode chamber was supplied via routes 8 and 13. The solution was combined with the cuprous chloride slurry in the above-mentioned generation tank, and a sodium chloride solution was separately introduced into the cathode chamber for electrolysis.

In this case, the specifications of the feeding and discharging of each part, the electrolytic operation conditions, etc. were as shown in Table 3.

Table 3 Detailed information / Outline (no change in content) The results are shown in Table 4.

Table 4

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram showing an example of the non-inventive method. 1. Electrolytic cell body, 2. Anode chamber, 3. Cathode chamber, 4.. Cation exchange membrane. Name of patent applicant Tsurumi Soda Co., Ltd. Procedural amendment (method) April 1980 φ Date Commissioner of the Patent Office Kazuo Wakasugi 1, Indication of case 1988 Patent Application No. 236415 3
, and the person making the corrections. (No change in content)

Claims (1)

[Claims] Hydrochloric acid or an aqueous solution of a metal chloride is supplied to the anode chamber of an electrolytic cell divided into an anode chamber and a cathode chamber via a 1S cation exchange membrane, and cuprous chloride is previously reacted with chlorine ions to the cathode chamber. Either supplying the chlorinated complex solution of cuprous chloride or/and supplying the chlorinated complex solution of cuprous chloride, or/and supplying cuprous chloride with chlorine ions present in the cathode chamber at a concentration sufficient to form the cuprous chloride chlorinated complex. A method for producing metallic copper and chlorine from a cuprous chloride solution, which comprises supplying copper, generating chlorine gas from an anode by electrolysis, and electrodepositing metallic copper on a cathode.