JPS6033380A - Purification of lead electrolytic process liquid - Google Patents

Abstract

PURPOSE:To remove Bi and Sb in a treating liquid with high efficiency, by bringing a lead electrolytic process liquid containing impurity ions into contact with a chelating ion exchange resin. CONSTITUTION:A process liquid, which is used in the electrolytic refining of lead and contains a Pb-ion and a Bi-ion and a Sb-ion as impurity ions, is brought into contact with a chelating ion exchange resin having an amino carboxylic acid group. By this treatment, Bi and Sb are adsorbed with the chelate resin and the purified treating liquid is supplied to a lead electrolytic process. The chelate resin having Bi and Sb adsorbed therewith is regenerated by using hydrochloric acid to elute Bi and Sb while the regenerated treating liquid is reused. By this purifying method, the Bi-concn. in an electrolyte is reduced and high purity lead can be prepared.

Description

[Detailed description of the invention] The present invention relates to a method for purifying a lead electrolysis process solution.

More specifically, the present invention includes a lead electrolytic process solution, that is, a lead electrolytic refining method, and processes that are repeated in such an electrolytic solution. The present invention relates to a method for effectively removing lead electrolytic process liquid.

Current methods of producing lead from lead raw materials include the blast furnace method,
Electric furnace method, IBP method, etc. are used.

The lead produced by these methods contains gold, silver, and
It contains a certain amount of valuable metals or impurities such as copper, bismuth, tin, arsenic, and antimony, and is called crude lead. Crude lead is purified in order to remove impurities and recover valuable metals from the crude lead, and the refining methods are broadly divided into dry methods and wet methods. Although the dry method is said to have a low refining cost, it is difficult to separate bismuth, so the wet method is the mainstream in Japan.

Electrolytic refining is carried out using a wet method typified by the Benz electrolysis method using silica-fluoric acid as an electrolyte, an all-crude lead anode, and electrolytic lead as a cathode. During this electrolysis, the lead in the anode crude lead is eluted as oxidized lead, which is deposited on the cathode plate for purification, but the impurities in the crude lead such as gold, silver, copper, bismuth, Since antimony and arsenic are metals with an electrification series similar to that of lead, they are not eluted during electrolysis and remain as a spongy metal on the anode, forming anode slime. However,
During actual operations, a small amount of metals more harmful than lead may be eluted and deposited, or the anode slime may become entangled in the lead deposits.
It becomes an impurity in the product. In particular, it is difficult to remove even with Harris refining, which is commonly used to purify bismuth lead and electrolytic lead, and it is a major impurity in refined lead. Therefore, there is an urgent need to manage lead electrolysis to prevent bismuth from being mixed in.

The following six causes can be considered for the contamination of bismuth into refining vessels during lead electrolytic refining, depending on the person. The first reason is that when the bismuth content in the anode crude lead is high, some bismuth is eluted into the electrolyte and deposited on the cathode vessel.

As a preventive measure, it is necessary to adequately control the level of bismuth in the sediment and crude lead in the anode. Second, there are physical causes such as anode slime falling off and floating in the electrolyte and adhering to the cathode, or a short circuit between the anode and cathode resulting in anode slime adhering to the cathode. To prevent this, measures have been taken such as increasing the strength of the anode slime and shortening the anode slime. Third, due to the circulation of the anode slime cleaning solution, bismuth gets mixed into the electrolyte and is deposited on the cathode. For anode slime,
It contains precious metals such as gold and silver, as well as silicic acid and lead in the electrolyte, and recovering these is extremely important from an economic and pollution prevention perspective. Normally, the anode slime is scraped off from the anode, and a lot is filtered out.
It is separated into slime and slime i=o. The slime is sent to the collection process of gold, silver, bismuth, etc., and the slime 1
The solution and cleaning solution are circulated to the electrolytic cell after removing bismuth, which is the main ingredient, through operations such as solution electrolysis and replacement. From the viewpoint of increasing the recovery rate of silicic acid and lead, it is better to completely wash the anode slime, but it is not easy to sufficiently remove the bismuth eluted from the slime liquid by washing, and therefore the slime In addition, there was a problem in that the slime could not be sufficiently washed in the slime washing process. Therefore, it is desired to establish a technology that can efficiently remove slime F liquid, cleaning liquid, and bismasket.

According to the present invention, if a lead electrolytic process solution containing lead ions, bismuth ions and antimony ions as impurities is brought into contact with a chelating ion exchange resin, the chelating ion exchange resin a-these bismuth The ability to selectively adsorb and remove antimony from work/matage. According to the present invention, lead ions are mixed with bismuth ions as impurities and/or antimony ions are brought into contact with a chelating ion exchange resin containing antimony ions. A method for purifying a lead electrolytic process solution is provided, in which the resin is adsorbed and the process liquid is supplied to a lead electrolytic process.

It is advantageous to reuse the resin adsorbed with bismuth and /11 by elution and regeneration with hydrochloric acid and silicofluoric acid.

It can be the electrolyte itself in the lead electrolysis process o, the Hobetz type lead electrolysis, which can be purified by the method of the present invention, and the composition of such an electrolyte includes, for example, Pb40~so1.
iI7t, free H2SiF6'40-120 fl/l
.

Bi 4-6 m9/l. It can be a slime P solution or a cleaning solution, which is produced from a Betsu-type lead electrolytic knife containing a liquid to be treated, and its composition includes, for example, Pb15.
0-250g/1. Free H2SiF610-60g/1
°B can be 140 to 60 m9/l.

Chelating ion exchange resins that can be used in the method of the invention are known and commercially available. For example, a chelating ion exchange resin having a teminocarboxylic acid group as a functional group has a general formula (in the formula, Mn represents an alkali metal atom, 1 and 2 hydrogen atoms, 7 is R, and 21-ff is an alkali metal atom, respectively). is obtained by three-dimensionally crosslinking a compound representing a hydrogen atom or an alkyl group having 1 to 6 carbon atoms with phenol and an aldehyde, and according to JP-A-54-121241, it is obtained by three-dimensionally cross-linking a compound representing a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and according to JP-A-54-121241, it can be used in an acidic electrogalvanizing bath. It is known that it is possible to reduce the concentration of iron ions in. As a commercially available chelating ion exchange resin having an aminocarboxylic acid group that can be used to carry out the method of the present invention, Unicelec UR-10, UR manufactured by Unitika Co., Ltd. -20, UR-30, UR-40
and UR-50, Sumitomo Chemical Co., Ltd.'s S ε Chelate Q-10HR Okobi Mc~30, Orkat Co., Ltd.'s Amberlite RO-718, and Mitsubishi Chemical Industries, Ltd.'s Diaion 0R-10 is a chelating ion exchange resin with an aminocarbo/e group as a functional group, and a chelating ion exchange resin with an aminoalkyl phosphate group as a functional group, such as Unitika Co., Ltd.'s ■ UNISEREC UR-33EN T, Sumitomo Chemical Co., Ltd.'s ■Sumikylate ES-467, chelating ion exchange resins with polyamine basic functional groups, such as Sumitomo Chemical Co., Ltd.'s ■Sumikile) KA-, 850O- and ■Diaion 0R-20 manufactured by Mitsubishi Chemical Industries, Ltd. and chelating ion exchange resins having a pyridine group as a functional group, such as ■Sumichelate CR-2 manufactured by Sumitomo Chemical Industries, Ltd.
can also be used in carrying out the method of the invention.

In carrying out the present invention or carrying out the invention, it is convenient to fill a column with the chelating ion exchange resin and to pass the liquid to be treated, that is, the column in the lead electrolysis process. In most cases, the flow rate (sv) may be 1 to 15/Hr and the processing temperature may be ambient temperature. This operation [J: So, the chelating ion exchange resin hardly adsorbs the lead in the lead electrolytic process solution,
Selectively adsorbs bismuth and antimony. As a result, bismuth U2rn9/l in slime P liquid with standard composition
- Below, bismuth id 0.1 in an electrolyte of standard composition
It can be lowered to below mg/i. In this way, the treatment solution, which has been reduced by an antimolbel for every 7 inches of bismuth, is supplied to the lead electrolysis process.

The chelating ion exchange resin in one column that has adsorbed bismuth and/or acetic acid can be reused by elution and regeneration with hydrochloric acid or silicofluoric acid. For example, when 2-6N hydrochloric acid and 2-8N hydrochloric acid are passed through the same column at svi~6, the adsorbed bismuth/antimony is eluted and at the same time regenerated into resin. and is ready for reuse.

According to the method of the present invention, it is possible to perform sufficient cleaning in the slime cleaning step, which could not be done in the past to suppress the elution of bismuth, and improve the recovery rate of silicate-treated lead. At the same time, the bismuth concentration in the electrolyte decreases,
Bismuth levels in refining vessels are reduced, allowing the production of high-purity lead.

The present invention will be further explained below using specific examples.

Example 1 A chelating ion exchange resin having an aminoalkyl phosphoric acid group as a functional group was packed into a 500 mlf column, Uniselect UR-3300T manufactured by Unitika Co., Ltd.
Pb 205.9 f/l, Bi 58.
Slime r liquid contained in 8 m9/l' 5 L 'z I L
/Hr (SV -2), Pb 20
3.2? /LSBi 1.8 mvt treatment solution was obtained. This means that the removal rate of B1 was 97%.

1 bismuth in the column [6N hydrochloric acid 1 if
The eluent obtained by passing the solution at IL/Hr (SV = 2) and passing water at 21'z11/Hr (SV = 2) was obtained. /i, Bi 85.5 m9
/l'g%l (7) There are six T.

Example 2 Chelating ion exchange resin having an ε-nocarbo/acid group as a functional group, Uniselect UR from Unitika Co., Ltd.
-50, packed into a soame2 column, and put P into the column.
b2υ1. I Y/L, Bi 51.4m9/l, S
Slime iF contained in b169omg/l-8! i, 5
When the liquid was passed at t f O, 5A/Hr (sv=i), Pb 200.8? /l.

Bi O, 5 mq/l, Sb 667 m9/1 (7
) A treated solution was obtained.

The removal rate of B1 is 99%, which makes a difference of 1.

4N silicofluoric acid 11. ? 3) 0.5 L/Hr (SV
= 1), and water 21'g-11/Hr.
(Eluent obtained by passing water at 5V=21, PI) 2.
3ri/l, Di 72.3m9/l, Sb 140
4 m9/l k including'b (D 76 tsufv.

Example 6 A chelating ion exchange resin having an aminoalkyl phosphate group as a functional group was packed into a 500 ml Yunishelenc UR-3300T column manufactured by Unitika Co., Ltd., and Pb 65.5 fl/l was added to the column. Bi 4.2m
Li/L.

A lead electrolyte containing 685.4'j/l f of free H2SiF was passed through 5t' of lead electrolyte at 11-/Hr (SV=2) to adsorb bismuth in the solution onto the resin. When electrolytic refining was performed using the obtained treatment solution as an electrolytic solution and a crude lead anode containing B1 and R0.6%, electrolytic lead with a Bi level of 2 ppm or less could be obtained.

Comparative Example Slime P'ri containing BiB125O? , feed the lead plate into a suspension tank and leave it there day and night. The concentration of residual bismuth in the liquid was 7 tons (n 7 s mg). This means that the Bi substitution rate (removal rate) was about 70.

Applicant: Dowa Mining Co., Ltd.

Claims (1)

[Claims] (11) Lead ion is a lead electrolytic process solution that contains bismuth ion as an impurity and antimony ion as an impurity? A method for purifying a lead electrolysis process solution, which comprises contacting a chelate ion exchange resin to adsorb the bismuth and antimony on the resin, and supplying the treatment solution to a lead electrolysis process. (2) Contact the lead electrolytic process solution containing bismuth ions and/or antimony ions as impurities with a kechelating ion exchange resin to process the bismuth/antimony into the resin. Then, the treated solution is supplied to the lead electrolytic process, and the lead electrolytic process solution is eluted and regenerated with hydrochloric acid or a-silifluoric acid for reuse of the adsorbed resin. purification method.