CN103695967A

CN103695967A - Method for resisting lead ion depletion of lead electrolyte

Info

Publication number: CN103695967A
Application number: CN201310748322.XA
Authority: CN
Inventors: 谢志刚; 尹升; 周彪
Original assignee: HUNAN GUIYANG YINXING NONFERROUS SMELTING CO Ltd
Current assignee: HUNAN GUIYANG YINXING NONFERROUS SMELTING CO Ltd
Priority date: 2013-12-31
Filing date: 2013-12-31
Publication date: 2014-04-02

Abstract

The invention discloses a method for resisting lead ion depletion of lead electrolyte. The method comprises the following steps: (1) preparing a lead anode plate by 88-92 percent of Pb, less than 4-5 percent of Sb, less than 4-6 percent of Bi, less than 0.06 percent of Cu, less than 0.035 percent of Sn and less than 1.5 percent of As; (2) controlling the temperature of the electrolyte at 45 DEG C, wherein the flowing speed of the electrolyte is 25 L/min, the electrolysis density is 200-210 A/m<2>, and an additive and the species are not changed. The method is characterized in that the change of lead ions is controlled by adjusting an immersion area of an anode and a cathode in an electrolytic tank and a polar distance between an anode plate and a cathode plate. Due to the method, the lead ions in the lead electrolyte can be stably controlled within a reasonable range, so that the depletion of the lead electrolyte is avoided.

Description

A kind ofly overcome lead electrolytic solution lead ion dilution method

Technical field

The present invention relates to a kind of non-ferrous metal metallurgy method, relate in particular to the dilution method of lead ion in lead electrolytic solution.

Background technology

The lead bullion purity of lead bullion melting output is in 96%-99% scope, all the other 1%-4% are the impurity such as the rare metals such as precious metal gold and silver, selenium, tellurium and copper, nickel, selenium, antimony and bismuth, the value of the precious metal in lead bullion will surpass plumbous value sometimes, must extract, and impurity component is to plumbous malleability and corrosion stability generation harmful effect, must remove, therefore will carry out refining to lead bullion.

The refining of lead bullion has two kinds of pyrorefining and electrorefinings, the lead refinery of China and Japan generally adopts electrorefining, world other countries all adopt fire refining process, and pyrorefining equipment and technology is simple, and construction cost is lower, energy consumption is low, with short production cycle, its shortcoming is that process is numerous and diverse, and intermediate product is wide in variety, all need individual curing, metal recovery rate is lower; Electrorefining productivity is high, and metal straight yield is high, is easy to mechanize and automatization, can an output high purity lead bullion, but construction investment is large, and the production cycle is longer.

Lead bullion electrorefining, during electrolysis, take fluosilicic lead plumbate and silicofluoric acid as dielectric medium, under direct current effect, lead bullion is electrolyzed to produce to lead bullion, electrolytic lead refining technical process is removed most Cu, Sn, As in lead bullion by pyrorefining, the content of adjusting Sb, meets the needs of electrolytic process, and casts qualified positive plate and two sections of operations compositions of electrolysis.

1. pyrorefining, molten lead copper removal, the solubleness of copper in plumbous liquid, along with the reduction of temperature, reduce, in theory, when the temperature of plumbous liquid is 326 ℃, copper content is 0.06%, and during the high plumbous liquid cooling of cupric, copper is separated out with solid solution state, because proportion is more plumbous little, floats over plumbous liquid surface and is removed with scum silica frost form, in plumbous liquid, there are arsenic, antimony existence to be, can generate copper arsenide and antimony copper hard to tolerate, be conducive to the removal of copper, adopt after liquation decoppering, cupric does not still reach requirement, should further adopt and add sulphur copper removal; Because arsenic, tin are greater than the plumbous avidity to oxygen to the avidity of oxygen, therefore use plumbous oxide as oxygenant, with sheet alkali, as slag former, to be combined with the oxide compound of arsenic, tin, generation is insoluble to the scum silica frost of plumbous liquid and is dragged for.

2. electrolysis, during electrolysis, makes negative electrode with electrolysis lead flake, lead after decopper(ing) is made anode, carries out electrolysis, in silicofluoric acid and silicofluoric acid lead water solution under direct current effect, anodic oxygen changes into lead ion and enters solution, and on negative electrode, in solution, lead ion reduction is separated out: anode Pb → Pb ²⁺+ 2e negative electrode Pb ²⁺in+2e → Pb electrolytic process, the more plumbous negative metal of standard potential, as iron, zinc, tin, nickel, bore and wait electrochemical solution together with lead to enter solution, and the more plumbous positive metal of electropotential, as silver, gold, copper, arsenic, hoof etc. do not dissolve and form the anode sludge and are sunken to cell bottom, through some cycles, anode scrap returns to refining furnace melting, negative electrode is separated out plumbous through fusing eliminating minute tin, arsenic, after stilba matter, cast lead bullion, the anode sludge is used for reclaiming precious metal, in the electrolyzer that electrolysis is made at interior corrosion proof lined Steel Concrete, carry out, the major technique condition of plumbous electrolysis is: electrolytic solution total acid content 120-160 g/L, leaded 90-125 g/L, electrolysis temperature 32-45 ℃, current density 120-200A/m ², with polar moment 95mm, the leaded 99.98%-99.99% of lead bullion.

The electrolysis in electrolytic process of lead ion in lead electrolytic solution, to negative plate, makes the lead ion in electrolytic solution can not keep balance, needs regularly to add yellow lead powder in electrolytic solution and makes lead ion supplement.

Summary of the invention

The technical problem that will solve required for the present invention is to overcome the deficiency existing in existing electrolysis tech, proposes a kind of lead electrolytic solution lead ion dilution method that overcomes, and meets the demand that present lead metallurgy industry is produced.

The present invention is achieved in that a kind of lead electrolytic solution lead ion dilution method that overcomes, and comprises following step:

(1) chloride plate grade: Pb:88～92%, Sb:< 4～5%, and Bi:< 4～6%, and Cu:< 0.06%, and Sn:< 0.035%, and As:< 1.5%.

(2) control electrolyte temperature at 45 ℃, electrolyte flow speed: 25L/min, electrolysis density, 200～210A/ ㎡, additive and kind are constant.

(3) by the regulating YIN and YANG utmost point, the pole span between the immersion area regulating YIN and YANG pole plate in electrolyzer is controlled the variation of lead ion.

A kind of advantage that overcomes lead electrolytic solution lead ion dilution method of the present invention is: by this kind of method, can stablize within the lead ion of controlling in lead electrolytic solution remains on a rational scope, be unlikely to make lead electrolytic solution dilution.

Accompanying drawing explanation

Fig. 1 is positive plate when electrolyzer soaks area and changes, electrolytic solution Pb ²⁺change control table.

Fig. 2 is positive plate when soaking area polar distance changes, electrolytic solution Pb ²⁺change control table.

Embodiment

Below in conjunction with embodiment, explain in detail technical scheme provided by the present invention, but not as the restriction to the claims in the present invention protection domain.

In the following embodiments, the raw material adopting is the Ag positive plate that lead bullion is manufactured, chloride plate grade: Pb:88～92%, Sb:< 4～5%, Bi:< 4～6%, Cu:< 0.06%, Sn:< 0.035%, As:< 1.5%, control electrolyte temperature at 45 ℃, electrolyte flow speed: 25L/min, electrolysis density, 200～210A/ ㎡, additive and kind are constant, the variation that immersion area by adjustment anode in electrolyzer and the pole span between positive plate are controlled lead ion.

Claims

1. overcome a lead electrolytic solution lead ion dilution method, comprise following step:

(1) chloride plate grade: Pb:88～92%, Sb:< 4～5%, and Bi:< 4～6%, and Cu:< 0.06%, and Sn:< 0.035%, and As:< 1.5%; (2) control electrolyte temperature at 45 ℃, electrolyte flow speed: 25L/min, electrolysis density, 200～210A/ ㎡, additive and kind are constant; It is characterized in that: the pole span between the immersion area regulating YIN and YANG pole plate by the regulating YIN and YANG utmost point in electrolyzer is controlled the variation of lead ion.