CN1094762A

CN1094762A - One-step Zn smelting technique by suspension electrolysis of ZnS

Info

Publication number: CN1094762A
Application number: CN93105469A
Authority: CN
Inventors: 樊远鉴; 张元福; 王绍和; 陈家蓉
Original assignee: Individual
Current assignee: Individual
Priority date: 1993-05-06
Filing date: 1993-05-06
Publication date: 1994-11-09
Anticipated expiration: 2013-05-06
Also published as: CN1034958C

Abstract

One step of zinc sulfide ore suspension electrolysis smelting technique belongs to chemistry and field of metallurgy, it is characterized in that leaching zinc sulfide ore also simultaneously at the anodic dissolution that contain zinc chloride of cathode compartment electrodeposition after purifying at the nascent state chlorine that the suspension electrolysis groove anolyte compartment of special construction produces with the chloride solution electrolysis, control suitable condition, produce GB470-83 one-level or secondary electrolytic zinc and zinc powder from zinc sulfide ore economically.Production Flow Chart is short, reduced investment, and environmentally safe, industrial scale is changeable, and cost is low.

The present invention is applicable to various zinc sulfide ores.

Description

One-step Zn smelting technique by suspension electrolysis of ZnS

The present invention relates to a kind of metallurgy and produce the method for metallic zinc, and relate to the method that a kind of hydrometallurgy is produced metallic zinc, be applicable to various chemistry and field of metallurgy.

The method of introducing in " heavy metal metallurgy " is as one of prior art of the present invention.The prior art is industrially to become zinc baking sand (ZnO), sulphur to make sulfuric acid through the pyrogenic process roasting zinc sulfide concentrates usually; Zinc baking sand be equipped with again the distillation of reduction coal fire method for behind the crude zinc again rectifying be finished product zinc; Or after zinc baking sand leached with dilute sulphuric acid, the purified solution electrolysis that obtains through a series of removal of impurity operations again, wet production is an electrolytic zinc, the shortcoming of the pyrometallurgy of zinc method of this technology is: operation is long, energy consumption height, SO ₂Environmental pollution consumes a large amount of refractory materialss, and labour intensity is big; The shortcoming of the zinc hydrometallurgy method of this technology is: SO is arranged equally ₂Environmental pollution, the relieving haperacidity investment is big, and sulfuric acid storage problem, transportation problem and leaching system are huge, anode precipitated oxygen during electrolysis, the workshop acid mist is big, and bath voltage height, current consumption reach weakness such as first investment is big greatly.Generated pyrometallurgical smelting when pyrogenic process and hydrometallurgy zinc high-temperature roasting zinc sulfide concentrates and be difficult to reduction, the zinc ferrite that hydrometallurgy is difficult to leach has increased difficulty of producing and the rate of recovery that has reduced zinc.

" non-ferrous metal " magazine 1987 the 5th interim " sulphide ores suspension electrolysis new technology " literary composition is as two of prior art.Be to be the porous polypropylene filter cloth by diaphragm for electrolytic cell in the prior art, its shortcoming is: (1) only plays the effect of separation ore pulp; (2) leach liquor cost height; (3) leaching yield of zinc is low, and technical process is long.

The purpose of this invention is to provide a kind of both pollution-freely, can obtain high-quality product again, flow process is short, the production method that cost is low.

Feature of the present invention is to adopt the electrolytic tank electrolysis chlorine of special construction to handle zinc sulfide ore, go on foot and finish by suspension leaching, electrolysis, purification one, be easy to the wet production process of industrial implementation, control suitable condition and reach effectively, produce the purpose of metallic zinc economically.

The present invention is applicable to from zinc sulfide ore that contains certain impurity or zinc sulfide concentrates and produces metallic zinc.Relevant constituent content is advisable in following scope: Zn＞40%, Pb≤2%, Fe≤8%; Lower for containing Zn, contain the higher raw material of Pb, Fe and also can use, just production process is complicated, and cost raises.

Among the present invention:

Suspension chlorination leaching and electrolysis are to carry out in the anolyte compartment of the built-in ion-exchange former of anti-chlorine corrosion and cathode compartment, and suspension electrolysis groove material is a furans glass reinforced plastic; Can have the compound groove and the series of a plurality of the anode chamber and the cathode chamber with suspension electrolysis groove set of monomers is synthetic according to industrial scale, each compound trough rim is equipped with acidproof jet flow sand pump and stirs anolyte compartment's ore pulp, anolyte and expand slurry and use steam heating, and its equipment is as shown in Figure 1.Anode is manufactured with aluminium sheet or titanium plate with graphite, negative electrode.

Suspension electrolysis groove structure is made up of furans glass reinforced plastic cell body (1), liquid-inlet pipe (2), film frame (3), ion-exchange former (4), jet flow agitator (5), upflow tube (6), anolyte compartment (7), cathode compartment (8).

Zinc sulfide concentrates is milled to below-100 orders in advance, according to the difference of raw material, controls [the Cl that consists of of leach liquor ^-] 2-5mol, HCl0.5～2N, Yu Weishui, liquid-solid ratio is 6～12: 1.70～100 ℃ of temperature, current density 300～1000A/m ², extraction time 4～8 hours.Meanwhile put into negative plate at cathode compartment and inject purification back liquid and circulation, control electrolytic solution contains Zn40～100g/L, acidity PH1～4, and temperature is carried out electrowinning zinc for 50～70 ℃.

After process is carried out one-period, anolyte and ore pulp are emitted clarification filtration, filter residue hot water washing and filtering, filter waste send and put forward the sulphur operation, diafiltration liquid retrieval system; Supernatant liquor deironing, arsenic, antimony, copper, cadmium, nickel, cobalt etc. are purified liquid and send and make cloudy liquid next time, and it is mining that electrolysis waste solution send the next cycle positive column to soak.The suspension electrolysis zinc leaching rate can reach 95%, cathode efficiency is greater than 93%, direct power consumption 800～950kwh/t, and the metallic zinc product meets GB470～83 1～2 grade zinc standard.

The present invention has following six advantages compared with the prior art:

1. technical process is simple, and zinc leaches and electrodeposition carries out in same equipment, has made full use of the dipolar electric energy of anode and cathode, save energy, low equipment investment.

2. the regeneration of chlorizating agent is to carry out simultaneously with electrolysis, need not increase operation and equipment.

3. zinc sulfide concentrates does not need roasting relieving haperacidity, has shortened living preface operation, has saved investment, has avoided SO ₂To the pollution of environment, can not resemble FeCl yet ₃Make chlorizating agent and bring too much iron ion like that into, increase the trouble of regeneration and deironing.

4. adopt the present invention to produce metallic zinc, the smelting recovery of zinc＞92% is higher than conventional production method, and product zinc reaches more than the GB470-83 secondary zinc.

5. industrial scale is changeable, to the concentrate wide adaptability.

6. main raw material(s) economy is cheap, consumes to lack, and production cost is low.

Example 1. is got zinc sulfide concentrates 90 grams that contain Zn50%, and granularity-200 order accounts for 39.8%, and all the other are less than 100 orders, with containing [Cl ^-] 4mol, HCl1.5mol, [Fe ⁺⁺⁺] leach liquor 1 lifting of 3.24g/L goes into suspension electrolysis groove anolyte compartment, control extraction temperature 80 ℃ ± 5, D _k700A/m ², the anolyte compartment puts into graphite anode, and cathode compartment is put into titanium negative plate and is stirred to tremble and leach and electrolysis, and cathode compartment electrolytic solution is the ZnCl through purifying ₂Solution, control utmost point chamber PH1～4,50～70 ℃ of catholyte electrolysis temperatures, and recycle.Suspension electrolysis leached after 5 hours, with anolyte and soak slag and emit clarification, filtration, filtrate and send purification, the filter residue hot water washing and filtering, oven dry send analysis, negative electrode to fold zinc through washing and drying, and quality can reach GB470-83 1～2 grade standard, contain Zn99.97%, slag contains zinc 4.1%.Zn leaching yield 96.1%.

Example 2. usefulness contain zinc sulfide ore 100 gram of Zn48.6%, are milled to-100 orders, operate to stir equally with example 1 with one liter of leach liquor and soak, wherein leach liquor [Cl ^-] 5 mol, HCl 1N[Fe ⁺⁺⁺] 5g/L, 70 ℃ of extraction temperatures of control, D _K550A/m ², cathodic area electrolytic solution contains Zn90g/L, PH1～4, and 55 ℃ of electrolysis temperatures suspend and leach electrolysis after 7 hours, and adopt with example 1 and handle the anode chamber and the cathode chamber product with quadrat method, Zn leaching yield 95.55%, slag contains zinc 4.5%, and product zinc contains zinc 99.98%.

Claims

1, a kind of hydrometallurgy is produced the method for metallic zinc, is gone on foot by direct electrolysis one and finishes, and it is characterized in that:

I) zinc sulfide concentrates directly enters the electrolyzer anode chamber that chloride solution is housed and is leached generation slag and leach liquor by the electrolytic chlorine that the chloride solution electrolysis produces;

Ii) the leach liquor of anolyte compartment is entered the electric tank cathode chamber after purifying, electrodeposition produce electrolysis zinc and waste electrolyte;

Iii) the waste electrolyte of cathode compartment generation will reenter the anolyte compartment as chloride solution and repeat above-mentioned steps.

2, produce the method for metallic zinc for the described hydrometallurgy of claim 1, it is characterized in that with electrolytic chlorine as the chlorizating agent that leaches zinc sulfide ore.

3, produce the method for metallic zinc for the described hydrometallurgy of claim 1, it is characterized in that consisting of of leaching agent (or waste electrolyte): " Cl ^-" 2～5mol, " HCl " 0.5～2N, Yu Weishui, liquid-solid ratio 6～12: 1,70～100 ℃ of temperature, current density 300～1000A/M ², 4～8 hours time.

4, a kind of claim 1,2,3 described hydrometallurgys of realizing are produced the electrolyzer of metallic zinc, it is characterized in that:

ⅰ) adopt the ion-exchange former to be isolated between the anolyte compartment of described electrolyzer and the cathode compartment;

ⅱ) be provided with the jet flow agitator bottom the described electrolyzer anode chamber;

ⅲ) the anode graphite of described electrolyzer, negative electrode is with aluminium sheet or titanium plate.