CN104562083A - Zinc hydrometallurgical process capable of reducing acid-zinc ratio of electrolyte under high manganese condition - Google Patents

Zinc hydrometallurgical process capable of reducing acid-zinc ratio of electrolyte under high manganese condition Download PDF

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Publication number
CN104562083A
CN104562083A CN201510042747.8A CN201510042747A CN104562083A CN 104562083 A CN104562083 A CN 104562083A CN 201510042747 A CN201510042747 A CN 201510042747A CN 104562083 A CN104562083 A CN 104562083A
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zinc
electrolysis
cycle liquid
ion concentration
under high
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CN104562083B (en
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王新文
段小维
刘亚雄
段宏志
杨斌
周新春
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Baiyin Nonferrous Group Co Ltd
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Baiyin Nonferrous Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06—Operating or servicing

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)

Abstract

The invention provides a zinc hydrometallurgical process capable of reducing the acid-zinc ratio of an electrolyte under a high manganese condition and aims at solving the problem of difficult production control during production due to large concentration change range of Mn<2+> ions in the circulating electrolyte in the prior art. According to the zinc hydrometallurgical process, in terms of different polar distances of a zinc electrodeposition electrolytic cell, the acid-zinc ratio of the circulating electrolyte is reduced according to different concentrations of the Mn<2+> ions in the electrolyte so as to ensure normal production; as a result, the normal production can be well controlled and the influence of different concentrations of the Mn<2+> ions on the electrolytic electrodeposition process at two polar distances is eliminated; in case of different polar distances, the method of reducing the acid-zinc ratio according to high and low concentrations of the Mn<2+> ions in the circulating electrolyte is adopted to reduce the harm of the concentration fluctuation of the Mn<2+> ions on zinc electrodeposition production to the utmost extent; and as a result, the negative plate burning and acid leakage accidents are reduced and the production is stabilized.

Description

The zinc wet method smelting process of electrolytic solution acid zinc ratio is reduced under high manganese condition
Technical field
The present invention relates to zinc hydrometallurgy field, under being specifically related to a kind of high manganese condition, reduce the zinc wet method smelting process of electrolytic solution acid zinc ratio.
Background technology
In Zinc Hydrometallurgy Process, electrolytic deposition process is a very important production link, and its General Principle and process are by the Zn in electrolysis cycle liquid 2+ionic adsorption is on negative electrode, and output zinc metal, anode release electronics also releases oxygen.In this course, the Mn in electrolytic solution 2+the effect of ion on positive plate is mainly:
2MnSO 4+3H 2O+5/2O 2=2HMnO 4+2H 2SO 4
2HMnO 4+3MnSO 4+2H 2O=5MnO 2+3H 2SO 4
And in this course, Mn 2+ion serves very crucial effect, namely in electrolysis cycle liquid, produces H 2sO 4; Discharge oxygen, the Manganse Dioxide of generation is solid matter, is adsorbed on positive plate or with circulation fluid and drops to bottom of electrolytic tank simultaneously.Therefore Zn in circulation fluid in electrolytic deposition process 2+ionic concn general control between 50-75g/l, output metallic zinc on negative electrode.Mn in circulation fluid 2+ion height is same produces impact greatly to electrolytic deposition process, requires Mn in general electrolytic solution 2+ionic concn between 2-8 g/l, Mn in electrolysis mixed solution 2+ion is too high and too lowly all exert an adverse impact to electrolysis, works as Mn 2+during ion < 2g/l or > 8g/l, all can produce impact greatly to electrodeposition, reduce unit dc consumption, even produce defective cathode zinc.
Since nearly ten years, along with the change of zinc ore concentrate impurity composition, cause Mn in zinc hydrometallurgy electrolysis cycle liquid accordingly 2+ion alters a great deal, and can rise to 25g/l very soon from 2 g/l, variation range is big, causes the difficulty being difficult to tackle: electrolytic bath temperature is elevated to 40-48 DEG C to electrolysis production; Cathode zinc quality declines, and leadedly often exceeds standard, and beam cathode zinc is leaded all below 0.003%, and under high manganese condition, leadedly reaches 0.005-0.010%, and then causes cathode zinc quality not reach zero level product; Cathode zinc output, by 340 tons/day, drops to 280-300 tons/days; Unit dc consumption rises to 3150KWh/t by 3050KWh/t, and current efficiency drops to about 88.0% by 91.0%; Bottom of electrolytic tank deposited silicon dioxide manganese increases, and circulation of elecrolyte worsens; Pipeline crystallization increases, and circular flow reduces; Unit dc consumption increases, and cathode zinc output reduces, in a word, and groove face difficult management.
Summary of the invention
The zinc wet method smelting process of electrolytic solution acid zinc ratio is reduced, to solve electrolysis cycle liquid Mn in prior art under the object of this invention is to provide a kind of high manganese condition 2+ionic concn variation range is large, causes production control to be difficult to the problem tackled when producing.
For this reason, the present invention adopts following technical scheme: the zinc wet method smelting process reducing electrolytic solution acid zinc ratio under a kind of high manganese condition, different from pole span at Zinc electrolysis electrolyzer, according to electrolytic solution Mn 2+ionic concn is different and reduce electrolysis cycle liquid acid zinc than ensureing that production is normal.
Further, be in 75mm electrolyzer at same pole span, electrolytic solution Mn 2+ionic concn, when 10-12g/l, controls sour zinc than being 2.8-3.0:1; Electrolytic solution manganese ion concentration, when 12-15g/l, controls sour zinc than being 2.6-2.8:1; Electrolytic solution manganese ion concentration, when 15-25g/l, controls sour zinc than being 2.0-2.6:1.
Further, be in 70mm electrolyzer at same pole span, electrolytic solution Mn 2+ionic concn, when 6.5-8g/l, controls sour zinc than being 2.6-3.0:1; Electrolytic solution Mn 2+ionic concn, when 8-12g/l, controls sour zinc than being 2.4-2.6:1; Electrolytic solution manganese ion concentration, when 12-25g/l, controls sour zinc than being 2.0-2.4:1.
Further, in Zinc electrolysis electrolytic process, take to open temperature in multiple stage cooling tower control flume is 38--43 DEG C, and bath voltage is 3.2-3.5V, and cathode area electric current is 450-500A/m 2, strengthening negative plate is smooth further, reduces anode and cathode short circuit of polar and occurs; Increase Strontium carbonate powder consumption, reduce cathode zinc containing lead doping.
Further, adopt vacuum take-off slotting to carry out groove clearly in Zinc electrolysis electrolytic process, the clear groove cycle is 20-25 days, improves electrolyzer and circulation line liquid flow rate, flow velocity.Be beneficial to electrolytic process fully to carry out.
The invention has the beneficial effects as follows:
1, reasonablely can control well and normally produce, eliminate the impact for electrolysis electrolytic deposition process in two kinds of pole spans of different manganese ion concentration.
2, in difference is with pole span, contained by electrolysis cycle liquid, manganese ion concentration height adopts the sour zinc ratio of reduction, decreases manganese ion concentration fluctuation to greatest extent to Zinc electrolysis disserve to produce, decreases negative plate and burn the saturating sour accident of plate, stabilize production.
3, by optimization production technical qualification, have found reasonable production technical controlling scope, 75mm is with improve cathode zinc output in polar distance electrolytic bath from 0.74 ~ 0.80 ton/groove. sky, 70mm with pole span 70mm with improve cathode zinc output in pole span from 0.72 ~ 0.78 ton/groove. sky, 75mm all reaches zero level product rate with pole span and 70mm with cathode zinc quality in polar distance electrolytic bath.
4, controlled by optimization production, improve zinc hydrometallurgy for Mn 2+the adaptability of ionic concn variation range.
Embodiment
In zinc hydrometallurgy electrolytic process, after optimization production controls, 75mm is with pole span and 70mm
In different manganese ion concentration content, different sour zinc is controlled as follows than testing data with pole span:
By above-mentioned test data analyzer, with the electrolyzer of pole span 75mm, reduce sour zinc than controlling needs at Mn 2+ionic concn starts when reaching more than 10g/l to reduce sour zinc ratio; With the electrolyzer of pole span 70mm, work as Mn 2+when ionic concn reaches more than 6.5g/l, start to reduce sour zinc ratio, to ensure that electrolysis electrolytic deposition process carries out smoothly, eliminate different mn ion for the impact of two kinds of pole spans for electrolysis electrolytic deposition process.
In zinc wet method smelting process, in order to can in electrolysis cycle liquid Mn 2+when ion variation range rises to 25g/l very soon from 2 g/l, stably manufactured reduces the zinc wet method smelting process of electrolytic solution acid zinc ratio under have employed high manganese condition, concrete technical measures are as follows:
Step 1: stoving oven is produced
In roasting process, need zinc baking sand to control about 0.4% containing residual sulphur; Concrete measure is: strengthen batching, keeps zinc ore concentrate water ratio 9.5-10%, controls maturing temperature 900-1000 0c, makes zinc ore concentrate sufficient combustion, and reducing residual sulphur affects for subsequent production; If residual sulphur, more than 0.4%, reaches more than 1.0%, greatly will increase subsequent production manganese mineral powder consumption, increase system Mn 2+ionic concn content.
Step 2: leach and produce
The concrete measure reducing manganese mineral powder consumption in leaching process is: first improve Manganse Dioxide in electrolysis vacuum slotting liquid and leaching the service efficiency in producing, use the Manganse Dioxide ore pulp that tetravalent manganese is high, be conducive to the add-on reducing solid manganese mineral powder; The add-on of next manganese mineral powder is generally at 6-8 tons/days, and just can meet to leach and produce normal production, because zinc baking sand contains residual sulphur more than 0.4%, reach about 1.0%, then add manganese mineral powder solid material, every day, add-on reached 12-48 ton/sky.
Step 3: clean liquid is produced
Qualified new liquid safeguards: produce one section of removing Cu, Cd foreign ion at clean liquid; Two sections of removing Co, Ni foreign ions.Mn 2+ionic concn content can not increase and decrease, and by stable operation, provides qualified new liquid, ensures the required new liquid quality of electrowinning process.
Step 4: electrolysis production
According to Site Detection Mn 2+ionic concn is 10-25g/l, cathode zinc leaded 0.005-0.010%, the production datas such as electrolyzer temperature 38-43 DEG C, cathode zinc output, circulation fluid resistance 0.031-0.035, unit dc consumption 3050-3150KWh/t, technician formulates conservative control acid zinc ratio;
For the electrolyzer of same pole span 75mm, work as Mn 2+ion is normal production when 2-10g/l, controls sour zinc than 3.0-3.8:1; When 10-12g/l, control sour zinc than being 2.8-3.0:1; Electrolytic solution manganese ion concentration, when 12-15g/l, controls sour zinc than being 2.6-2.8:1; Electrolytic solution Mn 2+ionic concn, when 15-25g/l, controls sour zinc than being 2.0-2.6:1;
For the electrolyzer of same pole span 70mm, electrolytic solution Mn 2+ion is normal production when 2-6.5g/l, and sour zinc ratio controls at 3.0-3.8:1; When 6.5-8g/l, control sour zinc than being 2.6-3.0:1; Electrolytic solution Mn 2+ionic concn, when 8-12g/l, controls sour zinc than being 2.4-2.6:1; Electrolytic solution Mn 2+ionic concn, when 12-25g/l, controls sour zinc than being 2.0-2.4:1;
Operator add new liquid consumption 0.3m flexibly according to such scheme in circulation fluid 3/ h. groove, to ensure that sour zinc is than within span of control;
Smooth in order to strengthen negative plate further in electrolysis production process, reduce anode and cathode short circuit of polar and occur; Increase Strontium carbonate powder consumption, reduce cathode zinc containing lead doping, take out multiple stage cooling tower, temperature in groove is dropped to 38--43 by 40-48 DEG C 0c;
In order to improve electrolyzer and circulation line liquid flow rate, flow velocity, being beneficial to electrolytic process and fully carrying out, by improving groove internal recycle flow 10%, strengthen the clear groove dynamics of electrolyzer slotting, the clear groove cycle shortened to 20-25 days by 30 days.
By the enforcement of above-mentioned concrete technical measures, can control electrolysis production process well more stablely, ensure groove face management steady ordered, produce cathode zinc that is up-to-standard, stable yield, ensure that electrolysis production is normally run, wherein cathode zinc quality is stable reaches No. zero zinc standard, and cathode zinc output can return to 320 tons/day---and 330 tons/day, than lower slightly under normal mn ion condition.Concrete outcome sees attached list.
The zinc wet method smelting process of electrolytic solution acid zinc ratio is reduced, Mn in electrolysis cycle liquid under the invention provides high manganese condition 2+when ionic concn variation range rises to 25g/l very soon from 2 g/l, adopt and reduce sour zinc than methodology, decrease manganese ion concentration fluctuation to greatest extent to Zinc electrolysis disserve to produce, decrease negative plate and burn the saturating sour accident of plate, stabilize production.
Above-described is only the preferred embodiments of the present invention.Should be understood that for the person of ordinary skill of the art, under technology enlightenment provided by the invention, as the common practise of this area, other equivalent modifications and improvement can also be made, also should be considered as protection scope of the present invention.

Claims (5)

1. reduce a zinc wet method smelting process for electrolytic solution acid zinc ratio under high manganese condition, it is characterized in that: be different from pole span at Zinc electrolysis electrolyzer, reduce electrolysis cycle liquid acid zinc according to electrolysis cycle liquid manganese ion concentration difference and produce normally than ensureing.
2. reduce the zinc wet method smelting process of electrolysis cycle liquid acid zinc ratio under high manganese condition according to claim 1, it is characterized in that: be in 75mm electrolyzer at same pole span, electrolysis cycle liquid manganese ion concentration, when 10-12g/l, controls sour zinc than being 2.8-3.0:1; Electrolysis cycle liquid manganese ion concentration, when 12-15g/l, controls sour zinc than being 2.6-2.8:1; Electrolysis cycle liquid manganese ion concentration, when 15-25g/l, controls sour zinc than being 2.0-2.6:1.
3. reduce the zinc wet method smelting process of electrolytic solution acid zinc ratio under high manganese condition according to claim 1, it is characterized in that: be in 70mm electrolyzer at same pole span, electrolysis cycle liquid manganese ion concentration, when 6.5-8g/l, controls sour zinc than being 2.6-3.0:1; Electrolysis cycle liquid manganese ion concentration, when 8-12g/l, controls sour zinc than being 2.4-2.6:1; Electrolytic solution manganese ion concentration, when 12-25g/l, controls sour zinc than being 2.0-2.4:1.
4. the zinc wet method smelting process of electrolysis cycle liquid acid zinc ratio is reduced under high manganese condition according to claim 1, it is characterized in that: in Zinc electrolysis electrolytic process, take to open temperature in multiple stage cooling tower control flume is 38--43 DEG C, bath voltage is 3.2-3.5V, and cathode area electric current is 450-500A/m 2.
5. reduce the zinc wet method smelting process of electrolysis cycle liquid acid zinc ratio under high manganese condition according to claim 1, it is characterized in that: in Zinc electrolysis electrolytic process, adopt vacuum take-off slotting to carry out groove clearly, the clear groove cycle is 20-25 d.
CN201510042747.8A 2015-01-28 2015-01-28 Zinc hydrometallurgical process capable of reducing acid-zinc ratio of electrolyte under different manganese ion conditions Active CN104562083B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105937040A (en) * 2016-06-24 2016-09-14 白银有色集团股份有限公司 Process for reducing cathode zinc direct-current current unit loss in zinc wet method smelting for processing high mixed ore
CN114134538A (en) * 2021-12-08 2022-03-04 昆明理工恒达科技股份有限公司 Zinc electrodeposition system suitable for high current density

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105937040A (en) * 2016-06-24 2016-09-14 白银有色集团股份有限公司 Process for reducing cathode zinc direct-current current unit loss in zinc wet method smelting for processing high mixed ore
CN105937040B (en) * 2016-06-24 2018-05-25 白银有色集团股份有限公司 It is a kind of to handle the technique that cathode zinc unit dc consumption is reduced in high miscellaneous ore deposit zinc hydrometallurgy
CN114134538A (en) * 2021-12-08 2022-03-04 昆明理工恒达科技股份有限公司 Zinc electrodeposition system suitable for high current density
CN114134538B (en) * 2021-12-08 2024-03-26 昆明理工恒达科技股份有限公司 Zinc electrowinning system suitable for high current density

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