CN1034958C

CN1034958C - One-step Zn smelting technique by suspension electrolysis of ZnS

Info

Publication number: CN1034958C
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: 1997-05-21
Anticipated expiration: 2013-05-06
Also published as: CN1094762A

Abstract

The present invention relates to a new one-step zinc smelting technique by suspension electrolysis of zinc sulphide ore, which belongs to the field of chemistry and metallurgy. The present invention is characterized in that nascent state chlorine produced by the electrolysis of chlorine salt solution in an anode chamber of a suspension electrolytic tank with a special structure is used for leaching out zinc sulphide ore; simultaneously, GB470-83 primary or secondary electrolytic zinc and zinc powder are economically and reasonably prepared from the zinc sulphide ore by controlling a proper condition through purified anode solution with zinc chloride on the electrodeposit of a cathode chamber. The present invention has the advantages of short production process, less investment, no pollution to environment, random production scale and low cost, and is suitable for all kinds of zinc sulphide ore.

Description

Method for preparing zinc by electrolyzing zinc sulfide ore and electrolytic bath thereof

The invention belongs to the technical field of electrochemical metallurgy, and particularly relates to a method and equipment for preparing electrolytic zinc by using zinc sulfide ore through wet metallurgy.

The wet zinc smelting method introduced in the "heavy metal metallurgy" is one of the prior arts of the present invention, and is characterized in that zinc concentrate is roasted into zinc calcine (ZnO) by a fluidized bed furnace, then leached by dilute sulfuric acid, and the leachate is purified and then is sent to electrolysis to produce electrolytic zinc. The disadvantages of this technique are: SO (SO)₂The environment is polluted; acid making and capital reporting are large; the storage and transportation of the sulfuric acid are large; the electrolytic acid mist is large, the leaching system is huge, and the power consumption is large. And the leached zinc ferrite reduces the recovery rate of zinc.

The 'sulfide ore suspension electrolysis new technology' in the No. 5 journal of nonferrous metals 1987 is taken as the second prior art, and the diaphragm used by the electrolysis cell in the prior art is porous polypropylene filter cloth, which has the defects that: (1) only plays a role in separating ore pulp; (2) the leaching solution has high cost, and (3) the leaching rate of zinc is low.

The invention aims to provide a method for preparing zinc by electrolyzing zinc sulfide ore and an electrolytic cell thereof, which are developed by utilizing an ion exchange cathode membrane technology aiming at the defects of the prior art.

The method adopts a suspension electrolytic tank with an ion exchange cathode membrane as a diaphragm of an anode chamber and a cathode chamber, wherein the anode chamber is filled with an acid chloride solution, and the cathode chamber is filled with leachate, and the method comprises the following specific steps and a chemical reaction process:

1. zinc sulfide ore which is ground to be below-100 meshes in advance is put into an anode chamber of an electrolytic cell, and is leached by chloride ions which are generated by electrolysis from leachate of the cathode chamber and selectively permeate through an ion exchange cathode membrane. The main chemical reaction is as follows:

2. ore pulp formed by leaching is discharged from the anode chamber, the ore pulp is clarified and filtered, filtrate and filter residue washing liquor are purified together to be used as leachate to be sent into the cathode chamber of the electrolytic cell, electrolytic zinc and waste electrolyte are produced by electrodeposition, and the main chemical reaction is as follows: (ii) a The filter residue is processedAfter washing and filtering with hot water, the waste residue is sent to a sulfur extraction process.

3. And waste electrolyte generated in the cathode chamber is sent to the anode chamber to be used as chloride solution for recycling.

In the method, the anode chamber acid chloride solution comprises the following components: all-grass of Chinese chess like CL^-2-5mol/L of HCL 0.5-2N; the anode chamber leaching conditions are as follows: the liquid-solid ratio is (6-12) to 1, the temperature is 70-100 ℃, the current density is 300-²Leaching for 4-8 hours, and using graphite as an anode; the conditions for electrodeposition in the cathode chamber were: PH1-4, temperature 50-70 deg.C, and aluminum plate or titanium plate as cathode.

The electrolytic tank adopts a suspension electrolytic tank, and comprises a furan glass fiber reinforced plastic tank body 1, a liquid inlet pipe 2, a membrane frame 3, an overflow pipe 6, an anode chamber 7 and a cathode chamber 8, wherein a diaphragm 4 between the cathode chamber 7 and the anode chamber 8 adopts an ion exchange cathode membrane, and the bottom of the anode chamber 8 is provided with a jet flow stirrer 5. The monomer cells can be combined into the desired series according to the scale of production.

Compared with the prior art, the invention has the following advantages:

1. the process flow is simple, the zinc leaching and the electrodeposition are carried out in the same equipment, the electric energy of the cathode and the anode is fully utilized, the direct power consumption is only 800-950KWH/T, and the energy and the equipment investment are saved.

2. The regeneration and the electrolysis of the chloride are carried out simultaneously, and no working procedure and equipment are needed to be added.

3. The zinc sulfide ore does not need to be roasted to prepare acid, the production process is shortened, the investment is saved, and SO is avoided₂And (5) pollution to the environment.

4. The smelting recovery rate of zinc is more than 92 percent, which is higher than that of the conventional production method, and the zinc product reaches more than second grade zinc of GB 470-83.

5. The production scale can be large or small, and the adaptability tozinc concentrate is wide.

6. The main raw materials are economical and cheap, the consumption is low, and the production cost is low.

The invention is especially suitable for treating zinc sulfide ore or zinc sulfide concentrate containing more than 40% of Zn, less than or equal to 2% of Pb and less than or equal to 8% of Fe, and can also be used for ore containing lower Zn and higher Pb and Fe.

FIG. 1 is a schematic structural diagram of an electrolytic cell of the invention, in which 1-a furan glass fiber reinforced plastic cell body, 2-a liquid inlet pipe, 3-a membrane frame, 4-an ion exchange cathode membrane, 5-a jet flow stirrer, 6-an overflow pipe, 7-an anode chamber and 8-a cathode chamber are shown.

Two specific embodiments are described below:

example 1: taking 90g of zinc sulfide concentrate containing Zn 50%, the granularity is-200 meshes and accounts for 39.8%, the rest is less than 100 meshes, and using all kinds of Zn containing [ (CL]^-〗4mol、HCL1.5mol、〖Fe ³⁺1 liter of acidic chloride solution which is 3.24g in the mass is put into the anode chamber of the suspension electrolytic cell of the invention for leaching, and the leaching temperature is controlled to be 80 +/-5 ℃ and the current density is controlled to be 700A/M²The anode chamber is provided with a graphite anode; the cathode chamber is put into a titanium cathode plate for agitation leaching and electrolysis, and the leaching solution of the cathode chamber is purified ZnCL₂Controlling the pH of the solution to 1-4 and the electrolysis temperature to 50-70 ℃, and sending the electrolysis waste liquid to the anode chamber for recycling. Afterthe anode chamber is leached for 5 hours, the formed ore pulp is discharged, clarified and filtered, filter residues are washed and filtered by hot water, dried and analyzed, filtrate and filter residue washing liquor are purified to be used as leachate to be sent to a cathode chamber for electrodeposition to generate electrolytic zinc and waste electrolyte, the electrolytic zinc is washed and dried, the quality can reach 1-2 pole standard of GB470-83, the electrolytic zinc contains Zn99.97%, the waste residue contains zinc 4.1%, and the leaching rate of Zn reaches 96.1%.

Example 2 Using 100 g of Zn48.6% zinc sulfide ore, grinding to-100 mesh, and extracting with 1L of acid chloride by the same procedure as in example 1, wherein [ (CL) is prepared^-〗5mol，HCL2mol，〖Fe³⁺5g in the leaching temperature of 70 ℃ and the current density of 550A/M²(ii) a The leachate in the cathode region contains 90g/L Zn, the pH is 1-4, the electrolysis temperature is 55 ℃, after suspension leaching electrolysis is carried out for 7 hours, the products in the cathode chamber and the anode chamber are treated by the same method as in example 1, the leaching rate of Zn is 95.55 percent, the zinc content in waste residues is 4.5 percent, and the zinc content in the products is 99.98 percent.

Claims

1. The utility model provides a suspension electrolysis groove for zinc is prepared in electrolysis of zinc sulfide ore deposit, includes furan glass steel cell body (1), feed liquor pipe (2), membrane frame (3) overflow pipe (6), anode chamber (7), cathode chamber (8), its characterized in that:

an ion exchange cathode membrane (4) is adopted as a diaphragm between the cathode chamber (7) and the anode chamber (8);

and a jet flow stirrer (5) is arranged at the bottom of the anode chamber (8).

2. A method for preparing zinc by electrolyzing zinc sulfide ore is characterized in that: using a suspension cell according to claim 1 and containing an acidic chloride solution in the anode compartment and a leach solution in the cathode compartment; the method comprises the following specific steps:

a. putting zinc sulfide ore which is ground to be below-100 meshes in advance into an anode chamber of an electrolytic cell for chlorination leaching;

b. b, discharging ore pulp formed by chlorination leaching in the step a from the anode chamber, clarifying and filtering the ore pulp, purifying filtrate and filter residue washing liquor together, and then conveying the purified filtrate serving as leachate into the cathode chamber, and electrodepositing to generate electrolytic zinc and waste electrolyte;

c. and c, feeding the waste electrolyte generated in the step b into the anode chamber to be used as an acid chloride solution for recycling.

3. The process for the electrolytic production of zinc from zinc sulphide ore according to claim 2, characterized in that:

a. the anode chamber acid chloride comprises the following components:

[CL^-]2-5mol/L，HCL0.5-2N；

b. the anode chamber leaching conditions are as follows:

the liquid-solid ratio is (6-12) to 1, the temperature is 70-100℃,

Current density 300-1000A/M²、

Leaching for 4-8 hours;

c. the conditions of electrodeposition in the cathode chamber are as follows:

the pH is 1-4, and the temperature is 50-70 ℃.