CN1077497A

CN1077497A - Technology for wet-process cupper smelting

Info

Publication number: CN1077497A
Application number: CN92102819A
Authority: CN
Inventors: 刘秉贤
Original assignee: Individual
Current assignee: Individual
Priority date: 1992-04-14
Filing date: 1992-04-14
Publication date: 1993-10-20

Abstract

The present invention is a technology for wet-process cupper smelting.

The present invention adopts liquor ferri trichloridi leaching cupric sulfide breeze according to hydrometallurgical principle, makes the sulfide of copper be converted into muriate and enter solution.The cupric leaching liquid is at diaphragm sell cathode compartment reduction system electrolytic copper, and the catholyte behind the extraction copper becomes liquor ferri trichloridi at the anolyte compartment of diaphragm sell oxidation regeneration, returns the leaching system.Soak slag and reclaim elemental sulfur through a kerosene or a hot dipping of benzene, with behind the sodium-chlor hot dipping recovery silver chloride, Gold Content is handled by gold ore by bringing up to 10-12 gram/tons for ore deposit 5-6 gram/tons again.

Description

Technology for wet-process cupper smelting

The present invention is a kind of technology for wet-process cupper smelting method.

The technological process of general pyrogenic process smelting copper is:

Will be from the cupric sulfide breeze in mine, roasting in temperature is lower than the stoving oven of breeze fusing point to drive away aqueous vapor and to remove a part of sulphur with the form of sulfurous gas, is made roasted ore.Then, roasted ore is mixed with lime carbonate, melting slagging-off in temperature is higher than their smelting furnace of fusing point forms matte:

Matte reduces in converter and makes blister copper:

Blister copper is cast big pole plate, makes anode in electrolyzer, and thin fine copper sheet is made negative electrode, and copper sulfate is made electrolytic solution, carries out electrorefining.Impure copper enters solution by anode, and fine copper is separated out at negative electrode, makes electrolytic copper:

The smeltery all adopts above pyrometallurgical smelting process system copper, needs through roasting, melting, and reduction three big stoves just can enter potroom.Facility investment is huge, the energy consumption height, and Working environment is arduous, and general medium and small mine does not have the production of ability tissue, and the ore outward transport had both increased expense, had strengthened the railway burden again.

The object of the invention be to propose a kind of invest little, equipment simple, processing ease, graceful environment, be suitable for the technology for wet-process cupper smelting of ungetable medium and small mine on-the-spot disposal worked copper breeze, the pyrometallurgical smelting investment is big, energy consumption is high to overcome, shortcomings such as production be can not organize flexibly, bigger economic benefit and social benefit created.

The principle of the invention is as follows:

Utilize the strong oxidizing property of ferric ion and the vattability of ferrous ion, make that sulphur root negative ion is oxidized to elemental sulfur in the insoluble metal sulfide, the valuable metal that dissociates is converted into muriate:

Different according to solubleness and electropotential are carried out Separation and Recovery then, at last with the ferrous chloride oxidation regeneration, set up leaching-reprocessing cycle system.

Technological process of the present invention is as follows:

At first adopt the liquor ferri trichloridi of 10-60%, between 15-135 ℃, leaching is from the cupric sulfide breeze in mine, leached 30-90 minute, the sulphur root negative ion of metallic sulfide is oxidized to elemental sulfur by ferric ion and enters and soak slag, ferric ion is reduced into ferrous ion, and the sulfide of copper is converted into soluble muriate and enters leaching liquid, and the sulfide of silver is converted into the little silver chloride of solubleness and enters and soak slag.Through liquid-solid separation, make the cupric leaching liquid.

To the processing of cupric leaching liquid, operation as follows all can reach purpose of the present invention:

(1), the cupric leaching liquid is directly as electrolytic solution, enters the cathode compartment of diaphragm sell, on thin fine copper sheet negative electrode, cupric ion is reduced into electrolytic copper:

Extract the catholyte behind the cupric ion, be sent to the anolyte compartment of diaphragm sell, on inert anode, ferrous ion is oxidized to ferric ion:

The regenerated liquor ferri trichloridi returns leaching, forms leaching-reprocessing cycle system.

(2), the cupric leaching liquid replaces with iron, cupric ion is reduced into copper sponge by iron, iron is oxidized to ferrous ion and enters solution:

Separate copper sponge, soak with after removing the iron filings that are mingled with dilute hydrochloric acid, as the raw material of producing cupric oxide, copper sulfate, electrolytic copper etc.Displacement liquid becomes ferric ion with oxidation ferrous ions such as oxygenant such as nitric acid, chlorine:

The regenerated ferric chloride solution returns leaching, forms leaching-reprocessing cycle system.

(3), the cupric leaching liquid replaces with iron, cupric ion is reduced into copper sponge by iron, iron is oxidized to ferrous ion and enters solution:

Separate copper sponge, soak with after removing the iron filings that are mingled with dilute hydrochloric acid, as the raw material of producing cupric oxide, copper sulfate, electrolytic copper etc.

Displacement liquid places the cathode and anode chamber of diaphragm sell respectively, and anolyte is oxidized to ferric chloride solution, returns leaching, forms leaching-regeneration system:

Catholyte is reduced into fe, is used to replace cupric leaching liquid system copper sponge:

When zinc ion concentration is to finite concentration in the circulation leaching liquid, needs to extract out and reclaim zinc, and then participate in circulation with acetone extract.

The barrier film of above-mentioned diaphragm sell can be homogeneous phase or out-phase anion-exchange membrane.

The present invention is to handle like this to soaking slag:

Make the silver chloride solid formation complex compound of indissoluble in the slag enter solution earlier with the elemental sulfur in kerosene or a hot dipping of the benzene recovery slag, and then with sodium-chlor or calcium chloride hot solution, iron powder replacement reclaims silver:

At this moment, the content of gold increases substantially in the slag, by bringing up to 10-12 gram/ton for ore deposit 5-6 gram/ton, can handle by gold ore.

Further specify technological process of the present invention for embodiment:

Embodiment 1:

In 1000 liter enamel reaction stills, add 500 kilograms of 30% liquor ferri trichloridis, 100 kilograms of cupric sulfide breezes (Cu22%, Zn2%, Ag200 gram/ton, Au6 gram/ton, 100 orders), stir leaching 1 hour at 95 ± 5 ℃, filtration, washing, wash water are incorporated filtrate into, obtain 300 kilograms of cupric leaching liquids.

Get 300 kilograms of this leaching liquids, place the cathode compartment of diaphragm sell, the fine copper thin slice is made negative electrode.The anolyte compartment adds 300 kilogram of 20% ferrous chloride solution, and graphite cake is made anode.Cathode current density 1.5-2 peace/square decimeter, normal temperature electrolysis 8 hours, catholyte is regenerated to brown by light green, iron trichloride content 19%, catholyte is reduced into light green by brown, and copper chloride content 5% gets 10.8 kilograms of electrolytic coppers.

Embodiment 2:

Method by embodiment 1 makes 300 kilograms of cupric leaching liquids, adds 7 kilograms of iron filings, and 5 kilograms on iron plate 60-70 ℃ of displacement 1 hour, gets 10.9 kilograms of copper sponges.Displacement liquid slowly feeds chlorine to saturated, iron trichloride content 34%.

Embodiment 3:

Method by embodiment 1 makes 600 kilograms of cupric leaching liquids, add 15 kilograms of iron filings, 10 kilograms on iron plate was 60-70 ℃ of displacement 1 hour, get 21.8 kilograms of copper sponges, displacement liquid place respectively diaphragm sell the cathode and anode chamber each 300 kilograms, iron plate is made negative electrode, graphite cake is made anode, cathode current density 3-3.5 peace/square decimeter, electrolysis 6 hours, anolyte is regenerated to brown by light green, iron trichloride content 32%.Catholyte is reduced into water white transparency by light green, makes 9 kilograms of fes.

Soak 75 kilograms of slags, add 100 kilograms of kerosene, in 60 ℃ of hot dippings 30 minutes, filtered while hot, cooling gets 15 kilograms of elemental sulfurs.

Soak slag with 100 kilograms of 30% sodium chloride solutions after carrying sulphur, soaked 30 minutes 95 ± 5 ℃ of commentaries on classics, filtration, filtrate are replaced with iron, reclaim argent 18 grams.

Soak surplus 60 kilograms at last of slags, contain gold 10 gram/tons, the down payment fine ore is handled.

More than three kinds of embodiment, all can obtain following overall target:

Copper transformation efficiency:＞99%

Silver raising recovery rate:＞90%

Sulfur recovery rate:＞95%

Zinc recovery:＞80%

Process of the present invention has following several advantage:

(1), the investment little, equipment is simple, processing ease is particularly suitable on the spot worked copper breeze of ungetable medium and small mine.

(2), one soaks Dai Sanlu, leaching liquid formation leaching-regeneration cycle system, energy consumption and cost decrease.

(3), recyclable associated valuable metals zinc, silver, gold and elemental sulfur.

(4), input-output ratio is high, social benefit is large.

Claims

1, a kind of technology for wet-process cupper smelting comprises the steps:

(1), with liquor ferri trichloridi leaching cupric sulfide breeze, make the sulfide of copper change into soluble muriate and enter leaching liquid, sulphur root negative ion is oxidized to elemental sulfur by ferric ion and enters and soak slag, ferric ion is reduced into ferrous ion.

(2), this cupric leaching liquid is directly as electrolytic solution, enters the cathode compartment of diaphragm sell, cupric ion is reduced into electrolytic copper at this.

(3), extract the catholyte behind the cupric ion, enter the anolyte compartment of diaphragm sell, at this, ferrous ion is oxidized to ferric ion.The regenerated liquor ferri trichloridi returns the leaching system.

2, a kind of technology for wet-process cupper smelting comprises the steps:

(1), with liquor ferri trichloridi leaching cupric sulfide breeze, make the sulfide of copper change into soluble muriate and enter leaching liquid, sulphur root negative ion is oxidized to elemental sulfur by ferric ion.

(2), this cupric leaching liquid replaces with iron, makes copper sponge.

(3), extract the displacement liquid behind the cupric ion, become ferric ion with oxidation ferrous ions such as oxygenant such as nitric acid, chlorine, the regenerated liquor ferri trichloridi returns the leaching system.