WO2015003538A1

WO2015003538A1 - Hydrometallurgical method of metal sulfides

Info

Publication number: WO2015003538A1
Application number: PCT/CN2014/079337
Authority: WO
Inventors: 张超
Original assignee: Zhang Chao
Priority date: 2013-07-12
Filing date: 2014-06-06
Publication date: 2015-01-15

Abstract

Disclosed is a hydrometallurgical method of metal sulfides, comprising: 1) adding a metal A sulfide into a leaching solution and finally generating a metal A complex, elemental sulfur and a reduced catalyst; and 2) filtering the leaching solution treated in step 1) and containing the metal A complex, the elemental sulfur and the reduced catalyst, injecting the leaching solution into an electrolytic bath, using an inert electrode as an anode and using metal A or an inert electrode as a cathode, and performing electrolyzing to obtain the metal A at the cathode. Compared with a conventional strong acid leaching process, the method in the present invention greatly reduces the corrosion on a device. According to the present invention, continuous circulation of leaching sulfides by using the leaching solution and regenerating the leaching solution is implemented by using a proper catalyst, a complexing agent and an electrolytic method.

Description

Wet smelting method for metal sulfides

The invention belongs to the field of metal sulfide hydrometallurgy technology, and relates to a method for electrolyzing metal sulfide into metal and elemental sulfur by electrochemical method. Background technique

Metal sulfides are the main components of sulfide minerals, including lead sulfide ore, copper sulfide ore, sulfide ore, barium sulfide ore, nickel sulfide ore. The smelting method of metal sulfide is divided into pyrometallurgical smelting and wet smelting. At present, the industrially mature one is pyrometallurgical smelting. For example, in the smelting of lead sulfide and copper sulfide, the sulfide ore is sequentially subjected to oxidative smelting, reduction smelting to obtain crude lead and blister copper, and then refined to obtain lead or copper with higher purity, and sulfur in the sulfide ore is in the flue gas. In the form of sulfur dioxide, sulfuric acid is produced in the tail gas absorption tower. However, in the process of smelting, a large amount of coke is consumed for the original 3⁄4i, and a large amount of lead or copper slag is generated in the pyrometallurgical smelting, which not only pollutes the environment, but also makes valuable metals. Loss, reducing the recovery rate of sulfur ore

In view of the low recovery rate of metal sulphide smelting metals and the serious environmental pollution, the wet smelting of metal sulphide has been rapidly developed. The wet smelting of metal sulfide mainly includes two parts: oxidation leaching and solution electrolysis. Among them, oxidative leaching mainly uses ferric ion as oxidant, and oxidizes metal sulfide into elemental sulphur and metal ion-containing solution in an acidic environment. The ferric iron is reduced to divalent iron, and then the leachate is regenerated by oxidation of air or other oxidant, and the metal ion-containing solution is electrolyzed to obtain metal and oxygen, thereby avoiding environmental pollution during the pyrometallurgical process. Compared with pyrometallurgical smelting, there is a higher metal recovery rate, but in the electrolysis process, the electrolysis voltage is very high, and the energy consumption is much higher than that of pyrometallurgical smelting.

In the reported metal sulfide hydrometallurgical process, the leaching of metal sulfides requires a leachate containing ferric ions at high pressure (P > 2, () MPa) and high temperature (T > 100 ° C). The leaching has a higher yield under the conditions, and then the metal ion-containing leachate is electrolyzed to obtain a metal, generally a metal powder is obtained at the cathode, and the metal powder is more easily oxidized by air during the smelting process. In the treatment, at the same time, in the electrolysis process, the electrolysis voltage is higher, for example, in the hydrometallurgy of copper sulfide and lead sulfide, the electrolysis process voltage is between 1,8 and 2.2V, so that the electrolysis energy of copper sulfide and lead sulfide It consumes up to nOOkWh/t and 500kWh/t, which is much higher than the cost of pyrometallurgical smelting. At the same time, it also consumes oxidants such as hydrogen peroxide and chlorine to reoxidize the divalent iron ions in the leachate to ferric ions to regenerate the leachate, further increasing the smelting cost of the sulfide ore.

The present invention provides a novel wet smelting method for metal sulfides according to the disadvantages of the prior art, and has the technical advantages of good refining effect and low energy consumption.

A wet smelting method for metal sulfides, comprising:

1) Adding metal A sulfide to the leachate, and finally forming a metal A complex, elemental

2) The leachate containing the metal A complex, the elemental sulfur, and the reduced catalyst after the step 1) is filtered and injected into the electrolytic cell, using the inert electrode as the anode metal A or the inert electrode as the cathode, and electrolyzing Metal A is obtained at the cathode.

Further, before step 1), step a: is further included:

The metal A sulfide containing the impurity metal sulfide is added to the pretreatment liquid for treatment, and the impurity metal sulfide in the metal A sulfide is converted into the metal A sulfide.

Further, the preferred method is, step a, further comprising:

The pretreatment liquid treated in the step a is subjected to metal replacement or electrolysis to recover the valuable metal and the pretreatment liquid is regenerated;

The step 2) further comprises: the reduced catalyst is reoxidized to a catalyst by electrochemical reaction at the anode, and the metal A complex is obtained at the cathode to obtain the metal A and the complexing agent, thereby recycling the leachate.

Further, in a preferred method, in the step a, the pretreatment liquid contains a complexing agent and a metal A lt , wherein the buffer solution is used to adjust the pH of the pretreatment liquid between 3.0 and 9,0. Further, a preferred method is that the metal A sulfide is one of copper, iron, zinc, antimony, nickel, cadmium, lead sulfide or chemical ore.

Further, in a preferred method, in the step a, the complexing agent is one of an α-amino acid, an aminocarboxylic acid group containing an aminodiacetic acid group or an aminoacetic acid group. Or several, at a concentration of 0,3-3.5 mol/L;

The metal A salt is one or more of the sulfate, nitrate oxide, chloride and acetate of the metal A, and the concentration is 0,05-1 „0 mol/L;

Wherein, the buffer solution is used in step a to maintain the pH value of the solution between 3.0-9,0, and the buffer solution contains hydrochloric acid, glycine-hydrochloric acid, ammonium acetate, acetic acid-sodium acetate, hexamethylenetetramine-hydrochloric acid. One or more of sodium dihydrogen phosphate-sodium hydroxide, sodium carbonate-carbonic acid hydrogen, at a concentration of 1-50 ° /. The solution, the reaction temperature is between 15 and 10 CTC.

Further, a preferred method is that the complexing agent is ethylenediamine diacetic acid, propylenediamine diacetic acid, ammonia triacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, ethylene glycol diethyl ether diamine tetraacetic acid , hydroxyethyl ethylenediamine triacetic acid, diethylenetriamine pentaacetic acid, aspartic acid, alanine, valine, glutamic acid, valine, tyrosine, phenylalanine, leucine, One or more of histidine, asparagine, glycine, threonine, serine, glutamine, citrulline, lysine, arginine cysteine, methionine, ornithine, concentration It is 0,3-3.5 moi/L.

Further, in a preferred method, in the step 1), the leach solution includes a complexing agent, a catalyst, a conductive salt, a metal salt A, an electrodeposition additive, and a buffer solution is used to adjust the pH to 1.5-10.0. between.

Further, in a preferred method, in the leach solution, the complexing agent is one or more of an alpha amino acid, an aminocarboxylic acid group containing an aminodiacetic acid group or an aminoacetic acid group, and a concentration thereof. 0.3-3.5 mol/L;

The catalyst is one or more of a cobalt salt, an iron salt, a manganese salt and a dichromate, and the concentration is 0,01-l, 0 mol/L;

In the conductive salt, the cation is one or more of Na ⁺ and K ΝΗ ₄ ⁺ , and the anion of the conductive salt is Cr, SO 4 ² ", N0 ₃ ", P ₂ O ₇ ⁴ - One or several, the concentration of the conductive salt is 0, 5 4 mol / L; The metal A salt is one or more of the sulfate, nitrate, oxide, chloride, acetate of the metal A, and the concentration is 0,05 1 „0 mol/L;

The electrodeposition additive is one or more of gelatin, bone glue, β-naphthol, rosin, sodium lignosulfonate, and the concentration is 0.1-9 g/L.

Further, a preferred method is that the complexing agent is ethylenediamine diacetic acid, propylenediamine diacetic acid, ammonia triacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, ethylene glycol diethyl ether diamine tetraacetic acid , hydroxyethyl ethylenediamine triacetic acid, diethylenetriamine pentaacetic acid, aspartic acid, alanine, valine, glutamic acid valine, valine, phenylalanine, leucine, One or more of histidine, asparagine, glycine, threonine serine, glutamine, citrulline, lysine, arginine cysteine, methionine, ornithine, at a concentration of 0,3-3.5 mol/L.

Further, the preferred method is, in step 1), further comprising:

When the metal A is copper, the buffer solution is used to control the pH of the solution between 1, 5 and 6.0, and the buffer solution contains pro-acid, ammonium acetate, hydrochloric acid-disodium hydrogen citrate, and sulfosalicylic acid hydrogen. One or more of potassium-sodium hydroxide, acetic acid-acetic acid #], a solution having a concentration of 1-50%;

When the metal A is lead, antimony, zinc, cadmium, nickel or iron, the buffer solution is used to control the pH of the solution between 4,5-10,0, and the buffer solution contains hydrochloric acid, acetic acid, ammonium, acetic acid-sodium acetate. One or more of ethanolamine hydrochloride, sodium carbonate-sodium bicarbonate, and a solution having a concentration of 1-50%.

Further, a preferred method is, in the step 2), further comprising: a reaction temperature of 15 U0 ° C and an electrolysis current density of 50 to 1000 A/m ² .

Further, the preferred method is, in step 2), further comprising:

The electrolysis process adopts constant current electrolysis. The electrolysis temperature is in the range of 15-45 °C, the anode current density is 50-2 ()0A/m ² , and the cathode current density is 100-300A/1H ² ;

The electrolysis temperature is in the range of 45-80 °C, the anode current density is 200-400 A/m ² , and the cathode current density is 300-600 A/m ² ;

The electrolysis temperature is in the range of 80 1 10 , the anode current density is 400-700 A/m ² , and the cathode current density is 600 1000 A/m ² .

After the above-mentioned scheme is adopted, the present invention can realize the conversion between the metal sulfides by using different solubility products of different metal sulfides in the solution, and further purify the sulfides. And the same invention The addition of the complexing agent can greatly increase the reaction rate, and the purification of the sulfide can be completed in a shorter period of time. The purified sulfide provides a high raw material basis for the subsequent leaching electrolysis and has a good technical effect.

Other features and advantages of the invention will be set forth in the description which follows, The objectives and other advantages of the invention may be realized and obtained by means of the structure particularly pointed in the appended claims. Specific Jfe way

The present invention is mainly based on the following principle, wherein, according to a preferred embodiment of the present invention, the Nernst equation for calculating the chemical reaction voltage is as follows:

Garden ^3⁄4圃

M ^→ M + sS

4- BS ' M + S; using 竽 sulphide electrolysis theoretical voltage is

E -宁² +卿 - If S/S ¹ ")

Such as copper sulfide,

4 keys, n-1 , K _sp (CuS)-6

.36

10 The theoretical decomposition voltage of copper sulfide calculated is 0.22V. For lead sulfide

I(3⁄4 ^2÷ F3⁄4 -→S2 , E(S/S ² ~) - L48¥, n-1, K _sp (PbS)-lx 10" ²⁸ , the calculated lead sulfide is 0.47V, so the current Excessively high metal sulfide hydrometallurgical electrolysis energy consumption can be theoretically reduced.

Adding a complexing agent to the solution, the solubility product of the metal sulfide is unchanged, and the true concentration of the metal ion in the solution is lowered (for example, a solution containing 0.5 mol/L ethylenediaminetetraacetic acid, O, lmol/L copper sulfate) , The true concentration of Cu ²⁺ is 1 χ l (y ¹⁹ moL/L), which increases the concentration, which in turn allows the oxidation of S ^{2 to} an electrochemically active catalyst in a weakly acidic or even higher pH environment. The elemental sulfur, the reduced catalyst can be regenerated at the anode through the electrolysis process, avoiding the high-energy anode deoxygenation reaction during the electrolysis process, so that the electrolysis voltage is much lower than the existing sulfide electrolysis voltage.

The present invention provides a method of wet smelting of economical, efficient and environmentally friendly metal sulfides in accordance with the above principles.

In a preferred embodiment, the wet smelting method of the metal sulfide of the present invention is specifically as follows, comprising the following steps:

Step 1: adding a metal A sulfide containing an impurity metal sulfide to the pretreatment liquid for treatment, and converting the impurity metal sulfide in the metal A sulfide into a metal A sulfide;

Step 2: adding the metal A sulfide treated by the step () to the leach solution, and finally forming a metal A complex, elemental sulfur, and a reduced catalyst;

Step 3: Inject the leachate and the metal A complex, the elemental sulfur, and the reduced catalyst in the step 2) into the electrolytic cell, using the inert electrode as the anode, the metal A or the inert electrode as the cathode, and electrolyzing The cathode obtained metal A.

Wherein, the step) is not necessary, and in the case where the amount of impurities in the metal A sulfide is not large, the step 2)-3) is directly taken without taking this step.

In the preferred embodiment, specifically, in step 1), the method includes:

Disposing a pretreatment liquid containing a complexing agent, a metal A salt, using a buffer solution to adjust a pH between 3,0 and 9.0, and adding a metal sulfide to make an impurity metal sulfide having a higher solubility product in the metal sulfide Conversion to metal A sulfide. (for example, zinc sulfide, manganese sulfide, iron sulfide, etc. in lead sulfide ore).

Wherein the complexing agent is one or more of an α-amino acid, an aminocarboxylic acid group containing an aminodiacetic acid group or an aminoacetic acid group, and has a concentration of 0.3 to 3, 5 mol/L.

The metal A salt is one or more of the sulfate, nitrate, oxide, chloride, and acetate of the metal A, and has a concentration of 0.05 l and 0 mol/L. The buffer solution is used to maintain the pH of the solution between 3,0 and 9.0. The buffer solution contains hydrochloric acid, glycine-hydrochloric acid, ammonium acetate, acetic acid-sodium acetate, hexamethylenetetramine-hydrochloric acid, dihydrogen phosphate. - one of sodium hydroxide, sodium carbonate-sodium bicarbonate, a solution having a mass concentration of 1-50%. The reaction temperature is between 15 and 1001. Separated pure after the reaction is completed The metal A sulfide and the pretreatment liquid. The pretreatment liquid recovers the genus by metal replacement or electrolysis and regenerates the pretreatment liquid.

' , also includes: configuration containing complexing agent, catalyst, conductive salt, metal A salt, electrodeposition additive, using a buffer solution to adjust the pH value between 1⁄5-10,0, the addition of the above metal A vulcanization The metal A sulfide, the catalyst reacts with the complexing agent to form a metal A complex, elemental sulfur, a reduced catalyst, and the leach solution is injected into the electrolytic cell through filtration.

Wherein, the electrolytic cell uses inert electrolysis as the anode, the metal A or the inert electrode as the cathode, and the reduced catalyst is reoxidized to the catalyst at the anode by electrolysis at the cathode to the metal A, and the leachate is regenerated and recycled.

Specifically, the complexing agent is one or more of an α-amino acid, an aminocarboxylic acid group containing an aminodiacetic acid group or an aminoacetic acid group, and has a concentration of 0.3 to 3, 5 mol/L. The cation of the conductive salt is one or more of Na ⁺ > K Ν 3⁄4 ⁺ , and the anion of the conductive salt is Cr, S0 ₄ ² " , N0 ₃ \

One or more of P ₂ 0 ₇ , the conductive salt concentration is 0.5-4 mol/L, _:

The catalyst is a concentration of 0.01 to 1.0 mol/L in the cobalt salt, iron salt, manganese and dichromate.

The metal A salt is one or more of the sulfate, nitrate, oxide, chloride, and acetate of the metal A, and has a concentration of 0,05-1.0 mol/L.

Electrodeposition was added as one or more of gelatin, bone glue, |3 naphthol, rosin, and lignosulfonic acid 3 at a concentration of 0.1 - 9 g/L. When the metal A is copper, the buffer solution is used to control the pH of the solution between 1, 5 and 6.0, and the buffer solution is hydrochloric acid - disodium hydrogen citrate, sodium sulfosasulfate potassium hydroxide, acetic acid - sodium acetate. One.

Further, in a preferred embodiment, when the metal A is lead, antimony, zinc, cadmium, nickel or iron, the buffer solution is used to control the pH of the solution between 4,5-10,0, and the buffer solution contains hydrochloric acid and acetic acid. Ammonium, acetic acid-acetic acid], hydrochloric acid-ethanolamine, sodium carbonate-^3⁄4 acid hydroplatinum, the mass concentration is -50% When the metal A is copper, use buffer solution control - at 1, 5 - 6.0 Between, the buffer solution is -

One of acetic acid-sodium acetate, a solution having a mass concentration of 1-50%. Among them, .Reaction temperature 15-1 10 At °C, the electrolysis current density is 50 1000 A/m ² . During the electrolysis process, the cell pressure rises by 0.2-0, and the electrolysis is stopped above 4V.

Further, in step 3), the electrolysis process adopts a constant current electrolysis method, and in the temperature range of the leaching liquid of 15- Ι ,, as the temperature of the leaching solution increases, the migration rate of ions in the solution increases, and the resistivity decreases. The polarization potential of the cathode and the anode is lowered. Therefore, in constant current electrolysis, the electrolysis temperature is in the range of 15-45 °C, the anode current density is 50-20 () A/m ² , and the cathode current density is 100-300 A/ m ² ; electrolysis temperature is in the range of 45-80 ° C, anode current density is 200 400 A / m ² , cathode current density is 300 600 A / m ² ; electrolysis temperature is in the range of 80-110 ° C, anode current density is 400 - 700A/m ² , cathode current density is 600 1000A/m ² .

The above metal A sulfide is one of copper, iron, zinc, antimony, nickel, cadmium, lead sulfide or sulfide ore.

The invention utilizes different solubility products of different metal sulfides in a solution to realize conversion between metal sulfides, thereby purifying sulfides.

For example, in zinc sulfide ore, the solubility products of zinc, iron, manganese and other impurities are much larger than lead sulfide. In the solution containing lead ions, lead ions spontaneously react with impurities such as zinc sulfide and manganese sulfide. The production of lead sulfide, zinc ions and manganese ions enables the purification of lead sulfide ore.

In the copper sulfide ore, the solubility product of copper sulfide is much smaller than the sulfide product of the impurity metals zinc, iron and lead. In the solution containing copper ions, the sulfide of zinc, iron and lead can be converted into copper sulfide. Purification of copper sulfide ore with impurity metal ions.

The addition of a complexing agent at the same time can greatly increase the reaction rate, and the purification of the sulfide can be completed in a shorter period of time. The purified sulfide provides a higher raw material basis for subsequent leaching electrolysis.

In addition, during the leaching process, the metal sulfide can be leached into a metal complex and elemental sulfur by catalytic catalysis under weak acid conditions by using a suitable complexing agent.

The corrosion of the apparatus of the present invention is substantially reduced compared to conventional strong acid leaching processes. At the same time, the invention adopts a suitable catalyst and a complexing agent and realizes a continuous circulation of the leaching solution of the leaching solution and the leaching liquid regeneration by the electrolysis method, that is, the leaching liquid is immersed in the electrolytic cell and the sulfide The circulation is continuously circulated, and the leachate is continuously regenerated and regenerated in the electrolytic cell by electrolysis. After the leaching solution, the sulphide is continuously leached, and the leaching of the sulphide is synchronized with the regeneration of the leaching solution.

In the conventional leaching process, the catalyst needs to consume the oxidant for regeneration, which not only increases the cost, but also greatly increases the cell pressure of the electrolysis process (the anode is a helium oxygen reaction during electrolysis), and the method of electrochemical oxidation of the present invention The regeneration residue is directly regenerated at the anode, which greatly reduces the cell pressure of the electrolysis, so that the electrolysis cell pressure of the lead sulfide ore is 0.6V (current density 200A/m ² ), and the electrolysis cell pressure of the copper sulfide ore is 0.4 V (current Density 200A/m ² ), the antimony sulfide ore has an electrolytic cell pressure of 0.35V (current density 200A/m ² ). Compared with traditional hydrometallurgy, the electrolytic energy consumption is saved by 70%, making the cost of hydrometallurgy even lower. At the level of pyrometallurgy. The invention can make the leaching of the sulfide synchronous with the electrolysis, and convert the sulfide into the metal and the elemental sulfur by electrolysis, thereby avoiding the possible environmental pollution of the sulfur dioxide and improving the conversion rate of the sulfide.

At the same time, in this solution, the complexing agent can significantly inhibit the discharge remaining in the cathode, so that the electrolysis tank does not require a membrane, and the effect of cathode metal deposition and anode catalyst regeneration can be achieved. The use of electrodeposition additives can significantly improve the deposition morphology of the cathode, resulting in a relatively flat cathode deposited metal. Elemental sulfur can be obtained by separation of the product after sulfide leaching.

For different metal sulfides, the S ² -concentration in the solution is different due to the difference in their solubility products, so that catalysts with different oxidizing powers are required for leaching, which allows different sulfides to be separated by leaching. For example, for impurities that cannot be converted in sulfides, copper sulfide in lead sulfide ore, because the solubility product of copper sulfide is much smaller than that of lead sulfide, the catalyst required for copper sulfide leaching is more oxidizing and can be subjected to fractional leaching. The separation is achieved by first leaching the lead sulfide in the lead sulphide ore, followed by secondary leaching of the copper sulphide so that the valuable metals in the sulphide are sufficiently recovered.

I) Dispose 10L pretreatment liquid containing 1.0 mol of diethylenetriaminepentaacetic acid and 0,7 mol/L lead oxide, add 5 kg of lead sulfide ore containing no copper, and stir the reaction at a constant temperature for 5 hours under 55- conditions. With pretreatment liquid. The pretreatment liquid is regenerated by electrolysis.

2) Add U) mol/L ammonia triacetate, 0,05 mol/L cobalt sulfate, lm() l/L sodium chloride, (moi/L lead oxide, 2 g/) in a 10 L reactor and a 10 L electrolytic cell. L gelatin leachate, The leachate is circulated between the reactor and the electrolysis cell, and the temperature of the leachate is maintained between 60 and 65 °C.

The pH of the leachate is maintained between 7.5 and 8,5 during the reaction with hydrazine hydrochloride buffer solution. In the reaction kettle, the lead sulfide ore obtained in the step 1) is added, and the anode in the electrolytic cell is a graphite plate of 30*30*0„5 (length*width*thickness) cm ³ , and the cathode is 30*30*0,1 (long *width*thickness) cm ³ lead plate, current density 400A/m ² constant current electrolysis. The lead sulfide electrolyzed into the reactor is all converted into elemental sulfur, and the electrolysis voltage is gradually increased to 1.0V to stop. In the leachate obtained, elemental sulfur is obtained, and lead is deposited in the electrolytic cell. During the electrolysis process, the electrolysis voltage is averaged at 0,65 V, and the electricity consumption per ton of lead in the electrolysis process is 167 kWM.

Example 2:

1) Dispose 100L pretreatment liquid containing 0,9mol ammonia triacetic acid and 0.3moi/L copper sulfate, add 10kg copper sulfide ore, and stir the reaction for 4 hours under the condition of 75-801: to make zinc in copper sulfide ore. Iron, manganese, lead and other impurities are converted into copper sulfide to separate the purified copper sulfide ore and pretreatment liquid. The pretreatment liquid is regenerated by electrolysis.

2) Adding 0,5 mol/L ethylenediaminetetraacetic acid, 0.011 mol/L, sulfuric acid 43⁄4, 2 mol/L potassium silicate, 0.2 mol/L copper sulphate, in a 50 L reactor and a 100 L electrolytic cell, 5g / L rosin, 0.5g / L β - naphthol leaching solution, leaching solution 釆 with acetic acid sodium acetate buffer solution to adjust the pH between 4.0 - 4. 5, the leaching solution in the reactor and the electrolytic cell After filtration and circulation, the temperature of the leachate is maintained between 90-951:. Copper sulfide autoclave, Step 1) is obtained, the electrolytic cell anode is 100 * 100 * 1 (length * width * thickness) cm ³ of titanium electrodes, cathode 100 0,1 * 100 * (L * W * Thick) cm ³ Stainless steel passivated with potassium permanganate, constant current electrolysis at a current density of 700 A/m ² . The copper sulfide in the electrolysis to the tank reactor was all converted into sulfur, at which time the electrolysis voltage was gradually increased to 0.85 V, and the reaction was stopped. The separation is reversed. The leachate in the kettle is subjected to elemental sulfur, and the cathode in the electrolytic cell is deposited. During the electrolysis process, the electrolysis voltage averages 0,6 V, and the electricity consumption per ton of copper in the electrolysis process is 500 kWM.

It should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art The technical solutions described in the foregoing embodiments may be modified, or some of the technical features may be equivalently replaced. Where within the spirit and principles of the present invention, Any modifications, equivalent substitutions, improvements, etc., are intended to be included within the scope of the present invention.

Claims

1. A hydrometallurgical smelting method for metal sulfides, characterized by including:

1) Add metal A sulfide to the leach solution, and finally generate metal A complex, elemental sulfur, and reduced catalyst;

2) Filter the leach solution containing metal A complex, elemental sulfur, and reduced catalyst processed in step 1) and then inject it into the electrolytic cell. Use an inert electrode as the anode, metal A or an inert electrode as the cathode, and pass Electrolysis yields metal A at the cathode. A hydrometallurgical smelting method for metal sulfides, characterized by:

Metal A sulfide containing impurity metal sulfide is added to the pretreatment liquid for treatment, and the impurity metal sulfide in the metal A sulfide is converted into metal A sulfide.

3. The hydrometallurgical smelting method of metal sulfides according to claim 2, characterized in that: in the pretreatment liquid treated in step a, metal replacement or electrolysis is used to recover valuable metals and make the pretreatment liquid. be regenerated;

Step 2) further includes: the reduced catalyst undergoes an electrochemical reaction at the anode and is re-oxidized into a catalyst, and the metal A complex is reduced at the cathode to obtain metal A and the complexing agent, thereby regenerating and recycling the leach solution.

4. The hydrometallurgical smelting method of metal sulfides according to claim 2, characterized in that in step a, the pretreatment liquid contains a complexing agent and a metal A salt, wherein a buffer solution is used to adjust the pretreatment liquid. The pH value of the treatment solution is between 3.0-9,0.

5. The hydrometallurgical smelting method of metal sulfides according to claim 〗 or 2, characterized in that the metal A sulfide is a sulfide or sulfide ore of copper, iron, zinc, bismuth, nickel, cadmium, and lead. one of them.

6. The hydrometallurgical smelting method of metal sulfides according to claim 4, characterized in that in step a, in the pretreatment liquid, the complexing agent is an α-amino acid and contains an aminodiacetic acid group. The metal A salt is one or more of sulfate, nitrate oxide, chloride, and acetate of metal A, with a concentration of 0.05-10 mol/L;

Among them, step a also includes:

A buffer solution is used to maintain the pH value of the solution between 3,0 and 9.0 during the reaction. The buffer solution contains hydrochloric acid, glycine-hydrochloric acid, ammonium acetate, sodium acetate, hexamethylenetetramine-hydrochloric acid, and phosphoric acid. One or more of sodium dihydrogen - sodium hydroxide, carbonic acid - hydrogen carbonate, with a mass concentration of

1-50% solution, reaction temperature between 15-iocrc.

7. The hydrometallurgical smelting method of metal sulfides according to claim 6, characterized in that the complexing agent is ethylenediaminediacetic acid, propylenediaminediacetic acid, nitrilotriacetic acid, iminodiacetic acid, ethanol Diamine tetraacetic acid, ethylene glycol diethyl ether diamine tetraacetic acid, hydroxyethyl ethylenediamine triacetic acid, diethylenetriamine pentaacetic acid, aspartic acid, alanine, valine, glutamic acid, proline Acid, amino acid, phenylalanine, leucine, histidine, asparagine, glycine, threonine, serine, glutamine, citrulline, lysine, arginine, cysteine , methionine, ornithine, one or more, the concentration is 0.3-3.5mol/L.

8. The hydrometallurgical smelting method of metal sulfides according to claim 1, characterized in that, in step 1), the leach solution includes complex residues, catalysts, conductive salts, metal A salts, and electrodeposition Add sodium chloride, and use buffer solution to adjust the pH value of the leach solution between 1.5 and 0.0.

9. The hydrometallurgical smelting method of metal sulfides according to claim 8, characterized in that in the leach solution, the complexing agent is an α-amino acid, containing an aminodiacetic acid group or a aminoacetic acid group. One or more of the aminocarboxylic complexing agents, the concentration is 0.3-3,5moi/L;

The catalyst is one or more of cobalt salt, iron salt, manganese salt and dichromate, with a concentration of 0.01-1.0 mol/L;

In the conductive salt, the cation is one or more of Na ⁺ K ⁺ and NH, and the anion of the conductive salt is cr, S0 ₄ ² -, N0 ₃ ·', P ₂ 0 ₇ ⁴ · One or more types of conductive salt, the concentration of conductive salt is 0.5-4mol/L;

The metal A salt is a sulfate, nitrate, oxide, chloride, acetate of metal A One or more of them, the concentration is 0,05 1„0mol/L;

The electrodeposition additive is one or more of gelatin, bone glue, β-naphthol, rosin, and sodium lignosulfonate, with a concentration of 0.1-9g/L.

10. The hydrometallurgical smelting method of metal sulfides according to claim 9, characterized in that the complexing agent is ethylenediaminediacetic acid, propylenediaminediacetic acid, nitrilotriacetic acid, iminodiacetic acid, ethanol Diamine tetraacetic acid, ethylene glycol diethyl ether diamine tetraacetic acid, hydroxyethyl ethylenediamine triacetic acid, diethylenetriamine pentaacetic acid, aspartic acid, alanine, valine, glutamic acid, proline Acid, amino acid, phenylalanine, leucine, histidine, asparagine, glycine, threonine, serine, glutamine, citrulline, lysine, arginine, cysteine , methionine, ornithine, one or more of them, the concentration is 0.3-3.5mol/L.

11. The hydrometallurgical smelting method of metal sulfides according to claim 1 or 8, characterized in that step 1) further includes:

When the metal A is copper, a buffer solution is used to control the pH value of the solution between 1,5-6.0. The buffer solution contains beneficial acids, ammonium acetate, hydrochloric acid-disodium hydrogen citrate, and hydrogen sulfosalicylate. One or more of potassium sodium hydroxide, acetic acid - acetic acid], a solution with a mass concentration of 1 to 50%;

When the metal A is lead, bismuth, zinc, cadmium, nickel, or iron, a buffer solution is used to control the pH value of the solution between 4.5 and 10.0. The buffer solution contains hydrochloric acid, ammonium acetate, acetic acid-sodium acetate, ethanolamine hydrochloride, and carbonic acid. Sodium - one or more types of sodium bicarbonate, a solution with a mass concentration of 1-50%.

12. The hydrometallurgical smelting method of metal sulfides according to claim 1, characterized in that, in step 2), further comprising:

The reaction temperature is 15-i iO°C, and the electrolysis current density is 50-1000A/m ² .

13. The hydrometallurgical smelting method of metal sulfides according to claim 1, wherein step 2) further includes:

The electrolysis process adopts constant current electrolysis, the electrolysis temperature is in the range of 15-45 °C, the anode current density is in the range of 50-20()A/ ^m2 , and the cathode current density is in the range of 100-300A/ ^m2 ; or,

The electrolysis temperature is in the range of 45-80 °C, the anode current density is in the range of 200-400A/m ² , and the cathode current density is in the range of 300-600A/1H ² ; The electrolysis temperature is in the range of 80 l lO'C, the anode current density is in the range of 400-700A/m ² , and the cathode current density is in the range of 600-1000A/m ² .