阅读说明：本技术 一种铜电解液净化资源综合利用的方法 (Method for comprehensively utilizing copper electrolyte purification resources ) 是由 王学文 王懿 孟钰麒 王明玉 田晟晖 于 2019-09-25 设计创作，主要内容包括：本发明公开了一种铜电解液净化资源综合利用的方法,铜电解液经预脱铜后,再经蒸发浓缩进一步结晶分离铜,然后往结晶后液中加入促进剂,促使杂质砷、锑、铋自净化沉淀析出,然后采用扩散渗析将自净化后液中的硫酸和硫酸盐分开,硫酸盐溶液则先用碱性物质调pH氧化除铁,除铁后液再用溶剂萃取法或分段中和净化法去除其中除Ni以外的二价及二价以上的阳离子,使铜、锌、钴等有价金属得到综合回收,最后在除杂后液中加入硫酸铵结晶析出硫酸镍铵,实现铜电解液净化工艺过程的资源化综合利用。本发明具有铜电解液净化效果好,资源综合利用率高,生产成本低,环境友好等优点,适合于铜电解液净化工业生产应用。(The invention discloses a method for comprehensively utilizing purified resources of copper electrolyte, which comprises the steps of pre-decoppering the copper electrolyte, further crystallizing and separating copper by evaporation and concentration, adding an accelerant into the crystallized liquid to promote self-purification precipitation of impurities arsenic, antimony and bismuth, separating sulfuric acid and sulfate in the self-purified liquid by diffusion dialysis, adjusting pH of the sulfate solution by using an alkaline substance to oxidize and remove iron, removing divalent and more than divalent cations except Ni from the iron-removed liquid by using a solvent extraction method or a segmented neutralization purification method to comprehensively recover valuable metals such as copper, zinc and cobalt, and finally adding ammonium sulfate into the impurity-removed liquid to crystallize and separate out nickel ammonium sulfate so as to realize resource comprehensive utilization of the purification process of the copper electrolyte. The method has the advantages of good purification effect of the copper electrolyte, high comprehensive utilization rate of resources, low production cost, environmental friendliness and the like, and is suitable for industrial production and application of copper electrolyte purification.)

1. A method for comprehensively utilizing copper electrolyte purification resources is characterized by comprising the following steps: the copper electrolyte is evaporated and concentrated to free H after pre-decoppering₂SO₄The concentration reaches 4-10 mol/L, the residual copper crystals are separated out after cooling, and crude copper sulfate and a first crystallized solution are obtained after filtering; the obtained crude copper sulfate returns to the pre-copper removal process to recover copper, the first crystallized solution is subjected to indirect self-purification to remove impurities such as arsenic, antimony and bismuth, and then sulfuric acid and sulfate in the first crystallized solution are separated through diffusion dialysis to obtain sulfuric acid and a sulfate solution; returning the obtained sulfuric acid solution to a copper electrolyte circulating system for continuous use, firstly adjusting the pH of the sulfuric acid solution to 3.2-4.1 by using an alkaline substance, carrying out blast oxidation to remove iron, and filtering to obtain iron-removing slag and iron-removing liquid;

removing bivalent and above-bivalent cations except Ni from the solution after iron removal by using a solvent extraction method, and carrying out phase separation to obtain a loaded organic phase and a first solution after impurity removal; the loaded organic phase is back extracted by inorganic acid solution, and valuable metals in the loaded organic phase are separated and recovered; or

Removing bivalent and above-bivalent cations except Ni by a sectional neutralization purification method, and filtering to obtain filter residues containing copper, zinc and cobalt and a second impurity-removed solution;

adding ammonium sulfate into the first impurity-removed liquid or the second impurity-removed liquid to crystallize double salt and enrich nickel, and filtering to obtain nickel ammonium sulfate crystals and a second crystallized liquid;

the obtained nickel ammonium sulfate crystal is directly sold as a product or is sold as a nickel sulfate product after pyrolysis; directly returning the second crystallized solution to a copper electrolyte circulating system, or adding an alkaline substance for neutralization to separate out residual nickel precipitate, and filtering to obtain nickel-containing neutralized slag and neutralized solution; the nickel-containing neutralization slag is returned to be used for adjusting the pH value of the sulfate solution, and the neutralized liquid wastewater is recycled, so that the resource comprehensive utilization of the copper electrolyte purification process is realized.

2. The method for comprehensively utilizing the copper electrolyte purification resources according to claim 1, characterized by comprising the following steps: the indirect self-purification is to add antimony or/and bismuth oxide and hydrate thereof as an accelerant into the first crystallized liquid to promote the mutual combination of impurities arsenic, antimony and bismuth therein to form arsenic antimonate precipitate; the molar ratio of Sb (III)/[ Sb (III)) + Bi (III)) + Sb (IV)) + Sb (V)) in the accelerator is 0.5-1;

the conditions of the indirect self-purification process are as follows: adding an accelerant according to the molar ratio of the As in the first crystallized liquid to the Sb in the accelerant being 1: 0.5-5, stirring and contacting for 0.5-5h at 25-105 ℃, and filtering to obtain a loaded accelerant and a self-purified liquid; the load promoter is desorbed and regenerated by alkali solution, the regenerated promoter returns to the indirect self-purification process for recycling, and the self-purified liquid adopts diffusion dialysis to separate the sulfuric acid from the sulfate.

3. The method for comprehensively utilizing the copper electrolyte purification resources according to claim 2, characterized by comprising the following steps: desorbing and regenerating the load-bearing promoter by using an alkali solution, namely adding water into the load-bearing promoter according to the solid-to-liquid ratio of 1: 2-10 g/mL, stirring, adjusting the pH value to 7.5-9.5 by using the alkali solution, stirring and leaching at 25-95 ℃ for 1-3 h to allow arsenic and bismuth in the load-bearing promoter to enter the solution, filtering to obtain a regenerated promoter and a reacted solution, continuously adding the alkali solution into the reacted solution, and adjusting the pH value to 12-14 at 50-100 ℃; or adding an acid solution into the reacted liquid, adjusting the pH value to 2.5-5.5 at 5-85 ℃, filtering to obtain bismuth-rich slag and a bismuth-removed liquid, adding lime into the bismuth-removed liquid for causticization, filtering to obtain calcium arsenate and an alkali solution, and returning the alkali solution for desorption and regeneration of the load promoter.

4. The method for the comprehensive utilization of the copper electrolyte purification resources according to claim 1 or 2, characterized in that: the diffusion dialysis is to separate sulfuric acid and sulfate in self-purified liquid by using an anion diffusion dialysis membrane to obtain sulfuric acid and sulfate solution, the obtained sulfuric acid solution is returned to a copper electrolyte circulating system for continuous use, and the sulfate solution is used for comprehensively recovering valuable metals;

the process parameters of diffusion dialysis are as follows: controlling the flow rate of the self-purified liquid to be 0.5-1.8L/h.m²And the flow rate ratio of the water to the self-purified liquid is 0.5-1.5: 1.

5. The method for the comprehensive utilization of the copper electrolyte purification resources according to claim 1 or 2, characterized in that: the alkaline substance is at least one selected from calcium oxide, calcium hydroxide, calcium carbonate, sodium hydroxide, sodium carbonate, sodium bicarbonate, solid containing nickel hydroxide or/and copper hydroxide or/and zinc hydroxide.

6. The method for the comprehensive utilization of the copper electrolyte purification resources according to claim 1 or 2, characterized in that: the solvent extraction is to perform single-stage or multi-stage contact extraction on an organic phase after saponification and a trapped fluid, wherein the single-stage contact time of the extraction is 5-35 min, the extraction temperature is 10-55 ℃, the extraction is performed under the condition that the pH is 3.5-5.5, divalent and above-divalent cations except nickel are separated, and a loaded organic phase and a first impurity-removed liquid are obtained by phase separation;

the organic phase consists of an extracting agent and a diluting agent, or consists of an extracting agent, a diluting agent and a phase regulator; the extractant is an acidic phosphate extractant, the diluent is kerosene, and the regulator is a high-carbon alcohol or neutral phosphorus type extractant; the volume percentage concentration of the acidic phosphate ester extractant in the organic phase is 5-35 percent, the volume percentage concentration of the diluent is 65-95 percent, and the volume percentage concentration of the phase regulator is 0-10 percent; the acidic phosphate extractant is selected from one of P204, P507, P538 and Cyanex 272;

the saponification means that the organic phase is selected from one of ammonia soap, sodium soap and nickel soap, and the saponification rate is 10-80%.

7. The method for comprehensively utilizing the copper electrolyte purification resources according to claim 6, characterized by comprising the following steps: the loaded organic phase is back extracted by an inorganic acid solution, and valuable metals in the loaded organic phase are separated and recovered; h in the inorganic acid solution⁺Concentration of 0.2-3 mol/L, Cl^-The concentration is 0-18 mol/L; carrying out single-stage or multi-stage contact back extraction on the loaded organic phase and the inorganic acid solution; multistage contact stripping process, H⁺Increasing the concentration sequentially, back-extracting the valuable metal ions one by one, or using H⁺Back extraction of impurity ions with the same concentration of back extraction liquid; the back extraction single-stage contact time is 5-50 min, the back extraction temperature is 15-50 ℃, and the inorganic acid is selected from sulfuric acid, hydrochloric acid or nitric acid.

8. The method for the comprehensive utilization of the copper electrolyte purification resources according to claim 1 or 2, characterized in that: and the segmented neutralization and purification comprises the steps of adding alkaline substances into the liquid after iron removal, grinding or stirring and ball milling, firstly adjusting the pH value to 4.2-5.6, hydrolyzing, precipitating and removing copper, filtering to obtain copper-rich slag and a liquid after copper removal, continuously adjusting the pH value of the solution to 5.7-7.2, hydrolyzing, precipitating and removing zinc, filtering to obtain zinc-rich slag and a liquid after zinc removal, then adding ammonium fluoride or sodium fluoride into the liquid after zinc removal to remove calcium and magnesium, simultaneously adding hydrogen peroxide or sodium persulfate to oxidize and remove cobalt, and filtering to obtain cobalt-rich slag and a second liquid after impurity removal.

9. The method for the comprehensive utilization of the copper electrolyte purification resources according to claim 1 or 2, characterized in that: adding ammonium sulfate into the first impurity-removed solution or the first impurity-removed solution according to the theoretical amount of nickel converted into nickel ammonium sulfate which is 0.8-1.2 times of the theoretical amount of the nickel ammonium sulfate complex salt, crystallizing at-5-35 ℃ for at least 0.5h to separate out Ni in the nickel ammonium sulfate complex salt by crystallization, and filtering to obtain nickel ammonium sulfate crystals and a second crystallized solution;

and directly returning the second crystallized solution to a copper electrolyte circulating system for continuous use, or neutralizing with an alkaline substance until the pH value is more than 9.5, precipitating residual nickel in the solution, filtering to obtain a nickel-containing precipitate and a neutralized solution, and returning the obtained nickel-containing precipitate to be used for adjusting the pH value of the sulfate solution.

10. The method for the comprehensive utilization of the copper electrolyte purification resources as claimed in claim 1, 2 or 9, wherein: directly selling the nickel ammonium sulfate crystal as a product, or pyrolyzing the nickel ammonium sulfate crystal at 380-830 ℃ for 1-5 h to convert the nickel ammonium sulfate crystal into anhydrous nickel sulfate, directly selling the obtained anhydrous nickel sulfate as a product, or adding water to dissolve the anhydrous nickel sulfate and then recrystallizing, filtering to obtain refined nickel sulfate and a third crystallized liquid, selling the refined nickel sulfate as a product, returning the third crystallized liquid to be continuously used as a dissolving liquid of the anhydrous nickel sulfate, and absorbing flue gas generated in the thermal decomposition process with water to obtain an ammonium sulfite solution;

the ammonium bisulfite solution is a mixed solution of ammonium sulfite and ammonium bisulfite, ammonia is firstly added into the mixed solution to be converted into an ammonium sulfite solution, then the ammonium sulfite solution is oxidized to be converted into an ammonium sulfate solution, and the obtained ammonium sulfate solution is returned to be continuously used as a crystallization agent of ammonium sulfate nickel double salt;

the oxidation is to add one of hydrogen peroxide, ozone, oxygen and air as an oxidant into the ammonium sulfite solution to convert the ammonium sulfite solution into an ammonium sulfate solution.

Technical Field

The invention belongs to the field of hydrometallurgy, and particularly relates to a method for comprehensively utilizing purification resources of a copper electrolyte, which is suitable for the comprehensive utilization of copper, acid, nickel, zinc, cobalt, arsenic, antimony, bismuth and the like in the purification process of the copper electrolyte.

Background

During copper electrorefining, the impurities contained in the anodic copper exhibit different behaviors, classified in their electrochemical order and their solubility in the electrolyte as follows:

the first type of impurities include zinc, iron, nickel, cobalt, lead, tin, and the like. They are more electronegative than copper and thus electrochemically dissolve at the anode. In which lead and tin form an electrolyte-insoluble sulphate-PbSO₄And Sn (OH)₂SO₄The contents of these two elements in the electrolyte are very limited. The rest of the electrolyte enters the electrolyte in an ionic state, and generally does not precipitate on the cathode.

The second class of impurities is mainly gold, silver and platinum group metals. They are more electropositive than copper and the electrolysis process is almost insoluble and proceeds directly to the anode sludge. But silver is present in small amounts as Ag₂SO₄And the silver enters the electrolyte, and under the action of chloride ions in the electrolyte, the silver is precipitated into anode mud by AgCl.

The third type of impurities are mainly compounds of oxygen, sulfur, selenium, tellurium, etc. (Cu)₂O、Cu₂S、Cu₂Se、Cu₂Te) which generally do not dissolve into the sludge during copper electrolysis.

The fourth class of impurities is mainly arsenic, antimony, bismuth. Their potential is close to that of copper, and during electrolysis they can be electrochemically dissolved together with (even preferentially) copper on the anode, can be precipitated on the cathode together with copper ions, and can enter the cathode in other forms, thus greatly reducing the quality of cathode copper. Therefore, the purification of the copper electrolyte is generally referred to As the removal of impurities As, Sb, and Bi.

In the copper electrolytic refining process, besides zinc, iron, nickel, cobalt, arsenic, antimony and bismuth, impurities such as calcium, magnesium, sodium, ammonium and the like are also generated in the copper electrolyte, the calcium, the magnesium and the sodium are mainly introduced in the anode copper demoulding and electrolytic cell repairing process, and the ammonium is a metabolite of thiourea which is an additive of copper electrolysis.

It is well known that although the electrodeposition decoppering and dedatating process has been used in industrial production for over 100 years, it has many drawbacks, such as: 1) the impurity removal efficiency is low, and the electric energy consumption is large; 2) black copper powder or sponge copper is separated out, so that the direct yield of copper is influenced; 3) producing highly toxic arsine gas. Therefore, people are studying new methods for purifying copper electrolyte to remove impurities As, Sb and Bi, including purifying copper electrolyte with stannic acid and active carbon, subjecting barium carbonate and carbonic acid to co-precipitation to remove Bi, extracting Sb and Bi with organic solvent, and adsorbing As, Sb, Bi and the like with antimony or bismuth-containing adsorbent. However, these methods can only be used for removing arsenic, antimony and bismuth as impurities, but cannot remove nickel, iron and other impurities. However, these methods cannot remove arsenic, antimony and bismuth in the copper electrolyte in proportion, so they can only be used as a supplement to the electrodeposition copper removal impurity removal process, and cannot completely replace the traditional copper electrolyte purification process. In order to realize the one-time removal of impurities As, Sb and Bi, a pressure vulcanization impurity removal process is recently proposed, and the obtained fluidized slag is returned to a copper pyrometallurgical smelting system for recovering copper, wherein the defects that the impurities As, Sb and Bi are not discharged and are in a dead cycle in the whole copper smelting system (pyrometallurgical smelting and electrolytic refining) are overcome.

The nickel is separated and recycled in the purification process of the copper electrolyte, not only because the recycled nickel has certain economic value, but also more importantly, the concentration of the Ni is increased to a certain degree, which is harmful to the copper electrolytic refining process. Recently, it is discovered that with the decrease of high-quality copper concentrate and the increase of the proportion of secondary copper in raw materials, the concentration of impurities such as zinc, iron, nickel, cobalt, magnesium and the like in the electrolyte tends to rise, so that the viscosity of the electrolyte increases, the current efficiency decreases, and the solution after nickel removal cannot return to a copper electrolysis circulating system for continuous use and can only be neutralized by lime as contaminated acid for treatment. In a word, along with the change of copper smelting raw materials, the traditional method for purifying the copper electrolyte is difficult to meet the process requirements of the existing copper electrolytic refining.

Disclosure of Invention

The invention aims to provide a method for comprehensively utilizing copper electrolysis purification resources, which can completely separate impurities in copper electrolyte without electrodeposition copper removal and impurity removal, and has high purification efficiency and low production cost.

The invention relates to a method for comprehensively utilizing purified resources of copper electrolyte₂SO₄The concentration is 4-10 mol/L, the residual copper crystals are separated out after cooling, and crude copper sulfate and a first crystallized solution are obtained after filtering; the obtained crude copper sulfate returns to the pre-copper removal process to recover copper, the first crystallized solution is subjected to indirect self-purification to remove impurities such as arsenic, antimony and bismuth, and then sulfuric acid and sulfate in the first crystallized solution are separated through diffusion dialysis to obtain sulfuric acid and a sulfate solution; returning the obtained sulfuric acid solution to a copper electrolyte circulating system for continuous use, firstly adjusting the pH of the sulfuric acid solution to 3.2-4.1 by using an alkaline substance, carrying out blast oxidation to remove iron, and filtering to obtain iron-removing slag and iron-removing liquid;

removing bivalent and above-bivalent cations except Ni from the solution after iron removal by using a solvent extraction method, and carrying out phase separation to obtain a loaded organic phase and a first solution after impurity removal; the loaded organic phase is back extracted by inorganic acid solution, and valuable metals in the loaded organic phase are separated and recovered; or

Removing bivalent and above-bivalent cations except Ni by a sectional neutralization purification method, and filtering to obtain filter residues containing copper, zinc and cobalt and a second impurity-removed solution;

adding ammonium sulfate into the first impurity-removed liquid or the second impurity-removed liquid to crystallize double salt and enrich nickel, and filtering to obtain nickel ammonium sulfate crystals and a second crystallized liquid;

the obtained nickel ammonium sulfate crystal is directly sold as a product or is sold as a nickel sulfate product after pyrolysis; directly returning the second crystallized solution to a copper electrolyte circulating system, or adding an alkaline substance for neutralization to separate out residual nickel precipitate, and filtering to obtain nickel-containing neutralized slag and neutralized solution; the nickel-containing neutralization slag is returned to be used for adjusting the pH value of the sulfate solution, and the neutralized liquid wastewater is recycled, so that the resource comprehensive utilization of the copper electrolyte purification process is realized.

The invention relates to a method for comprehensively utilizing copper electrolyte purification resources, wherein the cooling temperature is-5-25 ℃, and the cooling time is 5-15 h.

The invention relates to a method for comprehensively utilizing purified resources of copper electrolyte, wherein the indirect self-purification is to add antimony or/and bismuth oxide or hydrate thereof as an accelerant into the first crystallized liquid to promote the mutual combination of impurities arsenic, antimony and bismuth therein to form arsenic antimonate precipitate; the molar ratio of Sb (III)/[ Sb (III)) + Bi (III)) + Sb (IV)) + Sb (V)) in the accelerator is 0.5-1;

the conditions of the indirect self-purification process are as follows: adding an accelerant according to the molar ratio of the As in the first crystallized liquid to the Sb in the accelerant being 1: 0.5-5, stirring and contacting for 0.5-5h at 25-105 ℃, and filtering to obtain a loaded accelerant and a self-purified liquid; the load promoter is desorbed and regenerated by alkali solution, the regenerated promoter returns to the indirect self-purification process for recycling, and the self-purified liquid adopts diffusion dialysis to separate the sulfuric acid from the sulfate.

The invention relates to a method for comprehensively utilizing copper electrolyte purification resources, wherein the load promoter is desorbed and regenerated by using an alkali solution, namely the load promoter is added with water and stirred according to a solid-to-liquid ratio of 1: 2-10 g/mL, the pH value is adjusted to 7.5-9.5 by using the alkali solution, the load promoter is stirred and leached for 1-3 h at the temperature of 25-95 ℃, arsenic and bismuth in the load promoter enter the solution, the load promoter and a reacted solution are obtained by filtering, the alkali solution is continuously added into the reacted solution, and the pH value is adjusted to 12-14 at the temperature of 50-100 ℃; or adding an acid solution into the reacted liquid, adjusting the pH value to 2.5-5.5 at 5-85 ℃, filtering to obtain bismuth-rich slag and a bismuth-removed liquid, adding lime into the bismuth-removed liquid for causticization, filtering to obtain calcium arsenate and an alkali solution, and returning the alkali solution for desorption and regeneration of the load promoter.

The invention relates to a method for comprehensively utilizing copper electrolyte purification resources, wherein in the diffusion dialysis, sulfuric acid and sulfate in self-purified liquid are separated by using an anion diffusion dialysis membrane to obtain sulfuric acid and sulfate solution, the obtained sulfuric acid solution is returned to a copper electrolyte circulation system for continuous use, and the sulfate solution is used for comprehensively recovering valuable metals;

the process parameters of diffusion dialysis are as follows: controlling the flow rate of the self-purified liquid to be 0.5-1.8L/h.m²And the flow rate ratio of the water to the self-purified liquid is 0.5-1.5: 1.

The invention relates to a method for comprehensively utilizing the purification resources of a copper electrolyte, wherein the alkaline substance is at least one of calcium oxide, calcium hydroxide, calcium carbonate, sodium hydroxide, sodium carbonate, sodium bicarbonate and solid substances containing nickel hydroxide or/and copper hydroxide or/and zinc hydroxide.

The invention relates to a method for comprehensively utilizing copper electrolyte purification resources, wherein solvent extraction refers to single-stage or multi-stage contact extraction of an organic phase after saponification and a trapped fluid, the single-stage contact time of extraction is 5-35 min, the extraction is carried out under the conditions that the temperature is 10-55 ℃, and the pH is 3.5-5.5, divalent and above-divalent cations except nickel are separated, and a loaded organic phase and a first impurity-removed liquid are obtained by phase separation;

the organic phase consists of an extracting agent and a diluting agent, or consists of an extracting agent, a diluting agent and a phase regulator; the extractant is an acidic phosphate extractant, the diluent is kerosene, and the regulator is a high-carbon alcohol or neutral phosphorus type extractant; the volume percentage concentration of the acidic phosphate ester extractant in the organic phase is 5-45 percent, the volume percentage concentration of the diluent is 55-95 percent, and the volume percentage concentration of the phase regulator is 0-10 percent; the acidic phosphate extractant is selected from one of P204, P507, P538 and Cyanex 272;

the saponification means that the organic phase is selected from one of ammonia soap, sodium soap and nickel soap, and the saponification rate is 10-80%.

The invention relates to a method for comprehensively utilizing copper electrolyte purification resources, wherein a loaded organic phase is subjected to back extraction by using an inorganic acid solution, and valuable metals in the loaded organic phase are separated and recovered; h in the inorganic acid solution⁺Concentration of 0.2-3 mol/L, Cl^-The concentration is 0-18 mol/L; carrying out single-stage or multi-stage contact back extraction on the loaded organic phase and the inorganic acid solution; multistage contact stripping process, H⁺Increasing the concentration sequentially, back-extracting the valuable metal ions one by one, or using H⁺Back extraction of impurity ions with the same concentration of back extraction liquid; the contact time of the back extraction single stage is 5-50 min, the back extraction temperature is 15-50 ℃, and the inorganic acid is selected from sulfuric acid, hydrochloric acid or nitric acid.

The invention relates to a method for comprehensively utilizing purified resources of copper electrolyte, wherein the step of segmented neutralization and purification comprises the steps of adding alkaline substances into a liquid after iron removal, grinding or stirring and ball milling, firstly adjusting the pH value to 4.2-5.6, hydrolyzing, precipitating and removing copper, filtering to obtain copper-rich slag and a liquid after copper removal, continuously adjusting the pH value of the solution to 5.7-7.2, hydrolyzing, precipitating and removing zinc, filtering to obtain zinc-rich slag and a liquid after zinc removal, then adding ammonium fluoride or sodium fluoride into the liquid after zinc removal to remove calcium and magnesium, simultaneously adding hydrogen peroxide or sodium persulfate to oxidize and remove cobalt, and filtering to obtain cobalt-rich slag and a second liquid after impurity removal.

The invention relates to a method for comprehensively utilizing purified resources of copper electrolyte, wherein crystallization double salt is prepared by adding ammonium sulfate into first impurity-removed liquid or second impurity-removed liquid according to the theoretical amount of nickel converted into nickel ammonium sulfate which is 0.8-1.2 times of the theoretical amount of the nickel ammonium sulfate double salt, crystallizing at-5-35 ℃ for at least 0.5h to separate out Ni in the form of nickel ammonium sulfate double salt, and filtering to obtain nickel ammonium sulfate crystals and second crystallization liquid.

The invention relates to a method for comprehensively utilizing copper electrolyte purification resources, wherein the liquid after the second crystallization is directly returned to a copper electrolyte circulating system for continuous use, or is neutralized by alkaline substances until the pH value is more than 9.5, so that residual nickel is precipitated and separated out, a nickel-containing precipitate and the neutralized liquid are obtained by filtration, and the obtained nickel-containing precipitate is returned to be used for adjusting the pH value of a sulfate solution.

The invention relates to a method for comprehensively utilizing purified resources of copper electrolyte, wherein nickel ammonium sulfate crystals are directly sold as products, or the nickel ammonium sulfate crystals are pyrolyzed at 380-830 ℃ for 1-5 h to be converted into anhydrous nickel sulfate, the obtained anhydrous nickel sulfate is directly sold as products, or is recrystallized after being dissolved by water, refined nickel sulfate and third crystallized liquid are obtained by filtering, the refined nickel sulfate is sold as products, the third crystallized liquid is returned to be continuously used for dissolving the anhydrous nickel sulfate, and flue gas generated in the thermal decomposition process is absorbed by water to obtain ammonium sulfite salt solution;

the ammonium bisulfite solution is a mixed solution of ammonium sulfite and ammonium bisulfite, ammonia is firstly added into the mixed solution to be converted into an ammonium sulfite solution, then the ammonium sulfite solution is oxidized to be converted into an ammonium sulfate solution, and the obtained ammonium sulfate solution is returned to be continuously used as a crystallization agent of ammonium sulfate nickel double salt;

the oxidation is to add one of hydrogen peroxide, ozone, oxygen and air as an oxidant into the ammonium sulfite solution to convert the ammonium sulfite solution into an ammonium sulfate solution.

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

1. the method skillfully utilizes the solubility difference of copper sulfate and nickel sulfate in an acid solution, promotes copper crystallization and precipitation through evaporation and concentration, returns a crystallization product to pre-decoppering, converts copper in an electrolyte into cathode copper to the maximum extent, avoids the generation of black copper, and creates conditions for the separation and recovery of other valuable metals.

2. The method for comprehensively utilizing the copper electrolyte purification resources comprises the steps of adding an accelerant into copper sulfate crystallization mother liquor to promote arsenic, antimony and bismuth to be indirectly self-purified and precipitated, regenerating and recycling the load accelerant by using an alkaline solution, and directly separating and recovering the arsenic, antimony and bismuth in the copper electrolyte without electrodeposition copper removal and impurity removal.

3. According to the method for comprehensively utilizing the copper electrolyte purification resources, the sulfuric acid and the sulfate in the self-purified liquid are separated by diffusion dialysis, so that the separation and the reuse of the sulfuric acid are ensured, and the comprehensive recovery of valuable metals such as zinc, nickel, cobalt and the like in the copper electrolyte is realized.

4. According to the method for comprehensively utilizing the copper electrolyte purification resources, the copper electrolyte is subjected to solvent extraction or sectional neutralization purification to separate impurities such as zinc, cobalt and the like, ammonium sulfate is added into the solution, nickel in the copper electrolyte is crystallized and separated out in the form of nickel ammonium sulfate, and the nickel ammonium sulfate crystals are pyrolyzed to directly obtain a nickel sulfate product, so that the process of separating and recovering the qualified nickel sulfate product from the copper electrolyte is greatly simplified.

5. The method for comprehensively utilizing the copper electrolyte purification resources successfully realizes the comprehensive utilization of copper, acid, nickel, zinc, cobalt and the like in the copper electrolyte, and removes iron, sodium, calcium, magnesium and the like in the copper electrolyte, so that the copper electrolyte is thoroughly purified.

Drawings

FIG. 1 shows a conventional process flow for copper electrolyte purification.

Fig. 2 is a process flow of the comprehensive utilization of the copper electrolyte purification resources in embodiment 1 of the present invention.

Fig. 3 is a process flow of comprehensive utilization of copper electrolyte purification resources in example 3 of the present invention.

Detailed Description

The invention will now be further described with reference to the following examples, which are intended to illustrate the invention but not to limit it further.