A copper, zinc, germanium complexing agent R3T4, and a preparation method and application thereof

Abstract

The application discloses a copper, zinc and germanium complexing agent R3T4 and a preparation method and application thereof. The copper, zinc and germanium complexing agent R3T4 is prepared from raw materials of soluble ferric salt, vanadate, citrate and nitrate. The copper, zinc and germanium complexing agent R3T4 can be used in a wet leaching process of complex materials containing copper, zinc and germanium, has good stability, oxidation dissociation capacity and complexing and complexing effect in a high-acid and high-temperature system, can promote valuable metals such as copper, zinc and germanium to transform from a difficult-to-dissolve state to a soluble state, improve the leaching efficiency of the valuable metals, and is suitable for resource recycling of copper smelting flue dust, leaching residue and other complex multi-metal materials.

Description

Technical Field

[0001] This invention belongs to the field of metallurgical technology, specifically relating to a copper, zinc, and germanium flux R3T4, its preparation method, and its application. Background Technology

[0002] Polymetallic material resource utilization refers to the process of efficiently separating, enriching, and extracting copper, nickel, zinc, gold, silver, and rare metals (such as indium and rhenium) from complex solid waste, low-grade ores, or industrial by-products containing multiple valuable metals through physical, chemical, and biological means. The aim is to achieve "turning waste into treasure" and a closed loop of circular economy. Currently, wet leaching methods for complex materials such as copper, zinc, and germanium all suffer from high processing costs, low grades of valuable metals such as copper and germanium, and low recovery rates. Therefore, it is essential to develop a product and method that can solve the above-mentioned technical problems. Summary of the Invention

[0003] The first objective of this invention is to provide a copper, zinc, and germanium co-solvent R3T4; the second objective is to provide a method for preparing the copper, zinc, and germanium co-solvent R3T4; and the third objective is to provide applications of the copper, zinc, and germanium co-solvent R3T4.

[0004] The first objective of this invention is achieved by the fact that the copper, zinc, and germanium co-solvent R3T4 is prepared from soluble trivalent iron salts, vanadates, citrates, and nitrates.

[0005] The second objective of this invention is achieved by including pretreatment and evaporation crystallization steps, specifically including: A. Pretreatment: Dissolve the soluble ferric salt, vanadate, citrate and nitrate in water according to the formula, and add an alkaline adjuster under stirring until the pH of the system is 3.5~4.0 to obtain material a; B. Evaporation and crystallization: Material a is subjected to evaporation and crystallization reaction at a temperature of 68~78℃. After cooling, the target copper, zinc and germanium co-solvent R3T4 is obtained.

[0006] The specific steps are as follows: Using soluble ferric salts, vanadates, citrates, and nitrates as main raw materials, and adjusting the pH of the system with an alkaline regulator, the mixture is prepared through dissolution and mixing, pH adjustment, in-situ complexation, evaporation crystallization, and cooling. The preparation method includes: weighing soluble ferric salts, vanadates, citrates, and nitrates according to the formula ratio, dissolving them in water and mixing thoroughly; adding an alkaline regulator under stirring to adjust the pH of the system to 3.5–4.0; then carrying out an evaporation crystallization reaction at 68–78℃ for 1–3 hours; after the reaction, naturally cooling at room temperature for 2–4 hours to obtain copper, zinc, and germanium co-solvent R3T4.

[0007] The preparation principle is as follows: the preparation of R3T4 cosolvent belongs to the in-situ complexation-composite crystallization synthesis process. Soluble ferric salts, vanadates, citrates, and nitrates dissociate in aqueous solution to form Fe... 3+ Active components include vanadate, citrate, and nitrate; under pH 3.5–4.0 conditions, citrate reacts with Fe... 3+ A complexation reaction occurs, forming an iron-citric acid complex component, which inhibits iron ion hydrolysis and improves system stability. Vanadate ions form a vanadium oxidation active component in the weakly acidic system, while nitrate ions remain in the system as an auxiliary oxidation component. Subsequently, evaporation and crystallization are carried out at 68–78 °C, allowing the iron complex component, vanadium oxidation component, nitrate ions, and sodium salt component to co-enrich, composite, and crystallize, ultimately yielding a homogeneous and structurally stable composite copper, zinc, and germanium co-solvent, R3T4. This process differs from simple physical mixing of raw materials; instead, it achieves synergistic stabilization of multiple active components through pH control, in-situ complexation, and composite crystallization.

[0008] The principle of R3T4 as a co-solvent for copper, zinc, and germanium: In high-acid, high-temperature leaching systems, R3T4 co-solvent primarily promotes the transformation of valuable metals such as copper, zinc, and germanium from their insoluble to soluble states in complex materials through the synergistic effects of oxidative dissociation, complexation stabilization, and inhibition of passivation. Its iron, vanadium, and nitrate components enhance the system's oxidizing capacity, disrupting the stable bond structures formed by copper, zinc, and germanium with sulfides, oxides, ferrates, or silicates in the material, thus releasing the target metals into the solution. The citrate component can complex with copper, zinc, and germanium ions, reducing the risk of hydrolysis, precipitation, or re-adsorption, thereby improving the stability and leaching rate of the metals in the leachate.

[0009] The relevant chemical equation is as follows: MeO+2H + →Me 2+ +H2O MeS+2Fe 3+ →Me 2+ +2Fe 2+ +S 0 Me n+ +Cit 3- →Me-Cit In the formula, Me represents valuable metals such as Cu, Zn, and Ge, and Cit represents... 3- It represents citrate.

[0010] The third objective of this invention is achieved by the application of the copper, zinc, and germanium co-solvent R3T4 in the resource recovery process of copper smelting dust, leaching residue, and complex polymetallic materials.

[0011] The copper, zinc, and germanium co-solvent R3T4 described in this invention can be used in the wet leaching process of complex materials containing copper, zinc, and germanium. It has good stability, oxidative dissociation ability, and complexation and solubilization effect in high acid and high temperature systems. It can promote the conversion of valuable metals such as copper, zinc, and germanium from insoluble to soluble states, improve the leaching efficiency of valuable metals, and is suitable for the resource recovery of copper smelting dust, leaching residue, and other complex polymetallic materials. Detailed Implementation

[0012] The present invention will be further described below with reference to embodiments, but this is not intended to limit the present invention in any way. Any modifications or substitutions made based on the teachings of the present invention shall fall within the protection scope of the present invention.

[0013] The copper, zinc, and germanium co-solvent R3T4 described in this invention is prepared from soluble trivalent iron salts, vanadates, citrates, and nitrates.

[0014] The copper, zinc, and germanium co-solvent R3T4 is prepared from raw materials consisting of 2-10 parts by weight of soluble trivalent iron salt, 0.5-3 parts by weight of vanadate, 0.5-2 parts by weight of citrate, and 2-15 parts by weight of nitrate.

[0015] The preparation method of the copper, zinc, and germanium co-solvent R3T4 of the present invention includes pretreatment and evaporation crystallization steps, specifically including: A. Pretreatment: Dissolve the soluble ferric salt, vanadate, citrate and nitrate in water according to the formula, and add an alkaline adjuster under stirring until the pH of the system is 3.5~4.0 to obtain material a; B. Evaporation and crystallization: Material a is subjected to evaporation and crystallization reaction at a temperature of 68~78℃. After cooling, the target copper, zinc and germanium co-solvent R3T4 is obtained.

[0016] The cooling described in step B is natural cooling, and the cooling time is 2-4 hours.

[0017] The application of the copper, zinc, and germanium co-solvent R3T4 described in this invention is its application in the resource recovery process of copper smelting dust, leaching residue, and complex polymetallic materials.

[0018] The present invention will be further described below with reference to specific embodiments: Example 1

[0019] Weigh 20g of ferric sulfate, 5g of sodium vanadate, 5g of sodium citrate, and 20g of sodium nitrate, add them to 300mL of water and stir to dissolve. Slowly add sodium hydroxide solution to adjust the pH of the system to 3.5, obtaining material a. Evaporate and crystallize material a at 68℃, concentrating it to about 30% of its original volume. Stop heating, allow it to cool naturally for 2 hours, filter and collect the crystals to obtain copper, zinc, and germanium fluxing agent R3T4-1.

[0020] 100g of copper smelting dust was weighed, with Cu, Zn, and Ge contents of 18.32%, 11.64%, and 128.60g / t, respectively. A 120g / L sulfuric acid solution was added at a liquid-to-solid ratio of 3:1, along with 2g of R3T4-1. Leaching was carried out at 85℃ and a stirring speed of 400r / min for 2 hours. After leaching, solid-liquid separation was performed, and the leaching rates of Cu, Zn, and Ge were measured to be 92.68%, 94.15%, and 60.42%, respectively.

[0021] Under the same conditions and without the addition of R3T4-1, the leaching rates of Cu, Zn, and Ge were 83.25%, 86.42%, and 39.18%, respectively. After the addition of R3T4-1, the leaching rates of the three elements increased by 9.43, 7.73, and 21.24 percentage points, respectively.

[0022] Example 2

[0023] Weigh out 40g of ferric nitrate, 10g of ammonium metavanadate, 8g of sodium citrate, and 50g of potassium nitrate. Add them to 400mL of water and stir to dissolve. Slowly add potassium hydroxide solution to adjust the pH of the system to 3.6, obtaining material a. Evaporate and crystallize material a at 70℃, concentrating it to about 30% of its original volume. Stop heating and allow it to cool naturally for 2.5h. Filter and collect the crystals to obtain copper, zinc, and germanium co-solvent R3T4-2.

[0024] 100g of copper smelting dust was weighed and added to a 140g / L sulfuric acid solution at a liquid-to-solid ratio of 3:1, along with 3g of R3T4-2. The mixture was leached at 90℃ and a stirring speed of 400r / min for 2 hours. After leaching, solid-liquid separation was performed, and the leaching rates of Cu, Zn, and Ge were measured to be 95.47%, 96.82%, and 68.56%, respectively.

[0025] Under the same conditions and without the addition of R3T4-2, the leaching rates of Cu, Zn, and Ge were 86.74%, 88.63%, and 43.27%, respectively. After the addition of R3T4-2, the leaching rates of the three elements increased by 8.73, 8.19, and 25.29 percentage points, respectively.

[0026] Example 3

[0027] Weigh out 60g of ferric sulfate, 15g of sodium metavanadate, 12g of sodium citrate, and 80g of sodium nitrate. Add them to 500mL of water and stir to dissolve. Slowly add sodium hydroxide solution to adjust the pH of the system to 3.75, obtaining material a. Evaporate and crystallize material a at 73℃, concentrating it to about 30% of its original volume. Stop heating and allow it to cool naturally for 3 hours. Filter and collect the crystals to obtain copper, zinc, and germanium fluxing agent R3T4-3.

[0028] 100g of copper smelting dust was weighed and added to a 160g / L sulfuric acid solution at a liquid-to-solid ratio of 4:1, along with 5g of R3T4-3. Leaching was carried out at 90℃ and a stirring speed of 400r / min for 2.5h. After leaching, solid-liquid separation was performed, and the leaching rates of Cu, Zn, and Ge were measured to be 98.12%, 98.67%, and 78.45%, respectively.

[0029] Under the same conditions and without the addition of R3T4-3, the leaching rates of Cu, Zn, and Ge were 88.36%, 90.14%, and 46.82%, respectively. After the addition of R3T4-3, the leaching rates of the three elements increased by 9.76, 8.53, and 31.63 percentage points, respectively, indicating that R3T4-3 has a significant enhancing effect on the leaching of copper, zinc, and difficult-to-leach germanium-containing phases.

[0030] Example 4

[0031] Weigh out 80g of ferric chloride, 22g of ammonium metavanadate, 16g of potassium citrate, and 120g of ammonium nitrate. Add them to 650mL of water and stir to dissolve. Slowly add ammonia water to adjust the pH of the system to 3.9, obtaining material a. Evaporate and crystallize material a at 76℃, concentrating it to about 30% of its original volume. Stop heating and allow it to cool naturally for 3.5h. Filter and collect the crystals to obtain copper, zinc, and germanium co-solvent R3T4-4.

[0032] 100g of copper smelting leaching residue was weighed and added to a 180g / L sulfuric acid solution at a liquid-to-solid ratio of 5:1, along with 6g of R3T4-4. Leaching was carried out at 95℃ and a stirring speed of 400r / min for 3 hours. After leaching, solid-liquid separation was performed, and the leaching rates of Cu, Zn, and Ge were measured to be 93.74%, 95.31%, and 71.26%, respectively.

[0033] Under the same conditions and without the addition of R3T4-4, the leaching rates of Cu, Zn, and Ge were 79.68%, 83.52%, and 35.47%, respectively. After the addition of R3T4-4, the leaching rates of the three elements increased by 14.06, 11.79, and 35.79 percentage points, respectively, indicating that R3T4-4 can effectively activate the residual refractory copper, zinc, and germanium phases in the leaching residue.

[0034] Example 5

[0035] Weigh 100g of ferric nitrate, 30g of sodium vanadate, 20g of sodium citrate, and 150g of potassium nitrate. Add them to 800mL of water and stir to dissolve. Slowly add sodium hydroxide solution to adjust the pH of the system to 4.0, obtaining material a. Evaporate and crystallize material a at 78℃, concentrating it to about 30% of its original volume. Stop heating and allow it to cool naturally for 4 hours. Filter and collect the crystals to obtain copper, zinc, and germanium fluxing agent R3T4-5.

[0036] 100g of complex polymetallic material was weighed and added to a mixed acid solution containing 150g / L sulfuric acid and 20g / L hydrochloric acid at a liquid-to-solid ratio of 4:1. 8g of R3T4-5 was also added. The mixture was leached at 90℃ and a stirring speed of 400r / min for 3 hours. After leaching, solid-liquid separation was performed, and the leaching rates of Cu, Zn, and Ge were measured to be 96.25%, 97.14%, and 74.82%, respectively.

[0037] Under the same conditions and without the addition of R3T4-5, the leaching rates of Cu, Zn, and Ge were 84.63%, 87.29%, and 41.36%, respectively. After the addition of R3T4-5, the leaching rates of the three elements increased by 11.62, 9.85, and 33.46 percentage points, respectively, indicating that R3T4-5 has good adaptability to complex polymetallic materials from different sources.

Claims

1. A copper, zinc, and germanium co-solvent R3T4, characterized in that, The copper, zinc, and germanium co-solvent R3T4 is prepared from soluble trivalent iron salts, vanadates, citrates, and nitrates.

2. The copper, zinc, and germanium co-solvent R3T4 according to claim 1, characterized in that, The copper, zinc, and germanium co-solvent R3T4 is prepared from raw materials consisting of 2-10 parts by weight of soluble trivalent iron salt, 0.5-3 parts by weight of vanadate, 0.5-2 parts by weight of citrate, and 2-15 parts by weight of nitrate.

3. A method for preparing the copper, zinc, and germanium co-solvent R3T4 as described in claim 1 or 2, characterized in that, This includes pretreatment and evaporation crystallization steps, specifically: A. Pretreatment: Dissolve the soluble ferric salt, vanadate, citrate and nitrate in water according to the formula, and add an alkaline adjuster under stirring until the pH of the system is 3.5~4.0 to obtain material a; B. Evaporation and crystallization: Material a is subjected to evaporation and crystallization reaction at a temperature of 68~78℃. After cooling, the target copper, zinc and germanium co-solvent R3T4 is obtained.

4. The preparation method according to claim 3, characterized in that, The cooling described in step B is natural cooling, and the cooling time is 2-4 hours.

5. The application of the copper, zinc, and germanium co-solvent R3T4 as described in claim 1 or 2, characterized in that, The application of the copper, zinc, and germanium co-solvent R3T4 in the resource recovery process of copper smelting dust, leaching residue, and complex polymetallic materials.