Method for separating and enriching gallium, germanium and copper from pressurized zinc hydrometallurgy solution

Abstract

The invention relates to a method for separating and enriching gallium, germanium and copper from a pressurized zinc hydrometallurgy solution, which comprises the following steps: neutralization: adding Fe2O3 and ZnO into a zinc oxygen pressure leaching solution, and reducing the concentration of H2SO4 in the zinc oxygen pressure leaching solution to 2-4g / L to obtain a first solution; aging: adding polyacrylamide into the first solution, aging and then filtering to obtain a gallium enrichment and a pre-replacement solution; fe is added into the pre-replacement liquid, and copper enrichment and post-iron replacement liquid are obtained after solid-liquid separation; lead and zinc replacement: adding Pb and Zn into the iron replacement post-liquid, and carrying out solid separation to obtain germanium enrichment and zinc replacement post-liquid; the zinc oxygen pressure leaching solution comprises the following components: 150 to 200 g / L of Zn element, 10 to 15 g / L of Fe < 2 + >, 0.1 to 1 g / L of Fe < 3 + >, 100 to 1000 mg / L of Cu element, 100 to 1000 mg / L of As element, 10 to 25 g / L of H2SO4, 5 to 30 mg / L of Ga element and 5 to 30 mg / L of Ge element. The method overcomes the problems of incomplete replacement of gallium and germanium and complex phase in the existing pressurized zinc hydrometallurgy solution, improves the replacement rate of gallium and germanium, and realizes effective separation of gallium, germanium and copper.

Description

Technical Field

[0001] The invention relates to the technical field of separation and recovery of gallium and germanium, and in particular to a method for separating and enriching gallium, germanium and copper from a pressurized wet zinc smelting solution. Background Art

[0002] Gallium is an important basic material supporting the development of modern computers, 5G communications, aerospace, new energy, medicine and health, and national defense and military high-tech, and is directly related to national economic and strategic security.

[0003] Gallium and germanium are the main associated valuable elements in zinc concentrate, with a grade of 0.001-0.01wt.%. Traditional hydrometallurgy adopts the "roasting-leaching" method. Gallium and germanium are enriched in zinc leaching slag during the neutral leaching process. When the rotary kiln is used for subsequent volatilization, germanium is partially recovered from the zinc oxide dust. When the zinc concentrate is directly subjected to oxygen pressure leaching, gallium and germanium basically enter the solution, which is conducive to the recovery of gallium and germanium.

[0004] At present, the zinc powder replacement method is mainly used to recover gallium and germanium from pressurized wet zinc smelting solution. However, this method has a series of problems such as large zinc powder consumption, incomplete gallium and germanium replacement, complex gallium and germanium phases in the subsequent zinc powder replacement slag, lengthy gallium and germanium extraction process, and low recovery rate. Summary of the invention

[0005] Based on this, in order to overcome the problems of incomplete gallium-germanium replacement and complex phases in the existing pressurized wet zinc smelting solution, the present invention provides a method for separating and enriching gallium, germanium and copper from a pressurized wet zinc smelting solution, thereby improving the gallium-germanium replacement rate and achieving effective separation of gallium, germanium and copper.

[0006] A method for separating and enriching gallium, germanium and copper from a pressurized hydrometallurgical zinc solution comprises the following steps:

[0007] Neutralization: adding Fe2O3 and ZnO to the zinc oxygen pressure leaching solution to reduce the concentration of H2SO4 in the zinc oxygen pressure leaching solution to 2-4 g / L to obtain a first solution;

[0008] Aging: adding polyacrylamide to the first solution, aging and filtering to obtain a gallium-enriched product and a pre-replacement solution;

[0009] Iron replacement: adding Fe to the pre-replacement solution, and obtaining a copper-enriched product and an iron-replaced solution after solid-liquid separation;

[0010] Lead-zinc replacement: adding Pb and Zn to the iron-replaced liquid, and performing solid-solid separation to obtain a germanium-enriched product and a zinc-replaced liquid;

[0011] The zinc oxygen pressure leaching solution includes the following components: 150-200 g / L of Zn element, Fe 2+ 10~15g / L, Fe 3+0.1~1g / L, Cu element 100~1000mg / L, As element 100~1000mg / L, H2SO4 10~25g / L, Ga element 5~30mg / L, Ge element 5~30mg / L.

[0012] The chemical reaction equation involved in the present invention is as follows:

[0013] Neutralization: ZnO+2H+→Zn 2+ +H2O

[0014] Fe2O3+H + →Fe 3+ +H2O

[0015] Aging: NH4 + +Fe 3+ +SO4 2- +H2O→NH4Fe3(SO4)2(OH)6↓+H +

[0016] NH4 + +Ga 3+ +SO4 2- +H2O→NH4Ga3(SO4)2(OH)6↓+H +

[0017] Iron replacement: Cu 2+ +Fe→Cu↓+Fe 2+

[0018] Lead-zinc replacement: GeO4 4- +H++Zn→Ge↓+H2O+Zn 2+

[0019] GeO4 4- +H + +Pb→GeO2↓+PbSO4↓+H2O

[0020] AsO3 3- +H + +Pb→PbAs↓+H2O

[0021] Compared with the prior art, the advantages of the present invention are: (1) without affecting the zinc extraction in the main process, the efficient separation and directional enrichment of gallium, germanium and copper in the pressurized wet zinc smelting leaching solution is achieved; (2) the efficient removal of arsenic in the pressurized wet zinc smelting solution is achieved, reducing the difficulty of zinc recovery in the solution after subsequent zinc powder replacement; (3) the iron powder first replaces the copper, and then the zinc powder only needs to replace germanium, which significantly reduces the zinc powder consumption and reduces the production cost.

[0022] As a preferred solution, the amount of ZnO added is 4 to 12 times the amount of Fe2O3 based on the mass of Fe and Zn. 3+ If the concentration is too low, it will be unfavorable for the co-precipitation in the subsequent aging step, resulting in incomplete gallium precipitation; if the amount of zinc oxide added is too low, the Fe 3+ If the concentration is too high, the amount of precipitation will increase during the subsequent co-precipitation, thereby reducing the gallium grade in the gallium enriched product.

[0023] As a preferred embodiment, the neutralization further comprises: reacting at 80 to 90° C. for 0.5 to 1.5 hours.

[0024] As a preferred solution, the amount of polyacrylamide added is 0.1-0.5 g / L. If the amount of polyacrylamide added is too low, the aging efficiency is low, and it may even be impossible to fully age. If the amount of polyacrylamide added is too high, the cost increases and the gallium precipitation rate does not increase significantly.

[0025] As a preferred embodiment, the aging further comprises: aging at 80-90°C for 2-4h. If the aging time is too short, the aging cannot be complete, resulting in a low amount of gallium precipitation, and further resulting in a low gallium grade in the gallium enriched product; if the aging time is too long, the cost increases, and the gallium content of the gallium enriched product does not increase significantly.

[0026] As a preferred solution, the amount of Fe added is 0.25-1 g / L. Within this range, copper ions can be replaced as much as possible to avoid copper loss and iron waste.

[0027] As a preferred embodiment, the iron replacement further comprises: reacting at 80-90° C. for 0.5-1 h.

[0028] As a preferred solution, the total amount of Pb and Zn added is 2-3 g / L. Within this range, germanium can be replaced as much as possible, while the amount of germanium enrichment is reduced, the grade of germanium is improved, and subsequent recovery is facilitated.

[0029] As a preferred solution, the amount of Zn added is 4 to 19 times that of Pb by mass. If the amount of zinc added is too high, it will lead to incomplete germanium replacement and further germanium loss; if the amount of lead added is too high, the grade of germanium in the germanium enriched product will be low.

[0030] As a preferred embodiment, the lead-zinc replacement further comprises: reacting at 80-90° C. for 0.5-1 h. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 The invention discloses a process flow chart of a method for separating and enriching gallium, germanium and copper from a pressurized hydrometallurgical zinc solution. DETAILED DESCRIPTION

[0032] In order to further understand the present invention, the present invention is described in detail below in conjunction with the embodiments. However, it should be noted that the embodiments do not limit the scope of protection claimed for the present invention.

[0033] A method for separating and enriching gallium, germanium and copper from a pressurized hydrometallurgical zinc solution comprises the following steps:

[0034] Neutralization: adding Fe2O3 and ZnO to the zinc oxygen pressure leaching solution, wherein the amount of ZnO added is 4 to 12 times the amount of Fe2O3 based on the mass of Fe and Zn, reducing the concentration of H2SO4 in the zinc oxygen pressure leaching solution to 2 to 4 g / L, reacting at 80 to 90° C. for 0.5 to 1.5 h to obtain a first solution;

[0035] Aging: adding polyacrylamide to the first solution at a solid-liquid ratio of 0.1 to 0.5 g / L, aging at 80 to 90° C. for 2 to 4 hours, and obtaining a gallium-enriched product and a pre-replacement solution after solid-liquid separation;

[0036] Iron replacement: adding Fe to the pre-replacement solution at a solid-liquid ratio of 0.25-1 g / L, reacting at 80-90° C. for 0.5-1 h, and obtaining a copper-enriched product and an iron-replaced solution after solid-liquid separation;

[0037] Lead-zinc replacement: Pb and Zn are added to the iron-replaced liquid at a solid-liquid ratio of 2-3 g / L, wherein the amount of Zn added is 4-19 times that of Pb, and the reaction is carried out at 80-90° C. for 0.5-1 h. The germanium enriched product and the zinc-replaced liquid are obtained by solid separation, and the zinc-replaced liquid is subsequently subjected to a zinc recovery process.

[0038] The zinc oxygen pressure leaching solution includes the following components: 150-200 g / L of Zn element, Fe 2+ 10~15g / L, Fe 3+ 0.1~1g / L, Cu element 100~1000mg / L, As element 100~1000mg / L, H2SO4 10~25g / L, Ga element 5~30mg / L, Ge element 5~30mg / L.

[0039] In the embodiment of the present invention, the zinc oxygen pressure leaching solution includes the following components: Zn element 185g / L, Fe 2+ 12.5g / L, Fe 3+0.15g / L, Cu element 300mg / L, As element 500mg / L, H2SO4 25g / L, Ga element 25mg / L, Ge element 25mg / L; based on the mass of Fe and Zn, the added amount of ZnO is 7.3 times that of Fe2O3; based on the mass, the added amount of Zn is 9 times that of Pb.

[0040] Example 1

[0041] like Figure 1 As shown, a method for separating and enriching gallium, germanium and copper from a pressurized hydrometallurgical zinc solution comprises the following steps:

[0042] Neutralization: adding Fe2O3 and ZnO to the zinc oxygen pressure leaching solution to reduce the concentration of H2SO4 in the zinc oxygen pressure leaching solution to 2.5 g / L, reacting at 85°C for 1 hour to obtain a first solution;

[0043] Aging: adding polyacrylamide to the first solution at a solid-liquid ratio of 0.4 g / L, aging at 85° C. for 3 h, and obtaining a gallium-enriched product and a pre-replacement solution after solid-liquid separation;

[0044] Iron replacement: adding iron powder to the pre-replacement solution at a solid-liquid ratio of 0.6 g / L, reacting at 85° C. for 0.75 h, and obtaining a copper-enriched product and an iron powder-replaced solution after solid-liquid separation;

[0045] Lead-zinc replacement: lead powder and zinc powder are added to the iron powder replacement liquid at a solid-liquid ratio of 2.5 g / L, and the reaction is carried out at 85°C for 1 hour. The germanium enriched product and the zinc powder replacement liquid are obtained by solid separation, and the zinc powder replacement liquid is subsequently subjected to a zinc recovery process.

[0046] Example 2

[0047] A method for separating and enriching gallium, germanium and copper from a pressurized hydrometallurgical zinc solution comprises the following steps:

[0048] Neutralization: adding Fe2O3 and ZnO to the zinc oxygen pressure leaching solution to reduce the concentration of H2SO4 in the zinc oxygen pressure leaching solution to 3 g / L, reacting at 90°C for 1 hour to obtain a first solution;

[0049] Aging: adding polyacrylamide to the first solution at a solid-liquid ratio of 0.25 g / L, aging at 90° C. for 3 h, and obtaining a gallium-enriched product and a pre-replacement solution after solid-liquid separation;

[0050] Iron replacement: adding iron powder to the pre-replacement solution at a solid-liquid ratio of 0.5 g / L, reacting at 90° C. for 0.5 h, and obtaining a copper-enriched product and an iron powder-replaced solution after solid-liquid separation;

[0051] Lead-zinc replacement: lead powder and zinc powder were added to the iron powder replacement liquid at a solid-liquid ratio of 2.75 g / L, and the reaction was carried out at 90°C for 1 hour. The germanium enriched product and the zinc powder replacement liquid were obtained by solid separation, and the zinc powder replacement liquid was subsequently subjected to a zinc recovery process.

[0052] Example 3

[0053] A method for separating and enriching gallium, germanium and copper from a pressurized hydrometallurgical zinc solution comprises the following steps:

[0054] Neutralization: adding Fe2O3 and ZnO to the zinc oxygen pressure leaching solution to reduce the concentration of H2SO4 in the zinc oxygen pressure leaching solution to 2 g / L, reacting at 80°C for 1 hour to obtain a first solution;

[0055] Aging: adding polyacrylamide to the first solution at a solid-liquid ratio of 0.5 g / L, aging at 80° C. for 3 h, and obtaining a gallium-enriched product and a pre-replacement solution after solid-liquid separation;

[0056] Iron replacement: adding iron powder to the pre-replacement solution at a solid-liquid ratio of 0.75 g / L, reacting at 80° C. for 1 h, and obtaining a copper-enriched product and an iron powder-replaced solution after solid-liquid separation;

[0057] Lead-zinc replacement: lead powder and zinc powder are added to the iron powder replacement liquid at a solid-liquid ratio of 3.0 g / L, and the reaction is carried out at 80°C for 1 hour. The germanium enriched product and the zinc powder replacement liquid are obtained by solid separation, and the zinc powder replacement liquid is subsequently subjected to a zinc recovery process.

[0058] Example 4

[0059] A method for separating and enriching gallium, germanium and copper from a pressurized hydrometallurgical zinc solution comprises the following steps:

[0060] Neutralization: adding Fe2O3 and ZnO to the zinc oxygen pressure leaching solution to reduce the concentration of H2SO4 in the zinc oxygen pressure leaching solution to 4 g / L, reacting at 90°C for 1 hour to obtain a first solution;

[0061] Aging: adding polyacrylamide to the first solution at a solid-liquid ratio of 0.1 g / L, aging at 90° C. for 4 h, and obtaining a gallium-enriched product and a pre-replacement solution after solid-liquid separation;

[0062] Iron replacement: adding iron powder to the pre-replacement solution at a solid-liquid ratio of 0.25 g / L, reacting at 90° C. for 1 h, and obtaining a copper-enriched product and an iron powder-replaced solution after solid-liquid separation;

[0063] Lead-zinc replacement: lead powder and zinc powder are added to the iron powder replacement liquid at a solid-liquid ratio of 2.0 g / L, and the reaction is carried out at 90° C. for 0.75 h. The germanium enriched product and the zinc powder replacement liquid are obtained by solid separation, and the zinc powder replacement liquid is subsequently subjected to a zinc recovery process.

[0064] Example 5

[0065] A method for separating and enriching gallium, germanium and copper from a pressurized hydrometallurgical zinc solution comprises the following steps:

[0066] Neutralization: adding Fe2O3 and ZnO to the zinc oxygen pressure leaching solution to reduce the concentration of H2SO4 in the zinc oxygen pressure leaching solution to 3.5 g / L, reacting at 90°C for 1 hour to obtain a first solution;

[0067] Aging: adding polyacrylamide to the first solution at a solid-liquid ratio of 0.2 g / L, aging at 90° C. for 2 h, and obtaining a gallium-enriched product and a pre-replacement solution after solid-liquid separation;

[0068] Iron replacement: adding iron powder to the pre-replacement solution at a solid-liquid ratio of 1 g / L, reacting at 90° C. for 0.75 h, and obtaining a copper-enriched product and an iron powder-replaced solution after solid-liquid separation;

[0069] Lead-zinc replacement: lead powder and zinc powder were added to the iron powder replacement liquid at a solid-liquid ratio of 2.25 g / L, and the reaction was carried out at 90°C for 0.5 h. The germanium enriched product and the zinc powder replacement liquid were obtained by solid separation, and the zinc powder replacement liquid was subsequently subjected to a zinc recovery process.

[0070] Comparative Example 1

[0071] No Fe2O3 is added in the neutralization step, and the other steps are exactly the same as those in Example 2.

[0072] Comparative Example 2

[0073] Polyacrylamide was not added in the aging step, and the other steps were exactly the same as those in Example 2.

[0074] Comparative Example 3

[0075] No lead powder is added in the lead-zinc replacement step, and the other steps are exactly the same as those in Example 2.

[0076] Tables 1-6 are the results of the embodiments and comparative examples. It can be seen from the results in the table that the use of Fe2O3, ZnO and polyacrylamide is helpful to promote the directional enrichment of gallium in the form of yellow ammonium gallium vanadium precipitation. When Fe2O3 is not added (Comparative Example 1) and polyacrylamide is not added (Comparative Example 2), gallium precipitation is incomplete and the gallium recovery rate is significantly reduced. When lead powder and zinc powder are used as reducing agents to replace germanium, the introduction of lead forms lead sulfate precipitation on the one hand, forming a good filter cake layer during liquid-solid separation to prevent the loss of germanium in the liquid after zinc replacement. On the other hand, the introduction of lead helps to achieve complete removal of arsenic during the replacement process. When zinc powder is used as a reducing agent in Comparative Example 3, germanium will re-dissolve in the liquid after zinc powder replacement, resulting in a decrease in the germanium recovery rate, and the liquid after replacement still contains a high level of arsenic, and further arsenic removal is required in the subsequent zinc recovery process.

[0077] Table 1 Concentration of different elements in the materials of each step of Example 1

[0078] Ga Ge As Cu Stock solution (mg / L) 25 25 500 300 Fluid before replacement (mg / L) 0.5 25 480 300 Iron replacement solution (mg / L) 0.5 24 480 0 Zinc replacement solution (mg / L) 0.1 0.5 0 0 Recovery rate (%) 98 94 100 100

[0079] Table 2 Concentration of different elements in the materials of each step of Example 2

[0080] Ga Ge As Cu Stock solution (mg / L) 25 25 500 300 Fluid before replacement (mg / L) 0.25 25 470 300 Iron replacement solution (mg / L) 0.25 24.5 470 0 Zinc replacement solution (mg / L) 0.05 0.25 0 0 Recovery rate (%) 99 97 100 100

[0081] Table 3 Concentration of different elements in the materials of each step of Example 3

[0082] Ga Ge As Cu Stock solution (mg / L) 25 25 500 300 Fluid before replacement (mg / L) 0.4 25 490 300 Iron replacement solution (mg / L) 0.4 24 490 0 Zinc replacement solution (mg / L) 0.1 0.2 0 0 Recovery rate (%) 98.4 95.2 100 100

[0083] Table 4 Concentration of different elements in the materials of each step of Comparative Example 1

[0084] Ga Ge As Cu Stock solution (mg / L) 25 25 500 300 Fluid before replacement (mg / L) 8 25 470 300 Iron replacement solution (mg / L) 8 24.5 470 0 Zinc replacement solution (mg / L) 6 0.25 0 0 Recovery rate (%) 68 97 100 100

[0085] Table 5 Concentrations of different elements in the materials of each step of Comparative Example 2

[0086] Ga Ge As Cu Stock solution (mg / L) 25 25 500 300 Fluid before replacement (mg / L) 5 25 470 300 Iron replacement solution (mg / L) 5 24.5 470 0 Zinc replacement solution (mg / L) 4 0.25 0 0 Recovery rate (%) 80 97 100 100

[0087] Table 6 Concentration of different elements in the materials of each step of Comparative Example 3

[0088] Ga Ge As Cu Stock solution (mg / L) 25 25 500 300 Fluid before replacement (mg / L) 0.25 25 470 300 Iron replacement solution (mg / L) 0.25 24.5 470 0 Zinc replacement solution (mg / L) 0.05 2.5 100 0 Recovery rate (%) 90 90 80 100

Claims

1. A method for separating and enriching gallium, germanium and copper from a pressurized hydrometallurgical zinc solution, characterized in that: The following steps are involved: Neutralization: adding Fe2O3 and ZnO to the zinc oxygen pressure leaching solution to reduce the concentration of H2SO4 in the zinc oxygen pressure leaching solution to 2-4 g / L to obtain a first solution; Aging: adding polyacrylamide to the first solution, aging and filtering to obtain a gallium-enriched product and a pre-replacement solution; Iron replacement: adding Fe to the pre-replacement solution, and obtaining a copper-enriched product and an iron-replaced solution after solid-liquid separation; Lead-zinc replacement: adding Pb and Zn to the iron-replaced liquid, and performing solid-solid separation to obtain a germanium-enriched product and a zinc-replaced liquid; The zinc oxygen pressure leaching solution includes the following components: 150-200 g / L of Zn element, Fe 2+ 10~15g / L, Fe 3+ 0.1~1g / L, Cu element 100~1000mg / L, As element 100~1000mg / L, H2SO4 10~25g / L, Ga element 5~30mg / L, Ge element 5~30mg / L.

2. A method for separating and enriching gallium, germanium and copper from a pressurized hydrometallurgical zinc solution according to claim 1, characterized in that: Calculated by the mass of Fe and Zn, the added amount of ZnO is 4 to 12 times that of Fe2O3.

3. A method for separating and enriching gallium, germanium and copper from a pressurized hydrometallurgical zinc solution according to claim 2, characterized in that: The neutralization further comprises: reacting at 80 to 90° C. for 0.5 to 1.5 hours.

4. The method for separating and enriching gallium, germanium and copper from a pressurized hydrometallurgical zinc solution according to claim 1, characterized in that: The added amount of the polyacrylamide is 0.1-0.5 g / L.

5. A method for separating and enriching gallium, germanium and copper from a pressurized hydrometallurgical zinc solution according to claim 4, characterized in that: The aging further comprises: aging at 80-90° C. for 2-4 hours.

6. A method for separating and enriching gallium, germanium and copper from a pressurized hydrometallurgical zinc solution according to claim 1, characterized in that: The amount of Fe added is 0.25-1 g / L.

7. A method for separating and enriching gallium, germanium and copper from a pressurized hydrometallurgical zinc solution according to claim 6, characterized in that: The iron replacement further comprises: reacting at 80-90° C. for 0.5-1 h.

8. The method for separating and enriching gallium, germanium and copper from a pressurized hydrometallurgical zinc solution according to claim 1, characterized in that: The total added amount of Pb and Zn is 2-3 g / L.

9. A method for separating and enriching gallium, germanium and copper from a pressurized hydrometallurgical zinc solution according to claim 8, characterized in that: The amount of Zn added is 4 to 19 times that of Pb by mass.

10. A method for separating and enriching gallium, germanium and copper from a pressurized hydrometallurgical zinc solution according to claim 9, characterized in that: The lead-zinc replacement further comprises: reacting at 80-90° C. for 0.5-1 hour.

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