A germanium activated agent H-HJ01 and its preparation method and application

Abstract

The present invention discloses a Ge-activating agent H‑HJ01 and a preparation method and application thereof. The Ge-activating agent H‑HJ01 is prepared from raw materials of sulfur dioxide, sodium hydroxide, yellow phosphorus and sodium chloride through complexation reaction. The preparation method of the Ge-activating agent H‑HJ01 includes complexation reaction, vacuum distillation, cooling crystallization and air-cooling drying treatment steps. The application is the application of the Ge-activating agent H‑HJ01 in enriching low-grade germanium ore. The Ge-activating agent H‑HJ01 of the present invention can effectively improve the recovery rate of Ge enriched by pyrometallurgy, laying the foundation for the preparation of germanium chemicals. The Ge-activating agent H‑HJ01 of the present invention is applied to the pyrometallurgy enrichment of germanium in germanium-containing copper concentrate, and the comprehensive recovery rate of germanium is greater than 95%.

Description

Technical Field

[0001] The invention belongs to the technical field of metallurgy and chemical engineering, and specifically relates to a germanium activated agent H-HJ01 and a preparation method and application thereof. Background Art

[0002] Scattered metallic germanium is widely used in semiconductor materials, aerospace, nuclear physics detection, optical fiber communication, infrared optics, solar cells, chemical catalysts, and biomedical fields. In recent years, with the rapid development of the optical fiber communication industry and the solar cell industry, the global demand for germanium products is strong. Germanium is rarely associated with other mineral resources, and its comprehensive utilization technology is relatively immature.

[0003] The main methods for extracting germanium at home and abroad are: classical chlorination, volatilization, zinc powder replacement, distillation (alkaline earth metal chlorination distillation), fuming, extraction (liquid membrane extraction), ion exchange, etc. However, the classical chlorination, zinc powder replacement, extraction (liquid membrane extraction), and ion exchange are all based on extracting, separating, and enriching germanium from the enriched germanium raw material (smoke dust or germanium-containing aqueous solution). The enrichment of germanium is mainly through ore dressing and pyrometallurgical enrichment. Since germanium does not form alone in the primary ore, it is associated with lead, zinc, lignite, etc. It is difficult to separate a separate germanium ore through ore dressing. Therefore, the enrichment of germanium is first enriched into smoke dust or coal ash by pyrometallurgy and then enriched by wet method. During pyrometallurgical enrichment, due to the stable structure of the ore sample or slag, the multiple components, the complex components, and the mutual nesting and wrapping, the comprehensive recovery rate of germanium is generally low, and the economic benefits are not good. Therefore, it is very necessary to develop a product that can solve the above technical problems. Summary of the invention

[0004] The first purpose of the present invention is to provide a germanium-activated agent H-HJ01; the second purpose is to provide a method for preparing the germanium-activated agent H-HJ01; and the third purpose is to provide an application of the germanium-activated agent H-HJ01.

[0005] The invention aims at the problem that germanium material is not easy to reduce and volatilize and has low volatilization rate during pyrometallurgical enrichment, and prepares an agent H-HJ01 for activating germanium pyrometallurgical enrichment. The agent has good activity, an environmentally friendly preparation method and low cost.

[0006] The first object of the present invention is achieved in that the germanium activation agent H-HJ01 is prepared by complexing raw materials of sulfur dioxide, sodium hydroxide, yellow phosphorus and sodium chloride.

[0007] The second object of the present invention is achieved by comprising the steps of preparing liquid I, preparing liquid II, preparing a medicament and post-processing, specifically comprising:

[0008] A. Preparation of Liquid I: Prepare a sodium hydroxide solution with a concentration of 90-110 g / L by mixing the sodium hydroxide in the formula ratio to obtain Liquid I;

[0009] B. Preparation of Liquid II: Add 15-50 times the mass of water to the sodium chloride in the formula, stir to dissolve, then add the crushed yellow phosphorus with 10 mesh sieve in the formula, stir to obtain Liquid II;

[0010] C. Preparation of the reagent: Place liquid I and liquid II in a reaction tank, and introduce sulfur dioxide of a prescribed ratio to carry out complex reaction and homogenization to obtain complex reaction liquid a;

[0011] D. Post-treatment: The complex reaction solution a is subjected to reduced pressure distillation to obtain distillation residue b; the distillation residue b is cooled, crystallized, and dried to obtain the target germanium reagent H-HJ01.

[0012] The specific operations are as follows:

[0013] (1) Preparation of liquid I: prepare sodium hydroxide solution; (2) Preparation of liquid II: add a certain volume of water and a certain weight of NaCl into a closed tank, and then add crushed yellow phosphorus; (3) While spraying liquid I into liquid II, introduce SO2 gas (the pipeline is inserted into the bottom of the closed tank) to react and prepare liquid III; (4) Liquid III is distilled under reduced pressure and then cooled and crystallized to obtain solid activated I; (5) Solid activated I is air-dried to obtain germanium activation agent H-HJ01.

[0014] The method of the invention has a short and simple process flow and is easy to operate. The prepared activation agent has good selectivity for germanium, promotes the reduction and volatilization of germanium, greatly reduces the capture of germanium by slag, and greatly improves the performance of slag.

[0015] The Ge activation agent prepared by the present invention can interact with germanium and germanium compounds, not only effectively improving the reduction volatilization rate of germanium and reducing the capture capacity of the melt on germanium, but also improving the chemical composition, viscosity and fluidity of the melt, and reducing the furnace temperature of reduction volatilization, so that the germanium-containing materials that are not easy to reduce volatilize can reduce the volatilization of germanium. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 It is a schematic diagram of the process flow of the present invention. DETAILED DESCRIPTION

[0017] The present invention is further described below in conjunction with the embodiments, but the present invention is not limited in any way. Any changes or substitutions made based on the teachings of the present invention belong to the protection scope of the present invention.

[0018] The germanium activation agent H-HJ01 of the present invention is prepared by complexing raw materials of sulfur dioxide, sodium hydroxide, yellow phosphorus and sodium chloride.

[0019] The mass ratio of the raw materials sulfur dioxide, sodium hydroxide, yellow phosphorus and sodium chloride is: (40-90): (90-110): (1-50): (10-60).

[0020] The mass ratio of the raw materials sulfur dioxide, sodium hydroxide, yellow phosphorus and sodium chloride is: (48-80):100:(1-30):(20-40).

[0021] The preparation method of the germanium activated agent H-HJ01 of the present invention comprises the steps of preparing liquid I, preparing liquid II, preparing the agent and post-processing, specifically comprising:

[0022] A. Preparation of Liquid I: Prepare a sodium hydroxide solution with a concentration of 90-110 g / L by mixing the sodium hydroxide in the formula ratio to obtain Liquid I;

[0023] B. Preparation of Liquid II: Add 15-50 times the mass of water to the sodium chloride in the formula, stir to dissolve, then add the crushed yellow phosphorus with 10 mesh sieve in the formula, stir to obtain Liquid II;

[0024] C. Preparation of the reagent: Place liquid I and liquid II in a reaction tank, and introduce sulfur dioxide of a prescribed ratio to carry out complex reaction and homogenization to obtain complex reaction liquid a;

[0025] D. Post-treatment: The complex reaction solution a is subjected to reduced pressure distillation to obtain distillation residue b; the distillation residue b is cooled, crystallized, and dried to obtain the target germanium reagent H-HJ01.

[0026] The stirring speed in step B is 10~1000r / min.

[0027] The temperature of the complexation reaction in step C is 10-350°C.

[0028] The pH value at the end point of the complexation reaction in step C is controlled at 5.5-13.

[0029] In step C, the homogenization is carried out at a temperature of 50-100° C. for 0.5-200 h.

[0030] The temperature of the reduced pressure distillation in step D is 93-350°C.

[0031] The application of the agent H-HJ01 for activating germanium described in the present invention is the application of the agent H-HJ01 for activating germanium in the preparation of an activator.

[0032] The present invention is further described below with specific implementation cases:

[0033] Example 1

[0034] 1. Prepare 1L of 100g / L sodium hydroxide solution.

[0035] 2. Prepare 1L of 30g / L NaCl solution in a closed reactor under stirring, add 20g of yellow phosphorus, then close the feeding hole and stir at a speed of 300r / min.

[0036] 3. Use a pressure pump (the pump pressure is greater than the SO2 gas pressure) to pump 1L 100g / L sodium hydroxide solution into the phosphorus-containing NaCl solution, and at the same time, introduce 64g SO2 gas for reaction. The SO2 gas is controlled by flow and pressure, and the control method is (PV=nRT). The conditions for the complex reaction are: reaction temperature 150℃~155℃, reaction end point pH 7.5, yellow phosphorus added weight 20% of the solid base weight, SO2 gas added weight 64% of the solid base weight, and homogenization at 60℃ for 10h after the reaction is completed.

[0037] 4. The solution after the complexation reaction is transferred to a distillation kettle, evacuated to -0.05Mpa, and heated to 180℃~190℃ for distillation.

[0038] 5. The distillate is returned to the alkali solution or NaCl solution; the residual liquid is placed in a cooling crystallization tank.

[0039] 6. The crystals are blow-dried or naturally dried at room temperature to obtain the target germanium activated agent H-HJ01.

[0040] The germanium activation agent H-HJ01 prepared in this example was used for the experiment. 20 g of the germanium activation agent H-HJ01 prepared in this example was mixed into 1000 g of germanium-containing copper concentrate (germanium 1281 g / t) for molten pool volatilization. The germanium grade in the slag was 9 g / t, and the germanium volatilization rate was 99.5%.

[0041] 40 g of the germanium activation agent H-HJ01 prepared in this example was mixed into 1000 g of coal ash (germanium 4310 g / t) for molten pool volatilization. The germanium grade in the slag was 32 g / t, and the germanium volatilization rate was 99.3%.

[0042] Example 2

[0043] 1. Prepare 1L of 90g / L sodium hydroxide solution.

[0044] 2. Prepare 1L of 10g / L NaCl solution in a closed reactor under stirring, add 5g of yellow phosphorus, then close the feeding hole and stir at a speed of 20r / min.

[0045] 3. Use a pressure pump (the pump pressure is greater than the SO2 gas pressure) to pump 1L 100g / L sodium hydroxide solution into the phosphorus-containing NaCl solution, and at the same time, introduce 40g SO2 gas for reaction. The SO2 gas is controlled by flow and pressure, and the control method is (PV=nRT). The conditions for the complex reaction are: the reaction temperature is 50℃~85℃, the reaction end point pH is 5.8, the weight of yellow phosphorus added is 5% of the weight of the solid base, the weight of SO2 gas added is 40% of the weight of the solid base, and after the reaction is completed, it is homogenized at 53℃ for 150h.

[0046] 4. The solution after the complexation reaction is transferred to a distillation kettle, evacuated to -0.05Mpa, and heated to 110℃~160℃ for distillation.

[0047] 5. The distillate is returned to the alkali solution or NaCl solution; the residual liquid is placed in a cooling crystallization tank.

[0048] 6. The crystals are blow-dried or naturally dried at room temperature to obtain the target germanium activated agent H-HJ01.

[0049] The germanium activation agent H-HJ01 prepared in this example was used for the experiment. 20 g of the germanium activation agent H-HJ01 prepared in this example was mixed into 1000 g of germanium-containing copper concentrate (germanium 1323 g / t) for molten pool volatilization. The germanium grade in the slag was 9.2 g / t, and the germanium volatilization rate was 99.64%.

[0050] 40 g of the germanium activation agent H-HJ01 prepared in this example was mixed into 1000 g of coal ash (germanium 4530 g / t) for molten pool volatilization. The germanium grade in the slag was 34.5 g / t, and the germanium volatilization rate was 99.48%.

[0051] Example 3

[0052] 1. Prepare 1L of 110g / L sodium hydroxide solution.

[0053] 2. Prepare 1L of 20g / L NaCl solution in a closed reactor under stirring, add 30g of yellow phosphorus, and then close the feeding hole. The stirring speed is 900r / min.

[0054] 3. Use a pressure pump (the pump pressure is greater than the SO2 gas pressure) to pump 1L 100g / L sodium hydroxide solution into the phosphorus-containing NaCl solution, and at the same time, introduce 90g SO2 gas for reaction. The SO2 gas is controlled by flow and pressure, and the control method is (PV=nRT). The conditions for the complex reaction are: reaction temperature 200℃~320℃, reaction end point pH 12.5, yellow phosphorus added weight 30% of the solid base weight, SO2 gas added weight 90% of the solid base weight, and homogenization at 98℃ for 2h after the reaction is completed.

[0055] 4. The solution after the complexation reaction is transferred to a distillation kettle, evacuated to -0.05Mpa, and heated to 220℃~270℃ for distillation.

[0056] 5. The distillate is returned to the alkali solution or NaCl solution; the residual liquid is placed in a cooling crystallization tank.

[0057] 6. The crystals are blow-dried or naturally dried at room temperature to obtain the target germanium activated agent H-HJ01.

[0058] The germanium activation agent H-HJ01 prepared in this example was used for the experiment. 20 g of the germanium activation agent H-HJ01 prepared in this example was mixed into 1000 g of germanium-containing copper concentrate (germanium 1193 g / t) for molten pool volatilization. The germanium grade in the slag was 8.99 g / t, and the germanium volatilization rate was 99.48%.

[0059] 40 g of the germanium activation agent H-HJ01 prepared in this example was mixed into 1000 g of coal ash (germanium 4450 g / t) for molten pool volatilization. The germanium grade in the slag was 33.28 g / t, and the germanium volatilization rate was 99.45%.

[0060] Example 4

[0061] 1. Prepare 1L of 105g / L sodium hydroxide solution.

[0062] 2. Prepare 1L of 40g / L NaCl solution in a closed reactor under stirring, add 50g of yellow phosphorus, and then close the feeding hole and stir at a speed of 600r / min.

[0063] 3. Use a pressure pump (the pump pressure is greater than the SO2 gas pressure) to pump 1L 100g / L sodium hydroxide solution into the phosphorus-containing NaCl solution, and at the same time, introduce 48g SO2 gas for reaction. The SO2 gas is controlled by flow and pressure, and the control method is (PV=nRT). The conditions for the complex reaction are: the reaction temperature is 180℃~230℃, the reaction end point pH is 8.0, the weight of yellow phosphorus added is 50% of the weight of the solid base, the weight of SO2 gas added is 48% of the weight of the solid base, and after the reaction is completed, it is homogenized at 80℃ for 88h.

[0064] 4. The solution after the complexation reaction is transferred to a distillation kettle, evacuated to -0.05Mpa, and heated to 250℃~320℃ for distillation.

[0065] 5. The distillate is returned to the alkali solution or NaCl solution; the residual liquid is placed in a cooling crystallization tank.

[0066] 6. The crystals are blow-dried or naturally dried at room temperature to obtain the target germanium activated agent H-HJ01.

[0067] The germanium activation agent H-HJ01 prepared in this example was used for the experiment. 20 g of the germanium activation agent H-HJ01 prepared in this example was mixed into 1000 g of germanium-containing copper concentrate (germanium 1587 g / t) for molten pool volatilization. The germanium grade in the slag was 9.42 g / t, and the germanium volatilization rate was 99.49%.

[0068] 40 g of the germanium activation agent H-HJ01 prepared in this example was mixed into 1000 g of coal ash (germanium 4832 g / t) for molten pool volatilization. The germanium grade in the slag was 33.85 g / t, and the germanium volatilization rate was 99.43%.

[0069] Example 5

[0070] 1. Prepare 1L of 95g / L sodium hydroxide solution.

[0071] 2. Prepare 1L of 60g / L NaCl solution in a closed reactor under stirring, add 25g of yellow phosphorus, then close the feeding hole and stir at a speed of 500r / min.

[0072] 3. Use a pressure pump (the pump pressure is greater than the SO2 gas pressure) to pump 1L 100g / L sodium hydroxide solution into the phosphorus-containing NaCl solution, and at the same time, introduce 80g SO2 gas for reaction. The SO2 gas is controlled by flow and pressure, and the control method is (PV=nRT). The conditions for the complex reaction are: the reaction temperature is 100℃~140℃, the reaction end point pH is 6.5, the weight of yellow phosphorus added is 25% of the weight of the solid base, the weight of SO2 gas added is 80% of the weight of the solid base, and after the reaction is completed, it is homogenized at 95℃ for 60h.

[0073] 4. The solution after the complexation reaction is transferred to a distillation kettle, evacuated to -0.05Mpa, and heated to 150℃~230℃ for distillation.

[0074] 5. The distillate is returned to the alkali solution or NaCl solution; the residual liquid is placed in a cooling crystallization tank.

[0075] 6. The crystals are blow-dried or naturally dried at room temperature to obtain the target germanium activated agent H-HJ01.

[0076] The germanium activation agent H-HJ01 prepared in this example was used for the experiment. 20 g of the germanium activation agent H-HJ01 prepared in this example was mixed into 1000 g of germanium-containing copper concentrate (germanium 1378 g / t) for molten pool volatilization. The germanium grade in the slag was 9.15 g / t, and the germanium volatilization rate was 99.53%.

[0077] 40 g of the germanium activation agent H-HJ01 prepared in this example was mixed into 1000 g of coal ash (germanium 4189 g / t) for molten pool volatilization. The germanium grade in the slag was 31.22 g / t, and the germanium volatilization rate was 99.28%.

Claims

1. A germanium activation agent H-HJ01, characterized in that: The germanium activation agent H-HJ01 is prepared from raw materials of sulfur dioxide, sodium hydroxide, yellow phosphorus and sodium chloride through complexation reaction, including the preparation of liquid I, the preparation of liquid II, the preparation of the agent and the post-treatment steps, specifically including: A. Preparation of Liquid I: Prepare a sodium hydroxide solution with a concentration of 90-110 g / L by mixing the sodium hydroxide in the formula ratio to obtain Liquid I; B. Preparation of Liquid II: Add 15-50 times the mass of water to the sodium chloride in the formula, stir to dissolve, then add the crushed yellow phosphorus with 10 mesh sieve in the formula, stir to obtain Liquid II; C. Preparation of the reagent: Place liquid I and liquid II in a reaction tank, and introduce sulfur dioxide of a prescribed ratio to carry out complex reaction and homogenization to obtain complex reaction liquid a; The temperature of the complex reaction is 10-350°C, and the pH value at the end point of the complex reaction is controlled at 5.5-13; The homogenization is carried out at a temperature of 50-100°C for 0.5-200h; the temperature of the reduced pressure distillation is 93-350°C; D. Post-treatment: The complex reaction solution a is subjected to reduced pressure distillation to obtain a distillation residue b; the distillation residue b is cooled, crystallized, and dried to obtain the target germanium reagent H-HJ01; The mass ratio of the raw materials sulfur dioxide, sodium hydroxide, yellow phosphorus and sodium chloride is: (40-90): (90-110): (1-50): (10-60).

2. The agent H-HJ01 for activating germanium according to claim 1, characterized in that: The mass ratio of the raw materials sulfur dioxide, sodium hydroxide, yellow phosphorus and sodium chloride is: (48-80):100:(1-30):(20-40).

3. The agent H-HJ01 for activating germanium according to claim 1, characterized in that: The stirring speed in step B is 10~1000r / min.

4. An application of the agent H-HJ01 for activating germanium according to any one of claims 1 to 3, characterized in that: The application of the germanium activation agent H-HJ01 in the preparation of an activator.

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