Method for enriching germanium from germanium-containing material

Abstract

The invention discloses a method for enriching germanium from a germanium-containing material, which comprises the following steps: (1) uniformly mixing the germanium-containing material with iron slag, limestone and quartz sand to obtain a mixture; (2) adding water into the mixture, and granulating to obtain round granules; (3) adding the round granules into a fuming furnace, spraying pulverized coal, introducing air, and performing fuming volatilization; and collecting the volatilized smoke dust to obtain the germanium-rich smoke dust. According to the method, by controlling the excess air coefficient and the temperature of the feeding period, the volatilization period and the deslagging period, the germanium enrichment effect can be guaranteed, and meanwhile the germanium recovery rate is increased.

Description

Technical Field

[0001] This invention belongs to the field of metallurgical and chemical technology, and specifically relates to a method for enriching germanium from germanium-containing materials. Background Technology

[0002] Germanium is an important strategic metal, hailed as the "king of new materials," and is one of the key basic materials in fields such as optical fiber communication, solar cells, and infrared optical devices. In nature, germanium rarely forms independent minerals; it is mainly found as an associated mineral in lead-zinc ores and lignite.

[0003] Existing methods for enriching germanium from low-grade germanium-containing materials mainly include two types: wet and pyrometallurgical methods. Because the materials often contain other harmful elements that affect germanium enrichment, or contain other valuable elements themselves, wet enrichment processes are lengthy and costly. While existing pyrometallurgical enrichment processes generally show some enrichment effects in small-scale experiments, after industrialization, due to numerous uncontrollable factors in the material's reaction process, the enrichment effect of germanium in current industrialized pyrometallurgical enrichment processes is poor, and the germanium recovery rate is low. Summary of the Invention

[0004] Therefore, the object of the present invention is to provide a method for enriching germanium from germanium-containing materials.

[0005] In a first aspect, the present invention provides a method for enriching germanium from germanium-containing materials, comprising the following steps: (1) After the germanium-containing material is mixed evenly with iron slag, limestone and quartz sand, a mixture is obtained; (2) Add water to the mixture and granulate to obtain round granules; (3) Add the round granules to the fuming furnace, inject pulverized coal, and introduce air for fuming and volatilization; collect the volatilized dust to obtain germanium-rich dust; wherein: during the fuming and volatilization process, Feeding period: Control the amount of pulverized coal and the amount of air introduced to make the excess air coefficient α 0.9~1.1 and the feed temperature 1050~1200℃; Volatilization period: Control the amount of pulverized coal injected and the amount of air introduced to make the excess air coefficient α 0.8~0.9 and the volatilization temperature 1100~1300℃; the excess air coefficient α during the volatilization period should be at least 0.05 lower than that during the feeding period, and the volatilization temperature should be at least 50℃ higher than that during the feeding period. Slag discharge period: Control the amount of pulverized coal injected and the amount of air introduced to make the excess air coefficient α 0.95~1.1 and the slag discharge temperature 1200~1300℃; the slag discharge temperature should be at least 50℃ higher than the volatile matter temperature. Preferably, in step (1), the germanium-containing material is a wet germanium-containing leaching residue.

[0006] More preferably, the wet germanium-containing leaching residue has a water content of 12~28wt% and a germanium content of ≥500g / t (calculated based on dry germanium-containing leaching residue).

[0007] Preferably, in step (1), iron slag, limestone, and quartz sand are added to adjust the FeO / SiO2 ratio in the mixture to 1.1~1.7 and the CaO / SiO2 ratio to 0.35~0.8.

[0008] Preferably, in step (1), the mixture is mixed evenly until the mass deviation of each element in the mixture is no greater than 3% for Fe, no greater than 5% for Ge, and no greater than 3% for moisture content.

[0009] Preferably, in step (2), water is added to the mixture until the moisture content is 15-26%.

[0010] Preferably, in step (3), during the fuming and volatilization process, Feeding period: Control the amount of pulverized coal and the amount of air introduced to make the excess air coefficient α 1.0~1.1 and the feed temperature 1050~1100℃; Volatilization period: Control the amount of pulverized coal injected and the amount of air introduced to make the excess air coefficient α 0.8~0.9 and the volatilization temperature 1150~1200℃; Slag discharge period: Control the amount of pulverized coal and the amount of air introduced to make the excess air coefficient α 0.95~1.1 and the slag discharge temperature 1250~1300℃.

[0011] Preferably, in step (3), the feeding rate during the feeding period is 0.62~1.25 t / m. 2 ·h.

[0012] Preferably, in step (3), the evaporation time of the evaporation period is 40~80min.

[0013] Preferably, in step (3), the slag discharge time is 5 to 15 minutes.

[0014] Preferably, in step (3), the Ge content in the waste residue generated during the volatilization process is not higher than 50 g / t.

[0015] Compared with the prior art, one or more of the above technical solutions can achieve at least one of the following beneficial effects: In this invention, by controlling the excess air coefficient and temperature during the feeding period, volatilization period, and slag discharge period, the germanium enrichment effect can be guaranteed while improving the germanium recovery rate. Attached Figure Description

[0016] Figure 1 This is a process flow diagram of the method for enriching germanium from germanium-containing materials according to the present invention. Detailed Implementation

[0017] To facilitate understanding of the present invention, the present invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of protection of the present invention is not limited to the following specific embodiments. As mentioned above, in a first aspect, the present invention provides a method for enriching germanium from germanium-containing materials, comprising the following steps: (1) After the germanium-containing material is mixed evenly with iron slag, limestone and quartz sand, a mixture is obtained; (2) Add water to the mixture and granulate to obtain round granules; (3) Add the round granules to the fuming furnace, inject pulverized coal, and introduce air for fuming and volatilization; collect the volatilized dust to obtain germanium-rich dust; wherein: during the fuming and volatilization process, Feeding period: Control the amount of pulverized coal and the amount of air introduced to make the excess air coefficient α 0.9~1.1 (including but not limited to: 0.9, 0.92, 0.95, 0.98, 1.0, 1.02, 1.05, 1.08, 1.1, etc.) and the feed temperature 1050~1200℃ (including but not limited to: 1050, 1080℃, 1100℃, 1120℃, 1150℃, 1180℃, 1200℃, etc.). Volatilization period: Control the amount of pulverized coal injected and the amount of air introduced to make the excess air coefficient α 0.8~0.9 (including but not limited to: 0.8, 0.81, 0.82, 0.83, 0.84, 0.85, 0.86, 0.87, 0.88, 0.89, 0.9, etc.) and the volatilization temperature 1100~1300℃ (including but not limited to: 1100℃, 1120℃, 1150℃, 1180℃, 1200℃, 1220℃, 1250℃, 1280℃, 1300℃, etc.); the excess air coefficient α during the volatilization period should be at least 0.05 lower than that during the feeding period, and the volatilization temperature should be at least 50℃ higher than that during the feeding period; Slag discharge period: Control the amount of pulverized coal injected and the amount of air introduced to make the excess air coefficient α 0.95~1.1 and the slag discharge temperature 1200~1300℃ (including but not limited to: 1200℃, 1210℃, 1220℃, 1230℃, 1240℃, 1250℃, 1260℃, 1270℃, 1280℃, 1290℃, 1300℃, etc.); the slag discharge temperature should be at least 50℃ higher than the volatile matter temperature.

[0018] Research has revealed that, in the method of this invention, the excess air coefficient and temperature during the feeding period, volatilization period, and slag discharge period have a significant impact on the germanium enrichment effect and germanium recovery rate. In this invention, controlling the parameters at different stages of the fuming and volatilization process can better improve the germanium enrichment effect and recovery rate, thereby enhancing the germanium enrichment effect in industrial production.

[0019] Preferably, in step (1), the germanium-containing material is a wet germanium-containing leaching residue.

[0020] More preferably, the wet germanium-containing leaching residue has a water content of 12-28% and a germanium content of ≥500g / t (calculated based on dry germanium-containing leaching residue).

[0021] Preferably, in step (1), iron slag, limestone, and quartz sand are added to adjust the FeO / SiO2 ratio in the mixture to 1.1~1.7, including but not limited to: 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, etc.; and the CaO / SiO2 ratio to 0.35~0.8, including but not limited to: 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, etc.

[0022] This invention can better control the slag phase during the volatilization process by controlling FeO / SiO2 and CaO / SiO2, which is beneficial for the enrichment and recovery of germanium.

[0023] Preferably, in step (1), the mixture is mixed evenly until the mass deviation of each element in the mixture is no greater than 3% for Fe, no greater than 5% for Ge, and no greater than 3% for moisture content.

[0024] Preferably, in step (2), water is added to the mixture until the moisture content is 15-26%.

[0025] Preferably, in step (3), during the volatilization process, Feeding period: Control the amount of pulverized coal and the amount of air introduced to make the excess air coefficient α 1.0~1.1 and the feed temperature 1050~1100℃; Volatilization period: Control the amount of pulverized coal injected and the amount of air introduced to make the excess air coefficient α 0.8~0.9 and the volatilization temperature 1150~1200℃; Slag discharge period: Control the amount of pulverized coal and the amount of air introduced to make the excess air coefficient α 0.95~1.1 and the slag discharge temperature 1250~1300℃.

[0026] Preferably, in step (3), the feeding rate during the feeding period is 0.62~1.25 t / m. 2 ·h.

[0027] Preferably, in step (3), the evaporation time of the evaporation period is 40~80min, including but not limited to 40min, 50min, 60min, 70min, 80min, etc.

[0028] Preferably, in step (3), the slag discharge time is 5 to 15 minutes, including but not limited to: 5 minutes, 8 minutes, 10 minutes, 12 minutes, 15 minutes, etc.

[0029] Preferably, in step (3), the Ge content in the waste residue generated during the volatilization process is not higher than 50 g / t.

[0030] The process flow diagram of the method for enriching germanium from germanium-containing materials in this invention is as follows: Figure 1 As shown, the specific method can be found in the embodiments.

[0031] Example 1 In this embodiment, the contents of each major component in the completely dried germanium-containing leaching residue are as follows: Zn 6.5%, Ge 1200g / t, Cl 4.8%, As 0.6%, Si 15.8%, Fe 6.1%, S 1.8%, Na 2.6%.

[0032] The enrichment method for germanium is as follows: (1) Wet germanium-containing leaching residue (water content 27%) is mixed with iron slag, quartz sand and limestone according to FeO / SiO2=1.35, CaO / SiO2=0.6 and water content 23%. The mixture is mixed 8 times by a crane grab bucket to achieve the following uniformity: 10 points are randomly selected and the element deviation in the mixture is: Fe≯3%, Ge≯5%, water content≯3%; the mixture is obtained.

[0033] (2) Add water to the mixture to make the moisture content of the mixture reach 26%, and then granulate it through a cylindrical pellet mill to obtain the furnace feed. (3) The feed material is conveyed into the fuming furnace via a conveyor belt for fuming and volatilization. The resulting flue gas is then collected by a bag filter to obtain germanium-enriched dust. During the fuming and volatilization process: ① During the feeding period, control the pulverized coal injection rate and oxygen supply rate to maintain the excess air coefficient α at around 0.92, and control the feeding rate at 1.1 t / m. 2 • h, furnace temperature controlled at 1100℃; ② During the volatilization period, control the amount of pulverized coal and oxygen to maintain the excess air coefficient α at around 0.85, control the furnace temperature at 1200℃, and volatilize for 60 minutes; ③ During the slag discharge period, control the amount of pulverized coal and oxygen to maintain the excess air coefficient α at around 1.0, control the furnace temperature at 1250℃, control the slag discharge time at 8 minutes, discharge the slag, and after water quenching, obtain the waste slag.

[0034] Comparative Example 1 The process is basically the same as in Example 1, except that the parameter control during the fuming and volatilization process in step (3) is different, as follows: Comparative Example 1-1 ① During the feeding period, control the pulverized coal injection rate and oxygen supply rate to maintain the excess air coefficient α at around 0.92, and control the feeding rate at 1.1 t / m.2 • h, furnace temperature controlled at 1100℃; ② During the volatilization period, control the amount of coal injected and the amount of oxygen introduced to maintain the excess air coefficient α at around 0.92, control the furnace temperature at 1200℃, and volatilize for 60 minutes; ③ During the slag discharge period, control the amount of pulverized coal and oxygen to maintain the excess air coefficient α at around 0.92, control the furnace temperature at 1250℃, and control the slag discharge time at 8 minutes.

[0035] Comparative Examples 1-2 ① During the feeding period, control the pulverized coal injection rate and oxygen supply rate to maintain the excess air coefficient α at around 0.85, and control the feeding rate at 1.1 t / m. 2 • h, furnace temperature controlled at 1100℃; ② During the volatilization period, control the amount of pulverized coal and oxygen to maintain the excess air coefficient α at around 0.85, control the furnace temperature at 1200℃, and volatilize for 60 minutes; ③ During the slag discharge period, control the amount of pulverized coal and oxygen to maintain the excess air coefficient α at around 0.85, control the furnace temperature at 1250℃, and control the slag discharge time at 8 minutes.

[0036] Comparative Examples 1-3 ① During the feeding period, control the pulverized coal injection rate and oxygen supply rate to maintain the excess air coefficient α at around 1.0, and control the feeding rate at 1.1 t / m. 2 • h, furnace temperature controlled at 1100℃; ② During the volatilization period, control the amount of coal injected and the amount of oxygen introduced to maintain the excess air coefficient α at around 1.0, control the furnace temperature at 1200℃, and volatilize for 60 minutes; ③ During the slag discharge period, control the amount of pulverized coal and oxygen to maintain the excess air coefficient α at around 1.0, control the furnace temperature at 1250℃, control the slag discharge time at 8 minutes, discharge the slag, and after water quenching, obtain the waste slag.

[0037] Comparative Example 2 The process is basically the same as in Example 1, except that the parameter control during the fuming and volatilization process in step (3) is different, as follows: Comparative Example 2-1 ① During the feeding period, control the pulverized coal injection rate and oxygen supply rate to maintain the excess air coefficient α at around 0.92, and control the feeding rate at 1.1 t / m. 2 • h, furnace temperature controlled at 1100℃; ② During the volatilization period, control the amount of coal injected and the amount of oxygen introduced to maintain the excess air coefficient α at around 0.85, control the furnace temperature at 1100℃, and volatilize for 60 minutes; ③ During the slag discharge period, control the amount of pulverized coal and oxygen to maintain the excess air coefficient α at around 1.0, control the furnace temperature at 1100℃, control the slag discharge time at 8 minutes, discharge the slag (the slag viscosity is relatively high during slag discharge), and after water quenching, obtain the waste slag.

[0038] Comparative Example 2-2 ① During the feeding period, control the pulverized coal injection rate and oxygen supply rate to maintain the excess air coefficient α at around 0.92, and control the feeding rate at 1.1 t / m. 2 • h, furnace temperature controlled at 1200℃; ② During the volatilization period, control the amount of pulverized coal and oxygen to maintain the excess air coefficient α at around 0.85, control the furnace temperature at 1200℃, and volatilize for 60 minutes; ③ During the slag discharge period, control the amount of pulverized coal and oxygen to maintain the excess air coefficient α at around 1.0, control the furnace temperature at 1200℃, control the slag discharge time at 8 minutes, discharge the slag, and after water quenching, obtain the waste slag.

[0039] Comparative Examples 2-3 ① During the feeding period, control the pulverized coal injection rate and oxygen supply rate to maintain the excess air coefficient α at around 0.92, and control the feeding rate at 1.1 t / m. 2 • h, furnace temperature controlled at 1250℃; ② During the volatilization period, control the amount of pulverized coal and oxygen to maintain the excess air coefficient α at around 0.85, control the furnace temperature at 1250℃, and volatilize for 60 minutes; ③ During the slag discharge period, control the amount of pulverized coal and oxygen to maintain the excess air coefficient α at around 1.0, control the furnace temperature at 1250℃, control the slag discharge time at 8 minutes, discharge the slag, and after water quenching, obtain the waste slag.

[0040] Example 2 In this embodiment, the contents of each major component in the completely dried germanium-containing leaching residue are as follows: Zn 7.3%, Ge 1033 g / t, Cl 5.4%, As 0.7%, Si 14.8%, Fe 6.6%, S 1.9%, Na 2.4%.

[0041] The enrichment method for germanium is as follows: (1) Wet germanium-containing leaching residue (20% water content) is mixed with iron slag, quartz sand and limestone according to FeO / SiO2=1.2, CaO / SiO2=0.4 and water content of 15%. The mixture is mixed 8 times by a crane grab bucket to achieve the following uniformity: 10 points are randomly selected and the element deviation in the mixture is: Fe≯3%, Ge≯5%, water content≯3%; the mixture is obtained.

[0042] (3) Add water to the mixture to make the moisture content of the mixture reach 24%, and then granulate it through a cylindrical pellet mill to obtain the furnace feed. (3) The feed material is conveyed into the fuming furnace via a conveyor belt for fuming and volatilization. The resulting flue gas is then collected by a bag filter to obtain germanium-enriched dust. During the fuming and volatilization process: ① During the feeding period, control the pulverized coal injection rate and oxygen supply rate to maintain the excess air coefficient α at around 1.1, and control the feeding rate at 0.7 t / m. 2 • h, furnace temperature controlled at 1050℃; ② During the volatilization period, control the amount of coal injected and the amount of oxygen introduced to maintain the excess air coefficient α at around 0.8, control the furnace temperature at 1250℃, and volatilize for 40 minutes; ③ During the slag removal period, control the amount of pulverized coal and oxygen to maintain the excess air coefficient α at around 0.95, control the furnace temperature at 1300℃, control the slag removal time at 5 minutes, remove the slag, and after water quenching, obtain the waste slag.

[0043] Example 3 In this embodiment, the contents of each major component in the completely dried germanium-containing leaching residue are as follows: Zn 5.7%, Ge 1324 g / t, Cl 4.65%, As 0.48%, Si 17.8%, Fe 5.7%, S 1.2%, Na 2.3%.

[0044] The enrichment method for germanium is as follows: (1) Wet germanium-containing leaching residue (18% water content) is mixed with iron slag, quartz sand and limestone according to FeO / SiO2=1.6, CaO / SiO2=0.7 and water content of 12%. The mixture is mixed 8 times by a crane grab bucket to achieve the following uniformity: 10 points are randomly selected and the element deviation in the mixture is: Fe≯3%, Ge≯5%, water content≯3%; the mixture is obtained.

[0045] (2) Add water to the mixture to make the moisture content of the mixture reach 21%, and then granulate it through a cylindrical pellet mill to obtain the furnace feed. (3) The feed material is conveyed into the fuming furnace via a conveyor belt for fuming and volatilization. The resulting flue gas is then collected by a bag filter to obtain germanium-enriched dust. During the fuming and volatilization process: ① During the feeding period, control the pulverized coal injection rate and oxygen supply rate to maintain the excess air coefficient α at around 1.0, and control the feeding rate at 1.2 t / m. 2 • h, furnace temperature controlled at 1150℃; ② During the volatilization period, control the amount of coal injected and the amount of oxygen introduced to maintain the excess air coefficient α at around 0.9, control the furnace temperature at 1200℃, and volatilize for 80 minutes; ③ During the slag discharge period, control the amount of coal injection and oxygen supply to maintain the excess air coefficient α at around 1.1, control the furnace temperature at 1250℃, and control the slag discharge time at 15 minutes. The discharged slag is then water-quenched to obtain waste slag.

[0046] The Ge content in the flue dust and waste residue of Examples 1-3 and Comparative Examples 1-2 of the present invention was measured, and the results are shown in Table 1.

[0047] Table 1 The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be construed as limiting the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A method for enriching germanium from germanium-containing materials, characterized in that, Includes the following steps: (1) After the germanium-containing material is mixed evenly with iron slag, limestone and quartz sand, a mixture is obtained; (2) Add water to the mixture and granulate to obtain round granules; (3) Add the round granules to the fuming furnace, inject pulverized coal and introduce air for fuming and volatilization; collect the volatilized dust to obtain germanium-rich dust; wherein: during the fuming and volatilization process, Feeding period: Control the amount of pulverized coal and the amount of air introduced to make the excess air coefficient α 0.9~1.1 and the feed temperature 1050~1200℃; Volatilization period: Control the amount of pulverized coal injected and the amount of air introduced to make the excess air coefficient α 0.8~0.9 and the volatilization temperature 1100~1300℃; the excess air coefficient α during the volatilization period should be at least 0.05 lower than that during the feeding period, and the volatilization temperature should be at least 50℃ higher than that during the feeding period. Slag discharge period: Control the amount of pulverized coal injected and the amount of air introduced to make the excess air coefficient α 0.95~1.1 and the slag discharge temperature 1200~1300℃; the slag discharge temperature should be at least 50℃ higher than the volatile matter temperature.

2. The method for enriching germanium from germanium-containing materials according to claim 1, characterized in that, In step (1), the germanium-containing material is a wet germanium-containing leaching residue. And / or: The wet germanium-containing leaching residue has a water content of 12~28wt%; calculated based on the dry germanium-containing leaching residue, the germanium content is ≥500g / t.

3. The method for enriching germanium from germanium-containing materials according to claim 1, characterized in that, In step (1), iron slag, limestone, and quartz sand are added to adjust the FeO / SiO2 ratio in the mixture to 1.1~1.7 and the CaO / SiO2 ratio to 0.35~0.

8. And / or: Mix thoroughly until the mass deviation of each element in the mixture is no greater than 3% for Fe, no greater than 5% for Ge, and no greater than 3% for moisture content.

4. The method for enriching germanium from germanium-containing materials according to claim 1, characterized in that, In step (2), water is added to the mixture until the moisture content is 15-26%.

5. The method for enriching germanium from germanium-containing materials according to claim 1, characterized in that, In step (3), during the fuming and volatilization process: Feeding period: Control the amount of pulverized coal and the amount of air introduced to make the excess air coefficient α 1.0~1.1 and the feed temperature 1050~1100℃; Volatilization period: Control the amount of pulverized coal injected and the amount of air introduced to make the excess air coefficient α 0.8~0.9 and the volatilization temperature 1150~1200℃; Slag discharge period: Control the amount of pulverized coal and the amount of air introduced to make the excess air coefficient α 0.95~1.1 and the slag discharge temperature 1250~1300℃.

6. The method for enriching germanium from germanium-containing materials according to claim 1 or 5, characterized in that, In step (3), the feeding rate during the feeding period is 0.62~1.25 t / m. 2 ·h.

7. The method for enriching germanium from germanium-containing materials according to claim 1 or 5, characterized in that, In step (3), the evaporation time of the evaporation period is 40~80min.

8. The method for enriching germanium from germanium-containing materials according to claim 1, characterized in that, In step (3), the slag discharge time is 5 to 15 minutes.

9. The method for enriching germanium from germanium-containing materials according to claim 1, characterized in that, In step (3), the Ge content in the waste residue generated during the fuming and volatilization process is not higher than 50 g / t.

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