CN114715859A - Method for preparing 3N selenium from selenium slag - Google Patents
Method for preparing 3N selenium from selenium slag Download PDFInfo
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- CN114715859A CN114715859A CN202210437953.9A CN202210437953A CN114715859A CN 114715859 A CN114715859 A CN 114715859A CN 202210437953 A CN202210437953 A CN 202210437953A CN 114715859 A CN114715859 A CN 114715859A
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- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/02—Elemental selenium or tellurium
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The invention discloses a method for preparing 3N selenium from selenium slag. The invention provides a method for preparing 3N selenium by purifying selenium slag, which comprises the following steps: crushing and grinding the selenium slag into 200-mesh and 400-mesh powder, adding sulfuric acid to elute and remove copper, and carrying out solid-liquid separation to obtain copper liquid copper removal slag; adding a sodium sulfite solution into the decoppered slag, pressurizing and leaching, and performing solid-liquid separation to obtain leaching slag and a leaching solution; and (3) dripping sulfuric acid into the leachate for low-temperature precipitation to obtain red selenium, repeatedly washing the red selenium, and then, baking the red selenium at a high temperature by an infrared lamp to convert the red selenium into gray selenium which can reach the standard of 3N selenium. The invention adopts the processes of pressure leaching, low-temperature selenium precipitation and high-temperature transformation, has short process flow and high selenium recovery rate, and obtains the refined selenium with stable grade, thereby realizing the high-efficiency and simple treatment of the selenium slag.
Description
Technical Field
The invention belongs to the technical field of metallurgy, and particularly relates to a method for preparing 3N selenium from selenium slag.
Background
Selenium is an important rare and dispersive metal, and more than 90 percent of raw materials for extracting selenium come from copper anode mud. The process for purifying selenium from copper anode mud mainly comprises sulfating roasting, soda process and oxidizing roasting process, wherein selenium is oxidized and volatilized into smoke dust, and then is absorbed by water and reduced by sulfur dioxide to obtain crude selenium. The selenium slag is smelting slag which is obtained by purifying crude selenium by adopting purification treatment processes such as vacuum distillation, wet leaching and the like and is rich in selenium and precious metals, and the selenium content is 20-40%. The fire method of the selenium-rich material mainly adopts a sulfating roasting mode for recovery, and has the problems of large pollution, large energy consumption, long period and the like. Therefore, it is necessary to develop a method capable of solving the above problems.
Disclosure of Invention
The invention aims to provide a method for preparing 3N selenium from selenium slag.
The invention aims to realize the purpose, the method for preparing the 3N selenium by the selenium slag comprises the steps of pretreatment, pressure leaching, low-temperature selenium precipitation and high-temperature transformation, and specifically comprises the following steps:
A. pretreatment: ball-milling the selenium slag to obtain a material a, adding the material a into a sulfuric acid solution, stirring for reaction, and carrying out solid-liquid separation to obtain a copper liquid b and decoppered slag c;
B. pressure leaching:
1) preparing a sodium sulfite solution with the concentration of 280-300g/L to obtain a sodium sulfite solution d;
2) adding a sodium sulfite solution d into the decoppered slag c, and uniformly mixing to obtain a material e;
3) adding a dilute sulfuric acid solution into the material e to adjust the pH value to 6-7 to obtain a material f;
4) leaching the material f for 2-4 h at the pressure of 0.8-1.5MPa and the temperature of 100-150 ℃ to obtain a leaching solution g and leaching residues h;
C. low-temperature selenium deposition:
1) dropwise adding a sulfuric acid solution into the leaching solution g at a constant speed at the temperature of 20-40 ℃ for reaction, and then carrying out solid-liquid separation to obtain red selenium i, wherein the temperature is controlled not to exceed 40 ℃;
2) washing the red selenium i with water for multiple times until the pH value is 7 to obtain a material j;
D. high-temperature transformation: and (4) baking the material j until the ash selenium is obtained to obtain a target object.
The method comprises the steps of crushing and grinding selenium slag into 200-mesh and 400-mesh powder, adding sulfuric acid to elute and remove copper, and carrying out solid-liquid separation to obtain copper liquid copper-removed slag; adding a sodium sulfite solution into the decoppered slag, pressurizing and leaching, and carrying out solid-liquid separation to obtain leached slag and a leaching solution; and (3) dripping sulfuric acid into the leachate for low-temperature precipitation to obtain red selenium, repeatedly washing the red selenium, and then, baking the red selenium at a high temperature by an infrared lamp to convert the red selenium into gray selenium which can reach the standard of 3N selenium. The invention adopts the processes of pressure leaching, low-temperature selenium precipitation and high-temperature transformation to purify the selenium slag to prepare the 3N selenium, has short process flow and high selenium recovery rate, and obtains the refined selenium with stable grade, thereby realizing the high-efficiency and simple treatment of the selenium slag.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to be limiting in any way, and any modifications or alterations based on the teachings of the present invention are intended to fall within the scope of the present invention.
The method for preparing 3N selenium from selenium slag comprises the steps of pretreatment, pressure leaching, low-temperature selenium deposition and high-temperature transformation, and specifically comprises the following steps:
A. pretreatment: ball-milling the selenium slag to obtain a material a, adding the material a into a sulfuric acid solution, stirring for reaction, and carrying out solid-liquid separation to obtain a copper liquid b and decoppered slag c;
B. pressure leaching:
1) preparing a sodium sulfite solution with the concentration of 280-300g/L to obtain a sodium sulfite solution d;
2) adding a sodium sulfite solution d into the decoppered slag c, and uniformly mixing to obtain a material e;
3) adding a dilute sulfuric acid solution into the material e to adjust the pH value to 6-7 to obtain a material f;
4) leaching the material f for 2-4 h at the pressure of 0.8-1.5MPa and the temperature of 100-150 ℃ to obtain a leaching solution g and leaching residues h;
C. low-temperature selenium deposition:
1) dropwise adding a sulfuric acid solution into the leaching solution g at a constant speed at the temperature of 20-40 ℃ for reaction, and then carrying out solid-liquid separation to obtain red selenium i, wherein the temperature is controlled not to exceed 40 ℃;
2) washing the red selenium i with water for multiple times until the pH value is 7 to obtain a material j;
D. high-temperature transformation: and (4) baking the material j until the ash selenium is obtained to obtain a target object.
And B, ball milling the selenium slag in the step A to 200-400 meshes.
The concentration of the sulfuric acid solution in the step A is 150-250 g/L.
The reaction time in the step A is 1.5-2.5 h.
And the liquid-solid volume ratio of the sodium sulfite solution d to the decoppering slag c in the step B is (9-11): 1.
C, the volume ratio of the sulfuric acid solution to the leaching solution g in the step 1) is 1: (4-6).
The sulfuric acid solution is concentrated sulfuric acid.
And step 1) is to drip the sulfuric acid solution into the leaching solution g at a constant speed at the temperature of 20-40 ℃, and stir at a stirring speed of more than 200r/min for reaction.
The reaction time is 1-2 h.
And D, baking the material j under an infrared lamp at the temperature of more than 100 ℃.
The method for preparing 3N selenium by using selenium slag comprises the following specific operations:
1. ball-milling the selenium slag to 200-mesh 400-mesh, adding the selenium slag into 200g/L sulfuric acid solution at normal temperature, stirring and reacting for 2h, and carrying out solid-liquid separation to obtain copper liquid and copper-removed slag;
2. preparing a sodium sulfite solution according to the concentration of 280-300g/L, and mixing the sodium sulfite solution according to the liquid-solid ratio of 10: 1 adding the copper-removing slag, uniformly mixing, adding a dilute sulfuric acid solution to adjust the pH value of the solution to be within the range of 6-7, and leaching the solution at the pressure of 0.8-1.5Mpa and the temperature of 100-150 ℃ for 3 hours. (the order of addition of materials was not adjustable)
3. The temperature of the leached solution is more than 60 ℃, solid-liquid separation is carried out, and the leachate is cooled to normal temperature;
4. under the temperature condition of 20-40 ℃, the volume ratio of the leaching solution to the water is 5: 1, dropwise adding a sulfuric acid solution at a constant speed, wherein the stirring speed of the solution is more than 200r/min, the temperature of the leaching solution releases heat in the sulfuric acid dropwise adding process, water is supplemented in the process, and the temperature of the solution is ensured not to exceed 40 ℃. The reaction time is 1-2h, and after the reaction is finished, the solid-liquid separation is carried out to obtain the red selenium;
5. washing red selenium with water for multiple times until the pH value is 7;
6. placing the red selenium in an infrared lamp, and baking at a temperature higher than 100 ℃ until the red selenium is gray selenium.
Example 1
Ball-milling 100g of selenium slag (with the selenium content of 24.12%) to 200 meshes, pretreating with 200g/L sulfuric acid solution at normal temperature for 2h, and carrying out solid-liquid separation to obtain 90g of decoppered slag; preparing 900mL of sodium sulfite solution according to the concentration of 280g/L, adding the decoppered slag, uniformly mixing, adding a dilute sulfuric acid solution to adjust the pH value of the solution to 6, and leaching for 3 hours at the pressure of 0.8Mpa and the temperature of 150 ℃. After leaching, quickly filtering and cooling to normal temperature. And (3) putting the leachate into a water bath at the temperature of 20 ℃, uniformly dripping 180 mL of concentrated sulfuric acid at the rotating speed of 200r/min, reacting for 2h, and carrying out solid-liquid separation after the reaction is finished to obtain the red selenium. Washing red selenium with water for several times until pH is 7. The red selenium is placed under an infrared lamp, the temperature is higher than 100 ℃, and the red selenium is baked for 0.5h and is converted into gray selenium. The grade of selenium in the ash selenium is 99.98%.
Example 2
Ball-milling 100g of selenium slag (with the selenium content of 32.32%) to 200 meshes, pretreating with 200g/L sulfuric acid solution for 2h at normal temperature, and carrying out solid-liquid separation to obtain 86g of decoppered slag; 860mL of sodium sulfite solution is prepared according to the concentration of 300g/L, the decoppering slag is added, the dilute sulfuric acid solution is added after uniform mixing to adjust the pH value of the solution to 7, and the solution is leached for 3 hours under the pressure of 1.2Mpa and the temperature of 150 ℃. After leaching, quickly filtering and cooling to normal temperature. And (3) putting the leachate into a water bath at the temperature of 20 ℃, uniformly dripping 170 mL of concentrated sulfuric acid at the rotating speed of 300 r/min, reacting for 1h, and carrying out solid-liquid separation after the reaction is finished to obtain the red selenium. Washing red selenium with water for several times until pH is 6.5. The red selenium is placed under an infrared lamp, the temperature is higher than 100 ℃, and the red selenium is baked for 0.5h and is converted into gray selenium. The grade of selenium in the ash selenium is 99.99%.
Example 3
Ball-milling 100g of selenium slag (with the selenium content of 23.. 33%) to 400 meshes, pretreating 150g/L of sulfuric acid solution at normal temperature for 2.5 hours, and carrying out solid-liquid separation to obtain 91.35g of decoppered slag; 915mL of sodium sulfite solution is prepared according to the concentration of 290g/L, the decoppered slag is added, the dilute sulfuric acid solution is added after uniform mixing to adjust the pH value of the solution to 6, and the solution is leached for 4 hours at the pressure of 0.8Mpa and the temperature of 100 ℃. After leaching, quickly filtering and cooling to normal temperature. And (3) putting the leachate into a water bath at 40 ℃, uniformly dripping 186 mL of concentrated sulfuric acid at the rotating speed of 260 r/min, reacting for 3h, and carrying out solid-liquid separation after the reaction is finished to obtain the red selenium. Washing red selenium with water for several times until pH is 7. The red selenium is placed under an infrared lamp, the temperature is higher than 100 ℃, and the red selenium is baked for 0.8h and is converted into gray selenium. The grade of selenium in the ash selenium is 99.94%.
Example 4
Ball-milling 100g of selenium slag (with selenium content of 29.. 28%) to 200 meshes, pretreating 250g/L of sulfuric acid solution at normal temperature for 1.5h, and carrying out solid-liquid separation to obtain 88.67g of decoppered slag; 897mL of sodium sulfite solution is prepared according to the concentration of 285g/L, the decoppering slag is added, the dilute sulfuric acid solution is added after the uniform mixing to adjust the pH value of the solution to 6, and the solution is leached for 2 hours under the pressure of 0.8Mpa and the temperature of 100 ℃. After leaching, quickly filtering and cooling to normal temperature. Putting the leachate into a water bath at 40 ℃, uniformly dripping 177 mL of concentrated sulfuric acid at the rotating speed of 260 r/min, reacting for 2h, and carrying out solid-liquid separation after the reaction is finished to obtain the red selenium. Washing red selenium with water for several times until pH is 7. The red selenium is placed under an infrared lamp, the temperature is higher than 100 ℃, and the red selenium is baked for 0.6h and is converted into gray selenium. The grade of selenium in the ash selenium is 99.98%.
Claims (10)
1. The method for preparing 3N selenium from selenium slag is characterized by comprising the steps of pretreatment, pressure leaching, low-temperature selenium precipitation and high-temperature transformation, and specifically comprises the following steps:
A. pretreatment: ball-milling the selenium slag to obtain a material a, adding the material a into a sulfuric acid solution, stirring for reaction, and carrying out solid-liquid separation to obtain a copper liquid b and decoppered slag c;
B. pressure leaching:
1) preparing a sodium sulfite solution with the concentration of 280-300g/L to obtain a sodium sulfite solution d;
2) adding a sodium sulfite solution d into the decoppered slag c, and uniformly mixing to obtain a material e;
3) adding a dilute sulfuric acid solution into the material e to adjust the pH value to 6-7 to obtain a material f;
4) leaching the material f for 2-4 h at the pressure of 0.8-1.5MPa and the temperature of 100-150 ℃ to obtain a leaching solution g and leaching residues h;
C. low-temperature selenium deposition:
1) dropwise adding a sulfuric acid solution into the leaching solution g at a constant speed at the temperature of 20-40 ℃ for reaction, and then carrying out solid-liquid separation to obtain red selenium i, wherein the temperature is controlled not to exceed 40 ℃;
2) washing the red selenium i with water for multiple times until the pH value is 7 to obtain a material j;
D. high-temperature transformation: and (4) baking the material j until the ash selenium is obtained to obtain a target object.
2. The method for preparing 3N selenium from selenium slag according to claim 1, wherein the ball milling in the step A is to ball mill the selenium slag to 200-400 meshes.
3. The method for preparing 3N selenium from selenium slag according to claim 1, wherein the concentration of the sulfuric acid solution in the step A is 150-250 g/L.
4. The method for preparing 3N selenium from selenium slag according to claim 1, wherein the reaction time in the step A is 1.5-2.5 hours.
5. The method for preparing 3N selenium from selenium slag according to claim 1, wherein the liquid-solid volume ratio of the sodium sulfite solution d in the step B to the decoppered slag c is (9-11): 1.
6. The method for preparing 3N selenium from selenium slag according to claim 1, wherein the volume ratio of the sulfuric acid solution to the leaching solution g in the step 1) is 1: (4-6).
7. The method for preparing 3N selenium from selenium slag according to claim 1 or 6, wherein the sulfuric acid solution is concentrated sulfuric acid.
8. The method for preparing 3N selenium from selenium slag according to claim 1, wherein the step C1) is to drop a sulfuric acid solution into the leaching solution g at a constant speed at a temperature of 20-40 ℃, and stir at a stirring speed of more than 200r/min for reaction.
9. The method for preparing 3N selenium from selenium slag according to claim 1 or 8, wherein the reaction time is 1-2 h.
10. The method for preparing 3N selenium from selenium slag according to claim 1, wherein the baking in the step D is that the material j is placed under an infrared lamp and baked at the temperature of more than 100 ℃.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102086029A (en) * | 2010-12-04 | 2011-06-08 | 金川集团有限公司 | Method for extracting selenium from selenium-contained material |
| CN102491287A (en) * | 2011-12-11 | 2012-06-13 | 郴州市金贵银业股份有限公司 | Process for separating and recovering selenium from selenium-containing material |
| JP2012246197A (en) * | 2011-05-30 | 2012-12-13 | Pan Pacific Copper Co Ltd | Method for purifying selenium by wet process |
| CN109319746A (en) * | 2018-11-14 | 2019-02-12 | 昆明理工大学 | A kind of method of vacuum distillation-sodium sulfite combination method purification impure selenium |
| CN110817811A (en) * | 2019-12-12 | 2020-02-21 | 昆明冶金研究院有限公司 | Preparation method of high-purity selenium powder with uniform particle size distribution |
| CN111394584A (en) * | 2020-04-09 | 2020-07-10 | 金川集团股份有限公司 | Method for separating and extracting tellurium, selenium and copper from copper-tellurium slag |
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- 2022-04-25 CN CN202210437953.9A patent/CN114715859A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102086029A (en) * | 2010-12-04 | 2011-06-08 | 金川集团有限公司 | Method for extracting selenium from selenium-contained material |
| JP2012246197A (en) * | 2011-05-30 | 2012-12-13 | Pan Pacific Copper Co Ltd | Method for purifying selenium by wet process |
| CN102491287A (en) * | 2011-12-11 | 2012-06-13 | 郴州市金贵银业股份有限公司 | Process for separating and recovering selenium from selenium-containing material |
| CN109319746A (en) * | 2018-11-14 | 2019-02-12 | 昆明理工大学 | A kind of method of vacuum distillation-sodium sulfite combination method purification impure selenium |
| CN110817811A (en) * | 2019-12-12 | 2020-02-21 | 昆明冶金研究院有限公司 | Preparation method of high-purity selenium powder with uniform particle size distribution |
| CN111394584A (en) * | 2020-04-09 | 2020-07-10 | 金川集团股份有限公司 | Method for separating and extracting tellurium, selenium and copper from copper-tellurium slag |
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