Dissociating agent CG76 for leaching of antimony and its preparation method and application

Abstract

The application discloses a dissociation agent CG76 for antimony leaching, and a preparation method and application thereof. The dissociation agent CG76 for antimony leaching is prepared from raw materials, including sodium sulfide, sodium hydroxide, sodium carbonate, sulfur powder or a sodium polysulfide precursor, sodium sulfite or sodium thiosulfate, magnesium oxide, magnesium hydroxide, calcium oxide or calcium hydroxide. The dissociation agent KU54 for bismuth leaching can simultaneously realize alkali dissociation activation and sulfur complexing leaching of antimony in an alkaline sulfidation system, and can reduce sulfidation agent loss and impurity co-leaching through stable components and impurity inhibition components, and has the characteristics of simple process, good selectivity, high stability of leaching solution and strong adaptability for subsequent recovery.

Description

Technical Field

[0001] This invention belongs to the field of metallurgical technology, specifically relating to a dissociation agent CG76 for antimony leaching, its preparation method, and its application. Background Technology

[0002] Antimony is an important strategic non-ferrous metal, widely used in flame retardant materials, alloys, semiconductors, glass clarifying agents, and chemical catalysis. In nature and as a secondary resource in metallurgy, antimony exists primarily as stibnite (Sb₂S₃), antimony oxide (Sb₂O₃), antimonates, complex sulfides, and in association with lead, arsenic, iron, copper, and silicon. Due to the complex composition, fine particle size, and high impurity content of antimony-containing materials, conventional acid leaching, oxidative roasting, or single alkaline leaching methods often suffer from poor selectivity, unstable leaching rates, severe equipment corrosion, significant impurity co-leaching, and a heavy burden on subsequent purification.

[0003] In existing technologies, hydrochloric acid or chloride salt systems can promote the dissolution of some antimony oxide and antimony sulfide, but these systems are highly corrosive to equipment and easily cause impurities such as Fe, Pb, Cu, and As to simultaneously enter the solution, making subsequent separation difficult. NaOH alkali leaching alone has a certain leaching effect on oxidized antimony, but its ability to damage antimony sulfide minerals is insufficient, making it difficult to effectively open the Sb-S structure. While the Na₂S sulfide-alkali system can form soluble antimony thiocomplexes with antimony sulfide, the system's alkalinity, sulfur ion stability, and impurity suppression ability are insufficient, easily leading to problems such as low utilization rate of the sulfiding agent, poor stability of the leachate, sulfur oxidation loss, and fluctuations in the subsequent recovery process.

[0004] Therefore, developing a composite dissociation agent that combines strong alkali activation, sulfur complexation leaching, sulfide stabilization, impurity inhibition, and solid-liquid interface strengthening is of great significance for improving the leaching efficiency of antimony-containing materials, reducing impurity co-leaching, and improving the subsequent antimony recovery process. Summary of the Invention

[0005] The first objective of this invention is to provide a dissociation agent CG76 for leaching antimony; the second objective is to provide a method for preparing the aforementioned dissociation agent CG76 for leaching antimony; and the third objective is to provide applications of the aforementioned dissociation agent CG76 for leaching antimony.

[0006] The first objective of this invention is achieved by the fact that the antimony leaching dissociation agent CG76 is prepared from raw materials such as sodium sulfide, sodium hydroxide, sodium carbonate, sulfur powder or sodium polysulfide precursor, sodium sulfite or sodium thiosulfate, magnesium oxide, magnesium hydroxide, calcium oxide or calcium hydroxide.

[0007] The second objective of this invention is achieved by including precursor preparation and post-processing steps, specifically including: A. Precursor preparation: Sodium sulfide, sodium hydroxide, sodium carbonate, sulfur powder or sodium polysulfide precursor, sodium sulfite or sodium thiosulfate, magnesium oxide, magnesium hydroxide, calcium oxide or calcium hydroxide are placed in a closed alkali-resistant mixer according to the formula ratio. After adding the dispersing components, stir and spray deionized water to make the water content of the system 10~15%. Continue stirring for 50~70 minutes to obtain semi-dry precursor a. B. Post-processing: 1) Place the semi-dry precursor a in a sealed environment at 80~100℃ for 1~3h to obtain material b; 2) Material b is vacuum dried, cooled, crushed and sieved to obtain the leaching dissociation agent CG76 for antimony.

[0008] The specific steps are as follows: Sodium hydroxide, sodium carbonate, sodium citrate, sodium tartrate, sodium gluconate, sodium thiosulfate, sodium sulfite, and magnesium oxide or magnesium hydroxide, as specified in the formula, were placed in a sealed alkali-resistant mixer and stirred at 45°C for 40 min. Deionized water was then slowly sprayed in to bring the system's moisture content to approximately 12%, and stirring continued for 60 min to obtain a semi-dry precursor. This precursor was then activated at 90°C in a sealed environment for 2 h, removed, and vacuum-dried at 90°C for 4 h. After cooling, it was pulverized and passed through a 120-mesh sieve to obtain powdered CG76.

[0009] The third objective of this invention is achieved through the application of the antimony leaching dissociation agent CG76 in the antimony leaching process of antimony-containing materials; the specific operation is as follows: 100g of antimony-containing material of the stibnite type was added to 150g of CG76, and the liquid-to-solid ratio was controlled at 6mL / g. The reaction was carried out at 90℃ and 400r / min for 3h. After the reaction, the mixture was filtered to obtain an antimony-containing alkaline sulfide leaching solution and leaching residue. In this process, antimony mainly entered the liquid phase in the form of antimony thiourea complexes, while iron, lead, and some siliceous gangue were mainly retained in the residue phase.

[0010] The antimony leaching dissociation agent CG76 described in this invention can simultaneously achieve alkaline hydrolysis activation and sulfur complexation leaching of antimony in an alkaline sulfidation system. It also reduces the loss of sulfiding agent and co-leaching of impurities through stabilizing and suppressing components. It features a simple process, good selectivity, high stability of the leachate, and strong adaptability to subsequent recovery. Detailed Implementation

[0011] The present invention will be further described below with reference to embodiments, but this is not intended to limit the present invention in any way. Any modifications or substitutions made based on the teachings of the present invention shall fall within the protection scope of the present invention.

[0012] The antimony leaching dissociation agent CG76 described in this invention is prepared from raw materials such as sodium sulfide, sodium hydroxide, sodium carbonate, sulfur powder or sodium polysulfide precursor, sodium sulfite or sodium thiosulfate, magnesium oxide, magnesium hydroxide, calcium oxide or calcium hydroxide.

[0013] The antimony leaching dissociation agent CG76 is prepared from the following raw materials: 35-60 parts by weight of sodium sulfide, 20-45 parts by weight of sodium hydroxide, 5-15 parts by weight of sodium carbonate, 1-8 parts by weight of sulfur powder or sodium polysulfide precursor, 2-10 parts by weight of sodium sulfite or sodium thiosulfate, and 1-8 parts by weight of magnesium oxide, magnesium hydroxide, calcium oxide or calcium hydroxide.

[0014] The antimony leaching dissociation agent CG76 is prepared from raw materials comprising 45-55 parts by weight of sodium sulfide, 25-35 parts by weight of sodium hydroxide, 6-12 parts by weight of sodium carbonate, 2-5 parts by weight of sulfur powder or sodium polysulfide precursor, 3-6 parts by weight of sodium sulfite or sodium thiosulfate, and 2-5 parts by weight of magnesium oxide, magnesium hydroxide, calcium oxide or calcium hydroxide.

[0015] The method for preparing the antimony leaching dissociation agent CG76 according to the present invention includes precursor preparation and post-treatment steps, specifically including: A. Precursor preparation: Sodium sulfide, sodium hydroxide, sodium carbonate, sulfur powder or sodium polysulfide precursor, sodium sulfite or sodium thiosulfate, magnesium oxide, magnesium hydroxide, calcium oxide or calcium hydroxide are placed in a closed alkali-resistant mixer according to the formula ratio. After adding the dispersing components, stir and spray deionized water to make the water content of the system 10~15%. Continue stirring for 50~70 minutes to obtain semi-dry precursor a. B. Post-processing: 1) Place the semi-dry precursor a in a sealed environment at 80~100℃ for 1~3h to obtain material b; 2) Material b is vacuum dried, cooled, crushed and sieved to obtain the leaching dissociation agent CG76 for antimony.

[0016] The dispersing component mentioned in step A is one or more of sodium polyacrylate, sodium lignosulfonate, sodium hexametasulfate, and sodium carboxymethyl cellulose.

[0017] In step A, after adding the dispersing component, the stirring is carried out at a temperature of 40~50℃ for 30~50 minutes.

[0018] The vacuum drying temperature described in step 2) is 80~100℃, and the time is 3~5h.

[0019] The application of the antimony leaching dissociation agent CG76 described in this invention refers to its application in the antimony leaching process of antimony-containing materials.

[0020] The antimony impregnation of the antimony-containing material includes a main reaction and a post-treatment step, specifically including: A. Main reaction: Add antimony leaching dissociation agent CG76 to the antimony-containing material to be treated, control the liquid-solid ratio at 5~7mL / g, and react for 2~4h at a temperature of 80~100℃ and a stirring speed of 300~500r / min. B. Post-treatment: After the reaction is completed, the solution and leaching residue containing antimony are obtained by filtration.

[0021] The present invention will be further described below with reference to specific embodiments: Example 1

[0022] Weigh out 50 parts of sodium sulfide, 30 parts of sodium hydroxide, 8 parts of sodium carbonate, 4 parts of sulfur powder, 4 parts of sodium sulfite, 3 parts of magnesium oxide, and 1 part of sodium polyacrylate. Place them in a sealed alkali-resistant mixer and stir at 40°C for 40 min. Then, slowly spray deionized water to make the water content of the system 12%, and continue stirring for 60 min to obtain a semi-dry precursor. Activate the semi-dry precursor in a sealed environment at 90°C for 2 h, vacuum dry at 90°C for 4 h, cool, pulverize, and pass through a 120-mesh sieve to obtain CG76, a dissociation agent for leaching the target antimony.

[0023] Example 2

[0024] Weigh out 35 parts sodium sulfide, 20 parts sodium hydroxide, 5 parts sodium carbonate, 1 part sulfur powder, 2 parts sodium thiosulfate, 1 part magnesium hydroxide, and 0.5 parts sodium lignosulfonate. Place them in a sealed alkali-resistant mixer and stir at 30°C for 50 min. Then, slowly spray deionized water to make the water content of the system 10%, and continue stirring for 50 min to obtain a semi-dry precursor. Activate the semi-dry precursor in a sealed environment at 80°C for 3 h, vacuum dry at 80°C for 5 h, cool, pulverize, and pass through a 120-mesh sieve to obtain CG76, the dissociation agent for leaching the target antimony.

[0025] Example 3

[0026] Weigh out 45 parts of sodium sulfide, 25 parts of sodium hydroxide, 6 parts of sodium carbonate, 2 parts of sodium polysulfide precursor, 3 parts of sodium sulfite, 2 parts of calcium oxide, and 1.5 parts of sodium hexametaphosphate. Place them in a sealed alkali-resistant mixer and stir at 50°C for 30 min. Then, slowly spray deionized water to make the water content of the system 15%, and continue stirring for 50 min to obtain a semi-dry precursor. Activate the semi-dry precursor in a sealed environment at 100°C for 1 h, vacuum dry at 100°C for 3 h, cool, pulverize, and pass through a 120-mesh sieve to obtain CG76, the dissociation agent for leaching the target antimony.

[0027] Example 4

[0028] Weigh out 55 parts of sodium sulfide, 35 parts of sodium hydroxide, 12 parts of sodium carbonate, 5 parts of sulfur powder, 6 parts of sodium sulfite, 5 parts of calcium hydroxide, and 1 part of sodium carboxymethyl cellulose. Place them in a sealed alkali-resistant mixer and stir at 35°C for 45 min. Then, slowly spray deionized water to make the water content of the system 13%, and continue stirring for 55 min to obtain a semi-dry precursor. Activate the semi-dry precursor in a sealed environment at 85°C for 2.5 h, vacuum dry at 85°C for 3.5 h, cool, pulverize, and pass through a 120-mesh sieve to obtain CG76, the dissociation agent for leaching the target antimony.

[0029] Example 5

[0030] Weigh out 60 parts of sodium sulfide, 45 parts of sodium hydroxide, 15 parts of sodium carbonate, 8 parts of sulfur powder, 10 parts of sodium sulfite or sodium thiosulfate, 8 parts of magnesium oxide, and 1.2 parts of sodium lignosulfonate. Place them in a sealed alkali-resistant mixer and stir at 45°C for 35 min. Then, slowly spray deionized water to make the water content of the system 11%, and continue stirring for 55 min to obtain a semi-dry precursor. Activate the semi-dry precursor in a sealed environment at 95°C for 1.5 h, vacuum dry at 90°C for 4.3 h, cool, pulverize, and pass through a 120-mesh sieve to obtain CG76, the dissociation agent for leaching the target antimony.

[0031] Example 6

[0032] Weigh out 40 parts of sodium sulfide, 40 parts of sodium hydroxide, 10 parts of sodium carbonate, 6 parts of sulfur powder, 8 parts of sodium sulfite, 4 parts of magnesium oxide, and 0.8 parts of sodium polyacrylate. Place them in a sealed alkali-resistant mixer and stir at 36°C for 44 min. Then, slowly spray deionized water to make the water content of the system 13%, and continue stirring for 65 min to obtain a semi-dry precursor. Activate the semi-dry precursor in a sealed environment at 90°C for 2.5 h, vacuum dry at 88°C for 3.6 h, cool, pulverize, and pass through a 120-mesh sieve to obtain CG76, the dissociation agent for leaching antimony.

[0033] Example 7

[0034] 48 parts of sodium sulfide, 22 parts of sodium hydroxide, 9 parts of sodium carbonate, 3 parts of sodium polysulfide precursor, 8 parts of sodium thiosulfate, 8 parts of magnesium hydroxide, and 1.1 parts of sodium hexametaphosphate were weighed and placed in a sealed alkali-resistant mixer. The mixture was stirred at 42°C for 44 min. Deionized water was then slowly sprayed in to bring the system's water content to 13%, and stirring continued for 63 min to obtain a semi-dry precursor. The semi-dry precursor was activated in a sealed environment at 88°C for 1.3 h, then vacuum dried at 90°C for 4.3 h. After cooling, pulverizing, and passing through a 120-mesh sieve, the dissociation agent CG76 for leaching antimony was obtained.

[0035] Example 8

[0036] Weigh out 58 parts of sodium sulfide, 22 parts of sodium hydroxide, 7 parts of sodium carbonate, 8 parts of sulfur powder, 10 parts of sodium sulfite, 4 parts of calcium hydroxide, and 0.9 parts of sodium polyacrylate. Place them in a sealed alkali-resistant mixer and stir at 44°C for 38 min. Then, slowly spray deionized water to make the water content of the system 13%, and continue stirring for 66 min to obtain a semi-dry precursor. Activate the semi-dry precursor in a sealed environment at 95°C for 2.5 h, vacuum dry at 85°C for 3.8 h, cool, pulverize, and pass through a 120-mesh sieve to obtain CG76, the dissociation agent for leaching the target antimony.

[0037] Example 9

[0038] The leaching of antimony prepared in Example 3 was tested using the dissociation agent CG76, and the specific operation was as follows: 100g of antimony-containing material of the stibnite type was added, along with 10g of CG76. The liquid-to-solid ratio was controlled at 6mL / g, and the reaction was carried out at 90℃ and 400r / min for 3h. After the reaction, the mixture was filtered to obtain an antimony-containing alkaline sulfide leaching solution and leaching residue. The antimony leaching rate was 90.58%.

[0039] Example 10

[0040] The antimony leaching dissociation agent CG76 prepared in Examples 1, 2, 4, 5, 6, 7, and 8 were tested respectively, using the same method as in Example 9. The results all showed that the bismuth leaching rate reached more than 85% after adding the antimony leaching dissociation agent CG76 described in this invention.

[0041]

[0042] Comparative Example 1 NaOH leaching NaOH was used as the leaching agent to treat antimony-containing sulfide materials. This method has a certain leaching effect on oxidized antimony such as Sb₂O₃, but its complexing ability on antimony sulfide minerals such as Sb₂S₃ is insufficient, resulting in a low antimony leaching rate and a long reaction time.

[0043] Comparative Example 2 Single Na2S leaching Antimony-containing materials were treated using Na₂S as a single leaching agent. This method can induce some antimony to form antimony thio compounds that enter the solution, but the system alkalinity is insufficient, the sulfiding agent is easily oxidized by air, the leachate has poor stability, and the utilization rate of the sulfiding agent is low.

[0044] Comparative Example 3 A simple leaching process using NaOH and Na2S Leaching was performed using a simple mixed solution of NaOH and Na2S. Although this system can provide both alkalinity and sulfides, the components are not composite activated, resulting in limited stability of the sulfide state and dispersion at the solid-liquid interface. This can easily lead to problems such as uneven local reactions, particle surface passivation, and fluctuations in leaching efficiency.

[0045] Comparative Example 4 Leaching in acidic chlorination system Antimony-containing materials are leached using hydrochloric acid or chloride salt systems. This method has a strong dissolving ability for some antimony phases, but it is highly corrosive to equipment, consumes a lot of acid, and easily co-leaches impurities such as Fe, Cu, Pb, and As, making subsequent purification and separation difficult.

[0046] Compared with the above methods, the CG76 of the present invention can simultaneously achieve alkaline hydrolysis activation and sulfur complexation leaching of antimony in an alkaline sulfidation system, and reduce the loss of sulfiding agent and co-leaching of impurities through stabilizing components and impurity suppressing components. It has the characteristics of simple process, good selectivity, high stability of leaching solution and strong adaptability to subsequent recovery.

Claims

1. A dissociation agent CG76 for leaching antimony, characterized in that, The antimony leaching dissociation agent CG76 is prepared from raw materials such as sodium sulfide, sodium hydroxide, sodium carbonate, sulfur powder or sodium polysulfide precursor, sodium sulfite or sodium thiosulfate, magnesium oxide, magnesium hydroxide, calcium oxide or calcium hydroxide.

2. The antimony leaching dissociation agent CG76 according to claim 1, characterized in that, The antimony leaching dissociation agent CG76 is prepared from the following raw materials: 35-60 parts by weight of sodium sulfide, 20-45 parts by weight of sodium hydroxide, 5-15 parts by weight of sodium carbonate, 1-8 parts by weight of sulfur powder or sodium polysulfide precursor, 2-10 parts by weight of sodium sulfite or sodium thiosulfate, and 1-8 parts by weight of magnesium oxide, magnesium hydroxide, calcium oxide or calcium hydroxide.

3. The antimony leaching dissociation agent CG76 according to claim 1 or 2, characterized in that, The antimony leaching dissociation agent CG76 is prepared from raw materials comprising 45-55 parts by weight of sodium sulfide, 25-35 parts by weight of sodium hydroxide, 6-12 parts by weight of sodium carbonate, 2-5 parts by weight of sulfur powder or sodium polysulfide precursor, 3-6 parts by weight of sodium sulfite or sodium thiosulfate, and 2-5 parts by weight of magnesium oxide, magnesium hydroxide, calcium oxide or calcium hydroxide.

4. A method for preparing the antimony leaching dissociation agent CG76 according to any one of claims 1 to 3, characterized in that, This includes precursor preparation and post-processing steps, specifically: A. Precursor preparation: Sodium sulfide, sodium hydroxide, sodium carbonate, sulfur powder or sodium polysulfide precursor, sodium sulfite or sodium thiosulfate, magnesium oxide, magnesium hydroxide, calcium oxide or calcium hydroxide are placed in a closed alkali-resistant mixer according to the formula ratio. After adding the dispersing components, stir and spray deionized water to make the water content of the system 10~15%. Continue stirring for 50~70 minutes to obtain semi-dry precursor a. B. Post-processing: 1) Place the semi-dry precursor a in a sealed environment at 80~100℃ for 1~3h to obtain material b; 2) Material b is vacuum dried, cooled, crushed and sieved to obtain the leaching dissociation agent CG76 for antimony.

5. The preparation method according to claim 4, characterized in that, The dispersing component mentioned in step A is one or more of sodium polyacrylate, sodium lignosulfonate, sodium hexametasulfate, and sodium carboxymethyl cellulose.

6. The preparation method according to claim 4, characterized in that, In step A, after adding the dispersing component, the stirring is carried out at a temperature of 40~50℃ for 30~50 minutes.

7. The preparation method according to claim 4, characterized in that, The vacuum drying temperature described in step 2) is 80~100℃, and the time is 3~5h.

8. The application of CG76, a dissociation agent for leaching antimony according to any one of claims 1 to 3, characterized in that, The application of the antimony leaching dissociation agent CG76 in the antimony leaching process of antimony-containing materials.

9. The application according to claim 8, characterized in that, The antimony impregnation of the antimony-containing material includes a main reaction and a post-treatment step, specifically including: A. Main reaction: Add antimony leaching dissociation agent CG76 to the antimony-containing material to be treated, control the liquid-solid ratio at 5~7mL / g, and react for 2~4h at a temperature of 80~100℃ and a stirring speed of 300~500r / min. B. Post-treatment: After the reaction is completed, the solution and leaching residue containing antimony are obtained by filtration.

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