A method for separating and recovering antimony and bismuth from copper, arsenic, antimony, and bismuth-containing materials

Abstract

This invention discloses a method for separating and recovering antimony and bismuth from copper-, arsenic-, antimony-, and bismuth-containing materials. The method involves adding sulfuric acid during the processing of the copper-, arsenic-, antimony-, and bismuth-containing materials, allowing copper to enter the liquid and enriching antimony and bismuth elements into the slag. Liquid alkali is then added to the slag, allowing arsenic to enter the liquid and further enriching antimony and bismuth elements into the slag. Liquid alkali and sodium hydrosulfide are then added to the slag, allowing antimony to enter the liquid for recovery, while bismuth remains in the slag, achieving antimony-bismuth separation. The slag composition meets the requirements for bismuth concentrate. A composite silicate is added to the sulfidation liquid to remove impurities such as bismuth, copper, and lead into the slag. The liquid then enters a pressurized reactor, where a catalyst is added and forced-air oxidation is applied, oxidizing antimony and allowing it to enter the slag. After drying, sodium antimonate is obtained. This is the first time a process has been achieved that does not use a chloride salt system to separately produce bismuth concentrate and sodium antimonate. This process shortens the wet separation and recovery process of antimony and bismuth, eliminates the high-chlorine wastewater generated by the chloride salt system, is environmentally friendly, and achieves antimony and bismuth recovery rates of over 98%.

Description

Technical Field

[0001] This invention belongs to the field of non-ferrous metal metallurgy technology, and specifically discloses a method for separating and recovering antimony and bismuth from copper, arsenic, antimony and bismuth-containing materials. Background Technology

[0002] Bismuth is a widely used "green metal" found in metallurgical additives, low-melting-point alloys, chemicals, optoelectronic materials, pharmaceuticals, and defense. Antimony is a gray metal with a silvery luster, primarily used in the production of flame retardants, alloy materials for batteries, sliding bearings, and welding fluxes.

[0003] In copper and lead smelting processes, antimony and bismuth often accumulate alongside elements such as copper, arsenic, tellurium, and lead in byproducts like anode slime. During the precious metal recovery process, anode slime produces materials containing multiple elements such as copper, arsenic, antimony, bismuth, tellurium, or lead for impurity removal, resulting in highly complex chemical compositions and elemental valence states. Because these materials contain valuable elements like copper, bismuth, antimony, and tellurium, wet processing involves separation and extraction based on the different reactions of the material components with acids or alkalis. Generally, copper is removed using sulfuric acid leaching, and arsenic is removed using sodium hydroxide alkali leaching. The removal efficiency for copper and arsenic is excellent, generally exceeding 90%. Antimony and bismuth remain in the slag phase as raw materials for antimony and bismuth recovery.

[0004] Because bismuth reacts with hydrochloric acid to form easily soluble chlorobismuthic acid, most patents employ chloride salt systems for the separation and extraction of bismuth. Examples include patents CN202010024819.7 ("A Comprehensive Recovery Method for Prioritizing Copper Extraction from Copper-Containing Bismuth Materials via Hydrometallurgical Process"), CN201810034185.6 ("A Method for Producing High-Purity Bismuth Oxide from Bismuth-Containing Materials"), CN201811140061.2 ("A Method for Comprehensive Recovery and Reuse of Bismuth-Tellulose Materials"), and CN200710034666.9 ("A Process for Comprehensive Extraction of Valuable Metals from Bismuth-Containing Polymetallic Materials"). These patents all employ a chloride salt leaching method, allowing bismuth to enter the liquid phase. Bismuth oxide is produced through multiple processes, including leaching, neutralization, precipitation, and alkali conversion. This process is lengthy and generates large amounts of high-chlorine wastewater, which is difficult to treat. Summary of the Invention

[0005] This invention discloses a method for separating and recovering antimony and bismuth from copper, arsenic, antimony, and bismuth-containing materials, in order to solve any of the above-mentioned and other potential problems of the prior art.

[0006] To solve the above-mentioned technical problems, the technical solution of the present invention is: a method for separating and recovering antimony and bismuth from copper-, arsenic-, antimony-, and bismuth-containing materials. In this method, sulfuric acid is added during the processing of the copper-, arsenic-, antimony-, and bismuth-containing materials, allowing copper to enter the liquid and enriching antimony and bismuth elements into the slag. Liquid alkali is added to the slag, allowing arsenic to enter the liquid, further enriching antimony and bismuth elements into the slag. Liquid alkali and sodium hydrosulfide are then added to the slag, allowing antimony to enter the liquid and be recovered, while bismuth remains in the slag, thus achieving antimony-bismuth separation. The slag composition meets the requirements for bismuth concentrate. Composite silicates are added to the sulfidation liquid, allowing impurities such as bismuth, copper, and lead to enter the slag and be removed. The liquid then enters a pressurized reactor, where a catalyst is added and the mixture is oxidized by forced air, causing antimony to oxidize and enter the slag. After drying the slag, sodium antimonate is obtained.

[0007] Furthermore, the method specifically includes the following steps:

[0008] S1) Add a certain amount of sulfuric acid to the copper, arsenic, antimony and bismuth-containing material, heat to a certain temperature, react for a certain time, and then filter to obtain the first filtrate and the first filter residue.

[0009] S2) The first filter residue obtained in S1) is mixed with the alkaline solution in a certain proportion, heated to a certain temperature, reacted for a certain time, and then filtered to obtain the second filtrate and the second filter residue.

[0010] S3) The second filter residue obtained in S2) is mixed with the alkaline solution in a certain proportion, and a certain amount of sodium hydrosulfide is added. The mixture is heated to a certain temperature and reacted for a certain time. After filtration, the third filtrate and the third filter residue are obtained.

[0011] S4) Add a certain amount of composite silicate to the third filtrate obtained in S3), heat to a certain temperature, react for a certain time, and then filter to obtain the fourth filtrate and the fourth filter residue.

[0012] S5) Pump the fourth filtrate obtained in S4) into a pressurized reactor, add a certain amount of potassium permanganate and catechol, control the pressure and blow in compressed air, heat to a certain temperature, react for a certain time, and then filter to obtain the fifth filtrate and the fifth filter residue.

[0013] S6) The fifth filter residue obtained in S5) is dried in a dryer to obtain sodium antimonate.

[0014] Furthermore, in the copper-arsenic-antimony-bismuth-containing material in S1), copper, arsenic, antimony, and bismuth elements exist in the form of oxides or salts, with the following contents: 8.5–21.3 wt% Cu; 5.3–11.8 wt% As; 6.8–18.5 wt% Bi; and 9.3–22.1 wt% Sb.

[0015] Furthermore, the process parameters in S1) are: controlling the reaction acidity to 10-80 g / L, the liquid-solid ratio to 3-6:1, the temperature to 70-95℃, and the reaction time to 1-3 hours.

[0016] Furthermore, the process parameters in S2) are: controlling the reaction alkalinity to 10-60 g / L, the liquid-to-solid ratio to 3-6:1, the temperature to 70-95°C, and the reaction time to 1-3 hours.

[0017] Furthermore, the process parameters in S3) are as follows: control the reaction alkalinity to 40-100 g / L, add sodium hydrosulfide at 1-1.2 times the amount of antimony, liquid-solid ratio to 3-6:1, control the temperature to 80-110℃, and react for 1-4 hours.

[0018] Furthermore, the process parameters in S4) are:

[0019] The amount of the composite silicate added is 2.5–10 kg / m³. 3 The temperature is controlled at 70–95℃, and the reaction time is 1–3 hours.

[0020] Furthermore, the composite silicate is one of tricalcium silicate (C3S), dicalcium silicate (C2S), or tricalcium aluminate (C3A).

[0021] Furthermore, the process parameters in S5) are as follows:

[0022] The amount of potassium permanganate added is 0.1–0.2 kg / m³. 3 The amount of catechol added is 0.5–1 kg / m³. 3 The pressure is controlled at 0.9–1.2 MPa, the temperature at 80–140 °C, and the reaction time at 8–11 hours.

[0023] Furthermore, after processing by the method, the recovery rates of antimony and bismuth in the raw materials are both above 98%.

[0024] Beneficial technical effects of the present invention:

[0025] (1) For the first time, antimony and bismuth can be separated without using a chloride salt system, eliminating the generation of high-chlorine wastewater and making it environmentally friendly;

[0026] (2) Achieve separation and recovery of antimony and bismuth using a short-process, all-wet method;

[0027] (3) Bismuth concentrate and sodium antimonate were produced, with antimony and bismuth recovery rates both above 98%. Attached Figure Description

[0028] Figure 1 This invention provides a process flow for separating and recovering antimony and bismuth from copper, arsenic, antimony, and bismuth-containing materials. Detailed Implementation

[0029] The content of the present invention will be further described below with reference to the accompanying drawings and examples.

[0030] like Figure 1 As shown, the present invention discloses a method for separating and recovering antimony and bismuth from copper, arsenic, antimony, and bismuth-containing materials. The technical solution mainly includes the following steps:

[0031] Step 1

[0032] In copper, arsenic, antimony and bismuth materials, the elements mainly exist in the form of oxides or salts. During the treatment process, sulfuric acid is added, the reaction acidity is controlled at 10-80 g / L, the liquid-solid ratio is controlled at 3-6:1, the temperature is controlled at 70-95℃, and the reaction is carried out for 1-3 hours, so that copper enters the liquid phase in the form of CuSO4 and is removed by filtration, resulting in the first filter residue and the first filtrate.

[0033] Step 2

[0034] Add liquid alkali to the first filter residue obtained in step 1, control the reaction alkalinity to 10-60 g / L, the liquid-solid ratio to 3-6:1, control the temperature to 70-95℃, and react for 1-3 hours to allow arsenic to enter the liquid phase in the form of Na3AsO4 and be removed by filtration, thus obtaining the second filter residue and the second filtrate.

[0035] Step 3

[0036] Add liquid alkali to the second filter residue obtained in step 2, control the reaction alkalinity to 40-100 g / L, add sodium hydrosulfide at 1-1.2 times the amount of antimony, maintain a liquid-to-solid ratio of 4-6:1, control the temperature to 80-110℃, and react for 1-4 hours. This allows antimony to enter the liquid phase as Na3SbS3, while bismuth remains in the residue phase as Bi2S3. Filter to obtain the third filter residue and the third filtrate. The chemical composition of the third residue meets the industry standard YS / T 321-2005 for bismuth concentrate, and the bismuth recovery rate is over 98%.

[0037] Step 4

[0038] Add 2.5–10 kg / m³ of water to the third filtrate obtained in step 3. 3 The composite silicate is reacted at a temperature of 70-95℃ for 1-3 hours to adsorb and precipitate copper, bismuth, lead impurities and suspended matter in the liquid, and then filtered to obtain the fourth filter residue and the fourth filtrate.

[0039] Step 5

[0040] The fourth filtrate obtained in step 4 is pumped into a pressurized reactor, and 0.1–0.2 kg / m³ of [unspecified substance] is added. 3 Potassium permanganate, 0.5–1 kg / m³ 3 The catechol was oxidized to NaSb(OH)6 precipitate by blowing compressed air at a pressure of 0.9-1.2 MPa and a temperature of 80-140℃ for 8-11 hours. The fifth filter residue was obtained by filtration.

[0041] Step 6

[0042] The fifth residue obtained in step 5 is dried in a dryer at a controlled temperature of 100-140℃ to evaporate the moisture, thus obtaining sodium antimonate, which meets the industry standard YS / T 22-2010 for sodium antimonate, with an antimony recovery rate of over 98%.

[0043] Example 1:

[0044] In copper, arsenic, antimony, and bismuth-containing materials, the elements mainly exist in the form of oxides or salts, and the content of their main components is shown in Table 1.

[0045] Table 1. Composition and content of copper, arsenic, antimony, and bismuth-containing materials

[0046]

[0047] After slurrying with a liquid-to-solid ratio of 4:1, sulfuric acid was added to control the reaction acidity at 10 g / L, and the reaction was carried out at 80°C for 1 hour. The residue (a) was then filtered to obtain slag (a). Slag (a) was then slurryed with a liquid-to-solid ratio of 4:1, and liquid alkali was added to control the reaction alkalinity at 30 g / L. The reaction was carried out at 80°C for 1 hour, and the residue (b) was then filtered to obtain slag (c). Slag (b) was then slurryed with a liquid-to-solid ratio of 4:1, and liquid alkali was added to control the reaction alkalinity at 40 g / L. Sodium hydrosulfide was added at an amount equal to the amount of antimony, and the reaction was carried out at 80°C for 1 hour to obtain slag (c) and liquid (c). The composition of slag (c) is shown in Table 2. The chemical composition conforms to the bismuth concentrate industry standard YS / T 321-2005, and the bismuth recovery rate is 98.97%.

[0048] Table 2. Composition of produced slag (c)

[0049]

[0050] Add liquid (c) at 2.5 kg / m 3 The composite silicate was reacted at 70℃ for 1 hour to obtain liquid (d); liquid (d) was then pumped into a pressurized reactor and 0.1 kg / m³ of water was added. 3 Potassium permanganate, 0.5 kg / m³ 3 The catechol was subjected to compressed air at a controlled pressure of 0.9 MPa and a temperature of 80°C for 11 hours to obtain residue (e). The residue (e) was dried in a dryer at a controlled temperature of 105°C until the moisture content was reduced to below 0.3%. Its composition is shown in Table 3 and meets the industry standard of sodium antimonate YS / T22-2010. The antimony recovery rate is 99.21%.

[0051] Table 3. Sodium antimonate composition and content.

[0052]

[0053] Example 2

[0054] In copper, arsenic, antimony, and bismuth-containing materials, the elements mainly exist in the form of oxides or salts, and the content of their main components is shown in Table 4.

[0055] Table 4. Composition and content of copper, arsenic, antimony, and bismuth-containing materials

[0056]

[0057] After slurrying with a liquid-to-solid ratio of 5:1, sulfuric acid was added to control the reaction acidity at 40 g / L, and the reaction was carried out at 80℃ for 2 hours. The residue (a) was then filtered to obtain slag (a). After slag (a) was slurryed with a liquid-to-solid ratio of 5:1, liquid alkali was added to control the reaction alkalinity at 40 g / L, and the reaction was carried out at 80℃ for 2 hours. The residue (b) was then filtered to obtain slag (c). After slag (b) was slurryed with a liquid-to-solid ratio of 5:1, liquid alkali was added to control the reaction alkalinity at 50 g / L, and sodium hydrosulfide was added at 1.1 times the amount of antimony. The reaction was carried out at 85℃ for 2 hours to obtain slag (c) and liquid (c). The composition of slag (c) is shown in Table 5. The chemical composition conforms to the bismuth concentrate industry standard YS / T 321-2005, and the bismuth recovery rate is 99.06%.

[0058] Table 5. Composition of the produced slag (c)

[0059]

[0060] Add liquid (c) at 5 kg / m 3 The composite silicate was reacted at 80℃ for 2 hours to obtain liquid (d); liquid (d) was then pumped into a pressurized reactor and 0.15 kg / m³ of water was added. 3 Potassium permanganate, 0.75 kg / m³ 3 The catechol was subjected to compressed air at a controlled pressure of 1.0 MPa and a temperature of 110°C for 9 hours to obtain residue (e). The residue (e) was dried in a dryer at a controlled temperature of 120°C until the moisture content was reduced to below 0.3%. Its composition is shown in Table 6 and meets the industry standard of sodium antimonate YS / T22-2010. The antimony recovery rate is 98.91%.

[0061] Table 6. Sodium Antimonate Composition Content Table

[0062]

[0063] Example 3

[0064] In copper, arsenic, antimony and bismuth-containing materials, the elements mainly exist in the form of oxides or salts, and the content of their main components is shown in Table 7.

[0065] Table 7. Composition and Content of Materials Containing Copper, Arsenic, Antimony, and Bismuth

[0066]

[0067] After slurrying with a liquid-to-solid ratio of 6:1, sulfuric acid was added to control the reaction acidity at 80 g / L, and the reaction was carried out at 95°C for 3 hours. The residue (a) was then filtered to obtain slag (a). Slag (a) was then slurryed with a liquid-to-solid ratio of 6:1, and liquid alkali was added to control the reaction alkalinity at 60 g / L. The reaction was carried out at 95°C for 3 hours, and the residue (b) was then filtered to obtain slag (b). Slag (b) was then slurryed with a liquid-to-solid ratio of 6:1, and liquid alkali was added to control the reaction alkalinity at 60 g / L. Sodium hydrosulfide was added at 1.2 times the amount of antimony, and the reaction was carried out at 95°C for 4 hours to obtain slag (c) and liquid (c). The composition of slag (c) after drying is shown in Table 8. The chemical composition conforms to the bismuth concentrate industry standard YS / T 321-2005, and the bismuth recovery rate is 99.23%.

[0068] Table 8. Composition of the produced slag (c)

[0069]

[0070] Add liquid (c) at 10 kg / m 3 The composite silicate was reacted at 95℃ for 3 hours to obtain liquid (d); liquid (d) was then pumped into a pressurized reactor and 0.2 kg / m³ of water was added. 3 Potassium permanganate, 1.0 kg / m³ 3 The catechol was subjected to compressed air at a controlled pressure of 1.2 MPa and a temperature of 140°C for 8 hours to obtain residue (e). The residue (e) was dried in a dryer at a controlled temperature of 140°C until the moisture content was reduced to below 0.3%. Its composition is shown in Table 9 and meets the industry standard of sodium antimonate YS / T22-2010. The antimony recovery rate is 99.31%.

[0071] Table 9. Composition and content of sodium antimonate produced.

[0072]

[0073] The foregoing has provided a detailed description of a method for separating and recovering antimony and bismuth from copper-, arsenic-, antimony-, and bismuth-containing materials, as provided in the embodiments of this application. The descriptions of the embodiments above are merely for the purpose of helping to understand the method and its core ideas; furthermore, those skilled in the art will recognize that, based on the ideas of this application, there will be changes in the specific implementation methods and application scope. Therefore, the content of this specification should not be construed as a limitation of this application.

[0074] Certain terms are used in the specification and claims to refer to specific components. Those skilled in the art will understand that hardware manufacturers may use different names to refer to the same component. This specification and claims do not distinguish components based on differences in name, but rather on differences in function. The terms "comprising" and "including" used throughout the specification and claims are open-ended and should be interpreted as "comprising / including but not limited to". "Approximately" means that within an acceptable margin of error, those skilled in the art can solve the technical problem and substantially achieve the technical effect within a certain margin of error. The following descriptions in the specification are preferred embodiments for carrying out this application; however, these descriptions are for the purpose of illustrating the general principles of this application and are not intended to limit the scope of this application. The scope of protection of this application shall be determined by the appended claims.

[0075] It should also be noted that the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a product or system comprising a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a product or system. Without further limitation, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the product or system that includes said element.

[0076] It should be understood that the term "and / or" used in this article is merely a description of the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, and B existing alone. Additionally, the character " / " in this article generally indicates that the preceding and following related objects have an "or" relationship.

[0077] The foregoing description illustrates and describes several preferred embodiments of this application. However, as previously stated, it should be understood that this application is not limited to the forms disclosed herein and should not be construed as excluding other embodiments. It can be used in various other combinations, modifications, and environments, and can be altered within the scope of the application concept described herein through the foregoing teachings or techniques or knowledge in related fields. Any modifications and variations made by those skilled in the art that do not depart from the spirit and scope of this application should be within the protection scope of the appended claims.

Claims

1. A method for separating and recovering antimony and bismuth from copper-, arsenic-, antimony-, and bismuth-containing materials, characterized in that, The method involves adding sulfuric acid during the processing of copper, arsenic, antimony, and bismuth-containing materials, allowing copper to enter the liquid and enriching antimony and bismuth elements into the slag. Liquid alkali is then added to the slag, allowing arsenic to enter the liquid and further enriching antimony and bismuth elements into the slag. Liquid alkali and sodium hydrosulfide are then added to the slag, allowing antimony to enter the liquid for recovery, while bismuth remains in the slag, thus achieving antimony-bismuth separation. The slag composition meets the requirements for bismuth concentrate. Composite silicates are added to the sulfidation liquid, allowing bismuth, copper, lead, and impurities to enter the slag and be removed. The liquid then enters a pressurized reactor, where a catalyst is added for forced-air oxidation, oxidizing antimony and allowing it to enter the slag. After drying the slag, sodium antimonate is obtained.

2. The method according to claim 1, characterized in that, The method specifically includes the following steps: S1) Add a certain amount of sulfuric acid to the copper, arsenic, antimony and bismuth-containing material, heat to a certain temperature, react for a certain time, and then filter to obtain the first filtrate and the first filter residue. S2) The first filter residue obtained in S1) is mixed with the alkaline solution in a certain proportion, heated to a certain temperature, reacted for a certain time, and then filtered to obtain the second filtrate and the second filter residue. S3) The second filter residue obtained in S2) is mixed with the alkaline solution in a certain proportion, and a certain amount of sodium hydrosulfide is added. The mixture is heated to a certain temperature and reacted for a certain time. After filtration, the third filtrate and the third filter residue are obtained. S4) Add a certain amount of composite silicate to the third filtrate obtained in S3), heat to a certain temperature, react for a certain time, and then filter to obtain the fourth filtrate and the fourth filter residue. S5) Pump the fourth filtrate obtained in S4) into a pressurized reactor, add a certain amount of potassium permanganate and catechol, control the pressure and blow in compressed air, heat to a certain temperature, react for a certain time, and then filter to obtain the fifth filtrate and the fifth filter residue. S6) The fifth filter residue obtained in S5) is dried to obtain sodium antimonate.

3. The method according to claim 2, characterized in that, In the copper-arsenic-antimony-bismuth-containing material in S1), copper, arsenic, antimony, and bismuth elements exist in the form of oxides or salts, with the following contents: 8.5~21.3wt% Cu; 5.3~11.8wt% As; 6.8~18.5wt% Bi; and 9.3~22.1wt% Sb.

4. The method according to claim 2, characterized in that, The process parameters in S1) are: controlling the reaction acidity to 10~80g / L, the liquid-solid ratio to 3~6:1, the temperature to 70~95℃, and the reaction time to 1~3 hours.

5. The method according to claim 2, characterized in that, The process parameters in S2) are: control the reaction alkalinity to 10~60g / L, the liquid-solid ratio to 3~6:1, the temperature to 70~95℃, and the reaction time to 1~3 hours.

6. The method according to claim 2, characterized in that, The process parameters in S3) are as follows: control the reaction alkalinity to 40~100g / L, add sodium hydrosulfide at 1~1.2 times the amount of antimony, liquid-solid ratio to 3~6:1, temperature to 80~110℃, and reaction time to 1~4 hours.

7. The method according to claim 2, characterized in that, The process parameters in S4) are: The amount of the composite silicate added is 2.5–10 kg / m³. 3 The temperature is 70~95℃ and the reaction time is 1~3 hours.

8. The method according to claim 2, characterized in that, The process parameters in S5 are: The amount of potassium permanganate added is 0.1~0.2 kg / m³. 3 The amount of catechol added is 0.5~1 kg / m³. 3 The pressure is controlled at 0.9~1.2 MPa, the temperature at 80~140℃, and the reaction time at 8~11 hours.

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