Method for removing impurity cobalt in carbonylation alloy enriched noble metal material

Abstract

The invention discloses a method for removing impurity cobalt in a carbonylation alloy enriched noble metal material, which comprises the following steps: S1, mixing a novel extraction agent P507 and sulfonated kerosene, in a mixed solution, 20% of the P507 and 80% of the sulfonated kerosene, starting stirring, and uniformly mixing; s2, mixing feed liquid obtained after the carbonylation alloy enriched concentrate is subjected to distillation, chlorination dissolution filtration and gold extraction in the purification process with P507 to obtain an organic phase, carrying out primary cobalt extraction, and then, carrying out static phase separation to obtain an organic phase and a water phase; s3, organic phases obtained through primary cobalt extraction and secondary cobalt extraction are subjected to reverse extraction, specifically, a HCl solution of 2N is added into the organic phases, the reverse extraction phase ratio is O: A = 4: 1, reverse extraction and static phase separation are conducted, and a reverse extraction water phase serves as a raw material of a cobalt product to recycle cobalt; and S4, a water phase obtained through primary cobalt extraction and secondary cobalt extraction is subjected to platinum-palladium separation, platinum refining and palladium refining, and palladium and platinum powder products are produced.

Description

Technical Field

[0001] The present invention relates to the technical field of a process for purifying platinum, palladium and gold noble metals from a carbonyl alloy-enriched platinum concentrate, and in particular to a method for removing impurity cobalt from a carbonyl alloy-enriched noble metal material. Background Art

[0002] At present, the raw materials for precious metal refining are mainly carbonyl alloys. Compared with secondary alloys, the raw material composition of the two has changed greatly. The contents of platinum, palladium and gold in the output concentrate have slightly decreased, but the content of cobalt has increased significantly, from the original 0.86% to 16.38%. In the process of secondary alloy enrichment and purification, the quality of platinum-palladium-gold products is basically not affected due to the low cobalt content. However, the direct recovery rate and high quality rate of platinum, palladium and gold are directly affected due to the high cobalt content in the platinum concentrate enriched by carbonyl alloy. It is very difficult to purify palladium and refine platinum. The cobalt content in the product seriously exceeds the standard, which increases the workload of employees and affects the product quality. The direct recovery rate and high quality rate of platinum, palladium and gold cannot be guaranteed.

[0003] Therefore, a method for removing cobalt impurities from carbonyl alloy-enriched precious metal materials is proposed. Summary of the invention

[0004] In view of the above technical problems, the present invention provides a method for removing the impurity cobalt in the carbonyl alloy-enriched precious metal material.

[0005] In order to achieve the above object, the technical solution of the present invention is as follows: A method for removing cobalt impurities from a carbonyl alloy-enriched precious metal material comprises the following steps: S1. Mix the new extractant P507 and sulfonated kerosene. In the mixed solution, 20% is P507 and 80% is sulfonated coal. Stirring is started and mixed evenly. Then pure water is added in a ratio of 2:1. After stirring and washing, the phases are separated. The aqueous phase is treated as wastewater. 1 mol / L ammonia water is added to the organic phase in a ratio of 20:3. Mix and stir. After saponification, the phases are separated. The aqueous phase is recycled and the organic phase is used to extract cobalt. S2, the feed liquid of carbonyl alloy enriched concentrate after distillation, chlorination dissolution filtration and gold extraction in the purification process is mixed with P507 and the organic phase is subjected to a primary cobalt extraction, and then the phases are separated at rest to obtain an organic phase and an aqueous phase, wherein the extraction phase ratio of the primary cobalt extraction is: 0:A=4:1, and the pH value of the extracted aqueous phase is 4.2-5, and then the aqueous phase is subjected to a secondary cobalt extraction, and then the phases are separated at rest to obtain an organic phase and an aqueous phase, wherein the extraction phase ratio of the secondary cobalt extraction is: 0:A=4:1, and the pH value of the extracted aqueous phase is 4.2-5; S3, respectively, stripping the organic phases obtained from the primary cobalt extraction and the secondary cobalt extraction, specifically, adding 2N HCl solution to the organic phase, the stripping phase ratio: O:A=4:1, stripping, static phase separation, stripping water phase as the raw material of the cobalt product to recover cobalt, stripping oil phase enters the next cycle of washing, saponification, and cobalt extraction in step S1; S4. The aqueous phase obtained after the first and second cobalt extractions is subjected to platinum-palladium separation, platinum refining, and palladium refining to produce 99.99% palladium and platinum powder products.

[0006] Wherein, in step S1, the novel extractant P507 and sulfonated kerosene are uniformly mixed for 2 minutes.

[0007] Wherein, in the step S1, pure water is added for stirring and washing, and the washing times are twice, and each stirring and washing time is 5 minutes.

[0008] Wherein, in the step S1, the organic phase is added with ammonia water and mixed and stirred for 10 minutes, and then left to stand for 2 minutes for phase separation.

[0009] Wherein, in the step S2, the extraction time of cobalt is 10 minutes, and the phases are separated after standing for 2 minutes.

[0010] Wherein, in step S2, the extraction time of the secondary cobalt extraction is 5 minutes, and the static phase separation time is 2 minutes.

[0011] Wherein, in step S2, the temperature of the first cobalt extraction and the second cobalt extraction are both 20-28°C.

[0012] Wherein, in step S3, the stripping time is 10 minutes and the static phase separation time is 2 minutes.

[0013] The beneficial effects of the present invention are: 1. The present invention mainly utilizes the property of P507 to extract cobalt, and examines the sequence of palladium and gold extraction and various technical parameters, and produces platinum, palladium and gold products that meet various technical indicators.

[0014] 2. The invention mainly includes three parts: ① Use a new extractant P 507 and sulfonated kerosene to mix in a certain proportion, start stirring, mix evenly, then add a hydrochloric acid solution prepared with a certain proportion of pure water, stir and wash, separate the phases, the water phase is treated as wastewater, the organic phase is saponified with ammonia water and then separated, the water phase can be recycled, and the organic phase is used to extract cobalt. ② The liquid of the carbonyl alloy enriched concentrate after distillation, chlorination, dissolution, filtration, and gold extraction in the purification process is added with P 507 mixed with the organic phase in a certain proportion to extract cobalt, and the cobalt is extracted twice. ③ The organic phase after P507 extraction is added with a hydrochloric acid solution of a certain concentration and proportion for stripping, static phase separation, stripping water phase as the raw material of cobalt products to recover cobalt, stripping oil phase enters the next cycle of washing, saponification, and cobalt extraction, the water phase after P507 cobalt extraction is separated by platinum and palladium, platinum refining, and palladium refining to produce 99.99% palladium and platinum powder products.

[0015] 3. The main purpose and reaction of each operation of the present invention are: (1) Saponification: The organic phase after stripping can only be capable of extracting cobalt after being regenerated with alkali. The saponification rate is generally controlled at 70% to 75%. If the saponification rate is too high (over 80%), the organic phase will have high viscosity, making it difficult to separate the organic phase from the aqueous phase during the extraction process. The organic phase will mechanically carry a lot of liquid, and the saponification rate will be low, resulting in a low ability of the organic phase to extract cobalt. (2) Washing: Wash the small amount of nickel extracted into the organic phase into the aqueous phase; and let the liquid entrained in the organic phase settle; (3) Extraction: By controlling the pH value of the solution, the Co2+ in the mixed solution is extracted into the organic phase, 2NH4R+Co²+=CoR.+2NH4+; (4) Stripping: The cobalt in the loaded organic phase is stripped into the aqueous phase in a hydrochloric acid solution to achieve the purpose of purifying cobalt, CoR+2HCl=2HR+CoCl. In addition, this process requires that the pH value of the cobalt chloride solution after stripping is ≥3.5, which meets the pH value requirement of the cobalt chloride solution for oxalic acid precipitation of cobalt.

[0016] 4. The whole cobalt extraction process of the present invention is simple to operate, and the order of impurity removal is reasonably arranged. The cobalt in the feed liquid of the platinum concentrate enriched in carbonyl alloy after gold extraction can be completely removed by P507, without any influence on other precious metal platinum, palladium and gold ions in the feed liquid. In the subsequent platinum and palladium refining operation process, the direct recovery rate is high, the product quality rate is high, there is no rework, and at the same time, the efficiency is high, the cost is low, and the labor intensity is low. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] The present invention is further described below in conjunction with the accompanying drawings and embodiments: Figure 1 It is a process flow chart of the present invention; Figure 2 It is a schematic diagram of the effect of the pH of the feed solution on the cobalt extraction rate in the present invention. DETAILED DESCRIPTION

[0018] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is further described in detail below in conjunction with specific embodiments and with reference to the accompanying drawings. It should be understood that these descriptions are only exemplary and are not intended to limit the scope of the present invention. In addition, in the following description, the description of well-known structures and technologies is omitted to avoid unnecessary confusion of the concept of the present invention.

[0019] According to the data summarized from the previous exploratory experiments, a precious metals plant adopted 2-stage washing, 2-stage saponification, 6-stage countercurrent cobalt extraction, and 4-stage stripping for industrial production.

[0020] Example 1 Gold extraction liquid: Co2+17.64 g / L, Ni2+1.5 g / L, Au 2.46g / L, Pt8.94g / L, Pd4.83g / L, volume 1000L like Figure 1 As shown, ① the new extractant P 507 and the organic phase composition of sulfonated kerosene: 20% P 507 + 80% sulfonated coal, the two are evenly mixed for 2 minutes, 500L of pure water is added for washing at a ratio of 2:1, the washing times are twice, and the stirring and washing time is 5 minutes each time. The organic phase is saponified by adding 150L of 1mol / L ammonia water at a ratio of 20:3, mixed and stirred for 10 minutes, and then left to stand for 2 minutes for phase separation; ② the extraction phase ratio of the feed liquid of the carbonyl alloy enriched concentrate after gold extraction in the purification process and the cobalt extraction of the mixed organic phase of P 507 is: 0:A=4:1, 250L of the prepared organic phase is added, the extraction aqueous phase is adjusted to a pH value of 4.2-5 with hydrochloric acid, the extraction time is 10 minutes, and the phases are separated after standing for 2 minutes, and the secondary cobalt extraction is carried out, the organic phase is 250L, the extraction phase ratio is: 0:A=4:1, the pH value of the extraction aqueous phase is still 4.2-5, the extraction time is 5 minutes, and the phases are separated after standing for 2 minutes, and the temperature is: 20-28℃. ③ The stripping solution is 1000L of 2N HCl solution, the stripping phase ratio is: O:A=4:1, the extraction time is 10min, and the phases are separated after standing for 2min. The final metal content of the cobalt-extracted liquid is detected to be Co2+0.34 g / L, Ni2+1.43 g / L, Au 2.46g / L, Pt8.93g / L, and Pd4.85g / L.

[0021] From the analysis and detection data, it can be seen that after the gold-extracted liquid is subjected to P507 cobalt extraction, 98.07% of the cobalt is removed, and there is no effect on nickel, gold, platinum and palladium. The effect of using P507 to extract cobalt is very good.

[0022] Example 2 Gold extraction liquid: Co2+15.92 g / L, Ni2+1.3 g / L, Au 2.63g / L, Pt8.14g / L, Pd4.24g / L, volume 1000L like Figure 1 As shown, ① the new extractant P 507 and the organic phase composition of sulfonated kerosene: 20% P 507 + 80% sulfonated coal, the two are evenly mixed for 2 minutes, 500L of pure water is added for washing at a ratio of 2:1, the washing times are twice, and the stirring and washing time is 5 minutes each time. The organic phase is saponified by adding 150L of 1mol / L ammonia water at a ratio of 20:3, mixed and stirred for 10 minutes, and then left to stand for 2 minutes for phase separation; ② the extraction phase ratio of the feed liquid of the carbonyl alloy enriched concentrate after gold extraction in the purification process and the cobalt extraction of the mixed organic phase of P 507 is: 0:A=4:1, 250L of the prepared organic phase is added, the extraction aqueous phase is adjusted to a pH value of 4.2-5 with hydrochloric acid, the extraction time is 10 minutes, and the phases are separated after standing for 2 minutes, and the secondary cobalt extraction is carried out, the organic phase is 250L, the extraction phase ratio is: 0:A=4:1, the pH value of the extraction aqueous phase is still 4.2-5, the extraction time is 5 minutes, and the phases are separated after standing for 2 minutes, and the temperature is: 20-28℃. ③ The stripping solution is 1000L of 2N HCl solution, the stripping phase ratio is: O:A=4:1, the extraction time is 10min, and the phases are separated after standing for 2min. The final metal content of the cobalt-extracted liquid is detected to be Co2+0.13 g / L, Ni2+1.43 g / L, Au 2.62g / L, Pt8.14g / L, and Pd4.23g / L.

[0023] From the analysis and test data, it can be seen that after the gold-extracted liquid is subjected to P507 cobalt extraction, 99.18% of the cobalt is removed, and there is no effect on nickel, gold, platinum and palladium. The effect of using P507 to extract cobalt is very good.

[0024] Example 3 Gold extraction liquid: Co2+14.86 g / L, Ni2+1.5 g / L, Au 2.35g / L, Pt8.88g / L, Pd4.76g / L, volume 1000L like Figure 1As shown, ① the new extractant P 507 and the organic phase composition of sulfonated kerosene: 20% P 507 + 80% sulfonated coal, the two are evenly mixed for 2 minutes, 500L of pure water is added for washing at a ratio of 2:1, the washing times are twice, and the stirring and washing time is 5 minutes each time. The organic phase is saponified by adding 150L of 1mol / L ammonia water at a ratio of 20:3, mixed and stirred for 10 minutes, and then left to stand for 2 minutes for phase separation; ② the extraction phase ratio of the feed liquid of the carbonyl alloy enriched concentrate after gold extraction in the purification process and the cobalt extraction of the mixed organic phase of P 507 is: 0:A=4:1, 250L of the prepared organic phase is added, the extraction aqueous phase is adjusted to a pH value of 4.2-5 with hydrochloric acid, the extraction time is 10 minutes, and the phases are separated after standing for 2 minutes, and the secondary cobalt extraction is carried out, the organic phase is 250L, the extraction phase ratio is: 0:A=4:1, the pH value of the extraction aqueous phase is still 4.2-5, the extraction time is 5 minutes, and the phases are separated after standing for 2 minutes, and the temperature is: 20-28℃. ③ The stripping solution is 1000L of 2N HCl solution, the stripping phase ratio is: O:A=4:1, the extraction time is 10min, and the phases are separated after standing for 2min. The final metal content of the cobalt-extracted liquid is detected to be Co2+0.32 g / L, Ni2+1.43 g / L, Au 2.41g / L, Pt8.86g / L, and Pd4.72g / L.

[0025] From the analysis and detection data, it can be seen that after the gold-extracted liquid is subjected to P507 cobalt extraction, 97.84% of the cobalt is removed, and nickel, gold, platinum and palladium are basically not extracted. The effect of using P507 to extract cobalt is very good.

[0026] Example 4 like Figure 1 As shown, a method for removing impurity cobalt from a carbonyl alloy-enriched precious metal material comprises the following steps: S1. Mix the new extractant P507 and sulfonated kerosene. In the mixed solution, 20% is P507 and 80% is sulfonated coal. Stirring is started and mixed evenly. Then pure water is added in a ratio of 2:1. After stirring and washing, the phases are separated. The aqueous phase is treated as wastewater. 1 mol / L ammonia water is added to the organic phase in a ratio of 20:3. Mix and stir. After saponification, the phases are separated. The aqueous phase is recycled and the organic phase is used to extract cobalt. S2, the feed liquid of carbonyl alloy enriched concentrate after distillation, chlorination dissolution filtration and gold extraction in the purification process is mixed with P507 and the organic phase is subjected to a primary cobalt extraction, and then the phases are separated at rest to obtain an organic phase and an aqueous phase, wherein the extraction phase ratio of the primary cobalt extraction is: 0:A=4:1, and the pH value of the extracted aqueous phase is 4.2, and then the aqueous phase is subjected to a secondary cobalt extraction, and then the phases are separated at rest to obtain an organic phase and an aqueous phase, wherein the extraction phase ratio of the secondary cobalt extraction is: 0:A=4:1, and the pH value of the extracted aqueous phase is 4.2; S3, respectively, stripping the organic phases obtained from the primary cobalt extraction and the secondary cobalt extraction, specifically, adding 2N HCl solution to the organic phase, the stripping phase ratio: O:A=4:1, stripping, static phase separation, stripping water phase as the raw material of the cobalt product to recover cobalt, stripping oil phase enters the next cycle of washing, saponification, and cobalt extraction in step S1; S4. The aqueous phase obtained after the first and second cobalt extractions is subjected to platinum-palladium separation, platinum refining, and palladium refining to produce 99.99% palladium and platinum powder products.

[0027] Wherein, in step S1, the novel extractant P507 and sulfonated kerosene are uniformly mixed for 2 minutes.

[0028] Wherein, in the step S1, pure water is added for stirring and washing, and the washing times are twice, and each stirring and washing time is 5 minutes.

[0029] Wherein, in the step S1, the organic phase is added with ammonia water and mixed and stirred for 10 minutes, and then left to stand for 2 minutes for phase separation.

[0030] Wherein, in the step S2, the extraction time of cobalt is 10 minutes, and the phases are separated after standing for 2 minutes.

[0031] Wherein, in step S2, the extraction time of the secondary cobalt extraction is 5 minutes, and the static phase separation time is 2 minutes.

[0032] Wherein, in step S2, the temperature of the first cobalt extraction and the second cobalt extraction are both 20°C.

[0033] Wherein, in step S3, the stripping time is 10 minutes and the static phase separation time is 2 minutes.

[0034] Example 5 like Figure 1 As shown, a method for removing impurity cobalt from a carbonyl alloy-enriched precious metal material comprises the following steps: S1. Mix the new extractant P507 and sulfonated kerosene. In the mixed solution, 20% is P507 and 80% is sulfonated coal. Stirring is started and mixed evenly. Then pure water is added in a ratio of 2:1. After stirring and washing, the phases are separated. The aqueous phase is treated as wastewater. 1 mol / L ammonia water is added to the organic phase in a ratio of 20:3. Mix and stir. After saponification, the phases are separated. The aqueous phase is recycled and the organic phase is used to extract cobalt. S2, the feed liquid of carbonyl alloy enriched concentrate after distillation, chlorination dissolution filtration and gold extraction in the purification process is mixed with P507 and the organic phase is subjected to a primary cobalt extraction, and then the phases are separated at rest to obtain an organic phase and an aqueous phase, wherein the extraction phase ratio of the primary cobalt extraction is: 0:A=4:1, and the pH value of the extracted aqueous phase is 5, and then the aqueous phase is subjected to a secondary cobalt extraction, and then the phases are separated at rest to obtain an organic phase and an aqueous phase, wherein the extraction phase ratio of the secondary cobalt extraction is: 0:A=4:1, and the pH value of the extracted aqueous phase is 5; S3, respectively, stripping the organic phases obtained from the primary cobalt extraction and the secondary cobalt extraction, specifically, adding 2N HCl solution to the organic phase, the stripping phase ratio: O:A=4:1, stripping, static phase separation, stripping water phase as the raw material of the cobalt product to recover cobalt, stripping oil phase enters the next cycle of washing, saponification, and cobalt extraction in step S1; S4. The aqueous phase obtained after the first and second cobalt extractions is subjected to platinum-palladium separation, platinum refining, and palladium refining to produce 99.99% palladium and platinum powder products.

[0035] Wherein, in step S1, the novel extractant P507 and sulfonated kerosene are uniformly mixed for 2 minutes.

[0036] Wherein, in the step S1, pure water is added for stirring and washing, and the washing times are twice, and each stirring and washing time is 5 minutes.

[0037] Wherein, in the step S1, the organic phase is added with ammonia water and mixed and stirred for 10 minutes, and then left to stand for 2 minutes for phase separation.

[0038] Wherein, in step S2, the extraction time of cobalt is 10 minutes, and the phases are separated after standing for 2 minutes.

[0039] Wherein, in step S2, the extraction time of the secondary cobalt extraction is 5 minutes, and the static phase separation time is 2 minutes.

[0040] Wherein, in step S2, the temperature of the first cobalt extraction and the second cobalt extraction are both 28°C.

[0041] Wherein, in step S3, the stripping time is 10 minutes and the static phase separation time is 2 minutes.

[0042] The working principle of the present invention is: Process principle: The extraction ability of P507 for cobalt varies significantly under different pH conditions, so it is used to extract and separate cobalt in the solution. When the pH is 4.2-5, cobalt can be preferentially extracted by P507 into the organic phase, while nickel and other elements are basically not extracted. In addition, the washing section is further separated to wash away a small amount of nickel carried over from the organic phase, and the loaded organic phase is then stripped with hydrochloric acid to obtain a pure cobalt chloride solution. Figure 2The effect of the pH of the feed solution on the cobalt extraction rate.

[0043] It should be understood that the above specific embodiments of the present invention are only used to illustrate or explain the principles of the present invention, and do not constitute a limitation of the present invention. Therefore, any modifications, equivalent substitutions, improvements, etc. made without departing from the spirit and scope of the present invention should be included in the protection scope of the present invention. In addition, the appended claims of the present invention are intended to cover all changes and modifications that fall within the scope and boundaries of the appended claims, or the equivalent forms of such scope and boundaries.

Claims

1. A method for removing cobalt impurities from a carbonyl alloy-enriched precious metal material, characterized in that: The following steps are involved: S1. Mix the new extractant P507 and sulfonated kerosene. In the mixed solution, 20% is P507 and 80% is sulfonated coal. Stirring is started and mixed evenly. Then pure water is added in a ratio of 2:

1. After stirring and washing, the phases are separated. The aqueous phase is treated as wastewater. 1 mol / L ammonia water is added to the organic phase in a ratio of 20:

3. Mix and stir. After saponification, the phases are separated. The aqueous phase is recycled and the organic phase is used to extract cobalt. S2, the feed liquid of the carbonyl alloy enriched concentrate after distillation, chlorination dissolution filtration and gold extraction in the purification process is mixed with P 507 and the organic phase is subjected to a primary cobalt extraction, and then the phases are separated at rest to obtain an organic phase and an aqueous phase, wherein the extraction phase ratio of the primary cobalt extraction is: 0:A=4:1, and the pH value of the extracted aqueous phase is 4.2-5, and then the aqueous phase is subjected to a secondary cobalt extraction, and then the phases are separated at rest to obtain an organic phase and an aqueous phase, wherein the extraction phase ratio of the secondary cobalt extraction is: 0:A=4:1, and the pH value of the extracted aqueous phase is 4.2-5; S3, respectively, stripping the organic phases obtained from the primary cobalt extraction and the secondary cobalt extraction, specifically, adding 2N HCl solution to the organic phase, the stripping ratio is: O:A=4:1, stripping, static phase separation, stripping water phase as the raw material of the cobalt product to recover cobalt, stripping oil phase enters the next cycle of washing, saponification, and cobalt extraction in step S1; S4. The aqueous phase obtained after the first and second cobalt extractions is subjected to platinum-palladium separation, platinum refining, and palladium refining to produce 99.99% palladium and platinum powder products.

2. A method for removing cobalt impurities from carbonyl alloy-enriched precious metal materials according to claim 1, characterized in that: In step S1, the novel extractant P507 and sulfonated kerosene are uniformly mixed for 2 minutes.

3. A method for removing cobalt impurities from carbonyl alloy-enriched precious metal materials according to claim 1, characterized in that: In the step S1, pure water is added for stirring and washing, and the washing is performed twice, with each stirring and washing time being 5 minutes.

4. A method for removing cobalt impurities from carbonyl alloy-enriched precious metal materials according to claim 1, characterized in that: In step S1, the organic phase is added with aqueous ammonia and mixed and stirred for 10 minutes, and then left to stand for 2 minutes for phase separation.

5. A method for removing cobalt impurities from carbonyl alloy-enriched precious metal materials according to claim 1, characterized in that: In step S2, the extraction time of cobalt is 10 minutes, and the phases are separated by standing for 2 minutes.

6. A method for removing cobalt impurities from carbonyl alloy-enriched precious metal materials according to claim 1, characterized in that: In step S2, the extraction time of the secondary cobalt extraction is 5 minutes, and the static phase separation time is 2 minutes.

7. A method for removing cobalt impurities from carbonyl alloy-enriched precious metal materials according to claim 1, characterized in that: In step S2, the temperature of the primary cobalt extraction and the secondary cobalt extraction are both 20-28°C.

8. A method for removing cobalt impurities from carbonyl alloy-enriched precious metal materials according to claim 1, characterized in that: In step S3, the stripping time is 10 minutes and the static phase separation time is 2 minutes.

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