A method for preferentially extracting antimony from a lead-antimony co-associated ore

Abstract

The application discloses a method for preferentially extracting antimony from lead-antimony co-associated ores, comprising the following steps: mixing lead-antimony co-associated ore materials with sulfides and alkali according to certain proportions to obtain mixed materials; low-temperature roasting the mixed materials to obtain roasted materials; water leaching and solid-liquid separation treatment of the roasted materials to obtain water leaching solution; configuring the water leaching solution into an electrodeposition solution; and electrolytic deposition treatment of the electrodeposition solution to obtain antimony on a cathode. The low-temperature roasting-water leaching-electrodeposition process can realize preferential extraction of antimony and efficient separation of lead and antimony. Lead is enriched in the water leaching residue, which is helpful for subsequent extraction and smelting of lead, and avoids the industry common problem that lead-antimony intermediate alloy is difficult to separate in the traditional process. In the application, sulfides of antimony fully react with sodium sulfide and sodium hydroxide in the roasting process, and the reaction rate is faster than that in water solution leaching. Not only the reaction time is shortened, but also the consumption of sodium sulfide is significantly lower than the amount required in conventional alkaline hydrometallurgy of antimony.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of metal smelting, and particularly relates to a method for preferentially extracting antimony from lead-antimony co-associated ore. BACKGROUND

[0002] The method for extracting antimony from lead-antimony co-associated ore mainly includes fire method, wet method and biological method. The fire method mainly uses smelting reduction to process fragile pyrite lead-antimony ore, multi-metal lead-antimony co-associated ore and other lead-antimony ores, so as to obtain lead-antimony alloy intermediate product. Because the chemical properties of lead and antimony are similar, the behaviors of lead and antimony are similar in the smelting process, so it is extremely difficult to realize the separation of lead and antimony by the fire method. At present, the separation of lead-antimony alloy in industry generally adopts the two-time blowing reduction smelting process of a reverberatory furnace, the lead-antimony alloy is separated by blowing in the reverberatory furnace, so that the antimony is converted into antimony oxide powder into the flue dust, and then the reduction smelting and fire refining are carried out to produce crude antimony, which has problems of long process flow, high energy consumption, low comprehensive recovery rate of valuable metals, and large amount of waste gas and waste residue.

[0003] According to the wet smelting process of lead-antimony co-associated ore, the wet smelting process of lead-antimony co-associated ore can be roughly divided into two categories of acid wet smelting of antimony and alkaline wet smelting of antimony according to the properties of the leaching solution system. The acid wet smelting of antimony generally selects hydrochloric acid and ferric chloride as the leaching agent, and simultaneously adopts chlorination-dry distillation, so that the purity of the extracted crude antimony can reach 99%. However, this method uses chlorine gas, and the process may release chlorine gas or hydrogen chloride gas, which has a negative impact on the atmosphere. In addition, chlorine gas has high corrosiveness and toxicity, and there is a risk in the treatment process. The equipment also has high requirements for corrosion resistance. The alkaline wet smelting of antimony mainly uses a mixed solution of sodium sulfide and sodium hydroxide as the leaching solution, and generates soluble alkaline thioantimonite in the leaching process, so as to achieve the purpose of leaching antimony. However, in the leaching process, in order to achieve a high leaching rate of antimony, the concentration of the leaching solution, the leaching temperature and the leaching time need to be strictly controlled, the leaching time is relatively long, and the sodium sulfide needs to have a certain excess coefficient. Therefore, the content of sodium sulfide in the leaching solution is high, which causes the current efficiency of the subsequent electrolysis process to be low. In view of the problems of long process flow, low comprehensive recovery rate of valuable metals, high reaction energy consumption and large amount of alkali consumption in the existing antimony extraction technology of lead-antimony co-associated ore, it is urgent to develop a cleaner, more efficient and more economical smelting method.

[0004] Therefore, the prior art still needs to be further improved and promoted. SUMMARY

[0005] In view of the above problems in the prior art, the present application provides a method for preferentially extracting antimony from lead-antimony co-associated ore, which aims to solve the problems of long process flow, low comprehensive recovery rate of valuable metals and high process energy consumption in the existing method for extracting antimony from lead-antimony co-associated ore.

[0006] The technical scheme adopted by the present application to solve the above technical problems is as follows:

[0007] A method for preferentially extracting antimony from a lead-antimony co-associated ore, comprising:

[0008] Mixing lead-antimony co-associated ore material with sulfide and alkali in a certain proportion to obtain a mixture;

[0009] Roasting the mixture to obtain a roasted material;

[0010] Water leaching and solid-liquid separation treatment of the roasted material to obtain a water leaching solution;

[0011] Configuring the water leaching solution as an electrodeposition solution, and performing electrolytic deposition treatment on the electrodeposition solution to obtain antimony on the cathode.

[0012] The following is a preferred technical scheme of the present application, but is not a limitation on the technical scheme provided by the present application. Through the following preferred technical scheme, the purpose and beneficial effects of the present application can be better achieved and realized.

[0013] As a preferred technical scheme, the particle size of the lead-antimony co-associated ore material is -80 mesh to -200 mesh.

[0014] As a preferred technical scheme, the lead-antimony co-associated ore material and the sulfide and alkali are proportioned according to a mass ratio of 10:(1-3):(3-5) to obtain the mixture. The sulfide can be one or more of sodium sulfide, hydrogen sulfide, sodium sulfide, potassium sulfide, and potassium sulfide. The alkali includes one or more of sodium hydroxide, potassium hydroxide, calcium oxide, and calcium hydroxide.

[0015] As a preferred technical scheme, the roasting temperature is 150℃-200℃.

[0016] As a preferred technical scheme, in the water leaching treatment of the roasted material, the leaching solution is an aqueous solution selected from one of an aqueous neutral solution, a weakly acidic aqueous solution, and an alkaline aqueous solution.

[0017] As a preferred technical scheme, in the water leaching treatment of the roasted material, the water leaching temperature is 20℃-90℃, and the water leaching time is 0.5h-1h.

[0018] As a preferred technical scheme, the method for preferentially extracting antimony from lead-antimony co-associated ores, wherein, in the water immersion treatment of the roasting material, the ratio of the volume of the leaching solution to the weight of the roasting material is 2 mL:1 g to 10 mL:1 g.

[0019] As a preferred technical scheme, the method for preferentially extracting antimony from lead-antimony co-associated ores, wherein, in the water immersion treatment of the roasting material, the ratio of the volume of the leaching solution to the weight of the roasting material is 2 mL:1 g to 10 mL:1 g.

[0020] As a preferred technical scheme, the method for preferentially extracting antimony from lead-antimony co-associated ores, wherein, in the water immersion treatment of the roasting material, the ratio of the volume of the leaching solution to the weight of the roasting material is 2 mL:1 g to 10 mL:1 g. 3+ The concentration is 40 g / L to 120 g / L.

[0021] As a preferred technical scheme, the method for preferentially extracting antimony from lead-antimony co-associated ores, wherein, in the water immersion treatment of the roasting material, the ratio of the volume of the leaching solution to the weight of the roasting material is 2 mL:1 g to 10 mL:1 g. 2 The current density is 30 A / m 2 to 350 A / m 2 , and the electrodeposition temperature is 20℃ to 80℃.

[0022] Beneficial effects: compared with the prior art, the low-temperature roasting-water immersion-electrodeposition process can realize the preferential extraction of antimony and the efficient separation of lead and antimony. Lead is enriched in the water immersion residue, which is helpful for the subsequent extraction and smelting of lead, and avoids the industry common problem that lead-antimony intermediate alloy is difficult to separate in the traditional process. In the present application, the sulfide of antimony fully reacts with sodium sulfide and sodium hydroxide in the roasting process, and the reaction rate is faster than that in the water solution leaching. Not only is the reaction time shortened, but also the consumption of sodium sulfide is significantly lower than the amount required in the conventional alkaline hydrometallurgy of antimony. The method has the characteristics of short process flow, simple operation, low reagent consumption, high comprehensive recovery rate, etc., and is suitable for large-scale industrial production. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 is the method flow diagram provided by the present application for preferentially extracting antimony from lead-antimony co-associated ores;

[0024] Figure 2 is the XRD pattern of the lead-antimony co-associated ore (Wujimin) raw material provided in Example 1;

[0025] Figure 3 is the XRD pattern of the low-temperature roasting water immersion residue of the lead-antimony co-associated ore (Wujimin);

[0026] Figure 4 is the XRD pattern of the lead-antimony co-associated ore (Gaofeng ore) raw material provided in Example 2;

[0027] Figure 5XRD pattern of low-temperature roasting and water leaching residue of lead-antimony co-associated ore (Gaofeng mine) ;

[0028] Figure 6 Cathode deposition of antimony from leaching solution of lead-antimony co-associated ore (Wujij mine) in Example 1;

[0029] Figure 7 Cathode deposition of antimony from leaching solution of lead-antimony co-associated ore (Gaofeng mine) in Example 2;

[0030] Figure 8 Cathode deposition of antimony from leaching solution of lead-antimony co-associated ore (Gaofeng mine) in Example 3. DETAILED DESCRIPTION

[0031] The present application provides a method for preferentially extracting antimony from lead-antimony co-associated ore. In order to make the purpose, technical solution and effect of the present application more clear and explicit, the present application is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present application and do not limit the present application.

[0032] In addition, the features, operations or characteristics described in the specification can be combined in any appropriate manner to form various embodiments. Meanwhile, the steps or actions in the method description can also be sequentially changed or adjusted in a manner that is obvious to those skilled in the art. Therefore, the various sequences in the specification and the drawings are only for clear description of a certain embodiment, and do not mean that the sequence is necessary. The serial numbers of the components in this paper, such as "first", "second", etc., are only used to distinguish the described objects, and do not have any sequence or technical meaning.

[0033] The present application provides a method for preferentially extracting antimony from lead-antimony co-associated ore, comprising:

[0034] S10, mixing lead-antimony co-associated ore material with sodium sulfide and sodium hydroxide to obtain a mixture.

[0035] Specifically, in combination with Figure 1 The lead-antimony co-associated ore is crushed and ground to a certain particle size to obtain lead-antimony co-associated ore material; the lead-antimony co-associated ore material obtained by crushing is mixed with sodium sulfide, sodium hydroxide and a small amount of water in a certain proportion to obtain a mixture. By adding (spraying) a small amount of water, the mixture can be wetted, thereby promoting the further mixing of sodium sulfide, sodium hydroxide and lead-antimony co-associated ore material.

[0036] In the present application, the lead-antimony co-associated ore is crushed and refined, and the average particle size is-80 mesh to-200 mesh, such as-80 mesh, -100 mesh, -120 mesh, -150 mesh, -180 mesh and-200 mesh, etc. The proportion of the lead-antimony co-associated ore and the sulfide, the alkali is according to any ratio in the range of 10: (1-3) : (3-5), such as 10:1:4, 10:2:4, 10:3:4, 10:1:3, 10:1:5, etc. The mixed material is obtained by batching and uniformly mixing. In the direct alkali leaching, the leaching temperature cannot exceed the boiling point of water due to the limitation of water evaporation temperature. In order to improve the leaching efficiency, the sulfide needs to be excessive, and the liquid-solid ratio is large. In the pre-roasting-water leaching, the pre-roasting temperature is high, which can consume less alkali, use low liquid-solid ratio, obtain leaching solution with high antimony ion concentration and low sodium sulfide concentration, improve the current efficiency of electrodeposition, avoid the generation of polysulfide, and reduce the loss of gold and silver associated metals.

[0037] After the step S10, the step S20 of roasting the mixed material is further included to obtain the roasted material.

[0038] Specifically, the roasting temperature is any temperature in the range of 150℃ to 200℃, such as 150℃, 160℃, 170℃, 180℃, 190℃, 200℃, etc., and preferably 150℃ to 170℃; the roasting time is any time in the range of 0.5h to 2h, such as 0.5h, 1.0h, 1.5h, 2.0h, etc., and preferably 0.5h to 1.0h. During the roasting process, the following chemical reactions occur:

[0039]

[0040]

[0041] The roasting atmosphere is any one or mixture of air, compressed air, inert gas, which can be one or mixture of nitrogen or argon.

[0042] In the present application, low-temperature roasting makes the antimony-containing minerals (such as Sb2S3, Pb4FeSb6S 14After roasting, the sulfides of antimony in the present application and sodium sulfide, sodium hydroxide can completely react in the roasting process, and the reaction rate is faster than that in the water solution leaching, which not only helps to shorten the reaction time, but also significantly reduces the consumption of sodium sulfide compared with the conventional alkaline hydrometallurgy of antimony, so the reagent consumption is low, the separation effect of lead and antimony is good, and at the same time, the water leaching can realize the efficient leaching of antimony at a low liquid-solid ratio, and a solution with high concentration of antimony ions and low concentration of sodium sulfide can be obtained, which is beneficial to the smooth electro-deposition.

[0043] After the step S20, there is also a step S30 of water leaching and solid-liquid separation treatment of the roasting material to obtain a water leaching solution.

[0044] Specifically, the roasting material obtained in the step S20 is subjected to crushing and refining treatment and then water leaching to obtain a slurry, and the slurry is subjected to liquid-solid separation to obtain a water leaching residue and a water leaching solution.

[0045] In the present application, the leaching solution used in the water leaching is an aqueous solution, which can be one of a neutral aqueous solution, a weakly acidic aqueous solution and an alkaline aqueous solution, and is preferably a neutral aqueous solution; the preferred time of water leaching is 0.5h-1.0h; the temperature of water leaching is any temperature in the range of 20℃-90℃, such as 20℃-24℃, 24℃-30℃, 30℃-35℃, 35℃-40℃, 40℃-45℃, 45℃-50℃, 50℃-55℃, 55℃-60℃, 60℃-65℃, 65℃-70℃, 70℃-75℃, 75℃-80℃, 80℃-85℃, 85℃-90℃; the liquid-solid ratio of water leaching (i.e. the ratio of the volume of the water leaching solution to the weight of the roasting material) is any value in the range of 2mL:1g-10mL:1g.

[0046] After the step S30, there is also a step S40 of configuring the water leaching solution into an electro-deposition solution, and subjecting the electro-deposition solution to electrolytic deposition treatment to obtain antimony on the cathode.

[0047] Specifically, the slurry obtained in the step S30 is subjected to liquid-solid separation to obtain a water leaching residue and a water leaching solution. The obtained water leaching solution is configured into an electro-deposition solution, and direct current is passed to perform electrolytic deposition to obtain crude antimony product on the cathode; the water leaching residue is washed to obtain a lead-rich material, which is sent to a lead smelting process to extract lead; the washing water is returned to the water leaching process in the step S30 as a leaching solution; the liquid-solid separation process can be realized by any one of centrifugal separation, plate and frame pressure filtration or membrane filtration;

[0048] In the present invention, the liquid-to-solid ratio of the water-immersion residue washing (i.e., the ratio of the volume of the water washing liquid to the weight of the water-immersion residue) is any value in the range of 1 mL:1 g to 5 mL:1 g; the temperature of the washing water is ≥20°C, and the number of washings is 1 to 5 times, such as 1 time, 2 times, 3 times, 4 times, 5 times, etc., preferably 2 to 3 times; the electrolytic solution Sb prepared by the water immersion liquid is 3+ The concentration is controlled to be any concentration within the range of 40g / L to 120g / L, preferably Sb 3+ Concentration 70g / L~90g / L;

[0049] The current density of the electrolytic deposition is 30A / m 2 ~350A / m 2 , the preferred current density is 250A / m 2 ~350A / m 2 ; The electrodeposition temperature is 20℃~80℃, and the preferred electrodeposition temperature is 40℃~80℃.

[0050] The method for preferentially extracting antimony from lead-antimony co-existing ore provided by the present invention is further explained below through specific examples.

[0051] Example 1:

[0052] Table 1 Main components of lead-antimony co-existing ore (Wuji Mine) raw materials and low-temperature roasting water-leached slag.

[0053]

[0054] Step 1) crushing and grinding the above-mentioned lead-antimony co-existing ore (Wuji Mine) raw material to -200 mesh, accounting for 85%; the XRD pattern of the lead-antimony co-existing ore (Wuji Mine) raw material is as follows Figure 2 shown.

[0055] Step 2) 20 g of the lead-antimony co-existing ore obtained in step 1) was mixed with 2 g of sodium hydroxide, 24.49 g of sodium sulfide nonahydrate, and 5 ml of water;

[0056] Step 3) calcining the mixture obtained in step 2) at 160° C. for 0.5 h to obtain a calcined material;

[0057] Step 4) soaking the roasted material obtained in step 3) in water at 90° C., a liquid-to-solid ratio of 3, and a time of 0.5 h, washing once, and obtaining a water-soaked residue and a water-soaked liquid after liquid-solid separation;

[0058] Step 5) XRD of water-leached residue ( Figure 3 ) No antimony compounds were found. The antimony content in the low-temperature roasted water-leached slag in Table 1 was 2.01%, and the antimony leaching rate reached 95.12%;

[0059] Step 6) The water extract was concentrated to an antimony concentration of 80 g / L and the current density was 250 A / m2 , 50℃, 6h;

[0060] The cathode plate deposition after the electro-deposition is as follows Figure 6 The purity of the crude antimony in the cathode reaches 96.69%

[0061] Example 2

[0062] Table 2 Main components of the lead-antimony co-associated ore (Gaofeng ore) and the low-temperature roasting and water leaching residue.

[0063]

[0064] Step 1) The lead-antimony co-associated ore (Gaofeng ore) is crushed and ground to 85% of -150 mesh;

[0065] Step 2) The crushed material obtained in Step 1) is taken out, 20g of the crushed material is uniformly mixed with 3.5g of sodium hydroxide and 20g of sodium sulfide nonahydrate;

[0066] Step 3) The mixture obtained in Step 2) is roasted at 170℃ for 1h to obtain a roasted material;

[0067] Step 4) The roasted material obtained in Step 3) is subjected to water leaching at 60℃, liquid-solid ratio 1, time 1h, washed twice, and then subjected to liquid-solid separation to obtain a water leaching residue and a water leaching solution;

[0068] Step 5) Figure 4 The low-temperature roasting and water leaching residue does not contain antimony compounds. The content of antimony in the water leaching residue is 0.98%, and the leaching rate of antimony reaches 98.24%;

[0069] Step 6) The water leaching solution is concentrated to an antimony concentration of 90g / L, and then subjected to electro-deposition at a current density of 300A / m 2 , 60℃, 12h;

[0070] Step 7) The cathode plate deposition after the electro-deposition is as follows Figure 7 The purity of the crude antimony in the cathode reaches 97.22%.

[0071] Example 3

[0072] Step 1) The lead-antimony co-associated ore (Gaofeng ore) is crushed and ground to a particle size of 85% of -100 mesh;

[0073] Step 2) The crushed material obtained in Step 1) is taken out, 20g of the crushed material is uniformly mixed with 2g of sodium hydroxide and 18g of sodium sulfide nonahydrate;

[0074] Step 3) The mixture obtained in Step 2) is roasted at 160℃ for 1.5h to obtain a roasted material;

[0075] Step 4) The roasting material obtained in step 3) is subjected to water immersion at 70 DEG C, liquid-solid ratio 4, time 1.5h, and after liquid-solid separation, water immersion residue and water immersion liquid are obtained. The content of antimony in the leaching residue is 3.89%, and the leaching rate of antimony reaches 87.35%;

[0076] Step 5) The water immersion liquid is concentrated to an antimony concentration of 80g / L, and under the conditions of current density 350A / m 2 , 50 DEG C, electrodeposition 24h;

[0077] Step 6) The deposition of the cathode plate after electrodeposition is as follows Figure 8 , and the purity of the crude antimony on the cathode reaches 96.07%.

[0078] In summary, the present application provides a method for preferentially extracting antimony from lead-antimony co-associated ore, comprising the steps of: mixing lead-antimony co-associated ore material with sodium sulfide and sodium hydroxide to obtain a mixed material; roasting the mixed material to obtain a roasting material; subjecting the roasting material to water immersion and solid-liquid separation treatment to obtain water immersion liquid; configuring the water immersion liquid into electrodeposition liquid, and subjecting the electrodeposition liquid to electrolytic deposition treatment to obtain antimony on the cathode. The present application is aimed at lead-antimony co-associated ore, especially fragile jamesonite, and through the low-temperature roasting-water immersion-electrodeposition process, the preferential extraction of antimony and the efficient separation of lead and antimony can be realized. Lead is enriched in the water immersion residue, which is helpful for the subsequent extraction and smelting of lead, and avoids the industry common problem that lead-antimony intermediate alloy is difficult to separate in the traditional process. In the present application, the sulfide of antimony fully reacts with sodium sulfide and sodium hydroxide in the roasting process, and the reaction rate is faster than that in water solution leaching. Not only is it helpful to shorten the reaction time, but also the consumption of sodium sulfide is significantly lower than the amount required in conventional alkaline hydrometallurgy, and the leaching liquid with high antimony ion concentration and low sodium sulfide concentration can be obtained, which is conducive to the subsequent electrodeposition extraction of antimony. The present method has the characteristics of short process flow, simple operation, low reagent consumption, high comprehensive recovery rate, etc., and is suitable for large-scale industrial production.

[0079] It should be understood that the application of the present application is not limited to the above examples, and those of ordinary skill in the art can make improvements or changes according to the above description, and all these improvements and changes shall belong to the protection scope of the appended claims of the present application.

Claims

1. A method for preferentially extracting antimony from lead-antimony co-existing ore, characterized in that: include: The lead-antimony co-existing ore, sulfide and alkali are mixed in a certain proportion to obtain a mixture; calcining the mixed material to obtain a calcined material; The calcined material is subjected to water immersion and solid-liquid separation treatment to obtain a water immersion liquid; The aqueous immersion liquid is configured into an electrolytic solution, and the electrolytic solution is subjected to an electrolytic deposition process to obtain antimony on a cathode; The lead-antimony co-existing ore, the sulfide and the alkali are mixed in a mass ratio of 10:(1-3):(3-5) to obtain the mixed material; the roasting temperature is 150° C. to 170° C.; and the roasting time is 0.5 to 1.0 h; In the water leaching treatment of the calcined material, the ratio of the volume of the leaching solution to the weight of the calcined material is 2 mL:1 g to 10 mL:1 g; The lead-antimony co-existing ore is brittle sulfur lead-antimony ore.

2. The method for preferentially extracting antimony from lead-antimony co-existing ore according to claim 1, characterized in that: The particle size of the lead-antimony co-existing ore is -80 mesh to -200 mesh.

3. The method for preferentially extracting antimony from lead-antimony co-existing ore according to claim 1, characterized in that: In the water leaching treatment of the roasted material, the leaching liquid is an aqueous solution, and the aqueous solution is selected from one of an aqueous neutral solution, a weakly acidic aqueous solution, and an alkaline aqueous solution.

4. The method for preferentially extracting antimony from lead-antimony co-existing ore according to claim 1, characterized in that: In the water immersion treatment of the roasted material, the water immersion temperature is 20° C. to 90° C. and the water immersion time is 0.5 h to 1 h.

5. The method for preferentially extracting antimony from lead-antimony co-existing ore according to claim 1, characterized in that: The water leaching and solid-liquid separation treatment of the roasted material also obtains water leaching residue; the water leaching residue is washed to obtain washing liquid; and the washing liquid is used as the leachate for leaching the roasted material.

6. The method for preferentially extracting antimony from lead-antimony co-existing ore according to claim 1, characterized in that: Sb in the electrolytic solution 3+ The concentration is 40g / L~120g / L.

7. The method for preferentially extracting antimony from lead-antimony co-existing ore according to claim 6, characterized in that: The current density of the electrolytic deposition process is 30A / m 2 ~350A / m 2 , the electrodeposition temperature is 20℃~80℃.

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