Method for recovering antimony and lead by reducing smelting of antimony sulfide ore, antimony alkaline residue and lead anode slime

Abstract

The application relates to a method for recovering antimony and lead by reducing smelting of sulfide antimony ore, antimony alkaline residue and lead anode slime, and specifically comprises the following steps: crushing the sulfide antimony ore, the antimony alkaline residue, the lead anode slime, a reducing agent and a slagging agent to a certain granularity and mixing them according to a certain proportion; feeding the mixture into a reducing smelting furnace to perform reducing smelting, controlling smelting temperature and smelting time, and generating a crude lead-antimony alloy to realize recovery of lead and antimony resources. Compared with the prior art, the application fully utilizes the oxidation-reduction reaction between the sulfide antimony component in the sulfide antimony ore and the antimony oxide in the lead anode slime and the antimony alkaline residue and the change of the excess sulfur component to the traditional alkaline slag system, and based on the high alkaline content and structural characteristics of the antimony alkaline residue, the adding amount of the reducing agent and the slagging agent is reduced, and the reducing activity of lead and antimony is improved, so that the lead and antimony resources in the sulfide antimony ore, the antimony alkaline residue and the lead anode slime are recovered in a low energy consumption, low cost and high efficiency mode, and the method has the advantages of short process, low cost and the like, and has a good popularization and application prospect.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of hazardous waste resource disposal, and relates to a method for recovering antimony and lead by reducing smelting antimony sulfide ore, antimony alkaline slag and lead anode slime. BACKGROUND

[0002] The lead anode slime is a material produced in the process of lead electrolytic refining production, and contains a large amount of toxic elements such as arsenic and lead. If the lead anode slime is stored in the environment, the environmental threat and safety risk are extremely great. At the same time, the lead anode slime is rich in a large amount of valuable metals such as antimony, bismuth, lead and tin, and contains rare and precious metals such as gold and silver, and the resource recovery value is huge. In order to realize the resource utilization and harmless disposal of the lead anode slime, a large amount of research has been carried out by researchers at home and abroad and non-ferrous metal smelting enterprises.

[0003] At present, the treatment methods for the lead anode slime mainly include a pyrometallurgical treatment process and a hydrometallurgical-pyrometallurgical combined process. The traditional pyrometallurgical process generally adopts a reduction smelting method to recover the resources of antimony, lead and precious metals, and the process basic slag system is a sodium carbonate slag system. However, sodium carbonate can form a sodium passivation effect on the antimony and lead phase, which leads to a low recovery rate of antimony and lead in the treatment process, and problems such as a long production cycle, a large amount of alkali addition, high cost and high energy consumption.

[0004] Patent CN103397191A discloses a method for comprehensively and efficiently treating lead anode slime by using a top-blown furnace, which comprises the following steps: preparing a mixture, primary reduction smelting, gold capturing by reduction, secondary blowing, and recovering arsenic and antimony. Specifically, the lead anode slime, a slag-making agent, returned material and a reducing agent are uniformly mixed to obtain a mixture; fuel is sprayed into the top-blown furnace pool at a material weight ratio of 1-10%, and the smelting temperature of the top-blown furnace is controlled at 900-1200℃; after sufficient reaction, a slag layer is formed and discharged through a discharge port, and then recovered and treated; the lead reduced by the reducing agent captures gold and silver, and then sinks to form a lead layer, which is further refined after further blowing and then discharged through the discharge port; and the high-temperature smoke dust is cooled and dedusted by a waste heat recovery device to obtain arsenic and antimony smoke dust. However, in the implementation process of the patent, the arsenic is widely dispersed in the arsenic and antimony smoke dust, smelting slag and lead-antimony alloy, and the dispersion degree is large, so that the secondary pollution of arsenic is difficult to control. In the hydrometallurgical-pyrometallurgical combined process, the lead anode slime is generally first subjected to oxygen pressure alkali leaching for pre-arsenic removal, and the key parameters such as oxygen pressure, leaching temperature and alkali concentration are controlled in the process. Then, the leaching slag is combined with the reduction smelting method to recover the resources of antimony, lead and precious metals, which effectively avoids the dispersion of arsenic. However, in the method, the oxygen pressure leaching process is used in the early stage, and a large amount of arsenic is dispersed in the leaching solution, which is difficult to dispose and is easy to cause secondary pollution. In addition, a large amount of lead and antimony phases are converted into sodium plumbite and sodium antimonate, which are difficult to reduce, so that the lead and antimony contents in the slag are high in the reduction smelting process, which causes a serious loss of lead and antimony resources and further leads to a decrease in the recovery rate of precious metal resources. Therefore, how to effectively recover the resources of antimony, lead and other resources in the lead anode slime has become a problem that is extremely concerned by the non-ferrous metal smelting industry. SUMMARY

[0005] The present application aims to overcome at least one of the above-mentioned defects in the prior art and provides a method for recovering antimony and lead by reducing smelting of antimony sulfide ore, antimony alkaline residue and lead anode slime. The present application makes full use of the redox reaction between the antimony sulfide component in the antimony sulfide ore and the antimony oxide in the lead anode slime and the antimony alkaline residue and the change of the excess sulfur component to the traditional alkaline residue system, and based on the high alkaline content and structural characteristics of the antimony alkaline residue, reduces the addition amount of reducing agent and slag forming agent, and improves the reducing activity of lead and antimony, realizes low energy consumption, low cost and high efficiency recovery of lead and antimony resources in the antimony sulfide ore, antimony alkaline residue and lead anode slime materials, and at the same time has the advantages of short process, low cost and good popularization and application prospect.

[0006] The object of the present application can be achieved by the following technical solutions:

[0007] One of the technical solutions of the present application is to provide a method for recovering antimony and lead by reducing smelting of antimony sulfide ore, antimony alkaline residue and lead anode slime, which comprises the following steps:

[0008] (1) crushing the antimony sulfide ore, antimony alkaline residue, lead anode slime, reducing agent and slag forming agent to a certain particle size and uniformly mixing them according to a certain proportion;

[0009] (2) feeding the mixture into a reducing smelting furnace for cooperative reduction smelting, controlling the smelting temperature and smelting time, and generating a crude lead-antimony alloy to realize recovery of lead and antimony resources.

[0010] As a preferred technical solution, the crude lead-antimony alloy generated in the smelting process flows out through a metal liquid outlet, the produced slag is discharged through a slag outlet, and the generated flue gas is discharged into the atmosphere after waste heat recovery and flue gas treatment.

[0011] Further, the antimony content of the lead anode slime in step (1) is 1-50wt.%, and the lead content is 1-50wt.%.

[0012] Further, the antimony content of the antimony sulfide ore in step (1) is 15-70wt.%, the lead content is 0.1-10wt.%, and the sulfur content is 7-27wt.%.

[0013] Further, the mixing mass ratio of the antimony sulfide ore to the lead anode slime in step (1) is (5-50):100.

[0014] Further, the antimony content of the antimony alkaline residue in step (1) is 25-70wt.%, the lead content is 0.5-15wt.%, and the alkali in the antimony alkaline residue includes sodium carbonate or sodium hydroxide, and the alkali content is 5-25wt.%.

[0015] Further, the mass ratio of the antimony slag to the lead anode slime in step (1) is (10-40):100.

[0016] Further, the reducing agent in step (1) is at least one of coke, semi-coke, coal powder and natural gas, and the adding amount of the reducing agent is 1-10 wt.% of the lead anode slime.

[0017] Further, the slag forming agent in step (1) is at least one of sodium carbonate and sodium hydroxide, and the adding amount of the slag forming agent is 5-10 wt.% of the lead anode slime.

[0018] Further, the particle size of the antimony sulfide ore, the antimony slag, the lead anode slime, the reducing agent and the slag forming agent in step (1) is 10-200 mesh.

[0019] Further, the smelting temperature in step (2) is 800-1200 DEG C, and the smelting time is 60-150 min.

[0020] Compared with the prior art, the present application has the following advantages:

[0021] (1) The added antimony sulfide component in the present application can react with the antimony oxide component in the lead anode slime and the antimony slag by oxidation-reduction reaction, thereby reducing the adding amount of the traditional reducing agent such as coke, semi-coke, coal powder or natural gas, and achieving remarkable energy-saving effect;

[0022] (2) The excess sulfur component in the added antimony sulfide ore can change the traditional alkali type slag system, reduce the activity of the sodium salt slag forming agent in the smelting pool, improve the activity of lead and antimony, and improve the recovery rate of lead and antimony in the antimony sulfide ore, the antimony slag and the lead anode slime;

[0023] (3) The high alkali content in the added antimony slag can reduce the adding amount of the sodium carbonate or sodium hydroxide as the slag forming agent, and the present application has low cost, short process and good popularization and application prospect. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 The process flow chart of the antimony lead recovery method by reduction smelting of the antimony sulfide ore, the antimony slag and the lead anode slime in the embodiments of the present application is shown. DETAILED DESCRIPTION

[0025] The present application will be described in detail below in combination with specific embodiments. The embodiments are implemented on the basis of the technical scheme of the present application, and detailed implementation modes and specific operation processes are given, but the protection scope of the present application is not limited to the following embodiments.

[0026] The equipment used in the following examples, unless otherwise specified, represents the conventional equipment in the art; the reagents used, unless otherwise specified, represent the commercially available products or are prepared by the conventional methods in the art, which are not described in detail in the following examples, and can be achieved by the conventional experimental means in the art.

[0027] A method for recovering antimony and lead by reducing smelting antimony sulfide ore, antimony alkaline residue and lead anode slime, as shown in the following steps: Figure 1 The specific steps are as follows:

[0028] A certain amount of lead anode slime (lead content of 1-50wt.%, antimony content of 1-50wt.%), reducing agent (at least one of coke, semicoke, coal powder and natural gas, added amount of 1-10wt.% of lead anode slime), antimony sulfide ore (antimony content of 15-70wt.%, lead content of 0.1-10wt.%, sulfur content of 7-27wt.%), antimony alkaline residue (antimony content of 25-70wt.%, lead content of 0.5-15wt.%, alkali including sodium carbonate or sodium hydroxide, alkali content of 5-25wt.%, mixing mass ratio of antimony alkaline residue and lead anode slime of (10-40):100) and slagging agent (at least one of sodium carbonate and sodium hydroxide, added amount of 5-10wt.% of lead anode slime) are all ground to 10-200 mesh and uniformly mixed, then sent to a reducing smelting furnace for cooperative reduction smelting, the smelting temperature is controlled at 800-1200℃ and the smelting time is controlled at 60-150min, the generated crude lead-antimony alloy flows out through the metal liquid outlet, the generated slag is discharged through the slag outlet, and the generated flue gas is discharged into the atmosphere after waste heat recovery and flue gas treatment.

[0029] Example 1:

[0030] A method for recovering antimony and lead by reducing smelting antimony sulfide ore, antimony alkaline residue and lead anode slime, the specific steps are as follows:

[0031] 20 tons of lead anode slime (25wt.% of lead content, 32wt.% of antimony content), 1.6 tons of reducing agent (coke, the addition amount is 8wt.% of the lead anode slime), 4 tons of antimony sulfide ore (58wt.% of antimony content, 5wt.% of lead content, 20wt.% of sulfur content, the mixed mass ratio of the antimony sulfide ore and the lead anode slime is 20:100), 2 tons of antimony alkali residue (43wt.% of antimony content, 12wt.% of lead content, 15wt.% of sodium carbonate content, the mixed mass ratio of the antimony alkali residue and the lead anode slime is 10:100) and 1 ton of slagging agent (sodium carbonate, the addition amount is 5wt.% of the lead anode slime) are all ground to 20 mesh and uniformly mixed, and then are sent into a reduction smelting furnace for cooperative reduction smelting, the smelting temperature is controlled to be 1200℃ and the smelting time is controlled to be 90 minutes, the generated crude lead-antimony alloy flows out through a metal liquid outlet in the smelting process, the generated molten slag is discharged through a slag outlet, and the generated flue gas is discharged into the atmosphere after waste heat recovery and flue gas treatment.

[0032] After the mixture of the antimony sulfide ore, the antimony alkali residue and the lead anode slime in the above process is subjected to the cooperative reduction smelting, it is detected and analyzed that the antimony content in the molten slag is reduced to 1.21wt.% and the lead content is reduced to 0.12wt.%, and the process realizes the efficient recovery of the antimony and lead resources in the antimony sulfide ore, the antimony alkali residue and the lead anode slime.

[0033] Example 2:

[0034] A method for recovering antimony and lead by reduction smelting of antimony sulfide ore, antimony alkali residue and lead anode slime, the specific steps are as follows:

[0035] 30 tons of lead anode slime (31wt.% of lead content, 38wt.% of antimony content), 3 tons of reducing agent (semi-coke, the addition amount is 10wt.% of the lead anode slime), 10.5 tons of antimony sulfide ore (62wt.% of antimony content, 3wt.% of lead content, 24wt.% of sulfur content, the mixed mass ratio of the antimony sulfide ore and the lead anode slime is 35:100), 6 tons of antimony alkali residue (39wt.% of antimony content, 5wt.% of lead content, 10wt.% of sodium hydroxide content, the mixed mass ratio of the antimony alkali residue and the lead anode slime is 20:100) and 1.8 tons of slagging agent (sodium hydroxide, the addition amount is 6wt.% of the lead anode slime) are all ground to 10 mesh and uniformly mixed, and then are sent into a reduction smelting furnace for cooperative reduction smelting, the smelting temperature is controlled to be 1100℃ and the smelting time is controlled to be 150 minutes, the generated crude lead-antimony alloy flows out through a metal liquid outlet in the smelting process, the generated molten slag is discharged through a slag outlet, and the generated flue gas is discharged into the atmosphere after waste heat recovery and flue gas treatment.

[0036] After the mixture of antimony sulfide ore, antimony alkaline residue and lead anode slime in the above process is subjected to synergistic reduction smelting, detection analysis shows that the content of antimony in the slag is reduced to 1.09 wt.%, and the content of lead is reduced to 0.08 wt.%, and the process realizes efficient recovery of antimony and lead resources in the antimony sulfide ore, antimony alkaline residue and lead anode slime.

[0037] Example 3:

[0038] A method for recovering antimony and lead by reduction smelting of antimony sulfide ore, antimony alkaline residue and lead anode slime, and the specific steps are as follows:

[0039] After 20 t of lead anode slime (containing 50 wt.% of lead and 27 wt.% of antimony), 1.4 t of reducing agent (a mixture of coke and semi-coke with a mass ratio of 3:7, and the total amount of addition is 7 wt.% of the lead anode slime), 8 t of antimony sulfide ore (containing 63 wt.% of antimony, 0.7 wt.% of lead and 25 wt.% of sulfur, and the mixing mass ratio of the antimony sulfide ore and the lead anode slime is 40:100), 7 t of antimony alkaline residue (containing 45 wt.% of antimony, 0.9 wt.% of lead and 5 wt.% of sodium carbonate, and the mixing mass ratio of the antimony alkaline residue and the lead anode slime is 35:100) and 2 t of slagging agent (a mixture of sodium carbonate and sodium hydroxide with a mass ratio of 4:6, and the total amount of addition is 10 wt.% of the lead anode slime) are all ground to 100 mesh and uniformly mixed, and then sent to a reduction smelting furnace for synergistic reduction smelting, with the smelting temperature controlled at 1200°C and the smelting time controlled at 130 min. The coarse lead-antimony alloy generated during smelting flows out through the metal liquid outlet, the produced slag is discharged through the slag outlet, and the generated flue gas is discharged into the atmosphere after waste heat recovery and flue gas treatment.

[0040] After the mixture of antimony sulfide ore, antimony alkaline residue and lead anode slime in the above process is subjected to synergistic reduction smelting, detection analysis shows that the content of antimony in the slag is reduced to 1.09 wt.%, and the content of lead is reduced to 0.08 wt.%, and the process realizes efficient recovery of antimony and lead resources in the antimony sulfide ore, antimony alkaline residue and lead anode slime.

[0041] The above description of the embodiments is for the purpose of enabling a person of ordinary skill in the art to understand and use the invention. Those skilled in the art can easily make various modifications to these embodiments, and apply the general principles described herein to other embodiments without having to go through creative labor. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art without departing from the scope of the present invention should be within the scope of protection of the present invention.

Claims

1. A method for recovering antimony and lead by reducing smelting of antimony sulfide ore, antimony alkaline residue and lead anode slime, characterized in that, The method comprises the following steps: (1) crushing antimony sulfide ore, antimony alkaline residue, lead anode slime, reducing agent and slagging agent to a certain particle size and mixing them according to a certain proportion; (2) feeding the mixture into a reduction smelting furnace for reduction smelting, controlling the smelting temperature and smelting time, generating crude lead-antimony alloy to realize the recovery of lead-antimony resources; The sulfur content of the antimony sulfide ore in step (1) is 7-27 wt.%; The alkali content of the antimony alkaline residue in step (1) is 5-25 wt.%; The addition amount of the reducing agent in step (1) is 1-10 wt.% of the lead anode slime; The addition amount of the slagging agent in step (1) is 5-10 wt.% of the lead anode slime; The sulfur component in the added antimony sulfide ore reacts with the antimony oxide component in the lead anode slime and the antimony alkaline residue, reducing the addition amount of the reducing agent; The excess sulfur component in the added antimony sulfide ore changes the formation of the alkaline slag system, reduces the activity of the slagging agent in the molten pool, increases the activity of lead and antimony, and improves the recovery rate of lead and antimony in the materials of the antimony sulfide ore, the antimony alkaline residue and the lead anode slime; The high alkali content in the added antimony alkaline residue reduces the addition amount of the slagging agent.

2. The method according to claim 1, wherein the method is characterized by, The antimony content of the lead anode slime in step (1) is 1-50 wt.%, and the lead content is 1-50 wt.%.

3. The method according to claim 1, wherein the method is characterized by, The antimony content of the antimony sulfide ore in step (1) is 15-70 wt.%, and the lead content is 0.1-10 wt.%.

4. The method according to claim 1, wherein the method is characterized by, The mixing mass ratio of the antimony sulfide ore to the lead anode slime in step (1) is (5-50):

100.

5. The method according to claim 1, wherein the method is characterized by, The antimony content of the antimony alkaline residue in step (1) is 25-70 wt.%, and the lead content is 0.5-15 wt.%. The alkali in the antimony alkaline residue includes sodium carbonate or sodium hydroxide.

6. The method according to claim 1, wherein the method is characterized by, The mixing mass ratio of the antimony alkaline residue to the lead anode slime in step (1) is (10-40):

100.

7. The method according to claim 1, wherein the method is characterized by, The reducing agent in step (1) is at least one of coke, semicoke, coal powder and natural gas.

8. The method according to claim 1, wherein the method is characterized by, The slagging agent in step (1) is at least one of sodium carbonate and sodium hydroxide.

9. The method according to claim 1, wherein the method is characterized by, The crushing particle size of the antimony sulfide ore, the antimony alkaline residue, the lead anode slime, the reducing agent and the slagging agent in step (1) is 10-200 mesh.

10. The method according to claim 1, wherein the method is characterized by, The smelting temperature in step (2) is 800-1200 ℃, and the smelting time is 60-150 min.

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