Process for leaching antimony from complex antimony-containing materials

Abstract

The application discloses a kind of complex antimony-containing material high-efficiency antimony leaching method, solve the problem of low efficiency of antimony leaching and difficult solid-liquid separation when using conventional sodium sulfide alkali method to leach antimony.By alkali leaching and arsenic removal, copper and bismuth removal by chlorine salt reduction and acid leaching, and NaHS+NaOH combined antimony leaching after treatment, high-efficiency leaching and enrichment of antimony in complex antimony-containing material is realized.Compared with the leaching effect of sodium sulfide, the leaching efficiency of antimony is significantly improved, and the leaching rate of antimony in the process of NaHS+NaOH combined antimony leaching is stable at more than 96%.Compared with sodium sulfide, sodium hydrosulfide has the advantages of low price, low sodium content, low temperature and difficult crystallization, etc., so using sodium hydrosulfide instead of sodium sulfide to leach antimony can effectively reduce production cost, reduce sodium content in high-salinity wastewater from the source, and avoid the disadvantages of using liquid sodium sulfide storage tank, conveying pipeline, etc.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of non-ferrous metallurgy, in particular to a method for leaching antimony from complex antimony-containing materials. BACKGROUND

[0002] Antimony has a sulfur affinity and exists in the form of sulfide in minerals. With the increasing depletion of single antimony sulfide ore resources, complex antimony-containing materials have become important raw materials for preparing antimony metal materials. Antimony is widely used in battery materials, military industry and other fields.

[0003] Industrial antimony is mainly derived from complex antimony-containing materials produced in the process of refining gold and silver from anode mud in copper electrolytic refining process, stibnite and antimony gold ore. The complex antimony-containing material usually contains about 10-25% of antimony, most of which exists in the form of Sb2O3 and Sb2S3, and a small part exists in the form of SbOCl.

[0004] Chinese patent CN 110964904 A discloses a sodium sulfide alkaline leaching and electrowinning antimony process, and step 4 adopts sodium sulfide + caustic soda to leach antimony.

[0005] In the process of leaching antimony in Shixingjun et al. Research on automatic control system for alkali leaching of antimony-containing gold concentrate, NaOH + sodium sulfide process is adopted, and after automatic control of the leaching process, the antimony leaching rate is 93.17%.

[0006] Chinese patent CN 114941078 A discloses a method for inhibiting gold leaching during alkali leaching of antimony-containing gold concentrate, and the leaching reagent in step one is still sodium hydroxide solution + sodium sulfide.

[0007] In the above several antimony leaching cases, alkali solution + sodium sulfide is used to leach antimony, and there is no NaHS + NaOH combined leaching method. In the above cases, there is no pretreatment and impurity removal process, the utilization efficiency of sodium sulfide reagent is low, and the cost is high. SUMMARY

[0008] The purpose of the present application is to provide a method for leaching antimony from complex antimony-containing materials, and the specific steps of the method are as follows:

[0009] Step 1: alkali leaching and arsenic removal process, in order to improve the utilization efficiency of sodium hydrosulfide, the arsenic in the raw material is removed to reduce the consumption of sodium hydrosulfide by arsenic, the liquid-solid ratio (3-6):1 is controlled, a certain amount of alkali is added, the alkalinity of the reaction system is controlled (20-60) g / L, the reaction temperature is controlled (50-95) ℃, and the reaction time is controlled (1-4) hours, after the reaction is completed, the liquid and solid are separated, and the alkali leaching residue is obtained;

[0010] Step 2: Chloride salt reduction acid leaching process, the alkali leaching residue obtained in step 1 is subjected to chloride salt reduction acid leaching, the liquid-solid ratio (3-10):1, the reaction temperature (50-95) DEG C, the acidity (60-150) g / L, the chloride ion concentration (60-150) g / L, the quantitative sulfur dioxide (120-180) kg / t Sb is passed, the reaction time (2-10) h, after the reaction, the liquid-solid separation is carried out, and the reduction acid leaching residue is obtained;

[0011] Step 3: NaHS+NaOH combined antimony leaching process, the reduction acid leaching residue obtained in step 2 is subjected to NaHS+NaOH combined antimony leaching operation, the liquid-solid ratio (3-8):1, the system alkalinity (20-40) g / L, the sodium hydrosulfide concentration is (80-180) g / L, the temperature (80-110) DEG C, the reaction time (1-4) hours;

[0012] Step 4: After the reaction, the liquid-solid separation is carried out, and the high-quality antimony leaching liquid is obtained, which can be used for further recovery of antimony and preparation of antimony related products.

[0013] Preferably, in step 1, step 2 and step 4, the liquid after liquid-solid separation needs to be treated to reach the standard before being discharged.

[0014] Preferably, the NaHS+NaOH combined antimony leaching process is adopted, the solid-liquid separation is smooth, the antimony content of the antimony leaching residue is below 10%, and the antimony leaching rate is as high as 96%.

[0015] Preferably, the weight of the alkali leaching residue in step 1 and the weight of the acid leaching residue in step 2 are obtained by dry weighing.

[0016] Preferably, step 2 is to remove copper and bismuth from the raw material.

[0017] Compared with the prior art, the beneficial effects of the present application are: using sodium hydrosulfide instead of sodium sulfide as the antimony leaching sulfuration reagent can effectively solve the problems of difficult solid-liquid separation and low antimony leaching efficiency in conventional sodium sulfide alkali antimony leaching, and the antimony leaching rate can be increased from about 88% to more than 96%. After pretreatment and impurity removal, the utilization efficiency of sodium hydrosulfide is high, and the consumption of sulfuration reagent is significantly reduced; using sodium hydrosulfide instead of sodium sulfide for antimony leaching can effectively reduce the production cost, reduce the sodium content of high-salinity wastewater from the source, and the storage tank and the conveying pipeline do not need steam heating and insulation, which is easy to industrialize. BRIEF DESCRIPTION OF DRAWINGS

[0018] Figure 1 The process flow chart of the present application. DETAILED DESCRIPTION

[0019] In order to make the objects, technical solutions and advantages of the present application clearer, the present application will be further described in detail below with specific examples. It should be understood that the specific examples described herein are only used to explain the present application and not to limit the present application. Example 1

[0020] A certain amount of copper separation purification slag was taken, the liquid-solid ratio was controlled to be 4:1, the basicity was controlled to be 50 g / L, the reaction temperature was controlled to be 85 ℃, and the stirring time was controlled to be 3 hours. After the reaction was completed, the solid-liquid separation was performed, and the liquid was sent to waste water treatment to obtain alkali leaching slag. The alkali leaching slag was put into a reaction tank, the liquid-solid ratio was controlled to be 6:1, the reaction temperature was controlled to be 80 ℃, the acidity was controlled to be 110 g / L, the chloride ion concentration was controlled to be 90 g / L, 150 kg / t·Sb of sulfur dioxide was introduced, and the reaction time was controlled to be 6 hours. After the reaction was completed, the liquid-solid separation was performed to obtain reduced acid leaching slag 823 g (dry weight) containing 41.75% of antimony, and the reduced acid leaching liquid was further used to recover copper and bismuth therein. The reduced acid leaching slag was subjected to NaHS+NaOH combined antimony leaching operation, the liquid-solid ratio was controlled to be 5:1, the basicity was controlled to be 25 g / L, the sodium hydrosulfide concentration was controlled to be 130 g / L, the temperature was controlled to be 103 ℃, and the reaction time was controlled to be 2.5 hours. After the reaction was completed, the liquid-solid separation was performed to obtain high-quality antimony leaching 3.84 L containing 86.2 g / L of antimony, and the antimony leaching slag contained 7.35% of antimony, which was returned to a bismuth recovery system and used for antimony recovery after bismuth recovery. The antimony leaching rate in the NaHS+NaOH combined leaching process was 96.33%. Example 2

[0021] A certain amount of copper separation purification slag was taken, the liquid-solid ratio was controlled to be 5:1, the basicity was controlled to be 40 g / L, the reaction temperature was controlled to be 75 ℃, and the stirring time was controlled to be 4 hours. After the reaction was completed, the solid-liquid separation was performed, and the liquid was sent to waste water treatment to obtain alkali leaching slag. The alkali leaching slag was put into a reaction tank, the liquid-solid ratio was controlled to be 8:1, the reaction temperature was controlled to be 90 ℃, the acidity was controlled to be 130 g / L, the chloride ion concentration was controlled to be 80 g / L, 120 kg / t·Sb of sulfur dioxide was introduced, and the reaction time was controlled to be 4 hours. After the reaction was completed, the liquid-solid separation was performed to obtain reduced acid leaching slag 769 g (dry weight) containing 38.19% of antimony, and the reduced acid leaching liquid was further used to recover copper and bismuth therein. The reduced acid leaching slag was subjected to NaHS+NaOH combined antimony leaching operation, the liquid-solid ratio was controlled to be 7:1, the basicity was controlled to be 40 g / L, the sodium hydrosulfide concentration was controlled to be 100 g / L, the temperature was controlled to be 95 ℃, and the reaction time was controlled to be 4 hours. After the reaction was completed, the liquid-solid separation was performed to obtain high-quality antimony leaching 5.11 L containing 55.64 g / L of antimony, and the antimony leaching slag contained 5.67% of antimony, which was returned to a bismuth recovery system and used for antimony recovery after bismuth recovery. The antimony leaching rate in the NaHS+NaOH combined leaching process was 96.81%. Example 3

[0022] A certain amount of copper purification slag is taken, and the liquid-solid ratio is controlled to be 6:1, the basicity is controlled to be 30 g / L, the reaction temperature is controlled to be 95 ℃, and the stirring is controlled to be 2 hours. After the reaction is completed, the solid-liquid separation is performed, and the liquid is sent to waste water treatment, so as to obtain the alkali leaching residue. The alkali leaching residue is put into a reaction tank, the liquid-solid ratio is controlled to be 10:1, the reaction temperature is controlled to be 75 ℃, the acidity is controlled to be 80 g / L, the chloride ion concentration is controlled to be 110 g / L, 180 kg / t·Sb of sulfur dioxide is introduced, and the reaction time is controlled to be 10 hours. After the reaction is completed, the liquid-solid separation is performed, so as to obtain 788 g (dry weight) of the reduction acid leaching residue containing 47.34% of antimony, and the copper and bismuth in the reduction acid leaching liquid are further recovered. The reduction acid leaching residue is subjected to the NaHS+NaOH combined antimony leaching operation, the liquid-solid ratio is controlled to be 6:1, the basicity is controlled to be 30 g / L, the sodium hydrosulfide concentration is controlled to be 150 g / L, the temperature is controlled to be 98 ℃, and the reaction time is controlled to be 3 hours. After the reaction is completed, the liquid-solid separation is performed, so as to obtain the high-quality antimony leaching of 4.43 L containing 81.27 g / L of antimony, and the antimony leaching residue contains 8.12% of antimony, which is returned to the bismuth recovery system and is used for antimony recovery after the bismuth is recovered. The antimony leaching rate of the NaHS+NaOH combined leaching process reaches 96.51%.

[0023] The above merely describes the preferred embodiments of the present application, but the protection scope of the present application is not limited to this. Any person skilled in the art can make equivalent replacements or changes to the technical solutions and the inventive concept of the present application within the technical range disclosed by the present application, which should be covered in the protection scope of the present application.

Claims

1. A process for leaching antimony from complex antimony-bearing materials, characterised in that: The method for leaching antimony from the complex antimony-containing material comprises the following steps: Step 1: alkali leaching and arsenic removal process, in order to improve the utilization efficiency of sodium hydrosulfide, arsenic in the raw material is removed to reduce the consumption of sodium hydrosulfide by arsenic, the liquid-solid ratio is controlled to be 3-6:1, a certain amount of alkali is added, the alkalinity of the reaction system is controlled to be 20-60 g / L, the reaction temperature is controlled to be 50-95 ℃, the reaction time is controlled to be 1-4 hours, after the reaction is completed, the liquid and solid are separated, and the alkali leaching residue is obtained; Step 2: chloro salt reduction and acid leaching to remove copper and bismuth process, the alkali leaching residue obtained in step 1 is subjected to chloro salt reduction and acid leaching, the liquid-solid ratio is controlled to be 3-10:1, the reaction temperature is controlled to be 50-95 ℃, the acidity is controlled to be 60-150 g / L, the chloride ion concentration is controlled to be 60-150 g / L, 120-180 kg of sulfur dioxide is quantitatively introduced per ton of Sb, the reaction time is controlled to be 2-10 hours, after the reaction is completed, the liquid and solid are separated, and the reduction and acid leaching residue is obtained; Step 3: NaHS+NaOH combined antimony leaching process, the reduction and acid leaching residue obtained in step 2 is subjected to NaHS+NaOH combined antimony leaching operation, the liquid-solid ratio is controlled to be 3-8:1, the alkalinity of the system is controlled to be 20-40 g / L, the concentration of sodium hydrosulfide is controlled to be 80-180 g / L, the temperature is controlled to be 80-110 ℃, and the reaction time is controlled to be 1-4 hours; Step 4: after the reaction is completed, the liquid and solid are separated, and the leaching antimony liquid with high quality is obtained, which can be used for recovering antimony and preparing antimony related products.

2. The method according to claim 1, characterized in that: In steps 1, 2 and 4, the liquid separated after the liquid-solid separation needs to be treated to meet the standard before being discharged.

3. The method according to claim 1, characterized in that: By adopting the NaHS+NaOH combined antimony leaching process, the liquid and solid are smoothly separated, the antimony content in the antimony leaching residue is less than 10%, and the antimony leaching rate is as high as 96% or more.

4. The method according to claim 1, characterized in that: The weights of the alkali leaching residue in step 1 and the acid leaching residue in step 2 are obtained by dry weighing.

Images