Resourceful treatment method for lead bullion smelting smoke containing indium, germanium, tin and antimony

Abstract

The invention discloses a resourceful treatment method for crude lead smelting smoke containing indium, germanium, tin and antimony, and belongs to the technical field of comprehensive utilization of crude lead smelting smoke. Firstly, the crude lead smelting smoke is pulpified with a crude hydrochloride solution, then sulfuric acid is injected for curing, then dilution leaching is conducted, leaching residues are fed into crude lead smelting ingredients, and the crude lead smelting ingredients are obtained; transferring the leachate into a selective extraction separation system to selectively extract and separate tin, germanium and indium to respectively obtain tin oxide concentrate, germanium oxide concentrate and crude indium, selectively reducing and precipitating cadmium in indium extraction raffinate to obtain sponge cadmium, briquetting and casting to produce crude cadmium, concentrating the cadmium-removed raffinate with a membrane, and promoting cold crystallization by ethanol to separate out zinc sulfate crystals, and evaporating the mother liquor to remove ethanol, regenerating a crude hydrochloride solution, and returning to leach for use. The method comprehensively recovers seven metals including lead, antimony, tin, germanium, indium, cadmium and zinc, is high in separation coefficient, simple and smooth in process, low in investment, high in benefit, relatively good in industrial application value, high in metal leaching rate and recovery rate and low in treatment energy consumption, and basically realizes zero emission of three wastes.

Description

Technical Field

[0001] The present invention relates to a method for resource treatment of crude lead smelting fume, especially a method for resource treatment of crude lead smelting fume containing indium, germanium, tin and antimony, belonging to the technical field of comprehensive utilization of crude lead smelting fume. Background Art

[0002] The composition of crude lead smelting fume is complex, containing various non-ferrous metals and harmful elements, with obvious dual properties, namely resource property and pollution property. To eliminate pollution and turn waste into treasure, an efficient, energy-saving, low-pollution and large-scale treatment method is needed.

[0003] At present, the treatment methods for crude lead smelting fume are mainly divided into pyrometallurgy and hydrometallurgy.

[0004] The pyrometallurgy treatment equipment is relatively simple, and the smelting process flow is relatively short, but the production cycle is long, the working capital occupancy is large, the equipment is large, and after adding the dust collection system, the investment is high, which is easy to cause secondary pollution and the direct metal recovery rate is low.

[0005] The hydrometallurgy treatment has a relatively short production cycle, which is beneficial to the capital turnover, less investment, higher metal recovery rate, no flue gas generation, the lead-containing leaching residue is sent to the lead plant for lead recovery, no waste residue is discharged, which is beneficial to environmental protection.

[0006] Chinese Patent CN104263954 A discloses a method for comprehensive utilization of bottom-blown furnace fume in lead smelting. The fume from the bottom-blown furnace in lead smelting is added to dilute sulfuric acid with a mass concentration of 20% - 50% according to a solid-liquid ratio of 1:3 - 5, and stirred for reaction. After reacting for 1h - 2h, it is filtered. The filtrate is used to recover zinc and cadmium, and the filter residue is added to saturated brine containing hydrochloric acid according to a liquid-solid ratio of 1:2 - 4, heated to 70°C - 80°C, and reacted for 1h - 2h. After the reaction, it is filtered while it is hot, and the filtrate is used to prepare lead oxide products. This method separates lead from zinc and cadmium to prepare lead oxide, and the two-stage leaching is converted in one step, consuming a large amount of acid and alkali and having a high energy consumption.

[0007] Chinese Patent CN113549766A discloses a method for arsenic removal from lead smelting fume and recovery of valuable metals. Chinese Patent CN118880051A discloses a process for generating sponge cadmium by opening the cadmium circuit in lead smelting fume. Both of these methods use sulfuric acid to leach valuable metals, the leaching residue is returned to lead smelting, and the valuable metals including copper, zinc and cadmium are recovered after arsenic removal from the leaching solution. Obviously, the composition of this kind of lead smelting fume is relatively simple, and the recovered are also common heavy metals.

[0008] Some domestic scholars have carried out the recovery of scattered metals from crude lead smelting dust. For example, Gao Zhaoguo, etc. (Experimental study on indium extraction from lead dust containing indium [J]. Rare Metals. Volume 3, Issue 3) formulated an indium extraction process flow of two-stage sulfuric acid leaching, P204 extraction, sulfuric acid washing, hydrochloric acid stripping, and zinc powder replacement through the research and analysis of the properties and characteristics of lead dust containing indium. The test results show that under the conditions of initial leaching acidity of 200 g / L, oxidant dosage of 1.25%, leaching temperature of 95 °C, concentrated acid leaching time of 5 h, and dilute acid leaching time of 2 h, the indium leaching rate is 91.5%; under the conditions of extractant P204 concentration of 15%, phase ratio O / A = 1 / 15, and extraction time of 5 min, the extraction rate is 98%; using 6N hydrochloric acid as the stripping agent, the stripping rate of three-stage countercurrent stripping is 100%; for the zinc powder replacement of indium enriched solution, the replacement rate is greater than 99.7%. Lin Wenjun (Experimental study on comprehensive recovery of germanium and indium from flue dust [D]. Kunming University of Science and Technology, April 2006) used the flue dust from a certain place in Yunnan as the raw material. Based on the analysis of the raw material properties, a process of "leaching - extraction - stripping" for enriching and separating germanium and indium was adopted, and the experimental study on the recovery process of germanium and indium from the flue dust in this place was carried out to explore the conditions for enriching, separating, and efficiently recovering germanium and indium from the flue dust. The experimental study on the conditions for extracting and stripping indium from the sulfuric acid leaching solution was also carried out, and the experimental study on the conditions for extracting and stripping germanium from the indium extraction residue solution was carried out.

[0009] However, for a kind of crude lead smelting dust containing indium, germanium, tin, and antimony, the chemical composition is: indium 0.25% - 0.50%, germanium 0.03% - 0.05%, tin 1.0% - 2.5%, antimony 1.0% - 2.5%, bismuth 0.1% - 0.3%, copper 0.02% - 0.1%, cadmium 3.0% - 7.0%, zinc 2.0% - 5.0%, iron 7.0% - 10.0%, arsenic 5.0% - 10.0%, chlorine 3.0% - 5.0%, lead 15.0% - 25.0%, silver 0.002% - 0.01%, carbon 10.0% - 15.0%, sulfur 1.0% - 3.0%, moisture 0.01% - 5.0%. The valuable metals include indium, germanium, tin, antimony, cadmium, zinc, lead, etc., and the harmful elements include iron, arsenic, chlorine, etc. There are many valuable elements and harmful elements, and they interfere with each other. There is no mature experience for reference in constructing an efficient, energy-saving, low-pollution, and large-scale treatment method. Summary of the Invention

[0010] Aiming at the deficiencies of the existing technology, the purpose of the present invention is to provide a method for efficiently resource-processing crude lead smelting dust containing indium, germanium, tin, and antimony, specifically a new method with high metal leaching rate, high metal recovery rate, low energy consumption, and zero discharge of three wastes.

[0011] To solve the above problems, the technical solution provided by the present invention is as follows: A method for resource treatment of crude lead smelting dust containing indium, germanium, tin and antimony, comprising the following steps: A) Mixed acid leaching: putting the crude lead smelting dust into a crude hydrochloride solution, stirring to form a slurry, injecting concentrated sulfuric acid for ripening reaction, then diluting with the crude hydrochloride solution, and continuously stirring for leaching to obtain a leaching solution and leaching residues, and sending the leaching residues to the crude lead smelting batching; B) Selective extraction and separation: transferring the leaching solution obtained in step A into a selective extraction and separation system, first selectively extracting and separating tin, then selectively extracting and separating germanium, and finally selectively extracting and separating indium to obtain tin oxide concentrate, germanium oxide concentrate, crude indium and indium extraction residue solution respectively; C) Precipitation and crystallization separation: precipitating cadmium from the indium extraction residue solution obtained in step B to obtain sponge cadmium and cadmium-removed residue solution, melting the sponge cadmium into pellets to produce crude cadmium, concentrating the cadmium-removed residue solution by membrane and then promoting crystallization by ethanol to precipitate zinc sulfate crystals and mother liquor, evaporating ethanol from the mother liquor and recycling the ethanol for use in this step, and the ethanol-removed residue solution is the crude hydrochloride solution, which is returned to step A for use.

[0012] The crude lead smelting dust containing indium, germanium, tin and antimony uses sulfuric acid + crude hydrochloride as the leaching agent, which is essentially a mixed acid leaching of sulfuric acid and hydrochloric acid. It can not only make full use of the ability of inorganic acids to dissolve metal oxides, but also make full use of the ability of chloride ions to complex metal ions, synergistically promoting the transfer of metal ions into the leaching solution and improving the metal leaching rate.

[0013] After the crude lead smelting dust containing indium, germanium, tin and antimony is slurried with a crude hydrochloride solution, concentrated sulfuric acid is injected for ripening. Sulfuric acid reacts with metal oxides, releasing a large amount of chemical latent heat, which causes the pulp to be instantaneously heated to increase the temperature and even boil. Such high-temperature and high-acid leaching conditions can further improve the metal leaching rate. On the other hand, the chemical latent heat released by the reaction completely eliminates the need for an external heat source, which is beneficial to reducing the energy consumption of the resource treatment of crude lead smelting dust containing indium, germanium, tin and antimony. Of course, the high metal leaching rate also lays a solid foundation for a high metal recovery rate. By controlling the chloride ion concentration in the crude hydrochloride solution, other metal ions can be selectively leached in the salt-sulfuric acid mixed acid system, while lead remains in the leaching residues in the form of insoluble lead sulfate precipitate and is sent to the crude lead smelting batching. The valuable metals in the leaching solution are separated by selective extraction or precipitation crystallization methods, with high separation coefficients and high metal recovery rates.

[0014] It should be noted that the order of selective extraction and separation of tin, germanium and indium cannot be disrupted. The traditional methods of co-extracting indium and tin and total extraction of indium and germanium are not applicable to the mixed acid leaching solution system of the present invention. The indium extraction rate is low under high acid, and the germanium extraction separation coefficient is low under low acid. There is no feasible solution for the extraction and separation of tin and germanium.

[0015] The cadmium-removed residual liquid is treated by membrane concentration + ethanol-induced cooling crystallization method, which not only realizes the recovery of zinc in the form of zinc sulfate crystals, but also realizes the preliminary separation of chloride ions and sulfate ions. By evaporating ethanol instead of water, the solubility of zinc sulfate in the alcohol-water solution is relatively low, and the evaporation enthalpy of ethanol is relatively low, which is conducive to improving the recovery rate of zinc and reducing the energy consumption for treating crude lead dust. The waste residues generated during the process can all be transferred to the crude lead smelting batching, the waste water generated can all be incorporated into the crude hydrochloride solution and returned to leaching, and the waste gas can be absorbed by wet spray, basically achieving zero discharge of the three wastes.

[0016] To ensure the stable operation of the selective extraction system and realize the separation of tin and antimony, the preferred solution is that before the leaching solution obtained in step A is transferred to the selective extraction system, reduced iron powder is added, stirred and reacted to remove antimony to obtain spongy antimony and antimony-removed solution. The antimony-removed solution is then transferred to the selective extraction system, and the spongy antimony is sent to the antimony smelting batching.

[0017] The quality of the reduced iron powder has a great influence on the reduction of antimony, which not only affects the quality of spongy antimony, but also affects the dosage of the reduced iron powder. Further optimization is that the mass percentage of metallic iron in the reduced iron powder used is 88.0% - 95.0%, the particle size is ≤0.178mm, ensuring that the mass percentage of antimony in the spongy antimony is ≥45%, and the dosage of the reduced iron powder is 1.5 - 1.8 times the amount of metallic antimony.

[0018] In a further optimized implementation plan, the temperature of the above-mentioned stirring reaction for antimony removal is 40°C - 50°C, and the reaction time is 45min - 60min. If the temperature is too low, the reaction is incomplete; if the temperature is too high, the arsenic content in the spongy antimony is relatively high, which is not conducive to the separation of arsenic and antimony.

[0019] To ensure the leaching rate and recovery rate of metals, in the preferred method, before the leaching residue in step A is sent to the crude lead smelting batching, it is slurried with the crude hydrochloride solution and stirred and washed twice. The washing water produced is combined with the crude hydrochloride solution and returned to this step for use to avoid the entrainment and loss of metal ions transferred into the solution.

[0020] The mixed acid leaching solution of the crude lead smelting dust containing indium, germanium, tin and antimony contains 100g / L - 120g / L of free sulfuric acid and 65g / L - 70g / L of chloride ions, and the extraction rate of indium in this system is relatively low. Before selectively extracting indium in step B, the preferred solution is to add a neutralizing agent to adjust the free sulfuric acid content of the leaching solution to 25.0g / L - 35.0g / L, which not only ensures the selective extraction and separation of indium from other metal ions, but also ensures its relatively high extraction rate.

[0021] The above-mentioned neutralizing agent is further preferably zinc-cadmium slag dust, including the matured copper-cadmium slag in hydrometallurgical zinc smelting, blue powder in pyrometallurgical zinc smelting, and artificially synthesized zinc-cadmium carbonate slag. It can not only increase the concentration of metal cadmium ions in the leaching solution, create conditions for the efficient recovery of cadmium, avoid introducing other metal ions, but also make full use of the free sulfuric acid in the leaching solution.

[0022] To ensure the safety and stability of cadmium precipitation separation, in the preferred solution, before precipitating cadmium from the indium extraction residue in step C, hydrogen peroxide and a neutralizing agent are added to react to remove iron and arsenic, and the pH of the indium extraction residue is adjusted to 5.0 - 5.4, the total iron ion content is ≤ 0.02 g / L, and the total arsenic ion content is ≤ 0.001 g / L. The neutralizing agent is preferably quicklime powder, which is beneficial to removing surplus sulfate and fluoride ions, ensuring the stable operation of the system. At the same time, using the reaction latent heat of quicklime can avoid external heat sources and reduce energy consumption.

[0023] The crude lead smelting dust in step A is the dust collected from bottom-blowing, side-blowing or top-blowing crude lead smelting, containing 0.25% - 0.50% indium, 0.03% - 0.05% germanium, 1.0% - 2.5% tin, and 1.0% - 2.5% antimony. It is a type of crude lead smelting dust with a relatively high enrichment of rare and dispersed metals, having good value for comprehensive resource utilization.

[0024] Generally, in step B, the organic phase for selectively extracting tin has a composition of 40% (by volume) E6040 extractant - 10% P204 extractant - 50% solvent oil 260#; the organic phase for selectively extracting germanium has a composition of 10% (by volume) E356 extractant - 15% P204 extractant - 75% solvent oil 260#; the organic phase for selectively extracting indium has a composition of 30% (by volume) P204 extractant - 70% solvent oil 260#. The E6040 extractant is a phosphate ester composite extractant, the P204 extractant is diisooctyl phosphoric acid, and the E356 extractant is an isomeric alkyl hydroxamic acid composite extractant.

[0025] Compared with the prior art, the above technical solutions of the present invention have the following beneficial technical effects: A high-efficiency resource treatment method for crude lead smelting dust containing indium, germanium, tin, and antimony is provided, comprehensively recovering seven metals including lead, antimony, tin, germanium, indium, cadmium, and zinc. The process is simple and smooth, with low investment and high efficiency, having good industrial application value.

[0026] Using mixed acid leaching and coupling with concentrated acid aging technology, making use of the ability of inorganic acids to dissolve metal oxides, the ability of chloride ions to complex metal ions, and the reaction latent heat of chemical reactions, not only improves the metal leaching rate and ensures the metal recovery rate, but also reduces the energy consumption of the resource treatment of crude lead smelting dust containing indium, germanium, tin, and antimony.

[0027] Using selective reduction precipitation separation of antimony and cadmium and selective extraction separation of tin, germanium, and indium, the metal separation coefficient is high and the metal recovery rate is high.

[0028] Using membrane concentration and ethanol-induced cooling crystallization to recover zinc in the form of zinc sulfate crystals, and separating chloride ions and sulfate radicals, with high zinc recovery rate and low energy consumption.

[0029] In the resource treatment of crude lead smelting dust containing indium, germanium, tin and antimony, the waste residues generated during the process can all be transferred to the crude lead smelting batching, the waste water generated can all be incorporated into the crude hydrochloride solution and returned to leaching, and the waste gas can be absorbed by wet spraying, basically achieving zero discharge of the three wastes. Brief Description of the Drawings

[0030] Figure 1 It is a principle process flow chart of a resource treatment method for crude lead smelting dust containing indium, germanium, tin and antimony. Detailed Embodiments

[0031] To make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below in combination with the specific embodiments and with reference to the accompanying drawings. It should be understood that these descriptions are exemplary and are not intended to limit the scope of the present invention. In addition, in the following description, the description of well-known technologies is omitted to avoid unnecessarily confusing the concepts of the present invention.

[0032] The components of crude lead smelting dust are complex, rich in various valuable elements and harmful elements, and have the dual attributes of typical resourcefulness and pollution. Constructing an efficient, energy-saving, low-pollution and large-scale treatment method is an urgent need in the industry. Compared with pyrometallurgical treatment, hydrometallurgical treatment has obvious environmental and economic benefits. For a kind of crude lead smelting dust containing indium, germanium, tin and antimony, there is currently no available treatment method for reference. The inventor discloses an efficient resource treatment method, including the following steps: A) Mixed acid leaching: Put the crude lead smelting dust into the crude hydrochloride solution, stir and pulp, inject concentrated sulfuric acid for aging reaction, then dilute with the crude hydrochloride solution, continue to stir and leach to obtain a leaching solution and leaching residues, and send the leaching residues to the crude lead smelting batching; B) Selective extraction and separation: The leaching solution obtained in step A is transferred to a selective extraction and separation system. First, tin is selectively extracted and separated, then germanium is selectively extracted and separated, and finally indium is selectively extracted and separated to obtain tin oxide concentrate, germanium oxide concentrate and crude indium, as well as indium extraction residual liquid; C) Precipitation and crystallization separation: The indium extraction residual liquid obtained in step B precipitates cadmium to obtain sponge cadmium and cadmium-removed residual liquid. The sponge cadmium is pressed into pellets and melted and cast to produce crude cadmium. The cadmium-removed residual liquid is membrane-concentrated and then ethanol is used to promote cold crystallization to precipitate zinc sulfate crystals and mother liquor. The mother liquor is evaporated to remove ethanol, and the ethanol is recovered and returned to this step for use. The ethanol-removed residual liquid is the crude hydrochloride solution and is returned to step A for use.

[0033] To ensure the stable operation of the selective extraction system and achieve the separation of tin and antimony, the preferred solution is that before the leaching solution obtained in step A is transferred to the selective extraction system, reduction iron powder is added, stirred and reacted to remove antimony to obtain sponge antimony and antimony-removed liquid, and the antimony-removed liquid is then transferred to the selective extraction system, and the sponge antimony is sent to the antimony smelting batching.

[0034] To ensure the leaching rate and recovery rate of metals, in the preferred method, before the leaching residue described in step A is sent to the crude lead smelting burdening, it is slurried with concentrated hydrochloric acid salt solution and stirred and washed twice. The washing water produced is combined with the crude hydrochloric acid salt solution and returned to this step for use to avoid the entrainment and loss of metal ions transferred into the solution.

[0035] The mixed acid leaching solution of crude lead smelting soot containing indium, germanium, tin, and antimony contains 100 g / L to 120 g / L of free sulfuric acid and 65 g / L to 70 g / L of chloride ions. The extraction rate of indium metal in this system is relatively low. Before selectively extracting indium in step B, in the preferred scheme, a neutralizing agent is added to adjust the free sulfuric acid content of the leaching solution to 25.0 g / L to 35.0 g / L, which not only ensures the selective extraction and separation of indium from other metal ions but also ensures its relatively high extraction rate.

[0036] To ensure the safety and stability of cadmium precipitation separation, in the preferred scheme, before cadmium is precipitated from the indium extraction residue in step C, hydrogen peroxide and a neutralizing agent are added to react to remove iron and arsenic, and the pH of the indium extraction residue is adjusted to 5.0 to 5.4, the total iron ion content is ≤ 0.02 g / L, and the total arsenic ion content is ≤ 0.001 g / L. The neutralizing agent is preferably quicklime powder, which is conducive to removing the surplus sulfate and fluoride ions, ensuring the stable operation of the system, and at the same time using the reaction latent heat of quicklime to avoid external heat sources and reduce energy consumption.

[0037] The present invention comprehensively recovers seven metals including lead, antimony, tin, germanium, indium, cadmium, and zinc. The process is simple and smooth, with low investment and high efficiency, having good industrial application value. The leaching rate and recovery rate of metals are high, the energy consumption is low, and basically zero emissions of the three wastes are achieved.

[0038] The following lists some embodiments to further illustrate the present invention, which is convenient for those skilled in the art to implement and realize.

[0039] The crude lead smelting soot containing indium, germanium, tin, and antimony in the embodiment is the crude lead smelting soot from a certain area in Yunnan Province. Its chemical composition is in mass percentage: indium 0.25% - 0.50%, germanium 0.03% - 0.05%, tin 1.0% - 2.5%, antimony 1.0% - 2.5%, bismuth 0.1% - 0.3%, copper 0.02% - 0.1%, cadmium 3.0% - 7.0%, zinc 2.0% - 5.0%, iron 7.0% - 10.0%, arsenic 5.0% - 10.0%, chlorine 3.0% - 5.0%, lead 15.0% - 25.0%, silver 0.002% - 0.01%, carbon 10.0% - 15.0%, sulfur 1.0% - 3.0%, moisture 0.01% - 5.0%. The valuable metals include indium, germanium, tin, antimony, cadmium, zinc, lead, etc., and the harmful elements include iron, arsenic, chlorine, etc. There are many valuable elements and harmful elements, and they interfere with each other.

[0040] In the examples, the extractants E6040, E356, P204 and solvent oil 260# in the organic phase of the selective extraction system were all provided by Chuxiong Jiuhang Economic and Trade Co., Ltd. in Yunnan Province. Among them, E6040 is a phosphate ester composite extractant, P204 is diisooctyl phosphoric acid, and E356 is an isomeric alkyl hydroxamic acid composite extractant. The organic phase composition for selectively extracting tin is 40% E6040 - 10% P204 – 50% solvent oil 260# by volume percentage, the organic phase composition for selectively extracting germanium is 10% E356 - 15% P204 – 75% solvent oil 260# by volume percentage, and the organic phase composition for selectively extracting indium is 30% P204 – 70% solvent oil 260# by volume percentage. It should be noted that the order of selectively extracting and separating tin, germanium, and indium cannot be disrupted. The traditional methods of co-extracting indium and tin and fully extracting indium and germanium are not applicable to the mixed acid leaching solution system of the present invention. The extraction rate of indium is low under high acid conditions, and the separation coefficient of germanium is low under low acid conditions. There is no feasible solution for the extraction and separation of tin and germanium. Example 1

[0041] Inject 15.0 m 3 of fresh water, add 1250.0 kg of industrial salt under stirring, and dissolve it completely to obtain a crude hydrochloride solution containing 50.0 g / L of chloride ions. Add 30 t of crude lead smelting dust, containing 0.25% indium, 0.05% germanium, 2.5% tin, 1.0% antimony, 3.0% cadmium, 5.0% zinc, 25.0% lead, 7.0% iron, 10.0% arsenic, 5.0% chlorine, and 5.0% moisture, and stir to complete pulping. Inject 9.0 t of 98% industrial concentrated sulfuric acid, and continue stirring for concentrated acid ripening. The sulfuric acid reacts with the crude lead dust, releasing a large amount of chemical latent heat, and the pulp temperature naturally rises to 85°C - 95°C. Stir thoroughly for 16.0 h to complete the concentrated acid ripening. Supplement 75 m 3 of the crude hydrochloride solution containing 50 g / L of chloride ions, continue stirring for leaching for 2.5 h, and the pulp temperature naturally drops to 40°C - 50°C. Add 10.0 kg of 25 g / L bone glue solution and stir for 0.5 hours. The pulp settles well, and after pressure filtration, 83 m 3 of leaching solution and 30 t of wet leaching residue are obtained.

[0042] The leaching solution was sent for sample testing, containing indium 0.76 g / L, germanium 0.15 g / L, tin 7.43 g / L, antimony 3.01 g / L, cadmium 9.71 g / L, zinc 15.66 g / L, lead 1.45 g / L, iron 18.32 g / L, arsenic 22.95 g / L, chlorine 71.38 g / L, and free sulfuric acid 100 g / L. The metal leaching rate was calculated according to the formula: leaching rate % = amount of metal in leaching solution ÷ amount of metal in feedstock × 100%. The leaching rates of indium, germanium, tin, antimony, cadmium, zinc, lead, iron, arsenic, and chlorine were 88.53%, 87.37%, 86.55%, 87.66%, 94.26%, 91.21%, 1.69%, 76.22%, 66.83%, and 95.36% respectively.

[0043] The leaching residue was treated with 60 m 3 A crude hydrochloride solution containing 15 g / L of chloride ions was stirred at room temperature for pulping and washed countercurrently 2 times, each time for 2.0 h - 2.5 h, and then pressure filtered to obtain the washing solution and 30 t of lead sulfate mud residue.

[0044] The lead sulfate mud residue was sampled and tested, containing indium 0.020%, germanium 0.0067%, tin 0.42%, antimony 0.16%, cadmium 0.18%, zinc 0.48%, lead 26.14%, and moisture 24.5%. It was sent for batching in crude lead smelting. The metal leaching rate was calculated according to the formula: leaching rate % = (amount of metal in feedstock - amount of metal in leaching residue) ÷ amount of metal in feedstock × 100%. The leaching rates of indium, germanium, tin, antimony, cadmium, and zinc were 93.53%, 89.37%, 86.57%, 87.68%, 95.30%, and 92.28% respectively. Example 2

[0045] Take 40 m of the leaching solution from Example 1 3 , while keeping the temperature at 50 °C, weigh 180.6 kg of reduced iron powder according to 1.5 times the amount of antimony metal. The metal iron content of the reduced iron powder is 95.0%, all passing through a 80 - mesh standard sieve with a particle size ≤ 0.178 mm, and evenly added to the leaching solution through a hopper. Stir and react fully to remove antimony. After 45 min, stop stirring and pressure filter to obtain 263.0 kg of sponge antimony and 40 m 3 Antimony - removed solution.

[0046] The sponge antimony contains antimony 52.2%, arsenic 9.76%, tin 0.05%, indium 0.01%, germanium 0.002%, iron 23.5%, and moisture 14.5%. The metal recovery rate was calculated according to the formula: recovery rate % = amount of metal in product ÷ amount of metal in solution × 100%. The antimony recovery rate was 97.5%. Example 3

[0047] Take 40 m of the leaching solution from Example 1 3, while the temperature is maintained at 40℃, weigh 216.7kg of reduced iron powder according to 1.8 times the amount of antimony metal, the reduced iron powder has a metallic iron content of 88.0.0%, all of which pass through an 80-mesh standard sieve, with a particle size of ≤0.178mm, and add it evenly to the leaching solution through a hopper, stir it thoroughly to react and remove antimony, stop stirring after 60 minutes, filter by pressure, and obtain 296.6kg of sponge antimony and 40m 3 Antimony removal liquid.

[0048] The sponge antimony contains 45.8% antimony, 11.5% arsenic, 0.05% tin, 0.01% indium, 0.002% germanium, 33.5% iron and 14.2% water. The metal recovery rate is calculated according to the formula: recovery rate % = metal content in the product ÷ metal content in the solution × 100%, and the antimony recovery rate is 96.8%. Example 4

[0049] The antimony removal solutions of Example 2 and Example 3 were combined to contain 0.76 g / L indium, 0.15 g / L germanium, 7.43 g / L tin, 0.086 g / L antimony, 9.71 g / L cadmium, 15.66 g / L zinc, 21.12 g / L iron, 22.31 g / L arsenic, 71.38 g / L chlorine, and 98.57 g / L free sulfuric acid.

[0050] Take the above 80 m 3 The temperature of the antimony-removing liquid naturally drops to 30℃~35℃, and the organic phase for selective tin extraction is used to selectively extract tin. The residual tin extract contains 0.76g / L indium, 0.15g / L germanium, 0.0088g / L tin, 0.0032g / L antimony, 9.71g / L cadmium, 15.66g / L zinc, 21.12g / L iron, 22.31g / L arsenic, 71.38g / L chlorine, and 98.57g / L free sulfuric acid.

[0051] The tin-containing organic phase was washed, stripped, precipitated and dried to obtain 975.2 kg of tin oxide concentrate. The tin oxide concentrate contained 61.20% tin, 0.68% antimony, 9.76% arsenic, 0.0006% germanium, 0.001% indium and 0.53% water. The metal recovery rate was calculated according to the formula: recovery rate % = metal content in the product ÷ metal content in the solution × 100%, and the tin recovery rate was 99.88%.

[0052] The above-mentioned tin extraction residual liquid is naturally cooled to 25°C-30°C, and germanium is selectively extracted by using an organic phase for selective extraction of germanium. The germanium extraction residual liquid contains 0.76g / L indium, 0.004g / L germanium, 9.71g / L cadmium, 15.66g / L zinc, 20.88g / L iron, 22.31g / L arsenic, 71.38g / L chlorine, and 99.77g / L free sulfuric acid.

[0053] The negative germanium organic phase is washed, stripped, germanium precipitated, and dried to obtain 33.14 kg of germanium oxide concentrate. The germanium oxide concentrate contains 35.48% germanium and 0.68% moisture. The metal recovery rate is calculated according to the formula: Recovery rate % = Amount of metal in product ÷ Amount of metal in solution × 100%. The germanium recovery rate is 97.3%. Example 5

[0054] Take 40 m of the germanium extraction residue liquid in Example 4 3 , add 4800 kg of synthetic zinc-cadmium carbonate slag, which contains 25.8% zinc, 38.8% cadmium, and 25.6% moisture by mass percentage. Stir and react to reduce the acid content. React fully for 2.0 h, then filter press to obtain 500 kg of wet acid-reduced slag and 40 m 3 acid-reduced liquid. The acid-reduced liquid contains 0.75 g / L indium, 44.35 g / L cadmium, 38.7 g / L zinc, 20.88 g / L iron, 22.31 g / L arsenic, 71.38 g / L chlorine, and 35.0 g / L free sulfuric acid.

[0055] Use selective extraction for indium. The indium organic phase selectively extracts indium. The indium extraction residue liquid contains 0.015 g / L indium, 44.35 g / L cadmium, 38.7 g / L zinc, 20.88 g / L iron, 22.31 g / L arsenic, 71.38 g / L chlorine, and 35.0 g / L free sulfuric acid. The negative indium organic phase is washed, stripped, purified, displaced, briquetted, and melted to obtain 29.2 kg of crude indium. The crude indium contains 99.21% indium. The metal recovery rate is calculated according to the formula: Recovery rate % = Amount of metal in product ÷ Amount of metal in solution × 100%. The indium recovery rate is 96.56%. Example 6

[0056] Take 40 m of the germanium extraction residue liquid in Example 4 3 , add 4950 kg of synthetic blue powder in pyrometallurgical zinc smelting, which contains 15.8% zinc, 42.5% cadmium, and 0.5% moisture by mass percentage. Stir and react to reduce the acid content. React fully for 2.5 h, then filter press to obtain 480 kg of wet acid-reduced slag and 40 m 3 acid-reduced liquid. The acid-reduced liquid contains 0.75 g / L indium, 62.04 g / L cadmium, 35.11 g / L zinc, 20.88 g / L iron, 22.31 g / L arsenic, 71.38 g / L chlorine, and 25.0 g / L free sulfuric acid.

[0057] Indium is selectively extracted by the organic phase. The indium-containing residue after indium extraction contains 0.007 g / L of indium, 62.04 g / L of cadmium, 35.11 g / L of zinc, 20.88 g / L of iron, 22.31 g / L of arsenic, 71.38 g / L of chlorine, and 25.0 g / L of free sulfuric acid. The indium-loaded organic phase is washed, stripped, purified, displaced, pelletized, and melted to obtain 29.7 kg of crude indium. The crude indium contains 99.53% of indium. The metal recovery rate is calculated according to the formula: Recovery rate (%) = (amount of metal in the product ÷ amount of metal in the solution) × 100%. The indium recovery rate is 98.53%. Example 7

[0058] The indium extraction residues of Example 5 and Example 6 are combined, containing 53.2 g / L of cadmium, 36.9 g / L of zinc, 20.88 g / L of iron, 22.31 g / L of arsenic, 71.38 g / L of chlorine, and 30.0 g / L of free sulfuric acid.

[0059] Take 80 m of all the indium extraction residues 3 , start stirring, add hydrogen peroxide and a neutralizing agent to react to remove iron and arsenic, adjust the pH of the indium extraction residue to 5.2 - 5.4, the total iron ion content ≤ 0.02 g / L, and the total arsenic ion content ≤ 0.001 g / L. The neutralizing agent used is quicklime powder. The reaction is exothermic, so avoid external heating sources for heating. After the reaction is completed, 5.0 tons of wet iron-arsenic slag and 80 m 3 iron-removing solution are obtained. The iron-removing solution contains 51.8 g / L of cadmium, 31.3 g / L of zinc, and 68.35 g / L of chlorine.

[0060] First, adjust the iron-removing solution to pH = 3.0 with sulfuric acid, then weigh metal zinc powder at 0.60 times the amount of cadmium, and uniformly add it into the stirring iron-removing solution through a hopper to selectively precipitate cadmium at room temperature. The metal zinc powder in the hopper is added for 20 min - 25 min. After the addition is completed, react for another 20 min - 25 min, stop stirring, and settle and separate to obtain sponge cadmium and 80 m 3 cadmium-removing solution, containing 0.1 g / L of cadmium, 60.0 g / L of zinc, and 68.35 g / L of chlorine. The sponge cadmium is pelletized and melted to obtain 4130 kg of crude cadmium, containing 95.46% of cadmium and 4.4% of zinc. The metal recovery rate is calculated according to the formula: Recovery rate (%) = (amount of metal in the product ÷ amount of metal in the solution) × 100%. The cadmium recovery rate is 95.32%.

[0061] It should be noted that in this example, the cadmium-removing solution contains 60.0 g / L of zinc, 68.35 g / L of chlorine, and pH 5.4. Usually, an alkaline precipitant such as sodium carbonate is used to precipitate zinc to obtain crude zinc carbonate and mother liquor, and the mother liquor is desalted by triple-effect evaporation to produce crude salt, with relatively high energy consumption. Example 8

[0062] Take 80 m of the cadmium-removing solution in Example 7 3, containing 60.0 g / L of zinc, 68.35 g / L of chlorine, and a pH of 5.4. First, a three-stage and one-pass concentration is carried out using a reverse osmosis membrane, and 41.6 m 3 of permeate water and 38.4 m 3 of concentrate are collected, accounting for 52.0% and 48.0% respectively by volume percentage. The permeate water contains 0.02 g / L of zinc and 3.3 g / L of chlorine, and the concentrate contains 125.0 g / L of zinc and 138.8 g / L of chloride ions.

[0063] 38.4 m 3 of ethanol is added to the aforementioned concentrate. Ethanol accounts for 50% by volume percentage. The temperature is lowered to 5°C - 8°C while stirring, and crystallization is carried out for 2.0 h - 3.0 h. After centrifugal separation, 23.5 t of zinc sulfate crystals and 66.5 m 3 of mother liquor are obtained. The zinc sulfate crystals contain 20.1% of zinc and 0.47% of chlorine, and the mother liquor contains 1.15 g / L of zinc and 78.5 g / L of chloride ions. The metal recovery rate is calculated according to the formula: Recovery rate (%) = Metal amount in the product ÷ Metal amount in the solution × 100%. The zinc recovery rate in ethanol-induced cooling crystallization is 98.40%.

[0064] The aforementioned mother liquor is concentrated to recover ethanol and returned to ethanol-induced cooling crystallization, obtaining 28 m 3 of ethanol-evaporated residual liquid, containing 186.3 g / L of chloride ions, which is a crude hydrochloride solution. Example 9

[0065] The 28 m 3 of ethanol-evaporated residual liquid in Example 8 contains 186.3 g / L of chloride ions, and the 41.6 m 3 of permeate water contains 3.3 g / L of chlorine. The 60 m 3 of washing liquid in Example 1 contains 15 g / L of chloride ions. The cumulative volume is 129.6 m 3 , and they are combined into a crude hydrochloride solution containing 48.25 g / L of chloride ions.

[0066] 15.0 m 3 of the crude hydrochloride solution obtained after the aforementioned combination is injected, containing 48.25 g / L of chloride ions. 30 t of crude lead smelting dust is added, containing 0.50% of indium, 0.03% of germanium, 1.0% of tin, 2.5% of antimony, 7.0% of cadmium, 2.0% of zinc, 15.0% of lead, 10.0% of iron, 5.0% of arsenic, 3.0% of chlorine, and 0.01% of moisture. Stir to completely pulp. 9.0 t of 98% industrial sulfuric acid is injected, and continuous stirring is carried out for concentrated acid aging. The sulfuric acid reacts with the crude lead dust, releasing a large amount of chemical latent heat, and the pulp naturally heats up to 85°C - 95°C. Stir thoroughly for 8.0 h, and the concentrated acid aging is completed. 75 m 3, continue stirring and leaching for 2.5 h. The temperature of the pulp naturally drops to 40 °C - 50 °C. Add 10.0 kg of 25 g / L bone glue solution and stir for 0.5 h. The pulp settles well, then filter press to obtain 80 m 3 leachate and 31 t of wet leaching residue.

[0067] Send the leachate for sample testing. It contains indium 1.65 g / L, germanium 0.098 g / L, tin 3.21 g / L, antimony 8.22 g / L, cadmium 24.7 g / L, zinc 6.84 g / L, lead 0.89 g / L, iron 28.32 g / L, arsenic 12.5 g / L, chlorine 65.02 g / L, and free sulfuric acid 110 g / L. Calculate the metal leaching rate according to the formula: Leaching rate % = amount of metal in leachate ÷ amount of metal in feed × 100%. The leaching rates of indium, germanium, tin, antimony, cadmium, zinc, lead, iron, arsenic, and chlorine are 88.0%, 87.11%, 85.6%, 87.68%, 94.1%, 91.2%, 1.58%, 75.52%, 66.67%, and 95.46% respectively.

[0068] For the leaching residue, use the crude hydrochloride solution obtained by the aforementioned combination, add fresh water to make it 60 m 3 , with chloride ion content of 31.84 g / L. Stir and slurry at room temperature and wash countercurrently for 2 times, each time for 2.0 h - 2.5 h. Then filter press to obtain washing liquid and 32 t of lead sulfate mud residue.

[0069] Take a sample of the lead sulfate mud residue for inspection. It contains indium 0.040%, germanium 0.0040%, tin 0.17%, antimony 0.39%, cadmium 0.41%, zinc 0.19%, lead 18.58%, and moisture 25.5%. Send it for batching in crude lead smelting. Calculate the metal leaching rate according to the formula: Leaching rate % = (amount of metal in feed - amount of metal in leaching residue) ÷ amount of metal in feed × 100%. The leaching rates of indium, germanium, tin, antimony, cadmium, and zinc are 93.66%, 89.35%, 86.58%, 87.68%, 95.30%, and 92.38% respectively. Comparative Example 1

[0070] Take 300 g of crude lead smelting dust, containing 0.50% indium, 0.03% germanium, 1.0% tin, 2.5% antimony, 7.0% cadmium, 2.0% zinc, 15.0% lead, 10.0% iron, 5.0% arsenic, 3.0% chlorine, and 0.01% moisture. Add 150 ml of water and stir to completely pulpify. Inject 50.0 mL (about 90 g) of 98% industrial sulfuric acid, continue stirring for thick acid aging. The sulfuric acid reacts with the crude lead smelting dust, releasing a large amount of chemical latent heat, and the pulp temperature naturally rises to 85 °C - 95 °C. Stir thoroughly for 24.0 h to complete the thick acid aging. Dilute with 750 mL of water, continue stirring for leaching for 2.5 h, and the pulp temperature naturally drops to 20 °C - 30 °C. Add 10.0 mL of 25 g / L bone glue solution and stir for 0.5 hour. The pulp settles well, and then filter to obtain 800 mL of leaching solution and 310 g of wet leaching residue.

[0071] Send the leaching solution for sample testing, containing 1.27 g / L indium, 0.080 g / L germanium, 2.46 g / L tin, 2.60 g / L antimony, 23.12 g / L cadmium, 6.39 g / L zinc, 0.36 g / L lead, 24.93 g / L iron, 10.66 g / L arsenic, 10.7 g / L chlorine, and 110 g / L free sulfuric acid. Calculate the metal leaching rate according to the formula: Leaching rate % = amount of metal in leaching solution ÷ amount of metal in feedstock × 100%. The leaching rates of indium, germanium, tin, antimony, cadmium, zinc, lead, iron, arsenic, and chlorine are 68.0%, 71.11%, 65.6%, 27.68%, 88.1%, 85.2%, 0.65%, 66.48%, 56.85%, and 95.16% respectively.

[0072] It can be seen from the comparison with Comparative Example 1 that in Example 1 and Example 9, "mixed acid leaching of crude hydrochloride and concentrated sulfuric acid" was used, which significantly improved the metal leaching rate compared with "single sulfuric acid leaching" in Comparative Example 1, laying a foundation for subsequent metal recovery. Comparative Example 2

[0073] Carry out a comparative test according to the traditional extraction sequence of "tin precipitation - purification - indium extraction - germanium extraction" as follows: Take 15.0 L of the leaching solution from Example 1, containing 0.76 g / L indium, 0.15 g / L germanium, 7.43 g / L tin, 3.01 g / L antimony, 9.71 g / L cadmium, 15.66 g / L zinc, 1.45 g / L lead, 18.32 g / L iron, 22.95 g / L arsenic, 71.38 g / L chlorine, and 100 g / L free sulfuric acid.

[0074] First, add 420 g of industrial magnesium oxide to the leaching solution to adjust the free sulfuric acid in the leaching solution to 30.0 g / L. At the same time, inject 150 mL of 27.5% industrial hydrogen peroxide solution and stir for oxidative hydrolysis and tin precipitation at room temperature for 40 min, then filter to obtain tin mud residue and tin-removed solution.

[0075] The stannum-removing solution contains 0.68 g / L of indium, 0.11 g / L of germanium, 0.058 g / L of stannum, 1.25 g / L of antimony, 9.24 g / L of cadmium, 14.26 g / L of zinc, 0.15 g / L of lead, 16.88 g / L of iron, 17.44 g / L of arsenic, 69.42 g / L of chlorine, and 30.0 g / L of free sulfuric acid. Calculate the metal precipitation rate according to the formula: precipitation rate % = (metal amount in the solution before treatment - metal amount in the solution after treatment) ÷ metal amount in the solution before treatment × 100%. The precipitation rates of indium, germanium, stannum, antimony, cadmium, zinc, lead, iron, arsenic, and chlorine are 10.52%, 26.67%, 99.22%, 58.47%, 4.84%, 8.94%, 89.66%, 7.86%, 24.01%, and 2.74% respectively.

[0076] Then, add 100 g of reduced iron powder to the stannum-removing solution, stir and purify at room temperature for 60 min, and filter to obtain purification slag and purified solution.

[0077] The purified solution contains 0.66 g / L of indium, 0.10 g / L of germanium, 0.057 g / L of stannum, 0.035 g / L of antimony, 9.23 g / L of cadmium, 14.24 g / L of zinc, 0.056 g / L of lead, 23.51 g / L of iron, 15.65 g / L of arsenic, 69.42 g / L of chlorine, and 28.68 g / L of free sulfuric acid. Calculate the metal precipitation rate according to the formula: precipitation rate % = (metal amount in the solution before treatment - metal amount in the solution after treatment) ÷ metal amount in the solution before treatment × 100%. The precipitation rates of indium, germanium, stannum, antimony, cadmium, and zinc are 2.94%, 9.09%, 1.72%, 97.2%, 0.11%, and 0.14% respectively.

[0078] Using the purified solution as the feed liquid, selectively extract indium with 30% P204 extractant - 70% solvent oil 260# as the organic phase. The indium-containing residue after extraction contains 0.008 g / L of indium, 0.10 g / L of germanium, 0.037 g / L of stannum, 0.033 g / L of antimony, 9.11 g / L of cadmium, 14.19 g / L of zinc, 23.35 g / L of iron, 15.55 g / L of arsenic, 69.42 g / L of chlorine, and 28.68 g / L of free sulfuric acid. Calculate the metal extraction rate according to the formula: extraction rate % = (metal amount in the solution before treatment - metal amount in the solution after treatment) ÷ metal amount in the solution before treatment × 100%. The extraction rates of indium, germanium, stannum, antimony, cadmium, and zinc are 98.79%, 0%, 35.09%, 5.71%, 1.30%, and 0.35% respectively.

[0079] Using indium extraction residue as the feed solution, and 10% E356 extractant - 15% P204 extractant - 70% solvent oil 260# as the organic phase to selectively extract germanium. The indium extraction residue contains 0.007 g / L of indium, 0.003 g / L of germanium, 0.004 g / L of tin, 0.005 g / L of antimony, 9.08 g / L of cadmium, 14.16 g / L of zinc, 22.22 g / L of iron, 15.53 g / L of arsenic, 69.32 g / L of chlorine, and 28.76 g / L of free sulfuric acid. Calculate the metal extraction rate according to the formula: extraction rate % = (metal amount in the liquid before treatment - metal amount in the liquid after treatment) ÷ metal amount in the liquid before treatment × 100%. The extraction rates of indium, germanium, tin, antimony, cadmium, zinc, and iron are 12.5%, 97.0%, 89.19%, 84.85%, 0.33%, 0.21%, and 4.84% respectively.

[0080] By comparing with Comparative Example 2, it can be seen that the metal separation effect of Examples 3 to 8 using the process of "antimony precipitation - tin extraction - germanium extraction - indium extraction with acid reduction - cadmium precipitation" is significantly better than that of Comparative Example 2 using the process of "tin precipitation - purification - indium extraction - germanium extraction", and the metal recovery rate is higher.

[0081] It should be understood that the above specific embodiments of the present invention are only used for exemplary illustration or explanation of the principle of the present invention, and do not constitute a limitation to the present invention. Therefore, any modifications, equivalent replacements, improvements, etc. made without departing from the spirit and scope of the present invention shall be included within 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 boundary of the appended claims, or equivalent forms of such scope and boundary.

Claims

1. A method for resource treatment of crude lead smelting soot containing indium, germanium, tin and antimony, characterized in that, It includes the following steps: A) Mixed acid leaching: Put the crude lead smelting soot into the crude hydrochloride salt solution, stir and slurry, inject concentrated sulfuric acid for ripening reaction, then dilute with the crude hydrochloride salt solution, continue to stir and leach to obtain the leaching solution and leaching residue, and send the leaching residue to the crude lead smelting batching; B) Selective extraction and separation: Transfer the leaching solution obtained in step A to the selective extraction and separation system. First, selectively extract and separate tin, then selectively extract and separate germanium, and finally selectively extract and separate indium to obtain tin oxide concentrate, germanium oxide concentrate, crude indium and indium extraction residue solution respectively; C) Precipitation and crystallization separation: Precipitate cadmium from the indium extraction residue solution obtained in step B to obtain sponge cadmium and cadmium-free residue solution. The sponge cadmium is pressed into pellets and melted and cast to produce crude cadmium. The cadmium-free residue solution is membrane concentrated and then ethanol is used to promote cooling and crystallization to precipitate zinc sulfate crystals and mother liquor. The mother liquor is evaporated to remove ethanol, and the ethanol is recovered and returned to this step for use. The ethanol-free residue solution is the crude hydrochloride salt solution and is returned to step A for use.

2. The resource treatment method for crude lead smelting soot containing indium, germanium, tin and antimony according to claim 1, characterized in that, Before the leaching solution obtained in step A is transferred to the selective extraction system, add reduced iron powder, stir and react to remove antimony to obtain sponge antimony and antimony-removing solution. The antimony-removing solution is then transferred to the selective extraction system, and the sponge antimony is sent to the antimony smelting batching.

3. The method for resource treatment of crude lead smelting soot containing indium, germanium, tin and antimony according to claim 2, characterized in that, The mass percentage of metallic iron in the reduced iron powder is 88.0% - 95.0%, and the particle size is ≤0.178 mm.

4. The method for resource treatment of crude lead smelting dust containing indium, germanium, tin and antimony according to claim 3, wherein The temperature of the stirring reaction for antimony removal is 40°C - 50°C, and the reaction time is 45 min - 60 min.

5. The resource treatment method for the crude lead smelting soot containing indium, germanium, tin and antimony according to claim 1, characterized in that Before the leaching residue in step A is sent to the crude lead smelting batching, add the crude hydrochloride salt solution to slurry, stir and wash twice, and the washing water produced is combined with the crude hydrochloride salt solution and returned to this step for use.

6. The resource treatment method of crude lead smelting soot containing indium, germanium, tin and antimony according to claim 1, characterized in that Before selectively extracting indium in step B, add a neutralizing agent to adjust the free sulfuric acid content of the leaching solution to 25.0 g / L - 35.0 g / L.

7. The method for resource treatment of crude lead smelting dust containing indium, germanium, tin and antimony according to claim 6, characterized in that, The neutralizing agent is preferably zinc-cadmium slag dust, including copper-cadmium slag ripened in hydrometallurgical zinc smelting, blue powder in pyrometallurgical zinc smelting, and artificially synthesized zinc-cadmium carbonate slag.

8. A method for resource treatment of crude lead smelting dust containing indium, germanium, tin and antimony according to claim 1, characterized in that Before precipitating cadmium from the indium extraction residue solution in step C, add hydrogen peroxide and a neutralizing agent to react to remove iron and arsenic, adjust the pH of the indium extraction residue solution to 5.0 - 5.4, the total iron ion content ≤0.02 g / L, and the total arsenic ion content ≤0.001 g / L. The neutralizing agent is preferably quicklime powder.

9. The resource treatment method for crude lead smelting soot containing indium, germanium, tin and antimony according to any one of claims 1 to 8, characterized in that, The crude lead smelting soot in step A is the soot collected from bottom-blowing, side-blowing or top-blowing crude lead smelting, containing 0.25% - 0.50% indium, 0.03% - 0.05% germanium, 1.0% - 2.5% tin, and 1.0% - 2.5% antimony.

10. The resource treatment method for the crude lead smelting soot containing indium, germanium, tin and antimony according to any one of claims 1 to 8, characterized in that, In step B, the organic phase for selectively extracting tin has a composition of 40% (by volume) E6040 extractant - 10% P204 extractant - 50% solvent oil 260#, the organic phase for selectively extracting germanium has a composition of 10% (by volume) E356 extractant - 15% P204 extractant - 75% solvent oil 260#, and the organic phase for selectively extracting indium has a composition of 30% (by volume) P204 extractant - 70% solvent oil 260#. The E6040 extractant is a phosphate ester composite extractant, the P204 extractant is diisooctyl phosphoric acid, and the E356 extractant is an isomeric alkyl hydroxamic acid composite extractant.

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