Efficient sorting process for refractory lean indium tin antimony multi-metal resources

Abstract

The invention relates to the technical field of mineral processing, in particular to an efficient sorting process for refractory lean indium tin antimony multi-metal resources, which comprises the following steps: pre-treating the multi-metal resources, crushing, and sorting multi-metal particles obtained after crushing through a shaking table; magnetic separation and coarse screening are conducted, magnetic metal in the smashed multi-metal particles is preliminarily removed, and primary concentrate and tailings are obtained; multi-metal particle flotation: mixing the primary concentrate with water, introducing the mixture into a flotation tank, and pouring an activating agent, a collecting agent and an inhibitor to obtain crude metal containing indium, tin and antimony; oxidation reduction is conducted, tin and antimony are oxidized, and indium metal is separated out; and carrying out vacuum distillation, reducing the tin and antimony oxides into mixed metal of tin and antimony, feeding the mixed metal into vacuum distillation equipment, and separating out tin and antimony. The method comprises the steps of magnetic separation and vacuum distillation, the situation that different metals can be separated only through multiple times of flotation is avoided, the environmental friendliness is improved, meanwhile, the production cost can be reduced, and the production benefits are improved.

Description

Technical Field

[0001] The present invention relates to the technical field of mineral processing, and in particular to an efficient separation process for difficult-to-separate indium-poor, tin-antimony multi-metal resources. Background Art

[0002] my country is rich in difficult-to-select polymetallic resources, among which indium and tin reserves are among the highest in the world. However, the copper, zinc, cassiterite, iron sulfide and other minerals in the ores are finely embedded and have a close symbiotic relationship. Moreover, zinc minerals are mostly high-iron or ultra-high-iron sphalerite, with an iron content of more than 20%. Since copper, zinc and sulfur minerals are closely embedded, separation is difficult. In order to achieve the goal of separating polymetallic resources, it is necessary to adopt a production process of repeated flotation and screening.

[0003] In addition, the conventional flotation process uses copper sulfate and high alkali as activators, and the recovery rate of rare precious metals such as indium associated with new minerals is low, resulting in serious waste of resources. In addition, a large amount of pollutants such as waste water, waste gas, and waste residue are generated during the mineral processing process, which not only causes environmental pollution but also increases the difficulty and cost of mineral processing technology.

[0004] Therefore, there is a need for an efficient and environmentally friendly separation process for the difficult-to-select indium-poor, tin-antimony multi-metal resources. Summary of the invention

[0005] The main purpose of the present invention is to provide an efficient separation process for difficult-to-select indium-tin-antimony multi-metal resources, aiming to solve the problems of low efficiency and environmental pollution of existing difficult-to-select indium-tin-antimony multi-metal resources.

[0006] To achieve the above object, the present invention proposes a highly efficient separation process for difficult-to-separate indium-poor tin-antimony multi-metal resources, the method comprising the following steps:

[0007] Pre-treatment of multi-metal resources: crushing the difficult-to-select poor indium, tin and antimony multi-metal resources, and sorting the multi-metal particles obtained after crushing through a shaking table;

[0008] Magnetic coarse screening, sending the crushed multi-metal particles to the magnetic disk device to preliminarily remove the magnetic metals in the multi-metal particles to obtain primary concentrates and tailings;

[0009] Multi-metal particle flotation, mixing the primary concentrate with water to obtain slurry, then passing the slurry into a flotation tank, and pouring an activator, a collector, and a depressant into the flotation tank to obtain crude metals containing indium, tin, and antimony;

[0010] Redox, pouring the crude metal into an oxidation tank, causing tin and antimony to oxidize and indium metal to separate;

[0011] Vacuum distillation is used to reduce the oxides of tin and antimony to a mixed metal of tin and antimony, which is then fed into a vacuum distillation device to separate tin and antimony.

[0012] Furthermore, the multi-metal resource pre-treatment includes crushing the difficult-to-select indium-poor tin-antimony multi-metal resource, and sorting the multi-metal particles obtained after crushing through a shaking table, which includes:

[0013] The difficult-to-select poor indium, tin and antimony multi-metal resources are sent to the crushing equipment to obtain multi-metal resource fragments;

[0014] The polymetallic resource fragments are led to a shaking table device, through which the polymetallic fragments are desludged and sorted to obtain polymetallic particles.

[0015] Furthermore, the magnetic separation coarse screen sends the crushed multi-metal particles to the magnetic disk device to preliminarily remove the magnetic metals in the multi-metal particles to obtain the primary concentrate and tailings, which includes:

[0016] The crushed multi-metal particles are sent to a magnetic disk device, and the magnetic disk device is started to absorb and remove the magnetic metal particles inside the multi-metal particles, thereby preliminarily removing the magnetic metals in the multi-metal particles;

[0017] In the secondary shaking table gravity separation, the multi-metal particles that have been magnetically separated are directed back to the shaking table for re-separation to obtain primary concentrate and tailings.

[0018] Furthermore, the multi-metal particle flotation comprises the steps of mixing the primary concentrate with water to obtain a pulp, passing the pulp into a flotation tank, and pouring an activator, a collector, and a depressant into the flotation tank to obtain a crude metal containing indium, tin, and antimony:

[0019] The primary concentrate is passed into a stirring tank and mixed with water to obtain a slurry with a concentration of 20% to 30%;

[0020] The ore pulp is passed into the flotation tank, and the activator, collector and inhibitor are poured into the flotation tank to separate the polymetallic resources from the gangue;

[0021] Introducing air bubbles into the flotation tank, causing the polymetallic resources to adhere to the air bubbles to form a foam layer;

[0022] The foam layer is collected to obtain crude metal containing indium, tin and antimony.

[0023] Furthermore, the step of passing the ore pulp into a flotation tank, and pouring an activator, a collector, and a depressant into the flotation tank to separate the multi-metal resources from the gangue also includes:

[0024] Pass the slurry into the flotation tank and add a pH adjuster to adjust the pH value of the slurry to 8-10;

[0025] Adding an activator, a collector and a depressant into the flotation tank and stirring the tank so that the activator and the collector act on the polymetallic resources and the depressant acts on the gangue;

[0026] The activator is diethyl ((2-hydroxyethoxy) methyl) phosphonate (DEHEMP), the collector is a mixed solution of ethylthiocyanate, N-phenylacetoisoxamic acid (NPHA) and sodium carbonate, and the inhibitor is a complex of sodium hexametaphosphate and water glass.

[0027] Furthermore, the oxidation-reduction step of pouring the crude metal into an oxidation tank to oxidize tin and antimony and separate the indium metal further includes:

[0028] The crude metal containing indium, tin and antimony is placed in an Ausmelt furnace and heated to 400-700°C to oxidize the tin and antimony in the crude metal into oxides;

[0029] The mixed metals of tin, antimony oxide and indium are fed into an extraction tank and acid is poured in, and the pH value of the solution is adjusted to 2-3;

[0030] Pour an extractant into the extraction cell to extract an indium ion solution;

[0031] The indium ion solution is passed into an electrolytic cell for electrolysis to obtain indium metal.

[0032] Furthermore, the vacuum distillation, reducing the oxides of tin and antimony to a mixed metal of tin and antimony, and then feeding the mixed metal into a vacuum distillation device to separate tin and antimony, also includes the following steps:

[0033] The oxides of tin and antimony are fed into an Ausmelt furnace, and an inert atmosphere is filled into the Ausmelt furnace and heated to 300-700° C. to obtain a mixed metal of tin and antimony;

[0034] The mixed metal of tin and antimony is sent to a vacuum distillation device and heated to 1600-2200°C to separate liquid tin and liquid antimony;

[0035] Liquid tin and liquid antimony are cooled respectively in an inert atmosphere to obtain tin metal and antimony metal.

[0036] In the present invention, diethyl ((2-hydroxyethoxy) methyl) phosphonate (DEHEMP) is used as an activator, a mixed solution prepared by using ethylthiocyanate, N-phenylacetoisoxamic acid (NPHA) and sodium carbonate in a certain proportion is used as a collector, and a composite complex of sodium hexametaphosphate and water glass is used as an inhibitor, thereby improving the effect of the flotation process, effectively avoiding the waste of metal resources in the development of complex metal resources, and using a magnetic separation process and a vacuum distillation process at the same time, avoiding the need for multiple flotation separations to separate different metals, improving environmental friendliness, and reducing production costs and improving production efficiency. DETAILED DESCRIPTION

[0037] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0038] It should be noted that all directional indications in the embodiments of the present invention (such as up, down, left, right, front, back, etc.) are only used to explain the relative position relationship, movement status, etc. between the components in a certain specific posture. If the specific posture changes, the directional indication will also change accordingly.

[0039] In addition, the descriptions of "first", "second", etc. in the present invention are only used for descriptive purposes and cannot be understood as indicating or implying their relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" and "second" may explicitly or implicitly include at least one of the features. In addition, the technical solutions between the various embodiments can be combined with each other, but they must be based on the ability of ordinary technicians in the field to implement them. When the combination of technical solutions is contradictory or cannot be implemented, it should be deemed that such a combination of technical solutions does not exist and is not within the scope of protection required by the present invention.

[0040] The hydroxamic acid chelating agent involved in the present invention is a collector prepared by using ethylthiocyanate, N-phenylacetylisoxamic acid (NPHA, structural formula as formula 1), and sodium carbonate in a certain proportion, wherein NPHA can be obtained by structurally modifying benzohydroxamic acid. The hydroxamic acid collector can form a chelate ring on the surface of cassiterite through the polar groups in the hydroxamic acid, mainly through chemical adsorption, accompanied by physical adsorption, wherein benzohydroxamic acid is adsorbed on Pb 2+ NPHA has better selectivity and collection capacity under the activation of . NPHA has better flotation performance for cassiterite than benzohydroxamic acid, can separate cassiterite and other substances in a wide pH range, and can chelate into five-membered rings on the surface of minerals in the form of chemical adsorption. Ethylthiocyanate is an excellent selective collector with strong selectivity for antimony, high efficiency, low toxicity and easy preparation. Sodium carbonate can enhance the selectivity of collectors for minerals.

[0041]

[0042] It is understandable that a single flotation agent is difficult to meet the separation requirements of cassiterite and other minerals. In order to meet the separation requirements, it is necessary to add a suitable activator to optimize the pulp environment to achieve efficient separation of multi-metal resources. In the present invention, the activator is diethyl ((2-hydroxyethoxy) methyl) phosphonate (DEHEMP, structural formula as Formula 2), the power donation of DEHEMP will be styrenephosphonic acid and benzohydroxamic acid, the reaction site is mainly located on the phosphorus oxygen double bond and the hydroxyl group, and by combining with the Sn atom, the water transfer group of DEHEMP is directed toward the solution, thereby achieving the separation of cassiterite.

[0043]

[0044] In detail, it is difficult to ensure the separation of multi-metal resources from gangue only by using collectors and activators. In order to prevent gangue from participating in flotation, an inhibitor is needed to inhibit the gangue. The inhibitor in the present invention adopts a composite complex of sodium hexametaphosphate and water glass to achieve the inhibition of various gangues, especially quartz and feldspar in granite, so as to achieve efficient separation of complex ores.

[0045] The present invention includes application examples 1-3 and comparative examples 1 and 2 using the prior art:

[0046] (I) Separation technology of difficult to select indium, tin and antimony multi-metal resources

[0047] The following are the sorting processes of Examples 1-3 and Comparative Examples 1-2, and the specific steps are as follows:

[0048] Embodiment 1:

[0049] S1. Send the difficult-to-select poor indium, tin and antimony multi-metal resources into a jaw crusher for crushing to less than 100 μm, and sort the multi-metal particles obtained after crushing through a shaking table to desludging and preliminarily screen the ore;

[0050] S2, sending the crushed multi-metal particles to a magnetic disk device, starting the magnetic disk device for 2 hours, continuously turning the multi-metal particles on the magnetic disk device, and preliminarily removing the magnetic metals in the multi-metal particles;

[0051] S3, putting the multi-metal particles after removing the magnetic metals into the shaking table equipment again, starting the shaking table equipment for 3 hours, and obtaining primary concentrate and tailings;

[0052] S4, the primary concentrate and water are mixed in a volume ratio of 1:4 to obtain a slurry with a concentration of 20%, and then the slurry is passed into a flotation tank, lime is passed into the flotation tank until the pH value of the slurry is adjusted to 8, and then 400g / ton of ore (diethyl ((2-hydroxyethoxy) methyl) phosphonate (DEHEMP)), 800g / ton of ore (a mixed solution of diethyl ((2-hydroxyethoxy) methyl) phosphonate (DEHEMP) prepared in a ratio of 1:6:3) and 120g / ton of ore (composite complex of sodium hexametaphosphate and water glass) are poured into the flotation tank, and stirring is continued for 12h;

[0053] S5, introducing bubbles into the flotation tank and letting it stand for 1 hour. When the multi-metal resources adhere to the bubbles, the foam layer is collected and defoamed to obtain the crude metal. The crude metal is directed to an Ausmelt furnace, heated to 600° C., kept warm for 1 hour, and a nitrogen atmosphere is introduced to oxidize the tin and antimony in the crude metal to obtain a mixed metal containing tin, antimony oxide, and indium;

[0054] S6, adding the mixed metal into the extraction pool, and adjusting the pH value in the extraction pool to 2.0, adding di(2-ethylhexyl) phosphate as an extractant into the extraction pool, making the concentration of di(2-ethylhexyl) phosphate 1%, and fully stirring at 25° C. for 20 minutes to obtain an organic phase containing indium and a mixed metal solution;

[0055] S7, stripping the organic phase containing indium with 6 mol / L concentrated hydrochloric acid to obtain an indium ion solution, replacing the indium ion solution with zinc to obtain sponge indium, melting the sponge indium under the protection of glycerol to prepare an anode, placing the sponge indium anode in an electrolytic cell for electrolysis to obtain indium metal;

[0056] S8, sending the mixed metal solution into an Ausmelt furnace and filling it with inert gas, heating it to 700° C. to reduce the oxides of tin and antimony to obtain a mixed metal of tin and antimony, then sending the mixed metal of tin and antimony into a vacuum distillation device and heating it to 2000° C., so that the antimony metal volatilizes in a gaseous state and then condenses into liquid antimony on a condensation cover of the vacuum furnace, collecting the liquid antimony and discharging it, while the tin metal does not volatilize. The tin metal flows into an evaporation bottom plate in the vacuum furnace and then is discharged downward;

[0057] S9. Place the tin metal and the antimony metal in an inert gas and cool them down to room temperature to obtain tin metal and antimony metal.

[0058] Embodiment 2:

[0059] S1. Send the difficult-to-select poor indium, tin and antimony multi-metal resources into a jaw crusher for crushing to less than 75 μm, and sort the multi-metal particles obtained after crushing through a shaking table to desludging and preliminarily screen the ore;

[0060] S2, sending the crushed multi-metal particles to a magnetic disk device, starting the magnetic disk device for 2 hours, continuously turning the multi-metal particles on the magnetic disk device, and preliminarily removing the magnetic metals in the multi-metal particles;

[0061] S3, putting the multi-metal particles after the magnetic metal is removed into the shaking table equipment again, starting the shaking table equipment for 3 hours, and obtaining primary concentrate and tailings;

[0062] S4, the primary concentrate and water are mixed in a volume ratio of 1:4 to obtain a slurry with a concentration of 20%, and then the slurry is passed into a flotation tank, lime is passed into the flotation tank until the pH value of the slurry is adjusted to 8, and then 600g / ton of ore (diethyl ((2-hydroxyethoxy) methyl) phosphonate (DEHEMP)), 1000g / ton of ore (mixed solution of diethyl ((2-hydroxyethoxy) methyl) phosphonate (DEHEMP) prepared in a ratio of 1:6:3) and 150g / ton of ore (composite complex of sodium hexametaphosphate and water glass) are poured into the flotation tank, and stirring is continued for 12h;

[0063] S5, introducing bubbles into the flotation tank and letting it stand for 1 hour. When the multi-metal resources adhere to the bubbles, the foam layer is collected and defoamed to obtain the crude metal. The crude metal is directed to an Ausmelt furnace, heated to 600° C., kept warm for 1 hour, and a nitrogen atmosphere is introduced to oxidize the tin and antimony in the crude metal to obtain a mixed metal containing tin, antimony oxide, and indium;

[0064] S6, adding the mixed metal into the extraction pool, and adjusting the pH value in the extraction pool to 2.0, adding di(2-ethylhexyl) phosphate as an extractant into the extraction pool, making the concentration of di(2-ethylhexyl) phosphate 1%, and fully stirring at 25° C. for 20 minutes to obtain an organic phase containing indium and a mixed metal solution;

[0065] S7, stripping the organic phase containing indium with 6 mol / L concentrated hydrochloric acid to obtain an indium ion solution, replacing the indium ion solution with zinc to obtain sponge indium, melting the sponge indium under the protection of glycerol to prepare an anode, placing the sponge indium anode in an electrolytic cell for electrolysis to obtain indium metal;

[0066] S8, sending the mixed metal solution into an Ausmelt furnace and filling it with inert gas, heating it to 700° C. to reduce the oxides of tin and antimony to obtain a mixed metal of tin and antimony, then sending the mixed metal of tin and antimony into a vacuum distillation device and heating it to 2000° C., so that the antimony metal volatilizes in a gaseous state and then condenses into liquid antimony on a condensation cover of the vacuum furnace, collecting the liquid antimony and discharging it, while the tin metal does not volatilize. The tin metal flows into an evaporation bottom plate in the vacuum furnace and then is discharged downward;

[0067] S9. Place the tin metal and the antimony metal in an inert gas and cool them down to room temperature to obtain tin metal and antimony metal.

[0068] Embodiment 3:

[0069] S1. Send the difficult-to-select poor indium, tin and antimony multi-metal resources into a jaw crusher for crushing to less than 50 μm, and sort the multi-metal particles obtained after crushing through a shaking table to desludging and preliminarily screen the ore;

[0070] S2, sending the crushed multi-metal particles to a magnetic disk device, starting the magnetic disk device for 2 hours, continuously turning the multi-metal particles on the magnetic disk device, and preliminarily removing the magnetic metals in the multi-metal particles;

[0071] S3, putting the multi-metal particles after the magnetic metal is removed into the shaking table equipment again, starting the shaking table equipment for 3 hours, and obtaining primary concentrate and tailings;

[0072] S4, the primary concentrate and water are mixed in a volume ratio of 1:4 to obtain a slurry with a concentration of 20%, and then the slurry is passed into a flotation tank, lime is passed into the flotation tank until the pH value of the slurry is adjusted to 8, and then 1000g / ton of ore of activator (diethyl ((2-hydroxyethoxy) methyl) phosphonate (DEHEMP)), 1500g / ton of ore of collector (diethyl ((2-hydroxyethoxy) methyl) phosphonate (DEHEMP) mixed solution prepared in a ratio of 1:6:3), 200g / ton of ore of inhibitor (composite complex of sodium hexametaphosphate and water glass) are poured into the flotation tank, and stirring is continued for 12h;

[0073] S5, introducing bubbles into the flotation tank and letting it stand for 1 hour. When the multi-metal resources adhere to the bubbles, the foam layer is collected and defoamed to obtain the crude metal. The crude metal is directed to an Ausmelt furnace, heated to 600° C., kept warm for 1 hour, and a nitrogen atmosphere is introduced to oxidize the tin and antimony in the crude metal to obtain a mixed metal containing tin, antimony oxide, and indium;

[0074] S6, adding the mixed metal into the extraction pool, and adjusting the pH value in the extraction pool to 2.0, adding di(2-ethylhexyl) phosphate as an extractant into the extraction pool, making the concentration of di(2-ethylhexyl) phosphate 1%, and fully stirring at 25° C. for 20 minutes to obtain an organic phase containing indium and a mixed metal solution;

[0075] S7, stripping the organic phase containing indium with 6 mol / L concentrated hydrochloric acid to obtain an indium ion solution, replacing the indium ion solution with zinc to obtain sponge indium, melting the sponge indium under the protection of glycerol to prepare an anode, placing the sponge indium anode in an electrolytic cell for electrolysis to obtain indium metal;

[0076] S8, sending the mixed metal solution into an Ausmelt furnace and filling it with inert gas, heating it to 700° C. to reduce the oxides of tin and antimony to obtain a mixed metal of tin and antimony, then sending the mixed metal of tin and antimony into a vacuum distillation device and heating it to 2000° C., so that the antimony metal volatilizes in a gaseous state and then condenses into liquid antimony on a condensation cover of the vacuum furnace, collecting the liquid antimony and discharging it, while the tin metal does not volatilize. The tin metal flows into an evaporation bottom plate in the vacuum furnace and then is discharged downward;

[0077] S9. Place the tin metal and the antimony metal in an inert gas and cool them down to room temperature to obtain tin metal and antimony metal.

[0078] Comparative Example 1:

[0079] S1. Fuming enrichment: Mix the mixed concentrate and anthracite at a coal ratio of 45% and granulate them, then put them into a fuming furnace for fuming volatilization at a temperature of 1400°C and a volatilization time of 90 minutes. The smelting slag is sent to a solid waste treatment center to recover coal powder and other valuable metals. The volatilized smoke is collected to obtain oxygen powder and sent to the wet zinc smelting process.

[0080] S2. Hydrometallurgy: neutrally leaching the oxygen powder enriched by fuming, adding electrolytic zinc waste liquid with initial acid of 160-180g / L as base liquid, adding oxygen powder at a liquid-solid ratio of 3:1, controlling the temperature at 75-80℃, reacting for 60-70min, and then adjusting the endpoint pH value to 4.5-4.7 with oxygen powder, continuing stirring for 30min and filtering, returning the supernatant after neutral leaching to neutral leaching for base, and repeating this cycle once;

[0081] S3, the leached solution after one cycle (zinc concentration of 80-100g / L) is subjected to conventional iron removal and purification to obtain new electrolytic solution, which contains 80-100g / L zinc. Low zinc electrolysis method is used, and the current density is controlled at 400A / m 2 , the cell voltage is 5V, the zinc stripping cycle is 48 hours, the cathode accumulates zinc and then undergoes conventional smelting and casting to obtain zinc ingots;

[0082] S4, the neutral leaching residue is put into a reaction barrel mixed with electrolytic waste liquid and 98% concentrated sulfuric acid for acid leaching, the initial acid is controlled to 250g / L, the liquid-solid ratio is 2:1, the reaction temperature is controlled at 85-90℃, the concentrated leaching is 90-100min, and then water is added to the liquid-solid ratio of 4:1, and the leaching is 40-50min. After the reaction is completed, the solution is subjected to conventional purification, indium extraction, impurity removal, replacement, and casting to obtain a crude indium product containing 98.5% indium. The leached residue (lead mud) is sent to chloride salt treatment to further recover valuable metals such as tin, antimony, lead, and silver;

[0083] S5. Chloride treatment: put the lead mud into a reaction barrel with chloride solution (sodium chloride) at a solid-liquid ratio of 3:1 for chloride leaching, control the temperature at 60-70°C, react for 90-100 minutes, filter after the reaction, and the filter residue is the antimony slag product; add 50g / L sodium sulfate to the filtrate after chloride leaching to precipitate lead, react for 45 minutes, filter, the filter residue is lead slag, and the lead slag product is obtained after washing, add caustic soda to the filtrate after lead precipitation to precipitate zinc, adjust the pH to 5.5-6.0, react for 30-40 minutes, filter, and return the filter residue to the wet zinc smelting process for feeding; after the zinc precipitation filtrate is concentrated and evaporated, the evaporated water is used for other production water or directly discharged as clean water, the underflow chloride concentration after evaporation reaches 50%, and it is returned to the chloride leaching for recycling.

[0084] Comparative Example 2:

[0085] S1. Fuming enrichment: Mix the mixed concentrate and anthracite at a coal ratio of 55% and granulate them, then put them into a fuming furnace for fuming volatilization at a temperature of 1600°C and a volatilization time of 60 minutes. The smelting slag is sent to a solid waste treatment center to recover coal powder and other valuable metals. The volatilized smoke is collected to obtain oxygen powder and sent to the wet zinc smelting process.

[0086] S2. Hydrometallurgy: neutrally leaching the oxygen powder enriched by fuming, adding electrolytic zinc waste liquid with initial acid of 160-180g / L as base liquid, adding oxygen powder at a liquid-solid ratio of 3:1, controlling the temperature at 75-80℃, reacting for 60-70min, and then adjusting the endpoint pH value to 4.8-5.0 with oxygen powder, continuing stirring for 40min and filtering, returning the supernatant after neutral leaching to neutral leaching for base, and repeating this process for 3 times;

[0087] S3, the leached solution after three cycles (zinc concentration of 80-100g / L) is subjected to conventional iron removal and purification to obtain new electrolytic solution, which contains 80-100g / L zinc. Low zinc electrolysis method is used, and the current density is controlled at 400A / m 2 , the cell voltage is 5V, the zinc stripping cycle is 48 hours, the cathode accumulates zinc and then undergoes conventional smelting and casting to obtain zinc ingots;

[0088] S4, the neutral leaching residue is put into a reaction barrel mixed with electrolytic waste liquid and 98% concentrated sulfuric acid for acid leaching, the initial acid is controlled to 250g / L, the liquid-solid ratio is 3:1, the reaction temperature is controlled at 85-90℃, the concentrated leaching is 100-120min, and then water is added to the liquid-solid ratio of 5:1, and the leaching is 50-60min. After the reaction is completed, the solution is subjected to conventional purification, indium extraction, impurity removal, replacement, and casting to obtain a crude indium product containing 99.5% indium. The leached residue (lead mud) is sent to chloride salt treatment to further recover valuable metals such as tin, antimony, lead, and silver;

[0089] S5. Chloride treatment: put the lead mud into a reaction barrel with chloride solution (sodium chloride) at a solid-liquid ratio of 5:1 for chloride leaching, control the temperature at 70-80°C, react for 100-120 minutes, filter after the reaction, and the filter residue is the antimony slag product; add 60g / L sodium sulfate to the filtrate after chloride leaching to precipitate lead, react for 60 minutes, filter, the filter residue is lead slag, and the lead slag product is obtained after washing, add caustic soda to the filtrate after lead precipitation to precipitate zinc, adjust the pH to 6.0-6.5, react for 50-60 minutes, filter, and return the filter residue to the wet zinc smelting process for feeding; after the zinc precipitation filtrate is concentrated and evaporated, the evaporated water is used for other production water or directly discharged as clean water, the underflow chloride concentration after evaporation reaches 50%, and it is returned to the chloride leaching for recycling.

[0090] Among them, Examples 1-3 respectively used different proportions of activators, collectors, inhibitors and corresponding equipment parameters to obtain products obtained according to the technical means of the present invention and verify the corresponding data. Compared with Examples 1-2, the current existing technology was used. In order to achieve the separation of multi-metal resources, multiple flotation was performed, resulting in a large amount of energy waste and a large amount of waste gas and waste residue generated during the production process, which is not environmentally friendly and is quite different from the technical means recorded in the present invention. At the same time, the production efficiency and product results of the technical means in Examples 1-2 are insufficient compared with the technical solution in the present invention (see Table 1 below), and the difference in energy consumption is also quite significant.

[0091] (II) Metal recovery rate and purity test

[0092] Among them, taking indium metal as an example, the steps are:

[0093] S1. Weigh 1g of indium metal;

[0094] S2. Dissolve indium metal in 10 ml of 1 mol / L dilute hydrochloric acid and stir until the indium metal is completely dissolved;

[0095] S3, dilute the dissolved sample solution to 100 ml;

[0096] S4. Using an inductively coupled plasma mass spectrometer (ICP-MS) to determine the concentration of indium (mg / L) and the concentration of other impurity metals (mg / L) in the solution;

[0097] S5. Calculate the indium purity according to the purity formula: indium metal purity = (indium concentration / total metal concentration)*100%.

[0098] Table 1 Metal recovery rate and purity test data

[0099]

[0100] Experimental conclusion:

[0101] Through the experimental data of the above three groups of embodiments and two groups of control embodiments, it can be seen that the process adopted by the present invention, which adopts new activators, collectors, inhibitors and their corresponding processes and uses magnetic separation processes and vacuum distillation processes, has a higher metal recovery rate and purity, and can effectively avoid the waste of metal resources in the development of difficult-to-select poor indium, tin and antimony multi-metal resources.

[0102] In combination with all the above embodiments, the present invention uses diethyl ((2-hydroxyethoxy) methyl) phosphonate (DEHEMP) as an activator, a mixed solution prepared by ethylthiocyanate, N-phenylacetoisoxamic acid (NPHA) and sodium carbonate in a certain proportion as a collector, and a composite complex of sodium hexametaphosphate and water glass as an inhibitor, thereby improving the effect of the flotation process. In the development of complex metal resources, the waste of metal resources can be effectively avoided. At the same time, the magnetic separation process and the vacuum distillation process are used to avoid the need for multiple flotation to separate different metals, thereby improving environmental friendliness, reducing production costs, and improving production efficiency.

[0103] The above description is only a preferred embodiment of the present invention, and does not limit the patent scope of the present invention. All equivalent structural changes made by using the contents of the present invention specification under the inventive concept of the present invention, or directly / indirectly applied in other related technical fields are included in the patent protection scope of the present invention.

Claims

1. An efficient separation process for difficult-to-separate indium-poor tin-antimony multi-metal resources, characterized in that: The following steps are involved: Pre-treatment of multi-metal resources: crushing the difficult-to-select poor indium, tin and antimony multi-metal resources, and sorting the multi-metal particles obtained after crushing through a shaking table; Magnetic coarse screening, sending the crushed multi-metal particles to the magnetic disk device to preliminarily remove the magnetic metals in the multi-metal particles to obtain primary concentrates and tailings; Multi-metal particle flotation, mixing the primary concentrate with water to obtain slurry, then passing the slurry into a flotation tank, and pouring an activator, a collector, and a depressant into the flotation tank to obtain crude metals containing indium, tin, and antimony; Redox, pouring the crude metal into an oxidation tank, causing tin and antimony to oxidize and indium metal to separate; Vacuum distillation is used to reduce the oxides of tin and antimony to a mixed metal of tin and antimony, which is then fed into a vacuum distillation device to separate tin and antimony.

2. The efficient separation process of difficult-to-separate indium-poor tin-antimony multi-metal resources according to claim 1, characterized in that: The multi-metal resource pre-treatment comprises crushing the hard-to-select indium-poor tin-antimony multi-metal resource, and sorting the multi-metal particles obtained after crushing through a shaking table. The difficult-to-select poor indium, tin and antimony multi-metal resources are sent to the crushing equipment to obtain multi-metal resource fragments; The polymetallic resource fragments are led to a shaking table device, through which the polymetallic fragments are desludged and sorted to obtain polymetallic particles.

3. The efficient separation process of difficult-to-separate indium-poor tin-antimony multi-metal resources according to claim 1, characterized in that: The magnetic separation coarse screen sends the crushed multi-metal particles to the magnetic disk device to preliminarily remove the magnetic metals in the multi-metal particles to obtain the primary concentrate and tailings, which includes: The crushed multi-metal particles are sent to a magnetic disk device, and the magnetic disk device is started to absorb and remove the magnetic metal particles inside the multi-metal particles, thereby preliminarily removing the magnetic metals in the multi-metal particles; In the secondary shaking table gravity separation, the multi-metal particles that have been magnetically separated are directed back to the shaking table for re-separation to obtain primary concentrate and tailings.

4. The efficient separation process of difficult-to-separate indium-poor tin-antimony multi-metal resources according to claim 1, characterized in that: The multi-metal particle flotation comprises the steps of mixing the primary concentrate with water to obtain a pulp, passing the pulp into a flotation tank, and pouring an activator, a collector, and a depressant into the flotation tank to obtain a crude metal containing indium, tin, and antimony: The primary concentrate is passed into a stirring tank and mixed with water to obtain a slurry with a concentration of 20% to 30%; The ore pulp is passed into the flotation tank, and the activator, collector and inhibitor are poured into the flotation tank to separate the polymetallic resources from the gangue; Introducing air bubbles into the flotation tank, causing the polymetallic resources to adhere to the air bubbles to form a foam layer; The foam layer is collected to obtain crude metal containing indium, tin and antimony.

5. The efficient separation process of difficult-to-separate indium-poor tin-antimony multi-metal resources according to claim 4, characterized in that: The step of passing the ore pulp into a flotation tank, and pouring an activator, a collector, and a depressant into the flotation tank to separate the multi-metal resources from the gangue also includes: Pass the slurry into the flotation tank and add a pH adjuster to adjust the pH value of the slurry to 8-10; Adding an activator, a collector and a depressant into the flotation tank and stirring the tank so that the activator and the collector act on the polymetallic resources and the depressant acts on the gangue; The activator is diethyl ((2-hydroxyethoxy) methyl) phosphonate (DEHEMP), the collector is a mixed solution of ethylthiocyanate, N-phenylacetoisoxamic acid (NPHA) and sodium carbonate, and the inhibitor is a complex of sodium hexametaphosphate and water glass.

6. The efficient separation process of difficult-to-separate indium-poor tin-antimony multi-metal resources according to claim 1, characterized in that: The oxidation-reduction step of pouring the crude metal into an oxidation tank to oxidize tin and antimony and separate the indium metal also includes: The crude metal containing indium, tin and antimony is placed in an Ausmelt furnace and heated to 400-700°C to oxidize the tin and antimony in the crude metal into oxides; The mixed metals of tin, antimony oxide and indium are fed into an extraction tank and acid is poured in, and the pH value of the solution is adjusted to 2-3; Pour an extractant into the extraction cell to extract an indium ion solution; The indium ion solution is passed into an electrolytic cell for electrolysis to obtain indium metal.

7. The efficient separation process of difficult-to-separate indium-poor tin-antimony multi-metal resources according to claim 1, characterized in that: The vacuum distillation reduces the oxides of tin and antimony to a mixed metal of tin and antimony, and then feeds the mixed metal into a vacuum distillation device to separate tin and antimony, and the step also includes: The oxides of tin and antimony are fed into an Ausmelt furnace, and an inert atmosphere is filled into the Ausmelt furnace and heated to 300-700° C. to obtain a mixed metal of tin and antimony; The mixed metal of tin and antimony is sent to a vacuum distillation device and heated to 1600-2200°C to separate liquid tin and liquid antimony; Liquid tin and liquid antimony are cooled respectively in an inert atmosphere to obtain tin metal and antimony metal.

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