Efficient separation process for refractory indium-poor tin-antimony polymetallic resources

Abstract

The present application relates to the technical field of mineral processing, and particularly relates to a high-efficiency separation process for a refractory indium-poor tin-antimony polymetallic resource, comprising the following steps: polymetallic resource pretreatment, crushing treatment, and separation of the obtained polymetallic particles by a shaking table; magnetic separation coarse screening, preliminary removal of magnetic metals in the crushed polymetallic particles to obtain primary concentrate and tailings; polymetallic particle flotation, mixing the primary concentrate with water, pouring into a flotation tank, and adding an activator, a collector and an inhibitor to obtain a crude metal containing indium, tin and antimony; oxidation and reduction, oxidizing tin and antimony to separate indium metal; vacuum distillation, reducing the tin and antimony oxides into tin and antimony mixed metals, and then feeding the mixed metals into a vacuum distillation device to separate tin and antimony. The present application comprises magnetic separation and vacuum distillation, avoids the need for multiple flotation to separate different metals, improves the environmental friendliness, and reduces the production cost and improves the production efficiency.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of mineral processing, in particular to a high-efficiency separation process for a refractory indium-poor tin-antimony polymetallic resource. BACKGROUND

[0002] China is rich in refractory polymetallic resources, and the reserves of indium and tin are among the top in the world. However, the copper minerals, zinc minerals, cassiterite and iron sulfide minerals in the ore are finely disseminated, and the paragenetic relationship is close. Moreover, the zinc minerals are mostly high-iron or super-high-iron sphalerite, and the iron content can reach more than 20%. Due to the close dissemination of copper, zinc and sulfur minerals, separation is difficult. In order to achieve the goal of separating polymetallic resources, a multiple repeated flotation screening process is required.

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

[0004] Therefore, there is a need for an efficient and environmentally friendly high-efficiency separation process for a refractory indium-poor tin-antimony polymetallic resource. SUMMARY

[0005] The main purpose of the present application is to provide a high-efficiency separation process for a refractory indium-poor tin-antimony polymetallic resource, which aims to solve the problems of low efficiency and environmental pollution of the existing refractory indium-poor tin-antimony polymetallic resource.

[0006] To achieve the above-mentioned purpose, the present application provides a high-efficiency separation process for a refractory indium-poor tin-antimony polymetallic resource, which comprises the following steps:

[0007] The polymetallic resource is pretreated, and the refractory indium-poor tin-antimony polymetallic resource is crushed. The crushed polymetallic particles are separated by a shaking table.

[0008] The crushed polymetallic particles are sent to a magnetic disk device to preliminarily remove the magnetic metals in the polymetallic particles, and obtain a primary concentrate and a tailing.

[0009] The primary concentrate is mixed with water to obtain a slurry, which is then fed into a flotation tank. Activators, collectors and depressants are poured into the flotation tank to obtain a crude indium-tin-antimony metal.

[0010] The crude metal is poured into an oxidation tank to oxidize the tin and antimony, and separate the indium metal.

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

[0012] Further, the multi-metal resource pretreatment, the poor indium tin antimony multi-metal resource is broken, the multi-metal particles obtained after breaking are sorted by a shaking table, and the step includes:

[0013] The poor indium tin antimony multi-metal resource is sent to a crushing device to obtain multi-metal resource fragments;

[0014] The multi-metal resource fragments are sent to a shaking table device, and the multi-metal fragments are deslimed and sorted by the shaking table device to obtain multi-metal particles.

[0015] Further, the magnetic separation coarse screening, the crushed multi-metal particles are sent to a magnetic disk device, and the magnetic metal in the multi-metal particles is preliminarily removed to obtain primary concentrate and tailings, and the step includes:

[0016] The crushed multi-metal particles are sent to the magnetic disk device, and the magnetic metal particles in the multi-metal particles are adsorbed and removed by starting the magnetic disk device, and the magnetic metal in the multi-metal particles is preliminarily removed;

[0017] The secondary shaking table reselection, the multi-metal particles subjected to the magnetic separation are guided to the shaking table again for reselection to obtain primary concentrate and tailings.

[0018] Further, the multi-metal particle flotation, the primary concentrate is mixed with water to obtain ore slurry, the ore slurry is introduced into a flotation tank, and activator, collector, and depressor are poured into the flotation tank to obtain indium tin antimony coarse metal, and the step includes:

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

[0020] The ore slurry is introduced into a flotation tank, and activator, collector, and depressor are poured into the flotation tank to separate the multi-metal resource from gangue;

[0021] Air bubbles are introduced into the flotation tank to make the multi-metal resource adhere to the air bubbles to form a foam layer;

[0022] The foam layer is collected to obtain indium tin antimony coarse metal.

[0023] Further, the step of introducing the ore slurry into the flotation tank, pouring activator, collector, and depressor into the flotation tank to separate the multi-metal resource from gangue further includes:

[0024] The ore slurry is introduced into the flotation tank and a pH value adjusting agent is added to adjust the pH value of the ore slurry to 8 to 10;

[0025] Activator, collector, and depressor are added to the flotation tank, and stirring is performed to make the activator and collector act on the multi-metal resource and the depressor act on the gangue;

[0026] The activator is diethyl ((2-hydroxyethoxy) methyl) phosphonate (DEHEMP), the collecting agent is a mixed solution of ethylthiourea, N-phenylacetyl isoxazone (NPHA) and sodium carbonate, and the inhibitor is a complex compound of sodium hexametaphosphate and water glass.

[0027] Further, the step of oxidizing and reducing the crude metal to obtain the mixed metal of tin and antimony in the redox process further comprises:

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

[0029] The mixed metal containing the tin and antimony oxides and indium is sent to an extraction tank and poured into an acid solution, and the pH value of the solution is adjusted to 2-3;

[0030] The extraction agent is poured into the extraction tank to extract the indium ion solution;

[0031] The indium ion solution is sent to an electrolysis tank for electrolysis to obtain indium metal.

[0032] Further, the step of reducing the tin and antimony oxides into the mixed metal of tin and antimony and then sending the mixed metal to the vacuum distillation equipment to separate the tin and antimony in the vacuum distillation process further comprises:

[0033] The tin and antimony oxides are sent to an osmet furnace, inert gas is filled into the osmet furnace, and the osmet furnace is heated to 300-700 DEG C to obtain the mixed metal of tin and antimony;

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

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

[0036] In the present application, diethyl ((2-hydroxyethoxy) methyl) phosphonate (DEHEMP) is used as the activator, a mixed solution of ethylthiourea, N-phenylacetyl isoxazone (NPHA) and sodium carbonate prepared in a certain proportion is used as the collecting agent, and a complex compound of sodium hexametaphosphate and water glass is used as the inhibitor, thereby improving the effect of the flotation process, effectively avoiding waste of metal resources in the development of complex metal resources, and avoiding the need for multiple flotation to separate different metals, improving the environmental friendliness, reducing the production cost and improving the production efficiency. DETAILED DESCRIPTION

[0037] With reference to the drawings and embodiments of the present application, the technical solutions in the embodiments of the present application will be described clearly and completely. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments of the present application, all other embodiments obtained by a person of ordinary skill in the art without creative work fall within the scope of protection of the present application.

[0038] It should be noted that all directional indications, such as upper, lower, left, right, front, back, and the like, used in the embodiments of the present application are only used to explain the relative position relationship, movement condition and the like between components in a certain posture, and if the certain posture changes, the directional indications also change accordingly.

[0039] In addition, the description of "first", "second" and the like in the present application is only for the purpose of description, and cannot be understood as indicating or implying the relative importance of the indicated technical features or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first", "second" can explicitly or implicitly include at least one of the features. In addition, the technical solutions of each embodiment can be combined with each other, but it must be based on the fact that a person of ordinary skill in the art can realize it, and when the combination of technical solutions contradicts each other or cannot be realized, it should be considered that the combination of technical solutions does not exist, and is not within the scope of protection required by the present application.

[0040] In the present application, the specific components of the hydroxamic acid chelating agent selected are ethyldithizone, N-phenylacetyl isoxazoline (NPHA, structural formula as formula 1), and a collector prepared from sodium carbonate in a certain proportion. NPHA can be obtained by structural modification of benzyl hydroxamic acid. The hydroxamic acid collector can form a chelating ring on the surface of cassiterite through the polar group in the hydroxamic acid, mainly by chemical adsorption, accompanied by physical adsorption. The benzyl hydroxamic acid has better selectivity and collecting ability through activation of Pb 2+ NPHA has better flotation performance than benzyl hydroxamic acid on cassiterite, can separate cassiterite and other substances in a wider pH range, and can chelate into a five-membered ring on the surface of the mineral in the form of chemical adsorption. Ethyldithizone is an excellent selective collector with strong selectivity for antimony, high efficiency, low toxicity and easy to prepare. Sodium carbonate can enhance the selectivity of the collector to the mineral.

[0041]

[0042] It can be understood that a single flotation agent is difficult to meet the separation requirements of cassiterite and other minerals, and in order to meet the separation requirements, a suitable activator needs to be added to optimize the pulp environment, so as to realize efficient separation of multi-metal resources. In the present application, the activator is selected as diethyl ((2-hydroxyethoxy) methyl) phosphonate (DEHEMP, structural formula as formula 2), which is a gift of DEHEMP power supply. DEHEMP will react with styrene phosphonic acid and benzyl hydroxamic acid, and the reaction site is mainly located on the phosphorus-oxygen double bond and the hydroxyl group. By combining with Sn atoms, the water group of DEHEMP is directed towards the solution, so as to realize the separation of cassiterite.

[0043]

[0044] In detail, it is also difficult to separate multi-metal resources and gangue by only using collectors and activators. In order to avoid the participation of gangue in flotation during flotation, an inhibitor needs to be used to inhibit the gangue. In the present application, the inhibitor is a complex compound of sodium hexametaphosphate and water glass, which can inhibit a variety of gangues, especially quartz and feldspar in granite, so as to achieve efficient separation of complex ores.

[0045] Among them, the present application has application examples 1-3 and control examples 1 and 2 using prior art:

[0046] (I) Separation process of refractory indium-poor tin-antimony multi-metal resources

[0047] The separation processes of examples 1-3 and control examples 1-2 are as follows:

[0048] Example 1:

[0049] S1, the refractory indium-poor tin-antimony multi-metal resources are sent into a jaw crusher for crushing treatment, and are crushed to below 100 μm. The multi-metal particles obtained after crushing are separated by a shaking table, and the ore is deslimed and preliminarily screened;

[0050] S2, the crushed multi-metal particles are sent to a magnetic disk device, and the magnetic disk device is started for 2 hours, and the multi-metal particles on the magnetic disk device are continuously stirred, so as to preliminarily remove the magnetic metal in the multi-metal particles;

[0051] S3, the multi-metal particles after removing the magnetic metal are again put into a shaking table device, and the shaking table device is started for 3 hours, so as to obtain a primary concentrate and a tailing;

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

[0053] S5, introduce bubbles into the flotation tank and stand for 1h, when the multi-metal resources adhere to the bubbles, collect the foam layer and then defoam to obtain crude metal, guide the crude metal into an osmet furnace, heat to 600℃, keep warm for 1h and introduce a nitrogen atmosphere, oxidize tin and antimony in the crude metal to obtain a mixed metal containing tin, antimony oxide and indium;

[0054] S6, put the mixed metal into an extraction tank, adjust the pH value in the extraction tank to 2.0, put di(2-ethylhexyl) phosphate into the extraction tank as an extractant, so that the concentration of di(2-ethylhexyl) phosphate is 1%, and stir at 25℃ for 20 minutes to obtain an organic phase containing indium and a mixed metal solution;

[0055] S7, the organic phase containing indium is stripped with 6mol / L concentrated hydrochloric acid to obtain an indium ion solution, the indium ion solution is subjected to zinc replacement to obtain sponge indium, the sponge indium is melted to form an anode under the protection of glycerol, and the sponge indium anode is put into an electrolytic cell for electrolysis to obtain indium metal;

[0056] S8, the mixed metal solution is sent into an osmet furnace and inert gas is filled, heated to 700℃, so that the oxides of tin and antimony are reduced to obtain a mixed metal of tin and antimony, and then the mixed metal of tin and antimony is sent into a vacuum distillation device and heated to 2000℃, so that the antimony metal is volatilized in a gaseous state and condensed into liquid antimony on the vacuum furnace condensing cover, and the liquid antimony is collected and discharged, and the tin metal does not volatilize and flows into the evaporation tray in the vacuum furnace and then flows out downward;

[0057] S9, the tin metal and the antimony metal are respectively placed under the inert gas and cooled to room temperature to obtain tin metal and antimony metal.

[0058] Example 2:

[0059] S1, the refractory indium-poor tin-antimony multi-metal resource is sent into a jaw crusher for crushing treatment, and is crushed to below 75μm, and the multi-metal particles obtained after crushing are separated by a shaking table for desliming and preliminary screening of the ore;

[0060] S2, send the crushed multi-metal particles to the magnetic disk device, start the magnetic disk device 2h, continuously stir the multi-metal particles on the magnetic disk device, and preliminarily remove the magnetic metal in the multi-metal particles;

[0061] S3, the multi-metal particles after removing the magnetic metal are again put into the shaking table device, and the shaking table device is started for 3 hours to obtain primary concentrate and tailings;

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

[0063] S5, introduce bubbles into the flotation tank, and stand for 1h, when the multi-metal resources adhere to the bubbles, collect the foam layer and then defoam to obtain crude metal, guide the crude metal to the Osmund furnace, heat to 600℃, keep warm for 1h and introduce nitrogen atmosphere, oxidize tin and antimony in the crude metal to obtain mixed metal containing tin, antimony oxide and indium;

[0064] S6, put the mixed metal into an extraction tank, adjust the pH value in the extraction tank to 2.0, put di(2-ethylhexyl) phosphate into the extraction tank as an extractant, so that the concentration of di(2-ethylhexyl) phosphate is 1%, and stir at 25℃ for 20 minutes to obtain an organic phase containing indium and a mixed metal solution;

[0065] S7, the organic phase containing indium is back-extracted with 6mol / L concentrated hydrochloric acid to obtain an indium ion solution, the indium ion solution is subjected to zinc replacement to obtain sponge indium, the sponge indium is melted to form an anode under the protection of glycerol, and the sponge indium anode is put into an electrolytic cell to obtain indium metal;

[0066] S8, the mixed metal solution is sent into an Osmund furnace and inert gas is filled, heated to 700℃, so that the oxides of tin and antimony are reduced to obtain mixed metal of tin and antimony, and then the mixed metal of tin and antimony is sent into a vacuum distillation device and heated to 2000℃, so that the antimony metal is volatilized in a gaseous state and condensed into liquid antimony on the vacuum furnace condensing cover, and the liquid antimony is collected and discharged, and the tin metal does not volatilize and flows into the evaporation tray in the vacuum furnace and then flows out downward;

[0067] S9, the tin metal and the antimony metal are respectively placed under the inert gas and cooled to room temperature to obtain tin metal and antimony metal.

[0068] Example 3:

[0069] S1, send the refractory indium-poor tin-antimony polymetallic resources into a jaw crusher for crushing treatment, crush to below 50 pm, and separate the polymetallic particles obtained after crushing by a shaking table to remove mud and preliminarily screen the ore;

[0070] S2, send the crushed polymetallic particles to a magnetic disk device, start the magnetic disk device for 2 hours, continuously stir the polymetallic particles on the magnetic disk device, and preliminarily remove the magnetic metals in the polymetallic particles;

[0071] S3, re-put the polymetallic particles after removing the magnetic metals into a shaking table device, start the shaking table device for 3 hours, and obtain a primary concentrate and a tailing;

[0072] S4, mix the primary concentrate with water at a volume ratio of 1:4 to obtain a slurry with a concentration of 20%, then pass the slurry into a flotation tank, pass lime into the flotation tank to adjust the pH value of the slurry to 8, then pour 1000 g / t of ore (diethyl ((2-hydroxyethoxy) methyl) phosphonate (DEHEMP)) into the flotation tank, pour 1500 g / t of ore (a mixed solution of diethyl ((2-hydroxyethoxy) methyl) phosphonate (DEHEMP) prepared at a ratio of 1:6:3) into the flotation tank, pour 200 g / t of ore (a complex compound of sodium hexametaphosphate and water glass) into the flotation tank, and continuously stir for 12 hours;

[0073] S5, introduce bubbles into the flotation tank, and stand for 1 hour, when the polymetallic resources adhere to the bubbles, collect the foam layer, defoam to obtain a crude metal, guide the crude metal to an Osmund furnace, heat to 600 DEG C, keep warm for 1 hour, and introduce a nitrogen atmosphere, oxidize tin and antimony in the crude metal to obtain a mixed metal containing tin, antimony oxide and indium;

[0074] S6, put the mixed metal into an extraction tank, adjust the pH value in the extraction tank to 2.0, put di(2-ethylhexyl) phosphate into the extraction tank as an extractant, so that the concentration of di(2-ethylhexyl) phosphate is 1%, fully stir at 25 DEG C for 20 minutes to obtain an organic phase containing indium and a mixed metal solution;

[0075] S7, use 6 mol / L concentrated hydrochloric acid to strip the organic phase containing indium to obtain an indium ion solution, perform zinc replacement on the indium ion solution to obtain sponge indium, melt the sponge indium under the protection of glycerol to prepare an anode, and put the sponge indium anode into an electrolytic cell to obtain indium metal;

[0076] S8, the mixed metal solution is sent into an osmet furnace and filled with inert gas, heated to 700°C, so that the tin and antimony oxides are reduced to obtain a mixed metal of tin and antimony, and then the mixed metal of tin and antimony is sent into a vacuum distillation device and heated to 2000°C, so that the antimony metal is volatilized in a gaseous state and then condensed on a vacuum furnace condensing cover as liquid antimony, and the liquid antimony is collected and discharged, and the tin metal does not volatilize and flows into the evaporation tray in the vacuum furnace and then is discharged downward;

[0077] S9, the tin metal and the antimony metal are respectively placed under the inert gas and cooled to room temperature to obtain the tin metal and the antimony metal.

[0078] Comparative Example 1:

[0079] S1, fuming enrichment: the mixed concentrate is mixed with anthracite coal at a coal ratio of 45% to be granulated, and is put into a fuming furnace for fuming volatilization, the temperature is 1400°C, the volatilization time is 90 min, the smelting slag is sent to a solid waste treatment center to recover the coal powder and other valuable metals therein, and the volatilized dust is collected to obtain oxygen powder, which is sent to a zinc hydrometallurgy process;

[0080] S2, zinc hydrometallurgy: the fuming enriched oxygen powder is subjected to neutral leaching, electrolytic zinc waste liquid with initial acid of 160-180 g / L is added as a bottom liquid, the oxygen powder is put in according to a liquid-solid ratio of 3:1, the temperature is controlled at 75-80°C, the reaction is carried out for 60-70 min, then the oxygen powder is used to adjust the final pH value to 4.5-4.7, the stirring is continued for 30 min and filtration is carried out, the supernatant after neutral leaching is returned to the neutral leaching as a bottom liquid, and the cycle is repeated once;

[0081] S3, the leaching solution after one cycle (zinc concentration reaches 80-100 g / L) is subjected to conventional iron removal and purification to obtain a new solution for electrodeposition, the new solution for electrodeposition contains zinc of 80-100 g / L. Low-zinc electrolysis method is adopted, the current density is controlled at 400 A / m 2 , the cell voltage is 5 V, the zinc stripping period is 48 hours, and the accumulated zinc on the cathode is subjected to conventional melting and casting to obtain zinc ingots;

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

[0083] S5, chloro salt treatment: the lead mud is put into a reaction bucket with a chloro salt solution (sodium chloride) according to a solid-liquid ratio of 3:1 for chloro salt leaching, the temperature is controlled at 60-70°C, the reaction is carried out for 90-100 min, after the reaction is completed, filtration is carried out, and the filter residue is the antimony residue product; 50 g / L of sodium sulfate is added to the filtrate after chloro salt leaching for lead precipitation, the reaction time is 45 min, filtration is carried out, and the filter residue is the lead residue, after washing, the lead residue product is obtained, sodium carbonate is added to the filtrate after lead precipitation for zinc precipitation, the pH value is adjusted to 5.5-6.0, the reaction time is 30-40 min, filtration is carried out, and the filter residue is returned to the wet zinc smelting process for feeding; the filtrate after zinc precipitation is concentrated and evaporated, the evaporation sleep is used for other production water or directly discharged as clean water, the bottom stream after evaporation has a chloro salt concentration of 50%, and is returned to the chloro salt leaching for recycling.

[0084] Comparative example 2:

[0085] S1, fuming enrichment: the mixed concentrate is mixed with anthracite coal at a coal ratio of 55% for granulation, and is put into a fuming furnace for fuming volatilization, the temperature is 1600°C, and the volatilization time is 60 min, the smelting slag is sent to a solid waste treatment center for recovery of coal powder and other valuable metals therein, and the volatilized dust is collected to obtain oxygen powder, which is sent to a wet zinc smelting process;

[0086] S2, wet zinc smelting: the fuming enriched oxygen powder is subjected to neutral leaching, 160-180 g / L of electrolytic zinc waste liquid is added as a bottom liquid, the oxygen powder is put in according to a liquid-solid ratio of 3:1, the temperature is controlled at 75-80°C, the reaction is carried out for 60-70 min, the final pH value is adjusted to 4.8-5.0 by using the oxygen powder, stirring is continued for 40 min, and filtration is carried out, the supernatant after neutral leaching is returned to the neutral leaching for bottoming, and the cycle is repeated for 3 times;

[0087] S3, after the leaching liquid (zinc concentration reaches 80-100 g / L) that is cycled for 3 times is subjected to conventional iron removal and purification, an electrodeposition new liquid is obtained, the electrodeposition new liquid contains zinc at a concentration of 80-100 g / L. Low-zinc electrolysis is adopted, the current density is controlled at 400 A / m 2 , the cell voltage is 5 V, the zinc stripping cycle is 48 hours, and the accumulated zinc at the cathode is subjected to conventional melting and casting to obtain zinc ingots;

[0088] S4, the neutral leaching residue is put into a reaction bucket with a mixture of electrolytic waste liquid and concentrated sulfuric acid with a mass fraction of 98% for acid leaching, the initial acid concentration is controlled at 250 g / L, the liquid-solid ratio is 3:1, the reaction temperature is controlled at 85-90°C, the concentration leaching is carried out for 100-120 min, and then the liquid-solid ratio is adjusted to 5:1 by adding clean water, and the leaching is carried out for 50-60 min. After the reaction is completed, the solution is subjected to conventional purification, indium extraction, impurity removal, displacement and melting and casting to obtain a crude indium product containing indium at a purity of 99.5%, and the leaching residue (lead mud) is sent to chloro salt treatment for further recovery of valuable metals such as tin, antimony, lead and silver therein;

[0089] S5, chloro salt treatment: the lead slurry is put into a reaction bucket with a chloro salt solution (sodium chloride) according to a solid-liquid ratio of 5:1, the temperature is controlled at 70-80 DEG C, and the reaction is carried out for 100-120 min. After the reaction, filtration is carried out, and the filter residue is the antimony residue product. 60 g / L of sodium sulfate is added to the filtrate after the chloro salt leaching, lead is precipitated, the reaction time is 60 min, filtration is carried out, and the filter residue is the lead residue. After washing, the lead residue product is obtained. Sodium hydroxide is added to the filtrate after the lead precipitation, zinc is precipitated, the pH value is adjusted to 6.0-6.5, the reaction time is 50-60 min, filtration is carried out, and the filter residue is returned to the wet zinc smelting process for feeding. The filtrate after the zinc precipitation is concentrated and evaporated, the evaporation sleep is used for other production water or directly discharged as clean water. The bottom stream after evaporation has a chloro salt concentration of 50%, and is returned to the chloro salt leaching for recycling.

[0090] Among them, examples 1-3 respectively use different proportions of activator, collector, depressor and corresponding equipment parameters, and the products obtained according to the technical means in the application are obtained and the corresponding data are tested. The comparative examples 1-2 use the current prior art, in order to realize the separation of multi-metal resources, multiple flotation is carried out, which causes a large amount of energy waste and a large amount of waste gas and waste residue in the production process, which is not friendly to the environment, and is different from the technical means recorded in the application. At the same time, the production efficiency and product results of the technical means in comparative examples 1-2 are insufficient compared with the technical scheme in the application (see Table 1 below), and the difference in energy consumption is also significant.

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

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

[0093] S1, 1g of indium metal is weighed;

[0094] S2, the indium metal is dissolved in 10ml of 1mol / L dilute hydrochloric acid, and stirring is carried out until the indium metal is completely dissolved;

[0095] S3, the sample solution after dissolution is diluted to 100ml;

[0096] S4, the concentration of indium (mg / L) and the concentration of other impurity metals (mg / L) in the solution are determined by using an inductively coupled plasma mass spectrometer (ICP-MS);

[0097] S5, the purity of indium is calculated according to the purity formula, and the purity of indium metal = (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 three groups of examples and the two groups of control examples, it can be seen that the process adopted by the present application has high metal recovery rate and purity by adopting new activators, collectors, inhibitors and corresponding processes, and using the magnetic separation process and the vacuum distillation process, and in the development of the difficult-to-select indium-poor tin-antimony polymetallic resources, the waste of metal resources can be effectively avoided.

[0102] In combination with all the above examples, in the present application, diethyl ((2-hydroxyethoxy) methyl) phosphonate (DEHEMP) is used as an activator, a mixed solution prepared by ethylthiourea, N-phenylacetyl isoxazoline (NPHA) and sodium carbonate in a certain proportion is used as a collector, and a complex compound of sodium hexametaphosphate and water glass is used as an inhibitor, thereby improving the effect of the flotation process, and in the development of complex metal resources, the waste of metal resources can be effectively avoided, and the magnetic separation process and the vacuum distillation process are used, thereby avoiding the need for multiple flotation to separate different metals, improving the environmental friendliness, and also reducing the production cost and improving the production benefit.

[0103] The above only describes the preferred embodiments of the present application, and does not limit the patent scope of the present application, and any equivalent structural transformation made according to the content of the present application, or direct / indirect application in other related technical fields is included in the patent protection scope of the present application.

Claims

1. A high-efficiency separation process for a refractory indium-poor tin-antimony polymetallic resource, characterized in that, The method comprises the following steps: The multi-metal resource pretreatment is to crush the refractory indium-poor tin-antimony multi-metal resource, and the multi-metal particles obtained after crushing are sorted by a shaking table; The magnetic rough screening is to send the crushed multi-metal particles to a magnetic disk device to preliminarily remove the magnetic metal in the multi-metal particles, and obtain primary concentrate and tailings; The primary concentrate is sent into a stirring tank and mixed with water to obtain ore pulp with a concentration of 20%-30%, the ore pulp is sent into a flotation cell and a pH value regulator is added to adjust the pH value of the ore pulp to 8-10, an activator, a collector and an inhibitor are added to the flotation cell and stirring is performed, so that the activator and the collector act on the multi-metal resource and the inhibitor acts on the gangue, air bubbles are introduced into the flotation cell to make the multi-metal resource adhere to the air bubbles to form a froth layer, and the froth layer is collected to obtain crude metal containing indium, tin and antimony, wherein the activator is diethyl ((2-hydroxyethoxy) methyl) phosphonate (DEHEMP), the collector is a mixed solution of ethylthiourea, N-phenylacetyl isoxazone (NPHA) and sodium carbonate, and the inhibitor is a complex compound of sodium hexametaphosphate and water glass; The oxidation and reduction is to pour the crude metal into an oxidation tank to oxidize tin and antimony and separate indium metal; The vacuum distillation is to reduce the oxides of tin and antimony into mixed metal of tin and antimony, and then send the mixed metal into a vacuum distillation device to separate tin and antimony.

2. The efficient separation process of refractory indium-poor tin-antimony polymetallic resources according to claim 1, characterized in that, The multi-metal resource pretreatment is to crush the refractory indium-poor tin-antimony multi-metal resource, and the multi-metal particles obtained after crushing are sorted by a shaking table; The refractory indium-poor tin-antimony multi-metal resource is sent into a crushing device to obtain multi-metal resource fragments; The multi-metal resource fragments are sent to a shaking table device to remove mud and sort the multi-metal fragments to obtain multi-metal particles.

3. The efficient separation process of refractory indium-poor tin-antimony polymetallic resources according to claim 1, characterized in that, The magnetic rough screening is to send the crushed multi-metal particles to a magnetic disk device to prelimarily remove the magnetic metal in the multi-metal particles, and obtain primary concentrate and tailings; The crushed multi-metal particles are sent to the magnetic disk device, the magnetic disk device is started to adsorb and remove the magnetic metal particles in the multi-metal particles, and the magnetic metal in the multi-metal particles is preliminarily removed; The secondary shaking table reselection is to direct the multi-metal particles subjected to the magnetic selection to the shaking table again for re-sorting to obtain primary concentrate and tailings.

4. The efficient separation process of refractory indium-poor tin-antimony polymetallic resources according to claim 1, characterized in that, The oxidation and reduction is to pour the crude metal into an oxidation tank to oxidize tin and antimony and separate indium metal; The crude metal containing indium, tin and antimony is placed in an osmet furnace and heated to 400-700℃ to oxidize tin and antimony in the crude metal into oxides; The mixture containing indium metal, tin oxide and antimony oxide is sent into an extraction tank and acid solution is poured into the tank to adjust the pH value of the solution to 2-3; An extractant is poured into the extraction tank to extract indium ion solution; The indium ion solution is sent into an electrolysis cell for electrolysis to obtain indium metal.

5. The efficient separation process of refractory indium-poor tin-antimony polymetallic resources according to claim 1, characterized in that, The vacuum distillation is to reduce the oxides of tin and antimony into mixed metal of tin and antimony, and then send the mixed metal into a vacuum distillation device to separate tin and antimony. The tin and antimony oxide is sent into an osmet furnace, and the osmet furnace is filled with inert atmosphere and heated to 300-700 DEG C, to obtain tin and antimony mixed metal; The tin and antimony mixed metal is sent into a vacuum distillation device, and heated to 1600-2200 DEG C, to separate liquid tin and liquid antimony; The liquid tin and liquid antimony are respectively cooled under inert atmosphere, to obtain tin metal and antimony metal.

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