Method for separating and recovering valuable metal from industrial waste containing zirconium and yttrium

Abstract

The invention discloses a method for separating and recovering valuable metals from industrial waste containing zirconium and yttrium, which comprises the following steps: mixing the industrial waste containing zirconium with a flux, and roasting at high temperature to obtain an alkali fusion material; the alkali fusion material is crushed and levigated, water is added for stirring and leaching, and a water leaching material and a water leaching solution are obtained; adding water and hydrochloric acid into the water leaching material, controlling the pH value, stirring and leaching to obtain a transformation material and transformation liquid; mixing the transformed material with hydrochloric acid, heating, stirring and leaching to obtain acid leaching liquid and acid leaching residues; adding a zirconium precipitating agent into the pickle liquor, preserving heat, precipitating, filtering and separating to obtain basic zirconium sulfate and a yttrium-containing solution; roasting the basic zirconium sulfate at high temperature to obtain a zirconium oxide product; adding an oxalic acid solution into the yttrium-containing solution, preserving heat and settling to obtain yttrium oxalate and yttrium-deposited liquid; roasting yttrium oxalate at high temperature to obtain a yttrium oxide product; according to the method, valuable metal resources of zirconium and yttrium in the zirconium-yttrium industrial waste are separated and recycled, and high-value recycling treatment of the zirconium-yttrium waste is achieved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of non-ferrous metallurgy, and in particular to a method for separating and recovering valuable metals from zirconium-yttrium-containing industrial waste. BACKGROUND

[0002] China is the largest zirconium consumer in the world, and the degree of dependence on foreign zirconium resources has been high for a long time. Relevant data shows that the zirconium ore reserves in China account for only about 0.1% of the total reserves in the world, and more than 1 million tons of zirconium concentrate needs to be imported every year, with a dependence on foreign resources of more than 90%. At the same time, with the large-scale application of zirconium products and related materials, a large amount of zirconium processing waste will be generated every year, such as zirconium artificial gem processing grinding waste, zirconium-based composite refractory waste, etc. China is the world's most important zirconium artificial gem production and processing country. In the process of zirconium gem processing, a large amount of waste will be generated due to the need for cutting, grinding and other processes. This kind of waste usually contains 75%-95% zirconium oxide and 5%-20% yttrium oxide, and is a resource with high recycling value.

[0003] At present, there are studies on the recovery of valuable metals in zirconium-yttrium-containing solid waste by alkali fusion method and sulfuric acid acidification method.

[0004] Chinese patent CN105152211B discloses a method for producing zirconium oxychloride from zirconium-containing waste, which adopts the method of first preparing zirconium hydroxide, and then dissolving and crystallizing to obtain zirconium oxychloride. The overall process has a large amount of acid and alkali consumption.

[0005] Chinese patent CN101244843B discloses a method for recovering zirconium oxide and yttrium oxide from yttria-stabilized zirconia solid melt waste. The method recovers zirconium and yttrium in yttria-stabilized zirconia solid melt waste by sulfuric acid roasting, but SO2 flue gas is generated during the sulfuric acid roasting process, and ammonia water is used to adjust the pH of the solution during the zirconium sulfate aqueous solution-precipitation process, which will cause ammonia-nitrogen wastewater treatment problems in the subsequent process.

[0006] Therefore, it is an urgent problem for those skilled in the art to provide a method for separating and recovering valuable metals from zirconium-yttrium-containing industrial waste. SUMMARY

[0007] Therefore, the present application provides a method for separating and recovering valuable metals from zirconium-yttrium-containing industrial waste.

[0008] To solve the above technical problems, the present application adopts the following technical solutions:

[0009] A method for separating and recovering valuable metals from zirconium-yttrium-containing industrial waste, comprising the following steps:

[0010] (1) mixing zirconium-containing industrial waste with flux, and performing roasting treatment at high temperature to obtain alkali flux;

[0011] (2) crushing and grinding the alkali flux obtained in step (1), adding water to stir and leach, to obtain water leaching material and water leaching solution;

[0012] (3) adding water and hydrochloric acid to the water leaching material obtained in step (2), controlling the pH of the solution, stirring and leaching, to obtain transformation material and transformation solution;

[0013] (4) mixing the transformation material obtained in step (3) with hydrochloric acid, heating and stirring to leach, to obtain acid leaching solution and acid leaching residue;

[0014] (5) adding zirconium precipitating agent to the acid leaching solution obtained in step (4), and performing heat preservation and sedimentation, and then filtering to separate to obtain zirconium suboxide and yttrium-containing solution;

[0015] (6) performing roasting treatment at high temperature on the zirconium suboxide obtained in step (5) to obtain zirconium oxide product;

[0016] (7) adding oxalic acid solution to the yttrium-containing solution obtained in step (5), and performing heat preservation and sedimentation to obtain yttrium oxalate and yttrium-precipitated post-solution;

[0017] (8) performing roasting treatment at high temperature on the yttrium oxalate obtained in step (7) to obtain yttrium oxide product;

[0018] Preferably, in step (1), the flux is one or more of NaOH, Na2CO3 and KOH, the addition amount of the alkali flux is 2.2:1 to 1:1 based on the mass of the zirconium-yttrium waste, the roasting temperature is 700 to 1300℃, and the roasting time is 30 to 240 min.

[0019] Preferably, in step (2), the liquid-solid ratio of water to the alkali flux is 4:1 to 2:1, the leaching temperature is 40 to 55℃, and the leaching time is 30 to 80 min.

[0020] Preferably, in step (3), the liquid-solid ratio of water to the water leaching material is 2:1 to 1:1, the leaching temperature is 60 to 75℃, the leaching time is 50 to 90 min, and the pH of the solution is controlled to be 3 to 9.

[0021] Preferably, in step (4), the liquid-solid ratio of hydrochloric acid to the water leaching material is 2.5:1 to 1:1, the leaching temperature is 85 to 110℃, the leaching time is 60 to 180 min, and the hydrochloric acid is concentrated hydrochloric acid with a mass fraction of 36%.

[0022] Preferably, in the step (5), the zirconium precipitant is one or more of sulfuric acid, ammonium sulfate, the amount of which is calculated according to the zirconium concentration in the acid leaching solution, the amount of the zirconium precipitant is controlled so that the sulfur-zirconium ratio in the solution is 0.4:1-0.8:1, the zirconium precipitation temperature is maintained at 70-80°C, and the zirconium precipitation time is 2-6h.

[0023] Preferably, in the step (6), the calcination temperature is 900-1100°C, and the calcination time is 1-1.5h.

[0024] Preferably, in the step (7), the amount of oxalic acid is calculated according to the yttrium content in the yttrium-containing solution, the amount of oxalic acid is controlled so that the ratio of the amount of oxalic acid to the yttrium content is 1.5:1-2.5:1, the yttrium precipitation temperature is 70-80°C, and the yttrium precipitation time is 1-2.5h.

[0025] Preferably, in the step (8), the calcination temperature is 800-1000°C, and the calcination time is 0.5-1.5h.

[0026] Preferably, in the step (8), the zirconium-yttrium industrial waste includes 55-82% of ZrO2, 3-20% of Y2O3, and the rest of Fe2O3, SiO2, CaO, TiO2, and Al2O3 impurities, and the particle size of the industrial waste powder is less than 48μm.

[0027] The present application has the following technical effects relative to the prior art:

[0028] (1) In the present application, after the zirconium-yttrium waste is treated by alkali fusion, a water immersion + transformation step is introduced, which has the following effects: first, the residual alkali in the alkali fusion material is recovered and can be returned to the alkali fusion process for recycling, and the amount of hydrochloric acid used in the subsequent process is reduced; second, the transformation step removes most of the alkali metal elements in the water immersion material, which is beneficial to obtaining high-quality basic zirconium sulfate intermediate products in the subsequent zirconium precipitation step, and the zirconium ion concentration in the solution after the crystallization of the basic zirconium sulfate is very low, which is beneficial to obtaining high-purity yttrium-containing products in the subsequent operation;

[0029] (2) The present application realizes the separation and extraction of zirconium and yttrium valuable metals in zirconium-containing industrial waste, and the prepared zirconium oxide and yttrium oxide both have a purity of 99.9%, and the overall process has a small reagent consumption and no pollutant output. BRIEF DESCRIPTION OF DRAWINGS

[0030] Figure 1 The flowchart of the present application. DETAILED DESCRIPTION

[0031] Clearly, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative efforts are within the protection scope of the present application.

[0032] The application discloses a method for separating and recovering valuable metals from zirconium-yttrium-containing industrial waste, comprising the following steps:

[0033] (1) mixing the zirconium-containing industrial waste with a flux, the flux being one or more of NaOH, Na2CO3 and KOH, the addition amount of the alkaline flux being 2.2:1-1:1 in mass ratio to the zirconium-yttrium waste; and performing roasting treatment at high temperature, the roasting temperature being 700-1300 DEG C, and the roasting time being 30 min-240 min, to obtain an alkali smelting material;

[0034] (2) crushing and finely grinding the alkali smelting material obtained in the step (1), adding water to stir and leach, the liquid-solid ratio of water to the alkali smelting material being 4:1-2:1, the leaching temperature being 40-55 DEG C, and the leaching time being 30-80 min, to obtain a water leaching material and a water leaching solution;

[0035] (3) adding water and hydrochloric acid to the water leaching material obtained in the step (2), the liquid-solid ratio of water to the water leaching material being 2:1-1:1, controlling the pH of the solution to be 3-9, stirring and leaching, the leaching temperature being 60-75 DEG C, and the leaching time being 50-90 min, to obtain a transformation material and a transformation solution;

[0036] (4) mixing the transformation material obtained in the step (3) with hydrochloric acid, the hydrochloric acid being concentrated hydrochloric acid with a mass fraction of 36%, the liquid-solid ratio of the hydrochloric acid to the water leaching material being 2.5:1-1:1, stirring and leaching under heating, the leaching temperature being 85-110 DEG C, and the leaching time being 60-180 min, to obtain an acid leaching solution and an acid leaching residue;

[0037] (5) adding a zirconium precipitation agent to the acid leaching solution obtained in the step (4), the zirconium precipitation agent being one or more of sulfuric acid and ammonium sulfate, the addition amount of the zirconium precipitation agent being calculated according to the zirconium concentration in the acid leaching solution, the addition amount of the zirconium precipitation agent being controlled so that the sulfur-zirconium ratio in the solution is 0.4:1-0.8:1, the zirconium precipitation temperature being maintained at 70-80 DEG C, the zirconium precipitation time being 2-6 h, and the solution is kept warm and settled, to obtain a basic zirconium sulfate and a yttrium-containing solution through filtration and separation;

[0038] (6) performing roasting treatment on the basic zirconium sulfate obtained in the step (5) at high temperature, the roasting temperature being 900-1100 DEG C, and the roasting time being 1-1.5 h, to obtain a zirconium oxide product;

[0039] (7) adding oxalic acid solution to the yttrium-containing solution obtained in step (5), the amount of oxalic acid being calculated according to the content of yttrium in the yttrium-containing solution, the amount of oxalic acid being controlled to be 1.5:1-2.5:1 of the content of yttrium, the temperature for precipitating yttrium being 70-80℃, the time for precipitating yttrium being 1-2.5h, and the obtained yttrium oxalate and the solution after precipitating yttrium being obtained by heat preservation and sedimentation;

[0040] (8) roasting the yttrium oxalate obtained in step (7) at a high temperature to obtain yttrium oxide product, the roasting temperature being 800-1000℃, and the roasting time being 0.5-1.5h.

[0041] The zirconium-yttrium industrial waste includes 55-82% of ZrO2, 3-20% of Y2O3, and the rest of Fe2O3, SiO2, CaO, TiO2, and Al2O3 impurities, and the particle size of the industrial waste powder is less than 48μm.

[0042] Example 1:

[0043] As shown in the Figure 1 The application discloses a method for separating and recovering valuable metals from zirconium-yttrium industrial waste, which comprises the following steps:

[0044] (1) mixing the zirconium-yttrium industrial waste with sodium hydroxide according to a mass ratio of 1:1, and roasting the mixture at 1150℃ for 2.5h to obtain alkali fusion material;

[0045] (2) crushing and grinding the alkali fusion material to-150μm, mixing the material with water according to a liquid-solid ratio of 3:1, stirring and leaching the mixture at 50℃ for 60min, and filtering and separating the water leaching liquid and the water leaching material;

[0046] (3) mixing the water leaching material with water according to a liquid-solid ratio of 2:1, controlling the leaching temperature at 75℃, leaching for 80min, adding concentrated hydrochloric acid in the leaching process to keep the pH of the solution at about 5, and filtering and separating the transformation liquid and the transformation material;

[0047] (4) mixing the transformation material with concentrated hydrochloric acid according to a liquid-solid ratio of 1:1, adding water in an amount equal to that of the hydrochloric acid, keeping the heating leaching temperature at 100℃, leaching for 120min, and filtering and separating the acid leaching liquid and the acid leaching residue in a closed device with water vapor condensation and recovery.

[0048] (5) adding sulfuric acid according to the concentration of zirconium ions in the acid leaching liquid to make the sulfur-zirconium ratio (molar ratio) in the solution be 0.55-0.60:1, keeping the temperature for precipitating zirconium at about 75℃, and heat preserving for 3h to obtain the basic zirconium sulfate and the yttrium-containing solution by filtering and separating.

[0049] (6) roasting the obtained basic zirconium sulfate at 950℃ for 1h to obtain zirconium oxide product.

[0050] (7) adding oxalic acid to the yttrium-containing solution, the amount of oxalic acid added is about 2:1 (molar ratio) of the yttrium element content, the yttrium precipitation temperature is controlled at 75°C, and the yttrium precipitation time is 2h, and yttrium oxalate and the solution after yttrium precipitation are obtained by filtration separation.

[0051] (8) calcining the obtained yttrium oxalate at 900°C for 1h to obtain a yttria product.

[0052] The main element content of the zirconia product prepared according to the technical method described in Example 1 of the present application is ZrO2(HfO2)≥99.9%, Y2O3<0.001%, Fe2O3<0.0004%, TiO2<0.0002%, SiO2<0.0005%, Na2O<0.0009%, and the zirconium recovery rate is 97.20%;

[0053] The main element content of the yttria product is Y2O3≥99.94%, ZrO2(HfO2)<0.003%, Fe2O3<0.0013%, TiO2<0.0016%, SiO2<0.0008%, Na2O<0.0021%, and the yttrium recovery rate is 95.31%.

[0054] Example 2:

[0055] As shown in Figure 1 , the present application discloses a method for separating and recovering valuable metals from zirconium-yttrium industrial waste, comprising the following steps:

[0056] (1) uniformly mixing zirconium-yttrium industrial waste with sodium hydroxide according to a mass ratio of 1:0.8, and calcining and treating at 900°C for 2h to obtain alkali fusion material;

[0057] (2) crushing and grinding the alkali fusion material to-150μm, mixing with water according to a liquid-solid ratio of 3:1, stirring and leaching at 50°C for 60min, and filtering and separating to obtain water leaching liquid and water leaching material;

[0058] (3) mixing the water leaching material with water according to a liquid-solid ratio of 2:1, controlling the leaching temperature at 75°C, and leaching for 80min, adding concentrated hydrochloric acid in the leaching process to keep the solution pH at about 4, and filtering and separating to obtain transformation liquid and transformation material;

[0059] (4) mixing the transformation material with concentrated hydrochloric acid according to a liquid-solid ratio of 1:0.8, adding water in an amount equal to that of the hydrochloric acid, keeping the heating leaching temperature at 105°C, and leaching for 120min, and performing the reaction in a closed device with water vapor condensation and recovery, and filtering and separating to obtain acid leaching liquid and acid leaching residue.

[0060] (5) According to the concentration of zirconium ions in the acid leaching solution, concentrated sulfuric acid is added so that the sulfur-zirconium ratio (molar ratio) in the solution at this time is 0.55:1, the temperature of the zirconium precipitation is kept at about 75°C, and the holding time is 3h, and the basic zirconium sulfate and yttrium-containing solution are obtained by filtration separation.

[0061] (6) The obtained basic zirconium sulfate is calcined at 950°C for 1h to obtain the zirconia product.

[0062] (7) Oxalic acid is added to the yttrium-containing solution, the amount of oxalic acid added is about 2:1 (molar ratio) of the yttrium element content, the temperature of the yttrium precipitation is controlled at 75°C, the yttrium precipitation time is 2h, and the yttrium oxalate and the post-yttrium precipitation solution are obtained by filtration separation.

[0063] (8) The obtained yttrium oxalate is calcined at 900°C for 1h to obtain the yttrium oxide product.

[0064] The main element content of the zirconia product prepared according to the technical method described in Example 1 of the present application is ZrO2(HfO2)≥99.9%, Y2O3<0.001%, Fe2O3<0.0024%, TiO2<0.0032%, SiO2<0.0008%, Na2O<0.0018%, and the zirconium recovery rate is 77.62%;

[0065] The main element content of the yttrium oxide product is Y2O3≥99.9%, ZrO2(HfO2)<0.005%, Fe2O3<0.0013%, TiO2<0.0019%, SiO2<0.0011%, Na2O<0.0011%, and the yttrium recovery rate is 75.13%.

[0066] Example 3:

[0067] As shown in Figure 1 The present application discloses a method for separating and recovering valuable metals from zirconium-yttrium industrial waste, which comprises the following steps:

[0068] (1) The zirconium-yttrium industrial waste is mixed with sodium carbonate at a mass ratio of 1:1.5, and is calcined at 1100°C for 3h to obtain an alkali fusion material;

[0069] (2) The alkali fusion material is crushed and ground to-150μm, mixed with water at a liquid-solid ratio of 3:1, stirred and leached at 50°C for 60min, and filtered to obtain a water leaching solution and a water leaching material;

[0070] (3) The water leaching material is mixed with water at a liquid-solid ratio of 2:1, the leaching temperature is controlled at 75°C, the leaching time is 80min, concentrated hydrochloric acid is added during the leaching process to keep the pH of the solution at about 5, and the transformed solution and the transformed material are obtained by filtration separation;

[0071] (4) The above-mentioned transformed material is mixed with concentrated hydrochloric acid at a liquid-solid ratio of 1:1, and water is added in an amount equal to that of the hydrochloric acid, the leaching temperature is kept at 100 DEG C, and the leaching time is 120 min, the reaction is carried out in a closed device with water vapor condensation recovery, and the acid leaching liquid and acid leaching residue are obtained by filtration separation.

[0072] (5) According to the zirconium ion concentration in the acid leaching liquid, ammonium sulfate is added so that the sulfur-zirconium ratio (molar ratio) in the solution at this time is 0.60-0.65:1, the zirconium precipitation temperature is kept at about 80 DEG C, the holding time is 3 h, and the basic zirconium sulfate and yttrium-containing solution are obtained by filtration separation.

[0073] (6) The obtained basic zirconium sulfate is calcined at 950 DEG C for 1 h to obtain the zirconia product.

[0074] (7) Oxalic acid is added to the yttrium-containing solution, the amount of oxalic acid added is about 2:1 (molar ratio) of the yttrium element content, the yttrium precipitation temperature is controlled at 75 DEG C, the yttrium precipitation time is 2 h, and the yttrium oxalate and the post-yttrium precipitation liquid are obtained by filtration separation.

[0075] (8) The obtained yttrium oxalate is calcined at 900 DEG C for 1 h to obtain the yttria product.

[0076] The main element content of the zirconia product prepared according to the technical method described in Example 1 of the present application is ZrO2(HfO2)≥99.9%, Y2O3<0.0009%, Fe2O3<0.0014%, TiO2<0.0011%, SiO2<0.0012%, Na2O<0.0033%, and the zirconium recovery rate is 92.44%;

[0077] The main element content of the yttria product is Y2O3≥99.9%, ZrO2(HfO2)<0.002%, Fe2O3<0.0013%, TiO2<0.0016%, SiO2<0.0011%, Na2O<0.0018%, and the yttrium recovery rate is 90.35%.

[0078] Example 4:

[0079] As shown in Figure 1 The present application discloses a method for separating and recovering valuable metals from zirconium-yttrium industrial waste, comprising the following steps:

[0080] (1) The zirconium-yttrium industrial waste is mixed with potassium hydroxide at a mass ratio of 1:1.5, and is calcined at 1200 DEG C for 3 h to obtain an alkali fusion material;

[0081] (2) The alkali fusion material is crushed and ground to -150 μm, mixed with water at a liquid-solid ratio of 3:1, stirred and leached at 50 DEG C for 60 min, and the water leaching liquid and water leaching residue are obtained by filtration separation;

[0082] (3) The above water-impregnated material is mixed with water at a liquid-to-solid ratio of 2:1, the leaching temperature is controlled at 75°C, the leaching time is 80 min, concentrated hydrochloric acid is added during the leaching process to keep the pH of the solution at about 4, and the transformed liquid and the transformed material are separated by filtration;

[0083] (4) The above transformed material is mixed with concentrated hydrochloric acid at a liquid-to-solid ratio of 1:1, and water is added in an amount equal to that of the hydrochloric acid, the heating leaching temperature is kept at 100°C, the leaching time is 120 min, the reaction is carried out in a closed device with water vapor condensation and recovery, and the acid leaching liquid and the acid leaching residue are separated by filtration.

[0084] (5) According to the concentration of zirconium ions in the acid leaching liquid, sulfuric acid and ammonium sulfate are added to make the sulfur-zirconium ratio (molar ratio) in the solution at this time 0.65-0.70:1, the zirconium precipitation temperature is kept at about 8°C, the incubation time is 4 h, and the basic zirconium sulfate and the yttrium-containing solution are separated by filtration.

[0085] (6) The obtained basic zirconium sulfate is calcined at 950°C for 1 h to obtain a zirconia product.

[0086] (7) Oxalic acid is added to the yttrium-containing solution, the amount of oxalic acid added is about 2:1 (molar ratio) of the yttrium element content, the yttrium precipitation temperature is controlled at 75°C, the yttrium precipitation time is 2 h, and the yttrium oxalate and the post-yttrium precipitation liquid are separated by filtration.

[0087] (8) The obtained yttrium oxalate is calcined at 900°C for 1 h to obtain a yttria product.

[0088] The main element content of the zirconia product prepared according to the technical method described in Example 1 of the present application is ZrO2(HfO2)≥99.9%, Y2O3<0.001%, Fe2O3<0.0015%, TiO2<0.0021%, SiO2<0.0014%, Na2O<0.0016%, and the zirconium recovery rate is 91.84%;

[0089] The main element content of the yttria product is Y2O3≥99.9%, ZrO2(HfO2)<0.002%, Fe2O3<0.0009%, TiO2<0.0007%, SiO2<0.0008%, Na2O<0.0008%, and the yttrium recovery rate is 92.35%.

[0090] Example 5:

[0091] As shown in Figure 1 The present application discloses a method for separating and recovering valuable metals from zirconium-yttrium industrial waste, comprising the following steps:

[0092] (1) Zirconium yttrium industrial waste is mixed with sodium hydroxide, potassium hydroxide and sodium carbonate in a mass ratio of 1:0.5:0.5:1, and is calcined at 1250°C for 2.5h to obtain an alkali fusion material;

[0093] (2) The alkali fusion material is crushed and ground to -150μm, mixed with water in a liquid-solid ratio of 2:1, and stirred at 55°C for 60min to obtain a water leaching solution and a water leaching residue by filtration separation;

[0094] (3) The water leaching residue is mixed with water in a liquid-solid ratio of 2:1, and the leaching temperature is controlled at 75°C, the leaching time is 90min, concentrated hydrochloric acid is added during the leaching process to keep the pH of the solution at about 5, and a transformation solution and a transformation residue are obtained by filtration separation;

[0095] (4) The transformation residue is mixed with concentrated hydrochloric acid in a liquid-solid ratio of 1:1, and water is added in an amount equal to that of the hydrochloric acid, the leaching temperature is kept at 100°C, and the leaching time is 120min, and the reaction is carried out in a closed device with water vapor condensation recovery, and an acid leaching solution and an acid leaching residue are obtained by filtration separation.

[0096] (5) According to the concentration of zirconium ions in the acid leaching solution, sulfuric acid is added to make the sulfur-zirconium ratio (molar ratio) in the solution at this time 0.55-0.60:1, the zirconium precipitation temperature is kept at about 75°C, and the holding time is 3h, and an alkaline zirconium sulfate and a yttrium-containing solution are obtained by filtration separation.

[0097] (6) The obtained alkaline zirconium sulfate is calcined at 950°C for 1h to obtain a zirconia product.

[0098] (7) Oxalic acid is added to the yttrium-containing solution, the amount of oxalic acid added is about 2:1 (molar ratio) of the yttrium content, the yttrium precipitation temperature is controlled at 75°C, and the yttrium precipitation time is 2h, and yttrium oxalate and a post-yttrium precipitation solution are obtained by filtration separation.

[0099] (8) The obtained yttrium oxalate is calcined at 900°C for 1h to obtain a yttrium oxide product.

[0100] The main element content of the zirconia product prepared according to the technical method described in Example 1 of the present application is ZrO2(HfO2)≥99.9%, Y2O3<0.001%, Fe2O3<0.0019%, TiO2<0.0012%, SiO2<0.0015%, Na2O<0.0021%, and the zirconium recovery rate is 94.06%;

[0101] The main element content of the yttrium oxide product is Y2O3≥99.95%, ZrO2(HfO2)<0.002%, Fe2O3<0.0015%, TiO2<0.0006%, SiO2<0.0014%, Na2O<0.0006%, and the yttrium recovery rate is 93.02%.

[0102] The main chemical reactions involved in the present application are as follows:

[0103] ZrO2+2NaOH=Na2ZrO3+H2O

[0104] ZrO2+2KOH=K2ZrO3+H2O

[0105] ZrO2+2Na2CO3=Na2ZrO3+CO2

[0106] Na2ZrO3+2HCl=ZrO(OH)2+2NaCl

[0107] K2ZrO3+2HCl=ZrO(OH)2+2KCl

[0108] ZrO(OH)2+2HCl=ZrOCl2+2H2O

[0109] ZrOCl2+H2SO4=ZrOSO4+2HCl

[0110] ZrOCl2+(NH4)2SO4=ZrOSO4+2NH4Cl

[0111] zZrOSO4+(x-y+z)H2O=xZrO2·ySO3·zH2O+(x-y)H2SO4

[0112] 2YCl3+3H2C2O4=Y2(C2O4)3+6HCl.

[0113] The above description is only the preferred embodiments of the present application, and does not limit the technical scope of the present application in any way. Any slight modification, equivalent change and modification made according to the technical essence of the present application to the above embodiments are still within the scope of the technical solution of the present application.

Claims

1. A method for the recovery of valuable metals from zirconium- containing yttrium industrial waste, characterized in that, The method comprises the following steps: (1) mixing zirconium-containing industrial waste with flux, and performing roasting treatment at high temperature to obtain alkali flux; (2) crushing and grinding the alkali flux obtained in step (1), adding water and stirring to leach, to obtain water leaching material and water leaching solution; (3) adding water and hydrochloric acid to the water leaching material obtained in step (2), controlling the pH of the solution, stirring and leaching, to obtain transformation material and transformation solution; (4) mixing the transformation material obtained in step (3) with hydrochloric acid, heating and stirring to leach, to obtain acid leaching solution and acid leaching residue; (5) adding zirconium precipitating agent to the acid leaching solution obtained in step (4), keeping warm and settling, and filtering to separate to obtain zirconium subcarbonate and yttrium-containing solution; (6) performing roasting treatment at high temperature on the zirconium subcarbonate obtained in step (5) to obtain zirconium oxide product; (7) adding oxalic acid solution to the yttrium-containing solution obtained in step (5), keeping warm and settling, to obtain yttrium oxalate and yttrium precipitating solution; (8) performing roasting treatment at high temperature on the yttrium oxalate obtained in step (7) to obtain yttrium oxide product.

2. The method for separating and recovering valuable metals from zirconium-yttrium-containing industrial waste according to claim 1, characterized in that, In step (1), the flux is one or more of NaOH, Na2CO3 and KOH, the addition amount of the alkali flux is 2.2:1 to 1:1 in mass ratio to the zirconium-yttrium waste, the roasting temperature is 700 to 1300 DEG C, and the roasting time is 30 to 240 min.

3. The method for separating and recovering valuable metals from zirconium-yttrium-containing industrial waste according to claim 1, characterized in that, In step (2), the liquid-solid ratio of water to the alkali flux is 4:1 to 2:1, the leaching temperature is 40 to 55 DEG C, and the leaching time is 30 to 80 min.

4. The method for separating and recovering valuable metals from zirconium-yttrium-containing industrial waste according to claim 1, characterized in that, In step (3), the liquid-solid ratio of water to the water leaching material is 2:1 to 1:1, the leaching temperature is 60 to 75 DEG C, the leaching time is 50 to 90 min, and the pH of the solution is controlled to be 3 to 9.

5. The method for separating and recovering valuable metals from zirconium-yttrium-containing industrial waste according to claim 1, characterized in that, In step (4), the liquid-solid ratio of hydrochloric acid to the water leaching material is 2.5:1 to 1:1, the leaching temperature is 85 to 110 DEG C, the leaching time is 60 to 180 min, the hydrochloric acid is concentrated hydrochloric acid with a mass fraction of 36%, and the pH of the solution is controlled to be 1 to 2.

6. The method for separating and recovering valuable metals from zirconium-yttrium-containing industrial waste according to claim 1, characterized in that, In step (5), the zirconium precipitating agent is one or more of sulfuric acid and ammonium sulfate, the addition amount of the zirconium precipitating agent is calculated according to the zirconium concentration in the acid leaching solution, the addition amount of the zirconium precipitating agent is controlled so that the sulfur-zirconium ratio in the solution is 0.4:1 to 0.8:1, the zirconium precipitation temperature is kept at 70 to 80 DEG C, and the zirconium precipitation time is 2 to 6 h.

7. The method for separating and recovering valuable metals from zirconium-yttrium-containing industrial waste according to claim 1, characterized in that, In step (6), the roasting temperature is 900 to 1100 DEG C, and the roasting time is 1 to 1.5 h.

8. The method for separating and recovering valuable metals from zirconium-yttrium-containing industrial waste according to claim 1, characterized in that, In step (7), the addition amount of oxalic acid is calculated according to the yttrium content in the yttrium-containing solution, the addition amount of oxalic acid is controlled to be 1.5:1 to 2.5:1 in mass ratio to the yttrium content, the yttrium precipitation temperature is 70 to 80 DEG C, and the yttrium precipitation time is 1 to 2.5 h.

9. The method for separating and recovering valuable metals from zirconium-yttrium-containing industrial waste according to claim 1, characterized in that, In step (8), the roasting temperature is 800 to 1000 DEG C, and the roasting time is 0.5 to 1.5 h.

10. The method for separating and recovering valuable metals from zirconium-yttrium-containing industrial waste according to claim 1, characterized in that, In step (8), the zirconium-yttrium industrial waste comprises 55 to 82% of ZrO2, 3 to 20% of Y2O3, and the rest of Fe2O3, SiO2, CaO, TiO2 and Al2O3 impurities, and the particle size of the industrial waste powder is less than 48 μm.

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