CN113667840B - Method for extracting gallium metal by wet processing gallium nitride waste - Google Patents

Method for extracting gallium metal by wet processing gallium nitride waste Download PDF

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CN113667840B
CN113667840B CN202110975690.2A CN202110975690A CN113667840B CN 113667840 B CN113667840 B CN 113667840B CN 202110975690 A CN202110975690 A CN 202110975690A CN 113667840 B CN113667840 B CN 113667840B
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gallium
gallium nitride
leaching
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CN113667840A (en
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徐亮
赵�卓
张晓峰
田勇攀
张福元
张楷
孟金伟
杨文豪
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Anhui University of Technology AHUT
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B58/00—Obtaining gallium or indium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/008—Wet processes by an alkaline or ammoniacal leaching
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
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    • C25C1/22—Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
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Abstract

The invention discloses a method for extracting gallium metal by wet processing gallium nitride waste, belonging to the technical field of non-ferrous metallurgy. The invention adopts a wet process flow to extract metal gallium from waste gallium nitride, and the specific steps are (1) preparing an alkali solution; (2) adding the gallium nitride waste powder subjected to ball milling and drying treatment into a prepared alkali solution, and stirring to obtain mixed slurry; (3) carrying out oxygen pressure alkaline leaching treatment on the obtained mixed slurry, and stirring; (4) carrying out solid-liquid separation on the solid-liquid mixed slurry obtained by the oxygen pressure alkaline leaching treatment to obtain a gallium-containing leaching solution; (5) electrolyzing the obtained gallium-containing leaching solution, and washing a cathode product to obtain a gallium metal product. The recovery process has the advantages of short flow, environmental friendliness and low cost, and can effectively realize short-flow efficient recovery of gallium nitride waste.

Description

Method for extracting gallium metal by wet processing gallium nitride waste
Technical Field
The invention belongs to the technical field of nonferrous metallurgy, and particularly relates to a method for extracting gallium metal by wet processing of gallium nitride waste.
Background
Gallium is a precious rare metal, and currently, about 10% of the gallium in the world is derived from zinc smelting residues and the recovery and regeneration of other impurities. About 80% of the global gallium consumption is high purity gallium and ultra pure gallium, with nearly 95% of the gallium being used to make GaAs or GaN. Among them, gallium nitride has excellent semiconductor properties, and is widely applied to solid-state light sources, electronic power, microwave radio frequency devices and other aspects, and products thereof cover the fields of semiconductor lighting, mobile communication, energy internet, high-speed rail transit, new energy automobiles, consumer electronic products and the like.
However, with the upgrading of electronic products, the waste materials of gallium nitride are increasing gradually, and because the properties of gallium nitride are stable, the gallium nitride is difficult to recycle, and the existing recycling method has the disadvantages of long process flow, complex operation, generation of acid wastewater in the recycling process, serious pollution to the environment, difficulty in effectively recycling the gallium in the gallium nitride waste materials, and high recycling cost, which is not beneficial to industrial popularization.
Through search, relevant publications on recycling gallium from gallium nitride waste materials exist, for example, chinese patent application No. 201610128046.0, application date is: in 2016, 3, 7 days, the invention and creation name is: a method for recovering metal gallium from gallium nitride waste. The recovery method adopted by the application comprises the steps of placing gallium nitride in a reaction container under normal pressure, dropwise adding a mixed solution of sodium hydroxide and an oxidant into the reaction container, wherein the mass ratio of the sodium hydroxide to the oxidant in the mixed solution is 1: 0.5-9.5, until the gallium nitride is completely dissolved, and finally, the reaction liquid is electrodeposited to recover the gallium metal. The oxidant is hydrogen peroxide or sodium peroxide. However, in this application, because the properties of the gallium nitride waste are stable, thermodynamic and kinetic conditions of the atmospheric pressure leaching process are insufficient, which easily results in a low leaching rate and a low leaching rate of gallium, and finally affects the recovery rate of gallium. In addition, the application has a vague description on the recycling process of gallium nitride waste, and the conditions of the related process parameters are not clear.
Disclosure of Invention
1. Problems to be solved
The invention aims to overcome the defects of longer process, difficult gallium leaching and lower recovery rate in the process of extracting metal gallium from gallium nitride waste by adopting the prior art, and provides a method for extracting the metal gallium from the gallium nitride waste by wet treatment. The technical scheme of the invention can effectively solve the problems, has low recovery cost and is environment-friendly, and is beneficial to realizing the high-efficiency recovery of the gallium nitride waste.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention relates to a method for extracting gallium metal by wet processing gallium nitride waste, which comprises the following steps:
step one, preparing an alkali solution;
step two, adding gallium nitride waste powder subjected to ball milling and drying treatment into the alkali solution prepared in the step one, and stirring to obtain mixed slurry;
step three, carrying out oxygen pressure alkaline leaching treatment on the mixed slurry obtained in the step two, and stirring;
step four, carrying out solid-liquid separation on the solid-liquid mixed slurry obtained by the three-oxygen pressure alkaline leaching treatment to obtain a gallium-containing leaching solution;
and step five, electrolyzing the gallium-containing leaching solution obtained in the step four, and washing a cathode product to obtain a metal gallium product.
Furthermore, in the first step, the prepared alkali solution is single NaOH, KOH or a mixed solution of the NaOH and the KOH.
Furthermore, in the first step, the concentration of NaOH or KOH in the single alkali solution system is 2-8mol/L, and the concentrations of NaOH and KOH in the mixed system are 1-4mol/L respectively.
Furthermore, in the second step, the particle size of the gallium nitride waste powder is controlled to be less than 300 μm during ball milling, the drying temperature is 120-.
Furthermore, in the third step, when the alkaline leaching treatment is carried out under oxygen pressure, the reaction pressure is controlled to be 0.3-0.7Mpa, the reaction temperature is 110-150 ℃, the stirring speed is 250-450rpm, and the reaction time is 1-4 h.
Furthermore, in the third step, the oxygen pressure alkaline leaching treatment comprises two-stage leaching, wherein in the first stage leaching, the reaction pressure is controlled to be 0.3-0.4Mpa, the reaction temperature is 110-; when the second stage leaching is carried out, the reaction pressure is controlled to be 0.4-0.7Mpa, the reaction temperature is controlled to be 120-.
Furthermore, in the third step, when the mixed slurry is subjected to the oxygen pressure alkaline leaching treatment, a chlorine salt is contained in the mixed slurry.
Furthermore, in the fourth step, the solid-liquid separation temperature is controlled to be 40-60 ℃.
Furthermore, in the fifth step, the graphite or platinum plate is used as the anode of the electrolytic system, and the stainless steel plate, the titanium plate or the platinum plate is used as the cathode.
Further, in the fifth step, when the gallium-containing leaching solution is subjected to electrolytic treatment, the current density is controlled to be 30-100A/m 2 The temperature of the electrolyte is 20-80 ℃; washing until the pH value of the attached solution is 7.0-7.5. Wherein, the electrolyzed waste electrolyte can be returned to the oxygen pressure alkaline leaching treatment to be used as a leaching agent for recycling.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the method for extracting the metal gallium by wet processing the gallium nitride waste, disclosed by the invention, the gallium in the gallium nitride waste can be effectively recovered by carrying out two steps of operations of oxygen pressure alkaline leaching treatment and electrolytic deposition on the gallium nitride waste, the whole process flow is short, the operation is simple and convenient, the method is a full wet process flow, the high-temperature and high-pressure operation is not involved, the energy consumption can be effectively avoided, and the equipment maintenance cost is low. According to the invention, the whole process flow is optimally designed, so that the leaching efficiency of gallium can be effectively improved, and the recovery rate of gallium is further improved.
(2) According to the method for extracting the metal gallium by wet processing of the gallium nitride waste, disclosed by the invention, the oxygen pressure alkaline leaching process parameters are optimally designed, the proper pressure is controlled in the leaching process, and the leaching process is carried out at the temperature slightly higher than the boiling point of water.
(3) According to the method for extracting the metal gallium by treating the gallium nitride waste material by the wet method, the oxygen pressure alkaline leaching process adopts a two-stage leaching process, so that the leaching rate of the gallium can be further improved. 80-85% of gallium can be leached out through the first stage of leaching treatment, and the residual gallium can be completely leached out through the second stage of leaching treatment, wherein the leaching rate reaches more than 99%. Meanwhile, when the oxygen pressure alkaline leaching is carried out, chlorine-containing salt can be added to provide chloride ions in the solution and complex metal gallium ions, so that the leaching effect of gallium is further improved.
(4) According to the method for extracting gallium metal by treating gallium nitride waste materials by a wet method, during oxygen pressure alkaline leaching, nitrogen elements in the gallium nitride waste materials are oxidized into pollution-free N by controlling reaction pressure and reaction temperature 2 And the nitrogen oxides which are not in higher valence state can be directly discharged, and any waste gas pollution to the environment can not be caused. Meanwhile, waste electrolyte generated by gallium electrolytic deposition can be directly returned to an oxygen pressure leaching process to be used as a leaching agent for recycling, so that the high-efficiency comprehensive utilization of resources in the process of recovering and extracting gallium from gallium nitride waste is realized, and the method is environment-friendly.
(5) The invention relates to a method for extracting gallium metal by wet processing gallium nitride waste, which directly electrolyzes a gallium-containing solution obtained by oxygen pressure alkaline leaching, reduces and separates out gallium at a cathode by controlling electrochemical conditions such as reasonable electrolytic voltage, current density and the like, simultaneously inhibits the cathode reduction of impurity ions, and can obtain a gallium metal product with the purity of more than 99.9 percent by one-step electrolysis. Meanwhile, the electrolysis in the alkaline system can also effectively avoid the competitive discharge precipitation of hydrogen and gallium at the cathode, the current efficiency in the electrolysis process is high, and the method has obvious advantages compared with the electrolytic deposition process of gallium in an acid system.
Detailed Description
Aiming at the stable property of gallium nitride, the gallium nitride is difficult to dissolve in acid-base solution, so that the extraction of gallium metal from gallium nitride waste materials is difficult, and although some recovery process methods disclosed in the prior art can dissolve part of gallium nitride waste materials after treatment, pure gallium metal can be obtained through a series of subsequent treatments. However, during recovery, the leaching efficiency of gallium nitride is often low, and part of gallium nitride powder is still difficult to dissolve, so that the recovery loss of gallium metal is easy to cause. The invention relates to a method for extracting metal gallium by wet processing gallium nitride waste, which comprises the step of carrying out oxygen pressure leaching on the gallium nitride waste in an alkaline system to dissolve gallium into a leaching solution, and oxidizing nitrogen into environment-friendly N 2 And the gallium and the nitrogen are effectively separated in a gas phase. Then to the gallium-containingThe leachate is directly electrolyzed, gallium is reduced and separated out at the cathode by accurately controlling the electrochemical conditions, and meanwhile, impurity ions are prevented from being separated out, so that a gallium metal product is obtained. The recovery method has the advantages of high recovery rate, simple process, low cost, environmental friendliness and the like, and can realize short-flow high-efficiency comprehensive recovery of gallium nitride waste. The treatment process specifically comprises the following steps:
(1) accurately weighing NaOH, KOH or a solid mixture of the NaOH and the KOH into water, and preparing an alkali solution according to the concentration requirement: in a single alkali solution system, the concentration of NaOH or KOH is controlled to be 2-8mol/L, and the concentrations of NaOH and KOH in a mixed system are respectively 1-4 mol/L.
(2) Ball-milling the gallium nitride waste material to below 300 μm in advance, and drying at 120-150 deg.C for 24-72 h. And (2) adding the fully dried and ground gallium nitride waste powder into the alkali solution prepared in the step (1) to obtain mixed slurry.
(3) Performing oxygen pressure alkaline leaching on the mixed slurry obtained in the step (2), introducing oxygen into an autoclave, keeping the pressure at 0.4-0.7Mpa, the temperature at 110-150 ℃, the stirring speed at 250-450rpm, and the reaction time at 1-4h, so that the gallium is soluble GaO 2 - The form goes into solution and nitrogen is oxidized to N 2 The incoming gas phase is separated from the gallium.
It should be noted that, the oxygen pressure alkaline leaching treatment is performed on the mixed slurry, compared with the existing method for recovering gallium metal from gallium nitride waste by wet method, the method can dissolve most gallium nitride, and is convenient for leaching gallium subsequently. In order to further improve the leaching rate of gallium nitride, the invention adopts two-stage oxygen pressure alkaline leaching, specifically, the reaction pressure is controlled to be 0.3-0.4Mpa, the reaction temperature is 110-120 ℃, the reaction time is 2-4h, the high-efficiency leaching of 80-85% gallium can be preliminarily realized under the conditions of lower temperature and pressure by controlling the pressure, the temperature and the time, the required conditions are relatively mild, the energy consumption is low, and the loss of equipment is small. During the second stage leaching, the reaction pressure is controlled to be 0.4-0.7Mpa, the reaction temperature is controlled to be 120-150 ℃, and the reaction time is 1-3h, so that the wrapping of part of insoluble gallium in the raw materials can be effectively opened, the valuable element gallium is fully dissolved, the leaching rate of gallium is further improved, after the high-temperature high-pressure treatment (relative to the first stage leaching) of the second stage leaching, the leaching rate reaches more than 99%, the obtained leaching slag particles can be further crystallized and grown, the next step of solid-liquid separation is facilitated, and the production efficiency of the whole hydrometallurgy process is improved. In addition, when the oxygen pressure alkaline leaching is carried out, chlorine-containing salt can be added into the reaction system to enhance leaching. More optimally, the chlorine-containing salt is preferably hypochlorite or chlorate or a combination of hypochlorite and chlorate (the existing common hypochlorite and chlorate can be both used), the strong oxidizability of the chlorine-containing salt can also assist the oxidation recovery of the gallium nitride waste, the subsequent leaching of the insoluble gallium nitride is promoted, the treatment time of the whole process is saved, the recovery efficiency is effectively improved, and the recovery cost is reduced.
(4) And (4) carrying out solid-liquid separation on the solid-liquid mixed slurry obtained after the oxygen pressure alkaline leaching in the step (3) at the temperature of 40-60 ℃ to obtain the gallium-containing leaching solution.
(5) Electrolyzing the gallium-containing leaching solution obtained in the step (4), adopting a graphite or platinum plate as an anode, adopting a stainless steel plate, a titanium plate or a platinum plate as a cathode, and controlling the current density to be 30-100A/m 2 And (3) reducing and separating gallium at the cathode at the temperature of 20-80 ℃, and washing the cathode product with water until the pH of the attached solution is 7.0-7.5 to obtain a metal gallium product. In addition, the waste electrolyte generated after electrolysis can also be used as a leaching agent and recycled when the gallium nitride waste powder is subjected to alkaline leaching.
The invention is further described with reference to specific examples.
Example 1
The method for extracting gallium metal by wet processing gallium nitride waste materials in the embodiment specifically comprises the following steps:
(1) 80g of NaOH solid is accurately weighed and added into water to prepare 1L of 2mol/L alkali solution.
(2) Gallium nitride waste was ball milled to 300 μm or less in advance and dried at 120 ℃ for 72 hours. And (2) adding the fully dried and ground gallium nitride waste powder into the alkali solution prepared in the step (1) to obtain mixed slurry.
(3) When the mixed slurry in the step (2) is subjected to oxygen pressure alkaline leaching, sodium hypochlorite is dropwise added, oxygen is introduced into the autoclave, and the control is carried outStirring at 250rpm, first stage leaching at 0.35Mpa and 115 deg.C for 3 hr, and second stage leaching at 0.6Mpa and 130 deg.C for 2 hr to make gallium enter the solution in the form of soluble GaO 2-and nitrogen oxidized to N 2 The incoming gas phase is separated from the gallium.
(4) And (4) carrying out solid-liquid separation on the solid-liquid mixed slurry obtained after the oxygen pressure alkaline leaching in the step (3) at the temperature of 40 ℃ to obtain the gallium-containing leaching solution.
(5) And (4) electrolyzing the gallium-containing leachate obtained in the step (4), adopting graphite as an anode and a stainless steel plate as a cathode, controlling the current density to be 30A/m2, controlling the temperature of the electrolyte to be 20 ℃, reducing and separating gallium at the cathode, and washing a cathode product with water until the pH of an attached solution is 7.0 to obtain a metal gallium product.
By adopting the treatment method of the embodiment, the phase composition of the solid product is analyzed through X-ray diffraction, and the chemical compositions of the solid product and the liquid product are respectively analyzed through X-ray fluorescence spectroscopy and inductively coupled plasma spectroscopy, so that the gallium leaching rate in the oxygen pressure alkaline leaching process of the gallium nitride waste is 99.83%, the purity of the metal gallium product obtained through electrolysis is 99.95%, and the total recovery rate of gallium reaches 99.12%.
Example 2
The method for extracting gallium metal by wet processing gallium nitride waste materials in the embodiment specifically comprises the following steps:
(1) 320g of NaOH solid is accurately weighed and added into water to prepare 1L of alkali solution with the concentration of 8 mol/L.
(2) The gallium nitride waste is ball milled to below 300 μm in advance and dried at 150 ℃ for 24 h. And (2) adding the fully dried and ground gallium nitride waste powder into the alkali solution prepared in the step (1) to obtain mixed slurry.
(3) Carrying out oxygen pressure alkaline leaching on the mixed slurry obtained in the step (2), dripping sodium chloride and introducing oxygen into an autoclave, controlling the stirring speed to be 250rpm, controlling the reaction pressure to be 0.3Mpa, the reaction temperature to be 120 ℃ and the reaction time to be 2 hours when carrying out first-stage leaching, and controlling the reaction pressure to be 0.4Mpa, the reaction temperature to be 120 ℃ and the reaction time to be 3 hours when carrying out second-stage leaching to ensure thatGallium goes into solution as soluble GaO 2-and nitrogen is oxidized to N 2 The incoming gas phase is separated from the gallium.
(4) And (4) carrying out solid-liquid separation on the solid-liquid mixed slurry obtained after the oxygen pressure alkaline leaching in the step (3) at the temperature of 60 ℃ to obtain the gallium-containing leaching solution.
(5) Electrolyzing the gallium-containing leaching solution obtained in the step (4), adopting a platinum plate as an anode and a titanium plate as a cathode, and controlling the current density to be 100A/m 2 And (3) reducing and precipitating gallium at the cathode by using the temperature of the electrolyte at 80 ℃, and washing the cathode product with water until the pH of the attached solution is 7.5 to obtain the metal gallium product.
By adopting the treatment method of the embodiment, the phase composition of the solid product is analyzed through X-ray diffraction, and the chemical compositions of the solid product and the liquid product are respectively analyzed through X-ray fluorescence spectroscopy and inductively coupled plasma spectroscopy, so that the gallium leaching rate in the oxygen pressure alkaline leaching process of the gallium nitride waste is 99.25%, the purity of the metal gallium product obtained through electrolysis is 99.91%, and the total recovery rate of gallium reaches 99.02%.
Example 3
The method for extracting gallium metal by wet processing gallium nitride waste materials in the embodiment specifically comprises the following steps:
(1) 160g of NaOH solid is accurately weighed and added into water to prepare 1L of alkali solution with the concentration of 4 mol/L.
(2) Gallium nitride waste was ball milled to 300 μm or less in advance and dried at 130 ℃ for 48 hours. And (2) adding the fully dried and ground gallium nitride waste powder into the alkali solution prepared in the step (1) to obtain mixed slurry.
(3) Carrying out oxygen pressure alkaline leaching on the mixed slurry obtained in the step (2), dropwise adding sodium chloride and sodium hypochlorite, introducing oxygen into an autoclave, controlling the stirring speed to be 250rpm, controlling the reaction pressure to be 0.4Mpa, the reaction temperature to be 110 ℃ and the reaction time to be 4h when carrying out first-stage leaching, and controlling the reaction pressure to be 0.7Mpa, the reaction temperature to be 150 ℃ and the reaction time to be 1h when carrying out second-stage leaching to enable gallium to be soluble GaO 2- The form goes into solution and nitrogen is oxidized to N 2 The incoming gas phase is separated from the gallium.
(4) And (4) carrying out solid-liquid separation on the solid-liquid mixed slurry obtained after the oxygen pressure alkaline leaching in the step (3) at the temperature of 50 ℃ to obtain the gallium-containing leaching solution.
(5) Electrolyzing the gallium-containing leachate obtained in the step (4), wherein a platinum plate is used as an anode, a titanium plate is used as a cathode, and the current density is controlled to be 50A/m 2 And (3) reducing and precipitating gallium at the cathode at the temperature of the electrolyte of 40 ℃, and washing the cathode product with water until the pH of the attached solution is 7.0 to obtain a metal gallium product.
By adopting the treatment method of the embodiment, the phase composition of the solid product is analyzed through X-ray diffraction, and the chemical compositions of the solid product and the liquid product are respectively analyzed through X-ray fluorescence spectroscopy and inductively coupled plasma spectroscopy, so that the gallium leaching rate in the oxygen pressure alkaline leaching process of the gallium nitride waste is 99.52%, the purity of the metal gallium product obtained through electrolysis is 99.94%, and the total recovery rate of gallium reaches 99.18%.
Example 4
The method for extracting gallium metal by wet processing gallium nitride waste materials comprises the following steps:
(1) 280g of KOH solid is accurately weighed and added into water to prepare 1L of alkali solution with the concentration of 5 mol/L.
(2) Gallium nitride waste was ball milled to below 300 μm in advance and dried at 140 ℃ for 48 h. And (2) adding the fully dried and ground gallium nitride waste powder into the alkali solution prepared in the step (1) to obtain mixed slurry.
(3) Performing oxygen pressure alkaline leaching on the mixed slurry obtained in the step (2), dripping sodium chlorate, introducing oxygen into an autoclave, controlling the stirring speed to be 250rpm, controlling the reaction pressure to be 0.36Mpa and the reaction temperature to be 116 ℃ and the reaction time to be 3.5h when performing first-stage leaching, and controlling the reaction pressure to be 0.6Mpa and the reaction temperature to be 135 ℃ and the reaction time to be 2h when performing second-stage leaching to ensure that gallium is soluble GaO 2- The form goes into solution and nitrogen is oxidized to N 2 The incoming gas phase is separated from the gallium.
(4) And (4) carrying out solid-liquid separation on the solid-liquid mixed slurry obtained after the oxygen pressure alkaline leaching in the step (3) at the temperature of 40 ℃ to obtain the gallium-containing leaching solution.
(5) Electrolyzing the gallium-containing leaching solution obtained in the step (4), adopting graphite as an anode and a platinum plate as a cathode, and controlling the current density to be60A/m 2 And (3) reducing and precipitating gallium at the cathode by using the temperature of the electrolyte at 50 ℃, and washing the cathode product with water until the pH of the attached solution is 7.0 to obtain the metal gallium product.
By adopting the treatment method of the embodiment, the phase composition of the solid product is analyzed through X-ray diffraction, and the chemical compositions of the solid product and the liquid product are respectively analyzed through X-ray fluorescence spectroscopy and inductively coupled plasma spectroscopy, so that the gallium leaching rate in the oxygen pressure alkaline leaching process of the gallium nitride waste is 99.30%, the purity of the metal gallium product obtained through electrolysis is 99.92%, and the total recovery rate of gallium reaches 99.07%.
Example 5
The method for extracting gallium metal by wet processing gallium nitride waste materials in the embodiment specifically comprises the following steps:
(1) 100g of NaOH and 140g of KOH solid were accurately weighed and added to water to prepare 1L of an alkali solution having a concentration of 5 mol/L.
(2) Gallium nitride waste was ball milled to 300 μm or less in advance and dried at 130 ℃ for 72 hours. And (2) adding the fully dried and ground gallium nitride waste powder into the alkali solution prepared in the step (1) to obtain mixed slurry.
(3) Carrying out oxygen pressure alkaline leaching on the mixed slurry obtained in the step (2), dripping sodium hypochlorite and introducing oxygen into an autoclave, controlling the stirring speed to be 250rpm, controlling the reaction pressure to be 0.34Mpa and the reaction temperature to be 116 ℃ and the reaction time to be 2.8h when carrying out first stage leaching, and controlling the reaction pressure to be 0.55Mpa and the reaction temperature to be 140 ℃ and the reaction time to be 2.5h when carrying out second stage leaching, so that gallium enters the solution in a soluble GaO 2-form, and nitrogen is oxidized to be N 2 The incoming gas phase is separated from the gallium.
(4) And (4) carrying out solid-liquid separation on the solid-liquid mixed slurry obtained after the oxygen pressure alkaline leaching in the step (3) at the temperature of 55 ℃ to obtain the gallium-containing leaching solution.
(5) Electrolyzing the gallium-containing leaching solution obtained in the step (4), adopting graphite as an anode and a platinum plate as a cathode, and controlling the current density to be 80A/m 2 And (3) reducing and precipitating gallium at the cathode at the temperature of 70 ℃, and washing the cathode product with water until the pH of the attached solution is 7.5 to obtain the metal gallium product.
By adopting the treatment method of the embodiment, the phase composition of the solid product is analyzed through X-ray diffraction, and the chemical components of the solid product and the liquid product are respectively analyzed through X-ray fluorescence spectroscopy and inductively coupled plasma spectroscopy, so that the gallium leaching rate in the oxygen pressure alkaline leaching process of the gallium nitride waste is 99.48%, the purity of the metal gallium product obtained through electrolysis is 99.96%, and the total recovery rate of gallium reaches 99.21%.
Example 6
The method for extracting gallium metal by wet processing gallium nitride waste materials comprises the following steps:
(1) 100g of NaOH and 140g of KOH solid were accurately weighed and added to water to prepare 1L of an alkali solution having a concentration of 5 mol/L.
(2) Gallium nitride waste was ball milled to 300 μm or less in advance and dried at 130 ℃ for 72 hours. And (2) adding the fully dried and ground gallium nitride waste powder into the alkali solution prepared in the step (1) to obtain mixed slurry.
(3) Performing oxygen pressure alkaline leaching on the mixed slurry obtained in the step (2), introducing oxygen into an autoclave, controlling the stirring speed to be 250rpm, controlling the reaction pressure to be 0.34Mpa and the reaction temperature to be 116 ℃ and the reaction time to be 2.8h when performing first-stage leaching, and controlling the reaction pressure to be 0.55Mpa and the reaction temperature to be 140 ℃ and the reaction time to be 2.5h when performing second-stage leaching, so that gallium enters the solution in the form of soluble GaO 2-and nitrogen is oxidized to be N 2 The incoming gas phase is separated from the gallium.
(4) And (4) carrying out solid-liquid separation on the solid-liquid mixed slurry obtained after the oxygen pressure alkaline leaching in the step (3) at the temperature of 55 ℃ to obtain a gallium-containing leaching solution.
(5) Electrolyzing the gallium-containing leaching solution obtained in the step (4), adopting graphite as an anode and a platinum plate as a cathode, and controlling the current density to be 80A/m 2 And (3) reducing and precipitating gallium at the cathode at the temperature of 70 ℃, and washing the cathode product with water until the pH of the attached solution is 7.5 to obtain the metal gallium product.
By adopting the treatment method of the embodiment, the phase composition of the solid product is analyzed through X-ray diffraction, and the chemical compositions of the solid product and the liquid product are respectively analyzed through X-ray fluorescence spectroscopy and inductively coupled plasma spectroscopy, so that the gallium leaching rate in the oxygen pressure alkaline leaching process of the gallium nitride waste is 99.10%, the purity of the metal gallium product obtained through electrolysis is 99.94%, and the total recovery rate of gallium reaches 99.20%.

Claims (7)

1. A method for extracting gallium metal by wet processing gallium nitride waste materials is characterized by comprising the following steps:
step one, preparing an alkali solution;
step two, adding gallium nitride waste powder subjected to ball milling and drying treatment into the alkali solution prepared in the step one, and stirring to obtain mixed slurry;
thirdly, carrying out oxygen pressure alkaline leaching treatment on the mixed slurry obtained in the second step, and stirring; wherein, when the oxygen pressure alkaline leaching is carried out, the reaction pressure is controlled to be 0.3-0.7MPa, the reaction temperature is 110-150 ℃, the stirring speed is 250-450rpm, and the reaction time is 1-4 h; the oxygen pressure alkaline leaching treatment comprises two-stage leaching, wherein in the first stage leaching, the reaction pressure is controlled to be 0.3-0.4MPa, the reaction temperature is 110-120 ℃, and the reaction time is 2-4 h; when the second stage leaching is carried out, the reaction pressure is controlled to be 0.4-0.7MPa, the reaction temperature is controlled to be 120-;
step four, carrying out solid-liquid separation on the solid-liquid mixed slurry obtained by the three-oxygen pressure alkaline leaching treatment to obtain a gallium-containing leaching solution;
step five, electrolyzing the gallium-containing leaching solution obtained in the step four, and controlling the current density to be 30-100A/m 2 The temperature of the electrolyte is 20-80 ℃; washing until the pH value of the attached solution is 7.0-7.5, and washing the cathode product to obtain a gallium metal product.
2. The method for extracting gallium metal by wet processing gallium nitride waste according to claim 1, wherein the method comprises the following steps: in the first step, the prepared alkali solution is single NaOH, KOH or a mixed solution of the NaOH and the KOH.
3. The method for extracting gallium metal from gallium nitride waste by wet processing according to claim 2, wherein the method comprises the following steps: in the first step, in a single alkali solution system, the concentration of NaOH or KOH is 2-8mol/L, and the concentrations of NaOH and KOH in a mixed system are 1-4mol/L respectively.
4. The method for extracting gallium metal from gallium nitride waste material by wet processing according to claim 1, wherein the method comprises the following steps: in the second step, during ball milling, the particle size of the gallium nitride waste powder is controlled to be below 300 mu m, the drying temperature is 120 ℃ and 150 ℃, and the drying time is 24-72 h.
5. The method for extracting gallium metal from gallium nitride waste material by wet processing according to any one of claims 1-4, wherein the method comprises the following steps: in the third step, chlorine salt is contained in the mixed slurry when the mixed slurry is subjected to oxygen pressure alkaline leaching treatment.
6. The method for extracting gallium metal from gallium nitride waste by wet processing according to claim 5, wherein the method comprises the following steps: in the fourth step, the solid-liquid separation temperature is controlled to be 40-60 ℃.
7. The method for extracting gallium metal from gallium nitride waste by wet processing according to claim 5, wherein the method comprises the following steps: and in the fifth step, the graphite or platinum plate is used as an anode of the electrolytic system, and a stainless steel plate, a titanium plate or a platinum plate is used as a cathode of the electrolytic system.
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CN103388159B (en) * 2012-05-11 2016-08-03 格林美股份有限公司 A kind of method reclaiming gallium from nitrogen gallium garbage
CN105567982B (en) * 2016-03-07 2017-10-27 南京金美镓业有限公司 A kind of method that gallium is reclaimed in the waste material from gallium nitride
CN108677017A (en) * 2018-05-23 2018-10-19 汉能新材料科技有限公司 A kind of recovery method of copper indium gallium selenide waste material
CN109182787B (en) * 2018-11-01 2020-07-31 中南大学 Method for improving leaching rate of germanium and gallium in material containing germanium and gallium
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