CN117069139A - Method for preparing high-purity gallium oxide through acid electrolysis - Google Patents
Method for preparing high-purity gallium oxide through acid electrolysis Download PDFInfo
- Publication number
- CN117069139A CN117069139A CN202310806110.6A CN202310806110A CN117069139A CN 117069139 A CN117069139 A CN 117069139A CN 202310806110 A CN202310806110 A CN 202310806110A CN 117069139 A CN117069139 A CN 117069139A
- Authority
- CN
- China
- Prior art keywords
- gallium
- purity
- acid
- oxide
- gallium oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910001195 gallium oxide Inorganic materials 0.000 title claims abstract description 59
- 239000002253 acid Substances 0.000 title claims abstract description 31
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 29
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 119
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 119
- 239000012535 impurity Substances 0.000 claims abstract description 36
- 239000003792 electrolyte Substances 0.000 claims abstract description 29
- 238000004090 dissolution Methods 0.000 claims abstract description 26
- 229910021513 gallium hydroxide Inorganic materials 0.000 claims abstract description 24
- DNUARHPNFXVKEI-UHFFFAOYSA-K gallium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ga+3] DNUARHPNFXVKEI-UHFFFAOYSA-K 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 24
- 230000002378 acidificating effect Effects 0.000 claims abstract description 16
- 239000002244 precipitate Substances 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 13
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- -1 polyethylene Polymers 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000005554 pickling Methods 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 3
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000007086 side reaction Methods 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 6
- 238000011978 dissolution method Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 31
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- 239000007788 liquid Substances 0.000 description 16
- 238000004140 cleaning Methods 0.000 description 11
- 150000002739 metals Chemical class 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910052738 indium Inorganic materials 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 6
- 239000002893 slag Substances 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 150000002259 gallium compounds Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- FZHLWVUAICIIPW-UHFFFAOYSA-M sodium gallate Chemical compound [Na+].OC1=CC(C([O-])=O)=CC(O)=C1O FZHLWVUAICIIPW-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002601 GaN Inorganic materials 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 150000002258 gallium Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention discloses a method for preparing high-purity gallium oxide by acidic electrolysis, which comprises the following steps: acid washing the crude gallium to obtain pretreated crude gallium; (2) Placing the pretreated crude gallium obtained in the step (1) as an anode into an electrolytic tank containing an acidic electrolyte for electrochemical dissolution to obtain a gallium-containing solution; (3) Removing impurities from the gallium-containing solution obtained in the step (2) by using high-purity gallium, and performing liquid-solid separation on the replaced solution to obtain gallium-containing purified solution; (4) Neutralizing the gallium-containing purified solution obtained in the step (3) with ammonia water to precipitate gallium to obtain gallium hydroxide precipitate; (5) And (3) drying and roasting the gallium hydroxide precipitate obtained in the step (4) to obtain the 6N high-purity gallium oxide. The invention can adopt 2N crude gallium as raw material, adopts the electrochemical dissolution method under the acid electrolyte to prepare high-purity gallium oxide, has high production efficiency, less side reaction, less impurity ion content and low production cost, and is suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the field of metal compound preparation, and particularly relates to a production method of a gallium compound.
Background
With the rapid development of new energy, consumer electronics, communication systems, photovoltaic power generation, integrated circuits and other emerging industries, the semiconductor technology has been updated with technology iteration, and gallium oxide has been rapidly developed as a fourth-generation semiconductor material. Gallium oxide is an ultra-wide band gap semiconductor material with a band gap eg=4.9 eV, far beyond the semiconductor materials silicon carbide (3.4 eV), gallium nitride (about 3.3 eV) and silicon (1.1 eV). The gallium oxide-based power device has the characteristics of high withstand voltage, low loss, high efficiency, small size and the like, and compared with the loss of a silicon carbide-based device under the condition of the same withstand voltage, the gallium oxide-based power device is reduced by 86 percent, and the size is only about 1/5 of that of the silicon carbide-based power device. Meanwhile, the high breakdown field strength of gallium oxide ensures that the prepared device can be used under ultrahigh voltage, and is beneficial to improving the carrier collection efficiency. Currently, gallium oxide semiconductor products have shown wide development prospects. Therefore, with the further development of the semiconductor industry, gallium compounds prepared from high-purity gallium oxide will play a significant role in the modern technological development and defense industry.
The current mainstream production process of high-purity gallium oxide firstly needs to dissolve coarse gallium, then precipitate gallium to obtain gallium hydroxide, and then calcine to obtain gallium oxide. The dissolution system of gallium in the course of coarse gallium dissolution includes a strong acid dissolution system and an alkaline electrochemical dissolution system. The strong acid dissolution system is used for dissolving gallium, so that high-concentration strong acid is often required for effectively dissolving gallium, and impurity metals are greatly introduced into the gallic acid-containing solution, so that the subsequent precipitation and calcination are not facilitated to produce high-purity gallium oxide. The alkaline electrochemical dissolution system dissolves gallium metal, namely crude gallium is dissolved in electrochemical solution under alkaline condition, for example, patent CN102978649A adds 99.99% of industrial gallium into an electrolytic tank filled with 30% of sodium hydroxide solution by mass fraction, three-stage electrochemical dissolution is carried out to prepare sodium gallate solution, and then the sodium gallate solution is neutralized, washed, dried and roasted to obtain high-purity gallium oxide.
Therefore, the existing production method of the high-purity gallium oxide has the problems of more impurity ions, high production cost, more side reactions and the like when the crude gallium is dissolved, and the production method of the high-purity gallium oxide with less impurity ions, low production cost and less side reactions is significant for the industrialized production of the gallium oxide.
Disclosure of Invention
The invention aims to overcome the defects and the shortcomings in the background art, and provides a method for preparing high-purity gallium oxide by acidic electrolysis, which has the advantages of low production cost, less side reaction and product purity reaching more than 6N. In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a method for preparing high purity gallium oxide by acidic electrolysis, comprising the steps of:
(1) Pickling the crude gallium to obtain pretreated crude gallium; the coarse gallium can adopt 2N coarse gallium as a raw material, so that the limitation on the raw material is overcome, and the raw material generation cost is greatly reduced;
(2) Placing the pretreated crude gallium obtained in the step (1) as an anode into an electrolytic tank containing an acidic electrolyte for electrochemical dissolution to obtain a gallium-containing solution;
(3) Removing impurities from the gallium-containing solution obtained in the step (2) by using high-purity gallium, and performing liquid-solid separation on the replaced solution to obtain gallium-containing purified solution;
(4) Neutralizing the gallium-containing purified solution obtained in the step (3) with ammonia water to precipitate gallium to obtain gallium hydroxide precipitate;
(5) And (3) drying and roasting the gallium hydroxide precipitate obtained in the step (4) to obtain the 6N high-purity gallium oxide.
In the above method for producing high-purity gallium oxide by acid electrolysis, preferably, the acid electrolyte is H 2 SO 4 Solution or HCl solution, and controlling the pH value of the acidic electrolyte to be 1.0-2.5.
In the above method for producing high purity gallium oxide by acid electrolysis, it is preferable that the current density is controlled to 500 to 1000A/m at the time of electrochemical dissolution 2 。
In the electrochemical dissolution process, the pH value and the current density of the electrolyte need to be strictly controlled in consideration of side reactions, the content of impurity ions and other factors. The lower pH value is controlled to be beneficial to removing impurities, the concentration of the impurities in the electrolyte is reduced, when the pH value of the electrolyte is less than 1.0, the acidity is increased to enable more impurity metals to enter the electrolyte, and when the pH value is more than 2.5, the gallium is separated out due to the increase of the gallium concentration, so that the loss of gallium is caused. At the same time, the current density is controlled to be 500-1000A/m 2 Facilitating the dissolution of gallium and the removal of impurities when the current density is lower than 500A/m 2 The dissolution rate of gallium is relatively slow, when the current is more than 1000A/m 2 The excessive tank voltage can cause impurity metal ions to be dissolved in the electrolyte, which is unfavorable for the subsequent purification of the electrolyte. The main impurities in the crude gallium are indium, copper, lead and the like, in the electrochemical dissolution process, the impurities In, fe, cu, pb, ag, which have equal potential than gallium, are not dissolved in the anode, gather at the bottom of the anode region to become anode mud, and the impurities Ca, na, al and the like, which have potential less than gallium, are dissolved in the anode first, but are not precipitated at the cathode and remain in the electrolyte. When the gallium concentration in the anode chamber is more than 200g/L, part of the anode liquid is pumped out for subsequent purification treatment, and meanwhile, fresh electrolyte is replenished in the cathode chamber. The reactions mainly occurring during electrolysis are:
anode: ga-3e - ＝Ga 3+ ；
And (3) cathode: 2H (H) 2 O+2e - ＝H 2 ↑+2OH - ；
2H + +2e - ＝H 2 ↑。
In the above method for producing high purity gallium oxide by acid electrolysis, it is preferable that the high purity gallium used for removing impurities by substitution with high purity gallium is 6N high purity gallium. And (3) carrying out displacement purification by adopting high-purity gallium, and carrying out displacement removal on metal with lower metal activity than gallium to obtain a high-purity gallium solution. The replacement can be carried out by adopting high-purity gallium with the purity of 6N, and the purifying liquid generally contains ppm-level impurity metal indium and the like. Because the standard electrode potential of gallium is-0.549V, the standard electrode potential of indium is +0.33V, the activity of gallium is far higher than that of indium, and high-purity gallium can be adopted to replace and remove indium and most of impurity metals, thereby achieving the purpose of purifying gallium-containing solution.
In the above method for preparing high purity gallium oxide by acid electrolysis, it is preferable that the end point pH value of the neutralization precipitation is 3.5-6 during the neutralization precipitation, and the gallium hydroxide precipitation is washed to be neutral by deionized water. And washing the gallium hydroxide obtained by neutralization precipitation for a plurality of times to remove residual alkali liquor and mixed soluble metals. The main impurities in the gallium-containing solution are alkali metals or alkaline earth metals Ca, al and the like, the neutralizing agent adopts ammonia water instead of a strong alkaline sodium hydroxide solution, so as to avoid the influence of micro-particle precipitation of alkaline earth metals on the quality of gallium hydroxide caused by local over-high alkalinity in the process of adding the strong alkaline neutralizing agent, while the ammonia water is a weak alkaline substance and generates OH in the hydrolysis process - The purpose of neutralizing the gallium-containing solution is achieved, the pH value of the solution is controlled, and the quality of gallium hydroxide precipitation is guaranteed.
In the method for preparing high-purity gallium oxide by acidic electrolysis, preferably, concentrated sulfuric acid or concentrated hydrochloric acid is used for cleaning the crude gallium for 2-3 times, and the cleaning temperature is normal temperature after 20-30min each time; washing with deionized water for 3-5 times after pickling. The crude gallium is exposed in moist air for a long time, so that the crude gallium is easily oxidized into oxide, meanwhile, oil stains are adhered to the surface of the crude gallium, and the oxide and the oil stains on the surface of the crude gallium can be removed after the crude gallium is washed by concentrated acid, so that the influence of impurities on subsequent purification is reduced; and (3) washing the steel plate with deionized water for 3-5 times after concentrated acid washing, so that acid and impurities remained on the surface can be removed.
In the above method for preparing high purity gallium oxide by acid electrolysis, preferably, during electrochemical dissolution, the pretreated crude gallium is coated by a polyethylene or polypropylene filter bag and then used as an anode, a stainless steel plate is used as a cathode, and a diaphragm is used to divide the electrolytic cell into an anode chamber and a cathode chamber. The coarse gallium is used as anode, and the polyethylene or polypropylene filter bag is used for coating the coarse gallium of the anode, so that anode mud can be prevented from entering the electrolyte and polluting the electrolyte.
In the above method for preparing high purity gallium oxide by acid electrolysis, preferably, the drying and roasting are performed first and then, the drying temperature is controlled to be 80-120 ℃, the drying time is controlled to be 2-6 hours, the roasting temperature is controlled to be 500-800 ℃, and the roasting time is controlled to be 4-6 hours. The purity of the gallium oxide product obtained after roasting is more than 6N. When the roasting temperature is lower than 500 ℃, insufficient decomposition of gallium hydroxide can be caused, the quality of gallium oxide is influenced, and when the roasting temperature exceeds 800 ℃, a more serious agglomeration phenomenon can be caused, the appearance and the size are different, and the quality of gallium oxide is seriously influenced.
Compared with the prior art, the invention has the advantages that:
1. according to the method for preparing high-purity gallium oxide by acidic electrolysis, disclosed by the invention, the inert metal enters anode mud in the electrochemical dissolution process, so that the purification and impurity removal effects are achieved, the high-purity gallium salt solution is obtained, and the problem of more impurity ions caused by dissolving coarse gallium under the condition of strong acid is avoided; compared with an alkaline electrochemical dissolution system, the dissolution rate of gallium is improved, and the production efficiency is improved; the process is simple to operate, the phenomenon that gallium is deposited on a cathode under an alkaline system is avoided, and side reactions are few; in addition, the consumption of alkali can be greatly reduced, and the production cost is reduced.
2. The method for preparing the high-purity gallium oxide by acid electrolysis has the advantages that the neutralizing gallium deposition liquid returns to the system as electrolyte in the whole flow of the method, no waste water or waste gas is produced, the environment is polluted, the raw materials and auxiliary materials are easy to obtain, and the method is suitable for industrial mass production.
In general, the invention can prepare high-purity gallium oxide by adopting 2N crude gallium as a raw material and adopting an electrochemical dissolution method under an acid electrolyte, and the whole process has high production efficiency, less side reaction, less impurity ion content and low production cost, and is suitable for large-scale industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a process flow diagram of the method of the present invention for preparing high purity gallium oxide by acid electrolysis.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1:
as shown in fig. 1, a method for preparing high purity gallium oxide by acidic electrolysis includes the steps of:
(1) Coarse gallium with the gallium content of 99.52 percent is put into concentrated sulfuric acid and concentrated hydrochloric acid ratio of 1:1, carrying out normal-temperature chemical cleaning in a concentrated acid solution for 2 times, each time for 20min, and carrying out countercurrent washing with deionized water for 3 times after the crude gallium is cleaned.
(2) Preparing electrolyte with pH value of 1.0 from concentrated sulfuric acid and water, loading the prepared electrolyte into an electrolytic tank, sleeving a polyethylene filter bag on the chemically cleaned crude gallium, and loading the polyethylene filter bag into the electrolytic tank as an anodeElectrolysis is carried out, and the current density is controlled to be 900A/m 2 Carrying out electrochemical dissolution to obtain gallium-containing 280g/L of gallium solution; the anode mud recovers other valuable metals.
(3) The gallium-containing solution is replaced by high-purity gallium with the potential of the electrode being more than 6N, metal impurities which are more positive than that of the gallium are removed through replacement, the reaction temperature is controlled to be 60 ℃, the reaction time is 2 hours, liquid-solid separation is carried out after the replacement is completed, and purified liquid and purified slag are obtained, the purified liquid is subjected to the next neutralization treatment, and other valuable metals are recovered from the purified slag.
(4) Slowly adding a neutralizer ammonia water into the purifying liquid to neutralize, regulating the pH value of the solution to 6.0, stabilizing the pH value, continuously reacting for 30min, obtaining white gallium hydroxide precipitate after liquid-solid separation, and carrying out size mixing and cleaning on the precipitate with deionized water for a plurality of times until the pH value of the washing liquid is neutral, thus obtaining the high-purity gallium hydroxide.
(5) Drying gallium hydroxide at 80 ℃ and roasting for 5 hours at 550 ℃ to obtain the high-purity gallium oxide with the purity of more than 6N.
As a result of measurement, the content of impurity element In, cu, pb, zn, fe, ni, mg, cr, co, mn and the like in the high-purity gallium oxide in this example was 0.9ppm in total. The specific cases are shown in table 1 below.
Table 1: example 1 major impurity conditions of coarse gallium and high purity gallium oxide
Example 2:
as shown in fig. 1, a method for preparing high purity gallium oxide by acidic electrolysis includes the steps of:
(1) And (3) placing the crude gallium with the gallium content of 99.53% into concentrated sulfuric acid for normal-temperature chemical cleaning for 3 times, cleaning for 20min each time, and carrying out countercurrent washing for 4 times by using deionized water after the crude gallium is cleaned.
(2) Mixing concentrated sulfuric acid with waterPlacing electrolyte with pH value of 2.0, placing the prepared electrolyte into an electrolytic tank, sleeving a polyethylene filter bag on the chemically cleaned crude gallium, placing the sleeve into the electrolytic tank as an anode for electrolysis, and controlling the current density to be 600A/m 2 Carrying out electrochemical dissolution to obtain a gallium solution containing 240g/L gallium; the anode mud recovers other valuable metals.
(3) The gallium-containing solution is replaced by high-purity gallium with the potential of the electrode being more than 6N, metal impurities with the potential being more than that of the gallium are removed through replacement, the reaction temperature is controlled to be 50 ℃, the reaction time is 3 hours, liquid-solid separation is carried out after the replacement is finished, purified liquid and purified slag are obtained, the liquid is subjected to next neutralization treatment, and other valuable metals are recovered from the purified slag.
(4) And slowly adding ammonia water as a neutralizing agent into the purifying liquid to neutralize, regulating the pH value of the solution to 5.5, stabilizing the pH value, continuously reacting for 60min, separating liquid from solid to obtain white gallium hydroxide precipitate, and carrying out size mixing and cleaning on the precipitate with deionized water for multiple times until the pH value of the washing liquid is neutral, thereby obtaining the high-purity gallium hydroxide.
(5) Drying gallium hydroxide at 100 ℃, and roasting for 4 hours at 600 ℃ to obtain the high-purity gallium oxide with the purity of more than 6N.
The content of impurity element In, cu, pb, zn, fe, ni, mg, cr, co, mn and the like in the high-purity gallium oxide in this example was 0.89ppm in total. The specific cases are shown in table 2 below.
Table 2: example 2 major impurity conditions of coarse gallium and high purity gallium oxide
Example 3:
as shown in fig. 1, a method for preparing high purity gallium oxide by acidic electrolysis includes the steps of:
(1) And (3) placing the crude gallium with the gallium content of 99.55% into concentrated hydrochloric acid for normal-temperature chemical cleaning for 3 times, cleaning for 30min each time, and carrying out countercurrent washing for 4 times by using deionized water after the crude gallium is cleaned.
(2) Preparing electrolyte with pH value of 1.5 by concentrated hydrochloric acid and water, and thenFilling the prepared electrolyte into an electrolytic tank, sleeving a polyethylene filter bag for the chemically cleaned crude gallium, then filling the sleeve into the electrolytic tank as an anode for electrolysis, and controlling the current density to be 800A/m 2 Carrying out electrochemical dissolution to obtain gallium-containing 260g/L of gallium solution; the anode mud recovers other valuable metals.
(3) The gallium-containing solution is replaced by high-purity gallium with the potential of the electrode being more than 6N, metal impurities with the potential being more than that of the gallium are removed through replacement, the reaction temperature is controlled to be 55 ℃, the reaction time is 3 hours, liquid-solid separation is carried out after the replacement is finished, purified liquid and purified slag are obtained, the liquid is subjected to next neutralization treatment, and other valuable metals are recovered from the purified slag.
(4) Slowly adding a neutralizer ammonia water into the purifying liquid to neutralize, adjusting the pH value of the solution to 5, stabilizing the pH value, continuously reacting for 60min, obtaining white gallium hydroxide precipitate after liquid-solid separation, and carrying out slurry mixing and cleaning on the precipitate with deionized water for a plurality of times until the pH value of the washing liquid is neutral, thus obtaining the high-purity gallium hydroxide.
(5) Drying gallium hydroxide at 90 ℃, and roasting at 800 ℃ for 6 hours to obtain gallium oxide with more than 6N.
The content of impurity element In, cu, pb, zn, fe, ni, mg, cr, co, mn and the like in the high-purity gallium oxide in this example was 0.94ppm in total. The specific cases are shown in table 3 below.
Table 3: example 3 major impurity conditions of coarse gallium and high purity gallium oxide
Comparative example 1:
the production process of high purity gallium oxide includes the following steps:
(1) The crude gallium with the gallium content of 99.55% in the example 3 is put into concentrated hydrochloric acid to be subjected to normal-temperature chemical cleaning for 3 times, each time for 30min, and after the crude gallium is completely cleaned, deionized water is used for 4 times of countercurrent washing.
(2) Deionized water and a solution containing 30% NaOH are mixed according to the proportion of 1:1, adding the raw gallium into an electrolytic tank, taking the raw gallium as an anode and stainless steel as a cathode, and controlling electricityThe flow density was 800A/m 2 And (3) carrying out electrolysis for a certain time to obtain 260g/L of gallium-containing solution.
(3) Blending the electrolyte, filtering out scum and oxide film, neutralizing with acid, and controlling pH value to 5 to obtain white hydroxide precipitate gallium hydroxide.
(4) Repeatedly washing the white gallium hydroxide precipitate to remove the attached alkali. Drying the washed gallium hydroxide at 90 ℃, and roasting for 6 hours at 800 ℃ to obtain gallium oxide with more than 5N. The specific cases are shown in table 4 below.
Table 4: comparative example 1 major impurity conditions of coarse gallium and high-purity gallium oxide
As can be seen from example 3 and comparative example 1, the effect of example 3 is remarkable due to the comparative example, showing that electrochemical dissolution under an acidic electrolyte is superior to electrochemical dissolution under an alkaline electrolyte in terms of product quality.
Claims (8)
1. A method for preparing high purity gallium oxide by acidic electrolysis, comprising the steps of:
(1) Pickling the crude gallium to obtain pretreated crude gallium;
(2) Placing the pretreated crude gallium obtained in the step (1) as an anode into an electrolytic tank containing an acidic electrolyte for electrochemical dissolution to obtain a gallium-containing solution;
(3) Removing impurities from the gallium-containing solution obtained in the step (2) by using high-purity gallium, and performing liquid-solid separation on the replaced solution to obtain gallium-containing purified solution;
(4) Neutralizing the gallium-containing purified solution obtained in the step (3) with ammonia water to precipitate gallium to obtain gallium hydroxide precipitate;
(5) And (3) drying and roasting the gallium hydroxide precipitate obtained in the step (4) to obtain the 6N high-purity gallium oxide.
2. Preparation of high purity oxidation by acid electrolysis according to claim 1A method for preparing gallium, characterized in that the acid electrolyte is H 2 SO 4 Solution or HCl solution, and controlling the pH value of the acidic electrolyte to be 1.0-2.5.
3. The method for producing high purity gallium oxide by acid electrolysis according to claim 1, wherein the current density is controlled to 500 to 1000A/m at the time of electrochemical dissolution 2 。
4. The method for producing high-purity gallium oxide by acid electrolysis according to claim 1, wherein the high-purity gallium used for removing impurities by substitution with high-purity gallium is 6N high-purity gallium.
5. The method for producing high purity gallium oxide by acid electrolysis according to claim 1, wherein the neutralization precipitation is controlled to have an end point pH of 3.5 to 6.
6. The method for producing high-purity gallium oxide by acid electrolysis according to any one of claims 1 to 5, wherein the crude gallium is washed with concentrated sulfuric acid or concentrated hydrochloric acid 2 to 3 times for 20 to 30 minutes at room temperature during the acid washing; washing with deionized water for 3-5 times after pickling.
7. The method for preparing high purity gallium oxide by acidic electrolysis according to any one of claims 1 to 5, wherein the pretreated crude gallium is coated with a polyethylene or polypropylene filter bag and then used as an anode, a stainless steel plate is used as a cathode, and a diaphragm is used to divide the electrolytic cell into an anode chamber and a cathode chamber during electrochemical dissolution.
8. The method for producing high purity gallium oxide by acid electrolysis according to any one of claims 1 to 5, wherein the drying and firing are performed first and then, the drying temperature is controlled to be 80 to 120 ℃, the drying time is controlled to be 2 to 6 hours, the firing temperature is controlled to be 500 to 800 ℃, and the firing time is controlled to be 4 to 6 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310806110.6A CN117069139A (en) | 2023-07-03 | 2023-07-03 | Method for preparing high-purity gallium oxide through acid electrolysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310806110.6A CN117069139A (en) | 2023-07-03 | 2023-07-03 | Method for preparing high-purity gallium oxide through acid electrolysis |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117069139A true CN117069139A (en) | 2023-11-17 |
Family
ID=88718279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310806110.6A Pending CN117069139A (en) | 2023-07-03 | 2023-07-03 | Method for preparing high-purity gallium oxide through acid electrolysis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117069139A (en) |
-
2023
- 2023-07-03 CN CN202310806110.6A patent/CN117069139A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111455174A (en) | Method for preparing battery-grade nickel sulfate and cobalt sulfate from mixed nickel hydroxide cobalt | |
| CN112981104B (en) | Method for treating cadmium-containing waste residues and recycling metal cadmium | |
| CN108467942B (en) | Method for selectively leaching zinc, lead, gallium and germanium from zinc replacement slag | |
| CN107416908B (en) | A kind of method that low cost prepares high-purity sulphuric acid manganese solution | |
| CN111056576A (en) | Method for preparing battery-grade cobalt sulfate from low-grade cobalt-sulfur tailings | |
| CN101259956A (en) | Deep impurity-removing method for crude tellurium powder | |
| CN111180819B (en) | Preparation method of battery-grade Ni-Co-Mn mixed solution and battery-grade Mn solution | |
| US4030990A (en) | Process for recovering electrolytic copper of high purity by means of reduction electrolysis | |
| CN112499686A (en) | Method for preparing aluminum-doped battery-grade manganese oxyhydroxide by using waste manganese liquid | |
| CN114540641A (en) | Low-cost efficient open circuit and resource utilization method for arsenic in copper electrolysis | |
| CN112725621A (en) | Method for separating nickel, cobalt and manganese from waste lithium battery based on carbonate solid-phase conversion method | |
| CN115367776B (en) | Recovery method of lithium iron phosphate battery | |
| CN117069139A (en) | Method for preparing high-purity gallium oxide through acid electrolysis | |
| CN113789547B (en) | Purification method of copper electrolysis waste liquid | |
| CN110735048A (en) | Method for removing magnesium and fluorine from zinc-containing solution of wet-method zinc smelting | |
| AU2004319088B2 (en) | Method of recovering gallium | |
| JP3810963B2 (en) | Method for separating and concentrating Ga | |
| RU2553318C1 (en) | Gallium production method from alkali-aluminate solutions of alumina industry | |
| KR101258650B1 (en) | Process for preparing cupric oxide powder for electric plating | |
| CN216639668U (en) | Electrolytic device for preparing high-purity gallium | |
| CN115109943B (en) | Method for extracting and recovering copper, zinc, cobalt and manganese metals from copper-manganese-zinc-cobalt chloride solution step by step | |
| CN111647902B (en) | Treatment method of electrolytic solution of tellurium flat plate | |
| CN115566307B (en) | Method for recovering high-purity lithium oxalate and high-purity lithium hydroxide from waste lithium battery | |
| KR101752727B1 (en) | Method for recovering tin from tin residue | |
| CN115261626A (en) | Method for recovering gallium from gallium-zinc-containing material under normal pressure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |