CN115287456A - Method for recovering metal gallium from gallium nitride waste - Google Patents
Method for recovering metal gallium from gallium nitride waste Download PDFInfo
- Publication number
- CN115287456A CN115287456A CN202210810608.5A CN202210810608A CN115287456A CN 115287456 A CN115287456 A CN 115287456A CN 202210810608 A CN202210810608 A CN 202210810608A CN 115287456 A CN115287456 A CN 115287456A
- Authority
- CN
- China
- Prior art keywords
- gallium
- chloride
- gallium nitride
- molten salt
- waste
- 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
- 229910002601 GaN Inorganic materials 0.000 title claims abstract description 62
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 57
- 239000002699 waste material Substances 0.000 title claims abstract description 49
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 30
- 239000002184 metal Substances 0.000 title claims abstract description 30
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 56
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims abstract description 46
- 150000003839 salts Chemical class 0.000 claims abstract description 29
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000009833 condensation Methods 0.000 claims abstract description 21
- 230000005494 condensation Effects 0.000 claims abstract description 21
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 21
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 18
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 7
- 239000004065 semiconductor Substances 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 125000001309 chloro group Chemical class Cl* 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 150000003841 chloride salts Chemical class 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 238000011084 recovery Methods 0.000 description 17
- 239000007789 gas Substances 0.000 description 13
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 8
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 4
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- MHUWZNTUIIFHAS-XPWSMXQVSA-N 9-octadecenoic acid 1-[(phosphonoxy)methyl]-1,2-ethanediyl ester Chemical compound CCCCCCCC\C=C\CCCCCCCC(=O)OCC(COP(O)(O)=O)OC(=O)CCCCCCC\C=C\CCCCCCCC MHUWZNTUIIFHAS-XPWSMXQVSA-N 0.000 description 1
- 238000004131 Bayer process Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229940047047 sodium arsenate Drugs 0.000 description 1
- 229910052950 sphalerite Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- 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
- C22B7/001—Dry processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0632—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with gallium, indium or thallium
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
-
- 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
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/34—Electrolytic production, recovery or refining of metals by electrolysis of melts of metals not provided for in groups C25C3/02 - C25C3/32
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for recovering metal gallium from gallium nitride wastes, which comprises the steps of preparing gallium chloride by utilizing gallium nitride wastes, crushing the gallium nitride wastes, uniformly mixing the crushed gallium nitride wastes with anhydrous ammonium chloride, and carrying out thermal reaction on the obtained mixed raw materials to generate gas containing gallium chloride; and carrying out primary condensation on the obtained gallium chloride-containing gas through a condenser to obtain ammonium chloride solid and gallium chloride gas, carrying out secondary condensation on the gallium chloride gas to obtain gallium chloride solid, mixing the gallium chloride solid with other chloride to prepare molten salt electrolyte, and carrying out molten salt electrolysis to obtain metal gallium. The method can effectively treat the gallium nitride waste, has simple process, high preparation yield, low cost, environmental protection and safety, is suitable for mass production, and has good industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of metal gallium recovery, and particularly relates to a method for recovering gallium chloride and metal gallium from gallium nitride wastes.
Background
Gallium is a key strategic rare metal, a series of compounds prepared from the gallium are made into semiconductor materials, electron optical materials, novel functional materials, special alloys and the like, and the gallium is an important basic material for supporting the fields of new energy technologies, modern communication, semiconductor industry and the like. China is the largest native gallium producing country around the world, and supplies more than 70% of the global requirements for native gallium. With the rapid development of integrated circuits, high power semiconductors and solar photovoltaic industries in recent years, the demand for gallium has increased.
On the one hand, the distribution of gallium is very dilute, which is often present in other minerals in adsorbed state or as fine-grained independent minerals, such as bauxite and sphalerite. Therefore, almost all primary gallium is recovered from the alumina production recycle mother liquor as well as the zinc dross leach solution. Currently, 90% of gallium is sourced from the bayer process liquor in the production of alumina. But the natural resources are always limited and the exploitation of the resources is also always accompanied by environmental pollution. Therefore, the recycling of secondary resources of gallium has also attracted more and more attention, such as gallium nitride, gallium arsenide, etc. Gallium nitride and gallium arsenide are semiconductor materials that are currently widely used in the fields of optoelectronics and microelectronics, for example, as large screens, vehicle lights, traffic lights, semiconductor illumination lights, digital memory devices, wireless communication devices, photodetectors, and the like. If the gallium nitride-containing waste is discarded at will, a large amount of land resources are occupied, and the waste of precious rare metal gallium is caused. Due to age issues of the application products and the requirements of the new generations, more and more waste gallium nitride or waste gallium arsenide materials are emerging. The existing treatment methods mainly comprise a wet method and a fire method, or a method combining the wet method and the fire method. For example, patent CN201911024489.5 performs alkaline leaching on gallium arsenide waste residue, and then obtains sodium arsenate through evaporation crystallization, and finally obtains metal gallium through cyclone electrodeposition; in patent CN201610128046.0, gallium nitride, sodium hydroxide and an oxidant are mixed and dissolved, and then a reaction solution is subjected to electrodeposition to recover metal gallium; CN201210145214.9 adopts the mode of acid leaching, extraction and cyclone electrolysis to recover gallium nitride-containing waste; CN201420736886.1 proposes a device for recovering gallium nitride waste by using hydrogen thermal reduction. One problem commonly faced by the wet process flow is that a large amount of chemical reagents are required, the recovery flow is long, and the environmental protection is not enough. The main problems of the pyrogenic process are small production batch, poor safety and low yield.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a method for recovering gallium chloride and further recovering gallium metal from gallium nitride wastes.
In one aspect, the present invention provides a method for preparing gallium chloride from gallium nitride waste, comprising the following steps:
crushing gallium nitride waste;
step two, uniformly mixing the crushed gallium nitride waste with anhydrous ammonium chloride;
transferring the obtained mixed raw materials to a thermal reactor for thermal reaction to generate gas containing gallium chloride;
step four, the obtained gallium chloride-containing gas is condensed once through a condenser, and ammonium chloride solid and gallium chloride gas are separated and obtained;
and step five, carrying out secondary condensation on the gallium chloride gas to obtain a gallium chloride solid.
As a preferred embodiment, the crushed particles of the gallium nitride waste material are not larger than 100 meshes.
As a preferred example, the gallium nitride waste material crushing method may be one of ball mill crushing, squeeze crushing, impact crushing or mill crushing.
As a preferred embodiment, the anhydrous ammonium chloride is in powder form. And carrying out vacuum drying treatment on mixed powder obtained by mixing the gallium nitride waste and anhydrous ammonium chloride powder so as to remove water in the powder.
As a preferred embodiment, the mass ratio of the anhydrous ammonium chloride to the gallium nitride waste material is 2:1 to 5:1.
as a preferred embodiment, the mixed powder of the gallium nitride waste and the anhydrous ammonium chloride powder should be vacuum dried to remove water in the powder.
As a preferred embodiment, the thermal reactor should be provided with an exhaust channel to realize smooth condensation of the generated gas in the reactor into the condenser.
As a preferred embodiment, the thermal reactor should be capable of achieving a uniform high temperature field required to provide the reaction, with a temperature control error within 2 ℃.
As a preferred embodiment, the temperature of the thermal reaction is controlled to be 400-600 ℃.
As a preferred embodiment, the temperature of the primary condensation is 210-250 ℃.
As a preferred embodiment, the temperature of the secondary condensation is 40-60 ℃.
As a preferred embodiment, the temperature control error of the condenser is within +/-0.5 ℃.
As a preferred embodiment, the gallium nitride waste is derived from semiconductor materials containing gallium nitride components, including silicon substrate gallium nitride, sapphire substrate gallium nitride and the like, and gallium nitride waste in the production process thereof. Further preferably, the content of gallium nitride in the gallium nitride waste is not less than 1%.
In another aspect, the invention also provides a method for recovering metal gallium from gallium nitride waste, gallium chloride powder is obtained by adopting the method, the obtained gallium chloride powder is used as a raw material to prepare a molten salt electrolyte, and the obtained molten salt electrolyte is subjected to molten salt electrolysis to obtain the metal gallium.
Furthermore, the molten salt electrolyte is formed by mixing gallium chloride and other chlorine salts, and the mass fraction of the gallium chloride in the molten salt electrolyte is 40-80%.
Further, the other chloride salt includes any one or more of lithium chloride, sodium chloride, potassium chloride, magnesium chloride, or calcium chloride.
Further, the current density of the molten salt electrolysis is 5-10A/dm 2 。
Further, the temperature of the molten salt electrolysis is 120-750 ℃.
As can be seen from fig. 2, gallium nitride reacts with ammonium chloride: gaN(s) +3NH 4 Cl＝GaCl 3 (g)+4NH 3 (g) The Gibbs free energy is reduced along with the rise of the temperature, the Gibbs free energy is zero at about 300 ℃, the reaction can be carried out in the forward direction, the reaction process can be that ammonium chloride powder is heated and decomposed into hydrogen chloride and ammonia gas, and the hydrogen chloride gas reacts with gallium nitride to generate gallium chloride and ammonia gas. Therefore, theoretically, the thermal reaction of gallium nitride should be carried out above 300 ℃. From the production experiment, the difference of temperature also has a great influence on the recovery rate of gallium nitride: the reaction can not occur at a lower temperature, and the recovery rate is lower; at higher temperatures, the reaction takes place more rapidly, in particular the decomposition reaction of ammonium chloride, which in turn makes the reaction impossible and the recovery rate decreases. Therefore, the temperature range of 400-600 ℃ is selected in the application. Subsequently, by two-stage condensation, the first of which is to react NH at this temperature 3 (g)+HCl(g)＝NH 4 Cl recovers ammonium chloride after the thermal reaction, but does not liquefy or desublimate gallium chloride gas at the temperature; the second stage of condensation is to recover the gallium chloride gas as solid gallium chloride at the temperature through condensation and desublimation. And finally, preparing the gallium chloride solid into molten salt, and recovering the metal gallium by utilizing molten salt electrolysis.
The invention utilizes the method that gallium nitride waste material and ammonium chloride are thermally reacted to produce gallium chloride gas under the heating condition, then gallium chloride is recovered in a condensation mode, and gallium metal is recovered in a molten salt electrolysis mode to realize the recovery of gallium from the gallium nitride waste material, and the method has the advantages that:
(1) The using method has simple process, high operability and good industrial application prospect;
(2) The method utilizes the simple thermal reaction of ammonium chloride and gallium nitride to recover the gallium nitride, and has high safety;
(3) The method effectively improves the utilization rate of ammonium chloride by utilizing two-stage condensation and can also improve the purity of the recovered gallium chloride;
(4) The method can be suitable for industrial mass production by utilizing a mature fused salt electrolysis method.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a thermodynamic diagram of the thermal reaction of gallium nitride with ammonium chloride and the change in recovery.
Detailed Description
Specific embodiments of the present invention are described in detail with the understanding that the scope of the present invention is not limited by the specific embodiments.
In the following embodiment of the invention, the gallium nitride waste is from silicon substrate gallium nitride waste, wherein the mass fraction of gallium nitride is 30%. The recovery rate of gallium metal was calculated as follows
η＝m 1 *n 1 /m 0 *n 0
Wherein m is 0 Mass m of gallium nitride waste 1 Quality of the product obtained by molten salt electrolysis, n 0 Is the mass fraction of the gallium element in the gallium nitride waste, n 1 Is the mass fraction (i.e., purity) of gallium in the product obtained by molten salt electrolysis.
Example 1
A method of recovering gallium metal from gallium nitride waste, the method comprising the steps of:
step one, crushing gallium nitride waste materials to 150 meshes through ball milling;
step two, mixing anhydrous ammonium chloride powder and gallium nitride waste materials in a ratio of 2:1, uniformly mixing;
transferring the mixed powder to a thermal reactor, and carrying out thermal reaction at 400 ℃ to generate gallium chloride-containing gas;
step four, the gas produced by the reaction is condensed at 210 ℃ for the first time through a condenser, ammonium chloride solid and gallium chloride gas are separated, and the obtained ammonium chloride solid can be returned to the mixing stage of the step two for recycling;
step five, further condensing the obtained gallium chloride gas at 40 ℃ to obtain gallium chloride powder;
step six, mixing the obtained gallium chloride powder with lithium chloride and sodium chloride to prepare a molten salt electrolyte, wherein the mass ratio of gallium chloride is 50%;
step seven, taking metal platinum as a cathode and an anode, and the current density is 6A/dm 2 And the electrolysis temperature is 450 ℃, and the metal gallium is obtained by molten salt electrolysis.
The recovery rate of the gallium metal recovered by the process flow is 82.6 percent, and the purity is 99.85 percent.
Example 2
The method is the same as case 1, and is different from the following steps: (1) The mass ratio of the anhydrous ammonium chloride to the gallium nitride waste powder is 3:1; (2) the thermal reaction temperature is 450 ℃; (3) the condensation temperature of the first section is 215 ℃; (4) the condensation temperature of the second section is 45 ℃; (5) The current density is 6.5A/dm 2 The electrolysis temperature was 500 ℃.
The gallium metal is recovered through the process flow, the recovery rate is 82.1%, and the purity is 99.81%.
Example 3
The method is the same as case 1, and is different from the following steps: (1) The mass ratio of the anhydrous ammonium chloride to the gallium nitride waste powder is 2.5:1; (2) the thermal reaction temperature is 500 ℃; (3) the condensation temperature of the first section is 220 ℃; (4) the condensation temperature of the second section is 50 ℃; (5) The molten salt electrolyte consists of aluminum chloride and zinc chloride, and the current density is 7A/dm 2 The electrolysis temperature was 200 ℃.
The gallium metal is recovered through the process flow, the recovery rate is 86.3%, and the purity is 99.45%.
Example 4
The method is the same as case 1, and is different from the following steps: (1) Without waterThe mass ratio of the ammonium chloride to the gallium nitride waste powder is 2.5:1; (2) the thermal reaction temperature is 450 ℃; (3) the condensation temperature of the first stage is 215 ℃; (4) the condensation temperature of the second section is 42 ℃; (5) The molten salt electrolyte consists of aluminum chloride and zinc chloride, and the current density is 6A/dm 2 The electrolysis temperature was 150 ℃.
The gallium metal is recovered by the process flow, the recovery rate is 85.1 percent, and the purity is 99.56 percent.
Example 5
The method is the same as case 1, and is different from the following steps: (1) The mass ratio of the anhydrous ammonium chloride to the gallium nitride waste powder is 3:1; (2) the thermal reaction temperature is 450 ℃; (3) the condensation temperature of the first section is 215 ℃; (4) The molten salt electrolyte consists of aluminum chloride and magnesium chloride, and the mass percent of gallium chloride is 60%; (4) The current density is 6A/dm 2 The electrolysis temperature was 250 ℃.
The gallium metal is recovered by the process flow, the recovery rate is 83.5%, and the purity is 99.66%.
Example 6
The method is the same as case 1, and is different from the following steps: (1) The mass ratio of the anhydrous ammonium chloride to the gallium nitride waste powder is 3:1; (2) the thermal reaction temperature is 500 ℃; (3) The molten salt electrolyte consists of aluminum chloride and magnesium chloride, and the mass percent of gallium chloride is 55%; (4) The current density is 6.5A/dm 2 The electrolysis temperature was 300 ℃.
The gallium metal is recovered by the process flow, the recovery rate is 82.8%, and the purity is 99.59%.
Example 7
The method is the same as case 1, and is different from the following steps: (1) The mass ratio of the anhydrous ammonium chloride to the gallium nitride waste powder is 3:1; (2) the thermal reaction temperature is 500 ℃; (3) Other chlorine salts in the molten salt electrolyte are calcium chloride and magnesium chloride, and the mass percent of gallium chloride is 50%; (4) The current density is 5A/dm 2 The electrolysis temperature was 650 ℃.
The gallium metal is recovered through the process flow, the recovery rate is 82.9%, and the purity is 99.42%.
Example 8
The process was the same as in case 1, except that the thermal reaction temperature was 350 ℃.
The gallium metal is recovered through the process flow, the recovery rate is 18.2%, and the purity is 99.73%.
Example 9
The method is the same as case 1, and is different from the following steps: the thermal reaction temperature was 750 ℃.
The metal gallium is recovered by the process flow, the recovery rate is 81.7%, and the purity is 99.16%.
Claims (10)
1. A method for preparing gallium chloride by utilizing gallium nitride wastes is characterized by comprising the following steps:
crushing gallium nitride waste;
step two, uniformly mixing the crushed gallium nitride waste with anhydrous ammonium chloride;
transferring the obtained mixed raw materials to a thermal reactor for thermal reaction to generate gas containing gallium chloride;
step four, the obtained gallium chloride-containing gas is condensed once through a condenser, and ammonium chloride solid and gallium chloride gas are separated and obtained;
and step five, carrying out secondary condensation on the gallium chloride gas to obtain a gallium chloride solid.
2. The method according to claim 1, wherein the mass ratio of anhydrous ammonium chloride powder to gallium nitride waste is 2:1 to 5:1.
3. the method according to claim 1, wherein the temperature of the thermal reaction is 400 to 600 ℃.
4. The method according to claim 1, wherein the temperature of the primary condensation is 210-250 ℃; the temperature of the secondary condensation is 40-60 ℃.
5. The method of claim 1, wherein the gallium nitride waste is derived from a semiconductor material containing a gallium nitride component.
6. A method for recovering metal gallium from gallium nitride waste is characterized in that gallium chloride is obtained by the method of any one of claims 1 to 5, the obtained gallium chloride is used as a raw material to prepare a molten salt electrolyte, and the obtained molten salt electrolyte is subjected to molten salt electrolysis to obtain the metal gallium.
7. The method of claim 6, wherein the molten salt electrolyte is formed by mixing gallium chloride and other chlorine salts, and the mass fraction of the gallium chloride in the molten salt electrolyte is 40-80%.
8. The method of claim 7, wherein the other chloride salts comprise any one or more of lithium chloride, sodium chloride, potassium chloride, magnesium chloride, or calcium chloride.
9. The method of claim 6, wherein the current density of the molten salt electrolysis is 5 to 10A/dm 2 。
10. A method according to claim 6 wherein the temperature of the molten salt electrolysis is in the range 120 to 750 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210810608.5A CN115287456A (en) | 2022-07-11 | 2022-07-11 | Method for recovering metal gallium from gallium nitride waste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210810608.5A CN115287456A (en) | 2022-07-11 | 2022-07-11 | Method for recovering metal gallium from gallium nitride waste |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115287456A true CN115287456A (en) | 2022-11-04 |
Family
ID=83822341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210810608.5A Pending CN115287456A (en) | 2022-07-11 | 2022-07-11 | Method for recovering metal gallium from gallium nitride waste |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115287456A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102172458A (en) * | 2010-12-31 | 2011-09-07 | 东莞市中镓半导体科技有限公司 | Method and equipment for processing tail gas containing ammonium chloride |
| CN205907028U (en) * | 2016-08-01 | 2017-01-25 | 江苏省冶金设计院有限公司 | System for handle red mud |
| CN108374091A (en) * | 2018-03-30 | 2018-08-07 | 中国科学院过程工程研究所 | A kind of gallium for recycling the method for gallium in waste material from the gallium compound containing indissoluble and being obtained by this method |
| CN111501069A (en) * | 2020-06-02 | 2020-08-07 | 株洲科能新材料有限责任公司 | Molten salt electrolysis purification method of crude gallium |
| CN113087008A (en) * | 2021-03-31 | 2021-07-09 | 神华准能资源综合开发有限公司 | Preparation method of gallium chloride |
-
2022
- 2022-07-11 CN CN202210810608.5A patent/CN115287456A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102172458A (en) * | 2010-12-31 | 2011-09-07 | 东莞市中镓半导体科技有限公司 | Method and equipment for processing tail gas containing ammonium chloride |
| CN205907028U (en) * | 2016-08-01 | 2017-01-25 | 江苏省冶金设计院有限公司 | System for handle red mud |
| CN108374091A (en) * | 2018-03-30 | 2018-08-07 | 中国科学院过程工程研究所 | A kind of gallium for recycling the method for gallium in waste material from the gallium compound containing indissoluble and being obtained by this method |
| CN111501069A (en) * | 2020-06-02 | 2020-08-07 | 株洲科能新材料有限责任公司 | Molten salt electrolysis purification method of crude gallium |
| CN113087008A (en) * | 2021-03-31 | 2021-07-09 | 神华准能资源综合开发有限公司 | Preparation method of gallium chloride |
Non-Patent Citations (1)
| Title |
|---|
| KAZUKI NISHINAKA1 ET AL: "Pyrometallurgical Recovery of Gallium from GaN Semiconductor through Chlorination Process Utilizing Ammonium Chloride", MATERIALS TRANSACTIONS, vol. 58, no. 4, 24 February 2017 (2017-02-24), pages 688 - 691 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102266892B1 (en) | method for recovering nickel sulfate from waste comprising nickel | |
| CN110938742B (en) | Method for recovering and preparing sodium arsenate and metal gallium from gallium arsenide waste residues | |
| CN110028111A (en) | The preparation method of ternary anode material precursor and lithium carbonate | |
| CN115818675B (en) | Comprehensive utilization method of lithium-aluminum-containing waste electrolyte | |
| TW201425594A (en) | Recycling method of copper-indium-gallium-selenium residual target | |
| CN103663505B (en) | Method for treating potassium feldspar according to sub-molten salt method to prepare potassium carbonate | |
| CN113621814B (en) | Method for recovering gallium metal from gallium nitride waste material by adopting oxidizing roasting process | |
| CN108359802B (en) | The method of copper indium gallium selenide is recycled from copper indium gallium selenium solar hull cell waste material | |
| CN112645396B (en) | Method for treating fluorine-containing nickel slag generated in nitrogen trifluoride preparation process | |
| CN114317977A (en) | Method for recovering metal from waste lithium cobalt oxide battery | |
| CN115287456A (en) | Method for recovering metal gallium from gallium nitride waste | |
| CN113666410B (en) | Method for directly preparing gallium oxide by using gallium nitride waste | |
| CN114890443A (en) | System and process method for high-value utilization of lithium-containing waste | |
| CN113666409B (en) | Method for preparing gallium oxide by treating gallium nitride waste through acid method | |
| CN108425007A (en) | The method that copper indium gallium selenide is recycled from CIGS solar film battery chamber waste materials | |
| CN109266868B (en) | Method for recovering cadmium in cadmium sulfide | |
| CN110965125A (en) | Liquid phase synthesis method for preparing lead-based perovskite crystal by using waste lead-acid storage battery | |
| EP3643680A1 (en) | Coupled production of high purity silicon and alumina | |
| CN111977618B (en) | Method for removing impurity tellurium from crude selenium powder | |
| CN113667840B (en) | Method for extracting gallium metal by wet processing gallium nitride waste | |
| CN116177505B (en) | Method for efficiently recycling indium and phosphorus in indium phosphide waste material by using molten salt system | |
| CN112265987B (en) | Combined treatment method of fluosilicic acid wastewater and waste lithium ion battery carbon slag | |
| KR102472060B1 (en) | Method of recovering gallium | |
| CN116199251B (en) | Method for efficiently preparing gallium oxyhydroxide | |
| CN118047401A (en) | Method for reducing lithium content in lithium-rich electrolyte of aluminum electrolysis and recovering lithium |
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 |