CN104576848A - Method for recovering gallium from waste gallium nitride-based LEDs - Google Patents
Method for recovering gallium from waste gallium nitride-based LEDs Download PDFInfo
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- CN104576848A CN104576848A CN201410789418.5A CN201410789418A CN104576848A CN 104576848 A CN104576848 A CN 104576848A CN 201410789418 A CN201410789418 A CN 201410789418A CN 104576848 A CN104576848 A CN 104576848A
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- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 63
- 239000002699 waste material Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 44
- 229910002601 GaN Inorganic materials 0.000 title claims abstract description 43
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000000197 pyrolysis Methods 0.000 claims abstract description 83
- 238000011084 recovery Methods 0.000 claims abstract description 26
- 238000012216 screening Methods 0.000 claims abstract description 25
- 238000005272 metallurgy Methods 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims description 15
- 150000002259 gallium compounds Chemical class 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 17
- 239000002184 metal Substances 0.000 abstract description 17
- 238000000926 separation method Methods 0.000 abstract description 8
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 150000002739 metals Chemical class 0.000 abstract description 2
- 239000012141 concentrate Substances 0.000 abstract 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000002737 fuel gas Substances 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000003317 industrial substance Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying 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
- 239000000945 filler Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
- H01L33/0062—Processes for devices with an active region comprising only III-V compounds
- H01L33/0075—Processes for devices with an active region comprising only III-V compounds comprising nitride compounds
-
- 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
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for recovering gallium from waste gallium nitride-based LEDs (Light Emitting Diodes). The method comprises the following steps: performing pyrolysis, crushing-screening and grinding-screening on the waste gallium nitride-based LEDs, so as to obtain a chip concentrate of waste gallium nitride-based LEDs; performing the vacuum metallurgy separation on the gallium-containing chip concentrate to recover the elemental gallium. The method for recovering gallium from waste gallium nitride-based LEDs does not only effectively recover gallium in the waste gallium nitride-based LEDs, but also performs resourceful treatment on non-metallic components and other common metals during recovery. The method for recovering gallium from waste gallium nitride-based LEDs has prominent advantages in the reduction of environmental pollution and the improvement of resource utilization, and has characteristics of low cost, high efficiency, no pollution and the like.
Description
Technical field
The present invention relates to a kind of method reclaiming dissipated metal gallium from waste and old gallium nitride based light emitting diode, belong to the metal recovery in electron wastes, regeneration, resource technology field.
Background technology
Photodiode (LED) is the one in conventional electronic component diode, is a kind of a kind of device that electric energy can be become luminous energy, belongs to solid state light emitter.Current photodiode is widely used in research and production field, mainly comprises general illumination, landscape ornamental illumination, large screen display, backlight display, traffic signals display, auto lamp, road lighting etc.Wherein gallium nitride based light emitting diode has become most potential lighting system, and its research and apply receives the extensive attention of national governments especially and supports energetically, progressively replaces conventional illumination sources at present.Along with rolling up of semiconductor production amount, the fast development of whole LED industry, within for some time in future, LED product will welcome a large amount of dates of retirement being similar to the electronic product such as mobile phone, computer.If it is improper not reclaim LED or reclaim, for wherein contained all kinds of metals resources, especially dissipated metal gallium will be huge waste, also can produce potential harm to the health of the mankind simultaneously.
At present, the recovery of LED based on directly reuse again, be about to still can be luminous waste and old LED for requiring in lower product to light intensity, such as toy.But this method is with low content of technology, the higher economic value added of nothing, and does not really solve the recycling problem of gallium.Shenzhen City GeLinMei high New Technology Co., Ltd has been applied in 2011 patent " recovery method of waste and old diode germanium, gallium, indium, selenium " (patent No.: CN 102951618 A).The core of the method is acid wet dissolution, although the rate of recovery of dissipated metal very high (rate of recovery of selenium, indium, gallium, germanium is 98.2%, 98.1%, 97.9%, 98.6% respectively), but which create the acid waste liquid and waste residue that need process in a large number, add subsequent disposal difficulty and environmental pollution hidden danger.
Summary of the invention
The object of the present invention is to provide a kind of method of enriching and recovering dissipated metal gallium from waste and old gallium nitride based light emitting diode, gallium is able to enriching and recovering, also make the nonmetallic ingredient in waste and old photodiode and common valuable metal (copper, aluminium etc.) obtain Separation and Recovery simultaneously, contribute to solving the wasting of resources of waste and old gallium nitride based light emitting diode and potential problem of environmental pollution, realize the recovery to waste and old gallium nitride based light emitting diode, regeneration and recycling treatment.
A kind of method reclaiming gallium from waste and old gallium nitride based light emitting diode that the present invention proposes, by waste and old gallium nitride based light emitting diode through pyrolysis, again by the chip enrich body crushing-screening, grinding-screening obtains waste and old gallium nitride based light emitting diode, chip enrich body containing gallium is carried out vacuum metallurgy separation, reclaims and obtain Metallic Gallium.
In recovery method of the present invention, the rate of recovery of described gallium reaches more than 90%, and purity is greater than 90%.
In the present invention, described waste and old gallium nitride based light emitting diode is carried out nitrogen pyrolysis, comprise step: waste and old gallium nitride based light emitting diode is placed in high-temperature crucible by (a), and crucible is put into resistance furnace; Start nitrogen blow and vent system after the sealing of (b) resistance furnace, keep nitrogen atmosphere in stove; C () starting resistance stove power supply, is heated to design temperature the waste and old photodiode in crucible, then keeps temperature-resistant, make the abundant pyrolysis of the nonmetallic ingredient in raw material, pyrolysis obtains pyrolysis gas, pyrolysis oil, pyrolysis residue.
In the present invention, described pyrolysis is carried out under a nitrogen atmosphere, and pyrolysis temperature is 400 ~ 600 DEG C, and pyrolysis time is 10 ~ 60min.
In the present invention, described crushing-screening, grinding-screening obtain the chip enrich body of waste and old gallium nitride based light emitting diode, comprise step: described pyrolysis residue through crushing, sieving, is obtained screen overflow by (a); B described screen overflow is ground process, screening by (), the lower chip enrich body forming waste and old gallium nitride based light emitting diode of sieve.
In the present invention, the chip enrich body containing gallium compound is carried out vacuum metallurgy separation and comprise step: (a) described chip enrich body is placed in high-temperature crucible, and vacuum oven put into by crucible; Start vacuum system after the sealing of (b) vacuum oven to bleed, make the pressure of vacuum oven be 0.05 ~ 5.0Pa; C () starts vacuum furnace power supply, the mixture in crucible is heated to design temperature, then keeps temperature-resistant, makes fully decomposing containing gallium compound in material, gallium fully evaporates, keep the soaking time of setting, reclaim and obtain Metallic Gallium.
In the present invention, described vacuum metallurgy removal process is, starts vacuum oven power supply, the described chip enrich body in crucible is heated to 900 ~ 1200 DEG C, then keeps temperature-resistant, makes fully decomposing containing gallium compound in raw material, gallium fully evaporates; Wherein, soaking time is 1.0 ~ 3.0h.
Wherein, the condensation on condenser of gallium steam, condensing temperature interval is 350 ~ 800 DEG C, and the rate of recovery of gallium reaches more than 90%; Purity is greater than 90%.
In recovery method of the present invention, described nitrogen pyrolysis obtains pyrolysis gas, pyrolysis oil, pyrolysis residue.Wherein, described pyrolysis residue carries out follow-up crushing-screening, grinding-screening step.Described pyrolysis gas can be recovered as fuel gas.Described pyrolysis oil can be recovered as oil fuel or industrial chemicals.
In recovery method of the present invention, " waste and old gallium nitride based light emitting diode " refer to gallium nitride based light emitting diode encapsulation, test link produce defect ware and lose the elimination product that use value enters the date of retirement.
In recovery method of the present invention, the nonmetallic ingredient in waste and old gallium nitride based light emitting diode and other common metal components also obtain resource utilization respectively and reclaim.
In a specific embodiment, recovery method of the present invention adopts waste and old gallium nitride based light emitting diode pyrolysis---enrichment of-two-stage crushing and screening---, and-vacuum metallurgy separating gallium, comprises the following steps:
(1) waste and old gallium nitride based light emitting diode is placed in high-temperature crucible, then crucible is put into resistance furnace;
(2) start nitrogen blow and vent system after resistance furnace sealing, keep nitrogen atmosphere in stove;
(3) starting resistance stove power supply, is heated to 400 ~ 600 DEG C the waste and old photodiode in crucible, then keeps temperature-resistant, makes the abundant pyrolysis of the nonmetallic ingredient in raw material, and pyrolysis time is 10 ~ 60min;
(4), in pyrolytic process, with the sour gas in recycle of alkali liquor pyrolysis gas, all the other pyrolysis gas reclaim as fuel gas after drying;
(5) after pyrolysis terminates, pyrolysis oil sealed vessel reclaims, as fuel or industrial chemicals;
(6) pyrolysis residue is through crushing, and makes breeze particle diameter be 0.2 ~ 1.0mm, and through 18 eye mesh screen screenings, breeze can be used as filler or for the preparation of gac, is connected with metal frame enrichment on sieve of LED chip;
(7) carry out milled processed to the screen overflow of step (6), metal frame is separated with LED chip, through 40 eye mesh screen screenings, the aluminum metal frame of copper facing or silver reclaims on sieve, LED chip enrichment under sieve;
(8) screen underflow of step (7) is placed in high-temperature crucible, then crucible is put into vacuum oven;
(9) start vacuum system after vacuum oven sealing to bleed, make the pressure of vacuum oven be 0.05 ~ 5.0Pa;
(10) start vacuum furnace power supply, the mixture in crucible is heated to 900 ~ 1200 DEG C, then keeps temperature-resistant, make fully decomposing containing gallium compound in raw material, gallium fully evaporates, soaking time is 1.0 ~ 3.0h;
(11) gallium steam condensation on condenser, condensing temperature interval is 350 ~ 800 DEG C, and the rate of recovery of gallium reaches more than 90%, and purity is greater than 90%; Remaining residue is mainly silicon-dioxide, can be used for preparing quartz ware.
Recovery method of the present invention, first by the pyrolysis under a nitrogen of waste and old diode, pyrolysis final temperature is at 400 ~ 600 DEG C, and pyrolysis time keeps 10 ~ 60min, and make waste and old photodiode at utmost subtract appearance, structure becomes loose, is beneficial to breeze and metal separation; Then pyrolysis residue is crushed-screening, grinding-screening, breeze and copper facing or silver-colored aluminum metal frame are recycled, obtain light-emitting diode chip for backlight unit enrich body, as raw material, heat in a vacuum furnace, at pressure 0.05 ~ 5.0Pa, temperature is 900 ~ 1200 DEG C, and heat-up time is carry out under the condition of 1.0 ~ 3.0h containing the decomposition of gallium compound and the evaporation of metal, and gallium vapour condensation is on condenser, condensing temperature interval is 350 ~ 800 DEG C, and the rate of recovery and the purity of gallium reach more than 90%.In recovery method of the present invention, the dissipated metal gallium in waste and old gallium nitride based light emitting diode obtains effective regeneration, and nonmetallic ingredient obtains appropriate disposal simultaneously, and common valuable metal also obtains resource utilization and reclaims.In recovery method of the present invention, adopt the method for pyrolysis-crushing and screening-vacuum separation, easy and simple to handle feasible, there is the features such as cost is low, efficient, pollution-free.Each component of waste and old gallium nitride based light emitting diode is obtained for appropriate disposal of resources.Compare the method that tradition such as adopting baked wheaten cake and pickling reclaims valuable metal in electron wastes, the present invention has clear superiority in minimizing environmental pollution and energy-saving and emission-reduction.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet that the present invention reclaims the method for gallium from waste and old gallium nitride based light emitting diode.
Embodiment
In conjunction with following specific embodiments and the drawings, the present invention is described in further detail, and protection content of the present invention is not limited to following examples.Under the spirit and scope not deviating from inventive concept, the change that those skilled in the art can expect and advantage are all included in the present invention, and are protection domain with appending claims.Implement process of the present invention, condition, reagent, experimental technique etc., except the following content mentioned specially, be universal knowledege and the common practise of this area, the present invention is not particularly limited content.
Fig. 1 is the schematic diagram that the present invention reclaims the method for gallium from waste and old gallium nitride based light emitting diode.Essentially describe flow process of the present invention in figure, first waste and old photodiode is through nitrogen pyrolysis, and pyrolysis final temperature is 400 ~ 600 DEG C, and the pyrolysis hold-time is 10 ~ 60min; Pyrolysis gas, through alkali lye wash-out, is collected as fuel gas; Pyrolysis oil is collected as oil fuel or industrial chemicals.Then, pyrolysis residue is through crushing, and breeze particle diameter, at 0.2 ~ 1.0mm, is crossed 18 eye mesh screen screenings, collected breeze, for the preparation of gac; Screen overflow is through milled processed, and after 40 eye mesh screen screenings, the aluminum metal frame of copper facing or silver is recovered on sieve, obtains the chip enrich body of photodiode under sieve; Finally, chip enrich body carries out separation and Extraction through vacuum metallurgy method, and under suitable operating parameters, obtain dissipated metal gallium, its purity is greater than 90%.
Wherein, " waste and old gallium nitride based light emitting diode " refer to gallium nitride based light emitting diode encapsulation, test link produce defect ware and lose the elimination product that use value enters the date of retirement.
Wherein, " suitable operating parameters " refer to vacuum metallurgy separation system pressure 0.05 ~ 5.0Pa, Heating temperature 900 ~ 1200 DEG C, heat-up time 1.0 ~ 3.0h.
Embodiment 1
First waste and old gallium nitride based light emitting diode is carried out nitrogen pyrolysis, pyrolysis final temperature is 400 DEG C, and pyrolysis time is 60min.After pyrolysis terminates, collect pyrolysis gas, pyrolysis oil and pyrolysis residue respectively, pyrolysis gas and pyrolysis oil reclaim him and use.Pyrolysis residue is after crushing, and breeze particle diameter is 0.7 ~ 1.0mm, and cross 18 eye mesh screen screenings, breeze reclaims under sieve.Screen overflow is through grinding process, and after 40 eye mesh screen screenings, copper facing or silver-colored aluminum metal frame reclaim on sieve, the lower chip enrich body forming photodiode of sieve.Chip enrich body is put into crucible, then crucible is put into vacuum oven.Start vacuum system after vacuum oven sealing to bleed, the vacuum tightness of vacuum oven is between 1.0-5.0Pa.Start the heating member heating crucible in vacuum oven, crucible chips enrich body is heated to 1200 DEG C.Then keep temperature-resistant, make fully decomposing containing gallium compound in raw material, gallium fully evaporates, soaking time is 1.0h.Gallium steam is able to condensation on condenser, and in the present embodiment, condensing temperature interval is 500 ~ 800 DEG C, obtains Metallic Gallium, and the gallium rate of recovery is 95.0%, and purity is 92.8%.
In the process that vacuum metallurgy of the present invention reclaims, the condensing temperature interval of gallium steam is suitable for the temperature range of 350 ~ 800 DEG C, and the choosing of condensing temperature interval of gallium steam does not limit by other conditions, all can realize the recovery of Metallic Gallium in this temperature range.
Embodiment 2
First waste and old gallium nitride based light emitting diode is carried out nitrogen pyrolysis, pyrolysis final temperature is 500 DEG C, and pyrolysis time is 30min.After pyrolysis terminates, collect pyrolysis gas, pyrolysis oil and pyrolysis residue respectively, pyrolysis gas and pyrolysis oil reclaim him and use.Pyrolysis residue is after crushing, and breeze particle diameter is 0.5 ~ 0.8mm, and cross 18 eye mesh screen screenings, breeze reclaims under sieve.Screen overflow is through grinding process, and after 40 eye mesh screen screenings, copper facing or silver-colored aluminum metal frame reclaim on sieve, the lower chip enrich body forming photodiode of sieve.Chip enrich body is put into crucible, then crucible is put into vacuum oven.Start vacuum system after vacuum oven sealing to bleed, the vacuum tightness of vacuum oven is between 0.5-1.5Pa.Start the heating member heating crucible in vacuum oven, crucible chips enrich body is heated to 1100 DEG C.Then keep temperature-resistant, make fully decomposing containing gallium compound in raw material, gallium fully evaporates, soaking time is 3.0h.Gallium steam is able to condensation on condenser, and in the present embodiment, condensing temperature interval is 440 ~ 755 DEG C, obtains Metallic Gallium, and the gallium rate of recovery is 93.8%, and purity is 91.7%.
Embodiment 3
First waste and old gallium nitride based light emitting diode is carried out nitrogen pyrolysis, pyrolysis final temperature is 600 DEG C, and pyrolysis time is 10min.After pyrolysis terminates, collect pyrolysis gas, pyrolysis oil and pyrolysis residue respectively, pyrolysis gas and pyrolysis oil reclaim him and use.Pyrolysis residue is after crushing, and breeze particle diameter is 0.4 ~ 0.6mm, and cross 18 eye mesh screen screenings, breeze reclaims under sieve.Screen overflow is through grinding process, and after 40 eye mesh screen screenings, copper facing or silver-colored aluminum metal frame reclaim on sieve, the lower chip enrich body forming photodiode of sieve.Chip enrich body is put into crucible, then crucible is put into vacuum oven.Start vacuum system after vacuum oven sealing to bleed, the vacuum tightness of vacuum oven is between 0.1-1.0Pa.Start the heating member heating crucible in vacuum oven, crucible chips enrich body is heated to 1000 DEG C.Then keep temperature-resistant, make fully decomposing containing gallium compound in raw material, gallium fully evaporates, soaking time is 2.0h.Gallium steam is able to condensation on condenser, and in the present embodiment, condensing temperature interval is 390 ~ 710 DEG C, obtains Metallic Gallium, and the gallium rate of recovery is 94.7%, and purity is 92.2%.
Embodiment 4
First waste and old gallium nitride based light emitting diode is carried out nitrogen pyrolysis, pyrolysis final temperature is 550 DEG C, and pyrolysis time is 20min.After pyrolysis terminates, collect pyrolysis gas, pyrolysis oil and pyrolysis residue respectively, pyrolysis gas and pyrolysis oil reclaim him and use.Pyrolysis residue is after crushing, and breeze particle diameter is 0.2 ~ 0.5mm, and cross 18 eye mesh screen screenings, breeze reclaims under sieve.Screen overflow is through grinding process, and after 40 eye mesh screen screenings, copper facing or silver-colored aluminum metal frame reclaim on sieve, the lower chip enrich body forming photodiode of sieve.Chip enrich body is put into crucible, then crucible is put into vacuum oven.Start vacuum system after vacuum oven sealing to bleed, the vacuum tightness of vacuum oven is between 0.05-0.1Pa.Start the heating member heating crucible in vacuum oven, crucible chips enrich body is heated to 900 DEG C.Then keep temperature-resistant, make fully decomposing containing gallium compound in raw material, gallium fully evaporates, soaking time is 1.5h.Gallium steam is able to condensation on condenser, and in the present embodiment, condensing temperature interval is 350 ~ 685 DEG C, obtains Metallic Gallium, and the gallium rate of recovery is 93.5%, and purity is 91.8%.
Claims (6)
1. one kind is reclaimed the method for gallium from waste and old gallium nitride based light emitting diode, it is characterized in that, by waste and old gallium nitride based light emitting diode through pyrolysis, again by the chip enrich body crushing-screening, grinding-screening obtains waste and old gallium nitride based light emitting diode, the chip enrich body containing gallium compound reclaims through vacuum metallurgy and obtains Metallic Gallium.
2. from waste and old gallium nitride based light emitting diode, reclaim the method for gallium as claimed in claim 1, it is characterized in that, the rate of recovery of described gallium reaches more than 90%, and purity is greater than 90%.
3. from waste and old gallium nitride based light emitting diode, reclaim the method for gallium as claimed in claim 1, it is characterized in that, described pyrolysis is carried out under a nitrogen atmosphere, and pyrolysis temperature is 400 ~ 600 DEG C, and pyrolysis time is 10 ~ 60min.
4. from waste and old gallium nitride based light emitting diode, reclaim the method for gallium as claimed in claim 1, it is characterized in that, in described vacuum metallurgy removal process, the pressure of vacuum oven is 0.05 ~ 5.0Pa, start vacuum oven power supply, described chip enrich body in crucible is heated to 900 ~ 1200 DEG C, keeps temperature-resistant, until fully decomposing containing gallium compound in raw material, gallium fully evaporates; Wherein, soaking time is 1.0 ~ 3.0h.
5. from waste and old gallium nitride based light emitting diode, reclaim the method for gallium as claimed in claim 1, it is characterized in that, during described vacuum metallurgy reclaims, the condensation on condenser of gallium steam, condensing temperature interval is 350 ~ 800 DEG C.
6. from waste and old gallium nitride based light emitting diode, reclaim the method for gallium as claimed in claim 1, it is characterized in that, obtain pyrolysis gas, pyrolysis oil, pyrolysis residue through described pyrolytic process.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109055782A (en) * | 2018-08-24 | 2018-12-21 | 华南理工大学 | The leaching method of gallium in a kind of useless light emitting diode |
| TWI663001B (en) * | 2017-07-24 | 2019-06-21 | Dayeh University | Method for recovering waste light-emitting diode grains |
| CN112967948A (en) * | 2020-08-05 | 2021-06-15 | 重庆康佳光电技术研究院有限公司 | Metal gallium removing device and metal gallium removing method |
| CN113621814A (en) * | 2021-08-24 | 2021-11-09 | 安徽工业大学 | Method for recovering gallium metal in gallium nitride waste by adopting oxidizing roasting process |
| CN113652559A (en) * | 2021-08-20 | 2021-11-16 | 安徽工业大学 | Method for recovering rare and scattered metal gallium in gallium nitride waste material by pyrogenic process |
| CN114317973A (en) * | 2021-12-17 | 2022-04-12 | 北京工业大学 | Pyrolysis recovery method for organic components of waste light-emitting diodes |
| CN114577659A (en) * | 2022-01-26 | 2022-06-03 | 株洲科能新材料股份有限公司 | Method for detecting gallium content in gallium nitride material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1598016A (en) * | 2004-07-19 | 2005-03-23 | 昆明理工大学 | Process for comprehensive recovering gallium and arsenic from industrial waste material of gallium arsenide |
| CN101413064A (en) * | 2008-10-29 | 2009-04-22 | 南京金美镓业有限公司 | Vacuum decomposing apparatus for separating gallium arsenide as metal gallium and metal arsenic |
| CN103388159A (en) * | 2012-05-11 | 2013-11-13 | 深圳市格林美高新技术股份有限公司 | Method for recovering gallium from gallium nitride-containing wastes |
-
2014
- 2014-12-17 CN CN201410789418.5A patent/CN104576848B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1598016A (en) * | 2004-07-19 | 2005-03-23 | 昆明理工大学 | Process for comprehensive recovering gallium and arsenic from industrial waste material of gallium arsenide |
| CN101413064A (en) * | 2008-10-29 | 2009-04-22 | 南京金美镓业有限公司 | Vacuum decomposing apparatus for separating gallium arsenide as metal gallium and metal arsenic |
| CN103388159A (en) * | 2012-05-11 | 2013-11-13 | 深圳市格林美高新技术股份有限公司 | Method for recovering gallium from gallium nitride-containing wastes |
Cited By (11)
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|---|---|---|---|---|
| TWI663001B (en) * | 2017-07-24 | 2019-06-21 | Dayeh University | Method for recovering waste light-emitting diode grains |
| CN109055782A (en) * | 2018-08-24 | 2018-12-21 | 华南理工大学 | The leaching method of gallium in a kind of useless light emitting diode |
| CN112967948A (en) * | 2020-08-05 | 2021-06-15 | 重庆康佳光电技术研究院有限公司 | Metal gallium removing device and metal gallium removing method |
| CN112967948B (en) * | 2020-08-05 | 2022-05-20 | 重庆康佳光电技术研究院有限公司 | Gallium metal removing device and gallium metal removing method |
| CN113652559A (en) * | 2021-08-20 | 2021-11-16 | 安徽工业大学 | Method for recovering rare and scattered metal gallium in gallium nitride waste material by pyrogenic process |
| CN113652559B (en) * | 2021-08-20 | 2022-07-29 | 安徽工业大学 | Method for recovering rare and scattered metal gallium in gallium nitride waste material by pyrogenic process |
| CN113621814A (en) * | 2021-08-24 | 2021-11-09 | 安徽工业大学 | Method for recovering gallium metal in gallium nitride waste by adopting oxidizing roasting process |
| CN114317973A (en) * | 2021-12-17 | 2022-04-12 | 北京工业大学 | Pyrolysis recovery method for organic components of waste light-emitting diodes |
| WO2023108859A1 (en) * | 2021-12-17 | 2023-06-22 | 北京工业大学 | Pyrolysis recycling method for organic component in waste light-emitting diode |
| CN114577659A (en) * | 2022-01-26 | 2022-06-03 | 株洲科能新材料股份有限公司 | Method for detecting gallium content in gallium nitride material |
| CN114577659B (en) * | 2022-01-26 | 2024-02-06 | 株洲科能新材料股份有限公司 | Method for detecting gallium content in gallium nitride material |
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