CN104576848B - The method that gallium is reclaimed from waste and old gallium nitride based light emitting diode - Google Patents
The method that gallium is reclaimed from waste and old gallium nitride based light emitting diode Download PDFInfo
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- CN104576848B CN104576848B CN201410789418.5A CN201410789418A CN104576848B CN 104576848 B CN104576848 B CN 104576848B CN 201410789418 A CN201410789418 A CN 201410789418A CN 104576848 B CN104576848 B CN 104576848B
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- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 58
- 239000002699 waste material Substances 0.000 title claims abstract description 47
- 229910002601 GaN Inorganic materials 0.000 title claims abstract description 38
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000011084 recovery Methods 0.000 claims abstract description 30
- 238000012216 screening Methods 0.000 claims abstract description 25
- 238000005272 metallurgy Methods 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 6
- 238000000197 pyrolysis Methods 0.000 claims description 77
- 238000001291 vacuum drying Methods 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 20
- 150000002259 gallium compounds Chemical class 0.000 claims description 11
- 238000009833 condensation Methods 0.000 claims description 10
- 230000005494 condensation Effects 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 7
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 230000003287 optical effect Effects 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 16
- 239000002184 metal Substances 0.000 abstract description 16
- 239000004615 ingredient Substances 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 6
- 238000000227 grinding Methods 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000007789 sealing 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
- 238000001704 evaporation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000002893 slag Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment 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
- 239000002737 fuel gas Substances 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000003317 industrial substance Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000012545 processing Methods 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
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 239000000295 fuel oil Substances 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
- 239000000203 mixture Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 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
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005538 encapsulation Methods 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
- 239000000446 fuel Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000036541 health Effects 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
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 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 kind of method that gallium is reclaimed from waste and old gallium nitride based light emitting diode, by waste and old gallium nitride based light emitting diode by being pyrolyzed, the chip for obtaining waste and old gallium nitride based light emitting diode by crushing screening, grinding screening again is enriched with body, chip enrichment body containing gallium is subjected to vacuum metallurgy separation, recovery obtains Metallic Gallium.The present invention has not only effectively reclaimed the gallium in waste and old gallium nitride based light emitting diode, and in removal process, nonmetallic ingredient and other common metals is obtained recycling treatment.The present invention reduce environmental pollution and improve resource utilization in terms of advantage protrude, with cost it is low, efficient, it is pollution-free the features such as.
Description
Technical field
The present invention relates to a kind of method that dissipated metal gallium is reclaimed from waste and old gallium nitride based light emitting diode, belong to electronics
Metal recovery, regeneration, resource technology field in discarded object.
Background technology
Light emitting diode (LED) is one kind in conventional electronic component diode, is that a kind of electric energy can be changed into luminous energy
A kind of device, belongs to solid state light emitter.Current light emitting diode is widely used in research and production field, main bag
Containing general illumination, landscape ornamental illumination, large screen display, backlight is shown, traffic signals are shown, auto lamp, road lighting etc..Its
Middle gallium nitride based light emitting diode turns into most potential lighting system, and it is even more to receive national governments that it, which is studied with application,
Pay attention to and support energetically extensively, progressively replace conventional illumination sources at present.With the substantial increase of semiconductor production amount, entirely
The fast development of LED industry, LED product will be welcome similar to electronic products such as mobile phone, computers within following a period of time
A large amount of dates of retirement.It is especially dilute for all kinds of metals resources contained therein if it is improper that LED is not reclaimed or reclaimed
Dispersed metallic gallium, will be huge waste, at the same to the mankind health can also produce it is potentially hazardous.
At present, LED recovery is so that directly again based on reuse, the waste and old LED that can still will be lighted is used for luminous intensity requirement
In relatively low product, for example toy.But the method is with low content of technology, the higher economic value added of nothing, and real solution gallium
Recycling problem.Patent " waste and old diode is applied in 2011 in Shenzhen City GeLinMei high New Technology Co., Ltd
Germanium, gallium, indium, the recovery method of the selenium " (patent No.：CN 102951618 A).The core of this method is acid wet dissolution, although
The rate of recovery of dissipated metal is very high (selenium, indium, gallium, the rate of recovery of germanium are 98.2%, 98.1%, 97.9%, 98.6% respectively), but
The acid waste liquid and waste residue that need to largely handle are which created, subsequent treatment difficulty and environmental pollution hidden danger is added.
The content of the invention
It is an object of the invention to provide one kind from waste and old gallium nitride based light emitting diode enriching and recovering dissipated metal gallium
Method, gallium is able to enriching and recovering, at the same also cause waste and old light emitting diode in nonmetallic ingredient and common valuable metal
(copper, aluminium etc.) is separated and recovered, and helps to solve the wasting of resources of waste and old gallium nitride based light emitting diode and potential environment
Pollution problem, realizes the recovery, regeneration and recycling treatment to waste and old gallium nitride based light emitting diode.
A kind of method that gallium is reclaimed from waste and old gallium nitride based light emitting diode proposed by the present invention, by waste and old gallium nitride base
Light emitting diode is by pyrolysis, then obtains by crushing-screening, grinding-screening the chip of waste and old gallium nitride based light emitting diode
Body is enriched with, the chip enrichment body containing gallium vacuum metallurgy separation is subjected to, recovery obtains Metallic Gallium.
In recovery method of the present invention, the rate of recovery of the gallium reaches more than 90%, and purity is more than 90%.
It is described that waste and old gallium nitride based light emitting diode is subjected to nitrogen pyrolysis, including step in the present invention：(a) will be waste and old
Gallium nitride based light emitting diode is placed in high-temperature crucible, and crucible is put into resistance furnace；(b) nitrogen is started after resistance furnace sealing
Nitrogen atmosphere in aerating system, holding furnace；(c) start resistance furnace power supply, the waste and old light emitting diode in crucible is heated to set
Constant temperature degree, then keeping temperature is constant, the nonmetallic ingredient in raw material is fully pyrolyzed, and pyrolysis obtains pyrolysis gas, pyrolysis oil, heat
Solve slag.
In the present invention, the pyrolysis is carried out under a nitrogen atmosphere, pyrolysis temperature be 400~600 DEG C, pyrolysis time be 10~
60min。
In the present invention, the crushing-screening, grinding-screening obtain the chip enrichment of waste and old gallium nitride based light emitting diode
Body, including step：(a) by the pyrolysis residue it is crushed, screening, obtain oversize；(b) oversize is ground into processing, sieve
Point, the chip enrichment body of waste and old gallium nitride based light emitting diode is formed under sieve.
In the present invention, the chip enrichment body containing gallium compound is carried out into vacuum metallurgy separation includes step：(a) core
Piece enrichment body is placed in high-temperature crucible, and crucible is put into vacuum drying oven；(b) start vacuum system pumping after vacuum drying oven sealing, make
The pressure of vacuum drying oven is 0.05~5.0Pa；(c) start vacuum furnace power supply, the mixture in crucible is heated to setting temperature
Degree, then keeping temperature is constant, makes fully being decomposed containing gallium compound in material, gallium fully evaporates, and keeps the guarantor set
Warm time, recovery obtains Metallic Gallium.
In the present invention, the vacuum metallurgy removal process is to start vacuum drying oven power supply, and the chip in crucible is enriched with
Body is heated to 900~1200 DEG C, and then keeping temperature is constant, makes fully being decomposed containing gallium compound in raw material, gallium abundant
Evaporation；Wherein, soaking time is 1.0~3.0h.
Wherein, gallium steam is condensed on condenser, and condensation temperature interval is 350~800 DEG C, and the rate of recovery of gallium reaches 90%
More than；Purity is more than 90%.
In recovery method of the present invention, the nitrogen pyrolysis obtains pyrolysis gas, pyrolysis oil, pyrolysis residue.Wherein, the pyrolysis residue
Carry out follow-up crushing-screening, grinding-screening step.The pyrolysis gas can be recovered as fuel gas.The pyrolysis oil can quilt
Recovery is used as fuel oil or industrial chemicals.
In recovery method of the present invention, " waste and old gallium nitride based light emitting diode " refers to seal in gallium nitride based light emitting diode
Defect ware and lose the elimination product that use value enters the date of retirement that dress, test link are produced.
In recovery method of the present invention, nonmetallic ingredient and other common metal groups in waste and old gallium nitride based light emitting diode
Divide and also respectively obtain recycling recovery.
In a specific embodiment, recovery method of the present invention is pyrolyzed using waste and old gallium nitride based light emitting diode ----
Two-stage crushing and screening is enriched with ----vacuum metallurgy separating gallium, comprise 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) nitrogen atmosphere in nitrogen aerating system, holding furnace is started after resistance furnace sealing；
(3) start resistance furnace power supply, the waste and old light emitting diode in crucible is heated to 400~600 DEG C, then keep temperature
Degree is constant, the nonmetallic ingredient in raw material is fully pyrolyzed, and pyrolysis time is 10~60min；
(4) in pyrolytic process, with the sour gas in recycle of alkali liquor pyrolysis gas, remaining pyrolysis gas is after drying as fuel
Gas is reclaimed；
(5) after pyrolysis terminates, pyrolysis oil is reclaimed with sealing container, is used as fuel or industrial chemicals；
(6) pyrolysis residue is crushed so that breeze particle diameter is 0.2~1.0mm, is sieved through 18 eye mesh screens, breeze can conduct
Filler or for preparing activated carbon, the metal framework for being connected with LED chip is enriched with sieve；
(7) processing is ground to the oversize of step (6) so that metal framework is separated with LED chip, through 40 eye mesh screens
The aluminum metal framework of screening, copper facing or silver is reclaimed on sieve, and LED chip is enriched with sieve；
(8) screenings of step (7) is placed in high-temperature crucible, then crucible is put into vacuum drying oven；
(9) vacuum system pumping is started after vacuum drying oven sealing, the pressure for making vacuum drying oven is 0.05~5.0Pa；
(10) start vacuum furnace power supply, the mixture in crucible is heated to 900~1200 DEG C, then keeping temperature
It is constant, make fully being decomposed containing gallium compound in raw material, gallium fully evaporates, soaking time is 1.0~3.0h；
(11) gallium steam is condensed on condenser, and condensation temperature interval is 350~800 DEG C, and the rate of recovery of gallium reaches 90%
More than, purity is more than 90%；Remaining residue is mainly silica, available for preparing quartz ware.
Waste and old diode, is pyrolyzed by recovery method of the present invention under a nitrogen first, and pyrolysis final temperature is at 400~600 DEG C, pyrolysis
Time keeps 10~60min so that the at utmost volume reduction of waste and old light emitting diode, structure becomes loose, beneficial to breeze and metal
Separation；Then pyrolysis residue is crushed-sieved, grinding-screening so that breeze and copper facing or silver-colored aluminum metal framework are recycled,
Light-emitting diode chip for backlight unit enrichment body is obtained, as raw material, is heated in a vacuum furnace, in 0.05~5.0Pa of pressure, temperature is
900~1200 DEG C, the heat time, gallium steamed to carry out the decomposition containing gallium compound and the evaporation of metal under conditions of 1.0~3.0h
Gas is condensate on condenser, and condensation temperature interval is 350~800 DEG C, and the rate of recovery and purity of gallium reach more than 90%.The present invention
In recovery method, the dissipated metal gallium in waste and old gallium nitride based light emitting diode obtains effective regeneration, while nonmetallic ingredient is obtained
Appropriate disposal is arrived, common valuable metal also obtains recycling recovery.In recovery method of the present invention, using pyrolysis-crushing and screening-
The method of vacuum separation, it is easy to operate feasible, with cost it is low, efficient, it is pollution-free the features such as.The waste and old pole of gallium nitride base light emitting two
The each component of pipe is obtained for appropriate disposal of resources.Have compared to being reclaimed using the tradition such as baked wheaten cake and pickling in electron wastes
The method of valency metal, the present invention has a clear superiority in terms of environmental pollution and energy-saving and emission-reduction are reduced.
Brief description of the drawings
Fig. 1 is the schematic flow sheet for the method that the present invention reclaims gallium from waste and old gallium nitride based light emitting diode.
Embodiment
With reference to specific examples below and accompanying drawing, the present invention is described in further detail, protection content of the invention
It is not limited to following examples.Under the spirit and scope without departing substantially from inventive concept, those skilled in the art it is conceivable that change
Change and advantage is all included in the present invention, and using appended claims as protection domain.The process of the implementation present invention,
Condition, reagent, experimental method etc., are the universal knowledege and common knowledge of this area in addition to the following content specially referred to,
Content is not particularly limited in the present invention.
Fig. 1 reclaims the schematic diagram of the method for gallium for the present invention from waste and old gallium nitride based light emitting diode.Mainly retouched in figure
The flow of the present invention is stated, light emitting diode waste and old first is pyrolyzed through nitrogen, pyrolysis final temperature is 400~600 DEG C, when pyrolysis is kept
Between be 10~60min；Pyrolysis gas is eluted through alkali lye, is collected as fuel gas；Pyrolysis oil is used as fuel oil or industrial chemicals quilt
Collect.Then, pyrolysis residue is crushed, and breeze particle diameter crosses the screening of 18 eye mesh screens, breeze is collected, for preparing in 0.2~1.0mm
Activated carbon；The ground processing of oversize, after the screening of 40 eye mesh screens, the aluminum metal framework of copper facing or silver is recovered on sieve,
The chip enrichment body of light emitting diode is obtained under sieve；Finally, chip enrichment body carries out separation and Extraction by vacuum metallurgy method, suitable
Under suitable operating parameter, dissipated metal gallium is obtained, its purity is more than 90%.
Wherein, " waste and old gallium nitride based light emitting diode " refers in gallium nitride based light emitting diode encapsulation, test link production
Raw defect ware and lose the elimination product that use value enters the date of retirement.
Wherein, " suitable operating parameter " refers to 0.05~5.0Pa of vacuum metallurgy piece-rate system pressure, heating-up temperature 900
~1200 DEG C, 1.0~3.0h of heat time.
Embodiment 1
Waste and old gallium nitride based light emitting diode is subjected to nitrogen pyrolysis first, pyrolysis final temperature is 400 DEG C, and pyrolysis time is
60min.After pyrolysis terminates, pyrolysis gas, pyrolysis oil and pyrolysis residue are collected into respectively, and pyrolysis gas reclaims him with pyrolysis oil and used.Pyrolysis
After slag is crushed, breeze particle diameter is 0.7~1.0mm, crosses the screening of 18 eye mesh screens, and breeze is reclaimed under sieve.Oversize is through grinding place
Reason, after the screening of 40 eye mesh screens, copper facing or silver-colored aluminum metal framework are reclaimed on sieve, and the chip that light emitting diode is formed under sieve is rich
Collective.Chip enrichment body is put into crucible, then crucible is put into vacuum drying oven.Start vacuum system after vacuum drying oven sealing to take out
Gas, makes the vacuum of vacuum drying oven be between 1.0-5.0Pa.Start the calandria heating crucible in vacuum drying oven, crucible SMIS
Piece enrichment body is heated to 1200 DEG C.Then keeping temperature is constant, makes fully being decomposed containing gallium compound in raw material, gallium abundant
Evaporation, soaking time is 1.0h.Gallium steam is condensed on condenser, and condensation temperature interval is 500~800 in the present embodiment
DEG C, Metallic Gallium is obtained, the gallium rate of recovery is 95.0%, and purity is 92.8%.
During vacuum metallurgy of the present invention is reclaimed, the condensation temperature interval of gallium steam is applicable 350~800 DEG C of temperature model
Enclose, the selection that the condensation temperature of gallium steam is interval is not limited by other conditions, and Metallic Gallium can be realized in the temperature range
Recovery.
Embodiment 2
Waste and old gallium nitride based light emitting diode is subjected to nitrogen pyrolysis first, pyrolysis final temperature is 500 DEG C, and pyrolysis time is
30min.After pyrolysis terminates, pyrolysis gas, pyrolysis oil and pyrolysis residue are collected into respectively, and pyrolysis gas reclaims him with pyrolysis oil and used.Pyrolysis
After slag is crushed, breeze particle diameter is 0.5~0.8mm, crosses the screening of 18 eye mesh screens, and breeze is reclaimed under sieve.Oversize is through grinding place
Reason, after the screening of 40 eye mesh screens, copper facing or silver-colored aluminum metal framework are reclaimed on sieve, and the chip that light emitting diode is formed under sieve is rich
Collective.Chip enrichment body is put into crucible, then crucible is put into vacuum drying oven.Start vacuum system after vacuum drying oven sealing to take out
Gas, makes the vacuum of vacuum drying oven be between 0.5-1.5Pa.Start the calandria heating crucible in vacuum drying oven, crucible SMIS
Piece enrichment body is heated to 1100 DEG C.Then keeping temperature is constant, makes fully being decomposed containing gallium compound in raw material, gallium abundant
Evaporation, soaking time is 3.0h.Gallium steam is condensed on condenser, and condensation temperature interval is 440~755 in the present embodiment
DEG C, Metallic Gallium is obtained, the gallium rate of recovery is 93.8%, and purity is 91.7%.
Embodiment 3
Waste and old gallium nitride based light emitting diode is subjected to nitrogen pyrolysis first, pyrolysis final temperature is 600 DEG C, and pyrolysis time is
10min.After pyrolysis terminates, pyrolysis gas, pyrolysis oil and pyrolysis residue are collected into respectively, and pyrolysis gas reclaims him with pyrolysis oil and used.Pyrolysis
After slag is crushed, breeze particle diameter is 0.4~0.6mm, crosses the screening of 18 eye mesh screens, and breeze is reclaimed under sieve.Oversize is through grinding place
Reason, after the screening of 40 eye mesh screens, copper facing or silver-colored aluminum metal framework are reclaimed on sieve, and the chip that light emitting diode is formed under sieve is rich
Collective.Chip enrichment body is put into crucible, then crucible is put into vacuum drying oven.Start vacuum system after vacuum drying oven sealing to take out
Gas, makes the vacuum of vacuum drying oven be between 0.1-1.0Pa.Start the calandria heating crucible in vacuum drying oven, crucible SMIS
Piece enrichment body is heated to 1000 DEG C.Then keeping temperature is constant, makes fully being decomposed containing gallium compound in raw material, gallium abundant
Evaporation, soaking time is 2.0h.Gallium steam is condensed on condenser, and condensation temperature interval is 390~710 in the present embodiment
DEG C, Metallic Gallium is obtained, the gallium rate of recovery is 94.7%, and purity is 92.2%.
Embodiment 4
Waste and old gallium nitride based light emitting diode is subjected to nitrogen pyrolysis first, pyrolysis final temperature is 550 DEG C, and pyrolysis time is
20min.After pyrolysis terminates, pyrolysis gas, pyrolysis oil and pyrolysis residue are collected into respectively, and pyrolysis gas reclaims him with pyrolysis oil and used.Pyrolysis
After slag is crushed, breeze particle diameter is 0.2~0.5mm, crosses the screening of 18 eye mesh screens, and breeze is reclaimed under sieve.Oversize is through grinding place
Reason, after the screening of 40 eye mesh screens, copper facing or silver-colored aluminum metal framework are reclaimed on sieve, and the chip that light emitting diode is formed under sieve is rich
Collective.Chip enrichment body is put into crucible, then crucible is put into vacuum drying oven.Start vacuum system after vacuum drying oven sealing to take out
Gas, makes the vacuum of vacuum drying oven be between 0.05-0.1Pa.Start the calandria heating crucible in vacuum drying oven, crucible SMIS
Piece enrichment body is heated to 900 DEG C.Then keeping temperature is constant, makes fully being decomposed containing gallium compound in raw material, gallium abundant
Evaporation, soaking time is 1.5h.Gallium steam is condensed on condenser, and condensation temperature interval is 350~685 in the present embodiment
DEG C, Metallic Gallium is obtained, the gallium rate of recovery is 93.5%, and purity is 91.8%.
Claims (3)
1. a kind of method that gallium is reclaimed from waste and old gallium nitride based light emitting diode, it is characterised in that send out waste and old gallium nitride base
Optical diode is by pyrolysis, then the chip for obtaining waste and old gallium nitride based light emitting diode by crushing-screening, grinding-screening is rich
Collective, the chip enrichment body containing gallium compound is reclaimed through vacuum metallurgy obtains Metallic Gallium；Wherein, the pyrolysis is in condition of nitrogen gas
Lower to carry out, pyrolysis temperature is 400~600 DEG C, and pyrolysis time is 10~60min；In the vacuum metallurgy removal process, vacuum drying oven
Pressure be 0.05~5.0 Pa, start vacuum drying oven power supply, in crucible the chip enrichment body be heated to 900~1200
DEG C, keeping temperature is constant, until raw material in fully decomposed containing gallium compound, gallium fully evaporates；Wherein, soaking time is
1.0~3.0h；During the vacuum metallurgy is reclaimed, gallium steam is condensed on condenser, and condensation temperature interval is 350~800 DEG C.
2. the method for gallium is reclaimed from waste and old gallium nitride based light emitting diode as claimed in claim 1, it is characterised in that the gallium
The rate of recovery reach more than 90%, purity is more than 90%.
3. the method for gallium is reclaimed from waste and old gallium nitride based light emitting diode as claimed in claim 1, it is characterised in that pass through institute
State pyrolytic process and obtain pyrolysis gas, pyrolysis oil, pyrolysis residue.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410789418.5A CN104576848B (en) | 2014-12-17 | 2014-12-17 | The method that gallium is reclaimed from waste and old gallium nitride based light emitting diode |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410789418.5A CN104576848B (en) | 2014-12-17 | 2014-12-17 | The method that gallium is reclaimed from waste and old gallium nitride based light emitting diode |
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| Publication Number | Publication Date |
|---|---|
| CN104576848A CN104576848A (en) | 2015-04-29 |
| CN104576848B true CN104576848B (en) | 2017-09-19 |
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| TWI663001B (en) * | 2017-07-24 | 2019-06-21 | Dayeh University | Method for recovering waste light-emitting diode grains |
| CN109055782B (en) * | 2018-08-24 | 2020-12-22 | 华南理工大学 | Leaching method of gallium in waste light-emitting diode |
| 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 |
| 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 |
| CN113621814B (en) * | 2021-08-24 | 2022-06-21 | 安徽工业大学 | Method for recovering gallium metal from gallium nitride waste material 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 |
| 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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| 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 |
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| 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 |
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