CN106381390B - A kind of waste and old LED illumination light bulb recovery method - Google Patents

A kind of waste and old LED illumination light bulb recovery method Download PDF

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CN106381390B
CN106381390B CN201610823303.2A CN201610823303A CN106381390B CN 106381390 B CN106381390 B CN 106381390B CN 201610823303 A CN201610823303 A CN 201610823303A CN 106381390 B CN106381390 B CN 106381390B
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oxide
waste
copper
illumination light
light bulb
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CN106381390A (en
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刘虎
王立
饶郑刚
田婷芳
舒龙龙
章少华
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Delta Aluminium Industry Co ltd
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Nanchang University
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00—Obtaining noble metals
    • C22B11/04—Obtaining noble metals by wet processes
    • C22B11/042—Recovery of noble metals from waste materials
    • C22B11/046—Recovery of noble metals from waste materials from manufactured products, e.g. from printed circuit boards, from photographic films, paper or baths
    • 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
    • C22B13/00—Obtaining lead
    • C22B13/02—Obtaining lead by dry processes
    • C22B13/025—Recovery from waste materials
    • 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
    • C22B15/00—Obtaining copper
    • C22B15/0026—Pyrometallurgy
    • 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
    • C22B25/00—Obtaining tin
    • C22B25/06—Obtaining tin from scrap, especially tin 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B59/00—Obtaining rare earth metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/20—Electrolytic production, recovery or refining of metals by electrolysis of solutions of noble metals
    • 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)
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  • Materials Engineering (AREA)
  • Metallurgy (AREA)
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  • Manufacturing & Machinery (AREA)
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  • Electrochemistry (AREA)
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Abstract

The present invention provides a kind of waste and old LED illumination light bulb recovery methods, including：It is handled waste and old LED illumination light bulb to obtain plastic shell, radiating aluminium sheet, LED chip and circuit board, and plastic shell and radiating aluminium sheet is recycled；Electronic component on stripper circuit plate simultaneously recycles metallic tin, obtains bare board；LED chip and bare board are subjected to melting, obtain black copper, metallurgical slag and cigarette ash；The separation and purification that metallic copper, silver, gold, platinum and palladium are realized in processing are carried out to black copper；The extraction and separation that yttrium oxide, gadolinium oxide and cerium oxide are realized in processing are carried out to metallurgical slag；The extraction and separation that single high-purity indium oxide and gallium oxide is realized in processing are carried out to cigarette ash.Its metal effectively realized in waste and old LED illumination light bulb recycles entirely, and organic efficiency is high, comprehensive utilization good compatibility, is suitble to industrialized production.

Description

A kind of waste and old LED illumination light bulb recovery method
Technical field
The present invention relates to resources circulations to recycle field more particularly to a kind of waste and old LED illumination light bulb recovery method.
Background technology
Due to LED it is small, energy consumption is low, service life is long, brightness is high, energy conservation and environmental protection, the characteristics such as sturdy and durable, LED Light bulb has obtained extensive popularization and application, has the trend of substitution common energy-saving lamp.The LED bulb scrapped with this is also produced successively Raw, in general, LED light bubble structure includes plastic lamp shade, LED chip, aluminium radiator fin, nickel plating lamp cap and control circuit board, In contain a large amount of metals resources, including rare precious metal（Gold, silver, platinum and palladium）, copper and rare earth element（Yttrium, gallium and cerium）Deng.If If directly being abandoned with house refuse after discarded, environment is not only polluted, the waste of metals resources can be also caused.Therefore, efficient green Ground recycles waste and old LED illumination light bulb, realizes the recycling of valuable valuable resource, has great social and economic benefit.
Currently, the technology about the recycling of waste and old LED illumination light bulb is concentrated mainly on rare earth element recycling, as Chinese invention is special Sharp CN103374661 and CN103361485 individually discloses the method that rare precious metal in waste and old LED light is recycled in two kinds of extractions, Wet processing and electrochemical deposition method, which is respectively adopted, realizes time of rare precious metal gallium and gold and metallic aluminium in LED wafer It receives and utilizes.Patent of invention CN102861759 discloses a kind of waste and old by simply separating metal and the realization of nonmetallic materials method The recycling of LED light.Patent of invention CN102864309 discloses a kind of using silver-plated in hypertoxic Cymag recycling LED light Method.
But existing method is both for there is individually the component of recovery value to carry out processing recycling in LED light, and with wet method Based on.In practical applications, material all in LED light is all worth recycling, including is wherein worth higher control circuit board, existing Some recovery methods are undoubtedly incomplete, still result in the waste of resource.
Invention content
In view of the above-mentioned problems, the present invention provides a kind of waste and old LED illumination light bulb recovery method, efficiently solve existing time The problem of still resulting in waste of resources in receiving method.
Technical solution provided by the invention is as follows：
A kind of waste and old LED illumination light bulb recovery method, including：
S100 is handled waste and old LED illumination light bulb to obtain plastic shell, radiating aluminium sheet, LED chip and circuit Plate, and plastic shell and radiating aluminium sheet are recycled；
Electronic component on S200 stripper circuit plates simultaneously recycles metallic tin, obtains bare board；
The bare board obtained in the LED chip obtained in step S100 and step S200 is carried out melting by S300, is obtained black Copper, metallurgical slag and cigarette ash；
S400 to the black copper obtained in step S300 carry out processing realize metallic copper, silver, gold, platinum and palladium separation and Purification；
S500 carries out the metallurgical slag obtained in step S300 the extraction that yttrium oxide, gadolinium oxide and cerium oxide are realized in processing Take separation；
S600 carries out the cigarette ash obtained in step S300 the extraction that single high-purity indium oxide and gallium oxide is realized in processing Separation.
It is further preferred that specifically including in the step s 100：
Waste and old LED illumination light bulb is carried out thick break and obtains plastic shell and base component by S110；
Base component is carried out attrition crushing by S120, by screening, magnetic separation and selection by winnowing sort after obtain radiating aluminium sheet, LED chip, circuit board and nickel plating lamp cap；
Plastic shell is carried out clean and reuse by S130, while recycling radiating aluminium sheet and nickel plating lamp cap.
It is further preferred that specifically including in step s 200：Circuit board is carried out to scald tin processing, it will be on circuit board Electronics member device is removed and recycles metallic tin, wherein the temperature for scalding tin processing is 250 ~ 350 DEG C（Degree Celsius）, duration 5 ~15s（Second）；And/or
It is specifically included in step S300：The bare board that will be obtained in the LED chip obtained in step S100 and step S200 Shearing-crushing to size is 1 ~ 5cm（Centimetre）After carry out melting, obtain black copper, metallurgical slag and cigarette ash.
It is further preferred that being specifically included in step S400：
S410 carries out electrolysis to black copper and handles to obtain high purity copper and the earth of positive pole, and is recycled to metallic copper；
S420 carries out sulfating roasting to the earth of positive pole obtained in step S410 and handles to obtain the solution containing metallic copper and silver And leached mud；
S430 carries out replacement Treatment to the solution containing metallic copper and silver obtained in step S420 and obtains thick silver, right later Thick silver carries out refining electrolysis and obtains high purity silver and recycled；
S440 carries out secondary smelting to the leached mud obtained in step S420, obtains metallurgical slag and precious metals containing lead；
S450 handles the precious metals containing lead obtained in step S440 progress refinement oxide to obtain precious metal alloys；
S460 carries out separating-purifying to the precious metal alloys obtained in step S450 and obtains metallic silver, gold, platinum and palladium simultaneously It is recycled.
It is further preferred that in the step s 420：Calcination temperature is 450 ~ 700 DEG C, instead in sulfating roasting processing procedure Be 1 ~ 5h between seasonable, and in roasting material the concentrated sulfuric acid a concentration of 0.5 ~ 5mol/L（Mole every liter）, what is obtained contains metallic copper and silver Solution include Ag2SO4And CuSO4；And/or
It is specifically included in step S430：
S431 replaces the Ag in the solution containing metallic copper and silver using copper sheet2SO4Obtain thick silver；
S432 to thick silver refine being electrolysed and is obtained high purity silver and recycle；
The CuSO that S433 will be replaced in step S4314And obtained in step S420 containing metallic copper and silver it is molten CuSO in liquid4It sends back in step S410 and is electrolysed to obtain high purity copper and is recycled.
It is further preferred that being specifically included in step S440：Coal dust is added in the leached mud obtained in the step s 420 Secondary smelting is carried out with lead oxide, obtains metallurgical slag and precious metals containing lead；Wherein, the quality of coal dust is that stoichiometrically reaction needs 1.2 ~ 1.5 times, the quality of lead oxide is 2 ~ 5 times of the earth of positive pole quality obtained in step S410, and smelting temperature 1000 ~ 1250 DEG C, 0.5 ~ 2h of reaction time；And/or
It is specifically included in step S450：The precious metals containing lead obtained in step S440 is put into cupel(lation) furnace and carries out ash and blows and handle To precious metal alloys and lead oxide, and lead oxide is sent into step S440 and is recycled, wherein grey blowing temp is 900 ~ 1150 DEG C, the wind pressure of the air blasted is 1.47 ~ 1.96kPa（KPa）.
It is further preferred that being specifically included in step S460：
S461 will obtain precious metal alloys in step S450 and be dissolved in HNO3In, metallic silver is dissolved out and is carried It is pure；
S462 immerses remaining insoluble slag in step S461 in chloroazotic acid；
NaNO is added in your liquid that S463 is obtained in step S4622Metallic gold is restored and carries out precipitation separation；
Precipitation isolates platinum palladium enriched product after hydrazine hydrate is added in the platinum palladium solution that S464 is obtained in step S463；
HNO is added in the platinum palladium enriched product that S465 is obtained in step S4643With ammonium chloride be centrifuged out ammonium chloropalladate and The ammonification filter residue of ammonium chloroplatinate；
Ammonium hydroxide is added in the ammonification filter residue that S466 is obtained in step S465 is centrifugally separating to obtain filter residue ammonium chloroplatinate and filter Four ammonia palladium solution of liquid dichloro；
Concentrated hydrochloric acid is added in the four ammonia palladium solution of filtrate dichloro that S467 is obtained in step S466 and ammonium hydroxide carries out at refining Reason obtains palladium-containing solution；
Hydrazine hydrate reduction is added in the palladium-containing solution that S468 is obtained in step S467 to obtain palladium powder and carry out at recycling Reason；
The filter residue ammonium chloroplatinate obtained in step S466 progress heat resolve is obtained spongy platinum and carried out at recycling by S469 Reason.
It is further preferred that being specifically included in step S500：
S510 obtains acidolysis slag after the metallurgical slag obtained in step S300 is carried out acidolysis and dries；
The acidolysis slag obtained in step S510 and sodium hydroxide and/or potassium hydroxide are carried out ball milling mixing by S520, are gone forward side by side The processing of row alkali fusion；Wherein, the acidolysis slag and the mass ratio of sodium hydroxide and/or potassium hydroxide are 1:0.8~1:3, alkali fusion processing Time be 0.5 ~ 4h；
S530 uses the alkali fusion product obtained in deionized water washing step S520 up to neutrality and is dried；
S540 dissolves the alkali fusion product after being dried in step S530 in hydrochloric acid, wherein solid-to-liquid ratio 1:3~1:10；
S550 is obtained after carrying out oxalic acid precipitation, oxidizing roasting and extraction and separation to the re chloride that step S540 is obtained To single yttrium oxide, gadolinium oxide and cerium oxide.
It is further preferred that being specifically included in step S600：
S610 by the cigarette ash obtained in step S300 be dissolved in hydrochloric acid, sulfuric acid and phosphoric acid one kind or mixing in contained There is the solution of gallium and indium, wherein hydrogen ion concentration 3-8mol/L；
Gallium and indium is separated by extraction in S620, and extractant is P204 or P507 or PC88A；
S630 carries out back extraction as stripping workshop using HCl and obtains the solution containing gallium and indium；
S640 obtains high-purity indium oxide and gallium oxide respectively after oxalic acid precipitation and roasting.
Compared with prior art, waste and old LED illumination light bulb recovery method provided by the invention can bring following beneficial to effect Fruit：
In waste and old LED illumination light bulb recovery method provided by the invention, recycled plastic shell is sorted by broken dismantling, is dissipated Hot aluminium flake and nickel plating lamp cap, and low temperature preroast, waterpower sorting, wet screening and the removal of thermokalite group technology are used in this course Sial impurity, effectively increases organic efficiency.The combined method substep that pyrometallurgy and wet chemistry extract is used to recycle later Rare precious metal in LED chip and circuit board（Au Ag Pt Pd）, copper and rare earth element.As can be seen that provided by the invention Method can realize that the metal in waste and old LED illumination light bulb recycles entirely, and organic efficiency is high, comprehensive utilization good compatibility, is suitble to Industrialized production has great society and economic effect in today of resource growing tension and the serious pollution ecology society that digs up mine Benefit.
Description of the drawings
Below by a manner of clearly understandable, preferred embodiment is described with reference to the drawings, to above-mentioned characteristic, technical characteristic, Advantage and its realization method are further described.
Fig. 1 is waste and old LED illumination light bulb recovery method flow diagram in the present invention；
Fig. 2 is that waste and old LED illumination light bulb recycles specific embodiment flow chart in the present invention.
Specific implementation mode
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, control is illustrated below The specific implementation mode of the present invention.It should be evident that drawings in the following description are only some embodiments of the invention, for For those of ordinary skill in the art, without creative efforts, other are can also be obtained according to these attached drawings Attached drawing, and obtain other embodiments.
The waste and old LED illumination light bulb recovery method flow diagram provided as shown in Figure 1 for invention, can from figure Go out, includes in the waste and old LED illumination light bulb recovery method：Waste and old LED illumination light bulb is handled to obtain outside plastics by S100 Shell, radiating aluminium sheet, LED chip and circuit board, and plastic shell and radiating aluminium sheet are recycled；S200 stripping electricity Electronic component on the plate of road simultaneously recycles metallic tin, obtains bare board；The LED chip and step that S300 will be obtained in step S100 The bare board obtained in S200 carries out melting, obtains black copper, metallurgical slag and cigarette ash；S400 is to the black copper that is obtained in step S300 Carry out separation and purification that metallic copper, silver, gold, platinum and palladium are realized in processing；S500 to the metallurgical slag that is obtained in step S300 into The extraction and separation of yttrium oxide, gadolinium oxide and cerium oxide are realized in row processing；S600 is at the cigarette ash that is obtained in step S300 Reason realizes the extraction and separation of single high-purity indium oxide and gallium oxide.Based on this, below by way of specific embodiment（As shown in Figure 2） The waste and old LED illumination light bulb recovery method is described in detail：
Embodiment 1
Waste and old LED illumination light bulb is respectively obtained by thick broken, attrition crushing by way of screening, magnetic separation and selection by winnowing sorting Plastic shell（It is recycled after cleaning, including PC（Polycarbonate, makrolon/PBT（Polybutylene Terephthalate, polybutylene terephthalate (PBT)）Deng）, radiating aluminium sheet, LED chip and circuit board.Circuit board is put into boiling hot In tin stove, temperature is 250 DEG C, continues 15s, and the metallic tin after thawing is recycled.Remove the bare board and LED after electronic component Chip passes through shearing-crushing（It is cut into 1 ~ 5cm sizes）Enter melting in smelting furnace afterwards, blasts air and coal dust, smelting temperature 1200 DEG C, wherein the organic matter in bare board provides energy and reduces the additive amount of fine coal.Black copper, metallurgical slag and cigarette ash are obtained after melting, Due to the difference of the physicochemical properties of each metal, copper as noble metal collector, formed containing your gold such as Au Ag Pt Pd The copper alloy of category, and yttrium, bundle and cerium enter smelting slag in the form of an oxide, and Ga Element and indium are blown into cigarette ash.Copper Alloy obtains the high purity copper of purity 99.993%, the rate of recovery 97.5% after electrolysis.Copper anode mud passes through sulfating roasting technique Copper removal, wherein calcination temperature are 450 DEG C, reaction time 3h；By roasting material water dissolution, solution sulfuric acid concentration is 0.5mol/ L, Ag in solution2SO4Thick silver is replaced as using copper sheet, and CuSO4It returns to cupric electrolysis technique and recycles copper.Leached mud add coal dust and Lead oxide carries out secondary smelting and obtains precious metals containing lead, and the wherein quality of coal dust is stoichiometrically react needs 1.2 times, and lead oxide is Obtained precious metals containing lead is fitted into cupel(lation) furnace by 2 times of earth of positive pole quality, 1200 DEG C of smelting temperature, reaction time 0.5h, grey blowing temp It is 900 DEG C, blasts the air of 1.96 kPa wind pressure, a small amount of KNO is added3The oxidation of accelerating impurity metal improves ash and blows efficiency.It is expensive Metal alloy uses HNO first3Dissolving silver, gold, platinum and the palladium for then chloroazotic acid being used to leach in insoluble slag obtain " your liquid "；It is " expensive NaNO is added in liquid "2Selective reduction precipitates parting, and platinum palladium solution is heated to 90 DEG C after parting, and precipitation point after hydrazine hydrate is added Platinum palladium enriched product is obtained from after, is continued to use aqua regia dissolution, is added HNO3It is red thick liquid with ammonium chloride modulation solution, 2h is stood, ammonium chloropalladate can be obtained by being centrifuged（[(NH4)2Pd]Cl6）And ammonium chloroplatinate（[(NH4)2Pt]Cl6）Ammonification filter Slag, filter residue ammonia solvent, it is 9 to adjust pH, stirs 1h, can get filter residue ammonium chloroplatinate, filtrate after standing centrifugal solid-liquid separation Four ammonia palladium of dichloro（[Pd(NH3)4]Cl2）Solution.Concentrated hydrochloric acid, ammonium hydroxide refining is added in four ammonia palladium solution of dichloro, obtains purer containing palladium Solution, then with hydrazine hydrate reduction, obtain palladium powder；Ammonium chloroplatinate obtains spongy platinum by heat resolve.It is obtained after metallurgical slag acidolysis Acidolysis slag after drying, and sodium hydroxide and/or potassium hydroxide are 1 by the mass ratio of acidolysis slag and alkali:0.8 carries out ball milling Mixing, the alkali fusion 4h at 700 DEG C；Deionized water is used to wash alkali fusion product to it after neutral, to use 3mol/L's after drying Dissolving with hydrochloric acid stirs 1h, solid-to-liquid ratio 1:3, to obtain re chloride, eventually by oxalic acid precipitation, oxidizing roasting and Single high purity rare earth oxides are obtained after extraction and separation（REOs, Rare-Earth Oxide in as shown）, yttrium oxide （Y2O3）, gadolinium oxide（Gd2O3）And cerium oxide（Ce2O3）, the rate of recovery is respectively 98.6%, 95.4% and 97.2%.Cigarette ash uses salt Acid, sulfuric acid and phosphoric acid it is one such or mixing, hydrogen ion concentration 4mol/L, at 50 DEG C stir 10h, obtain contain gallium and indium Solution, then pass through multi-stage continuous extraction separating gallium and indium, extractant P204（Di-(2-ethylhexyl)phosphoric acid ester）, and adopt Use HCl（Hydrochloric acid）It is stripped as stripping workshop, the solution containing gallium and indium is obtained respectively using oxalic acid precipitation and after roasting Obtain the oxide that purity is more than 99.99% gallium and indium（Ga in as shown2O3And In2O3）, the rate of recovery is respectively 92.6% He 91.9%.It is noted that after the spent acid generated in integrated artistic, lye are by neutralisation treatment, middle water recycles.
Embodiment 2
Waste and old LED illumination light bulb is respectively obtained by thick broken, attrition crushing by way of screening, magnetic separation and selection by winnowing sorting Plastic shell（It is recycled after cleaning, including PC/PBT etc.）, radiating aluminium sheet, LED chip and circuit board.Circuit board is put into boiling hot tin In stove, temperature is 300 DEG C, continues 10s, and the metallic tin after thawing is recycled, and removes bare board and LED chip after electronic component Pass through shearing-crushing（It is cut into 1 ~ 5cm sizes）Enter melting in smelting furnace afterwards, blasts air and coal dust, 1250 DEG C of smelting temperature, Wherein, the organic matter in bare board provides energy and reduces the additive amount of fine coal.Black copper, metallurgical slag and cigarette ash are obtained after melting, by In the difference of the physicochemical properties of each metal, copper as noble metal collector, formed containing the noble metals such as Au Ag Pt Pd Copper alloy, and yttrium, bundle and cerium enter smelting slag in the form of an oxide, and Ga Element and indium are blown into cigarette ash.Copper closes The high purity copper of purity 99.995%, the rate of recovery 98.1% are obtained after Jin Jing electrolysis.Copper anode mud is removed by sulfating roasting technique Copper, wherein calcination temperature are 500 DEG C, reaction time 4h；By roasting material water dissolution, solution sulfuric acid concentration is 1mol/L, molten Ag in liquid2SO4Thick silver is replaced as using copper sheet, and CuSO4It returns to cupric electrolysis technique and recycles copper.Leached mud adds coal dust and oxidation Lead carries out secondary smelting and obtains precious metals containing lead, and the wherein quality of coal dust is stoichiometrically react needs 1.3 times, and lead oxide is anode Obtained precious metals containing lead is fitted into cupel(lation) furnace by 2.5 times of shale amount, 1250 DEG C of smelting temperature, reaction time 1h, and grey blowing temp is 950 DEG C, the air of 1.80 kPa wind pressure is blasted, a small amount of KNO is added3The oxidation of accelerating impurity metal improves ash and blows efficiency.Your gold Belong to alloy and uses HNO first3Dissolving silver, gold, platinum and the palladium for then chloroazotic acid being used to leach in insoluble slag obtain " your liquid "；" your liquid " Middle addition NaNO2Selective reduction precipitates parting, and platinum palladium solution is heated to 90 DEG C, after precipitating separation after addition hydrazine hydrate after parting Platinum palladium enriched product is obtained, continues to use aqua regia dissolution, adds HNO3It is red thick liquid with ammonium chloride modulation solution, stands 3h, ammonium chloropalladate can be obtained by being centrifuged（[(NH4)2Pd]Cl6）And ammonium chloroplatinate（[(NH4)2Pt]Cl6）Ammonification filter residue, Filter residue ammonia solvent, it is 9.5 to adjust pH, stirs 1h, can get filter residue ammonium chloroplatinate, filtrate two after standing centrifugal solid-liquid separation Four ammonia palladium of chlorine（[Pd(NH3)4]Cl2）Solution.Concentrated hydrochloric acid, ammonium hydroxide refining is added in four ammonia palladium solution of dichloro, obtains purer molten containing palladium Liquid, then with hydrazine hydrate reduction, obtain palladium powder；Ammonium chloroplatinate obtains spongy platinum by heat resolve.It is obtained after metallurgical slag acidolysis Acidolysis slag after drying, in sodium hydroxide and/or potassium hydroxide one kind or mix, by the mass ratio of acidolysis slag and alkali be 1: 1.2 carry out ball milling mixings, the alkali fusion 3.5h at 700 DEG C, use deionized water wash alkali fusion product to its for neutrality after, after drying Using the dissolving with hydrochloric acid of 4mol/L, 1.5h, solid-to-liquid ratio 1 are stirred:5, it is heavy eventually by oxalic acid to obtain re chloride It forms sediment, obtain single high purity rare earth oxides, yttrium oxide, gadolinium oxide and cerium oxide, the rate of recovery point after oxidizing roasting and extraction and separation It Wei 93.5%, 98.3% and 95.8%.Cigarette ash is using hydrochloric acid, sulfuric acid and phosphoric acid is one such or mixing, hydrogen ion concentration are 5mol/L stirs 2h at 60 DEG C, obtains the solution containing gallium and indium, then passes through multi-stage continuous extraction separating gallium and indium, extraction Agent is P507（Di-2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester）, and be stripped as stripping workshop using HCl, contain gallium The oxide for being more than 99.99% gallium and indium using purity is obtained after oxalic acid precipitation and roasting respectively with the solution of indium, rate of recovery difference For 93.1% and 93.0%.It is noted that after the spent acid generated in integrated artistic, lye are by neutralisation treatment, middle water cycle makes With.
Embodiment 3
Waste and old LED illumination light bulb is respectively obtained by thick broken, attrition crushing by way of screening, magnetic separation and selection by winnowing sorting Plastic shell（It is recycled after cleaning, including PC/PBT etc.）, radiating aluminium sheet, LED chip and circuit board.Circuit board is put into boiling hot tin In stove, temperature is 350 DEG C, continues 5s, and the metallic tin after thawing is recycled, and removes bare board and LED chip after electronic component Pass through shearing-crushing（It is cut into 1 ~ 5cm sizes）Enter melting in smelting furnace afterwards, blasts air and coal dust, 1300 DEG C of smelting temperature, Wherein, the organic matter in bare board provides energy and reduces the additive amount of fine coal.Black copper, metallurgical slag and cigarette ash are obtained after melting, by In the difference of the physicochemical properties of each metal, copper as noble metal collector, formed containing the noble metals such as Au Ag Pt Pd Copper alloy, and yttrium, bundle and cerium enter smelting slag in the form of an oxide, and Ga Element and indium are blown into cigarette ash.Copper closes The high purity copper of purity 99.995%, the rate of recovery 97.9% are obtained after Jin Jing electrolysis.Copper anode mud is removed by sulfating roasting technique Copper, wherein calcination temperature are 550 DEG C, reaction time 5h；By roasting material water dissolution, solution sulfuric acid concentration is 2mol/L, molten Ag in liquid2SO4Thick silver is replaced as using copper sheet, and CuSO4It returns to cupric electrolysis technique and recycles copper.Leached mud adds coal dust and oxidation Lead carries out secondary smelting and obtains precious metals containing lead, and the wherein quality of coal dust is stoichiometrically react needs 1.4 times, and lead oxide is anode Obtained precious metals containing lead is fitted into cupel(lation) furnace by 3 times of shale amount, 1000 DEG C of smelting temperature, reaction time 1.5h, and grey blowing temp is 1000 DEG C, the air of 1.70kPa wind pressure is blasted, a small amount of KNO is added3The oxidation of accelerating impurity metal improves ash and blows efficiency.It is expensive Metal alloy uses HNO first3Dissolving silver, gold, platinum and the palladium for then chloroazotic acid being used to leach in insoluble slag obtain " your liquid "；It is " expensive NaNO is added in liquid "2Selective reduction precipitates parting, and platinum palladium solution is heated to 90 DEG C after parting, and precipitation point after hydrazine hydrate is added Platinum palladium enriched product is obtained from after, is continued to use aqua regia dissolution, is added HNO3It is red thick liquid with ammonium chloride modulation solution Body stands 4h, and ammonium chloropalladate can be obtained by being centrifuged（[(NH4)2Pd]Cl6）And ammonium chloroplatinate（[(NH4)2Pt]Cl6）Ammonia Change filter residue, filter residue ammonia solvent, it is 10 to adjust pH, stirs 1h, can get filter residue ammonium chloroplatinate after standing centrifugal solid-liquid separation, Four ammonia palladium of filtrate dichloro（[Pd(NH3)4]Cl2）Solution.Concentrated hydrochloric acid, ammonium hydroxide refining is added in four ammonia palladium solution of dichloro, obtains purer Palladium-containing solution, then with hydrazine hydrate reduction, obtain palladium powder；Ammonium chloroplatinate obtains spongy platinum by heat resolve.After metallurgical slag acidolysis The acidolysis slag of acquisition after drying, in sodium hydroxide and/or potassium hydroxide one kind or mix, by the quality of acidolysis slag and alkali Than being 1:1.5 carry out ball milling mixings, the alkali fusion 3h at 600 DEG C, use deionized water to wash alkali fusion product to it as after neutral, baking The dissolving with hydrochloric acid that 5mol/L is used after dry, stirs 2h, solid-to-liquid ratio 1:7, to obtain re chloride, eventually by oxalic acid Single high purity rare earth oxides, yttrium oxide, gadolinium oxide and cerium oxide, the rate of recovery are obtained after precipitation, oxidizing roasting and extraction and separation Respectively 97.3%, 95.8% and 96.3%.Cigarette ash is using hydrochloric acid, sulfuric acid and phosphoric acid is one such or mixing, hydrogen ion concentration are 6mol/L stirs 4h at 70 DEG C, obtains the solution containing gallium and indium, then passes through multi-stage continuous extraction separating gallium and indium, extraction Agent is PC88A（2- ethylhexyls phosphonic acids-mono- 2- ethylhexyl esters）, and be stripped as stripping workshop using HCl, contain There are the oxide that the solution of gallium and indium is more than 99.99% gallium and indium using purity is obtained after oxalic acid precipitation and roasting respectively, the rate of recovery Respectively 92.5% and 91.8%.It is noted that after the spent acid generated in integrated artistic, lye are by neutralisation treatment, middle water follows Ring uses.
Embodiment 4
Waste and old LED illumination light bulb is respectively obtained by thick broken, attrition crushing by way of screening, magnetic separation and selection by winnowing sorting Plastic shell（It is recycled after cleaning, including PC/PBT etc.）, radiating aluminium sheet, LED chip and circuit board.Circuit board is put into boiling hot tin In stove, temperature is 250 DEG C, continues 5s, and the metallic tin after thawing is recycled, and removes bare board and LED chip after electronic component Pass through shearing-crushing（It is cut into 1 ~ 5cm sizes）Enter melting in smelting furnace afterwards, blasts air and coal dust, 1350 DEG C of smelting temperature, Wherein, the organic matter in bare board provides energy and reduces the additive amount of fine coal.Black copper, metallurgical slag and cigarette ash are obtained after melting, by In the difference of the physicochemical properties of each metal, copper as noble metal collector, formed containing the noble metals such as Au Ag Pt Pd Copper alloy, and yttrium, bundle and cerium enter smelting slag in the form of an oxide, and Ga Element and indium are blown into cigarette ash.Copper closes The high purity copper of purity 99.992%, the rate of recovery 96.7% are obtained after Jin Jing electrolysis.Copper anode mud is removed by sulfating roasting technique Copper, wherein calcination temperature are 600 DEG C, reaction time 2h；By roasting material water dissolution, solution sulfuric acid concentration is 3mol/L, molten Ag in liquid2SO4Thick silver is replaced as using copper sheet, and CuSO4It returns to cupric electrolysis technique and recycles copper.Leached mud adds coal dust and oxidation Lead carries out secondary smelting and obtains precious metals containing lead, and the wherein quality of coal dust is stoichiometrically react needs 1.5 times, and lead oxide is anode Obtained precious metals containing lead is fitted into cupel(lation) furnace by 3.5 times of shale amount, 1050 DEG C of smelting temperature, reaction time 2h, and grey blowing temp is 1050 DEG C, the air of 1.6 kPa wind pressure is blasted, a small amount of KNO is added3The oxidation of accelerating impurity metal improves ash and blows efficiency.It is expensive Metal alloy uses HNO first3Dissolving silver, gold, platinum and the palladium for then chloroazotic acid being used to leach in insoluble slag obtain " your liquid "；It is " expensive NaNO is added in liquid "2Selective reduction precipitates parting, and platinum palladium solution is heated to 90 DEG C after parting, and precipitation point after hydrazine hydrate is added Platinum palladium enriched product is obtained from after, is continued to use aqua regia dissolution, is added HNO3It is red thick liquid with ammonium chloride modulation solution Body stands 5h, and ammonium chloropalladate can be obtained by being centrifuged（[(NH4)2Pd]Cl6）And ammonium chloroplatinate（[(NH4)2Pt]Cl6）Ammonia Change filter residue, filter residue ammonia solvent, it is 9.5 to adjust pH, stirs 1h, can get filter residue chloroplatinic acid after standing centrifugal solid-liquid separation Ammonium, four ammonia palladium of filtrate dichloro（[Pd(NH3)4]Cl2）Solution.Four ammonia palladium solution of dichloro be added concentrated hydrochloric acid, ammonium hydroxide refining, obtain compared with Pure palladium-containing solution, then with hydrazine hydrate reduction, obtain palladium powder；Ammonium chloroplatinate obtains spongy platinum by heat resolve.Metallurgical slag acid The acidolysis slag obtained after solution after drying, in sodium hydroxide and/or potassium hydroxide one kind or mix, by acidolysis slag and alkali Mass ratio is 1:2 carry out ball milling mixing, and the alkali fusion 2.5h at 500 DEG C uses deionized water to wash alkali fusion product to it as neutrality Afterwards, the dissolving with hydrochloric acid of 2mol/L is used after drying, stirs 1.5h, solid-to-liquid ratio 1:8, to obtain re chloride, finally By obtaining single high purity rare earth oxides, yttrium oxide, gadolinium oxide and oxidation after oxalic acid precipitation, oxidizing roasting and extraction and separation Cerium, the rate of recovery are respectively 96.6%, 95.0% and 94.6%.Cigarette ash using hydrochloric acid, sulfuric acid and phosphoric acid it is one such or mixing, hydrogen Ion concentration is 7mol/L, and 6h is stirred at 80 DEG C, obtains the solution containing gallium and indium, then passes through multi-stage continuous extraction separating gallium And indium, extractant P507, and be stripped as stripping workshop using HCl, the solution containing gallium and indium is heavy using oxalic acid It forms sediment and obtains the oxide that purity is more than 99.99% gallium and indium after roasting respectively, the rate of recovery is respectively 90.8% and 91.3%.It says Bright, after the spent acid that is generated in integrated artistic, lye are by neutralisation treatment, middle water recycles.
Embodiment 5
Waste and old LED illumination light bulb is respectively obtained by thick broken, attrition crushing by way of screening, magnetic separation and selection by winnowing sorting Plastic shell（It is recycled after cleaning, including PC/PBT etc.）, radiating aluminium sheet, LED chip and circuit board.Circuit board is put into boiling hot tin In stove, temperature is 300 DEG C, continues 10s, and the metallic tin after thawing is recycled, and removes bare board and LED chip after electronic component Pass through shearing-crushing（It is cut into 1 ~ 5cm sizes）Enter melting in smelting furnace afterwards, blasts air and coal dust, 1400 DEG C of smelting temperature, Wherein, the organic matter in bare board provides energy and reduces the additive amount of fine coal.Black copper, metallurgical slag and cigarette ash are obtained after melting, by In the difference of the physicochemical properties of each metal, copper as noble metal collector, formed containing the noble metals such as Au Ag Pt Pd Copper alloy, and yttrium, bundle and cerium enter smelting slag in the form of an oxide, and Ga Element and indium are blown into cigarette ash.Copper closes The high purity copper of purity 99.996%, the rate of recovery 97.2% are obtained after Jin Jing electrolysis.Copper anode mud is removed by sulfating roasting technique Copper, wherein calcination temperature are 650 DEG C, reaction time 1h；By roasting material water dissolution, solution sulfuric acid concentration is 4mol/L, molten Ag in liquid2SO4Thick silver is replaced as using copper sheet, and CuSO4It returns to cupric electrolysis technique and recycles copper.Leached mud adds coal dust and oxidation Lead carries out secondary smelting and obtains precious metals containing lead, and the wherein quality of coal dust is stoichiometrically react needs 1.4 times, and lead oxide is anode Obtained precious metals containing lead is fitted into cupel(lation) furnace by 4 times of shale amount, 1100 DEG C of smelting temperature, reaction time 1.5h, and grey blowing temp is 1100 DEG C, the air of 1.5 kPa wind pressure is blasted, a small amount of KNO is added3The oxidation of accelerating impurity metal improves ash and blows efficiency.It is expensive Metal alloy uses HNO first3Dissolving silver, gold, platinum and the palladium for then chloroazotic acid being used to leach in insoluble slag obtain " your liquid "；It is " expensive NaNO is added in liquid "2Selective reduction precipitates parting, and platinum palladium solution is heated to 90 DEG C after parting, and precipitation point after hydrazine hydrate is added Platinum palladium enriched product is obtained from after, is continued to use aqua regia dissolution, is added HNO3It is red thick liquid with ammonium chloride modulation solution Body stands 6h, and ammonium chloropalladate can be obtained by being centrifuged（[(NH4)2Pd]Cl6）And ammonium chloroplatinate（[(NH4)2Pt]Cl6）Ammonia Change filter residue, filter residue ammonia solvent, it is 9 to adjust pH, stirs 1h, can get filter residue ammonium chloroplatinate after standing centrifugal solid-liquid separation, Four ammonia palladium of filtrate dichloro（[Pd(NH3)4]Cl2）Solution.Concentrated hydrochloric acid, ammonium hydroxide refining is added in four ammonia palladium solution of dichloro, obtains purer Palladium-containing solution, then with hydrazine hydrate reduction, obtain palladium powder；Ammonium chloroplatinate obtains spongy platinum by heat resolve.After metallurgical slag acidolysis The acidolysis slag of acquisition after drying, in sodium hydroxide and/or potassium hydroxide one kind or mix, by the quality of acidolysis slag and alkali Than being 1:2.5 carry out ball milling mixings, the alkali fusion 1.5h at 400 DEG C, use deionized water wash alkali fusion product to its for neutrality after, The dissolving with hydrochloric acid that 3mol/L is used after drying, stirs 1h, solid-to-liquid ratio 1:9, to obtain re chloride, eventually by grass Single high purity rare earth oxides, yttrium oxide, gadolinium oxide and cerium oxide, recycling are obtained after acid precipitation, oxidizing roasting and extraction and separation Rate is respectively 94.2%, 92.8% and 91.9%.Cigarette ash using hydrochloric acid, sulfuric acid and phosphoric acid it is one such or mixing, hydrogen ion concentration For 8mol/L, 8 h are stirred at 90 DEG C, obtain the solution containing gallium and indium, then pass through multi-stage continuous extraction separating gallium and indium, extraction It is P204 to take agent, and is stripped as stripping workshop using HCl, and the solution containing gallium and indium uses oxalic acid precipitation and roasting Obtain the oxide that purity is more than 99.99% gallium and indium respectively afterwards, the rate of recovery is respectively 91.8% and 92.9%.It is noted that whole After the spent acid that is generated in body technology, lye are by neutralisation treatment, middle water recycles.
Embodiment 6
Waste and old LED illumination light bulb is respectively obtained by thick broken, attrition crushing by way of screening, magnetic separation and selection by winnowing sorting Plastic shell（It is recycled after cleaning, including PC/PBT etc.）, radiating aluminium sheet, LED chip and circuit board.Circuit board is put into boiling hot tin In stove, temperature is 350 DEG C, continues 15s, and the metallic tin after thawing is recycled, and removes bare board and LED chip after electronic component Pass through shearing-crushing（It is cut into 1 ~ 5cm sizes）Enter melting in smelting furnace afterwards, blasts air and coal dust, 1200 DEG C of smelting temperature, Wherein, the organic matter in bare board provides energy and reduces the additive amount of fine coal.Black copper, metallurgical slag and cigarette ash are obtained after melting, by In the difference of the physicochemical properties of each metal, copper as noble metal collector, formed containing the noble metals such as Au Ag Pt Pd Copper alloy, and yttrium, bundle and cerium enter smelting slag in the form of an oxide, and Ga Element and indium are blown into cigarette ash.Copper closes The high purity copper of purity 99.992%, the rate of recovery 98.5% are obtained after Jin Jing electrolysis.Copper anode mud is removed by sulfating roasting technique Copper, wherein calcination temperature are 700 DEG C, reaction time 4h；By roasting material water dissolution, solution sulfuric acid concentration is 5mol/L, molten Ag in liquid2SO4Thick silver is replaced as using copper sheet, and CuSO4It returns to cupric electrolysis technique and recycles copper.Leached mud adds coal dust and oxidation Lead carries out secondary smelting and obtains precious metals containing lead, and the wherein quality of coal dust is stoichiometrically react needs 1.3 times, and lead oxide is anode Obtained precious metals containing lead is fitted into cupel(lation) furnace by 5 times of shale amount, 1150 DEG C of smelting temperature, reaction time 1h, and grey blowing temp is 1150 DEG C, the air of 1.47 kPa wind pressure is blasted, a small amount of KNO is added3The oxidation of accelerating impurity metal improves ash and blows efficiency.Noble metal Alloy uses HNO first3Dissolving silver, gold, platinum and the palladium for then chloroazotic acid being used to leach in insoluble slag obtain " your liquid "；In " your liquid " NaNO is added2Selective reduction precipitates parting, and platinum palladium solution is heated to 90 DEG C after parting, is obtained after separation is precipitated after addition hydrazine hydrate To platinum palladium enriched product, continues to use aqua regia dissolution, add HNO3It is red thick liquid with ammonium chloride modulation solution, stands 3h, ammonium chloropalladate can be obtained by being centrifuged（[(NH4)2Pd]Cl6）And ammonium chloroplatinate（[(NH4)2Pt]Cl6）Ammonification filter residue, Filter residue ammonia solvent, it is 10 to adjust pH, stirs 1h, can get filter residue ammonium chloroplatinate, filtrate two after standing centrifugal solid-liquid separation Four ammonia palladium of chlorine（[Pd(NH3)4]Cl2）Solution.Concentrated hydrochloric acid, ammonium hydroxide refining is added in four ammonia palladium solution of dichloro, obtains purer molten containing palladium Liquid, then with hydrazine hydrate reduction, obtain palladium powder；Ammonium chloroplatinate obtains spongy platinum by heat resolve.It is obtained after metallurgical slag acidolysis Acidolysis slag after drying, in sodium hydroxide and/or potassium hydroxide one kind or mix, by the mass ratio of acidolysis slag and alkali be 1: 3 carry out ball milling mixings, the alkali fusion 0.5h at 800 DEG C, use deionized water wash alkali fusion product to its for neutrality after, adopted after drying With the dissolving with hydrochloric acid of 4mol/L, 2h, solid-to-liquid ratio 1 are stirred:10, to obtain re chloride, eventually by oxalic acid precipitation, Single high purity rare earth oxides, yttrium oxide, gadolinium oxide and cerium oxide are obtained after oxidizing roasting and extraction and separation, the rate of recovery is respectively 93.8%, 96.7% and 95.8%.Cigarette ash using hydrochloric acid, sulfuric acid and phosphoric acid it is one such or mixing, hydrogen ion concentration 3mol/ L stirs 10 h at 30 DEG C, obtains the solution containing gallium and indium, then by multi-stage continuous extraction separating gallium and indium, extractant is PC88A, and be stripped as stripping workshop using HCl, the solution containing gallium and indium is using after oxalic acid precipitation and roasting points Not Huo get purity be more than 99.99% gallium and indium oxide, the rate of recovery is respectively 92.4% and 93.5%.It is noted that whole work After the spent acid that is generated in skill, lye are by neutralisation treatment, middle water recycles.
It should be noted that above-described embodiment can be freely combined as needed.The above is only the preferred of the present invention Embodiment, it is noted that for those skilled in the art, in the premise for not departing from the principle of the invention Under, several improvements and modifications can also be made, these improvements and modifications also should be regarded as protection scope of the present invention.

Claims (8)

1. a kind of waste and old LED illumination light bulb recovery method, which is characterized in that wrapped in the waste and old LED illumination light bulb recovery method It includes：
S100 is handled waste and old LED illumination light bulb to obtain plastic shell, radiating aluminium sheet, LED chip and circuit board, and right Plastic shell and radiating aluminium sheet are recycled；
Electronic component on S200 stripper circuit plates simultaneously recycles metallic tin, obtains bare board；
The bare board obtained in the LED chip obtained in step S100 and step S200 is carried out melting by S300, is obtained black copper, is smelted Slag and cigarette ash；
S400 carries out the black copper obtained in step S300 the separation and purification that metallic copper, silver, gold, platinum and palladium are realized in processing； It specifically includes：
S410 carries out electrolysis to black copper and handles to obtain high purity copper and the earth of positive pole, and is recycled to metallic copper；
S420 to the earth of positive pole that is obtained in step S410 carry out sulfating roasting handle to obtain solution containing metallic copper and silver and Leached mud；
S430 carries out replacement Treatment to obtaining the solution containing metallic copper and silver in step S420 and obtains thick silver, later to thick silver into Row refining electrolysis obtains high purity silver and is recycled；
S440 carries out secondary smelting to the leached mud obtained in step S420, obtains metallurgical slag and precious metals containing lead；
S450 handles the precious metals containing lead obtained in step S440 progress refinement oxide to obtain precious metal alloys；
S460 obtains metallic silver, gold, platinum and palladium to the precious metal alloys progress separating-purifying obtained in step S450 and carries out Recycling；
S500 carries out the metallurgical slag obtained in step S300 the extraction point that yttrium oxide, gadolinium oxide and cerium oxide are realized in processing From；
S600 carries out the cigarette ash obtained in step S300 the extraction and separation that single high-purity indium oxide and gallium oxide is realized in processing.
2. waste and old LED illumination light bulb recovery method as described in claim 1, which is characterized in that
It specifically includes in the step s 100：
Waste and old LED illumination light bulb is carried out thick break and obtains plastic shell and base component by S110；
Base component is carried out attrition crushing by S120, and radiating aluminium sheet, LED core are obtained after being sorted by screening, magnetic separation and selection by winnowing Piece, circuit board and nickel plating lamp cap；
Plastic shell is carried out clean and reuse by S130, while recycling radiating aluminium sheet and nickel plating lamp cap.
3. waste and old LED illumination light bulb recovery method as described in claim 1, which is characterized in that
It specifically includes in step s 200：Circuit board is carried out to scald tin processing, the electronics member device on circuit board is removed and returned Receive metallic tin, wherein the temperature for scalding tin processing is 250~350 DEG C, and duration is 5~15s；And/or
It is specifically included in step S300：The bare board obtained in the LED chip obtained in step S100 and step S200 is sheared It is crushed to after size is 1~5cm and carries out melting, obtain black copper, metallurgical slag and cigarette ash.
4. waste and old LED illumination light bulb recovery method as described in claim 1, which is characterized in that
In the step s 420：Calcination temperature is 450~700 DEG C in sulfating roasting processing procedure, the reaction time is 1~5h, and A concentration of 0.5~5mol/L of the concentrated sulfuric acid in roasting material, the obtained solution containing metallic copper and silver includes Ag2SO4And CuSO4； And/or
It is specifically included in step S430：
S431 replaces the Ag in the solution containing metallic copper and silver using copper sheet2SO4Obtain thick silver；
S432 to thick silver refine being electrolysed and is obtained high purity silver and recycle；
The CuSO that S433 will be replaced in step S4314And in the solution containing metallic copper and silver obtained in step S420 CuSO4It sends back in step S410 and is electrolysed to obtain high purity copper and is recycled.
5. waste and old LED illumination light bulb recovery method as described in claim 1, which is characterized in that
It is specifically included in step S440：Coal dust is added in the leached mud obtained in the step s 420 and lead oxide carries out secondary smelting Refining, obtains metallurgical slag and precious metals containing lead；Wherein, the quality of coal dust is stoichiometrically react needs 1.2~1.5 times, lead oxide Quality is 2~5 times of earth of positive pole quality obtained in step S410, and 1000~1250 DEG C of smelting temperature, the reaction time 0.5~ 2h；And/or
It is specifically included in step S450：By the precious metals containing lead obtained in step S440 be put into cupel(lation) furnace carry out ash blow processing obtain it is expensive Metal alloy and lead oxide, and lead oxide is sent into step S440 and is recycled, wherein grey blowing temp is 900~1150 DEG C, The wind pressure of the air blasted is 1.47~1.96kPa.
6. waste and old LED illumination light bulb recovery method as described in claim 1, which is characterized in that specifically wrapped in step S460 It includes：
S461 will obtain precious metal alloys in step S450 and be dissolved in HNO3In, metallic silver is dissolved out and is purified；
S462 immerses remaining insoluble slag in step S461 in chloroazotic acid；
NaNO is added in your liquid that S463 is obtained in step S4622Metallic gold is restored and carries out precipitation separation；
Precipitation isolates platinum palladium enriched product after hydrazine hydrate is added in the platinum palladium solution that S464 is obtained in step S463；
HNO is added in the platinum palladium enriched product that S465 is obtained in step S4643It is centrifuged out ammonium chloropalladate and chloroplatinic acid with ammonium chloride The ammonification filter residue of ammonium；
Ammonium hydroxide is added in the ammonification filter residue that S466 is obtained in step S465 is centrifugally separating to obtain filter residue ammonium chloroplatinate and filtrate two Four ammonia palladium solution of chlorine；
Concentrated hydrochloric acid is added in the four ammonia palladium solution of filtrate dichloro that S467 is obtained in step S466 and ammonium hydroxide carries out refining treatment and obtains To palladium-containing solution；
Hydrazine hydrate reduction is added in the palladium-containing solution that S468 is obtained in step S467 to obtain palladium powder and be recycled；
The filter residue ammonium chloroplatinate obtained in step S466 progress heat resolve is obtained spongy platinum and is recycled by S469.
7. the waste and old LED illumination light bulb recovery method as described in claims 1 or 2 or 3, which is characterized in that in step S500 It specifically includes：
S510 obtains acidolysis slag after the metallurgical slag obtained in step S300 is carried out acidolysis and dries；
The acidolysis slag obtained in step S510 and sodium hydroxide and/or potassium hydroxide are carried out ball milling mixing by S520, and carry out alkali Molten processing；Wherein, the acidolysis slag and the mass ratio of sodium hydroxide and/or potassium hydroxide are 1:0.8~1:3, alkali fusion processing Time is 0.5~4h；
S530 uses the alkali fusion product obtained in deionized water washing step S520 up to neutrality and is dried；
S540 dissolves the alkali fusion product after being dried in step S530 in hydrochloric acid, wherein solid-to-liquid ratio 1:3~1:10；
It is obtained after re chloride progress oxalic acid precipitation, oxidizing roasting and extraction and separation that S550 obtains step S540 single Yttrium oxide, gadolinium oxide and cerium oxide.
8. the waste and old LED illumination light bulb recovery method as described in claims 1 or 2 or 3, which is characterized in that in step S600 It specifically includes：
S610 by the cigarette ash obtained in step S300 be dissolved in hydrochloric acid, sulfuric acid and phosphoric acid one kind or mixing in obtain containing metal The solution of gallium and indium, wherein hydrogen ion concentration 3-8mol/L；
Gallium and indium is separated by extraction in S620, and extractant is P204 or P507 or PC88A；
S630 carries out back extraction as stripping workshop using HCl and obtains the solution containing gallium and indium；
S640 obtains high-purity indium oxide and gallium oxide respectively after oxalic acid precipitation and roasting.
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