CN108441637B - The method of valuable metal is recycled from the useless chip of copper indium gallium selenium solar hull cell - Google Patents
The method of valuable metal is recycled from the useless chip of copper indium gallium selenium solar hull cell Download PDFInfo
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- CN108441637B CN108441637B CN201810220326.3A CN201810220326A CN108441637B CN 108441637 B CN108441637 B CN 108441637B CN 201810220326 A CN201810220326 A CN 201810220326A CN 108441637 B CN108441637 B CN 108441637B
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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
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/02—Elemental selenium or tellurium
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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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0078—Leaching or slurrying with ammoniacal solutions, e.g. ammonium hydroxide
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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
- C22B58/00—Obtaining gallium or indium
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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
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- 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
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- 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
- C25C1/22—Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
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- 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
Abstract
The present invention provides a kind of method that valuable metal is recycled from the useless chip of copper indium gallium selenium solar hull cell, belongs to resource secondary and utilizes technical field.The useless chip of copper indium gallium selenide (CIGS) solar film battery is carried out substrate desquamation by this method；Ammonia leaching is carried out to the valuable metal layer after removing, ammonia leaching solution and ammonia leaching residue are obtained by solid-liquor separation after leaching；Cathode copper is obtained after ammonia leaching solution extraction, electrodeposition；Ammonia leaching residue carries out alkali leaching, obtains alkali immersion liquid and alkali phase analysis by solid-liquor separation after leaching；Alkali phase analysis carries out acidleach again and obtains pickle liquor and acid leaching residue, and acid leaching residue returns to ammonia leaching；SO is passed through into pickle liquor2Reduction obtains the impure selenium that purity is greater than 98%, and filtrate is obtained after filtering；Filtrate reduction, purification obtain high purity indium；Alkali immersion liquid is obtained by removal of impurities containing molybdenum, the slag of tin and filtrate；Filtrate is electrolysed to obtain thick gallium, and thick gallium purifies to obtain high purity gallium.The present invention can be realized the efficient selective leaching of copper, indium, gallium, selenium, have a good application prospect.
Description
Technical field
The present invention relates to resource secondaries to utilize technical field, particularly relates to a kind of useless from copper indium gallium selenium solar hull cell
The method of valuable metal is recycled in chip.
Background technique
CIGS solar film battery has the characteristics that low cost, easy for installation, applied widely, and application prospect is very wide
It is wealthy.In production CIGS cell process, a large amount of CIGS waste material can be generated, CIGS target, the CIGS electricity that cannot be such as fully utilized
Pond defective products etc..And in these waste materials in addition to containing heavy metal copper, also containing rare metals such as indium, gallium and selenium.For be conducive to indium,
The sustainable utilization of the rare metals such as gallium and selenium and heavy metal copper needs to be separated and be separately recovered, to facilitate further
Ground recycles, to guarantee the sustainable development of CIGS thin film solar cell material.
It evaporates in Chinese patent CN105886767A by the selenium in CIGS waste material is first acidizing fired, then again to residue
Three kinds of metals separated, especially to dividing the lye containing gallium generated in indium step and divide in gallium step solution of the gained containing gallium
Processing is merged, and electrodeposition extraction raffinate may return to electrodeposition containing circulation electrodeposition is carried out in Gallium solution, to realize gallium
Efficiently, circulation and stress.This method extracting operation step is complicated.
United States Patent (USP) US5779877 by discarded copper and indium Se solar cell broken, salt Ore Leaching, two electrode separation copper,
Selenium and indium, then evaporation, decomposition obtains the mixture of indium and zinc oxide, and oxidation distillation separates copper and selenium.But this method process
Long, two electrolysis separate metal process and are difficult to control, and oxidation distillation separation is not thorough, and selenium recovery is low, and final products are only
Metallic compound, rare metal could be obtained by needing to be further processed, while the applicability of this method is restricted, and can not be solved
The certainly recycling problem of gallium.
Chinese patent CN104018186A provides a kind of recovery method of copper indium gallium selenide, carries out CIGS waste material as anode
Electrolytic recovery indium, for the sediments such as earth of positive pole by leaching, leachate recycles gallium by electrodeposition；Leached mud passes through acidleach, alkali tune
Acid, then be separately added into reducing agent and selenium and copper is separately recovered.Although this method process is simple, asking for impurity doping is not considered comprehensively
Topic；Not only contain these four valuable metal elements in CIGS waste material, also contains a small amount of Zn, Cd, Mo, Al and Sn impurity.
Chinese patent CN102296178A discloses a kind of recovery method of copper indium gallium selenide.This method first with hydrochloric acid with
The mixed solution of hydrogen peroxide dissolves the metal-powder comprising copper indium gallium selenide, after isolating selenium using hydrazine, is set with indium metal
Swap out copper, combines dispersion strip liquor to separate indium with gallium finally by brace type liquid film.However the leaching rate of this method metal is simultaneously
It is not high, toxic gaseous hydrochlorides and the chlorine etc. of pollution environment, reaction are easy to produce with hydrochloric acid and hydrogen peroxide dissolution CIGS waste material
Process is also very fierce, and restores the hydrazine hydrate that uses of selenium also toxicity is stronger, and operating process is relatively hazardous, also be easy to cause environment dirty
Dye.
To sum up, copper indium gallium selenide waste material recovery method in the prior art that there are comprehensive recoveries is low, separation not exclusively,
The problems such as danger complicated for operation, high production cost, big environmental pollution, it would be highly desirable to it is useless to invent a kind of CIGS for being able to solve the above problem
Chip recovery method.
Summary of the invention
The technical problem to be solved in the present invention is to provide one kind to recycle from the useless chip of copper indium gallium selenium solar hull cell
The method of valuable metal
It is as follows that the method comprising the steps of:
(1) stainless steel/glass substrate removing: the useless chip of copper indium gallium selenium solar hull cell is subjected to substrate desquamation, is obtained
To valuable metal layer；
(2) ammonia soaks: the valuable metal layer that step (1) is obtained carries out ammonia leaching, is obtained after the completion of leaching by solid-liquor separation
Ammonia leaching solution and ammonia leaching residue；
(3) extraction, electrodeposition: cathode copper will be obtained after the extraction of ammonia leaching solution obtained in step (2), electrodeposition；
(4) alkali soaks: ammonia leaching residue obtained in step (2) being carried out alkali leaching, obtains alkali by solid-liquor separation after the completion of leaching
Immersion liquid and alkali phase analysis；
(5) acidleach: alkali phase analysis obtained in step (4) is subjected to acidleach with inorganic acid, is divided admittedly after the completion of leaching by liquid
From pickle liquor and acid leaching residue is obtained, ammonia leaching is carried out in acid leaching residue return step (2)；
(6) it sinks selenium: being passed through SO in the pickle liquor obtained in step (5)2, it restores and obtains the impure selenium that purity is greater than 98%,
Filtrate one is obtained after filtering；
(7) it restores, purify: the reduction of filtrate one obtained in step (6) being obtained into thick indium, thick indium further purifies and obtains height
Pure indium and slag containing aluminium, tin；
(8) it cleans: alkali immersion liquid obtained in step (4) is cleaned to obtain containing molybdenum, the slag of tin and filtrate two；
(9) it is electrolysed, purifies: the electrolysis of filtrate two obtained in step (8) being obtained into thick gallium, thick gallium purifies to obtain high purity gallium.
Wherein:
The copper indium gallium selenium solar hull cell handled in step (1) give up chip containing Cu 15~25%, In 15~25%,
Ga 15~25%, Se 40~60%, and a small amount of Zn, Cd, Mo, Al and Sn impurity.
It is containing ammonia or ammonia and ammonium salt mixed solution that ammonia, which soaks leaching agent used, in step (2), and leaching agent concentration is with NH3It counts, is
50~350g/L, extraction temperature are 30~90 DEG C, and extraction time is 0.5~5h, and solid-to-liquid ratio is 1:1~1:10g/mL before leaching.
The NaOH or KOH that alkali leaching is 30%~80% with mass concentration in step (4) are leaching agent, in natural pressure condition
Lower alkali leaching, wherein it is 30~150 DEG C that alkali, which soaks temperature, and extraction time is 0.5~5h, and solid-to-liquid ratio is 1:1~1:10g/ before leaching
mL。
Acidleach is inorganic acid with acid in step (5), and acidleach temperature is 30~150 DEG C, and extraction time is 0.5~5h, is leached
Preceding solid-to-liquid ratio is 1:1~1:10g/mL.
SO in step (6)2Intake are as follows: SO2Se the mass ratio of the material 1.0~1.5 in the amount and raw material of substance.
It is that iron powder, hydrazine hydrate, formaldehyde and both of which or three's arbitrary proportion are mixed that reducing agent used is restored in step (7)
Close object；The method inclusion region smelting process of purifying crude indium, vacuum melting method, vacuum distillation method, Solid phase electrolysis method, segregation purification
Method, hydrogen plasma arc melting method.
The method of purification of thick gallium includes low-temperature electrolytic purification, area smelting refinement or both combined purifying in step (9).
The advantageous effects of the above technical solutions of the present invention are as follows:
The method achieve the leachings of the efficient selective of copper, indium, gallium, selenium；The problem of having comprehensively considered metal impurities doping,
Metal target separation is complete；This programme operation is relatively easy, without operational hazards, pollution-free problem.
Detailed description of the invention
Fig. 1 is the method and process stream of the invention that valuable metal is recycled from the useless chip of copper indium gallium selenium solar hull cell
Cheng Tu.
Specific embodiment
To keep the technical problem to be solved in the present invention, technical solution and advantage clearer, below in conjunction with attached drawing and tool
Body embodiment is described in detail.
The present invention provides a kind of method that valuable metal is recycled from the useless chip of copper indium gallium selenium solar hull cell.
As shown in Figure 1, that the method comprising the steps of is as follows:
(1) stainless steel/glass substrate removing: the useless chip of copper indium gallium selenium solar hull cell is subjected to substrate desquamation, is obtained
To valuable metal layer；
(2) ammonia soaks: the valuable metal layer that step (1) is obtained carries out ammonia leaching, is obtained after the completion of leaching by solid-liquor separation
Ammonia leaching solution and ammonia leaching residue；
(3) extraction, electrodeposition: cathode copper will be obtained after the extraction of ammonia leaching solution obtained in step (2), electrodeposition；
(4) alkali soaks: ammonia leaching residue obtained in step (2) being carried out alkali leaching, obtains alkali by solid-liquor separation after the completion of leaching
Immersion liquid and alkali phase analysis；
(5) acidleach: alkali phase analysis obtained in step (4) is subjected to acidleach with inorganic acid, is divided admittedly after the completion of leaching by liquid
From pickle liquor and acid leaching residue is obtained, ammonia leaching is carried out in acid leaching residue return step (2)；
(6) it sinks selenium: being passed through SO in the pickle liquor obtained in step (5)2, it restores and obtains the impure selenium that purity is greater than 98%,
Filtrate one is obtained after filtering；
(7) it restores, purify: the reduction of filtrate one obtained in step (6) being obtained into thick indium, thick indium further purifies and obtains height
Pure indium and slag containing aluminium, tin；
(8) it cleans: alkali immersion liquid obtained in step (4) is cleaned to obtain containing molybdenum, the slag of tin and filtrate two；
(9) it is electrolysed, purifies: the electrolysis of filtrate two obtained in step (8) being obtained into thick gallium, thick gallium purifies to obtain high purity gallium.
In order to more clearly from show technical solution provided by the present invention and generated technical effect, below with tool
The method provided by the present invention that valuable metal is recycled from CIGS refuse battery chip is described in detail in body embodiment.
Embodiment 1
As shown in Figure 1, the implementation steps of the embodiment include: that 50g CIGS refuse battery chip is taken to carry out substrate desquamation, use
The ammonia and ammonium salt mixture solution of certain mass concentration are that leaching agent carries out ammonia leaching to the valuable metal layer after removing, and leaching agent is dense
Degree is with NH3Meter is 200g/L, and solid-to-liquid ratio is 1:5g/mL before leaching, and extraction temperature is 30 DEG C, extraction time 5h, leaches and completes
Ammonia leaching solution and ammonia leaching residue are obtained by solid-liquor separation afterwards；It can get cathode copper after ammonia leaching solution extraction, electrodeposition；Ammonia leaching residue quality
The NaOH solution that concentration is 80% is that alkali soaks leaching agent in atmospheric conditions, and the extraction temperature of the dipped journey of alkali is 40 DEG C, when leaching
Between be 4.5h, leach before solid-to-liquid ratio be 1:10g/mL, leaching alkali immersion liquid and alkali phase analysis are obtained by solid-liquor separation after rolling.After alkali leaching
Obtained alkali phase analysis is that leaching agent carries out acidleach with the concentrated sulfuric acid, and the extraction temperature of acidleach process is 80 DEG C, extraction time 5h, leaching
Preceding solid-to-liquid ratio is 1:1g/mL out, and leaching obtains pickle liquor and acid leaching residue by solid-liquor separation after rolling, and acid leaching residue returns to ammonia leaching；It is past
SO is passed through in pickle liquor2, intake SO2Se the mass ratio of the material 1.5mol/mol in the amount and raw material of substance, can restore to obtain pure
Degree is greater than 98% impure selenium, and filtrate is obtained after filtering；Fe powder is added into filtrate can restore to obtain thick indium, and thick indium is molten by vacuum again
The high purity indium that purity is greater than 99.9% can be obtained in the purification of refining method；Alkali immersion liquid is obtained by removal of impurities containing molybdenum, the slag of tin and filtrate；Filtrate
Electrolysis obtains thick gallium, then area smelting refinement obtains high purity gallium.
Embodiment 2
The implementation steps of the embodiment include: that 100g CIGS refuse battery chip is taken to carry out substrate desquamation, dense with certain mass
Spending the solution containing ammonia is that leaching agent carries out ammonia leaching to the valuable metal layer after removing, and leaching agent concentration is with NH3Meter is 350g/L,
Solid-to-liquid ratio is 1:10g/mL before leaching, and extraction temperature is 60 DEG C, and extraction time 3h is obtained after the completion of leaching by solid-liquor separation
Ammonia leaching solution and ammonia leaching residue；It can get cathode copper after ammonia leaching solution extraction, electrodeposition；The KOH that ammonia leaching residue mass concentration is 60% is molten
Liquid is that alkali soaks leaching agent under an increased pressure, and the extraction temperature of the dipped journey of alkali is 30 DEG C, extraction time 4.5h, solid-liquid before leaching
Than for 1:5g/mL, leaching obtains alkali immersion liquid and alkali phase analysis by solid-liquor separation after rolling.The alkali phase analysis obtained after alkali leaching is used certain dense
Spending hydrochloric acid is that leaching agent carries out acidleach, and the extraction temperature of acidleach process is 30 DEG C, extraction time 0.5h, and solid-to-liquid ratio is before leaching
1:5g/mL, leaching obtain pickle liquor and acid leaching residue by solid-liquor separation after rolling, and acid leaching residue returns to ammonia leaching；It is passed through into pickle liquor
SO2, intake SO2Se the mass ratio of the material 1.0mol/mol in the amount and raw material of substance can restore to obtain purity greater than 98%
Impure selenium obtains filtrate after filtering；Hydrazine hydrate solution is added into filtrate can restore to obtain thick indium, and thick indium is mentioned by zone melting method again
The pure high purity indium that purity can be obtained and be greater than 99.9%；Alkali immersion liquid is obtained by removal of impurities containing molybdenum, the slag of tin and filtrate；Filtrate is electrolysed
It purifies to obtain high purity gallium to thick gallium, then low-temperature electrolytic.
Embodiment 3
The implementation steps of the embodiment include: that 50g CIGS refuse battery chip is taken to carry out substrate desquamation, dense with certain mass
The ammonia and ammonium salt mixture solution of degree are that leaching agent carries out ammonia leaching to the valuable metal layer after removing, and leaching agent concentration is with NH3Meter,
For 50g/L, solid-to-liquid ratio is 1:10g/mL before leaching, and extraction temperature is 60 DEG C, extraction time 3h, solid by liquid after the completion of leaching
Isolated ammonia leaching solution and ammonia leaching residue；It can get cathode copper after ammonia leaching solution extraction, electrodeposition；Ammonia leaching residue mass concentration is 50%
NaOH solution be that alkali soaks leaching agent in atmospheric conditions, the extraction temperature of the dipped journey of alkali is 90 DEG C, extraction time 3h, is leached
Preceding solid-to-liquid ratio is 1:5g/mL, and leaching obtains alkali immersion liquid and alkali phase analysis by solid-liquor separation after rolling.The alkali phase analysis obtained after alkali leaching is used
Certain density nitric acid is that leaching agent carries out acidleach, and the extraction temperature of acidleach process is 150 DEG C, extraction time 4h, before leaching
Solid-to-liquid ratio is 1:1g/mL, and leaching obtains pickle liquor and acid leaching residue by solid-liquor separation after rolling, and acid leaching residue returns to ammonia leaching；Toward acidleach
SO is passed through in liquid2, intake SO2Se the mass ratio of the material 1.2mol/mol in the amount and raw material of substance can restore to obtain purity big
In 98% impure selenium, filtrate is obtained after filtering；Formalin is added into filtrate can restore to obtain thick indium, and thick indium passes through segregation again and mentions
The high purity indium that purity is greater than 99.9% can be obtained in pure method purification；Alkali immersion liquid is obtained by removal of impurities containing molybdenum, the slag of tin and filtrate；Filtrate
Electrolysis obtains thick gallium, then area smelting refinement obtains high purity gallium.
Embodiment 4
The implementation steps of the embodiment include: that 100g CIGS refuse battery chip is taken to carry out substrate desquamation, dense with certain mass
Degree is that leaching agent carries out ammonia leaching to the valuable metal layer after removing containing ammonia solution, and solid-to-liquid ratio is 1:10g/mL before leaching, and is leached
Temperature is 60 DEG C, extraction time 3h, obtains ammonia leaching solution and ammonia leaching residue by solid-liquor separation after the completion of leaching；Ammonia leaching solution extraction,
It can get cathode copper after electrodeposition；Ammonia leaching residue is leaching agent alkali under an increased pressure with the NaOH solution that mass concentration is 50%
Leaching, the extraction temperature of the dipped journey of alkali are 150 DEG C, extraction time 3h, and solid-to-liquid ratio is 1:5g/mL before leaching, and leaching passes through after rolling
Solid-liquor separation obtains alkali immersion liquid and alkali phase analysis.The alkali phase analysis obtained after alkali leaching is that leaching agent carries out acidleach, acidleach with the concentrated sulfuric acid
The extraction temperature of journey is 80 DEG C, extraction time 4h, and solid-to-liquid ratio is 1:1g/mL before leaching, and leaching is obtained by solid-liquor separation after rolling
To pickle liquor and acid leaching residue, acid leaching residue returns to ammonia leaching；SO is passed through into pickle liquor2, intake SO2In the amount and raw material of substance
Se the mass ratio of the material 1.3mol/mol can restore to obtain the impure selenium that purity is greater than 98%, filtrate is obtained after filtering；It is added into filtrate
Fe powder can restore to obtain thick indium, and thick indium passes through the purification of Solid phase electrolysis method again can be obtained the high purity indium that purity is greater than 99.9%；Alkali leaching
Liquid is obtained by removal of impurities containing molybdenum, the slag of tin and filtrate；Filtrate is electrolysed to obtain thick gallium, then low-temperature electrolytic purifies to obtain high purity gallium.
Embodiment 5
The implementation steps of the embodiment include: that 50g CIGS refuse battery chip is taken to carry out substrate desquamation, dense with certain mass
The ammonia and ammonium salt mixture solution of degree are that leaching agent carries out ammonia leaching to the valuable metal layer after removing, and solid-to-liquid ratio is 1 before leaching:
6g/mL, extraction temperature are 90 DEG C, extraction time 3h, obtain ammonia leaching solution and ammonia leaching residue by solid-liquor separation after the completion of leaching；Ammonia
It can get cathode copper after immersion liquid extraction, electrodeposition；Ammonia leaching residue is leaching agent in normal pressure item with the KOH solution that mass concentration is 30%
Alkali soaks under part, and the extraction temperature of the dipped journey of alkali is 60 DEG C, extraction time 4h, and solid-to-liquid ratio is 1:1g/mL before leaching, and leaching is after rolling
Alkali immersion liquid and alkali phase analysis are obtained by solid-liquor separation.The alkali phase analysis obtained after alkali leaching is leaching with the concentrated nitric acid of certain mass concentration
Agent carries out acidleach, and the extraction temperature of acidleach process is 90 DEG C, extraction time 3h, and solid-to-liquid ratio is 1:10g/mL before leaching, and leaches
Pickle liquor and acid leaching residue are obtained by solid-liquor separation after complete, acid leaching residue returns to ammonia leaching；SO is passed through into pickle liquor2, intake is
Se the mass ratio of the material 1.5mol/mol in the amount and raw material of SO2 substance can restore to obtain the impure selenium that purity is greater than 98%, after filtering
Obtain filtrate；Hydrazine hydrate solution is added into filtrate can restore to obtain thick indium, and thick indium passes through the purification of hydrogen plasma arc melting method again can
Obtain the high purity indium that purity is greater than 99.9%；Alkali immersion liquid is obtained by removal of impurities containing molybdenum, the slag of tin and filtrate；Filtrate is electrolysed to obtain thick
Gallium, then area smelting refinement obtain high purity gallium.
The above is a preferred embodiment of the present invention, it is noted that for those skilled in the art
For, without departing from the principles of the present invention, several improvements and modifications can also be made, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (5)
1. a kind of method for recycling valuable metal from the useless chip of copper indium gallium selenium solar hull cell, it is characterised in that: including
Steps are as follows:
(1) stainless steel/glass substrate removing: the useless chip of copper indium gallium selenium solar hull cell is subjected to substrate desquamation, is had
Valence metal layer；
(2) ammonia soaks: the valuable metal layer that step (1) is obtained carries out ammonia leaching, obtains ammonia leaching by solid-liquor separation after the completion of leaching
Liquid and ammonia leaching residue；
(3) extraction, electrodeposition: cathode copper will be obtained after the extraction of ammonia leaching solution obtained in step (2), electrodeposition；
(4) alkali soaks: ammonia leaching residue obtained in step (2) being carried out alkali leaching, obtains alkali immersion liquid by solid-liquor separation after the completion of leaching
With alkali phase analysis；
(5) acidleach: alkali phase analysis obtained in step (4) is subjected to acidleach with inorganic acid, is obtained after the completion of leaching by solid-liquor separation
To pickle liquor and acid leaching residue, acid leaching residue return step (2) is middle to carry out ammonia leaching；
(6) it sinks selenium: being passed through SO in the pickle liquor obtained in step (5)2, reduction obtains the impure selenium that purity is greater than 98%, after filtering
Obtain filtrate one；
(7) it restores, purify: the reduction of filtrate one obtained in step (6) being obtained into thick indium, thick indium further purifies and obtains high purity indium
With the slag containing aluminium, tin；
(8) it cleans: alkali immersion liquid obtained in step (4) is cleaned to obtain containing molybdenum, the slag of tin and filtrate two；
(9) it is electrolysed, purifies: the electrolysis of filtrate two obtained in step (8) being obtained into thick gallium, thick gallium purifies to obtain high purity gallium；
The copper indium gallium selenium solar hull cell handled in the step (1) give up chip containing Cu 15~25%, In 15~25%,
Ga 15~25%, Se 40~60%；
Acidleach is inorganic acid with acid in the step (5), and acidleach temperature is 30~150 DEG C, and extraction time is 0.5~5h, is leached
Preceding solid-to-liquid ratio is 1:1~1:10g/mL；
SO in the step (6)2Intake are as follows: SO2Se the mass ratio of the material is 1.0~1.5 in the amount and raw material of substance.
2. the method according to claim 1 that valuable metal is recycled from the useless chip of copper indium gallium selenium solar hull cell,
It is characterized by: in the step (2) ammonia soak leaching agent used be containing ammonia or ammonia and ammonium salt mixed solution, leaching agent concentration with
NH3Meter is 50~350g/L, and extraction temperature is 30~90 DEG C, and extraction time is 0.5~5h, and solid-to-liquid ratio is 1:1~1 before leaching:
10g/mL。
3. the method according to claim 1 that valuable metal is recycled from the useless chip of copper indium gallium selenium solar hull cell,
It is characterized by: alkali leaching is 30%~80% with mass concentration in the step (4) NaOH or KOH are leaching agent, alkali leaching temperature
Degree is 30~150 DEG C, and extraction time is 0.5~5h, and solid-to-liquid ratio is 1:1~1:10g/mL before leaching.
4. the method according to claim 1 that valuable metal is recycled from the useless chip of copper indium gallium selenium solar hull cell,
It is characterized by: restoring reducing agent used in the step (7) is that iron powder, hydrazine hydrate, formaldehyde and both of which or three appoint
Meaning scalemic thereof；The method inclusion region smelting process of purifying crude indium, vacuum melting method, vacuum distillation method, Solid phase electrolysis method, partially
Analyse method of purification, hydrogen plasma arc melting method.
5. the method according to claim 1 that valuable metal is recycled from the useless chip of copper indium gallium selenium solar hull cell,
It is characterized by: the method for purification of thick gallium includes low-temperature electrolytic purification, area smelting refinement or both combination in the step (9)
Purification.
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| CN110117724B (en) * | 2019-04-04 | 2021-04-06 | 湖南工程学院 | Method for recovering indium in indium-containing slag by carbothermic reduction |
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| CN104017995A (en) * | 2014-06-24 | 2014-09-03 | 株洲冶炼集团股份有限公司 | Method for recycling copper, indium, gallium and selenium from indium gallium selenium wastes containing copper |
| CN104032136A (en) * | 2014-06-24 | 2014-09-10 | 株洲冶炼集团股份有限公司 | Method for recycling copper, indium, gallium and selenium from waste material |
| US8834818B2 (en) * | 2010-11-26 | 2014-09-16 | Molycorp Minerals Canada Ulc | Treatment of indium gallium alloys and recovery of indium and gallium |
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| CN1718786A (en) * | 2005-07-25 | 2006-01-11 | 方建军 | Normal temperature normal pressure ammonia infusion-extraction-electrodeposition-slag infusion flotation of copper oxide green ore |
| US8834818B2 (en) * | 2010-11-26 | 2014-09-16 | Molycorp Minerals Canada Ulc | Treatment of indium gallium alloys and recovery of indium and gallium |
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