CN108441637A - The method that valuable metal is recycled in giving up chip from copper indium gallium selenium solar hull cell - Google Patents
The method that valuable metal is recycled in giving up chip from copper indium gallium selenium solar hull cell Download PDFInfo
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- CN108441637A CN108441637A CN201810220326.3A CN201810220326A CN108441637A CN 108441637 A CN108441637 A CN 108441637A CN 201810220326 A CN201810220326 A CN 201810220326A CN 108441637 A CN108441637 A CN 108441637A
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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 recycling valuable metal in giving up chip from 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 stripping, 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, and alkali immersion liquid and alkali phase analysis are obtained by solid-liquor separation after leaching；Alkali phase analysis carries out acidleach and obtains pickle liquor and acid leaching residue again, and acid leaching residue returns to ammonia leaching；SO is passed through into pickle liquor2Reduction obtains the impure selenium that purity is more 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 realize 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 that valuable metal is recycled in chip.
Background technology
CIGS solar film batteries have the characteristics that low cost, easy for installation, applied widely, and application prospect is very wide
It is wealthy.In producing CIGS cell process, a large amount of CIGS waste materials are will produce, CIGS targets, 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 contain the 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 is needed to be detached and is separately recovered, to facilitate further
Ground recycles, to ensure the sustainable development of CIGS thin film solar cell material.
It is evaporated in Chinese patent CN105886767A by the selenium in CIGS waste materials is first acidizing fired, then again to residue
Three kinds of metals detached, especially to dividing the lye containing gallium generated in indium step and dividing in gallium step solution of the gained containing gallium
Processing is merged, and electrodeposition extraction raffinate may return to and wait for that containing in Gallium solution for electrodeposition carries out cycle electrodeposition, 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 obtain the mixture of indium and zinc oxide, oxidation distillation detaches copper and selenium.But this method flow
Long, two electrolysis detach 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 needs further processing that could obtain rare metal, 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, is carried out CIGS waste materials 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 flow is simple, asking for impurity doping is not considered comprehensively
Topic；Not only contain these four valuable metal elements in CIGS waste materials, 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 detach 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 tod produce with hydrochloric acid and dioxygen water dissolution CIGS waste materials
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 dirt
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 complicated for operation dangerous, production cost is high, environmental pollution is big, it would be highly desirable to it is useless to invent a kind of CIGS that can be solved the above problems
Chip recovery method.
Invention content
It is recycled in giving up chip from copper indium gallium selenium solar hull cell the technical problem to be solved in the present invention is to provide one kind
The method of valuable metal
It is as follows that the method comprising the steps of：
(1) stainless steel/glass substrate stripping：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 by solid-liquor separation after the completion of leaching
Ammonia leaching solution and ammonia leaching residue；
(3) extraction, electrodeposition：In step (2) cathode copper will be obtained after the ammonia leaching solution extraction of gained, electrodeposition；
(4) alkali soaks：The ammonia leaching residue of gained in step (2) is subjected to alkali leaching, alkali is obtained by solid-liquor separation after the completion of leaching
Immersion liquid and alkali phase analysis；
(5) acidleach：The alkali phase analysis of gained in step (4) is subjected to acidleach with inorganic acid, is divided admittedly by liquid after the completion of leaching
From pickle liquor and acid leaching residue is obtained, ammonia leaching is carried out in acid leaching residue return to step (2)；
(6) heavy selenium：Into step (5) SO is passed through in the pickle liquor of gained2, it restores and obtains the impure selenium that purity is more than 98%,
Filtrate one is obtained after filtering；
(7) it restores, purify：The reduction of filtrate one of gained in step (6) is obtained into thick indium, further purification obtains height to thick indium
Pure indium and slag containing aluminium, tin；
(8) it cleans：The 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 of gained in step (8) is 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.
Ammonia leaching leaching agent used is to leach agent concentration containing ammonia or ammonia and ammonium salt mixed solution with NH in step (2)3It 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 before leaching:1~1:10g/mL.
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 before leaching:1~1:10g/
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 be：SO2The amount of Se substances is than 1.0~1.5 in the amount and raw material of substance.
Reduction reducing agent used is that iron powder, hydrazine hydrate, formaldehyde and both of which or three's arbitrary proportion are mixed 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 the two combined purifying in step (9).
The above-mentioned technical proposal of the present invention has the beneficial effect that：
The method achieve the leachings of the efficient selective of copper, indium, gallium, selenium；The problem of having considered metal impurities doping,
Metal target separation is complete；This programme operation is relatively easy, without operational hazards, pollution-free problem.
Description of the drawings
Fig. 1 is the method and process stream that valuable metal is recycled in the useless chip of slave copper indium gallium selenium solar hull cell of the invention
Cheng Tu.
Specific implementation mode
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 recycling valuable metal in giving up chip from 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 stripping：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 by solid-liquor separation after the completion of leaching
Ammonia leaching solution and ammonia leaching residue；
(3) extraction, electrodeposition：In step (2) cathode copper will be obtained after the ammonia leaching solution extraction of gained, electrodeposition；
(4) alkali soaks：The ammonia leaching residue of gained in step (2) is subjected to alkali leaching, alkali is obtained by solid-liquor separation after the completion of leaching
Immersion liquid and alkali phase analysis；
(5) acidleach：The alkali phase analysis of gained in step (4) is subjected to acidleach with inorganic acid, is divided admittedly by liquid after the completion of leaching
From pickle liquor and acid leaching residue is obtained, ammonia leaching is carried out in acid leaching residue return to step (2)；
(6) heavy selenium：Into step (5) SO is passed through in the pickle liquor of gained2, it restores and obtains the impure selenium that purity is more than 98%,
Filtrate one is obtained after filtering；
(7) it restores, purify：The reduction of filtrate one of gained in step (6) is obtained into thick indium, further purification obtains height to thick indium
Pure indium and slag containing aluminium, tin；
(8) it cleans：The 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 of gained in step (8) is 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 technique effect, below with tool
The method that valuable metal is recycled in the refuse battery chip provided by the present invention from CIGS is described in detail in body embodiment.
Embodiment 1
As shown in Figure 1, the implementation steps of the embodiment include：It takes 50g CIGS refuse battery chips to carry out substrate desquamation, uses
The ammonia of certain mass concentration is that leaching agent carries out ammonia leaching to the valuable metal layer after stripping with ammonium salt mixture solution, and leaching agent is dense
Degree is with NH3Meter is 200g/L, and solid-to-liquid ratio is 1 before leaching:5g/mL, extraction temperature are 30 DEG C, extraction time 5h, leach and complete
Ammonia leaching solution and ammonia leaching residue are obtained by solid-liquor separation afterwards；Cathode copper is can get after ammonia leaching solution extraction, electrodeposition；Ammonia leaching residue quality
A concentration of 80% NaOH solution 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 obtain alkali immersion liquid and alkali phase analysis 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
Solid-to-liquid ratio is 1 before going out:1g/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 past
SO is passed through in pickle liquor2, intake SO2The amount ratio 1.5mol/mol of Se substances, can restore to obtain pure in the amount and raw material of substance
Impure selenium of the degree more than 98%, obtains filtrate 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 more 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：100g CIGS refuse battery chips are taken to carry out substrate desquamation, it is dense with certain mass
It is that leaching agent carries out ammonia leaching to the valuable metal layer after stripping to spend the solution containing ammonia, leaches agent concentration with NH3Meter is 350g/L,
Solid-to-liquid ratio is 1 before leaching:10g/mL, extraction temperature are 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；Cathode copper is can get 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 being 1:5g/mL, leaching obtain 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
It is that leaching agent carries out acidleach to spend hydrochloric acid, 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 SO2The amount ratio 1.0mol/mol of Se substances in the amount and raw material of substance can restore to obtain purity more 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 carried by zone melting method again
The pure high purity indium that purity can be obtained and be more 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：50g CIGS refuse battery chips are taken to carry out substrate desquamation, it is dense with certain mass
The ammonia of degree is that leaching agent carries out ammonia leaching to the valuable metal layer after stripping with ammonium salt mixture solution, leaches agent concentration with NH3Meter,
For 50g/L, solid-to-liquid ratio is 1 before leaching:10g/mL, extraction temperature are 60 DEG C, extraction time 3h, solid by liquid after the completion of leaching
Isolated ammonia leaching solution and ammonia leaching residue；Cathode copper is can get 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, leaching obtain 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, leaching obtain 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 SO2The amount ratio 1.2mol/mol of Se substances 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 is carried by segregation again
The high purity indium that purity is more 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：100g CIGS refuse battery chips are taken to carry out substrate desquamation, it is dense with certain mass
Degree is that leaching agent carries out ammonia leaching to the valuable metal layer after stripping containing ammonia solution, and solid-to-liquid ratio is 1 before leaching:10g/mL is leached
Temperature is 60 DEG C, and extraction time 3h obtains ammonia leaching solution and ammonia leaching residue after the completion of leaching by solid-liquor separation；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%
The extraction temperature of leaching, the dipped journey of alkali is 150 DEG C, extraction time 3h, and solid-to-liquid ratio is 1 before leaching:5g/mL, leaching pass 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 before leaching:1g/mL, leaching are 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
The amount ratio 1.3mol/mol of Se substances can restore to obtain the impure selenium that purity is more than 98%, filtrate is obtained after filtering；It is added into filtrate
Fe powder can restore to obtain thick indium, and the high purity indium that purity is more than 99.9% can be obtained by the purification of Solid phase electrolysis method again in thick indium；Alkali soaks
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：50g CIGS refuse battery chips are taken to carry out substrate desquamation, it is dense with certain mass
The ammonia of degree is that leaching agent carries out ammonia leaching to the valuable metal layer after stripping with ammonium salt mixture solution, and solid-to-liquid ratio is 1 before leaching:
6g/mL, extraction temperature are 90 DEG C, and extraction time 3h obtains ammonia leaching solution and ammonia leaching residue after the completion of leaching by solid-liquor separation；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 before leaching:1g/mL, 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 before leaching:10g/mL is leached
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
The amount ratio 1.5mol/mol of Se substances in the amount and raw material of SO2 substances can restore to obtain the impure selenium that purity is more than 98%, after filtering
Obtain filtrate；Hydrazine hydrate solution is added into filtrate can restore to obtain thick indium, and thick indium again can by the purification of hydrogen plasma arc melting method
Obtain the high purity indium that purity is more 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 the 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 (8)
1. a kind of method for recycling valuable metal in useless chip from copper indium gallium selenium solar hull cell, it is characterised in that：Including
Steps are as follows：
(1) stainless steel/glass substrate stripping：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, and ammonia leaching is obtained by solid-liquor separation after the completion of leaching
Liquid and ammonia leaching residue；
(3) extraction, electrodeposition：In step (2) cathode copper will be obtained after the ammonia leaching solution extraction of gained, electrodeposition；
(4) alkali soaks：The ammonia leaching residue of gained in step (2) is subjected to alkali leaching, alkali immersion liquid is obtained by solid-liquor separation after the completion of leaching
With alkali phase analysis；
(5) acidleach：The alkali phase analysis of gained in step (4) is subjected to acidleach with inorganic acid, is obtained by solid-liquor separation after the completion of leaching
To pickle liquor and acid leaching residue, acid leaching residue return to step (2) is middle to carry out ammonia leaching；
(6) heavy selenium：Into step (5) SO is passed through in the pickle liquor of gained2, reduction obtains the impure selenium that purity is more than 98%, after filtering
Obtain filtrate one；
(7) it restores, purify：The reduction of filtrate one of gained in step (6) is obtained into thick indium, further purification obtains high purity indium to thick indium
With the slag containing aluminium, tin；
(8) it cleans：The 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 of gained in step (8) is obtained into thick gallium, thick gallium purifies to obtain high purity gallium.
2. the method that valuable metal is recycled in the useless chip according to claim 1 from copper indium gallium selenium solar hull cell,
It is characterized in that：The copper indium gallium selenium solar hull cell handled in the step (1) gives up chip containing Cu 15~25%, In 15
~25%, Ga 15~25%, Se 40~60%.
3. the method that valuable metal is recycled in the useless chip according to claim 1 from copper indium gallium selenium solar hull cell,
It is characterized in that：In the step (2) ammonia leaching leaching agent used be containing ammonia or ammonia and ammonium salt mixed solution, leach 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 before leaching:1~1:
10g/mL。
4. the method that valuable metal is recycled in the useless chip according to claim 1 from copper indium gallium selenium solar hull cell,
It is characterized in that：The NaOH or KOH that alkali leaching is 30%~80% with mass concentration in the step (4) 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 before leaching:1~1:10g/mL.
5. the method that valuable metal is recycled in the useless chip according to claim 1 from copper indium gallium selenium solar hull cell,
It is characterized in that：Acidleach is inorganic acid with acid in the step (5), and acidleach temperature is 30~150 DEG C, extraction time is 0.5~
5h, solid-to-liquid ratio is 1 before leaching:1~1:10g/mL.
6. the method that valuable metal is recycled in the useless chip according to claim 1 from copper indium gallium selenium solar hull cell,
It is characterized in that：SO in the step (6)2Intake be：SO2In the amount and raw material of substance the amount ratio of Se substances be 1.0~
1.5。
7. the method that valuable metal is recycled in the useless chip according to claim 1 from copper indium gallium selenium solar hull cell,
It is characterized in that：Reduction reducing agent used is that iron powder, hydrazine hydrate, formaldehyde and both of which or three appoint in the step (7)
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.
8. the method that valuable metal is recycled in the useless chip according to claim 1 from copper indium gallium selenium solar hull cell,
It is characterized in that：The method of purification of thick gallium includes low-temperature electrolytic purification, area smelting refinement or the two combination in the step (9)
Purification.
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| CN110117724A (en) * | 2019-04-04 | 2019-08-13 | 湖南工程学院 | A kind of recovery method of indium in carbon thermal reduction slag containing indium |
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