CN109802005A - The recovery method of thin-film solar cells chip - Google Patents
The recovery method of thin-film solar cells chip Download PDFInfo
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- CN109802005A CN109802005A CN201811512350.0A CN201811512350A CN109802005A CN 109802005 A CN109802005 A CN 109802005A CN 201811512350 A CN201811512350 A CN 201811512350A CN 109802005 A CN109802005 A CN 109802005A
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Abstract
The present invention relates to technical field of solar batteries, in particular to a kind of recovery method of thin-film solar cells chip.Itself the following steps are included: by chip impregnate agent solution in immersion treatment, make active material layer from the substrate of chip be detached from；Mixed solution containing active material clast after elution is separated by solid-liquid separation to obtain filter residue, is dissolved being put into leaching agent after filter residue pickling, leachate is obtained, the leaching agent is the mixed solution of dioxysulfate water；The multiple element in leachate is isolated by one of resins exchange, extraction and chemical reaction or various ways.In the case where not broken ring steel-cald bottom, separate active material layer with steel-cald bottom, and complete the recycling of each ingredient in subsequent wet process.Stainless steel substrates can not be destroyed and completely be recycled.More useless chip, volume substantially reduce the active layer filter residue to fall off, reduce the transportation cost and equipment cost of centralized recovery active material layer rare precious metal.
Description
Technical field
The present invention relates to technical field of solar batteries, in particular to a kind of returning for thin-film solar cells chip
Receiving method.
Background technique
With the rapid development of solar battery industry, the total output of solar components also fast lifting, however, with too
The increase of positive energy battery service life is inferred, in the near future according to the service life of solar photovoltaic assembly, it will is had big
The photovoltaic module of amount is scrapped, and in the production process of solar components, also has defective products appearance.Therefore, solar components
The problem of recycling, has been put on agenda.The metals such as indium, gallium, cadmium, titanium would generally be used in thin film solar component, it is expensive,
Some such as unreasonable recycling, then can bring very big pollution after component is scrapped to environment.However, containing on thin film solar chip
The active material layer of MULTILAYER COMPOSITE, substrate are usually stainless steel base, and in the wet method leaching process in recycling, being easy will be stainless
Iron and active material layer in steel are immersed in solution system together, cause larger difficulty, mesh for the separation of subsequent metallic element
Before there is no preferable method to be separately separated out active material layer, without damaging stainless steel base.In addition, active material layer leaches
Into after solution, containing different kinds of ions such as copper, indium, gallium, selenium, cadmium, zinc, molybdenum, iron, ingredient is complex, and there is presently no more
Reasonable manner carries out separating-purifying.
For at present, there are mainly three types of the active material separation methods of thin-film solar cells chip: first is that directly acid is molten
Useless chip is directly thrown into the system of inorganic acid or inorganic acid oxidizer and leaches by method, but be easy to will be stainless for this method
Ferro element in steel dissolves out together.Second is that high-temperature calcination, but high-temperature calcination energy consumption is high, and fluorine-containing, selenium in photovoltaic fin
Equal elements, can generate toxic gas, seriously pollute environment after burning.Third is that using the method for subzero treatment, but subzero treatment needs
Want liquid nitrogen, at high cost and be not easy to realize, the measures demoulding such as the photovoltaic fin after deep cooling also needs manually to tap is not suitable for industrialization.
Therefore, the active material layer recycling of the useless chip of thin-film solar cells is a problem urgently to be resolved at present.
Summary of the invention
In order to solve the above-mentioned technical problem or it at least is partially solved above-mentioned technical problem, this application provides a kind of thin
The recovery method of film solar cell chip.
The embodiment of the present invention is achieved in that
A kind of recovery method of thin-film solar cells chip comprising following steps:
Elution: by thin-film solar cells chip in soaking agent immersion treatment, make active material layer from thin film solar
The substrate of battery chip is detached from, and the soaking agent is alkaline solution；
It leaches: the mixed solution containing active material clast after elution being separated by solid-liquid separation to obtain filter residue, by the filter
It is put into leaching agent and is dissolved after slag pickling, obtain leachate, the leaching agent is the mixed solution of acid and hydrogen peroxide；
Element sepatation: the multiple element in leachate is isolated by way of wet separation.
Further, the soaking agent includes at least one of sodium hydroxide and potassium hydroxide.
Further, the soaking agent further includes one of sodium hypochlorite, sodium carbonate, potassium carbonate and postassium hypochlorite or several
Kind.
Further, in elution step, the soaking agent is the sodium hydroxide solution of concentration 1% to 5%；Soaking temperature
It is 10 DEG C to 80 DEG C, elution time 0.1h-0.5h.
Further, described to impregnate the sodium hydroxide solution that agent solution is concentration 30% to 50%, by thin film solar electricity
Chamber chip takes out after impregnating 10S-60S in impregnating agent solution, toasts 0.1-5h at 100-800 DEG C.
Further, 0.1-5h will be eluted in water after the baking of thin-film solar cells chip.
Further, it will be put into the sodium hydroxide solution of concentration 1% to 5% and wash after the baking of thin-film solar cells chip
De- 0.1-5h.
It further, during elution further include strengthening to elute by ultrasonic device.
Further, in leaching step, the leaching agent is the mixed solution of sulfuric acid and hydrogen peroxide, in Leaching Systems
In, the mass fraction of sulfuric acid is 10%, and the mass fraction of hydrogen peroxide is 2%；Extraction time is 1h, and extraction temperature is 95 DEG C.
Further, the thin-film solar cells chip is copper-indium-galliun-selenium film solar cell chip, in element point
From including: the molybdenum element separated using basic resin or amine extractant in the leachate in step.
Further, in element sepatation step further include: after isolating molybdenum element, repeatedly added into the leachate
Sulfide is successively settled out copper sulfide, cadmium sulfide, selenium simple substance, sulphur simple substance, indium sulfide and vulcanization gallium.
The beneficial effect of the embodiment of the present invention is:
The recovery method of thin-film solar cells chip of the present invention makes active material in the case where not broken ring steel-cald bottom
The bed of material is separated with steel-cald bottom, and the recycling of each ingredient is completed in subsequent wet process.Stainless steel substrates can not be destroyed
To complete recycling.More useless chip, volume substantially reduce the active layer filter residue to fall off, and it is dilute to reduce centralized recovery active material layer
The transportation cost and equipment cost of noble metal.
Specific embodiment
It, below will be to the skill in the embodiment of the present application in order to make those skilled in the art more fully understand application scheme
Art scheme is clearly and completely described, it is clear that and described embodiment is only the embodiment of the application a part, without
It is whole embodiments.Based on the embodiment in the application, those of ordinary skill in the art are not before making creative work
Every other embodiment obtained is put, shall fall within the protection scope of the present application.
It should be noted that the description and claims of this application term " includes " and " having " and their times
What is deformed, it is intended that cover it is non-exclusive include, for example, containing the process, method of a series of steps or units need not limit
In step or unit those of is clearly listed, but may include be not clearly listed or it is solid for these process, methods
The other step or units having.For those of ordinary skills, it can understand that above-mentioned term exists as the case may be
Concrete meaning in the application.
Embodiment 1
A kind of recovery method of thin-film solar cells chip comprising following steps:
(1) chip that gives up prepares: preparing 10kg departing from the thin-film solar cells chip of resin film.
(2) it elutes: thin-film solar cells chip being put into 1% sodium hydroxide solution and carries out heating immersion, solution
Volume is 50L, maintains the temperature at 10 DEG C, while strengthening elution using ultrasonic device, continues 0.1h and stop, at this point, active material
Layer is detached from from substrate, is entered with debris form and is formed mixed liquor in solution, and substrate (stainless steel base) is not destroyed, and uses strainer
Pull substrate out.
In this step, active material layer is generally included by metallic elements such as copper, indium, galliums, and alkaline solution soaking agent has
Stronger dissociation can dissociate less amount of Cu in active material layer2+、In3+And Ga3+, above-mentioned ion is in alkaline solution
It can occur to react as follows:
Cu2++2OH?→Cu(OH)2
In3++3OH?→In(OH)3
Ga3++3OH?→Ga(OH)3
Under the action of alkaline solution, the dissociation site of active material layer usually occurs on the interface connecting with substrate,
It can contribute to the separation of active material layer and substrate, there are also a small amount of solution defections to occur on the surface of active material layer, so that
The structural stability of active material layer reduces, and it is clast that fragmentation is easy under interference.
(3) it leaches: the mixed solution containing active material clast after elution being separated by solid-liquid separation to obtain filter residue, solid-liquid point
Lye from after retains recycling, for impregnating the useless chip of elution next group thin-film solar cells.Filter residue is passed through into sulfuric acid
After quick wash, it is put into the leaching agent of the mixed solution composition of sulfuric acid and hydrogen peroxide and is leached, control liquid-solid ratio is 2:1,
Wherein the mass fraction of sulfuric acid is 10%, and the mass fraction of hydrogen peroxide is 2%；Extraction time is 1h, and extraction temperature is 95 DEG C, this
When Leaching Systems mixed liquor become it is limpid, active material layer clast is all dissolved in leachate.
In the step, the conversion process of each ingredient is as follows:
2CuInxGa(1-x)Se2+6H++9H2O2→2Cu2++2xIn3++ 2 (1-x) Ga3++2SeO3 2-+12H2O
ZnO+2H+→Zn2++H2O
CdS+8H2O2→Cd2++SO4 2-+8H2O+2O2
Mo+3H2O2→MoO4 2-+2H2O+2H+
(4) element sepatation: the multiple element in leachate is isolated by way of wet separation, and is carried out at purification
Reason.
Embodiment 2
A kind of recovery method of copper-indium-galliun-selenium film solar cell chip comprising following steps:
Useless chip prepares: preparing 10kg departing from the copper-indium-galliun-selenium film solar cell chip of resin film.
Elution: copper-indium-galliun-selenium film solar cell chip being put into 5% sodium hydroxide solution and carries out heating immersion,
Liquor capacity is 50L, maintains the temperature at 80 DEG C, while strengthening elution using ultrasonic device, continues 5h and stop, at this point, active material
The bed of material is detached from from substrate, is entered with debris form and is formed mixed liquor in solution, and substrate (stainless steel base) is not destroyed, with leakage
Spoon pulls substrate out.
Material conversion process in elution process is referring to embodiment 1.
It leaches: the mixed solution containing active material clast after elution is separated by solid-liquid separation to obtain filter residue, be separated by solid-liquid separation
Lye afterwards retains recycling, for impregnating the useless chip of elution next group thin-film solar cells.Filter residue is fast by hydrochloric acid
After speed washing, it is put into the leaching agent of the mixed solution composition of hydrochloric acid and hydrogen peroxide and is leached, control liquid-solid ratio is 2:1,
The mass fraction of middle hydrochloric acid is 10%, and the mass fraction of hydrogen peroxide is 2%；Extraction time is 1h, and extraction temperature is 95 DEG C, at this time
The mixed liquor of Leaching Systems becomes limpid, and active material layer clast is all dissolved in leachate.
Material conversion process in leaching process is referring to embodiment 1.
Element sepatation: it is separated off in leachate first with D314 macroreticular weakly base acrylic acid type anion exchange resin
Molybdenum element, molybdenum element is more mature and conveniently using the means that ion exchange or extractant are separated, in order to avoid for rear
Continue the interference of other elements processing, preferentially separates molybdenum element in the present embodiment, preferentially isolate molybdenum in the application other embodiments
The principle of element is identical as the present embodiment, repeats no more；Then 0.95 times of copper ion theoretical amount of vulcanization is added into leachate
Sodium is settled out copper sulfide, reaction equation are as follows:
Cu2++S2-→CuS
Then it is filtered, copper sulfide filter residue is retained；1.05 times of cadmium ion theoretical amount of sulphur is continuously added into liquid phase again
Change sodium, be settled out cadmium sulfide, reaction equation are as follows:
Cd2++S2-→CdS
Then it is filtered, cadmium sulfide filter residue is disposed as dangerous waste；The theory of selenium, indium and gallium summation is continuously added to liquid phase
The vulcanized sodium of 1.2 times of amount restores and is settled out selenium simple substance, sulphur simple substance, indium sulfide, the mixing slag for vulcanizing gallium, reaction equation are as follows:
6H++SeO3 2-+2S2-→Se+2S+3H2O
In3++S2-→In2S3
Ga3++S2-→Ga2S3
Then it is filtered, filtered liquid phase, which can return, is used as leaching agent in leaching step, or can supplement suitable
For in next group leaching step after the hydrochloric acid and hydrogen peroxide of amount.The selenium of solid phase, sulphur, indium sulfide, the mixing slag for vulcanizing gallium are with before
State isolated vulcanization copper ashes to merge, carry out sulfating roasting and water logging to slag is merged, it is subsequent be separately recovered elemental selenium, indium,
Gallium, copper Related product.
Embodiment 3
A kind of recovery method of copper-indium-galliun-selenium film solar cell chip comprising following steps:
Useless chip prepares: preparing 10kg departing from the copper-indium-galliun-selenium film solar cell chip of resin film.
Elution: copper-indium-galliun-selenium film solar cell chip being put into 3% sodium hydroxide solution and carries out heating immersion,
Liquor capacity is 50L, maintains the temperature at 60 DEG C, while strengthening elution using ultrasonic device, continues 1h and stop, at this point, active material
The bed of material is detached from from substrate, is entered with debris form and is formed mixed liquor in solution, and substrate (stainless steel base) is not destroyed, with leakage
Spoon pulls substrate out.
Material conversion process in elution process is referring to embodiment 1.
It leaches: the mixed solution containing active material clast after elution is separated by solid-liquid separation to obtain filter residue, be separated by solid-liquid separation
Lye afterwards retains recycling, for impregnating the useless chip of elution next group thin-film solar cells.Filter residue is fast by nitric acid
After speed washing, it is put into the leaching agent of the mixed solution composition of nitric acid and hydrogen peroxide and is leached, control liquid-solid ratio is 2:1,
The mass fraction of middle nitric acid is 10%, and the mass fraction of hydrogen peroxide is 2%；Extraction time is 1h, and extraction temperature is 95 DEG C, at this time
The mixed liquor of Leaching Systems becomes limpid, and active material layer clast is all dissolved in leachate.
Material conversion process in leaching process is referring to embodiment 1.
Element sepatation: the molybdenum element in leachate is removed with methyl tricapryl ammonium chloride extraction and separation, then to leachate
The middle potassium sulfide for being added 0.95 times of copper ion theoretical amount, is settled out copper sulfide, reaction equation are as follows:
Cu2++S2-→CuS
Then it is filtered, copper sulfide filter residue is retained；The P204 extractant for being again 10% with concentration, the case where pH is 0
Lower extraction of indium is stripped to obtain liquid after rich indium extracts with the hydrochloric acid solution of 2mol/L, and zincification powder substitution obtains the thick indium of simple substance, reactional equation
Formula are as follows:
2In3++3Zn→3Zn2++2In
1.05 times of cadmium ion theoretical amount of potassium sulfide is added in leachate after extraction of indium, is settled out cadmium sulfide, reactional equation
Formula are as follows:
Cd2++S2-→CdS
Then it is filtered, cadmium sulfide filter residue is disposed as dangerous waste；The P204 that concentration is 10% is added to leachate to extract
Agent extracts gallium in the case where pH is 1.1, liquid after being stripped to obtain rich gallium extraction with the hydrochloric acid solution of 2mol/L, basified after extraction to make
After liquid, Metallic Gallium is obtained through electrolysis；The potassium sulfite of remaining 1.2 times of amount of selenium element theory of reduction is added to leachate, at 50 DEG C
At a temperature of, precipitate reduction selenium, reaction equation are as follows:
2H++2SO3 2-+SeO3 2-→Se+2SO4 2-+H2O
Selenium simple substance is obtained by filtration.Liquid phase can be used for the leaching step of next group after supplementing suitable nitric acid and hydrogen peroxide
In.
Embodiment 4
A kind of recovery method of copper-indium-galliun-selenium film solar cell chip comprising following steps:
Useless chip prepares: preparing 10kg departing from the copper-indium-galliun-selenium film solar cell chip of resin film.
Elution: copper-indium-galliun-selenium film solar cell chip being put into 30% sodium hydroxide solution and is impregnated, molten
Liquid product is 50L, is pulled out after continuing 10s.It is put into oven for baking, 100 DEG C of temperature range, is taken out after continuing 0.1h.Then it puts
Enter and eluted in 50L water, while strengthening elution using ultrasonic device, continues 0.1h and stop.At this point, active material layer from substrate (no
Rust steel base) it is detached from, entered with debris form and forms mixed liquor in solution, and substrate is not destroyed, and pulls substrate out with strainer.
Material conversion process in elution process is referring to embodiment 1.
It leaches: the mixed solution containing active material clast after elution is separated by solid-liquid separation to obtain filter residue, be separated by solid-liquid separation
Lye afterwards retains recycling, for impregnating the useless chip of elution next group thin-film solar cells.Filter residue is fast by sulfuric acid
After speed washing, it is put into the leaching agent of the mixed solution composition of sulfuric acid and hydrogen peroxide and is leached, control liquid-solid ratio is 2:1,
The mass fraction of middle sulfuric acid is 10%, and the mass fraction of hydrogen peroxide is 2%；Extraction time is 1h, and extraction temperature is 95 DEG C, at this time
The mixed liquor of Leaching Systems becomes limpid, and active material layer clast is all dissolved in leachate.
Material conversion process in leaching process is referring to embodiment 1.
Element sepatation: the molybdenum element being separated off first with D380 macroporous weakly basic anion exchange resin in leachate,
Then 0.95 times of copper ion theoretical amount of vulcanized sodium is added into leachate, is settled out copper sulfide, is filtered, copper sulfide filter residue
It retains；The P204 extractant for being again 30% with concentration, the extraction of indium in the case where pH is 0.4 are anti-with the hydrochloric acid solution of 8mol/L
Extraction obtains liquid after rich indium extraction, and zincification plate replaces to obtain the thick indium of simple substance.Cadmium ion theoretical amount 1.05 is added in leachate after extraction of indium
Vulcanized sodium again, is settled out cadmium sulfide, is filtered, and cadmium sulfide filter residue is disposed as dangerous waste；Concentration, which is added, to leachate is
30% P204 extractant extracts gallium in the case where pH is 2, is stripped to obtain liquid after rich gallium extracts with the hydrochloric acid solution of 8mol/L,
After extraction after basified liquid making, Metallic Gallium is obtained through electrolysis；The sulfurous of remaining 1.2 times of amount of selenium element theory of reduction is added to leachate
Sour sodium, at a temperature of 80 DEG C, selenium simple substance is obtained by filtration in precipitate reduction selenium.Liquid phase can after supplementing suitable sulfuric acid and hydrogen peroxide
In leaching step for next group.
Material conversion process during element sepatation is referring to embodiment 3.
Embodiment 5
A kind of recovery method of copper-indium-galliun-selenium film solar cell chip comprising following steps:
Useless chip prepares: preparing 10kg departing from the copper-indium-galliun-selenium film solar cell chip of resin film.
Elution: copper-indium-galliun-selenium film solar cell chip being put into 50% sodium hydroxide solution and is impregnated, molten
Liquid product is 50L, is pulled out after continuing 60s.It is put into oven for baking, 800 DEG C of temperature range, is taken out after continuing 5h.It is then placed in
It is eluted in the mixed aqueous solution of 50L potassium hydroxide and sodium chloride, wherein the concentration of potassium hydroxide is 5%, and the concentration of sodium chloride is
10%, while strengthening elution using ultrasonic device, continue 5h and stops.At this point, active material layer is de- from substrate (stainless steel base)
From, entered with debris form and forms mixed liquor in solution, and substrate is not destroyed, and pulls substrate out with strainer.
Material conversion process in elution process is referring to embodiment 1.
It leaches: the mixed solution containing active material clast after elution is separated by solid-liquid separation to obtain filter residue, be separated by solid-liquid separation
Lye afterwards retains recycling, for impregnating the useless chip of elution next group thin-film solar cells.Filter residue is fast by sulfuric acid
After speed washing, it is put into the leaching agent of the mixed solution composition of sulfuric acid and hydrogen peroxide and is leached, control liquid-solid ratio is 2:1,
The mass fraction of middle sulfuric acid is 10%, and the mass fraction of hydrogen peroxide is 2%；Extraction time is 1h, and extraction temperature is 95 DEG C, at this time
The mixed liquor of Leaching Systems becomes limpid, and active material layer clast is all dissolved in leachate.
Material conversion process in leaching process is referring to embodiment 1.
Element sepatation: it is separated off the molybdenum element in leachate first with DK type macropore exchanger resin, then to leachate
The middle vulcanized sodium for being added 0.95 times of copper ion theoretical amount, is settled out copper sulfide, is filtered, and copper sulfide filter residue is retained；Again with dense
The P204 extractant that degree is 20%, the extraction of indium in the case where pH is 0.5 are stripped to obtain rich indium extraction with the hydrochloric acid solution of 5mol/L
Liquid afterwards, zincification powder substitution obtain the thick indium of simple substance.1.05 times of cadmium ion theoretical amount of vulcanized sodium is added in leachate after extraction of indium, sinks
Form sediment cadmium sulfide out, is filtered, and cadmium sulfide filter residue is disposed as dangerous waste；The P204 that concentration is 20% is added to leachate to extract
Agent extracts gallium in the case where pH is 1.5, liquid after being stripped to obtain rich gallium extraction with the hydrochloric acid solution of 6mol/L, basified after extraction to make
After liquid, Metallic Gallium is obtained through electrolysis；The sodium sulfite of remaining 1.2 times of amount of selenium element theory of reduction is added to leachate, at 70 DEG C
At a temperature of, selenium simple substance is obtained by filtration in precipitate reduction selenium.Liquid phase can be used for next group after supplementing suitable sulfuric acid and hydrogen peroxide
Leaching step in.
Material conversion process during element sepatation is referring to embodiment 3.
Embodiment 6:
A kind of recovery method of copper-indium-galliun-selenium film solar cell chip comprising following steps:
Useless chip prepares: preparing 10kg departing from the copper-indium-galliun-selenium film solar cell chip of resin film.
Elution: copper-indium-galliun-selenium film solar cell chip being put into 40% sodium hydroxide solution and is impregnated, molten
Liquid product is 50L, is pulled out after continuing 35s.It is put into oven for baking, 500 DEG C of temperature range, is taken out after continuing 3h.It is then placed in
It is eluted in 50L water, while strengthening elution using ultrasonic device, continued 2h and stop.At this point, active material layer is from substrate (stainless steel
Substrate) it is detached from, entered with debris form and forms mixed liquor in solution, and substrate is not destroyed, and pulls substrate out with strainer.
Material conversion process in elution process is referring to embodiment 1.
It leaches: the mixed solution containing active material clast after elution is separated by solid-liquid separation to obtain filter residue, be separated by solid-liquid separation
Lye afterwards retains recycling, for impregnating the useless chip of elution next group thin-film solar cells.Filter residue is fast by sulfuric acid
After speed washing, it is put into the leaching agent of the mixed solution composition of sulfuric acid and hydrogen peroxide and is leached, control liquid-solid ratio is 2:1,
The mass fraction of middle sulfuric acid is 10%, and the mass fraction of hydrogen peroxide is 2%；Extraction time is 1h, and extraction temperature is 95 DEG C, at this time
The mixed liquor of Leaching Systems becomes limpid, and active material layer clast is all dissolved in leachate.
Material conversion process in leaching process is referring to embodiment 1.
Element sepatation: it is separated off in leachate first with D314 macroreticular weakly base acrylic acid type anion exchange resin
Then 0.95 times of copper ion theoretical amount of vulcanized sodium is added into leachate, is settled out copper sulfide, is filtered for molybdenum element, sulphur
Change copper filter residue to retain；The vulcanized sodium for continuously adding 1.05 times of cadmium ion theoretical amount into liquid phase again, is settled out cadmium sulfide, carries out
Filter, cadmium sulfide filter residue are disposed as dangerous waste；1.2 times of theoretical amount of vulcanized sodium of selenium, indium and gallium summation is continuously added to liquid phase, also
Mixing slag that is former and being settled out selenium simple substance, sulphur simple substance, indium sulfide, vulcanization gallium, is filtered, filtered liquid phase can return to leaching
It is used as leaching agent in step out, or suitable acid can be supplemented and be used in next group elution step with after hydrogen peroxide.Solid phase
Selenium, sulphur, indium sulfide, vulcanize gallium mixing slag merges with aforementioned isolated vulcanization copper ashes, to merging slag progress sulphation roasting
Burning and water logging, it is subsequent that elemental selenium, indium, gallium, copper Related product is separately recovered.
Material conversion process during element sepatation is referring to embodiment 2.
Embodiment 7:
A kind of recovery method of copper-indium-galliun-selenium film solar cell chip comprising following steps:
Useless chip prepares: preparing 10kg departing from the copper-indium-galliun-selenium film solar cell chip of resin film.
Elution: copper-indium-galliun-selenium film solar cell chip being put into 45% sodium hydroxide solution and is impregnated, molten
Liquid product is 50L, is pulled out after continuing 20s.It is put into oven for baking, 300 DEG C of temperature range, is taken out after continuing 4h.It is then placed in
It is eluted in 50L water, while strengthening elution using ultrasonic device, continued 2h and stop.At this point, active material layer is from substrate (stainless steel
Substrate) it is detached from, entered with debris form and forms mixed liquor in solution, and substrate is not destroyed, and pulls substrate out with strainer.
Material conversion process in elution process is referring to embodiment 1.
It leaches: the mixed solution containing active material clast after elution is separated by solid-liquid separation to obtain filter residue, be separated by solid-liquid separation
Lye afterwards retains recycling, for impregnating the useless chip of elution next group thin-film solar cells.Filter residue is fast by sulfuric acid
After speed washing, it is put into the leaching agent of the mixed solution composition of sulfuric acid and hydrogen peroxide and is leached, control liquid-solid ratio is 2:1,
The mass fraction of middle sulfuric acid is 10%, and the mass fraction of hydrogen peroxide is 2%；Extraction time is 1h, and extraction temperature is 95 DEG C, at this time
The mixed liquor of Leaching Systems becomes limpid, and active material layer clast is all dissolved in leachate.
Material conversion process in leaching process is referring to embodiment 1.
Element sepatation: the molybdenum element in leachate is removed with Alamine 304 extraction and separation, copper is then added into leachate
The vulcanized sodium that 0.95 times of ionic theory amount, is settled out copper sulfide, is filtered, and copper sulfide filter residue is retained；It is again 15% with concentration
P204 extractant, the extraction of indium in the case where pH is 0.8, liquid after being stripped to obtain rich indium extraction with the hydrochloric acid solution of 4mol/L adds
Zine plate replaces to obtain the thick indium of simple substance.1.05 times of cadmium ion theoretical amount of vulcanized sodium is added in leachate after extraction of indium, is settled out sulphur
Cadmium is filtered, and cadmium sulfide filter residue is disposed as dangerous waste；The P204 extractant that concentration is 15% is added to leachate, in pH
Gallium is extracted in the case where being 0.3, is stripped to obtain liquid after rich gallium extracts with the hydrochloric acid solution of 6.5mol/L, after extraction after basified liquid making,
Metallic Gallium is obtained through electrolysis；The sodium sulfite of remaining 1.2 times of amount of selenium element theory of reduction is added to leachate, in 75 DEG C of temperature
Under, selenium simple substance is obtained by filtration in precipitate reduction selenium.Liquid phase can be used for the elution of next group after supplementing suitable acid and hydrogen peroxide
In step.
Material conversion process during element sepatation is referring to embodiment 3.
Embodiment 8:
A kind of recovery method of active material in copper-indium-galliun-selenium film solar cell chip comprising following steps:
Useless chip prepares: preparing 10kg departing from the copper-indium-galliun-selenium film solar cell chip of resin film.
Elution: copper-indium-galliun-selenium film solar cell chip being put into 45% sodium hydroxide solution and is impregnated, molten
Liquid product is 50L, is pulled out after continuing 20s.It is put into oven for baking, 300 DEG C of temperature range, is taken out after continuing 4h.It is then placed in
It is eluted in the sodium hydroxide solution that 50L concentration is 1%, while strengthening elution using ultrasonic device, continued 2h and stop.At this point, living
Property material layer be detached from from substrate (stainless steel base), entered in solution with debris form and form mixed liquor, and substrate is not destroyed,
Substrate is pulled out with strainer.
Material conversion process in elution process is referring to embodiment 1.
It leaches: the mixed solution containing active material clast after elution is separated by solid-liquid separation to obtain filter residue, be separated by solid-liquid separation
Lye afterwards retains recycling, for impregnating the useless chip of elution next group thin-film solar cells.Filter residue is fast by sulfuric acid
After speed washing, it is put into the leaching agent of the mixed solution composition of sulfuric acid and hydrogen peroxide and is leached, control liquid-solid ratio is 2:1,
The mass fraction of middle sulfuric acid is 10%, and the mass fraction of hydrogen peroxide is 2%；Extraction time is 1h, and extraction temperature is 95 DEG C, at this time
The mixed liquor of Leaching Systems becomes limpid, and active material layer clast is all dissolved in leachate.
Material conversion process in leaching process is referring to embodiment 1.
Element sepatation: the molybdenum element being separated off first with D380 macroporous weakly basic anion exchange resin in leachate,
Then 0.95 times of copper ion theoretical amount of vulcanized sodium is added into leachate, is settled out copper sulfide, is filtered, copper sulfide filter residue
It retains；The P204 extractant for being again 20% with concentration, the extraction of indium in the case where pH is 0.9 are anti-with the hydrochloric acid solution of 4mol/L
Extraction obtains liquid after rich indium extraction, and zincification powder substitution obtains the thick indium of simple substance.Cadmium ion theoretical amount 1.05 is added in leachate after extraction of indium
Vulcanized sodium again, is settled out cadmium sulfide, is filtered, and cadmium sulfide filter residue is disposed as dangerous waste；Concentration, which is added, to leachate is
15% P204 extractant extracts gallium in the case where pH is 1.1, is stripped after obtaining rich gallium extraction with the hydrochloric acid solution of 6.5mol/L
Liquid after extraction after basified liquid making, obtains Metallic Gallium through electrolysis；Remaining 1.2 times of amount of selenium element theory of reduction is added to leachate
Sodium sulfite, at a temperature of 75 DEG C, selenium simple substance is obtained by filtration in precipitate reduction selenium.Liquid phase is after supplementing suitable acid and hydrogen peroxide
It can be used in the elution step of next group.
Material conversion process during element sepatation is referring to embodiment 3.
Embodiment 9
A kind of recovery method of copper-indium-galliun-selenium film solar cell chip comprising following steps:
Useless chip prepares: preparing 10kg departing from the copper-indium-galliun-selenium film solar cell chip of resin film.
Elution: copper-indium-galliun-selenium film solar cell chip is put into the mixed aqueous solution of sodium hydroxide and sodium hypochlorite
Heating immersion is carried out, liquor capacity 50L, naoh concentration 2%, sodium hypochlorite concentration is 1%, maintains the temperature at 65
DEG C, at the same using ultrasonic device strengthen elution, continue 1h stop, at this point, active material layer from substrate be detached from, with debris form into
Enter and forms mixed liquor in solution, and substrate (stainless steel base) is not destroyed, and pulls substrate out with strainer.Wherein sodium hypochlorite has
Alkalescent and strong oxidizing property facilitate the dissociation of active material layer in soaking process, enhance elution effect.
Material conversion process in elution process is referring to embodiment 1.
It leaches: the mixed solution containing active material clast after elution is separated by solid-liquid separation to obtain filter residue, be separated by solid-liquid separation
Lye afterwards retains recycling, for impregnating the useless chip of elution next group thin-film solar cells.Filter residue is fast by sulfuric acid
After speed washing, it is put into the leaching agent of the mixed solution composition of sulfuric acid and hydrogen peroxide and is leached, control liquid-solid ratio is 2:1,
The mass fraction of middle sulfuric acid is 10%, and the mass fraction of hydrogen peroxide is 2%；Extraction time is 1h, and extraction temperature is 95 DEG C, at this time
The mixed liquor of Leaching Systems becomes limpid, and active material layer clast is all dissolved in leachate.
Material conversion process in leaching process is referring to embodiment 1.
Element sepatation: it is separated off the molybdenum element in leachate first with DK type macropore exchanger resin, then to leachate
The middle vulcanized sodium for being added 0.95 times of copper ion theoretical amount, is settled out copper sulfide, is filtered, and copper sulfide filter residue is retained；Again with dense
The P204 extractant that degree is 20%, the extraction of indium in the case where pH is 0.2 are stripped to obtain rich indium extraction with the hydrochloric acid solution of 5mol/L
Liquid afterwards, zincification powder substitution obtain the thick indium of simple substance.1.05 times of cadmium ion theoretical amount of vulcanized sodium is added in leachate after extraction of indium, sinks
Form sediment cadmium sulfide out, is filtered, and cadmium sulfide filter residue is disposed as dangerous waste；The P204 that concentration is 20% is added to leachate to extract
Agent extracts gallium in the case where pH is 1.8, liquid after being stripped to obtain rich gallium extraction with the hydrochloric acid solution of 6mol/L, basified after extraction to make
After liquid, Metallic Gallium is obtained through electrolysis；The sodium sulfite of remaining 1.2 times of amount of selenium element theory of reduction is added to leachate, at 70 DEG C
At a temperature of, selenium simple substance is obtained by filtration in precipitate reduction selenium.Liquid phase can be used for next group after supplementing suitable sulfuric acid and hydrogen peroxide
Leaching step in.
Material conversion process during element sepatation is referring to embodiment 3.
In the specific implementation process, the solute for agent solution being impregnated in elution step can be selected from sodium hydroxide, hydroxide
One or more of potassium, lithium hydroxide, rubidium hydroxide and cesium hydroxide are considered in terms of cost, corrosivity and specific requirements,
Furthermore sodium hypochlorite, ozone, sodium carbonate, potassium carbonate, sulphur can also be added in preferably potassium hydroxide or sodium hydroxide in soaking agent
One or more of sour sodium, potassium sulfate, sodium chloride, potassium chloride, postassium hypochlorite, for strengthening dissociation；In leaching step, leach
Acid in agent can be selected from hydrochloric acid, nitric acid or sulfuric acid；The sulfide being added in element sepatation step is selected from vulcanized sodium or vulcanization
Potassium.The basic resin used in element sepatation step be selected from D314 macroreticular weakly base acrylic acid type anion exchange resin,
D380 macroporous weakly basic anion exchange resin and DK type macropore exchanger resin；Amine extractant is selected from methyl tricapryl ammonium chloride
Or Alamine 304.
It should be noted that the theoretical amount of each ion is according to recycling thin-film solar cells chip in each embodiment of the application
Total amount and every kind of ion plating density be calculated, can theoretically calculate the component of every kind of ion.
It should be noted that the active material layer in the present invention is that thin-film solar cells is honored as a queen by de-, on substrate
Multilayer composite layer, substrate are usually stainless steel base, then contain a large amount of metal or nonmetalloid in active material layer
Can for recycle, recyclable element therein include but is not limited to one of copper, indium, gallium, selenium, cadmium, zinc, sulphur and molybdenum or
A variety of, the occurrence status of above-mentioned each element includes but is not limited to one of copper indium gallium selenide, zinc oxide, simple substance molybdenum and cadmium sulfide
Or it is a variety of.
Section Example is described by the way of progressive or arranged side by side in this specification, the highlights of each of the examples are
With the difference of other embodiments, the same or similar parts in each embodiment may refer to each other.
The above is only a specific embodiment of the invention, make skilled artisans appreciate that or realizing of the invention.It is right
A variety of modifications of these embodiments will be apparent to one skilled in the art, general original as defined herein
Reason can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, it originally will not be limited
It is formed on the embodiments shown herein, and is to fit to consistent with applied principle herein and features of novelty widest
Range.
Claims (10)
1. a kind of recovery method of thin-film solar cells chip, which comprises the following steps:
Elution: by thin-film solar cells chip in soaking agent immersion treatment, make active material layer from thin-film solar cells
The substrate of chip is detached from, and the soaking agent includes at least one of sodium hydroxide and potassium hydroxide；
It leaches: the mixed solution containing active material clast after elution is separated by solid-liquid separation to obtain filter residue, by the filter residue acid
It is put into leaching agent and is dissolved after washing, obtain leachate, the leaching agent is the mixed solution of acid and hydrogen peroxide；
Element sepatation: the multiple element in leachate is isolated by way of wet separation.
2. recovery method according to claim 1, which is characterized in that the soaking agent further include sodium hypochlorite, sodium carbonate,
One or more of potassium carbonate, postassium hypochlorite.
3. recovery method according to claim 1, which is characterized in that in elution step, the soaking agent is concentration 1%
To 5% sodium hydroxide solution；Soaking temperature is 10 DEG C to 80 DEG C, elution time 0.1h-0.5h.
4. recovery method according to claim 1, which is characterized in that in elution step, the immersion agent solution is dense
The sodium hydroxide solution of degree 30% to 50% takes after thin-film solar cells chip is impregnated 10S-60S in impregnating agent solution
Out, 0.1-5h is toasted at 100-800 DEG C, carries out elution processing after baking.
5. recovery method according to claim 4, which is characterized in that in elution step, by thin-film solar cells core
0.1-5h is eluted in water after piece baking.
6. recovery method according to claim 4, which is characterized in that in elution step, by thin-film solar cells core
It is put into the sodium hydroxide solution of concentration 1% to 5% after piece baking and elutes 0.1-5h.
7. recovery method according to claim 1, which is characterized in that during elution further include strong by ultrasonic device
Change elution.
8. recovery method according to claim 1, which is characterized in that in leaching step, the leaching agent be sulfuric acid and
The mixed solution of hydrogen peroxide, in Leaching Systems, the mass fraction of sulfuric acid is 10%, and the mass fraction of hydrogen peroxide is 2%；It leaches
Time is 1h, and extraction temperature is 95 DEG C.
9. recovery method according to claim 1, which is characterized in that the thin-film solar cells chip is copper indium gallium selenide
Thin-film solar cells chip.
10. recovery method according to claim 9, which is characterized in that include: to be set using alkalinity in element sepatation step
Rouge or amine extractant separate the molybdenum element in the leachate, then repeatedly add sulfide into the leachate, successively
It is settled out copper sulfide, cadmium sulfide, selenium simple substance, sulphur simple substance, indium sulfide and vulcanization gallium, by sediment through sulfating roasting and water logging,
Isolate elemental selenium, indium, gallium, copper.
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