CN108754153A - The recovery method and recovery system of the useless chip of copper indium gallium selenide - Google Patents

The recovery method and recovery system of the useless chip of copper indium gallium selenide Download PDF

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Publication number
CN108754153A
CN108754153A CN201810669830.1A CN201810669830A CN108754153A CN 108754153 A CN108754153 A CN 108754153A CN 201810669830 A CN201810669830 A CN 201810669830A CN 108754153 A CN108754153 A CN 108754153A
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oxidizing roasting
copper
functional layer
indium gallium
gallium selenide
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李红科
李胜春
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Hanergy New Material Technology Co Ltd
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Hanergy New Material Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001—Dry processes
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B15/00—Obtaining copper
    • C22B15/0026—Pyrometallurgy
    • C22B15/0056—Scrap treating
    • 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
    • C22B15/0067—Leaching or slurrying with acids or salts thereof
    • C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
    • 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
    • C22B15/0084—Treating solutions
    • C22B15/0086—Treating solutions by physical methods
    • 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
    • C22B34/00—Obtaining refractory metals
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/34—Obtaining molybdenum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B58/00—Obtaining gallium or indium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid leaching
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/22—Electrolytic production, recovery or refining of metals by electrolysis of solutions of metals not provided for in groups C25C1/02 - C25C1/20
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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Abstract

The present invention relates to the recovery methods and system of a kind of useless chip of copper indium gallium selenide.The recovery method includes：Oxidizing roasting is carried out to copper indium gallium selenide material, so that the film functional layer in the copper indium gallium selenide material is detached with underlay substrate, and obtains the flue gas containing selenium oxide gas；The flue gas containing selenium oxide gas is handled, to obtain elemental selenium；The film functional layer is handled, to respectively obtain elemental copper, simple substance indium and Metallic Gallium.The technical solution can realize the separation of CIGS thin-film functional layer and underlay substrate, in order to reduce the purification difficulty of copper indium gallium selenide and improve its rate of recovery.

Description

The recovery method and recovery system of the useless chip of copper indium gallium selenide
Technical field
The present invention relates to the recycling of the recovery technology field of copper indium gallium selenide material more particularly to a kind of useless chip of copper indium gallium selenide Method and recovery system.
Background technology
It is increasingly aggravated with increasingly serious and traditional energy environmental pollution the influence of current energy crisis, exploitation one Kind, which cleans reproducible novel energy, seems particularly significant.It is inexhaustible, nexhaustible due to solar energy cleanliness without any pollution, because This has become the utilization of solar energy the strategic decision of countries in the world sustainable development source.
Copper-indium-galliun-selenium film solar cell is high with its transformation efficiency, life cycle cost is low, without performance degradation, generated energy The characteristics such as big and have received widespread attention.Specifically, the absorbed layer of copper-indium-galliun-selenium film solar cell be by copper, indium, The yellow copper structure that four kinds of gallium, selenium elements are formed according to optimal proportion, the wave-length coverage for caning absorb spectrum is wide, in addition to non-crystalline silicon Outside the absorbable limit of visible spectrum of solar cell, near infrared spectrum of the wavelength between 700~2000nm can also be covered, Therefore average daily generating dutation is long, and for the crystal silicon solar batteries of same power level, daily gross generation can surpass Go out 20% or so.
Its technology of preparing can substantially be divided into：Polynary steaming technique altogether, sputtering and selenization technique technology, electro-deposition techniques and painting Cloth technology etc..In view of prior art technology is relatively low for the utilization rate of raw material, will produce in its production process a large amount of Copper indium gallium selenide waste material, these waste material include mainly copper indium gallium selenide chamber material and the useless chip of copper indium gallium selenide, wherein except weight is contained Except metallic copper, also contain the rare metals such as indium, gallium, selenium, therefore copper indium gallium selenide waste material is carried out to efficiently separate recycling just The cycling and reutilization of valuable metal can be achieved.
But not only complex process, steps flow chart are long for the recovery method of copper indium gallium selenide waste material at present, but also the rate of recovery compared with It is low, especially flexible copper indium gallium selenide waste material there is also being difficult to detach between film functional layer and stainless steel lining bottom, So that stainless steel lining bottom is dissolved in solution if using wet-treating, to cause impurity element to increase, causes recycling purification more Add difficulty, and the weight at stainless steel lining bottom accounts for 95% or more of useless chip gross weight, for being affected for transportation cost, because This also receives certain limitation in terms of commercial Application.
Invention content
In order to overcome in copper indium gallium selenide material underlay substrate and film functional layer to be difficult to detach and caused by purification of metals it is difficult The problem that degree is big and the rate of recovery is low, the embodiment of the present invention provide a kind of recovery method and recovery system of the useless chip of copper indium gallium selenide. The technical solution is as follows：
According to a first aspect of the embodiments of the present invention, a kind of recovery method of the useless chip of copper indium gallium selenide, including step are provided S1-S3：
Step S1:Pretreatment is processed by shot blasting the give up side of chip of copper indium gallium selenide, makes to be located at lining in film functional layer The molybdenum electrode layer of base plate surface exposes；
Step S2:First segment oxidizing roasting is handled, and at a temperature of 350-500 DEG C, is roasted to the copper indium gallium selenide chip that gives up, Obtain the flue gas containing selenium oxide gas and fired slags；
Step S3:Second segment oxidizing roasting is handled, and at a temperature of 800-1000 DEG C, is roasted again to the fired slags It burns, the film functional layer in the useless chip of the copper and indium gallium is made to be detached with underlay substrate.
In one embodiment, the pretreatment is the molybdenum electricity made in film functional layer positioned at underlay substrate surface Pole layer exposes 3-5cm.
In one embodiment, the second segment oxidizing roasting processing makes the film work(in the useless chip of the copper indium gallium selenide Ergosphere is detached with underlay substrate, including：
During the second segment oxidizing roasting is handled, the underlay substrate table is located at into the film functional layer The molybdenum electrode layer in face is blown pressure-air, so that the molybdenum electrode layer occurs oxidation fusion and accelerates the film functional layer from institute State the stripping on underlay substrate surface.
It is in one embodiment, described that the film functional layer in the useless chip of the copper indium gallium selenide is made to be detached with underlay substrate, Further include：
During being blown pressure-air to the molybdenum electrode layer, by perching knife by the film functional layer from the lining The sur-face peeling of substrate.
In one embodiment, recovery method of the invention further includes step S4：
Step S4:To first segment oxidizing roasting obtain the flue gas containing selenium oxide gas and second segment oxidizing roasting separation Film functional layer is respectively processed, and obtains pure selenium, gallium, indium, copper.
In one embodiment, described to handle the flue gas containing selenium oxide gas, obtaining pure selenium S5 includes：
The selenium oxide gas is absorbed from the flue gas containing selenium oxide gas using spray process, to obtain selenous acid Solution；
Acidic materials are added into the selenous acid solution and reduction treatment is carried out to the selenous acid solution, to obtain State elemental selenium.
In one embodiment, the film functional layer is handled, obtaining fine copper, indium and gallium S6 includes：
Cooling treatment is carried out to the film functional layer, to obtain including at least the target thin film layer of copper, indium, gallium；
The target thin film layer is chemically treated, to respectively obtain fine copper, indium and gallium.
According to a second aspect of the embodiments of the present invention, a kind of recovery system of the useless chip of copper indium gallium selenide is provided, including：Polishing Device, oxidizing roasting device, gas treatment means and separating treatment mechanism；
The burnishing device, for before the chip that gives up to copper indium gallium selenide carries out oxidizing roasting, giving up to the copper indium gallium selenide The side of chip is processed by shot blasting, so as to reveal positioned at the metal conducting layer on the underlay substrate surface in the film functional layer Go out；
The oxidizing roasting device, for copper indium gallium selenide give up chip carry out oxidizing roasting so that copper indium gallium selenide give up chip In film functional layer detached with underlay substrate, and obtain the flue gas containing selenium oxide gas.
The oxidizing roasting device can be roaster, including：
Furnace body, including oxidizing roasting area and the flue that is connected to the oxidizing roasting area, the oxidizing roasting area is used for Oxidizing roasting is carried out to the useless chip of the copper indium gallium selenide, the flue is for being discharged the flue gas containing selenium oxide gas；
Movable hearth furnace bottom is located at the lower section of the furnace body, for driving the copper indium gallium selenide to give up chip across the furnace body Inside；
Stripping off device is located at the end in the oxidizing roasting area, for by the film functional layer from the underlay substrate Sur-face peeling；
Heat power engineering system includes multiple burners positioned at the oxidizing roasting area, for the oxidizing roasting area to be heated to Preset calcination temperature；
The high-pressure oxidation gas piping, for electric positioned at the molybdenum on the underlay substrate surface into the film functional layer Pole layer injection high-pressure oxidation gas, so that the molybdenum electrode layer occurs oxidation fusion and accelerates the film functional layer from the lining The stripping of base plate surface；
The stripping perching knife is used for the film work(during being blown high-pressure oxidation gas to the molybdenum electrode layer Sur-face peeling of the ergosphere from the underlay substrate.
The gas treatment means, for handling the flue gas containing selenium oxide gas, to obtain elemental selenium；
The separating treatment mechanism, for handling the film functional layer, to respectively obtain elemental copper, simple substance indium And Metallic Gallium.
In one embodiment, the furnace body further includes feed zone and cooling discharging area, and positioned at the feed zone with Multiple partition walls between the oxidizing roasting area between the oxidizing roasting area and the cooling discharging area；
Wherein, the cooling discharging area be used for the film functional layer carry out cooling treatment, with obtain include at least copper, The target thin film layer of indium, gallium, the separating treatment mechanism is for handling the target thin film layer, to respectively obtain simple substance Copper, simple substance indium and Metallic Gallium.
In one embodiment, the oxidizing roasting area includes the first oxidizing roasting area and the second oxidizing roasting area, described It is separated also by the partition wall between first oxidizing roasting area and second oxidizing roasting area, and the flue is located at described the One oxidizing roasting area；
First oxidizing roasting area is used to carry out first segment oxidizing roasting processing to the useless chip material of the copper indium gallium selenide, To obtain the intermediate material of the flue gas containing selenium oxide gas and the useless chip of copper indium gallium selenide, and contain selenium oxide by described The flue gas of gas is discharged from the flue；
Second oxidizing roasting area is used to carry out the intermediate material of the useless chip of the copper indium gallium selenide second segment oxidation roasting Burning processing, by the film functional layer from the sur-face peeling of the underlay substrate.
The technical solution that the embodiment of the present invention provides can include the following benefits：
On the one hand the technical solution can make selenium element in high-temperature oxydation ring by carrying out oxidizing roasting to the useless chip of copper and indium gallium Selenium oxide gas is converted in border, in order to handle the selenium oxide gas, to obtain elemental selenium, on the other hand may be used also Make the molybdenum electrode layer in film functional layer positioned at underlay substrate surface that oxidation fusion occur, in order to realize film functional layer and lining The separation of substrate, then purification processes are carried out based on the film functional layer after separation, to obtain elemental copper, simple substance indium and simple substance Gallium.So, the technical program to copper indium gallium selenide give up chip recycle when, can be by film functional layer and underlay substrate phase Mutually separation, therefore can effectively avoid the component of underlay substrate being introduced in the target layer of recovery processing, to The purification difficulty of copper indium gallium selenide can be reduced, the rate of recovery of the valuable metals such as copper indium gallium selenide is improved.Underlay substrate (stainless steel simultaneously Substrate) and metal molybdenum can also be recycled.
It should be understood that above general description and following detailed description is only exemplary and explanatory, not It can the limitation present invention.
Description of the drawings
The drawings herein are incorporated into the specification and forms part of this specification, and shows the implementation for meeting the present invention Example, and be used to explain the principle of the present invention together with specification.
Fig. 1 is the recovery method schematic diagram one according to the copper indium gallium selenide material shown in an exemplary embodiment；
Fig. 2 is the recovery method schematic diagram two according to the copper indium gallium selenide material shown in an exemplary embodiment；
Fig. 3 is the recovery method flow chart according to the copper indium gallium selenide material shown in an exemplary embodiment；
Fig. 4 is the recovery system module map one according to the copper indium gallium selenide material shown in an exemplary embodiment；
Fig. 5 is the planar structure schematic diagram according to the roaster shown in an exemplary embodiment；
Fig. 6 is the cross-sectional view according to the roaster shown in an exemplary embodiment；
Fig. 7 is the treatment process procedure chart according to the useless chip of copper indium gallium selenide shown in an exemplary embodiment.
Specific implementation mode
Example embodiments are described in detail here, and the example is illustrated in the accompanying drawings.Following description is related to When attached drawing, unless otherwise indicated, the same numbers in different drawings indicate the same or similar elements.Following exemplary embodiment Described in embodiment do not represent and the consistent all embodiments of the present invention.On the contrary, they be only with it is such as appended The example of the consistent device and method of some aspects being described in detail in claims, of the invention.
Based on this, technical solution provided in an embodiment of the present invention is related to a kind of recovery method of copper indium gallium selenide chip, can use It is separated and recovered in the valuable metal in copper-indium-galliun-selenium film solar cell waste material.As shown in Figure 1, the recovery method May include step S1-S3：
Step S1:Pretreatment is processed by shot blasting the give up side of chip of copper indium gallium selenide, makes to be located at lining in film functional layer The molybdenum electrode layer of base plate surface exposes；
Step S2:First segment oxidizing roasting is handled, and at a temperature of 350-500 DEG C, is roasted to the copper indium gallium selenide chip that gives up, Obtain the flue gas containing selenium oxide gas and fired slags；
Step S3:Second segment oxidizing roasting is handled, and at a temperature of 800-1000 DEG C, is roasted again to the fired slags It burns, the film functional layer in the useless chip of the copper and indium gallium is made to be detached with underlay substrate.
Based on the above process, it is contemplated that copper indium gallium selenide give up chip carry out oxidizing roasting the first purpose be that film can be made Oxidation fusion occurs positioned at the molybdenum electrode layer on underlay substrate surface in functional layer, in order to realize film functional layer and underlay substrate Separation.In order to ensure molybdenum electrode layer can adequately catalytic oxidation atmosphere and hot environment, therefore useless to copper indium gallium selenide Before chip carries out oxidizing roasting, as shown in Fig. 2, being processed by shot blasting to the give up side of chip of copper indium gallium selenide, so that film work( Expose positioned at the molybdenum electrode layer on underlay substrate surface in ergosphere.
Wherein, it needs the material size being processed by shot blasting that can be arranged between 3-5cm, can both ensure molybdenum electricity in this way Outside pole layer is exposed to, and it is unlikely to waste excessive material.In the present embodiment, burnishing device example may be used in the polishing treatment It as polishing machine carries out, but can also be realized, this not made here specific by way of manually polishing and polishing for example, by using sand paper It limits.
Based on this, the present embodiment is by being processed by shot blasting the give up side of chip of copper indium gallium selenide, so that molybdenum electrode layer gold Belong to conductive layer to expose outside, the metal of molybdenum electrode layer and effective contact area of oxidizing atmosphere can be increased in this way, to advantageous In the oxidation and stripping of realizing molybdenum electrode layer.
It is exemplary, when valuable metal of the present embodiment in the chip that gives up to copper indium gallium selenium solar cell recycles, tool Body process is as follows：Chip can be given up to copper indium gallium selenide first under 350-500 degree, high temperature oxidation roasting processing is carried out, so that wherein Selenium element oxidation reaction occurs and generates selenium oxide (boiling point is 340-350 degree, and sublimation temperature is 315 degree) gas and with cigarette Gas is discharged.It so that copper indium gallium selenide is given up chip under 800-1000 degree, carry out high temperature oxidation roasting processing, position in film functional layer The molybdenum trioxide that metal conducting layer such as molybdenum electrode in underlay substrate surface occurs high-temperature oxydation reaction and generates molten state is (molten Point is 795 degree), to realize the separation of underlay substrate and film functional layer；Wherein, the temperature of high temperature oxidation roasting technique should It is sufficient for the occurrence condition of above-mentioned chemical reaction and the melting temperature of metal oxide, and oxidizing atmosphere can pass through control The ratio of air is adjusted.Then the flue gas containing selenium oxide gas can be handled, so that selenium oxide gas therein It can be reduced to elemental selenium, to realize the recycling of elemental selenium.Finally can pair with underlay substrate phase separation film functional layer into Row processing, to respectively obtain the valuable elements such as copper, indium, gallium and molybdenum.
The technical solution that the embodiment of the present invention is provided, by copper indium gallium selenide give up chip carry out oxidizing roasting, on the one hand Selenium element can be made to be converted to selenium oxide gas in high-temperature oxidation environment, in order to handle the selenium oxide gas, to Elemental selenium is obtained, on the other hand can also make the molybdenum electrode layer in film functional layer positioned at underlay substrate surface that oxidation fusion occur, In order to realize the separation of film functional layer and underlay substrate, then purification processes are carried out based on the film functional layer after separation, from And obtain elemental copper, simple substance indium and Metallic Gallium.So, the technical program to copper indium gallium selenide give up chip recycle when, Film functional layer can be separated from each other with underlay substrate, therefore can effectively avoid the component of underlay substrate being introduced to In the target layer of recovery processing, so as to reduce the purification difficulty of copper indium gallium selenide, while the rate of recovery of copper indium gallium selenide is improved.
It is exemplary, it, can when valuable metal of the present embodiment in the chip that gives up to copper indium gallium selenium solar cell recycles Including step S4, detailed process is as follows：
Step S4:To first segment oxidizing roasting obtain the flue gas containing selenium oxide gas and second segment oxidizing roasting separation Film functional layer is respectively processed, and obtains pure selenium, gallium, indium, copper.
Wherein, film functional layer refers to other film layers in addition to crossing underlay substrate in copper indium gallium selenium solar cell It is referred to as, such as may include electrode layer, absorbed layer, transition zone and Window layer etc..
Below by taking the flexible copper indium gallium selenide solar cell at stainless steel lining bottom gives up chip as an example, in conjunction with Fig. 3 to the present invention's Recovery method is specifically described.
First, polishing length, which is 3-5cm, so that film function is processed by shot blasting to the give up side of chip of copper indium gallium selenide The molybdenum electrode layer for being located at underlay substrate surface in layer exposes.
Then, to copper indium gallium selenide give up chip carry out first segment oxidizing roasting processing, calcination temperature control at 300-500 DEG C Between, roasting time controlled between 30-50 minutes, so that selenium element therein occurs oxidation reaction and generates corresponding oxidation Selenium gas, chemical reaction equation are as follows：Se+O2=SeO2.The selenium oxide gas can together be discharged with flue gas, there remains at this time The roasting of the useless chip of copper indium gallium selenide is looked into.
Then, to copper indium gallium selenide give up chip roasting look into carry out second segment oxidizing roasting processing, calcination temperature control exists Between 800-1000 DEG C, roasting time controlled between 30-90 minutes, so as to be located at stainless steel lining bottom surface in film functional layer Molybdenum electrode layer oxidation reaction can occur and generate the molybdenum trioxide of molten state, chemical reaction equation is as follows：2Mo+3O2= 2MoO3.It in the process, can also be to injection pressure-air at the position of molybdenum electrode layer, to accelerate the oxidation fusion of metal molybdenum, together When can also by perching knife by film functional layer from the sur-face peeling at stainless steel lining bottom.Due in film functional layer with underlay substrate phase The molybdenum electrode layer of contact is in molten condition, therefore can readily realize stripping of the film functional layer from stainless steel lining bottom surface From, the stainless steel lining bottom obtained at this time can be reused after the washing, molybdenum oxide it is recovered and handle after can also be again It utilizes.At the same time, which can also promote the conductive copper wire and film functional layer that are located at film function layer surface originally It is detached from, to obtain individual copper wire.
Then, the selenium oxide gas in flue gas is absorbed using spray absorber, so that selenium oxide gas is dissolved in water And selenous acid solution is formed, chemical reaction equation is as follows：SeO2+H2O=H2SeO3.On this basis, into selenous acid solution Addition sulfuric acid is warming up to 70 DEG C and is passed through sulfur dioxide gas adjusting its pH value between 1-2.5, so that sub- Selenic acid occurs reduction reaction and generates elemental selenium, and chemical reaction equation is as follows：H2SeO3+2SO2+H2O=Se+2H2SO4.The change Required elemental selenium can be obtained by filtering by learning the product of reaction, and selenium recovery therein is and remaining up to 98% or more Filtrate is circularly used for deselenization processing.It should be noted that：Selenium oxide gas is the product of first segment oxidizing roasting processing, therefore This step can handle in first segment oxidizing roasting and complete to carry out later, be had no with the sequencing of second segment oxidizing roasting processing Conflict.
Finally, cooling treatment is carried out to the film functional layer removed from stainless steel lining bottom surface, with obtain comprising copper, indium, The fired slags of the film layers such as gallium, then routinely technology is chemically treated to the fired slags, to respectively obtain elemental copper, simple substance indium With the separation and recovery of the valuable metals such as Metallic Gallium.
The recovery method of the present invention is given below by embodiment and is further explained.
Embodiment 1
Polishing length, which is 5cm, so that in film functional layer is processed by shot blasting to give up one end of chip of copper indium gallium selenide first Molybdenum electrode positioned at stainless steel lining bottom surface is exposed.Then the chip that gives up is placed in oxidizing roasting stove and is moved with furnace bottom, with It is easy to implement two-stage oxidizing calcination process.The calcination temperature of first segment oxidizing roasting processing is 350 DEG C, roasting time 50min, Selenium element can be oxidized into selenium oxide gas and as flue gas is discharged by the flue that is connected to the oxidizing roasting stove at this time, then Selenous acid solution is formed through the absorption of spray absorber, sulfur dioxide gas is then acidified and be passed through using sulfuric acid, so that sub- Selenic acid occurs reduction reaction and obtains elemental selenium.The calcination temperature of second segment oxidizing roasting processing is 800 DEG C, and roasting time is 90min is directly blown using pressure-air to the molybdenum electrode of stainless steel lining bottom surface in the end of this section of oxidizing roasting technique, with Make metal molybdenum layer that oxidizing fusion constantly occur, and under the injection effect of pressure-air and the release effect of perching knife, film Functional layer is detached with stainless steel lining bottom, and obtains target thin film layer, copper wire and stainless steel lining bottom through supercooling.Finally to institute The separation and recovery to valuable elements such as copper, indium, galliums, gained can be realized using the processing of following conventional chemicals in the target thin film layer obtained Stainless steel lining bottom and copper wire also recyclable recycling, to increase the utilization rate of product.
Aimed thin film is placed in ball mill and carries out ball-milling treatment by the first step, to obtain grain size in 80 mesh mesh below Mark powder.
Second step measures the sulfuric acid solution of a concentration of 3mol/L, and above-mentioned target powder is added in the solution and is heated up It to 95 DEG C, then is passed through air into the solution after heating and impregnates 12 hours, filtrate is then obtained by filtration, is mainly wrapped in the filtrate Include metallic element copper, indium, gallium.
Third walks, and a concentration of 10% sodium hydroxide is added into above-mentioned filtrate, and pH value adjustment to 1.8 then adds Enter extractant example AD-100N with to copper ion carry out room temperature extraction, extraction conditions be using 400ml extractants carry out 2 grades 10 times The ratio of extraction, extractant and solution is 1:1, each extraction time is 6min, then carries out room temperature back extraction to extract liquor again To obtain copper-bath, back extraction condition is to carry out 10 grades of back extraction using the sulfuric acid of 400ml, 1.5mol/L, extractant and The ratio of back extraction acid is 1:1, each back-extraction time is 6min.
4th step, is electrolysed copper-bath, to obtain the high purity metal copper that purity is 99.95%, wherein electricity Solution voltage is 1.8V, current density 250A/m2, electrolyte temperature is 50 DEG C or so, electrolysis time 4h, chemical reaction side Journey is as follows：2CuSO4+2H2O=2H2SO4+2Cu+O2。
A concentration of 10% NaOH is added in the extraction extraction raffinate walked to third for 5th step, by pH value adjustment to 13.5, with Standing separation after extraction extraction raffinate is heated to 85 DEG C afterwards and is kept for 0.5 hour takes supernatant liquor, and is filtered water to precipitation It washes, gained filter residue is indium hydroxide, and acquired solution is sodium solution gallate.
6th step, sodium solution gallate is electrolysed with obtain purity be 99.6% gallium, decomposition voltage 2.5V, Current density is 200A/m2, electrolyte temperature is 50 DEG C or so, electrolysis time 6h.
7th step, indium hydroxide is dissolved in the hydrochloric acid of 0.5mol/L, 500mL, using zine plate to phosphide element into line replacement, To obtain the indium metal that purity is 99%, reaction temperature is 55 DEG C, time swap 8h.
By above-mentioned processing procedure, copper indium gallium selenide give up copper in chip, indium, gallium, selenium element the rate of recovery be copper 95%, indium 96%, gallium 96%, selenium 97%.
The recycling to elemental copper, simple substance indium and Metallic Gallium can be realized based on the above process, the metal purity obtained in this way It is high.Certainly, the present embodiment is merely illustrative the chemical treating process of above-mentioned target thin film layer, can also use it Its chemical treating process substitute, as long as be that by elemental copper, simple substance indium and Metallic Gallium purification recycling, here for Recovery method is not especially limited.
Embodiment 2
According to the condition of embodiment 1, only to copper indium gallium selenide give up chip polishing length be 4cm, first segment oxidizing roasting The calcination temperature of processing is 400 DEG C, roasting time 40min, and the calcination temperature of second segment oxidizing roasting processing is 900 DEG C, roasting The burning time be 70min, carry out embodiment 2 recovery processing, copper indium gallium selenide give up chip in copper, indium, gallium, selenium element the rate of recovery be Copper 95%, indium 96%, gallium 97%, selenium 97%.
Embodiment 3
According to the condition of embodiment 1, only to copper indium gallium selenide give up chip polishing length be 3cm, first segment oxidizing roasting The calcination temperature of processing is 500 DEG C, roasting time 30min, and the calcination temperature of second segment oxidizing roasting processing is 1000 DEG C, roasting The burning time be 30min, carry out embodiment 3 recovery processing, copper indium gallium selenide give up chip in copper, indium, gallium, selenium element the rate of recovery be Copper 95%, indium 96%, gallium 97%, selenium 97%.
By above-described embodiment it is found that using technology of the invention, useless chip polishing pretreatment, two-stage oxidizing are roasted, is high It calms the anger injection oxidizing gas or air and lift-off technology can efficiently separate copper indium gallium selenide and give up chip film layer, copper indium gallium selenide etc. is valuable The rate of recovery of element is high, and stainless steel lining bottom, molybdenum element, copper wire can also recycle, and simplify technological process, reduce equipment It is required that improving separating effect, recycling for film layer, stainless steel lining bottom and copper wire raw material is realized, is received significant Technical benefits.
Correspondingly, technical solution provided in an embodiment of the present invention further relates to a kind of recovery system of the useless chip of copper indium gallium selenide, It can be used for separating and recovering the valuable element in copper-indium-galliun-selenium film solar cell waste material.As shown in figure 4, the recycling System may include：Oxidizing roasting device 10, gas treatment means 20 and separating treatment mechanism 30.
The oxidizing roasting device 10, for copper indium gallium selenide give up chip carry out oxidizing roasting so that copper indium gallium selenide give up core Film functional layer in piece is detached with underlay substrate, and obtains the flue gas containing selenium oxide gas；
The gas treatment means 20, for handling the flue gas containing selenium oxide gas, to obtain elemental selenium；
The separating treatment mechanism 30, for handling film functional layer, with respectively obtain elemental copper, simple substance indium and Metallic Gallium.
It should be noted that：Gas treatment means 20 and separating treatment mechanism 30 may relate to multiple devices or equipment, As long as a combination thereof can realize above-mentioned function, other to be not especially limited.
The technical solution that the embodiment of the present invention is provided, by the way that the copper indium gallium selenide chip that gives up to be placed in oxidizing roasting device 10 To carry out oxidizing roasting, on the one hand selenium element can be made to be converted to selenium oxide gas in high-temperature oxidation environment, in order to pass through gas Body processing mechanism 20 handles the selenium oxide gas, to obtain elemental selenium, on the other hand can also make in film functional layer Oxidation fusion occurs for the molybdenum electrode layer positioned at underlay substrate surface, in order to realize the separation of film functional layer and underlay substrate, Purification processes are carried out based on the film functional layer after separation by separating treatment mechanism 30 again, to obtain elemental copper, simple substance indium And Metallic Gallium.So, the technical program to copper indium gallium selenide give up chip recycle when, can be by film functional layer and substrate Substrate is separated from each other, therefore can effectively avoid the target layer that the component of underlay substrate is introduced to recovery processing In, so as to reduce the purification difficulty of copper indium gallium selenide, while improving the rate of recovery of copper indium gallium selenide.
In this example embodiment, in order to ensure coming into full contact with for molybdenum electrode and oxidizing atmosphere, as shown in figure 5, described time Receipts system can also include such as polishing machine of burnishing device 40, which can be used for giving up to copper indium gallium selenide the side of chip It is processed by shot blasting, so as to expose positioned at the molybdenum electrode layer on underlay substrate surface in film functional layer.So, the present embodiment By being processed by shot blasting to the give up side of chip of copper indium gallium selenide, molybdenum electrode layer and effective contact surface of oxidizing atmosphere can be increased Product, to be advantageously implemented the oxidation and stripping of molybdenum electrode layer.
Optionally, roaster may be used in the oxidizing roasting device 10 in the embodiment of the present invention.As shown in Fig. 6 and Fig. 7, The structure of the roaster may include mainly：
Furnace body 101, including furnace roof 1011, furnace wall 1012 and partition wall 1013, the partition wall 1013 can be by the inside of furnace body 101 It is divided into feed zone 101a, oxidizing roasting area 101b and cooling discharging area 101c, the oxidizing roasting area 101b can be used for copper The useless chip of indium gallium selenium carries out oxidizing roasting；
Flue 102 is connected positioned at the top of furnace body 101 and with oxidizing roasting area 101b, the flue 102 can be used for by The flue gas discharge containing selenium oxide gas that the useless chip of copper indium gallium selenide is generated by oxidizing roasting；
Stripping off device 103 is located at the end of oxidizing roasting area 101b, including high-pressure oxidation gas piping 1031 and stripping Perching knife 1032；The high-pressure oxidation gas piping 1031 can be used for being located at into film functional layer the gold on 1001 surface of underlay substrate Belong to conductive layer 1002 and be blown pressure-air, so that metal conducting layer 1002 occurs oxidation fusion and accelerates film functional layer from lining The stripping on 1001 surface of substrate, the stripping perching knife 1032 can be used for being blown pressure-air to metal conducting layer 1002 Simultaneously by film functional layer from the sur-face peeling of underlay substrate 1001；
Heat power engineering system 104 includes multiple burners positioned at oxidizing roasting area 101b, and the mode of radiant heating can be used by oxygen Change roast area 101b and be heated to preset calcination temperature, and is adjusted in stove by controlling the proportioning (air-fuel ratio) of air and combustion gas Temperature and oxidizing atmosphere；Wherein, burner can be arranged in the inside of the furnace wall of oxidizing roasting area 101b 1012, and height can be with It is located at furnace roof 1011 at the position of 2/3 furnace body height；
Movable hearth furnace bottom 105 is located at the lower section of furnace body 101, can be used for that copper indium gallium selenide material 100 is driven to pass through furnace body 101 Internal each region；
Furnace bottom holder and transmission system 106 are located on the pedestal of 105 lower section of movable hearth furnace bottom, can be used for controlling removable The movement of furnace bottom 105 with it is static.
It should be noted that：In order to ensure that give up chip 100 of copper indium gallium selenide can follow movable hearth furnace bottom 105 to pass through furnace body 101 each region, then between partition wall 1013 need to extend downwardly from furnace roof 1011 and keep certain between rotatable stove bottom 105 Away from, in order to for copper indium gallium selenide give up chip 100 by reserving channel.In addition, the lower section at movable hearth furnace bottom 105 can be with Water seal arrangement 107 is set, is scurried into inside furnace body 101 with the gas in waterproof and water drainage system.
Based on above structure, in order to realize the oxidizing roasting processing of point temperature section, the oxidizing roasting area 101b can be with It is further separated by partition wall 1013, to be divided into close to the first oxidizing roasting area of feed zone 101a and close to cooling discharging area The second oxidizing roasting area of 101c, and flue 102 is located at the top in the first oxidizing roasting area.Wherein, the first oxidizing roasting area can For to copper indium gallium selenide give up chip carry out first segment oxidizing roasting processing, to obtain the flue gas containing selenium oxide gas and copper and indium The intermediate material of gallium selenium, and the flue gas containing selenium oxide gas is discharged from flue 102；Second oxidizing roasting area can be used for copper The intermediate material of indium gallium selenium carries out second segment oxidizing roasting processing, by film functional layer from the sur-face peeling of underlay substrate, this When underlay substrate and film functional layer will be transmitted to cooling discharging area 101c successively with movable hearth furnace bottom 105, and it is cooling go out Material area 101c can be used for carrying out cooling treatment to film functional layer, to obtain including at least the target thin film layer of copper, indium, gallium etc..
So, the present embodiment is used as oxidizing roasting device 10 by using roaster, can be useless to copper indium gallium selenide Chip carries out the oxidizing roasting processing of point temperature section, to obtain the flue gas containing selenium oxide gas, underlay substrate and at least Include the target thin film layer of copper, indium, gallium.
On this basis, the embodiment of the present invention on the one hand can be by gas treatment means 20 come to containing selenium oxide gas Flue gas carry out absorb and reduction treatment on the other hand can be 30 come pairs by separating treatment mechanism in order to obtain elemental selenium Target thin film layer is chemically treated, with and with respectively obtain the valuable metals such as elemental copper, simple substance indium and Metallic Gallium.
Optionally, the gas treatment means 20 may include spray absorber and reduction apparatus.Wherein, spray absorber It is connected with flue 102, can be used for absorbing oxygen by the way of spray from the flue gas containing selenium oxide gas that flue is discharged Change selenium gas to obtain selenous acid solution, and reduction apparatus can be used for acidic materials being added into selenous acid solution and to selenous acid Solution carries out reduction treatment, to extract the elemental selenium.
Optionally, the separating treatment mechanism 30 can include but is not limited to ball mill, filter device, extraction equipment, electricity Device and chemical reaction equipment etc. are solved, such as may be used chemically treated to the progress of target thin film layer in above-mentioned recovery method Method and step is handled, to realize the recycling to elemental copper, simple substance indium and Metallic Gallium.Certainly, the present embodiment can also use Other chemical treating processes substitute, and 30 need of separating treatment mechanism choose corresponding place according to selected chemical treatment method at this time Manage device.
Those skilled in the art will readily occur to its of the present invention after considering specification and putting into practice disclosure disclosed herein Its embodiment.This application is intended to cover the present invention any variations, uses, or adaptations, these modifications, purposes or Person's adaptive change follows the general principle of the present invention and includes undocumented common knowledge in the art of the invention Or conventional techniques.The description and examples are only to be considered as illustrative, and true scope and spirit of the invention are by following Claim is pointed out.
It should be understood that the invention is not limited in the precision architectures for being described above and being shown in the accompanying drawings, and And various modifications and changes may be made without departing from the scope thereof.The scope of the present invention is limited only by the attached claims.

Claims (10)

  1. The recovery method of chip 1. a kind of copper indium gallium selenide is given up, includes the following steps：
    Pretreatment is processed by shot blasting the give up side of chip of copper indium gallium selenide, makes to be located at underlay substrate surface in film functional layer Molybdenum electrode layer expose；
    First segment oxidizing roasting is handled, and at a temperature of 350~500 DEG C, is roasted, is obtained containing aerobic to the copper indium gallium selenide chip that gives up Change the flue gas and fired slags of selenium gas；
    Second segment oxidizing roasting is handled, and at a temperature of 800~1000 DEG C, is roasted again to the fired slags, makes the copper Film functional layer in the useless chip of indium gallium is detached with underlay substrate.
  2. 2. recovery method according to claim 1, the pretreatment is to make to be located at underlay substrate surface in film functional layer Molybdenum electrode layer expose 3-5cm.
  3. 3. recovery method according to claim 1 or 2, the second segment oxidizing roasting processing, keep the copper indium gallium selenide useless Film functional layer in chip is detached with underlay substrate, including：
    During the second segment oxidizing roasting is handled, into the film functional layer positioned at the underlay substrate surface Molybdenum electrode layer is blown pressure-air, so that the molybdenum electrode layer occurs oxidation fusion and accelerates the film functional layer from the lining The stripping of base plate surface.
  4. 4. recovery method according to claim 3, described to make the film functional layer in the useless chip of the copper indium gallium selenide and lining Substrate detaches, and further includes：
    During being blown pressure-air to the molybdenum electrode layer, by perching knife by the film functional layer from the substrate base The sur-face peeling of plate.
  5. 5. recovery method according to claim 1, further includes：First segment oxidizing roasting is obtained containing selenium oxide gas Flue gas and the film functional layer of second segment oxidizing roasting separation are respectively processed, and obtain pure selenium, gallium, indium, copper.
  6. 6. recovery method according to claim 5, described to handle the flue gas containing selenium oxide gas, obtain Pure selenium includes：
    The selenium oxide gas is absorbed from the flue gas containing selenium oxide gas using spray process, it is molten to obtain selenous acid Liquid；
    Acidic materials are added into the selenous acid solution and reduction treatment is carried out to the selenous acid solution, to obtain the list Matter selenium.
  7. 7. recovery method according to claim 5 handles the film functional layer, fine copper, indium and gallium packet are obtained It includes：
    Cooling treatment is carried out to the film functional layer, to obtain including at least the target thin film layer of copper, indium, gallium；
    The target thin film layer is chemically treated, to respectively obtain fine copper, indium and gallium.
  8. The recovery system of chip 8. a kind of copper indium gallium selenide is given up, including：Burnishing device, oxidizing roasting device, gas treatment means and Separating treatment mechanism；
    The burnishing device, for give up to copper indium gallium selenide chip carry out oxidizing roasting before, to the copper indium gallium selenide give up chip Side be processed by shot blasting so that in the film functional layer positioned at the underlay substrate surface metal conducting layer expose；
    The oxidizing roasting device is roaster, including：
    Furnace body, including oxidizing roasting area and the flue that is connected to the oxidizing roasting area, the oxidizing roasting area are used for institute It states the useless chip of copper indium gallium selenide and carries out oxidizing roasting, the flue is for being discharged the flue gas containing selenium oxide gas；
    Movable hearth furnace bottom is located at the lower section of the furnace body, for driving the copper indium gallium selenide to give up chip across the interior of the furnace body Portion；
    Stripping off device is located at the end in the oxidizing roasting area, for by the film functional layer from the table of the underlay substrate It removes in face；
    Heat power engineering system includes multiple burners positioned at the oxidizing roasting area, for the oxidizing roasting area to be heated to preset Calcination temperature；
    The high-pressure oxidation gas piping, the molybdenum electrode layer for being located at the underlay substrate surface into the film functional layer It is blown high-pressure oxidation gas, so that the molybdenum electrode layer occurs oxidation fusion and accelerates the film functional layer from the substrate base The stripping of plate surface；
    The stripping perching knife is used for the film functional layer during being blown high-pressure oxidation gas to the molybdenum electrode layer From the sur-face peeling of the underlay substrate；
    The gas treatment means, for handling the flue gas containing selenium oxide gas, to obtain elemental selenium；
    The separating treatment mechanism, for handling the film functional layer, to respectively obtain elemental copper, simple substance indium and list Matter gallium.
  9. 9. recovery system according to claim 8, the furnace body further includes feed zone and cooling discharging area, and is located at institute State multiple partition walls between the oxidizing roasting area and the cooling discharging area between feed zone and the oxidizing roasting area；
    Wherein, the cooling discharging area be used for the film functional layer carry out cooling treatment, with obtain include at least copper, indium, The target thin film layer of gallium, the separating treatment mechanism for handling the target thin film layer, with respectively obtain elemental copper, Simple substance indium and Metallic Gallium.
  10. 10. recovery system according to claim 9, the oxidizing roasting area includes the first oxidizing roasting area and the second oxidation Roast area separates between first oxidizing roasting area and second oxidizing roasting area also by the partition wall, and the cigarette Road is located at first oxidizing roasting area；
    First oxidizing roasting area is used to carry out first segment oxidizing roasting processing to the useless chip of the copper indium gallium selenide, to obtain State the flue gas containing selenium oxide gas and the intermediate material of copper indium gallium selenide, and by the flue gas containing selenium oxide gas from institute State flue discharge；
    Second oxidizing roasting area is used to carry out second segment oxidizing roasting processing to the intermediate material of the copper indium gallium selenide, will Sur-face peeling of the film functional layer from the underlay substrate.
CN201810669830.1A 2018-06-26 2018-06-26 The recovery method and recovery system of the useless chip of copper indium gallium selenide Pending CN108754153A (en)

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Publication number Priority date Publication date Assignee Title
CN102951618A (en) * 2011-08-31 2013-03-06 深圳市格林美高新技术股份有限公司 Method for recycling germanium, gallium, indium and selenium in waste diode
CN103459624A (en) * 2011-06-03 2013-12-18 住友金属矿山株式会社 Method for recovering valuable metals
CN203382807U (en) * 2013-07-18 2014-01-08 荆门市格林美新材料有限公司 Oxidizing roasting equipment for recovered germanium, gallium, indium and selenium
TW201540844A (en) * 2014-04-28 2015-11-01 Univ Nat Cheng Kung Recovery method by heat-treating copper-indium-gallium-selenium residual target material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103459624A (en) * 2011-06-03 2013-12-18 住友金属矿山株式会社 Method for recovering valuable metals
CN102951618A (en) * 2011-08-31 2013-03-06 深圳市格林美高新技术股份有限公司 Method for recycling germanium, gallium, indium and selenium in waste diode
CN203382807U (en) * 2013-07-18 2014-01-08 荆门市格林美新材料有限公司 Oxidizing roasting equipment for recovered germanium, gallium, indium and selenium
TW201540844A (en) * 2014-04-28 2015-11-01 Univ Nat Cheng Kung Recovery method by heat-treating copper-indium-gallium-selenium residual target material

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Application publication date: 20181106