CN103978021B - A kind of useless crystal silicon solar energy battery plate method for disassembling and recycling - Google Patents
A kind of useless crystal silicon solar energy battery plate method for disassembling and recycling Download PDFInfo
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- CN103978021B CN103978021B CN201410192135.2A CN201410192135A CN103978021B CN 103978021 B CN103978021 B CN 103978021B CN 201410192135 A CN201410192135 A CN 201410192135A CN 103978021 B CN103978021 B CN 103978021B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/20—Waste processing or separation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/82—Recycling of waste of electrical or electronic equipment [WEEE]
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Abstract
The invention discloses a kind of useless crystal silicon solar energy battery plate method for disassembling and recycling, the useless aluminum frame of crystal silicon solar energy battery plate, safety glass, silicon wafer, aluminum, silver, copper classification recovery can be realized.The method that the method uses heat treatment technics to combine with chemical method realizes useless crystal silicon solar energy battery edges of boards frame, glass reclaims and separates with silicon wafer, and valuable metal and silicon wafer reclaim.Not only reduce recycling difficulty, be simultaneously achieved the innoxious of tail gas, prevent and treat secondary pollution, protect environment；Wherein, alkali leaching process and acidleach process solution and recycle, and reduce reagent consumption, decrease the generation amount of spent acid, salkali waste, reduce end waste disposal fee and use.
Description
Technical field
The invention belongs to field of solid waste treatment, disassemble realization particularly to the one crystal silicon solar energy battery plate that gives up
The method that resource classification reclaims.
Background technology
From the nineties in last century, China establishes the small-sized demonstrative project of solar energy in some fields.2002, country used up
Volt solves the electrical problem in Wu electricity township, and photovoltaic consumption reaches 15.5MWp, has promoted the development of photovoltaic industry.Since two thousand five,
The volume of production of China's solaode develops with the rate of rise of annual 100%, and continuous 5 annual productions of 2007-2011 occupy the world
First.Within 2011, solar cell yield is more than 20GW, exceedes the 50% of whole world total output.According to industrial development planning, 2015
20GW and 50GW is respectively reached with the accumulative installed capacity of the year two thousand twenty China photovoltaic system.
The life-span that generally uses of solar panel is 25 years, after exceeding service life, and the transformation efficiency of solaode
Can drastically decline, until losing efficacy, scrapping.The solar panel that the nineties in last century installs will be scrapped in succession.Although solar energy
Battery includes silicon system solaode, compound semiconductor cell, organic semiconductor battery and Nano semiconductor battery.But in early days
Solar module be mostly monocrystal silicon and polycrystal silicon cell assembly.The most how to process and crystal after scrapping
In silicon solar cell plate, Resource recovery needs to merit attention.
Crystal silicon solar energy battery plate is made up of outer rim, glass, encapsulating material, backboard, rosette and solaode
(see figure 1).Outer rim material is generally aluminium alloy；The glass of battery front side is low ferrum safety glass；Encapsulating material is typically selected
Ethylene-vinyl acetate copolymer (EVA)；Backboard is polyvinyl fluoride composite membrane (TPT), and TPT haves three layers, and middle one layer is poly-to benzene
Dioctyl phthalate second diester (PET), additionally two-layer is polyvinyl fluoride (PVF, Tedlar film).By the welding combination of multiple monocell sheets one
Rising and be referred to as convergent belt, for connecting the both positive and negative polarity of each piece of cell piece, convergent belt is tin-coated copper strip.The lamination order of whole cell panel
It is: safety glass, EVA, battery, EVA and backboard to be laminated rear surrounding and embedded in aluminum frame from top to bottom, the wiring at back
Box connects with convergent belt and draws the electric current of entire plate, forms a complete cell panel.
Solar panel main material composition accounting is shown in Table 1.
Table 1 solar panel summary of materials (kg/KWp) (2012)
| Material | Silicon | Silver | Aluminum | Glass | Copper | Plastics |
| Quality | 3.101 | 0.03 | 12.771 | 54.721 | 0.451 | 17.091 |
By Fig. 1 and Biao 1 it can be seen that in solar panel each component occurrence status more single, aluminum frame, copper, glass
Deng composition, there is certain recovery value.Based on solaode panel material occurrence status, set up rational disassembling technology route,
Being possible not only to solve the process handling problems of useless solar panel, the high-efficiency cleaning that also can realize resource reclaims.
Summary of the invention
It is an object of the invention to provide a kind of useless crystal silicon solar energy battery plate method for disassembling and recycling, useless crystalline substance can be realized
The classification of the aluminum frame of body silicon solar cell plate, safety glass, silicon wafer, aluminum, silver, copper is reclaimed.
It is an object of the invention to be achieved through the following technical solutions:
A kind of useless crystal silicon solar energy battery plate method for disassembling and recycling, described method for disassembling and recycling includes following
Step:
A, first being put in airtight firing equipment by useless crystal silicon solar energy battery plate and heat, under high temperature, heating makes aluminum
The parts of plastics such as alloy framework, copper cash, cell piece and safety glass can be completely separable, backboard are melted into ashes by heat treatment,
Tail gas empties after incinerator burning disposal；After equipment to be heated cooling, sort out aluminum alloy frame, copper cash and safety glass
Recycle；
B, cell piece after above-mentioned steps a heat treatment at room temperature, with dipping by lye, treat alkali liquor and cell piece surface
After aluminium paste reacts completely, obtain aluminum cell sheet, aluminum cell sheet will be gone to take out, obtain containing aluminum alkali liquor；
The described alkali liquor containing aluminum can be repeated several times utilization, and the alkali liquor containing aluminum can be used for preparing sodium polyaluminate product；
C, the alkali leaching of above-mentioned steps b process after go aluminum cell sheet once purged, with acid solution soak, by cell piece surface
Ag leaches, and obtains silver battery sheet, goes silver battery sheet to take out by described, obtain argentiferous acid solution；
After the repeated repeatedly utilization of described acid solution when Ag is at concentrations up to 500mg/L, add excessive hydrochloric acid and obtain silver chloride
Precipitation, then obtain argentum powder with zinc powder reduction, Ag is recycled；
D, the acidleach of above-mentioned steps c process after remove silver battery sheet, surface is still covered with blue silicon nitride anti-reflection, adds
Hydrofluoric acid solution (HF solution), when question response is completely rear, obtains the cell piece of silicon nitride；Cell piece obtains pure after over cleaning
Clean silicon wafer, through polycrystalline silicon ingot casting machine ingot casting, obtains described polycrystal silicon ingot.
Further, aqueous slkali described in step b is NaOH solution, and its mass concentration is 20% ~ 40%.
Further, acid solution described in step c is HNO3Solution, its molar concentration is 5 ~ 10mol/L.
The present invention provides the benefit that compared to existing technology:
1, the method for the invention improves value-added content of product: a step can obtain aluminum alloy frame, plating after high temperature pyrolysis
Stannum copper cash and safety glass, can Direct Classification reclaim, and reclaims material added value and improves；
2, exhaustive classification reclaims metal and silicon wafer: the alkali leaching process of cell piece and acidleach process and achieve aluminum and silver respectively
The classification of two kinds of metals is reclaimed, and can get again pure silicon wafer through HF solution and cleaning；
3, reduce recycling difficulty: the aluminum frame that obtains directly recycling by once pyrolysis, safety glass and
Copper cash, then carries out stepwise disposal for cell piece, and recovery process is simple, easy to operate feasible；
4, tail gas hazard-free: the tail gas producing high-temperature heat treatment process carries out burning disposal, prevents and treats secondary pollution, protection
Environment；
5, reagent consumption is decreased: alkali leaching process and acidleach process solution and recycle, and reduce reagent consumption, decrease
Spent acid, the generation amount of salkali waste, reduce end waste disposal fee and use；
6, the method that the method for the invention uses heat treatment technics and chemical method to combine realizes the useless crystalline silicon sun
Energy cell panel frame, glass reclaim and separate with silicon wafer, and valuable metal and silicon wafer reclaim.
The invention will be further described with case study on implementation below in conjunction with the accompanying drawings.
Accompanying drawing explanation
Fig. 1 crystal silicon solar energy battery board plane figure；
Fig. 2 is useless crystal silicon solar energy battery plate disassembling technology route map.
Detailed description of the invention
Embodiment 1
A kind of useless crystal silicon solar energy battery plate method for disassembling and recycling, described method for disassembling and recycling includes following
Step:
A, first being put in airtight firing equipment by useless crystal silicon solar energy battery plate and heat, under high temperature, heating makes aluminum
The parts of plastics such as alloy framework, copper cash, cell piece and safety glass can be completely separable, backboard are melted into ashes by heat treatment,
Tail gas empties after incinerator burning disposal；After equipment to be heated cooling, sort out aluminum alloy frame, copper cash and safety glass
Recycle；
B, cell piece after above-mentioned steps a heat treatment at room temperature, with dipping by lye, treat alkali liquor and cell piece surface
After aluminium paste reacts completely, obtain aluminum cell sheet, aluminum cell sheet will be gone to take out, obtain containing aluminum alkali liquor；
C, the alkali leaching of above-mentioned steps b process after go aluminum cell sheet once purged, with acid solution soak, by cell piece surface
Ag leaches, and obtains silver battery sheet, goes silver battery sheet to take out by described, obtain argentiferous acid solution；
D, the acidleach of above-mentioned steps c process after remove silver battery sheet, surface is still covered with blue silicon nitride anti-reflection, adds
HF solution, when question response is completely rear, obtains the cell piece of silicon nitride；Cell piece obtains pure after ultra-pure water cleans 3 times
Silicon wafer, through polycrystalline silicon ingot casting machine ingot casting, obtain polycrystal silicon ingot.
Further, aqueous slkali described in step b is NaOH solution, and its mass concentration is 20% ~ 40%.
Further, acid solution described in step c is HNO3Solution, its molar concentration is 5 ~ 10mol/L.
Further, described in step b, the alkali liquor in aluminum can be repeated several times utilization, and the alkali liquor containing aluminum can be used for preparing sodium polyaluminate
Product.
Further, after the repeated repeatedly utilization of acid solution described in step c when Ag is at concentrations up to 500mg/L, added
Amount hydrochloric acid obtains silver nitride precipitation, then obtains argentum powder with zinc powder reduction.
Each raw material described in the present embodiment is on market the conventional products sold, and the equipment used in the present embodiment is also
It is on market the conventional products sold.
Embodiment 2
The present embodiment is the preferably change scheme on the basis of embodiment 1, it is provided that useless crystal silicon solar energy battery plate is torn open
Solve recovery and treatment method.Part same as in Example 1 in the present embodiment, refer to the content disclosed in embodiment 1 and manages
Solving, embodiment 1 disclosure should also be as the content as the present embodiment, is not repeated description herein.
Described method for disassembling and recycling comprises the following steps:
A, first useless crystal silicon solar energy battery plate is put into airtight firing equipment (RX3 series-18KW box tempering resistance
Stove) in heat, final temperature 540 DEG C, heat time heating time 3h, enabling aluminum alloy to framework, copper cash, cell piece and safety glass can
Completely separable, the parts of plastics such as backboard is melted into ashes by heat treatment, and tail gas empties after incinerator burning disposal.To be heated
After equipment cooling, sort out aluminum alloy frame, copper cash and safety glass and recycle.
Cell piece after b, heat treatment at room temperature, with concentration 30%NaOH excess dipping by lye about 45min, treats alkali liquor
After reacting completely with the aluminium paste on cell piece surface, the cell piece after removing aluminum takes out, and obtains containing aluminum alkali liquor.Due to concentration of lye
Height, aluminum amount is low, and therefore alkali liquor can be used to repeatedly extract, and the alkali liquor containing aluminum after repeatedly utilizing can be used for preparing sodium polyaluminate and produces
Product, are recycled utilization.
C, alkali leaching process after go aluminum cell sheet once purged, be 7mol/L HNO by concentration3Solution soaking 40min is left
The right side, leaches the Ag on cell piece surface, and the cell piece after removing silver takes out, and obtains argentiferous acid solution, and acid solution is repeated repeatedly to be utilized
After when Ag concentration height, Ag is recycled, obtains containing silver products.
D, acidleach process after remove silver battery sheet, surface is still covered with blue silicon nitride anti-reflection, add 10% HF molten
Liquid, about 20min, treats that blueness is decorporated completely, when not having bubble to produce, obtains the cell piece of silicon nitride.Cell piece is through super
Pure water obtains pure silicon wafer after cleaning 3 times, obtains polycrystal silicon ingot through polycrystalline silicon ingot casting machine ingot casting.
Claims (5)
1. a useless crystal silicon solar energy battery plate method for disassembling and recycling, it is characterised in that described in disassemble recycling side
Method comprises the following steps:
A, first being put in airtight firing equipment by useless crystal silicon solar energy battery plate and heat, under high temperature, heating enables aluminum alloy to
Framework, copper cash, cell piece and safety glass can be completely separable, and the parts of plastics including backboard is by heat treatment chemical conversion ash
Cinder, tail gas empties after incinerator burning disposal；After equipment to be heated cooling, sort out aluminum alloy frame, copper cash and tempering
Glass recycles；
B, cell piece after above-mentioned steps a heat treatment at room temperature, with dipping by lye, treat the aluminium paste of alkali liquor and cell piece surface
Completely after reaction, obtain aluminum cell sheet, aluminum cell sheet will be gone to take out, obtain containing aluminum alkali liquor；
Alkali liquor described in step b is NaOH solution, and its mass concentration is 20% ~ 40%；
C, the alkali leaching of above-mentioned steps b process after go aluminum cell sheet once purged, soak with acid solution, the Ag on cell piece surface soaked
Go out, obtain silver battery sheet, go silver battery sheet to take out by described, obtain argentiferous acid solution；
Acid solution described in step c is HNO3Solution, its molar concentration is 5 ~ 10mol/L；
D, the acidleach of above-mentioned steps c process after remove silver battery sheet, surface is still covered with blue silicon nitride anti-reflection, adds HF molten
Liquid, when question response is completely rear, obtains the cell piece of silicon nitride；Cell piece obtains pure silicon wafer after over cleaning.
Useless crystal silicon solar energy battery plate method for disassembling and recycling the most according to claim 1, it is characterised in that step
Described in b, the alkali liquor in aluminum can be repeated several times utilization, and the alkali liquor containing aluminum can be used for preparing sodium polyaluminate product.
Useless crystal silicon solar energy battery plate method for disassembling and recycling the most according to claim 1, it is characterised in that step
After the repeated repeatedly utilization of acid solution described in c when Ag concentration height, Ag is recycled.
Useless crystal silicon solar energy battery plate method for disassembling and recycling the most according to claim 3, it is characterised in that described
The recovery method of Ag is, when described Ag is at concentrations up to 500mg/L, adds excessive hydrochloric acid and obtains silver nitride precipitation, then use zinc powder
Reduction obtains argentum powder.
Useless crystal silicon solar energy battery plate method for disassembling and recycling the most according to claim 1, it is characterised in that step
The silicon wafer finally given in d, through polycrystalline silicon ingot casting machine ingot casting, obtains polycrystal silicon ingot.
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| C06 | Publication | ||
| PB01 | Publication | ||
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