CN103978021A - Waste crystalline silicon solar cell panel disassembling and recovering method - Google Patents
Waste crystalline silicon solar cell panel disassembling and recovering method Download PDFInfo
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- CN103978021A CN103978021A CN201410192135.2A CN201410192135A CN103978021A CN 103978021 A CN103978021 A CN 103978021A CN 201410192135 A CN201410192135 A CN 201410192135A CN 103978021 A CN103978021 A CN 103978021A
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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]
Abstract
The invention discloses a waste crystalline silicon solar cell panel disassembling and recovering method. The method can realize the classification recovery of aluminum frames, toughened glass, silicon wafers, aluminum, silver and copper of waste crystalline silicon solar cell panels. The method adopts a heat treatment technology and a chemical technology combination technique to realize the frame and glass recovery of the waste crystalline silicon solar cell panels, the silicon wafer separation, and the valuable metal and silicon wafer recovery. The method has the advantages of recovery treatment difficulty reduction, tail gas harmlessness realization, secondary pollution control and environment protection; and an alkali dipping treatment and acid dipping treatment solution can be recycled, so the reagent consumption is reduced, the waste acid and waste alkali generation amount is reduced, and the final waste treatment cost is reduced.
Description
Technical field
The invention belongs to solid waste process field, particularly a kind of useless crystal silicon solar energy battery plate is disassembled the method that resource classification reclaims that realizes.
Background technology
From the nineties in last century, China has set up the small-sized demonstrative project of solar energy in some fields.2002, country solved the electrical problem in Wu electricity township with photovoltaic, and photovoltaic consumption reaches 15.5MWp, has promoted the development of photovoltaic industry.Since two thousand five, the output of China's solar cell develops with annual 100% rate of rise, and continuous 5 annual productions of 2007-2011 rank first in the world.Within 2011, solar cell yield exceedes 20GW, exceedes 50% of global total output.According to industrial development planning, within 2015, reach respectively 20GW and 50GW with the accumulative total installed capacity of the year two thousand twenty China photovoltaic system.
Be 25 years the general service life of solar panel, exceedes after service life, and the transformation efficiency of solar cell can sharply decline, until lost efficacy, scrap.The solar panel that install the nineties in last century will be scrapped in succession.Although it is solar cell, compound semiconductor battery, organic semiconductor battery and Nano semiconductor battery that solar cell comprises silicon.But the early stage solar module overwhelming majority is monocrystalline silicon and polycrystal silicon cell assembly.Therefore how to process and crystal silicon solar energy battery plate from scrapping in reclaim resource and need to merit attention.
Crystal silicon solar energy battery plate forms (see figure 1) by outer rim, glass, encapsulating material, backboard, terminal box and solar cell.Outer rim material is generally aluminium alloy; The glass of battery front side is low iron safety glass; Encapsulating material is generally selected ethylene-vinyl acetate copolymer (EVA); Backboard is polyvinyl fluoride composite membrane (TPT), and TPT haves three layers, and middle one deck is PET (PET), and two-layer is in addition polyvinyl fluoride (PVF, Tedlar film).Multiple monocell sheet soldering group are combined and are called convergent belt, and for connecting the both positive and negative polarity of each cell piece, convergent belt is tin-coated copper strip.The lamination order of whole cell panel is from top to bottom: safety glass, EVA, battery, EVA and backboard, and after lamination completes, surrounding embeds in aluminium frame, and the terminal box at back and convergent belt join and draw the electric current of entire plate, form a complete cell panel.
Solar panel main material composition accounting is in table 1.
Table 1 solar cell plate material summary sheet (kg/KWp) (2012)
| Material | Silicon | Silver | Aluminium | Glass | Copper | Plastics |
| Quality | 3.101 | 0.03 | 12.771 | 54.721 | 0.451 | 17.091 |
Can be found out by Fig. 1 and table 1, in solar panel, each component occurrence status is more single, and the compositions such as aluminium frame, copper, glass have certain recovery value.Based on solar cell plate material occurrence status, set up rational disassembling technology route, not only can solve the processing handling problems of useless solar panel, the high-efficiency cleaning that also can realize resource reclaims.
summary of the invention
The object of this invention is to provide a kind of useless crystal silicon solar energy battery plate method for disassembling and recycling, can realize aluminium frame, safety glass, silicon wafer, aluminium, silver, the copper classification of useless crystal silicon solar energy battery plate and reclaim.
The object of the invention is 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 comprises the following steps:
A, first the crystal silicon solar energy battery plate that will give up is put into airtight firing equipment and is heated, under high temperature, heating can separate aluminum alloy frame, copper cash, cell piece and safety glass completely, the parts of plastics such as backboard change into ashes by heat treatment, and tail gas is emptying after incinerator burning disposal; After equipment to be heated is cooling, sorts out aluminum alloy frame, copper cash and safety glass and recycle;
B, cell piece after above-mentioned steps a heat treatment at room temperature, with dipping by lye, after treating the aluminium paste complete reaction on alkali lye and cell piece surface, obtain aluminum cell sheet, will go aluminum cell sheet to take out, and obtain containing aluminium alkali lye;
The described aluminium alkali lye that contains can repeatedly utilize, and can be used for preparing poly-sodium aluminate product containing aluminium alkali lye;
C, above-mentioned steps b alkali soak the aluminum cell sheet that goes after treatment after cleaning, and soak with acid solution, and the Ag on cell piece surface is leached, and obtain silver battery sheet, will described in go silver battery sheet to take out, obtain argentiferous acid solution;
Described acid solution during up to 500mg/L, adds excessive hydrochloric acid to obtain silver nitride precipitation until Ag concentration after repeatedly utilizing, then obtains silver powder with zinc powder reduction, and Ag is recycled;
D, the above-mentioned steps c acidleach silver battery sheet that goes after treatment, surface is still coated with blue silicon nitride anti-reflection layer, adds hydrofluoric acid solution (HF solution), when question response is completely rear, obtains the cell piece of denitrification SiClx; Cell piece obtains pure silicon wafer after cleaning, and 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 HNO
3solution, its molar concentration is 5 ~ 10mol/L.
the present invention's beneficial effect is compared to existing technology:
1, the method for the invention has improved value-added content of product: after high temperature pyrolysis, can a step obtain aluminum alloy frame, tinned wird and safety glass, can Direct Classification reclaim, recover materials added value improves;
2, comprehensive classification recovery metal and silicon wafer: the alkali of cell piece soaks processing and the classification recovery that has realized respectively aluminium and money kind metal is processed in acidleach, can obtain again pure silicon wafer through HF solution and cleaning;
3, reduced recycling difficulty: obtain aluminium frame, safety glass and the copper cash that can directly recycle by a pyrolysis, then carry out stepwise disposal for cell piece, recovery process is simple, easy to operate feasible;
4, tail gas hazard-free: the tail gas that high-temperature heat treatment process is produced carries out burning disposal, control secondary pollution, has protected environment;
5, reduced reagent consumption: alkali soaks to be processed and acidleach Treatment Solution recycles, and has reduced reagent consumption, has reduced the generation of spent acid, salkali waste, the disposal cost of reduction end refuse;
6, the method for the invention adopts the useless crystal silicon solar energy battery edges of boards frame of method realization, the glass that heat treatment technics combines with chemical method to reclaim and separate with silicon wafer, and valuable metal and silicon wafer recovery.
Below in conjunction with accompanying drawing and case study on implementation, the invention will be further described.
Brief description of the drawings
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 comprises the following steps:
A, first the crystal silicon solar energy battery plate that will give up is put into airtight firing equipment and is heated, under high temperature, heating can separate aluminum alloy frame, copper cash, cell piece and safety glass completely, the parts of plastics such as backboard change into ashes by heat treatment, and tail gas is emptying after incinerator burning disposal; After equipment to be heated is cooling, sorts out aluminum alloy frame, copper cash and safety glass and recycle;
B, cell piece after above-mentioned steps a heat treatment at room temperature, with dipping by lye, after treating the aluminium paste complete reaction on alkali lye and cell piece surface, obtain aluminum cell sheet, will go aluminum cell sheet to take out, and obtain containing aluminium alkali lye;
C, above-mentioned steps b alkali soak the aluminum cell sheet that goes after treatment after cleaning, and soak with acid solution, and the Ag on cell piece surface is leached, and obtain silver battery sheet, will described in go silver battery sheet to take out, obtain argentiferous acid solution;
D, the above-mentioned steps c acidleach silver battery sheet that goes after treatment, surface is still coated with blue silicon nitride anti-reflection layer, adds HF solution, when question response is completely rear, obtains the cell piece of denitrification SiClx; Cell piece obtains pure silicon wafer after ultra-pure water cleans 3 times, through polycrystalline silicon ingot casting machine ingot casting, obtains 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 HNO
3solution, its molar concentration is 5 ~ 10mol/L.
Further, described in step b, can repeatedly utilize containing aluminium alkali lye, can be used for preparing poly-sodium aluminate product containing aluminium alkali lye.
Further, acid solution described in step c during up to 500mg/L, adds excessive hydrochloric acid to obtain silver nitride precipitation until Ag concentration after repeatedly utilizing, then obtains silver powder with zinc powder reduction.
Each raw material described in the present embodiment is the conventional products of selling on market, and the equipment adopting in the present embodiment is also the conventional products of selling on market.
embodiment 2
The present embodiment is the preferredization scheme on the basis of embodiment 1, and useless crystal silicon solar energy battery plate method for disassembling and recycling is provided.The part identical with embodiment 1 in the present embodiment, please refer to disclosed content in embodiment 1 and understands, and the disclosed content of embodiment 1 also should be served as the content of the present embodiment, is not repeated in this description herein.
Described method for disassembling and recycling comprises the following steps:
A, first the crystal silicon solar energy battery plate that will give up is put into airtight firing equipment (the box tempering resistance furnace of RX3 series-18KW) and is heated, 540 DEG C of final temperatures, heat time 3h, aluminum alloy frame, copper cash, cell piece and safety glass can be separated completely, the parts of plastics such as backboard change into ashes by heat treatment, and tail gas is emptying after incinerator burning disposal.After equipment to be heated is cooling, sorts out aluminum alloy frame, copper cash and safety glass and recycle.
Cell piece after b, heat treatment at room temperature, with the excessive dipping by lye 45min of concentration 30%NaOH left and right, after treating the aluminium paste complete reaction on alkali lye and cell piece surface, by going the cell piece after aluminium to take out, obtains containing aluminium alkali lye.Because concentration of lye is high, aluminium amount is low, and therefore alkali lye can be used to repeatedly lixiviate, and the aluminium alkali lye that contains after repeatedly utilizing can be used for preparing poly-sodium aluminate product, is recycled utilization.
C, alkali soak after treatment go aluminum cell sheet through clean after, with concentration be 7mol/L HNO
3solution soaks 40min left and right, and the Ag on cell piece surface is leached, and by going the cell piece after silver to take out, obtains argentiferous acid solution, and acid solution in the time that Ag concentration is high, is recycled Ag after repeatedly utilizing, and obtains containing silver products.
D, the acidleach silver battery sheet that goes after treatment, surface is still coated with blue silicon nitride anti-reflection layer, adds 10% HF solution, and about 20min treats that blueness decorporates completely, while thering is no Bubble formation, obtains the cell piece of denitrification SiClx.Cell piece obtains pure silicon wafer after ultra-pure water cleans 3 times, obtains polycrystal silicon ingot through polycrystalline silicon ingot casting machine ingot casting.
Claims (7)
1. a useless crystal silicon solar energy battery plate method for disassembling and recycling, is characterized in that, described method for disassembling and recycling comprises the following steps:
A, first the crystal silicon solar energy battery plate that will give up is put into airtight firing equipment and is heated, under high temperature, heating can separate aluminum alloy frame, copper cash, cell piece and safety glass completely, the parts of plastics such as backboard change into ashes by heat treatment, and tail gas is emptying after incinerator burning disposal; After equipment to be heated is cooling, sorts out aluminum alloy frame, copper cash and safety glass and recycle;
B, cell piece after above-mentioned steps a heat treatment at room temperature, with dipping by lye, after treating the aluminium paste complete reaction on alkali lye and cell piece surface, obtain aluminum cell sheet, will go aluminum cell sheet to take out, and obtain containing aluminium alkali lye;
C, above-mentioned steps b alkali soak the aluminum cell sheet that goes after treatment after cleaning, and soak with acid solution, and the Ag on cell piece surface is leached, and obtain silver battery sheet, will described in go silver battery sheet to take out, obtain argentiferous acid solution;
D, the above-mentioned steps c acidleach silver battery sheet that goes after treatment, surface is still coated with blue silicon nitride anti-reflection layer, adds HF solution, when question response is completely rear, obtains the cell piece of denitrification SiClx; Cell piece obtains pure silicon wafer after cleaning.
2. useless crystal silicon solar energy battery plate method for disassembling and recycling according to claim 1, is characterized in that, aqueous slkali described in step b is NaOH solution, and its mass concentration is 20% ~ 40%.
3. useless crystal silicon solar energy battery plate method for disassembling and recycling according to claim 1, is characterized in that, acid solution described in step c is HNO
3solution, its molar concentration is 5 ~ 10mol/L.
4. useless crystal silicon solar energy battery plate method for disassembling and recycling according to claim 1, is characterized in that, described in step b, can repeatedly utilize containing aluminium alkali lye, can be used for preparing poly-sodium aluminate product containing aluminium alkali lye.
5. useless crystal silicon solar energy battery plate method for disassembling and recycling according to claim 1, is characterized in that, acid solution described in step c in the time that Ag concentration is high, is recycled Ag after repeatedly utilizing.
6. useless crystal silicon solar energy battery plate method for disassembling and recycling according to claim 5, it is characterized in that, the recovery method of described Ag is, when described Ag concentration is during up to 500mg/L, add excessive hydrochloric acid to obtain silver nitride precipitation, then obtain silver powder with zinc powder reduction.
7. useless crystal silicon solar energy battery plate method for disassembling and recycling according to claim 1, is characterized in that, the silicon wafer finally obtaining in steps d, through polycrystalline silicon ingot casting machine ingot casting, obtains described polycrystal silicon ingot.
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| CN105436191A (en) * | 2015-12-14 | 2016-03-30 | 常州天合光能有限公司 | Recovery method of high-purity silicon in waste solar cells |
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| CN105750297A (en) * | 2016-02-22 | 2016-07-13 | 成都振中电气有限公司 | Solar cell panel recycling device |
| CN106801143A (en) * | 2017-01-22 | 2017-06-06 | 东莞佐佑电子科技有限公司 | A kind of method for reclaiming waste and old solar panel silver |
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