JP2016190177A - Method for recovering valuable material from solar battery panel and processing device for recovering the same - Google Patents
Method for recovering valuable material from solar battery panel and processing device for recovering the same Download PDFInfo
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- 239000004065 semiconductor Substances 0.000 claims abstract description 75
- 229920000642 polymer Polymers 0.000 claims abstract description 61
- 239000011521 glass Substances 0.000 claims abstract description 43
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 229910001220 stainless steel Inorganic materials 0.000 claims description 20
- 239000010935 stainless steel Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 16
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 239000004332 silver Substances 0.000 claims description 12
- 229910001120 nichrome Inorganic materials 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 230000032258 transport Effects 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 3
- 238000003618 dip coating Methods 0.000 claims description 3
- 230000007246 mechanism Effects 0.000 claims description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229940100890 silver compound Drugs 0.000 claims 3
- 150000003379 silver compounds Chemical class 0.000 claims 3
- 239000007788 liquid Substances 0.000 claims 2
- 239000002351 wastewater Substances 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 11
- 238000004064 recycling Methods 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 235000011089 carbon dioxide Nutrition 0.000 abstract 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 21
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 21
- 239000011651 chromium Substances 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
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- 229910021607 Silver chloride Inorganic materials 0.000 description 7
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- 238000007725 thermal activation Methods 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
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- 239000005977 Ethylene Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
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- 239000011019 hematite Substances 0.000 description 2
- 229910052595 hematite Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- -1 CaCO 3 Inorganic materials 0.000 description 1
- 241000257161 Calliphoridae Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- 229910002515 CoAl Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910000943 NiAl Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910004116 SrO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 241000710779 Trina Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 235000013334 alcoholic beverage Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
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- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
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- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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Classifications
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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
-
- 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]
Landscapes
- Processing Of Solid Wastes (AREA)
Abstract
Description
本発明は、太陽電池パネルから有価物を回収する方法及び回収するための処理装置に関する。 The present invention relates to a method for recovering valuable materials from a solar cell panel and a processing apparatus for recovering.
本発明者の一人は有機物、ポリマー、ガス体等の被処理物を分解する方法として、半導体を真性電気伝導領域となる温度に加熱して電子・正孔キャリアーを大量に発生させ、被処理物を加熱処理により発現した強力な酸化力を持つ正孔に接触させ、酸素の存在下において被処理物を完全分解する処理方法（半導体の熱活性法，Ｔｈｅｒｍａｌ Ａｃｔｉｖａｔｉｏｎ ｏｆ Ｓｅｍｉ−Ｃｏｎｄｕｃｔｏｒｓ，以後ＴＡＳＣと略称する）について提案した（特許文献１、非特許文献１）。ＴＡＳＣ法で使用できる半導体は高温、酸素雰囲気で安定な半導体であれば良い。従って、酸化物半導体が好んで用いられる。酸化物半導体の例として、ＢｅＯ、ＣａＯ、ＣｕＯ、Ｃｕ２Ｏ、ＳｒＯ２、ＢａＯ、ＭｇＯ、ＮｉＯ、ＣｅＯ２、ＭｎＯ、ＧｅＯ、ＰｂＯ、ＴｉＯ、ＶＯ、ＺｎＯ、ＦｅＯ、ＰｄＯ、Ａｇ２Ｏ、ＴｉＯ２、ＭｏＯ２、ＰｂＯ２、ＩｒＯ２、ＲｕＯ２、Ｔｉ２Ｏ３、ＺｒＯ２、Ｙ２Ｏ３、Ｃｒ２Ｏ３、ＺｒＯ２、ＷＯ３、ＭｏＯ３、ＷＯ２、ＳｎＯ２、Ｃｏ３Ｏ４、Ｓｂ２Ｏ３、Ｍｎ３Ｏ４、Ｔａ２Ｏ５、Ｖ２Ｏ５、Ｎｂ２Ｏ５、ＭｎＯ３、Ｆｅ２Ｏ３、Ｙ２Ｏ２Ｓ、ＭｇＦｅ２Ｏ４、ＮｉＦｅ２Ｏ４、ＺｎＦｅ２Ｏ４、ＺｎＣｏ２Ｏ４、ＭｇＣｒ２Ｏ４、ＦｅＣｒＯ４、ＣｏＣｒＯ４、ＣｏＣｒＯ４、ＺｎＣｒ２Ｏ４、ＣｏＡｌ２Ｏ４、ＮｉＡｌ２Ｏ４等がある。この中で、酸化クロム（Ｃｒ２Ｏ３）は高温安定性（融点：約２２００℃）に優れ、さらにアルコール飲料等で見られる緑色瓶のガラス染色にも使われる安全な材料である。また、酸化鉄（α−Ｆｅ２Ｏ３：ヘマタイト）は安全で廉価な材料であるので実用性が高い。 One of the inventors of the present invention is a method for decomposing an object to be processed such as an organic substance, a polymer, a gas body, etc., by heating a semiconductor to a temperature that becomes an intrinsic electric conduction region to generate a large amount of electron / hole carriers, Is a treatment method (semiconductor thermal activation of semiconductor-conductors, hereinafter abbreviated TASC). (Patent Document 1, Non-Patent Document 1). A semiconductor that can be used in the TASC method may be a semiconductor that is stable in a high temperature and oxygen atmosphere. Therefore, an oxide semiconductor is preferably used. Examples of oxide semiconductors include BeO, CaO, CuO, Cu 2 O, SrO 2 , BaO, MgO, NiO, CeO 2 , MnO, GeO, PbO, TiO, VO, ZnO, FeO, PdO, Ag 2 O, TiO. 2, MoO 2, PbO 2, IrO 2, RuO 2, Ti 2 O3, ZrO 2, Y 2 O 3, Cr 2 O 3, ZrO 2, WO 3, MoO 3, WO 2, SnO 2, Co 3 O 4 , Sb 2 O 3 , Mn 3 O 4 , Ta 2 O 5 , V 2 O 5 , Nb 2 O 5 , MnO 3 , Fe 2 O 3 , Y 2 O 2 S, MgFe 2 O 4 , NiFe 2 O 4 , ZnFe 2 O 4, ZnCo 2 O 4, MgCr 2 O 4, FeCrO 4, CoCrO 4, CoCrO 4, ZnCr 2 O 4, CoAl 2 O 4, NiAl 2 O 4 Hitoshigaa . Among these, chromium oxide (Cr 2 O 3 ) is excellent in high-temperature stability (melting point: about 2200 ° C.) and is a safe material used for glass dyeing of green bottles found in alcoholic beverages and the like. In addition, iron oxide (α-Fe 2 O 3 : hematite) is a safe and inexpensive material and thus has high practicality.
ＴＡＳＣ法において用いられる酸化物半導体は室温においては絶縁体に近い電気抵抗値を示すが、温度上昇に伴い価電子帯から伝導帯へのバンド間遷移（真性伝導）が顕著になり、３５０−５００℃では価電子帯と伝導帯に、それぞれ、大量の正孔（電子の抜けた孔）と電子が生成される。価電子帯に発生した正孔は強力な酸化力を有し、ポリマー等から結合電子を奪い、ポリマー内に不安定なカチオン・ラジカルを形成させる。次に、このラジカルが被分解物であるポリマー内を伝播することによりポリマー全体を不安定化し、ポリマーは自滅するような形でエチレンのような小分子に裁断化（ラジカル開裂）され、空気中の酸素と反応して水と二酸化炭素に完全分解される。つまり、分解過程は正孔の酸化力によるラジカルの形成、ラジカル開裂によるフラグメント化、そして裁断化された分子と酸素との完全燃焼の３つから構成される。本手法はポリマーの厚みが２０ｍｍ以上でもラジカルの伝播が起こり、被分解物の内部まで分解効果が及ぶのが特徴である。
また、繊維強化プラスチックに同じＴＡＳＣ法を用いて、プラスチックを完全分解し、カーボン・ファイバーやグラス・ファイバー等の強化繊維をほぼ無傷で完全回収する方法を提案した（特許文献２、非特許文献２）。この方法は、強化繊維プラスチック材の強度の源である長繊維を切断することなく、そのままの状態で回収できるので、コスト高のカーボン・ファイバー等のリサイクルには非常に有用である。さらに、強化繊維に限らず、無機物とポリマー等から構成される複合材料から、無機物だけを回収できる普遍性のある方法である。
An oxide semiconductor used in the TASC method exhibits an electrical resistance value close to that of an insulator at room temperature. However, an interband transition (intrinsic conduction) from a valence band to a conduction band becomes remarkable as the temperature rises, and 350-500 At ℃, a large number of holes (holes from which electrons have been released) and electrons are generated in the valence band and the conduction band, respectively. The holes generated in the valence band have a strong oxidizing power, take away the bonding electrons from the polymer or the like, and form unstable cation radicals in the polymer. Next, this radical propagates in the polymer that is the decomposition product, destabilizing the entire polymer, and the polymer is cut into small molecules such as ethylene (radical cleavage) in a form that self-destructs, and in the air Reacts with oxygen and completely decomposes into water and carbon dioxide. In other words, the decomposition process consists of the formation of radicals by the oxidizing power of holes, fragmentation by radical cleavage, and complete combustion of the cut molecules and oxygen. This technique is characterized in that radical propagation occurs even when the thickness of the polymer is 20 mm or more, and the decomposition effect reaches the inside of the decomposition target.
In addition, the same TASC method is used for fiber-reinforced plastics, and a method of completely disassembling the plastics and completely recovering the reinforcing fibers such as carbon fibers and glass fibers without damage is proposed (Patent Document 2, Non-Patent Document 2). ). This method is very useful for recycling high-cost carbon fibers and the like because it can be recovered as it is without cutting the long fibers that are the source of strength of the reinforcing fiber plastic material. Furthermore, it is a universal method capable of recovering not only the reinforcing fiber but also the inorganic material from the composite material composed of the inorganic material and the polymer.
太陽光発電システムは燃料を必要としないので資源枯渇の心配がなく、クリーンなエネルギーを供給して環境に負荷を与えない有用な技術であり、最近急速に普及が進展している。太陽電池システムの主要構成要素である太陽電池パネルの耐用年数は２０−３０年と言われ、今後大量の処理需要の発生が見込まれる。太陽電池パネルの部品をそのまま再使用するリユースはコスト面から経済性に乏しく、不要部材を処理して有価物である強化ガラス、太陽電池セル、インター・コネクタなどを素材として回収するリサイクル技術の確立が望まれている。 Solar power generation systems do not require fuel, so there is no concern about resource depletion, and they are a useful technology that supplies clean energy and does not give an impact to the environment. The service life of solar cell panels, which are the main components of the solar cell system, is said to be 20-30 years, and a large amount of processing demand is expected in the future. Reuse of solar panel components as they are is not economical from a cost standpoint. Establish recycling technology to process unnecessary materials and recover valuable materials such as tempered glass, solar cells, and inter-connectors. Is desired.
しかしながら、現状の太陽電池モジュールの大部分は、セル部とガラス基板が、例えば、熱可塑型の樹脂であるＥＶＡ（エチレン酢酸ビニル共重合樹脂：エチレンビニルアセテート）により接着された構造となっている。ＥＶＡはセルが大気にさらされて腐食することなどを防いでいるが、逆にセル部やガラスを分離して取り出そうとすると、ＥＶＡを効率的に除去する方法がないために取り出しが困難であり、リサイクル技術は実用化されていないのが実情である。一般にポリマーを室温・空気中で加熱分解すると燃焼方法にも依存するが、多くの炭化物等に由来する黒状残渣が残存することが知られている。 However, most of the present solar cell modules have a structure in which the cell portion and the glass substrate are bonded by, for example, EVA (ethylene vinyl acetate copolymer resin: ethylene vinyl acetate) which is a thermoplastic resin. . EVA prevents the cell from being exposed to the atmosphere and corroded, but conversely, if the cell part or glass is separated and taken out, it is difficult to take out because there is no way to remove EVA efficiently. In fact, recycling technology has not been put to practical use. Generally, it is known that when a polymer is thermally decomposed at room temperature and in air, a black residue derived from many carbides or the like remains, depending on the combustion method.
ＥＶＡを除去して太陽電池素子構成材料の回収をするための方法として、特開２０１４−１０８３７５号には、炉内酸素濃度が１〜３体積％、装置炉内の温度を「予備加熱部：３００℃」「熱処理部：５００℃」となる様に昇温し、「予備加熱部滞在時間：２０分」「熱処理部滞在時間：２０分」となる周回コンベアの回転速度を合わせる。結晶Ｓｉ系パネルを連続処理装置に入れて、セル部及びガラス基板に結合したＥＶＡ封止材を爆発現象や炭化を起こすことなく除去して、太陽電池素子の構成材料を、安全に低コストで回収できる、と記載されている。爆発を抑制するためには酸素濃度を下げることが好ましいが、これはポリマーの炭化を促進することにつながり、処理速度が低下する等の問題点が残る。また、特開２００４−４２０３３号には従来の硝酸浸漬法を改良し、太陽電池パネルを浸漬する７０℃以上８０℃以下に加温した硝酸に界面活性剤を添加することにより、従来１００時間かかっていたＥＶＡの分解時間を約半分の５０時間に短縮することができた、と記載されている。処理中にセルが割れることなく回収できる利点はあるものの、処理時間が依然として長く、更に強酸を用いるなどから実用的とは言えない。さらに、塩素系溶剤として知られるトリクロール・エチレン（通称トリクレン）を８０℃に加熱し、１０日間浸漬する方法も報告されている（非特許文献３）。しかし、塩素系溶剤の使用、ならびに加熱自体が環境負荷となる。 As a method for recovering the solar cell element constituent material by removing EVA, Japanese Patent Application Laid-Open No. 2014-108375 discloses that the oxygen concentration in the furnace is 1 to 3% by volume and the temperature in the apparatus furnace is “preheating part: The temperature is raised to 300 ° C. and “heat treatment part: 500 ° C.”, and the rotational speed of the circulating conveyor is adjusted to be “preheating part stay time: 20 minutes” and “heat treatment part stay time: 20 minutes”. Put the crystalline Si panel in the continuous processing equipment and remove the EVA sealing material bonded to the cell part and the glass substrate without causing an explosion phenomenon or carbonization, so that the constituent material of the solar cell element can be safely and at low cost. It is described that it can be recovered. In order to suppress the explosion, it is preferable to reduce the oxygen concentration. However, this leads to promotion of carbonization of the polymer, and problems such as a reduction in processing speed remain. JP-A-2004-42033 improves the conventional nitric acid dipping method, and by adding a surfactant to nitric acid heated to 70 ° C. or higher and 80 ° C. or lower for dipping the solar cell panel, it takes 100 hours conventionally. It is described that the degradation time of EVA that had been reduced could be reduced to about half of 50 hours. Although there is an advantage that the cells can be recovered without cracking during the treatment, the treatment time is still long, and further, it is not practical because a strong acid is used. Furthermore, a method in which trichlorethylene (commonly known as trichlene) known as a chlorine solvent is heated to 80 ° C. and immersed for 10 days has been reported (Non-patent Document 3). However, the use of chlorinated solvents and heating itself are environmental loads.
また、太陽電池モジュールを処理するための前処理としてＡｌ製などの外枠のついた状態の太陽電池パネルから外枠を外す作業が必要であるが、特開２０１４−１１６３６３号公報には、太陽電池パネルをクランプ部により固定した状態で、フレームに対して内側から外側に押圧された状態のヘッド部を太陽電池パネルの外周に沿って走行させると、この太陽電池パネルの外周に沿ってフレームが引き剥がされると記載されている。機械的な力により強引に引きはがすので、コストと手間がかかる手法である。実用化されている方法においても機械的な力で引きはがす方法が採用されている（非特許文献４）。
そこで、外枠の取外しとＥＶＡの除去に、本出願の方法である「半導体の熱活性技術（ＴＡＳＣ）」を適用するならば、ＴＡＳＣ法はポリマーを水と二酸化炭素に完全分解するクリーンな技術であるので、太陽電池パネルから有価物であるガラス、太陽電池セル、インター・コネクタなどを容易にかつ安価に回収するシステムを構築しうる。
Moreover, although the operation | work which removes an outer frame from the solar cell panel with the outer frame of Al etc. as a pre-process for processing a solar cell module is required, JP, 2014-116363, A With the battery panel fixed by the clamp part, when the head part pressed from the inside to the outside with respect to the frame is run along the outer periphery of the solar cell panel, the frame moves along the outer periphery of the solar cell panel. It is described as being peeled off. This method is costly and troublesome because it is forcibly removed by mechanical force. Even in a method that has been put to practical use, a method of peeling by mechanical force is employed (Non-Patent Document 4).
Therefore, if the “thermal activation technology of semiconductor (TASC)” which is the method of the present application is applied to the removal of the outer frame and the removal of EVA, the TASC method is a clean technology that completely decomposes the polymer into water and carbon dioxide. Therefore, it is possible to construct a system that easily and inexpensively collects glass, solar battery cells, inter-connectors, and the like that are valuable materials from the solar battery panel.
前述したように、太陽電池パネルのリサイクルにおいては、パネルから外枠を取り外す簡便な方法がなく、太陽電池素子のＥＶＡ等のポリマーを除去することが困難であり、太陽電池素子構成材料の回収の実用化を妨げていた。この問題を半導体の熱活性法（ＴＡＳＣ）で解決し、太陽電池パネル中のＥＶＡ等のポリマーを完全分解して、外枠を取り外すと共に有価物である外枠、ガラス、太陽電池セル、インター・コネクタなどを回収する方法を提供することを課題とする。また、太陽電池セルを構成するシリコン・ウェーファーと金属電極を分別して回収する方法を提供することを課題とする。 As described above, in the recycling of solar cell panels, there is no simple method for removing the outer frame from the panel, and it is difficult to remove polymers such as EVA of the solar cell elements, and the recovery of the solar cell element constituent materials is difficult. It was hindering practical use. This problem is solved by the semiconductor thermal activation method (TASC), the polymer such as EVA in the solar panel is completely decomposed, the outer frame is removed and the valuable outer frame, glass, solar cell, inter- It is an object of the present invention to provide a method for collecting a connector or the like. It is another object of the present invention to provide a method for separating and collecting a silicon wafer and a metal electrode constituting a solar battery cell.
本発明においては、半導体の熱活性技術（ＴＡＳＣ）を太陽電池パネルの解体に適用し、被処理物である太陽電池パネルの表面に太陽電池パネルの外枠がついたままの状態で、酸化物半導体を接触させ、酸素存在下において、酸化物半導体が真性電気伝導領域となる温度で被処理物を加熱することにより、ＥＶＡ等のポリマーを完全分解して有価物である外枠、ガラス、太陽電池セル、インター・コネクタを回収する。回収した太陽電池セルから銀電極を濃硝酸で溶解し、これに塩酸を滴下してＡｇＣｌとして回収して、さらに残ったシリコン・ウェーファーを分別・回収する。 In the present invention, the semiconductor thermal activation technology (TASC) is applied to the disassembly of the solar cell panel, and the surface of the solar cell panel that is the object to be processed is still attached with the outer frame of the solar cell panel. A semiconductor is brought into contact, and in the presence of oxygen, the object to be processed is heated at a temperature at which the oxide semiconductor becomes an intrinsic electric conduction region, thereby completely decomposing a polymer such as EVA, which is a valuable material such as an outer frame, glass, solar Collect battery cells and inter-connectors. The silver electrode is dissolved with concentrated nitric acid from the collected solar cells, and hydrochloric acid is added dropwise to collect it as AgCl, and the remaining silicon wafer is separated and collected.
太陽電池パネルは、電極を介して相互に接続された太陽電池セルの受光面側に強化ガラスが配置され、太陽電池セルの周辺部分がＥＶＡ等のポリマーによって密封充填され、有機物フィルムからなるバック・シートがＥＶＡ等のポリマーの裏面側に接着された構造の太陽電池モジュールに外枠が取り付けられている。
本発明者は、このような太陽電池パネルからＥＶＡ等のポリマーを完全分解して除去し、有価物を回収するために、鋭意実験を重ね、以下の経緯を経て本発明に至った。
ＴＡＳＣ法によるポリマーの分解は、前述したように、正孔の酸化により生成したラジカルがポリマーから結合電子を奪い、ポリマーを不安定化して小分子に裁断されるプロセスである。ラジカルは２０ｍｍ以上でも伝播すると述べたが、本課題ではラジカルがどの程度ポリマー内を伝播できるかが、問題解決の鍵となる。
上述した太陽電池モジュールの構造から判断すると、仮に、底部のバック・シートに酸化物半導体を接触させたとすると、バック・シートの上には（無機物である）太陽電池セルが一面に張り巡らされているため、ラジカルの伝播はここで途切れてしまい、太陽電池セルとガラスの界面まで及ばないと想定した。そこで、太陽電池パネルから外枠を含まないように太陽電池モジュール片（１２０×１２０×５ｍｍ）を切り出し、モジュール片の横方向の４辺に酸化物半導体の分散膜を塗布し、ラジカルを横方向に走らせる実験を行った。当初は２０ｍｍをはるかに超える６０ｍｍまでラジカルが走破するとは見通せなかったが、実際のＴＡＳＣ処理の結果、驚くべきことに、太陽電池モジュールはバック・シートを含め、総てのポリマーは完全分解され、モジュール片からガラス、シリコン・ウェーファー、インター・コネクタが分離回収され、ポリマーに充填されていた無機物も残渣として回収できた。
In the solar panel, a tempered glass is disposed on the light receiving surface side of the solar cells connected to each other through electrodes, and the peripheral portion of the solar cell is hermetically filled with a polymer such as EVA, and is formed of an organic film. An outer frame is attached to a solar cell module having a structure in which a sheet is bonded to the back side of a polymer such as EVA.
The present inventor has conducted extensive experiments in order to completely decompose and remove polymers such as EVA from such a solar cell panel and recover valuable materials, and has reached the present invention through the following processes.
As described above, the decomposition of the polymer by the TASC method is a process in which radicals generated by hole oxidation deprive the polymer of bond electrons, destabilize the polymer and cut into small molecules. Although it has been stated that radicals propagate even when they are 20 mm or more, the extent to which radicals can propagate in the polymer is the key to solving the problem.
Judging from the structure of the solar cell module described above, if an oxide semiconductor is brought into contact with the bottom back sheet, solar cells (which are inorganic) are stretched over the back sheet. Therefore, it was assumed that the propagation of radicals was interrupted here and did not reach the interface between the solar cell and the glass. Therefore, a solar cell module piece (120 × 120 × 5 mm) is cut out from the solar cell panel so as not to include the outer frame, an oxide semiconductor dispersion film is applied to the four sides of the module piece in the lateral direction, and the radicals are laterally distributed. An experiment was carried out. Initially, radicals could not be expected to run to 60 mm, much more than 20 mm, but as a result of the actual TASC treatment, surprisingly, the solar cell module, including the back sheet, all polymers were completely decomposed, Glass, silicon wafer, and interconnector were separated and collected from the module piece, and the inorganic substance filled in the polymer could also be collected as a residue.
さらに驚くべきことは、モジュール片４辺のコーティングを３辺、２辺、１辺としても全く同じ結果が得られたことである。つまり、ラジカルはパネルの１２０ｍｍ四方の面内でも十分に伝播していたことが確認された。この結果を踏まえて、モジュール片のバック・シートを、酸化物半導体を担持したハニカムの上に載せてＴＡＳＣ処理を施したところ、すべてのポリマーは完全分解され、モジュールからガラス、シリコン・ウェーファー、インター・コネクタが分離回収することができた。結果として、ラジカルはバック・シートの上に全面に並べられた太陽電池セルの間の僅かなスペースを通してガラス面にまで伝播し、充填されていたポリマーを完全分解することがわかった。モジュールのバック・シートを、酸化物半導体を担持したハニカムの上に載せてＴＡＳＣ処理を施す手法はバック・シートを下にして、パネル片を単に触媒担持ハニカムの上に置くだけの操作であるので、酸化物半導体の塗布工程も必要なく、さらに酸化物半導体の粉が回収物に混入することがない最もクリーンな処理方法である。以上の結果から、モジュールが部分的に酸化物半導体と接触しているだけで、接触点でラジカルが生成し、これがモジュール全体に伝播して、すべてのポリマーを分解することがわかったので、次にＡｌ外枠がついた状態のままの太陽光パネルの４隅の内の一か所から１２０ｍｍ四方を切りだし、バック・シートを、酸化物半導体を担持したハニカムの上に載せてＴＡＳＣ処理を施したところ、すべてのポリマーは完全分解され、外枠、ガラス、シリコン・ウェーファー、インター・コネクタを分離回収することができた。外枠とモジュールは有機物を介してのりづけされる形で結合されているので、外枠を取り外すには強力な力を必要とするが、ＴＡＳＣ処理により容易に分離回収できることが確認でき、本発明は完成した。 What is more surprising is that the same result was obtained even when the coating on the four sides of the module piece was made of three sides, two sides and one side. That is, it was confirmed that radicals were sufficiently propagated even in a 120 mm square surface of the panel. Based on this result, when the back sheet of the module piece was placed on the honeycomb supporting the oxide semiconductor and subjected to TASC treatment, all the polymers were completely decomposed, and from the module to the glass, silicon wafer, The inter connector was able to separate and collect. As a result, it was found that the radical propagates to the glass surface through a small space between the solar cells arranged on the entire surface of the back sheet and completely decomposes the filled polymer. The method of placing the module back sheet on the honeycomb supporting the oxide semiconductor and performing the TASC process is simply placing the panel piece on the catalyst supporting honeycomb with the back sheet down. This is the cleanest processing method that does not require an oxide semiconductor coating step and that the oxide semiconductor powder does not enter the recovered material. From the above results, it was found that radicals were generated at the contact points only when the module was only partially in contact with the oxide semiconductor, which propagated throughout the module and decomposed all the polymers. A 120mm square is cut out from one of the four corners of the solar panel with the Al outer frame attached to it, and the back sheet is placed on the honeycomb supporting the oxide semiconductor and subjected to TASC treatment. As a result, all the polymers were completely decomposed, and the outer frame, glass, silicon wafer, and interconnector could be separated and recovered. Since the outer frame and the module are bonded together through an organic substance, a strong force is required to remove the outer frame, but it can be confirmed that it can be easily separated and recovered by the TASC process. Is completed.
すなわち、本発明に係る太陽電池パネルから有価物を回収する方法は、被処理物である太陽電池パネルを、前記太陽電池パネルの外枠がついたままの状態で、前記太陽電池パネルのバック・シートに酸化物半導体を接触させ、酸素存在下において、前記酸化物半導体が真性電気伝導領域となる温度で前記被処理物を加熱することにより、前記被処理物中のポリマーを分解除去し、解体物から有価物を回収することを特徴とする。 That is, the method for recovering valuable materials from the solar cell panel according to the present invention includes a solar cell panel, which is an object to be processed, with the outer frame of the solar cell panel still attached. An oxide semiconductor is brought into contact with the sheet, and in the presence of oxygen, the object to be processed is heated at a temperature at which the oxide semiconductor becomes an intrinsic electric conduction region, whereby the polymer in the object to be processed is decomposed and disassembled. It is characterized by recovering valuable materials from the materials.
また、本発明に係る太陽電池パネルから有価物を回収するための処理装置は、被処理物である太陽電池パネルを、前記太陽電池パネルの外枠がついたままの状態で、前記太陽電池パネルのバック・シートに酸化物半導体を接触させながら搬送する搬送装置と、前記被処理物を、前記酸化物半導体が真性電気伝導領域となる温度以上に加熱する加熱処理部と、前記加熱処理部内にエアを供給するエアの供給機構と、前記加熱処理部において前記被処理物中のポリマーを分解除去して得られる解体物から、有価物を回収する回収部とを備えることを特徴とする。
また、前記解体物から有価物を回収する回収部において、まず外枠を回収し、次にガラスを回収し、次に太陽電池セルおよびインター・コネクターを回収することにより、分別・回収することを特徴とする。
Moreover, the processing apparatus for recovering valuable materials from the solar cell panel according to the present invention is configured such that the solar cell panel that is the object to be processed is attached to the solar cell panel with the outer frame of the solar cell panel still attached. A conveying device that conveys the oxide semiconductor in contact with the back sheet, a heat treatment unit that heats the object to be processed to a temperature at which the oxide semiconductor becomes an intrinsic electric conduction region, and a heat treatment unit. An air supply mechanism that supplies air, and a recovery unit that recovers valuable materials from a dismantled product obtained by decomposing and removing the polymer in the object to be processed in the heat processing unit.
In the collection section for collecting valuable materials from the dismantled material, the outer frame is first collected, then the glass is collected, and then the solar cells and the inter-connectors are collected to be separated and collected. Features.
本発明によれば、太陽電池パネルを半導体の熱活性法（ＴＡＳＣ）で処理することにより、有機物であるＥＶＡ等のポリマーを完全分解して除去することができるので、解体物から有価物である外枠、ガラス、太陽電池セル、インター・コネクタを低コストで短時間に回収することができる。また、ＥＶＡ等のポリマーを完全分解、除去することにより、廃物サイズの縮小という効果も得られる。さらに、酸処理により太陽電池セルから銀とシリコン・ウェーファーを分別して回収できる。 According to the present invention, by treating a solar cell panel with a semiconductor thermal activation method (TASC), a polymer such as EVA that is an organic substance can be completely decomposed and removed, so that it is a valuable resource from a dismantled product. The outer frame, glass, solar battery cell, and inter-connector can be collected in a short time at a low cost. Further, by completely decomposing and removing a polymer such as EVA, an effect of reducing the waste size can be obtained. Furthermore, silver and silicon wafers can be separated and recovered from solar cells by acid treatment.
太陽電池は使用できる最小の単位であるセルをつなぎ合わせ、ガラスやポリマーで保護したものを太陽電池モジュールと呼び、太陽電池モジュールをアルミニウム製などの枠に入れてパネル状にしたものを太陽電池パネルと呼んでいる。さらに太陽電池パネルを並べたものは太陽電池アレイと呼ばれている。家の屋根等に設置されているものは太陽電池アレイである。本願における処理単位は、使用寿命を終えた太陽電池パネルまたは製造過程で不良品となった太陽電池パネルである。
単結晶または多結晶のシリコンからなる太陽電池セルは、ｐ型のシリコン・ウェーファーの上部にｎ型シリコン層を形成し、さらに電極等を配置したものである。太陽電池セル３は図１に示すように、金属のインター・コネクタ４により電極が相互に接続され、端子６を通して外部の電極に接続されている。太陽電池セル３の受光面側には３−５ｍｍ程度の厚さの強化ガラス２が配置される。結合された太陽電池セル３の周辺はＥＶＡ等のポリマー４で密閉充填される。その後、バック・シート７がＥＶＡ等のポリマー５に接着される。バック・シート７は様々な性能をもつ有機物フィルムである。Ａｌ製などの外枠１は有機物である接着剤によって太陽電池モジュール８の外側に固定されている。
A solar cell is the smallest unit that can be used by connecting cells together and protected by glass or polymer. This is called a solar cell module, and the solar cell module is put into a panel made of aluminum or other material. It is called. Furthermore, the array of solar cell panels is called a solar cell array. What is installed on the roof of a house is a solar cell array. The processing unit in the present application is a solar cell panel that has finished its service life or a solar cell panel that has become defective during the manufacturing process.
A solar battery cell made of monocrystalline or polycrystalline silicon is formed by forming an n-type silicon layer on a p-type silicon wafer and further arranging electrodes and the like. As shown in FIG. 1, the solar cells 3 are connected to each other by metal interconnectors 4 and are connected to external electrodes through terminals 6. A tempered glass 2 having a thickness of about 3-5 mm is disposed on the light receiving surface side of the solar battery cell 3. The periphery of the combined solar cells 3 is hermetically filled with a polymer 4 such as EVA. Thereafter, the back sheet 7 is adhered to a polymer 5 such as EVA. The back sheet 7 is an organic film having various performances. The outer frame 1 made of Al or the like is fixed to the outside of the solar cell module 8 with an adhesive that is an organic substance.
太陽電池パネル９から太陽電池セル３等を回収するためには、まず太陽電池パネル９を太陽電池パネル９の外枠１がついたままの状態で、電気炉１２内で、空気中５００℃で２０−３０分間Ｃｒ２Ｏ３等の酸化物半導体１６と接触させ、ポリマー成分（フレームとパネルを固定するポリマー、充填物としてのＥＶＡ等のポリマー５、下地のバック・シート７、外枠の接着剤など）を完全分解し、パネル片を完全解体する。太陽電池パネル９に酸化物半導体１６を接触させる方法としては、酸化物半導体をコーティングしたハニカム１０（触媒担持ハニカム）上に、太陽電池パネル９をパネルのバック・シート７を下（つまり、受光面を上）に置く方法、太陽電池パネルのバック・シートに酸化物半導体１６を付着させる方法、酸化処理されて表面が酸化クロムになっているニクロム線を太陽電池パネルのバック・シートに接触させる方法のいずれかを用いることができる。さらに、太陽電池パネルのバック・シートに酸化物半導体１６を付着させる方法には、酸化物半導体１６の懸濁液にディップ・コーティングする方法または酸化物半導体１６の分散液をスプレーする方法や、筆などで塗布する方法がある。図１は半導体坦持ハニカム１０上に太陽電池パネル９を、バック・シート７が半導体酸化物１６に接触するように置いた場合を示している。ハニカムは通気性のある支持体で代替することができる。本発明において、通気性を有する支持体とは、多孔質状あるいはハニカム状の良好な通気性を有する支持体を意味する。ＴＡＳＣ法では裁断化された分子を水と炭酸ガスに完全分解するには十分な酸素が必要であり、被処理物を通気性の高い支持体上に支持して処理する方法が効果的である。 In order to recover the solar battery cells 3 and the like from the solar battery panel 9, first, the solar battery panel 9 is left in the electric furnace 12 with the outer frame 1 of the solar battery panel 9 attached, at 500 ° C. in the air. Contact with oxide semiconductor 16 such as Cr 2 O 3 for 20-30 minutes, polymer component (polymer for fixing frame and panel, polymer 5 such as EVA as filler, back sheet 7 of base, adhesion of outer frame Completely disassemble the agent, etc., and disassemble the panel piece completely. As a method of bringing the oxide semiconductor 16 into contact with the solar cell panel 9, the solar cell panel 9 is placed under the back sheet 7 of the panel (that is, the light receiving surface) on the honeycomb 10 (catalyst carrying honeycomb) coated with the oxide semiconductor. ), A method of attaching the oxide semiconductor 16 to the back sheet of the solar cell panel, and a method of bringing the nichrome wire, which has been oxidized and whose surface is chromium oxide, into contact with the back sheet of the solar cell panel Either of these can be used. Furthermore, the oxide semiconductor 16 can be attached to the back sheet of the solar cell panel by a method of dip-coating the oxide semiconductor 16 suspension, a method of spraying a dispersion of the oxide semiconductor 16, or a brush. There is a method of applying by, for example. FIG. 1 shows a case where a solar cell panel 9 is placed on a semiconductor-supporting honeycomb 10 so that the back sheet 7 is in contact with the semiconductor oxide 16. The honeycomb can be replaced by a breathable support. In the present invention, the air permeable support means a porous or honeycomb support having good air permeability. In the TASC method, sufficient oxygen is necessary to completely decompose the cut molecules into water and carbon dioxide gas, and a method of supporting an object to be treated on a highly breathable support is effective. .
処理後のパネルは外枠が外れて四方を取り囲むように残り、熱強化ガラス２がひび割れている状態になっているので、まず外枠１を回収する。次いでガラス２、太陽電池セル３、インター・コネクタ４、残渣等を効率良く分離するために外枠１を回収後の太陽電池パネル９を網目のあるステンレス網１７の上に移すと良い。ステンレス網１７を傾け、低周波数で振動させると、ポリマーに含有されていた無機物の白い残渣はメッシュを通して落下し、ガラス２塊、太陽電池セル３、インター・コネクタ４はステンレス網１７を滑り落ちることにより、分別回収することができる。酸化物半導体担持ハニカム１０の上に太陽電池パネル９を置く場合は、ハニカムに予め溝１８を設け、ステンレス網１７をはめ込んでおけば、ステンレス網１７上の残渣物をハニカムからとり外すことがより容易になるので好ましい。 The treated panel remains so that the outer frame is removed and surrounds the four sides, and the heat strengthened glass 2 is in a cracked state, so the outer frame 1 is first recovered. Next, in order to efficiently separate the glass 2, the solar battery cell 3, the inter-connector 4, the residue and the like, the solar battery panel 9 after the outer frame 1 is recovered may be moved onto a meshed stainless steel mesh 17. When the stainless steel mesh 17 is tilted and vibrated at a low frequency, the white residue of the inorganic substance contained in the polymer falls through the mesh, and the glass 2 lump, the solar cell 3 and the inter connector 4 slide down the stainless steel mesh 17. Can be collected separately. In the case where the solar cell panel 9 is placed on the oxide semiconductor supporting honeycomb 10, it is possible to remove the residue on the stainless steel mesh 17 from the honeycomb by previously providing the groove 18 with the stainless steel mesh 17. Since it becomes easy, it is preferable.
このようにして、太陽電池パネル９にＴＡＳＣ処理を施した後の解体物から、容易に外枠１、耐熱ガラス２、太陽電池セル３、インター・コネクタ４が図２に示すように回収される。
回収した太陽電池セル２の受光面には格子状の銀電極、裏面にはＡｌの電極が全面に形成されている。この内、高価な銀は、まず濃硝酸液で溶解し、次に、塩酸を滴下して、塩化物（ＡｇＣｌ）として単離する。その後、塩化銀を還元して銀を回収する。残ったシリコン・ウェーファーはメタル・フリーのシリコン基板として回収される。
In this manner, the outer frame 1, the heat-resistant glass 2, the solar battery cell 3, and the inter connector 4 are easily recovered from the dismantled product after the TASC treatment is performed on the solar battery panel 9, as shown in FIG. .
A grid-like silver electrode is formed on the light receiving surface of the collected solar battery cell 2 and an Al electrode is formed on the entire back surface. Of these, expensive silver is first dissolved in concentrated nitric acid solution, and then hydrochloric acid is added dropwise to isolate it as chloride (AgCl). Thereafter, silver chloride is reduced to recover silver. The remaining silicon wafer is collected as a metal-free silicon substrate.
太陽電池パネル９から外枠１、耐熱ガラス２、太陽電池セル３、インター・コネクタ４を回収する実用的な方法としては、連続処理装置を用いるのが良い。これは太陽電池パネル９が搬送される搬送装置上に、搬入部、予備加熱部、加熱処理部、冷却部、搬出部、分別回収部を連結して備える。ハニカム上に置かれた太陽電池パネル９は搬送部から搬入され、加熱処理部にてＴＡＳＣ処理が行われ、搬出部から搬出されて、分別回収部で外枠１、耐熱ガラス２、太陽電池セル３、インター・コネクタ４が分別回収される。 As a practical method for recovering the outer frame 1, the heat-resistant glass 2, the solar battery cell 3, and the inter connector 4 from the solar battery panel 9, it is preferable to use a continuous processing apparatus. This is provided with a carry-in part, a preheating part, a heat treatment part, a cooling part, a carry-out part, and a separation / recovery part connected to a transport device on which the solar cell panel 9 is transported. The solar battery panel 9 placed on the honeycomb is carried in from the transport section, subjected to TASC processing in the heat treatment section, unloaded from the carry-out section, and separated in the separation and recovery section, the outer frame 1, the heat resistant glass 2, and the solar battery cell. 3. The inter connector 4 is collected separately.
連続処理装置１９において搬入部、搬出部及び分別回収部では太陽電池パネル９を載せたハニカム１０を一定速度で連続的に搬送し、予備加熱部、加熱処理部及び冷却部を一体化したＴＡＳＣ処理室では停止状態でＴＡＳＣ処理を行うシステムでもよい。 In the continuous processing apparatus 19, the carry-in unit, the carry-out unit, and the separation and recovery unit continuously transport the honeycomb 10 on which the solar cell panel 9 is placed at a constant speed, and integrate the preheating unit, the heating unit, and the cooling unit. The room may be a system that performs TASC processing in a stopped state.
実施例１
Ｃｈａｎｇｚｈｏｕ Ｔｒｉｎａ Ｓｏｌａｒ Ｅｎｅｒｇｙ Ｃｏ． Ｌｔｄ．製の太陽電池パネル（型式：ＴＳＭ−０５ＤＣ８０．０８）を用いて実験を行った。まず、約８００×１６００×４０ｍｍの大きさの太陽電池パネルからＡｌ製の外枠１がついたままの状態で４隅の内の一か所をダイヤモンド・カッターで切断し、１２０×１２０×４０ｍｍの太陽電池パネル９の１片を切り出し、ＴＡＳＣ処理の解体試料とした。太陽電池パネル９から外枠１を除いた太陽電池モジュール８の上面は約３．５ｍｍのガラス２板、最下面には約０．５ｍｍ程度の充填剤の入った白色のポリマー・シート（バック・シート７）があり、ガラス２板とポリマー・シートの中間には太陽電池セルを保護する約１ｍｍ程度の透明の樹脂層があった。この太陽電池パネル９はＡｌ製の外枠１と太陽電池モジュール８の固定には、太陽電池モジュール８の１片のベース体と同じポリマー・バインダーが使用されていた。
Example 1
Changzhou Trina Solar Energy Co. Ltd .. An experiment was performed using a solar cell panel (model: TSM-05DC80.08). First, from a solar cell panel having a size of about 800 × 1600 × 40 mm, with the outer frame 1 made of Al still attached, one of the four corners was cut with a diamond cutter, and 120 × 120 × 40 mm A piece of the solar cell panel 9 was cut out and used as a dismantled sample for TASC treatment. The upper surface of the solar cell module 8 excluding the outer frame 1 from the solar cell panel 9 is a glass plate of about 3.5 mm, and a white polymer sheet (back back) containing about 0.5 mm of filler on the lowermost surface. There was a sheet 7), and there was a transparent resin layer of about 1 mm protecting the solar battery cell between the two glass plates and the polymer sheet. In this solar cell panel 9, the same polymer binder as that of the single base body of the solar cell module 8 was used for fixing the outer frame 1 made of Al and the solar cell module 8.
太陽電池パネル９の１片のバック・シート７を下にして、酸化物半導体１６としてＣｒ２Ｏ３をコーティングしたコージライト（２ＭｇＯ・２Ａｌ２Ｏ３・５ＳｉＯ２）組成のハニカム１０上に載せた。酸化物半導体１６はＴＡＳＣ処理においてそれ自体は変化・消耗することなく、これに接触している被処理物中の有機物を分解・除去する作用をするので、酸化物半導体１６を担持したハニカム１０は触媒担持ハニカムとも称する。太陽電池パネル５の１片を載せた触媒担持ハニカム１０を図３の電気炉１２に入れて、空気導入口１４から空気を導入しながらヒーター１３に通電して５００℃まで昇温し、３０分間５００℃に制御した。この後温度制御の電源をオフにして冷却した。以上の一連のＴＡＳＣ処理により、Ａｌ外枠１を固定する接着剤ポリマー、パネル片のバック・シート７および充填剤を構成するポリマーは完全に分解され、外枠１はモジュール片から外れて分離されており、モジュール片部分からは下層から順に、インター・コネクタ４／太陽電池セル３／インター・コネクタ４、さらに細かくひび割れしたガラス１塊が得られた。分解されたポリマーは水と炭酸ガスとなり、空気排気口１５から排出される。酸化物半導体１６（Ｃｒ２Ｏ３）と太陽電池パネル９はバック・シート７表面でのみ接触しているが、酸化物半導体１６に発現する酸化力により、バック・シート７表面でポリマーから結合電子を奪い、ポリマー内に不安定なカチオン・ラジカルが形成される。このラジカルが被分解物であるポリマー内を伝播することによりポリマー全体を不安定化し、ポリマーは自滅するような形でエチレンのような小分子に裁断化（ラジカル開裂）され、空気中の酸素と反応して水と二酸化炭素に完全分解される。これがＴＡＳＣ法の特徴である。つまり、ポリマー表面でラジカルが一度形成されると、厚み方向に次々に分解反応が続くので、充填剤の領域まで完全分解が実現する。
実験は１２０×１２０×５ｍｍの太陽電池モジュール片で行ったが、以上で述べたＴＡＳＣ法の特徴により、本手法は８００×１６００×４０ｍｍの大きさの太陽電池パネルに適用可能である。すなわち、Ａｌ外枠を一切取り外すことなく、四方を外枠に取り囲まれた太陽電池パネルをそのままＴＡＳＣ処理することにより、外枠の取り外しとポリマーの分解・除去を同時に実現できる。
A piece of the back sheet 7 of the solar cell panel 9 was placed on the honeycomb 10 having a cordierite (2MgO.2Al 2 O 3 .5SiO 2 ) composition coated with Cr 2 O 3 as the oxide semiconductor 16. . The oxide semiconductor 16 does not itself change or wear out in the TASC process, and acts to decompose and remove organic substances in the object to be processed which are in contact therewith. Also called a catalyst-supporting honeycomb. The catalyst-supporting honeycomb 10 on which one piece of the solar cell panel 5 is placed is placed in the electric furnace 12 shown in FIG. 3, and the heater 13 is energized while introducing air from the air introduction port 14 and the temperature is raised to 500 ° C. for 30 minutes. The temperature was controlled at 500 ° C. Thereafter, the temperature control power supply was turned off to cool. Through the above series of TASC processes, the adhesive polymer for fixing the Al outer frame 1, the back sheet 7 of the panel piece, and the polymer constituting the filler are completely decomposed, and the outer frame 1 is separated from the module piece. From the lower part of the module, an inter connector 4 / solar cell 3 / inter connector 4 and a lump of finely cracked glass were obtained in order from the lower layer. The decomposed polymer becomes water and carbon dioxide gas and is discharged from the air exhaust port 15. The oxide semiconductor 16 (Cr 2 O 3 ) and the solar cell panel 9 are in contact with each other only on the surface of the back sheet 7. And unstable cation radicals are formed in the polymer. This radical propagates in the polymer, which is the decomposition target, destabilizes the whole polymer, and the polymer is cut into small molecules such as ethylene (radical cleavage) in such a way that it self-destructs. Reacts and decomposes completely into water and carbon dioxide. This is a feature of the TASC method. That is, once radicals are formed on the polymer surface, the decomposition reaction continues in the thickness direction, so that complete decomposition is realized up to the filler region.
Although the experiment was performed using a 120 × 120 × 5 mm solar cell module piece, this technique can be applied to a solar cell panel having a size of 800 × 1600 × 40 mm due to the characteristics of the TASC method described above. That is, without removing the Al outer frame at all, TASC treatment is performed on the solar cell panel surrounded by the outer frame as it is, so that the outer frame can be removed and the polymer can be decomposed and removed at the same time.
分解されたパネルを、５メッシュのステンレス網１７に移した。これを約３０度傾け、低周波数で振動させると、ガラス２塊は転がるように落下した。次に、周波数を上げて振動させると、太陽電池セル３ならびにインター・コネクタ４も落下し、分別・回収することができた。この間に、ポリマーに含有されていた無機物の白い残渣（充填物：ＴｉＯ２，ＣａＣＯ３，ＳｉＯ２等）はメッシュを通して落下した。以上の操作で、図２に示すように、外枠１、ガラス２塊、太陽電池セル３ならびにインター・コネクタ４は容易に分別できた。ステンレス網１７を傾ける角度は２０度以上４０度以下が好ましい。またガラス２塊を落下させるための振動数（第１の振動数）は５Ｈｚ以上で２０Ｈｚ以下の範囲で、太陽電池セル３ならびにインター・コネクタ４を落下させるための振動数（第２の振動数）は１０Ｈｚ以上で２００Ｈｚ以下の範囲で、ガラスの厚みおよび太陽電池セルの構造などに依存して最適値に設定すればよい。振動の強さは分別・回収ができるように、適宜調整するのが良い。 The disassembled panel was transferred to a 5 mesh stainless steel mesh 17. When this was tilted about 30 degrees and vibrated at a low frequency, the two glass lumps fell to roll. Next, when the frequency was increased and the cells were vibrated, the solar cells 3 and the inter-connector 4 were also dropped and could be separated and collected. During this time, inorganic white residues (filler: TiO 2 , CaCO 3 , SiO 2, etc.) contained in the polymer dropped through the mesh. By the above operation, as shown in FIG. 2, the outer frame 1, the glass 2 lump, the solar battery cell 3, and the inter connector 4 could be easily separated. The angle at which the stainless steel mesh 17 is inclined is preferably 20 degrees or more and 40 degrees or less. The frequency for dropping the two glass blocks (first frequency) is in the range of 5 Hz to 20 Hz, and the frequency for dropping the solar cells 3 and the inter-connector 4 (second frequency). ) May be set to an optimum value in the range of 10 Hz to 200 Hz depending on the thickness of the glass and the structure of the solar battery cell. The intensity of vibration should be adjusted as appropriate so that it can be separated and collected.
インター・コネクタ４は幅２ｍｍ、厚みが０．２ｍｍ、長さが１００ｍｍ程度の金属であり、蛍光Ｘ線分析の結果、銅と錫が主成分であることが分かった。また、太陽電池セル３の受光面には格子状の電極がスクリーン印刷されていた。太陽電池セル３ならびに格子状の電極材料は、蛍光Ｘ線分析の結果、それぞれシリコンならびに銀が主成分であることが判明した。太陽電池セル３の受光面上の銀電極は以下の手順により、ＡｇＣｌとして回収した。まず、銀電極のついた太陽電池セル３を濃硝酸で溶解し、薄黄色の溶液を得た。次に、これに塩酸を滴下し、銀をＡｇＣｌとして沈殿させた。水洗後にろ過・乾燥させ、ＡｇＣｌの粉末を得た。９．６ｇの太陽電池セルから、０．３ｇのＡｇＣｌを回収した（約３．２重量％）。 The inter-connector 4 is a metal having a width of 2 mm, a thickness of 0.2 mm, and a length of about 100 mm. As a result of fluorescent X-ray analysis, it was found that copper and tin are the main components. Further, a grid-like electrode was screen-printed on the light receiving surface of the solar battery cell 3. As a result of fluorescent X-ray analysis, it was found that the solar cell 3 and the grid electrode material are mainly composed of silicon and silver, respectively. The silver electrode on the light receiving surface of the solar battery cell 3 was collected as AgCl by the following procedure. First, the solar battery cell 3 with the silver electrode was dissolved with concentrated nitric acid to obtain a light yellow solution. Next, hydrochloric acid was added dropwise thereto to precipitate silver as AgCl. After washing with water, filtration and drying were performed to obtain AgCl powder. From 9.6 g of solar cells, 0.3 g of AgCl was recovered (about 3.2% by weight).
実施例２
実施例１で使用した太陽電池パネル９から、同様の太陽電池パネル９の１片を切り出した。酸化物半導体１６として、実施例１で使用したＣｒ２Ｏ３の代わりにα−Ｆｅ２Ｏ３（酸化鉄：ヘマタイト）を用い、実施例１と同様のＴＡＳＣ処理を行った。その結果、実施例１と同様に外枠１、ガラス２塊、太陽電池セル３ならびにインター・コネクタ４を良好な状態で分別・回収することができた。
Example 2
A piece of the same solar cell panel 9 was cut out from the solar cell panel 9 used in Example 1. As the oxide semiconductor 16, α-Fe 2 O 3 (iron oxide: hematite) was used instead of Cr 2 O 3 used in Example 1, and the same TASC treatment as in Example 1 was performed. As a result, as in Example 1, the outer frame 1, the glass 2 lump, the solar battery cell 3, and the inter connector 4 could be separated and collected in a good state.
実施例３
実施例１と同じ手法で、１２０×１２０×４０ｍｍの太陽電池パネル５の１片を切り出し、ＴＡＳＣ処理の解体試料とした。太陽電池パネル片のバック・シートに、Ｃｒ２Ｏ３分散膜を図４のように筆でストライプ状に数か所塗布した。太陽電池パネル片を無垢（Ｃｒ２Ｏ３を担持していない）のハニカムの上に置いて、実施例１と同じ手順でＴＡＳＣ処理をしたところ、Ａｌ外枠１を固定する接着剤ポリマー、パネル片のバック・シート７および充填剤を構成するポリマーは完全に分解され、外枠１はモジュール片から外れて分離されており、モジュール片部分からは下層から順に、インター・コネクタ４／太陽電池セル３／インター・コネクタ４、さらに細かくひび割れしたガラス２塊が得られた。
Example 3
In the same manner as in Example 1, a piece of 120 × 120 × 40 mm solar cell panel 5 was cut out and used as a dismantled sample for TASC treatment. On the back sheet of the solar cell panel piece, a Cr 2 O 3 dispersion film was applied in several stripes with a brush as shown in FIG. When the solar cell panel piece was placed on a solid honeycomb (which does not carry Cr 2 O 3 ) and subjected to TASC treatment in the same procedure as in Example 1, an adhesive polymer and panel for fixing the Al outer frame 1 were obtained. The back sheet 7 of the piece and the polymer constituting the filler are completely decomposed, the outer frame 1 is separated from the module piece and separated from the module piece part in order from the lower layer to the interconnector 4 / solar cell. 3 / interconnector 4 and two more cracked glass pieces were obtained.
実施例４
発熱体であるニクロム（Ｎｉ−Ｃｒ）線を湿潤水素で１０５０℃、５分ほど酸化すると、Ｎｉ−Ｃｒ成分のうち、Ｃｒのみが酸化され３ミクロン程度のＣｒ２Ｏ３膜が形成される。還元剤である水素で酸化すると言うのは奇異な感じがするが、１０５０℃近傍で、Ｈ２Ｏが分解し、放出される酸素でＣｒが酸化されるメカニズムである。この酸化膜は強固であり、基体から剥がれることもない。図４の塗布した酸化物半導体を、Ｃｒ２Ｏ３処理をしたニクロム線で置き換えてバック・シートに接触させる。無垢のハニカムの上にニクロム線を置き、さらにその上に実施例１と同じ手法で得た太陽電池パネル片を載せ、実施例１と同じ手順でＴＡＳＣ処理をしたところ、Ａｌ外枠１を固定する接着剤ポリマー、パネル片のバック・シート７および充填剤を構成するポリマーは完全に分解され、外枠１はモジュール片から外れて分離されており、モジュール片部分からは下層から順に、インター・コネクタ４／太陽電池セル３／インター・コネクタ４、さらに細かくひび割れしたガラス２塊が得られた。
Ｎｉ−Ｃｒ−Ｃｒ２Ｏ３をロッド状にして複数並べ、太陽電池パネル９のバック・シート７に接触させた状態で電流を流せば発熱するので、ＴＡＳＣ効果を促進することができる。
Example 4
When the nichrome (Ni—Cr) wire, which is a heating element, is oxidized with wet hydrogen at 1050 ° C. for about 5 minutes, only the Cr in the Ni—Cr component is oxidized and a Cr 2 O 3 film of about 3 microns is formed. Although it seems strange to oxidize with hydrogen as a reducing agent, it is a mechanism in which H 2 O is decomposed at around 1050 ° C. and Cr is oxidized by released oxygen. This oxide film is strong and does not peel off from the substrate. The coated oxide semiconductor of FIG. 4 is replaced with a Cr 2 O 3 treated nichrome wire and brought into contact with the back sheet. A nichrome wire was placed on a solid honeycomb, and a solar cell panel piece obtained by the same method as in Example 1 was placed on the honeycomb and TASC treatment was performed in the same procedure as in Example 1. As a result, Al outer frame 1 was fixed. The adhesive polymer, the back sheet 7 of the panel piece, and the polymer constituting the filler are completely decomposed, and the outer frame 1 is separated from the module piece and separated from the module piece portion in order from the lower layer. Connector 4 / solar cell 3 / inter-connector 4 and two more broken glass pieces were obtained.
When a plurality of Ni—Cr—Cr 2 O 3 are arranged in a rod shape and are brought into contact with the back sheet 7 of the solar cell panel 9, heat is generated when a current is passed, so the TASC effect can be promoted.
実施例５
実施例１もしくは実施例２において、太陽電池パネル９の１片のバック・シート７を下にして、酸化物半導体１６をコーティングしたハニカム１０上に載せる際に、ガラス等を回収する便宜のために図５のようにステンレス網１７を挿入する。予め、ハニカムには溝１８を掘っておき、溝深さ以下の厚みをもつステンレス網１７をはめ込めるようにしておく。こうすれば、ハニカムに坦持された酸化物半導体１６はパネル片のバック・シート７表面と接触するので、ＴＡＳＣ処理には支障がなく、かつＴＡＳＣ処理後に解体物を別途用意したステンレス網１７に移す工程を経ることなく、ステンレス網１７とステンレス網１７上の解体物をハニカムから外し、実施例１に記載した方法でガラス２塊、太陽電池セル３ならびにインター・コネクタ４を容易に分別することができる。
Example 5
In Example 1 or Example 2, when placing the back sheet 7 of the solar cell panel 9 on the honeycomb 10 coated with the oxide semiconductor 16, the glass or the like is collected for convenience. The stainless steel mesh 17 is inserted as shown in FIG. In advance, a groove 18 is dug in the honeycomb so that a stainless net 17 having a thickness equal to or less than the groove depth can be fitted. In this way, since the oxide semiconductor 16 carried on the honeycomb comes into contact with the surface of the back sheet 7 of the panel piece, there is no problem in the TASC process, and the dismantled material is separately prepared after the TASC process. Without passing through the transferring process, the stainless steel mesh 17 and the dismantled material on the stainless steel mesh 17 are removed from the honeycomb, and the glass 2 lump, the solar battery cell 3 and the inter connector 4 are easily separated by the method described in the first embodiment. Can do.
実施例６
太陽電池パネル９のＴＡＳＣ処理を連続的に行うには図６に示した太陽電池パネル用ＴＡＳＣ連続処理装置１９を用いるのが良い。溝１８を掘った酸化物半導体坦持ハニカム１０の上に、ステンレス網１７、太陽電池パネル９の１片を順に載せて、装置入口側の搬入部２０に置く。付着させた酸化物半導体または酸化したニクロム線によって酸化物半導体をバック・シートと接触させる場合は、無垢のハニカムの上にこれらを載せて他は同様とする。ハニカムと一体となってその上に置かれたステンレス網１７、太陽電池パネル９の１片は搬入部２０から搬出部２４に渡って設置されている搬送装置により、約１００ｍｍ／ｍｉｎの搬送速度で連続的に搬送される。予備加熱部２１、加熱処理部２２、冷却部２３には空気が外部から導入される。ハニカムと太陽電池パネル９の１片は予備加熱部２１を通過する間に５００℃に加熱される。約１０００ｍｍに渡って５００℃に制御された加熱処理部２２であるＴＡＳＣ処理部を通過するときにＴＡＳＣ処理が行われ、パネル片の中の有機物成分が完全に分解除去される。冷却部２３を通過する間に冷却が行われる。なお、室温まで冷却される必要はなく、冷却される温度は適宜でよい。冷却部２３から出てきたハニカム上の解体物からは有機物がＴＡＳＣ処理により完全に分解除去されており、搬出部２４において外枠１が分離回収され、ハニカムが除かれ、ステンレス網１７とその上の解体物が搬出部２４に戻される。搬出部２４を経て分別回収部２５に送られると分別回収部２５において、実施例１に記載された方法により無機物の白い残渣を、メッシュを通して落下させる。第一振動によりステンレス網１７から滑り落ちたガラス２と第２振動によりステンレス網１７から滑り落ちた太陽電池セル３およびインター・コネクタ４は分別・回収される。
Example 6
In order to continuously perform the TASC processing of the solar cell panel 9, it is preferable to use the solar cell panel TASC continuous processing device 19 shown in FIG. One piece of the stainless steel net 17 and the solar cell panel 9 is placed in this order on the oxide semiconductor-supporting honeycomb 10 in which the groove 18 has been dug, and placed in the carry-in portion 20 on the apparatus entrance side. When the oxide semiconductor is brought into contact with the back sheet by the deposited oxide semiconductor or oxidized nichrome wire, the same applies except that these are placed on a solid honeycomb. One piece of the stainless steel mesh 17 and the solar cell panel 9 placed integrally with the honeycomb is transferred at a transfer speed of about 100 mm / min by a transfer device installed from the carry-in part 20 to the carry-out part 24. Conveyed continuously. Air is introduced into the preliminary heating unit 21, the heat treatment unit 22, and the cooling unit 23 from the outside. One piece of the honeycomb and the solar cell panel 9 is heated to 500 ° C. while passing through the preheating portion 21. The TASC process is performed when passing through the TASC processing unit, which is the heat processing unit 22 controlled to 500 ° C. over about 1000 mm, and the organic components in the panel pieces are completely decomposed and removed. Cooling is performed while passing through the cooling unit 23. Note that it is not necessary to cool to room temperature, and the temperature to be cooled may be appropriate. Organic substances are completely decomposed and removed by TASC treatment from the dismantled material on the honeycomb that has come out of the cooling unit 23, and the outer frame 1 is separated and collected in the carry-out unit 24, the honeycomb is removed, and the stainless steel mesh 17 and above The dismantled product is returned to the carry-out unit 24. When sent to the separation collection unit 25 via the carry-out unit 24, the white residue of the inorganic substance is dropped through the mesh by the method described in Example 1 in the separation collection unit 25. The glass 2 slid down from the stainless steel mesh 17 due to the first vibration and the solar cells 3 and the inter-connectors 4 slid down from the stainless steel mesh 17 due to the second vibration are separated and collected.
連続処理装置１９において搬入部２０から搬出部２４に至るすべての経路を一定速度で搬送すると述べたが、搬入部２０、搬出部２４及び分別回収部２５では太陽電池パネル９を載せたハニカムを一定速度で連続的に搬送し、予備加熱部２１、加熱処理部２２及び冷却部２３を一体化したＴＡＳＣ処理室では停止状態でＴＡＳＣ処理を行うシステムでもよい。この場合、ＴＡＳＣ処理室には入口・出口の扉を持った電気炉が中央に置かれており、太陽電池パネル９を載せたハニカムの搬入の際には、入口の扉が開き、炉内に被処理物が運ばれ、入口が閉じられる。そして、処理後には出口側の扉が開き、ＴＡＳＣ処理されたハニカム上の解体物が搬出される。バッチ方式を踏襲した本システムは搬送制御がやや複雑になるが、メリットは温度管理がし易いこと、必要な酸素を制御できることであり、着実なＴＡＳＣ処理が可能である。 In the continuous processing apparatus 19, it has been described that all the routes from the carry-in unit 20 to the carry-out unit 24 are conveyed at a constant speed. In the TASC processing chamber that continuously conveys at a speed and integrates the preheating unit 21, the heating processing unit 22, and the cooling unit 23, a system that performs the TASC processing in a stopped state may be used. In this case, an electric furnace having an entrance / exit door is placed in the center in the TASC processing chamber, and when the honeycomb on which the solar cell panel 9 is loaded, the entrance door opens, The workpiece is carried and the inlet is closed. After the treatment, the door on the outlet side is opened, and the dismantled material on the honeycomb subjected to the TASC treatment is carried out. This system, which is based on the batch method, is slightly complicated in transport control, but the advantages are that it is easy to manage temperature and that it can control the necessary oxygen, so that steady TASC processing is possible.
本発明によれば、半導体の熱活性（ＴＡＳＣ）法を用いて太陽電池パネルから有価物である外枠、ガラス、太陽電池セル、インター・コネクタを低コストで短時間に回収することができるので、今後大量の処理需要の発生が見込まれる太陽光発電システムの廃棄物に対して、従来実現されていなかったリサイクルを実用的な事業として成立させえて、産業上の利用可能性は大きい。 According to the present invention, it is possible to recover valuable outer frames, glass, solar cells, and inter-connectors from solar panels at a low cost in a short time using a semiconductor thermal activation (TASC) method. The industrial applicability of the solar power generation system waste, which is expected to generate a large amount of processing demand in the future, can be established as a practical business.
１ 外枠
２ ガラス
３ 太陽電池セル
４ インター・コネクタ
５ ＥＶＡ等のポリマー
６ 端子
７ バック・シート
８ 太陽電池モジュール
９ 太陽電池パネル
１０ 酸化物半導体担持ハニカム
１１ 台
１２ 電気炉
１３ ヒーター
１４ 空気導入口
１５ 空気排気口
１６ 酸化物半導体
１７ ステンレス網
１８ 溝
１９ 太陽電池パネル用ＴＡＳＣ連続処理装置
２０ 搬入部
２１ 予備加熱部
２２ 加熱処理部
２３ 冷却部
２４ 搬出部
２５ 分別回収部
DESCRIPTION OF SYMBOLS 1 Outer frame 2 Glass 3 Solar cell 4 Inter connector 5 Polymers, such as EVA 6 Terminal 7 Back sheet 8 Solar cell module 9 Solar cell panel 10 Oxide semiconductor carrying honeycomb 11 Unit 12 Electric furnace 13 Heater 14 Air inlet 15 Air exhaust port 16 Oxide semiconductor 17 Stainless steel mesh 18 Groove 19 TASC continuous processing device 20 for solar cell panel 20 Loading section 21 Preheating section 22 Heat processing section 23 Cooling section 24 Unloading section 25 Sorting and collecting section
Claims (20)
回収物の中の太陽電池セルを硝酸に浸漬することにより、前記太陽電池セルの電極である銀または銀の化合物を溶解し、さらに塩酸を滴下することによって銀または銀の化合物の塩化物を生じさせ、銀または銀の化合物を回収することを特徴とする請求項１ないし請求項７に記載の太陽電池パネルから有価物を回収する方法。 After decomposing the polymer in the object to be processed and recovering valuable materials from the disassembled material,
By immersing the solar cells in the recovered material in nitric acid, the silver or silver compound that is the electrode of the solar cell is dissolved, and further, hydrochloric acid is added dropwise to produce a chloride of silver or a silver compound. The method for recovering valuable materials from the solar cell panel according to claim 1, wherein silver or a silver compound is recovered.
前記解体物をステンレス網上に移し、２０度以上４０度以下の範囲で基板を傾け、第１の振動数で振動させ、まずガラス塊を落下・分離させ、次に、第２の振動数で振動させて、太陽電池セルとインター・コネクターを落下・分離させることを特徴とする請求項１ないし請求項７に記載の太陽電池パネルから有価物を回収する方法。 As a method of decomposing and removing the polymer in the object to be processed and recovering valuable materials from the dismantled product,
The dismantled product is transferred onto a stainless steel net, the substrate is tilted within a range of 20 degrees to 40 degrees, and is vibrated at a first frequency. First, the glass block is dropped and separated, and then at a second frequency. The method for recovering valuable materials from the solar cell panel according to claim 1, wherein the solar cell and the interconnector are dropped and separated by vibration.
前記解体物から有価物を回収する過程は、前記連続処理装置内の分別回収部において、まず外枠を回収し、次にガラスを回収し、次に太陽電池セルおよびインター・コネクターを回収することにより、分別・回収されることを特徴とする請求項１ないし７または請求項９ないし１１に記載の太陽電池パネルから有価物を回収する方法。 The process of decomposing and removing the polymer in the object to be processed by heating the object to be processed in the presence of oxygen is introduced into a continuous processing apparatus that conveys the support on which the object is mounted, The oxide semiconductor in the continuous processing apparatus is performed by passing through a temperature region that becomes an intrinsic electric conduction region,
In the process of recovering valuable materials from the dismantled material, the separation and recovery unit in the continuous processing apparatus first recovers the outer frame, then recovers the glass, and then recovers the solar cells and the interconnector. The method for recovering a valuable material from a solar cell panel according to claim 1, wherein the valuable material is recovered by separation.
前記被処理物を、前記酸化物半導体が真性電気伝導領域となる温度以上に加熱する加熱処理部と、
前記加熱処理部内にエアを供給するエアの供給機構と、
前記加熱処理部において前記被処理物中のポリマーを分解除去して得られる解体物から、有価物を回収する回収部とを備えることを特徴とする太陽電池パネルから有価物を回収するための処理装置。 A transport device that transports the solar cell panel to be processed while the oxide semiconductor is in contact with the back sheet of the solar cell panel, with the outer frame of the solar cell panel still attached,
A heat treatment unit that heats the object to be processed to a temperature at which the oxide semiconductor becomes an intrinsic electric conduction region;
An air supply mechanism for supplying air into the heat treatment unit;
A process for recovering valuable material from a solar cell panel, comprising: a recovery unit that recovers valuable material from a dismantled product obtained by decomposing and removing the polymer in the object to be processed in the heat treatment unit apparatus.
In the recovery unit for recovering valuable materials from the dismantled material, the outer frame is first recovered, the glass is then recovered, and then the solar cells and the interconnector are recovered, thereby being separated and recovered. The processing apparatus for collect | recovering valuables from the solar cell panel of Claim 13 thru | or 19.
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