201130764 六、發明說明： 【發明所屬之技術領域】 本發明係一種涉及於固體廢物處理與陶瓷的技術領 域，尤指太陽能板廢棄物再利用而製成玻璃陶究。 【先前技術】 按由全球面臨氣候變遷，造成暖化日益嚴重以及能源 逐漸耗竭等問題，各國積極投入發展替代能源及綠色科技 產業，其中運用太陽能來發電的綠色科技，是許多國家積 極推動的方向，由於太陽能電池是將太陽能轉換成電能的 裝置，需有陽光才能運作，太陽能電池與蓄電池串聯，將 有陽光時所產生的電能先行儲存，以供無陽光時放電使 用。使用中較沒有釋放二氧化碳等破壞生態環境問题，因 而被視為未來重要新興能源。 一般而言，太陽能電池利用太陽光直接發電的光電半 導體薄片，該薄片在接受太陽光等光線照射，即可輸出電 壓及電流’而太陽能電池（又可稱晶片或是碎晶’分成非晶 矽、多晶、單晶）在設計所需要的電流進行切割後焊接箔條 導線，完成之後用箔條串聯成一組，再和強化玻璃層層疊 置，並且進行真空封裝以製成稱太陽能板，而數個太陽能 板組成方陣。 太陽能電池有分成薄膜太陽能電池，以及矽晶圓太陽 能電池，根據行政院環保署公佈資料顯示，2007年國内市 場約含3，998，295 kg/y之太陽能板（太陽能板是組裝太 201130764 陽能板廠商所製造之單晶矽、多晶矽及薄膜），太陽能板廢 棄量約191 ’ 186 kg/y ，其中廢薄膜類太陽能電池約8， 603 kg/y ’廢矽晶類太陽能電池約171，111 kg/y。薄膜 類廢棄太陽能電池的玻璃矽含量高達（68. 35%)，因此如何 處理這些廢棄物，也是一項重要問題，發明人因此思考， 如能將廢棄太陽能板廢玻璃資源化再利用，將可有效解決 太陽能板廢玻璃之問題。 【發明内容】 本發明者鑑於前述的問題，進而用心研究開發， 因此本發明主要目的係在提供一種太陽能板廢玻璃 燒製成玻璃陶瓷之方法及產品，其主要是將廢棄太陽 能板，以最低成本而再利用為玻璃陶瓷之原料，有效 減少廢棄太陽能板玻璃，並將廢棄材料轉換為有價值 的再利用資源。 為了可達到前述的目的，本發明所運用的技術手 段係在於提供一種太陽能板廢玻璃燒製成玻璃陶瓷 之方法，其係包含： 備料：將數太陽能板廢玻璃集中一起，該太陽能板 廢玻璃是太陽能板製品製造時發生損毀及生命週期 結束後所產生之廢棄物； 研磨成粉末：太陽能板廢玻璃研磨成粉末，研磨粉 末細度範圍為100〜400m2/kg; 加壓成型：將研磨後的粉末施以12〇〜22〇 範圍内的壓力，以岐成型為指^形狀的基體； 201130764 ，理·.將别述加壓成型的該基體，送入高溫爐加 熱以構成k結體’熱處理條件是加熱 加 60(TC〜85〇t之間，而熱處理時間是在w小時在 熱速率範圍是在5〜20 玻璃陶究成品：燒结體宗·占無+ β 疋成熱處理階段，自高溫爐 取出而冷卻之後即為玻璃陶瓷成品。 因此依據本發明的技術手段’本發明可以獲得的 功效簡要說明如下所列： 卜本發明以廢棄太陽能板，作為製作玻璃陶瓷之 原料，其廢棄太陽能板玻璃的矽含量高達68 35%，透 過本發明的製法，未來將可有效減少每年所產生8, 6〇3 kg廢棄太陽能板玻璃，減少廢棄物的產生。 2本發明開拓太陽能板廢玻璃的再利用途徑以及 市場需求量，提高產品單位價值，建立具市場性的再 生原料應用技術，有效解決太陽能廢玻璃處置問題。 3、利用太陽能板廢玻璃做為玻璃陶瓷材料，可降低以 往製ie玻璃陶瓷多是需要1〇〇〇。〇以上的熱處理溫度，因此 本發明可以降低生產玻璃陶瓷的成本，同時減少能源損耗。 【實施方式】 為使貴審查委員對本發明之目的、特徵及功效能夠有 更進一步之瞭解與認識，以下茲請配合【圖式簡單說明】 詳述如后： 本發明係一種太陽能板廢玻璃燒製成玻璃陶瓷 之方法及產品，請配合參看第一圖’其係為製法流程 201130764 圖’顯不製法流程依序是： 備料（10):將太陽能板廢玻璃集中一起；本發明 所指太陽能板廢玻璃是指太陽能板製品製造時發生 損毀及生命週期結束後所產生之廢棄物，而太陽能板 廢玻璃材料化學元素組成，經XRF Fluorescence)，以利用X射線螢光原理，來測量太 板廢玻璃化學組成的每一種元素，分析之後，太 ^ 陽能板廢玻璃主要成分是以Si〇2為主，所佔百分比為 68. 35%，而 CaO 及 Na2〇 分別佔 5· 61%及 7. 66%，而組 成分析可配合如附件一的表1所示。 研磨成粉末（20):將太陽能板廢玻璃研磨成粉 末，而本發明所需粉末粒徑分布可如第二圖所示，其 中粉末之粒徑於38〜125 e m佔89, 27%，大於！25以m 佔6.92%，而小於38…占3 81%。研磨流程中， 是首先將太陽能板廢玻璃經由破碎手段以形成小塊 •玻璃，再利用球磨機研磨成粉末並控制其細度，研磨 粉末細度範圍為100-400n]Vkg，較佳細度為3〇〇 m /kg。本發明所使用之材料經以微波消化後來測定其 重金屬總量如附件一的表2所示，各重金屬皆低於最 :偵測極限。而太陽能板廢破璃依據環保署公告之 事業廢棄物毒性特性溶出程序_NIEAR2〇ii〇t」固 體廢棄物重金屬溶出程序部份進行溶出實驗，再利用 原子吸收光譜儀测定溶出液過遽後重金屬含 實驗結果如附件一的表3所示，各重金屬皆低於 取小谓測極限，兹以說明本發明準備再利用的太陽能 201130764 板廢玻璃，其重金屬含量完全符合不傷害人體的安全 標準。 加壓成型（30):將研磨後的粉末透過油壓機械， 將前述太陽能板廢玻璃粉末，施以120〜220 kgf/cm2 範圍内的壓力，以固定成型為板狀體或是其它指定形 狀的基體，較佳壓力狀態為200 kgf/cm2。 熱處理（40):本發明是將前述加壓成型的基體， 送入高溫爐加熱以構成燒結體，而高溫爐的窯燒氣氛 環境可以是供氧或是厭氧狀態，本發明燒結熱處理條 件如下所列： 加熱燒結溫度範圍--6〇〇。(：-850。(：，較佳熱處理 溫度為850°C ; 熱處理時間--；L〜4小時，較佳熱處理時間為2小 時； 加熱速率範圍--5-20 °C /min，較佳加熱速率為5 °C/min。 ‘ 太陽能板廢玻璃之DTA(熱差分析）結果如附件二 的圖1所示’太陽能板廢玻璃主要成份Si〇2熔點為 1710°C，但因為玻璃中含有Na0使得熔點下降，故在 熱處理7 0 0 C左右形成黏製流特性，並在熱差分析 (DTA )圖上有一明顯之寬闊吸熱峰產生。本發明使 用X-ray繞射儀（XRD)分析太陽能板廢玻璃，分析 結果如附件二的圖2所示。 由於太陽能板廢玻璃為無定形之非結晶結構故 其繞射圖形呈現許多雜訊而無明顯繞射峰，當燒結溫 201130764 度達到800°C在21. 46。開始出現一明顯繞射峰，此位 置為Si〇2晶相’而在30.06及35·60出現另外兩個明 顯繞射峰，此位置為CaA12〇4晶相，燒結體之表面微 結構是如附件三所示。由圖中可見燒結體經6〇(rc燒 結處理後，其表面粉體間可以觀察到明顯頸部成長現 象’這是由於粉體原子藉由表面擴散機制所造成。在 燒結溫度650eC圖中表面空隙明顯較6〇(Tc減少，其 % 因在較咼溫度下原子具有較高動能導致擴散速率增 加。當燒結溫度達到70(TC ’由於矽酸鹽類熔融形成 黏滯流（玻璃化）填滿孔隙，因此其表面呈現光滑且不 具外部孔隙。表面結晶結構是在燒結至8〇〇°c以後開 始出現，和XRD分析結果相符。 玻璃陶瓷成品（50):當燒結體在完成熱處理階 段’自咼溫爐取出而冷卻之後即為玻璃陶瓷，玻璃陶 究的硬度、抗折強度，都透過本發明的製法而有可靠 • 確實的效果。請參看第三圖所示，玻璃陶瓷在燒結時 密度之變化可知結構之緻密化程度，依本發明的方 法’將太陽能板廢玻璃製成的玻璃陶瓷，其不同燒結 溫度之密度變化情形’此由燒結溫度為6〇〇的 2. 05 ’隨著燒結溫度提升至65(rc、70(rc、75〇〇C、 800 °C及850 °C後’燒結體之密度分別為2. 143、 2.252、2.36、2.5及2.547，由上述可知，玻璃陶究 之後、度隨燒結溫度提升而有上升的趨勢，因此燒結溫 度愈高’玻璃陶瓷成品的結構愈緻密。 此外，透過本發明的製法，本發明可以適度提昇 201130764 燒結體的機械性質，請參看第四圖，當繞結溫度為6〇〇 °C、650t、700°C、750°C、80(TC 及 85〇t：時广燒结 體之硬度由60(TC至650°C是呈比例上昇，65〇。〇近^ 持平穩定，到了 80(TC，玻璃陶瓷的燒結體硬度更為 提昇，此乃玻璃陶瓷的緻密化而提昇了機械性質提 升。而再配合第五圖，其為玻璃陶瓷在各燒結溫度之 抗折強度變化，在燒結過程中，是呈上昇穩定趨勢， 在75(TC至80(TC又一明顯提昇，可見破璃陶曼在燒 結時’其抗折強度隨著燒結溫度升高至8〇〇〇c左右確 實有提升效果，此乃玻璃陶瓷在燒結過程中，燒結體 表面之黏製流燒結現象增進燒結體緻密化效果=對完 成的玻璃陶瓷，其機械強度發展有正面效果。 上述實施例僅為例示性說明本發明之技術及其功效，而非用 於限制本發明。任何熟於此項技術人士均可在不違背本發明之技 術原理及精_情況下，耻述魏例進行修改及變化 ，因此本 發月之權彻她圍應如後所述之帽專利範圍所列。 201130764 【圖式簡單說明】 (一）圖式部分 第一圖係本發明較佳實施例之方塊流程圖。 第二圖係本發明較佳實施例之太陽能板廢玻璃研磨成粉末的 粒徑分佈圖。 第三圖係本發明較佳實施例之太陽能板廢玻璃，在各種熱處 理溫度的密度顯示圖。 第四圖係本發明較佳實施例之太陽能板廢玻璃各熱處理溫度 的硬度顯示圖。 第五圖係本發明較佳實施例之太陽能板廢玻璃各熱處理溫度 的抗折強度顯示圖。 附件一：太陽能板廢玻璃的組成分析以及重金屬情況顯示表。 附件二:太陽能板廢玻璃的在DTA與XRD分析圖表。 附件三:太陽能板廢玻璃熱處理溫度的表面組織放大分析照 片° ® 【主要元件符號說明】 《本發明》 (10)備料 (20)研磨成粉末 (30)加壓成型 (40)玻璃陶瓷成品 (50)熱處理 11201130764 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a technical field related to solid waste treatment and ceramics, and more particularly to the recycling of solar panel waste to produce glass ceramics. [Previous technology] According to the global climate change, causing increasingly serious warming and gradual depletion of energy, countries are actively investing in the development of alternative energy and green technology industries. The use of solar energy to generate green technology is a positive direction for many countries. Since the solar cell is a device that converts solar energy into electrical energy, it needs sunlight to operate. The solar cell is connected in series with the battery, and the electric energy generated when there is sunlight is stored first for discharge when there is no sunlight. In use, it does not release carbon dioxide and other environmental damage problems, so it is regarded as an important new energy source in the future. In general, a solar cell uses an optoelectronic semiconductor wafer that directly generates electricity by sunlight, and the sheet can output voltage and current when it is irradiated with sunlight, etc., and the solar cell (also called a wafer or a broken crystal) is divided into an amorphous crucible. , polycrystalline, single crystal) after the current required for the design is cut, the foil strip wires are welded, and after completion, the foil strips are connected in series, and then laminated with the tempered glass layer, and vacuum-packed to form a solar panel. Several solar panels form a square matrix. The solar cells are divided into thin film solar cells and silicon wafer solar cells. According to the data released by the Environmental Protection Agency of the Executive Yuan, the domestic market contains about 3,998,295 kg/y solar panels in 2007 (the solar panels are assembled too 201130764 yang). The amount of solar panels discarded is about 191 '186 kg/y, and about 8,603 kg/y of waste film solar cells. About 171 waste silicon solar cells. 111 kg/y. The waste glass-based waste solar cells have a high glass cerium content (68. 35%), so how to deal with these wastes is also an important issue. The inventors therefore think that if the waste solar glass waste glass can be recycled and reused, it will be Effectively solve the problem of solar panel waste glass. SUMMARY OF THE INVENTION The present inventors have made in mind research and development in view of the foregoing problems, and therefore the main object of the present invention is to provide a method and a product for firing a solar panel waste glass into a glass ceramic, which is mainly to waste solar panels to a minimum. The cost is reused as a raw material for glass ceramics, which effectively reduces waste solar panel glass and converts waste materials into valuable reuse resources. In order to achieve the foregoing objects, the technical means used in the present invention is to provide a method for burning solar glass waste glass into glass ceramics, which comprises: preparing materials: collecting solar panels waste glass together, the solar panel waste glass It is the waste generated during the manufacture of solar panel products and the waste generated after the end of the life cycle; grinding into powder: the solar glass waste glass is ground into powder, the fineness of the grinding powder ranges from 100 to 400 m2/kg; pressure molding: after grinding The powder is applied at a pressure in the range of 12 〇 to 22 ,, and is formed into a matrix of the shape of the shape of the ;; 201130764, Li.. The substrate which is press-formed is sent to a high temperature furnace to be heated to form a k-shaped body' The heat treatment condition is heating plus 60 (TC~85〇t, while the heat treatment time is in the heat rate range of 5~20 in the heat rate range of 5~20 glass ceramics finished product: sintered body Zong·zhan + β 疋 into heat treatment stage, After being taken out from the high temperature furnace and cooled, it is a finished glass ceramic. Therefore, according to the technical means of the present invention, a brief description of the functions that can be obtained by the present invention is as follows: Abandoning solar panels, as a raw material for making glass ceramics, the waste solar panel glass has a germanium content of up to 68 35%. Through the production method of the present invention, in the future, it is possible to effectively reduce 8, 6〇3 kg of discarded solar panel glass produced each year, and reduce The production of waste. 2 The invention develops the recycling route of solar panel waste glass and the market demand, improves the unit value of the product, establishes a market-oriented application technology of recycled raw materials, and effectively solves the problem of disposal of solar waste glass. The waste glass is used as a glass ceramic material, which can reduce the heat treatment temperature of the conventional glass ceramics. Therefore, the present invention can reduce the cost of producing the glass ceramics while reducing energy loss. To enable your review committee to have a better understanding and understanding of the purpose, features and effects of the present invention, please refer to the following [detailed description of the drawings] as follows: The present invention is a solar panel waste glass fired into glass ceramics. Method and product, please refer to the first picture 'the system is the manufacturing process 201130764 The process of the process of the display process is as follows: Preparation (10): Collecting the waste glass of the solar panel together; the waste glass of the solar panel referred to in the present invention refers to the waste generated during the manufacture of the solar panel product and the waste generated after the end of the life cycle. And the chemical element composition of the solar panel waste glass material, by XRF Fluorescence, to measure each element of the chemical composition of the waste glass of the Taiban using the principle of X-ray fluorescence. After analysis, the main component of the waste glass of the solar panel is Si〇2 is the main component, accounting for 68.35%, while CaO and Na2〇 account for 5.61% and 7.66%, respectively, and the composition analysis can be combined with Table 1 as shown in Annex 1. Grinding into a powder (20): grinding the solar panel waste glass into a powder, and the particle size distribution of the powder required by the present invention can be as shown in the second figure, wherein the particle diameter of the powder is 38 to 125 em, which is 89, 27%, which is larger than ! 25 is 6.92% in m, and less than 38... accounting for 3 81%. In the grinding process, the solar panel waste glass is firstly formed into small pieces and glass through a crushing means, and then ground into a powder by a ball mill and controlled in fineness thereof. The fineness of the grinding powder ranges from 100 to 400 n] Vkg, and the fineness is preferably 3〇〇m /kg. The materials used in the present invention were subjected to microwave digestion and the total amount of heavy metals was measured as shown in Table 2 of Annex I, and each heavy metal was below the maximum: detection limit. The solar panel waste glass is subjected to the dissolution test according to the EPA's commercial waste toxicity characteristic dissolution procedure _NIEAR2〇ii〇t" solid waste heavy metal dissolution procedure, and the atomic absorption spectrometer is used to determine the heavy metal content after the dissolution of the solution. The experimental results are shown in Table 3 of Annex I. Each heavy metal is lower than the minimum measurement limit. The solar energy 201130764 waste glass prepared for reuse according to the present invention has a heavy metal content which fully meets the safety standard of not harming the human body. Press molding (30): the ground powder is passed through a hydraulic machine, and the solar glass waste glass powder is applied at a pressure in the range of 120 to 220 kgf/cm 2 to be fixed into a plate shape or other specified shape. The substrate has a preferred pressure state of 200 kgf/cm2. Heat treatment (40): In the present invention, the pressure-molded substrate is sent to a high-temperature furnace to be heated to form a sintered body, and the kiln atmosphere of the high-temperature furnace may be an oxygen supply or an anaerobic state, and the sintering heat treatment conditions of the present invention are as follows Listed: Heating and sintering temperature range - -6 〇〇. (: -850. (:, preferably heat treatment temperature is 850 ° C; heat treatment time -; L ~ 4 hours, preferably heat treatment time is 2 hours; heating rate range -5-20 ° C / min, preferably) The heating rate is 5 °C/min. 'The DTA (thermal difference analysis) results of the solar panel waste glass are shown in Figure 1 of Annex II. The melting point of the main component of the solar panel waste glass, Si〇2, is 1710 ° C, but because of the glass The inclusion of Na0 causes the melting point to decrease, so that a viscosity flow characteristic is formed around the heat treatment of 700 ° C, and a broad broad endothermic peak is produced on the thermal differential analysis (DTA) map. The present invention uses an X-ray diffractometer (XRD). The solar panel waste glass is analyzed, and the analysis results are shown in Figure 2 of Annex 2. Since the solar panel waste glass is amorphous and amorphous, its diffraction pattern exhibits many noises without obvious diffraction peaks when the sintering temperature is 201130764 degrees. It reaches 800 ° C at 21. 46. A distinct diffraction peak begins to appear, this position is Si〇2 crystal phase' and two other significant diffraction peaks appear at 30.06 and 35·60. This position is CaA12〇4 crystal phase. The surface microstructure of the sintered body is as shown in Annex III. 6 体 after the rc sintering process, a significant neck growth phenomenon can be observed between the surface powders. This is due to the surface diffusion mechanism of the powder atoms. The surface voids in the 650eC sintering temperature are significantly higher than 6〇. (Tc is reduced, the % is due to the higher kinetic energy of the atom at higher temperatures, resulting in an increase in the diffusion rate. When the sintering temperature reaches 70 (TC' is filled with pores due to the formation of viscous flow (vitrification) by the strontium-based melting, The surface is smooth and has no external pores. The surface crystal structure begins to appear after sintering to 8 ° C and is consistent with the XRD analysis. Glass ceramic finished product (50): When the sintered body is in the heat treatment stage, it is taken out from the furnace. After cooling, it is a glass ceramic. The hardness and bending strength of the glass ceramics are all reliable and reliable through the method of the present invention. Please refer to the third figure, the change of the density of the glass ceramic during sintering can be known. The degree of densification, according to the method of the present invention, the glass ceramics made of solar panel waste glass, the density of which varies with different sintering temperatures. The density of the sintered body is 2. 143, 2.252, 2.36 after the sintering temperature is raised to 65 (rc, 70 (rc, 75 ° C, 800 ° C and 850 ° C). , 2.5 and 2.547, as can be seen from the above, after the glass is tempered, the degree increases with the increase of the sintering temperature, so the higher the sintering temperature, the denser the structure of the finished glass ceramic. Furthermore, the invention can be made by the method of the invention. Moderately improve the mechanical properties of the 201130764 sintered body, please refer to the fourth figure. When the winding temperature is 6〇〇°C, 650t, 700°C, 750°C, 80 (TC and 85〇t: wide sintered body The hardness is increased from 60 (TC to 650 ° C, 65 〇. 〇近^ Flat and stable, to 80 (TC, the hardness of the sintered ceramics is more enhanced, this is the densification of glass ceramics and enhances the mechanical properties. And with the fifth figure, it is the glass ceramic at each sintering temperature The change of the flexural strength is a rising trend during the sintering process. At 75 (TC to 80 (the TC is further improved, it can be seen that when the glass is sintered), its flexural strength increases with the sintering temperature. There is indeed a lifting effect around 8〇〇〇c. This is the sintering process of the glass ceramic during the sintering process. The sintering phenomenon on the surface of the sintered body enhances the densification effect of the sintered body = positive effect on the mechanical strength development of the finished glass ceramic. The above embodiments are merely illustrative of the technology of the present invention and its effects, and are not intended to limit the present invention. Anyone skilled in the art can swear Wei without violating the technical principles and fineness of the present invention. The amendments and changes are made in this case, so the right of this month will be listed in the patent scope of the cap as described later. 201130764 [Simple description of the drawings] (1) The first part of the figure is preferred. The block diagram of the embodiment is a particle size distribution diagram of the solar panel waste glass ground into a powder according to a preferred embodiment of the present invention. The third figure is a solar panel waste glass according to a preferred embodiment of the present invention, in various heat treatments. The density is shown in Fig. 4. The fourth figure is a hardness diagram of each heat treatment temperature of the solar panel waste glass according to the preferred embodiment of the present invention. The fifth figure is the bending resistance of each heat treatment temperature of the solar panel waste glass according to the preferred embodiment of the present invention. Intensity display diagram. Annex 1: Composition analysis of solar panel waste glass and display table of heavy metals. Annex 2: DTA and XRD analysis charts of solar panel waste glass. Annex III: Surface microstructure amplification analysis photos of solar panel waste glass heat treatment temperature ° ® [Main component symbol description] "The invention" (10) Preparation (20) Grinding into powder (30) Press forming (40) Glass ceramic finished product (50) Heat treatment 11