1375587 六、發明說明： - .【發明所屬之技術領域】 本發明係關於一種回收廢棄面板中液晶之方法及裝 置’更特別關於其中的循環萃取方法。 【先前技術】 液晶顯示器具有薄型化、輕量化、低耗電耋、無輻射 污染、且能與半導體製程相容等優點，其使用量、生產量、 及廢棄量均大幅上升。雖然液晶是否有害仍未定論’但將 未去除液晶之廢棄面板焚化或掩埋皆有可能造成環境汙 染。雖然液晶用量只占面板總重量的〇· 1_0 2〇/〇左右’卻會 因法規使面板玻璃無法回收再利用。目前台灣已是世界最 大的LCD出產國之一，而歐盟於2003年所公佈之廢電機/ 電子 6又備才日令（Waste Eiectrical and Electronics Equipment ’簡稱WEEE)已要求製造販賣者需負責販售物的 回收。可預知的是未來幾年内廢棄的LCD面板會越來越 多，若能有效率的自廢棄面板中取出液晶甚至將回收的液 晶再利用，將可同時達到環保與經濟的雙重效果。 近年來’陸續有廢棄面板處理相關的專利發表。 JP.2001-337305先將偏光板以手撕方式去除並將框膠部份 切除後，再碎裂面板，接著以溶劑將面板中的液晶洗下回 收。此方法必須先去除偏光板和框膠，流程較繁雜，且以 沖洗的方式將液晶取下將耗費大量溶劑。 JP2002-166259以液晶溶於熱水中，再將溶液冷卻至室 溫，使液晶與水分離回收。然而經本發明之發明人實驗， 1375587 -r *' 發現熱水對大部分液晶之溶解效果非常差，此方法將耗費 大量的熱能卻無法有效回收.液晶。._ JP2002-254059 .以電氣分離的方法，於水中將廢棄面板 破碎後’再以溶劑洗提面板上的液晶。利用超音波振盪或 攪拌幫助溶解液晶後，再將溶劑蒸乾後可取得液晶。此方 法以電氣分離的方式分離廢棄面板後，其封裝材料必然會 溶於上述之溶劑。由於此方法並未提及回收液晶之溶劑會 溶解封裝材料的問題，亦未提及純化回收液晶的方法，因 籲 此回收之液晶材料將含有大量封裝材料而無法直接庳用。 TW 2004-04884先去除框膠，再以溶劑溶解液:或以 吹氣法或離心機將液晶取下後，利用減壓蒸餾法將液晶中 之不純物去除或用吸附劑去除離子，回收液晶。此方法回 收之液晶需進-步添加液晶單體才能與原有之液晶組成相 同。此方法須先去除面板上之框膠部分避免污染，而純化 f晶的方式為管柱層析，回收後的液晶材料又需添加液晶 • 早體才能再使用，均大幅增加回收液晶的複雜度與成本。 JP2006-G896G5使賴師非極性之混合有機溶劑取 出液晶’再以管柱層析純化回收之液晶產物。此方法的純 化方式為管柱層析，於大量回收應用上較困難，且回收後 的液晶材料亦需添加液晶單體才能再使用。 ㈣G6·购76湘減壓加熱將面板中之液晶和有機 物揮發’藉由冷凝方式分離载流氣體、液晶和其他有機物。 此方法並未直接碎裂液晶面板，且減壓加熱的方法會將液 2及其他有機物(如封裝材料）自面板同時分離出來。此方 法並未提及純化回收液晶的方法，因此回收之液晶材料將 1375587 含有大量封裝材料而無法直接應用。 上述這些方法有些處理步驟繁雜、有些只適用於特定 液晶、有些會改變液晶配方等，應用上仍有許多可改善的 空間，因此本發明提供一種連續式回收廢棄面板中液晶之 方法，可應用於處理市面上大部分之液晶面板，而且取出 之液晶雜質少且配方組成不變，僅需以先前發表之液晶純 化方法（中華民國的專利1282359和1297282)進行純化後即 可再利用。 【發明内容】 本發明提供一種回收廢棄面板中液晶之方法，包括⑴ 碎裂廢棄面板後，以溶劑浸泡碎裂之廢棄面板，使溶劑溶 解碎裂之廢棄面板中的液晶及封裝材料以形成萃取液；（ii) 冷卻萃取液以析出封裝材料，使封裝材料與萃取液固液分 離，接著過濾吸附萃取液；（iii)加熱萃取液使溶劑形成蒸氣 並冷凝形成回收溶劑；（iv)以回收溶劑浸泡碎裂之廢棄面 板，形成萃取液；以及0)重複步驟（ii)至（iv)直到面板中之 液晶皆溶解於萃取液，再將溶劑去除以得到回收液晶。 本發明亦提供一種回收廢棄面板中液晶之裝置，包括 萃取槽，具有基本過濾功能位於萃取槽底部；控溫裝置， 位於萃取槽中或位於萃取槽與過濾吸附裝置之間；收集 槽，具有加熱裝置加熱收集槽；第一儲存槽，位於萃取槽 上方且連接至萃取槽；第二儲存槽，位於萃取槽與過濾吸 附裝置下方；以及冷凝裝置，分別連接至收集槽及第一儲 6 ⑧ 1375587 存槽，且位於第一儲存槽及收集槽上方；其中萃取槽、收 集槽、與第二儲存槽分別以管線連接至三向閥，且過濾-吸 附裝置位於萃取槽與三向閥之間。 【實施方式】 本發明回收廢棄面板中液晶的方法如第1圖之流程圖 所示。首先，碎裂廢棄面板後，以溶劑浸泡廢棄面板，使 溶劑溶解廢棄面板之液晶以形成萃取液。廢棄面板之來源 可為工廠製程的報廢產品，亦可為使用一段時間後的回收 物。本發明碎裂廢棄面板的方法為事先拆解邊框至只剩液 晶盒(cell)部分後直接壓碎，不需移除框膠等封裝材料。在 本發明一實施例中，碎裂後之液晶面板碎片尺寸小於1〇〇 平方公分。適用於本發明之溶劑可為C6_10之烷類如正己 烷，C3_5之醇類如異丙醇，C2_4之醚類如乙醚，C3_5之酮類 如丙酮、丁酮或戊酮，或上述之混合溶劑。值得注意的是， 本發明以浸泡而非沖洗（flush)方式溶解廢棄面板中的液 晶。由於碎裂之廢棄面板之間具有空隙，沖洗方式將無法 使溶劑流入該些空隙以溶解此部份的液晶，使回收效率下 降。反之，浸泡方式可穩定的讓溶劑流入上述空隙。在本 發明一實施例中，浸泡碎裂廢棄面板之溶劑其液面高度高 於最頂端的廢棄面板。在本發明一實施例中，浸泡時間約 介於10分鐘至1小時。值得注意的是，此步驟之溶劑亦會 溶解部份的封裝材料。 接著將萃取液降溫，使萃取液中溶解度較差之封裝材1375587 VI. Description of the Invention: - Technical Field to Which the Invention pertains The present invention relates to a method and apparatus for recycling liquid crystal in an waste panel, more particularly to a cyclic extraction method therein. [Prior Art] Liquid crystal displays have advantages such as thinness, light weight, low power consumption, no radiation pollution, and compatibility with semiconductor processes, and their usage, throughput, and waste have increased significantly. Although it is still unclear whether the liquid crystal is harmful, the incineration or burying of the waste panel without removing the liquid crystal may cause environmental pollution. Although the amount of liquid crystal used only accounts for 〇·1_0 2〇/〇 of the total weight of the panel, the panel glass cannot be recycled and reused due to regulations. At present, Taiwan is already one of the largest LCD producers in the world, and the Waste Eiectrical and Electronics Equipment (WEEE) announced by the European Union in 2003 has required manufacturers to sell. Recycling of things. It is foreseeable that there will be more and more discarded LCD panels in the next few years. If the liquid crystals can be taken out of the waste panel efficiently and the recovered liquid crystals can be reused, the environmental and economic effects can be achieved at the same time. In recent years, there have been patents related to the disposal of discarded panels. JP. 2001-337305 first removes the polarizing plate by hand tearing and cuts off the sealant portion, then breaks the panel, and then washes the liquid crystal in the panel with solvent to recover it. This method must first remove the polarizing plate and the frame glue, the process is complicated, and it takes a lot of solvent to remove the liquid crystal by rinsing. In JP2002-166259, the liquid crystal is dissolved in hot water, and the solution is cooled to room temperature to separate and recover the liquid crystal and water. However, according to the experiment of the inventors of the present invention, 1375587 -r *' found that the dissolution effect of hot water on most liquid crystals is very poor, and this method consumes a large amount of heat energy but cannot be efficiently recovered. ._ JP2002-254059 . In the method of electrical separation, after the waste panel is broken in water, the liquid crystal on the panel is eluted with a solvent. The liquid crystal is obtained by dissolving the liquid crystal by ultrasonic vibration or stirring, and then evaporating the solvent. When the method separates the waste panel by electrical separation, the encapsulating material is inevitably dissolved in the above solvent. Since this method does not mention the problem that the solvent for recovering the liquid crystal dissolves the encapsulating material, there is no mention of a method for purifying and recovering the liquid crystal, because the recycled liquid crystal material will contain a large amount of encapsulating material and cannot be directly used. TW 2004-04884 first removes the sealant, and then removes the liquid crystal by a solvent solution: or by a blow method or a centrifuge, and then removes the impurities in the liquid crystal by a vacuum distillation method or removes ions with an adsorbent to recover the liquid crystal. The liquid crystal recovered by this method needs to be added with a liquid crystal monomer in order to be the same as the original liquid crystal composition. This method must first remove the sealant on the panel to avoid contamination, and the way to purify the f crystal is column chromatography. The recovered liquid crystal material needs to be added with liquid crystal and the early body can be reused, which greatly increases the complexity of recycling the liquid crystal. With cost. JP2006-G896G5 removes the recovered liquid crystal product by column chromatography using a non-polar mixed organic solvent. The purification method of this method is column chromatography, which is difficult to use in a large amount of recycling, and the liquid crystal material after the recovery also needs to be added with a liquid crystal monomer. (4) G6· purchased 76 ° decompression heating to volatilize the liquid crystal and organic matter in the panel. The carrier gas, liquid crystal and other organic matter are separated by condensation. This method does not directly break the liquid crystal panel, and the method of heating under reduced pressure separates the liquid 2 and other organic substances (such as packaging materials) from the panel at the same time. This method does not mention the method of purifying and recovering liquid crystals, so the recovered liquid crystal material will contain a large amount of packaging material and cannot be directly applied. Some of the above methods are complicated in processing steps, some are only applicable to specific liquid crystals, some may change liquid crystal formulations, etc., and there are still many spaces for improvement in application. Therefore, the present invention provides a method for continuously recovering liquid crystals in waste panels, which can be applied to Most of the liquid crystal panels on the market are processed, and the liquid crystal impurities taken out are small and the formulation composition is unchanged. It can be reused only after being purified by the previously published liquid crystal purification method (patent of the Republic of China, patents 1282359 and 1297282). SUMMARY OF THE INVENTION The present invention provides a method for recovering liquid crystal in a waste panel, comprising: (1) disintegrating the waste panel after disintegrating the waste panel, so that the solvent dissolves the liquid crystal and the encapsulating material in the discarded panel to form an extraction (ii) cooling the extract to precipitate the encapsulating material, separating the encapsulating material from the extract, followed by filtering the adsorbent extract; (iii) heating the extract to form a vapor and condensing to form a recovery solvent; (iv) recycling The solvent is used to soak the fragmented waste panel to form an extract; and 0) repeating steps (ii) to (iv) until the liquid crystals in the panel are dissolved in the extract, and then removing the solvent to obtain a recovered liquid crystal. The invention also provides a device for recovering liquid crystal in a waste panel, comprising an extraction tank having a basic filtering function at the bottom of the extraction tank; a temperature control device located in the extraction tank or between the extraction tank and the filter adsorption device; the collecting tank having heating The device heats the collection tank; the first storage tank is located above the extraction tank and connected to the extraction tank; the second storage tank is located below the extraction tank and the filter adsorption device; and the condensation device is respectively connected to the collection tank and the first storage 6 8 1375587 The storage tank is located above the first storage tank and the collecting tank; wherein the extraction tank, the collecting tank and the second storage tank are respectively connected to the three-way valve by a pipeline, and the filtration-adsorption device is located between the extraction tank and the three-way valve. [Embodiment] The method for recovering the liquid crystal in the waste panel of the present invention is as shown in the flow chart of Fig. 1. First, after the waste panel is broken, the waste panel is soaked in a solvent to dissolve the liquid crystal of the waste panel to form an extract. The source of the discarded panel can be a scrapped product of the factory process, or it can be a recycled product after a period of use. The method for disintegrating the waste panel of the present invention is to directly disassemble the frame until only the liquid crystal cell portion is crushed, and it is not necessary to remove the encapsulating material such as the frame glue. In an embodiment of the invention, the fragmented liquid crystal panel has a chip size of less than 1 平方 square centimeter. The solvent suitable for use in the present invention may be a C6-10 alkane such as n-hexane, a C3_5 alcohol such as isopropanol, a C2_4 ether such as diethyl ether, a C3-5 ketone such as acetone, methyl ethyl ketone or pentanone, or a mixed solvent thereof. . It is noted that the present invention dissolves the liquid crystals in the waste panel by soaking rather than flushing. Due to the gap between the shredded waste panels, the flushing method will not allow the solvent to flow into the gaps to dissolve the liquid crystals, which will reduce the recovery efficiency. On the contrary, the immersion method can stably allow the solvent to flow into the above gap. In one embodiment of the invention, the solvent that soaks the fractured waste panel has a liquid level that is higher than the topmost waste panel. In one embodiment of the invention, the soaking time is between about 10 minutes and 1 hour. It is worth noting that the solvent in this step will also dissolve part of the packaging material. The extract is then cooled to provide a poor solubility in the extract.
7 1375587 料析出形成固體。固化之封裝材料與萃取液固液分離後， 萃取液經過濾吸附裝置以去除其中非液晶成分的雜質。在 本發明一實施例中，上述之冷卻溫度約介於10°c至-60°c之 間。過濾吸附之步驟中可只靠重力過濾，或利用惰性氣體 加壓過濾，例如：使用純度99.99%以上之氮氣、氦氣、氬 氣或其混合氣體。 接著加熱過濾吸附後之萃取液使溶劑形成蒸氣。冷凝 蒸氣形成回收溶劑，可再一次浸泡上述碎裂之廢棄面板形 成第二批的萃取液。將第二批的萃取液冷卻以析出封裝材 料後，過濾吸附萃取液。接著再次加熱、冷凝以形成回收 溶劑，並用以浸泡碎裂之廢棄面板。重複上述步驟2至10 次，直到碎裂之廢棄面板上無殘留任何液晶為止，最後將 萃取液加熱、冷凝形成回收溶劑儲存於儲存槽中，而收集 槽中將只剩下回收之液晶。如此一來，最後回收之液晶純 度較高，不需繁複之純化製程。 接著將回收之液晶卸下並置於抽氣櫃，使殘留的少數 溶劑自然揮發。在本發明一實施例中，可進一步加熱溶劑 加速揮發或以惰性氣體吹乾液晶以去除殘留之溶劑，適當 的惰性氣體為只要吹乾過程不發生反應即可，如高純度之 氮氣、氦氣、氬氣或其混合氣體。由於本發明在過濾吸附 前已降溫使萃取液中的封裝材料析出，接著以過濾吸附步 驟去除雜質，因此去除殘留溶劑後之回收液晶其純度與原 料類似，且回收效率高達95%以上。在本發明的實施例中， 回收液晶的性質：配方已與市售之液晶組成幾乎相同，可 直接進行純化去除水分和金屬離子後再次利用而不需額外 ⑧ 1375587 添加液晶單體。 · 除了上述回收方法外，本發明亦提供一種回收裝.置如 第2圖所示。上述回收裝置具有萃取槽11、儲存槽12及 14、與收集槽13。萃取槽11與收集槽13兩者間以連通管 18A連接，且萃取槽11下方依序設有濾板22、開關閥43、 及過濾吸附裝置15。回收裝置亦具有冷凝裝置17，分別以 連通管18B及18C連接至收集槽13及儲存槽12。在本發 明一實施例中，可調整收集槽13與過濾吸附裝置15之相 對高度以縮短收集槽13與冷凝裝置17之間的距離（即連通 管18B之長度）。當連通管18B的長度越短，回收溶劑所需 的能量越少。當收集槽13之高度低於過濾吸附裝置15， 則過濾吸附後之萃取液將可藉重力流入收集槽13中。另一 方面，若收集槽13之高度高於過濾吸附裝置15，則需另 外架設泵浦16連接三向閥29及收集槽13以將萃取液抽至 收集槽13。 如此一來，可先經補液口 24將溶劑加入儲存槽12。 溶劑經開關閥42流入萃取槽11後，溶解碎裂之廢棄面板 所含的液晶及封裝材料。上述之萃取液經冷卻後，流經遽 板22、開關閥43、過濾吸附裝置15、三向閥29、連通管 18A、及開關閥44以進入收集槽13中。收集槽13中之溶 劑經加熱後產生之蒸氣會經由連通管18B到達冷凝裝置 17,冷凝後之液滴會經由連通管18C及開關閥41流入儲存 槽12，達成循環的效果。除了將溶劑加入儲存槽12外， 亦可經補液P 25將溶劑加入收集槽13，其循環過程與前 述類似。上述回收裝置亦具有儲存槽14以儲存萃取結束後 1375587 之溶劑，以及氣體加壓裝置。上述氣體加壓裝置包括氣體 -鋼瓶31及氣壓控制裝置33，雨者間以連通管32連接，用 以加壓過濾萃取溶劑。前述之氣壓控制裝置可控制加壓 過濾時萃取槽11内之氣壓大小，加壓過濾氣壓可控制在 〇〜60 psi。此外，在加壓過濾的步驟中，需關閉開關閥41 以維持萃取槽11的壓力。在加壓過濾結束後，需開啟開關 閥41使萃取槽U洩壓。 萃取槽11具有進出料口 21及觀景窗23。進出料口 21 係用以將碎裂之廢棄面板置入/移出萃取槽U，其進出量介 於1公斤至1000公斤。觀景窗23係用以確認溶劑液面是 否覆蓋最上層之碎裂面板。 萃取槽11下之濾板22其作用在於濾除玻璃碎屑。上 述遽板係用以避免玻璃碎屑進入過濾吸附裝置15和去除 液晶中粒徑較大之雜質，其孔徑介於 0·2μπι 至 ΙΟμπ 之間^ 濾板22可進一步含有濾網，其材質可為不鏽鋼或塑膠材質 以固定濾板。在本發明一實施例中，濾網材質為不鏽鋼， 其孔徑介於0.1mm至lmm之間。滤板材質包括聚乙婦7 1375587 The material precipitated to form a solid. After the solidified encapsulating material is separated from the extract by solid-liquid separation, the extract is filtered through an adsorption device to remove impurities of the non-liquid crystal component. In an embodiment of the invention, the cooling temperature is between about 10 ° C and -60 ° c. The step of filtering and adsorbing may be carried out by gravity only, or by inert gas pressure filtration, for example, using nitrogen, helium, argon or a mixture thereof having a purity of 99.99% or more. The adsorbed extract is then heated and filtered to form a vapor. The condensed vapor forms a recovery solvent which can be immersed again to form a second batch of the extract. After the second batch of the extract was cooled to precipitate the package material, the adsorbed extract was filtered. It is then heated again, condensed to form a recovery solvent, and used to soak the fractured waste panels. Repeat the above steps 2 to 10 times until no liquid crystal remains on the broken waste panel. Finally, the extract is heated and condensed to form a recovery solvent and stored in the storage tank, and only the recovered liquid crystal will remain in the collection tank. As a result, the final recovered liquid crystal has a higher purity and does not require a complicated purification process. The recovered liquid crystal is then removed and placed in a suction cabinet to allow a small amount of residual solvent to naturally evaporate. In an embodiment of the present invention, the solvent may be further heated to accelerate volatilization or the liquid crystal is dried by an inert gas to remove residual solvent. The appropriate inert gas is as long as the reaction does not occur during the drying process, such as high-purity nitrogen gas and helium gas. , argon or a mixture thereof. Since the present invention has been cooled before filtration and adsorption to precipitate the encapsulating material in the extract, and then the impurities are removed by the filtration adsorption step, the recovered liquid crystal after removing the residual solvent has a purity similar to that of the original material, and the recovery efficiency is as high as 95% or more. In the embodiment of the present invention, the properties of the liquid crystal are recovered: the formulation has almost the same composition as the commercially available liquid crystal, and can be directly purified to remove moisture and metal ions and reused without additional 8 1375587 to add a liquid crystal monomer. In addition to the above-described recovery method, the present invention also provides a recovery apparatus as shown in Fig. 2. The above recovery apparatus has an extraction tank 11, storage tanks 12 and 14, and a collection tank 13. The extraction tank 11 and the collection tank 13 are connected by a communication pipe 18A, and a filter plate 22, an on-off valve 43, and a filter adsorption device 15 are sequentially disposed below the extraction tank 11. The recovery unit also has a condensing unit 17 which is connected to the collecting tank 13 and the storage tank 12 by communicating pipes 18B and 18C, respectively. In an embodiment of the invention, the relative height of the collection tank 13 and the filter adsorption unit 15 can be adjusted to shorten the distance between the collection tank 13 and the condensing unit 17 (i.e., the length of the communication tube 18B). The shorter the length of the communication tube 18B, the less energy is required to recover the solvent. When the height of the collecting tank 13 is lower than that of the filter adsorption device 15, the filtered adsorbed extract liquid can flow into the collecting tank 13 by gravity. On the other hand, if the height of the collecting tank 13 is higher than that of the filter adsorption unit 15, the pump 16 is additionally connected to the three-way valve 29 and the collecting tank 13 to pump the extract to the collecting tank 13. In this way, the solvent can be first introduced into the storage tank 12 through the refill port 24. After the solvent flows into the extraction tank 11 through the on-off valve 42, the liquid crystal and the encapsulating material contained in the fragmented waste panel are dissolved. After the above-mentioned extract is cooled, it flows through the crucible 22, the on-off valve 43, the filter adsorption device 15, the three-way valve 29, the communication tube 18A, and the on-off valve 44 to enter the collection tank 13. The vapor generated by heating the solvent in the collecting tank 13 reaches the condensing device via the communicating pipe 18B. The condensed liquid droplets flow into the storage tank 12 through the communicating pipe 18C and the opening and closing valve 41, thereby achieving the effect of circulation. In addition to the addition of the solvent to the storage tank 12, the solvent may be added to the collection tank 13 via the rehydration liquid P25, and the circulation process is similar to the above. The above recovery device also has a storage tank 14 for storing the solvent of 1375587 after the end of the extraction, and a gas pressurizing device. The gas pressurizing device includes a gas-cylinder 31 and a gas pressure control device 33, and the rainers are connected by a communication pipe 32 for extracting the solvent by pressure filtration. The aforementioned air pressure control device can control the air pressure in the extraction tank 11 during pressure filtration, and the pressure filtration air pressure can be controlled at 〇~60 psi. Further, in the step of pressure filtration, the on-off valve 41 is closed to maintain the pressure of the extraction tank 11. After the end of the pressure filtration, the opening and closing valve 41 is opened to depressurize the extraction tank U. The extraction tank 11 has an inlet and outlet port 21 and a viewing window 23. The inlet and outlet ports 21 are used to place the shredded waste panels into/out of the extraction tank U, and the inflow and outflow ranges from 1 kg to 1000 kg. The viewing window 23 is used to confirm whether the solvent level covers the uppermost fragmented panel. The filter plate 22 under the extraction tank 11 functions to filter out glass debris. The filter plate is used to prevent glass debris from entering the filter adsorption device 15 and removing impurities having a large particle size in the liquid crystal, and the pore diameter is between 0·2 μπι and ΙΟμπ. The filter plate 22 may further comprise a filter mesh, and the material thereof may be It is made of stainless steel or plastic to fix the filter plate. In an embodiment of the invention, the filter mesh is made of stainless steel and has a diameter between 0.1 mm and 1 mm. Filter plate material includes poly-wife
明-實施例中結構為濾網/濾板/吸附劑/濾膜/滤板/遽網 組合之多層結構。遽板及遽網材f同前述，親材質則為 (PE)或聚丙稀(pp)、或棚矽酸破璃(pyrex⑧）。過濾吸附裝 15In the embodiment, the structure is a multi-layer structure of a combination of a sieve/filter plate/adsorbent/filter/filter plate/遽 mesh. The fascia and 遽 mesh material f are the same as the above, and the pro-material is (PE) or polypropylene (pp), or pyrex8. Filter adsorption device 15
(pyrex®)或分于師。 .” 土 υ·)μιη之間。在本發明一實施 ϋ化銘氧化叾夕、砍酸Is、硼>5夕酸玻璃 上述濾材及吸附劑可在萃取液自萃取 1375587 槽11流入收集槽13時，去除不屬於液晶的雜質。 .在本發明一實施例中，_萃取槽11具有控溫裝置以降低 萃取液之溫度，使溶解的封裝材料析出形成固體。在本發 明另一實施例中，控溫裝置係設置於濾板22與過濾吸附裝 置15之間，亦可達上述效果。 實際使用上，先將溶劑加入儲存槽12後，流入萃取槽 11中浸泡碎裂之廢棄面板形成萃取液，萃取液即液晶與溶 劑之溶液（含有少量封裝材料）。先以控溫裝置降低萃取液 的溫度’接著以氣體鋼瓶31經連通管32將過濾氣體送至 萃取槽Π以加壓上述萃取液，並以氣壓控制閥33控制氣 壓大小，使其經濾板22及過濾吸附裝置15以去除雜質後， 經連通管18A進入收集槽13。收集槽13具有加熱裝置27 加熱上述之萃取液，使溶劑形成蒸氣’並使液晶保留於收 集槽13中。上述加熱裝置27的加熱溫度端視溶劑沸點而 定。溶劑蒸氣經連通管18B進入冷凝裝置17，冷凝後形成 之液滴經連通管18C流入儲存槽12。待萃取槽11中之萃 取液經降溫及過濾吸附後完全流入收集槽13後，再打開開 關閥42使儲存槽12之回收溶劑流入萃取槽11，以再次浸 泡碎裂之液晶面板形成第二批萃取液。第二批萃取液經降 溫及加壓過濾吸附後流入收集槽13，再進行加熱回收溶 劑。上述浸泡、降溫、過濾吸附、回收溶劑之循環步驟河 進行到碎裂之廢棄面板無殘留任何液晶為止。最後，萃取 槽11中的溶劑（無液晶溶解其中）在過濾吸附後並不流入收 集槽13，而是流入儲存槽μ中。收集槽13中回收之液晶 可藉由卸料口 26流出收集。在本發明一實施例中，係以三 1375587 向閥29控制萃取液/溶劑流入收集槽13/儲存槽14。 -上述之連通管18A、18B、18C、及32胃之材質可為 PTFE、不鏽鋼、或破璃如市售之j>yrex⑧。上述之萃取槽 11、收集槽13、冷凝裝置π、儲存槽12與14、及過濾吸 附裝置15均為獨立構件並可分別拆卸組裝，有利於後續設 備清潔維護。 經上述回收方法及設備回收之液晶，其所含之溶劑極 少，所含之雜質比例極低’且回收效率高達95%以上。 綜上所述’本發明與習知技藝相較具有下列優點。首 先’本發明直接碎裂整塊面板，而不需事先去除框膠等封 裝材料’可降低回收步驟的複雜度。其次，本發明以浸泡 方式而非沖洗方式溶解液晶’可有效提高液晶的溶解度並 減少溶劑用量。三者，本發明以降溫方式使萃取液所溶之 封裝材料析出，固液分離可簡化回收液晶的純化步驟。最 後回收之液晶純度極高且配方比例不變，不需添加液晶 單體’只需經過先前發表之液晶純化方法即可直接應用於 產業。 〜5 為了讓本發明之目的、特徵、和優點能更明顯易懂， 下文特舉數實施例，作詳細說明如下： 【實施例】 實施例1 取某廠15对廢棄面板21片，其使用之液晶為扭轉向 列型（簡稱TN-Q1) ’碎裂後以丙酮為萘取溶劑，經本發明 之回收方法（請參考第1圖）與裝置回收液晶（請參考第2 ⑧ 12 1375587 圖）。值得注意的是，實施例1中的回收裝置不含有控溫裝 置及過濾吸.附裝置15。首先於200_0mL之萃取槽11中置入 lOOOmL的破碎面板。接著取3000 mL之丙酮作為萃取溶 劑加入儲存槽12中，接著打開開關閥42讓溶劑流入萃取 槽11，浸泡破碎面板30分鐘形成萃取液。接著萃取液經 濾板22過濾後流至收集槽13,以90°C水浴加熱收集槽13 使萃取液中的丙酮形成蒸氣。以冷凝裝置17將丙酮蒸氣凝 結形成液滴流入儲存槽12,待萃取槽11内之萃取液完全 流入收集槽13後，再打開開關閥42讓回收溶劑流入萃取 槽11以進行下一次的浸泡。上述循環中，每次溶劑經加 熱、蒸餾冷凝、浸泡破碎面板、和過濾的循環時間約為45 分鐘，上述流程總共需實施三次，即可完成一次萃取，萃 取完成後將丙酮去除則可取得回收液晶。預估液晶含量為 6.3克，實際回收量為6.6克，回收率超過95%。原始液晶 之氣相層析質譜（以下簡稱GCMS)圖譜如第3圖所示，其 性質如第1表所示。回收液晶之GCMS圖譜如第4圖所示。 由第3圖及第4圖比較可知，上述未經控溫、過濾吸附處 理之回收液晶仍有不少雜質。以丙酮溶解上述回收液晶 後，佐以-20度低溫冷析和過濾吸附裝置15處理，將其中 各種雜質進行析出與過濾吸附，所用吸附劑包含分子篩與 氧化鋁、硼矽酸玻璃等，其結果GCMS圖譜如第5圖所示， 其性質如第1表所示。由第5圖與第3圖之比較可知，經 冷析及過濾吸附處理後之回收液晶的雜質含量大幅減少。(pyrex®) or divided into divisions. Between the soil and the μιη. In the implementation of the present invention, the above-mentioned filter medium and adsorbent can be introduced into the collecting tank from the extracting solution 1375587 tank 11 in the extraction liquid, the sulphuric acid Is, the slashing acid Is, the boron > At 1300, impurities not belonging to the liquid crystal are removed. In an embodiment of the invention, the extraction tank 11 has a temperature control device to lower the temperature of the extract to precipitate the dissolved encapsulant to form a solid. In another embodiment of the present invention The temperature control device is disposed between the filter plate 22 and the filter adsorption device 15, and can achieve the above effects. In actual use, after the solvent is added to the storage tank 12, the waste panel is poured into the extraction tank 11 to form a waste panel. The extract, the extract is a solution of liquid crystal and solvent (containing a small amount of encapsulating material). First, the temperature of the extract is lowered by a temperature control device. Then, the gas is sent to the extraction tank through the communicating tube 32 through the gas cylinder 31 to pressurize the above. The extract liquid is controlled by the air pressure control valve 33 to pass through the filter plate 22 and the filter adsorption device 15 to remove impurities, and then enters the collecting tank 13 through the communication pipe 18A. The collecting tank 13 has a heating device 27 for heating. The extract is described so that the solvent forms a vapor and the liquid crystal remains in the collecting tank 13. The heating temperature of the heating device 27 depends on the boiling point of the solvent. The solvent vapor enters the condensing device 17 through the communicating tube 18B, and the liquid is formed after condensation. The drip through tube 18C flows into the storage tank 12. After the extract in the tank 11 to be extracted is cooled and filtered and adsorbed, it completely flows into the collecting tank 13, and then the opening and closing valve 42 is opened to cause the recovered solvent of the storage tank 12 to flow into the extraction tank 11 to be again Soaking the fragmented liquid crystal panel to form a second batch of extract liquid. The second batch of extract liquid is adsorbed by cooling and pressure filtration, and then flows into the collecting tank 13, and then heats and recovers the solvent. The above-mentioned cycle steps of soaking, cooling, filtering adsorption, and recovering the solvent The river proceeds to the fragmented waste panel without any residual liquid crystal. Finally, the solvent in the extraction tank 11 (without liquid crystal dissolved therein) does not flow into the collection tank 13 after the filtration adsorption, but flows into the storage tank μ. The collection tank 13 The recovered liquid crystal can be collected by the discharge port 26. In one embodiment of the invention, the extract/solvent inflow is controlled to the valve 29 by three 1375587. 13/storage tank 14. - The above-mentioned connecting tubes 18A, 18B, 18C, and 32 may be made of PTFE, stainless steel, or broken glass such as commercially available j>yrex 8. The above-mentioned extraction tank 11, collecting tank 13, and condensation The device π, the storage tanks 12 and 14 , and the filter adsorption device 15 are independent components and can be disassembled and assembled separately, which is beneficial to the subsequent equipment cleaning and maintenance. The liquid crystal recovered by the above recovery method and equipment contains few solvents, including The impurity ratio is extremely low' and the recovery efficiency is as high as 95% or more. In summary, the present invention has the following advantages over the prior art. First, the present invention directly breaks the entire panel without removing the sealant in advance. The encapsulating material 'reduces the complexity of the recycling step. Secondly, the present invention dissolves the liquid crystal by immersion rather than rinsing to effectively increase the solubility of the liquid crystal and reduce the amount of solvent. In the third aspect, the present invention precipitates the encapsulating material in which the extract is dissolved by means of a cooling method, and the solid-liquid separation simplifies the purification step of recovering the liquid crystal. The final recovered liquid crystal is extremely pure and the formulation ratio is constant, and no need to add liquid crystal monomer can be directly applied to the industry through the previously published liquid crystal purification method. In order to make the objects, features, and advantages of the present invention more comprehensible, the following detailed description of the embodiments will be described as follows: [Embodiment] Example 1 A pair of 15 discarded panels of a factory are used, and the use thereof is used. The liquid crystal is a twisted nematic type (TN-Q1 for short). After the fragmentation, acetone is used as a solvent for the naphthalene. The recovery method of the present invention (please refer to Fig. 1) and the device are used to recover the liquid crystal (refer to Fig. 2 8 12 1375587). . It is to be noted that the recovery apparatus of the first embodiment does not contain the temperature control means and the filter suction attachment means 15. First, a 1000 mL crushing panel was placed in the extraction tank 11 of 200_0 mL. Next, 3000 mL of acetone was introduced as an extraction solvent into the storage tank 12, and then the on-off valve 42 was opened to allow the solvent to flow into the extraction tank 11, and the panel was immersed for 30 minutes to form an extract. Then, the extract was filtered through a filter plate 22, and then passed to a collecting tank 13, and the collecting tank 13 was heated in a water bath at 90 ° C to form acetone in the extract to form a vapor. The acetone vapor is condensed by the condensing device 17 to form droplets flowing into the storage tank 12. After the extract liquid in the extraction tank 11 completely flows into the collecting tank 13, the opening and closing valve 42 is opened to allow the recovered solvent to flow into the extraction tank 11 for the next immersion. In the above cycle, each time the solvent is heated, distilled and condensed, soaked and crushed, and the filtration cycle time is about 45 minutes. The above process needs to be performed three times in total to complete one extraction. After the extraction is completed, the acetone can be removed for recovery. liquid crystal. The liquid crystal content is estimated to be 6.3 g, the actual recovery is 6.6 g, and the recovery rate is over 95%. The gas chromatography mass spectrometry (hereinafter referred to as GCMS) spectrum of the original liquid crystal is shown in Fig. 3, and its properties are shown in Table 1. The GCMS spectrum of the recovered liquid crystal is shown in Fig. 4. As can be seen from the comparison of Fig. 3 and Fig. 4, the above-mentioned uncontrolled temperature, filtered adsorption treatment of the recovered liquid crystal still has a lot of impurities. After the above-mentioned recovered liquid crystal is dissolved in acetone, it is treated by a -20 degree low-temperature cold precipitation and filtration adsorption device 15, and various impurities are precipitated and filtered and adsorbed, and the adsorbent used includes molecular sieve, alumina, borosilicate glass, etc. The GCMS spectrum is shown in Figure 5, and its properties are shown in Table 1. From the comparison between Fig. 5 and Fig. 3, it is understood that the impurity content of the recovered liquid crystal after the cold precipitation and the filtration adsorption treatment is drastically reduced.
13 1375587 第1表 測試項目 經冷析和過濾吸附處理之 回收液晶 原始液晶 流動黏度(20°C，cps) 23 23 澄清點（Tc，°C) 86.3 86.7 臨界電壓Vth (4.0μπι之液晶盒） 1.38伏特 1.38伏特 Pitch值（4·Ομπι之液晶盒） 55.0μιη 59.2μπι 阻值(Qcm) 1.1Ε+12 6.20Ε+13 含水率(ppm) 62.0 36.6 折射率(Δη) 0.089 0.089 介電性(Δε) 10.4 10.3 純度(GCMS，％) >99.5 100 實施例2 與實施例1類似，差別在於萃取溶劑由丙酮換成正己 烷，收集槽13之水浴溫度則為85°C，且在萃取槽11中加 裝控溫裝置、在收集槽13與萃取槽11之間架設了過濾吸 附裝置15。其GCMS圖譜如第6圖所示。由第6圖與第3 圖之比較可知，實施例2之回收液晶的組成與原始液晶非 常類似。 實施例3 取某廠32吋廢棄面板76片，其使用之液晶為垂直配 向型（簡稱VA-C1)，碎裂後以正己烷為萃取溶劑，經本發 明之回收方法（如第1圖所示）與裝置（如第2圖所示）回收液 晶，首先於30L之萃取槽中置入20L的破碎面板。接著取 40L之正己烷作為萃取溶劑加入儲存槽中，接著使萃取溶 劑流入萃取槽，浸泡破碎面板30分鐘形成萃取液。接著萃 1375587 取液經控溫、過濾吸附後之萃取液流至收集槽，以90〇C水 •浴加熱收集槽使萃取液中的正·己烷形成蒸氣。以冷凝裝置 將正己烧条氣凝結形成液滴流入儲存槽，待萃取槽内之萃 取液完全流入收集槽後’再讓回收溶劑流入萃取槽以進行 下一次的浸泡。上述循環中，每次溶劑經加熱、蒸餾冷凝、 浸泡破碎面板、冷卻以析出封裝材料、及過濾吸附的循環 時間約為40分鐘，上述流程總共需實施三次，即可完成一 次萃取，萃取完成後將剩餘之正己烷溶劑蒐集於儲存槽 • 中’由收集槽中取出含有少量正己烷之液晶，接著去除剩 餘之正己烷後則可得到回收液晶。預估液晶含量為76克， 實際回收量為74.5克，回收率超過95%，其性質如第2表 所示’其GCMS圖譜如第8圖所示。將回收之液晶經 1282359和1297282之液晶純化方法再純化後，性質如第2 表所示。原始液晶之GCMS圖譜如第7圖所示，其性質如 第2表所示。由第7圖與第8圖之比較可知，回收液晶的 組成與原始液晶非常類似。此外，實施例3有進一步將回 鲁 收量放大到670片廢棄面板，預估液晶含量為670克，實 際回收量為650g，回收率超過95%。除了回收時間較長以 外，回收液晶之GCMS圖譜與第8圖相同。再者，進一步 將回收之液晶經1282359和1297282之液晶純化方法再純 化後灌入面板測試片進行電壓保持率（VHR)測試，並將新 • 品液晶灌入面板測試片進行數值比對。分別將上述兩片測 試片進行可靠性試驗（長時間高溫烘烤，簡稱RA)，並在試驗 前後分別於兩片測試片之相.同的兩個位置（中央點和框膠 點）進行電壓保持率測試（VHR)測試，結果發現灌入回收液 15 1375587 晶之面板測試片不論是在RA前後其兩個位置之電壓保持 率皆名-灌入新品-液晶之面板測試片於RA前後之-數-值、相...... 近，如第.3表所示，証明本發明之回收方法亦適用於大量 回收。 第2表 測試項目 回收液晶 經再純化之回收液晶 原始液晶 流動黏度(20°C, cps) 20 20 21 澄清點(Tc，°C) 75.5 75.2 75.0 臨界電壓Vth (4.0μπι之 液晶盒） 3.12伏特 3.13伏特 3.10伏特 阻值(Ωαη) 5.8Ε+11 1.4Ε+14 5.0Ε+13 含水率(ppm) 58.5 39.7 45.0 折射率(Δη) 0.081 0.082 0.082 介電性(Δε) -3.0 -3.0 -3.1 純度(GCMS,%) >99.5 >99.5% 100 第3表 電壓保持率測試(VHR) 中央點 框膠點 回收液晶 新品液晶 回收液晶 新品液晶 RA前 98.2 % 98.1 % 97.6 % 97.5 % RA後 96.9 % 97.2 % 87.8 % 86.3 % 實施例4 取某廠兩種32吋廢棄面板60片，其使用之液晶為不 同之垂直配向型（簡稱VA-C1及VA-C2)，碎裂後以正己烷 為萃取溶劑，經本發明第2圖所示之回收裝置回收液晶。 本例使用之溶劑添加量與實驗反應參數和實施例3相同。 預估液晶含量為60克，實際回收量為60g，回收率超過 1375587 .- 95%，回收液晶之GCMS圖譜如第10圖所示。原始液晶 . (VA_-C2)之GCMS圖譜如第9圖所-示。由第· 7凰.、第9亂 與第10圖之比較可知，回收液晶的組成與原始液晶非常類 似。由實施例4可t正明，本技術可應用於市面上廢棄面中 的液晶回收再處理，一樣具有極高回收率。 雖然本發明已以數個較佳實施例揭露如上，然其並非 用以限定本發明，任何熟習此技藝者，在不脫離本發明之 精神和範圍内，當可作任意之更動與潤飾，因此本發明之 • 保護範圍當視後附之申請專利範圍所界定者為準。13 1375587 Table 1 Test item Recovery of liquid crystal raw liquid crystal flow viscosity (20 ° C, cps) by cold analysis and filtration adsorption treatment 23 23 Clarification point (Tc, ° C) 86.3 86.7 Threshold voltage Vth (4.0 μπι liquid crystal cell) 1.38 volts 1.38 volts Pitch value (4·Ομπι liquid crystal cell) 55.0μιη 59.2μπι Resistance (Qcm) 1.1Ε+12 6.20Ε+13 Water content (ppm) 62.0 36.6 Refractive index (Δη) 0.089 0.089 Dielectric (Δε 10.4 10.3 Purity (GCMS, %) > 99.5 100 Example 2 Similar to Example 1, except that the extraction solvent was changed from acetone to n-hexane, and the water bath temperature of the collection tank 13 was 85 ° C, and in the extraction tank 11 A temperature control device is installed in the middle, and a filter adsorption device 15 is placed between the collection tank 13 and the extraction tank 11. Its GCMS map is shown in Figure 6. As is apparent from comparison of Fig. 6 and Fig. 3, the composition of the recovered liquid crystal of Example 2 is very similar to that of the original liquid crystal. Example 3 A piece of waste 32 sheets of a 32-inch factory was taken, and the liquid crystal used was a vertical alignment type (abbreviated as VA-C1), and after the fragmentation, n-hexane was used as an extraction solvent, and the recovery method of the present invention (as shown in FIG. 1) ) The liquid crystal was recovered from the apparatus (as shown in Fig. 2), and a 20 L fracture panel was first placed in a 30 L extraction tank. Next, 40 L of n-hexane was added as an extraction solvent to the storage tank, and then the extract solvent was poured into the extraction tank, and the panel was immersed for 30 minutes to form an extract. Then, 1375587 is taken, and the extract obtained by the temperature control and filtration adsorption flows to the collecting tank, and the collecting tank is heated in a bath of 90 〇C water to form a vapor of n-hexane in the extract. The condensing device is used to condense the condensed gas to form a droplet into the storage tank, and the extract liquid in the extraction tank completely flows into the collecting tank, and then the recovery solvent flows into the extraction tank for the next immersion. In the above cycle, each time the solvent is heated, distilled and condensed, soaked and crushed, and cooled to precipitate the encapsulating material, and the filtration and adsorption cycle time is about 40 minutes. The above process needs to be performed three times in total to complete one extraction, after the extraction is completed. The remaining n-hexane solvent is collected in a storage tank. The liquid crystal containing a small amount of n-hexane is taken out from the collection tank, and then the remaining n-hexane is removed to obtain a recovered liquid crystal. The liquid crystal content is estimated to be 76 g, the actual recovery is 74.5 g, and the recovery is over 95%. The properties are as shown in Table 2, and the GCMS spectrum is shown in Fig. 8. After the recovered liquid crystals were further purified by the liquid crystal purification methods of 1282359 and 1297282, the properties are as shown in Table 2. The GCMS spectrum of the original liquid crystal is shown in Fig. 7, and its properties are shown in Table 2. As can be seen from the comparison of Fig. 7 and Fig. 8, the composition of the recovered liquid crystal is very similar to that of the original liquid crystal. In addition, in Example 3, the recovery amount was further enlarged to 670 discarded panels, and the liquid crystal content was estimated to be 670 g, and the actual recovery amount was 650 g, and the recovery rate was over 95%. The GCMS spectrum for recovering liquid crystals is the same as in Fig. 8 except that the recovery time is long. Furthermore, the recovered liquid crystals are further purified by the liquid crystal purification methods of 1282359 and 1297282, and then poured into the panel test piece for voltage maintenance ratio (VHR) test, and the new liquid crystal is poured into the panel test piece for numerical comparison. The above two test pieces were respectively subjected to a reliability test (long-time high-temperature baking, referred to as RA), and voltages were applied to the same two positions (center point and frame glue point) of the two test pieces before and after the test. The retention rate test (VHR) test found that the panel test piece of 15 1375587 crystal was filled with the voltage retention rate of both positions before and after RA - pouring into the new product - the panel test piece of liquid crystal before and after RA - number-value, phase... Near, as shown in the table of Table 3, it is proved that the recovery method of the present invention is also suitable for mass recovery. Table 2 Test item recovery liquid crystal re-purified recovered liquid crystal original liquid crystal flow viscosity (20 ° C, cps) 20 20 21 Clarification point (Tc, ° C) 75.5 75.2 75.0 threshold voltage Vth (4.0μπι liquid crystal cell) 3.12 volts 3.13 volts 3.10 volts resistance (Ωαη) 5.8Ε+11 1.4Ε+14 5.0Ε+13 Water content (ppm) 58.5 39.7 45.0 Refractive index (Δη) 0.081 0.082 0.082 Dielectricity (Δε) -3.0 -3.0 -3.1 Purity (GCMS,%) >99.5 >99.5% 100 Table 3 voltage retention test (VHR) Central point frame glue point recovery LCD new liquid crystal recovery LCD new liquid crystal RA before 98.2% 98.1 % 97.6 % 97.5 % RA after 96.9 % 97.2 % 87.8 % 86.3 % Example 4 Take 60 pieces of two 32-inch discarded panels from a factory. The liquid crystals used are different vertical alignment types (referred to as VA-C1 and VA-C2), and the samples are extracted with n-hexane after fragmentation. The solvent is recovered by the recovery apparatus shown in Fig. 2 of the present invention. The solvent addition amount used in this example was the same as that of the experimental reaction parameters. The liquid crystal content is estimated to be 60 g, the actual recovery amount is 60 g, the recovery rate is over 1375587 . - 95%, and the GCMS spectrum of the recovered liquid crystal is as shown in Fig. 10. The GCMS spectrum of the original liquid crystal (VA_-C2) is shown in Fig. 9. From the comparison of the seventh phoenix, the ninth chaos and the tenth graph, the composition of the recovered liquid crystal is very similar to that of the original liquid crystal. According to the embodiment 4, the present technology can be applied to the liquid crystal recycling and reprocessing in the waste surface of the market, and has the same high recovery rate. While the invention has been described above in terms of several preferred embodiments, it is not intended to limit the invention, and the invention may be modified and modified without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims.
17 1375587 【圖式簡單說明】 二- 第1圖〜係-本發明一實施例中，回收廢棄面板中液晶之-- - 流程圖； 第2圖係本發明一實施例中，回收廢棄面板中液晶之 裝置示意圖； 第3圖係本發明實施例1中，原始液晶TN-Q1之GCMS 圖譜； 第4圖係本發明實施例1中，回收液晶之GCMS圖譜； 第5圖係本發明實施例1中，經冷析和過濾吸附之回 鲁 收液晶之GCMS圖譜； 第6圖係本發明實施例2中，經過濾吸附之回收液晶 之GCMS圖譜；17 1375587 [Simple description of the drawings] II - Fig. 1 - system - in one embodiment of the present invention, recycling liquid crystal in a waste panel - a flow chart; Fig. 2 is an embodiment of the present invention, recycling waste panels FIG. 3 is a GCMS spectrum of the original liquid crystal TN-Q1 in the first embodiment of the present invention; FIG. 4 is a GCMS spectrum of the liquid crystal recovered in the first embodiment of the present invention; and FIG. 5 is an embodiment of the present invention. In the first embodiment, the GCMS spectrum of the liquid crystal is recovered by cold analysis and filtration; and FIG. 6 is a GCMS spectrum of the liquid crystal recovered by filtration adsorption in the second embodiment of the present invention;
第7圖係本發明實施例3中，原始液晶VA-C1之GCMS 圖譜； 第8圖係本發明實施例3中，回收液晶之GCMS圖譜； 第9圖係本發明實施例4中，原始液晶VA-C2之GCMS 圖譜；以及 · 第10圖係本發明實施例4中，回收液晶之GCMS圖 譜。 【主要元件符號說明】 11〜萃取槽； 12、14〜儲存槽； 13〜收集槽；· 18 ⑧7 is a GCMS spectrum of the original liquid crystal VA-C1 in the third embodiment of the present invention; FIG. 8 is a GCMS spectrum of the liquid crystal recovered in the third embodiment of the present invention; and FIG. 9 is an original liquid crystal in the fourth embodiment of the present invention. GCMS spectrum of VA-C2; and Fig. 10 is a GCMS spectrum of liquid crystal recovered in Example 4 of the present invention. [Main component symbol description] 11~ extraction tank; 12, 14~ storage tank; 13~ collection tank; · 18 8