201006541 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、低耗電量、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0.1-0.2%左右，卻會 因法規使面板玻璃無法回收再利用。目前合灣已是世界最 大的LCD出產國之一，而歐盟於2003年所公佈之廢電機/ 電子设傷指令（Waste Electrical and Electronics201006541 VI. Description of the Invention: [Technical Field] The present invention relates to a method and apparatus for recycling liquid crystal in a waste panel, more particularly to a cyclic extraction method therein. [Prior Art] Liquid crystal displays have the advantages of 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, incineration or burying of the waste panel without removing the liquid crystal may cause environmental pollution. Although the amount of liquid crystal is only about 0.1-0.2% of the total weight of the panel, the panel glass cannot be recycled and reused due to regulations. At present, Hewan is one of the world's largest LCD producing countries, and the European Union announced in 2003 the Waste Electrical and Electronics Injury Command (Waste Electrical 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！XD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。 JP2001-337305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 且Μ 收。此方法必須先去除偏光板和框膠，流程較繁雜 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，使液晶與水分離时。然而，經本㈣之發明人實驗， 201006541 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。Equipment's referred to as WEEE) has required manufacturers to be responsible for the recycling of the merchandise. Predictable is abandoned in the next few years! There will be more and more XD panels. If you can take out the liquid crystal from the waste panel and reuse the recycled liquid crystal, it will achieve both environmental protection and economical effects. ^In recent years, there have been patents related to discarded panel processing. . JP2001-337305 first removes the polarizing plate by hand tearing and cuts off the sealant part, then breaks the panel, and then washes the liquid crystal in the panel back with a solvent and collects it. This method must first remove the polarizing plate and the frame glue, and the process is complicated. The method of rinsing removes the liquid crystal and consumes a lot of solvent. In JP2002-166259, the liquid crystal is dissolved in hot water, and the solution is cooled to room temperature to separate the liquid crystal from the water. However, according to the inventor's experiment of this (4), 201006541 found that the hot water dissolves very poorly on most liquid crystals. This method consumes a large amount of heat energy but cannot effectively recover the liquid crystal.
JP2002-254059以電乳分離的方法，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 授拌幫助溶解液晶後，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 此回收之液晶材料將含有大量封裝材料而無法直接應用。 TW 2004-04884先去除框膠，再以溶劑溶解液晶或以 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 收之液晶需進一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 ，晶的方式為管柱層析，回收後的液晶材料又需添加液晶 單體才能再使用’均大幅增加回收液晶的複雜度與成本。 JP2006-089605使用極性和非極性之混合有機溶劑苹 出液晶’再以管柱層析純化回收之液晶產物。此方法的绅 化方式為管柱層析，於大量回收應用上較困難，且回收種 的液晶材料亦需添加液晶單體才能再使用。 TP2(K)6_184376利用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載流氣體、液晶和其他有機物。 ，方法並未直接碎裂液晶面板，且減壓加熱的方法會將液 、曰曰及其他有機物（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 201006541 含有大量：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 液曰曰有二會改變液晶配方等，應用上仍有許多可改善的 工間目此本發明提供—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 液B曰雜質夕且配方組成不變，僅需以先前發表之液晶純 化方法（中華民國的專利1282359 * 12972 化後即 可爯利用。 參 【發明内容】 :發明提供一種回收廢棄面板中液晶之方法，包括⑴ 劑浸泡碎裂之廢棄面板，使溶剩溶 冷卻‘取浚、把板中的液晶及封裴材料以形成萃取液；⑼ 離，接著封裝㈣，使封裝材料與萃取液固液分 取液；⑽加熱萃取液使溶劑形成蒸氣 並冷凝形成回收溶劑；㈣ 财 板，形成萃取液.以;5 r劑次泡碎裂之廢棄面 液晶皆溶重複步驟⑼至㈣直到面板中之 種再將溶劑去除以得到回收液晶。 萃取槽，:有包括 二萃取槽中或位於萃取槽舆過===集 上方且連接至萃取榑.第一 轉槽’位於萃取槽 附裝·置下方;以及連:於萃取槽與祕 置77別連接至收集槽及第一儲 6 201006541 存槽，且位於第一儲存槽及收集槽上方；其中 集槽、與第二儲存槽分別以管線連接至三向間 、收 附裝置位於萃取槽與三向閥之間。一―’且過攄吸JP2002-254059 uses a method of electro-milk separation to break up the waste panel in water and then elute the liquid crystal on the panel with a solvent. After supersonic oscillation or mixing is used to help dissolve the liquid crystal, the solvent is evaporated to obtain a liquid crystal. 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, nor the method for purifying and recovering the liquid crystal, the recovered liquid crystal material will contain a large amount of encapsulating material and cannot be directly applied. TW 2004-04884 first removes the sealant, dissolves the liquid crystal in a solvent, or removes the liquid crystal by a blowing method or a centrifuge, and 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 further added with a liquid crystal monomer 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 purification method is the column chromatography, and the liquid crystal material after the recovery needs to add the liquid crystal monomer to be used again, which greatly increases the complexity of recycling the liquid crystal. cost. JP2006-089605 uses a mixed organic solvent of a polar and a non-polar solvent to remove the liquid crystal product and then purifies the recovered liquid crystal product by column chromatography. The method of deuteration of this method is column chromatography, which is difficult to use in a large amount of recycling, and the liquid crystal material of the recovered species also needs to be added with a liquid crystal monomer. TP2(K)6_184376 decomposes the liquid crystal and organic matter in the panel by decompression heating to separate carrier gas, liquid crystal and other organic substances by condensation. The method does not directly break the liquid crystal panel, and the method of heating under reduced pressure separates liquid, hydrazine 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 recycled liquid crystal material will contain a large amount of materials: 201006541 and cannot be directly applied. Some of the above-mentioned methods are complicated in processing steps, some are only applicable to specific liquids, two are liquid crystal formulations, and the like, there are still many improvements in the application. The present invention provides a method for continuously recovering liquid crystal in waste panels. It can be used to process most of the liquid crystal panels on the market, and the liquid B is removed from the impurities and the composition of the composition is unchanged. It can be used only after the previously published liquid crystal purification method (the patent of the Republic of China patent 1282359 * 12972). The invention provides a method for recovering liquid crystal in a waste panel, comprising: (1) immersing and disintegrating the waste panel, dissolving the dissolved solution, taking the liquid crystal in the plate and sealing the material to form an extract; (9) leaving, then encapsulating (4), taking the encapsulating material and the extract liquid to separate the liquid; (10) heating the extract to form a vapor and condensing to form a recovery solvent; (4) the rich plate, forming an extract; Repeat the steps (9) to (4) until the liquid in the panel is removed, and then remove the solvent to obtain the recovered liquid crystal. The extraction tank: includes two extraction tanks or The extraction tank is over the === set and connected to the extraction crucible. The first trough is located below the extraction tank attachment and placement; and the connection: the extraction tank and the secret 77 are connected to the collection tank and the first storage 6 201006541 The storage tank is located above the first storage tank and the collecting tank; wherein the collecting tank and the second storage tank are respectively connected by a pipeline to the three-way space, and the collecting device is located between the extraction tank and the three-way valve. Sucking
【實施方式J 所示本的方法如第1圖之流程圖 可為工廠製程的報廢產品，亦時t來源 物。本發明碎裂廢棄面板的方法為事先拆回收 後直接壓碎’不需移除框膠等封裝㈣剩： ΐ:二裂後之液晶面板碎片尺寸小於1。。 烧，C之醇之溶劑可為c-之烧類如正己 c3_5t_如異丙醇，k之贿 如丙酮、丁 _或六獅，—叫13-5 <剩類 本發明以浸泡而非冲=合溶劑。值得注意的是， 晶。由於碎裂之廢棄(flusl°方式溶解廢棄面板中的液 使溶劑流人如空間具有空隙1沖洗方式將無法 降。反之，浸；的液晶，使回收效率下 發明-實施例中，浸、、包=㈣☆劑流人上述空隙。在本 於最項端的廢棄面板2裂廢棄面板之溶劑其液面高度高 介於10分鐘幻小時本3發明一實施例中’浸泡時間約 溶解部份的封襄材料、。值得注意的是，此步驟之溶劑亦會 接著將萃取液降'甚，使萃取液.中溶解度較差之封裝材 201006541 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 201006541 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n、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、開關闕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ι3及儲存槽12。在本發 明一實施例中，可調整收集槽13與過濾吸附裝置丨5之相 對if?度以縮短收集槽13與冷凝裝置Η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。當收集糟13之高度低於過滤吸附裝置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，条收集槽13之向度高於過濾吸附裝置15，則需另 外架設泵浦丨6連接二向閾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η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，流經濾 板22、開關閥43、過濾吸附裝置15、三向闕29、連通管 18A、及開關閥44以進入收集槽ο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， 亦可經補液口 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M以儲存萃取妗束後 201006541 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33，兩者間以連通管32連接，用 以加壓過濾萃取溶劑。前述之氣壓控制裝置33可控制加壓 過;慮時萃取槽11内之氣壓大小，加壓過濾、氣壓可控制在 0〜60 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π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11，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 述濾板係用以避免玻璃碎屑進入過濾吸附裝置15和去除 液aa中粒徑較大之雜質’其孔徑介於Q.2gm至之間。 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。濾板材質包括聚乙烯 (PE)、或聚丙稀(PP)、或彌;g夕酸破璃(pyrex⑧）。過濾吸附裝 置15可為單層或多層結構，可用以去除其餘雜質。在本發 明一實施例中結構為濾網/濾板/吸附劑/濾膜/濾板/濾網 組合之多層結構。遽板及據網材質同前述，滤膜材質則為 ，偏二氟乙烯(PVDF)或聚四氣乙稀(pTFE)，兩者皆俗稱鐵 氣龍，其孔徑介於〇.1μπ^ 〇 5μηι之間。在本發明一實施 例中’吸附劑可為氧化銘、氧化石夕、石夕酸銘、侧石夕酸破璃 (pyre,或分子_。上述—及吸_可在萃取液自萃取 201006541 槽11流入收集槽13時，去除不屬於液晶的雜質。 在本發明實施例中，萃取槽1 1具有控潘裝置以降低-萃取液之溫度，使溶解的封裝材料析出形成固艨。在本發 明另一實施例中，控溫裝置係設置於濾板2 2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’接著以氧體鋼瓶31經連通管3.2將過濾、氣體送至 萃取槽11以加廢上述萃取液，並以氣壓控制闕33控制氣 壓大小，使其經濾板22及過滤吸附裝置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π，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 溫及加壓過滤吸附後流入收集槽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可 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14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 11 201006541 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ΙδΑ、18B、18C v及32之材質可為 PTFE、不錄鋼、或玻璃如市售之pyrex⑧。上述之萃取槽 U、收集槽13、冷凝裝置17、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。 综上所述，本發明與習知技藝相較具有下列優點。首 Ο 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，固液分雞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。 ⑩ 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吋廢棄面板21片’其使用之液晶為扭轉向 列型（簡稱TN-Q1)，碎裂後以丙酮為萃取溶劑，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 12 201006541 $ S 主意的是，實施例1中的回收裝置不含有控溫裝 ’及附裴置15。首先於2〇〇〇mL之萃取槽η中置入 1〇 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1 破碎面板3G分鐘形成萃取液。接著萃取液經[The method shown in Embodiment J is as shown in the flow chart of Fig. 1 and can be a scrapped product of a factory process, and is also a source of t. The method for disintegrating the waste panel of the present invention is directly crushed after being pre-removed and recycled. The package is not required to be removed. (4) Remaining: ΐ: The size of the liquid crystal panel after the splitting is less than 1. . The solvent of the alcohol of C can be c-burned such as hexamethylene c3_5t_such as isopropyl alcohol, bri brittle such as acetone, butyl or lion, - 13-5 < residual type of the invention to soak instead Punching = solvent. It is worth noting that the crystal. Disintegration due to fragmentation (flusl ° dissolves the liquid in the waste panel so that the solvent flows into the space such as the space has a gap 1 flushing mode will not fall. Conversely, the liquid crystal of the dip; the recycling efficiency of the invention - in the example, dip, Package = (4) ☆ agent flow in the above gap. In the waste panel of the most end, the solvent of the waste panel is high in the liquid level of 10 minutes. In the first embodiment of the invention, the soaking time is about the dissolved part. Sealing material, it is worth noting that the solvent of this step will then reduce the extract evenly, so that the solubility of the package material 201006541 in the extract is precipitated to form a solid. The solidified packaging material and the extract liquid-liquid separation Thereafter, the extract is filtered to adsorb impurities in the non-liquid crystal component. In an embodiment of the invention, the cooling temperature is between about 10 ° C and -60 ° c. Filter by gravity or pressurize with inert gas, for example, use nitrogen, helium, argon or a mixture thereof with a purity of 99.99% or more. Then heat and filter the adsorbed extract to form a solvent. Vapor. The condensed vapor forms a recovery solvent, which can be once again immersed in the fragmented waste panel to form a second batch of extract. After the second batch of the extract is cooled to precipitate the encapsulating material, the adsorbed extract is filtered, and then heated and condensed again. To form a recovery solvent and to soak the scraped waste panel. 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 a storage tank. However, only the recovered liquid crystal will remain in the collection tank. As a result, the liquid crystal finally recovered has a high purity and does not require a complicated purification process. Then, the recovered liquid crystal is removed and placed in a suction cabinet to make a small amount of residual solvent. Naturally volatilization. In an embodiment of the present invention, the solvent may be further heated to accelerate volatilization or the liquid crystal may be 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. , helium, argon or a mixture thereof. Since the invention has been cooled prior to filtration adsorption, the encapsulation in the extract The material is precipitated, and then the impurities are removed by the filtration adsorption step, so that the recovered liquid crystal after removing the residual solvent has a purity similar to that of the raw material, and the recovery efficiency is as high as 95% or more. In the embodiment of the present invention, the property of the liquid crystal is recovered: the formulation has been combined with the city The liquid crystal composition sold is almost the same, and can be directly purified to remove moisture and metal ions and reused without additional 201006541. In addition to the above recovery method, the present invention also provides a recovery device as shown in Fig. 2. The recovery device has an extraction tank n, 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 and a switch 阙 43 are sequentially disposed below the extraction tank 11. And a filter adsorption device 15. The recovery device also has a condensing device 17 connected to the collection tank ι3 and the storage tank 12 by communication pipes 18B and 18C, respectively. In an embodiment of the present invention, the relative degree of the collecting tank 13 and the filtering adsorption unit 丨 5 can be adjusted to shorten the distance between the collecting tank 13 and the condensing unit ( (i.e., the length of the communicating 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 collection waste 13 is lower than the filtration adsorption device 15', the filtrate after the adsorption adsorption will flow into the collection tank 13 by gravity. On the other hand, if the strip collecting groove 13 has a higher degree of orientation than the filter adsorption unit 15, the pump unit 6 is additionally connected to the two-way threshold 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 η 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 filter plate 22, the on-off valve 43, the filter adsorption device 15, the three-way crucible 29, the communication tube 18A, and the on-off valve 44 to enter the collection tank ο. 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 introduced into the collection tank 13 through the replenishing port 25, and the circulation process is similar to the above. The above-mentioned recovery apparatus also has a storage tank M for storing the solvent of the 201006541 after the extraction of the bundle, and a gas pressurizing means. The gas pressurizing device includes a gas cylinder 31 and a gas pressure control device 33, which are connected by a communication pipe 32 for extracting a solvent by pressure filtration. The foregoing air pressure control device 33 can control the pressure; the pressure in the extraction tank 11 can be controlled, and the pressure filtration and the air pressure can be controlled at 0 to 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 π. 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 11 in an amount of between 1 kg and 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 above filter plate is used to prevent the glass crumb from entering the filter adsorption device 15 and the impurity having a larger particle diameter in the removal liquid aa' having a pore diameter of between Q.2 gm and between. The filter plate 22 may further comprise a filter mesh 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. The filter plate material includes polyethylene (PE), or polypropylene (PP), or yoghurt (pyrex8). The filter adsorption unit 15 can be a single layer or a multilayer structure that can be used to remove remaining impurities. In one embodiment of the invention, the structure is a multilayer structure of a screen/filter plate/adsorbent/filter/filter plate/filter combination. The material of the seesaw and the net is the same as the above, and the material of the filter is polyvinylidene fluoride (PVDF) or polytetrafluoroethylene (pTFE), both of which are commonly known as iron gas dragons, and their pore diameters are between 〇.1μπ^ 〇5μηι between. In an embodiment of the present invention, the adsorbent may be oxidized, oxidized stone, shi shi yin, side yue acid yre (pyre, or molecular _. the above - and _ _ can be extracted in the extract from the 201006541 tank When flowing into the collecting tank 13, the impurities not belonging to the liquid crystal are removed. In the embodiment of the present invention, the extraction tank 11 has a control device to reduce the temperature of the extract, and the dissolved encapsulating material is precipitated to form a solid. In another embodiment, the temperature control device is disposed between the filter plate 22 and the filter adsorption device 15, and can also achieve the above effects. 'In actual use, the solvent is first added to the storage tank 12, and then poured into the extraction tank 11 to be soaked. The fragmented waste panel forms an extract, which is a solution of liquid crystal and solvent (containing a small amount of packaging material). First, the temperature of the extract is lowered by a temperature control device, and then the oxygen cylinder 31 is filtered and gas is sent through the communication tube 3.2. The extraction tank 11 is added to the extraction tank, and the gas pressure is controlled by the gas pressure control unit 33 to pass through the filter plate 22 and the filter adsorption unit 15 to remove impurities, and then enter the collection tank 13 through the communication tube 18A. The collection tank 13 has plus The device 27 heats the above extract to form 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 π through the communicating tube 18B, and after condensation The formed droplets flow into the storage tank 12 through the communication tube 18C. After the extract in the extraction tank 11 is cooled and filtered and adsorbed, it completely flows into the collection tank 13, and then the opening and closing valve 42 is opened to cause the recovery solvent of the storage tank 12 to flow into the extraction tank 11 The second batch of extract liquid is formed by re-soaking the fragmented liquid crystal panel. The second batch of extract liquid is adsorbed by the temperature drop and the pressure filter, and then flows into the collecting tank 13, and then heats and recovers the solvent. The above soaking, cooling, filtering adsorption, and recovering the solvent The recycling step can be carried out until no liquid crystal remains on the fragmented waste panel. Finally, the solvent in the extraction tank 11 (without liquid crystal dissolved therein) does not flow into the collection tank 13 after filtration adsorption, but * flows into the storage tank 14 The liquid crystal recovered in the collecting tank 13 can be collected by the discharge port 26. In an embodiment of the invention, the valve is controlled by the valve 31. The liquid/solvent flows into the collecting tank 13/storage tank 14. The above-mentioned connecting tubes ΙδΑ, 18B, 18C v and 32 may be made of PTFE, unrecorded steel, or glass such as commercially available pyrex8. The above extraction tank U, collection The tank 13, the condensing device 17, the storage tanks 12 and 14, and the filter adsorption device 15 are independent members and can be disassembled and assembled separately, which is beneficial to the subsequent equipment cleaning and maintenance. The liquid crystal contained in the above-mentioned recovery method and equipment contains the solvent Very few, the proportion of impurities contained 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 shatters the entire panel without It is necessary to remove the encapsulating material such as sealant in advance to reduce 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 of the chickens simplifies the purification step of recovering the liquid crystal. The final 'recovered liquid crystals are extremely pure and have a constant formulation ratio. No need to add liquid crystal monomers, they 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: [Examples] Example 1 Take 15 pieces of discarded panels of a factory and use them. The liquid crystal is a twisted nematic type (TN-Q1 for short), and after acetone is used as an extraction solvent, the liquid crystal is recovered by the recycling method of the present invention (please refer to FIG. 1) and the device (please refer to the 2nd 12 201006541 $ S idea is The recovery device in the first embodiment does not contain the temperature control device and the attachment device 15. First, a 1 破碎 crushing panel is placed in the extraction tank η of 2 〇〇〇 mL, and then 3000 mL of acetone is added as an extraction solvent. In the storage tank 12, the on-off valve 42 is then opened to allow the solvent to flow into the extraction tank 1 to break the panel for 3 minutes to form an extract.
;慮，22過;慮後流至收集肖u，以9〇〇c水浴加熱收集槽13 使萃取液巾的两則彡成蒸氣。以冷凝裝置17將丙酮蒸氣凝 結形成液滴流人儲存槽12，待萃取槽n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、条顧冷凝、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’上述未經控蓋、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度低溫冷析和過滤'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表所不。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。 13 201006541 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 (4·0μιη之液晶盒） 1.38伏特 1.38伏特 Pitch值（4.Ομιη之液晶盒） 55.0μιη 59.2μιη 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。 Θ 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 14 201006541 取液經控溫、過濾吸附後之萃取液流至收集槽，以90°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 將正己烷蒸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 收量放大到670片廢棄面板，預估液晶含量為67〇克實 際回收量為65〇g，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肩位置（中央點和框膠 點）進行電墨保持率測試（VH_試，結果發現灌入回收液 15 201006541 晶之面板測試片不論是在RA前後其兩個位置之電壓保持 率皆與權入新品液晶之面板測試片於RA前後之I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(4.〇nm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 讎點 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 16 201006541 95%，回收液晶之GCMS圖譜如第10圖所示。 (VK2)之GCMS圖譜如第_9圏戶斤示。由第7爾^ 、文曰日 與第10圖之比較可知，回收液晶的組成與原始液晶 似。由實施例4可証明，本技術玎應用於市面上=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^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满飾，因此本發明之 攀保護範圍當視後附之申請專利範圍所界定者為準。;, 22; After that, it flows to the collection Xiaou, and the collection tank 13 is heated in a 9〇〇c water bath to make the two extracts into a vapor. The acetone vapor is condensed by the condensing device 17 to form a droplet flow person storage tank 12. After the extract liquid in the extraction tank n completely flows into the collection tank 13, the inlet valve 42 is reopened and the recovery solvent flows into the extraction tank 11# for the next time. soak. In the above cycle, the cycle time of each solvent heating, condensing, immersing and crushing the panel, and filtering 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. Recover liquid crystals. 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, there are still many impurities in the recovered liquid crystal which has not been controlled and subjected to the filtration adsorption treatment. After dissolving the above-mentioned recovered liquid crystal in acetone, it is treated by -20 degree low-temperature cold precipitation and filtration 'adsorption device 15 to precipitate various impurities and filter adsorption, and the adsorbent used includes molecular sieve, alumina, borosilicate glass, etc. As a result, the GCMS spectrum is as shown in Fig. 5, and its properties are as 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 adsorption treatment by the cold precipitation and filtration is greatly reduced. 13 201006541 Table 1 Test item Recovery of liquid crystal raw liquid crystals by cold analysis and filtration adsorption treatment (20 ° C, cps) 23 23 Clarification point (Tc, °C) 86.3 86.7 Threshold voltage Vth (4·0μιη) 1.38 volt 1.38 volt Pitch value (4. Ομιη liquid crystal cell) 55.0μιη 59.2μιη resistance value (Qcm) 1.1Ε+12 6.20Ε+13 water content (ppm) 62.0 36.6 refractive index (Δη) 0.089 0.089 dielectric property ( 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. A temperature control device is installed in the eleventh, 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.实施 Example 3 Take a 32-piece waste panel of a 32-inch factory, the liquid crystal used is a vertical alignment type (abbreviated as VA-C1), and after pulverization, n-hexane is used as an extraction solvent, and the recovery method of the present invention (as shown in FIG. 1) The liquid crystal was recovered and shown in the apparatus (as shown in Fig. 2). First, a 20 L fracture panel was 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, the extract 14 is passed through a temperature-controlled, filtered and adsorbed extract to a collecting tank, and the collecting tank is heated in a 90 ° C water bath to form a vapor of n-hexane in the extract. The hexane vapor is condensed by a condensing device to form droplets flowing into the storage tank, and the extract liquid in the extraction tank is completely flowed into the collecting tank, and then the recovered 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 was estimated to be 76 g, and the actual recovery amount was 74.5 g. The recovery rate was over 95%, and its properties were as shown in Table 2, and its 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. Further, in Example 3, the amount of recovery was further enlarged to 670 sheets of discarded panels, and the estimated liquid crystal content was 67 gram, and the actual recovery amount was 65 〇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 were further purified by the liquid crystal purification methods of 1282359 and 1297282, and then poured into the panel test piece for voltage holding ratio (VHR) test, and the new liquid crystal was poured into the panel test piece for numerical comparison. The above two test pieces were respectively subjected to reliability test (long-time high-temperature baking, referred to as RA), and ink-holding was performed on the same shoulder position (center point and frame glue point) of the two test pieces before and after the test. Rate test (VH_ test, found that the liquid is poured into the liquid 15 201006541. The voltage test rate of the crystal panel test piece before and after the RA is similar to the I value of the panel test piece of the new liquid crystal before and after RA. As shown in Table 3, it is proved that the recovery method of the present invention is also suitable for mass recovery. The second table test item recovers the liquid crystal and repurifies the 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. 〇nm cell) 3.12 volts 3.13 volts 3.10 volts resistance (Ωαη) 5.8Ε+11 1.4Ε+14 5.0Ε+13 Moisture 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) Center Point Recycling LCD new product LCD recycling LCD new LCD RA 98.2 % 98.1 % 97.6 % 97.5 % RA 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 for short). -C2), after the fragmentation, using n-hexane as an extraction solvent, the liquid crystal is recovered by the recovery apparatus shown in Fig. 2 of the present invention. The solvent addition amount used in this example is the same as the experimental reaction parameter and the third embodiment. 60 grams, the actual recovery is 60g, the recovery rate is more than 16 201006541 95%, the GCMS spectrum of the recovered liquid crystal is shown in Figure 10. The GCMS spectrum of (VK2) is shown in the _9 圏 斤 。. According to the comparison between Wenyu Day and Figure 10, the composition of the recovered liquid crystal is similar to that of the original liquid crystal. It can be proved by the embodiment 4 that the present technique is applied to the liquid crystal recycling and disposal in the market, and has the same high recovery. The present invention has been disclosed in the above-described preferred embodiments, and is not intended to limit the invention, and any one skilled in the art can make any changes without departing from the spirit and scope of the invention. And the full decoration, so the scope of protection of the present invention The attachment as defined in the following claims and the range of their equivalents.
17 201006541 【圖式簡單說明】 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_Qi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 攀 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； 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 β 第1〇圖係本發明實施例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；， . 201006541 15〜過濾吸附裝置； 1j5〜栗.浦， 17〜冷凝裝置； 18A、18B、18C、32〜連通管； 21〜進出料口； 22〜濾板； 23〜觀景窗； 24、25〜補液口； • 26~卸料口； 27〜加熱裝置； ..2 9〜三向閥 31〜氣體鋼瓶； 33〜氣壓控制裝置； 41、42、43、44~開關閥 °17 201006541 [Simplified description of the drawings] FIG. 1 is a flow chart of recovering liquid crystal in a waste panel according to an embodiment of the present invention; FIG. 2 is a schematic diagram of a device for recovering liquid crystal in a waste panel according to an embodiment of the present invention; 3 is a gcMS map of the original liquid crystal TN_Qi in the first embodiment of the present invention; FIG. 4 is a gCms map of the liquid crystal recovered in the first embodiment of the present invention; and FIG. 5 is a cold analysis and filtration in the first embodiment of the present invention. The GCMS spectrum of the liquid crystal is adsorbed back; the sixth figure is the GCMS spectrum of the recovered liquid crystal by filtration adsorption in the second embodiment of the present invention; and the seventh is the GCMS spectrum of the original liquid crystal VA-C1 in the third embodiment of the present invention. 8 is a GCMS spectrum of the liquid crystal recovered in Embodiment 3 of the present invention; FIG. 9 is a GCMS spectrum of the original liquid crystal VA-C2 in Embodiment 4 of the present invention; and FIG. 1 is a fourth embodiment of the present invention. In the process, the GCMS spectrum of the liquid crystal is recovered. [Main component symbol description] 11~ extraction tank; 12, 14~ storage tank; 13~ collection tank;, . 201006541 15~filtration adsorption device; 1j5~ Li, Pu, 17~ condensation device; 18A, 18B, 18C, 32 ~Connected pipe; 21~Inlet and outlet; 22~Filter plate; 23~View window; 24,25~Refill port; •26~Discharge port; 27~Heating device; ..2 9~Three-way valve 31~ Gas cylinder; 33~ air pressure control device; 41, 42, 43, 44~ switch valve °
1919