201102362 六、發明說明： 【發明所屬之技術領域】 本發明係一種氫氧化四曱基銨的回收設備，尤其係一 種能將廢水中的氫氧化四曱基銨與各種金屬分離，予以純 化回收重新利用來降低成本的回收設備。 【先前技術】201102362 VI. Description of the invention: [Technical field of invention] The present invention relates to a recovery device of tetradecyl ammonium hydroxide, in particular to a method for separating and purifying tetramethylammonium hydroxide from various metals in waste water, and purifying and recycling it. Recycling equipment that is used to reduce costs. [Prior Art]
氫氧化四曱基錢（Tetramethylammonium Hydroxide， TMAH)大量地使用在半導體與光電等電子高科技產業中， 以作為黃光製程中的顯影劑（Developer) » —般光電廢 和半導體廠所排放的廢水中除了 ΤΜΑΗ之外，還有光阻劑 及各種低濃度的鋁、鈣、鐵、銅、鉀、鎂、鈉等金屬離子， 由半導體製程或光電製程所產生的廢水勢必會含有氫氧化 四甲基銨，由於氫氧化四甲基銨具有強鹼性，因此氫氧化 四甲基銨於處理時僅當作一般腐蝕性化學物質處置，進行 如焚化或生物法等方式處理。所以，氫氧化四子基銨會造 成環境的負擔，且氫氧化四ρ基銨中尚具有其它化學物質 因此無法供半導體與光電等電子的製造業者重新使用，所 以使製造業者的製作成本無法降低。 如本國第98114596號專利申請案，已經揭露一種有 效回收丁麵的裝置與方法，能夠有效移除光阻劑，但是 因為廢水中除了光阻劑之外’尚包含各種金屬離子所： 上述專利案仍無法將廢水中的金屬離子去除，而造成目X 所回收的氫氧化四？基狀純度無法㈣，因此，目= 於光電廠和半導體廠所排放之廢水的處理方法仍然有= 改善之處，來降低整體製程的成本，並且能狗減少排出之 201102362 廢水對於環境的污染。 【發明内容】 本發明人有鑑於既有方法無法同時分離回收光電廢和 半導體廠所排放之廢水中的TMAH和各種金屬離子，因此 經過長期的研究以及不斷的試驗之後，終於發明出此氫氧 化四曱基銨的回收設備。 本發明之目的係在於提供一種能將廢水中的氫氧化四 甲基銨與各種金屬分離予以純化回收重新利用來降低成本 的氫氧化四曱基銨的回收設備。 為達上述目的，本發明之氫氧化四曱基銨（TMAH)的回 收設備，其係包括： 一廢液槽，其係包括含有氫氧化四甲基錄、光阻劑以 及金屬離子的廢液； 一鈉濾系統’其係與該廢液槽相連通，該鈉濾系統係 具有至少一鈉濾裝置和一幫浦’該鈉濾裝置係與該廢液槽 連通’且該幫浦係設置在該納據裝置和廢液槽之間； 一金屬離子回收樹脂塔’其係連通於該鈉濾系統； 一氫氧化四甲基銨樹脂塔，其係連通於該金屬離子回 收樹脂塔，且包括至少一 TMAH吸著樹脂塔； 一回收處理水收集槽，其係以管線連接至該鈉濾系統 以及該TMAH吸著樹脂塔； 至少一硫酸氫氧化四甲基銨[(tma)2so4]收液槽，其係 連通於該TMAH吸著樹脂塔，以收集硫酸氫氧化四甲基銨； 一離子消除樹脂塔，其係連通於該硫酸氫氧化四甲基 銨收液槽’其係消除硫酸根離子（so42.)或氯離子（c丨-); 201102362 一 TMAH回收槽，其係連通於該離子消除樹脂塔，以 收集純化的ΤΜΑΗ溶液》 較佳的是，該氫氧化四曱基銨樹脂塔係一種氫氧化四 曱基銨轉塔式（Merry-Go-Round, MGR system)樹脂塔，其 包括二TMAH吸著樹脂塔，其係連通於該金屬離子回收樹 脂塔。 其中，該氫氧化四甲基銨的回收設備尚包括一預渡裝 置’其係設置在該廢液槽和鈉濾系統之間，該鈉據裝置係 與該預濾裝置連通’且該鈉濾系統之幫浦係設置在該鈉渡 裝置和該預濾裝置之間。 其中’該氫氧化四曱基銨的回收設備尚包括一過渡裝 置’其係詨置於該離子消除樹脂塔和該TMAH回收槽之間， 以令該TMAH回收槽係連接於該過濾裝置。 其中’該氫氧化四甲基銨的回收設備尚包括一低TMAH 收液槽，其係設置於該金屬離子回收樹脂塔和該回收處理 水收集槽之TMAH吸著樹脂塔之間，且連通於各TMAH吸 著樹脂塔。 該金屬離子回收樹脂塔為螯合性陽離子交換樹脂或是 強酸性（SAC)陽離子樹脂。 該金屬離子回收樹脂塔的再生方式為逆向再生的樹脂 塔。 其中’該離子消除樹脂塔中具有強鹼性樹脂〔以〇Η 型（OH form)的型式操作〕，以去除廢水中的硫酸根或氯離 子’產生純化的TMAH溶液。 該離子消除樹脂塔為滿床式逆向再生的樹脂塔。 .201102362 該氫氧化四曱基銨的回收設備尚包括一樹脂逆洗塔， 以作為樹脂再生及逆洗時之用途。 本發明又關於一種氫氧化四曱基銨（TMAH)的回收方 法'包括： 提供含有TMAH、光阻劑和金屬離子及其他雜質的廢 水； 將該廢水經由鈉濾處理，而移除廢水中的光阻劑，以 得到第一回收處理水； 將該第一回收處理水經由金屬離子回收樹脂作用而移 除該第一回收處理水中的金屬離子，以得到第二回收處理 水； 將該第二回收處理水藉由TMAH吸著陽離子樹脂吸附 部分TMAH，經由再生而獲得具有硫酸氫氧化四甲基銨 [(TMA)2S〇4]或氯化氫氧化四甲基銨[(TMA)CI]的液體； 再將具有硫酸氫氧化四甲基銨或氣化氫氧化四甲基銨 • 的液體經由強鹼性樹脂處理，以移除硫酸根離子（s〇42·)或 氣離子（CI-)，而得到純化的TMAH溶液。 較佳的是，該第二回收處理水係藉由轉塔方式（Merry-Tetramethylammonium Hydroxide (TMAH) is widely used in the high-tech industries such as semiconductors and optoelectronics as a developer in the yellow process (Developer). In addition to germanium, there are photoresists and various low-concentration metal ions such as aluminum, calcium, iron, copper, potassium, magnesium, sodium, etc. The wastewater generated by semiconductor process or photoelectric process is bound to contain tetramethyl hydroxide. Since the ammonium tetramethylammonium hydroxide has a strong basicity, the tetramethylammonium hydroxide is treated as a general corrosive chemical substance at the time of treatment, and is treated by incineration or biological methods. Therefore, tetraammonium hydroxide hydride causes a burden on the environment, and there are other chemicals in the tetra-p-ammonium hydroxide, so that it cannot be reused by manufacturers of semiconductors and optoelectronics, so that the manufacturing cost of the manufacturer cannot be lowered. . As disclosed in Japanese Patent Application No. 98114596, an apparatus and method for efficiently recovering dough is disclosed, which can effectively remove the photoresist, but because the waste water contains various metal ions in addition to the photoresist: Still can't remove the metal ions in the wastewater, and cause the hydrogen hydroxide recovered by the target X? The purity of the base cannot be (4). Therefore, the treatment method of wastewater discharged from the photovoltaic power plant and the semiconductor plant still has = improvement to reduce the cost of the overall process, and the dog can reduce the environmental pollution caused by the discharged 201102362 wastewater. SUMMARY OF THE INVENTION The present inventors have invented the hydrogen peroxide after long-term research and continuous testing in view of the inability of the existing method to simultaneously separate and recover TMAH and various metal ions in waste water discharged from photovoltaic waste and semiconductor plants. Tetramethylammonium recovery equipment. SUMMARY OF THE INVENTION An object of the present invention is to provide a recovery apparatus for tetraammonium hydroxide which can be used for separating and recovering tetramethylammonium hydroxide from waste water and purifying and recycling it to reduce the cost. In order to achieve the above object, the apparatus for recovering tetrakid ammonium hydroxide (TMAH) of the present invention comprises: a waste liquid tank comprising a waste liquid containing tetramethyl hydroxide, a photoresist, and a metal ion; a sodium filtration system that is in communication with the waste liquid tank, the sodium filtration system having at least one sodium filtration device and a pump 'the sodium filtration device is in communication with the waste liquid tank' and the pump system is set Between the reagent device and the waste liquid tank; a metal ion recovery resin column 'connected to the sodium filter system; a tetramethylammonium hydroxide resin column connected to the metal ion recovery resin column, and Including at least one TMAH sorbent resin tower; a recovery treatment water collection tank connected by pipeline to the sodium filtration system and the TMAH sorbent resin tower; at least one tetramethylammonium sulfate [(tma)2so4] a liquid tank connected to the TMAH sorbent resin tower for collecting tetramethylammonium sulfate sulfate; an ion-eliminating resin tower connected to the tetramethylammonium sulfate sulphate tank to eliminate sulfuric acid Root ion (so42.) or chloride ion (c丨-); 201102362 A TMAH recovery tank is connected to the ion-eliminating resin column to collect the purified ruthenium solution. Preferably, the ruthenium hydroxide-based resin tower is a tetramethylammonium hydroxide turret (Merry- Go-Round, MGR system) A resin tower comprising a two TMAH sorbent resin column connected to the metal ion recovery resin column. Wherein, the recovery device of tetramethylammonium hydroxide further comprises a pre-fitting device disposed between the waste liquid tank and the sodium filtration system, the sodium data device is in communication with the pre-filtration device' and the sodium filter A pumping system of the system is disposed between the sodium bypass device and the pre-filtration device. Wherein the recycling device of the tetraammonium hydroxide further comprises a transition device disposed between the ion-eliminating resin column and the TMAH recovery tank to connect the TMAH recovery tank to the filtering device. Wherein the recovery device of the tetramethylammonium hydroxide further comprises a low TMAH liquid collection tank disposed between the metal ion recovery resin column and the TMAH sorption resin column of the recovery treatment water collection tank, and is connected to Each TMAH sucks the resin tower. The metal ion recovery resin column is a chelating cation exchange resin or a strongly acidic (SAC) cationic resin. The metal ion recovery resin column is regenerated in a reversely regenerated resin column. Wherein the ion-eliminating resin column has a strong basic resin [operating in the form of an OH form] to remove sulfate or chloride ions in the wastewater to produce a purified TMAH solution. The ion-eliminating resin column is a full-bed reverse-recycled resin column. .201102362 The recycling equipment of tetradecyl ammonium hydroxide also includes a resin backwashing tower for use as a resin for regenerating and backwashing. The invention further relates to a method for recovering tetrakid ammonium hydroxide (TMAH) comprising: providing wastewater containing TMAH, a photoresist, metal ions and other impurities; treating the wastewater by sodium filtration to remove waste water a photoresist to obtain a first recycled treated water; removing the metal ions in the first recovered treated water by the first recovered treated water via a metal ion recovery resin to obtain a second recovered treated water; Recycling the treated water by absorbing the cationic resin adsorption moiety TMAH by TMAH, and obtaining a liquid having tetramethylammonium sulfate [(TMA) 2S〇4] or tetramethylammonium chloride [(TMA)CI] by regeneration; The liquid having tetramethylammonium sulfate or tetramethylammonium hydroxide is further treated with a strong basic resin to remove sulfate ions (s〇42·) or gas ions (CI-). A purified TMAH solution was obtained. Preferably, the second recovered water system is by means of a turret (Merry-
Go-Round, MGR system)吸 附部分 TMAH 。 其中，該廢水，經由納據處理之前，肖進行一預遽步驟， 以移除廢水中的固態雜質。 其中，該廢水移除硫酸根或氯離子後，尚包括進行一 過濾步驟，以獲得無雜質之純化的TMAH溶液。 較佳的《’該金屬料回收樹脂為冑合型離子交換樹 脂或強酸性（SAC)陽離子交換樹脂。該強酸性陽離子交換 201102362 樹脂係採用逆向再生方式進行再生，逆向再生方式為屋床 水型（water blocking)或滿床式（pack)。用於再生的再生藥 劑為硫酸或鹽酸。 其中，該TMAH吸著樹脂為Η型（H-form)強酸性（SAC) 陽離子交換樹脂或Η型（H-form)弱酸性（WAC)陽離子交換 樹脂，用以交換廢水中的四甲基銨根離子（TMA〇。 其中，以轉塔式進行的TMAH吸著樹脂的再生方式為 籲 正向再生，而再生水為去離子水》 其中，該強驗性樹脂係去除廢水中的硫酸根或氯離 子，以產生純化的TMAH溶液。而該強鹼性樹脂飽和後係 利用氫氧化鈉（NaOH)或氫氧化鉀（KOH)溶液進行再生。 藉由本發明之氫氧化四曱基銨的回收設備，能夠將廢 水中的光阻劑藉由鈉濾方式去除，而金屬離子能藉由離子 交換樹脂而移除，所以能夠得到純化的TMAH溶液，以將 其中的TMAH回收再利用，以減低其對於環境造成的污染。 _ 【實施方式】 請參看第一圖所示，本發明之氫氧化四甲基銨的回收 設備，係包括： 廢液槽（10)’其係包括含有氫氧化四曱基按、光阻 劑以及金屬離子的廢液； 一預遽裝置（11)，其係連通於該廢液槽（10); 一鈉濾系統（20)，其係與該第一預粗濾裝置（1 ”相連 通’該納濾系統（20)係具有六個鈉濾裝置（21)和一幫浦 (22)，各鈉濾裝置（21)内設有一鈉濾膜（23)，以令該鈉濾裝 置（21)内部形成一第一分離室（24)和第二分離室（25)，接近 201102362 該第-粗預㈣置（11)的㈣I置（21)之第—分離室（24)係 與該第一粗遽裝置（11)相連接，且該等納渡裝fi(21)的第 -分離室(24)皆相互連通，該幫浦(22)係設置在鈉渡裝置 (21)和第-過《置（11)之間’以提供該等㈣裝置（21)足 夠的壓力； 一金屬離子回收樹脂塔（30),其係連通於該鈉濾系統 (20)之該等鈉瀘裝置（21)的第二分離室（25)，該金屬離子回 收樹脂塔（30)具有螯合型陽離子交換樹脂或強酸性（SAC) 陽離子樹脂，該金屬離子回收樹脂塔（3〇)為逆向再生的樹 脂塔； 一低TMAH收液槽（31}’其係連通於該金屬離子回收 樹脂塔（30)，以收集去除金屬離子的廢水； 一氫氧化四甲基銨樹脂塔（40)，請附加參看第四圖所 示，其係一種轉塔式的系統（Merry-Go-Round, MGR system)，其包括二TMAH吸著樹脂塔（41,42)，連通於該 金屬離子回收樹脂塔（30); 一回收處理水收集槽（50)，其係以管線連接至該鈉濾 系統（20)以及該等TMAH吸著樹脂塔（41,42); 二硫酸氫氧化四甲基銨[(TMA)2S04]收液槽（60)，其係 連通於該等TMAH吸著樹脂塔（41,42)，以收集硫酸氫氧化 四甲基銨； 一離子消除樹脂塔（70)，其係連通於該硫酸氫氧化四 甲基銨收液槽（60)，該離子消除樹脂塔（70)為滿床式樹脂 塔’其内部具有強鹼性樹脂，以去除廢水中的硫酸根或氣 離子，產生純化的TMAH溶液； 201102362 一樹脂逆洗塔（71)，其係連通於該消除樹脂塔（70) ’ 以將TMAH沖提出來； 一過濾裝置（72)，其係連通於該離子消除樹脂塔（70)。 一 TMAH回收槽（80)，其係連接於該第二粗濾裝置 (72)，以收集該純化的TMAH溶液。 本發明之氫氧化四甲基銨（TMAH)的回收方法，係利用 上述裝置進行，其包括： 提供含有TMAH、光阻劑和金屬離子（如鋁、鈣、鐵、 銅、鉀、鎂、鈉等金屬離子）的廢水，將其注入該廢液槽（10); 將該廢液槽（10)中的廢水經過預濾裝置（1彳）過濾，再 經由鈉濾系統（20)之幫浦送至鈉濾裝置（21)中，藉由鈉濾 系統處理後移除廢水中的光阻劑，以得到第一回收處理 水； 將該第一回收處理水送至金屬離子回收樹脂塔（3〇)， 經由金屬離子回收樹脂的作用而移除該第一回收處理水中 的金屬離子’以得到第二回收處理水； 將該第二回收處理水送至該低TMAH收液槽（31)中， 再由該低TMAH枚液槽（31)經幫浦作用而送至該氫氧化四 甲基銨樹脂塔（40)的二TMAH吸著樹脂塔（4142)，藉由 TMAH吸著樹月日以轉塔式（merry_g〇_r〇und)吸附部分 TMAH ’將-般的回收水和再生後的硫酸氫氧化四甲基錄 [(TMA)2S04R氣減氧化四甲基錄的再生液液體分別送 該回收處理水收集槽（5Q)和該等硫酸氫氧化四 槽（60)十； 枚吹液 再將具有硫酸氫氧化四甲基錄或氯化氣氧化四甲基録 201102362 的液體送往該離子消除樹脂塔（70)以強鹼性樹脂處理後移 除硫酸根和氣離子’而得到純化的TMAH溶液，該離子消 除樹脂塔（70)可連接一樹脂逆洗塔（71)，用於再生及逆洗 時，純化樹脂之用； 該純化的TMAH經由過濾裝置（72)的過濾後，可再送 回該低TMAH收液槽（31)，經過氫氧化四甲基銨樹脂塔（40) 和離子消除樹脂塔（70)再一次的處理；或者可直接送至該 TMAH回收槽（80)中。 請參看第二圖所示’其係顯示金屬離子回收樹脂塔（3〇|) 以正向再生方式進行再生，其缺點為容易使金屬離子漏 出0 請參看第三圖所示，其係顯示金屬離子回收樹脂塔（30) 以逆向再生方式進行再生，發現並無金屬離子洩漏的問 題’故本發明之金屬離子回收樹脂塔（3〇)採甩逆向再生方 式進行再生。 經過該金屬離子回收樹脂塔（30)後的TMAH溶液可用 納分析儀或感應耦合電漿質譜分析儀（ICp_ms)來偵測溶液 中的金屬離子濃度。 藉由納濾系統（20)能约除去廢水中的光阻劑，且藉由 螯合型離子交換樹脂或強酸性（SAC)陽離子樹脂而去除金屬 離子，而得到純化的TMAH溶液，將其回收再利用，而降 低排放出去之廢水對於環境的污染，並且降低相關產業的 製造成本，因此極具產業利用性。 【圖式簡單說明】 第一圖係本發明之回收裝置的管線分佈示意圖。 201102362 第意圖。 第 二圖係本發明之金屬離子回收樹脂 三圖係本發明之金屬離子回收樹月旨 意圖。 塔之正向再生示 给·之逆向再生示 第四圖係本發明之氫氧化四甲基銨轉塔式（Me「「y_G〇_ Round, MGR system)樹脂塔的詳細管線示意圖。 【主要元件符號說明】Go-Round, MGR system) absorbing part TMAH. Wherein, before the wastewater is treated by the nanometer, a preliminary step is performed to remove solid impurities in the wastewater. Wherein, after removing the sulfate or chloride ion from the wastewater, a filtration step is further included to obtain a purified TMAH solution without impurities. Preferably, the metal recovery resin is a chelating ion exchange resin or a strongly acidic (SAC) cation exchange resin. The strong acid cation exchange 201102362 resin is regenerated by reverse regeneration, and the reverse regeneration method is a water blocking or a pack. The regenerating agent for regeneration is sulfuric acid or hydrochloric acid. Wherein, the TMAH absorbing resin is an H-form strong acid (SAC) cation exchange resin or a H-form weakly acidic (WAC) cation exchange resin for exchanging tetramethylammonium in waste water. Root ion (TMA〇. Among them, the regeneration mode of the TMAH sorption resin in the turret type is called forward regeneration, and the reclaimed water is deionized water), wherein the strong resin removes sulfate or chlorine in the wastewater. Ion to produce a purified TMAH solution, which is saturated with sodium hydroxide (NaOH) or potassium hydroxide (KOH) solution after being saturated. By using the tetraammonium hydroxide recovery device of the present invention, The photoresist in the wastewater can be removed by sodium filtration, and the metal ions can be removed by the ion exchange resin, so that the purified TMAH solution can be obtained to recycle the TMAH therein to reduce the environment. [Conditions] Please refer to the first figure, the recycling equipment of tetramethylammonium hydroxide of the present invention includes: a waste liquid tank (10)' which includes a tetraruthenium hydroxide group Photoresist And a waste liquid of metal ions; a pre-twisting device (11) connected to the waste liquid tank (10); a sodium filtration system (20) connected to the first pre-fine filtration device (1) The nanofiltration system (20) has six sodium filtration devices (21) and a pump (22), and each sodium filtration device (21) is provided with a sodium filtration membrane (23) to make the sodium filtration device ( 21) internally forming a first separation chamber (24) and a second separation chamber (25), close to 201102362, the first-thick pre-fourth (11) (4) I-position (21) of the first separation chamber (24) The first roughing device (11) is connected, and the first separation chambers (24) of the nanofabricated fi(21) are connected to each other, and the pump (22) is disposed in the sodium ferroelectric device (21) and the first - passing "between (11) to provide sufficient pressure for the (4) device (21); a metal ion recovery resin column (30) which is connected to the sodium filtration system (20) a second separation chamber (25) of (21), the metal ion recovery resin column (30) having a chelating type cation exchange resin or a strongly acidic (SAC) cationic resin, and the metal ion recovery resin column (3 〇) is reversely regenerated Resin tower A low TMAH liquid collection tank (31}' is connected to the metal ion recovery resin tower (30) to collect waste water for removing metal ions; a tetramethylammonium hydroxide resin tower (40), please refer to the fourth As shown in the figure, it is a turret type system (Merry-Go-Round, MGR system), which comprises two TMAH sorbent resin towers (41, 42) connected to the metal ion recovery resin tower (30); Recycling treatment water collection tank (50) connected by pipeline to the sodium filtration system (20) and the TMAH sorbent resin tower (41, 42); tetramethylammonium disulfate [(TMA) 2S04] a liquid receiving tank (60) connected to the TMAH sorbent resin towers (41, 42) for collecting tetramethylammonium sulfate sulfate; an ion-eliminating resin tower (70) connected to the hydrogen sulfate Oxidation of tetramethylammonium chloride receiving tank (60), the ion-eliminating resin tower (70) is a full-bed resin tower having a strong basic resin inside to remove sulfate or gas ions in the wastewater to produce purified TMAH Solution; 201102362 a resin backwashing tower (71) connected to the elimination resin column (70)' to flush TMAH; A filter device (72) is in communication with the ion-eliminating resin column (70). A TMAH recovery tank (80) is coupled to the second coarse filtration unit (72) to collect the purified TMAH solution. The method for recovering tetramethylammonium hydroxide (TMAH) of the present invention is carried out by using the above apparatus, comprising: providing TMAH, a photoresist, and a metal ion (such as aluminum, calcium, iron, copper, potassium, magnesium, sodium) The wastewater of the metal ion) is injected into the waste liquid tank (10); the waste water in the waste liquid tank (10) is filtered through a pre-filtration device (1彳), and then pumped through the sodium filtration system (20). It is sent to the sodium filter device (21), and the photoresist in the waste water is removed after being treated by the sodium filter system to obtain the first recovered treated water; the first recovered treated water is sent to the metal ion recovery resin column (3) 〇), removing the metal ions in the first recovery treatment water by the action of the metal ion recovery resin to obtain the second recovery treatment water; and sending the second recovery treatment water to the low TMAH collection tank (31) And the low TMAH liquid tank (31) is sent to the two TMAH sorbent resin tower (4142) of the tetramethylammonium hydroxide resin tower (40) by a pumping action, and the tree is sucked by TMAH. In the turret type (merry_g〇_r〇und) adsorption part TMAH 'will be the general recovery of water and regenerated sulfur Tetramethyl hydroxide [(TMA) 2S04R gas-reducing tetramethyl-reported regenerant liquid is sent to the recovery treatment water collection tank (5Q) and the four tanks of sulfuric acid sulphate (60) ten; A liquid having tetramethyl sulphate oxychloride or chlorinated tetramethyl sulphide 201102362 is sent to the ion-eliminating resin column (70) to remove sulfate and gas ions after treatment with a strong basic resin to obtain purified TMAH. a solution, the ion-eliminating resin column (70) may be connected to a resin backwashing tower (71) for purifying the resin for regeneration and backwashing; the purified TMAH may be filtered by the filtering device (72). The low TMAH collection tank (31) is returned to the tetramethylammonium hydroxide resin column (40) and the ion-eliminating resin column (70) for further treatment; or directly to the TMAH recovery tank (80). Please refer to the second figure, which shows that the metal ion recovery resin tower (3〇|) is regenerated in a forward regeneration mode. The disadvantage is that metal ions are easily leaked out. See the third figure, which shows the metal. The ion-recovery resin column (30) was regenerated by reverse regeneration, and it was found that there was no problem of leakage of metal ions. Therefore, the metal ion-recovery resin column (3〇) of the present invention was regenerated by reverse regeneration. The TMAH solution after passing through the metal ion recovery resin column (30) can be used to detect the concentration of metal ions in the solution by means of a nano analyzer or an inductively coupled plasma mass spectrometer (ICp_ms). The nanofiltration system (20) can remove the photoresist in the wastewater, and the metal ion is removed by a chelate ion exchange resin or a strong acid (SAC) cationic resin to obtain a purified TMAH solution, which is recovered. Reuse, and reduce the pollution of the discharged wastewater to the environment, and reduce the manufacturing costs of related industries, so it is highly industrially applicable. BRIEF DESCRIPTION OF THE DRAWINGS The first figure is a schematic diagram of the pipeline distribution of the recovery apparatus of the present invention. 201102362 The first intention. The second drawing is a metal ion recovery resin of the present invention. The three figures are the intention of the metal ion recovery tree of the present invention. The fourth diagram of the reverse regeneration of the tower is shown in detail. The fourth diagram is a detailed pipeline diagram of the tetramethylammonium hydroxide turret of the present invention (Me "" y_G〇_ Round, MGR system) resin tower. Symbol Description】
(1〇)廢液槽 （11)預濾裝置 (2〇>鈉濾系統 （21)鈉濾裝置 (22)幫浦 （23)納濾膜 (24)第一分離室 （25)第二分離室 (30) (30’）金屬離子回收樹脂塔 (31) 低TMAH收液槽 (40)氫氧化四曱基録樹脂塔 (41,42) TMAH吸著樹脂塔 (50)回收處理水收集槽 (60)硫酸氫氧化四甲基銨收液槽 (70)離子消除樹脂塔 （71)樹脂逆洗塔 (72)過濾裝置 （80) TMAH回收槽 11 [S3(1〇) waste tank (11) pre-filter unit (2〇> sodium strain system (21) sodium filter unit (22) pump (23) nanofiltration membrane (24) first separation chamber (25) second Separation chamber (30) (30') metal ion recovery resin tower (31) low TMAH liquid collection tank (40) tetrahydrocarbyl hydroxide resin tower (41, 42) TMAH sorbent resin tower (50) recovery treatment water collection Tank (60) Tetramethylammonium sulfate sulphate tank (70) Ion-eliminating resin tower (71) Resin backwashing tower (72) Filtration unit (80) TMAH recovery tank 11 [S3