201126283 六、發明說明： 【發明所屬之技術領域】 料係關於一種自対氫氧化四燒基銨之廢液回收及 純化風氧化喊基狀方法。尤其 ^收及 ί氫氧化四烷基銨轉換成為四烷1銨之酸鹽;，ΐί ? ==化’隨後將所得，之酸鹽電解 【先ΐίΐΓ 时及純減氧化哺細之方法。 氫氧化四烷基銨為電子零件產業，諸如 板;ί，電路板產業等常用丄二 為酸驗中和=^錢。風氧化四燒基錢為有機性強驗’亦可作 用於各活性劑、電解質及橡膠添加劑等可廣泛應201126283 VI. Description of the invention: [Technical field to which the invention pertains] The material system relates to a method for recovering and purifying a wind-oxidized shunt base from a waste liquid of tetrazolium hydroxide. In particular, the conversion of tetraalkylammonium hydroxide to tetra-ammonium 1-ammonium salt; ΐί ? ==化' followed by electrolysis of the resulting acid salt [first ΐ ΐΓ ΐΓ and pure oxidative feeding method). Tetraalkylammonium hydroxide is an electronic component industry, such as a board; ί, the circuit board industry and the like are commonly used for acid testing and neutralization = ^ money. The wind-oxidized four-burning base is a strong organic test. It can also be used for various active agents, electrolytes and rubber additives.
銨及ί解::液，其主賴 Υ會』^生顯衫廢液之處理方法一般係與工礙内廢酸進行pH 晉Ui ne物降解性差、活性污泥剩養不易、處理設備ί 之方^。，因此近期有發展出許多回收及純化氫氧化四甲基錢 f國專利號__(相當於台灣專利公告號你備)揭示 ί(ΝΡ 之再生處理方法及裝置，係利用奈米過濾 有四甲基録離子之含光阻義影廢液得到 f液及β透液，濃縮液主要含有光阻劑等雜質，滲透液主要 3有四甲基鋪子；接著使用電透析或轉單元對滲透液及/ ? < 4 201126283 ，濃縮液進行濃縮純化處理及以陽離子交換樹脂及/或陰離子 父換樹脂進行純化而除去雜質。 一然而，以奈米過濾膜(NF膜)處理含有四甲基銨離子之含 ^且麵影廢液時’於低濃度情況下奈米過濾獻過遽速度 快’但有-定比例的四甲基銨鹽會殘留於濃縮液中，此部份濃 ΐΐί ΐ阻劑濃度較高(因被W膜搁截下）。隨著濃縮液濃度 曰间滲透壓亦加大，致使過濾膜之過濾速度變慢或增高壓力， 3有過濾、，度及效率變差之_。而單純使渗透液經電滲析或 電解回收氫氧化四甲基銨會造成回收率過低，若使师濃縮液 通過電滲析或電解脫鹽槽以進—步回收濃縮物内之四甲基錄 鹽時，將因光阻劑而對電滲析或電解膜之使用壽命造成影塑， 且由於電滲析或f解膜健昂貴因此亦影響了回 曰 業利用價值。 、 因此，本發明之目的係提供一種自含有氫氧化四烷基敍之 廢液’尤其是自顯影廢液回收及純化氫氧化四烷基銨之方法， 可克服習知技術缺點提高回收率及降低回收成本。 【發明内容】 依?士發明’提供—種自含有氫氧化四絲叙廢液回收 及純化氫氧化四絲狀方法，該練至少包含氫氧化四驗 及光阻劑等雜質，該方法至少包括下列步驟： ⑴藉由酸使該廢液t之氫氧化四⑨轉換成四絲録之酸 鹽，形成含四烷基銨之酸鹽的廢液； (2)使該含日絲叙酸鹽的廢舰過具有奈料赫之分離 裝置’於該奈米過爐膜之漠縮側獲得含光阻劑及其他雜質之濃 縮液及於該奈米過濾膜之滲透側含有四烷基銨之酸鹽的 液； =)持續進行步驟(2)之該過遽分離步驟，於濃縮侧之濃縮液電 導度値大於2__em社時，賊分贼置之過濾膜濃縮 側添加純水繼續進行過濾直至滲透液側之滲透液體積達最初 處理廢液體積之90體積％以上；及 [Si 5 201126283 酸鹽崎域基錢之 廢液中，該含有氫氧化四纖之 ::可》用本技藝悉知之用以將氫氧 ΐλ=ί _細_，於树财並 ==ί ^ 陽軒交賴脂或弱_ _子交換^Ammonium and ί solution::Liquid, its main Υ Υ ^ ^ ^ 显 显 废 废 之 之 ^ 生 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显 显The square ^. Therefore, in the near future, there have been many patents for the recovery and purification of tetramethylammonium hydroxide. The national patent number __ (equivalent to the Taiwan Patent Bulletin No.) reveals that ί (ΝΡ regeneration treatment method and device, using nanofiltration has four Methyl recording ion containing photoresist photocopying waste liquid to obtain f liquid and β liquid permeation, the concentrated liquid mainly contains impurities such as photoresist, the permeate mainly has a tetramethyl shop; then uses electrodialysis or transfer unit to permeate And / ? < 4 201126283 , the concentrate is concentrated and purified and purified by cation exchange resin and / or anion parent resin to remove impurities. However, treatment with nanofiltration membrane (NF membrane) containing tetramethylammonium When the ion contains ^ and the surface waste liquid, the nanofiltration is fast at low concentration, but the tetramethylammonium salt in a certain proportion will remain in the concentrate, and this part is concentrated. The concentration of the agent is high (due to being trapped by the W film). As the concentration of the concentrate increases, the osmotic pressure increases, causing the filtration rate of the filter membrane to slow down or increase the pressure. 3 The filtration, degree and efficiency are deteriorated. _. And simply make the permeate electrodialysis or electricity The recovery of tetramethylammonium hydroxide will result in a low recovery rate. If the concentrate is passed through an electrodialysis or electrolytic desalting tank to recover the tetramethyl salt in the concentrate, it will be charged by the photoresist. The service life of dialysis or electrolytic membrane is caused by shadowing, and it is also expensive due to electrodialysis or f-solution. Therefore, the object of the present invention is to provide a self-containing tetraalkyl hydride. The method of recovering and purifying tetraalkylammonium hydroxide from the waste liquid, especially the self-developing waste liquid, can overcome the shortcomings of the prior art, improve the recovery rate and reduce the recovery cost. [Summary of the Invention] The method for recovering and purifying the oxidized tetrafilament waste liquid comprises at least four tests of hydroxide and a photoresist, and the method comprises at least the following steps: (1) oxidizing the waste liquid t by acid 4 9 is converted into a tetralithic acid salt to form a waste liquid containing a tetraalkylammonium acid salt; (2) the waste ship containing the Japanese silk sulphate is passed through a separation device having a Naihehe The deserted side of the rice furnace film is light-containing a concentrate of the agent and other impurities and a solution containing a salt of a tetraalkylammonium on the permeate side of the nanofiltration membrane; =) continuing the step of separating the step of the step (2), and conducting the concentrate on the concentration side When the degree is greater than 2__em, the thief is placed on the concentrated side of the filter membrane to add pure water to continue filtration until the volume of the permeate on the permeate side reaches 90% by volume of the volume of the initial treatment waste; and [Si 5 201126283 In the waste liquid of the domain base money, the four-fiber hydride containing:: can be used in the art to use the hydrogen oxyhydroxide λ = ί _ fine _, Yu Shucai and = ί ^ Yang Xuan Weak _ _ sub-exchange ^
無機_如鹽酸、雜、硫酸、碳酸等沖提再生細g = 酉=。㈡將有機酸或無機酸例如鹽酸、確酸、硫酸、&酸等 直接加入氫氧化四烷基銨溶液中將其中和至pHi2〜3。 ^發明中，所謂「四絲錄之酸鹽」意指藉由酸使氮氧化 四烧基銨⑽雜變舰鑛叙鹽。所紅雜將視用以中 和之酸種類而定，例如使用鹽酸作為中和酸時，該四烷基録之 酸鹽係指氯化四烷基銨，而使用硫酸時，則指硫酸四烷基銨 等。使用其他酸時亦同。 本發明之上述方法步驟(2)中使用之具有奈米過濾膜裝置 至少包含一》辰縮槽’係用以容納其中所含的氫氧化四烧基銨經 轉換處理成四烷基銨之酸鹽後之廢液；一濾液槽，係用以容納 通過奈米過濾膜之含四烷基錄之酸鹽之滲透液；一奈米過遽膜 管，係用以將四烷基銨之酸鹽與光阻劑及高價金屬如：Fe、 A1等進行分離；一純水桶，係用以於濃縮槽供給純水；以及 一泵浦，用以將純水自純水桶泵入濃縮槽中。將於濃縮槽中之 含光阻劑、高價金屬及四烷基銨之酸鹽之液體經由幫浦加壓經 過奈米過濾膜管而分離，其壓力較好設定為5〜25 kg/cm2，可 於滤液槽中獲得已去除光阻劑及高價金屬等雜質之主要成分 為四烷基銨之酸鹽之滲透液及於濃縮槽獲得主要為含光阻劑 及高價金屬等雜質之濃縮液。 201126283 步驟(2)中’所用之奈米過遽膜可使 幻Ί气子量為100〜1000之奈米過遽膜管，且可使用一或 濾、膜管，當使用多個過濾膜管時，可以串聯及並聯任意 組合使用。 本發明方法之上述步驟(2)中，添加於濃縮槽中之純水 可使用原水、超純水或去離子水。 道發明方法之上述步驟⑶中，係於濃縮側之濃縮液電 200(%s/cm以上時，於該分離裝置之過濾膜濃縮 續進行過濾、直至渗透_之渗透液_達最初 ί之90體積％以上。於奈米滤膜⑽膜)分離裝置 巧過遽時間增加’由於濃縮端四烧基錢鹽之濃度逐漸上 縮端祕壓亦逐漸升^祕顧速度下降。因奈米 f慮膜(NF膜)表面為帶負電荷，過濾過程中膜表面產生 、、曲’於過義溶液時相當於逆渗透黯縮之效果使 度值逐漸上升，當電導度值提升至2〇〇〇_cm以 i 水於濃職巾，彻财面產生肪效 祕！1中四燒基叙酸鹽萃取通過奈米過滤膜 if=率電導度下降、絲透液電導度增加而 進行之方法之麵附，騎㈣之渗透液 四严錄Ϊ予所含之四炫基錄之酸鹽轉換成氫氧化 畜：叙並r收。將四炫基録之酸鹽電解/電透析轉換成氫 ί 炫忒:===極= 201126283 併入本文供參考。Inorganic _ such as hydrochloric acid, miscellaneous, sulfuric acid, carbonic acid, etc., regenerate fine g = 酉 =. (2) An organic acid or an inorganic acid such as hydrochloric acid, acid, sulfuric acid, & acid or the like is directly added to a tetraalkylammonium hydroxide solution to neutralize it to pHi 2 to 3. In the invention, the so-called "four-screen acid salt" means that the nitrogen is oxidized by an acid to oxidize the tetraalkylammonium (10). The erythromic acid will depend on the type of acid used for neutralization. For example, when hydrochloric acid is used as the neutralizing acid, the tetraalkylate salt refers to tetraalkylammonium chloride, and when sulfuric acid is used, it refers to sulfuric acid. Alkyl ammonium and the like. The same applies when using other acids. The nanofiltration membrane device used in the above method step (2) of the present invention comprises at least one "cylinder" for accommodating the acid of the tetraalkylammonium hydroxide contained therein to be converted into a tetraalkylammonium acid. a waste liquid after salt; a filtrate tank for containing a pervaporate containing a tetraalkylate acid salt through a nanofiltration membrane; a nanometer membrane tube for the acid of a tetraalkylammonium The salt is separated from the photoresist and the high-priced metal such as Fe, A1, etc.; a pure water tank is used for supplying pure water in the concentration tank; and a pump is used to pump pure water from the pure water tank into the concentration tank. The liquid containing the photoresist, the high-valent metal and the tetraalkylammonium acid salt in the concentration tank is separated by the pressure of the pump through the nanofiltration membrane tube, and the pressure is preferably set to 5 to 25 kg/cm 2 . A permeate of a tetraalkylammonium acid salt in which a main component such as a photoresist and a high-valent metal is removed can be obtained in the filtrate tank, and a concentrate mainly containing a photoresist such as a photoresist and a high-valent metal can be obtained in the concentration tank. 201126283 In step (2), the nano-pass film used in the film can make a nano-passing film tube with a magical gas volume of 100~1000, and can use one or filter tube, when using multiple filter tubes. In time, it can be used in any combination of series and parallel. In the above step (2) of the method of the present invention, the pure water added to the concentration tank may be raw water, ultrapure water or deionized water. In the above step (3) of the method of the invention, when the concentrate liquid 200 on the concentration side is above (% s/cm or more, the filtration membrane of the separation device is concentrated and filtered until the permeate _ the permeate _ reaches the initial ί 90 More than 5% by volume. In the nanofiltration membrane (10) membrane), the separation device has increased the time of sputum by the time of gradual increase in the concentration of the condensed end of the four-burning base salt. The surface of the NF membrane is negatively charged, and the surface of the membrane is generated during the filtration process. The effect of the reverse osmosis contraction is gradually increased when the membrane is used in the over-sense solution. When the conductivity value is increased, the conductivity value is increased. To 2 〇〇〇 _cm to i water in the thick job towel, the face of the money to create a fat effect! The extraction of 1 sulphuric acid salt by the nanofiltration membrane if= rate conductivity decreases, the silk liquid permeability increases the method of the method attached, riding (four) of the permeate four strict recording to the included four The acid salt of the base record is converted into a hydrogenated animal: The electrolysis/electrodialysis of the acid salt/electrolysis of Si Xuji is converted into hydrogen ί 忒 : === 极 = 201126283 is incorporated herein by reference.
本，明之絲中’在步驟⑴藉由酸使鋪影廢液中之氣 ^匕^銨^細絲狀_，職含四絲狀酸鹽的 或之後，亦可紐_影廢液進行預處理，以及 ^^4)之電解之前使輯魏行碱理，該物處理舉例 及預先純化，該等濃縮可舉例為例如蒸發濃縮、逆 it ^縮、膜蒸織縮等’以達到適當濃度。預先純化可舉 Ξίϋ，活性碳處理、陽離子交換樹脂及/或陰離子交換 =等去除微量之㈣如光_、陽離子及/或陰離子等微量 7之預先純化，以達到各工業電子用純度為目的之純化步 【實施方式】 實施例 纽，下ϊ以實施_確說明本發明’但不應將其解釋為限制 *A二日之ί圍。帛1圖係說明奈米過遽膜⑽膜〉分離具體實 ^置’氣氧化四甲基録濃度係由酸驗滴定分析，四甲基銨之 酸鹽回收率係由式： 與0參透液電導度X滲透液體積)/(經酸中和後四曱基錄之酸踏 之電導度X最初處理液體積)χ 100% ·" r算而得，光_前糾料W見紋綺於波長 ==測魏絲听岐性，絲舰齡表示光阻 實施例1 試樣溶液係由液晶顯示器(LCD)廠A公司於製造過程中， 由顯影製程舰職π錢取樣之顯影廢液。賴影廢液 析所含^氫氧化四甲基銨濃度為G.66重量％，且以紫外光-可 見光吸光計於波長設定為28Qnm偵測其吸光度為Q 6〇2。取 5^.30L該顯影廢液經32% Ηα將其pH調整至適於奈米過遽膜 为，裝置之pH為6."1，即為試樣溶液，此時已將其内戶一 之氫氧化四甲基銨轉換減化四甲基銨，以電導度計測得的氣 201126283 化四甲”EC物0^。 a灣通過—包含奈米過濾膜(NF膜)分離裝置(為 it’該裝置使狀奈錄舰⑽ 一二司所製造之OT90_2540,且該分離裝置具備 日®t以谷納其中所含的氫氧化四曱基銨經轉換處理 二，後之顯影廢液；一濾液槽，係用以容納通過奈 二^之1化四曱基錄之參透液；—奈米過_管，係用 夺鼠化四曱基銨與光阻劑及高價金屬如：Fe、Al等進行分 ⑽純水桶’係用以於濃縮槽供給純水；以及一泵浦，利用Ben, in the silk of the 'in the step (1) by the acid in the shadowing waste liquid ^ 匕 ^ ammonium ^ filamentous _, the content of the four-filament acid salt or after, can also be used The treatment, and the electrolysis of ^^4), before the electrolysis, the treatment of the substance and pre-purification, the concentration can be exemplified by, for example, evaporation concentration, reverse condensation, membrane distillation, etc. to achieve the appropriate concentration . Pre-purification can be carried out by using activated carbon treatment, cation exchange resin and/or anion exchange = etc. (4) Pre-purification of traces such as photo-, cation and/or anion to achieve the purity of various industrial electronics. Purification step [Embodiment] The embodiment is exemplified, and the squat is implemented to clarify the invention', but it should not be construed as limiting the *A two-day range.帛1 diagram shows that the nano-peripheral membrane (10) membrane is separated from the specific one. The gas-oxidized tetramethyl group concentration is analyzed by acid titration. The recovery rate of tetramethylammonium salt is from: Conductivity X permeate volume) / (Electrochemical conductivity of the acid base after the acid neutralization, X initial treatment liquid volume) χ 100% · " r calculated, light _ front correction W see 绮At the wavelength == measuring the Weiss hearing, the silk age indicates the photoresist. Example 1 The sample solution is produced by the liquid crystal display (LCD) factory A company, and the developing waste liquid is sampled by the developing process ship π money. . The concentration of tetramethylammonium hydroxide contained in the Laiwu waste liquid was G.66% by weight, and the absorbance was Q 6〇2 at a wavelength of 28Qnm by an ultraviolet-visible light absorption meter. Take 5^.30L of the developing waste liquid to adjust the pH to 32% Ηα, and the pH of the device is 6."1, which is the sample solution. A tetramethylammonium hydroxide conversion to reduce tetramethylammonium, measured by a conductivity meter, 201126283, tetra-"EC" 0 ^ a bay pass - containing nanofiltration membrane (NF membrane) separation device (for It's the device OT90_2540 manufactured by the Naihu Ship (10) and the second division, and the separation device is provided with the development waste liquid after the conversion treatment of the tetramethylammonium hydroxide contained in the gluten; a filtrate tank for accommodating a penetrating liquid recorded by a naphthyl group; a nanometer _ tube, which is a mouse-based tetradecyl ammonium and a photoresist and a high-valent metal such as Fe, Al and the like (10) pure water bucket ' is used to supply pure water in the concentration tank; and one pump is utilized
2=自純水桶泵人濃縮槽中。奈米過濾、膜之分離裝置之初 為O.lL/min、初始壓力為8 5kg/cm2，隨著分離裝置起 Ϊ5式樣溶液於激縮射開始被濃縮域量逐漸降低，為保持流 置一定壓力需隨之增加而予以調整。 當，縮液侧所偵測電導度值提升至2〇〇〇〇μ3/(；ιη以上時； 此時流量為(UL/min、壓力為，啟祕水泵浦，開 始以O.lL/min之速度添加純水(較好為去離子水)於濃縮槽中， 直至滲透槽中溶液體積至49.5L停止試驗。 於滲透侧所收集之滲透液體積為49 5升，其pH經測得為 7.46,以電導度計測得氯化四甲基錢電導度EC為5530 ps/cm， 以紫外光-可見光吸光計設定於波長為28〇nm偵測其吸光度為 0.027，由試驗前之吸光度可知光阻劑殘留量減少相當多，且 由試驗前之電導度，可計算出氣化四甲基銨回收率為 (553〇χ49.5)/(717〇χ5〇·3)= 75.9〇〇/0)。 實施例2 試樣溶液配製及奈米濾膜(NF膜)分離裝置起動條件係同 實施例1所示。試樣溶液的氫氧化四甲基銨(ΤΜΑΗ)濃度、酸 中和後氯化四甲基銨電導度(EC)、體積、調整後ρΗ值及光阻 劑吸收值(280nmabs)如下表1所示。 當濃縮液側所偵測電導度值提升至20000ps/cm以上時； 此時流量為O.lL/min、壓力為14.9kg/cm2，開始以0.08/min之 201126283 子水於軸射，直至濃縮射殘留溶液小於 道洛與ΐ施例1同樣測巧參透側之滲透液之氣化四甲美錄雷 收;:其劑吸收值，並計算氯化四甲“回 比較例1 實施奈米濾膜⑽膜)分離裝置起動條件係同 ί ί 絲.幢未赠賴料加純水(ί 美銨電導ΐΐοί 2氧化四甲基錄濃度(ΤΜΑΗ)、氯化四甲2 = from the pure bucket pump in the human concentration tank. The nanofiltration and membrane separation device is initially O.lL/min, and the initial pressure is 85 kg/cm2. With the separation device, the 5 sample solution is gradually reduced in the concentration field at the beginning of the stimuli, in order to keep the flow constant. The pressure needs to be adjusted to increase. When the conductivity value detected on the liquid-reducing side is raised to 2〇〇〇〇μ3/(;ιη以上; at this time the flow rate is (UL/min, pressure is, the water pump is activated, starting with O.lL/ At the speed of min, pure water (preferably deionized water) is added to the concentration tank until the solution volume in the permeate tank reaches 49.5 L. The volume of the permeate collected on the permeate side is 49 5 liters, and the pH is measured. The conductivity of the tetramethyl chlorination chloride was 5.530 ps/cm measured by a conductivity meter, and the absorbance was 0.027 at a wavelength of 28 〇nm by an ultraviolet-visible absorbance meter. The absorbance before the test was known. The amount of photoresist residue is reduced considerably, and the conductivity of gasified tetramethylammonium can be calculated from the conductivity before the test (553〇χ49.5)/(717〇χ5〇·3)= 75.9〇〇/0 Example 2 Preparation of sample solution and starting conditions of the nanofiltration membrane (NF membrane) separation device are shown in the same manner as in Example 1. The concentration of tetramethylammonium hydroxide (ΤΜΑΗ) in the sample solution, and the chlorine after acid neutralization. The conductivity (EC), volume, adjusted pH value and photoresist absorption (280 nmabs) of tetramethylammonium are shown in Table 1. The electricity detected on the concentrate side When the degree is increased to more than 20,000 ps/cm; at this time, the flow rate is 0.1 L/min, the pressure is 14.9 kg/cm2, and the injection is started at 0.08/min of 201126283 water, until the residual solution is less than Dorothy and ΐ. Example 1 also measured the permeation of the permeate on the permeate side of the gasification of the four meridians; the absorption value of the agent, and calculated the tetramethyl chloride "back to the comparative example 1 implementation of the nanofiltration membrane (10) membrane) separation device starting conditions It is the same as ί ί 丝. The building has not given the material plus pure water ( 美 铵 电 电 ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί 、 、 、
8積、調整後姆絲賴嶋(_ 始被慮：工f，;;，中開 敕本π丄认仏！ / 2 馮保符里為一疋，壓力需隨之調 正不大於40kg/cm (此為設備操作壓力極限），直 殘留溶液小於1L停止試驗。 H辰縮槽中 與實施例1同樣測定渗透側之滲透液之氯化四甲基録電 2 及光阻劑吸收值’並計算氯化四甲基録回 收率，其結果不於下表1〇 比較例2 试樣溶液配製及奈米遽膜輯膜)分離裝置起動條件係同 ^施例1所示’但於分離_中並未約農縮槽中添加純 離子水)。離溶液的絲細？基^(ΤΜΑΗ)濃度、氯化 ，錢電導度(EC)、體積、調整後阳似光_吸收值腿 abs)如下表1所示。 將該試樣溶峨著過魏置起動試樣錄於濃縮槽中開 始被滚縮造成流量下降，為保持流量—定壓力规之調整至不 大於40kg/cm ’直至濃縮槽中殘留溶液小於江停止試驗。 與實施例1囉測定參透側之滲透液之氯化四甲基錢濃 度、體積、pH值及光阻劑濃度，並計算氣化四甲基銨回收 其結果示於下表1。 201126283 表1 實施例1 實施例2 比較例1 比較例2 試樣溶液 ΤΜΑΗ% 0.66 0.66 0.66 0.66 經鹽酸中和 電導度值 EC(ps/cm) 7170 7200 7540 7200 vol. (L) 50.30 50.30 50.00 50.00 pH值 6.991 7.294 9.228 6.473 280nm abs 0.602 0.629 0.774 0.648 渗透液 電導度值 EC(“s/cm) 5530 6120 3620 4230 vol. (L) 49.5 50 46.5 48.3 pH值 7.46 7.66 9.16 7.04 280nm abs 0.027 0.036 0.015 0.019 TMAC1 回收率〇/0 75.90% 84.49% 44.65% 56.75%8 product, adjusted after Ms Lai 嶋 (_ began to be considered: work f,;;, 敕 敕 丄 丄 / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / / (This is the operating pressure limit of the equipment), the straight residual solution is less than 1L to stop the test. In the same manner as in the first embodiment, the chlorinated tetramethyl chloride recording 2 and the photoresist absorption value of the permeate on the permeate side are determined in the same manner as in the first embodiment. Calculate the recovery rate of tetramethyl chloride. The results are not as shown in Table 1 below. Comparative Example 2 Preparation of sample solution and film preparation of the separation membrane of the nano-membrane separation device are the same as those in the first example. There is no pure ionized water added to the tank. Thinner from the solution? Base ^ (ΤΜΑΗ) concentration, chlorination, money conductivity (EC), volume, adjusted positive light _ absorption value legs abs) as shown in Table 1. The sample is dissolved in the starter sample and recorded in the concentration tank, and the flow rate is decreased by rolling, so as to maintain the flow rate-fixing pressure gauge to not more than 40 kg/cm ' until the residual solution in the concentration tank is smaller than the river. Stop the test. The chlorinated tetramethylammonium concentration, volume, pH, and photoresist concentration of the permeate on the permeate side were measured in the same manner as in Example 1 and the vaporized tetramethylammonium was recovered. The results are shown in Table 1 below. 201126283 Table 1 Example 1 Example 2 Comparative Example 1 Comparative Example 2 Sample solution ΤΜΑΗ% 0.66 0.66 0.66 0.66 Neutralization conductivity value EC (ps/cm) 7170 7200 7540 7200 vol. (L) 50.30 50.30 50.00 50.00 pH 6.991 7.294 9.228 6.473 280nm abs 0.602 0.629 0.774 0.648 Permeate conductivity value EC ("s/cm" 5530 6120 3620 4230 vol. (L) 49.5 50 46.5 48.3 pH 7.46 7.66 9.16 7.04 280nm abs 0.027 0.036 0.015 0.019 TMAC1 Recovery rate 0/0 75.90% 84.49% 44.65% 56.75%
由上表1之結果可知，依據本發明之方法所回收之氯化四 y基錄比f分離過程中未於濃縮槽中添加純水的比較例1及2 可回收$向比例的四甲基録之酸鹽，故於後續利用電解將氣化 =甲基錄轉換回氫氧化四甲基_，可獲得較比較例高的回收 〇 上述實施例1及2中所收集之滲透液隨後可利用例如曰本 /寺開昭57_181385以及美國專利號第5968338中所述 即I將其崎含之祕四T基鋪換喊氧化四甲基 叙(鹼鹽），並予以回收再利用。 【圖式簡單說明】 無 【主要元件符號說明】 無From the results of the above Table 1, it can be seen that the comparative examples 1 and 2 in which no pure water was added to the concentration tank during the separation of the four y groups recorded in the method of the present invention can recover the ratio of tetramethyl groups. Recorded acid salt, so after the subsequent use of electrolysis to convert gasification = methyl record back to tetramethyl methoxide _, a higher recovery than the comparative example can be obtained. The permeate collected in the above examples 1 and 2 can then be utilized. For example, 曰本/寺开昭57_181385 and U.S. Patent No. 5,968, 338, I will replace the sulphur tetramethyl sulphate (alkali salt) with its secret four-base slab and recycle it. [Simple diagram description] None [Main component symbol description] None