201002627 30925pif 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種利用逆滲透裝置從含磷酸水回收 磷酸的方法及裝置，且特別是有關於一種可以從蝕刻液晶 基板或晶圓以及其他電子設備後的含有碟酸的洗條廢水中 回收可抑制真菌、酵母等微生物的產生的磷酸等有價物質 和作為處理水的純水的回收磷酸的方法及裝置。 【先前技術】 在液晶基板或晶圓以及其他電子設備的蝕刻中，使用 含有磷酸的蝕刻液。蝕刻製程中產生的高濃度的廢蝕刻液 被回收以再生利用，但蝕刻後的電子設備經純水洗滌，生 成大量的低濃度的洗滌廢水。上述洗滌廢水除含有作為蝕 刻液成分的麟酸、罐酸、醋酸以及其他酸成分等以外，還 含有藉由钱刻而溶出的金屬離子以及其他雜質，但大部分 為純水。 以往，將上述蝕刻洗滌廢水與其他廢水混合進行處 理。作為一般的含磷酸或氟酸的廢水的處理技術，可以列 舉凝集沉澱處理。但是，對磷酸或氟酸進行凝集沉澱處理 時，由於使用大量的藥物和產生大量的污泥，因而產生處 ^成本上升、環境負荷增大等問題。此外，由於在凝集沉 澱處理中添加大量的藥物，故使水溶性離子增加，這盥水 回收時逆滲透膜製程的操作壓力上升引起的動力成^增 加、處理水質惡化、產生污垢(scale)、以及在離子交換^ 中再生劑的使用量増加有關聯。 5 201002627 30925pif 在曰本專利特開2006 — 75820號中，使用離子交換 脂除去磷酸、硝酸等的離子，回收純水以及磷酸鹽。但是、， 此方法雖然是以磷酸鹽(磷酸二氫鈉等）的形式進行回=， 但填酸鹽幾乎沒有銷路，磷酸的納鹽由於溶解度小1 狀時磷酸的含有率低，難以運輸，形成鉀鹽時^氧化= 饧格而。另外，為了形成磷酸二氫鈉，有人展示了向H裉 陽離子樹脂中通入液體的方法，但卻存在以下缺點° = ^::脂的再生：’鹽酸等酸被消耗；而在陰離子樹脂的 再生中，所用的氫氧化納也被白白地排出等。 若使料滲透_難#上_子交換㈣ 離’則真菌、酵母等有害微生物在咖上增殖，膜 =差上升’透過水量下降。控制真S、酵母等有宝微生 物時，有物理控制(增殖抑制、除菌、阻斷、殺 =(增f中抑T化學控制(增殖抑制、藥物殺菌)、生 增殖抑制包括：溫度控制、化學物質# =U)，殺菌包括：低溫㈣、高溫殺3、電磁波殺 化氫等)、液殺ΐ劑^菌劑(E: ’、臭氧、過氧 劑等）、固if過氧化氯水、有機系殺菌 固定化殺菌劑(㈣第四m、光催化劑系殺菌劑等）、 用高，設備費 引起的培旬，逆滲透琪的性能;變氣質 201002627 30925pif 體权菌劑(EO、曱酸等）、有機系殺菌劑等用於化學控制的 樂物還存在毒性或環境負荷的問題。若真菌、酵母等有害 微生物在膜面上繁殖，則使樹脂或逆渗透膜發生堵塞，無 法穩定運轉，而產生的真菌、酵母等微生物又難以除去， 特別是在離子交換樹脂或逆滲透膜中，由於不能使用氧化 劑，所以沒有相應的方法。 【發明内容】 本發明之課題在於提供一種回收磷酸的方法及裝置， 此方法不使用特別的藥物等’利用簡單的構成和操作，可 以低成本且高效率地從含磷酸水中以高濃度的可運輸的液 狀回收抑制真菌、酵母等微生物的產生、可作為回收物的 高純度的磷酸。 本發明提出一種從含磷酸離子水回收磷酸的方法及裝 置。 (1) 一種回收磷酸的方法，使用逆滲透裝置對含磷酸水 進行膜分離處理以回收磷酸，該方法的特徵在於： 在逆滲透裝置中，對調整成pH小於等於2、磷酸濃度 大於等於600 mg/L、且導電率大於等於200 mS/m的調整 含磷酸水進行膜分離處理。 (2) —種回收磷酸的方法，使用逆滲透裝置對含磷酸水 進行膜分離處理以回收磷酸，該方法的特徵在於： 將調整成pH小於等於2、磷酸濃度大於等於6〇〇 、且導電率大於等於200 mS/m的調整含磷酸水間斷 地供給逆滲透裝置，以進行膜分離處理。 201002627 30925pif 其中逆滲透裝置形 (3)如上述(1)或(2)所記載之方法 成大於等於兩段的構成， 在第-段的逆滲透裝置巾，對調整含磷酸水進行膜分 離處理， 在第二段以後的逆滲透裝置中，對第一段的逆渗透裝 置的磷酸濃縮液進行第二段以後的膜分離處理。 …（4)如上述(1)〜(3)中任一項所記載之方法，其中供給 疋渗透裝置_整含雜水是在被處理含雜水中加入鱗 酸以調整至預定值的調整含鱗酸水。 、、，、（5)如上述(1)〜(4)中任一項所記載之方法，其中供給 逆滲透裝置的調整含磷酸水是在被處理含磷酸水中加入逆 滲透裴置的磷酸濃縮液及/或蒸發濃縮裝置的磷酸溶液，以 °周整至預定值的調整含碟酸水。 (6)—種磷酸回收裝置，從含磷酸水中回收磷酸，所述 裳置包括： 含磷酸水調整部，其將被處理含磷酸水調整成pH小 於等於2、碟酸濃度大於等於600 mg/L、且導電率大於等 於200 mS/m的調整含麟酸水； 逆渗透裝置，其對調整成pH小於等於2、碟酸漢度大 於等於600 mg/L、且導電率大於等於2〇〇 mS/m的調整含 碌酸水進行膜分離處理’以使磷酸以外的酸與水一同透過 至透過液室側’並在濃縮液室侧濃縮鱗酸； 含磷酸水供給部，其向逆滲透裝置之濃縮液室侧供給 調整含磷酸水； 201002627 30925pif 過液； 透過液取出部，其從逆滲透裝置之透過液室侧取出 透 循ί哀路徑，其將一部分濃縮磷酸液從逆滲透裝置之产 縮液室侧循環至含磷酸水調整部；以及 辰 濃縮磷酸液取出部，其取出來自逆滲透裝置之濃 室侧的剩餘部分。 f" (Ό如上述(6)所記載之裝置，其中逆滲透裝置形成兩 段的構成， 具有第一段磷酸濃縮液供給部，上述供給部向第二段 逆滲透裝置供給第一段逆滲透裝置的第一段磷酸濃縮液； 其中循環路徑的構成方式為：將第二段磷酸濃縮液的 一部分從第二段逆滲透裝置之濃縮液室側循環至含磷峻 調整部； 濃縮碟酸液取出部的構成方式為：從第二段逆滲逯裝 置之濃縮液室侧取出第二段磷酸濃縮液的剩餘部分。 (8)如上述(7)所記载之裝置，其具有蒸發濃縮農置， 上述蒸發ί辰縮裝置蒸發濃縮從第二段逆渗透裝置之濃縮液 室側取出的第二段磷酸濃縮液的剩餘部分。 本發明中，作為處理對象的含磷酸水只要是含有磷酸 的水即可’沒有限制，但其中含有的鱗酸離子大於等於50 mg/L而小於6〇〇 mg/L (調整含磷酸水的磷酸濃度大於等於 1500 mg/L時’含碟酸水中含有的磷酸離子大於等於5〇 mg/L而小於i500mg/L)、pH超過2而小於等於3(調整含 碟酸水的pH小於等於1.5時，含填酸水的pH超過1.5而 201002627 30925pif 小於等於3)、且導電率小於2〇〇 mS/m (調整含磷酸水的導 電率大於等於1800mS/m時，含磷酸水的導電率小於18〇〇 mS/m)。 在任一種情況下，酸性水作為處理對象，較佳的是， 除含有磷酸離子外，均可含有硝酸離子'醋酸離子等酸成 分、其他陰離子、以及金層離子等陽離子和其他雜質，但 較佳的是’在處理前先除去陽離子。本發明中，特別適於 從含有硝酸離子、醋酸離子等其他酸成分的含磷酸水中除 去猶離子、醋酸離子等其他酸成分，以回收高純度_ 酸。特別是作為處理對象的較佳的含碟酸水，包括在利用 含磷酸的蝕刻液蝕刻液晶基板或晶圓以及其他電子設備後 進行純水洗滌時產生的低濃度的洗滌廢水。 一當上述被處理含磷酸水與上述調整含磷酸水相比pH 向而濃度低時，真g、酵母等有害微生物在逆渗透膜的膜 面繁瘦’導致膜職’所以在本發財，為了從含鱗酸水 中回收填酸，在逆滲透裝置中，對將賴酸水、特別是除 去了陽離子的含磷酸水調整成pH小於等於2、較佳的是^ 於等於1.5、鱗酸濃度大於等於_ mg/L、較佳的是大於 等於1500mg/L、且導電率大於等於2〇〇 mS/m、較佳的是 大於等於1800 mS/m的調整含磷酸水進行膜分離處理。上 述調整含磷酸水在膜分離處理階段只要達到上述pH、磷酸 濃度及導電率即可，所以在膜分離處理中，被逆滲透裝置 之濃縮室濃縮時’在濃縮狀態下只要達到上述pH、鱗酸濃 唐；5道雪銮gp ·?Γ。 201002627 30925pif 在向逆渗透裝置供給被處理含鱗酸水的階段，若被處 理含磷酸水與上述調整含磷酸水相比pH高而濃度低，則 對被處理含磷酸水進行調整。在逆滲透裝置為一段以及大 於等於兩段的情況下，供給第一段之逆滲透裝置的被處理 含磷酸水與上述調整含磷酸水相比PH高而濃度低。在逆 滲透裝置為大於等於兩段的情況下，由於第一段之逆滲透 裝置_酸濃縮液達到低pH、高濃度，所以不必對第^段 以後供給的磷酸濃縮液的pH及濃度進行調整。 將尚pH、低浪度的被處理含填酸水調整成低pH、高 濃，時，較佳的是，向被處理含鱗酸水中注入酸以調整阳 及濃度；制麵是，加人猶作為酸，_整成預定值 的調整含魏水。加人到被處理含_水巾的磷酸可以使 用逆滲透裳置之俩濃驗及/或紐濃縮裝置的填酸溶 液逆/參透裝置中的磷駿濃縮液，其中硝酸、醋酸等雜質 ，除去’破浪度〶’因此較佳的是循環使用。蒸發濃縮 ^置中的雜溶液是轉透裝置的濃難、制是蒸發濃 縮第二段的濃驗時㈣縮磷酸溶液，可以循環使用。 、如此地调整成低pH、高濃度的調整含填酸水 ，若在逆 、、，透裝置中對其進行膜分離處理，則真菌、酵母等有害微 生物在逆滲賴謂_繁轉肋制。祕，即使不使 用氧化劑等特藥物或紫外料殺菌裝置等，也不會發 2微生物的繁剌起的轉透朗堵塞，*會出現膜間 Μ Γ上升或透過水置的下降’逆滲透裝置可以穩定運 轉。由於有害微生物抑制效果會剌—定減，所以也可 201002627 30925pif 以間斷地供給調整含磷酸水，但較佳的是繼續供給調整含 磷酸水。 即，調整成低pH、高濃度的調整含磷酸水，通常較佳 的是供給逆滲透裝置以進行膜分離處理，但也可以間斷地 供，逆滲透裝置以進行臈分離處理。在後一種情況下，通 常疋將比上述調整含磷酸水之ρΉ高而濃度低的被處理含 鱗酸水直接供給逆滲透裝置以進行膜分離處理，可以間斷 地供給調整成低ρΗ、高漠度的調整含鱗酸水、例如卜] 天供給1次、例如供給卜2小時左右，以進行膜分離處理。 =種情況下，將被處理含磷酸水直接供給逆滲透裝置以進 行膜分離處理’可以間斷地注入磷酸，以調整含碟 PH及濃度。 本發明中，在將含磷酸水供給逆滲透裝置之前， ^于前處理、即除去包括_子及/或_子細的 特別是藉W料了陽離子的含磷酸水作騎象、 濃度’提高膜分離處理所產生的磷酸與 其他酸的分離效果。這種情況下，可賈興 由沉澱分離、過渡等除去固體物質，還可^、即藉 即利用陽離子交換樹脂除去金屬離子等陽離子仃前處理、 :陰離子交換樹脂除去高氯酸、有機酸錯合物等 專。作為上述刮處理製程中使用的前處理癸、丢 目的所採用的一般裝置。 x ’使用上述 蝕刻後的洗滌廢水中所含的銦、鐵、紹 在膜分離製程中導致逆滲透(RO)膜堵夷，& a的金屬離子 土而鬲氯酸等達到 12 201002627 30925pif 兩濃度時導致膜㈣’因此藉由除去上述_ 子’可以防止膜堵塞和損傷等，因此較佳。作 ‘ 換樹脂，可以使用魏性或_性_ _ = rH形的強酸性陽離子交換樹脂來交換除去=離; 時’處理液的酸成分增加’容易調整至小於等於PH3: 此較佳。作秘離子交換翻旨，可从μ : f" 交換樹脂可以使㈣祕或弱驗性的陰離子交換樹 離子父換樹脂以猶形式等暖形式使用，使雜、确酸了 醋酸等通過，除去其他雜質陰離子。 在^發明中，膜分離製程中的逆渗透裝置也稱作r〇 裝置、’錯由逆渗透(RO)膜劃分成透過液室和濃縮液室，此 逆參透裝置的構成方式為：將含罐酸水在小於2、 碟酸濃度大於料6GG mg/L、轉電枝於等於· ms/m 的條件下供給濃駭室側，以進行逆料轉理，使碟酸 以外的酸與水-同透過至透過液錢，啊在濃縮液室侧 濃縮喊。在逆滲透裝置之濃縮液室侧形成有：供认含鱗 酸水的含磷酸水供給部、以及取出濃縮雜液的濃縮魏 液取出部。在逆滲透裝置之透過液室侧形成有取 的透過液取出部。在濃縮磷酸液取出部與含磷酸水供給部 之間可以形成循環路徑，上述循環路徑將從濃_酸^取 出部取出的濃縮磷酸液作為調整用的磷酸循環至濃縮液室 側。 / 當逆滲透裝置為兩段構成時，具有第—段碟酸濃縮液 供給部，此供給部將第一段逆滲透裝置的第一段磷酸濃縮 13 201002627 30925pif 第二段逆滲透裝置，循環路徑的構成方 第農T 一 第二段逆滲透裝置之濃縮液室 側狀至第-段之逆滲透裝置之濃縮液室側 ==成方ί可以是··從第二段逆參透裝置= 液至側取出弟二段磷酸濃縮液的剩餘部分。藉此 裝置的磷酸濃縮液供給第二段逆滲透裝置以 土; Τ第二段逆參透裝置的磷酸濃縮液的 =透膜是-種半透膜，其利用浸透壓使水透過、或 “Hi較高的高壓以供㈣皮處理液’藉* ,的材質只要具有上述特性即可，沒有特別限 ;透===稱聚;r系透過膜、纖维* 多孔性支撲體上开μ ίίϊ參透膜’但較佳的是於微 的複合逆滲賴。上具有_分離性的活性表層 a 透Ί要具備上述逆滲透膜即可，但較佳的 機構、集水機構等一體化的膜組 有其透農置。對膜組件沒有特別限定’例如 ί 平面膜組件、螺旋膜組件、中空絲膜組件 梦署、t述膜纪件的逆渗透裝置可以使用習知的逆渗透 扭ίί的疋在低壓下操作的高透過性的逆滲透襄置。201002627 30925pif VI. Description of the Invention: [Technical Field] The present invention relates to a method and apparatus for recovering phosphoric acid from phosphoric acid-containing water using a reverse osmosis device, and more particularly to a method for etching a liquid crystal substrate or wafer and A method and apparatus for recovering phosphoric acid, such as phosphoric acid, which inhibits the production of microorganisms such as fungi and yeast, and purified water as pure water for treating water, are recovered from the washing liquid waste water containing the acid acid after the other electronic equipment. [Prior Art] An etching solution containing phosphoric acid is used for etching a liquid crystal substrate or a wafer and other electronic devices. The high-concentration waste etching liquid generated in the etching process is recovered for recycling, but the etched electronic equipment is washed with pure water to produce a large amount of low-concentration washing wastewater. The washing wastewater contains, in addition to linonic acid, can acid, acetic acid, and other acid components as components of the etching solution, metal ions and other impurities eluted by money, but most of them are pure water. Conventionally, the above etching washing wastewater is mixed with other wastewater for treatment. As a general treatment technique for wastewater containing phosphoric acid or hydrofluoric acid, agglomeration precipitation treatment can be mentioned. However, when agglomerating and precipitating a phosphoric acid or a hydrofluoric acid, a large amount of a drug is used and a large amount of sludge is generated, which causes problems such as an increase in cost and an increase in environmental load. In addition, since a large amount of a drug is added in the agglutination precipitation treatment, the water-soluble ions are increased, and the power generation due to an increase in the operating pressure of the reverse osmosis membrane process during the recovery of the hydrophobic water is increased, the treated water quality is deteriorated, and scale is generated. And the amount of regenerant used in the ion exchange ^ is related. 5 201002627 30925pif In Japanese Patent Laid-Open No. 2006-75820, ions such as phosphoric acid and nitric acid are removed using an ion exchange grease, and pure water and phosphate are recovered. However, although this method is carried out in the form of phosphate (sodium dihydrogen phosphate, etc.), there is almost no sales of the acid-filled acid salt, and the sodium salt of the phosphoric acid has a low content of phosphoric acid when the solubility is small, and it is difficult to transport. When the potassium salt is formed, ^ oxidation = 饧格. In addition, in order to form sodium dihydrogen phosphate, a method of introducing a liquid into a H裉 cation resin has been shown, but the following disadvantages exist: ^ = :: Regeneration of fat: 'acid such as hydrochloric acid is consumed; and in anionic resin During regeneration, the sodium hydroxide used is also discharged in vain. If the material is allowed to permeate, the harmful microorganisms such as fungi and yeast proliferate on the coffee, and the membrane = difference rises. When controlling the precious microorganisms such as true S and yeast, there are physical controls (proliferation inhibition, sterilization, blocking, killing) (increasing f, suppressing T chemical control (proliferation inhibition, drug sterilization), and inhibiting growth and proliferation include: temperature control, Chemical substance # = U), sterilization includes: low temperature (four), high temperature kill 3, electromagnetic wave hydrogen peroxide, etc.), liquid acaricide ^ bacteria (E: ', ozone, peroxide, etc.), solid if chlorine peroxide Organic bactericidal fixed bactericide ((4) fourth m, photocatalyst bactericide, etc.), high, equipment cost, Pei Xun, reverse osmosis performance; variable temperament 201002627 30925pif Phytotoxicity agent (EO, 曱Musical substances such as acids and the like, organic bactericides, etc., which are used for chemical control, also have problems of toxicity or environmental load. If harmful microorganisms such as fungi and yeast multiply on the membrane surface, the resin or reverse osmosis membrane is clogged and cannot be stably operated, and microorganisms such as fungi and yeast are difficult to remove, especially in ion exchange resins or reverse osmosis membranes. Since there is no way to use an oxidant, there is no corresponding method. SUMMARY OF THE INVENTION An object of the present invention is to provide a method and an apparatus for recovering phosphoric acid, which can be used at a low concentration and high efficiency from a phosphoric acid-containing water at a low concentration without using a special drug or the like. The liquid recovery of transportation inhibits the production of microorganisms such as fungi and yeast, and can be used as a highly purified phosphoric acid. The present invention provides a method and apparatus for recovering phosphoric acid from water containing phosphate ions. (1) A method for recovering phosphoric acid, which comprises a membrane separation treatment for recovering phosphoric acid using a reverse osmosis device, wherein the method is characterized in that: in a reverse osmosis device, the pH is adjusted to be equal to or lower than 2, and the phosphoric acid concentration is greater than or equal to 600. The membrane-separated treatment is carried out by adjusting the phosphoric acid-containing water containing mg/L and having a conductivity of 200 mS/m or more. (2) A method for recovering phosphoric acid, which uses a reverse osmosis device to perform membrane separation treatment on phosphoric acid-containing water to recover phosphoric acid, and the method is characterized in that: the pH is adjusted to be equal to or lower than 2, the phosphoric acid concentration is 6 大于 or more, and conductive The adjusted phosphoric acid-containing water having a rate of 200 mS/m or more is intermittently supplied to the reverse osmosis device for membrane separation treatment. 201002627 30925pif wherein the reverse osmosis device (3) has a configuration of two or more stages as described in the above (1) or (2), and the membrane is separated by adjusting the phosphoric acid-containing water in the reverse osmosis apparatus of the first stage. In the reverse osmosis apparatus after the second stage, the phosphoric acid concentrate of the reverse osmosis apparatus of the first stage is subjected to membrane separation treatment after the second stage. (4) The method according to any one of the above (1) to (3), wherein the supply of the osmosis device _ the entire water-containing water is adjusted to a predetermined value by adding scaly acid to the treated water-containing water. Squama water. The method according to any one of the above (1) to (4), wherein the adjusted phosphoric acid-containing water supplied to the reverse osmosis device is a phosphoric acid concentrated by adding a reverse osmosis gas to the treated phosphoric acid-containing water. The phosphoric acid solution of the liquid and/or evaporation concentrating device is adjusted to a predetermined value for the period of time. (6) a phosphoric acid recovery device for recovering phosphoric acid from phosphoric acid-containing water, the skirt comprising: a phosphoric acid-containing water adjustment unit that adjusts the treated phosphoric acid-containing water to have a pH of less than or equal to 2 and a dish acid concentration of 600 mg or more. L, and the conductivity is greater than or equal to 200 mS / m of the adjustment of linonic acid water; reverse osmosis device, the pair is adjusted to pH less than or equal to 2, the acidity of the dish is greater than or equal to 600 mg / L, and the conductivity is greater than or equal to 2 〇〇 The mS/m is adjusted to contain the acid water to carry out the membrane separation treatment 'so that the acid other than phosphoric acid is passed through to the permeate chamber side together with the water' and the sulphuric acid is concentrated on the concentrate chamber side; the phosphoric acid water supply portion is reverse osmosis The concentrated liquid chamber side supply of the device is adjusted to contain phosphoric acid water; 201002627 30925pif liquid permeate; the permeate liquid take-out portion is taken out from the permeate liquid chamber side of the reverse osmosis device, and a part of the concentrated phosphoric acid liquid is removed from the reverse osmosis device The production-reducing liquid chamber side is circulated to the phosphoric acid-containing water adjusting portion; and the condensed phosphoric acid liquid-removing portion is taken out, and the remaining portion from the rich chamber side of the reverse osmosis device is taken out. The apparatus according to the above (6), wherein the reverse osmosis device has a two-stage configuration, and has a first-stage phosphoric acid concentrate supply unit, and the supply unit supplies the first-stage reverse osmosis to the second-stage reverse osmosis unit. a first stage phosphoric acid concentrate of the device; wherein the circulation path is configured by circulating a portion of the second stage phosphoric acid concentrate from the concentrated liquid chamber side of the second stage reverse osmosis device to the phosphorus containing adjustment portion; concentrating the dish acid solution The take-out portion is configured to take out the remaining portion of the second-stage phosphoric acid concentrate from the concentrated liquid chamber side of the second-stage reverse osmosis device. (8) The device according to the above (7), which has an evaporation enrichment farm The evaporation portion is evaporated to concentrate the remaining portion of the second-stage phosphoric acid concentrate taken out from the concentrate chamber side of the second-stage reverse osmosis device. In the present invention, the phosphoric acid-containing water to be treated is only phosphoric acid-containing. Water can be 'no limit, but it contains selenate ions greater than or equal to 50 mg / L and less than 6 〇〇 mg / L (adjust the phosphoric acid containing phosphoric acid concentration of 1500 mg / L or more) Phosphate The amount is greater than or equal to 5〇mg/L and less than i500mg/L), and the pH exceeds 2 and is less than or equal to 3 (when the pH of the acid containing water is less than or equal to 1.5, the pH of the acid-containing water exceeds 1.5 and 201002627 30925pif is less than or equal to 3) And the electrical conductivity is less than 2〇〇mS/m (when the conductivity of the phosphoric acid-containing water is 1800mS/m or more, the conductivity of the phosphoric acid-containing water is less than 18〇〇mS/m). In either case, the acidic water is treated as Preferably, the object contains, in addition to the phosphate ion, an acid component such as a nitrate ion, an anion, or a cation such as a gold layer ion, and other impurities, but it is preferred to remove the cation before the treatment. In the present invention, it is particularly suitable for removing other acid components such as helium ions and acetate ions from phosphoric acid-containing water containing other acid components such as nitrate ions and acetate ions to recover high-purity acid. Containing disc acid water, including low-concentration washing wastewater produced by pure water washing after etching a liquid crystal substrate or wafer and other electronic equipment using an etching solution containing phosphoric acid. When the water is lower in pH than the above-mentioned adjustment of the phosphoric acid-containing water, the harmful microorganisms such as true g and yeast are thin on the membrane surface of the reverse osmosis membrane, resulting in a film occupation, so in order to recover from the scaly water The acid, in the reverse osmosis device, adjusts the water containing lysine, particularly the phosphate-containing water from which the cation has been removed, to a pH of 2 or less, preferably 1.5 or more, and a lactic acid concentration of ≥ mg/L or more. Preferably, the membrane-separated treatment is performed by adjusting the phosphoric acid-containing water to be 1500 mg/L or more and having a conductivity of 2 〇〇 mS/m or more, preferably 1800 mS/m or more. In the stage, as long as the above pH, phosphoric acid concentration and electrical conductivity are achieved, in the membrane separation treatment, when concentrated in the concentration chamber of the reverse osmosis apparatus, the above-mentioned pH and squaraine concentration are achieved in the concentrated state; 5 ferrets gp ·? 201002627 30925pif In the stage of supplying the treated scaly water to the reverse osmosis device, if the treated phosphoric acid-containing water has a higher pH than the above-mentioned adjusted phosphoric acid-containing water and the concentration is low, the treated phosphoric acid-containing water is adjusted. In the case where the reverse osmosis apparatus is one section and more than two stages, the treated phosphoric acid-containing water supplied to the reverse osmosis unit of the first stage has a higher pH and a lower concentration than the above-mentioned adjusted phosphoric acid-containing water. In the case where the reverse osmosis device is two or more stages, since the reverse osmosis device of the first stage _acid concentrate reaches a low pH and a high concentration, it is not necessary to adjust the pH and concentration of the phosphoric acid concentrate supplied after the second stage. . When the pH of the treated, low-wave treated acid-containing water is adjusted to a low pH and a high concentration, it is preferred to inject acid into the treated scaly acid water to adjust the cation and the concentration; Still as an acid, the adjustment of _ into a predetermined value contains Wei water. Adding to the treated phosphoric acid containing _ water towel can use the reverse osmosis two-in-one and/or the concentrating solution of the concentrating solution of the phosphoric acid solution in the reverse/penetration device, wherein impurities such as nitric acid and acetic acid are removed. The 'breaking wave' is therefore preferred for recycling. Evaporation and concentration. The miscellaneous solution in the middle is the concentration of the transflective device. The system is a concentrated solution for the second stage of evaporation and condensation. (IV) The phosphoric acid solution can be recycled. In this way, it is adjusted to a low pH and a high concentration to adjust the acid-containing water. If it is subjected to membrane separation treatment in a reverse, and permeating device, the harmful microorganisms such as fungi and yeast are reversed. . The secret, even if you do not use special drugs such as oxidants or UV sterilizer, etc., there will be no turbidity of the microbial turbidity, and there will be a decrease in the membrane 或 或 or a decrease in the permeation of the water. It can run stably. Since the harmful microbial inhibitory effect will be reduced or decreased, it is also possible to supply the phosphoric acid-containing water intermittently at 201002627 30925pif, but it is preferable to continue to supply and adjust the phosphoric acid-containing water. Namely, it is preferable to adjust the phosphoric acid-containing water to a low pH and a high concentration, and it is usually preferred to supply the reverse osmosis device for the membrane separation treatment, but it may be intermittently supplied to the reverse osmosis device for the hydrazine separation treatment. In the latter case, generally, the treated scaly acid water having a higher concentration than the above-mentioned adjusted phosphoric acid-containing water is directly supplied to the reverse osmosis device for membrane separation treatment, and can be intermittently supplied and adjusted to a low pH and high desert. The degree of adjustment of the scaly acid-containing water, for example, is supplied once a day, for example, for about 2 hours, to perform a membrane separation treatment. In the case of the case, the treated phosphoric acid-containing water is directly supplied to the reverse osmosis device to perform the membrane separation treatment. The phosphoric acid may be intermittently injected to adjust the pH and concentration of the disk. In the present invention, before the supply of the phosphoric acid-containing water to the reverse osmosis device, the pre-treatment, that is, the removal of the phosphoric acid-containing water containing the cations, especially the cations, is carried out. The separation effect of the phosphoric acid produced by the separation treatment with other acids is separated. In this case, Jiaxing can remove solid matter by precipitation separation, transition, etc., and can also remove cations such as metal ions by cation exchange resin, pretreatment, anion exchange resin to remove perchloric acid, and organic acid error. Compounds and other specialties. It is a general device used for the pre-treatment and the purpose of use in the above-mentioned scraping process. x 'Using indium, iron, and so on contained in the above-mentioned etched washing wastewater, causing reverse osmosis (RO) membrane blocking in the membrane separation process, & a metal ion soil and chloric acid to reach 12 201002627 30925pif The concentration causes the film (4) to be 'removed by the removal of the above-mentioned _', thereby preventing film clogging, damage, and the like. For the "replacement of the resin, the strong acid cation exchange resin of the Wei or _ _ _ = rH shape can be used for exchange removal = the increase of the acid component of the treatment liquid is easily adjusted to less than or equal to PH3: this is preferable. The secret ion exchange can be used to remove the resin from the μ: f" exchange resin to make the (4) secret or weakly anion exchange tree ion-replacement resin in the form of warmth, etc. Other impurity anions. In the invention, the reverse osmosis device in the membrane separation process is also referred to as an r〇 device, and the fault is divided into a permeate chamber and a concentrate chamber by a reverse osmosis (RO) membrane. The reverse permeation device is constructed in such a manner as to contain The tank acid water is supplied to the concentrated chamber side at a concentration of less than 2, the acid concentration of the dish is greater than 6 GG mg/L, and the electrophoresis is equal to · ms/m, in order to carry out the reverse material transfer, so as to make acid and water other than the dish acid. The same as the through to the liquid money, ah concentrated on the side of the concentrate room. On the concentrated liquid chamber side of the reverse osmosis apparatus, a phosphoric acid-containing water supply unit for supplying scaly water and a concentrated Wei liquid take-out portion for taking out the concentrated liquid are formed. A permeated liquid take-out portion is formed on the permeate chamber side of the reverse osmosis device. A circulation path is formed between the concentrated phosphoric acid solution take-out portion and the phosphoric acid-containing water supply portion, and the concentrated phosphoric acid liquid taken out from the concentrated-acid extraction portion is circulated to the concentrated liquid chamber side as phosphoric acid for adjustment. / When the reverse osmosis device is composed of two stages, it has a first-stage disc acid concentrate supply portion, and the supply portion concentrates the first stage phosphoric acid of the first-stage reverse osmosis unit 13 201002627 30925pif second stage reverse osmosis device, circulation path The composition of the second section of the reverse osmosis device of the second section of the reverse osmosis device to the side of the concentrate chamber of the reverse osmosis device of the first stage == square ί can be ·················· The remaining part of the second-stage phosphoric acid concentrate was taken to the side. The phosphoric acid concentrate of the device is supplied to the second-stage reverse osmosis device to the soil; the phosphoric acid concentrate of the second-stage reverse-permeation device is permeable membrane, which is a semi-permeable membrane, which uses water to permeate the water, or “Hi” The higher the high pressure for the (four) skin treatment liquid 'borrow*, the material as long as it has the above characteristics, there is no special limit; through === weigh; r-type permeable membrane, fiber * porous baffle open μ Ίί ϊ ϊ ' 但 但 但 但 但 但 但 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' 。 。 。 。 。 。 。 。 。 There is no specific limitation on the membrane module. For example, the flat membrane module, the spiral membrane module, the hollow fiber membrane module, and the reverse osmosis device can use the conventional reverse osmosis. The high permeability reverse osmosis device operated at low pressure.
、&酸水、特別是除去了陽離子的含鱗酸水在pH 201002627 30925pif 丄‘等‘1的條件下在逆滲透裝置中進行膜分離處理時， 、。曰 >等碟酸以外的酸與水一同透過逆滲透膜，移動 。、至側’從透過液室侧取出。填酸被阻止透過逆渗 ' 、’殘留於濃縮液室側被濃縮，因此可以作為磷酸濃縮 液從濃縮液它如，^ Μ至侧進行回收。此時，雖然有少量的除磷酸以 外的酸殘留在濃縮液中 ，但在磷酸濃度大於等於600 mg/L 的條件Ti%行齡離處理時 ，磷酸以外的酸的阻止率變 低、而透過率變高，因此可以回收高純度的磷酸濃縮液。 供給逆/參透敦置的含磷酸水的壓力可以是0.3〜5 MPa，較 佳的是0.5〜3MPa。 在逆渗透膜的透過中，比較離子性物質與非離子性物 質的透過時’即使是相同程度的分子量，但在逆滲透膜阻 jh率方面’可以說離子性物質較非離子性物質絕對地容易 被阻止。但是’在磷酸不易解離的、pH小於等於2的條件 下進行逆滲透膜處理時，磷酸的阻止率較硝酸和醋酸絕對 地變馬’可以分別回收硝酸和醋酸等磷酸以外的酸和磷酸。 若濃縮液的磷酸濃度過高，則由於浸透壓的關係而無 法進行膜處理，所以濃縮液之磷酸濃度之上限為15重量百 分比(wt%) ’較佳的是10 wt%。若邊循環上述磷酸濃度的 濃縮液’邊在循環的濃縮液中加入被處理的含磷酸水，將 ?農縮液一部分一部分地作為鱗酸濃縮液取出，以進行一過 式的處理，則可以維持上述磷酸濃度而高效率地進行處理。 邊循環濃縮液邊進行膜處理時’濃縮液的循環次數越 多’嶙酸以外的酸與逆滲透膜接觸而透過膜的機會就越 15 201002627 30925pif 多’可以進一步降低濃縮液中磷酸以外的酸的濃度。此時， 若填酸濃度超過15 Wt%，則無法進行膜處理，所以在濃縮 液中加入稀釋水進行稀釋，之後循環並進行逆滲透處理， 從而可以進一步降低磷酸以外的酸的濃度，可以回收高純 度的磷酸濃縮液。作為稀釋水，可以循環使用從透過水中 除去了雜質的回收水。 從透過液室側取出的逆滲透裝置的透過水，由於其中 含有透過的磷酸、硝酸、醋酸等酸，所以藉由利用雜質除 去裝置從逆滲透裝置的透過水中除去上述酸以及其他雜 質，可以回收純水。這種情況下，雜質除去裝置可以採用 使用離子交換樹脂的離子交換裝置、生物處理裝置等。 另一方面，從濃縮液室側取出的磷酸濃縮液，雖然其 中的硝酸和醋酸等磷酸以外的酸的大部分已被除去，但為 了進一步除去上述成分以提高回收磷酸液的純度和濃度， 可以藉由後處理來進行純化。作為藉由後處理進行的純 化，可以藉由陰離子交換從磷酸濃縮液中除去磷酸以外的 酸來進行純化。這種情況下，設置陰離子交換裝置作為純 化裝置’將濃縮液通入陰離子交換樹脂層中，從濃縮液中 除去硝酸等的強酸離子，可以回收幾乎不含硝酸等的強酸 離子的高濃度的鱗酸。 當逆滲透裝置為大於等於兩段的構成時，將調整含碌 酸水供給第一段之逆滲透裝置以進行膜分離處理，將第一 段之逆滲透裝置的磷酸濃縮液供給第二段以後的逆滲透裝 置以進行第二段以後的膜分離處理。這種情況下，逆渗透 16 201002627 30925pif 裝置具有第一段磷酸濃縮液供給部，此供給部將第一段逆 滲透裝置的第一段磷酸濃縮液供給第二段逆滲透裝置，循 環路徑的構成方式為：將第二段磷酸濃縮液的分從第 一段逆滲透襞置之濃縮液室側循環至含磷酸水調整部；而 濃縮磷酸液取出部的構成方式為：將第二段磷酸濃縮液的 剩餘部分從第二段逆滲透裝置之濃縮液室側取出。上述已 取出的第二段磷酸濃縮液進一步用蒸發濃縮裝置進行蒸發 濃縮，可以回收作為磷酸濃縮液。還可以將已蒸發濃縮白^ 磷酸濃縮液循環至含磷酸水調整部，用作調整用磷酸。、 即，當以第二段逆滲透裝置透過的磷酸液中殘留醋酸 時，即使用陰離子交換樹脂也不能將醋酸完全除去，因此 為了除去醋酸等揮發性成分以提高回收磷酸液的純度和濃 度，以蒸發濃縮裝置進行蒸發濃縮，將水和揮發性成分^ 同除去以/農縮碟酸液，從而可以回收幾乎不含醋酸等揮發 性成分的尚濃度的罐酸。蒸發濃縮裝置可以使用旋轉蒸 儀等習知的裝置。 … 猎由上述操作而回收的碟酸可用作回收物，並且可以 以高濃度的液狀進行運輸，而且可以作為高純度的濃縮磷 酸進行回收。在本發明中，雖然是在小於等於pH2的條件 下進行逆滲透處理，但被處理含磷酸水通常以小於等於 pH3的酸性狀‘悲、而得到，因此藉由注入所回收的麟駿作為 pH調節劑，可以容易地進行調節。另外，利用用於回收磷 酸的方法及裝置’藉由簡單的構成和操作，可以將含碟酸 水調整至pH小於等於2、磷酸濃度大於等於6〇〇 mg/L、 17 201002627 30925pif 且導電率大於等於200mS/m。 藉由上述操作來調節pH、磷酸濃度及導電率，以調整 磷酸濃縮液進行供給，並進行逆滲透處理，從而抑制直菌、 酵母等微生物的產生，可以回收高純度磷酸。藉此f減少 了藥物的使用量及廢棄物的生成量，降低了處理成本' 可 以回收可作為回收物的高純度的濃縮磷酸及純水。回收磷 酸除了用於調整含磷酸水以外，還可以浸潰從逆滲透装置 中取出的逆渗透組件，用於真菌、酵母等微生物 制處理等。 基於上述，根據本發明，由於逆滲透裝置的構成方式 為：在逆滲透裝置中對將含磷酸水、特別是除去 的含磷酸水調節成pH小於等於2、磷酸濃度大於等於6〇〇 mg/L、且導電率大於等於2〇〇 mS/m的調整含磷酸水進行 臈分離處理，所以不使用特別的藥物等，利用簡單的構成 和操作，能夠低成本且高效率地從含磷酸水中以高濃度的 可運輸的液狀回收抑制真菌、酵母等微生物的產生、$ 為回收物的高純度的磷酸。 為讓本發明之上述特徵和優點能更明顯易懂，下文特 舉實施例，並配合所附圖式作詳細說明如下。 、 【實施方式】 以下，利用圖示來說明本發明之實施方式。圖i是實 施方式中__收方法及裝置的流程圖。i為原水槽， 貯f原水(被處理含磷酸水）1&。2為前處理裝置，由^離 子乂換裝置、陰離子交換裝置以及其他雜質除去裝置構And <acid water, especially the scaly acid water from which the cation has been removed, is subjected to membrane separation treatment in a reverse osmosis apparatus under the conditions of pH 201002627 30925pif 丄 'etc.曰 > Acids other than the dish acid are transported through the reverse osmosis membrane together with water. , to the side 'taken out from the side of the permeate chamber. The acid is prevented from passing through the reverse osmosis ', and remains on the side of the concentrate chamber to be concentrated. Therefore, it can be recovered as a phosphoric acid concentrate from the concentrate, for example, to the side. At this time, although a small amount of acid other than phosphoric acid remains in the concentrate, when the concentration of phosphoric acid is 600 mg/L or more, Ti% is aged, and the rate of acid other than phosphoric acid is lowered and transmitted. The rate becomes high, so that a high-purity phosphoric acid concentrate can be recovered. The pressure of the phosphoric acid-containing water supplied to the reverse/seepage may be 0.3 to 5 MPa, preferably 0.5 to 3 MPa. In the permeation of the reverse osmosis membrane, when the ionic material and the nonionic substance are transmitted, even if the molecular weight is the same, the reverse osmotic membrane resistance jh rate can be said that the ionic substance is more absolute than the nonionic substance. Easy to be blocked. However, when the reverse osmosis membrane treatment is carried out under conditions in which the phosphoric acid is not easily dissociated and the pH is 2 or less, the inhibition rate of phosphoric acid is substantially changed from that of nitric acid and acetic acid, and acid and phosphoric acid other than phosphoric acid such as nitric acid and acetic acid can be recovered, respectively. When the phosphoric acid concentration of the concentrate is too high, the membrane treatment cannot be performed due to the relationship of the impregnation pressure. Therefore, the upper limit of the phosphoric acid concentration of the concentrate is 15 weight percent (wt%)', preferably 10 wt%. When the concentrated phosphate containing the phosphoric acid concentration is circulated, the treated phosphoric acid-containing water is added to the concentrated concentrated liquid, and a part of the agricultural condensate is taken out as a scaly acid concentrate for one-time treatment. The above phosphoric acid concentration is maintained and the treatment is carried out efficiently. When the membrane treatment is carried out while circulating the concentrated liquid, the more the number of cycles of the concentrated liquid, the more the acid other than citric acid contacts the reverse osmosis membrane and the chance of permeating the membrane is 15 201002627 30925pif more can further reduce the acid other than phosphoric acid in the concentrate. concentration. At this time, if the acid concentration exceeds 15 Wt%, the membrane treatment cannot be performed. Therefore, the dilution liquid is added to the concentrate to be diluted, and then the reverse osmosis treatment is performed, thereby further reducing the concentration of the acid other than the phosphoric acid and recovering the acid. High purity phosphoric acid concentrate. As the dilution water, recovered water from which impurities are removed from the permeated water can be recycled. The permeated water of the reverse osmosis device taken out from the permeate chamber side contains an acid such as permeated phosphoric acid, nitric acid or acetic acid, and therefore can be recovered by removing the acid and other impurities from the permeated water of the reverse osmosis device by the impurity removing device. Pure water. In this case, the impurity removing device may be an ion exchange device, a biological treatment device or the like using an ion exchange resin. On the other hand, the phosphoric acid concentrate taken out from the concentrate chamber side has a large portion of the acid other than phosphoric acid such as nitric acid and acetic acid removed, but in order to further remove the above components to improve the purity and concentration of the recovered phosphoric acid solution, Purification is carried out by post treatment. Purification by post-treatment can be carried out by removing an acid other than phosphoric acid from the phosphoric acid concentrate by anion exchange. In this case, an anion exchange device is provided as a purification device, and the concentrate is introduced into the anion exchange resin layer, and strong acid ions such as nitric acid are removed from the concentrate to recover a high concentration scale containing almost no strong acid ions such as nitric acid. acid. When the reverse osmosis device has a configuration of two or more stages, the reverse osmosis device for supplying the acid-containing water to the first stage is adjusted to perform the membrane separation treatment, and the phosphoric acid concentrate of the first-stage reverse osmosis device is supplied to the second stage. The reverse osmosis device performs the membrane separation treatment after the second stage. In this case, the reverse osmosis 16 201002627 30925pif device has a first stage phosphoric acid concentrate supply unit, and the supply unit supplies the first stage phosphoric acid concentrate of the first stage reverse osmosis unit to the second stage reverse osmosis unit, and the circulation path is constituted. The method comprises the following steps: recycling the second-stage phosphoric acid concentrated liquid from the concentrated liquid chamber side of the first-stage reverse osmosis chamber to the phosphoric acid-containing water regulating portion; and the concentrated phosphoric acid liquid extracting portion is configured by: concentrating the second-stage phosphoric acid The remainder of the liquid is withdrawn from the concentrate chamber side of the second stage reverse osmosis unit. The second concentrated phosphoric acid concentrate which has been taken out is further subjected to evaporation concentration by an evaporation concentrating device, and can be recovered as a phosphoric acid concentrated liquid. It is also possible to circulate the evaporated concentrated white phosphoric acid concentrate to the phosphoric acid-containing water adjusting portion for use as the phosphoric acid for adjustment. In other words, when acetic acid remains in the phosphoric acid solution that has passed through the second-stage reverse osmosis device, the acetic acid cannot be completely removed by using an anion exchange resin. Therefore, in order to remove volatile components such as acetic acid, the purity and concentration of the recovered phosphoric acid solution are improved. Evaporation and concentration are carried out by an evaporating and concentrating device, and water and volatile components are removed in the same manner as the agricultural liquid, so that a still-concentrated can acid having almost no volatile component such as acetic acid can be recovered. The evaporation concentrating device can use a conventional device such as a rotary evaporator. ... The dish acid recovered by the above operation can be used as a recyclate, and can be transported in a high concentration liquid, and can be recovered as a high-purity concentrated phosphoric acid. In the present invention, although the reverse osmosis treatment is carried out under the condition of pH 2 or less, the treated phosphoric acid-containing water is usually obtained in an acidic state of pH 3 or less, so that the recovered Lin Chun is used as the pH. The conditioning agent can be easily adjusted. In addition, the method and apparatus for recovering phosphoric acid can be adjusted to a pH of less than or equal to 2, a phosphoric acid concentration of 6 〇〇mg/L or more, and a conductivity of 6 201002627 30925pif by a simple configuration and operation. Greater than or equal to 200mS/m. By adjusting the pH, the phosphoric acid concentration, and the conductivity by the above operation, the phosphoric acid concentrate is adjusted and supplied, and reverse osmosis treatment is performed to suppress the generation of microorganisms such as bacteria and yeast, and high-purity phosphoric acid can be recovered. This reduces the amount of drug used and the amount of waste generated, and reduces the cost of treatment. It can recover high-purity concentrated phosphoric acid and pure water that can be used as recyclables. In addition to the phosphoric acid-containing water, the recovered phosphoric acid can be impregnated with the reverse osmosis module taken out from the reverse osmosis device for microbial treatment such as fungi and yeast. Based on the above, according to the present invention, the reverse osmosis device is configured in such a manner that the phosphoric acid-containing water, particularly the phosphate-containing water to be removed, is adjusted to have a pH of 2 or less and a phosphoric acid concentration of 6 〇〇 mg or more in the reverse osmosis device. L, and the adjusted phosphoric acid-containing water having a conductivity of 2 〇〇 mS/m or more is subjected to hydrazine separation treatment, so that it is possible to inexpensively and efficiently use the phosphoric acid-containing water with a simple configuration and operation without using a special drug or the like. High-concentration transportable liquid recovery inhibits the production of microorganisms such as fungi and yeast, and is a high-purity phosphoric acid of recyclate. The above described features and advantages of the present invention will become more apparent from the description of the appended claims. [Embodiment] Hereinafter, embodiments of the present invention will be described with reference to the drawings. Figure i is a flow chart of the method and apparatus for receiving __ in the embodiment. i is the original water tank, storing raw water (treated with phosphoric acid water) 1 & 2 is a pretreatment device, which consists of an ion exchange device, an anion exchange device, and other impurity removal devices.
1S 201002627 30925pif 成，但較佳的是’按照至少設有陽離子交換 陽離子的方式構成。3為調整液槽，貯存調ί液(難t 酸水）3a°4為第1⑽（逆_裝置、5為第 分別藉由Rcm4a、5a劃分成透财室4b、5b:: 室4c、5c。6為後處理裝置，由離子交換 ^液 裝置、以及其他雜質除去裝置構成。^生物處理 發濃縮裝置，9為調整__，]〇心㈣醆/為蒸 Γ.': 水”a供、、.〇弟1 RO裝置4的濃縮液室 調整用顧槽9構成濃_岐取㈣ = L4上的泵P2、調整液槽3以及H 、循衣路在 整部。 计PH構成含磷酸水調 在上述磷酸回收裝置中，將進 藉由沉澱分離、過濾等除去了雜質 二二:離； 水)從管線L1導入原水槽1中。原纽，U从離子 離子4陽離子，但較佳的是，進一步 I屬 錯合物等的陰離子等雜質。前處理水：其：道有機酸 液槽3中。 < s線L3導入調整 作為原水的含磷酸水通常 態而得到，但在PH小於等於2 、3的酸性狀 時’將調整用雜液9a從調整用^ #逆滲透處理 循環至調整液槽3。此時，用PH 經循環路徑L4 的調整液3a的PH，控制設置於猶環路徑^=2内 19 201002627 30925pif 將調整液3a的pH調節至小於等於2。這種情況下’若使 濃縮磷酸液循環以調節至小於等於pH2,則調整液3a被調 整成磷酸濃度大於等於600 mg/L、且導電率大於等於 200mS/m。需要說明的是，在圖1中，雖然是利用pH計 來調整調整液3a的pH，但也可以使用比重計和導電率計 來調節磷酸濃度和導電率。 調整液槽3的含磷酸水經加壓泵P加壓，從管線L5 導入第1RO裝置4之濃縮液室4c中，利用RO膜4a進行 膜分離(逆滲透處理），使硝酸、醋酸等磷酸以外的酸和水 一同透過至透過液室4b側，在濃縮液室4c侧濃縮磷酸。 中和含磷酸水，在中性狀態下進行逆滲透處理時，硝酸、 醋酸等磷酸以外的酸的鹽和磷酸的鹽均不透過r〇膜4a， 而是在濃縮液室4c側被濃縮。相對於此，若不中和含磷酸 水，而是在pH小於等於2的條件下將其導入r〇裝置4 中進行RO處理，則磷酸被R〇膜4a阻止透過，在濃縮液 室4c側被濃縮，而硝酸、醋酸等磷酸以外的酸和水一同透 過至透過液室4b侧而被分離。 由於供給第1RO裝置4的調整含磷酸水被調節至小 於等於pH2、較佳的是小於等於pm 5、磷酸濃度大於等 於6〇〇 mg/L、較佳的是大於等於15〇〇 mg/L、且導電率大 於等於200 mS/m、較佳的是大於等於18〇〇 mS/m，因此藉 由將該調整含碌酸水供給第丨R〇裝置4以進行膜分離處 可抑制真菌、酵母等有害微生物在逆渗透膜的膜面上 ”殖。因此，即使不使用特別的藥物等，也不會發生由微 20 201002627 30925pif 的逆滲透膜的堵塞’不會出現膜間壓差的 ^升或透過水1的下降，逆滲透健可_錢轉。由於 有害微生物抑制效果將持續—定程度，所以可以間斷地供 給調整含魏水，但較麵是繼續供給鑛含填酸水。 透過至第1RO裝置4之透過液室扑側的透過液從管 線L6導入後處理裝置6中，利用離子交換裝置、生物處 理裳置、其他雜質除去裝置除去透過RO膜4a的硝酸、醋 酸等的陰離子錢其他轉，從管線L7排出。除去了上 述雜質的純水從管線L8回收到时水槽7中，貯存起來 作為回收水7a，從管線L9取出。 以一段式的RO裝置進行膜處理時，對經第1 R〇裝置 之/辰縮液至4c >辰縮的濃縮液進行後處理，可以得到回收填 酉文，但以兩段式的RO裴置進行膜處理時，將經第丨R〇 裝置之濃縮液室4c濃縮的濃縮液從管線L11導入第2 R〇 裝置5之濃縮液室5c中，利用膜5a進行膜分離(逆滲 透處理）’使醋酸等磷酸以外的酸和水一同透過至透過液室 5b側，在濃細液室5c側濃縮碟酸。藉此，碟酸的純度及 濃度已變高的濃縮液中的一部分從第2 R〇裝置5之濃縮 液室5c經管線L12導入調整用磷酸槽9中，貯存起來作 為調整用磷酸液9a。 第2 RO裝置5的濃縮液的剩餘部分從管線L1〇導入 蒸發濃縮裝置8中’進行蒸發濃縮。蒸發濃縮裝置8中產 生的含醋酸的冷凝水，從管線L14導入後處理裳置6中以 除去雜質’回收純水。以蒸發濃縮裝置8進行蒸發濃縮、 201002627 30925pif Φ t 濃縮水，縣線U5啊到回收鱗酸 ^理If"程中，可以進行除去俩以及其他雜質 ^處^回收磷酸槽10的回收嶙酸液伽還可以通過循環 路徑L4將其中的一部分循環至補敕 1刀倨衣主調整液槽3中，將剩餘部 刀作為回收魏從管線L16取出。透過第2 r〇裝置5之 RO膜5a到達透過液室5b侧的透過液，從管線1導入 後處理裝置6中以除去雜質，回收純水。 按照上述方法回收的回收磷酸液10&可作為回收物， ，且以高濃度的液狀被回收’所以實壯可以運輸，而且 可以作為高純度的濃縮磷酸進行回收。這種情況下，將調 整成pH小於等於2、磷酸濃度大於等於6〇() mg/L、且導 電率大於專於200 mS/m的調整含磷酸水供給R〇裝置，以 進行臈分離處理，藉此即使不使用特別的藥物等，也可以 抑制真菌、酵母等微生物的產生，以進行膜分離處理。藉 匕"T以減少藥物的使用量及廢棄物的生成量、降低處理 成本’可以回收高純度的濃縮磷酸及純水。 實施例 以下，對本發明之實施例進行說明。在各例中，除阻 止率以及特別指示外，％表示wt%。 〔實施例1〜6、比較例1〜4〕： 使用含有11000 mg/L的磷酸、1000 mg/L的硝酸、1000 mg/L的醋酸的導電率為1150 mS/m、pH1.3的標準含填酸 水’將其用純水稀釋以調節pH等，得到表1的原水(調整 含碟酸水）。需要說明的是，表丨中，比較例1是將標準含 22 201002627 30925pif 磷酸水用純水稀釋後用氫氧化鈉調節pH，從而調整成表1 所示的磷酸濃度及PH的原水。另外’實施例6是將原水 標準含磷酸水直接用作原水的例子。實施例1〜2則設計 成：在濃縮狀態下，使pH小於等於2、磷酸濃度大於等於 600 mg/L、導電率大於等於200 mS/m。 表1 pH 磷酸〔mg/L] 導電率〔mS/m〕 比較例1 5.5 100 40 比較例2 3.3 100 62 比較例3 2.8 | 150 66 比較例4 2.4 280 102 實施例1 2.1 330 126 實施例2 1.9 600 170 實施例3 1,7 1600 355 實施例4 L5 5000 612 實施例5 1.4 8500 795 實施例6 1.3 11000 1150 作為模擬圖1之逆滲透裝置的平膜試驗裝置，使用下 述裝置：利用燒結多孔板’將剪切成直徑為32mm(j)的圓形 的曰東電工(股)製逆滲透膜ES —20的平膜按有效膜徑29 ππηφ支樓、安裝在内徑為32 ιηπιφ的不銹鋼(SUS304)製小徑 平膜單元中，利用泵向單元的濃縮液室供給原水，與滯留 的濃縮液混合，利用背壓閥排出濃縮液，以調節濃縮液操 作壓力，在濃縮液室内用轉子攪拌，使濃縮液循環、均勻 23 201002627 30925pif 化的裝置。 以1 mL/分鐘的流量向上述平膜試驗裝置之 =表1的原水(調整含細水），用轉子麟單的供 與滯留的濃縮液混合，同時調節背翻，使=體， 等(G.5 mL/分鐘），進行膜分離。 =j 壓力作為操作壓力，如表2 玟耜作時的 不變，繼續進行膜分離。㈣不4 ’轉此操作壓力 圖2所示。另外，、運轉透過流束隨時間的變化如 後姓束運鏟Λ 時(比較例1是在通水20小時 ，束運轉’比較例2是在通水 Ζ 各例在通水6G小時後结 讀、、、。束運轉，其他 以及各成分的阻止率如表^轉各成分的濃度、 算出。利用式〔（1-透過水的濃度/濃縮水的濃度)χΐ〇〇〕 表2 比較例1 ----— 操作壓力 [MPa) 08 ---— — PH 卜〕 ~ 一 5 — 3 濃縮水; 磷酸 Cmg/L] 127 — ------— 1----- 阻止率 導電率 〔mS/m〕 磷酸 〔％〕 硝酸 [%) 醋酸 〔％〕 比較例2 丨一 0.8 60 >99.5 94 96.7 比較例3 比較例4 i施ST 〇 e 125 72 >99.5 89.5 90 4 0.8—'~ --—--- 0.8 2.5 255 112 >00 ^ 85.3 87.1 」·3— _1.9 475 180 一"—— >99.5 82 84 實施例2 --- 1.1 600 1100~~ 225 Γ>99.5 79 82 實施 333 >99.5 66 70 實施例4 1.7 1.7 2950 890 >99.5 48 55 實施例5 2.4 1.5 1.4 9300 15800 2850 4700 _^99.5 -0.5 1.2 實施例6 2 9 >99.5 -7.7 -5.1 1.3 20600 ——~—-1 一 6200 >99.5 •25 -20 24 201002627 30925pif 將實施例1、4以及比較例1〜3所得的濃縮水用培養 皿進行培養試驗。培養基為添加抗生素的pDA培養基， 30 C下在恒溫槽中培養。上述培養皿培養試驗的結果，在 中只色真囷產頁青徽囷（penicilUuln chrysogenum)形成 多/固菌落。另外，pH小於等於3時產生的真菌菌種為鐮刀 菌(fusariumspp.)。培養皿培養試驗的結果、即直至肉眼觀 察到真菌菌落的天數如表3所示。表3中，「大於等於1〇 天」表示在10天的培養試驗中沒有觀察到菌落。 表3 直至觀 察到菌落的天數「士] pH5 pH3 pH2.5 pH2 L pH1.5 1 3 7 大於等於10夭 大於等於10天 作為模擬圖1之逆滲透裝置的一段式R〇膜通水試藏 裝置’使用按照-部分農縮液循環的方式構 電 製超低壓芳香族聚醯胺型R0膜（容器為^ 〇 水淡水化用S2容器）的4英寸新品膜組件之濃縮液室和調 整液槽的裝置，將實關i錢4的原水(調整含填酸水） 以鹽水水量5 L/分鐘從調整液槽供給尺〇裝置之濃縮室， 進订膜分離，將-部分濃縮液循環至調整液槽，將另一部 分濃縮液及透過液循環至原水槽，處理i個月，使達到表 2的水質。處理1個月後的處理結果如表4所示。 25 201002627 30925pif 表4 原水的種類 操作 CMPal 實施例1 0.8 實施例4 1.7 碟酸阻止率 〔％〕 99.8 99.8 壓差 20 25 透過水量 迦〕 60 50 由表4可知：將實施例1以及4的原水處理⑽月後， 在處理性能上沒有確認到大的差別。但是，當研^處理! 泥(shme)的附著狀況時，在實 ， 槽的液面計的電極上掛有^絲狀 ίί泥原水處理中，1㈣後也未發現絲 由以υ可知.藉由在逆滲透裝置中對將不含離 子的含魏水調節成小於等於ρΗ2、_是小於等於 pHl.5、磷酸濃度大於等於_mg/L、特別是大於等於 mg/L、且導電率大於等於·㈣加、特別是大於等於職 mS/m的調整含碟酸水進行膜分離處理 藥，情況下，利用簡單的構成和操作，可 水中回收抑制額、酵母等微生物的產生、有用的 的磷酸。 又 綜上所述，本發明可應用於從含磷酸水回收磷酸以及 純水的方法雜置、制是適於從侧液晶基板和晶圓以 及其他電子設備後的洗滌廢水中回收磷酸等有價物質和作 為處理水的純水的回收磷酸的方法與裝置。 雖然本發明已以實施例揭露如上，然其並非用以限定 26 201002627 30925pif 本發明，任何所屬技術領域中具有通常知識者，在不脫離 本發明之精神和範圍内，當可作些許之更動與潤飾，故本 發明之保護範圍當視後附之申請專利範圍所界定者為準。 【圖式簡單說明】 圖1是實施方式中的磷酸回收方法及裝置的流裎圖。 圖2是顯不貫施例之結果的曲線圖。 【主要元件符號說明】 / 1 :原水槽 ' la:原水 2 :前處理裝置 3:調整液槽 3a :調整液 4 :第1RO裝置 4a、5a : RO 膜 4b、5b :透過液室 4c、5c :濃縮液室 U 5 :第2 RO裝置 6 :後處理裝置 7:回收水槽 7a :回收水 8:蒸發濃縮裝置 9:調整用磷酸槽 9a :調整用磷酸液 10 :回收磷酸槽 27 201002627 30925pif 10a :回收磷酸液 LI〜L6 :管線 P卜P2 :泵 pH : pH 計1S 201002627 30925pif is formed, but preferably is constructed in such a manner as to have at least a cation exchange cation. 3 is to adjust the liquid tank, store the liquid (difficult acid water) 3a ° 4 is the first (10) (reverse - device, 5 is divided into the translucent chamber 4b, 5b by Rcm4a, 5a:: chamber 4c, 5c 6 is a post-treatment device, which is composed of an ion exchange liquid device and other impurity removal devices. ^ Biological treatment and concentration device, 9 is adjustment __,] 〇心(四) 醆 / is steam Γ. ': water" a for ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, The water is adjusted in the phosphoric acid recovery device, and the impurities are removed by precipitation separation, filtration, etc., and the water is introduced into the raw water tank 1 from the line L1. The original U, U is from the ion ion 4 cation, but preferably Further, it is an impurity such as an anion such as a complex compound. Pretreatment water: It is in the organic acid solution tank 3. < s line L3 is introduced and adjusted as a raw water containing phosphoric acid water in the normal state, but in PH When the acidity is less than or equal to 2 or 3, 'the adjustment miscellaneous liquid 9a is circulated from the adjustment treatment ## reverse osmosis treatment to the adjustment liquid tank 3. At this time, the PH solution is used. The pH of the adjusting liquid 3a of the loop path L4 is controlled to be set in the loop of the Juxta ring ^=2. 19 201002627 30925pif The pH of the adjusting solution 3a is adjusted to be less than or equal to 2. In this case, 'If the concentrated phosphoric acid solution is circulated to be adjusted to be smaller than When the pH is equal to pH 2, the adjustment liquid 3a is adjusted to have a phosphoric acid concentration of 600 mg/L or more and a conductivity of 200 mS/m or more. In addition, in FIG. 1, the pH of the adjustment liquid 3a is adjusted by using a pH meter. However, the phosphoric acid concentration and the conductivity may be adjusted by using a hydrometer and a conductivity meter. The phosphoric acid-containing water in the adjustment tank 3 is pressurized by the pressurizing pump P, and introduced into the concentrated liquid chamber 4c of the first RO unit 4 from the line L5. The membrane separation (reverse osmosis treatment) is carried out by the RO membrane 4a, and an acid other than phosphoric acid such as nitric acid or acetic acid is passed through to the permeate chamber 4b side together with the water, and the phosphoric acid is concentrated on the concentrate chamber 4c side. When the reverse osmosis treatment is carried out in a neutral state, a salt of an acid other than phosphoric acid such as nitric acid or acetic acid and a salt of phosphoric acid are not permeated through the r 〇 film 4a, but are concentrated on the side of the concentrated liquid chamber 4c. Contains phosphoric acid water, but at a pH of 2 or less When it is introduced into the r〇 device 4 for RO treatment, the phosphoric acid is blocked by the R〇 film 4a, and concentrated on the concentrated liquid chamber 4c side, and acid other than phosphoric acid such as nitric acid or acetic acid is passed through to the permeate chamber. 4b is separated. The adjusted phosphoric acid-containing water supplied to the first RO device 4 is adjusted to be equal to or lower than pH 2, preferably pm 5 or less, and the phosphoric acid concentration is 6 〇〇 mg/L or more, preferably greater than or equal to 15 〇〇 mg / L, and the electrical conductivity is greater than or equal to 200 mS / m, preferably greater than or equal to 18 〇〇 mS / m, so by supplying the adjusted acid-containing water to the third R 〇 device 4 for film The separation site can inhibit the harmful microorganisms such as fungi and yeast from colonizing the membrane surface of the reverse osmosis membrane. Therefore, even if a special drug or the like is not used, the clogging of the reverse osmosis membrane by the micro 20 201002627 30925pif does not occur, and there is no drop in the pressure difference between the membranes or the decrease in the permeate water 1 . . Since the harmful microbial inhibition effect will continue to be determined, the Wei-containing water can be supplied intermittently, but the surface is continuously supplied with the ore-filled acid water. The permeated liquid that has passed through the permeate chamber of the first RO device 4 is introduced into the post-treatment device 6 from the line L6, and the nitric acid, acetic acid, or the like that has passed through the RO membrane 4a is removed by an ion exchange device, a biological treatment device, or another impurity removing device. The other turns of the anion money are discharged from the line L7. The pure water from which the above impurities are removed is recovered from the line L8 and stored in the water tank 7 as the recovered water 7a, and taken out from the line L9. When the membrane treatment is carried out by a one-stage RO apparatus, the concentrated liquid which has been subjected to the first R〇 device to the 4c > condensed solution is subjected to post-treatment, and the recovered filling text can be obtained, but the two-stage RO is obtained. When the membrane treatment is carried out, the concentrate concentrated by the concentrate chamber 4c of the second crucible device is introduced into the concentrate chamber 5c of the second R crucible device 5 from the line L11, and membrane separation is performed by the membrane 5a (reverse osmosis treatment). The acid other than phosphoric acid such as acetic acid is passed through to the side of the permeate chamber 5b together with water, and the acid is concentrated on the side of the concentrated liquid chamber 5c. As a result, a part of the concentrate having a high purity and concentration of the acid is introduced into the phosphoric acid tank 9 for adjustment from the concentrated liquid chamber 5c of the second R unit 5 via the line L12, and stored as the phosphoric acid solution 9a for adjustment. The remaining portion of the concentrate of the second RO device 5 is introduced into the evaporation concentration device 8 from the line L1 ’ 'evaporation and concentration. The condensed water containing acetic acid produced in the evaporation concentrating device 8 is introduced into the post-treatment skirt 6 from the line L14 to remove impurities, and the pure water is recovered. Evaporative concentration device 8 for evaporation and concentration, 201002627 30925pif Φ t concentrated water, county line U5 ah to recover sulphuric acid If" in the process, can remove two and other impurities ^ recovery of the recovery tank 10 recovery of citrate The gamma can also be circulated through the circulation path L4 to the 敕 1 knife 倨 main adjustment liquid tank 3, and the remaining knives are taken out as the recovery Wei from the line L16. The permeated liquid that has passed through the RO membrane 5a of the second r-device 5 reaches the permeate chamber 5b side, is introduced into the post-treatment apparatus 6 from the line 1 to remove impurities, and the pure water is recovered. The recovered phosphoric acid solution 10 & recovered as described above can be recovered as a recovered material and can be transported in a high-concentration liquid state. Therefore, it can be transported as a highly purified concentrated phosphoric acid. In this case, the adjusted phosphoric acid-containing R 〇 device is adjusted to have a pH of 2 or less, a phosphoric acid concentration of 6 〇 () mg/L or more, and a conductivity greater than 200 mS/m. Thereby, even if a special drug or the like is not used, the production of microorganisms such as fungi and yeast can be suppressed to perform membrane separation treatment. By using 匕"T to reduce the amount of drug used and the amount of waste generated, and to reduce the cost of treatment, it is possible to recover high-purity concentrated phosphoric acid and pure water. EXAMPLES Hereinafter, examples of the invention will be described. In each case, % means wt% except for the blocking rate and the special indication. [Examples 1 to 6 and Comparative Examples 1 to 4]: A conductivity of 1150 mS/m and a pH of 1.3 using a phosphoric acid containing 11,000 mg/L, 1000 mg/L of nitric acid, and 1000 mg/L of acetic acid. The acid-containing water was diluted with pure water to adjust the pH and the like, and the raw water of Table 1 (adjusted with disc acid water) was obtained. In the surface, Comparative Example 1 is a raw water obtained by diluting the standard containing 22 201002627 30925pif phosphoric acid water with pure water and adjusting the pH with sodium hydroxide to adjust the phosphoric acid concentration and pH shown in Table 1. Further, Example 6 is an example in which raw water standard phosphoric acid-containing water is directly used as raw water. Examples 1 to 2 were designed such that, under concentration, the pH was less than or equal to 2, the phosphoric acid concentration was 600 mg/L or more, and the conductivity was 200 mS/m or more. Table 1 pH phosphoric acid [mg/L] Conductivity [mS/m] Comparative Example 1 5.5 100 40 Comparative Example 2 3.3 100 62 Comparative Example 3 2.8 | 150 66 Comparative Example 4 2.4 280 102 Example 1 2.1 330 126 Example 2 1.9 600 170 Example 3 1,7 1600 355 Example 4 L5 5000 612 Example 5 1.4 8500 795 Example 6 1.3 11000 1150 As a flat membrane test apparatus simulating the reverse osmosis apparatus of Fig. 1, the following apparatus was used: sintering The perforated plate 'will be cut into a 32-mm (j) circular 曰东电工(股) reverse osmosis membrane ES-20 flat membrane according to the effective membrane diameter 29 ππηφ branch, installed in the inner diameter of 32 ηηπιφ In a small-diameter flat membrane unit made of stainless steel (SUS304), raw water is supplied to the concentrated liquid chamber of the unit by a pump, mixed with the retained concentrated liquid, and the concentrated liquid is discharged by a back pressure valve to adjust the operating pressure of the concentrated liquid, and is used in the concentrated liquid chamber. The rotor is agitated to circulate the concentrate, evenly 23 201002627 30925pif device. At a flow rate of 1 mL/min, the raw water of the above-mentioned flat membrane test apparatus = Table 1 (adjusted with fine water), mixed with the retained concentrate of the rotor lining, and adjusted for back-turning, so that the body, etc. G. 5 mL/min), membrane separation. =j Pressure is used as the operating pressure, as shown in Table 2, and the membrane separation is continued. (D) No 4 </ turn this operation pressure shown in Figure 2. In addition, the running through the stream changes with time, such as the last surname shovel (comparative example 1 is in the water for 20 hours, the beam is running 'comparison example 2 is in the water rafts, each case is 6G after the water is passed The reading, the, and the beam operation, and the other groups and the blocking rate of each component are calculated by the concentration of each component, and the calculation formula is used. [Using the concentration of the permeated water/concentration of the concentrated water] 表 Table 2 Comparative Example 1 ----- Operating pressure [MPa) 08 ---- — PH 卜] ~ 1-5 — 3 concentrated water; phosphoric acid Cmg / L] 127 — ------ 1- 1----- blocking rate Conductivity [mS/m] Phosphoric acid [%] Nitric acid [%) Acetic acid [%] Comparative Example 2 丨-0.8 60 > 99.5 94 96.7 Comparative Example 3 Comparative Example 4 i Shi ST 〇e 125 72 > 99.5 89.5 90 4 0.8—'~ ------ 0.8 2.5 255 112 >00 ^ 85.3 87.1 ”·3— _1.9 475 180 A "—— >99.5 82 84 Example 2 --- 1.1 600 1100~~ 225 Γ>99.5 79 82 Implementation 333 >99.5 66 70 Example 4 1.7 1.7 2950 890 > 99.5 48 55 Example 5 2.4 1.5 1.4 9300 15800 2850 4700 _^99.5 -0.5 1.2 Example 6 2 9 >99.5 - 7.7 -5.1 1.3 2060 0 ——~—-1 A 6200 > 99.5 • 25 -20 24 201002627 30925pif The concentrated water obtained in Examples 1 and 4 and Comparative Examples 1 to 3 was subjected to a culture test using a culture dish. The medium was pDA medium supplemented with antibiotics, and cultured in a thermostat at 30 C. As a result of the culture dish culture test described above, multi/solid colonies were formed in the penicil Uuln chrysogenum. Further, the fungal species produced when the pH is 3 or less is Fusariumspp. The results of the culture dish culture test, i.e., the number of days until the fungal colonies were observed by the naked eye, are shown in Table 3. In Table 3, "greater than or equal to 1 day" means that no colonies were observed in the 10-day culture test. Table 3 The number of days until the colony was observed "Shen" pH5 pH3 pH2.5 pH2 L pH1.5 1 3 7 Greater than or equal to 10 夭 greater than or equal to 10 days as a one-stage R 〇 membrane water test of the reverse osmosis device of Figure 1. The apparatus 'constructs a concentrated liquid chamber and a regulating solution of a 4-inch new membrane module of an ultra-low pressure aromatic polyamine type R0 membrane (container is a S2 container for water purification) according to the circulation of a part of the agricultural shrinkage liquid. In the tank device, the raw water of the real money (adjusted with acid-filled water) will be supplied to the concentrating chamber of the scale device from the adjusting liquid tank with a saline water amount of 5 L/min, and the film will be separated and the partial concentrate will be recycled to Adjust the tank and circulate another part of the concentrate and permeate to the original water tank for 1 month to reach the water quality of Table 2. The treatment results after 1 month of treatment are shown in Table 4. 25 201002627 30925pif Table 4 Raw water Type Operation CMPal Example 1 0.8 Example 4 1.7 Disc Acid Blocking Rate [%] 99.8 99.8 Pressure Difference 20 25 Permeate Water Volume] 60 50 It can be seen from Table 4 that the raw water treatments of Examples 1 and 4 are treated after 10 months. There is no big difference in performance. Yes, when the grinding process is done! When the mud (shme) is attached, the electrode of the liquid level meter of the tank is hung in the form of silky water. After 1 (four), the silk is not found. By adjusting the Wei-containing water containing no ions to ρΗ2, _ is less than or equal to pH 1.5, phosphoric acid concentration is greater than or equal to _mg/L, especially greater than or equal to mg/L, and the conductivity is greater than that in the reverse osmosis device. It is equal to (4) plus, especially, the adjustment of the mS/m is equal to or equal to the mS/m, and the membrane-dissolving treatment is carried out, and in the case of the membrane separation treatment, it is possible to recover the amount of microorganisms such as yeast and the like in the water by a simple configuration and operation. Further, the present invention can be applied to a method of recovering phosphoric acid and pure water from a phosphoric acid-containing water, and is suitable for recovering phosphoric acid from washing wastewater after side liquid crystal substrates and wafers and other electronic equipment. Method and apparatus for recovering phosphoric acid from valuable materials and as pure water for treating water. Although the invention has been disclosed above by way of example, it is not intended to limit the invention of the invention, which is generally known in the art. The scope of protection of the present invention is defined by the scope of the appended patent application, without departing from the spirit and scope of the invention. It is a flow chart of the phosphoric acid recovery method and apparatus in the embodiment. Fig. 2 is a graph showing the result of the inconsistency of the example. [Explanation of main component symbols] / 1 : Original water tank 'la: Raw water 2: Pretreatment device 3 : Adjustment liquid tank 3a: Adjustment liquid 4: First RO unit 4a, 5a: RO membranes 4b, 5b: Permeate liquid chambers 4c, 5c: Concentrated liquid chamber U5: Second RO device 6: Aftertreatment device 7: Recovery water tank 7a :Recovered water 8 : Evaporation and concentration device 9 : Phosphoric acid tank 9a for adjustment: Phosphoric acid solution for adjustment 10 : Recovery of phosphoric acid tank 27 201002627 30925pif 10a : Recovery of phosphoric acid liquid LI to L6 : Pipeline P Bu P2 : Pump pH : pH meter