201238912 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種分離方法及分離裝置。 【先前技術】 自先前以來，作為㈣液，已知有包含氮氟酸與氣化鍵 者。又’自此種飯刻液且供用於餘刻之後之钱刻廢液中回 收氫氟酸（氟）的技術亦廣為人知（例如參照 於專利文獻it，記載有藉由使碳酸㈣包含氫敗酸與 敦化錄之㈣液中進行反應，而將氟^二氧切之含有 率較少之高純度1化弼並進行回收，&而由所回收之氣化 弼再次製造蝕刻液用之氫氟酸的方法。 然而’於此種方法中’無法自_液中直接分離、回收 氫I酸1 ’於製絲化詞並進行回收之後，需要 化舞製成氫說酸之製程’而無法進行有效之回收。又，由 触刻廢液直至製造新的触刻液(氣氣酸)中之製程較多，於 其中途大量地產生二次廢液。因此，亦有環境保護性較差 之問題。X’由㈣程較多，故而亦有裝置構成大型化、 複雜化之問題。 [先前技術文獻] [專利文獻] [專利文獻1]曰本專利特開 【發明内容】 [發明所欲解決之問題] 本發明之目的在於提供— 平5-170435號公報 種可自至少包含氫氟酸 、氟化 160736.doc 201238912 氫敍、U㈣及水之混切中，簡單地分離高 氟酸與氟化氫銨的分離方法及分離裝置。 mi [解決問題之技術手段] 可藉 本發明係為了解決上述課題之至少— 乂 分而成者’ 由以下之形態或應用例之形式而實現。 [應用例1] 至少包含氫氟酸、 分別分離上述氫氟 氟化氫銨、氟 酸與上述氟化 本發明之分離方法係 矽酸銨及水之混合酸中 氫録者， 其特徵在於：其包括如下步驟： 藉由蒸趨上述混合酸’而回收作為顧出液之包含上述氫 氟酸及水之第1液體’細收作為殘留產物之包含上述敦 化氫錄及上述W酸铵之第2液體的&蒸館步驟； 藉由蒸餾上述第!液體’而自上述第i液體中主要將上述 水加以分離1而回收作為殘留產物之上述氫氧酸之濃度 高於上述第1液體之第3液體的第2蒸餾步驟； 自上述第2液體中使包含上述氟化氫銨及上述氟矽酸銨 之第1固體結晶之結晶步驟； 使上述第1固體溶解於包含氨與水性溶劑之液體令並析 出沈澱物，而獲得包含上述沈澱物之第3液體之析出步 驟；及 自上述第3液體中去除上述沈澱物、過剩之氨及水，而 獲得包含上述氟化氫錄之固形物之固體回收步驟。 藉此，可自混合酸中分別以相對較高之濃度及純度，簡 160736.doc 201238912 單地分離、回收高純度之氫氟酸與氟化氫銨。 [應用例2] 於本發明之分離方法中，較佳為於上述析出步驟中，以 上述氨相對於上述氟化氫銨及上述氟矽酸銨之化學當量比 成為1.0至3.0之範圍的方式，使上述氨進行反應。 藉此，可更多地析出主要包含二氧化矽之沈澱物。因 此’可提高氟化氫敍之純度。 [應用例3] 於本發明之分離方法中，較佳為對液溫進行調整以使上 述第3液體成為室溫。 藉此，可於第3液體之液體中析出更多之沈澱物。因 此’可提高所獲得之氟化氫銨之純度。 [應用例4] 於本發明之分離方法中’較佳為於上述析出步驟中，利 用準備使上述氨溶解於上述水性溶劑中之液體並使上述 第1固體溶解於該液體中；或準備使上述第丨固體溶解於上 述水性溶劑中之液體，並使氣體之上述氨與該液體接觸而 溶解中之至少一種方法而進行。 藉此’可有效地使氣化氫錢及氟料錢與氨接觸而進行 反應。尤其是導人氨氣之方法可不增加水分，而僅增 之化學當量比。 曰 [應用例5] 於本發明之分離方法中，較佳為上述第2蒸館步驟中之 上述第i液體之加熱溫度為低於上述&蒸鶴步驟中的上述 160736.doc 201238912 混合酸之加熱溫度之設定溫度。 藉此’於自第1液體中去除水分之情形時，可減少混入 至經去除之餾出液中而與水分一併去除之氫氟酸的量。因 此’可提高氫敗酸之產率。 [應用例6] 於本發明之分離方法中，較佳為上述混合酸係藉由對包 含石夕之材料進行姓刻處理而產生之飯刻廢液。 藉此，可再利用蝕刻廢液，並可實現蝕刻處理之低成本 化。又，由於可減少廢棄之廢液之量，故而於環境方面較 優異。 [應用例7] 本發明之分離裝置之特徵在於：其包含本發明之分離方 法。 藉此，可提供一種自混合酸中，分離、回收高濃度且高 純度之氫氟酸與氟化氫錄卡之至少任一者的裝置。 【實施方式】 以下，基於隨附圖式所示之較佳實施形態，詳細地說明 本發明之分離方法及分離裝置。 圖1係本發明之較佳實施形態之分離裝置的概略圖，圖2 係用以說明本發明之較佳實施形態之分離方法的概略圖， 圖3〜圖5係用以說明實施例之表及測定圖。 1·分離裝置 首先’對分離裝置1之構成進行說明。 圖1所示之分離裝置1例示有蒸餾裝置，以自各個步驟之 160736.doc 201238912 热顧裝置中獲得之館出液提取至201238912 VI. Description of the Invention: [Technical Field to Which the Invention Is Ascribed] The present invention relates to a separation method and a separation device. [Prior Art] Since the prior art, as the (iv) liquid, those containing nitrogen oxyfluoride and gasification bonds have been known. Further, a technique for recovering hydrofluoric acid (fluorine) from such a meal liquid and for use in the waste liquid after the remaining time is also widely known (for example, referring to the patent document it, it is described that the carbonic acid (4) contains hydrogen sulphuric acid. The reaction is carried out in the liquid (4) of Dunhua, and the high-purity ruthenium having a low fluorine content is recovered and recovered, and the hydrogen fluoride for the etching liquid is re-manufactured from the recovered gasified ruthenium. The method of acid. However, in this method, it is impossible to directly separate and recover hydrogen I acid 1 ' from the liquid, and after the silking word is recovered and recovered, it is necessary to make a process of making hydrogen into acid. Effective recycling. In addition, there are many processes in the process of producing a new contact liquid (gas-gas acid), and a large amount of secondary waste liquid is generated in the middle. Therefore, there is also a problem of poor environmental protection. The number of X's is more than (4), so there is also a problem that the device is large and complicated. [Prior Art Document] [Patent Document] [Patent Document 1] This patent is open to the public [Invention] [The invention is intended to solve Problem] The object of the present invention is to provide - Ping 5-170435 The method can simply separate the separation method and separation device of high-fluoric acid and ammonium hydrogen fluoride from at least hydrofluoric acid, fluorination 160736.doc 201238912 hydrogen, U (four) and water mixed cutting. mi [Technical means to solve the problem The present invention can be achieved by the following forms or application examples in order to solve at least the above problems. [Application Example 1] At least hydrofluoric acid is contained, and the above-mentioned ammonium hydrogen fluoride fluoride is separately separated. Fluoric acid and the above-mentioned fluorination The separation method of the present invention is a hydrogen-catalyzed mixed acid of ammonium citrate and water, which is characterized in that it comprises the following steps: recovery by the evaporation of the mixed acid' as the inclusion of the drug The first liquid of the hydrofluoric acid and the water is finely collected as a residual product, and the second liquid containing the above-mentioned Dunhua hydrogen recording and the above-mentioned W acid ammonium salt; and the vaporization step of the second liquid by distillation; In the liquid i, the water is mainly separated by 1 to recover a second distillation step in which the concentration of the hydroxy acid as a residual product is higher than the third liquid of the first liquid; and the second liquid is contained in the second liquid. a crystallization step of the first solid crystal of ammonium hydrogen fluoride and the above ammonium fluoroantimonate; a step of precipitating the third solid by dissolving the first solid in a liquid containing ammonia and an aqueous solvent and depositing a precipitate to obtain a precipitate containing the precipitate And removing the precipitate, excess ammonia and water from the third liquid to obtain a solid recovery step comprising the solid matter recorded by the hydrogen fluoride. Thereby, the relatively high concentration and purity can be separately obtained from the mixed acid. , s. 160736.doc 201238912 Separate and recover high-purity hydrofluoric acid and ammonium hydrogen fluoride. [Application Example 2] In the separation method of the present invention, preferably, in the above-mentioned precipitation step, the ammonia is relative to the hydrogen fluoride. The ammonia is reacted in such a manner that the stoichiometric ratio of ammonium and the above ammonium fluoroantimonate is in the range of 1.0 to 3.0. Thereby, a precipitate mainly containing cerium oxide can be precipitated more. Therefore, the purity of hydrogen fluoride can be improved. [Application Example 3] In the separation method of the present invention, it is preferred to adjust the liquid temperature so that the third liquid becomes room temperature. Thereby, more precipitate can be deposited in the liquid of the third liquid. Therefore, the purity of the obtained ammonium hydrogen fluoride can be improved. [Application Example 4] In the separation method of the present invention, it is preferred that in the above-described precipitation step, a liquid in which the ammonia is dissolved in the aqueous solvent is prepared and the first solid is dissolved in the liquid; or The second solid is dissolved in the liquid in the aqueous solvent, and at least one of the ammonia of the gas is brought into contact with the liquid to be dissolved. Thereby, it is possible to effectively react the vaporized hydrogen money and the fluorine material with ammonia. In particular, the method of introducing ammonia can increase the chemical equivalent ratio without increasing the moisture.应用 [Application Example 5] In the separation method of the present invention, preferably, the heating temperature of the ith liquid in the second steaming step is lower than the above-mentioned 160736.doc 201238912 mixed acid in the steaming step The set temperature of the heating temperature. By this, when the water is removed from the first liquid, the amount of hydrofluoric acid which is mixed into the removed distillate and removed together with the water can be reduced. Therefore, the yield of hydrogen sulphuric acid can be increased. [Application Example 6] In the separation method of the present invention, it is preferred that the mixed acid is a rice waste liquid produced by subjecting a material containing a stone to a surname. Thereby, the etching waste liquid can be reused, and the etching process can be reduced in cost. Further, since the amount of waste liquid to be discarded can be reduced, it is excellent in terms of environment. [Application Example 7] The separation device of the present invention is characterized in that it comprises the separation method of the present invention. Thereby, it is possible to provide a device for separating and recovering at least one of a high concentration and high purity hydrofluoric acid and a hydrogen fluoride recording card from a mixed acid. [Embodiment] Hereinafter, a separation method and a separation apparatus of the present invention will be described in detail based on preferred embodiments shown in the accompanying drawings. 1 is a schematic view of a separating apparatus according to a preferred embodiment of the present invention, and FIG. 2 is a schematic view for explaining a separating method of a preferred embodiment of the present invention, and FIGS. 3 to 5 are diagrams for explaining the embodiment. And measurement chart. 1. Separation device First, the configuration of the separation device 1 will be described. The separation device 1 shown in Fig. 1 is exemplified by a distillation apparatus for extracting the liquid obtained from the library obtained from the 160736.doc 201238912 thermal device of each step.
:排列複數 操作以線内方式進行分離。 狀敌取至回收容器300中，或自蒸 並將該等餾出液及殘留產物移至 的供給部中之分批式分離方法作為—例 ，亦可構成如下之分離方法：排列複數 於裝置間以輸液管進行連接，並藉由閥: Arrange multiple operations to separate inline. The batch separation method in which the enemy is taken into the recovery container 300 or from the supply portion to which the distillate and the residual product are transferred is also taken as an example, and the separation method may be configured as follows: Connected with an infusion tube and with a valve
[(NH4)HF2]、氟石夕酸錄[(NH4)2SiF6]及水之混合酸剛 :’分別以高純度且相對較高之濃度分離、回收氫氟酸與 氟化氫銨之裝置（蒸餾裝置）。除該蒸餾裝置以外，亦可將 化學藥品彼此混合，或使用過濾沈澱物之裝置，但省略圖 混合酸100例如為蝕刻廢液。具體而言，例如為利用包 a氫氟酸及氟化氫錢之飯刻液，對包含砂之構件進行姓刻 處理後之廢液。作為該包含矽之構件，例如可列舉各種玻 璃或水晶等。 於此種混合酸1 00中，於蝕刻處理中未反應之氫氟酸及 氟化氫錄殘留有相當量之各自之成分。因此，可藉由分別 回收該等，而再次用作蝕刻液之成分。 如此’可藉由自蝕刻廢液中分離未反應之蝕刻成分，而 實現#刻廢液之再利用，並可實現蝕刻處理之低成本化。 又’因經廢棄處理之蝕刻廢液之量減少，故而亦可發揮優 異之環境保護性。 混合酸100中之分離前之氫氟酸的濃度並無特別限定， 160736.doc 201238912 例如為1〇〜20痛左右。又，混合酸1〇〇中之分離前之氣化 氫銨的濃度並無特別限定，例如為25〜35 wt%左右。又， 混合酸100中之分離前之矽的漢度並無特別限定，例如為 0.1 〜1.0 wt%左右。 此處，混合酸100中之氫氟酸、氟化氫銨、矽之濃度可 以如下之方式求出。 (矽之濃度測定） 使用 ICP 發光分析裝置（Inductive CQupled piasma SPeCtr〇meter，電感耦合電漿光譜儀）(例如，島津製作所股 份有限公司製造，製品名「ICPs_751〇」），進行混合酸 1〇〇中所含之金属元素之定性及定量分析。藉此，由於混 合酸100中之金屬原子僅為矽，故而藉此可求出混合酸1〇〇 中之矽之濃度A(mol/l)。 (氟化氫銨之濃度測定） 使用紫外可見分光光度計（例如，島津製作所股份有限 公司製造’製品名「IUV-1240」），實施靛酚藍 (indophenol blue)吸光光度法，藉此，可求出混合酸1〇〇中 之氟化氫敍及氟矽酸錢所具有之（NH4+)的合計濃产 B(m〇l/l)。如上所述，因混合酸1〇〇中之矽係以氟矽酸銨之 形式而存在，故而可藉由自合計濃度B中減去氟矽酸銨所 具有之（ΝΗβ)濃度2A，而求出混合酸1〇〇中之氟化氫銨之 濃度 C(mol/l)。即 C=B-2A。 (氫氟酸之濃度測定） 使用電位差自動滴定裝置（例如’京都電子工業股份有 160736.doc 201238912 限公司製造，製品名「AT·5 1 〇」），測定混合酸1 〇〇之酸濃 度。具體而言，藉由利用〇.1 mol/dm3之氫氧化鈉水溶液進 行中和滴定，而測定混合酸100之酸濃度。藉此，可求出 混合酸100中之氛氟酸、氟化氫錄及氟碎酸敍所具有之人 計酸漠度D。因於上文中，已知混合酸1〇〇中之氣梦酸錢濃 度A及氣化氣敍?農度B ’故而可藉由自合計酸濃度D中減去 氟矽酸銨所具有之酸濃度4A、氟化氫銨所具有之酸濃度 B，而求出混合酸100中之氫氟酸濃度E(m〇i/i)。即e=d_ 4A-B 〇 以上，對混合酸100中之氫氟酸、氟化氫銨、矽之濃度 之測定方法的一例進行說明。 如圖1所示’本實施形態之分離裝置1含有：蒸餾罐（蒸 餾容器）11、對蒸餾罐11供給混合酸100之供給部丨2、加熱 燕顧罐11之加熱部13、攪拌蒸餾罐丨丨内之混合酸1〇〇之搜 拌機構14、冷卻由蒸餾罐丨丨所產生之蒸氣而獲得餾出液 200之冷卻部15、回收餾出液2〇〇之回收部“、及排氣處理 機構17。 於構成分離裝置1之各部分中，可與混合酸丨〇〇接觸者分 別具有耐酸性。於本實施形態中，藉由以聚四氟乙烯 (PTFE，Polytetrafluoroethene)構成可與混合酸丨〇〇接觸之 部位而賦予耐酸性。 再者，作為賦予耐酸性之方&，並不限定於&，例如亦 可為以氣乙烯樹脂、丙烯酸樹脂等耐酸性塑膠構成可與混 合酸10 0接觸之部位夕古 丨位之方法，或以於利用金屬材料構成之 160736.doc 201238912 本體之表面上塗佈氟系樹脂者構成可與混合酸1〇〇接觸之 位的方法。因該等金屬與耐酸性樹脂之混合材料的熱導 性較佳，故而可於短時間内藉由自外部加溫、冷卻而進行 液溫調整，因此較合適。 (供給部12) 於供給部12中蓄積有混合酸1〇〇。此種供給部12係設置 於蒸餾罐11之上方《於連通供給部12與蒸餾罐^之流路之 中途設置有旋塞181，可藉由對該旋塞181進行操作，而將 蓄積於供給部12中之混合酸100供給至蒸餾罐丨丨，或相反 地停止該供給。 (蒸餾罐11) 蒸餾罐11係用以蒸餾混合酸100之槽。於此種蒸餾罐^ 中，形成有將所產生之蒸氣誘導至冷卻部15之誘導管路 π 1。又，於蒸餾罐i丨内設置有測量混合酸i 之溫度之溫 度計191、及測量於誘導管路i i i内流動之蒸氣之溫度的溫 度計192。 (加熱部13) 加熱部13具有經由蒸餾罐丨丨而加熱混合酸1 〇〇之功能。 作為加熱部13，例如，如本實施形態所示，可包括以包覆 蒸餾罐11之下側部分之方式設置的加熱套。此種加熱部 可以基於溫度計191、192之感測結果，而使混合酸1〇〇及 蒸氣之溫度成為特定溫度之方式而控制其驅動。 再者’作為加熱部丨3，只要可加熱混合酸1〇〇，則並不 限定於上述構成。 160736.doc 201238912 (攪拌機構14) 分離裝置1較佳為含有攪拌機構i 4。 授拌機構14具有攪拌蒸餾罐11内之混合酸1 〇〇之功能。 °丁藉由一面利用攪拌機構14攪拌混合酸1〇〇，一面進行蒸 餾，而於混合酸1 00内促進物質移動，並抑制固體（固形物） 之結晶等。尤其可抑制於液面或容器之内壁之附近的因濃 度之定域而引起之結晶等。 此種攪拌機構14構成為含有配置於蒸餾罐1丨内之攪拌棒 (Stir bar)141、載置有蒸餾罐U及加熱部13之熱攪拌器（攪 拌裝置）142，並利用熱攪拌器142使攪拌棒141旋轉，而攪 拌混合酸1 〇〇。 再者，亦可使用不具有加熱機構之攪拌器，代替具備加 熱機構之熱攪拌器142。又，即便不具備攪拌器，亦可以 利用於容器之壁面上施加振動等物理方法，使蒸餾罐"内 之液體流動之方式進行擾拌。 (冷卻部15) 冷卻部1 5具有冷卻因加熱混合酸丨〇〇而產生之蒸氣，而 獲得餾出液200之功能。作為此種冷卻部丨5，可使用通常 已知之冷卻管。即，冷卻部15構成為含有内管151、外管 152，蒸氣於内管151内流動，且冷卻水於内管151與外管 152之間流動。藉此’利用冷卻水使於内管15丨内流動之蒸 氣冷卻而液化，從而獲得餾出液200。 再者’只要可獲得餾出液200,則内管151之長度或冷卻 水之溫度等並無特別限定。 160736.doc 201238912 (回收部〗6) 回收部16係與冷卻部15連結’具有回收館出液之功 能。於此種回收部16之底部設置有旋塞182，可藉由對該 旋塞進行操作’而將積存於时部16中之㈣液細排 出至分離裝置1之外部（例如，如圖1所示之回收容器 (排氣處理機構17) 排氣處理機構（氣體清洗部）17具有對未由冷卻部Η而液 化之排氣進行中和處理之功能。此種排氣處理機構Η含有 儲存水或驗性清洗液彻之容器，並藉由在清洗液彻内誘 導排氣而進行排氣之中和處理。 以上，對分離裝置1之構成進行說明。 2.氫氟酸之分離方法 繼而’對自混合酸100中分離、回收氫敦酸之方法（本發 明之分離方法）進行說明。 將概略圖示於圖2之本發明之分離方法包括：第五蒸傲步 驟、及第2蒸餾步驟。以下所說明之分離方法係於第}蒸餾 步驟中自混合酸⑽中提取餘出液綱後，於第❻顧步驟 中自該顧出液200中提取殘留產物_者。亦可為以於& 蒸館步驟結束後’實施第2蒸館步驟之分批方式進行處理 之方法’及將於第1蒸顧步驟與第2蒸顧步驟中分別使用之 蒸顧装置排列設置’將該等之間以輸液管連接，並藉由閥 钿作及泵操作等進行處理之線内方式中之任一種方式。 (第1蒸顧步驟） 例如，自供給部12對蒸餾罐11供給混合酸100 ’並利用 160736.doc -12- 201238912 加熱部13將混合酸100加埶 …至特疋溫度，藉此於大氣壓下 f真傑混合酸1 00。此時，亦可^丨m , 亦可利用攪拌機構14攪拌蒸餾罐 11内之混合酸1 〇 〇。作爲，’日人 料叱合酸10〇之加熱溫度(上述特定 溫度），並無特別限定，例如為120〜14(rc左右。 藉此，自混合酸⑽中主要將水與氫氟酸蒸發， 氣分別經由誘導管路111而到達冷卻部15。利用冷卻部^ 冷卻到達冷卻部15之蒸氣，而成為館出液（第i液體）200, 並回收至回收部16卜回收至回收部16之館出液200係以 水與虱氟酸作為主成分之濃度相對較低的I化氫 酸水溶液）。 机 此處’作為館出液200之氫氟酸濃度，並無特別限定， 於將混合酸100之氫氟酸濃度設為A(wt%)時，較佳為 0.75A〜l.lA(wt%)左右。 又’作為餾出液200而回收之氫氟酸之產率(%)，即“餾 出液200中所含之氫氟酸之量/混合酸1〇〇中所含之氣說酸 之幻X刚}較佳為55。/。以上左右。藉此，可使作為館出液 200而回收之氫氟酸之量充分。 又’顧出液200之顧出量（％)，即{(销出液200之重量/混 合酸⑽之重量)><100}並無特別限定，較佳為55〜7〇%左 右。藉此，可確保裝置之安全性，且可獲得充分量 液 200。 可藉由充分地實施此種第以館步驟，而自混合酸ι〇〇中 分離水與氫氟酸。 (第2蒸餾步驟） 160736.doc •13- 201238912 於結束上述第1蒸餾步驟後，將存在於蒸餾罐11中之殘 留產第2液體)500自蒸餾罐"中排出並移至未圖示之 回收容器巾。再者，該殘留產物5〇〇係以如下所述之 供給至其他處理。 繼而，於空蒸餾裝置1中，自供給部12對蒸餾罐1丨供給 上述餾出液200，並利用加熱部丨3將餾出液2〇〇加熱至特定 溫度，藉此於大氣壓下蒸餾餾出液200。此時，亦可利用 撥拌機構14搅拌蒸顧罐u内之館出液2〇〇。作為顧出液_ 之加熱溫度（上述特定溫度），並無特別限定，例如為 100〜12(TC左右。 藉此，自餾出液200中使水與少量之氫氟酸蒸發，其蒸 氣經由誘導管路丨丨1而到達冷卻部丨5。到達冷卻部丨5之蒸 氣由冷卻部15冷卻，而於回收部16中回收濃度相對較低之 氟化氫酸。 可藉由充分地實施此種第2蒸館步驟，而自德出液2〇〇中 分離多於氫氟酸之水。即，可濃縮餾出液2〇〇，且於結束 第2蒸飽步驟後’殘留於蒸顧罐1丨内之殘留產物（第3液 體）600成為氫氟酸濃度高於餾出液2〇〇之氟化氫酸（氫氟酸 水溶液）。 尤其可藉由將第2蒸餾步驟中之餾出液200之加熱溫度設 定為低於第1蒸餾步驟中的混合酸1 〇〇之加熱溫度，而於自 館出液2 0 0中去除水分時，減少混入至經去除之鶴出液中 而與水分一併去除之氫氟酸的量。因此，可提高氫氟酸之 產率。 160736.doc .14· 201238912 此處’作為殘留產物600之氫氟酸漢度，並無特別限 定，於將混合酸100之氫氟酸濃度設為A(wt%)時，較佳為 2.0A〜3.0A(wt%)左右。 又，作為殘留產物600而回收之氫氟酸之產率㈧卜即 {(殘留產物600中所含之氫氟酸之量/混合酸丨〇〇中所含之氫 氟酸之量）xl00}較佳為3〇%以上左右β藉此，可使作為殘 留產物600而回收之氳氟酸之量充分。 以如此方式而獲得之殘留產物6〇〇(氟化氫酸）可再次用 作蝕刻液。於用作蝕刻液之時’例如，亦可與新的蝕刻液 混合使用。又’亦可將殘留產物6〇〇用於用以調節新的蝕 刻液之氫氟酸濃度的用途中。 以上，對自混合酸1〇〇中分離氫氟酸之方法進行說明。 根據此種方法，可簡單且有效地自混合酸中分離、回收 濃度相對較高之高純度之氫氟酸。又，因可藉由將自钮刻 廢=中分離、回收之化學品混合而生成新的飯刻液，故而 可實現蝕刻廢液之再利用，並可實現蝕刻處理之低成本 化。又’因可減少不被再利用之廢棄處理之敍刻廢液之 量’故而亦可發揮優異之環境保護性。 3.氟化氫銨之分離方法 "Γ自於上述氫氟酸之分離方法之中途獲得之殘留產物 5〇〇中分離、回收敦化氫敍。以下，基於圖2對該分離方法 進行說明。 藉由冷卻等使於上述第1蒸鮮驟中獲得之殘留產物5〇〇 結晶，而析出包含氟化氫銨及氟矽酸銨之第丨固體510。再 160736.doc 15 201238912 者，根據來自混合酸100之水之蒸發量，亦有即便不進行 上述冷部，亦析出包含氟化氫銨及氟矽酸銨之固體510之 情形。 繼而，於乾燥第1固體510後，使該第丨固體510完全溶解 於氨水中而獲得溶液（第3液體）7〇〇。將該溶液7〇〇冷卻直至 大致室溫，或放置該溶液直至成為室溫而析出沈澱物（第2 固體）。於該例示中，使用事先使氨溶解於水性溶劑中之 氨水，但作為其他實施形態，亦可於使固體51〇完全溶解 於水性溶劑中後，於其中冒入氨氣氣泡而溶解氨。只要為 獲得以下式所示之析出反應之方法，則可使用各種方法。 (NH4)2SiF6+NH4+H20—6NH4F + Si02| 對經過該析出反應（沈澱反應）之第3液體進行過濾，而 分離成以二氧化矽作為主體之二氧化矽沈澱物71〇(第2固 體）與包含氟化氫銨之濾液8〇〇。 自δ亥濾液800中蒸發去除水及過剩之NH3，而獲得經乾燥 之第3固體810。於該第3固體810中，例如包含95 wt%左右 之氟化氫銨與氟化銨，且氟矽酸銨僅殘留有於實用上可允 許之程度。 如此，藉由使用氨而析出沈澱物（第2固體），而可以高 濃度（高純度）從自混合酸中分離之第1固體510中分離、 回收氟化氫録。 以上，基於圖示之實施形態，對本發明之分離方法及； 離裝置進行說明，但本發明之分離方法及分離裝置並非p丨 定於該等者’亦可添加其他任意之構成物或步驟。又，£ 160736.doc •16- 201238912 對複數個蒸餾步驟、結晶步驟及析出步驟之組合進行說 明，但即便僅實施利用複數個蒸餾步驟對氫氟酸進行分離 之分離方法’亦可提供環境保護性良好之再生技術。 [實施例] 以下，對本發明之具體實施例進行說明。 (實施例1) 準備蝕刻廢液的混合酸。再者，該混合酸之分離前之氫 氟酸濃度為16.4 wt%，氟化氫銨之分離前之濃度為27 4 wt°/〇，發之分離前之濃度為〇.35 wt%，剩餘部分大致為 水。該等濃度之測定係使用上述裝置及方法而進行（關於 以下所述之濃度亦相同）。 [第1蒸餾步驟] 將混合酸500 g投入至蒸餾罐内，並於大氣壓下，將混 合酸加熱至120°C，藉此進行蒸餾。藉此，獲得作為餾出 液A之敗化氫酸（氫氟酸水溶液）。實施該步驟直至爾出量 達到60%，從而獲得297 g餾出液A。 測定顧出液A中之各成分之濃度’結果氫氟酸之濃度為 16.1 wt/ii，I化氫叙之濃度為〇.〇3 wt%，碎之濃度為〇〇2 wt%。氫氟酸相對於混合酸之產率為58 9%。 [第2蒸餾步驟] 繼而，將於第1蒸餾步驟中獲得之餾出液A投入至蒸餾罐 内，並於大氣壓下，將餾出液A加熱至12〇。〇，藉此進行蒸 餾。藉此，獲得作為餾出液B之相對較低濃度之氟化氫 酸。貫施該步驟直至館出量達到8〇〇/0，從而獲得丨84 g傑出 160736.doc -17· 201238912 液B。再者，測令於 .， '疋餘出液B中之各成分之濃度，結果氫氟 西文之濃度為6.7 vvt%，ϋ儿匕 , 氟化氫錄之濃度為〇 wt%，矽之濃度 為 0.01 wt% 〇 另方面，自蒸餾罐中獲得10〇 g殘留產物c。測定殘留 產物C中之各_ &人>、Λ 。 或刀之濃度，結果氫氟酸之濃度為3 3.3 —氟化氫銨之濃度為〇 wt°/。，矽之濃度為〇.〇2 wt〇/。。 又氫I酉文相對於混合酸之產率為40.6%。 如此’可回收作為殘留產物c之高濃度且高純度之氫氟 酸。將以上之結果示於圖3。 [分離步驟] 刀離步驟包括.結晶步驟、析出步驟、及固體回收少 驟。 利用第1蒸餾步驟，自蒸餾罐中獲得85 g殘留產物E^首 先，於結晶步驟中，於殘留產物D中析出第丨固體（固形物 成分），利用沈澱法使該第1固體自殘留產物D中分離，姐 進行乾燥。測定第1固體之成分，結果含有氟化氫銨900 wt%、氟矽酸銨 10.0 Wt0/〇。 繼而’作為析出步驟，將第1固體混合於28 wt%之敦水 中’並於室溫下使其完全溶解而獲得第3液體。使其溶解 於相對於氟化氫銨與氟矽酸銨之化學當量比相當於2〜3倍 之氨水中。例如使第1固體30 g溶解於28 wt%之氨水100 g 中。作為室溫’較佳為20C至25C。作為液溫調整，可使 用利用放置之緩冷卻、及利用怪溫槽之強制性溫度調節 等。 I60736.doc •18· 201238912 對析出沈澱物（第2固體710)之第3溶液進行過濾。作為 過濾方法’使用定量濾紙3C及抽氣過濾，亦可使用其他過 濾材料或離心分離機等，將沈澱物（第2固體710)自第3溶液 中分離。 繼而，作為固體回收步驟，自該濾液8〇〇中使水分與過 剩之氨蒸發，而獲得氟化氫銨與氟化錢之粉末狀之混合物 (第3固體81〇)。 以如此方式可自於氫氟酸之分離方法之中途獲得之殘留 產物500中’回收高純度之氟化氫銨與氟化銨之混合物（第 3固體810)。 使用粉末X射線繞射裝置RINT-TTR(Rigakii股份有限公 司製造）測定該所獲得之粉末狀之混合物（第3固體81 〇)。 又，作為比較試樣’亦同樣地測定第丨固體。作為所獲得 之測定圖’第1固體之測定圖示於圖4中，經回收之說化氫 銨與氟化銨之混合物（第3固體8 10)的測定圖示於圖5中。 於圖5所示之第3固體810中未測定到圖4所示之氟矽酸錄 (NKhSiF6的吸收峰值。因此，可確認利淘本申請案之分 離方法’可回收高純度之氟化氫銨與氟化銨。 如此’可將藉由蒸發而獲得之高濃度之氫氟酸、及藉由 結晶及利用氨之矽之去除而獲得之高純度的氟化氫銨與氟 化敍之混合粉末作為原料而進行回收。由於使用該等原 料’可再次製備包含高純度之氫氟酸與氟化氫銨之蝕刻液 等，並可提供簡單之再生技術，故而具有減輕環境負荷之 效果。 160736.doc -19- 201238912 【圖式簡單說明】 圖1係本發明之較佳實施形態之分離裝置的概略圖。 圖2係用以說明本發明之較佳實施形態之分離方法的概 略圖β 圖3係用以說明實施例之表。 圖4係用以說明實施例之X射線繞射圖。 圖5係用以說明實施例之X射線繞射圖。 【主要元件符號說明】 1 分離裝置 11 蒸鶴罐 12 供給部 13 加熱部 14 攪掉機構 15 冷卻部 16 回收部 17 排氣處理機構 100 現合酸 111 誘導管路 141 攪掉棒 142 熱搜拌器 151 内管 152 外管 181 旋塞 182 旋塞 160736.doc 201238912 191 192 200 300 400 500 510 600 700 710 800 810 溫度計 溫度計 餾出液 回收容器 清洗液 殘留產物 第1固體 殘留產物 液體 第2固體 溶液 第3固體 160736.doc -21 -[(NH4)HF2], fluorite oxime acid [(NH4)2SiF6] and mixed acid of water: 'The apparatus for separating and recovering hydrofluoric acid and ammonium hydrogen fluoride in high purity and relatively high concentration respectively (distillation device) ). In addition to the distillation apparatus, chemicals may be mixed with each other or a device for filtering the precipitate may be used, but the mixed acid 100 is omitted, for example, an etching waste liquid. Specifically, for example, it is a waste liquid in which a member containing sand is subjected to a surname treatment using a cooking fluid containing a hydrofluoric acid and a hydrogen fluoride. Examples of the member containing the crucible include various kinds of glass, crystal, and the like. In such a mixed acid 100, hydrofluoric acid and hydrogen fluoride which were not reacted in the etching treatment were recorded to have a considerable amount of respective components. Therefore, it can be reused as a component of the etching liquid by separately recovering these. Thus, the unreacted etching component can be separated from the etching waste liquid to realize the reuse of the etching liquid, and the etching process can be reduced in cost. Further, since the amount of etching waste liquid which has been disposed of is reduced, it is also advantageous in environmental protection. The concentration of the hydrofluoric acid before the separation in the mixed acid 100 is not particularly limited, and 160736.doc 201238912 is, for example, about 1 to 20 pains. Further, the concentration of the vaporized ammonium hydroxide before the separation in the mixed acid is not particularly limited, and is, for example, about 25 to 35 wt%. Further, the degree of enthalpy before separation in the mixed acid 100 is not particularly limited and is, for example, about 0.1 to 1.0 wt%. Here, the concentration of hydrofluoric acid, ammonium hydrogen fluoride or hydrazine in the mixed acid 100 can be determined as follows. (Measurement of the concentration of 矽) Using an ICP luminescence analyzer (Inductive CQupled piasma SPeCtr〇meter, inductively coupled plasma spectrometer) (for example, manufactured by Shimadzu Corporation, product name "ICPs_751〇"), mixed acid 1〇〇 Qualitative and quantitative analysis of the metal elements contained. Thereby, since the metal atom in the mixed acid 100 is only ruthenium, the concentration A (mol/l) of ruthenium in the mixed acid 1 。 can be obtained. (Measurement of Concentration of Ammonium Bifluoride) Using an ultraviolet-visible spectrophotometer (for example, 'product name "IUV-1240" manufactured by Shimadzu Corporation), indophenol blue absorption spectrophotometry can be used. The hydrogen fluoride in the mixed acid is the sum of the (NH4+) rich in B (m〇l/l). As described above, since the lanthanum in the mixed acid is present in the form of ammonium fluoroantimonate, the concentration of (ΝΗβ) of 25% of ammonium fluoroantimonate can be subtracted from the total concentration B. The concentration C (mol/l) of ammonium hydrogen fluoride in the mixed acid was measured. That is, C=B-2A. (Measurement of the concentration of hydrofluoric acid) The acid concentration of the mixed acid was measured using a potentiometric auto-titration device (for example, 'Kyoto Electronics Industry Co., Ltd., 160736.doc 201238912, Ltd., product name "AT·5 1 〇"). Specifically, the acid concentration of the mixed acid 100 was measured by neutralization titration using a sodium hydroxide aqueous solution of mol.1 mol/dm3. Thereby, the acidity D of the fluorinated acid, the hydrogen fluoride, and the fluorinated acid in the mixed acid 100 can be determined. Because of the above, it is known that the concentration of the acid in the mixed acid 1 and the gasification of the gas, the agricultural degree B', can be obtained by subtracting the acid of ammonium fluoroantimonate from the total acid concentration D. The concentration of the hydrofluoric acid E (m〇i/i) in the mixed acid 100 was determined at a concentration of 4A and an acid concentration B of ammonium hydrogen fluoride. That is, e = d_ 4A - B 〇 or more, an example of a method for measuring the concentration of hydrofluoric acid, ammonium hydrogen fluoride or hydrazine in the mixed acid 100 will be described. As shown in Fig. 1, the separation apparatus 1 of the present embodiment includes a distillation tank (distillation vessel) 11, a supply unit 供给 for supplying the mixed acid 100 to the distillation tank 11, a heating unit 13 for heating the stalk tank 11, and a stirring distillation tank. The mixing mechanism of the mixed acid 1 in the crucible 14 cools the vapor generated by the distillation tank to obtain the cooling portion 15 of the distillate 200, and the recovery portion of the distillate 2, and the recovery portion The gas treatment mechanism 17. The respective components constituting the separation device 1 can have acid resistance with each of the contacts of the mixed acid bismuth. In the present embodiment, it can be composed of polytetrafluoroethylene (PTFE). In addition, the acid-resistant side is not limited to the &, and may be made of an acid-resistant plastic such as a gas-ethylene resin or an acrylic resin. A method of mixing a portion of the acid contact with the stagnation of the acid, or a method of coating the fluororesin on the surface of the body with a metal material, may be a method of contacting the mixed acid. Due to such gold The heat-conductive property of the mixed material with the acid-resistant resin is preferable, and therefore, the liquid temperature can be adjusted by heating and cooling from the outside in a short time, which is preferable. (Supply unit 12) The supply unit 12 accumulates The supply unit 12 is disposed above the distillation tank 11. "The cock 181 is provided in the middle of the flow path between the communication supply unit 12 and the distillation tank, and the cock 181 can be operated by The mixed acid 100 accumulated in the supply unit 12 is supplied to the distillation tank, or the supply is reversed. (Distillation tank 11) The distillation tank 11 is a tank for distilling and mixing the acid 100. An induction line π 1 for inducing the generated vapor to the cooling portion 15 is formed. Further, a thermometer 191 for measuring the temperature of the mixed acid i is disposed in the distillation tank i, and the measurement is performed in the induction line iii. Thermometer 192 of the temperature of the vapor (heating unit 13) The heating unit 13 has a function of heating and mixing the acid 1 through the distillation tank. The heating unit 13 may be included in the coating as shown in the present embodiment. The way of the lower side portion of the distillation tank 11 The heating unit can control the driving of the mixed acid 1〇〇 and the vapor to a specific temperature based on the sensing results of the thermometers 191 and 192. Further, as the heating unit ,3, The mixing apparatus 1 is not limited to the above configuration. 160736.doc 201238912 (stirring mechanism 14) The separating apparatus 1 preferably includes a stirring mechanism i 4. The feeding mechanism 14 has a mixing in the stirring distillation tank 11. The function of the acid 1 ° is carried out by stirring the mixed acid 1 利用 with a stirring mechanism 14 to promote the movement of the substance in the mixed acid 100, and suppressing the solid (solid matter) crystal or the like. In particular, it is possible to suppress crystallization or the like caused by the localization of the concentration in the vicinity of the liquid surface or the inner wall of the container. The stirring mechanism 14 is configured to include a stirring bar (141) disposed in the distillation tank 1 and a hot stirrer (stirring device) 142 on which the distillation can U and the heating unit 13 are placed, and the hot agitator 142 is used. The stirring bar 141 was rotated while stirring the mixed acid 1 〇〇. Further, a stirrer having no heating means may be used instead of the heat stirrer 142 having a heating means. Further, even if the stirrer is not provided, a physical method such as vibration can be applied to the wall surface of the container to disturb the flow of the liquid in the distillation tank. (Cooling Unit 15) The cooling unit 15 has a function of cooling the vapor generated by heating and mixing the acid hydrazine to obtain the distillate 200. As such a cooling portion 丨5, a commonly known cooling pipe can be used. That is, the cooling unit 15 is configured to include the inner tube 151 and the outer tube 152, and the vapor flows in the inner tube 151, and the cooling water flows between the inner tube 151 and the outer tube 152. By this, the vapor flowing in the inner tube 15 is cooled and liquefied by the cooling water to obtain the distillate 200. Further, as long as the distillate 200 is obtained, the length of the inner tube 151 or the temperature of the cooling water is not particularly limited. 160736.doc 201238912 (Recycling section) 6 The collection unit 16 is connected to the cooling unit 15 and has a function of collecting the liquid from the collection hall. A cock 182 is disposed at the bottom of the recovery portion 16, and the liquid (4) stored in the time portion 16 can be finely discharged to the outside of the separation device 1 by operating the cock (for example, as shown in FIG. Recovery container (exhaust gas treatment unit 17) The exhaust gas treatment unit (gas cleaning unit) 17 has a function of neutralizing the exhaust gas that is not liquefied by the cooling unit 。. The exhaust gas treatment mechanism Η contains stored water or a test. The cleaning liquid is completely sealed, and the exhaust gas is neutralized by inducing exhaust gas in the cleaning liquid. The configuration of the separation device 1 will be described above. 2. The separation method of hydrofluoric acid is then The method of separating and recovering hydrogenated acid in the mixed acid 100 (the separation method of the present invention) will be described. The separation method of the present invention schematically shown in Fig. 2 includes a fifth steaming step and a second distillation step. The separation method described is the step of extracting the residual liquid from the mixed acid (10) in the distillation step, and extracting the residual product from the donor liquid 200 in the step of the second step. After the steaming step, the second steaming is carried out. The method of processing in the batch mode of the step and the arrangement of the steaming device used in the first steaming step and the second steaming step are respectively connected by the infusion tube, and by the valve And any one of the in-line methods of processing such as a pump operation. (First steaming step) For example, the mixed acid 100' is supplied from the supply unit 12 to the distillation tank 11, and the heating unit 13 is used by 160736.doc -12-201238912 The mixed acid 100 is added to the temperature of the mixture to the temperature of the mixture, whereby the mixture of the acid is 1 00 at atmospheric pressure. At this time, the mixed acid in the distillation tank 11 can also be stirred by the stirring mechanism 14. The heating temperature (the above specific temperature) of the Japanese niobium acid 10 并无 is not particularly limited, and is, for example, about 120 to 14 (rc). Thereby, water and hydrogen fluoride are mainly used in the self-mixing acid (10). The acid is evaporated, and the gas reaches the cooling unit 15 via the induction line 111. The vapor that has reached the cooling unit 15 is cooled by the cooling unit, and becomes the liquid (i-liquid) 200, and is collected in the recovery unit 16 for recovery to recovery. The Department of Department 16 of the Department of Liquid 200 is based on water and hydrofluoric acid as the main component The concentration of the hydrofluoric acid as the lower liquid 200 is not particularly limited, and the concentration of the hydrofluoric acid of the mixed acid 100 is set to A (wt%). Preferably, it is about 0.75 A to 1.1 A (wt%). The yield (%) of hydrofluoric acid recovered as the distillate 200, that is, "hydrofluoric acid contained in the distillate 200". The amount of the acid contained in the mixed acid 1 说 说 酸 酸 酸 酸 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳Further, the amount (%) of the liquid 200 is not particularly limited, and is preferably about 55 to 7 % by weight (<100%). . Thereby, the safety of the device can be ensured, and a sufficient amount of liquid 200 can be obtained. Water and hydrofluoric acid can be separated from the mixed acid oxime by sufficiently carrying out such an incorporation step. (Second distillation step) 160736.doc •13-201238912 After the completion of the first distillation step, the residual second liquid) 500 present in the distillation tank 11 is discharged from the distillation tank " Recycling container towel. Further, the residual product 5 is supplied to other treatments as described below. Then, in the empty distillation apparatus 1, the distillate 200 is supplied from the supply unit 12 to the distillation tank 1丨, and the distillate 2〇〇 is heated to a specific temperature by the heating unit 丨3, thereby distilling off at atmospheric pressure. Drain 200. At this time, it is also possible to use the mixing mechanism 14 to stir the steam discharged from the hall in the tank u. The heating temperature (the specific temperature mentioned above) is not particularly limited, and is, for example, about 100 to 12 (about TC). Thereby, water and a small amount of hydrofluoric acid are evaporated from the distillate 200, and the vapor thereof is passed through The line 丨丨1 is induced to reach the cooling unit 丨5. The vapor reaching the cooling unit 丨5 is cooled by the cooling unit 15, and the hydrogen fluoride at a relatively low concentration is recovered in the recovery unit 16. This can be sufficiently performed. 2 The steaming step is carried out, and more water than hydrofluoric acid is separated from the 2 hydrazine solution. That is, the distillate can be concentrated 2 〇〇, and after the second steaming step is finished, it remains in the steaming tank 1 The residual product (third liquid) 600 in the crucible is a hydrofluoric acid (hydrofluoric acid aqueous solution) having a hydrofluoric acid concentration higher than that of the distillate. In particular, the distillate 200 in the second distillation step can be used. The heating temperature is set lower than the heating temperature of the mixed acid 1 第 in the first distillation step, and when the water is removed from the outlet liquid 200, the mixing is reduced to the removed crane liquid and is combined with the moisture. The amount of hydrofluoric acid removed. Therefore, the yield of hydrofluoric acid can be increased. 160736.doc .14· 2 01238912 Here, as the hydrofluoric acid of the residual product 600, there is no particular limitation. When the hydrofluoric acid concentration of the mixed acid 100 is A (wt%), it is preferably 2.0 A to 3.0 A (wt%). Further, the yield of hydrofluoric acid recovered as the residual product 600 (8) is {(the amount of hydrofluoric acid contained in the residual product 600 / the amount of hydrofluoric acid contained in the mixed acid bismuth) Xl00} is preferably about 3% or more, whereby the amount of the hydrofluoric acid recovered as the residual product 600 can be sufficiently obtained. The residual product 6〇〇 (hydrogen fluoride) obtained in this manner can be used again. An etchant. When used as an etchant, 'for example, it can also be mixed with a new etchant. Also, the residual product 6 亦可 can be used for the purpose of adjusting the concentration of hydrofluoric acid in a new etchant. The method for separating hydrofluoric acid from the mixed acid 1 以上 is described above. According to this method, the high-purity hydrofluoric acid having a relatively high concentration can be separated and recovered from the mixed acid simply and efficiently. , because a new cooking liquid can be generated by mixing chemicals separated and recycled from the button. In addition, the etching waste liquid can be reused, and the etching process can be reduced in cost, and the environmental protection can be exhibited because the amount of the waste liquid can be reduced by the disposal of the waste that is not reused. 3. Separation method of ammonium hydrogen fluoride "ΓSeparation and recovery of Dunhua hydrogen from the residual product 5〇〇 obtained by the above-mentioned separation method of hydrofluoric acid. Hereinafter, the separation method will be described based on Fig. 2 . Cooling or the like, the residual product obtained in the first steaming step is crystallized, and precipitates the second solid 510 containing ammonium hydrogen fluoride and ammonium fluoroantimonate. Further, 160736.doc 15 201238912, according to the mixed acid 100 The evaporation amount of water may also be a case where the solid 510 containing ammonium hydrogen fluoride and ammonium fluoroantimonate is precipitated even if the cold portion is not carried out. Then, after the first solid 510 was dried, the second solid 510 was completely dissolved in aqueous ammonia to obtain a solution (third liquid). The solution was cooled to about room temperature, or the solution was allowed to stand at room temperature to precipitate a precipitate (second solid). In this example, ammonia water in which ammonia is dissolved in an aqueous solvent in advance is used. However, as another embodiment, after solid 51〇 is completely dissolved in an aqueous solvent, ammonia gas bubbles may be introduced therein to dissolve ammonia. As long as a method of obtaining a precipitation reaction represented by the following formula is used, various methods can be used. (NH4)2SiF6+NH4+H20-6NH4F + SiO2| The third liquid which has undergone the precipitation reaction (precipitation reaction) is filtered to be separated into a cerium oxide precipitate 71 以 which is mainly composed of cerium oxide (second solid) ) 8 滤液 with a filtrate containing ammonium hydrogen fluoride. Water and excess NH3 are removed by evaporation from the delta filtrate 800 to obtain a dried third solid 810. The third solid 810 contains, for example, about 95% by weight of ammonium hydrogen fluoride and ammonium fluoride, and ammonium fluoroantimonate remains only to a practical extent. In this manner, by using ammonia to precipitate a precipitate (second solid), hydrogen fluoride can be separated and recovered from the first solid 510 separated from the mixed acid at a high concentration (high purity). Although the separation method and the separation device of the present invention have been described based on the embodiments shown in the drawings, the separation method and the separation device of the present invention are not limited to those of the above, and any other constituents or steps may be added. Further, £160736.doc •16-201238912 describes a combination of a plurality of distillation steps, crystallization steps, and precipitation steps, but even if only a separation method using a plurality of distillation steps to separate hydrofluoric acid is provided, environmental protection can be provided. Good regeneration technology. [Examples] Hereinafter, specific examples of the invention will be described. (Example 1) A mixed acid of an etching waste liquid was prepared. Further, the concentration of the hydrofluoric acid before the separation of the mixed acid is 16.4 wt%, the concentration of the ammonium hydrogen fluoride before the separation is 27 4 wt ° /〇, and the concentration before the separation is 〇.35 wt%, and the remainder is roughly For water. The measurement of these concentrations was carried out using the above apparatus and method (the concentrations are also the same as described below). [First Distillation Step] 500 g of the mixed acid was placed in a distillation pot, and the mixed acid was heated to 120 ° C under atmospheric pressure to carry out distillation. Thereby, oxidized hydrogen acid (aqueous hydrofluoric acid solution) as the distillate A was obtained. This step was carried out until the amount of effluent reached 60%, thereby obtaining 297 g of distillate A. The concentration of each component in the drug A was measured. As a result, the concentration of hydrofluoric acid was 16.1 wt/ii, the concentration of hydrogen peroxide was 〇.〇3 wt%, and the concentration of the crushed was 〇〇2 wt%. The yield of hydrofluoric acid relative to the mixed acid was 58 9%. [Second distillation step] Next, the distillate A obtained in the first distillation step was charged into a distillation tank, and the distillate A was heated to 12 Torr under atmospheric pressure. 〇, by which distillation is carried out. Thereby, a relatively low concentration of hydrogen fluoride as distillate B was obtained. This step is applied until the volume of the library reaches 8〇〇/0, so that 丨84 g outstanding 160736.doc -17· 201238912 liquid B is obtained. Furthermore, the concentration of the components in the effluent B is 6.7 vvt%, the concentration of hydrogen fluoride is 〇wt%, and the concentration of strontium is 0.01 wt% On the other hand, 10 g of residual product c was obtained from the distillation tank. Each of _ & person >, Λ in the residual product C was measured. Or the concentration of the knife, the concentration of hydrofluoric acid is 3 3.3 - the concentration of ammonium hydrogen fluoride is 〇 wt ° /. The concentration of 矽 is 〇.〇2 wt〇/. . Further, the yield of hydrogen I relative to the mixed acid was 40.6%. Thus, a high concentration and high purity hydrofluoric acid as the residual product c can be recovered. The above results are shown in Fig. 3. [Separation Step] The knife separation step includes a crystallization step, a precipitation step, and a small amount of solid recovery. Using the first distillation step, 85 g of the residual product E^ is obtained from the distillation tank. First, in the crystallization step, the ruthenium solid (solid content) is precipitated in the residual product D, and the first solid self-residue product is precipitated by a precipitation method. Separated in D, the sister is dry. The component of the first solid was measured, and as a result, it contained 900 wt% of ammonium hydrogen fluoride and 10.0 Wt0/〇 of ammonium fluoroantimonate. Then, as a precipitation step, the first solid was mixed in 28 wt% of water, and completely dissolved at room temperature to obtain a third liquid. It is dissolved in ammonia water equivalent to 2 to 3 times the stoichiometric ratio of ammonium hydrogen fluoride to ammonium fluoroantimonate. For example, 30 g of the first solid is dissolved in 100 g of 28 wt% aqueous ammonia. The room temperature ' is preferably from 20C to 25C. As the liquid temperature adjustment, it is possible to use the slow cooling by the use and the forced temperature adjustment using the strange temperature tank. I60736.doc •18· 201238912 The third solution of the precipitated precipitate (second solid 710) was filtered. As the filtration method, the quantitative filter paper 3C and the suction filtration are used, and the precipitate (second solid 710) may be separated from the third solution by using another filter material or a centrifugal separator. Then, as a solid recovery step, water and excess ammonia were evaporated from the filtrate 8 to obtain a powdery mixture of ammonium hydrogen fluoride and fluorinated money (third solid 81 〇). In this manner, a mixture of high-purity ammonium hydrogen fluoride and ammonium fluoride can be recovered from the residual product 500 obtained in the middle of the separation method of hydrofluoric acid (third solid 810). The obtained powdery mixture (third solid 81 〇) was measured using a powder X-ray diffraction apparatus RINT-TTR (manufactured by Rigakii Co., Ltd.). Further, the second solid was measured in the same manner as the comparative sample. The measurement chart of the obtained first solid is shown in Fig. 4, and the measurement of the mixture of the recovered ammonium hydroxide and ammonium fluoride (the third solid 8 10) is shown in Fig. 5 . The fluoroantimonate recording (the absorption peak of NKhSiF6 shown in Fig. 4) was not measured in the third solid 810 shown in Fig. 5. Therefore, it was confirmed that the separation method of the application of the present application can recover high-purity ammonium hydrogen fluoride and Ammonium fluoride. Thus, a high-concentration hydrofluoric acid obtained by evaporation, and a high-purity mixed product of ammonium hydrogen fluoride and fluoride obtained by crystallization and removal with ammonia can be used as a raw material. Recycling is carried out. By using these raw materials, an etching solution containing high-purity hydrofluoric acid and ammonium hydrogen fluoride can be prepared again, and a simple regeneration technique can be provided, thereby reducing the environmental load. 160736.doc -19- 201238912 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view of a separating apparatus according to a preferred embodiment of the present invention. Fig. 2 is a schematic view showing a separating method of a preferred embodiment of the present invention. Fig. 3 is a view for explaining the implementation. Fig. 4 is a diagram for explaining an X-ray diffraction pattern of an embodiment. Fig. 5 is a diagram for explaining an X-ray diffraction pattern of an embodiment. [Description of main components] 1 Separating device 11 Steaming can 12 Supply section 13 Heating section 14 agitating mechanism 15 cooling section 16 recovery section 17 exhaust gas treatment mechanism 100 acid generator 111 induction line 141 agitating rod 142 hot water hopper 151 inner tube 152 outer tube 181 cock 182 cock 160736.doc 201238912 191 192 200 300 400 500 510 600 700 710 800 810 Thermometer Thermometer Distillate Recovery Container Cleaning Solution Residual Product 1st Solid Residue Product Liquid 2nd Solid Solution 3rd Solid 160736.doc -21 -