201238899 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’作為於玻璃材料、水晶等之加工中所使用 之姓刻液’已知有包含氫氟酸與氟化敍者。又，自此種钱 刻液且供用於蝕刻之後之蝕刻廢液中回收氟的技術亦廣為 人知（例如參照專利文獻1) » 於專利文獻1中’記載有藉由使碳酸鈣於包含氫氟酸與 氟化銨之蝕刻液中進行反應，而將氟製成二氧化矽之含有 率較少之高純度氟化鈣並進行回收，從而由所回收之氟化 約再次製造蝕刻液用之氫氟酸的方法。 然而，於此種方法中，無法自蝕刻液中直接分離、回收 氟化銨。即，於製成氟化鈣並進行回收之後，需要將該氟 化鈣製成氟化銨之製程，而無法進行有效之回收。又，由 蚀刻廢液直至製造新的蝕刻液（氟化銨）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 ’由於製程較多’故而亦有裂置構成大型化、 複雜化之問題。 [先前技術文獻] [專利文獻] [專利文獻1 ]曰本專利特開平5_丨70435公報 【發明内容】 [發明所欲解決之問題] 160669.doc 201238899 本發明之目的在於提供—種可自至少含有氟化氫銨與石夕 化合物之固體狀之混合物中簡單地分離高純度之氟化氫銨 的分離方法、及用以實施該分離方法之分離裝置。 [解決問題之技術手段] 本發明係為了解決上述課題之至少一部分而成者，可藉 由以下之形態或應用例之形式而實現。 [應用例1] 本發明之分離方法係自含有氟化氫銨與矽化合物之固體 狀之混合物中分離上述氟化氫銨者， 其特徵在於：包括如下步驟： 獲得使上述混合物溶解於溶劑中而成之第1溶液之準備 步驟； 藉由將上述第1溶液冷卻並進行結晶，而析出含有上述 矽化合物多於上述混合物之固體狀之第丨固體，從而自上 述第1溶液中分離成上述第i固體與第2溶液之第丨結晶步 驟；及 藉由將上述第2溶液冷卻至低於上述第 析出上述氟化氫銨之含有率高於上述混 並進行結晶，而 — -----巧干肉；^上现此 勿之第2固體’從而自上述第2溶液中分離上述第2固體 第2結晶步驟。 藉此’可簡單地分離、回收高純度之氟化氫銨。 [應用例2] 中於分離方法中’較佳為於上述第I结晶步 上迷第1溶液冷卻至30〜60。(：。 160669.doc 201238899 藉此，可分離、回收作兔笛 作為第2固體之更高純度之氟化氫 锻。 [應用例3] 於本發明之分離方法φ，齢 ^ Ϋ 較佳為於上述第2結晶步驟 中，將上述第2溶液冷卻至^ 藉此，可分離、回收作兔笛 作為第2固體之更鬲純度之氟化氫 铵。 [應用例4] 於本發明之分離方法中’較佳為於上述準備步驟中，一 面加熱上述溶劑與上述混合物，_面使其溶解。 精此’可利用第1結晶步驟芬货 aa步驟及第2結晶步驟有效地進行結 晶。 [應用例5] 於本發明之分離方法中’較佳為經乾燥之上述第2固體 中之上述氟化氫銨的含有率為95 wt%以上。 藉此’可使作為第2固體而分離之氟化氫録之濃度（純 度）足夠再利用。· [應用例6] 本發明之分離裝置之特徵在於：其具有本發明之分離方 法。 藉此，可提供-種可簡單地分離、回收高純度之氟化氫 敍之裝置。 【實施方式】 以下，基於隨附圖式所不之較佳實施形態，詳細地說明 160669.doc 201238899 * · * 本發明之分離方法及分離裝置。 圖1係用以實施本發明之較佳實施形態之分離方法的分 離裝置之概略圖’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係用以說明實施例之表。 1.結晶裝置（本發明之分離裝置） 如圖1所示，結晶裝置1含有：儲存溶液200之容器U， 及對今器11内之溶液200進行加熱、冷卻之溫度調節裝置 12。再者，作為溫度調節裝置12之構成，只要可將溶液 200之溫度調節成特定溫度，則並無特別限定。 又，於該結晶裝置1中，較佳為亦可具備攪拌溶液2〇〇之 攪拌機構丨3，該攪拌機構13含有位於溶液2〇〇内之搜拌棒 131、及使攪拌棒131旋轉之攪拌器132。再者，即便不具 備授拌器，亦可以利用於容器之壁面上施加振動等物理方 法’使容器11内之内容物流動之方式進行攪拌。 結晶裝置1係用以藉由對容器u内供給溶液200，並利用 溫度調節裝置12冷卻溶液200，而將溶液200之溫度降低至 特定溫度，從而自溶液200中析出固體的裝置。利用此種 裝置而對溶液200實施下述第}結晶步驟、及第2結晶步 驟。 再者，溶液200係使以氟化氫銨[(NH4)HF2]作為主成分 之固體ιοί、及以作為矽化合物之氟矽酸銨[(NH^2SiF^作 為主成分之固體102的混合物1〇〇溶解於溶劑3〇〇中而成之 第h谷液201，或於第1結晶步驟中獲得之第2溶液2〇2。 2·氟化氫銨之分離方法 160669.doc 201238899 繼而，基於圖2，對自混合物100中分離、回收高純声 氣化氯錢之方法（本發明之分離方法）進行說明。 自混合物100中分離氟化氫銨之方法包括：準備步驟、 第1結晶步驟、及第2結晶步驟。以下，依序對該等弗 進行說明。 (準備步驟） 本步驟係獲得使混合物100溶解於溶劑300中而成之 溶液2 01之步驟。 首先’準備以氟化氫銨作為主成分之固體1〇1、及以 石夕酸錢作為主成分之固體1〇2之混合物1〇〇。作為現合物 _中之固體101之含有率(氟化氫銨之濃度)，並無特別阳 疋例如為80〜9〇 wt%左右。 繼而，使該混合物1〇〇溶解於溶劑3〇〇中而獲得 為溶劑_，只要可溶解混合物1。。，則並無特別 限疋，例如可使用蒸餾水等水。 100又’一較佳為於本步驟中…面加熱溶劑3。0與混合物 ’一面進行混合物1()()於溶劑300中之溶解。藉此，可 ^:合物_對於溶劑之溶解度，故而可有二地進行 之溶解。又，如下所述，於冷卻溶液細時，可 有效地析出析出物。201238899 VI. Description of the Invention: [Technical Field to Be Invented] The present invention relates to a separation method and a separation device. [Prior Art] Hydrofluoric acid and fluorinated have been known as the name of the engraving used in the processing of glass materials, crystals, and the like. Further, a technique for recovering fluorine from an etching waste liquid for etching after such etching is known (for example, refer to Patent Document 1) » Patent Document 1 describes that calcium carbonate is contained in hydrofluoric acid. The reaction is carried out in an etching solution with ammonium fluoride, and the fluorine is made into a high-purity calcium fluoride having a small content of cerium oxide and recovered, thereby re-manufacturing the fluorochemical for the etching liquid from the recovered fluorination. The method of acid. However, in this method, ammonium fluoride cannot be directly separated and recovered from the etching solution. That is, after the calcium fluoride is produced and recovered, it is necessary to prepare the calcium fluoride into a process of ammonium fluoride, and it is impossible to carry out effective recovery. Further, there are many processes for etching the waste liquid until a new etching liquid (ammonium fluoride) is produced, and a large amount of secondary waste liquid is generated in the middle. Therefore, there are also problems of poor environmental protection. X ’ has a large number of processes, so there are also problems of large-scale and complicated rupture. [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. A separation method for simply separating high-purity ammonium hydrogen fluoride in a mixture containing at least a solid mixture of ammonium hydrogen fluoride and a compound of a compound, and a separation device for carrying out the separation method. [Technical means for solving the problem] The present invention has been made in order to solve at least a part of the above problems, and can be realized by the following forms or application examples. [Application Example 1] The separation method of the present invention is characterized in that the ammonium hydrogen fluoride is separated from a solid mixture containing ammonium hydrogen fluoride and a hydrazine compound, and the method comprises the steps of: dissolving the mixture in a solvent; a step of preparing a solution; and cooling the crystallization of the first solution to form a solid ruthenium solid containing the ruthenium compound more than the mixture, thereby separating the ith solid from the first solution a second crystallization step of the second solution; and crystallization by lowering the content of the second solution to be lower than the above-mentioned precipitation of the ammonium hydrogen fluoride, and - crystallization is dried; The second solid crystallization step is separated from the second solution by the second solid. By this, high-purity ammonium hydrogen fluoride can be easily separated and recovered. [Application Example 2] In the separation method, it is preferred that the first solution is cooled to 30 to 60 on the first crystallization step. (: 160669.doc 201238899 Thereby, the rabbit flute can be separated and recovered as a higher purity hydrogen fluoride forging of the second solid. [Application Example 3] The separation method φ, 齢^ Ϋ in the present invention is preferably as described above. In the second crystallization step, the second solution is cooled to thereby separating and recovering ammonium bifluoride which is a higher purity of the second solid as a second flute. [Application Example 4] In the separation method of the present invention Preferably, in the preparation step, the solvent and the mixture are heated to dissolve the surface, and the crystal is efficiently crystallized by the first crystallization step amber step and the second crystallization step. [Application 5] In the separation method of the present invention, the content of the ammonium hydrogen fluoride in the second solid which is preferably dried is 95 wt% or more. By this, the concentration of hydrogen fluoride separated as the second solid can be recorded (purity). [Application Example 6] The separation device of the present invention is characterized in that it has the separation method of the present invention, whereby a device capable of easily separating and recovering high-purity hydrogen fluoride can be provided. Implementation The separation method and the separation device of the present invention are described in detail below based on the preferred embodiment of the accompanying drawings. Figure 1 is a preferred embodiment of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 2 is a schematic view for explaining a separation method of a preferred embodiment of the present invention, and FIG. 3 is a table for explaining the embodiment. 1. Crystallizing apparatus (separating apparatus of the present invention) As shown in Fig. 1, the crystallization apparatus 1 includes a container U for storing the solution 200, and a temperature adjusting device 12 for heating and cooling the solution 200 in the present device 11. Further, as a constitution of the temperature adjusting device 12, The temperature of the solution 200 can be adjusted to a specific temperature, and is not particularly limited. Further, in the crystallization apparatus 1, it is preferable to further include a stirring mechanism 丨3 for stirring the solution 2, and the stirring mechanism 13 is contained in the solution. The stir bar 131 in the crucible and the agitator 132 that rotates the stir bar 131. 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 make the inside of the container 11 The crystallization apparatus 1 is configured to reduce the temperature of the solution 200 to a specific temperature by supplying the solution 200 to the container u and cooling the solution 200 by the temperature adjusting device 12, thereby from the solution 200. A device for depositing a solid. The solution crystallization step and the second crystallization step are carried out on the solution 200. The solution 200 is a solid ιοί with ammonium hydrogen fluoride [(NH4)HF2] as a main component. And in the first crystallization step, the ammonium fluoroantimonate as a ruthenium compound [(NH^2SiF^ as a main component of the solid 102 mixture 1〇〇 dissolved in the solvent 3〇〇) The second solution obtained was 2〇2. 2. Separation method of ammonium hydrogen fluoride 160669.doc 201238899 Next, a method of separating and recovering high-purity sonicated chlorine money from the mixture 100 (the separation method of the present invention) will be described based on Fig. 2 . The method for separating ammonium hydrogen fluoride from the mixture 100 includes a preparation step, a first crystallization step, and a second crystallization step. Hereinafter, the same will be described in order. (Preparation step) This step is a step of obtaining a solution 210 in which the mixture 100 is dissolved in the solvent 300. First, a mixture of a solid 1〇1 containing ammonium hydrogen fluoride as a main component and a solid 1〇2 containing as a main component of a sulphuric acid was prepared. The content of the solid 101 (concentration of ammonium hydrogen fluoride) in the present invention is not particularly high, for example, about 80 to 9 〇 wt%. Then, the mixture was dissolved in a solvent of 3 Torr to obtain a solvent_ as long as the mixture 1 was dissolved. . There is no particular limitation. For example, water such as distilled water can be used. Preferably, in the step of heating, the solvent 3 is mixed with the mixture, and the mixture 1 () () is dissolved in the solvent 300. Thereby, the solubility of the compound can be made to the solvent, so that it can be dissolved in two places. Further, as described below, when the cooling solution is fine, precipitates can be effectively precipitated.
並無特別限定， ’較佳為50〜70°C 作為本步驟中之溶劑300之加熱溫度， 例如於使用蒸餾水作為溶劑300之情形時 左右。 (第1結晶步驟） 160669.doc 201238899 本步驟係藉由將第丨溶液201冷卻並進行結晶，而析出含 有氟矽酸銨多於混合物100之固體（第！固體）4〇〇，從而自第 1溶液201中分離成固體4〇〇與第2溶液2〇2之步驟。 例如，將第i溶液2〇1加入至容器U中…㈣“Μ 液2〇1，一面利用溫度調節裝置12將第丨溶液2〇ι冷卻至特 定溫度。藉此’自第i溶液201中析出含有^^酸敍多於混 合物100之固體（第i固體）40卜繼而，使用沈殿法，自第i 溶液加中分離固體再者，以下將自第i溶液201中去 除固體400之溶液作為第2溶液202。 作為第1溶液2(H之冷卻溫度，並無特別限定，較佳為 3〇〜崎左右，更佳為35〜贼左右。藉此，最終可分離、 回收更高純度之氟化氫錄。 再者’雖並無特別限定’但經乾燥之固體楊中之氣化 氫銨之含有率為7〇〜8〇 wt%。 (第2結晶步驟） 本步驟係藉由將第2溶液202冷卻至低於第以晶步驟之 溫度並進行結晶，而析出氣化氫録之含有率高於混合物 100之固體(第2固體)500’從而自第2溶液2〇2中分離固體 500之步驟。 利用溫度調節裝置12將 亦可一面攪拌溶液一面 含有較多之氟化氫銨之 第2溶液202中分離、回 將第2 >谷液202加入至容器η中， 溶液202冷卻至特定溫度。此時， 進行。藉此，自第2溶液202中析出 固體500。繼而，使用沈澱法，自 收固體500 » 160669.doc 201238899 广經乾燥之固體500中包含含有率高於混合物ι〇〇之氟化 乳銨。即，可將高純度之敦化氫銨作為固體5〇〇而進行分 離、回收。至於固體中之氟化氣録之含有率，並無特 . 別限定’較佳為％ wt%以上，更佳為96 wt%以上。 . 又，作為第2溶液202之冷卻溫度，並無特別限定，較佳 為5:2代左右，更佳為5〜1〇t：左右。藉此，可將更高純度 之氟化氫銨作為固體5〇〇而進行分離、回收。 以上，對自混合物100分離氟化氫銨之分離方法進行說 明。 ° 根據此種方法，可簡單且有效地分離、回收高純度之氣 化氫銨。所回收之氟化氫銨例如可用作蝕刻液之原料。藉 此’可實現蝕刻處理之低成本化。 3 ·混合物1 〇〇 混合物100例如係以如下之方式而獲得者。 作為例如於對玻璃材料、水晶等進行钱刻處理時所使用 之蝕刻液，已知有包含氫氟酸[HF]、氟化氫銨[(Nh4)HF2] 及水[HaO]者。又’於使用過之蝕刻液（蝕刻廢液）中進而包 含矽，該矽係於蝕刻廢液中以矽化合物，具體而言，以氣 矽酸銨[(NH4)2SiF6]之形式而存在。 於此種蝕刻廢液中，殘留有相當量之於蝕刻處理中未反 應之氟化氫銨。因此，可藉由分離、回收氟化氫銨，而將 所回收之氟化氫銨再次用作蝕刻液（或蝕刻液之材料）^本 發明之分離方法可較佳用於自蝕刻廢液中回收氟化氫錢之 用途。 160669.doc 201238899 由蝕刻廢液形成新的蝕刻液，藉此可實現蝕刻廢液之再 利用，並可實現餘刻處理之低成本化。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。 蝕刻廢液中之氫氟酸之濃度並無特別限定，例如為 10 20 wt/。左右。又，蝕刻廢液中之氟化氫銨之濃度並無 特別限定，例如為25〜35 wt%左右。又，姓刻廢液中之石夕 (氟矽酸銨）之濃度並無特別限定，例如為〇ι〜ι〇认㈧左 右。 此處，蝕刻廢液中之氫氟酸、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 C()upied PiasmaIt is not particularly limited, and is preferably 50 to 70 ° C as the heating temperature of the solvent 300 in this step, for example, when distilled water is used as the solvent 300. (1st crystallization step) 160669.doc 201238899 This step is carried out by cooling the ruthenium solution 201 and crystallization, thereby precipitating a solid containing a mixture of ammonium fluoroantimonate and more than 100 (solid: 4), thereby 1 The step of separating the solid solution 4 and the second solution 2〇2 into the solution 201. For example, the i-th solution 2〇1 is added to the container U... (4) "The liquid 2〇1, while the second solution 2 is cooled to a specific temperature by the temperature adjusting device 12. Thus, from the i-th solution 201 Precipitating a solid containing a mixture of more than 100 (i-solid) 40, and then separating the solid from the i-th solution by using the shoal method, and then removing the solution of the solid 400 from the ith solution 201 as follows The second solution 202. The first solution 2 (the cooling temperature of H is not particularly limited, but is preferably about 3 Å to about 崎, more preferably about 35 to thief. Thereby, higher purity can be finally separated and recovered. Further, 'there is no particular limitation', but the content of the vaporized ammonium hydroxide in the dried solid poplar is 7 〇 to 8 〇 wt%. (Second crystallization step) This step is performed by the second solution 202. The step of cooling to a temperature lower than the temperature of the first crystal step and performing crystallization, and precipitating the vaporized hydrogen content to be higher than the solid of the mixture 100 (second solid) 500' to separate the solid 500 from the second solution 2〇2 The temperature adjusting device 12 can also be used to stir the solution while containing more The second solution 202 of ammonium hydrogen fluoride is separated, and the second > trough liquid 202 is added to the vessel η, and the solution 202 is cooled to a specific temperature. At this time, the solid 500 is precipitated from the second solution 202. Then, using the precipitation method, the self-receiving solid 500 » 160669.doc 201238899 The dried solid 500 contains the ammonium fluoride fluoride having a higher content than the mixture ι〇〇. That is, the high-purity ammonium hydride can be used as the solid 5 The content of the fluorinated gas recorded in the solid is not particularly limited. It is preferably % wt% or more, more preferably 96 wt% or more. Also, as the second solution The cooling temperature of 202 is not particularly limited, but is preferably about 5:2 generations, more preferably about 5 to 1 〇t:, whereby higher-purity ammonium hydrogen fluoride can be separated as a solid 5 、. The separation method of separating ammonium hydrogen fluoride from the mixture 100 will be described above. ° According to this method, high-purity vaporized ammonium hydrogen halide can be easily and efficiently separated and recovered. The recovered ammonium hydrogen fluoride can be used, for example, as an etching solution. Raw material 3) Mixture 1 The ruthenium mixture 100 is obtained, for example, in the following manner. As an etching liquid used for, for example, a glass material, a crystal, or the like, it is known to contain hydrogen. Fluoric acid [HF], ammonium hydrogen fluoride [(Nh4)HF2] and water [HaO]. Further, in the used etching solution (etching waste liquid), ruthenium is further contained in the etching waste liquid. Specifically, it exists in the form of ammonium phthalate [(NH4)2SiF6]. In such an etching waste liquid, a considerable amount of ammonium hydrogen fluoride which is unreacted in the etching treatment remains. Therefore, the recovered ammonium hydrogen fluoride can be reused as the etching liquid (or the material of the etching liquid) by separating and recovering ammonium hydrogen fluoride. The separation method of the present invention can be preferably used for recovering hydrogen fluoride from the etching waste liquid. use. 160669.doc 201238899 A new etching solution is formed by the etching waste liquid, whereby the etching waste liquid can be reused, and the cost of the residual processing can be reduced. Further, since the amount of the etching waste liquid to be disposed of is reduced, it is possible to exhibit excellent environmental protection. The concentration of hydrofluoric acid in the etching waste liquid is not particularly limited and is, for example, 10 20 wt/. about. Further, the concentration of ammonium hydrogen fluoride in the etching waste liquid is not particularly limited, and is, for example, about 25 to 35 wt%. Further, the concentration of Shishi (ammonium fluoroantimonate) in the surname of the waste liquid is not particularly limited, and is, for example, 〇ι~ι〇 (8). Here, the concentration of hydrofluoric acid, ammonium hydrogen fluoride, and cesium in the etching waste liquid can be determined as follows. (Measurement of concentration of cesium) Using ICP luminescence analyzer (Inductive C() upied Piasma
Spectr〇meterL合錢光譜儀）(例如，島津製作所股 份有限公W造，製品名「ICPS_751G」），進行㈣廢液 中所含之金屬元素之定性及定量分析。藉此，由於敍刻廢 液中之金屬原子僅為石夕，故而藉此可求出钱刻廢液中之石夕 (氟矽酸銨）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 1 島津製作所股份有限 公司製造，製品名「IUV_124〇」）， 貫知狀紛藍（indophenol blue)吸光光度法，藉此，可求出 .A, 刻廢液中之氟化氫銨及 敗石夕酸敍所具有之（NH，的合舛 4 。袅度B(m〇1/1)。如上所 述，因蝕刻廢液中之石夕係以氣 ^ ^ ^ 秋夂形式而存在，故而 可猎由自合计濃度B中減去濃度A， 而求出触刻廢液中之 160669.doc 201238899 氟化IL敍之濃度C(mol/l)。即C=B-2A。 (氫氟酸之濃度測定）Spectr〇meterL Hefei Spectrometer) (for example, Shimadzu Corporation's share of the company's shares, product name "ICPS_751G"), and (4) qualitative and quantitative analysis of the metal elements contained in the waste liquid. Thereby, since the metal atom in the waste liquid is only Shi Xi, the concentration A (mol/l) of the stone (ammonium fluoroantimonate) in the waste liquid can be obtained. (Measurement of the concentration of ammonium hydrogen fluoride) Using an ultraviolet-visible spectrophotometer (Example 1 manufactured by Shimadzu Corporation, product name "IUV_124〇"), the indophenol blue spectrophotometry can be used to obtain .A, the ammonium hydrogen fluoride in the waste liquid and the sulphate acid (NH, the combination of 4, the degree B (m〇1/1). As mentioned above, due to the etching of the waste liquid in the eve It exists in the form of gas ^ ^ ^ autumn ,, so the concentration A can be subtracted from the total concentration B, and the concentration of 160 1966.doc 201238899 fluorinated IL in the etched waste liquid is determined. ), ie C=B-2A. (Measurement of the concentration of hydrofluoric acid)
使用電位差自動滴定裝置（例如，京都電子工業股份有 限公司製造，製品名「AT_510」），測定蝕刻廢液之酸濃 度。具體而言，藉由利用〇.1 m〇l/dm3之氫氧化鈉水溶液進 行中和滴定’而測定蝕刻廢液之酸濃度。藉此，可求出蝕 刻廢液中之氫氟酸之濃度。因於上文中，已知蝕刻廢液中 之氟矽酸錢濃度A及氟化氳錢濃度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4 a、氟化氫銨所 具有之酸濃度B，而求出蝕刻廢液中之氫氟酸濃度E (mol/l)。即 e=d-4A-B。 以上，對蝕刻廢液中之氫氟酸、氟化氫銨、矽之濃度之 測定方法的一例進行說明。 若蒸餾此種蝕刻廢液’則回收包含氫氟酸及水之顧出 液並且回收包含敗化氫錢及氟石夕酸錄之殘留產物。並 且’例如藉由將殘留產物冷卻等而產生結晶，從而析出含 有氟化氫銨、氟矽酸銨之混合物。最後，可藉由自殘留產 物中去除上述混合物，並乾燥所去除之混合物，而獲得含 有氟化氫铵、及氟♦酸錢之固體狀之混合物I 〇〇。 以上’基於圖示之實施形態，對本發明之分離方法及分 離裝置進行說明’但本發明之分離方法及分離裝置並非限 毛於該等者’亦可添加其他任意之構成物或步驟。 [實施例] 以下，對本發明之具體實施例進行說明。 160669.doc 11 - 201238899 (實施例1) 準備作為蝕刻廢液之混合酸。再者，該混合酸之氫氟酸 濃度為12.6 wt%，氟化氫銨之濃度為27.6 wt%，矽（氟矽酸 銨）之濃度為0.4 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）。 [蒸餾步驟] 繼而’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。(： ’藉此進行蒸餾。實施該步驟 直至餾出量達到60% ’從而獲得193 g殘留產物a。 繼而，將殘留產物A冷卻至2〇。〇，而於殘留產物A内析 出固體。自殘留產物A中分離上述固體，並進行乾燥，藉 此獲得97 g固體B。測定固體B之成分，結果於固體B中包 含氟化氫敍85.1 wt%、氟矽酸錄丨丨〇 wt〇/。。The acid concentration of the etching waste liquid is measured using a potentiometric automatic titrator (for example, manufactured by Kyoto Electronics Industry Co., Ltd., product name "AT_510"). Specifically, the acid concentration of the etching waste liquid was measured by performing neutralization titration with a sodium hydroxide aqueous solution of 〇.1 m〇l/dm3. Thereby, the concentration of hydrofluoric acid in the etched waste liquid can be determined. Since the fluoroantimonic acid concentration A and the fluorinated ruthenium concentration b in the etching waste liquid are known as above, the acid concentration of the ammonium fluoroantimonate can be subtracted from the total acid concentration D by 4 a, The acid concentration B of the ammonium hydrogen fluoride was used to determine the concentration of hydrofluoric acid E (mol/l) in the etching waste liquid. That is, e=d-4A-B. As described above, an example of a method for measuring the concentration of hydrofluoric acid, ammonium hydrogen fluoride or hydrazine in the etching waste liquid will be described. If such an etching waste liquid is distilled, the solvent containing hydrofluoric acid and water is recovered and the residual product containing the deficient hydrogen and the fluorite acid is recovered. Further, the crystals are produced by, for example, cooling the residual product, thereby precipitating a mixture containing ammonium hydrogen fluoride and ammonium fluoroantimonate. Finally, the mixture I 〇〇 can be obtained by removing the above mixture from the residual product and drying the removed mixture to obtain a solid containing ammonium hydrogen fluoride and fluoro acid. The separation method and the separation device of the present invention have been described above based on the embodiments shown in the drawings. However, 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. [Examples] Hereinafter, specific examples of the invention will be described. 160669.doc 11 - 201238899 (Example 1) A mixed acid as an etching waste liquid was prepared. Further, the mixed acid had a hydrofluoric acid concentration of 12.6% by weight, a ammonium hydrogen fluoride concentration of 27.6 wt%, and a cesium (ammonium fluoroantimonate) concentration of 0.4 wt. The rest is roughly water. The determination of the concentrations is carried out using the apparatus and method described above (the concentrations are also the same as described below). [Distillation step] Then, 500 g of the mixed acid was put into a distillation tank, and the mixed acid was heated to 120 under atmospheric pressure. (: 'The distillation is carried out. This step is carried out until the amount of the distillate reaches 60%' to obtain 193 g of the residual product a. Then, the residual product A is cooled to 2 Torr, and the solid is precipitated in the residual product A. The solid was separated from the residual product A, and dried, whereby 97 g of a solid B was obtained. The component of the solid B was measured, and as a result, hydrogen fluoride was contained in the solid B in an amount of 85.1 wt%, and the fluoroantimonic acid was wt.
[準備步驟;I 繼而於50 g蒸館水中混合80 g固體B，並於50。(：下使 其完全溶解而獲得130 g第1溶液C(以下僅稱作「溶液 C」）。 [第1結晶步驟] 繼而’將溶液C冷卻至35t，而於溶液(：中析出第i固體[Preparation step; I then mix 80 g of solid B in 50 g of steaming water and at 50. (: The solution was completely dissolved to obtain 130 g of the first solution C (hereinafter simply referred to as "solution C"). [First crystallization step] Then 'solution C was cooled to 35 t, and the solution was precipitated in the solution (: solid
D(以下僅稱作「固體D」）。繼而，利用沈殿法，自溶液C 中分離固體D，並齡煙阳雜n ^ I yi? 孕乙炼固體D。糟此獲得1 3 g固體D。測定 固體D之成分’結果於固體〇中含有氟化氫銨” 7 4、氟 石夕酸敍21.3 wt%。 160669.doc •12· 201238899 [第2結晶步驟] 繼而，將108 g自溶液C中分離（去除）固體！)後之第2溶液 冷部至，而於第2溶液中析出第2固體E(以下僅稱作 固體E」）。繼而，利用沈澱法，自第2溶液中分離固體 E，並乾燥固體E。藉此獲得14 g固體E。測定固體E之成 分，結果於固體E中含有氟化氫銨96 6 wt%、氟矽酸銨3.4 來自溶液a之氟化氫銨之產率為291%。 如此，可回收作為固體E之高純度之氟化氫銨。 再者’以上之結果示於圖3» 【圖式簡單說明】 圖1係用以實施本發明之較佳實施形態之分離方法的八 離裝置之概略圖。 刀 態之分離方法的概 圖2係用以說明本發明之較佳實施形 略圖。 圖3係用以說明實施例之表。 【主要元件符號說明】 1 結晶裝置 11 容器 12 溫度調節裝置 13 攪拌機構 100 混合物 101 固體 102 固體 131 攪拌棒 I60669.doc 201238899 132 攪拌器 200 溶液 201 第1溶液 202 第2溶液 300 溶劑 400 第1固體 500 第2固體 160669.doc -14-D (hereinafter simply referred to as "solid D"). Then, using the Shen Dian method, the solid D is separated from the solution C, and the age of Yanyang is n ^ I yi? The result is that 1 3 g of solid D is obtained. The content of the solid D component was determined to contain ammonium hydrogen fluoride in the solid hydrazine. 7 4, fluorite oxime acid 21.3 wt%. 160669.doc •12· 201238899 [second crystallization step] Then, 108 g was separated from the solution C After the solid solution was removed (the solid solution was added), the second solid E was precipitated in the second solution (hereinafter simply referred to as solid E). Then, solid E was separated from the second solution by a precipitation method, and solid E was dried. Thereby 14 g of solid E was obtained. The component of the solid E was measured, and as a result, the yield of ammonium hydrogen fluoride (96 wt%) and ammonium fluoroantimonate 3.4 from the solution a in the solid E was 291%. In this way, ammonium bifluoride as a high purity of solid E can be recovered. Further, the above results are shown in Fig. 3» [Schematic description of the drawings] Fig. 1 is a schematic view of an occlusion device for carrying out the separation method of the preferred embodiment of the present invention. Fig. 2 is a schematic view showing a preferred embodiment of the present invention. Figure 3 is a table for explaining the embodiment. [Main component symbol description] 1 Crystallization device 11 Container 12 Temperature adjustment device 13 Stirring mechanism 100 Mixture 101 Solid 102 Solid 131 Stir bar I60669.doc 201238899 132 Stirrer 200 Solution 201 1st solution 202 2nd solution 300 Solvent 400 1st solid 500 second solid 160669.doc -14-