201235300 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種自含有硼化合物及鹼金屬化合物之排 水或固形排出物回收硼酸之硼酸之回收方法及回收裝置。 【先前技術】 於含有硼成分之玻璃之製造中，在自玻璃熔融爐排出之 排氣中，以相對較高之濃度含有硼酸或硫等各種物質。 因此’該排氣不可直接釋放至大氣中，例如，於藉由氫 氧化納等驗進行處理而去除有害之物質後，釋放至大氣 中。 藉由此種排氣之淨化而副生之排水或固形排出物作為產 業廢棄物而受到處理之情形較多。 而於°亥荨排水或固形排出物中，大量含有硼化合物 或鹼金屬化合物等有用之物質。特別A，硼酸係高價，若 可自已對排氣進行處理之排水等回收該硼酸並再利用，則 可降低含有硼成分之玻璃之製造成本。又，就環境問題之 觀點而言，亦較佳為儘可能地自排水或固形排出物回收有 :此’提出有如下各種方法：不限定於藉由含有硼成分 ::璃之製造中之排氣處理而副生之排水，而自包含硼化 a物之排水或固形排出物回收《等之回收方法。 之=時:獻1中’記載有如τ情形:於將對在玻璃 乾燥而用作淨化而獲得之排水中和後，進行 162544.doc 201235300 呈體而令 金如 八 5 ’ #由噴霧塔使自玻璃熔融爐排出之排氣與水 接觸而進杆、落/μ _>、〇» — 乎化、或者進而藉由濕式電集塵機對利用水進 〜淨之排氣進行淨化，從而釋放至大氣中。此時，於藉 由’”、石灰對自喷霧乾燥機或濕式電集塵機排出之排水進行 中和後’進行乾燥而將所獲得之固形成分再利用作玻璃原 料。 又’於專利文獻2中，記載有如下情形：藉由對自玻璃 熔融爐等排出之包含棚酸等之排氣進行冷卻，而與排氣之 淨化一併對硼酸進行回收。 具體而言’藉由水㈣式冷卻機構與线混合式冷卻機 構之併用等方法，將排氣冷卻至㈣以下，藉此將排氣甲 之氣體狀之硼酸析出為固體，接著，藉由乾式電集塵機對 硼酸進行回收，且對排氣進行淨化。 進而，於專利文獻3中，印恭古上丁 。己戟有如下之硼酸之回收方 法：自對成為廢液之鍍鎳液吱钮矣 π伙4鋁表面處理液、於玻璃製造 中排出之排水等包含硼之排水谁 F八進仃處理而吸附有硼的離子 轉換樹脂之棚酸之回收方法。 於該方法中，首先向吸附有棚 ’硕之離子轉換樹脂參透硫酸 而獲得硼溶離液。於在該硼溶離 離/夜中添加氫氧化鈉而進行 中和後，藉由進行加熱濃縮而倍* 叩便、酸鈉析出分離。於將所 剩餘之母液冷卻至35〜4〇t後，夭1 — 无添加硫酸而將pH值調整至 4〜6 ’藉此使石朋酸析出，從而拉 错由離心分離機等對棚酸進 行分離，藉此對硼酸進行回收。 先行技術文獻 162544.doc 201235300 專利文獻 專利文獻1:曰本專利特開2004-238236號公報 專利文獻2:日本專利特開2〇〇3_3〇533 1號公報 專利文獻3:日本專利特開2002-29732號公報 【發明内容】 發明所欲解決之問題 藉由利用該等方法，彳自包含棚化合物等之排水或固形 排出物等回收硼酸而再利用。 此處，於自玻璃熔融爐等排出之排氣中，不僅包含於爐 内熔解之成分，而且亦包含所使用之燃料之燃燒排氣成 分0 因此’於專利文m中記載之方法係於使用重油作為破 璃熔融爐之燃料之情形等、在排氣中包含硫化合物之情形 時’硫酸鹽等硫化合物亦作為再利用之玻璃原料投入於玻 璃熔融爐内。如此’若於玻璃原料中包含硫酸等硫化合 物：則產生如下等問題：除逐漸自原料進入外之硫成分受 到濃縮，從而玻璃之品質下降。 因此’於該方法中，僅可對藉由使用有實質上不含硫之 燃料之排氣之淨化而副生的排水等進行處理。 、相同地’如專利文獻2中記载之方法，於對排氣進行冷 部而將賴作為固體進行析出/时之方法中， 中包切之情形時，若亦將排氣冷卻至顿酸作為固體而析 出之孤度為止，則排氣之溫度成為酸露點以下且 酸。若析出硫酸，則產生裝置為' 瓜 ^ 入成為於回收 162544.doc 201235300 之硼酸中亦包含硫酸之結果。 因此，於該方法φ，+ 中亦僅可對使用有實質上不含硫之燃 料之排氣進行處理 與此相對’若為專利文獻3巾記載之方法，則如使用重 油作為玻璃熔融爐之燃料之情形般，亦可自對包含硫成分 之排氣進行處理而副生之排水等回收硼酸。 」而於。亥方法中’進行利用離子轉換樹脂之排水之處 理’故需要使蝴自離子轉換樹脂溶離之順序，從而於排水 濃度較高之情形時’存在於排水處理中必需之離子轉換樹 月曰裝置變知非；^大之類之問題β χ，於衛容離液含有除硼 西义外之夕種物質之情形時，無法充分地回收高純度之硼 酸。 本發明之目的在於解決上述先前技術之問題點，且在於 提供一種硼酸之回收方法及回收裝置，該硼酸之回收方法 如亦可對處理包含硫成分之排氣而副生之排水等、包含硫 成分之液體或固形物進行處理，又，亦可自高濃度之液 體、或含有除硼化合物外之各種物質之液體或固形物回收 高純度之硼酸。 解決問題之技術手段 為了達成上述目的’本發明提供一種硼酸之回收方法 (1)’其係自包括包含硼化合物與驗金屬化合物之排水、及 固形排出物中之至少一者之被處理液回收硼酸的硼酸之回 收方法，且 於向上述被處理液添加酸而調整為小於pH 4後進行濃 162544.doc 201235300 縮、或於對上述被處理液進行濃縮後添加酸而調整為小於 pH 4， 對經上述濃縮及pH值調整且不包含不溶解物之被處理液 進行冷卻，而作為已析出硼酸結晶之水溶液， 自已析出上述硼酸結晶之水溶液分離該硼酸結晶， 將對該硼酸結晶進行分離後之濾液之5〇〜9〇質量％添加 至進行上述?辰縮及pH值調整前之被處理液中， 對向上述經分離之硼酸結晶添加硼酸水溶液或水之再結 晶用被處理液進行加熱，而將硼酸結晶溶解，對該加熱且 使硼酸結晶溶解之再結晶用被處理液進行冷卻，而作為已 再析出硼酸結晶之水溶液，並自已再析出上述硼酸結晶之 水溶液分離該硼酸結晶， 將對該再析出之硼酸結晶進行分離後之濾液之至少一部 分添加至進行上述濃縮及pH值調整前的被處理液中。 又，本發明提供一種硼酸之回收方法，其係自包括 包含硼化合物與鹼金屬化合物之排水、及固形排出物中之 至少一者之被處理液回收硼酸的硼酸之回收方法，且 於向上述被處理液添加酸而調整為小於pH 4後，進行濃 縮而使鹼金屬鹽析出，從而自已析出鹼金屬鹽之上述被處 理液去除鹼金屬鹽， 或對上述被處理液進行濃縮而使鹼金屬鹽析出，於自已 析出驗金屬鹽之上述被處理液去除驗金屬鹽後，添加酸而 調整為小於pH 4， 向上述經浪及pH值調整且已去除上述驗金屬鹽之被處 162544.doc 201235300 理液’添加水而進行稀釋， 對該經稀釋之被處理液進行冷卻，❿作為已析出删酸結 晶之水溶液， 自已析出上述硼酸結晶之水溶液分離該硼酸結晶， 將對該硼酸結晶進行分離後之濾液添加至進行上述濃縮 及pH值調整前之被處理液中， 對向上述分離之硼酸結晶添加硼酸水溶液或水之再結晶 用被處理液進行加熱’而將餐結晶溶解，對該加敎且使 蝴酸結晶溶解之再結晶用被處理液進行冷卻，而作為已再 析出硼酸結晶之水溶液’並自已再析出上述硼酸結晶之水 溶液分離該硼酸結晶， 將對該再析出之魏結晶進行分離後之濾液之至少一部 分添加至進行上述濃縮及pH值調整前的被處理液中。 又’本發明提供一種硼酸之回收裝置⑴，其係自包括 包含硼化合物與鹼金屬化合物之排水、及固形排出物中之 至少一者之被處理液回收硼酸的裝置，且包括： 濃縮裝置，其對上述被處理液進行濃縮； pH值凋整裝置，其添加酸而將被處理液之邱值調整為 小於4 ; 晶析袭置，其對上述經pH值調整且不包含不溶解物之被 處理液進行冷卻’而作為已析出硼酸結晶之水溶液； 回收裝置’其自上述水溶液分離回收所析出之硼酸結 晶； 送液裝置’其向進行上述漠縮及PH值調整前之被處理液 162544.doc 201235300 進給對該硼酸結晶進行分離回收後之濾液之5〇〜90質量 % ； 加熱溶解裝置，其對向上述分離回收之硼酸結晶添加硼 酸水溶液或水之再結晶用被處理液進行加熱，而將硼酸結 晶溶解； 晶析裝置’其對該加熱且使硼酸結晶溶解之再結晶用被 處理液進行冷卻’而作為已再析出硼酸結晶之水溶液； 回收裝置’其自上述水溶液分離回收再析出之硼酸結 晶，及 送液裝置，其向進行上述濃縮&pH值調整前之被處理液 進給對該再析出之硼酸結晶進行分離回收後之濾液的至少 一部分。 又，本發明提供一種硼酸之回收裝置（2)， 其係自包括包含硼化合物與鹼金屬化合物之排水、及固 形排出物中之至少一者之被處理液回收硼酸的裝置，且包 括： 濃縮裝置，其對上述被處理液進行濃縮而使鹼金屬鹽析 出； 去除裝置，其自被處理液去除所析出之鹼金屬鹽； pH值调整裝置’其添加酸而將被處理液之pH值調整為 小於4 ; 晶析# W，# ^ /、對已藉由上述去除裝置去除驗金屬鹽且已 藉由上述pH值調整裝置調整pH值之被處理液進行冷卻， 而作為已析出硼酸結晶之水溶液； 162544.doc 201235300 回收裝置’其自上述水溶液分離回收所析出之硼酸結 晶； 送液裝置其向進行上述濃縮及pH值調整前之被處理液 進給對該硼酸結晶進行分離回收後之濾液； 加熱浴解裝置，其對向上述分離回收之硼酸結晶添加硼 酸水〉谷液或水之再結晶用被處理液進行加熱，而將硼酸結 晶溶解； 晶析裝置，其對該加熱且使硼酸結晶溶解之再結晶用被 處理液進行冷卻，而作為已再析出硼酸結晶之水溶液； 回收裝置’其自上述水溶液分離回收再析出之硼酸結 晶；及 送液裝置’其向進行上述濃縮及pH值調整前之被處理液 進給對該再析出之硼酸結晶進行分離回收後之濾液的至少 一部分。 發明之效果 根據本發明，可藉由簡易之操作，自藉由自棚石夕酸玻璃 之製造步驟排出之含有硼酸之排氣的淨化而副生之排水或 固形排出物等、包含硼化合物與鹼金屬化合物之排水或固 形排出物回收高純度之石朋酸。 【實施方式】 以下’參照隨附圖式’詳細地對本發明之硼酸之回收方 法進行說明。 圖1表示本發明之硼酸之回收方法（第1態樣）之一例的流 私圖’圖2表示本發明之硼酸之回收方法（第2態樣）之一例 162544.doc •10· 201235300 的流程圖。 如圖1、圖2所示’本發明之硼酸之回收方法（以下，亦 簡稱為回收方法）係如下者：利用因冷卻引起之晶析（釺a 化’晶析），自被處理液回收硼酸。以下，若未特定為第^觸 樣、或第2態樣，則作為第丨態樣與第2態樣之共通之内容 進行說明。 枣發明中之排水及固形排出物中之任一者均包含硼化合 物與鹼金屬化合物。於本發明中，硼化合物與鹼金屬化合 物存在區別，硼酸鈉等包含硼原子與鹼金屬原子之化合物 係若未特別提及，則視為硼化合物。因此，驗金屬化:物 若未特別提及，則為不包含蝴原子之驗金屬化合物。又， 硼化合物並不限定於驗金屬，亦可包含各種構成元素。相 同地，驗金屬化合物亦可包含除蝴外之各種構成元素。 本發明中之排水包括包含硼化合物與鹼金屬化合物之 1物^明中之固形排出物包括包含钱合物與驗金屬化 5物之固體(粉體等)。該等排水與固形排出物亦可含有除 硼化合物與鹼金屬化合物外之化合物。 該等係自制化合物或驗金屬化合 步驟排出者，特佳為白你A 处主（工業性 排出之抽产偽 下以之硼矽酸破璃之製造步驟 ^與鹼性的鹼金屬化合物水溶液接觸 步驟排出之排水或固形排出物。 ㈣之排乳處理 本發明中之被處理液係包 至少—者β3上述排水及固形排出物令之 者之破處理液，且如圖1或圖2所_ 情形時，可為妯kI 圖2所不，於上述排水之 排水本身，亦可為向排水添加水而獲得之水 162544.doc ，U · 201235300 稀釋液。於上述固形排出物之情形時為向固形排出物添加 水而獲得之水溶液。又，如圖1或圖2所示，可使用上述排 水作為向固形排出物添加之水，又，亦可利用水對固形排 出物與排水之混合物進行稀釋而作為本發明中之被處理 液。 進而’亦可將包含使下述之硼酸結晶析出且對該結晶進 行分離後之硼酸之水溶液（濾液等）用作稀釋水的至少一部 分0 進而，又，該等被處理液亦可為混合該2個以上者。 作為本發明中之排水及固形排出物，例示有於如 FPDplat Panel Display，平板顯示器）用玻璃、太陽電池用 玻璃等中所使用之硼矽酸玻璃之製造中，在對自玻璃熔融 爐、炼融玻璃成形爐等排出之排氣進行淨化時副生之排水 或固形排出物作為一例。 於硼石夕酸玻璃之製造中，氧化硼為揮發性，藉此自熔融 中途之向溫之玻璃原料或熔融玻璃揮發氧化硼，混入燃燒 排氣等排出氣體中’從而作為含有氧化硼之排氣，自硼矽 酸玻璃之製造步驟排出。因此，需要該排氣之淨化，而為 了進行有效之淨化’於較多情形時，使用鹼性化合物之水 /谷液或粉末而進行淨化。作為驗性化合物，可使用驗金屬 化合物’特別是可使用鈉化合物。作為具體之鹼金屬化合 物’可列舉氫氧化鈉、碳酸氫鈉、碳酸鈉等水溶性之鹼性 納化合物。 於圖3中’概念性地表示該排氣之淨化流程之一例。 162544.doc 12 201235300 於圖3所示之淨化流程中，首先，於冷卻塔中，藉由水 或氫氧化鈉水溶液，將自用以製造硼矽酸玻璃之破螭熔融 爐排出之排氣冷卻至赋左右。此時，視需要添加氫氧 化鈉或碳酸氫鈉（於圖3中，僅表記氫氧化鈉水溶液）作為除 害藥劑。 u 接著，視需要向經冷卻之排氣添加碳酸氫鈉粉末等，藉 由過濾袋進行淨化。進而，於文丘襄霧化器中，藉由氫氧 化鈉等對藉由過濾袋而淨化之排氣進行處理而淨化’從而 作為經淨化之排氣釋放至大氣中。再者，於該排氣之淨化 ;L程中添加之氫氧化鈉等鹼金屬化合物能夠以固體添加， 亦可作為水溶液添加、或者亦可添加固體及水溶液之兩 於該淨化流程中’在藉由過濾袋而捕集之固形之廢品、 或來自文丘裏霧化器之廢液中，含有硼酸、氧化硼、硼酸 鈉、氫氧化鈉、氯化鈉、氟化鈉、硫酸鈉、硝酸鈉等各種 蝴化合物或鹼金屬化合物。 因此，於本發明之回收方法中，可將於該淨化流程中藉 由過濾袋而捕集之固形之廢品用作本發明中之固形排出 又可將自文丘裏霧化器排出之廢液用作本發明中之 排液。再者，以下亦將該等廢液或固形廢品稱為排 形排出物》 即，於本發明之賴之时方法中，在對因圖3所示之 排氧之淨化流程產生之副生物進行處理的情形時，將自文 丘義霧化器排出之排水作為包含硼化合物與驗金屬化合物 I62544.doc 201235300 之排水。又，將藉由過濾袋 棚化合物與驗金屬化合物之 明中之被處理液係使用該等 而捕集之固形排出物作為包含 固形排出物》因此，上述本發 而獲得。 再者，於在圖3所示之排氣之淨化流程中，自冷卻技亦 排出包含缝合物與驗金屬化合物之固形之廢品或廢液之 情形時，該等與藉由過遽袋而捕集之固形排出物或自文丘 裏霧化器排出之排水相同地’亦可用作包含硼化合物與鹼 金屬化合物之排水或固形排出物。 又’於本發明之回收方法中’作為包含硼化合物盥鹼金 屬化合物之排水或固形排出#，並不限定於藉由上述财 酸玻璃製造步驟中之排氣之淨化而副生之排水或固形排出 物’可例示包含硼化合物與驗金屬化合物之各種排水或固 形排出物。 發月中之固形排出物及排水中之任—者除侧化合物 驗金屬化合物外，均亦可包含硫化合物、氣化合物、氣, 合：等。除蝴化合物與驗金屬化合物外之該等成分係如 述:義&作為構成兀素而不包含侧與驗金屬中之任一者 托^因此，例如，上述氣化鈉、氟化鈉、硫酸鈉、； &鈉等ίτ本發明中之驗金屬化合物。本發明中之固形排 物及排水中之任一者均亦可少量含有硫化合物、氣化 物、氟化合物，但較佳為實質上不含有。 本發明中之固形排出物及排水中所包含之硼化合物較, 戶㈣與《鈉。本發明中之固形排出物及排水 之鹼金屬化合物較佳為主要為硫酸鈉與氯化鈉，丨 162544.doc 201235300 該等外亦可包含相對少量之氟化鈉或硝酸鈉等。 作為本發明中之固形排出物及排水中所包含之化合物之 構成元素比（質量比），以將硼量（質量）設為1之相對比，較 佳為鹼金屬量為〇_6〜13、硫量為〇〜6、及氯量為〇〜6。= 者，該構成元素比中之硫或氣主要為硫酸鈉或氣化鈉等鹼 金屬化合物中之元素。 作為包含為此種構成元素比之各種化合物之固形排出物 及排水，藉由自硼矽酸玻璃製造步驟排出之排氣之淨化而 副生之排水或固形排出物為代表性者。本發明可自此種排 水或固形排出物回收高純度之硼酸。 作為包含上述排水及固形排出物中之至少—者之本發明 中之被處理液中所包含的各構成元素之濃度，較佳為硼濃 度為10 40 g/L，鈉濃度為20〜400 g/L，硫濃度為〇〜2〇〇 Μ’氣濃度為〇〜扇g/L。再者，該各構成元素濃度中之 硫及氯主要為鹼金屬化合物中之構成元素。 又’考慮為被處理液中之較多化合物受到離子化。例 如，考慮為侧酸離子、納離子、硫酸離子、氯化物離子、 既化物離子、石肖酸離子等存在於被處理液中。 ^者、’破處理液較佳為不包含不溶解成分。然而只要 二進仃加熱而作為加熱水溶液之階段中不包含不溶解 根i需要則^包含藉由加熱而溶解之不溶解成分。亦可 成分。 愿寻而自加熱前之被處理液去除不溶解 於本發明之回收方法中 ’作為較佳之態樣，如圖1所示 162544.doc •15- 201235300 般對此種被處理液進行加熱而作為加熱水溶液1加熱水 溶液需要為不包含不溶解物者。於即便為加熱水溶液亦存 在不浴解物之情形時，藉由過遽等而去除不溶解成分。 力…水/合液之加熱溫度並無特別限定但較佳為Μ。以 上。於加熱水溶液之加熱溫度小於50°C時，硼酸之回收率 較低，又，析出之蝴酸結晶不會充分成長，故產生分離性 能變差之不良。 加熱水溶液之加熱溫度較佳為1〇〇<t以下，進而較佳為 70〇C 〜80〇C。 藉此’可提高硼酸結晶之回收率及分離性能。 如上所述，於本發明之回收方法中，該被處理液之加熱 係作為較佳之態樣而進行者’且並非為必需之步驟。 接著，向加熱水溶液（於不進行加熱之情形時為被處理 液’以下’將被處理液與加熱水溶液亦簡稱為被處理液） 添加酸，將pH值調整為小於4。 於本發明中，可如上所述般藉由pH值調整裝置（pH值調 整箱），以於已加熱之狀態下成為小於pH 4(於未加熱之情 形時，將被處理液之pH值設為小於pH 4，以下相同）之方 式’對被處理液之pH值進行調整，藉此可回收純度較高之 硼酸結晶。又，藉由在冷卻晶析前對pH值進行調整，可於 使水溶液中之鹼金屬硼酸鹽轉化成硼酸後，進行冷卻操 作，從而硼酸結晶之粒形或粒徑之控制變得容易。進而， 藉此亦可提高硼酸之純度。 又，於經pH值調整之被處理液之pH值為4以上時，在被 162544.doc -16- 201235300 處理液之固形成分濃度較高之情形時，無法回收充分之純 度之硼酸。鹼金屬硼酸鹽等雜質之量較多之硼酸係難以再 用作不包含鹼金屬成分之硼矽酸玻璃等之原料。又，於進 一步藉由再結晶法對所獲得之硼酸進行純化之情形時，亦 難以獲得尚純度之删酸。 經pH值調整之被處理液之pH值小於4，較佳為3·5以下， 更佳為小於3.5，進而較佳為1〜3。 藉此，可回收更高純度之硼酸結晶。 對被處理液之PH值調整中所使用之酸並無特別限定，可 利用硫酸、鹽酸、硝酸等各種無機酸。作為此種酸，較佳 為硫酸。 於自藉由自硼矽酸玻璃之玻璃熔融爐排出之排氣之淨化 而副生的排水等回收硼酸之情形時，在該排水等中包含硫 酸離子之情形較多。因此，藉由在？11值調整中使用硫酸， 可抑制多餘之成分向被處理液添加。 又，若於pH值調整中使用鹽酸，則存在氣化物離子成為 腐蝕晶析裝置之原因之虞，從而更佳為硫酸之使用。 再者，於本發明之回收方法中，pH值調整並不限定於在 對被處理液進行加熱後進行。 即，如於圖1中虛線所示，被處理液之pH值調整可於進 行上述被處理液之加熱前進行、或者亦可於進行下述之濃 縮後進行。 經PH值調整之被處理液較佳為於進行冷卻前藉由濃縮裝 置進仃濃縮’從而作為經濃縮之被處理液。藉由進行濃 162544.doc 201235300 細’可提高侧酸之回收率。 作為濃縮裝置’例如可使用如下公 等：於經減壓之濃縮結晶罐内，自 裝置 荨加熱流體之複數個傳熱管之表面噴布被處 = 縮裝置中’使濃縮結晶罐内之被處理液藉 ^遭 至對複數個傳熱管進行喷布之喷嘴。β 衣，循環 濃縮裝置中所產生之蒸氣受到冷凝而導入至冷 内，該冷凝水箱之冷凝水利用於稀釋用水、各裂置之^ 水、或者回收步驟中之結晶之清洗水等中。 於本發明之回收方法φ 根據破處理液中之硼及鈉（Na) 之濃度，選擇要應用紅態樣及下述之第2態樣中之哪個。 ^在對被處理液進行濃縮及PH值調整而直至適於晶析之 棚濃度為止時，未析出仏鹽之情形時，較佳為第】態樣。 :在對被處理液進行濃縮而直至適於晶析之删濃度為止 時、或對被處理液進行濃縮及pH值調整直至適於晶析之蝴 濃度為止時’析出Na鹽之情形時，較佳為下述之第2態 樣。 ’ «濃縮及pH值調整前之被處理液中所包含 之納㈣與卵）之質量比（Na/B)，選擇要應用第i態樣及 下述之第2態樣令之哪個。 於被處理液包含^25〇4及沁〇之情形時，若質量比 (Na/B)為3·6以下’則較佳為第丨態樣，若質量比（_晴 過3.6，則較佳為第2態樣。 於被處理液不包含jsja 1S O jf, -h >6. χτ /-! 1 2S〇4而包3 NaC1之情形時，若質量 I62544.doc 201235300 比（Na/B)為39以下’則較佳 々矛&樣，右質量比（Na/B) 超過3.9，則較佳為第2態樣。 於被處理液包含犯28〇4而 个匕3 NaC1之情形時，若質詈 比（Na/B)為3.1以下，則較佳為 …， 職佳為第1態樣，若質量比(Na/B) 超過3.1 ’則較佳為第2態樣。 於二態樣…縮係進行至不會析出不溶解物之程 ^ ’所謂此處所言之不溶解物係指進行濃縮及阳值 =、结果含有成分因超過飽和溶解度而析出之結晶固 體0 、2,%樣_，濃縮係以析出作為不溶解物之驗金 獻之方式進行。使被處理液中所包含之作為鹼金屬鹽之201235300 VI. Description of the Invention: [Technical Field] The present invention relates to a method and a recovery apparatus for recovering boric acid from boric acid or a solid effluent containing a boron compound and an alkali metal compound. [Prior Art] In the production of glass containing a boron component, various substances such as boric acid or sulfur are contained in a relatively high concentration in the exhaust gas discharged from the glass melting furnace. Therefore, the exhaust gas cannot be directly released into the atmosphere, for example, after being treated by a hydrogen hydride treatment to remove harmful substances, and then released into the atmosphere. Drainage or solid discharges that are by-produced by such exhaust gas purification are often treated as industrial waste. In addition, a large amount of a useful substance such as a boron compound or an alkali metal compound is contained in the water drainage or solid discharge. In particular, boric acid is expensive, and if the boric acid is recovered and reused by draining the exhaust gas, the manufacturing cost of the glass containing the boron component can be reduced. Further, from the viewpoint of environmental problems, it is also preferable to recover as much as possible from the drain or the solid discharge: this has proposed various methods as follows: not limited to the row in the manufacture of the boron-containing component::glass Gas treatment and by-product drainage, and recovery from the drainage or solid discharge containing boride a substance. In the case of "1", it is described as the case of τ: after the neutralization of the drainage obtained by drying in the glass for purification, 162544.doc 201235300 is presented and the gold is as good as eight 5' # by the spray tower The exhaust gas discharged from the glass melting furnace is brought into contact with water to enter the rod, fall/μ_, or 〇», or to be purified by the wet electric dust collector to remove the exhaust gas from the water to the net exhaust gas, thereby releasing to In the atmosphere. At this time, after the neutralization of the drainage discharged from the spray dryer or the wet electric dust collector by '', lime' is dried, and the obtained solid component is reused as a glass raw material. Further, Patent Document 2 In the case where the exhaust gas containing arsenic acid or the like discharged from a glass melting furnace or the like is cooled, the boric acid is recovered by purifying the exhaust gas. Specifically, 'cooling by water (four) type The combined use of the mechanism and the line hybrid cooling mechanism, the exhaust gas is cooled to (4) or less, whereby the gaseous boric acid of the exhaust gas is precipitated as a solid, and then the boric acid is recovered by the dry electric dust collector, and the row is discharged. In addition, in Patent Document 3, Ink has been used as a method for recovering boric acid as follows: from the nickel plating liquid to the waste liquid, the 表面 伙 4 4 aluminum surface treatment liquid, in the glass A method for recovering arsenic acid containing an ion-converting resin which adsorbs boron and which is adsorbed by boron, which is discharged in the manufacturing process, etc. In this method, firstly, the ion-converting resin After the sulfuric acid is permeated to obtain a boron dissolving solution, sodium hydroxide is added to the boron-dissolved/night to neutralize, and then concentrated by heating and concentrated, and the sodium salt is separated and separated. The remaining mother liquid is cooled to After 35~4〇t, 夭1—the pH is adjusted to 4~6′ without adding sulfuric acid, so that the sphagic acid is precipitated, and the steric acid is separated by a centrifugal separator or the like, thereby performing boric acid. Japanese Patent Laid-Open No. 2004-238236 Patent Document 2: Japanese Patent Laid-Open Publication No. Hei No. Hei. JP-A-2002-29732 SUMMARY OF THE INVENTION Problems to be Solved by the Invention By using these methods, boric acid is recovered from a drain or a solid discharge containing a shed compound or the like, and reused. The discharged exhaust gas contains not only the components melted in the furnace but also the combustion exhaust gas component of the fuel used. Therefore, the method described in Patent Document m is based on the use of heavy oil as a glass melting furnace. In the case of a material, etc., when a sulfur compound is contained in the exhaust gas, a sulfur compound such as a sulfate is also introduced into the glass melting furnace as a glass raw material to be reused. Thus, if a sulfur compound such as sulfuric acid is contained in the glass raw material: The following problems: In addition to the gradual addition of sulfur components from the raw material, the quality of the glass is reduced. Therefore, in this method, only the purification of the exhaust gas using a fuel containing substantially no sulfur can be used. The raw water is treated in the same manner as in the method described in Patent Document 2, and in the case where the exhaust gas is cooled in the cold portion and the lanthanum is precipitated as a solid. When the exhaust gas is cooled to a degree of separation of the acid as a solid, the temperature of the exhaust gas becomes an acid dew point or lower and the acid is formed. When the sulfuric acid is precipitated, the generating device is made into the boric acid of 162544.doc 201235300. It also contains the result of sulfuric acid. Therefore, in the method φ, +, only the exhaust gas using the fuel containing substantially no sulfur can be treated. If the method described in Patent Document 3 is used, the heavy oil is used as the glass melting furnace. In the case of the fuel, boric acid may be recovered from the treatment of the exhaust gas containing the sulfur component and the drainage of the by-product. And. In the hai method, 'the treatment of the drainage using the ion-converting resin' is required, so the order of detaching the butterfly from the ion-conversion resin is required, so that when the drainage concentration is high, the ion-transformation tree-reed device which is necessary for the drainage treatment is changed. Knowing the problem; ^ big problem such as β χ, in the case of Weirong liquid containing the substance of the night of the addition of boron, it is not able to fully recover high-purity boric acid. The object of the present invention is to solve the above problems of the prior art, and to provide a method and a recovery device for recovering boric acid, which can also be used for treating waste water containing sulfur components, such as drainage, including sulfur. The liquid or solid matter of the component is treated, and the high-purity boric acid can also be recovered from a liquid of high concentration or a liquid or solid matter containing various substances other than the boron compound. Means for Solving the Problems In order to achieve the above object, the present invention provides a method for recovering boric acid (1) which is recovered from a liquid to be treated including at least one of a drain containing a boron compound and a metal test compound, and a solid discharge. a method for recovering boric acid of boric acid, which is adjusted to be less than pH 4 after adding acid to the liquid to be treated, and then concentrated to 162544.doc 201235300, or concentrated after the concentration of the liquid to be treated, and adjusted to be less than pH 4, The liquid to be treated which has been subjected to the above concentration and pH adjustment and does not contain insoluble matter is cooled, and as an aqueous solution in which boric acid crystals have been precipitated, the boric acid crystal is separated from the aqueous solution in which the boric acid crystal has been precipitated, and the boric acid crystal is separated. 5 to 9 9% by mass of the filtrate is added to the liquid to be treated before the above-mentioned reduction and pH adjustment, and the treatment liquid for recrystallization in which the boric acid aqueous solution or water is added to the separated boric acid crystal is heated. And the boric acid crystal is dissolved, and the recrystallization for heating and dissolving the boric acid crystal is cooled by the liquid to be treated, and Further, an aqueous solution of boric acid crystals is precipitated, and the boric acid crystal is separated from the aqueous solution of the boric acid crystal, and at least a part of the filtrate obtained by separating the re-precipitated boric acid crystal is added to the treatment before the concentration and pH adjustment. In the liquid. Moreover, the present invention provides a method for recovering boric acid, which is a method for recovering boric acid from boric acid, which comprises at least one of a drainage liquid containing a boron compound and an alkali metal compound, and a solid effluent, and After the acid to be treated is adjusted to be less than pH 4, the alkali metal salt is precipitated, and the alkali metal salt is removed from the liquid to be treated from which the alkali metal salt has been precipitated, or the alkali metal is concentrated to form an alkali metal. Salt is precipitated, and after removing the metal salt from the above-mentioned treated liquid of the metal salt, the acid is added and adjusted to be less than pH 4, and the above-mentioned wave and pH adjustment are performed and the above-mentioned metal salt is removed. 162544.doc 201235300 The chemical liquid is diluted with water, and the diluted liquid to be treated is cooled, and the aqueous solution is precipitated as an acid solution. The boric acid crystal is separated by separating the boric acid crystal from the aqueous solution of the boric acid crystal. The filtrate is added to the treated liquid before the above concentration and pH adjustment, and boron is added to the separated boric acid crystal. The acid aqueous solution or the recrystallization of water is heated by the liquid to be treated to dissolve the meal crystal, and the recrystallized recrystallized solution which is dissolved in the crystallized acid crystal is cooled as the aqueous solution in which the boric acid crystal has been reprecipitated. The boric acid crystal is separated from the aqueous solution of the above boric acid crystal, and at least a part of the filtrate obtained by separating the re-precipitated Wei crystal is added to the liquid to be treated before the concentration and pH adjustment. Further, the present invention provides a boric acid recovery device (1) which is a device for recovering boric acid from a liquid to be treated comprising at least one of a drain containing a boron compound and an alkali metal compound, and a solid discharge, and comprising: a concentration device, The liquid to be treated is concentrated; the pH isolating device is added with acid to adjust the value of the liquid to be treated to less than 4; the crystallization is carried out, and the pH is adjusted and does not contain insoluble matter. The treated liquid is cooled as an aqueous solution in which boric acid crystals have been precipitated; the recovery device 'separates and recovers the precipitated boric acid crystals from the aqueous solution; and the liquid feeding device 'processes the liquid to be treated before the above-mentioned dispersion and pH adjustment 162544 .doc 201235300 Feeding 5〇~90% by mass of the filtrate after separation and recovery of the boric acid crystals; heating and dissolving device for heating the treated liquid by adding a boric acid aqueous solution or water to the boric acid crystal separated or recovered as described above And dissolving the boric acid crystal; the crystallization apparatus 'cooling the recrystallization for the boric acid crystal by the treatment liquid for cooling An aqueous solution in which boric acid crystals have been reprecipitated; a recovery device that separates and recovers boric acid crystals from the aqueous solution, and a liquid feeding device that feeds the treated liquid before the concentration and pH adjustment to the reprecipitation The boric acid crystals are subjected to at least a part of the filtrate after separation and recovery. Further, the present invention provides a boric acid recovery device (2) which is a device for recovering boric acid from a liquid to be treated comprising at least one of a drain containing a boron compound and an alkali metal compound, and a solid discharge, and comprising: a device for concentrating the liquid to be treated to precipitate an alkali metal salt; a removing device for removing the precipitated alkali metal salt from the liquid to be treated; and a pH adjusting device for adjusting the pH of the liquid to be treated by adding an acid Is less than 4; crystallization # W, # ^ /, the treated liquid which has been removed by the above-mentioned removal device and whose pH has been adjusted by the above-mentioned pH adjusting device is cooled, and as the precipitated boric acid crystal Aqueous solution; 162544.doc 201235300 recovery device 'separating and recovering boric acid crystals precipitated from the aqueous solution; and feeding the liquid to the liquid to be treated before the concentration and pH adjustment, and separating and recovering the boric acid crystals a heating bathing device which adds boric acid water to the boric acid crystal separated and recovered as described above, and recrystallizes the liquid to be recrystallized with the liquid to be treated, and boron is heated. The acid crystal is dissolved; the crystallization apparatus is configured to cool the recrystallized solution of the boric acid crystal which is heated and dissolved in the boric acid crystal as an aqueous solution in which the boric acid crystal has been reprecipitated; and the recovery apparatus 'separates and recovers the boric acid which is re-precipitated from the aqueous solution. And a liquid feeding device that feeds at least a part of the filtrate obtained by separating and recovering the re-precipitated boric acid crystals to the liquid to be treated before the concentration and pH adjustment. Advantageous Effects of Invention According to the present invention, it is possible to use a simple operation to purify a waste water or a solid discharge or the like from the purification of a boric acid-containing exhaust gas discharged from a manufacturing process of a glass sulphate glass, and to contain a boron compound and The drain or solid effluent of the alkali metal compound recovers high purity staphic acid. [Embodiment] Hereinafter, a method for recovering boric acid of the present invention will be described in detail with reference to the accompanying drawings. Fig. 1 is a flow chart showing an example of a method for recovering boric acid according to the present invention (a first aspect). Fig. 2 is a view showing a flow of a boric acid recovery method (second aspect) of the present invention. 162544.doc •10·201235300 Figure. As shown in Fig. 1 and Fig. 2, the method for recovering boric acid according to the present invention (hereinafter also referred to simply as the method for recovery) is as follows: crystallization by cooling (crystallization) is used to recover from the liquid to be treated. Boric acid. Hereinafter, unless otherwise specified as the first touch or the second aspect, the description will be made as a common condition between the second aspect and the second aspect. Any of the drainage and solid effluent in the jujube invention comprises a boron compound and an alkali metal compound. In the present invention, a boron compound is distinguished from an alkali metal compound, and a compound containing a boron atom and an alkali metal atom such as sodium borate is regarded as a boron compound unless otherwise specified. Therefore, metallization: if not specifically mentioned, it is a metal compound that does not contain a butterfly atom. Further, the boron compound is not limited to the metal test, and may contain various constituent elements. Similarly, the metal compound may also contain various constituent elements other than the butterfly. The drainage in the present invention includes a solid effluent containing a boron compound and an alkali metal compound, and includes a solid (powder or the like) containing a clathrate and a metallization. The drainage and solids discharges may also contain compounds other than boron compounds and alkali metal compounds. These are the self-made compounds or the metallization step discharge, especially for the white you A (the industrial discharge of the production of the borax citrate glass manufacturing steps ^ contact with the alkaline alkali metal compound aqueous solution The drainage or solid discharge discharged in the step. (4) The milk discharge treatment The liquid to be treated in the present invention is at least the treatment liquid of the above-mentioned drainage and solid discharges of β3, and as shown in Fig. 1 or Fig. 2 In the case of 妯kIFig. 2, the drain of the drain itself may be 162544.doc, U · 201235300 diluted water obtained by adding water to the drain. In the case of the solid discharge described above, An aqueous solution obtained by adding water to the solid effluent. Further, as shown in FIG. 1 or FIG. 2, the above-mentioned drainage can be used as water added to the solid effluent, and the mixture of the solid effluent and the drainage can be diluted with water. Further, as the liquid to be treated in the present invention, it is also possible to use an aqueous solution (filtrate or the like) containing boric acid which precipitates the following boric acid crystals and separates the crystals as at least a part of the dilution water. Further, the above-mentioned liquid to be treated may be a mixture of the two or more. The drainage and solid discharges in the present invention are exemplified in glass for FPDplat Panel Display, flat panel display, glass for solar cells, and the like. In the production of the borosilicate glass to be used, a by-product drainage or solid discharge is taken as an example when purifying the exhaust gas discharged from a glass melting furnace or a smelting glass forming furnace. In the manufacture of borax sorbic acid glass, boron oxide is volatile, thereby volatilizing boron oxide from the glass raw material or molten glass in the middle of melting, and is mixed into the exhaust gas such as combustion exhaust gas, thereby serving as a row containing boron oxide. Gas is discharged from the manufacturing steps of borosilicate glass. Therefore, the purification of the exhaust gas is required, and in order to carry out effective purification, in many cases, the water/valley liquid or powder of the alkaline compound is used for purification. As the test compound, a metal test compound can be used, and in particular, a sodium compound can be used. The specific alkali metal compound 'is a water-soluble basic nano compound such as sodium hydroxide, sodium hydrogencarbonate or sodium carbonate. An example of the purification process of the exhaust gas is conceptually shown in Fig. 3 . 162544.doc 12 201235300 In the purification process shown in Figure 3, first, in the cooling tower, the exhaust gas discharged from the smelting furnace for producing borosilicate glass is cooled by water or aqueous sodium hydroxide solution to Assign left and right. At this time, sodium hydroxide or sodium hydrogencarbonate (in the case of Fig. 3, only an aqueous sodium hydroxide solution) is added as a detoxification agent as needed. u Next, add sodium bicarbonate powder or the like to the cooled exhaust gas as needed, and purify it by a filter bag. Further, in the Venturi atomizer, the exhaust gas purified by the filter bag is treated by sodium hydroxide or the like to be purified, and is released into the atmosphere as purified exhaust gas. Further, in the purification of the exhaust gas; the alkali metal compound such as sodium hydroxide added in the L process can be added as a solid, or can be added as an aqueous solution, or two solid and aqueous solutions can be added in the purification process. The solid waste collected by the filter bag or the waste liquid from the venturi atomizer contains boric acid, boron oxide, sodium borate, sodium hydroxide, sodium chloride, sodium fluoride, sodium sulfate, sodium nitrate, etc. Various butterfly compounds or alkali metal compounds. Therefore, in the recovery method of the present invention, the solid waste which can be collected by the filter bag in the purification process can be used as the solid waste in the present invention and can be used to discharge the waste liquid from the venturi atomizer. It is used as a drain in the present invention. In addition, the waste liquid or the solid waste is also referred to as a discharge effluent in the following, that is, in the method of the present invention, the accessory organism produced by the purification process of the oxygen discharge shown in FIG. 3 is performed. In the case of treatment, the drainage discharged from the venturi atomizer is used as the drainage containing the boron compound and the metal compound I62544.doc 201235300. Further, the solid waste discharged by using the liquid to be treated in the filter bag compound and the metal test compound is used as a solid-containing discharge, and thus the present invention is obtained. Furthermore, in the purification process of the exhaust gas shown in FIG. 3, when the self-cooling technique also discharges the solid waste or waste liquid containing the suture and the metal compound, the same is captured by the bag. The solid discharge of the collection or the drainage discharged from the venturi atomizer can also be used as a drainage or solid discharge comprising a boron compound and an alkali metal compound. Further, in the recovery method of the present invention, as the drainage or solid discharge # containing the boron compound ruthenium metal compound, it is not limited to the drainage or solid form by the purification of the exhaust gas in the above-mentioned acid-acid glass production step. The effluent 'can be exemplified by various drainage or solid discharges containing a boron compound and a metal test compound. In the solid discharge and the drainage in the month of the moon, the sulfur compound, gas compound, gas, and the like may be contained in addition to the side compound metal compound. The components other than the butterfly compound and the metal test compound are as described above: the composition & as a constituent element, and does not include any of the side and the test metal. Therefore, for example, the above-mentioned gasified sodium, sodium fluoride, Sodium sulfate, & sodium, etc. The metal compound in the present invention. Any of the solid waste and the drainage in the present invention may contain a sulfur compound, a gasification substance or a fluorine compound in a small amount, but it is preferably substantially not contained. The solid effluent in the present invention and the boron compound contained in the wastewater are compared with those of the household (4) and "sodium." Preferably, the solid effluent and the alkali metal compound for drainage in the present invention are mainly sodium sulfate and sodium chloride, and 162 162 544.doc 201235300 may also contain a relatively small amount of sodium fluoride or sodium nitrate. The ratio of the constituent elements (mass ratio) of the solid effluent in the present invention and the compound contained in the wastewater is preferably a ratio of the amount of boron (mass) to 1, preferably 碱 6 to 13 The amount of sulfur is 〇~6, and the amount of chlorine is 〇~6. If the sulfur or gas in the constituent element ratio is mainly an element in an alkali metal compound such as sodium sulfate or sodium gasification. The solid waste and the drainage which are contained in the composition of such a constituent element are representative of the drainage or solid discharge by the purification of the exhaust gas discharged from the borosilicate glass production step. The present invention recovers high purity boric acid from such drain or solids effluent. The concentration of each constituent element contained in the liquid to be treated in the present invention containing at least the above-mentioned drainage and solid discharge is preferably a boron concentration of 10 40 g/L and a sodium concentration of 20 to 400 g. /L, the sulfur concentration is 〇~2〇〇Μ' gas concentration is 〇~fan g/L. Further, sulfur and chlorine in the concentration of each constituent element are mainly constituent elements in the alkali metal compound. Further, it is considered that a large amount of compounds in the liquid to be treated are ionized. For example, it is considered that a side acid ion, a nano ion, a sulfate ion, a chloride ion, an ion, a succinic acid ion, or the like is present in the liquid to be treated. Preferably, the 'breaking treatment liquid does not contain insoluble components. However, as long as the dihydrazine is heated and does not contain insoluble in the stage of heating the aqueous solution, the insoluble component which is dissolved by heating is contained. It can also be ingredients. It is desirable to find that the treated liquid before heating is not dissolved in the recycling method of the present invention. As a preferred aspect, the liquid to be treated is heated as shown in Fig. 1 162544.doc •15-201235300. Heating the aqueous solution 1 to heat the aqueous solution is required to be such that it does not contain insoluble matter. In the case where the aqueous solution is not dehydrated even when the aqueous solution is heated, the insoluble component is removed by enthalpy or the like. The heating temperature of the water/water mixture is not particularly limited, but is preferably Μ. the above. When the heating temperature of the heated aqueous solution is less than 50 °C, the recovery of boric acid is low, and the crystallized crystals precipitated are not sufficiently grown, so that the separation performance is deteriorated. The heating temperature of the heated aqueous solution is preferably 1 Torr < t or less, and more preferably 70 〇C to 80 〇C. By this, the recovery and separation performance of boric acid crystals can be improved. As described above, in the recovery method of the present invention, the heating of the liquid to be treated is carried out as a preferred embodiment and is not an essential step. Then, acid is added to the heated aqueous solution (the liquid to be treated and the heated aqueous solution are also simply referred to as the liquid to be treated in the case where the liquid is not heated), and the acid is added to adjust the pH to less than 4. In the present invention, the pH adjusting device (pH adjusting box) can be used to be less than pH 4 in the heated state as described above (when the temperature is not heated, the pH of the liquid to be treated is set. The pH of the liquid to be treated is adjusted in a manner smaller than pH 4 and the same as the following, whereby the boric acid crystal having a higher purity can be recovered. Further, by adjusting the pH before cooling crystallization, the alkali metal borate in the aqueous solution can be converted into boric acid and then cooled, whereby the control of the grain shape or particle size of the boric acid crystal can be facilitated. Further, the purity of boric acid can also be increased by this. Further, when the pH of the liquid to be treated adjusted by pH is 4 or more, when the solid content of the treatment liquid of 162544.doc -16 - 201235300 is high, it is impossible to recover boric acid of sufficient purity. Boric acid having a large amount of impurities such as an alkali metal borate is difficult to be used as a raw material such as borosilicate glass which does not contain an alkali metal component. Further, in the case where the boric acid obtained is further purified by a recrystallization method, it is also difficult to obtain acid purity of a purity. The pH of the liquid to be treated adjusted to pH is less than 4, preferably 3 or less, more preferably less than 3.5, still more preferably 1 to 3. Thereby, a higher purity boric acid crystal can be recovered. The acid to be used for adjusting the pH of the liquid to be treated is not particularly limited, and various inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid can be used. As such an acid, sulfuric acid is preferred. In the case where boric acid is recovered by the purification of the exhaust gas discharged from the glass melting furnace of the borosilicate glass, the sulphuric acid ions are often contained in the drainage or the like. So by? Sulfuric acid is used in the 11-value adjustment to suppress the addition of excess components to the liquid to be treated. Further, when hydrochloric acid is used for pH adjustment, vapor ions are a cause of corrosion of the crystallization apparatus, and it is more preferably used for sulfuric acid. Further, in the recovery method of the present invention, the pH adjustment is not limited to being carried out after heating the liquid to be treated. That is, as shown by the broken line in Fig. 1, the pH adjustment of the liquid to be treated may be carried out before the heating of the liquid to be treated, or may be carried out after the concentration described below. The pH-adjusted liquid to be treated is preferably concentrated by a concentration device before being cooled to serve as a concentrated treated liquid. The recovery of the side acid can be improved by performing a thick 162544.doc 201235300 fine. As the concentrating device, for example, the following can be used: in the concentrated crystallization tank under reduced pressure, the surface of the plurality of heat transfer tubes from the apparatus 荨 heating fluid is sprayed in the condensing device to make the crystallization tank The treatment liquid is taken up to a nozzle for spraying a plurality of heat transfer tubes. The β-cloth, the vapor generated in the circulation concentrating device is condensed and introduced into the cold, and the condensed water of the condensed water tank is used for the dilution water, the water for each cleavage, or the crystallization water in the recovery step. In the recovery method φ of the present invention, which of the second aspect to be applied is selected according to the concentration of boron and sodium (Na) in the treatment liquid. In the case where the concentration of the liquid to be treated is adjusted and the pH is adjusted until the concentration of the shed suitable for crystallization, the yttrium salt is not precipitated, and it is preferably the first aspect. : When the concentration of the liquid to be treated is concentrated until the concentration is suitable for crystallization, or when the liquid to be treated is concentrated and the pH is adjusted until the concentration of the butterfly suitable for crystallization is precipitated, the Na salt is precipitated. Jia is the second aspect of the following. The mass ratio (Na/B) of the concentration (Na/B) contained in the treated liquid before concentration and pH adjustment is selected, which one of the ith state and the second aspect pattern to be applied is selected. In the case where the liquid to be treated contains ^25〇4 and 沁〇, if the mass ratio (Na/B) is less than 3·6, it is preferably the first aspect. If the mass ratio (_ qing is over 3.6, then Good for the second aspect. If the treated liquid does not contain jsja 1S O jf, -h >6. χτ /-! 1 2S〇4 and 3 NaC1, if the mass I62544.doc 201235300 ratio (Na/ B) is 39 or less, and it is preferable that the right mass ratio (Na/B) exceeds 3.9, which is preferably the second aspect. The treated liquid contains 28〇4 and a 匕3 NaC1 In the case, if the mass ratio (Na/B) is 3.1 or less, it is preferably..., and the service is preferably the first aspect. If the mass ratio (Na/B) exceeds 3.1', the second aspect is preferred. In the two-state... the process of shrinkage is carried out until the insoluble matter is not precipitated. 'The so-called insoluble matter as used herein refers to the concentration and the positive value =, and the result contains the crystalline solid which precipitates out of the saturated solubility. 2,% sample_, the concentration is carried out in the form of a gold deposit as an insoluble matter, and the contained liquid is contained as an alkali metal salt.
Na现例如硫酸納（Na2S〇4)或氯化納⑽α)等作為雜 析出。 無，第1態樣、第2態樣，為了提高蝴酸之回收率，均較 佳為藉由濃縮而經pH值調整之被處理液之固形成分漠度設 為15質量％以上。換言之，較佳為進行濃縮直至被處理液 之固形成分濃度成為15質量％以上為止。 曰另-方©’因操作之難度、或因不充分之㈣W起之結 晶品質之劣化，濃縮後之被處理液之固形成分濃度較佳為 3 〇質量％以下。 濃縮溫度並無特別限定，但較佳為50t: 〜100t。藉由將 濃縮之溫度設為上述範圍内，可提高硼酸之回收率。該濃 縮時之溫度亦可與被處理液製造時或pH值調整時之被處理 液之溫度不同。通常，以與PH值調整後之被處理液相同程 162544.doc •19· 201235300 度之溫度、或高於其之溫度進行濃縮。又，於減壓濃縮等 中亦可成為pH值調整後之被處理液之溫度以下。減壓係 車义佳為以10000 Pa〜8〇〇〇〇 pa進行更佳為以20000Na is now precipitated as, for example, sodium sulphate (Na2S〇4) or sodium (10)a chloride. In the first aspect and the second aspect, in order to improve the recovery rate of the acid, it is preferable that the solid solution concentration of the liquid to be treated adjusted by the concentration is 15% by mass or more. In other words, it is preferred to carry out concentration until the solid content concentration of the liquid to be treated is 15% by mass or more. The concentration of the solid content of the liquid to be treated after concentration is preferably 3 〇 mass% or less due to the difficulty of the operation or the deterioration of the crystal quality due to the insufficient (four) W. The concentration temperature is not particularly limited, but is preferably 50 t: 〜100 t. By setting the concentration temperature to the above range, the recovery of boric acid can be improved. The temperature at the time of concentration may be different from the temperature of the liquid to be treated when the liquid to be treated is manufactured or when the pH is adjusted. Usually, it is concentrated at the same temperature as or higher than the temperature of the liquid to be treated, which is adjusted to the pH value of 162544.doc •19·201235300 degrees. Further, it may be equal to or lower than the temperature of the liquid to be treated after pH adjustment in concentration under reduced pressure or the like. Decompression system Che Yijia is better at 10,000 Pa~8〇〇〇〇 pa for 20,000
Pa〜70000 Pa進杆。:渔…从 丁 濃縮後之加熱水溶液之溫度與上述經 加熱之被處理液之溫度相同’較佳為5〇。。〜⑽它，特佳 7(TC 〜80〇C 。 ·、 而於第1態樣中，較佳為，在無論以哪種條件進行 濃縮之情形時，均不會藉由濃縮而生成不溶解物。 又於第2態樣中，當考慮設備負擔時，相對於濃縮後 之液體析出之鹼金屬鹽較佳為不超過1〇質量％。 於第2態樣之情形時’藉由對濃縮裝置之循環泵之葉輪 之前端速度進行調整，而對析出之Na鹽之粒徑進行控制’ 並於去除步驟中，選擇性地去除Na鹽。 具體而5 ’將循環|之葉輪之前端速度設為例如 m/sec，藉此將作為析出之⑽鹽之氣化鈉、硫酸鈉之粒徑 設為H)0〜300叫左右。此時，未期望而析出之侧酸結晶之 粒徑為20〜50 μηι，藉由接碎+ # „ μ猎由後續之旋風器，可將作為雜質之Na 鹽自包含硼酸之濃縮液分離。 再者’作為固液分離裝置，並不限^於旋風器，亦可使 用利用橫型連續式離心分離機之大粒徑結晶之分離或利用 流動層之分級、或者批次式沈降分離法等。 於第2 _樣中’此處’於濃縮步驟前進行向被處理液添 加酸之PH值調整步驟，因此於預先將被處理液中之驗金屬 硼酸鹽轉化成石朋酸與驗金屬鹽後進行濃縮’故亦包含藉由 162544.doc •20- 201235300 該轉化而產生之鹼金屬鹽，且於濃縮步驟中，可使鹼金屬 鹽之結晶成長，藉此於去除步驟中，可有效地去除驗金屬 鹽。 於第2態樣之情形時，藉由旋風器而去除作為雜質之Na 鹽之結晶之被處理液係作為晶析原液而導入至晶析原液箱 内。向晶析原液箱内添加稀釋用水而稀釋被處理液（稱為 稀釋步驟）。如此，藉由稀釋用水對被處理液進行稀釋， 因此於後續之晶析步驟中，可抑制除硼酸結晶外之雜質之 析出。 .再者，於本發明之回收方法中，如上所述般對以如圖i 或圖2所示之『(被處理液之加熱—)pH值調整—濃縮』之順 序（以下，稱為實施形態1)進行處理並無限定。 即，作為第1態樣及第2態樣之其他實施形態，亦可作為 如下之被處理液：於將被處理液加熱至5〇t以上後（然而， 此處亦如上所述般加熱並非必須）進行濃縮，以經濃縮之 被處理液（於第2態樣之情形時，在進行濃縮而使作為雜質 之Na鹽結晶析出後，藉由旋風器去除心鹽結晶之被處理 液）為50t以上之狀態，添加硫酸等酸而進行pH值調整， 將PH值調整為小於4、較佳為3.5以下、更佳為小於3卜 進而較佳為1 3之已濃縮之經pH值調整之被處理液（以下， 稱為實施形態2)。 再者，此時，亦因與之前相同之原因，已濃縮之經阳值 調整之被處理液之固形成分濃度亦較佳為15質量％以上， 又’較佳為30質量％以下。 I62544.doc 21 201235300 於實施形態1中，藉由濃縮裝置，對添加硫酸而進行pH 值調整後之酸性較強之被處理液進行加熱濃縮，因此濃縮 裝置需要使用難以腐蝕之高價之材料。另一方面，於實施 形態2中，於藉由濃縮裝置之濃縮步驟後進行pH值調整步 驟，因此與實施形態1相比，濃縮裝置無需使用高價之材 料，從而可降低成本。 進而，作為第2態樣之其他實施形態，可列舉以下實施 形態。 (第2態樣之實施形態3) 於第2態樣之實施形態2中，在去除步驟與晶析步驟之間 设置PH值調整步驟，但於該情形時，存在如下情形：作為 向去除步驟後之被處理液（相當於鹼金屬鹽之飽和溶液）添 加藉由pH值調整而伴隨鹼金屬硼酸鹽之轉化產生之鹼金屬 鹽之結果，重新生成鹼金屬鹽之結晶。於該情形時，存在 士下It形：驗金屬鹽結晶係總量供給至晶析原液箱内，故 為了：制鹼金屬鹽之結晶向晶析步驟混入而使用之稀釋用 :之里變多。#此’存在如下情形:稀釋晶析原液中之硼 夂濃度亦下降，於晶析步驟中析出之硼酸結晶之量減少。 於該情形時，作為與第2態樣之實施形態i、2不同之形 態’亦可於濃縮步驟與去除步驟之間，設置PH值調 (未圖示）β 於該實施形態中’藉由去除㈣去除藉由ΡΗ值調整 金屬鹽之結日日日之至少—部分，藉此與在去除步 ”曰曰析步驟之間設置阳值調整步驟之情形相比 I62544.doc •22· 201235300 稀釋用水之量，從而可掸 旦 m 了藉由晶析步驟回收之硼酸之 重。然而，於該情开名拉 , 、’去除步驟以PH值較低之狀態進 故於減輕去除步驟中之耐醆性之負擔之情形時，較佳 f於去除步驟與晶析步驟之間設置PH值調整步驟。再者， 錯由添加硫酸而析出之鹼 •屬孤，，·口日日易於變為微結晶，故 於藉由旋風器等而對鹼厶厘 金屬麗之結日日進行分離之情形時， 亦存在鹼金屬鹽之結晶盔 曰曰無法有效地去除之可能性，於該情 形時’較佳為於濃縮步驟前進行硫酸添加。 (第2態樣之實施形態4) 於漠縮步驟前’以被處理液中之驗金屬《鹽之至少-部分轉化成硼酸與驗金屬鹽之方式進行PH值調整（較佳為 阳4〜6’更佳為忡4〜55，進而較佳為阳4〜5)，進而，亦 可於去除步驟後，為了提高硼酸純度而進行pH值調整(較 佳為小於PH4，更佳為pH i〜3)(未圖示）。 於該實施形態中’藉由濃縮裝置進行處理之液體之阳值 相對較高’因此高價之材料之使用受到抑制，⑼而可降低 成本，並且於濃縮步驟前，驗金屬棚酸鹽之至少一部分進 2轉化，藉此伴隨於此而產生之鹼金屬鹽成長為適於藉由 /辰縮步驟去除之大小之粒徑，故可藉由去除步驟有效地去 除，其結果，稀釋用水之量得到抑制，從而可增加藉由晶 析步驟析出之硼酸結晶之量。 接著，將經pH值調整之被處理液（較佳為已濃縮之經pH 值調整之被處理液）冷卻至某種溫度為止，從而使硼酸結 晶析出。即，藉由晶析裝置（結晶罐），利用因所謂之冷卻 162544.doc •23· 201235300 引起之sa析（冷卻晶析）而使蝴酸結晶析出。於冷卻晶析 中’作為伴隨藉由冷卻操作使水溶液之溫度下降，而硼酸 結晶之溶解度下降之結杲，析出硼酸結晶。以下，將該冷 卻操作之終點之溫度稱為冷卻溫度。 於本發明中，藉由利用晶析，可自含有硼化合物或鹼金 屬化合物之被處理液’選擇性地回收硼酸。又，可藉由晶 析而選擇性地回收硼酸，因此亦可自對包含硫成分之排氣 進行淨化而副生之排水或固形排出物回收硼酸。進而，如 上所述’於藉由酸對加熱水溶液進行pH值調整後，藉由冷 部晶析而析出硼酸結晶’藉此硼酸結晶之粒形或粒徑之控 制變得容易。進而，可提高回收之硼酸結晶之純度。 特別是，於第2態樣之情形時，於冷卻晶析之前，對被 處理液進行濃縮而使作為雜質之鹼金屬鹽析出並去除，因 此即便為鹼金屬鹽之濃度較高之被處理液，亦可回收純度 較高之硼酸。 再者，亦如專利文獻3所示，即便為於對包含硼酸（硼化 合物）之被處理液進行冷卻後，添加硫酸等而將pH值調整 為特定之酸性之方法，亦可使硼酸之結晶析出而回收硼 酸。 然而，於該方法中，藉由pH值之調整而瞬間析出硼酸之 結晶，故易於向蝴酸結晶中取入Na鹽等雜質，又，因係货 結晶而附著包含附著於結晶表面上之Na鹽等雜質之水之量 增加，故於在被處理液中存在各種化合物之情形時，無法 獲得高純度之硼酸結晶。 162544.doc •24- 201235300 又，該處理順序係瞬間析出硼酸結晶，故產生硼酸結晶 之形狀變形之不良。 上述冷卻溫度並無特別限定，但較佳為3〇β(：以上且小於 贼。於冷卻溫度為50〇c以上時，無法充分地析出侧酸結 晶，而產生回收率變差之不良。 反之，於冷卻s度小於3(rc日夺，產生硫酸納等驗金屬化 合物之結晶作為混晶而析出之不良。 進而，冷卻前之經pH值調整之被處理液之溫度與冷卻溫 度的差為HTC以上為宜，較佳為2〇t以上。特佳為坑以 上。藉由使該溫度差變大，可提高硼酸結晶之回收率。 藉此，可將雜質之混入抑制為最小限，從而可更加提高 删酸結晶之回收率。 再者’因#經阳㈣整之被處理液進行冷卻引起之觸酸 結晶之析出較佳為於減壓下進行。 藉由在減壓下進行冷卻而進行硼酸結晶之析出，可抑制 於採用套管冷卻方式之情形時擔憂之向傳熱面之鏽皮生 、從而裝置之維濩變得谷易，並且藉由減少硼酸結晶之 損失，可提高硼酸之回收率。 再者’此時之屋力之高度並無特別限定，但於冷卻開始 時，杈佳為以10000 Pa〜70000 Pa進行減壓更佳為以 20000 Pa〜6G_ pa進行減|，於冷卻結束時，較佳為以 1〇〇〇 Pa〜15_ Pa進行越，更佳為以2咖 行減壓。 延 於藉由經p Η值調整之被處理液之冷卻而使蝴酸之結晶析 I62544.doc •25· 201235300 出後，在回收步驟中，藉由回收裝置（離心分離機）將所析 出之結晶自水溶液分離，從而回收硼酸之結晶。此時，包 含結晶之水溶液之溫度較佳為維持為上述冷卻溫度、較佳 為30C以上且小於50 °C而進行分離操作。 硼酸結晶之分離方法並無特別限定，可利用過濾、離心 分離、沈降等各種用以自液體中分離固體成分之公知之分 離方法。 此處，於對硼酸結晶進行分離後之濾液中，包含未析出 之硼酸。 因此，較佳為，藉由送液裝置，向包含排水及固形排出 物中之至少一者之被處理液進給該濾液，從而再利用（以 下’亦稱為向上述被處理液添加濾液）作上述被處理液之 原料。即，較佳為，將該濾液用作上述排液或固形排出物 之稀釋水等。例如，可將藉由上述過濾袋而捕集之固形排 出物與該滤液之混合物添加至上述被處理液而使用（咬者 用作被處理液）’又，亦可根據需要，向固形排出物與渡 液之混合物添加水而作為上述被處理液。藉此，可更提言 自上述排液或固形廢品之硼酸之回收率。 此處’於最初對硼酸結晶進行分離之剩餘之遽液中，不 僅包含較多之硼酸’而且亦包含雜質。因此，於第丨蘇樣 中’若該濾液向被處理液之使用量過多，則隨之雜質受到 濃縮而被處理液中之雜質濃度成為高濃度，從而存 卞仕·無法 進行適當之處理之虞。 因此，添加至被處理液中而再利用之濾液較佳為作為、请 162544.doc -26- 201235300 =二:分。具體而言，添加至被處理液中之濾液相對於 子硼L晶進行分離後之濾液整體，較佳為設為5〇質量 ‘90質量％。藉此’可防止因被處理液中之雜質之增加而 引起之不良影響，並且較佳地實現删酸之回收率提高。 於第2態樣中，藉由濃縮裝i使被處理液中所包含 T作為雜質之Na鹽濃縮並析出，從而藉由作為絲裝置之 旋風器進行去除，因此於對驗金屬鹽濃度較高之被處理液 行濃縮之情形時，亦可幾乎不包含鹼金屬之結晶而獲得 辰縮後之液體。因此’添加至被處理液中而再利用之遽液 =為據液之至少—部分，較佳為全部。藉此，可較佳地 提高硼酸之回收率。 無响第1嘘樣及第2態樣，均廢棄對硼酸結晶進行回收後 之處理水之-部分’而將殘餘部返還至上述添加步驟，因 Μ由對處理水之廢棄量進行調整’即於被處理液之驗金 屬鹽濃度較高，且於濃縮步驟或去除步驟中施加負荷之情 形時’使處理水之廢棄量變多，從而可使濃縮步驟或去除 步驟變得容易。另-方面’於濃縮步驟或去除步驟之負荷 不大之凊形時，使處理水之廢棄量變少、，從而可提高棚酸 之回收率。 如此，藉由本發明之回收方法回收之硼酸結晶係充分高 純度者，亦可直接用作硼矽酸玻璃之原料等。 然而，根據用途等，亦存在所回收之硼酸結晶並未充分 ’月洗，而硼酸結晶之純度未滿足期望之值之情形。於該情 形時，亦可藉由不包含鹼金屬成分之硼酸水溶液或水，對 162544.doc •27- 201235300 所回收之硼酸結晶進行清洗。再者，硼酸結晶之清洗係藉 由公知之方法進行即可。再者，所謂不包含鹼金屬成分之 硼酸水溶液係指，不僅不包含鹼金屬化合物，而且不包含 硼酸鈉等包含鹼金屬原子之硼化合物、除該等化合物外之 包含鹼金屬原子之化合物、鹼金屬離子等之硼酸水溶液。 又，根據用途等，亦存在所回收之硼酸結晶之純度並不 充分高之情形。於該情形時’較佳為，藉由進行再次晶析 (再結晶處理），而更提高硼酸結晶之純度。亦可根據需 要，將再結晶處理進行2次以上，但通常可藉由丨次之再結 晶處理’獲得充分高純度之硼酸結晶。 如圖1或圖2所示，於再結晶處理中，向所回收之硼酸結 晶添加水（或不包含鹼金屬成分之硼酸水溶液，或作為下 述之再結晶後之濾液之硼酸水溶液，以下，亦可將該等稱 為硼酸水溶液）’而作為再結晶用被處理液，並藉由利用 加熱溶解裝置進行加熱，將硼酸結晶溶解。 對用以對再結晶用被處理液進行調製之水或硼酸水溶液 之添加S並無特別限定，只要根據硼酸結晶之量等而適當 設定即可。又，對加熱溫度亦無特別限定，只要為可將硼 酸結晶溶解之溫度即可，但較佳為5〇<t〜1〇(rc，進而較佳 · 為 7〇°C 〜80°C。 接著，將再結晶用被處理液冷卻至3(rc以上且小於 5〇°C，從而使硼酸結晶再析出。即，藉由利用晶析裝置 (結晶罐）之冷卻晶析，使硼酸結晶再析出。再結晶用被處 理液之冷卻前之溫度與冷卻後之溫度之差為1〇β(：以上為 162544.doc -28- 201235300 且較佳為2 0 C以上。特佳為3 0 °C以上。錯由使該溫度差 變大，可提高再結晶處理中之硼酸結晶之回收率。 冷卻溫度範圍之限定原因與之前之晶析時相同。又，因 與之前相同之原因，利用冷卻之硼酸結晶之再析出較佳為 於與之前相同之減壓下進行。 以此方式’於藉由冷卻晶析而使硼酸之結晶再析出後， 與上述相同地藉由公知之方法，利用回收裝置（離心分離 機）再次自包含硼酸結晶之水溶液分離硼酸結晶，從而回 收經再結晶處理之蝴酸結晶。 藉由利用該再結晶處理之純化而獲得之硼酸結晶係鹼金 屬化合物等雜質進一步較少、且更高純度之硼酸結晶。 此處’於在該再結晶處理中’再次對硼酸結晶進行分離 後之渡液（以下’稱為再結晶後之濾液）中，亦包含未析出 之硼酸。 因此，如圖1或圖2所示，該再結晶後之濾液亦與上述硼 酸結晶分離後之濾液相同地，較佳為，藉由送液裝置，向 包含排水及固形排出物中之至少一者之被處理液進給至少 一部分’從而再利用作上述被處理液之原料（以下，亦稱 為向上述被處理液添加濾液）。藉此，可更提高自被處理 液之硼酸之回收或再結晶處理中之回收率。 又，此時，亦與之前相同地，亦可向該濾液中添加/混 合固形排出物而添加加入至被處理液中（或者亦可作為被 處理液）。 較佳為，將對上述再析出之硼酸結晶進行分離後之濾液 162544.doc •29· 201235300 之5〜100質量％、較佳為1〇〜75質量％、更佳為15〜5〇質量％ 添加至進行上述濃縮及pH值調整前之被處理液中，又，較 佳為將該濾液之〇〜95質量°/〇、較佳為25〜90質量％、更佳為 50〜85質量％添加至上述再結晶用被處理液中。 此處，於該再結晶後之濾液中，亦包含鹼金屬化合物等 雜質。然而，再結晶後之濾液中所包含之雜質係附著或者 混入於藉由一次晶析而分離之硼酸結晶中之雜質，就量之 方面而言為微量。 因此，A了提高姻酸之回收率，再結晶後之濾液再利用 作上述被處理液之原料，且儘可能較多地添加至被處理液 中之情形有利，特佳為將其總量添加至被處理液中而再利 用0 藉由本發明之回收方法獲得之硼酸中之鹼金屬含量（換 算為驗金屬原子之量）較佳為〇.5質量％以下，更佳為刪 PPm以下^進而較佳為5GQpp喊下^於本發明之回收方法 中’對再結晶處理前之硼酸而言，.可將鹼金屬含量設為 〇·5質量％以下。又，藉由進 人冉結日日處理，可將鹼金 屬έ量設為500 ppm以下。 本發明之排水及固形排出物中之任-者均較佳為自使自 硼矽酸玻璃之製造步驟排出也 卜虱與鹼性之鹼金屬化合物 水/谷液接觸之排氣處理步驟 ^驟排出的排水或固形排出物^ 作為硼矽酸玻璃，較佳為 之氧化物)較少、或實質上二屬成刀(鈉或卸等驗金屬 頁#上不包含鹼金屬成分之(即，益鹼 之）硼矽酸玻璃。 …驗 162544.doc 201235300 作為硼料玻璃，以氧化物基準之f量百分率表示，較 佳為下述組成⑴進而⑺之脅酸玻璃 '然而，下述r表示 鹼金屬…，亦可少量(較佳為以總量計3質量％以下， 更佳為2質量％以下’進而較佳為巧量％以下）含有除下述 外之金屬氧化物（Fe2〇3、Sn〇2等）、非金屬氧化物（硫氧化 物（S03)等）、鹵（C卜F)等。Pa ~ 70000 Pa into the pole. : Fishing ... The temperature of the heated aqueous solution after concentration from butyl is the same as the temperature of the heated liquid to be treated ‘preferably 5 〇. . ~ (10) It is particularly good 7 (TC ~ 80 〇 C. · · · In the first aspect, it is preferred that in the case of concentration under any condition, it will not be dissolved by concentration. Further, in the second aspect, when considering the burden on the device, the alkali metal salt precipitated with respect to the concentrated liquid is preferably not more than 1% by mass. In the case of the second aspect, 'by concentration The speed of the front end of the impeller of the circulation pump of the device is adjusted, and the particle size of the precipitated Na salt is controlled' and in the removal step, the Na salt is selectively removed. Specifically, the 5' will cycle the front end of the impeller For example, m/sec, the particle size of the vaporized sodium and sodium sulfate as the precipitated (10) salt is set to H) from 0 to 300. At this time, the particle size of the side acid crystal which is not expected to be precipitated is 20 to 50 μm, and the Na salt as an impurity can be separated from the concentrated liquid containing boric acid by crushing + # „ μ hunting by a subsequent cyclone. Furthermore, as a solid-liquid separation device, it is not limited to a cyclone, and it is also possible to use a separation of large-size crystals using a horizontal continuous centrifugal separator or a classification using a fluidized bed, or a batch-type sedimentation separation method. In the second sample, 'here', before the concentration step, the pH adjustment step of adding acid to the liquid to be treated is performed, so that the test metal borate in the liquid to be treated is converted into the stone salt and the metal salt in advance. After concentration, it also contains the alkali metal salt produced by the conversion of 162544.doc •20-201235300, and in the concentration step, the alkali metal salt crystal can be grown, thereby effectively removing the alkali metal salt in the removal step. In the case of the second aspect, the liquid to be treated which removes the crystal of the Na salt as an impurity by the cyclone is introduced into the crystallization solution tank as a crystallization stock solution. Dilute water with dilution The liquid to be treated (referred to as a dilution step). Thus, the treated liquid is diluted by the dilution water, so that in the subsequent crystallization step, precipitation of impurities other than boric acid crystals can be suppressed. Further, in the present invention In the recycling method, as described above, the process of "concentration of the pH of the liquid to be treated - concentration" (hereinafter referred to as embodiment 1) as shown in FIG. 1 or FIG. 2 is not performed. In other embodiments, the first embodiment and the second embodiment may be used as a liquid to be treated after heating the liquid to be treated to 5 〇t or more (however, as described above) The heating is not required to be concentrated to concentrate the treated liquid (in the case of the second aspect, after the concentration of the Na salt as an impurity is precipitated, the treated liquid of the heart salt crystal is removed by a cyclone In a state of 50 t or more, an acid such as sulfuric acid is added to adjust the pH, and the pH is adjusted to be less than 4, preferably 3.5 or less, more preferably less than 3, and still preferably 1 3 of the concentrated pH. Adjusted liquid to be treated (hereinafter, referred to as an implementation form) State 2). At this time, for the same reason as before, the concentration of the solid solution of the concentrated liquid to be treated is preferably 15% by mass or more, and is preferably 30% by mass. In the first embodiment, in the first embodiment, the highly acidic liquid to be treated after adjusting the pH by adding sulfuric acid is heated and concentrated by the concentration device. Therefore, the concentrating device needs to use a material which is difficult to corrode. On the other hand, in the second embodiment, since the pH adjustment step is performed after the concentration step of the concentrating device, the concentrating device does not need to use a high-priced material as compared with the first embodiment, and the cost can be reduced. Other embodiments of the second aspect include the following embodiments. (Embodiment 3 of the second aspect) In the second embodiment of the second aspect, the pH adjustment step is provided between the removal step and the crystallization step. However, in this case, there is a case where the removal step is performed. The latter liquid to be treated (corresponding to a saturated solution of an alkali metal salt) is added with the alkali metal salt which is produced by the conversion of the alkali metal borate by pH adjustment, and crystals of the alkali metal salt are regenerated. In this case, there is a sub-Sita shape: the total amount of the metal salt crystal system is supplied to the crystallization solution tank, so that the dilution is used in order to mix the crystal of the alkali metal salt into the crystallization step: . #此' There is a case where the concentration of boronium in the diluted crystallization solution is also lowered, and the amount of boric acid crystals precipitated in the crystallization step is decreased. In this case, as a form different from the second embodiment, i and 2, a pH adjustment (not shown) β may be provided between the concentration step and the removal step in the embodiment. Removal (4) Removal of at least a portion of the date of the metal salt by the enthalpy value, thereby reducing the dilution of the step between the removal step and the decanting step. I62544.doc •22· 201235300 dilution The amount of water can be used to recover the weight of boric acid recovered by the crystallization step. However, in the case of the name, the removal step is carried out in a state where the pH is low, and the resistance is reduced in the removal step. In the case of a burden of inertia, it is preferred to set a pH adjustment step between the removal step and the crystallization step. Further, the alkali precipitated by the addition of sulfuric acid is an orphan, and the mouth is prone to become microscopic. Crystallization, when the day of the separation of the alkali 厶 金属 丽 藉 藉 藉 藉 藉 藉 藉 藉 厶 厶 厶 厶 厶 厶 厶 厶 厶 厶 厶 厶 厶 碱 碱 碱 碱 碱 碱 碱 碱 碱 碱 碱 碱 碱 碱 碱 碱It is preferred to add sulfuric acid before the concentration step. Embodiment 4 of the second aspect 4) Before the process of the shrinking step, the pH value is adjusted by the metal in the liquid to be treated, at least partially converted into boric acid and metal salt (preferably yang 4 to 6). 'More preferably 忡4 to 55, further preferably yang 4 to 5), and further, pH adjustment may be carried out in order to increase the purity of boric acid after the removal step (preferably less than PH4, more preferably pH i~) 3) (not shown). In this embodiment, the positive value of the liquid treated by the concentrating device is relatively high, so that the use of a material having a high price is suppressed, (9) the cost can be reduced, and before the concentration step, At least a part of the metal sulphonate is converted into 2, whereby the alkali metal salt produced along with this grows into a particle size suitable for removal by the step of shrinking, so that it can be effectively removed by the removing step, As a result, the amount of dilution water is suppressed, so that the amount of boric acid crystals precipitated by the crystallization step can be increased. Next, the pH-adjusted treated liquid (preferably concentrated and pH-adjusted is treated) Liquid) is cooled to a certain temperature to make boron The acid crystals are precipitated, that is, the crystallized acid crystals are precipitated by a crystallization apparatus (crystallization tank) by sa precipitation (cooling crystallization) caused by so-called cooling 162544.doc •23·201235300. The boric acid crystal is precipitated as a crucible in which the solubility of the boric acid crystal is lowered by the cooling operation, and the temperature at the end of the cooling operation is referred to as a cooling temperature. In the present invention, by using the crystal The boric acid can be selectively recovered from the liquid to be treated containing the boron compound or the alkali metal compound. Further, the boric acid can be selectively recovered by crystallization, so that the exhaust gas containing the sulfur component can be purified. Boric acid is recovered from the by-product drainage or solid effluent. Further, as described above, 'the pH of the heated aqueous solution is adjusted by acid, and the boric acid crystals are precipitated by crystallization in the cold portion', whereby the boric acid crystal grains or grains are formed. The control of the path becomes easy. Further, the purity of the recovered boric acid crystals can be improved. In particular, in the case of the second aspect, the liquid to be treated is concentrated to precipitate and remove the alkali metal salt as an impurity before cooling and crystallization, so that the liquid to be treated having a higher concentration of the alkali metal salt is used. It is also possible to recover boric acid of higher purity. In addition, as shown in the patent document 3, even if the liquid to be treated containing boric acid (boron compound) is cooled, and the pH is adjusted to a specific acidity by adding sulfuric acid or the like, the crystal of boric acid can be crystallized. The boric acid is recovered by precipitation. However, in this method, since the crystal of boric acid is precipitated instantaneously by the adjustment of the pH value, it is easy to take impurities such as Na salt into the acid crystal, and to adhere to the Na which adheres to the crystal surface due to the crystal of the product. Since the amount of water such as a salt is increased, when a variety of compounds are present in the liquid to be treated, high-purity boric acid crystals cannot be obtained. 162544.doc •24- 201235300 In addition, this treatment sequence precipitates boric acid crystals instantaneously, resulting in poor deformation of the shape of boric acid crystals. The cooling temperature is not particularly limited, but is preferably 3 〇 β (: or more and less than a thief. When the cooling temperature is 50 〇 c or more, the side acid crystals are not sufficiently precipitated, and the recovery rate is deteriorated. In the case where the cooling s degree is less than 3 (the rc is obtained, the crystal of the metal compound such as sodium sulfate is precipitated as a mixed crystal, and the difference between the temperature of the liquid to be treated and the cooling temperature before cooling is It is preferably HTC or more, preferably 2 〇t or more. Particularly preferably, it is a pit or more. By increasing the temperature difference, the recovery rate of boric acid crystals can be increased. Thereby, the mixing of impurities can be suppressed to a minimum. The recovery rate of the acid-removing crystals can be further improved. Further, the precipitation of the acid-accepting crystals caused by the cooling of the treated liquid by the cation (four) is preferably carried out under reduced pressure by cooling under reduced pressure. The precipitation of boric acid crystals can be inhibited from the rust skin on the heat transfer surface when the casing cooling method is used, so that the maintenance of the device becomes easy, and the boric acid can be improved by reducing the loss of boric acid crystals. Recovery rate In addition, the height of the house power at this time is not particularly limited, but at the start of cooling, the pressure is preferably reduced from 10,000 Pa to 70,000 Pa to 20,000 Pa to 6 G_Pa, and at the end of cooling. Preferably, it is carried out at a pressure of 1 〇〇〇 Pa 〜 15 _ Pa, and more preferably at a pressure of 2 kPa. The crystallization of the acid is precipitated by cooling the liquid to be treated adjusted by the p Η value. Doc •25· 201235300 After the release, in the recovery step, the precipitated crystals are separated from the aqueous solution by a recovery device (centrifugal separator) to recover the crystals of boric acid. At this time, the temperature of the aqueous solution containing the crystals is preferably maintained. The separation operation is carried out at the above-mentioned cooling temperature, preferably 30 C or more and less than 50 ° C. The method for separating the boric acid crystal is not particularly limited, and various kinds of solid components for separating solid components from liquid can be used by filtration, centrifugation, sedimentation, and the like. Here, the filtrate obtained by separating the boric acid crystals contains boric acid which is not precipitated. Therefore, it is preferable that at least one of the drain and the solid discharge is contained by the liquid supply means. The liquid to be treated is fed to the filtrate to be reused (hereinafter, also referred to as adding a filtrate to the liquid to be treated) as a raw material of the liquid to be treated. That is, preferably, the filtrate is used as the above-mentioned liquid discharge or solid discharge. a dilution water or the like of the material. For example, a mixture of the solid waste collected by the filter bag and the filtrate may be added to the liquid to be treated (the bite is used as a liquid to be treated). It is necessary to add water to the mixture of the solid waste and the liquid to be used as the liquid to be treated. Thus, the recovery rate of boric acid from the above-mentioned liquid discharge or solid waste can be further mentioned. Here, the separation of boric acid crystals is initially performed. The remaining sputum contains not only a large amount of boric acid but also impurities. Therefore, if the filtrate is used in a large amount in the liquid to be treated, the impurities are concentrated and the liquid is treated. The impurity concentration becomes a high concentration, so that it cannot be properly handled. Therefore, it is preferable to add the filtrate to be reused in the liquid to be treated, please 162544.doc -26- 201235300 = two: minutes. Specifically, the whole filtrate obtained by separating the filtrate added to the liquid to be treated with respect to the boron boron crystals is preferably made of 5 Å by mass of '90% by mass. Thereby, it is possible to prevent adverse effects due to an increase in impurities in the liquid to be treated, and it is preferable to achieve an increase in recovery of acid scavenging. In the second aspect, the Na salt containing T as an impurity in the liquid to be treated is concentrated and precipitated by the concentrating device i, and is removed by a cyclone as a wire device, so that the concentration of the metal salt in the test is high. When the liquid to be treated is concentrated, the liquid of the alkali metal can be hardly obtained to obtain the liquid after the shrinkage. Therefore, the sputum added to the liquid to be treated and reused is at least a part of the liquid, preferably all. Thereby, the recovery of boric acid can be preferably improved. In the case of the first sample and the second aspect, the portion of the treated water after the recovery of the boric acid crystals is discarded, and the residue is returned to the above-mentioned addition step because the amount of the treated water is adjusted. When the concentration of the metal salt to be treated is high, and the load is applied in the concentration step or the removal step, the amount of waste of the treated water is increased, so that the concentration step or the removal step can be facilitated. On the other hand, when the load of the concentration step or the removal step is not large, the amount of waste of the treated water is reduced, and the recovery rate of the shed acid can be improved. As described above, the boric acid crystal recovered by the recovery method of the present invention is sufficiently high in purity, and can be directly used as a raw material of borosilicate glass. However, depending on the use and the like, there is also a case where the recovered boric acid crystals are not sufficiently 'monthly washed, and the purity of the boric acid crystals does not satisfy the desired value. In this case, the boric acid crystals recovered from 162544.doc •27-201235300 can also be cleaned by an aqueous solution of boric acid or water which does not contain an alkali metal component. Further, the cleaning of the boric acid crystals may be carried out by a known method. In addition, the boric acid aqueous solution which does not contain an alkali metal component does not contain an alkali metal compound, and does not contain a boron compound containing an alkali metal atom, such as sodium borate, a compound containing an alkali metal atom other than these compounds, and a base. An aqueous solution of boric acid such as a metal ion. Further, depending on the use, etc., the purity of the recovered boric acid crystals may not be sufficiently high. In this case, it is preferred to further increase the purity of the boric acid crystal by performing recrystallization (recrystallization treatment). Further, if necessary, the recrystallization treatment may be carried out twice or more, but usually, a sufficiently high-purity boric acid crystal can be obtained by recrystallization treatment. As shown in FIG. 1 or FIG. 2, in the recrystallization treatment, water (or an aqueous solution of boric acid which does not contain an alkali metal component, or an aqueous solution of boric acid which is a filtrate after recrystallization as described below) is added to the recovered boric acid crystal, and the following, The so-called boric acid aqueous solution can be used as a liquid to be treated for recrystallization, and the boric acid crystals are dissolved by heating by a heating and dissolving device. The addition S of water or a boric acid aqueous solution to prepare a liquid to be treated for recrystallization is not particularly limited, and may be appropriately set according to the amount of boric acid crystal or the like. Further, the heating temperature is not particularly limited as long as it is a temperature at which boric acid crystals can be dissolved, but preferably 5 〇 < t 〜 1 〇 (rc, further preferably 7 〇 ° C to 80 ° C Next, the recrystallization reaction liquid is cooled to 3 (rc or more and less than 5 〇 ° C to recrystallize the boric acid crystals. That is, the boric acid is crystallized by cooling crystallization by a crystallization apparatus (crystallization tank). Further, the difference between the temperature before cooling of the liquid to be treated for recrystallization and the temperature after cooling is 1 〇β (: 162544.doc -28 - 201235300 and preferably 2 0 C or more. Particularly preferably 3 0 The above-mentioned temperature difference becomes large, and the recovery rate of the boric acid crystal in the recrystallization treatment can be improved. The limitation of the cooling temperature range is the same as that in the previous crystallization. Further, for the same reason as before, the use The re-precipitation of the cooled boric acid crystals is preferably carried out under the same reduced pressure as before. In this manner, after the crystallization of boric acid is reprecipitated by cooling crystallization, the same method as described above is utilized. The recovery unit (centrifugal separator) again contains boric acid crystals The boric acid crystals are separated by an aqueous solution to recover the crystallized crystals which have been subjected to the recrystallization treatment. The boric acid crystals obtained by the purification by the recrystallization treatment are further less and have higher purity boric acid crystals. The ferrite which is separated from the boric acid crystal in the recrystallization treatment (hereinafter referred to as the filtrate after recrystallization) also contains undeposited boric acid. Therefore, as shown in FIG. 1 or FIG. 2, The recrystallized filtrate is also fed to the treated liquid containing at least one of the drain and the solid effluent by the liquid feeding device in the same manner as the filtrate after the boric acid crystal separation. Further, it is used as a raw material of the liquid to be treated (hereinafter, also referred to as adding a filtrate to the liquid to be treated), whereby the recovery rate from the recovery of boric acid or the recrystallization treatment of the liquid to be treated can be further improved. In the same manner as before, the solid waste may be added/mixed to the filtrate and added to the liquid to be treated (or may be used as the liquid to be treated). 5 to 100% by mass, preferably 1 to 75% by mass, more preferably 15 to 5% by mass, of the filtrate 162544.doc •29·201235300 after the above-mentioned re-precipitated boric acid crystals are added. In the liquid to be treated before concentration and pH adjustment, it is preferable to add 滤液 to 95 mass%/〇, preferably 25 to 90% by mass, more preferably 50 to 85% by mass, to the above-mentioned filtrate. In the liquid to be treated for crystallization, impurities such as an alkali metal compound are also contained in the filtrate after the recrystallization. However, the impurities contained in the filtrate after recrystallization are adhered or mixed by one crystallization. The impurities in the separated boric acid crystals are in a small amount in terms of the amount. Therefore, A improves the recovery rate of the in-situ acid, and the recrystallized filtrate is reused as a raw material of the above-mentioned treated liquid, and is added as much as possible. It is advantageous in the case of the liquid to be treated, and it is particularly preferable to add the total amount to the liquid to be treated and reuse 0. The alkali metal content of the boric acid obtained by the recovery method of the present invention (converted to the amount of the metal atom to be inspected)佳为〇.5质量% or less More preferably, the amount of the alkali metal is 5% by mass or less, and the amount of the alkali metal is 5% by mass or less. Further, the amount of alkali metal strontium can be set to 500 ppm or less by day-to-day treatment. Any of the drainage and solid effluent of the present invention is preferably an exhaust gas treatment step which is brought into contact with the alkaline alkali metal compound water/glutle solution from the production step of the borosilicate glass. The discharged drainage or solid discharge ^ as a borosilicate glass, preferably an oxide) is less, or substantially two is a knife (sodium or unloaded metal page # does not contain an alkali metal component (ie, Boric acid glass. ICP 544544.doc 201235300 As a boron glass, expressed as a percentage of the oxide based on the amount of f, preferably the following composition (1) and (7) the sour acid glass 'however, the following r represents The alkali metal may be a small amount (preferably, the total amount is 3% by mass or less, more preferably 2% by mass or less, further preferably less than 5% by weight), and the metal oxide (Fe2〇3) other than the following is contained. , Sn 〇 2, etc.), non-metal oxides (sulfur oxide (S03), etc.), halogen (C Bu F), and the like.
SiO2:40〜85 質量 ％、Al2〇3:1〜22 質量 ％、B2〇3:2〜2〇 質量 〇/〇、MgO:0〜8 質量 ％、Ca〇:〇〜14 5 質量 ％、Sr〇 〇〜24 質量 %、BaO:0〜30質量 ％、R2〇:〇〜1〇 質量。 含有 Si02.58 〜66質量。/。、a12〇3:15 〜22 質量％、b2〇3:5〜12 質量 ％、MgO:〇〜8 質量。/〇、CaO:〇〜9 質量。/〇、SrO:3〜12.5 質 量 ％、BaChO〜2 質量 〇/〇、Mg〇+CaO+SrO+BaO:9〜18 質量。/〇之 無驗玻璃…（2)。 耐熱容器或理化學用器具等中所使用之包含鹼金屬成分 之硼矽酸玻璃通常係於上述組成（1)中，鹼金屬成分（R2〇) 含有率為2~10質量％左右之硼矽酸玻璃。 另一方面，作為用作液晶顯示元件之基板之硼矽酸玻 璃，可使用驗金屬成分較少之硼矽酸玻璃，更佳為使用稱 為無驗删♦酸玻璃之驗金屬成分極其少之硼石夕酸玻璃。稱 為無鹼硼矽酸玻璃（無鹼玻璃）之硼矽酸玻璃係於上述組成 (1)中，驗金屬成分（R2〇)含有率為0 · 1質量％以下之顺石夕酸 玻璃，且係於上述組成（2)中，除不可避免地包含作雜質 外，實質不含有驗金屬氧化物之（例如驗金屬氧化物為〇. 1 質量％以下）硼矽酸玻璃。 162544.doc •31 · 201235300 作為本發明中之排水或固形排出物之排出源之硼矽酸玻 璃的製造步驟中之硼矽酸玻璃較佳為上述鹼金屬成分較少 之（即，小於2質量。/〇硼矽酸玻璃，更佳為鹼金屬成分 質量％以下之硼矽酸玻璃。特佳為稱為上述無鹼硼矽酸玻 璃之驗金屬成分極其少之（即，為〇丨質量％以下）硼矽酸玻 璃。 上述硼矽酸玻璃中之鹼金屬成分之量成為對藉由本發明 而回收之硼酸之使用前進行制約之必要條件β根據作為所 回收之硼酸中之雜質之鹼金屬成分的量，可用作硼矽酸玻 璃原料之硼矽酸玻璃之種類受到制約。若所回收之硼酸中 之驗金屬成分之量較多，則存在如下之虞：該硼酸變得難 以用作鹼金屬成分較少之硼矽酸玻璃之原料，特別是無法 用作無鹼硼矽酸玻璃之原料。 因此，如上所述，藉由本發明之回收方法而獲得之硼酸 中之鹼金屬含量（換算成鹼金屬原子之量）較佳為〇 5質量％ 以下，更佳為1000 ppm以下。進而較佳為500 ppm以下。 此種純度較高之硼酸可用作無鹼硼矽酸玻璃之原料。 因此，例如，可將自藉由自無鹼硼矽酸玻璃之製造步驟 排出之排氣之處理而副生的排液或固形排出物回收之硼酸 再利用作該無鹼硼矽酸玻璃（鹼金屬含量小於2質量％之硼 矽酸玻璃）之原料。 以上，詳細地對本發明之硼酸之回收方法進行了說明， 但本發明並不限定於上述例，當然亦可於不脫離本發明之 主旨之範圍内，進行各種改良或變更。 162544.doc -32· 201235300 實施例 、下列舉本發明之具體實施例而更詳細地對本發明進 y、月再者，本發明當然不限定於以下之實施例。 <第1態樣> [實施例1 ] 藉由圖3所示之淨化流程，對自用以製造删石夕酸玻璃之 玻璃溶融爐排出之排氣進行淨化。於該淨化流程中，向自 文丘裏霧化器排出之排水中’溶解藉由過濾袋捕集之固形 排出物，藉此調製出成為處理對象之液體（以下，將該液 體稱為母液體）。 將該母液體取出1000 mL，首先，加熱至乃它而作為加 熱水溶液。接著，向加熱水溶液添加硫酸，將？11值調整為 2 ° 接著’以75 C將該經pH值調整之加熱水溶液濃縮至即將 析出固體為止。於該經濃縮之加熱水溶液（經pH值調整） 中’分別含有硼32 g/L、鈉60 g/L、.硫酸離子61 g/L。 將經濃縮之加熱水溶液（經pH值調整）自75。(：冷卻至35°C 為止，從而使硼酸結晶析出。 以3 5t對已使硼酸結晶析出之被處理液進行過濾，從而 回收硼酸結晶。 藉由離子層析法對所回收之硼酸之純度進行測定，結果 所回收之硼酸結晶中之雜質濃度中，硫酸離子為0.7質量 %，納為0.4質量％。 [實施例2] 162544.doc -33- 201235300 向實施例1中所回收之硼酸結晶添加75它之水溶液成為 飽和水溶液之量的水，而作為再結晶用被處理液。將該再 結晶用被處理液加熱至75°c而將硼酸結晶之總量溶解，從 而製造飽和水溶液。 接著’將上述75。(：之飽和水溶液冷卻至35它為止，從而 使硼酸結晶再析出。 以35°C對已使硼酸結晶再析出之水溶液進行過濾，從而 回收硼酸結晶。 與實施例1相同地對所回收之硼酸之純度進行測定，結 果硼酸結晶中之雜質、鈉離子、硫酸離子、氣離子、氟離 子均為100 ppm以下。 [比較例1] 除調整對加熱水溶液進行pH值調整之硫酸之添加量，將 經pH值調整之加熱水溶液之pH值設為4外，與實施例1相 同地回收硼酸結晶。 與實施例1相同地對所回收之硼酸結晶之純度進行測 定’結果所回收之硼酸結晶中之雜質濃度中，硫酸離子為 1.7質量％，鈉為1.0質量％。 [比較例2] 將與實施例1相同之母液體取出1 〇〇〇 mL，加熱至75°C為 止。將該加熱水溶液冷卻至35°C為止而使鈉之硼酸鹽析 出’此後向經冷卻之水溶液添加硫酸，將pH值調整為2， 轉化成硼酸結晶。 與實施例1相同地過濾、回收所析出之棚酸結晶。 162544.doc -34- 201235300 之純度進行測 % ’鈉為1.8質 與實施例1相同地對所回收之 ’《人、、，〇 gg 定’結果雜質濃度中，硫酸離子為2.4質量 量％。 根據以上之結果，本發明之效果明確。 <第2態樣> [實施例3 ] 藉由圖3所示之淨化流程，對自用以製造㈣酸破璃之 玻璃溶解爐排出之職進行淨化^淨化流程中，將自 文丘裏霧化器排出之排水用作原液。於第2態樣中，在被 處理液中，含有多量之驗金屬鹽。為了再現本流程中之被 處理液’以獲得提高了鹼金屬鹽濃度之被處理液為目的， 調製向自洗滌II排出之原液添加有硫酸納' 氯化納之液體 (以下’將該液體稱為母液體）。 將该母液體取出1440 mL，添加硫酸而將？1^值調整為 2。 接著，以75t對該經pH值調整之液體進行濃縮，使固形 成分析出。接著，藉由使用濾紙進行過濾而分離成固形成 分與上清液。固形成分為69 g。再者，濃縮時之冷凝水為 43 0 g 〇 藉由離子層析法對該固形成分進行分析，結果鈉含有 36.2質量％ ’硫酸離子含有44 4質量％，氯化物離子含有 1 7.8質量。/。，硼含有〇.9質量％。因此，可考慮為該固形成 分主要為硫酸鈉與氯化鈉之混晶。SiO2: 40 to 85 mass%, Al2〇3:1 to 22% by mass, B2〇3: 2 to 2〇, mass 〇/〇, MgO: 0 to 8% by mass, Ca〇: 〇~14 5 mass%, Sr 〇〇~24% by mass, BaO: 0 to 30% by mass, R2〇: 〇~1〇. Contains Si02.58 ~ 66 mass. /. , a12〇3:15~22% by mass, b2〇3:5~12% by mass, MgO: 〇~8 mass. /〇, CaO: 〇~9 quality. /〇, SrO: 3~12.5 Mass %, BaChO~2 Mass 〇/〇, Mg〇+CaO+SrO+BaO: 9~18 mass. /〇之无无玻璃...(2). The borosilicate glass containing an alkali metal component used in a heat-resistant container or a chemical-chemical device or the like is usually in the above composition (1), and the alkali metal component (R2〇) has a boron bismuth content of about 2 to 10% by mass. Acid glass. On the other hand, as the borosilicate glass used as the substrate of the liquid crystal display element, a borosilicate glass having a small metal component can be used, and it is more preferable to use a metal component called a non-destructive acid glass. Boric acid glass. A boron phthalic acid glass called an alkali-free borosilicate glass (alkali-free glass) is in the above composition (1), and the metal component (R2 〇) has a content of 0. 1% by mass or less. Further, in the above composition (2), in addition to inevitably containing impurities, the borosilicate glass is substantially not contained in the metal oxide (for example, the metal oxide is 0.1% by mass or less). 162544.doc •31 · 201235300 The borosilicate glass in the production step of the borosilicate glass as the discharge source of the drainage or solid effluent in the present invention preferably has a small amount of the above alkali metal component (ie, less than 2 mass) 〇 〇 〇 矽 矽 , , , , , , , 碱 碱 碱 碱 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The following is a boron bismuth silicate glass. The amount of the alkali metal component in the borosilicate glass is a necessary condition for restricting the use of boric acid recovered by the present invention, and is based on an alkali metal component as an impurity in the recovered boric acid. The amount of the borosilicate glass which can be used as the raw material of the borosilicate glass is restricted. If the amount of the metal component in the recovered boric acid is large, there is a possibility that the boric acid becomes difficult to be used as a base. A raw material of a boric acid glass having a small metal component, in particular, cannot be used as a raw material of an alkali-free borosilicate glass. Therefore, as described above, an alkali metal in boric acid obtained by the recovery method of the present invention The amount (calculated as the amount of the alkali metal atom) is preferably 5% by mass or less, more preferably 1,000 ppm or less, still more preferably 500 ppm or less. Such a higher purity boric acid can be used as the alkali-free borosilicate glass. Therefore, for example, boric acid recovered from the discharge or solid discharge recovered by the treatment of the exhaust gas discharged from the production process of the alkali-free borosilicate glass can be reused as the alkali-free borosilicate. The raw material of the glass (boric acid glass having an alkali metal content of less than 2% by mass). The method for recovering boric acid of the present invention has been described in detail above, but the present invention is not limited to the above examples, and it is of course possible not to deviate from the present invention. Various modifications and changes are possible within the scope of the gist of the invention. 162544.doc -32·201235300 Embodiments The present invention will be described in more detail with reference to the specific embodiments of the present invention, and the present invention is of course not limited thereto. The following examples: <First aspect> [Example 1] The exhaust gas discharged from the glass melting furnace for producing dendroxic acid glass was purified by the purification flow shown in Fig. 3. Purification process In the drain discharged from the venturi atomizer, 'dissolving the solid discharge collected by the filter bag, thereby preparing a liquid to be treated (hereinafter, this liquid is referred to as a mother liquid). Take 1000 mL, first, heat it to heat as an aqueous solution. Next, add sulfuric acid to the heated aqueous solution to adjust the value of ?11 to 2 °. Then 'concentrate the pH-adjusted heated aqueous solution at 75 C to the solid to be precipitated. So far, the concentrated heated aqueous solution (adjusted by pH) contains boron 32 g/L, sodium 60 g/L, and sulfate ion 61 g/L, respectively. The concentrated heated aqueous solution (adjusted by pH) ) From 75. (: Cooled to 35 ° C to precipitate boric acid crystals. The treated liquid from which boric acid crystals have been precipitated is filtered at 35 Torr to recover boric acid crystals. The purity of the recovered boric acid was measured by ion chromatography. As a result, among the impurity concentrations in the boric acid crystal recovered, the sulfate ion was 0.7% by mass and the sodium was 0.4% by mass. [Example 2] 162544.doc -33-201235300 To the boric acid crystal recovered in Example 1, 75 aqueous solution of the aqueous solution was added as a saturated aqueous solution to obtain a liquid to be treated for recrystallization. This recrystallization was heated to 75 ° C with the liquid to be treated to dissolve the total amount of boric acid crystals, thereby producing a saturated aqueous solution. Then 'will be 75 above. (The saturated aqueous solution was cooled to 35°, and the boric acid crystals were reprecipitated. The aqueous solution in which the boric acid crystals were reprecipitated was filtered at 35 ° C to recover the boric acid crystals. The boric acid recovered was the same as in Example 1. When the purity was measured, the impurities, sodium ions, sulfate ions, gas ions, and fluoride ions in the boric acid crystal were all 100 ppm or less. [Comparative Example 1] In addition to adjusting the amount of sulfuric acid added to adjust the pH of the heated aqueous solution, The pH of the heated aqueous solution adjusted to pH was set to 4, and the boric acid crystal was recovered in the same manner as in Example 1. The purity of the recovered boric acid crystal was measured in the same manner as in Example 1 in the boric acid crystal recovered as a result. In the impurity concentration, the sulfate ion was 1.7% by mass, and the sodium was 1.0% by mass. [Comparative Example 2] The same mother liquid as in Example 1 was taken out to 1 mL, and heated to 75 ° C. The heated aqueous solution was cooled. Sulfate of sodium was precipitated until 35 ° C. Thereafter, sulfuric acid was added to the cooled aqueous solution, and the pH was adjusted to 2 to be converted into boric acid crystal. The same procedure as in Example 1 was carried out. The benzene acid crystals precipitated were recovered. 162544.doc -34- 201235300 The purity of the sample was measured. 'Sodium was 1.8. The same as in Example 1, the impurity concentration of the recovered 'human, 〇 定 定 定' results was According to the above results, the effect of the present invention is clear. <Second aspect> [Example 3] In the purification process of the glass dissolution furnace, the drainage discharged from the venturi atomizer is used as a stock solution. In the second aspect, a large amount of metal salt is contained in the liquid to be treated. In the process of the present invention, in order to obtain a liquid to be treated which has an increased alkali metal salt concentration, a liquid in which sodium sulphate sodium chloride is added to the raw liquid discharged from the washing II is prepared (hereinafter, the liquid is referred to as a mother) Liquid). The mother liquid was taken out of 1440 mL, and sulfuric acid was added to adjust the value of ?1 to 2. Next, the pH-adjusted liquid was concentrated at 75 t to analyze the solid formation. Next, by using filter paper. Filtered and separated into solid The composition and the supernatant were solidified into 69 g. Further, the concentration of the condensed water was 43 0 g. The solid component was analyzed by ion chromatography, and the sodium contained 36.2% by mass. 'The sulfate ion contained 44 4 The mass %, the chloride ion contains 17.8 mass%, and the boron contains 〇.9 mass%. Therefore, it is considered that the solid component is mainly a mixed crystal of sodium sulfate and sodium chloride.
於向該上清液添加5 wt%之純水後，自75。(：冷卻至35°C J62544.doc •35- 201235300 為止，從而使硼酸結晶析出。以3 5 °C對已使硼酸結晶析出 之被處理液進行過濾，從而回收硼酸結晶。 藉由離子層析法對所回收之硼酸結晶之純度進行測定， 結果所回收之硼酸結晶中之雜質濃度中，硫酸離子為〇.4 質量％ ’氣化物離子為〇 · 7質量。/〇。 [實施例4] 於向藉由與實施例3相同之操作獲得之上清液添加1 〇 wt0/。之純水後，自75»c冷卻至35<t為止，從而使硼酸結晶 析出。以3 5 C對已使硼酸結晶析出之被處理液進行過濾， 從而回收硼酸結晶。 藉由離子層析法對所回收之硼酸結晶之純度進行測定， 結果所回收之硼酸結晶中之雜質濃度中，硫酸離子為〇4 質量°/〇 ’氣化物離子為〇 8質量0/〇。 [比較例3]After adding 5 wt% of pure water to the supernatant, it was 75. (: Cooling to 35 ° C J62544.doc • 35 - 201235300 to precipitate boric acid crystals. The treated liquid which has been crystallized by boric acid crystallization is filtered at 35 ° C to recover boric acid crystals. The purity of the recovered boric acid crystal was measured by the method, and as a result, among the impurity concentrations in the boric acid crystal recovered, the sulfate ion was 〇.4 mass% 'the vaporization ion was 〇·7 mass. /〇. [Example 4] After obtaining the supernatant liquid by adding 1 〇wt0/ of pure water by the same operation as in Example 3, it was cooled from 75»c to 35 lt. t to precipitate boric acid crystals. The treated liquid which precipitates boric acid crystals is filtered to recover boric acid crystals. The purity of the recovered boric acid crystals is measured by ion chromatography, and as a result, among the impurity concentrations in the boric acid crystals recovered, the sulfate ions are 〇4. The mass ° / 〇 ' vaporization ion is 〇 8 mass 0 / 〇. [Comparative Example 3]
硼酸結晶。 藉由離子層析法對所回收之硼酸結晶之純名 結果所回收之硼酸結晶中之雜質濃度中，硫 之純度進行測定， ^ ’硫酸離子為0.5 質量％，氣化物離子為6 7質量0/〇。Boric acid crystals. The purity of sulfur in the boronic acid crystal recovered from the pure name of the recovered boric acid crystal by ion chromatography was determined, ^ 'sulfate ion was 0.5% by mass, and vaporized ion was 67 mass 0/ Hey.
裡修正或變更。 明進行了說明，但 與精神，而實施各 162544.doc -36- 201235300 本申請案係基於2011年2月22日φ过a T %之曰本專利申請 2011-035896、及 2011年 9月 26 日申請 > 口 + 由<曰本專利申請2011- 209254者，且其内容以參照之形式併入本文。 產業上之可利用性 可自硼矽酸玻璃之製造步驟中排出 坊 ®之排水或固形排出物 等、包含硼化合物與鹼金屬化合物之妯 <徘水或固形排出物， 回收可用作硼矽酸玻璃原料之硼酸。【圖式簡單說明】 圖1係用以對本發明之硼回收方法（第i態樣）之一 說明之流程圖。 圖2係用以對本發明之棚回收方法（第2態 說明之流程圖。 圖3係用以對藉由本發明之爛回收方法進行處 理液之一例進行說明的概念圖。 例進行 例進行 理之被處 162544.doc 37-Corrected or changed. Ming made a description, but with the spirit, and implemented each 162544.doc -36- 201235300 This application is based on February 22, 2011 φ over a T % of this patent application 2011-035896, and September 26, 2011 Japanese Application < </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> </ RTI> <RTIgt; The industrial availability can be derived from the drainage or solid effluent of the diarrhea glass, the borax or the solid effluent containing the boron compound and the alkali metal compound, and the recovery can be used as boron. Boric acid of citric acid glass raw material. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart for explaining one of the boron recovery methods (the i-th aspect) of the present invention. Fig. 2 is a flow chart for explaining a method for recovering a shed according to the present invention. Fig. 3 is a conceptual diagram for explaining an example of a treatment liquid by the rotting recovery method of the present invention. Being at 162544.doc 37-