TW201243109A - Apparatus for electrolyzing sulfuric acid and method for electrolyzing sulfuric acid - Google Patents

Apparatus for electrolyzing sulfuric acid and method for electrolyzing sulfuric acid Download PDF

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TW201243109A
TW201243109A TW101107844A TW101107844A TW201243109A TW 201243109 A TW201243109 A TW 201243109A TW 101107844 A TW101107844 A TW 101107844A TW 101107844 A TW101107844 A TW 101107844A TW 201243109 A TW201243109 A TW 201243109A
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sulfuric acid
anode
electrolysis
cathode
route
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TW101107844A
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Chinese (zh)
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TWI518209B (en
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Hiroki Domon
Kouji Fujii
Junko Kosaka
Masaaki Kato
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Chlorine Eng Corp Ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/28—Per-compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/22—Inorganic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/042—Electrodes formed of a single material
    • C25B11/043—Carbon, e.g. diamond or graphene
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Automation & Control Theory (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Abstract

The present invention relates to an apparatus for producing sulfuric acid that contains a large amount of an oxidizing substance by electrolyzing sulfuric acid, and specifically relates to an apparatus for safely and highly efficiently producing electrolyzed sulfuric acid that contains a large amount of an oxidizing substance by producing diluted sulfuric acid that is controlled in temperature and concentration within an electrolysis apparatus and then electrolyzing the diluted sulfuric acid under temperature-controlled conditions. The present invention provides an apparatus for electrolyzing sulfuric acid, which comprises a positive electrode-side electrolysis unit and a negative electrode-side electrolysis unit, and which is provided with, at least within the positive electrode-side electrolysis unit: a positive electrode-side diluted sulfuric acid generation loop A for diluting concentrated sulfuric acid, which is a supplied starting material, and then adjusting the temperature and the concentration of the thus-diluted sulfuric acid to desired values; and a positive electrode-side electrolyzed sulfuric acid generation loop B for producing electrolyzed sulfuric acid by electrolyzing the diluted sulfuric acid, the temperature and the concentration of which are adjusted to desired values in the loop A, and then adjusting the temperature and the concentration of the thus-produced electrolyzed sulfuric acid to desired values. The present invention also provides a method for electrolyzing sulfuric acid.

Description

201243109 六、發明說明： 【發明所屬之技術領域】 本發月係關於—種藉由將硫酸電解而進行大量含有氧化 ：⑨物質之電解韻之製造的輕f解裝置及硫酸電解方法 者。纟羊細而j ga .. ： 、。關於一種藉由於硫酸電解裝置内生成溫度及 廣度、·主管理之稀釋硫酸，進而，將該溫度及濃度經管理之稀 釋瓜酉夂電解而向效率且安全地生成含有氧化性物質之電解 硫酸的硫酸電解心及硫酸電解方法者。 【先前技術】 先月J作4金屬 < 電解電鍍前處王里劑或触刻劑、半導體元 件中之化予研磨處理/機械研磨處理中之氧化劑、濕式 77析中之有機物之氧化劑、石夕晶圓之清洗劑等各種製造步驟 或仏查V驟中所使用之藥劑，而使用過硫酸。已知該過硫酸 被稱作氧化性物質」，藉由硫酸之電解而生成，已經工業 規模地進行電解製造。 於本發明中，所謂「氧化性物質」，係指過硫酸、過氧單 ^硫酸等過硫酸、過氧化氫，所謂「電解硫酸」，係指含有藉 ,纟將硫酸電解所製造之該等氧化性物質及未反應之硫酸者。 含有於將硫酸電解之裝置中生成之氧化性㈣及未反應 之硫酸的電解硫酸(以下’僅稱作「電解硫酸」）於半導體製 造步驟中’用作賊織者用於污染有機物或污染金屬等之 去除°對於該’it ’ &知氧化性物質濃度越為高濃度去除 101107844 3 201243109 效果越高，對硫酸電料置要求可生成濃度更高地含有氧化 ㈣質之電解硫酸、藉由電解之氧化性物質之生成效率更 南、及生成之氧化性物質之分解性較低。於硫酸電解中，為 了生成高濃度地含魏化性物f之轉魏，使藉由電解之 氧化f生物質之生成效率更高，降低該氧化性物質之分解性， 而要求向硫酸電解裝置中供給調整至所需漢度之低濃度硫 酸。 然而，通常硫酸係作為98%或96%之濃硫酸而銷售，因 此為了向硫酸電解裝置中供給調整過濃度之經稀釋之低濃 度之硫酸(亦稱作稀釋硫酸），需要對工場之藥液供給設備重 新進行專用之蓄積儲罐或供給配管施工，於此情形時，需要 大筆設備成本。又，由於低濃度之硫酸與濃硫酸相比體積較 大’因此與搬送濃硫酸相比，產生藥品之搬送成本亦增大之 問題。 若可於硫酸電解裝置内效率良好地調整硫酸濃度，則一面 最小限度地抑制設備成本、搬送成本等製備稀釋硫酸之成 本’ 一面將低濃度之硫酸電解而高效率地生成氧化性物質的 硫酸電解成為可能《又，若可將構成根據濃硫酸生成稀釋硫 酸之機構與根據稀釋硫酸生成含有氧化性物質之電解硫2 之機構的機器及生產線儘量共用化，則可達成硫酸電解 之小型化及簡易化。 於記載有於電解槽中將硫酸電解而生成過硫酸之專利文 101107844 4 201243109 獻1之段落ooii中，記載有「藉由將用以生成過硫酸之硫 酸之濃度範圍設為2〜11 mol/L之低濃度硫酸，可提高過硫 酉文之生成效率」。 於提出過硫酸供給系統之專利文獻2之段落〇〇26中，記 載有「關於供給至電解反應裝置中之電解液之硫酸濃度之範 圍’藉由設為10〜18 M(mol/L)之低濃度硫酸，可提高過硫 酸之生成效率」。 於專利文獻3之段落0012及段落0018中，記載有「藉由 使用/農度不同之硫酸作為電解液，而提高用以生成電解硫酸 之電流效率，並且效率良好且穩定地生成氧化性物質之方 法」。 然而，於專利文獻1〜3所記載之方法中，雖然揭示有藉 由將低》辰度之硫酸電解而生成變為高效率，但並無關於硫酸 之濃度調整之方法之揭示。 為了製造低濃度之稀釋硫酸，通常，需要將濃硫酸與純水 混合而適當地調整硫酸濃度，但於將硫酸與純水混合時，產 生大量之稀釋熱，而大量產生由爆沸或稀釋熱所引起之蒸氣 或霧。因此，若來自進行硫酸濃度調整之儲罐或設備之排氣 無任何處理便連接至排氣設備或除害設備，則導致硫酸混入 排氣設備或除害設财，因此，具有直接__#或性能 之劣化之問題。 於專利文獻4中’揭示有使用氣液分離手段作為去除由電 101107844 201243109 解反應裝置產生之電解氣體中所含之硫酸的方法。然而，儘 管藉由於裝置内調整硫酸濃度時產生之蒸氣或霧之硫酸較 電解氣體中所含之硫酸多，但關於調整硫酸濃度時產生之蒸 氣及霧之去除並無揭示，關於硫酸濃度調整方法亦無揭示。 於專利文獻5中’具有對用於清洗之硫酸進行再濃縮後， 進行稀釋及冷卻並進行再電解而生成過硫酸之方法之記 載，但由於暫時對以低濃度進行供給之用於清洗之硫酸進行 濃縮，而淨化性不同，而且具有安全性之問題。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2008-66464號公報 [專利文獻2]曰本專利特開2008-111184號公報 [專利文獻3]曰本專利特開2010-34521號公報 [專利文獻4]曰本專利特開2007-262532號公報 [專利文獻5]曰本專利特開2008-244310號公報 【發明内容】 (發明所欲解決之問題） 本發明之目的在於提供一種如下之硫酸電解裝置及硫酸 電解方法：去除將濃硫酸稀釋成低濃度之硫酸時產生之稀釋 熱及電解時產生之熱，調整可高效率地生成氧化性物質之電 解條件’抑制由稀釋熱所引起之霧或蒸氣之產生，進而，亦 將由混入排氣系統之霧或蒸氣所引起之硫酸等之凝結液滴 101107844 6 201243109 自排氣系統中去除，效率更高地電解生成氧化 安全且穩定地運作。 貝 (解決問題之手段） 本發明為了解決上述課題而提供一種硫酸電解裝置】，盆 係具有陽極側電解部2〇與陰極側電解部23而成者’其特徵 在於：至少於陽極側電解部2()内設置有陽極側稀釋硫酸生 成路線A及陽極側電解硫酸生成路線b，該陽極侧稀釋硫 酸生成路線A係稀釋作為供給原料之濃硫酸，並將經稀釋 之稀釋硫酸調整至所需之溫度及濃度，該陽_電解硫酸生 成路線B係將該稀釋硫酸生成路線A中所生成之稀釋硫酸 =解而生成轉俩，且將财狀電解雜調整至所需之 溫歧濃度，上述陽極侧稀釋硫酸生成路線A係依照陽極 诸罐31 極側濃硫酸供給部32與陽極侧冷卻器％之 順序進行配置，利㈣極側旁路配f %賴等連接而形成 路線進而’於雜線A内之任—位置連接可將向路線A 内供給純水之陽極側純水供給配管10，進而，連接用於向 ^述陽極側濃硫酸供給部32供給濃硫酸之陽極側濃硫酸供 ^盲★ 7上述陽極侧電解硫酸生成路線B係利用陽極側 =¼配f 37連接上述陽極側儲罐31與包含由隔膜$形成之 陽：至4、陰極室7之電解槽2中之内部設置有陽極3的陽 極至4而形成路線，將自上述陽極側濃硫酸供給配管w向 陽極側;農硫酸供給部32供給之濃硫酸，係利用自上述陽極 101107844 201243109 側純水供給配管ίο供給之純水稀釋，且將經稀釋之低濃度 之硫酸於在上述路線A内循環之期間調整至所需之溫度及 濃度，而生成調整至所需之溫度及濃度之稀釋硫酸，成 之稀釋硫酸經由構成上述路線B之陽極側循環配管P向上 述電解槽2之陽極室4供給，而於該陽極室4中生成電解硫 酸，且將所生紅電解顧於在上述路線B内循環之期^ 調整至所需之溫度及濃度，而生成調整至所需之溫度及濃度 之電解硫酸。 又本發明之第2解決手段在於提供上述硫酸電解襄置， 其進而於上述陰極侧電解部23之裝置内設置有陰極側稀釋 硫酸生成路、線A’及陰極側電解路、線B，，該陰極側稀釋硫酸 生成路線A ’係稀釋作為供給原料之濃硫酸而製成低濃度之 硫酸’且㈣低|紅硫酸難輯需之溫度及濃度該陰極 側電解路線B，係將該稀釋硫酸生成路線A,中所生成之稀釋 硫酸通人錄極t 7 β騎循環，陰極觸懸酸生成路線 Α’係依照陰極側儲罐38、陰極側濃硫酸供給部％與陰極側 冷卻器41之順序進行配置，利用陰極側旁路配管43將該等 連接而形成路線，進而，於該路線Α，内之任一位置連接可 將向路線Α’内供給純水之陰極側純水供給配管12，進而， 連接用於向上述陰極側濃硫酸供給部39供給濃硫酸之濃硫 酸供給配管29，陰極側電解路線Β，係利用陰極側循環配管 44連接上述陰極側儲罐38與包含由隔膜5形成之陽極室 101107844 8 201243109 之電解#2中之内料置有陰極 Γ 將自陰極侧濃硫酸供給配管柳二二 管Γ 彻自上述陰_純水供給配 路線Α ΓΓ ，將㈣狀⑽度之贼於在上述 整至所翻調整至所需之溫度及濃度，而生成調 由槿成t之度及、4度之轉魏，所生从轉硫酸係經 述路線B'之陰極側循環配管44向電解 室4供仏，狄4_ 、丨右壮 敫…；上述路線㈣循環之期間進行經溫度及濃 又凋之稀釋硫酸之電解。 /本發明之第3解決手段在於提供一種硫酸電解裝置， 其係於上述陽極側儲罐31上部經由陽極氣體出σ配管1〇2 以依序串聯遠^ ^ <方式’連接陽極側氣液分離機構91及陽 極側油務分離n 92，於該陽極㈣液分離機構91及該陽極 側’由霧77離92之各自之底部，具備連通用以排出儲存於 各自之内部之液體的陽極側氣液分離機構91與陽極側油霧 分離11 92之構造之排液手段而成。 又’本發明之第4解決手段在於提供一種硫酸電解裝置， 其係於上述陽極側儲罐31上部經由陽極氣體出口配管ι〇2 以依序串聯連通之方式，連接陽極側氣液分離機構91及陽 極側油霧分離器92,於該陽極側氣液分離機構91及該陽極 側油霧分離器92之各自之底部，具備連通用以排出儲存於 各自之内部之液體的陽極侧氣液分離機構91與陽極側油霧 101107844 9 201243109 分離益92之構造之排液手段，並且進而於上述陰極側儲罐 38上部經由陰極氣體出口配管⑻以依序串聯連通之方 式，連接陰極側氣液分離機構96及陰極側油霧分離器97, 於該陰極側氣液分離機構96及該陰極側油霧分離器Μ之各 自之底部’具備連利轉出儲存於各自之㈣的陰極側氣 液分離機構96與陰極側油霧分離器97之構造之排液手段而 成。 又’本發明之第5解決手段在於提供一種硫酸電解裝置， 其中’於上述陽極㈣霧分離^ 92連財純分解機構 93 〇 又’本發明之第6解決手段在於提供一種硫酸電解裝置， 中於上述陰極側油霧分離器97連接有氫處理機構。 又本發明之第7之解決手段在於提供一種硫酸電解裝 置，其構成為：於上述稀釋硫酸生成路線A中，並列設置 複數個上述陽極側儲罐，於在一個該陽極侧儲罐中蓄積所生 成之含有氧化性物質的電解硫酸後，對閥進行切換後於其他 陽極側儲罐中生成含有特定濃度之氧化性物質的電解硫酸。 又，本發明之第8解決手段在於提供 一種硫酸電解裝置， 其構成為：於將一個陽極侧儲罐中蓄積之含有特定濃度之氧 化性物質的電解硫酸向硫酸電解裝置外之使用點輸送之期 間’使用另一陽極側儲罐生成含有特定濃度之氧化性物質之 電解硫酸^ 101107844 201243109 又，本發明之第9解決手段在於提供一種硫酸電解裝置， 其中’上述陽極3為導電性金剛石電極。 又，本發明之第H)解決手段在於提供K酸電解I 置，其中，上述隔膜5為氟樹脂系陽離子交換膜或經親水^ 處理之多孔質氟系樹脂膜。 又’本發明之第11解決手段在於提供一種硫酸電解方 法，其特徵在於：使用上述任一種硫酸電解裝置， 至所需之溫度及濃度之電解硫酸。 整 又，本發明之第 » z解決乎#又在於提供一種硫酸電解方 法，其特徵在於：使用上述任一種硫酸電解裝置，並且使用 多孔質氟系樹脂膜作為上述隔膜5，於因陽離子通過該多 質氟系樹輯時所攜帶之攜帶水，肢上騎極電解部 之陰極側電解路線B|中循環的稀釋硫酸溶液之液量增加 時’藉由定期地或於上述陰極側儲罐38之液面達到特定之 高度時排出特定量之液體，而防止該陰極側儲罐之溢出之 、、又，本發明之第13解決手段在於提供—種硫酸電解方 法’其特徵在於··於使用上述任―種硫酸電解裝置，並且< 用多孔質氟緖賴作為上述隔膜5，於因陽離子通過2 孔質敦系樹脂膜時所攜帶之攜帶水，使上述陰極電解部I 之路線At所生成之獅碰賴之韻濃度τ降為特^ 濃度以下之情形時，藉由於上述陰極側濃硫酸供給部％ = 補充湲硫酸而轉之稀釋硫酸濃度。 101107844 201243109 又，本發明之第14解決手段在於提供上述任一硫酸電解 方法，其中，於上述陽極側電解部20 0之稀釋硫酸生成路 線Α或上述陰極側電解部23内之稀釋硫酸生成路線a，令， 以電解前之稀釋硫酸之溫度成為贼以下之方式進行溫度 調整。 又’本發明之第15解決手段在於提供上述任一硫酸電解 方法’、其中’於上述陽極側電解部2G内之電解硫酸生成路 線B或上述陰極側電解部23内之陰極侧電解路線B，中，將 經電解之電解液之溫度調整為抓以下。 又’本發明之第16解決手段在於提供上述任—種硫酸電 方法’其中，於上述陽極侧電解部2〇内之稀釋硫酸生成 路線A或上述陰極側電解部23内之稀釋硫酸生成路線a， 中’以電解前之稀釋硫酸之顧濃度成為2〜1()咖 式進行濃度調整。 (發明效果）201243109 VI. Description of the Invention: [Technical Field] The present invention relates to a light-f-solution apparatus and a sulfuric acid electrolysis method which are produced by electrolyzing sulfuric acid to a large amount of electrolysis containing 9 substances.纟羊细和j ga .. : ,. An electrolytic sulfuric acid containing an oxidizing substance is efficiently and safely produced by electrolytically diluting the temperature and concentration of the sulfuric acid in the sulfuric acid electrolysis apparatus by the main management of the diluted sulfuric acid. Sulfuric acid electrolysis core and sulfuric acid electrolysis method. [Prior Art] The first moon is made of 4 metal < wang sulphate or etchant in the pre-electrolytic plating, the oxidant in the polishing treatment/mechanical grinding treatment, the oxidant in the wet type 77 organic matter, and the stone Persulfuric acid is used in various manufacturing steps such as a wafer cleaning agent or a chemical used in the V-crush. It is known that this persulfuric acid is called an oxidizing substance, and it is produced by electrolysis of sulfuric acid, and has been electrolytically produced on an industrial scale. In the present invention, the term "oxidizing substance" means persulfuric acid or hydrogen peroxide such as persulfuric acid or peroxymonosulfuric acid, and the term "electrolytic sulfuric acid" means that it is produced by electrolysis of sulfuric acid. Oxidizing substances and unreacted sulfuric acid. Electrolytic sulfuric acid (hereinafter referred to as "electrolytic sulfuric acid") contained in oxidizing (4) and unreacted sulfuric acid produced in a device for electrolyzing sulfuric acid is used as a thief in contaminating organic matter or contaminating metals in a semiconductor manufacturing process. The removal of the 'it' & oxidative substance concentration is higher concentration 101107844 3 201243109 The higher the effect, the sulfuric acid electric material is required to produce a higher concentration of oxidized (tetra) oxidized sulfuric acid, by electrolysis The oxidizing substance is more efficient in generating the oxidizing substance and has a lower decomposition property. In sulfuric acid electrolysis, in order to produce a high-concentration containing Wei-transfering substance f, the production efficiency of the oxidized biomass by electrolysis is higher, and the decomposition property of the oxidizing substance is lowered, and the sulfuric acid electrolysis apparatus is required. The medium is supplied with a low concentration of sulfuric acid adjusted to the desired degree. However, in general, sulfuric acid is sold as 98% or 96% concentrated sulfuric acid. Therefore, in order to supply an adjusted concentration of diluted low-concentration sulfuric acid (also referred to as diluted sulfuric acid) to a sulfuric acid electrolysis apparatus, a chemical solution for the workshop is required. The supply equipment is re-constructed for dedicated storage tanks or supply piping, and in this case, a large equipment cost is required. Further, since the sulfuric acid having a low concentration is relatively bulky compared with the concentrated sulfuric acid, the transportation cost of the drug is also increased as compared with the transportation of the concentrated sulfuric acid. In the sulfuric acid electrolysis apparatus, the sulfuric acid concentration can be efficiently adjusted, and the sulfuric acid electrolysis can be efficiently produced by electrolyzing a low-concentration sulfuric acid while minimizing the cost of preparing the sulfuric acid, such as equipment cost and transportation cost. It is possible to achieve the miniaturization and simplicity of sulfuric acid electrolysis by sharing the equipment and production line that constitutes a mechanism for producing dilute sulfuric acid based on concentrated sulfuric acid and electrolyzed sulfur 2 containing an oxidizing substance based on dilute sulfuric acid. Chemical. In paragraph ooii, which describes the electrolysis of sulfuric acid to produce persulfuric acid in an electrolytic cell, it is described as "by setting the concentration range of sulfuric acid used to form persulfuric acid to 2 to 11 mol/ The low concentration of sulfuric acid in L can increase the production efficiency of persulfate. In the paragraph 〇〇26 of Patent Document 2 which proposes a persulfuric acid supply system, "the range of the sulfuric acid concentration with respect to the electrolyte supplied to the electrolytic reaction device" is described as being set to 10 to 18 M (mol/L). Low concentration of sulfuric acid can increase the production efficiency of persulfuric acid." In paragraphs 0012 and 0018 of Patent Document 3, it is described that "the use of sulfuric acid having a different degree of agricultural power as an electrolytic solution improves the current efficiency for generating electrolytic sulfuric acid, and efficiently and stably generates an oxidizing substance. method". However, in the methods described in Patent Documents 1 to 3, it has been revealed that high-efficiency is produced by electrolysis of a low-temperature sulfuric acid, but there is no disclosure of a method for adjusting the concentration of sulfuric acid. In order to produce a low concentration of diluted sulfuric acid, it is usually necessary to mix concentrated sulfuric acid with pure water to appropriately adjust the sulfuric acid concentration, but when sulfuric acid is mixed with pure water, a large amount of dilution heat is generated, and a large amount of heat is generated by boiling or dilution. The vapor or mist caused. Therefore, if the exhaust gas from the storage tank or equipment for adjusting the sulfuric acid concentration is connected to the exhaust equipment or the detoxification equipment without any treatment, the sulfuric acid is mixed into the exhaust equipment or the waste is saved, so that there is a direct __# Or the problem of deterioration of performance. In Patent Document 4, a method of using a gas-liquid separation means as a method of removing sulfuric acid contained in an electrolytic gas generated by a reaction apparatus of Electric Power 101107844 201243109 is disclosed. However, although the sulfuric acid contained in the vapor or mist generated by adjusting the sulfuric acid concentration in the apparatus is more than the sulfuric acid contained in the electrolytic gas, the removal of the vapor and the mist generated when the sulfuric acid concentration is adjusted is not disclosed, and the sulfuric acid concentration adjustment method is disclosed. There is no disclosure. In Patent Document 5, there is a description of a method of re-concentrating sulfuric acid for washing, followed by dilution and cooling, and re-electrolysis to produce persulfuric acid, but temporarily supplying sulfuric acid for cleaning at a low concentration. Concentration, different purification, and safety issues. [Prior Art Document] [Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-66464 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-111184 (Patent Document 3) [Patent Document 4] Japanese Patent Application Publication No. 2007-262532 (Patent Document 5), JP-A-2008-244310, SUMMARY OF INVENTION [Problems to be Solved by the Invention] Provided is a sulfuric acid electrolysis device and a sulfuric acid electrolysis method which are capable of removing the heat of dilution generated when diluting concentrated sulfuric acid into a low concentration of sulfuric acid and the heat generated during electrolysis, and adjusting the electrolysis conditions for efficiently generating an oxidizing substance 'suppressed by dilution The generation of mist or vapor caused by heat, and further, the condensation droplets of sulfuric acid or the like caused by mist or vapor mixed into the exhaust system are removed from the exhaust system, and the electrolysis is more efficient and stable. Working. In order to solve the above problems, the present invention provides a sulfuric acid electrolysis apparatus in which a pot system includes an anode-side electrolysis unit 2〇 and a cathode-side electrolysis unit 23, which is characterized in that it is at least an anode-side electrolysis unit. 2 () is provided with an anode side diluted sulfuric acid production route A and an anode side electrolytic sulfuric acid production route b, the anode side diluted sulfuric acid production route A is diluted as a raw material of concentrated sulfuric acid, and the diluted diluted sulfuric acid is adjusted to a desired The temperature and the concentration, the cation-electrolytic sulphuric acid formation route B is formed by diluting the diluted sulphuric acid generated in the diluted sulfuric acid formation route A to generate a conversion, and adjusting the chemical sulphur to the desired temperature difference concentration, The anode-side diluted sulfuric acid production route A is arranged in the order of the anode side concentrated side sulfuric acid supply unit 32 and the anode side cooler unit %, and the (four)-pole side bypass is connected with the f% lag to form a route and then In the line A, the anode-side pure water supply pipe 10 for supplying pure water to the route A can be connected, and further, the supply of concentrated sulfur to the anode-side concentrated sulfuric acid supply unit 32 can be connected. The anode side concentrated sulfuric acid is provided for blindness. 7 The above-mentioned anode side electrolytic sulfuric acid formation route B is connected to the anode side storage tank 31 by the anode side and the f 37, and comprises the anode formed by the separator $: to 4, the cathode chamber 7 The anode of the anode 3 is provided in the inside of the electrolytic cell 2 to form a route, and the concentrated sulfuric acid supply pipe w from the anode side is supplied to the anode side; the concentrated sulfuric acid supplied from the agricultural sulfuric acid supply unit 32 is used from the anode 101107844 201243109 side. The pure water supply pipe is diluted with pure water supplied, and the diluted low concentration sulfuric acid is adjusted to the desired temperature and concentration during the cycle in the above route A to generate a dilution adjusted to the desired temperature and concentration. Sulfuric acid, the diluted sulfuric acid is supplied to the anode chamber 4 of the electrolytic cell 2 via the anode-side circulating piping P constituting the above-mentioned route B, and electrolytic sulfuric acid is generated in the anode chamber 4, and the red oxide is produced in consideration of the above route. The period of B internal circulation is adjusted to the desired temperature and concentration to produce electrolytic sulfuric acid adjusted to the desired temperature and concentration. Further, according to a second aspect of the present invention, the sulfuric acid electrolysis device is provided, and further, a cathode-side diluted sulfuric acid generation path, a line A', a cathode-side electrolysis path, and a line B are provided in the apparatus of the cathode-side electrolysis unit 23. The cathode-side diluted sulfuric acid production route A' is diluted with concentrated sulfuric acid as a raw material to prepare a low-concentration sulfuric acid' and (4) low-red sulfuric acid is difficult to prepare the temperature and concentration of the cathode-side electrolysis route B, which is the diluted sulfuric acid In the route A, the dilute sulfuric acid generated in the route A is generated, and the cathodic contact acid generation route is based on the cathode side storage tank 38, the cathode side concentrated sulfuric acid supply part%, and the cathode side cooler 41. In order to arrange the route, the cathode side bypass piping 43 is connected to form a route, and the cathode side pure water supply pipe 12 that supplies the pure water to the route Α' is connected at any position in the route Α. Further, a concentrated sulfuric acid supply pipe 29 for supplying concentrated sulfuric acid to the cathode-side concentrated sulfuric acid supply unit 39 is connected, and a cathode-side electrolysis route is connected to the cathode-side storage tank by a cathode-side circulation pipe 44. 38 is provided with a cathode in the electrolyte #2 including the anode chamber 101107844 8 201243109 formed of the separator 5, and a cathode sulfuric acid is supplied from the cathode side to the tube of the second tube. The cathode is supplied from the above-mentioned cathode_pure water supply route Α The thief of the (four) shape (10) degree is adjusted to the required temperature and concentration in the above-mentioned whole to the desired temperature, and the degree of the transformation is determined by the degree of 槿成和, and the rotation of the 4 degree is transferred from the sulfuric acid system. The cathode side circulation pipe 44 of B' supplies the electrolysis chamber 4 with enthalpy, di 4_, 丨 right 敫 敫;; during the above route (4), the electrolysis of the diluted sulfuric acid by temperature and concentration is carried out. The third solution of the present invention is to provide a sulfuric acid electrolysis apparatus which is connected to the anode side of the anode side storage tank 31 via the anode gas out of the sigma piping 1〇2 in series. The separation mechanism 91 and the anode side oil separation n 92 are provided on the anode side of the anode (four) liquid separation mechanism 91 and the anode side from the bottom of each of the mists 77 and 92 to discharge the liquids stored in the respective interiors. The gas-liquid separation mechanism 91 and the anode side oil mist separation 11 92 are formed by a liquid discharge means. Further, the fourth means of solving the present invention is to provide a sulfuric acid electrolysis apparatus which is connected to the anode side gas-liquid separation mechanism 91 in such a manner that the upper portion of the anode side storage tank 31 is connected in series via the anode gas outlet piping ι 2 in sequence. And an anode side oil mist separator 92, at the bottom of each of the anode side gas-liquid separation mechanism 91 and the anode side oil mist separator 92, is provided with an anode side gas-liquid separation that communicates with the liquid stored in each of the respective interiors. The mechanism 91 and the anode side oil mist 101107844 9 201243109 separate the liquid discharge means of the structure of the benefit 92, and further connect the cathode side gas-liquid separation to the cathode side of the cathode side storage tank 38 via the cathode gas outlet piping (8) in series. The mechanism 96 and the cathode side oil mist separator 97 have the bottom side of each of the cathode side gas-liquid separation mechanism 96 and the cathode side oil mist separator ', and have a cathode side gas-liquid separation which is stored in the respective (4) The mechanism 96 is formed by a liquid discharge means of the structure of the cathode side oil mist separator 97. Further, the fifth solution of the present invention is to provide a sulfuric acid electrolysis device, wherein 'the above-mentioned anode (four) mist separation is the same as the sixth solution of the present invention is to provide a sulfuric acid electrolysis device, A hydrogen treatment mechanism is connected to the cathode side oil mist separator 97. According to a seventh aspect of the present invention, there is provided a sulfuric acid electrolysis apparatus comprising: a plurality of the anode side storage tanks arranged in parallel in the diluted sulfuric acid generation route A, and accumulating in one of the anode side storage tanks After the generated electrolytic sulfuric acid containing the oxidizing substance is generated, the valve is switched, and then electrolytic sulfuric acid containing a specific concentration of the oxidizing substance is formed in the other anode side storage tank. Further, an eighth aspect of the present invention provides a sulfuric acid electrolysis apparatus which is configured to transport an electrolytic sulfuric acid containing a specific concentration of an oxidizing substance accumulated in an anode side storage tank to a point of use outside a sulfuric acid electrolysis apparatus. During the period of 'using another anode side storage tank to generate an electrolytic sulfuric acid containing a specific concentration of oxidizing substance ^ 101107844 201243109 Further, a ninth solution of the present invention is to provide a sulfuric acid electrolysis apparatus, wherein 'the anode 3 described above is a conductive diamond electrode. Further, in the H) solution of the present invention, the K acid electrolysis is provided, wherein the separator 5 is a fluororesin-based cation exchange membrane or a hydrophilic fluorine-based resin film treated with a hydrophilic treatment. Further, the eleventh solution of the present invention is to provide a sulfuric acid electrolysis method characterized by using any of the above-described sulfuric acid electrolysis devices to electrolyzed sulfuric acid at a desired temperature and concentration. Further, the present invention is directed to a sulfuric acid electrolysis method, which is characterized in that any of the above-described sulfuric acid electrolysis devices is used, and a porous fluorine-based resin film is used as the separator 5, because the cations pass through the The carrying water carried in the multi-fluorine-based tree series, when the amount of the diluted sulfuric acid solution circulating in the cathode-side electrolysis route B| on the limb riding electrolysis section is increased, by periodically or in the cathode side storage tank 38 When the liquid level reaches a certain height, a certain amount of liquid is discharged, and the overflow of the cathode side storage tank is prevented, and the 13th solution of the present invention is to provide a sulfuric acid electrolysis method, which is characterized in that In any of the above-described sulfuric acid electrolysis devices, and using the porous fluxon as the separator 5, the channel of the cathodic electrolysis portion I is at the point of carrying water when the cation passes through the two-hole resin film. When the generated lion's rhythm concentration τ falls below the specific concentration, the dilute sulfuric acid concentration is converted by the above-mentioned cathode side concentrated sulfuric acid supply portion % = supplemental sulfuric acid. According to a further aspect of the present invention, in the fourth aspect of the present invention, there is provided a sulfuric acid electrolysis method, wherein the diluted sulfuric acid formation route in the anode-side electrolysis unit 20 or the dilute sulfuric acid generation route in the cathode-side electrolysis unit 23 is provided. , order, to adjust the temperature of the diluted sulfuric acid before electrolysis to the thief below. Further, the fifteenth solution of the present invention is to provide any of the above-described sulfuric acid electrolysis methods, in which the electrolysis sulfuric acid production route B in the anode-side electrolysis portion 2G or the cathode-side electrolysis route B in the cathode-side electrolysis portion 23 is In the middle, the temperature of the electrolytic solution to be electrolyzed is adjusted to be the following. Further, the "16th solution of the present invention is to provide the above-described sulfuric acid electrolysis method" in which the diluted sulfuric acid production route A in the anode-side electrolysis portion 2 or the diluted sulfuric acid production route in the cathode-side electrolysis portion 23 is a. In the middle of the dilute sulfuric acid before electrolysis, the concentration is adjusted to 2~1 (). (effect of the invention)

=本發明之硫酸電解裝置及硫酸電解方法，可於硫酸電 、内生成所需之管理至特定之溫度及濃度的稀釋硫 酸’進而，藉由可將該稀釋硫酸於經溫度管理之條件下電L Γ且ΤΙ率且安全地生獻量含魏化歸質之電解硫 、夂，可以較高之電流效率製造利用先前技術無法達成之高 濃度且含有氧化性物質的電解溶液。 f實施方式；] 101107844 12 201243109 以下，參照圖式詳細地說明本發明之實施之一例。 圖1係表示本發明之硫酸電解裝置例之圖。硫酸電 解裝置Η系具有陽極側電解部2〇與陰極側電解部η而成， 2為電解槽。該電解槽2係藉由隔膜5而劃分為陽極室々與 陰極室7 ’於陽極室4内設置有陽極3，於陰極室7内設置 有陰極6。陽極室4係設置於硫酸電解裝置1之陽極側電解 部2〇中，本發明之特徵在於以下述之方式構成該陽極側電 於陽極側電解部20形成有陽極側稀釋硫酸生成路線Α血 陽極側電解硫酸生成路線B。首先，於圖！所例示之裝置中’ 陽極側稀釋硫酸生成路線A係依照陽極側儲罐Μ、陽極側 虞硫酸供給部32、陽極侧循環泵33、陽極側冷卻器Μ之順 =進行配置’利用陽極㈣路配f 36將該等連接而形成路 而且’以可藉由配置於陽極側冷卻器34與陽極側儲罐 ^間之陽極側旁路閥35而中斷路線㈣之液之循環之方 式構成。 又，於圖！所例示之裝置中，於陽極側儲罐3】連接有陽 玉側純水供給崎1G，於陽__酸供給部％連接有陽 j !/遭邊供給配官27。自陽極側漠硫酸供給配管π經由 陽極側濃硫酸供給閥28而向陽極側濃硫酸供給部^供給之 =酸’係於__ 31内利用自陽極側純水供給配管 經由陽極_水供給閥u而供給之純水轉而製成低濃 101107844 13 201243109 度之硫酸。經稀釋之硫酸係於在路線A内循環之期間調整 至所需之溫度及濃度。陽極側稀釋硫酸生成路線A中所生 至所需之溫度及濃度的稀釋硫酸，係向構成陽極側 ▲生成路線B之電解槽2之陽極室4中供給而進行 電解。關於陽極側電解硫酸生成路線B係如下所述。 夫:墙中，供給至陽極側儲㈣内之純水係使用 ^不之累積流量計或設置於儲罐中之液面計而進行定 篁，並供給至陽極侧儲罐31 +。於累積㈣計中可❹ = 、科裏奥利式等者’藉由根據累積流量計 U 之測定值或信號而控制機器控制純水之供认The sulfuric acid electrolysis device and the sulfuric acid electrolysis method of the present invention can generate the desired diluted sulfuric acid to a specific temperature and concentration in the sulfuric acid, and further, the diluted sulfuric acid can be powered under temperature management conditions. L Γ ΤΙ 且 安全 ΤΙ 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 含 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解 电解f embodiment;] 101107844 12 201243109 Hereinafter, an example of the implementation of the present invention will be described in detail with reference to the drawings. Fig. 1 is a view showing an example of a sulfuric acid electrolysis device of the present invention. The sulfuric acid electrolysis apparatus has an anode-side electrolysis unit 2〇 and a cathode-side electrolysis unit η, and 2 is an electrolysis cell. The electrolytic cell 2 is divided into an anode chamber 々 and a cathode chamber 7 by a separator 5, and an anode 3 is provided in the anode chamber 4, and a cathode 6 is provided in the cathode chamber 7. The anode chamber 4 is provided in the anode side electrolysis unit 2 of the sulfuric acid electrolysis device 1, and the present invention is characterized in that the anode side is electrically formed on the anode side, and the anode side is formed with an anode side diluted sulfuric acid generation route. Side electrolysis of sulfuric acid produces route B. First of all, in the picture! In the exemplified apparatus, the anode-side diluted sulfuric acid generation route A is configured in accordance with the anode side storage tank Μ, the anode side 虞 sulfuric acid supply unit 32, the anode side circulation pump 33, and the anode side cooler Μ = "using the anode (four) road The f 36 is connected to form a path and is configured to interrupt the circulation of the liquid in the route (4) by the anode side bypass valve 35 disposed between the anode side cooler 34 and the anode side storage tank. Also, in the picture! In the exemplified apparatus, the anode-side tank 3 is connected to the pure jade-side pure water supply to the Saki 1G, and the Yu-Y-acid supply unit % is connected to the yoke. The anode-side sulfuric acid supply pipe π is supplied to the anode-side concentrated sulfuric acid supply unit via the anode-side concentrated sulfuric acid supply valve 28, and the acid is supplied from the anode-side pure water supply pipe via the anode-water supply valve in the __31. u The pure water supplied is turned into a low-concentration 101107844 13 201243109 sulfuric acid. The diluted sulfuric acid is adjusted to the desired temperature and concentration during the cycle in Route A. The diluted sulfuric acid which is obtained at the desired temperature and concentration in the sulfuric acid generation route A on the anode side is supplied to the anode chamber 4 constituting the anode side ▲ electrolytic cell 2 of the route B to be electrolyzed. The anode-side electrolytic sulfuric acid formation route B is as follows. In the wall, the pure water supplied to the anode side storage (4) is fixed using a cumulative flow meter or a liquid level meter installed in the storage tank, and supplied to the anode side storage tank 31 +. In the cumulative (four) calculation, the ❹ 、, Corioli type, etc. control the operability of the machine controlled pure water by the measured value or signal of the cumulative flow meter U

或供給停止。再者，陽_純水供給配管H)之連接部Z 不限定於圖1之你丨+，立& ”不右為路線A内，其設置位置亦可為 :意處。21為陽極室入口闕，22為陽極室出口闕，藉由適 極側旁路間35與該等闕’而稀釋硫酸分別於稀 爪-夂生成路線A或電解硫酸生成路線B中循環。又，μ 為陰極室入口閥，25為陰極室出口闕。 陽極側電解硫酸生成路線B仙如下方式而構成：利用 陽極側循環配管37連接電解槽2之_ 4與__ 而^成路線，則配置於各配管途中之閥，而陽極侧稀 4生成路線A巾所生成之稀釋硫酸可於陽極側電 酸生成路線B中循環。 巩 於上述路線B中，進行於上述路線A中經溫度及濃度調 101107844 201243109 整之稀釋硫酸之電解，而生成電解硫酸，將於在上述路線B 中循環之期間所生成之電解硫酸與於上述路線A中經調整 之稀釋硫酸混合，將電解硫酸調整至所需之溫度及濃度。 又，關於該等配皆或機器之接液部分，需要使用對硫酸或含 有氧化性物質之硫酸具有耐|虫性之材料。例如可使用聚四氟 乙烯(PTFE，P〇lytetrafluorethylene)或四氟乙烯_全氟烷基乙 烯醚共聚合物(PFA，P〇lyfluoroalk〇xy)等氟樹脂或石英等。 圖1中之23係表示硫酸電解裝置丨之陰極側電解部者。 於陰極側電解部23内，與陽極侧電解部2()相同地形成有將 濃硫酸調整至所需之溫度及濃度之稀釋硫酸的陰極側稀釋 硫酸生成祕A’與將於祕線A，巾經調整之轉硫酸通入 至陰極室7中循環之陰極側電解路線b，。 ’由陰極側儲罐38、 泵40、陰極側冷卻器 上述路線A1於圖1所例示之裳置中 陰極側濃硫酸供給部39、陰極侧循環 〇、陰極财路閥42、陰極側旁路配f 43、及配置於各配 管途中之閥構成。而且，於該例示之I置中，陰極·罐 料接㈣極舰水供純管12,陰_濃频供給部％ 連接有陰極侧濃械供給配f 29。將自陰_濃硫酸供給 配管29經由陰極側濃硫酸供給閥3q向陰極側濃硫酸供給部 39供給之濃硫酸係於陰極側儲罐38内利用自陰極側純水供 給配管12經由陰極侧純水供給閥13向陰極側儲罐38供給 之純水稀釋，而成為低濃度之稀釋硫酸。而且，該稀釋硫酸 101107844 201243109 係於在上述路線A，内循環之期間調整至所需之溫度及濃 度。5周整至所需之溫度及濃度之稀釋硫酸係向設置於上述路 線B’中之電解槽2之陰極室7中供給而進行電解。 只要以供給陰極側儲罐38内之純水係使用未圖示之累積 々L里或各儲罐所具備之液面計而定量，並供給至陰極側儲 罐38中之方式構成即可。累積流量計可使用超音波式或電 磁式、科裏奥利式等，藉由來自累積流量計或液面感測器之 測疋值或信號而控制機器控制純水之供給或供給停止。再 者’陰極側純水供給配管12之連接部分只要為路線A’内， 其設置位置可為任意處。 又’關於該等配管或機器之接液部分，需要使用對硫酸或 含有氧化性物質之硫酸具有耐蝕性之材料，例如使用PTFE 或PFA等氟樹脂或石英等。 上述陰極側電解路線B'係由電解槽2之陰極室7、陰極側 擔％配管44、陰極側儲罐38與配置於各配管途中之閥配置 成路線狀而構成。於陰極側電解部23内之上述路線B,中進 行稀釋硫酸之電解’但電極反應僅產生氫氣’不生成電解硫 酸’因此於上述路線B’内，調整至所需之溫度及濃度之稀 釋硫酸進行循環。 陽極側濃硫酸供給部32及陰極側濃硫酸供給部39，可配 置於陽極側循環泵33及陰極側循環泵40之入口側、出口側 之任一處。然而，於將濃硫酸供給至經升壓之純水中之情形 101107844 201243109 時’於經升壓之位置產生由濃硫 熱及氣泡，因此具有進—步升壓之^^=顯著之發Or the supply stops. Furthermore, the connection portion Z of the yang-pure water supply pipe H) is not limited to the one of the 图+, and the 立& ” is not in the route A, and the setting position may also be: intention. 21 is the anode chamber The inlet port, 22 is the anode chamber outlet port, and the diluted sulfuric acid is circulated in the thin-claw-夂 formation route A or the electrolytic sulfuric acid formation route B by the appropriate-side bypass passage 35 and the 阙', respectively, and μ is the cathode. The chamber inlet valve, 25 is the cathode chamber outlet port. The anode side electrolysis sulfuric acid generation route B is configured as follows: the anode side circulation pipe 37 is connected to the electrolytic cell 2 by _ 4 and __ and the route is arranged in each pipe. The valve on the way, and the diluted sulfuric acid generated by the anode side dilute 4 generation route A can be circulated in the anode side electroacid formation route B. In the above route B, the temperature and concentration adjustment in the above route A is carried out 101107844 201243109 The electrolysis of the diluted sulfuric acid to produce electrolytic sulfuric acid, the electrolytic sulfuric acid generated during the cycle in the above route B is mixed with the adjusted diluted sulfuric acid in the above route A, and the electrolytic sulfuric acid is adjusted to the desired temperature and Concentration. Again, about this For the liquid-repellent part of the machine or the machine, it is necessary to use a material resistant to sulfuric acid or sulfuric acid containing an oxidizing substance. For example, polytetrafluoroethylene (PTFE, P〇lytetrafluorethylene) or tetrafluoroethylene-perfluoroalkane can be used. A fluororesin such as a vinylidene ether copolymer (PFA, P〇lyfluoroalk〇xy), or quartz, etc. The 23 in Fig. 1 indicates a cathode-side electrolysis unit of a sulfuric acid electrolysis apparatus, and is in the cathode-side electrolysis unit 23, and an anode. The side electrolysis unit 2 () is similarly formed with a dilute sulfuric acid to adjust the desired temperature and concentration of the dilute sulfuric acid to the cathode side to dilute the sulfuric acid to form a secret A' and to the secret line A, the adjusted sulfuric acid is passed to the cathode. The cathode side electrolysis route b circulating in the chamber 7 is 'recharged by the cathode side storage tank 38, the pump 40, the cathode side cooler, the above-described route A1, the cathode side concentrated sulfuric acid supply portion 39, and the cathode side cycle illustrated in Fig. 1 〇, cathode financial path valve 42, cathode side bypass arrangement f 43 , and a valve arranged in the middle of each pipe. Moreover, in the example I, the cathode and the tank material are connected to the (four) pole ship water supply for the pure pipe 12, Yin_concentrated frequency supply unit% connected with cathode side thickener supply f 29. The concentrated sulfuric acid supplied from the cathode-concentrated sulfuric acid supply pipe 29 to the cathode-side concentrated sulfuric acid supply unit 39 via the cathode-side concentrated sulfuric acid supply valve 3q is supplied to the cathode side storage tank 38 via the cathode-side pure water supply pipe 12 via the cathode-side pure water supply pipe 12 The cathode-side pure water supply valve 13 is diluted with pure water supplied from the cathode-side storage tank 38 to become a low-concentration diluted sulfuric acid. Moreover, the diluted sulfuric acid 101107844 201243109 is adjusted to the required period during the internal circulation of the above-mentioned route A. Temperature and concentration: The diluted sulfuric acid which was supplied to the required temperature and concentration for 5 weeks was supplied to the cathode chamber 7 of the electrolytic cell 2 provided in the above route B' for electrolysis. The pure water supplied to the cathode side storage tank 38 may be configured to be quantified by using a liquid level meter (not shown) or a liquid level meter provided in each of the storage tanks, and supplied to the cathode side storage tank 38. The accumulating flow meter can control the supply of the machine-controlled pure water or the supply stop by using the ultrasonic or electro-magnetic type, Coriolis type, etc., by the measured value or signal from the cumulative flow meter or the level sensor. Further, the connecting portion of the cathode-side pure water supply pipe 12 may be any position as long as it is in the route A'. Further, it is necessary to use a material having corrosion resistance to sulfuric acid or sulfuric acid containing an oxidizing substance, for example, a fluororesin such as PTFE or PFA, or quartz, etc., for the liquid-contacting portion of the piping or the machine. The cathode-side electrolysis route B' is constituted by a cathode chamber 7 of the electrolytic cell 2, a cathode-side hydrogen storage pipe 44, a cathode-side storage tank 38, and a valve disposed in the middle of each pipe. In the above-mentioned route B in the cathode-side electrolysis section 23, electrolysis of diluted sulfuric acid is performed, but the electrode reaction produces only hydrogen gas, which does not generate electrolytic sulfuric acid. Therefore, in the above route B', the diluted sulfuric acid is adjusted to the desired temperature and concentration. Loop. The anode-side concentrated sulfuric acid supply unit 32 and the cathode-side concentrated sulfuric acid supply unit 39 can be disposed at either the inlet side or the outlet side of the anode side circulation pump 33 and the cathode side circulation pump 40. However, in the case where concentrated sulfuric acid is supplied to the pressurized pure water 101107844 201243109, the sulfur is generated from the concentrated pressure and the bubble is generated, so that there is a significant increase in the pressure of the step-up stepping.

而言，較佳為配置於陽極側循環泉二=性之方面 ♦ X 及陰極侧循環泵4D 硫酸濃度可利用供給至上述陽極側稀釋硫酸生成 路線Α及陰極側__生成㈣Α，巾之 成 為已知之濃硫酸之體積比率進行，整 里辰度 用累積流量料騎定量机各種賴之體積可使 於本發明中，較佳為使用導電性金剛石 3。於此情形時’與使用pt〇b〇2 ^迷陽極 ，過電壓b，因此過魏生歧率較高，並且無論化 了生亦或機綱久性均較高，不產生來自陽極之污染，因此 成清毅較高之作為電軸H錄及作為 t物之?解硫酸。就上述理由而言，較理想為電解槽2中所 使用之陽極3使用導電性金剛石電極。 力一万面，關於陰極6,就淨化性之方面而言，較理相為 =用耐錄優異之導電性金剛石電極，亦可使用由對硫酸且 有耐錄之料貴金屬、或鈦、鍅、紐、蚊類閥金屬以及 如石墨或玻璃石墨之碳材所構成之電極。 根據本發明者等人之研究，於調整硫酸濃度時，若於循環 系統内具備電解槽2之路線B中進行，則藉由稀釋熱而電 解槽2之内部變高溫，隔膜5有損傷。因此，於本發明中， 為避免此種情形’硫酸濃度調整巾係於陽極側電解部内 101107844 17 201243109 藉由回避向電解槽2中之通液，向陽極側旁路 订通液之路線A而進行循環冷卻。又，由於s進 於陰極側電解部23内，藉由回避向電解槽2 °之理由， 向陰極側旁路配管43中進行通液之路線：之:液，而 並進行硫酸之漠度調整及溫度調整。 仃趣令部 之=陽::嶋部…“及陰極側電解部23中 稀釋1所引 酸濃度調整，則具有產生大量由硫酸之 ㈣之蒸氣或霧之情形。於本發明中，將藉由電解 所攜帶之該等蒸氣或霧送至電解氣體之除害 置外之排出目的地’為了防止顧該等，較佳為於 連接於陽極側儲罐31之陽極氣體出口配管102之後面，設 置氣液分離機構97與陽極側油霧分離器92。同樣地，較佳 為於連接於陰極側儲罐38之陰極氣體出口配管103之後面 設置陰極側氣液分離手段96與陰極側油霧分離器97。 繼而’對藉由電解所產生之電解氣體進行說明。電解槽2 之陽極室中產生之陽極氣體具有包含有毒之臭氧之情形。因 此’於陽極側油霧分離器92後面，較理想為設置臭氧分解 觸媒作為臭氧除害手段93而將臭氧還原為氧而無害化或者 利用空氣或惰性氣體充分地稀釋而放出至裒置外。作為臭氧 分解觸媒，使㈣氧化狀情形較多，但於與#值較低之 硫酸等酸溶液接觸之情形時，存在過氧化猛溶解，而臭氧分 解能力消失之情形。又，即便接觸之液體為水，於臭氧分解 101107844 201243109 觸媒表面由水覆蓋之情形時，臭氧氣體與觸媒變得無法接 觸，因此於此情形時，臭氧分解能力亦消失。因此，為了於 裝置内處理臭氧且使裝置安全地運作，較佳為藉由氣液分離 機構97及油霧分離器92而自電解氣體中去除霧及蒸氣。 又，預先考慮供給霧或存在冷凝之可能性之蒸氣之情形除 外，於送氣所使用之配管通常為使用不鏽鋼等金屬製配管之 情形，藉由與硫酸霧或冷凝之接觸而進行腐蝕，因此基本上 無需將含有該等之電解氣體排出至裝置外。 由於電解槽2之陰極室中產生之陰極氣體之氫具有可燃 性、爆炸性，因此較理想為於陰極側油霧分離器97之後面 設置氫燃燒觸媒，將所產生之氫氣與空氣混合並使其燃燒， 轉換成無害之水蒸氣而排出，或者利用空氣或惰性氣體充分 地稀釋而排出至裝置外。氫燃燒觸媒具有使空氣與氫燃燒而 對氫進行除害之功能，較多為使用含有貴金屬之觸媒作為用 以燃燒之有效成分。通常，於觸媒表面由水等液體覆蓋之情 形時，氫氣與觸媒無法接觸，因此氳燃燒能力消失。又，預 先考慮供給霧或存在冷凝之可能性之蒸氣之情形除外，於送 氣所使用之配管通常為使用不鏽鋼等金屬製配管之情形 時，藉由與硫酸霧或冷凝之接觸而進行腐蝕，因此基本上無 需將含有該等之電解氣體排出至裝置外。 關於陽極侧氣液分離機構91及陰極側氣液分離機構96， 可使用配管或儲罐等容器利用電解氣體與電解氣體中之液 101107844 19 201243109 體之比重差而分離電解產生氣體與硫酸之機構者、或使容器 内之電解氣體之滯留時間變長，以使霧落入容器内之機構者 等。油霧分離器92及97可使用筒狀容器之中使用具有耐藥 品性之材質之絲網或多孔質材料者、或者使電解氣體之滯留 時間變長以使霧落下者等。又，藉由冷卻氣液分離機構或油 霧分離器或連接該等之配管而降低飽和水蒸氣壓，藉此，使 電解氣體中之水分凝結而增大氣液分離機構或油霧分離器 中之水分去除效率，減少向後續生產線之帶出量亦為有效之 手段。 若於陽極側氣液分離機構91、陰極側氣液分離機構96、 陽極側油霧分離器92及陰極側油霧分離器97中混入大量之 蒸氣或霧，則存在内部蓄積液體而堵塞氣體流路，無法進行 陽極側儲罐31及陰極側儲罐38之排氣之情形。因此，較佳 為陽極側氣液分離機構91、陰極側氣液分離機構96、陽極 側油霧分離器92及陰極側油霧分離器97定期對内部所蓄積 之液體進行排液。 陽極側氣液分離機構91及陽極側油霧分離器92之排液， 係藉由打開陽極側氣體配管排液閥94而由陽極側排液配管 95進行。陰極側氣液分離機構96及陰極側油霧分離器97 之排液，係藉由打開陰極側氣體配管排液閥99而由陰極側 排液配管100進行。 此處，對氣液分離、各機器之目的與電解硫酸裝置運作時 101107844 20 201243109 之樣子進行說明。 (1)硫酸稀釋時 ’但於歸硫酸進 有於較配管廣闊 雖然於路線A中設置有陽極侧冷卻器34， 行稀釋時，液溫度上升至高於室溫。此時， 之陽極側儲罐31之氣體空間内存在含有陽極側儲罐W内所 蓄積之成為稀釋硫酸濃度、溫度變平衡之水蒸氣壓的氣體 (空氣)之可能性。該含水蒸氣氣體係於含水蒸氣氣體接觸之 室溫下之儲罐壁面或配管壁面進行冷卻而水滴進行凝縮。 硫酸稀釋運作係最初於陽極侧儲罐31或配管内蓄積規定 量之純水，於循環途中注入規定量之硫酸，並進行混人者， 因此陽極侧儲罐31内之液面伴隨硫酸之注入而上升，陽極 側儲罐31内之氣體緩慢地向陽極側儲罐31外（陽極氣體出 口配管102上部）排出，而產生空氣之流動。伴隨該空氣之 流動，而上述附著於壁面上之水滴移動至陽極氣體出口配管 102 中。 (2)電解時 電解時係與上述（1 )不同，|出絲經3丨& % hPreferably, it is disposed on the anode side of the circulation spring = ♦ X and the cathode side circulation pump 4D sulfuric acid concentration can be supplied to the anode side diluted sulfuric acid generation route 阴极 and the cathode side __ generation (four) Α, the towel becomes It is known that the volume ratio of concentrated sulfuric acid is carried out, and the volume of the full-scale sulphuric acid is used in the present invention. It is preferable to use the conductive diamond 3. In this case, 'with the use of pt〇b〇2 ^ anodic anode, over-voltage b, so the excessive Weisheng rate is high, and no matter whether it is normal or long-term, it does not cause pollution from the anode, so Cheng Qingyi is higher as the electric axis H recorded and used as the t material to dissolve sulfuric acid. For the above reasons, it is preferable to use a conductive diamond electrode for the anode 3 used in the electrolytic cell 2. With respect to the cathode 6, in terms of purification, the phase is = the conductive diamond electrode excellent in resistance to recording, and the noble metal or titanium or tantalum which is resistant to sulfuric acid and resistant to recording can also be used. , New Zealand, mosquito valve metal and electrodes made of carbon materials such as graphite or glass graphite. According to the study by the inventors of the present invention, when the sulfuric acid concentration is adjusted, if it is carried out in the route B including the electrolytic cell 2 in the circulation system, the inside of the electrolytic cell 2 is heated by the heat of dilution, and the separator 5 is damaged. Therefore, in the present invention, in order to avoid such a situation, the sulfuric acid concentration adjusting napkin is in the anode side electrolysis unit 101107844 17 201243109 by bypassing the liquid passage into the electrolytic cell 2, bypassing the route A of the through liquid to the anode side. Perform circulating cooling. In addition, since s enters the cathode-side electrolysis unit 23, the route of the liquid passage is performed to the cathode-side bypass pipe 43 by the avoidance of the electrolysis cell 2°, and the sulfurization adjustment is performed. And temperature adjustment. In the case of the 令 令 = 阳 阳 阳 “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ “ 阴极 阴极 阴极 阴极 阴极 阴极 阴极 阴极 阴极 阴极 阴极 阴极 阴极It is preferable that the vapor or mist carried by the electrolysis is sent to the discharge destination outside the detoxification of the electrolysis gas. In order to prevent this, it is preferable to be connected to the anode gas outlet pipe 102 of the anode side storage tank 31, The gas-liquid separation mechanism 97 and the anode-side oil mist separator 92 are provided. Similarly, it is preferable to provide a cathode-side gas-liquid separation means 96 and a cathode side oil mist after the cathode gas outlet pipe 103 connected to the cathode side storage tank 38. Separator 97. Then, the electrolysis gas generated by electrolysis is described. The anode gas generated in the anode chamber of the electrolysis cell 2 has a toxic ozone content. Therefore, it is behind the anode side oil mist separator 92. It is preferable to provide an ozone decomposing catalyst as an ozone detoxification means 93, and reduce ozone to oxygen to be harmless or to be sufficiently diluted with air or an inert gas to be released to the outside of the crucible. As an ozone decomposing catalyst, Oxidation is more common, but in the case of contact with an acid solution such as sulfuric acid having a lower value of #, there is a case where the peroxidation is dissolved and the ozone decomposition ability is lost. Further, even if the contact liquid is water, the ozone is decomposed 101107844 201243109 When the surface of the catalyst is covered with water, the ozone gas and the catalyst become inaccessible, so in this case, the ozone decomposition ability also disappears. Therefore, in order to treat the ozone in the device and operate the device safely, it is preferable. The mist and the vapor are removed from the electrolysis gas by the gas-liquid separation mechanism 97 and the oil mist separator 92. In addition, in consideration of the supply of mist or the possibility of condensation, the piping used for the air supply is usually In the case of using a metal pipe such as stainless steel, corrosion is performed by contact with sulfuric acid mist or condensation, so that it is basically unnecessary to discharge the electrolytic gas containing the same to the outside of the apparatus. The cathode gas generated in the cathode chamber of the electrolytic cell 2 The hydrogen is flammable and explosive, so it is preferable to provide a hydrogen combustion catalyst on the back side of the cathode side oil mist separator 97. The generated hydrogen gas is mixed with air and burned, converted into harmless water vapor and discharged, or is sufficiently diluted with air or inert gas to be discharged to the outside of the device. The hydrogen combustion catalyst has a function of burning air and hydrogen to remove hydrogen. The function of the damage is mostly the use of a catalyst containing a precious metal as an active ingredient for combustion. Usually, when the surface of the catalyst is covered with a liquid such as water, the hydrogen and the catalyst are not in contact, and thus the combustion ability of the crucible disappears. In the case where the supply of mist or the possibility of condensation is considered in advance, the piping used for the air supply is usually made of a metal pipe such as stainless steel, and is corroded by contact with sulfuric acid mist or condensation. It is not necessary to discharge the electrolytic gas containing the above to the outside of the apparatus. The anode-side gas-liquid separation mechanism 91 and the cathode-side gas-liquid separation mechanism 96 can use a liquid in the electrolytic gas and the electrolytic gas using a container such as a pipe or a storage tank 101107844 19 201243109 The difference in the proportion of the body and the separation of the electrolysis gas and sulfuric acid institutions, or the electrolytic gas in the container The residence time becomes longer, so that the mist falls into the container or the like. The oil mist separators 92 and 97 can be used by using a screen or a porous material of a material having a chemical resistance in a cylindrical container, or by increasing the residence time of the electrolytic gas to cause the mist to fall. Further, by cooling the gas-liquid separation mechanism or the oil mist separator or connecting the pipes, the saturated water vapor pressure is lowered, whereby the moisture in the electrolytic gas is condensed to increase the gas-liquid separation mechanism or the oil mist separator. Water removal efficiency and reduced throughput to subsequent production lines are also effective means. When a large amount of vapor or mist is mixed in the anode-side gas-liquid separation mechanism 91, the cathode-side gas-liquid separation mechanism 96, the anode-side oil mist separator 92, and the cathode-side oil mist separator 97, the liquid is accumulated inside and the gas flow is blocked. In the case of the road, the exhaust of the anode side storage tank 31 and the cathode side storage tank 38 cannot be performed. Therefore, it is preferable that the anode-side gas-liquid separation mechanism 91, the cathode-side gas-liquid separation mechanism 96, the anode-side oil mist separator 92, and the cathode-side oil mist separator 97 periodically discharge the liquid accumulated inside. The liquid discharge from the anode side gas-liquid separation mechanism 91 and the anode side oil mist separator 92 is performed by the anode side liquid discharge pipe 95 by opening the anode side gas pipe discharge valve 94. The discharge of the cathode side gas-liquid separation means 96 and the cathode side oil mist separator 97 is performed by the cathode side discharge pipe 100 by opening the cathode side gas pipe discharge valve 99. Here, the description of the gas-liquid separation, the purpose of each machine, and the operation of the electrolytic sulfuric acid plant 101107844 20 201243109 will be described. (1) When sulfuric acid is diluted ‘But in sulfuric acid, it is wider than the piping. Although the anode side cooler 34 is provided in the route A, the liquid temperature rises above room temperature when diluted. At this time, there is a possibility that the gas space of the anode side storage tank 31 contains a gas (air) which is accumulated in the anode side storage tank W and which is a water vapor pressure which is diluted in sulfuric acid concentration and temperature is balanced. The aqueous vapor gas system is cooled at a storage tank wall surface or a piping wall surface at a room temperature where the vapor-containing gas is contacted, and the water droplets are condensed. The sulfuric acid dilution operation first accumulates a predetermined amount of pure water in the anode side storage tank 31 or the piping, and injects a predetermined amount of sulfuric acid in the circulation, and mixes it, so that the liquid level in the anode side storage tank 31 is accompanied by the injection of sulfuric acid. On the other hand, the gas in the anode side storage tank 31 is slowly discharged to the outside of the anode side storage tank 31 (the upper portion of the anode gas outlet piping 102) to generate a flow of air. With the flow of the air, the water droplets adhering to the wall surface move into the anode gas outlet pipe 102. (2) During electrolysis, the electrolysis is different from (1) above, and the filament is 3丨 & % h

之混合所產生之熱係快速地於陽極侧冷卻器％中去除，但 電解槽2中所產生之由電解所引起之熱係提高電解液之溫 度’而供給至陽極側儲罐31内，因此推測水蒸氣(水滴）之 101107844 21 201243109 產生較上述（1)多。進而，於電解時，藉由電解而自電極產 生電解氣體，且作為微細氣泡而含於電解液中。該微細氣泡 於陽極側儲罐31内自電解液中向氣相中移動，但當微細氣 泡於液面處裂開時產生微細之飛沫，其係作為霧而含於陽極 側儲罐31内之氣體中。 (3)各機構 連接於陽極側氣液分離機構91上部之陽極側油霧分離器 92,係可藉由使具有微細孔之分離膜不通過霧而分離氣體分 子與霧（由於微細而浮游於氣體中之液滴）者。伴隨藉由該分 離膜而分離之霧之分離量增加，可緩慢地變成液滴，並作為 液而流動。 由陽極側氣液分離機構91分離之液體a由於重力（自重) 而向氣液分離機構91下側流動。又，藉由利用陽極側油霧 分離器92分離之霧聚集而變成液滴，由於自重而向陽極側 油霧分離器92下側流動，轉移至陽極側氣液分離機構91 中。由陽極側油霧分離器92分離之液體b係於陽極側氣液 分離機構91中以與上述液體a相同之方式向陽極側氣液分 離機構91下側流動。向陽極側氣液分離機構91下側流動之 液體a及b係於陽極側氣體配管排液閥94之前面聚集，於 陽極側氣體配管排液閥94打開時利用自重排出至裝置外。 因此，對於由氣液分離機構或油霧分離器分離之液體之排 出，各機器之高度位置之關係較為重要，至少需要自上方向 101107844 22 201243109 下讀序設為陽極側_分_ 92、陽_氣液分離機構 91、陽極側氣體配管排液閥94。氣體配管排液閥94之開閉 之時機係任意選擇。 再者，較佳為於連接於陰極側氣液分離機構96之上部之 陰極側油霧分離器97中亦相同。 為了间效地進行氣液分離機構及油霧分離器内之排液，利 用f力差即可。例如，於陽極侧排液配管95及陰極側排液 配二削中設置未圖示之減壓器，藉由對氣液分離機構與油 霧:離^内進行減壓而形成陽極氣體及陰極氣體相反方向 之孔體流’藉此’可高效地對氣液分離機構及油霧分離器内 之硫酸進行排液。 作為另#去，於陽極側油霧分離器92及陰極側油霧分 °之出π侧设置未圖示之惰性氣體供給部，而利用惰 性氣體將纽分離機構與油霧分㈣时射祕極氣體及 丢木礼體相反方向’藉此，可高效地對氣液分離機構及油霧 分離器内之猶進行排液。作為情性氣體，例如可使用氮氣。 電解槽2中所使用之隔膜5較佳為使用經親水化處理之多 ^質氟系樹㈣魏樹脂系騎子交顧。於使用氣樹脂系 交換敵情科，於_子自馳__侧透過離 換膜f _所攜帶之攜帶水陽極之硫酸濃 又迎電解時間之流逝而上升，並且陽極側之液量減少，陰極 之硫酸濃度因由攜帶水稀釋而下降，並且液量增加。 101107844 23 201243109 陰極側之液量管理係藉由陰極儲罐排出閥113之開閉而 進行，無論定期排出之情形，還是利用儲罐中之液面高度進 行管理之情形，均藉由打開陰極儲罐排出閥113而利用自重 將液排出至裝置外。排出量之管理可採取各種方法，例如， 可藉由於陰極側儲罐38内設置測定Low位置之液面感測 器，進行液排出直至液面來到該感測器位置時關閉陰極儲罐 排出閥113而進行管理。作為陰極儲罐排出閥113打開之時 機，可使用下述情形之任一者：監視電解時間與通電電流 值，根據其等算出攜帶水量而於攜帶水量達到規定值時刻打 開之情形、與於陰極側儲罐38内設置測定High位置之液面 感測器，進行攜帶水儲存直至液面增加至該感測器位置時打 開之情形。 再者’平衡陰極側儲罐38之空間之氣體可自陰極氣體除 害機器98通過陰極氣體出口配管1〇3而流入。 若因攜帶水而陰極液增加，則陰極側儲罐％之液面上升 而超過陰極側儲罐38之容量，因此於陰極側儲罐％中，於 儲罐液面達到特定之高度時打開陰極儲罐排出閥ιΐ3，由陰 極儲罐排出配管112排出特定量液體，藉此防止蓄積量: 剩。關於陰極側儲罐38之液面之管理，可使用未圖示之液 面感測器等。如此，於因陽離子通過多孔質氟系樹脂膜時所 攜帶之攜帶水使陰極電解部23之稀釋硫酸溶液之液量辦加 時，定期或於陰極侧儲罐38之液面達到蚊之高度時^出 101107844 24 201243109 特定量之液體，藉此可防止陰極側儲罐38之溢出。 另一方面，若不對陰極液進行排液而繼續使用，則由於攜 帶水而陰極之硫酸進一步稀釋而濃度下降且導電率大幅度 下降。於不交換陰極液而長時間使㈣，亦可以藉由未圖示 之硫酸濃度計監視陰崎之俩濃度，自陰_硫酸供給部 39補充濃硫酸而變為一定濃度之方式進行控制。 例如，測定電解時間與電流值，求出根據測定值所算出之 攜帶水量’繼而’算出電解前經調整之陰極側儲罐38内之 電解液量及對該硫酸濃度添加上述攜帶水量時之硫酸濃 度’於所算出之硫酸濃度較規定範ϋ⑽薄之情形時，算出 為了回歸至狀範圍内而應添加之硫酸量，—面利用流量計 對所舁出之硫酸量進行定量，—面自陰極側硫酸供給部％ 向陰極侧電解路線Β，運作狀態處注人濃硫酸，藉此可控制 陰極液中之《濃度。為了減少電解條件之變動，較為重要 的疋使濃硫酸之注人速度遲緩而以於供給至溫度管理及槽 中之硫酸濃度不脫離規定範ϋ内之方式進行管理。 於陽極側電解部20中之路線以，於特定時間之電解 後，到達特定之氧化性物 硫酸’係由陽極細& f 4度之陽極職罐31内之電解 二極儲罐排出配管ιι〇、陽極 裝置外之使用點供給 侧電解路線B.内，於特=於陰極側電解部23中之陰極 之電解液係自陰極儲罐排屮電解後’陰極側健罐38内 罐排出配管112、陰極儲罐排出閥113 101107844 25 201243109 向裝置外排出。 若陽:側儲罐31内之電解硫酸變空 硫 f之調整。㈣，為了降罐咖量，較“進行濃产The heat generated by the mixing is quickly removed in the anode side cooler %, but the heat generated by the electrolysis in the electrolytic cell 2 increases the temperature of the electrolyte and is supplied to the anode side storage tank 31, so It is assumed that 101107844 21 201243109 of water vapor (water droplets) is produced more than the above (1). Further, at the time of electrolysis, an electrolysis gas is generated from the electrode by electrolysis, and is contained in the electrolytic solution as fine bubbles. The fine bubbles move from the electrolyte to the gas phase in the anode side storage tank 31, but when the fine bubbles are cracked at the liquid surface, fine droplets are generated, which are contained in the anode side storage tank 31 as mist. In the gas. (3) Each of the mechanisms is connected to the anode-side oil mist separator 92 at the upper portion of the anode-side gas-liquid separation mechanism 91, and the gas molecules and the mist are separated by the separation membrane having the fine pores without passing through the mist (due to fine floating) The droplets in the gas). As the amount of separation of the mist separated by the separation membrane increases, it becomes a droplet and slowly flows as a liquid. The liquid a separated by the anode-side gas-liquid separation mechanism 91 flows to the lower side of the gas-liquid separation mechanism 91 due to gravity (self-weight). In addition, the mist separated by the anode-side oil mist separator 92 is aggregated to become droplets, and flows to the lower side of the anode-side oil mist separator 92 by its own weight, and is transferred to the anode-side gas-liquid separation mechanism 91. The liquid b separated by the anode-side oil mist separator 92 flows to the lower side of the anode-side gas-liquid separation mechanism 91 in the same manner as the liquid a in the anode-side gas-liquid separation mechanism 91. The liquids a and b flowing to the lower side of the anode side gas-liquid separating means 91 are collected in front of the anode side gas piping discharge valve 94, and are discharged to the outside of the apparatus by the own weight when the anode side gas piping discharge valve 94 is opened. Therefore, for the discharge of the liquid separated by the gas-liquid separation mechanism or the oil mist separator, the relationship between the height positions of the machines is important, at least from the upper direction 101107844 22 201243109, the reading order is set to the anode side _ minute _ 92, yang _ gas-liquid separation mechanism 91, anode side gas piping discharge valve 94. The timing of opening and closing of the gas piping drain valve 94 is arbitrarily selected. Further, it is preferably the same in the cathode side oil mist separator 97 connected to the upper portion of the cathode side gas-liquid separation mechanism 96. In order to perform the liquid discharge in the gas-liquid separation mechanism and the oil mist separator in an effective manner, the difference in force can be utilized. For example, a pressure reducer (not shown) is provided in the anode side discharge pipe 95 and the cathode side discharge pipe, and the anode gas and the cathode are formed by decompressing the gas-liquid separation mechanism and the oil mist: The pore flow in the opposite direction of the gas 'by this' can efficiently drain the sulfuric acid in the gas-liquid separation mechanism and the oil mist separator. As an alternative, an inert gas supply unit (not shown) is provided on the π side of the anode side oil mist separator 92 and the cathode side oil mist, and the inert gas is used to separate the separation mechanism from the oil mist (four). In the opposite direction of the gas and the wood body, it is possible to efficiently discharge the liquid in the gas-liquid separation mechanism and the oil mist separator. As the inert gas, for example, nitrogen gas can be used. The separator 5 used in the electrolytic cell 2 is preferably a hydrophilized poly-fluorinated tree (tetra) Wei resin-based rider. In the use of the gas-resin system for the exchange of the enemy's family, the sulphuric acid-carrying water-carrying sulphuric acid enriched by the exchange membrane f _ is oscillated on the _ sub-self___ side and rises, and the amount of liquid on the anode side is reduced, the cathode The sulfuric acid concentration is lowered by dilution with carrier water, and the amount of liquid is increased. 101107844 23 201243109 The liquid level management on the cathode side is carried out by opening and closing the cathode storage tank discharge valve 113, regardless of the periodic discharge or the management of the liquid level in the storage tank, by opening the cathode storage tank. The valve 113 is discharged and the liquid is discharged to the outside of the apparatus by its own weight. The management of the discharge amount can be carried out by various methods. For example, the liquid level discharge can be performed by the liquid level sensor in the cathode side storage tank 38 for measuring the Low position, and the liquid storage can be stopped until the liquid level comes to the sensor position. The valve 113 is managed. As a timing at which the cathode storage tank discharge valve 113 is opened, any of the following cases may be used: monitoring the electrolysis time and the energization current value, calculating the amount of water carried according to the calculation, and opening the case when the amount of water to be carried reaches a predetermined value, and the cathode A liquid level sensor for measuring the High position is provided in the side storage tank 38, and the water storage is carried out until the liquid level is increased to the position of the sensor. Further, the gas which balances the space in the cathode side storage tank 38 can flow from the cathode gas depleting machine 98 through the cathode gas outlet piping 1〇3. If the catholyte is increased by carrying water, the liquid level of the cathode side storage tank % rises and exceeds the capacity of the cathode side storage tank 38. Therefore, in the cathode side storage tank %, the cathode is opened when the liquid level of the storage tank reaches a certain height. The tank discharge valve ιΐ3 discharges a specific amount of liquid from the cathode tank discharge pipe 112, thereby preventing the accumulation amount: remaining. For the management of the liquid level of the cathode side storage tank 38, a liquid level sensor or the like (not shown) can be used. When the amount of the diluted sulfuric acid solution of the cathode electrolysis unit 23 is increased by the carried water carried by the cation through the porous fluorine-based resin film, the liquid level of the cathode side storage tank 38 reaches the height of the mosquito periodically. ^ 101107844 24 201243109 A specific amount of liquid, whereby the overflow of the cathode side tank 38 can be prevented. On the other hand, if the catholyte is not drained and continues to be used, the sulfuric acid of the cathode is further diluted by the carrying of water, and the concentration is lowered and the conductivity is largely lowered. In the case where the cathode liquid is not exchanged for a long period of time (4), the concentration of the two is also monitored by a sulfuric acid concentration meter (not shown), and the concentrated sulfuric acid is supplied from the cathode-sulfuric acid supply unit 39 to a constant concentration. For example, the electrolysis time and the current value are measured, and the amount of water carried out based on the measured value is determined. Then, the amount of the electrolyte in the cathode side storage tank 38 adjusted before the electrolysis is calculated, and the sulfuric acid is added when the amount of the carried water is added to the sulfuric acid concentration. When the concentration of sulfuric acid is lower than the predetermined concentration (10), the amount of sulfuric acid to be added in order to return to the range of the range is calculated, and the amount of sulfuric acid to be extracted is quantified by a flow meter. The side sulfuric acid supply unit % is electrolyzed to the cathode side, and concentrated sulfuric acid is injected into the operating state, thereby controlling the concentration in the catholyte. In order to reduce the fluctuation of the electrolysis conditions, it is more important that the concentration of the concentrated sulfuric acid is delayed, and the concentration of the sulfuric acid supplied to the temperature management and the tank is managed without departing from the predetermined range. The route in the anode-side electrolysis section 20 is such that, after electrolysis at a specific time, the specific oxidizing agent sulfuric acid is discharged from the anode of the anode and the anode of the tank 4 of the anode of the tank. 〇, the use point outside the anode device, the supply side of the electrolysis route B., the electrolyte of the cathode in the cathode-side electrolysis unit 23 is discharged from the cathode storage tank, and the tank is discharged from the cathode side tank 38. 112. Cathode tank discharge valve 113 101107844 25 201243109 Discharge to the outside of the unit. Ruoyang: The adjustment of the electrolytic sulfuric acid in the side storage tank 31 to empty sulfur f. (4) In order to reduce the amount of cans, it is more

或導電率等特性值，於特性值維持規定-I 期間反覆使用陰極液。降士 不履陰極側之溫度、濃度管 係到過硫酸生成效率尤非直接關 仁就下述理由而言，較佳為進行管 王即，由於產生如下情形等，而需要陰極側之溫 陰極㈣通過料陽軒交_之_ 4向陽麵 傳遞溫度，而阻礙將陽極液溫度收人規定_内之情形；陽 極液與陰極液之濃度*同之情形；纟於作騎離子交換膜之 隔膜5成為兩極液濃度差之界面，而成為稀釋熱產生之場 所，變得難以進行電解液之溫度控制，對過硫酸生成效率造 成影響之情形；由於過熱而作為陽離子交換膜之隔膜5劣化 或辱生尺寸變化之情形；由於過熱而產生水蒸氣氣泡，槽之 電阻變大等。 圖2係表示圖1之硫酸電解裝置1之硫峻濃度調整及電解 之步驟之圖。陽極侧電解部20中之步驟係如2所示，由 以下各步驟構成。 1) 純水供給步驟 由陽極侧純水供給配管10向陽極側儲罐31中供給純水。 2) 純水循環步驟 驅動陽極側泵33而使純水循環。此時，陽極室4中不通 101107844 26 201243109 液，而經由陽極侧旁路配管36使純#_ 3) 濃硫酸供給步驟 、’’内循衣0 由陽極侧濃硫酸供給部3 之純水中’並繼續循環，藉此將濃二 ΓΓΓΓ軸純纽合後不久料通塌極侧冷卻器 4可直接去_魏錢料 熱’抑制蒸氣或霧之產生。進而，可抑制由稀釋4= =酸，之溫度上升,保護周邊之：之 閥專免於“熱所引起之破損或變形等。 4) 氣體出口配管排液步驟 94蝴簡排液配管 排;侧氣液分離機構91及陽極側油霧分離器92之 Λ步驟係於上述3)丨農硫酸供給步驟、下述5)稀釋硫 I濃度調整步驟及6)電解步射隨時進行。 1 5) 硫酸溫度及濃度調整步驟 -面於路線Α㈣稀釋雜溶液進行_冷卻直 7度《下、純為域抓《τ—面崎齡 酸溫度為3m之溶液中氧化性物質產生之電流=2 因此較佳為於電解前冷卻至耽以下。又，較佳為= =度設為2〜1G _/卜若硫酸濃度超過1G啸，二 0錄物f之電流效率急劇下降，電流效率變為60%以 另方面，若未達2 mol/L，則成為氧化性物質之原料 101107844 27 201243109 之溶液令之硫酸離子變少，電流效率下降至ό〇%以下，因此 其較佳為將硫酸濃度設為上述範圍内。 如上所述於在陽極側電解部20+進行步驟之期間，如圖 2所不’亦可於陰極側電解部23 ^㈣之方式進行以下 步驟。 1) 純水供給步驟 由陰極側純水供給配管12將純水供給至陰極側儲罐38 中。 2) 純水循環步驟 」區動陰極舰40使純水於路線A，内循環。此時，於陰極 中、液而、、生由陰極側旁路配管43於陰極側儲罐38 中使純水循環。 3) 漠硫酸供給步驟 "ΠΓ硫酸供給部39將濃硫酸供給至於路線A.内循 :=中：續進行循環，藉此將濃硫酸與純水混合。於 =:=τ與純水混合後不久溶液進入陰極侧冷 釋熱’抑制蒸氣或霧之產生 ^ 對於循環流量為2〇%以下之流旦、右、/硫酸之供給流量相 之陰極慮_供給部3^、;^可抑獅_熱所引起 泵、閥等免於由高熱所•二：周邊之配管、 4) 氣體出口配管排液步驟 101107844 28 201243109 藉由打開陰極側氣體配管排液閥99而由陰極側排液配管 進行陰極側氣液分離機構96及陰極側油霧分離器97之 排液。該步驟係於上述3)濃硫酸供給步驟、下述5)稀釋硫 ，酸濃度調整步職6)電解步财隨時進行。 5)硫酸溫度及濃度調整步驟 一面於路線A’内對稀釋硫酸溶液進行循環冷卻直至成為 所需之溫度以下、較佳為溫度3〇t以下，-面進行混合直 至變均句為止。於硫酸濃度為抑以下之溶液中生成氧化 性物質之電流效率較高，因此較佳為於電解前冷卻至3(TC 以下。 又硫酉夂濃度較佳為設為2〜1〇 m〇l/L。若疏酸滚度超過 l〇mol/L ’财成氧化性物f之電流效率急劇下降電流效 2成為6G%以下，另—方面，若成為未達2m‘，則成為 氧化|1物吳之原料之溶液Ψ之硫酸離子變少，因此電流效率 下降至60%以下，因此其較佳為將硫酸濃度設為上述範圍 内0 為了將陽極側與陰極側完全地分離，而於陽極側及陰極侧 所進行之1)〜5)之步驟相同，且可各自完全獨立地進行。 如上所述’於陽極側與陰極側中之陽極側稀釋硫酸生成路 線A及陰極側稀釋硫酸生成路線A，中，調整至所需之溫度 及所品之辰度的稀釋硫酸，係於陽極侧電解硫酸生成路線B 及陰極側電解路線B，之電解步驟中進行電解。 101107844 29 201243109 6) 電解步驟 電解步^係於上豸1)〜5)於陽極側、陰極側均結束後所進 行之將稀釋魏雜⑽之㈣。使_破歸於陽極側 電解部20及陰極側電解部23均進行循環而進行電解。若將 溶液溫度設為3(TC以下則電流效率較高，故而電解中之溶 液溫度較佳為管理至30Ϊ以下。 7) 陽極液（電解硫酸)供給步驟 於電解步驟中所生成之電解硫酸係於陽極側電解部2〇之 路線B中調整至所需之溫度及所需之濃度後，由使用點供 給。將其稱作電解硫酸液供給步驟。於該電解硫酸液供給步 驟中’於上述電解步驟中電解特定時間後，或藉由未圖示之 濃度監視器監視氧化性物質濃度’將濃度到達特定之濃度之 陽極液供給至體系外。軸供給至抗關剝轉置或钮刻裝 置等中，但所連接之裝置或設備並無限定。 、 於本發明之硫酸電解裝置中，可將用以測定氧化性物質濃 度或硫酸濃度之濃度監視m於裝置内或對電解硫酸進 行通液之外部配管中。利用濃度監視器獲得之測定值，可用 於供給至電解槽中之電流值之控制、或自清洗裝置等硫酸電 解裝置向對電解硫酸進行送液之裝置之運轉信號或送液信 號或警告等㈣之輸a時機紋等。再者，作為濃度監視器 之測定方式並無特別限制。 ° 8) 陰極液排液步驟 101107844 30 201243109 於電解步驟中陰極液由於攜帶水而增加，若陰極側儲罐 38之液面達到特定位置，則陰極儲罐排出閥113暫時打開 而排出少量陰極液。 ： 於電解步驟中所生成之陰極液係由陰極側電解部23之陰 . 極側電解路線B’排出。將其稱作陰極液排液步驟。於該陰 極液排液步驟中，為將由攜帶水稀釋之陰極液自陰極侧儲罐 38中全部排出之轉。其可預先設定陰極液之使用次數並 於到H人數後進行排液，亦可利用未圖示之硫酸濃度計測 定陰極液之硫酸濃度並於濃度下降至特定值時進行排液。再 者，陰極排液步驟亦可與陽極液供給步驟同時進行，但無法 與電解步驟同時進行。 於本發明之其他例中，亦可於陽極侧電解部20内搭載2 個以上之陽極側儲罐，例如，藉由每個儲罐分配向裝置外之 送液專用、稀釋硫酸調整專用、電解專用之類功能，或送液 專用、稀釋硫酸調整與電解步驟專用之類功能之分配，亦可 效率良好地於短時間内大量生成含有氧化性物質之硫酸。亦 =可於陰_電解部23 h相同之方式具備具有複數個儲罐 5之機構。硫酸電解裝置1亦可搭載2台以上之槽2，亦 可於1台電解槽中設置2對以上之陽陰極組而形成雙極構 造。 « 圖3係表示於陽極側電解部2〇中設置複數個陽極侧儲罐 之例之圖雖然陰極側電解部23未圖示，但與圖^中之陰 101107844 201243109 極侧電解部23相同。為矣 加袖碰 4N為表不於路線A中並列設置第丨陽極 」=49及第2陽極側儲罐5〇，於第^陽極側儲罐的中 斤生成之3有氧化性物質之電解硫酸後，可對切換闕 51〜58進行切換砂第2陽_觸50中生成含有特定濃 度之氧化性物質之電解硫酸的硫酸電解裝置者^藉由設 種方式， (1) 於第1陽_卿49巾f積轉之硫酸，於切換各閥 而於第2陽極側儲罐5G中以相同之方式製造電解硫酸之期 間可自第1陽極侧儲罐49向使用點供給電解硫酸。藉由 反覆進行該步驟’可連續地無中斷地供給電解硫酸，並且 (2) 可於第1陽極侧儲罐49與第2陽極側儲罐％中製造、 蓄積各自之硫酸濃度、氧化性物質濃度之電解硫酸，並向兩 個位置之使用點進行送液或自丨台裝置向所要求之氧化能 力不同之使用步驟進行送液。 再者’如上所述，陰極側電解部23巾之陰極側儲罐亦可 以與陽極側儲罐相同之方式設置複數個。 圖4係表示圖3之硫酸電解裝置丨之硫酸濃度調整及電解 之步驟之圖。為冷卻器或硫酸混合器僅為一個（共用）之情形 者。首先’以下對圖4之左側所示之步驟進行說明。 1)純水供給步驟 打開切換閥55，由陽極側純水供給配管1〇將純水供給至 陽極侧儲罐49中。供給之水量可藉由利用來自設置於儲罐 101107844 32 201243109 49中之液面感測器的信號或來自設置於陽極側純水供給配 管10中之累積流量計之信號關閉切換閥55而定量。再者， 附屬於陽極側儲罐50之切換閥52、54為關閉狀態。 2) 純水循環步驟 驅動陽極側栗33使純水循環。此時，陽極侧旁路闕％ 設為打開狀態，陽極室出口閥22、陽極室入口闕21設為關 閉狀態。於陽極室4中不通液，純水經由陽極側旁路配管 36而於路線a内進行循環。 3) 濃硫酸供給步驟 由陽極側濃硫酸供給部32將濃硫酸供給至於路線A内進 行循環之純水中，繼續進行循環，藉此將濃硫酸與純水混 合。於該方法中，於將濃硫酸與純水混合後不久溶液進入陽 極側冷卻器34中，因此可直接去除濃硫酸與純水混合時所 產生之稀釋熱’抑㈣氣或霧之產生。進而，可抑制由稀釋 熱所引起之陽極側濃硫酸供給部32之溫度上升，保護周邊 _管I %等免於由南熱所彳丨起之破損或變形等。 4) 氣體出口配管排液步驟 陽極側離機構91及陽極側油霧分離器％之排液， 係藉由打開陽極側氣體配管排_ 94而由陽極側排液配管 進行該步驟係於上述3)濃硫酸供給步驟、下述^稀釋 硫酸濃度調整步驟及6)電解步驟中隨時進行。 5) 硫酸溫度及濃度調整步驟 101107844 33 201243109 一面於陽極側稀釋硫酸生成政 取路線A内對稀釋硫酸溶液進 行循環冷卻直頌需之溫“下、較佳為溫度卿以下一 面進行混合。㈣韻溫度為机以下之餘巾生成氧化 性物質之電流效率較高，因此如Or a characteristic value such as conductivity, and the catholyte is repeatedly used while the characteristic value is maintained at the prescribed -I. It is not the direct reason that the temperature and concentration of the pipe on the cathode side are not on the cathode side. For the following reasons, it is preferable to carry out the temperature of the cathode on the cathode side due to the following situation. (4) Passing the temperature of the yang yang _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ (5) becomes an interface between the two-electrode liquid concentration difference, and becomes a place where the dilution heat is generated, and it becomes difficult to control the temperature of the electrolytic solution, which affects the production efficiency of persulfuric acid; the separator 5 which is a cation exchange membrane is deteriorated or insulted by overheating. In the case of a change in the size of the raw material; water vapor bubbles are generated due to overheating, and the resistance of the groove becomes large. Fig. 2 is a view showing the steps of adjusting the sulfur concentration and electrolysis of the sulfuric acid electrolysis device 1 of Fig. 1. The steps in the anode-side electrolysis section 20 are as shown in 2, and are constituted by the following steps. 1) Pure water supply step Pure water is supplied to the anode side storage tank 31 from the anode side pure water supply pipe 10. 2) Pure water circulation step The anode side pump 33 is driven to circulate pure water. At this time, 101107844 26 201243109 liquid is not supplied to the anode chamber 4, and pure #_3) concentrated sulfuric acid supply step, ''inner recirculation 0' is supplied to the pure water of the anode side concentrated sulfuric acid supply unit 3 via the anode side bypass piping 36. 'And continue to cycle, so that after the thick two shafts are purely bonded, the material can be directly removed to the side of the cooler 4 can directly reduce the generation of steam or fog. Further, it is possible to suppress the temperature rise by dilution 4 = = acid, and protect the periphery: the valve is exclusively protected from "damage or deformation caused by heat, etc. 4" gas outlet pipe discharge step 94 butterfly discharge pipe row; The steps of the side gas-liquid separation mechanism 91 and the anode-side oil mist separator 92 are performed in the above 3) the sulphuric acid supply step, the following 5) the diluted sulfur I concentration adjustment step, and 6) the electrolysis step at any time. Sulfuric acid temperature and concentration adjustment step - surface in the Α (4) dilute the mixed solution _ cooling straight 7 degrees "under, pure for the field to grasp the τ - surface acid acid temperature of 3m solution in the solution of the current generated by the = 2 Preferably, it is cooled to below 电解 before electrolysis. Further, it is preferable that == degree is set to 2~1G _/ If the concentration of sulfuric acid exceeds 1G, the current efficiency of the recording material f decreases sharply, and the current efficiency becomes 60%. On the other hand, if it is less than 2 mol/L, the solution of the oxidizing substance 101107844 27 201243109 will reduce the amount of sulfate ions and reduce the current efficiency to less than ό〇%. Therefore, it is preferable to set the sulfuric acid concentration to Within the above range, as described above, in the anode side electrolysis section 20+ In the case of the cathode side electrolysis unit 23 (4), the following steps can be performed as follows: 1) The pure water supply step supplies the pure water to the cathode side storage tank 38 from the cathode side pure water supply pipe 12 2) The pure water circulation step" zone moves the cathode ship 40 so that the pure water circulates in the route A. At this time, pure water is circulated in the cathode side storage tank 38 by the cathode side bypass piping 43 in the cathode, the liquid, and the raw material. 3) Desert sulfuric acid supply step "ΠΓ sulfuric acid supply unit 39 supplies concentrated sulfuric acid to route A. Inside: = Medium: The cycle is continued, whereby concentrated sulfuric acid is mixed with pure water. Shortly after the =:=τ is mixed with pure water, the solution enters the cathode side to release heat. 'Suppresses the generation of steam or mist. ^ For the flow rate of the flow rate of the flow, the flow rate of the flow rate of 2% or less. The supply unit 3^,; ^ can suppress the lion_heat caused by the pump, the valve, etc. from the high heat • 2: the surrounding piping, 4) the gas outlet piping draining step 101107844 28 201243109 by opening the cathode side gas piping discharge The valve 99 is discharged from the cathode side gas-liquid separation mechanism 96 and the cathode side oil mist separator 97 by the cathode side discharge pipe. This step is carried out in the above 3) concentrated sulfuric acid supply step, 5) dilute sulfur, acid concentration adjustment step 6) electrolysis step. 5) Sulfuric acid temperature and concentration adjustment step The diluted sulfuric acid solution is circulated and cooled in the route A' until it is at a desired temperature or lower, preferably at a temperature of 3 Torr or less, and the surface is mixed until it becomes a uniform sentence. It is preferred to generate an oxidizing substance in a solution having a sulfuric acid concentration of less than or equal to a lower concentration. Therefore, it is preferably cooled to 3 (TC or less) before electrolysis. The concentration of sulfonium is preferably set to 2 to 1 〇m〇l. /L. If the acidity rolling degree exceeds 1〇mol/L, the current efficiency of the oxidized substance f decreases sharply, and the current efficiency 2 becomes 6G% or less. On the other hand, if it becomes less than 2m', it becomes oxidation|1 The solution of the raw material of Wuwu has less sulfuric acid ions, so the current efficiency drops below 60%, so it is preferable to set the sulfuric acid concentration to be within the above range. 0 In order to completely separate the anode side from the cathode side, and to the anode The steps 1) to 5) performed on the side and the cathode side are the same, and can be carried out completely independently of each other. As described above, in the anode-side dilute sulfuric acid production route A and the cathode-side diluted sulfuric acid production route A in the anode side and the cathode side, the diluted sulfuric acid adjusted to the desired temperature and the degree of the product is attached to the anode side. Electrolysis of sulfuric acid is generated in route B and cathode side electrolysis route B, and electrolysis is carried out in the electrolysis step. 101107844 29 201243109 6) Electrolysis step The electrolysis step is performed on the anode side 1) to 5). After the end of the anode side and the cathode side, the Wei (10) (4) is diluted. The electrolysis unit 20 and the cathode side electrolysis unit 23 are both circulated and electrolyzed. If the temperature of the solution is set to 3 (the current efficiency is higher than TC, the temperature of the solution in the electrolysis is preferably managed to 30 Ϊ or less. 7) The anolyte (electrolytic sulphuric acid) supply step is the electrolytic sulfuric acid system generated in the electrolysis step. After being adjusted to the desired temperature and the required concentration in the route B of the anode side electrolysis unit 2, it is supplied from the use point. This is called an electrolytic sulfuric acid supply step. In the electrolytic sulfuric acid supply step, after the electrolysis for a certain period of time in the electrolysis step, or by monitoring the concentration of the oxidizing substance by a concentration monitor (not shown), the anolyte whose concentration reaches a specific concentration is supplied to the outside of the system. The shaft is supplied to the anti-off stripping or button engraving device, etc., but the connected device or device is not limited. In the sulfuric acid electrolysis apparatus of the present invention, the concentration for measuring the concentration of the oxidizing substance or the concentration of the sulfuric acid can be monitored in the external piping of the apparatus or the electrolytic sulfuric acid. The measured value obtained by the concentration monitor can be used for the control of the current value supplied to the electrolytic cell, or the operation signal or the liquid supply signal or warning of the device for supplying the liquid to the electrolytic sulfuric acid from a sulfuric acid electrolysis device such as a cleaning device (4) The loss of a time machine and so on. Further, the measurement method of the concentration monitor is not particularly limited. ° 8) Catholyte draining step 101107844 30 201243109 In the electrolysis step, the catholyte is increased by carrying water. If the liquid level of the cathode side tank 38 reaches a specific position, the cathode tank discharge valve 113 is temporarily opened to discharge a small amount of catholyte. . The catholyte generated in the electrolysis step is discharged from the cathode side electrolysis route B' of the cathode side electrolysis portion 23. This is called a catholyte draining step. In the cathode liquid discharge step, all of the catholyte diluted with the carried water is discharged from the cathode side storage tank 38. The number of times of use of the catholyte can be set in advance, and the liquid can be discharged after reaching the number of H. The concentration of sulfuric acid in the catholyte can be measured by a sulfuric acid concentration meter (not shown), and the liquid can be discharged when the concentration falls to a specific value. Further, the cathode draining step may be performed simultaneously with the anolyte supply step, but not simultaneously with the electrolysis step. In another example of the present invention, two or more anode-side storage tanks may be mounted in the anode-side electrolysis unit 20, and for example, each of the storage tanks may be used for dispensing liquid outside the apparatus, dilute sulfuric acid adjustment, and electrolysis. Special functions such as special functions for liquid supply, dilute sulfuric acid adjustment, and electrolysis steps can be used to efficiently produce a large amount of sulfuric acid containing oxidizing substances in a short period of time. Also, a mechanism having a plurality of storage tanks 5 can be provided in the same manner as the cathode-electrolysis unit 23h. The sulfuric acid electrolysis device 1 may be equipped with two or more tanks 2, or two or more pairs of anode and cathode groups may be provided in one electrolytic cell to form a bipolar structure. Fig. 3 is a view showing an example in which a plurality of anode side storage tanks are provided in the anode side electrolysis unit 2A. Although the cathode side electrolysis unit 23 is not shown, it is the same as the cathode side electrolysis unit 23 in Fig. 101107844 201243109. For the 矣 袖 碰 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 After sulfuric acid, it is possible to switch the cesium 51 to 58 to switch the sulphuric acid electrolysis device containing the oxidizing substance of a specific concentration to the sulphuric acid in the second cation 50. By means of the seeding method, (1) in the first yang _ In the case where the electrolytic sulfuric acid is produced in the same manner as in the second anode side storage tank 5G, the electrolytic sulfuric acid can be supplied from the first anode side storage tank 49 to the use point during the switching of the valves. By repeating this step, the electrolytic sulfuric acid can be continuously supplied without interruption, and (2) the respective sulfuric acid concentration and oxidizing substance can be produced and accumulated in the first anode side storage tank 49 and the second anode side storage tank %. The concentration of electrolytic sulfuric acid is sent to the point of use at two locations or from the station to the required oxidizing capacity. Further, as described above, the cathode side storage tank of the cathode side electrolysis portion 23 may be provided in plural in the same manner as the anode side storage tank. Fig. 4 is a view showing the steps of adjusting the sulfuric acid concentration and electrolysis of the sulfuric acid electrolysis apparatus of Fig. 3. It is only one (shared) case for the cooler or the sulfuric acid mixer. First, the steps shown on the left side of Fig. 4 will be described below. 1) Pure water supply step The switching valve 55 is opened, and pure water is supplied from the anode-side pure water supply pipe 1 to the anode-side storage tank 49. The amount of water supplied can be quantified by closing the switching valve 55 by a signal from a liquid level sensor provided in the storage tank 101107844 32 201243109 49 or a signal from an accumulated flow meter provided in the anode side pure water supply pipe 10. Further, the switching valves 52, 54 attached to the anode side storage tank 50 are in a closed state. 2) Pure water circulation step The anode side pump 33 is driven to circulate pure water. At this time, the anode side bypass port % is set to the open state, and the anode chamber outlet valve 22 and the anode chamber inlet port 21 are set to the closed state. The anode chamber 4 is not permeable, and the pure water is circulated in the route a via the anode side bypass piping 36. 3) Concentrated sulfuric acid supply step The concentrated sulfuric acid supply unit 32 supplies the concentrated sulfuric acid to the pure water circulated in the route A, and continues the circulation, thereby mixing the concentrated sulfuric acid with the pure water. In this method, the solution enters the anode side cooler 34 shortly after the concentrated sulfuric acid is mixed with the pure water, so that the dilution heat generated by the mixing of the concentrated sulfuric acid and the pure water can be directly removed. Further, it is possible to suppress an increase in temperature of the anode-side concentrated sulfuric acid supply unit 32 due to the heat of dilution, and to protect the periphery_tube I% from damage or deformation caused by the heat of the south. 4) Gas outlet pipe discharge step The discharge of the anode side separation mechanism 91 and the anode side oil mist separator % is performed by opening the anode side gas pipe row _ 94 by the anode side discharge pipe. The concentrated sulfuric acid supply step, the following dilute sulfuric acid concentration adjustment step, and the 6) electrolysis step are performed at any time. 5) Sulfuric acid temperature and concentration adjustment step 101107844 33 201243109 One side of the diluted sulfuric acid on the anode side is formed in the political route A. The diluted sulfuric acid solution is circulated and cooled to the temperature required for the lower side, preferably the lower side of the temperature. (4) Rhyme The temperature is higher than that of the machine under the machine to generate oxidizing substances, so the current efficiency is high.

此心佳為於電解前冷卻至30°C 以下。 又，硫酸濃度較佳為設為2〜ln 1/τ 1Q mol/L。若硫酸濃度超過 1 〇 mol/L ’則生成氧化性物質之雷 又電流效率急劇下降，電流效This is good for cooling to below 30 °C before electrolysis. Further, the sulfuric acid concentration is preferably set to 2 to ln 1 / τ 1 Q mol / L. If the concentration of sulfuric acid exceeds 1 〇 mol/L ', the oxidizing substance is thundered and the current efficiency is drastically reduced.

率成為60%以下’另一方面，名:士、也4 A 右成為未達2 m〇l/L，則成為 氧化性物質之原料之溶液中之硫酸離子變少，因此電流效率 下降至60%以下，因此其較佳為將硫酸濃度設為上述範圍 内。 =上述之方式於陽極财之陽極側稀釋硫酸生成路線a 中，调整至所需之溫度及所需之濃度的稀釋硫酸係於陽極側 電解硫酸生成路線B之電解步驟中進行電解。 6)電解步驟 電解步驟係於上述D〜5)結束後所崎之將稀釋硫酸溶 ^電解之步驟。雖然於圖4中關於陰極側未圖*，但亦可以 與上述圖2中之情形相同之方式而於陰極側以與陽極側相 同之方式進行上述丨）〜5)之各步驟。 #於陽極側電解部2G中使稀釋硫酸溶液循環而進行電解。 *字;谷液’里度设為3〇。匸以下則電流效率較高，因此電解中 之溶液溫度較佳為管理成30°C以下。 101107844 34 201243109 關閉陽極侧旁路閥3 5，打開陽極室出Π閥2 2、陽極室入 口閥21 ’而於陽極側儲罐的與陽極室4之間循環。 ;電解槽2巾供給直流電流’利用既定供給電流進行規定 ‘彳]之電解’而獲得含有規定濃度之氧化性物質之電解硫 酸。關閉切換閥51、qI , * ^ 53而生成之含有規定濃度之氧化性 物質之電解硫酸蓄積於陽極儲罐49中。 7)陽極液（電解硫酸)供給步驟 ;電解步驟巾所生成之電解硫酸係於陽極侧電解部Μ之 陽極側電解硫酸生成路線B中，調整至所需之溫度及所需 之氧化性物質濃度，而向使用點供給。將其稱作電解硫酸液 供給步驟。於該電解硫酸液供給步驟中，於上述電解步驟中 電解特疋時間後，或藉由未圖示之濃度監視器監視氧化性物 質漢度，而將濃度到達特定之濃度之陽極液供給至體系外。 雖然供給至抗㈣剝離裝置或烟裝置等中，但所連接之裝 置或設備並無限定。 如圖4之右側所示，與該7)陽極液供給步驟同時進行， ' 讀上述υ相同之方式對陽極側儲罐50供給純水，其後如 : 下所述，進行1)— 6)。 1)純水供給步驟 打開切換閥56,由陽極側純水供給配管1〇將純水供仏至 陽極側儲罐50。供給之水量可藉由利用來自設置於儲罐％ 中之液面感測器的信號或來自設置於陽極側純水供給配管 101107844 35 201243109 10中之累積机置計之信號關閉切換閥56而定量。再 屬於陽極側儲罐50之切換閥52、54為打開狀態。，附 2)純水循環步驟 驅動陽極側果33使純水進钢盾環。此時，陽極側 35設為打開狀態，陽極室出口閥22、陽極室人 ^ 關閉狀態。於陽極室4中不通液，純水經由陽極側h = 36於路線A内猶環。 严配& 3) ?農硫酸供給步驟 由陽極側濃琉醆供給部32將濃硫酸供給至於路線A内進 行循環之純水中，繼續進行循環，藉此將濃硫酸與純水混 合。於該方法中，於將濃硫酸與純水混合後不久溶液進入陽 極側冷卻器34中，因此可直接去除濃硫酸與純水混合時所 產生之稀釋熱，抑制蒸氣或霧之產生。進而，可抑制由稀釋 熱所引起之陽極侧濃硫酸供給部32之溫度上升，保護周邊 之配管、栗、閥等免於由高熱所引起之破損或變形等。 4) 氣體出口配管排液步驟 藉由打開陽極侧氣體配管排液閥94而由陽極側排液配管 95進行陽極側氣液分離機構91及陽極侧油霧分離器92之 排液。該步驟係於上述3)濃硫酸供給步驟、下述5)稀釋硫 酸濃度調整步驟及6}電解步驟中隨時進行。 5)硫酸溫度及濃度調整步驟 一面於路線A内對稀釋硫酸溶液進行循環冷卻直至所需 101107844 36 201243109 之溫度以下、較佳為溫度成為贼以下—面進行混人 ，溫=為卿以下之溶液中氧化性物質生成之電^率: 间，因此較佳為於電解前冷卻至3〇。〇以下。 又，硫酸濃度較佳為設為 穴力 7、四任於•峰 成氧化性物質之電流效率較1G _ 、 工 < 規酸向。若点 以下，則成為氧化性物質之原料之溶液中之硫: 離子較少，因此電流效率下降。 吸 ，調整至所需之溫 之電解步驟中進行 以上述之方式於陽極側中之路線A中 度及所需之濃度的稀釋硫酸係於路線B 電解。 6)電解步驟 電解步驟係於上述丨)〜5)結束後所進行之將稀釋硫酸溶 液電解之步驟。氣然於圖4中關於陰極側並未圖示，但亦可 以與上述圖2巾之情形相同之方式哺陽極齡同之方式 於陰極側進行上述1)〜5)之各步驟。 於陽極側電解部20 +，使稀釋硫酸溶液循環而進行電 解。右將浴液溫度設為30。(：以下則電流效率較高，因此電 解中之溶液溫度較佳為管理成3〇°c以下。 關閉陽極側旁路閥35 ’打開陽極室出口閥22、陽極室入 口閥21，使稀釋硫酸溶液於陽極側儲罐％與陽極室4之間 進行循環。 於電解槽2巾供給直流電流，利用既定供給電流進行規定 101107844 37 201243109 時間之電解，而獲得含有規定濃度之氧化性物質之電解硫 酸。繼而’關_換閥52、54 ’生成之含有規定濃度之氧 化性物質之電解硫酸係蓄積至陽極儲罐5〇中。 其後，自陽極側儲罐50向使用點供給電解硫酸，而且於 陽極側儲罐49中開始純水供給步驟，反覆進行上述操作。 [實施例] 以下，列舉實施例及比較例更加具體地說明本發明，但本 發明並不限定於以下之實施例。 <實施例1> 利用圖1及圖2所示之硫酸電解裝置及硫酸電解方法進 行。 關於搭載於電解槽2中之陽極3及陰極6，分別使用於口 仫200 mm<i)之矽板上摻硼而賦予導電性之被覆金剛石的導 電性金剛石電極。電流密度設為100 A/dm2。 硫酸溫度及濃度調整步驟於陽極侧、陰極側均為如下所 不，利用純水對濃硫酸進行稀釋，對經溫度調整之特定濃度 之稀釋硫酸進行調整。 陽極側之程序如下所示。 1) 由陽極側純水供給配管10向陽極側儲罐31進行純水供 給並蓄積。純水之供給量係使用未圖示之超音波方式之累積 流量計進行稱重而供給。 2) 驅動陽極側循環泵33使純水於路線A内循環。 101107844 38 201243109 )自1%極側/辰硫酸供給部32將濃硫酸供給至於路線a内 循環之純水中，而生成稀釋硫酸。濃硫酸之供給量係使用未 圖示之超音波方式之累積流量計進行稱重而供給。 4)藉由濃硫酸與純水之混合所產生之稀釋熱係於循環中 ·. 於陽極側冷卻器34中進行冷卻，溫度調整至3GX：以下，並 且利用純水對濃硫酸進行稀釋之稀釋碎l酸溶液係藉由循環 而充分地攪拌並混合。 陰極側之程序如下所示。 1) 由陰極側純水供給配管丨2向陰極側儲罐3 8進行純水供 給並蓄積。純水之供給量係使用未圖示之超音波方式之累積 流量計進行稱重並供給。 2) 驅動陰極側循環泵4〇使純水於路線A，内進行循環。 3) 自陰極侧濃硫酸供給部39將濃硫酸供給至於路線A，内 進行循環之純水中，而生成稀釋硫酸。濃硫酸之供給量係使 用未圖示之超音波方式之累積流量計進行稱重而供給。 4) 藉由濃硫酸與純水之混合所產生之稀釋熱，係於循環中 -- 於陰極側冷卻器41中進行冷卻，溫度調整至3〇〇c以下，並 ' 且利用純水對濃硫酸進行稀釋之稀釋硫酸溶液，係藉由循環 而充分地攪拌並混合。 在陽極侧及陰極側硫酸濃度調整及溫度調整結束後，陽極 側係藉由打開閥21與閥22，關閉閥35而構成路線B，陰 極側係藉由打開陰極室入口閥24與陰極室出口閥25，關閉 101107844 39 201243109 陰極侧旁路閥42而構成陰極側電解路線&面分別向電 解槽中循環供給稀釋硫酸溶液，一面對電解槽供給直流電流 而進行電解’而生成含有氧化性物質之電解硫酸。 繼而，藉由上述方法，將電解前之硫酸濃度於硫酸濃度調 整步驟後進-步於1.8〜16.7 mol/L之範圍内進行調整。陰 極液亦於陰極侧應用相同之方法進行濃度調整。冷卻稀釋硫 酸溶液後，進行電解。條件設為如下。 t流密度 ΓΤππ Δ1 陽極電解液（對關東化學股份 有限公司製造之EL-UM^f ί 量％硫酸進行稀釋） 貞 1 \j\j r\/um 1.8 mol/L 2.0 mol/L 2.3 mol/L 3.7 mol/L 5.3 mol/L 7.1 mol/L 9.2 mol/L 10.0 mol/L 11.5 mol/L 14.1 mol/L 15.4 mol/L 16.7 mol/L 陰極電解液 奧陽極雪解液相ISl 陽極電解液量 ~- 陰極電解液量 -~ 8.5 L ~6T ~ 匙解時之陽極循； >帘| 3 L/min 電解時之陰極循埽泊ψ - 4 L/min 電解液溫度 30*C以下 隔膜 若電解^中乏领酸濃度為 以上，則使用進行親水化之多孔質 PTFE膜。 … 若電解液中之、·酸濃度為以 下，則使用陽_離子交換膜》 自電解部分岔之未圖示之取樣配管對利用上述程序及上 述條件進行電解之稀釋硫酸進行取樣，藉由KI滴定法測定 稀釋硫酸中生成之氧化性物質之總量。 表1表示藉由供於電解之稀釋硫酸溫度而測定相同體積 谷量密度中之總氧化性物質濃度之測定例。硫酸濃度為3 /7 mol/L。若溫度超過30¾則所得之濃度下降。 101107844 40 201243109 [表i] 試驗ϋ" 號 run! 34 RUN2 RUN3~ RUN4~ RUN5~ RUN6* 總氧化性物質濃度 (mol/L) 0.66 Τό5~ 0.54The rate is 60% or less. On the other hand, the name: Shi, and 4 A, the right is less than 2 m〇l/L, and the amount of sulfate ions in the solution which is the raw material of the oxidizing substance is reduced, so the current efficiency is lowered to 60. % or less, so it is preferable to set the sulfuric acid concentration within the above range. = The above method is carried out in the anode side dilute sulfuric acid production route a of the anode, and the diluted sulfuric acid adjusted to the desired temperature and the desired concentration is electrolyzed in the electrolysis step of the anode side electrolytic sulfuric acid formation route B. 6) Electrolysis step The electrolysis step is a step of diluting sulfuric acid dissolved electrolysis after the end of the above D to 5). Although the cathode side is not shown in Fig. 4, the steps of the above-mentioned 丨) to 5) may be performed on the cathode side in the same manner as in the above-described Fig. 2 in the same manner as the anode side. In the anode-side electrolysis unit 2G, the diluted sulfuric acid solution is circulated to perform electrolysis. *Word; Valley Liquid' is set to 3 inches. In the following, the current efficiency is high, so the temperature of the solution in the electrolysis is preferably managed to be 30 ° C or lower. 101107844 34 201243109 Close the anode side bypass valve 35, open the anode chamber outlet valve 2, and the anode chamber inlet valve 21' to circulate between the anode side tank and the anode chamber 4. The electrolytic cell 2 supplies a direct current "electrolysis" of a predetermined concentration by a predetermined supply current to obtain an electrolytic sulfuric acid containing a predetermined concentration of an oxidizing substance. The electrolytic sulfuric acid containing the oxidizing substance having a predetermined concentration generated by closing the switching valves 51, qI, *^ 53 is accumulated in the anode storage tank 49. 7) an anolyte (electrolytic sulphuric acid) supply step; the electrolyzed sulphuric acid produced by the electrolysis step is applied to the anode side electrolysis sulphuric acid formation route B of the anode side electrolysis section, and is adjusted to a desired temperature and a desired oxidizing substance concentration. And supply to the point of use. This is called an electrolytic sulfuric acid supply step. In the electrolytic sulfuric acid supply step, after the electrolysis period in the electrolysis step, or by monitoring the oxidizing substance by a concentration monitor not shown, the anolyte having a concentration reaching a specific concentration is supplied to the system. outer. Although it is supplied to an anti-(4) peeling device or a smoke device or the like, the connected device or equipment is not limited. As shown on the right side of Fig. 4, the anode liquid supply step is carried out simultaneously with the 7) anolyte supply step, and the anode side storage tank 50 is supplied with pure water in the same manner as described above, and thereafter, as described below, 1) - 6) . 1) Pure water supply step The switching valve 56 is opened, and pure water is supplied to the anode side storage tank 50 by the anode side pure water supply pipe 1 . The amount of water supplied can be quantified by closing the switching valve 56 by a signal from a liquid level sensor provided in the tank % or by a signal from an accumulator set in the anode side pure water supply piping 101107844 35 20124310910. . The switching valves 52, 54 belonging to the anode side storage tank 50 are in an open state. , 2) Pure water circulation step Drive the anode side fruit 33 to make pure water into the steel shield ring. At this time, the anode side 35 is set to the open state, and the anode chamber outlet valve 22 and the anode chamber are closed. No liquid is passed through the anode chamber 4, and pure water passes through the anode side h = 36 in the route A. Strictly-mixed & 3) Agrochemical sulfuric acid supply step The concentrated sulfuric acid is supplied to the pure water circulated in the route A by the anode-side concentrated supply unit 32, and the circulation is continued, whereby the concentrated sulfuric acid is mixed with the pure water. In this method, the solution enters the anode side cooler 34 shortly after the concentrated sulfuric acid is mixed with the pure water, so that the dilution heat generated when the concentrated sulfuric acid is mixed with the pure water can be directly removed, and the generation of vapor or mist is suppressed. Further, it is possible to suppress the temperature rise of the anode-side concentrated sulfuric acid supply unit 32 due to the heat of dilution, and to protect the surrounding piping, the chestnut, the valve, and the like from damage or deformation caused by high heat. 4) Gas outlet pipe discharge step The anode side gas discharge pipe 91 is opened, and the anode side gas-liquid separation mechanism 91 and the anode side oil mist separator 92 are discharged by the anode-side discharge pipe 94. This step is carried out at any time in the above 3) concentrated sulfuric acid supply step, the following 5) diluted sulfuric acid concentration adjustment step, and 6} electrolysis step. 5) Sulfuric acid temperature and concentration adjustment step: in the route A, the diluted sulfuric acid solution is circulated and cooled until the temperature of 101107844 36 201243109 is required, preferably the temperature is below the thief - the surface is mixed, and the temperature is the solution below The electrical conductivity of the oxidizing substance is: between, so it is preferred to cool to 3 Torr before electrolysis. 〇The following. Further, the concentration of sulfuric acid is preferably set to be a hole force of 7, and the current efficiency of the oxidizing substance is higher than that of 1G _ , work < When it is below the point, the sulfur in the solution which is a raw material of the oxidizing substance: Since the number of ions is small, the current efficiency is lowered. Suction, adjustment to the desired temperature in the electrolysis step is carried out in the above manner in the anode side of the route A and the desired concentration of the diluted sulfuric acid is applied to Route B electrolysis. 6) Electrolysis step The electrolysis step is a step of electrolyzing the diluted sulfuric acid solution after completion of the above-mentioned 丨) to 5). Although the cathode side is not shown in Fig. 4, the steps of the above 1) to 5) may be carried out on the cathode side in the same manner as in the case of the above-mentioned Fig. 2 towel. The diluted sulfuric acid solution is circulated and electrolyzed in the anode side electrolysis unit 20 + . Set the bath temperature to 30 on the right. (The following is the current efficiency is high, so the temperature of the solution in the electrolysis is preferably managed to be less than 3 ° C. Close the anode side bypass valve 35 'open the anode chamber outlet valve 22, the anode chamber inlet valve 21, so that the diluted sulfuric acid The solution is circulated between the anode side storage tank % and the anode chamber 4. The DC current is supplied to the electrolytic cell 2, and the electrolytic solution of the predetermined concentration of the oxidizing substance is obtained by performing the electrolysis of the predetermined 101107844 37 201243109 by the predetermined supply current. Then, the electrolytic sulfuric acid containing the oxidizing substance of a predetermined concentration generated by the 'off_switches 52, 54' is accumulated in the anode storage tank 5, and thereafter, the electrolytic sulfuric acid is supplied from the anode side storage tank 50 to the use point, and The pure water supply step is started in the anode side storage tank 49, and the above operation is repeated. [Examples] Hereinafter, the present invention will be more specifically described by way of examples and comparative examples, but the present invention is not limited to the following examples. Example 1> The sulfuric acid electrolysis apparatus and the sulfuric acid electrolysis method shown in Fig. 1 and Fig. 2 are used. The anode 3 and the cathode 6 mounted in the electrolytic cell 2 are respectively made Mu to port 200 mm < i) of boron-doped silicon plate to impart electrically conductive diamond electrode coated with the conductive diamond. The current density is set to 100 A/dm2. The sulfuric acid temperature and concentration adjustment steps are as follows on the anode side and the cathode side, and the concentrated sulfuric acid is diluted with pure water to adjust the temperature-adjusted concentration of the diluted sulfuric acid. The procedure on the anode side is as follows. 1) The anode-side pure water supply pipe 10 supplies and accumulates pure water to the anode-side storage tank 31. The supply amount of pure water is supplied by weighing using an ultrasonic flowmeter (not shown). 2) The anode side circulation pump 33 is driven to circulate pure water in the route A. 101107844 38 201243109) The concentrated sulfuric acid is supplied from the 1% pole side/sulphuric acid supply unit 32 to the pure water circulated in the route a to produce diluted sulfuric acid. The supply amount of concentrated sulfuric acid is supplied by weighing using an accumulation flowmeter of an ultrasonic method not shown. 4) The dilution heat generated by the mixing of concentrated sulfuric acid and pure water is in the circulation. The cooling is performed in the anode side cooler 34, the temperature is adjusted to 3 GX: or less, and the dilution of the concentrated sulfuric acid is diluted with pure water. The crushed acid solution was thoroughly stirred and mixed by circulation. The procedure on the cathode side is as follows. 1) Purified water is supplied and accumulated by the cathode-side pure water supply pipe 2 to the cathode-side storage tank 38. The supply amount of pure water is weighed and supplied using an accumulative flow meter of an ultrasonic method (not shown). 2) Drive the cathode side circulation pump 4〇 to circulate the pure water in the route A. 3) The concentrated sulfuric acid supply unit 39 supplies the concentrated sulfuric acid from the cathode side to the route A, and the purified water is circulated therein to produce diluted sulfuric acid. The supply amount of concentrated sulfuric acid is supplied by weighing using an accumulation flowmeter of an ultrasonic method (not shown). 4) The dilution heat generated by the mixing of concentrated sulfuric acid and pure water is in the circulation - cooling in the cathode side cooler 41, the temperature is adjusted to below 3 〇〇c, and 'with pure water to the thick The diluted sulfuric acid solution diluted with sulfuric acid is thoroughly stirred and mixed by circulation. After the adjustment of the sulfuric acid concentration on the anode side and the cathode side and the temperature adjustment are completed, the anode side is closed by opening the valve 21 and the valve 22 to close the valve 35, and the cathode side is opened by opening the cathode chamber inlet valve 24 and the cathode chamber outlet. The valve 25 closes the 101107844 39 201243109 cathode side bypass valve 42 to form a cathode side electrolysis route & a surface, which supplies a diluted sulfuric acid solution to the electrolytic cell, and supplies a direct current to the electrolytic cell to perform electrolysis, thereby generating oxidation resistance. Electrolytic sulfuric acid of matter. Then, by the above method, the sulfuric acid concentration before electrolysis is adjusted in the range of 1.8 to 16.7 mol/L after the sulfuric acid concentration adjustment step. The cathode solution was also subjected to the same method for concentration adjustment on the cathode side. After cooling the diluted sulfuric acid solution, electrolysis was carried out. The conditions are set as follows. T-flow density ΓΤππ Δ1 anolyte (diluted by EL-UM^f ̄ quantity % sulfuric acid manufactured by Kanto Chemical Co., Ltd.) 贞1 \j\jr\/um 1.8 mol/L 2.0 mol/L 2.3 mol/L 3.7 mol/L 5.3 mol/L 7.1 mol/L 9.2 mol/L 10.0 mol/L 11.5 mol/L 14.1 mol/L 15.4 mol/L 16.7 mol/L Catholyte Anodic Snow Solution Liquidion IS1 Anolyte Amount ~- Catholyte amount -~ 8.5 L ~6T ~ Anode circulation when spoon solution; > Curtain | 3 L/min Cathodic circulation in electrolysis - 4 L/min Electrolyte temperature 30*C or less When the concentration of the spent acid in the electrolysis is more than or equal to the above, a porous PTFE film which is hydrophilized is used. ... If the acid concentration in the electrolyte is below, use a positive ion-exchange membrane to sample the diluted sulfuric acid electrolyzed by the above procedure and the above conditions from a sampling pipe (not shown) by electrolysis. The total amount of oxidizing substances formed in the diluted sulfuric acid is determined by titration. Table 1 shows measurement examples in which the concentration of the total oxidizing substance in the same volume density is measured by the temperature of the diluted sulfuric acid supplied to the electrolysis. The concentration of sulfuric acid is 3 / 7 mol / L. If the temperature exceeds 303⁄4, the resulting concentration decreases. 101107844 40 201243109 [Table i] Test ϋ" No. run! 34 RUN2 RUN3~ RUN4~ RUN5~ RUN6* Total oxidizing substance concentration (mol/L) 0.66 Τό5~ 0.54

TJT 1.11 - 45 1,11_____ 可知根據總氧化性物質~一·—~^~~______ & 、度所求出之電流效率自3(TC附 近大幅度下降，可知為了效傘自& L L附 +良好地生成氧化性物質， 用製成30C以下之稀釋錢進行電解較為有效。 表2表示將硫酸濃度設為U〜⑽睛時之總氧化性 物質濃度與電流效率之結果1流密度設為議A/dm2，體 積容量密度設為25 Ah/L。可知根據總氧化性物質濃度所求 出之電流效率係於硫酸濃度為2.〇〜丨〇 〇 m〇1/L時，顯示6〇% 以上之區域，於硫酸濃度較其更稀之區域及更濃之區域中電 流效率急劇下降。 [表2]TJT 1.11 - 45 1,11_____ It is known that the current efficiency obtained from the total oxidizing substance ~1·~~~~______ & degree is greatly reduced from 3 (the vicinity of TC), it is known that the effect is from the umbrella & LL + It is effective to form an oxidizing substance well, and it is effective to carry out electrolysis by making a dilution of 30 C or less. Table 2 shows the result of the total oxidizing substance concentration and current efficiency when the sulfuric acid concentration is U~(10), and the flow density is set to 1 A/dm2, the volumetric capacity density is set to 25 Ah/L. It is known that the current efficiency determined from the total oxidizing substance concentration is 6 〇 when the concentration of sulfuric acid is 2. 〇~丨〇〇m〇1/L. In the region above %, the current efficiency drops sharply in areas where the sulfuric acid concentration is thinner than in the leaner region. [Table 2]

|硫酸濃度 | (mol/L) 電流密度 (A/dm2) 體積冢 (Ah/L、& 溶液溫度 (°C) 總氧化性物質濃度 (mol/L) RUN7 I 1.8 100 〇 25 54 RUN8 2.0 100 0.28 60 RUN9 2.3 100 25 0.32 69 RUN 10 3.7 100 25 ^ 0.36 nn RUN 11 5.3 100 ----- It 25 〇 35 75 RUN 12 I 7.1 _ 100 25^ 0.34 η λ RUN 13 1 9.2 100 fH 0.29 A艾 RUN 14 10.0 100 00 0.28 RUN 15 11.5 100 DU 0.19 42 RUN 16 14.1 100 0.13 29 RUN 17 15.4 100 25~~~ 0.11 ΟΛ RUN 18 | 16.7 100 it— Z外 0.06 1 A —-----, 1 H 101107844 41 201243109 表3表示於電解中持續電解液之冷卻並保持3〇°C之例、 與於電解中中止冷卻而藉由因電解所引起之發熱而電解液 溫度上升至51°C之例。 [表3] 硫酸濃度 電流密度 體積容量密 溶液溫 (mol/L) (A/dm2) 度(Ah/L) 度CC) JlUNlTT3.7 100 190 30 ΚϋΝ2(ΓιΓ 3 7 100 190 51 總氧化性 物質濃度 [m〇l£L') 1.51 ~〇J2 根據表3可知，持續冷卻至3(TC之例係獲得氧化性物質 濃度1.51 m〇i/L，與其相對地，於電解中中止冷卻並藉由因 電解所引起之發熱而電解液溫度上升至51。(：之例係氧化性 物質濃度停留於0.72 mol/L，無法進行效率良好之電解。 <比較例1 > 繼而，作為比較例 、 〜、…个辫弋渑合位置 設為陽極側儲罐内，進而，不設置氣液分離機構及油霧分離 器之情形。於該比較例1之稀釋硫酸生成步驟中，冷卻並不 適當，而產生裝置故障。 〃 :比#乂例1中，為了調整6 m〇i/L之稀纒 儲罐上邱稀擇疏酸溶液，而自 轉上㈣儲罐内投人超純水2 ^之98質量。目锗罐下部投入5.9 “㈣酸麵均為室溫。料水供給流量 、'mm 98質量％硫酸供給流量為〇2〜"、 於儲罐内部藉由因超純水與硫酸之現軸。 而溶液溫度上并m L1 厅產生之稀釋熱 升，因此產生大量蒸氣。由於 出口配管之内壁附著有污點。 、★而於氣體 101107844 42 201243109 ;8質里％硫^之供給結束後，㈣起動*使溶液 = 中循環’將稀釋硫酸溶液冷卻至25°C。冷卻 束$使/合液於儲罐與電解槽中循環，而開始電解。電解 $之錢咖度為27°C ’陽極及陰極之氣體出口配管之氣體 :β ^ 5 kPa ’但於電解開始10分鐘後陰極儲罐之氣壓急 劇上升至J達200 kPa，成為異常，故而於儲罐與電解槽中 止溶液循環。 此時ϋ為由雜之稀釋熱所產生之蒸氣，於設置於陰極 2罐與作為陰極侧除害設備*設置之氫燃燒塔之間的過渡 器之内。Ρ ’滯留有凝結有硫酸稀釋時產生之霧及蒸氣之液 體由於5亥液體而氣體過濾器發生堵塞，因此陰極氣體於陰 極儲罐與職ϋ之間㈣而產生高壓。解放殘壓後，於拆却 槽時，於陽離子交換獏中有貫通穴。 (產業上之可利用性） 根據本發明之额電解裝置及硫酸電解方法，可於震置内 生成溫度及濃度經管理之稀釋硫酸，進而藉由將該稀釋硫酸 :於經溫度管理之條件下電解，而可高效率且安全地生成含有 :氧化性物質之硫酸。進而，可提供—種可利用較高之電流效 率製造利用先前技術無法達成之高濃度氧化性物質溶液，可 穩定地生成氧化性活物f之硫酸轉裝置及贿電解方法。 【圖式簡單說明】 ° 圖1係表示本發明之硫酸電解裝置之一例之整體圖。 101107844 43 201243109 圖2係說明藉由圖1之硫酸電解裝置而進行之硫酸之溫度 及濃度調整、電解、供給、排液處理等各步驟的步驟圖。 圖3係表示本發明之硫酸電解裝置之另一例中之陽極側 電解部20之圖。 圖4係說明藉由圖3之硫酸電解裝置而進行之硫酸之溫度 及濃度調整、電解、供給、排液處理等各步驟之步驟圖。 【主要元件符號說明】 A 陽極側稀釋硫酸生成路線 B 陽極側電解硫酸生成路線 A' 陰極侧稀釋硫酸生成路線 B' 陰極側電解路線 1 硫酸電解裝置 2 電解槽 3 陽極 4 陽極室 5 隔膜 6 陰極 7 陰極室 10 陽極侧純水供給配管 11 陽極侧純水供給閥 12 陰極側純水供給配管 13 陰極側純水閥 101107844 44 201243109 20 陽極側電解部 21 陽極室入口閥 22 陽極室出口閥 23 陰極側電解部 24 陰極室入口閥 25 陰極室出口閥 27 陽極側濃硫酸供給配管 28 陽極側濃硫酸供給閥 29 陰極侧濃硫酸供給配管 30 陰極側濃硫酸供給閥 31 陽極侧儲罐 32 陽極側濃硫酸供給部 33 陽極側循環泵 34 陽極側冷卻器 35 陽極側旁路閥 36 陽極側旁路配管 37 陽極側循環配管 38 陰極側儲罐 39 陰極側濃硫酸供給部 40 陰極側循環泵 41 陰極側冷卻器 42 陰極侧旁路閥 101107844 45 201243109 43 陰極側旁路配管 44 陰極側循環配管 49 第1陽極侧儲罐 50 第2陽極侧儲罐 51 〜58 切換閥 91 陽極側氣液分離機構 92 陽極側油霧分離器 93 臭氧分解機構 94 陽極側氣體配管排液閥 95 陽極側排液配管 96 陰極側氣液分離機構 97 陰極側油霧分離器 98 陰極氣體除害機器 99 陰極側氣體配管排液閥 100 陰極側排液配管 102 陽極氣體出口配管 103 陰極氣體出口配管 110 陽極儲罐排出配管 111 陽極儲罐排出閥 112 陰極儲罐排出配管 113 陰極儲罐排出閥 101107844 46|Sulfuric acid concentration | (mol/L) Current density (A/dm2) Volume 冢 (Ah/L, & solution temperature (°C) Total oxidizing substance concentration (mol/L) RUN7 I 1.8 100 〇25 54 RUN8 2.0 100 0.28 60 RUN9 2.3 100 25 0.32 69 RUN 10 3.7 100 25 ^ 0.36 nn RUN 11 5.3 100 ----- It 25 〇35 75 RUN 12 I 7.1 _ 100 25^ 0.34 η λ RUN 13 1 9.2 100 fH 0.29 A Ai RUN 14 10.0 100 00 0.28 RUN 15 11.5 100 DU 0.19 42 RUN 16 14.1 100 0.13 29 RUN 17 15.4 100 25~~~ 0.11 ΟΛ RUN 18 | 16.7 100 it—Z outside 0.06 1 A —-----, 1 H 101107844 41 201243109 Table 3 shows an example in which the electrolyte is continuously cooled and maintained at 3 ° C in electrolysis, and the temperature of the electrolyte rises to 51 ° C by the heat generated by the electrolysis during the electrolysis. [Table 3] Sulfuric acid concentration Current density Volume capacity dense solution temperature (mol/L) (A/dm2) Degree (Ah/L) Degree CC) JlUNlTT3.7 100 190 30 ΚϋΝ2 (ΓιΓ 3 7 100 190 51 Total oxidation Substance concentration [m〇l£L') 1.51 ~〇J2 According to Table 3, continuous cooling to 3 (TC example obtained oxidizing substance concentration 1.51 m〇i / L, and In contrast, in the electrolysis, the cooling is stopped and the temperature of the electrolyte rises to 51 by the heat generated by the electrolysis. (In the example, the concentration of the oxidizing substance stays at 0.72 mol/L, and efficient electrolysis cannot be performed. Comparative Example 1 > Next, as a comparative example, a combination position was set in the anode side storage tank, and further, a gas-liquid separation mechanism and an oil mist separator were not provided. In the step of diluting the sulfuric acid formation, the cooling is not appropriate, and the device is malfunctioning. 〃: In the case of #1, in order to adjust the 6 m〇i/L of the dilute storage tank, the sulfuric acid solution is rotated. (4) The quality of the ultra-pure water in the storage tank is 2 ^ 98. The lower part of the tank is 5.9" (4) The acid surface is room temperature. The feed water supply flow rate, 'mm 98% by mass sulfuric acid supply flow rate is 〇2~" Inside the tank is made by the current axis of ultrapure water and sulfuric acid. At the temperature of the solution, the dilution heat generated by the chamber L L1 is increased, thus generating a large amount of vapor. A stain is attached to the inner wall of the outlet pipe. , ★ and gas 101107844 42 201243109; 8 after the supply of % sulfur ^, (4) start * make the solution = medium cycle 'cool the diluted sulfuric acid solution to 25 ° C. The cooling bundle is allowed to circulate in the storage tank and the electrolytic cell to start electrolysis. The energy of the electrolysis is 27 °C 'The gas of the gas outlet pipe of the anode and the cathode: β ^ 5 kPa ' But after 10 minutes from the start of electrolysis, the pressure of the cathode storage tank rises sharply to J up to 200 kPa, which becomes abnormal, so The solution is circulated in the storage tank and the electrolytic cell. At this time, the vapor generated by the mixed heat of dilution is contained in the transition between the cathode 2 tank and the hydrogen burning tower provided as the cathode side detoxification apparatus*. Ρ 'The liquid that has accumulated the mist and vapor generated when the sulfuric acid is diluted is clogged with the gas filter due to the liquid of 5 liters. Therefore, the cathode gas generates a high pressure between the cathode storage tank and the stern (4). After liberating the residual pressure, there is a through hole in the cation exchange crucible when the tank is removed. (Industrial Applicability) According to the electrolysis device and the sulfuric acid electrolysis method of the present invention, a temperature and a concentration of the diluted sulfuric acid managed can be generated in the shaking, and the diluted sulfuric acid can be used under temperature management conditions. By electrolysis, sulfuric acid containing an oxidizing substance can be produced efficiently and safely. Further, it is possible to provide a sulfuric acid transfer apparatus and a brittle electrolysis method which can produce a high-concentration oxidizing substance solution which cannot be achieved by the prior art using a high current efficiency, and can stably generate an oxidizing live matter f. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a general view showing an example of a sulfuric acid electrolysis device of the present invention. 101107844 43 201243109 Fig. 2 is a flow chart showing the steps of temperature, concentration adjustment, electrolysis, supply, and draining of sulfuric acid by the sulfuric acid electrolysis apparatus of Fig. 1. Fig. 3 is a view showing the anode-side electrolysis portion 20 in another example of the sulfuric acid electrolysis device of the present invention. Fig. 4 is a view showing the steps of various steps such as temperature and concentration adjustment of sulfuric acid, electrolysis, supply, and draining treatment by the sulfuric acid electrolysis apparatus of Fig. 3. [Main component symbol description] A anode side diluted sulfuric acid generation route B anode side electrolytic sulfuric acid production route A' cathode side diluted sulfuric acid generation route B' cathode side electrolysis route 1 sulfuric acid electrolysis device 2 electrolytic cell 3 anode 4 anode chamber 5 separator 6 cathode 7 Cathode chamber 10 Anode side pure water supply pipe 11 Anode side pure water supply valve 12 Cathode side pure water supply pipe 13 Cathode side pure water valve 101107844 44 201243109 20 Anode side electrolysis section 21 Anode chamber inlet valve 22 Anode chamber outlet valve 23 Cathode Side electrolysis unit 24 cathode chamber inlet valve 25 cathode chamber outlet valve 27 anode side concentrated sulfuric acid supply pipe 28 anode side concentrated sulfuric acid supply valve 29 cathode side concentrated sulfuric acid supply pipe 30 cathode side concentrated sulfuric acid supply valve 31 anode side storage tank 32 anode side concentrated Sulfuric acid supply unit 33 anode side circulation pump 34 anode side cooler 35 anode side bypass valve 36 anode side bypass pipe 37 anode side circulation pipe 38 cathode side storage tank 39 cathode side concentrated sulfuric acid supply unit 40 cathode side circulation pump 41 cathode side Cooler 42 Cathode side bypass valve 101107844 45 201243109 43 Cathode side bypass piping 44 Cathode side circulation pipe 49 First anode side storage tank 50 Second anode side storage tank 51 to 58 Switching valve 91 Anode side gas-liquid separation mechanism 92 Anode side oil mist separator 93 Ozone decomposition mechanism 94 Anode side gas piping discharge valve 95 Anode side drain pipe 96 Cathode side gas-liquid separator 97 Cathode side oil mist separator 98 Cathode gas detoxification machine 99 Cathode side gas pipe drain valve 100 Cathode side drain pipe 102 Anode gas outlet pipe 103 Cathode gas outlet pipe 110 Anode tank discharge piping 111 Anode tank discharge valve 112 Cathode tank discharge piping 113 Cathode tank discharge valve 101107844 46

Claims (1)

201243109 七、申請專利範園·· 1.一種硫酸電解裝置，其係具有陽極側電解部2()與陰極 側電解部23而成之瑞I電解^置1，其特徵在於. 於陽極侧電解部20内至少設置有陽極側稀釋硫酸生成路 線A與陽極側電解硫酸生成路線B，該陽極側稀釋硫酸生 成路線A係稀釋作為供給原料之濃硫酸並將經稀釋之硫酸 凋整至所需之溫度及?辰度，忒除極側電解硫酸生成路線B 係將該稀釋硫酸生成路線A中所生成之稀釋硫酸電解而生 成電解硫酸’且將所生成之電解硫酸調整至所需之溫度及濃 度， 又/ 上述陽極側稀釋硫酸生成路線A係依照陽極侧儲罐31、 陽極側濃硫酸供給部32及陽極側冷卻器34之順序進行配 置’利用陽極側旁路配管36將該等連接而形成路線，進而 於該路線A内之任-位置連接可向路線A内供給純水之陽 極側純水供給配管1G’進而連接可用於向上述陽極側濃硫 酸供給部32供給濃硫酸之陽極侧濃硫酸供給配管27， 上述陽極側電解硫酸生成路線B係利用陽極側循環配管 37’將上述陽極侧儲罐31、與包含㈣㈣$形成之陽極室心 陰極室7之電解槽2中之内部設置有陽極3的陽極室4連接 而形成路線， 將自上述陽極側濃硫酸供給配管27供給至陽極側濃硫酸 供給部32之濃疏酸’利用自上述陽極側純水供給配管1〇 101107844 201243109 供給之純水進行稀釋’且將經稀釋之低濃度之硫酸於在上述 路線A _環之期_整至所需之溫度及濃度，而生成調 整至所需之溫度及濃度之稀釋硫酸， 所生成之稀釋硫酸經由構成上述路線B之陽極側循環配 管37而向上述電解槽2之陽極室4供給，於該陽極室*中 生成電解雜’且賴生成之轉额於在上述路線B内 循環之期_整至所需之溫度及濃度，而生成調整至所需之 溫度及濃度之電解硫酸。 2.如申凊專利範圍第丨項之硫酸電解裝置，其中，進而於 上述陰極側電解部23之裝置内設置有陰極側稀釋硫酸生成 路線A，與陰極側電解路線B，，該陰極側稀釋硫酸生成路線 ^係稀釋作為供給顆之濃硫酸而製成低濃度之硫酸，並將 該低濃度之硫酸調整至所需之溫度及濃度，該陰極側電解路 線㈣使該稀釋硫酸生成路線A，中生成之稀釋硫酸於陰極 陰極侧稀釋硫酸生成路線A,係依照陰極側儲罐38、陰極 側濃硫酸供給部39與陰極侧冷卻器Μ之财進行配置二且 利用陰極侧旁路配管43將該等連接而形成路線，進而㈣ 内之任-位置連接可向路線A，内供給純水之陰^ :給配^ 12，進而連接可用於向上述陰極側濃硫酸供 、··。部39供給濃硫酸之濃硫酸供給配管29， 陰極側電解路線B，係利用陰極側循環配管44將上述陰極 101107844 48 201243109 側儲罐38、與包含由隔膜5形成之陽極室4、陰極室7之電 解槽2中之内部設置有陰極6的陰極室7連接而形成路線， 將自陰極侧濃硫酸供給配管29供給至陰極側濃硫酸供給 ' 部39之濃硫酸’利用自上述陰極側純水供給配管12供給之 X 純水稀釋，將經稀釋之低濃度之硫酸於在上述路線A，内循 ”·環之期間調整至所需之溫度及濃度，而生成調整至所需之溫 度及濃度之稀釋硫酸， 所生成之稀釋硫酸經由構成上述路線B,之陰極側循環配 管44而向電解槽2之陰極室4供給，於在路線&内循環之 期間將經溫度及濃度調整之稀釋硫酸電解。 札啤*丄，貝义硫醗電解裝1，丹係於上述 極側儲罐31上部經由陽極氣體出口配管⑽卩依序串聯: 通之方式’連接陽極織液分離機構％及陽極側油霧如 ^陽極側氣液分離機構91及該陽極側油霧分㈣ 陽極:二具備用以排出各自之内部所儲存之嶋^ %極側讀分離機構91與陽極側油霧分 液手段而成。 心稱仏之有 4.如申請專利範圍第2 極側儲罐31上邱姆士… 电解裝置’其係於上述陽 通之方式，連接腸仏ρ - “〇2以依序串聯連 逆接陽極侧氣液分離機楢 器92,於令陽朽… 钱構91及除極侧油霧分離 於該除極侧氣液分離機構91 92之底邱，目# 及°亥知極侧油霧分離器 之底。卜具備用以排出各自 101107844 W4所鍺存之液體的連通 49 201243109 陽極侧氣液分離機構91與陽極側油霧分離器％之構造之排 液手段，並且 進而於上述陰極側儲罐38上部經由陰極氣體出口配管 1〇3以依料聯連通之方式，連接陰極職液分離機構％ 及陰極側_分離H 97，於贿極職液分離機構％及該 陰極侧油霧分離器97之底部，具備用以排出各自之内部所 儲存之液體的連通陰極側氣液分離機構％與陰極側油霧分 離器97之構造之排液手段而成。 5. 如申請專利範圍第3或4項之硫酸電解裝置，並中，於 上述陽極側油霧分離器92連接有臭氧分解機構％。 6. 如申凊專利範圍第4項之硫酸電解裝置，其中，於上述 陰極側油霧分離器97連接有氫處理機構。 7·如申喷專利範圍第i或2項之硫酸電解裝置，1中，於 上述稀釋硫酸生成路線A中，並列設置複數個上述陽極側 儲罐’於-個該陽極側儲罐中蓄積所生成之包含氧化性物質 的電解硫酸後’對間進行切換後於其他陽極侧儲罐中生成包 含特定漠度之氧化性物質之電解碗酸。 8. 如申明專利範圍第7項之硫酸電解裝置，其中，構成為 於將-個陽極侧儲罐中蓄積之含有特定濃度之氧化性物質 的電解硫酸向硫酸電解|置外之使用點輸送之期 -陽極^罐^含有特定濃度之氧化性㈣之電解硫酸另 9. 如申5月專利範圍第1或2項之硫酸電解裝置，其中，上 101107844 50 201243109 述陽極3為導電性金剛石電極。 !〇.如申請專利第】或2項之硫酸電解裝置，其中， 上述隔膜5為氟樹脂系陽離子交換膜或經親水化處理 孔質氟系樹脂膜。 / η.-種硫酸電解方法，其特徵在於：使用申請專利範圍 第1至10項中任一項之硫酸電解震置生成調整至所需之 度及濃度之電解硫酸。 /jnL 12.-種硫酸電解方法，其特徵在於：使用申請專 第1至1G項中任—項之硫酸電解裝置，並且使用多孔質氣 糸樹脂膜作為上述隔膜5，於因陽離子通過該多孔質 脂膜時所攜帶之攜帶水，使於上述陰㈣解部23之陰極側 電解路線B'中循環之稀釋硫酸溶液之液量增加時，藉由定 於上述陰極側館罐38之液面達到狀之高度時排出 ，疋里之液體，而防止該陰極側儲罐38之溢出。 h 邊電解方法’其特徵在於：使用申請專利範圍 L 貞中任—項之硫酸電解裝置，並且使用多孔質氟 ^树月曰膜作為上述隔膜5’於因陽離子通過該多孔質氟系樹 、寺所攜卞之攜帶水，使於上述陰極電解部u之路線a’ ^所生成之稀釋硫酸溶液之硫酸濃度下降至特定濃度以下 夺藉由向上述陰極側濃硫酸供給部39補充濃硫酸 而保持-定範圍之稀釋硫酸濃度。 申明專利範圍第U至13項中任一項之硫酸電解方 101107844 51 201243109 法，其中，於上述陽極側電解部20内之稀釋硫酸生成路線 A或上述陰極側電解部23内之稀釋硫酸生成路線A'中，以 電解前之稀釋硫酸之溫度成為30°C以下之方式進行溫度調 整。 15. 如申請專利範圍第11至13項中任一項之硫酸電解方 法，其中，於上述陽極側電解部20内之電解硫酸生成路線 B或上述陰極側電解部23内之陰極側電解路線K中，將經 電解之電解液之溫度調整為30°C以下。 16. 如申請專利範圍第11至13項中任一項之硫酸電解方 法，其中，於上述陽極側電解部20内之稀釋硫酸生成路線 A或上述陰極側電解部23内之稀釋硫酸生成路線A'中，以 電解前之稀釋硫酸之硫酸濃度成為2〜10 mol/L之方式進行 濃度調整。 101107844 52201243109 VII. Application for Patent Fan Park·· 1. A sulfuric acid electrolysis device having an anode-side electrolysis unit 2 () and a cathode-side electrolysis unit 23, which is characterized in that it is electrolyzed on the anode side. The portion 20 is provided with at least an anode side diluted sulfuric acid formation route A and an anode side electrolytic sulfuric acid formation route B. The anode side diluted sulfuric acid formation route A dilutes the concentrated sulfuric acid as a raw material and dilutes the diluted sulfuric acid to a desired state. The temperature and the degree of annihilation, the removal of the electrolyzed sulphuric acid from the polar side, the route B, electrolysis of the diluted sulphuric acid produced in the dilute sulphuric acid formation route A to produce electrolytic sulphuric acid, and the generated electrolyzed sulphuric acid is adjusted to the desired temperature and concentration. In addition, the anode-side diluted sulfuric acid generation route A is arranged in the order of the anode-side storage tank 31, the anode-side concentrated sulfuric acid supply unit 32, and the anode-side cooler 34, and is connected by the anode-side bypass piping 36. The route is further connected to the anode side pure water supply pipe 1G' for supplying pure water to the route A in the position-position connection in the route A, and the connection can be used for supplying the concentrated sulfuric acid to the anode side. The portion 32 supplies the concentrated sulfuric acid supply pipe 27 of the concentrated sulfuric acid to the anode side, and the anode side electrolytic sulfuric acid production route B connects the anode side storage tank 31 and the anode chamber cathode and cathode chamber 7 including the (four) (four) $ by the anode side circulation pipe 37'. In the electrolytic cell 2, the anode chamber 4 in which the anode 3 is provided is connected to form a route, and the concentrated acid supplied from the anode-side concentrated sulfuric acid supply pipe 27 to the anode-side concentrated sulfuric acid supply unit 32 is utilized. The water supply pipe 1〇101107844 201243109 is supplied with pure water for dilution' and the diluted low-concentration sulfuric acid is adjusted to the desired temperature and concentration during the above-mentioned route A_ring to the desired temperature. And the diluted sulfuric acid produced at a concentration, the diluted sulfuric acid produced is supplied to the anode chamber 4 of the electrolytic cell 2 via the anode-side circulation piping 37 constituting the above-described route B, and an electrolytic impurity is generated in the anode chamber*. The electrolytic sulfuric acid adjusted to the desired temperature and concentration is generated during the cycle of the above route B to the desired temperature and concentration. 2. The sulfuric acid electrolysis apparatus according to claim 2, wherein the cathode side dilution sulfuric acid generation route A and the cathode side electrolysis route B are provided in the apparatus of the cathode side electrolysis section 23, and the cathode side is diluted. The sulfuric acid generation route is diluted as a concentrated sulfuric acid to supply a low concentration of sulfuric acid, and the low concentration of sulfuric acid is adjusted to a desired temperature and concentration, and the cathode side electrolysis route (4) causes the diluted sulfuric acid to generate a route A, The diluted sulfuric acid produced in the cathode is diluted with the sulfuric acid in the cathode side to form a route A, which is arranged in accordance with the cathode side storage tank 38, the cathode side concentrated sulfuric acid supply unit 39, and the cathode side cooler, and is configured by the cathode side bypass piping 43. These connections form a route, and the any-position connection in (4) can supply the pure water to the channel A, and the connection can be used to supply the concentrated sulfuric acid to the cathode side. The portion 39 supplies the concentrated sulfuric acid supply pipe 29 of concentrated sulfuric acid, and the cathode side electrolysis route B, the cathode 101107844 48 201243109 side storage tank 38 and the anode chamber 4 and the cathode chamber 7 including the separator 5 are formed by the cathode side circulation pipe 44. In the electrolytic cell 2, the cathode chamber 7 in which the cathode 6 is provided is connected to form a route, and the concentrated sulfuric acid supply pipe 29 from the cathode side is supplied to the concentrated sulfuric acid supply to the cathode side, and the concentrated sulfuric acid is supplied from the cathode side. The X pipe of the supply pipe 12 is diluted with pure water, and the diluted low-concentration sulfuric acid is adjusted to the desired temperature and concentration during the cycle of the above-mentioned route A to generate the desired temperature and concentration. The diluted sulfuric acid is produced, and the diluted sulfuric acid produced is supplied to the cathode chamber 4 of the electrolytic cell 2 via the cathode side circulation pipe 44 constituting the above route B, and the diluted sulfuric acid adjusted by temperature and concentration is adjusted during the route & Electrolysis. The beer is 丄, 贝 醗 醗 醗 醗, the Dan is in the upper part of the above-mentioned pole side tank 31 via the anode gas outlet pipe (10) 卩 in series: The liquid separation mechanism % and the anode side oil mist such as the anode side gas-liquid separation mechanism 91 and the anode side oil mist portion (4) anode: two are provided for discharging the respective internal storage of the 极^% pole side read separation mechanism 91 and the anode The side oil mist is divided into liquid. The heart is called 4. There is a 2nd pole side tank 31 on the patent application scope. [The electrolysis device is connected to the intestines ρ - " 〇2 is connected in series with the anode side gas-liquid separator 92 92, in order to make the yang... The structure and the de-polar oil mist are separated from the depolarization side gas-liquid separation mechanism 91 92. Qiu, head# And the bottom of the well-known side oil mist separator. a liquid discharging means for discharging the liquid of each of the liquids and liquids separating means 91 and the anode side oil mist separating means 91, which are connected to the liquids of the respective 101107844 W4, and further configured to pass through the upper portion of the cathode side storage tank 38. The cathode gas outlet pipe 1〇3 is connected to the cathode working fluid separation mechanism % and the cathode side _ separation H 97 in the manner of the material communication, at the bottom of the brittle electrode separation mechanism % and the cathode side oil mist separator 97, The liquid discharge means for connecting the cathode-side gas-liquid separation means % and the cathode-side oil mist separator 97 for discharging the liquid stored in each of them is provided. 5. The sulfuric acid electrolysis device according to claim 3 or 4, wherein the anode side oil mist separator 92 is connected to the ozone decomposing mechanism %. 6. The sulfuric acid electrolysis device according to claim 4, wherein the cathode side oil mist separator 97 is connected to a hydrogen treatment mechanism. 7. In the sulfuric acid electrolysis device according to item i or item 2 of the patent application scope, in the above-mentioned dilute sulfuric acid production route A, a plurality of the above-mentioned anode side storage tanks are disposed side by side in one of the anode side storage tanks. After the electrolytic sulfuric acid containing the oxidizing substance is generated, the electrolytic bowl acid containing the specific oxidizing substance is generated in the other anode side storage tank after switching between the two. 8. The sulfuric acid electrolysis device according to the seventh aspect of the invention, wherein the electrolyzed sulfuric acid containing a specific concentration of the oxidizing substance accumulated in the anode-side storage tank is transported to the point of use of the sulfuric acid electrolysis The sulphuric acid electrolysis device according to the first or second aspect of the patent application of the above-mentioned Japanese Patent Publication No. 1 or No. 2, wherein the anode 3 is a conductive diamond electrode. The sulfuric acid electrolysis device according to the invention of claim 2, wherein the separator 5 is a fluororesin-based cation exchange membrane or a hydrophilized porous fluororesin membrane. / η.-A method for electrolyzing sulfuric acid, characterized in that electrolytic sulfuric acid adjusted to a desired degree and concentration is produced by using the sulfuric acid electrolysis of any one of claims 1 to 10. /jnL 12. A method for electrolyzing sulfuric acid, characterized in that a sulfuric acid electrolysis device according to any one of the items 1 to 1G is used, and a porous gas ruthenium resin film is used as the separator 5, because the cation passes through the porous The carrier water carried in the lipid film increases the liquid amount of the diluted sulfuric acid solution circulating in the cathode side electrolysis route B' of the negative (four) solution portion 23 by the liquid level of the cathode side canister 38 When the height of the shape is reached, the liquid in the crucible is discharged, and the overflow of the cathode side storage tank 38 is prevented. The h-side electrolysis method is characterized in that: the sulfuric acid electrolysis device of the patent application scope L 贞 is used, and a porous fluorinated eucalyptus membrane is used as the separator 5' in the passage of the porous fluorinated tree by the cation. The water carried by the temple carries the water to reduce the sulfuric acid concentration of the diluted sulfuric acid solution formed in the route a' of the cathode electrolysis unit u to a specific concentration or less, and the concentrated sulfuric acid supply portion 39 is supplied with the concentrated sulfuric acid to the cathode side. Maintain - a range of diluted sulfuric acid concentrations. The sulfuric acid electrolysis unit 101107844 51 201243109 according to any one of the above-mentioned items, wherein the dilute sulfuric acid formation route in the anode side electrolysis section 20 or the dilute sulfuric acid generation route in the cathode side electrolysis section 23 is used. In A', the temperature is adjusted so that the temperature of the diluted sulfuric acid before electrolysis becomes 30 degrees C or less. 15. The sulfuric acid electrolysis method according to any one of the above-mentioned claims, wherein the electrolysis sulfuric acid formation route B in the anode side electrolysis section 20 or the cathode side electrolysis route K in the cathode side electrolysis section 23 is used. In the middle, the temperature of the electrolytic solution to be electrolyzed is adjusted to 30 ° C or lower. 16. The sulfuric acid electrolysis method according to any one of the items 11 to 13, wherein the diluted sulfuric acid formation route A in the anode side electrolysis section 20 or the diluted sulfuric acid generation route A in the cathode side electrolysis section 23 In the middle, the concentration was adjusted so that the sulfuric acid concentration of the diluted sulfuric acid before electrolysis became 2 to 10 mol/L. 101107844 52
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