JP4712915B1 - 電解装置および微酸性電解水の製造方法 - Google Patents
電解装置および微酸性電解水の製造方法 Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 159
- 239000000460 chlorine Substances 0.000 claims abstract description 67
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 67
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000000203 mixture Substances 0.000 claims abstract description 49
- 238000010790 dilution Methods 0.000 claims abstract description 28
- 239000012895 dilution Substances 0.000 claims abstract description 28
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000007865 diluting Methods 0.000 claims abstract description 15
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 15
- -1 chlorine ions Chemical class 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 96
- 239000000243 solution Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims description 4
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims 1
- 230000002829 reductive effect Effects 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 7
- 230000002159 abnormal effect Effects 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
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- 230000001590 oxidative effect Effects 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Inorganic materials Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229910000457 iridium oxide Inorganic materials 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 241000070918 Cima Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 1
- 229940005991 chloric acid Drugs 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000005183 environmental health Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000015424 sodium Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
- C02F1/4674—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation with halogen or compound of halogens, e.g. chlorine, bromine
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/002—Construction details of the apparatus
- C02F2201/004—Seals, connections
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4612—Controlling or monitoring
- C02F2201/46125—Electrical variables
- C02F2201/4614—Current
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4612—Controlling or monitoring
- C02F2201/46145—Fluid flow
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4616—Power supply
- C02F2201/4617—DC only
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4618—Supplying or removing reactants or electrolyte
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
【解決手段】塩素イオンを含む含塩素組成物を電解し、被電解液を希釈して次亜塩素酸を含む微酸性電解水を製造するための電解装置300は、被電解液を希釈するため希釈水流路111を提供する容器115と、容器115の内部に配置され、複数の平板電極の間に規定される無隔膜の単位電解セルを含む電極スタック101と、単位電解セルを画成し、単位電解セルに対応する位置で含塩素組成物を供給するための開口107と、開口107に連通し、含塩素組成物を単位電解セルに供給する前に貯留するための貯留部108とを備える電極保持枠110とを備え、単位電解セルと、貯留部108とを連通する開口107の全面積Sが10mm2以下とされている。
【選択図】図1
Description
前記被電解液を希釈するため希釈水流路を提供する容器と、
前記容器の内部に配置され、複数の平板電極の間に規定される無隔膜の単位電解セルと、
前記単位電解セルを画成し、前記単位電解セルに対応する位置で含塩素組成物を供給するための開口と、前記開口に連通し、前記含塩素組成物を前記単位電解セルに供給する前に貯留するための貯留部とを有する電極保持枠とを備え、前記単位電解セルと、前記貯留部とを連通する前記開口の全面積Sが10mm2以下であり、かつ、
(1)上限電流値を超えた状態または下限電流値を下回った状態が所定の時間を超えて継続した場合。
(2)希釈水の供給が止まった場合や希釈水が設定しきい値を下回る低流量となった場合。
上述した(1)、(2)の条件が満たされた場合、制御装置332は、通電および希塩酸の供給を停止させ、装置および環境衛生上の不都合が発生しないようにする。
初期電解電流の挙動を検討するために、図3に示した電解装置を作成し、貯留部と電極間隙の合計容積の容積比を、約8%に固定し、開口107の単位セル毎の全面積を変えながら、初期電解電流を測定した。定電圧電源はコーセル社製PBF75-9、電流測定には、シーマ電子社製の、電流測定用精密抵抗を利用した測定システムを使用した。電解槽は4セルで構成した。なお、含塩素化合物としては塩酸(高杉製薬社製食品添加物グレード)を使用して、その濃度を6質量%とした。また、希釈水は、水道水を使用し、流量を300L/hrとし、設定定格電流を3Aとした。
(実験例2)
実験例1で使用した電解装置および電解条件を用い、貯留部108の容積を電極間隙の容積に対して、0.42%、0.83%、2.1%と変化させたことを除き、実験例1と同様の実験を行って、貯留部の容積と、電解槽の電極間隙の合計容積との比{(貯留部の容積/電極間隙の合計容積)}×100の関係を検討した。その実験条件および結果を表2に示す。
(実験例3)
実験例1、実験例2および図3で説明した電解装置を使用し、電解槽は、平板電極のサイズを50mm×200mm、厚さ1mmで、陽極として作用する面は酸化イリジウムで、陰極として作用する面は白金で被覆した。平板電極の間隔を、2mmとし、平板電極の全周を、硬質塩化ビニール樹脂製の電極保持枠に設けられた厚さ1mm、深さ3mmの溝に嵌入して固定した。4セルで構成し、各電極間隙空間の容積は17cm3であった。貯留部を、直径3mm、長さ17mmの円筒穴で容積を0.12cm3とした。このとき、貯留部の容積の電極間隙の合計容積に対する比は、約0.18%であった。
101 電極スタック
101a 平板電極
103 ターミナル電極端子棒
104 供給管
105 水密シール
106 シール要素
107 開口
108 貯留部
109 開口
110 電極保持枠
110a 電極保持枠
110b スロット
111 希釈水流路
112 インレットポート
113 アウトレットポート
114 台座
115 容器
116 シール要素
118 上部プレート
120 下部プレート
300 電解装置
311 希釈水流路
320 電磁弁
321 フロースイッチ
322 定流量弁
323 チェック弁
324 希塩酸タンク
325 希塩酸ポンプ
327 スタティックミキサー
328 希釈水流路
329 流路
330 電流センサー
331 直流電源
332 制御装置
Claims (9)
- 塩素イオンを含む含塩素組成物を電解し、被電解液を希釈して次亜塩素酸を含む微酸性電解水を製造するための定電圧電源を含む電解装置であって、
前記被電解液を希釈するため希釈水流路を提供する容器と、
前記容器の内部に配置され、複数の平板電極の間に規定される無隔膜の単位電解セルと、
前記単位電解セルを画成し、前記単位電解セルに対応する位置で含塩素組成物を供給するための開口と、前記開口に連通し、前記含塩素組成物を前記単位電解セルに供給する前に貯留するための貯留部とを有する電極保持枠とを備え、
前記単位電解セルと、前記貯留部とを連通する前記開口の全面積Sが10mm2以下であり、かつ、
- さらに貯留部容積の電極間隙の合計容積に対する比が、0.1%〜8%の範囲とされる、請求項1に記載の電解装置。
- 前記単位電解セルあたり前記開口が少なくとも2以上配設される、請求項1または2に記載の電解装置。
- 前記開口が多孔質材料の孔で規定される、請求項1〜3のいずれか1項に記載の電解装置。
- 貯留部容積の電極間隙の合計容積に対する比が、0.1〜4%以下である、請求項1〜4のいずれか1項に記載の電解装置。
- 最も外側に配置される前記平板電極の両外側面は、前記希釈水により冷却される、請求項1〜5のいずれか1項に記載の電解装置。
- 前記含塩素組成物は、塩酸水溶液、アルカリ金属塩化物またはアルカリ土類金属塩化物およびこれらのいかなる混合物である含塩素組成物から選択される、請求項1〜6のいずれか1項に記載の電解装置。
- 請求項1〜7のいずれか1項に記載の電解装置に塩酸水溶液、含塩素組成物を供給し、複数の平板電極の間に規定される無隔膜の単位電解セルに電圧を印加することにより、前記含塩素組成物を電気分解して次亜塩素酸を含む被電解液を生成する、微酸性電解水の製造方法。
- 前記含塩素組成物は、塩酸水溶液、アルカリ金属塩化物またはアルカリ土類金属塩化物およびこれらのいかなる混合物である含塩素組成物から選択される、請求項8記載の微酸性電解水の製造方法。
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