JP7566867B2 - 紫外線促進酸化プロセス制御のための過酸化水素のオンサイト電気化学的生成の制御 - Google Patents
紫外線促進酸化プロセス制御のための過酸化水素のオンサイト電気化学的生成の制御 Download PDFInfo
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- JP7566867B2 JP7566867B2 JP2022502916A JP2022502916A JP7566867B2 JP 7566867 B2 JP7566867 B2 JP 7566867B2 JP 2022502916 A JP2022502916 A JP 2022502916A JP 2022502916 A JP2022502916 A JP 2022502916A JP 7566867 B2 JP7566867 B2 JP 7566867B2
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Description
本明細書で開示される態様および実施形態は、一般に、in-situ電気化学的過酸化水素発生器を含む促進酸化システム、およびこれを操作または構築する方法に向けたものである。
近年、多くの研究により、促進酸化プロセス(AOPs)が多くの用途、特に水処理に適していることが示された(Legrini, O., Oliveros, E., Braun, A. M. (1993). 「Photochemical Processes for Water Treatment.」 Chm. Rev. 1093,93,671-698; Boltonら (1996). 「Figures of Merit for the technical development and application of Advanced Oxidation Processes.」 J. of Advanced Oxidation Technologies, 1,113-17)。
NaOCl+H2O2 → NaCl+H2O+O2
H2O2+UV → 2・OH
(H2O2のO-O結合の均一結合開裂により、2・OHラジカルが生成される)
アノード、カソード、およびアノードとカソードとの間に配置された陽イオン交換膜を含む電気化学セルにおける過酸化水素の生成を評価するための試験を実施した。この試験の結果は、図20に示されている。この図において、青色の曲線は、酸素を含まない水を用いた電気化学セルの性能試験から得られたものであり、オレンジ色の曲線は、水が酸素で飽和されるまで大気圧で酸素をバブリングした水を用いた電気化学セルの試験から得られたものである。図に示すように、過酸化水素の生成速度は、まず電圧の上昇とともに増加し、その後さらに電圧の上昇とともに減少した。より低い電圧では、過酸化水素の生成速度は、水中の酸素濃度によって制限されていると考えられる。より高い電圧(ゼロに近い)では、過酸化水素の生成速度は低い電流によって制限されたと考えられる。
チタンメッシュで形成された各面積10cm2の平板電極を有する電解セルの電圧対電流の特徴を調べる試験を行った。試験では、酸素を添加していない水、または60barの圧力で酸素にさらされた後の水のいずれかを、異なる流量でセルに流した。その結果を図23のチャートに示す。見てわかるように、試験した各条件において、印加電圧の絶対値が増加する(より負になる)と電流が増加する(より負になる)。電流対電圧の増加量が最も低いのは、酸素無添加および流量ゼロの条件であった(0_O2_0_フロー曲線)。酸素無添加の水の流量が毎分18リットルまで増加すると(0_O2_18LPM曲線)、特定の電圧で観測される電流は、酸素無添加、流量ゼロの条件と比較して増加した。酸素水を毎分16リットル電解セルに流した場合(O2_60bar_16LPM曲線)には、特定の電圧で観測される電流がさらに増加した。これらの結果から、電解セルに流す水が追加の酸素を含有するにつれて、酸素と水との反応を起こすのに使用される電流を供給する電解セルの能力が高まることがわかった。これらの結果から、電解セルに流す水に酸素を添加することで、H2O2などの反応物を生成し得ることがわかる。
電解セル内で溶液中の過酸化水素濃度が時間経過とともにどのように増加するかを評価する試験を行った。カーボンクロスで形成されたカソードと、混合金属酸化物で形成されたアノードとで電解セルを形成した。アノードとカソードは、5mMのNa2SO4溶液80mlの中に配置した。酸素を30分間バブリングした。電極に5mAの電流を流した。30分の通電後、溶液中の過酸化水素濃度は12.75ppmであった。2時間の通電後、過酸化水素濃度は、29.75ppmに上昇した。これらの結果から、過酸化水素の電解生成は、通電時間が長くなるほど、より高濃度の過酸化水素を溶液中に生成し得ることがわかった。
UVAOP反応器での汚染物質(1,4-ジオキサンおよびフミン酸、各濃度0.65mg/L)破壊に対するpHの影響を評価するための試験を実施した。UV照射量は650mJ/cm2、過酸化水素濃度は2mg/L、温度は89°Fであった。この試験の結果は、図24に示されている。図24のチャートから分かるように、汚染物質の破壊率は、pHの低下とともに増加したが、pHが中性以下になると破壊率の増加は、有意には増加しなかった。これらの結果は、汚染物質の破壊を最適化するために、H2O2酸化剤を用いたUVAOP反応器を中性または酸性のpHで運転することが望ましい可能性があることを示している。
UVAOP反応器でのH2O2の活性化に対するpHの影響を評価するための試験を実施した。UV照射量は、650mJ/cm2、反応器内の溶液のTOCは、0.65mg/L、過酸化水素濃度は、2mg/L、温度は、89°Fであった。この試験の結果は、図25に示されている。図25のチャートから観察できるように、H2O2の活性化率(活性化パーセント)は、試験条件下で約10%であり、pHは、検出可能な影響を有しない。これらの結果は、H2O2の活性化率の変化が、上記実施例4で観察された、より低いpHレベルにおける汚染物質破壊率の増加の原因である可能性が低かったことを示している。
UVAOP反応器におけるH2O2の活性化率に及ぼすH2O2濃度とUV照射量との影響を評価するための試験を実施した。UV照射量は、1300mJ/cm2または650mJ/cm2のいずれかであり、反応器内の溶液のTOCは、0.65mg/L、温度は、89°Fであった。この試験の結果は、図2に示されている。図26のチャートから観察できるように、H2O2濃度が酸化剤の活性化に観察可能な影響を及ぼさなかった一方で、UV照射量を650mJ/cm2から1300mJ/cm2に増加させると、H2O2の活性化率が約10%から約30%に増加した。これらの結果は、H2O2の活性化率は、UV照射量の増加に伴って非線形に増加し、UV照射量をあるパーセント増加させると、UVAOP反応器に供給する溶液中のH2O2の濃度が同じパーセント増加した場合よりも、利用できるヒドロキシラジカルの量により大きな影響を与えることを示している。
UVAOP反応器において、異なるUV照射量と異なるH2O2濃度とで、1,4-ジオキサンおよびフミン酸の破壊量を評価する試験を実施した。1,4-ジオキサンを用いた試験の結果を図26に示し、フミン酸を用いた試験の結果を図27に示す。これらのデータは、UV照射量を増加させることが、両方の汚染物質の破壊を増加させるのに有意な効果を有することを示す。1,4-ジオキサンの破壊は、H2O2濃度とともに増加したが、予想外に、フミン酸の破壊は、H2O2濃度の増加とともに減少した。これらの結果は、異なる汚染物質の破壊は、異なる過酸化水素濃度で最適化され得ることを示す。また、溶液中にH2O2を含まないで動作するUVAOP反応器と対照的に、H2O2の存在により汚染物質の濃縮速度が増加することも確認された。
Claims (20)
- 化学線放射反応器、
過酸化水素を生成するように構成され、電解液源と化学線放射反応器との間に流体連通する出口を有する電気化学セル、
電気化学セルの入口と連通する酸素源、
前記化学線放射反応器の出口に流体的に結合された導管、および、
前記化学線放射反応器の出口の下流で前記導管と流体連通している該出口を有する第2の電気化学セルであって、前記導管内の処理水溶液中に存在する過酸化水素をクエンチする化学薬剤を生成するように構成された前記第2の電気化学セルを含む、水処理システム。 - 電解液源を電気化学セルの入口に流体的に結合する第1の導管、および、
電気化学セルの出口と化学線放射反応器の入口とを流体的に結合する第2の導管をさらに含む、請求項1に記載のシステム。 - 電気化学セルの出口が、電解液源を電気化学セルの入口に流体的に結合する導管の導入点に流体的に結合される、請求項1に記載のシステム。
- 前記化学線放射反応器が、紫外線促進酸化プロセス反応器である、請求項1に記載のシステム。
- 電解液が水を含む、請求項1に記載のシステム。
- 電気化学セルの出口に結合された貯蔵タンクをさらに含む、請求項1に記載のシステム。
- 前記第2の電気化学セルの出口に結合された貯蔵タンクをさらに含む、請求項1に記載のシステム。
- 前記化学薬剤が、次亜塩素酸ナトリウムを含む、請求項1に記載のシステム。
- 前記導管が、前記化学線放射反応器の前記出口を前記第2の電気化学セルの入口に流体的に連結している、請求項1に記載のシステム。
- 前記第2の電気化学セルの前記出口が、前記化学線放射反応器の前記出口の下流にある前記導管の導入点に流体的に結合されている、請求項1に記載のシステム。
- 水溶液中の1つ以上の汚染物質の濃度を測定するように構成されたセンサをさらに含み、前記センサは、前記化学線放射反応器の上流または前記化学線放射反応器の下流のいずれかに配置される、請求項1から10のいずれかに記載のシステム。
- 前記センサと通信し、前記1つ以上の汚染物質の測定された濃度に応答して、前記システムの1つ以上の動作パラメータを調整するように構成されたコントローラをさらに含む、請求項11に記載のシステム。
- 前記1つ以上の動作パラメータは、前記電気化学セルに加えられる電力、前記第2の電気化学セルに加えられる電力、前記化学線放射反応器に加えられる電力、および前記電気化学セル、前記第2の電気化学セル、もしくは前記化学線放射反応器のうちの1つを通る電解液または水溶液の流量のうちの1つを含む、請求項12に記載のシステム。
- 前記酸素源は、前記電気化学セルの上流で前記電解液に前記酸素を導入するように構成される、請求項12に記載のシステム。
- 前記コントローラは、前記1つ以上の汚染物質の前記測定された濃度に応答して、前記電解液への前記酸素の導入速度を調節するようにさらに構成される、請求項14に記載のシステム。
- 前記電解液源からの電解液の1つ以上の測定された特徴または前記化学線放射反応器で生成される処理水溶液の1つ以上の測定された特徴に基づいて、前記貯蔵タンクから前記化学線放射反応器への過酸化水素の流量を調整するように構成されたコントローラをさらに含む、請求項6に記載のシステム。
- 前記電解液源からの電解液の1つ以上の測定された特徴または前記化学線放射反応器で生成された処理水溶液の1つ以上の測定された特徴に基づいて、前記貯蔵タンクから前記化学線放射反応器の前記出口の下流の前記導管への次亜塩素酸ナトリウムの流量を調整するように構成されたコントローラをさらに含む、請求項7に記載のシステム。
- 前記化学線放射反応器の下流に、処理水溶液中の過酸化水素の濃度を測定するように構成されたセンサをさらに含む、請求項1から10のいずれかに記載のシステム。
- 前記センサと通信し、前記過酸化水素の測定濃度に基づいて前記第2の電気化学セルの1つ以上の動作パラメータを調整するように構成されたコントローラをさらに含む、請求項18に記載のシステム。
- 前記第2の電気化学セルの前記1つ以上の動作パラメータは、前記第2の電気化学セルに加えられる電力、前記第2の電気化学セルへの電解液の流量、前記第2の電気化学セルからの次亜塩素酸ナトリウムの流量、または前記第2の電気化学セルで生成される次亜塩素酸ナトリウムの濃度のうちの1つ以上を含む、請求項19に記載のシステム。
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