JP6777130B2 - 膜用水処理薬品及び膜処理方法 - Google Patents
膜用水処理薬品及び膜処理方法 Download PDFInfo
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- JP6777130B2 JP6777130B2 JP2018190257A JP2018190257A JP6777130B2 JP 6777130 B2 JP6777130 B2 JP 6777130B2 JP 2018190257 A JP2018190257 A JP 2018190257A JP 2018190257 A JP2018190257 A JP 2018190257A JP 6777130 B2 JP6777130 B2 JP 6777130B2
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Separation Using Semi-Permeable Membranes (AREA)
Description
このため、腐植物質が含まれている表層水や地下水、並びに食品・飲料製造工場における排水等には、ポリフェノール等のフェノール性ヒドロキシ基を有する有機化合物が含まれることとなるため、これらの水を被処理水としてRO膜処理すると、RO膜給水中のフェノール性ヒドロキシ基を有する有機化合物によるRO膜の閉塞が問題となる。
RO膜に限らず、食品・飲料原料由来のポリフェノールを含有する被処理水を精密濾過膜等の分離膜で処理する場合にも、ポリフェノールが濾過膜に捕捉され、膜閉塞の問題が発生する可能性がある。
このため、このような前処理ではなく、膜給水に添加して、ポリフェノール等のフェノール性ヒドロキシ基を有する有機化合物による膜汚染を防止する水処理薬品が望まれる。
即ち、本発明は以下を要旨とする。
(A) 該濃縮水を孔径0.45μmのフィルターで濾過して得られた濾過水について、紫外可視分光光度計を用いて50mmセルで測定した波長260nmの吸光度(abs(50mmセル))が0.01〜5.0
(B) 該濃縮水の全有機炭素(TOC)もしくは不揮発性有機炭素(NPOC)濃度が0.01〜100mg/L
(C) 該濃縮水の多価金属カチオンの濃度が1mg/L以上
即ち、腐植物質等のフェノール性ヒドロキシ基およびカルボキシル基を有する有機化合物による膜閉塞要因として、フェノール性ヒドロキシ基およびカルボキシル基を有する有機化合物に含有されるカルボキシル基と水中に共存するカルシウムイオン等の多価金属カチオンが結合して架橋化することで高分子化し、高分子化した有機化合物が膜面に付着することが挙げられる。カルボキシル基とスルホ基とを有する高分子化合物、特に式(1)で表される高分子化合物を用いることによって、この高分子化合物に含有されるカルボキシル基がカルシウムイオン等の多価金属カチオンと優先的に結合し、一方で、AMPS又はHAPS由来のR基の静電反発力によって膜への付着が防止され、膜汚染、膜閉塞が抑制されると考えられる。
Rが−C(=O)−NH−C(CH3)2−CH2SO3Hである構造単位(b)は、モノマー原料として2−アクリルアミド−2−メチルプロパンスルホン酸(AMPS)を用いることで、高分子化合物に導入することができる。また、Rが−CH2OCH2−CH(−OH)−CH2SO3Hである構造単位(b)は、モノマー原料として、3−アリルオキシ−2−ヒドロキシプロパンスルホン酸(HAPS)を用いることで、高分子化合物に導入することができる。
構造単位(a)は、モノマー原料としてアクリル酸(AA)を用いることで、高分子化合物に導入することができる。
また、上記式(1)で表される高分子化合物としては、次亜リン酸構造単位(a)及び構造単位(b)との反応物であるホスフィノポリカルボン酸であってもよい。ホスフィノポリカルボン酸としては、構造単位(a)及び構造単位(b)として、それぞれAA、AMPSを用いた場合には、例えばBWA社製のBelclene(登録商標)400を好適に用いることができる。
「フェノール性ヒドロキシ基」とは、芳香環に結合したヒドロキシ基のことであり、それを有する有機化合物としては、例えば、フミン酸、フルボ酸、エラグ酸、フェノール酸、タンニン、カテキン、ルチン、アントシアニン、及び合成されたフェノール樹脂などが挙げられる。
なお、フェノール性ヒドロキシ基を有する有機化合物がポリフェノール等の高分子の場合の重量平均分子量は、GPC法で測定し、標準プルランによる検量線を用いて算出した、プルラン換算の値である。
これらの被処理水に含まれるフェノール性ヒドロキシ基を有する有機化合物の濃度は、当該被処理水の種類により異なるが、通常0.01〜10mg/L程度である。
(A) 該濃縮水を孔径0.45μmのフィルターで濾過して得られた濾過水について、紫外可視分光光度計を用いて50mmセルで測定した波長260nmの吸光度(abs(50mmセル))が0.01〜5.0、特に0.1〜1.0。
(B) 該濃縮水の全有機炭素(TOC)もしくは不揮発性有機炭素(NPOC)濃度が0.01〜100mg/L、特に1〜10mg/L。
ここで、TOC、NPOCは燃焼式酸化法等により測定することができる。
(C) 該濃縮水の多価金属カチオンの濃度が1mg/L以上、特に10〜100mg/L。
<試験溶液の調製>
フェノール性ヒドロキシ基を有する有機化合物としてカナディアンフルボ溶液(UV260値が0.8になるよう調整)、塩化カルシウム100mg/L、評価薬剤1mg/L(有効成分として)を含有する水溶液(純水をベース)を調製し、更に、少量の水酸化ナトリウム水溶液又は硫酸水溶液でpHを6.5〜6.6に調整して試験溶液Iとした。
カナディアンフルボは、分子量10000のフェノール性ヒドロキシ基を有する有機化合物であり、試験溶液Iのフェノール性ヒドロキシ基を有する有機化合物濃度は約2.2mg/Lである。
別に、カナディアンフルボと評価薬剤を添加しなかったこと以外は試験溶液Iと同様にして試験溶液IIを調製した(参考例1)。
また、塩化カルシウムと評価薬剤を添加しなかったこと以外は試験溶液Iと同様にして試験溶液IIIを調製した(参考例2)。
更に、評価薬剤を添加しなかったこと以外は、試験溶液Iと同様にして試験溶液IVを調製した(比較例1)。
試験装置としては、図1に示す平膜試験装置を用いた。
この平膜試験装置は、有底有蓋の円筒状容器1の高さ方向の中間位置に平膜セル2を設けて容器内を原水室1Aと透過水室1Bとに仕切り、この容器1をスターラー3上に設置し、ポンプ4で被処理水を配管11を介して原水室1Aに給水すると共に、容器1内の攪拌子5を回転させて原水室1A内を攪拌し、透過水を透過水室1Bより配管12を介して取り出すと共に、濃縮水を原水室1Aより配管13を介して取り出すものである。濃縮水取り出し配管13には圧力計6と圧力調整バルブ7が設けられている。
上記の試験溶液I〜IVと試験装置を用い、以下の条件でRO膜通水試験を行った。
RO膜:ポリアミド系RO膜(日東電工社製「ES20」)
温度:24〜25℃
RO膜回収率:75%(4倍濃縮)
試験溶液I〜IVの通水試験で得られる濃縮水の水質は下記表2に示す通りである。
これに対して、Caを含んでいても、カナディアンフルボを含まない試験溶液IIや、カナディアンフルボを含んでいてもCaを含まない試験溶液IIIでは、フラックスの低下は殆ど見られないことから、本発明による効果(薬剤無添加の比較例1に対するフラックスの向上効果)は、多価金属カチオン共存下でのフェノール性ヒドロキシ基を有する有機化合物に対する分散効果であり、カルシウム系スケール防止剤とは異質の効果であることが分かる。
1A 原水室
1B 透過水室
2 平膜セル
3 スターラー
Claims (5)
- フェノール性ヒドロキシ基を有する有機化合物を含む被処理水を膜分離処理するに当たり、該膜の給水に請求項1に記載の膜用水処理薬品を添加することを特徴とする膜処理方法。
- 前記膜用水処理薬品を、前記被処理水に、前記高分子化合物の濃度が0.01〜50mg/Lとなるように添加する請求項2に記載の膜処理方法。
- 前記膜分離処理が逆浸透膜処理であって、該逆浸透膜処理で得られる濃縮水が、下記条件(A)及び/又は(B)と、下記条件(C)とを満たす請求項2又は3に記載の膜処理方法。
(A) 該濃縮水を孔径0.45μmのフィルターで濾過して得られた濾過水について、紫外可視分光光度計を用いて50mmセルで測定した波長260nmの吸光度(abs(50mmセル))が0.01〜5.0
(B) 該濃縮水の全有機炭素(TOC)もしくは不揮発性有機炭素(NPOC)濃度が0.01〜100mg/L
(C) 該濃縮水の多価金属カチオンの濃度が1mg/L以上 - 前記逆浸透膜処理における濃縮倍率が3倍以上である請求項4に記載の膜処理方法。
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