201026612 六、發明說明： 【發明所屬之技術領域】 本發明係關於在對工業用水進行膜分離處理來製造出 純水時，或是對廢水的處理水進行膜分離處理來製造出純 水及/或製程用水時，或是對海水及/或鹹水進行膜分離處 理來製造出飲料水等的生活用水或各工業用水時等，可提 高在膜分離處理之前所進行之凝聚處理的效率，並改善提 φ 供至膜分離處理之水的MFF値之膜分離處理方法。 【先前技術】 膜分離處理技術，係使用於從工業用水之純水的製造 、從廢水處理水之純水或製程用水的製造、從海水或鹹水 之飲料水等的生活用水或工業用水的製造等之多種的水處 理領域中。 此等膜分離處理時，在膜分離處理之前，一般係進行 φ 被處理水（原水）的凝聚·固液分離處理。此凝聚處理， 一般係使用無機凝聚劑之聚氯化鋁或氯化鐵，並不會倂用 有機系高分子凝聚劑。亦即，在不伴隨膜分離處理之一般 的廢水或用水之凝聚處理中，以凝聚塊體的粗大化爲目的 ，與無機凝聚劑一同倂用聚丙烯醯胺系的陰離子性高分子 凝聚劑或陽離子系高分子凝聚劑，此等高分子凝聚劑，即 使是微量，當殘留於凝聚處理水中時，會引起膜污染，使 穿透流束（通量）降低，所以在膜分離處理之前所進行之 凝聚處理中，幾乎不會被使用。 -5- 201026612 以 MF (微孔過爐：Micropore Filtration)膜、UF (超過 濾：Ultrafiltration )膜、RO (逆滲透：Rev er se Osmosis )膜等對原水進行膜分離處理時，在膜分離處理之前所進 行之凝聚、固液分離等之前處理的製程及其組合有多數種 ，以往一般所採用的基本製程如以下所述。 a) 凝聚處理製程 將無機凝聚劑添加至原水使進行反應後，藉由浮起裝 置或沉澱裝置來進行固液分離。 b) 過濾製程 將以無機凝聚劑所處理之凝聚處理水通水至砂過濾或 雙層過濾裝置，以去除粒徑5μιη至2〜3 μιη爲止的微粒子 。然後，爲了去除溶解性有機物，亦有進行活性碳吸附處 理之情況。 此外，該前處理，除了凝聚處理製程中的凝聚劑添加 之外，作爲藥劑處理，亦可適當地添加用以防止系統內之 生物的繁殖之次氯酸鈉、有機系殺菌·制菌劑、RO膜劣 化原因之殘留氯的分解劑、RO膜之垢生成防止劑等。 此等前處理，係藉由以原水的污濁度與膜分離處理所 預測之損害，以及最終求取之處理水的水準來適當地選定 使用。 然而，上述以往的凝聚處理製程中，殘留有水溶性的 膜污染物質，雖因原水的污濁度存在有程度上的差異，但 -6- 201026612 至少會產生膜污染，R〇膜、UF膜中必須停止處理來進行 膜的化學洗淨，甚至需進行膜模組的更換’此外’ MF膜 中必須進行單元更換。 此膜污染物質大致可分爲有機物及無機物。 當中，膜污染無機物係以下列方式產生，由於原水中 之無機離子與二氧化矽在膜分離處理中的濃縮，使其超過 溶解度而結垢，此外，起因於無機凝聚劑之鋁、鐵係作爲 φ 極微粒子的羥化物膠體而殘留，不僅直接污染膜，並且藉 由與水中的二氧化矽結合進行結垢化而產生者。 另一方面，膜污染有機物可視爲隨著自然水界微生物 活動、及廢水的生物處理所代謝生成之多醣類，此外，起 因於自然界的腐植之腐植酸·富里酸系物質亦作爲膜污染 物質。 凝聚處理製程中，係要求盡可能地去除此等有機系膜 污染物質，但在依據無機凝聚劑所進行之凝聚處理中，會 φ 殘留有無法去除的膜污染物質。 該具體物質，可推測有不帶電之中性多醣類、以及僅 帶有極少電荷之多醣類。 進行膜分離處理之水（膜供應水）的膜過濾性（膜污 染性）之指標，有「MFF値」。此MFF値的測定手法如 下所述。 i)在依據混凝試驗器所進行之凝聚處理中，獲得1 0 0 0 ml以上的凝聚處理水。 Π)將凝聚處理水靜置30分鐘使凝聚塊體沉澱。 -7- 201026612 iii) 將ii)的凝聚處理水，以Νο·5Α(5μιη孔）濾紙從 清澄層開始逐漸進行過濾，最終將包含凝聚塊體之凝聚處 理水的全量進行過濾。 iv) 將所得之1 000 ml以上的濾液，以每500 ml放入 於2個量筒。 v) 使用孔徑〇.45μιη、直徑47 mm之硝化纖維素製的 薄膜過濾器，在66 kPa(500 mmHg)的減壓化下將第1 個量筒的濾液500 ml進行過濾，並測量此時的過濾所需 時間T1。接著同樣對另1個量筒的濾液5〇0 ml進行減壓 過濾，並測定此時的過濾所需時間T2。 vi) 以下列式算出MFF値。 MFF = T2/T 1 此値愈接近1.00，可評估爲愈是可作爲膜供應水之良 好水質的水，且難以污染膜之水。一般而言，MFF値爲 1 . 1以下者，乃適合作爲膜供應水。 例如，自來水（栃木縣野木町町水）的MFF爲1.03〜1.06 ，平均爲1 .05，就有機污染的程度來看，可說是作爲膜供 應水之理想的水質。 本申請人係提出下列技術作爲對生物處理原水、生物 處理水進行膜分離處理時改善膜供應水的水質之技術，亦 即，首先將具有酚性羥基之高分子添加至生物處理水後， 添加作爲無機凝聚劑之氯化鐵進行凝聚處理，並將該處理 水進行膜分離處理之方法，以及由乙烯酚系聚合物所形成 之生物處理水用凝聚促進劑（專利文獻1 )。 -8- 201026612 然而，依據此方法所得之膜供應水的MFF爲1.3，並 非可安定地獲得令人滿足的水準（MFFS1.1)之技術。 此外，由於聚乙烯酚系聚合物較昂貴，即使可減少無 機凝聚劑添加量，亦無法充分地降低全體藥劑的成本。 專利文獻2中，記載有專利文獻1所用之聚乙烯酚作 爲非離子系界面活性劑的不溶化劑。 當中，係對構造與聚乙烯酚類似之酚醛型酚樹脂進行 φ 評估’此樹脂由於其處理水的TOC (全有機碳）較原水（ 處理對象水）還高，所以不適合作爲同處理劑。 惟酚樹脂較便宜，所以就成本面來看，較聚乙烯酚系 聚合物爲有例。 專利文獻1:日本特開2007-7563號公報 專利文獻2 :日本特許第2 8 3 0 2 0 1號公報 【發明內容】 φ 本發明係鑒於上述以往的情況而創作出之發明，其目 的係提供一種在將酚系高分子化合物的鹼溶液添加至原水 後’添加無機凝聚劑進行凝聚處理，將凝聚處理水進行固 液分離’並將所得之分離水進行膜分離處理時，可改善膜 供應水的水質’並長時間地持續進行安定且有效率的膜分 離處理之膜分離處理方法。 本發明者們爲了解決上述課題而進行精心探討，結果 發現’藉由將具有酚性羥基之鹼可溶性且在中性區及/或 高鹽類存在下爲不溶化之酚系高分子化合物的鹼溶液稀釋 -9- 201026612 爲特定濃度並添加至原水，更能夠改善膜供應水的MFF 値。 亦即，在添加酚系高分子化合物的鹼溶液之凝聚處理 中，係利用此酚系高分子化合物於中性區析出之性質’使 膜污染有機物凝聚而去除。然而，就同樣理由來看’所析 出之酚系高分子化合物彼此會聚集、析出，變得無法與被 處理水中的膜污濁物質進行反應，而具有需增加必要之酚 系高分子化合物的添加量之問題。 相對於此，藉由充分地降低添加酚系高分子化合物時 之酚系高分子化合物的濃度，並充分地稀釋酚系高分子化 合物的鹼溶液來添加，可降低凝聚處理系內之酚系高分子 化合物彼此的聚集頻率，防止其析出而失去凝聚劑的功能 ，而更進一步地改善膜供應水的MFF値，並且可降低酚 系高分子化合物本身的添加量，達到藥劑使用量及藥劑成 本的降低。 此外，如上所述，雖然酚樹脂較便宜，但由於添加此 ，使凝聚處理水的TO C較原水更高，而不適合作爲凝聚 處理劑。根據本發明者們的探討，此原因可考量爲在所添 加之酚樹脂中，殘存有較多在中性區不會析出之樹脂成分 ，此會導致處理水之TOC的上升。 對於此類酚樹脂，依循本發明充分地稀釋再添加至原 水，可減少添加量本身，降低酚樹脂對處理水的殘留量， 而解決TOC上升的問題。 一般而言，凝聚處理藥劑，係在物理上可允許的範圍 -10- 201026612 內以高濃度的條件添加至原水。例如，聚氯化鋁係藉由泵 浦’直接將A1203之10 wt%的製品原液注入。 本發明中所用之酚系高分子化合物的鹼溶液，其酚系 高分子化合物濃度爲20 wt/vol%，顯示出充分的流動性， 一般係調製爲10~35 wt/vol%的濃度，並可直接將此添加 至原水。 因此，以往將酚系高分子化合物設爲如此高濃度之鹼 φ 溶液來添加，但藉由本發明者們的探討，當將此酚系高分 子化合物稀釋爲以往未曾出現之低濃度來添加時，可大幅 改善凝聚處理水的MFF値，此外亦可降低必要的添加量 〇 本發明係根據此發現所達成者，並以下列爲要旨。 第1型態之膜分離處理方法，爲將酚系高分子化合物 的鹼溶液添加至海水或電傳導度1 000 ms/m以上之含有高 鹽類的水之被處理水後，添加無機凝聚劑進行凝聚處理， ❿ 將凝聚處理水進行固液分離，並將所得之分離水進行膜分 離處理之方法，其特徵爲：該酚系高分子化合物，爲具有 酚性羥基之鹼可溶性，且在中性區及/或高鹽類存在下爲 不溶化之高分子化合物，並將該高分子化合物作爲高分子 化合物濃度0.1 Wt/vol%以下的鹼溶液而添加至該被處理 水。 第2型態之膜分離處理方法’爲將酚系高分子化合物 的鹼溶液添加至電傳導度未滿1 000 mS/m的被處理水後， 添加無機凝聚劑進行凝聚處理’將凝聚處理水進行固液分 -11 - 201026612 離’並將所得之分離水進行膜分離處理之方法，其特徵爲 :該酚系高分子化合物，爲具有酚性羥基之鹼可溶性，且 在中性區及/或高鹽類存在下爲不溶化之高分子化合物， 並將該高分子化合物作爲高分子化合物濃度1 Wt/vol%以 下的鹼溶液而添加至該被處理水。 第3型態之膜分離處理方法，在第1或第2型態中， 係將含有1〜35 wt/vol%的前述酚系高分子化合物之鹼溶液 ’以泵浦吐出定量後，在即將添加至前述被處理水時，以 水稀釋再添加至該被處理水。 根據本發明，藉由將具有酚性羥基之鹼可溶性且在中 性區及/或高鹽類存在下爲不溶化之酚系高分子化合物（ 以下有僅稱爲「酚系高分子化合物」時）的鹼溶液，作爲 原水的凝聚處理劑予以稀釋並添加至原水，可防止所添加 之酚系高分子化合物成爲膜污染有機物及TOC成分，而 獲得低MFF値之高水質的膜供應水，藉此可防止膜污染 ，降低膜的化學洗淨或更換頻率，並且長時間地進行安定 且有效率的膜分離處理。 【實施方式】 以下詳細說明本發明之實施型態。 [原水的種類] 本發明中，作爲處理對象的原水並無特別限制，例如 有提供至膜分離處理之各種工業用水、廢水的處理水、海 -12- 201026612 水、鹹水等。 [酚系高分子化合物的種類] 本發明中所用之酚系高分子化合物，係具有酚性羥基 ，爲鹼可溶性，且在中性區及/或高鹽類存在下爲不溶化 者，具體而言有下列所列舉者。 Φ 〈酚系樹脂〉 (1)酚與甲醛之縮合物 (2) 甲酚與甲醛之縮合物 (3) 二甲苯酚與甲醛之縮 (4 )將上述（1 )〜（3 )的酚系樹脂進行烷化所製得 之經烷改質的酚系樹脂 此等酚系樹脂可爲酚醛型或是甲酚型，或是兩者的混 合物。使用何種酚系樹脂者，可藉由原水的種類來選擇使 參 用更有效果者。 酸醛型酚系樹脂、甲酚型酚系樹脂的重量平均分子量 (Mw ) ’較佳爲1 〇〇〇以上，例如丨ooom 〇〇〇〇()，特佳爲 1000-20000° <聚乙烯酚系聚合物> (5)乙嫌酚同元聚合物 (ό)經改質的乙烯酚同元聚合物 (7 )乙稀酣及/或經改質的乙烯酚與疏水性乙烯單體 -13- 201026612 之共聚物 上述（6)之經改質的乙烯酚同元聚合物，例如有經 烷基或芳基等所取代之乙烯酚、鹵化乙烯酚等，苯基經任 意化合物進行化學修飾後的乙烯酣。 此外，（7 )之疏水性乙烯單體，例如有乙烯、丙烯 腈、甲基丙烯酸甲酯等之水不溶性或水難溶性之乙烯單體 。此類疏水性乙烯單體與乙烯酚及/或經改質的乙烯酚之 共聚物中之乙烯酚及/或經改質的乙烯酚的比例，以莫耳 比較佳爲0.5以上，特佳爲〇.7以上。 前述（5)〜（7)之乙烯酚系聚合物，其重量平均分 子量（Mw)較佳爲1〇〇〇以上，例如1〇〇〇〜100000，特佳 爲1 000-20000’如此分子量的聚合物，一般是以粉末來提 供。 此等酚系高分子化合物，可單獨使用1種或混合2種 以上而使用。 [酚系高分子化合物的鹼溶液] 上述酚系高分子化合物，由於不溶或難溶於水，所以 係溶解或分散於可溶解於水之溶劑等，構成爲溶液狀或乳 化液來使用。所用之溶劑，例如有丙酮等酮類、乙酸甲酯 等酯類、甲醇等醇類等之水溶性有機溶劑、鹼水溶液、胺 等’本發明中，係使用苛性鈉（NaOH )、苛性鉀（KOH )等之鹼劑而構成爲溶液。 稀釋前之酚系高分子化合物的鹼水溶液，一般係調製 -14 - 201026612 爲鹼劑濃度3〜25 wt/wt%’酚系高分子化合物濃度ι〇〜35 wt/wt% 〇 [酚系高分子化合物之添加時的濃度] 本發明中，當被處理水爲海水或電傳導度1000 ms/m 以上之含有高鹽類的水時’係以酚系高分子化合物之鹼溶 液中的濃度成爲〇.1 wt/vol%以下之方式稀釋酚系高分子 φ 化合物而添加至被處理水。當將酚系高分子化合物的鹼溶 液添加至被處理水時之酚系高分子化合物濃度超過1 wt/vol%時，無法獲得本發明之前述效果。 另一方面，當被處理水爲電傳導度未滿1 000 mS/m的 水時，酚系高分子化合物的鹼溶液添加時之酚系高分子化 合物濃度爲1 wt/vol%即可，因此係以成爲該濃度之方式 ’來稀釋酚系高分子化合物的鹼溶液。 稀釋的有效性，在酚系高分子化合物容易析出之原水 φ 中爲顯著，在鹽類濃度高的海水或電傳導度1000 mS/m以 上之高鹽類濃度的水中特別有效。 爲此類高鹽類濃度的原水時，酚系高分子化合物添加 時之濃度較佳爲更低，鹼溶液中之酚系高分子化合物濃度 較佳爲 0.1 Wt/vol%以下，例如 〇.〇1 〜0.1 wt/v〇i%。 若是鹽類濃度不如海水般的高，且電傳導度爲300 mS/m以下之原水’則鹼溶液中之酚系高分子化合物的添 加時濃度’較佳爲〇 . 1〜1 . 〇 w t / v 〇 1 %。 不論何種情況，當酚系高分子化合物的濃度高時，無 -15- 201026612 法充分獲得本發明之前述效果，相反地，若過低，則所添 加之酚系高分子化合物的鹼溶液之稀釋水量增多，因而較 不佳。 [酚系高分子化合物的稀釋方法] 依循本發明將上述稀釋溶液添加至原水時，較佳爲直 接將以往構成爲鹼劑濃度 3~25 wt/wt%、l〇~35 wt/wt%的 酚系高分子化合物濃度之酚系高分子化合物的鹼溶液’或 g 是先將酚系高分子化合物濃度稀釋爲3~10 wt/vol%，以泵 浦吐出定量後，在即將添加至原水時，以稀釋水將酚系高 分子化合物稀釋爲特定濃度以下再添加至原水。另一方面 ，在準備預先將酚系高分子化合物稀釋爲特定濃度以下之 酚系高分子化合物的鹼溶液，並添加至原水之方法中，必 須準備用於稀釋溶液的貯留、添加之大型設備，此外，於 稀釋溶液中會生成不溶化物，使凝聚效果降低，因而較不 佳。 ❹ 此外，如此將酚系高分子化合物稀釋爲特定濃度以下 後，至添加至原水爲止之時間愈短愈佳，較佳大致爲數秒 〜10秒。當此時間愈長，於稀釋溶液中會生成不溶化物， 使凝聚效果降低，因而較不佳。 用於稀釋之水’較佳爲鹽類濃度低的水，較佳爲電傳 導度100 mS/m以下、PH6以上之水。在海水般之鹽類濃 度高的水或是酸性水中’酚系高分子化合物會聚集、析出 ，因而較不佳。 -16- 201026612 [酚系高分子化合物的添加量] 對原水之酚系高分子化合物的添加量，係因原水的水 質、所用之酚系高分子化合物的種類、鹼溶液中之酚系高 分子化合物濃度等而有所不同，無法以一槪全’一般而言 ，酚系高分子化合物的添加量爲0.1〜20 mg/L，尤其爲 0.3〜10 rng/L，例如較佳爲，可因應原水及酚系高分子化 • 合物及該鹼溶液中的濃度，設定爲下列添加量。 [第1表] 原水的種類 驗溶液中之酸系局分子 化合物濃度(wt/vol%) 酚系高分子化合物添加量 (mg/L) 海水等之含有高鹽類的水 0.01-0.1 0.5-2 河川水、工業用水 0.1-1.0 0.3〜1.0 生物處理水 0.1-1.0 0.5-10 [酚系高分子化合物添加後的反應時間] 將酚系高分子化合物添加至原水後至添加無機凝聚劑 爲止之時間’亦即酚系高分子化合物的反應時間，較佳係 設爲1分鐘以上。此反應時間，若反應槽、貯留槽或中繼 槽容量等可容許者’則愈長愈佳，例如較佳爲5分鐘〜i 〇 分鐘。此外，此反應槽較佳爲適當地進行攪拌，但若在最 初即可將酚系高分子化合物的鹼溶液完全混合至被處理水 全體時，則亦可不進行之後的攪拌。 [酣系高分子化合物與無機凝聚劑的添加順序] -17- 201026612 本發明中’係將酣系高分子化合物添加至原水後再添 加無機凝聚劑。當同時將酚系高分子化合物與無機凝聚劑 添加至原水’或是將無機凝聚劑添加至接近於酚系高分子 化合物的添加場所之場所時，酚系高分子化合物與無機凝 聚劑會直接反應’結果無法獲得酚系高分子化合物的添加 效果，且爲了補償因反應所消耗的量，而使藥劑的必須添 加量增加。 當使酚系高分子化合物在無機凝聚劑之後才添加時， 酚系高分子化合物會以未凝聚的狀態殘留，成爲膜分離阻 礙物，導致MFF値惡化。 [無機凝聚劑] 於酚系高分子化合物添加後所添加之無機凝聚劑，可 使用聚氯化鋁、硫酸鋁、氯化鋁等之鋁系凝聚劑；氯化鐵 、硫酸鐵、聚硫酸鐵等之鐵系凝聚劑。此等可單獨使用1 種或倂用2種以上。 無機凝聚劑的選定，例如當單獨將該無機凝聚劑添加 至原水時，作爲可獲得最優良效果之無機凝聚劑，該添加 量較佳係設爲，凝聚處理水的MFF値即使添加該量以上 的無機凝聚劑亦不會改善，或是僅有些許改善之添加量。 此無機凝聚劑的添加量，係因原水的水質或無機凝聚 劑的種類、所要求之MFF値而有所不同，一般相對於原 7K 爲 30~500 mg/L。 201026612 [膜分離處理] 本發明中，膜分離處理所用之分離膜，可爲MF (微 孔過濾）膜、UF (超過濾）膜、RO (逆滲透）膜、NF ( 奈米過濾：Nanofiltration)等的任一種。膜的型態可爲平 膜、管狀膜、中空線等的任一種，亦可爲浸漬膜。膜的材 質例如有 PVDF (聚二氟亞乙嫌：Polyvinylidene Fluoride )、PE (聚乙烯）、PP (聚丙烯）等，但不限定於此。 實施例 以下係舉出實驗例、實施例及比較例，來更具體地說 明本發明。 以下，酚系高分子化合物係使用下列所示者。 PVF2000 ：聚乙烯酚（Mw = 2000 ) FR6000 ：酚醛型酚樹脂（Mw = 6000 ) FR2000:酚醛型酚樹脂（Mw = 2000 ) φ 上述酚系高分子化合物的鹼溶液，P VF2000中係使用 1 8 w t / w t %的苛性鈉水溶液，F R 6 0 0 0及F R 2 0 0 0中使用3 0 wt/wt%的苛性鈉水溶液，此等酚系高分子化合物的鹼溶液 之稀釋’爲了防止酚系高分子化合物的析出，係以純水來 進行，濃度係針對每個實驗來進行調整。 此外’無機凝聚劑係使用下列所示者，並以純水將市 售品稀釋爲製品濃度1 0 w/v%來使用。 FC :氯化鐵市售品（FeCl3濃度38 wt% ) LAC :液體氯化鋁市售品（Al2〇3濃度10·4 wt%) 19- 201026612 LAS :液體硫酸鋁市售品（Al2(S〇3)3濃度27 wt%) PAC :液體氯化鋁市售品（Al2〇3濃度10.5 wt%) [實驗例1 :低濃度添加所形成之效果的實證] 將PVF2000、FR6000及FR2000的鹼水溶液，分別以 純水稀釋爲酚系高分子化合物濃度 3 600 mg/L ( 0.36 wt/vol%)，分別將此稀釋液1ml，滴入至藉由鹼的添加 而調整爲5.8〜9.0的pH之海水或野木町水並進行混合， 使水中的酚系高分子化合物濃度成爲36 mg/L，測定各個 的pH與濁度，結果如第1圖（海水）及第2圖（野木町 水）所示。 從第1圖、第2圖中可得知下列結果。 當將酚系高分子化合物的鹼水溶液添加至海水時’在 pH5.8~9.0的條件下產生劇烈的混濁（濁度=22〜30 )，不 論P Η爲何，其程度均箱爲同等程度。亦即’藉由海水中 之高濃度鹽類的作用，使偏離之酚性羥基的負帶電被封鎖 ，失去溶解性，使酚系高分子化合物聚集並成爲不溶化’ 因而產生濁質。 如此，當原水爲海水時’由於會使原先讓有效成分與 欲作用的膜污染物質進行反應前所添加之酚系高分子化合 物彼此結合，所以無法獲得M F F的改善。 此時，可推測爲當充分地稀釋酚系高分子化合物的鹼 溶液時，酚系高分子化合物的密度減少’降低酚系高分子 化合物彼此聚集的機率，到達膜污染物質而進行反應’亦 -20- 201026612 即’可使膜污染物質與酚系高分子化合物進行反應，而獲 得本發明之效果。 另一方面，爲野木町水時，在中性區中，不論何種酚 系高分子化合物均產生濁度，在pH7.5~8.5或以上的鹼性 區中，濁度產生較少並趨近於零。 比較濁度產生pH時，聚乙烯酚（PVF2000 )係從更 高的pH値開始產生。酚醛型酚樹脂（FR6000、FR2000 ) φ 中’分子量較大者，濁度値、濁度產生pH稍高。 然而，不論何種酚系高分子化合物，在中性區中均會 產生酚系高分子化合物的聚集、不溶化。 此可推測爲以低濃度添加酚系高分子化合物的鹼溶液 者，爲MFF更爲改善，且必要添加量亦降低之理由。 [實施例及比較例] 以下實施例及比較例中，係以下列實驗方法來進行。 <實驗方法> (1)原水調整至24±2°C，取其1100 ml至燒杯，並 以使用有宮本製作所製的MJS-6N之混凝試驗來進行凝聚 處理。 混凝試驗的攪拌、反應條件如下所示。 •酚系高分子化合物的鹼溶液，係在1 5 0 rpm的攪拌 下添加，並在1 5 〇 rpm下進行5分鐘的攪拌反應。 •無機凝聚劑係在150 rpm的攪拌下添加，並在150 -21 - 201026612 rpm下進行10分鐘的急速攪拌以及在5〇 rpm下進行〗〇分 鐘的緩速攪拌。 .處理pH’在鋁系凝聚劑中設爲ρίί6以上，當凝聚 劑添加後PH未滿6時’以大致成爲pH6.1之方式，藉由 5 wt/vol%的苛性鈉水溶液進行中和。在鐵系凝聚劑中設爲 pH5以上’當pH未滿5時’以大致成爲ph5.2之方式， 藉由5 wt/vol%的苛性鈉水溶液進行中和。 (2)將（1)所得之凝聚處理水靜置30分鐘，使凝 聚塊體沉澱。 (3 )將（2 )的凝聚處理水，以N〇. 5 ( 5 μιη孔）濾紙 從清澄層開始逐漸進行過濾，最終將包含凝聚塊體之凝聚 處理水的全量進行過濾。 (4 )將所得之1 〇〇〇 ml以上的濾液，以每5 00 ml放 入於2個量筒。 (5)使用Millipore社製之孔徑〇.45μιη、直徑47mm 之硝化纖維素製的薄膜過濾器’在66 kPa ( 500 mmHg ) 的減壓下將第1個量筒的濾液5 0 0 m 1進行過濾，並測量 此時的過濾所需時間T 1。接著同樣對另1個量筒的濾液 5 0 0 m 1進行減壓過濾，並測定此時的過濾所需時間T 2 ’ 算出 MFF = T2/T1。 水溫係以成爲測定時的24±2°C之方式來調整實驗室溫 度，並記錄測定時的水溫。201026612 VI. Description of the Invention: [Technical Field] The present invention relates to a method for producing pure water by performing membrane separation treatment of industrial water to produce pure water, or by performing membrane separation treatment on treated water of wastewater. When the process water is used, or the seawater and/or salt water is subjected to membrane separation treatment to produce domestic water such as beverage water or industrial water, the efficiency of the coagulation treatment performed before the membrane separation treatment can be improved and improved. A membrane separation treatment method for MFF which is supplied to the membrane separation treatment. [Prior Art] The membrane separation treatment technology is used for the production of pure water from industrial water, the production of pure water or process water from wastewater treatment water, and the production of domestic or industrial water from seawater or salt water. A variety of water treatment areas. In the membrane separation treatment, agglomeration/solid-liquid separation treatment of φ treated water (raw water) is generally performed before the membrane separation treatment. In the coagulation treatment, polyaluminum chloride or ferric chloride which is an inorganic coagulant is generally used, and an organic polymer coagulant is not used. In other words, in the general treatment of wastewater or water coagulation treatment without a membrane separation treatment, a polyacrylamide-based anionic polymer flocculant or an inorganic coagulant is used together with the purpose of coarsening the agglomerate. The cationic polymer flocculating agent, even if it is a trace amount, when it remains in the coagulation-treated water, it causes membrane fouling and reduces the penetrating flux (flux), so it is performed before the membrane separation process. In the coagulation process, it is hardly used. -5- 201026612 When the raw water is subjected to membrane separation treatment with MF (Micropore Filtration) membrane, UF (Ultrafiltration: Ultrafiltration) membrane, RO (Reverse Osmosis: Rever Osmosis) membrane, etc., membrane separation treatment There have been many types of processes and combinations thereof before coagulation, solid-liquid separation, etc., and the basic processes generally used in the past are as follows. a) Coagulation treatment process The inorganic coagulant is added to the raw water to carry out the reaction, and then the solid-liquid separation is carried out by a floating device or a sedimentation device. b) Filtration process The agglomerated water treated with the inorganic coagulant is passed through a sand filtration or double-layer filtration device to remove fine particles having a particle size of 5 μm to 2 to 3 μm. Then, in order to remove the dissolved organic matter, there is also a case where the activated carbon adsorption treatment is carried out. In addition, in this pretreatment, in addition to the addition of the coagulant in the coagulation treatment process, as the chemical treatment, sodium hypochlorite, organic sterilization, bacteriostatic agent, and RO membrane deterioration for preventing the growth of organisms in the system may be appropriately added. The residual chlorine decomposition agent, the RO film scale formation inhibitor, and the like. These pretreatments are appropriately selected and used by the contamination of the raw water and the damage predicted by the membrane separation treatment, and the level of the treated water finally obtained. However, in the above-mentioned conventional coagulation treatment process, water-soluble membrane contaminants remain, and although there is a degree of difference in the degree of contamination of the raw water, at least -6-201026612 may cause membrane fouling, R 〇 membrane, UF membrane The treatment must be stopped to carry out the chemical cleaning of the membrane, and even the replacement of the membrane module is required. In addition, the unit replacement must be carried out in the MF membrane. The membrane pollutants can be roughly classified into organic matter and inorganic matter. Among them, the membrane-contaminated inorganic substance is produced in the following manner, because the inorganic ions in the raw water and the cerium oxide are concentrated in the membrane separation treatment, so that they exceed the solubility and scale, and in addition, the aluminum and iron based on the inorganic coagulant act as The hydroxyl colloid of the φ microparticles remains and not only directly contaminates the membrane, but also is produced by scaling with cerium oxide in water. On the other hand, membrane-contaminated organic matter can be regarded as a polysaccharide that is metabolized by microbial activities in natural water and biological treatment of wastewater. In addition, humic acid and fulvic acid substances derived from natural humic substances are also used as membrane pollutants. . In the coagulation treatment process, it is required to remove such organic film contaminants as much as possible. However, in the coagulation treatment by the inorganic coagulant, membrane contaminants which cannot be removed remain in φ. As the specific substance, it is presumed that there are uncharged neutral polysaccharides and polysaccharides having only a small amount of charge. "MFF値" is an index of membrane filterability (film fouling property) of water (membrane supply water) for membrane separation treatment. The measurement method of this MFF is as follows. i) In the coagulation treatment by the coagulation tester, agglomerated treated water of 1 000 ml or more is obtained. Π) The coagulated water was allowed to stand for 30 minutes to precipitate agglomerates. -7- 201026612 iii) The condensed water of ii) is gradually filtered from the clear layer by Νο·5Α (5μιηη) filter paper, and finally the total amount of the agglomerated water containing the agglomerate is filtered. Iv) The resulting filtrate of more than 1 000 ml is placed in 2 cylinders per 500 ml. v) Using a membrane filter made of nitrocellulose having a pore size of 45.45 μm and a diameter of 47 mm, 500 ml of the filtrate of the first measuring cylinder was filtered under reduced pressure of 66 kPa (500 mmHg), and the measurement was performed at this time. Filter the time T1 required. Then, 5 〇 0 ml of the filtrate of the other measuring cylinder was filtered under reduced pressure, and the time T2 required for filtration at this time was measured. Vi) Calculate MFF値 by the following formula. MFF = T2/T 1 This recovery is close to 1.00, which can be evaluated as the water that can be used as a good water supply for the membrane, and it is difficult to contaminate the water of the membrane. In general, MFF 値 is 1.1 or less, and is suitable as a film supply water. For example, the MFF of the tap water (Yumakicho, Tochigi) is 1.03 to 1.06, and the average is 1.05. It is the ideal water quality for the membrane supply water in terms of the degree of organic pollution. The present applicant has proposed the following technique as a technique for improving the water quality of a membrane supply water when performing membrane separation treatment on biologically treated raw water or biologically treated water, that is, first adding a polymer having a phenolic hydroxyl group to biological treatment water, and then adding A method of agglomeration treatment of ferric chloride as an inorganic coagulant, a membrane separation treatment of the treated water, and a coagulation accelerator for biological treatment water formed of a vinyl phenol-based polymer (Patent Document 1). -8- 201026612 However, the membrane supplied water obtained by this method has an MFF of 1.3 and is not stable to obtain a satisfactory level (MFFS 1.1) technique. Further, since the polyvinyl phenol-based polymer is relatively expensive, the cost of the entire pharmaceutical agent cannot be sufficiently reduced even if the amount of the inorganic coagulant added can be reduced. Patent Document 2 describes a polyethylene phenol used in Patent Document 1 as an insolubilizer for a nonionic surfactant. Among them, the phenolic phenol resin having a structure similar to that of polyvinylphenol was evaluated as φ. This resin is not suitable as a treating agent because its TOC (total organic carbon) of treated water is higher than that of raw water (treated water). However, the phenol resin is relatively inexpensive, so that it is a case of a polyethylene phenol-based polymer in terms of cost. Patent Document 1: Japanese Laid-Open Patent Publication No. 2007-7563 (Patent Document 2): Japanese Patent No. 2,800,020, the disclosure of the present invention is hereby incorporated by reference. When the alkali solution of the phenol-based polymer compound is added to the raw water, and the inorganic coagulant is added to carry out the coagulation treatment, and the coagulated water is subjected to solid-liquid separation, and the obtained separated water is subjected to membrane separation treatment, the film supply can be improved. The water quality of water 'and a membrane separation treatment method for stable and efficient membrane separation treatment for a long time. In order to solve the above problems, the present inventors have intensively studied and found that an alkali solution of a phenol-based polymer compound which is insoluble by a base having a phenolic hydroxyl group and insoluble in the presence of a neutral region and/or a high salt is found. Dilution -9- 201026612 is a specific concentration and added to the raw water, which can improve the MFF 値 of the membrane supply water. In the coagulation treatment of the alkali solution to which the phenol-based polymer compound is added, the film-contaminated organic matter is agglomerated and removed by utilizing the property of the phenol-based polymer compound to precipitate in the neutral zone. However, for the same reason, the phenol-based polymer compounds which are deposited are aggregated and precipitated, and it is impossible to react with the film fouling substance in the water to be treated, and it is necessary to increase the amount of the phenol-based polymer compound to be added. The problem. On the other hand, by sufficiently reducing the concentration of the phenol-based polymer compound when the phenol-based polymer compound is added and sufficiently diluting the alkali solution of the phenol-based polymer compound, the phenolic system in the coagulation treatment system can be lowered. The frequency of aggregation of the molecular compounds is prevented from being precipitated to lose the function of the coagulant, and the MFF of the film supply water is further improved, and the amount of the phenol-based polymer compound itself can be reduced, thereby achieving the amount of the drug used and the cost of the drug. reduce. Further, as described above, although the phenol resin is relatively inexpensive, since this is added, the TO C of the coagulated water is made higher than that of the raw water, and is not suitable as a coagulation treatment agent. According to the investigation by the inventors of the present invention, it is considered that in the phenol resin to be added, a large amount of resin component which does not precipitate in the neutral region remains, which causes an increase in the TOC of the treated water. For such a phenol resin, it is sufficiently diluted according to the present invention to be added to the raw water, thereby reducing the amount of addition itself, reducing the residual amount of the phenol resin to the treated water, and solving the problem of an increase in TOC. In general, the coacervation treatment agent is added to the raw water at a high concentration in a physically permissible range -10- 201026612. For example, polyaluminum chloride is injected directly into the stock solution of 10 wt% of A1203 by pumping. The alkali solution of the phenol-based polymer compound used in the present invention has a phenol-based polymer compound concentration of 20 wt/vol%, and exhibits sufficient fluidity, and is generally prepared to have a concentration of 10 to 35 wt/vol%. This can be added directly to the raw water. Therefore, in the past, the phenol-based polymer compound was added as such a high-concentration alkali φ solution, but when the phenol-based polymer compound was diluted to a low concentration which has not been conventionally added, it was investigated by the present inventors. The MFF(R) of the coagulated water can be greatly improved, and the necessary amount of addition can be reduced. The present invention has been made based on this finding, and the following are the gist of the present invention. The membrane separation treatment method of the first type is an inorganic flocculant after adding an alkali solution of a phenol-based polymer compound to seawater or treated water containing high-salt water having an electrical conductivity of 1 000 ms/m or more. a method of performing a coagulation treatment, ❿ a solid-liquid separation of the coagulated water, and a membrane separation treatment of the obtained separated water, wherein the phenol-based polymer compound is alkali-soluble with a phenolic hydroxyl group, and is in the middle A polymer compound which is insoluble in the presence of a chemical region and/or a high salt is added to the water to be treated as an alkali solution having a polymer compound concentration of 0.1 Wt/vol% or less. The membrane separation treatment method of the second type is a method in which an alkali solution of a phenol-based polymer compound is added to water to be treated having an electrical conductivity of less than 1 000 mS/m, and an inorganic coagulant is added for agglomeration treatment. A solid-liquid fraction -11 - 201026612 is a method for separating and separating the obtained separated water, characterized in that the phenol-based polymer compound is alkali-soluble with a phenolic hydroxyl group, and is in a neutral region and/or Or a polymer compound which is insoluble in the presence of a high salt, and the polymer compound is added to the water to be treated as an alkali solution having a polymer compound concentration of 1 Wt/vol% or less. In the membrane separation treatment method of the third type, in the first or second type, an alkali solution containing 1 to 35 wt/vol% of the phenol-based polymer compound is pumped and quantified, and When it is added to the above-mentioned water to be treated, it is diluted with water and added to the water to be treated. According to the present invention, a phenol-based polymer compound which is insoluble in a base having a phenolic hydroxyl group and is insoluble in the presence of a neutral region and/or a high salt (hereinafter referred to simply as "phenolic polymer compound") The alkali solution is diluted as a coagulation treatment agent of raw water and added to the raw water, thereby preventing the added phenol-based polymer compound from becoming a membrane-contaminated organic substance and a TOC component, thereby obtaining a membrane water having a high MFF of high MFF. It can prevent membrane fouling, reduce the chemical cleaning or replacement frequency of the membrane, and perform stable and efficient membrane separation treatment for a long time. [Embodiment] Hereinafter, embodiments of the present invention will be described in detail. [Type of Raw Water] In the present invention, the raw water to be treated is not particularly limited, and for example, various industrial waters and wastewater treatment water supplied to the membrane separation treatment, sea water, seawater, water, salt water, and the like are provided. [Type of phenol-based polymer compound] The phenol-based polymer compound used in the present invention has a phenolic hydroxyl group, is alkali-soluble, and is insoluble in the presence of a neutral region and/or a high salt, specifically There are the following listed. Φ <phenolic resin> (1) condensate of phenol and formaldehyde (2) condensate of cresol and formaldehyde (3) condensation of xylenol and formaldehyde (4) The phenolic system of the above (1) to (3) Alkyl-modified phenol-based resin obtained by alkylation of a resin These phenol-based resins may be a phenolic type or a cresol type, or a mixture of the two. Which phenolic resin is used can be selected by the type of raw water to make the application more effective. The weight average molecular weight (Mw )' of the acid phenol type phenol resin and the cresol type phenol type resin is preferably 1 Å or more, for example, 丨ooom 〇〇〇〇 (), particularly preferably 1000-20000 ° < Ethylene phenolic polymer> (5) B-phenolic phenolic polymer (ό) modified vinyl phenolic polymer (7) Ethylene hydride and/or modified vinyl phenol and hydrophobic vinyl Copolymer of the body-13-201026612 The modified ethylene phenolic homopolymer of the above (6), for example, an alkylphenol substituted with an alkyl group or an aryl group, a halogenated vinyl phenol, etc., the phenyl group is subjected to any compound Chemically modified vinyl hydrazine. Further, the hydrophobic ethylene monomer of (7) is, for example, a water-insoluble or water-insoluble ethylene monomer such as ethylene, acrylonitrile or methyl methacrylate. The ratio of the vinyl phenol and/or the modified vinyl phenol in the copolymer of the hydrophobic ethylene monomer and the vinyl phenol and/or the modified vinyl phenol is preferably 0.5 or more, more preferably 〇.7 or above. The ethylene phenol-based polymer of the above (5) to (7) preferably has a weight average molecular weight (Mw) of 1 Å or more, for example, 1 Å to 100,000, particularly preferably 1 000 to 20,000 Å. The polymer is generally provided as a powder. These phenol-based polymer compounds may be used singly or in combination of two or more kinds. [Alkali solution of a phenol-based polymer compound] The phenol-based polymer compound is dissolved or dispersed in a solvent soluble in water, and is used as a solution or an emulsified liquid, since it is insoluble or poorly soluble in water. Examples of the solvent to be used include a ketone such as acetone, an ester such as methyl acetate, a water-soluble organic solvent such as an alcohol such as methanol, an aqueous alkali solution, an amine, etc. In the present invention, caustic soda (NaOH) and caustic potash are used. An alkali agent such as KOH) is used as a solution. The aqueous alkali solution of the phenol-based polymer compound before dilution is generally prepared by -14 to 20,266,612. The concentration of the alkali agent is 3 to 25 wt/wt%. The concentration of the phenolic polymer compound is ι 〇 35 wt/wt% 〇 [phenolic high In the present invention, when the water to be treated is seawater or water having a high conductivity of 1000 ms/m or more, the concentration in the alkali solution of the phenol-based polymer compound becomes The phenol-based polymer φ compound is diluted to 1 wt/vol% or less and added to the water to be treated. When the concentration of the phenol-based polymer compound when the alkali solution of the phenol-based polymer compound is added to the water to be treated exceeds 1 wt/vol%, the above effects of the present invention cannot be obtained. On the other hand, when the water to be treated is water having an electrical conductivity of less than 1 000 mS/m, the concentration of the phenol-based polymer compound when the alkali solution of the phenol-based polymer compound is added is 1 wt/vol%. The alkali solution of the phenol-based polymer compound is diluted in the form of the concentration. The effectiveness of the dilution is remarkable in the raw water φ in which the phenol-based polymer compound is easily precipitated, and is particularly effective in seawater having a high salt concentration or water having a high salt concentration of 1000 mS/m or more. When the raw water having a high salt concentration is used, the concentration of the phenol-based polymer compound is preferably lower, and the concentration of the phenol-based polymer compound in the alkali solution is preferably 0.1 Wt/vol% or less, for example, 〇.〇. 1 to 0.1 wt/v〇i%. If the concentration of the salt is not as high as that of seawater, and the original conductivity of the electrical conductivity is 300 mS/m or less, the concentration of the phenolic polymer compound in the alkali solution is preferably 〇. 1~1. 〇wt / v 〇1 %. In any case, when the concentration of the phenol-based polymer compound is high, the above-described effects of the present invention are sufficiently obtained without the -15-201026612 method, and conversely, if it is too low, the alkali solution of the phenol-based polymer compound to be added is used. The amount of dilution water is increased, which is less preferred. [Dilution Method of Phenolic Polymer Compound] When the above diluted solution is added to raw water according to the present invention, it is preferred to directly form an alkali agent concentration of 3 to 25 wt/wt% and 10 to 35 wt/wt%. The alkali solution ' or g of the phenol-based polymer compound having a concentration of the phenol-based polymer compound is diluted with the concentration of the phenol-based polymer compound to 3 to 10 wt/vol%, and is pumped and discharged, and then added to the raw water. The phenolic polymer compound is diluted to a specific concentration or lower with dilution water and added to the raw water. On the other hand, in the method of preparing an alkali solution in which a phenol-based polymer compound is diluted to a specific concentration or less of a phenol-based polymer compound and adding it to raw water, it is necessary to prepare a large-scale apparatus for storing and adding a diluted solution. Further, insolubles are formed in the diluted solution to lower the agglomeration effect, which is less preferable. Further, in the case where the phenol-based polymer compound is diluted to a specific concentration or less, the shorter the time until the addition to the raw water, the better, and it is preferably about several seconds to 10 seconds. When this time is longer, insolubles are formed in the diluted solution, so that the agglomeration effect is lowered, which is less preferable. The water used for dilution' is preferably water having a low salt concentration, preferably water having an electric conductivity of 100 mS/m or less and a pH of 6 or more. The phenolic polymer compound is aggregated and precipitated in water or acid water having a high concentration of seawater, and thus is inferior. -16- 201026612 [Addition amount of phenol-based polymer compound] The amount of phenol-based polymer compound in raw water is based on the water quality of the raw water, the type of phenol-based polymer compound used, and the phenol-based polymer in the alkali solution. The concentration of the compound may be different, and the amount of the phenolic polymer compound may be 0.1 to 20 mg/L, especially 0.3 to 10 rng/L, for example, preferably, it may be The concentration of the raw water and the phenol-based polymer compound and the alkali solution is set to the following addition amount. [Table 1] Types of raw water test The concentration of the acid-based compound in the solution (wt/vol%) The amount of the phenol-based polymer compound (mg/L) Water containing high salt such as seawater 0.01-0.1 0.5- 2 River water, industrial water 0.1-1.0 0.3~1.0 Biological treatment water 0.1-1.0 0.5-10 [Reaction time after addition of phenolic polymer compound] Adding phenolic polymer compound to raw water until inorganic coagulant is added The reaction time of the phenolic polymer compound at the time ' is preferably 1 minute or longer. The reaction time is as long as the allowable amount of the reaction tank, the storage tank or the relay tank is as long as possible, for example, preferably 5 minutes to 1 minute. In addition, it is preferable that the reaction tank is appropriately stirred. However, when the alkali solution of the phenol-based polymer compound is completely mixed to the entire water to be treated at the beginning, the subsequent stirring may not be performed. [Addition procedure of fluorene-based polymer compound and inorganic coagulant] -17- 201026612 In the present invention, an inorganic coagulant is added after adding a fluorene-based polymer compound to raw water. When the phenol-based polymer compound and the inorganic coagulant are simultaneously added to the raw water or the inorganic coagulant is added to a place close to the addition site of the phenol-based polymer compound, the phenol-based polymer compound directly reacts with the inorganic coagulant. As a result, the effect of adding a phenol-based polymer compound could not be obtained, and in order to compensate for the amount consumed by the reaction, the amount of the chemical to be added was increased. When the phenol-based polymer compound is added after the inorganic coagulant, the phenol-based polymer compound remains in an unagglomerated state, and becomes a membrane separation inhibitor, which causes deterioration of MFF. [Inorganic coagulant] An inorganic coagulant added after the addition of the phenol-based polymer compound can be an aluminum-based coagulant such as polyaluminum chloride, aluminum sulfate or aluminum chloride; ferric chloride, iron sulfate, and polyferric sulfate; Iron-based coagulants. These may be used alone or in combination of two or more. When the inorganic coagulant is added to the raw water alone, the inorganic coagulant is preferably added as the inorganic coagulant having the most excellent effect, and the MFF of the coagulated water is added or more. The inorganic coagulant will not improve, or only a slight increase in the amount added. The amount of the inorganic coagulant added varies depending on the quality of the raw water, the type of the inorganic coagulant, and the required MFF, and is generally 30 to 500 mg/L with respect to the original 7K. 201026612 [Film separation treatment] In the present invention, the separation membrane used for membrane separation treatment may be MF (microporous filtration) membrane, UF (ultrafiltration) membrane, RO (reverse osmosis) membrane, NF (nanofiltration: Nanofiltration). Any of the others. The type of the film may be any of a flat film, a tubular film, a hollow wire, or the like, or may be an impregnated film. The material of the film is, for example, PVDF (Polyvinylidene Fluoride), PE (polyethylene), PP (polypropylene), etc., but is not limited thereto. EXAMPLES Hereinafter, the present invention will be more specifically described by way of Experimental Examples, Examples and Comparative Examples. Hereinafter, the phenolic polymer compound is as follows. PVF2000: Polyvinylphenol (Mw = 2000) FR6000: Phenolic phenol resin (Mw = 6000) FR2000: Phenolic phenol resin (Mw = 2000) φ Alkaline solution of the above phenol-based polymer compound, used in P VF2000 Wt / wt % of caustic soda aqueous solution, FR 600 and FR 2 0 0 0 use 30 wt/wt% aqueous caustic soda, dilution of alkali solution of these phenolic polymer compounds' to prevent phenolic The precipitation of the polymer compound was carried out in pure water, and the concentration was adjusted for each experiment. Further, the 'inorganic coagulant' was used as follows, and the commercial product was diluted with pure water to a product concentration of 10 w/v%. FC: Commercially available ferric chloride (FeCl3 concentration: 38 wt%) LAC: Liquid aluminum chloride commercial product (Al2〇3 concentration: 10.4 wt%) 19-201026612 LAS: Liquid aluminum sulfate commercial product (Al2(S) 〇3)3 concentration: 27 wt%) PAC: Liquid aluminum chloride commercial product (Al2〇3 concentration: 10.5 wt%) [Experimental Example 1: Empirical study on the effect of low concentration addition] The alkali of PVF2000, FR6000 and FR2000 The aqueous solution was diluted with pure water to a concentration of phenol-based polymer compound of 3 600 mg/L (0.36 wt/vol%), and 1 ml of the diluted solution was added dropwise to a pH adjusted to 5.8 to 9.0 by addition of a base. The seawater or the wild wood water is mixed and the concentration of the phenolic polymer compound in the water is 36 mg/L, and the pH and turbidity are measured. The results are shown in Fig. 1 (sea water) and Fig. 2 (wilakichi water). Shown. The following results can be seen from Fig. 1 and Fig. 2. When an aqueous alkali solution of a phenol-based polymer compound is added to seawater, vigorous turbidity (turbidity = 22 to 30) occurs under the conditions of pH 5.8 to 9.0, and the degree of the box is the same regardless of P Η. That is, by the action of a high concentration of salts in seawater, the negative charge of the deviated phenolic hydroxyl group is blocked, the solubility is lost, and the phenolic polymer compound is aggregated and insolubilized, thereby generating turbidity. When the raw water is seawater, the phenol-based polymer compound added before the reaction between the active ingredient and the membrane-contaminating substance to be acted on is combined with each other, so that the improvement of M F F cannot be obtained. In this case, when the alkali solution of the phenol-based polymer compound is sufficiently diluted, the density of the phenol-based polymer compound is reduced to reduce the probability of aggregation of the phenol-based polymer compound and reach the membrane contaminant and react. 20-201026612 That is, the effect of the present invention can be obtained by reacting a membrane-contaminated substance with a phenol-based polymer compound. On the other hand, in the case of the wild wood water, in the neutral zone, no matter what kind of phenolic polymer compound produces turbidity, in the alkaline zone of pH 7.5 to 8.5 or more, the turbidity is less and tends to occur. Nearly zero. When turbidity is used to produce pH, polyvinyl phenol (PVF2000) is produced starting from a higher pH 値. The phenolic phenol resin (FR6000, FR2000) φ has a larger molecular weight, and the turbidity and turbidity produce a slightly higher pH. However, regardless of the phenol-based polymer compound, aggregation and insolubilization of the phenol-based polymer compound occur in the neutral region. This is presumed to be an alkali solution in which a phenol-based polymer compound is added at a low concentration, and MFF is more improved, and the amount of addition is also lowered. [Examples and Comparative Examples] In the following examples and comparative examples, the following experimental methods were carried out. <Experimental method> (1) Raw water was adjusted to 24 ± 2 ° C, and 1100 ml thereof was taken to a beaker, and coagulation treatment was carried out using a coagulation test of MJS-6N manufactured by Miyamoto Seisakusho Co., Ltd. The stirring and reaction conditions of the coagulation test are as follows. An alkali solution of a phenol-based polymer compound was added under stirring at 150 rpm, and stirred for 5 minutes at 15 rpm. • The inorganic coagulant was added under stirring at 150 rpm, and vigorously stirred for 10 minutes at 150 -21 - 201026612 rpm and slow stirring at 〇 〇 at 5 rpm. The treatment pH' was set to ρίί6 or more in the aluminum-based coagulant, and when the pH was less than 6 after the addition of the coagulant, the mixture was neutralized by a 5 wt/vol% aqueous solution of caustic soda at a pH of substantially 6.1. In the iron-based agglomerating agent, pH 5 or higher was used, and when the pH was less than 5, it was neutralized by a 5 wt/vol% aqueous solution of caustic soda in a manner of approximately ph5.2. (2) The coagulation treatment water obtained in (1) was allowed to stand for 30 minutes to precipitate agglomerated mass. (3) The coagulated water of (2) is filtered with N〇. 5 (5 μηη pore) filter paper from the clear layer, and finally the entire amount of the agglomerated water containing the agglomerate is filtered. (4) The obtained filtrate of 1 〇〇〇 ml or more was placed in two measuring cylinders per 50,000 ml. (5) The filtrate of the first measuring cylinder was filtered at a reduced pressure of 66 kPa (500 mmHg) using a membrane filter made of Millipore Co., Ltd., a pore size 〇.45 μm and a diameter of 47 mm. And measure the time T 1 required for filtration at this time. Subsequently, the filtrate of the other measuring cylinder was further filtered under reduced pressure, and the time required for filtration T 2 ' at this time was measured to calculate MFF = T2 / T1. The water temperature was adjusted to a laboratory temperature of 24 ± 2 ° C at the time of measurement, and the water temperature at the time of measurement was recorded.
過濾時間雖因水的黏性係數而產生變化’亦即因水溫 而產生變化，但若在同一溫度進行測量’則T2/T1=MFF 201026612 之溫度的影響可被抵銷。 (6 )測定殘餘濾液的紫外線吸光度（波長260 nm、 5 0 mm單元）及TOC (全有機碳）濃度。 26〇nm紫外線吸光度（UV吸光度），主要爲具有 C = C雙鍵之有機物的吸收，並測量作爲酚系高分子化合物 之處理水中的殘留量標準。 φ [實施例I及比較例I (海水）] 將在日本東京都大田區城南島（城南島公園）所採集 之海水用作爲原水（電傳導度3400 mS/m、pH8.38)。此 原水的凝聚處理中，合適的是氯化鐵（FC)。將FC用作 爲凝聚劑並調查FC添加量與MFF之關係的結果，係如第 3圖所示，即使再如何增加F C添加量，M F F的極限仍爲 1.14。從該結果中，將酚系高分子化合物的評估之FC添 加量設爲80mg/L。此時之MFF爲1.158。 φ 接著，使用以純水稀釋酚系高分子化合物的鹼溶液而 藉此調整出第2表所示之各酚系高分子化合物濃度者，並 以第2表所示之各酚系高分子化合物的添加量，將酚系高 分子化合物的鹼溶液添加至海水後，進行添加有80 mg/L 的FC之混凝試驗，進行MFF及UV吸光度的測定，並調 查M F F改善率。 此等結果如第2表所示。 -23- 201026612 [第2表] [實施例I及實施例I (海水）] 紛系筒分子化合物f 險溶液 FC添 加量 mg/L) MFF改 善率 紛糸局分 子化合物 的種類 酚系高分子 化合物濃度 (w/v%) 酚系高分子 化合物添加 量(mg/L) MFF 値(-) UV 吸光度 比較例1-1 ^mr iiH. — 丨丨丨_ _ «Μ、、 80 1.158 0.111 實施例1-1 FR2000 0.03 1.2 80 1.066 58 0.119 實施例1-2 FR2000 0.1 1.2 80 1.078 51 0.121 比較例1-2 FR2000 0.3 1.2 80 1.127 20 0.122 比較例1-3 FR2000 1.0 1.2 80 1.151 4 0.121 比較例1-4 FR2000 1.0 2.4 80 1.143 9 0.129 實施例1-3 FR6000 0.03 1.2 80 1.058 63 0.117 實施例1-4 FR6000 0.1 1.2 80 1.065 59 0.118 比較例1-5 FR6000 0.3 1.2 80 1.148 6 0.118 比較例1-6 FR6000 1.0 1.2 80 1.162 -3 0.119 比較例1-7 FR6000 1.0 2.4 80 1.158 0 0.125 實施例1-5 PVF2000 0.03 1.2 80 1.069 56 0.112 實施例1-6 PVF2000 0.1 1.2 80 1.075 53 0.113 比較例1-8 PVF2000 0.3 1.2 80 1.160 -1 0.113 比較例1-9 PVF2000 1.0 1.2 80 1.156 1 0.114 比較例1-10 PVF2000 1.0 2.4 80 1.155 2 0.116 ※MMF改善率=(酚系高分子化合物倂用時的MFF-FC單獨 的 MFF) + (FC 單獨的 MFF-1.000)xl00(%) 從第2表中可得知下列結果。 實施例1-1,2中，當將酚醛型酚樹脂FR2000的鹼溶液 濃度設爲〇·〇3 wt/vol% (表中爲「w/v%」，以下相同）、 O.lwt/vol%時，可在1.2mg/L的添加量下使MFF成爲約 1.07之良好程度，相對於單獨的氯化鐵之MFF，可獲得 5 0 %以上的M F F改善率。 201026612 MFF改善率，係以單獨使用無機凝聚劑時的MFF ( 1.158 )與測量的MFF値（實施例1-1中爲1.066)之差（0.092 ) 作爲改善値，並以完全無膜過濾阻礙物時的MFF1.000與單 獨使用無機凝聚劑時的MFF値之差（〇· 1 58 )除上此値，並 乘以 100 而顯示爲 MFF 改善率（0.092/0.1 58x 1 00 = 5 8 (%)) 。以下亦相同。 此外，當將FR2000添加時的鹼溶液中濃度設爲〇.3 • wt/vol%時，MFF改善率降低至 20%，此外，當設爲 1.0 wt/vol%時，MFF改善率降低至4%。 在分子量較大的FR6000中，同樣的’當鹼溶液中濃 度爲 〇.〇3 wt/vol%、0_1 wt/vol%時，MFF 改善率爲 50% 以 上，爲0.3 wt/vol%、1.0 wt/vol%時，幾乎未改善。此外 ，在 1.0 wt/vol%時，即使將添加量增加至 2倍的 2.4 mg/L，亦未獲得改善效果。 聚乙烯酚的PVF2000中，亦與FR6000爲相同之結果 ❿ [實施例II及比較例11 (下水道處理水）] A市標準活性污泥法下水道處理水（高速過濾後、電 傳導度58 mS/m)的凝聚處理中，合適的是液體氯化鋁（ LAC )。將LAC用作爲凝聚劑並調查LAC添加量與MFF 之關係的結果，係如第4圖所示’即使再如何增加LAC 添加量，MFF的極限仍爲1.18。從該結果中’將酚系高分 子化合物的評估之LAC添加量設爲1〇〇 mg/L。此時之 -25- 201026612 MFF 爲 1 .1 78。 接著’使用以純水稀釋酚系高分子化合物的鹼溶液而 藉此調整出第3表所示之各酚系高分子化合物濃度者，並 以第3表所示之各酚系高分子化合物的添加量，將酚系高 分子化合物的鹼溶液添加至下水道處理水後’進行添加有 100 mg/L的LAC之混凝試驗，進行MFF、TOC及UVK 光度的測定，並調查MFF改善率。 此等結果如第3表所示。Although the filtration time varies depending on the viscosity coefficient of water, that is, changes due to water temperature, if the measurement is performed at the same temperature, the influence of the temperature of T2/T1 = MFF 201026612 can be offset. (6) The ultraviolet absorbance (wavelength 260 nm, 50 mm unit) and TOC (total organic carbon) concentration of the residual filtrate were measured. The 26 〇nm ultraviolet absorbance (UV absorbance) is mainly the absorption of an organic substance having a C=C double bond, and the residue amount in the treated water as a phenol-based polymer compound is measured. φ [Example I and Comparative Example I (seawater)] Seawater collected in Seongnam Island (Shonan Island Park), Ota City, Tokyo, Japan was used as raw water (electrical conductivity 3400 mS/m, pH 8.38). In the coagulation treatment of the raw water, iron chloride (FC) is suitable. Using FC as a coagulant and investigating the relationship between the amount of FC added and MFF, as shown in Fig. 3, even if the amount of F C added was increased, the limit of M F F was 1.14. From the results, the FC addition amount of the evaluation of the phenol-based polymer compound was 80 mg/L. The MFF at this time is 1.158. φ Next, the alkali solution of the phenol-based polymer compound is diluted with pure water to adjust the concentration of each phenol-based polymer compound shown in the second table, and each phenol-based polymer compound shown in the second table is used. The addition amount of the phenol-based polymer compound was added to seawater, and a coagulation test in which 80 mg/L of FC was added was carried out to measure MFF and UV absorbance, and the MFF improvement rate was examined. These results are shown in Table 2. -23- 201026612 [Table 2] [Example I and Example I (seawater)] Cascade molecular compound f dangerous solution FC addition amount mg/L) MFF improvement rate categorized molecular compound type phenol-based polymer Compound concentration (w/v%) phenol-based polymer compound addition amount (mg/L) MFF 値(-) UV absorbance comparison example 1-1 ^mr iiH. — 丨丨丨_ _ «Μ,, 80 1.158 0.111 Implementation Example 1-1 FR2000 0.03 1.2 80 1.066 58 0.119 Example 1-2 FR2000 0.1 1.2 80 1.078 51 0.121 Comparative Example 1-2 FR2000 0.3 1.2 80 1.127 20 0.122 Comparative Example 1-3 FR2000 1.0 1.2 80 1.151 4 0.121 Comparative Example 1 -4 FR2000 1.0 2.4 80 1.143 9 0.129 Example 1-3 FR6000 0.03 1.2 80 1.058 63 0.117 Example 1-4 FR6000 0.1 1.2 80 1.065 59 0.118 Comparative Example 1-5 FR6000 0.3 1.2 80 1.148 6 0.118 Comparative Example 1-6 FR6000 1.0 1.2 80 1.162 -3 0.119 Comparative Example 1-7 FR6000 1.0 2.4 80 1.158 0 0.125 Example 1-5 PVF2000 0.03 1.2 80 1.069 56 0.112 Example 1-6 PVF2000 0.1 1.2 80 1.075 53 0.113 Comparative Example 1-8 PVF2000 0.3 1.2 80 1.160 -1 0.113 Comparative Example 1-9 PVF2000 1.0 1.2 80 1.156 1 0.1 14 Comparative Example 1-10 PVF2000 1.0 2.4 80 1.155 2 0.116 *MMF improvement rate = (MFF-FC alone MFF when phenolic polymer compound is used) + (FC alone MFF-1.000) xl00 (%) From the 2 The following results are available in the table. In Examples 1-1 and 2, the alkali solution concentration of the novolac type phenol resin FR2000 was set to 〇·〇3 wt/vol% ("w/v%" in the table, the same applies hereinafter), O.lwt/vol In the case of %, the MFF can be made to a good level of about 1.07 at an added amount of 1.2 mg/L, and an MFF improvement rate of 50% or more can be obtained with respect to MFF of iron chloride alone. 201026612 MFF improvement rate is the difference between the MFF ( 1.158 ) when the inorganic coagulant is used alone and the measured MFF 値 (1.066 in Example 1-1) as the improvement of enthalpy, and the complete membrane-free filtration inhibitor The difference between MFF1.000 and MFF値 when using an inorganic coagulant alone (〇·1 58 ) is divided by this 値 and multiplied by 100 to show the MFF improvement rate (0.092/0.1 58x 1 00 = 5 8 (%) )). The same is true below. Further, when the concentration in the alkali solution when FR2000 was added was set to 〇.3 • wt/vol%, the MFF improvement rate was lowered to 20%, and further, when it was set to 1.0 wt/vol%, the MFF improvement rate was lowered to 4 %. In the FR6000 with a larger molecular weight, the same 'when the concentration in the alkali solution is 〇.〇3 wt/vol%, 0_1 wt/vol%, the MFF improvement rate is 50% or more, 0.3 wt/vol%, 1.0 wt. When /vol%, it hardly improved. In addition, at 1.0 wt/vol%, no improvement was obtained even if the addition amount was increased to 2 times 2.4 mg/L. In the PVF2000 of polyvinyl phenol, the same result as FR6000 实施 [Example II and Comparative Example 11 (Sewer-treated water)] A city standard activated sludge process sewer treatment water (high-speed filtration, electrical conductivity 58 mS/ In the coagulation treatment of m), liquid aluminum chloride (LAC) is suitable. Using LAC as a coagulant and investigating the relationship between LAC addition and MFF is shown in Figure 4. Even if the LAC addition is increased, the MFF limit is 1.18. From the results, the LAC addition amount of the evaluation of the phenolic polymer compound was set to 1 〇〇 mg/L. At this time -25- 201026612 MFF is 1.11. Then, the alkali solution of the phenol-based polymer compound is diluted with pure water to adjust the concentration of each phenol-based polymer compound shown in Table 3, and the phenol-based polymer compound shown in Table 3 is used. The addition amount was added to the sewer-treated water after adding the alkali solution of the phenol-based polymer compound to the coagulation test in which LAC was added at 100 mg/L, and the MFF, TOC, and UVK luminosity were measured, and the MFF improvement rate was examined. These results are shown in Table 3.
-26- 201026612 [第3表] [實施例II及比較例II (下水道處理水）] 酚系高分子化合物鹼溶液 LAC 添加量 (mg/L) MFF 値㈠ MFF 改善率 (%说 UV 吸光 度 TOC (mg/L) 酚系高分 子化合物 的種類 酚系高分子 化合物濃度 (w/v%) 酚系高分 子化合物 添加量 (mg/L) 比較例II-1 4rrr τΓΓΓ J » 100 1.178 一 0.146 7.62 實施例II-1 FR2000 0.3 2.0 100 1.068 62 0.161 7.91 實施例II-2 FR2000 1 2.0 100 1.077 57 0.162 7.93 比較例Π-2 FR2000 3 2.0 100 1.144 19 0.161 7.93 比較例Π-3 FR2000 10 2.0 100 1.152 15 0.163 8.01 比較例Π-4 FR2000 10 4.0 100 1.103 42 0.182 8.40 比較例II-5 FR2000 10 6.0 100 1.078 56 0.202 8.81 實施例Π-3 FR6000 0.3 2.0 100 1.057 68 0.158 7.78 實施例Π-4 FR6000 1 2.0 100 1.054 70 0.158 7.80 比較例Π-6 FR6000 3 2.0 100 1.138 22 0.159 7.89 比較例Π_7 FR6000 10 2.0 100 1.158 11 0.159 7.90 比較例II-8 FR6000 10 4.0 100 1.124 30 0.177 8.33 比較例Π-9 FR6000 10 6.0 100 1.084 53 0.190 8.62 實施例Π-5 PVF2000 0.3 2.0 100 1.055 69 0.148 7.61 實施例Π-6 PVF2000 1 2.0 100 1.059 67 0.149 7.63 比較例II-10 PVF2000 3 2.0 100 1.144 19 0.148 7.71 比較例II-11 PVF2000 10 2.0 100 1.156 12 0.149 7.64 比較例II-12 PVF2000 10 4.0 100 1.104 42 0.151 7.71 比較例II-13 PVF2000 10 6.0 100 1.073 59 0.154 7.88 ※MMF改善率=(酚系高分子化合物倂用時的MFF-LAC單獨 的 MFF) + (LAC 單獨的 MFF-1.000)xl00(%) -27- 201026612 從第3表中可得知下列結果。 實施例11-1，2中，當將酚醛型酚樹脂FR2000的鹼溶 液濃度設爲0.3 wt/vol%、1 wt/vol%時，可在2.0 mg/L的 添加量下使MFF成爲約1.07之良好程度，相對於單獨的 液體氯化鋁之MFF，可獲得約60%的MFF改善率。 此外，當將FR2000添加時的鹼溶液中濃度設爲3 wt/vol%時，MFF改善率降低至 19%，當設爲 10 wt/vol% 時，M F F改善率降低至1 5 %。 在分子量較大的FR6 000中，同樣地，鹼溶液中濃度 爲 0.3 wt/vol%、1 wt/vol%時之 MFF改善率約爲 70%，爲 3wt/vol%時，MFF改善率降低至22%，爲 10wt/vol%時， M F F改善率降低至1 1 %。 FR2000、FR6000，當鹼溶液中濃度爲 10 wt/vol%時 ，爲了獲得與鹼溶液中濃度0.3〜1.0 wt/vol%時爲同等之效 果，均必須將添加率增加至3倍左右。 其結果爲，凝聚·過濾處理水的UV吸光度、TOC均 因應添加量的增加而增加。 聚乙烯酚的PVF2000中，在鹼溶液中濃度0.3〜1.0 wt/vol%、添加率2.0 mg/L下，亦可獲得約70%的MFF改 善率，但在3~10 wt/vol%時，MFF改善率降低至19~12% 〇 當驗溶液中濃度爲 1 〇 w t / v ο 1 %時，爲了獲得與 0.3~1.0 wt/vol%時爲同等之效果，與 FR2000、FR6000 相 201026612 同，必須設爲約3倍的添加量。 [實施例III及比較例III (生物擦體法處理水）] B工廠廢水生物撐體法處理水（高速過據後 '電傳導 度104 mS/m)的凝聚處理中，合適的是液體硫酸鋁（LAS )。將LAS用作爲凝聚劑並調査LAS添加量與MFF之關 係的結果，係如第5圖所示，即使再如何增加LA S添加量 φ ，MFF的極限仍爲1.30，爲存在有許多無機凝聚劑所無法 去除之膜污染物質的水。 因此，係將酚系高分子化合物的評估之LAS添加量設 爲 318 mg/L。此時之 MFF 爲 1.322。 接著，使用以純水稀釋酚系高分子化合物的鹼溶液而 藉此調整出第4表所示之各酚系高分子化合物濃度者，並 以第4表所示之各酚系高分子化合物的添加量，將酚系高 分子化合物的鹼溶液添加至生物撐體法處理水後，進行添 9 加有3 1 8 mg/L的LAS之混凝試驗，進行MFF、TOC及 UV吸光度的測定’並調查MFF改善率。 此等結果如第4表所示。 -29 - 201026612 [第4表] [實施例ΠΙ及比較例III (生物擦體法處理水）] 酚系高分子化合物- 驗溶液 LAS 添加量 (mg/L) MFF 値(-) MFF 改善率 UV 吸光 度 TOC (mg/L) 酚系高 分子化 合物的 種類 酚系高分子 化合物濃度 (w/v%) 酚系高分 子化合物 添加量 (mg/L) 比較例III-1 •frjr· 1111* 318 1.322 — 0.148 2.66 實施例III-1 FR2000 0.3 5.0 318 1.097 70 0.179 2.96 實施例III-2 FR2000 1 5.0 318 1.104 68 0.180 3.02 比較例III-2 FR2000 3 5.0 318 1.188 42 0.179 3.05 比較例ΠΙ-3 FR2000 10 5.0 318 1.203 37 0.180 3.11 比較例III-4 FR2000 10 10.0 318 1.144 55 0.211 4.02 比較例ΠΙ-5 FR2000 10 15.0 318 1.098 70 0.244 4.56 實施例III-3 FR6000 0.3 5.0 318 1.078 76 0.176 2.87 實施例ΙΠ-4 FR6000 1 5.0 318 1.105 67 0.177 2.93 比較例ΙΠ-6 FR6000 3 5.0 318 1.194 40 0.175 3.01 比較例ΠΙ-7 FR6000 10 5.0 318 1.224 30 0.176 3.08 比較例ΠΙ-8 FR6000 10 10.0 318 1.123 62 0.206 3.88 比較例ΠΙ-9 FR6000 10 15.0 318 1.112 65 0.234 4.22 實施例III-5 PVF2000 0.3 5.0 318 1.088 73 0.150 2.64 實施例III-6 PVF2000 1 5.0 318 1.117 64 0.151 2.66 * 比較例ΠΙ-10 PVF2000 3 5.0 318 1.203 37 0.152 2.67 比較例ΙΠ-11 PVF2000 10 5.0 318 1.243 25 0.150 2.66 比較例ΙΠ-12 PVF2000 10 10.0 318 1.162 50 0.161 2.73 比較例ΠΙ-13 PVF2000 10 15.0 318 1.096 70 0.167 2.81 ※MMF改善率=(酚系高分子化合物倂用時的MFF-LAS單獨 的 MFF) + (LAS 單獨的 MFF-1.000)xl00(%) 從第4表中可得知下列結果。 實施例ΙΠ-1,2中，當將酚醛型酚樹脂FR2 000的鹼溶 -30- 201026612 液濃度設爲0.3 wt/vol%' 1 wt/vol%時’可在5.0 mg/L的 添加量下使MFF成爲約1.1之良好程度’相對於單獨的液 體硫酸鋁之MFF，可獲得約70%的MFF改善率。 此外，當將添加時的鹼溶液中濃度設爲3 wt/vol%時， MFF改善率降低至42%，當設爲1 〇 wt/vol%時，MFF改善 率降低至3 7 %。 在分子量較大的FR6000中，同樣地’鹼溶液中濃度 爲 0.3 wt/vol%、1 wt/vol % 時之 MFF 改善率約爲 70%’ 爲 3 wt/vol%時，MFF改善率降低至40%，爲 10 wt/vol%時 ，M F F改善率降低至3 0 %。 FR2000 ' FR6000，當鹼溶液中濃度爲 1 〇 wt/vo 1 %時 ，爲了獲得與鹼溶液中濃度0.3〜1.0 wt/vol%時爲同等之效 果，均必須將添加率增加至2~3倍左右。 其結果爲，凝聚.過濾處理水的UV吸光度、TOC均 因應添加量的增加而大幅增加。 聚乙烯酚的 PVF2000中，在鹼溶液中濃度 〇.3~1.0 wt/vol%、添加率5.0 mg/L下，亦可獲得60~70%的MFF 改善率，但在驗溶液中濃度爲3〜10 wt/vol %時，MFF改善 率降低至37〜25%。 當鹼溶液中濃度爲10 wt/vol%時，爲了獲得與0.3〜1 wt/vol %時爲同等之效果，必須設爲約3倍的添加量。 [實施例IV及比較例IV ( C市工業用水）] C市工業用水（電傳導度26 mS/m)的凝聚處理中， 201026612 合適的是聚氯化鋁（PAC)。將PAC用作爲凝聚劑並調査 PAC添加量與MFF之關係的結果，係如第6圖所示，在 PAC添加量45 mg/L時’可獲得MFF爲1.1〇，然而，即 使再如何增加添加量，亦未觀察到MFF的改善。 因此，係將酚系高分子化合物的評估之PAC添加量 設爲45 mg/L。此時之MFF爲1.097。 接著，使用以純水稀釋酚系高分子化合物的鹼溶液而 藉此調整出第5表所示之各酚系高分子化合物濃度者，並 以第5表所示之各酚系高分子化合物的添加量，將酚系高 分子化合物的鹼溶液添加至工業用水後，進行添加有45 mg/L的PAC之混凝試驗，進行MFF、TOC及UV吸光度 的測定，並調查M F F改善率。 此等結果如第5表所示。 -32- 201026612 [第5表] [實施例IV及比較例IV ( C市工業用水）] 酚系高分子化合物鹼溶液 酚系高 酚系高分 酚系高分 PAC MFF 値㈠ MFF UV吸 光度 TOC (mg/L) 分子化 合物的 子化合物 濃度 子化合物 添加量 添加量 (mg/L) 改善率 (%谈 種類 (w/v%) (mg/L) 比較例IV-1 Ατττ. Till J > \N 45 1.097 0.122 1.72 實施例ιν-1 FR2000 0.3 0.3 45 1.041 58 0.125 1.76 實施例IV-2 FR2000 1 0.3 45 1.043 56 0.124 1.77 赢 比較例IV-2 FR2000 3 0.3 45 1.066 32 0.126 1.78 比較例IV-3 FR2000 10 0.3 45 1.072 26 0.124 1.78 比較例IV-4 FR2000 10 0.6 45 1.052 46 0.129 1.84 比較例IV-5 FR2000 10 1.0 45 1.044 55 0.133 2.01 實施例IV-3 FR6000 0.3 0.3 45 1.042 57 0.124 1.75 實施例IV-4 FR6000 1 0.3 45 1.045 54 0.124 1.76 比較例IV-6 FR6000 3 0.3 45 1.071 27 0.123 1.75 比較例IV-7 FR6000 10 0.3 45 1.077 21 0.124 1.76 比較例IV-8 FR6000 10 0.6 45 1.052 46 0.126 1.81 比較例IV-9 FR6000 10 1.0 45 1.044 55 0.131 1.97 實施例IV-5 PVF2000 0.3 0.3 45 1.052 46 0.123 1.71 實施例IV-6 PVF2000 1 0.3 45 1.053 45 0.122 1.72 比較例IV-10 PVF2000 3 0.3 45 1.074 24 0.123 1.72 比較例IV-11 PVF2000 10 0.3 45 1.078 20 0.123 1.73 比較例IV-12 PVF2000 10 0.6 45 1.057 41 0.124 1.75 比較例IV-13 PVF2000 10 1.0 45 1.048 51 0.126 1.77 ※MMF改善率=(酚系高分子化合物倂用時的MFF-PAC單獨 的 MFF) + (PAC 單獨的 MFF-1.000)xl00(%) 從第5表中可得知下列結果。 實施例IV-1，2中，當將酚醛型酚樹脂FR2000的鹼溶 -33 - 201026612 液濃度設爲0.3 wt/vol%、1 wt/vol%時，可在0.3 mg/L的 添加量下使MFF成爲約1.05以下之非常良好的程度’相 對於單獨的聚氯化鋁之MFF，可獲得50%以上的MFF改 善率。 本例中，酚系高分子化合物的必要添加量，相較於下 水道處理水及工廠廢水生物撐體處理水，爲1/10之極 少的量。此可考量爲無機凝聚劑PAC單獨的添加量較少 ，其所達成之MFF爲1.0之極爲良好之値’所以膜污染物 @ 質的絕對量較前述2種水爲極少之故。 當將F R 2 0 0 0添加時的鹼溶液中濃度設爲3 w t / v ο 1 %時 ，MFF改善率降低至32%，當設爲1〇 wt/vol %時，MFF改 善率降低至2 6 %。 在分子量較大的FR6000中’同樣地’鹼溶液中濃度 爲0.3 wt/vol%、1 wt/vol%時之MFF改善率爲50以上％ ’ 爲3 wt/vol%時，MFF改善率降低至27% ’爲10 wt/vol% 時，M F F改善率降低至2 1 %。 @ FR2000、FR6000，當驗溶液中濃度爲1〇 wt/vol %時 ，爲了獲得與鹼溶液中濃度0·3〜K0 wt/vol%時爲同等之效 果，均必須將添加率增加至3倍左右。 酚醛型酚樹脂中，於凝聚.過濾後，樹脂成分的一部 份會殘留於處理水中’但藉由將鹼溶液中濃度設爲1 wt/vol%以下來添加，可在〇.3 mg/L的極少添加量下’達 到充分之膜過濾性的改善’其結果可防止處理水中之T 〇 C 的上升。 -34- 201026612 聚乙烯酚的？乂？2000中，在鹼溶液中濃度0.3〜1.0 wt/vol%、添加率0.3 mg/L下，亦可獲得45%的MFF改善 率，但在濃度爲 3~10 wt/vol%時，MFF改善率降低至 24〜2 0% ° 此外，當鹼溶液中濃度爲10 wt/vol%時，爲了獲得與 0.3〜1 wt/vol%時爲同等之效果，必須設爲約3倍的添加量 〇 φ 從以上實施例及比較的結果中，可得知下列結果。 (1)在膜分離處理之前所進行之凝聚處理中，將酚 系高分子化合物的鹼溶液構成爲酚系高分子化合物濃度1 wt/vol%以下的稀釋溶液來添加，然後添加無機凝聚劑進 行凝聚處理，藉此，可將處理水的膜過濾性指標之MFF， 較單獨使用無機凝聚劑時的達成値更改善50%以上。 當酚系高分子化合物添加時的鹼溶液中濃度爲10 wt/vol%時，爲了獲得同樣的膜過濾性改善率，必須設爲3 _ 倍至2倍的量。 根據本發明，可大幅降低膜過濾性改善所需之酚系高 分子化合物添加量，因此可大幅縮減處理費用。 此外，酚系高分子化合物中，酚醛型酚樹脂的鹼溶液 ，當樹脂成分殘留於凝聚處理水側’且添加量多時，會使 處理水的TOC上升，所以並不適合用作爲凝聚.清澄化 藥劑，但依循本發明，藉由添加作爲稀薄溶液，可藉由必 要添加率的降低，而發揮尤其是作爲膜分離處理的前處理 之凝聚劑的有效性。 -35- 201026612 此外，在作爲海水的膜分離處理的前處理之凝聚處理 中’藉由作爲將酷系高分子化合物驗溶液的濃度設爲0.1 wt/vol %以下之更稀薄的溶液來添加，相對於單獨使用無 機凝聚劑時的凝聚處理，更能夠改善膜過濾性指標MFF 爲5 0〜60% ° 當酚系高分子化合物鹼溶液的濃度超過1 wt/vol%時 ，即使增加添加量，亦幾乎無法改善M F F値。 以上係使用特定型態來詳細說明本發明，但對該業者 而言，可明瞭的是在不脫離本發明之意圖與範圍下可進行 種種變更。 本申請案係依據在2008年10月30日所申請之曰本 專利申請案（日本特願2008-280103)及在2008年11月 27日所申請之日本專利申請案（日本特願2008-302635 ) ，並藉由援引而編入該內容全體。 【圖式簡單說明】 第1圖爲顯示實驗例1之海水的pH與酚系高分子化 合物添加時的濁度之關係的圖表。 第2圖爲顯示實驗例1之野目町水的pH與酚系高分 子化合物添加時的濁度之關係的圖表。 第3圖爲顯示實驗例I及比較例I之FC添加量與 MFF之關係的圖表。 第4圖爲顯示實驗例II及比較例II之LAC添加量與 MFF之關係的圖表。 201026612 第5圖爲顯示實驗例III及比較例III之LAS添加量 與MFF之關係的圖表。 第6圖爲顯示實驗例IV及比較例IV之PAC添加量 與MFF之關係的圖表。-26- 201026612 [Table 3] [Example II and Comparative Example II (Sewer-treated water)] phenol-based polymer compound alkali solution LAC addition amount (mg/L) MFF 値 (1) MFF improvement rate (% said UV absorbance TOC (mg/L) Phenolic polymer compound type Phenolic polymer compound concentration (w/v%) Phenolic polymer compound addition amount (mg/L) Comparative Example II-1 4rrr τΓΓΓ J » 100 1.178 A 0.146 7.62 Example II-1 FR2000 0.3 2.0 100 1.068 62 0.161 7.91 Example II-2 FR2000 1 2.0 100 1.077 57 0.162 7.93 Comparative Example Π FR2000 3 2.0 100 1.144 19 0.161 7.93 Comparative Example Π FR2000 10 2.0 100 1.152 15 0.163 8.01 Comparative Example FR2000 10 4.0 100 1.103 42 0.182 8.40 Comparative Example II-5 FR2000 10 6.0 100 1.078 56 0.202 8.81 Example Π-3 FR6000 0.3 2.0 100 1.057 68 0.158 7.78 Example Π-4 FR6000 1 2.0 100 1.054 70 0.158 7.80 Comparative Example Π-6 FR6000 3 2.0 100 1.138 22 0.159 7.89 Comparative Example Π7 FR6000 10 2.0 100 1.158 11 0.159 7.90 Comparative Example II-8 FR6000 10 4.0 100 1.124 30 0.177 8.33 Comparative Example Π-9 FR6000 10 6.0 100 1.084 53 0.190 8.62 EXAMPLES Π-5 PVF2000 0.3 2.0 100 1.055 69 0.148 7.61 Example Π-6 PVF2000 1 2.0 100 1.059 67 0.149 7.63 Comparative Example II-10 PVF2000 3 2.0 100 1.144 19 0.148 7.71 Comparative Example II-11 PVF2000 10 2.0 100 1.156 12 0.149 7.64 Comparative Example II-12 PVF2000 10 4.0 100 1.104 42 0.151 7.71 Comparative Example II-13 PVF2000 10 6.0 100 1.073 59 0.154 7.88 *MMF improvement rate = (MFF-LAC alone MFF when phenolic polymer compound is used) + (LAC MFF-1.000 alone) xl00(%) -27- 201026612 The following results are available from Table 3. In Examples 11-1 and 2, when the alkali solution concentration of the novolac type phenol resin FR2000 was set to 0.3 wt/vol% or 1 wt/vol%, the MFF was made to be about 1.07 at an added amount of 2.0 mg/L. The degree of goodness is about 60% MFF improvement compared to the MFF of liquid aluminum chloride alone. Further, when the concentration in the alkali solution when FR2000 was added was set to 3 wt/vol%, the MFF improvement rate was lowered to 19%, and when it was set to 10 wt/vol%, the M F F improvement rate was lowered to 15%. In the FR6 000 having a relatively large molecular weight, the MFF improvement rate at a concentration of 0.3 wt/vol% and 1 wt/vol% in the alkali solution is about 70%, and when the ratio is 3 wt/vol%, the MFF improvement rate is lowered to When 22% is 10wt/vol%, the MFF improvement rate is reduced to 11%. FR2000 and FR6000, when the concentration in the alkali solution is 10 wt/vol%, in order to obtain the same effect as the concentration in the alkali solution of 0.3 to 1.0 wt/vol%, the addition ratio must be increased to about 3 times. As a result, the UV absorbance and TOC of the agglomerated and filtered water increased as the amount of addition increased. In PVF2000 of polyvinylphenol, an alkalinity solution concentration of 0.3 to 1.0 wt/vol% and an addition rate of 2.0 mg/L can also obtain an improvement rate of MFF of about 70%, but at 3 to 10 wt/vol%, The MFF improvement rate is reduced to 19~12%. When the concentration in the test solution is 1 〇wt / v ο 1 %, in order to obtain the same effect as 0.3~1.0 wt/vol%, it is the same as FR2000 and FR6000 phase 201026612. Must be set to about 3 times the amount added. [Example III and Comparative Example III (Bioabrasive treatment of water)] In the coagulation treatment of B plant wastewater biological support method (high-speed after the passage of 'electric conductivity 104 mS/m), liquid sulfuric acid is suitable. Aluminum (LAS). Using LAS as a coagulant and investigating the relationship between the amount of LAS added and MFF, as shown in Fig. 5, even if the amount of addition of VL is increased, the limit of MFF is still 1.30, which is the presence of many inorganic coagulants. Water that cannot remove the membrane contaminants. Therefore, the LAS addition amount of the phenol-based polymer compound was set to 318 mg/L. The MFF at this time is 1.322. Then, the alkali solution of the phenol-based polymer compound is diluted with pure water to adjust the concentration of each phenol-based polymer compound shown in Table 4, and the phenol-based polymer compound shown in Table 4 is used. When the amount of the phenol-based polymer compound was added to the bio-supporting method, the coagulation test was carried out by adding 9 to 181 mg/L of LAS, and the MFF, TOC, and UV absorbance were measured. And investigate the MFF improvement rate. These results are shown in Table 4. -29 - 201026612 [Table 4] [Examples and Comparative Example III (Bioabrasive treatment of water)] Phenolic polymer compound - Solution LAS addition amount (mg/L) MFF 値(-) MFF improvement rate UV absorbance TOC (mg/L) Type of phenolic polymer compound Phenolic polymer compound concentration (w/v%) Phenolic polymer compound addition amount (mg/L) Comparative Example III-1 • frjr· 1111* 318 1.322 — 0.148 2.66 Example III-1 FR2000 0.3 5.0 318 1.097 70 0.179 2.96 Example III-2 FR2000 1 5.0 318 1.104 68 0.180 3.02 Comparative Example III-2 FR2000 3 5.0 318 1.188 42 0.179 3.05 Comparative Example ΠΙ-3 FR2000 10 5.0 318 1.203 37 0.180 3.11 Comparative Example III-4 FR2000 10 10.0 318 1.144 55 0.211 4.02 Comparative Example ΠΙ-5 FR2000 10 15.0 318 1.098 70 0.244 4.56 Example III-3 FR6000 0.3 5.0 318 1.078 76 0.176 2.87 Example ΙΠ-4 FR6000 1 5.0 318 1.105 67 0.177 2.93 Comparative Example -6 FR6000 3 5.0 318 1.194 40 0.175 3.01 Comparative Example ΠΙ FR6000 10 5.0 318 1.224 30 0.176 3.08 Comparative Example ΠΙ FR6000 10 10.0 318 1.123 62 0.206 3.88 Comparative Example -9 FR6000 10 15 .0 318 1.112 65 0.234 4.22 Example III-5 PVF2000 0.3 5.0 318 1.088 73 0.150 2.64 Example III-6 PVF2000 1 5.0 318 1.117 64 0.151 2.66 * Comparative Example PV-10 PVF2000 3 5.0 318 1.203 37 0.152 2.67 Comparative Example -11 PVF2000 10 5.0 318 1.243 25 0.150 2.66 Comparative Example PV-12 PVF2000 10 10.0 318 1.162 50 0.161 2.73 Comparative Example PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV PV MFF-LAS alone MFF) + (LAS alone MFF-1.000) xl00 (%) The following results are known from Table 4. In Example ΙΠ-1, 2, when the concentration of the alkali-soluble -30-201026612 solution of the novolac type phenol resin FR2 000 is set to 0.3 wt/vol% '1 wt/vol%', the amount of addition can be 5.0 mg/L. Under the MFF of about 1.1, the MFF improvement rate of about 70% can be obtained with respect to the MFF of the liquid aluminum sulfate alone. Further, when the concentration in the alkali solution at the time of addition was set to 3 wt/vol%, the MFF improvement rate was lowered to 42%, and when it was set to 1 〇 wt/vol%, the MFF improvement rate was lowered to 37%. In the FR6000 having a larger molecular weight, when the MFF improvement rate at the concentration of 0.3 wt/vol% and 1 wt/vol% in the alkali solution is about 70%' is 3 wt/vol%, the MFF improvement rate is lowered to 40%, when 10 wt/vol%, the MFF improvement rate is reduced to 30%. FR2000 'FR6000, when the concentration in the alkali solution is 1 〇wt/vo 1%, in order to obtain the same effect as the concentration in the alkali solution of 0.3 to 1.0 wt/vol%, the addition rate must be increased to 2 to 3 times. about. As a result, the UV absorbance and TOC of the agglomerated and filtered water greatly increased in response to an increase in the amount of addition. In the PVF2000 of polyvinylphenol, the concentration of FF.3~1.0 wt/vol% in the alkali solution and the addition rate of 5.0 mg/L can also obtain the MFF improvement rate of 60-70%, but the concentration in the test solution is 3 At ~10 wt/vol %, the MFF improvement rate is reduced to 37 to 25%. When the concentration in the alkali solution is 10 wt/vol%, in order to obtain an effect equivalent to 0.3 to 1 wt/vol%, it is necessary to set the addition amount to about three times. [Example IV and Comparative Example IV (Industrial Water in City C)] In the coagulation treatment of industrial water (electrical conductivity: 26 mS/m) in City C, 201026612 is suitable as polyaluminum chloride (PAC). When PAC was used as a coagulant and the relationship between the amount of PAC added and MFF was investigated, as shown in Fig. 6, when the amount of PAC added was 45 mg/L, the MFF was 1.1 〇, however, even if the addition was increased The amount of MFF was also not observed. Therefore, the amount of PAC added for evaluation of the phenol-based polymer compound was set to 45 mg/L. The MFF at this time was 1.097. Then, the alkali solution of the phenol-based polymer compound is diluted with pure water to adjust the concentration of each phenol-based polymer compound shown in Table 5, and the phenol-based polymer compound shown in Table 5 is used. The addition amount was added to the industrial water using an alkali solution of a phenol-based polymer compound, and a coagulation test in which 45 mg/L of PAC was added was carried out to measure MFF, TOC, and UV absorbance, and the MFF improvement rate was examined. These results are shown in Table 5. -32- 201026612 [Table 5] [Example IV and Comparative Example IV (C Industrial Water)] Phenolic polymer compound alkali solution Phenol-based high phenol-based high-phenol-based high-altitude PAC MFF 値 (1) MFF UV absorbance TOC (mg/L) Sub-compound of molecular compound Concentration of added amount of compound (mg/L) Improvement rate (% by type (w/v%) (mg/L) Comparative Example IV-1 Ατττ. Till J > \N 45 1.097 0.122 1.72 Example ιν-1 FR2000 0.3 0.3 45 1.041 58 0.125 1.76 Example IV-2 FR2000 1 0.3 45 1.043 56 0.124 1.77 Win Comparative Example IV-2 FR2000 3 0.3 45 1.066 32 0.126 1.78 Comparative Example IV- 3 FR2000 10 0.3 45 1.072 26 0.124 1.78 Comparative Example IV-4 FR2000 10 0.6 45 1.052 46 0.129 1.84 Comparative Example IV-5 FR2000 10 1.0 45 1.044 55 0.133 2.01 Example IV-3 FR6000 0.3 0.3 45 1.042 57 0.124 1.75 Example IV-4 FR6000 1 0.3 45 1.045 54 0.124 1.76 Comparative Example IV-6 FR6000 3 0.3 45 1.071 27 0.123 1.75 Comparative Example IV-7 FR6000 10 0.3 45 1.077 21 0.124 1.76 Comparative Example IV-8 FR6000 10 0.6 45 1.052 46 0.126 1.81 Comparative Example IV-9 FR6000 10 1. 0 45 1.044 55 0.131 1.97 Example IV-5 PVF2000 0.3 0.3 45 1.052 46 0.123 1.71 Example IV-6 PVF2000 1 0.3 45 1.053 45 0.122 1.72 Comparative Example IV-10 PVF2000 3 0.3 45 1.074 24 0.123 1.72 Comparative Example IV-11 PVF2000 10 0.3 45 1.078 20 0.123 1.73 Comparative Example IV-12 PVF2000 10 0.6 45 1.057 41 0.124 1.75 Comparative Example IV-13 PVF2000 10 1.0 45 1.048 51 0.126 1.77 *MMF improvement rate = (MFF when phenolic polymer compound is used) -PAC alone MFF) + (PAC alone MFF-1.000) xl00 (%) The following results are known from Table 5. In the examples IV-1, 2, when the alkali-soluble -33 - 201026612 liquid concentration of the novolac type phenol resin FR2000 is set to 0.3 wt/vol%, 1 wt/vol%, the addition amount of 0.3 mg/L can be used. A very good degree of MFF of about 1.05 or less is made, and an MFF improvement rate of 50% or more can be obtained with respect to MFF of a single polyaluminum chloride. In this example, the amount of the phenol-based polymer compound to be added is as small as 1/10 as compared with the sewage treated water and the plant wastewater biological support treated water. This can be considered as the inorganic coagulant PAC alone is added in a small amount, and the MFF achieved by the method is extremely good. Therefore, the absolute amount of the film contaminant @ is extremely small compared to the above two kinds of water. When the concentration in the alkali solution when FR 2 0 0 is added is set to 3 wt / v ο 1 %, the MFF improvement rate is reduced to 32%, and when it is set to 1 〇 wt/vol %, the MFF improvement rate is lowered to 2 6 %. In the FR6000 having a larger molecular weight, the MFF improvement rate is 0.3 wt/vol% and the MFF improvement rate at 1 wt/vol% is 50% by % when the concentration is 3 wt/vol%, and the MFF improvement rate is lowered to When 27% ' is 10 wt/vol%, the MFF improvement rate is reduced to 21%. @ FR2000, FR6000, when the concentration in the test solution is 1〇wt/vol %, in order to obtain the same effect as the concentration of 0·3~K0 wt/vol% in the alkali solution, the addition rate must be increased to 3 times. about. In the phenolic phenol resin, after coagulation, a part of the resin component remains in the treated water after filtration, but it is added by setting the concentration in the alkali solution to 1 wt/vol% or less, and it can be added at 〇.3 mg/ With the addition of L, the "improvement of sufficient membrane filterability" is achieved, and as a result, the rise of T 〇C in the treated water can be prevented. -34- 201026612 Polyvinylphenol? Hey? In 2000, at a concentration of 0.3 to 1.0 wt/vol% in an alkali solution and an addition rate of 0.3 mg/L, a MFF improvement rate of 45% was obtained, but at a concentration of 3 to 10 wt/vol%, the MFF improvement rate was obtained. When the concentration in the alkali solution is 10 wt/vol%, in order to obtain the same effect as 0.3 to 1 wt/vol%, it is necessary to set the addition amount to about 3 times 〇φ. From the results of the above examples and comparisons, the following results were obtained. (1) In the coagulation treatment performed before the membrane separation treatment, the alkali solution of the phenol-based polymer compound is added as a diluted solution having a phenol-based polymer compound concentration of 1 wt/vol% or less, and then an inorganic coagulant is added thereto. By the coagulation treatment, the MFF of the membrane filterability index of the treated water can be improved by 50% or more compared with the achievement of the inorganic coagulant alone. When the concentration in the alkali solution when the phenol-based polymer compound is added is 10 wt/vol%, in order to obtain the same membrane filterability improvement rate, it is necessary to set it as 3 to 2 times. According to the present invention, the amount of the phenol-based high molecular compound required for the improvement of the membrane filtration property can be greatly reduced, so that the treatment cost can be greatly reduced. In addition, in the phenol-based polymer compound, when the resin component remains on the agglomerated water side, and the amount of the alkali solution of the phenolic phenol resin increases, the TOC of the treated water rises, so it is not suitable for use as agglomeration. The drug, but according to the present invention, by adding as a thin solution, the effectiveness of the coagulant, particularly as a pretreatment for the membrane separation treatment, can be exerted by a reduction in the necessary addition ratio. -35-201026612 In addition, in the coagulation treatment of the pretreatment of the membrane separation treatment of seawater, it is added as a thinner solution in which the concentration of the test solution of the cool polymer compound is 0.1 wt/vol% or less. When the concentration of the phenol-based polymer compound alkali solution exceeds 1 wt/vol%, the amount of the phenol-based polymer compound alkali solution is increased by more than 1 wt/vol%, and the amount of the phenol-based polymer compound alkali solution is increased by more than 1 wt/vol%. It is also almost impossible to improve MFF値. The present invention has been described in detail with reference to the specific embodiments thereof, and it is obvious to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention. This application is based on a patent application filed on October 30, 2008 (Japanese Patent Application No. 2008-280103) and a Japanese patent application filed on Nov. 27, 2008 (Japanese Patent Application No. 2008-302635) ) and incorporated into the content by reference. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the relationship between the pH of seawater of Experimental Example 1 and the turbidity at the time of addition of a phenol-based polymer compound. Fig. 2 is a graph showing the relationship between the pH of the Nogata-machi water of Experimental Example 1 and the turbidity when the phenol-based polymer compound is added. Fig. 3 is a graph showing the relationship between the amount of addition of FC in Experimental Example I and Comparative Example I and MFF. Fig. 4 is a graph showing the relationship between the amount of LAC added and the MFF of Experimental Example II and Comparative Example II. 201026612 Fig. 5 is a graph showing the relationship between the amount of LAS added and the MFF of Experimental Example III and Comparative Example III. Fig. 6 is a graph showing the relationship between the amount of PAC added and the MFF of Experimental Example IV and Comparative Example IV.
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