(吸附材擔載體) 本發明之吸附材擔載體係將以氧(氫氧)化鐵為主成分之粒子擔載於多孔質之支持體上而成之吸附材擔載體，BET比表面積為50 m2
/g以上。 此處，所謂「粒子」意指以氧(氫氧)化鐵為主成分之成分於吸附材擔載體中並非連續地而是斷續地存在，且利用多孔質之支持體而維持該存在狀態者，並非限定粒子本身之形狀。又，所謂「擔載而成」係表現吸附材擔載體之狀態者，並非限定製造方法。 本發明之吸附材擔載體較佳為比表面積較大。具體而言，BET比表面積較佳為100 m2
/g以上。 氧(氫氧)化鐵於對陰離子之吸附性方面優異。 本發明之吸附材擔載體中之以氧(氫氧)化鐵為主成分之粒子較佳為氧(氫氧)化鐵之含有率為99質量%以上，鐵化合物以外之物質之含有率為1質量%以下。最佳為氧(氫氧)化鐵之含有率實質上為100質量%者。 根據結晶結構之差異，氧(氫氧)化鐵有α型、β型、γ型、非晶質型等。該等之中，β-氧(氫氧)化鐵於吸附性能方面特別優異，適用於磷酸根離子、亞磷酸根離子、次磷酸根離子、硫酸根離子、硝酸根離子、氟化物離子等之吸附材。又，就容易形成穩定之奈米分散液之方面而言，亦適用作奈米分散液之原料。 β-氧(氫氧)化鐵通常為羥基之一部分被取代為氯化物離子。若於製造或使用之過程中與水接觸，則該氯化物離子被去除而殘留小型之空孔。認為該空孔係與氟等之陰離子之吸附，進而認為本發明之有效率之陰離子吸附亦係源自該空孔之特徵。 就比表面積較大，陰離子吸附效率高之方面而言，本發明之吸附材擔載體中之氧(氫氧)化鐵較佳為β-氧(氫氧)化鐵。 以上述之氧(氫氧)化鐵為主成分之粒子較佳為平均晶粒直徑為10 nm以下，更佳為3 nm以下。 由本發明者等人明確，該平均晶粒直徑越小，於水中用作磷酸吸附材之情形時之磷酸吸附速度越快。 平均晶粒直徑D係利用X射線繞射，根據β-氧(氫氧)化鐵所特有之2θ＝35°附近之繞射線，使用下述謝樂之式而計算。 D＝Kλ/βcosθ 其中，β係修正起因於裝置之機械寬度的實際之繞射峰之半值寬，K係謝樂常數，λ係X射線之波長。 此種以平均晶粒直徑為3 nm以下之β-氧(氫氧)化鐵為主成分之粒子如下所述，可藉由將固體狀之β-氧(氫氧)化鐵進行濕式粉碎而獲得。 關於本發明之吸附材擔載體，其真密度雖然支持體之種類而異，但較佳為2 g/cm3
以上。真密度例如可藉由依據JIS Z 8807之方法進行測定。多孔質之支持體為低密度，且將一定量以上之以β-氧(氫氧)化鐵為主成分之粒子擔載於其上，藉此可將真密度設為上述範圍。 更具體而言，本發明之吸附材擔載體較佳為以β-氧(氫氧)化鐵為主成分之粒子占吸附材擔載體總量之60質量%以上。 藉由將本發明之吸附材擔載體設為上述任一範圍，可達成高效率之吸附。 (製造方法) 本發明之吸附材擔載體於該製造方法中並無特別限定，作為以β-氧(氫氧)化鐵為主成分之粒子之原料，較佳為使用包含將以β-氧(氫氧)化鐵為主成分之固體成分粉碎為一定之粒度之粒子、及溶劑之分散液。 作為該分散液之製造方法，例如可列舉於溶劑中進行濕式粉碎而直接使之分散之方法(製造法A)。於該方法中，較佳為進行粉碎直至平均粒徑d50成為0.2 μm以下。平均粒徑更佳為0.02～0.2 μm，進而較佳為0.05～0.15 μm。又，較佳為d90設為1 μm以下，較佳為粒徑處於0.01～1 μm之範圍。 又，於藉由上述濕式粉碎而獲得之粒子中，結晶之形狀為粒狀。此處，所謂粒狀，係意指並非針狀或者板狀，更具體而言，結晶之長徑/短徑之比為3以下。 作為上述所使用之溶劑，使用水或以水為主成分之溶液而製成水性分散液最容易，故而較佳。 另一方面，於需要有機溶劑等其他溶劑之情形時，亦可自水性分散液，藉由溶劑置換而製成有機溶劑等其他溶劑中之分散液。例如，藉由一面於超濾膜中將溶劑混合於水性分散液中一面進行溶劑交換，可獲得向該溶劑之分散液。又，藉由在水性分散液中混合沸點高於水之溶劑，且利用旋轉蒸發器等去除水，可獲得於該溶劑中之分散液。 進而，就吸附材擔載體之製造容易之方面而言，藉由以上方法所獲得之分散液較佳為奈米分散液。所謂奈米分散液係指於粒徑1 μm以下之所謂奈米粒子分散於液相中而成之分散液中，藉由靜置或通常之離心操作而粒子不沈澱者。 於將以上之各分散液作為原料而製造本發明之吸附材擔載體之情形時，未必需要黏合劑。 作為該分散液之製造方法，又，例如可列舉使藉由乾式粉碎而獲得之粒子分散於溶劑中之方法(製造法B)。該方法於將平均粒徑d50設為5 μm以上之情形時較佳。於該情形時，平均粒徑較佳為70 μm以下。於將該分散液作為原料而製造本發明之吸附材擔載體之情形時，較佳為併用黏合劑，或代替黏合劑而併用於上述溶劑中進行濕式粉碎而直接使之分散而成之分散液。 繼而，可藉由在使上述分散液混合分散於支持體之原料之後，由其進行成形之方法，或者自外部將上述分散液添加於固體之支持體之方法，而進行擔載。藉由該等，可製造吸附性能優異，而且回收、脫附等之操作容易之吸附材。 於使用在混合分散於支持體之原料後由其進行成形之方法之情形時，作為支持體之原料，使用各種樹脂，作為上述分散液，較佳為使用使微粒子分散於對該樹脂具有相溶性之溶劑者。 於使用自外部將上述分散液添加於固體之支持體之方法之情形時，較佳為將支持體浸漬於上述分散液後，使支持體乾燥之方法。 上述分散液之溶劑並無特別限定，可列舉水、各種有機溶劑、該等之混合物、或者視需要例如使黏合劑、界面活性劑、消泡劑等添加劑溶解於以上之液體而獲得之溶液。 作為上述分散液，於使用於溶劑中將以β-氧(氫氧)化鐵為主成分之粒子粉碎直至平均粒徑d50成為0.2 μm以下而成之分散液之情形時，由於該粒子本身具有與黏合劑同樣之效果，故而未必需要黏合劑。 該方法於操作容易，而且將以β-氧(氫氧)化鐵為主成分之粒子擔載於支持體表面，而變得能夠進行有效率之吸附及脫附之方面較佳。 作為上述以β-氧(氫氧)化鐵為主成分之固體，較佳為藉由包括使含鐵化合物之溶液與鹼進行反應，於pH值9以下生成沈澱物之步驟的方法所獲得之乾燥凝膠。 作為上述鐵化合物，較佳為鐵鹽，尤其是3價之鐵鹽。具體而言，可列舉：氯化鐵、硫酸鐵、硝酸鐵等，其中尤佳為氯化鐵。 上述鹼係為了中和酸性之鐵化合物水溶液，生成包含氧(氫氧)化鐵之沈澱而使用。具體而言，可列舉：氫氧化鈉、氫氧化鉀、氫氧化鈣、氨、碳酸鈉、碳酸鉀、碳酸鈣等，其中尤佳為氫氧化鈉。 沈澱物之精製時之pH值更佳為調整為pH值3.3～6之範圍。 藉由以上方法所獲得之以氧(氫氧)化鐵為主成分之沈澱物可進行過濾分離而回收，若將其乾燥則成為乾燥凝膠。 進而，於以上之步驟之後，較佳為實施使沈澱物乾燥之步驟，及使該乾燥物與水接觸之後，使之乾燥之步驟。 使沈澱物乾燥之步驟較佳為於120℃以下進行，更佳為於100～120℃下進行。乾燥溫度於低溫時需要時間，不適用於有效率之製造。又，高溫時有陰離子吸附部位變少之傾向，進而高溫時轉化為氧化鐵，因此欠佳。乾燥可於空氣中、真空中、或惰性氣體中進行。 認為於使乾燥物與水接觸之步驟中，氯化鈉等雜質溶出，其後殘留細孔，比表面積增大並且陰離子吸附部位亦增加。 使乾燥物與水接觸之後，去除水，再次使之乾燥。較佳為該乾燥步驟亦於與上述相同之條件下進行。 藉由以上方法所獲得之乾燥凝膠包含β-氧(氫氧)化鐵作為主成分。 本發明之吸附材擔載體亦可於氣相中，例如為了吸附排氣中之有害物質等而使用，較佳為於液相中使用。 通常，於液相中使用吸附材之情形時，液體中所含之成分藉由擴散而到達細孔中需要時間，因此達到吸附平衡需要時間。另一方面，若使吸附材以微粒子之形式分散於液體中，則快速地達到吸附平衡，但微粒子之分離、回收存在問題。本發明之吸附材擔載體係具有同時解決該等問題之目的者，因此尤其適合於液相中使用。 作為上述液相，若吸附材擔載體以外之部分為均勻之液相，則可無問題地使用，例如亦可使用有機溶劑溶液，但較佳為以有害物質之去除、有用物質之回收等為目的，於水溶液中使用。 本發明之吸附材擔載體尤其適用於陰離子吸附材。進而，適用於氟及磷酸吸附材，其中適用於磷酸吸附材。 於本發明之吸附材擔載體之製造時，用以將吸附材與載體結合之黏合劑並非必須，但為了使結合變得更牢固而製成耐受長期反覆使用者，亦可併用黏合劑。尤其於以β-氧(氫氧)化鐵為主成分之粒子之平均粒徑d50為5 μm以上之情形時，較佳為併用黏合劑。 黏合劑於用作陰離子吸附材擔載體時並無不妥，較佳為於pH值2.5～pH值12.5之範圍內穩定，更佳為於pH值1～14之範圍內穩定。 又，黏合劑不得為因覆蓋吸附材之表面而使吸附性能降低者。 黏合劑之材質只要符合以上之條件則無特別限定，例如可使用無機化合物。由於無機化合物通常採用粒子狀之形狀，故而覆蓋吸附材之表面之情況較少，適用於黏合劑。 以氧(氫氧)化鐵為主成分之粒子，尤其是平均粒徑d50為5 μm以上之粒子之質量，與黏合劑之質量之比較佳為7：3～10：0。 作為上述無機化合物，可例示選自鋯、鈦及錫中之金屬之化合物。尤佳為上述之金屬之氧化物或氫氧化物。 其中，尤佳為包含氧化鋯之分散液。若使用氧化鋯分散液作為黏合劑，則以氧(氫氧)化鐵為主成分之粒子不僅擔載於支持體表面部，亦擔載至支持體中之細孔，藉此本吸附材擔載體之吸附效率變得非常高。 於該情形時，以氧(氫氧)化鐵為主成分之粒子、與氧化鋯之質量比較佳為8：2～9.5：0.5。即便進一步增多氧化鋯，吸附效率亦不會進一步提高，即便就費用之方面而言亦較佳為該範圍。 另一方面，黏合劑亦可為聚烯烴系樹脂。樹脂中亦存在有覆蓋吸附材之表面之虞者，但由於聚烯烴系樹脂為疏水性，故而無此種擔憂。又，就吸附材擔載體之製造容易之方面而言，聚烯烴系樹脂較佳為乳液形態。 作為聚烯烴系樹脂，可例示：聚乙烯(直鏈狀低密度聚乙烯等低密度聚乙烯、中密度聚乙烯、高密度聚乙烯等)；聚丙烯；乙烯-丙烯共聚物；乙烯或丙烯與其他α-烯烴之共聚物；進而乙烯或丙烯與(甲基)丙烯酸、(甲基)丙烯酸酯、乙酸乙烯酯、乙烯醇、苯乙烯等不飽和單體之共聚物等。 本發明之吸附材擔載體所使用之支持體只要為多孔質則無特別限定，為了於用作陰離子吸附材擔載體時無不妥，尤佳為於pH值2.5～pH值12.5之範圍內穩定，更佳為於pH值1～14之範圍內穩定。 又，就加工容易之方面而言，本發明之吸附材擔載體所使用之支持體較佳為多孔質高分子材料。 於僅使用水作為溶劑之情形時，作為多孔質高分子材料，亦可無關親水性或疏水性而使用。作為高分子材料，具體而言，可列舉：纖維素等天然高分子、纖維素衍生物等半合成高分子、聚烯烴、聚苯乙烯、聚丙烯酸酯、聚乙酸乙烯酯、聚氯乙烯、聚乙烯醇、聚胺基甲酸酯、聚酯、聚碳酸酯、酚系樹脂、尿素樹脂、聚醯亞胺等合成高分子。 其中，尤佳為聚烯烴系樹脂。如上所述，由於聚烯烴系樹脂為疏水性，故而無覆蓋吸附材之表面而使吸附性能降低之情況。 又，作為使該等材料成為多孔質之方法，可使用相分離法、發泡法、融合法、提取法、化學處理法、延伸法等各種方法。 支持體之形狀並無特別限定，可例示海綿狀、片狀、粒子狀等，根據用途自該等適當選擇。其中，海綿狀者之具體之形狀(矩形、球形等)並無特別限定，就於製造擔載體時吸附材容易擔載於內部，且於使用時吸附對象液體以短時間到達內部之方面而言，較佳為尺寸較小。又，就相同含義而言，更佳為片狀或粒子狀，該片材之厚度或該粒子之直徑較佳為設為5 mm以下。又，亦可自以上之各形狀將複數者組合而使用。 作為支持體，可預先製成上述之各形狀，亦可於製造擔載體後進行切割，而製備為具有特定之形狀或者尺寸者。 本發明之吸附材擔載體與分散液相同，具有吸附速度較高之特徵。 該吸附速度可藉由如下所述之批次式吸附試驗進行測定。 準備利用鹽酸將pH值調整為固定之磷換算濃度為400 mg/L之磷酸二氫鉀水溶液150 mL。於其中投入吸附材1 g，並於室溫下進行攪拌。於一定時間後對水溶液採樣，測定磷酸根離子濃度，並求出吸附量。 又，於以上之試驗中，可經時性地求出磷酸根離子吸附量，根據經時變化消失之時間點之吸附量，估算最終吸附量。更簡便而言，可根據24小時後之吸附量，估算最終吸附量。 本發明之吸附材擔載體於該方法中，於將水溶液之pH值調整為3.5之情形時，24小時後磷換算吸附量成為25 mg以上，較佳為成為30 mg以上。 又，本發明之吸附材擔載體之特徵係於在水中用作陰離子吸附材之過程中，pH值明顯上升。具體而言，該特徵由下述方法顯示。 準備利用鹽酸將pH值調整為固定之磷換算濃度為400 mg/L之磷酸二氫鉀水溶液150 mL。向其中投入吸附材擔載體1 g，並於室溫下進行攪拌。於一定時間後對水溶液採樣，測定pH值。 本發明之吸附材擔載體於該方法中，於將水溶液之pH值調整為3.5之情形時，相對於1小時後之水溶液之pH值，24小時後之水溶液之pH值上升0.3以上。 且說，用作本發明之吸附材擔載體之材料的β-氧(氫氧)化鐵於不進行粉碎等之狀態下，即便用作吸附材亦幾乎不會帶來水溶液之pH值之變化。 該等之原因係藉由下述方式進行推測。於不進行粉碎等處理之β-氧(氫氧)化鐵，羥基位於如磷酸根離子之較大之陰離子之不能容易到達之細孔中。此種細孔係尤其藉由氯離子脫離而形成者。另一方面，本發明之吸附材擔載體由於此種細孔結構受到破壞，故而磷酸根離子亦容易到達該羥基之附近。 不進行粉碎等處理之β-氧(氫氧)化鐵亦有大型之空孔，因此可吸附吸附速度較慢者之磷酸根離子。 於本發明之吸附材擔載體中，繼而，變為所吸附之陰離子與羥基交換，該陰離子直接鍵結於吸附材之狀態，與此同時，羥基以氫氧離子之形式釋出於水中，因此水溶液之pH值上升。但是，推測不進行粉碎等處理之β-氧(氫氧)化鐵不產生此種置換，因此亦不產生pH值之上升。 進而，本發明所使用之β-氧(氫氧)化鐵中之氯離子之含量較佳為0.5質量%以上，更佳為3質量%以上。 根據以上所述，認為本發明之吸附材擔載體並非僅單純地吸附陰離子，其後陰離子成為鍵結於吸附材擔載體而不容易解離之狀態，因此發揮出較高之吸附效率。 [實施例] 其次，藉由本發明之實施例更詳細地進行說明，但本發明並非受其限定者。 測定方法 (粉末X射線繞射) X射線繞射(XRD，X ray diffraction)圖案係使用X射線繞射裝置Ultima IV(Rigaku公司製造)進行測定。測定使用CuKα球管。平均晶粒直徑係自XRD，依據謝樂之式而算出。 (比表面積) 使用比表面積測定裝置MacsorbHM 1210(Mountech公司製造)，藉由氣體吸附法測定比表面積。 (TEM觀察) 試樣之TEM(Transmission Electron Microscopy，穿透式電子顯微鏡)觀察係使用穿透式電子顯微鏡JEM 2010F(JEOL公司製造，加速電壓200 kV)進行。 (氧(氫氧)化鐵中之氯離子之含量) 將氧(氫氧)化鐵試樣溶解於3M硫酸之後，利用鹼性溶液進行稀釋，使鐵成分沈澱，並利用過濾器進行過濾而回收濾液，藉由離子層析法(日本Dionex公司製造之DX-500型)進行定量。 (分散液之粒度分佈) 關於微米單位之分散液之粒徑，使用雷射繞射/散射式粒度分佈測定裝置LA-920(堀場製作所製造)，對體積基準之累積50%粒徑(D50)、及體積基準之累積90%粒徑(D90)進行測定。 奈米分散液之粒徑、粒度分佈、累積50%粒徑(D50)、及累積90%粒徑(D90)係使用動態光散射粒度分佈測定裝置Zetasizer Nano S(Spectris公司製造)進行測定。 (真密度) 進行利用氦氣置換法之真密度測定(乾式密度計：AccuPyc 1340TC，島津製作所・Micromeritics公司製造)。 參考例1(氧(氫氧)化鐵之製造) 於氯化鐵(FeCl3
)水溶液中，一面於室溫下調整為pH值6以下一面滴加氫氧化鈉(NaOH)水溶液，將NaOH之最終添加量設為NaOH/FeCl3
(莫耳比)＝2.75而使之反應，獲得氧(氫氧)化鐵之粒子懸浮液。所獲得之懸浮液中之粒子之平均粒徑d50為17 μm。 對懸浮液進行過濾分離後，於空氣中120℃下進行乾燥，並利用離子交換水進行清洗，進而於空氣中120℃下進行乾燥，獲得氧(氫氧)化鐵之粉末(粉末A)。 藉由上述方式獲得之氧(氫氧)化物粉末(粉末A)之粒徑為0.25 mm～5 mm。藉由X射線繞射，確認結晶結構為β-氧(氫氧)化鐵，平均晶粒直徑為5 nm。 將利用穿透式電子顯微鏡(TEM)觀察之情況示於圖1。結晶形狀係幾乎為縱橫比1：3以下之粒狀。利用TEM觀察所得之晶粒直徑為5～10 nm，各個結晶為粒狀，該等凝結而形成粒子。 又，比表面積為280 m2
/g，氯離子含量為5.8 wt%。 參考例2(氧(氫氧)化鐵吸附材粒子之製造) 利用針磨機對氧(氫氧)化鐵粉末(粉末A)進行乾式粉碎，獲得圖2所示之粒度分佈之粉末(粉末B)。粉末B之粒徑範圍為0.6～300 μm，平均粒徑為26.5 μm。 參考例3(去除10 μm以下之粒子之製造) 利用篩孔10 μm之尼龍篩網包裹粉末B，並放入離子交換水中，充分地進行清洗而去除粒徑10 μm以下者，獲得粒徑範圍8～300 μm、平均粒徑40.3 μm之粉末(粉末C)。 將以上之粉末B、粉末C(篩上物)及過篩品(上述之去除成分)之粒徑分佈示於圖2。 參考例4(氧(氫氧)化鐵之奈米分散液之製造) 將粉末B以固形物成分濃度成為10質量%之方式混合於離子交換水中之後，利用珠磨機(氧化鋯珠，珠粒直徑1 mm)進行30分鐘粗粉碎，製成懸浮液。進而，利用珠磨機(氧化鋯珠，珠粒直徑0.1 mm)對其進行60分鐘粉碎，而獲得分散液D。藉由該粉碎，懸浮為茶色之液體變為黑色且透明之奈米分散液D。 奈米分散液D之pH值為2.8，平均粒徑d50為0.15 μm，d90為0.27 μm，等電點為pH值7.1。 又，於50℃下使本分散液D乾燥而獲得之粉末之結晶結構係β-氧(氫氧)化鐵，晶粒直徑為2 nm，比表面積為285 m2
/g。 實施例1～4(吸附材擔載體之製造) 反覆進行使下述之各分散液於室溫下含浸於下述之各支持體，並取出，於約50℃下使之乾燥之步驟，藉此製作吸附材擔載體。 再者，於以下之實施例3及4中使用之分散液E係粒徑60～100 nm、pH值2.2、固形物成分濃度10質量%之氧化鋯(ZrO2
)之奈米分散液，用作黏合劑。 ＜支持體＞ ・支持體1：高分子製連續氣孔海綿，1 cm見方，氣孔率90% ・支持體2：聚烯烴製吸水片材，厚度2 mm，吸水率1000% ＜吸附材擔載體之製作＞ (實施例1) 使分散液D含浸於支持體1並使之乾燥，而製造擔載體中之氧(氫氧)化鐵含量為78.0 wt%之擔載體1。 (實施例2) 使分散液D含浸於支持體2並使之乾燥，進而切割為1 cm見方，而製造擔載體中之氧(氫氧)化鐵含量為78.1 wt%之擔載體2。 (實施例3) 製備以固形物成分質量比氧(氫氧)化鐵：氧化鋯＝80：20將分散液D與分散液E混合之液體，使本混合分散液含浸於支持體2並使之乾燥，進而切割為1 cm見方，而製造擔載體中之氧(氫氧)化鐵含量為76.1 wt%之擔載體)。 (實施例4) 將粉末C添加於分散液E並進行混合，而製備固形物成分質量比氧(氫氧)化鐵：氧化鋯＝80：20之分散液，使本分散液含浸於支持體1並使之乾燥，而製造擔載體中之氧(氫氧)化鐵含量為82.5 wt%之擔載體4。 對以上之各擔載體測定真密度及比表面積。將其結果示於表1。 試驗例1(磷酸吸附試驗) 將磷酸二氫鉀溶解於離子交換水中，並利用鹽酸將pH值調整為3.5，而製備磷換算濃度為400 mg/L之試驗液G。 於試驗液G之150 mL中，浸漬擔載體1～4之各擔載體之含有氧(氫氧)化鐵1 g之量，並於室溫下攪拌，進行吸附試驗。於特定之時間後採取液體，利用濾筒與固形物成分進行分離，藉由ICP(Inductive Coupling Plasma，電感耦合電漿法)分析溶液中之磷濃度，算出磷吸附量。同時測定pH值。將結果示於表1。 [表1]
根據上述可知，本發明之吸附材擔載體係磷酸之吸附速度與吸附量優異。又，顯示出隨著磷酸之吸附而pH值上升之特徵。 試驗例2(耐鹼性試驗) 將擔載體1～4浸漬於pH值2.5之鹽酸水中及pH值12.5之氫氧化鈉水中各1週後，進行水洗、乾燥，並進行外觀檢查。於全部擔載體，未見到試驗前後之變化。(Adsorbent material carrier) The adsorbent material carrier of the present invention is an adsorbent material carrier in which particles containing oxygen (hydrogen) iron as a main component are supported on a porous support, and the BET specific surface area is 50 m 2 / g or more. Here, the "particle" means that a component containing oxygen (hydrogen) iron as a main component does not exist continuously but intermittently in an adsorbent carrier, and the existence state is maintained by a porous support. This does not limit the shape of the particles themselves. The term "supported by" means a state expressing the state of the carrier of the adsorbent, and is not limited to a manufacturing method. The adsorbent carrier of the present invention preferably has a large specific surface area. Specifically, the BET specific surface area is preferably 100 m 2 / g or more. Oxygen (hydroxide) iron is excellent in the adsorption property to anions. The particles containing oxygen (hydroxide) as the main component in the adsorbent carrier of the present invention preferably have an oxygen (hydroxide) content of 99% by mass or more, and the content of substances other than iron compounds 1 mass% or less. Most preferably, the content of oxygen (hydroxide) iron is substantially 100% by mass. According to the difference in crystal structure, there are α-type, β-type, γ-type, and amorphous type iron oxide (hydroxide). Among them, β-oxygen (hydroxide) iron is particularly excellent in adsorption performance, and is suitable for phosphate ions, phosphite ions, hypophosphite ions, sulfate ions, nitrate ions, fluoride ions, etc. Adsorption material. Moreover, it is also suitable as a raw material of a nano dispersion liquid from the point of being easy to form a stable nano dispersion liquid. Beta-oxy (hydroxide) iron is usually part of the hydroxyl group and is replaced with chloride ion. If it comes into contact with water during manufacture or use, the chloride ions are removed and small pores remain. It is considered that the pores are adsorbed with anions such as fluorine, and it is further believed that the efficient anion adsorption of the present invention is also derived from the characteristics of the pores. In terms of a large specific surface area and high anion adsorption efficiency, the iron (hydroxide) oxide in the adsorbent carrier of the present invention is preferably β-oxygen (hydroxide) iron. The particles containing the above-mentioned oxygen (hydroxide) iron as a main component preferably have an average crystal grain diameter of 10 nm or less, and more preferably 3 nm or less. It is clear from the present inventors that the smaller the average crystal grain diameter is, the faster the phosphoric acid adsorption rate is when used as a phosphoric acid adsorbent in water. The average crystal grain size D is calculated using X-ray diffraction, based on the diffraction around 2θ = 35 °, which is peculiar to β-oxygen (hydroxide) iron, using the following formula of Xie Le. D = Kλ / βcosθ where β is the half width of the actual diffraction peak resulting from the mechanical width of the device, K is the Xerox constant, and λ is the wavelength of X-rays. Such particles containing β-oxygen (hydroxide) iron having an average grain diameter of 3 nm or less as a main component are described below. The solid β-oxygen (hydroxide) iron can be wet-pulverized as described below. And get. The true density of the adsorbent carrier of the present invention is preferably 2 g / cm 3 or more, although the type of the support varies. The true density can be measured, for example, by a method according to JIS Z 8807. The porous support has a low density, and a certain amount or more of particles containing β-oxygen (hydroxide) iron as a main component are supported thereon, whereby the true density can be set to the above range. More specifically, the adsorbent carrier of the present invention is preferably such that particles containing β-oxygen (hydroxide) iron as a main component account for 60% by mass or more of the total amount of the adsorbent carrier. By setting the adsorption material carrier of the present invention to any of the above ranges, high-efficiency adsorption can be achieved. (Manufacturing method) The adsorbent carrier of the present invention is not particularly limited in this manufacturing method. As a raw material for particles containing β-oxygen (hydroxide) iron as a main component, it is preferable to use a material containing β-oxygen (Hydroxy) The solid content of iron hydroxide is pulverized into particles of a certain particle size and a solvent dispersion. As a manufacturing method of this dispersion liquid, the method of carrying out wet pulverization in a solvent, and dispersing it directly is mentioned, for example (manufacturing method A). In this method, it is preferable to perform pulverization until the average particle diameter d50 becomes 0.2 μm or less. The average particle diameter is more preferably 0.02 to 0.2 μm, and still more preferably 0.05 to 0.15 μm. The d90 is preferably 1 μm or less, and the particle diameter is preferably in the range of 0.01 to 1 μm. Further, among the particles obtained by the above-mentioned wet pulverization, the shape of the crystals was granular. Here, the term "granular" means not a needle-like shape or a plate-like shape, and more specifically, the ratio of the major axis to the minor axis of the crystal is 3 or less. As the solvent used above, it is easiest to use water or a solution containing water as a main component to prepare an aqueous dispersion, so it is preferred. On the other hand, when another solvent such as an organic solvent is required, a dispersion liquid in another solvent such as an organic solvent can also be prepared from an aqueous dispersion liquid by replacing the solvent. For example, a solvent can be obtained by mixing solvents in an aqueous dispersion while performing solvent exchange in an ultrafiltration membrane. In addition, a solvent having a boiling point higher than water is mixed with the aqueous dispersion, and the water is removed by a rotary evaporator or the like to obtain a dispersion in the solvent. Furthermore, in terms of ease of production of the adsorbent carrier, the dispersion liquid obtained by the above method is preferably a nano-dispersion liquid. The so-called nano-dispersion refers to a dispersion in which so-called nano particles having a particle diameter of 1 μm or less are dispersed in a liquid phase, and the particles are not precipitated by standing or ordinary centrifugation. When manufacturing the adsorption | suction material carrier of this invention using each said dispersion liquid as a raw material, a binder is not necessarily required. As a manufacturing method of this dispersion liquid, the method of manufacturing the particle | grains obtained by dry-grinding in the solvent (manufacturing method B) is mentioned, for example. This method is preferable when the average particle diameter d50 is 5 μm or more. In this case, the average particle diameter is preferably 70 μm or less. In the case of using the dispersion liquid as a raw material to produce the adsorbent carrier of the present invention, it is preferably a dispersion obtained by using a binder in combination or by using wet disintegration in the above solvent instead of the binder and dispersing it directly. liquid. Then, the dispersion can be supported by a method of mixing and dispersing the dispersion liquid in the raw material of the support, and then forming the dispersion, or by externally adding the dispersion liquid to a solid support. With these, an adsorbent having excellent adsorption performance and easy handling such as recovery and desorption can be produced. In the case of using a method in which raw materials are dispersed after being mixed and dispersed in a support, various resins are used as the raw materials of the support, and as the above-mentioned dispersion liquid, it is preferable to use fine particles dispersed in the resin to have compatibility The solvent. When the method of adding the said dispersion liquid to the solid support body from the outside is used, the method of immersing a support body in the said dispersion liquid, and drying a support body is preferable. The solvent of the dispersion liquid is not particularly limited, and examples thereof include water, various organic solvents, and mixtures thereof, or a solution obtained by dissolving additives such as a binder, a surfactant, and an antifoaming agent in the above liquid, if necessary. As the above-mentioned dispersion, when the particles containing β-oxy (hydroxide) iron as the main component are pulverized in a solvent until the average particle diameter d50 becomes 0.2 μm or less, the particles themselves have It has the same effect as an adhesive, so it is not necessary. This method is easy to operate, and supports particles having β-oxygen (hydroxide) iron as a main component on the surface of the support, so that it becomes possible to perform efficient adsorption and desorption. As the solid containing β-oxygen (hydroxide) iron as the main component, it is preferably obtained by a method including a step of reacting a solution of an iron-containing compound with a base to form a precipitate at a pH value of 9 or lower. Dry the gel. As the iron compound, an iron salt is preferred, and a trivalent iron salt is particularly preferred. Specific examples include ferric chloride, ferric sulfate, and ferric nitrate. Among them, ferric chloride is particularly preferred. The base is used to neutralize an acidic iron compound aqueous solution and generate a precipitate containing iron (hydrogen) oxide. Specific examples include sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia, sodium carbonate, potassium carbonate, and calcium carbonate. Among these, sodium hydroxide is particularly preferred. The pH during the purification of the precipitate is more preferably adjusted to a pH range of 3.3 to 6. The precipitate containing oxygen (hydroxide) iron as a main component obtained by the above method can be separated by filtration and recovered, and if dried, it becomes a dry gel. Furthermore, after the above steps, it is preferable to perform a step of drying the precipitate, and a step of drying the precipitate after being brought into contact with water. The step of drying the precipitate is preferably performed at 120 ° C or lower, and more preferably at 100 to 120 ° C. Drying temperature takes time at low temperatures and is not suitable for efficient manufacturing. In addition, there is a tendency that the number of anion adsorption sites decreases at high temperatures, and further it is converted to iron oxide at high temperatures, which is not preferable. Drying can be performed in air, vacuum, or inert gas. It is considered that in the step of bringing the dried matter into contact with water, impurities such as sodium chloride are eluted, and thereafter pores remain, the specific surface area increases, and the anion adsorption site also increases. After the dried substance was brought into contact with water, the water was removed and dried again. Preferably, this drying step is also performed under the same conditions as described above. The dry gel obtained by the above method contains β-oxy (hydroxide) iron as a main component. The adsorbent carrier of the present invention can also be used in the gas phase, for example, to adsorb harmful substances in the exhaust gas, etc., and is preferably used in the liquid phase. Generally, when an adsorbent is used in the liquid phase, it takes time for the components contained in the liquid to reach the pores by diffusion, so it takes time to reach the adsorption equilibrium. On the other hand, if the adsorbent is dispersed in the liquid in the form of fine particles, the adsorption equilibrium will be quickly reached, but there is a problem in the separation and recovery of the fine particles. The adsorbent carrier of the present invention has the purpose of simultaneously solving these problems, and is therefore particularly suitable for use in a liquid phase. As the liquid phase, if the part other than the adsorbent carrier is a homogeneous liquid phase, it can be used without any problems. For example, an organic solvent solution can also be used. However, it is preferred to remove harmful substances and recover useful substances. Purpose, use in aqueous solution. The adsorbent carrier of the present invention is particularly suitable for an anionic adsorbent. Furthermore, it is suitable for a fluorine and phosphoric acid adsorbent, and among them, it is suitable for a phosphoric acid adsorbent. In the manufacture of the adsorbent material carrier of the present invention, an adhesive for binding the adsorbent with the carrier is not necessary, but in order to make the bond stronger, it can be made to withstand long-term repeated users, and an adhesive can also be used together. In particular, when the average particle diameter d50 of particles containing β-oxy (hydroxide) iron as a main component is 5 μm or more, it is preferable to use a binder in combination. The binder is not inconvenient when used as a carrier for an anion adsorbent, and is preferably stable in the range of pH 2.5 to pH 12.5, and more preferably in the range of pH 1 to 14. In addition, the adhesive must not be one that reduces the adsorption performance by covering the surface of the adsorbent. The material of the adhesive is not particularly limited as long as it meets the above conditions, and for example, an inorganic compound can be used. Inorganic compounds are usually in the shape of particles, so they rarely cover the surface of the adsorbent and are suitable for adhesives. The mass of particles containing oxygen (hydroxide) iron as the main component, especially those having an average particle diameter d50 of 5 μm or more, is better than that of the binder in a range of 7: 3 to 10: 0. Examples of the inorganic compound include compounds of a metal selected from zirconium, titanium, and tin. Particularly preferred are the oxides or hydroxides of the aforementioned metals. Among them, a dispersion liquid containing zirconia is particularly preferred. When a zirconia dispersion is used as a binder, particles containing oxygen (hydroxide) iron as a main component are supported not only on the surface of the support but also on the pores in the support. The adsorption efficiency of the carrier becomes very high. In this case, the quality of particles containing oxygen (hydroxide) iron as the main component and the quality of zirconia is preferably 8: 2 to 9.5: 0.5. Even if the zirconia is further increased, the adsorption efficiency will not be further improved, and even in terms of cost, this range is preferable. On the other hand, the adhesive may be a polyolefin-based resin. There is a concern that the surface of the adsorbent is covered in the resin, but since the polyolefin resin is hydrophobic, there is no such concern. In addition, in terms of ease of production of the adsorbent carrier, the polyolefin resin is preferably in the form of an emulsion. Examples of polyolefin resins include polyethylene (low-density polyethylene such as linear low-density polyethylene, medium-density polyethylene, and high-density polyethylene); polypropylene; ethylene-propylene copolymers; and ethylene or propylene and Copolymers of other α-olefins; further copolymers of ethylene or propylene with unsaturated monomers such as (meth) acrylic acid, (meth) acrylate, vinyl acetate, vinyl alcohol, styrene, etc. The support used for the adsorbent material carrier of the present invention is not particularly limited as long as it is porous. In order to be used as an anion adsorbent material carrier, it is preferably stable in the range of pH 2.5 to pH 12.5 , More preferably stable in the range of pH 1 to 14. Moreover, from the viewpoint of easy processing, the support used in the adsorbent carrier of the present invention is preferably a porous polymer material. When only water is used as the solvent, the porous polymer material may be used regardless of hydrophilicity or hydrophobicity. Specific examples of the polymer material include natural polymers such as cellulose, semi-synthetic polymers such as cellulose derivatives, polyolefins, polystyrene, polyacrylate, polyvinyl acetate, polyvinyl chloride, and poly Synthetic polymers such as vinyl alcohol, polyurethane, polyester, polycarbonate, phenolic resin, urea resin, and polyimide. Among these, polyolefin resin is particularly preferable. As described above, since the polyolefin resin is hydrophobic, there is no case where the surface of the adsorbent is covered and the adsorption performance is lowered. As a method for making these materials porous, various methods such as a phase separation method, a foaming method, a fusion method, an extraction method, a chemical treatment method, and an extension method can be used. The shape of the support is not particularly limited, and examples thereof include a sponge shape, a sheet shape, and a particle shape, and may be appropriately selected from these depending on the application. Among them, the specific shape (rectangular, spherical, etc.) of the sponge-like one is not particularly limited, in terms of the fact that the adsorbent is easily carried inside when the carrier is manufactured, and the target liquid reaches the inside in a short time during use. , Preferably smaller size. Moreover, in the same meaning, a sheet shape or a particle shape is more preferable, and the thickness of the sheet or the diameter of the particles is preferably 5 mm or less. Furthermore, plural shapes can be used in combination from the above shapes. As the support, each of the shapes described above can be made in advance, or it can be cut to produce a specific shape or size after the carrier is manufactured. The adsorption material carrier of the present invention is the same as the dispersion liquid, and has the characteristic of high adsorption speed. The adsorption speed can be measured by a batch adsorption test described below. Prepare 150 mL of potassium dihydrogen phosphate aqueous solution with a fixed phosphorus conversion concentration of 400 mg / L using hydrochloric acid to adjust the pH value. 1 g of an adsorbent was put into this, and it stirred at room temperature. After a certain period of time, the aqueous solution was sampled, the phosphate ion concentration was measured, and the amount of adsorption was determined. In addition, in the above test, the amount of phosphate ion adsorption can be obtained over time, and the final amount of adsorption can be estimated based on the amount of adsorption at the time point when the change over time disappears. More simply, the final adsorption amount can be estimated based on the adsorption amount after 24 hours. In the method of the adsorbent carrier of the present invention, when the pH value of the aqueous solution is adjusted to 3.5, the phosphorus equivalent adsorption amount after 24 hours becomes 25 mg or more, and preferably 30 mg or more. In addition, the adsorption material carrier of the present invention is characterized in that the pH value is significantly increased during the use as an anion adsorption material in water. Specifically, this feature is shown by the following method. Prepare 150 mL of potassium dihydrogen phosphate aqueous solution with a fixed phosphorus conversion concentration of 400 mg / L using hydrochloric acid to adjust the pH value. 1 g of an adsorbent carrier was put into this, and it stirred at room temperature. After a certain period of time, the aqueous solution was sampled and the pH was measured. In the method of the adsorbent carrier of the present invention, when the pH value of the aqueous solution is adjusted to 3.5, the pH value of the aqueous solution after 24 hours increases by 0.3 or more relative to the pH value of the aqueous solution after 1 hour. In addition, the β-oxygen (hydroxide) iron used as a material of the adsorbent carrier of the present invention hardly causes a change in the pH value of the aqueous solution even when used as an adsorbent without being pulverized. These reasons are estimated by the following methods. In β-oxy (hydroxide) iron without pulverization or the like, the hydroxyl group is located in pores which cannot be easily reached by larger anions such as phosphate ions. Such pores are formed especially by the release of chloride ions. On the other hand, since the pore structure of the adsorbent carrier of the present invention is damaged, phosphate ions easily reach the vicinity of the hydroxyl group. Β-oxygen (hydroxide) iron without pulverization and other treatments also has large pores, so it can adsorb phosphate ions with a slower adsorption rate. In the adsorbent carrier of the present invention, the adsorbed anion is then exchanged with a hydroxyl group, and the anion is directly bonded to the adsorbent. At the same time, the hydroxyl group is released into the water in the form of hydroxide ions. The pH of the aqueous solution rises. However, it is presumed that β-oxygen (hydroxide) iron, which is not subjected to processing such as pulverization, does not cause such substitution, and therefore does not cause a rise in pH. Furthermore, the content of chloride ions in the β-oxy (hydroxide) iron used in the present invention is preferably 0.5% by mass or more, and more preferably 3% by mass or more. Based on the foregoing, it is considered that the adsorbent carrier of the present invention does not simply adsorb anions, and thereafter the anions are in a state of being easily bonded to the adsorbent carrier and not easily dissociated, and thus exhibit a high adsorption efficiency. [Examples] Next, examples of the present invention will be described in more detail, but the present invention is not limited thereto. Measurement method (powder X-ray diffraction) The X-ray diffraction (XRD) pattern is measured using an X-ray diffraction device Ultima IV (manufactured by Rigaku). The CuKα bulb was used for the measurement. The average grain diameter is calculated from XRD and is based on Xie Le's formula. (Specific surface area) The specific surface area was measured by a gas adsorption method using a specific surface area measuring device MacsorbHM 1210 (manufactured by Moontech). (TEM observation) The TEM (Transmission Electron Microscopy) observation of the sample was performed using a transmission electron microscope JEM 2010F (manufactured by JEOL, accelerating voltage 200 kV). (Content of Chloride Ion in Oxygen (Hydroxy) Oxide) After the oxygen (hydroxide) iron sample is dissolved in 3M sulfuric acid, it is diluted with an alkaline solution to precipitate iron components, and filtered with a filter to The filtrate was recovered and quantified by ion chromatography (DX-500 model manufactured by Japan Dionex Corporation). (Particle Size Distribution of Dispersion Liquid) About the particle size of the dispersion liquid in micron units, a laser diffraction / scattering type particle size distribution measuring device LA-920 (manufactured by HORIBA, Ltd.) was used to accumulate a 50% particle size (D50) on a volume basis , And the volume-based cumulative 90% particle size (D90) was measured. The particle diameter, particle size distribution, cumulative 50% particle diameter (D50), and cumulative 90% particle diameter (D90) of the nano-dispersion were measured using a dynamic light scattering particle size distribution measuring device Zetasizer Nano S (manufactured by Spectris). (True density) A true density measurement using a helium replacement method (dry density meter: AccuPyc 1340TC, manufactured by Shimadzu Corporation and Micromeritics) was performed. Reference example 1 (manufacturing of oxygen (hydroxide) iron) In an aqueous solution of ferric chloride (FeCl 3 ), an aqueous solution of sodium hydroxide (NaOH) was added dropwise while adjusting the pH to 6 or less at room temperature. The final addition amount was set to NaOH / FeCl 3 (molar ratio) = 2.75 and reacted to obtain a particle suspension of oxygen (hydroxide) iron. The average particle diameter d50 of the particles in the obtained suspension was 17 μm. After the suspension was filtered and separated, the suspension was dried at 120 ° C in the air, washed with ion-exchanged water, and further dried at 120 ° C in the air to obtain a powder of oxygen (hydroxide) iron (powder A). The particle size of the oxygen (hydroxide) powder (powder A) obtained in the above manner is 0.25 mm to 5 mm. By X-ray diffraction, it was confirmed that the crystal structure was β-oxygen (hydroxide) iron, and the average crystal grain size was 5 nm. The observation by a transmission electron microscope (TEM) is shown in FIG. 1. The crystal shape is almost granular with an aspect ratio of 1: 3 or less. Observed by TEM, the obtained crystal grains have a diameter of 5 to 10 nm, each crystal is granular, and these coagulate to form particles. The specific surface area was 280 m 2 / g, and the chloride ion content was 5.8 wt%. Reference Example 2 (Production of oxygen (hydroxide) iron adsorbent particles) Dry pulverization of the oxygen (hydroxide) iron powder (powder A) with a pin mill to obtain a powder having a particle size distribution shown in FIG. 2 (powder B). The particle diameter of powder B ranges from 0.6 to 300 μm, and the average particle diameter is 26.5 μm. Reference example 3 (manufactured by removing particles below 10 μm) Wrapped powder B with a nylon mesh with a sieve opening of 10 μm, put it into ion-exchanged water, and thoroughly cleaned to remove those with a particle diameter of 10 μm or less to obtain a particle size range A powder (powder C) of 8 to 300 μm and an average particle diameter of 40.3 μm. The particle size distributions of the above powder B, powder C (on the sieve), and sieved products (the above-mentioned removed components) are shown in FIG. 2. Reference Example 4 (Production of nanometer dispersion of oxygen (hydroxide) iron) Powder B was mixed with ion-exchanged water so that the solid content concentration became 10% by mass, and then a bead mill (zirconia beads, beads) was used. The particle diameter was 1 mm) and coarsely pulverized for 30 minutes to prepare a suspension. Furthermore, this was pulverized with a bead mill (zirconia beads, bead diameter 0.1 mm) for 60 minutes to obtain a dispersion liquid D. As a result of the pulverization, the brown suspension liquid becomes black and transparent nano-dispersion liquid D. The pH value of the nano-dispersion D was 2.8, the average particle diameter d50 was 0.15 μm, d90 was 0.27 μm, and the isoelectric point was pH 7.1. The crystal structure of the powder obtained by drying the dispersion D at 50 ° C was β-oxy (hydroxide) iron, the crystal grain diameter was 2 nm, and the specific surface area was 285 m 2 / g. Examples 1 to 4 (manufacturing of an adsorbent carrier) The steps of impregnating each of the following dispersions at room temperature with the following supports were taken out and dried at about 50 ° C. This makes an adsorbent carrier. Furthermore, the dispersion liquid E used in the following Examples 3 and 4 is a nano-dispersion solution of zirconia (ZrO 2 ) having a particle diameter of 60 to 100 nm, a pH value of 2.2, and a solid content concentration of 10% by mass. As a binder. ＜ Supports ＞ ・ Support 1: Continuous pore foam made of high polymer, 1 cm square, with a porosity of 90%. ・ Support 2: Polyolefin water-absorbent sheet, thickness 2 mm, water absorption rate 1000%. Production> (Example 1) The dispersion 1 was impregnated with the support 1 and dried to prepare a support 1 having an oxygen (hydrogen) iron content of 78.0 wt% in the support. (Example 2) The dispersion 2 was impregnated with the support 2 and dried, and then cut into 1 cm squares to produce a support 2 having an oxygen (hydroxide) iron content of 78.1 wt% in the support. (Example 3) A liquid was prepared by mixing the dispersion liquid D and the dispersion liquid E with a solid content mass ratio of oxygen (hydroxide) iron: zirconia = 80:20, and impregnating the mixed dispersion liquid into the support 2 and making It was dried, and then cut into 1 cm square, and a carrier having an oxygen (hydrogen) iron content of 76.1 wt% in the carrier was manufactured). (Example 4) Powder C was added to Dispersion E and mixed to prepare a dispersion having a solid content ratio of oxygen (hydroxide) iron: zirconia = 80:20, and the dispersion was impregnated in a support. 1 and allowed to dry to produce a carrier 4 having an oxygen (hydroxide) iron content of 82.5 wt% in the carrier. The true density and specific surface area of each of the above carriers were measured. The results are shown in Table 1. Test Example 1 (Phosphoric acid adsorption test) Potassium dihydrogen phosphate was dissolved in ion-exchanged water, and the pH was adjusted to 3.5 using hydrochloric acid to prepare a test solution G having a phosphorus-converted concentration of 400 mg / L. In 150 mL of the test solution G, 1 g of each of the carriers 1 to 4 containing oxygen (hydroxide) iron was impregnated, and stirred at room temperature to perform an adsorption test. The liquid was taken after a specific time, and the solid components were separated using a filter cartridge. The concentration of phosphorus in the solution was analyzed by ICP (Inductive Coupling Plasma) to calculate the amount of phosphorus adsorption. At the same time, the pH was measured. The results are shown in Table 1. [Table 1] From the above, it can be seen that the adsorption material carrier-based phosphoric acid of the present invention has excellent adsorption speed and adsorption amount. In addition, it has a characteristic that the pH value increases with the adsorption of phosphoric acid. Test Example 2 (Alkali resistance test) The carriers 1 to 4 were immersed in hydrochloric acid water having a pH of 2.5 and sodium hydroxide water having a pH of 12.5, and then washed, dried, and inspected for appearance. No change was observed before and after the test on all the carriers.