201008606 六、發明說明 【發明所屬之技術領域】 本發明關於有機化合物所污染的土壤及/或地下水之 淨化劑，以及使用該淨化劑的淨化方法。 【先前技術】 土壤及地下水中的有機物污染對環境所造成的影響係 q 變明顯，隨著各式各樣的規定之整備，到目前爲止所積蓄 、放置的污染之淨化係變成必要。此處的有機物係主要指 難以被生物分解的有機物，相當於農藥、防腐劑、石油及 其餾份中所含有的芳香族化合物、齒化有機化合物等。 對於此有機物污染，嘗試物理的、化學的、生物的各 式各樣淨化方法。就物理的淨化方法而言，污染場所的淨 化雖然可能，但是有需要二次處理所去除的污染物質之缺 點。生物的淨化方法雖然是對周邊環境的影響少之方法， Q 但是對於高濃度的污染有難以適用的缺點。相對於此等， 化學的淨化方法由於將對象污染物質分解，具有特徵爲不 需要二次處理，對於高濃度的污染亦可適用。 已知藉由添加過氧化氫等的氧化劑及當作觸媒的可供 應鐵離子之化合物（例如：硫酸亞鐵•七水合物等），產 生羥自由基，使此自由基與有機物反應，而將有機物氧化 分解的芬頓（Fenton )法。於化學的淨化方法之中，嘗試 應用此芬頓法將有機化合物所污染的土壤淨化（參照專利 文獻1 )。 -5- 201008606 據說通常的芬頓法之最合適pH範圍爲3〜4，在pH 範圍爲中性以上的反應中，觸媒的鐵離子會變成氫氧化物 而沈澱，幾乎不進行反應，在此PH3〜4的最合適pH範 圍進行土壤淨化時，由於土壤中的重金屬成分之溶出，有 二次污染之發生或擴大的可能性，有地下構造物的鋼骨或 地下配管發生腐蝕之虞。爲了彌補此缺點，有提案使用緩 衝劑，在中性附近的一定pH進行淨化。 於專利文獻2、3中，爲了防止污染有機物的分解所 造成的pH降低，設計出氧化劑與緩衝劑的添加，但是並 沒有載明防止鐵等的觸媒之金屬離子在高pH範圍的沈澱 之手段，取決於氧化劑的種類或淨化場所的環境，由於鐵 等的地下水中所含有的金屬成分之沈澱，而發生流路、配 管的堵塞，在淨化作業有產生問題的可能性。 又，爲了防止鐵等的觸媒之金屬離子的沈澱，有設計 出添加氧化劑以及螯合劑的技術。專利文獻4中雖然主要 以防止鐵的沈澱爲目的，進行螯合劑的添加，但是由於所 使用的pH範圍在酸性側，故所規定的添加莫耳比之範圍 ，對於鐵而言爲1/3左右的少量，若考量液體的pH範圍 ，則重金屬的溶出等之發生二次污染的危險性係殘留著。 又，於專利文獻5中，雖然設計出螯合劑與氧化劑的倂用 ，但是螯合劑的添加目的僅爲防止鐵等的金屬離子之沈澱 ，沒有採取防止緩衝劑等所致的pH降低之手段，若考量 液體的pH範圍，則重金屬的溶出等所造成的二次污染之 可能性高。 -6 - 201008606 對此，亦有設計出添加中性附近的Fe螯合物之手法 。專利文獻6中提案起先注入氧化劑，然後注入F e整合 物的手法。然而，但是並沒有採取防止起先添加的氧化劑 所造成的pH降低之手段。於作爲較佳的氧化劑所提示的 過氧化氫中’由於通常添加磷酸系的安定劑’PH爲1〜4 ，故作用場所的PH會降低，有發生重金屬的溶出等之二 次污染的可能性。 φ 又，專利文獻6中，揭示同時注入氧化劑與Fe螯合 物的手法。然而，於同時注入氧化劑與Fe螯合物的情況 ，在與混合的同時，氧化劑開始分解，在離開注入地方的 場所，有氧化劑無法到達的缺點。 專利文獻7中揭示將生物分解性螯合劑與pH緩衝劑 一起加到地中，與地中的鐵生成錯合物後，將作用場所的 pH保持在5〜10而添加氧化劑的方法。然而，由於在此 方法中，作爲較佳的氧化劑所提示的過氧化氫係在觸媒存 0 在下添加，故在離開注入地方的場所，有氧化劑無法到達 之缺點。 再者，前述專利文獻2、3、5〜7中爲了控制任何作 用場所的pH ’使用pH緩衝劑，必須在淨化地點調合氧化 劑、觸媒溶液以及pH緩衝劑。 [專利文獻1]特開平7-75772號公報 [專利文獻2]特開2004-202357號公報 [專利文獻3]特開2004-3 05959號公報 [專利文獻4]特開2002-159959號公報 201008606 [專利文獻5]特開2000-3 0 1 1 72號公報 [專利文獻6]日本發明專利3 793 〇84號公報 [專利文獻7] WO2006- 1 23 574號公報 【發明內容】 發明所欲解決的問題 本發明係鑒於如上述的先前技術之各種問題點而提案 者，目的爲提供對周邊環境、生態系統等不會造成影響， 可簡便地應用於在原位置淨化有機化合物所污染的土壤及 /或地下水之方法，而且可安全且有效地淨化處理從注入 地方到比較遠的地方爲止之廣範圍，及對於高濃度污染也 能淨化處理的土壤及/或地下水之淨化劑，以及使用該淨 化劑的土壤及/或地下水之淨化方法。 解決問題的手段 本發明者們爲了解決上述問題點，進行專心致力的硏 φ 究，結果發現含有過氧化氫水、檸檬酸、水，檸檬酸的質 子數經調整的水溶液之本發明的淨化劑，係（1 )即使添 加於土壤及/或地下水中，作用場所的pH之變動也少， (2)即使在添加於土壤及/或地下水中之前將淨化劑稀 釋，其pH也在中性附近而比較安全，及（3)作用場所的 過氧化氫之安定性良好。再者，發現藉由將本發明的淨化 劑以原液或稀釋而加到經有機物所污染的土壤及/或地下 水中’不需要另途調製pH緩衝劑，重金屬亦不會溶出’ -8- 201008606 可淨化廣範圍，而完成本發明。 即，本發明關於以下所示的土壤及/或地下水之淨化 劑，以及土壤及/或地下水的淨化方法。 <1>一種土壤及/或地下水之淨化劑，其特徵爲含 有： (A) 100重量份的過氧化氫， (B) 至少10重量份的檸檬酸，及 φ (C)以（A)過氧化氫與（B)檸檬酸的合計爲100 重量份時，至少1 5重量份的水，而且添加 (D)鹼化合物，其用於滿足下式之檸檬酸（B)的質 子數， 檸檬酸（B )的質子數=〇.〇5χΜ〜0·80χΜ (1) (式（1)中，Μ表示檸檬酸（Β)的莫耳數）。 < 2 > 如上述< 1 >記載的土壤及/或地下水之淨化劑，其 Q 中使用過氧化氫爲60重量％以下的過氧化氫水溶液。 < 3 > 如上述< 1 >記載的土壤及/或地下水之淨化劑，其 中使用過氧化氫爲3 0〜43重量％的過氧化氫水溶液。 < 4 > 如上述< 1>〜< 3>中任一項記載的土壤及/或地下 水之淨化劑，其中鹼化合物係從鹼金屬氫氧化物、鹼金屬 氧化物、鹼金屬過氧化物、鹼土類金屬氫氧化物、鹼土類 金屬氧化物、鹼土類金屬過氧化物、氨、胺、氫氧化四級 -9- 201008606 銨所組成族群所選出的1種以上之化合物。 < 5 > 一種土壤及/或地下水之淨化方法，其係有機化合物 所污染的土壤及/或地下水之淨化方法，其特徵爲：添加 (A) 100重量份的過氧化氫， (B) 至少10重量份的檸檬酸，及 (C) 以（A)過氧化氫與（B)檸檬酸的合計爲100 重量份時，至少1 5重量份的水，而且添加 (D) 鹼化合物，其用於滿足下式之檸檬酸（B)的質 子數， 檸檬酸（B )的質子數=0_05χΜ〜0·80χΜ (2) (式（2)中，Μ表示檸檬酸（Β)的莫耳數）。 < 6 > 如上述<5>記載的土壤及/或地下水之淨化方法， 其中鹼化合物係從鹼金屬氫氧化物、鹼金屬氧化物、鹼金 屬過氧化物、鹸土類金屬氫氧化物、鹼土類金屬氧化物、 鹼土類金屬過氧化物、氨、胺、氫氧化四級銨所組成族群 所選出的1種以上之化合物。 < 7 > 如<5>、<6>中任一項記載的土壤及/或地下水之 淨化方法，其中預先調製（A) 、 ( Β ) 、（C)及（D) 當作淨化劑，將該淨化劑以原液或稀釋而添加。 < 8 > 如上述<5>〜<7>中任一項記載的土壤及/或地下 -10- 201008606 水之淨化方法，其中在（A) 、( B ) 、（C)及（D)的 添加後，將從過渡金屬單體、過渡金屬氧化物、過渡金屬 鹽、過渡金屬螯合物所組成族群所選出的至少1種加到土 壤及/或地下水中。 < 9 > 如上述<8>記載的土壤及/或地下水之淨化方法， 其中過渡金屬係二價鐵及/或三價鐵。 < 1 0 > 如上述<8>、<9>中任一項記載的土壤及/或地下 水之淨化方法，其中過渡金屬螯合物係由下述式（3)所 示的雙羧甲基胺系螯合劑所構成， R-N ( CH2COOX) 2 ( 3 ) (式（3)中，R表示不含氮原子的有機基，X表示Η 或鹼金屬）。 < 1 1 > 如上述< 1 〇 >記載的土壤及/或地下水之淨化方法， 其中前述式（3)中的R係-CH(CH3) COOX、 •CH ( COOH) C2H4COOX、-CH ( COOX) CH2COOX 或 -C2H4S03X ( X係H或鹼金屬）。 < 12> 如上述< 8>〜< 11>記載的土壤及/或地下水之淨 化方法，其中添加從過渡金屬單體、過渡金屬氧化物、過 渡金屬鹽、過渡金屬螯合物所組成族群所選出的至少1種 及pH緩衝劑。 201008606 < 1 3 > 如上述<5>〜< 12>記載的土壤及/或地下水之淨 化方法，其中在原位置將土壤及/或地下水淨化。 < 1 4 > 如上述<5>〜< 13>記載的土壤及/或地下水之淨 化方法，其中對進行生物整治處理的土壤及/或地下水’ 添加（A) ' ( B ) 、（C)及（D)。 發明的效果 本發明的淨化劑所致的土壤及/或地下水的淨化方法 係具有以下的效果。 (1 )由於添加在中性附近經安定化的過氧化氫水溶 液，故不會溶出重金屬，可使過氧化氫到達與注入地方有 距離的場所，可擴大土壤及/或地下水的淨化範圍。 (2 )由於添加在中性附近經安定化的過氧化氫水溶 液，故可防止與淨化無關聯的過氧化氫之分解，可高效率 地利用過氧化氫。 (3) 由於邊將土壤及/或地下水保持在中性附近， 邊添加鐵等的過渡金屬離子，故不溶解重金屬，可分解污 染源的有機化合物。 (4) 由可預先製造調合有pH緩衝劑的濃稠過氧化氫 水溶液，故在淨化地點不需要調合作業，可簡便地使用。 因此，依照本發明，對周邊環境、生態系統等不會造 成影響，可在原位置安全且有效地淨化有機化合物所污染 -12- 201008606 的土壤及/或地下水。 【實施方式】 實施發明的最佳形態 本發明的淨化對象之土壤及/或地下水係被有機物所 污染者。作爲該有機物，例如可舉出農藥、防腐劑、石油 及其餾份所含有的芳香族化合物、鹵化烴等。作爲石油及 Φ 其餾份所含有芳香族化合物，可舉出甲苯、苯等。作爲有 機氯化合物.，可舉出三氯乙烯（TCE )、四氯乙烯（PCE )等。 本發明所用的過氧化氫係沒有特別的限制，較佳爲使 用工業用過氧化氫水溶液。 工業用過氧化氫水溶液中的過氧化氫之濃度係沒有特 別的限制，但是由於比60重量％高的濃度之過氧化氫水溶 液係取得困難，故較佳爲60重量％以下，更佳爲不是危險 0 物的45重量％以下之過氧化氫水溶液，而且從輸送成本的 觀點來看，較佳爲過氧化氫濃度30重量％以上的過氧化氫 水溶液。 本發明的淨化劑含有檸檬酸，其目的爲將過氧化氫在 中性條件下安定化及賦予pH緩衝劑能力。 本發明所用的檸檬酸係可使用工業用、試藥用、食品 添加用、藥典的任何者。可使用水溶液、水合物、酐及此 等的鹽。於本發明的淨化劑中，檸檬酸濃度的下限雖然被 淨化對象的土壤及/或地下水中之鐵量所影響，但是相對 -13- 201008606 於100重量份的過氧化氫而言，至少含有10重量份。當 檸檬酸低於10重量份時，在通常的土壤及/或地下水中 ，過氧化氫的安定性降低，淨化範圍變窄。 相對於100重量份的過氧化氫而言，檸檬酸的更佳配 合量爲10〜50重量份。 於本發明的淨化劑中，視需要可更含有當作安定化劑 之檸檬酸以外的安定化劑（例如8-羥基喹啉、1，10_菲繞 啉、苯并三唑、尿素、四級銨鹽、吡咯烷酮羧酸類、脂肪 族胺、硝基化合物、磺胺酸、醇類、酚類、苯基二醇醚、 羧酸 '醇胺、胺基羧酸鹽、醇酸、水楊酸、α-酮基羧酸酯 、醛-羧酸酯、矽酸鹽、錫酸鹽、鉬、锆及鈮、植酸 '亞 硫酸鹽、硫系安定化劑、工業用過氧化氫水溶液中所通常 添加的磷酸系安定化劑）。 相對於過氧化氫與檸檬酸的合計100重量份而言，本 發明的淨化劑含有至少1 5重量份的水。若水的含量少於 此’則檸檬酸及/或檸檬酸鹽會析出，淨化劑的組成有不 安定之虞。再者，當使用工業用過氧化氫水溶液時，水的 含量係考慮包含工業用過氧化氫水溶液中所預先含有的水 。水的更佳含量爲160〜2000重量份。 於本發明的淨化劑中，除了過氧化氫及檸檬酸，亦摻 合鹼化合物。鹼化合物的摻合係爲了調整淨化劑中所含有 的檸檬酸之質子數。將從檸檬酸的酸基而來的氫原子及氫 離子稱爲質子，質子數係表示從此等檸檬酸的酸基而來的 氫原子及氫離子之和的數。由於檸檬酸具有3個羧基，故 -14- 201008606 當不添加鹼化合物時，淨化劑的檸檬酸之質子數係成爲理 論配合的檸檬酸之莫耳數的3倍。 此處，若在淨化劑中摻合檸檬酸及鹼化合物，則藉由 與該鹼化合物的陽離子之反應，而消耗淨化劑中的來自檸 檬酸的羧基之氫原子及氫離子（質子），對應於鹼化合物 的添加量而減少。即，若在本發明的淨化劑中添加檸檬酸 及鹼化合物，則淨化劑中的檸檬酸之質子數係對應於鹼化 0 合物的添加量而降低。 如上述地，當不添加鹼化合物時，淨化劑中的檸檬酸 之質子數係成爲理論配合的檸檬酸之莫耳數的3倍，但是 於本發明中，重要的爲使此淨化劑中的檸檬酸之質子數在 比理論値少的一定範圍。 本發明中，藉由鹼化合物來調整淨化劑所含有的檸檬 酸之質子數，使滿足式（1)。 檸檬酸（B )的質子數=〇·〇5χΜ〜0.80xM ( 1 ) Q (式（1)中，Μ表示淨化劑中所配合的檸檬酸（Β) 的莫耳數）。 本發明的式（1)之淨化劑中的檸檬酸之質子數，係 表示淨化劑中所含有的從檸檬酸的酸基而言氫原子與氫離 子之和。於本發明中，藉由調整鹼化合物對淨化劑的添加 量，可調整淨化劑中的檸檬酸之質子數，使滿足式（1) 〇 例如，當檸檬酸的莫耳數爲1莫耳時，由於式（1) 所算出的檸檬酸之質子數範圍爲0.05〜0.80，故在添加氫 -15- 201008606 氧化鈉等之1價陽離子的鹼金屬氫氧化物當作驗化合物之 際’藉由添加2.20〜2.95莫耳的如下述式所示的該鹼化合 物，可成爲最合適的檸檬酸之質子數範圍。 Μχ3-Αι=Μχ ( 0.05 〜0.80) A!=Mx[3- ( 0.05 〜0.80) ] = Μχ[2·95 〜2.20] (上述式中’ Μ表示所配合的檸檬酸之莫耳數；、表 示所配合的1價陽離子的驗化合物之莫耳數）。 又’於添加氫氧化鎂等的2價陽離子之鹼土類金屬氫 氧化物之際，藉由添加1.10〜1.475莫耳的如下述式所示 的該鹼化合物，可成爲最合適的檸檬酸之質子數範圍。 Μχ3-Α2χ2 = Μχ ( 0.05〜0.80) Α2χ2 = Μχ〔 3- ( 0.05~0.80 )〕 Α2 = Μχ [ 2.95-2.20 ] —2 = Μχ〔 1 .475〜1 · 1 〇〕 (上述式中，Μ表示所配合的檸檬酸之莫耳數。八2表 示所配合的2價陽離子的鹼化合物之莫耳數）。 又，3價以上的陽離子的鹼化合物之添加量範圍，亦 可與上述同樣地求得。再者，亦可組合1價陽離子的鹼化 合物與2價陽離子的鹼化合物。於該情況下，可適宜選擇 兩者的比例，以使檸檬酸的質子數在式（1)所規定的範 圍內。 淨化劑所含有的檸檬酸之質子數若大於式（1 )所規 定的範圍，則稀釋該淨化劑後時的pH變過低，作業者的 危險性變高，使用機器的腐蝕危險性變高。再者，添加於 土壤及/或地下水中而被地下水稀釋後時的PH變過低’ -16- 201008606 導致重金屬的溶出而提高二次污染的危險性。檸檬酸的質 子數若小於式（1 )所規定的範圍，則稀釋該淨化劑後時 的pH緩衝能力減弱，過氧化氫的分解有變快之虞，或重 金屬或砷的溶出所致的二次污染之危險性有提高之虞。 本發明的檸檬酸之質子數的調整所用的鹼化合物係其 水溶液顯示鹼性的化合物，較佳爲從鹼金屬氫氧化物、鹼 金屬氧化物、鹼金屬過氧化物、鹼頒金屬氫氧化物、鹼土 0 類金屬氧化物、鹼土類金屬過氧化物、氨、胺、氫氧化四 散銨所組成族群所選出的1種以上之化合物。 作爲鹼金屬氫氧化物，較佳爲氫氧化鈉、氫氧化鉀、 氫氧化鋰。作爲鹼金屬氧化物，較佳爲氧化鈉、氧化鉀、 氧化鋰。作爲鹼金屬過氧化物，較佳爲過氧化鈉、過氧化 鉀、過氧化鋰。 作爲鹼土類金屬氫氧化物，較佳爲氫氧化鎂、氫氧化 鈣。作爲鹼土類金屬氧化物，較佳爲氧化鎂、氧化鈣。作 @ 爲鹼土類金屬過氧化物，較佳爲過氧化鎂、過氧化鈣。 作爲胺，較佳爲甲胺、二甲胺、三甲胺、乙胺、二乙 胺、三乙胺、丙胺、異丙胺、二異丙胺、第二丁胺、第三 丁胺。作爲氫氧化四級銨，較佳爲氫氧化四甲銨，特佳爲 從氫氧化鈉、氫氧化鉀、氫氧化鎂及氨所選出的一種以上 之化合物。 本發明的淨化劑，只要以滿足前述式（1 )的方式來 調製，則亦可含有中性鹽。作爲中性鹽，較佳爲強酸與強 鹼之中和所生成的正鹽，例如可舉出氯化鈉、氯化鉀、氯 -17- 201008606 化鎂、氯化鈣、硫酸鈉、硫酸鉀、硫酸鎂、硝酸鈉、硝酸 鉀等。 用於調製本發明的淨化劑之裝置係沒有特別的限制， 可使用一般廣泛使用的附攪拌機之混合槽。混合槽的材質 可爲不銹鋼等的具有耐過氧化氫性者。 調製本發明的淨化劑之程序係沒有限制，可採用在過 氧化氫水溶液中添加檸檬酸及/或檸檬酸鹽，接著添加氫 氧化鈉水溶液的方法等。又，本發明的淨化劑係可預先調 合而輸送到淨化地點，也可在淨化地點調合。 本發明的土壤及/或地下水之淨化方法，係將本發明 的淨化劑照原樣地或稀釋而加到土壤及/或地下水中。又 ，於土壤及/或地下水中，以檸檬酸的質子數滿足式（1 )的方式，亦可將各成分分別地加到土壤及/或地下水中 ，以淨化有機化合物所污染的土壤及/或地下水。淨化劑 的添加方法係沒有特別的限制，可使用注入、壓入、噴射 、攪拌、自然擴散、滲透等。又，藉由在與添加位置不同 的位置進行抽吸、減壓，亦可控制添加的速度或方向。 當將本發明的淨化劑稀釋而使用時，可稀釋成任意的 濃度而使用。稀釋劑較佳爲水，亦可以使用含pH緩衝劑 的水溶液。 於將本發明的淨化劑加到土壤及/或地下水中之際， pH較佳爲5〜8，更佳爲5.5〜7。若將pH低的淨化劑加 到土壤及/或地下水中，則導致重金屬的溶出，二次污染 的危險性提高，或有發生地下構造物的鋼筋或地下配管的 -18- 201008606 腐餽之虞。又，如下水道法的基準値所示地，若排水的 pH爲5以下，則有損傷地下構造物之虞。根據此觀點， 淨化劑的pH亦較佳爲5以上。當pH低時，較佳爲以稀 釋劑來調整pH後而使用。 當使用本發明的淨化劑來淨化土壤及/或地下水時， 亦可倂用過渡金屬等的觸媒，進行更快速的淨化。於添加 淨化劑後，亦可添加觸媒，但是當污染爲高濃度時，較佳 0 的形態爲交互添加淨化劑與觸媒。 前述觸媒係從過渡金屬單體、過渡金屬氧化物、過渡 金屬鹽、過渡金屬螯合物所組成族群所選出的至少一種之 過渡金屬化合物，作爲過渡金屬，較佳爲二價的鐵及/或 三價的鐵。更佳可使用硫酸鐵、氯化鐵、氧化鐵、硝酸鐵 、硫化鐵、氫氧化鐵、氧基氫氧化鐵、鐵螯合物等，特佳 爲鐵螯合物。 前述觸媒的形態係沒有特別的限制，可使用水溶液、 Q 懸浮液、粉體、氣溶膠，從操作的簡便性來看較佳爲水溶 液。 用於調製前述螯合物的螯合劑係沒有特別的限制，從 環境負荷的觀點來看較佳爲選擇生物分解性者，例如可使 用下述式（3)所示的雙羧甲基胺系螯合劑。 R-N ( CH2COOX) 2 ( 3 ) (式（3)中，R表示不含氮原子的有機基，X表示Η 或驗金屬）。 作爲前述X的鹼金屬，可舉出鈉（Na)、鉀（κ)等 -19- 201008606 。較佳爲R表示不含氮原子的碳數1〜10之有機基，更佳 表示碳數1〜4之有機基。更佳爲R係不含氮原子的有機 基，表示含有從-COOX及-S03X所組成族群所選出的至少 1個者。特佳爲R係不含氮原子的碳數1〜4之有機基， 表示含有從-COOX及-S03X所組成族群所選出的至少1個 者。 於上述式（3 )所示的雙羧甲基胺系生分解性螯合劑 之中，特佳爲式（3)中的R表示- CH(CH3) COOX、 -CH ( COOH) C2H4COOX、-CH ( COOX) CH2COOX 或 -C2H4S03X ( X係H或鹼金屬）者。 作爲如此的雙羧甲基胺系生物分解性螯合劑之例，可 舉出甲基甘胺酸二乙酸、麩胺酸二乙酸、天冬胺酸二乙酸 、2-胺基乙烷磺酸二乙酸及此等的鈉鹽等。 螯合劑的添加若不足，則發生氫氧化鐵的沈澱，由於 過剩地添加會妨礙淨化，故較佳爲相對於1莫耳的鐵離子 而言使用0.5〜4·0倍之莫耳比的螯合劑。特別地，相對於 1莫耳的鐵離子而言，螯合劑爲1.0〜2_0倍的莫耳比時， 螯合劑的添加效果高而較宜。觸媒水溶液的螯合劑濃度較 佳爲 50 〜20000mg/L。 爲了抑制土壤及/或地下水的pH變動，前述觸媒較 佳爲與pH緩衝劑一起使用。作爲pH緩衝劑，較佳爲碳 酸系。作爲碳酸系緩衝劑，可使用碳酸鈉、碳酸鉀、碳酸 鈣、碳酸鎂、碳酸氫鈉、碳酸氫鉀等。其中，從成本或溶 解度、pH的觀點來看，宜單獨使用碳酸氫鈉，或倂用碳 -20- 201008606 酸氫鈉與碳酸鈉。作爲pH緩衝劑，使用硼酸或磷酸者係 有由於硼酸或磷酸而造成地下水的污染之虞，醋酸係有妨 礙芬頓反應之虞，故不宜。淨化對象的pH若在5〜10的 範圍，則即使發生pH的降低，也未必需要添加pH緩衝 劑，但是爲了縮短淨化期間，宜添加pH緩衝劑以控制在 p Η 7 〜9。 本發明係可應用於原位置淨化及/或場外的二次處理 。又，藉由使用本發明的淨化劑當作氧源及/或營養源， 在進行生物整治（bioremediation)處理的土壤及/或地 下水之淨化處理中亦可利用。 〔實施例〕 接著顯示實施例來更具體說明本發明。惟本發明不受 以下的實施例所限制。再者，過氧化氫的濃度係經由過錳 酸鉀滴定法來求得。 ❹ <實施例1 > 使FeS〇4 · 7H20 (和光純藥（股）製特級試藥）溶解 在純水中，調製模擬地下水。於3 5重量％過氧化氫水溶液 (三菱瓦斯化學（股）製工業用）中，添加相對於100重 量份的過氧化氫而言20重量份的檸檬酸（無水）（小宗 化學藥品（股）製特級試藥）、鹼與檸檬酸的莫耳比成爲 氫氧化鈉/檸檬酸=2.85/ 1(莫耳比）之氫氧化鈉（和光 純藥（股）製特級試藥）、及純水（相對於過氧化氫與檸 -21 - 201008606 檬酸的添加量的合計100重量份而言568重量份），使溶 解而調製淨化劑（相對於過氧化氫與檸檬酸之添加量的合 計100重量份而言含水量723重量份）。以過氧化氫濃度 成爲1.0重量％、Fe離子濃度成爲25mg/kg的方式，將 模擬地下水及淨化劑混合，置入三角燒瓶內，在50°C的恆 溫水槽中靜置24小時。由靜置前後的過氧化氫濃度來比 較過氧化氫的安定性。表1中顯示其結果。 <比較例1 > 除了代替實施例1的檸檬酸（無水），使用DL-酒石 酸（關東化學（股）製特級試藥），鹼與酒石酸的莫耳比 成爲氫氧化鈉/酒石酸=1.95/ 1以外，與實施例1同樣地 調製淨化劑。但是相對於過氧化氫與檸檬酸的添加量之合 計1〇〇重量份而言，純水的追加添加量爲567重量份，調 整後的淨化劑中之含水量爲722重量份。以過氧化氫濃度 成爲1.0重量％、Fe離子濃度成爲25mg/kg的方式，將 模擬地下水及淨化劑混合，置入三角燒瓶內，在50°C的恆 溫水槽中靜置24小時。由靜置前後的過氧化氫濃度來比 較過氧化氫的安定性。表1中顯示其結果。 <比較例2 > 除了代替實施例1的檸檬酸（無水），使用DL-蘋果 酸（關東化學（股）製特級試藥），鹼與蘋果酸的莫耳比 成爲氫氧化鈉/蘋果酸=1.95/1以外，與實施例1同樣地 -22- 201008606 調製淨化劑。但是相對於過氧化氫與檸檬酸的 計1 〇 〇重量份而言，純水的追加添加量爲5 6 5 整後的淨化劑中之含水量爲7 2 0重量份。以過 成爲1.〇重量％、Fe離子濃度成爲25mg/kg 模擬地下水及淨化劑混合，置入三角燒瓶內，： 溫水槽中靜置24小時。由靜置前後的過氧化 較過氧化氫的安定性。表1中顯示其結果。 加量之合 量份，調 化氫濃度 方式，將 5 0 °C的恆 濃度來比201008606 VI. Description of the Invention [Technical Field] The present invention relates to a soil and/or groundwater purification agent contaminated with an organic compound, and a purification method using the same. [Prior Art] The influence of organic matter pollution in soil and groundwater on the environment becomes obvious. With the preparation of various regulations, the purification system of pollution accumulated and placed so far becomes necessary. The organic system herein mainly refers to an organic substance which is difficult to be biodegraded, and corresponds to an aromatic compound, a toothed organic compound, and the like contained in a pesticide, a preservative, petroleum, and a fraction thereof. For this organic contamination, try various physical, chemical, and biological purification methods. In terms of physical purification methods, although the purification of contaminated sites is possible, there is a need to reprocess the removed pollutants. Although the biological purification method is a method that has little influence on the surrounding environment, Q has a disadvantage that it is difficult to apply to high-concentration pollution. In contrast, the chemical purification method is characterized in that it does not require secondary treatment because it decomposes the target pollutant, and it is also applicable to high-concentration pollution. It is known that by adding an oxidizing agent such as hydrogen peroxide or a compound capable of supplying an iron ion (for example, ferrous sulfate heptahydrate or the like) as a catalyst, a hydroxyl radical is generated to cause the radical to react with an organic substance. A Fenton method that oxidatively decomposes organic matter. Among the chemical purification methods, the Fenton method is attempted to purify the soil contaminated with the organic compound (refer to Patent Document 1). -5- 201008606 It is said that the most suitable pH range of the usual Fenton method is 3 to 4. In the reaction in which the pH range is neutral or higher, the iron ions of the catalyst become hydroxide and precipitate, and almost no reaction occurs. When the pH is most suitable in the pH range of pH 3 to 4, the dissolution of heavy metals in the soil may cause the occurrence or expansion of secondary pollution, and the corrosion of the steel or underground piping of the underground structure may occur. In order to compensate for this drawback, it has been proposed to use a buffer to purify at a certain pH near neutral. In Patent Documents 2 and 3, in order to prevent pH drop caused by decomposition of contaminated organic matter, the addition of an oxidizing agent and a buffer is designed, but the precipitation of metal ions of a catalyst for preventing iron or the like in a high pH range is not disclosed. In the meantime, depending on the type of the oxidant or the environment of the purification site, the clogging of the flow path and the piping may occur due to the precipitation of the metal component contained in the groundwater such as iron, which may cause problems in the purification operation. Further, in order to prevent precipitation of metal ions of a catalyst such as iron, a technique of adding an oxidizing agent and a chelating agent has been devised. In Patent Document 4, the chelating agent is added mainly for the purpose of preventing precipitation of iron. However, since the pH range used is on the acidic side, the range of the prescribed molar ratio is 1/3 for iron. A small amount of the left and right, if the pH range of the liquid is considered, the risk of secondary pollution such as elution of heavy metals remains. Further, in Patent Document 5, a chelating agent and an oxidizing agent are designed, but the purpose of the chelating agent is to prevent precipitation of metal ions such as iron, and there is no means for preventing pH reduction due to a buffer or the like. When the pH range of the liquid is considered, the possibility of secondary pollution caused by elution of heavy metals or the like is high. -6 - 201008606 In this regard, there is also a method of adding a Fe chelate near neutral. Patent Document 6 proposes a method of injecting an oxidant first and then injecting an F e integrator. However, there is no means to prevent pH reduction caused by the oxidant added at first. In hydrogen peroxide which is a preferred oxidizing agent, the pH of the site is lowered by 1 to 4 because of the addition of a phosphate stabilizer. The possibility of secondary pollution such as dissolution of heavy metals may occur. . φ Further, Patent Document 6 discloses a method of simultaneously injecting an oxidizing agent and a Fe chelating agent. However, in the case where the oxidizing agent and the Fe chelate are simultaneously injected, the oxidizing agent starts to decompose at the same time as the mixing, and there is a disadvantage that the oxidizing agent cannot be reached at a place away from the injection place. Patent Document 7 discloses a method in which a biodegradable chelating agent is added to a ground together with a pH buffering agent to form a complex with iron in the ground, and the pH of the working site is maintained at 5 to 10 to add an oxidizing agent. However, in this method, hydrogen peroxide, which is a preferred oxidizing agent, is added under the catalyst, so that there is a disadvantage that the oxidizing agent cannot be reached at a place where it is left. Further, in the above-mentioned Patent Documents 2, 3, and 5 to 7, in order to control the pH of any workplace, pH is used, and it is necessary to mix an oxidizing agent, a catalyst solution, and a pH buffer at a purification site. [Patent Document 1] JP-A-2004-202357 (Patent Document 3) JP-A-2004-205959 (Patent Document 4) JP-A-2002-159959 [Patent Document 5] Japanese Laid-Open Patent Publication No. 2000-3 0 1 1 (Patent Document 6) Japanese Patent No. 3 793 〇 84 (Patent Document 7) WO2006- 1 23 574 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The present invention has been made in view of various problems of the prior art as described above, and aims to provide a soil which is not contaminated by the surrounding environment, the ecosystem, etc., and can be easily applied to the soil contaminated with organic compounds in the original position and/or Or a method of groundwater, and it can safely and effectively purify a wide range from the place of injection to a relatively distant place, and a purifying agent for purifying the treated soil and/or groundwater for high-concentration pollution, and using the purifying agent Soil and/or groundwater purification methods. Means for Solving the Problems In order to solve the above problems, the inventors of the present invention have focused on the above-mentioned problems, and as a result, have found a purifying agent of the present invention containing an aqueous solution of hydrogen peroxide, citric acid, water, and citric acid having a reduced number of protons. (1) Even if it is added to soil and/or groundwater, the pH of the action site changes little, and (2) even if the purifying agent is diluted before being added to the soil and/or groundwater, the pH is near neutral. It is safer, and (3) the stability of hydrogen peroxide in the workplace is good. Furthermore, it has been found that by adding the purifying agent of the present invention to the soil and/or groundwater contaminated by organic matter as a stock solution or dilution, it is not necessary to prepare a pH buffer, and heavy metals are not dissolved. -8- 201008606 The invention can be completed by purifying a wide range. That is, the present invention relates to a soil and/or groundwater purifying agent shown below, and a method of purifying soil and/or groundwater. <1> A soil and/or groundwater purifying agent comprising: (A) 100 parts by weight of hydrogen peroxide, (B) at least 10 parts by weight of citric acid, and φ (C) by (A) When the total of hydrogen peroxide and (B) citric acid is 100 parts by weight, at least 15 parts by weight of water, and (D) an alkali compound is added for satisfying the number of protons of citric acid (B) of the following formula, lemon The number of protons of acid (B) = 〇.〇5χΜ~0·80χΜ (1) (In the formula (1), Μ represents the molar number of citric acid (Β)). < 2 > The soil and/or groundwater purification agent according to the above <1>, wherein a hydrogen peroxide solution having a hydrogen peroxide content of 60% by weight or less is used as Q. <3> The soil and/or groundwater purifying agent according to the above <1>, wherein a hydrogen peroxide aqueous solution having a hydrogen peroxide content of 30 to 43% by weight is used. The soil and/or groundwater purifying agent according to any one of the above-mentioned items, wherein the alkali compound is derived from an alkali metal hydroxide, an alkali metal oxide or an alkali metal. One or more compounds selected from the group consisting of oxides, alkaline earth metal hydroxides, alkaline earth metal oxides, alkaline earth metal peroxides, ammonia, amines, and quaternary ammonium hydroxide-9-201008606 ammonium. < 5 > A method for purifying soil and/or groundwater, which is a method for purifying soil and/or groundwater contaminated by an organic compound, characterized by adding (A) 100 parts by weight of hydrogen peroxide, (B) At least 10 parts by weight of citric acid, and (C) at least 15 parts by weight of water, and (D) a base compound, when 100 parts by weight of (A) hydrogen peroxide and (B) citric acid are combined, The number of protons used to satisfy the citric acid (B) of the following formula, the number of protons of citric acid (B) = 0_05 χΜ ~ 0 · 80 χΜ (2) (In the formula (2), Μ represents the molar number of citric acid (Β) ). [6] The method for purifying soil and/or groundwater according to the above <5>, wherein the alkali compound is oxidized from an alkali metal hydroxide, an alkali metal oxide, an alkali metal peroxide, or an alumina metal. One or more compounds selected from the group consisting of a substance, an alkaline earth metal oxide, an alkaline earth metal peroxide, ammonia, an amine, and a quaternary ammonium hydroxide. The method for purifying soil and/or groundwater according to any one of <5>, wherein the (A), ((), (C), and (D) are prepared in advance. A purifying agent, which is added as a stock solution or diluted. The method for purifying soil and/or underground-10-201008606 water according to any one of the above-mentioned <5>, wherein, in (A), (B), (C) and After the addition of (D), at least one selected from the group consisting of a transition metal monomer, a transition metal oxide, a transition metal salt, and a transition metal chelate is added to the soil and/or groundwater. <9> The method for purifying soil and/or groundwater according to the above <8>, wherein the transition metal is ferrous iron and/or ferric iron. The method for purifying soil and/or groundwater according to any one of the above-mentioned items, wherein the transition metal chelate compound is a double represented by the following formula (3). A carboxymethylamine-based chelating agent, RN (CH2COOX) 2 (3) (in the formula (3), R represents an organic group containing no nitrogen atom, and X represents an anthracene or an alkali metal). < 1 1 > The method for purifying soil and/or groundwater according to the above <1>, wherein R in the above formula (3) is -CH(CH3)COOX, •CH(COOH)C2H4COOX, - CH (COOX) CH2COOX or -C2H4S03X (X-based H or alkali metal). <12> The method for purifying soil and/or groundwater described in the above <8>~<11>, wherein the addition is composed of a transition metal monomer, a transition metal oxide, a transition metal salt, and a transition metal chelate compound. At least one selected from the group and a pH buffer. The method for purifying soil and/or groundwater described in the above <5> to <12>, wherein the soil and/or groundwater is purified at the original position. < 1 4 > The method for purifying soil and/or groundwater according to the above <5> to <13>, wherein (A) ' ( B ) is added to the soil and/or groundwater subjected to the bioremediation treatment, (C) and (D). EFFECTS OF THE INVENTION The method for purifying soil and/or groundwater by the purifying agent of the present invention has the following effects. (1) Since a hydrogen peroxide aqueous solution which is stabilized in the vicinity of neutral is added, heavy metals are not eluted, and hydrogen peroxide can be reached at a distance from the injection site, thereby expanding the purification range of the soil and/or groundwater. (2) Since a hydrogen peroxide aqueous solution which is stabilized in the vicinity of neutral is added, decomposition of hydrogen peroxide which is not associated with purification can be prevented, and hydrogen peroxide can be utilized efficiently. (3) Since the transition metal ions such as iron are added while keeping the soil and/or groundwater near neutral, the heavy metals are not dissolved, and the organic compounds of the pollution source can be decomposed. (4) Since a thick aqueous solution of hydrogen peroxide mixed with a pH buffer can be prepared in advance, it is not necessary to adjust the cooperation at the purification site, and it can be easily used. Therefore, according to the present invention, the surrounding environment, the ecosystem, and the like are not affected, and the soil and/or groundwater contaminated by the organic compound -12-201008606 can be safely and effectively purified in the original position. [Embodiment] The best mode for carrying out the invention The soil and/or groundwater of the object to be purified according to the present invention is contaminated with organic matter. Examples of the organic substance include a pesticide, a preservative, an aromatic compound contained in petroleum and a fraction thereof, a halogenated hydrocarbon, and the like. Examples of the aromatic compound contained in the petroleum and Φ fractions include toluene and benzene. Examples of the organic chlorine compound include trichloroethylene (TCE) and tetrachloroethylene (PCE). The hydrogen peroxide used in the present invention is not particularly limited, and an industrial hydrogen peroxide aqueous solution is preferably used. The concentration of hydrogen peroxide in the aqueous hydrogen peroxide solution for industrial use is not particularly limited. However, since it is difficult to obtain a hydrogen peroxide aqueous solution having a concentration higher than 60% by weight, it is preferably 60% by weight or less, more preferably not An aqueous hydrogen peroxide solution having a concentration of 45% by weight or less of a dangerous substance is preferably an aqueous hydrogen peroxide solution having a hydrogen peroxide concentration of 30% by weight or more from the viewpoint of transportation cost. The scavenger of the present invention contains citric acid for the purpose of stabilizing hydrogen peroxide under neutral conditions and imparting a pH buffering agent. The citric acid used in the present invention may be any of industrial, pharmaceutical, food, and pharmacopoeia. Aqueous solutions, hydrates, anhydrides and the like can be used. In the purifying agent of the present invention, the lower limit of the citric acid concentration is affected by the amount of iron in the soil and/or groundwater of the object to be purified, but at least 10 in terms of 100 parts by weight of hydrogen peroxide relative to -13 to 201008606. Parts by weight. When the citric acid is less than 10 parts by weight, the stability of hydrogen peroxide is lowered in the usual soil and/or groundwater, and the purification range is narrowed. The citric acid is more preferably compounded in an amount of 10 to 50 parts by weight based on 100 parts by weight of hydrogen peroxide. In the purifying agent of the present invention, if necessary, it may further contain a stabilizer other than citric acid as a stabilizer (for example, 8-hydroxyquinoline, 1,10-phenanthroline, benzotriazole, urea, tetra Grade ammonium salts, pyrrolidone carboxylic acids, aliphatic amines, nitro compounds, sulfanilic acids, alcohols, phenols, phenyl glycol ethers, carboxylic acid 'alcoholamines, amine carboxylates, alkyds, salicylic acid, Alpha-ketocarboxylates, aldehyde-carboxylates, citrates, stannates, molybdenum, zirconium and hafnium, phytic acid 'sulfites, sulfur-based stabilizers, industrial hydrogen peroxide solutions Added phosphoric acid stabilizer)). The purifying agent of the present invention contains at least 15 parts by weight of water with respect to 100 parts by weight of the total of hydrogen peroxide and citric acid. If the water content is less than this, citric acid and/or citrate will precipitate, and the composition of the scavenger may be unstable. Further, when an industrial hydrogen peroxide aqueous solution is used, the water content is considered to include water previously contained in the industrial hydrogen peroxide aqueous solution. A more desirable content of water is from 160 to 2000 parts by weight. In the purifying agent of the present invention, in addition to hydrogen peroxide and citric acid, an alkali compound is also blended. The blending of the alkali compound is to adjust the number of protons of citric acid contained in the purifying agent. The hydrogen atom and the hydrogen ion derived from the acid group of citric acid are referred to as protons, and the number of protons indicates the sum of the sum of hydrogen atoms and hydrogen ions derived from the acid groups of the citric acid. Since citric acid has three carboxyl groups, -14-201008606 When no alkali compound is added, the proton number of citric acid of the purifying agent is three times that of the theoretically mixed citric acid. Here, when citric acid and an alkali compound are blended in the purifying agent, a hydrogen atom and a hydrogen ion (proton) derived from a carboxyl group of citric acid in the purifying agent are consumed by reaction with a cation of the alkali compound. It is reduced by the amount of the base compound added. That is, when citric acid and an alkali compound are added to the purifying agent of the present invention, the number of protons of citric acid in the purifying agent is lowered in accordance with the amount of addition of the alkalizing compound. As described above, when the alkali compound is not added, the number of protons of citric acid in the purifying agent is three times that of the theoretically blended citric acid, but in the present invention, it is important to make the scavenger The number of protons in citric acid is in a certain range less than the theoretical enthalpy. In the present invention, the number of protons of the citric acid contained in the purifying agent is adjusted by the alkali compound so as to satisfy the formula (1). The number of protons of citric acid (B) = 〇 · 〇 5 χΜ ~ 0.80 x M ( 1 ) Q (In the formula (1), Μ represents the molar number of citric acid (Β) in the purifying agent). The number of protons of citric acid in the purifying agent of the formula (1) of the present invention is the sum of hydrogen atoms and hydrogen ions derived from the acid group of citric acid contained in the purifying agent. In the present invention, by adjusting the amount of the alkali compound added to the scavenger, the number of protons of citric acid in the purifying agent can be adjusted so as to satisfy the formula (1), for example, when the molar number of citric acid is 1 mol. Since the proton number of citric acid calculated by the formula (1) ranges from 0.05 to 0.80, when an alkali metal hydroxide of a monovalent cation such as hydrogen-15-201008606 sodium oxide is added as a test compound, The addition of 2.20 to 2.95 moles of the base compound as shown in the following formula can be the most suitable range of proton number of citric acid. Μχ3-Αι=Μχ (0.05 to 0.80) A!=Mx[3-(0.05 to 0.80)] = Μχ[2·95 ～2.20] (In the above formula, Μ indicates the molar number of citric acid to be blended; The number of moles of the test compound indicating the complexed monovalent cation). Further, when an alkaline earth metal hydroxide of a divalent cation such as magnesium hydroxide is added, the base compound represented by the following formula is added in an amount of 1.10 to 1.475 mol to obtain the most suitable proton of citric acid. Number range. Μχ3-Α2χ2 = Μχ (0.05~0.80) Α2χ2 = Μχ[ 3-( 0.05~0.80 )] Α2 = Μχ [ 2.95-2.20 ] —2 = Μχ [ 1 .475~1 · 1 〇] (In the above formula, Μ The number of moles of citric acid to be blended is shown. 八 2 represents the molar number of the alkali compound of the divalent cation to be compounded). Further, the range of the amount of the alkali compound added to the cation having a trivalent or higher valence can be determined in the same manner as described above. Further, an alkali compound of a monovalent cation and an alkali compound of a divalent cation may be combined. In this case, the ratio of the two may be appropriately selected so that the number of protons of citric acid is within the range defined by the formula (1). When the number of protons of citric acid contained in the purifying agent is larger than the range defined by the formula (1), the pH at the time of diluting the purifying agent becomes too low, the risk of the operator becomes high, and the risk of corrosion of the use machine becomes high. . Furthermore, when added to soil and/or groundwater and diluted by groundwater, the pH becomes too low. -16- 201008606 Causes the dissolution of heavy metals and increases the risk of secondary pollution. If the number of protons of citric acid is less than the range specified by formula (1), the pH buffering capacity after dilution of the purifying agent is weakened, the decomposition of hydrogen peroxide is rapidly increased, or the dissolution of heavy metals or arsenic is caused by two. The risk of secondary pollution has increased. The alkali compound used for the adjustment of the proton number of citric acid of the present invention is a compound which exhibits a basicity in an aqueous solution, preferably an alkali metal hydroxide, an alkali metal oxide, an alkali metal peroxide or an alkali metal hydroxide. One or more compounds selected from the group consisting of alkaline earth metal oxides, alkaline earth metal peroxides, ammonia, amines, and tetraammonium hydroxide. As the alkali metal hydroxide, sodium hydroxide, potassium hydroxide or lithium hydroxide is preferred. As the alkali metal oxide, sodium oxide, potassium oxide or lithium oxide is preferred. As the alkali metal peroxide, sodium peroxide, potassium peroxide or lithium peroxide is preferred. As the alkaline earth metal hydroxide, magnesium hydroxide or calcium hydroxide is preferred. As the alkaline earth metal oxide, magnesium oxide or calcium oxide is preferred. @ is an alkaline earth metal peroxide, preferably magnesium peroxide or calcium peroxide. As the amine, preferred are methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, diisopropylamine, second butylamine and thiramine. As the quaternary ammonium hydroxide, tetramethylammonium hydroxide is preferred, and more preferably one or more compounds selected from sodium hydroxide, potassium hydroxide, magnesium hydroxide and ammonia. The purifying agent of the present invention may contain a neutral salt as long as it is prepared so as to satisfy the above formula (1). The neutral salt is preferably a positive salt formed by neutralizing a strong acid with a strong base, and examples thereof include sodium chloride, potassium chloride, chlorine-17-201008606 magnesium, calcium chloride, sodium sulfate, and potassium sulfate. , magnesium sulfate, sodium nitrate, potassium nitrate, and the like. The apparatus for modulating the purifying agent of the present invention is not particularly limited, and a mixing tank with a mixer which is generally widely used can be used. The material of the mixing tank may be hydrogen peroxide resistant to stainless steel or the like. The procedure for preparing the purifying agent of the present invention is not limited, and a method of adding citric acid and/or citrate to an aqueous hydrogen peroxide solution followed by adding an aqueous sodium hydroxide solution may be employed. Further, the purifying agent of the present invention may be previously transferred to a purification site or may be blended at a purification site. The method for purifying soil and/or groundwater of the present invention is to add the purifying agent of the present invention to the soil and/or groundwater as it is or diluted. Further, in the soil and/or groundwater, the number of protons of citric acid satisfies the formula (1), and the components may be separately added to the soil and/or groundwater to purify the soil contaminated with the organic compound and/or Or groundwater. The method of adding the scavenger is not particularly limited, and injection, press-in, jetting, stirring, natural diffusion, infiltration, and the like can be used. Further, the speed or direction of addition can be controlled by suctioning and decompressing at a position different from the added position. When the purifying agent of the present invention is diluted and used, it can be diluted to an arbitrary concentration and used. The diluent is preferably water, and an aqueous solution containing a pH buffer may also be used. When the scavenger of the present invention is added to the soil and/or groundwater, the pH is preferably from 5 to 8, more preferably from 5.5 to 7. If a low-purifying purifying agent is added to the soil and/or groundwater, the dissolution of heavy metals may occur, and the risk of secondary pollution may increase, or the reinforcement of the underground structure or the underground piping may be -18- 201008606. . In addition, as shown in the following reference to the waterway method, if the pH of the drainage is 5 or less, the underground structure is damaged. From this point of view, the pH of the scavenger is also preferably 5 or more. When the pH is low, it is preferred to adjust the pH with a diluent to use it. When the purifying agent of the present invention is used to purify soil and/or groundwater, a catalyst such as a transition metal may be used for faster purification. After the addition of the purifying agent, the catalyst may be added, but when the contamination is high, the preferred form of 0 is to add the purifying agent and the catalyst interactively. The catalyst is at least one transition metal compound selected from the group consisting of a transition metal monomer, a transition metal oxide, a transition metal salt, and a transition metal chelate, and as the transition metal, preferably a divalent iron and/or Or a trivalent iron. More preferably, iron sulfate, iron chloride, iron oxide, iron nitrate, iron sulfide, iron hydroxide, iron oxyhydroxide, iron chelate or the like can be used, and an iron chelate compound is particularly preferable. The form of the catalyst is not particularly limited, and an aqueous solution, a Q suspension, a powder, or an aerosol can be used, and an aqueous solution is preferred from the viewpoint of ease of handling. The chelating agent for preparing the chelate compound is not particularly limited, and from the viewpoint of environmental load, it is preferred to select a biodegradable one. For example, a biscarboxymethylamine group represented by the following formula (3) can be used. Chelating agent. R-N (CH2COOX) 2 ( 3 ) (In the formula (3), R represents an organic group containing no nitrogen atom, and X represents ruthenium or a metal test). Examples of the alkali metal of X include sodium (Na), potassium (κ), and the like -19-201008606. Preferably, R represents an organic group having 1 to 10 carbon atoms which does not contain a nitrogen atom, more preferably an organic group having 1 to 4 carbon atoms. More preferably, the R-based organic group containing no nitrogen atom means at least one selected from the group consisting of -COOX and -S03X. Particularly preferred is an organic group having 1 to 4 carbon atoms which does not contain a nitrogen atom, and represents at least one selected from the group consisting of -COOX and -S03X. Among the dicarboxymethylamine-based biodegradable chelating agents represented by the above formula (3), it is particularly preferred that R in the formula (3) represents -CH(CH3)COOX, -CH(COOH)C2H4COOX, -CH (COOX) CH2COOX or -C2H4S03X (X-based H or alkali metal). Examples of such a dicarboxymethylamine-based biodegradable chelating agent include methyl glycine diacetic acid, glutamic acid diacetic acid, aspartic acid diacetic acid, and 2-aminoethane sulfonic acid. Acetic acid and such sodium salts and the like. If the addition of the chelating agent is insufficient, precipitation of iron hydroxide occurs, and since excessive addition hinders purification, it is preferable to use a chelate ratio of 0.5 to 4.0 times the molar ratio with respect to 1 mol of iron ions. mixture. In particular, when the chelating agent is 1.0 to 2_0 times the molar ratio with respect to 1 mole of iron ions, the effect of adding the chelating agent is high and it is preferable. The concentration of the chelating agent in the aqueous solution of the catalyst is preferably from 50 to 20,000 mg/L. In order to suppress the pH fluctuation of the soil and/or groundwater, the above catalyst is preferably used together with a pH buffer. As the pH buffer, a carbonic acid type is preferred. As the carbonic acid buffer, sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate or the like can be used. Among them, from the viewpoints of cost, solubility, and pH, it is preferred to use sodium hydrogencarbonate alone or to use carbon-20-201008606 sodium hydrogencarbonate and sodium carbonate. As a pH buffering agent, it is not preferable to use boric acid or phosphoric acid because of contamination of groundwater by boric acid or phosphoric acid, and acetic acid may hinder the Fenton reaction. When the pH of the object to be purified is in the range of 5 to 10, it is not necessary to add a pH buffer even if the pH is lowered. However, in order to shorten the purification period, a pH buffer should be added to control p Η 7 to 9. The invention is applicable to primary position purification and/or off-site secondary treatment. Further, by using the purifying agent of the present invention as an oxygen source and/or a nutrient source, it can also be used in the purification treatment of soil and/or ground water subjected to bioremediation treatment. [Examples] Next, examples will be shown to more specifically explain the present invention. However, the invention is not limited by the following examples. Further, the concentration of hydrogen peroxide is determined by a potassium permanganate titration method. ❹ <Example 1 > FeS〇4·7H20 (a special grade drug manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in pure water to prepare simulated groundwater. Adding 20 parts by weight of citric acid (anhydrous) to 100 parts by weight of hydrogen peroxide in a 35 wt% aqueous hydrogen peroxide solution (for Mitsubishi Gas Chemical Industries) (small chemical products) ) a special grade test), a molar ratio of alkali to citric acid to sodium hydroxide / citric acid = 2.85 / 1 (mole ratio) sodium hydroxide (Wako Pure Chemical Co., Ltd. special grade test), and pure Water (568 parts by weight based on 100 parts by weight of the total amount of hydrogen peroxide and lemon-21 - 201008606 citric acid added), and dissolved to prepare a purifying agent (total amount of addition of hydrogen peroxide and citric acid) The water content is 723 parts by weight based on 100 parts by weight. The simulated groundwater and the scavenger were mixed so that the hydrogen peroxide concentration was 1.0% by weight and the Fe ion concentration was 25 mg/kg, placed in an Erlenmeyer flask, and allowed to stand in a constant temperature water bath at 50 ° C for 24 hours. The stability of hydrogen peroxide was compared by the concentration of hydrogen peroxide before and after standing. The results are shown in Table 1. <Comparative Example 1 > In place of citric acid (anhydrous) of Example 1, DL-tartaric acid (a special grade reagent manufactured by Kanto Chemical Co., Ltd.) was used, and the molar ratio of alkali to tartaric acid became sodium hydroxide/tartaric acid = 1.95 A purifying agent was prepared in the same manner as in Example 1 except for 1/. However, the amount of pure water added is 567 parts by weight, and the water content in the adjusted purifying agent is 722 parts by weight based on 1 part by weight of the total amount of hydrogen peroxide and citric acid added. The simulated groundwater and the scavenger were mixed so that the hydrogen peroxide concentration was 1.0% by weight and the Fe ion concentration was 25 mg/kg, placed in an Erlenmeyer flask, and allowed to stand in a constant temperature water bath at 50 ° C for 24 hours. The stability of hydrogen peroxide was compared by the concentration of hydrogen peroxide before and after standing. The results are shown in Table 1. <Comparative Example 2 > In addition to the citric acid (anhydrous) of Example 1, DL-malic acid (a special grade reagent manufactured by Kanto Chemical Co., Ltd.) was used, and the molar ratio of alkali to malic acid became sodium hydroxide/apple. In the same manner as in Example 1, except that the acid was 1.95/1, the cleaning agent was prepared in the range of -22 to 201008606. However, the amount of water added to the purifying agent after the addition of pure water is 720 parts by weight based on 1 part by weight of hydrogen peroxide and citric acid. The mixture was mixed with 1.5% by weight, and the Fe ion concentration was changed to 25 mg/kg. The simulated groundwater and the scavenger were mixed and placed in a conical flask. The mixture was allowed to stand in a warm water bath for 24 hours. Peroxidation before and after standing is more stable than hydrogen peroxide. The results are shown in Table 1. The amount of the combined amount, the hydrogen concentration is adjusted, and the constant concentration of 50 °C is compared.
-23- 201008606 I嗽 (備註） 較佳的質子數範圍※ 0.04-0.67 0.05-0.85 0.06-0.95 有無Fe 沈澱 無沈澱 無沈澱 無沈澱 過氧化氫 殘存率 93.0% 0.0% 1.4% «1 i S _ 翻 m Os Ο 0.000重量％ 0-014重量％ 初期過氧化 氮濃度 1.00重量％ 1.〇〇重量％ 1.00重量％ 24小時靜 置後的pH 00 00 卜’ 初期 PH 寸 VO 〇\ 安定化劑 的質子數 0.13 0.05 0.06 氫氧化鈉 的莫耳數 I m 00 (N 1 Β S ο (Ν 2.328mmol 安定化劑的 莫耳數 I B m m 00 O ·—( 疆 00 VO ρ 1.1937mmol 安定化劑 檸檬酸 酒石酸 蘋果酸 實施例1 比較例1 比較例2 醒爝sMrfMNi敏.Λ3>嵌俶s53«^(I)悄«製长谳：醒爝鏑屮鎰※ -24- 201008606 實施例1的結果顯示檸檬酸將過氧化氫在中性附近安 定化。相對地，比較例1及比較例2的結果顯示酒石酸及 蘋果酸無法將過氧化氫在中性附近安定化。 <比較例3 > 除了鹼與檸檬酸的莫耳比爲氫氧化鈉/檸檬酸=3.00 / 1以外，於與實施例1相同的條件下調製淨化劑（相對 0 於過氧化氫與檸檬酸的添加量之合計100重量份而言純水 的追加添加量爲568重量份，淨化劑中的含水量爲723重 量份），比較過氧化氫的安定性。表2中顯示其結果。 -25- 201008606 (備註） 較佳的質子數範圍※ 0.04-0.67 0.04-0.67 過氧化氫 殘存率 93.0% 0.5% _翠 f喪!瓣 S 0.93重量％ 0.006重量％ 初期過氧化 氫濃度 1.00重量％ 1.05重量％ 24小時靜 置後的pH 00 'Ο OS 初期 PH 寸 ^0 rn 棒檬酸的 質子數 0.13 0.00 氫氧化鈉 的莫耳數 2.383mmol 謹 S r4 棒檬酸的莫 耳數 0.8363mmol 1 s rn 2 〇 氫氧化鈉 /棒檬酸 (莫耳比) 2.85/1 3.00/1 實施例1 比較例3 醒 s 親 •N 氍 mt s 93 輙 觀 撇 醒 iS •ΟΒΓ 顯 屮1» 鎰 ※-23- 201008606 I嗽(Remarks) Preferred proton number range ※ 0.04-0.67 0.05-0.85 0.06-0.95 With or without Fe Precipitation No precipitation No precipitation No precipitation Hydrogen peroxide Residual rate 93.0% 0.0% 1.4% «1 i S _ Turn m Os 0.000 0.000% by weight 0-014% by weight Initial nitrogen peroxide concentration 1.00% by weight 1. 〇〇 Weight % 1.00% by weight pH after 24 hours of standing 00 00 卜 'Initial PH inch VO 〇\ stabilizer Number of protons 0.13 0.05 0.06 Molar number of sodium hydroxide I m 00 (N 1 Β S ο (Ν 2.328mmol molar amount of amylating agent IB mm 00 O ·—( Xinjiang 00 VO ρ 1.1937mmol stabilizer citric acid Tartrate Malic Acid Example 1 Comparative Example 1 Comparative Example 2 Awake sMrfMNi Sensitive. Λ3> Embedding s53 «^(I) ««制长谳: Awake 爝镝屮镒 ※ -24- 201008606 The results of Example 1 show lemon The acid stabilized hydrogen peroxide in the vicinity of neutrality. In contrast, the results of Comparative Example 1 and Comparative Example 2 showed that tartaric acid and malic acid could not stabilize hydrogen peroxide in the vicinity of neutrality. <Comparative Example 3 > In addition to alkali The molar ratio to citric acid is other than sodium hydroxide / citric acid = 3.00 / 1 The purifying agent was prepared under the same conditions as in Example 1 (additional amount of pure water was 568 parts by weight based on 100 parts by weight of the total amount of hydrogen peroxide and citric acid added, and the water content in the purifying agent) The stability of hydrogen peroxide was compared with 723 parts by weight. The results are shown in Table 2. -25- 201008606 (Remarks) Preferred range of protons ※ 0.04-0.67 0.04-0.67 Residual rate of hydrogen peroxide 93.0% 0.5% _翠f funnel! Petal S 0.93 wt% 0.006 wt% initial hydrogen peroxide concentration 1.00 wt% 1.05 wt% pH after 24 hours of standing 00 'Ο OS initial PH inch ^0 rn proton number of citrate 0.13 0.00 hydrogen Molar number of sodium oxide 2.383 mmol Sr4 molar number of citric acid 0.8363 mmol 1 s rn 2 〇 sodium hydroxide / citrate (mol ratio) 2.85/1 3.00/1 Example 1 Comparative Example 3 s 亲·N 氍mt s 93 輙观撇醒 iS •ΟΒΓ 显屮1» 镒※
-26- 201008606 實施例1的結果顯示當藉由鹼化合物來調整而滿足本 發明的檸檬酸之質子數時，過氧化氫被安定化。相對於此 ，比較例3的結果顯示當不滿足本發明的檸檬酸之質子數 時，過氧化氫未被安定化。 <實施例2〜5 > 於3 5重量％過氧化氫水溶液（三菱瓦斯化學（股）製 _ 工業用）中，添加相對於100重量份的過氧化氫而言2〇 重量份的檸檬酸（無水）（小宗化學藥品（股）製特級試 藥）、氫氧化鈉及純水，使溶解而調製淨化劑。淨化劑中 的鹼與檸檬酸的莫耳比係氫氧化鈉/檸檬酸=2 ·95〆1〜 2.2 0 / 1。所追加添加的純水量及淨化劑中的含水量係如 表3所示。表3中顯示所調製的淨化劑之pH。 <比較例4 > 參 除了鹼與檸檬酸的莫耳比爲氫氧化鈉/檸檬酸=2.10 / 1以外，與實施例2〜5同樣地調製淨化劑。所追加添加 的純水量及淨化劑中的含水量係如表3所示°表3中顯示 所調製的淨化劑之pH。 -27- 201008606 ε嗽 淨化劑的含水量 (重量份） ※※ m CN CN 726 726 純水追加添加量 (重量份） ※※ 00 \〇 569 569 卜 (備註） 較佳的質子數範圍※ 0.28-4.45 0.39-6.28 0.28-4.53 0.12-1.94 0.14-2.31 淨化劑 的pH vd 5 〇 in On 檸檬酸的 質子數 0.28 1.18 1.98 1.93 2.60 氫氧化鈉的 莫耳數 1 ε 荽 cn i cn (N <N 14.998mmol 5.327mmol 6.069mmol 檸檬酸的莫 耳數 I B cn vn in 謹 o ΙΓϊ 00 5.6597mmol 2.4215mmol 2.8901mmol 氫氧化鈉 /檸檬酸 (莫耳比) 2.95/1 2.85/1 2.65/1 2.20/1 2.10/1 實施例2 實施例3 實施例4 實施例5 比較例4 醒爝S鎰屮M^l饀繼«:£33«矻(1)悄«鍵长撇：醒蘚鎰屮Ms·鎰※ ffllM輅δ#0φ}_®οοι嘘4-1啦S趑職爨鄯碱^嫲頰^※※ -28- 201008606 實施例2〜5及比較例4的結果顯示當檸檬酸的質子 數滿足本發明的範圍時，淨化劑的pH成爲5.0以上’淨 化劑的pH係合適。 <實施例6 > 使FeS04 · 7H20 (和光純藥（股）製特級試藥）溶解 在純水中，調製模擬地下水。於3 5重量％過氧化氫水溶液 Φ (三菱瓦斯化學（股）製工業用）中，添加相對於100重 量份的過氧化氫而言1 〇〇重量份的檸檬酸（無水）（小宗 化學藥品（股）製特級試藥）、鹼與檸檬酸的莫耳比成爲 氫氧化鈉/檸檬酸=2.85/ 1 (莫耳比）之氫氧化鈉（和光 純藥（股）製特級試藥）、及純水（相對於過氧化氫與檸 檬酸的添加量的合計100重量份而言278重量份），使溶 解而調製淨化劑（相對於過氧化氫與檸檬酸之添加量的合 計100重量份而言含水量3 70重量份）。 〇 以過氧化氫濃度成爲1.0重量％、Fe離子濃度成爲 2 5mg/ kg的方式，將模擬地下水及淨化劑混合，置入三 角燒瓶內，在5 0 °C的恆溫水槽中靜置2 4小時。由靜置前 後的過氧化氫濃度來比較過氧化氫的安定性。表4中顯示 其結果。 <實施例7 > 除了相對於1〇〇重量份的過氧化氫而言使實施例6的 檸檬酸的含量成爲50重量份的檸檬酸以外，與實施例6 -29- 201008606 同樣地調製淨化劑（相對於過氧化氫與檸檬酸的添加量的 合計1 〇〇重量份而言純水的追加添加量爲43 3重量份，淨 化劑中的含水量爲559重量份）。以過氧化氫濃度成爲 1.0重量％、Fe離子濃度成爲25mg/ kg的方式，將模擬地 下水及淨化劑混合，置入三角燒瓶內，在50°C的恆溫水槽 中靜置24小時。由靜置前後的過氧化氫濃度來比較過氧 化氫的安定性。表4中顯示其結果。 <實施例8 > 除了相對於1〇〇重量份的過氧化氫而言使實施例6的 檸檬酸的含量成爲20重量份的檸檬酸以外，與實施例6 同樣地調製淨化劑（相對於過氧化氫與檸檬酸的添加量的 合計100重量份而言純水的追加添加量爲5 69重量份，淨 化劑中的含水量爲723重量份）。以過氧化氫濃度成爲 1.0重量％、Fe離子濃度成爲25mg/kg的方式，將模擬地 下水及淨化劑混合，置入三角燒瓶內，在5 0 °C的恆溫水槽 中靜置24小時。由靜置前後的過氧化氫濃度來比較過氧 化氫的安定性。表4中顯示其結果。 <實施例9 > 除了相對於1〇〇重量份的過氧化氫而言使實施例6的 檸檬酸的含量成爲10重量份的檸檬酸以外，與實施例6 同樣地調製淨化劑（相對於過氧化氫與檸檬酸的添加量的 合計1〇〇重量份而言純水的追加添加量爲636重量份，淨 -30- 201008606 化劑中的含水量爲804重量份）。以過氧化氫濃度成爲 1.0重量％、Fe離子濃度成爲25mg/kg的方式，將模擬地 下水及淨化劑混合，置入三角燒瓶內，在50°C的恆溫水槽 中靜置24小時。由靜置前後的過氧化氫濃度來比較過氧 化氫的安定性。表4中顯示其結果。 <比較例5 > φ 除了相對於100重量份的過氧化氫而言使實施例6的 檸檬酸的含量成爲5重量份的檸檬酸以外，與實施例6同 樣地調製淨化劑（相對於過氧化氫與檸檬酸的添加量的合 計100重量份而言純水的追加添加量爲673重量份，淨化 劑中的含水量爲850重量份）。以過氧化氫濃度成爲1.0 重量％、Fe離子濃度成爲25mg/kg的方式，將模擬地下 水及淨化劑混合，置入三角燒瓶內，在5 0。(：的恆溫水槽中 靜置24小時。由靜置前後的過氧化氫濃度來比較過氧化 Q 氫的安定性。表4中顯示其結果。 <比較例6 > 除了相對於1〇〇重量份的過氧化氫而言使實施例6的 檸檬酸的含量成爲2重量份的檸檬酸以外，與實施例6同 樣地調製淨化劑（相對於過氧化氫與檸檬酸的添加量的合 計1 0 0重量份而言純水的追加添加量爲6 9 8重量份，淨化 劑中的含水量爲880重量份）。以過氧化氫濃度成爲1.0 重量％、Fe離子濃度成爲25mg/kg的方式，將模擬地下 -31 - 201008606 水及淨化劑混合，置入三角燒瓶內，在50 °C的恆溫水槽中 靜置24小時。由靜置前後的過氧化氫濃度來比較過氧化 氫的安定性。表4中顯示其結果。 <實施例1 〇 > 除了代替實施例8的氫氧化鈉，使用氫氧化鉀，鹼與 檸檬酸的莫耳比爲氫氧化鉀/檸檬酸=2.85/ 1 (莫耳比） 以外’與實施例8同樣地調製淨化劑（相對於過氧化氫與 檸檬酸的添加量的合計100重量份而言純水的追加添加量 爲5 6 1重量份，淨化劑中的含水量爲71 6重量份）。以過 氧化氫濃度成爲1.0重量％、Fe離子濃度成爲25mg/ kg 的方式’將模擬地下水及淨化劑混合，置入三角燒瓶內， 在5 0°C的恆溫水槽中靜置24小時。由靜置前後的過氧化 氫濃度來比較過氧化氫的安定性。表4中顯示其結果。 <實施例1 1 > 除了代替實施例8的氫氧化鈉，使用氫氧化鎂，氫氧 化鎂/檸檬酸=1.425 / 1 (莫耳比）以外，與實施例8同 樣地調製淨化劑（相對於過氧化氫與檸檬酸的添加量的合 計100重量份而言純水的追加添加量爲567重量份，淨化 劑中的含水量爲722重量份）。以過氧化氫濃度成爲1.0 重量％、Fe離子濃度成爲25 mg/kg的方式，將模擬地下 水及淨化劑混合，置入三角燒瓶內，在5 (TC的恆溫水槽中 靜置24小時。由靜置前後的過氧化氫濃度來比較過氧化 -32- 201008606 氫的安定性。表4中顯示其結果。 <實施例1 2 > 除了代替實施例8的氫氧化鈉，使用氨，氨/檸檬酸 = 2.85/ 1 (莫耳比）以外，與實施例8同樣地調製淨化劑 (相對於過氧化氫與檸檬酸的添加量的合計1〇〇重量份而 言純水的追加添加量爲568重量份，淨化劑中的含水量爲 ❹ 723重量份）。以過氧化氫濃度成爲1.0重量％、Fe離子 濃度成爲25mg/kg的方式，將模擬地下水及淨化劑混合 ，置入三角燒瓶內，在50°C的恆溫水槽中靜置24小時。 由靜置前後的過氧化氫濃度來比較過氧化氫的安定性。表 4中顯示其結果。 <實施例1 3 > 除了代替實施例8的氫氧化鈉，使用氫氧化鈉及氨， Q 氫氧化鈉/氨/檸檬酸=1.425/1.425/1 (莫耳比）以外 ，與實施例8同樣地調製淨化劑（相對於過氧化氫與檸檬 酸的添加量的合計100重量份而言純水的追加添加量爲 572重量份，淨化劑中的含水量爲727重量份）。以過氧 化氫濃度成爲1.0重量％、Fe離子濃度成爲25mg/kg的 方式’將模擬地下水及淨化劑混合，置入三角燒瓶內，在 50 °C的恆溫水槽中靜置24小時。由靜置前後的過氧化氫 濃度來比較過氧化氫的安定性。表4中顯示其結果。 -33- 201008606 〈實施例1 4 > 除了代替實施例8的氫氧化鈉’使用氫氧化鈉及氫氧 化鎂，氫氧化鈉/氫氧化鎂/檸檬酸=1·42 5/0.713/1 ( 莫耳比）以外，與實施例8同樣地調製淨化劑（相對於過 氧化氫與檸檬酸的添加量的合計1〇〇重量份而言純水的追 加添加量爲5 70重量份，淨化劑中的含水量爲725重量份 )。以過氧化氫濃度成爲1 ·〇重量％、Fe離子濃度成爲 2 5mg/ kg的方式，將模擬地下水及淨化劑混合，置入三 角燒瓶內，在50°C的恆溫水槽中靜置24小時。由靜置前 後的過氧化氫濃度來比較過氧化氫的安定性。表4中顯示 其結果。 -34- 20 8 寸撇 06上1 編0醒 擊1 S 1鎰 0.21 〜3.33 0.10-1.58 0.04 〜0.67 0.02 〜0.33 0.01 〜0.17 0.004〜0.07 0.04 〜0,67 0.04 〜0.68 0.04-0.67 0.04 〜0.67 0.04-0.67 有無Fe 沈澱 1 L無沈澱 無沈澱 無沈澱 無沈澱 無沈澱 無沈澱 無沈澱 無沈澱 無沈澱 無沈澱 過氧化氫 殘存率 1 1 ! 80.8% 87.9% 91.5% 84.5% 22.6% 19.7% 93.4% 81.6% 92.5% 90.2% 1 90.7% 1« 1« ?S s S <N圮 0.81重量％ ilmll ipt oo 00 ο 0.92重量％ 0.85重量％ 0.23重量％ _ 翻 〇 0.93重量％ _ tlmll ιρι] (Nl 00 ο 0.92重量％ _ ®1 On 〇 Os 〇 初期過氧化 氫濃度 1.01重量％ 〇Μ ilmj] 糊 Ο 1—^ 1.01重量％ 1.00重量％ 1.01重量％ LOOMS% 1.00重景％ _ ilmll ρπ] Ο r—Η _ 〇 _ _ O 1.05 軍暈°/〇 24小時靜 置後的pH 卜·· VI 〇 ρ 卜 Ο 00 檸檬酸的 質子數 0.62 0.30 0.13 0.06 0.03 0.01 0.13 0.14 0.13 0.13 0.13 鹼的 莫耳數 11.866mmol 5.622mmol 2.375mmol 1.188mmol 0_593mmol 0.238mmol 2.386mmol 1.202mmol 2.382mmol NaOH 1.189mmol NH3 1.189mmoI NaOH 1.187mmol Mg(0H)2 0.593mmol 邏 氫氧化鈉 氫氧化鈉 氫氧化鈉 氫氧化鈉 氫氧化鈉 氫氧化鈉 氫氧化鉀 氫氧化鎂 减 氫氧化鈉及 氣 氫氧化鈉及 氫氧化鎂 1 檸檬酸的莫 耳數 1 B 寸 VO 1.9728mmol 0.8334mmol 0.4168mmol 0.2082mmol 0.0835mmol 1 ε m 00 ο i ε Ζ ο 1 ε Os in 00 o 1 ε m oo o 0.8329mmol 檸檬酸(重量份) /過氧化氫 (重量份） 100/100 50/100 20/100 10/100 5/100 2/100 20/100 20/100 20/100 20/100 20/100 實施例6 實施例7 實施例8 實施例9 比較例5 比較例6 實施例10 實施例11 實施例12 實施例13 實施例14 醒潁sM-ia-N趑職¾¾¾¾矻(一)悄狃翘长嗽：醒玀鐮屮鲰盈玴鎰※ -35- 201008606 實施例6〜14的結果顯示當淨化劑中含有l〇重量份 以上的檸檬酸時，過氧化氫殘存率高，過氧化氫被安定化 。另一方面，比較例5及比較例6的結果顯示當淨化劑的 檸檬酸低於10重量份時，過氧化氫殘存率顯著降低’過 氧化氫未被安定化，而且看到鐵的沈澱。以上的結果顯示 含有至少1 〇重量份的檸檬酸之中性附近的淨化劑’係適 合作爲能將過氧化氫安定化的淨化劑。 <實施例15〜16> 除了氫氧化鈉與檸檬酸的莫耳比成爲氫氧化鈉/檸檬 酸=2.85/1，添加氯化鈉或硫酸鉀當作中性鹽以外，與實 施例8同樣地調製淨化劑，比較過氧化氫的安定性。中性 鹽與檸檬酸的莫耳比在實施例15中爲氯化鈉/檸檬酸 = 0.5/1，在實施例16中爲硫酸鉀/檸檬酸=0.25/1。又 ，實施例15中相對於過氧化氫與檸檬酸的添加量之合計 100重量份而言，純水的追加添加量爲566重量份，淨化 劑中的含水量爲721重量份，實施例16中相對於過氧化 氫與檸檬酸的添加量之合計1〇〇重量份而言，純水的追加 添加量5 65重量份，淨化劑中的含水量爲720重量份。表 5中顯示其結果。 -36- 201008606 備註） 較佳的質子 數範圍※ 0.04-0.67 0.04-0.67 有無Fe 沈澱 無沈澱 無沈澱 過氧化氫 殘存率 86.3% 85.7% 醎与 ί嫲埘 七S _ 0.91重量％ 0.90重量％ 初期過氧 化氫濃度 1.05重量％ 1.05重量％ 24小時靜 置後的pH 寸 寸 1> 檸檬酸的 質子數 0.13 0.12 鹼的莫耳數 2.376mmol 2.375mmol 中性鹽 氯化鈉 硫酸鉀 檸檬酸的莫 耳數 0.8336mmol 0.8332mmol 檸檬酸(重量份) /過氧化氫 (重量份） 20/100 20/100 實施例15 實施例16 画SS 鐮lfM-N^_»s33»^(I) 拭-ffl鍵长撇：醒玀鏟屮 Ms·鎰※ -37- 201008606 實施例15及實施例16顯示淨化劑含有中性鹽時’過 氧化氫亦被安定化。 〈實施例17〜20> 調製過氧化氫濃度爲6.55重量％、檸檬酸濃度爲 0.65 5重量％、氫氧化鈉濃度爲0.3 89重量％的淨化劑（相 對於過氧化氫與檸檬酸的添加量的合計1〇〇重量份而言純 水的追加添加量爲1 1 1 7重量份，淨化劑中的含水量爲 1286重量份）。又，使純水溶解在Fe化合物中而調製鐵 離子濃度爲0.20重量％的觸媒水溶液。觸媒水溶液的調製 在實施例17中係使FeS04 · 7H20 (和光純藥（股）製特 級試藥）溶解在純水中而調製，在實施例18中係使0.116 克 FeS04 . 7H20、0.209 克 0.5M 硫酸及 0.220 克 BASF 日 本（股）製40重量％甲基甘胺酸二乙酸三鈉鹽（MGDA， 商品名「Trilon Μ (註冊商標）」）溶解在純水中而調製 ，在實施例19中係使0.127克FeS04. 7Η20及0.459克 中部CHELEST (股）製（S, S )-乙二胺二琥珀酸三鈉鹽 (EDDS，商品名「CHELEST EDDS-35」）溶解在純水中 而調製，在實施例20中係使0.130克FeS04· 7H20及 0.183克50重量％葡糖酸水溶液溶解在純水中而調製。 於131mL的管瓶（vial)中，加入l〇〇mL的溶解有 5 3.3mg/ L之濃度的當作揮發性有機化合物之四氯乙烯（ PCE)的模擬污染水、lmL的淨化劑、10mL的碳酸氫鈉/ 碳酸鈉所組合成的緩衝劑（碳酸氫鈉濃度18.7g/L，碳酸 -38- 201008606 鈉濃度0.10g/L) 、lmL的觸媒水溶液、19mL的純水後 ，密閉及在室溫實施淨化試驗。自反應開始起經過一小時 後，藉由頂空氣相層析法來分析反應液，比較PCE分解能 力。表6中顯示其結果。-26- 201008606 The results of Example 1 show that when the number of protons of citric acid of the present invention is satisfied by adjustment with an alkali compound, hydrogen peroxide is stabilized. On the other hand, the results of Comparative Example 3 show that hydrogen peroxide was not stabilized when the number of protons of citric acid of the present invention was not satisfied. <Examples 2 to 5 > In a 35 wt% aqueous hydrogen peroxide solution (manufactured by Mitsubishi Gas Chemical Co., Ltd.), 2 parts by weight of lemon was added with respect to 100 parts by weight of hydrogen peroxide. Acid (anhydrous) (special grade drug for small chemical products), sodium hydroxide and pure water are dissolved to prepare a purifying agent. The molar ratio of the base in the scavenger to the citric acid is sodium hydroxide/citric acid = 2 · 95 〆 1 to 2.2 0 / 1. The amount of pure water added and the water content in the purifying agent are shown in Table 3. The pH of the prepared scavenger is shown in Table 3. <Comparative Example 4> A purifying agent was prepared in the same manner as in Examples 2 to 5 except that the molar ratio of the base to the citric acid was sodium hydroxide/citric acid = 2.10 /1. The amount of pure water added and the water content in the purifying agent are as shown in Table 3, and the pH of the prepared scavenger is shown in Table 3. -27- 201008606 Water content (parts by weight) of ε嗽 Purifying agent ※※ m CN CN 726 726 Additional amount of pure water (parts by weight) ※※ 00 \〇569 569 卜 (Remarks) Preferred range of protons ※ 0.28 -4.45 0.39-6.28 0.28-4.53 0.12-1.94 0.14-2.31 pH of the scavenger vd 5 〇in On Number of protons of citric acid 0.28 1.18 1.98 1.93 2.60 Molar number of sodium hydroxide 1 ε 荽cn i cn (N < N 14.998mmol 5.327mmol 6.069mmol Moir number of citric acid IB cn vn in o o ΙΓϊ 00 5.6597mmol 2.4215mmol 2.8901mmol Sodium hydroxide / citric acid (Morby) 2.95/1 2.85/1 2.65/1 2.20/1 2.10/1 Example 2 Example 3 Example 4 Example 5 Comparative Example 4 Awake S爝M^l饀 Following «:£33«矻(1) 悄«键长撇: Awakening Ms·镒※ ffllM辂δ#0φ}_®οοι嘘4-1 趑 趑 爨鄯 嫲 嫲 ^ ^ ※ ※ ※ ※ ※ ^ ^ ^ ^ -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 -28 In the range of the present invention, the pH of the purifying agent is 5.0 or more. The pH of the purifying agent is suitable. <Example 6 > FeS04 · 7H20 (Wako Pure Chemical Co., Ltd.) The reagent is dissolved in pure water to prepare a simulated groundwater. In a 5% by weight aqueous hydrogen peroxide solution Φ (for Mitsubishi Gas Chemical Industry), 1 〇 is added relative to 100 parts by weight of hydrogen peroxide. 〇 parts by weight of citric acid (anhydrous) (special grade drug made by small chemical (stock)), molar ratio of alkali to citric acid to hydroxide of sodium hydroxide / citric acid = 2.85 / 1 (mole ratio) Sodium (a special grade drug manufactured by Wako Pure Chemical Industries Co., Ltd.) and pure water (278 parts by weight based on 100 parts by weight of the total amount of hydrogen peroxide and citric acid added) are dissolved to prepare a scavenger (relative to The water content is 3 70 parts by weight based on 100 parts by weight of the total amount of hydrogen peroxide and citric acid added, and the simulated groundwater is simulated so that the hydrogen peroxide concentration is 1.0% by weight and the Fe ion concentration is 25 mg/kg. The scavenger was mixed, placed in an Erlenmeyer flask, and allowed to stand in a constant temperature water bath at 50 ° C for 24 hours. The stability of hydrogen peroxide was compared by the concentration of hydrogen peroxide before and after standing. The results are shown in Table 4. <Example 7 > except for 1〇 The purifying agent was prepared in the same manner as in Example 6 -29-201008606 except that the content of citric acid of Example 6 was 50 parts by weight of citric acid in terms of parts by weight of hydrogen peroxide (relative to the addition of hydrogen peroxide and citric acid). The total amount of pure water added was 43 3 parts by weight in total of 1 part by weight, and the water content in the purifying agent was 559 parts by weight. The simulated ground water and the purifying agent were mixed so that the hydrogen peroxide concentration was 1.0% by weight and the Fe ion concentration was 25 mg/kg, placed in an Erlenmeyer flask, and allowed to stand in a constant temperature water bath at 50 ° C for 24 hours. The stability of hydrogen peroxide was compared by the concentration of hydrogen peroxide before and after standing. The results are shown in Table 4. <Example 8> A purifying agent was prepared in the same manner as in Example 6 except that the content of citric acid of Example 6 was 20 parts by weight of citric acid per 1 part by weight of hydrogen peroxide. The total amount of pure water added was 569 parts by weight based on 100 parts by weight of the total amount of hydrogen peroxide and citric acid added, and the water content in the cleaning agent was 723 parts by weight. The simulated ground water and the purifying agent were mixed so that the hydrogen peroxide concentration was 1.0% by weight and the Fe ion concentration was 25 mg/kg, placed in an Erlenmeyer flask, and allowed to stand in a constant temperature water bath at 50 ° C for 24 hours. The stability of hydrogen peroxide was compared by the concentration of hydrogen peroxide before and after standing. The results are shown in Table 4. <Example 9> A purifying agent was prepared in the same manner as in Example 6 except that the content of citric acid of Example 6 was 10 parts by weight of citric acid per 1 part by weight of hydrogen peroxide. The amount of pure water added was 636 parts by weight in total of 1 part by weight of hydrogen peroxide and citric acid added, and the water content in the net -30-201008606 agent was 804 parts by weight. The simulated ground water and the purifying agent were mixed so that the hydrogen peroxide concentration was 1.0% by weight and the Fe ion concentration was 25 mg/kg, placed in an Erlenmeyer flask, and allowed to stand in a constant temperature water bath at 50 ° C for 24 hours. The stability of hydrogen peroxide was compared by the concentration of hydrogen peroxide before and after standing. The results are shown in Table 4. <Comparative Example 5 > φ A cleaning agent was prepared in the same manner as in Example 6 except that the content of citric acid of Example 6 was changed to 5 parts by weight of citric acid per 100 parts by weight of hydrogen peroxide. The total amount of pure water added was 673 parts by weight, and the water content in the cleaning agent was 850 parts by weight based on 100 parts by weight of the total amount of hydrogen peroxide and citric acid added. The simulated underground water and the purifying agent were mixed so that the hydrogen peroxide concentration was 1.0% by weight and the Fe ion concentration was 25 mg/kg, and placed in a conical flask at 50%. (Still in a constant temperature water bath for 24 hours. The stability of the hydrogen peroxide was compared by the hydrogen peroxide concentration before and after standing. The results are shown in Table 4. <Comparative Example 6 > In the same manner as in Example 6, except that the content of the citric acid of Example 6 was 2 parts by weight of citric acid, the amount of the hydrogen peroxide was adjusted in the same manner as in Example 6 (the total amount of the added amount of hydrogen peroxide and citric acid) The amount of addition of pure water is 690 parts by weight, and the water content in the cleaning agent is 880 parts by weight. The hydrogen peroxide concentration is 1.0% by weight and the Fe ion concentration is 25 mg/kg. The simulated underground -31 - 201008606 water and purifier were mixed, placed in an Erlenmeyer flask, and allowed to stand in a constant temperature water bath at 50 °C for 24 hours. The hydrogen peroxide stability was compared by the concentration of hydrogen peroxide before and after standing. The results are shown in Table 4. <Example 1 〇> In addition to the sodium hydroxide of Example 8, potassium hydroxide was used, and the molar ratio of the base to the citric acid was potassium hydroxide / citric acid = 2.85 / 1 (Morby) is prepared in the same manner as in the eighth embodiment. The amount of the pure water added is 461 parts by weight based on 100 parts by weight of the total amount of hydrogen peroxide and citric acid added, and the water content in the cleaning agent is 71 6 parts by weight. The method was such that the concentration was 1.0% by weight and the Fe ion concentration was 25 mg/kg. The simulated groundwater and the purifying agent were mixed, placed in an Erlenmeyer flask, and allowed to stand in a constant temperature water bath at 50 ° C for 24 hours. The hydrogen peroxide concentration was compared to the stability of hydrogen peroxide. The results are shown in Table 4. <Example 1 1 > In addition to the sodium hydroxide of Example 8, magnesium hydroxide, magnesium hydroxide/citric acid = 1.425 was used. In the same manner as in the case of the first embodiment, the amount of the pure water added is 567 parts by weight, based on 100 parts by weight of the total amount of hydrogen peroxide and citric acid added, and the cleaning agent is used. The water content in the medium is 722 parts by weight. The simulated groundwater and the purifying agent are mixed and placed in a conical flask at a concentration of 5 wt% of hydrogen peroxide and a concentration of Fe ions of 25 mg/kg. Allow to stand in a constant temperature water bath for 24 hours. The hydrogen peroxide concentration before and after the comparison was compared to the stability of hydrogen peroxide-32-201008606. The results are shown in Table 4. <Example 1 2 > In addition to the sodium hydroxide instead of Example 8, ammonia, ammonia/ In the same manner as in Example 8, except that citric acid was 2.85/1 (mole ratio), a purifying agent was added (the amount of pure water added to the total amount of hydrogen peroxide and citric acid added was 1 part by weight). 568 parts by weight, the water content in the purifying agent was 723723 parts by weight. The simulated groundwater and the scavenger were mixed and placed in an Erlenmeyer flask so that the hydrogen peroxide concentration was 1.0% by weight and the Fe ion concentration was 25 mg/kg. It was allowed to stand in a constant temperature water bath at 50 ° C for 24 hours. The stability of hydrogen peroxide was compared by the concentration of hydrogen peroxide before and after standing. The results are shown in Table 4. <Example 1 3 > In addition to the sodium hydroxide of Example 8, sodium hydroxide and ammonia were used, Q sodium hydroxide/ammonia/citric acid = 1.425/1.425/1 (mole ratio), and examples In the same manner, the amount of the pure water added was 572 parts by weight based on 100 parts by weight of the total amount of hydrogen peroxide and citric acid added, and the water content in the cleaning agent was 727 parts by weight. The simulated groundwater and the purifying agent were mixed in such a manner that the hydrogen peroxide concentration was 1.0% by weight and the Fe ion concentration was 25 mg/kg. The mixture was placed in an Erlenmeyer flask and allowed to stand in a constant temperature water bath at 50 ° C for 24 hours. The stability of hydrogen peroxide was compared by the concentration of hydrogen peroxide before and after standing. The results are shown in Table 4. -33- 201008606 <Example 1 4 > In addition to the sodium hydroxide used in place of Example 8, 'sodium hydroxide and magnesium hydroxide were used, sodium hydroxide/magnesium hydroxide/citric acid=1·42 5/0.713/1 ( In the same manner as in Example 8, the scavenger was prepared in the same manner as in Example 8 (the amount of the pure water added was 5 70 parts by weight based on the total amount of the added amount of the hydrogen peroxide and the citric acid added, and the purifying agent was used. The water content in the amount was 725 parts by weight). The simulated groundwater and the scavenger were mixed so that the hydrogen peroxide concentration became 1 · 〇 by weight and the Fe ion concentration was 25 mg / kg, placed in a triangular flask, and allowed to stand in a constant temperature water bath at 50 ° C for 24 hours. The stability of hydrogen peroxide was compared from the concentration of hydrogen peroxide before and after standing. The results are shown in Table 4. -34- 20 8 inch 撇 06 on 1 编 0 wake up 1 S 1 镒 0.21 ~ 3.33 0.10-1.58 0.04 ~ 0.67 0.02 ~ 0.33 0.01 ~ 0.17 0.004 ~ 0.07 0.04 ~ 0, 67 0.04 ~ 0.68 0.04-0.67 0.04 ~ 0.67 0.04-0.67 With or without Fe Precipitation 1 L No precipitation No precipitation No precipitation No precipitation No precipitation No precipitation No precipitation No precipitation No precipitation No precipitation Hydrogen peroxide residual rate 1 1 ! 80.8% 87.9% 91.5% 84.5% 22.6% 19.7% 93.4% 81.6% 92.5% 90.2% 1 90.7% 1« 1« ?S s S <N圮0.81% by weight ilmll ipt oo 00 ο 0.92% by weight 0.85% by weight 0.23% by weight _ Translation 0.93% by weight _ tlmll ιρι] (Nl 00 ο 0.92% by weight _ ®1 On 〇Os 〇 Initial hydrogen peroxide concentration 1.01% by weight 〇Μ ilmj] Paste 1—^ 1.01% by weight 1.00% by weight 1.01% by weight LOOMS% 1.00Review % _ ilmll ρπ] Ο r —Η _ 〇 _ _ O 1.05 Military halo ° / 〇 24 hours after standing still pH · VI 〇 00 00 citric acid proton number 0.62 0.30 0.13 0.06 0.03 0.01 0.13 0.14 0.13 0.13 0.13 alkali molar number 11.866mmol 5.622mmol 2.375mmol 1.188mmol 0_593mmol 0.238mmol 2.386mmol 1.202mmol 2 .382mmol NaOH 1.189mmol NH3 1.189mmoI NaOH 1.187mmol Mg(0H)2 0.593mmol sodium hydroxide sodium hydroxide sodium hydroxide sodium hydroxide sodium hydroxide potassium hydroxide magnesium hydroxide minus sodium hydroxide and hydrogen Sodium Oxide and Magnesium Hydroxide 1 Molybdenum Number of Citric Acid 1 B Inch VO 1.9728mmol 0.8334mmol 0.4168mmol 0.2082mmol 0.0835mmol 1 ε m 00 ο i ε Ζ ο 1 ε Os in 00 o 1 ε m oo o 0.8329mmol Lemon Acid (parts by weight) / hydrogen peroxide (parts by weight) 100/100 50/100 20/100 10/100 5/100 2/100 20/100 20/100 20/100 20/100 20/100 Example 6 Implementation Example 7 Example 8 Example 9 Comparative Example 5 Comparative Example 6 Example 10 Example 11 Example 12 Example 13 Example 14 Awakening sM-ia-N 趑 3 3⁄43⁄43⁄43⁄4矻 (1) 狃 狃 嗽 嗽 嗽: awake猡镰屮鲰盈玴镒* -35- 201008606 The results of Examples 6 to 14 show that when the scavenger contains 1 part by weight or more of citric acid, the residual ratio of hydrogen peroxide is high, and hydrogen peroxide is stabilized. On the other hand, the results of Comparative Example 5 and Comparative Example 6 showed that when the citric acid of the purifying agent was less than 10 parts by weight, the residual ratio of hydrogen peroxide was remarkably lowered. "Hydrogen peroxide was not stabilized, and precipitation of iron was observed. The above results show that the purifying agent in the vicinity of the neutral phase of citric acid containing at least 1 part by weight is suitable as a purifying agent capable of stabilizing hydrogen peroxide. <Examples 15 to 16> The same procedure as in Example 8 except that the molar ratio of sodium hydroxide to citric acid was changed to sodium hydroxide/citric acid = 2.85/1, and sodium chloride or potassium sulfate was added as a neutral salt. The cleaning agent is prepared to compare the stability of hydrogen peroxide. The molar ratio of the neutral salt to the citric acid was sodium chloride/citric acid = 0.5/1 in Example 15, and potassium sulfate/citric acid = 0.25/1 in Example 16. In addition, in Example 15, the total amount of pure water added was 566 parts by weight, and the water content in the cleaning agent was 721 parts by weight, based on 100 parts by weight of the total amount of hydrogen peroxide and citric acid added, and Example 16 The amount of the pure water added was 5 65 parts by weight, and the water content in the purifying agent was 720 parts by weight based on 1 part by weight of the total amount of hydrogen peroxide and citric acid added. The results are shown in Table 5. -36- 201008606 Remarks) Preferred proton number range ※ 0.04-0.67 0.04-0.67 With or without Fe precipitation No precipitation No precipitation Hydrogen peroxide residual rate 86.3% 85.7% 醎 and 嫲埘 嫲埘 S S S _ 0.91% by weight 0.90% by weight Initial Hydrogen peroxide concentration 1.05 wt% 1.05 wt% pH after 24 hours of standing 1> Number of protons of citric acid 0.13 0.12 Molar number of base 2.376 mmol 2.375 mmol Neutral salt sodium chloride potassium sulfate citrate molar number 0.8336mmol 0.8332mmol Citric acid (parts by weight) / hydrogen peroxide (parts by weight) 20/100 20/100 Example 15 Example 16 Drawing SS 镰lfM-N^_»s33»^(I) Wipe-ffl bond length撇: Wake-up shovel Ms·镒* -37- 201008606 Example 15 and Example 16 show that hydrogen peroxide is also stabilized when the purifying agent contains a neutral salt. <Examples 17 to 20> A scavenger (with respect to the addition amount of hydrogen peroxide and citric acid) having a hydrogen peroxide concentration of 6.55 wt%, a citric acid concentration of 0.65 wt%, and a sodium hydroxide concentration of 0.389 wt% was prepared. The total amount of pure water added was 1 117 parts by weight in total of 1 part by weight, and the water content in the purifying agent was 1286 parts by weight. Further, pure water was dissolved in the Fe compound to prepare a catalyst aqueous solution having a iron ion concentration of 0.20% by weight. The preparation of the aqueous solution of the catalyst was prepared by dissolving FeS04. 7H20 (a special grade reagent manufactured by Wako Pure Chemical Industries Co., Ltd.) in pure water in Example 17, and in Example 18, 0.116 g of FeS04. 7H20, 0.209 g was prepared. 0.5M sulfuric acid and 0.220 g of BASF Japan's 40% by weight methyl glycine diacetate trisodium salt (MGDA, trade name "Trilon® (registered trademark))) was dissolved in pure water to prepare. In the middle of the system, 0.127 g of FeS04. 7Η20 and 0.459 g of central CHELEST (s, S)-ethylenediamine disuccinic acid trisodium salt (EDDS, trade name "CHELEST EDDS-35") was dissolved in pure water. Further, in Example 20, 0.130 g of FeS04·7H20 and 0.183 g of a 50% by weight aqueous solution of gluconic acid were dissolved in pure water to prepare a solution. In a 131 mL vial (vial), 10 mL of a simulated contaminated water, 1 mL of scavenger, 10 mL of tetrachloroethylene (PCE) dissolved in volatile organic compounds at a concentration of 5 3.3 mg/L was added. A buffer solution composed of sodium bicarbonate/sodium carbonate (sodium bicarbonate concentration 18.7 g/L, carbonic acid-38-201008606 sodium concentration 0.10 g/L), 1 mL of aqueous catalyst solution, 19 mL of pure water, sealed, and The purification test was carried out at room temperature. One hour after the start of the reaction, the reaction liquid was analyzed by headspace gas chromatography to compare the decomposition ability of PCE. The results are shown in Table 6.
-39- 201008606 9撇 (備註） 較佳的質子數範圍※ 0.002〜0.027 0.002-0.027 0.002-0.027 0.002-0.027 1小時後 PH 〇〇 卜 (N 初期 PH 〇〇 00 S 寸 PCE 分解率 23% 100% 25% 32% 1小時後 PCE濃度 m ε ο B 1 初期 PCE濃度 B 卜 〇 S 卜 ο ε 卜 Ο o 觸媒 A £ Fe2+-MGDA Fe2+-EDDS Fe2+-葡糖酸 檸檬酸的質子數 0.005 0.005 0.005 0.005 鹼的莫耳數 0.972mmol 0.972mmol 0.972mmol 0.972mmol 檸檬酸的莫 耳數 0.0341 mmol 0.0341mmol 0.034 lmmol 0.0341mmol 實施例17 實施例18 實施例19 實施例20 画ss鎰^^M·N氍職i:s¾»矻(l)悄¢M长谳：醒§i鉍屮MS¾鎰※-39- 201008606 9撇(Remarks) Preferred proton number range ※ 0.002~0.027 0.002-0.027 0.002-0.027 0.002-0.027 After 1 hour PH ( (N initial PH 〇〇00 S inch PCE decomposition rate 23% 100 % 25% 32% PCE concentration after 1 hour m ε ο B 1 Initial PCE concentration B 〇 〇 S ο ε Ο Ο o Catalyst A £ Fe2+-MGDA Fe2+-EDDS Fe2+-gluconate citrate proton number 0.005 0.005 0.005 0.005 Molar number of base 0.972 mmol 0.972 mmol 0.972 mmol 0.972 mmol Moir number of citric acid 0.0341 mmol 0.0341 mmol 0.034 lmmol 0.0341 mmol Example 17 Example 18 Example 19 Example 20 Drawing ss镒^^M·N氍Job i:s3⁄4»矻(l) ¢¢M 长谳:Wake up §i铋屮MS3⁄4镒※
-40- 201008606 實施例17〜2〇顯示在鐵觸媒的存在下，揮發性有機 化合物進行分解。再者’實施例18顯示當使用雙羧甲基 胺系蟹合劑時’揮發性有機化合物進行大幅分解。 產業上的利用可能性 依照本發明，可對周邊環境、生態系統等不造成影響 ’在原位置安全且有效地淨化有機化合物所污染的土壤及 ® /或地下水。-40-201008606 Examples 17 to 2〇 show that the volatile organic compounds are decomposed in the presence of an iron catalyst. Further, Example 18 shows that the volatile organic compound is largely decomposed when a biscarboxymethylamine-based crab mixture is used. INDUSTRIAL APPLICABILITY According to the present invention, it is possible to prevent the surrounding environment, the ecosystem, and the like from being affected, and to safely and effectively purify the soil and the groundwater contaminated with the organic compound in the original position.
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