201038467 六、發明說明： 【發明所屬之技術領域】 本發明係關於使用於被化學物質所污染之土壤及/或 地下水的淨化之淨化劑，以及使用該淨化劑之淨化方法。 【先前技術】 土壤及/或地下水的污染對生活環境造成較大影響之 _ 情況乃極爲明顯，因此係訂定出水質污染防治法及土壤污 Ο 染對策法等。然而，從土壤污染對策法的施行開始至今5 年，化學物質污染仍接連顯現，而必須加以淨化。在此， 所謂化學物質，主要相當於難以藉由生物所分解之難分解 性有機化合物、農藥、防腐劑、石油及該餾份中所含之芳 香族化合物、氰化物等。 針對此類化學物質污染，係嘗試進行物理性、化學性 、生物性或是組合此等之各種淨化方法。物理性方法，例 Q 如在挖掘去除中，雖然可進行污染場所的淨化，但仍有需 對所去除之污染物質進行二次處理之缺點。此外，生物性 方法，例如生物強化雖然具有對周邊環境的影小較少之優 點，但具有難以運用在高濃度污染或複合污染之缺點。相 對於此，在化學性淨化方法中，可分解污染物質，所以不 需進行二次處理，並且不具分解對象的選擇性，所以亦可 運用在高濃度污染或複合污染。 化學性分解方法，最普遍的是使用過氧化氫之費頓反 應（Fenton Reaction)。專利文獻1中，係提出一種將氧 201038467 化劑與調整至pH5〜8之Fe螯合觸媒水溶液注入至原位置 環境之手法。專利文獻1中，係提出有首先注入氧化劑後 再注入鐵螯合觸媒水溶液之手法，以及同時注入氧化劑與 鐵螯合觸媒水溶液之手法，但在預先混合氧化劑與鐵螯合 觸媒水溶液時，在混合的同時氧化劑亦開始分解，所以當 長時間放置混合液時，污染物質的淨化能量降低之可能性 提局。 專利文獻2中，係提出一種生物分解性螯合劑與過氧 化氫添加至原位置環境之淨化方法。然而，專利文獻2係 —種將生物分解性螯合劑與pH緩衝劑一同添加至地面中 ，與地面中的鐵生成錯合物後，在將作用場所的p Η保持 在5〜1 0之狀態下添加氧化劑之方法，所以必須分別準備 淨化所需的藥劑，於淨化現場再分別進行，過氧化氫的稀 釋、生物分解性螯合劑溶液的調製、pH緩衝劑的調製。 該技術中，必須分別單獨進行過氧化氫的稀釋以及螯合劑 溶液的調製之理由，在於尙無可在過氧化氫水溶液中安定 地保持螯合劑之技術之故。 [專利文獻1]日本特許第3793084號公報 [專利文獻2] WO2006-123574號公報 【發明內容】 (發明所欲解決之課題） 本發明係鑒於上述先前技術的問題點而創作出之發明 ’其在於提供一種即使以土壤及/或地下水的淨化所需之 -6- 201038467 調配比來混合過氧化氫水溶液與螯合劑，亦可藉 地抑制過氧化氫及螯合劑的分解來進行淨化藥劑1 配，而能夠降低淨化現場的藥劑調製負荷之含有 物分解的螯合劑之安定性佳之過氧化氫水溶液。 (用以解決課題之手段） 本發明者們係爲了解決上述課題而進行精心 ^ 果發現，爲了將生物分解性螯合劑添加於一般流 之過氧化氫水溶液，必須選擇甲基甘胺酸二乙酸 分解性螯合劑，添加磷酸並構成pH2.5〜5之過氧 液，藉此可提高過氧化氫及甲基甘胺酸二乙酸的 因而完成本發明。 亦即，本發明係提供下列所示之過氧化氫水 使用其之土壤及/或地下水的淨化方法。 [1 ] 一種過氧化氫水溶液，爲使用於被化學 Q 染之土壤及/或地下水的淨化之過氧化氫水溶液 爲：該過氧化氫水溶液係含有甲基甘胺酸二乙酸 且 pH 爲 2.5~5。 [2] 如[1 ]之過氧化氫水溶液，其中甲基甘 酸的濃度爲〇. 重量％。 [3] 如[1 ]之過氧化氫水溶液，其中過氧化 爲25〜45重量％。 [4] 如[1 ]之過氧化氫水溶液，其中磷酸 由長時間 的事前調 可進行生 探討，結 通的濃度 作爲生物 化氫水溶 安定性， 溶液以及 物質所污 ，其特徵 及隣酸， 胺酸二乙 氫的濃度 的濃度爲 201038467 [5] —種土壤及/或地下水的淨化方法，爲被化學物 質所污染之土壤及/或地下水的淨化方法，其特徵係包含 :將如[1 ]〜[4 ]中任一項之過氧化氫水溶液，以原液或經稀 釋添加於淨化對象之過氧化氫水溶液添加步驟。 [6] 如[5]之淨化方法，其中在前述過氧化氫水溶液 添加步驟前，包含：將鐵離子調配於該過氧化氫水溶液之 鐵離子調配步驟。 [7] 如[5]之淨化方法，其中在前述過氧化氫水溶液 添加步驟前或後，包含：將鐵離子供應至淨化對象之鐵離 子供應步驟。 [8] 如[5 ]〜[7 ]之中任一項之淨化方法，其中更使用 pH緩衝劑將淨化中之淨化對象的pH保持在5〜9。 發明之效果： 根據本發明，由於可長時間地抑制使用於土壤及/或 地下水的淨化之過氧化氫水溶液中之過氧化氫及螯合劑白勺 分解，所以可進行含有生物分解性螯合劑之過氧化氫水@ 液的事前調配，達成淨化現場之藥劑調製負荷的大幅降# ，並且該過氧化氫水溶液能夠極有效地作用於污染化學@ 質的分解。 【實施方式】 本發明之過氧化氫水溶液，爲使用於被化學物質卩斤$ 染之土壤及/或地下水的淨化之過氧化氫水溶液，其特摧戈 -8- 201038467 爲：該過氧化氫水溶液係含有甲基甘胺酸二乙酸及磷酸， 且 pH 爲 2.5~5。 (1 )淨化對象 本發明中，爲淨化對象之土壤及/或地下水，主要是 受到難以藉由生物所分解之難分解性有機化合物、農藥、 防腐劑、石油及該餾份中所含之甲苯、苯等之芳香族化合 Λ 物、三氯乙烯（TCE )、四氯乙烯（PCE )等之有機氯化 〇 合物、氰化物等之化學物質所污染。 (2 )過氧化氫水溶液 本發明之過氧化氫水溶液中的過氧_化氫濃度，就安全 性及運送成本降低之觀點來看，爲25〜45重量％，較佳爲 30〜45重量％。 本發明中所使用之生物分解性螯合劑，爲甲基甘胺酸 Q 二乙酸（以下有稱爲「MGDA」時）。在本發明之過氧化 氫水溶液中的濃度，較佳爲〇 · 1 ~ 5重量％，尤佳爲0.1〜4 重量％ ’特佳爲I〜2重量％。當較0.1重量％還低時，淨 化效果可能會降低。當較5重量％還高時，雖然可獲得淨 化效果，但就考量到經濟性、過氧化氫水溶液的安定性時 ’較佳爲0·1〜5重量％的範圍。 本發明之磷酸，例如有偏磷酸、焦磷酸、正磷酸、縮 合磷酸鹽等，此等可單獨使用1種或組合2種以上使用。 本發明中’特佳爲正磷酸。 -9 - 201038467 本發明之磷酸濃度，相對於本發明之過氧化氫水溶液 ，較佳爲0.1〜10重量％，尤佳爲0·5〜5重量％，特佳爲 0.7〜3.5重量％。當較0.1重量％還低時，過氧化氫水溶 液及MGD Α的安定性可能會降低。當較1〇重量％還高時 ，即使可保持過氧化氫水溶液及MGDA的安定性’但就 考量到經濟性時，較佳爲〇 . 1〜1 〇重量％的範圍。 本發明之過氧化氫水溶液中，正磷酸的一部分解離， 主要是作爲磷酸二氫離子及游離磷酸而存在，正磷酸以外 的磷酸亦相同，其一部分係解離而存在。本發明之過氧化 氫水溶液中的磷酸濃度，是指將該過氧化氫水溶液中之游 離磷酸以及因解離所產生的所有離子的合計濃度，換算爲 游離磷酸濃度之値。 本發明之過氧化氫水溶液的PH爲2.5〜5，較佳爲 3〜4.5，特佳爲pH3〜4.2。當過氧化氫水溶液的pH爲前述 範圍外時，水溶液之MGDA的安定性顯著降低，當含有 甲基甘胺酸二乙酸及磷酸之過氧化氫水溶液的pH爲前述 pH的範圍外時，可使用pH調整劑。pH調整劑可使用無 機酸、氫氧化鹼金屬、氫氧化鹼土類金屬等，較佳爲硫酸 、氫氧化鈉。 本發明中所使用之MGDA的市售品，一般爲三鈉鹽 ，所以其單獨的水溶液呈強鹼性。因此，將M GD A、磷酸 添加於本發明之過氧化氫水溶液的順序，較佳爲磷酸、 MGDA之順序，藉由依此順序添加，可將過氧化氫水溶液 維持爲酸性。當然，若進行冷卻等的安全對策則亦可依 -10- 201038467 M G D A、磷酸之順序添加。 (3 )淨化方法 本發明之土壤及/或地下水的淨化方法，爲被化學物 質所污染之土壤及/或地下水的淨化方法，其特徵係包含 :將上述本發明之過氧化氫水溶液，以原液或經稀釋添加 於淨化對象之過氧化氫水溶液添加步驟。 _ 對於使用本發明之過氧化氫水溶液來淨化土壤及/或 〇 地下水時之藥劑濃度，已進行例示說明，但本發明並不限 於該說明內容。 本發明之土壤及/或地下水的淨化方法中，可藉由添 加從完全分解淨化對象的污染所需之過氧化氫的量的1當 量至1 00 0倍當量的過氧化氫來實現。當少於此量時，淨 化不充分，過多時亦無法獲得如期望般的效果，並不具經 濟性。過氧化氫注入濃度，可考量淨化對象之地下水量的 0 稀釋來決定，較佳爲相對於注入水量爲0.5〜5%。一般過 氧化氫濃液的濃度爲3 5 %，所以現場中的稀釋倍率可由 此決定。 接著，本發明之土壤及/或地下水的淨化方法中之淨 化對象的鐵離子濃度（以鐵螯合的方式存在，係換算爲鐵 離子濃度來記載），100mg/L者即爲充分。本發明之生物 分解性螯合劑的必要量，相對於淨化對象的鐵離子濃度， 較佳爲0.5〜2當量’從前述稀釋倍率中，螯合劑的濃度可 由此決定。當少於此量時’分解不充分，過多時亦無法獲 -11 - 201038467 得效果，並不具經濟性。 當鐵離子於淨化對象的地下水中存在適當量 上述本發明之過氧化氫水溶液，以原液或經稀釋 化對象。當鐵離子不足時，較佳係在淨化現場中 子調配至本發明之過氧化氫水溶液後再添加於淨 或是在將本發明之過氧化氫水溶液添加於淨化對 ，將鐵離子供應至淨化對象。鐵離子源，例如有 或氯化亞鐵等之鐵鹽，較佳爲硫酸亞鐵。鐵鹽的 無特別限制，可藉由所要求之污染的等級來適當 一般而言，鐵鹽的供應量換算爲硫酸亞鐵，相對 象全體爲〇〜〇.1重量％。鐵鹽的供應方法，例如 置在土壤中之井等的設備，將構成爲水溶液之鐵 土壤及/或地下水之方法等。鐵鹽水溶液的濃度 0~10重量％。 將本發明之過氧化氫水溶液以原液或經稀釋 化對象時之方法，並無特別限制，可運用注入、 壓噴射、高壓噴射攪拌、噴霧、藥劑對揚水曝氣 入等之所有工法。 若淨化中之淨化對象的pH爲5〜9的範圍中 中的pH緩衝能較充分時，亦不一定需添加pH 但當添加本發明之過氧化氫水溶液使淨化對象的 降低，或是因污染物質的分解，使氯化物離子或 而導致淨化對象的p Η過度降低時，重金屬溶出 污染的危險性會被提高。因此，當有ρ Η過度降 時，可將 添加於淨 ，將鐵離 化對象， 象前或後 硫酸亞鐵 使甩量並 地選擇。 於淨化對 有藉由設 鹽供應至 ，較佳爲 添加於淨 壓入、高 系統的注 ，且土壤 緩衝劑， ΡΗ過度 羧酸生成 等之二次 低的疑慮 -12 - 201038467 時’較佳係使用p Η緩衝劑將淨化中之淨化對象的p Η保 持在5 ~ 9。 在此所使用之pH緩衝劑’可爲化學手冊等當中所介 紹者’就鐵的沉澱抑制及環境調合之觀點來看，較佳爲碳 酸系緩衝劑。碳酸系緩衝劑’例如有碳酸鈉、碳酸鉀、碳 酸鈣、碳酸鎂、碳酸氫鈉、碳酸氫鉀等。在這當中，就成 本及溶解度、pH之觀點來看’較佳爲單獨使用碳酸氫鈉 或是倂用碳酸氫鈉與碳酸鈉。pH緩衝劑，以使淨化中之 淨化對象的PH成爲5〜9之方式來適當的添加即可，但由 於碳酸離子及碳酸氫離子具有自由基清除效果，所以較佳 爲避免過度使用。 [實施例] 以下藉由實施例來具體地說明本發明，但本發明並不 限定於以下的實施例。201038467 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a purifying agent for purifying soil and/or ground water contaminated with a chemical substance, and a purifying method using the purifying agent. [Prior Art] The situation that the pollution of soil and/or groundwater has a great impact on the living environment is extremely obvious. Therefore, the Water Pollution Prevention Law and the Soil Pollution Control Law are formulated. However, five years after the implementation of the Soil Pollution Control Act, chemical pollution has continued to appear and must be purified. Here, the chemical substance mainly corresponds to a hardly decomposable organic compound which is difficult to be decomposed by a living, a pesticide, a preservative, petroleum, an aromatic compound or cyanide contained in the fraction, and the like. For the contamination of such chemicals, various purification methods such as physical, chemical, biological or a combination are attempted. Physical methods, for example, Q. Although it is possible to purify a contaminated site during excavation and removal, there is still a disadvantage of requiring secondary treatment of the removed pollutants. In addition, biological methods, such as biofortification, have the advantage of having less impact on the surrounding environment, but have the disadvantage of being difficult to apply to high concentration pollution or combined pollution. In contrast, in the chemical purification method, the pollutants can be decomposed, so that secondary treatment is not required, and the selectivity of the decomposition target is not obtained, so that it can be applied to high-concentration pollution or combined pollution. The most common method of chemical decomposition is the use of Fenton Reaction of hydrogen peroxide. Patent Document 1 proposes a method of injecting an oxygen 201038467 agent and an aqueous solution of a Fe chelate catalyst adjusted to pH 5 to 8 into an original position environment. Patent Document 1 proposes a method of first injecting an oxidizing agent and then injecting an aqueous solution of an iron chelate catalyst, and a method of simultaneously injecting an oxidizing agent and an aqueous solution of an iron chelate catalyst, but when the oxidizing agent and the iron chelate catalyst aqueous solution are mixed in advance. At the same time as the oxidizing agent starts to decompose while being mixed, when the mixed liquid is left for a long time, there is a possibility that the purification energy of the pollutants is lowered. Patent Document 2 proposes a purification method in which a biodegradable chelating agent and hydrogen peroxide are added to an in-situ environment. However, in Patent Document 2, a biodegradable chelating agent is added to the ground together with a pH buffering agent, and after forming a complex with iron in the ground, the p Η at the action site is maintained at 5 to 10 Since the method of adding an oxidizing agent is carried out, it is necessary to separately prepare a chemical agent required for purification, and perform separately at the purification site, dilution of hydrogen peroxide, preparation of a biodegradable chelating agent solution, and preparation of a pH buffering agent. In this technique, the reason for separately diluting hydrogen peroxide and preparing a chelating agent solution is that the chelating agent cannot be stably maintained in an aqueous hydrogen peroxide solution. [Patent Document 1] Japanese Patent No. 3793084 [Patent Document 2] WO2006-123574 SUMMARY OF INVENTION Technical Problem The present invention has been made in view of the problems of the prior art described above. It is to provide a hydrogen peroxide aqueous solution and a chelating agent even if the mixing ratio of -6-201038467 required for the purification of soil and/or groundwater is used to suppress the decomposition of hydrogen peroxide and a chelating agent. Further, it is possible to reduce the hydrogen peroxide aqueous solution having a good stability of the chelating agent which decomposes the content of the chemical preparation load at the purification site. (Means for Solving the Problems) The inventors of the present invention have made in order to solve the above problems, and in order to add a biodegradable chelating agent to a general aqueous hydrogen peroxide solution, it is necessary to select methylglycine diacetic acid. The decomposable chelating agent is added with phosphoric acid to form a peroxygen solution having a pH of 2.5 to 5, whereby hydrogen peroxide and methylglycine diacetic acid can be increased, thereby completing the present invention. That is, the present invention provides a method for purifying soil and/or groundwater using the hydrogen peroxide water shown below. [1] An aqueous hydrogen peroxide solution for purifying a chemically Q-dyed soil and/or groundwater by using an aqueous hydrogen peroxide solution containing methylglycine diacetic acid and having a pH of 2.5~ 5. [2] An aqueous hydrogen peroxide solution according to [1], wherein the concentration of methylglycolic acid is 〇.% by weight. [3] An aqueous hydrogen peroxide solution according to [1], wherein the peroxidation is from 25 to 45% by weight. [4] For example, [1] aqueous hydrogen peroxide solution, in which phosphoric acid can be prolonged by a long period of time, the concentration of the junction is used as the solubility of biological hydrogen, the solubility of the solution and the substance, and the acidity, The concentration of dihydrogen chloride is 201038467 [5] - a method for purifying soil and/or groundwater, a method for purifying soil and/or groundwater contaminated by chemical substances, characterized by: The aqueous hydrogen peroxide solution according to any one of [4] is added as a stock solution or an aqueous hydrogen peroxide solution added to the object to be purified. [6] The purification method according to [5], wherein before the step of adding the aqueous hydrogen peroxide solution, comprising: an iron ion compounding step of formulating iron ions in the aqueous hydrogen peroxide solution. [7] The purification method according to [5], wherein before or after the aforesaid hydrogen peroxide aqueous solution addition step, the iron ion supply step of supplying iron ions to the purification target is included. [8] The purification method according to any one of [5] to [7], wherein a pH buffer is further used to maintain the pH of the purified object in the purification at 5 to 9. Advantageous Effects of Invention According to the present invention, since decomposition of hydrogen peroxide and a chelating agent in an aqueous hydrogen peroxide solution used for purification of soil and/or groundwater can be suppressed for a long period of time, a biodegradable chelating agent can be used. The pre-distribution of the hydrogen peroxide water @ liquid achieves a significant drop in the preparation load of the purification site, and the hydrogen peroxide aqueous solution can be extremely effectively applied to the decomposition of the pollution chemical. [Embodiment] The aqueous hydrogen peroxide solution of the present invention is an aqueous hydrogen peroxide solution used for purifying soil and/or groundwater contaminated with a chemical substance, and the special hydrogen peroxide is used as the hydrogen peroxide solution. The aqueous solution contains methylglycine diacetic acid and phosphoric acid, and has a pH of 2.5 to 5. (1) Purification target In the present invention, the soil and/or groundwater to be purified is mainly subjected to hardly decomposable organic compounds, pesticides, preservatives, petroleum, and toluene contained in the fraction which are difficult to be decomposed by the organism. It is contaminated with chemical substances such as aromatic compounds such as benzene, organic chlorinated compounds such as trichloroethylene (TCE) and tetrachloroethylene (PCE), and cyanide. (2) Hydrogen Peroxide Solution The peroxygen-hydrogen concentration in the aqueous hydrogen peroxide solution of the present invention is 25 to 45% by weight, preferably 30 to 45% by weight, from the viewpoint of safety and reduction in transportation cost. . The biodegradable chelating agent used in the present invention is methylglycine Q diacetic acid (hereinafter referred to as "MGDA"). The concentration in the aqueous hydrogen peroxide solution of the present invention is preferably from 1.7 to 5% by weight, particularly preferably from 0.1 to 4% by weight, particularly preferably from 1 to 2% by weight. When it is lower than 0.1% by weight, the purification effect may be lowered. When the amount is more than 5% by weight, the cleaning effect can be obtained, but it is preferably in the range of from 0.1 to 5% by weight in consideration of economy and stability of the aqueous hydrogen peroxide solution. The phosphoric acid of the present invention may be, for example, metaphosphoric acid, pyrophosphoric acid, orthophosphoric acid or condensed phosphate. These may be used alone or in combination of two or more. In the present invention, it is particularly preferred to be orthophosphoric acid. -9 - 201038467 The phosphoric acid concentration of the present invention is preferably 0.1 to 10% by weight, particularly preferably 0.5 to 5% by weight, particularly preferably 0.7 to 3.5% by weight, based on the aqueous hydrogen peroxide solution of the present invention. When it is lower than 0.1% by weight, the stability of the aqueous hydrogen peroxide solution and the MGD oxime may be lowered. When the weight is more than 1% by weight, even if the stability of the aqueous hydrogen peroxide solution and MGDA can be maintained, it is preferably in the range of 1% to 1% by weight. In the aqueous hydrogen peroxide solution of the present invention, a part of orthophosphoric acid is dissociated, and it mainly exists as a dihydrogen phosphate ion and a free phosphoric acid, and phosphoric acid other than orthophosphoric acid is also the same, and some of them are dissociated and exist. The concentration of phosphoric acid in the aqueous hydrogen peroxide solution of the present invention means the total concentration of the free phosphoric acid in the aqueous hydrogen peroxide solution and all the ions generated by the dissociation, and is converted into the free phosphoric acid concentration. The aqueous hydrogen peroxide solution of the present invention has a pH of 2.5 to 5, preferably 3 to 4.5, particularly preferably 3 to 4.2. When the pH of the aqueous hydrogen peroxide solution is outside the above range, the stability of MGDA of the aqueous solution is remarkably lowered, and when the pH of the aqueous solution containing hydrogen peroxide of methylglycine diacetic acid and phosphoric acid is outside the range of the aforementioned pH, it can be used. pH adjuster. As the pH adjuster, inorganic acid, alkali metal hydroxide, alkaline earth metal hydroxide or the like can be used, and sulfuric acid or sodium hydroxide is preferred. The commercially available product of MGDA used in the present invention is generally a trisodium salt, so that its single aqueous solution is strongly alkaline. Therefore, the order of adding M GD A and phosphoric acid to the aqueous hydrogen peroxide solution of the present invention is preferably the order of phosphoric acid or MGDA, and by adding in this order, the aqueous hydrogen peroxide solution can be maintained acidic. Of course, if safety measures such as cooling are performed, it may be added in the order of -10-201038467 M G D A and phosphoric acid. (3) Purification method The method for purifying soil and/or groundwater according to the present invention is a method for purifying soil and/or groundwater contaminated by a chemical substance, characterized in that the aqueous hydrogen peroxide solution of the present invention is used as a stock solution. Or a step of adding an aqueous hydrogen peroxide solution added to the purification target by dilution. The concentration of the agent used in the purification of soil and/or strontium groundwater using the aqueous hydrogen peroxide solution of the present invention has been exemplified, but the present invention is not limited to the description. In the method for purifying soil and/or groundwater of the present invention, it can be achieved by adding 1 to 100 times equivalent of hydrogen peroxide from the amount of hydrogen peroxide required to completely decompose the object to be cleaned. When it is less than this amount, the purification is insufficient, and if it is too much, the effect as expected is not obtained, and it is not economical. The hydrogen peroxide injection concentration can be determined by considering the dilution of the groundwater amount of the object to be purified, preferably 0.5 to 5% with respect to the amount of water to be injected. Generally, the concentration of the hydrogen peroxide concentrate is 35 %, so the dilution ratio in the field can be determined. Next, in the soil and/or groundwater purification method of the present invention, the iron ion concentration (existed as iron chelate, which is expressed as iron ion concentration) in the purification target is 100 mg/L. The amount of the biodegradable chelating agent of the present invention is preferably 0.5 to 2 equivalents with respect to the concentration of iron ions to be purified. From the aforementioned dilution ratio, the concentration of the chelating agent can be determined. When it is less than this amount, the decomposition is not sufficient. If it is too much, it will not be obtained. -11 - 201038467 The effect is not economical. When the iron ions are present in the groundwater to be purified, an appropriate amount of the above aqueous hydrogen peroxide solution of the present invention is present as a stock solution or a diluted object. When the iron ions are insufficient, it is preferably added to the hydrogen peroxide aqueous solution of the present invention at the purification site, and then added to the purification or the hydrogen peroxide aqueous solution of the present invention is added to the purification pair to supply the iron ions to the purification. Object. The iron ion source is, for example, an iron salt such as ferrous chloride or the like, preferably ferrous sulfate. The iron salt is not particularly limited and can be suitably determined by the grade of the required contamination. Generally, the supply amount of the iron salt is converted into ferrous sulfate, and the relative amount is 〇~〇.1% by weight. The method of supplying the iron salt, for example, a device such as a well placed in the soil, and a method of forming the iron soil and/or groundwater of the aqueous solution. The concentration of the aqueous iron salt solution is 0 to 10% by weight. The method of using the aqueous hydrogen peroxide solution of the present invention as a stock solution or a diluted object is not particularly limited, and any of the methods such as injection, pressure jet, high-pressure jet agitation, spraying, and aeration of a potion into a water can be used. If the pH buffering energy in the range of pH 5 to 9 in the purification target is sufficient, it is not necessary to add pH, but when the hydrogen peroxide aqueous solution of the present invention is added, the purification target is lowered or contaminated. When the decomposition of the substance causes the chloride ions or the p Η of the purification target to be excessively lowered, the risk of contamination of the heavy metal is increased. Therefore, when there is excessive drop of ρ ,, it can be added to the net, and the iron is ionized, and the ferrous sulfate is selected before and after. For purification, there is a concern that the supply of salt is provided, preferably added to the net press-in, high system, and the soil buffer, bismuth excessive carboxylic acid formation, etc. -12 - 201038467 The p Η is used to maintain the p Η of the purified object in the purification at 5 to 9. The pH buffer used herein can be referred to in the chemical handbook or the like. From the viewpoint of precipitation inhibition of iron and environmental conditioning, a carbonate buffer is preferred. The carbonic acid buffering agent 'for example is sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate or the like. Among them, from the viewpoints of cost, solubility, and pH, it is preferred to use sodium hydrogencarbonate alone or sodium hydrogencarbonate and sodium carbonate. The pH buffering agent may be appropriately added so that the pH of the object to be purified in the purification is 5 to 9. However, since the carbonate ion and the hydrogencarbonate ion have a radical scavenging effect, it is preferable to avoid excessive use. [Examples] Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited to the following examples.
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[參考例1~7] 第1表係顯示依據先前方法所得知之各種生物分解性 螯合劑的苯分解率。試驗步驟如下所示。 (1 )調製出含有約80mg/L的苯之模擬污染水（a) 〇 (2 )調製出以等莫耳混合有FeS〇4 . 710 (和光純 藥製特級試藥）與生物分解性螯合劑之生物分解性鐵螯合 劑的濃液（b )。 -13- 201038467 (3 )製備碳酸氫鈉（小宗化學製一級§式藥）作爲緩 衝劑。 (4)將攪梓子放入於內容量l34mL的耐壓玻璃瓶， 使用 35 %工業用過氧化氫水溶液（Mitsubishi Gas Chemical製）與前述（a)〜（c)，調製出苯初期濃度 78.1mg/L，過氧化氫濃度480mg/L ’碳酸氫鈉濃度 17.6mM，鐵換算濃度15mg/L(螯合劑/鐵莫耳比爲1)的 溶液，以容器上部無氣相部分之方式將容器岔閉。 (5 )室溫下攪拌1小時’取出反應液並提供至頂空 採樣G C - M S分析（氣相層析質譜分析）。 <生物分解性螯合劑的略稱> MGDA :甲基甘胺酸二乙酸（BASF製） GLDA :穀胺酸二乙酸（Chelest製） ASDA ：天門冬胺酸二乙酸（Mitsubishi Rayon製） ESDA :牛磺酸二乙酸（Chelest製） EDDS :乙二胺二琥珀酸（Chelest製） HIDA :羥乙基亞胺基二乙酸（Chelest製） HGCA:葡萄庚酸（Chelest製） 此等生物分解性螯合劑，一般市面上係作爲鈉鹽所販 售。惟實施例及比較例中，係經游離酸換算後表示。 -14- 201038467 [第1表] 螯合劑 反應液的 度[mg/L] 苯分解率 初期pH 初期 分解後 [%] 參考例1 MGDA 8.1 78.1 21.4 72.6 …參煙2_… GLDA .......8.2 … 78.1 — 33.0 57.8 參考例3 ASDA 8.3 78.1 65.7 15.9 參考例4 ESDA 8.0 78.1 57.7 26.2 參考例5 EDDS 8.1 78.1 69.1 11.5 參考例6 HIDA 8.1 78.1 65.8 15.8 參考例7 HGCA 7.8 78.1 75.9 2.8[Reference Examples 1 to 7] The first table shows the benzene decomposition rate of various biodegradable chelating agents known from the prior methods. The test procedure is as follows. (1) Prepare a simulated contaminated water containing about 80 mg/L of benzene (a) 〇 (2) to prepare a molar mixture of FeS〇4. 710 (a special grade drug manufactured by Wako Pure Chemical Industries Co., Ltd.) and a biodegradable chelate A concentrate (b) of a biodegradable iron chelating agent. -13- 201038467 (3) Preparation of sodium hydrogencarbonate (small chemical type § formula) as a buffer. (4) The mash was placed in a pressure-resistant glass bottle having a content of 34 mL, and an initial concentration of benzene of 78.1 was prepared using a 35% industrial hydrogen peroxide aqueous solution (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and the above (a) to (c). Mg/L, hydrogen peroxide concentration 480mg / L 'sodium bicarbonate concentration 17.6mM, iron concentration of 15mg / L (chelating agent / iron molar ratio of 1) solution, the container is not in the upper part of the container Closed. (5) Stir at room temperature for 1 hour. The reaction solution was taken out and supplied to the headspace. Sampled G C - M S analysis (gas chromatography mass spectrometry). <Abbreviation of biodegradable chelating agent> MGDA: methylglycine diacetic acid (manufactured by BASF) GLDA: glutamic acid diacetic acid (manufactured by Chelest) ASDA: aspartic acid diacetic acid (manufactured by Mitsubishi Rayon) ESDA : Taurine diacetic acid (manufactured by Chelest) EDDS: ethylenediamine disuccinic acid (manufactured by Chelest) HIDA: hydroxyethyliminodiacetic acid (manufactured by Chelest) HGCA: grape heptanoic acid (manufactured by Chelest) Chelating agents are generally sold on the market as sodium salts. In the examples and comparative examples, the results are shown in terms of free acid. -14- 201038467 [Table 1] Degree of chelating agent reaction solution [mg/L] Benzene decomposition rate initial pH after initial decomposition [%] Reference Example 1 MGDA 8.1 78.1 21.4 72.6 ... Shenyan 2_... GLDA ..... ..8.2 ... 78.1 — 33.0 57.8 Reference Example 3 ASDA 8.3 78.1 65.7 15.9 Reference Example 4 ESDA 8.0 78.1 57.7 26.2 Reference Example 5 EDDS 8.1 78.1 69.1 11.5 Reference Example 6 HIDA 8.1 78.1 65.8 15.8 Reference Example 7 HGCA 7.8 78.1 75.9 2.8
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[實施例1、2 ] (1 )使用45%工業用過氧化氫水溶液（Mitsubishi Gas Chemical公司製）與40重量％ MGDA水溶液（BASF 製），調製出含有MGDA1.4重量％、磷酸（正磷酸）3_5 重量％、過氧化氫3 5重量％之水溶液。 (2 )使用氫氧化鈉（和光純藥製試藥）’將上述（1 )中所調製之水溶液調整爲第2表所示之ρΗ(ρΗ3·1' Ο 4.1 )，製得水溶液（A )。 (3 )將各水溶液（A )靜置於5 01的恆溫水槽中1 星期，比較各成分的殘存率。結果如第2表所示。 [比較例1 ~ 3 ] 除了將pH調整爲2.1、5.1、6.0之外’其他進行與 實施例1、2相同之實驗。 [比較例4〜6 ] -15- 201038467 除了使用GLDA ( Chelest製）作爲生物分解性螯合 劑之外，其他進行與實施例1、2及比較例2相同之實驗 [第2表] 螯合劑 水溶液(A)的 成分殘存率[%1 初期pH 過氧化氫 螯合劑 實施例1 MGDA 3.1 98.4 82.0 實施例2 MGDA 4.1 97.5 87.2 比較例1 MGDA 2.1 97.6 37.4 比較例2 MGDA 5.1 91.9 39.3 比較例3 MGDA 6.0 76.4 0.0 比較例4 GLDA 3.1 96.1 0.0 比較例5 GLDA 4.1 96.9 19.4 比較例6 GLDA 5.1 80.9 0.0 [比較例7、8 ] 除了使用硫酸將含有MGDA的過氧化氫水溶液（ MGDA1.4重量％、不含磷酸）的pH調整爲3.0(比較例 7 ) ，4 · 1 (比較例8 )之外，其他進行與實施例1、2相同 之實驗。此時的硫酸添加量，分別爲〇·43重量％，〇.40 重量％。結果如第3表所示。 -16 - 201038467 [第3表] 螯合劑 水溶液(A)的 初期pH 成分殘1 字率[%] 過氧化氫 螯合劑 比較例7 MGDA 3.0 97.0 68.2 比較例8 MGDA 4.1 88.0 57.5 [實施例3〜6] 除了將MGDA的濃度設定爲0.35〜5.0重量％之外， 其他進行與實施例1、2相同之實驗。結果如第4表所示 ❹ [第4表]. MGDA濃度 水溶液(A)的 初期pH 成分殘存率[%] 過氧化氫 螯合劑 實施例3 0.35 4.2 96.1 85.4 實施例4 0.70 4.2 96.5 88.2 實施例5 3.5 4.2 96.1 78.7 實施例6 5.0 4.1 94.7 79.0 〇 [實施例7〜1 1] 除了將磷酸濃度設定爲0.1 8〜7.0重量％，並使用硫 酸（實施例7〜9 )或氫氧化鈉（實施例1 0、1 1 )作爲pH 調整劑之外，其他進行與實施例2相同之實驗。結果如第 5表所示。 [實施例12〜16] 除了將磷酸濃度設定爲0.1 8〜7.0重量％，並使用硫 -17- 201038467 酸作爲p Η調整劑之外’其他進行與實施例2相同之實驗 。結果如第5表所示。 [第5表] 磷酸濃度 [%] 水溶液⑷的 初期pH 成分殘; 字率[%] 過氧化氫 螯合劑 實施例7 0.18 4.1 實施例8 0.35 4.2 77.2 實施例9 0.70 4.2 78.7 實施例10 1.75 4.2 98.3 82.3 實施例11 7.0 4.1 96.9 78.0 實施例12 0.18 3.1 實施例13 0.35 3.1 68.6 實施例14 0.70 3.2 70.2 實施例15 1.75 3.2 71.3 實施例16 7.0 3.2 97.7 60.2 [實施例17、18] (】）調製出含有約60mg/L的苯之模擬污染水 〇 (2 )製備FeS04 . 7H20 ( b )作爲鐵源。 (3 )製備碳酸氫鈉（c )作爲緩衝劑。 (4 )將攪拌子放入於內容量1 3 4 m L的耐壓玻璃瓶， 調製出含有MGDA1.4重量％與磷酸（正磷酸）3.5重量 %之3 5重量％過氧化氫水溶液後，使用氫氧化鈉（和光 純藥製試藥）調整pH，製得ρΗ4·1的水溶液（B )。使用 水溶液（Β )與前述（a ) ~ ( c )，調製出苯初期濃度 62’8mg/L，過氧化氫濃度 500mg/L ’碳酸氫鈉濃度 -18- 201038467 17.6mM，鐵換算濃度5mg/L( MGDA/鐵莫耳比爲1 .1 )或 鐵換算濃度l5mg/L ( MGDA/鐵莫耳比爲0.4 )的溶液，以 容器上部無氣相部分之方式將容器密閉。 (5)室溫下攪拌1天，取出反應液並提供至頂空採 樣GC-MS分析（氣相層析質譜分析）。結果如第6表所 不 。 0 [實施例19] 調製出含有MGDA3.5重量％與磷酸（正磷酸）3.5 重量％之3 5重量％過氧化氫水溶液後，使用氫氧化鈉（ 和光純藥製試藥）調整pH，製得pH3.9的水溶液（C )。 使用前述水溶液（C )來取代實施例1 7〜1 8的水溶液（B )，並使用實施例1 7〜1 8的（a ) ~ ( c )，調製出苯初期 濃度 62.8mg/L，過氧化氫濃度 500mg/L，碳酸氫鈉濃度 17.6mM，鐵換算濃度1 5mg/L ( MGDA/鐵莫耳比爲0.9) q 的溶液，除此之外，其他進行與實施例1 7~ 1 8相同之實驗 。結果如第6表所不。 [第6表][Examples 1 and 2] (1) Using 45% industrial hydrogen peroxide aqueous solution (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 40% by weight of MGDA aqueous solution (manufactured by BASF), 1.4% by weight of MGDA and phosphoric acid (orthophosphoric acid) were prepared. An aqueous solution of 3_5 wt% and 35 wt% hydrogen peroxide. (2) Using sodium hydroxide (a reagent manufactured by Wako Pure Chemical Industries, Ltd.), the aqueous solution prepared in the above (1) is adjusted to ρΗ (ρΗ3·1' Ο 4.1) shown in Table 2 to prepare an aqueous solution (A). . (3) Each aqueous solution (A) was allowed to stand in a constant temperature water bath of 510 for one week, and the residual ratio of each component was compared. The results are shown in Table 2. [Comparative Examples 1 to 3] The same experiments as in Examples 1 and 2 were carried out except that the pH was adjusted to 2.1, 5.1, and 6.0. [Comparative Examples 4 to 6] -15-201038467 The same experiment as in Examples 1, 2 and Comparative Example 2 was carried out except that GLDA (manufactured by Chelest) was used as the biodegradable chelating agent. [Second Table] A chelating agent aqueous solution (A) Component Residual Rate [%1 Initial pH Hydrogen Peroxide Chelator Example 1 MGDA 3.1 98.4 82.0 Example 2 MGDA 4.1 97.5 87.2 Comparative Example 1 MGDA 2.1 97.6 37.4 Comparative Example 2 MGDA 5.1 91.9 39.3 Comparative Example 3 MGDA 6.0 76.4 0.0 Comparative Example 4 GLDA 3.1 96.1 0.0 Comparative Example 5 GLDA 4.1 96.9 19.4 Comparative Example 6 GLDA 5.1 80.9 0.0 [Comparative Examples 7, 8] In addition to the use of sulfuric acid, an aqueous solution of hydrogen peroxide containing MGDA (MGDA 1.4% by weight, excluding The same experiment as in Examples 1 and 2 was carried out except that the pH of the phosphoric acid was adjusted to 3.0 (Comparative Example 7) and 4·1 (Comparative Example 8). The amount of sulfuric acid added at this time was 〇·43% by weight and 〇40% by weight, respectively. The results are shown in Table 3. -16 - 201038467 [Table 3] Initial pH of the chelating agent aqueous solution (A) Residual 1% [%] Hydrogen peroxide chelating agent Comparative Example 7 MGDA 3.0 97.0 68.2 Comparative Example 8 MGDA 4.1 88.0 57.5 [Example 3~ 6] The same experiment as in Examples 1 and 2 was carried out except that the concentration of MGDA was set to 0.35 to 5.0% by weight. The results are shown in Table 4. [Table 4]. Initial pH component residual ratio of MGDA concentration aqueous solution (A) [%] Hydrogen peroxide chelating agent Example 3 0.35 4.2 96.1 85.4 Example 4 0.70 4.2 96.5 88.2 Example 5 3.5 4.2 96.1 78.7 Example 6 5.0 4.1 94.7 79.0 〇 [Examples 7 to 1 1] In addition to setting the phosphoric acid concentration to 0.18 to 7.0% by weight, and using sulfuric acid (Examples 7 to 9) or sodium hydroxide (implementation) Example 1 0, 1 1) The same experiment as in Example 2 was carried out as the pH adjuster. The results are shown in Table 5. [Examples 12 to 16] The same experiment as in Example 2 was carried out except that the phosphoric acid concentration was set to 0.18 to 7.0% by weight, and sulfur -17-201038467 acid was used as the p Η adjusting agent. The results are shown in Table 5. [Table 5] Phosphoric acid concentration [%] Initial pH component of aqueous solution (4) Residual; Word rate [%] Hydrogen peroxide chelating agent Example 7 0.18 4.1 Example 8 0.35 4.2 77.2 Example 9 0.70 4.2 78.7 Example 10 1.75 4.2 98.3 82.3 Example 11 7.0 4.1 96.9 78.0 Example 12 0.18 3.1 Example 13 0.35 3.1 68.6 Example 14 0.70 3.2 70.2 Example 15 1.75 3.2 71.3 Example 16 7.0 3.2 97.7 60.2 [Example 17, 18] ()) Modulation FeS04. 7H20 (b) was prepared as an iron source by simulating contaminated water hydrazine (2) containing about 60 mg/L of benzene. (3) Preparation of sodium hydrogencarbonate (c) as a buffer. (4) The stirrer was placed in a pressure-resistant glass bottle having a content of 1 3 4 m L to prepare a 35 wt% aqueous hydrogen peroxide solution containing 1.4 wt% of MGDA and 3.5 wt% of phosphoric acid (orthophosphoric acid). The pH was adjusted using sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) to prepare an aqueous solution (B) of ρΗ4·1. Using an aqueous solution (Β) and the above (a) ~ (c), an initial concentration of benzene of 62'8 mg / L, a concentration of hydrogen peroxide of 500 mg / L ' sodium bicarbonate concentration -18 - 201038467 17.6 mM, iron concentration of 5 mg / A solution having a L (MGDA/iron molar ratio of 1.1) or an iron-converted concentration of 15 mg/L (MGDA/iron molar ratio of 0.4) is sealed in such a manner that the upper portion of the container has no gas phase portion. (5) Stir at room temperature for 1 day, and take out the reaction solution and provide to headspace sampling GC-MS analysis (gas chromatography mass spectrometry). The results are as shown in Table 6. [Example 19] After preparing a 35 wt% hydrogen peroxide aqueous solution containing 3.5 wt% of MGDA and 3.5 wt% of phosphoric acid (orthophosphoric acid), pH was adjusted using sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.). An aqueous solution (C) of pH 3.9 was obtained. The aqueous solution (B) of the above Examples 17 to 18 was replaced by the aqueous solution (C), and the initial concentration of benzene was adjusted to 62.8 mg/L using the examples (7) to (c) of Examples 17 to 18. A solution having a hydrogen peroxide concentration of 500 mg/L, a sodium hydrogencarbonate concentration of 17.6 mM, and an iron-converted concentration of 15 mg/L (MGDA/iron molar ratio of 0.9) q was carried out in the same manner as in Example 1 7 to 18 The same experiment. The results are as shown in Table 6. [Table 6]
Fe [mg/L] MGDA/Fe [莫耳比] 反應液的 初期pH 苯濃度『mg/L] 苯分解率 [%] 初期 分解後 實施例Π 5 1.1 8.4 62.8 4.0 94 實施例18 15 0.4 7.5 62.8 1.4 98 實施例19 15 0.9 7.4 62.8 0.01 100 如第6表所示，使用實施例I7〜19之含有MGDA及 -19- 201038467 磷酸且p Η爲2.5〜5之本發明的過氧化氫水溶液之系統’ 其污染物質的分解效果佳。 產業上之可利用性： 根據本發明，由於可長時間地抑制使用於土壤及/或 地下水的淨化之過氧化氫水溶液中之過氧化氫及螯合劑的 分解’所以可進行含有生物分解性螯合劑之過氧化氫水溶 液的事前調配，達成淨化現場之藥劑調製負荷的大幅降低 ，並且可提高污染化學物質的分解效率。 -20-Fe [mg/L] MGDA/Fe [Morby] Initial pH of the reaction solution Benzene concentration "mg/L] Benzene decomposition rate [%] Example after initial decomposition 1.1 5 1.1 8.4 62.8 4.0 94 Example 18 15 0.4 7.5 62.8 1.4 98 Example 19 15 0.9 7.4 62.8 0.01 100 As shown in Table 6, the aqueous hydrogen peroxide solution of the present invention containing MGDA and -19-201038467 phosphoric acid and having p Η 2.5 to 5 as in Examples I7 to 19 was used. The system's decomposition of pollutants is good. INDUSTRIAL APPLICABILITY According to the present invention, since decomposition of hydrogen peroxide and a chelating agent in an aqueous hydrogen peroxide solution used for purification of soil and/or groundwater can be suppressed for a long period of time, biodegradable chelate can be carried out. The prior preparation of the mixture of the hydrogen peroxide aqueous solution achieves a drastic reduction in the preparation load of the chemical at the purification site, and can improve the decomposition efficiency of the contaminated chemical. -20-