TWI653073B - Tcs (triclosan) treatment system and method thereof for soil, sludge and water - Google Patents

Tcs (triclosan) treatment system and method thereof for soil, sludge and water Download PDF

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TWI653073B
TWI653073B TW107125545A TW107125545A TWI653073B TW I653073 B TWI653073 B TW I653073B TW 107125545 A TW107125545 A TW 107125545A TW 107125545 A TW107125545 A TW 107125545A TW I653073 B TWI653073 B TW I653073B
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electrode
composite metal
triclosan
iron
metal
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TW201934162A (en
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袁菁
陳彥圻
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國立高雄大學
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Abstract

一種三氯沙處理方法包含:提供一電動力整治裝置;將一三氯沙待整治物容置於該電動力整治裝置,且該三氯沙待整治物包含一三氯沙污染物;將一二價金屬-鐵/鋁複合金屬氧化電極設置於該電動力整治裝置之三氯沙待整治物,而該二價金屬-鐵/鋁複合金屬氧化電極包含一電極芯層及一複合金屬電極外層,且該電極芯層由一含鋁金屬材料製成,且該複合金屬電極外層由一含二價金屬-鐵複合金屬材料製成;在該電極芯層及複合金屬電極外層之間形成一氧化還原反應區域;及利用該含鋁金屬材料及含二價金屬-鐵複合金屬材料適當結合一過硫酸鹽材料,以便適當進行催化降解或礦化處理該三氯沙待整治物之三氯沙污染物。 A method for treating triclosan comprises: providing an electric power rectifying device; arranging a triclosan to be rectified into the electric power rectifying device, and the triclosan to be treated comprises a triclosan contaminant; The divalent metal-iron/aluminum composite metal oxide electrode is disposed on the triclosan to be rectified in the electrodynamic rectification device, and the divalent metal-iron/aluminum composite metal oxidation electrode comprises an electrode core layer and a composite metal electrode outer layer And the electrode core layer is made of an aluminum-containing metal material, and the outer layer of the composite metal electrode is made of a divalent metal-iron composite metal material; an oxidation is formed between the electrode core layer and the outer layer of the composite metal electrode Reducing the reaction zone; and suitably combining the persulfate material with the aluminum-containing metal material and the divalent metal-iron composite metal material for proper catalytic degradation or mineralization treatment of the triclosan of the triclosan to be treated Things.

Description

於土壤、底泥及水體中三氯沙處理系統及其方法 Triclosan treatment system and method thereof in soil, sediment and water body

本發明係關於一種於土壤、底泥及水體中三氯沙〔TCS,Triclosan〕處理系統及其方法;特別是關於一種於土壤、底泥及水體中三氯沙處理系統及其方法採用二價金屬-鐵/鋁複合金屬氧化電極;更特別是關於一種於土壤、底泥及水體中三氯沙處理系統及其方法採用鈷-鐵/鋁複合金屬氧化電極,以催化降解或礦化處理環境〔土壤、水體或地下水〕中的污染物-三氯沙。 The present invention relates to a system and method for treating triclosan (TCS, Triclosan) in soil, sediment and water; in particular, a method for treating triclosan in soil, sediment and water body and method thereof Metal-iron/aluminum composite metal oxide electrode; more particularly, a system for treating triclosan in soil, sediment and water body and method thereof using cobalt-iron/aluminum composite metal oxide electrode for catalytic degradation or mineralization treatment environment Contaminant - triclosan in [soil, water or groundwater].

有關習用電動力土壤整治裝置,例如:中華民國專利第TW-I571326號〝複合金屬氧化電極構造及其製造方法〞之發明專利案,其揭示一種複合金屬氧化電極構造及其製造方法。該複合金屬氧化電極構造包含一金屬氧化電極、一電極芯層及一電極外層,而該電極芯層由一第一金屬材料製成,且該電極外層由一第二金屬材料製成。該電極外層設置於該電極芯層上,以組成該金屬氧化電極。在電動力土壤整治上,利用該第一金屬材料及第二金屬材料之氧化還原電位適當產生一自發反應,以便該第一金屬材料可供應電子,以利該第二金屬材料之氧化第二金屬還原形成零價第二金屬,再於水中進行芬頓反應,以便進行降解或礦化一有機污染物。該第一金屬材料選自鋁或含鋁材料,而該第二金屬材料選自鐵或含鐵材料。 The invention relates to a conventional electric power soil remediation device, for example, a composite metal oxide electrode structure and a manufacturing method thereof of the Republic of China Patent No. TW-I571326, which discloses a composite metal oxide electrode structure and a manufacturing method thereof. The composite metal oxide electrode structure comprises a metal oxide electrode, an electrode core layer and an electrode outer layer, and the electrode core layer is made of a first metal material, and the electrode outer layer is made of a second metal material. The outer layer of the electrode is disposed on the electrode core layer to constitute the metal oxide electrode. In the electrodynamic soil remediation, a spontaneous reaction is appropriately generated by using the redox potential of the first metal material and the second metal material, so that the first metal material can supply electrons to facilitate oxidation of the second metal material to the second metal. The reduction forms a zero-valent second metal, which is then subjected to a Fenton reaction in water for degradation or mineralization of an organic contaminant. The first metallic material is selected from aluminum or an aluminum containing material, and the second metallic material is selected from iron or a ferrous material.

前述第TW-I571326號之複合金屬氧化電極構 造及其製造方法僅適用於降解或礦化有機污染物之處理作業,且該複合金屬氧化電極為鐵/鋁複合金屬氧化電極。因此,習用複合金屬氧化電極構造及其製造方法必然存在進一步改良之需求,以適用於其它污染物之處理。 The composite metal oxide electrode structure of the aforementioned TW-I571326 The manufacturing method and the manufacturing method thereof are only applicable to the treatment of degraded or mineralized organic pollutants, and the composite metal oxide electrode is an iron/aluminum composite metal oxide electrode. Therefore, the conventional composite metal oxide electrode structure and its manufacturing method necessarily have further improvement requirements for the treatment of other pollutants.

另一習用電動力土壤整治裝置,例如:中華民國專利第TW-M377425號〝環境電動力技術之中空透水性電極棒結構〞之新型專利案,其揭示一種中空透水性電極棒結構,其包含:一電場裝置使預設區域內之土壤產生電場,其具有一正極及一負極;至少二電極棒分別設於各該正、負極上,該電極棒呈中空桿狀,其中央以軸線方向形成一空間,並以徑向穿設之至少一滲孔,為可連通該空間至電極棒外徑緣之通孔;利用各該電極棒分別設於各該正極及負極上,當產生電場時,土壤內之陰離子開始朝向正極游移;重金屬陽離子及溶解在水中之有機物則皆朝向負極游移,並可滲入至該空間內以集中,可方便於配合一抽出裝置將該空間內之重金屬污染物予以抽出。 Another conventional electric power soil remediation device, for example, a new patent of the hollow water-permeable electrode rod structure of the environmental electric power technology of the Republic of China Patent No. TW-M377425, which discloses a hollow water-permeable electrode rod structure, which comprises: An electric field device generates an electric field in the soil in the predetermined region, and has a positive electrode and a negative electrode; at least two electrode rods are respectively disposed on each of the positive and negative electrodes, the electrode rod is in the shape of a hollow rod, and the center thereof is formed in the axial direction. a space, and at least one perforated hole that is radially penetrated, is a through hole that can connect the space to an outer diameter edge of the electrode rod; and each of the electrode rods is respectively disposed on each of the positive electrode and the negative electrode, and when an electric field is generated, the soil The anion in the beginning begins to migrate toward the positive electrode; the heavy metal cation and the organic matter dissolved in the water all migrate toward the negative electrode, and can be infiltrated into the space for concentration, which can be conveniently extracted by a withdrawal device to remove heavy metal contaminants in the space.

另一習用電動力土壤整治裝置,例如:中華民國專利第TW-I249441號〝電動力整治重金屬污染土壤之系統與方法〞之發明專利案,其揭示一種電動力整治系統與其方法。電動力反應槽為開放式,將不同寬度之子槽可置入該電動力反應槽內,可供作土壤子槽、緩衝子槽、電極區等。 Another conventional electric power soil remediation device, for example, the Republic of China Patent No. TW-I249441, the system and method for rectifying heavy metal contaminated soil by the electric power, discloses an electrodynamic remediation system and a method thereof. The electrodynamic reaction tank is open, and sub-grooves of different widths can be placed in the electrodynamic reaction tank, and can be used as a soil sub-tank, a buffer sub-tank, an electrode area, and the like.

另一習用電動力土壤整治裝置,例如:中華民國專利第TW-I408258號〝電動力法採用雙金屬氧化物電極之再生系統〞之發明專利案,其揭示一種電動力法採用雙金屬氧化物電極之再生系統。該再生系統包含一電源裝置、一陰極及一陽極。該電源裝置用以供應電動力移除污染物之所需電力至該陰極及陽極。該陰極電性連接於該電源裝置,且該陰極連接一待再生元件之一第一端。該陽極 電性連接於該電源裝置,且該陽極連接該待再生元件之一第二端,以便自該待再生元件進行電動力移除污染物。該陽極係屬一雙金屬氧化電極,如此該雙金屬氧化電極在該陽極進行污染物降解。 Another conventional electric power soil remediation device, for example, the Republic of China Patent No. TW-I408258, the electric power method using a dual metal oxide electrode regeneration system, the invention patent case, which discloses an electrodynamic method using a double metal oxide electrode Regeneration system. The regeneration system includes a power supply unit, a cathode, and an anode. The power supply unit is configured to supply electric power to remove the required power of the contaminants to the cathode and the anode. The cathode is electrically connected to the power supply device, and the cathode is connected to a first end of a component to be regenerated. The anode Electrically connected to the power supply device, and the anode is connected to a second end of the component to be regenerated to electrically remove contaminants from the component to be regenerated. The anode is a double metal oxide electrode such that the double metal oxide electrode undergoes contaminant degradation at the anode.

另一習用電動力土壤整治裝置,例如:中華民國專利第TW-I280952號〝改善土壤〔污泥〕鉛、銅含量之方法〞之發明專利案,其揭示一種改善土壤〔污泥〕鉛、銅含量之方法可維持pH中性,且具提升去除土壤〔污泥〕重金屬效率。將陽、陰二電極設置在操作液儲存槽中,且不與土壤〔污泥〕直接接觸,並對處理土壤〔污泥〕施加一直流電壓。 Another conventional electric power soil remediation device, for example, the Republic of China Patent No. TW-I280952, a method for improving the lead and copper content of soil [sludge], which discloses an improved soil (sludge) lead and copper. The method of content can maintain pH neutrality and improve the efficiency of removing heavy metals from soil [sludge]. The anode and cathode electrodes are placed in the operating fluid storage tank, and are not in direct contact with the soil [sludge], and a DC voltage is applied to the treated soil [sludge].

另一習用電動力土壤整治裝置,例如:中華民國專利第TW-293056號〝被污染非均質土壞之原位補救〞之發明專利案,其揭示一種被污染非均質土壤區域之原位補救方法。該原位補救方法包含〔a〕將處理被污染非均質土壞區域中污染物之物質投入至少該被污染非均質土壤區域中一液體可滲透區域,以於該被污染非均質土壤區域中形成一處理區,〔b〕傳導直接電流通過被污染非均質土壤區域中至少一低滲透性土壤區,介於第一電極和具有相反電荷之第二電極之間,其中〔i〕第一電極位在被污染非均質土壤區域之首端,而第二電極則位於被污染非均質土壤區域之相對端或〔ii〕第一電極位在每個低滲透性土壤區域之首端,及第二電極位在每個低滲透性土壤區域之相對端,〔1〕以造成一種由第二電極至第一電極之電滲透流,〔2〕造成一種離子污染物朝相反電荷電極方向的電遷移移動,或〔3〕造成一種由第二電極至第一電極的電滲透流及一種離子污染物朝相反電荷電極方向的電遷移移動,並且〔c〕應用一種橫過被污染非均質土壤區域之水壓降,以造成一種由被污染非均質土壤區域之高壓端至被污染非均 質土壤區域之低壓端的水壓流。 Another conventional electrodynamic soil remediation device, for example, the Republic of China Patent No. TW-293056, an in-situ remedy for contaminated heterogeneous soil, discloses an in-situ remedy for contaminated heterogeneous soil regions. . The in-situ remedy method comprises [a] introducing a substance for treating pollutants in a bad area of the contaminated heterogeneous soil into at least one liquid permeable region of the contaminated heterogeneous soil region to form in the contaminated heterogeneous soil region. a treatment zone, [b] conducting a direct current through at least one low permeability soil zone in the contaminated heterogeneous soil zone between the first electrode and the second electrode having opposite charges, wherein [i] the first electrode site At the head end of the contaminated heterogeneous soil region, the second electrode is located at the opposite end of the contaminated heterogeneous soil region or [ii] the first electrode is at the beginning of each low permeability soil region, and the second electrode Located at the opposite end of each low permeability soil region, [1] to cause an electroosmotic flow from the second electrode to the first electrode, [2] to cause an electromigration movement of an ionic contaminant toward the opposite charge electrode, Or [3] causing an electroosmotic flow from the second electrode to the first electrode and an electromigration movement of an ionic contaminant toward the opposite charge electrode, and [c] applying a cross-contamination Water pressure drop homogeneous soil area to create a contamination by the contaminated heterogeneous soil region to the high-voltage terminal is the non-flat The water pressure at the low pressure end of the soil area.

另外,關於習用電動力土壤整治技術,其亦揭示於許多國外專利,例如:中國專利公告第CN-102527707號、美國專利第US-6193867號及美國專利公開第US-2006163068號申請案。 In addition, regarding the conventional electrodynamic soil remediation technology, it is also disclosed in many foreign patents, for example, the Chinese Patent Publication No. CN-102527707, the U.S. Patent No. US-A-No. No. 6,193,867, and the U.S. Patent Publication No. US-2006163068.

事實上,前述中華民國專利第TW-M377425號、第TW-I249441號、中國專利公告第CN-102527707號及美國專利第US-6193867號為僅屬採用傳統式惰性電極進行電動力整治土壤技術而已。然而,傳統式惰性電極亦僅能移除污染物部分而已,即其仍具有無法有效進行全面土壤整治的技術問題。 In fact, the aforementioned Republic of China Patent No. TW-M377425, No. TW-I249441, Chinese Patent Publication No. CN-102527707, and U.S. Patent No. US-A-No. No. 6,193,867 are only the use of conventional inert electrodes for electrodynamic remediation of soil technology. . However, the conventional inert electrode can only remove the contaminant portion, that is, it still has technical problems that cannot effectively perform overall soil remediation.

另外,前述中華民國專利公告第TW-I408258號採用複合金屬氧化電極,即採用改良式之雙金屬氧化物電極及其再生系統。然而,許多複合金屬電極通常為選擇由貴重金屬製成,因此其仍具有製造成本價格較昂貴及較不符合經濟效益之技術前題。 In addition, the aforementioned Republic of China Patent Publication No. TW-I408258 employs a composite metal oxide electrode, that is, an improved double metal oxide electrode and a regeneration system thereof. However, many composite metal electrodes are typically made of precious metals, so they still have the technical premise that manufacturing costs are relatively expensive and less economical.

另外,前述中華民國專利公告第TW-I280952號之改善土壤〔污泥〕鉛、銅含量之方法及第TW-293056號之被污染非均質土壤區域之補救方法僅為被污染土壤的一般修護技術方法而已,其仍具有無法有效進行全面整治土壤的技術問題。 In addition, the aforementioned method of improving the soil (sludge) lead and copper content of the Republic of China Patent No. TW-I280952 and the remedy of the contaminated heterogeneous soil area of TW-293056 are only general repairs of contaminated soil. Technical methods only have technical problems that cannot effectively rectify the soil.

前述專利公告中華民國專利第TW-I571326號、第TW-M377425號、第TW-I249441號、第TW-I408258號、第TW-I280952號、第TW-293056號、第CN-102527707號、美國專利第US-6193867號及美國專利公開第US-2006163068號僅為本發明技術背景之參考及說明目前技術發展狀態而已,其並非用以限制本發明之範圍。 The aforementioned patent publications, Republic of China Patent No. TW-I571326, No. TW-M377425, No. TW-I249441, No. TW-I408258, No. TW-I280952, No. TW-293056, No. CN-102527707, U.S. Patent The present invention is based on the state of the art and is not intended to limit the scope of the present invention.

有鑑於此,本發明為了滿足上述技術問題及需求,其提供一種二價金屬-鐵/鋁複合金屬氧化電極構造及其 製造方法,其於一金屬氧化電極設置一電極芯層及一複合金屬電極外層,而該電極芯層及複合金屬電極外層包含一第一金屬材料及一第二複合金屬材料,且將該複合金屬電極外層設置於該電極芯層上,且利用該第一金屬材料及第二複合金屬材料適當結合一過硫酸鹽材料,以便進行催化降解或礦化處理環境中的三氯沙污染物,因此相對於習用鐵/鋁複合金屬氧化電極構造及其製造方法可適用於處理環境中的三氯沙污染物。 In view of the above, in order to meet the above technical problems and needs, the present invention provides a divalent metal-iron/aluminum composite metal oxide electrode structure and a manufacturing method, wherein an electrode core layer and a composite metal electrode outer layer are disposed on a metal oxide electrode, and the electrode core layer and the composite metal electrode outer layer comprise a first metal material and a second composite metal material, and the composite metal is An outer layer of the electrode is disposed on the electrode core layer, and the first metal material and the second composite metal material are appropriately combined with a persulfate material to perform triclosan pollutants in a catalytic degradation or mineralization environment, and thus The conventional iron/aluminum composite metal oxide electrode structure and its manufacturing method can be applied to the treatment of triclosan pollutants in the environment.

本發明之主要目的係提供一種於土壤、底泥及水體中三氯沙處理系統及其方法,其將一二價金屬-鐵/鋁複合金屬氧化電極設置於一三氯沙待整治物,並於該二價金屬-鐵/鋁複合金屬氧化電極包含一電極芯層及一複合金屬電極外層,而該電極芯層及複合金屬電極外層包含一第一金屬材料及一第二複合金屬材料,且將該複合金屬電極外層設置於該電極芯層上,且利用該第一金屬材料及第二複合金屬材料適當結合一過硫酸鹽材料,以便進行催化降解或礦化處理環境中的三氯沙污染物,且達成處理環境中的三氯沙污染物之功效。 The main object of the present invention is to provide a triclosan treatment system and a method thereof in soil, sediment and water, wherein a divalent metal-iron/aluminum composite metal oxidation electrode is disposed on a triclosan to be treated, and The divalent metal-iron/aluminum composite metal oxide electrode comprises an electrode core layer and a composite metal electrode outer layer, and the electrode core layer and the composite metal electrode outer layer comprise a first metal material and a second composite metal material, and The composite metal electrode outer layer is disposed on the electrode core layer, and the first metal material and the second composite metal material are appropriately combined with a persulfate material for catalytic degradation or triclosan pollution in the mineralized treatment environment. And achieve the efficacy of treating triclosan pollutants in the environment.

本發明之另一目的係提供一種二價金屬-鐵/鋁複合金屬氧化電極構造及其製造方法,其於一金屬氧化電極設置一電極芯層及一複合金屬電極外層,而該電極芯層及複合金屬電極外層包含一第一金屬材料及一第二複合金屬材料,且將該複合金屬電極外層設置於該電極芯層上,且利用該第一金屬材料及第二複合金屬材料適當結合一過硫酸鹽材料,以便進行催化降解或礦化處理環境中的三氯沙污染物,且達成處理環境中的三氯沙污染物之功效。 Another object of the present invention is to provide a divalent metal-iron/aluminum composite metal oxide electrode structure and a method for fabricating the same, wherein an electrode core layer and a composite metal electrode layer are disposed on a metal oxide electrode, and the electrode core layer and The outer layer of the composite metal electrode comprises a first metal material and a second composite metal material, and the outer layer of the composite metal electrode is disposed on the electrode core layer, and the first metal material and the second composite metal material are appropriately combined A sulphate material for catalytic degradation or mineralization of triclosan in a treated environment and achieving the efficacy of treating triclosan in the environment.

為了達成上述目的,本發明較佳實施例之於土壤、底泥及水體中三氯沙處理系統包含: 一電動力整治裝置;一三氯沙待整治物,其容置於該電動力整治裝置,且該三氯沙待整治物包含一三氯沙污染物;至少一二價金屬-鐵/鋁複合金屬氧化電極,其設置於該電動力整治裝置之三氯沙待整治物,且該二價金屬-鐵/鋁複合金屬氧化電極包含一內芯層及一外表層;一電極芯層,其設置於該二價金屬-鐵/鋁複合金屬氧化電極之內芯層,而該電極芯層由一第一金屬材料製成,且該第一金屬材料為一含鋁金屬材料;一複合金屬電極外層,其設置於該二價金屬-鐵/鋁複合金屬氧化電極之外表層,而該複合金屬電極外層由一第二複合金屬材料製成,且該第二複合金屬材料為一含二價金屬-鐵複合金屬材料;及一氧化還原反應區域,其形成在該電極芯層及複合金屬電極外層之間;其中在整治該三氯沙待整治物時,利用該二價金屬-鐵/鋁複合金屬氧化電極增強一硫酸根自由基的移動能力,且利用該第一金屬材料及第二複合金屬材料適當結合一過硫酸鹽材料,以便適當進行催化降解或礦化處理該三氯沙待整治物之三氯沙污染物。 In order to achieve the above object, the preferred embodiment of the present invention in the soil, sediment and water body of the triclosan treatment system comprises: An electric power rectification device; a triclosan to be rectified, which is placed in the electrodynamic remediation device, and the triclosan to be rectified comprises a triclosan contaminant; at least one divalent metal-iron/aluminum composite a metal oxide electrode disposed in the electrochlorination device of the triclosan to be rectified, and the divalent metal-iron/aluminum composite metal oxide electrode comprises an inner core layer and an outer skin layer; an electrode core layer, the setting An inner core layer of the divalent metal-iron/aluminum composite metal oxide electrode, wherein the electrode core layer is made of a first metal material, and the first metal material is an aluminum-containing metal material; and a composite metal electrode outer layer And the outer layer of the composite metal electrode is made of a second composite metal material, and the second composite metal material is a divalent metal- An iron composite metal material; and a redox reaction region formed between the electrode core layer and the outer layer of the composite metal electrode; wherein the divalent metal-iron/aluminum composite metal is utilized in rectifying the triclosan to be rectified Oxidation electrode enhancement The ability of the sulfate radical to move, and the first metal material and the second composite metal material are appropriately combined with a persulfate material to appropriately perform catalytic degradation or mineralization treatment of the triclosan of the triclosan to be treated Things.

為了達成上述目的,本發明較佳實施例之於土壤、底泥及水體中三氯沙處理方法包含:提供一電動力整治裝置;將一三氯沙待整治物容置於該電動力整治裝置,且該三氯沙待整治物包含一三氯沙污染物;將一二價金屬-鐵/鋁複合金屬氧化電極設置於該電動力整治裝置之三氯沙待整治物,而該二價金屬-鐵/鋁複合金屬氧化電極包含一電極芯層及一複合金屬電極外層,且該電極芯層由一含鋁金屬材料製成,且該複合金屬 電極外層由一含二價金屬-鐵複合金屬材料製成;在該電極芯層及複合金屬電極外層之間形成一氧化還原反應區域;及利用該二價金屬-鐵/鋁複合金屬氧化電極增強一硫酸根自由基的移動能力,且利用該含鋁金屬材料及含二價金屬-鐵複合金屬材料適當結合一過硫酸鹽材料,以便適當進行催化降解或礦化處理該三氯沙待整治物之三氯沙污染物。 In order to achieve the above object, the method for treating triclosan in soil, sediment and water body according to a preferred embodiment of the present invention comprises: providing an electric power rectification device; and arranging a triclosan to be rectified into the electrodynamic rectification device And the triclosan to be treated comprises a triclosan contaminant; a divalent metal-iron/aluminum composite metal oxide electrode is disposed in the electrochlorination device of the triclosan to be rectified, and the divalent metal - the iron/aluminum composite metal oxide electrode comprises an electrode core layer and a composite metal electrode outer layer, and the electrode core layer is made of an aluminum-containing metal material, and the composite metal The outer layer of the electrode is made of a divalent metal-iron composite metal material; a redox reaction region is formed between the electrode core layer and the outer layer of the composite metal electrode; and the divalent metal-iron/aluminum composite metal oxide electrode is used for reinforcement The ability of a sulfate radical to move, and the aluminum-containing metal material and the divalent metal-iron composite metal material are appropriately combined with a persulfate material for proper catalytic degradation or mineralization treatment of the triclosan to be treated. Triclosan contaminants.

為了達成上述目的,本發明較佳實施例之二價金屬-鐵/鋁複合金屬氧化電極構造包含:一金屬氧化電極,其為一陽極,且該金屬氧化電極用於電動力土壤或水〔或地下水〕整治;一電極芯層,其由一第一金屬材料製成,且該第一金屬材料為一含鋁金屬材料;及至少一複合金屬電極外層,其由一第二複合金屬材料製成,而該第二複合金屬材料為一含二價金屬-鐵複合金屬材料,且將該複合金屬電極外層設置於該電極芯層上,以形成一二價金屬-鐵/鋁複合金屬氧化電極;其中該電極芯層及複合金屬電極外層組成該金屬氧化電極,且利用該金屬氧化電極之第一金屬材料及第二複合金屬材料適當結合一過硫酸鹽材料,以便進行催化降解或礦化處理環境中的三氯沙污染物。 In order to achieve the above object, a divalent metal-iron/aluminum composite metal oxide electrode structure according to a preferred embodiment of the present invention comprises: a metal oxide electrode which is an anode, and the metal oxide electrode is used for electrodynamic soil or water [or Groundwater] remediation; an electrode core layer made of a first metal material, and the first metal material is an aluminum-containing metal material; and at least one composite metal electrode outer layer made of a second composite metal material And the second composite metal material is a divalent metal-iron composite metal material, and the outer layer of the composite metal electrode is disposed on the electrode core layer to form a divalent metal-iron/aluminum composite metal oxide electrode; The electrode core layer and the outer layer of the composite metal electrode constitute the metal oxide electrode, and the first metal material and the second composite metal material of the metal oxidation electrode are appropriately combined with a persulfate material for catalytic degradation or mineralization treatment environment. Triclosan contaminants.

本發明較佳實施例之該複合金屬電極外層具有一鈷鐵氧磁體結構或一鈷鐵氧結晶結構。 In the preferred embodiment of the present invention, the outer layer of the composite metal electrode has a cobalt ferrite magnet structure or a cobalt iron oxide crystal structure.

本發明較佳實施例之該二價金屬-鐵/鋁複合金屬氧化電極為一圓柱體或一扁柱體。 In the preferred embodiment of the invention, the divalent metal-iron/aluminum composite metal oxide electrode is a cylinder or a flat cylinder.

本發明較佳實施例之該圓柱體或扁柱體組成一電極陣列。 In the preferred embodiment of the invention, the cylinder or the flat cylinder constitutes an electrode array.

本發明較佳實施例之該過硫酸鹽材料包含過 硫酸鈉材料、過硫酸鉀材料、具硫酸根自由基材料或其任意組合。 The persulfate material of the preferred embodiment of the invention comprises Sodium sulfate material, potassium persulfate material, sulfated radical material or any combination thereof.

為了達成上述目的,本發明較佳實施例之二價金屬-鐵/鋁複合金屬氧化電極製造方法包含:將至少一第一金屬棒進行酸洗,並取出該第一金屬棒,且該第一金屬棒由一含鋁金屬材料製成;將該第一金屬棒浸漬於一第二複合金屬離子溶液,並取出該第一金屬棒,且該第二複合金屬離子溶液為一含二價金屬-鐵金屬離子溶液;將該第一金屬棒進行預先烘乾;及將該第一金屬棒進行高溫烘烤鍛燒,以便在該第一金屬棒上形成至少一第二複合金屬層,以形成一二價金屬-鐵/鋁複合金屬氧化電極。 In order to achieve the above object, a method for manufacturing a divalent metal-iron/aluminum composite metal oxide electrode according to a preferred embodiment of the present invention comprises: pickling at least one first metal rod, and taking out the first metal rod, and the first The metal bar is made of an aluminum-containing metal material; the first metal bar is immersed in a second composite metal ion solution, and the first metal bar is taken out, and the second composite metal ion solution is a divalent metal- Iron metal ion solution; pre-baking the first metal rod; and subjecting the first metal rod to high temperature baking and calcining to form at least one second composite metal layer on the first metal rod to form a Divalent metal-iron/aluminum composite metal oxide electrode.

本發明較佳實施例之該第一金屬棒形成一電極芯層,且該第二複合金屬層包覆該電極芯層。 In the preferred embodiment of the invention, the first metal rod forms an electrode core layer, and the second composite metal layer covers the electrode core layer.

本發明較佳實施例之該第二複合金屬層形成一複合金屬電極外層,且將該複合金屬電極外層設置於該電極芯層上。 In the preferred embodiment of the present invention, the second composite metal layer forms a composite metal electrode outer layer, and the composite metal electrode outer layer is disposed on the electrode core layer.

本發明較佳實施例在該第二複合金屬層上形成另一複合金屬層,以便形成一多層複合金屬層。 In a preferred embodiment of the invention, another composite metal layer is formed on the second composite metal layer to form a multilayer composite metal layer.

本發明較佳實施例利用該二價金屬-鐵/鋁複合金屬氧化電極增強一硫酸根自由基於環境中的移動能力。 The preferred embodiment of the present invention utilizes the divalent metal-iron/aluminum composite metal oxide electrode to enhance the free mobility of the monosulfate based on the environment.

1‧‧‧金屬氧化電極 1‧‧‧Metal Oxidation Electrode

1a‧‧‧金屬氧化電極 1a‧‧‧Metal Oxidation Electrode

1’‧‧‧金屬氧化電極 1'‧‧‧Metal Oxidation Electrode

10‧‧‧電極芯層 10‧‧‧electrode core

11‧‧‧氧化還原反應區域 11‧‧‧redox reaction zone

20‧‧‧複合金屬電極外層 20‧‧‧Composite metal electrode outer layer

20a‧‧‧第一複合金屬電極外層 20a‧‧‧First composite metal electrode outer layer

20b‧‧‧第二複合金屬電極外層 20b‧‧‧Second composite metal electrode outer layer

第1圖:本發明第一較佳實施例之二價金屬-鐵/鋁複合金屬氧化電極構造之立體示意圖。 Fig. 1 is a perspective view showing the structure of a divalent metal-iron/aluminum composite metal oxide electrode according to a first preferred embodiment of the present invention.

第2圖:本發明較佳實施例之二價金屬-鐵/鋁複合金屬氧化電極製造方法之流程示意圖。 Fig. 2 is a flow chart showing a method for producing a divalent metal-iron/aluminum composite metal oxide electrode according to a preferred embodiment of the present invention.

第3圖:本發明較佳實施例之二價金屬-鐵/鋁複合金屬 氧化電極構造採用浸漬液二價金屬濃度對電極塗佈率之曲線示意圖。 Figure 3: Divalent metal-iron/aluminum composite metal in accordance with a preferred embodiment of the present invention The oxidation electrode structure is a schematic diagram showing the curve of the divalent metal concentration of the immersion liquid to the electrode coating rate.

第4圖:本發明較佳實施例之二價金屬-鐵/鋁複合金屬氧化電極構造進行X光繞射分析之圖譜示意圖。 Fig. 4 is a schematic view showing the X-ray diffraction analysis of the structure of the divalent metal-iron/aluminum composite metal oxide electrode of the preferred embodiment of the present invention.

第5圖:本發明第二較佳實施例之二價金屬-鐵/鋁複合金屬氧化電極構造之立體示意圖。 Fig. 5 is a perspective view showing the structure of a divalent metal-iron/aluminum composite metal oxide electrode according to a second preferred embodiment of the present invention.

第6圖:本發明第三較佳實施例之二價金屬-鐵/鋁複合金屬氧化電極構造之立體示意圖。 Figure 6 is a perspective view showing the structure of a divalent metal-iron/aluminum composite metal oxide electrode according to a third preferred embodiment of the present invention.

第7圖:本發明第三較佳實施例之二價金屬-鐵/鋁複合金屬氧化電極構造組成電極陣列之立體示意圖。 Fig. 7 is a perspective view showing the configuration of an electrode array of a divalent metal-iron/aluminum composite metal oxide electrode according to a third preferred embodiment of the present invention.

第8圖:本發明較佳實施例之於土壤、底泥及水體中三氯沙處理方法之流程示意圖。 Figure 8 is a schematic view showing the flow of a method for treating triclosan in soil, sediment and water according to a preferred embodiment of the present invention.

為了充分瞭解本發明,於下文將舉例較佳實施例並配合所附圖式作詳細說明,且其並非用以限定本發明。 In order to fully understand the present invention, the preferred embodiments of the present invention are described in detail below, and are not intended to limit the invention.

本發明較佳實施例之於土壤、底泥及水體中三氯沙處理系統及其方法與二價金屬-鐵/鋁複合金屬氧化電極構造及其用於土壤整治方法適用於各種電動力土壤〔污泥〕整治裝置,例如:電動力土壤〔或水、環境〕現場〔in-situ〕整治裝置,但其並非用以限制本發明之範圍。另外,本發明較佳實施例之本發明較佳實施例之二價金屬-鐵/鋁複合金屬氧化電極構造、其製造方法及其用於土壤整治方法適用於整治處理環境〔例如:土壤、底泥或地下水〕中的三氯沙污染物,但其並非用以限定本發明之應用範圍。 The preferred embodiment of the present invention is a triclosan treatment system and method thereof in soil, sediment and water body, and a divalent metal-iron/aluminum composite metal oxide electrode structure and a method for the soil remediation applied to various electrodynamic soils [ Sludge] remediation device, for example: electrodynamic soil (or water, environment) in-situ remediation device, but it is not intended to limit the scope of the invention. In addition, the divalent metal-iron/aluminum composite metal oxide electrode structure of the preferred embodiment of the present invention, the manufacturing method thereof and the method for the soil remediation are suitable for remediation treatment environment (for example, soil and bottom). The triclosan contaminant in mud or groundwater is not intended to limit the scope of application of the present invention.

一般而言,由於人類廣泛使用藥品及個人保健用品〔Pharmaceuticals Personal care products,PPCSPS〕,因此在土壤或地下體水中造成嚴重的污染,其中三氯沙〔TCS,5-氯-2-(2,4-二氯苯氧基)苯酚〕為一種新興污染物。三氯沙可由處理廠未處理排放方式或經由其他途徑流 佈於環境中,由於其對土壤具有較高之親和力,故常存在於土壤及底泥中。在環境中對於三氯沙之降解及礦化高級氧化處理方法包含光催化法、化學氧化法〔芬頓法、臭氧法等〕及電化學法等。然而,化學氧化法大多因需添加額外的化學藥劑而產生大量底泥,另還需考慮整治所產生之中間產物是否造成更嚴重的二次污染。 In general, due to the widespread use of pharmaceuticals and personal care products (PPCSPS) by humans, it causes serious pollution in soil or underground water, among which triclosan [TCS, 5-chloro-2-(2, 4-Dichlorophenoxy)phenol is an emerging contaminant. Triclosan can be discharged from untreated discharge by treatment plants or through other routes It is often found in the soil and sediment because it has a high affinity for the soil. The advanced oxidation treatment methods for the degradation and mineralization of triclosan in the environment include photocatalysis, chemical oxidation (Fenton method, ozone method, etc.) and electrochemical methods. However, most of the chemical oxidation methods require the addition of additional chemicals to produce a large amount of sediment, and it is also necessary to consider whether the intermediate products produced by the remediation cause more serious secondary pollution.

本發明採用技術名詞〝二價金屬-鐵/鋁複合金屬〞為以〝二價金屬材料及鐵材料與鋁材料〞或〝含二價金屬材料及含鐵材料與含鋁材料〞合成一複合金屬,並以〝鈷-鐵/鋁複合金屬〞或〝含鈷-鐵/鋁複合金屬〞舉例說明,但其並非用以限定本發明之範圍。 The invention adopts the technical term 〝 divalent metal-iron/aluminum composite metal ruthenium to synthesize a composite metal of bismuth metal material and iron material and aluminum material bismuth or bismuth containing divalent metal material and ferrous material and aluminum alloy material. And samarium-cobalt-iron/aluminum composite metal ruthenium or ruthenium-containing cobalt-iron/aluminum composite metal ruthenium is exemplified, but it is not intended to limit the scope of the invention.

第1圖揭示本發明第一較佳實施例之二價金屬-鐵/鋁複合金屬氧化電極構造之立體示意圖。請參照第1圖所示,本發明第一較佳實施例之二價金屬-鐵/鋁複合金屬氧化電極構造包含一金屬氧化電極1、一電極芯層〔electrode core〕10及一複合金屬電極外層〔composite metallic electrode shell layer〕20,而該電極芯層10由該第一金屬材料製成,且該複合金屬電極外層20由該第二複合金屬材料〔即,鈷-鐵/鋁複合金屬材料、含鈷-鐵/鋁複合金屬材料或其它二價金屬-鐵/鋁複合金屬材料〕製成。即該第一金屬材料配置於該電極芯層10,而該第二複合金屬材料設置於該複合金屬電極外層20。 Fig. 1 is a perspective view showing the structure of a divalent metal-iron/aluminum composite metal oxide electrode according to a first preferred embodiment of the present invention. Referring to FIG. 1 , the divalent metal-iron/aluminum composite metal oxide electrode structure of the first preferred embodiment of the present invention comprises a metal oxide electrode 1, an electrode core 10 and a composite metal electrode. a composite metallic electrode shell layer 20, wherein the electrode core layer 10 is made of the first metal material, and the composite metal electrode outer layer 20 is made of the second composite metal material (ie, a cobalt-iron/aluminum composite metal material) Made of cobalt-iron/aluminum composite metal material or other divalent metal-iron/aluminum composite metal material. That is, the first metal material is disposed on the electrode core layer 10, and the second composite metal material is disposed on the composite metal electrode outer layer 20.

請再參照第1圖所示,舉例而言,該金屬氧化電極1為一圓柱體〔cylinder〕或其它斷面形狀長條體〔elongated rod〕,例如:多角形斷面長條體或齒輪形斷面長條體,且該複合金屬電極外層20對應設置於該電極芯層10上,以便在該電極芯層10及複合金屬電極外層20之間形成一氧化還原反應區域11。 Referring to FIG. 1 again, for example, the metal oxide electrode 1 is a cylinder or an elongated rod, for example, a polygonal section elongated body or a gear shape. The laminated metal strip outer layer 20 is correspondingly disposed on the electrode core layer 10 to form a redox reaction region 11 between the electrode core layer 10 and the composite metal electrode outer layer 20.

請再參照第1圖所示,舉例而言,該電極芯層 10及複合金屬電極外層20組成該金屬氧化電極1,且利用該金屬氧化電極1之第一金屬材料及第二複合金屬材料適當結合一過硫酸鹽材料,例如:過硫酸鈉材料〔SPS,Sodium persulfate〕、過氧硫酸鉀材料〔PMS,Potassium peroxymonosulfate〕、具硫酸根自由基材料或其任意組合,以便適當進行催化〔catalyze〕降解或礦化處理環境中的三氯沙污染物。 Please refer to FIG. 1 again, for example, the electrode core layer 10 and the composite metal electrode outer layer 20 constitutes the metal oxide electrode 1, and the first metal material and the second composite metal material of the metal oxidation electrode 1 are appropriately combined with a persulfate material, for example, sodium persulfate material [SPS, Sodium Persulfate], potassium peroxosulfate (PMS, Potassium peroxymonosulfate), sulfated radical material or any combination thereof to properly catalyze the degradation or triclosan in the mineralized treatment environment.

第2圖揭示本發明較佳實施例之二價金屬-鐵/鋁複合金屬氧化電極製造方法之流程示意圖,其包含四個主要步驟S1至S4,但其並非用以限定本發明之步驟順序,在不脫離本發明範圍之下,可適當變更、分割、增加、合併或減少本發明較佳實施例之步驟順序。請參照第1及2圖所示,舉例而言,該金屬氧化電極1之製造適用於第2圖所示之二價金屬-鐵/鋁複合金屬氧化電極製造方法。 2 is a schematic flow chart showing a manufacturing method of a divalent metal-iron/aluminum composite metal oxide electrode according to a preferred embodiment of the present invention, which comprises four main steps S1 to S4, but it is not intended to limit the sequence of steps of the present invention. The order of the steps of the preferred embodiment of the invention may be modified, divided, added, combined or reduced as appropriate without departing from the scope of the invention. Referring to FIGS. 1 and 2, for example, the metal oxide electrode 1 is manufactured by applying the method for producing a divalent metal-iron/aluminum composite metal oxide electrode shown in FIG.

請參照第2圖所示,本發明較佳實施例之二價金屬-鐵/鋁複合金屬氧化電極製造方法包含第一步驟S1:首先,將至少一第一金屬棒〔例如:直徑為5或10mm、長度為10cm之鋁棒或其它尺寸規格〕以一酸性溶液〔例如:稀釋硫酸溶液,其硫酸與水之比例為1:2〕進行酸洗一預定時間〔例如:約為6分鐘〕,並取出該第一金屬棒。 Referring to FIG. 2, a method for manufacturing a divalent metal-iron/aluminum composite metal oxide electrode according to a preferred embodiment of the present invention includes a first step S1: first, at least one first metal rod (for example, a diameter of 5 or 10mm, 10cm long aluminum rod or other size specifications] pickled with an acidic solution (for example: diluted sulfuric acid solution, the ratio of sulfuric acid to water is 1:2) for a predetermined time (for example: about 6 minutes), And taking out the first metal rod.

請再參照第2圖所示,本發明較佳實施例之二價金屬-鐵/鋁複合金屬氧化電極製造方法包含第二步驟S2:接著,將該第一金屬棒浸漬於一第二複合金屬離子溶液〔例如:濃度約0.172M或0.86M之FeCl3溶液及濃度約0.172M、0.36M、0.5M、0.75M、0.86M或1.032M之CoCl2‧H2O溶液之共溶液〕一預定時間,並取出該已浸漬第一金屬棒。 Referring to FIG. 2 again, the manufacturing method of the divalent metal-iron/aluminum composite metal oxide electrode according to the preferred embodiment of the present invention comprises a second step S2: subsequently, the first metal rod is immersed in a second composite metal. An ionic solution (for example, a FeCl3 solution having a concentration of about 0.172 M or 0.86 M and a total solution of a CoCl 2‧H 2 O solution having a concentration of about 0.172 M, 0.36 M, 0.5 M, 0.75 M, 0.86 M, or 1.032 M) for a predetermined period of time and taken out The first metal rod has been impregnated.

請再參照第2圖所示,本發明較佳實施例之二價金屬-鐵/鋁複合金屬氧化電極製造方法包含第三步驟 S3:接著,將該已浸漬第一金屬棒以一預定溫度〔約105℃〕進行預先烘乾一預定時間〔例如:約10分鐘〕,以獲得該已烘乾第一金屬棒。 Referring to FIG. 2 again, the manufacturing method of the divalent metal-iron/aluminum composite metal oxide electrode according to the preferred embodiment of the present invention includes the third step. S3: Next, the impregnated first metal rod is pre-baked at a predetermined temperature [about 105 ° C] for a predetermined time (for example, about 10 minutes) to obtain the dried first metal rod.

請再參照第2圖所示,本發明較佳實施例之二價金屬-鐵/鋁複合金屬氧化電極製造方法包含第四步驟S4:接著,將該已烘乾第一金屬棒以一預定溫度〔約500至600℃,例如:500℃、550℃或600℃〕進行高溫烘烤鍛燒一預定時間〔例如:約1至10分鐘〕,以便在該第一金屬棒上形成至少一第二複合金屬層。本發明另一較佳實施例可選擇將該第一金屬棒以一預定溫度〔約500至600℃〕進行最後高溫烘烤鍛燒一預定時間〔例如:約60分鐘〕。 Referring to FIG. 2 again, the manufacturing method of the divalent metal-iron/aluminum composite metal oxide electrode according to the preferred embodiment of the present invention includes a fourth step S4: then, the dried first metal rod is at a predetermined temperature. [about 500 to 600 ° C, for example: 500 ° C, 550 ° C or 600 ° C] high temperature baking calcination for a predetermined time [eg, about 1 to 10 minutes] to form at least a second on the first metal rod Composite metal layer. In another preferred embodiment of the present invention, the first metal bar may be subjected to a final high temperature baking and calcination at a predetermined temperature [about 500 to 600 ° C] for a predetermined time (for example, about 60 minutes).

請再參照第1及2圖所示,該第一金屬棒形成該電極芯層10,且該複合金屬電極外層20包覆該電極芯層10。即,將該複合金屬電極外層20設置於該電極芯層10上,以形成一二價金屬-鐵/鋁複合金屬氧化電極。舉例而言,該複合金屬電極外層20具有一鈷鐵氧磁體結構、一鈷鐵氧結晶結構〔例如:CoFe2O4結晶型態〕或其它二價金屬鐵氧磁體結構。 Referring to FIGS. 1 and 2 again, the first metal rod forms the electrode core layer 10, and the composite metal electrode outer layer 20 covers the electrode core layer 10. That is, the composite metal electrode outer layer 20 is disposed on the electrode core layer 10 to form a divalent metal-iron/aluminum composite metal oxide electrode. For example, the composite metal electrode outer layer 20 has a cobalt ferrite magnet structure, a cobalt iron oxide crystal structure (for example, a CoFe 2 O 4 crystal form) or other divalent metal ferrite magnet structure.

請再參照第1及2圖所示,在整治土壤或水體時,利用該二價金屬-鐵/鋁複合金屬氧化電極增強一硫酸根自由基〔sulfate radical〕於環境中的移動能力,以便適當進行催化降解或礦化處理環境中的三氯沙污染物。 Referring to Figures 1 and 2, the divalent metal-iron/aluminum composite metal oxide electrode is used to enhance the mobility of the sulfate radical in the environment during the remediation of soil or water. Conducting triclosan contaminants in a catalytically degraded or mineralized environment.

第3圖揭示本發明較佳實施例之二價金屬-鐵/鋁複合金屬氧化電極構造採用浸漬液二價金屬濃度對電極塗佈率之曲線示意圖。請參照第3圖所示,本發明較佳實施例選擇製備一鈷-鐵/鋁複合金屬氧化電極。隨著製備液中鈷濃度上升,其電極表面鈷塗佈量上升;當鈷濃度超過0.86M後,其有效二價鈷塗佈量開始下降,而鐵之塗佈量卻上 升。另外,在製備液中鈷濃度達0.75M時,鈷鐵塗佈比例達最大1.1;當鈷濃度再提升至0.86M時,鈷鐵塗佈比例較低。 Fig. 3 is a view showing the curve of the divalent metal-iron/aluminum composite metal oxide electrode structure of the preferred embodiment of the present invention using the divalent metal concentration of the impregnation liquid to the electrode coating rate. Referring to FIG. 3, in the preferred embodiment of the present invention, a cobalt-iron/aluminum composite metal oxide electrode is selectively prepared. As the cobalt concentration in the preparation liquid rises, the amount of cobalt coating on the surface of the electrode increases; when the cobalt concentration exceeds 0.86 M, the effective amount of cobalt coating starts to decrease, while the coating amount of iron is on. Rise. In addition, when the cobalt concentration in the preparation liquid reaches 0.75 M, the cobalt iron coating ratio reaches a maximum of 1.1; when the cobalt concentration is further increased to 0.86 M, the cobalt iron coating ratio is low.

第4圖揭示本發明較佳實施例之二價金屬-鐵/鋁複合金屬氧化電極構造進行X光繞射〔XRD,X ray diffraction〕分析之圖譜示意圖。請參照第4圖所示,本發明較佳實施例選擇製備一鈷-鐵/鋁複合金屬氧化電極,並以XRD晶體繞射實驗時,所塗佈之鐵鋁金屬氧化物經過X光繞射分析後,於2 θ=30.7、36.5、38、55.6、65具有數個較強之特徵峰值,其為CoFe2O4之結晶結構(JCPDS No:00-022-1068),其峰值分別對應之晶格平面指數分別為(2 2 0)、(3 1 1)、(2 2 2)、(4 0 0)、(5 1 1)及(4 4 0)。 Fig. 4 is a view showing a map of X-ray diffraction (XRD) analysis of a divalent metal-iron/aluminum composite metal oxide electrode structure according to a preferred embodiment of the present invention. Referring to FIG. 4, in a preferred embodiment of the present invention, a cobalt-iron/aluminum composite metal oxide electrode is selected and X-ray diffraction is applied to the coated iron-aluminum metal oxide by XRD crystal diffraction. After analysis, there are several strong characteristic peaks at 2θ=30.7, 36.5, 38, 55.6, and 65, which are the crystal structures of CoFe2O4 (JCPDS No: 00-022-1068), and their peaks correspond to the lattice planes respectively. The indices are (2 2 0), (3 1 1), (2 2 2), (4 0 0), (5 1 1), and (4 4 0).

請再參照第3及4圖所示,將製備液鈷濃度分別選擇為0M、0.172M、0.43M、0.86M,製備溫度600℃,鍛燒次數為10次下製備之電極,進行表面材料晶格結構分析,並以主要所產生之CoFe2O4尖晶石結構〔cubic spinel structure〕在2 θ=36.5下所產生之特徵峰,進行CoFe2O4晶體結構完整性之比較。在鈷濃度為0M時,並無產生尖晶石結構之特徵峰;當鈷濃度提升至0.172M時,其2 θ=36.5之特徵峰波形較紊亂,即其晶體結構較為複雜;當鈷濃度為0.43M時,分裂特徵峰消失,即其晶體結構形成較單一;當鈷濃度再提升為0.86M時,其特徵峰強度提升,且波型亦較尖銳,即提升其晶體結構的穩定性。 Please refer to the third and fourth figures, and select the electrode cobalt concentration to be 0M, 0.172M, 0.43M, 0.86M, the preparation temperature is 600 ° C, the number of calcination times is 10 times, and the surface material crystal is prepared. The structure of the lattice was analyzed, and the structural peaks of CoFe2O4 crystals were compared with the characteristic peaks produced by the main CuFe2O4 cubic spinel structure at 2θ=36.5. When the cobalt concentration is 0M, there is no characteristic peak of spinel structure; when the cobalt concentration is increased to 0.172M, the characteristic peak waveform of 2θ=36.5 is disordered, that is, the crystal structure is more complicated; when the cobalt concentration is At 0.43M, the splitting characteristic peak disappears, that is, its crystal structure is formed relatively single; when the cobalt concentration is further increased to 0.86M, the characteristic peak intensity is improved, and the wave shape is sharper, that is, the stability of the crystal structure is improved.

請再參照第3及4圖所示,在整治土壤或水體時,利用該鈷-鐵/鋁複合金屬氧化電極增強硫酸根自由基於環境中的移動能力。 Referring to Figures 3 and 4, the cobalt-iron/aluminum composite metal oxide electrode is used to enhance the freedom of movement of the sulfate based on the environment during the treatment of soil or water.

第5圖揭示本發明第二較佳實施例之二價金屬-鐵/鋁複合金屬氧化電極構造之立體示意圖,其對應於第1圖之二價金屬-鐵/鋁複合金屬氧化電極構造。請參照第5 圖所示,相對於第一實施例,本發明第二較佳實施例之金屬氧化電極1a包含一電極芯層10、一第一複合金屬電極外層20a及一第二複合金屬電極外層20b。 Fig. 5 is a perspective view showing the structure of a divalent metal-iron/aluminum composite metal oxide electrode according to a second preferred embodiment of the present invention, which corresponds to the divalent metal-iron/aluminum composite metal oxide electrode structure of Fig. 1. Please refer to section 5 As shown in the figure, the metal oxide electrode 1a of the second preferred embodiment of the present invention comprises an electrode core layer 10, a first composite metal electrode outer layer 20a and a second composite metal electrode outer layer 20b.

請再參照第2及5圖所示,本發明第二較佳實施例之金屬氧化電極1a可選擇重複第一步驟S1至第四步驟S4數次〔例如:10次〕,如第2圖所示。在該第一複合金屬電極外層20a上形成該第二複合金屬電極外層20b,以便形成一多層複合金屬層。最後,可選擇將該第一金屬棒以一預定溫度〔約500至600℃〕進行最後高溫烘烤鍛燒一預定時間〔例如:約60分鐘〕。 Referring to FIGS. 2 and 5 again, the metal oxide electrode 1a of the second preferred embodiment of the present invention may repeat the first step S1 to the fourth step S4 several times (for example, 10 times), as shown in FIG. Show. The second composite metal electrode outer layer 20b is formed on the first composite metal electrode outer layer 20a to form a multilayer composite metal layer. Finally, the first metal bar may be subjected to a final high temperature baking and calcination at a predetermined temperature [about 500 to 600 ° C] for a predetermined time (for example, about 60 minutes).

第6圖揭示本發明第三較佳實施例之二價金屬-鐵/鋁複合金屬氧化電極構造之立體示意圖,其對應於第1圖之二價金屬-鐵/鋁複合金屬氧化電極構造。請參照第6圖所示,相對於第一實施例,本發明第三較佳實施例之金屬氧化電極1’包含一電極芯層10及一複合金屬電極外層20,且該金屬氧化電極1’為一扁柱體,以便增加在該電極芯層10及複合金屬電極外層20之間形成一氧化還原反應區域11。 Fig. 6 is a perspective view showing the structure of a divalent metal-iron/aluminum composite metal oxide electrode according to a third preferred embodiment of the present invention, which corresponds to the structure of the divalent metal-iron/aluminum composite metal oxide electrode of Fig. 1. Referring to FIG. 6, the metal oxide electrode 1' of the third preferred embodiment of the present invention comprises an electrode core layer 10 and a composite metal electrode outer layer 20, and the metal oxide electrode 1' is opposite to the first embodiment. It is a flat cylinder to increase the formation of a redox reaction region 11 between the electrode core layer 10 and the composite metal electrode outer layer 20.

第7圖揭示本發明第三較佳實施例之二價金屬-鐵/鋁複合金屬氧化電極構造組成電極陣列之立體示意圖,其對應於第1圖之二價金屬-鐵/鋁複合金屬氧化電極構造。請參照第7圖所示,選擇將數個該金屬氧化電極1’以一預定排列間距組成一扁柱體電極陣列,以便依不同需求配置不同數量的該金屬氧化電極1’,且可容置於一電動力土壤現場整治裝置或一電動力土壤整治槽內。 FIG. 7 is a perspective view showing the electrode array of the divalent metal-iron/aluminum composite metal oxide electrode according to the third preferred embodiment of the present invention, which corresponds to the divalent metal-iron/aluminum composite metal oxide electrode of FIG. structure. Referring to FIG. 7 , a plurality of the metal oxide electrodes 1 ′ are selected to form a flat cylindrical electrode array at a predetermined arrangement pitch, so as to configure different numbers of the metal oxide electrodes 1 ′ according to different requirements, and can be accommodated. In an electrodynamic soil site remediation device or an electrodynamic soil remediation tank.

請再參照第1、5及7圖所示,同樣的,選擇將數個該金屬氧化電極1或1a以一預定排列間距組成一圓柱體電極陣列,且該圓柱體電極陣列或扁柱體電極陣列可選擇排列形成各種形狀的電極陣列。或,本發明另一較佳 實施例可選擇將數個該金屬氧化電極1或1a及數個該金屬氧化電極1’混合編排形成一混編電極陣列。 Referring to Figures 1, 5 and 7, again, a plurality of the metal oxide electrodes 1 or 1a are selected to form a cylindrical electrode array at a predetermined arrangement pitch, and the cylindrical electrode array or the flat cylinder electrode The array can be arranged to form an array of electrodes of various shapes. Or, another preferred embodiment of the invention The embodiment may optionally combine a plurality of the metal oxide electrodes 1 or 1a and a plurality of the metal oxide electrodes 1' to form a mixed electrode array.

第8圖揭示本發明較佳實施例之於土壤、底泥及水體中三氯沙處理方法之流程示意圖。請參照第1及8圖所示,本發明較佳實施例之於土壤、底泥及水體中三氯沙處理方法包含步驟S1:首先,提供一電動力整治裝置〔例如:電動力土壤整治裝置、電動力土壤現場整治裝置、電動力底泥整治裝置、電動力底泥現場整治裝置、電動力水整治裝置或電動力環境現場整治裝置〕或一電動力整治系統。 Figure 8 is a flow chart showing the process of treating triclosan in soil, sediment and water in a preferred embodiment of the present invention. Referring to Figures 1 and 8, the method for treating triclosan in soil, sediment and water body according to a preferred embodiment of the present invention comprises the step S1: First, an electrodynamic remediation device is provided (for example, an electrodynamic soil remediation device) , electric power soil site remediation device, electric power bottom mud remediation device, electric power bottom mud site remediation device, electric power water remediation device or electric power environment site remediation device) or an electric power remediation system.

請參照第1及8圖所示,本發明較佳實施例之於土壤、底泥及水體中三氯沙處理方法包含步驟S2:接著,將一三氯沙待整治物〔例如:水、地下水體、土壤、底泥或污泥〕容置於該電動力整治裝置,且該三氯沙待整治物包含一三氯沙污染物。 Referring to Figures 1 and 8, the method for treating triclosan in soil, sediment and water body according to a preferred embodiment of the present invention comprises the step S2: Next, a triclosan is to be rectified (for example: water, groundwater) The body, the soil, the sediment or the sludge is placed in the electric power remediation device, and the triclosan to be treated contains a triclosan contaminant.

請參照第1及8圖所示,本發明較佳實施例之於土壤、底泥及水體中三氯沙處理方法包含步驟S3:接著,將該二價金屬-鐵/鋁複合金屬氧化電極或金屬氧化電極1設置於該電動力整治裝置之三氯沙待整治物,而該二價金屬-鐵/鋁複合金屬氧化電極包含該電極芯層10及複合金屬電極外層20,且該電極芯層10由一含鋁金屬材料製成,且該複合金屬電極外層20由一含二價金屬-鐵複合金屬材料〔例如:鈷-鐵/鋁複合金屬材料、含鈷-鐵/鋁複合金屬材料或其它二價金屬-鐵/鋁複合金屬材料〕製成。 Referring to Figures 1 and 8, the method for treating triclosan in soil, sediment and water body according to a preferred embodiment of the present invention comprises the step S3: subsequently, the divalent metal-iron/aluminum composite metal oxide electrode or The metal oxide electrode 1 is disposed on the triclosan to be rectified in the electrodynamic curing device, and the divalent metal-iron/aluminum composite metal oxide electrode comprises the electrode core layer 10 and the composite metal electrode outer layer 20, and the electrode core layer 10 is made of an aluminum-containing metal material, and the composite metal electrode outer layer 20 is composed of a divalent metal-iron composite metal material (for example: cobalt-iron/aluminum composite metal material, cobalt-iron/aluminum composite metal material or Other divalent metal-iron/aluminum composite metal materials are made.

請參照第1及8圖所示,本發明較佳實施例之於土壤、底泥及水體中三氯沙處理方法包含步驟S4:接著,在三氯沙整治處理操作時,在該電極芯層10及複合金屬電極外層20之間形成一氧化還原反應區域11〔如第1圖之虛線所示〕。 Referring to Figures 1 and 8, the method for treating triclosan in soil, sediment and water body according to a preferred embodiment of the present invention comprises the step S4: then, in the operation of the triclosan rectification treatment, in the electrode core layer A redox reaction region 11 is formed between the 10 and the composite metal electrode outer layer 20 (shown by a broken line in Fig. 1).

請參照第1及8圖所示,本發明較佳實施例之於土壤、底泥及水體中三氯沙處理方法包含步驟S5:接著,利用該二價金屬-鐵/鋁複合金屬氧化電極或金屬氧化電極1增強一硫酸根自由基的移動能力,且利用該含鋁金屬材料及含二價金屬-鐵複合金屬材料適當結合一過硫酸鹽材料,以便適當進行催化降解或礦化處理該三氯沙待整治物之三氯沙污染物。 Referring to Figures 1 and 8, the method for treating triclosan in soil, sediment and water body according to a preferred embodiment of the present invention comprises the step S5: subsequently, using the divalent metal-iron/aluminum composite metal oxide electrode or The metal oxide electrode 1 enhances the mobility of the monosulfate radical, and appropriately combines the persulfate material with the aluminum-containing metal material and the divalent metal-iron composite metal material to appropriately perform catalytic degradation or mineralization treatment. The triclosan contaminant of the chlorine sand to be rectified.

前述較佳實施例僅舉例說明本發明及其技術特徵,該實施例之技術仍可適當進行各種實質等效修飾及/或替換方式予以實施;因此,本發明之權利範圍須視後附申請專利範圍所界定之範圍為準。本案著作權限制使用於中華民國專利申請用途。 The foregoing preferred embodiments are merely illustrative of the invention and the technical features thereof, and the techniques of the embodiments can be carried out with various substantial equivalent modifications and/or alternatives; therefore, the scope of the invention is subject to the appended claims. The scope defined by the scope shall prevail. The copyright limitation of this case is used for the purpose of patent application in the Republic of China.

Claims (10)

一種於土壤、底泥及水體中三氯沙處理系統,其包含:一電動力整治裝置;一三氯沙待整治物,其容置於該電動力整治裝置,且該三氯沙待整治物包含一三氯沙污染物;至少一二價金屬-鐵/鋁複合金屬氧化電極,其設置於該電動力整治裝置之三氯沙待整治物,且該二價金屬-鐵/鋁複合金屬氧化電極包含一內芯層及一外表層;一電極芯層,其設置於該二價金屬-鐵/鋁複合金屬氧化電極之內芯層,而該電極芯層由一第一金屬材料製成,且該第一金屬材料為一含鋁金屬材料;一複合金屬電極外層,其設置於該二價金屬-鐵/鋁複合金屬氧化電極之外表層,而該複合金屬電極外層由一第二複合金屬材料製成,且該第二複合金屬材料為一含二價金屬-鐵複合金屬材料;及一氧化還原反應區域,其形成在該電極芯層及複合金屬電極外層之間;其中在整治該三氯沙待整治物時,利用該第一金屬材料及第二複合金屬材料適當結合一過硫酸鹽材料,以便適當進行催化降解或礦化處理該三氯沙待整治物之三氯沙污染物。 A triclosan treatment system in soil, sediment and water body, comprising: an electric power rectification device; a triclosan to be rectified, which is placed in the electrodynamic remediation device, and the triclosan is to be rectified The invention comprises a triclosan contaminant; at least one divalent metal-iron/aluminum composite metal oxide electrode, which is disposed in the electrochlorination device, the triclosan to be rectified, and the divalent metal-iron/aluminum composite metal oxide The electrode comprises an inner core layer and an outer skin layer; an electrode core layer disposed on the inner core layer of the divalent metal-iron/aluminum composite metal oxide electrode, and the electrode core layer is made of a first metal material. And the first metal material is an aluminum-containing metal material; a composite metal electrode outer layer is disposed on the outer surface of the divalent metal-iron/aluminum composite metal oxide electrode, and the composite metal electrode outer layer is composed of a second composite metal Made of a material, and the second composite metal material is a divalent metal-iron composite metal material; and a redox reaction region formed between the electrode core layer and the outer layer of the composite metal electrode; wherein the third is rectified Chlorhexaside When the object, using the first metallic material and the second composite material suitable combination of a metal persulfate material in order to appropriately triclosan contaminant mineralization process or catalytic degradation the regulation thereof be of triclosan. 依申請專利範圍第1項所述之於土壤、底泥及水體中三氯沙處理系統,其中該複合金屬電極外層具有一鈷鐵氧磁體結構或一鈷鐵氧結晶結構。 The triclosan treatment system in soil, sediment and water body according to claim 1 of the patent application, wherein the outer layer of the composite metal electrode has a cobalt ferrite magnet structure or a cobalt ferrosilicon crystal structure. 依申請專利範圍第1項所述之於土壤、底泥及水體中三氯沙處理系統,其中該二價金屬-鐵/鋁複合金屬氧化電極為一圓柱體或一扁柱體。 The triclosan treatment system in soil, sediment and water body according to claim 1 of the patent application scope, wherein the divalent metal-iron/aluminum composite metal oxidation electrode is a cylinder or a flat cylinder. 依申請專利範圍第3項所述之於土壤、底泥及水體中三氯沙處理系統,其中該圓柱體或扁柱體組成一電極陣列。 The triclosan treatment system in soil, sediment and water body according to item 3 of the patent application scope, wherein the cylinder or the flat cylinder constitutes an electrode array. 依申請專利範圍第1項所述之於土壤、底泥及水體中 三氯沙處理系統,其中該過硫酸鹽材料包含過硫酸鈉材料、過硫酸鉀材料、具硫酸根自由基材料或其任意組合。 According to the scope of the patent application, in the soil, sediment and water body A sulphate treatment system wherein the persulfate material comprises sodium persulfate material, potassium persulfate material, sulfated radical material, or any combination thereof. 一種於土壤、底泥及水體中三氯沙處理方法,其包含:提供一電動力整治裝置;將一三氯沙待整治物容置於該電動力整治裝置,且該三氯沙待整治物包含一三氯沙污染物;將一二價金屬-鐵/鋁複合金屬氧化電極設置於該電動力整治裝置之三氯沙待整治物,而該二價金屬-鐵/鋁複合金屬氧化電極包含一電極芯層及一複合金屬電極外層,且該電極芯層由一含鋁金屬材料製成,且該複合金屬電極外層由一含二價金屬-鐵複合金屬材料製成;在該電極芯層及複合金屬電極外層之間形成一氧化還原反應區域;及利用該含鋁金屬材料及含二價金屬-鐵複合金屬材料適當結合一過硫酸鹽材料,以便適當進行催化降解或礦化處理該三氯沙待整治物之三氯沙污染物。 A method for treating triclosan in soil, sediment and water body, comprising: providing an electric power rectification device; arranging a triclosan to be rectified into the electrodynamic rectification device, and the triclosan is to be rectified The invention comprises a triclosan contaminant; a divalent metal-iron/aluminum composite metal oxidation electrode is disposed on the triclosan to be rectified in the electrodynamic rectification device, and the divalent metal-iron/aluminum composite metal oxidation electrode comprises An electrode core layer and a composite metal electrode outer layer, wherein the electrode core layer is made of an aluminum-containing metal material, and the composite metal electrode outer layer is made of a divalent metal-iron composite metal material; Forming a redox reaction region between the outer layer of the composite metal electrode; and appropriately combining the persulfate material with the aluminum-containing metal material and the divalent metal-iron composite metal material for proper catalytic degradation or mineralization treatment The triclosan contaminant of the chlorine sand to be rectified. 依申請專利範圍第6項所述之於土壤、底泥及水體中三氯沙處理方法,其中該含二價金屬-鐵複合金屬材料為一含鈷鐵複合金屬材料。 The method for treating triclosan in soil, sediment and water according to item 6 of the patent application scope, wherein the divalent metal-iron composite metal material is a cobalt-iron composite metal material. 依申請專利範圍第6項所述之於土壤、底泥及水體中三氯沙處理方法,其中將該複合金屬電極外層設置於該電極芯層上。 The method for treating triclosan in soil, sediment and water according to item 6 of the patent application scope, wherein the outer layer of the composite metal electrode is disposed on the electrode core layer. 依申請專利範圍第6項所述之於土壤、底泥及水體中三氯沙處理方法,其中在該複合金屬電極外層上形成另一複合金屬層,以便形成一多層複合金屬層。 The method for treating triclosan in soil, sediment and water according to claim 6 of the patent application, wherein another composite metal layer is formed on the outer layer of the composite metal electrode to form a multilayer composite metal layer. 依申請專利範圍第6項所述之於土壤、底泥及水體中三氯沙處理方法,其中利用該二價金屬-鐵/鋁複合金屬氧化電極增強一硫酸根自由基於環境中的移動能力。 The method for treating triclosan in soil, sediment and water according to item 6 of the patent application scope, wherein the divalent metal-iron/aluminum composite metal oxide electrode is used to enhance the free movement of the monosulfate based on the environment.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5398756A (en) 1992-12-14 1995-03-21 Monsanto Company In-situ remediation of contaminated soils
US20140255099A1 (en) 2013-03-11 2014-09-11 Geosyntec Consultants, Inc. In situ remediation of soils and ground water containing organic contaminants
TW201634138A (en) 2015-03-27 2016-10-01 國立高雄大學 Composite metallic oxidation electrode structure and manufacturing method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5398756A (en) 1992-12-14 1995-03-21 Monsanto Company In-situ remediation of contaminated soils
US20140255099A1 (en) 2013-03-11 2014-09-11 Geosyntec Consultants, Inc. In situ remediation of soils and ground water containing organic contaminants
TW201634138A (en) 2015-03-27 2016-10-01 國立高雄大學 Composite metallic oxidation electrode structure and manufacturing method thereof

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