1280952 九、發明說明： 【發明所屬之技術領域】 本發明主要係揭示一種改善土壤（污泥）鉛、銅含量之 方法’尤其是指一種可維持pH中性且具提升重金屬移除效 率之處理方法。 【先前技術】 • 國内外許多因有害事業廢棄物的不當處置而造成的土 壌（污泥）重金屬污染問題不斷浮現，這些重金屬污染嚴重 地對居民健康及生態造成危害，極需加以有效整治與復 月。由於土壤（污泥）的成分複雜且性質各異，因此在進 行整/〇復育時也有相當多不同的技術，就處理技術與場址 的關係可分為三類： 第一類為現地（in-situ)處理技術：指未經過開挖污 柒土壤程序，直接在現地進行污染物之處理； _ 第二類為現場（on-site)處理：經過開挖程序後直接 在現場處理； 第二類為離場（ex-situ)處理：開挖受污染土壤（污 泥）後將土壤（污泥）運離場址再進行處理。 然而在眾多土壤（污泥）整治技術中，現地處理技術 因其在經濟面的優勢及對場址的低破壞性，具有高度商業 化潛力，其中電動力（Electrokinetics, EK)復育技術是 近年來新崛起且極具發展潛力的處理方法，其主要優點 為：（1)可以在異質性高且滲透性低之土壤（污泥）介質中 1280952 產生均勻之電滲透流；（2)可以控制電滲透流流動方向；（3) ： 對污染物的去除效率良好；（4)具有相當高的經濟效益；（5) 可同時與其他整治技術整合使用；（6)可適用之污染物類型 十分廣泛。 目前所應用的電動力技術，通常在操作程序中，正極 附近的電解質液的pH值會維持在2左右，相反的，在靠近 負極區域的pH值則高達12左右，由於酸受電場驅動而向 φ 負極移動，在酸鋒移動的過程中可能造成土壤（污泥）的 酸化（acidifi-cation)而破壞土壤（污泥）中的成分，並 導致土壤（污泥）顆粒的界達電位可能會因為土壤（污泥） 的酸化而產生電性逆轉（界達電位為正值），其造成電渗透 &的料降低甚料致反向流㈣影響絲絲並降低電 ML效率，重金屬污染物常易累積於陰極處，使得污染整治 失敗。另外，即使重金屬自土壤（污泥）中移除後，形成重 金屬廢水仍需後續處理，造成整治成本過高。因此，有鑑 • 於上述習知方法之缺失，本發明人乃發明出一種『改善土 壤（污泥)錯、銅含量之方法』，其係可克服上述習式方法 【發明内容】 半之顏2善土壤(巧泥)錯、銅含量之方法』所欲解 I、、亏ΤΙ中鱼在於，該習知方法僅將電極直接安置於土 Ϊ直土壤(污泥）面直接接觸，因此導致土壤（污 知作溶液邱的影響，使得土壌（污泥）變化梯 1280952 度過大，造成系統電滲透流不穩定、 作時間加長轉低，並且破壞土壌\，屬效率隨操 習知方法有改善之必要。 組成。因此’該 本發明『改善土壌（污泥）錯、銅含量 要實施方法係將陽、陰二電極安置在操作液儲存=其主 該陽極可實施為惰性電極，陰極可實施 二’且 皆不與土壤（污泥）直接接觸，且操作液屬兩者 低毒性的電解質液混合適t濃度的t合劑為:衝且 輸送裝置將陰極溶液輸送至陽極儲槽，以、^错由一 統；藉此，在去除土壌（污泥）重金屬過程中系 泥)PH維持中性，且移除之重金屬更可電鑛於(污 而無須後續廢水處理。 、K板上’ 其他目的、優點和本發明的新穎特性將從 描述與相關的附圖更加顯明。 ^评、、，田的 【實施方式】 茲舉一較 有關本發明所採用之技術、手段及其功效， 佳實施例並配合圖式詳述如後： 之用，在專 請參閱圖一至圖六，圖中所示者僅供說明 利申請上並不受此種系統之限制。 請先參閱第-圖，為本發明之方法示意圖。參昭 所不’本發明係揭示有-種改善土壤（污泥)錯、飼含 方法，其所需使用到的裝置至少包含有：二電 及陰極2G)、—直流電源供應器30、-抽送泵浦4〇及= 1280952 叮衣填操作液50 (含螯合劑之緩衝溶液，其中螯合劑為 EDTA 納鹽（ethylene diaminetetraacetic acid)，該缓衝 >谷液之電解質為碳酸鈉、碳酸鉀、麟酸鈉與填酸鉀等無害 鹽類’其濃度維持於〇· 〇〇5至〇· 01M之間）之操作液儲存 區·’其中該陽極1〇係為惰性電極（如··石墨、白金、DSA (形狀文定陽極，Dimensi〇na!y stable Anode))，而陰極 為金屬電極（如··鉛、銅與不銹鋼等金屬電極）。於本實施 例中忒％極10為石墨，而陰極2〇於本實施例中為金屬， 上述違一電極10、20皆須懸置於該操作液儲存區中而 不與土壤7〇(污泥）接觸，本實施例中，待處理土壌7〇(污 泥）是置於該二電極10、20之間。1280952 IX. Description of the invention: [Technical field to which the invention pertains] The present invention mainly discloses a method for improving the content of lead and copper in soil (sludge), in particular, a treatment for maintaining pH neutrality and improving the removal efficiency of heavy metals. method. [Prior Art] • Many domestic and foreign soil and sludge (sludge) heavy metal pollution problems caused by improper disposal of hazardous industrial wastes are constantly emerging. These heavy metal pollutions seriously cause harm to residents' health and ecology, and they need to be effectively rectified and restored. month. Due to the complex composition and different nature of the soil (sludge), there are quite a few different techniques for the whole/cultivation. The relationship between treatment technology and site can be divided into three categories: The first category is the local ( In-situ) treatment technology: refers to the process of polluting soil without excavation, directly processing the pollutants in the field; _ The second type is on-site treatment: after the excavation process, it is directly processed on site; The second category is ex-situ treatment: after excavating contaminated soil (sludge), the soil (sludge) is transported away from the site for further treatment. However, in many soil (sludge) remediation technologies, the in-situ treatment technology has high commercial potential due to its economic advantages and low destructiveness to the site. Among them, electrokinetics (EK) remediation technology is in recent years. The main advantages of the newly emerging and highly promising treatment methods are: (1) Uniform electroosmotic flow can be produced in 1280952 in soil (sludge) medium with high heterogeneity and low permeability; (2) can be controlled The direction of electroosmotic flow; (3): good removal efficiency of pollutants; (4) has considerable economic benefits; (5) can be integrated with other remediation technologies at the same time; (6) the types of pollutants that can be applied are very widely. At present, the electrodynamic technology used is usually maintained in the operating procedure, the pH of the electrolyte near the positive electrode is maintained at about 2, and conversely, the pH near the negative electrode is as high as about 12, because the acid is driven by the electric field. φ The movement of the negative electrode may cause the acidifi-cation of the soil (sludge) to destroy the components in the soil (sludge) during the movement of the acid front, and may cause the boundary potential of the soil (sludge) particles to be Because of the acidification of the soil (sludge), the electrical reversal (the positive potential is positive), which causes the electro-osmosis & material to decrease, which is expected to cause reverse flow (4) affecting the filament and reducing the electrical ML efficiency, heavy metal pollutants It is often easy to accumulate at the cathode, which makes the pollution remediation fail. In addition, even if heavy metals are removed from the soil (sludge), the formation of heavy metal wastewater still requires subsequent treatment, resulting in excessive remediation costs. Therefore, in view of the lack of the above-mentioned conventional methods, the inventors have invented a "method for improving soil (sludge) error and copper content, which can overcome the above-mentioned conventional method [invention content] 2 The method of good soil (smart mud) and copper content is to solve the problem of I, and the fish in the deficit. The conventional method only directly places the electrode directly on the soil (sludge) surface of the soil, thus causing The soil (stained as a solution to the effect of the solution, so that the soil shovel (sludge) change ladder 1280952 is too large, resulting in unstable system electroosmotic flow, longer and slower, and destroying soil ,, the efficiency is improved with the practice method Therefore, the composition of the present invention is to improve the soil (sludge) error and copper content. The method is to place the anode and cathode electrodes in the operating fluid storage. The anode can be implemented as an inert electrode, and the cathode can be implemented. The two's are not in direct contact with the soil (sludge), and the operating fluid is a low toxicity electrolyte solution mixed with a suitable concentration of t mixture: the rushing device delivers the cathode solution to the anode storage tank, to ^ By the same system; in this way, in the process of removing heavy metals from soil (sludge), the pH of the mud is maintained neutral, and the removed heavy metals can be electro-mineralized (stained without subsequent wastewater treatment. Advantages and novel features of the present invention will be more apparent from the description and the associated drawings. [Embodiment], [Embodiment] [Embodiment] A technique, a method, and an effect thereof, which are more relevant to the present invention, For details, please refer to Figure 1 to Figure 6. The figures are for illustrative purposes only and are not subject to such system. Please refer to the figure - Schematic diagram of the method. The invention discloses that there is a method for improving soil (sludge) error and feeding, and the device to be used at least includes: two electric and cathode 2G), DC power supply 30, - pumping pump 4 〇 and = 1280952 叮 filling operation liquid 50 (a buffer solution containing a chelating agent, wherein the chelating agent is ethylene diaminetetraacetic acid, the buffer > the electrolyte of the valley liquid is carbonic acid Sodium, potassium carbonate, sodium cinnamate An operating fluid storage area with an innocuous salt such as potassium acetate, whose concentration is maintained between 〇·〇〇5 and 〇·01M··where the anode 1 is an inert electrode (eg, graphite, platinum, DSA) (Dimensi〇na!y stable Anode)), and the cathode is a metal electrode (such as metal electrodes such as lead, copper and stainless steel). In the present embodiment, the 忒% pole 10 is graphite, and the cathode 2 is metal in the embodiment, and the above-mentioned electrodes 10 and 20 are suspended in the operating fluid storage area without being soiled. Mud) contact, in this embodiment, the soil 7 〇 (sludge) to be treated is placed between the two electrodes 10, 20.
一參閱第二圖，為本方法現場安裝俯視圖。參照該圖所 二本毛月於污染土壌7〇(污泥）挖掘一環繞區域（不限形 狀准本實施例中係為方形）以作為操作液儲存區60,利 用隔水材料8G覆於操作液儲存區⑼周邊及底層（即可形 f儲存槽結構），使得操作液5Q不朗漏；另外，可再 且网尺，料8〇在操作液儲存區6〇内圍成一作用區， ::用區71二側分別懸置陽極ι〇與陰極 設直、供應_電壓梯度2 1 單元，ΐηΐ陰極20端，此為本發縣本處理 時處理複肢大核理單元同 在此必/頁另外注意的是，該陽極10與陰極20之間 1280952 更架設有-輸送襄置90(. 送裝置90係可將陰極2 J、中為—輸水官），該輸 與該贿浦40形成為—操端’藉此以 循環系統）。 、楯％系統（pH中和之 參閱第三圖，為第-圓 所示，本發明之隔?二：:端侧剖視圖；參照該圖 ^水材枓80於接觸土壤 污染土壤70(污泥）中，同理，㈣:作液儲存£ 60傳入 泥)接觸面，亦須透過透水孔污染土壤7〇(污 送至陰極20。 #孔81叹得重金屬污染物可傳 在此，必須特別說明的是，陽才亟1〇 因為若是陽極1。直接接觸於污;f壤： j，P使本方法擁有水循環中和系統，靠近陽錢處之 =70(污泥）仍快速被酸化，無法達到預期之去除效果； 同理’陰極20亦須避免直接接觸土壤7〇 (污泥），否則， U域土壤70 (污泥）將受驗影響，且造成重金屬沉積而 …、/移除，而上述a又施之配置，即促使被處理土壤7〇(污 泥）於pH中性下，有效地被處理。 最後’請參閱第四及第五圖’係本發明實際應用於受 錯與鋼污染土壤時（土壤樣本由台中地區污染場址採集，其 污染為工廠廢水排放所造成），分析方法採用環保署「土壤 檢測方法總則（NIEAS103.60C)」、「重金屬檢測方法總 則（NIEA M103.01C)」及 NIEA C304· 00B ;其中，在本實驗 中係以EDTA-Na2為操作液（電解液），儲存區與作用區間 1280952 之操作液為含螯合劑之緩衝溶液，其中螯合劑為edta納鹽 (ethylene diaminetetraacetic acid);該緩衝溶液之電 解質為碳酸鈉、破酸鉀、磷酸鈉與磷酸鉀等無害鹽類，其 濃度維持於〇· 005至〇· 01M之間。試驗中之受錯污染土壤 的初始濃度如第四圖所示，其約為6,〇〇〇 mg/kg，處理15 天後約為2, 500 mg/kg。 而第四圖中的anode position即是靠近陽極的土壤之 重金屬濃度變化線，middle position即是採取中間土壤， cathode position 即為靠近陰極土壤，而 regresi〇nHne 則是迴歸趨勢線’可由迴歸趨勢線得知其斜率為214，故 可推論每天每公斤土壤可去除214毫克—鉛。第五圖亦顯 示，本方法對銅金屬污染土壤具有頗佳之處理效果。此外， 處理過程中土壤的pH值變化如第六圖所示，其皆能維持在 穩定的中性pH值，符合本設計之要求。而為考慮安全因 素操作電机白維持於I 〇安培以下，即操作電壓梯度於 試驗中均為2·〇 v/cm以下。 、 就以上所述可以歸納出本發明具有以下之優點： s本發Θ改善土壤（污泥）錯、銅含量之方法』，其係 :陽極分別置放於操作液儲存區中，二者皆不與土 的雷紐#、、、細’且操作液可以具有高pH緩衝且低毒性 置將陰適當，的螯合劑為之，並藉由-輸送裝 透水孔進入土形成一循環系統，操作液藉由 此，在去除土瑜2 處理土壤規模而定）；憑 ' 亏泥）重金屬的過程中，可保持土壤（污 1280952 泥)pH維持中性，且移除之重金屬可電鑛於設於陰極端的 陰極板上，無織續廢水處理；是故本發明具有非破壞性、 較快的去除效率、節省成本職定的酸驗環境，實為-極 具進步性之環境工程設計。 ;本發明已透過最佳實施例的詳細圖式加以描述。熟習 該項技係可從最佳實_衍生許多變化㈣須背離本 發明的崎。目此，最佳實施例不致限制本發明的範嗜。 本發明的範疇係定義於申請專利範圍。 【圖式簡單說明】 第一圖.為具提升重金屬去除功效且維持土壤pH中性電 動力處理方法示意圖。 第二圖··為方法現場安褒俯視圖。 第二圖·為電極安裝局部放大圖。 第四圖：為土壤中鉛去除效率圖。 • 第五圖·為土壤中銅去除效率圖。 第六圖·為土壌中pH值變化圖。 【主要元件符號說明】 10陽極 40抽送泵浦 70 土壤 81透水孔 陰極 50操作液 71作用區 90輪送裝置 3〇直流電源供應器 60操作液儲存區 別隔水材料 11Referring to the second figure, a top view of the method is installed on site. Referring to the second section of the figure, the surrounding area is excavated in the contaminated soil layer 7 (sludge) (the shape is not square in this embodiment) as the operating fluid storage area 60, and the operation is performed by the water-repellent material 8G. The liquid storage area (9) is surrounded by the bottom layer and the bottom layer (ie, the shape of the storage tank structure), so that the operating liquid 5Q is not leaked; in addition, the net weight can be further divided into an active area in the operating liquid storage area 6〇. :: Use the two sides of the area 71 to suspend the anode and the cathode respectively, and supply the voltage gradient 2 1 unit, ΐηΐ cathode 20 end, which is the same as the treatment of the compound limb large-scale nuclear unit in this county. Note that the page between the anode 10 and the cathode 20 is more than 1280952. The delivery device 90 is provided. 40 is formed as - the end of the 'circulation system'.楯% system (see the third figure for pH neutralization, shown as the first circle, the second side of the present invention: the end side cross-sectional view; referring to the figure ^the water material 枓80 in contact with the soil contaminated soil 70 (sludge ), in the same way, (4): the storage surface of the liquid 60% of the contact surface, the soil must be contaminated through the permeable hole 7 〇 (stained to the cathode 20. #孔81 sighs heavy metal contaminants can be transmitted here, must In particular, Yangcai 亟1〇 because if it is the anode 1. Direct contact with the soil; f soil: j, P makes the method have a water circulation neutralization system, close to the sun money = 70 (sludge) is still quickly acidified The expected removal effect cannot be achieved; similarly, the cathode 20 must also avoid direct contact with the soil 7 (sludge). Otherwise, the U-zone soil 70 (sludge) will be affected by the test and cause heavy metal deposition... In addition, the above-mentioned a configuration is to promote the treatment of the soil 7 sludge (sludge) under pH neutrality, and is effectively processed. Finally, please refer to the fourth and fifth figures. When the soil is contaminated with steel (the soil samples are collected from the pollution site in Taichung area, and the pollution is factory waste) The method of analysis is based on the EPA's General Guidelines for Soil Testing Methods (NIEAS103.60C), the General Principles for the Detection of Heavy Metals (NIEA M103.01C) and NIEA C304·00B. Among them, EDTA- is used in this experiment. Na2 is the operating liquid (electrolyte), and the operating liquid in the storage area and the working interval 1280952 is a buffer solution containing a chelating agent, wherein the chelating agent is ethylene diaminetetraacetic acid; the electrolyte of the buffer solution is sodium carbonate, acid-breaking The concentration of harmless salts such as potassium, sodium phosphate and potassium phosphate is maintained between 〇·005 and 〇·01M. The initial concentration of the contaminated soil in the test is as shown in the fourth figure, which is about 6, 〇〇 〇mg/kg, about 2,500 mg/kg after 15 days of treatment. The anode position in the fourth figure is the heavy metal concentration change line of the soil near the anode, the middle position is the middle soil, and the cathode position is Close to the cathode soil, and regresi〇nHne is the regression trend line' can be learned from the regression trend line with a slope of 214, so it can be inferred that 214 mg-lead can be removed per kg of soil per day. It shows that the method has a good treatment effect on copper-contaminated soil. In addition, the pH value of the soil during the treatment is as shown in the sixth figure, and it can maintain a stable neutral pH value, which meets the requirements of this design. In order to consider the safety factor, the motor white is maintained below I ampere, that is, the operating voltage gradient is less than 2 〇v/cm in the test. According to the above, the present invention can be summarized as follows: A method for improving the soil (sludge) error and copper content, wherein the anodes are respectively placed in the operating fluid storage area, neither of which is different from the earth's Rein #, ,, and the operating liquid may have High pH buffering and low toxicity, the chelating agent is suitable for yin, and a circulatory system is formed by transporting the permeable pores into the soil, and the operating liquid is thereby determined by removing the soil size of the soil turbidity 2; In the process of 'depleting mud' heavy metal, the pH of the soil (soil 1280952 mud) can be kept neutral, and the removed heavy metal can be electro-mineralized on the cathode plate provided at the cathode end, without woven wastewater treatment; Non-destructive, Quick removal efficiency, cost savings given the post mortem acid environment, in fact - with a very progressive design of environmental engineering. The invention has been described in the detailed drawings of the preferred embodiments. Familiar with this technology can derive many changes from the best real (4) must be away from the invention of the Saki. Accordingly, the preferred embodiment does not limit the scope of the invention. The scope of the invention is defined in the scope of the patent application. [Simple description of the diagram] The first figure is a schematic diagram of a neutral electrokinetic treatment method for improving the removal efficiency of heavy metals and maintaining soil pH. The second picture is a top view of the method site. The second figure is a partial enlarged view of the electrode installation. Figure 4: Diagram of lead removal efficiency in soil. • Figure 5 is a graph of copper removal efficiency in soil. Figure 6 is a plot of pH change in soil. [Main component symbol description] 10 anode 40 pumping pump 70 Soil 81 water permeable hole Cathode 50 operating fluid 71 action zone 90 wheeling device 3 〇 DC power supply 60 Operating fluid storage area Waterproof material 11