201136843 六、發明說明： 【發明所屬之技術領域】 本發明係有關於一種乳化液，尤指一種奈米尺寸乳化 液之製備及其應用，該乳化液可應用於整治土壤與地下水 層中之含氣有機物污染。 【先前技術】201136843 VI. Description of the Invention: [Technical Field] The present invention relates to an emulsion, and more particularly to the preparation and application of a nano-sized emulsion, which can be used for remediation of soil and groundwater layers. Gas organic pollution. [Prior Art]
長期以來，含氣有機溶劑為地下水常見的有機污染物 質之一’其主要包含四氣乙烯（perchl〇roethene，PCE)、三 氯乙烯（trichloroethene，TCE)及其部份還原後之反式與順 式一氯乙稀（trans- and cis-dichloroethene，trans- and cis-DCE)、氣乙烯（vinyi chi〇ride，VC)等。由於 PCE、TCE 的 來源主要是經由人工合成，在工業中常廣泛的被使用來當 作金屬脫脂溶劑、稀釋劑，或乾洗店用作去潰劑（乾洗劑）。 然而常因使用過程處理不當，導致有多處場址及其地下水 層受到氯化有機溶劑污染的現象。台灣重大的污染場址有 台灣美國無線電公司（Radio Company 〇f America，RCA)桃 園廠、中國石油化學工業開發公司安順廠等，其污染的範 圍都深深影響地下水水質。該等污染場址儘管經過多年整 治，但要降低土壌内的污染物質’使其達到飲用水之標準， 仍極為困難。傳統物理、化學處理方式效果有限，並耗費 成本與時間。 因此’以生物4复育的$式處理氯化有機溶劑所污染的 地下水層最為值得探討。整治土地與地下水中之含氣有機 化合物之生物復育處理主要分為好氧處理、厭氧處理（還原 脫氣反應。，其中處理效果以厭氧處理為顯著。高氧化態之⑸ 4 201136843 氣化有機溶劑之降解有賴厭氧脫氣反應。厭氧脫氯法係指 在厭氧環境下$供電子供給者使高氧化態之氣化有機溶= 進行脫氯反應，但在自然之地下水層環境中，厭氧脫氯過 程中常因缺乏大量之電子供應者而受到限制，導致無法將 污染物完全降解》 國際間已有商品化之乳化液產品供用於以生物復育方 式處理含氯有機溶劑。現有的乳化液產品的油顆粒平均粒 徑在500〜1000奈米以上且其製備方法需要消耗大量能源， • 而由於地下水層中玢土（Silt)中最小的顆粒直徑為2微米 (μιη)，且以圓形顆粒作簡單計算，其僅能容許約3丨〇奈米 以下的油顆粒通過’因此現有的乳化液產品使用於地下水 層傳輸時，會因孔隙小而油顆粒大，造成堵塞或傳輸距離 不足的問題。 市售之乳化液已經被利用來進行管柱試驗，針對有無 添加乳化液成份後’比對其PCE、TCE、cis-DCE、VC、 乙烯（ethene)之濃度分佈曲線’發現有添加乳化液之樣本以 cis-DCE、VC居多，顯示乳化液能有效降低PCE、TCE之 濃度（Cameron and Robert，20〇4)，然而乳化液的顆粒粒徑 亦會影響到其在地下水層中之傳輸情形，當粒徑越小時， 已證實其在地下水層中有較佳的傳輸效率，其分布亦會較 為均勻。 基於上述可見，此技術領域中存在有對於乳化液之需 求’特別是一種粒徑小於500 nm的乳化液，其於整治並 復育受污染的地下水層的用途上具有顯著的傳輸效率與以 及均句分布之特性，而較大之油顆粒之乳化液則是針對預 201136843 先漠縮高度親油之污染物之用。 【發明内容】 有鑒於現有技術缺乏一種乳化液，所需的乳化液含 油顆粒粒徑小於謂奈米，較佳的是介於9奈米至 奈米之間的奈米乳化劑，且其主要為天然無毒性、 分解之材料所組成’可以適當的擴散速率於諸如土壤、地 下水層或底泥等環境介質中進行擴散作用，或者可作為環For a long time, the gas-containing organic solvent is one of the common organic pollutants in groundwater. It mainly contains tetrakiethylene (perchl〇roethene, PCE), trichloroethene (TCE) and its partially reduced trans and cis. Trans- and cis-dichloroethene (trans- and cis-DCE), propylene (vinyi chi〇ride, VC) and the like. Since the source of PCE and TCE is mainly through artificial synthesis, it is widely used in the industry as a metal degreasing solvent, a diluent, or a dry cleaner as a de-crushing agent (dry cleaning agent). However, due to improper handling due to the use process, many sites and their groundwater layers are contaminated by chlorinated organic solvents. The major polluting sites in Taiwan include the Radio Company 〇f America (RCA) Taoyuan Plant and the China Petroleum Chemical Industry Development Corporation Anshun Plant. The scope of pollution has a profound impact on groundwater quality. Although these contaminated sites have been rectified for many years, it is still extremely difficult to reduce the pollutants in the soil to meet the drinking water standards. Traditional physical and chemical treatments have limited effectiveness and cost and time. Therefore, the groundwater layer contaminated with the chlorinated organic solvent treated by Bio 4 is most worth exploring. The biological remediation treatment of gas-containing organic compounds in land and groundwater is mainly divided into aerobic treatment and anaerobic treatment (reduction degassing reaction. The treatment effect is remarkable by anaerobic treatment. High oxidation state (5) 4 201136843 gas The degradation of organic solvents depends on the anaerobic degassing reaction. The anaerobic dechlorination method refers to the gasification of the high oxidation state by the electron donor in an anaerobic environment. The dechlorination reaction is carried out, but in the natural groundwater layer. In the environment, anaerobic dechlorination is often limited by the lack of a large number of electron suppliers, resulting in the inability to completely degrade the pollutants. Internationally available commercial emulsion products for the treatment of chlorine-containing organic solvents by biological remediation. The existing emulsion product has an average particle size of oil particles of 500 to 1000 nm or more and requires a large amount of energy to be produced. • Since the smallest particle diameter of the silica in the groundwater layer (Silt) is 2 μm (μιη) And with a simple calculation of round particles, it can only allow oil particles of less than 3 nanometers to pass through. Therefore, the existing emulsion products are used in groundwater layer transmission. When the pores are small and the oil particles are large, the blockage or the transmission distance is insufficient. The commercially available emulsion has been used for the column test, and the presence or absence of the emulsion component is compared to its PCE, TCE, cis. -DCE, VC, ethene concentration distribution curve 'The sample with added emulsion is mostly cis-DCE, VC, which shows that the emulsion can effectively reduce the concentration of PCE and TCE (Cameron and Robert, 20〇4). However, the particle size of the emulsion also affects its transport in the groundwater layer. When the particle size is smaller, it has been proved to have better transmission efficiency in the groundwater layer, and its distribution will be more uniform. There is a demand for emulsions in this technical field, in particular an emulsion having a particle size of less than 500 nm, which has significant transmission efficiency and uniform distribution in the use of remediation and re-contamination of contaminated groundwater layers. The characteristics, while the emulsion of the larger oil particles is for the pre-201136843 to pre-drink high-lipophilic pollutants. [Invention] In view of the lack of a kind of milk in the prior art Liquid, the required oil-containing particle size of the emulsion is smaller than the nanometer, preferably a nano-emulsifier between 9 nm and nanometer, and it is mainly composed of natural non-toxic, decomposed materials. Diffusion can be carried out in an environmental medium such as soil, groundwater or sediment, or as a ring
境介質中的微生物代謝反應之電子供給來源，以降解污： 物。再者’殘餘的含有污染物的油顆粒可有效提高污染物 的生物可及性’藉以破除可能的生物分解瓶頸’而達到促 進污染物分解之目的，以供用於土壤整治與生物復 理。 為了達到上述目的，本發明係提供一種乳化液的製備 方法’其係包含下列步驟： 混合界面活性劑以及食用油，以形成一乳化原液，其 中該界面活性劑係具有一親水親油平衡值ΑΝ⑺沖… lipophile balance，HLB)介於 5 至 16 之間； 將該礼化原液與水混合，形成一乳化稀釋液丨以及 將該乳化稀釋液加熱至一介於75t至125力之間的溫 度，並且加壓至表計壓力介於〇〇至15大氣壓力下，並 持續到該乳化稀釋液由現濁變為叫澄清，以取得一乳化液， 其中所述的礼化液係具有粒徑介於9至i 〇〇〇奈米的油顆 粒’其中具有9至1〇〇奈米的油顆粒之乳化液以奈米乳 化液稱之@具有1 〇〇至i綱奈米的油顆粒之乳化液，則 以一般乳化液稱之。 201136843 依據本發明，該混合界面活性劑以及食用油，以形成 一乳化原液的步驟係包含：利用磁石攪拌器以一為5〇至 1000 rpm的轉速以磁石攪拌該界面活性劑以及該食用油， 錯以避免氣泡產生。 較佳的，所述的界面活性劑混合物係包含任何比例的 下列者，其中各單一成分不為零：聚氧乙烯山梨醇單油酸 龍（polyoxyethylenesorbitan monooleate) (Tween 80)、聚氧 乙稀山梨醇單月桂酸酯（p〇ly〇xyethylene s〇rbitan • m〇n〇laurate) (Tween 20)與（Z)-單-9-十八烯酸脱水山梨醇酯 (Sorbitan (Z)-mono-9-octadecenoate) (Span 80)。 更佳的’所述的界面活性劑係由13: 1.3 :2 4體積份 比的聚氧乙烯山梨醇單油酸酯、聚氧乙烯山梨醇單月桂酸 醋與（Z)-單-9-十八烯酸脱水山梨醇酯所組成。 依據本發明’於該將該乳化原液與水混合，形成一乳 化稀釋液的步驟中，食用油於該乳化稀釋液中之總量不大 於5 0°/。體積百分比，以乳化稀釋液的總體積為基礎。 _ 較佳的，將該乳化原液與水混合步驟包含：將乳化原 液與水以一介於1 :〇至1:99之間的體積比混合，形成該乳 化稀釋液，亦即乳化原液的體積稀釋倍數為1至1 〇〇倍。 較佳的’所述的食用油係選自於由下列者所構成的群 組：大豆油、花生油、玉米油、撖欖油、葵花油、棕櫚油、 葡萄軒油、菜籽油、米糠油以及它們的組合》更佳的，所 述的食用油係大豆油。如所知者，食用油價格低廉、取得 谷易，並符合食品級需求，並能夠有效的提供電子促進厭 氧還原脫氯反應，且對污染之控制也有所幫助（黃，2〇〇2)。 201136843 依據本發明，所述的大豆油係約5 1%亞麻油（un〇ieic oil) (C18H32〇2)、23%之油酸（oleic acid) (C18H34〇2)、7°/。亞 麻油酸（linolenic acid) (Cl8H3()〇2)、4%硬脂酸（stearic acid) (C18H3602)及 10%棕櫚酸（palmitic acid)(C16H32〇2)。以上為 一般大豆油之大約百分比’所有大豆油均可以本發明之方 法配製成為奈米乳化液或一般乳化液。 依據本發明，用語「油顆粒」意指由界面活性劑與食 用油所形成的粒子，其可藉由所屬領域中已知的方法進行 粒徑量測，較佳的係可藉由動態光散射方式量測出。 本發明亦提供一種由前述乳化液的製備方法所製備而 得的乳化液。 早父住的’所述的奈米乳化液係 奈米的油顆粒，一般乳化液具有粒徑介於100至1000奈 ϋπ:太:又更佳的，所述的奈米乳化液係具有粒徑介 、9至70奈米的油顆粒。 依據本發明，所述的乳化液可進—步進行 或是不經稀釋而直接使用。 丹便用 本發明亦提供_種土壤、底泥或其他 質處理方法，其包含： < %境介 將如前所述的乳化液與一定 文污染之環境介質混合以進二“或其他 «及回收該被濃縮於乳㈣中^染物 =刀佈， 理的土壤底泥或其他受污染之環境介質。…到-經處 本發明亦提供_ # 供種％丨兄整治方法，其包含. 將如前所述的.乳化 液庄入一党污染的環境；以及 201136843 令該乳化液與該受污染的環境中之微生物接觸，作為 該微生物還原作用之電子供應者，藉以將該受污染的環境 中的污染物予以去除。 依據本發明，所述的受污染的環境係例如，但不限於： 受污染的土壤、地下水層以及底泥。 依據本發明，所述的污染物包含齒化有機化合物或其 他可被分解或還原的污染物質。所述的函化有機化合物或 其他可被分解或還原的污染物質可為，但不限於：戴奥辛、 • 齒化°夫°南、多漠二苯_、五氯紛、氯苯、目氯乙缔、三氯 乙烯、二氣乙烯、氯乙烯、四氯甲烷、三氣甲烷、二氣甲 烷、氣甲烷、六氣乙烷、五氣乙烷、四氣乙烷、三氣乙烷、 風乙院、鼠乙烧、尚氯酸鹽（perehl〇rate)以及甲基第二丁 基鱗（methyl tert-butyl ether，MTBE)。 前述的乳化液可基於保存問題或者運送考量等特定需 求，於址上（on-site)或者址外（〇ff_site)製備，而施用於該 受污染的環境。 •本發明的乳化液，其油顆粒粒徑為9奈米至1〇〇〇奈 米，經證實其奈米乳化液所含的油顆粒（平均粒徑1 奈 米）可傳輸至適當距離，而仍具有可供達1〇 乙」之pcE 與TCE進行還原脫氣所需的電子當量，遠優於現有技術之 孔化液產品。依據本發明的乳化液可依據需求予以調整， 例如’具有平均粒徑介於9奈米至1〇〇奈米之油顆粒可以 阻礙，而能具有—增加的傳輸距離的功效；而具有1〇〇 奈米至1000奈米的油顆粒可以應用於小面積且較敏感之 巧染地區，避免污染物藉著融入乳化液而由；亏染場址擴散 201136843 出去。依據本發明之乳化液可作為整治助劑外，也可作為 冋正辛醇水刀配係數（octanol-water partition coefficient, Kow)的污染物之預先濃縮之用，所述的高正辛醇水分配係 數的/亏染物係例如多溴二苯鍵（p〇lybrominated diphenyl ethers, PBDEs)、多氯聯苯（p〇iyChi〇rinate(j biphenyls，PCBs) 等’其等係極易溶入油相中，而藉由本發明之奈米乳化液 或一般乳化液予以濃縮回收，而達到整治受污染環境的目 的0An electronic source of microbial metabolic reactions in the medium to degrade the soil: Furthermore, 'residual oil particles containing contaminants can effectively increase the bioavailability of contaminants' to break down possible biodegradation bottlenecks' to promote the decomposition of pollutants for soil remediation and biological remediation. In order to achieve the above object, the present invention provides a method for preparing an emulsion comprising the steps of: mixing a surfactant and an edible oil to form an emulsified stock solution, wherein the surfactant has a hydrophilic-lipophilic balance ΑΝ (7) Lipophile balance (HLB) between 5 and 16; mixing the ritual stock solution with water to form an emulsified diluent 丨 and heating the emulsified diluent to a temperature between 75 and 125 psi, and Pressurizing until the gauge pressure is between 〇〇 and 15 atmospheres, and continuing until the emulsified diluent changes from turbidity to clarification to obtain an emulsion, wherein the liquefied liquid has a particle size between Oil granules of 9 to i 〇〇〇 nano 'an emulsion of oil granules having 9 to 1 nan of nanometers is called an emulsion of oil particles having a particle size of 1 〇〇 to i. , it is called a general emulsion. According to the present invention, the step of mixing the surfactant and the edible oil to form an emulsified stock solution comprises: stirring the surfactant and the edible oil with a magnet at a speed of 5 Torr to 1000 rpm using a magnet stirrer, Wrong to avoid bubbles. Preferably, the surfactant mixture comprises any proportion of the following, wherein each single component is not zero: polyoxyethylene sorbitol monooleate (Tween 80), polyoxyethylene sorbent pear Alcohol monolaurate (p〇ly〇xyethylene s〇rbitan • m〇n〇laurate) (Tween 20) and (Z)-mono-9-octadecenoic acid sorbitan ester (Sorbitan (Z)-mono- 9-octadecenoate) (Span 80). More preferably, the surfactant is composed of 13:1.3:2 4 parts by volume of polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan monolaurate and (Z)-mono-9- It consists of sorbitan octadecyl ester. According to the present invention, in the step of mixing the emulsified stock solution with water to form an emulsified diluent, the total amount of the edible oil in the emulsified diluent is not more than 50 ° /. Percent by volume based on the total volume of the emulsified diluent. Preferably, the step of mixing the emulsified stock solution with water comprises: mixing the emulsified stock solution with water in a volume ratio of between 1: 〇 and 1:99 to form the emulsified diluent, that is, the volume dilution of the emulsified stock solution The multiple is 1 to 1 times. Preferably, the edible oil is selected from the group consisting of soybean oil, peanut oil, corn oil, eucalyptus oil, sunflower oil, palm oil, grape linseed oil, rapeseed oil, rice bran oil And a combination thereof, more preferably, the edible oil is soybean oil. As known, edible oils are inexpensive, obtain Gu Yi, and meet food-grade requirements, and can effectively provide electrons to promote anaerobic reductive dechlorination, and also help to control pollution (Huang, 2〇〇2) . 201136843 According to the present invention, the soybean oil is about 51% un〇ieic oil (C18H32〇2), 23% oleic acid (C18H34〇2), 7°/. Linolenic acid (Cl8H3()〇2), 4% stearic acid (C18H3602) and 10% palmitic acid (C16H32〇2). The above is about a percentage of the average soybean oil. All of the soybean oil can be formulated into a nanoemulsion or a general emulsion by the method of the present invention. According to the invention, the term "oil particles" means particles formed from a surfactant and an edible oil, which can be measured by particle size by methods known in the art, preferably by dynamic light scattering. Method measurement. The present invention also provides an emulsion prepared by the method for producing the aforementioned emulsion. The rice granules of the nano-emulsions of the early fathers are generally emulsified with a particle size of 100 to 1000 ϋ π: too: and more preferably, the nano emulsifier has a granule It is a medium particle with 9 to 70 nanometers of oil. According to the invention, the emulsion can be used either directly or without dilution. Dan uses the invention to also provide soil, sediment or other quality treatment methods, which include: <% the emulsion as described above is mixed with the environmental medium of the pollution of the text to enter the second "or other « And recovering the soil sediment or other contaminated environmental medium concentrated in the milk (4), the dyed cloth, the soil sediment or the other contaminated environmental medium. The present invention also provides _ #供种丨丨兄治治方法, which includes. Embedding the emulsion as described above into a one-party contaminated environment; and 201136843 bringing the emulsion into contact with microorganisms in the contaminated environment as an electron supplier of the microbial reduction, thereby contaminating the contaminated Contaminants in the environment are removed. According to the present invention, the contaminated environment is, for example, but not limited to: contaminated soil, groundwater layer, and sediment. According to the present invention, the contaminant comprises a toothed organic a compound or other contaminant that can be decomposed or reduced. The functional organic compound or other contaminant that can be decomposed or reduced can be, but is not limited to, Dioxin, • Toothing, South, Dibenzobenzene, pentachlorois, chlorobenzene, methyl chloride, trichloroethylene, diethylene, vinyl chloride, tetrachloromethane, tri-gas methane, di-methane, methane, hexa-ethane, five gases Ethane, tetra-ethane ethane, tri-ethane ethane, Fengyiyuan, hamster, perehl〇rate, and methyl tert-butyl ether (MTBE). The emulsion can be prepared on-site or on-site (〇ff_site) based on specific requirements such as preservation issues or shipping considerations, and applied to the contaminated environment. • The emulsion of the present invention, its oil granules The diameter is from 9 nm to 1 nm. It has been confirmed that the oil particles (average particle size of 1 nm) contained in the nano emulsion can be transported to an appropriate distance and still have a capacity of up to 1 〇. The electron equivalent required for reductive degassing of pcE and TCE is far superior to prior art pore fluid products. The emulsion according to the present invention can be adjusted according to requirements, for example, 'oil particles having an average particle diameter of 9 nm to 1 nm can be hindered, and can have an effect of increasing the transmission distance; and having 1 〇 Oil particles from 〇n to 1000nm can be applied to small-area and sensitive sensitive areas to avoid pollutants from being mixed into the emulsion; the contaminated site spreads out 201136843. The emulsion according to the present invention can be used as a refining aid, or can be used as a preconcentration of a contaminant of an octanol-water partition coefficient (Kow), said high n-octanol water. The distribution coefficient/defects are, for example, p〇lybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (p〇iyChi〇rinate (j biphenyls, PCBs), etc., which are easily soluble in the oil phase. In addition, the nanoemulsion or the general emulsion of the present invention is concentrated and recovered to achieve the purpose of rectifying the polluted environment.
【實施方式】 本發明係提供一種乳化液的製備方法，其係包含下列 步驟：混合界面活性劑以及食用油，以形成一乳化原液， 其中該界面活性劑係具有一親水親油平衡值（hydr〇phiie lipophile balance，HLB)介於 5 至 16 之間。 本發明將進一步藉由下面的實施例來作說明，但應明 瞭的是’ 1¾等實施例僅為說明之用，而不應被視為本發明 的實施上的限制。 實施例 實施例1奈米乳化液製備及粒徑分析 本實施例中係以相反轉溫声 .. . 付恤度居(phase inversion t^npemure method，PIT meih〇d)製備奈米乳化劑，並且動 態光散射方式分析形成的奈米油顆粒之尺寸。 Ϊ S] 相反轉，皿度法係藉由界面活性劑的物理化學特性進行 作用，其適用於非離子型界面活性劑巾，透過溫度的變化 改變界面活性劑的親水及親油性，於低溫時為水包油㈣h water，o/w)型態，於高溫時，則成為油包水（W & 〇丨1，_) 10 201136843 5•二 ▲ /JH·度逐濟升而使水包油（〇/w)轉換成油包水（w/0)型 墟，在待均勻降溫後，降低至自然彎曲度下再形成水包油 型態而達到分散油顆粒、降低粒徑之效果。 實驗方法 1.奈米乳化液原液製備： 先將三種市售食品級界面活性劑：聚氧乙烯山梨醇單 ^ lg (p〇Iy〇xyethylenes〇rbitan monooieate) (Tween 80) > t氧乙稀山梨醇單月桂酸酯（polyoxyethylene sorbitan m〇n〇laUrate) (Tween 2〇)與（幻_單_9_十八烯酸脱水山梨醇酯 (Sorbitan (Z)-m〇no-9-〇cta(iecenoate) (span 80)以體積份 1.3 : 1_3 : 2.4進行配製此三種食品級界面活性劑均來自[Embodiment] The present invention provides a method for preparing an emulsion, comprising the steps of: mixing a surfactant and an edible oil to form an emulsified stock solution, wherein the surfactant has a hydrophilic-lipophilic balance value (hydr) 〇phiie lipophile balance (HLB) is between 5 and 16. The invention will be further illustrated by the following examples, but it should be understood that the embodiments are merely illustrative and are not to be considered as limiting. EXAMPLES Example 1 Preparation of Nano Emulsion and Particle Size Analysis In this example, a nano emulsifier was prepared by a phase inversion t^npemure method (PIT meih〇d). And the size of the formed nano oil particles was analyzed by dynamic light scattering. Ϊ S] Reverse rotation, the dish method works by the physicochemical properties of the surfactant, which is suitable for non-ionic surfactant wipes. The change of temperature changes the hydrophilicity and lipophilicity of the surfactant. For water-in-oil (4) h water, o / w) type, at high temperature, it becomes water-in-oil (W & 〇丨 1, _) 10 201136843 5 • 2 ▲ / JH · degree increase and make the water bag The oil (〇/w) is converted into a water-in-oil (w/0) type market. After being uniformly cooled, it is reduced to a natural curvature and then formed into an oil-in-water type to achieve the effect of dispersing the oil particles and reducing the particle size. Experimental method 1. Preparation of nanoemulsion stock solution: Firstly, three kinds of commercially available food grade surfactants: polyoxyethylene sorbitol monog lg (p〇Iy〇xyethylenes〇rbitan monooieate) (Tween 80) > t oxyethylene Polyoxyethylene sorbitan m〇n〇laUrate (Tween 2〇) and (Fantasy_single_9_octadecenoic acid sorbitan ester (Sorbitan (Z)-m〇no-9-〇cta (iecenoate) (span 80) formulated in parts by volume 1.3 : 1_3 : 2.4 These three food grade surfactants are from
Sigma-Aldrich，其在台灣台中地區之代理商為友和貿易股 份有限公司）’並利用磁石攪拌器使其均勻混合（轉速約為 5〇至1000 rpm)，由於界面活性劑易起泡，於配製過程中 須盡量降低氣泡之產生，配製總體積量為1〇體積份。將 混合均勻後之界面活性劑，緩慢加入丨體積份之大豆油（台 糖公司），使食用油能均句混合於界面活性劑中，等待其穩 定’在此實施例令’混合的界面活性劑的親水親油平衡值 (HLB)為13.0。2.乳化液之製備 此部份之製備方法分為三種，分述如下： (1)將已穩定之乳化液原液，利用水稀釋J 至100倍（取1體積份原液加入i至99體積份之 水）後，置入滅菌爸中，其滅菌條件為12b 分鐘以上、等於或大於-大氣壓加壓，使乳化液 於滅菌釜中達PIT溫度以上。 11 201136843 (2) 將已穩定之乳化原液，利用水稀釋1至 100倍（取1體積份原液加入1至99體積份之水） 後，直接加熱攪拌，使稀釋後乳化液達ριτ溫度 以上。 (3) 將已穩定之乳化原液，利用高於pit溫 度之水稀釋1至1 〇〇倍（取】體積份原液加入i至 99體積份之水）後，使稀釋時之乳化液達ριτ溫度 以上。 經以上三種步驟之一或是三種任意可能之組合均可， 起初乳化液為尚溫之狀態’於降溫的過程中，須搖晃咬是 授拌使其混合’降溫直到室溫左右，此乳化液之油顆粒平 均粒徑為9至1 000奈米（粒徑分布圖如第一圖所示）。 2.油顆粒尺寸量測： 奈米油顆粒之尺寸是以Zetasizer® Nano ZS (Malvern Instruments，Worcestershire，UK)量測而得。前述經稀釋之 乳化液置入一容量4毫升之供先學量測的方型試管中，再 置入該儀器之量測位置。此儀器以動態光散射方式進行量 測。所得之數據為平均粒徑與多分散指數（p〇lydispersivhy lndex)，水與礦物油之折射指數分別設定為1.330及1.460。 實驗結果 以食品級界面活性劑將植物油（大豆油）乳化配製而成 的奈米乳化液，經由動態光散射儀將雷射光射入待測樣品 中’油顆粒使得雷射光散射，而油顆粒本身因不規則的布 朗運動使散射雷射光改變，計算出油顆粒粒徑大小。测量 出粒徑大小分佈，其乳化液中油顆粒粒徑大小為1 3至6 7 12 201136843 奈米（nm)，如第一圖以及表1所示。 __ 表1奈米乳化液油顆粒粒徑分布 峰 直徑(nm) 強度 (%intensity) 寬度(nm) z平均值 (diameter, nm): 多分散 指數 (PDI) 截距 (intercept) 結果品 質： 峰1 67.29 89.5 26.87 45.79 0.271 峰2 13.01 10.5 3.030 0.958 佳 峰3 0.000 0.0 0.000 實施例2奈米乳化液傳輸狀況分析 爲了解奈米乳化液於地下水層傳輸之狀況，本實施例 利用小型管柱的傳輸實驗，模擬地下水層之移動情形，並 採用溴化鈉（NaBr)為追蹤劑，嘗試計算奈米乳化液之遲滯 情形。由於NaBr在地下水層中，在土壤顆粒中，解離後 之溴離子（Br )較氯離子（C1·)安定，且對土壤的吸附性非常 小（李，1991)，因此在本管柱實驗中以NaBj>來當作追蹤劑 ，因本貫驗所收集到的樣本體積較小，須經由稀釋後再行 測量其導電度，故選用高濃度之NaBr (175g/L)來進行傳輸 實驗之比較。 實發才法 1·管柱實驗方法： b柱材質為透明pvc管，直徑1.7cm，長i5cm ’管 柱的兩端各放5片細小孔隙之不鏽鋼墊片，加以阻隔，避 免填充物石英砂流出，組裝管枉之零件。選用的石英砂為 5種中^粒徑之混砂，填充管柱前經先將石英砂放入滅菌 爸中滅菌，並玫入振盪機中將石英砂中的雜質、氣泡移除， 再放入去離子水中搜拌，以確保石英砂中完全沒有氣泡才 I S1 13 201136843 進行管柱填充以備用。 卜 裝好之官柱，分別以直徑3 mm細小管線連接上 十筒幫浦（KDS-200, KD Scientific，Holliston，MA, USA)， 採用針筒幫浦進行定I、-* 、、± λ其★ a α疋里々IL速庄入官柱之中，並以由下往上 注入之方式避免實驗造成短流之現象。首先分別將配製好 的不米乳化液（含5%奈米乳化液原液）、仏以（mg/L)各取 0.5 mL ’主入管線中，再以每管6〇 mL之針筒，依據一般砂Sigma-Aldrich, its agent in Taichung, Taiwan, is a friend and trade company)' and uses a magnetic stirrer to evenly mix it (about 5 〇 to 1000 rpm). Because the surfactant is easy to foam, it is formulated. In the process, the generation of bubbles should be minimized, and the total volume of the preparation is 1 volume. The evenly mixed surfactant is slowly added to the soy volume of soybean oil (Taiwan Sugar Co., Ltd.), so that the edible oil can be uniformly mixed in the surfactant, waiting for it to stabilize the 'in this example' mixed surfactant. The hydrophilic-lipophilic balance (HLB) is 13.0. 2. Preparation of the emulsion The preparation method of this part is divided into three types, which are described as follows: (1) The stabilized emulsion stock solution is diluted J to 100 times with water. (1 volume part of the stock solution is added to i to 99 parts by volume of water), and then placed in a sterilized dad, the sterilization condition is 12b minutes or more, equal to or greater than - atmospheric pressure, so that the emulsion reaches the PIT temperature in the sterilizer. . 11 201136843 (2) Dilute the stabilized emulsified stock solution by 1 to 100 times with water (1 to 99 parts by volume of 1 part by volume of the stock solution), and then directly heat and stir to make the diluted emulsion reach a temperature above ριτ. (3) Dilute the stabilized emulsified stock solution with water above the pit temperature by 1 to 1 ( times (take the volume of the stock solution to add i to 99 parts by volume of water), then let the emulsion at the time of dilution reach the ριτ temperature. the above. Through one of the above three steps or any combination of the three possibilities, the initial emulsion is in a state of being warm. In the process of cooling, the shake must be shaken to mix and mix to 'cool down to room temperature, the emulsion The oil particles have an average particle size of 9 to 1,000 nm (the particle size distribution is as shown in the first figure). 2. Oil particle size measurement: The size of the nano oil particles was measured by Zetasizer® Nano ZS (Malvern Instruments, Worcestershire, UK). The diluted emulsion was placed in a 4 ml volume test tube for the first measurement and placed in the measurement position of the instrument. This instrument is measured by dynamic light scattering. The data obtained are the average particle size and polydispersity index (p〇lydispersivhy lndex), and the refractive indices of water and mineral oil are set to 1.330 and 1.460, respectively. Experimental results A nano-emulsion prepared by emulsification of vegetable oil (soybean oil) with a food-grade surfactant, and laser light is injected into the sample to be tested by a dynamic light scattering instrument. 'The oil particles scatter the laser light, and the oil particles themselves The particle size of the oil particles is calculated by the irregular Brownian motion changing the scattered laser light. The particle size distribution was measured, and the particle size of the oil particles in the emulsion was 13 to 6 7 12 201136843 nm (nm) as shown in the first figure and Table 1. __ Table 1 Nano-emulsion oil particle size distribution Peak diameter (nm) Strength (%intensity) Width (nm) z-average (diameter, nm): Polydispersity index (PDI) Intercept (Result) Result quality: Peak 1 67.29 89.5 26.87 45.79 0.271 Peak 2 13.01 10.5 3.030 0.958 Jiafeng 3 0.000 0.0 0.000 Example 2 Analysis of the transmission state of nanoemulsion In order to understand the state of transport of nanoemulsion in the groundwater layer, this embodiment utilizes the transmission of small column. Experiments, simulating the movement of the groundwater layer, and using sodium bromide (NaBr) as a tracer, attempted to calculate the hysteresis of the nanoemulsion. Since NaBr is in the groundwater layer, in the soil particles, the bromide ion (Br) after dissociation is more stable than the chloride ion (C1·), and the adsorption to the soil is very small (Li, 1991), so in this column experiment NaBj> is used as a tracking agent. Because the sample collected by this test is small, it must be diluted to measure its conductivity. Therefore, a high concentration of NaBr (175g/L) is used for the transmission experiment. . Actual hair method 1. Pillar test method: b column material is transparent pvc tube, diameter 1.7cm, length i5cm 'There are 5 small pores of stainless steel spacers at both ends of the column to block the quartz sand Flow out and assemble the parts of the pipe. The selected quartz sand is mixed with 5 kinds of medium-sized particles. Before filling the column, the quartz sand is first placed in the sterilization dad to be sterilized, and the impurities and bubbles in the quartz sand are removed into the oscillating machine, and then placed. Mix in deionized water to ensure that there are no bubbles in the quartz sand. I S1 13 201136843 Fill the column for use. The installed column is connected to the 10-tube pump (KDS-200, KD Scientific, Holliston, MA, USA) with a small 3 mm diameter pipeline, and the syringe pump is used to set I, -*, and ± λ. Its ★ a α疋里々IL speed into the official column, and from the bottom up to avoid the phenomenon of short-flow experiments. First, prepare the prepared non-rice emulsion (containing 5% nano-emulsion stock solution), and take 0.5 mL of each (mg/L) into the main pipeline, and then use a 6-mL syringe per tube. General sand
質土壤中地下水層之平均流速換算後之值，& 〇 5机W 之机速推入管柱之中，於特定時間點就流出溶液進行採 樣並加以分析其總碳量（total carbon，TC)與導電度。 2.分析方法： 將各時間點收集到的奈米乳化液樣本，取2〇〇 mg (約 200 μ!〇進行固體TC分析其含碳量，並依注入之奈米乳化 液濃度比率（5%)，自行建立本實驗之檢量線（y=2 4378xi〇_4， R 0.9994)換算回收集到之樣本濃度比率。NaBr因收集體 積少，故取400 定量到10 mL (稀釋2〇倍），再利用導 電度計測量其導電度值（μ8/(：ΙΪ〇。 、结果與討論 1.管柱設計與組裝 本實施例首先估算實驗之參數，其石英砂孔隙率為0.3 至0.4間，故通過此管柱之孔隙體積（p〇re v〇lume，ρν)約 為13.24毫升。由於以兩支重複的管柱分別進行實驗，於 貫驗前’分別測量各管柱之水力傳輸係數Κ值，以確保其 官柱之差異性不大，測量方法為變水頭試驗（falling head measurement)，是藉由水頭差、流經的時間計算出κ值， m 14 201136843 如附件 1 所示（T〇dd，1959; Freeze，1979)。 其中各參數如下所示： a 0.0256 cm2 A 0.7225 cm2 L 15 cm H〇 113.5 cm Hj 63.5 cmThe average flow rate of the groundwater layer in the soil is converted to the value, and the machine speed of the 〇5 machine W is pushed into the column. The solution is sampled at a specific time point and analyzed for total carbon (TC). ) and conductivity. 2. Analytical method: Take the nano-emulsion sample collected at each time point, take 2 〇〇mg (about 200 μ! 〇 for solid TC analysis of its carbon content, and according to the ratio of injected nano-emulsion concentration (5 %), establish the calibration curve of this experiment (y=2 4378xi〇_4, R 0.9994) and convert back to the sample concentration ratio collected. NaBr takes 400 to 10 mL (diluted 2 times) due to the small collection volume. Then, the conductivity value is measured by a conductivity meter (μ8/(: ΙΪ〇., results and discussion 1. Column design and assembly. This example first estimates the parameters of the experiment, and the quartz sand porosity is between 0.3 and 0.4. Therefore, the pore volume (pνre v〇lume, ρν) passing through the column is about 13.24 ml. Since the experiments are carried out with two repeated columns, the hydraulic transmission coefficients of each column are measured separately before the inspection. Depreciation, to ensure that the difference between the official column is not large, the measurement method is the falling head measurement, which is calculated by the head difference and the time of the flow, m 14 201136843 as shown in Annex 1 ( T〇dd, 1959; Freeze, 1979). The parameters are as follows : a 0.0256 cm2 A 0.7225 cm2 L 15 cm H〇 113.5 cm Hj 63.5 cm
依據上述公式計算而得 ，q κ俚分別 為.〇.l54Cmsec-i、0.161cmsec-丨，在以同—針筒幫浦推 動兩管柱之情況，此差異可造成約4_3%之誤差。 2·追蹤劑傳輸實驗結果 本實施例在管柱實驗中模擬地下水層的傳輸情形，將 測得的NaBr以體積與導電度作分佈圖，加以探討 比較其傳輸情形、可能發生之狀況，如第二圖所示。本實 驗結果中，發現NaBr於回收樣本的累積體積為2〇mL時， 導電度值開始明顯上升，在32 mL時達到最高值，但過了 40 mL郃沒有降至背景值，由於NaBr對土壌之吸附性小， 適合用來當追蹤劑，但其延散係數也較大（李，1991)，因 而其NaBr不會只在一個孔隙體積（p〇re ，pv)水量 之體積中即完全出來’由於本實施例以針筒幫浦注入管柱 中’因而導致注入之體積受到限制，故無法完整看到 之下降至接近原背景值之情形。 ΐ S] 15 .201136843 3.奈米乳化液傳輸實驗結果 如第—圖所示，奈米乳化液則是很快的在回收樣本的 累積體積為5 mL時，即有稍微上升現象，而丨5 mL後有 明顯上升，到35 mL開始有緩慢下降之趨勢，卻也還無法 看出月，..具下降之現象β由於奈米乳化液是以界面活性劑乳 化大豆油而成’油顆粒本身較水分子為輕，且本實驗以由 下往上之注入方式，此外，本實驗注入之奈米乳化液具有 兩種主要粒徑分佈，有1〇%之奈米乳化液其粒徑為13奈 鲁 米左右，因而可能導致迅速通過管柱，才會於5mL之後 即開始出現。由於以〇.5 mL之5%奈米乳化液注入管柱中， 因此將其推算經由40 mL (約3_4天）後，有約8〇%之奈米 乳化液流出管柱，顯示能將大部分之乳化液傳輸通過此管 柱，因此據以推算出傳輸距離。以一般大豆油之成分為約 51%亞麻油（linoleic 〇il) (Ci8h32〇2)、23%之油酸（〇leic acid) (C18H34〇2)、7% 亞麻油酸（iin〇ienie acid) (CuH3()02)、4% ^ 硬脂酸（stearic acid)(C18H3602)及 10%棕櫚酸（palmitic acid) (c〗6H32〇2) ’此比例為一般大豆油之比例，其他大豆由亦適 用，依據些分子是可計算其理論上單位質量可供應之電子 當量約為0.40 eq/g，而PCE與TCE還原為乙烯所需電子 畠量分別為0.048 eq/g與0.046 eq/g，則本實施例之奈米 乳化有機會在中細砂層土壤中傳輸至約87公尺之距離， 仍可能可供10 ppb之PCE與TCE進行還原脫氣所需。比 較NaBr與奈米乳化液之出流濃度情況，經過扣除實驗用 管線中多餘之水體積後’可得實際之PV約為13.1 cm3， 而實際之有效孔隙率約為0.38。奈米乳化液在15公分砂 16 201136843 層管柱中之傳輸速度為溴化鈉 比值為1.01。 追蹤劑之傳輸 速度相當，其Calculated according to the above formula, q κ 俚 is respectively 〇.l54Cmsec-i, 0.161cmsec-丨, in the case of pushing the two columns with the same-sleeve pump, this difference can cause an error of about 4_3%. 2. Tracking agent transmission experiment results In this example, the transmission of groundwater layer is simulated in the column experiment. The measured NaBr is used as a distribution map of volume and conductivity to investigate the transmission situation and possible conditions, such as The two figures are shown. In the results of this experiment, it was found that when the cumulative volume of NaBr in the recovered sample was 2〇mL, the conductivity value began to rise significantly, reaching the highest value at 32 mL, but after 40 mL 郃 did not fall to the background value, due to NaBr versus soil It has low adsorption and is suitable for use as a tracer, but its elongation coefficient is also large (Li, 1991), so its NaBr will not be completely out of the volume of one pore volume (p〇re, pv). 'Because the syringe pump is injected into the column in this embodiment', the volume of the injection is limited, so that it cannot be seen down to the original background value. ΐ S] 15 .201136843 3. The results of the nano-emulsion transfer experiment are shown in the figure - the nano-emulsion is very fast, when the cumulative volume of the recovered sample is 5 mL, there is a slight increase, and 丨After 5 mL, there is a significant increase, and the trend of slow decline begins at 35 mL, but it is still unable to see the month. The phenomenon of decline is due to the fact that the nanoemulsion is made of surfactant-emulsified soybean oil. It is lighter than water molecules, and the experiment is carried out from bottom to top. In addition, the nanoemulsion injected in this experiment has two main particle size distributions, and 1%% of the nanoemulsion has a particle size of 13 Narumi or so, which may lead to rapid passage through the column, will begin to appear after 5mL. Since 5% of the 5% nanoemulsion was injected into the column, it was estimated that after about 40% (about 3-4 days), about 8% of the nanoemulsion flowed out of the column, indicating that it could be large. Part of the emulsion is transported through this column, so the transmission distance is derived accordingly. The composition of general soybean oil is about 51% linoleic 〇il (Ci8h32〇2), 23% oleic acid (C18H34〇2), 7% linoleic acid (iin〇ienie acid) (CuH3()02), 4% ^ stearic acid (C18H3602) and 10% palmitic acid (c〗 6H32〇2) 'This ratio is the ratio of general soybean oil, other soybeans are also Applicable, based on the fact that some molecules are calculated to theoretically supply an electron equivalent of about 0.40 eq/g per unit mass, and the electron enthalpy required for reduction of PCE and TCE to ethylene is 0.048 eq/g and 0.046 eq/g, respectively. The nano emulsification of this example has the opportunity to transfer to a soil of about 87 meters in the middle fine sand layer soil, and it is still possible to supply 10 ppb of PCE and TCE for reduction and degassing. Comparing the outflow concentration of the NaBr and nanoemulsion, after deducting the excess water volume in the experimental pipeline, the actual PV is about 13.1 cm3, and the actual effective porosity is about 0.38. The transmission speed of the nanoemulsion in a 15 cm sand 16 201136843 layer column is a sodium bromide ratio of 1.01. The transmission rate of the tracking agent is equivalent, and its
綜合NaBr與奈米乳化液之出流水 發現其在傳輸的過程中，所橫跨涵蓋的體積過’二 二二顯不其在官柱的傳輸過程中擴散作 :本貫施例之流速參照典型之地下水層之傳輪情形，其： 因可能也受到流速較慢之影響1而這也顯示當將夺米乳 化液注入地下水層日夺，能藉由擴散作用、其粒徑較小之關 輸得更均自，推測能更有效率的給予厭氧還原脫 虱作用扣供電子供給來源以達到地下水層整治之目的。 本實施例結果發現一食品級之界面活性劑盥市隹之大 豆油可製作出油顆粒粒徑介於13 i 67纟米之奈:乳化 液’且在2.85孔隙體積水量流過之情況下回收之乳化劑相 當於約80%之注入量（估計比值為〇82)，故本發明之奈米 乳化有機會在中細砂層土壤中傳輸至約8·7公尺之距離， 仍可供Η)μ“·丨之PCE與TCE進行還原脫氯所需。因此 在設置注入點時.，較市售之乳化液產品可降低其初設工程 費約90%，同時也可有效降低後續維護操作f用。此結果 顯示本發明所使用之奈米乳化液在傳輸速度及流佈情況遠 優於目前市售之做為電子供應者之乳化液產品。 【圖式簡單說明】 第一圖係奈米乳化液粒徑分佈圖。 第二圖係NaBr之導電度hs/cm)分佈圖。 第三圖係奈米乳化液之濃度比率（％)分佈圖。 m 17 201136843 【主要元件符號說明】 (無） 【附件簡單說明】 附件1 :變水頭試驗（falling head measurement)之裝置 示意圖。The outflow of NaBr and nanoemulsions was found to be in the process of transport, and the volume covered by the crossover was not diverged during the transmission of the column: the flow rate of the present example is typical. The grounding situation of the groundwater layer, which: It may also be affected by the slower flow rate 1 and this also shows that when the rice emulsion is injected into the groundwater layer, it can be diffused and its particle size is small. More uniform, it is speculated that the anaerobic reduction and deodorization effect can be more efficiently deducted from the source of electron supply to achieve the purpose of remediation of the groundwater layer. The results of this example show that a food-grade surfactant, 盥市隹之 soybean oil can be produced with an oil particle size of 13 i 67 之N: emulsion ' and recovered in the case of 2.85 pore volume of water flowing through The emulsifier is equivalent to about 80% of the injection amount (estimated ratio is 〇82), so the nano emulsification of the present invention has the opportunity to be transported in the middle fine sand layer soil to a distance of about 8.7 meters, which is still available for Η) μ"·丨PCE and TCE are required for reductive dechlorination. Therefore, when setting the injection point, the commercially available emulsion product can reduce the initial construction cost by about 90%, and can also effectively reduce the subsequent maintenance operation. This result shows that the nano-emulsion used in the present invention is far superior to the currently commercially available emulsion product as an electron supplier in terms of transmission speed and flow distribution. [Simplified illustration] The first figure is a nano-emulsified product. The particle size distribution map. The second graph is the distribution of conductivity (hs/cm) of NaBr. The third graph is the concentration ratio (%) distribution of the nanoemulsion. m 17 201136843 [Explanation of main component symbols] (none) [A brief description of the attachment] Attachment 1: Variable head test (f Alling head measurement) schematic diagram.
t SI 18t SI 18