TWI478877B - Degradation of chlorinated hydrocarbon compounds and methods for their preparation - Google Patents
Degradation of chlorinated hydrocarbon compounds and methods for their preparation Download PDFInfo
- Publication number
- TWI478877B TWI478877B TW102100920A TW102100920A TWI478877B TW I478877 B TWI478877 B TW I478877B TW 102100920 A TW102100920 A TW 102100920A TW 102100920 A TW102100920 A TW 102100920A TW I478877 B TWI478877 B TW I478877B
- Authority
- TW
- Taiwan
- Prior art keywords
- oil
- composition
- degrading
- preparation
- calcium peroxide
- Prior art date
Links
Landscapes
- Processing Of Solid Wastes (AREA)
Description
本發明是有關於一種降解含氯碳氫化合物用組成物及其製備方法,特別是指一種包含經植物油包覆的過氧化鈣奈米顆粒的降解含氯碳氫化合物用組成物及其製備方法。The present invention relates to a composition for degrading a chlorine-containing hydrocarbon and a preparation method thereof, and particularly to a composition for degrading a chlorine-containing hydrocarbon containing calcium peroxide nanoparticle coated with vegetable oil and a preparation method thereof .
生物整治技術(bioremediation)具有能減低或去除污染物毒性、經濟效益較佳及不破壞污染場址之原有用途等優點,近年來已普遍被應用於整治遭受含氯碳氫化合物污染的污染場址上,其中,含氯碳氫化合物又可分為高氯數的含氯碳氫化合物(例如:四氯乙烯、三氯乙烯等)及低氯數的含氯碳氫化合物(例如:1,1-二氯乙烯、順式-1,2-二氯乙烯、反式-1,2-二氯乙烯、氯乙烯等)。Bioremediation has the advantages of reducing or eliminating the toxicity of pollutants, better economic benefits and not destroying the original use of contaminated sites. In recent years, it has been widely used to remediate pollution fields contaminated by chlorinated hydrocarbons. At the site, the chlorinated hydrocarbons can be further divided into high chlorine number chlorine-containing hydrocarbons (for example: tetrachloroethylene, trichloroethylene, etc.) and low chlorine number chlorine-containing hydrocarbons (for example: 1, 1-Dichloroethylene, cis-1,2-dichloroethylene, trans-1,2-dichloroethylene, vinyl chloride, etc.).
生物整治技術的原理是利用微生物使含氯碳氫化合物脫氯,以達到降解含氯碳氫化合物的目的,又可分為厭氧處理及好氧處理。於厭氧處理中,植物油或由植物油所製成的乳化液可用來作為微生物進行厭氧還原脫氯反應時的生長基質及電子供給者,讓具有厭氧發酵能力的微生物將此電子供給者先行發酵形成氫 氣後,藉由不同物種微生物氫氣傳遞(inter-species hydrogen transfer),將氫氣提供給厭氧鹵呼吸菌群(halorespiring bacteria),以使高氯數含氯碳氫化合物進行還原脫氯反應,達到降解含氯碳氫化合物的目的。於好氧處理中,釋氧化合物(oxygen release compounds,ORC),例如過氧化氫、過碳酸鈉、過氧化金屬(過氧化鎂及過氧化鈣)等,會釋出氧氣以供好氧微生物進行好氧處理,以使低氯數含氯碳氫化合物進行氧化脫氯反應,達到降解所有含氯碳氫化合物的目的。The principle of bioremediation technology is to use microorganisms to dechlorinate chlorinated hydrocarbons to achieve the purpose of degrading chlorinated hydrocarbons, and can be divided into anaerobic treatment and aerobic treatment. In anaerobic treatment, vegetable oil or emulsion made of vegetable oil can be used as a growth substrate and electron supplier for anaerobic reductive dechlorination reaction of microorganisms, and microorganisms with anaerobic fermentation ability can be used as an electron supplier first. Fermentation to form hydrogen After the gas, hydrogen is supplied to the anaerobic halophilic bacteria by inter-species hydrogen transfer, so that the high chlorine number chlorocarbon is subjected to reductive dechlorination reaction. Degradation of chlorine-containing hydrocarbons. In aerobic treatment, oxygen release compounds (ORC), such as hydrogen peroxide, sodium percarbonate, metal peroxides (magnesium peroxide and calcium peroxide), release oxygen for aerobic microorganisms. Aerobic treatment to oxidize and dechlorinate low chlorine number chlorine-containing hydrocarbons to achieve the purpose of degrading all chlorine-containing hydrocarbons.
以往整治一遭受含氯碳氫化合物污染的污染場址時大多採用兩階段注入的方式,該方式的第一階段為先注入電子供給者於該污染場址中,以讓高氯數的含氯碳氫化合物進行還原脫氯反應,此時若脫氯不完全則會生成毒性更高的低氯數含氯碳氫化合物,因此會於第二階段時注入釋氧化合物於該污染場址中,以讓低氯數含氯碳氫化合物進行氧化脫氯反應。但該方式的缺點為:低氯數含氯碳氫化合物是在第一階段時生成的,但第二階段注入的釋氧化合物未必會移動到含有低氯數含氯碳氫化合物的區域,而無法完全讓低氯數含氯碳氫化合物進行氧化脫氯反應。In the past, when a pollution site contaminated with chlorinated hydrocarbons was rectified, a two-stage injection method was used. The first stage of the method was to inject the electron supplier into the pollution site to allow high chlorine content. The hydrocarbon undergoes a reductive dechlorination reaction. If the dechlorination is incomplete, a less toxic chlorine-containing hydrocarbon is formed, so that the oxygen release compound is injected into the contaminated site in the second stage. In order to carry out oxidative dechlorination of low chlorine number chlorine-containing hydrocarbons. However, the disadvantage of this method is that the low chlorine number chlorine-containing hydrocarbon is formed in the first stage, but the oxygen release compound injected in the second stage does not necessarily move to the area containing the low chlorine number chlorine-containing hydrocarbon, and It is impossible to completely oxidize and dechlorinate low-chlorinated chlorine-containing hydrocarbons.
由上述可知,若能開發出一種能同時在同一區域提供電子供給者及釋氧化合物的材料,確保釋氧化合物會到達含有低氯數含氯碳氫化合物的區域,以使低氯數含氯碳氫化合物於生成時能立即地進行氧化脫氯 反應,對於整治遭受含氯碳氫化合物污染的污染場址是很有幫助的。From the above, it can be seen that if a material capable of supplying an electron donor and an oxygen-releasing compound simultaneously in the same region can be developed, it is ensured that the oxygen-releasing compound reaches a region containing a low chlorine number chlorine-containing hydrocarbon so that the chlorine content is low. Oxidative dechlorination of hydrocarbons immediately upon formation The reaction is very helpful in remediating contaminated sites that are contaminated with chlorinated hydrocarbons.
因此,本發明之第一目的,即在提供一種降解含氯碳氫化合物用組成物的製備方法。該方法能製備出一種能同時在同一區域提供電子供給者及釋氧化合物的材料,確保釋氧化合物會到達含有低氯數含氯碳氫化合物的區域,以使低氯數含氯碳氫化合物於生成時能立即地進行氧化脫氯反應。Accordingly, a first object of the present invention is to provide a process for preparing a composition for degrading a chlorine-containing hydrocarbon. The method can prepare a material capable of providing an electron donor and an oxygen releasing compound simultaneously in the same region, ensuring that the oxygen releasing compound reaches a region containing a low chlorine number chlorine-containing hydrocarbon to make a low chlorine number chlorine-containing hydrocarbon The oxidative dechlorination reaction can be carried out immediately at the time of formation.
於是,本發明降解含氯碳氫化合物用組成物的製備方法包含以下步驟:提供一油相溶液,包含過氧化鈣奈米顆粒、一植物油組份及一親油性界面活性劑;提供一包含水及一親水性界面活性劑的水相溶液;及將該油相溶液及該水相溶液進行一乳化處理,以獲得一降解含氯碳氫化合物用組成物,該降解含氯碳氫化合物用組成物包含過氧化鈣奈米顆粒、乳化液及經植物油包覆的過氧化鈣奈米顆粒。Thus, the method for preparing a composition for degrading a chlorocarbon-containing compound of the present invention comprises the steps of: providing an oil phase solution comprising calcium peroxide nanoparticles, a vegetable oil component and a lipophilic surfactant; providing a water containing And an aqueous phase solution of a hydrophilic surfactant; and emulsification treatment of the oil phase solution and the aqueous phase solution to obtain a composition for degrading a chlorine-containing hydrocarbon, the composition for degrading the chlorine-containing hydrocarbon The material comprises calcium peroxide nano particles, an emulsion and calcium peroxide nanoparticles coated with vegetable oil.
因此,本發明之第二目的,即在提供一種降解含氯碳氫化合物用組成物。Accordingly, a second object of the present invention is to provide a composition for degrading a chlorine-containing hydrocarbon.
於是,本發明降解含氯碳氫化合物用組成物是利用上述的製備方法所製得,該降解含氯碳氫化合物用組成物包含過氧化鈣奈米顆粒、乳化液及經植物油包覆的過氧化鈣奈米顆粒。Thus, the composition for degrading a chlorocarbon-containing compound of the present invention is obtained by the above-described preparation method, and the composition for degrading the chlorocarbon-containing compound comprises calcium peroxide nanoparticles, an emulsion, and a vegetable oil-coated product. Calcium oxide nanoparticle.
本發明製備方法所製得的降解含氯碳氫化合物用組成物由於包含過氧化鈣奈米顆粒、乳化液及經植物油包覆的過氧化鈣奈米顆粒,能同時在同一區域提供電子供給者及釋氧化合物的材料,確保釋氧化合物會到達含有低氯數含氯碳氫化合物的區域,以使低氯數含氯碳氫化合物於生成時能立即地進行氧化脫氯反應,而有助於含氯碳氫化合物的降解。The composition for degrading a chlorine-containing hydrocarbon prepared by the preparation method of the present invention can provide an electron supplier in the same region at the same time by containing calcium peroxide nano particles, an emulsion and a calcium peroxide nanoparticle coated with vegetable oil. And the material of the oxygen-releasing compound ensures that the oxygen-releasing compound will reach the region containing the low-chlorinated chlorine-containing hydrocarbon, so that the low-chlorinated chlorine-containing hydrocarbon can be immediately oxidatively dechlorinated when it is formed, which is helpful. Degradation of chlorinated hydrocarbons.
圖1是一釋氧速率圖,說明實施例2及3的降解含氯碳氫化合物用組成物在緩衝溶液為pH=5.8時,在各種海水離子強度下之釋氧速率;圖2是一釋氧速率圖,說明實施例2及3的降解含氯碳氫化合物用組成物在緩衝溶液為pH=8.0時,在各種海水離子強度下之釋氧速率;圖3是一釋氧速率圖,說明實施例2及3的降解含氯碳氫化合物用組成物在緩衝溶液為pH=7.0時,在各種海水離子強度下之釋氧速率;圖4是一K值與海水離子強度關係圖,說明實施例2及3的降解含氯碳氫化合物用組成物在各種海水離子強度下之釋氧速率;圖5是一K值與pH值關係圖,說明實施例2及3的降解含氯碳氫化合物用組成物在各種pH值時之穩定度;圖6是一粒徑分佈圖,說明實施例1的降解含氯碳 氫化合物用組成物的油顆粒粒徑分佈。BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph of oxygen release rate, illustrating the oxygen release rates of the compositions of the degraded chlorine-containing hydrocarbons of Examples 2 and 3 at various seawater ionic strengths in a buffer solution of pH = 5.8; The oxygen rate diagram illustrates the oxygen release rate of the composition for degrading the chlorocarbon compound of Examples 2 and 3 at various seawater ionic strengths when the buffer solution is pH=8.0; FIG. 3 is a diagram of the oxygen release rate, illustrating The deoxidation chlorinated hydrocarbon compositions of Examples 2 and 3 have an oxygen release rate at various seawater ionic strengths when the buffer solution is pH=7.0; FIG. 4 is a graph showing the relationship between the K value and the seawater ion intensity, indicating the implementation. The oxygen release rates of the compositions of the chlorinated hydrocarbons of Examples 2 and 3 at various seawater ionic strengths; Figure 5 is a plot of K values versus pH values illustrating the degradation of chlorinated hydrocarbons of Examples 2 and 3. The stability of the composition at various pH values; Figure 6 is a particle size distribution diagram illustrating the degradation of the chlorine-containing carbon of Example 1. The particle size distribution of the oil particles of the composition for a hydrogen compound.
本發明降解含氯碳氫化合物用組成物的製備方法包含以下步驟:提供一油相溶液,包含過氧化鈣奈米顆粒、一植物油組份及一親油性界面活性劑;提供一包含水及一親水性界面活性劑的水相溶液;及將該油相溶液及該水相溶液進行一乳化處理,以獲得一降解含氯碳氫化合物用組成物,該降解含氯碳氫化合物用組成物包含過氧化鈣奈米顆粒、乳化液及經植物油包覆的過氧化鈣奈米顆粒。The preparation method of the composition for degrading a chlorine-containing hydrocarbon of the present invention comprises the steps of: providing an oil phase solution comprising calcium peroxide nano particles, a vegetable oil component and a lipophilic surfactant; providing a water and a water An aqueous phase solution of a hydrophilic surfactant; and an emulsification treatment of the oil phase solution and the aqueous phase solution to obtain a composition for degrading a chlorine-containing hydrocarbon, the composition for degrading the chlorocarbon-containing compound Calcium peroxide nanoparticle, emulsion and calcium peroxide nanoparticle coated with vegetable oil.
較佳地,該水相溶液用量與該油相溶液用量(水相溶液/油相溶液)的體積比範圍為0.2至4。更佳地,該水相溶液用量與該油相溶液用量(水相溶液/油相溶液)的體積比範圍為0.5至3。Preferably, the volume ratio of the aqueous phase solution to the oil phase solution amount (aqueous phase solution/oil phase solution) ranges from 0.2 to 4. More preferably, the volume ratio of the aqueous phase solution to the oil phase solution (aqueous phase solution/oil phase solution) ranges from 0.5 to 3.
該油相溶液的製法並無特別的限制,可採用例如(製法一):將該過氧化鈣奈米顆粒與該植物油組份先混合獲得一混合液,再使該混合液與該親油性界面活性劑進行混合,以得到該油相溶液;及(製法二):將該過氧化鈣奈米顆粒與該親油性界面活性劑先混合獲得一混合液,再使該混合液與該植物油組份進行混 合,以得到該油相溶液。混合過程可採用藥匙攪拌、攪拌器攪拌、渦流震盪機(Vortex)震盪、超音波探針震盪等方式。較佳地,該植物油組份與親油性界面活性劑的體積比例為1:25至125:25。The method for preparing the oil phase solution is not particularly limited, and for example, (Process 1): the calcium peroxide nanoparticle is first mixed with the vegetable oil component to obtain a mixed solution, and the mixture is mixed with the lipophilic interface. The active agent is mixed to obtain the oil phase solution; and (Process 2): the calcium peroxide nanoparticle is first mixed with the lipophilic surfactant to obtain a mixed solution, and then the mixed solution and the vegetable oil component are mixed Mix Combine to obtain the oil phase solution. The mixing process can be carried out by means of stirring of the spoon, stirring of the stirrer, oscillation of the vortex oscillating machine (Vortex), and oscillation of the ultrasonic probe. Preferably, the volume ratio of the vegetable oil component to the lipophilic surfactant is from 1:25 to 125:25.
較佳地,當植物油組份與親油性界面活性劑的總體積範圍為5至150 ml時,該過氧化鈣奈米顆粒的用量範圍為0.1至0.5 g。Preferably, the calcium peroxide nanoparticle is used in an amount ranging from 0.1 to 0.5 g when the total volume of the vegetable oil component and the lipophilic surfactant is in the range of 5 to 150 ml.
較佳地,該水相溶液用量與該植物油組份及親油性界面活性劑的總用量(水相溶液/植物油組份+親油性界面活性劑)的體積比範圍為0.5至3。Preferably, the volume ratio of the aqueous phase solution to the total amount of the vegetable oil component and the lipophilic surfactant (aqueous phase solution/vegetable oil component + lipophilic surfactant) ranges from 0.5 to 3.
該水相溶液的製法及混合所使用的設備並無特別的限制,可採用例如將水與該親水性界面活性劑置於攪拌器中攪拌均勻混合即可。較佳地,以該水相溶液的總體積為100 vol%,該水的用量範圍為90至99 vol%,該親水性界面活性劑的用量範圍為1至10 vol%。更佳地,以該水相溶液的總體積為100 vol%,該水的用量為98 vol%,該親水性界面活性劑的用量為2 vol%。The apparatus used for the preparation and mixing of the aqueous phase solution is not particularly limited, and for example, water and the hydrophilic surfactant may be placed in a stirrer to be stirred and uniformly mixed. Preferably, the total volume of the aqueous phase solution is 100 vol%, the amount of water is in the range of 90 to 99 vol%, and the hydrophilic surfactant is used in an amount ranging from 1 to 10 vol%. More preferably, the total volume of the aqueous phase solution is 100 vol%, the amount of water used is 98 vol%, and the amount of the hydrophilic surfactant is 2 vol%.
該乳化處理的方法並無特別限制,例如但不限於:相反轉溫度法、注射法、微流體法、均質攪拌法及超音波法(Sonication)。較佳地,該乳化處理是超音波法。於本發明的具體例中,是先將該油相溶液及該水相溶液混合均勻,再利用一功率為100瓦的超音波探針進行超音波乳化法。The method of the emulsification treatment is not particularly limited, and examples thereof include, but are not limited to, a reverse temperature method, an injection method, a microfluid method, a homogenization stirring method, and a supersonic method (Sonication). Preferably, the emulsification treatment is an ultrasonic method. In a specific example of the present invention, the oil phase solution and the aqueous phase solution are first uniformly mixed, and then an ultrasonic emulsification method is performed using an ultrasonic probe having a power of 100 watts.
以下將針對本發明降解含氯碳氫化合物用組成物的製備方法所使用的各個組份進一步說明:The respective components used in the preparation method of the composition for degrading a chlorine-containing hydrocarbon of the present invention are further explained below:
該過氧化鈣奈米顆粒並無特別限制,可選用一般市售品。The calcium peroxide nanoparticle is not particularly limited, and a general commercial product can be used.
較佳地,該過氧化鈣奈米顆粒的粒徑範圍是5至100 nm。Preferably, the calcium peroxide nanoparticle has a particle size ranging from 5 to 100 nm.
較佳地,該過氧化鈣奈米顆粒是經聚乙二醇改質的過氧化鈣奈米顆粒或經聚氧乙烯山梨醇酐單油酸酯[Polyoxyethylene(20)sorbitan monooleate,Tween 80]改質的過氧化鈣奈米顆粒,其中,該聚乙二醇的重量平均分子量範圍為190至210。於本發明的一具體例中,該經聚乙二醇改質的過氧化鈣奈米顆粒是依據Journal of Hazardous Materials,192(2011),1437-1440一文進行製備,所使用的聚乙二醇為德國Merck公司之品名為PEG200的聚乙二醇。於本發明的另一具體例中,是使用該經聚氧乙烯山梨醇酐單油酸酯改質的過氧化鈣奈米顆粒。Preferably, the calcium peroxide nanoparticle is modified by polyethylene glycol modified calcium peroxide nanoparticles or modified by polyoxyethylene (20) sorbitan monooleate (Tween 80). A fine calcium peroxide nanoparticle, wherein the polyethylene glycol has a weight average molecular weight ranging from 190 to 210. In a specific embodiment of the present invention, the polyethylene glycol-modified calcium peroxide nanoparticle is prepared according to the Journal of Hazardous Materials, 192 (2011), 1437-1440, and the polyethylene glycol used. It is a polyethylene glycol of the German company Merck which is called PEG200. In another embodiment of the invention, the calcium oxysorbate nanoparticles modified with polyoxyethylene sorbitan monooleate are used.
較佳地,該植物油組份的熔點範圍是一50至40℃,使用此熔點範圍的植物油組份可避免過氧化鈣過早接觸地下水而提早開始釋氧抑制了含氯碳氫化合物的厭氧還原脫氯。Preferably, the vegetable oil component has a melting point in the range of 50 to 40 ° C. The use of the vegetable oil component of the melting point range avoids premature contact of the calcium peroxide with groundwater and early initiation of oxygen release inhibits anaerobic of the chlorocarbon-containing compound. Reduce dechlorination.
較佳地,該植物油組份包含椰子油、棕櫚 油、大豆油、葵花籽油、油菜籽油、花生油、棉子油、棕櫚核仁油、玉米油、橄欖油。於本發明之一具體例中,該植物油包含椰子油及棕櫚油,且椰子油用量與棕櫚油用量的體積比例為1:1。Preferably, the vegetable oil component comprises coconut oil, palm Oil, soybean oil, sunflower oil, rapeseed oil, peanut oil, cottonseed oil, palm kernel oil, corn oil, olive oil. In one embodiment of the invention, the vegetable oil comprises coconut oil and palm oil, and the volume ratio of coconut oil to palm oil is 1:1.
較佳地,該親油性界面活性劑為親油性非離子型界面活性劑。Preferably, the lipophilic surfactant is a lipophilic nonionic surfactant.
較佳地,該親油性界面活性劑是選自於山梨醇酐單月桂酸酯(Sorbitan monolaurate,Span 20)、山梨醇酐單油酸酯(Sorbitan monooleate,Span 80)或此等之一組合。Preferably, the lipophilic surfactant is selected from the group consisting of sorbitan monolaurate (Span 20), sorbitan monooleate (Span 80) or a combination thereof.
較佳地,該親水性界面活性劑為親水性非離子型界面活性劑。Preferably, the hydrophilic surfactant is a hydrophilic nonionic surfactant.
較佳地,該親水性界面活性劑是選自於聚氧乙烯山梨醇酐單月桂酸酯[Polyoxyethylene(20)sorbitan monolaurate,Tween 20]、聚氧乙烯山梨醇酐單棕櫚酸酯[Polyoxyethylene(20)sorbitan monopalmitate,Tween 40]、聚氧乙烯山梨醇酐單硬脂酸酯[Polyoxyethylene(20)sorbitan monostearate,Tween 60]、聚氧乙烯山梨醇酐單油酸酯[Polyoxyethylene(20)sorbitan monooleate,Tween 80]或此等之一組合。Preferably, the hydrophilic surfactant is selected from the group consisting of polyoxyethylene (20) sorbitan monolaurate (Tween 20), polyoxyethylene sorbitan monopalmitate [Polyoxyethylene (20). )sorbitan monopalmitate, Tween 40], polyoxyethylene (20) sorbitan monostearate, Tween 60], polyoxyethylene sorbitan monooleate [Polyoxyethylene (20) sorbitan monooleate, Tween 80] or a combination of these.
本發明降解含氯碳氫化合物用組成物是由上述降解含氯碳氫化合物用組成物的製備方法所製得,該降解含氯碳氫化合物用組成物包含過氧化鈣奈米顆粒、乳化液及經植物油包覆的過氧化鈣奈米顆粒。The composition for degrading a chlorine-containing hydrocarbon of the present invention is obtained by the above-described method for preparing a composition for degrading a chlorine-containing hydrocarbon, and the composition for degrading a chlorine-containing hydrocarbon comprises calcium peroxide nanoparticles, an emulsion And calcium peroxide nanoparticles coated with vegetable oil.
較佳地,該降解含氯碳氫化合物用組成物的平均粒徑範圍是10至5000 nm。Preferably, the composition for degrading the chlorocarbon-containing compound has an average particle diameter ranging from 10 to 5000 nm.
本發明將就以下實施例來作進一步說明,但應瞭解的是,該實施例僅為例示說明之用,而不應被解釋為本發明實施之限制。The present invention will be further illustrated by the following examples, but it should be understood that this embodiment is intended to be illustrative only and not to be construed as limiting.
將3 g(0.027 mol)氯化鈣(CaCl2 ,廠商:美國J.T.Baker公司)、30 ml去離子水、15 ml氨水溶液(濃度1 M,0.0428 mol),及120 ml(0.675 mol)聚乙二醇200(polyethylene glycol 200,簡稱PEG 200,廠商:Merck)混合均勻,接著加入15 ml(0.1323 mol)過氧化氫水溶液(廠商:Sigma-aldrich,濃度30 wt%)形成一混合溶液,將該混合溶液放入一溫度控制在40℃的超音波洗淨震盪機(廠商:三角洲新儀器公司,型號:DC600H)中進行震盪混合2小時,該混合溶液的顏色會從無色漸漸轉變成黃色,此時該混合溶液的pH值約為9,接著加入氫氧化鈉溶液(濃度1 N)於該混合溶液中,使該混合溶液的pH上升至11.5,以產生氫氧化鈣沉澱物,再 用氫氧化鈉溶液(濃度1 N)清洗氫氧化鈣沉澱物三次後,以去離子水清洗氫氧化鈣沉澱物三次,即得到製備例1過氧化鈣奈米顆粒(粒徑:11.88±1.737 nm)。反應方程式如下所示:CaCl2 +H2 O2 → CaO2(hydrate) +2HCl3 g (0.027 mol) calcium chloride (CaCl 2 , manufacturer: JTBaker, USA), 30 ml deionized water, 15 ml aqueous ammonia solution (concentration 1 M, 0.0428 mol), and 120 ml (0.675 mol) polyethylene Alcohol 200 (polyethylene glycol 200, PEG 200 for short, Vendor: Merck) was uniformly mixed, and then 15 ml (0.1323 mol) of an aqueous hydrogen peroxide solution (manufacturer: Sigma-aldrich, concentration: 30 wt%) was added to form a mixed solution, and the mixture was mixed. The solution was placed in a supersonic cleaning shaker (manufacturer: Delta New Instrument Co., Ltd., model: DC600H) controlled at 40 ° C for 2 hours, and the color of the mixed solution gradually changed from colorless to yellow. The mixed solution has a pH of about 9, and then a sodium hydroxide solution (concentration 1 N) is added to the mixed solution to raise the pH of the mixed solution to 11.5 to produce a calcium hydroxide precipitate, and then sodium hydroxide. After the calcium hydroxide precipitate was washed three times with a solution (concentration: 1 N), the calcium hydroxide precipitate was washed three times with deionized water to obtain a calcium peroxide nanoparticle of Preparation Example 1 (particle diameter: 11.88 ± 1.737 nm). The reaction equation is as follows: CaCl 2 + H 2 O 2 → CaO 2 (hydrate) + 2 HCl
2 HCl+2NH3 → 2NH4 Cl2 HCl+2NH 3 → 2NH 4 Cl
NH4 Cl+NaOH → NH3 (g)+NaCl+H2 ONH 4 Cl+NaOH → NH 3 (g) + NaCl + H 2 O
將3 g(0.027 mol)氯化鈣溶解於30 ml去離子水中,接著再加入15 ml氨水溶液(濃度1 M,0.0428 mol)及2 ml的聚氧乙烯山梨醇酐單油酸酯(Tween 80)後混合均勻形成一混合溶液,接著取45 ml的過氧化氫水溶液(濃度30 wt%),將其以每秒鐘1滴的速率慢慢滴入於該混合溶液中,再於室溫攪拌下反應2小時,得到一微黃色溶液。接著加入氫氧化鈉溶液(濃度1 N)於該微黃色溶液中,使該微黃色溶液的pH調整至11.5,得到一白色懸浮液,過濾該白色懸浮液得到白色沉澱物後,將該白色沉澱物以氫氧化鈉溶液請洗3次,再加入100 ml磷酸緩衝鹽水(phosphate buffered saline,濃度0.01 M,pH=5.8),於80℃下進行真空烘乾2小時,即得到製備例2過氧化鈣奈米顆粒。Dissolve 3 g (0.027 mol) of calcium chloride in 30 ml of deionized water, followed by 15 ml of aqueous ammonia (concentration 1 M, 0.0428 mol) and 2 ml of polyoxyethylene sorbitan monooleate (Tween 80) After mixing, a mixed solution is uniformly formed, and then 45 ml of an aqueous hydrogen peroxide solution (concentration: 30 wt%) is taken, and it is slowly dropped into the mixed solution at a rate of 1 drop per second, and then stirred at room temperature. The reaction was carried out for 2 hours to give a slightly yellow solution. Then, a sodium hydroxide solution (concentration: 1 N) was added to the slightly yellow solution to adjust the pH of the slightly yellow solution to 11.5 to obtain a white suspension. After filtering the white suspension to obtain a white precipitate, the white precipitate was obtained. The solution was washed 3 times with sodium hydroxide solution, and then added with 100 ml of phosphate buffered saline (concentration 0.01 M, pH=5.8), and vacuum-dried at 80 ° C for 2 hours to obtain preparation example 2 peroxidation. Calcium nanoparticles.
於厭氧箱中將0.1 g製備例1的過氧化鈣奈米顆粒與 1 ml植物油組份(由體積比例1:1的椰子油及棕櫚油所組成;椰子油及棕櫚油的供應廠商:德意化工,食品級)於渦流震盪機(美國VORTEX-GENIE2公司,型號為G650)下混合均勻,形成一混合液。接著於一50 ml離心瓶中加入1 ml該混合液及5 ml的Span 80(供應廠商:Sigma-aldrich)形成一油相溶液。將0.2 ml的Tween 20(供應廠商:Sigma-aldrich)與9.8 ml的去離子水混合,形成一含2 vol% Tween 20的水相溶液,將10 ml的水相溶液加入該離心瓶中,以渦流震盪機(廠商:Scientific Industries,型號:Vortex-Genue 2 G650)混合均勻後,利用超音波探針(廠商:Virtis company,型號:Virsonic 100,功率:100瓦,時間:20秒)製備出降解含氯碳氫化合物用組成物,該組成物中包含過氧化鈣奈米顆粒、乳化液及經植物油包覆的過氧化鈣奈米顆粒。0.1 g of the calcium peroxide nanoparticle of Preparation Example 1 was placed in an anaerobic tank 1 ml vegetable oil component (composed of coconut oil and palm oil in a volume ratio of 1:1; coconut oil and palm oil supplier: German and Italian chemical, food grade) in vortex oscillating machine (VORTEX-GENIE2, USA, model number G650) is uniformly mixed to form a mixed solution. Then, 1 ml of this mixture and 5 ml of Span 80 (supplier: Sigma-aldrich) were added to a 50 ml centrifuge bottle to form an oil phase solution. 0.2 ml of Tween 20 (supplier: Sigma-aldrich) was mixed with 9.8 ml of deionized water to form an aqueous phase solution containing 2 vol% Tween 20, and 10 ml of the aqueous phase solution was added to the centrifuge bottle to The vortex oscillating machine (manufacturer: Scientific Industries, model: Vortex-Genue 2 G650) was uniformly mixed, and the degradation was prepared using an ultrasonic probe (manufacturer: Virtis company, model: Virsonic 100, power: 100 watts, time: 20 seconds). A composition for a chlorine-containing hydrocarbon comprising calcium peroxide nanoparticle, an emulsion, and calcium peroxide nanoparticles coated with vegetable oil.
以相同於實施例1的方法製備實施例2至3,差別在於實施例2至3是使用市售的過氧化鈣(99%,粒徑小於75 μm),及使用的植物油組份含有不同比例的椰子油及棕櫚油。Examples 2 to 3 were prepared in the same manner as in Example 1, except that Examples 2 to 3 used commercially available calcium peroxide (99%, particle size less than 75 μm), and the vegetable oil components used contained different ratios. Coconut oil and palm oil.
除了依據表1改變組份種類及用量外,實施例4至19使用製備例2過氧化鈣奈米顆粒、不同製法及混合方式進行,其中,實施例4至6是將製備例2過氧化鈣奈 米顆粒與植物油組份先以藥匙攪拌均勻獲得一混合液,接著再加入親油性界面活性劑Span 80,以獲得一油相溶液;接著再將油相溶液與含有2 vol% Tween 20的水相溶液,利用超音波探針(廠商:Virtis company,型號:Virsonic 100,功率:最大功率,時間:20-30秒)製備出降解含氯碳氫化合物用組成物。實施例7至9是將製備例2過氧化鈣奈米顆粒與植物油組份先以超音波探針(功率為3瓦,時間:20-30秒)震盪均勻獲得一混合液,接著再加入親油性界面活性劑Span 80並以超音波探針震盪(功率為3瓦,時間:20-30秒)震盪均勻,以獲得一油相溶液;接著再將油相溶液與含有2 vol% Tween 20的水相溶液,利用超音波探針(功率:最大功率,時間:20-30秒)製備出降解含氯碳氫化合物用組成物。實施例10至13是將製備例2過氧化鈣奈米顆粒與親油性界面活性劑Span 80先以超音波探針(功率為3瓦,時間:20-30秒)震盪均勻獲得一混合液,接著再加入植物油組份並以超音波探針震盪(功率為3瓦,時間:20-30秒),以獲得一油相溶液;接著再將油相溶液與含有2 vol% Tween 20的水相溶液,利用超音波探針(功率:最大功率,時間:20-30秒)製備出降解含氯碳氫化合物用組成物。實施例14至19是將製備例2過氧化鈣奈米顆粒與親油性界面活性劑Span 80先以渦流震盪機震盪均勻獲得一混合液,接著再加入植物油組份並以渦流震盪機,以獲得一油相溶液;接著再將油 相溶液與含有2 vol% Tween 20的水相溶液,利用超音波探針(功率:最大功率,時間:20-30秒)製備出降解含氯碳氫化合物用組成物。Except for changing the type and amount of the components according to Table 1, Examples 4 to 19 were carried out using the calcium peroxide nanoparticles of Preparation Example 2, different preparation methods and mixing methods, wherein Examples 4 to 6 were Preparations 2 of calcium peroxide. Nai The rice granules and the vegetable oil component are first stirred uniformly with a spatula to obtain a mixed solution, followed by the lipophilic surfactant Span 80 to obtain an oil phase solution; and then the oil phase solution and the water containing 2 vol% Tween 20 For the phase solution, a composition for degrading a chlorine-containing hydrocarbon was prepared using an ultrasonic probe (manufacturer: Virtis company, model: Virsonic 100, power: maximum power, time: 20-30 seconds). In Examples 7 to 9, the calcium peroxide nanoparticle of Preparation Example 2 and the vegetable oil component were first shaken by an ultrasonic probe (power: 3 watts, time: 20-30 seconds) to obtain a mixed solution, and then added to the parent. The oily surfactant Span 80 is oscillated with an ultrasonic probe (power of 3 watts, time: 20-30 seconds) to obtain an oil phase solution; then the oil phase solution is contained with 2 vol% Tween 20 The aqueous phase solution was prepared by using an ultrasonic probe (power: maximum power, time: 20-30 seconds) to decompose a composition containing a chlorine-containing hydrocarbon. In Examples 10 to 13, the calcium peroxide nanoparticles of Preparation Example 2 and the lipophilic surfactant Span 80 were first vortexed with an ultrasonic probe (power: 3 watts, time: 20-30 seconds) to obtain a mixed solution. Then add the vegetable oil component and oscillate with an ultrasonic probe (power is 3 watts, time: 20-30 seconds) to obtain an oil phase solution; then the oil phase solution and the water phase containing 2 vol% Tween 20 For the solution, a composition for degrading a chlorine-containing hydrocarbon was prepared using an ultrasonic probe (power: maximum power, time: 20-30 seconds). In Examples 14 to 19, the calcium peroxide nanoparticles of Preparation Example 2 and the lipophilic surfactant Span 80 were first vortexed by a vortex oscillating machine to obtain a mixed liquid, and then the vegetable oil component was added and vortexed to obtain a mixture. An oil phase solution; then oil A phase solution and an aqueous phase solution containing 2 vol% of Tween 20 were used to prepare a composition for degrading a chlorine-containing hydrocarbon using an ultrasonic probe (power: maximum power, time: 20-30 seconds).
製備實施例1至19之降解含氯碳氫化合物用組成物所使用的組分種類及用量由表1所示。The kinds and amounts of the components used in the compositions for degrading chlorine-containing hydrocarbons of Preparation Examples 1 to 19 are shown in Table 1.
配製pH=5.8、7.0及8.0的磷酸鈉緩衝溶液。配製方式為先製備Na2 HPO4 的儲備溶液(stock solution)(濃度1.0 M)及NaH2 PO4 的儲備溶液(濃度1.0 M),再依表2所示的用量取Na2 HPO4 的儲備溶液及NaH2 PO4 的儲備溶液,並將兩者混合後再加入900 ml去離子水,即得到pH=5.8、7.0及8.0的磷酸鈉緩衝溶液。A sodium phosphate buffer solution of pH = 5.8, 7.0 and 8.0 was prepared. The preparation method is to prepare a stock solution of Na 2 HPO 4 (concentration 1.0 M) and a stock solution of NaH 2 PO 4 (concentration 1.0 M), and then take the reserve of Na 2 HPO 4 according to the amount shown in Table 2. The solution and the stock solution of NaH 2 PO 4 , and the two were mixed, and then 900 ml of deionized water was added to obtain a sodium phosphate buffer solution of pH=5.8, 7.0 and 8.0.
接著於pH=5.8、7.0及8.0的磷酸鈉緩衝溶液中,依據海水離子總表添加三種海水離子強度(或海水鹽度),取氯離子19.36 g/L、鈉離子10.78 g/L、鎂離子1.283 g/L、硫酸根離子1.807 g/L、鈣離子0.413 g/L、鉀離子0.399 g/L當作100%的海水離子強度;10%的海水離子強度則各離子濃度稀釋10倍;0%的海水離子強度則不添加任何離子,配製出9種緩衝溶液。各由表3所示,且pH值及海水離子強度所模擬的環境分別為:河川與海水交接處(海水離子強度100%)、感潮河段(海水離子強度10%)、未跟海水接觸的河川(海水 離子強度0%)、高氯數碳氫化合物尚未被微生物分解的地下水(pH≒8.0)、無受含氯碳氫化合物污染的地下水(pH≒7.0),與高氯數碳氫化合物已被微生物分解至低氯數碳氫化合物(pH≒5.8)。Then, in the sodium phosphate buffer solution of pH=5.8, 7.0 and 8.0, three seawater ionic strengths (or seawater salinity) were added according to the seawater ion master table, and the chloride ion was 19.36 g/L, the sodium ion was 10.78 g/L, and the magnesium ion was obtained. 1.283 g/L, sulfate ion 1.807 g/L, calcium ion 0.413 g/L, potassium ion 0.399 g/L as 100% seawater ionic strength; 10% seawater ionic strength diluted 10 times for each ion concentration; % of the seawater ionic strength was added without any ions, and nine buffer solutions were prepared. The environment simulated by pH and seawater ion intensity is shown as follows: the intersection of river and seawater (100% seawater ionic strength), the tidal reaches (10% seawater ionic strength), and no contact with seawater. River (sea water Ionic strength 0%), high-chlorinated hydrocarbons that have not been decomposed by microorganisms (pH ≒ 8.0), groundwater contaminated with chlorinated hydrocarbons (pH ≒ 7.0), and high chlorinated hydrocarbons have been microbial Decomposes to low chlorine hydrocarbons (pH ≒ 5.8).
以下為方便描述量測方式,以實施例2的降解含氯碳氫化合物用組成物進行說明,實施例3依照相同方式進行量測。Hereinafter, the composition for degrading the chlorine-containing hydrocarbon of Example 2 will be described in order to facilitate the description of the measurement method, and Example 3 is measured in the same manner.
先將上述9種緩衝溶液各取200 ml分別放入9個500 ml的厭氧瓶中,再於該等厭氧瓶中加入5 ml的實施例2降解含氯碳氫化合物用組成物,進行混合後得到9個待測液。接著於0分鐘、30分鐘、60分鐘、2小時、4小時、4小時、4小時、8小時、24小時、3天、7天及28天時利用針筒吸取5 ml待測液到溶氧計 (廠商:台灣Lutron公司,型號:DO-5510)的檢測管中,檢測釋氧速率。實施例2及3組成物的釋氧速率結果見圖1至3。First, 200 ml of each of the above 9 kinds of buffer solutions were placed in nine 500 ml anaerobic bottles, and then 5 ml of the composition for degrading the chlorocarbon-containing compound of Example 2 was added to the anaerobic bottles. After mixing, 9 liquids to be tested were obtained. Then, using the syringe to take 5 ml of the test solution to the dissolved oxygen at 0 minutes, 30 minutes, 60 minutes, 2 hours, 4 hours, 4 hours, 4 hours, 8 hours, 24 hours, 3 days, 7 days and 28 days. meter The oxygen release rate was measured in a test tube (manufacturer: Taiwan Lutron, model: DO-5510). The results of the oxygen release rate of the compositions of Examples 2 and 3 are shown in Figures 1 to 3.
以實施例1的降解含氯碳氫化合物用組成物進行管柱實驗。A column column experiment was carried out using the composition for degrading a chlorine-containing hydrocarbon of Example 1.
為了瞭解降解含氯碳氫化合物用組成物去除地下水層中之三氯乙烯的效果,利用管柱實驗模擬四種類型的地下水層(高濃度三氯乙烯、含高濃度三氯乙烯及腐植酸、低濃度三氯乙烯,含低濃度三氯乙烯及腐植酸),再將實施例1降解含氯碳氫化合物用組成物通入管柱中。以下將針對管柱實驗步驟做進一步說明:In order to understand the effect of degrading the composition of chlorine-containing hydrocarbons to remove trichloroethylene from the groundwater layer, four types of groundwater layers (high concentrations of trichloroethylene, high concentrations of trichloroethylene and humic acid, The low concentration of trichloroethylene, containing a low concentration of trichloroethylene and humic acid, was passed through the column of Example 1 to degrade the chlorinated hydrocarbon composition. The following is a further explanation of the column experiment steps:
(1)管柱填充:先將五種粒徑(75 μm、130 μm、200 μm、300 μm、600 μm)的玻璃砂均先以濃度為20%的硝酸進行酸洗步驟,再以去離子水清洗,以待後續填充管柱時使用。(1) Column packing: firstly, the glass sands of five particle sizes (75 μm, 130 μm, 200 μm, 300 μm, 600 μm) are first subjected to a pickling step with a concentration of 20% nitric acid, followed by deionization. Wash with water for later use when filling the column.
將一玻璃管柱(內徑1.7公分,長12公分)的底端以一個具有7毫米孔洞的5號矽膠塞塞住,再於管柱內放置5片具有細小孔隙的不鏽鋼墊片,以避免後續填充的玻璃砂流出。接著,將一鐵氟龍管線***該矽膠塞的孔洞中,再以一銅閥連接該鐵氟龍管線。再將清洗過的玻璃砂依一般土壤分佈比例填充至該管柱 內,填充後管柱內玻璃砂的長度為9.5公分,均勻係數D60/D10為1.74(D60表示累積重量百分比60%之粒徑;D10表示累積重量百分比10%之粒徑)。接著同樣先放入5片具有細小孔隙的不鏽鋼墊片,再以具有7毫米孔洞的5號矽膠塞塞住該管柱頂端,然後同樣接上鐵氟龍管線及銅閥。為避免於填充過程中有氣泡存在管柱中,上述組裝及填充作業均在水中進行,且充填完成的管柱以肉眼檢視,若管柱內無氣泡存在,方可進行後續管柱實驗。填充完的管柱標示為管柱(I)。接著以同樣方式填充管柱(II)至(IV)。The bottom end of a glass column (1.7 cm inner diameter, 12 cm long) was plugged with a No. 5 silicone plug with a 7 mm hole, and five stainless steel spacers with small pores were placed in the column to avoid Subsequent filled glass sand flows out. Next, a Teflon line is inserted into the hole of the glue plug, and the Teflon line is connected by a copper valve. The cleaned glass sand is then filled to the column according to the general soil distribution ratio. Inside, the length of the glass sand in the post-filled column was 9.5 cm, and the uniformity coefficient D60/D10 was 1.74 (D60 represents a cumulative weight percentage of 60% of the particle size; D10 represents a cumulative weight percentage of 10% of the particle size). Next, five stainless steel shims with fine pores were placed first, and then the top of the column was stoppered with a No. 5 silicone plug having a hole of 7 mm, and then the Teflon line and the copper valve were also connected. In order to avoid the presence of air bubbles in the column during the filling process, the above assembly and filling operations are carried out in water, and the filled column is visually inspected. If there are no bubbles in the column, the subsequent column experiment can be performed. The filled column is labeled as the column (I). The columns (II) to (IV) are then filled in the same manner.
接著以水頭降落法(Falling head measurement)量測管柱(I)至(IV)的水力傳導係數(K值,代表地下水在含水層中流動的難易程度,數值越大表示水流動越容易),以確認充填後的管柱具備相似的砂層特性。K值的計算公式如下所示:
其中,a=量測水頭處之水管之斷面積;A=填充砂質之管柱之斷面積;L=砂質管柱之砂質長度;H0 =實驗前之水頭高;H1 =實驗後之水頭高;t=H0 到H1 所經過的時間。管柱(I)至(IV)的水力傳導係數結果為表4所示。由表4的結果可知管柱(I)至(IV)的砂層特性相似,可用於製備模擬地下水層的管柱。Where a = the area of the water pipe at the water head; A = the area of the column filled with sand; L = the length of the sand column; H 0 = the height of the head before the experiment; H 1 = experiment The head after the water is high; t = H 0 to H 1 elapsed time. The hydraulic conductivity coefficients of the columns (I) to (IV) are shown in Table 4. It can be seen from the results of Table 4 that the sand layers of the columns (I) to (IV) have similar properties and can be used to prepare the column for simulating the groundwater layer.
(2)模擬地下水層之管柱的製備:(2) Preparation of the column for simulating the groundwater layer:
(I)含高濃度三氯乙烯及腐植酸的管柱[管柱(I)]:取上述管柱(I),分別將腐植酸及三氯乙烯先後注入管柱內,詳細流程如下:(i)腐植酸的注入---以去離子水不斷進流沖洗管柱至少24小時,待沖洗完成後將210 mg的腐植酸溶於0.42 ml去離子水後再注入管柱中,待密閉迴流至少24小時後,以每採樣點為1 PV[10 ml,PV為孔隙體積(Pore volume)]的方式收集出流樣品,並利用液體總碳分析儀(廠商:O-I-Analytical型號:1020A)分析每PV出流樣品的腐植酸量[分析方法參照台灣環檢所公告的水中總有機碳檢測-燃燒/紅外線測定法(NIEA W530.51C)],直到腐植酸的出流量趨近於零,經過52 PV(520 ml)後,以腐植酸的初始量減去腐植酸的總出流量,即得知管柱中腐植酸的殘餘量為0.244 mg(0.116%);(ii)三氯乙烯的注入---接著注入0.25 mg(25 ppm)的三氯乙烯於管柱中,待密閉迴流至少24小時後,利用一密閉的頂空樣品瓶以自動頂空萃取儀(廠商:Perkin Elmer,型號:TurboMatrix 40)進行採樣,每採樣點為1 PV(10 ml),將該頂空樣品瓶置於85℃環境下30分鐘,使三氯乙烯揮發至該頂空樣品瓶的瓶頂,接著將三氯乙烯導入氣相層析儀[GC-ECD,PerkinElmer Clarus 580,所使用管柱為Agilent J&W HP-5(30 m×0.32 mm,film 0.25 μm),分析方法參照台灣環檢所公告的NIEA M700.01C方法],直到三氯乙烯的出流量接近零,經過35 PV後,以三氯乙烯的初始量減去三氯乙烯的總出流量,即可得知管柱中三氯乙烯的殘餘量為0.1851 mg。(I) Column with high concentration of trichloroethylene and humic acid [column (I)]: Take the above column (I), and inject humic acid and trichloroethylene into the column, respectively. The detailed process is as follows: i) Injecting humic acid---washing the column with deionized water for at least 24 hours. After the completion of the rinsing, dissolve 210 mg of humic acid in 0.42 ml of deionized water and then inject into the column. After at least 24 hours, the flow sample was collected at a sampling point of 1 PV [10 ml, PV is the Pore volume], and analyzed by a liquid total carbon analyzer (manufacturer: OI-Analytical model: 1020A). The amount of humic acid per PV outflow sample [analytical method refers to the total organic carbon detection in the water announced by the Taiwan Environmental Protection Institute - combustion / infrared measurement method (NIEA W530.51C)] until the humic acid output flow approaches zero, after After 52 PV (520 ml), the total amount of humic acid was subtracted from the initial amount of humic acid, that is, the residual amount of humic acid in the column was 0.244 mg (0.116%); (ii) the injection of trichloroethylene --- Then inject 0.25 mg (25 ppm) of trichloroethylene into the column, and after a closed reflow for at least 24 hours, use a closed Empty Vial headspace extraction automatic sampling instrument (Manufacturer: TurboMatrix 40: Perkin Elmer, model), each sample point 1 PV (10 ml), the headspace vial was placed in an environment of 85 ° C for 30 minutes to volatilize trichloroethylene to the top of the headspace vial, and then the trichloroethylene was introduced into a gas chromatograph [GC- ECD, PerkinElmer Clarus 580, the column used is Agilent J&W HP-5 (30 m × 0.32 mm, film 0.25 μm), the analytical method is based on the NIEA M700.01C method announced by the Taiwan Environmental Protection Institute, until the output of trichloroethylene The flow rate is close to zero. After 35 PV, the total amount of trichloroethylene is subtracted from the initial amount of trichloroethylene, and the residual amount of trichloroethylene in the column is 0.1851 mg.
(II)含高濃度三氯乙烯的管柱[管柱(II)]:除了未注入腐植酸以及三氯乙烯的分析共經過70 PV外,其餘流程與上述高濃度三氯乙烯且含腐植酸之管柱的流程相同,最後得到管柱中三氯乙烯的殘餘量為0.218 mg。(II) Column with high concentration of trichloroethylene [column (II)]: except for the uninjected humic acid and the analysis of trichloroethylene through 70 PV, the other processes with the above-mentioned high concentration of trichloroethylene and containing humic acid The process of the column was the same, and finally the residual amount of trichloroethylene in the column was 0.218 mg.
(III)含低濃度三氯乙烯及腐植酸的管柱[管柱(III)]:除了腐植酸的分析共經過60 PV、三氯乙烯的分析共經過35 PV,以及所注入三氯乙烯的量為0.025 mg(2.5 ppm)外,其餘流程與上述高濃度三氯乙烯且含腐植酸之管柱的流程相同,最後得到管柱中腐植酸的殘餘量為0.289 mg(0.138%),三氯乙烯的殘餘量為0.0153 mg。(III) Columns containing low concentrations of trichloroethylene and humic acid [column (III)]: In addition to the analysis of humic acid, a total of 60 PV, trichloroethylene analysis, a total of 35 PV, and the injection of trichloroethylene The amount of 0.025 mg (2.5 ppm) was the same as that of the high-concentration trichloroethylene and humic acid-containing column. The residual amount of humic acid in the column was 0.289 mg (0.138%). The residual amount of ethylene was 0.0153 mg.
(IV)含低濃度三氯乙烯的管柱[管柱(IV)]: 除了未注入腐植酸、所注入三氯乙烯的量為0.025 mg(2.5 ppm),以及三氯乙烯的分析共經過23 PV外,其餘流程與上述高濃度三氯乙烯且含腐植酸之管柱的流程相同,最後得到管柱中三氯乙烯的殘餘量為0.0234 mg。(IV) Columns containing low concentrations of trichloroethylene [column (IV)]: Except that humic acid was not injected, the amount of trichloroethylene injected was 0.025 mg (2.5 ppm), and the analysis of trichloroethylene passed through 23 PV, the other procedures were the same as those of the above-mentioned high-concentration trichloroethylene and containing humic acid. The process was the same, and finally the residual amount of trichloroethylene in the column was 0.0234 mg.
(3)三氯乙烯去除率測試:為方便描述測試過程,下面以管柱(I)進行說明。(3) Trichloroethylene removal rate test: In order to facilitate the description of the test process, the following is a description of the column (I).
將4 ml的實施例1之降解含氯碳氫化合物用組成物注入上述管柱(I)中,用頂空樣品瓶以每採樣點為1 PV(10 ml)的方式收集出流樣品,每PV出流樣品是利用自動頂空萃取儀及GC-ECD分析所含的三氯乙烯量,以固體有機碳分析儀(廠商:O-I-Analytical,型號:1020A)分析所含的實施例1降解含氯碳氫化合物用組成物的量,經過25 PV後,可得到三氯乙烯移除量及組成物出流量,再進一步計算管柱(I)的三氯乙烯去除率及每單位體積之組成物的三氯乙烯吸附量。管柱(II)至(IV)是以類似管柱(I)的方式進行測試,差別在於管柱(III)及(IV)是分別經過23 PV後得到三氯乙烯移除量及組成物出流量。實驗結果見表5。4 ml of the degraded chlorocarbon-containing composition of Example 1 was injected into the above-mentioned column (I), and a flow sample was collected by using a headspace vial at a sampling point of 1 PV (10 ml). The PV outflow sample is the amount of trichloroethylene contained in the analysis by the automatic headspace extractor and GC-ECD, and the degradation of the sample contained in Example 1 is analyzed by a solid organic carbon analyzer (manufacturer: OI-Analytical, model: 1020A). The amount of the composition of the chlorocarbon hydrocarbon, after 25 PV, the amount of removal of trichloroethylene and the flow rate of the composition can be obtained, and the removal rate of trichloroethylene and the composition per unit volume of the column (I) can be further calculated. The amount of trichloroethylene adsorbed. The columns (II) to (IV) are tested in a similar manner to the column (I), except that the columns (III) and (IV) are obtained after 23 PV respectively to obtain the amount of trichloroethylene removed and the composition flow. The experimental results are shown in Table 5.
以粒徑量測儀(廠商:Malvern Instruments,Worcestershire,型號:Zetasizer® Nano ZS)對實施例1及實施例4至19降解含氯碳氫化合物用組成物進行油 顆粒粒徑分析,水與油脂折射指數分別設定為1.330及1.460,其結果由表6所示。實施例1降解含氯碳氫化合物用組成物的粒徑分佈圖由圖6所示。In the particle size measuring instrument (Manufacturer: Malvern Instruments, Worcestershire, Model: Zetasizer ® Nano ZS) of 4-19 for the degradation of chlorinated hydrocarbon oil with a particle size analysis of Example 1 and composition Example, water and fat The refractive indices were set to 1.330 and 1.460, respectively, and the results are shown in Table 6. The particle size distribution chart of the composition for degrading the chlorine-containing hydrocarbon of Example 1 is shown in Fig. 6.
a:三氯乙烯去除率=(三氯乙烯去除量)÷(三氯乙烯殘餘量)a: Trichloroethylene removal rate = (trichloroethylene removal amount) ÷ (trichloroethylene residual amount)
在圖1至3中,可發現實施例2及3的組成物不論在何種環境下,在前三個小時已開始釋氧,這是因為組成物中的過氧化鈣奈米顆粒與緩衝溶液直接接觸而釋氧所致。於圖1中(pH=5.8),實施例2及3的組成物於不同海水離子強度下,皆大約在4小時後減少釋氧,直到大約312小時後釋氧量又開始提昇,顯示組成物中之經植物油包覆的過氧化鈣奈米顆粒開始釋氧。圖2及3的結果大致與圖1相同。In Figures 1 to 3, it can be found that the compositions of Examples 2 and 3 have started to release oxygen in the first three hours regardless of the environment, because the calcium peroxide nanoparticles and the buffer solution in the composition Direct contact and release of oxygen. In Figure 1 (pH = 5.8), the compositions of Examples 2 and 3 reduced oxygen release after about 4 hours at different seawater ionic strengths, and the oxygen release amount began to increase again after about 312 hours, indicating composition. The calcium peroxide nanoparticles coated with vegetable oil begin to release oxygen. The results of Figures 2 and 3 are substantially the same as Figure 1.
為了更瞭解實施例2及3的組成物與pH值及海水離子強度間的關係,由釋氧速率測試的實驗數 據分析作圖而獲得一階動力反應方程式(first-order reaction),再透過此方程式求出各種條件下的K值,K值越大表示釋氧速率越快(亦即經植物油包覆的過氧化鈣奈米顆粒之植物油被破壞,使得過氧化鈣與緩衝溶液接觸而開始釋氧),K值越小表示釋氧速率越慢(亦即植物油能穩定地包覆過氧化鈣奈米顆粒,使過氧化鈣緩慢地釋氧)。將所得K值分別與pH值及海水離子強度作圖,所得結果分別由圖4及5所示。In order to better understand the relationship between the compositions of Examples 2 and 3 and the pH and seawater ionic strength, the number of experiments by the rate of oxygen release rate test According to the analysis, a first-order reaction equation is obtained, and then the K value under various conditions is obtained by the equation. The larger the K value, the faster the oxygen release rate (that is, the vegetable oil coating) The vegetable oil of the calcium oxide nanoparticle is destroyed, so that the calcium peroxide is contacted with the buffer solution to start oxygen release, and the smaller the K value, the slower the oxygen release rate (that is, the vegetable oil can stably coat the calcium peroxide nanoparticle, Calcium peroxide is slowly released to oxygen). The obtained K values were plotted against pH and seawater ion intensity, respectively, and the results are shown in Figures 4 and 5, respectively.
在圖4中(K值與海水離子強度關係圖),可明顯看出實施例3之組成物(僅使用椰子油)的K值隨著海水離子強度的增加而大幅提昇,表示海水離子強度越強,對於植物油的破壞力就越高。反觀實施例2之組成物(使用棕櫚油與椰子油之混合),不管在哪種海水離子強度下,其K值差異不大,表示實施例2之組成物中的植物油可以穩定存在任何海水離子強度環境中,造成此現象主要原因是因為棕櫚油成分中含有39%油酸(oleic acid)與10.5%亞麻油酸(linoleic acid),而椰子油成分中含有6.0%油酸與2.5%亞麻油酸,油酸含有一個雙鍵與羧酸,亞麻油酸含有兩個雙鍵,因此棕櫚油比較能抵抗離子的破壞,故由棕櫚油與椰子油混合的植物油比單純只用椰子油更可以穩定包覆過氧化鈣奈米顆粒,也就是實施例2之組成物可適用於各種海水離子強度之環境。In Fig. 4 (the relationship between the K value and the seawater ion intensity), it is apparent that the K value of the composition of Example 3 (only coconut oil) is greatly increased as the seawater ion intensity increases, indicating that the seawater ion intensity is higher. Strong, the more destructive to vegetable oil. In contrast, the composition of Example 2 (using a mixture of palm oil and coconut oil) has no difference in K value regardless of the seawater ionic strength, indicating that the vegetable oil in the composition of Example 2 can stably exist in any seawater ion. In the strong environment, the main reason for this phenomenon is that palm oil contains 39% oleic acid and 10.5% linoleic acid, while coconut oil contains 6.0% oleic acid and 2.5% linseed oil. Acid, oleic acid contains a double bond and carboxylic acid, linoleic acid contains two double bonds, so palm oil is more resistant to ion damage, so the vegetable oil mixed with palm oil and coconut oil is more stable than pure coconut oil alone. The coated calcium peroxide nanoparticle, that is, the composition of Example 2, can be applied to various seawater ion intensity environments.
在圖5中(K值與pH值關係圖),實施例3 之組成物在較低pH值環境中無法穩定存在,但可穩定存在於中、高pH值的環境中。實施例2之組成物能穩定存在於低pH值環境中,且整體趨勢顯示pH值越高植物油穩定度越好。In Figure 5 (K value versus pH value), Example 3 The composition does not exist stably in a lower pH environment, but can be stably present in medium and high pH environments. The composition of Example 2 can be stably present in a low pH environment, and the overall trend shows that the higher the pH, the better the vegetable oil stability.
實施例1的降解含氯碳氫化合物用組成物在低濃度三氯乙烯的管柱中不論是否含有腐植酸,去除三氯乙烯的效率能達到82%以上,每單位體積之組成物的三氯乙烯吸附量能達到0.00357 mg/ml以上;在高濃度三氯乙烯的管柱中不論是否含有腐植酸,去除效率三氯乙烯的效率能達14%以上,每單位體積之組成物的三氯乙烯吸附量能達到0.00802 mg/ml以上,因此可證明實施例1的降解含氯碳氫化合物用組成物不論在何種地下水層中皆能有效吸附含氯碳氫化合物,而有利於提升生物處理效率,及達到很好的去除效率。The composition for degrading the chlorocarbon-containing compound of Example 1 can remove trichloroethylene by more than 82% in the column of the low-concentration trichloroethylene, whether or not it contains humic acid, and the trichlorochloride per unit volume of the composition The amount of ethylene adsorbed can reach above 0.00357 mg/ml; in the column of high concentration of trichloroethylene, whether or not it contains humic acid, the efficiency of removing trichloroethylene can reach more than 14%, and the composition per unit volume of trichloroethylene The adsorption amount can reach above 0.00802 mg/ml, so it can be proved that the composition for degrading the chlorocarbon compound of Example 1 can effectively adsorb chlorine-containing hydrocarbons regardless of the groundwater layer, thereby contributing to the improvement of biological treatment efficiency. And achieve good removal efficiency.
在圖6中可發現,實施例1降解含氯碳氫化合物用組成物的三個主要波峰之油顆粒粒徑為4391 nm、1821 nm及447.8 nm,其分布百分比分別為23.3%、41.6%及35.1%,平均粒徑為936.9 nm。並由表6得知,實施例4至19之降解含氯碳氫化合物用組成物因粒徑小於土壤空隙而能有效地於土壤地下水層中傳輸。It can be found in Fig. 6 that the particle diameters of the oil particles of the three main peaks of the composition for degrading the chlorocarbon-containing compound of Example 1 are 4391 nm, 1821 nm and 447.8 nm, and the distribution percentages thereof are 23.3% and 41.6%, respectively. 35.1%, the average particle size is 936.9 nm. It is also known from Table 6 that the compositions for degrading chlorine-containing hydrocarbons of Examples 4 to 19 can be efficiently transported in the soil groundwater layer because the particle size is smaller than the soil voids.
綜上所述,本發明製備方法所製得的降解 含氯碳氫化合物用組成物能於污染場址中同時且於同一區域提供電子供給者及釋氧化合物,且平均粒徑小於土壤空隙而能有效地於土壤地下水層中傳輸,並能於不同的土攘地下水層環境下持續緩慢地釋氧,還能有效吸附含氯碳氫化合物,而有利於提升生物處理效率,及達到很好的去除效率。In summary, the degradation produced by the preparation method of the present invention The chlorinated hydrocarbon composition can provide electron donors and oxygen releasing compounds simultaneously in the same site in the contaminated site, and the average particle size is smaller than the soil voids and can be effectively transported in the soil groundwater layer, and can be different The continuous release of oxygen in the groundwater environment of the soil can effectively adsorb chlorine-containing hydrocarbons, which is beneficial to improve biological treatment efficiency and achieve good removal efficiency.
惟以上所述者,僅為本發明之較佳實施例而已,當不能以此限定本發明實施之範圍,即大凡依本發明申請專利範圍及專利說明書內容所作之簡單的等效變化與修飾,皆仍屬本發明專利涵蓋之範圍內。The above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent changes and modifications made by the patent application scope and patent specification content of the present invention, All remain within the scope of the invention patent.
Claims (10)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
TW102100920A TWI478877B (en) | 2013-01-10 | 2013-01-10 | Degradation of chlorinated hydrocarbon compounds and methods for their preparation |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
TW102100920A TWI478877B (en) | 2013-01-10 | 2013-01-10 | Degradation of chlorinated hydrocarbon compounds and methods for their preparation |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201427912A TW201427912A (en) | 2014-07-16 |
TWI478877B true TWI478877B (en) | 2015-04-01 |
Family
ID=51725964
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW102100920A TWI478877B (en) | 2013-01-10 | 2013-01-10 | Degradation of chlorinated hydrocarbon compounds and methods for their preparation |
Country Status (1)
Country | Link |
---|---|
TW (1) | TWI478877B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI616409B (en) * | 2015-11-19 | 2018-03-01 | 裕山環境工程股份有限公司 | Emulsive composition and method of preparing the same |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW201125649A (en) * | 2010-01-28 | 2011-08-01 | Univ Nat Sun Yat Sen | Degradable and slow-releasing material for enhancing chemical oxidation of contaminated soil and groundwater |
-
2013
- 2013-01-10 TW TW102100920A patent/TWI478877B/en not_active IP Right Cessation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW201125649A (en) * | 2010-01-28 | 2011-08-01 | Univ Nat Sun Yat Sen | Degradable and slow-releasing material for enhancing chemical oxidation of contaminated soil and groundwater |
Also Published As
Publication number | Publication date |
---|---|
TW201427912A (en) | 2014-07-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Zhang et al. | AOPs-based remediation of petroleum hydrocarbons-contaminated soils: Efficiency, influencing factors and environmental impacts | |
Hamamoto et al. | Effects of pH on nano-bubble stability and transport in saturated porous media | |
Cui et al. | Chemical oxidation of benzene and trichloroethylene by a combination of peroxymonosulfate and permanganate linked by in-situ generated colloidal/amorphous MnO2 | |
AU2008305539B2 (en) | Method for extraction and surfactant enhanced subsurface contaminant recovery | |
Chen et al. | Electrokinetic techniques, their enhancement techniques and composite techniques with other processes for persistent organic pollutants remediation in soil: a review | |
WO2012170028A1 (en) | Compositions and methods for oil spill remediation | |
US20100209194A1 (en) | System for soil, groundwater, and surface water remediation, and related methods | |
Cha et al. | Removal of oil and oil sheen from produced water by pressure-assisted ozonation and sand filtration | |
Corpuz et al. | Enhanced removal of mixed metal ions from aqueous solutions using flotation by colloidal gas aphrons stabilized with sodium alginate | |
WO2021091840A1 (en) | A method and apparatus for in-situ removal of per- and poly-fluoroalkyl substances | |
Zhao et al. | Advanced nanomaterials for degrading persistent organic pollutants | |
Mazloomi et al. | Remediation of Fuel Oil Contaminated Soils by Activated Persulfate in the Presence of MnO 2. | |
US20170354837A1 (en) | Destruction of dense nonaqueous phase liquids (dnapls) using a time-release formulation | |
Kwon et al. | Remediation of NAPL-contaminated porous media using micro-nano ozone bubbles: Bench-scale experiments | |
TWI478877B (en) | Degradation of chlorinated hydrocarbon compounds and methods for their preparation | |
TWI511935B (en) | A novel emulsion as a remedy for soil, groundwater, sediments, and other environmental matrices | |
CN101596542A (en) | The method of remedying DDT polluted soil by ultrasonic wave | |
WO2012078568A2 (en) | Gum arabic encapsulation of reactive particles for enhanced delivery during subsurface restoration | |
JP2011025105A (en) | Method of decontaminating soil and underground water contaminated with organic chlorine compound | |
TWI806589B (en) | Micro-emulsion substrate, method of forming the same and application of using the same | |
JP2001300506A5 (en) | ||
JP2001300506A (en) | Method for cleaning contaminated ground components | |
Batagoda et al. | In situ remediation of passaic river sediments using ultrasound and ozone nanobubbles | |
Geiger | Nanoscale and microscale iron emulsions for treating DNAPL | |
Trzcinski et al. | Comparison of perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA) and perfluorobutane sulfonate (PFBS) removal in a combined adsorption and electrochemical oxidation process |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
MM4A | Annulment or lapse of patent due to non-payment of fees |