| 研究生: |
阮台彥 Nguyen Thanh |
|---|---|
| 論文名稱: |
以奈米零價鐵和雙金屬鐵觸媒對含五氯酚土壤之整治效率探討 Remediation of Pentachlorophenol-contaminated Soil with Nano-zero Valent Iron and Bimetallic Iron |
| 指導教授: |
張木彬
Moo Been Chang |
| 口試委員: | |
| 學位類別: |
碩士 Master |
| 系所名稱: |
工學院 - 環境工程研究所 Graduate Institute of Environmental Engineering |
| 畢業學年度: | 100 |
| 語文別: | 英文 |
| 論文頁數: | 55 |
| 中文關鍵詞: | 脫氯 、含五氯酚土壤 、雙金屬鐵觸媒 、奈米零價鐵 |
| 外文關鍵詞: | PCP contaminated soil, bimetallic iron, nano zerovalent iron, dechlorination |
| 相關次數: | 點閱:20 下載:0 |
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零價鐵和雙金屬鐵觸媒已被應用於降解水相中含氯化合物。本研究探討應用實驗室合成之奈米零價鐵(nZVI)及工業用的雙金屬鐵觸媒(BioCAT)以降解含五氯苯酚(PCP)之沙質土壤之還原動力和機制之研究。nZVI和BioCAT降解五氯苯酚(PCP)符合一階動力,nZVI對土壤泥漿中之五氯酚的去除率達98%,但主要歸因於nZVI的表面吸附,脫氯效率僅有4%。相較之下,經21天BioCAT處理後之脫氯效率約70%、PCP去除率則為90%。推測原因乃鐵和雙金屬鐵之間反應速率的差異,可能涉及氯酚與活性氫在奈米鐵上之競爭吸附以及鐵觸媒表面鏽蝕的吸附影響。中間產物的形成以及氯的釋放證實PCP之脫氯。此外,在反應過程中pH值上升和ORP值急劇下降也證明PCP的還原脫氯機制。最終產物包含三種TeCP同分異構物、四種TrCP同分異構物、四種DCP同分異構物。本研究也提出nZVI和BioCAT之PCP脫氯途徑。還原脫氯反應後,這些中間產物之毒性低於PCP。這些低氯數氯酚比PCP更容易在環境中生物降解或光降解。研究結果顯示BioCAT可應用於含PCP土壤之處理。
關鍵字:脫氯、奈米零價鐵、雙金屬鐵觸媒、含五氯酚土壤
Zerovalent iron and bimetallic iron have been studied mostly for the degradation of chlorinated compounds in aqueous phase. In this study, laboratory synthesized particles of nano zerovalent iron and commercial bimetallic iron were applied to investigate the reduction kinetics and degradation mechanisms of pentachlorophenol (PCP) spiked sandy soil. Degradation of PCP by nZVI and BioCAT follows the first-order kinetics. The 98% PCP removal efficiency from soil slurries in contact with nano zerovalent iron (nZVI) was mostly attributable to adsorption to nZVI surfaces and only 4% was due to dechlorination. By comparison, approximately 70% dechlorination rate were achieved along with 90% PCP removal efficiency with BioCAT dosage of 600 mg after 21 days of treatment. Possible explainations for the differences in the reaction rates between iron and bimetallic iron may involve competitive sorption of chlorinated phenols and reactive hydrogen on iron and catalytic surfaces as well as the effects of sorption on corrosion. PCP dechlorination was confirmed by the appearance of the intermediate products as well as chloride release. Additionally, the increase of pH values and rapid decrease of ORP values during the reaction also proved reductive dechlorination of PCP. The lower chlorinated phenols and the endproduct including three TeCP isomers; four TrCP isomers; four DCP isomers; two MCP isomers and phenol by BioCAT were found. The intermediates by nZVI contained one TeCP isomer, one TCP isomer. The stepwise dechlorination pathways of PCP by nZVI and BioCAT were proposed in this study. After reductive dechlorination reactions, these intermediates are less toxic than PCP. Furthermore, these lower chlorinated phenols can be biodegraded or photodegraded more easily than PCP in the environment. These findings indicate that using BioCAT with mild temperature and no pH adjustment could have implications for field treatment of PCP-contaminated soil.
REFERENCES
Arning MD, Minteer SD, 2007. Handbook of Electrochemistry: Electrode Potentials. Elsevier, 813-827.
Balasubramaniam R, Ramesh KAV, Dillmann P, 2003. Characterization of rust on ancient Indian iron. Current Science 85, 1546-1555.
Banerji SK, Wei SM, 1993. Pentachlorophenol interactions with soil. Water, Air, and Soil Pollution 69, 149-163.
Biernat RJ, Robins RG, 1972. High temperature potential/pH diagrams for the iron-water and iron-water-sulfur systems. Electrochimica Acta 17, 1261-1283.
Chang MC, Kang HY, 2009. Remediation of pyrene-contaminated soil by synthesized nanoscale zero-valent iron particles. Journal of Environmental Science and Health 44, Part A, 576-582.
Choe S, Chang YY, Hwang KY, Khim J, 2000 . Kinetics of reductive denitrification by nanoscale zero-valent iron. Chemosphere 41, 1307.
Choi JH, Choi SJ, Kim YH, 2008. Hydrodechlorination of 2,4,6-tri¬chlorophenol for a permeable reactive barrier using ze¬ro-valent iron and catalyzed iron. Korean Journal Chemical Engneering. 25, 493-500.
Dai Y, Li F, Ge F, Zhu F, Wu L, Yang X, 2006. Mechanism of the enhanced degradation of pentachlorophenol by ultra¬sound in the presence of elemental iron. Journal of Hazardous Materials 137, 1424-1429.
dela Cruz ALN, Gehling W, Lomnicki S, Cok R, Dellinger B, 2011. Detection of environmentally persistent free radicals at a superfund wood treating site. Environmental Science and Technology 45, 6356-636.
Elliot DW, Lien HL, Zhang WX, 2009. Degradation of lindan by zero-valent iron nanoparticles. Journal of Environmental Engineering 135, 317-324.
Glavee GN, Klabunde KJ, Sorensen C, Hadjipanayis GC, 1995. Chemistry of borohydride reduction of iron(II) and iron(III) ions in aqueous and nonaqueous media. Formation of nanoscale Fe, FeB and Fe2B powders. Inorganic Chemistry 34, 28-35.
Gunawardana B, Singhal N, Swedlund P, 2011. Degradation of chlorinated phenols by zero valent iron and bimetals of iron: a review. Environmental Engineering Research 16, 187-203.
Gunawardana B, Singhal N, Swedlund P, 2012. Dechlorination of pentachlorophenol by zero valent iron and bimetals: effect of surface characteristics and bimetal preparation procedure. Proceedings of the Annual International Conference on Soils, Sediments, Water and Energy 17, 68-81.
He Y, Xu J, Wang H, Zhang Q, Muhammad A, 2006. Potential contributions of clay minerals and organic matter to pentachlorophenol retention in soil. Chemosphere 65, 497-505.
Hwang YH, Kim DG, Shin HS, 2011. Effects of synthesis conditions on the characteristics and reactivity of nano scale zero valent iron. Applied Catalysis B: Environmental 105, 144-150.
Johnson TL, Scherer MM, Trantnyek PG, 1996. Kinetics of halogenated organic compound degradation by iron metal. Environmental Science and Technology 30, 2634-2640.
Jou CJ, 2008. Degradation of pentachlorophenol with zero-va¬lence iron coupled with microwave energy. Journal of Hazardous Materials 152, 699-702.
Kastanek F, Maleterova Y, Kastanek P, Rott J, Jiricny V, Jiratova K, 2007.Complex treatment of wastewater and groundwater contaminated by halogenated organic compounds. Desalination 211, 261-271.
Kennes C, Wu WM, Bhatnagar L, Zeikus JG, 1996. Anaerobic dechlorination and mineralization of pentachlorophenol and 2,4,6-trichlorophenol by methanogenic pentachlorophenol-degrading granules. Applied Microbiology and Biotechnology 44, 801-806.
Keum YS, Li QX, 2005. Reductive debromination of polybrominated diphenyl ethers by zerovalent iron. Environmental Science and Technology 39, 2280–2286.
Kim YH, Carraway ER, 2000. Dechlorination of pentachlorophe¬nol by zero valent iron and modified zero valent irons. Environmental Science and Technology 34, 2014-2017.
Kim YH, Carraway ER, 2003. Dechlorination of chlorinated phenols by zero valent zinc. Environmental Technology 24, 1455-1463.
Li L, Fan M, Brown RC, Leeuwen JV, Wang J, Wang W, Song Y, Zhang P, 2006. Synthesis, properties, and environmental applications of nanoscale iron-based materials: a review. Environmental Science and Technology 36, 405-431.
Liao CJ, Chung TL, Chen WL, Kuo SL, 2007. Treatment of PCP-contaminated soil using nano-scale zero-valent iron with hydrogen peroxide. Journal of Molecular Catalysis A: Chemical 265, 189-194.
Lien HL, Zhang WX, 2007. Nanoscale Pd/Fe bimetallic particles: Catalytic effects of palladium on hydrodechlorination. Applied Catalyst B: Environmental 77, 110-116.
Liu Y, Yang F, Yue PL, Chen G, 2001. Catalytic dechlorination of chlorophenols in water by palladium/iron. Water Research 35, 1887-1890.
Liu ZL, Wang HB, Lu QH, Du GH, Peng L, Du YQ, Zhang SM, Yao KL, 2004. Synthesis and characterization of ultrafine well-dispersed magnetic nanoparticles. Journal of Magnetism and Magnetic Materials, 283-258.
Lowry GV, Johnson KM, 2004. Congener-specific dechlorination of dissolved PCBs by microscale and nanoscale zerovalent iron in a water/methanol solution, Environmental Science and Technology 38, 5208–5216.
Morales J, Hutcheson R, Cheng IF, 2002. Dechlorination of chlorinated phenols by catalyzed and uncatalyzed Fe0 and Mg0 particles. Journal of Hazardous Materials B90, 97–108.
Mueller NC, Nowack B, 2010. Nano zero valent iron – The solution for water and soil remediation? Report of the Observatory NANO. Available at www.observatorynano.eu.
Ngo TT, Chang MB, 2012. Investigation of the degradation of pentachlorophenol in sandy soil via low-temperature pyrolysis. Journal of Hazardous Materials 229-230, 411-418.
Noubactep C, 2008. A critical review on the process of con¬taminant removal in Fe0-H2O systems. Environmental Technology 29, 909-920.
Nurmi JT, Tratnyek PG, Sarathy V, Baer DR, Amonette JE, 2005. Characterization and properties of metallic iron nanoparticles: Spectroscopy, electrochemistry, and kinetics. Environmental Science and Technology 39, 1221-1230.
Ponder SM, Darab JG, Bucher J, Caulder D, Craig I, Davis L, Edelstein N, Lukens W, Nitsche H, Rao LF, Shuh DK, Mallouk TE, 2001. Surface chemistry and electrochemistry of supported zero-valent iron nanoparticles in the remediation of aqueous metal contaminants. Chemistry of Materials 13, 479-486.
Reddy KR, Karri MR, 2008. Removal and degradation of pentachlorophenol in Clayey Soil using nanoscale iron particles. GeoCongress: Geotechnics of Waste Management and Remediation, 463-470.
Satapanajaru T, Anurakpongsatorn P, Pengthamkeerati P, Boparai H, 2008. Remediation of atrazine-contaminated soil and water by nano zerovalent iron. Water Air Soil Pollution 192, 349-359.
Schrick B, Hydutsky BW, Blough JL, Mallouk TE, 2004. Delivery vehicles for zerovalent metal nanoparticles in soil and groundwater. Chemistry of Materials 16, 2187-2193.
Schwarzenbach RP, Gschwend PM, Imboden DM, 2003. Environmental Organic Chemistry, second edition. A John Wiley & Son, Inc., Publication.
Shih YH, Hsu CY, Su YF, 2011. Reduction of hexachlorobenzene by nanoscale zero-valent iron, pH effects, and degradation mechanism. Separation and Purification Technology 76, 268-274.
Shih YH, Tai YT, 2010. Reaction of decabrominated diphenyl ether by zerovalent iron nanoplarticles. Chemosphere 78, 1200-1206.
Shiu WY, Ma KC, Varhanickova D, Mackay D, 1994. Chlorophenols and alkylphenols: a review and correlation of environmen¬tally relevant properties and fate in an evaluative environ¬ment. Chemosphere 29, 1155-1224.
Sun YP, Li XQ, Cao J, Zhang WX, Wang HP, 2006. Characterization of zero-valent iron nanoparticles. Advances in Colloid and Interface Science 120, 47-56.
U.S. Environmental Protection Agency. Priority pollutants [Internet]. Washington, DC: U.S. Environmental Protection Agency; c2011 [cited 2011 Jun 6]. Available from: http://wa-ter.epa.gov/scitech/methods/cwa/pollutants.cfm.
Wei J, Xu X, Liu Y, Wang D, 2006. Catalytic hydrodechlorina¬tion of 2,4-dichlorophenol over nanoscale Pd/Fe: reaction pathway and some experimental parameters. Water Research 40, 348-354.
Windt WD, Aelterman P, Verstraete W, 2005. Bioreductive deposition of palladium (0) nanoparticles on Shewanella oneidensis with catalytic activity towards reductive dechlorination of polychlorinated biphenyls. Environmental Microbiology 7, 314-325.
Zhang W, Quan X, Wang J, Zhang Z, Chen S, 2006. Rapid and complete dechlorination of PCP in aqueous solution using Ni–Fe nanoparticles under assistance of ultrasound. Chemosphere 65, 58–64.
Zhang WX, 2003. Nanoscale iron particles for environmental remediation: an overview. Journal of Nanoparticle Research 5, 323-332.
Zhang WX, Wang CB, 1997. Synthesizing nanoscale iron particles for rapid and complete dechlorination of TCE and PCBs. Environmental Science and Technology 31, 2154-2156.
Zhou T, Li Y, Lim TT, 2010. Catalytic hydrodechlorination of chlo¬rophenols by Pd/Fe nanoparticles: comparisons with other bimetallic systems, kinetics and mechanism. Separation and Purification Technology 76, 206-214.