Title

以鈀/高密度聚乙烯觸媒及氫氣在超臨界二氧化碳中降解2﹐4-二溴聯苯

Translated Titles

Reduction of 2,4- Dibromobiphenyl by Palladium/High-density polyethylene with Hydrogen Gas in Supercritical Carbon Dioxide

Authors

李彥儒

Key Words

2﹐4-二溴聯苯 ; 降解 ; 超臨界二氧化碳 ; supercritical carbon dioxide ; degradation ; 2﹐4 - dibromobiphenyl.

PublicationName

中原大學化學研究所學位論文

Volume or Term/Year and Month of Publication

2014年

Academic Degree Category

碩士

Advisor

葉華光

Content Language

繁體中文

Chinese Abstract

多溴聯苯(PBBs,Polybrominated biphenyls)在自然界的存在對人體健康有害,當物質由工廠或桶裝、瓶裝等容器釋放出來時,就會排放到環境中,將多溴聯苯暴露到空氣裡,還有當你接觸到它或是經由呼吸、攝取含有多溴聯苯的食物或飲料,甚至是皮膚接觸等等都有可能讓多溴聯苯進入體內,對人體健康造成傷害。 本研究利用將高密度聚乙烯置於高壓槽中,溫度130℃,超臨界二氧化碳壓力為200atm,反應3小時後,讓壓力於幾秒內降至常壓下,再將微孔洞HDPE及palladium hexafluoroacetylacetonate置於高壓槽中, 使用90℃的溫度,於超臨界二氧化碳100atm下,再反應3小時,最後快速洩壓於常壓,之後將氫氣導入高壓槽中,並在溫度 90℃下維持約10分鐘,製作成我們本次研究所需要的觸媒。 透過Pd/HDPE(Palladium hexafluoroacetylacetonate High-density polyethylene)為觸媒降解多溴聯苯當中的2,4- dibromobiphenyl,使其在高溫下可以降解成毒性較低的bicyclohexane(雙環己烷)、biphenyl(聯苯)、cyclohexylbenzene(環己苯),並且透過加入內標法定量在各個溫度、壓力、流速下或是回收體積等等各種變因中的降解後殘留百分比。開發出一種可以有效降解多溴聯苯的方法,而且我們發現,研究中的反應時間相比其他研究優化許多,甚至對於相同降解時間的光降解研究而言,本研究(99.4%)降解率也比該研究(91.3%)高。在溫度上本研究只需要90゚C的溫度就可以對二溴聯苯進行降解,相較於雜多酸鋅鹽催化反應的320゚C高溫而言,本研究較為節能。 透過本研究可以使二溴聯苯降解的更完全,使用節能又對環境無害的超臨界二氧化碳萃取法透過這樣的方法,讓連生物都難分解的二溴聯苯有機汙染物能更有效的降解成對環境較無害的產物。

English Abstract

Under this study, we use the high-pressure tank into the HDPE the temperature is greater than 130 ℃ under pressure 200atm, the reaction for 3 hours, after which the pressure was decreased to atmospheric conditions in a matter of seconds, the microporous HDPE hole into the high pressure vessel and palladium hexafluoroacetylacetonate, with greater than 90 ℃ in temperature, pressure 100atm, and then reacted for 3 hours, and finally at atmospheric pressure rapidly, then the high pressure hydrogen gas is introduced into said groove, and at 90 ℃ maintaining about 10 minutes, the experiment produced a catalyst we need. Before making use of the catalyst Pd / HDPE will be placed in a supercritical system, the use of 90 degrees and the pressure 200atm the reaction for 8 hours and then extraction with a flow rate of 0.3 to 0.5 of the supercritical carbon dioxide charged 300ml six hours, then using gas chromatography Gas chromatography-mass spectrometry (GC-MS) coupled with previously by the standard Bicyclohexane, Cyclohexylbenzene, Biphenyl, 2,4-Dibiromobiphenyl and 4 - chlorobiphenyl make the calibration curve, to match the standard method quantitatively obtain optimum catalyst degradation rate of 99.4%.

Topic Category 基礎與應用科學 > 化學
理學院 > 化學研究所
Reference
  1. 2. Environ. Sci. Technol., 2010, 44 (16), pp 6068–6073 Publication Date:July 22,2010 Copyright © 2010 American Chemical Society。
    連結:
  2. 6. Hale,Robert C.,et al. "Polybrominated diphenyl ether flame retardants in the North American environment." Environment International 29.6 (2003):771-779。
    連結:
  3. 8. Kimbrough,Renate D. "Human health effects of polychlorinated biphenyls (PCBs) and polybrominated biphenyls (PBBs)." Annual review of pharmacology and toxicology 27.1 (1987):87-111.
    連結:
  4. 10. Jacobs, Lee W.,Sheng-Fu Chou,and James M. Tiedje. "Fate of polybrominated biphenyls (PBB's) in soils。 Persistence and plant uptake."Journal of agricultural and food chemistry 24.6 (1976): 1198-1201。
    連結:
  5. 12. Journal of Environmental and Public Health Volume 2012 (2012), Article ID 713696, 52 pages。
    連結:
  6. 13. Lynn B. Willett, Constance J. Brumm, Cynthia L. Williams J. Agric. Food Chem., 1978, 26 (1), pp 122–125。
    連結:
  7. 14. Environ Res. 1977 Feb;13(1):74-93. Review. No abstract available。
    連結:
  8. 15. Eyster, Janet T., Harold EB Humphrey, and Renate D. Kimbrough. "Partitioning of polybrominated biphenyls (PBBs) in serum, adipose tissue, breast milk, placenta, cord blood, biliary fluid, and feces." Archives of Environmental Health: An International Journal 38.1 (1983): 47-53.
    連結:
  9. 16. Weil,William B.,et al。"The effect of polybrominated biphenyl on infants and young children." The Journal of pediatrics 98.1 (1981):47-51。
    連結:
  10. 17. Kimbrough,Renate D. "Human health effects of polychlorinated biphenyls (PCBs) and polybrominated biphenyls (PBBs)." Annual review of pharmacology and toxicology 27.1 (1987):87-111。
    連結:
  11. 18. Lambert,George H.,et al. "The caffeine breath test and caffeine urinary metabolite ratios in the Michigan cohort exposed to polybrominated biphenyls:a preliminary study。" Environmental health perspectives 89 (1990): 175。
    連結:
  12. 20. Kimbrough, Renate D. "Human health effects of polychlorinated biphenyls (PCBs) and polybrominated biphenyls (PBBs)." Annual review of pharmacology and toxicology 27.1 (1987): 87-111。
    連結:
  13. 21. Bahn,Anita K.,et al。 "Hypothyroidism in workers exposed to polybrominated biphenyls。" The New England journal of medicine 302.1 (1980):31。
    連結:
  14. 23. Damstra T,Jurgelski W Jr, Posner HS,Vouk VB,Bernheim NJ,Guthrie J,Luster M,Falk HL. Toxicity of polybrominated biphenyls (PBBs) in Domestic and laboratory animals, Environ Health Perspect,1982 Apr;44:175-88。
    連結:
  15. 25. Jensen,Richard K.,et al。"Polybrominated biphenyls as promoters in experimental hepatocarcinogenesis in rats." Carcinogenesis 3.10 (1982):1183-1186。
    連結:
  16. 27. Johnson,Lynda K.,Christopher M. Killian, and Maurice Brookhart. "New Pd (II)-and Ni (II)-based catalysts for polymerization of ethylene and。 alpha.-olefins."Journal of the American Chemical Society 117.23 (1995): 6414-6415。
    連結:
  17. 28. Khare,Neeraj P.,et al。"Steady-state and dynamic modeling of commercial slurry high-density polyethylene (HDPE) processes." Industrial & engineering chemistry research 41.23 (2002): 5601-5618。
    連結:
  18. 30. Johnson,Lynda K.,Christopher M. Killian,and Maurice Brookhart. "New Pd (II)-and Ni (II)-based catalysts for polymerization of ethylene and. alpha.-olefins."Journal of the American Chemical Society 117.23 (1995):6414-6415。
    連結:
  19. 31. Ueki,M. M.,and M. Zanin. "Influence of additives on the dielectric strength of high-density polyethylene." Dielectrics and Electrical Insulation,IEEE Transactions on 6.6 (1999):876-881。
    連結:
  20. 32. Young,R. J., et al. "Deformation mechanisms in oriented high-density polyethylene。" Journal of Materials Science 8.1 (1973):23-36。
    連結:
  21. 33. Kurelec,L., et al. "Strain hardening modulus as a measure of environmental stress crack resistance of high density polyethylene." Polymer 46.17 (2005): 6369-6379。
    連結:
  22. 34. Osman,Maged A.,and Ayman Atallah。"High‐Density Polyethylene Micro‐and Nanocomposites:Effect of Particle Shape,Size and Surface Treatment on Polymer Crystallinity and Gas Permeability." Macromolecular rapid communications 25.17 (2004):1540-1544。
    連結:
  23. 35. Tincer,T.,and M. Coşkun。"Melt blending of ultra high molecular weight and high density polyethylene: the effect of mixing rate on thermal,mechanical, and morphological properties。" Polymer Engineering & Science 33.19 (1993):1243-1250。
    連結:
  24. 36. Bartczak,Z.,et al. "Toughness mechanism in semi-crystalline polymer blends:II. High-density polyethylene toughened with calcium carbonate filler particles."Polymer 40.9 (1999):2347-2365。
    連結:
  25. 37. Nakayasu,H.,H. Markovitz,and D. J. Plazek。"The frequency and temperature dependence of the dynamic mechanical properties of a high density polyethylene." Journal of Rheology 5 (1961):261。
    連結:
  26. 38. Debras,Guy,and Hugo Vandaele。"Process for producing polyethylene having a broad molecular weight distribution。" U.S. Patent No. 5,639,834. 17 Jun. 1997。
    連結:
  27. 39. Shah,Basit H.,and Ron Darby。"Prediction of polyethylene melt rheological properties from molecular weight distribution data obtained by gel permeation chromatography。" Polymer Engineering & Science 16.8 (1976):579-584。
    連結:
  28. 40. Hsuan,Y. G.,and R. M. Koerner。"Antioxidant depletion lifetime in high density polyethylene geomembranes." Journal of Geotechnical and Geoenvironmental Engineering 124.6 (1998): 532-541。
    連結:
  29. 41. Suzuoki,Yasuo,et al. "Investigation of space charge in high-density polyethylene using thermal-pulse response." JAP. J. APPL. PHYS. 24.5 (1985):604-609。
    連結:
  30. 43. Plotkin,S. Ya。"Wollaston and the early history of powder metallurgy。" Powder Metallurgy and Metal Ceramics 8.12 (1969):1035-1037。
    連結:
  31. 44. Mitchell,Roger H.,and Reid R. Keays。"Abundance and distribution of gold,palladium and iridium in some spinel and garnet lherzolites:implications for the nature and origin of precious metal-rich intergranular components in the upper mantle。" Geochimica et Cosmochimica Acta 45.12 (1981): 2425-2442。
    連結:
  32. 45. Lynch,J. F.,and Ted B. Flanagan。"Dynamic equilibrium between chemisorbed and absorbed hydrogen in the palladium/hydrogen system." The Journal of Physical Chemistry 77.22 (1973):2628-2634。
    連結:
  33. 46. Worsham Jr,J. E., M. K. Wilkinson,and C. G. Shull。"Neutron-Diffraction Observations on the Palladium-hydrogen and Palladium-deuterium systems."Journal of Physics and Chemistry of Solids 3.3 (1957):303-310。
    連結:
  34. 47. Jewell,Linda L.,and Burtron H. Davis。"Review of absorption and adsorption in the hydrogen–palladium system." Applied Catalysis A:General 310 (2006):1-15。
    連結:
  35. 48. Clewley,J. D.,et al。"Thermodynamic properties of hydrogen and deuterium dissolved in palladium at low concentrations over a wide temperature range." J. Chem. Soc.,Faraday Trans。1 69 (1973):449-458。
    連結:
  36. 49. Ward,Timothy L.,and Tien Dao。"Model of hydrogen permeation behavior in palladium membranes." Journal of Membrane Science 153.2 (1999):211-231。
    連結:
  37. 50. Maitlis,Peter。 Metal Complexes:The Organic Chemistry of Palladium。Academic Press,1971。
    連結:
  38. 53. Lee,Ming‐Way,and R. Glosser。"Pressure concentration isotherms of thin films of the palladium‐hydrogen system as modified by film thickness, hydrogen cycling, and stress." Journal of applied physics 57.12 (1985):5236-5239。
    連結:
  39. 54. Shao,M. H.,et al. "Palladium monolayer and palladium alloy electrocatalysts for oxygen reduction." Langmuir 22.25 (2006):10409-10415。
    連結:
  40. 55. Shao,M. H.,et al. "Palladium monolayer and palladium alloy electrocatalysts for oxygen reduction." Langmuir 22.25 (2006):10409-10415。
    連結:
  41. 56. Albers,Peter,Jörg Pietsch,and Stewart F. Parker. "Poisoning and deactivation of palladium catalysts." Journal of Molecular Catalysis A:Chemical 173.1 (2001):275-286。
    連結:
  42. 57. Past,present,and possible future applications of supercritical fluid extraction technology。Journal of chemical education,1996,73.12:1163。
    連結:
  43. 61. Villard P.J.Phys,1896,5:455。
    連結:
  44. 67. Debenedetti,Pablo G.,and R. C. Reid。"Diffusion and mass transfer in supercritical fluids。" AIChE journal 32.12 (1986):2034-2046。
    連結:
  45. 68. Benjamin,T. Brooke. "Bifurcation phenomena in steady flows of a viscous fluid. I. Theory." Proceedings of the Royal Society of London. A. Mathematical and Physical Sciences 359.1696 (1978):1-26。
    連結:
  46. 69. 吳俊毅,2003以超臨界二氧化碳萃取海豹油之研究,國立成功大學化學研究所碩士論文。
    連結:
  47. 70. R.C.Reid,J.M.Prausnitz and B.E.Poling,The Properties of Gases and Liquids,4th Ed.,McGraw-Hill,New York,(1987)。
    連結:
  48. 71. 桂椿雄,超臨界流體之簡介,科儀新知,1994,11(4)44-48。
    連結:
  49. 72. King,Jerry W. "Fundamentals and applications of supercritical fluid extraction in chromatographic science." Journal of chromatographic science 27.7 (1989):355-364。
    連結:
  50. 74. J Hazard Mater. 2009 Apr 15;163(1):231-8. doi: 10.1016/j.jhazmat.2008.06.082. Epub 2008 Jul 1。
    連結:
  51. 76. Tian, Li-Ching, and Sao-Ming Wu. "Determination of chemical oxygen demand in aqueous environmental samples by segmented flow-injection analysis."Analytica chimica acta 261.1 (1992): 301-305。
    連結:
  52. 82. Liu, H.,Liu,G.,Fan,J.,Zhou,Q.,Zhou,H.,Zhang,N.,et al. (2011)。Photoelectrocatalytic degradation of 4,4′-dibromobiphenyl in aqueous solution on TiO2 and doped TiO2 nanotube arrays。Chemospher,82(1),43-47。
    連結:
  53. 83. Gong,X. G.,and John W. Wilkins。 "Hyper molecular dynamics with a local bias potential." Physical Review B 59.1 (1999): 54-57。
    連結:
  54. 1. J. Agric. Food Chem.,1978,26 (1), pp 122–125 Publication Date: January 1978。
  55. 3. Environ. Sci. Technol.,2001,35 (23),pp 4585–4591 Publication Date:October 30,2001 Copyright © 2001 American Chemical Society。
  56. 4. Environ. Sci. Technol.,2001,35 (19),pp 3830–3833 Publication Date : August 25,2001 Copyright © 2001 American Chemical Society。
  57. 5. Environ. Sci. Technol.,2009, 43 (11),pp 4200–4206 Publication Date: April 29,2009 Copyright © 2009 American Chemical Society。
  58. 7. Lee W. Jacobs, Sheng-Fu Chou,James M. Tiedje J. Agric. Food Chem., 1976, 24 (6), pp 1198–1201。
  59. 9. Sierra Rayne, Michael G. Ikonomou and Peter S. Ross, Graeme M. Ellis, Lance G. Barrett-Lennard Environ. Sci. Technol., 2004, 38 (16), pp 4293–4299。
  60. 11. Jiang, Jheng-jie. The distribution of Persistent Organic Compounds in the sediments of the Coastal Areas along the Southwestern Taiwan。Diss. Thesis. National Sun Yat-sen University, Taiwan, 2006。
  61. 19. Dent,J. G.,K. J. Netter,and J. E. Gibson。"Effects of chronic administration of polybrominated biphenyls on parameters associated with hepatic drug metabolism。" Research communications in chemical pathology and pharmacology 13.1 (1976): 75-82。
  62. 22. Environ. Sci. Technol., 2013,47 (12),pp 6071–6081 Publication Date:May 1,2013 Copyright © 2013 American Chemical Society。
  63. 24. Stoewsand,G. S.,J. B. Babish,and H. C. Wimberly。 "Inhibition of hepatic toxicities from polybrominated biphenyls and aflatoxin B in rats fed cauliflower."Journal of environmental pathology and toxicology 2.2 (1978): 399。
  64. 26. The Research Service. U.S.V.A. Hospital; the Department oj Anatomy,and the Unit for Laboratory Animal Medicine,University of Michigan Medical School,Ann Arbor,Michigan 48104 Received March,5. 1975,ENVIRONMENTAL RESEARCH 10, 390-396 (1975) 。
  65. 29. Ewen,John A.,and Howard C. Welborn Jr. "Process and catalyst for producing reactor blend polyolefins。" U.S. Patent No. 4,937,299. 26 Jun. 1990。
  66. 42. Holden,Norman E。"History of the Origin of the Chemical Elements and their Discoverers." National Nuclear Data Center (NNDC)。http://www. nndc. bnl. gov/content/elements. html (2001)。
  67. 51. Gryaznov,V. M."Hydrogen permeable palladium membrane catalysts."Platinum Met. Rev 30.2 (1986): 68。
  68. 52. Knapton,A. G. "Palladium alloys for hydrogen diffusion membranes." Platinum Met. Rev 21.2 (1977):44。
  69. 58. 胡英著,近代化工熱力學,上海;上海科技文獻出版社,1994.133。
  70. 59. Hannay J B.Hogarth J.Proc.Roy.Soc,1879.29:324。
  71. 60. Hannay J B.Proc.Roy.Sco.1880,30:484,Hannay J B.Hogarth J.Proc.Roy.Soc,1879.29:324。
  72. 62. Prins A.Acad.Sci,Amsterdam,1915,17:1095。
  73. 63. Pilat S,Godlewicz M.US 2 188 012。
  74. 64. Katz D L,Kurate F.Ind.Eng.Chem,1940,32:817。
  75. 65. K.Stephan and K.Lucas,Viscosity of Dense Fluid,Press,New York,(1979)。
  76. 66. E.Klesper,Angew.Chem.Int.Engl.,17 (16978) 738。
  77. 73. 魏,燕,李樹芬,和田玉松江。“超聲波輔助提取工藝。” 化學工業與工程進度21.9(2002):649-651。
  78. 75. 梁新義, et al. "超聲促進浸漬法製備催化劑 LaCoO3/γ-Al2O3 Supported Catalyst LaCoO3/γ-Al2O3 Prepared by Impregnating under Ultrasound." 物理化學學報19.7 (2003): 666-669。
  79. 77. 王孝武, et al. "黃磷廢水處理工藝比較." 環境工程學報 4.10 (2003): 57-60。
  80. 78. Chen,Jin-yang;Li,Zhi;Ruan,Ru-yi;Liu,Gui-yang ,From Shanghai Daxue Xuebao,Ziran Kexueban (2010),16(5),482-487。
  81. 79. Zhu,Lin;Ji,Caihong;Li,Xiaoli;Han, Pingfang,From Nanjing Gongye Daxue Xuebao,Ziran Kexueban (2009),31(3),92-96。
  82. 80. Noggle 著 謝從卿 譯 安和出版社,黃定加 著 高立出版社 。
  83. 81. Wang, Lei;Zhu,Yongjun;Lu,Xiaoping From Nanjing Gongye Daxue Xuebao,Ziran Kexueban (2007),29(2),102-105。