电视机外壳塑料再生脱卤研究
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摘要
随着我国社会经济的发展,废旧电子塑料量日益增加,如何安全处置废旧电子塑料成为人们日益关注的重大问题。
含溴阻燃剂(PBDEs)具有优异的防火性能,常被添加到电子塑料中。PBDEs具有神经毒性,特别是含溴高聚物燃烧及热裂时容易产生有毒、致癌、致畸的多溴代苯并二噁英(PBDD)和多溴代苯并呋喃(PBDF)。同时由于这两类物质具有较强的脂溶性而且性质稳定,由PBDEs蓄积作用而造成的环境、食品污染问题已引起欧盟、美国等发达国家高度关注。欧盟公布的《关于在电子电器设备中禁止使用某些有害物质指令》(RoHS指令)将PBDEs列为禁用阻燃剂。本文针对其中最关键的塑料热解脱卤及强化脱卤再生的理论及技术进行了相关研究。
本文采用傅里叶变换红外光谱法、元素分析法、热重分析法、气相色谱质谱联用分析法、高效液相色谱法等多种分析方法对废旧电视机塑料外壳的组分进行了分析。结果表明:电视机外壳塑料的主要成分是高抗冲聚苯乙烯(HIPS),含溴阻燃剂多以十溴联苯醚形式存在,并含有少量低溴联苯醚,并且含量超过欧盟RoHS标准的规定含量,而金属元素的含量均符合欧盟RoHS标准的规定;本文进而研究了电视机外壳塑料热解反应动力学,确定了其热解脱溴的最佳工艺条件,在此基础上提出了添加剂强化脱溴方案,并结合溶剂法达到提高阻燃剂的脱除效率而保护塑料力学性能的目的。
With the economic development of China, the number of waste electrical and electronic plastics is growing, and how to treat these plastics has become one of most serious issues.
As brominated flame retardants, Polybrominated diphenyl ethers (PBDEs) is a kind of excellent flame retardants, which was often added to the electronic plastics. However, PBDEs is neurotoxic. Especially, during combustion and thermal cracking, brominated polymer can generate PBDD and PBDF, strong fat-soluble and nature-stable substances, which are toxic, carcinogenic and teratogenic. Accumulating PBDEs causes environmental and food pollution, which has attracted attentions of the European Union, the United States and other developed countries. "The Restriction of the use of certain hazardous substances in electrical and electronic equipment" (RoHS) from the EU will prohibit PBDEs as flame retardants used in electrical and electronic plastics. In this paper, the research foucuses on the theory and technology of debromination, intensification of debromination and regeneration of plastics.
ICP-AES, FTIR, elemental analysis, TG-DSC, GC-MS, HPLC and other modern analytical methods were used for analysis of waste TV shell plastics components in this paper.The results showed that: the main component of TV shell plastic is high impact polystyrene (HIPS), brominated flame retardants includes mainly Deca-BDE, and a small amount of Lowbromine biphenyl ethers. Meanwhile, the content of Deca-BDE is more than standard content of the EU RoHS, the content of metal elements is in line with standard requirements of the EU RoHS. It also studied on thermal decomposition reaction kinetics of TVshell plastics to determine its optimum thermal technology conditions of debromination. On this basis, it come up with additive-debromination programs, combining with solvent- debromination program in order to achieve the purpose of increasing removal rate of Deca-BDE and protecting mechanical properties of plastics.
含溴阻燃剂(PBDEs)具有优异的防火性能,常被添加到电子塑料中。PBDEs具有神经毒性,特别是含溴高聚物燃烧及热裂时容易产生有毒、致癌、致畸的多溴代苯并二噁英(PBDD)和多溴代苯并呋喃(PBDF)。同时由于这两类物质具有较强的脂溶性而且性质稳定,由PBDEs蓄积作用而造成的环境、食品污染问题已引起欧盟、美国等发达国家高度关注。欧盟公布的《关于在电子电器设备中禁止使用某些有害物质指令》(RoHS指令)将PBDEs列为禁用阻燃剂。本文针对其中最关键的塑料热解脱卤及强化脱卤再生的理论及技术进行了相关研究。
本文采用傅里叶变换红外光谱法、元素分析法、热重分析法、气相色谱质谱联用分析法、高效液相色谱法等多种分析方法对废旧电视机塑料外壳的组分进行了分析。结果表明:电视机外壳塑料的主要成分是高抗冲聚苯乙烯(HIPS),含溴阻燃剂多以十溴联苯醚形式存在,并含有少量低溴联苯醚,并且含量超过欧盟RoHS标准的规定含量,而金属元素的含量均符合欧盟RoHS标准的规定;本文进而研究了电视机外壳塑料热解反应动力学,确定了其热解脱溴的最佳工艺条件,在此基础上提出了添加剂强化脱溴方案,并结合溶剂法达到提高阻燃剂的脱除效率而保护塑料力学性能的目的。
With the economic development of China, the number of waste electrical and electronic plastics is growing, and how to treat these plastics has become one of most serious issues.
As brominated flame retardants, Polybrominated diphenyl ethers (PBDEs) is a kind of excellent flame retardants, which was often added to the electronic plastics. However, PBDEs is neurotoxic. Especially, during combustion and thermal cracking, brominated polymer can generate PBDD and PBDF, strong fat-soluble and nature-stable substances, which are toxic, carcinogenic and teratogenic. Accumulating PBDEs causes environmental and food pollution, which has attracted attentions of the European Union, the United States and other developed countries. "The Restriction of the use of certain hazardous substances in electrical and electronic equipment" (RoHS) from the EU will prohibit PBDEs as flame retardants used in electrical and electronic plastics. In this paper, the research foucuses on the theory and technology of debromination, intensification of debromination and regeneration of plastics.
ICP-AES, FTIR, elemental analysis, TG-DSC, GC-MS, HPLC and other modern analytical methods were used for analysis of waste TV shell plastics components in this paper.The results showed that: the main component of TV shell plastic is high impact polystyrene (HIPS), brominated flame retardants includes mainly Deca-BDE, and a small amount of Lowbromine biphenyl ethers. Meanwhile, the content of Deca-BDE is more than standard content of the EU RoHS, the content of metal elements is in line with standard requirements of the EU RoHS. It also studied on thermal decomposition reaction kinetics of TVshell plastics to determine its optimum thermal technology conditions of debromination. On this basis, it come up with additive-debromination programs, combining with solvent- debromination program in order to achieve the purpose of increasing removal rate of Deca-BDE and protecting mechanical properties of plastics.
引文
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[4] Silke Rupp, Jorg W. Metzger. Brominated–chlorinated diphenyl ethers formed by thermolysis of polybrominated diphenylethers at low temperatures [J]. Chemosphere, 2005, 60: 1644-1651.
[5] M P Luda, A. I. Balabanovich, A. Hornung, G. Camino. Thermal degradation of a brominated bisphenol A derivative [J]. Polym Adv Technol, 2003, 14: 741-748.
[6] F Fonnum, E Mariussen, T Reistad. Molecular mechanisms involved in the toxic effects of polychlorinated biphenyls (PCBs) and brominated flame retardants (BFRs) [J]. J Toxicol Environ Health, Part A, 2006, 69: 21-35.
[7] L Tange, D Drohmann. Waste electrical and electronic equipment plastics with brominated flame retardants from legislation to separate treatment thermal process [J]. Polym Degrad Stab, 2005, 88: 35-40.
[8]姜宾延,吴彩斌.电子垃圾的危害及其机械处理技术现状[J].再生资源研究, 2005, (3): 23- 26.
[9]约翰·沙伊斯著.聚合物回收[M].北京:化学工业出版社, 2004.
[10] Dodbiba G. Combination of sink- float separation and flotation technique for purification of shredded PET- bottle from PE or PP flakes [J]. Metallic Ore Dressing Abroad, 2003, (3): 31- 37
[11] Mihai Lungu. Electrical separation of plastic materials using the triboelectric effect[J]. Minerals Engineering, 2004, 17(1): 69-75.
[12] Mihai L. Progress of the Reusing and Recycling Technologies of the Waste Plastics [J]. Mineral Eng, 2004, 17: 69-75.
[13] Schlett Z, Claici F, et al. A new static separator for metallic particles from metal plastic mixtures, using eddy currents [J]. Mineral Eng, 2002, 15: 111-113.
[14]刘芳,吴小华. PC回收料/ABS塑料合金的研究[J].塑料工业, 2001, 29(4): 9-11.
[15] Baymod B. Dawson, Susan D. Landry. Reusing ability of Flame Retardant HIPS, PC/ABS, an PPO/HIPS used in Electrical and Electronic Equipment [J]. Research and Development, 2005, 9: 61-64.
[16]木村亮.日本松下开发出塑料回收利用新技术[J].再生资源研究, 2003, (1): 43.
[20] Busselle L D, Moore T A, Shoemaker J M, et al. Proceeding of IEEE International Symposium on Electronics and the Environment. USA: Danvers Ma, 1999, 192.
[21]陈烈强,彭绍洪,甘舸,蔡明招.废旧电子电气设备的资源化与无害化技术[J].环境科学与技术, 2005, (03): 90-92.
[22] Kang H K, Schoenung J M. Proceeding of IEEE International Symposium on Electronics and the Environment. USA: Phonenix. Ar, 2004, 226.
[23] Fisher M M, Mark F E, Kingsbury T, et al. Proceeding of IEEE International Symposium on Electronics and the Environment. USA: New Orlean La, 2005, 83.
[24] Lein Tangea, Dieter Drohmann. Waste electrical and electronicequipment plastics with brominated flame retardants from legislation to separate treatment thermal processes [J]. Polymer Degradation and Stability, 2005, 88(1): 35- 40.
[25] Johannes Karl Fink. Pyrolysis and combustion of polymer wastes in combination with metallurgical processes and the cement industry [J]. Journal of Analytical and Applied Pyrolysis, 1999, 51(1- 2): 239- 252.
[26] Hai YongKang, Julie M Schoenung. Electronic waste recycling: A review of U.S.infrastructure and technology options [J]. Resources, Conservation and Recycling, 2005, 45(4): 368- 400.
[27]叶能魁.中欧废旧电子电器回收处理技术交流会资料汇编.北京:中国家用电器协会废旧电子电器再生利用分会, 2005, 45.
[28] Okajima I. Proceeding of IEEE International Symposium on Electronics and the Environment. USA: Denver Co, 2001, 986.
[29] Hongtao Wang, Maya Hirahara, Motonobu Goto, et al. Extraction of flame retardants from electronic printed circuit board by supercritical carbon dioxide [J]. J. of Supercritical Fluids, 2004, 29(3): 251- 256.
[30]龙中柱,高勇.超临界反应技术在废旧塑料回收再生利用方面的应用[J].化工进展, 2001, (5): 15- 20.
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