臺灣博碩士論文加值系統

中文摘要

本研究以熱裂解法處理廢監視器塑膠外殼，探討其裂解後固體產品（焦碳）再利用之可行性，例如，作為橡膠輪胎添加劑，亦探討殘餘物經蒸汽活化後之特性，以作為其他再利用方式之參考數據。研究主要可分為三部分：（1）廢電腦監視器塑膠外殼熱裂解固體產品（焦碳）物性分析、（2）焦碳經蒸汽活化後其物性分析與（3）評估廢電腦監視器塑膠外殼熱裂解固體產品再利用之可行性。

以375與425℃恆溫裂解廢電腦塑膠物質兩小時，分別可獲得約14.74與9.45％之固體產品，固體產物比例隨裂解溫度提高而降低。在元素分析方面，碳元素所含比例最高，皆約含有80％以上，且沒發現氧與硫元素存在。與市售碳黑特性比較，廢電腦塑膠物質裂解後所得之固體產物之比表面積與孔隙度遠小於市售碳黑（N330），與元素分析結果比較，初步探討原因可能因焦碳中含有大量之氫元素，表示仍有部分碳氫化合物附著於焦碳孔隙與表面上，而使焦碳之比表面積值與孔隙度偏小。

375 與425℃恆溫裂解廢電腦塑膠物質所得之固體產物經400～600℃蒸汽活化後，平均重量消失百分率分別為25.19～50.52％與 4.97～11.47％。其結果顯示，焦碳活化後重量消失百分率隨活化溫度提高而增加，初步探討原因可能因焦碳在熱裂解時，仍有部分碳氫化合物附著於焦碳孔隙與表面上，經由蒸汽蒸煮進行反應，而去除了部份附著於表面之碳氫化合物，而使焦碳重量消失。

焦碳經蒸汽活化後其粒徑有變小之趨勢，其變化與活化溫度有關，溫度越高所得產品粒徑越小，在活化溫度為600℃時，所得之產品粒徑約相近於市售碳黑（N330）；比表面積值與總孔體積隨活化溫度提高而變大。與市售碳黑相較下，其比表面積與孔隙度亦較小於市售碳黑（N330）。

不同焦碳添加量對輪胎性質的影響，其結果顯示，經由蒸汽活化後之焦碳其對橡膠補強性較優於未活化之原焦碳，但仍略不足市售碳黑之性能。在硬度分析方面，不同活化後焦碳添加量對輪胎硬度影響似乎不顯著，且其值（64JIS）與T_30CN330（62JIS）相近。
關鍵字：廢電腦、熱裂解、碳黑、橡膠輪胎。

Abstract

This study investigated the practicability for reusing the residues as an additive in tire from the pyrolysis of plastics in waste computer monitor. The properties of steam activated residues were determined to proide the useful data for other utilizations. This study include three parts:
1. Analyzing the physical properties of solid product residues from the pyrolysis of the plastic in waste computer monitor.
2.Analyzing the physical properties of steam activated residues.
3. Evaluating the practicality for reusing the residues from the pyrolysis of plastics in waste computer monitor.
The percentages of solid products were 14.74% and 9.54% for the pyrolysis temperature of 375 and 425℃, respectively. The residues decreased with increasing pyrolysis temperature. For the elemental analysis, the percentages of C were above 80%. S and O were not observed in the residues.Comparing with commercialized carbon black, the specific surface area and porous from the pyrolysis of waste plastic were smaller than those of carbon black. Investigating the results of the elemental analysis, there was about 5％ H in the residuses. It revealed that the hydrocarbons remained in the residues resulted in a small specific surface area and pore size.
The residues obtained from the pyrolysis temperatures of 375 and 425℃ were activated with steam. The results indicated that the average weight losses were 25.9-50.52％ and 4.97-11.47％, respectively. One noted that the rate of weight loss decreasd with increased the activating temperature. This might be ascribed to the further reaction of hydrocarbon in the residues.
After activating, the pore size of residues varied inversely with activating temperature. The pore size of residues after activating at 600℃ was closed to that of
commercialized carbon black (N330). Also, the specific surface area and the total pore volume increased with activating temperature. The specific surface area and the total pore volume obtained from steam activated residues were smaller carbon black.
Finally, we discussed the effects of the ratios of additives on the properties of the tire sample. The result indicated that the physical properties of steam activated residues is better than those of residues without steam activation. For the hardness analysis, the effects of the addition of additives obtained at different activating temperatures on the hardness of tire was insignificant.
Key Words : waste computer, pyrolysis, carbon black, tire.

目錄

封面內頁
簽名頁
授權書…………………………………………………………….......iii
中文摘要……………………………………………………………...iv
英文摘要……………………………………………………………...vi
誌謝…………………………………………………………………viii
目錄…..………………………………………………………………ix
圖目錄……………………………………………………………….xii
表目錄……………………………………………………………….xiv
符號說明…………………………………………………………...xvi
第一章 緒論 1
1.1 研究緣起 1
1.2 研究目的 2
1.3 研究內容與方法 2
第二章 文獻回顧與基本理論 6
2.1 電腦報廢量 6
2.2 廢電腦塑膠物質熱裂解相關研究 8
2.3膠輪胎產業與碳黑需求量 11
2.4國內外熱裂解相關研究 21
2.5焦碳活化 26
第三章 實驗設備與材料 32
3.1實驗方法 32
3.2 恆溫裂解實驗 32
3.3焦碳活化實驗 36
3.4殘餘物焦碳性質分析 38
3.4.1 元素分析 38
3.4.2 粒徑大小 40
3.4.3 比表面積 41
3.4.4 孔隙度 42
3.5 橡膠混煉程序及橡膠成品性質量測 43
3.5.1 橡膠混煉程序 43
3.5.2 最適加硫時間 46
3.5.3 硬度試驗 48
第四章 結果與討論 52
4.1.裂解廢電腦塑膠物質固、液與氣體百分比組成分析 52
4.2焦碳與市售碳黑（N330）性質分析 52
4.2.1元素分析 52
4.2.2粒徑分析 56
4.2.3比表面積與孔隙度 56
4.3活化後焦碳性質分析 61
4.3.1 活化後焦碳元素分析 64
4.3.2 活化後焦碳粒徑分析 67
4.3.3 活化後焦碳比表面積與孔隙度 67
4.3.4 焦碳活化最佳操作條件 76
4.4 橡膠混煉程序 78
4.4.1 最適加硫時間分析 78
4.4.2橡膠試片物理性質分析 78
第五章 結論與建議 96
5.1 結論 96
5.2 建議 100
參考文獻……………………………………………………………101
附錄A 相關聚合物之結構式 105
附錄B 標準偏差 106
附錄C 固體殘餘物之掃描式電子顯微鏡(SEM)分析..................107

參考文獻

1.www.epa.gov.tw
2.Ariyadejwanich, P., Tanthapanichakoon, W., Nakagawa, K., Mukai, S. R. and Tamon, H., “Preparation and Characterization of Mesoporous Activated Carbon from Waste Tires,” Carbon, Vol. 41, PP.157~164 (2003).
3.Barbooti, M. M., Mohamed, T. J., Hussain A. A. and Abas, F. O., “Optimization of Pyrolysis Condition of Scrap Tires under Inert Gas Atmosphere,” Journal of Analytical and Applied Pyrolysis, Vol. 72, PP.165~170 (2004).
4.Chen, J. H., Chen, K. S. and Tong, L. Y., “On the Pyrolysis Kinetics of Scrap Automotive Tires,” Journal of Hazardous Materials, Vol. 84, PP.43~55 (2001).
5.Day, M., Cooney, J. D. and Touchette, B. C., “Pyrolysis of Mixed Plastics Used in the Electronics Industry,” Journal of Analytical and Applied Pyrolysis, Vol. 52, PP.199-224, (1999).
6.Dong, D., Tasaka, S., Aikawa, S., Kamiya, S., Inagaki, N. and Inoue, Y., “Thermal Degradation of Acrylonitrile-Butadiene-Styrene Terpolymer in Bean Oil,” Polymer Degradation and Stability, ” Vol. 73, PP. 319~326 (2001).
7.Gersten, J., Fainberg, V., Garbar A., Hetsroni, G. and Shindler Y., “Utilization of Waste Polymers through One-Stage Low Temperature Pyrolysis with Oil Shale,” Fuel, Vol. 78, PP. 987-990 (1999).
8.Herrera, M., Matuschek, G. and Kettrup, A., “Fast Identification of Polymer Additives by Pyrolysis-gas Chromatography/Mass Spectrometry,” Journal of Analytical and Applied Pyrolysis, Vol. 70, PP. 35~42 (2003)
9.Kaminsky, W. and Mennerich, C., “Pyrolysis of Synthetic Tire Rubber in A Fluidised-Bed Reactor to Yield 1,3-Butadiene, Styrene and Carbon Black,” Journal of Analytical and Applied Pyrolysis, Vol. 58~89, PP.803~811 (2001).
10.Li, A. M., Li, X. D., Li, S. Q., Ren, T., Shang, .N, Chi, Y., Yan, J. H. and Cen, K. F., “Experimental Studies on Municipal Solid Waste Pyrolysis in a Laboratory-Scale Rotary Kiln,” Energy, Vol. 24, PP. 209~218 (1999).
11.Lin, J. P., Chang, C. Y. and Wu, C. H., “Pyrolysis Kinetics of Rubber Mixtures,” Journal of Hazardous Materials, Vol.58, PP.227~236 (1998).
12.Minkova, V., Razvigorova , M., Bjornbom , E., Zanzi, R., Budinova , T.and Petrov, N., “Effect of water vapour and biomass natureon the yield and quality of the pyrolysis products from biomass,” Fuel Processing Technology, Vol.70,PP. 53~61(2001)
13.Nasr, G. M., Badawy, M. M., Gwaily, S. E., Shash, N. M. and Hassan, H. H., “Thermophysical Properties of Butyl Rubber Loaded with Different Types of Carbon Black,” Polymer Degradation and Stability, Vol. 48, PP. 237~241 (1995).
14.Otowa, T., Nojima,Y. and Miyazaki, T., “Development of KOH Activated High Surface Area Carbon and Its Application to Drinking Water Purification,” PII, Vol. S0008-6233, PP. 00076-6（1997）.
15.Pantea, D., Darmstadt, H., Kaliaguine, S. and Roy, C., “Heat-Treatment of Carbon Blacks Obtained by Pyrolysis of Used Tires. Effect on the Surface Chemistry, Porosity and Electrical Conductivity,” Journal of Analytical and Applied Pyrolysis, Vol. 67, PP.55~76 (2003).
16.Park, S. J.and Kim, F. D., “Influence of Actication Temperature on Adsorption Characteristics of Activated Carbon Fiber Composites,” Carbon Vol. 39,PP.1741~1746（2001）.
17.Pastor-Villegas, J. and Duran-Valle, C. J., “Pore Structure of Activated Carbons Prepared by Carbon and Steam Activation at Different Temperatures from Extracted Rockrose,” Carbon, Vol.40, PP.397~402（2002）.
18.Roy, C., Rastegar, A., Kaliaguine, S. and Darmstsdt, H., “Physicochemical Properties of Carbon Blacks from Vacuum Pyrolysis of Used Tires,” Plastics, Rubber and Composites Processing and Applications, Vol. 23, PP. 21~30 (1995).
19.Suzuki, M. and Wilkie, C. A., “The thermal Degradation of Acrylonitrile/Butadiene/Styrene Terpolymer as Study by TGA/FTIR,” Polymer Degradation and Stability, Vol. 47, PP. 217~222 (1995a).
20.Teng, H.,Ho, J. A. and Hsu, Y. F., “Preparation of Activated Carbons from Bituminous Coals with CO2 Activation—Influence of coal Oxidation, ” PII, Vol. S0008-6223, PP.01137-6(1996).
21.Warhurst, A. W., Fowler, G. D., McConnachie, g. L. and Pollard, S.J. T., “ Pore Structure and Adsorption Characteristics of Steam Pyrolysis Carbons from Moringa Oleifera,” PII, Vol.S0008-6223, PP. 00053-5(1997).
22.Williams, P. T. and Besler, S., “Pyrolysis-Thermogravemetric Analysis of Tyres Components,”Fuel, Vol.74(9), PP. 1277-1283（1995）
23.Yang, M. H., “The Thermal Degradation Ofacrylonitrile-Butadiene -Styrene Terpolymer under Various Gas Condition,” Polymer testing, Vol.19, PP.105-110, (2000).
24.方明譯，輪胎膠料中各種材料的相互作用，Taiwan Rubber Industries，台灣區橡膠工業同會，2003。
25.王月英，橡膠業產業調查與技術，第144期，交通銀行徵信處，2003。
26.楊思廉，新材料塑膠，高立圖書公司，1983。
27.吳照雄，陳柏強，廢電腦塑膠物質熱裂解資源回收之研究（1/3），中華民國環境工程學會第17屆廢棄物處理研討會，2002。
28.吳照雄，林建興，廢電腦塑膠物質熱裂解資源回收之研究（2/3），中華民國環境工程學會第18屆廢棄物處理研討會，2003。
29.黃正義，張四立，李清華，陳志恆，楊奉儒，廢輪胎回收清除處理費率及補貼費率檢討計畫，行政院環境保護署研究報告，2001。
30.黃文魁，兩岸橡膠製品產業競合分析，工業技術研究院產業經濟與資訊服務中心，2003。
31.楊承哲，活性團聯合聚合物接枝包覆碳黑之奈米複合微粒的合成、性質與溶劑中分散特性，國立台灣大學化學工程學研究所碩士學位論文（2002）。
32.賴耿陽編著，碳材料化學與工學，復漢出版社，1990。
33.稻垣道夫、大谷杉郎、大谷朝男共著，賴耿陽譯著，碳材料碳纖維工學，復漢出版社，PP.48 (1986)
34.謝立生，碳黑物性與應用入門，高分子工業，高分子工業雜誌社，1998。
35.謝錦松、黃正義，固體廢棄物處理，高立圖書（2001）。
36.謝建德，活性碳孔隙結構與製備條件對液相吸附的影響，中原大學化學工程學系研究所碩士論文（1998）。
37.韓文騰，以碳黑及PAN 氧化纖維不織布補強酚醛樹脂製作碳/碳複合材料及其性質和微結構之探討，逢甲大學材料科學與工程研究所碩士論文（2003）。