臺灣博碩士論文加值系統

對苯二甲酸被廣泛使用在各種石化產品上，如聚對苯二甲酸乙二酯、聚酯纖維、聚酯膜等。在對苯二甲酸製程中往往排放具有高濃度的對苯二甲酸和苯甲酸等其它有機酸，且每製造一噸的對苯二甲酸會產生3-10m3(含5-300g/L COD)的廢水，所以對苯二甲酸製程所產生的廢水需經再處理以符合排放標準。
本研究是使用含浸法將活性碳浸漬在硝酸銅溶液中，再將銅改質之活性碳吸附分離對苯二甲酸及苯甲酸，並與未改質活性碳做比較。由於改質過程中有許多影響因子，因此使用Plackett-Burman部份因子設計法篩選尋找主要的影響因子，再利用全因子實驗設計法找出各影響因子的主要效應與相互影響效應，最後利用改質活性碳進行不同溫度下之單成分及雙成分吸附實驗並尋找最吻合之吸附平衡模式。
根據Plackett-Burman實驗設計法，硝酸含浸濃度、硝酸含浸時間、硝酸銅含浸濃度、煅燒溫度為主要影響活性碳吸附的重要因子，因此使用全因子實驗設計，其最佳製備條件為硝酸含浸濃度為1N、硝酸含浸時間為24h、硝酸銅含浸濃度為0.05N、煅燒溫度為250℃，等溫吸附實驗結果顯示：經由銅改質之活性碳，苯甲酸及對苯二甲酸其吸附量皆大於未改質之活性碳，於高溫下吸附量較大，而未改質之活性碳則具有相反效果，苯甲酸的親合力大於對苯二甲酸，雙成份吸附平衡可成功地由IAST與Freundlich模式預測，或是由Modified Langmuir模式預測。

Terephthalic acid is widely used in a variety of petrochemical products, such as polyethylene terephthalate, polyester fiber, and polyester film. For every ton of TPA produced, about 3–10 m3 of wastewater is produced with very high amount of organic content (5–300 g/L COD). So terephthalic acid process wastewater needs suitable treatment to comply with the emissions standards.
In this study, activated carbon was modified with copper nitrate by impregnation method, and then used to adsorb and separate terephthalic acid and benzoic acid to compare with the performance of the original activated carbon. Because the modification process involved many influencing factors, the Plackett-Burman design method was applied to screen the main factors, and the full factorial experiment design method was used to find the main effects and interaction effects. Finally, single and binary component of adsorption equilibriums were measured at different temperatures and suitable adsorption isotherm models were found.
According to the Plackett-Burman method, the nitric acid concentration, nitric acid impregnation time, impregnant concentration, and calcination temperature are important factors for carbon adsorption capacity. From the full factorial design method, the best conditions found were 1N nitric acid concentration, 24hr nitric acid impregnation time, 0.05N impregnant concentration, and 250℃ calcination temperature. The adsorption equilibrium results showed that the adsorption capacities for benzoic acid and terephthalic acid onto the modified carbon were higher than the original carbon; both capacities increased with increasing temperature. The binary adsorption data can be successfully predicted by the IAST along with the Freundlich model or the modified Langmuir model.

誌謝i
ABSTRACTii
摘要iii
目錄iv
表目錄viii
圖目錄x
第一章前言1
1.1 研究背景1
1.2 研究目的2
第二章文獻回顧3
2.1 對苯二甲酸製程廢水3
2.1.1 廢水來源3
2.1.2 對苯二甲酸(Terephthalic acids)特性5
2.1.3 苯甲酸(Benzoic acids)特性5
2.1.4 常見處理方法10
2.2 活性碳吸附理論13
2.2.1 活性碳簡介13
2.2.2 吸附原理14
2.3 銅改質活性碳程序15
2.3.1 酸處理的影響15
2.3.2 含浸法16
2.3.3 金屬觸媒之煅燒17
2.3.4 含浸法製備金屬觸媒17
2.3.5 影響因子20
2.4 實驗設計法20
2.4.1 實驗設計的目的與意義20
2.4.2 Plackett-Burman21
2.4.3 全因子實驗設計法23
2.5 等溫吸附25
第三章實驗30
3.1 實驗藥品與儀器30
3.1.1 實驗藥品30
3.1.2 實驗儀器30
3.2 實驗步驟31
3.2.1 活性碳前處理31
3.2.2 活性碳改質處理程序32
3.2.3 批次實驗33
3.3 檢量線測定34
3.3.1 UV/vis檢量線34
3.3.2 原子吸收光譜之檢量線41
3.4 實驗設計法44
3.4.1 Plackett-Burman實驗44
3.4.2 全因子實驗44
3.5 等溫吸附實驗48
第四章結果與討論52
4.1 活性碳之特性分析52
4.1.1 BET表面之測定與分析52
4.1.2 FTIR之測定與分析52
4.1.3 XRD之測定與分析54
4.2 實驗設計之結果與探討54
4.2.1 Plackett-Burman實驗設計58
4.2.2 24全因子實驗設計68
4.2.3 原子吸收光譜儀之測定與分析79
4.3等溫吸附實驗之結果與探討79
4.3.1改質與未改質之單一成份吸附79
4.3.2 改變溫度之影響81
4.3.3 改質與未改質之雙成份吸附103
第五章結論121
參考文獻123

1.Vione, D., Minero, Claudio.,Maurino, Valter.,Carlotti, M. Eugenia.,Picatonotto, Tatiana.,Pelizzetti, Ezio, Degradation of phenol and benzoic acid in the presence of a TiO2-based heterogeneous photocatalyst. Applied Catalysis B: Environmental, 2005. 58(1-2): p. 79-88.
2.Zhang, Z., Ma, Liping.,Zhang, Xu-Xiang.,Li, Weixin.,Zhang, Yan.,Wu, Bing.,Yang, Liuyan.,Cheng, Shupei, Genomic expression profiles in liver of mice exposed to purified terephthalic acid manufacturing wastewater. Journal of Hazardous Materials, 2010. 181(1-3): p. 1121-1126.
3.Joung, J.Y., Lee, Hae Woo.,Choi, Hyeoksun.,Lee, Min Woo.,Park, Jong Moon, Influences of organic loading disturbances on the performance of anaerobic filter process to treat purified terephthalic acid wastewater. Bioresource Technology, 2009. 100(8): p. 2457-2461.
4.Kim, J.Y., Woo, Seung Han.,Lee, Min Woo.,Park, Jong Moon, Sequential treatment of PTA wastewater in a two-stage UASB process: Focusing on p-toluate degradation and microbial distribution. Water Research, 2012. 46(8): p. 2805-2814.
5.Zhang, X.-X., Sun, Shi-Lei.,Zhang, Yan.,Wu, Bing.,Zhang, Zong-Yao.,Liu, Bo.,Yang, Liu-Yan.,Cheng, Shu-Pei, Toxicity of purified terephthalic acid manufacturing wastewater on reproductive system of male mice (Mus musculus). Journal of Hazardous Materials, 2010. 176(1-3): p. 300-305.
6.Thiruvenkatachari, R., T. Ouk Kwon, and I. Shik Moon, Degradation of Phthalic Acids and Benzoic Acid from Terephthalic Acid Wastewater by Advanced Oxidation Processes. Journal of Environmental Science and Health, Part A: Toxic/Hazardous Substances & Environmental Engineering, 2006. 41(8): p. 1685-1697.
7.Chandrasekara Pillai, K., T.O. Kwon, and I.S. Moon, Degradation of wastewater from terephthalic acid manufacturing process by ozonation catalyzed with Fe2+, H2O2 and UV light: Direct versus indirect ozonation reactions. Applied Catalysis B: Environmental, 2009. 91(1-2): p. 319-328.
8.Anbia, M. and S. Salehi, Synthesis of polyelectrolyte-modified ordered nanoporous carbon for removal of aromatic organic acids from purified terephthalic acid wastewater. Chemical Engineering Research and Design, 2012. 90(7): p. 975-983.
9.Zuo, X., Niu, Fenghui.,Snavely, Kirk.,Subramaniam, Bala.,Busch, Daryle H., Liquid phase oxidation of p-xylene to terephthalic acid at medium-high temperatures: multiple benefits of CO2-expanded liquids. Green Chemistry, 2010. 12(2): p. 260.
10.Jiang, Q., Xiao, Yang.,Tan, Ze.,Li, Qing-Hong.,Guo, Can-Cheng, Aerobic oxidation of p-xylene over metalloporphyrin and cobalt acetate: Their synergy and mechanism. Journal of Molecular Catalysis A: Chemical, 2008. 285(1-2): p. 162-168.
11.Hans A. KREBS, D.W.a.M., STUBBS and Alberto SOLS and Francisco BEDOYA, Studies on the mechanism of the antifungal action of benzoate. Biochem. J., 1983. 214: p. 657-663.
12.Park, T.-J., Lim, Jong Sung.,Lee, Youn-Woo.,Kim, Sung-Hyun, Catalytic supercritical water oxidation of wastewater from terephthalic acid manufacturing process. The Journal of Supercritical Fluids, 2003. 26(3): p. 201-213.
13.Veriansyah, B. and J.-D. Kim, RETRACTED: Supercritical water oxidation for the destruction of toxic organic wastewaters: A review. Journal of Environmental Sciences, 2007. 19(5): p. 513-522.
14.Karthik, M., Dafale, Nishant.,Pathe, Pradyumna.,Nandy, Tapas, Biodegradability enhancement of purified terephthalic acid wastewater by coagulation–flocculation process as pretreatment. Journal of Hazardous Materials, 2008. 154(1-3): p. 721-730.
15.Zhu, G.-F., Wu, Peng.,Wei, Qun-Shan.,Lin, Jian-yi.,Gao, Yan-Li.,Liu, Hai-Ning, Biohydrogen production from purified terephthalic acid (PTA) processing wastewater by anaerobic fermentation using mixed microbial communities. International Journal of Hydrogen Energy, 2010. 35(15): p. 8350-8356.
16.Pophali, G.R., Khan, R.,Dhodapkar, R. S.,Nandy, T.,Devotta, S., Anaerobic–aerobic treatment of purified terephthalic acid (PTA) effluent; a techno-economic alternative to two-stage aerobic process. Journal of Environmental Management, 2007. 85(4): p. 1024-1033.
17.Chidambara Raj, C.B., Ramkumar, N.,Haja jahabar siraj, A.,Chidambaram, Sp, Biodegradation of Acetic, Benzoic, Isophthalic, Toluic and Terephthalic Acids Using a Mixed Culture: Effluents of PTA Production. Process Safety and Environmental Protection, 1997. 75(4): p. 245-256.
18.Soni, R.K., S. Soam, and K. Dutt, Studies on biodegradability of copolymers of lactic acid, terephthalic acid and ethylene glycol. Polymer Degradation and Stability, 2009. 94(3): p. 432-437.
19.Thiruvenkatachari, R., Kwon, Tae Ouk.,Jun, Jung Chul.,Balaji, Subramanian.,Matheswaran, Manickam.,Moon, Il Shik, Application of several advanced oxidation processes for the destruction of terephthalic acid (TPA). Journal of Hazardous Materials, 2007. 142(1-2): p. 308-314.
20.Shafaei, A., M. Nikazar, and M. Arami, Photocatalytic degradation of terephthalic acid using titania and zinc oxide photocatalysts: Comparative study. Desalination, 2010. 252(1-3): p. 8-16.
21.Hirakawa, T., K. Yawata, and Y. Nosaka, Photocatalytic reactivity for O2− and OH radical formation in anatase and rutile TiO2 suspension as the effect of H2O2 addition. Applied Catalysis A: General, 2007. 325(1): p. 105-111.
22.Pesavento, M., Profumo, Antonella.,Alberti, Giancarla.,Conti, Fabio, Adsorption of lead(II) and copper(II) on activated carbon by complexation with surface functional groups. Analytica Chimica Acta, 2003. 480(1): p. 171-180.
23.Toles, C.A., W.E. Marshall, and M.M. Johns, Surface functional groups on acid-activated nutshell carbons. Carbon, 1999. 37: p. 1207–1214.
24.Zhua, Z.H., L.R. Radovicb, and G.Q. Lua Effects of acid treatments of carbon on N2O and NO reduction by carbon-supported copper catalysts. Carbon, 2000. 38: p. 451–464.
25.Jaramillo, J., V. Gomez-Serrano, and P.M. Alvarez, Enhanced adsorption of metal ions onto functionalized granular activated carbons prepared from cherry stones. Journal of Hazardous Materials, 2009. 161(2-3): p. 670-676.
26.Xu, D., Dai, P.,Guo, Q.,Yue, X., Improved hydrogen generation from alkaline NaBH4 solution using cobalt catalysts supported on modified activated carbon. International Journal of Hydrogen Energy, 2008. 33(24): p. 7371-7377.
27.Zhou, D.-M., Wang, Yu-Jun.,Wang, Han-Wei.,Wang, Shen-Qiang.,Cheng, Jie-Min, Surface-modified nanoscale carbon black used as sorbents for Cu(II) and Cd(II). Journal of Hazardous Materials, 2010. 174(1-3): p. 34-39.
28.Chuang, K.-H., Lu, Chi-Yuan.,Wey, Ming-Yen.,Huang, Ya-Ni, NO removal by activated carbon-supported copper catalysts prepared by impregnation, polyol, and microwave heated polyol processes. Applied Catalysis A: General, 2011. 397(1-2): p. 234-240.
29.Haro, M., Ruiz, B.,Andrade, M.,Mestre, A. S.,Parra, J. B.,Carvalho, A. P.,Ania, C. O., Dual role of copper on the reactivity of activated carbons from coal and lignocellulosic precursors. Microporous and Mesoporous Materials, 2012. 154: p. 68-73.
30.Bian, J., Wei, X. W.,Jin, Y. R.,Wang, L.,Luan, D. C.,Guan, Z. P., Direct synthesis of dimethyl carbonate over activated carbon supported Cu-based catalysts. Chemical Engineering Journal, 2010. 165(2): p. 686-692.
31.Zhenping Zhu, Z.L., Shoujun Liu, Hongxian Niu, Tiandon Hu ,Tao Liu ,Yaning Xie, NO reduction with NH3 over an activated carbon-supported copper oxide catalysts at low temperatures. Applied Catalysis B: Environmental, 2000. 26: p. 25–35.
32.Calvo, L., Gilarranz, M. A.,Casas, J. A.,Mohedano, A. F.,Rodriguez, J. J., Hydrodechlorination of alachlor in water using Pd, Ni and Cu catalysts supported on activated carbon. Applied Catalysis B: Environmental, 2008. 78(3-4): p. 259-266.
33.Moreno-Pirajan, J.C., Tirano, Joaquin.,Salamanca, Brisa.,Giraldo, Liliana, Activated Carbon Modified with Copper for Adsorption of Propanethiol. International Journal of Molecular Sciences, 2010. 11(3): p. 927-942.
34.Zhao, J., Z. Liu, and D. Sun, TPO–TPD study of an activated carbon-supported copper catalyst–sorbent used for catalytic dry oxidation of phenol. Journal of Catalysis, 2004. 227(2): p. 297-303.
35.Tomas Berling and Per Runeson, Efficient Evaluation of Multifactor Dependent System Performance Using Fractional Factorial Design. IEEE Transactions on Software Engineering, 2003. 29 p. 769-781.
36.Wang, J. and W. Wan, Experimental design methods for fermentative hydrogen production: A review. International Journal of Hydrogen Energy, 2009. 34(1): p. 235-244.
37.Araujo, P.W. and R.G. Brereton, Experimental design I. Screening,. Trends in Analytical Chemistry 1996. 15(1): p. 26-31.
38.Allen, S., G. J.McKay, and J.F. Porter, Adsorption isotherm models for basic dye adsorption by peat in single and binary component systems. Journal of Colloid and Interface Science, 2004. 280(2): p. 322-333.
39.Tan, I.A.W., A.L. Ahmad, and B.H. Hameed, Adsorption of basic dye on high-surface-area activated carbon prepared from coconut husk: Equilibrium, kinetic and thermodynamic studies. Journal of Hazardous Materials, 2008. 154(1-3): p. 337-346.
40.Liu, H., Liu, Weifeng.,Zhang, Jian.,Zhang, Chenglu.,Ren, Liang.,Li, Ye, Removal of cephalexin from aqueous solutions by original and Cu(II)/Fe(III) impregnated activated carbons developed from lotus stalks Kinetics and equilibrium studies. Journal of Hazardous Materials, 2011. 185(2-3): p. 1528-1535.
41.Vasanth Kumar, K. and S. Sivanesan, Equilibrium data, isotherm parameters and process design for partial and complete isotherm of methylene blue onto activated carbon. Journal of Hazardous Materials, 2006. 134(1-3): p. 237-244.
42.Kumar, S., Zafar, Mohd.,Prajapati, Jitendra K..,Kumar, Surendra.,Kannepalli, Sivaram, Modeling studies on simultaneous adsorption of phenol and resorcinol onto granular activated carbon from simulated aqueous solution. Journal of Hazardous Materials, 2011. 185(1): p. 287-294.
43.Chern, J.-M.a.C.-Y.W., Desorption of dye from activated carbon beds: effects of temperature, pH, and alcohol. Water Research, 2001. 35: p. 4159-4165.
44.Lee, I.H., Y.-C. Kuan, and J.-M. Chern, Equilibrium and kinetics of heavy metal ion exchange. Journal of the Chinese Institute of Chemical Engineers, 2007. 38(1): p. 71-84.
45.Srivastava, V.C., I.D. Mall, and I.M. Mishra, Equilibrium modelling of single and binary adsorption of cadmium and nickel onto bagasse fly ash. Chemical Engineering Journal, 2006. 117(1): p. 79-91.
46.Deveci, H., Yazıcı, E. Y.,Alp, I.,Uslu, T., Removal of cyanide from aqueous solutions by plain and metal-impregnated granular activated carbons. International Journal of Mineral Processing, 2006. 79(3): p. 198-208.
47.Papageorgiou, S.K., Katsaros, F. K.,Kouvelos, E. P.,Kanellopoulos, N. K., Prediction of binary adsorption isotherms of Cu2+, Cd2+ and Pb2+ on calcium alginate beads from single adsorption data. Journal of Hazardous Materials, 2009. 162(2-3): p. 1347-1354.
48.S. Al-Asheh, F.B., R. Al-Omari, Z. Duvnjak, Predictions of binary sorption isotherms for the sorption of heavy metals by pine bark using single isotherm data. Chemosphere, 2000. 41: p. 659-665.
49.Sismanoglu, T., Y. Kismir, and S. Karakus, Single and binary adsorption of reactive dyes from aqueous solutions onto clinoptilolite. Journal of Hazardous Materials, 2010. 184(1-3): p. 164-169.