臺灣博碩士論文加值系統

本研究選用竹山地區三至五年生竹齡之孟宗竹（學名：Phyllostachys pubescens）為原料，英文名稱為Moso bamboo，探討孟宗竹材於不同之活化劑、碳化溫度及碳化時間，製備具較高表面積性質之孟宗竹活性碳。伐採時，依竹稈之離地高度分成基段（2.5m 以下）、中段（2.5〜4.9m）與末段（4.9〜7.3m），在此採用中段（2.5〜4.9m）部位，再各自裁切成3x5cm長之圓竹段，檢測其含水率約45%，將其浸泡於不同比率之氫氧化鉀(KOH)或磷酸(H3PO4)並在500℃、600℃、700℃、800℃不同碳化溫度及不同之碳化時間下進行碳化，探討所製備之孟宗竹活性碳之產率、BET表面積、孔徑分佈、碘值吸附、亞甲基藍脫色力、IR表面官能基、SEM表面觀察、酸鹼值；探討不同之碳化溫度、碳化時間及不同種類與比率之活化劑對於製備孟宗竹活性碳之特性的影響，並找出每種活化劑之最佳製備參數。
在本研究設定之試驗條件範圍內，孟宗竹較適宜之碳化條件如對氫氧化鉀而言，其所需碳化溫度為800℃，碳化時間為120 min及氫氧化鉀比率為250%所製得之活性碳為最佳，具有較高之比表面積(2533.64 m2/g)，微孔面積達1879.63 m2/g，微孔體積達0.9462 cm3/g。而以磷酸當活化劑時，其所需之碳化溫度為500℃、碳化時間120 min及磷酸比率為150%時所製得之活性碳為最佳，可獲得較高之比表面積（1579.83 m2/g），微孔面積達895.36 m2/g，微孔體積達0.7314 cm3/g。透過亞甲基藍脫色力(20~300 mg/g)與碘值吸附量試驗(800~1300 mg/g)可以間接證明其比表面積高低之關連性，推估孔洞分佈狀態，而透過SEM觀察得知藉由KOH碳化的活性碳比H3PO4碳化後的表面較多孔構造，透過FTIR的分析可以發現活性碳表面含有C=O,C=C,-CH,-CH3,-CH2與-OH等官能基。

This paper reports the quality of activated carbon manufactured from 3 to 5 years old Moso bamboo (Phyllostachysheterocycla). Upon harvesting, bamboo culms were separated into basalsections (ground level to 2.5 m), mid sections (2.5 m to 4.9 m) and topsections (4.9 m to 7.3 m). Mid sections of moisture is about 45%. In this study, Moso bamboo was used as the precursor for activated carbon preparation. The preparation process consisted of potassium hydroxide and phosphoric acid impregnation at different impregnation ratio followed by carbonization at 500-800 °C for 60-120 min. Activated carbon was analyzed for Methylene blue Number, Iodine Number Brunauer
-Emmett-Teller (BET) surface area, and pore surface area, pore volume, surface function group, PH value, and SEM micrographs.
It is concluded that the best carbonization conditions for Moso bamboo were 800℃(KOH) ,500℃(H3PO4), and 120 min. The best conditions for obtaining activated carbon were 800℃, KOH impregnation ratio 250%, and a 120 minutes carbonization time. The activated carbon obtained under these conditions had 2533.64 m2 /g for BET surface area, 1879.63 m2 /g for micro-pore surface area, and 0.9462 cm3/g for micro-pore volume. The best conditions for obtaining activated carbon were 500℃, H3PO4 impregnation ratio 150%, and a 120 minutes carbonization time. The activated carbon obtained under these conditions had 1579.83 m2 /g for BET surface area, 895.36 m2 /g for micro-pore surface area, and 0.7314 cm3/g for micro-pore volume.
In addition, based on the relationships established and when the Methylene Blue Number and Iodine Number falls between 20 mg/g to 300 mg/g and 800 mg/g to 1300 mg/g, the BET surface area, micro pore surface area, and micro pore volume can be estimated from the Methyl Blue Number and Iodine Number. An SEM study showed that carbons produced from KOH activation have a more compact surface than H3PO4 activation. The FTIR analysis identified the presence of C=O,C=C,-CH,-CH3,-CH2 and–OH on the surface of carbons.

中文摘要 I
英文摘要 II
致 謝 IV
表目錄 VII
圖目錄 VIII
壹、前言 1
貳、文獻回顧 3
2.1製備活性碳原料 3
2.2 活性碳製備原理 4
2.化學活化法 7
2.3 活性碳的特性 10
2.3-1 比表面積 10
2.3-2 孔隙結構 10
2.3-3 表面官能基 12
2.4 活性碳的種類 14
2.5 活性碳的應用 16
2.6 吸附種類 17
2.7 吸附原理說明 17
2.7-1 等溫吸附曲線 17
2.7-2 吸附模式 20
2.8 相關研究 25
2.9 研究構想 28
參.實驗設備與方法 30
3.1 實驗材料及藥品 30
3.1.2 實驗器材及藥品 30
3.1.3實驗步驟 32
3.1.4 性質測定 33
3.1.4-1灰分含量測定 33
3.1.4-2平衡含水率測定 33
3.1.4-3元素分析 34
3.1.4-5比表面積與孔隙性質分析 35
3.1.4-6掃描式電子顯微鏡觀察(SEM observations surface) 35
3.1.4-7酸鹼(PH)值測定 36
3.1.4-8 亞甲基藍(Methylene blue)脫色力 37
3.1.4-9 碘值(Iodine value) 39
3.1.4-10表面官能基分析(Functional group anaylysis) 40
肆.結果與討論 41
4.1 孟宗竹基本性質檢測 41
4.2 碳化溫度與碳化時間影響 42
4.2-1產率(Yield) 42
4.2-2 BET比表面積探討 44
4.2-4 碘值吸附量 47
4.2-5 亞甲基藍脫色試驗 49
4.2-6 FT-IR活性碳表面官能基鑑定 51
4.2-7 活性碳之酸鹼值測定 54
4.3 活化劑比率之影響 56
4.3-1產率(Yield) 56
4.3-2 BET比表面積之影響 58
4.3-3 碘值吸附量 60
4.4 FESEM(場發射電子顯微鏡)活性碳表面構造觀察 64
五.結論 76
六.參考文獻 78

1. Kinoshita, K. (1988) Carbon electrochemical and physicochemical
properties. John wiley & sons, Inc. p.10
2. Tay, J. H., Chen, X. G., Jeyaseelan, S. and Graham, N. (2001), A comparative study of anaerobically digested and undigested sewage sludges in preparation of activated carbons. Chemosphere. 44, 53-57
3. Pis, J. J., Mahamud, M., Pajares, J. A., Parra, J. B. and Bansal, R. C.(1998), Preparation of active carbons from coal: PartⅢ: Activation ofchar. Fuel Processing Technology., 57, 149-161
4. Tseng, H., Yeh, T. S., Hsu, L. Y. (1998), Preparation of activated carbon from bituminous coal with phosphoric acid activation. Carbon. 36, 1387-1395
5. Ahmadpour, A. and Do, D. D. (1996), The preparation of active carbons from coal by chemical and physical activation. Carbon., 34,471-479
6. Liu, Z., Ling, L., Qiao, W. and Liu, L. (1999), Effect of hydrogen on the mesopore development of pitch-based spherical activated carbon containing iron during activation by steam. Carbon. 37, 2063-2066
7. Lozano-Castello, D., Lillo-Rodenas, M. A., Cazorla-Amoros, D.,Linares-Solano, A. (2001), Preparation of activated carbons from Spanish anthractile: Ⅰ.Activation by KOH. Carbon. 39, 741-749
8. Laszlo, K., Bota, A., Nagy, L. G. and Cabasso, I. (1999), Porous carbon from polymer waste materials. Colloids and Surfaces A:Physicochemical and Engineering Aspects. 151, 311-320
9. Streat, M., Patrick, J. W. and Camporro Perez, M. J. (1995), Sorption of phenol and para-chlorophenol from water using conventional and novel activated carbons. Water Research. 29, 467-472
10. Gierak, a. (1995), Preparation, characterization and adsorption application of spherical carbon adsorbents obtained from sulfonated polymers. Materials Chemistry and Physics. 41, 28-35
11. Nagano, S., Tamon, H., Adzumi, T., Nakagawa, K. and Suzuki, T. (2000), Activated carbon from municipal waste, Carbon, 38, 915-920
12. Shawwa, A. R., D. W. Smith and D. C. Sego. (2001) Color and chlorinated organics removal from pulp mills wastewater using activated petroleum coke. Wat. Res. 35( 3):745-749.
13. Lua, A. C. and J. Guo.(2000) Activated carbon prepared from oil palm stone by one-step CO2 activation for gaseous pollutant removal. Carbon 38:1089-1097.
14. Yun, C. H., Y. H. Park and C. R. Park (2001) Effects of pre-carbonization on porosity development of activated carbons from rice straw. Carbon 39:562-563.
15. 劉曾旭（1998）活性碳製造技術及應用。產業調查與技術127： 84-97。
16.Ahmadpour, A. and D. D .Do,(1996) The preparation of Active Carbon form Coal by Chemical and Physical Activation , Carbon, 34, p471.
17. Caturla, F., Molina-Sabio, M. and Rodrfguez-Reinoso F.(1991) Preparation of Activated Carbon by Chemical Activation with ZnCl2, Carbon, 29, p7, 999.
18. Ehrburger, P., Addoun, A., Addoun, F. and Donnet, J. B.(1986) Carbonization of Coals in The Presence of Alkaline Hydroxodes and Carbonates:
Formation of Activated Carbons, Fuel, 65, p1447
19. Yamashita, Y. and Ouchi, K.(1982) Influence of Alikali on the Carbonization Process -I, Carbonization of 3 ,5-Dimethylphenol-Forrnaldehyde Resin with NaOH, Carbon, 20, p4.1
20.Hassler J. W. (1974) Purification with Activated Carbon .Industrial Commerical Enviroment. Chemical Publishing Co. Inc, New York.
21.Jagtoyen M, Thwaits M,Stencel J, Maenaney B.,Derbyshire F.(1992) Carbon,30 1089.
22.Laine J., Yunes S.(1992) Effect of the Preparation Method on the Pore Size Distribution of Activated Carbon form Cocount Shell. Carbon 30,601.
23. Spivey, J. J., 1988,Recovery of volatile organics from small industrial sources, Environ. Prog., 7, pp.31-40.
24. Rodriguez-Reinoso F. (1998) The role of carbon materials in heterogeneous catalysis. Carbon 36: 159-175.
25. Laszlo, K., Josepovits, K., and Tombacz, E., (2001),Analysis of active sites on synthetic carbon surfaces by various methods, Analytical Sciences, 17, pp.1741-1744.
26. Biniak, S., Pakula, M., Szymanski, G. S., and Swiatkowski, A., (1999) ,Effect of activated carbon surface oxygen-and/or nitrogen-containing groups on adsorption of copper（Ⅱ）Ions from aqueous solution, Langmuir, 15, pp.6117.
27. Hall, C. R, and Holmes, R. J., (1992) ,The preparation and properties of some activated carbons modified by treatment with phosgene or chlorine, Carbon, 30, pp.173.
28. Park, S. J., and Kim, K. D., (2001) ,Influence of activation temperature on adsorption characteristics of activated carbon fiber composites, Carbon, 39, pp.1741-1746.
29. Boehm, H. P. (1994) Some aspects of the surface chemistry of carbon blacks and other carbons. Carbon 32:759.
30. Corapcioglu, M. O., and Huang, C. P., (1987) ,The surface acidity and characterization of some commercial activated carbon, Carbon, 25, pp.569.
31. Vasilyeva, G. K., V. D. Kreslavski and P. J. Shea (2002) Catalytic oxidation of TNT by activated carbon. Chemosphere 47: 311–317.
32. Gregg, S. J.; Sing, K. S. W.(1982) Adsorption, Surface and Porosity; Academic Press: London.
33. Freundlich, H. (1907) Ueber die Adsorption in Loesungen. Z. physik. Chem. 57:385-470.
34. Langmuir, I.(1918)The adsorption of gases on plane surfaces of glass, mica and platinum. J. Amer. Chem. Soc. 40:1361-1403.
35. Brunauer, S., P. H. Emmett and E. Teller (1938) Adsorption of gases in multimolecular layers. J. Amer. Chem. Soc. 40:1361-1403.
36. Volesky, B. (2001) Biosorption: Application aspects -Process simulation tools. In: Ciminelli VST & Garcia O Jr (Eds) Biohydrometallurgy: Fundamentals, Technology and Sustainable Development, Part B. p. 69–80.
37. Nasrin R. K., Marta C., Giselle S. and Janusz G.,(2000) Production of Microand Mesoporous Activated Carbon from Paper Mill Sludge I. Effect of Zinc Chloride Activation, Carbon, 38, p1905.
38. Rodríguez-Reinoso, F., Molina-Sabio, M. and Gonzalez, M. T., (1995) Use of Steam and CO2 as Activating Agents in the Preparation of Activated Carbons , Carbon, 33, p15.
39. Halsey, G. D. (1948) Physical adsorption on non-uniform surfaces. J. Chem.
Phys. (16):931-945.
40.D. Lozano-Castello´, M.A. Lillo-Ro´denas,D.Cazorla-Amoro´s, A.Linares-Solano, (2001) Preparation of activated carbons from Spanish anthracite I. Activation by KOH Carbon 39 741.
41. A.Linares-Solano et. al.(2001) Preparation of activated carbons from Spanish anthracite II. Activation by NaOH Carbon 39751-759
42. A.Linares-Solano et. al.(2003) Understanding chemical reactions between carbons and NaOH and KOH An insight into the chemical activation mechanism.Carbon 41 267-275.
43. L. Chunlan et al. (2005) Effect of pre-carbonization of petroleum cokes on chemical activation process with KOH Carbon 43 2295
44. A. Namane. et al. (2005) Determination of the adsorption capacity of activated carbon made from coffee grounds by chemical activation with ZnCl2 and H3PO4. Journal of Hazardous Materials B119 189–194
45. S. Ismadji et al. (2006) High surface area activated carbon prepared from cassava peel by chemical activation. Bioresource Technology 97 734–739.
46. B. Corcho-Corral et al. (2006) Preparation and textural characterisation of activated carbon from vine shoots (Vitis vinifera) by H3PO4－Chemical activation. Applied Surface Science 252
47.M.T.Kartel et al.(2006) Preparation of porous carbons by chemical activation of polyethyleneterephthalate. Carbon 44 1013-1024
48. M. Olivares-Marı´n,et al.(2006) Preparation of activated carbon from cherry stones by chemical activation with ZnCl2.Applied Surface Science 252 5967–5971
49. Cyrus Arjmand et al. (2006) Chemical Production of Activated Carbon from Nutshells and Date Stones chem. Eng. Technol. ,29,No.8,986-991
50. 洪崇彬 (2002) 木質廢棄物製造之碳化材的基本性質與利用。國立台灣大學森林學研究所博士論文第1-115 頁。
51.W.T Tsai, S.F Chien, H.F. Sun.(2001) Cleaner Production of Carbon Adsorbent by utilizing agricultural waste corn cob, Resources, Conservation and Recycling 32
52. 李堅 (1991) 林產科學新篇。東北林業大學出版社 P.123
53. Illan-Gomez. et al.(1996)Activated Carbons from Spanish Coal. 2. Chemical Activation, Energy Fuels, 10, p1 108,
54. Teng. H. et al (1999) Porosity Carbons Prepared from Bituminous Coal with Potassium Hydroxide Activation, md. Eng. Chern. Res., 38, p294.7
55. M. Jagtoyen, F. Derbyshire, Carbon 1998, 36, 1085.
56.彭瀞玉 (2003) 檳榔桿應用於活性碳製造之研究。國立嘉義大學林業與自然資源研究所碩士班P49。
57. 吳豐智、曾如玲(1999)木質廢棄物製備活性碳之研究。技術學刊14(4) :533-540。
58. T.Zhang et al (2004), Preparation of activated carbon from forest and agricultural residues through CO2 activation
Chem. Eng. J. 105, 53-59