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研究生:黃國峰
研究生(外文):Kuo-Feng Huang
論文名稱:硫氫化鈉對木質素模式物脫甲基動力學之研究
論文名稱(外文):Studies on The Demethylation Kinetics of Lignin Model Compounds in NaSH
指導教授:汪淮汪淮引用關係
指導教授(外文):Hweig Wang
學位類別:碩士
校院名稱:國立臺灣大學
系所名稱:森林學研究所
學門:農業科學學門
學類:林業學類
論文種類:學術論文
論文出版年:1999
畢業學年度:87
語文別:中文
論文頁數:105
中文關鍵詞:硫氫化鈉木質素模式物製漿反應速率活化能反應動力學
外文關鍵詞:Sodium sulfateLignin model compoundsPulpRelative reaction rateActivation energyKinetics
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  為探討居於主流地位之硫酸鹽製漿法在蒸煮時,有關木質素之脫甲基動力學,故以硫氫化鈉(6 %)為蒸煮液,利用6種木質素模式物,並以160、170及180 °C三種溫度蒸煮,再使用高效液相層析儀分析其成分之變化,以計算反應速率及其活化能。
  試驗結果顯示:影響脫甲基反應之因子有蒸煮液之pH值、不同結構之官能基、官能基對甲氧基之位置、反應時間和反應溫度皆對反應速率有影響,其中反應時間愈長、反應溫度愈高則反應之效應愈好。當提高溫度皆會促進反應物之反應速率,在對位之官能基為羧基和鄰位含有羥基時,反應速率增加之效應最好,且不同位置及官能基皆會影響反應速率,當對位之官能基為醛基時,其反應的效果最好;而在中性狀態時,活化能最低。在pH值之效應方面,除了對甲氧基苯甲醛會隨著pH值升高,而反應速率降低外,其它5種則隨著pH值升高而增加,顯示當升高pH值會增加脫甲氧基之效率,但若木質素之結構含有醛基時則會影響脫甲氧基之效果。當比較不同木質素模式物之活化能時,發現在中性和鹼性時其活化能之變化較大。
In order to find out about the kinetics of lignin demethylation in sulfate pulping, which is the main stream of pulping processes. In this study, six lignin model compounds were cooked with NaSH (6%) cooking liquor at three different temperatures 160、170 and 180 °C. After cooking, HPLC was used to analyze their changes in chemical compositions in order to calculate their relative reaction rate and activation energy.
The experimental results are summarized as follows:The factors affecting demethylation reaction are the pH value of cooking liquor, different functional groups, the relative position of functional groups to methoxyl groups, cooking time and cooking temperature. All of which affected the relative reaction rate. The longer the reaction time and higher the reaction temperature would result higher relative reaction rate. The increase in temperature rising would accelerate the relative reaction rate of the reactant, especially when the carboxyl group is in the para-position and hydroxyl group in the ortho-position. Both different position and functional groups would affect the relative reaction rate. The para-functional group of aldehyde would result the best relative reaction rate; and would have the lowest activation energy under neutral condition. Regarding to the effect of pH value, except p-anisaldehyde would decrease the relative reaction rate when the pH increased, the other five model compounds would increase the relative reaction rate as the pH increased, which indicated that the increase in pH value would increase the efficiency of demethylation. But when the lignin contains aldehyde group would affect the efficiency of demethylation. On comparing the activation energy of different lignin model compounds, it was found that the great variation in activation energy occurred in the neutral to alkali pH range.
一、前言…………………………………………………………… 1
二、文獻回顧……………………………………………………… 5
(一)木質素化學…………………………………………… 5
1、木質素化學概述…………………………………… 5
2、木質素光譜分析…………………………………… 6
3、木質素構成元素之分析…………………………… 10
4、木質素之結構模式化合物………………………… 16
(二)鹼法製漿之木質素反應……………………………… 21
1、β─芳香醚鍵之醚化酚型結構…………………… 22
2、β─芳醚鍵之游離酚型結構……………………… 22
3、α─醚鍵之結構…………………………………… 23
4、甲氧基……………………………………………… 24
5、縮合反應…………………………………………… 24
6、發色團之形成……………………………………… 26
7、整個脫木質素程序………………………………… 27
(三)亞硫酸鹽法製漿之木質素反應……………………… 29
1、酸性狀態下醚鍵的裂解…………………………… 30
2、中性、鹼性狀態下醚鍵之裂解…………………… 32
3、縮合反應…………………………………………… 32
(四)脫木質素之動力學…………………………………… 34
(五)脫甲基之反應………………………………………… 35
三、試驗材料、設備與方法……………………………………… 37
(一)試驗材料……………………………………………… 37
(二)試驗設備……………………………………………… 37
(三)試驗方法……………………………………………… 38
四、結果與討論…………………………………………………… 40
(一)4-甲基苯甲醚(4-methyl anisole )之反應………… 44
(二)對甲氧基苯甲醇(Anisealcohol)之反應…………… 51
(三)對甲氧基苯甲醛(P-anisaldehyde )之反應……… 58
(四)鄰甲氧基酚(Guaiacol )之反應…………………… 65
(五)苯甲醚(Anisole)之反應…………………………… 72
(六)對甲氧基苯甲酸(p-anisic acid)之反應…………… 79
(七) pH值對木質素結構之影響………………………… 85
五、結論…………………………………………………………… 86
六、參考文獻……………………………………………………… 87
陶泰來譯、Smook著 (1985) 製漿造紙技術手冊,食貨出版社。109-139頁。
陳信泰 (1979) 台灣檜木製材廢料製漿之研究。台灣大學森林學研究所碩士論文。32頁。
陳信泰、賴元榮、谷雲川 (1993) 脫木質素之區域化學效應,1.酸性製漿法。中華林學季刊 26(1):93-128。
陳信泰、賴元榮、谷雲川 (1994) 脫木質素之區域化學效應,2.鹼性製漿法。中華林學季刊 27(3):105-118。
張上鎮 (1989) 光譜分析之利器─霍氏紅外線光譜分析。林產工業8(4):112-124。
張上鎮、王升陽 (1995) 碳─13核磁共振光譜在木質素化學分析之應用。中華林學季刊 28(3):73-84。
Alder, E. and K. Lundquist (1961) Estimation of "uncondensed" phenolic units in spruce lignin. Acta Chem. Scand. 15:223-224.
Adler, E., S. Delin and K. Lundquist (1959) Phenylcoumaran elements in spurce lignin. Acta Chem. Scand. 13:2149-2150.
Beatson, R. P., C. Gancet and C. Heitner (1984) The topochemistry of black spruce sulfonation. Tappi. 67(3):82-85.
Bjorkman, A. and B. Person (1957) Studies on finely divided wood, part 2, the properties of lignins extracted with neutral solvents from softwoods and hardwoods. Svensk Papperstidning 60:158-169.
Bolker, H. I. and N. G. Somerville (1963) Infrared spectroscopy of lignins Ⅱ, lignin in unbleached pulps. Pulp Paper Mag. Can. 64T:187-193.
Casey, J. P. (1981) Pulp and Paper Chemistry and Chemical Technology 1:377-378, 411-418.
Chen, H. T. (1992) Ph. D. Thesis. The influence of antheraquinone on the sulfite delignification. State University of New York, College of Environmental Science and Forestry. pp.1-71,75-86.
Fengel, D. and G. Wegener (1983) Wood Chemistry, Ultrastructure Reactions. Walter de Gruyter & Co, Berlin. pp.132-148,282-284.
Freudenberg, K. and G. C. Sidhu (1961) Zur Kenntnis des Lignins der Buche und Fichte. Holzforschung. 20:105-109.
Gierer, J. and B. Koutek (1969) The cleavage of aromatic methylethers by neutral sulphite. A kinetic investigation. Acta Chem. Scand. 23(4):1343-1351.
Gierer, J.(1970) The reaction of lignin during pulping. A description and comparison of conventional pulping processes. Svensk Papperstidning. 73:571-596.
Gierer, J. and I. Norean (1980a) On the course of delignification during kraft pulping. Holzforschung. 34(6):197-200.
Gierer, J., S. Ljunggren, P. Ljungquist and I. Noren (1980b) The reactions of lignin during sulfate pulping. Part 18. The significance of α-carbonyl groups for the cleavage of β-aryl ether structures. Svensk Papperstidning. 83(3):75-82.
Gellerstedt, G. and J. Gierer (1968) The reaction of lignin during neutral sulphite cooking Ⅰ. The behaviour of β-Arylether structures. Acta Chem. Scand. 22(8):2510-2518.
Gellerstedt, G. and J. Gierer (1971) The reactions of lignin during acidic sulphite pulping. Svensk Papperstidning. 74:117-127.
Gellerstedt, G. (1976) The reactions of lignin during sulfite pulping. Svensk Papperstidning. 79:537-543.
Hearon, W. M., W. S. Macgregor and D. W. Goheen (1962) Sulfur chemicals from lignin. Tappi. 45(1):28-34.
Hergert, H. L. (1960) Infrared spectra of lignin and related compounds Ⅱ, conifer lignin and model compounds. J. Org. Chem. 25:405-413.
Hon, D. N.-S. and N. Shiraishi (1991) Wood and Cellulosic Chemistry. Marcel Dekker, Inc. New York and Basel. pp.113-175.
Johansson, B., J. Mjoberg, P. Sandstrom and A. Teder (1984) Modified continuous kraft pulping - now a reality. Svensk Papperstidning. 87(10):30-35.
Keskin, A. and G. J. Kubs (1994) Kinetics of neutral sulfite semichemical and neutral sulfite semichemical-anthraquinone pulping. J. Wood Chem. and Tech. 14(1):103-117.
Kolboe, S. and G. Ellefsen (1962) Infrared investigations of lignin, a discussion of some recent results. Tappi. 45:163-166.
Hudo, M. and T. Kondo (1971) Studies of the hydrophilic properties of lignin. Tappi. 54(12):2046-2050.
Lo, C. F., H. A. Schroeder, M. L. Laverr and H. Aft (1971) Low-molecular-weight lignin sulfonates. Ⅰ. Isolation from a softwood lignin product. Tappi. 54(10):1731-1733.
Ludwig, C. H., B. J. Nist and J. L. McCarthy (1964) Lignin ⅩⅢ, the high resolution nuclear magnetic resonance spectroscopy of protons in acetylated lignins. J. Amer. Chem. Soc. 80:1196-1202.
Lundquist, K. (1979) NMR studies of lignins 2, interpretation of the 1H NMR spectrum of acetylated birch lignin. Acta Chem. Scand. B33:27-30.
Lundquist, K. (1980) NMR studies of lignins 4, investigation of spruce lignin by 1H NMR spectroscopy. Acta Chem. Scand. B34:21-26.
Macleod, J. M. (1986) Alkaline sulfite-anthraquinone pulp from aspen. Tappi. 69(8):106-109.
Mansson, P. (1983) Quantitative determination of phenolic and total hydroxyl groups in lignins. Holzforschung. 37:143-146.
Matsukura, M. and A. Sakakibara (1969) On the heterogeneous distribution of chemical structure in lignin. Mokuzai Gakkaishi. 15:35-39.
Miksche, G. E. and S. Larsson (1971) Gaschromatographische analyse von ligninoxydationsprodukten, V, zwei trimere abbauprodukte aus fichtenlignin. Acta Chem. Scand., 25:673-679.
Nimz, H. (1974) Beech lignin-proposal of a constitutional scheme. Angew. Chem. 13:313-321.
Norden, S. and A. Teder (1979) Modified kraft processes for softwood bleached-grade pulp. Tappi 62(7):49-51.
Pursiainen, S., S. Hiljanen, P. Uusitalo, K. Kovasin and M. Saukkonen (1990) Mill-scale experiences of extended delignification with Super Batch cooking method. Tappi 73(8):115-122.
Ronals, G. M. (1969) Pulp and Paper Manufacture Vol. 1, The Pulping of Wood. McGRAW - KILL Book Company New York. p. 422.
Sarkanen, K. V. (1971) Precursors and their polymerization, in Lignins. Wiley-Interscience, New York. p.154.
Sarkanen, k. V., F. G. Chirkin and B. F. Hrutfiord (1963) Base-catalyzed hydrolysis of aromatic ether linkages in lignin. Ⅰ. The rate of hydrolysis methoxyl groups by sodium hydroxide. Tappi 46(6):375-379.
Schoning, A. G. and G. Johansson (1965) Absorptiometric determination of acid-soluble lignin in semichemical bisulfite pulps and in some woods and plants. Svensk Papperstidning. 68:607-613.
Sjostrom, E. (1977) The behavior of wood polysaccharides during alkaline pulping processes. Tappi. 60(9):151-154.
Sjodin, L. and B. Pettersson (1987) Two case studies on the cold blow technique for batch kraft pulping. Tappi. 70(2):72-76.
Smook, G. A. (1982) Handbook for Pulp & Paper Technologists. pp.34, 63.
Sjoblom, K., J. Mjoberg and N. Hartler (1983) Extended delignification in kraft cooking through improved selectivity. Paperi ja Puu. 65(4):227-240.
Tender, A. and L. Olm (1981) Extended deligninfication by combination of modified kraft pulping and oxygen bleaching. Paperi ja Puu. 63(4a):315-326.
Wegener, G., M. Przyklenk, and D. Fengel (1983) Hexafluoropropanol as valuable solvent for lignin in UV and IR spectroscopy. Holzforschung 37:303-307.
Yamasaki, T. and K. Hata (1978) Isolation and characterization of syringyl component rich lignin. Holzforschung. 32(2):44-47.
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