臺灣博碩士論文加值系統

本試驗擇用台灣製漿工業常用樹種針葉材台灣二葉松與闊葉材玫瑰桉，於實驗室內製備不同活性鹼性質之硫酸鹽紙漿，依Björkman 1956 Standard Method研製球磨木質素及木質素-碳水化合物複合體，分析基本物理與化學性質並供作實驗材料。
九株常見之白腐菌，經篩選漂白性、檢測生理特性及木質素過氧化氫等六種分泌酵素活性後，其中Phanerochaete chrysosporium 、彩絨革蓋菌（Trametes versicolor）與樺革襉菌（Lenzites betulina）三株，選擇性指數值高，顯示對木質素之降解具選擇性。Lenzites betulina 可生長於 pH 3-10 間，且適合於 pH 8-10 強鹼性下生長；就溫度來看Lenzites betulina 可生長於 15-45℃，最適溫度為 30-45℃， Lenzites betulina 之生長速率亦相當快，適合做進一步生物漂白之研究菌株。
針、闊葉材未漂硫酸鹽紙漿進行靜態生物性白腐菌處理，經分析紙漿化學及物理性質前後的差異後得知，紙漿卡巴值隨處理時間增加而降低，並伴隨白度的增加，粘度則稍呈下降。白腐菌進行生物漂白後紙漿以0.5N NaOH 進行鹼萃，相較於控制組，不同活性鹼性質之硫酸鹽紙漿，鹼萃濾液中可溶性木質素均明顯增加，亦即紙漿經白腐菌處理後之漂白性明顯增加。
以甘露聚醣用量2 IU/g （每克絕乾紙漿）或與木聚醣2-4 IU/g個別或同時進行前處理，紙漿經單段半纖維素處理後，卡巴值略為降低，白度相對略增，粘度因木聚醣及甘露聚醣，能選擇性去除紙漿殘餘半纖維素，而留存豐富的高分子量纖維素片段，能有限度地改善粘度。
不同活性鹼性質的未漂硫酸鹽紙漿經2-10 IU/g木聚醣處理後，濾液之可見光吸收區域波長400-600nm均無明顯特性吸收，與對照組相較，波長237nm、280nm處明顯出現特性吸收，顯示木聚醣確有其作用。木聚醣處理段與鹼萃段所釋出之發色團之紫外-可見光吸收圖譜有所不同，鹼萃段溶出物質在波長205nm處較波長237nm有明顯吸收，木聚醣處理可促進鹼萃時殘餘木質素之移除，釋出發色團基。
球磨木質素、木質素-碳水化合物複合體在室溫下，應用DEAE-Sephadex A-50管柱進一步分離出中性C-I-M片段、(Lignin-rich) C-I-R片段與酸性(Acidic) C-I-A片段等三個片段，分別進行生物性白腐菌處理，由膠體滲透層析圖譜可知，紙漿進行生物漂白過程中，各分離木質素分子量可見產生移行，玫瑰桉木質素-碳水化合物複合體經P. chrysosporium處理後波形變寬大，出現木質素分子量聚合現象。L. betulina明顯降解玫瑰桉木質素-碳水化合物複合體及中性C-I-M片段，其分子量分佈有明顯增大之變化。
固定化白腐菌試驗將白腐菌培養於聚胺基甲酸乙酯泡棉，Trametes versicolor培養於溫度25℃、維持150rpm震盪下四天即可長滿。針、闊葉材硫酸鹽紙漿(濃度2.0% w/v )應用固定化技術經14天靜態處理，可增加若干紙漿白度並降低卡巴值。另應用海藻膠鈣包覆菌體之固定化處理技術，進行掃瞄式電子顯微鏡觀察，可見白腐菌增殖於聚胺基甲酸乙酯泡棉及海藻膠鈣之表面及內部。與未使用固定化技術之生物漂白紙漿相較，利用白腐菌固定化技術，可得完全無菌絲之紙漿，應用海藻膠鈣包覆菌體之固定化處理技術所得紙漿得率高，紙漿性質與未使用固定化之生物漂白處理者相當，處理後聚胺基甲酸乙酯泡棉置回生長箱中保持靜態七天、溫度維持4℃，可重複使用。

Kraft pulps prepared from softwood Pinus taiwanensis and hardwood Eucalyptus grandis, milled wood lignin and lignin-carbohydrate complex were prepared according to Björkman 1956 Standard Method in laboratory. The basic physical and chemical properties of these materials were analyzed.
Nine common white-rot fungi in Taiwan were selected through screening of biobleaching activity. After examining of physiological properties and enzyme activity such as lignin peroxidase in vitro, Phanerochaete chrysosporium, Trametes versicolor and Lenzites betulina showed high selection index. It showed that there three white-rot fungi were capable to degradate lignin. Lenzites betulina could grow between pH 3 to 10 with optimum value between pH 8 and 10. Lenzites betulina had fast growing rate, it could grow between 15 to 45℃, the optimum temperatures ranged from 30 to 45℃, it was suitable for biobleaching study.
Unbleached kraft pulp of softwood and hardwood directly treated with white-rot fungi in a static state. Comparing the differences from chemical and physical properties of kraft pulps before and after biobleaching, the kappa number of kraft pulp decreased, the brightness increased and the viscosity decreased slightly. Pulps after fungi pretreatment was extracted with 0.5N NaOH, comparing with the controls, pulps with different alkalinity, the soluble lignin of alkali extraction increased. i.e. The bleachability of Pulps after white-rot fungi pretreatment increased significantly.
Pulps were treated with mannase （2 IU/g）or/and xylanase （2-4 IU/g）. After a single hemicellulase sequence, the kappa number of pulps decreased slightly, the brightness increased and the viscosity could be improved. That was because of the mannase or/and xylanase could remove the residual hemicellulose on the pulps and preserve abundant high molecular weight cellulose fragment.
After the alkali extraction of kraft pulps pretreated with xylanase,there were no absorbance spectra in the visible range 400-600nm. Comparing with the controls, xylanase—released materials absorbed strongly at 237nm and 280nm. This indicated that xylanase improved the removal of residual lignin and release of chromophores.The UV/VIS spectra of released materials were different between xylanase treatment and alkali-extraction. Alkali- extraction released materials absorbed at 205nm more strongly than at 237nm.Xylanase could enhance the removal of residual lignin after alikali extraction and release of chromophores.
Milled wood lignin and lignin-carbohydrate complex were isolated to (Netural) C-I-M, (Lignin-rich) C-I-R and (Acidic) C-I-A fragments by DEAE-Sephadex A-50 at room temperature. Each fragment was treated with white-rot fungi. The molecular weight of isolated lignin shifted significantly by Gel Permeation Chromatography during the process of biobleaching. Lignin-carbohydrate complex of Eucalyptus grandis showed polymerization phenomenon as shown by GPC spectrum after P. chrysosporium treatment.
Fungal immobilization of white-rot fungus Trametes versicolor grew on polyurethane foam after 4 days under 25℃ and 150 rpm condition. Kraft pulp ( 4 g o.d., consistency 2.0 %w/v) contained 30 immobilized polyurethane foam cubes could increase some brightness and reduce kappa number after 14 days. After cell immobilization by calcium alginate-entrapment , hyperplasia was observed on the surface and inside of polyurethane foam and calcium alginate as shown by SEM. Comparing immobilization with biobleaching, the immobilization of white-rot fungus would get mycelium free pulp. The yield of pulp was high by cell immobilization by calcium alginate-entrapment. Characteristics of immobilized pulp are similar to those biobleached ones. Immobilization of fungus on polyurethane foam allows the repeated use after storage at 4℃ for 7 days in a growth chamber.

目 錄
頁次
目 錄…………………………………………….……..….…….. I
表目次 ………………………………………………………….. IV
圖目次 ……………………………………………….…..…….. VIII
摘要 ……………………………………………..…..……….. XXI
Summary .…………………………………………..………….. XXIII
壹、緒言 ………………………………………...……………… 1
貳、文獻回顧 ………………………………..…………………. 3
一、紙漿漂白工業之現況…………………………….……….. 3
二、紙漿工業生物技術之發展………………………………... 8
三、生物漂白之研究…………………………………………... 11
（一）白腐菌概述……………………………………………… 11
（二）木質素之白腐菌降解…………………………………… 16
（三）白腐菌的二次代謝系統………………………………… 15
（四）生物漂白有關研究……………………………………… 16
四、木聚醣前處理…………………………………………… 17
（一） 半纖維素與木聚醣……………………………………... 17
（二）木聚醣水解機制 ……………………………………... 20
（三）真菌所產生的木聚醣………………………………… 22
（四）木聚醣在紙漿工業的應用 …………………………. 24
六、木質素-碳水化合物複合體……………………………….. 28
七、固定化微生物……………………………………………… 30
（一） 固定化微生物技術之發展與優點…………………….. 30
（二） 以海藻膠鈣包覆菌體之固定化處理技術…………….. 33
（三）單槽式連續流動攪拌槽反應…………………………… 34
八、生物技術應用於木質纖維材料之展望…………….…….. 35
參、材料與方法 ……………………………..……..………… 36
一、試驗材料 ………………………………….…………….. 36
二、白腐菌漂白株的蒐集、篩選與生理特性……………….. 40
三、生物前處理……………………………………………….. 51
四、球磨木質素與木質素-碳水化合物複合體之製備及性質 53
五、白腐菌處理球磨木質素………………………………….. 59
六、木醣處理球磨木質素………………………………….. 59
七、固定化處理技術與單槽式連續流動攪拌槽反應器……… 59
八、紙漿漂白促進效果評估…….…………………………… 63
肆、結果與討論 ………………………………………………. 64
一、白腐菌的篩選與生理特性………………………………… 64
（一）腐朽性試驗……………………………………………… 64
（二）簡易木質素降解性試驗………………………………… 68
（三）簡易生物漂白性試驗…………………………………… 73
（四）生理特性………………………………………………… 76
二、生物漂白…………………………………………………… 46
（一）白腐菌處理紙漿………………………………………… 81
（二）木聚醣與甘露聚醣處理紙漿…………………… 86
（三）生物前處理對硫酸鹽紙漿漂白之促進效果…………… 88
三、發色團基釋放特性………………………………………… 91
（一）硫酸鹽紙漿經木聚醣處理後濾液之紫外-可見光吸收圖譜分析……………………………………………………… 91
（ 二）硫酸鹽紙漿經木聚醣處理後鹼萃濾液之紫外-可見光吸收圖譜分析………………………………………………… 95
四、球磨木質素之製備及性質………………………………… 101
（一）粒徑分析………………………………………………… 101
（二）收率比…………………………………………………… 103
（三）元素分析………………………………………………… 104
（四）紫外-可見光譜分析…………………………………… 105
（五）傅立葉紅外線光譜分析………………………………… 107
（六）碳-13核磁共振光譜(13C-NMR) ……………………… 111
（七）質子核磁共振光譜(1H-NMR) ………………………… 113
五、木質素-碳水化合物複合體片段分離與分子量分布……. 116
（一）收率比…………………………………………………… 117
（二）膠體滲透層析…………………………………………… 118
（三）分子量計算……………………………………………… 119
六、生物漂白處理後球磨木質素性質………………………… 125
（一）傅立葉紅外線光譜分析………………………………… 125
（二）膠體滲透層析…………………………………………… 130
七、固定化處理………………………………………………… 133
（一）聚胺基甲酸乙酯泡棉生長曲線………………………… 133
（二）掃瞄式電子顯微鏡觀察………………………………… 134
（三）固定化生物處理UKP對紙張性質的影響…………… 137
（四）重複使用效果…………………………………………… 139
八、連續攪拌式醱酵槽氧化還原電位監測……… 141
伍、結論………………………………………………………… 145
陸、參考文獻 ………………………………………………….. 147
表目次
表1.Table 1. 針葉材 ISO白度88-90 %之牛皮紙漿漂白工廠排放廢水中COD與AOX (Axegärd et al., 1993)Typical discharges of COD and AOX from modern standard processes for production of bleached softwood kraft pulp of ISO-brightness 88-90%. AL=aerated lagoon, AS=actived sludge treatment (Axegärd et al., 1993). .…………………….……………………………. 4
表2.Table 2. 化學漿漂白未來十年或計畫中有機鹵化物AOX值降低標準(Rennel et al.,1995)Decided or planned regulations for emission of chlorined organic compounds measured as AOX (kg/adt) from chemical pulp bleaching. (Rennel et al.,1995)……………………………………….……… 5
表3.Table 3. 產生木聚醣之微生物(Subramaniyan and Prema, 2000)Various microorganisms with xylanase-producing activity. (Subramaniyan and Prema, 2000)…………….………… 23
表4.Table 4. 試材成份分析Chemical composition of the wood………………….…. 37
表5.Table 5. 試材未漂牛皮紙漿性質Characteristics of unbleached kraft pulp………….…...... 39
表6.Table 6. 所用白腐菌、來源、培養基The white rot fungi and their source,medium.…...….….. 41
表7.Table 7. MALT AGAR培養基The procedures and the results of Gram stain….……...... 42
表8.Table 8. YM AGAR培養基Medium of YM AGAR………………….…...…………. 42
表9.Table 9. Nitrogen-limiting BIII /glucose medium之組成The composition of Nitrogen-limiting BIII /glucose medium.………………………………………….……… 45
表10.Table 10. BIII medium之組成The composition of BIII medium……...………………... 46
表11.Table 11. 微量金屬溶液之組成The composition of basal trace element solution..….…... 46
表12.Table 12. DNS分析法所需藥品The reagents of DNS method.….……………………..… 48
表13.Table 13. 白腐菌降解木質素之選擇性Selection index (SI) of white-rot fungi……….………… 67
表14. Table 14. E. grandis 木粉簡易木質素降解性試驗結果Results of screening of lignin-degrading fungi by E. grandis powder simple plate-test……...…..…..…………………. 71
表15. Table 15. P. taiwanensis 木粉簡易木質素降解性試驗結果Results of screening of lignin-degrading fungi by P. taiwanensis powder simple plate-test…………………... 72
表16.Table 16. 簡易闊葉材未漂硫酸鹽紙漿生物漂白性試驗結果Results of screening of biobleaching fungi by HWKP simple plate-test...…….…………………………………. 74
表17. Table 17. 簡易針葉材未漂硫酸鹽紙漿生物漂白性試驗結果Results of screening of biobleaching fungi by SWKP simple plate-test……………………………………………..…. 75
表18.Table 18. 白腐菌酵素活性測定(U/L)Enzyme activity of white-rot fungi (U/L)……………..... 80
表19.Table 19. 台灣二葉松硫酸鹽紙漿經木聚醣與（或）甘露醣處理結果Characteristic of P. taiwanensis kraft pulp treated with xylanase(XYL), mamnase(MAN) or both enzyme (XYL+MAN)……………………………….…………... 86
表20.Table 20. 玫瑰桉硫酸鹽紙漿經木聚醣與（或）甘露聚醣處理結果Characteristic of E. grandis kraft pulp treated with xylanase(XYL), mamnase(MAN) or both enzyme (XYL+MAN)….……………………………………….... 87
表21.Table 21. 生物性前處理紙漿施做鹼萃濾液波長280nm之吸收度The absorbance (280nm) of alkaline extraction filtrate after biological pretreatment（Estimate of pulp bleachablity）………………………………...…..…….. 89
表22.Table 22. 球磨木木質素與木質素-碳水化合物複合體之收率比Yields of extractives MWL and LCC………………...... 103
表23.Table 23. 元素分析Analytical compositions of lignins………………………104
表24.Table 24. MWL 與LCC之UV吸收係數Absorption coefficint of MWL and LCC………………..106
表25.Table 25. 木質素-碳水化合物複合體片段之收率比Yields of extractives MWL and LCC………………….. 116
表26.Table 26. 分離木質素重量平均分子量值Mw of isolated lignin..……………………………….... 121
表27Table 27. 白腐菌固定化處理與一般生物漂白紙漿性質之比較Difference of pulp properties between immobiolization and biobleaching………………….. ………………….….. 138
表28.Table 28. 重複使用P. chrysosporium固定化之泡棉處理台灣二葉松硫酸鹽紙漿性質之比較Comparing with the properties of reused PU with P. chrysosporium kraft pulp…………………………….. 139
表29.Table 29. 重複使用P. chrysosporium增殖之海褐藻膠鈣處理台灣二葉松硫酸鹽紙漿性質之比較Comparing with the properties of reused Ca-alginate with P. chrysosporium kraft pulp…….……………….…….... 140
圖目次
圖 1.Fig. 1. Dioxin、chlorinted dioxin與chlorinted furans類分子之化學結構Chemical structure of dioxin,chlorinated dioxin and chlorinated furans ……..……………………………..…………….…… 3
圖 2.Fig. 2. Phanerochaete chrysosporium木質素降解圖(Kirk,1993)Scheme depicting the lignin-degrading system of Phanerochaete chrysosporium(Kirk,1993)……………..…..……….…….... 13
圖 3.Fig. 3. 白腐菌木質素降解圖(Watanabe et al.,2002)Schematic illustration of lignin-degradation by selective white rot fungi(Watanabe et al.,2002)…………..…….…………… 14
圖 4.Fig. 4. 單電子傳遞系統( Shimada and Takahashi, 1991)A one-electron transfer system ( Shimada and Takahashi, 1991)……………………………………….………..………. 16
圖 5.Fig. 5. 木聚醣之化學結構圖。包含各種不同取代基所鍵結之位置 (Kulkarni, 1999)Chemical structure of xylan. Point out the different substituents binding site(Kulkarni, 1999)………………………………… 19
圖 6.Fig. 6. 植物木聚醣基本結構圖及xylanase攻擊位置 (Biely, 1985)A hypothetical plant xylan and the sites of its attack by microbial xylanolytic enzymes. (Biely, 1985)……….……… 21
圖 7.Fig. 7. 未漂牛皮漿LCC示意圖，箭號所指為木醣作用點(Daneault et al.1994)Possible structure of LCC in unbleached kraft pulp.arrow shows Possible sites os xylanase hydrilysis.……………..………… 25
圖 8.Fig. 8. 針葉材牛皮漿經半纖維素作用增進去木質素作用之假想圖"x"表酵素作用點 (Daneault et al. 1994)possible route to enhanced delignification of softwood kraft pulp by hemicellulase.Enzyme hydrolysis site are shown by"x"…. 26
圖 9.Fig. 9. 松材木質素與Arabino-4-o-methylglucuronoxylan間推測之ester鍵結(Watanabe and Koshijima 1988)Proposed structure of ester linkage between lignin and arabino-4-o-methylglucuro-Noxylan in pine(Watanabe and Koshijima 1988) ……………………………………….……….…..…... 29
圖 10.Fig. 10. 松材木質素與Glucomannan間推測之Ether鍵結(Watanabe et al.,1989)Proposed structure of ether linkage between lignin and glucomannan in pine(Watanabe et al.,1989)…………...…..... 29
圖 11.Fig. 11. DNS檢量線DNS standard curve.……………………………………….… 49
圖 12.Fig. 12. 球磨木質素製備流程圖Preparation of milled wood lignin(MWL) and lignin-carbohydrate complex (LCC) fractions from wood………… 55
圖 13.Fig.13. 單槽式連續流動攪拌槽反應器Single tank Continuous-flow Stirred Tank Reactor……….... 62
圖 14.Fig. 14. 白腐菌P. chrysosporium 8週培養後的台灣赤楊木塊Alnus formosana block after wood decay with white-rot fungus P. chrysosporium.……..………………….………..……..…. 64
圖 15.Fig. 15. 白腐菌P. coccineus 8週培養後的台灣赤楊木塊Alnus formosana block after wood decay test with white rot fungus P. coccineus………………………………..………….. 65
圖 16.Fig. 16. 白腐菌P. chrysosporium 4,6,8週培養後的台灣赤楊木塊Alnus formosana block after 4,6,8 weeks wood decay test with white rot fungus P. chrysosporium……...……….………….. 66
圖 17.Fig. 17. T. versicolor於0.1% Gallic acid PDA之顏色變化Color change of T. versicolor in 0.1% Gallic acid PDA …..…68
圖 18.Fig. 18. T.abietinum 於0.1% Gallic acid PDA之顏色變化I Color change of T.abietinum in 0.1% Gallic acid PDA.…… 69
圖 19.Fig. 19. P. chrysosporium於0.05% RBBR PDA之顏色變化Color change of P. chrysosporium in 0.05% RBBR PDA….. 69
圖 20.Fig. 20. P. coccineus 於0.01% GU WA之顏色變化p Color change of P. coccineus in 0.01% GU WA…..….…. 70
圖 21.Fig. 21. P. chrysosporium 於0.05% RBBR WA之顏色變化Color change of P. chrysosporium in 0.05% RBBR WA….. 70
圖 22.Fig. 22. P. coccineus於0.01% GU FA之顏色變化Color change of P. coccineus in 0.01% GU FA.…………… 73
圖 23.Fig. 23. P. chrysosporium 於0.05% RBBR FA之顏色變化Color change of P. chrysosporium in 0.05% RBBR FA.……. 73
圖 24.Fig. 24. 白腐菌生長速率Glowth rate of white rot fungi.…………………………….... 76
圖 25.Fig. 25. pH 對菌株生長之影響Effect of pH on mycelial growth(PDA medium,8℃,7 day)…. 77
圖 26.Fig. 26. 溫度對菌株生長之影響Effect of temperature on mycelial groth……………..……... 78
圖 27.Fig. 27. 木質素之誘導培養Ligninase production……………...……………………….… 79
圖 28.Fig. 28. 玫瑰桉硫酸鹽紙漿經白腐菌P. chrysosporium處理白度、黏度、卡巴值之經日變化Pulp brightness,viscosity,kappa number as a function of incubation time for HWKP treated with white-rot fungi P. chrysosporium………………………………………………. 81
圖 29.Fig. 29. 玫瑰桉硫酸鹽紙漿經白腐菌T. versicolor處理白度、黏度、卡巴值之經日變化Pulp brightness,viscosity,kappa number as a function of incubation time for HWKP treated with white-rot fungi T. versicolor……………………………………………………. 82
圖 30.Fig. 30. 玫瑰桉硫酸鹽紙漿經白腐菌L. betulina處理白度、黏度、卡巴值之經日變化Pulp brightness,viscosity,kappa number as a function of incubation time for HWKP treated with white-rot fungi L. betulina……………………………………………………. 82
圖 31.Fig. 31. 玫瑰桉硫酸鹽紙漿經白腐菌P. coccineus處理白度、黏度、卡巴值之經日變化Pulp brightness,viscosity,kappa number as a function of incubation time for HWKP treated with white-rot fungi P. coccineus……………………………………….…………… 83
圖 32.Fig. 32. 二葉松硫酸鹽紙漿經白腐菌P. chrysosporium處理白度、黏度、卡巴值之經日變化Pulp brightness, .viscosity,kappa number as a function of incubation time for SWKP treated with white-rot fungi P. chrysosporium.…………….….…………………………..…. 83
圖 33.Fig. 33. 二葉松硫酸鹽紙漿經白腐菌T. versicolor處理白度、黏度、卡巴值之經日變化Pulp brightness,viscosity,kappa number as a function of incubation time for SWKP treated with white-rot fungi T. versicolor.……………….………………………………….. 84
圖 34.Fig. 34. 二葉松硫酸鹽紙漿經白腐菌L. betulina處理白度、黏度、卡巴值之經日變化Pulp brightness,viscosity,kappa number as a function of incubation time for SWKP treated with white-rot fungi L. betulina……………………………….....………………….. 84
圖 35.Fig. 35. 二葉松硫酸鹽紙漿經白腐菌P. coccineus處理白度、黏度、卡巴值之經日變化Fig. 35. Pulp brightness,viscosity,kappa number as a function of incubation time for SWKP treated with white-rot fungi P. coccineus ……………………………………….…………... 85
圖 36.Fig. 36. 台灣二葉松硫酸鹽紙漿經2 IU/g木醣處理後釋出液之紫外光吸收圖譜。UV spectra of the Pinus taiwanensis kraft pulp released liguor after 2 IU/g xylanase pretreatment….……………………… 91
圖 37.Fig. 37. 針葉材台灣二葉松硫酸鹽紙漿經4 IU/g木醣處理後釋出液之紫外光吸收圖譜。UV spectra of the Pinus taiwanensis kraft pulp released liguor after 2 IU/g xylanase pretreatment.…………………………. 92
圖 38.Fig. 38. 台灣二葉松硫酸鹽紙漿經10 IU/g木醣處理後釋出液之紫外光吸收圖譜。UV spectra of the Pinus taiwanensis kraft pulp after 10 IU/g xylanase pretreatment………………………………………. 93
圖 39.Fig. 39. 2 IU/g木醣前處理硫酸鹽紙漿進行鹼萃釋放液之紫外-可見光吸收圖譜UV/VIS spectra of the Pinus taiwanensis kraft pulp after 2 IU/g xylanase pretreatment and alkali extraction…….…………. 96
圖 40.Fig. 40. 4 IU/g木醣前處理硫酸鹽紙漿進行鹼萃釋放液之紫外-可見光吸收圖譜。UV/VIS spectra of the Pinus taiwanensis kraft pulp after 4 IU/g xylanase pretreatment and alkali extraction………………… 97
圖 41.Fig. 41. 10 IU/g木醣前處理硫酸鹽紙漿進行鹼萃釋放液之紫外-可見光吸收圖譜。UV/VIS spectra of the Pinus taiwanensis kraft pulp after 10 IU/g xylanase pretreatment and alkali extraction. …………... 98
圖 42.Fig. 42. 研磨後木粉顆粒Wood particales after grinding in a ball mill.(Photograph taken in microscopes).………………………..…………………… 101
圖 43.Fig. 43. 不同研磨時間之粒徑變化Change of distribution curve during milling with different time………………………………………………………… 102
圖 44.Fig. 44. 不同木粉用量之粒徑變化Change of distribution curve during milling with different dosage.……………………………………………………. 102
圖 45.Fig. 45. MWL 與 LCC 紫外光圖譜分析UV/VIS spectrum of MWL and LCC……..………………. 105
圖 46.Fig. 46. MWL 與 LCC之λmax與吸收度UV λmax and absorbance of MWL and LCC.………..…. 106
圖 47.Fig. 47. 台灣二葉松球磨木質素與玫瑰桉球磨木質素傅立葉紅外線光譜分析FTIR spectra of MWL.………………………………..…… 107
圖 48.Fig. 48. 台灣二葉松球磨木質素與玫瑰桉球磨木質素1000-2000 cm-1 傅立葉紅外線光譜分析FTIR adsorption 1000-2000 cm-1 spectra of MWL ………... 109
圖 49.Fig. 49. 台灣二葉松球磨木質素與LCC 傅立葉紅外線光譜分析W FTIR adsorption spectra of MWL and LCC of Pinus taiwanensis ………………………..…………….…….…… 109
圖 50.Fig. 50. 台灣二葉松球磨木質素與LCC 1000-1800 cm-1傅立葉紅外線光譜分析FTIR adsorption 1000-1800 cm-1 spectra of MWL and LCC of P. taiwanensis…….…………….…………………………. 109
圖 51.Fig. 51. 玫瑰桉球磨木質素與LCC 傅立葉紅外線光譜分析FTIR adsorption spectra of MWL and LCC of Eucalyptus grandis.……………………………………………….……. 110
圖 52.Fig. 52. 玫瑰桉球磨木質素與LCC 1000-1800 cm-1傅立葉紅外線光譜分析FTIR adsorption 1000-1800 cm-1 spectra of MWL and LCC of E. grandis…………………..……………………………... 110
圖 53.Fig. 53. 台灣二葉松與玫瑰桉之MWL碳-13核磁共振光譜13C-NMR spectra of MWL of P.taiwanensis and E. grandi ……………………………………………………………… 111
圖 54.Fig. 54. 台灣二葉松木質素質子核磁共振光譜1H-NMR spectrum of MWL in CDCl3.………….……..…. 113
圖 55.Fig. 55. 台灣二葉松LCC質子核磁共振光譜1H-NMR spectrum of LCC in CDCl3 of P. taiwanensis…….114
圖 56.Fig. 56. 玫瑰桉松LCC質子核磁共振光譜1H-NMR spectrum of LCC in CDCl3 of E. grandis………….115
圖 57.Fig. 57. 玫瑰桉MWL與LCC分子量分布GPC of MWL and LCC of E. grandi..……….…………… 117
圖 58.Fig. 58. 台灣二葉松LCC分子量片段分布GPC of LCC of P. taiwanensis.…………………………. 118
圖 59.Fig. 59. Polystyrene 檢量線Standard curve of Polystyrene.………………………....…. 119
圖 60.Fig. 60. ELCC分子量推測Estimate of ELCC Mw..…………..…………………..…… 120
圖 61.Fig. 61. EMWL分子量推測Estimate of EMWL Mw...……….………………………… 120
圖 62.Fig. 62. 玫瑰桉球磨木質素與LCC經木聚醣 10-100U 處理後傅立葉紅外線光譜分析FTIR spectra of MWL and LCC of Eucalyptus grandis after 10-100unit xylanase treatment…………..……….…………… 125
圖 63.Fig. 63. 台灣二葉松球磨木質素與LCC經木醣 10-300U 處理後傅立葉紅外線光譜分析FTIR spectra of MWL and LCC of Pinus taiwanensis after 10-300unit xylanase treatment.……………………………..…. 126
圖 64.Fig. 64. 台灣二葉松球磨木質素與LCC經木醣 10-300U 處理後傅立葉紅外線光譜分析FTIR spectra of MWL and LCC of Pinus taiwanensis after 10-300unit xylanase treatment.………………….…………….. 127
圖 65.Fig. 65. A.A.18%玫瑰桉硫酸鹽紙漿經P. chrysosporium、T. versicolor、L. betulina處理後傅立葉紅外線光譜分析FTIR adsorption spectra of A.A 18% Eucalyptus grandis kraft pulp after P. chrysosporium、T. versicolor、L. betulina treatment……………....……………………………..…….. 128
圖 66.Fig. 66. A.A.18%台灣二葉松硫酸鹽紙漿經P. chrysosporium、T. versicolor、L. betulina處理後傅立葉紅外線光譜分析FTIR adsorption spectra of A.A 18% Pinus taiwanensis kraft pulp after P. chrysosporium、T. versicolor、L. betulina treatment ……………………..………………………..…... 129
圖 67.Fig. 67. ELCC經P. chrysosporium、L. betulina處理後分子量片段移行 GPC of ELCC after P. chrysosporium、Trametes versicolor 、L. betulina treatment....……………………..……………… 130
圖 68.Fig. 68 台灣二葉松LCC經P. chrysosporium、Trametes versicolor 、L. betulina 處理後分子量移行GPC of 2LCC after P. chrysosporium、Trametes versicolor 、L. betulina treatment. ………………..………………….… 131
圖 69.Fig. 69. 玫瑰桉LCC經L. betulina 處理後分子量移行GPC of ELCC after L. betulina treatment…………………....132
圖 70.Fig. 70. 不同均質菌絲液接種量固定於聚胺基甲酸乙酯泡棉生長曲線Growth curve of PU form with different suspension……….. 114
圖 71.Fig. 71. 海褐藻膠鈣SEM觀察SEM of Ca-alginate………………....………..……………...134
圖 72.Fig. 72. 海褐藻膠鈣SEM觀察（2）SEM of Ca-alginate….……………..………………….…… 134
圖 73.Fig. 73. PU 泡棉SEM觀察SEM of PU form.…………………………………..………. 135
圖 74.Fig. 74. P. chrysosporium增殖於海褐藻膠鈣SEM觀察SEM of Ca-alginate with P. chrysosporium.……………... 135
圖 75.Fig. 75. Trametes versicolor 增殖於海褐藻膠鈣SEM觀察SEM of Ca-alginate with T.versicolor…………………..… 136
圖 76.Fig. 76. P. chrysosporium增殖於PU 泡棉SEM觀察SEM of PU form with P. chrysosporium …………………...136
圖 77.Fig. 77. T. versicolor增殖於PU SEM觀察SEM of Ca-alginate with T. versicolor….………………….. 137
圖 78.Fig. 78. 台灣二葉松活性鹼18%硫酸鹽紙漿經白腐菌P. chrysosporium以連續攪拌式醱酵槽培養Redox電位及溶氧（DO）反應紀錄Redox and Do record of 18% kraft pulp of Pinus taiwanensis after P. chrysosporium by CSTR………………………...141
圖 79.Fig. 79. 台灣二葉松活性鹼18%硫酸鹽紙漿經白腐菌L. betulina 以連續攪拌式醱酵槽培養Redox電位及溶氧（DO）反應紀錄Redox and Do record of 18% kraft pulp of Pinus taiwanensis after L. betulina by CSTR….……………..…..…….…… 142
圖 80.Fig. 80. 玫瑰桉活性鹼18%硫酸鹽紙漿經白腐菌T. versicolor 以連續攪拌式醱酵槽培養Redox電位反應紀錄Redox and record of 18% kraft pulp of E. grandis after T. versicolor by CSTR.……………………..……..………. 143

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