臺灣博碩士論文加值系統

隨著紙漿需求量增加，用於造紙原料的木材原生漿及回收漿需求量亦隨之提升，木材原生漿有價昂及環境等疑慮，而回收漿之性質隨回收次數增加而降低，需尋找替代之原料，因此本研究以非木纖維之農業廢棄物稻草為原料製備紙漿。傳統製漿工業以化學製漿法為主，其廢水對環境較不友善且收率較低，本研究擬探討以機械製程進行稻草機械漿的製備，並生產香菇菌屬真菌Lentinus sp.漆酶，探討漆酶處理對紙張性質的影響。
試驗主要分三部分：（1）Lentinus sp.的培養及漆酶的生產、（2）紙漿漆酶處理對紙漿及紙張性質的影響、及（3）稻草機械漿紙張性質的最適化。真菌培養及漆酶生產分別以三角燒瓶及醱酵槽進行。紙漿及紙張性質測定包含紙漿之組成分如卡巴值、木質素含量；紙張之強度性質如環壓指數、斷裂長度及破裂指數；纖維間的結合性如厚度、密度、光散射係數；及纖維強度之零跨距抗張指數等。
試驗結果顯示Lentinus sp.真菌在pH 4.5條件下培養有最佳的漆酶生產效率，培養至第13天可生產漆酶活性24.5 U/mL。並檢討出紙漿漆酶酵素處理處理的最適條件為50℃、pH 4.7及添加1.5％水合紫脲酸（Violuric acid monohydrate）做為中間介質。
漆酶中間介質系統處理可降低紙漿木質素含量，稻草機械漿及針葉樹硫酸鹽化學漿木質素含量分別降低4.0及22.5％。但漆酶酵素處理並無法明顯降低稻草機械漿磨漿動力，且所得紙張之力學強度稍差。稻草機械漿之環壓指數、斷裂長度及零跨距抗張指數分別降低25.5、18.9及30.7％。針葉樹硫酸鹽紙漿之環壓指數、破裂指數及斷裂長度分別降低6.8、12.5、9.7％。推論是因漆酶處理使與半纖維素分子鍵結之木質素分子間互相交聯成較大分子，影響了紙張中纖維的強度及纖維間結合性所致。
稻草機械漿之厚度、嵩度、及與結構性質相關的性質極佳如環壓強度、及挺度等，但抗張強度及破裂強度性質較差，應用此稻草機械漿在製備瓦楞紙箱之裱面紙板或瓦楞芯紙時不宜單獨使用，應配合未漂白化學紙漿或瓦楞廢紙紙漿混合抄紙，添加40％針葉樹硫酸鹽紙漿即可使稻草機械漿達到瓦楞芯紙品質的應用標準。

The demand for pulp is increasing. Such a marked increase has been the result of the demand of wood virgin pulp and recovered pulp. During the price of wood virgin pulp and fibres cannot be recycled indefinitely, it needs to search an alternative to these source. Thus, in this study, agriculture residues, straw is used for source of pulp. Chemical pulp process is the main process of traditional pulp industries. During the effluent of chemical pulp process is not environmentally friendly, this study used a mechanical process to producing mechanical straw pulp. This study also cultivated Lentinus sp. for producing laccase which used for increasing pulp and paper properties.
This study is divided into three parts: (1) Cultivation of Lentinus sp. and producing of laccase (2) The effect of Lentinus sp. laccase treatment on pulp and paper properties. (3) The optimization of mechanical straw pulp paper properties. Cultivation of Lentinus sp. is implementing in flask or fermenter. Measurement items of pulp and paper included kappa number, lignin content, crush index, breaking length, zero-span tensile index, bursting index, thickness, apparent density and scattering coefficient.
The results show that an initial pH of 4.5 was the best for optimal growth and laccase production by Lentinus sp. The optimal temperature of laccase treatment is 50℃. The optimal pH of laccase treatment is 4.7. Additional 1.5% violuric acid monohydrate as mediator.
Laccase-mediator system treatment decreased lignin content of pulp effectively. Lignin content of mechanical straw pulp and unbleached softwood kraft pulp decreased 4.0 and 22.5%, respectively. But enzymatic treatment of laccase have no effect on decreasing energy of beating of mechanical straw pulp. And the strength properties of paper a little less. Crush index, breaking length and zero-span tensile index of mechanical straw pulp decreased 25.5, 18.9 and 30.7%, respectively. And Crush index, bursting index and breaking length of unbleached softwood kraft pulp decreased 6.8, 12.5 and 9.7%, respectively.
The results show that thickness, bulk and properties of structure(formation, air permeance, crush index and stiffness) of mechanical straw pulp is remarkable. But the properties of tensile and bursting are rather poor. Thus, the C. S. F. of this mechanical straw pulp should less than 200 mL when it apply to the production of liner board and corrugating medium paper. And it is unsuitable for use it alone. It should mixed with unbleached chemical pulp or recovered pulp from corrugated board. The properties of mechanical straw pulp which mixtures 40% unbleached softwood kraft pulp complied with CNS standard.

摘要i
Abstract iii
目次 v
表目次ix
圖目次 x

第一章 緒言1
第二章 文獻回顧4
一、木材的組成分及結構4
（一）木材的組成分4
（二）木材細胞壁的結構6
二、非木纖維在製漿造紙工業之應用7
三、化學漿與機械漿9
（一）化學製漿法9
（二）機械製漿法10
四、紙張及紙板之產量及用途11
（一）世界各地紙張及紙板之產量11
（二）紙張及紙板之用途12
五、瓦楞紙板12
（一）裱面紙板（Liner board）12
1. 牛皮裱面紙板（Kraft liner；K liner）12
2. 次級裱面紙板（Jute liner；J Liner）13
3. 耐水裱面紙板及撥水裱面紙板13
4. 白色裱面紙板13
（二）瓦楞芯紙（Corrugating medium paper）13
1. 一般瓦楞芯紙13
2. 強化瓦楞芯紙13
（三）裱面紙板及瓦楞芯紙的規格14
六、木質素氧化酵素15
（一）木質素過氧化酵素15
（二）錳過氧化酵素15
（三）多功能過氧化酵素16
（四）漆酶16
1. 漆酶的作用機制16
2. 漆酶的來源17
3. 真菌漆酶的性質18
（1）真菌漆酶的一般性質18
（2）同工酶18
（3）漆酶基質的種類18
（4）pH對漆酶的活性及穩定性的影響19
（5）溫度對漆酶的活性及穩定性的影響19
4. 真菌漆酶的生產19
（1）漆酶的誘導生產19
（2）pH值對漆酶生產的影響20
（3）溫度對漆酶生產的影響20
5. 真菌漆酶在生物科技上之應用20
（1）脫木質素反應及紙漿漂白上之應用20
（2）木質纖維素的聚合21
（3）廢棄物的去除22
（4）其他應用22
6. 漆酶中間介質系統在脫木質素反應上的應用22
（1）漆酶中間介質系統的作用機制22
（2）中間介質的種類23
第三章 材料與方法26
一、菌種26
二、試驗材料26
（一）紙漿26
（二）藥品26
1. Lentinus sp.的培養26
2. Lentinus sp.產漆酶活性之測定26
3. 紙漿之Lentinus sp.產漆酶處理27
4. 醇苯抽出物測定27
5. 全纖維素測定27
6. 酸不溶性木質素含量測定27
7. 卡巴值27
三、Lentinus sp.漆酶的生產27
（一）Lentinus sp.的小量培養（三角燒瓶）27
（二）Lentinus sp.的大量培養（醱酵槽） 28
1. 母液的培養28
2. 醱酵槽培養28
四、漆酶活性測定29
五、菌絲重量測定29
六、培養之最適pH值29
七、漆酶處理的最適條件評估30
（一）漆酶處理的最適pH值30
（二）漆酶處理的最適溫度評估30
八、稻草機械漿的製備30
九、磨漿30
（一）荷蘭式打漿機打漿法30
（二）盤磨機30
十、紙漿之漆酶處理31
十一、原料、紙漿及紙張性質的測定31
（一）化學組成分分析31
1. 含水率測定31
2. 灰分含量測定31
3. 醇苯萃取物含量測定32
4. 全纖維素含量測定32
5. 酸不溶性木質素含量測定33
6. 酸溶性木質素含量測定33
（二）紙漿性質的評估34
1. 卡巴值的測定34
2. 游離度的測定35
（三）紙張性質的評估35
1. 厚度的測定35
2. 環壓強度的測定36
3. 破裂強度的測定36
4. 抗張強度的測定37
5. 零跨距抗張強度的測定37
6. 光散射係數的測定38
十二、統計分析39
第四章 結果與討論 40
一、Lentinus sp.的培養及漆酶的生產40
二、Lentinus sp.產漆酶處理的最適條件評估43
(一) Lentinus sp.產漆酶處理之最適處理pH的評估43
(二) Lentinus sp.產漆酶處理的最適溫度評估44
三、Lentinus sp.產漆酶處理對稻草機械漿磨漿動力的影響45
四、不同游離度對稻草機械漿手抄紙性質的影響46
五、漆酶處理對稻草機械漿及針葉樹硫酸鹽漿的影響47
（一）Lentinus sp.產漆酶處理對紙漿木質素含量的影響47
（二）Lentinus sp.產漆酶處理對手抄紙性質的影響48
六、不同混漿比例的紙張性質51
七、漆酶中間介質處理對稻草機械漿與針葉樹硫酸鹽紙漿混漿之手抄紙性質的影響53
第五章 結論 55
第六章 參考文獻57

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