TEMPO氧化体系选择性氧化未漂非木浆的研究
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摘要
以未漂麦草浆和竹浆为原料,研究了TEMPO-NaBr-NaClO体系氧化前后纸浆性质及纤维形貌的变化情况,并对其氧化过程进行了动力学分析。结果表明,未漂麦草浆和竹浆的TEMPO氧化过程均遵循二级反应动力学方程。经TEMPO氧化后,麦草浆和竹浆的羧基含量大幅提高,分别达569.8μmol/g和716.7μmol/g,而纸浆黏度和热稳定性则均显著下降。此外,氧化前后纤维微观形貌、尺寸变化不大,而结晶度则有所增加,但仍保持了天然纤维素I型的结晶结构。
In this study,unbleached wheat straw and bamboo pulps were oxidized by TEMPO-NaBr-NaClO system. Both the fiber morphologies and properties of pulps before and after oxidation were studied. Besides,the kinetics of oxidation process was analyzed. The results showed that both TEMPO-NaClO-NaBr oxidation processes of unbleached wheat straw and bamboo pulps could be described by second-order reaction kinetics equation. After oxidation the contents of carboxyl groups in wheat straw and bamboo pulps increased significantly and reached 569. 8 μmol/g and 716. 7 μmol/g,respectively. However,the viscosity and thermal stability of the pulps were obviously decreased.Moreover,the microstructure and size of the fibers were almost unchanged before and after the oxidation. The crystalline structure of celluloseⅠof the pulps were maintained after oxidation,while the crystalline indices were slightly increased.
In this study,unbleached wheat straw and bamboo pulps were oxidized by TEMPO-NaBr-NaClO system. Both the fiber morphologies and properties of pulps before and after oxidation were studied. Besides,the kinetics of oxidation process was analyzed. The results showed that both TEMPO-NaClO-NaBr oxidation processes of unbleached wheat straw and bamboo pulps could be described by second-order reaction kinetics equation. After oxidation the contents of carboxyl groups in wheat straw and bamboo pulps increased significantly and reached 569. 8 μmol/g and 716. 7 μmol/g,respectively. However,the viscosity and thermal stability of the pulps were obviously decreased.Moreover,the microstructure and size of the fibers were almost unchanged before and after the oxidation. The crystalline structure of celluloseⅠof the pulps were maintained after oxidation,while the crystalline indices were slightly increased.
引文
[1]ZHAN Huai-yu.Supply and Utilization of Non-wood Fibers and Waste Papers in China’s Paper Industry[J].China Pulp&Paper,2010,29(8):56.詹怀宇.我国造纸用非木材纤维和废纸原料供应与利用[J].中国造纸,2010,29(8):56.
[2]ZHAN Huai-yu,FU Shi-yu,LI Hai-long.The development overview and technical progress of China non-wood fiber pulping of bamboo and straw[J].China Pulp&Paper Industry,2011,32(9):12.詹怀宇,付时雨,李海龙.我国非木材纤维制浆的发展概况与技术进步(之一)竹子与麦草[J].中华纸业,2011,32(9):12.
[3]HUANG Yu,WANG Lin-shan,XING Ying,et al.Research progress in modification of non-wood plant fibers[J].Chemical Engineering,2010,38(10):21.黄昱,王林山,邢莹,等.非木材植物纤维改性研究进展[J].化学工程,2010,38(10):21.
[4]Zhang Qian,Fu Shi Yu,Li Hai Long,et al.Morphology and Property Analysis of Bagasse Pulp by TEMPO-Mediated Oxidation[J].Paper Science&Technology,2012,31(4):27.张倩,付时雨,李海龙,等.TEMPO氧化体系氧化蔗渣浆的性能及形貌分析[J].造纸科学与技术,2012,31(4):27.
[5]De Nooy Arjan E J,Besemer Arie C,Van Bekkum Herman.Highly selective nitroxyl radical-mediated oxidation of primary alcohol groups in water-soluble glucans[J].Carbohydrate Research,1995,269(1):89.
[6]Isogai Akira,Kato Yumiko.Preparation of Polyuronic Acid from Cellulose by TEMPO-mediated Oxidatio[J].Cellulose,1998,5(3):153.
[7]Saito Tsuguyuki,Isogai Akira.TEMPO-mediated oxidation of native cellulose.The effect of oxidation conditions on chemical and crystal structures of the water-insoluble fractions[J].Biomacromolecules,2004,5(5):1983.
[8]MAO Lian-shan,MA Pu,LIU Gui-nan,et al.Study on TEMPO-mediated Selective Oxidation of TMP Long Fibers[J].China Pulp&Paper,2009,28(7):7.毛连山,马朴,刘桂南,等.机械浆长纤维的TEMPO选择性催化氧化[J].中国造纸,2009,28(7):7.
[9]Dai Lei,Long Zhu,Zhang Dan.Research progress in preparation and application of TEMPO-oxidized cellulose nanofibers[J].Journal of Materials Engineering,2015,43(8):84戴磊,龙柱,张丹.TEMPO氧化纤维素纳米纤维的制备及应用研究进展[J].材料工程,2015,43(8):84.
[10]Isogai Akira.Wood nanocelluloses:fundamentals and applications as new bio-based nanomaterials[J].Journal of Wood Science,2013,59(6):449.
[11]Dai Lei,Long Zhu,Chen Le.Application of TEMPO/Na Br/Na Cl O in papermaking[J].Transactions of China Pulp and Paper,2015,30(2):58.戴磊,龙柱,陈乐.TEMPO/Na Br/Na Cl O氧化体系在造纸中的应用[J].中国造纸学报,2015,30(2):58.
[12]Qian Jing Rong,Tang Ai Min,Song Jian Kang.Effectet of TEMPO Selective Oxidation on Cellulose-Morphology and Paper Properties[J].Paper&Paper Making,2010,29(10):22.钱荣敬,唐爱民,宋建康.TEMPO选择性氧化对纤维形态及成纸性能的影响[J].纸和造纸,2010,29(10):22.
[13]Yao Wen Run,Xu Qing Hua,Jin Li Qiang,et al.Effects of TEMPO/Na Br/Na Cl O-oxidation of Nanocrystalline Cellulose on Its Properties[J].Chemistry&Industry of Forest Products,2015,35(2):31.姚文润,徐清华,靳丽强,等.TEMPO/Na Br/Na Cl O氧化对纳米微晶纤维素性能的影响[J].林产化学与工业,2015,35(2):31.
[14]Jovana Milanovic,Mirjana Kostic,Petar Skundric.Structure and properties of TEMPO-oxidized cotton fibers[J].Chemical Industry&Chemical Engineering Quarterly,2012,18(2):473.
[15]HOU Qing-xi,CHAI Xin-sheng,ZHU Jun-yong.Determination of the Carboxyl Groups in Fibers by Headspace Gas Chromatography[J].China Pulp&Paper,2005,24(9):5.侯庆喜,柴欣生,朱俊勇.应用顶空气相色谱测定纸浆纤维的羧基含量[J].中国造纸,2005,24(9):5.
[16]Dai Lu,Dai Hong Qi,Yuan Yang Chun,et al.Study on oxidation kinetic of cotton fibers oxidation with TEMPO[J].Journal of Nanjing Forestry University(Natural Science Edition),2011,35(2):93.戴路,戴红旗,袁洋春,等.TEMPO氧化体系氧化棉纤维的动力学研究[J].南京林业大学学报:自然科学版,2011,35(2):93.
[17]Sbiai Adil,Kaddami Hamid,Sautereau Henry,et al.TEMPO-mediated oxidation of lignocellulosic fibers from date palm leaves[J].Carbohydrate Polymers,2011,86(4):1445.
[18]Sun Bin,Gu Chun Ju,Ma Jin Hong,et al.Kinetic study on TEMPO-mediated selective oxidation of regenerated cellulose[J].Cellulose,2005,12(1):59.
[19]Brodin Fredrik Wernersson,Theliander Hans.A comparison of softwood and birch kraft pulp fibers as raw materials for production of TEMPO-oxidized pulp,MFC and superabsorbent foam[J].Cellulose,2013,20(6):2825.
[20]Dang Zheng,Zhang Jian Guo,Ragauskas Arthur J.Characterizing TEMPO-mediated oxidation of ECF bleached softwood kraft pulps[J].Carbohydrate Polymers,2007,70(3):310.
[21]Pei Ji Cheng.Lignocellulosic Chemisty[M].Beijing:China Light Industry Press,2012.裴继诚.植物纤维化学[M].北京:中国轻工业出版社,2012.
[22]Saito T,Shibata I,Isogai A,et al.Distribution of carboxylate groups introduced into cotton linters by the TEMPO-mediated oxidation[J].Carbohydrate Polymers,2005,61(4):414.
[23]Li Lin,Zhao Shuai,Zhang Jin,et al.TEMPO-mediated oxidation of microcrystalline cellulose:Influence of temperature and oxidation procedure on yields of water-soluble products and crystal structures of water-insoluble residues[J].Fibers&Polymers,2013,14(3):352.
[24]Alemdar A,Sain M.Isolation and characterization of nanofibers from agricultural residues-Wheat straw and soy hulls[J].Bioresource Technology,2008,99(6):1664.
[25]Alila S,Besbes I,Vilar M R,et al.Non-woody plants as raw materials for production of microfibrillated cellulose(MFC):A comparative study[J].Industrial Crops&Products,2013,41(2):250.
[26]Kuramae Ryota,Saito Tsuguyuki,Isogai Akira.TEMPO-oxidized cellulose nanofibrils prepared from various plant holocelluloses[J].Reactive&Functional Polymers,2014,85:126.
[27]Meng Qi Jun,Li Hai Long,Fu Shi Yu,et al.The non-trivial role of native xylans on the preparation of TEMPO-oxidized cellulose nanofibrils[J].Reactive&Functional Polymers,2014,85:142.
[28]Potthast A,Schiehser S,Rosenau T,et al.Oxidative modifications of cellulose in the periodate system-reduction and beta-elimination reactions[J].Holzforschung,2009,63(63):12.
[29]Shibata Izumi,Isogai Akira.Depolymerization of cellouronic acid during TEMPO-mediated oxidation[J].Cellulose,2003,10(2):151.
[30]Isogai Akira,Saito Tsuguyuki,Fukuzumi Hayaka.TEMPO-oxidized cellulose nanofibers[J].Nanoscale,2011,3(1):71.
[31]Zhu Guang Yong,Zhu Xian,Xiao Zuo Bing,et al.Study of cellulose pyrolysis using an in situ visualization technique and thermogravimetric analyzer[J].Journal of Analytical&Applied Pyrolysis,2012,94(94):126.
[32]Orfao J J M,Antunes F J A,Figueiredo J L.Pyrolysis kinetics of lignocellulosic materials—three independent reactions model[J].Fuel,1999,78(3):349.
[33]Ouajai S,Shanks R A.Composition,structure and thermal degradation of hemp cellulose after chemical treatments[J].Polymer Degradation&Stability,2005,89(2):327.
[34]Fukuzumi Hayaka,Saito Tsuguyuki,Okita Yusuke,et al.Thermal stabilization of TEMPO-oxidized cellulose[J].Polymer Degradation&Stability,2010,95(9):1502.
[2]ZHAN Huai-yu,FU Shi-yu,LI Hai-long.The development overview and technical progress of China non-wood fiber pulping of bamboo and straw[J].China Pulp&Paper Industry,2011,32(9):12.詹怀宇,付时雨,李海龙.我国非木材纤维制浆的发展概况与技术进步(之一)竹子与麦草[J].中华纸业,2011,32(9):12.
[3]HUANG Yu,WANG Lin-shan,XING Ying,et al.Research progress in modification of non-wood plant fibers[J].Chemical Engineering,2010,38(10):21.黄昱,王林山,邢莹,等.非木材植物纤维改性研究进展[J].化学工程,2010,38(10):21.
[4]Zhang Qian,Fu Shi Yu,Li Hai Long,et al.Morphology and Property Analysis of Bagasse Pulp by TEMPO-Mediated Oxidation[J].Paper Science&Technology,2012,31(4):27.张倩,付时雨,李海龙,等.TEMPO氧化体系氧化蔗渣浆的性能及形貌分析[J].造纸科学与技术,2012,31(4):27.
[5]De Nooy Arjan E J,Besemer Arie C,Van Bekkum Herman.Highly selective nitroxyl radical-mediated oxidation of primary alcohol groups in water-soluble glucans[J].Carbohydrate Research,1995,269(1):89.
[6]Isogai Akira,Kato Yumiko.Preparation of Polyuronic Acid from Cellulose by TEMPO-mediated Oxidatio[J].Cellulose,1998,5(3):153.
[7]Saito Tsuguyuki,Isogai Akira.TEMPO-mediated oxidation of native cellulose.The effect of oxidation conditions on chemical and crystal structures of the water-insoluble fractions[J].Biomacromolecules,2004,5(5):1983.
[8]MAO Lian-shan,MA Pu,LIU Gui-nan,et al.Study on TEMPO-mediated Selective Oxidation of TMP Long Fibers[J].China Pulp&Paper,2009,28(7):7.毛连山,马朴,刘桂南,等.机械浆长纤维的TEMPO选择性催化氧化[J].中国造纸,2009,28(7):7.
[9]Dai Lei,Long Zhu,Zhang Dan.Research progress in preparation and application of TEMPO-oxidized cellulose nanofibers[J].Journal of Materials Engineering,2015,43(8):84戴磊,龙柱,张丹.TEMPO氧化纤维素纳米纤维的制备及应用研究进展[J].材料工程,2015,43(8):84.
[10]Isogai Akira.Wood nanocelluloses:fundamentals and applications as new bio-based nanomaterials[J].Journal of Wood Science,2013,59(6):449.
[11]Dai Lei,Long Zhu,Chen Le.Application of TEMPO/Na Br/Na Cl O in papermaking[J].Transactions of China Pulp and Paper,2015,30(2):58.戴磊,龙柱,陈乐.TEMPO/Na Br/Na Cl O氧化体系在造纸中的应用[J].中国造纸学报,2015,30(2):58.
[12]Qian Jing Rong,Tang Ai Min,Song Jian Kang.Effectet of TEMPO Selective Oxidation on Cellulose-Morphology and Paper Properties[J].Paper&Paper Making,2010,29(10):22.钱荣敬,唐爱民,宋建康.TEMPO选择性氧化对纤维形态及成纸性能的影响[J].纸和造纸,2010,29(10):22.
[13]Yao Wen Run,Xu Qing Hua,Jin Li Qiang,et al.Effects of TEMPO/Na Br/Na Cl O-oxidation of Nanocrystalline Cellulose on Its Properties[J].Chemistry&Industry of Forest Products,2015,35(2):31.姚文润,徐清华,靳丽强,等.TEMPO/Na Br/Na Cl O氧化对纳米微晶纤维素性能的影响[J].林产化学与工业,2015,35(2):31.
[14]Jovana Milanovic,Mirjana Kostic,Petar Skundric.Structure and properties of TEMPO-oxidized cotton fibers[J].Chemical Industry&Chemical Engineering Quarterly,2012,18(2):473.
[15]HOU Qing-xi,CHAI Xin-sheng,ZHU Jun-yong.Determination of the Carboxyl Groups in Fibers by Headspace Gas Chromatography[J].China Pulp&Paper,2005,24(9):5.侯庆喜,柴欣生,朱俊勇.应用顶空气相色谱测定纸浆纤维的羧基含量[J].中国造纸,2005,24(9):5.
[16]Dai Lu,Dai Hong Qi,Yuan Yang Chun,et al.Study on oxidation kinetic of cotton fibers oxidation with TEMPO[J].Journal of Nanjing Forestry University(Natural Science Edition),2011,35(2):93.戴路,戴红旗,袁洋春,等.TEMPO氧化体系氧化棉纤维的动力学研究[J].南京林业大学学报:自然科学版,2011,35(2):93.
[17]Sbiai Adil,Kaddami Hamid,Sautereau Henry,et al.TEMPO-mediated oxidation of lignocellulosic fibers from date palm leaves[J].Carbohydrate Polymers,2011,86(4):1445.
[18]Sun Bin,Gu Chun Ju,Ma Jin Hong,et al.Kinetic study on TEMPO-mediated selective oxidation of regenerated cellulose[J].Cellulose,2005,12(1):59.
[19]Brodin Fredrik Wernersson,Theliander Hans.A comparison of softwood and birch kraft pulp fibers as raw materials for production of TEMPO-oxidized pulp,MFC and superabsorbent foam[J].Cellulose,2013,20(6):2825.
[20]Dang Zheng,Zhang Jian Guo,Ragauskas Arthur J.Characterizing TEMPO-mediated oxidation of ECF bleached softwood kraft pulps[J].Carbohydrate Polymers,2007,70(3):310.
[21]Pei Ji Cheng.Lignocellulosic Chemisty[M].Beijing:China Light Industry Press,2012.裴继诚.植物纤维化学[M].北京:中国轻工业出版社,2012.
[22]Saito T,Shibata I,Isogai A,et al.Distribution of carboxylate groups introduced into cotton linters by the TEMPO-mediated oxidation[J].Carbohydrate Polymers,2005,61(4):414.
[23]Li Lin,Zhao Shuai,Zhang Jin,et al.TEMPO-mediated oxidation of microcrystalline cellulose:Influence of temperature and oxidation procedure on yields of water-soluble products and crystal structures of water-insoluble residues[J].Fibers&Polymers,2013,14(3):352.
[24]Alemdar A,Sain M.Isolation and characterization of nanofibers from agricultural residues-Wheat straw and soy hulls[J].Bioresource Technology,2008,99(6):1664.
[25]Alila S,Besbes I,Vilar M R,et al.Non-woody plants as raw materials for production of microfibrillated cellulose(MFC):A comparative study[J].Industrial Crops&Products,2013,41(2):250.
[26]Kuramae Ryota,Saito Tsuguyuki,Isogai Akira.TEMPO-oxidized cellulose nanofibrils prepared from various plant holocelluloses[J].Reactive&Functional Polymers,2014,85:126.
[27]Meng Qi Jun,Li Hai Long,Fu Shi Yu,et al.The non-trivial role of native xylans on the preparation of TEMPO-oxidized cellulose nanofibrils[J].Reactive&Functional Polymers,2014,85:142.
[28]Potthast A,Schiehser S,Rosenau T,et al.Oxidative modifications of cellulose in the periodate system-reduction and beta-elimination reactions[J].Holzforschung,2009,63(63):12.
[29]Shibata Izumi,Isogai Akira.Depolymerization of cellouronic acid during TEMPO-mediated oxidation[J].Cellulose,2003,10(2):151.
[30]Isogai Akira,Saito Tsuguyuki,Fukuzumi Hayaka.TEMPO-oxidized cellulose nanofibers[J].Nanoscale,2011,3(1):71.
[31]Zhu Guang Yong,Zhu Xian,Xiao Zuo Bing,et al.Study of cellulose pyrolysis using an in situ visualization technique and thermogravimetric analyzer[J].Journal of Analytical&Applied Pyrolysis,2012,94(94):126.
[32]Orfao J J M,Antunes F J A,Figueiredo J L.Pyrolysis kinetics of lignocellulosic materials—three independent reactions model[J].Fuel,1999,78(3):349.
[33]Ouajai S,Shanks R A.Composition,structure and thermal degradation of hemp cellulose after chemical treatments[J].Polymer Degradation&Stability,2005,89(2):327.
[34]Fukuzumi Hayaka,Saito Tsuguyuki,Okita Yusuke,et al.Thermal stabilization of TEMPO-oxidized cellulose[J].Polymer Degradation&Stability,2010,95(9):1502.
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