漂白蔗渣浆中半纤维素含量对其TEMPO氧化性能的影响
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摘要
以碱法提取半纤维素后的漂白蔗渣浆为原料,研究2,2,6,6-四甲基哌啶-1-氧自由基(TEMPO)氧化过程,探讨半纤维素含量对不同氧化程度漂白浆TEMPO氧化过程及氧化浆性能的影响。结果表明在氧化剂用量充足的情况下,减少纸浆中的半纤维素含量有利于加快氧化速率并延长氧化时间,从而促进羧基的生成,并且氧化程度越高促进作用越明显。半纤维素的存在一定程度上阻碍了氧化剂进入纤维内部,不利于TEMPO反应的进行。由于氧化降解反应,纸浆中半纤维素含量的减少以及氧化剂用量增加,会使氧化后浆料的聚合度和得率有所降低。
Bleached bagasse pulp after hemicellulose-alkaline-extraction was used as the raw material to study its TEMPO(2,2,6,6-tetramethyl-1-piperidinyloxy) oxidation processes. Effects of hemicellulose contents on TEMPO oxidation of bleached pulp with different oxidation degrees and oxidized-pulp performance were investigated. The results show that decrease of hemicellulose content can accelerate oxidation and prolong the oxidation process when the oxidant is sufficient, which promotes the formation of carboxyl groups. Such effects were more obvious with higher oxidation degree of pulp. Hemicellulose obstructs the entering of oxidant into inner fiber, which is not available for the TEMPO reaction. Due to cellulose oxidative degradation, reduce of hemicellulose and increase of oxidant can decrease polymerization degree and oxidized-slurry yield.
Bleached bagasse pulp after hemicellulose-alkaline-extraction was used as the raw material to study its TEMPO(2,2,6,6-tetramethyl-1-piperidinyloxy) oxidation processes. Effects of hemicellulose contents on TEMPO oxidation of bleached pulp with different oxidation degrees and oxidized-pulp performance were investigated. The results show that decrease of hemicellulose content can accelerate oxidation and prolong the oxidation process when the oxidant is sufficient, which promotes the formation of carboxyl groups. Such effects were more obvious with higher oxidation degree of pulp. Hemicellulose obstructs the entering of oxidant into inner fiber, which is not available for the TEMPO reaction. Due to cellulose oxidative degradation, reduce of hemicellulose and increase of oxidant can decrease polymerization degree and oxidized-slurry yield.
引文
[1]LEE H V,HAMID S B,ZAIN S K.Conversion of lignocellulosic biomass to nanocellulose:structure and chemical process[J].The Scientific World Journal,2014,2014(4):631013-631033.
[2]陈良,汤骏,李丹杰,等.桥连结构对聚合物微球负载型TEMPO稳定性及催化氧化性能的影响[J].高校化学工程学报,2017,31(4):877-883.CHEN L,TANG J,LI D J,et al.Effects of bridge structure on stability and catalytic oxidation performance of polystyrene microsphere supported TEMPO[J].Journal of Chemical Engineering of Chinese Universities,2017,31(4):877-883.
[3]FRASCHINI C,CHAUVE G,BOUCHARD J.TEMPO-mediated surface oxidation of cellulose nanocrystals(CNCs)[J].Cellulose,2017,24(7):2775-2790.
[4]OKITA Y,SAITO T,ISOGAI A.Entire surface oxidation of various cellulose microfibrils by TEMPO-mediated oxidation[J].Biomacromolecules,2010,11(6):1696-1700.
[5]李英豪,耿延训,徐化能.乙酰化纳米纤维素纤维的制备及其凝胶机制研究[J].高校化学工程学报,2018,32(1):208-214.LI Y H,GENG Y X,XU H N.Preparation of acetylated cellulose nanofibrils and its gelation behavior[J].Journal of Chemical Engineering of Chinese Universities,2018,32(1):208-214.
[6]SAITO T,NISHIYAMA Y,PUTAUX J L,et al.Homogeneous suspensions of individualized microfibrils from TEMPO-catalyzed oxidation of native cellulose[J].Biomacromolecules,2006,7(6):1687-1691.
[7]ISOGAI A,SAITO T,FUKUZUMI H.TEMPO-oxidized cellulose nanofibers[J].Nanoscale,2011,3(1):71-85.
[8]SAITO T,HIROTA M,TAMURA N,et al.Oxidation of bleached wood pulp by TEMPO/NaClO/NaClO2 system:effect of the oxidation conditions on carboxylate content and degree of polymerization[J].Journal of Wood Science,2010,56(3):227-232.
[9]杨淑蕙.植物纤维化学[M].北京:中国轻工业出版社,2010:264-284.YANG S H.Lignocellulosic chemistry[M].Beijing:China Light Industry Press,2010:264-284.
[10]KURAMAE R,SAITO T,ISOGAI A.TEMPO-oxidized cellulose nanofibrils prepared from various plant holocelluloses[J].Reactive&Functional Polymers,2014,85(S1):I 126-133.
[11]CHAKER A,ALILA S,MUTJéP,et al.Key role of the hemicellulose content and the cell morphology on the nanofibrillation effectiveness of cellulose pulps[J].Cellulose,2013,20(6):2863-2875.
[12]SAITO T,HIROTA M,TAMURA N,et al.Individualization of nano-sized plant cellulose fibrils by direct surface carboxylation using TEMPO catalyst under neutral conditions[J].Biomacromolecules,2009,10(7):1992-1996.
[13]HIROTA M,TAMURA N,SAITO T,et al.Water dispersion of cellulose II nanocrystals prepared by TEMPO-mediated oxidation of mercerized cellulose at pH 4.8[J].Cellulose,2010,17(2):279-288.
[14]LIIMATAINEN H,VISANKO M,SIRVI?J A,et al.Enhancement of the nanofibrillation of wood cellulose through sequential periodate-chlorite oxidation[J].Biomacromolecules,2012,13(5):1592-1597.
[15]RODIONOVA G,SAITO T,LENES M,et al.TEMPO-mediated oxidation of norway spruce and eucalyptus pulps:preparation and characterization of nanofibers and nanofiber dispersions[J].Journal of Polymers&the Environment,2013,21(1):207-214.
[16]蒙启骏.半纤维素对TEMPO氧化纸浆制备纳米纤维素的影响[D].广州:华南理工大学,2015MENG Q J.The effects of hemicellulose on nanocellulose preparation by TEMPO-mediated oxidation from pulps[D].Guangzhou:South China University of Technology,2015.
[17]邓仲斌.蔗渣浆二氧化氯漂白过程中AOX减量技术研究[D].南宁:广西大学,2012.DENG Z B.Study on AOX reduction technology in the process of chlirine bleaching for bagasse pulp[D].Nanning:Guangxi University,2012.
[18]彭云云,武书彬,程江娜,等.离子色谱法测定蔗渣半纤维素中的单糖及糖醛酸含量[J].造纸科学与技术,2009,28(5):10-12.PENG Y Y,WU S B,CHENG J N,et al.Determination of monosaccharides and uronic acids in bagasse hemicellulose by ion chromatography[J].Paper Science&Technology,2009,28(5):10-12.
[19]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):5-9.HOU Q X,CHAI X S,ZHU J Y.Determination of the carboxyl groups in fibers by headspace gas chromatography[J].China Pulp&Paper,2005,24(9):5-9.
[20]李海龙,詹怀宇,张倩,等.TEMPO氧化对硫酸盐竹浆性能及纤维形态的影响[J].湖北造纸,2012(3):2-5.LI H L,ZHAN H Y,ZHANG Q,et al.Effect of TEMPO oxidation on properties and fiber morphology of kraft bamboo slurry[J].Hubei Pulp&Paper,2012(3):2-5.
[21]PENG F,REN J L,XU F,et al.Fractional study of alkali-soluble hemicelluloses obtained by graded ethanol precipitation from sugar cane bagasse[J].Journal of Agricultural&Food Chemistry,2010,58(3):1768-1776.
[22]SYVERUD K,CHINGA-CARRASCO G,TOLEDO J,et al.A comparative study of eucalyptus and pinus radiata pulp fibres as raw materials for production of cellulose nanofibrils[J].Carbohydrate Polymers,2011,84(3):1033-1038.
[23]HAQUE M A,CHO K M,BARMAN D N,et al.A potential cellulose microfibril swelling enzyme isolated from Bacillus sp.AY8enhances cellulose hydrolysis[J].Process Biochemistry,2015,50(5):807-815.
[24]戴路.预处理对TEMPO氧化体系的促进及动力学研究[D].南京:南京林业大学,2011.DAI L.The effect of pretreatment on TEMPO oxidation system and kinetic study[D].Nanjing:Nanjing Forestry University,2011.
[25]BESBES I,VILAR M R,BOUFI S.Nanofibrillated cellulose from alfa,eucalyptus and pine fibres:preparation,characteristics and reinforcing potential[J].Carbohydrate Polymers,2011,86(3):1198-1206.
[26]SANG X,QIN C,TONG Z,et al.Mechanism and kinetics studies of carboxyl group formation on the surface of cellulose fiber in a TEMPO-mediated system[J].Cellulose,2017,24(6):2415-2425.
[27]HOMMA I,ISOGAI T,SAITO T,et al.Degradation of TEMPO-oxidized cellulose fibers and nanofibrils by crude cellulase[J].Cellulose,2013,20(2):795-805.
[2]陈良,汤骏,李丹杰,等.桥连结构对聚合物微球负载型TEMPO稳定性及催化氧化性能的影响[J].高校化学工程学报,2017,31(4):877-883.CHEN L,TANG J,LI D J,et al.Effects of bridge structure on stability and catalytic oxidation performance of polystyrene microsphere supported TEMPO[J].Journal of Chemical Engineering of Chinese Universities,2017,31(4):877-883.
[3]FRASCHINI C,CHAUVE G,BOUCHARD J.TEMPO-mediated surface oxidation of cellulose nanocrystals(CNCs)[J].Cellulose,2017,24(7):2775-2790.
[4]OKITA Y,SAITO T,ISOGAI A.Entire surface oxidation of various cellulose microfibrils by TEMPO-mediated oxidation[J].Biomacromolecules,2010,11(6):1696-1700.
[5]李英豪,耿延训,徐化能.乙酰化纳米纤维素纤维的制备及其凝胶机制研究[J].高校化学工程学报,2018,32(1):208-214.LI Y H,GENG Y X,XU H N.Preparation of acetylated cellulose nanofibrils and its gelation behavior[J].Journal of Chemical Engineering of Chinese Universities,2018,32(1):208-214.
[6]SAITO T,NISHIYAMA Y,PUTAUX J L,et al.Homogeneous suspensions of individualized microfibrils from TEMPO-catalyzed oxidation of native cellulose[J].Biomacromolecules,2006,7(6):1687-1691.
[7]ISOGAI A,SAITO T,FUKUZUMI H.TEMPO-oxidized cellulose nanofibers[J].Nanoscale,2011,3(1):71-85.
[8]SAITO T,HIROTA M,TAMURA N,et al.Oxidation of bleached wood pulp by TEMPO/NaClO/NaClO2 system:effect of the oxidation conditions on carboxylate content and degree of polymerization[J].Journal of Wood Science,2010,56(3):227-232.
[9]杨淑蕙.植物纤维化学[M].北京:中国轻工业出版社,2010:264-284.YANG S H.Lignocellulosic chemistry[M].Beijing:China Light Industry Press,2010:264-284.
[10]KURAMAE R,SAITO T,ISOGAI A.TEMPO-oxidized cellulose nanofibrils prepared from various plant holocelluloses[J].Reactive&Functional Polymers,2014,85(S1):I 126-133.
[11]CHAKER A,ALILA S,MUTJéP,et al.Key role of the hemicellulose content and the cell morphology on the nanofibrillation effectiveness of cellulose pulps[J].Cellulose,2013,20(6):2863-2875.
[12]SAITO T,HIROTA M,TAMURA N,et al.Individualization of nano-sized plant cellulose fibrils by direct surface carboxylation using TEMPO catalyst under neutral conditions[J].Biomacromolecules,2009,10(7):1992-1996.
[13]HIROTA M,TAMURA N,SAITO T,et al.Water dispersion of cellulose II nanocrystals prepared by TEMPO-mediated oxidation of mercerized cellulose at pH 4.8[J].Cellulose,2010,17(2):279-288.
[14]LIIMATAINEN H,VISANKO M,SIRVI?J A,et al.Enhancement of the nanofibrillation of wood cellulose through sequential periodate-chlorite oxidation[J].Biomacromolecules,2012,13(5):1592-1597.
[15]RODIONOVA G,SAITO T,LENES M,et al.TEMPO-mediated oxidation of norway spruce and eucalyptus pulps:preparation and characterization of nanofibers and nanofiber dispersions[J].Journal of Polymers&the Environment,2013,21(1):207-214.
[16]蒙启骏.半纤维素对TEMPO氧化纸浆制备纳米纤维素的影响[D].广州:华南理工大学,2015MENG Q J.The effects of hemicellulose on nanocellulose preparation by TEMPO-mediated oxidation from pulps[D].Guangzhou:South China University of Technology,2015.
[17]邓仲斌.蔗渣浆二氧化氯漂白过程中AOX减量技术研究[D].南宁:广西大学,2012.DENG Z B.Study on AOX reduction technology in the process of chlirine bleaching for bagasse pulp[D].Nanning:Guangxi University,2012.
[18]彭云云,武书彬,程江娜,等.离子色谱法测定蔗渣半纤维素中的单糖及糖醛酸含量[J].造纸科学与技术,2009,28(5):10-12.PENG Y Y,WU S B,CHENG J N,et al.Determination of monosaccharides and uronic acids in bagasse hemicellulose by ion chromatography[J].Paper Science&Technology,2009,28(5):10-12.
[19]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):5-9.HOU Q X,CHAI X S,ZHU J Y.Determination of the carboxyl groups in fibers by headspace gas chromatography[J].China Pulp&Paper,2005,24(9):5-9.
[20]李海龙,詹怀宇,张倩,等.TEMPO氧化对硫酸盐竹浆性能及纤维形态的影响[J].湖北造纸,2012(3):2-5.LI H L,ZHAN H Y,ZHANG Q,et al.Effect of TEMPO oxidation on properties and fiber morphology of kraft bamboo slurry[J].Hubei Pulp&Paper,2012(3):2-5.
[21]PENG F,REN J L,XU F,et al.Fractional study of alkali-soluble hemicelluloses obtained by graded ethanol precipitation from sugar cane bagasse[J].Journal of Agricultural&Food Chemistry,2010,58(3):1768-1776.
[22]SYVERUD K,CHINGA-CARRASCO G,TOLEDO J,et al.A comparative study of eucalyptus and pinus radiata pulp fibres as raw materials for production of cellulose nanofibrils[J].Carbohydrate Polymers,2011,84(3):1033-1038.
[23]HAQUE M A,CHO K M,BARMAN D N,et al.A potential cellulose microfibril swelling enzyme isolated from Bacillus sp.AY8enhances cellulose hydrolysis[J].Process Biochemistry,2015,50(5):807-815.
[24]戴路.预处理对TEMPO氧化体系的促进及动力学研究[D].南京:南京林业大学,2011.DAI L.The effect of pretreatment on TEMPO oxidation system and kinetic study[D].Nanjing:Nanjing Forestry University,2011.
[25]BESBES I,VILAR M R,BOUFI S.Nanofibrillated cellulose from alfa,eucalyptus and pine fibres:preparation,characteristics and reinforcing potential[J].Carbohydrate Polymers,2011,86(3):1198-1206.
[26]SANG X,QIN C,TONG Z,et al.Mechanism and kinetics studies of carboxyl group formation on the surface of cellulose fiber in a TEMPO-mediated system[J].Cellulose,2017,24(6):2415-2425.
[27]HOMMA I,ISOGAI T,SAITO T,et al.Degradation of TEMPO-oxidized cellulose fibers and nanofibrils by crude cellulase[J].Cellulose,2013,20(2):795-805.