摘要
本文对麦草原料制备化学机械浆高白度漂白化学机械浆主要的制浆性能进行了对比研究,比较了三种不同的化学药品用于预浸渍阶段(碱性过氧化氢预处理、果胶酶/碱性过氧化氢预处理、中性亚硫酸钠预处理)对未漂白浆的光学和物理性能的影响,包括成浆白度、成浆强度指标、纤维筛分级分,而且也比较了磨浆的比能耗和废水污染负荷。研究结果表明:麦草原料经过碱性H_2O_2 (1.5%用量H_2O_2,2.0%用量NaOH,0.4%用量DTPA)预处理,制得的纸浆具有较高的白度和良好的物理强度。且磨浆废水污染负荷较低。纸浆的碱性过氧化氢可漂性较好。
选用过氧化氢(P)、过氧乙酸(Pa)和硼氢化钠(B)等不同类型的漂白药剂经过筛选试验,并分别优化了各自单段漂白的适宜条件。并对P/Pa/B进行了不同组合序列的漂白效果进行了研究。研究结果表明,过氧乙酸与过氧化氢最佳组合方式为PaP_1P_2 (过氧乙酸用量1.0%,两段H_2O_2用量皆为5%),这种漂白方式漂后麦草化机浆白度可以达到72.83%ISO;经过P_1P_2B (两段5.0%用量H_2O_2漂白,后续1.0%用量的NaBH_4还原)三段漂白后,漂白麦草化学机械浆的白度可达73.98%ISO。对比研究了新鲜麦草和储存麦草化机浆的漂白性能发现,麦草原料经过一段时间贮存后,对所制得的纸浆的后续漂白会带来负面影响,试验结果表明:麦草原料经过12个月时间的贮存,制得的麦草化学机械浆以相同的漂白工艺,即PaP_1P_2和P_1P_2B的工艺漂白后,成浆白度分别为67.09%ISO,70.83%ISO,因此原料的新鲜程度对于禾草类原料的化学机械浆的漂白性能影响十分显著。
漂白废液的研究结果表明:麦草化学机械浆纸浆P_1P_2B漂白工艺三段漂白废水BOD与COD总发生量分别为149.06kg/t浆和384.24kg/t浆,均低于PaP_1P_2漂白工艺三段漂白废水BOD与COD总发生量;从漂白废液气相色谱/质谱分析检测结果可以看出:两种漂白废液的主要污染物质成分构成较为相近,均含有芳香族化合物和脂肪族化合物,但是Pa漂白废液中酯类有机物和4, 4`-二羟基二苯丙烷的相对含量明显高于NaBH_4漂白废液的相对含量。这可以用来解释Pa漂白废液的污染负荷高于NaBH_4漂白废液污染负荷的现象。
麦草化学机械浆经过H_2O_2(用量4%、6%、8%、10%)漂白,纸浆酸化前后成浆白度(%ISO)存在明显差异,纸浆酸化后白度增值最小的为9.85个百分点,增值最大的16.12个百分点,同时酸化后成浆b*值也明显减小(趋向蓝色)。
纸浆返黄试验的结果表明:麦草化学机械浆经过PaP_1P_2、P_1P_2B处理与单独使用H_2O_2漂白相比,纸张白度稳定性明显提高;相比之下,硼氢化钠处理后,纸浆白度稳定性比过氧乙酸的处理效果明显,这主要是硼氢化钠处理纸浆以后,木质素结构中羰基数量的减少,从而增加了成浆白度稳定性。
通过对木质素碱性硝基苯氧化产物以及1H-NMR谱图分析的结果可以看出,麦草化学机械浆纸浆经过碱性H_2O_2漂白,以及后续NaBH_4还原处理以后,其中,香草醛约占40%～48%,紫丁香醛约占41%～53.10%,对羟苯甲醛约占6%～9%,说明麦草原料以及化机浆漂白后木质素属G-S-H型木质素。
麦草化学机械浆纸浆经过碱性H_2O_2漂白,木质素中酚羟基含量(0.29个/C9)略高于原料中的酚羟基含量(0.28个/C9),说明H_2O_2漂白不能有效地减少木质素中酚羟基这类助色基团的数量。麦草化机浆H_2O_2漂白后,总的羰基含量由原料木质素中的0.1063个/C9减少到0.0782个/C9,减少了26.43%;而后续使用NaBH_4还原处理纸浆木质素中共轭羰基数量由H_2O_2漂白后的0.0782个/C9下降到0.0235个/C9,减少了69.95%,这是由于NaBH_4还原处理后,与苯环的共轭结构,被还原成Cα-OH结构;破坏了木质素中共轭发色基团,提高了成浆白度及其白度稳定性。
The pulping properties of wheat straw materials by chemi-mechanical pulping process were investigated and compared in this thesis. Investigations on influences of impregnation using three kinds of pretreatments process(alkaline peroxide pretreatment, pectinase /alkaline peroxide pretreatment, neutral sodium sulfite pretreatment ) on unbleached chemimechanical pulps including optical and physical properties, were carried, such as coarse pulp brightness, coarse pulp strength, results of fiber screen classified parts , and specific energy consumption of refing process and COD load of effluent generated by pulping process were also contrasted. Results shows that higher pulp brightness, lower pollution load of effluent generated by refining process, better pulp strength and bleaching performance can be gathered through chemi-mechanical pulping process.Therefore, alkaline hydrogen peroxide pretreatment is a feasible method for wheat straw chemical mechanical pulping process.
High brightness of wheat straw chemi-mechanical pulp bleached by peracetic acid and sodium borohydride combined with alkaline peroxide was gained. The final pulp brightness could be 72.38% ISO under the Pa optimal condition(peracetic acid dosage 1.0%, bleaching time 120min, pH 5, pulp consistency 20%), associated with two stage 5.0% H_2O_2 for multi-stage bleaching (PaP_1P_2 bleaching process)of wheat straw chemical mechanical pulp; The final brightness of wheat straw chemi-mechanical pulp bleached by NaBH_4 (NaBH_4 dosage 1.0%, bleaching time 60min, pH 10-11, pulp consistency 10%)associated with two stage 5.0% H_2O_2 could be 73.98%ISO. After storage for period of time, the appearance color of wheat straw becomes darker and deeper due to the changes of lignin from wheat straw materials, which adding the bleaching difficuty. The brightness of pulp made by wheat straw material storaged for 12 months could only be achieved at 67.09%ISO and 70.83%ISO respectively, using the same bleaching process(PaP_1P_2, P_1P_2B1.0 ), Results shows that the short storage-time material is important to wheat straw chemi-mechanical bleaching.
The research on effluent from bleached pulp indicated that both COD value and BOD value of bleaching effluent from wheat straw chemi-mechanical pulp P_1P_2B bleaching stages are lower than that of PaP_1P_2, which are 149.06 kg/t pulp and 384.24 kg/t pulp respectively. The molecular structures of pollutant in these two kinds of effluent are similar, both contain aromatic compounds and aliphatic compounds, which can be determined by chromatography and mass spectrometry. The content of esters organic compounds and 4,4`-(1-methylethylidene) bis- organicas from Pa bleaching effluent is obviously higher than the content of organicas from NaBH_4 bleaching effuent. This could be one of the reasons which result in the pollution load of Pa bleaching effluent is higher than that of NaBH_4 bleaching effluent.
There is an obvious difference for wheat straw chemi-mechanical brightness of pulp bleached by H_2O(24%、6%、8%、10% dosage)after acidfication, the pulp least brightness gain can be reached by 9.85 % ISO, the maximal brightness gain can be reached by 16.12 % ISO, and b* value decreased after acidfication
Pulp yellowing experiment results show that wheat straw chemi-mechanical pulp brightness stabilization is significantly improved using 1.0% peracetic acid or 1.0% NaBH_4 compared with H_2O_2 bleaching results; in contrast, the treatment efficiency for pulp brightness stabilization treated by 1.0% NaBH_4 is more obvious than the pulp stabilization treated by 1.0% peracetic acid. Improvement of brightness stabilization can be judged by quantity of carboxyl, because of the quantity of carboxyl of lignin from pulp treated by NaBH_4 decreasing, the pulp brightness stabilization is improved.
Determination of nitrobenzene oxidation products of lignin by GC and spectra analysis for ~1H-NMR show that the lignin of wheat straw materials, chemi-mechanical pulps ,pulp bleached by alkaline H_2O_2 and pulps treated by H_2O_2/NaBH_4 is a G-S-H type lignin (the proportion of guaiacylpropane units 40%～48%, syringylpropane units is about 41%～53.10%, and p-hydroxyphenylpropane units is about 6%～9%).
Amount of auxochrome phenolic hydroxyl(0.29 unit/C9)in lignin from H_2O_2 bleaching chemi-mechanical pulp is slightly higher than one of material(0.28 unit/C9), so amount of auxochrome phenolic hydroxyl can not be effectively decreased by alkaline peroxide bleaching process. Conjugated carbonyl content in lignin from H_2O_2 bleaching chemi-mechanical pulp decreases by 26.43% from 0.1063 unit/C9 to 0.0782 unit/C9, the content of conjugated carbonyl in lignin from pulp reduced by NaBH_4 decreases further by 69.95% from 0.0782 unit/C9 to 0.0235 unit/C9. Conjugated carbonyl in lignin from wheat straw chemi-mechanical pulp was reduced from Cα=O structure to Cα-OH structure by NaBH_4 reducing process after H_2O_2 bleaching process, this is the reason for pulp brightness improvement and pulp brightness stablilization increase.
引文
[1]中国造纸协会.中国造纸工业2006年年度报告[J].中华纸业, 2007, . 28( 6):6-9
[2]王鸿文.中国造纸工业利用非木材纤维制浆现状和前景展望[C]华东六省一市造纸学会第二十一届学术年会论文集,2007,32
[3]张国中,黄海东.秸秆综合利用研究发展及展望[J]湖北农机化,2004,(6):24
[4]国家粮油信息中心http://www.cnmf.net/news/echo.php?id=42628
[5] Kim Y S, Kurahashi A, Meshituska G. Characteristics of the chemical structure of lignin in fast-growing poplar[J]. Mokuzai gakkaishi. 1996,42(8):782
[6] Sun R C et al. Fractional isolation and characterization of polysaccharides from iol palm trunk and empty fruit bunch fibers[J]. Holzforschung,1999,53:253
[7] Kim Y S,Structural feature of lignin in cell-walls of normal and fast growling poplar-linkage types of all-bound hydroxybenzoic and hydroxycinnamic acids[J]. Mokuzai gakkaishi. 1995,41(9):837
[8] Pan X G,Sano Y,Ito T. Atmospheric acetic acid pulping of rice straw II: Behavior of ash silica in rice straw during atmospheric acetic acid pulping and bleaching[J]. Holzforschung,1999,53:49.
[9]王菊华主编.中国造纸原料纤维特性及纤维图谱[M].北京:中国轻工出版社,1999,130-131
[10]邬义明主编.植物纤维化学[M].北京:中国轻工出版社,1999,34
[11]李忠正.禾草类纤维制浆可持续发展的研究[J].国际造纸,1999,18(3):14-16
[12]李忠正.禾草类纤维制浆特性及进一步发展我国非木材纤维造纸的对策[J]中华纸业,2006,27(2):6-7
[13]周亚军,袁志润.高得率浆的特性与应用[J]国际造纸,2007,26(1):1-10
[14]房桂干,沈兆邦.发展高得率浆生产是保证我国造纸工业可持续发展的重要途径之一[J]江苏造纸,2001,(1):7-9
[15]万金泉,陈中豪.非木材化学机械浆.北方造纸,1994,(3),30.
[16]胡志军,李友明.第三代磨浆机—双螺杆挤浆机[J]湖北造纸,2005,(1):39-42
[17]王平,沈晓阳,薛强.双螺杆磨浆机的研究与应用[J]中国造纸,2004,23(1):45
[18] Xu E.C., Sabourin, M.J. Evaluation of化学机械浆and BCTMP for market pulp from South America Eucalyptus. Tappi,1998,82(12):75-82.
[19] Johan Sundholm, Joseph A. Kurdin. Papermaking Science and Technology[M],Book 5: Mechnical Pulping. New York: Tappi Press,edited by Jan Sundholm,KCL,The Finnish Pulp and Paper Research Institute. 2000,245-247
[20] Gierer J. Basic Principles of Bleaching - Part1 : Cationic and Radical Processes[J]. Holzforschung,1990,44(5):367-394
[21] Gierer J. Basic Principles of Bleaching-Part 2:Anionic Processes[J]. Holzforschung,1990,44(6):395-400
[22] Josef Gierer. Finn Imsgard. The reaction of lignins with oxygen and hydrogen perxide in alkaline media[J]. Svensk Papperstidning, 1977, (16):510。
[23]邹鸿春,谭国民.几种助剂在过氧化氢漂白中的应用[j]纸和造纸,2004,1(1):34-35
[24] Liebergott N. Peracid delignification and bleaching of chemical pulps PartⅠ:delignification[J]. Pulp and Paper Canada,1996,97(2):21-26
[25] Liebergott N.Peracid delignification and bleaching of chemical pulps Part II:oxidation[Jj].Pulp and Paper Canada,1996,97(5):73-76
[26]王传虎,方荣生.过氧乙酸制备及稳定性研究[J]化学推进剂与高分子材料,2006,4(1):55-57
[27] J A Dean,Handbook of Organic Chemistry[J]. Mcgraw-Hill Book Company,1987,8-14
[28] W Muller-Litz,et al. Peracetic acid bleaching:a chlorine-free and environmentally compatible process. ITB (Dyeing/Printing/Finishing),1997,43(3):37-38
[29]邹艳洁,徐立新,郝玲.过氧乙酸漂液的稳定性及其稳定剂的研究[J]中华纸业,2006,27(3):63-66
[30]陆海燕,姚培正.四乙酰乙二胺对过硼酸钠活化作用的研究[J]日用化学工业,2003,33(1):15-18
[31] C.Leduc,M.Garceau,C.Daneault and S.Robert. Bleaching of a mechanical pulp with Sodium Percarbonate and Amineborane-Bleaching Response and Brightness Atability[J]. JPPS,2002,28(5):171-175
[32]陈嘉翔主编.制浆原理与工程[M].北京:中国轻工业出版社,1990,10:275
[33]林涛,殷学风,刘建连.甲脒亚磺酸(FAS)用于磨木机械浆漂白的研究[J]西南造纸,2004,33(3):23
[34] P M Sharman.BCTMP growth-demand to continue world- wide during future decades[J]. PPI special report. 1991,S2-S30
[35] T K Kirk,et al. Biotechnology applications and implications for the pulp and paper industry[J]. Tappi Journal,1983,66(5):45-51
[36] Viikari. Bleaching with enzymes. Proceedings of the Third International Conference on Biotechnology in the Pulp and Paper Industry,Stockholm,1986:67-69.
[37] J.S. Tolan. Survey of xylanase enzyme usage in bleaching in Canada[J]. PPC,1995,96(12):107-110
[38]洪枫,刘明山,房桂干,沈兆邦.木聚糖酶预处理对麦草化学机械浆可漂性及白度的改善[J]林产化学与工业,2001,21(1):21-28
[39] Puls J,et al. Biotechnology in Pulp and Paper Manufacture.[J] Ch. 1990,16:183-190
[40]劳嘉葆.聚木糖酶的漂白作用[J].西南造纸,2005,34(6):45
[41]白延坤,刘秉钺,何连芳.果胶酶及其在制浆造纸上的应用[J].中国造纸学报,2006,21(2):88-91
[42] Ridey,O`Neill B L, Mohnen M A,et al. Structure,biosynthesis and oligogacturonide-related signaling[J]. Phytochemistry,2001,57:929
[43] Thornton J. Enzymatic degradation of polygalacturonic acids released from mechanical pulp during peroxide bleaching[J] Tappi,1994,77(3):161
[44] Michelle Ricard,José-Antonio Orccotoma,Jim Ling,et al. Pectinase reduces cationic chemical costs in peroxide-bleached mechanical grades[C]. Pacwest2004 Technical Papers-Session 2B-Mechanical Pulping/Papermaking,2004,216-217
[45] Ian Reid,Michelle Ricard. Pectinase in papermaking:solving retention problems in mechanical pulps bleached with hydrogen peroxide[J]. Enzyme and Microbial Technoliogy,2000,26(2):115
[46]白木,周洁.生物技术在造纸工业中的应用[J].浙江造纸,2003,27(3):43
[47]黄文荣,陈中豪.木质素的研究与应用前景[J]江苏造纸,2003,(1):19
[48] Warren JR,Marshall BJ. Unidentified curved bacilli on gastric epithelium in active chronic gastritis[J]. Lancet,1983,1(8336):3~5
[49]葛培锦麦草木聚糖酶-烧碱法化学机械浆制浆研究[D],南京林业大学博士论文,2005,17
[50]马邕文,陈中豪木质素结构对麦草化机浆白度及可漂性的影响[M]中国造纸学报,1998,(3):34
[51] Nimz H.H.,Robert D. Carbon-13 NMR Spectra of Lignins,8. Stuctural Differences between Lignins of Hardwoods,Sofrwoods,Grasses,and Compression Wood. Holzforschung,1981,35:16-26
[52]南京林业大学主编.木材化学[M].北京:中国林业出版社,1987,69.
[53]张爱萍,刘传富.光谱技术在木质素结构分析中的应用[J]中国造纸学报,2007,22(3):97
[54]钟颖,樊永明仪器分析在木质素化学中的应用[J]现代仪器,2006,3:11
[55] Sun X F,Sun R C,Tomkinson J,et al. Isolation and characterization of lignins,hemicelluloses and celluloses from wheat straw by alkaline peroxide treatment. Cellulose chemistry and technology,2003,37:283
[56]方惠群,于俊生,史坚编著.仪器分析[M].北京:科学出版社,2002,2:271.
[57] Strong F C. Theoretical Basis of the Bouguer-Beer Law of Radiation Absorption[J]. Anal Chem, 1952,(24):338-342.
[58] Strong F C. Theoretical Basis of the Bouguer-Beer Law of Radiation Absorption-Correction[J]. Anal Chem,1952,(24):2013.
[59]杨崎峰,詹怀宇.纤维的表面性能及表面分析技术[J].中国造纸学报,2005,2(20):189.
[60] Duchesne,Isabelle,Daniel. Ultrastructure of Wood Fiber Surfaces as Shown by a Variety Microscopic Methods-a Review[J]. Nodic Pulp and Paper Reserch Journal. 1999,14(2):129.
[61]周学飞.核磁共振法在研究木质素和碳水化合物结构方面的应用[J]中国造纸学报,1998, (13):86.
[62]张志城余贻骥.化学机械法制浆[M/OL].[出版社不详]. [2008-2-20]. http://baike7.com/baike/%C%BB%FA%D0%B5%B7%A8%D6%C6%BD%AC.html.
[63] Eric Chao Xu.非木材纤维的化学机械浆制浆第一部分:红麻和谷草类纤维原料[J].国际造纸, 2000,19(6):1.
[64] Tahara.T. Journal of Fermentation Technology[J]. 1972,50(9):655-656.
[65]陈嘉翔,李元禄,张志芬等.制浆原理与工程[M].北京:中国轻工业出版社,1990,152.
[66]刊讯.用果胶酶预处理木片的机械制浆[J].纸和造纸. 2005,(5):102.
[67]陈嘉翔,李元禄,张志芬等.制浆原理与工程[M].北京:中国轻工业出版社1990,10:220.
[68]李忠正.禾草类纤维制浆特性及进一步发展我国非木材纤维造纸的对策[J].中华纸业, 2006,27(2):7.
[69] Pan G X,Leary G J.The bleachability of wheat straw alkaline peroxide mechanical pulp[J],Cellulose Chem. Technol,2000,34:537-547
[70] Liebergott N. Peracid delignification and bleaching of chemical pulps,PartⅠ:delignification[J]. Pulp and Paper Canada. 1996,97(2):21-26.
[71] Liebergott N. Peracid delignification and bleaching of chemical pulps,PartⅡ:oxidation[J]. Pulp and Paper Canada.1996,97(3):73-76.
[72]林涛,殷学风,刘建连.甲脒亚磺酸(FAS)用于磨木机械浆漂白的研究[J].西南造纸,2004,33(3):23-25.
[73]屈维均主编制浆造纸试验[M]北京:轻工业出版社,1990,108
[74] G. A. Smook,Hand book for pulp and paper technologists[J],Reprint by Angus Wilde Publications inc. 2001,59-62
[75] Xu E.C., Sabourin, M.J. Evaluation of化学机械浆and BCTMP for market pulp from South America Eucalyptus[J] Tappi,1998,82(12):75-82
[76] PAN G X. Thomson Ci and Leary G J. The role of ferulic acid removal during bleaching of wheat straw mechanical pulp with peroxygenreagents[J]. Holzforsehung. 2003,57(3):282-288
[77]沈葵忠,房桂干,储富祥等杉木CTMP浆高温高浓度过氧化氢漂白[C]江苏省造纸学会第九届学术年会论文集,2007,307
[78]李忠正等麦草原料几种蒸煮方法反应历程的比较[J].中国造纸,1983,2(3):21
[79]李忠正,洪启清,张大同.试论麦草制浆的规律性[J].中国造纸,1986,5(1):24-28.
[80] Sun R C,Salisbury D,Tomkinson J. Chemical composition of lipophilic extractives released during the hot water treatment of wheat straw. Bioresource Technol. 2003,88:95-101.
[81] Sun R C, Mark Lawther J,Banks W B. Influence of alkaline pre-treatments on the cell wall components of wheat straw. Industrial crops and products,1995,4:127-145.
[82] W Muller-Litz,et al. Peracetic acid bleaching:a chlorine-free and environmentally compatible process. ITB (Dyeing/Printing/Finishing),1997,43(3):37-38.
[83] Schlesinger HI,Brown HC, Finholt AE, et al. Sodium borohydride, its hydrolysis and its use as a reducing agent and in the generation of hydrogen. J Am Chem Soc,1953,75:215-218.
[84] Brown HC,Brown CA. New,highly active metal catalysts for the hydrolysia of borohydride. J Am Chem Soc,1962,84:1493-1494.
[85] Davis WD, Mason LS,Stegman G. The heats of formation of sodium borohydride,lithium borohydride and lithium aluminum hydride. J Am Chem Soc,1949,71:2775-2781.
[86] Kreevoy MM,Jacobson RW. The rate of decomposition of NaBH4 in basic aqueous solutuions[J]. Ventron Alembic. 1979,15(2):2-3.
[87] Amendola SC,Sharp-Goldman SL,Janjua MS, et al, A safe portable hydrogen generator using aqueous borohydride solutions and Ru catalyst[J]. Int J Hydrogen Energy,2000,25(10):969-975.
[88]罗巨生.化学热磨机械浆连二亚硫酸钠第二段漂白技术研究[J].中华纸业,2002,25(3):34.
[89] Robert L,Irvine et al. An Organic Loading Study of Fullscale Sequencing Batch Reactors[J]. JWPFC,1985,57(8):56-58
[90]王双飞,高扬.白腐菌处理前后苇浆CEH漂白废液中氯代酚类化合物的气相色谱/质谱分析[J].中国造纸学报,1996,11:36.
[91] Sutherland J B,Selby A L,Freemanm J P,et al. Appl. Environ. Microbiol. 1991,57(11):3310.
[92]武书彬,梁文芷.尾叶桉碱性亚硫酸钠化机浆制浆废水的污染废液负荷及特性[J].中国造纸,1995,14(2):9.
[93]高扬,闫冰,张曾等.白腐菌生化降解前后废液的气相色谱/质谱分析[J].中国造纸学报,2002, 17(1): 44.
[94] Munch J W,Eichelberger J W,et al. Evaluation of 48 Compounds for Possible Inclusion in US EPA Method 524.2, Revision 3.0:Expansion of the Method Analyte List to Tatal of 83 Compounds. J. Chromatogr. Sci. 1992,30(12):471
[95] Morales A,Birkholz D A,Hrudey S E,et al. Methodologies for the Measurement of Chlorinated Organic Compounds in the Environment, Chlorophenols and Related Compounds. 1992 Spring Conference:Canadian Pulp & Paper Association,Technical Section,Session:6:Environment,Paper (2):13(May 16,1992:CPPA)
[96]陈嘉翔主编.制浆原理与工程[M].北京:中国轻工出版社,1995,328-329.
[97] Pauler N,Paper optics. Lorentzen & Wettrre, Sweden.Puebla, C. Whiteness assessment: a primer. Axiphos GmbH[M], Germany, 2004,28-30
[98]李昭成,杨桂花,孔凡功.利用调色原理提高纸张白度的研究[J].山东轻工业学院学报,2002,3(16):59-62.
[99] Neish,A.C. Monomeric Intermediates in the Boothesis of Lignin in Constitution and Biosynthesis of Lignin[J],Frendenberg K. etc Ed. Springer-Verlag,Berlin,1968,5-43.
[100]中野凖三，樋口隆昌等.木材化学[M].鲍禾,李忠正译.北京:中国林业出版社,1989,229.
[101]周亚军,袁志润,江智华.高得率浆的特性与应用[J].国际造纸,2007,26(1):1.
[102] Zhou Y,Zou X. Achieving Desired End-use Performance by Using HYP in Wood-free Coated Papers[C]. 2003 International Mechanical Pulping Conference,Quebec City,Canada. 2003,368-370
[103]周亚军,袁志润.高得率浆白度稳定性及返黄抑制的研究[J].国际造纸,2007,26 (4):5.
[104] Gurnagul N, et al. The Mechanical Permanence of Paper: A literature review[J]. JPPS,1993, 19(4):160.
[105] Zou X. During Storage and Shipping,Nitrogen Oxiges Can Cause Rapid Yellowing and Degradation of Pulp and Paper Products[C]. 88th PAPTAC Annual Meeting. Montreal,QC. 2002,52-57.
[106] Nolan P,Van den Akker J A,Wink W A. The Fading of Groundwood by Light. II. The Physical Mechanism of Fading[J]. Paper Trade J.,1945,121(11):101.
[107] Davidson R S. The Photodegradation of Some Naturally Occuring Polymers[J]. J.Phtochem. Photobiol. B:Biology,1996,(33):3.
[108] Heitner C. Light-Induced Yellowing of Wood-Containing Papers, AnEvaluation of the Mechanism, in Phtochemistry of Lignocellulosic Materials, ACS Symp. Series 531[M]. Washington DC:heitner C and Scaiano J C,Editors,1993,2.
[109] Leary G J. Recent Progress in Understanding and In hibiting the light-Induced Yellowing of Mechanical Pulps[J]. JPPS,1994,20(6):154.
[110] Forssk?hl I. Towards An Understanding of the Photoyellowing of Pulps and papers[J]. Trends in Photochem,1994,3:503.
[111] Fang Guigan. Light-induced Yellowing Mechanism of Poplar化学机械浆Pulps and Its` Inhibition Measures[D]. 2002,98.
[112] Tschirner U,Dence C. Attempts to Photostabilize Norway Spruce TMP by Chemical Modification[J]. Paperi ja Puu,1988,70(4):338.
[113] D. Fengel,G. Wegener. Wood Chemistry Ultracture[J], Reactions,1982,132.
[114]中野凖三，樋口隆昌等.木材化学[M]鲍禾,李忠正译.北京:轻工业出版社,1988,169.
[115] E. Adler. Lignin chemistry– Past, present and future[J]. Wood Sci Technol, 1977,(11):170.
[116] H. Nimz. Das Lignin der Buche - Entwurfeines Konstitutsionsschemas[J]. Angew Chem. 1974,86:336.
[117] K. Kratzl,et al. Constitution of the side chains of lignin[J].Tappi. 1957,40:269.
[118] O.Goldschmid. Determination of phenolic hydroxyl content of lignin preparations by ultraviolet spectrophotometry[J]. Anal. Chem. 1954,26:1421.
[119] B. L. Lenz. Application of nuclear magnetic resonance spectroscopy to characterization of lignin[J] Tappi. 1968,51:511.
[120] A.Bjorkman,et al. Studies on finely divided wood. Part3. Extraction of lignin-carbohydrate complexes with neutral sovents[J]. Svensk Pappeistidning-Nordisk Cellulosa, 1957,60(7):285.
[121] Butler,et al. Precipitation of Sulfides form Homogeneous Solutions by Thioacetamide Anal. Chem 1956,28:1468.
[122] E.Adler,et al. The Present State of the Problem of Lignin–Carbohydrate Bonds[J]. Svensk Papperstidn 1958,61:641.
[123] P. Mansson. Gel permeation chromatographic study of the molecular weight distribution of tannins in the wood, bark and leaves of Eucalyptus sppHolzforschung. 1983,37:143
[124] O. Faix,et al. The influence of particle size and concentration in transmission and diffuse reflectance spectroscopy of wood.[J] Holzforschung,1992,46:221-226
[125]中野准三著.木质素的化学基础和应用[M]高洁等译.北京:中国轻工业出版社,1990,46-53
[126] T.Higuchi,et al. Method of increasing oral absorption of. beta.-lactam antibioticsJapan[J] Wood Rrs,1972,18:183
[127] M.Erichson,et al. Analysis Using Gas-Chromatography of Lignin Oxidation-Products .8. Structure of Spruce Lignin. Acta[J],Chem. Scand. 1973,27:1673
[128] I.A. Pearl,et al. Cellulose Column Chromatographic Separation of lignin Oxidation Products[J]. Tappi, 1956,39;171.
[129] Sun,R. C.,Tomkinson J.,Sun S. F.,et al. Fractional isolation and physico-soluble lignins from fast-growing poplar wood[J]. Polymer,2000,41:8409.
[130] Evtuguin, D. V., Neto., C. P., Silva, et al. Comprehensive study on the chemical structure of dioxane lignin feom plantation eucalyptus globlus Wood[J]. J. Agric. Food Chem., 2001,49:4252.
[131] Knut Lundquist,Brita Ohlsson,Rune Simonson. Isolation of lignin by means of liquid-liquid extraction[J]. Svensk Paperstidning,1977,(5):143.
[132] Stephen Y. Lin,Carlton W. Dence. Methods in Lignin Chemistry[M]. New York:1992,243.
[133] Stephen Y. Lin,Carlton W. Dence. Methods in Lignin Chemistry[M]. New York:1992,301-303.
[134] M, Mona, Bylund, et al. Svensk Papperstidn[J] 1977,73:521.
[135]石淑兰,何福望.制浆造纸分析与检测[M].北京:中国轻工业出版社,2003,56-59
[136] Erich Adler et al. Zur Kennois der Carbonylgruppen in Lignin[J] I Acra Chem. Scand,1959,13(1):75-96.
[137]陈嘉翔,余家鸾.植物纤维化学结构的研究方法[M].广东:华南理工大学出版社,1989,136
[138]Josef Gierer. Basic Principles of Bleaching[J]. Holzforschung,1990,44(6):395.
[139]谢来苏,詹怀宇.制浆原理与工程[M],北京:中国轻工业出版社,2001,254.
[140]马邕文,陈中豪.木质素结构对麦草化机浆白度及可漂性的影响[J]中国造纸学报,1998,13:37
[141] H. P. Naveau, Can. J. Chem[M]. 1969,46:1893.
[142] Fu shiyu, FTIR Analysis of Residual Lignin in Kraft Pulp during Biobleaching[J]. Jurnal of Celulose Science and Technology, 2000,8 (2):30-31.
[143]陈嘉翔,余家鸾.植物纤维化学结构的研究方法[M].广州:华南理工大学出版社,1989,89-92
[144] Sun R C,Tomkison J,Wang S Q,et al. Characterization of lignins from wheat straw by alkaline peroxide treatment[J]. Polymer Degradationand Stability,2000,(67):101-109.
[145] Sun R C, Sun X. F, Wang S. Q, et al Ester and ether linkages between hydroxycinnamic acids and lignins from wheat、rice、rye、and barley straws, maize stems, and fast-growing poplar wood[J]. Industrial Crops and Products,2002,(15):179-188.
[146] Bassilakis R,Carangelo R M,Wojtowicz M A. TG-FTIR analysis of biomass pyrolysis[J]. Fuel,2001,80:1765-1786.
[147]中野准三.木质素的化学[M].高洁等译北京:轻工业出版社. 1988:230.
[148]中野凖三，樋口隆昌等.木材化学.鲍禾,李忠正译.北京:轻工业出版社,1988,169.
[149] Schmidt J.A.,Heitner C.,J. Wood Chem and Technol.,1993,13(3):309-325