【作者】 王东香；

【导师】 陆文达；

【作者基本信息】 东北林业大学 ， 木材科学与技术， 2001， 博士

【摘要】 由酸雨引发的土壤中铝的活化和营养成分的淋失，严重影响着世界众多地区森林和农作物的正常生长、发育。而我国中小型造纸企业的制浆黑液排放问题，不仅严重污染环境，而且危及企业本身的生存、发展。本研究从利用黑液、改良酸性土壤的角度，开展了工业硫酸盐木素（KL）用作土壤改良剂的研究，讨论了磺化改性过程中各反应因子对磺化效果的影响；分析了氧碱处理改性木素的化学结构特征；应用紫外光谱（UV）、傅立叶转换红外光谱（FTIR）、气相色谱（GC）、电感等离子体耦合发射光谱（ICP）、凝胶过滤色谱（GFC）、核磁共振谱（NMR）等现代波谱技术，探讨了改性木素与铝离子(Al³⁺)的结合机理；通过种植实验综合评估了改性木素在缓解铝毒、改良土壤方面的效果。 电导滴定实验得出，改性木素中的酸性基因可以分成三类，即强酸性基团（A）、中等酸性基团（B）和弱酸性基因（C）。自由基磺化处理的反应机理，主要是在酚羟基的邻位引入了磺酸基（A）。磺化木素S-1的FTIR谱图1217和1143cm^-1吸收强度增大的信息（和KL相比），佐证了磺酸基的引入。 氧碱处理改性木素的化学分析结果见下表；┌────┬────┬─────┬────────────────┬────┐│改性本素│OCH₃（%）│总糖（%） │C₉单元式 │COOH（%） │├────┼────┼─────┼────────────────┼────┤│O₄ │8.49 │0.07 │C₉H_10.45O_3.7（OCH₃）₀₅₃│10.82 │└────┴────┴─────┴────────────────┴────┘ 氧碱处理改性木素的化学分析结果表明，改性木素的羧基含量明显增加，在氧碱处理的过程中，由于芳环的开裂，形成了己二烯二酸结构，因此改性木素具有较高的反应活性，易与Al³⁺形成络合。硝基苯氧化和¹HNMR分析结果辅证了改性木素中仍保留有KL中高分子的组分，使得制备的样品在酸性环境中，不仅易与Al³⁺络合，而且还具有较强的吸附和缓冲性能。 通过对Al³⁺改性木素混合液在不同pH值下的凝胶色谱分析，我们得出Al/S-1随着pH的不同而改变，Al/S-1代表的是每摩尔改性木素络合Al³⁺的量。PH5.8时，Al/S-1最大为0.358。即每摩尔改性木素络合Al³⁺的最大量为0.358摩尔。木素-铝络合物的形成进一步被电位滴定证实。 由氧-碱和自由基磺化处理的改性木素种植实验的结果表明：磺化木素和氧-碱处理改性木素能明显减缓铝毒，改善植物根系的生长情况，不同的改性木素，减缓铝毒的能力不同，对植物根系生长的影响也就不同，这与改性木素的结构组成或者说与改性木素中官能团的种类、含量密切相关。苏木精染色实验从另一角度也证实了上述结论。 本研究为中、小型造纸企业制浆黑液的利用提供了科学依据，其改性木素作为土壤改良剂在防止土壤酸化，保护生态环境方面具有现实意义。更多还原

【Abstract】 It is well known that Al ions eluted into soil solution under acidic conditions have a serious toxic effect to plant and forest. The problem of draining black liquor of middle and small-scaled Papermaking Company, not only polluted the environment seriously, but also endangered their existence and development. In this study, new soil conditioning agents were developed from Kraft lignin. We modified Kraft lignin by radical sulfonation and alkaline -oxygen treatment .T’he effect of the reaction factor on the sulfonation were studied. The chemical structure feature of modified lignin by alkaline-oxygen treatment was analyzed. Interaction between Al 3+ and modified lignin was examined by FTIR> GC, K^ GFC, NMR etc. The ability of modified lignin to retard the A13+ toxicity and improve the soil condition was evaluated by planting experiment.Conductometric titration of modified lignin indicate that acidic groups in the modified lignin can be classed into three groups, the strongly acidic group (A), intermediately acidic group (B) and weakly acidic group (C). Sulfonic acid group was introduced to or/Ao-position of phonlic hydroxyl group during radical sulfonation treatment. Introduction of sulfonic acid group to Kraft lignin by radical sulfonation could be confirmed also by the increased intensities of band at 1217 cm"1 and 1142 cm’1 in its FTIR spectrum.The chemical analysis result of modified lignin by alkaline-oxygen treatment is as following:The chemical analysis result of modified lignin by alkaline-oxygen treatment showed that the carboxyl group of modified lignin increased, since muconic acid type structure were generated from phenolic structure by ring-open reaction during alkaline-oxygen treatment. The analysis result of alkaline nitrobenzene oxidation and ’H NMR proved that amount of high molecular weight composition of KL still retention in the modified lignin. These characteristics of modified lignin are good for the formation of complex between A13+ and modified lignin under acid condition. Meanwhile these modified lignin also have properties of absorption and buffering in soil system.The GFC experiment of the mixture of Al3+and modified lignin showed that Al/S-1 changed under different pH condition. Al/S-1 stand for the amount of Al3+absorbed by each mol. of modified lignin. When pH5.8, the Al/S-1 reached maximum, about 0.358 mol.. The formation of complex between modified lignin and A13+ were further confirmed by potentionmetric titration.The planting experiment of modified lignin showed that both sulfonated lignin and alkaline -oxygen treatment lignin could retard the toxicity of aluminum to the growth of root elongation, although their efficiencies were different and depended on the chemical structure of modified lignin, namely the type and content of function group in the modified lignin. This was also proved by hematoxylin staining experiment.更多还原