多功能球形木质素基吸附材料的制备及其性能研究
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摘要
木质素是唯一能从可再生资源中取得的芳香族化合物，并且无毒价廉，其开发和利用有着重要价值。目前工业木质素的主要来源是造纸工业，现代造纸企业采用先进的废水回用技术与设施，以充分利用制浆造纸废水中的有用物质及水资源等，但其中大量的木质素通常作为燃料使用，有的甚至未经处理直接排放，造成严重的资源浪费和环境污染。因此研究利用工业木质素，对于综合治理造纸工业废水污染、充分利用天然资源具有重要的现实意义。本文从综合利用造纸工业废弃资源的角度出发，研究了木质素磺酸盐与甲醛的反相悬浮缩聚反应，以及木质素基球形树脂的制备与性能。
进行了原料木质素磺酸钙(CLS)的主要结构特点及反应性研究，表明它是由一系列非晶态的、明显具有取代酚结构特征的大分子和小分子所组成的混合物；存在大量酚型愈创木基结构单元和少量对羟苯基结构单元，且结构单元之间多以醚键连接；含有较多量羟基、磺酸基、甲氧基和少量的羰基等活性基团；质均相对分子质量为2505，多分散性指数为1.55。
详细研究了木质素磺酸钙与甲醛的反相悬浮缩聚反应，以无毒价廉的液体石蜡作为分散相，合成了粒径可控的球形木质素磺酸盐树脂RLS；并通过正交试验进一步优化聚合反应条件，不仅大大缩短了聚合成球时间，而且显著提高了产品的强度和交换容量。实验室优化条件为：相比3：1，搅拌速度200rpm，木质素磺酸钙浓度50％，体系酸度3mol／L(HCl)，甲醛用量7％，聚合温度95℃。优化条件下得到的RLS球形规整，粒度均匀，含水量61.20％，转型膨胀率12.5％，全交换容量3.46mmol／g(干)。
RLS的外观呈黑色不透明圆球状，利用多种现代分析测试手段对RLS的结构进行表征。扫描电镜和扫描探针显微镜观察结果表明RLS的外表为凹凸不平状，内部结构不均匀，分为凝胶和孔隙两部分，具有疏松多孔的结构特征。压汞测孔和BET分析结果显示干态样品的孔径分布在100nm以下，平均孔径为10.46nm，比表面积大于10m~2／g；湿树脂的孔隙率为43.27％，孔容为1.578mL／g。X射线衍射分析表明RLS为非晶态结构；CLS、RLS和吸附Cr~(3+)后的RLS在综合热分析的程序升温过程中具有明显不同的失重规律和热效应。
木质素磺酸钙及RLS的胺化改性研究表明，用季铵基醚化剂3-氯-2-羟丙基-三甲基氯化铵(CHPTA)对球形木素树脂RLS进行直接醚化改性，可以使木素树脂中引入一定量的季铵基团，从而得到一种具有多种功能基团的球形木素基吸附剂ARLS。实验室优化条件下得到的改性产物的阴离子全交换容量可达0.67mmol／g，
Lignin is the sole aromatic compound that can be obtained from renewable resources. It is renewable, non-toxic and commercially available, which makes lignin utilization be a valuable work. Nowadays, most lignin applications are based on technical lignins, which are mostly separated during pulping process. In modern paper industry, most useful materials and water rescources can be well reused by the application of advanced treatment technology for the spent liquors of pulping and papermaking. However, a large number of lignin in the spent liquors were used as a source of fuel, or discharged without any treatment process, which caused consequent heavy waste of resources and severe pollution of environment. So, research on the utilization of technical lignin is very important and significant to treat with the watsewater from paper mill and to make full utilazation of natural resource. In order to comprehensively utilize the waste resource of paper industry, the reversed phase suspension polymerization of formaldehyde and lignosulphonate, and the preparation and performances of sphereic lignin based resin were investigated in this paper.
The structural characteristics and reactivity of raw material have been studied, the results indicate that the calcium lignosulfonate(CLS) is a mixture of amorphous macromolecule and micromolecule with phenolic lignin units. It comprises many guaiacyl phenols and few p-hydroxy phenols, and most of the units are bonded with ether links. Besides, It comprises a variety of functional groups, such as hydroxyl, sulphonic group, methyoxyl and carbonyl. Mass-average molecular weight of the CLS is 2505, and polydispersity index is 1.55.
the reversed phase suspension polymerization of formaldehyde and CLS has been invenstigated systematically, and a spherical lignin-based resin (RLS) with controllable size range in liquid paraffin which is a cheap and non-toxic dispersing medium was developed. The process conditions for the preparation of RLS were optimizd by orthogonal experiments so as to shorten reaction time and to improve the strength and ion exchange capacity of the product. The optimun conditions include 3:1 of phase ratio, 200 r/min of stirring speed, 50% of the CLS concentration, 3mol/L HC1 of acdity, and 7% of formaldehyde dosage and 95℃. The RLS obtained at optimun conditions was characterized with full spheric shape, narrow particle size range, 61.20% of water retention and high adsorptive capacity. 12.5% of form
进行了原料木质素磺酸钙(CLS)的主要结构特点及反应性研究，表明它是由一系列非晶态的、明显具有取代酚结构特征的大分子和小分子所组成的混合物；存在大量酚型愈创木基结构单元和少量对羟苯基结构单元，且结构单元之间多以醚键连接；含有较多量羟基、磺酸基、甲氧基和少量的羰基等活性基团；质均相对分子质量为2505，多分散性指数为1.55。
详细研究了木质素磺酸钙与甲醛的反相悬浮缩聚反应，以无毒价廉的液体石蜡作为分散相，合成了粒径可控的球形木质素磺酸盐树脂RLS；并通过正交试验进一步优化聚合反应条件，不仅大大缩短了聚合成球时间，而且显著提高了产品的强度和交换容量。实验室优化条件为：相比3：1，搅拌速度200rpm，木质素磺酸钙浓度50％，体系酸度3mol／L(HCl)，甲醛用量7％，聚合温度95℃。优化条件下得到的RLS球形规整，粒度均匀，含水量61.20％，转型膨胀率12.5％，全交换容量3.46mmol／g(干)。
RLS的外观呈黑色不透明圆球状，利用多种现代分析测试手段对RLS的结构进行表征。扫描电镜和扫描探针显微镜观察结果表明RLS的外表为凹凸不平状，内部结构不均匀，分为凝胶和孔隙两部分，具有疏松多孔的结构特征。压汞测孔和BET分析结果显示干态样品的孔径分布在100nm以下，平均孔径为10.46nm，比表面积大于10m~2／g；湿树脂的孔隙率为43.27％，孔容为1.578mL／g。X射线衍射分析表明RLS为非晶态结构；CLS、RLS和吸附Cr~(3+)后的RLS在综合热分析的程序升温过程中具有明显不同的失重规律和热效应。
木质素磺酸钙及RLS的胺化改性研究表明，用季铵基醚化剂3-氯-2-羟丙基-三甲基氯化铵(CHPTA)对球形木素树脂RLS进行直接醚化改性，可以使木素树脂中引入一定量的季铵基团，从而得到一种具有多种功能基团的球形木素基吸附剂ARLS。实验室优化条件下得到的改性产物的阴离子全交换容量可达0.67mmol／g，
Lignin is the sole aromatic compound that can be obtained from renewable resources. It is renewable, non-toxic and commercially available, which makes lignin utilization be a valuable work. Nowadays, most lignin applications are based on technical lignins, which are mostly separated during pulping process. In modern paper industry, most useful materials and water rescources can be well reused by the application of advanced treatment technology for the spent liquors of pulping and papermaking. However, a large number of lignin in the spent liquors were used as a source of fuel, or discharged without any treatment process, which caused consequent heavy waste of resources and severe pollution of environment. So, research on the utilization of technical lignin is very important and significant to treat with the watsewater from paper mill and to make full utilazation of natural resource. In order to comprehensively utilize the waste resource of paper industry, the reversed phase suspension polymerization of formaldehyde and lignosulphonate, and the preparation and performances of sphereic lignin based resin were investigated in this paper.
The structural characteristics and reactivity of raw material have been studied, the results indicate that the calcium lignosulfonate(CLS) is a mixture of amorphous macromolecule and micromolecule with phenolic lignin units. It comprises many guaiacyl phenols and few p-hydroxy phenols, and most of the units are bonded with ether links. Besides, It comprises a variety of functional groups, such as hydroxyl, sulphonic group, methyoxyl and carbonyl. Mass-average molecular weight of the CLS is 2505, and polydispersity index is 1.55.
the reversed phase suspension polymerization of formaldehyde and CLS has been invenstigated systematically, and a spherical lignin-based resin (RLS) with controllable size range in liquid paraffin which is a cheap and non-toxic dispersing medium was developed. The process conditions for the preparation of RLS were optimizd by orthogonal experiments so as to shorten reaction time and to improve the strength and ion exchange capacity of the product. The optimun conditions include 3:1 of phase ratio, 200 r/min of stirring speed, 50% of the CLS concentration, 3mol/L HC1 of acdity, and 7% of formaldehyde dosage and 95℃. The RLS obtained at optimun conditions was characterized with full spheric shape, narrow particle size range, 61.20% of water retention and high adsorptive capacity. 12.5% of form
引文
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