摘要
充分利用天然可再生资源,生产“环境友好”的绿色产品以及开发绿色化学工艺已成为当前化学、化工及其交叉学科研究热点。木质素是自然界丰富的天然高分子聚合物,是一种可再生资源;工业木质素磺酸盐主要来自造纸废液,来源丰富、价格低廉、无毒,是一种阴离子表面活性剂,可广泛用作水煤浆添加剂、混凝土减水剂、农药分散剂、陶瓷助磨剂等。木质素磺酸盐的应用性能与其物化性能密切相关,而木质素磺酸盐在溶液中的行为又会影响其在界面的吸附性能,因此,研究木质素磺酸盐的溶液行为及其在界面吸附机理对提高其应用性能具有重要意义。然而由于木质素磺酸盐结构的不确定性和成分的复杂性,导致木质素磺酸盐的溶液行为及其在界面的吸附行为研究难以得出规律性结果,影响了木质素磺酸盐的应用研究进展。本文系统研究了离子强度及pH值等因素对木质素磺酸钠在溶液中的聚集行为及气/液界面、固/液界面吸附行为的影响,揭示了木质素磺酸盐在界面的吸附机理。此研究对木质素磺酸盐的资源化利用具有重要的理论意义和应用价值。
本文首先以粗木质素磺酸钠为原料,比较了树脂法、超滤法、长链胺法和溶剂萃取法的提纯效果与效率。红外光谱、元素分析、凝胶渗透色谱等测试结果表明,溶剂萃取法不能达到提纯目的;树脂法、超滤法、长链胺法可除去相对分子量小于1000的杂质,粗木质素磺酸钠经提纯后木质素磺酸钠含量从59.0%提高到90.0%左右,且提纯样品的重均分子量和数均分子量均增大。从产品收率、提纯效果及提纯工艺三个方面分析得出超滤提纯法最优。因此,本文采用截留分子量为2500的超滤膜对粗木质素磺酸钠进行了提纯,为后续研究提供原料。
采用电位滴定仪、Zeta电位仪、表面张力仪、静态荧光仪、动态光散射仪(DLS)等表征技术研究了离子强度和pH值对木质素磺酸钠在溶液中聚集行为的影响。结果表明木质素磺酸钠在水溶液中的临界聚集浓度(CAC)为0.05 g/L。当浓度低于CAC时,溶液中存在大量的单分子和少量聚集体;当浓度高于CAC时,单分子数量减少,聚集体数量急剧增加。单分子和聚集体的粒径分别为8 nm和80 nm左右,其单分子和聚集体的内核均由疏水骨架构成,内核中包含部分弱电离基团如羧基和酚羟基;疏水核的表面不均匀分布着磺酸根及少量的酚羟基。随着浓度增大木质素磺酸钠聚集程度增大;随着pH值增大,疏水核内的弱电离基团发生电离,由于静电斥力作用木质素磺酸钠的疏水内核由紧密变得疏松,其单分子和聚集体粒径增大;离子强度增大,屏蔽了木质素磺酸钠分子间的静电斥力使得聚集程度增大,聚集体粒径增大。
采用动态表面张力仪及LB膜天平研究了离子强度和pH值对木质素磺酸钠在气/液界面吸附行为的影响。结果表明,木质素磺酸钠在气/液界面吸附是一个缓慢的过程,随着离子强度增大和pH值减小木质素磺酸钠溶液表面张力降低。木质素磺酸钠在气/液界面形成不稳定的可溶性单分子膜,随着浓度增大、pH值减小和离子强度增大,气/液界面膜稳定性变差。大分子量的木质素磺酸钠优先吸附于气/液界面,随着浓度增大小分子量的分子也逐步吸附于气/液界面,浓度继续增大,分子在气/液界面由混乱不规则的排列状态逐步变成有序而紧密的排列状态。
研究了温度、pH值、离子强度及脲对木质素磺酸钠在TiO_2/水界面吸附的影响,测定了吸附前后木质素磺酸钠分子量的变化。结果表明,温度升高和pH值减小,吸附速率增大;随着离子强度增大,吸附速率先减小后增大。随着温度升高、离子强度增大和pH值减小饱和吸附量增大,而随着脲的加入饱和吸附量减小;且大分子量的木质素磺酸钠优先吸附于TiO_2/水界面。不同温度、pH值和加入脲时吸附等温线符合Langmuir单层吸附模型,而加入NaCl后,则符合Freundlich单层吸附模型。
研究了温度、pH值、离子强度及脲对木质素磺酸钠在活性炭/水界面吸附的影响,测定了吸附前后木质素磺酸钠分子量的变化。结果表明,温度变化对吸附影响较小。随着pH值降低、离子强度增大,吸附速率和饱和吸附量增大,但随着脲的加入饱和吸附量减小,且小分子量的木质素磺酸钠优先吸附于活性炭/水界面。不同温度、pH值和加入脲时吸附等温线符合Langmuir单层吸附模型;而加入NaCl后,则符合Freundlich单层吸附模型。
研究表明,木质素磺酸钠在TiO_2和活性炭表面的吸附过程都存在着静电吸附、氢键吸附和疏水作用吸附,属于单层多点式吸附。随着温度升高,木质素磺酸钠在TiO_2颗粒表面的吸附速率和吸附量增大,而对其在活性炭表面的吸附几乎没有影响。相同条件下其在活性炭表面的吸附量约为TiO_2表面的10倍,大分子量的木质素磺酸钠优先吸附于TiO_2表面,而小分子量的木质素磺酸钠优先吸附于活性炭表面,这是由于活性炭比TiO_2孔结构丰富、比表面积大而造成的。溶液pH值减小和离子强度增大木质素磺酸钠在两种吸附剂表面吸附量均增加。脲的加入使木质素磺酸钠在活性炭和TiO_2表面的吸附量减小;与在TiO_2表面相比,脲使木质素磺酸钠在活性炭表面吸附量降低的程度更明显,这说明木质素磺酸钠在活性炭表面吸附过程中,活性炭表面活性基团产生了较大氢键作用。研究结果可为木质素磺酸盐在金属氧化物和多孔非极性固体颗粒上的吸附研究和应用提供理论参考。
Making full use of natural renewable resources and producing environmentally friendly green materials through green catalytic processes have become the prime frontier research in the linked fields of chemistry and chemical engineering. Lignin is the main component of the plant cell wall; it exists widely in nature, and it is the second most abundant biopolymer (after cellulose) on earth. Lignosulfonates come from the byproducts of the pulp and paper industry; they are renewable, low cost, nontoxic and abundant. As a kind of anionic surfactant, lignosulfonates can be widely used as a coal-water slurry additive, a concrete water-reducing agent, a pesticide dispersant, a ceramic grinding agent and so on. The application performance of lignosulfonates is closely related to their physicochemical properties, such as their surface activity and adsorption performance (which is affected by the solution behavior of lignosulfonates) at the interface. Thus, study on the solution behavior of lignosulfonates and its adsorption mechanism at interface has an important meaning for improving its application performance. But it is difficult to obtain regularity results from the studies on the solution behavior and interface adsorption mechanism of lignosulfonates as the uncertaincy structure and composition complexity of lignosulfonates. In this thesis we report on studies of the influence of ionic strength and pH on the solution behavior of lignosulfonates and their adsorption at the air/liquid and solid/liquid interfaces. The structure of lignosulfonates in aqueous solution and their adsorption mechanism at interfaces are analyzed. This research can provide theoretical instruction for industrial applications of lignosulfonates. This research has an important theoretical significance and application value for the utilization of lignosulfonates as resources.
Firstly, commercial sodium lignosulfonate (SL) was purified with the ionic-resin method, ultrafiltration, long chain aliphatic amine extraction and solvent extraction. The structure, composition and molecular weight distribution of raw SL and purified SL were characterized by infra-red spectroscopy, elementary analysis and gel chromatography. Experimental results indicated that solvent extraction did not purify raw SL efficiently. The ionic-resin method, ultrafiltration and long chain aliphatic amine extraction removed impurities with molecular weight less than 1000; after purification, the content of lignosulfonate was raised from 59.0% to 90.0%; the number average molecular weight and weight average molecular weight of purified SL increased. Ultrafiltration is the most favourable purification method, as measured by the purified SL yields, the purification efficiency and the purification technology. Consequently, in this thesis we chose the purified SL (PSL) obtained from the ultrafiltration method with 2500 ultrafiltraion membrane as our research sample for studing the solution behavior of PSL and the adsorption of PSL at air/liquid and solid/liquid interfaces.
Secondly, the solution behaviors of PSL at different ionic strengths and pH values have been investigated by means of acid-base titration, surface tension, viscosity, fluorescence spectrometry and dynamic light scattering (DLS) experiments. Results showed that the critical aggregate concentration (CAC) of PSL was 0.05g/L; when the concentration of PSL was below CAC, there were a few of PSL aggregates in solution; when the concentration was above CAC, the number of PSL aggregates increased sharply. The average dimensions of PSL molecules and PSL aggregates in aqueous solution were about 8 nm and 80 nm, respectively. The surface of PSL aggregates was mainly covered by sulfonic groups and a few of phenolic hydroxyl groups, and the core of PSL aggregates was generated by hydrophobic chains. The hydrophobic core was loose and contained many weakly ionized groups such as carboxyls and phenolic hydroxyl groups. Increasing the PSL concentration favoured aggregation of PSL. While along with the increasing of the pH value, the number of ionic groups in the hydrophobic core also increased, and the PSL hydrophobic core became looser; thus the diameter of PSL aggregates increased as the pH value increased. The electrostatic repulsion between PSL molecules can be shielded by addition of salt, so that the diameter of PSL aggregates increased as the ionic strength increased.
Thirdly, the influence of ionic strength and pH on the adsorption behavior of PSL at the air/liquid interface was studied by a dynamic tension meter and an LB film balance. The results showed that the adsorption of PSL at the air/liquid interface was a slow process. The surface tension of PSL solutions decreased as the ionic strength increased and the pH value decreased. PSL could form unstable and soluble films at the air/liquid interface; furthermore, the stability of the PSL film at the air/liquid interface decreased as the concentration of PSL and ionic strength increased and the pH values decreased. The results indicated that the PSL with higher molecular weight was preferably adsorbed at the air/liquid interface, and then the PSL with lower molecular weight was adsorbed at the air/liquid interface when the concentration of PSL increased. In addition, the arrangement of PSL at the air/liquid interface turned from disorderly to orderly as the concentration of PSL increased.
Fourthly, the influences of temperature, pH, ionic strength and addition of urea on the adsorption of PSL at TiO_2/water interface were investgated. The molecular weights of PSL before and after adsorption were determined. The experimental results showed that the adsorption rate of PSL at TiO_2/water interface increased as the temperature increased and decreased as the pH value increased, while it decreased first and increased later with the ionic strength increased. The adsorption amount increased as the temperature and ionic strength increased, but decreased with the pH value increased and addition of urea. The PSL with higher molecular weight was first adsorbed at TiO_2/water interface. The adsorption isotherms of PSL at TiO_2/water interface conformed to the Langmuir adsorption model at different temperatures, pH values and with addition of urea, but with addition of NaCl, the adsorption isotherms of PSL at TiO_2/water interface corresponded to the Freundlich adsorption model.
Fifthly, the influences of temperature, pH, ionic strength and addition of urea on the adsorption of PSL at active carbon/water were researched. The molecular weights of PSL before and after adsorption were determined. The experimental results showed that temperature had little influence on the adsorption of PSL at active carbon/water interface. The adsorption rate and adsorption amount of PSL increased with increasing of ionic strength increased and decreasing of pH value, but the adsorption amount of PSL decreased with addition of urea. The PSL with lower molecular weight was first adsorbed at the active carbon/water interface. The adsorption isotherms of PSL at active carbon/water interface conformed to the Langmuir adsorption model at different temperatures, pH values and with addition of urea; however, it corresponded to the Freundlich adsorption model with addition of NaCl.
Based on the experimental exploration, it was concluded that PSL absorbed at TiO_2/water and active carbon/water interfaces by means of electrostatic interaction, hydrogen bonding and hydrophobic interaction. There had some differences between the two adsorbent processes. Firstly,the adsorption rate and amount of PSL at TiO_2/water interface increased as temperature increased, while the temperature did not have an effect on the adsorption of PSL at active carbon/water interface. Secondly, the adsorption amount of PSL at the active carbon /water interface was 10 times as the TiO_2/water interface under the same conditions. Thirdly, the PSL with higher molecular weight was preferably absorbed to the TiO_2/water interface, while the opposite happened at active carbon/water interface because of their rich porous structure and higher specific surface area. The decrease of the pH value and the increase of the ionic strength had the same effect on the adsorption behavior when PSL were adsorbed on the two adsorbents. With addition of urea, the adsoption amount of PSL on the two adsorbents decreased, and the reduced degree on active carbon surface is bigger than that on TiO_2 surface. It indicated that the hydrogen interaction was larger when PSL adsorbed on active carbon than that on TiO_2 surface. The results could provide a significant insight in understanding the adsorption and application of PSL on the metallic oxide and porous nonpolar particles.
引文
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