基于超声波辅助相转移催化磺化腐植酸实验的研究.docVIP

  基于超声波辅助相转移催化磺化腐植酸实 验研究# 赵宇，胡国新** 5 10 15 20 25 30 35 40 （上海交通大学机械与动力工程学院,上海 200240） 摘要：通过使用稀硫酸对腐植酸在有相转移催化剂的条件下进行磺化实验研究，得到在使用 季铵盐做相转移催化剂时，四丁基溴化铵的催化效果最好。在四丁基溴化铵为相转移催化剂 条件下进行单因素实验研究了硫酸浓度、超声作用参数等对腐植酸磺化度的影响，并对反应 产物进行了 FTIR、拉曼光谱及 XPS 等分析进一步证明了稀硫酸对腐植酸在有相转移催化剂 的条件下的磺化机理。最后，通过设计正交试验得到：用相转移催化剂四丁基溴化铵的条件 下进行针对磺化腐植酸的优选方案为超声功率为 120W，超声作用时间为 30 分钟，添加相 转移催化剂四丁基溴化铵为 0.02g，温度控制在 85为佳。 关键词：能源化学；腐植酸；磺化；相转移催化剂；超声作用 中图分类号：TQ083+.4 Ultrasound promoted sulfonation of humic acid using dilute sulfuric acid in the presence of phase transfer catalyst ZHAO Yu, HU Guoxin (Mechanical and Power Engineering School,Shanghai Jiao Tong University, Shanghai 200240) Abstract: In this paper a sulfuric acid/ humic acid(HA) system with quaternary ammonium salts as phase-transfer catalysts were employed in the sulfonation of humic acid. Four quaternary ammonium salts catalytic systems with ultrasound were carried out, tetrabutyl ammonium bromide behaved as the optimum active catalys. In order to attain a higher sulfonation degree of humic acid, orthogonal experiments of dilute sulfuric acid sulfonated humic acid system with tetrabutyl ammonium bromide as phase-transfer catalysts were carried out in the flask to investigate the effect of main factors, namely, temperature, ultrasound power, ultrasound time and catalyst dose on sulfonation degree. The range analysis and analysis of variance (ANOVA) were applied for the results of orthogonal experiments. Results showed that the optimal condition for humic acid sulfonation should be A4B4C1D1, namely, temperature, ultrasound power density, ultrasound time and catalyst dose were 85 °C, 12W·ml-1, 30min and 0.02g, respectively. Key words: Energy Chemistry; Humic acid; Sulfonation; Phase Transfer Catalyst; Ultrasonication 0 引言 通常腐植酸可以被用来在农业、工业、医药、畜牧、环保方面作为抗旱剂、生长剂、饲 料添加剂、石油钻井液处理剂、陶瓷增强剂、锅炉除垢剂等[1]。腐植酸分子结构中含有芳香 基、酚羟基、羰基、甲氧基以及羧基等活性基团[2]，而正由于存在有这些活性基团所以可以 、[4] 发挥腐植酸的使用效果通常会将其磺化、硝化、氧解、氨化等化学方法进行改性处理，具体 说就是腐植酸可以在一定条件下引入其他活性基团，克服腐植酸自身的某些固有缺点，制造 出具有很高生物活性的腐植酸衍生物。而所谓腐植酸磺化就