Page 57 - 精细化工2019年第12期

第 36 卷第 12 期 精 细 化 工 Vol.36, No.12
2019 年 12 月 FINE CHEMICALS Dec. 2019

功能材料
腐植酸/淀粉复合微球的制备及工艺优化

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苏秀霞 ，胡金龙 ，张 婧 1,2 ，晏春苗 ，徐 佳
（1. 陕西科技大学 教育部轻化工助剂化学与技术重点实验室，陕西 西安 710021；2. 咸阳职业技术学
院，陕西 咸阳 712000）
摘要：以腐植酸（HA）和可溶性淀粉（St）为原料，N,N'-亚甲基双丙烯酰胺（MBAA）为交联剂，过硫酸钾/
亚硫酸氢钠（K 2 S 2 O 8 /NaHSO 3 ）为复合引发剂，采用反相乳液聚合法合成了腐植酸/淀粉复合微球（CSM）。结合
响应曲面设计，探讨了 m(HA)∶m(St)、K 2 S 2 O 8 /NaHSO 3 用量、MBAA 用量、复合乳化剂用量、反应温度等因素
对 CSM 吸附 Cr(Ⅵ)性能的影响。结果表明，合成 CSM 的最佳工艺条件为：m(HA)∶m(St)=1.51∶1.00、MBAA
用量 40%（以 St 质量为基准，下同）、K 2 S 2 O 8 /NaHSO 3 用量 40%/40%、复合乳化剂〔m(Span-80): m(Tween-20)=3:1〕
用量 80%、反应温度 50 ℃、反应时间 3 h。在该条件下合成的 CSM 对 Cr(Ⅵ) （10 mg/L）的去除率达到 99.91%，
吸附量为 1.9980 mg/g。利用 FTIR、SEM、激光粒度分布仪、XRD 和 TGA 对 CSM 进行了结构表征和性能测试，
结果显示 HA 和 St 成功反应，所得 CSM 形状规则，表面粗糙，粒径分布均匀，平均粒径为 13.79 μm，结晶度
（相较于 St）降低，具有较好的热稳定性。
关键词：腐植酸；复合微球；反相乳液聚合；优化；吸附性能；功能材料
中图分类号：TQ424.3 文献标识码：A 文章编号：1003-5214 (2019) 12-2385-09

Preparation and Process Optimization of Humic
Acid/Starch Composite Microspheres

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SU Xiu-xia , HU Jin-long , ZHANG Jing , YAN Chun-miao , XU Jia
（1. Key Laboratory of Auxiliary Chemistry and Technology for Chemical Industry, Ministry of Education, Shaanxi
University of Science & Technology, Xi'an 710021, Shaanxi, China; 2. Xianyang Vocational Technical College, Xianyang
712000, Shaanxi, China）
Abstract: Humic acid/starch composite microspheres (CSM) were prepared by reverse phase emulsion
polymerization method using humic acid (HA) and soluble starch (St) as raw materials,
N,N'-methylenebisacrylamide (MBAA) as cross-linking agent, potassium persulfate/sodium hydrogen
sulfite (K 2S 2O 8/NaHSO 3) as initiator. Response surface methodology was used to investigated the effects of
m(HA)∶m(St), K 2S 2O 8/NaHSO 3 dosage, MBAA dosage, composite emulsifier dosage and temperature on
the adsorption properties of CSM. The results showed that the optimum conditions for the synthesis of CSM
were obtained as follows: mass ratio of HA to St 1.51∶1.00, MBAA dosage 40% (based on the mass of St,
the same below), K 2S 2O 8/NaHSO 3 dosage 40%/40%, composite emulsifier〔m(Span-80): m(Tween-20)=3:1〕
dosage 80%, reaction temperature 50 ℃, and reaction time was 3 h. Under the above-mentioned conditions,
the removal rate of CSM for Cr(Ⅵ) (10 mg/L) reached 99.91%, the adsorption capacity was 1.9980 mg/g.
The CSM was characterized by FTIR, SEM, laser particle size distribution analyzer, XRD and TGA. It was
found that HA and St reacted successfully, the CSM was regular in shape and rough in surface with a
uniform particle size distribution. The average particle size was 13.79 μm. The crystallinity of CSM
decreased compared with that of St. In addition, the CSM had good thermal stability.
Key words: humic acid; composite microspheres; inverse emulsion polymeriztion;optimization; adsorption
properties; functional materials

收稿日期：2019-05-04; 定用日期：2019-06-11; DOI: 10.13550/j.jxhg.20190392
基金项目：陕西省科技厅科技计划项目（2014K10-20）；咸阳市科技计划项目（2018K02-49）
作者简介： 苏秀霞（1964—），女，教授，E-mail：suxiuxia@sust.edu.cn。联系人：胡金龙（1991—），男，硕士生，E-mail：1239145233@qq.com。