纺织学报 ›› 2019, Vol. 40 ›› Issue (10): 26-32.doi: 10.13475/j.fzxb.20180903507

• 纤维材料 • 上一篇    下一篇

内涂覆锰氧化物聚(甲基)丙烯酸酯中空纤维制备及其对亚甲基蓝的脱色性能

郭东艳1,2, 徐乃库1,2(), 肖长发1,2   

  1. 1.天津工业大学 材料科学与工程学院, 天津 300387
    2.天津工业大学 分离膜与膜过程国家重点实验室, 天津 300387
  • 收稿日期:2018-09-13 修回日期:2018-12-26 出版日期:2019-10-15 发布日期:2019-10-23
  • 通讯作者: 徐乃库
  • 作者简介:郭东艳(1991—),女,硕士生。主要研究方向为有机高分子纤维材料。
  • 基金资助:
    国家自然科学基金项目(51103099);天津市应用基础及前沿技术研究计划项目(12JCQNJC01600);教育部高等学校博士学科点专项科研基金项目(20111201120002);中国博士后基金项目(2014M550143);中国博士后基金项目(2015T80221)

Preparation of poly(meth)acrylate hollow fiber with internal coating of manganese oxide and its capability to decolorize dyes of methylene blue

GUO Dongyan1,2, XU Naiku1,2(), XIAO Changfa1,2   

  1. 1. School of Material Science and Engineering, Tiangong University, Tianjin 300387, China
    2. State Key Laboratory of Separation Membranes and Membrane Processes, Tiangong University, Tianjin 300387, China
  • Received:2018-09-13 Revised:2018-12-26 Online:2019-10-15 Published:2019-10-23
  • Contact: XU Naiku

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摘要：

为提升聚(甲基)丙烯酸酯中空纤维对流经其内部亚甲基蓝(MB)水体的脱色效果,采用溶液聚合法合成甲基丙烯酸丁酯-甲基丙烯酸羟乙酯共聚物和丙烯酸丁酯-甲基丙烯酸羟乙酯共聚物,采用湿法纺丝纺制中空纤维,并采用内涂覆工艺将原位生成的锰氧化物通过络合作用固定于中空纤维内部。利用场发射扫描电子显微镜、X射线电子能谱仪分析功能化处理前后中空纤维形貌和表面元素变化,确定锰氧化物组成,并借助总有机碳分析仪、电感耦合等离子体发射光谱仪对MB脱色过程进行研究。结果表明,涂覆锰氧化物后,其强氧化作用使流经中空纤维内部MB溶液的脱色率由最初的10%提高至78.7%,且多次使用后对MB的脱色率仍远高于10%。

关键词: 废水脱色, 中空纤维, 内涂覆工艺, 锰氧化物, 亚甲基蓝

Abstract:

In order to enhance the decolorization efficiency of methylene blue (MB) when it flows in the poly(meth)acrylate hollow fiber, the blend solution of poly (butyl methacrylate-co-hydroxyethyl methacrylate) and poly (butyl acrylate-co-hydroxyethyl methacrylate) synthesized via solution polymerization was used as spinning dope to prepare the above hollow fiber through wet spinning. The process of internal coating was then designed to immobilize in-situ generated manganese oxide onto the inside of hollow fiber through complexation. Meanwhile, the changes of morphology and surface element of hollow fibers before and after functionalization were analyzed by using field emission scanning electron microscopy and X-ray electron spectroscopy, and the composition of manganese oxide was then determined. Additionally, total organic carbon analyzer and inductively coupled plasma atomic emission spectrometer were used to investigate the decolorization of MB. The results show that as far as the hollow fiber prepared after coating is considered, when the aqueous solution of MB flowed into its inside decolorization efficiency is increased from original 10% to 78.7%, and the decolorization efficiency is much higher than 10% even though the manganese oxide-coated hollow fiber is used for several times. It is clear that the strong oxidation of manganese oxide is responsible for the improvement of decolorization efficiency.

Key words: decolorization of waste water, hollow fiber, internal coating, manganese oxide, methylene blue

中图分类号: 

  • TQ342.8

表1

硫酸水解时间对亚甲基蓝脱色率的影响"

样品 1 h 2 h 3 h
HF1 73.3 66.6 60.4
HF2 78.6 69.7 63.9
HF3 76.3 67.7 62.1

表2

高锰酸钾氧化时间对亚甲基蓝脱色率的影响"

样品 0.5 h 1 h 2 h
HF1 70.6 73.3 76.2
HF2 67.7 78.6 79.8
HF3 61.9 70.6 75.1

图1

HF2和HF2-b的FESEM照片"

图2

HF2和HF2-b 的XPS全谱图"

图3

HF2-b 的Mn2p3/2 电子局部XPS谱图"

图4

重复使用HF2-b 过程中亚甲基蓝脱色率"

表3

脱色前后亚甲基蓝溶液中总有机碳以及锰离子的质量浓度"

样品编号 总有机碳质量浓度 锰离子质量浓度
L1 2.24 0.40
L2 2.41 0.98
L3 2.92 1.02
L4 2.98 1.52
L5 4.05 1.84
20 mg/L MB 8.62

图5

Mn2p3/2电子局部XPS谱图"

表4

锰氧化物中Mn(Ⅱ)、Mn(Ⅲ)和Mn(Ⅳ)的相对含量"

样品 Mn(Ⅱ) Mn(Ⅲ) Mn(Ⅳ)
HF2-b 3.9 42.5 53.6
HF2-b-1 11.7 46.4 41.9
HF2-b-2 21.2 42.7 36.1
HF2-b-3 27.7 39.9 32.4
HF2-b-4 39.4 31.5 29.1
HF2-b-5 40.5 33.8 25.7
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