Nanoporous PVDF - based Membranes for lonic Dye Removal from Aqueous solutions and filtration machanisms therein : Doctoral Thesics- Major: Chemical and Material Engineering

長庚大學化工與材料工程學系

博士論文

Department of Chemical and Materials Engineering

Chang Gung University

Doctoral Dissertation

具奈米微孔的聚偏二氟乙烯及其複合薄膜用於離子性染料的

去除及其分離機制的探討

Nanoporous PVDF-based Membranes for Ionic Dye Removal

from Aqueous Solutions and Filtration Mechanisms Therein

指導教授：呂幸江 博士

Advisor: Shing-jiang Jessie Lue, Ph.D.

研究生：鄭氏德芳

Graduate Student: Tran Thi Tuong Van

中華民國 108 年 12 月

December 2019

-iii￾Acknowledgements

I would like to extend acknowledgements to many people who so generously assisted me

during my Ph.D. studying time.

First and foremost, truly deep gratitude goes to Professor Shingjiang Jessie Lue, my

dedicated and expert advisor. Since my first day in graduate school, she gave me continuing

academic support and offered me so many wonderful opportunities. Under her guidance, I

learned how to define a research problem, conduct scientific research and finally publish the

result. I also benefited a lot from joining in various related works of the laboratory. In addition,

participating in conferences brought me eye-opening and fascinating experiences.

Special thanks go to Professors of Chemical and Materials Engineering Department who

provided me plenty of precious knowledge and warm encouragement. I am very appreciative to

nice and helpful officers at every section in Chang Gung University.

Sincere thanks go to willing generations of labmates in Microcontamination & Membrane

Separation Laboratory who enthusiastically helped me in lab works and many other things. In

particular, deep thanks come to Doctor S. Rajesh Kumar who supplied me invaluable advices

during my writing process. I am so thankful to my Taiwanese and international friends for

sharing with and supporting me during classes, experiments and life. Thank you all for turning

my time in CGU into unforgettable memories ever.

Sincere gratitude goes to my managers and colleagues at Institute of Environmental

Science, Engineering and Management, Industrial University of Ho Chi Minh City in Vietnam

who facilitated my Ph.D. study and sent me many kind encouragements.

Last but not least, I would like to wholeheartedly thank my dear family and parents for

endless love and support. This thesis is dedicated to them.

-iv￾摘要

本文探討了各種有機染料在聚偏氟乙烯（PVDF）超濾膜上的過濾行為，發現

Donnan 排斥機制在染料分離中為主要分離機制。PVDF 膜對兩性離子若丹明

B（RhB，1.1%）的截留率極低，而對陽離子亞甲基藍（MB，45.6%）的截留

率中等；但對陰離子染料，鉻黑 T（EBT，83.5%）和萘酚藍的截留率高。黑

色（NBB，89.1%）。兩性離子或相同電荷的混合染料溶液（RhB-MB，RhB￾NBB 和 EBT-NBB）顯示出的染料去除率與其成分的單一染料溶液相似。相

反，由於分子間的相互作用，帶相反電荷的染料（MB-NBB）的混合溶液形

成微米級的聚集體，導致染料幾乎完全被去除、並提高了滲透率。在多次循

環過濾過程中證明了膜過濾性能的穩定性。接下來，本文研究了氧化石墨烯

（GO）和聚乙烯基吡咯烷酮（PVP）添加劑在 PVDF 混成膜的個別和加成作

用。結果顯示 PVP 的主要作用是增強膜的孔隙率，而 GO 的顯著貢獻是降低

了膜表面電荷。含有 GO 和 PVP 的 PVDF 膜在膜孔隙率，水接觸角和 Zeta 電

位特性方面表現出累加效應，並使 PVDF 的結晶型態由轉變至較親水的

型。在 pH 值為 4-10 的純水和染料溶液（NBB 和 MB-NBB）中，濾液的滲透

率從純 PVDF（P），GO 混合 PVDF（PG），PVP 混合 PVDF（PP）和 GO￾PVP 混合 PVDF（PPG）膜逐漸增加。其中，GO 和 PVP 的引入分別使滲透率

增加了幾倍和幾十倍。由於 Donnan 排斥機理，所有膜均表現出高於 80%的染

料排斥率，與微弱的染料吸附能力。由於 GO 和 PVP 的累加作用，PPG 膜具

有出色的高滲透性（953.0–1353.0 L m-2 h

-1 MPa-1）和傑出的脫色率（83.2–

91.4%），本研究證實這種複合 PVDF 膜在實際染料廢水處理應用中開了一條

可行的路。

關鍵字：離子染料；聚偏二氟乙烯；氧化石墨烯；聚乙烯吡咯烷酮；Donnan

排除；分子間相互作用；加乘作用；膜通透性