氧化石墨烯對聚醯胺/聚丙烯腈複合薄膜滲透蒸發效能之影響

Effect of graphene oxide on pervaporation performance of polyamide/polyacrylonitrile TFC membrane

黃承駿(Chen-Chun Huang)

指導教授 ： 黃書賢 ； 李魁然

中原大學/工學院/化學工程研究所/碩士(2012年)

https://doi.org/10.6840/cycu201200621

摘要

本研究係以二胺單體1,2-Bis(2-aminoethoxy)ethane (BAE)與醯氯單體1,3,5-Benzenetricarbonyl trichloride (TMC)，在改質的聚丙烯腈(modified polyacrylonitrile, mPAN)非對稱基材膜表面進行界面聚合反應。而為了增加複合薄膜之效能，研究中於水相單體溶液中添加Graphene oxide (GO)無機層狀材料增加透過路徑以提升選擇性。首先使用FT-IR、XRD、AFM及XPS對自行合成之GO進行鑑定，結果發現GO是屬於單層分散於水中，且具有親水性含氧官能基-COOH等；針對複合薄膜之鑑定，則是使用SEM觀察其表面及截面之結構型態，並且進一步利用新穎的分析技術─正子湮滅光譜技術分析添加GO層狀材料對聚醯胺層結構之影響，則將有助於釐清薄膜結構與滲透蒸發效能之間的關聯性。
　　研究中發現，隨著GO層狀材料添加量增加，將會改變原本聚醯胺結構之分離機制，並且進一步影響其透過效能，同時聚醯胺層厚度亦會隨著GO添加量之增加而有所下降；此外，由正子湮滅技術分析結果得知，GO層狀材料係以均勻狀態分布於聚醯胺層之中。
　　此外，藉由吸附實驗得知GO層狀材料的造成薄膜分離機制主要受到擴散選擇主導，同時探討滲透蒸發操作條件對效能之影響，如操作溫度、進料濃度、操作壓力、及進料種類等。實驗結果顯示，添加150ppmGO於水相單體溶液中進行界面聚合所製備複合薄膜，在操作溫度25°C下應用於滲透蒸發分離90wt%乙醇水溶液，其透過量約545g/m2 h，透過端水濃度約97.1wt%，此結果相較於未添加GO層狀複合薄膜，其透過效能有所提升。

關鍵字

氧化石墨烯 ； 界面聚合 ； 聚醯胺 ； 滲透蒸發

並列摘要

To improve the pervaporation performance of polyamide thin-film composite (TFC) membranes prepared by interfacial polymerization between 1,2-bis(2-aminoethoxy)ethane (BAE) monomer and 1,3,5-benzenetricarbonyl trichloride (TMC) monomer, graphene oxide (GO) were added into the BAE monomer solution to prepare polyamide-GO/mPAN composite membranes. The synthesized GO was characterized by FT-IR, XRD, AFM and XPS, and the results showed that GO was single layer sheet with hydrophilic functional group such as –COOH groups. Surface and cross-section morphologies of TFC membranes were observed by SEM. In order to further realize the effect of GO content on polyamide layer structure, the positron annihilation spectroscopy (PAS) coupled with a variable monoenergy slow positron beam (VMSPB) is utilized to detect the depth profile of multilayer structure through the polyamide-GO/mPAN composite membrane to correlate with pervaporation performance.
It was found that GO content altered pervaporation mechanism of polyamide-GO/mPAN TFC membranes, so that the separation performance improved. On the other hand, the thickness of polyamide layer decreased with increasing GO content. In addition, GO were distributed in the polyamide layer by the interfacial polymerization process from the results of doppler-broadened energy spectrum (DBES) results.
The effect of GO concentration on the pervaporation mechanism through polyamide-GO/mPAN composite membrane were diffusion control. The effects of operating condition of pervaporation process, such as the operating temperature, feed concentration, permeate pressure, and feed component, were also investigated. From the results of the pervaporation separation experiments, the polyamide-150ppmGO/mPAN had excellent performance of 90wt% aqueous ethanol solution, which is a permeation flux of 545 g/m2 h and a water concentration in permeate of 97.1 wt%.

並列關鍵字

graphene oxide ； pervaporation ； interfacial polymerization ； polyamide

參考文獻

2. 魏士偉, 聚醯胺/醋酸纖維酯複合膜應用於滲透蒸發分離之研究, 中原大學化學工程學系碩士學位論文 (2009).

22. 黃書賢, 界面聚合聚醯胺複合膜應用於滲透蒸發分離程序之研究, 中原大學化學工程學系博士學位論文 (2008).

39. 蘇郁蕙,幾丁聚醣混成膜中無機材成份對滲透蒸發效能之影響,中原大學化學工程學系碩士學位論文 (2004)

53. J.S. Bunch, S.S. Verbridge, J.S. Alden, A.M. van der Zande, J.M. Parpia, H.G. Craighead, P.L. McEuen, Impermeable atomic membranes from graphene sheets, Nano Lett. 8 (2008) 2458-2462.

3. S. Zhang, E. Drioli, Review: pervaporation membranes, Sep. Sci. Technol. 30 (1995) 1–31.