複合膜中界面聚合層的氣體分離性質

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姓名

蔡傑(Chieh Tsai) 查詢紙本館藏

畢業系所

化學工程與材料工程學系

論文名稱

複合膜中界面聚合層的氣體分離性質
(Gas separation properties of interfacially polymerized layers in thin film composite membranes)

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摘要(中)

利用薄膜來進行氣體分離是一種低耗能的技術，但高選擇性的薄膜往往通量很低，高通量的薄膜選擇性又不佳，因此如何同時提高薄膜的分離效率與氣體通量一直是研究的重心。廣泛使用於製備逆滲透及奈米過濾膜的界面聚合法，可以製作出一層薄且緊密的分離層，藉由此方法，有可能得到一個高通量且高選擇性的氣體分離薄膜，但在文獻中鮮少報導。
近幾年來有幾篇文獻，報告利用界面聚合法製作的複合膜來進行氣體分離，但大部分的研究都是在探討增加薄膜的含氮比例來提升二氧化碳/甲烷或是二氧化碳/氮氣的分離，卻很少關於最困難的氧/氮分離的報導。於是在這篇研究中，我們使用使用四種水相單體diethylenetriamine (DETA)，m-phenylene diamine (m-PD) ，melamine，piperazine (PIP)，兩種有機相單體1,3,5-benzenetricarbonyl chloride (TMC) ，cyanuric chloride (CC)進行界面聚合，探討單體的立體構型，反應官能基的數目，與含氮量的多寡對分離效率的影響，也探討反應時間以及單體濃度比的效應。
氧/氮分離的結果發現，薄膜的含氮量與氧/氮選擇比之間關連不大，聚合時薄膜的分子交聯程度與高分子堆疊的方式應是影響選擇比的主要原因，線性以及過度網狀交聯都不利於提高選擇比，兩相單體均為平面構型且鍵結於同一平面也容易產生缺陷，兩相單體反應官能基比為3:2且其中一單體為非平面構型者，具有高選擇比與不錯的氣體通量(如：1%PIP/1%TMC具有7.72 kg h-1 m-2 atm-1的氧氣通量，0.74 kg h-1 m-2 atm-1的氮氣通量以及選擇比10.43)。增加聚合時間對氧氣、氮氣的分離效率並沒有助益，反而會因為薄膜厚度增加而減少氣體通量，而兩相單體重量百分比為1:1時所得到的薄膜，分離效率較佳。

摘要(英)

Gas separation by membrane is an energy saving separation technology. However, high selectivity membranes are often defeated by their low permeation fluxes and high flux membranes usually suffer from their low selectivity. Therefore, how to obtain a high flux and highly selective gas separation membrane is always a major research emphasis in membrane technology. Interfacial polymerization, a technique often used in RO and NF membrane fabrication, can produce a thin and dense layer on a supporting membrane. The thin film composite (TFC) membrane by interfacial polymerization should be a good candidate of high flux and high selectivity gas separation membrane. However, limited reports mentioned about the gas separation properties of TFC membranes. Although there have emerged a couple reports in the recent year about using TFC membranes for CO2/CH4 and CO2/N2 separation. The focus was on increasing membrane polarity in order to enhancing CO2 solubility. No comments were on the structure of thin layers for gas separation, particularly on O2/N2 separation. We, therefore, tried to compare the gas separation properties of many interfacial polymerized layers by selecting 4 aqueous phase monomers: diethylenetriamine (DETA), m-phenylenediamine (mPD), melamine, and pieprazine (PIP), and 2 organic phase monomers: trimethyl chloride (TMC) and cyanuric chloride (CC). We intended to study how the shape, the number of functional groups, and the nitrogen content of monomers affect membrane performance. The effects of reaction time and monomer concentration were also under investigation.
The experiment results showed that the permselectivity was not related to nitrogen content. The degree of cross-linkage and the packing of polymer chains strongly affected membrane performance. Linear polymer and over crosslinking were not favorable. Planar aqueous and organic phase monomers forming crosslinking network at the same plane created defects in the layer. We have found that the optimum ratio of reacting groups of monomers in two phases is 3:2. It could be demonstrated by the membrane synthesized by 1%PIP and 1%TMC, which had an oxygen flux of 7.72 kg h-1 m-2 atm-1 and a permselectivity of 10.43. To increase polymerization time was not beneficial to membrane selectivity. On the contrary, it decreased gas permeability by increasing membrane thickness. We also found that the 1:1 concentration ratio of monomers was required to maintain membrane selectivity.

關鍵字(中)

★ 氣體分離
★ 界面聚合

關鍵字(英)

★ gas separation
★ interfacial polymerization

論文目次

中文摘要 I
Abstract VII
圖目錄 XIII
表目錄 XV
第一章緒論 1
1-1 研究背景 1
1-1-1 使用薄膜分離的優點 2
1-1-2 不同薄膜材料的選擇 2
1-1-3 氣體分離膜的種類 4
1-1-4 界面聚合膜之優點 5
1-1-5 氣體分離膜的應用 5
1-2 研究動機及目的 8
第二章文獻回顧 10
2-1 簡介：氣體分離膜 10
2-2 發展史 10
2-3 氣體分離的機制及原理 13
2-3-1 薄膜構造 13
2-3-2 薄膜型態與氣體傳送之間的關係 14
2-4 氣體分離之傳送理論 18
2-4-1 氣體分離的過程 18
2-4-2 氣體分離之機制 19
2-4-3 氣體分子在薄膜中的傳送量 19
2-4-4 穿透係數(Permeability coefficient) 22
2-5-5 選擇性 (Permselectivity) 22
2-5 氣體分離膜之製備方法 24
2-6 影響界面聚合法主要因素 30
2-6-1 水相單體或有機相單體的選擇 30
2-6-2 水相溶液或有機相溶液的濃度 32
2-6-3 界面聚合反應時間 32
第三章實驗藥品、儀器設備與流程 35
3-1 實驗藥品 35
3-2 實驗儀器設備 36
3-3 實驗方法流程 37
3-3-1 基材膜製備 37
3-3-2 Polyamide薄膜製備 38
3-3-3 實驗架構 40
3-4 薄膜性質測試 41
3-4-1 掃描式電子顯微鏡鑑定薄膜型態 (Scanning Electronic Microscope) 41
3-4-2 X射線光電子能譜 (X-ray Photoelectron Spectroscopy) 42
3-4-3 氣體通量實驗 42
3-5 高分子化學結構 44
第四章結果與討論 47
4-1 表面與截面型態結構變化 48
4-2 氧/氮分離特性 58
4-2-1不同聚合單體合成之選擇層的氮氣通量 59
4-2-2 不同聚合單體合成之選擇層的氧/氮選擇比 61
4-2-3 不同界面聚合單體濃度對氣體分離膜通量的影響 62
4-3 分離層含氮量對氧/氮選擇性之影響 65
4-4 各種膜氧/氮分離的綜合表現 73
結論 75
參考文獻 76

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指導教授

阮若屈、胡蒨傑
(Ruoh-Chyu Ruaan、Chien-Chieh Hu)

審核日期

2011-7-27

推文