臺灣博碩士論文加值系統

本研究是利用實驗室合成的聚偏二氟乙烯(Polyvinylidene fluoride, PVDF)平板式薄膜，來組裝模組進行濃縮過濾和透析過濾用於玻尿酸分離純化之效能探討，合成薄膜的組成為PVDF、磷酸三乙酯(Triethyl phosphate, TEP)及Tween-20的混合溶液，將改變沉澱槽之組成成分以製備不同結構之薄膜，探討其薄膜結構對蒸餾操作之影響。以單成分HA溶液以及HA/LY雙成分溶液為實驗對象，並採用批次恆壓型式，針對攪拌速度、電解質種類和電解質濃度等操作變數之改變進行實驗分析。
研究結果顯示，隨著沉澱槽TEP wt%的比例增加，在濃縮過濾其濃縮程度都會優於沒改質的薄膜其濾液累積體積比沒改質的還來的多，而在HA透析過濾其濾速都會高於沒改質的薄膜，是由於隨著TEP在沉澱槽的比例增加薄膜表面皮層結構不易形成，且大孔洞數變多。加入攪拌可有效降低過濾阻力而提高濾速，電解質離子強度越大，使玻尿酸分子萎縮捲曲的程度越大，使得HA堆積形態越為緊密，濾速相對較低；而電解質造成LY與薄膜以及HA之間的靜電作用力降低，使LY不易吸附於膜面上，較易通過薄膜，提高移除效率。

The synthesized polyvinylidene fluoride (PVDF) flat-sheet membrane was used in concentrate filtration and diafiltration for separation and purification of hyaluronic acid. The flat membranes were prepared from the dope solution of PVDF, Triethyl phosphate(TEP) and Tween-20, and varying the concentration of TEP in the coagulation bath. The membrane structures were observed by the SEM analysis. In this study, the HA solution and the mixture solution of HA/LY were used as the feed solution, and experimented by adopting Concentrate filtration and diafiltration in a dead-end stirred cell. The experimented results were discussed under different operating conditions such as stirred rate, electrolyte type and electrolyte concentration.
The results shows that concentrate filtration’s concentration and accumulation filtrate better than original membranes which prepared by higher weigh percent of TEP solution. In the diafiltration for HA the flux higher performance than original membranes. Membrane have large pore size in the top surface is increasing the weight percent of TEP in coagulant bath. Addition of stirring can reduce the filtration resistance and improve the permeate flux. The permeate flux decreases with the increase of ion strength of electrolyte which causes the HA molecules become more shrunken and then form a compact deposited layer on membrane surface. However, the LY molecules can pass through the membrane more easily as the electrolyte is added. The strength of electrode ion will hinder the surface charge of LY, and decrease the electrostatic interference between LY molecules and membrane.

目錄
致謝 I
中文摘要 II
英文摘要 III
目錄 IV
圖目錄 VII
表目錄 IX
第1章 緒論 1
1.1 前言 1
1.2 薄膜分離 1
1.3 薄膜型態與模組 5
1.4 濃度極化與結垢現象 6
1.5 研究目的 8
第2章 文獻回顧 11
2.1 玻尿酸 11
2.1.1 玻尿酸之發現 12
2.1.2 玻尿酸之純化 13
2.1.3 玻尿酸之應用 15
2.2 透析過濾相關研究 17
2.2.1 透析過濾之理論分析 17
2.2.2 透析過濾純化效果之研究 18
2.2.3 透析過濾之應用 20
2.3 影響濾速之因素 20
2.4 提升濾速之方法 22
2.5 濾速分析模式 23
2.6 薄膜製備方法 28
第3章 實驗裝置與方法 33
3.1 實驗裝置 33
3.2 實驗藥品 34
3.3 薄膜製備 35
3.4 實驗步驟 36
3.5 薄膜性質分析 36
3.5.1 薄膜的形態和表面孔洞分析 36
3.5.2 薄膜膜厚及孔隙度測試 37
3.5.3 接觸角測試 37
3.6 操作條件 38
3.7 分析方法 38
3.7.1 玻尿酸含量之測定 38
3.7.2 蛋白質含量之測定 40
3.7.3 阻隔率(Rejection, Rj) 41
3.7.4 移除率(Reduction, Rd) 42
3.7.5 保留液濃度 42
3.8 實驗後薄膜之清洗 42
第4章 結果與討論 45
4.1 薄膜特性與結構分析 45
4.1.1 薄膜SEM結構分析 45
4.1.2 薄膜之孔隙度 46
4.1.3 薄膜之接觸角 46
4.2 薄膜純水濾速 47
4.3 濃縮過濾之過濾行為 48
4.3.1 攪拌速度對濃縮過濾之影響 48
4.3.2 不同PVDF薄膜對濃縮過濾之影響 48
4.4 單成分溶液之透析過濾行為 49
4.4.1 攪拌速度對單成份溶液之影響 49
4.4.2 不同PVDF薄膜對HA濾液通量之影響 49
4.4.3 不同PVDF薄膜對HA阻隔濾之影響 50
4.4.4 進料濃度對單成分溶液之影響 50
4.4.5 電解質對單成分溶液之影響 51
4.5 雙成分HA/LY溶液之透析過濾行為 51
4.5.1 電解質種類 51
4.5.2 電解質濃度 52
4.5.3 分離效率 52
4.5.4 HA之阻隔率 53
4.5.5 過濾之阻力分析 54
4.5.6 PVDF-T40與不膜材濾速比較 54
4.5.7 不同膜材性能比較 54
4.5.8 電解質之移除 55
第5章 結論 76
參考文獻 80
附錄A 88
附錄B 89

圖目錄
Fig. 1-1 The classification of membrane separation process [2]. 9
Fig. 1-2 The diagram of (a)dead end filtration and (b)cross-flow filtration [3]. 10
Fig. 2-1 The biosynthetic pathway for HA production in S. zooepidemicus[53]. 25
Fig. 2-2 The processes of HA production in S. zooepidemicus[53]. 26
Fig. 2-3 The Schematic diagram of diafiltration. 27
Fig. 2-4 Typical methods to reduce concentration polarization and fouling in pressure driving membrane processes [2]. 28
Fig. 2-5 Schematic representation of the isothermal phase behavion of a nonsolvent-solvent-polymer system consisting of a one-phase region (І),a two-phase region (П) and a gel (Ш) [54] . 31
Fig. 2-6 Schematic representation of mass transfer occurring at the membrane/ coagulant surface. ：flux of coagulant, ：flux of solvent [54] 32
Fig. 3-1 The experimental set-up of diafiltration operation. 43
Fig. 4-1 PVDF平板薄膜之SEM 5k倍率上表面結構圖 56
Fig. 4-2 PVDF平板薄膜之SEM 10k倍率上表面結構圖 57
Fig. 4-3 PVDF平板薄膜之SEM 5k倍率下表面結構圖 58
Fig. 4-4 PVDF平板薄膜之SEM截面結構圖 59
Fig. 4-5 PVDF平板薄膜之SEM 3k倍率之上截面結構圖 60
Fig. 4-6不同PVDF薄膜之純水濾速 61
Fig. 4-7 不同壓力下 PVDF(T40)之純水濾速 61
Fig. 4-8固定時間不同攪拌速度下PVDF(T40)其濃縮過濾下HA率速對時間比較圖 62
Fig. 4-9 濃縮過濾在固定狀態下不同PVDF薄膜之濃縮過濾下HA濾速對時間比較圖 62
Fig. 4-10在固定120分鐘下攪拌速度對濃縮過濾之濾液累積體積之影響 63
Fig. 4-11 不同攪拌速度下PVDF(T40)其透析過濾HA濾速比較圖 63
Fig. 4-12 在固定120分鐘下不同攪拌速度再透析過濾對濾速的影響 64
Fig. 4-13 在壓力200kPa跟轉速400rpm不同PVDF薄膜HA的阻隔率 64
Fig. 4-14 不同進料濃度對透析過濾濾速影響 65
Fig. 4-15 不同電解質濃度對HA透析過濾濾速影響 65
Fig. 4-16 不同電解質對HA/LY過濾濾速之影響 66
Fig. 4-17不同電解質對HA/LY透析過濾濾速之影響 66
Fig. 4-18不同電解質對HA/LY透析過濾濾速之影響 67
Fig. 4-19 不同電解質濃度(NaCl)對HA/LY透析過濾之影響 67
Fig. 4-20 不同電解質濃度(KCl)對HA/LY透析過濾之影響 68
Fig. 4-21 不同電解質濃度(MgCl2)對HA/LY透析過濾之影響 68
Fig. 4-22 HA/LY溶液中不同種類的電解質對的LY穿透濃度影響 69
Fig. 4-23 不同濃度MgCl2對HA/LY溶液的LY穿透濃度影響-69
Fig. 4-24 HA/LY溶液中不同的電解質和濃度對HA阻隔濾之影響 70
Fig. 4-25 電解質濃度對阻力的影響 70
Fig. 4-26 不同電解質(0.01M)之阻力分析 71
Fig. 4-27不同電解質(0.5M)之阻力分析 71
Fig. 4-28 PVDF(T40)薄膜跟商業模的濾速比較 72
Fig. 4-29 PVDF(T40)與商業模之LY穿透濃度比較 72
Fig. 4-30 PVDF(T40)與商業模之HA阻隔率比較 73
Fig. 4-31 商業膜之阻力分析 73
Fig. 4-32電解質移除與透析體積圖 74

表目錄
表 1-1 The classification of driving force in different operation process [2]. 9
表 3-1製膜液組成與製備條件 44
表 3-2 玻尿酸之性質 44
表 3-3溶菌酶之性質 44
表 4-1 PVDF薄膜基本結構與物性分析 74
表 4-2商業膜之性質 75

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