臺灣博碩士論文加值系統

乙烯-冰片烯共聚物為新世代工程塑膠，環烯烴共聚物(COC)，的一種，在其生產程序中，乙烯在甲苯及冰片烯混合溶液中的溶解度將會影響COC中乙烯基團比例，因此我們欲探討不同操作條件下，乙烯的溶解度情形，並使用熱力學模式進行關聯，以增加對未知條件下之預測能力。
本研究主要探討不同溫度、壓力下，乙烯在甲苯、冰片烯及COC混合溶液之溶解度情形。實驗溫度為323.15 K、373.15 K及423.15 K，壓力範圍5bar至25bar，混合溶液中冰片烯含量為0wt%至85wt%，COC含量為0wt%至28%。實驗方法採用壓力下降法，利用平衡槽之壓力變化判斷系統是否達平衡，為靜態式平衡法。實驗結果發現乙烯在上述混合溶液中的溶解度將隨壓力上升而增加，但隨溫度上升而下降；不同溫度下，甲苯與冰片烯混合溶液組成比例的不同對乙烯溶解度的影響情形將有所不同；混合溶液中COC的含量增加時，將會使乙烯的溶解度下降。
對於熱力學模式的關聯，我們選用Peng-Robinson 狀態方程式(PR EOS)並配合凡得瓦單一流體(vdW1)混合律及Zhong-Masuoka (Z-M)混合律兩種，計算方式採用泡點壓力計算法，進行數據關聯，以求得最佳化之雙成分交互作用參數。為了進行其他溫度的預測，我們將關聯所得的交互作用參數以溫度的線性關係表示，對於乙烯與甲苯雙成分系統，vdW1及Z-M混合律的交互作用參數與溫度具優異的線性關係；乙烯、甲苯與冰片烯三成分系統，vdW1混合律的交互作用參數隨溫度變化情形較難預測，而Z-M混合律的交互作用參數則是與溫度呈線性關係；乙烯、甲苯、冰片烯與COC四成分系統，vdW1及Z-M混合律的交互作用參數與溫度的關係較難預測。我們以PR EOS配合vdW1及Z-M混合律進行關聯，結果皆相當精確，AAD值在5%內。

Ethylene-norbornene copolymer is one of the new high quality engineering plastics, polycyclic olefin copolymer (COC). In the producing process, attaching of ethylene group in COC is affected by the solubility of ethylene in toluene and norbornene mixtures. So this study was measuring the solubility of ethylene at different conditions, and correlating the solubility by thermodynamic model. The correlation parameters will be used to predict the solubility of ethylene of conditions when the experimental data are not available.
In this study, the solubility of ethylene at various temperatures (323.15 K-423.15 K), pressures (5bar-25bar), concentration of norbornene (0-85wt%), and concentration of COC (0-40wt%) in toluene were measured by a pressure decaying method. The results show that the solubility of ethylene increases with increasing pressure, decreases with increasing temperature. The solubility of ethylene in mixtures is affected by the composition of mixtures. When concentration of COC in mixtures was increased, the solubility of ethylene in mixtures will be decreased.
The solubility data were correlated by the Peng-Robinson equation of state (PR EOS) with the van der Waals one-fluid (vdW1) and the Zhong-Masuoka (Z-M) mixing rules using bubble pressure calculation method with the binary interaction parameters, Lij or kij. For predicting the solubility of ethylene in mixtures at other temperatures, the binary interaction parameters were showed linear relationship with temperature. For ethylene and toluene binary system, the binary interaction parameters of vdW1 and Z-M mixing rules curve very linearly dependent on temperature. For ethylene, toluene, and norbornene ternary system, the binary interaction parameters of Z-M mixing rule have very good linear relationship with temperature, but not vdW1 mixing rule. For ethylene, toluene, norbornene, and COC quaternary system, the linear relationship with temperature is not valid. Finally, PR EOS with vdW1 or Z-M mixing rules was used to correlate the experimental results with good accuracy.

中文摘要 Ⅰ
英文摘要 Ⅱ
目錄 Ⅲ
圖目錄 Ⅴ
表目錄 Ⅶ
符號說明 Ⅸ
第一章 緒論 1
1.1 前言 1
1.2 環烯烴共聚物(COC) 1
1.3 研究動機 2
第二章 熱力學理論及模式 4
2.1 汽液相平衡準則 4
2.2汽液相平衡計算 4
2.3 逸壓係數 5
2.4 狀態方程式 5
2.4.1 單分子型狀態方程式(EOS for Simple Molecules) 6
2.4.2 鏈狀型狀態方程式(EOS for Chain Molecules) 7
2.4.2結合型狀態方程式(EOS for Associating Molecules) 7
2.5 混合律 8
2.5.1 單參數凡得瓦單一流體混合律(vdW1) 8
2.5.2 Wong-Sandler(W-S)混合律 9
2.5.3 Zhong-Masuoka(Z-M)混合律 10
第三章 文獻回顧 12
3.1 輕質氣體與溶劑雙成分系統 12
3.2 輕質氣體與高分子雙成分系統 12
3.3 溶劑與高分子雙成分系統 14
3.4 輕質氣體、溶劑與高分子三成分系統 17
第四章 實驗部份 18
4.1 實驗藥品 18
4.2 實驗方法 18
4.2.1 裝置單元介紹 19
4.2.2 實驗步驟 20
4.3 檢量線製作 20
4.3.1 乙烯檢量線製作 21
4.3.2 甲苯檢量線製作 21
4.3.3 甲苯-冰片烯檢量線製作 21
4.4 乙烯溶解度之計算 21
4.5 可靠性試驗 23
4.6 正式實驗 23
4.7 關聯模式 23
4.7.1 高分子參數之求得 24
4.7.2 氣液相平衡關聯 25
第五章 結果與討論 26
5.1 檢量線的擬合 26
5.1.1 乙烯檢量線擬合 26
5.1.2 甲苯檢量線擬合 26
5.1.3 甲苯-冰片烯檢量線擬合 26
5.2 可靠性試驗 27
5.3 正式實驗 27
5.3.1 乙烯與甲苯之雙成分系統 27
5.3.2 溶解度的經驗關聯式 28
5.3.3乙烯、甲苯與冰片烯之三成分系統 28
5.3.4乙烯、甲苯、冰片烯與COC之四成分系統 30
第六章 結論 32
參考文獻 33
圖 40
表 53
Appendix A. Equation of State 65
Appendix B. GCVOL method 68
Appendix C. Development of solubility model 71

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