本研究主要量測酸性氣體二氧化碳在混合醇胺水溶液系統(Triethanolamine (TEA) + Piperazine (PZ) + Water (H2O))下的氣液平衡溶解度數據，所探討的系統濃度分別為:2 kmol × m-3 TEA + 0.5 ～1.5 kmol × m-3 PZ 以及 3 kmol × m-3 TEA + 0.5～1.5 kmol × m-3 PZ；溫度範圍為40, 60, 以及 80 °C；二氧化碳分壓範圍為0.7～160 kPa。
迴歸部份選擇以Kent and Eisenberg (1976) 提出的熱力學模式來建立本系統的氣液平衡熱力學模式，並利用所建立的熱力學模式來描述本實驗的數據，最終可以得到令人滿意的結果。
而在文獻上的氣液平衡數據獨缺本研究所選擇的系統TEA + PZ + H2O ，所以除了提供一組新的實驗系統數據之外，所建立的熱力學計算模式也可作為吸收酸性氣體設備方面的參考依據。

New experimental results have been presented for the solubilities of carbon dioxide in mixtures of Triethanolamine (TEA) + Piperazine (PZ) + Water (H2O) have been measured at 40, 60, and 80 °C and at partial pressures of acid gases up to 160 kPa.
The concentration ranges of the ternary mixtures studied were 2 kmol × m-3 TEA + 0.5 to 1.5 kmol × m-3 PZ and 3 kmol × m-3 TEA + 0.5 to 1.5 kmol × m-3 PZ aqueous solutions.
The modified Kent-Eisenberg model has been used to represent the solubility of mixtures of CO2 in the considered ternary solutions. And the model reasonably reproduces the equilibrium partial pressures of CO2 above the ternary solutions for the systems.

摘要............................................................................................................. I
Abstract ......................................................................................................II
致謝.......................................................................................................... III
目錄.......................................................................................................... IV
表目錄......................................................................................................VI
圖目錄.....................................................................................................VII
第1 章 緒論.............................................................................................. 1
1.1 前言................................................................................................. 1
1.2 酸性氣體吸收技術介紹................................................................. 2
1.3 醇胺簡介......................................................................................... 3
1.4 TEA (Triethanolamine)及PZ (Piperazine)介紹.............................. 5
1.4.1 TEA ............................................................................................ 5
1.4.2 PZ ............................................................................................... 6
1.5 研究目的......................................................................................... 9
第2 章 原理............................................................................................ 10
2.1 氣液平衡model 文獻回顧........................................................... 10
2.1.1 Ideal Solution Model:............................................................... 10
2.1.2 Activity Coefficient Model: ..................................................... 11
2.2 氣液平衡模式建立....................................................................... 13
2.2.1 理論......................................................................................... 13
2.2.2 計算......................................................................................... 15
第3 章 實驗............................................................................................ 17
3.1 文獻之氣液平衡實驗設備與分析法........................................... 17
3.1.1 實驗設備................................................................................. 17
3.1.2 分析法..................................................................................... 17
3.2 實驗藥品....................................................................................... 18
3.3 實驗裝置....................................................................................... 21
3.4 實驗步驟....................................................................................... 23
3.5 吸收負載(α)量測........................................................................... 23
3.6 CO2 分壓( CO2 P )計算...................................................................... 24
第4 章 結果與討論................................................................................ 25
4.1 對照實驗....................................................................................... 25
4.2 氣液平衡數據量測結果............................................................... 25
4.3 氣液平衡模式預測....................................................................... 48
第5 章 結論............................................................................................ 65
符號說明.................................................................................................. 66
參考文獻.................................................................................................. 68
附錄A...................................................................................................... 74


表目錄
Table 1-1 常用醇胺之結構式................................................................. 4
Table 1-2 Literature data of CO2 and H2S solubility in TEA systems .... 7
Table 1-3 Literature data of CO2 and H2S solubility in PZ systems....... 8
Table 3-1 文獻之氣液平衡實驗設備.................................................. 19
Table 3-2 TEA 及PZ 之熱物性質....................................................... 20
Table 4-1 Solubility of CO2 in 2 kmol ⋅ m
-3
MDEA solution at 40℃ .. 26
Table 4-2 Solubility of CO2 in 2 kmol ⋅ m
-3
TEA solution ................... 28
Table 4-3 Solubility of CO2 in 2 kmol ⋅ m
-3
TEA + 0.5 kmol ⋅ m
-3
PZ
solution ................................................................................ 29
Table 4-4 Solubility of CO2 in 2 kmol ⋅ m
-3
TEA + 1.0 kmol ⋅ m
-3
PZ
solution ................................................................................ 30
Table 4-5 Solubility of CO2 in 2 kmol ⋅ m
-3
TEA + 1.5 kmol ⋅ m
-3
PZ
solution ................................................................................ 31
Table 4-6 Solubility of CO2 in 3 kmol ⋅ m
-3
TEA solution ................... 32
Table 4-7 Solubility of CO2 in 3 kmol ⋅ m
-3
TEA + 0.5 kmol ⋅ m
-3
PZ
solution ................................................................................ 33
Table 4-8 Solubility of CO2 in 3 kmol ⋅ m
-3
TEA + 1.0 kmol ⋅ m
-3
PZ
solution ................................................................................ 34
Table 4-9 Solubility of CO2 in 3 kmol ⋅ m
-3
TEA + 1.5 kmol ⋅ m
-3
PZ
solution ................................................................................ 35
Table 4-10 本研究所採用之氣液平衡常數及亨利定律常數.............. 53
Table 4-12 迴歸所得之氣液平衡參數.................................................. 54



圖目錄
Figure 3-1 氣液平衡實驗裝置圖........................................................... 22
Figure 4-1 Solubility of CO2 in 2 kmol ⋅ m
-3
MDEA solution in 40℃ .. 27
Figure 4-2 Solubility of CO2 in 2 kmol ⋅ m
-3
TEA solution..................... 36
Figure 4-3 Solubility of CO2 in 2 kmol ⋅ m
-3
TEA + 0.5 kmol ⋅ m
-3
PZ
solution................................................................................... 37
Figure 4-4 Solubility of CO2 in 2 kmol ⋅ m
-3
TEA + 1.0 kmol ⋅ m
-3
PZ
solution................................................................................... 38
Figure 4-5 Solubility of CO2 in 2 kmol ⋅ m
-3
TEA + 1.5 kmol ⋅ m
-3
PZ
solution................................................................................... 39
Figure 4-6 Solubility of CO2 in 3 kmol ⋅ m
-3
TEA solution..................... 40
Figure 4-7 Solubility of CO2 in 3 kmol ⋅ m
-3
TEA + 0.5 kmol ⋅ m
-3
PZ
solution................................................................................... 41
Figure 4-8 Solubility of CO2 in 3 kmol ⋅ m
-3
TEA + 1.0 kmol ⋅ m
-3
PZ
solution................................................................................... 42
Figure 4-9 Solubility of CO2 in 3 kmol ⋅ m-3 TEA + 1.5 kmol ⋅ m-3 PZ
solution................................................................................... 43
Figure 4-10 Solubility of CO2 in Aqueous TEA + PZ solutions at 40℃.
Points: data；Lines: calculated by Kent-Eisenberg model. .. 45
Figure 4-11 Solubility of CO2 in Aqueous TEA + PZ solutions at 60℃.
Points: data；Lines: calculated by Kent-Eisenberg model. .. 46
Figure 4-12 Solubility of CO2 in Aqueous TEA + PZ solutions at 80℃.
Points: data；Lines: calculated by Kent-Eisenberg model. .. 47
Figure 4-13 Comparison of predicted and measured partial pressure for
CO2 in 2 kmol ⋅ m
-3
TEA systems. ......................................... 49
Figure 4-14 Comparison of predicted and measured partial pressure for
CO2 in 3 kmol ⋅ m
-3
TEA systems. ......................................... 50
Figure 4-15 Comparison of predicted and measured partial pressure for
CO2 in total systems at 40, 60, and 80℃. .............................. 51
Figure 4-16 Correlation of the solubility for CO2 in aqueous 2 kmol ⋅ m
-3
TEA solution. Points: data；Lines: calculated by
Kent-Eisenberg model............................................................ 55
Figure 4-17 Correlation of the solubility for CO2 in aqueous 5 kmol ⋅ m
-3
TEA solution. Points: data；Lines: calculated by
Kent-Eisenberg model............................................................ 56
Figure 4-18 Correlation of the solubility for CO2 in aqueous TEA
solutions at 25℃. Points: data；Lines: calculated by
Kent-Eisenberg model............................................................ 57
Figure 4-19 Prediction of solubility data for CO2 in 2 kmol ⋅ m
-3
TEA +
0.5 kmol ⋅ m
-3
PZ aqueous solution from 20℃ to 100℃.
Points: data；Lines: calculated by Kent-Eisenberg model. .. 58
Figure 4-20 Prediction of solubility data for CO2 in 2 kmol ⋅ m
-3
TEA +
1.0 kmol ⋅ m
-3
PZ aqueous solution from 20℃ to 100℃.
Points: data；Lines: calculated by Kent-Eisenberg model. .. 59
Figure 4-21 Prediction of solubility data for CO2 in 2 kmol ⋅ m
-3
TEA +
1.5 kmol ⋅ m
-3
PZ aqueous solution from 20℃ to 100℃.
Points: data；Lines: calculated by Kent-Eisenberg model. .. 60
Figure 4-22 Prediction of solubility data for CO2 in 3 kmol ⋅ m
-3
TEA +
0.5 kmol ⋅ m
-3
PZ aqueous solution from 20℃ to 100℃.
Points: data；Lines: calculated by Kent-Eisenberg model. .. 61
Figure 4-23 Prediction of solubility data for CO2 in 3 kmol ⋅ m
-3
TEA +
1.0 kmol ⋅ m
-3
PZ aqueous solution from 20℃ to 100℃.
Points: data；Lines: calculated by Kent-Eisenberg model. .. 62
Figure 4-24 Prediction of solubility data for CO2 in 3 kmol ⋅ m
-3
TEA +
1.5 kmol ⋅ m
-3
PZ aqueous solution from 20℃ to 100℃.
Points: data；Lines: calculated by Kent-Eisenberg model. .. 63

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