臺灣博碩士論文加值系統

本論文利用數值分析法模擬雙塔五步驟以矽膠作為吸附劑去吸附煙道廢氣中混合氣體（15%CO2和85%N2）的真空變壓吸附（Vacuum Pressure Swing Adsorption, VPSA）程序，目的是將二氧化碳及氮氣分離回收，以達到二氧化碳捕捉封存。
本系統數學方程式的建立包括（1）線性驅動模式、（2）Ergun equation、（3）成分m在吸附床內的質量平衡方程式和（4）吸附床之能量平衡方程式，將這四大方程式無因次化且透過正交配置法將偏微分方程式轉換成常微分方程式，再利用FORTRAN語言的電腦程式建立此模擬系統，去模擬出各個階段吸附床中每個位置壓力、莫耳分率等變化，其中數學方程式所包含的參數及操作條件是參考Yan et al.這篇文獻。
雖然現階段無法完整模擬出真空變壓吸附由第一階段到第五階段之結果，其可能的原因為考量到壓力隨著吸附床在軸方向上的變化，以及邊界條件的假設，但是在於數學模型四大方程式的詳細建構上是完整可被利用的。

A vacuum pressure swing adsorption(VPSA) process that used silica gel as adsorbent to capture CO2 from dry flue gas(15%CO2/85%N2) by two-bed five-steps operation is investigated through the numerical simulation method. The feature of this process is to capture high concentration carbon dioxide and nitrogen gas, and carbon dioxide can be recovered and stored.
The four mathematical equation (1) linear driving force,(2) Ergun equation,(3) component m mass balance equation in adsorption bed,(4) energy balance equation in adsorption bed are established on this simulation system. First, let the four mathematical equation to dimensionless unit. Secondary, the partial differential equation is transformed into the ordinary differential equation solved by orthogonal collocation method. The simulation system to find the each position pressure and mole fraction etc. on adsorption bed in every step is established by Fortran programming language. The operating parameters and conditions used in this study are referred to the paper Yan et al.
Currently, we can’t complete simulation whole VPSA process from first step to fifth step, the possible causes include that we consider the pressure varies with the adsorption bed in the axial direction and the assume of boundary condition, but in the detailed of the mathematical model for the four equations is completely useful.
Keyword：vacuum pressure swing adsorption、silica gel、carbon dioxide、nitrogen、orthogonal collocation method

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誌謝 iii
摘要 iv
Abstract v
目錄 vi
圖目錄 ix
表目錄 x
第一章 緒論 - 1 -
1.1研究動機 - 1 -
1.2研究目的 - 4 -
第二章 原理及文獻回顧 - 5 -
2.1吸附基本原理 - 5 -
2.1.1吸附現象 - 5 -
2.1.2吸附種類 - 7 -
2.1.3吸附氣體原理 - 10 -
2.1.4變壓吸附程序簡介 - 11 -
2.1.5等溫吸附曲線 - 12 -
2.2文獻回顧 - 20 -
2.2.1變壓吸附程式之發展 - 20 -
2.2.2以PSA製程回收二氧化碳的應用 - 23 -
2.2.3變壓吸附步驟 - 25 -
2.3 程序模擬範例簡介 - 27 -
第三章 數學模式與研究方法 - 32 -
3.1數學模式之基本假設 - 33 -
3.2統御方程式 - 34 -
3.2.1數學模式 - 34 -
3.2.2定義無因次變數及無因次化 - 39 -
3.2.3正交配置法 - 41 -
3.3邊界條件 - 44 -
3.4自由度分析 - 54 -
3.5電腦求解步驟 - 56 -
第四章 結果與討論 - 59 -
4.1 Step1加壓步驟模擬結果 - 59 -
4.2 Step2吸附步驟模擬結果 - 64 -
第五章 結論 - 69 -
參考文獻 - 71 -
符號說明 - 73 -

圖目錄
圖2-1吸附及脫附作用示意圖 - 6
圖2-2IUPAC歸類的六種平衡吸附曲線 - 15
圖2-3VPSA5步驟操作示意圖 - 28
圖3-1電腦流程步驟 - 58
圖4-程序模擬中加壓步驟之壓力隨操作時間關係圖 - 60
圖4-2 範例文獻吸附床內壓力隨操作時間之關係圖 - 60
圖4-3程序模擬中加壓步驟之CO2莫耳分率隨操作時間關圖 - 62
圖4-4程序模擬中加壓步驟之CO2在固相隨操作時間關係圖 - 62
圖4-5程序模擬中加壓步驟之N2莫耳分率隨操作時間關係圖 - 63
圖4-6程序模擬中加壓步驟之N2在固相隨操作時間關係圖 - 63
圖4-7程序模擬中吸附步驟之壓力隨操作時間關係圖 - 65
圖4-8程序模擬中吸附步驟之CO2莫耳分率隨軸向位置關係圖 - 66
圖4-10程序模擬中吸附步驟之不同位置的CO2莫耳分率隨操作時間關係圖 - 67
圖4-11程序模擬中吸附步驟之CO2在固相隨軸向位置關係圖 - 68
圖4-12範例文獻吸附步驟結束時之CO2在固相隨軸向位置關係圖 - 68

表目錄
表2-1 物理吸附及化學吸附主要差異比較表 - 9 -
表2-3 比較從煙道廢氣中捕捉二氧化碳之性能 - 24 -
表2-4 VPSA系統各階段操作時間及總操作時間 - 27 -
表2-5 VPSA系統操作方向 - 29 -
表2-6 VPSA吸附床之參數 - 30 -
表2-7 VPSA吸附劑之參數 - 30 -
表2-8 二氧化碳與氮氣之Langmuir model相關參數 - 30 -
表2-9 系統其它操作參數 - 31 -

[1]H.Yan, Q.Fu, Y.Zhou, D.Li, and D.Zhang, “CO2 capture from dry flue gas by pressure vacuum swing adsorption: A systematic simulation and optimization,” Int. J. Green house Gas Control, 51, pp.1–10, 2016.
[2]J.D.Figueroa, T.Fout, S.Plasynski, H.McIlvried, and R. D.Srivastava, “Advances in CO2 capture technology-The U.S. department of energy’s carbon sequestration program,” Int. J. Greenh. Gas Control, 2, pp.9–20, 2008.
[3]S. J.Davis, K.Caldeira, and H. D.Matthews, “Future CO2 emissions and climate change from existing energy infrastructure,” Science, 329, 2010.
[4]S.Solomon et al., “IPCC, Climate change 2007: the physical science basis. contribution of working group I to the fourth assessment report of the intergovernmental panel on climate change,” pp.302–804, 2007.
[5]工業技術研究院化學工業研究所, “二氧化碳回收技術.”
[6]朱育廷, “正己醇 / 正戊醇水溶液在活性碳之雙成份吸附平衡,” 長庚大學, 2006.
[7]盧贊生, “用沸石作分離及吸附程序之研究,” 國立清華大學, 1988.
[8]杜奕旻, “二氧化碳/甲烷雙成分混合氣體之變壓吸附模擬研究,” 長庚大學, 2016.
[9]K. S. W. S.S.J.Gregg, Adsorption,surface area and porosity.
[10]K. S. K.Douglas M. Ruthven, Shamsuzzaman Farooq, Pressure Swing Adsorption. .
[11]L. H.Shendalman and J. E.Mitchell, “A study of heatless adsorption in the model system CO2 in He, I,” Chem. Eng. Sci., 27, pp.1449–1458, 1972.
[12]K.Weaver andC. E.Hamrin, “Separation of hydrogen isotopes by heatless adsorption,” Chem. Eng. Sci., 29, pp.1873–1882, 1974.
[13]E. S.Kikkinides, J. A.Ritter, and R. T.Yang, “Pressure swing adsorption for simultaneous purification and sorbate recovery,” J. Chinese Inst. Chem. Eng., vol. 22, pp. 399–407, 1991.
[14]Y. J.Kim, Y. S.Nam, andY. T.Kang, “Study on a numerical model and PSA (pressure swing adsorption) process experiment for CH4/CO2 separation from biogas,” Energy, 91, pp.732–741, 2015.
[15]J.Ling, P.Xiao, A.Ntiamoah, D.Xu, P.Webley, and Y.Zhai, “Strategies for CO2 capture from different CO2 emission sources by vacuum swing adsorption technology,” Chinese J. Chem. Eng., 24, pp.460–467, 2016.
[16]D.Li et al., “Experiment and simulation for separating CO2/N2 by dual-reflux pressure swing adsorption process,” Chem. Eng. J., 297, pp.315–324, 2016.
[17]S.-H.Cho, J.-H.Park, H.-T.Beum, S.-S.Han, and J.-N.Kim, “A 2-stage PSA process for the recovery of CO2 from flue gas and its power consumption,”, pp.405–410., 2004
[18] D.Ko, R.Siriwardane, and L. T.Biegler, “Optimization of pressure swing adsorption and fractionated vacuum pressure swing adsorption processes for CO2 capture,” 2005.
[19]J.Zhang, P. A.Webley, and P.Xiao, “Effect of process parameters on power requirements of vacuum swing adsorption technology for CO2 capture from flue gas,” Energy Convers. Manag., 49, pp.346–356, 2008.
[20]Z.Liu, C. A.Grande, P.Li, J.Yu, and A. E.Rodrigues, “Multi-bed vacuum pressure swing adsorption for carbon dioxide capture from flue gas,” Sep. Purif. Technol., 81, pp.307–317, 2011.
[21]L.Wang et al., “Experimental evaluation of adsorption technology for CO2 capture from flue gas in an existing coal-fired power plant,” Chem. Eng. Sci., 101, pp.615–619, 2013.
[22]Jérôme Merel, M.Clausse, and F.Meunier, “Experimental investigation on CO2 post−combustion capture by indirect thermal swing adsorption using 13X and 5A zeolites,” 2007.
[23]C.Shen, Z.Liu, P.Li, and J.Yu, “Two-stage VPSA process for CO2 capture from flue gas using activated carbon beads,” Ind. Eng. Chem. Res., 51, pp.5011–5021, 2012.
[24]B.R.B, S.W.E, and L.E.N, Transport phenomena.