由於溫室效應的影響，二氧化碳之減量一直是目前各方面所關心的重要議題。除了各種以二氧化碳為原料的反應研究被大量探討外，前提是需先將廢氣中的二氧化碳分離與濃縮出來，才能用以作為後續反應原料。在本實驗中是使用分離、濃縮氧氣且已經商業化的多床體變壓吸附法來分離混合氣中的二氧化碳，而混合氣的氣體比例是模擬火力發電廠所產生的廢氣。
藉由改變進料流速、旋轉閥的速度、進料濃度、進料溫度以及底部出口端的速度來增加二氧化碳的濃縮比以及回收率。然而結果顯示，由於受到原本用來分離回收氧氣的多床體變壓吸附法影響，所得到的二氧化碳濃縮比不高。儘管這些受到這些限制，從實驗結果當中依然可以了解到如何去改裝多床體變壓吸附法來回收二氧化碳。

Due to the green house effect, the reduction and recovery technology of carbon dioxide becomes an important research topic nowadays. In addition to the researches about using carbon dioxide as a reactant, the recovery and concentration of carbon dioxide from waste gas are the key issues. In this study, multiple-bed-PSA module designed to separate and concentrate oxygen from air for medical purpose and a commercial product was used to study the feasibility of recovery CO2 from gaseous mixture. The gaseous mixture was simulation of waste gas from power plant.
The influences of some operation parameters of multiple-bed PSA including feed flow rate, rotary valve speed, CO2 concentration, feed temperature, and bottom-outlet flow rate were studied in various conditions. The results show the CO2 concentration was low under the physical limitation. In spite of the limitation, the results can be used to repack the multiple-bed PSA for CO2 recovery.

ACKNOWLEDGEMENTS ………………………………………………...i
ABSTRACT (English) ii
ABSTRACT (Chinese) iii
TABLE OF CONTENTS iv
LIST OF TABLES vii
LIST OF FIGURES viii
GLOSSARY OF NOTATION xi
CHAPTER 1 INTRODUCTION 1
1.1 Background 1
1.2 Objectives and Scope 6
CHAPTER 2 LITERATURE REVIEW 9
2.1 CO2 Recovery Methods 9
2.1.1 Physical Method 9
2.1.2 Chemical Method 9
2.1.3 Biological Method 11
2.2 The Principle of PSA 12
2.2.1 Four-step Single-bed PSA 13
2.2.2 Four-step Dual-bed PSA 16
2.2.3 Other Operations 19
2.3 Multiple-bed PSA 21
2.4 Microporous Adsorbents 21
2.4.1 Selectivity 21
2.4.2 Mechanism Separation 25
2.4.3 Zeolites 26
CHAPTER 3 EXPERIMENT 32
3.1 Experimental Materials 32
3.2 Experimental Apparatus and Equipment 32
3.3 Procedures 32
3.3.1 Measurement of CO2 and N2 Concentration 32
3.3.2 Experimental Procedures 36
3.3.3 Experimental Conditions 42
3.3.4 Multiple-bed PSA Process Description 45
CHAPTER 4 RESULTS AND DISCUSSION 46
4.1 Calculation of the Breakthrough Time by Wave Theory 46
4.2 The Results of Column Experiment 49
4.2.1 Breakthrough Curve 49
4.2.2 Adsorption Isotherm 60
4.2.3 The Prediction of Breakthrough 61
4.3 The Results of multiple-bed-PSA Experiment 64
4.3.1 Effect of Rotary Valve Speed 64
4.3.2 Effect of CO2 Concentration 69
4.3.3 Effect of Feed Flow Rate 72
4.3.4 Effect of Flow Rate of Bottom Outlet 75
4.3.5 Effect of Feed Temperature 80
CHAPTER 5 CONCLUSIONS 86
5.1 General Conclusion 86
5.2 Future Work 87
REFERENCES 88

Advanced Specialty Gas Equipment Web Site (2006). from http://www. asge-online.com./pdf/MSieves.pdf.
Break, D. W. (1974). Zeolite Molecular Sieves, 10th ed. Canada, John Wiley and Sons, Inc.
Chen, J. Y. (2004). Study of carbon dioxide recovery and utilization by pressure swing adsorption related process. Unpublished doctoral dissertation, National Central University, Taiwan. (in Chinese)
Chern, J. M. and Chien, Y. W. (2002). Adsorption of nitrophenol onto activated carbon: isotherms and breakthrough curves. Water Research, 36, 647-655.
Chou, C. T. and Chen, C. Y. (2004). Carbon dioxide recovery by vacuum swing adsorption. Separation and Purification Technology, 39, 51-65.
Chue, K. T., Kim, J. N., Yoo, Y. J., Cho, S. H., and Yang, R. T. (1995). Comparison of activated carbon and zeolite 13X for CO2 recovery from flue gas by pressure swing adsorption. Industrial Engineering Chemistry Research, 34, 591-598.
Chung, M. S. (2000). Simulation of two vacuum swing adsorption processes for SO2 recovery. Unpublished master dissertation, National Central University, Taiwan. (in Chinese)
Elwell, L. C. and Grant, W. S. (2005). Technical overview of carbon dioxide capture technologies for coal-fired power plants. from http://www.mpr.com/energy/extras/co2_capture.pdf.
Environmental Protection Agency Web Site (2004). from http://www.epa. gov/globalwarmimg/kids/greenhouse.html.
Gupta, H. and Fan, L. S. (2002). Carbonation-calcination cycle using high reactivity calcium oxide for carbon dioxide separation from flue gas. Industrial Engineering Chemistry Research, 41, 4035-4042.
Herzog, H. (1999). An introduction to CO2 separation and capture technologies. from http://sequestration.mit.edu/pdf/introduction_to_ capture.pdf.
Herzog, H. and Falk-Pedersen, O. (2000). The kvaerner membrane contactor: lessons from a case study in how to reduce capture costs. Fifth International Conference on Greenhouse Gas Control Technologies Carins Australia, 121-125.
Hsieh, J. C. (1997). Confines of united nation framework convention on climate change for CO2 emission. The Libertytimes Post. (in Chinese).
Jobic, H., Paoli, H., Méthivier, A., Ehlers, G., Kärger, J., and Krause, C. (2003). Diffusion of n-hexane in 5A zeolite studied by the neutron spin-echo and pulsed-field gradient NMR techniques. Microporous and Mesoporous Materials, 59, 113-121.
Jung, T. S. and Shiang, M. J. (2005). Greenhouse effect make the flowers in bloom spring effloresce in fall. Science Development, 388, 66-71.
Kim, M. B., Lee, S. J., Choi, D. K. and Lee, C. H. (2005). Kinetic separation of CO2/CH4 mixture using carbon molecular sieve by two-bed PSA. Nonisothermal Operation from http://aiche.confex.com/aiche/2005 /techprogram/P25657.html.
Ko, D., Siriwardane, R., and Biegler, L. T. (2003). Optimization of a pressure-swing adsorption process using zeolite 13X for CO2 sequestration. Industrial Engineering Chemistry Research, 42, 339-348.
Lin, C. C. and Liu, W. T. (2006). The technology of CO2 recovery http://www.itri.org.tw/cfc/co2/15/ gw15_4.pdf (in Chinese).
Mark, R., and Worral, R. (2000). Greenhouse gas key performance indicators for Australian coal mines. CSIRO Exploration and Mining, Fifth International Conference on Greenhouse Gas Control Technologies Cairns Australia, 1020-1025.
Pidwirny Michael (2006). The Greenhouse Effect from http://www. physicalgeography.net/fundamentals/7h.html.
Ruthven, D. M., Raghavan, N. S, and Hassan, M. M. (1986). Adsorption and diffusion of nitrogen and oxygen in a carbon molecular sieve. Chemical Engineering Science, 41, 1325-1332.
Ruthven, D. M. (1984). Principles of adosrption and adsorption process. Published simultaneously in Canada, United States of America, 10.
Sherwood, T. K., Pigford, R. L., Wilke, C. R. (1975). Mass transfer, Chapter 10, New York, McGraw-Hill.
Sircar, S. (1989). Pressure swing adsorption technology. Adsorption Science and Technology, 158, 285-321.
Sircar, S., (2001). Applications of gas separation by adsorption for the future, Adsorption Science and Technology, 19, 5, 347.
Siriwardane, R. V., Shen, M. S., Fisher, E. P., and Poston, J. A. (2001). Adsorption of CO2 on molecular sieves and activated carbon. Energy & Fuels, 15, 279-284.
Skarstrom, C. W. (1960). Method and apparatus for fractionating gaseous mixtures by adsorption. U. S. Patent, 2944627.
Turnock, P. H. and Kadlec, R. H. (1971). Separation of nitrogen and methane via periodic adsorption. AIChE J., 17, 2, 335-342.
Council for Sustainable Development Taiwan, (2002). UNFCCC National Communication of the Republic of China (Taiwan), 2-23(in Chinese)
Wikipedia Web Site (2006a). Kyoto Protocol from http://en.wikipedia.org /wiki/Kyoto_Protocol.
Wikipedia Web Site (2006b). Carbon Dioxide Sink from http://en.wikipedia.org /wiki/Carbon_sequestration.