本研究之主要目的為製備適合化學迴圈釋氧程序之銅系載氧體，探討氧化銅釋氧與氧化之反應動力，並應用於石墨燃燒。實驗結果顯示：氧化銅於氮氣氣氛下進行釋氧程序時，隨著反應溫度提高，氧化銅分解速率隨之增加；而氧化過程中，反應溫度提高，不僅提高氧化反應速率，也加速氧化銅釋氧，因此造成氧化轉化率下降。研究結果亦發現，氧化銅與合成氣反應，會生成熔點低的銅金屬，因此易產生凝結團聚現象。
本研究並將氧化銅與氧化鋯混合，以製備具有高機械強度及反應特性的複合載氧體。結果顯示氧化銅與氧化鋯比例為2比3時，於合成氣及氮氣反應操作下具有50次氧化還原迴圈數。然而當氧化銅含量高於氧化鋯時，易造成氧化銅與合成氣反應時，會生成較多的液相銅，燒結並覆蓋氧化鋯，導致粒徑增加、比表面積減少以及氧化還原迴圈數下降。本研究亦利用澱粉作為載氧體孔洞生成劑，可有效提升載氧體之反應性，載氧體並可穩定進行2000圈的氧化還原操作，然而，添加過多澱粉於氧化銅/氧化鋯複合載氧體會導致機械強度降低。
本研究亦將氧化銅/氧化鋯複合載氧體與石墨置入固定床反應器進行測試，調整載氧體顆粒尺寸與反應溫度，探討載氧體與石墨之化學迴圈釋氧程序(CLOU)及化學迴圈程序(CLP)反應，實驗結果顯示於CLOU程序中以氧化銅/氧化鋯載氧體與石墨之燃燒良好。相對於CLP程序中，先將石墨被氣化後再與載氧體燃燒，完全轉換燃料所耗費的時間降低3倍。

Preparation of Cu-based oxygen carrier and combustion of graphite in CLOU was investigated in this study. The reaction kinetics for decomposition and oxidation of CuO oxygen carrier in CLOU was studied. Experimental results indicated that in decomposition process, the decomposition rate was increased with increasing reaction temperature thus decomposition conversion was increased. On the contrary, in oxidation processes, the oxidation conversion decreased due to decomposition rate was tent to oxidation rate with increasing reaction temperature. The experiment also revealed that CuO reacted with syngas was obvious agglomeration due to reducing CuO to Cu, and Cu was exhibited lower melting temperature.
In order to increase the mechanical strength of carriers and increase the reactivity for carriers with syngas, CuO oxygen carriers were prepared with ZrO2 as inert support by mechanical mixing. The results showed that CuO/ZrO2 composed of 60 % ZrO2 was better redox reactivity than that reactivity of CuO under nitrogen and syngas atmosphere after 50 redox cycles. Higher ratio of CuO to ZrO2 was disadvantageous since liquid sintering lead to increase in particle size, decrease in surface area and number of redox cycles. Annealed at 1000 oC of CuO/ZrO2 was found adequate mechanical strength and induce the highest reduction conversion under syngas and nitrogen atmosphere due to smaller average particle size. After sintering process, the reactivity was decreased thus mixing 1.25 mg starch could be increased reactivity and number of 2000 redox cycles. However, the crush strength of CuO/ZrO2 was decreased with increasing starch content.
CuO/ZrO2 oxygen carrier was used in subsequent experiment of graphite combustion in fixed bed reactor. The combustion mechanism of graphite and oxygen carrier in CLOU was investigated with various particle sizes of CuO/ZrO2 and reaction temperatures. It revealed that CuO/ZrO2 oxygen carrier with particle size between 0.3-0.5 mm reacted at 950 oC in CLOU has three times lower time for 100% conversion of graphite than gasification of graphite and combustion in CLP.

Abad, A., I. Adanez-Rubio, P. Gayan, F. Garcı’a-Labiano, L.F. de Diego and J. Adanez, “Demonstratin of Chemical-looping with Oxygen Uncoupling (CLOU) Process in a 1.5 kWth Continuously Operating Unit Using a Cu-based Oxygen Carrier,” Int. J. Greenhouse Gas Control, Vol. 6, pp. 189-200 (2012).
Adanez-Rubio, I., P. Gayan, F. Garcı’a-Labiano, L.F. de Diego, J. Adanez and A. Abad, “Development of CuO-based Oxygen-carrier Materials Suitable for Chemical-looping with Oxygen Uncoupling (CLOU) Process,” Energy Procedia, Vol. 4, pp. 417-424 (2011).
Adanez-Rubio, I., P. Gayan, A. Abad, L.F. de Diego, F. Garcı’a-Labiano and J. Adanez, “Evaluation of a Spray-dried CuO/MgAl2O4 Oxygen Carrier for the Chemical-looping with Oxygen Uncoupling (CLOU) Process,” Energy Fuels, Vol. 26, pp. 3069-3081 (2012).
Adanez, J., L.F. de Diego, F. Garcı’a-Labiano, P. Gayan and A. Abad, “Selection of Oxygen Carriers for Chemical-looping Combustion,” Energy Fuels, Vol. 18, pp. 371-377 (2004).
Adanez, J., A. Cuadrat, A. Abad, P. Gayan, L.F. de Diego and F. Garcı’a-Labiano, “Ilmenite Activation during Consecutive Redox Cycles in Chemical-looping Combustion,” Energy Fuels, Vol. 24, pp.1402-1413 (2010).
Albano, M.P., L.B. Garrido, K. Plucknett and L.A. Genova, “Processing of Porous Yttria-stabilized Zirconia Tapes: Influence of Starch Content and Sintering Temperature,” Ceram. Int., Vol. 35, pp. 1783-1791 (2009).
Almeida, F.A., E.C. Botelho, F.C.L. Melo, T.M.B. Campos and G.P. Thim, “Influence of Cassava Starch Content and Sintering Temperature on the Alumina Consolidation Technique,” J. Eur. Ceram. Soc., Vol. 29, pp. 1587-1594 (2009).
Arjmand, M., A.M. Azad, H. Leion, A. Lyngfelt and T. Mattisson, “Prospects of Al2O3 and MgAl2O4-supported CuO Oxygen Carriers in Chemical-looping Combustion (CLC) and Chemical-looping with Oxygen Uncoupling,” Energy Fuels, Vol. 25, pp.5493-5502 (2011).
Azimi, G., H. Leion, T. Mattison and A. Lyngfelt, “Chemical-looping with Oxygen Uncoupling Using Combined Mn-Fe Oxides, Testing in Batch Fluidized Bed,” Energy Procedia, Vol. 4, pp. 370-377 (2011).
Berguerand, N. and A. Lyngfelt, “The Use of Petroleum Coke as Fuel in a 10 kWth Chemical-looping Combustor,” Int. J. Greenhouse Gas Control, Vol. 2, pp. 169-179 (2008).
Bhattacharya, P. and K. Chattopadhyay, “Nano Al2O3-Pb and SiO2-Pb Cermets by Sol-gel Technique and the Phase Transformation Study of the Embedded Pb Particles,” Nanostuct. Mater., Vol. 12, pp. 1077-1080 (1999).
Cao, Y. and W.P. Pan, “Investigation of Chemical Looping Combustion by Solid Fuels. 1. Process Analysis,” Energy Fuels, Vol. 20, pp. 1836-1844 (2006).
Chadda, D., J.D. Ford and M.A. Fahim, “Chemical Energy Storage by the Reaction Cycle CuO/Cu2O,” Int. J. Energy Res., Vol. 13, pp. 63-73 (1989).
Cho, P., T. Mattisson and A. Lyngfelt, “Comparison of Iron-, Nickel-, Copper- and Manganese-based Oxygen Carriers for Chemical-looping Combustion,” Fuel. Vol. 83, pp. 1215-1225 (2004).
Cho, P., T. Mattisson and A. Lyngfelt, “Defluidization Conditions for a Fluidized Bed of Iron Oxide-, Nickel Oxide-, and Manganese Oxide-containing Oxygen Carriers for Chemical-looping Combustion,” Ind. Eng. Chem. Res., Vol. 45, pp. 968-977 (2006).
Chuang, S.Y., J.S. Dennis, A.N. Hayhurst and S.A. Scott, “Development and Performance of Cu-based Oxygen Carriers for Chemical-looping Combustion,” Combust. Flame, Vol. 154, pp. 109-121 (2008).
Corbella, B.M., L.F. de Diego, F. Garcı’a-Labiano, J. Adanez and J.M. Palacios, “The Performance in a Fixed Bed Reactor of Copper-based Oxides on Titania as Oxygen Carriers for Chemical Looping Combustion of Methane,” Energy Fuels, Vol. 19, pp. 433-441 (2005).
Corbella, B.M., L.F. de Diego, F. Garcla-Labiano, J. Adanez and J. M. Palacios, “Characterization and Performance in a Multicycle Test in a Fixed-bed Reactor of Silica-supported Copper Oxide as Oxygen Carrier for Chemical-looping Combustion of Methane,” Energy Fuels, Vol. 20, pp. 148-154 (2006).
Cuadrat, A., A. Abad, F. Garcı’a-Labiano, P. Gayan, L.F. de Diego and J. Adanez, “Ilmenite as Oxygen Carrier in a Chemical Looping Combustion System with Coal,” Energy Procedia, Vol. 4, pp. 362-369 (2011).
Davies, D.E., U.R. Evans and J.N. Agar, “The Oxidation of Iron at 175 to 350 oC,” Proc. R. Soc. London, Ser. A, Vol. 225, pp. 443-462 (1954).
Dennis, J.S., S.A. Scott and A.N. Hayhurst, “In situ Gasification of Coal using Steam with Chemical Looping: A Technique for Isolating CO2 from Burning a Solid Fuel,” J. Energy Inst., Vol. 79, pp. 187-190 (2006).
de Diego, L.F., F. Garcı’a -Labiano, J. Adanez, P. Gayan, A. Abad, B.M. Corbella and J.M. Palacios, “Development of Cu-based Oxygen Carriers for Chemical-looping Combustion,” Fuel, Vol. 83, pp. 1749-1757 (2004).
Dueso, C., A. Abad, F. Garcia-Labiano, L.F. de Diego, P. Gayan and J. Adanez, “Reactivity of a NiO/Al2O3 Oxygen Carrier Prepared by Impregnation for Chemical-looping Combustion,” Fuel, Vol. 89, pp. 3399-3409 (2010).
Eyring, E.M., G. Konya, J.S. Lighty, A.H. Sahir, A.F. Sarofim and K. Whitty, “Chemical Looping with Copper Oxide as Carrier and Coal as Fuel,” Oil gas sci. technol., Vol. 66, pp.209-221 (2011).
Evans, A.G. and C.H. Hsueh, “Behavior of Large Pores during Sintering and Hot Isostatic Pressing,” J. Am. Ceram. Soc., Vol. 69, pp. 444-448 (1986).
Figueroa, J.D., 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. Greenhouse Gas Control, Vol. 2, pp. 9-20 (2008).
Foglar, H.S., “Elements of Chemical Reaction Engineering,” Pearson Education, Inc., U.S., (1999).
Gadalla, A.M.M., W.F. Ford and J. White, “Equilibrium Relationships in the System CuO-Cu2O-SiO2,” Trans. Br. Ceram. Soc., Vol. 62, pp. 57 (1963).
Gao, Z., L. Shen, J. Xiao, C. Qing and Q. Song, “Use of Coal as Fuel for Chemical-looping Combustion with Ni-based Oxygen Carrier,” Ind. Eng. Chem. Res., Vol. 47, pp. 9279-9287 (2008).
Gayan, P., C. Dueso, A. Alberto, J. Adanez, L.F. de Diego and F. Garcı’a-Labiano, “NiO/Al2O3 Oxygen Carriers for Chemical-looping Combustion Prepared by Impregnation and Deposition-precipitation Methods,” Fuel, Vol. 88, pp. 1016-1023 (2009).
Gayan, I., I. Adanez-Rubio, A. Abad, L.F. de Diego, F. Garcı’a-Labiano and J. Adanez, “Development of Cu-based Oxygen Carrier for Chemical-looping with Oxygen Uncoupling (CLOU) Process,” Fuel, Vol. 96, pp. 226-238 (2012).
Hautman, D.J., F.L. Dryer, K.P. Schug and I. Glassman, “A Multiple-step Overall Kinetic Mechanism for the Oxidation of Hydrocarbons,” Combust. Sci. Technol., Vol. 25, pp. 219-235 (1981).
Jerndal, E., T. Mattisson and A. Lyngfelt, “Thermal Analysis of Chemical-looping Combustion,” Chem. Eng. Res. Des., Vol. 84, pp. 795-806 (2006).
Jin, H. and M. Ishida, “Reactivity Study on Natural-gas-fueled Chemical-looping Combustion by a Fixed-bed Reactor,” Ind Eng Chem Res., Vol. 41, pp. 4004-4007 (2002).
Johansson, M., T. Mattisson and A. Lyngfelt, “Investigation of Fe2O3 with MgAl2O4 for Chemical-looping Combustion,” Ind. Eng. Chem. Res., Vol. 43, pp. 6978-6987 (2004).
Johansson, M., T. Mattisson and A. Lyngfelt, “Investigation of Mn3O4 with Stabilized ZrO2 for Chemical-looping Combustion,” Chem. Eng. Res. Des., Vol. 84, pp. 807-818 (2006).
Leion, H., T. Mattisson and A. Lyngfelt, “The use of Petroleum Coke as Fuel in Chemical-looping Combustion,” Fuel, Vol. 86, pp. 1947-1958 (2007).
Leion, H., “Capture of CO2 from Solid Fuels Using Chemical-looping Combustion and Chemical-looping with Oxygen Uncoupling,” Thesis for the degree of doctor of philosophy in department of chemical and biological engineering environmental inorganic chemistry, Sweden (2008a).
Leion, H., A. Lyngfelt, M. Johansson, E. Jerndal and T. Mattisson, “The Use of Ilmenite as an Oxygen Carrier in Chemical-looping Combustion,” Chem. Eng. Res. Des., Vol. 86, pp. 1017-1023 (2008b).
Leion, H., E. Jerndal, B.M. Steenari, S. Hermansson, M. Israelsson, E. Jansson, M. Johnsson, R. Thunberg, A. Vadenbo, T. Mattisson and A. Lyngfelt, “Solid Fuels in Chemical-looping Combustion Using Oxide Scale and Unprocessed Iron Ore as Oxygen Carriers,” Fuel, Vol. 88, pp.1945-1954 (2009a).
Leion, H., Y. Larring, E. Bakken, R. Bredesen, T. Mattisson and A. Lyngfelt, “Use of CaMn0.875Ti0.125O3 as Oxygen Carrier in Chemical-looping with Oxygen Uncoupling,” Energy Fuels. Vol. 23, pp. 5276-5283 (2009b).
Leion, H., T. Mattisson, and A. Lyngfelt, “Using Chemical-looping with Oxygen Uncoupling (CLOU) for Combustion of Six Different Solid Fuels,” Energy Procedia, Vol. 1, pp. 447-453 (2009c).
Li, F., H.R. Kim, D. Sridhar, F. Wang, L. Zeng, J. Chen and L.S. Fan, “Syngas Chemical Looping Gasification Process: Oxygen Carrier Particle Selection and Performance,” Energy Fuels, Vol. 23, pp. 4182-4189 (2009).
Li, Z.S., Y.Y. Wen and N.S. Cai, “Chemical looping Combustion of Petroleum Coke with Co-based Oxygen Carrier,” 1st meeting of the high temperature solid looping cycles network, oviedo, spain (2009b).
Lin, F.J.T., L.C. de Jonghe and M.N. Rahaman, “Initial Coarsening and Microstructural Evolution of Fast-fired and MgO-doped Alumina,” J. Am. Ceram. Soc., Vol. 80, pp. 2891-2896 (1997).
Lyon, R.K. and J.A. Cole, “Unmixed Combustion: An Alternative to Fire,” Combust. Flame, Vol. 121, pp. 249-261 (2000).
Maneshian, M.H. and A. Simchi, “Solid Sate and Liquid Phase Sintering of Mechanically Activated W-20 wt. % Cu Powder Mixture,” J. Alloys Compd., Vol. 463, pp. 153-159 (2008).
Mattisson, T. and A. Lyngfelf, “Capture of CO2 Using Chemical-looping Combustion, ” First Biennial Meeting of the Scandinavian-Nordic Section of the Combustion Institute, Goteborg, Sweden (2001).
Mattisson, T., A. Jardnas and A. Lyngfelt, “Reactivity of Some Metal Oxides Supported on Alumina with Alternating Methane and Oxygen : Application for Chemical-looping Combustion,” Energy Fuels, Vol. 17, pp. 643-651 (2003).
Mattisson, T., M. Johansson, and A. Lyngfelt, “Multicycle Reduction and Oxidation of Different Types of Iron Oxide Particles Application to Chemical-looping Combustion,” Energy Fuels, Vol. 18, pp. 628-637 (2004).
Mattisson, T., M. Johansson and A. Lyngfelt,“CO2 Capture from Coal Combustion Using Chemical-looping-reactivity Investigation of Fe, Ni and Mn Based Oxygen Carriers Using Syngas,” The Clearwater Coal Conference (2006a).
Mattisson, T., M. Johansson and A. Lyngfelt, “The Use of NiO as an Oxygen Carrier in Chemical-looping Combustion,” Fuel, Vol. 85, pp. 736-747 (2006b).
Mattisson, T., Q. Zafa, M. Johansson and A. Lyngfelt, “Chemical-looping Combustion as a New CO2 Management Technology,” First Regional Symposium on Carbon Management, Dhahran, Saudi-Arabia (2006c).
Mattisson, T., H. Leion and A. Lyngfelt, “Chemical-looping with Oxygen Uncoupling Using CuO/ZrO2 with Petroleum Coke,” Fuel. Vol. 88, pp. 683-690 (2009a).
Mattisson, T., A. Lyngfelt and H. Leion, “Chemical-looping with Oxygen Uncoupling for Combustion of Solid Fuels,” Int. J. Greenhouse Gas Control, Vol. 3, pp. 11-19 (2009b).
Mohamed, N.R., “Sintering of Ceramics,” U.S.A, Taylor & Francis Group (2008).
Nasar, R.S., M. Cerqueira, E. Longo and J.A. Varela, “Sintering Mechanisms of ZrO2•MgO with Addition of TiO2 and CuO,” Ceram. Int., Vol. 30, pp. 571-577 (2004).
Noggle, J. H., “Physical Chemistry,” United Kingdom, TBS The Book Service Ltd. (1984).
Pitchumani, R., O. Zhupanska, G.M.H. Meesters and B. Scarlett, “Measurement and Characterization of Particle Strength Using a New Robotic Compression Tester,” Powder Technol., Vol. 143-144, pp. 56-64 (2004).
Prisedsky, V.V. and V.M. Vinogradov, “Fragmentation of Diffusion Zone in High-temperature Oxidation of Copper,” J. Solid State Chem., Vol. 177, pp. 4258-4268 (2004).
Richter, H.J. and K.F. Knoche, “Reversibility of Combustion Processes, in Efficiency and Costing –second Law Analysis of Processes,” ACS symposium series, Vol. 235, pp. 71–85 (1983).
Rosenzweig, C., D. Karoly, M. Vicarelli, P. Neofotis, Q. Wu and G. Casassa, “Attributing Physical and Biological Impacts to Anthropogenic Climate Change,” Nature, Vol. 453, pp. 353-357 (2008).
Ryden, M., A. Lyngfelt and T, Mattisson, “CaMn0.875Ti0.125O3 as Oxygen Carrier for Chemical-looping Combustion with Oxygen Uncoupling (CLOU)-experiments in a Continuously Operating Fluidized-bed Reactor System,” Energy Procedia, Vol. 4, pp. 341-348 (2011a).
Ryden, M., A. Lyngfelt and T, Mattisson, “Combined Manganese/Iron Oxides as Oxygen Carrier for Chemical Looping Combustion with Oxygen Uncoupling (CLOU) in a Circulating Fluidized Bed Reactor System,” Int. J. Greenhouse Gas Control, Vol. 5, pp. 356-366 (2011b).
Scheffe, J.R., M.D. Allendorf, E.N. Coker, B.W. Jacobs, A.H. McDaniel and A.W. Weimer, “Hydrogen Production via Chemical Looping Redox Cycles Using Atomic Layer Deposition-synthesized Iron Oxide and Cobalt Ferrites,” Chem.Mater., Vol. 23, pp. 30-38 (2011).
Shen, L., J. Wu, Z. Gao and J. Xiao, “Reactivity Deterioration of NiO/Al2O3 Oxygen Carrier for Chemical Looping Combustion of Coal in a 10 kWth Reactor,” Combust. Flame, Vol. 156, pp. 1377-1385 (2009).
Shulman, A., E. Cleverstam, T. Mattisson and A. Lyngfelt, “Manganese/Iron, Manganese/Nickel and Manganese/Silicon Oxide Used in Chemical-looping with Oxygen Uncoupling (CLOU) for Combustion of Methane,” Energy Fuels, Vol. 23, pp. 5269-5275 (2009).
Shulman, A., E. Cleverstam, T. Mattisson and A. Lyngfelt, “Chemical-looping with Oxygen Uncoupling Using Mn/Mg-based Oxygen Carriers-oxygen Release and Reactivity with Methane,” Fuel, Vol. 90, pp. 941-950 (2011).
Zafar, Q., T. Mattisson and B. Gevert, “Integrated Hydrogen and Power Production with CO2 Capture Using Chemical-looping Reforming-redox Reactivity of Particles of CuO, Mn2O3, NiO, and Fe2O3 Using SiO2 as a Support,” Ind. Eng. Chem. Res., Vol. 44, pp. 3485-3496 (2005).
Zafar, Q., T. Mattisson and B. Gevert, “Redox Investigation of Some Oxides of Transition-state Metals Ni, Cu, Fe, and Mn Supported on SiO2 and MgAl2O4,” Energy Fuels, Vol. 20, pp. 34-44 (2006).
Zaharescu, M., S. Mihaiu, S. Zuca and K. Matiasovsky, “Contribution to the Study of SnO2-based Ceramics,” J. Mater. Sci., Vol. 26, pp. 1666-1672 (1991).
Zhu, Y., K. Mimura and M. Isshiki, “Oxidation Mechanism of Cu2O to CuO at 600-1050 oC,” Oxid. Met., Vol. 62, pp. 207-222 (2004).
Zhu, Y., K. Mimura and M. Isshiki, “Influence of Oxide Grain Morphology on Formation of the CuO Scale during Oxidation of Copper at 600-1000 oC,” Corros. Sci., Vol. 47, pp. 537-544 (2005).