Cu/Co/Mn基氧载体释氧动力学及机理研究

梅道锋; 赵海波; 马兆军; 杨伟进; 方彦飞; 郑楚光

Cu/Co/Mn基氧载体释氧动力学及机理研究

华中科技大学煤燃烧国家重点实验室, 湖北武汉 430074

基金项目: 国家自然科学基金(50721005, 50936001); 教育部新世纪优秀人才支持计划(NCET-10-0395)。

详细信息

通讯作者:
赵海波,E-mail:klinsmannzhb@163.com,Tel:027-87545526-8208,Fax:027-87545526。

中图分类号: O643
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出版历程
- 收稿日期: 2012-08-06
- 修回日期: 2012-10-12
- 刊出日期: 2013-02-28

Oxygen release kinetics and mechanism study on Cu-, Co-, Mn-based oxygen carrier

State Key Laboratory of Coal Combustion, Huazhong University of Science & Technology, Wuhan 430074, China

摘要

摘要: 以溶胶凝胶法制备了CuO/CuAl₂O₄、Co₃O₄/CoAl₂O₄以及Mn₂O₃/Al₂O₃氧载体,在流化床反应器中CO₂气氛下研究了不同温度下氧载体释氧特性,并通过分析得到各氧载体的释氧动力学机理函数、活化能及指前因子等重要参数。释氧过程中,氧载体CuO/CuAl₂O₄中CuO、CuAl₂O₄均为活性相,释氧后转化为Cu₂O及CuAlO₂,而Co₃O₄/CoAl₂O₄及Mn₂O₃/Al₂O₃中CoAl₂O₄和Al₂O₃均为惰性相,仅有Co₃O₄和Mn₂O₃参与释氧并分别转化为CoO和Mn₃O₄。三种氧载体的释氧过程均可由成核-核生长机理描述,释氧初期氧载体经化学反应形成新的活性核心,随后活性核心聚集形成还原态的氧载体团簇。各氧载体释氧的机理函数G(x)有不同的表达式,CuO/CuAl₂O₄、Co₃O₄/CoAl₂O₄、Mn₂O₃/Al₂O₃释氧的活化能E分别为226.37、130.06和65.90 kJ/mol,相对应的指前因子A分别为2.99×10⁶、4.96×10³和27.37 s^-1。
- 动力学机理 /
- 活化能 /
- 化学链氧解耦 /
- 富氧燃烧 /
- 氧载体
Abstract: Sol-gel derived CuO/CuAl₂O₄, Co₃O₄/CoAl₂O₄ and Mn₂O₃/Al₂O₃ oxygen carriers were studied in a fluidized bed reactor under CO₂ atmosphere, where the oxygen release characteristics under different temperatures were focused. The mechanism function and kinetics parameters in the oxygen release were obtained from the experimental data. In the process of oxygen release, the phases of CuO and CuAl₂O₄ performing as active components decompose to Cu₂O and CuAlO₂ with O₂ generation. While, only Co₃O₄ and Mn₂O₃ can release oxygen in Co₃O₄/CoAl₂O₄ and Mn₂O₃/Al₂O₃ oxygen carriers, in which Co₃O₄ and Mn₂O₃ are respectively reduced to CoO and Mn₃O₄; and CoAl₂O₄ and Al₂O₃ perform as inert carrier. The kinetic analysis show that the oxygen release of three oxygen carriers can be described by the nucleation and nuclei growth model. This means that after O₂ release the Cu-O bond (as an example) in the oxygen carrier is broken, generates Cu₂O active sites diffusing away from the reduction centers, and comes together to form Cu₂O clusters. The mechanism function G(x), the activation energy and the pre-exponential factor have different expressions or different values for different oxygen carriers. The activation energies in the oxygen release of CuO/CuAl₂O₄, Co₃O₄/CoAl₂O₄ and Mn₂O₃/Al₂O₃ oxygen carriers, are 226.37, 130.06 and 65.90 kJ/mol respectively; and the pre-exponential factors are 2.99×10⁶ s^-1, 4.96×10³ s^-1 and 27.37 s^-1 respectively.
- kinetic mechanism /
- activation energy /
- chemical looping with oxygen uncoupling /
- oxy-fuel combustion /
- oxygen carrier

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参考文献(17)

XIONG J, ZHAO H, ZHENG C, LIU Z, ZENG L, LIU H, QIU J. An economic feasibility study of O₂/CO₂ recycle combustion technology based on existing coal-fired power plants in China[J]. Fuel, 2009, 88(6): 1135-1142.

LYNGFELT A, MATTISSON T. Trestegsförbränning för avskiljning av koldioxid. Sweden, 2005.

ABAD A, ADÁNEZ-RUBIO I, GAYÁN P, GARCÍA-LABIANO F, DIEGO L F, ADÁNEZ J. Demonstration of chemical-looping with oxygen uncoupling (CLOU) process in a 1.5kW_th continuously operating unit using a Cu-based oxygen-carrier[J]. Int. J. of Greenh. Gas Con., 2012, 6(1): 189-200.

MATTISSON T, LYNGFELT A, LEION H. Chemical-looping with oxygen uncoupling for combustion of solid fuels[J]. Int. J. Greenh. Gas Con., 2009, 3(1): 11-19.

LEION H, MATTISSON T, LYNGFELT A. Using chemical-looping with oxygen uncoupling (CLOU) for combustion of six different solid fuels[J]. Energy Procedia, 2009, 1(1): 447-453.

LEION H, MATTISSON T, LYNGFELT A. Chemical Looping Combustion of Solid Fuels in a Laboratory Fluidized-bed Reactor[J]. Oil & Gas Science and Technology–Revue d’IFP Energies nouvelles, 2011, 66(2): 201-208.

ADÁNEZ-RUBIO I, GAYÁN P, GARCÍA-LABIANO F, DIEGO L F, ADNEZ J, ABAD A. Development of CuO-based oxygen-carrier materials suitable for Chemical-Looping with Oxygen Uncoupling (CLOU) process[J]. Energy Procedia, 2011, 4(1): 417-424.

GAYÁN P, ADÁNEZ-RUBIO I, ABAD A, DIEGO L F, GARCÍA-LABIANO F, ADÁNEZ J. Development of Cu-based oxygen carriers for Chemical-Looping with Oxygen Uncoupling (CLOU) process[J]. Fuel, 2012, 96(1): 226-238.

ARJMAND M, AZAD A, LEION H, LYNGFELT A, MATTISSON T. Prospects of Al₂O₃ and MgAl₂O₄-Supported CuO Oxygen Carriers in Chemical-Looping Combustion (CLC) and Chemical-Looping with Oxygen Uncoupling (CLOU)[J]. Energy Fuels, 2011, 25(11): 5493-5502.

WEN Y, LI Z, XU L, CAI N. Experimental Study of Natural Cu Ore Particles as Oxygen Carriers in Chemical Looping with Oxygen Uncoupling (CLOU)[J]. Energy Fuels, 2012, 26(6): 3919-3927.

LI Z, ZHANG T, CAI N. Experimental Study of O₂-CO₂ Production for the Oxyfuel Combustion Using a Co-Based Oxygen Carrier[J]. Ind. Eng. Chem. Res., 2008, 47(19): 7147-7153.

ZHANG T, LI Z, CAI N. Continuous O₂-CO₂ production using a Co-based oxygen carrier in two parallel fixed-bed reactors[J]. Korean J. Chem. Eng., 2009, 26(3): 845-849.

SHULMAN A, CLEVERSTAM E, MATTISSON T, LYNGFELT A. Manganese/Iron, Manganese/Nickel, and Manganese/Silicon Oxides Used in Chemical-Looping With Oxygen Uncoupling (CLOU) for Combustion of Methane[J]. Energy Fuels, 2009, 23(10): 5269-5275.

AZIMI G., LEION H, MATTISSON T, LYNGFELT A. Chemical-looping with oxygen uncoupling using combined Mn-Fe oxides, testing in batch fluidized bed[J]. Energy Procedia, 2011, 4(1): 370-377.

梅道锋, 赵海波, 马兆军, 郑楚光. Fe₂O₃/Al₂O₃ 氧载体制备方法的研究[J]. 燃料化学学报, 2012, 40(7): 795-802. MEI Dao-feng, ZHAO Hai-bo, MA Zhao-jun, ZHENG Chu-guang. Preparation method study on Fe₂O₃/Al₂O₃ oxygen carrier[J]. Journal of Fuel Chemistry and Technology, 2012, 40(7): 795-802.

赵海波, 刘黎明, 徐迪, 郑楚光, 刘国军, 蒋林林. 气体燃料化学链燃烧技术中的溶胶凝胶Ni基氧载体研究[J]. 燃料化学学报, 2008, 36(3): 261-266. ZHAO Hai-bo, LIU Li-ming, XU Di, ZHENG Chu-guang, LIU Guo-jun, JIANG Lin-lin. NiO/NiAl₂O₄ oxygen carriers prepared by sol-gel for chemical-looping combustion fueled by gas[J]. Journal of Fuel Chemistry and Technology, 2008, 36(3): 261-266.

胡荣祖, 高胜利, 赵凤起, 史启祯, 张同来, 张建军. 热分析动力学[M]. 北京: 科学出版社, 2008. 127-131. HU Rong-zhu, GAO Sheng-li, ZHAO Feng-qi, SHI Qi-zhen, ZHANG Tong-lai, ZHANG Jian-jun. Thermal Analysis Kinetics[M]. Beijing: Science Press, 2008. 127-131.

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