三维有序大孔Fe<sub>2</sub>O<sub>3</sub>为载氧体的生物质热解气化实验研究

赵坤; 何方; 黄振; 魏国强; 李海滨; 赵增立

三维有序大孔Fe₂O₃为载氧体的生物质热解气化实验研究

赵坤^1,2,
何方^1,,
黄振¹,
魏国强^1,2,
李海滨¹,
赵增立¹

1.
中国科学院广州能源研究所, 中国科学院可再生能源与天然气水合物重点实验室, 广东广州 510640;
2.
中国科学院大学, 北京 100049

基金项目: 国家自然科学基金(51076154);"十二五"国家科技支撑计划(2011BAD15B05)。

详细信息

通讯作者:
何方,Tel:020-87057721,E-mail:hefang@ms.giec.ac.cn。

中图分类号: TK6
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出版历程
- 收稿日期: 2012-09-11
- 修回日期: 2012-12-10
- 刊出日期: 2013-03-30

Biomass pyrolysis/gasification using three dimensional ordered macroporous (3DOM) Fe₂O₃ as an oxygen carrier

1.
The Key Laboratory of Renewable Energy and Gas Hydrate of Chinese Academy of Sciences, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China;
2.
University of Chinese Academy of Sciences, Beijing 100049, China

摘要

摘要: 采用无皂乳液聚合法制备单分散聚苯乙烯(PS)微球,并以硝酸盐为原料、柠檬酸为络合剂制备前驱体溶液,通过浸渍和焙烧得到三维有序大孔(3DOM) Fe₂O₃,并通过SEM、XRD、BET和压汞仪对3DOM Fe₂O₃进行表征。采用热重-质谱联用的方法,以3DOM Fe₂O₃为载氧体,对生物质在氦气气氛下的热解气化进行研究,探讨3DOM Fe₂O₃载氧体在生物质热解气化过程中代替纯氧、富氧空气或水蒸气作为生物质气化剂的可能性,并与普通分析纯Fe₂O₃与生物质热解气化的实验结果进行对比,分析3DOM Fe₂O₃在提高载氧体反应活性方面的作用。结果表明,制备的3DOM Fe₂O₃呈现排列规整的三维有序多孔形貌,层与层间通过三维孔道相连,并呈交替排列。通过与分析纯Fe₂O₃的XRD谱图对比,发现制得的3DOM Fe₂O₃为纯Fe₂O₃,无其他杂质相的存在。热重-质谱分析结果表明,Fe₂O₃作为载氧体在高温段促成了生物质气化反应的发生。与分析纯的Fe₂O₃作对比,当载氧体为三维有序大孔结构时,生物质的最大失重率提高了7.1%,气化阶段的最大失重速率提高了0.29%/min,CO、CO₂、CH₄在高温段出现两个连续的析出峰。
- TG-MS /
- 三维有序大孔 /
- 载氧体 /
- 生物质 /
- 热解气化
Abstract: Polystyrene spheres were prepared by soap free emulsion polymerization method,then three dimensional ordered macroporous (3DOM) oxides Fe₂O₃ were successfully prepared after impregnation and calcination using nitrates as raw materials and citric acid as complexing agent. The samples were characterized by the techniques of scanning electron microscopy (SEM), X-ray diffraction(XRD), BET and mercury porosimetry. Pyrolysis and gasification of biomass with Fe₂O₃ as oxygen carriers in helium atmosphere were carried out in a thermogravimetric analyzer coupled with mass spectrometry (TG-MS). The possibility of 3DOM Fe₂O₃ functioning as gasification agent in biomass gasification substituted for pure oxygen, oxygen-enriched air or steam were investigated. Furthermore, a comparison experiment was carried out by using analytically pure Fe₂O₃ to analysis the high-performance of 3DOM Fe₂O₃. The characterization results showed that 3DOM Fe₂O₃ presented a three-dimensional ordered macroporous morphology, its tiers were arranged alternatively and connected through three-dimensional pore structures. By contrast with the XRD pattern of analytically pure Fe₂O₃. TG-MS results showed that Fe₂O₃ contributed to biomass gasification in high temperature stage. When used 3DOM Fe₂O₃ as oxygen carrier, the maximum weight loss and maximum weight loss rate raised 7.1% and 0.29%/min in the gasification stage, respectively, meanwhile two generation peaks of CO, CO₂, and CH₄ appeared in the MS curves.
- TG-MS /
- 3DOM /
- oxygen carrier /
- biomass /
- pyrolysis gasification

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参考文献(13)

De DIEGO L F, ORTIZ M, GARCIA-LABIANO F, ADÁNEZ J, ABAD A, GAYÁN P. Hydrogen production by chemical-looping reforming in a circulating fluidized bed reactor using Ni-based oxygen carriers[J]. J Power Sources, 2009, 192(1): 27-34.

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基载氧体研究[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.)

张璐. 化学链燃烧技术中载氧体CaSO₄的性能研究. 武汉:华中科技大学, 2009. (ZHANG Lu. Experimental Investigation of CaSO4 for Chemical-Looping Combustion. Wuhan: Huazhong University of Science and Technology, 2009.

De DIEGO L F, ORTIZ M, ADANEZ J, GARCÍA-LABIANO F, ABAD A, GAYN P. Synthesis gas generation by chemical-looping reforming in a batch fluidized bed reactor using Ni-basedoxygen carriers[J]. Chem Eng J, 2008, 144(2): 289-298.

JOHANSSON M, MATTISSON T, LYNGFELT A, ABAD A. Using continuous and pulse experiments to compare two promising Nickel-based oxygen carriers for use in chemical-looping technologies[J]. Fuel, 2008, 87(6): 988-1001.

BOLHAR-NORDENKAMP F J, PROLL T, KOLBITSCH P, HOFBAUER H. Performance of a NiO-based oxygen carrier for chemical looping combustion and reforming in a 120 kW unit[J]. Energy Procedia, 2009, (1): 19-25.

黄振, 何方, 李海滨, 赵增立. 天然铁矿石为载氧体的生物质化学链气化制合成气实验研究[J]. 燃料化学学报, 2012, 40(3): 300-308. (HUANG Zhen, HE Fang, LI Hai-bing, ZHAO Zeng-li. Synthesis gas generation by chemical-looping gasification of biomass using natural hematite as oxygen carrier[J]. Journal of Fuel Chemistry and Technology, 2012, 40(3): 300-308.)

SADAKANE M, ASANUMA T, KUBO J, UEDA W. Facile procedure to prepare three-dimensionally ordered macroporous (3DOM) perovskite-type mixed metal oxides by colloidal crystal templating method[J]. Chem Mater, 2005, 17(13): 3546-3551.

BLANCO A, CHOMSKI E, GRABTCHAK S, IBISATE M, JOHN S, LEONARD S W, LOPEZ C, MESEGUER F, MIGUEZ H, MONDIA J P, OZIN G A, TOADER O, van DRIEL H M. Large-scale synthesis of a silicon photonic crystal with a complete three dimensional bandgap near 1.5 micrometres[J]. Nature, 2000, 405(6785): 437-440.

TESSIER P M, VELEV O D, KALAMBUR A T, RABOLT J F, LENHOFF A M, KALER E W. Assembly of gold nanostructured films templated by colloidal crystals and use in surface-enhanced Raman spectroscopy [J]. J Am Chem Soc, 2000, 122(39): 9554-9555.

SORENSEN E M, BARRY S J, JUNG H-K, RONDINELLI J M, VAUGHEY J T, POEPPELMEIER K R. Three-dimensionally ordered macroporous Li₄Ti₅O₁₂: Effect of wall structure on electrochemical properties[J]. Chem Mater, 2006, 18(2): 482-489.

徐俊峰, 刘坚, 赵震, 张桂臻, 段爱军, 姜桂元, 徐春明. 三维有序大孔钙钛矿LaFeO₃催化剂的制备及其催化炭黑颗粒燃烧性能[J]. 催化学报, 2010, 31(2): 236-341. (XU Jun-feng, LIU Jian, ZHAO Zhen, ZHANG Gui-zhen, DUAN Ai-jun, JIANG Gui-yuan, XU Chun-ming. Preparation and catalytic performance of three-dimensionally orderedmacroporous perovskite-type LaFeO₃ catalyst for soot combustion[J]. Chinese Journal of Catalysis, 2010, 31(2): 236-341.)

赵铁鹏, 高德淑, 雷钢铁, 李朝晖. 三维有序大孔α-Fe₂O₃的制备及电化学性能研究[J]. 化学学报, 2009, 67(17): 1957-1961. (ZHAO Tie-peng, GAO De-shu, LEI Gang-tie, LI Zhao-hui. Fabrication and electrochemical properties of three-dimensionally ordered macroporous α-Fe₂O₃[J]. Acta Chimica Sinica, 2009, 67(17): 1957-1961.)

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