表面形貌控制增强铁基载氧体与褐煤化学链燃烧反应活性

doi:10.7503/cjcu20140756

摘要/Abstract

摘要：

为探究载氧体形貌控制获取适用于化学链燃烧的高活性表面结构载氧体的可行性, 以Fe₂O₃作为模型载氧体, 从理论上对比研究Fe₂O₃的高弥勒指数晶面(104)和Fe₂O₃自然裸露的最主要晶面之一(001)的表面电子特性, 结果表明, Fe₂O₃(104)的电子结构更有利于表面与煤模型分子的相互作用. 基于理论分析结果, 从实验上控制制备了单晶载氧体Fe₂O₃(104)/Al₂O₃, 研究了该载氧体与褐煤的化学链燃烧反应特性. Fe₂O₃(104)/Al₂O₃比传统浸渍法制备的载氧体Fe₂O₃/Al₂O₃具有更高的反应活性, 与理论计算结果一致. 元素分析表明, Fe₂O₃(104)/Al₂O₃与褐煤反应的积碳量远少于Fe₂O₃/Al₂O₃与褐煤反应的积碳量. 对比新鲜载氧体及再生后载氧体的结构发现, Fe₂O₃(104)/Al₂O₃在反应过程中不断进行氧化还原反应而发生结构弛豫后, 仍然能通过氧化再生. 这表明形貌控制制备可为化学链燃烧技术开发新型高效载氧体提供新思路.

关键词: 化学链燃烧, 吸附, 载氧体, CO2, Fe2O3, 密度泛函理论

Abstract:

We selected Fe₂O₃ as the model oxygen carrier for chemical looping combustion(CLC) to theoretically detect the electronic properties of the high index surface(104) and the referenced low index surface(001). Fe₂O₃(104) exhibits better electronic structure for the interaction to lignite. Then, based on the theoretical calculations, Fe₂O₃(104) supported on Al₂O₃ was obtained via surface-controlled preparation. The reaction between lignite and the prepared Fe₂O₃(104)/Al₂O₃ is more efficient than the reaction between lignite and the reference Fe₂O₃/Al₂O₃ prepared via traditional impregnation method, which corresponds to the theoretical calculations. Ultimate analysis shows less carbon deposit on the reduced Fe₂O₃(104)/Al₂O₃ than on the reduced Fe₂O₃/Al₂O₃. Further, the fresh and the regenerated oxygen carrier were characterized, which verified the regeneration ability of Fe₂O₃(104) after severe structural relaxation during the reaction processes. These findings indicate that morphological control of oxygen carrier is very rewarding and will throw light to the next generation of highly efficient oxygen carriers for CLC technology.

Key words: Chemical looping combustion, Adsorption, Oxygen carrier, CO2, Fe2O3, Density functional theory

中图分类号:

TrendMD:

覃吴, 林常枫, 程伟良, 肖显斌. 表面形貌控制增强铁基载氧体与褐煤化学链燃烧反应活性. 高等学校化学学报, 2015, 36(1): 116.

QIN Wu, LIN Changfeng, CHENG Weiliang, XIAO Xianbin. Enhancing the Activity of Iron Based Oxygen Carrier via Surface Controlled Preparation for Lignite Chemical Looping Combustion^†. Chem. J. Chinese Universities, 2015, 36(1): 116.

图/表 10

Fig.1 Schematic progress of chemical-looping combustion(CLC)

Fig.2 Layers model of Fe2O3(104) 2×1(A) and Fe2O3(001) 2×2(B) super-cell surfaces

Table 1 Mass fraction(%) of component and element of lignite sample studied in dried air*

F	V	A	M	C	H	O	N	S
42.33	37.43	8.77	11.47	57.01	3.41	15.59	1.05	0.49

Fig.3 Isosurfaces and energies of HOMO, LUMO, and the band gap for Fe2O3(104)(A) and Fe2O3(001)(B)

Fig.4 TEM images of Fe2O3(104) nanorods(A)(inset: high magnification), SEM image(B) and XRD pattern of the prepared Fe2O3(104)/Al2O3(C)

Fig.5 TEM images of the referenced Fe2O3(A)(inset: high magnification), SEM image(B) and XRD pattern of the referenced Fe2O3/Al2O3(C)

Fig.6 Mass loss for lignite pyrolysis(a) and lignite reaction with Fe2O3(104)/Al2O3(b) or the referenced Fe2O3/Al2O3(c)

Fig.7 FTIR spectra for lignite pyrolysis(A) and CLC reaction between lignite and Fe2O3(104)/Al2O3(B)

Fig.8 XRD patterns(A,B) and SEM images(A‘, B‘) of the used(A, A‘) and the regenerated Fe2O3(104)/Al2O3(B, B‘)

Table 2 Elemental content(%) for Fe2O3(104)/Al2O3 and the referenced Fe2O3/Al2O3 after reaction with lignite

Oxygen carrier	C	H	N
Fe₂O₃(104)/Al₂O₃	0.101	0.014	0.017
Referenced Fe₂O₃/Al₂O₃	0.380	0.157	0.141

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