LaMn1-x-yFexCoyO3-δ钙钛矿载氧体用于化学链部分氧化

doi:10.11949/0438-1157.20200158

摘要/Abstract

摘要：

采用溶胶-凝胶法制备了B位Fe和Co共取代的LaMn_1-_x_-_yFe_xCo_yO_3-_δ钙钛矿型复合氧化物，并用于化学链甲烷部分氧化制合成气。X射线衍射（XRD）结果表明Fe和Co均进入了LaMnO₃的晶格形成钙钛矿晶相，活性和稳定性测试表明LaMn_1/3Fe_1/3Co_1/3O_3-_δ载氧体具有最佳的化学链甲烷部分氧化性能。CH₄程序升温还原（CH₄-TPR）表征发现LaMn_1/3Fe_1/3Co_1/3O_3-_δ具有比LaBO₃（B=Co， Mn， Fe）更高的甲烷活化能力和晶格氧迁移性能。甲烷恒温脉冲反应（CH₄-pulse reaction）进一步证实了B位离子的协同作用可以提高LaBO₃（B=Co， Mn， Fe）的表面反应速率。程序升温氢气还原（H₂-TPR）表明，LaMn_1/3Fe_1/3Co_1/3O_3-_δ中晶格氧具有适中的氧化还原能力，适合用于化学链甲烷部分氧化。

关键词: 部分氧化, 化学链, 甲烷, 钙钛矿, 合成气, 载氧体

Abstract:

LaMn_1-_x_-_yFe_xCo_yO_3-_δ perovskite-type composite oxides co-substituted with B-site Fe and Co were prepared by the sol-gel method, and used for the chemical looping partial oxidation of methane to syngas. The XRD results suggest that Fe and Co were incorporated into the lattice of LaMnO₃ and formed perovskite phase. Reactivity and stability tests show that LaMn_1/3Fe_1/3Co_1/3O_3-_δ oxygen carrier has the best reaction performance. CH₄-TPR results indicate that LaMn_1/3Fe_1/3Co_1/3O_3-_δ has higher methane activation and lattice oxygen migration rates than those of LaBO₃ (B=Co, Mn, Fe). CH₄-pulse reaction further confirms that the synergistic effect of B-site ion substitution can improve the surface reaction rate of LaBO₃ (B=Co, Mn, Fe). H₂-TPR results show that the lattice oxygen in LaMn_1/3Fe_1/3Co_1/3O_3-_δ has moderate redox capacity, which is suitable for partial oxidation of methane.

Key words: partial oxidation, chemical looping, methane, perovskite, syngas, oxygen carrier

中图分类号:

TQ 028.8

苏迎辉,郑浩,张磊,曾亮. LaMn_1-_x_-_yFe_xCo_yO_3-_δ钙钛矿载氧体用于化学链部分氧化[J]. 化工学报, 2020, 71(11): 5265-5277.

Yinghui SU,Hao ZHENG,Lei ZHANG,Liang ZENG. LaMn_1-_x_-_yFe_xCo_yO_3-_δ perovskite based oxygen carriers for chemical looping partial oxidation[J]. CIESC Journal, 2020, 71(11): 5265-5277.

图/表 11

图1 新鲜样品 LaCoO3、LaMnO3、LaFeO3、LaMn1/3Fe1/3Co1/3O3-δ的XRD谱图

Fig.1 XRD patterns of the fresh samples: LaMnO3, LaFeO3, LaCoO3 and LaMn1/3Fe1/3Co1/3O3-δ

表1 新鲜LaMn1-x-yFexCoyO3-δ载氧体晶胞结构参数

Table 1 Structure parameters of the fresh LaMn1-x-yFexCoyO3-δ oxygen carriers

样品	晶胞参数 a₀ /?	(110) 晶面 2θ/(°)	晶粒尺寸 /nm
LaMnO₃	3.911	32.368	47.1
LaMn_1/3Fe_1/3Co_1/3O_3-_δ	3.888	32.628	24.4
LaMn_1/3Fe_1/6Co_1/2O_3-_δ	3.897	32.572	31.4
LaMn_1/6Fe_1/3Co_1/2O_3-_δ	3.901	32.369	25.1
LaMn_7/15Fe_1/3Co_1/5O_3-_δ	3.891	32.716	30.9
LaMn_1/3Fe_1/2Co_1/6O_3-_δ	3.899	32.639	28.1

图2 新鲜样品不同Co、Fe添加量的LaMn1-x-yFexCoyO3-δ载氧体XRD谱图

Fig.2 XRD patterns of fresh LaMn1-x-yFexCoyO3-δ samples with different amounts of Co and Fe

图3 LaMn1-x-yFexCoyO3-δ在甲烷部分氧化阶段的气体产物分布

Fig.3 Reaction performance of LaMn1-x-yFexCoyO3-δ in CL-POM

图4 不同LaMn1-x-yFexCoyO3-δ样品的气体产物随时间变化情况

Fig.4 Reactivity as a function of reaction time over LaMn1-x-yFexCoyO3-δ samples

图5 LaMn1-x-yFexCoyO3-δ载氧体900℃下循环稳定性测试结果

Fig.5 Cyclic stability test of LaMn1-x-yFexCoyO3-δ oxygen carriers for continuous redox cycles in CL-POM at 900℃

图6 LaMn1/3Fe1/3Co1/3O3-δ载氧体10个循环稳定性测试前后的XRD谱图

Fig.6 XRD patterns of LaMn1/3Fe1/3Co1/3O3-δ oxygen carriers before and after 10 cycles stability test

图7 新鲜载氧体的H2-TPR谱图

Fig.7 H2-TPR profiles of fresh oxygen carriers

图8 新鲜载氧体CH4-TPR质谱图

Fig.8 CH4 -TPR mass spectra of fresh oxygen carriers

图9 新鲜载氧体在900℃的CH4脉冲的气体组分

Fig.9 Gas components during CH4 pulses at 900℃ over fresh oxygen carriers

图10 甲烷还原反应后LaMn1-x-yFexCoyO3-δ载氧体TPO测试结果

Fig.10 TPO results of LaMn1-x-yFexCoyO3-δ oxygen carriers after methane reduction stage

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