MgX<sub>2</sub>O<sub>4</sub> (X=Mn、Fe、Cr) 型尖晶石B位点阳离子对乙烷化学链氧化脱氢生成乙烯的影响

LIANG Xiaocen; WANG Xuemei; XING Zifan; MAO Min; SONG Da; LI Yang; LONG Tao; ZHOU Yuchao; CHEN Peili; HE Fang

doi:10.1016/S1872-5813(24)60434-2

MgX₂O₄ (X=Mn、Fe、Cr) 型尖晶石B位点阳离子对乙烷化学链氧化脱氢生成乙烯的影响

doi: 10.1016/S1872-5813(24)60434-2

梁晓岑^{1, 2,},
王雪梅^{1, 2,},
幸子凡^{1, 2,},
毛敏^{1, 2,},
宋达^{3, 4,},
李杨^3,,
龙涛^{1, 2,},
周宇超^{1, 2,},
陈佩丽³,
何方^{1, 2, ,}

1.
桂林理工大学化学与生物工程学院, 广西桂林 541006
2.
桂林理工大学化学与生物工程学院广西电化学与磁化学功能材料重点实验室, 广西桂林 541006
3.
中国科学院广州能源研究所, 广东广州 510640
4.
中国科学技术大学能源科学与工程学院, 安徽合肥 230000

详细信息

中图分类号: O643.36
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出版历程
- 收稿日期: 2023-12-04
- 修回日期: 2024-01-31
- 录用日期: 2024-01-31
- 网络出版日期: 2024-03-30

Impact of B-site cations of MgX₂O₄ (X=Mn, Fe, Cr) spinels on the chemical looping oxidative dehydrogenation of ethane to ethylene

LIANG Xiaocen^{1, 2
,},
WANG Xuemei^{1, 2
,},
XING Zifan^{1, 2
,},
MAO Min^{1, 2
,},
SONG Da^{3, 4
,},
LI Yang^3
,,
LONG Tao^{1, 2
,},
ZHOU Yuchao^{1, 2
,},
CHEN Peili³,
HE Fang^{1, 2
, ,}

1.
College of Chemistry and Bioengineering, Guilin University of Technology, Guilin 541006, China
2.
Guangxi Key Laboratory of Electrochemical and Magneto-chemical Functional Materials, College of Chemistry and Bioengineering, Guilin University of Technology, Guilin 541006, China
3.
Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China
4.
School of Energy Science and Engineering, University of Science and Technology of China, Hefei 230000, China

More Information

Corresponding author: E-mail: hefang@glut.edu.cnE-mail: hefang@glut.edu.cn

摘要

摘要: 化学链循环氧化脱氢技术（CL-ODH）是一个多功能的平台，它可以利用载氧体中晶格氧的选择性氧化这一特性，实现乙烷向乙烯的高值化转化。本研究探讨了MgX₂O₄（X=Cr、Fe或Mn）型尖晶石载氧体中B位元素对乙烷CL-ODH性能的影响。采用固定床和H₂-TPR、O₂-TPD、TG、原位拉曼、SEM、TEM等方法对MgX₂O₄尖晶石进行了性能测试和表征。结果表明，MgCr₂O₄仅释放微量表面吸附氧，更倾向于催化乙烷转化为焦炭和氢气。MgFe₂O₄通过提供更多的表面晶格氧，促进乙烷深度氧化成CO₂。MgMn₂O₄载氧体在乙烷CL-ODH反应中能够释放出大量的体相晶格氧，它可以选择性燃烧氢气以推进反应正向进行，增加乙烯的选择性，实现了73.7%的乙烷转化率和81.46%的乙烯选择性。此外，MgMn₂O₄催化剂在乙烷CL-ODH反应中进行了30次的氧化还原循环实验，表现出稳定的反应性能，在整个循环测试中乙烯收率大约为62%。MgX₂O₄尖晶石氧化物中B位元素影响了其晶格氧的供应能力，从而影响了其在乙烷CL-ODH反应中的性能。
- 乙烷CL-ODH /
- MgX₂O₄尖晶石型载氧体 /
- 乙烷生产乙烯 /
- MgMn₂O₄
Abstract: Chemical looping oxidative dehydrogenation (CL-ODH) provides a multifunctional conversion platform that can take advantage of the selective oxidation of lattice oxygen in oxygen carrier to achieve high-valued ethane to ethylene conversion. In this study, we explored the effect of B-site element in MgX₂O₄ (X=Cr, Fe, or Mn) spinel-type oxygen carriers on the performance of ethane CL-ODH. The properties test and characterization of MgX₂O₄ spinel were tested by fixed bed and H₂-TPR, O₂-TPD, TG, in-situ Raman, SEM, and TEM. The results showed that because MgCr₂O₄ only released a small amount of adsorbed surface oxygen, it tended to catalyze the conversion of ethane to coke and hydrogen. MgFe₂O₄ facilitated the deep oxidation of ethane into CO₂ by providing more surface lattice oxygen. Meanwhile, since a significant amount of bulk lattice oxygen was released by the MgMn₂O₄ oxygen carrier, it could burn hydrogen in a targeted manner to advance the reaction and increased ethylene's selectivity. Thereby, MgMn₂O₄ achieved an ethane conversion of 73.7% with an ethylene selectivity of 81.46%. Furthermore, the MgMn₂O₄ catalyst demonstrated stable reactivity and an ethylene yield of about 62% in ethane CL-ODH over the 30 redox cycles. The screening tests indicated that the B-site elements in MgX₂O₄ spinel oxides could significantly influence their ability to supply lattice oxygen, thereby affecting their performance in ethane CL-ODH reaction.
- ethane CL-ODH /
- MgX₂O₄ spinel-type oxygen carrier /
- ethane to ethylene /
- MgMn₂O₄

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Figure 1 Process diagram of ethane CL-ODH reaction

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Figure 2 XRD patterns of the fresh oxygen carriers

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Figure 3 Scanning electron microscopy of fresh oxygen carriers MCO (a), MFO (b), MMO (c)

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Figure 4 Transmission electron microscope and lattice fringe calculation of fresh oxygen carriers MCO (a), MFO (b), MMO (c)

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Figure 5 Ethylene yield of MCO (a), MFO (b), MMO (c), hydrogen conversion (d), total yield (e) and C balance (f)

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Figure 6 XRD patterns of fresh and reduced oxygen carriers

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Figure 7 Scanning electron microscopy of reduced oxygen carriers MCO (a), MFO (b), MMO (c)

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Figure 8 XPS of oxygen carrier before and after reaction: O 1s (a)−(c), Cr 2p (d), Fe 2p (e) and Mn 2p (f)

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Figure 9 CO₂-TPD (a), H₂-TPR (b), O₂-TPD (c) and TG (d) of fresh oxygen carriers

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Figure 10 In-situ Raman results for MCO (a) and MMO (b) at 775 °C

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Figure 11 Ethylene yield (a) and XRD patterns (b) of MMO before and after the 30 consecutive redox cycles at 775 °C

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Table 1 Specific surface areas of fresh oxygen carriers of MCO, MFO and MMO

	S_BET/(m²·g⁻¹)	v_pore/(cm³·g⁻¹)	Average pore diameter d/nm
MgCr₂O₄	21.002	0.142	27.071
MgFe₂O₄	14.638	0.057	15.464
MgMn₂O₄	7.716	0.035	18.248

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Table 2 Content changes of O 1s and B-position elements before and after reaction

	O_Ⅰ		O_Ⅱ		O_Ⅲ		O_(Ⅱ+Ⅲ)/ O_Ⅰ		Change of valence state of B-site ions
	fresh	reduced	fresh	reduced	fresh	reduced	fresh	reduced		fresh	reduced
MgCr₂O₄	59.26	54.61	25.78	39.38	14.96	6.01	0.69	0.83	Cr⁶⁺/Cr³⁺	0.70	0.57
MgFe₂O₄	57.50	39.17	36.03	40.05	6.46	20.78	0.74	1.55	Fe³⁺/Fe²⁺	1.07	0.76
MgMn₂O₄	50.71	30.81	34.12	63.00	15.16	6.19	0.97	2.24	Mn⁴⁺/(Mn³⁺+Mn²⁺)	0.55	0.37

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