Effect of Ba content on chemical looping dry reforming of methane performance of (La0.5Sr0.5)1-x Ba x Fe0.6Co0.4O3

doi:10.11949/0438-1157.20230687

Abstract

Abstract:

Chemical looping dry reforming of methane (CL-DRM) has the potential as an efficient technology to achieve carbon neutrality in terms of converting CH₄ and CO₂ to various value-added products with the minimal separation requirements. Currently, a major challenge facing this technology is the design and development of oxygen carriers with good reactivity and stability. Herein, the Ba-substituted (La_0.5Sr_0.5)_1-_x Ba _x Fe_0.6Co_0.4O₃ perovskite oxides with the anchored nanoparticles as the novel oxygen carriers were synthesized and investigated for the redox performance in the CL-DRM process based on various characterization technologies. It is found that La_0.35Sr_0.35Ba_0.3Fe_0.6Co_0.4O₃ oxygen carrier (x=0.3) increases the amount of oxygen consumed (5.29 mmol·g^-1) and shows a higher oxygen diffusion rate to achieve the CH₄ conversion of 84.3% and syngas yield of 15.23 mmol·g^-1 in the CH₄ reduction step. Meanwhile, the syngas selectivity of 95.8%, the CO selectivity of 70.0% and carbon deposition of 1.36 mmol·g^-1 can be obtained. Analysis of the gas generation rate during methane reduction shows that Ba substitution can optimize the lattice structure of the oxygen carrier, leading to high ion mobility, promoting rapid diffusion of oxygen in the bulk phase, and thus improving CH₄ conversion. Furthermore, the excellent oxygen carrier also exhibits the high structure stability and the stable regeneration ability by CO₂ during the successive redox cycles.

Key words: chemical looping reforming, methane, carbon dioxide, syngas, perovskite oxides, oxygen carrier

摘要：

化学链甲烷干重整可将CH₄和CO₂转化为各种增值产品，是一种具有低分离要求的高效反应技术，并可助力碳中和。目前，该技术面临的一个主要挑战是设计和开发具有良好反应性和稳定性的载氧体。合成了Ba取代的具有锚定纳米颗粒的(La_0.5Sr_0.5)_1-_x Ba _x Fe_0.6Co_0.4O₃钙钛矿氧化物，将其用作化学链甲烷干重整的载氧体，通过多种表征手段和性能评价，研究了该类材料的物化性质和氧化还原性能。结果表明，在所有样品中，La_0.35Sr_0.35Ba_0.3Fe_0.6Co_0.4O₃在甲烷部分氧化过程中可实现84.3%的甲烷转化率、15.23 mmol·g^-1的合成气产量以及最高的氧消耗量(5.29 mmol·g^-1)，显示出优异的氧扩散速率，同时具有95.8%的合成气选择性、70.0%的CO选择性和1.36 mmol·g^-1的积炭。对甲烷还原过程中气体生成速率的分析表明，Ba取代可以优化载氧体的晶格结构，导致高的离子迁移率，促进氧在体相中的快速扩散，进而提升CH₄转化。此外，氧化还原循环测试表明该载氧体具有较优异的结构稳定性和较好的再生能力。

关键词: 化学链重整, 甲烷, 二氧化碳, 合成气, 钙钛矿, 载氧体

CLC Number:

TQ 519

Liuqing YANG, Zirui ZHAO, Junshe ZHANG, Jinjia WEI. Effect of Ba content on chemical looping dry reforming of methane performance of (La_0.5Sr_0.5)_1-_x Ba _x Fe_0.6Co_0.4O₃[J]. CIESC Journal, 2023, 74(10): 4286-4301.

杨柳青, 赵子瑞, 张军社, 魏进家. 钡含量对（La_0.5Sr_0.5）_1-_x Ba _x Fe_0.6Co_0.4O₃化学链甲烷干重整性能的影响[J]. 化工学报, 2023, 74(10): 4286-4301.

Figures/Tables 16

Table 1 Chemical compositions and abbreviations of the samples

样品	缩写
La_0.45Sr_0.45Ba_0.1Fe_0.6Co_0.4O₃	LSB10FC
La_0.4Sr_0.4Ba_0.2Fe_0.6Co_0.4O₃	LSB20FC
La_0.35Sr_0.35Ba_0.3Fe_0.6Co_0.4O₃	LSB30FC
La_0.3Sr_0.3Ba_0.4Fe_0.6Co_0.4O₃	LSB40FC
La_0.25Sr_0.25Ba_0.5Fe_0.6Co_0.4O₃	LSB50FC

Fig.1 Schematic diagram of CL-DRM experimental reaction device

Fig.2 XRD patterns of the prepared oxygen carriers with different Ba contents

Fig.3 FT-IR spectra of the prepared oxygen carriers with different Ba contents

Fig.4 SEM images of the prepared oxygen carriers with different Ba contents

Fig.5 H2-TPR profiles of the prepared oxygen carriers with different Ba contents

Fig.6 CH4-TPR profiles over different oxygen carriers and onset reaction temperatures of high temperature phase during CH4-TPR

Fig.7 O2-TPD profiles of the prepared oxygen carriers

Fig.8 Evolution of the temporal gaseous product over as-prepared oxygen carries during the CL-DRM process

Fig.9 Quantitative analysis of different oxygen carriers during the CL-DRM process

Table 2 Methane conversion， the amount of O consumed and replenished for different oxygen carriers

载氧体	无限定还原时间的CL-DRM过程			限定还原时间的CL-DRM过程
载氧体	转化率/%	消耗氧量/(mmol·g^-1)	补充氧量/(mmol·g^-1)	转化率/%	消耗氧量/(mmol·g^-1)	补充氧量/(mmol·g^-1)
LSB10FC	67.1	8.00	4.82	83.0	4.12	3.91
LSB20FC	58.0	7.53	5.15	82.6	4.38	4.75
LSB30FC	68.9	6.68	5.54	84.3	5.29	5.24
LSB40FC	44.3	7.36	5.59	73.0	4.37	4.36
LSB50FC	45.2	7.17	5.17	67.3	4.64	4.90

Fig.10 Evolution of the temporal gaseous product over as-prepared oxygen carriers during the CL-DRM process with 30 min reduction

Fig.11 Quantitative analysis of different oxygen carriers during the CL-DRM process with 30 min reduction

Table 3 Comparison of performance for different oxygen carriers

载氧体	反应温度/℃	CH₄还原步骤			氧变化量/ (mmol·g^-1)	CO₂分解步骤	文献
载氧体	反应温度/℃	CH₄转化率/%	合成气选择性/%	合成气产率/(mmol·g^-1)	氧变化量/ (mmol·g^-1)	转化率/%	文献
La_0.5Ce_0.5FeO₃	850	82	93	4.2	—	约92	[42]
LaFe_0.8Al_0.2O₃	900	约85	>95	3.4	—	约85	[25]
La_0.85Sr_0.15Fe_0.95Al_0.05O_3-_δ	900	约80 (20%X_OC)	>99	—	—	约97	[43]
LSB30FC	900	84.3	95.8	15.23	5.29	—	本文

Fig.12 Catalytic oxidation of methane over different oxygen carriers during 30 min reduction

Fig.13 Redox stability of LSB30FC for CL-DRM

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Effect of Ba content on chemical looping dry reforming of methane performance of (La_0.5Sr_0.5)_1-_x Ba _x Fe_0.6Co_0.4O₃

钡含量对（La_0.5Sr_0.5）_1-_x Ba _x Fe_0.6Co_0.4O₃化学链甲烷干重整性能的影响

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