钡含量对（La0.5Sr0.5）1-x Ba x Fe0.6Co0.4O3化学链甲烷干重整性能的影响

doi:10.11949/0438-1157.20230687

摘要/Abstract

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

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

中图分类号:

TQ 519

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.

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.

图/表 16

表1 样品的化学组成与缩写

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

图1 CL-DRM实验反应装置示意图

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

图2 不同Ba含量载氧体的XRD谱图

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

图3 不同Ba含量载氧体的FT-IR谱图

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

图4 不同Ba含量载氧体的SEM图

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

图5 不同Ba含量载氧体的H2-TPR谱图

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

图6 不同Ba含量载氧体的CH4-TPR谱图及高温阶段的起始温度变化

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

图7 不同Ba含量载氧体的O2-TPD谱图

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

图8 不同Ba含量载氧体的化学链甲烷干重整过程

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

图9 化学链甲烷干重整过程不同Ba含量载氧体的量化分析

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

表2 不同载氧体的甲烷转化率、消耗氧量和补充氧量

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

图10 不同Ba含量载氧体的化学链甲烷干重整过程（30 min的还原过程）

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

图11 化学链甲烷干重整过程（30 min还原过程）不同Ba含量载氧体的量化分析

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

表3 不同载氧体的性能比较

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

图12 30 min的还原过程中不同载氧体的甲烷催化氧化

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

图13 LSB30FC的氧化还原稳定性

Fig.13 Redox stability of LSB30FC for CL-DRM

参考文献 43

1	Li X Y, Pei C L, Gong J L. Shale gas revolution: catalytic conversion of C₁—C₃ light alkanes to value-added chemicals[J]. Chem, 2021, 7(7): 1755-1801.
2	王保文, 张港, 刘同庆, 等. CeO₂/CuFe₂O₄氧载体CH₄化学链重整耦合CO₂热催化还原研究[J]. 化工学报, 2022, 73(12): 5414-5426.
	Wang B W, Zhang G, Liu T Q, et al. Research on chemical looping reforming of CH₄ by CeO₂ doped CuFe₂O₄ oxygen carrier coupled with CO₂ thermocatalytic reduction[J]. CIESC Journal, 2022, 73(12): 5414-5426.
3	Song S, Song H, Li L M, et al. A selective Au-ZnO/TiO₂ hybrid photocatalyst for oxidative coupling of methane to ethane with dioxygen[J]. Nature Catalysis, 2021, 4(12): 1032-1042.
4	Koolen C D, Luo W, Züttel A. From single crystal to single atom catalysts: structural factors influencing the performance of metal catalysts for CO₂ electroreduction[J]. ACS Catalysis, 2023, 13(2): 948-973.
5	王峰, 张顺鑫, 余方博, 等. 光催化CO₂还原制碳氢燃料系统优化策略研究[J]. 化工学报, 2023, 74(1): 29-44.
	Wang F, Zhang S X, Yu F B, et al. Optimization strategy for producing carbon based fuels by photocatalytic CO₂ reduction[J]. CIESC Journal, 2023, 74(1): 29-44.
6	刘彦铄, 王新赫, 张军社, 等. 太阳能甲烷重整反应器研究进展[J]. 化工进展, 2019, 38(12): 5339-5350.
	Liu Y S, Wang X H, Zhang J S, et al. Progress in solar methane reforming reactors[J]. Chemical Industry and Engineering Progress, 2019, 38(12): 5339-5350.
7	Huang Y, Sun W J, Qin Z C, et al. The role of China’s terrestrial carbon sequestration 2010—2060 in offsetting energy-related CO₂ emissions[J]. National Science Review, 2022, 9(8): nwac057.
8	Hu Q Q, Li Y Z, Wu J C, et al. Extraordinary catalytic performance of nickel half-metal clusters for light-driven dry reforming of methane[J]. Advanced Energy Materials, 2023, 13(21): 2300071.
9	Buelens L C, Galvita V V, Poelman H, et al. Super-dry reforming of methane intensifies CO₂ utilization via Le Chatelier’s principle[J]. Science, 2016, 354(6311): 449-452.
10	Yang L Q, Zhao Z R, Cui C Y, et al. Effect of nickel and cobalt doping on the redox performance of SrFeO_3- _δ toward chemical looping dry reforming of methane[J]. Energy & Fuels, 2023, 37(16): 12045-12057.
11	蔡润夏, 李凡星. 复杂氧化物载氧体的调变策略及在过程强化中的应用[J]. 化工学报, 2021, 72(12): 6122-6130.
	Cai R X, Li F X. Tailoring the thermodynamic properties of complex oxides for thermochemical air separation and beyond[J]. CIESC Journal, 2021, 72(12): 6122-6130.
12	Zhu Q Y, Zhou H, Wang L, et al. Enhanced CO₂ utilization in dry reforming of methane achieved through nickel-mediated hydrogen spillover in zeolite crystals[J]. Nature Catalysis, 2022, 5(11): 1030-1037.
13	Luo M, Shen R C, Qin Y J, et al. Conversion and syngas production of toluene as a biomass tar model compound in chemical looping reforming[J]. Fuel, 2023, 345: 128203.
14	Zhu X, Imtiaz Q, Donat F, et al. Chemical looping beyond combustion—a perspective[J]. Energy & Environmental Science, 2020, 13(3): 772-804.
15	Li D Y, Xu R D, Gu Z H, et al. Chemical-looping conversion of methane: a review[J]. Energy Technology, 2020, 8(8): 1900925.
16	Zeng L, Cheng Z, Fan J A, et al. Metal oxide redox chemistry for chemical looping processes[J]. Nature Reviews Chemistry, 2018, 2(11): 349-364.
17	Sun Z, Russell C K, Whitty K J, et al. Chemical looping-based energy transformation via lattice oxygen modulated selective oxidation[J]. Progress in Energy and Combustion Science, 2023, 96: 101045.
18	Zeng D W, Kang F W, Qiu Y, et al. Iron oxides with gadolinium-doped cerium oxides as active supports for chemical looping hydrogen production[J]. Chemical Engineering Journal, 2020, 396: 125153.
19	Luo C Q, Dou B L, Zhang H, et al. Co-production of hydrogen and syngas from chemical looping water splitting coupled with decomposition of glycerol using Fe-Ce-Ni based oxygen carriers[J]. Energy Conversion and Management, 2021, 238: 114166.
20	Zhang R J, Cao Y, Li H B, et al. The role of CuO modified La_0.7Sr_0.3FeO₃ perovskite on intermediate-temperature partial oxidation of methane via chemical looping scheme[J]. International Journal of Hydrogen Energy, 2020, 45(7): 4073-4083.
21	马源, 肖晴月, 岳君容, 等. CeO₂-Al₂O₃复合载体负载Ni基催化剂催化CO _x 共甲烷化性能[J]. 化工进展, 2023, 42(5): 2421-2428.
	Ma Y, Xiao Q Y, Yue J R, et al. CO _x co-methanation over a Ni-based catalyst supported on CeO₂-Al₂O₃ composite[J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2421-2428.
22	Hwang J, Rao R R, Giordano L, et al. Perovskites in catalysis and electrocatalysis[J]. Science, 2017, 358(6364): 751-756.
23	Wang Y H, Robson M J, Manzotti A, et al. High-entropy perovskites materials for next-generation energy applications[J]. Joule, 2023, 7(5): 848-854.
24	Zhang J S, Haribal V, Li F X. Perovskite nanocomposites as effective CO₂-splitting agents in a cyclic redox scheme[J]. Science Advances, 2017, 3(8): e1701184.
25	Xia X, Chang W X, Cheng S W, et al. Oxygen activity tuning via FeO₆ octahedral tilting in perovskite ferrites for chemical looping dry reforming of methane[J]. ACS Catalysis, 2022, 12(12): 7326-7335.
26	Chang H, Bjørgum E, Mihai O, et al. Effects of oxygen mobility in La-Fe-based perovskites on the catalytic activity and selectivity of methane oxidation[J]. ACS Catalysis, 2020, 10(6): 3707-3719.
27	Joo S, Kim K, Kwon O, et al. Enhancing thermocatalytic activities by upshifting the d-band center of exsolved Co-Ni-Fe ternary alloy nanoparticles for the dry reforming of methane[J]. Angewandte Chemie International Edition, 2021, 60(29): 15912-15919.
28	Zhang D W, De Santiago H A, Xu B Y, et al. Compositionally complex perovskite oxides for solar thermochemical water splitting[J]. Chemistry of Materials, 2023, 35(5): 1901-1915.
29	Shannon R D. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides[J]. Acta Crystallographica Section A, 1976, 32(5): 751-767.
30	Yang L Q, Zhang J S, Wei J J. Highly active La_0.35Sr_0.35Ba_0.3Fe_1- _x Co _x O₃ oxygen carriers with the anchored nanoparticles for chemical looping dry reforming of methane[J]. Fuel, 2023, 349: 128771.
31	Klaas L, Bulfin B, Kriechbaumer D, et al. Impact of the Sr content on the redox thermodynamics and kinetics of Ca_1– _x Sr _x MnO_3– _δ for tailored properties[J]. Physical Chemistry Chemical Physics, 2023, 25(13): 9188-9197.
32	Sifontes Á B, Del Toro R S, Ávila E, et al. Chitosan templated synthesis of strontium-iron-oxygen nanocrystalline system[J]. Ceramics International, 2015, 41(10): 13250-13256.
33	Srilakshmi C, Saraf R, Shivakumara C. Effective degradation of aqueous nitrobenzene using the SrFeO_3- _δ photocatalyst under UV illumination and its kinetics and mechanistic studies[J]. Industrial & Engineering Chemistry Research, 2015, 54(32): 7800-7810.
34	Naveenkumar A, Kuruva P, Shivakumara C, et al. Mixture of fuels approach for the synthesis of SrFeO_3– _δ nanocatalyst and its impact on the catalytic reduction of nitrobenzene[J]. Inorganic Chemistry, 2014, 53(22): 12178-12185.
35	Yang L Q, Li X F, Zhang X Z, et al. Supercritical solvothermal synthesis and formation mechanism of V₂O₃ microspheres with excellent catalytic activity on the thermal decomposition of ammonium perchlorate[J]. Journal of Alloys and Compounds, 2019, 806: 1394-1402.
36	杨柳青, 何志帅, 张雄志, 等. 纳米Fe₃O₄的制备及其催化高氯酸铵热分解性能的研究[J]. 现代化工, 2016, 36(11): 94-97.
	Yang L Q, He Z S, Zhang X Z, et al. Preparation of Fe₃O₄ nanoparticles and its catalytic performance for thermal decomposition of ammonium perchlorate[J]. Modern Chemical Industry, 2016, 36(11): 94-97.
37	Li Y F, Zhang W Q, Zheng Y, et al. Controlling cation segregation in perovskite-based electrodes for high electro-catalytic activity and durability[J]. Chemical Society Reviews, 2017, 46(20): 6345-6378.
38	Barbero B P, Cadús L E, Marchetti S G. Determination of Fe(Ⅳ) species in partially substituted perovskite La_0.6Ca_0.4FeO₃ [J]. Hyperfine Interactions, 2009, 194(1): 367-379.
39	Feng N J, Wu Y, Meng J, et al. Catalytic combustion of soot over Ce and Co substituted three-dimensionally ordered macroporous La_1- _x Ce _x Fe_1- _y Co _y O₃ perovskite catalysts[J]. RSC Advances, 2015, 5(111): 91609-91618.
40	Zhang L, Xu W B, Wu J A, et al. Identifying the role of A-site cations in modulating oxygen capacity of iron-based perovskite for enhanced chemical looping methane-to-syngas conversion[J]. ACS Catalysis, 2020, 10(16): 9420-9430.
41	Neal L M, Shafiefarhood A, Li F X. Dynamic methane partial oxidation using a Fe₂O₃@La_0.8Sr_0.2FeO_3- _δ core-shell redox catalyst in the absence of gaseous oxygen[J]. ACS Catalysis, 2014, 4(10): 3560-3569.
42	Zhang X H, Pei C L, Chang X, et al. FeO₆ octahedral distortion activates lattice oxygen in perovskite ferrite for methane partial oxidation coupled with CO₂ splitting[J]. Journal of the American Chemical Society, 2020, 142(26): 11540-11549.
43	Donat F, Müller C R. CO₂-free conversion of CH₄ to syngas using chemical looping[J]. Applied Catalysis B: Environmental, 2020, 278: 119328.

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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

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

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