Performance and durability of cobalt doped SrTi0.3Fe0.7O3-δ anode SOFC fueled with by-product gas from chemical industry

doi:10.11949/0438-1157.20220470

Abstract

Abstract:

Chemical by-product gas is a flammable and complex gas with a certain calorific value, but its purification and reuse have always been low in economic benefits, and most of them are treated by direct combustion. In respond to the current demand for chemical industry to carry out green and low-carbon transition, this paper investigates the performance of solid oxide fuel cell (SOFC) to generate electricity using by-product gas from chemical industry. B-site cobalt doped Sr_0.95Ti_0.33Fe_0.6Co_0.07O_3-_δ (STFC) perovskite oxide anode is prepared by high-temperature solid-phase synthesis method which based on SrTi_0.3Fe_0.7O_3-_δ (STF) perovskite oxide with high mixed oxygen ion and electron conduction capacity. STFC anode structure, electrochemical performance and durability are systematically characterized by using different types and ratios of simulated chemical by-product gases as a fuel. The results show that Co_0.28Fe_0.72 nanoparticles were in situ precipitated after reduction of STFC perovskite oxide in humidified hydrogen. The electrochemical performance test in different types of simulated chemical by-product gases showed that, the small polarization impedance and high output power density are obtained for STFC anode. And the single cell operates for excellent long-term stability under complex fuels with rich hydrocarbon components.

Key words: fuel cells, carbon reduction, chemical by-product gas, perovskite anode, nanomaterials, electrochemistry

摘要：

化工副产气是具有一定热值的可燃性复杂气体，但一直以来提纯再利用经济效益低，大多采用直接燃烧的方法处理。针对当前化学工业开展绿色低碳转型的需求，研究了固体氧化物燃料电池(SOFC)采用化工副产气发电的性能。以SrTi_0.3Fe_0.7O_3-_δ (STF)钙钛矿氧化物为基础，采用高温固相合成法制备了B位Co掺杂的Sr_0.95Ti_0.33Fe_0.6Co_0.07O_3-_δ (STFC)阳极，以不同种类和组成的模拟化工副产气作为燃料，系统研究了单电池的电化学性能和稳定性。结果表明，STFC钙钛矿氧化物在加湿氢气中还原后原位析出Co_0.28Fe_0.72纳米合金颗粒；以其为阳极的SOFC单电池在多种模拟化工副产气燃料下实现了高性能运行，表现出较小的极化阻抗和良好的电化学性能输出；在含有多种碳氢组分的复杂燃料下表现出卓越的长期运行稳定性。

关键词: 燃料电池, 碳减排, 化工副产气, 钙钛矿阳极, 纳米材料, 电化学

CLC Number:

TQ 150.9

Wanchen ZHANG, Xiaoyang CHEN, Qiuqiu LYU, Qin ZHONG, Tenglong ZHU. Performance and durability of cobalt doped SrTi_0.3Fe_0.7O_3-_δ anode SOFC fueled with by-product gas from chemical industry[J]. CIESC Journal, 2022, 73(9): 4079-4086.

张婉晨, 陈晓阳, 吕秋秋, 钟秦, 朱腾龙. Co掺杂SrTi_0.3Fe_0.7O_3-_δ 阳极SOFC在化工副产气燃料下的性能及稳定性[J]. 化工学报, 2022, 73(9): 4079-4086.

Figures/Tables 8

Table 1 Composition and heat value of typical by-product gases

化工工艺源	副产气组成/%(体积)	热值(LHV)/(MJ/m³)
炼油	N₂ 13.1、CO₂ 0.7、CO 1.3、H₂ 30.6、CH₄ 35.1、C₂H₆ 10.9、C₃H₈ 8.3	30~32
丙烷脱氢	H₂、CO₂、CO、CH₄、C₂H₄、C₂H₆、C₃H₆、C₃H₈	25~27
炼焦工业	H₂ 54~60、CH₄ 19~24、CO、CO₂	17~19
合成氨	NH₃ 17.9、H₂ 46.5、N₂ 15.1、CH₄ 46.5、Ar	13~15
碳化硅合成	CO 70~90、CO₂ 2~3、H₂1~5、N₂ 1~3、CH₄ 2~4	10~14

Table 2 The compositions of simulated by-product gas and by-product gas in refinery section

编号	气体组成	比例
1	H₂、CO₂、CO	x(CO₂)=10%，y(H₂)=6%~45 %，z(CO)=100%-x-y
2	H₂、CO₂、CH₄	x(CO₂)=10%，y(CH₄)=3%~12 %，z(H₂)=100%-x-y
3	某化工企业炼油工段副产气	N₂ (13.1%)、CO₂ (0.7%)、CO (1.3%)、H₂ (30.6%)、CH₄ (35.1%)、C₂H₆ (10.9%)、C₃H₈ (8.3%)

Fig.1 XRD pattern of STFC calcined in air at 1100℃ and reduced in wet hydrogen at 800℃ (a); SEM image of STFC reduced in wet hydrogen at 800℃ (b)

Fig.2 Electrochemical performance of STFC cell under simulated by-product gases at 800℃.(a), (b) Current density-voltage-power density (J-V-P) curves of STFC cell under CO2-H2-CO and CO2-H2-CH4 fuels; (c), (e), (d), (f) Electrochemical impedance spectroscopy (EIS) and the corresponding DRT analysis of STFC cell under CO2-H2-CO and CO2-H2-CH4 fuels

Fig.3 Variations in electrochemical performance of STFC anode cell under simulated by-product fuels

Fig.4 J-V-P curves of single cell under by-product gas at 800℃ (a); EIS results of single cell under by-product gas at 800℃ (b)

Fig.5 Long-term stability of STFC anode cell and variations of each tail gases under byproduct gas at 800°C

Fig.6 Schematic of fuel oxidation mechanism (a); SEM image of STFC anode after long-term operation (b)

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