Co掺杂SrTi0.3Fe0.7O3-δ 阳极SOFC在化工副产气燃料下的性能及稳定性

doi:10.11949/0438-1157.20220470

摘要/Abstract

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

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

中图分类号:

TQ 150.9

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.

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.

图/表 8

表1 典型化工副产气的组成及热值

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

表2 模拟化工副产气及炼油某工段副产气组成

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%)

图1 STFC粉体在1100℃空气煅烧和在800℃氢气(约3% H2O)还原后XRD谱图(a); STFC粉体在800℃氢气(约3% H2O)还原后SEM图(b)

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)

图2 800℃时STFC阳极在不同组成模拟副产气中的电化学性能:(a), (b) CO2-H2-CO及CO2-H2-CH4燃料体系下单电池的电流密度-电压-功率密度(J-V-P)曲线;(c), (e), (d), (f) CO2-H2-CO及CO2-H2-CH4燃料体系下单电池的电化学阻抗谱(EIS)与相应的DRT分析

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

图3 单电池在模拟副产气燃料下电化学性能的变化

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

图4 800 ℃时STFC单电池在副产气燃料下的电流密度-电压-功率密度曲线及(a)； 800℃时STFC单电池在副产气燃料下的电化学阻抗谱图(b)

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)

图5 800℃时电池在副产气燃料下的长期稳定性和尾气各组分产物变化

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

图6 燃料氧化机制示意图(a)；副产气长期运行后STFC阳极的SEM图像(b)

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

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