改性BaFe2O4载氧体生物质化学链气化特性

doi:10.11949/0438-1157.20211437

摘要/Abstract

摘要：

以溶胶凝胶法制备了BaFe₂O₄载氧体以及Ni、Ce、K修饰的BaFe₂O₄载氧体，筛选出最佳载氧体为10%(质量)K修饰的BaFe₂O₄载氧体(10K-BF)，探究了不同反应条件对其性能的影响，通过H₂-TPR、XRD、SEM、BET对载氧体表征。实验结果表明，Ni、Ce、K的添加均提高了载氧体的合成气产率，10K-BF载氧体在水蒸气与生物质质量比(S/B)等于3，过氧系数α=0.20，反应温度800℃时，气化效果最好，合成气产率1.864 m³/(kg Biomass)，氢气产率1.038 m³/(kg Biomass)，碳转化率90.49%，积炭率1.33%，10次循环后仍有较高的气体产率及碳转化率。H₂-TPR表明10K-BF载氧体在300℃开始释氧，在生物质热解的初始阶段即可参与反应，有利于焦油的裂解；XRD表明10K-BF载氧体再生后可以恢复部分尖晶石结构。

关键词: 生物质, 气化, 合成气, 积炭率, 铁酸钡

Abstract:

The BaFe₂O₄ oxygen carrier and BaFe₂O₄ oxygen carrier modified by Ni, Ce and K were prepared by the sol-gel method, and the best oxygen carrier was selected as 10%(mass) K modified BaFe₂O₄ (10K-BF), and the difference was explored. The effect of reaction conditions on its performance was characterized by H₂-TPR, XRD, SEM, and BET on the oxygen carrier. The experimental results showed that the addition of Ni, Ce and K all increase the syngas yield. The 10K-BF oxygen carrier exhibited the best performance when the mass ratio of steam to biomass (S/B) was equal to 3, peroxygen coefficient α=0.20 and t=800℃. Its syngas yield was 1.864 m³/(kg Biomass), hydrogen production rate was 1.038 m³/(kg Biomass), carbon conversion rate was 90.49% and carbon deposition rate was 1.33%. After 10 cycles, there was still a high syngas yield and carbon conversion rate. H₂-TPR result indicated that the 10K-BF oxygen carrier starts to release oxygen at 300°C and can participate in the reaction at the initial stage of biomass pyrolysis, which is beneficial to the cracking of tar. XRD characterization showed that the 10K-BF oxygen carrier can recover part of the spinel structure after regeneration.

Key words: biomass, gasification, syngas, carbon deposition rate, barium ferrite

中图分类号:

TK 6

袁聪, 蒲舸, 高杰, 贾帅辉. 改性BaFe₂O₄载氧体生物质化学链气化特性[J]. 化工学报, 2022, 73(3): 1359-1368.

Cong YUAN, Ge PU, Jie GAO, Shuaihui JIA. Biomass chemical-looping gasification characteristics of K-modified BaFe₂O₄ oxygen carrier[J]. CIESC Journal, 2022, 73(3): 1359-1368.

图/表 12

表1 松木屑的元素分析及低位热值（LHV）

Table 1 Elemental analysis and LHV of pine samples

Ultimate analysis/%(质量，干燥基)						LHV/(MJ/kg)
C	H	O	N	S	A	LHV/(MJ/kg)
47.42	6.31	43.13	0.01	0.36	2.77	18.41

图1 固定床反应系统图

Fig.1 Fixed bed reaction system diagram

图2 BF、10Ni-BF、10Ce-BF、10K-BF四种载氧体反应性能

Fig.2 Reaction performance of four oxygen carriers: BF，10Ni-BF，10Ce-BF and 10K-BF

图3 负载不同质量的K的影响

Fig.3 The influence of load with different quality of K

图4 温度的影响

Fig.4 The influence of temperature

图5 水蒸气含量的影响

Fig.5 The influence of water vapor content

图6 过氧系数的影响

Fig.6 The influence of peroxygen coefficient

图7 循环次数的影响

Fig.7 The influence of the number of cycles

图8 10K-BF的H2-TPR曲线

Fig.8 H2-TPR curve of 10K-BF

图9 BF与10K-BF载氧体的XRD谱图

Fig.9 XRD pattern of BF and 10K-BF carriers

图10 不同循环次数下10K-BF的XRD谱图

Fig.10 XRD pattern of 10K-BF under different cycles

图11 不同循环次数下载氧体的SEM表征

Fig.11 SEM characterization of the downloaded oxygen at different cycles

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改性BaFe₂O₄载氧体生物质化学链气化特性

Biomass chemical-looping gasification characteristics of K-modified BaFe₂O₄ oxygen carrier

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