MnFeO3和MnFe2O4氧载体在稻草化学链气化中的应用

doi:10.11949/0438-1157.20190798

摘要/Abstract

摘要：

通过溶胶凝胶燃烧法合成了MnFeO₃和MnFe₂O₄两种锰铁复合氧载体。通过原位红外实验探究其与稻草的化学链气化过程，发现其加速了稻草热解产物的析出，并通过气化反应促进CO和CO₂的产生，提高了碳转化率。固定床实验结果表明MnFeO₃和MnFe₂O₄在与水蒸气耦合气化的条件下大幅提高了合成气中H₂和CO的产率，气化效率分别达到94.49%和92.76%。并通过XRD分析，发现MnFeO₃和MnFe₂O₄在气化过程主要还原为(Fe,Mn)O，且在氧化反应后能回到初始晶相。在固定床的10次循环实验以及SEM的结果表明，MnFeO₃在循环反应中逐渐形成的颗粒状多孔结构有利于维持稳定的气化效率，而MnFe₂O₄由于团聚和烧结作用形成了块状结构，气化效率呈缓慢下降趋势。因此，认为MnFeO₃在生物质化学链气化中具有更好的适用性。

关键词: 生物质, 气化, 合成气, 锰铁复合氧载体, 化学链

Abstract:

The reactivity of oxygen carriers is curial for biomass chemical looping gasification (CLG) process. Two kinds of manganese-iron composite oxygen carriers of MnFeO₃ and MnFe₂O₄ were synthesized by sol-gel combustion method. Though the in situ infrared, CLG experiments with straw were carried out. It indicated that the ferromanganese composite oxides accelerated the release rate of pyrolysis products and enhanced the yield of CO and CO₂, which promoted the carbon conversion efficiency. Further tests in fix-bed were to prove the feasibility of MnFeO₃ and MnFe₂O₄ and the influence by coupling with steam. It showed that components of H₂ and CO in syngas could be improved significantly by introducing steam and the gasification efficiency for MnFeO₃ and MnFe₂O₄ was 94.49% and 92.76% individually. The XRD analysis demonstrated that MnFeO₃ and MnFe₂O₄ transformed to a combination of (Fe, Mn)O during the reduction process and both of them exhibit recyclable crystalline phase variation. Moreover, multiple redox tests showed MnFe₂O₄ exhibited a decreasing tendency of gasification efficiency because of agglomeration, its typical surface morphology changed from scattered particles to blocky structure. However, MnFeO₃ formed a granular porous structure which helped to maintain a stable reactivity. Thus, MnFeO₃ was considered to have better applicability in CLG process.

Key words: biomass, gasification, syngas, ferromanganese composite oxygen carriers, chemical looping

中图分类号:

TK 6

陈智豪, 廖艳芬, 莫菲, 刘桂才, 余昭胜, 马晓茜. MnFeO₃和MnFe₂O₄氧载体在稻草化学链气化中的应用[J]. 化工学报, 2019, 70(12): 4835-4846.

Zhihao CHEN, Yanfen LIAO, Fei MO, Guicai LIU, Zhaosheng YU, Xiaoqian MA. Application of MnFeO₃ and MnFe₂O₄ as oxygen carriers for straw chemical looping gasification[J]. CIESC Journal, 2019, 70(12): 4835-4846.

图/表 13

表1 稻草元素分析、工业分析与热值分析（干基）

Table 1 Proximate and ultimate analysis of rice straw (dry basis)

工业分析/%(mass)			元素分析/%(mass)					热值/(MJ/kg)
挥发分	灰分	固定碳	C	H	N	S	O^①	热值/(MJ/kg)
76.32	8.14	15.54	42.48	6.24	0.55	0.03	42.56	17.50

图1 固定床反应系统结构

Fig.1 Schematic of fixed bed reactor system

图2 化学链气化红外谱图

Fig.2 FTIR spectra of gaseous products from chemical looping gasification

图3 吸收峰随时间变化曲线

Fig.3 Time-varying FTIR absorbance of gas product generated from reactions

图4 各组分气体在惰性气氛下的产量

Fig.4 Yield of each component gas in an inert atmosphere

表2 化学链气化过程的性能评价

Table 2 Performance evaluation of chemical looping gasification process

氧载体	未添加水蒸气			添加水蒸气
氧载体	η/%	η _C/%	G _v/(m³/kg)	η/%	η _C/%	G _v/(m³/kg)
none	52.85	55.7	0.60	81.37	83.58	1.11
Fe₂O₃	56.66	72.81	0.75	88.21	90.47	1.44
MnFeO₃	56.94	74.57	0.79	94.49	96.89	1.61
MnFe₂O₄	61.28	76.37	0.85	92.76	93.28	1.58

图5 MnFe2O4循环反应结果

Fig.5 Multiple redox reaction with MnFe2O4

图6 MnFeO3循环反应结果

Fig.6 Multiple redox reaction with MnFeO3

图7 氧载体的XRD分析结果

Fig.7 XRD results of oxygen carriers

图8 氧载体释氧过程的晶体结构变化

Fig.8 Crystal transform during reduction process

表3 氧载体晶体参数

Table 3 Crystal parameters of oxygen carriers

氧载体	空间群	晶胞常数	晶夹角	Mn—O/?	Fe—O/?
Fe₂O₃	R -3 c	a=b=4.986，c=13.502	α =β=90°，γ=120°	—	2.1095
MnFeO₃	I a -3	a=b=c=9.365	α=β=γ=90°	2.0245	2.0245
MnFe₂O₄	F d -3 m	a=b=c=8.498	α =β=γ=90°	2.0446	2.0134

图9 MnFe2O4在不同循环后的SEM图

Fig.9 SEM images of MnFe2O4 in multiple redox cycles

图10 MnFeO3在不同循环后的SEM图

Fig.10 SEM images of MnFeO3 in multiple redox cycles

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MnFeO₃和MnFe₂O₄氧载体在稻草化学链气化中的应用

Application of MnFeO₃ and MnFe₂O₄ as oxygen carriers for straw chemical looping gasification

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