基于化学链燃烧的转炉放散煤气利用研究

doi:10.11949/j.issn.0438-1157.20181452

摘要/Abstract

摘要：

在固定床反应器和热重分析仪上对浸渍法制备的过渡金属氧化物载氧体MnO₂/Al₂O₃、Fe₂O₃/Al₂O₃和CuO/Al₂O₃与转炉放散煤气中CO的反应特性进行了研究，并结合比表面积分析、脉冲化学吸附和扫描电镜等手段表征了CuO/Al₂O₃的循环寿命性能。结果表明，在上述三种载氧体中CuO/Al₂O₃表现出了最佳的反应活性，反应进行2 min时的CO转化率在225℃以上的反应温度下就能达到90%。在350℃、还原反应空速4000 h^-1和氧化反应空速159 h^-1的条件下，CuO/Al₂O₃能够保持良好且稳定的CO脱除性能和机械强度，因而具有良好的循环寿命。据此，提出了基于化学链燃烧的转炉放散煤气利用新工艺，本工艺可安全利用间歇排放的转炉放散煤气，并实现对用户的连续供热。

关键词: 转炉放散煤气, CO, 化学链燃烧, 载氧体, 还原, 氧化, 循环寿命, 固定床反应器

Abstract:

Characteristics of the reduction reactions between transition metal oxide oxygen carriers (OCs) including MnO₂/Al₂O₃, Fe₂O₃/Al₂O₃ and CuO/Al₂O₃ prepared by an impregnation method and CO in converter off-gas were investigated using a fixed bed reactor and a thermogravimetric analyzer. Surface area analysis, pulse chemisorption and scanning electron microscopy were used to characterize the cycle life performance of CuO/Al₂O₃. The results show that CuO/Al₂O₃ exhibit the best reactivity among the three OCs, and the CO conversion at the reaction time of 2 min reach 90% when the reaction temperature is 225℃ or higher. Moreover, CuO/Al₂O₃ can maintain the high and stable performance of CO removal and mechanical strength at 350℃, a gas hourly space velocity (GHSV) of 4000 h^-1 in the reduction reaction and a GHSV of 159 h^-1 in the oxidation reaction, exhibiting an excellent redox cycle life. Based on these findings, a new process based on CLC has been proposed, with which the intermittently discharged converter off-gas can be safely utilized, thereby achieving the continuous heat supply to users.

Key words: converter off-gas, carbon monoxide, chemical-looping combustion, oxygen carrier, reduction, oxidation, cycle life, fixed-bed reactor

中图分类号:

X 756

武永健, 罗春欢, 魏琳, 朱探金, 苏庆泉. 基于化学链燃烧的转炉放散煤气利用研究[J]. 化工学报, 2019, 70(5): 1923-1931.

Yongjian WU, Chunhuan LUO, Lin WEI, Tanjin ZHU, Qingquan SU. Utilization of converter off-gas based on chemical-looping combustion[J]. CIESC Journal, 2019, 70(5): 1923-1931.

图/表 10

图1 典型的转炉生产周期

Fig.1 A typical operating cycle in converter steelmaking process

图2 载氧体的反应性能评价装置

Fig.2 Schematic of experimental apparatus for evaluation of OCs

图3 样品失重和热流曲线

Fig.3 Weight loss and heat flow curves for Fe2O3/Al2O3, MnO2/Al2O3, and CuO/Al2O3

图4 三种载氧体的还原反应中，空速2000 h-1时， 450℃下，出口气体中CO浓度随反应时间的变化及 X C O , 2 随反应温度的变化

Fig.4 In reduction reaction for three OCs at 2000 h-1, outlet CO concentration versus reaction time at 450℃(a), and X C O , 2 versus reaction temperature(b)

图5 空速4000 h-1、温度350℃，CuO/Al2O3的还原反应出口气体中CO浓度和 X R , t 随时间的变化(a)及空速159 h-1、温度350℃，Cu/Al2O3的氧化反应出口气体中O2浓度和 X O , t 随时间的变化(b)

Fig.5 Outlet CO concentration and X R , t versus time in reduction reaction of CuO/Al2O3 at 350℃ and 4000 h-1(a), and outlet O2 concentration and X O , t versus time in oxidation reaction of Cu/Al2O3 at 350℃ and 159 h-1(b)

图6 CuO/Al2O3样品的扫描电镜图

Fig.6 SEM images of CuO/Al2O3 samples

图7 CuO/Al2O3循环寿命实验中， X C O , 2 、还原反应的床层压降、载氧体的平均破碎强度随循环次数的变化

Fig.7 X C O , 2 , pressure drop in reduction reaction and average crushing strength of OCs versus cycle times in cyclic life experiment of CuO/Al2O3

表1 不同循环次数下的CuO/Al2O3的比表面积、孔容、孔径及CO吸附量

Table 1 Specific surface area, pore volume, average pore size and CO adsorption for CuO/Al2O3 under different cycle times

循环次数	比表面积/(m²?g^-1)	孔容/(ml?g^-1)	平均孔径/nm	CO化学吸附量/(ml?g^-1)
0	164.78	0.376	9.12	1.60
3000	156.81	0.382	9.87	1.43
6000	145.52	0.375	10.41	1.15
9000	131.44	0.381	12.15	0.54
12000	114.54	0.389	13.60	0.32

图8 基于化学链燃烧的转炉放散煤气利用新工艺

Fig.8 New process for utilization of converter off-gas based on CLC

表2 还原反应和氧化反应的热力学数据

Table 2 Thermodynamic data for reduction and oxidation reactions

反应		$Δ G 350 ℃ 0$ / (kJ·mol^-1)	$Δ H 350 ℃ 0$ / (kJ·mol^-1)
还原反应	2CuO + CO $?$ Cu₂O + CO₂	-154.56	-146.22
还原反应	Cu₂O + CO $?$ 2Cu + CO₂	-105.38	-113.80
氧化反应	4Cu + O₂ $?$ 2Cu₂O	-246.45	-339.58
氧化反应	2Cu₂O + O₂ $?$ 4CuO	-148.10	-274.74

表2 还原反应和氧化反应的热力学数据

Table 2 Thermodynamic data for reduction and oxidation reactions

反应		$Δ G 350 ℃ 0$ / (kJ·mol^-1)	$Δ H 350 ℃ 0$ / (kJ·mol^-1)
还原反应	2CuO + CO $?$ Cu₂O + CO₂	-154.56	-146.22
还原反应	Cu₂O + CO $?$ 2Cu + CO₂	-105.38	-113.80
氧化反应	4Cu + O₂ $?$ 2Cu₂O	-246.45	-339.58
氧化反应	2Cu₂O + O₂ $?$ 4CuO	-148.10	-274.74

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