MDEA/DETA/[Bmim][BF4]/H2O相变吸收剂的开发及性能

doi:10.16085/j.issn.1000-6613.2024-1295

摘要/Abstract

摘要：

为降低碳捕集成本，本文提出了一种由N-甲基二乙醇胺（MDEA）、二乙基三胺（DETA）、1-丁基-3-甲基咪唑四氟硼酸盐离子液体（[Bmim][BF₄]）和水组成的新型相变吸收剂用于CO₂捕集。其中，MDEA作为主要吸收剂，添加少量DETA作为活化剂，引入[Bmim][BF₄]作为分相剂，研究了MDEA基相变吸收剂的分相性能、分相机理、CO₂吸收和再生性能。结果表明，通过改变[Bmim][BF₄]的浓度可以有效实现对相变吸收剂的分相体积分数、分相时间和两相CO₂负载的调控。基于分相结果和¹³C核磁共振（NMR）分析，阐明了其吸收和分相机理，贫富液发生分相的关键在于氨基甲酸盐浓度的影响。吸收和再生性能实验表明，离子液体的存在显著提高了初始吸收速率，且吸收剂可以适应一定范围的温度变化影响。新型吸收剂具有较低的再生能耗，主要表现为反应热和潜热的降低。其再生能耗可降低到1.99GJ/t CO₂，比30%单乙醇胺（MEA）低48.8%。

关键词: CO₂捕集, 相变吸收剂, N-甲基二乙醇胺, 氨基甲酸盐, 再生能耗

Abstract:

To reduce the carbon capture cost, a novel phase change absorbent composed of N-methyldiethanolamine (MDEA), diethylenetriamine (DETA), 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquids ([Bmim][BF₄]) and water was proposed for CO₂ capture. Among them, MDEA was used as the main absorbent, a small amount of DETA was added as the activator, and [Bmim][BF₄] was introduced as the phase splitter. The phase separation properties, phase separation mechanism, CO₂ absorption and regeneration performance of MDEA-based phase change absorbent were investigated. The results showed that the modulation of the fractional volume ratio, phase separation time and CO₂ loading of the two phases of phase change absorbents could be effectively achieved by changing the concentration of [Bmim][BF₄]. Based on the phase separation results and ¹³C NMR analysis, the absorption and phase separation mechanisms were elucidated and the key for the phase separation of the rich and poor phases was the effect of carbamate concentration. The absorption and regeneration performance experiments indicated that the presence of ionic liquid significantly increased the initial absorption rate and the absorbent could adapt to the effects of temperature changes in a certain range. The new absorbent had a low regeneration energy consumption, which was mainly due to the reduction of reaction heat and latent heat. Its regeneration energy consumption can be reduced to 1.99GJ/t CO₂, which was 48.8% lower than that of 30% MEA.

Key words: CO₂ capture, phase change absorbent, N-methyldiethanolamine (MDEA), carbamate, regeneration energy consumption

中图分类号:

TQ028

王栋, 贾瑞琪, 张博, 张娇娇, 肖家旺, 张亮亮. MDEA/DETA/[Bmim][BF₄]/H₂O相变吸收剂的开发及性能[J]. 化工进展, 2025, 44(10): 5891-5898.

WANG Dong, JIA Ruiqi, ZHANG Bo, ZHANG Jiaojiao, XIAO Jiawang, ZHANG Liangliang. Development and performance of phase change absorbent for MDEA/DETA/[Bmim][BF₄]/H₂O[J]. Chemical Industry and Engineering Progress, 2025, 44(10): 5891-5898.

图/表 15

图1 二氧化碳吸收实验装置示意图

图2 再生实验装置示意图

图3 MDEA基吸收剂的相变现象

表1 MDEA/DETA/[Bmim][BF4]吸收剂的分相结果

吸收剂	富CO₂相体积分数/%	分相时间/min	相变点对应的CO₂负载/mol∙L^-1
3M1D	0	0	0
3M1D1.2B	86.81	12	1.37
3M1D1.5B	72.22	7	0.92
3M1D1.8B	59.26	5	0.74

图4 MDEA基相变吸收剂的分相比例

图5 富贫相CO2负载随总CO2负载的变化

图6 不同CO2负载下吸收剂的密度

图7 分子结构和碳原子编号

图8 MDEA/DETA/[Bmim][BF4]溶液的13C NMR谱（α代表不同CO2负载）

表2 各组分在两相中的分布

α/mol∙L^-1	液相	MDEA/mol∙L^-1	DETA/mol∙L^-1	氨基甲酸盐/mol∙L^-1	(HCO₃^-/CO₃^2-)/mol∙L^-1	[Bmim][BF₄]/mol∙L^-1
0.91	富CO₂相	2.28	0.62	0.16	0	0.08
0.91	贫CO₂相	0.99	0	0	0	0.29
1.51	富CO₂相	3.21	1.08	0.79	0.04	0.09
1.51	贫CO₂相	0.64	0	0	0	0.21

图9 相变吸收剂CO2吸收和分相机理

图10 不同MDEA基吸收剂的CO2吸收性能

图11 温度对吸收性能的影响

图12 不同吸收剂的再生能耗估算

图13 循环次数对解吸率的影响

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MDEA/DETA/[Bmim][BF₄]/H₂O相变吸收剂的开发及性能

Development and performance of phase change absorbent for MDEA/DETA/[Bmim][BF₄]/H₂O

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