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

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

Abstract

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

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

CLC Number:

TQ028

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.

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.

Figures/Tables 15

References 23

[1]	REICHSTEIN Markus, BAHN Michael, CIAIS Philippe, et al. Climate extremes and the carbon cycle[J]. Nature, 2013, 500(7462): 287-295.
[2]	ZHANG Xiaowen, HUANG Yufei, YANG Jian, et al. Amine-based CO₂ capture aided by acid-basic bifunctional catalyst: Advancement of amine regeneration using metal modified MCM-41[J]. Chemical Engineering Journal, 2020, 383: 123077.
[3]	GOTO Kazuya, YOGO Katsunori, HIGASHII Takayuki. A review of efficiency penalty in a coal-fired power plant with post-combustion CO₂ capture[J]. Applied Energy, 2013, 111: 710-720.
[4]	RAO Anand B, RUBIN Edward S. A technical, economic, and environmental assessment of amine-based CO₂ capture technology for power plant greenhouse gas control[J]. Environmental Science & Technology, 2002, 36(20): 4467-4475.
[5]	Juan LYU, LIU Sen, LING Hao, et al. Development of a promising biphasic absorbent for postcombustion CO₂ capture: Sulfolane + 2-(methylamino)ethanol + H₂O[J]. Industrial & Engineering Chemistry Research, 2020, 59(32): 14496-14506.
[6]	ZHANG Shihan, SHEN Yao, WANG Lidong, et al. Phase change solvents for post-combustion CO₂ capture: Principle, advances, and challenges[J]. Applied Energy, 2019, 239: 876-897.
[7]	BAI Liju, LU Shijian, ZHAO Qizheng, et al. Low-energy-consuming CO₂ capture by liquid-liquid biphasic absorbents of EMEA/DEEA/PX[J]. Chemical Engineering Journal, 2022, 450: 138490.
[8]	ZHANG Shihan, SHEN Yao, SHAO Peijing, et al. Kinetics, thermodynamics, and mechanism of a novel biphasic solvent for CO₂ capture from flue gas[J]. Environmental Science & Technology, 2018, 52(6): 3660-3668.
[9]	JIA Ruiqi, XU Yihang, ZHANG Jiaojiao, et al. A novel phase change absorbent with ionic liquid as promoter for low energy-consuming CO₂ capture[J]. Separation and Purification Technology, 2023, 315: 123740.
[10]	LIAN Shaohan, SONG Chunfeng, LIU Qingling, et al. Recent advances in ionic liquids-based hybrid processes for CO₂ capture and utilization[J]. Journal of Environmental Sciences, 2021, 99: 281-295.
[11]	LIU Fei, FANG Mengxiang, DONG Wenfeng, et al. Carbon dioxide absorption in aqueous alkanolamine blends for biphasic solvents screening and evaluation[J]. Applied Energy, 2019, 233: 468-477.
[12]	ZHOU Xiaobin, JING Guohua, Bihong LYU, et al. Low-viscosity and efficient regeneration of carbon dioxide capture using a biphasic solvent regulated by 2-amino-2-methyl-1-propanol[J]. Applied Energy, 2019, 235: 379-390.
[13]	WANG Lidong, LIU Shanshan, WANG Rujie, et al. Regulating phase separation behavior of a DEEA-TETA biphasic solvent using sulfolane for energy-saving CO₂ capture[J]. Environmental Science & Technology, 2019, 53(21): 12873-12881.
[14]	LIU Fan, SHEN Yao, SHEN Li, et al. Sustainable ionic liquid organic solution with efficient recyclability and low regeneration energy consumption for CO₂ capture[J]. Separation and Purification Technology, 2021, 275: 119123.
[15]	ZHOU Xiaobin, LI Xiaoling, WEI Jianwen, et al. Novel nonaqueous liquid-liquid biphasic solvent for energy-efficient carbon dioxide capture with low corrosivity[J]. Environmental Science & Technology, 2020, 54(24): 16138-16146.
[16]	JIANG Wufeng, LI Xiaoshan, GAO Ge, et al. Advances in applications of ionic liquids for phase change CO₂ capture[J]. Chemical Engineering Journal, 2022, 445: 136767.
[17]	CHIU Li-Feng, LIU Hsiao-Fen, LI Menghui. Heat capacity of alkanolamines by differential scanning calorimetry[J]. Journal of Chemical & Engineering Data, 1999, 44(3): 631-636.
[18]	YANG Jie, YU Xinhai, AN Lin, et al. CO₂ capture with the absorbent of a mixed ionic liquid and amine solution considering the effects of SO₂ and O₂ [J]. Applied Energy, 2017, 194: 9-18.
[19]	JIA Ruiqi, WU Qing, ZHANG Liangliang, et al. CO₂ absorption mechanism and kinetic modeling of mixed amines with ionic liquid activation[J]. AIChE Journal, 2024, 70(9): e18493.
[20]	HAIDER Md Belal, HUSSAIN Zakir, KUMAR Rakesh. CO₂ absorption and kinetic study in ionic liquid amine blends[J]. Journal of Molecular Liquids, 2016, 224: 1025-1031.
[21]	LEITES I L. Thermodynamics of CO₂ solubility in mixtures monoethanolamine with organic solvents and water and commercial experience of energy saving gas purification technology[J]. Energy Conversion and Management, 1998, 39(16/17/18): 1665-1674.
[22]	MALINOWSKI Janusz J, DAUGULIS Andrew J. Salt effects in extraction of ethanol, 1-butanol and acetone from aqueous solutions[J]. AIChE Journal, 1994, 40(9): 1459-1465.
[23]	Mar OLAYA M, GARCÍA Angela N, MARCILLA Antonio. Liquid-liquid-solid equilibria for the quaternary system water + acetone + 1-butanol + sodium chloride at 25℃[J]. Journal of Chemical & Engineering Data, 1996, 41(4): 910-917.

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

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

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

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

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

MDEA/DETA/[Bmim][BF₄]/H₂O相变吸收剂的开发及性能

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 15

References 23

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	CHEN Siming, LIU Jingchao, ZHONG Zhixuan, ZHANG Xinzhu, ZHU Tianhao, PENG Yiqing, YOU Sai, WANG Yikai, YUAN Jiajun, ZHANG Yongchun. Development and application of deep eutectic solvents in carbon dioxide capture [J]. Chemical Industry and Engineering Progress, 2025, 44(9): 5377-5390.
[2]	ZHANG Wenjing, HUANG Zhixin, LI Shiteng, DENG Shuai, LI Shuangjun. Biomass carbon aerogels for CO₂ adsorbents [J]. Chemical Industry and Engineering Progress, 2025, 44(9): 5018-5032.
[3]	HUANG Ke’er, LIU Jiahao, LI Haoming, ZHOU Tianhang, GAO Jinsen, LAN Xingying. Self-diffusion coefficients in the process of carbon capture by amine solvents based on molecular dynamics simulation [J]. Chemical Industry and Engineering Progress, 2025, 44(8): 4352-4364.
[4]	YU Ziyu, CHEN Xiaofei, HOU Chunguang, YUE Dianhe, PENG Yuelian, AN Quanfu. Comparative study of vapor pervaporation and vacuum membrane distillation in dicarbamate dehydration [J]. Chemical Industry and Engineering Progress, 2025, 44(6): 3247-3257.
[5]	FU Zijun, SONG Xuehang, SHEN Qun, WANG Xiaobo, GU Jiaming, WANG Danfeng, WEI Wei, SUN Nannan. Carbon footprint analysis of integrated CO₂ capture and methanation technology based on life cycle assessment [J]. Chemical Industry and Engineering Progress, 2025, 44(5): 2879-2887.
[6]	DOU Yu, WANG Wenxuan, FAN Chunlei, MA Jiliang, LIANG Cai, CHEN Xiaoping. Preparation of vaterite CaCO₃ by mineralizing CO₂from desulfurized gypsum [J]. Chemical Industry and Engineering Progress, 2025, 44(4): 2328-2337.
[7]	ZHANG Yating, MA Xiaomei, LI Keke, JIA Jia, CHEN Meng, DAI Liang, GAO Xitong. Recent advances on CDs/g-C₃N₄ heterostructure: Construction and photocatalytic application [J]. Chemical Industry and Engineering Progress, 2025, 44(10): 5751-5763.
[8]	LI Letian, LU Shijian, LIU Hanxiao, WU Liming, LIU Ling, KANG Guojun. Progress of desorption and regeneration of organic amine-enriched liquids [J]. Chemical Industry and Engineering Progress, 2025, 44(1): 490-499.
[9]	WANG Ning, LU Shijian, LIU Ling, LIANG Jing, LIU Miaomiao, SUN Mengyuan, KANG Guojun. Research progress of catalytic regeneration for energy-efficient CO₂ capture in amine absorption system [J]. Chemical Industry and Engineering Progress, 2025, 44(1): 445-464.
[10]	LU Shijian, ZHANG Juanjuan, YANG Fei, LIU Ling, CHEN Siming, KANG Guojun, FANG Qinqin. Research progress of amine escape control technology by chemical absorption method [J]. Chemical Industry and Engineering Progress, 2024, 43(8): 4562-4570.
[11]	ZHI Yuan, MA Jiliang, CHEN Xiaoping, LIU Daoyin, LIANG Cai. Decarbonization capability of supported Na-based CO₂ adsorbents prepared by fluidized bed spray impregnation [J]. Chemical Industry and Engineering Progress, 2024, 43(6): 2961-2967.
[12]	LIU Kefeng, LIU Taoran, CAI Yong, HU Xuesheng, DONG Weigang, ZHOU Huaqun, GAO Fei. Progress in research and engineering demonstration of CO₂ capture technology [J]. Chemical Industry and Engineering Progress, 2024, 43(6): 2901-2914.
[13]	MIAO Yihe, WANG Yaozu, LIU Yuhang, ZHU Xuancan, LI Jia, YU Lijun. Research progress on the improving effect of additives on supported amine adsorbents for carbon capture [J]. Chemical Industry and Engineering Progress, 2024, 43(5): 2739-2759.
[14]	GAO Fanxiang, LIU Yang, ZHANG Guiquan, QIN Feng, YAO Jiantao, JIN Hui, SHI Jinwen. Research progress of wet process synergistic desulfurization and decarbonization technology for coal-fired flue gas [J]. Chemical Industry and Engineering Progress, 2024, 43(5): 2324-2342.
[15]	SUN Weiji, LIU Lang, FANG Zhiyu, ZHU Mengbo, XIE Geng, HE Wei, GAO Yuheng. Technique of wet carbonation of modified magnesium slag [J]. Chemical Industry and Engineering Progress, 2024, 43(4): 2161-2173.