新型相变有机胺吸收捕集CO2技术研究进展

doi:10.16085/j.issn.1000-6613.2022-1019

摘要/Abstract

摘要：

CO₂捕集、利用与封存（CCUS）技术是实现碳减排的关键技术之一，有机胺吸收技术是目前研究最广泛、最成熟的CO₂捕集技术，已有少数工业应用案例。吸收剂是吸收技术的核心，吸收剂的研发创新是该领域的热点方向。相比于单一相的有机胺吸收剂，相变吸收剂在吸收CO₂后产生相变行为，仅需对富相进行再生，可大幅减少再生体积，降低再生能耗。本文介绍了传统混合胺相变吸收体系的典型工艺、吸收机理和吸收剂研究进展，分析了吸收剂吸收CO₂后富相黏度高、富相体积占比大及其导致的再生能耗增加的问题。本文系统梳理了为解决上述问题而研发的四种新型的相变吸收体系，分别为空间位阻胺混合型相变吸收剂、物理溶剂混合型相变吸收剂、醇胺混合型相变吸收剂、催化剂-有机胺复合型相变吸收剂，对各类新型相变吸收体系的设计构建原理及性能强化机制进行了分析。最后，基于对研究进展的深入分析，提出了相变吸收剂的未来研究方向。

关键词: 二氧化碳捕集, 化学吸收, 相变吸收剂, 再生能耗, 催化再生

Abstract:

CO₂ capture, utilization and storage (CCUS) technology is one of the key technologies to achieve carbon emission reduction. The organic amine absorption technology is the most widely studied and mature CO₂ capture technology, which already has a few industrial application cases. The absorbent is the core of absorption technology. The R&D and innovation of absorbent is the hot topic in this field. Compared with single-phase organic amine absorbents, the biphasic absorbent can significantly reduce the regeneration volume and the regeneration energy consumption, wherein, the homogenous absorbent can be separated into two phases after absorbing CO₂, and only the CO₂-rich phase needs to be regenerated. This paper introduced the typical process, absorption mechanism and research progress of traditional mixed amine biphasic absorbent systems, and analyzed the problems in high viscosity, high rich phase ratio after CO₂ absorption and the resulted increment of regeneration energy consumption. Four types of mixed biphasic absorbents to solve the above problems were systematically combed, including sterically hindered amine mixed biphasic absorbents, physical solvent mixed biphasic absorbents, alcohol amine mixed biphasic absorbents and catalyst-organic amine mixed biphasic absorbents. Moreover, the design and construction principle and performance strengthening mechanism of the aforementioned biphasic absorbents were analyzed. Finally, based on the in-depth analysis of the current research progress, the future research direction of biphasic absorbent was proposed.

Key words: carbon dioxide capture, chemical absorption, biphasic absorbent, regeneration energy consumption, catalytic regeneration

中图分类号:

X511

符乐, 杨阳, 徐文青, 耿錾卜, 朱廷钰, 郝润龙. 新型相变有机胺吸收捕集CO₂技术研究进展[J]. 化工进展, 2023, 42(4): 2068-2080.

FU Le, YANG Yang, XU Wenqing, GENG Zanbu, ZHU Tingyu, HAO Runlong. Research progress in CO₂ capture technology using novel biphasic organic amine absorbent[J]. Chemical Industry and Engineering Progress, 2023, 42(4): 2068-2080.

图/表 12

参考文献 71

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吸收剂			实验条件				富相体积分数/%	吸收负荷/mol CO₂·(mol胺)^-1	富相黏度/mPa·s	再生效率/%	再生能耗/GJ·(t CO₂)^-1	参考文献
伯/仲胺	叔胺	空间位阻胺	气体流速/mL·min^-1	CO₂体积分数/%	吸收温度/℃	再生温度/℃	富相体积分数/%	吸收负荷/mol CO₂·(mol胺)^-1	富相黏度/mPa·s	再生效率/%	再生能耗/GJ·(t CO₂)^-1	参考文献
TETA	DEEA	—	60	100	40	—	44.0	0.95	1505.0	59.9	—	[42]
TETA	DEEA	AMP	60	100	40	—	67.2	3.32^①	185.5	92.3	—	[42]
DETA	PMDETA	—	60	100	40	120	38.0	0.613	541.0	25.1	2.40	[30]
DETA	PMDETA	AMP	60	100	40	120	43.0	0.634	152.0	80.9	1.83	[30]

吸收剂			实验条件				富相体积分数/%	吸收负荷/mol CO₂·(mol胺)^-1	富相黏度/mPa·s	再生效率/%	再生能耗/GJ·(t CO₂)^-1	参考文献
伯/仲胺	叔胺	空间位阻胺	气体流速/mL·min^-1	CO₂体积分数/%	吸收温度/℃	再生温度/℃	富相体积分数/%	吸收负荷/mol CO₂·(mol胺)^-1	富相黏度/mPa·s	再生效率/%	再生能耗/GJ·(t CO₂)^-1	参考文献
TETA	DEEA	—	60	100	40	—	44.0	0.95	1505.0	59.9	—	[42]
TETA	DEEA	AMP	60	100	40	—	67.2	3.32^①	185.5	92.3	—	[42]
DETA	PMDETA	—	60	100	40	120	38.0	0.613	541.0	25.1	2.40	[30]
DETA	PMDETA	AMP	60	100	40	120	43.0	0.634	152.0	80.9	1.83	[30]

吸收剂			实验条件				富相体积分数/%	吸收负荷 /molCO₂·(mol胺)^-1	再生能耗 /GJ·(tCO₂)^-1	参考文献
伯/仲胺	叔胺	物理溶剂	气体流速 /mL·min^-1	CO₂体积分数/%	吸收温度 /℃	再生温度 /℃	富相体积分数/%	吸收负荷 /molCO₂·(mol胺)^-1	再生能耗 /GJ·(tCO₂)^-1	参考文献
MEA	—	正丙醇	500	100	45	110	56.4	0.48	2.40	[15]
AEP	—	正丙醇	240	100	40	120	58.0	1.26	2.74	[44]
DETA	—	正丙醇	100	100	30	110	41.7	1.08	2.12	[45]
AMP/MEA	—	DEGDME	2000	12	40	120	—	0.40	2.70	[32]
MEA	—	环丁砜	110	15	40	120	49.1	0.485	2.67	[46]
TETA	DEEA	环丁砜	120	100	30	110	39.0	0.984	1.81	[47]
DETA	PMDETA	环丁砜	120	100	30	110	27.1	1.22	1.86	[48]
AMP/MEA	PMDETA	DMSO	80	100	40	120	56.8	0.88	2.30	[49]
TETA	—	1-MI	200	100	45	120	41.1	1.75	2.26	[10]

吸收剂			实验条件				富相体积分数/%	吸收负荷 /molCO₂·(mol胺)^-1	再生能耗 /GJ·(tCO₂)^-1	参考文献
伯/仲胺	叔胺	物理溶剂	气体流速 /mL·min^-1	CO₂体积分数/%	吸收温度 /℃	再生温度 /℃	富相体积分数/%	吸收负荷 /molCO₂·(mol胺)^-1	再生能耗 /GJ·(tCO₂)^-1	参考文献
MEA	—	正丙醇	500	100	45	110	56.4	0.48	2.40	[15]
AEP	—	正丙醇	240	100	40	120	58.0	1.26	2.74	[44]
DETA	—	正丙醇	100	100	30	110	41.7	1.08	2.12	[45]
AMP/MEA	—	DEGDME	2000	12	40	120	—	0.40	2.70	[32]
MEA	—	环丁砜	110	15	40	120	49.1	0.485	2.67	[46]
TETA	DEEA	环丁砜	120	100	30	110	39.0	0.984	1.81	[47]
DETA	PMDETA	环丁砜	120	100	30	110	27.1	1.22	1.86	[48]
AMP/MEA	PMDETA	DMSO	80	100	40	120	56.8	0.88	2.30	[49]
TETA	—	1-MI	200	100	45	120	41.1	1.75	2.26	[10]

吸收剂		实验条件				吸收负荷 /mol CO₂·(mol胺)^-1	再生效率 /%	参考文献
伯/仲胺	添加剂	气体流速/mL·min^-1	CO₂体积分数/%	吸收温度/℃	再生温度/℃	吸收负荷 /mol CO₂·(mol胺)^-1	再生效率 /%	参考文献
EMEA	H₂O	265	100	40	110	0.799	38.8	[59]
EMEA	乙醇	265	100	40	110	0.547	100.0	[59]
TETA/AMP	H₂O	80	100	40	120	0.95	38.8	[41]
TETA/AMP	乙醇	80	100	40	120	1.00	95.4	[41]

新型相变有机胺吸收捕集CO₂技术研究进展

Research progress in CO₂ capture technology using novel biphasic organic amine absorbent

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有机胺	催化剂	实验条件			总酸位点 /µmol·g^-1	性能提升	参考文献
有机胺	催化剂	CO₂体积分数/%	吸收温度/℃	再生温度/℃	总酸位点 /µmol·g^-1	性能提升	参考文献
3.33mol/L MEA	TiO(OH)₂	15	40	30~88	—	DR提高4500%，DA提高68.8%	[63]
5mol/L MEA	SZMF	15	40	98	—	RE降低28%～40%	[64]
5mol/L MEA	Al₂O₃	—	—	65~96	935	RE降低27%	[65]
5mol/L MEA	Al₂O₃/HZSM-5	—	—	65~96	1050	RE降低23%～34%	[65]
5mol/L MEA	ZrO₂	15	40	40-88	126.3	DR提高54%	[66]
5mol/L MEA	ZnO	15	40	40-88	122.7	DR提高54%	[66]
5mol/L MEA	AgO-Ag₂CO₃	15	40	40~82	—	DR提高1010%，CC提高52%	[67]
5mol/L MEA	SO₄^2-/ZrO₂	—	—	98	2796.1	RE降低9.8%	[68]
MEA-AMP-PZ	HZSM-5	15	40	90~98	9502.1	DR提高121%，RE降低61.6%	[69]
5mol/L MEA	SO₄^2-/ZrO₂-HZSM-5	50	25	30~98	1596.0	DR提高37%，DA提高40% RE降低31%	[70]
5mol/L MEA	Fe-Zr@BS	15	40	55~98	610	RE降低33%	[71]

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