相变吸收捕集烟气中CO2技术的发展现状

doi:10.16085/j.issn.1000-6613.2021-0740

摘要/Abstract

摘要：

化学吸收法作为目前最有效的CO₂捕集技术，吸收剂常用有机胺，但过高的再生能耗和成本限制了其在工业中的应用。基于传统有机胺溶剂开发出来的相变吸收剂被认为可以大幅减少解吸能耗，成为近几年研究的热点。本文详细介绍了相变吸收剂的常见类型、分相机理，并根据其具体组成进行了种类划分，对比分析了常用相变吸收剂和传统乙醇胺（MEA）吸收液的再生能耗，并指出温度、CO₂负荷以及相分离等因素对相变吸收剂的工艺流程长期运行稳定性的影响。在制备相变吸收剂的过程中，可加入活化剂来降低CO₂富液黏度，加入助溶剂来提高传质特性。本文阐述了现有相变吸收剂的挥发、降解和腐蚀等特性的研究现状。最后，结合研究现状和烟气捕集需求对相变吸收剂今后的研究方向给出了建议。

关键词: 二氧化碳捕集, 化学吸收, 相变吸收剂, 再生能耗, 稳定性

Abstract:

Chemical solvent absorption is currently the most effective CO₂ capture technology, and organic amines are commonly used as absorbents. However, its application in industry is limited due to its high regeneration energy consumption and high cost. Phase-change absorbers developed on the basis of traditional organic amine solvents are considered to be able to significantly reduce the energy consumption of desorption, which has become a research hotspot in recent years. In this paper, the common types and phase separation mechanism of phase change absorbers are introduced in detail, and the types are classified according to their specific composition. The regeneration energy consumption of the common phase-change absorbent and the traditional MEA absorbent is compared and analyzed. It also points out the influence of temperature, CO₂ load and phase separation on the long-term stability of the process flow of the phase change absorbent. In the process of preparing phase change absorber, an activator can be added to reduce the viscosity of CO₂ rich liquid, and a cosolvent can be added to improve the mass transfer characteristics. The research status of volatilization, degradation and corrosion characteristics of phase-change absorbent is reviewed. Finally, some suggestions on the future research direction of phase-change absorbers are given based on the research status and the requirements of flue gas capture.

Key words: CO₂ capture, chemical absorption, phase-change absorbent, regeneration energy, stability

中图分类号:

X511

张卫风, 周武, 王秋华. 相变吸收捕集烟气中CO₂技术的发展现状[J]. 化工进展, 2022, 41(4): 2090-2101.

ZHANG Weifeng, ZHOU Wu, WANG Qiuhua. Recent developments of phase-change absorption technology for CO₂ capture from flue gas[J]. Chemical Industry and Engineering Progress, 2022, 41(4): 2090-2101.

图/表 8

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类型	体系	特点
单元基吸收剂	MDEA+正丁醇+水	最优条件下吸收剂在膜器内停留时间仅为数秒，CO₂的解吸率均高于80%，最高可达92%^［17］
	MEA+叔丁醇+水	相比于质量分数为30%的MEA水溶液，MEA/叔丁醇/水相变吸收剂具有更高的循环负载和更少的解吸液量^［18］
	MEA+1-丙醇+水	与传统的质量分数为30%的MEA水溶液相比，初始吸收率更高，循环负载量增加了一半^［19］
多元混合吸收剂	TETA+DEEA	下层相吸收CO₂达到90%以上，合适的吸收和解吸温度分别为30℃和90℃^［20］
	DMCA+TETA	有较高的CO₂吸收循环能力，良好的相分离行为和较低的再生热。与5mol/L MEA相比，TETA-DMCA的再生能耗可降低约40%^［21］
	MAPA+DEEA	具有较低的挥发性，相比于质量分数为30%的MEA水溶液其再生能耗可以进一步降低^［22］
	DMCA+MCA+AMP	有良好的相变温度，高CO₂净负荷以及良好的抗氧化降解和热降解能力，且能耗可降至2.0GJ·(t CO₂)^-1 以下^［14］
无水吸收剂	MEA+三甘醇	醇不参与反应，仅MEA和CO₂反应，MEA浓度为5mol/L，吸收剂循环处理量高，能耗接近 2.0GJ·(t CO₂)^-1，优于MEA+水吸收剂^［23］
无水吸收剂	MEA+环丁砜	MEA/环丁砜相变溶剂的总再生能耗为2.67GJ·(t CO₂)^-1，与传统的5mol/L MEA相比，降低了31%^［24］

类型	体系	特点
单元基吸收剂	MDEA+正丁醇+水	最优条件下吸收剂在膜器内停留时间仅为数秒，CO₂的解吸率均高于80%，最高可达92%^［17］
	MEA+叔丁醇+水	相比于质量分数为30%的MEA水溶液，MEA/叔丁醇/水相变吸收剂具有更高的循环负载和更少的解吸液量^［18］
	MEA+1-丙醇+水	与传统的质量分数为30%的MEA水溶液相比，初始吸收率更高，循环负载量增加了一半^［19］
多元混合吸收剂	TETA+DEEA	下层相吸收CO₂达到90%以上，合适的吸收和解吸温度分别为30℃和90℃^［20］
	DMCA+TETA	有较高的CO₂吸收循环能力，良好的相分离行为和较低的再生热。与5mol/L MEA相比，TETA-DMCA的再生能耗可降低约40%^［21］
	MAPA+DEEA	具有较低的挥发性，相比于质量分数为30%的MEA水溶液其再生能耗可以进一步降低^［22］
	DMCA+MCA+AMP	有良好的相变温度，高CO₂净负荷以及良好的抗氧化降解和热降解能力，且能耗可降至2.0GJ·(t CO₂)^-1 以下^［14］
无水吸收剂	MEA+三甘醇	醇不参与反应，仅MEA和CO₂反应，MEA浓度为5mol/L，吸收剂循环处理量高，能耗接近 2.0GJ·(t CO₂)^-1，优于MEA+水吸收剂^［23］
无水吸收剂	MEA+环丁砜	MEA/环丁砜相变溶剂的总再生能耗为2.67GJ·(t CO₂)^-1，与传统的5mol/L MEA相比，降低了31%^［24］

类型	体系	特点
氨基酸盐溶液	牛磺酸钾	固液分离温度为40℃，与30% MEA基准相比，可将捕获过程的总能量降低15％^［32］
K₂CO₃溶液	高浓度K₂CO₃溶液	低成本、低毒性、不易挥发，能够吸收多杂质的CO₂、SO _x 和NO _x 以及有价值的副产物的产生^［33］
K₂CO₃溶液	K₂CO₃溶液+MEA	向K₂CO₃中添加MEA会有效提高吸收速率^［34］
冷氨水溶液	冷氨水溶液	低成本，化学稳定和对氧气的高稳定性，较高的CO₂负载能力^［35］
非水溶液吸收剂	脯氨酸钾+乙醇	与30% MEA水溶液相比，使用脯氨酸钾+乙醇溶液可以显著提高CO₂的溶解度，尤其在低CO₂负荷下^［36］
非水溶液吸收剂	AMP/PZ/DME	具有高吸收负荷和再生效率，吸收CO₂后，富含CO₂的下相体积占溶液总体积的43%，而约占总负载的94%^［37］

类型	体系	特点
氨基酸盐溶液	牛磺酸钾	固液分离温度为40℃，与30% MEA基准相比，可将捕获过程的总能量降低15％^［32］
K₂CO₃溶液	高浓度K₂CO₃溶液	低成本、低毒性、不易挥发，能够吸收多杂质的CO₂、SO _x 和NO _x 以及有价值的副产物的产生^［33］
K₂CO₃溶液	K₂CO₃溶液+MEA	向K₂CO₃中添加MEA会有效提高吸收速率^［34］
冷氨水溶液	冷氨水溶液	低成本，化学稳定和对氧气的高稳定性，较高的CO₂负载能力^［35］
非水溶液吸收剂	脯氨酸钾+乙醇	与30% MEA水溶液相比，使用脯氨酸钾+乙醇溶液可以显著提高CO₂的溶解度，尤其在低CO₂负荷下^［36］
非水溶液吸收剂	AMP/PZ/DME	具有高吸收负荷和再生效率，吸收CO₂后，富含CO₂的下相体积占溶液总体积的43%，而约占总负载的94%^［37］

试剂	浓度	相变形式	再生能耗 /MJ·(kg CO₂)^-1	参考文献
MEA	30%	—	4.22	［51］
MEA/1-丙醇/水	30%	液-液	2.40	［19］
MEA/环丁砜	4mol/L	液-液	2.67	［24］
TETA/DEEA	5mol/L	液-液	2.7	［20］
TETA/DMCA	4mol/L	液-液	2.6	［21］
MAPA/DEEA	7mol/L	液-液	2.2~2.4	［22，52］
AEEA/DEEA	20%+60%	液-液	2.46	［53］
DMCA/MCA/AMP	(3+1+1)mol/L	液-液	2.0	［14］
脯氨酸钾/乙醇	3.3~5.9mol/kg乙醇	液-固	2.0~2.5	［36］
牛磺酸钾溶液	4mol/L	液-固	3.25	［32］
AMP/PZ/DME	1mol/kg	液-固	1.61	［37］
K₂CO₃溶液	20%~40%	液-固	2.0~2.5	［33］
冷氨水溶液	30%	液-固	2.5	［35］

相变吸收捕集烟气中CO₂技术的发展现状

Recent developments of phase-change absorption technology for CO₂ capture from flue gas

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