相变吸收酸性气体的发展现状

doi:10.16085/j.issn.1000-6613.2020-0129

摘要/Abstract

摘要：

酸性气体，如CO₂、SO₂和H₂S的过量排放已经造成温室效应或酸雨等一系列环境危害。传统的溶剂吸收法由于技术成熟、成本低廉而得到了广泛应用，但它依然存在吸收剂再生能耗高、产物附加值低的缺点。近年来，一种新的吸收方式，相变吸收（即均相体系在吸收酸性气体后分为两相，酸性气体主要富集于其中一相），引起了人们的广泛关注。该法在吸收剂再生时只需要对其中的富相进行处理，从而减少了处理量，降低了解吸能耗，且富相中的酸性气体作为一种已经被改性的原料可以直接用于合成含硫或含碳化学品，从根本上避免再生过程。本文阐述了相变吸收的研究现状，依次对CO₂、SO₂以及H₂S体系作了详细的介绍。将相变吸收分为液-液相变、液-固相变两类，介绍了两种相变吸收的研究进展，并分析比较了它们优缺点。在实际使用中，不同领域应综合考虑。目前，相变吸收实现了吸收剂对SO₂气体的质量吸收量为1.56g SO₂ /g DMEA，对H₂S的为0.205g H₂S/ g DBN，对CO₂的摩尔吸收量为1.87mol CO₂/mol （TETA/PEG200），与其他方法相比，相变吸收的吸收量非常高。这些结果表明相变吸收是一种极具潜力的酸性气体捕集方式。

关键词: 酸性气体捕集, 相变吸收, 有机溶剂, 过程强化

Abstract:

Excessive emissions of acid gases, such as CO₂, SO₂, and H₂S, have caused a range of threats to the environment, for instance, the greenhouse effect and acid rain. Traditional solvent absorption technology has been widely used due to its maturity and low costs. However, there are still some shortcomings, such as intensive energy consumption during the regeneration process, low-value compounds, etc. Recently, phase-change absorption, in which, the homogeneous solution forms two phases upon acid gas loading, and the acid gas mainly concentrates in one phase, has captured wide concern. This technology only needs to treat with the gas-rich phase during regeneration, resulting in the reduction of the regenerated amount and energy saving. Besides, the acid gas in rich phase could act as a modified raw material, which could be used to synthesize carbon/sulfur-containing chemicals, thus avoiding the regeneration process fundamentally. This review introduced the recent researches of phase-change absorption technology, which included CO₂, SO₂, and H₂S gas. This technology was divided into liquid-liquid and liquid-solid phase-change absorption and its comprehensive advantages and disadvantages were summarized and compared. The two types of phase-change absorption technology should be considered comprehensively in practical application. At present, the mass absorption capacity was 1.56g SO₂/g DMEA, 0.205g H₂S/g DBN and the molar absorption capacity was 1.87mol CO₂/mol (TETA/PEG200) in phase-change absorption process, which is reported as the super high value in the literature. This indicates phase-change absorption is a promising method in acid gas capture.

Key words: capture of acid gas, phase-change absorption, organic solvent, process intensification

中图分类号:

O06-1

赵文波, 李广振, 许胜超, 李雪霏, 王志友. 相变吸收酸性气体的发展现状[J]. 化工进展, 2021, 40(1): 401-414.

Wenbo ZHAO, Guangzhen LI, Shengchao XU, Xuefei LI, Zhiyou WANG. Recent developments of acid gas absorption by phase-change[J]. Chemical Industry and Engineering Progress, 2021, 40(1): 401-414.

图/表 12

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吸收方法	吸收剂	吸收量	反应条件
钙法脱硫^[36]	Ca(OH)₂	0.12g/g	60min
海水法脱硫^[37]	海水	7.463mmol/L	25℃
离子液体^[38,39,40]	GT [P4442][BTFA]	0.44g/g 0.61g/g	20℃,1.0atm
低共熔法^[41]	Emim-EG（2∶1）己内酰胺/乙酰胺	1.15g/g 0.497g/g	30℃,0.1MPa
相变吸收^[29,30]	DMCHA/LP DMEA/正十六烷 Emim-AA	1.19g/g 1.56g/g 1.39g/g	20℃, 1atm

吸收方法	吸收剂	吸收量	反应条件
钙法脱硫^[36]	Ca(OH)₂	0.12g/g	60min
海水法脱硫^[37]	海水	7.463mmol/L	25℃
离子液体^[38,39,40]	GT [P4442][BTFA]	0.44g/g 0.61g/g	20℃,1.0atm
低共熔法^[41]	Emim-EG（2∶1）己内酰胺/乙酰胺	1.15g/g 0.497g/g	30℃,0.1MPa
相变吸收^[29,30]	DMCHA/LP DMEA/正十六烷 Emim-AA	1.19g/g 1.56g/g 1.39g/g	20℃, 1atm

名称	相对分子质量	理论吸收能力 /mol·mol^-1
乙醇胺（MEA）	61.01	0.5
二乙醇胺（DEA）	105.14	0.5
三乙醇胺（TEA）	149.19	1.0
N-甲基二乙醇胺（MDEA）	119.16	1.0

名称	相对分子质量	理论吸收能力 /mol·mol^-1
乙醇胺（MEA）	61.01	0.5
二乙醇胺（DEA）	105.14	0.5
三乙醇胺（TEA）	149.19	1.0
N-甲基二乙醇胺（MDEA）	119.16	1.0

吸收剂类别	典型吸收剂	优势	存在问题
热钾碱法	K₂CO₃	低成本、低毒性、低挥发性、无降解	吸收速率低，不适合电厂烟气等低分压的情况，高温下设备易腐蚀
醇胺类	MEA，DEA，MDEA，EDA，PZ	伯胺和仲胺吸收速率高；叔胺再生能耗低	不能同时满足高吸收率和低再生能耗；易氧化
氨水	NH₃·H₂O	成本低；脱除效率和吸收负荷高，再生能耗低	吸收再生过程中挥发性大
混合胺^[83]	MEA/PZ，MDEA/PZ，空间位阻胺类	同时具有高吸收负荷、吸收速率和低再生能耗	受限于胺类自身的性质，再生性提升有限
离子液体^[84]	氨基功能化离子液体	CO₂具有高选择性；高吸收负荷和低再生能耗	成本高，黏度大，吸收速率慢
相变吸收剂^[28]	DPA/DMCA等液液相变；EDA/PEG300等液固相变	CO₂富相体积小，大大降低再生能耗；相变过程可促进反应向右移，增大吸收负荷	富相黏度较大