复配醇胺溶液对CO2的吸收解吸性能及其降解性能

doi:10.16085/j.issn.1000-6613.2021-0545

摘要/Abstract

摘要：

比较了9种不同配方醇胺溶液对CO₂的吸收解吸性能。其中，N-乙基乙醇胺（EMEA）+二乙氨基乙醇（DEEA）+哌嗪（PZ）和2-氨基-2-甲基-1,3丙二醇（AMPD）+哌嗪（PZ）+水（H₂O）两种溶液的吸收解吸的稳定性最佳，平均解吸率高于94.00%。本文对这两种溶液进行了144h热降解和96h氧化降解实验，结果表明热降解后的EMEA+DEEA+PZ溶液的吸收解吸性能稳定性较高，每千克溶液对CO₂的平均吸收量、平均解吸量略有升高，分别升高1.58L、0.35L，平均解吸率下降2.04%；而氧化降解造成每千克EMEA+DEEA+PZ溶液对CO₂的平均吸收量、平均解吸量分别下降0.45L、1.75L，平均解吸率下降2.25%；热降解对于AMPD+PZ+H₂O溶液吸收解吸性能影响较大，造成每千克该溶液对CO₂的平均吸收量、平均解吸量分别下降5.63L、4.03L，平均解吸率升高2.32%；在经过氧化降解之后，每千克AMPD+PZ+H₂O溶液对CO₂的平均吸收量、平均解吸量分别下降1.05L、0.70L，平均解吸率升高0.59%。液质联用分析结果表明，热降解导致EMEA浓度减小了19.67%，AMPD浓度减小了71.89%；氧化降解导致EMEA浓度减小了18.18%，AMPD浓度减小了74.53%。由此说明，EMEA+DEEA+PZ比AMPD+PZ+H₂O具有更佳的抗降解性能。同时，根据电喷雾质谱结果对两种溶液的热降解、氧化降解的机理进行推测，热降解中生成恶唑烷酮类物质，氧化降解则是生成酸类物质。其中，氧化降解对两种溶液都造成了负面影响，而热降解则不然。

关键词: 醇胺, 二氧化碳捕集, 吸收, 解吸, 降解

Abstract:

The CO₂ absorption and desorption performances of nine alcohol amines were compared. Among them, there were two kinds of solutions that showed the better stability of absorption-desorption performance, which contained N-ethylethanolamine (EMEA)+diethylaminoethanol (DEEA)+piperazine (PZ) and 2-amino-2-methyl-1,3-propanediol (AMPD)+piperazine (PZ)+H₂O. The average desorption rate of the solvents were above 94.0% after two cyclic tests. The solutions were subjected to thermal degradation for 144h and oxidative degradation for 96h. It was found that the absorption-desorption performance of EMEA+DEEA+PZ solution after thermal degradation was stable. The average absorption amount and desorption amount of the solution increased slightly by 1.58L CO₂/kg solution and 0.35L CO₂/kg solution, respectively, and the average desorption rate decreased by 2.0%. While oxidative degradation caused the average absorption amount and desorption amount of the solution to decrease by 0.45L CO₂/kg solution and 1.75L CO₂/kg solution, respectively, and the average desorption rate decreased by 2.3%. The thermal degradation had a distinct impact on the absorption-desorption performance of AMPD+PZ+H₂O solution, which caused a decrease in the average absorption amount and desorption amount of the solution by 5.63L CO₂/kg solution and 4.03L CO₂/kg solution, respectively, and the average desorption rate increased by 2.3%. After oxidative degradation, the average absorption amount and desorption amount of the solution decreased by 1.05L CO₂/kg solution and 0.70L CO₂/kg solution, respectively, and the average desorption rate increased by 0.6%.The liquid mass spectrometry analysis showed that the concentrations of EMEA and AMPD decreased by 19.7% and 71.8% due to thermal degradation, 18.2% and 74.5% due to oxidative degradation, respectively. The thermal and oxidative degradation experiments demonstrated that EMEA+DEEA+PZ had the better anti-degradation performance than AMPD+PZ+H₂O. The mechanisms of thermal and oxidative degradation of the two kinds of alcohol amines were speculated based on the results of electrospray mass spectrometry, in which oxazolidinones were generated in thermal degradation and acids were generated in oxidative degradation. In both cases, oxidative degradation had negative effects on both solutions, while thermal degradation did not.

Key words: alcohol amines, CO₂ capture, absorption, desorption, degradation

中图分类号:

TQ028

李红, 吉轲, 齐天勤机, 李晓静, 万慧慧, 张永春, 陈绍云. 复配醇胺溶液对CO₂的吸收解吸性能及其降解性能[J]. 化工进展, 2022, 41(2): 1025-1035.

LI Hong, JI Ke, Tianqinji QI, LI Xiaojing, WAN Huihui, ZHANG Yongchun, CHEN Shaoyun. Properties of CO₂ absorption-desorption based on alcohol amines solutions and their degradation[J]. Chemical Industry and Engineering Progress, 2022, 41(2): 1025-1035.

图/表 27

表3 复配溶液的配方

序号	复配溶液	质量分数/%
1	AEEA+H₂O	30+70
2	AEEA+MEA+DEEA+H₂O	7.5+15+7.5+70
3	AEEA+GI+H₂O	30+50+20
4	AEEA+SUL+PZ^①	30+60+10
5	AMP+DEA+MDEA+H₂O	10+10+10+70
6	AMP+DMSO+AEEA^②	27+63+10
7	AMPD+PZ+H₂O	20+10+70
8	EMEA+DEEA+PZ^③	27+63+10
9	MDEA+MEA+PZ^④	30+50+20

图1 CO2吸收解吸装置示意图1—N2气瓶；2—CO2气瓶；3—质量流量计；4,11—缓冲瓶；5—冷凝管；6—三口烧瓶；7—磁力转子；8—恒温油浴锅；9—测温热电偶；10—干燥器；12—湿式流量计

图2 氧化降解装置示意图1—N2+O2混合气气瓶：2—压力表；3—磁力转子；4—高压反应釜；5—测温热电偶；6—恒温油浴锅

图3 热降解装置示意图1—烘箱；2—高压反应釜；3—压力表；4—N2气瓶

图4 复配醇胺溶液的吸收稳定性比较

图5 复配醇胺溶液的解吸稳定性对比

图6 复配醇胺溶剂的二次解吸率对比

图7 EMEA+DEEA+PZ溶液降解前后吸收量对比a—未降解的EMEA+DEEA+PZ；b—热降解后的EMEA+DEEA+PZ；c—氧化降解后的EMEA+DEEA+PZ

图8 EMEA+DEEA+PZ溶液降解前后解吸量对比a—未降解的EMEA+DEEA+PZ；b—热降解后的EMEA+DEEA+PZ；c—氧化降解后的EMEA+DEEA+PZ

图9 EMEA+DEEA+PZ溶液降解前后解吸率对比a—未降解的EMEA+DEEA+PZ；b—热降解后的EMEA+DEEA+PZ；c—氧化降解之后的EMEA+DEEA+PZ

图10 AMPD+PZ+H2O溶液降解前后吸收量对比a—未降解的AMPD+PZ+H2O；b—热降解后的AMPD+PZ+H2O；c—氧化降解后的AMPD+PZ+H2O

图11 AMPD+PZ+H2O溶液降解前后解吸量对比a—未降解的AMPD+PZ+H2O；b—热降解后的AMPD+PZ+H2O；c—氧化降解后的AMPD+PZ+H2O

图12 AMPD+PZ+H2O溶液降解前后解吸率对比a—未降解的AMPD+PZ+H2O；b—热降解之后的AMPD+PZ+H2O；c—氧化降解之后的AMPD+PZ+H2O

图13 EMEA与AMPD在热降解过程中的浓度变化

图14 EMEA与AMPD在氧化降解过程中的浓度变化

图15 EMEA+DEEA+PZ溶液在热降解前ESI-MS图

图16 EMEA+DEEA+PZ溶液在热降解后ESI-MS图

图17 EMEA+DEEA+PZ热降解的机理分析

图18 AMPD+PZ+H2O溶液在热降解前ESI-MS图

图19 AMPD+PZ+H2O热降解后ESI-MS图

图20 AMPD+PZ+H2O热降解机理分析

图21 EMEA+DEEA+PZ氧化降解前ESI-MS图

图22 EMEA+DEEA+PZ氧化降解后ESI-MS图

图23 EMEA+DEEA+PZ氧化降解机理分析

图24 AMPD+PZ+H2O氧化降解前ESI-MS图

图25 AMPD+PZ+H2O氧化降解后ESI-MS图

图26 AMPD+PZ+H2O氧化降解机理分析

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复配醇胺溶液对CO₂的吸收解吸性能及其降解性能

Properties of CO₂ absorption-desorption based on alcohol amines solutions and their degradation

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