基于N-乙基乙醇胺非水CO2吸收剂的抗氧化剂

doi:10.16085/j.issn.1000-6613.2019-0403

摘要/Abstract

摘要：

N-乙基乙醇胺（EMEA）+二乙氨基乙醇（DEEA）非水溶液是新型CO₂吸收剂，CO₂吸收量0.68mol CO₂/ mol EMEA、CO₂解吸量0.62mol CO₂/ mol EMEA及再生能耗7554kJ /kg溶剂，综合性能显著优于文献报道的其他CO₂非水吸收剂。但溶剂在工业应用中由于气源伴生的氧气影响，会发生氧化降解。本文研究了配方溶剂的氧化降解性和6种抗氧化剂[丁酮肟、乙醛肟、丙酮肟、N,N'-双亚水杨-1,2-丙二胺(BPPD)、邻苯三酚和碳酰肼]的抗氧化作用。EMEA+DEEA溶剂在13%O₂（体积分数）下氧化30天降解率为7.33%（质量分数）。根据电喷雾质谱结果，推测出EMEA通过两种途径氧化，第一种途径为EMEA担载CO₂生成氨基甲酸盐，然后发生氧化反应，该产物可与EMEA发生酯化反应。氨基甲酸盐也可发生自身酯化反应，然后发生氧化反应。第二种途径为EMEA直接氧化成乙氨基乙酸，然后由两种途径继续反应。第一种途径为乙氨基乙酸继续氧化为羟基乙酸，羟基乙酸可继续与DEEA反应生成N-二乙基-4-羟基-丙酯，第二种途径是乙氨基乙酸直接与EMEA发生羧合反应。DEEA可直接氧化为N-二乙基乙酸，然后与EMEA发生羧合反应。6种抗氧化剂抗氧化效果差异明显，6种抗氧化剂对EMEA+DEEA非水溶液的抗氧化效果顺序为：乙醛肟＞丁酮肟＞丙酮肟＞BPPD≈碳酰肼>邻苯三酚。EMEA+DEEA+乙醛肟抗降解性能最好，降解率为4.00%。

关键词: 非水溶液, 氧化, 二氧化碳, 二氧化碳捕集, 吸收, 烟道气, 抗氧化

Abstract:

The non-aqueous solution of N-ethylethanolamine (EMEA) + diethylaminoethanol (DEEA) is a novel CO₂ absorbent, which has high CO₂ capacity (0.68mol CO₂/mol EMEA), high regeneration efficiency (91%) and low energy consumption (7554kJ/kg solvent). However, oxidative degradation, which decreases CO₂ capture efficiency, occurs due to the existence of oxygen in flue gas. In this paper, the oxidative degradation of the solvent and the antioxidant effects of the six oxidation inhibitors [butanone oxime, acetaldoxime, acetone oxime, N, N'-bis(salicylidene)-1,2-diaminopropane(BPPD), pyrogallol and carbohydrazide] were studied. The degradation percentage of EMEA+DEEA solution in 13% O₂+ 87% N₂ is 7.33% for 30 days. The oxidative degradation products of EMEA+DEEA solution were qualitatively detected by electrospray ionization mass spectrometry (ESI-MS). The results showed that EMEA is oxidized in two routes. The first route is EMEA reacts with CO₂ to form carbamate, which can be further oxidized by oxygen. The carbamate can also undergo a self-esterification reaction, followed by an oxidation reaction. The second route is the direct oxidation of EMEA to ethylaminoacetic acid, then continued in two ways. The first way is the oxidation of ethylaminoacetic acid to glycolic acid, which can react with DEEA to form N-diethyl-4-hydroxy-propyl ester, and the second way is the reaction of ethylglycine with EMEA. DEEA can be directly oxidized to N-diethylacetic acid and then carboxylated with EMEA. The antioxidant effects of the six oxidation inhibitors are significantly different, which were in the order of: acetaldehyde oxime＞butanone oxime＞acetone oxime＞BPPD≈carboxhydrazide＞pyrogallol. The mixture of EMEA+DEEA+acetaldehyde oxime has the best oxidation resistance with the degradation percentage of 4.00%.

Key words: non-aqueous solvent, oxidation, carbon dioxide, CO₂capture, absorption, flue gas, anti-oxidation

中图分类号:

TQ028

储可弘,陈绍云,李强,张华,张永春. 基于N-乙基乙醇胺非水CO₂吸收剂的抗氧化剂[J]. 化工进展, 2019, 38(12): 5565-5571.

Kehong CHU,Shaoyun CHEN,Qiang LI,Hua ZHANG,Yongchun ZHANG. Oxidation inhibitor for thylethanolamine based non-aqueous CO₂ absorbent[J]. Chemical Industry and Engineering Progress, 2019, 38(12): 5565-5571.

图/表 10

图1 CO2吸收解吸实验装置1—流量计；2—冷凝管；3,4—干燥器；5—缓冲瓶；6—恒温油浴锅；7—三口烧瓶；8—聚四氟转子；9—温度计；10—湿式流量计

图2 氧化降解实验装置1—气体钢瓶；2—抗震压力表；3—恒温油浴；4—聚四氟转子；5—高压反应釜

图3 担载有CO2的EMEA+DEEA溶液氧化降解30天后的ESI-MS谱图

表1 m/z 值及其对应的分子结构

m/z值	归属及结构
90.0910
118.1223
134.1172
175.1438
201.1593
219.1697
241.1901
291.2420
267.2273

图4 EMEA+DEEA溶液氧化降解反应机理

图5 氧化30天EMEA+DEEA溶液相对碱度变化趋势图

图6 氧化30天后EMEA+DEEA溶液相对碱度降低量

图7 氧化30天非水溶液EMEA含量变化趋势图

图8 氧化30天后EMEA降解量

图9 氧化30天后CO2饱和担载量降低率

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基于N-乙基乙醇胺非水CO₂吸收剂的抗氧化剂

Oxidation inhibitor for thylethanolamine based non-aqueous CO₂ absorbent

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