利用13C NMR技术探究叔胺溶液中HCO3-的生成

doi:10.11949/j.issn.0438-1157.20150898

化工学报 ›› 2015, Vol. 66 ›› Issue (9): 3719-3725.DOI: 10.11949/j.issn.0438-1157.20150898

利用¹³C NMR技术探究叔胺溶液中HCO₃^-的生成

张瑞, 李末霞, 罗潇, 梁志武

CO₂捕获与封存国际合作中心(iCCS), 化石能源低碳化高效利用湖南省重点实验室, 湖南大学化学化工学院, 湖南长沙 410082

收稿日期:2015-06-11 修回日期:2015-06-30 出版日期:2015-09-05 发布日期:2015-09-05
通讯作者: 梁志武
基金资助:
国家自然科学基金项目(U13171004)。

Investigation of formation of bicarbonate in tertiary amines using ¹³C NMR technique

ZHANG Rui, LI Moxia, LUO Xiao, LIANG Zhiwu

Joint International Center for CO₂ Capture and Storage (iCCS), Hunan Provincial Key Laboratory for Cost-effective Utilization of Fossil Fuel Aimed at Reducing CO₂ Emissions, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, Hunan, China

Received:2015-06-11 Revised:2015-06-30 Online:2015-09-05 Published:2015-09-05
Supported by:
supported by the National Natural Science Foundation of China (U13171004).

摘要/Abstract

摘要：

利用¹³C NMR技术对CO₂捕获叔胺溶剂进行了碳元素的定量研究,主要考察了对胺溶剂解吸热影响较大的HCO₃^-的生成规律。重点对叔胺分子结构中羟基官能团(-OH)、羟烷基数目、烷基支链及氮原子(N)所连接烷基链大小对胺溶剂生成HCO₃^-的影响。在20℃条件下分别对1 mol·L^-1具有不同CO₂负载的1-二甲基氨基-2-丙醇(1DMA2P)、N-甲基二乙醇胺(MDEA)、3-二甲氨基-1-丙醇(3DMA1P)、二乙氨基-2-丙醇(1DEA2P)、N,N-二乙基乙醇胺(DEEA)、N,N-二甲基乙醇胺(DMMEA)及三乙醇胺(TEA)溶液进行了¹³C NMR测试研究。实验结果显示:在相同浓度的叔胺水溶液中,同一CO₂负载下的叔胺-CO₂-水体系中HCO₃^-的含量顺序为:DMMEA > MDEA>3DMA1P > 1DMA2P > TEA > DEEA > 1DEA2P。通过对各叔胺分子结构中N原子的电子云密度大小及空间位阻效应分析,得出如下结论:3DMA1P分子中-OH官能团离N原子的距离大于其在DMMEA分子中的距离,导致其生成了较少的HCO₃^-;DMMEA分子中N原子上连接的烷基链小于DEEA分子中N原子上的烷基链,导致DMMEA溶液中生成了更多的HCO₃^-;MDEA分子中羟烷基数目少于TEA分子中的羟烷基数目,且MDEA比TEA多了一个甲基,导致MDEA溶液中含有更多的HCO₃^-;3DMA1P相比1DMA2P、DEEA相比1DEA2P分子中都少了一个甲基支链,导致3DMA1P溶液相比1DMA2P溶液、DEEA溶液相比1DEA2P溶液生成了更多的HCO₃^-。

关键词: 核磁共振, 二氧化碳, 吸收, 叔胺

Abstract:

The amount of bicarbonate is a very important factor for energy consumption in solvent regeneration in CO₂ capture process. More bicarbonate in rich amines will lead to lower energy cost in CO₂ desorption process. To get a preciously knowledge of the formation of bicarbonate in tertiary amines for design a better absorbent for CO₂ capture, a series of tertiary amines such as N-diethylethanolamine (DEEA),1-dimethylamino-2-propanol (1DMA2P), 1-diethylamino-2-propanol (1DEA2P), 3-dimethyl-amino-1-propanol (3DMA1P), N-methyldiethanolamine (MDEA), dimethylmonoethanolamine (DMMEA) and triethanolamine (TEA) with various CO₂ loading at 1 mol·L^-1 were investigated using ¹³C NMR technology at 293.15 K. The amount of bicarbonate was calculated by the chemical shift of bicarboante/carboante in ¹³C NMR spectra. The results showed that the order of the amount of bicarbonate in those tertiary amines is DMMEA > MDEA > 3DMA1P > 1DMA2P > TEA > DEEA > 1DEA2P. Considering the effects of electron density of nitrogen atom (N) and the steric hinderance in those tertiary amines to the formation of bicarbonate in those aqueous tertiary amines solution, it can be concluded that 1) the aqueous 3DMA1P solution produced more bicarbonate compared to DMMEA for its nearer distance of OH to N; 2) the less hydroxyalkyl and one more methyl in amine molecular structure connected to N in MDEA compared to TEA led to more bicarbonate generation; 3) a smaller alkyl connected to N in DMMEA molecular structure compare to DEEA resulted in more bicarbonate was generated in aqueous DMMEA solution; and 4) one more methyl branch existed in 1DMA2P and 1DEA2P molecular structures compared to 3DMA1P and DEEA, respectively, leading to less bicarbonate generation.

Key words: NMR, carbon dioxide, absorption, tertiary amine, bicarbonate

中图分类号:

TQ028.8

张瑞, 李末霞, 罗潇, 梁志武. 利用¹³C NMR技术探究叔胺溶液中HCO₃^-的生成[J]. 化工学报, 2015, 66(9): 3719-3725.

ZHANG Rui, LI Moxia, LUO Xiao, LIANG Zhiwu. Investigation of formation of bicarbonate in tertiary amines using ¹³C NMR technique[J]. CIESC Journal, 2015, 66(9): 3719-3725.

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利用¹³C NMR技术探究叔胺溶液中HCO₃^-的生成

Investigation of formation of bicarbonate in tertiary amines using ¹³C NMR technique

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