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1.
To explore the effect of amine chain length on CO2 absorption performance, the reaction kinetics of CO2 absorption in aqueous 1-dimethylamino-2-propanol (DMA2P), 1-diethylamino-2-propanol (DEA2P), 2-(methylamino)ethanol (MAE), and 2-(ethylamino)ethanol (EAE) solutions with different concentrations were explored using the stopped-flow apparatus. Additionally, Density Functional Theory (DFT) calculations were conducted to examine the reaction mechanism and the free energy barrier of the elementary reactions underlying CO2 absorption in these four aqueous amine solutions. Kinetic models for CO2 absorption in tertiary amines and secondary amines were established, based on the base-catalyzed hydration mechanism and the zwitterion mechanism, respectively, both of which perform well in predicting the relationship between k0 and the amine concentration. The free energy barrier obtained by DFT is consistent with the activation energy barrier trend obtained by experiment. In addition, the effect of chain length on the free energy barrier was investigated through the chemical bond and weak interaction analysis.  相似文献   

2.
The objective of the present work was to find the accurate kinetic models and mechanism for CO2 absorption into tertiary amine solution, aiming at understanding the contribution of the CO2 reaction with H2O, OH, and tertiary amines on the overall reaction rate. First, the kinetics of CO2 absorption into water instead of a buffer solution were studied using the stopped-flow technique at 293–313 K, with initial CO2 molar concentration of 1.1–37.3 mM. The experimental first-order reaction rate constant () was determined to be about 1000 times larger than the value for CO2 absorption into buffer solution reported in the reference. The was then correlated by a proposed semiempirical model and a simplified theoretical model, giving the activation energy for CO2 reacting with H2O as fitted by the simplified theoretical model in good agreement with the value of previous research. Also, the pH values and hydroxyl ion concentrations of aqueous Diethylaminoethanol (DEEA) solutions were determined at 293–313 K, with DEEA molar concentration of 0.1–0.4 M and CO2 loading of 0–0.626 mol/mol. In addition, the observed first-order reaction rate constant ( k0_DEEA ) of binary DEEA-H2O solution with DEEA molar concentration of 0.1–0.4 M reacting with CO2 was determined at 293–313 K. It should be pointed out that the kinetic experiments of CO2 absorption into DEEA solution was done with the molar ratio of DEEA to CO2 fixed at 20. The values of k0_DEEA were then fitted and predicted by four models (i.e., termolecular model, base-catalyzed model, the improved model, and Khalifah model). The results show the improved model and Khalifah model can predict k0_DEEA well with an average absolute relative difference (AARD) <5%. The predicted results indicate that the contribution of OH to k0_DEEA cannot be ignored for the absorption of CO2 into tertiary amine solutions, and could be responsible for 50–70% of the total absorption reaction rate. Furthermore, the k0 value of CO2 absorption into aqueous triethanolamine and CO2-loaded DEEA solution were further investigated and comprehensively discussed, suggesting that both pK a and the CO2 solubility affect k0 , with pK a having a much more significant effect. © 2018 American Institute of Chemical Engineers AIChE J, 65: 652–661, 2019  相似文献   

3.
以MDEA为主体的混合胺溶液吸收CO2研究进展   总被引:4,自引:0,他引:4  
陈颖  赵越超  梁宏宝  张宏宇 《陕西化工》2014,(3):531-534,538
综述了近年来乙醇胺、二乙醇胺、哌嗪、碳酸酐酶以及离子液体与N-甲基二乙醇胺的混合溶液用于CO2吸收的研究进展;分析了混合溶液的吸收机理和CO2吸收的动力学;讨论了混合溶液组成、体系温度、压力等对吸收性能的影响;并对该法未来的研究方向和发展前景进行了展望.  相似文献   

4.
In the present work, the kinetics of the reactive absorption of CO2 in 1-dimethylamino-2-propanol (1DMA2P) solution were experimentally measured using a laminar jet absorber over a temperature range of 298–313 K, 1DMA2P concentration range of 0.5–2.0 mol/L, and CO2 loading range of 0–0.06 mol CO2/mol amine. The measured kinetics data were then used to develop a comprehensive numerical kinetics model using a FEM-based COMSOL software. The reaction rate model of the CO2 absorption into 1DMA2P solution were then validated by comparing model rates with the experimental rates. An excellent agreement of model data with experimental data was achieved with an absolute average deviation (AAD) of 6.5%. In addition, vapor–liquid equilibrium plots of all ions in the 1DMA2P-H2O-CO2 system were also developed. Further, this work has provided an effective criterion for evaluating CO2 absorption, that can be used for both the conventional amines and alternative amines for the purpose of providing guidelines or information on how to effectively screen solvents.  相似文献   

5.
In order to establish an accurate kinetic model for the aqueous amine blends, monoethanolamine (MEA), 2-(ethylamino) ethanol (EAE), and 3-(diethylamino)-1-propanol (3DEA1P) have been chosen as a typical CO2 absorption trisolvents. The reaction kinetics of aqueous amine blends with carbon dioxide have been investigated first combining experiments and molecular simulations. The stopped-flow technology has been used to obtain the observed reaction rate constant of the overall reactions over the temperature range of 293 to 313 K and at different amine concentrations. A theoretical kinetic model, based on the first-principles quantum-mechanical simulations, has been put forward to interpret the reactions between CO2 and the aqueous trisolvent amine blends systems. The proposed model, based on the zwitterion mechanism and the base-catalyzed mechanism, shows good prediction with an acceptable absolute average deviation (AAD) of 6.32%, and has been found to be satisfactory in determining the kinetics of the involved complicated reactions.  相似文献   

6.
张中林  刘道银  董伟  吴烨  孟庆敏  陈晓平 《化工学报》2014,65(10):4101-4109
利用热重分析仪、扫描电镜和氮吸附仪对不同粒径的K2CO3颗粒和负载型K2CO3/Al2O3二氧化碳吸收剂的碳酸化特性进行研究。负载后的吸收剂比表面积和孔隙结构得到较大改善,使得碳酸化反应速率和转化率均提高,吸收剂碳酸化特性得到改善。纯K2CO3颗粒吸收剂的反应速率和转化率随着粒径的增加而减小,负载型吸收剂的反应速率和转化率随着粒径的增加略增大。研究了不同粒径和反应时间对K2CO3/Al2O3颗粒微观结构的影响,结果表明K2CO3/Al2O3颗粒具有较稳定的微观结构。采用负载型粒子模型对K2CO3/Al2O3吸收剂吸收CO2碳酸化过程进行研究,所建立的粒子模型计算结果与试验值吻合较好。利用建立的模型对不同CO2浓度下K2CO3/Al2O3吸收剂碳酸化反应特性进行模拟计算,模拟结果具备一定的合理性和准确性,为开展进一步研究提供了基础。  相似文献   

7.
Experimental data and a model for the initial kinetics of CO2 into 3‐(methylamino)propylamine (MAPA) solutions are presented in work. MAPA has been tested as an activator for tertiary amines with encouraging results. The measurements were performed in a string of discs contactor and, as no initial kinetics data are available in literature, additional measurements were carried out and in a wetted wall column. The obtained overall mass‐transfer coefficients from both apparatuses are in reasonable agreement. To obtain values for the observed kinetic constant, , the experimental results were interpreted using a two‐film mass‐transfer model and invoking the pseudo‐first order assumption. Needed experimental values for density, viscosity, and Henry's law coefficient for CO2 were measured and are given. The results indicate that MAPA is almost twice as fast as piperazine, eight times faster than 2‐(2‐aminoethyl‐amino)ethanol (AEEA), and 15 times faster than monoethanolamine, when comparing unloaded 1 M solutions at 25°C. The observed kinetic constant was modeled using the direct mechanism. The final expression for can be applied for any concentration and temperature within the experimental data range, and, together with the presented physical data, comprises a complete model for calculating absorption fluxes. © 2014 American Institute of Chemical Engineers AIChE J, 60: 3792–3803, 2014  相似文献   

8.
CO2 diluted with N2 was absorbed by aqueous DEA solutions in a high shear jet absorber consisting of a high pressure stainless steel vessel with a pressure nozzle at the top. The results show that equilibrium conditions can be rapidly reached under high shear conditions. CO2 removal expressed by moles of CO2 absorbed per mole of DEA increased with gas flow rate and decreased with liquid flow rate. The overall mass transfer capacity coefficient Kg a was found to increase with gas flow rate and solution concentration. Kg a went through a maximum with solution flow rate. Increasing the CO2 partial pressure was found to decrease Kg a.  相似文献   

9.
利用5 L的气液固三相机械搅拌反应器,研究了Li2CO3碳化三相反应动力学。对影响碳化过程的诸因素进行了深入的研究和探讨。结果表明,Li2CO3的碳化率随CO2压力、气流大小、搅拌速度的增大而增大;随反应温度、固体浓度、颗粒粒径、物料填充度的增大而减小。通过对实验数据的拟合得出实验范围内该过程的动力学方程;得出该过程受控于化学反应,并计算出了该过程的表观活化能-17.37 kJ/mol。该研究为Li2CO3碳化工艺条件的优化和反应器的设计等问题提供了基本理论依据。  相似文献   

10.
刘敦禹  程潜  金晶 《化工进展》2018,37(Z1):35-42
采用基于pH测量的CO2吸收速率研究方法。将pH与溶液中的成分相关联,采用分段拟合获得CO2吸收速率,获得溶液成分对吸收速率的影响规律。对于低浓度的NaOH来说,吸收速率一直保持不变直到CO2物理吸收到NaHCO3溶液中。对于高浓度的NaOH,NaOH完全转化成Na2CO3时,吸收速率降低。但在两个吸收阶段中,吸收速率不变,CO2物理吸收到NaHCO3中时,吸收速率随CO2饱和度的增加而降低。对CO2吸收到NaOH中,CO2和钠离子浓度都促进吸收,钠离子浓度影响更大;对于CO2吸收到Na2CO3中,当Na2CO3浓度大于0.05mol/L,吸收速率不随浓度增加;对于CO2吸收到NaHCO3中,低浓度的钠可以促进CO2吸收,而高浓度的钠抑制CO2吸收,这主要由于析盐的作用。为避免CO2大量吸收,优先选择0.5mol/L以上浓度的NaHCO3。  相似文献   

11.
12.
The kinetics of CO2 absorption into aqueous solutions of N,N‐diethylethanolamine (DEEA), and N,N‐dimethylethanolamine (DMEA), and their blends with monoethanolamine (MEA) have been studied in a stopped‐flow apparatus. The kinetics experiments were carried out at the concentrations of DEEA and DMEA varying from 0.075 to 0.175 kmol/m3, respectively, and that of MEA ranging between 0.0075 and 0.0175 kmol/m3, over the temperature range of 293–313 K. Two kinetics models are proposed to interpret the reaction in the blended amine systems and the results show that the model which incorporates the base‐catalyzed hydration mechanism and termolecular mechanism resulted in a better prediction. Furthermore, the kinetics behaviors of CO2 absorption into two blended systems are comprehensively discussed according to their molecular structures. It can be concluded that the interaction between tertiary amines and primary amines as well as the alkyl chain length of tertiary amines have a significant influence on the kinetics. © 2017 American Institute of Chemical Engineers AIChE J, 64: 1350–1358, 2018  相似文献   

13.
二氧化碳、碳酸氢盐与有机伯胺和仲胺反应机理   总被引:3,自引:1,他引:2       下载免费PDF全文
采用停留光谱法和核磁共振(氢谱)法系统地研究了二氧化碳(aq)、碳酸氢盐与一乙醇胺(MEA)、L-氨基丙醇(2-AP)、1-氨基-2-丙醇(1-AP)、N-甲基正丙胺(IBA)、3-氨基丙醇(3-AP)、二乙醇胺(DEA)、吗啉(MORP)、哌啶(PIPD)和4-哌啶甲醇(4-PIPDM)在水溶液中25℃下的反应动力学,阐明其反应机理,给出二氧化碳、碳酸氢盐与有机胺的反应速率常数、氨基甲酸盐质子化常数和氨基甲酸盐的稳定常数。研究发现:二氧化碳与伯胺和仲胺的反应速率常数与其氨基甲酸盐的稳定常数具有线性关系。发现氨基甲酸盐稳定常数代表液态有机胺(氨)分子的空间位阻效应、溶剂化效应和电子效应的协同作用,它对于设计新型液态有机胺分子具有重要理论指导作用。  相似文献   

14.
The kinetics for the reactions of carbon dioxide with 2‐amine‐2‐methyl‐1‐propanol (AMP) and carbon dioxide (CO2) in both aqueous and nonaqueous solutions were measured using a microfluidic method at a temperature range of 298–318 K. The mixtures of AMP‐water and AMP‐ethylene glycol were applied for the working systems. Gas‐liquid bubbly microflows were formed through a microsieve device and used to determine the reaction characteristics by online observation of the volume change of microbubbles at the initial flow stage. In this condition, a mathematical model according to zwitterion mechanism has been developed to predict the reaction kinetics. The predicted kinetics of CO2 absorption in the AMP aqueous solution verified the reliability of the method by comparing with literatures’ results. Furthermore, the reaction rate parameters for the reaction of CO2 with AMP in both solutions were determined. © 2015 American Institute of Chemical Engineers AIChE J, 61: 4358–4366, 2015  相似文献   

15.
N-methylcyclohexylamine (MCA) and N-cyclohexyl-1,3-propanediamine (CHAP) have been suggested, in mixtures with lipophilic amines, as potential phase change solvents for CO2 capture applications, and subsequently studied as promising alternatives to monoethanolamine (MEA) for minimizing the desorber's energy requirements. In this study, new high pressure experimental data were obtained for the solubility of CO2 in aqueous solutions containing MCA or CHAP at 313 and 333 K. The obtained data were used to parameterize the modified Kent–Eisenberg model. In this direction, CHAP was modeled assuming a “principle of independent reactivity,” that is, that the reactivity of each amine group does not depend on the potential reaction of the other one. It was shown that through this approach the model can be successfully applied to diamines using the relevant equations of amine mixtures.  相似文献   

16.
A thermodynamically consistent model for the carbon dioxide (CO2) absorption in aqueous alkanolamine system is of great importance in the research and development of a CO2 capture process. To facilitate the development of thermodynamic models, linear Gibbs free energy, enthalpy, and heat capacity relationships using well-known amines as reference are used to correlate the standard reference state properties of ionic species with those of molecular species in the electrolyte system, which has been approved to provide a reliable and consistent way to estimate required parameters when there is minimal or no appropriate experimental data available. The proposed relationships have been applied to the development of an electrolyte nonrandom two liquid (NRTL) activity coefficient model for CO2 absorption in aqueous 1-amino-2-propanol (A2P) solution, as an example to demonstration the methodology. With limited vapor–liquid equilibrium data and other thermodynamic properties, the parameters in the electrolyte NRTL model are identified with good accuracy.  相似文献   

17.
In this work, Diethanolamine (DEA) was considered as an activator to enhance the CO2 capture performance of Monoethanolamine (MEA). The addition of DEA into MEA system was expected to improve disadvantages of MEA on regeneration heat, degradation, and corrosivity. To understand the reaction mechanism of blended MEA‐DEA solvent and CO2, 13C nuclear magnetic resonance (NMR) technique was used to study the ions (MEACOO, DEACOO, MEA, DEA, MEAH+, DEAH+, , ) speciation in the blended MEA‐DEA‐CO2‐H2O systems with CO2 loading range from 0 to 0.7 mol CO2/mol amine at the temperature of 301 K. The different ratios of MEA and DEA (MEA: DEA = 2.0:0, 1.5:0.5, 1.0:1.0, and 0:2.0) were studied to comprehensively investigate the role of DEA in the system of MEA‐DEA‐CO2‐H2O. The results revealed that DEA performs the coordinative role at the low CO2 loading and the competitive role at high CO2 loading. Additionally, the mechanism was also proposed to interpret the reaction process of the blended solvent with CO2. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2515–2525, 2018  相似文献   

18.
利用完全煅烧后的CaO和粉煤灰(Fly Ash)为材料制备了CaO/FA吸收剂。在350~650℃温度范围内对其碳酸化反应特性进行了研究。考察了不同质量比的CaO/FA吸收剂吸收CO2的性能。利用XRD、N2吸附等表征手段对吸收剂反应前后产物进行了表征。结果表明:通过水合反应过程,吸收剂比表面积增大,孔径在5~40nm范围内属于中孔,有利于减小CO2向颗粒内部的扩散阻力。CaO/FA吸收剂CO2吸收量随温度的升高而增加。当CaO与粉煤灰的质量比为3:1时制备的吸收剂具有最好的CO2吸收能力,在650℃时其最大CO2吸收量达到了227.13mg/g。通过多次循环试验后,吸附剂仍保持较高的CO2吸收量与稳定吸收性能。失活模型可以很好地预测CaO/FA吸收剂吸收CO2的过程,并得到了理想的吸收速率常数和失活速率常数。  相似文献   

19.
A set of poly[N‐oligo(ethylene oxide)yl 4‐vinylpyridinium tosylate] (P4VOEOOTs) has been prepared by spontaneous polymerization of 4‐vinylpyridine. This method gives a grafted polyelectrolyte having a positive charge on every backbone pyridinic moiety. The P4VP15Ts, P4VP164Ts, P4VP350Ts and P4VP750Ts aqueous solution conductivities were determined in the concentration range from 6 × 10?4 to 10?2 M at 25 °C. The variation of the conductivity versus concentration of the investigated system exhibits typical polyelectrolyte behaviour. The polyelectrolyte mobility was found to be dependent on the oligo(ethylene oxide) (OEO) side‐chain length. Manning's rod‐like model fails to describe these results. A simple steric effect is proposed to explain the influence of the OEO length. Copyright © 2003 Society of Chemical Industry  相似文献   

20.
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