Solubilities and diffusivities of N2O and CO2 in aqueous sulfolane solutions

The solubilities of N₂O and CO₂ in aqueous sulfolane solutions and pure sulfolane solvent, and the diffusivities of N₂O in aqueous sulfolane solutions were measured and correlated over the temperature range from 20° to 85°C; also, the data for density and viscosity that were needed in this experimental work were measured. This experiment revealed that the parameter of N₂O analogy method depends not only on the temperature, but also on the character of the solvent. Therefore, different solvents possess different analogy parameters. Only for dilute aqueous solutions can the parameter be replaced by the analogy parameter of water. The results also proved that the sum of volume fractions contribution is a simple method to estimate the solubility in aqueous sulfolane solutions over the whole range of the concentrations and experimental temperatures, with an average deviation of less than 4·0%.     

压力对N-甲基二乙醇胺混合哌嗪水溶液脱碳速率的影响

通过实验室填料塔研究了加压下(0. 2—0. 6MPa)哌嗪 (PZ)混合N 甲基二乙醇胺 (MDEA)水溶液吸收CO2的动力学。研究结果表明当CO2 分压大于 0. 1MPa时,压力会强化在气液界面的表面扰动,使得CO2 吸收速率较常压模型值大,并且该速率随压力的增大而增加。得到了哌嗪混合MDEA水溶液脱碳常压动力学模型的压力修正式。     

A comparative kinetics study of CO2 absorption into aqueous DEEA/MEA and DMEA/MEA blended solutions

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     

环丁砜对乙醇胺溶液吸收和解吸CO2的影响

利用物理溶剂环丁砜替代部分水,采用气液搅拌实验装置和真实热流量热法测定了环丁砜对乙醇胺（MEA）溶液吸收和解吸二氧化碳（CO₂）过程的影响,考察了CO₂循环负载、吸收速率、吸收热和解吸热等性质变化。研究表明：环丁砜对MEA溶液负载CO₂的吸收热影响较小,但对吸收速率、循环吸收容量和解吸过程影响较大。环丁砜可降低MEA溶液对CO₂的表观吸收速率,且随CO₂负载量的增大,降幅也逐渐变大。环丁砜有利于富液解吸过程,加快解吸速率,增大CO₂解吸程度,同时单位热流负荷、单位冷流负荷和单位能耗均有不同程度的降低。在燃煤电厂烟气条件下,20% MEA+20% sulfolane体系相对20% MEA体系,其表观吸收速率平均降低约10%,CO₂循环吸收容量增加24%,单位CO₂解吸能耗降低18%。     

Solubility of H2S and CO2 in sulfolane

The solubility of H, S and CO₂ in sulfolane (tetrahydrothiophene-1, 1—dioxide) has been measured at 40°C and 100°C at pressures up to 2350 kPa and 5900 kPa respectively. The Henry's constants obtained from the data are in agreement with those of Rivas and Prausnitz.     

以MDEA为主体的混合胺溶液吸收CO2研究进展

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.     

Mass transfer of carbon dioxide in aqueous polyacrylamide solution with methyldiethanolamine

Carbon dioxide was absorbed into aqueous polyacrylamide (PAA) solution containing methyl-diethanolamine (MDEA) in a flat-stirred vessel to investigate the effect of non-Newtonian rheological behavior of PAA on the rate of chemical absorption of CO₂, where the reaction between CO₂ and MDEA was assumed to be a first-order reaction with respect to the molar concentration of CO₂ and MDEA, respectively. The liquid-side mass transfer coefficient (k_L), which was obtained from the dimensionless empirical equation containing the viscoelasticity properties of a non-Newtonian liquid, was used to estimate the enhancement factor due to chemical reaction. PAA with elastic property of non-Newtonian liquid made the rate of chemical absorption of CO₂ accelerate compared with a Newtonian liquid     

Absorption of co2 into aqueous tertiary amine/mea solutions

Absorption rates for CO₂ into aqueous solutions of TEA, MDEA and blends of MEA with MDEA and TEA were measured in a stirred cell by a method similar to that used by Laddha and Danckwerts (1981). Second order rate constants for CO₂-TEA and CO₂-MDEA were obtained from the single amine data for temperatures in the range of 25-60°C. A modified pseudo first order model based on the film theory is used to predict the rate of absorption of CO₂ into mixed amine solutions. This model accounts for the variation of amine concentration in the film and assumes a shuttle mechanism for rate enhancement. Bulk liquid concentrations of the various species present are obtained from a simplified thermodynamic model. The model predicts absorption rates that are in agreement with experimental measurements.     

Equilibrium solubility of H2S and CO2 and their mixtures in a mixed solvent

The solubility of hydrogen sulphide, carbon dioxide, and their mixtures has been measured at 40° and 100°C in a mixed solvent consisting of 20.9 wt% MDEA (methyldiethanolamine), 30.5 wt% sulfolane (tetrahydrothiophene-1, 1-dioxide), and 48.6 wt% water. The results have been compared with those for aqueous 2.0 mol/dm³ MDEA and an analogous mixed solvent, containing AMP (2-amino-2-methyl-1-propanol), which are available in the literature. These data were used to modify the solubility model of Deshmukh and Mather (1981) to account for the mixed solvent effects on the system thermodynamics. Results show that the model is useful as a first approximation in predicting acid gas solubilities; agreement with experiment was generally found to be within £15%.     

Numerical investigation on CO2 absorbed in aqueous N‐methyldiethanolamine + piperazine

A multiphase and multicomponent mass transfer model of CO₂ absorbed in aqueous N‐methyldiethanolamine and piperazine (PZ) was built in the study. In the model, a simple method of mass transfer between phases was proposed. Besides, the hydrodynamics, thermodynamics, and complex reversible chemical reaction were considered simultaneously. The model was validated by comparing with the previous experimental data which showed that simulated results can represent the experimental data with reasonable accuracy. Based on the model, the effects of gas velocity, liquid load and CO₂ loading on the absorption rate, and enhancement factor were analyzed. Model results showed that the enhancement factor increased with a rising gas velocity while decreased with a rising liquid load or CO₂ loading. The change of enhancement factor with CO₂ loading was similar to that of equilibrium concentration of PZ which indicated that PZ was significant to the absorption process. Furthermore, the distributions of specie concentrations were discussed in detail. © 2016 American Institute of Chemical Engineers AIChE J, 63: 2386–2393, 2017     

The development of kinetics model for CO2 absorption into tertiary amines containing carbonic anhydrase

CO₂ absorption into aqueous solutions of two tertiary alkanolamines, namely, MDEA and DMEA with and without carbonic anhydrase (CA) was investigated with the use of the stopped‐flow technique at temperatures in the range of 293–313 K, CA concentration varying from 0 to 100 g/m³ in aqueous MDEA solution with the amine concentration ranging from 0.1 to 0.5 kmol/m³, and CA concentration varying from 0 to 40 g/m³ in aqueous DMEA solution with the amine concentration ranging from 0.05 to 0.25 kmol/m³. The results show that the pseudofirst‐order reaction rate (k_{0, amine}; s^?1) is significantly enhanced in the presence of CA as compared with that without CA. The enhanced values of the kinetic constant in the presence of CA has been calculated and a new kinetics model for reaction of CO₂ absorption into aqueous tertiary alkanolamine solutions catalyzed by CA has been established and used to make comparisons of experimental and calculated pseudo first‐order reaction rate constant (k_{0, with CA}) in CO₂‐MDEA‐H₂O and CO₂‐DMEA‐H₂O solutions. The AADs were 15.21 and 15.17%, respectively. The effect of pKa on the CA activities has also been studied by comparison of CA activities in different tertiary amine solutions, namely, TEA, MDEA, DMEA, and DEEA. The pKa trend for amines were: DEEA > DMEA > MDEA > TEA. In contrast, the catalyst enhancement in amines was in the order: TEA> MDEA> DMEA> DEEA. Therefore, it can be seen that the catalyst enhancement in the amines decreased with their increasing pKa values. © 2017 American Institute of Chemical Engineers AIChE J, 2017     

N-甲基二乙醇胺溶液对H2S和CO2的吸收模拟

采用N-甲基二乙醇胺(MDEA)吸收炼化过程中干气及液态烃中过量的H2S和CO2,以达到生产要求。文中利用PRO/II软件对MDEA溶液吸收H2S和CO2的过程,采用合适的热力学模型(Electrolyte-NRTL),建立吸收塔模型进行模拟。研究了进料气液质量比、进料温度、操作压力、塔板高度、吸收液浓度等条件的改变对吸收效果的影响,并对操作条件进行评估。MDEA溶液对CO2的吸收效果不是很理想,由于伯、仲胺可直接与CO2反应,故向溶液中添加DEA,采用PRO/II的Kent-Eisenberg模型对MDEA/DEA混合胺的吸收状况进行模拟,其吸收效果较理想。文中对现有装置提出了一些技术改造建议。     

MDEA与哌嗪、二乙醇胺混合溶液吸收二氧化碳速率研究

Absorption rate of CO2 into aqueous solution of N-methyldiethanolamine (MDEA) blended with diethanolamine (DEA) and piperazine (PZ) was studied and a kinetic model was established. It is shown that homogeneous activation mechanism could explain this absorption process. The absorption rate coefficients of carbon dioxide into MDEA aqueous solution blended with DEA, PZ or DEA PZ were compared with each other. The results demonstrated that the different activation effect of DEA, PZ and DEA PZ on the carbon dioxide absorption comes from the difference in CO2 combination rate, transport of PZ and DEA to MDEA and the regeneration rate of PZ and DEA.     

Reaction kinetics of 2‐((2‐aminoethyl) amino) ethanol in aqueous and non‐aqueous solutions using the stopped‐flow technique

Observed pseudo‐first‐order rate constants (k_o) for the reaction between CO₂ and 2‐((2‐aminoethyl) amino) ethanol (AEEA) were measured using the stopped‐flow technique in an aqueous system at 298, 303, 308 and 313 K, and in non‐aqueous systems of methanol and ethanol at 293, 298, 303 and 308 K. Alkanolamine concentrations ranged from 9.93 to 80.29 mol m^?3 for the aqueous system, 29.99–88.3 mol m^?3 for methanol and 44.17–99.28 mol m^?3 for ethanol. Experimentally obtained rate constants were correlated with two mechanisms. For both the aqueous‐ and non‐aqueous‐AEEA systems, the zwitterion mechanism with a fast deprotonation step correlated the data well as assessed by the reported statistical analysis. As expected, the reaction rate of CO₂ in the aqueous‐AEEA system was found to be much faster than in methanol or ethanol. Compared to other promising amines and diamines studied using the stopped‐flow apparatus, the pseudo‐first‐order reaction rate constants were found to obey the following order: PZ (cyclic‐diamine) > EDA (diamine) > AEEA (diamine) > 3‐AP (primary amine) > MEA (primary amine) > EEA (primary amine) > MO (cyclic‐amine). The reaction rate constant of CO₂ in aqueous‐AEEA was double that in aqueous‐MEA, and the difference increased with an increase in concentration. All reaction orders were practically unity. With a higher capacity for carbon dioxide and a higher reaction rate, AEEA could have been a good substitute to MEA if not for its high thermal degradation. AEEA kinetic behaviour is still of interest as a degradation product of MEA. © 2012 Canadian Society for Chemical Engineering     

Kinetics of CO2 absorption into a novel 1‐diethylamino‐2‐propanol solvent using stopped‐flow technique

A stopped‐flow apparatus was used to measure the kinetics of carbon dioxide (CO₂) absorption into aqueous solution of 1‐diethylamino‐2‐propanol (1DEA2P) in terms of observed pseudo‐first‐order rate constant (k_o) and second‐order reaction rate constant (k₂), in this work. The experiments were conducted over a 1DEA2P concentration range of 120–751 mol/m³, and a temperature range of 298–313 K. As 1DEA2P is a tertiary amine, the base‐catalyzed hydration mechanism was, then, applied to correlate the experimental CO₂ absorption rate constants obtained from stopped‐flow apparatus. In addition, the pK_a of 1DEA2P was experimentally measured over a temperature range of 278–333 K. The Brønsted relationship between reaction rate constant (obtained from stopped‐flow apparatus) and pK_a was, then, studied. The results showed that the correlation based on the Brønsted relationship performed very well for predicting the absorption rate constant with an absolute average deviation of 5.2%, which is in an acceptable range of less than 10%. © 2014 American Institute of Chemical Engineers AIChE J, 60: 3502–3510, 2014     

Acceleration of the reaction of carbon dioxide into aqueous 2-amino-2-hydroxymethyl-1,3-propanediol solutions by piperazine addition

In this work, the kinetics of the reaction between CO₂ and piperazine-activated aqueous solutions of a sterically hindered alkanolamine, 2-amino-2-hydroxymethyl-1,3-propanediol (AHPD) was studied in a wetted wall column contactor at 303.15, 313.15 and 323.15 K. The AHPD concentration in the aqueous solutions was kept at while the piperazine (PZ) concentration varied in the range . Under pseudo-first-order CO₂ absorption conditions, the overall pseudo-first-order rate constants were determined and reaction rate parameters were calculated with a non-linear regression from the overall reaction rate constant. The ratio of the diffusivity and Henry's law constant for CO₂ in solutions was estimated by applying the N₂O analogy and the Higbie penetration theory, using the physical absorption data of CO₂ and N₂O in water and of N₂O in amine solutions. Piperazine was found to be an effective activator in the aqueous AHPD solutions, as the addition of small amounts of PZ to these solutions has a significant effect on the enhancement of the CO₂ absorption rate for all studied temperatures.     

填料塔中哌嗪二胺吸收低浓度SO_2的传质性能

为满足有机胺法脱硫设计开发的需要,采用动态吸收法测定了填料塔中哌嗪二胺(PA-A)水溶液吸收低浓度SO2的体积总传质系数KGa,考察了吸收工艺参数如吸收液中的PA-A浓度和初始pH值、液相流率、吸收温度、进气SO2浓度及流速等对KGa的影响。结果表明:KGa随着吸收液中的PA-A浓度和初始pH值、液相喷淋密度的增加而增大;随着吸收温度、气相流率及进气SO2浓度的增加而减小。通过实验结果分析得到体积总传质系数KGa与气液相流率比(qG/qL)之间符合指数关系式,该经验关系可用于工程设计计算。     

低分压CO2在有机胺水溶液中的溶解度

建立了一套用于测定低分压CO2在有机胺水溶液中溶解度的实验装置。在298、308 K下分别测定了低分压CO2在较低浓度的乙醇胺(MEA)、二乙醇胺(DEA)水溶液中的溶解度。结果表明,在较低的溶解度下,CO2在有机胺水溶液中的平衡分压接近于0;当溶解度增大到一定程度后,平衡分压随其增加而急剧增大,同时,温度的升高和有机胺浓度的增大均能增大CO2的平衡分压。通过实验数据拟合得到的理论模型参数与实验值符合较好。     

Prediction of equilibrium solubility of CO2 in aqueous alkanolamines using differential evolution algorithm

The design of sour‐gas treating processes with alkanolamine solvents requires knowledge of the vapour–liquid equilibrium (VLE) of the aqueous acid gas–alkanolamine systems. Representation of the experimental data with a thermodynamically rigorous model is required, so that one can systematically correlate and predict the VLEs of these systems. The modified Clegg–Pitzer equations have been used to correlate and predict the VLE of CO₂ in the aqueous N‐methyldiethanolamine (MDEA) and 2‐amino‐2‐methyl‐1‐propanol (AMP) systems. Differential evolution (DE), an evolutionary computational technique, has been used for parameter estimation of the developed VLE model in an effort to predict the VLE of CO₂ in aqueous MDEA and AMP solutions with a comparable accuracy to that by using the non‐traditional simulated annealing (SA) and deterministic technique like Levenberg–Marquardt (LM), if not better. In this work, the DE/rand‐best/1/bin strategy has been used for finding near global minimum solutions to the multivariable optimization problem as a part of the numerical solution of the developed model.