Modeling of CO2 equilibrium solubility in a novel 1‐Diethylamino‐2‐Propanol Solvent

In this work, the equilibrium solubility of CO₂ in a 1‐diethylamino‐2‐propanol (1DEA2P) solution was determined as a function of 1DEA2P concentration (over the range of 1–2 M), temperature (in the range of 298–333 K), and CO₂ partial pressure (in the range of 8–101 kPa). These experimental results were used to fit the present correlation for K₂ (Kent‐Eisenberg model, Austgen model, and Li‐Shen model). It was found that all of the models could represent the CO₂ equilibrium solubility in 1DEA2P solution with ADDs for Kent‐Eisenberg model, Austgen model, and Li‐Shen model of 6.3, 7.3, and 12.2%, respectively. A new K₂ correlation model, the Liu‐Helei model, was also developed to predict the CO₂ equilibrium solubility in 1DEA2P solution with an excellent ADD of 3.4%. In addition, the heat of absorption of CO₂ in 1DEA2P solution estimated by using the Gibbs‐Helmholtz equation was found to be ?45.7 ± 3.7 kJ/mol. Information and guidelines about effectively using data for screened solvents is also provided based on the three absorption parameters: CO₂ equilibrium solubility, second order reaction constant (k₂), and CO₂ absorption heat. © 2017 American Institute of Chemical Engineers AIChE J, 63: 4465–4475, 2017     

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     

Investigation mechanism of DEA as an activator on aqueous MEA solution for postcombustion CO2 capture

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     

Kinetics of CO2 absorption by aqueous 3‐(methylamino)propylamine solutions: Experimental results and modeling

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     

Determination of kinetics of CO2 absorption in solutions of 2‐amino‐2‐methyl‐1‐propanol using a microfluidic technique

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     

Comprehensive reaction kinetics model of CO2 absorption into 1-dimethylamino-2-propanol solution

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.     

A new model for correlation and prediction of equilibrium CO2 solubility in N‐methyl‐4‐piperidinol solvent

In this work, the equilibrium CO₂ solubility in the aqueous tertiary amine, N‐methyl‐4‐piperidinol (MPDL) was measured over a range of temperatures, CO₂ partial pressures and amine concentrations. The dissociation constant of the MPDL solution was determined as well. A new thermodynamic model was developed to predict the equilibrium CO₂ solubility in the MPDL‐H₂O‐CO₂ system. This model, equipped with the correction factor (C_f), can give reasonable prediction with an average absolute deviation of 2.0%, and performs better than other models (i.e., KE model, Li‐Shen model, and Hu‐Chakma). The second‐order reaction rate constant (k₂) of MPDL and the heat of CO₂ absorption (–ΔH_abs) into aqueous MPDL solutions were evaluated as well. Based on the comparison with some conventional amines, MPDL revealed a high‐equilibrium CO₂ loading, reasonably fast absorption rate when compared with other tertiary amines, and a low energy requirement for regeneration. It may, therefore, be considered to be an alternative solvent for CO₂ capture. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3395–3403, 2017     

A cobalt metal‐organic framework with small pore size for adsorptive separation of CO2 over N2 and CH4

In this study, a new cobalt‐based metal‐organic framework (MOF), [ (μ₃‐OH)₂(ipa)₅(C₃O₂)(DMF)₂] (CoIPA) was synthesized. The crystal structure analysis shows that CoIPA is constructed by Co₆(μ₃‐OH)₂ units linked by isophthalic acid forming a sxb topology and it possesses a small pore size of about 4 Å. The new MOF has been characterized using multiple experimental methods. Monte Carlo and Molecular Dynamic simulations were employed to investigate adsorption equilibrium and kinetics in terms of capacity and diffusivity of CO₂, N₂, and CH₄ on CoIPA. The gas adsorption isotherms collected experimentally were used to verify the simulation results. The activated CoIPA sample exhibits great gas separation ability at ambient conditions for CO₂/N₂ and CO₂/CH₄ with selectivity of around 61.4 and 11.7, respectively. The calculated self‐diffusion coefficients show a strong direction dependent diffusion behavior of target molecules. This high adsorption selectivity for both CO₂/N₂ and CO₂/CH₄ makes CoIPA a potential candidate for adsorptive CO₂ separation. © 2017 American Institute of Chemical Engineers AIChE J, 63: 4532–4540, 2017     

Kinetics and new mechanism study of CO2 absorption into water and tertiary amine solutions by stopped-Flow technique

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 ( k_{0_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 k_{0_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 k_{0_DEEA} well with an average absolute relative difference (AARD) <5%. The predicted results indicate that the contribution of OH⁻ to k_{0_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     

Ni/CaO‐Al2O3 bifunctional catalysts for sorption‐enhanced steam methane reforming

Ni/CaO‐Al₂O₃ bifunctional catalysts with different CaO/Al₂O₃ mass ratios were prepared by a sol–gel method and applied to the sorption‐enhanced steam methane reforming (SESMR) process. The catalysts consisted mainly of Ni, CaO and Ca₅Al₆O₁₄. The catalyst structure depended strongly on the CaO/Al₂O₃ mass ratio, which in turn affected the CO₂ capture capacity and the catalytic performance. The catalyst with a CaO/Al₂O₃ mass ratio of 6 or 8 possessed the highest surface area, the smallest Ni particle size, and the most uniform distribution of Ni, CaO, and Ca₅Al₆O₁₄. During 50 consecutive SESMR cycles at a steam/methane molar ratio of 2, the thermodynamic equilibrium was achieved using the catalyst with a CaO/Al₂O₃ mass ratio of 6, and H₂ concentration profiles for all the 50 cycles almost overlapped, indicating excellent activity and stability of the catalyst. Moreover, a high CO₂ capture capacity of 0.44 was maintained after 50 carbonation–calcination cycles, being almost equal to its initial capacity (0.45 ). © 2014 American Institute of Chemical Engineers AIChE J, 60: 3547–3556, 2014     

Thermodynamic validation of 1‐alkyl‐3‐methylimidazolium carboxylates as task‐specific ionic liquids for H2S absorption

Solubilities of H₂S in five 1‐alkyl‐3‐methylimidazolium carboxylates ionic liquids (ILs) have been measured at temperatures from 293.15 to 333.15 K and pressures up to 350 kPa. It is shown that these ILs have significantly larger absorption capacities for H₂S than those common ILs reported in the literature. The solubility is found to increase dramatically with the increasing alkalinity of the anions and slightly with the increasing length of the alkyl chains on the cations. It is further demonstrated that the absorption isotherms are typically nonideal. With the assumption of complex formation between H₂S and ILs, a reaction equilibrium thermodynamic model is developed to correlate the experimental solubilities. The model favors a reaction mechanism of AB₂ type that two IL molecules interact with one H₂S molecule. Thermodynamic parameters such as Henry's law constants, reaction equilibrium constants, and heat of complex formation are also calculated to evaluate the absorption process of H₂S in these ILs. © 2012 American Institute of Chemical Engineers AIChE J, 59: 2227–2235, 2013     

Kinetics of the absorption of carbon dioxide into aqueous ammonia solutions

Experiments were performed in a customized double stirred tank reactor to study the kinetics of CO₂ absorption into NH₃ solutions at concentrations ranging from 0.42 to 7.67 kmol·m^?3 and temperatures between 273.15 and 293.15 K. The results show that the reactive absorption was first order with respect to CO₂ but fractional order (1.6–1.8) with respect to ammonia. Experimental data can be satisfactorily interpreted by a termolecular mechanism using and . © 2016 American Institute of Chemical Engineers AIChE J, 62: 3673–3684, 2016     

Removal of Hg0 from flue gas using two homogeneous photo‐fenton‐like reactions

Removal of Hg⁰ using two homogeneous Photo‐Fenton‐Like reactions was first investigated in a photochemical reactor. Effects of process parameters on Hg⁰ removal were studied. Free radical and reaction products were analyzed. Removal pathways of Hg⁰ were discussed. Simultaneous removal of Hg⁰, NO, and SO₂ is also studied briefly. The results show that UV power, wavelength, H₂O₂ concentration, and solution pH have great effects on Hg⁰ removal. Hg⁰, and SO₂ concentrations, solution temperature, Fe³⁺, Cu²⁺, , and concentrations also have significant effects on Hg⁰ removal. However, concentrations of CO₂, NO, O₂, Cl^?, , , SiO₂, Al₂O₃, and Fe₂O₃ only have slight effects on Hg⁰ removal. Hg⁰/NO/SO₂ can be simultaneously removed by Photo‐Fenton‐Like reactions. ·OH was captured, and / /Hg²⁺ were also detected. Removals of Hg⁰ by photochemical oxidation and ·OH oxidation play a major role, and removal of Hg⁰ by H₂O₂ oxidation only plays a secondary role in removal of Hg⁰. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1322–1333, 2015     

Generic AI models for mass transfer coefficient prediction in amine-based CO2 absorber,Part II: RBFNN and RF model

In this work, the radial basis function neural network (RBFNN) and random forest (RF) algorithms were employed to develop generic AI models predicting mass transfer coefficient in amine-based CO₂ absorber. The models with operating parameters as input gave quite different prediction performance in different CO₂ absorption systems. To secure better applicability, extra parameters related to amine type and packing characteristics were introduced to reasonably describe mass transfer behaviors, respectively. Moreover, the generic models were proposed by considering all influencing factors of mass transfer in CO₂ absorber column. Furthermore, the performance of BPNN, RBFNN, and RF models was completely compared and fully discussed in terms of AARE. All three generic models could predict mass transfer coefficient of CO₂ absorber very well. It was found that the BPNN models provide the best predication with AAREs of below 5%. The developed generic model could serve as a fast and efficient tool for preliminary selection and evaluation of potential amines for CO₂ absorption. The framework of generic ML model development was also clearly presented, which could provide theoretical basis and practical guidance for the implementation and application of ML models in the carbon capture field.     

An experimental and theoretical study on the effects of amine chain length on CO2 absorption performance

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.     

AI models for correlation of physical properties in system of 1DMA2P-CO2-H2O

In this work, the density, viscosity, and specific heat capacity of pure 1-dimethylamino-2-propanol (1DMA2P) as well as aqueous unloaded and CO₂-loaded 1DMA2P solution (with a CO₂ loading of 0.04–0.70 mol CO₂/mol amine) were measured over the 1DMA2P concentration range of 0.5–3.0 mol/L and temperature range of 293–323 K. The observed experimental results of these thermophysical properties of the 1DMA2P-H₂O-CO₂ system were correlated using empirical models as well as artificial neural network (ANN) models (namely, back-propagation neural network [BPNN] and radial basis function neural network [RBFNN] models). It was found that the developed BPNN and RBFNN models could predict the experimental results of 1DMA2P-H₂O-CO₂ better than correlations using empirical models. The results could be treated as one of the accurate and potential methods to predict the physical properties for aqueous amine CO₂ absorption systems.     

New method of kinetic modeling for CO2 absorption into blended amine systems: A case of MEA/EAE/3DEA1P trisolvent blends

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.     

Nanostructured high‐energy xLi2MnO3·(1‐x)LiNi0.5Mn0.5O2 (0.3 ≤ x ≤ 0.6) cathode materials

Nanostructured lithium‐manganese‐rich nickel‐manganese‐oxide xLi₂MnO₃·(1‐x)LiNi_0.5Mn_0.5O₂ (0.3 ≤ x ≤ 0.6) composite materials were synthesized via spray pyrolysis using mixed nitrate precursors. All the materials showed a composite structure consisting of Li₂MnO₃ (C2/m) and LiNi_0.5Mn_0.5O₂ components, and the amount of Li₂MnO₃‐phase appeared to increase with x, as observed from XRD analysis. These composite materials showed a high‐discharge capacity of about 250 mAhg^?1. In the range of x considered, the layered 0.5Li₂MnO₃·0.5LiNi_0.5Mn_0.5O₂ materials displayed the highest capacity and superior cycle stability. Nonetheless, voltage suppression from a layered‐spinel phase transition was observed for all the composites produced. This voltage suppression was dependent of the amount of Li₂MnO₃ phase present in the composite structure. © 2013 American Institute of Chemical Engineers AIChE J 60: 443–450, 2014     

Novel Fe/MnK‐CNTs nanocomposites as catalysts for direct production of lower olefins from syngas

Novel Fe/MnK‐CNTs nanocomposites are developed as catalysts for direct production of lower olefins from syngas, delivering a high iron time yield of 337.2 μmol_CO· ·s^?1 with 51.3%C selectivity toward C₂?C₄ olefins under the optimal reaction conditions (270°C, 2.0 MPa, 30,000 mL h^?1 ). These catalysts are optimized by varying calcination temperature from 150 to 400°C. Multiple techniques including transmission electron microscopy, Elemental mapping, X‐ray diffraction, X‐ray photoelectron spectroscopy, H₂‐temperature‐programmed reduction, and Raman were employed to reveal the relationship between the catalyst nature and unique catalytic behavior. In particular, the resultant catalyst from the calcination temperature of 220°C exhibits the highest selectivity of C₂?C₄ olefins as well as good stability, which are enabled by the trade‐off among the effects of iron particle sizes, promoters, metal‐support interaction and support surface chemistry. Moreover, influences of reaction temperature, reaction pressure and space velocity are also investigated. © 2016 American Institute of Chemical Engineers AIChE J, 63: 154–161, 2017     

Removal of NO from flue gas using UV/S2 process in a novel photochemical impinging stream reactor

A novel photochemical impinging stream reactor was developed for the first time. Removal process of NO from flue gas using sulfate radical ( ·) and hydroxyl radical (·OH) from UV‐light activation of persulfate (UV/S₂ advanced oxidation process) was investigated in the novel reactor. Experiments were conducted to evaluate the effects of S₂ concentration, solution pH, UV power, solution temperature, liquid‐gas ratio, flue gas flow, NO, SO₂,and O₂ concentrations on removal of NO. Mechanism and kinetics of NO removal were also studied. The results show that increasing UV power, solution temperature, S₂ concentration, or solution circulation rate promotes NO removal. Increasing solution pH (1.2–11.9), NO concentration or flue gas flow weakens NO removal. O₂ concentration has no significant effect on NO removal. · and ·OH were the major active species for NO removal. Absorption rate equation and kinetic parameters of NO removal were obtained. © 2017 American Institute of Chemical Engineers AIChE J, 63: 2968–2980, 2017