Modeling of H2S, CO2 + H2S, and CH4 + CO2 Solubilities in Aqueous Monoethanolamine and Methyldiethanolamine Solutions

Plakia, Anthoula; Voutsas, Epaminondas

doi:10.1021/acs.iecr.0c00467

Cited by 15 publications

(33 citation statements)

References 61 publications

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“…To evaluate performance of the absorbent, H 2 S solubility is used as a primary performance indicator, which is generally reported in mol H 2 S/mol absorbent at various operating temperatures and pressures. Numbers of high potential physical solvents have been investigated and can be exampled as: (i) physical organic solvents of n -dodecane, sulfolane, N -methylimidazole (NMP), and γ-butyrolactone (GBL) and (ii) ionic liquids of 1-butyl-3-methylimidazolium methylsulfate ([bmim][MeSO 4 ]) and 1-ethyl-3-methylimidazolium ethylsulfate ([emim][EtSO 4 ]). − The chemical solvents, which are typical alkanolamine solvents, include monoethanolamine (MEA), 2-amino-2-methyl-1-propanol (AMP), N -methyldiethanolamine (MDEA), and diisopropanolamine (DIPA). − Additionally, combining the physical process and reversible process of blending alkanolamines with organic solvents or ionic liquids has also been considered. Examples of the hybrid solvents are MDEA + sulfolane, NMP + MEA, and MDEA + 1-butyl-3-methylimidazolium acetate [bmim][acetate]. − …”

Section: Introductionmentioning

confidence: 99%

Applied Artificial Neural Network for Hydrogen Sulfide Solubility in Natural Gas Purification

et al. 2021

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Solubility of hydrogen sulfide (H2S) in 46 single and blended physical absorbents, amines, ionic liquids, and hybrid absorbents of amines + ionic liquids and amines + physical absorbents was successfully predicted based on artificial neural networks (ANNs). Three neural network algorithms of Levenberg–Marquardt (LM), Bayesian regularization (BR), and scaled conjugate gradient (SCG) were applied for architecting the ANN models. The results showed that both the number of hidden neurons and the prediction algorithm affected the prediction of H2S solubility. Based on the mean square error (MSE) and determination coefficient (R 2), the most attractive model was the LM-ANN model with 17 hidden neurons. As a result, very satisfactory prediction performance (for the testing data set) with an MSE of 0.0014 and an R 2 of 0.9817 was obtained from the developed LM-ANN model. Additionally, a parity chart confirmed that the predicted solubility of H2S well aligned with the experimental data. To effectively absorb H2S and maintain high solubility of H2S, the absorbent should be well complied with the operating pressure. For a low-pressure range of less than 100 kPa, amines are very attractive. As the pressure elevated to 100–1000 kPa, amines and hybrid amine + physical absorbents are suggested. Lastly, at a high pressure over 1000 kPa, physical absorbents and ionic liquids are recommended.

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Section: Introductionmentioning

confidence: 99%

Applied Artificial Neural Network for Hydrogen Sulfide Solubility in Natural Gas Purification

et al. 2021

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“…As a case study for CASpy, we investigate the binary CO 2 and H 2 S absorption from an ideal gas phase to aqueous MDEA. In the CO 2 /MDEA/water system, we have four reactions: normalC normalO 2 ( a q . ) + 2 normalH 2 normalO ⇄ normalH normalC normalO 3 − + normalH 3 normalO + normalH normalC normalO 3 − + normalH 2 normalO ⇄ normalC normalO 3 2 − + normalH 3 normalO + normalM normalD normalE normalA normalH + + normalH 2 normalO ⇄ normalM normalD normalE normalA + normalH 3 normalO + 2 normalH 2 normalO ⇄ normalH 3 normalO + + normalO normalH − By combining…”

Section: Methodsmentioning

confidence: 99%

“…In this study, we develop a chemical reaction equilibrium solver in Python called CASpy and use it to solve binary (and single-component) CO 2 and H 2 S absorption isotherms in aqueous methyldiethanolamine (MDEA) solutions (see the Supporting Information for source code for CASpy version 0.1.6). We study the absorption of CO 2 and H 2 S in aqueous MDEA solutions because it is relevant to biogas upgrading and acid gas (CO 2 and H 2 S) removal from natural gas. − Molecular simulation is a natural choice for this application as simulations allow studies without the difficulty of working with H 2 S (due to safety and environmental concerns), and eliminate the low accuracy of experiments at low partial pressures of acid gases. , For this purpose, we first derive an expression for the equilibrium constant as a function of μ i ex and μ i 0 of species i , temperature, and volume using a mole fraction-based equilibrium constant and develop software to solve chemical reaction equilibria in combination with absorption. A schematic representation of the scheme of our chemical reaction equilibrium solver is shown in Figure .…”

Section: Introductionmentioning

confidence: 99%

Solving Chemical Absorption Equilibria using Free Energy and Quantum Chemistry Calculations: Methodology, Limitations, and New Open-Source Software

Polat

Meyer

Houriez

et al. 2023

J. Chem. Theory Comput.

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We developed an open-source chemical reaction equilibrium solver in Python (CASpy, ) to compute the concentration of species in any reactive liquid-phase absorption system. We derived an expression for a mole fraction-based equilibrium constant as a function of excess chemical potential, standard ideal gas chemical potential, temperature, and volume. As a case study, we computed the CO2 absorption isotherm and speciation in a 23 wt % N-methyldiethanolamine (MDEA)/water solution at 313.15 K, and compared the results with available data from the literature. The results show that the computed CO2 isotherms and speciations are in excellent agreement with experimental data, demonstrating the accuracy and the precision of our solver. The binary absorptions of CO2 and H2S in 50 wt % MDEA/water solutions at 323.15 K were computed and compared with available data from the literature. The computed CO2 isotherms showed good agreement with other modeling studies from the literature while the computed H2S isotherms did not agree well with experimental data. The experimental equilibrium constants used as an input were not adjusted for H2S/CO2/MDEA/water systems and need to be adjusted for this system. Using free energy calculations with two different force fields (GAFF and OPLS-AA) and quantum chemistry calculations, we computed the equilibrium constant (K) of the protonated MDEA dissociation reaction. Despite the good agreement of the OPLS-AA force field (ln[K] = −24.91) with the experiments (ln[K] = −23.04), the computed CO2 pressures were significantly underestimated. We systematically investigated the limitations of computing CO2 absorption isotherms using free energy and quantum chemistry calculations and showed that the computed values of μ i ex are very sensitive to the point charges used in the simulations, which limits the predictive power of this method.

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“…The SO 2 emission related to environmental pollution issues mainly originated from the consumption of worldwide fossil fuel energy. Flue-gas desulfurization (FGD) has been developed to eliminate SO 2 from effluent gases for several decades in the industry. − For a long time, limestone scrubbing, − ammonia scrubbing, − and aqueous organic amines − are adopted as the traditional FGD. However, the above-mentioned technologies tenderly resulted in secondary pollution due to inevitable drawbacks such as unusable byproducts and organic vapor.…”

Section: Introductionmentioning

confidence: 99%

Guanidinium-Based Ionic Liquids for High-Performance SO₂ Capture and Efficient Conversion for Cyclic Sulfite Esters

Geng

et al. 2022

Ind. Eng. Chem. Res.

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Functionalized ionic liquids (ILs) show great potential in the application of fuel gas desulfurization. Herein, we report the synthesis and function of two new 1,1,3,3-tetramethylguanidine-based ILs (TMG-based ILs), 1,1,3,3-tetramethylguanidine methoxyacetate ([TMG][MOAc]) and 1,1,3,3-tetramethylguanidine ethoxyacetate ([TMG][EOAc]). As contrast, two traditional TMG-based ILs, 1,1,3,3-tetramethylguanidine tetrafluoroborate ([TMG][BF4]) and 1,1,3,3-tetramethylguanidine acetate ([TMG][Ac]) were synthesized. [TMG][EOAc] exhibited the highest SO2 capacity (10.33 mol·kg–1 ILs), during which the solubility of SO2 in the ILs was investigated with a reaction equilibrium thermodynamic model (RETM). Remarkably, the absorbed SO2 transformed into cyclic sulfite esters with high yields (up to 99%) in [TMG][MOAc] without a traditional desorption process. Thanks to its good stability, the cycloaddition reaction is fully revisable in [TMG][MOAc] in five cycling measurements. These coupled applications and molecular insights demonstrate a new type of functional material for SO2 capture and its value-added conversion and also provide a new strategy to deal with harmful gas in the most convenient way.

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Modeling of H₂S, CO₂ + H₂S, and CH₄ + CO₂ Solubilities in Aqueous Monoethanolamine and Methyldiethanolamine Solutions

Cited by 15 publications

References 61 publications

Applied Artificial Neural Network for Hydrogen Sulfide Solubility in Natural Gas Purification

Applied Artificial Neural Network for Hydrogen Sulfide Solubility in Natural Gas Purification

Solving Chemical Absorption Equilibria using Free Energy and Quantum Chemistry Calculations: Methodology, Limitations, and New Open-Source Software

Guanidinium-Based Ionic Liquids for High-Performance SO₂ Capture and Efficient Conversion for Cyclic Sulfite Esters

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Modeling of H2S, CO2 + H2S, and CH4 + CO2 Solubilities in Aqueous Monoethanolamine and Methyldiethanolamine Solutions

Cited by 15 publications

References 61 publications

Applied Artificial Neural Network for Hydrogen Sulfide Solubility in Natural Gas Purification

Applied Artificial Neural Network for Hydrogen Sulfide Solubility in Natural Gas Purification

Solving Chemical Absorption Equilibria using Free Energy and Quantum Chemistry Calculations: Methodology, Limitations, and New Open-Source Software

Guanidinium-Based Ionic Liquids for High-Performance SO2 Capture and Efficient Conversion for Cyclic Sulfite Esters

Contact Info

Product

Resources

About

Modeling of H₂S, CO₂ + H₂S, and CH₄ + CO₂ Solubilities in Aqueous Monoethanolamine and Methyldiethanolamine Solutions

Guanidinium-Based Ionic Liquids for High-Performance SO₂ Capture and Efficient Conversion for Cyclic Sulfite Esters