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     

Numerical simulation of the mass transfer process of CO2 absorption by different solutions in a microchannel

The flow and mass transfer characteristics of CO₂ absorption in different liquid phases in a microchannel were studied by numerical simulation. The mixture gas phase contained 5 vol% CO₂ and 95 vol% N₂ , and the different liquid phases were water, ethanol solution, 0.2 M monoethanolamine solution, and 0.2 M NaOH solution, respectively. Based on the permeation theory, the distribution of velocity and concentration in the slug flow was obtained by local simulation of flow and mass transfer coupling and was described in depth. The influence of contact time and bubble velocity on the mass transfer of the whole bubble was highlighted. The volumetric mass transfer coefficient on the bubble cap and liquid film, CO₂ absorption rate, and enhancement factor were calculated and analyzed. The results showed that the volumetric mass transfer coefficients of chemical absorption were ~3 to 10 times that of physical absorption and the CO₂ was absorbed more completely in chemical absorption. The new empirical correlations for predicting the mass transfer coefficient of the liquid phase were proposed respectively in physical absorption and chemical absorption, which were compared with the empirical formulas in the literature. The volumetric mass transfer coefficients obtained by predictive correlations are in good agreement with those obtained by simulation in this paper. This work made a basic prediction for CO₂ absorption in microchannel and provides a foundation for later experimental research.     

Absorption of carbon dioxide into aqueous blends of 2-amino-2-methyl-1-propanol and monoethanolamine

This work presents an investigation of CO₂ absorption into aqueous blends of 2-amino-2-methyl-1-propanol (AMP) and monoethanolamine (MEA). The acid gas mass transfer has been modeled using equilibrium-mass transfer-kinetics-based combined model to describe CO₂ absorption into the amine blends according to Higbie's penetration theory. The effect of contact time and relative amine concentration on the rate of absorption and enhancement factor were studied by absorption experiment in a wetted wall column at atmospheric pressure. The model was used to estimate the rate coefficient of the reaction between CO₂ and monoethanolamine at 313 K from experimentally measured absorption rates. A rigorous parametric sensitivity test has been done to identify the key systems’ parameters and quantify their effects on the mass transfer using the mathematical model developed in this work. The model predictions have been found to be in good agreement with the experimental rates of absorption of CO₂ into (AMP+MEA+H₂O).     

Removal of carbon dioxide by absorption in mixed amines: modelling of absorption in aqueous MDEA/MEA and AMP/MEA solutions

This work presents an investigation of CO₂ absorption into aqueous blends of methyldiethanolamine (MDEA) and monoethanolamine (MEA), as well as 2-amino-2-methyl-1-propanol (AMP) and monoethanolamine (MEA). The combined mass transfer–reaction kinetics–equilibrium model to describe CO₂ absorption into the amine blends has been developed according to Higbie's penetration theory following the work of Hagewiesche et al. (Chem. Eng. Sci. 50 (1995) 1071). The model predictions have been found to be in good agreement with the experimental rates of absorption of CO₂ into (MDEA+MEA+H₂O) of this work and into (AMP+MEA+H₂O) reported by Xiao et al. (Chem. Eng. Sci. 55 (2000) 161), measured at higher contact times using wetted wall contactor. The good agreement between the model predicted rates and enhancement factors and the experimental results indicate that the combined mass transfer–reaction kinetics–equilibrium model with the appropriate use of model parameters can effectively represent CO₂ mass transfer for the aqueous amine blends MDEA/MEA and AMP/MEA.     

Absorption of carbon dioxide into aqueous blends of 2-amino-2-methyl-1-propanol and diethanolamine

This work presents an experimental and theoretical investigation of CO₂ absorption into aqueous blends of 2-amino-2-methyl-1-propanol (AMP) and diethanolamine (DEA). The CO₂ absorption into the amine blends is described by a combined mass transfer-reaction kinetics-equilibrium model, developed according to Higbie's penetration theory. The model predictions have been found to be in good agreement with the experimental rates of absorption of CO₂ into (AMP+DEA+H₂O). The good agreement between the model predicted rates and enhancement factors and the experimental results indicate that the combined mass transfer-reaction kinetics-equilibrium model with the appropriate use of model parameters can effectively represent CO₂ mass transfer for the aqueous amine blends AMP/DEA.     

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 carbon dioxide into aqueous solutions of piperazine activated 2-amino-2-methyl-1-propanol

In this work, new experimental data on the rate of absorption of CO₂ into piperazine (PZ) activated aqueous solutions of 2-amino-2-methyl-1-propanol (AMP) are reported. The absorption experiments using a wetted wall contactor have been carried out over the temperature range of 298-313 K and CO₂ partial pressure range of 2-14 kPa. PZ is used as a rate activator with a concentration ranging from 2 to 8 wt%, keeping the total amine concentration in the solution at 30 wt%. The CO₂ absorption into the aqueous amine solutions is described by a combined mass transfer-reaction kinetics-equilibrium model, developed according to Higbie's penetration theory. Parametric sensitivity analysis is done to determine the effects of possible errors in the model parameters on the accuracy of the calculated CO₂ absorption rates from the model. The model predictions have been found to be in good agreement with the experimental results of rates of absorption of CO₂ into aqueous (PZ+AMP). The good agreement between the model predicted rates and enhancement factors and the experimental results indicates that the combined mass transfer-reaction kinetics-equilibrium model with the appropriate use of model parameters can effectively represent CO₂ mass transfer in PZ activated aqueous AMP solutions.     

Chemical Absorption of Carbon Dioxide into Aqueous PEO Solution of Monoethanolamine

Abstract

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

Absorption of Carbon Dioxide into Ionic Liquid of 2-Hydroxy Ethylammonium Lactate

Abstract

Absorption of carbon dioxide into organic solvents such as DMA, NMP, DMSO, and DMF with the 2-hydroxy ethylammonium lactate (HEAL) ionic liquid was investigated using a batch stirred tank with a plane of gas-liquid interface in a range of 0–2.0 kmol/m³ of HEAL and 298–318 K at 101.3 kPa. The absorption of CO₂ was analyzed with the film model accompanied by the zwitterion mechanism of CO₂ with HEAL. The proposed model fits the experimental data of the enhancement factor due to the ready, chemical absorption of CO₂ in different solvents, temperatures, and HEAL concentrations. The reaction rate constant of CO₂ with HEAL was correlated linearly with the solubility parameter of the solvent.     

Effect of Chemical Reaction and Mass Transfer on Ozonation of the Azo Dyes Reactive Black 5 and Reactive Orange 96

Ozonation of wastewater containing azo dye has been studied to evaluate the enhancement of ozone mass transfer from O₂O₃ gas into water with the presence of chemical reactions in a bubble column reactor. Experiments were performed at different initial dye concentrations and at various gas flow rates. C.I. Reactive Black 5 (RB 5) and C.I. Reactive Orange 96 (RO 96) have been chosen as representative model substances being found in wastewater from textile-finishing wastewater. Results show that the rate of ozone mass transfer increases with increasing initial dye concentration and gas flow rate. Consequently, an enhancement factor E for ozone mass transfer with chemical reaction could be calculated which increases with dye concentration. The chemical reaction between ozone and dye enhanced the mass transfer within the liquid film of the gas liquid boundary. The greatest enhancement factor for wastewater containing RO 96 of 2050 mgL^?1 is E = 15.4 compared with E = 9.1 for RB 5 of 3800 mgL^?1, both for gas flow rates of 19 Lh^?1. For lower gas flow rates, higher enhancement factors were observed, particularly for RO 96.     

Absorption of carbon dioxide in aqueous MDEA solution coupling dust suppression under atomization

ABSTRACT

Large amounts of CO₂ and dust particles coming from power plant flue need to be captured and removed before flue is discharged into the air. In present work, absorption of carbon dioxide in aqueous N-methylidiethanolamine (MDEA) solution coupling dust suppression has been studied in an atomization absorption column, with MDEA concentrations ranging from 0.1 to 0.5mol/L, and with atomization frequencies ranging from 50 to 80 HZ. The obtained experimental results show that absorption rate of CO₂ in aqueous MDEA solution can be enhanced when the absorption process couples a dust suppression one under the condition of atomization. The reason for it is attributed to the adsorption of droplets on the solid particles which restrains the amount of entrainment and makes more droplets contact with gas so as to increase effective mass transfer area, thus resulting in the increase of CO₂ absorption rate. The range of obtained enhancement factor is from 1.1 to 1.7. Mass transfer enhancement factor increases with the increase of MDEA concentration and atomization frequency at a certain range. Effective mass transfer areas and entrainment ratios suppressed have been calculated based on theoretic research. The results calculated agree with our experimental phenomena, and support the enhancement mass transfer mechanism proposed.     

A model of acid gas absorption/stripping using methyldiethanolamine with added acid

A nonequilibrium stage model was developed for the absorption and stripping of H₂S and CO₂ using aqueous methyldiethanolamine (MDEA). Heat and mass transfer are calculated for each stage assuming the liquid is well mixed and the gas moves in plug flow. The vapour-liquid equilibrium is represented by an empirical expression that was fit to experimental data. The mass transfer enhancement factor for CO₂ is based on the surface renewal theory with approximations made to the reaction term by the method of DeCoursey. Calculation of H₂S absorption assumes an instantaneous reaction rate at the gas/liquid interface and accounts for enhancement by equilibrium chemical reactions. Results were generated at Claus tail gas conditions using available equilibrium and rate data for 50 wt% MDEA. The amount of H₂S in the absorber outlet gas, or H₂S leak, was used to measure system performance. The base case resulted in a H₂S leak of 98 ppm with 20 absorber stages, 25 stripper stages, and a steam rate of 1.7 lb/gal solvent. Adding 0.05 equivalents of acid per mole of MDEA to the aqueous solution reduced the H₂S leak to 6 ppm and the steam rate to 1.2 lb/gal. Reducing the base case stripper pressure of 2.0 atm to 1.0 atm reduced the H₂S leak to 22 ppm. Analysis of McCabe-Thiele plots generated by the model showed that system performance improved after adding acid or reducing the stripper pressure because the H₂S equilibrium in the stripper was linearized.     

Absorption of carbon dioxide into glycidyl methacrylate solution containing the triethylamine immobilized ionic liquid on MCM-41 catalyst

An ionic liquid (TEA-MS41), triethylamine-immobilized on chloropropyl-functionalized MCM-41, was synthesized by a grafting technique through a co-condensation method and used as a catalyst in the reaction of carbon dioxide with glycidyl methacrylate (GMA). CO₂ was absorbed into the heterogeneous system of the GMA solution and dispersed with solid particles of the catalyst in a batch stirred tank with a plane gas-liquid interface at 101.3 kPa. The absorption of CO₂ was analyzed by using mass transfer accompanied by chemical reactions based on film theory. The proposed model fits the measured data of the enhancement factor to obtain the reaction rate constants. Solvents such as N,N-dimethylacetamide, N-methyl-2-pyrrolidinone, and dimethyl sulfoxide influenced the reaction rate constants.     

Simultaneous absorption of carbon dioxide,sulfur dioxide,and nitrogen dioxide into aqueous 1, 8-diamino-p-menthane

3 gaseous mixtures of CO₂, SO₂, and NO₂ were simultaneously absorbed into 1, 8-diamino-p-menthane (DAM) in a stirred, semi-batch tank with a planar, gas-liquid interface within a range of 0–2.0 kmol/m³ of DAM, 0.05–0.3 atm of CO₂, 0.0025–0.04 atm of SO₂, and 298.15–323.15 K at a fixed NO₂ of 0.001 atm to measure their total molar fluxes. Diffusivity and Henry constants of CO₂, SO₂, and NO₂ were obtained using the reference data, measured by N₂O analogy. The mass transfer coefficient of each gas, needed to obtain the absorption rate without a chemical reaction, was modified with viscosity of aqueous DAM solution. In CO₂-SO₂-NO₂-DAM system accompanied by first-order reaction with respect to CO₂ and instantaneous reactions with respect to SO₂ and NO₂, the enhancement factors of CO₂ and SO₂ were obtained by using an approximate solution of mass balances consisting of reaction regimes of two gases, one of which reacts instantaneously, and then, the enhancement factor of NO₂ by comparing the instantaneous rates of SO₂ and NO₂. The observed values of the molar flux approached to the calculated values very well.     

Microporous hollow fibres for carbon dioxide absorption: Mass transfer model fitting and the supplying of carbon dioxide to microalgal cultures

A method of supplying CO₂ to photosynthetic algal cultures was developed based on mass transfer measurements of CO₂ through microporous hydrophobic hollow fibres for various gas and liquid flow rates. A mathematical model was derived to describe the mass transfer. The designed hollow fibre module led to overall mass transfer coefficient values ranging from 1·26 × 10⁻³ to 2·64 × 10⁻³ cm s⁻¹. Higher efficiencies of the CO₂ transmission were obtained at high liquid flow rates and low gas flow rates. The use of microporous hydrophobic hollow fibres enabled an enhancement of the carbon dioxide transfer per area of membrane surface by a factor of 10, in comparison to operation with silicone tubing. The hollow fibre module was operated in an external bypass to a 1 dm³ microalgae culture vessel. In this system the algal growth pattern was similar to that obtained with a control culture where CO₂ was bubbled. However, the dissolved oxygen concentration was always lower in the vessel in which CO₂ was supplied by the module. © 1998 SCI.     

Simultaneous absorption of carbon dioxide,sulfur dioxide and nitrogen dioxide into aqueous 2-amino-2-methy-1-propanol

The absorption mechanism of three acidic gases in alkali solution, such as the system of carbon dioxide, sulfur dioxide, and nitrogen dioxide in 2-amino-2-methyl-1-propanol (AMP), was used to predict the simultaneous absorption rates using the film theory. Diffusivity, Henry constant and mass transfer coefficient of each gas were used to obtain the theoretical enhancement factor of each component. The theoretical molar fluxe of each gas was obtained by an approximate solution of mass balances with reaction regions of the first order reaction of CO₂ and instantaneous reactions of SO₂ and NO₂ in CO₂-SO₂-NO₂-AMP system. From the comparison between the theoretical total fluxes of these gases and the measured ones, the solubility and the reaction rate between each gas and AMP influenced its molar flux.     

Enhanced weathering to capture atmospheric carbon dioxide: Modeling of a trickle-bed reactor

Enhanced weathering (EW) of alkaline minerals can potentially capture CO₂ from the atmosphere at gigaton scale, but the reactor design presents great challenges. We model EW with fresh water in a counter-current trickle flow packed bed batch of 1–10 mm calcite particles. Weathering kinetics are integrated with the mass transfer of CO₂ incorporating transfer enhancement by chemical reaction. To avoid flooding, flow rates must be reduced as the particles shrink due to EW. The capture rate is mainly limited by slow transfer of CO₂ from gas to liquid although slow dissolution of calcite can also play a role in certain circumstances. A bed height of at least 7–8 m is required to provide sufficient residence time. The results highlight the need to improve capture rate and reduce energy and water consumption, possibly through enriching the feed with CO₂ and further chemical acceleration of the mass transfer.     

Numerical calculation of simultaneous mass transfer of two gases accompanied by complex reversible reactions

A discretization technique is described, which makes it possible to calculate numerically mass transfer behaviour between two media in which complex chemical reactions occur. To show the stability of the technique it has been applied to the industrially well-known system of simultaneous absorption or desorption of H₂S and CO₂ to or from an amine solution, accompanied by simultaneously occurring strongly interfering overall chemical reaction(s) of complex, non elementary kinetics. For previously published limit cases of the transfer system considered, i.e. for the single transfer of H₂S or CO₂ accompanied by reversible chemical reaction, a comparison has been made with analytical and approximate solutions of previous authors. The agreement is very good. In studying simultaneous transfer of H₂S and CO₂, on which hardly any previous work was available, special attention has been paid to the effects of the reversibility of the reactions involved. It has been shown how, under certain conditions due to reversibility occurring in the transferzone, desorption takes place though absorption would be expected on basis of the driving forces. This revealed that not only enhancement factors larger than unity but also smaller, even negative values are possible.     

Dynamic modeling and simulation of absorption of carbon dioxide into seawater

In order to elucidate the dynamic performance of the CO₂ ocean disposal process, effects of operating parameters, such as gas flow rate, salinity and temperature, on the absorption of CO₂ into seawater were examined. The rate-based model consisting of the rates of chemical reaction and gas-liquid mass transfer was developed for simulating dynamic process of CO₂ ocean disposal. In modeling, non-ideal mixing characteristics in the gas and liquid phases are described using a tanks-in-series model with backflow. Experiments were performed to verify dynamic CO₂ absorption prediction capability of the proposed model in a cylindrical bubble column. The operation was batch and continuous with respect to liquid phase and gas phase, respectively. Experimental results indicate that the CO₂ gas injection rate increased the absorption rate but the increase in salinity concentration caused inhibition of the absorption of CO₂. The proposed model could describe the present experimental results for the dynamic changes and the steady-state values of dissolved CO₂ concentration and hydrogen ion concentration. The proposed model might effectively handle the prediction of the absorption of CO₂ into seawater in the CO₂ ocean disposal.     

Computational fluid dynamics simulation of reactive absorption of CO2 in a structured packed column

In this study, multiphase Eulerian computational fluid dynamics (CFD) modelling is developed to predict the hydrodynamics, mass transfer, and chemical absorption of CO₂ using a monoethanolamine (MEA) solution in a structured packed column. First, the hydrodynamic simulation of liquid dispersion in a structured packed bed using a two-dimensional CFD is performed. The simulation results of the radial distribution of the liquid holdup are compared with the literature experimental data. The model prediction matches the experimental data at the top position of the column, whereas a slight deviation is found at the bottom position of the column. Using a validated CFD model, the reactive mass transfer is modelled to study CO₂ capture in a structured packed column with Mellapak 500.X. The model results are compared to the literature experimental results of CO₂ mole fractions along the height of the column. It is found that the model results match the experimental findings. Furthermore, CFD modelling is extended to investigate the influence of operating conditions such as gas and liquid velocities on CO₂ removal efficiency. The present CFD model demonstrates the porous media approach for reactive absorption of CO₂ in a structural packed bed.