Efficient capture of carbon dioxide with novel mass‐transfer intensification device using ionic liquids

A novel mass‐transfer intensified approach for CO₂ capture with ionic liquids (ILs) using rotating packed bed (RPB) reactor was presented. This new approach combined the advantages of RPB as a high mass‐transfer intensification device for viscous system and IL as a novel, environmentally benign CO₂ capture media with high thermal stability and extremely low volatility. Amino‐functionalized IL (2‐hydroxyethyl)‐trimethyl‐ammonium (S)?2‐pyrrolidinecarboxylic acid salt ([Choline][Pro]) was synthesized to perform experimental examination of CO₂ capture by chemical absorption. In RPB, it took only 0.2 s to reach 0.2 mol CO₂/mol IL at 293 K, indicating that RPB was kinetically favorable to absorption of CO₂ in IL because of its efficient mass‐transfer intensification. The effects of operation parameters on CO₂ removal efficiency and IL absorbent capacity were studied. In addition, a model based on penetration theory was proposed to explore the mechanism of gas–liquid mass transfer of ILs system in RPB. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2957–2965, 2013     

Absorption of Carbon Dioxide into Aqueous Xanthan Gum Solution Containing Monoethanolamine

Abstract

Carbon dioxide was absorbed into the aqueous xanthan gum (XG) solution in the range of 0–0.151 wt% containing monoethanolamine (MEA) of 0–2 kmol/m³ in a flat‐stirred vessel with the impeller of 0.05 m and agitation speed of 50 rpm at 25°C and 0.101 MPa to measure the absorption rate of CO₂. The volumetric liquid‐side mass transfer coefficient (k_La_L) of CO₂ decreased with increasing XG concentration, and was correlated with the empirical formula having the rheological behavior of XG solution. The chemical absorption rate of CO₂ was estimated by the film theory using the values of k_La_L and physicochemical properties of CO₂ and MEA. The aqueous XG solutions made the rate of absorption of CO₂ accelerated compared with the Newtonian liquid based on the same viscosity of the solution.     

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.     

Surfactant adsorption onto activated carbon and its effect on absorption with chemical reaction

The effects of surfactant contaminations and activated carbon addition on physical gas absorption, and absorption with fast and instantaneous reaction (sulphite oxidation, carbon dioxide absorption into sodium hydroxide and monoethanol amine (MEA) solutions) have been studied in a stirred cell with a flat gas/liquid interface. Surfactants significantly decrease the liquid-side mass transfer coefficient k_L even at very small concentrations. The surfactants can be removed by adsorption onto activated carbon (“surfactant grazing”).In absorption with fast chemical reaction of the gas (sulphite oxidation), the liquid side mass transfer coefficient k_L has no effect on the absorption rate and, consequently, there are no effects of surfactant and activated carbon. CO₂ absorption into sodium hydroxide solution may occur in the instantaneous absorption regime; then, any change in k_L causes a proportional change in the absorption rate. In CO₂ absorption into MEA solution, however, in the instantaneous regime, much stronger effects of surfactant and of its removal by activated carbon are observed. It is suggested that in the absence of surfactants surface convection (Marangoni instability) may occur in MEA solutions.     

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.     

Mass‐transfer rate enhancement for CO2 separation by ionic liquids: Theoretical study on the mechanism

To promote the development of ionic liquid (IL) immobilized sorbents and supported IL membranes (SILMs) for CO₂ separation, the kinetics of CO₂ absorption/desorption in IL immobilized sorbents was studied using a novel method based on nonequilibrium thermodynamics. It shows that the apparent chemical‐potential‐based mass‐transfer coefficients of CO₂ were in three regions with three‐order difference in magnitude for the IL‐film thicknesses in microscale, 100 nm‐scale, and 10 nm‐scale. Using a diffusion‐reaction theory, it is found that by tailoring the IL‐film thickness from microscale to nanoscale, the process was altered from diffusion‐control to reaction‐control, revealing the inherent mechanism for the dramatic rate enhancement. The extension to SILMs shows that the significant improvement of CO₂ flux can be obtained theoretically for the membranes with nanoscale IL‐films, which makes it feasible to implement CO₂ separation by ILs with low investment cost. © 2015 American Institute of Chemical Engineers AIChE J, 61: 4437–4444, 2015     

Prediction of CO2/O2 absorption selectivity using supported ionic liquid membranes (SILMs) for gas–liquid membrane contactor

Given their unique and tunable properties as solvents, ionic liquids (ILs) have become a favorable solvent option in separation processes, particularly for capturing carbon dioxide (CO₂). In this work, a simple method that can be used to screen the suitable IL candidates was implemented in our modified gas–liquid membrane contactor system. Solubilities, selectivities of CO₂, nitrogen (N₂), and oxygen (O₂) gases in imidazolium-based ILs and its activity coefficients in water and monoethanolamine (MEA) were predicted using conductor-like screening model for real solvent (COSMO-RS) method over a wide range of temperature (298.15–348.15?K). Results from the analysis revealed that [emim] [NTf₂] IL is a good candidate for further absorption process attributed to its good hydrophobicity and CO₂/O₂ selectivity characteristics. While their miscibility with pure MEA was somehow higher, utilizing the aqueous phase of MEA would be beneficial in this stage. Data on absorption performances and selectivity of CO₂/O₂ are scarce especially in gas–liquid membrane contactor system. Therefore, considering [emim] [NTf₂] IL as a supporting material in supported ionic liquid membranes (SILMs), using aqueous phase of MEA as an absorbent would result in a great membrane-solvent combination system in furthering our gas–liquid membrane contactor process. In conclusion, COSMO-RS is a potentially great predictive utility to screen ILs for specified separation applications. In addition, this work provides useful results for the [emim] [NTf₂]-SILMs to be extensively applied in the field of CO₂ capture and selective O₂ removal.     

Development of ethanolamine‐based ionic liquid membranes for efficient CO2/CH4 separation

This study is focused on the development of ionic liquids (ILs) based polymeric membranes for the separation of carbon dioxide (CO₂) from methane (CH₄). The advantage of ILs in selective CO₂ absorption is that it enhances the CO₂ selective separation for the ionic liquid membranes (ILMs). ILMs are developed and characterized with two different ILs using the solution‐casting method. Three different blend compositions of ILs and polysulfone (PSF) are selected for each ILMs 10, 20, and 30 wt %. Effect of the different types of ILs such as triethanolamine formate (TEAF) and triethanolamine acetate (TEAA) are investigated on PSF‐based ILMs. Field emission scanning electron microscopy analysis of the membranes showed reasonable homogeneity between the ILs and PSF. Thermogravimetric analysis showed that by increasing the ILs loading thermal stability of the membranes improved. Mechanical analysis on developed membranes showed that ILs phase reduced the amount of plastic flow of the PSF phase and therefore, fracture takes place at gradually lower strains with increasing ILs content. Gas permeation evaluation was carried out on the developed membranes for CO₂/CH₄ separation between 2 bar to 10 bar feed pressure. Results showed that CO₂ permeance increases with the addition of ILs 10–30 wt % in ILMs. With 20–30 wt % TEAF‐ILMs and TEAA‐ILMs, the highest selectivity of a CO₂/CH₄ 53.96 ± 0.3, 37.64 ± 0.2 and CO₂ permeance 69.5 ± 0.6, 55.21 ± 0.3 is observed for treated membrane at 2–10 bar. The selectivity using mixed gas test at various CO₂/CH₄ compositions shows consistent results with the ideal gas selectivity. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45395.     

Absorption of carbon dioxide into aqueous colloidal silica solution with different sizes of silica particles containing monoethanolamine

Carbon dioxide was absorbed into an aqueous nanometer-sized colloidal silica solution in a flat-stirred vessel at 25 °C and 101.3 kPa to measure the absorption rate of CO₂. The concentrations of silica were in the range of 0–31 wt% and the sizes were 7, 60, and 111 nm. The solution contained monoethanolamine (MEA) of 0–2.0 kmol/m³. The volumetric liquid-side mass transfer coefficient (k _L a) of CO₂ was correlated with the empirical formula representing the rheological property of silica solution. The use of the aqueous colloidal silica solution resulted in a reduction of the absorption rate of CO₂ compared with Newtonian liquid based on the same viscosity of the solution. The chemical absorption rate of CO₂ was estimated by film theory using k _L a and physicochemical properties of CO₂ and MEA.     

Automated measurements of gas‐liquid mass transfer in micropacked bed reactors

Gas‐liquid mass transfer in micropacked bed reactors is characterized with an automated platform integrated with in‐line Fourier transform infrared spectroscopy. This setup enables screening of a multidimensional parameter space underlying absorption with chemical reaction. Volumetric gas‐liquid mass‐transfer coefficients (k_La) are determined for the model reaction of CO₂ absorption in a methyl diethanolamine/water solution. Parametric studies are conducted varying gas and liquid superficial velocities, packed bed dimensions and packing particle sizes. The results show that k_La values are in the range of 0.12～0.39 s^?1, which is about one‐to‐two orders of magnitude larger than those of conventional trickle beds. An empirical correlation predicts k_La in micropacked bed reactors in good agreement with experimental data. © 2017 American Institute of Chemical Engineers AIChE J, 64: 564–570, 2018     

Removal of carbon dioxide from flue gases in packed column using ionic liquids

The study of CO₂ absorption in ionic liquids (ILs): [Emim] [Ac], [Bmim] [Ac] in a packed column is presented. The influence of mass transfer resistances, initial CO₂ concentration, absorption temperature and 2, 5, 10% wt. water addition on CO₂ removal efficiency was investigated. The resistance in series model and estimated values of enhancement factor were used to predict with good accuracy mass fluxes of absorbed carbon dioxide for both ILs. The CO₂ absorption efficiency in packed column depends on temperature and initial CO₂ concentration. The addition of small amounts of water to [Emim][Ac] is of minor effect on CO₂ absorption.     

Comparison of the rate of CO2 absorption into aqueous ammonia and monoethanolamine

Aqueous ammonia has been proposed as an absorbent for use in CO₂ post combustion capture applications. It has a number of advantages over MEA such as high absorption capacity, low energy requirements for CO₂ regeneration and resistance to oxidative and thermal degradation. However, due to its small molecular weight and large vapour pressure absorption must be carried at low temperature to minimise ammonia loss. In this work the rate of CO₂ absorption into a falling thin film has been measured using a wetted-wall column for aqueous ammonia between 0.6 and 6 mol L^?1, 278–293 K and 0–0.8 liquid CO₂ loading. The results were compared to 5 mol L^?1 MEA at 303 and 313 K. It was found that the overall mass transfer coefficient for aqueous ammonia was at least 1.5–2 times smaller than MEA at the measured temperatures. From determination of the second-order reaction rate constant k₂ (915 L mol^?1 s^?1 at 283 K) and activation energy E_a (61 kJ mol^?1) it was shown that the difference in mass transfer rate is likely due to both the reduced temperature and differences in reactivity between ammonia and MEA with CO₂.     

Oxygen mass transfer coefficient in bubble column slurry reactor with ultrafine suspended particles and neural network prediction

The gas–liquid volumetric mass transfer coefficient was determined by the dynamic oxygen absorption technique using a polarographic dissolved oxygen probe and the gas–liquid interfacial area was measured using dual‐tip conductivity probes in a bubble column slurry reactor at ambient temperature and normal pressure. The solid particles used were ultrafine hollow glass microspheres with a mean diameter of 8.624 µm. The effects of various axial locations (height–diameter ratio = 1–12), superficial gas velocity (u_G = 0.011–0.085 m/s) and solid concentration (ε_S = 0–30 wt.%) on the gas–liquid volumetric mass transfer coefficient k_La_L and liquid‐side mass transfer coefficient k_L were discussed in detail in the range of operating variables investigated. Empirical correlations by dimensional analysis were obtained and feed‐forward back propagation neural network models were employed to predict the gas–liquid volumetric mass transfer coefficient and liquid‐side mass transfer coefficient for an air–water–hollow glass microspheres system in a commercial‐scale bubble column slurry reactor. © 2012 Canadian Society for Chemical Engineering     

Mass Transfer Analysis of CO2 Capture by PVDF Membrane Contactor and Ionic Liquid

Post‐combustion processes based on ionic liquids (ILs) and membrane contactors are attractive alternatives to traditional systems. Here, a gas stream composed of 15 % CO₂ and 85 % N₂ flowed through the lumen side of a hollow‐fiber membrane contactor containing poly(vinylidene fluoride)‐IL (PVDF‐IL) fibers. The IL 1‐ethyl‐3‐methylimidazolium acetate [emim][Ac] served as an absorbent due to its high chemical absorption and CO₂ solubility. The overall mass transfer coefficient (K_overall), activation energy (E_a), and resistances of the hollow‐fiber membrane were quantified. The K_overall value was one order of magnitude higher than those reported in previous works with conventional solvents, and the E_a was lower than formerly stated values for other solvents. A theoretical simulation was conducted to estimate the operational parameters required for 90 % CO₂ capture and to quantify intensification effects related to CO₂ absorption in a packed column.     

Mass transfer performance and correlations for CO2 absorption into aqueous blended of DEEA/MEA in a random packed column

The mass transfer performance of CO₂ absorption into blended N,N‐diethylethanolamine (DEEA)/ethanolamine (MEA) solutions was investigated using a lab‐scale absorber (H = 1.28 m, D = 28 mm) packed with Dixon ring random packing. The mass transfer coefficient K_Ga_v, the unit volume absorption rate Φ, outlet concentration of CO₂ (y_CO2), and the bottom temperature T_bot of CO₂ in aqueous DEEA/MEA solutions were determined over the feed temperature range of 298.15–323.15 K, lean CO₂ loading of 0.15–0.31 mol/mol, over a wide range of liquid flow rate of 3.90–9.75 m³/m²‐h, by using inert gas flow rate of 26.11–39.17 kmol/m²‐h and 6–18 kPa CO₂ partial pressure. The results show that liquid feed temperature, lean CO₂ loading, liquid flow rate, and CO₂ partial pressure had significant effect on those parameters. However, the inert gas flow rate had little effect. To allow the mass transfer data to be really utilized, K_Ga_v and y_out correlations for the prediction of mass transfer performance were proposed and discussed. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3048–3057, 2017     

Carbon Dioxide Absorption into Stirred Emulsions of n‐Alkanes

Volumetric mass transfer coefficients k_La for CO₂ absorption into n‐alkane/water emulsions were determined at oil volume fractions of 0–100 % in a stirred tank at a stirring speed of 1000 min^?1. The oil was n‐heptane, n‐hexadecane, or n‐dodecane. The decrease of k_La with increasing volume fraction of dispersed oil can be uniformly correlated to the emulsion viscosity with the power of ?0.72. Only the addition of n‐heptane caused a strong increase of the mass transfer coefficient. Upon addition of the surfactant sodium dodecyl sulfate to n‐heptane emulsions, k_La decreased as for the other oils. The increase can therefore be attributed to the spreading of n‐heptane on the bubble surface enabling gas‐oil contact, whereas spreading is inhibited by the ionic surfactant.     

Enhanced gravimetric CO2 capacity and viscosity for ionic liquids with cyanopyrrolide anion

Ionic Liquids (ILs) are considered as alternative solvents for the separation of CO₂ from flue gas due mainly to their CO₂ affinity and thermal stability. The cation architecture in a matrix of ammonium and mostly phosphonium‐based ILs with 2‐cyanopyrrolide as the anion to evaluate its impact on gravimetric CO₂ absorption capacity, viscosity, and thermal stability and the three fundamental properties vital for application realization are systematically investigated. Among the investigated ILs, [P2,2,2,8][2‐CNpyr] demonstrated the lowest viscosity, 95 cP at 40°C, and highest CO₂ uptake, 114 mg CO₂ per g IL at 40°C. Combined effects of asymmetry and the optimized chain lengths also resulted in improved thermal stability for [P2,2,2,8][2‐CNpyr], with a mass loss rate of 1.35 × 10^?6 g h^?1 (0.0067 mass % h^?1) at 80°C. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2280–2285, 2015     

UNIFAC model for ionic liquid‐CO2 systems

The new group binary interaction parameters of UNIFAC model (a_nm and a_mn) between CO₂ and 22 ionic liquid (IL) groups were obtained by means of correlating the solubility data of CO₂ in pure ILs at different temperatures (>273.2 K). We measured the CO₂ solubility at low temperatures down to 243.2 K in pure ILs, i.e., [OMIM]⁺[BF₄]^? and [OMIM]⁺[Tf₂N]^?, and their equimolar amount of mixture, in order to fill the blank of solubility data at low temperatures and also to justify the applicability of UNIFAC model over a wider temperature range. It was verified that UNIFAC model can be used for predicting the CO₂ solubility in pure ILs and in the binary mixture of ILs both at high (>273.2 K) and low temperatures (<273.2 K) effectively, as well as identifying the new structure–property relation. This is the first work to extend the UNIFAC model to IL‐CO₂ systems. © 2013 American Institute of Chemical Engineers AIChE J 60: 716–729, 2014     

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     

Instantaneous Mass Transfer under Gas‐Liquid Taylor Flow in Circular Capillaries

The mass transfer process under CO₂‐water Taylor flow was experimentally investigated in circular capillaries with different lengths. The measured volumetric mass transfer coefficient k_La was found to reduce with the increase of mass transfer time under the same operational conditions. With computational fluid dynamics simulations, the instantaneous k_La values decreased sharply at the initial stage of the mass transfer process. The effects of numerous experimental parameters on separated contribution of k_La were investigated for different dimensionless mass transfer times. The instantaneous k_La values for arbitary transfer times could be calculated and agreed well with experimental data.