Parametric studies of carbon dioxide absorption into highly concentrated monoethanolamine solutions

Carbon dioxide (CO₂) absorption into highly concentrated solutions of monoethanolamine (MEA) was studied. The effect of operating parameters on the overall mass transfer coefficient (K_Ga_v) was determined in a pilot‐plant scale absorption unit. The (K_Ga_v) increased at low solution concentrations, decreased at intermediate concentrations, and increased as the concentration became high (54 wt%). The (K_Ga_v) increased with an increasing liquid flow rate, decreased with an increase in either the CO₂ loading or the CO₂ partial pressure, and was not affected by the inert gas flow rate. Finally, structured 4A Gempak packing produced (K_Ga_v) values twice as high as randomly packed IMTP#15 or 16‐mm Pall Ring systems.     

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     

Mathematical modelling of mass-transfer and hydrodynamics in CO2 absorbers packed with structured packings

This paper presents a mechanistic model that can predict mass-transfer performance and provide an insight into dynamic behavior within structured packings used for CO₂ absorption. The model was built upon the kinetics and thermodynamics of the absorption system, as well as the liquid irrigation features and the geometry of packing elements. A computer program (Fortran 90) was written to simulate CO₂ absorption into aqueous solutions of sodium hydroxide (NaOH) and monoethanolamine (MEA) in a column packed with Gempak 4A, Mellapak 500Y and Mellapak 500X. The simulation gave essential information, including the concentration of CO₂ in gas-phase, concentration of reactive species in the liquid-phase, system temperature, mass-transfer coefficients (k_G and k_L), and effective interfacial area (a_e) for mass-transfer at different axial positions along the absorption column. The simulation also provided liquid distribution plots representing the quality of liquid distribution or maldistribution across the cross-section of the column. Verification of the model was achieved by comparing simulation results with experimental data. Very good agreement was found for wide ranges of operating and design parameters, including liquid load and initial liquid distribution pattern.     

Carbon dioxide absorption in a cross-flow rotating packed bed

This work investigates the feasibility of applying the cross-flow rotating packed bed (RPB) to the removal of carbon dioxide (CO₂) by absorption from gaseous streams. Monoethanolamine (MEA) aqueous solution was used as the model absorbent. Also, other absorbents such as the NaOH and 2-amino-2-methyl-1-propanol (AMP) aqueous solutions were compared with the MEA aqueous solution. The CO₂ removal efficiency was observed as functions of rotor speed, gas flow rate, liquid flow rate, MEA concentration, and CO₂ concentration. Experimental results indicated that the rotor speed positively affects the CO₂ removal efficiency. Our results further demonstrated that the CO₂ removal efficiency increased with the liquid flow rate and the MEA concentration; however, decreased with the gas flow rate and the CO₂ concentration. Additionally, the CO₂ removal efficiency for the MEA aqueous solution was superior to that for the NaOH and AMP aqueous solutions. Based on the performance comparison with the conventional packed bed and the countercurrent-flow RPB, the cross-flow RPB is an effective absorber for CO₂ absorption process.     

填料塔中碳酸钾/哌嗪混合吸收液脱除CO2的体积传质系数

The process of removing dilute CO2 from air by using me mixtures of K2CO3 and piperazine (PZ) was conducted in a random packed tower at 25℃. The results showed that PZ increased the absorption rate of CO2 into aqueous K2 CO3 much more effectively than MEA or DEA. The volumetric overall mass transfer coefficient (KGa) of dilute CO2 absorption into K2CO3/PZ was measured. The KGa value was evaluated over the ranges of main operating variables: the concentration of CO2 in inlet gas, gas flow rate, liquid loading, CO2 loading in liquid phase, and the concentrations of K2CO3 and PZ. The test showed that KGa could be remarkably improved by increasing liquid loading and the concentration of PZ, and decreasing the concentration of CO2 in inlet gas, as well as the gas flow rate and CO2 loading in liquid phase.     

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.     

Potential of different additives to improve performance of potassium carbonate for CO<Subscript>2</Subscript> absorption

The performance of potassium carbonate (K₂CO₃) solution promoted by three amines, potassium alaninate (K-Ala), potassium serinate (K-Ser) and aminoethylethanolamine (AEEA), in terms of heat of absorption, absorption capacity and rate was studied experimentally. The experiments were performed using a batch reactor, and the results were compared to pure monoethanolamine (MEA) and K₂CO₃ solutions. The heat of absorption of K₂CO₃+additive solution was calculated using the Gibbs-Helmholtz equation. In addition, a correlation for prediction of CO₂ loading was presented. The results indicated that absorption heat, absorption rate and loading capacity of CO₂ increase as the concentration of additive increases. The blend solutions have higher CO₂ loading capacity and absorption rate when compared to pure K₂CO₃. The heat of CO₂ absorption for K₂CO₃+additive solutions was found to be lower than that of the pure MEA. Among the additives, AEEA showed the highest CO₂ absorption capacity and absorption rate with K₂CO₃. In conclusion, the K₂CO₃+AEEA solution with high absorption performance can be a potential solvent to replace the existing amines for CO₂ absorption.     

Comparison of Overall Gas‐Phase Mass Transfer Coefficient for CO2 Absorption between Tertiary Amines in a Randomly Packed Column

The mass transfer performance of CO₂ absorption into an innovative tertiary amine solvent, 1‐dimethylamino‐2‐propanol (1DMA2P), was investigated and compared with that of methyldiethanolamine (MDEA) in a packed column with random Dixon‐ring packing. All experiments were conducted under atmospheric pressure. The effects of inert gas flow rate, amine concentration, liquid flow rate, CO₂ loading, and liquid temperature on mass transfer performance were analyzed and the results presented in terms of the volumetric overall mass transfer coefficient (K_Ga_v). The experimental findings clearly indicate that 1DMA2P provided better mass transfer performance than MDEA. For both 1DMA2P and MDEA solutions, the K_Ga_v increased with rising amine concentration and liquid flow rate, but decreased with higher CO₂ loading. The inert gas flow rate only slightly affected the K_Ga_v. A satisfactory correlation of K_Ga_v was developed for the 1DMA2P‐CO₂ system.     

Intensification of G/L absorption in microstructured falling film. Application to the treatment of chlorinated VOC’s – part I: Comparison between structured and microstructured packings in absorption devices

The absorption of tetrachloroethylene – the VOC – in di-ethyl-hexyl-adipate – the solvent – was carried out as an example of gaseous waste treatment. Two gas–liquid contactors were used: a column provided with as structured Sulzer EX^® packing and a microstructured falling-film absorber provided with thin vertical channels, manufactured by the Institut für Mikrotechnik Mainz (IMM). The overall transfer coefficient of VOC, K_Ga, was calculated from the absorption efficiency of the various runs carried out, allowing comparison of the two gas–liquid contactors. Due to the high solubility of the considered VOC, mass transfer was shown to be mainly controlled by gas-side transfer rates. Transfer coefficient K_Ga of the two absorbers were found to be comparable, but with gas and liquid velocity in the microstructured absorber from one to two orders of magnitude below those in the column, expressing the high transfer performance offered by the microsystem. Moreover, the thickness of the liquid film in the channels was below 100 μm, much lower than that in a structured packing near 500 μm. This shows that lower liquid flow rates can be used for efficient absorption in the microsystem. It is shown that contrary to conventional structured packing, the designed contact specific area in the microabsorber strictly corresponds to the interfacial G/L surface. This enables more compact and to miniaturize G/L contactors to be designed.     

Controllable preparation of nano-CaCO3 in a microporous tube-in-tube microchannel reactor

In this work, nano-CaCO₃ particles with tunable size have been synthesized via CO₂/Ca(OH)₂ precipitation reaction in a microporous tube-in-tube microchannel reactor (MTMCR) with a throughput capacity up to 400 L/h for CO₂ and 76.14 L/h for liquid. The overall volumetric mass-transfer coefficient (K_La) of CO₂ absorption into Ca(OH)₂ slurry in the MTMCR has been deduced and analyzed. To control the particle size, the effect of operating conditions including initial Ca(OH)₂ content, gas volumetric flow rate, liquid volumetric flow rate, micropore size, and annular channel width was investigated. The results indicated that the mass transfer in the MTMCR can be greatly enhanced in contrast with a stirred tank reactor, and the particle size can be well controlled by tuning the operating parameters. The nano-CaCO₃ particles with an average size of 28 nm and a calcite crystal structure were synthesized, indicating that this process is promising for mass production of nanoparticles.     

An experimental/computational study of steric hindrance effects on CO2 absorption in (non)aqueous amine solutions

The reaction kinetics and molecular mechanisms of CO₂ absorption using nonaqueous and aqueous monoethanolamine (MEA)/methyldiethanolamine (MDEA)/2-amino-2-methy-1-propanol (AMP) solutions were analyzed by the stopped-flow technique and ab initio molecular dynamics (AIMD) simulations. Pseudo first-order rate constants (k₀) of reactions between CO₂ and amines were measured. A kinetic model was proposed to correlate the k₀ to the amine concentration, and was proved to perform well for predicting the relationship between k₀ and the amine concentration. The experimental results showed that AMP/MDEA only took part in the deprotonation of MEA-zwitterion in nonaqueous MEA + AMP/MEA + MDEA solutions. In aqueous solutions, AMP can also react with CO₂ through base-catalyzed hydration mechanism beside the zwitterion mechanism. Molecular mechanisms of CO₂ absorption were also explored by AIMD simulations coupled with metadynamics sampling. The predicted free-energy barriers of key elementary reactions verified the kinetic model and demonstrated the different molecular mechanisms for the reaction between CO₂ and AMP.     

CO2 capture into aqueous solutions of piperazine activated 2-amino-2-methyl-1-propanol

In this work, experimental data and a simplified vapor–liquid equilibrium (VLE) model for the absorption of CO₂ into aqueous solutions of piperazine (PZ) activated 2-amino-2-methyl-1-propanol (AMP) are reported. The purpose of the work was to find the AMP/PZ system with the highest concentration and cyclic capacity, which could be used in the industry without forming solid precipitations at operational temperatures. The effect of the AMP/PZ ratio and the total concentration level of amine was studied. The highest possible ratio of AMP/PZ, which does not form solid precipitates during the absorption of CO₂ at 40 °C (40 wt% amine), was identified. Considering the maximum loading found in the screening tests for AMP/PZ (3+1.5 M) and for 30 wt% MEA systems, the AMP/PZ system has about 128% higher specific cyclic capacity if operating between 40 and 80 °C, and almost twice the CO₂ partial pressure at 120 °C compared to MEA.     

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.     

Kinetics of carbon dioxide absorption and desorption in aqueous alkanolamine solutions using a novel hemispherical contactor—II: Experimental results and parameter estimation

In Part 1 of this paper, detailed design of the hemispherical apparatus and a rigorous mathematical model applied to CO₂ absorption and desorption in and from aqueous alkanolamine solutions was presented with some preliminary results. This part of the paper provides detailed results on CO₂-amine kinetics under absorption and desorption conditions and present new estimates of the kinetic parameter for aqueous solutions of monoethanolamine (MEA), diethanolamine (DEA), methyl-diethanolamine (MDEA) and 2-amino-2-methyl-1-propanol (AMP). The absorption experiments were conducted at near atmospheric pressure with pure humidified CO₂ at 293-323 K using initially unloaded solutions. The desorption experiments were performed at 333-383 K for CO₂ loadings between 0.02 to 0.7 mol of CO₂ per mole of amine using humidified nitrogen gas as a stripping medium at total system pressure ranging from 110 to 205 kPa.The new rigorous mathematical model discussed in Part 1 was used in conjunction with a non-linear regression technique to estimate the kinetic parameters. In all cases, the new model predicts the experimental results well. Also, the new results clearly demonstrate that the theory of absorption with reversible chemical reaction could be used to predict desorption rates. The zwitterion mechanism adequately describes the reactions between CO₂ and carbamate forming amines such as MEA, DEA and AMP. The reactions between CO₂ and aqueous MDEA solutions are best described by a base-catalyzed hydration reaction mechanism. The kinetic data obtained show that desorption experiments could be used to determine both forward and backward rate constants accurately. The absorption experiments, on the other hand, could only be used to determine forward rate constants. It was found that at all operating conditions used in this study, the kinetic parameters for MEA, DEA and AMP obtained using absorption data could not be extrapolated to predict desorption rates. However, for MDEA, these data could be used successfully to obtain reasonably good predictions of desorption rates.     

CO<Subscript>2</Subscript> capture using aqueous solutions of K<Subscript>2</Subscript>CO<Subscript>3</Subscript>+2-methylpiperazine and monoethanolamine: Specific heat capacity and heat of absorption

The specific heat capacity, heat of CCO₂ absorption, and CCO₂ absorption capacity of aqueous solutions of potassium carbonate (K₂CO₃)+2-methylpiperazine (2-MPZ) and monoethanolamine (MEA) were measured over various temperatures. An aqueous solution of K₂CO₃+2-MPZ is a promising absorbent for CCO₂ capture because it has high CCO₂ absorption capacity with improved absorption rate and degradation stability. Aqueous solution of MEA was used as a reference absorbent for comprison of the thermodynamic characteristics. Specific heat capacity was measured using a differential scanning calorimeter (DSC), and heat of CCO₂ absorption and CCO₂ absorption capacity were measured using a differential reaction calorimeter (DRC). The CCO₂-loaded solutions had lower specific heat capacities than those of fresh solutions. Aqueous solutions of K₂CO₃+2-MPZ had lower specific heat capacity than those of MEA over the temperature ranges of 303-353 K. Under the typical operating conditions for the process (CCO₂ loading=0.23mol-CCO₂·mol^?1-solute in fresh solution, T=313 K), the heat of absorption (?ΔHabs) of aqueous solutions of K₂CO₃+2-MPZ and MEA were approximately 49 and 75 kJ·mol-CO₂, respectively. The thermodynamic data from this study can be used to design a process for CCO₂ capture.     

A three-zone mass transfer model for a rotating packed bed

A rotating packed bed (RPB) is recognized for its merits in chemical process intensification. In most studies of RPB mass transfer modeling, however, the effects of the end and cavity zones have not been taken into consideration, since it was very difficult to distinguish the end and bulk zones by hydrodynamics and mass transfer process. In this work, the radial thickness of the end zone was obtained by developing a probability method and imaging experiments to separate the end and bulk zones. A three-zone model, including end, bulk, and cavity zones, of the overall gas-side volumetric mass transfer coefficient (K_Ga)t was first established. Experiments of dissolved MEA chemisorption of CO₂ were carried out to validate the proposed three-zone mass transfer model. The results of the MEA-CO₂ absorption experiments showed that the experimentally obtained values of CO₂ absorption efficiency were in agreement within ±20% with the model predictions.     

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.     

CO2 absorption capacity using aqueous potassium carbonate with 2-methylpiperazine and piperazine

Various amines as a promoter have been added to the K₂CO₃ solution in order to improve the performance of the CO₂ absorption process. Piperazine (PZ) and 2-methylpiperazine (2-MPZ), cyclic diamines were used as promoters in this study. The equilibrium partial pressure of CO₂ $(P_{{\text{CO}}_2}^1)$ and pressure changes were measured at 313, 333 and 353 K condition of flue gas using VLE (vapor–liquid equilibrium) equipment. The results show that 2-MPZ possesses the ability to promote CO₂ absorption capacity. The K₂CO₃/2-MPZ solution had an equilibrium partial pressure of CO₂ that was lower than that of the MEA solution at 333 K.     

Characteristics of absorption/regeneration of CO2–SO2 binary systems into aqueous AMP + ammonia solutions

To examine the characteristics of absorption and regeneration, the simultaneous removal efficiency of carbon dioxide/sulfur dioxide (CO₂/SO₂), the CO₂ absorption amount, and the CO₂ loading value of an ammonia (NH₃) solution added to 2-amino-2-methyl-1-propanol (AMP) were investigated using the continuous absorption and regeneration process. The performances of this system, such as the removal efficiency of CO₂ and SO₂, absorption amount, and CO₂ loading, were evaluated under various operating conditions. Based on the experimental study, the optimum conditions were a liquid circulation rate of 90 mL/min and gas flow rate of 7.5 L/min. The addition of NH₃ into aqueous AMP solution increased the absorption rate and loading ratio of CO₂ and raised the removal efficiencies of CO₂ and SO₂ to over 90% and over 98%, respectively.