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 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     

Influence of polyethylene oxide on absorption of carbon dioxide into aqueous <Emphasis Type="Italic">N</Emphasis>-methyldiethanolamine solution

Carbon dioxide was absorbed into aqueous polyethylene oxide (PEO) solution containing N-methyldiethanolamine (MDEA) in a flat-stirred vessel to investigate the effect of non-Newtonian rheological behavior of PEO on the chemical absorption rate of CO₂, where the reaction between CO₂ and MDEA was assumed to be a first-order reaction with respect to the concentration of CO₂ and MDEA, respectively. A unified correlation equation containing the Deborah number, which reflects the viscoelastic properties of a non-Newtonian liquid, was used to obtain the volumetric liquid-side mass transfer coefficient of carbon dioxide in aqueous PEO solution. The elastic properties of PEO accelerated the absorption rate of CO₂ compared with that of a Newtonian liquid based on the same values of viscosity.     

The development of kinetics model for CO2 absorption into tertiary amines containing carbonic anhydrase

CO₂ absorption into aqueous solutions of two tertiary alkanolamines, namely, MDEA and DMEA with and without carbonic anhydrase (CA) was investigated with the use of the stopped‐flow technique at temperatures in the range of 293–313 K, CA concentration varying from 0 to 100 g/m³ in aqueous MDEA solution with the amine concentration ranging from 0.1 to 0.5 kmol/m³, and CA concentration varying from 0 to 40 g/m³ in aqueous DMEA solution with the amine concentration ranging from 0.05 to 0.25 kmol/m³. The results show that the pseudofirst‐order reaction rate (k_{0, amine}; s^?1) is significantly enhanced in the presence of CA as compared with that without CA. The enhanced values of the kinetic constant in the presence of CA has been calculated and a new kinetics model for reaction of CO₂ absorption into aqueous tertiary alkanolamine solutions catalyzed by CA has been established and used to make comparisons of experimental and calculated pseudo first‐order reaction rate constant (k_{0, with CA}) in CO₂‐MDEA‐H₂O and CO₂‐DMEA‐H₂O solutions. The AADs were 15.21 and 15.17%, respectively. The effect of pKa on the CA activities has also been studied by comparison of CA activities in different tertiary amine solutions, namely, TEA, MDEA, DMEA, and DEEA. The pKa trend for amines were: DEEA > DMEA > MDEA > TEA. In contrast, the catalyst enhancement in amines was in the order: TEA> MDEA> DMEA> DEEA. Therefore, it can be seen that the catalyst enhancement in the amines decreased with their increasing pKa values. © 2017 American Institute of Chemical Engineers AIChE J, 2017     

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.     

Mass transfer investigation and operational sensitivity analysis of amine-based industrial CO2 capture plant

In this article, the industrial process of CO₂ capture using monoethanolamine as an aqueous solvent was probed carefully from the mass transfer viewpoint. The simulation of this process was done using Rate-Base model, based on two-film theory. The results were validated against real plant data. Compared to the operational unit, the error of calculating absorption percentage and CO₂ loading was estimated around 2%. The liquid temperature profiles calculated by the model agree well with the real temperature along the absorption tower, emphasizing the accuracy of this model. Operational sensitivity analysis of absorption tower was also done with the aim of determining sensitive parameters for the optimized design of absorption tower and optimized operational conditions. Hence, the sensitivity analysis was done for the flow rate of gas, the flow rate of solvent, flue gas temperature, inlet solvent temperature, CO₂ concentration in the flue gas, loading of inlet solvent, and MEA concentration in the solvent. CO₂ absorption percentage, the profile of loading, liquid temperature profile and finally profile of CO₂ mole fraction in gas phase along the absorption tower were studied. To elaborate mass transfer phenomena, enhancement factor, interfacial area, molar flux and liquid hold up were probed. The results show that regarding the CO₂ absorption, the most important parameter was the gas flow rate. Comparing liquid temperature profiles showed that the most important parameter affecting the temperature of the rich solvent was MEA concentration.     

Results from trialling aqueous NH3 based post-combustion capture in a pilot plant at Munmorah power station: Absorption

Australia's Commonwealth Scientific and Industrial Research Organization (CSIRO) and Delta Electricity have developed, commissioned and operated an A$7 million aqueous NH₃ based post-combustion capture (PCC) pilot plant at the Munmorah black coal fired power station in Australia. The results from the pilot plant trials will be used to address the gap in know-how on application of aqueous NH₃ for post-combustion capture of CO₂ and other pollutants in the flue gas and explore the potential of the NH₃ process for application in the Australia power sector. This paper is one of a series of publications to report and discuss the experimental results obtained from the pilot plant trials and primarily focuses on the absorption section.The pilot plant trials have confirmed the technical feasibility of the NH₃ based capture process. CO₂ removal efficiency of more than 85% can be achieved even with low NH₃ content of up to 6 wt%. The NH₃ process is effective for SO₂ but not for NO in the flue gas. More than 95% of SO₂ in the flue gas is removed in the pre-treatment column using NH₃. The mass transfer coefficients for CO₂ in the absorber as functions of CO₂ loading and NH₃ concentration have been obtained based on pilot plant data.     

Reduction of amine mist emissions from a pilot-scale CO2 capture process using charged colloidal gas aphrons

In the CO₂ capture process from coal-derived flue gas where amine solvents are used, the flue gas can entrain small liquid droplets into the gas stream leading to emission of the amine solvent. The entrained drops, or mist, will lead to high solvent losses and cause decreased CO₂ capture performance. In order to reduce the emissions of the fine amine droplets from CO₂ absorber, a novel method using charged colloidal gas aphron (CGA) generated by an anionic surfactant was developed. The CGA absorption process for MEA emission reduction was optimized by investigating the surfactant concentration, stirring speed of the CGA generator, and capture temperature. The results show a significant reduction of MEA emissions of over 50% in the flue gas stream exiting the absorber column of a pilot scale CO₂ capture unit.     

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.     

Simultaneous Absorption of H2S and Co2 Into Aqueous Methyldiethanolamine

Abstract

The tertiary araine methyldiethanolamine (MDEA) is finding increasing application as a chemical solvent for selective absorption of hydrogen sulfide from gases containing hydrogen sulfide and carbon dioxide. Gas streams of this type include some natural gases, synthetic gases from coal and heavy oil gasification and tail gases from sulfur plants. Selectivity for H2S is needed either to enrich Glaus sulfur plant feed in H2S or to remove only H₂S when CO₂ removal is not necessary or economic. For the absorption of hydrogen sulfide into MDEA, the reaction which occurs can be considered to be instantaneous while carbon dioxide undergoes a second-order reaction with MDEA.

In this work, the simultaneous absorption of two gases into a liquid containing a reactant with which both gases react is modelled using the film theory. Physical properties and kinetic rate parameters used in the model have been measured in our laboratory. The model is used to study the effect of process variables on the selectivity of MDEA for H₂S over C0₂. The simultaneous absorption of H₂S and CO₂ gases into aqueous MDEA is studied experimentally using a continuous stirred tank absorber. Experimental absorption rates are compared to predictions based on a multicomponent mass transfer model. The average deviations of the theoretical calculations from the experimental results are 10.2% and 12.9% for C0₂ and H₂S, respectively.     

Absorption of co2 into aqueous tertiary amine/mea solutions

Absorption rates for CO₂ into aqueous solutions of TEA, MDEA and blends of MEA with MDEA and TEA were measured in a stirred cell by a method similar to that used by Laddha and Danckwerts (1981). Second order rate constants for CO₂-TEA and CO₂-MDEA were obtained from the single amine data for temperatures in the range of 25-60°C. A modified pseudo first order model based on the film theory is used to predict the rate of absorption of CO₂ into mixed amine solutions. This model accounts for the variation of amine concentration in the film and assumes a shuttle mechanism for rate enhancement. Bulk liquid concentrations of the various species present are obtained from a simplified thermodynamic model. The model predicts absorption rates that are in agreement with experimental measurements.     

Numerical simulation of CO2 absorption into aqueous methyldiethanolamine solutions

The CO₂ absorption rate into aqueous N-methyldiethanolamine solutions was measured using a stirred cell with a flat gas-liquid interface. The measurements were performed in the temperature range of 293.15 to 333.15 K for various amine concentrations and CO₂ partial pressures. A numerical model of mass-transfer with complex chemical reactions based on the film theory was developed to interpret the experimental results. The model predictions have been found to be in good agreement with the experimental values of CO₂ absorption rates. A comparison is made between the enhancement factor predicted from the detailed model and the approximate solution of mass transfer equations with chemical reaction. The numerical results indicate that under the present experimental conditions, the effect of the reaction between CO₂ and OH^? on the observed mass transfer rates is negligible. The detailed mass transfer model was used for simulating the CO₂ absorption process in terms of the enhancement factor under a variety of operating conditions.     

Mass Transfer Flux of CO2 into Methyldiethanolamine Solution in a Reactive-Absorption Process

The mass transfer parameters of both gas and liquid phases affect the mass transfer flux of CO₂ in absorption processes. In this study, an accurate correlation is proposed to calculate the CO₂ mass transfer flux in an absorption-reactive process by methyldiethanolamine (MDEA) solution using the Buckingham π theorem. The various parameters include film parameter, CO₂ loading, concentration ratio, partial-to-total pressure ratio, film thickness ratio, and diffusion ratio which are incorporated in the model. An average absolute relative error of 4.4 % for the calculation of mass transfer flux was stated.     

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.     

Separation of CO2 by 2-amino-2-methyl-1-propanol aqueous solution in microporous hydrophobie hollow fiber contained liquid membrane

The absorption of CO₂ from a mixture of CO₂/N₂ gas was carried out using a flat-stirred vessel and the polytetrafluoroethylene hollow fiber contained aqueous 2-amino-2-methyl-1-propanol (AMP) solution. The reaction of CO₂ with AMP was confirmed to be a second order reversible reaction with fast-reaction region. The mass transfer resistance in the membrane side obtained from the comparison of the measured absorption rates of CO₂ in a hollow fiber contained liquid membrane with a flat-stirred vessel corresponded to about 90% of overall-mass-transfer resistance. The mass transfer coefficient of hollow fiber phase could be evaluated, which was independent of CO₂ loading.     

PGSS-drying: Mechanisms and modeling

Micronization of polyethylene glycol from aqueous solutions has been successfully performed with particles from gas-saturated solutions (PGSS)-drying process, producing spherical PEG particles with average particle size of 10 μm and residual water content below 1 wt%. Based on experimental results, an analysis of the fundamentals of the process has been developed, discussing mass and energy balances, phase equilibrium conditions, mass transfer rates and atomization mechanisms. Some discrepancies between experimentally observed moisture concentration in powder and calculations based on the mass balance and the phase equilibrium have been observed, which have been attributed to the kinetic evolution of pressure and temperature along the expansion path. The static mixer used to saturate the solution with CO₂ has been analyzed with phase equilibrium and mass transfer calculations, concluding that a significant fraction of water is extracted to the gas phase already in the static mixer, and high CO₂ concentrations are achieved in the liquid due to the high solubility of CO₂ in PEG. All experimental trends of variation of particle size with process parameters can be explained considering a flash-boiling atomization mechanism dependant on the concentration of CO₂ in the solution after the static mixer.     

A study on the reaction between CO2 and alkanolamines in aqueous solutions

Literature data on the rates of reaction between CO₂ and alkanolamines (MEA, DEA, DIPA, TEA and MDEA) in aqueous solution are discussed. These data induced us to carry out absorption experiments of CO₂ into aqueous DEA, DIPA, TEA and MDEA solutions from which the respective rate constantsThe results for DEA and DIPA were analysed by means of a zwitterion-mechanism which was derived from the mechanism originally proposed by Danckwerts [1The reaction rate of CO₂ with aqueous TEA and MDEA solutions shows a significant base catalysis effect which is also reported by Donaldson and Nguy     

Characteristics of CO2 Absorption into Aqueous Ammonia

Abstract

Aqueous ammonia was investigated as a new absorbent of the chemical absorption process for CO₂ capture from combustion flue gas. The effects of the temperature and concentration of aqueous ammonia on CO₂ absorption in a semi‐batch reactor were studied by interpreting breakthrough curves. Raman spectroscopy analysis of CO₂ loaded aqueous ammonia provided concentration changes of bicarbonate, carbonate, and carbamate as well as CO₂ sorption capacity at given time during the absorption with 13 wt% aqueous ammonia at 25°C. It was observed that carbamate formation was dominating at the early stage of absorption. Then, the bicarbonate formation took over the domination at the later stage while the carbonate remained unchanged.     

Enhancement of CO2 capture in the MDEA solution by introducing TETA or TETA-AEP mixtures as an activator

TETA or TETA-AEP mixtures were used as an activator to enhance CO₂ capture in the MDEA solution. The effect of amount and type of activators, and the viscosity of absorbents on CO₂ capture were discussed. The results showed that the positive effect of TETA-AEP mixtures on CO₂ capture in the MDEA solution was greater than that of TETA. The optimal absorbent was No. V, whose CO₂ absorption capacity/desorption efficiency was 3.08 times/1.18 times of No. ?. The viscosity had a little influence on CO₂ absorption and an obvious effect on CO₂ desorption.     

Carbon dioxide absorption kinetics in potassium threonate

The absorption of carbon dioxide in potassium threonate aqueous solutions is studied at concentrations ranging from 0.1 to 3 M and temperatures from 293 to 313 K. This study includes experimental density, viscosity, solubility of N₂O and absorption kinetics of CO₂ (using a stirred cell reactor) data obtained for the various potassium threonate solutions. The diffusion coefficients of CO₂ and potassium threonate in the absorption solutions are estimated using a modified Stokes-Einstein relation. N₂O solubility is interpreted using the Schumpe [1993. The estimation of gas solubilities in salt-solutions. Chemical Engineering Science 48(1), 153-158] model and CO₂ physical solubility estimated. Physical absorption experiments were performed in the stirred cell in order to determine the physical mass transfer coefficients. The kinetics results are interpreted using both the pseudo-first-order and the DeCoursey approaches. It was concluded that CO₂ absorption in the aqueous potassium threonate solutions is well represented by