Degradation of alkanolamine blends by carbon dioxide

Aqueous solutions of MDEA, MDEA + DEA and MDEA + MEA containing 4.2 kmol/m³ total amine, were contacted with CO₂ at a partial pressure of 2.58 MPa and temperatures ranging from 120 to 180°C, in a stainless steel batch reactor. The reaction products include the known degradation compounds of the amines as well as products formed from secondary interactions in the amine blends. The rate of degradation was first order in the amines and, in magnitude, followed the sequence MDEA < MEA < DEA. Furthermore, the rate constant for MDEA was independent of amine substitution level and blend constituents. From a practical standpoint, MDEA + DEA blends would require frequent DEA make-up to maintain treating efficiency.     

Absorption of carbon dioxide in alkanolamines in the presence of fine activated carbon particles

The rates of absorption of CO₂ into water and 0.1 kmol/m³ aqueous solutions of MEA, DEA and AMP were measured in a stirred cell with a flat gas-liquid interface in the presence of fine activated carbon particles. Experiments showed that the rates of absorption increased significantly with increases in the loading of activated carbon up to about 6 kg/m³ and thereafter remained constant.     

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.     

The solubility of carbon dioxide and hydrogen sulfide in a 35 wt% aqueous solution of methyldiethanolamine

The solubility of hydrogen sulfide and carbon dioxide in an aqueous solution containing 35 wt% methyldiethanolamine (MDEA) (3.04 kmol/m³, 4.52 mol/kg) has been measured at 40° and 100°C at partial pressures of the acid gas up to 530 kPa. Some data for hydrogen sulfide in a 50 wt% solution of MDEA (4.38 kmol/m³, 8.39 mol/kg) were also obtained. Also, densities of CO₂-aqueous MDEA solutions were measured at 40°C.     

A comparative kinetics study of CO2 absorption into aqueous DEEA/MEA and DMEA/MEA blended solutions

The kinetics of CO₂ absorption into aqueous solutions of N,N‐diethylethanolamine (DEEA), and N,N‐dimethylethanolamine (DMEA), and their blends with monoethanolamine (MEA) have been studied in a stopped‐flow apparatus. The kinetics experiments were carried out at the concentrations of DEEA and DMEA varying from 0.075 to 0.175 kmol/m³, respectively, and that of MEA ranging between 0.0075 and 0.0175 kmol/m³, over the temperature range of 293–313 K. Two kinetics models are proposed to interpret the reaction in the blended amine systems and the results show that the model which incorporates the base‐catalyzed hydration mechanism and termolecular mechanism resulted in a better prediction. Furthermore, the kinetics behaviors of CO₂ absorption into two blended systems are comprehensively discussed according to their molecular structures. It can be concluded that the interaction between tertiary amines and primary amines as well as the alkyl chain length of tertiary amines have a significant influence on the kinetics. © 2017 American Institute of Chemical Engineers AIChE J, 64: 1350–1358, 2018     

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     

Investigation mechanism of DEA as an activator on aqueous MEA solution for postcombustion CO2 capture

In this work, Diethanolamine (DEA) was considered as an activator to enhance the CO₂ capture performance of Monoethanolamine (MEA). The addition of DEA into MEA system was expected to improve disadvantages of MEA on regeneration heat, degradation, and corrosivity. To understand the reaction mechanism of blended MEA‐DEA solvent and CO₂, ¹³C nuclear magnetic resonance (NMR) technique was used to study the ions (MEACOO^‐, DEACOO^–, MEA, DEA, MEAH⁺, DEAH⁺, , ) speciation in the blended MEA‐DEA‐CO₂‐H₂O systems with CO₂ loading range from 0 to 0.7 mol CO₂/mol amine at the temperature of 301 K. The different ratios of MEA and DEA (MEA: DEA = 2.0:0, 1.5:0.5, 1.0:1.0, and 0:2.0) were studied to comprehensively investigate the role of DEA in the system of MEA‐DEA‐CO₂‐H₂O. The results revealed that DEA performs the coordinative role at the low CO₂ loading and the competitive role at high CO₂ loading. Additionally, the mechanism was also proposed to interpret the reaction process of the blended solvent with CO₂. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2515–2525, 2018     

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.     

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.     

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     

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     

Absorption of carbon dioxide into aqueous solution of 2-amino-2-methy-1-propanol and 1, 8-diamino-p-menthane

Carbon dioxide was absorbed into an aqueous solution containing two reactants of 2-amino-2-methyl-1-propanol (AMP) and 1,8-diamino-p-menthane (DAM) in a stirred semi-batch tank with a planar gas-liquid interface within a range of 0?C3.0 kmol/m³ of AMP, 0?C0.2 kmol/m³ of DAM, and 298.15?C323.15 K at 15% of CO₂ and 101.3 kPa. Diffusivity, Henry constant and mass transfer coefficient of CO₂ in the mixed solution of AMP and DAM were used to calculate the theoretical enhancement factor of CO₂, which was obtained by an approximated solution of mass balances with the instantaneous and fast regime in CO₂-AMP-DAM system. The method of the classification of the chemical regime in the heterogeneous system was used to determine the enhancement factor by adding DAM under the limited concentration of AMP.     

Investigation of CO2 solubility in monoethanolamine hydrochloride based deep eutectic solvents and physical properties measurements

Deep eutectic solvents (DESs) have drawn a growing research interest for applications in a wide range of scientific and industrial arenas. However, a limited effort has been reported in the area of gas separation processes and particularly the carbon dioxide capture. This study introduces a novel set of DESs that were prepared by complexing ethylenediamine (EDA), monoethanolamine (MEA), tetraethylenepentamine (TEPA), triethylenetetramine (TETA) and diethylenetriamine (DETA) as hydrogen bond donors to monoethanolamide hydrochloride (EAHC) salt as a hydrogen bond acceptor. The absorption capacity of CO₂ was evaluated by exploiting a method based on measuring the pressure drop during the absorption process. The solubility of different DESs was studied at a temperature of 313.15 K and initial pressure of 0.8 MPa. The DES systems 1EAHC:9DETA, 1EAHC:9TETA and 1EAHC:9TEPA achieved the highest CO₂ solubility of 0.6611, 0.6572 and 0.7017 mol CO₂·(mole DES)⁻¹ respectively. The results showed that CO₂ solubility in the DESs increased with increasing the molar ratio of hydrogen bond donor. In addition, the CO₂ solubility increased as the number of amine groups in the solvent increases, therefore, increasing the alkyl chain length in the DESs, resulted in increasing the CO₂ solubility. FTIR analysis confirms the DES synthesis since no new functional group was identified. The FTIR spectra also revealed the carbamate formation in DES-CO₂ mixtures. In addition, the densities and viscosities of the synthesized DESs were also measured. The CO₂ initial investigation of reported DESs shows that these can be potential alternative for conventional solvents in CO₂ capture processes.     

Selective Removal of Carbon Dioxide from Wet CO2/H2 Mixtures via Facilitated Transport Membranes containing Amine Blends as Carriers

The selective separation of carbon dioxide (CO₂) from a wet gaseous mixture of CO₂/H₂ through facilitated transport membranes containing immobilized aqueous solutions of monoethanolamine (MEA), diethanolamine (DEA), ethylenediamine (EDA) and monoprotonated ethylenediamine (EDAH⁺) and their blends was experimentally investigated. The effect of CO₂ partial pressure, amine concentration, feed side pressure and amine species on the CO₂ and H₂ permeances were studied. The CO₂ permeability through amine solution membranes decreased with increasing CO₂ feed partial pressure but the H₂ permeance was almost independent of the H₂ partial pressure. A comparison of experimental results showed that single or blended amines with low viscosity and a moderate equilibrium constant, i.e., large forward and reverse reaction rate of CO₂‐amine, are suitable for effective separation of CO₂. The permeability of CO₂ generally increased with an increase in amine concentration, although this increase may be compromised by the salting out effect and decrease in diffusivities of species. The results obtained indicated that CO₂ permeance across a variety of amines are in the order of DEA (2 M) > MD (2 M) > MD (1 M) > MEA (2 M) > MEA (4 M) > MD (4 M) > DEA (1 M) > DEA (4 M) > MEA (1 M) for various concentrations of MEA + DEA blend and are in the order of EDAH⁺ (2 M) > DEA (2 M) > MH (2 M) > DH (2 M) > ED (2 M) > EDA (2 M) > MEA (2 M) for various blends of amine.     

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 constants were derived. The experimental technique was similar to that used by Laddha and Danckwerts[30].The results for DEA and DIPA were analysed by means of a zwitterion-mechanism which was derived from the mechanism originally proposed by Danckwerts[16The reaction rate of CO₂ with aqueous TEA and MDEA solutions shows a significant base catalysis effect which is also reported by Donaldson and Nguy     

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.     

The absorption rate of CO2/SO2/NO2 into a blended aqueous AMP/ammonia solution

The Inter-governmental Panel on Climate Change (IPCC) reported that human activities result in the production of greenhouse gases (CO₂, CH₄, N₂O and CFCs), which significantly contribute to global warming, one of the most serious environmental problems. Under these circumstances, most nations have shown a willingness to suffer economic burdens by signing the Kyoto Protocol, which took effect from February 2005. Therefore, an innovative technology for the simultaneously removal carbon dioxide (CO₂) and nitrogen dioxide (NO₂), which are discharged in great quantities from fossil fuel-fired power plants and incineration facilities, must be developed to reduce these economical burdens. In this study, a blend of AMP and NH₃ was used to achieve high absorption rates for CO₂, as suggested in several publications. The absorption rates of CO₂, SO₂ and NO₂ into aqueous AMP and blended AMP+NH₃ solutions were measured using a stirred-cell reactor at 293, 303 and 313 K. The reaction rate constants were determined from the measured absorption rates. The effect of adding NH₃ to enhance the absorption characteristics of AMP was also studied. The performance of the reactions was evaluated under various operating conditions. From the results, the reactions with SO₂ and NO₂ into aqueous AMP and AMP+NH₃ solutions were classified as instantaneous reactions. The absorption rates increased with increasing reaction temperature and NH₃ concentration. The reaction rates of 1, 3 and 5 wt% NH₃ blended with 30 wt% AMP solution with respect to CO₂/SO₂/NO₂ at 313 K were 6.05～8.49×10^?6, 7.16–10.41×10^?6 and 8.02～12.0×10^?6 kmol m^?2s^?1, respectively. These values were approximately 32.3–38.7% higher than with aqueous AMP solution alone. The rate of the simultaneous absorption of CO₂/SO₂/NO₂ into aqueous AMP+NH₃ solution was 3.83–4.87×10^?6 kmol m^?2s^?1 at 15 kPa, which was an increase of 15.0–16.9% compared to 30 wt% AMP solution alone. This may have been caused by the NH₃ solution acting as an alternative for CO₂/SO₂/NO₂ controls from flue gas due to its high absorption capacity and fast absorption rate.     

Effect of addition of weak acids on CO<Subscript>2</Subscript> desorption from rich amine solvents

Experiments were conducted to study the effect of addition of four weak acids (adipic, suberic, phthalic and sebacic acids) on the regeneration of three types of CO₂-loaded rich solvents (Monoethanolamine (MEA), Diethanolamine (DEA) and Methyldiethanolamine (MDEA)). It was found that CO₂ could be released faster and in a larger quantity when the amount of acid added to the solvent was increased while other desorption conditions were maintained unchanged. Adipic acid appeared to be more effective than phthalic, suberic and sebacic acids in enhancing solvent regeneration rate. Among the three amines investigated, MEA had the highest CO₂ desorption rate, while DEA saved the most energy. The effect of adipic acid residue in the MEA solvent on CO₂ absorption was also investigated. The residue acid reduced the absorption capacity of the MEA solvent significantly when the solvent concentration was low and slightly when the concentration was high.     

Non-oxidative thermal degradation of amines: GCMS/FTIR spectra analysis and molecular modeling

Aqueous amino solvents, such as monoethanolamine (ETA/MEA), methyl diethanolamine (MDEA) or amine blends, are the most widely used solvents in commercial CO₂ or acid gas separation applications. These commercial solvents have various disadvantages, such as the possibilities of the solvent to be degraded. This research examines the impact of non-oxidative thermal degradations on the performance of the CO₂ absorption and the degradation mechanism of amine solvents. The impact of degradation was conducted by measuring the CO₂ solubility of solvent that had been heated to 120°C for 2 h. Although the performance of CO₂ absorption was not significantly reduced, the degradation of amines was found. Supported by Fourier Transform Infrared (FTIR) and Gas Chromatography/Mass Spectrometer result, the suspected products of non-oxidative thermal degradation of MDEA were MEA and acetone.     

The analysis of solubility,absorption kinetics of CO2 absorption into aqueous 1‐diethylamino‐2‐propanol solution

In this present work, the CO₂ absorption performance of aqueous 1‐diethylamino‐2‐propanol (1DEA2P) solution was studied with respect to CO₂ equilibrium solubility, absorption kinetics, and absorption heat. The equilibrium solubility of CO₂ in 2M 1DEA2P solution was measured over the temperature range from 298 to 333 K and CO₂ partial pressure range from 8 to101 kPa. The absorption kinetics data were developed and analyzed using the base‐catalyzed hydration mechanism and artificial neural network models (radial basis function neural network [RBFNN] and back‐propagation neural network [BPNN] models) with an acceptable absolute average deviation of 10% for base‐catalyzed hydration mechanism, 2.6% for RBFNN model and 1.77% for BPNN model, respectively. The CO₂ absorption heat of 1DEA2P was estimated to be ?43.6 kJ/mol. In addition, the ions (1DEA2P, 1DEA2PH⁺, , CO₃^2?) speciation plots of the 1DEA2P‐CO₂‐H₂O system were developed to further understand the reaction process of 1DEA2P with CO₂. Based on a comparison with conventional amines (e.g., MEA, DEA, MDEA) and alternative amines (i.e., 1DMA2P and 4‐(diethylamino)?2‐butanol [DEAB]), 1DEA2P exhibited good performance with respect to CO₂ equilibrium solubility, reaction kinetics, and CO₂ absorption heat. Meanwhile, the overall evaluation of 1DEA2P for application in CCS in terms of absorption and desorption is presented, giving helpful information for the screening of these novel amines. © 2017 American Institute of Chemical Engineers AIChE J, 63: 2694–2704, 2017