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.     

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.     

Kinetics of the absorption of carbon dioxide into mixed aqueous solutions of 2-amino-2-methyl-l-propanol and piperazine

The reaction kinetics of the absorption of CO₂ into aqueous solutions of piperazine (PZ) and into mixed aqueous solutions of 2-amino-2-methyl-l-propanol (AMP) and PZ were investigated by wetted wall column at 30-40 °C. The physical properties such as density, viscosity, solubility, and diffusivity of the aqueous alkanolamine solutions were also measured. The N₂O analogy was applied to estimate the solubilities and diffusivities of CO₂ in aqueous amine systems. Based on the pseudo-first-order for the CO₂ absorption, the overall pseudo first-order reaction rate constants were determined from the kinetic measurements. For CO₂ absorption into aqueous PZ solutions, the obtained second-order reaction rate constants for the reaction of CO₂ with PZ are in a good agreement with the results of Bishnoi and Rochelle (Chem. Eng. Sci. 55 (2000) 5531). For CO₂ absorption into mixed aqueous solutions of AMP and PZ, it was found that the addition of small amounts of PZ to aqueous AMP solutions has significant effect on the enhancement of the CO₂ absorption rate. For the CO₂ absorption reaction rate model, a hybrid reaction rate model, a second-order reaction for the reaction of CO₂ with PZ and a zwitterion mechanism for the reaction of CO₂ with AMP was used to model the kinetic data. The overall absolute percentage deviation for the calculation of the apparent rate constant k_app is 7.7% for the kinetics data measured. The model is satisfactory to represent the CO₂ absorption into mixed aqueous solutions of AMP and PZ.     

Modelling Vapour − Liquid Equilibrium of CO2 in Aqueous N‐Methyldiethanolamine through the Simulated Annealing Algorithm

The modified Clegg‐Pitzer equation is used to correlate and predict the vapor‐liquid equilibrium of the CO₂‐MDEA‐H₂O system. Simulated annealing (SA), a computational stochastic technique for finding near global minimum solutions to optimization problems, has been used for parameter estimation in the model to predict VLE of CO₂ in aqueous MDEA solution. The solubility of CO₂ in aqueous solutions of 23.8 wt % and 30.0 wt % of N‐methyldiethanolamine (MDEA) has been measured over the temperature range of 303‐323 K and CO₂ partial pressure range of 1 to 100 kPa. The model predicted equilibria have been found to be in good agreement with the experimental results of VLE measurement of this work as well as those in the open literature. In this work, the SA technique has been used as an alternative to the traditional Levenberg‐Marquardt (LM) technique, to predict the VLE data accurately.     

Absorption of carbon dioxide by the absorbent composed of piperazine and 2-amino-2-methyl-1-propanol in PVDF membrane contactor

This paper tests the performance of microporous polyvinylidinefluoride (PVDF) hollow fiber in a gas absorption membrane process (GAM) using the aqueous solutions of piperazine (PZ) and 2-amino-2-methyl-1-propanol (AMP). Experiments were conducted at various gas flow rates, liquid flow rates and absorbent concentrations. Experimental results showed that wetting ratio was about 0.036% when used with the aqueous alkanolamine solutions, while that was 0.39% with aqueous piperazine solutions. The CO₂ absorption rates increased with increasing both liquid and gas flow rates at N_Re < 20. The increase of the PZ concentration showed an increase of absorption rate of CO₂. The CO₂ absorption rate was much enhanced by the addition of PZ promoter. The resistance of membrane was predominated as using a low reactivity absorbent and can be neglected as using absorbent of AMP aqueous solution. The resistance of gas-film diffusion was dominated as using the mixed absorbents of AMP and PZ. An increase of PZ concentration, the resistance of liquid-film diffusion decreased but resistance of gas-film increased. Overall, GAM systems were shown to be an effective technology for absorbing CO₂ from simulated flue gas streams, but the viscosity and solvent-membrane relationship were critical factors that can significantly affect system performance.     

Vapor–liquid equilibrium in amino acid salt system: Experiments and modeling

Vapor–liquid equilibrium (VLE) measurements were carried out for both unloaded and CO₂ loaded aqueous amino acid salt (AAS) solutions of the potassium salt of sarcosine (KSAR). Vapor–liquid equilibrium for unloaded solutions; 1.0–5.0 M KSAR was measured using a Swietoslawski ebulliometer for temperatures 40, 60, 80 and 100 °C and for total pressures 4.08–97.8 kPa while vapor–liquid equilibrium for CO₂ loaded solutions of 3.5 M KSAR was measured using both low and high temperature VLE apparatuses for 40, 60, 80, 100 and 120 °C and for CO₂ partial pressures ranging from 0.03 to 971 kPa. A thermodynamic model representing the AAS solvent system was developed using the extended UNIQUAC framework. The developed model accurately predicts the equilibrium speciation in loaded solutions from ¹³C NMR data and gives a very good representation of the solubility of CO₂ in the amino acid salt solution as well as the total pressure of the unloaded system at all measured temperatures, loadings and pressures.     

Vapor–liquid equilibrium in aqueous amine amino acid salt solution: 3-(methylamino)propylamine/sarcosine

Vapor–liquid equilibrium (VLE) measurements were conducted for both unloaded and CO₂ loaded aqueous amine amino acid salt (AAAS) solutions; 3-(methylamino)propylamine/sarcosine (SARMAPA). Vapor–liquid equilibrium for unloaded solutions for 1.0–5.0 M SARMAPA were measured using a Swietoslawski ebulliometer for temperatures 40–100 °C and for total pressures 4.08–99.1 kPa. CO₂ equilibrium was determined for loaded 5 M SARMAPA using low and high temperature VLE apparatuses from 40 to 120 °C. A thermodynamic model representing equilibrium in the H₂O–AAAS–CO₂ system was developed using the extended UNIQUAC thermodynamic framework. The developed model predicts simplified speciations in H₂O–SARMAPA–CO₂ system and adequately correlates the experimental total and partial pressure data with an average absolute deviation of 8.9%.     

Simultaneous absorption of CO<Subscript>2</Subscript> and SO<Subscript>2</Subscript> into aqueous AMP/NH<Subscript>3</Subscript> solutions in binary composite absorption system

To enhance the absorption rate for CO₂ and SO₂, aqueous ammonia (NH₃) solution was added to an aqueous 2-amino-2-methyl-1-propanol (AMP) solution. The simultaneous absorption rates of AMP and a blend of AMP+ NH₃ for CO₂ and SO₂ were measured by using a stirred-cell reactor at 303 K. The process operating parameters of interest in this study were the solvent and concentration, and the partial pressures of CO₂ and SO₂. As a result, the addition of NH₃ solution into aqueous AMP solution increased the reaction rate constants of CO₂ and SO₂ by 144 and 109%, respectively, compared to that of AMP solution alone. The simultaneous absorption rate of CO₂/SO₂ on the addition of 1 wt% NH₃ into 10 wt% AMP at a p _A1 of 15 kPa and p _A2 of 1 kPa was 5.50×10⁻⁶ kmol m⁻² s⁻¹, with an increase of 15.5% compared to 10 wt% AMP alone. Consequently, the addition of NH₃ solution into an aqueous AMP solution would be expected to be an excellent absorbent for the simultaneous removal of CO₂/SO₂ from the composition of flue gas emitted from thermoelectric power plants.     

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.     

The physical solubilities and diffusivities of N<Subscript>2</Subscript>O and CO<Subscript>2</Subscript> in aqueous ammonia solutions on the additions of AMP,glycerol and ethylene glycol

Carbon dioxide (CO₂) is a major greenhouse gas, the emissions of which should be reduced. There are various technologies for the effective separation of CO₂. Of these, chemical absorption methods are generally accepted as the most effective. The monoethanolamine (MEA) process is an effective way to remove CO₂, but is an expensive option for the separation of CO₂ from massive gas-discharging plants. Therefore, ammonia solution, which is less expensive and more effective than MEA, was used for the removal of CO₂. In this study, the physical solubility of N₂O in (ammonia+water), (ammonia+2-amino-2-methyl-1-propanol+water), (ammonia+glycerol+water) and (ammonia+ ethylene glycol+water) was measured at 293, 303, 313, 323 K. Additive concentrations of 1, 3, and 5 wt% AMP, glycerol and ethylene glycol were added for each 9 wt% ammonia solution. A solubility apparatus was used to investigate the solubility of N₂O in ammonia solutions. The diffusivity was measured with a wetted wall column absorber. The “N₂O analogy” is used to estimate the solubility and diffusivity of CO₂ in the aqueous ammonia solutions. OriginPro 7.5 was used to correlate the solubility and diffusivity of N₂O in ammonia solutions. The parameters of the correlation were determined from the measured solubility and diffusivity.     

CO2 Capture by Liquid Solvents and their Regeneration by Thermal Decomposition of the Solid Carbonated Derivatives

The chemical capture of CO₂ by either aqueous Na₂CO₃ and K₂CO₃ or nonaqueous solutions of the amines 2‐amino‐2‐methyl‐1‐propanol (AMP) or piperazine (PZ) is described. The captured CO₂ is stored as solid NaHCO₃, KHCO₃, and AMP or PZ carbamates. Solid NaHCO₃ and KHCO₃ are decomposed at 200 °C and 250 °C, respectively, to regenerate the carbonates for their reuse. In the experiments with AMP or PZ, the solid carbamates are decomposed at 80 °C–110 °C to regenerate the free amines. The absence of water in the desorption‐regeneration step is intriguing and could have the potential of reducing one of the major disadvantages of aqueous absorbents, namely the energy cost of the regeneration step and amine degradation, yet preserving the efficiency of the absorption in the liquid phase.     

Effects of piperazine concentration and operating conditions on the solubility of CO2 in AMP solution at low CO2 partial pressure

In this study, new equilibrium solubility data for carbon dioxide in aqueous solutions of 2-amino-2-methyl-1-propanol and piperazine (PZ) are provided. The two famous Deshmukh–Mather and Kent Eisenberg thermodynamic models are utilized to predict the CO₂ absorption. The experimental data show that the solubility of CO₂ decreases as the temperature increases. Our data suggest that the addition of PZ has different effects on CO₂ absorption under different partial pressure of the CO₂ in the gas stream. For high partial pressure, the addition of PZ promotes the absorption performance. However, at low CO₂ partial pressure, PZ addition results in less saturated CO₂ loading. The Deshmukh–Mather model can provide an accurate prediction of the experimental data at high partial pressure of CO₂ (i.e. AAD = 3.4%) whereas the modified Kent–Eisenberg model can capture the inverse effects of the PZ at low partial pressure and provides a relatively good approximation of experimental data at low partial pressure (i.e. AAD = 10%).     

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.     

Kinetics and modeling of carbon dioxide absorption into aqueous solutions of piperazine

In this work, the kinetics of the reaction between CO₂ and aqueous piperazine (PZ) have been estimated over the temperature range of 298-313 K from the absorption data obtained in a wetted wall contactor. The absorption data are obtained for the PZ concentrations of 0.2- and for CO₂ partial pressures up to 5 kPa. A coupled mass transfer-kinetics-equilibrium mathematical model based on Higbie's penetration theory has been developed with the assumption that all reactions are reversible. The model is used to estimate the rate constants from the experimental data for absorption of CO₂ in aqueous PZ. The estimated rate constants of this study are in good agreement with those reported in the literature.     

Surface Tensions of Carbonated 2‐Amino‐2‐methyl‐1‐propanol and Piperazine Aqueous Solutions

Surface tensions of carbonated 2‐amino‐2‐methyl‐1‐propanol (AMP) and piperazine (PZ) aqueous solutions were measured by a surface tension meter which employs the Wilhemy plate principle. A thermodynamic model was proposed to correlate the surface tensions of both CO₂‐unloaded and CO₂‐loaded aqueous solutions by introducing the contribution of CO₂ loading into the formulation of surface tension. Based on experiments and calculations, the effects of temperature, mass fractions of amines, and CO₂ loading on surface tensions of carbonated aqueous solutions were demonstrated.     

Solubility of CO2 in 15, 30, 45 and 60 mass% MEA from 40 to 120 °C and model representation using the extended UNIQUAC framework

New experimental data for vapor–liquid equilibrium of CO₂ in aqueous monoethanolamine solutions are presented for 15, 30, 45 and 60 mass% MEA and from 40 to 120 °C. CO₂ partial pressures over loaded MEA solutions were measured using a low temperature equilibrium apparatus while total pressures were measured with a high temperature equilibrium apparatus. Experimental data are given as CO₂ partial pressure as function of loading in solution for temperatures from 40 to 80 °C and as total pressures for temperatures from 60 to 120 °C for the different MEA concentrations. The extended UNIQUAC model framework was applied and model parameters were fitted to the new experimental VLE data and physical CO₂ solubility data from the literature. The model gives a good representation of the experimental VLE data for CO₂ partial pressures and total pressures for all MEA concentrations with an average absolute relative deviation (AARD) of 24.3% and 11.7%, respectively, while the physical solubility data were represented with an AARD of 2.7%. Further, the model predicts well literature data on freezing point depression, excess enthalpy and liquid phase speciation determined by NMR.     

CO2 capture solvent selection by combined absorption-desorption analysis

A method was developed for selection of promising solvents based on CO₂ absorption experiments at 40 °C and 9.5 kPa CO₂ partial pressure followed by desorption of the same solvents at 80 °C down to 1.0 kPa CO₂ partial pressure. Experiments conducted on 13 solvent systems under atmospheric conditions revealed the solvents absorption and desorption characteristics and these were compared with 1.0 M, 2.5 M, 5.0 M and 10.0 M MEA. Results showed that absorption or stripping data alone were not sufficient in making robust solvent selection decisions, and that combined data analysis was necessary. 1.0 M tetraethylenepentamine (TEPA) and 5.0 M MEA showed the best performance in terms of absorption rate. 1.5 M Bis-(3-dimethylaminopropyl) amine (TMBPA) was easy to desorb, has high absorption capacity; and when promoted it showed the best performance in terms of CO₂ carrying capacity. At the test conditions, 1.5 M TMBPA promoted with 1.0 M PZ showed the best potential for efficient CO₂ removal at reduced cost of all systems tested. Its cyclic capacity in mol CO₂/mol amine was found to be 70% higher than that of 5 M MEA.     

Aqueous piperazine derivatives for CO2 capture: Accurate screening by a wetted wall column

Concentrated aqueous piperazine (PZ) has been identified as a better solvent for CO₂ capture than monoethanolamine (MEA), because it has a greater rate of CO₂ absorption and greater CO₂ capacity. This work evaluates the effect of substitute groups on PZ performance. Many previous screening studies measured absorption/desorption with CO₂/N₂ sparging, which lacks accuracy and cannot be used to estimate actual absorber performance. In this work a wetted wall column was used to accurately measure absorption/desorption rate at typical rich and lean CO₂ loading (α) and simulate performance of real packing. The method also provides accurate measurement of CO₂ solubility at 40-100 °C. This study provided rate and solubility data at 40-100 °C and practical ranges of CO₂ loading for 8 m 1-methylpiperazine (1-MPZ), 8 m 2-methylpiperazine (2-MPZ), 4 m 2-MPZ/4 m PZ, 7.7 m N-(2-hydroxyethyl)piperazine (HEP), 6 m 1-(2-aminoethyl)piperazine (AEP), 8 m 2-piperidine ethanol (2-PE), and 2 m trans-2,5-dimethylpiperazine (2,5-DMPZ). With the measurements of CO₂ flux (NCO₂) and equilibrium driving force, liquid film mass transfer coefficients (k_g′) are calculated. The rate decreases as of 1-MPZ = PZ > 2-MPZ/PZ > 2-MPZ > HEP > MEA > AEP = 2-PE. This method also allows bracketing and determination of equilibrium CO₂ partial pressure (^*PCO₂) at each condition. Semi-empirical solubility models of CO₂ for each amine were regressed from experimental solubility data to find the lean and rich CO₂ loading corresponding to 0.500 kPa and 5 kPa CO₂ partial pressure respectively. Based on the solubility model, the actual operating capacity of the solvents without overstripping decreases in the sequence of 2-PE > 2-MPZ > 2-MPZ/PZ > 1-MPZ > PZ > HEP > AEP > MEA. The enthalpy of CO₂ absorption (ΔH_abs) of all the piperazine derivatives is around 70 kJ/mol CO₂.     

Analysis of the heat of reaction and regeneration in alkanolamine-CO<Subscript>2</Subscript> system

The estimation of regeneration heat of absorbent is important because it is a key factor that has an effect on the process efficiency. In this study, thermal stability and regeneration heat of aqueous amine solutions such as monoethanolamine (MEA), 2-amino-2-methyl-1-propanol (AMP), N-methyldiethanolamine (MDEA), and 1,8-diamino-pmenthane (KIER-C3) were investigated by using TGA-DSC analysis. The thermal characteristics of the fresh and CO₂ rich amine solutions were estimated. The CO₂ rich amine solutions were obtained by VLE experiments at T=40 °C. The regeneration heat of aqueous MEA solution was 76.991–66.707 kJ/mol-CO₂, which is similar to heat of absorption. The reproducibility of the results was obtained. The regeneration heat of aqueous KIER-C3 20 wt% solution (1.68 M) was lower than that of aqueous MEA 30 wt% solution (4.91 M). Therefore, the KIER-C3 can be used as an effective absorbent for acid gas removal.     

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.