Experimental and theoretical investigation of solubility of carbon dioxide in concentrated aqueous solution of 2-amino-2-methyl-1-propanol and piperazine

In this work, new experimental results for the (vapour + liquid) equilibrium (VLE) of CO₂ in piperazine (PZ)-activated concentrated aqueous 2-amino-2-methyl-1-propanol (AMP) are presented for the temperature range of (303 to 328) K and PZ concentration range of (2 to 8) wt.%, keeping the total amine concentration in the solution at 40% and 50 wt.%. The partial pressures of CO₂ are in the range of (0.2 to 1500) kPa. The electrolyte non-random two-liquid (ENRTL) theory has been used to develop the VLE model for the quaternary system (CO₂ + AMP + PZ + H₂O) to describe the equilibrium behaviour of the solution. The CO₂ cyclic capacity of these solvents is determined between the rich and lean CO₂ loadings. It is found that the CO₂ cyclic capacity increases with the addition of PZ in aqueous AMP and also with the increase in AMP concentration in the aqueous solution. However, solid precipitation has been observed for 50 wt.% total amine concentration below T = 318 K for all relative compositions of AMP and PZ in the solvent at higher CO₂ loading. The model results of equilibrium composition, pH of the loaded solution and amine volatility of the mixed solvent system, are also presented.     

CO2/H2 separation by facilitated transport membranes immobilized with aqueous single and mixed amine solutions: Experimental and modeling study

An experimental and theoretical analysis to separate CO₂ using facilitated transport membranes immobilized with different aqueous single and mixed amine solutions have been performed. The membranes containing monoethanolamine (MEA), diethanolamine (DEA), monoprotonated ethylenediamine (EDAH⁺) and piperazine (PZ), as well as aqueous blends of PZ with MEA, DEA or EDAH⁺ were considered. The aqueous solution of PZ showed the highest CO₂ permeation rate with respect to other single amine solutions. Therefore blends of PZ with MEA, DEA and EDAH⁺ increased the permeance of carbon dioxide through mixed amine membranes.     

(Vapour + liquid) equilibria (VLE) of CO2 in aqueous solutions of 2-amino-2-methyl-1-propanol: New data and modelling using eNRTL-equation

This work presents new experimental results for carbon dioxide (CO₂) solubility in aqueous 2-amino-2-methyl-1-propanol (AMP) over the temperature range of (298 to 328) K and CO₂ partial pressure of about (0.4 to 1500) kPa. The concentrations of the aqueous AMP lie within the range of (2.2 to 4.9) mol · dm^?3. A thermodynamic model based on electrolyte non-random two-liquid (eNRTL) theory has been developed to correlate and predict the (vapour + liquid) equilibrium (VLE) of CO₂ in aqueous AMP. The model predictions have been in good agreement with the experimental data of CO₂ solubility in aqueous blends of this work as well as those reported in the literature. The current model can also predict speciation, heat of absorption, enthalpy of CO₂ loaded aqueous AMP, pH of the loaded solution, and AMP volatility.     

CO2 solubility in aqueous solutions of N-methyldiethanolamine+piperazine by electrolyte NRTL model

Accurate modeling of the solubility behavior of CO₂ in the aqueous alkanolamine solutions is important to design and optimization of equipment and process. In this work, the thermodynamics of C_O2 in aqueous solution of N-methyldiethanolamine (MDEA) and piperazine (PZ) is studied by the electrolyte non-random two liquids (NRTL) model. The chemical equilibrium constants are calculated from the free Gibbs energy of formation, and the Henry’s constants of CO₂ in MDEA and PZ are regressed to revise the value in the pure water. New experimental data from literatures are added to the regression process. Therefore, this model should provide a comprehensive thermodynamic representation for the quaternary system with broader ranges and more accurate predictions than previous work. Model results are compared to the experimental vapor-liquid equilibrium (VLE), speciation and heat of absorption data, which show that the model can predict the experimental data with reasonable accuracy.     

High-pressure phase behaviour of binary (CO2 + nicotine) and ternary (CO2 + nicotine + solanesol) mixtures

This work paper presents vapour–liquid equilibrium (VLE) data for binary (CO₂ + nicotine) and ternary (CO₂ + nicotine + solanesol) mixtures, at 313.2 K and 6, 8 and 15 MPa. The (CO₂ + nicotine) system exhibits three phases (L₁L₂V) in equilibrium at 8.37 MPa. It is estimated that this system most likely follows the type-III phase behaviour. In the ternary system, the presence of solanesol in the vapour phase was detected only at the pressure of 15 MPa. At this pressure, partition coefficients and separation factors for solanesol/nicotine were calculated for different initial nicotine/solanesol compositions and a strong influence of composition was found. The results were modelled using the Peng–Robinson equation of state (PR EOS) coupled with the Mathias–Klotz–Prausnitz (MKP) mixing rule (PR–MKP model). Good correlations of the binary data, particularly in the case of the (CO₂ + nicotine) mixture, were obtained. However, the model could not correlate the ternary data.     

Acid gases partial pressures above a 50 wt% aqueous methyldiethanolamine solution: Experimental work and modeling

Aqueous amine solutions are widely used in the industry for acid gas removal. In order to treat natural gas or refinery process streams, an accurate knowledge of solubility data of carbon dioxide, hydrogen sulfide and other sulfur species in aqueous amine solutions is required. In this paper, new equilibrium measurements on 50 wt% aqueous methyldiethanolamine solution with CO₂ and H₂S have been produced. A simple way to correlate the data has been searched and found. First, a model proposed by Posey et al. in 1996, then a Deshmukh–Mather model are used to correlate “vapor–liquid” equilibria. The Posey et al. model lacks accuracy to represent the experimental data, especially for high loadings. The Deshmukh–Mather model shows good agreement as long as the total loading (H₂S + CO₂) does not reach 1.0.     

High-pressure vapor–liquid equilibria for CO2 + alkanol systems and densities of n-dodecane and n-tridecane

An apparatus based on the static-analytic method was used to measure the vapor–liquid equilibria (VLE) for CO₂ + alkanol systems. Equilibrium measurements for the CO₂ + 1-propanol system were performed from 344 to 426 K. For the case of the CO₂ + 2-propanol system, measurements were made from 334 to 443 K, and for the CO₂ + 1-butanol were obtained from 354 to 430 K. VLE data were correlated with the Peng–Robinson equation of state using the classical and the Wong–Sandler mixing rules. Moreover, compressed liquid densities for the n-dodecane and n-tridecane were obtained via a vibrating tube densitometer at temperatures from 313 to 363 K and pressures up to 25 MPa. The Starling and Han (BWRS), and The five-parameter Modified Toscani-Swarcz (MTS) equations were used to correlate them. The experimental density data were compared with those from literature, and with the calculated values obtained from available equations for these n-alkanes.     

Correlation of CO2 solubility in N-methyldiethanolamine + piperazine aqueous solutions using extended Debye–Hückel model

Solubility data of CO₂ in aqueous N-methyldiethanolamine (MDEA) solutions of concentration (2.52, 3.36, and 4.28) kmol/m³ were obtained at temperatures (313, 323, and 343) K and partial pressures ranging from about (30 to 5000) kPa. A thermodynamic model based on extended Debye–Hückel theory was applied to predict and correlate of CO₂ solubility in various aqueous amine solutions. The effect of piperazine (PZ) concentration on CO₂ loading in MDEA solutions was determined at PZ concentration (0.36, 0.86, and 1.36) kmol/m³. Using experimental data in various temperatures the interaction parameters of activity coefficient model for these systems were determined. The results show the model consistency with experimental and literature data and PZ is beneficial to the CO₂ loading. The comparison of results of this study with previous data work shows the wide range of CO₂ loading considered in this work and the better agreement of model with experimental data. The average absolute relative deviation percent (δ_AAD) for all data points were 8.11%.     

Modeling solubility of acid gases in alkanolamines using the nonelectrolyte Wilson-nonrandom factor model

The nonelectrolyte Wilson-nonrandom factor local composition model (N-Wilson-NRF) by Haghtalab and Mazloumi is applied for modeling the vapor–liquid equilibrium of the acid gases (CO₂ and H₂S)–alkanolamine–water systems. The model is used to calculate the nonideality of species in liquid phase through the activity coefficient equations. In this work, we use the N-Wilson-NRF model for short-range forces in the aqueous electrolyte system of alkanolamines by using the concept of ion-pair. For the long-range interaction the Pitzer–Debye–Hückel theory is applied. The model is used to correlation of the solubility data of CO₂ and H₂S in aqueous monoethanolamine (MEA), diethanolamine (DEA), methyldiethanolamine (MDEA) and 2-amino-2methyl-1-propanol (AMP) systems over wide range of temperature (0–140 °C), partial pressure (0.001–1000 kPa) and acid gases loading (0.001–1.0 mol gas/mol amine). To show the predictability of the model, the interaction parameters without any additional adjustable parameters are used to predict the solubility of CO₂ in aqueous AMP solution at different conditions. The results of the model show a very good agreement with the experimental data.     

New isothermal vapor–liquid equilibria for the CO2 + n-nonane,and CO2 + n-undecane systems

Experimental vapor–liquid equilibria (VLE) for the CO₂ + n-nonane and CO₂ + n-undecane systems were obtained by using a 100-cm³ high-pressure titanium cell up to 20 MPa at four temperatures (315, 344, 373, and 418 K). The apparatus is based on the static-analytic method; which allows fast determination of the coexistence curve. For the CO₂ + n-nonane system, good agreement was found between the experimental data and those reported in literature. No literature data were available for the CO₂ + n-undecane system at high temperature and pressure. Experimental data were correlated with the Peng–Robinson equation of state using the classical and the Wong–Sandler mixing rules.     

Rate‐Based Modeling of CO2 Absorption into Piperazine‐Activated Aqueous N‐Methyldiethanolamine Solution: Kinetic and Mass Transfer Analysis

A comprehensive two‐dimensional mathematical model based on surface renewal theory has been developed to analyze the CO₂ absorption into piperazine (PZ)‐activated aqueous N‐methyldiethanolamine (MDEA) solvent by taking into account the structured packed bed column hydraulics, mass transfer resistances, and chemical reactions. The modeling results have been validated with the experimental data reported in the literature, and they have been found to be in good agreement with the experimental results. The effects of amine concentration, liquid temperature, initial CO₂ partial pressure, liquid flow rate, and CO₂ loading on the mass transfer performance have been evaluated in terms of overall mass transfer coefficient (K _Ga_v). The overall mass transfer coefficient and absorption flux of CO₂ into aqueous MDEA+PZ blended solution have been calculated over the CO₂ partial pressure range of 4–16 kPa, temperature range of 298–333 K, and solvent concentration of 1–3 M. To evaluate the performance of different solvents on separation process, some common industrial chemical absorbents including monoethanolamine (MEA), diethanolamine (DEA), triethylamine (TEA), MDEA and PZ were compared with a MDEA+PZ blended solution. The results indicate that CO₂ absorption reaction with PZ is faster than that with MDEA, but also adding small amounts of PZ as a promoter to MDEA solvents improves significantly the absorption rate. The results show that CO₂ absorption reaction with the MDEA+PZ blended solution is faster than that with TEA and MDEA, also comparable with DEA, but slower than those with MEA and PZ. The modeling results illustrate that the K _Ga_v enhances with increasing the solvent concentration, liquid temperature, and liquid flow rate, but reduces with increasing the CO₂ loading and initial CO₂ partial pressure. In addition, the reaction kinetics in terms of enhancement factor was found to decrease as the CO₂ loading enhances and increase as the operating temperature rises.     

An FTIR spectroscopic study and quantification of 2-amino-2-methyl-1-propanol,piperazine and absorbed carbon dioxide in concentrated aqueous solutions

This study reports the investigation of carbon dioxide (CO₂) absorption into an amine blend solution of 2-amino-2-methyl-1-propanol (AMP) and piperazine (PZ). The reaction in the liquid phase between CO₂ and the amines were qualitatively and quantitatively monitored by Fourier Transform Mid-Infrared spectroscopy (mid-FTIR). A multivariate partial least square regression (PLS2) model was obtained to quantify free or non-reacted AMP and PZ and absorbed CO₂ in all chemical forms, i.e. no differentiation was made into carbonates or carbamates. The calibration model was constructed using a single wide region and 270 calibration samples. The concentration of AMP, PZ and CO₂ from 568 samples were simultaneously predicted with low relative errors.     

Thermodynamics of aqueous potassium carbonate,piperazine, and carbon dioxide

CO₂ solubility was measured in a wetted-wall column in 0.6–3.6 molal (m) piperazine (PZ) and 2.5–6.2 m potassium ion (K⁺) at 40–110 °C. Piperazine speciation was determined using ¹H NMR for 0.6–3.6 m piperazine (PZ) and 3.6–6.2 m potassium ion (K⁺) at 25–70 °C. The capacity of CO₂ in solution increases as total solute concentration increases and compares favorably with estimates for 7 m (30 wt.%) monoethanolamine (MEA). The presence of potassium in solution increases the concentration of CO₃²⁻/HCO₃⁻ in solution, buffering the solution. The buffer reduces protonation of the free amine, but increases the amount of carbamate species. These competing effects yield a maximum fraction of reactive species at a potassium to piperazine ratio of 2:1.A rigorous thermodynamic model was developed, based on the electrolyte nonrandom two-liquid (ENRTL) theory, to describe the equilibrium behavior of the solvent. Modeling work established that the carbamate stability of piperazine and piperazine carbamate resembles primary amines and gives approximately equal values for the heats of reaction, ΔH_rxn (18.3 and 16.5 kJ/mol). The pK_a of piperazine carbamate is twice that of piperazine, but the ΔH_rxn values are equivalent (∼−45 kJ/mol). Overall, the heat of CO₂ absorption is lowered by the formation of significant quantities of HCO₃⁻ in the mixed solvent and strongly depends on the relative concentrations of K⁺ and PZ, ranging from −40 to −75 kJ/mol.     

VLE of CO2 + glycerol + (ethanol or 1-propanol or 1-butanol)

Vapour-liquid equilibrium of CO₂ + [0.00871 glycerol + 0.99129 (ethanol or 1-propanol or 1-butanol)] mixtures was measured at the temperatures of 313.15 K and 333.15 K, and close to the critical line, at pressures up to 12 MPa. On the liquid side, the bubble points measured for these ternary mixtures follow closely the behaviour of VLE reported by several authors for the corresponding binary mixtures without glycerol. On the vapour side, however, dew points for the ternary mixtures deviate significantly from VLE results for the binaries. A correlation of the results obtained for the CO₂ + glycerol + ethanol mixture with the Peng-Robinson equation of state, admitting quasi-binary behaviour, equally yields good agreement on the liquid side, and significant deviations on the vapour side.     

Equilibrium solubility of carbon dioxide in 2(methylamino)ethanol

In this paper the equilibrium solubility of carbon dioxide in 1.0 M, 2.0 M and 4.0 M 2(methylamino)ethanol (MAE) is measured at 303, 313 and 333 K, and at CO₂ partial pressures ranging from 1 to 100 kPa using stirred cell reactor. The Kent-Eisenberg model was used to predict the solubility of carbon dioxide in MAE solutions. The equilibrium constant representing hydrolysis of carbamate ion is correlated with temperature, CO₂ partial pressure and amine concentration by non-linear regression, using experimental results of carbamate ion concentrations. The model predicted results showed good agreement with the experimental solubility results. The solubility profile of CO₂ in MAE showed better performance when compared with other commercial amines.     

Thermodynamics of aqueous solutions of methyldiethanolamine and diisopropanolamine

The vapour–liquid equilibrium (VLE) of the systems of water + methyldiethanolamine (MDEA) and water + diisopropanolamine (DIPA) was measured at several temperatures with a static total pressure apparatus. The solid–liquid equilibrium (SLE) of the same systems was measured at low amine concentrations by means of two experimental methods: a visual method and a Differential Scanning Calorimeter (DSC). The activity coefficients of water + MDEA were modelled with the NRTL equations. The model parameters were regressed from VLE, SLE and excess enthalpy data from this work and from the literature. The model developed in this work was compared with models found in the literature. The NRTL equations were also used to model the activity coefficients of the system of water + DIPA. The model parameters were fitted from the VLE and SLE data measured in this work.     

Solubility of Carbon Dioxide in Aqueous Mixtures of DIPA + MDEA and DIPA + PZ Solutions

The new data for solubility of carbon dioxide are reported in mixed solvents containing (2.00 to 2.50 kmol/m³) Diisopropanolamine (DIPA), (0.86 to 1.36) kmol/m³) Piperazine (PZ), (0.86 to 1.36) kmol/m³) N‐methyldiethanolamine (MDEA) and water, keeping the amine total concentration in the aqueous solution at 3.36 kmol/m³ for temperatures from (40 to 70) °C and CO₂ partial pressures in the range of (30 to 5000) kPa. Experimental solubility results were represented by the mole ratio of CO₂ per total amine in the liquid mixture. Results show that at a given partial pressure of CO₂ the solubility of CO₂ in the DIPA solutions is lower than solubility in MDEA or PZ solutions and the CO₂ loading increased with decreasing temperature and increasing CO₂ partial pressure.     

Study of the behaviour of the azeotropic mixture ethanol–water with imidazolium-based ionic liquids

In this work, experimental data of isobaric vapour–liquid equilibria for the ternary system ethanol + water + 1-hexyl-3-methylimidazolium chloride ([C₆mim][Cl]) and for the corresponding binary systems containing the ionic liquid (ethanol + [C₆mim][Cl], water + [C₆mim][Cl]) were carried out at 101.300 kPa. VLE experimental data of binary and ternary systems were correlated using the NRTL equation. In a previous work [N. Calvar, B. González, E. Gómez, A. Domínguez, J. Chem. Eng. Data 51 (2006) 2178–2181], the VLE of the ternary system ethanol + water + [C₄mim][Cl] was determined and correlated, so we can study the influence of different ionic liquids in the behaviour of the azeotropic mixture ethanol–water.     

Viscosity of ionic liquid mixtures of 1-alkyl-3-methylimidazolium hexafluorophosphate + CO2

The viscosities of the mixtures 1-hexyl-3-methylimidazolium hexafluorophosphate ([HMIM][PF₆]) + CO₂ and 1-octyl-3-methylimidazolium hexafluorophosphate ([OMIM][PF₆]) + CO₂ were measured with a rolling ball viscometer. The CO₂ mole fraction for one mixture ranged up to 0.434 and the other up to 0.447. The viscosities were measured at 293.15-353.15 K and 10-20.0 MPa. The experimental uncertainty in viscosity was estimated to be within ±3.0%. The experimental data were compared with McAllister's three-body model, which correlated with the experimental data within average absolute deviations of 5.9%.