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.     

Simultaneous Absorption of Carbon Dioxide and Sulfur Dioxide into Aqueous 2-Amino-2-Methy-1-Propanol

Abstract

Carbon dioxide and sulfur dioxide were simultaneously absorbed into aqueous 2-amino-2-methyl-1-propanol (AMP) in a stirred semi-batch tank with a planar gas-liquid interface within a range of 0–4.0 kmol/m³ of AMP, 0.03–0.3 mole fraction of CO₂, 0.005–2 mole fraction of SO₂, and 298–318 K. Absorption data of each gas in the CO₂-AMP and SO₂-AMP systems are obtained to verify their reaction regimes, based on film theory, respectively, which are used to analyze the simultaneous absorption mechanisms of CO₂ and SO₂ in the CO₂-SO₂-AMP systems. The measured absorption rates of CO₂ and SO₂ are compared to those formulated by an approximate solution of the mass balances with simultaneous reactions.     

Simultaneous Absorption of Carbon Dioxide and Nitrogen Dioxide into Aqueous 2-amino-2-methy-1-propanol

Carbon dioxide and nitrogen dioxide were simultaneously absorbed into aqueous 2-amino-2-methyl-1-propanol (AMP) in a stirred semi-batch tank with a planar gas-liquid interface within a range of 0–4.0 kmol/m³ of AMP, 0.03–0.3 atm of CO₂, 0.005–0.2 atm of NO₂, and 298–318 K. Absorption data of each gas in the CO₂-AMP and NO₂-AMP systems were obtained to verify their reaction regimes, based on film theory, respectively, which were then used to analyze the simultaneous absorption mechanisms of CO₂ and NO₂ in the CO₂-NO₂-AMP systems. The measured absorption rates of CO₂ and NO₂ were compared to those formulated by an approximate solution of the mass balances with simultaneous reactions.     

New AMP/polyamine blends for improved CO2 capture: Study of kinetic and equilibrium features

2-Amino-2-methyl-1-propanol (AMP), which is the sterically hindered form of monoethanolamine (MEA), is a credible substitute to conventional CO₂-capturing solvents. Its performance can be improved by blending with a highly reactive polyamine promoter. Two such aqueous blends of AMP/TETA and AMP/TEPA were chosen here (TETA = triethylenetetramine and TEPA = tetraethylenepentamine). The kinetics of CO₂ absorption in the proposed blends was investigated at 308, 313, and 318 K using the stirred cell technique. The concentrations of AMP and polyamine were varied between 2 to 3 kmol/m³ and 0.1 to 0.5 kmol/m³, respectively. From the measured values of the fast pseudo-first order constants, the second-order rate constants for the reactions of CO₂ with TETA (14 695 m³/(kmol s)) and TEPA (19 250 m³/(kmol s)) were determined at T = 313 K. Both TETA and TEPA react faster with CO₂ than MEA. Further, the respective activation energy values were found (40 and 37 kJ/mol). Finally, the equilibrium solubility of CO₂ for both blends was measured at T = 303 K. The loading capacity was higher than that for the aqueous blends of AMP/MEA, AMP/DEA, and AMP/MDEA (here, DEA and MDEA denote diethanolamine and N-methyldiethanolamine). The highest value of loading capacity (1.12 mol CO₂/mol amine at 2.01 kPa equilibrium partial pressure of CO₂) was noted in AMP/TEPA mixtures. The new findings on our proposed blends will strengthen the AMP/polyamine application in CO₂ separation.     

Simultaneous absorption of carbon dioxide,sulfur dioxide,and nitrogen dioxide into aqueous 1, 8-diamino-p-menthane

3 gaseous mixtures of CO₂, SO₂, and NO₂ were simultaneously absorbed into 1, 8-diamino-p-menthane (DAM) in a stirred, semi-batch tank with a planar, gas-liquid interface within a range of 0–2.0 kmol/m³ of DAM, 0.05–0.3 atm of CO₂, 0.0025–0.04 atm of SO₂, and 298.15–323.15 K at a fixed NO₂ of 0.001 atm to measure their total molar fluxes. Diffusivity and Henry constants of CO₂, SO₂, and NO₂ were obtained using the reference data, measured by N₂O analogy. The mass transfer coefficient of each gas, needed to obtain the absorption rate without a chemical reaction, was modified with viscosity of aqueous DAM solution. In CO₂-SO₂-NO₂-DAM system accompanied by first-order reaction with respect to CO₂ and instantaneous reactions with respect to SO₂ and NO₂, the enhancement factors of CO₂ and SO₂ were obtained by using an approximate solution of mass balances consisting of reaction regimes of two gases, one of which reacts instantaneously, and then, the enhancement factor of NO₂ by comparing the instantaneous rates of SO₂ and NO₂. The observed values of the molar flux approached to the calculated values very well.     

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.     

Characteristics of absorption and regeneration of carbon dioxide in aqueous 2-amino-2-methyl-1-propanol/ammonia solutions

In this study, the removal efficiency, absorption amount, and loading value of CO₂ into aqueous blended 2-amino-2-methyl-1-propanol (AMP)/ammonia (NH₃) solutions were measured by using the absorption and regeneration continual process. The effect of adding NH₃ to enhance absorption characteristics of AMP was investigated. The performance was evaluated under various operating conditions. As a result, the method of blending AMP and NH₃ was not adequate because of a problem with scale formation. Consequently, NH₃ of 1, 3, 5, and 7 wt% was added to 30 wt% AMP. Of these additions, 5 wt% NH₃ was the optimum concentration because the CO₂ removal efficiency and absorption amount were almost 100% and 2.17 kg CO₂/kg absorbent, respectively. Also, the scale problem was almost absent. As the regenerator temperature varied from 80–110 °C, the loading of rich amine was almost constant, but the loading of lean amine was decreased as the regenerator temperature increased. Thus, the optimum regenerator temperature was 110 °C in this experiment.     

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

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

Effect of gas-liquid phase compositions on NO2 and NO absorption into ammonium-sulfite and bisulfite solutions

The effect of gas-liquid phase compositions on NO and NO₂ absorption into ammonium-sulfite and bisulfite solutions is investigated. Preliminary experiment results indicate that the concentrations of (NH₄)₂SO₃ or NH₄HSO₃ solution and the molar ratio for HSO₃⁻ to the total solution concentrations all have significant impact on NO₂ and NO absorption rates. While the solution concentration is constant, the absorption of NO_x mixture is strongly related to the ratio NO₂/NO_x. The absorption rate of NO is primarily affected by NO₂ inlet concentration, and the NO absorption rate reaches the maximum value in (NH₄)₂SO₃ solution with the increase of NO₂ inlet concentration, which is determined by the reaction of NO and NO₂ with SO₃²⁻ as well as NO formation. Moreover, when the solution is NH₄HSO₃ the best ratio of NO₂/NO for the maximum value of the NO absorption rate becomes less or smaller. Meanwhile, the presence of NO in the gas phase is also favorable to the absorption rate of NO₂ in ammonium-sulfite or bisulfite solutions. The total results suggest that the coexistence of NO and NO₂ in the flue gas could enhance the absorption of each other to some extent.     

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.     

Simultaneous Absorption of Carbon Dioxide and Sulfur Dioxide into Aqueous 1,8-Diamino-p-menthane

Abstract

Carbon dioxide and sulfur dioxide were simultaneously absorbed into aqueous 1,8-diamino-p-menthane (DAM) in a stirred semi-batch tank with a planar gas-liquid interface within a range of 0–2.0 kmol/m³ of DAM, 0.01–0.12 mole fraction of CO₂, 0.001–0.012 mole fraction of SO₂, and 298-318 K. Absorption data of each gas in the CO₂-DAM and SO₂-DAM systems are obtained to verify their reaction regimes, based on film theory, respectively, which are used to analyze the simultaneous absorption mechanisms of CO₂ and SO₂ in the CO₂-SO₂- DAM systems. In the simultaneous absorption rate of CO₂ and SO₂ into DAM solution, the absorption of CO₂ belongs to the second-order reaction of finite rate and the absorption of SO₂ belongs to the instantaneous reaction regime.     

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.     

Kinetic Studies on NO2 Absorption into Ammonium Sulfite Solutions

The absorption reactions of NO₂ into (NH₄)₂SO₃ solution were investigated in a stirred tank reactor. The kinetic regime of the absorption reaction was identified and the effects of various experimental parameters were studied. The experimental results indicated that the absorption of NO₂ into (NH₄)₂SO₃ solution is accompanied by a fast pseudo-first-order reaction. It was found that the NO₂ absorption rates were enhanced by the increasing concentration of (NH₄)₂SO₃ but nearly remained constant if the concentration is greater than 0.1 mol/L. The absorption rates also increased with increasing the reaction temperature and the concentration of NO₂ in inlet gas, but decreased as the oxygen concentration increased.     

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.     

Improvement in CO2 absorption and reduction of absorbent loss in aqueous NH3/triethanolamine/2-amino-2-methyl-1-propanol blends

Changes in the CO₂ absorption rates and capacities of the absorbent 2-amino-2-methyl-1-propanol (AMP), blended with NH₃ and other additives, were investigated toward performance improvement. The NH₃-blended absorbent removed CO₂ more efficiently than the AMP absorbent alone. However, absorbent loss through NH₃ evaporation was observed under these conditions. A second absorbent, the tertiary amine triethanolamine (TEA), which has a low vapor pressure, was selected and blended with the NH₃/AMP system to reduce NH₃ evaporation. Its effects on NH₃ loss and the absorption rate and capacity of the NH₃/AMP system were investigated, and the optimum blending ratios were determined. In addition, the absorbent blend at the optimum blending ratio was compared to AMP alone and the commercially available absorbent monoethanolamine at the same weight ratio. The thermal stabilities of the absorbents, under conditions used in the CO₂ absorption process, were compared by thermogravimetric analysis.     

Absorption of carbon dioxide in piperazine activated concentrated aqueous 2-amino-2-methyl-1-propanol solvent

In this work new experimental data on the rate of absorption of CO₂ into piperazine (PZ) activated concentrated aqueous solutions of 2-amino-2-methyl-1-propanol (AMP) over the temperature range 303–323 K are presented. The absorption experiments have been carried out in a wetted wall contactor over CO₂ partial pressure range of 5–15 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 40 wt%. The physical properties such as density and viscosity of concentrated aqueous AMP+PZ, as well as physical solubility of CO₂ in concentrated aqueous AMP+PZ, are also measured. New experimental data on vapor liquid equilibrium (VLE) of CO₂ in these concentrated aqueous solutions of AMP+PZ in the temperature range of 303–323 K have also been presented. The VLE measurements are carried out in an equilibrium cell in CO₂ pressure range of 0.1–140 kPa. A thermodynamic model based on electrolyte non-random two-liquid (eNRTL) theory is used to represent the VLE of CO₂ in aqueous AMP+PZ. Liquid phase speciations are estimated considering the nonideality of concentrated solutions of the amines and the calculated activity coefficients by eNRTL model. The CO₂ absorption in the aqueous amine solutions is described by a combined mass transfer-reaction kinetics model developed according to Higbie's penetration theory. The model predictions have been found to be in good agreement with the experimental results of the rates of absorptions of CO₂ into aqueous AMP+PZ.     

Removal of CO2 and/or SO2 from gas streams by a membrane absorption method

Studies were made on the membrane absorption of CO₂ and/or SO₂ using hydrophobic microporous hollow-fibre (HF) membrane modules. The absorbent liquids used were aqueous solutions of NaOH, K₂CO₃, alkanolamines and Na₂SO₃, flowing on the lumen side of the HF in laminar flow. A semi-empirical correlation was derived for the gas-phase mass-transfer coefficient on the shell side, by including geometrical factors of the HFs and the shell tube in the general correlation for mass transfer. It was found that the CO₂ absorption rate in various aqueous solutions of alkalis and alkanolamines is successfully described by a model based on gas diffusion through the membrane pores subsequent to gas absorption accompanied by chemical reaction. The simultaneous membrane absorption of SO₂ and CO₂ was also studied using aqueous Na₂SO₃ solution, the selective removal of SO₂ to CO₂ being successfully achieved when both the liquid flow rate and solute concentration are low. This suggests that this membrane absorption method provides an energy saving process for SO₂ removal from flue gases.     

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     

CO2‐Switchable Oil/Water Emulsion for Pipeline Transport of Heavy Oil

By mixing an aqueous solution of tertiary amine, N,N‐dimethylethanolamine (DMEA), with naphthenic acid (RCOOH) derived from heavy oil, a CO₂ switchable zwitterionic surfactant (RCOO^?DMEAH⁺) aqueous system was constructed. The CO₂ switchability of this zwitterionic surfactant was confirmed by visual inspection, pH measurements, and conductivity tests, i.e., the RCOO^?DMEAH⁺ decomposed into RCOOH, DMEAH⁺ and HCO₃^? after bubbling CO₂ through but switched back to its original state by subsequent bubbling N₂ through at 80 °C to remove the CO₂. The interfacial tension tests of heavy oil in DMEA aqueous solutions indicated that the solution containing 0.5 wt% of DMEA and 0.2 wt% of NaCl resulted in the lowest interfacial tension. The O/W emulsion formed when aqueous solutions of DMEA were used to emulsify heavy oil exhibited the best performance when the oil/water volume ratio, DMEA concentration, and NaCl concentration were 65:35, 0.5 and 0.2 wt%, respectively. The feasibility of pipeline transport of the O/W heavy oil emulsion was evaluated. The results illustrated that the demulsification of the O/W emulsion after transport could be easily realized by bubbling CO₂ through. Although demulsification efficiency still needs to be improved, the recycling of the aqueous phase after demulsification by removal of CO₂ looks promising.     

Absorption of carbon dioxide into aqueous colloidal silica solution with different sizes of silica particles containing monoethanolamine

Carbon dioxide was absorbed into an aqueous nanometer-sized colloidal silica solution in a flat-stirred vessel at 25 °C and 101.3 kPa to measure the absorption rate of CO₂. The concentrations of silica were in the range of 0–31 wt% and the sizes were 7, 60, and 111 nm. The solution contained monoethanolamine (MEA) of 0–2.0 kmol/m³. The volumetric liquid-side mass transfer coefficient (k _L a) of CO₂ was correlated with the empirical formula representing the rheological property of silica solution. The use of the aqueous colloidal silica solution resulted in a reduction of the absorption rate of CO₂ compared with Newtonian liquid based on the same viscosity of the solution. The chemical absorption rate of CO₂ was estimated by film theory using k _L a and physicochemical properties of CO₂ and MEA.