Kinetics of absorption of carbon dioxide in aqueous piperazine solutions

In the present work the absorption of carbon dioxide into aqueous piperazine (PZ) solutions has been studied in a stirred cell, at low to moderate temperatures, piperazine concentrations ranging from 0.6 to , and carbon dioxide pressures up to 500 mbar, respectively. The obtained experimental results were interpreted using the DeCoursey equation [DeCoursey, W., 1974. Absorption with chemical reaction: development of a new relation for the Danckwerts model. Chemical Engineering Science 29, 1867-1872] to extract the kinetics of the main reaction, 2PZ+CO₂→PZCOO^-+PZH⁺, which was assumed to be first order in both CO₂ and PZ. The second-order kinetic rate constant was found to be at a temperature of , with an activation temperature of . Also, the absorption rate of CO₂ into partially protonated piperazine solutions was experimentally investigated to identify the kinetics of the reaction . The results were interpreted using the Hogendoorn approach [Hogendoorn, J., Vas Bhat, R., Kuipers, J., Van Swaaij, W., Versteeg, G., 1997. Approximation for the enhancement factor applicable to reversible reactions of finite rate in chemically loaded solutions. Chemical Engineering Science 52, 4547-4559], which uses the explicit DeCoursey equation with an infinite enhancement factor which is corrected for reversibility. Also, this reaction was assumed to be first order in both reactants and the second-order rate constant for this reaction was found to be at 298.15 K.     

Kinetics of the absorption of carbon dioxide into aqueous ammonia solutions

Experiments were performed in a customized double stirred tank reactor to study the kinetics of CO₂ absorption into NH₃ solutions at concentrations ranging from 0.42 to 7.67 kmol·m^?3 and temperatures between 273.15 and 293.15 K. The results show that the reactive absorption was first order with respect to CO₂ but fractional order (1.6–1.8) with respect to ammonia. Experimental data can be satisfactorily interpreted by a termolecular mechanism using and . © 2016 American Institute of Chemical Engineers AIChE J, 62: 3673–3684, 2016     

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.     

Kinetics of carbon dioxide reaction with diethylaminoethanol in aqueous solutions

Differential rates of CO₂ adsorption into 0.90, 0.47 and 0.24 M aqueous solutions of 2-(diethylamino)ethanol (DEAE) were measured at 323 K over a wide range of carbonation ratios. A rigorous thermodynamic model was used to define species activities which were coupled with Danckwerts' gas-liquid reaction model to deduce the kinetics. The reaction of CO₂ with this highly basic tertiary amine occurs by two pathways: (1) a minor path via the CO₂ reaction with hydroxide ion and (2) a predominant reaction pathway that can be characterized by its first order dependency on the free amine concentration. The second reaction was proposed to involve an internal salt-like intermediate,.     

Kinetics of carbon dioxide absorption into catalysed potassium carbonate solutions

Carbon dioxide was absorbed in potassium carbonate-bicarbonate buffer solutions. Some of these solutions contained arsenious ion as catalyst. The experiments were performed in a wetted wall absorber, in conditions of stagnant gas phase and at constant temperature, with the aim of elucidating the influence of the carboante ion concentration on the catalytic process. A kinetic equation was obtained, that was critically compared with the experimental data published previously by various investigators.     

Kinetics of carbon dioxide chemical absorption into cyclic amines solutions

Chemical reaction kinetics between carbon dioxide with two cyclic amines (pyrrolidine and piperidine) have been studied using a stirred tank reactor with a planar interfacial area. The operational variables considered in this work have been the amine concentration in the liquid phase and the reaction temperature. Specific absorption rates have been determined under different experimental conditions. Results indicate that the absorption process occurs in a pseudo first reaction regime exhibited first‐order kinetic with respect carbon dioxide and a second order for both cyclic amines. The reaction‐rate constant was determined under the different experimental conditions, and it was correlated depending on the temperature by means of an Arrhenius type equation. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Kinetics of absorption of carbon dioxide into aqueous solutions of 2-amino-2-hydroxymethyl-1,3-propanediol

In this work the kinetics of the reaction between CO₂ and a sterically hindered alkanolamine, 2-amino-2-hydroxymethyl-1,3-propanediol (AHPD) were determined at temperatures of 303.15, 313.15 and 323.15 K in a wetted wall column contactor. The AHPD concentration in the aqueous solutions was varied in the range 0.5-2.4 kmol m⁻³. The ratio of the diffusivity and Henry's law constant for CO₂ in solutions was estimated by applying the N₂O analogy and the Higbie penetration theory, using the physical absorption data of CO₂ and N₂O in water and of N₂O in amine solutions. Based on the pseudo-first-order for the absorption of CO₂, the overall pseudo-first-order rate constants were determined from the kinetics measurements. By considering the zwitterion mechanism for the reaction of CO₂ with AHPD, the zwitterion deprotonation and second-order rate constants were calculated. The second-order rate constant, k₂, was found to be 285, 524, and 1067 m³ kmol⁻¹ s⁻¹ at 303.15, 313.15, and 323.15 K, respectively.     

Absorption of carbon dioxide into aqueous colloidal silica solution with diisopropanolamine

Carbon dioxide was absorbed into the aqueous nanometer-sized colloidal silica solution of 0–31 wt% and diisopropanolamine of 0–2 kmol/m³ in a flat-stirred vessel with the impeller of various sizes and speeds at 25 °C and 0.101 MPa to measure the absorption rate of CO₂. The volumetric liquid-side mass transfer coefficient (k_La) of CO₂ was used to obtain the empirical correlation formula containing the rheological behavior of the aqueous colloidal silica solution. Reduction of the measured k_La was explained by the viscoelastic properties of the aqueous colloidal silica solution. The theoretical value of the absorption rate of CO₂ was estimated from the model based on the film theory accompanied by chemical reaction and compared with the measured value.     

Kinetics of carbon dioxide absorption in aqueous solution of diethylenetriamine (DETA)

A string of discs contactor was used to measure the kinetics CO₂ absorption in unloaded aqueous solution with the diethylenetriamine (DETA) concentrations ranging between 1.0 and 2.9 kmol m⁻³ and at temperatures ranging between 298.1 and 332.3 K. The reaction rates strongly increase as the increasing the concentrations and temperatures. Both the termolecular and the zwitterion models were applied to interpret the experimental data and gave identical results for all practical purposes. The reaction order with respect to the DETA concentration is found to vary slightly with temperature between 1.71 and 1.76 with an average of about 1.73. Both DETA and water contribute as a base in carbamate formation. It was found that fitting of experimental data to the termolecular mechanism gave statistically more robust results than fitting to the zwitterion mechanism.     

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.     

Oxygen absorption in aqueous sulphur dioxide solutions

An improved kinetic model of catalytic oxidation of tetravalent sulphur in aqueous solutions has been suggested, based on oxygen absorption experiments carried out in a stirred tank with a plane interface. The model comprises a chemical network of catalyst (manganous soluble salt) transformations and a set of step rate equations with the appropriate kinetic constants determined. It indicates the possible enhancement of tetravalent sulphur oxidation by applying conditions of the manganous dimer maximum concentration.     

Kinetics of the reaction of carbon dioxide with aqueous sodium and potassium carbonate solutions

Kinetics for CO₂ absorption into 5–30 wt-% sodium carbonate solutions and 5–50 wt-% potassium carbonate solutions up to 70 °C were studied in a string of discs apparatus under conditions, in which the reaction of CO₂ could be assumed pseudo-first-order. The experimental data were evaluated based on the use of activities in the reaction rate expressions. The second order kinetic constant for the CO₂ reaction CO₂+OH^??HCO₃^? at infinite dilution is discussed and an expression for it is obtained up to 70 °C.The difference between the activity and concentration based kinetic constants were found to be small at low concentrations, where the apparent Henry’s law constant is close to that at infinite dilution in water. However, at high concentrations (high apparent Henry’s law constants), the difference was bigger. Using the activity based approach, the second order kinetic constant was calculated, compared to the second order kinetic constant in infinite dilution and found to be independent of both carbonate concentration and the cation present in the solution.     

Kinetics of oxygen absorption in aqueous sodium dithionite solutions

The absorption and reaction of oxygen in aqueous alkaline solutions of sodium dithionite has been experimentally investigated in a novel gas-liquid contactor. The novel gas-lift bubble column contactor was used to study the kinetics over wide ranges of reactant concentrations, temperature, and pH. The oxygen-sodium dithionite reaction was found to be first-order with respect to dithionite in the range of dithionite concentration < 0.1 M, and second-order in the range of dithionite concentration > 0.1 M. The reaction with respect to oxygen was found to be zero-order for all dithionite concentrations. These results and experimental investigations of the effect of solution alkalinity and temperature on the reaction rate are consistent with previous findings obtained in different gas-liquid contactors. The results thus confirm the feasibility of using the gas-lift bubble column for the kinetics of gas-liquid reactions.     

Gas absorption with consecutive chemical reaction: Absorption of carbon dioxide into aqueous amine solutions

Experiments were carried out over a wide range of contact time for the absorption of carbon dioxide into aqueous amine solutions. It was suggested from the experimental results with a laminar liquid-jet, a wetted wall column and a quiescent liquid absorber that the present absorption processes should be analyzed by a gas absorption with the consecutive reaction of the form of A + 2B →k_I R and A + R →k_II Products. The values of rate constants for the second-order first reaction step (k₁) for the diethanolamine and triethanolamine were estimated as 1340 and 16.8 1/mol-sec, respectively. The value of rate constant for the second reaction step was found to be constant irrespective of the liquid reactant.     

Equilibrium between carbon dioxide and aqueous monoethanolamine solutions

The partial pressure of carbon dioxide has been measured over aqueous monoethanolamine solutions (1.0, 2.5, 3.75 and 5.0 N) at temperatures of 25, 40, 60, 80, 100 and 120°C. Partial pressures of CO₂ ranged between 0.2 and 6616 kPa.^b The results extend previously published data to higher partial pressures. Comparisons have been made with two methods of prediction based upon a thermodynamic model.     

Investigation on kinetics of carbon dioxide absorption in aqueous solutions of monoethanolamine + 1, 3-diaminopropane

ABSTRACT

Environmental concerns from global warming and climate change demand carbon dioxide separation from post-combustion gases. Important parameters are involved in choosing the suitable solvent for carbon dioxide separation, including the reaction rate of carbon dioxide and the solvent. In this paper, the kinetics of carbon dioxide (CO₂) absorption in aqueous solutions of Monoethanolamine (MEA) + 1,3-Diaminopropane (DAP), a diamine containing two primary amino group, was developed. The measurements were performed in a stirred cell with a horizontal gas-liquid interface in the temperature range of 313.15–333.15 K and aqueous solutions of 10 wt% MEA + 5 wt% DAP and 12.5 wt% MEA + 2.5 wt% DAP. Experiments were conducted in an isothermal batch reactor with a horizontal gas-liquid interface under pseudo-first-order conditions, enabling the determination of the overall kinetic rate constant from the pressure drop method. Second-order reaction rate constants of CO₂ absorption in amine solutions were estimated using the calculated initial absorption rate. It was found that the rate constants in MEA+ DAP solutions were greater than in MEA solutions which means that DAP increases the reaction rate.