To screen amine solvents for application in CO2 capture from coal-fired power plants, the equilibrium CO2 partial pressure and liquid film mass transfer coefficient were characterized for CO2-loaded and highly concentrated aqueous amines at 40 – 100 °C over a range of CO2 loading with a Wetted Wall Column (WWC). The acyclic amines tested were ethylenediamine, 1,2-diaminopropane, diglycolamine®, methyldiethanolamine (MDEA)/Piperazine (PZ), 3-(methylamino)propylamine, 2-amino-2-methyl-1-propanol and 2-amino-2-methyl-1-propanol/PZ. The cyclic amines tested were piperazine derivatives including proline, 2-piperidineethanol, N-(2-hydroxyethyl)piperazine, 1-(2-aminoethyl)piperazine, N-methylpiperazine (NMPZ), 2-methylpiperazine (2MPZ), 2,5-trans-dimethylpiperazine, 2MPZ/PZ, and PZ/NMPZ/1,4-dimethylpiperazine (1,4-DMPZ). The cyclic CO2 capacity and heat of CO2 absorption were estimated with a semi-empirical vapor-liquid-equilibrium model. 5 m MDEA/5 m PZ, 8 m 2MPZ, 4 m 2MPZ/4 m PZ and 3.75 m PZ/3.75 m NMPZ/0.5 m 1,4-DMPZ were identified as promising solvent candidates for their large CO2 capacity, fast mass transfer rate and moderately high heat of absorption. The speciation in 8 m 2MPZ and 4 m 2MPZ / 4 m PZ at 40 °C at varied CO2 loading was investigated using quantitative 1H and 13C nuclear magnetic resonance (NMR) spectroscopy. In 8 m 2MPZ at 40 °C over the CO2 loading range of 0 – 0.37 mol CO2/mol alkalinity, more than 75% of the dissolved CO2 exists in the form of unhindered 2MPZ monocarbamate, and the rest is in the form of bicarbonate and dicarbamate; 19% - 56% of 2MPZ is converted to 2MPZ carbamate at 0.1 - 0.37 mol CO2/mol alkalinity. A rigorous thermodynamic model was developed for 8 m 2MPZ in the framework of the Electrolyte Nonrandom Two-Liquid (ENRTL) model. At 40 °C, the reaction stoichiometry for 2MPZ and CO2 is around 2 at lean loading but diminishes to 0 at rich loading. Bicarbonate becomes the major product at CO2 loading greater than 0.35 mol/mol alkalinity. The predicted heat of CO2 absorption is 75 kJ/mol at 140 °C and decreases with temperature when CO2 loading is above 0.25. The mass transfer rate data for 8 m 2MPZ was represented with a rate-based WWC model created in Aspen Plus®. The reaction rate was described with termolecular mechanism on an activity basis. With minor CO2 loading adjustment and regression of pre-exponential kinetic constants and diffusion activation energy, a majority of the measured CO2 fluxes in the WWC experiments were fitted by the model within ±20% over 40 – 100 °C and 0.1 – 0.37 mol CO2/mol alkalinity. The diffusion activation energy for 8 m 2MPZ at the rich loading is about 28 kJ/mol. The activity-based reaction rate constant at 40 °C for 2MPZ carbamate formation catalyzed by 2MPZ is 1.94×1010 kmol/m3•s. The calculated liquid film mass transfer coefficients are in close agreement with the experimental values. The liquid film mass transfer rate is dependent on the diffusion coefficients of amine and CO2 to the same extent at lean loading and 40 °C. The sum of the powers for the two diffusivities is approximately equal to 0.5 over the loading range of 0 – 0.4 mol CO2/mol alkalinity. The sum of the powers for the dependence of the liquid film mass transfer coefficient on the carbamate formation rate constants (k2MPZ-2MPZ and k2MPZCOO--2MPZ) approaches 0.5 at very lean loading at low temperature, but it decreases as CO2 loading and temperature is increased. At 100 °C, the physical liquid film mass transfer coefficient is the most important factor that determines the liquid mass transfer rate. The pseudo-first order region shifts to higher range of physical liquid film transfer coefficient as temperature increases. / text

The effective mass transfer area (a [subscript e]), liquid film mass transfer coefficient (k [subscript L]), and gas film mass transfer coefficient (k [subscript G]) of eleven structured packings and three random packings were measured consistently in a 0.428 m packed column. Absorption of CO₂ with 0.1 gmol/L NaOH with 3.05 m packing was used to measure a [subscript e], while air stripping of toluene from water with 1.83 m packing was used to measure k [subscript L], and absorption of SO₂ with 0.1 gmol/L NaOH with 0.51 m packing was used to measure k [subscript G]. The experiments were conducted with liquid load changing from 2.5 to 75 m³/(m²*h) and gas flow rate from 0.6 to 2.3 m/s. Packings with surface area from 125 to 500 m²/m³ and corrugation angle from 45 to 70 degree were tested to explore the effect of packing geometries on mass transfer. The effective area increases with packing surface area and liquid flow rate, and is independent of gas velocity. The packing corrugation angle has an insignificant effect on mass transfer area. The ratio of effective area to surface area decreases as surface area increases due to the limit of packing wettability. A correlation has been developed to predict the mass transfer area with an average deviation of 11%. [Mathematical equation]. The liquid film mass transfer coefficient is only a function of liquid velocity with a power of 0.74, while the gas film mass transfer coefficient is only a function of gas velocity with a power of 0.58. Both k [subscript L] and k [subscript G] increase with packing surface area, and decrease with corrugation angle. A new concept, Mixing Point Density, was introduced to account for effect of the packing geometry on k[subscript L] and k [subscript G]. Mixing Point Density represents the frequency at which liquid film is refreshed and gas is mixed. The mixing point density can be calculated by either packing characteristic length or by surface area and corrugation angle: [mathematical equation]. The dimensionless k [subscript L] and k [subscript G] models can then be developed based on the effects of liquid/gas velocity, mixing point density, packing surface area: [mathematical equation] [mathematical equation]. Mi is the dimensionless form of Mixing Point Density (M), which is M divided by a [subscript P]³. Because Mi is only a function of corrugation angle (θ), it is a convenient transformation to represent the effect of θ on mass transfer parameters. An economic analysis of the absorber was conducted for a 250 MW coal-fired power plant. The optimum operating condition is between 50 to 80 % of flooding, and the optimum design is to use packing with 200 to 250 m²/m³ surface area and high corrugation angle (60 to 70 degree). The minimum total cost ranges from $4.04 to $5.83 per tonne CO₂ removed with 8 m PZ.