Absorber performance and configurations for CO2 capture using aqueous piperazine

Absorber design for CO2 capture with amine solvents is complicated by the presence of temperature gradients and multiple rate controlling mechanisms (chemical reaction and convective mass transfer). The development of rigorous rate-based models has created the opportunity to study the performance limiting mechanisms in detail. A structured approach was developed to validate absorber models, identify limiting phenomena, and develop configurations that specifically address limiting mechanisms. A rate-based model utilizing concentrated aqueous piperazine (PZ) was the focus of model validation and process development. The model was validated using pilot plant data, matching the number of transfer units (NTU) within + 1% while identifying a systematic bias (loading measurement) between the model and pilot plant data. The validated model was used to define limiting cases (isothermal and adiabatic absorbers) to study the effects of operating conditions on the formation of temperature-induced mass transfer pinches. The method allowed for screening of intercooling benefits – high CO2 applications (15% - 27% CO2) require intercooling over the entire practical loading range for PZ and benefit significantly from simple in-and-out intercooling with limited additional benefit expected from advanced design. Low CO2 (4% CO2) applications are expected to benefit the most from improved intercooling, but also have the largest operating window without the need for intercooling (< 0.22 mol CO2/mol alkalinity for 8 m PZ). An analogous approach was developed to study rate mechanisms. A mass transfer parameter sensitivity analysis approach was developed to identify the relative contribution to overall mass transfer resistance of each mechanism as a function of operating conditions and position in the absorber column. The pseudo-first order and instantaneous reaction asymptotic solutions to the reaction-diffusion problem were used to define a dimensionless parameter that quantifies the approach of the modeling results to the limiting conditions and was found to be predictive of the relative liquid film resistance (diffusion vs. reaction) at all conditions. The results of the analysis indicated that the absorber is strongly diffusion controlled, has limited gas-film resistance, and that equilibrium constraints at the rich end of the absorber (depletion of free amine) significantly increase diffusion limitations. Finally, the validation and mechanistic studies provided the basis for four new absorber configurations: 1) integration of a spray nozzle in the intercooling loop, 2) solvent recycle intercooling, 3) integrated flue gas and solvent cooling functions, 4) hybrid intercooling (high intensity contacting with intercooling). Each approach coupled mass transfer enhancement with intercooling and provided new degrees of freedom for operation and design of absorbers for CO2 capture.