Modeling of carbon dioxide absorption/stripping by aqueous methyldiethanolamine/piperazine

Frailie, Peter Thompson, II
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Rigorous thermodynamic and kinetic models were developed in Aspen Plus® Rate SepTM for 8 m PZ, 5 m PZ, 7 m MDEA/2 m PZ, and 5 m MDEA/5 m PZ. Thermodynamic data was regressed using a sequential regression methodology, and incorporated data for all amine, amine/water, and amine/water/CO₂ systems. The sensitivity of CO₂ absorption rate was determined in a wetted wall column simulation in Aspen Plus®, and the results were used in Microsoft Excel to determine the optimum reaction rates, activation energies, and binary diffusivities. Density, viscosity, and binary diffusivity are calculated using user-supplied FORTRAN subroutines rather than built-in Aspen Plus® correlations. Three absorber configurations were tested: adiabatic, in-and-out intercooling, and pump-around intercooling. The two intercooled configurations demonstrated comparable improvement in capacity and packing area, with the greatest improvement in 8 m PZ occurring between lean loadings of 0.20 and 0.25 mol CO₂/mol alkalinity. The effects of absorber temperature and CO₂ removal were tested in the adiabatic and in-and-out intercooled configurations. For 7 m MDEA/2 m PZ at a lean loading of 0.13 mol CO₂/mol alkalinity reducing the absorber temperature from 40 °C to 20 °C increases capacity by 64% without an appreciable increase in packing area. Increasing CO₂ removal from 90% to 99% does not double the packing area due to favorable reaction rates at the lean end of the absorber. Two stripper configurations were tested: the simple stripper and the advanced flash stripper. For all amines, absorber configurations, and lean loadings the advanced flash stripper demonstrated the better energy performance, with the greatest benefit occurring at low lean loadings. An economic estimation method was developed that converts purchased equipment cost and equivalent work to $/MT CO₂. The method is based on economic factors proposed by DOE-NETL and IEAGHG. The total cost of CO₂ decreases as lean loading decreases for all amines and configurations. Increasing CO₂ removal from 90% to 99% results in a 1% increase in the total cost of CO₂ capture. Decreasing absorber temperature for 7 m MDEA/2 m PZ from 40 °C to 20 °C decreases total cost of CO₂ capture by up to 9.3%.