Role of absorber and desorber units and operational conditions for N-nitrosamine formation during amine-based carbon capture

The formation of carcinogenic N-nitrosamines from reactions between solvent amines and flue gas NOx is an important concern for the application of amine-based processes to capture CO2 post-combustion. Using an advanced test rig with interconnected absorber and desorber units, we evaluated the importance for N-nitrosamine formation of the desorber relative to the absorber, and any synergism between the two units. Variations in desorber temperature and in flue gas composition indicated that N-nitrosamine formation from fresh monoethanolamine (MEA) occurred predominantly in the absorber. N-nitrosamine formation was driven by high NO2 and O2 flue gas concentrations, although NO also contributed. In contrast, N-nitrosamine formation from piperazine (PZ) was driven by reactions with nitrite in the heated desorber, and accelerated concurrent with nitrite accumulation. A complementary experiment simulating aged MEA solvent (high nitrite, 1.5% sarcosine as a proxy of secondary amine degradation products) suggested the desorber becomes an order of magnitude more important than the absorber for N-nitrosamine formation. For fresh MEA solvent, increasing the desorber temperature from 110 °C to 130 °C promoted thermal decomposition of N-nitrosamines, reducing N-nitrosamine accumulation rates two-fold. Compared to the test rig, the prevailing practice of using separate absorber columns and autoclave-like treatments to mimic desorber units predicted the direction, but underestimated the magnitude of N-nitrosamine formation. Because N-nitros...