Amine Thermal Degradation (by Lili Lyddon)

In DEA degradation mechanism, Hydrocarbon Processing, October 1982, A. Meisen and M. L.

Kennard discuss the fact that DEA and MDEA thermal degradation is minimal up to 400F.
Although the degradation of DEA is caused by reaction with CO2 and not temperature alone,
temperature does affect the rate of degradation caused by reaction with CO2. This reference
states: Degradation increases strongly with temperature. This is not due to thermal breakdown
of DEA, but it requires the presence of carbon dioxide. Design and operation of DEA units must
avoid creation of elevated temperature throughout the plants. Heat transfer surfaces of DEA
stripper-reboilers (especially when gas fired) are particularly prone to formation of localized hot
spots. To prevent such hot spots in operating plants, DEA circulation through the stripperreboiler should be kept high and steam (or gas) temperature kept low. In many DEA units only
the bulk solution temperatures are measured. It must be remembered that the skin
temperatures of heat transfer surfaces can be very much higher, particularly during process
upsets. Reliance upon bulk temperatures is therefore inadequate.
In the paper Reduce amine plant solvent losses, Part 2 from Hydrocarbon Processing, June
1994, E. J. Stewart and R. A. Lanning mention that the thermal degradation of amines
accelerates above 350F, so the skin temperature of direct fired reboilers should be kept below
350F. They recommend a reboiler operation with an amine bulk temperature below
260F(126.67C) . This reference goes on to say: With hot oil and steam heating systems,
risk of thermal degradation is low since the heat media is usually not operated at high
temperature. However, in fired-reboiler operation, the temperature of amine on the tubes
surface can easily exceed 350F. In fired reboilers, forced circulation is often used to maintain
low skin temperatures. The rule of thumb is to maintain amine skin temperatures between
300F and 325F, and not exceed 350F. for these temperatures a conservative design heat flux
of less than 8000 Btu/ft2 of tube area is recommended.