Amine and Glycol Gas Recovery Methods
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satishchemengAmine and Glycol Gas Recovery Methods
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satishchemengDimethyl ethers & Poly ethylene Glycol
Methanol
Advantages of Physical and Chemical Solvents
CHEMICAL ABSORPTION:
AMINES:
Amines are compounds formed from ammonia (NH3) by replacing one or more of the
hydrogen atoms with another hydrocarbon group.
Replacement of single hydrogen produces a primary amine, replacement of two
hydrogen atoms produces a secondary amine, and replacement of all three of the
hydrogen atoms produces a tertiary amine.
The amines are used in water solutions in concentrations ranging from approximately 10 to 65
wt% amines
Amines remove H2S and CO2 in a two-step process:
1. The gas dissolves in the liquid (physical absorption).
2. The dissolved gas, which is a weak acid, reacts with the weakly basic amines.
Absorption from the gas phase is governed by the partial pressure of the H2S
and CO2 in the gas, whereas the reactions in the liquid phase are controlled by the reactivity of
the dissolved species.
A. H2S REACTION:
Regardless of the structure of the amine, H2S reacts rapidly with the primary,
secondary, or tertiary amine via a direct protontransfer reaction, as shown in Equation
5.1, to form the amine hydrosulfide
The reaction is shown for a tertiary amine but applies to primary and secondary
amines as well
B. CO2 REACTION
Co2 Reaction with Tertiary amine:
The reaction between the amine and the CO2 is more complex because CO2 reacts via
two different mechanisms(One is given above). When dissolved in water, CO2,
hydrolyzes to form carbonic acid, which, in turn, slowly dissociates to bicarbonate.
The bicarbonate then undertakes an acid−base reaction with the amine to yield the
overall reaction shown by Equation 5.2.
CO2 reaction with mono and Di Amines:
This second reaction mechanism for CO2, which forms the amine salt of a substituted
carbamic acid, is called the carbamate formation reaction and occurs only with the
primary and secondary amines. The CO2 reacts with one primary or secondary amine
molecule to form the carbamate intermediate, which in turn reacts with a second amine
molecule to form the amine salt.
The rate of CO2 reaction via carbamate formation (5.3) is much faster than the CO2
hydrolysis reaction (5.2) , but slower than the H2S acid−base reaction.
CO2 Loading of amines:
The stoichiometry of the carbamate reaction indicates that the capacity of the amine solution for
CO2 is limited to 0.5 moles of CO2 per mole of amine if the only reaction product is the amine
carbamate.
However, the carbamate undergoes partial hydrolysis to form bicarbonate, which
regenerates free amine. Hence, CO2 loadings greater than 0.5, as seen in some plants
that employ diethanolamine (MDEA), are possible through the hydrolysis of the
carbamate intermediate to bicarbonate
Hence, it is clear higher loading of CO2 is possible by using the tertiary amines
because of different reaction mechanism even though the reaction is slow.
Why tertiary Amines cannot remove complete CO2 :
The fact that CO2 absorption occurs by two reaction mechanisms with different
kinetic characteristics, significantly affects the relative absorption rates of H2S and
CO2 among the different alkanolamines
If not tertiary:
For primary and secondary amines, little difference exists between the H2S and CO2
reaction rates because of the availability of the rapid carbamate formation for CO2
absorption. Therefore, the primary and secondary amines achieve essentially complete
removal of H2S and CO2.
If Tertiary:
However, because the tertiary amines have no labile hydrogen, they cannot form the
carbamate. Tertiary amines must react with CO2 via the slow hydrolysis mechanism in
Equation 5.2. With only the slow acid−base reaction available for CO2 absorption,
methyldiethanolamine (MDEA) and several of the formulated MDEA products
yield significant selectivity toward H2S relative to CO2, and, consequently, all of the
H2S is removed while some of the CO2 “slips” through with the gas. Because the CO2
reaction with water to form bicarbonate is slow and the H2S reaction is fast for MDEA,
the H2S reaction is considered gas-phase limited and the CO2 reaction is considered
liquid-phase limited.
For the reactions discussed above, high pressures and low temperatures drive the
reactions to the right, whereas high temperatures and low pressures favor the reverse
reaction, which thus provides a mechanism for regeneration of the amine solution
