SOLVENTS USED FOR CO2 ABSORPTION

• Monoethanolamine(MEA) - It is used as a solvent for CO2 absorption

Chemistry of the MEA –
 .
• The equilibrium constants for the reaction are temperature dependent and follow
the dependence given
lnKx = A + (B/T) + C lnT + DT
In this case, T is the temperature in °K. The constants A, B, C, D for the different
for different reactions.
Absorption of CO2 and regeneration of solvent:
Flue gases that enter through the bottom of the absorber and the lean MEA solvent
which is coming from the top of the absorber. Temperature condition in the
absorber is 40 °C and high pressure. water wash to remove any entrained MEA that
may be carried out along with the vent gas that is stripped of CO2. It also serves the
function of cooling the vent gas before it is released to the atmosphere. In the
reboiler of the desorber heat duty is arises from three different requirements:1)
Sensible heat to raise the temperature of the rich stream to that in the desorber .
2) . Heat to produce steam to maintain driving force for transfer of CO2 from liquid
phase to gas phase .3) Heat of reaction to reverse the absorption reaction and
release CO2 .
 Temperature dependent parameters for
equilibrium constants in MEA system
Reaction A B C D
Kx
(3-3) 132.89 -13445.9 -22.47 0 9.59*10-18

(3-4) 231.46 -12092.1 -36.78 0 9.07*10-9

(3-5) -0.52 -2545.53 0 0 1.74*10-4

(3-6) -3.038 -7008.3 0 -0.00313 3.39*10-12

(3-7) 216.05 -12431.7 -35.48 0 1.09*10-12

 Thermochemistry in the MEA system
Reactions -ΔH (kcal/g
mol )

T 25°C 80°C 120°C

CO2(g) ----- CO2(aq) 4.9 2.9 1.3

CO2(aq) + H2 O ----- HCO3 - + H+ -2.2 1.7 4.7

MEA(aq) + H+ ----- MEA+ 12.0 12.2 12.1

MEA(aq) + HCO3 - -----> MEACOO+ + H2O 4.3 5.1 5.4

Overall reaction 18.9 21.9 23.6

.
. Potassium Carbonate
Benson performed solubility studies on the K2CO3-KHCO3-CO2 system and found that the use
of a 60% solution was prohibitive near 120°C (boiling point) because precipitation occurred at
a bicarbonate conversion of only 35%. The 50% solution was also not useful, because near the
boiling point of 113 C, precipitation takes place when the conversion to bicarbonate exceeded
48%. However, with a 40% solution, precipitation did not take place at 107 C (boiling point)
until a bicarbonate conversion of 90%. Hence, it is feasible to employ a 40 or 45% K2CO3
solution if the conversion to bicarbonate does not exceed 90 or 80% respectively.

Chemistry of the potassium carbonate

The overall reaction when carbon dioxide is absorbed in a solution of potassium
carbonate and potassium bicarbonate is given by
K2CO3 + CO2 + H2O ------> 2KHCO3 ΔH = -143 kJ /gmol
 Potassium Carbonate Process description

• the absorber typically operates at high pressures (> 10 atm). At these

high pressures, there is sufficient driving force in the absorber for
transfer of CO2 from the gas phase to the liquid phase. The process
operates at a high temperature (> 100 °C) and CO2 is absorbed at
nearly the same temperature as it is desorbed. Thus, the need for
cooling the flue gas before entry into the absorber is eliminated as is
the need 120 for cross-heat exchanger between the absorber and
desorber.
some steam needs to be supplied in the desorber for providing sensible
heat to the solution. This sensible heat requirement however is much
lower than that in the amine process.
.
 Chilled ammonia

• Two variations of this process have been discussed in this literature.

The first is the Aqua Ammonia process in which an aqueous ammonia
solution is used to capture CO2 with the absorption occurring at room
temperature
• The second variation is the chilled ammonia process In this process,
the absorption of CO2 in the ammonia solution is carried out under
refrigerated conditions in the temperature range of 0 to 10 °C
Chemistry of the chilled ammonia
 .

• CO2 is solubilized in the solution in the carbonate, bicarbonate and

carbamate forms. It is important to consider the carbamate formation
since this is a significant reaction. Many studies of the ammonia system
ignore the formation of the carbamate species and this results in a much
lower estimated heat of reaction.
Vapour-Liquid Equilibrium in H2O-MEA-
CO2
*)Several studies have been carried out on the solubility of CO2 in aqueous MEA
solution. Some experimental data covers a wide range of temperatures, pressures
and loadings, however it is available only for 30 mass % MEA. There is also a strong
need for more data in the very low loading and pressure regions for modeling
purposes. Thus an up-to-date VLE data set for the H2O-MEA-CO2 system, spanning
a large concentration range, is clearly needed
*) None of the existing models have used the solubility of N2O in MEA which by
utilizing the so-called N2O analogy gives a measure of the physical solubility, or
Henry’s law constant of CO2 in the aqueous MEA solution. Through the physical
solubility of CO2, the activity coefficient of CO2 can be calculated. Hessen (2010)
showed that existing models give CO2 activity coefficients.
Activity coefficient model
In H2O-MEA-CO2 System the existence of neutral specie pure MEA and H2O, and
ionic species – HCO3- and carbamate ion MEACOO- in the equilibrated liquid
phase have been considered.

• For simplicity, the free molecular species CO2 and the ionic species CO3-2 and OH-
in the liquid phase have been neglected since concentration of these species are
very low compared to the other species present in the equilibrated liquid phase.

*But observed that neglecting the concentration of free molecular CO2, and OH-
and CO3-2 ions in the liquid phase in this system for CO2 loading below 1.0 does not
result in significant error in the VLE predictions
*)The objectives of this work are to present a consistent VLE data set for MEA through experimental VLE measurements for 15,
30, 45 and 60 wt% MEA in the low and high CO2 loading regions from 40 to 120 *C use these data together with CO2 solubility
data based on the N2O analogy, to provide a rigorous equilibrium model based on the extended UNIQUAC model framework
*) The extended UNIQUAC model results for the N2O (physical) solubility of 30 wt% MEA are shown in figure 1. The average
absolute relative deviation (AARD) value of 2.7% indicates a very good representation of experimental data
 Process Intensification Systems
Process intensification uses or combines technologies to produce significantly
smaller, cleaner or more energy efficient processes. Process intensification will
reduce process footprint, save on energy inputs, and reduce overall costs for
equipment. 

Proprietary reactor-mixer is a classic

example of process-intensifying equipment.
Motivation for using PI in Post-combustion
CO2 capture with solvents process
• It was reported that a 500 MWe supercritical coal fired power plant operating at
46% efficiency releases over 8,000 tonnes of CO2 per day . PCC using solvents
based on the conventional technology (i.e. using packed columns) requires very
large packed columns.
• Dynamic modelling and simulation study of a 500MWe sub-critical coal-fired
power plant by Lawal . showed that two absorbers of 17m in packing height and
9m in diameter will be needed to separate CO2 from the flue gas.
• These huge packed columns translate into high capital costs. A significant amount
of steam from power plants has to be used for solvent regeneration. This
translates into high thermal efficiency penalty. It is reported that 3.2 to 4.5 MJ
energy is required to capture per kg of CO2 using MEA solvent.
• On the other hand, PI has potentials of significant capital cost reduction and also
to improve process dynamics.
Now there are general approaches to PI with the aim to
improve process performance

• (a) Reducing equipment size using an intensified field (e.g.

centrifugal, electrical, microwave).
• (b) Simplifying processes by integrating multiple process tasks in a
single item of equipment.
• (c) Reducing equipment size by reducing its scale of structure.

• Some typical PI studies are presented in Table 2 to evaluate the most

preferred option for CO2 capture application.