Absorption of CO2 into Aqueous Potassium Salt Solutions of L-Alanine and

L-Proline

Introduction

The objective of this study is evaluate the CO2 absorption capacity and absorption heat of the
aqueous solutions of L-alanina and L-proline potassium salts.. The experiment has been
performed in the semi batch absorption system and differential reaction calorimeter. The
structure of L –alanine is similar to that of glycine, simplest amino acid.the L-alanine has the
higher absorption capacity. L-proline another amino acid classifies as secondary amino acid
have a structure of 5 membered ring with an amino functionality included. The co2 loaded
absorbents were investigated by using nuclear magnetic resonance (NMR) spectroscopy. The
results are compated with conventional solvents such as primary amine, monoethanolamine
(MEA) and secondary amine, diethanolamine (DEA).

The potassium salt of L proline show the absorption rate of 0.68 mol of CO2/mol of solute
higher than the MEA which is 0.5 mol of CO2/mol of solute for MEA. The experimental
conditions are 2.5M solution and temperature range of 298K to 313 K. the absorption heat of
potassium salt of L-alanine is 53.26 kJ/mol much lower than that of MEA that is 81.77 kJ/mol.
The lower absorption heat means less amount of energy is required that make it more favorable.
Potassium shows the highest capturing efficiency because of its outstanding saturation
concentration for higher solubility. The carbondioxide is slightly acidic in nature as the source of
potassium salt of L-proline and L- alanine is KOH anf amino acids so they KOH is a strong
alkaline in nature make the absorbance easy.

Experimental section

 Semi-batch Absorption System

The semi batch absorption system measures the absorption capacities of absorbents. The
apparatus consist of gas mixer, reactor, water bath, mass flow controller, a stainless steel reactor,
sampling valve, condenser, magnetic stirrer, GC, and back-pressure regulator. The K type
thermocouple used to check the temperature and pressure conditions. The gas chromatograph has
been used to measure the carbon dioxide bobbling out after being passes through absorbent.
  Differential reaction calorimeter

It measures the heat of absorbance, consists of two mechanically agitated glass reactors, cooloing
water and thermostatic jacket to maintain the temperature, agitator, thermocouple, inlet gas port,
optional probe, motor, impeller, solvent, reactor, calibration probe, thermocouple, thermostat,
reference reactor, and GC.

The measurement of the reaction heat was conducted by following three steps:

1. calibration before reaction

2. reaction
3. calibration after reaction

The main principle of the reaction heat determination is that the exchanged heat between the
reaction mixture and wall of reactor is proportional to the area under the ΔT versus time curve.
The temperature difference between the two reactors was recorded and termed as a function of
the time.

Result and discussion

Carbon dioxide absorption capacity

As shown I figure the comparison between amines such as MEA and DEA with amino acid salts
such as potassium salt of L-proline and L-alanine has
been done on two temperature profiles such as 298K
and 313K. in the graph the y axis is plotted on ratio of
Ci and Co, inlet and outlet concentration of carbon
dioxide. The initial CO2 is 30% an discharge after
been contact with absorbent. The results indicate the lower value of ratio shows that amino acid
salt solution had higher CO2 absorption capacity than the amine solutions. MEA and DEA
solution saturated more slowly in 50 min. the figure shows that the absorption is a function of
time as temperature increases amino acid salt solution has the breakthrough faster than amines.
As the temperature increase because increase in vapour pressure that overall decreases the
solubility of carbon dioxide. As we know amines form table carbamate that pauses the
absorption of carbon dioxide while in case of amino acid salt solution bicarbonates are formed
due to steric hindrance.

Comparing the amino acid salts L- proline has absorption rate that is slower and unstable
because carbon dioxide is more impeded into it, as a characteristic of pentagon ring while the
absorption capacity of secondary and primary amino acids almost same.

The primary amines MEA has lower absorption capacity in comparison to the potassium L-
alaninate, it also possesses the larger heat of absorption then amino acid salts, the carbamate in
the latter case is unstable while in the former case it is very stable. The L-alanine carbamate
hydrolyzes to bicarbonate and carbonates. As a result amino acid is expected to yield high
regeneration efficiency as it possesses high absorption capacity and low heat of absorption.

Speciation.

NMR spectroscopy was used to determine the species in the aqueous potassium salts of L-
alanine and L-proline. NMR analysis utilized a sample of the semi-batch absorption system
calculated at a temperature of 298 K. The 13C and 1 H NMR spectra of the CO2-loaded MEA,
DEA, potassium L-alaninate, and potassium L-prolinate solutions are analyzed. As the
carbamate and bicarbonate/carbonate are accompanying to CO2. The carbon peaks seem at the
low field (165− 160 ppm) in the 13C NMR spectra,the electrons of the carbons are deshielded by
the oxygen atoms.

In the 1NMR spectrum, the four groups of peak of hydrogen in free MEA and MEA carbamate
seems to be four triplets. The results shows the presence of free amine, carbamate and
bicarbonate in MEA and DEA solutions. L-alanine and L-proline carbon of carbonyl group
appeared at the lower field frequency of 184.51 and 182.49 ppm. The production of the
bicarbonate and carbonate in the aqueous potassium L-alaninate solution was very pronounced
because the carbamate shows low stability, it is easily hydrolyzed into bicarbonate and
carbonate. The carbamate was hydrolyzed to the bicarbonate and carbonate because of the
methyl group in L-alanine.The results displayed that aqueous potassium L-alaninate and
potassium L-prolinate contains a significant amount of bicarbonate and carbonate.