Effect of pH on desorption of CO2 from

alkanolamine - rich solvents

Cite as: AIP Conference Proceedings 1864, 020091 (2017); https://doi.org/10.1063/1.4992908
Published Online: 03 August 2017

Min Du

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AIP Conference Proceedings 1864, 020091 (2017); https://doi.org/10.1063/1.4992908 1864, 020091

© 2017 Author(s).
Effect of pH on Desorption of CO2 from alkanolamine - Rich
Solvents
Min Du

School of shipping and naval architecture, Chongqing Jiaotong University, Chongqing 400074, China
a)
Corresponding author:dm-god@126.com

Abstract. Adipic acid was used as a pH regulator, which was added to 0.4 mol/L MEA, DEA and MDEA solvents during
CO2 desorption process. It is found that when pH value of the solvents swing between 8-10, CO2 desorption rate enhanced,
and energy consumption has declined obviously. This research may have reference significance on optimization of
alkanolamine CO2 capture process.

Key words: Regulation of pH; Alkanolamine; CO2 desorption.

INTRODUCTION
Alkanolamine is an import absorbent which is commercially used for CO2 capture. An important bottleneck is its
high energy requirement of CO2 desorption. The main research direction is how to reduce its energy consumption.
In recent years, one kind of researches is to find absorbents with high absorption rate and low energy requirement
of CO2 desorption. [1,2]. Another one is to optimize the parameters during the process of CO 2 absorption and desorption.
In this work, Q Xiang[3] studied the effect of temperature, CO2 loading on CO2 absorption on the mass transfer
coefficients of CO2 absorption in aqueous ammonia solution. H Rashid[4] studied the effect of flow and gas
concentration on CO2 uptake based on the Kent-Eisenberg Thermodynamic Model. For pH, Emier[5] proposed the
possibility of changing the pH value to reduce CO 2 desorption energy consumption, Bo feng[6] verified this view, but
did not analyze the effect of pH.
Based on the zwitterionic theory, the formula of CO2 reaction rate was obtained. The main factors that may affect
the “CO2-alkanolamine-H2 O” reaction system were analyzed, and the influence of pH value was verified
experimentally.

MECHANISM ANALYSIS
The mechanism of zwitterion is proposed by Caplow[7], followed by Danckwerts.[8] which has been improved and
supplemented by the mechanism, including the formation and deprotonation process of zwitterions.
When CO2 enters the liquid phase, the absorption process of the mass transfer rate is mainly determined by its
absorption rate, for the "CO2 -alkanolamine-H2O" reaction system, CO2 is absorbed and eventually form a relatively
stable carbamate and bicarbonate , The absorption rate of the reaction consists of three parts, as shown in formula (1):

rCO rCO2 a min e  rCO OH   rCO2 H2O (1)

2 2

Green Energy and Sustainable Development I

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 rCO2  H 2O is the reaction rate of hydrolysis of carbon dioxide,which is shown in formula (2). CO 2 is difficult to
dissolve in water, and the hydrolysis rate is very low. The order of magnitude is much smaller than its reaction rate
with alkanolamine [10], it is generally negligible.

CO2  2H 2 O l H 3O   HCO3 (2)

rCO OH  is the rate at which CO2 generates bicarbonate ions. The rate is much higher than that of CO2 hydrolysis,
2

but also slightly lower than the CO2 and amine solvent reaction rate. However, in the process of CO 2 absorption by
tertiary amine, CO2 and MDEA do not react directly in the actual industrial decarburization system (1 atmosphere
pressure, 30-60 ćIn the ionization of the OH- reaction, the reaction rate determines the rate of CO2 absorption reaction.
The reaction rate can be determined by formula (3) as following:

* 
rCO OH  KOH  [CO2 ][OH ] (3)
2

*
K OH  is the reaction rate constant of CO2 and OH-, according to some experimental results, Pinsent [10]
*
determines the empirical formula of K OH  as formula (4):

2895
*
lg KOH  13.635  (4)
T

rCO2 a min e is the rate of reaction between CO 2 and alkanolamine, which is dominant in the rate of CO2 absorption.
According to zwitterion theory[9], it is assumed that the zwitterion concentration meets the pseudo-first order reaction
condition, The equation for the rate of CO2 absorption is shown in equation (5)˖

k 2 [CO2 ][ R1 R2 NH ]
rCO2 a min e 
k1 (5)
1
6kb [ B]

Where k2 is the rate constant of CO2 and alkanolamine forward reaction (negative sign represents the reaction
direction), k1 is the rate constant of the reverse reaction, and kb is the rate constant of the reaction between the Alkaline
substance and the zwitterion. Sada[11] investigated the rate of CO2 dissolution in aqueous MEA solution in a spray
column apparatus, which reflects the first-order reaction rate of CO2 with MEA. It is shown that the pseudo-first-order
reaction rate determines the rate of CO2 uptake in MEA-CO2 reaction.
I can be seen from equation (3) and (4) that the reaction rate of CO 2 and OH- is proportional to the concentration
of [OH- ] in the solution, ie, the absorption rate of CO 2 increases with increasing pH of the solution. It is found that the
pH value of the solution is an important factor affecting the rate of CO 2 absorption, and the reaction is reversible. In
the process of CO2 desorption, the reaction proceeds in reverse. In this process, the pH value of the solution is also a
key factor affecting the desorption rate. In order to verify the effect of pH on the desorption of CO 2 from MEA, the
relevant experimental research in this paper was conducted.

EXPERIMENTAL
The experiments were carried out using 0.4mol/L MEA, DEA and MDEA Aqueous solutions respectively. Adipic
acid was used to adjust the pH value of rich solvent. There are two reasons, one is to add some strong acid can cause
a large number of instantaneous precipitation of CO2, pH value of the solution at this time is nonsense, another is that
adipic acid has a certain pH buffer characteristics, the solution can be stable in some range of pH.
Experimental diagram of CO2 absorption process is shown in Figure1, the structure of absorber is "spray + tray"
type; Using N2 as an inert gas, to facilitate the analysis of CO2 concentration changes; Using FTIR to monitor CO2
concentration; In order to avoid the absorption of CO 2 from mixed gas, using silica gel as a desiccant. Absorption part
is for the preparation of rich solvent, and determining the CO2 loading.

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 FIGURE 1. Experimental diagram of CO2 absorption

Desorption process is shown in Figure 2, as found in previous experiments, water vapor vaporization heat
accounted for most of the desorption energy consumption, making the desorption energy consumption more dependent
on the desorption time. The solution was heated by heating N 2 to reduce the percentage of vaporization heat in the
heat of regeneration . FTIR is still used to monitor the CO2 concentration.

FIGURE 2. Experimental diagram of CO2 desorption

RESULTS AND DISCUSSION

In the desorption process, it was found that there was a small amount of CO2 precipitated immediately after adding
acids. The addition of several acids in the desorption process was completely dissolved at high temperature. After the
desorption, the solution is naturally cooled to room temperature, and the pH value was slightly rebounded. Under the
same experimental conditions, Samples added acid in its desorption process can accelerate the CO 2 deposition rate.
Figure 3a-c shows the CO2 concentration curves for the desorption processes of three alkanolamine solutions with
addition of adipic acids. It can be seen that the CO2 concentration in all desorption processes follows the three stages
of "increasing - reaching peak - decreasing". First, the temperature of desorption solvents rise to boiling state, then
CO2 precipitation is more slowly, but with the temperature increase, the rate of precipitation gradually increased,
followed by the solution temperature stable at the desorption temperature, this stage CO 2 average desorption The rate
of CO2 reaches the maximum. The peak concentration reflects the maximum CO2 precipitation rate. At this point the
corresponding pH range is favorable for desorption. And then with the decrease of the amount of CO 2 in the solution,
the equilibrium direction of the reaction hinders the precipitation of CO2, and the gradual decrease of the precipitation
rate becomes smooth. The concentration of CO 2 in the mixed gas of CO2 and 480mL / min in desorption process can
be used to characterize the real-time precipitation rate of CO 2. The higher the concentration, the higher the
precipitation rate and the higher the precipitation rate. The maximum desorption rate of CO2 is increased by acid
addition, the average desorption rate is increased throughout the desorption process, and the third stage is reduced to
a shorter level, shortening the heating time. For all desorption processes, the precipitation rate of CO 2 increased
significantly after adding acid, and the rate of CO2 precipitation continued to increase with the increase of acid addition.

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 The effect of MEA on the precipitation of CO2 was more strongly than that of DEA and MDEA. For the 0.4mol/L
solution, the peak concentration of the solution is very significant, when adding 30g/L adipic acid. MEA, DEA and
MDEA were 686%, 333% and 545% higher than those in the conventional desorption process.

140000 120000

120000 no acid added no acid added

10g/L adipic acid added 100000
10g/L adipic acid added
20g/L adipic acid added 20g/L adipic acid added

CO2 Concentration (ppm)

CO2 Concentration(ppm)

100000 30g/L adipic acid added 30g/L adipic acid added

80000

80000
60000
60000

40000
40000

20000
20000

0 0
0 200 400 600 800 1000 1200 1400 1600 1800 0 200 400 600 800 1000 1200

Time(s) Time(s)

FIGURE3a CO2 concentration curves of 0.4mol/L FIGURE3b CO2 concentration curves of 0.4mol/L
MEA regeneration with adipic acid added DEA regeneration with adipic acid added

80000

no acid added
60000
CO2 Concentration(ppm)

10g/L adipic acid added

20g/L adipic acid added
30g/L adipic acid added

40000

20000

0
0 200 400 600 800 1000 1200 1400 1600 1800

Time(s)

FIGURE3c CO2 concentration curves of 0.4mol/L MDEA regeneration with adipicacid added

Figure 4 shows the corresponding energy consumption of CO2 desorption for the deferent pH of the depleted
solution after desorption. It can be seen that the energy consumption decreases with the decrease of the pH value of
the solution for all the rich solvent desorption processes. When the pH value is between 8 and 10, for 0.4 mol/L MDEA,
the energy consumption of CO 2 desorption decreased by 2633.5kJ/mol after the pH value of the absorption liquid was
decreased from 9.41 to 8.75, which was equivalent to 67.65%
4500

4000
Energy consumption(kJ/mol CO2)

0.4M MEA
3500 0.4M DEA
0.4M MDEA

3000

2500

2000

1500

1000
4 5 6 7 8 9 10 11

pH

FIGURE4 Effect of pH on Desorption Energy Consumption of 0.4mol / L Solvent

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 According to the formula (5), the desorption rate of CO2 increases with the decrease of pH value, the experimental
results are consistent, and the reaction rate increases significantly with the decrease of pH. Based on the mechanism
of zwitterion and the theory of reaction equilibrium,as [H+] increases, desorption of CO2 reactions to precipitate CO 2
in the reverse direction, and the most sensitive pH range is 8-10.
In this pH range, the energy consumption of CO 2 desorption is significantly reduced, and the pH value of the
desorption process can be optimized based on this result. This conclusion is true for low concentrations of monoamines,
but further verification still need to be conducted for high concentrations or combined amines, and pH-sensitive range
are undoubtedly present.

CONCLUSION
In this paper, the pH value of CO2 desorption process was optimized. Based on the zwitterion theory, it is concluded
that the decrease of the pH value of the desorption solvent can reduce the energy consumption, and the experimental
results well validate this point.
The experimental results show that there exits sensitive pH range for the three solutions of MEA, DEA and MDEA.
When pH swing between 8-10, the energy consumption of CO2 desorption changes more than the original 50%. The
study can be a complement to the optimization of parameters for Alkanolamine CO 2 scrubbing process.

ACKNOWLEDGMENTS
This research was financially supported by Scientific and Technological Research Program of Chongqing
Municipal Education Commission˄Grant No. KJ30418˅and the open project of Key Laboratory of Low-grade
Energy Utilization Technologies and Systems (Chongqing University), Ministry of Education of China(Grant No.
LLEUTS201401)

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