MATEC Web of Conferences 400, 02009 (2024) https://doi.org/10.

1051/matecconf/202440002009
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Characterization of Loading Rate of CO2 with Mono Ethanol

Amine Continuous Reactor Experimentation & Titrimetric
CO2 Loading Evaluation
N. Sriniwasa Prabhu1,*, S. Govindaradjane1, Raman Saravanane1
1Puducherry Technological University, Puducherry, India
*Corresponding author email: sriniwasaprabhu@ptuniv.edu.in

Abstract. This study delves into leveraging a continuous reactor experiment setup for CO2 Capture
using Mono Ethanol Amine (MEA). A series of experiments were conducted utilizing various
concentrations of MEA from 10% to 30% wt/wt under controlled conditions to determine their CO2
loading rates. The continuous reactor system offered insights into the kinetics and equilibrium
behaviours of the MEA-CO2 interaction. The CO2 loading with MEA solvents is estimated using a
titrimetric method, the UOP 829-821 which consumes less resources for research in a laboratory
setup. This enabled repetitive and reciprocal loading rate assessments of CO2 loading rate analysis
with MEA solvents. The CO2 content in the experimented amine samples ranged from 0.13 to 0.45
mol CO2 / mol MEA while varying the CO2 concentration between 10% to 20% and MEA
Concentration from 10% to 30% for a range of absorption time periods. The CO 2 loading
performance showed only a marginal performance improvement was found between 20% and 30%
MEA concentration. The results of this study can help pave pathways for more efficient MEA based
CO2 Capture Technologies.
Keywords: CCS, CO2 Capture, MEA, CO2 Continuous Reactor, Titrimetric CO2 Loading
Estimation

1. Introduction
The dire need to combat climate change has necessitated cutting edge solutions, with Carbon Capture and Storage
(CCS) emerging as the critical technology against rising greenhouse gas emissions. Among various CCS
methodologies, Post-Combustion Capture (PCC) holds an unavoidable stature, given its capability to retrofit into
industrial infrastructures, providing an effective and practical means to mitigate carbon dioxide (CO 2) emissions.

Industries like Coal, Cement and Steel are some of the prime contributors to anthropogenic CO2 emissions,
contributing substantially to the global carbon footprint [1]. Addressing this challenge demands the integration of
PCC within industrial processes, an approach that involves capturing CO 2 emissions post-combustion, thereby
preventing their release into the atmosphere, and subsequently creating pathways for utilization and/or
sequestering them in secure geological formations.

Nations worldwide, including India, have pledged to curb their emissions and transition towards sustainable
practices. The Intergovernmental Panel on Climate Change (IPCC) emphasizes the urgency of such actions to
limit global warming and mitigate the associated adverse impacts. For India, a country experiencing rapid
industrial growth, the adoption of PCC aligns seamlessly with its commitment to the global climate agenda [2].
By integrating PCC into its industrial landscape, India not only contributes substantively to the global effort but
also upholds the integrity of its INDC commitments. This integration is pivotal, ensuring a resilient and sustainable
trajectory for the nation's industrial development while fostering global climate resilience.

Currently, industries have started adopting the first go-to decarbonization measures like energy efficiency and
renewable energy adoption. Whereas, IPCC and International Energy Agency (IEA) has substantiated in their
reports that without Direct CO2 Capture Technology it will be near impossible to reach Net-Zero State in the realm
of CO2 Emission Mitigation [3].

Mono Ethanol Amine (MEA), a primary amine, exhibits high affinity for CO 2, making it an excellent candidate
for PCC applications. MEA's significance lies in its widespread application as a solvent in CO 2 capture processes
[4,5]. In PCC, MEA-based solutions act as absorbents, selectively capturing CO 2 from industrial flue gases. The
subsequent regeneration of MEA, often through thermal means, enables the release of captured CO 2 for
sequestration or utilization [6,7].

1This method can be found through ASTM International and is a titrimetric method to determine CO 2 in ethanolamine
solutions.

© The Authors, published by EDP Sciences. This is an open access article distributed under the terms of the Creative Commons Attribution License 4.0
(https://creativecommons.org/licenses/by/4.0/).
MATEC Web of Conferences 400, 02009 (2024) https://doi.org/10.1051/matecconf/202440002009
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MEA's utility becomes furthermore significant because of its cost-effectiveness, wide market availability and less
logistic constraints [7,8,9]. As a primary amine, MEA is produced on a large scale, contributing to its affordability.
The widespread industrial use of MEA in sectors such as the production of detergents and textiles ensures its
consistent availability [10], reducing logistical challenges associated with procurement.

Unlike batch reactors, continuous systems provide real-time data, allowing precise control and enhanced
scalability [11,12]. Continuous reactor estimations offer insights into MEA's dynamic behaviour, improving
process efficiency and facilitating industrial implementation.

2. Experimental Setup
2.1 Equipment and Reagents
Commercial-grade CO2 with a purity of 99 % was purchased from a local vendor in Puducherry. MEA with a
purity of 99 % was from Pon Pure Chemicals Co., based in India. All materials were used as received without
further purification. The chemicals were diluted to desired molarity levels using double distilled water. Dilution
of CO2 was done using air obtained from a small lab vacuum pump of 50 lpm capacity. The gas flow levels were
maintained using rotameters from S.Y Industries, Thane, India. Janatics Pressure Gauges of 10 bar capacity with
a resolution of 0.5 bar and Temperature Gauges of 150 °C capacity with a resolution of 2.5 °C were used. Methanol
(99% purity), Sulfuric Acid solution, Sodium Hydroxide Solution, Thymolphthalein indicator were the main
chemical reagents used.

2.2 Experimental Apparatus

The schematic of the continuous absorption reactor used in the study is given in Figure 1. The continuous reactor
consists of a gas dilution setup, absorption column, spray system, solvent circulation pumps, reservoirs, sample
collection points, solvent thermal regenerator, and PLC thermostat control for the heating. The entire experimental
setup is hoisted on a skid made up of Mild Steel.

The dilution of CO2 gas to varying concentrations from 8% to 20% using ambient air obtained from a lab vacuum
pump is performed using two rotameters. The CO 2 rotameter is of 10 lpm capacity and 0.5 lpm resolution. The
Air rotameter is of 50 lpm capacity and 1 lpm resolution. The experiments were repeated several times to average
out any errors due to flow fluctuations in the rotameter.

The absorber and stripper reactors in the setup are cylindrical vessels constructed from Stainless Steel (SS) 304
grade, ensuring durability and resistance to corrosion. All solvent connections within the system are also
fabricated from SS 304, maintaining consistency in material choice for reliability and chemical resistance. The
lines carrying the Air/CO2 mixture are made of pneumatic tubing crafted from Teflon material, chosen for its
excellent chemical inertness and pressure carrying capacity.

The Monoethanolamine (MEA) chemical is stored in a Polypropylene tank, which offers a cost-effective and
chemically resistant solution for containing the solvent. From this tank, the MEA is pumped into the system as
needed. To regulate the flow of substances at various points within the setup, SS 304 type Gate Valves are
employed, as depicted in Figure 1. These valves provide precise control and are noted for their robustness and
longevity.

Additionally, all thermocouple contactors are made from SS 304, ensuring accurate temperature readings and
compatibility with the other components. Both the absorber and stripper vessels are equipped with advanced
temperature and pressure sensors, enabling precise monitoring and control of the process conditions within these
critical reactors. This comprehensive and carefully selected material setup ensures the system's efficiency,
reliability, and longevity.

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Figure 1. Lab Scale Continuous CO2 Absorption Reactor - Process Schematic

The absorber operates in a counter-current flow condition between the diluted CO2 stream and the MEA solvent.
The MEA solvent is sprayed with a single-spray nozzle and the CO2 stream enters from the bottom of the absorber
column. The air entry portion is provided with an umbrella setup to avoid solvent entering the air inlet. This
umbrella setup will also be resourceful in increasing the residence time of the solvent spray and provides improved
surface contact area between the CO2 stream and the MEA stream. The absorption column is held in place inside
the skid.

Solvent recirculation is achieved through use of a chemical pump. The pump is made up of Polypropylene to
avoid any corrosion from the solvent used. The maximum flow of the pump is 30 lpm and can provide a water
head of 0.5 bar. The recirculation system consists entirely of SS 304 lines of ½” diameters throughout the system.

The MEA solvent is stored in polypropylene containers within the skid. These chemical tanks are connected to
the solvent recirculation system. These tanks are also provided with sampling ports to take solvents before, during
and after the experiments.

The reactor also contains a thermal stripper to regenerate loaded CO 2 using Ceramic Band Heaters. The
temperature of the heaters was controlled using temperature controller with a PLC 2 system (Program Logic
Controller). This PLC system offers automatic power cut off to the heaters as soon as the temperature of the
stripper exceeds the desired temperature. The band heaters are insulated with rock wool padding for safety. The
reactor system was installed with both a pressure and temperature sensor in both the absorber and the stripper.
2.3 Procedure

The MEA solvent was prepared to necessary concentrations as laid out in Table 1. The solvent concentration was
varied to 10%, 20% and 30% wt/wt using double distilled water. This MEA solvent was loaded on to the chemical
tanks in the reactors. The CO2 dilution was varied from 10% to 20% as mentioned in Table 1.

In the system, the solvent recirculation system was first initiated to operate the system in a continuous mode. The
solvent spray was started, and level was maintained in both the absorber and stripper vessels to reach steady state.
Only after this step, the CO2 flow was initiated from the CO2 cylinders controlled by the rotameter. The pressure
in the absorber vessel was checked to ensure it is well below 0.5 bar. Higher pressure in the absorber vessel will
result in reduced absorption of CO2 with MEA solvent.

The experiment was conducted for various time intervals to also ensure that complete absorption of CO 2 with
MEA is achieved to saturation. The recirculation cycles were also monitored for varied counts as mentioned in
Table 1.

2 PLC Thermostat is Programmable Logic Controller for temperature control

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Table 1. Operation Parameter of the Continuous CO2 Absorption Column

Parameter Variation Range

Solvent Concentration 10%, 20% and 30% wt/wt

CO2 Concentration 10%, 15%, 20% vol/vol

Recirculation Time 10, 20, 30 minutes

The continuous reactor was operated for each set of condition and samples were collected from the sampling ports
provided in the chemical tanks. The stripper was used to regenerate the MEA after each experiment run and the
CO2 loading was estimated to ensure release of absorbed CO 2 which was found to be on average 90%. The
regeneration temperature was maintained at 110 °C to ensure complete regeneration possible.

3. Data Observation
3.1 CO2 Loading Measurements

The UOP Method 829-82 [13] facilitated systematic calculation of loading rates of CO2 with MEA solvent. It is
a method used for titrimetric determination of CO2 in ethanolamine solutions. The CO2 loaded samples were
dissolved in anhydrous methanol to estimate the loading rates. This solution will be titrated against a standard
methanolic sodium hydroxide (MeONa) solution to calculate the CO 2 content. Hence, this method is also referred
to as the MeONa method.

Methanol solution of 100ml is taken in a 500ml Erlenmeyer flask and thymolphthalein indicator. 0.5 M
Methanolic Sodium Hydroxide solution is prepared and titrated against this Methanol solution to a light blue
colour while constantly stirring the solution in the flask. This titrant value is recorded as B. This represents the
Methanol Blank value.

Now, 10ml of the CO2 loaded sample is taken in a pipette and added to the Erlenmeyer flask. The light blue colour
disappears. This sample and methanol solution is now titrated against 0.5 M MeONa solution till light blue colour
appears. This titrant value is recorded as A. The CO2 content of the sample can now be calculated using the
formula given below [13],

3.2 (𝐴−𝐵)𝑀
Cu.ft of CO2 / gallon of sample = (1)
𝑉

Where,
A – Total volume of Standard MeONa added in ml
B – Volume of Standard MeONa added for methanol blank in ml
M – Molarity of MeONa
V – Sample Volume in ml

4. Results and Analysis

4.1 CO2 Loading Rates

The estimated CO2 loading rates are summarized in Table 2.

Table 2. Summary of Experiment Results

10% MEA 20% MEA 30% MEA

10 mins -* 10 mins 0.18 10 mins 0.20

10% CO2 20 mins 0.13 20 mins 0.26 20 mins 0.28

30 mins 0.15 30 mins 0.28 30 mins 0.31

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10 mins -* 10 mins 0.25 10 mins 0.35

15% CO2 20 mins 0.19 20 mins 0.32 20 mins 0.36

30 mins 0.21 30 mins 0.36 30 mins 0.39

10 mins -* 10 mins 0.35 10 mins 0.40

20% CO2 20 mins 0.32 20 mins 0.40 20 mins 0.43

30 mins 0.35 30 mins 0.42 30 mins 0.45

- All loading rates are expressed in mol CO2 / mol of amine.

- For 10% MEA and <10 mins of recirculation, values are low for titrimetric measurements*

5. Conclusion
The continuous reactor was used to estimate the CO2 loading with MEA solvent under various operating
conditions of solvent concentration, CO2 dilution and recirculation periods. The titrimetric procedure to estimate
the CO2 content in the amine samples were useful to estimate the absorption load with minimal resources at the
lab scale. The CO2 load values fall well within the previously reported range of 0.2 to 0.5 mol CO 2 per mol of
MEA [8]. The continuous reactor has been monument in practically ensuring the absorption capacity of MEA
solvents at various concentrations.

The CO2 levels in the tested amine samples varied between 0.13 to 0.45 mol CO2 / mol MEA. This variability was
achieved by adjusting the CO2 concentration within the range of 10% to 20%, and the MEA concentration from
10% to 30% over different absorption time periods. It was observed that the CO 2 loading performance
demonstrated a direct correlation with the CO2 concentration in the inlet stream. Nevertheless, there was only a
slight improvement in performance noted when the MEA concentration increased from 20% to 30%.

Albeit being a titrimetric method, the UOP 829-82 can be used confidently in this experiment because there are
no alkaline carbonates or acidic compounds resulting from amine decomposition [14]. The continuous reactor
ensured complete saturation and quicker process flow to avoid amine decomposition. There are also no presence
of Sulfur dioxide or Hydrogen Sulphide in this experiment which could affect the titration process in this
experiment setup. In addition, to ensure amine decomposition is not present, the CO2 loaded samples were
regenerated in the stripper section in the continuous reactor and then the samples were again tested for presence
of any CO2 content.

The insights gained from this experiment have significant implications for direct CO2 capture high climate
polluting industrial sectors like Coal, Cement, Steel, Ore processing and Chemical manufacturing. Especially
through optimized CO2 capture processes using MEA solvents. The challenges include dynamic heterogeneous
emission stream with varying CO2 concentrations and contaminants. Both these can be overcome by using a
continuous reactor and a versatile chemical absorbent like MEA even at low concentrations.

To further improve the CO2 capture process, several strategies can be considered:

Enhanced MEA Solvents: Use of additives and catalysts that can help reduce the volatility and energy requirement
to desorb CO2 from MEA can be revolutionary in the Carbon Capture domain.

Innovative Reactor Designs: Designing advanced reactors with improved heat and mass transfer characteristics
can facilitate quicker and more complete CO2 absorption and desorption cycles.

Operational Optimization: Using the most advanced control systems to accurately control temperature, pressure,
and flow rates to maximize CO2 capture efficiency while minimizing energy consumption.

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Utilization of Renewable Energy: The cost of capture can be brought down drastically by utilizing abundant
renewable energy sources to power the CO2 capture and release processes. This can provide an added benefit of
further reducing the carbon footprint of the carbon capture process.

By carefully studying the experimental behaviour of MEA-CO2 in such continuous reactor setup can fast track
the process of designing the optimum CO2 Capture systems for industries at commercial and large scale adoptions
in the quickest time possible.
Acknowledgments

The authors acknowledge that no funding support was received for conducting this experiment.

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