HALDIA INSTITUTE OF TECHNOLOGY

DEPARTMENT OF CHEMICAL ENGINEERING

Project Report

A study on
Kinetics of CO2 absorption in aqueous amine solution

Submitted by –

Kunal Roy 14/CH/21 10300614021

Neha Mandhare 14/CH/26 10300614026

Paramita Maiti L15/CH/69 10300615069

During the year 2017-2018

----------------------------- ------------------------------------
Project Guide Head of Department
Dr. Asit K. Saha Prof. (Dr.) T.K. Mana
ABSTRACT

The emission of the Green House Gases is a big concern as the accumulation of gases leads
to the temperature increment of more than 20 C will lead us to severe consequences. The
consequences of too high global warming will be melting of glaciers, leading to reduced water and
food resources. The sea level will rise, and there will be more extreme weather, more draughts,
and more floods. CO2 is the most important greenhouse gas, and most efficient way should be
adopted to minimize the emission of CO2.

Aqueous amine solvents have been extensively studied for the purpose of CO2 absorption
to reduce emissions from sources such as industrial power stations. In order to reduce CO2
emissions from a power plant, CO2 can be captured either from the syngas that is to be burned or
from the flue gases exiting the energy conversion process. However, to improve the economic
viability of carbon capture technologies, solvents with higher CO2 absorption capacity and faster
kinetics are required. The choice of the promising molecules depends on many physical and
chemical characteristics (like absorption capacity, kinetics reaction between amine, reaction
enthalpy and solvent stability and toxicity). This work focuses on the absorption capacity of CO2
and the reaction rates of single amines.

In this project we will study, SHAs (Sterically Hindered Amine) such as AMP (2-amino 2-
methyl 1-propanol) are used for determining the absorption capacity and kinetics of CO2
absorption and also MEA (Mono-ethanolamine) for standardizing the experimental set up before
performing experiment using a wetted wall column and stirred cell reactor. The absorption of CO2
gas in amine in an absorber will be studied. The reaction is done by mass transfer followed by
chemical reaction and the experiment data will be obtained by assuming and fitting data for
determining the order of the reaction. The results will be obtained to develop a kinetics model for
CO2 reaction with SHAs solutions which shows the absorption of CO2.

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 ACKNOWLEDGMENT

Apart from the efforts of myself, the success of any project depends largely on the
encouragement and guidelines of many others. I take this opportunity to express my gratitude to
the people who have been instrumental in the successful completion of this report.

I would like to show my greatest appreciation to my respected teacher Dr. Asit K. Saha of
Chemical Engineering Department, Haldia Institute of Technology for giving me a very interesting
project in “Kinetics of CO2 absorption in aqueous amine solution” and also for his tremendous
support and help. Without his encouragement and guidance, this report would not have been
materized.

I would also like to express my heartfelt gratitude to our respected H.O.D Mr. Tapas Kumar
Mandal for giving me this opportunity to present this report in front of you.

The constant guidance anf support received from all my family members throughout the
completion of this report is also worth mentioning. And last but not the least I would also like to
thank my group members without whose opinions and ideas the completion of this report would
not have been possible.

Neha Mandhare:

Kunal Roy:

Parimoita Maity:

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 CONTENT

SL. TITLE
NO.
1.0. INTRODUCTION
2.0. OBJECTIVE
3.0. LITERATURE
4.0. NOTATION & ABBREVIATION

5.0. THEORY
5.1. REACTION MECHANISM
5.2. FILM THEORY
5.3. PSEUDO FIRST ORDER REACTION
6.0. EXPERIMENTAL SETUP & PREPARATION
6.1. MATERIALS
6.2. EQUIPMENTS AND PROCESS
6.3. ANALYSIS OF CARBONATION BY-PRODUCTS
7.0. CALCULATION

8.0. DISCUSSION OF RESULTS

9.0. CONCLUSION
10.0. FUTURE DEVELOPMENTS

11.0. REFERENCES

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1.0. INTRODUCTION -
Anthropogenic global warming has been acknowledged as one of the extreme environmental
issues in the present scenario. The global average surface temperature has increased gradually
with an approximation of 1.4 and 5.8° C during the time period 1990–2100 conferring to the
United Nation's Intergovernmental Panel on Climate Change report (Intergovernmental Panel on
Climate Change, 2001). Fossil fuels are the leading sources of energy consumed in the world to
the tune of 86% owing to the massive development of worldwide economies with added
disadvantage of responsible element for 65% of anthropogenic CO2 emissions globally (BP, 2015).
The energy outlook (Internaltional Energy Agency , 2012) reported that the energy demand and
CO2 discharges will rise even higher while fossil fuels continue the prevailing energy sources.
Electricity, heat generation and transportation are the main contributing segments and
responsible for two-third of the worldwide CO2 emanations which depends heavily on coal, the
highest carbon-intensive fossil fuel. The average global CO2 concentration in the atmosphere
displays a steady escalation of 405.70 ppm on February 09, 2017 as compared to 316 ppm on the
year 1958 which was recorded at Mauna Loa Observatory (Scripps Institution of Oceanography,
2016). According to the Intergovernmental Panel on Climate Change (IPCC), emission of
greenhouse gas (GHG) must be reduced by 50% to 80% by 2050 to circumvent intense

Figure 1Schematic Representation of various CO2 Capture Processes (Intergovernmental Panel on Climate Change, 2001).

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consequences of global warming. A global warming with average temperature increment of more
than 20 C will lead us to severe consequences, and IPCC has therefore specified that GHG
emissions should be reduced by 50 to 80% by 2050 (Stangeland, 2007). The consequences of too
high global warming will be melting of glaciers, leading to reduced water and food resources. The
sea level will rise, and there will be more extreme weather, more draughts, and more floods. CO2 is
the most important greenhouse gas, and anthropogenic CO2 emissions are mainly a consequence
of fossil fuels being the most important global energy sources (Stangeland, 2007).

Many solutions are realized or investigated to trap carbon dioxide. There are different types of
CO2 capture systems (Figure 1). The concentration of CO2 in the gas stream, the pressure of the
gas stream and the fuel type (solid or gas) are important factors in selecting the capture system
(Intergovernmental Panel on Climate Change, 2001).
 Post-Combustion: Post-combustion capture of CO2 in power plants is economically
feasible under specific conditions. It is used to capture CO2 from part of the flue gases from a
number of existing power plants.
 Pre-Combustion: The technology required for pre-combustion capture is widely applied
in fertilizer manufacturing and in hydrogen production. Although the initial fuel conversion
steps of pre-combustion are more elaborate and costly, the higher concentrations of CO2 in the
gas stream and the higher pressure make the separation easier.
 Oxy-fuel Combustion: Oxy-fuel combustion is in the demonstration phase and uses high
purity oxygen. This results in higher concentrations of CO2 in the gas stream and, henceforth,
it will be easier in separation of CO2 and in increased energy requirements in the separation of
oxygen from air.

To reduce the discharge of anthropogenic CO2 concentration in the atmosphere, absorption of

CO2 through chemical solvent is the most effective and well established technology, because
chemical solvents offer a high chemical potential necessary for selective capture of CO2 from flue
gas (power plant or industrial) having low CO2 partial pressure (Rao & Rubin, 2002). Aqueous
alkanol-amine solutions are extensively used for the removal of acid gas impurities such as carbon
dioxide (CO2) and hydrogen sulfide (H2S) from natural gas, refinery off gas, fossil fueled power
plant flue gas, petroleum chemical plants and synthesis gas from ammonia production industries.
CO2 capture with a regenerative solvent is treated to be a mature technology since it has been
efficiently applied as CO2 elimination technology in industrial applicability. An extensive diversity
of alkanolamines such as mono-ethanolamine (MEA), di-ethanolamine (DEA), di-iso-propanol-
amine (DIPA), N-methyl-di-ethanolamine (MDEA), tri-ethanolamine (TEA) and 2-amino-2-
methyl-1-propanol (AMP) can be used as an absorbent for the removal of CO2 gas from the
industrial flue gas (Rangwala, Morrell, Mather, & Ottoo, 1992; Kohl & Nielsen, 1997; Rinker,
Ashour, & Sandall, 2000; Furhacker, Pressl, & Allabashi, 2003; DeMontigny, Tontiwachwuthikul,
& Chakma, 2005). CO2 capture through chemical absorption process has lot of advantages, such
as:

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  Combination of reaction and separation in a single process unit.
 Significantly, higher CO2 removal efficiency.
 Solvent regeneration for further use of the absorbent with added advantage of selective
capture and nearly pure CO2 can be attained after stripping of CO2 loaded solvent.
 Mature technology for great extent of industrial appropriateness (Hamzehie, et al., 2014;
Kenarsari, et al., 2013).

Noticeably, there is no single solvent present which offers all outstanding characteristics for CO2
capture through absorption process. Therefore, substantial enquiries are going on towards
improvement of appropriate absorbent possessing the characteristics of high reactivity with greater
CO2 loading capacity in addition to lower energy requirement for solvent regeneration and lower
operation cost (Khan, Halder, & Saha, 2017).

Very recently, an emergent attention has been paid using enhanced and activated alkanol-
amine solvents, e.g. PZ activated MDEA or AMP, for CO2 removal in order to take improvement
of the reasonably high rate of reaction of CO2 with the activating agent integrated with the
compensation of high loading capacity of MDEA or AMP. It is reported in the published literature
that PZ is more effective than any conventional rate activators due to its very high reaction rate
kinetics with CO2 (US Patent Patent No. 4,336,233, 1982). Despite the fact that available literature
on the use of primary, secondary or tertiary alkanolamines for removal of CO2 is extensive but
information regarding CO2 absorption with aqueous PZ solvent scheme is limited. This may be
attributed to the fact that, in process industries, PZ is used as an accelerator with other amines
rather than as an individual solvent. Although several investigations on the thermodynamic and
physicochemical properties of CO2–PZ and CO2–PZ-activated alkanolamines have been explored
in the open published paper (Aroua & Mohd Salleh, 2004; Bishnoi & Rochelle, 2000; Bishnoi &
Rochelle, 2002a; Bishnoi & Rochelle, 2002b; Derks, Dijkstra, Hogendoorn, & Versteeg, 2005;
Ermatchkov, Perez-Salgado, & Maurer, 2003; Liu, Zhang, & Xu, 1999) (Seo & Hong, 2000; Xu,
Zhang, Qin, Gao, & Liu, 1992; Zhang, Zhang, Qin, & Zheng, 2001). PZ is a cyclic diamine and
the aqueous solution of PZ has been used as an absorbent for the CO2 gas removal process in
addition to its higher specific absorption rate and higher CO2 loading performances (Khan, Halder,
& Saha, 2016).

2-amino-2-methyl-1-propanol (AMP), which is the hindered form of MEA, is considered as

one of the most important hindered amines for the industrial gas treatment processes. Hence, the
knowledge about the mechanism and kinetics of the reaction of CO2 and AMP is very important
since this is indispensable for the rational design of the absorption equipment and the treating
processes employing AMP as the absorbent. Although, thermodynamic and physio-chemical
properties and industrial applications of CO2-AMP systems have been discussed at length in
previous literature (Sartori & Savage, 1983; Chakraborty, Astarita, & Bischoff, 1986; Saha,
Bandyopadhyay, & Biswas, 1993), studies on the reaction kinetics of CO2-AMPare limited.

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 In this present work, new results on the absorption of CO2 into aqueous solutions of AMP in a
model laboratory wetted wall column will be presented. In order to make a thorough investigation
of the kinetics, measurements of the rates of absorption will be done at different contact times,
partial pressures of CO2 and concentrations of the amine. Besides this, the rates of absorption of
CO2 into aqueous solutions of MEA will also be measured in order to compare the value of the
rate constant for CO2-MEA reaction with that available in the open literature and thus verify the
validity of the experimental method will be adopted for the CO2-AMP system.

2.0. OBJECTIVE –

Chemical absorption of CO2 by aqueous solvents, mainly amines, has been studied for
decades by numerous researchers with satisfying results. The developed models include both
kinetic and thermodynamic aspects and are aiming to optimize the absorption. It is only recently
though, that these attempts include dynamic characteristics and more realistic representations of
the process.
Here, we are mainly going to find out the better amines for CO2 absorption purpose which
will have higher rate of reaction and absorption capacity. In this respect, SHA (Sterically Hindered
amines) like PZ and AMP are of better result. From literature review, study of kinetics of CO2
absorption is very scanty. That’s why our main objectives of this project are as follows –

 Outline briefly the common modeling approaches in the field of post-combustion CO2 absorption
 New ways of absorption of CO2 in amine solution.
 Determining the kinetics of the absorption of CO2 in amine solutions.
 Finally, the aims to conclude on the prediction efficiency of several models, comparing, to the point
it is possible, results of different researchers which are based on the same experimental data. [12]

3.0. LITERATURE -
Chemical absorption (or reactive absorption) is the
process where a gas is absorbed by a liquid phase with
combination of reaction and absorptive mass transport.
Amine – based systems, carbonate – based systems,
aqueous ammonia and ionic liquids – based systems are
typical systems for chemical absorption. In specific for
CO2 capture, chemical absorption involves the reaction of CO2 with a chemical solvent forming
a weakly bonded intermediate compound, a process that can be reversed applying heat and
resulting to the original solvent and a CO2 stream [3]. The regeneration process is the most
demanding by means of energy, as it may cost upto 14% of the power plant efficiency [4]. During
chemical absorption the flue gas enters usually an absorption tower where it contacts counter
current the solvent under low temperature (40– 60 1C). The rich in CO2 solvent is compressed,
heated in an exchanger and inserted in the desorption column (stripper) where it is regenerated
under low pressure (close to ambient) and high temperatures (100–140 1C). There generated (lean)

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 solvent exits the column and re- enters the absorber after dissipating its heat in the rich solvent
through the above-mentioned exchanger. The chemical absorption process will be initially
performed using amine aqueous solvents. The most mature and commercially applied amine is
Mono ethanol amine (MEA) due to its high absorptive capacity. MEA is considered an attractive
solvent at low partial pressures of CO2 in the flue gas due to its fast reaction rates compared to
that of secondary and tertiary amines [5]. Other common amines are Di ethanol amine (DEA),
Methyl di ethanol amine (MDEA), Diglycol amine (DGA), and Di isopropanol amine (DIPA) or
mixtures of amines that are characterized by satisfactory reaction rates and lower regeneration
energy than MEA. Piperazine is usually added as a promoter as it has been found to have faster
reaction rates than MEA. Due to its high volatility though, its application in CO2 absorption is
more expensive and is still under development. A special category of amines is sterically hindered
amines (SHA) that e.g. 2-Amino-2- methyl-1-propanol (AMP) and Piperazine (PZ). SHA form
more unstable carbamates in comparison with other amines. Thus, they are more efficient during
regeneration, as the unstable carbamates are easier to be reversed, leading therefore to quicker
desorption and less energy requirements. Alternative solvents for chemical absorption are aqueous
ammonia, ionic liquids and potassium carbonate. In specific, aqueous ammonia is a strongly
promising solvent characterized by many assets, as high absorption efficiency, high absorption
capacity, low energy requirement for absorbent regeneration and wide distribution of resources
[12].

4.0. NOTATION AND ABREVIATION –

o AMP= 2-amino-2-methyl-1-propanol.
o MEA= Mono-ethanolamine.
o MDEA= Methyl-di-ethanolamine.
o PZ= Piperazine.
o TEA= Tri-ethanolamine.
o DEA= Di-ethanolamine.
o DIPA=Di-iso-propanolamine.

5.0. THEORY -
The theory of gas-liquid absorption with chemical reaction is now well known
(Danckwerts, 1920); only the principal equations to be used for the interpretation of the
experimental results are recalled here.

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5.1. REACTION MECHANISM

5.1.1. Absorption reaction schemes

The following chemical reactions occur with CO2 gas in the aqueous primary amine solution
(R-NH2 with R= (CH2)2-OH for MEA) or secondary amines (RR´-NH) with the development of a
zwitterion intermediate, forming a carbamate (Danckwerts, 1979).

CO2 + 2RR´NH ⇌ RR´NCO− + RR´NH2+ (1)

Where R represents as alkyl group and R´ signifies H for primary amines and alkyl for secondary
amines. The zwitterion mechanism originally proposed by (Caplow, 1968) and reintroduced by
(Danckwerts, 1979) is largely established as the reaction mechanism for Eq. (1).

CO2 + RR´NH ⇌ RR´NH + COO− (2)

RR´NH + COO− + B´ ⇌ RR´NCOO− + B´H + (3)

The above mentioned absorption reaction mechanism involves primarily two steps: formation of
the CO2-amine zwitterions Eq. (2), and base catalyzed deprotonation of these zwitterions Eq. (3).
B denotes a base which could be amine, OH-, or H2O (Blauwhoff, Versteeg, & Van Swaaij, 1984).
In case of primary and secondary amines, such as, MEA, DEA, etc., the formation of amine-
carbamates Eq. (3) is quite stable.

In case of tertiary amine i.e. MDEA, the reaction between of CO2 gas with conventionally
used MDEA may occur through the following reaction steps (Blauwhoff, Versteeg, & Van Swaaij,
1984). MDEA, which does not have a hydrogen atom attached to the nitrogen atom, therefore the
reaction takes place through the formation of bicarbonate.

CO2 + H2 O ⇌ H + + HCO− 3 (4)

R1 R 2 R 3 N + H ⇌ R1 R 2 R 3 NH +
+
(5)
CO2 + R1 R 2 R 3 N + H2 O ⇌ R1 R 2 R 3 NH + + HCO−
3 (6)

Where R1, R2 and R3 represent as alkyl group and for MDEA, R1= CH3 and R2, R3 = (CH2)2-OH.
The reactivity of MDEA with CO2 is reasonably slow because, there is no carbamate formation
takes place. On the other hand the solvent regeneration cost is lower since the reaction heat released
in bicarbonate formation is lower than that of carbamate formation.

Piperazine (PZ) which is a cyclic diamine and relatively very new established absorbent for
the CO2 gas capture from the flue gas which is mainly used as a rate activator with conventional
absorbent like MDEA and AMP. The proposed reaction of CO2 gas with aqueous solution of PZ
follows the reaction steps mentioned
hereunder (Bishnoi & Rochelle, 2000; Ermatchkov, Perez-Salgado, & Maurer, 2003).

CO2 + PZ + H2 O ⇌ PZCOO− + H3 O+ (7)

CO2 + PZCOO− + H2 O ⇌ PZ(COO− )2 + H3 O+ (8)

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CO2 + OH − ⇌ HCO− 3 (9)
HCO−3 + H 2 O ⇌ CO2−
3 + H3 O
+
(10)
PZ + H3 O+ ⇌ PZH + + H2 O (11)
PZCOO− + H3 O+ ⇌ PZH + COO− + H2 O (12)
2H2 O ⇌ H3 O+ + OH − (13)

In case of sterically hindered amine (one form of primary amine) such as AMP, the amine-
carbamate formation is unstable and it undergoes carbamate reversible reaction as follows (Sartori
& Savage, 1983).

CO2 + RNH2 + H2 O ⇌ RNH3+ + HCO3− (14)

CO2 + RNH2 ⇌ RNH2+ COO− (15)
RNH2+ COO− + B ⇌ RNHCOO− + BH + (16)
RNH2+ COO− + RNH2 ⇌ RNHCOO− + RNH3+ (17)
RNH2+ COO− + H2 O ⇌ RNHCOO− + H3 O+ (18)
RNH2+ COO− + OH − ⇌ RNHCOO− + H2 O (19)

Conferring to Eq. (4), in case of hindered amines one mole of CO2 is absorbed per mole of amine.
Steric effects influence the stability of amine-carbamate formed due to reaction of amine with CO2.
It is suggested that due to instability of the carbamate formed, these readily undergo hydrolysis to
form bicarbonate, releasing free amine that again reacts with CO2 (Chakraborty, Astarita, &
Bischoff, 1986).

5.1.2. Regeneration reaction schemes

The thermal disintegration of regenerable carbamate and the absorption by products gives off
CO2 from the absorbed solution of ammonium compounds. The following three potential reactions
could be answerable for the release of CO2 during the thermal regeneration.

𝑅𝑁𝐻𝐶𝑂𝑂− + 𝐻2 𝑂 ⇌ 𝐶𝑂2 + 𝑅𝑁𝐻2 + 𝑂𝐻 − (20)

𝐻𝐶𝑂3− ⇌ 𝐶𝑂2 + 𝑂𝐻 − (21)
𝐶𝑂32− + 𝐻2 𝑂 ⇌ 𝐶𝑂2 + 2𝑂𝐻 − (22)

From Eq. (20), it can be seen that carbamate (RNHCOO-) is transformed into amine and CO2. The
enthalpy of dissociation for CO2 release depends on the stability of carbamate formation. The
molecular structure of AMP is hindered structure, and as a result carbamates dissociate easily in
comparison with other primary and secondary amines (Khan, Halder, & Saha, 2016).

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5.2. FILM THEORY

The overall absorption of carbon dioxide can be divided into two steps, physical and
chemical absorption. The physical absorption is described by the diffusion of CO2 from the
gaseous phase through an interface in to the liquid phase. The chemical absorption is then
described by the reaction CO2 undergoes while in the liquid phase [3,9]. The physical mass
transfer, can be described by the two-film theory [10] where the mass transfer of CO2 is explained
by different diffusion steps. These steps include the transport of CO2 from the bulk gas phase to
the interface and then the transport of CO2 from the interface to the bulk of the solvent. Figure 4.1
shows the mass transfer of CO2 from the gas to the bulk liquid, including fast reaction. The
transport through the gas phase is described by Fick’s first law and the driving force is the gradient
of the chemical potential, which can be translated to the concentration gradient and thus be
estimated by the partial pressure of carbon dioxide. For the liquid side the driving force can be
estimated by the concentration difference in the film. If a reaction takes place in the liquid the two-
film theory is not valid. To account for the reaction an enhancement factor can be introduced.
Since the reaction occurs on the liquid side of the system, the enhancement factor is introduced in
the description of the flux through the liquid film. The expressions for the flux through the gas and
liquid film are given in equations (6) and (7). [13]

𝑁𝐶𝑂2,𝑔 = 𝑘𝑔 (𝑃𝐶𝑂2,𝑏𝑢𝑙𝑘 − 𝑃𝐶𝑂2,𝑖 ) (23)

∗
𝑁𝐶𝑂2,𝑙 = 𝐸. 𝑘𝐿 (𝐶𝐶𝑂2,𝑖 − 𝐶𝐶𝑂2,𝑏𝑢𝑙𝑘 ) = 𝑘𝑔′ . (𝑃𝐶𝑂2,𝑖 − 𝑃𝐶𝑂2,𝑏𝑢𝑙𝑘 ) (24)

Here 𝑁𝐶𝑂2,𝑔 and 𝑁𝐶𝑂2,𝑙 are the fluxes while 𝑘𝑔 and 𝑘𝑙 are the mass transfer coefficients for
the gas and liquid film, respectively. 𝑃𝐶𝑂2,𝑏𝑢𝑙𝑘 and 𝑃𝐶𝑂2,𝑖 are the partial pressures of CO2 in the
gas bulk and at the gas side of the interface. 𝐶𝐶𝑂2,𝑖 and 𝐶𝐶𝑂2,𝑏𝑢𝑙𝑘 are the concentrations of CO2 at
the liquid interface and in the liquid bulk. P* CO2, bulk is the liquid bulk concentration of CO2
expressed as a partial pressure, k’g is the liquid side mass transfer coefficient and E is the
enhancement factor.

Figure 2:Illustration of mass transfer from gas to liquid bulk with fast chemical reaction

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 When the system is at equilibrium the concentration at the liquid interface can be calculated
from the equilibrium gas pressure at the interface using Henry’s constant. According to the two-
film theory and the assumption of fast reaction where the reaction only takes place in the liquid
film, an overall mass transfer coefficient, KG, can be introduced which includes both the gas side
and the liquid side mass transfer coefficient, as described in equation
1 1 𝐻𝑐𝑜2 1 1
= + = + (25)
𝐾𝐺 𝑘𝑔 𝐸.𝑘𝑙0 𝑘𝑔 ′
𝑘𝑔

The overall flux of CO2 from the gas phase to the liquid in the system can be described by KG and
the driving force:

∗
𝑁𝐶𝑂2 = 𝐾𝐺 . (𝑃𝐶𝑂2,𝑏𝑢𝑙𝑘 − 𝑃𝐶𝑂2,𝑏𝑢𝑙𝑘 ) (26)

where PCO2,bulk is described by the logarithmic mean pressure difference (LMPD) which is defined
as follows:
𝑃𝐶𝑂2,𝑖𝑛 −𝑃𝐶𝑂2,𝑜𝑢𝑡
𝐿𝑀𝑃𝐷 = 𝑃𝐶𝑂2,𝑏𝑢𝑙𝑘 = 𝑃𝐶𝑂2,𝑖𝑛 (27)
ln( )
𝑃𝐶𝑂2,𝑜𝑢𝑡

5.3. PSEUDO – FIRST ORDER REACTIONS

Absorption of CO2 into aqueous amine solutions normally follows a second order reaction
which makes the determination of the enhancement factor quite complex [12]. If instead the
experiments are conducted in the pseudo first order regime it allows for a simplified model as the
enhancement factor can be set equal to the Hatta number under these conditions [13]. The pseudo-
first order regime is defined by a fast reaction and requires the concentration of amine to be high
enough not to change in the gas-liquid interface during the absorption so that it can be considered
constant [14].

To verify that the reaction follows the pseudo-first order regime, the Hatta number must be
larger than 3 and lower than the infinite enhancement factor, 𝐸∞ [13].

3 < 𝐻𝑎 ≪ 𝐸∞ (28)

The Hatta number is defined by Equation (12). It includes the rate constants for both the
carbamate and bicarbonate formation (bicarbonate is formed in aqueous solutions) together with
the concentrations of the involved species, CMEA and COH. DCO2 is the diffusivity of CO2, kOH is
the rate constant for the bicarbonate formation and kl0 the physical liquid mass transfer.

√(𝑘2 .𝐶𝑀𝐸𝐴 +𝑘𝑂𝐻 .𝐶𝑂𝐻 ).𝐷𝐶𝑂2

𝐻𝑎 = (29)
𝑘𝑙0

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 The infinite enhancement factor is the enhancement factor obtained for instantaneous
reactions where the absorbent is depleted at the interface. It can be calculated according to equation
(13), using the diffusivities of amine and CO2 in the liquid phase and the concentration of amine
and CO2 in the bulk and at the interface, respectively. 𝑣𝑎𝑚 is the ratio amine to CO2 in the reaction
obtained from the reaction mechanism.
𝑏𝑢𝑙𝑘
𝐷𝐴𝑚,𝐿 .𝐶𝑎𝑚
𝐸∞ = 1 + 𝑖𝑛𝑡 (30)
𝑣𝑎𝑚 .𝐷𝐶𝑂2,𝐿 .𝐶𝐶𝑂2

In the case where the condition described in equation (11) is valid, and the reaction is of
pseudo-first order, one can assume that the enhancement factor is equal to the Hatta number based
on the following correlation:
𝐻𝑎
𝐸 = tanh 𝐻𝑎 (31)

For values of x higher than or equal to 3, tanh(x) is approximately equal to 1. Thus, the
enhancement factor can be set equal to the Hatta number [13].

6.0. EXPERIMENTAL SETUP & PREPARATION-

6.1. MATERIALS:

The chemicals used will be CO2, NaOH, MEA, HCl. All chemicals will be used without
further purification. The aqueous solutions of MEA wiil be prepared by mixing with distilled
deionized water.
For the comparison of different determination methods, we used the data of the reaction of
aqueous solution of MEA and carbon dioxide, was used for the validation of the new method. All
experiments were carried out using deionised water and carbon dioxide.

For performing the experiment, the below mentioned chemicals were required to prepared –
 1 N MEA Solution
 0.1 N NaOH Solution
 0.1 N HCl Solution
 BaCl2 Solution
 Bromoceresol green Indicator
 Phenolphthalein Indicator

Methylaminoethanol (MEA) -
The alkanolamine used in this work is 2-methylamino ethanol (MAE) liquid from ACROS
Organics with purity 99%. The formula of MAE is CH3NHCH2CH2OH. Its properties are given
in Table 4.1. The amine was used as received without further purification. The solution is prepared
by adding distilled water to the pure amine to the desired concentration. Necessary precautions are
taken to avoid any exposure of the sample to the air during the preparation period. The

Page | 14
concentration is verified every two weeks to cater for any evaporation that might occur which
could affect the pH of the solution.

Table 1: Chemical and physical properties of MAE

Property MAE
Synonyms 2-(methylamino)ethanol (MAE)
Structure CH3NHCH2CH2OH
Molecular Weight (g/mol) 75.11
Density (g.cm-3) 0.935
Melting Point (oC) -3
Boiling Point (oC) 155-156
Flash Point (oC) 90
Vapour Pressure, mmHg at 20oC 0.7
pH , 1M 11.6
Physical State Liquid
Colour Colourless
Stability Stable under ordinary conditions
Solubility Soluble and Miscible

Barium Chloride
Solid Barium Chloride, (BaCl2) is from Merck Chemicals. The solution is prepared by adding
distilled water to the solid to the desired strength (38.2g / 100g of water).

Hydrochloric Acid and Sodium Hydroxide

Standard hydrochloric acid, (HCl) of 0.1N and sodium hydroxide (NaOH) of 0.1 N solutions are
obtained from Merck Chemicals, and prepared according to instructions.

Nitrogen and Carbon Dioxide Gases

Pure, oxygen free N2 and CO2 gases are purchased from a local company with minimum purity
of 99.8%. For the 1% CO2 – N2 gas mixture, a ready mixed gas cylinder from MOX-LINDE
Gases Sdn. Bhd. is used.

Filter Paper
ALBET 502 filter papers are used throughout this experiment to ensure all solid carbonates are
collected during the analysis section.

6.2. EQUIPMENTS AND PROCESS:-

6.2.1. EQUIPMENT 1: Wetted Wall Column -

At first, MEA will be used to standardize the experiment set up. To measure the absorption
flux in a gas-liquid system a wetted wall column (WWC) can be used. This is a counter-current
approach where the gas enters at the bottom of the column and exits at the top. An absorbing liquid
medium is pumped and distributed on to a known surface area from the top, exiting at the bottom

Page | 15
of the column. An illustration of the wetted wall column will be used in this study is presented in
Figure 3.1.

Figure 3:Schematic overview of the wetted wall column (left) and experimental set – up (right)

The gas will be introduced to the reactor by three evenly distributed inlets at the bottom of
the reactor. The absorbing medium will be pumped through a stainless steel cylindrical tube and
distributed as a thin film on the outer surface of the tube, before it exits at the bottom. The contact
area can thus be obtained from calculations using the tube dimensions and by adding the
dimensions of the liquid film and dome (at the top of the tube) resulting from the liquid distribution.
The experimental temperature will be kept constant through an external cooling system where
water with a set temperature will be circulated in a cooling jacket around the reactor.

Figure 3.1 also shows the experimental set-up. The pump circulating the absorbing medium
will be placed directly after the column to avoid build-up of liquid in the column. Temperature
will be measured both at the inlet and outlet of the reactor to monitor any temperature difference
due to the exothermic absorption reaction. The gas will be saturated with solvent before it enters
the reactor. The saturator will be placed in the water bath to make sure the gas holds approximately
the same temperature as the absorbing medium. On/off-valves enables the user to choose whether
to run the gas through the reactor, or in by-pass mode for calibration.

Gas flows will be measured by using Rotameter mass flow. The theoretical loading will be
calculated by the flux obtained from the experiments and the time the gas stream will be lead
through the reactor. The molar content of the amine will be calculated from the concentration and
volume or mass used in the experiment. The loading will be defined as mole CO2 per mole amine,
according to equation (15).

(𝑛𝑐𝑜2 )𝑎𝑏𝑠
𝑙𝑜𝑎𝑑𝑖𝑛𝑔 = (𝑛𝑎𝑚𝑖𝑛𝑒 )𝑜
(32)

Page | 16
 For some experiments regeneration during the experiment will be necessary. This will be
done by introducing pure nitrogen to the system between each data point. As pure nitrogen will be
introduced the concentration difference will cause the previously absorbed CO2 to desorb from
the system leading to a decrease of the system loading. Nitrogen will be introduced for 15 min –
1.5 hours, depending on the amount of CO2 absorbed, to obtain sufficient regeneration. [13]

6.2.2. EQUIPMENT 2: Stirred Cell reactor -

The experiments were performed

in a stirred cell reactor consists of three
parts (Fig. 4): the lower flange on the
liquid side, the gas side flange and a
jacketed glass tube between them. Within
the flanges made of stainless steel, several
devices such as rotary transmission lead
through, temperature sensors, a pressure
transducer and in- and outlet valves for
gas and liquid are located. The liquid and
gas phases are stirred separately, with
opposite directions of rotation, and the
stirrers can be adjusted electronically to
the desired speed, with an accuracy of 9 /
1 rpm. Eight specially developed baffles
inside the reactor prevent vortexing during
stirring the liquid phase and ensure a flat
horizontal interface. The flanges are
equipped with electrical heating to reduce
Figure 5: Stirred Cell Reactor
heat losses. Furthermore, they permit
shorter heating-up times for experiments
at higher temperatures. Two storage
vessels equipped with heat exchangers are
used to provide the reactor with the liquid
solution and the gas at the required
temperatures. During experiments, the
temperatures of the liquid and gas phases
and the total pressure inside the reactor
were recorded by a personal computer data Figure 4: Stirred Cell Reactor
acquisition system.

A schematic diagram of the stirred cell absorber is shown in Figure 5. The stirred cell
absorber chamber with a water jacket which is connected to a water bath. Deionised water is used
in the double jacket to provide isothermal operating conditions. The entire assembly was proven
to have no leak. The liquid phase stirrer with two blades placed halfway down the liquid’s depth.
Both the gas and liquid phase stirrers were driven by the same shaft at speeds 0 - 2500 rpm that
can be adjusted electronically within an accuracy of ± 1 rpm. A metal pipe with 10 cm3 volume
was used for storage gas. It was wound around the metal flange which was temperature controlled

Page | 17
by an independent controller based on an electric heater. This equipment unit is used to provide
the required temperature for the gas. Both the upper and bottom metal flanges and the storage gas
pipe are thermally insulated to improve the accuracy of the temperature control.

Figure 6: Schematic diagram of Stirred Cell absorber[1- water bath,2- solution tank, 3- stirred cell chamber, 4- stirrer of liquid,
5- baffles, 6- stirrer of gas, 7- storage pipe of gas, 8- metal flange

PROCEDURE -

For the kinetics measurements of absorption runs, the stirred tank absorber was operated
batchwise with respect to both the gas phase and the liquid phase. For each experimental run, 500
- 600 cm3 volume of the freshly prepared (1 N) MEA solution is fed into the chamber and degassed
under vacuum for approximately 0.5 - 1 hour. Once the degassing process is complete, the liquid
is kept under vacuum (i.e. approx. 3.1 kPa at 298.15 K) in preparation for the experimental run
and data collection. The storage gas pipe is filled with the gas to be studied (CO2) at 500 kPa
(gauge) and then heated to the specified temperature. The temperature of metal flange was kept a
little higher (+0.3 K) than that of the liquid to avoid condensation on the surface of the metal
flange. After approximately 1 hour, the equilibria of both temperature and gas-liquid are reached,
CO2 is introduced into the chamber in 5 s and the absorption starts immediately. The total gas
pressure, the temperatures of the liquid and gas phases and the agitation speed (rps) in the reactor
are recorded using a data acquisition system (data logger, Agilent BenchLink 34972A). The partial

Page | 18
pressure of the gas A at the experimental condition was corrected for the vapor pressure of the
solution as follows.
𝑣 𝑣
𝑃𝐴 = 𝑃𝑡𝑜𝑡𝑎𝑙 − (𝑃𝑁2 + 𝑥𝐻2𝑂 𝑃𝐻2𝑂 + 𝑥𝑀𝐸𝐴 𝑃𝑀𝐸𝐴 ) (33)

where PN2 is the partial pressure of nitrogen, Pv H2O is the water vapor pressure, Pv
MEA is the vapor pressure of MEA, xH2O and xMEA are the mole fraction of water and MEA,
respectively.
For each experiment with CO2 absorption in MEA solution, and the initial partial pressure
of CO2 was low, 3 - 5 kPa, to satisfy the criterion for a pseudo-first-order reaction, as given by
Danckwerts [7] as follows:

3 < 𝐻𝑎 ≪ 𝐸∞

here Ha is Hatta number [8] and E is the limiting case of absorption, the infinite enhancement
factor, for a single irreversible reaction. E is defined as the enhancement factor given instantaneous
conversion of reactants. The rate of absorption is thus completely being limited by the diffusion
of the governing components. This is approximated by Higbie [9] as

𝐷 𝐷 𝐶 𝐻
𝐸∞ = √𝐷 𝐶𝑂,𝐿 + √ 𝐷𝑀𝐸𝐴,𝐿 𝑣𝑀𝐸𝐴 𝑃 𝐶𝑂2 (34)
𝑀𝐸𝐴,𝐿 𝐶𝑂,𝐿 𝑀𝐸𝐴 𝐶𝑂2

Here 𝑣𝑀𝐸𝐴 is the stoichiometric coefficient of MEA, HCO2 is the Henry’s constant, DCO2,L
and DMEA,L are the diffusivities of CO2 and MEA in the liquid, respectively. According to equation
(3), if CMEA is large enough or PCO2/HCO2 small enough, E will be large enough to satisfy the
criterion given by equation (2). In practice, to meet the pseudo first order reaction criterion, the
requirement for the PCO2 is different for different reaction systems. For example, the CO2 partial
pressure is not required to be as low to meet one of the criterion conditions (Ha<<E ) for
methyldiethanolamine (MDEA) + CO2 reaction system. But for MEA + CO2, it is required that
the CO2 partial pressure is low because of the high Ha value (or high reaction rate).
The influence of the CO2 liquid loading on the rate of the reverse reaction is only 1% at
the maximum as checked by Cornelisse et al. [10]. In this work, about 3 5 kPa CO2 (1.4 L) was
used for the absorption measurement in 0.5 L MEA solution.
To check the influence of gas phase resistance on the measurement of chemical absorption,
the reaction rate constants of MEA+CO2 were measured under different inert gas pressures at
303.15 K. The experimental concentrations of MEA were 1 and 3 M with H2O as a solvent and 3
M with ethyleneglycol as a solvent, respectively. The gas and liquid stirrer speed was 1 rps.

6.3. ANALYSIS OF CARBONATION BY-PRODUCTS –

Carbonation of an aqueous ammonium solution forms complex ammonium and carbonate

salts. The by-products are mixtures of ammonium bicarbonate, ammonium carbonate, complex
salts of carbonate and bicarbonate, ammonium hydroxide, and other compounds. It is desirable to
know the compound mix under various absorber conditions. In order to maximize the carbon
dioxide loading with ammonium ion, it would be desirable to maximize ammonium bicarbonate

Page | 19
formation, because one ammonium ion will combine with one mole of CO2, whereas in
ammonium carbonate formation, one ammonium ion only combines with ½ mole of CO2.
A method was developed by Parsons Chemical Analysis Group at NETL to determine
carbonate, bicarbonate and hydroxide quantitatively using phenolphthalein and total alkalinity
titrimetric methods.
The wet methods of analysis are summarized as follows: Saturated barium chloride is
added to an aliquot of a diluted sample to precipitate any carbonate. The development of a pink
color upon addition of phenolphthalein indicates the presence of hydroxide. If present, the
hydroxide is titrated with 0.1N HCl, giving hydroxide alkalinity. Bromocresol green indicator is
added and titration continued to the endpoint for total alkalinity/carbonate alkalinity determination.
This method presupposes the incompatibility of hydroxide and bicarbonate alkalinities (Method
2320B, Standard Methods for the Examination of Water and Wastewater, 18th edition, 1993).
If no pink color develops upon the addition of phenolphthalein indicator to a sample treated
with barium chloride, the absence of hydroxide is indicated. The sample is then titrated to a
bromocresol green endpoint with 0.1N hydrochloric acid for a total alkalinity measurement. A
second volume of sample is treated with excess 0.1N sodium hydroxide to convert any bicarbonate
to carbonate. All of the carbonate is precipitated with barium chloride. The excess sodium
hydroxide is immediately titrated with 0.1N hydrochloric acid to determine the bicarbonate
concentration. The carbonate concentration in the original sample (before the conversion step) is
calculated from the total alkalinity and bicarbonate concentrations. Below are the given images
taken while performing the experiment –

Carbonated MEA Solution sample Addition of BaCl2 in sample

Page | 20
 Filtrate with phenolphthalein
Precipitate of BaCO3 after filteration
(Pink Colour)

Adding Bromoceresol Green Titrate with 0.1 N HCl Titrate with 0.1 N HCl
Indicator (Blue Colour) (Blue to Yellow) (Pink to Colourless)

Page | 21
 BaCO3 ppt with exess NaOH Taking sample and adding phH Titrate with 0.1 N HCl
(Pink Colour) (Pink to Colourless)

The following reactions takes place during titration reaction –

𝐶𝑂2 + 𝑅𝑁𝐻2 𝑅𝑁𝐻𝐶𝑂𝑂− + 𝐻 + (35)

𝑅𝑁𝐻𝐶𝑂𝑂− + 𝐻2 𝑂 𝑅𝑁𝐻2 + 𝐻𝐶𝑂3− (36)
𝐻𝐶𝑂3− + 𝐵𝑎𝐶𝑙2 𝐵𝑎𝐶𝑂3 + 𝐻𝐶𝑙 (37)
𝐵𝑎𝐶𝑂3 + 𝐻𝐶𝑙 𝐵𝑎𝐶𝑙2 + 𝐶𝑂2 + 𝐻2 𝑂 (38)

7.0. CALCULATION –

 RUN 1:

Sample of carbonated MEA(1N) taken = 50 ml

Volume of BaCl2 added = 55 ml

Part I: When adding phH in 10ml part of sample (for hydroxide)

Volume of 0.1N HCL titrated = 10.3 ml

Part II: Adding bromoceresol green indicator and titrated against HCl

Volume of 0.1 HCl used = 7 ml

𝑉𝐻𝐶𝑙 𝑀𝐻𝐶𝑙 7∗0.1
Loading Capacity = 𝛼 = = = 0.035
2 𝑉𝑠𝑎𝑚𝑝𝑙𝑒 𝑀𝑀𝐸𝐴 2∗10∗1

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 where,
α represents CO2 loading in mole CO2 per mole amine, VHCl is the
volume of HCl needed to neutralize the basic species in ml, MHCl is the molarity
of HCl used for neutralization. Vsample is the volume of each of the three samples,
and MAmine is the molarity of the amine solution in N

Part III: Carbonate precipitate treated with exess NaOH and titrated with HCl

Volume of NaOH added = 99.5 ml

Volume of sample taken = 10 ml
Volume of 0.1 HCl used = 3.3 ml
𝑉𝐻𝐶𝑙 𝑀𝐻𝐶𝑙 3.3
Loading Capacity = 𝛼 = = = 0.0825
2 𝑉𝑠𝑎𝑚𝑝𝑙𝑒 𝑀𝑀𝐸𝐴 2∗10∗2

Therefore, Total loading capacity of CO2 is 0.035 + 0.0825 = 0.1175

 RUN 2:

Sample of carbonated MEA(1N) taken = 50 ml

Volume of BaCl2 added = 66.5 ml

Part I: When adding phH in 10ml part of sample (for hydroxide)

Volume of 0.1N HCL titrated = 13.8 ml

Part II: Adding bromoceresol green indicator and titrated against HCl

Volume of 0.1 HCl used = 4.8 ml

𝑉𝐻𝐶𝑙 𝑀𝐻𝐶𝑙 4.8∗0.1
Loading Capacity = 𝛼 = = = 0.024
2 𝑉𝑠𝑎𝑚𝑝𝑙𝑒 𝑀𝑀𝐸𝐴 2∗10∗1

where,
α represents CO2 loading in mole CO2 per mole amine, VHCl is the
volume of HCl needed to neutralize the basic species in ml, MHCl is the molarity
of HCl used for neutralization. Vsample is the volume of each of the three samples,
and MAmine is the molarity of the amine solution in N

Page | 23
Part III: Carbonate precipitate treated with exess NaOH and titrated with HCl

Volume of NaOH added = 90 ml

Volume of sample taken = 10 ml
Volume of 0.1 HCl used = 3.4 ml

For BaCl2,
𝑉𝐻𝐶𝑙 3.4
Loading Capacity = 𝛼 = = = 0.085
2 𝑉𝑠𝑎𝑚𝑝𝑙𝑒 ∗2 2∗10∗2

Therefore, Total loading capacity of CO2 is 0.024 + 0.085 = 0.109

 RUN 3:

Sample of carbonated MEA(1N) taken = 20 ml

Volume of BaCl2 added = 25 ml

Part I: When adding phH in 10ml part of sample (for hydroxide)

Volume of 0.1N HCL titrated = 11.4 ml

Part II: Adding bromoceresol green indicator and titrated against HCl

Volume of 0.1 HCl used = 5.1 ml

𝑉𝐻𝐶𝑙 𝑀𝐻𝐶𝑙 5.1∗0.1
Loading Capacity = 𝛼 = = = 0.0255
2 𝑉𝑠𝑎𝑚𝑝𝑙𝑒 𝑀𝑀𝐸𝐴 2∗10∗1

where,
α represents CO2 loading in mole CO2 per mole amine, VHCl is the
volume of HCl needed to neutralize the basic species in ml, MHCl is the molarity
of HCl used for neutralization. Vsample is the volume of each of the three samples,
and MAmine is the molarity of the amine solution in N

Part III: Carbonate precipitate treated with exess NaOH and titrated with HCl

Volume of NaOH added = 91 ml

Volume of sample taken = 10 ml
Volume of 0.1 HCl used = 3.2 ml
𝑉𝐻𝐶𝑙 𝑀𝐻𝐶𝑙 3.2
Loading Capacity = 𝛼 = = = 0.08
2 𝑉𝑠𝑎𝑚𝑝𝑙𝑒 𝑀𝑀𝐸𝐴 2∗10∗2

Therefore, Total loading capacity of CO2 is 0.0255 + 0.08 = 0.1055

Page | 24
8.0. DISCUSSION OF RESULTS: -
Successive analyses for carbon dioxide were reproducible to within better than 0.2%.
Sources of error include those usually associated with volumetric measurements as well as the
negligible error caused by barium carbonate solubility near 0 "C [solubility product 7 x 10-9 (g
ion/l.)2 at 16 "C] (4). On this basis, the maximum relative error of a determination is =k0.5%. The
time spent in one determination of both the amine and carbon dioxide concentration of a single
sample was about 15 minutes and somewhat less when multiple samples were analyzed. Apart
from its usefulness in carbon dioxide analysis, the method can be extended to the determination of
any acid gas in solution, existing in the free state or as a thermally unstable compound.

The sole requirement is that a suitable metal salt be used to form an insoluble precipitate
with the gas. For example, hydrogen sulfide in amines and hydroxides can be determined in a
completely analogous manner, using the chloride of cadmium, lead, manganese, or mercury, the
sulfides of these being insoluble. The method can also be used to determine both carbon dioxide
and hydrogen sulfide if these are present together.

Carbon dioxide can be selectively precipitated with barium chloride (barium sulfide being
soluble) and removed from solution. Both gases form insoluble precipitates with any of the above
metals allowing the determination of total acid gas; hence, no complication arises from the
presence of both gases. A further advantage of the technique is the removal of the suspended iron
and sludge commonly found in gas sweetening units, which would otherwise prevent the use of
visual indicators for titration. The inherent precision and rapidity of this procedure combined with
complete freedom from the need for any special equipment recommend the method for the
determination of acid gases both singly and as mixtures.

ECONOMIC EVALUATION

The flue gas enters at the bottom of the absorber with 15% CO2 (dry basis). In the absorber
CO2 is absorbed by absorbent and the absorbent is recirculated back to the absorber from the
regenerator.

In this sample calculation, the aqueous ammonia solution has 8% wt NH3 equivalent. The
solution lean loading is 0.035 mole CO2 per mole solution from the regenerator. The rich CO2
loading from the bottom of absorber is 0.0825 mole CO2 per mole solution. Therefore,
approximately 50% of CO2 in the ammonium solution is regenerated.

Page | 25
9.0. CONCLUSION -

Thermal regeneration of standard solutions revealed that regeneration of up to 60% of the

carbon in a bicarbonate solution may be regenerated. Ammonium carbonate solution resulted in
approximately 38% carbon regeneration under the same temperature condition. Cycling test results
demonstrated that a 62% reduction in regeneration energy is possible due to the higher loading
capacity of an aqueous ammonia solution, the lower heat of reaction, and the lower heat of
vaporization when compared to standard MEA solutions.

A flow system is being constructed for continuous operation absorption and regeneration
steps. A parametric study will include temperature, ammonia concentration, CO2 concentration,
and flow rates of reactants. Future research work will additionally investigate removals of sulfur
dioxide and nitric oxides with the ammonia solution.

10.0. FUTURE DEVELOPMENTS –

The tests described in this paper carried out in order to verify the plant operation and the
performance of every equipment in the design conditions. In particular, the tests on MEA-based
CO2 capture section allowed to verify the hypothesis considered for data processing. A large series
of experimental campaigns has been planned in order to verify the performance of every equipment
in different operating conditions. In particular, as for CO2 capture section, a series of tests will be
carried out in order to evaluate the effect of the main operating parameters, such as temperature,
CO2 partial pressure, CO2 loading, gas flow rate and solvent composition.

Temperature influences chemical and physical equilibrium of the process, together with all
the chemical-physical parameters such as viscosity, density and so on [22]. Therefore, the need to
evaluate the effects of a temperature variation on the absorption system suggests to carry out a
series of experimental tests with different operating temperatures. CO2 partial pressure can be
indirectly modified by varying steam injection in CO-shift process or through a direct carbon
dioxide injection upwards carbon capture section. This parameter influences mass transfer and
CO2 reaction into liquid phase, but only a little variation of global removal efficiency is expected
[23]. An increasing of gas flow rate (which can be controlled through the compressor which sends
syngas to the hydrogen production line) involves a rise of the effective interfacial area between
liquid and gas phases; therefore, a rise of the whole absorption efficiency, up to a maximum value,
is expected. Obviously, MEA concentration influences the process up to a maximum value,
depending to the kind of reactor [23-24]. As a matter of facts, the increasing MEA concentration
involves a higher amount of active solvent available to react with carbon dioxide; moreover, this
increasing involves a rise of solvent viscosity, which effects will be evaluated in the experimental
tests.

A large series of studies demonstrate that it is possible to enhance the reaction rate by using
proper additives mixed in the aqueous alkanolamine solution [25-26]. In particular, a significant
increasing of absorption performance can be obtained by mixing MEA with piperazine [11] or
AMP (2-amino-2-methyl-1-propanol) [27]. A series of experimental tests has been planned in
Page | 26
order to verify, in the Sotacarbo pilot plant, the process performance in these operating conditions.
Moreover, appears interesting the possibility to carry out a series of experimental tests with
different solvent blends [28], with particular reference to an aqueous solution of MEA and MDEA
(methyldiethanolamine) [29]. With a relatively simple plant modifying, it will be possible to test
the CO2 absorption system at different pressures.

Moreover, the design of a solvent regeneration system is currently under development. The
introduction of this system will allow the possibility to test the integrated absorption and
regeneration process and to reduce the operating costs of the experimental tests. This system will
be optimized for the regeneration of MEA-based solvents but, due to its flexibility, it will allow to
operate with different solvent solutions. Finally, the possibility to feed the gasifier with a mixture
of oxygen and carbon dioxide as oxidant agent has been investigated with preliminary tests [30].
The effects of these operating conditions on the integrated CO-shift and CO2 absorption system
will be investigated.

Page | 27
11.0. REFERENCES
[1] http://bellona.org/news/ccs/2007-10-why-co2-capture-and-storage-ccs-is-an-important-strategy-to-
reduce-global-co2-emissions.
[2] IPCC. IPCC Special Report on Carbon Dioxide Capture and Storage. Prepared by Working Group
III of the Intergovernmental Panel on Climate Change [Metz, B.O. Davidson, H. C. de Coninck, M.
Loos, and L. A. Meyer (eds.)]. Cambridge University Press, in, Cambridge University Press,
Cambridge, United Kingdom and New York, NY, USA, 2005, pp. 442.
[3] A.B. Rao, E.S. Rubin, A technical, economic, and environmental assessment of amine-based CO2
capture technology for power plant greenhouse gas control, Environmental science & technology,
36 (2002) 4467-4475.
[4] G. Pellegrini, R. Strube, G. Manfrida, Comparative study of chemical absorbents in post-combustion
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[5] A. Adeosun, N.E. Hadri, E. Goetheer, and M.R.M. Abu-Zahra, Absorption of CO2 by Amine Blends
Solution: An Experimental Evaluation, International Journal Of Engineering And Science, 3 (2013)
12-23.
[6] B. Mandal, A. Biswill be, S. Bandyopadhyay, Absorption of carbon dioxide into aqueous blends of
2-amino-2-methyl-1-propanol and di-ethanolamine, Chemical Engineering Science, 58 (2003)
4137-4144.
[7] Kohl A, Riesenfeld F. Gas purification. Houston: Gulf Pub Co; 1985.
[8] A. Bello, R.O. Idem, Comprehensive study of the kinetics of the oxidative degradation of CO2
loaded and concentrated aqueous monoethanolamine (MEA) with and without sodium metavanadate
during CO2 absorption from flue gases, Industrial & Engineering Chemistry Research, 45 (2006)
2569-2579.
[9] B.A. Oyenekan, G.T. Rochelle, Energy performance of stripper configurations for CO2 capture by
aqueous amines, Industrial & Engineering Chemistry Research, 45 (2006) 2457-2464.
[10] R. Strube, G. Pellegrini, G. Manfrida, The environmental impact of post-combustion CO2 capture
with MEA, with aqueous ammonia, and with an aqueous ammonia-ethanol mixture for a coal-fired
power plant, Energy, 36 (2011) 3763-3770.
[11] B. Mandal, S. Bandyopadhyay, Absorption of carbon dioxide into aqueous blends of 2-amino-2-
methyl-1-propanol and mono-ethanolamine, Chemical Engineering Science, 61 (2006) 5440-5447.
[12] I.P. Koronaki, L. Prentza, V. Papaefthimiou, Modeling of CO2 capture via chemical absorption
processes – An extensive literature review, 50 (2015) 547-566.
[13] Hanna Karlsson, helena Svensson, rate of absorption for CO2 absorption systems using a wetted
wall column, 114(2017) 2009 - 2023

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