APPLICATION OF IONIC LIQUIDS FOR

EFFICIENT REMOVAL OF CARBON

DIOXIDE, AND HYDROGEN SULFIDE
GASES IN PETROLEUM REFINING
PROCESSES
BY
UDOGRI OBARO
22PCN02464
SUPERVISED BY
DR ABRAHAM VICTORIA
OUTLINE
 Abstract

 Introduction

 Aim and Objectives

 Significant and Scope

 Literature review

 Methodology

 Result and Discussion

 Conclusion

 References
 ABSTRACT
This study presents a comprehensive simulation-based investigation employing Aspen HYSYS and density functional
theory (DFT) to evaluate the efficacy of an ionic liquid (IL) for the efficient removal of sulfur dioxide (SO2) and
Hydrogen Sulphide (H2S) gases from an untreated gas system. Ionic liquids have emerged as promising candidates for
gas absorption due to their tunable properties and high selectivity. Through rigorous simulation studies, the performance
of the IL in capturing SO2, H2S was systematically analyzed under varying operating conditions. Aspen HYSYS
simulations were utilized to model the gas absorption process, while DFT calculations provided insights into the
molecular-level interactions between the IL and the target gases. The results elucidate the adsorption mechanisms,
highlighting the role of IL structure and gas properties in determining the absorption efficiency. Additionally, the effects
of temperature, pressure, and IL concentration on the absorption capacity were investigated to optimize process
conditions. This interdisciplinary approach combines process simulation with quantum chemical calculations, providing
a comprehensive understanding of the IL-mediated gas removal process. The findings contribute to the development of
efficient gas separation technologies and underscore the potential of ILs in addressing environmental challenges
associated with gas emissions.
INTRODUCTION
Gas purification is a vital process in the oil and gas industry, aimed at removing impurities from
various gas streams to meet specific quality and regulatory requirements (Smith, 2019). The
purification of gases is crucial for several reasons; including ensuring the safety of equipment and
pipelines, meeting product specifications, reducing environmental emissions, and enhancing the
efficiency of downstream processes (Jones et al., 2020). A key aspect related to gas purification in
the oil and gas industry is the impurities in Gas Streams, natural gas, and associated petroleum gases
(APGs) often contain impurities such as sulfur compounds (e.g., hydrogen sulfide), carbon dioxide
(CO2), nitrogen compounds (e.g., nitrogen oxides) (Brown & White, 2018). These impurities can
have detrimental effects on infrastructure, equipment, and end products, as well as pose health and
safety risks (Johnson, 2017).
INTRODUCTION
Ionic Liquid as absorbent

Ionic liquids (ILs) are a class of non-molecular compounds that are composed solely of ions. They have melting
points lower than 100 °C. ILs have many advantages over traditional organic solvents including negligible
vapor pressure at room temperature as well as high thermal stability, making them nearly ideal solvents in
extraction techniques.

Why Ionic Liquid

The reason for Ionic liquid is attributed to its reduced environmental impact. Ionic liquids are less volatile and
can potentially be less harmful to the environment compared to some traditional solvents. Also if proven
effective and economically viable, the Ionic Liquid-based gas absorption process could be integrated into
various industries which include the oil and gas industry among several others
INTRODUCTION
• Dehydration
• Sweetening
• Fractionation

 Dehydratio
Gases n
Well  Sweetening
Oil
Stream  Desalting
Water  Stabilizatio
n

• Oil removal
• Treatment

Schematic Diagram showing the separation of the well stream into

different phases
Source: Lecture note
 Aim and objectives
The study is aimed at evaluating the ionic liquid capacity to absorb and H2S gases
The following are the objectives:
• Carry out Literature review on Absorption and other methods of removal of
impurities from gas stream.
• Provide a comprehensive understanding of the principles, mechanisms, and
technologies involved in gas purification processes for the removal of impurities such
as sulfur compounds, carbon dioxide, nitrogen compounds.
• Investigate the kinetics and thermodynamics of gas-solid and gas-liquid interactions
during gas purification processes, aiming to optimize reaction rates, equilibrium
conditions, and separation efficiencies for different impurities in gas streams.
Scope
The scope of this work is simulation studies

Significant
This project tends to address the broader significance of ionic liquids, and their
unique properties and aims to apply this knowledge to develop more efficient
processes for gas absorption, specifically targeting environmentally impactful
gases.
LITERATURE REVIEW
S/N AUTHORS TITLE WORK DONE GAP

1 Elmobarak, W. F., Current status of capture with ionic Study and comparison of CO₂ • Lack of physicochemical and
Almomani, F., liquids: Development and progress absorption capacity of formulated thermodynamic data
Tawalbeh, M., Al- hybrid solvent with water • Lack of data on the stability of ILs
Othman, A., Martis,
R., & Rasool, K.
(2023).
2 Tianxiang Zhao, Efficient capture and conversion to Study to design absorbents for both Durability and breakdown/degradation
Xiaoqing Yang, cyclic sulfites by protic ionic liquid- capture and conversion, cycloaddition of ionic liquids
Zhuoheng Tu, based deep eutectic solvents under reaction between and epoxides
Xingbang Hu(2023). mild conditions mediated in
PIL-based DESs
3 Chunyan Ma, Nan capture using ionic liquid-based absorption capacity of formulated Process optimization and sensitivity
Wang, Nannan Ye, hybrid solvents from experiment to hybrid solvents with water, DEPG, or analysis was not considered
Xiaoyan Ji, 2021 process evaluation PC as a cosolvent was studied and
compared.

4 Taslim Ur Rashid, Ionic liquids: Innovative fluids for Summary of recent advances on the No report on other relevant issues such
2020 sustainable gas separation Ionic Liquid in gas separation from as environmental impact, higher
from industrial waste stream the industrial waste stream temperature conditions, long-term
stability of IL, especially at elevated
temperature.
LITERATURE REVIEW
S/N AUTHORS TITLE WORK DONE GAP

5 Barbara B. Polesso, Supported ionic liquids as The effect of physical Lack of safety, environmental, and
Franciele L. Bernard, highly efficient and low-cost immobilization of two ionic health studies. To prevent
Henrique Z. material for / CH4 separation liquids with different anions on environmental pollution, application
Ferrari,Evando A. process two mesoporous support for ILs’ toxicity and biodegrade ability
Duarte, separation need to be thoroughly assessed.
Felipe Dalla Vecchia,
Sandra Einloft, 2019
6 Shuhang Ren, Yucui Ionic liquids: Study the effect of Ionic The solubility enthalpy, heat capacity,
Hou, Kai Zhang, Weize Functionalization and Liquid as solvent for capturing and biological stability are important
Wu, 2017 absorption of from flue gas data for designing process and
applications, but they are seldom
reported in the literature

7 M. Hasib-ur- Ionic liquids for capture- Summary of the work High viscosity, so mass transfer a
Rahman, M. Siaj, F. Development and progress emanating from the patent as major concern; Longer equilibrium
Larachi, 2010 well as scientific literature, time
going on the use of ionic liquid
for capturing carbon dioxide.
METHODOLOGY
This work was carried out using the following methods
Density Functional Theory(DFT)
Absorption simulation studies using Aspen Hysys Software
Density Functional Theory(DFT)
Design of Experiment

Materials:
Ionic Liquid (1-methyl-1 propylpiperidinium
Bis(trifluoromethanesulfonyl)-imide)
METHODOLOGY
Steps
 The following was first carried out using the Density Functional Theory:
1. Adsorption energies and binding energy
2. Quantum theory of atoms in molecules(QTAIM) and Non covalent Interaction (NCI)
3. Thermodynamics

 Next several analysis was then carried out using Aspen Hysys to find the optimal process operating
condition at which the Acid gas sweetening plant will operate at, to achieve high acid gas removal as well
as optimal recovery of natural gas from the absorber.

 Finally, Design of Experiment software was used to interpret the result and for visualization. Statistical
analysis, and correlation studies was done on the result.
Justification for the Ionic Liquid
Used

Thermal
Stability

Non-
Non-toxic corrosive
1-methyl-1 in nature
propylpiperidinium
bis(trifluoromethanesul
fonyl)-imide

Good
Non- viscosity
volatile value of
about 89cP
Through investigation of the atoms of the cation [MPPIP] and anion
[TFSI] involved in the absorption of CO2 and H2S using density
function theory, we observed that the CO2 molecule was bonded to
the anion [TFSI] while the H2S molecule was bonded to the cation
[MPPIP]. This result tends to validate the theory of electronegativity
and molecular orbital theory.
Result and Discussion
1ST RUN
OPTIMIZED
RESULT OF CO2
ABSORPTION

• From the figure, the total

energy gotten from optimized
step 1 is -2152.39102hartree.
2ND RUN
OPTIMIZED
RESULT OF CO2
ABSORPTION

• the total energy for

optimized step 2 is -
2152.4385hartree
 correspondin
Summation of the g Binding
Total Energy per atomic energy from Energy
Run No. run (Hartree) dimer (Hartree) (Hartree)
1 2152.39102 -2151.807853 4304.198873
2 2152.4385 -2151.807853 4304.246353

We can observe that run 1 require the least amount of energy for binding
of CO2 to [TSFI] to take place and thus will be chosen to be the most
optimized structure orientation. From the analysis performed on DFT,
the bond angle for run 1 was gotten as 63.82676 o and this implies that at
this orientation, the ionic liquid will require the least amount of bonding
energy of 4304.198873hartree which is equivalent to 1.876520594308e-
14j to absorb CO2 from natural gas. The energy is required is seen to be
very small and thus absorption of CO2 gas will take effect easily.
 1ST RUN OPTIMIZED
RESULT OF H2S
ABSORPTION

• From the figure we

observethat the total energy
gotten from optimized step
1 is -2151.807853hartree
2ND RUN OPTIMIZED
RESULT OF H2S
ABSORPTION

• total energy for

optimized step 2 is -
2151.807853hartree.
 Summation of the
Total Energy per run atomic energy from corresponding Binding
Run No. (Hartree) dimer (Hartree) Energy (Hartree)

1 2151.74552 -2151.807853 4303.553373

2 2152.04013 -2151.807853 4303.847983

From the above, we can observe that run 1 require the least amount of
energy for binding of H2S to [MPPIP] to take place and thus will be
chosen to be the most optimized structure orientation. From the analysis
performed on DFT, the bond angle for run 1 was gotten as 55.99963 o
and this implies that at this orientation, the ionic liquid will require the
least amount of bonding energy of 4304.198873hartree which is
equivalent to 1.876239172822e-14j to absorb H2S from natural gas.
The energy is required is seen to be very small and thus absorption of
H2S gas will take effect easily.
Study of 1-methyl-1propylpiperidinium bis(trifluoromethanesulfonyl)-imide used in absorption of acid
gases (CO2 and H2S) from natural gas using aspen hysys V12
 TEMPERATURE SENSITIVITY ANALYSIS ON CO2 AND H2S REMOVAL IN ABSORBER UNIT

Temperature Analysis Temperature Analysis

553.5 178.52

178.5

553.45 178.48

178.46
553.4

H2S Flowrate (Kg/hr)

CO2 Flowrate (Kg/hr)

178.44

178.42
553.35
178.4

178.38
553.3
178.36

553.25 178.34

178.32

553.2 178.3
12 16 20 24 28 32 36 40 44 48 52 56 60 64 68 72 76 78 80 82 84 86 12 16 20 24 28 32 36 40 44 48 52 56 60 64 68 72 76 78 80 82 84 86

Temperature (C) Temperature (C)

A temperature sensitivity analysis on the amount of methane and ethane recovered in the sweet gas after absorption

Temperature Sensitivity Analysis Temperature Sensitivity Analysis

1742 0.342

0.34
1740
Flowrate of Methane (Kg/hr)

Flowrate of Ethane (Kg/hr)

0.338
1738

0.336
1736
0.334

1734
0.332

1732
0.33

1730 0.328
10 30 50 70 90 11
0
13
0
15
0
17
0
19
0
21
0
23
0
25
0
27
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270

Temperature (C) Temperature (C)

Pressure sensitivity analysis on CO2 and H2S removal in absorber unit

Pressure Analysis Pressure Analysis

553.47 553.47

553.465 553.465

553.46 553.46

H2S mass flowrate (Kg/hr)

553.455 553.455
CO2 Flowrate (Kg/hr)

553.45 553.45

553.445 553.445

553.44 553.44

553.435 553.435

553.43 553.43

553.425 553.425

553.42 553.42
50 00 50 00 50 00 50 00 50 00 50 00 50 00 50 50 50 50 50 50 50 50 50 00 50 00 50 00 50 00 50 00 50 00 50 00 50 50 50 50 50 50 50 50
15 16 16 17 17 18 18 19 19 20 20 21 21 22 22 23 24 25 26 27 28 29 15 16 16 17 17 18 18 19 19 20 20 21 21 22 22 23 24 25 26 27 28 29

Pressure(Kpa) Pressure (KPa)

Concentration sensitivity analysis on the amount of CO2 and H2S removed from the absorber

Concentration Sensitivity Analysis Concentration sensitivity Analysis

556 178.47202

554 178.472

552
178.47198

550
178.47196
CO2 Flowrate (Kg/hr)

H2S Flowrate (Kg/hr)

548
178.47194
546
178.47192
544

178.4719
542

540 178.47188

538 178.47186

536
0 0 0 0 0 0 0 0 0 0 0 0 0 0 178.47184
1 00 1 06 1 10 1 14 1 18 1 22 1 26 1 30 1 34 1 38 1 42 1 48 1 52 1 56 00 60 00 40 80 20 60 00 40 80 20 80 20 60
10 10 11 11 11 12 12 13 13 13 14 14 15 15
Ionic-Liquid-Flowrate (Kgmole/hr)
Ionic-Liquid-Flowrate (Kgmole/hr)
 Concentration sensitivity analysis on the amount of methane and ethane recovered from the absorber

Ionic-Liquid Analysis Ionic-Liquid Analysis

4000 250

3500

200
3000

Flowrate of Ethane (kg/hr)

Methane Flowrate (Kg/hr)

2500
150

2000

100
1500

1000
50

500

0 0
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
50 60 70 80 90 1 00 1 10 1 20 1 30 1 40 1 50 1 60 1 70 1 80 50 55 60 65 70 75 80 85 90 95 100 105 110 115 120 125 130 135 140 145 150 155 160 165 170 175 180

Ionic-Liquid Flowrate (Kg/hr) Flowrate of Ionic-Liquid (kg/hr)

DOE Analysis

From the figure above, we could observe that the standard error is low, and since a coefficient
estimate or effect estimate's uncertainty or variability is measured by the standard error. The
standard error will show the potential deviation between the estimated and true values.
It’s good to note that the square root of the estimate's variance is used to compute standard error,
which is then used to create confidence intervals and run hypothesis tests. A low standard error as
we got from our statistical calculation indicates that the deviation of the estimated response or
yield from the actual yield is low and thus the model is a valid one.
From the figure above, we can deduce that the factor AB is the most significant, since it’s p-
value is less than 0.05 and thus will be used to find the optimal response of the yield.
The accuracy of the model being developed was checked by calculating the rsquare,
adj-rsquare and predicted rsquare and the result was seen in figure 20 below. The
percentage of the response variable variance that a linear model can explain is
called r-squared (R2), which is a statistical measure of how near the data are to the
fitted regression line. It is also referred to as the coefficient of determination. Thus,
from our result gotten below, we can deduce that 46.18% of data in out model are
closed to a fitted regression line whereas the goodness of fit of this regression
model is about 21.34%
The optimized response can be seen in fig 21 below and studied as thus, the line with the
highest response corresponds to that with a pressure of about 28.5bar and temperature of
224oc and the intersection of these two values, when taken upwards towards the z-axis and
read carefully gives a response of about 95% in the yield axis, meaning that from
statistical analysis performed, the optimized combined factors being the pressure and
temperature will result to a 95% absorption of acid gases from natural gas.
CONCLUSION
The study of the use of 1-methyl-1 propylpiperidinium Bis(trifluoromethanesulfonyl)-imide as
ionic liquid for the removal of acid gas was seen as being successful, due to:

• The less corrosive and toxicity nature of the ionic liquid

• It’s stability to heat and cheapness made it a favorable solvent to be used in acid gas
sweetening.

Furthermore, the thermodynamic study of how 1-methyl-1 propylpiperidinium

Bis(trifluoromethanesulfonyl)-imide is used as an absorbent is studied and it was deduced that

• The CO2 molecule will be favorable attached to the anion part of this salt which is
Bis(trifluoromethanesulfonyl)-imide
• The H2S molecule will be favorably attached to the cation part of this salt which is 1-methyl-
1 propylpiperidinium and this bonding is due to the electronegativity effect of the atoms
involved in molecular bonding.
• Also, the binding energy required for CO2 bonding as well as H2S bonding with 1-methyl-1
propylpiperidinium bis(trifluoromethanesulfonyl)-imide was calculated and it was
discovered that both acid gases needed a minute amount of energy with a value of
1.876520594308e-14j for CO2 bonding and 1.876239172822e-14j for H2S bonding. This
implies that the removal of these acid gases from natural gas stream will occur swiftly with
little energy requirement, thus making the process an energy efficient process.
• The analysis carried out on aspen hysys revealed that certain process variable will affect the
rate at which the acid gases are being removed from the absorber unit. The temperature of
sour gas was a major process variable that was seen to affect the degree of acid gas removal
and it was deduced that the sour gas (feed gas) should have its optimal temperature range as
50oc - 78oc for adequate removal of acid gas from the absorber as well as maximum recovery
of the sweet gas in the top of the absorber column.
• Pressure sensitivity analysis was performed as well on the absorber unit, and
we deduced also that the optimal operating pressure of the absorber unit
should be a pressure of 1800kpa in order to achieve high percentage of acid
gas removal from the sour gas and maximum recovery of sweet gas at the
top of the absorber unit
• The ionic liquid concentration sensitivity analysis was performed in the
absorber unit, and we deduced that although high concentration of the ionic
liquid will imply high percentage recovery of ionic liquid, it also implies low
percentage recovery of sweet gas at the top of the absorber, as more
molecules of the sweet gas will partake in mass transfer from the gaseous
state to the liquid state.
DOE was used to carry out statistic analysis on the absorption of the process and predict
independent factors and how well they can be combined to affect the response
The standard error of various factors gotten from statistical analysis was seen to be a small
value, thus meaning that the intended model to be built was close to the actual model.
The accuracy of the model was evaluated as well by calculating the rsquare and adj-rsquare of
model, which gave us a value of 46.18% and 21.64% respectively. The yield was also evaluated
with a 3-D model to give an optimal response of over 90%, implying that the rate of absorption
of acid gases using 1-methyl-1 propylpiperidinium bis(trifluoromethanesulfonyl)-imide as the
ionic liquid will result to over 90% removal of CO2 and H2S from the natural gas.
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•

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•