Article Not peer-reviewed version

Optimization of Carbon Capture &

Hydrogen Production via Steam

Reforming: A Simulation-Based

Case Study

*
Ahmed Nazmus Sakib , Ahnaf Tahmid Shabab , Md. Firoz Ahmed

Posted Date: 21 July 2023

doi: 10.20944/preprints202307.1509.v1

Keywords: Aspen HYSYS; SMR; pinch analysis; PCC; hydrogen; carbon capture; MEA-MDEA

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Article

Optimization of Carbon Capture & Hydrogen

Production via Steam Reforming: A Simulation-
Based Case Study
Ahmed Nazmus Sakib 1,*, Ahnaf Tahmid Shabab 2 and Md. Firoz Ahmed 3
1 Dept. of Aerospace and Mechanical Engineering, University of Oklahoma, Norman, OK 73019, USA
2 Dept. of Chemical Engineering and Polymer Science, Shahjalal University of Science & Technology,
Sylhet-3114, Bangladesh.
3 Dept. of Chemistry, Wayne State University, 42 W Warren Ave, Detroit, MI 48202, USA.

* Correspondence: [email protected]

Abstract: Hydrogen has been considered a future energy carrier for decades and the demand for
hydrogen in refineries is always upward due to the revival of new technologies. The steam methane
reforming method is frequently employed because of its high hydrogen generation efficiency at a
cheap cost and minimal negative impact on the environment. But depending on the type of
feedstock, one unit of hydrogen generate 9-10 units of CO2 that is needed to be treated for
environmental sustainability. Therefore, the optimization of hydrogen production and CO2 capture
is very important to address. The simulation research was conducted to anticipate and optimize
steam reforming using Aspen HYSYS. A conversion-type reactor was used to develop this
simulation-based model. The primary goal of this work is to investigate and optimize the
production efficiency of hydrogen and the mitigation of CO2 that is generated from the steam
reforming process by varying process parameters. CO2 capture efficiency was investigated at the
different yields for hydrogen production and was found that a maximum of 98.8% of the CO2 can
be absorbed using the proposed carbon capture system. Later, the Aspen Energy Analyzer tool
revealed potential improvements for energy and cost optimization.

Keywords: Aspen HYSYS; SMR; pinch analysis; PCC; hydrogen; carbon capture; MEA-MDEA

1. Introduction
The primary source of electricity generation and greenhouse gas emissions around the globe is
fossil fuel-fired power plants. Coal-fired power plants account for 38% of the global electricity
generation and 38% of CO production, leading to global warming [1,2]. The recent release of the
Intergovernmental Panel on Climate Change (IPCC) in 2022 stated that global warming resulted in
widespread shrinkage in cryosphere and ocean warming absorbing more than 90% of excess heat in
the climate system. Also, global warming is likely to exceed 1.5°C between 2030 and 2052 if it
continues to increase at the current rate which is against the IPCC 2022 goal [3]. The ever-surging
demand for energy in recent years has highlighted the need for investigations around cost-effective
and sustainable energy production to mitigate the climatic crises. This need is highly essential in
industries such as petroleum refineries due to high energy consumption. In the refinery process, the
most energy-consuming processes are crude distillation, followed by the hydrotreater, reforming,
and vacuum distillation, emitting more than 1100 million tons of CO per year [4,5]. Therefore, the
inclusion of CO capture and storage (CCS) in conventional-fossil fuel-based hydrogen production
processes can result in tens of millions of dollars of profit (i.e., a constitute for building materials,
formation of synthetic fuels) in the long run for refineries [6–8] and serve as a climate change
diminution approach.

© 2023 by the author(s). Distributed under a Creative Commons CC BY license.

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Due to the highly reactive nature of hydrogen atoms, it instantaneously reacts with other
elements [9,10]. Therefore, despite it being abundant in nature and the cosmos, it can never be
discovered in its purest form [11]. So, these chemicals must be decomposed or reformed to get pure
hydrogen as gas or liquid. Hydrogen is considered a key raw ingredient for the petroleum and
petrochemical industries and a byproduct of numerous petroleum refining and chemical
manufacturing processes such as chlorine synthesis, photobiological water splitting, and others [12].
Therefore, significant ambitious strategies [13–17] have been undertaken not only by international
energy agencies [18] but also by different states and industries to establish a hydrogen economy.
Hydrogen is acknowledged as one of the future's clean energy vectors [5]. It is an excellent
alternative to produce lighter, cleaner fuels and reduce our reliance on fossil fuels. The LHV of
hydrogen combustion is approximately 143 MJ/kg, which is three times that of petroleum [19].
Hydrogen can be used in fuel cells, devices that convert raw hydrogen into electrical energy for use
in electric automobiles and power plants [20], and thus can serve as a replacement for combustion
engines. Currently, in the USA alone, hydrogen production is approximately 14 million tons per year
(MT/y), which is enough to power about 3 million cars or about 8 million homes [21].
Among the technologies for hydrogen production, the two prominent technologies are steam
reforming [22] and electrolysis [23,24]. Steam reforming with and without conventional CO2 capture
technologies are termed blue hydrogen and grey hydrogen, respectively. On the other hand,
hydrogen produced through water electrolysis using renewable electricity is called green hydrogen
[25,26]. Using an electric current, electrolysis separates water into its constituent parts [24]. The
production of green hydrogen through electrolysis is still an expensive process and even more using
other renewable energy sources such as wind and solar energy to drive the electrolysis process [27].
Moreover, according to DOE reports, the capture of CO2 is an expensive and technologically
challenging process costing more than 400 million dollar for each unit [28,29]. There are several
methods for the production of hydrogen such as partial oxidation used to produce hydrogen and
carbon monoxide by combining oxygen with hydrocarbons (such as natural gas, naphtha, petroleum
coke, or coal) [30–33]. Ammonia decomposition is another method for the separation of ammonia
into its essential components, hydrogen, and nitrogen [34]. Additionally, the emerging technologies
which include various biogas production options using gasification [35] or pyrolysis processes [36],
or biomass fermentation with microorganisms [37,38], and newly developed photo-electrochemical
water splitting [39] and thermochemical processes, including microbial electrolysis [40] for splitting
of water into H and O with lower energy compared to conventional electrolysis [41].
From all these methods, steam methane reforming is a well-matured technology with an
efficiency of over 75-85% [42–44], the highest of any commercial hydrogen generation process, and
runs at or near its maximum capability [45]. Moreover, it is the most often employed technique where
natural gas (methane) or other light hydrocarbons like ethane or propane reacts with steam in the
presence of a catalyst. This process of hydrogen production is comparatively cheaper than the other
methods and will continue to dominate for the upcoming decades. The well-developed natural gas
distribution system in the United States is a major determinant of the overall cost of hydrogen
production which makes this particular process most economically feasible over the other production
process. However, this process owing to a few constraints and challenges of high carbon products
released, which is almost 7 kg CO / kg H [19] which is against the goal of the recent COP27.
Nowadays, the government, research communities, and industries are more concerned with
environmentally benign technologies and CO mitigation, being the primary source of greenhouse
gas, which must be captured before release. Moreover, CO is acidic, and as a result, it cannot be
sequestrated underwater or in the ocean as it may reduce the pH of the water which would adversely
affect the ecohydrology [46]. Furthermore, to avoid environmental pollution and bringing a
sustainable green economy, every industry and production factory must minimize the CO2 emission
to the atmosphere [47]. Therefore, adequate CO2 capture and storage technologies are essential to
protect the atmospheric environment from the potential CO2 pollution. Carbon capture and storage
can be classified as follows- i) carbon-positive, ii) carbon-neutral, and iii) carbon-negative processes
[48–50]. Carbon-positive processes continue to release CO2 into the atmosphere, whereas near-
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carbon-neutral processes do not release any CO2 and carbon-negative processes reduce the amount
of CO2 that is already present in the atmosphere [51].
Since the SMR will continue to dominate the production of hydrogen for at least the next decade,
it is essential to maximize its production and minimize CO2 emissions from this technology. There
have been numerous studies [19,27,35,52–56] have been done on the production of hydrogen using
steam reforming and capturing the emitted CO from SMR. While there are different methods for
CO capture, ‘Post-Combustion Capture (PCC)’ which is one of the three major methods has shown
superiority over other methods as it does not require serious alteration in the existing plant design
and configuration before it can be implemented [57] and can be easily retrofitted into new ones[58].
In addition, PCC has some major advantages including capturing more than 90% of the CO and
ensuring the highest purity in the captured CO . Aqueous amine-based technology is a chemical
absorption process recognized as the most mature for PCC of CO [59,60]. Studies have shown that
amine based CO absorption method can capture up to 100% of the CO present in the flue gas while
maintaining the purity more than 99% [61,62]. Besides this, amine based solvents are quite
inexpensive as well as widely available and thermally stable compared to other methods of carbon
dioxide capture [62]. Aqueous mono-ethanolamine (MEA) and Methyl Diethanolamine (MDEA) are
considered fundamental solvents for PCC technology because of their high separation selectivity for
CO and their rapid rate of reaction [59,60,63]. The major barriers faced the implementation of CCS
is the high cost for carbon capture and the post carbon capture procedure [7,8,61,64]. A properly
integrated heat exchanger network system will reduce this cost [61,64]. High purity of carbon dioxide
will lead to the reduction of the production cost of the processes where CO is necessary [7,8,61]. In
this study, Pinch Analysis (PA) has been done in a couple of the most energy demanding streams to
optimize the heat integration. This also serves to debottleneck operations, optimize utility use, and
improve the energy efficiency of overall systems [65]. The multi-stage compression is performed in
several phases to maintain thermal equilibrium [56]. CO capture technologies which are long been
discussed which are applicable for steam reforming hydrogen plants. But fewer references are
available on removing CO from flue gas though interest of technology is growing. While several
carbon capture and hydrogen production methods and strategies have been developed, this
comprehensive review carefully investigates the gap in this field and describes a simulation-based
method that could be a game-changer in this field of research. The goal of this work is two-fold- i) to
present a unique approach and set a baseline for simultaneously increasing the production of
hydrogen and, ii) improving the removal of CO from the SMR system.

2. Model Development and Process Simulation

2.1. System Description

The process flow diagram for the steam methane reforming considered in this study is depicted
in Figure 1. This work thoroughly investigates hydrogen production via steam reforming and the
CO capture that evolves during the process. The reforming reaction of methane and steam is a highly
endothermic reaction. Therefore, this reaction is usually carried out at higher temperatures of 800-
1000℃ and at a pressure of about 14-20 atm which are the set operating conditions. The reaction
between methane and steam produces H and CO in the reactor-1 with a molar ratio CH : H O of
1:3 based on the following reaction formula:
CH4 + H2 O → 3H2 + CO ΔH= 206 kJ/mol (1)
For fast reforming reactions, a catalyst bed reactor is usually used [66]. The catalytic reactor
concept has been explored for steam reforming of tars in the producer gas and to promote the water-
gas shift reaction to maximize hydrogen production [66]. Also, research has been carried out to
introduce a combined catalyst/sorbent system to replace three catalytic reactors. Following this
reforming process, the Water Gas Shift (WGS) takes place in reactor-2 to reduce the carbon monoxide
content at the outlet of reactor-1 where the SMR reaction took place. Thus, the flue gas is then fed
into the reactor -2 for WGS reaction to remove the CO produced in reaction (2) and increase the
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hydrogen production. WSG reaction is moderately exothermic, therefore occurs at lower

temperatures (300-400℃) than the reaction (1) to facilitates it [35]. The reaction follows as,
CO + H2 O → H2 + CO2 ΔH= -41 kJ/mol (2)
Afterward, the produced hydrogen is separated from the flue gas using a separator, and the rest
of the flue gas is sent to a cooler to reduce the temperature followed by a water separator. About
99.72% of the water and 1.13% CO is separated as the bottom cut of the water separator. The
remaining products leave the separator as the top stream. This top stream then goes into the CO
absorber column where an amine solvent solution is added from the top of the column. This amine
solution absorbs the CO present in the flue gas and leaves the column from the bottom as the CO
Rich solution and the clean flue gas leaves the column as the top product of the carbon capture
column.

Figure 1. Process flow diagram of the proposed steam methane reforming process.

2.2. Model Assumptions

Some of the key assumptions used in this process modeling are:
• All components possess adiabatic boundaries.
• Kinetic exergy and potential exergy overlooked for all the system components.
• Usage of catalyst is considered.
• Formation of coke is overlooked due to negligible concentration.
• The outlet stream temperature of the reactors is considered as reactor’s temperature.
• Tray efficiency in absorption column is assumed to be 100%.

2.3. Model Description

Typically, a steam reforming process involves two successive shift reactors for hydrogen
generation followed by hydrogen and carbon dioxide separators [66]. The production of hydrogen
via steam methane reforming process, and simultaneous capture of carbon dioxide using an amine
solution were investigated. The simulation-based steady-state model as shown in the Figure 1 was
developed using Aspen HYSYS V12.1. Peng Robinson equations of state and Acid Gas- Chemical
solvent fluid packages were used to estimate the thermodynamic properties of the components and
the mixtures in the streams.
Water is heated for steam generation and a multi-stage compressor mechanism is employed
(Figure 1) to increase the pressure of the natural gas. The mole fraction of natural gas was considered
1 for methane. So, the gas is compressed in the first compressor and an inter-cooler is employed for
cooling down the high-temperature gas. This process is repeated at least twice to ensure the data
reproducibility capacity of the system. Then, methane and steam were mixed and heated in HE-2
before entering the conversion-type steam reforming reactor (reactor- 1). Conversion type reactors
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are the simplest type of reactor in HYSYS. Because of its simplicity it is extremely useful for designing
complex reactors [67,68].
Here, a counter-current shell and tube configuration is assumed for all the heat exchangers.
Natural gas and steam are heated-up to produce syngas (CO + H ) according to the endothermic
steam methane reforming reaction-1. The water gas shift (WGS) reaction for high CO conversion is
favored at lower temperatures. Therefore, the overhead product of the reactor-1 was cooled using
HE-2 and HE-3 and fed into the WGS reactor (reactor-2). After that, the overhead product goes into
the shell side of HE-4 for cooling before going into the hydrogen splitter. Hence, a cooling stream
loop was introduced around the WGS reactor.
The remaining flue gases from the Hydrogen splitter (S-1) which is not good for the environment
is fed into the carbon capture and storage system (CCS). Before that the stream is cooled down and
then most of the water is separated from the stream using a separator (S2) to achieve a better carbon
dioxide capture. Natural and refinery gases contain acid gases like hydrogen sulfide (H S) and carbon
dioxide (CO ). A refinery usually consumes 1.5% to 8% of feed as fuel depending on the complexity
of operation. A refinery having capacity of 300,000 bbl per day usually accountable for CO emission
of 0.8 to 4.2 million tons per year [69]. Natural gas can contain up to 28 percent hydrogen sulfide gas
( H S ), which may be considered as air pollutant near petroleum refineries and in oil and gas
extraction areas [70]. The major acid gases are hydrogen sulfide (H S) and carbon dioxide (CO ).
Because of the corrosivity of acid gases in the presence of water, the toxicity of H S, and the lack of
heating value of (CO ), the gases must be purified prior to use with the aid of aqueous solutions of
alkanolamines. They react reversibly with acid gases and therefore are generally used to remove them
[20]. Chemical reaction processes remove the H S and/or CO from the gas stream by chemical
reaction with a material in the solvent solution [70]. Clause process [71] is one of the most popular
methods for removal of large quantities of H S where one third of the H S to be removed, is burnt
to form sulphur dioxide. The reaction is an exothermic one. Then the produced SO reacts with the
unreacted H S to form high quality sulphur (purity>99.9%) [71].
2H2 S + O2 → SO2 + 2H2 O ΔH= -519 kJ/mol (3)
3
2H2 S + SO2 → S8 + 2H2 O ΔH= -146 kJ/mol (4)
8
In this simulation, MEA and MDEA are used as aqueous solvent according to the industrial case.
Likewise, amines and polyamines have been employed as low-cost and effective CO capture
support materials [72]. They offer several benefits over other CO capture systems, including a
reduced regeneration energy penalty when compared to aqueous amine solutions and a higher
moisture tolerance when compared to some of their physi-sorbent equivalents, such as MOFs [67,68].
The gas-sweetening facility has twenty identical amine trains and a suitable pressure gradient across
the column for an efficient CO removal.

2.4. Fluid Packages

2.4.1. Peng-Robinson
The Peng-Robinson equation of state (Peng and Robinson, 1976) is satisfactory for predicting the
gas phase properties of CO and can be used to determine the enthalpy and entropy of a fluid or
fluid mixture as a function of temperature and pressure [69].
This law is not working if the gas pressure is below the triple point due to the discontinuity of
physical and chemical characteristics of gases. For instance, there is no latent heat of fusion found for
gases beyond the triple point. However, the enthalpy estimation of a specific gas relative to a selected
state is possible by using the Peng-Robinson equation of state unless the fluid is not obeying the ideal
gas law [70]. Additional terms including reduced temperature, compressibility factor and acentric
factors are included in the enthalpy and entropy function while fluid does not obey ideal law [73].
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2.4.2. Acid Gas – Chemical solvent

The Acid Gas – Chemical Solvent package in Acid Gas technology supports is used to prepare
the solvents including Methyl Diethanolamine (MDEA), Diethanolamine (DEA), Mono
Ethanolamine (MEA), Diglycolamine (DGA), Diisopropanolamine (DIPA), Piperazine (PZ), and
Triethanolamine (TEA). Additional supports are provided for multiple (>2 types) solvent blends
including Sulfolane + DIPA, Sulfolane + MDEA, Sulfolane + MDEA + PZ, MDEA + MEA + DEA and
any two chemicals solvent blend. The Acid Gas - Chemical Solvents package is developed with the
Peng-Robinson equation of state for vapor phase and electrolyte nonrandom two-liquid (eNRTL) for
electrolyte thermodynamics [73,74].

2.5. Pinch Analysis

Pinch analysis is a method used to reduce the energy consumption of the process by optimizing
the energy recovery methods [75,76]. It examines potential heat exchanges between cold (requiring
heat) and hot (emitting heat) streams to reduce irreversibility. The process data is represented as an
array of energy flows or streams as a function of heat load (or enthalpy) vs. temperature. These data
are integrated for all of the plant's streams to generate composite curves, one for all "hot streams"
(streams that release heat) and one for all "cool streams" (requiring heat). The point of closest
approach between the hot and cold composite curves is the pinch temperature (pinch point or plain
pinch), and it is the point where design is most limited [75,76]. Consequently, the energy objectives
may be met by utilizing heat exchangers to recover heat between hot and cold streams by identifying
this location and beginning the design process there. In fact, cross-pinch heat transfers between
streams with temperatures above and below the pinch are frequently seen during the pinch study.
By eliminating these exchanges through alternate pairing, the process reaches its energy goal [77].

3. Results and Discussion

3.1. Production Variation with Change of Process Parameters

This section discusses the outcome of the modeling and the H production. The process
optimization for efficient system functioning is described in depth. In addition, the model was used
to assess the impact of modifying the most critical parameters. Some critical parameters considered
include Steam to Carbon ratio (S/C), molar flow, temperature, and mole fraction.
The higher the steam to carbon ratio, the lower the residual methane will be for a given reformer
outlet temperature. Hence, less fuel energy is required in the furnace. Figure 2 shows the change in
the molar flow of the hydrogen produced at the splitter with the change of the S/C (at different
methane flowrates).
The S/C ratio was considered from 1 to 10, and change in hydrogen production was observed.
With increasing S/C ratio the production also increased. However, after reaching an equilibrium
point at S/C ratio of 2 the production of hydrogen remained the same even with the increasing ratio.
Thus, when the S/C ratio reached 10 there was no significant effect on the hydrogen production. The
reactors used in the simulation are conversion-type reactors as mentioned earlier. In conversion-type
reaction, the percent of conversion remains constant throughout the process. Therefore, the
production did not vary after reaching an equilibrium point. The increasing S/C ratio will have a
negative effect on the CCS in the later part of the production as the increasing S/C will lead to the
increase in the production of flue gas and water formation. However, an optimum S/C ratio of 3 [78]
was maintained for the cost-minimization of the production process.
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Figure 2. Hydrogen production vs S/C.

Figure 3 shows the variation in flow rates of liquid water and the flue gas at the outlet-stream of
water separator (S-2). As observed from the graph, the flow rate of liquid water increases drastically
with increasing S/C. With the variation of the S/C ratio from 1 to 10, the flow rate varies between 0 to
30420 kgmole/h. However, with the increase of S/C, the formation of flue gas did not vary that much.
It reached a peak of 3605 kgmole/h at S/C of 2 and then decreased to 3419 kgmole/h. Thus, the effect
of increasing S/C resulted in no significant change in the flue gas flow rate but a drastic increase in
the liquid water flow rate is observed. On the other hand, the pure hydrogen production was 9360
kgmole/h at S/C of 1 as displayed in Figure 4. The maximum conversion rate which was 11520
kgmole/h reported when S/C ratio was 2 and remains constant after reaching this equilibrium point.
This result indicates that the production of hydrogen did not vary with increasing S/C ratio. Thus, it
only increases the cost of the process. Increasing S/C also has an adverse effect on the separator as the
separator needs to remove more water before the flue gas is transferred to the carbon dioxide
separator.

Figure 3. Hydrogen, Liquid water, and Flue gas flowrate of S-2 vs S/C.

Figure 4 shows the change in mole fraction for methane and carbon monoxide in reactor 1 with
the change of the S/C. The S/C ratio was considered from 1 to 10, and the mole fraction of CO and
methane gas varied from 0.22 to 0.06 and 0.05 to 0.01, respectively. The lowest point was attained
when the S/C was 10.
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Figure 4. Mole fraction of methane and CO in reactor 1 vs S/C ratio.

Figure 5 demonstrates the change in the overall UA of the heat exchangers 2 and 3 to S/C ratio,
the values considered for the S/C ratio were from 1 to 10. For heat exchanger (HE)-2, the resultant UA
varied from 0.1 to 2.7 kJ/C-h, respectively. The graph shows that in the initial stages, the overall UA
would barely have an effect; however, with the increase in the S/C ratio from 6, the heat exchanger
UA starts increasing. However, the UA was significantly affected when the S/C ratio exceeded 7,
demonstrating that when S/C > 5, discernible results were observed. At S/C ratio 8, an abrupt peak
was observed where change in the UA was recorded from 6.00E+06 to 1.50E+07 kJ/C-h. Nevertheless,
the peak values of the UA were retained at 2.7e+07 kJ/C-h when S/C set at10. In contrast, the recorded
UA values for HE-3 was ranged from 8.00E+05 to -8.00E+05kJ/C-h, The UA of the heat exchanger
increases with the increase in S/C up to S/C = 5.5. However, when the S/C ratio is approaching 6, a
dramatic downward slope of UA was recorded with a minimum value of -2000x105 kJ/C-h. Here,
higher overall heat transfer coefficient signifies better heat transfer between the fluids and works
better where higher heat transfer is required. On the other hand, lower heat transfer represents the
medium is better for insulation purpose [79]. The negative value of UA indicates the reverse direction
of heat transfer inside the heat exchanger.

Figure 5. Overall UA of Heat Exchanger 2 and Heat Exchanger 3 vs S/C.

Figure 6 demonstrate the percentage of separated liquid water in the separator S-2 with varying
cooled flue temperature. The value considered for the temperature was in the range of 30 to 240℃.
The highest separation was almost 99.8% which is recorded at 30℃. Afterward, the amount of water
that had been isolated began to decrease gradually. Eventually, at 190℃, the percent of liquid water
separated in S-2 became 0 (zero) and remains the same for the rest of the study. Unless the water is
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removed earlier before entering the absorber, this water would create barrier in the column while
separating the CO from the flue gas. Thus, this separation of water makes the CCS more efficient.

Figure 6. Liquid water separation (%) vs Cooled flue gas temperature.

Figure 7 indicates the significance of using a cooler beforehand the flue gas enters the Separator-
2 and CO absorber. As observed from the graph, with an increase in the flue gas temperature the
absorption capability of the absorption column decreases. It can be observed that at lower
temperatures the column performs the best, having an efficiency of capturing 100% of CO in the
flue gas. The effect of flue gas’s temperature on liquid water removal is already described in figure
6. However, it can be observed that the temperature not only affects the removal of water in separator
2 but also the CO concentration in the flue gas. At lower temperature, about 2% of CO goes with
water which decreases as the temperature increases.

Figure 7. Effect of flue gas temperature on 𝐶𝑂 capture and water separation.

3.2. Pinch Analysis:

For the system, four streams are considered for pinch analysis:
Stream 1, from the initial water to the mixer
Stream 2, from the output of compressor 1 to the input of compressor 2
Stream 3, from the output of the hydrogen splitter to the input of the water separator
Stream 4, from the output steam turbine in the Rankine cycle subsystem to the water pump.
The streams are described numerically in the table below:
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10

Table 1. Stream data for pinch analysis.

Start Target
Stream Heat Load ∆𝐇
Stream No Temperature Temperature
Type (kW)
(℃) (℃)
1 Cold 30 247.7 5.45 ∗ 108
2 Hot 222.6 30 2.85 ∗ 107
3 Hot 316.7 40 3.096 ∗ 108
4 Hot 207.8 99.96 5.31 ∗ 108

Figures 8 and 9 represent the current model's composite and grand composite curves. It should
be noted that this analysis is done independently of the current heat exchanger system, using the
information related to the reactors and separators. This way, the analysis can be used to either
validate or improve the heat exchanger network. The pinch analysis assumes that the minimum
temperature difference between the hot and cold streams is 10°C to find a theoretical minimum for
the modeled system. Heating and cooling utilities would be required outside of process exchange
sections. It was revealed that there is a requirement for one (1) additional heat exchanger for this
optimized heat integration network which is the major contributor to the increase in overall cost. This
leaves room for further optimization of the overall process.

Figure 8. Composite Curve.

Figure 9. Grand Composite Curve.

According to the pinch analysis finding, this system's theoretical minimum hot utility
requirement is 245 KW. However, after the heat exchanger network design, the requirement for the
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11

hot utility was reduced to 0 kW. Therefore, it can be demonstrated that the current heat exchanger
network is adequate to save the hot energy possible through heat exchange. As for the requirement
for cooling utility, it theoretically required about 90 MW which was optimized by 0.3% requiring
99.7% of the required cooling utility. If the system has not yet been constructed and is still in the
design phase, it may be recommended to use the alternative network to save money on the heat
exchanger network.

3.3. Reformer 1 Yield Variation

Conversion type reactors are the simplest type of the reactor in Aspen HYSYS [80,81]. Due to
their simplicity the yield needs to be defined at the beginning of the designing process leaving less
room for investigating the effect of the change of process parameter on the final product. However,
the steam methane reforming process is a well matured process, and the overall conversion efficiency
is about 65-85% [44]. Therefore, the yield of the reformer 1 was varied with in an acceptable
conversion yield of the reforming process and the H production, flue gas formation and CO
capture process were investigated.

Table 2. CO removal rate at different reformer yield.

Amine
Flue Gas 𝐂𝐎𝟐 Removal
Reformer 𝐇𝟐 Production 𝐂𝐎𝟐 Formation Used
Formation (%) in
Yield (kgmole/hr) (kgmole/hr) (kgmole/
(kgmole/hr) Absorber
hr)
80 11520 8640 2880 100 14450
70 10080 9360 2520 100 15000

60 8640 10080 2160 99.99 16200

3.3.1. Multi-Stage Compression

Initially, methane was compressed before mixing with water and feeding into the reactor. The
compression of methane was done in multiple stages because compression generates heat. Therefore,
the compressed gas needs to be cooled before sending into the next compressor, making the
compression less adiabatic, but more isothermal.
The effect of compressing methane in a multi-stage process to single-stage compression is shown
in Figure 10. As observed from the graph, the rise in temperature of the gas in the three-stage
compression is not higher than single stage compression. The usage of interstage cooling also has a
significant effect on compression. This phenomenon resulted in a less adiabatic and more isothermal
condition because there is no significant increase in temperature.
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Figure 10. Multistage vs Single Stage Compression (Temperature Effect).

3.5. Carbon Capture System (CCS)

Different absorbents (MDEA, MEA, Propylene carbonate) are simulated to determine the most
efficient solvent for this carbon capture system. Upon reviewing a wide range of research work
[57,59–63,72,82–88], rate of carbon dioxide capture depends on the temperature of the solvent.
However, absorption increases with increasing temperature and decreases once a certain
temperature is reached. Several studies have been conducted to find out the optimum temperature
for both solvent and flue to achieve highest CO capture [57,82]. Therefore, the flue gas, which was
released at a higher temperature, needed to be cooled down for efficient absorption.
Absorption of CO varies depending on the characteristics of the solvents. Therefore, a suitable
solvent selection is important to ensure the highest efficiency of CO absorption. Two of the most
used amines in large scale industrial production are MEA, and MDEA which have shown higher
percentage of CO2 absorption [84]. Consequently, these two as well as Propylene Carbonate, which
is also used as a solvent, were considered for further case study in order to select the most suitable
amine.
Figure 11 indicates the variation of absorption column temperature and pressure profile. As
observed from the plot, the temperature of the column started rising around stage 13. On the other
hand, the pressure profile throughout the column remained linear.

Figure 11. Temperature and pressure profile of the absorption column.

Figure 12 provides information on the concentration of CO at different stages of the absorption

column. The plot revealed that there was no CO present above stage 12 and the concentration raised
rapidly as we go to the bottom stages of the column. It showed that the maximum amount CO was
in the bottom stage of the column indicating that the amine was absorbing the CO in the flue gas.
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Figure 12. Concentration of 𝐶𝑂 (%) at different absorption column stages.

Figure 13 compares the percentage of CO absorbed in the solvent along with the change of
concentration of different solvents (using single amine only). Each of the solvent were studied under
the same condition to find out the most suitable solvent for absorption. The mole fraction of amine
solvents to H S was varied between 0.1 to 0.8 and thus, the absorption of CO were studied. CO
absorption varied from the minimum value of 75.02% to maximum of 95.60% for different solvents.
Based upon the study, the highest CO capture is achieved while using MEA and at a molar fraction
of 0.1005 to H S. Thus, it was selected for highest efficiency to CO2 capture.

Figure 13. Mole Fraction of Solvents to 𝐻 𝑆 vs 𝐶𝑂 Absorbed (%).

Figure 14 indicates the change in the molar flow of the CO in CCS with respect to the change
of solvent_in flow rate. Solvent flowrate from 11500 to 15000 kgmole/h is considered as long as the
column converged successfully. However, the increase of absorption of CO became less significant
with respect to the increase of molar flow of the CCS solvent as the curve became flatter. That is why
an acceptable value was chosen.
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Figure 14. Molar flow of the CCS Liquid vs the molar flow of Solvent.

Figure 15 indicates the highest overall CO removal from the flue gas that enters the absorption
column using different amines (using single amine or multiple amines mixed). The plots indicates
that the maximum absorption of 98.87% of the produced CO in the flue gas was absorbed in the CO
absorber and goes out of the column as the bottom stream that previously was about only 0.37%, was
achieved when a mixture of MEA and MDEA amines were used. It also gave information that a
maximum of about 95.6% absorption was achieved with MEA, 93.5% with poly carbonate, and the
lowest absorption among these three of 91.6% was achieved while using MDEA. Additionally, the
mixture of MEA and MDEA can absorb the maximum of 100% of the CO present in the flue gas
entering the CO capture absorption column as some of the CO leaves the flue gas stream with
liquid water at water separator. Other similar case studies have shown CO capture from flue gas
efficiency ranging from 80% to highest of 97.27% [61,89–91].

Figure 15. CO capture from the flue gas entering the absorption column using different amines.

Figure 16 compares the (%) of molar concentration of the major absorbed CO in the CCS liquid
with the variation of the solvent inlet temperature. The plot indicates that the maximum of 98.87% of
the produced CO in steam reforming process was absorbed only at certain temperatures. When the
solvent’s temperature exceeded that certain temperature, the CO absorption efficiency decreased,
and it continued with increasing solvent’s inlet temperature. Case studies revealed when the inlet
temperature of the solvent was less than 50℃, the solvent absorbed the CO with maximum
efficiency. However, as the temperature increased, the absorption efficiency decreased gradually,
89.02% at 64℃, to finally 68.18% of total CO produced at 90℃.

Figure 16. CO absorption in CCS liquid variation vs Amine solvent_ in temperature.

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3.6. ASPEN Energy Analyzer

ASPEN Energy Analyzer tool uses pinch technology in all the utility to optimize the process.
Figure 17 gives information about the possible scope optimization.

Figure 17. Possible Utility Optimization.

The figure shows that the total utility used is about 784 MW, in which hot utility is about 511.4
MW and cold utility is about 272.5 MW. It can be optimized to save about 24.9% for hot utility and
46.6% for cold utility which will be a savings of 32.43% in gross. Figure 13 also displayed that carbon
emissions could be reduced from 157.7 tons/h to 106.6 tons/h which will be~ 32.44% saving in total.
In addition, this process is a high energy demanding as reported in the graphical representation in
Figure 13 Therefore, it is essential to optimize the process to reduce the overall production cost.

4. Conclusion
In this study, a comprehensive investigation of performed on the performance of the overall
production by varying various design parameters. The study revealed that the S/C ratio significantly
impacts flue gas formation and the carbon capture system. Due to the simple nature of the
conversion-type reactors, the hydrogen production did not vary after reaching an equilibrium point.
Moreover, the flue gas formation and CO capture largely depend on the yield of reactor 1 which
was revealed in a case study. Another important finding of this simulation-based investigation is
how the change in process parameters affects the CCS which shows that an effective CCS depends
not only on the temperature and pressure but also on the solvent itself, molar flow, and mole fraction.
Case studies revealed that the temperature of the flue gas and the separation of the liquid water from
the flue gas increased the overall performance of the CCS. Before the process optimization, only 0.37%
of the produced CO was separated from the absorber column as the bottom stream. Moreover, only
8.29% of the amine left the column as the bottom stream whereas it should have been 100% of the
amine leaving with the absorbed CO . Again, the temperature of the flue gas also contributes to the
water content removal from the flue gas. It was also found that the high water content in the flue gas
contributes to the inefficiency of the absorber column. Therefore, to make this process efficient, the
flue gas needed to be cooled down (40℃) to ensure that the water is separated before it enters the
absorption column. The temperature (41℃) and molar concentration (MDEA: MEA= 0.4: 0.6) of the
amine solvent are also vital in an efficient CCS. The effect of using a mixture of two amines enhanced
the overall carbon capture process. The pinch analysis and Aspen energy analyzer revealed that the
process can be optimized and thus the overall cost can be reduced.
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Author Contributions: Conceptualization, A. N. S; methodology- A.N.S and A.T.S.; software- A.N.S., A.T.S.
validation, A.N.S, M.F.A, A. T. S. ; formal analysis-, A.N.S. and A. T. S. ; data cu-ration, A.N. S. and A. T.S.;
writing—original draft preparation, A.N. S. and A. T. S.; writing—review and editing, A.N.S., A.T.S.
visualization, A.T.S. and M.F.A.; supervision, A. N.S., and M. F. A.; All authors have read and agreed to the
published version of the manuscript.

Funding: This research received no external funding.

Conflicts of Interest: The authors declare no conflict of interest.

Appendix A

Nomenclature
SMR Steam Methane Reforming
LHV Lower Heating Value
MDEA Methyl Diethanolamine
DEA Diethanolamine
MEA Mono Ethanolamine
CCS Carbon Capture and Storage
PCC Post Combustion Capture
PA Pinch Analysis
WGS Water Gas Shift
COP Climate Change Conference of Parties
DGA Diglycolamine
DIPA Di-isopropanolamine
PZ Piperazine
TEA Triethanolamine

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