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Green hydrogen and electrical power production through the integration of

CO2 capturing from biogas: Process optimization and dynamic control

Article in Energy Reports · September 2021

DOI: 10.1016/j.egyr.2021.06.048

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Energy Reports 7 (2021) 293–307

www.elsevier.com/locate/egyr

6th International Conference on Advances on Clean Energy Research, ICACER 2021 April
15–17, 2021, Barcelona, Spain

Green hydrogen and electrical power production through the

integration of CO2 capturing from biogas: Process optimization and
dynamic control
Somboon Sukpancharoena ,∗, Natacha Phetyimb
a Division of Mechatronics and Robotics Engineering, Rajamangala University of Technology Thanyaburi, Pathum Thani, 12110, Thailand
b Department of Chemical and Materials Engineering, Faculty of Engineering, Rajamangala University of Technology Thanyaburi, Pathum
Thani, 12110, Thailand
Received 18 May 2021; accepted 9 June 2021

Abstract
This study describes the optimization of a modelling process concerning biogas’ use to generate green hydrogen and electrical
power. The Aspen Plus simulation tool is used to model the procedure, and the approach employed to limit the emissions of
gas from the hydrogen production process will be the CO2 capture method. This technique uses slack lime (Ca(OH)2 ) to
absorb CO2 capture since it is readily available. The study analyzes many critical parameters in the process, including the
temperature and pressure in the steam reforming (SR) and the water gas shift (WGS) reactions along with the steam to carbon
ratio (S/C) to determine how the production of green hydrogen and electrical power will be influenced. Electricity generation is
achieved by taking the residual water from the SR, WGS, carbonation reactions and converting it to the vapour phase, allowing
the steam to pass through the turbine to generate electricity. To examine the effects of the synchronized critical parameters,
response surface methodology (RSM) was used, thus allowing the optimal operational conditions to be determined in the form
of an optimized zone for operation. The result of parameter optimization gave the maximum green hydrogen production of
211.46 kmol/hr, and electric power production of 2,311.68 kWh, representing increases of 34.86% and 5.62%, respectively
when using 100 kmol/hr of biogas. In addition, control structures were also built to control the reactors’ temperature in the
dynamic section. The tuning parameters can control the SR and WGS system’s reactor to maintain the system in approximately
0.29 h and 0.32 h, respectively.
⃝c 2021 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the scientific committee of the 6th International Conference on Advances on Clean Energy Research, ICACER,
2021.

Keywords: Green hydrogen production; Electrical power production; Optimization; CO2 capture; Process dynamic and control; Biogas

1. Introduction
Hydrogen has considerable potential as a fossil fuel alternative since it serves as an energy source that generates
minimal greenhouse gas emissions levels, thereby meeting the current goals of green and clean energy. To be
∗ Corresponding author.
E-mail addresses: somboon_s@rmutt.ac.th (S. Sukpancharoen), nattacha.p@en.rmutt.ac.th (N. Phetyim).

https://doi.org/10.1016/j.egyr.2021.06.048
2352-4847/⃝ c 2021 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the scientific committee of the 6th International Conference on Advances on Clean Energy Research,
ICACER, 2021.
S. Sukpancharoen and N. Phetyim Energy Reports 7 (2021) 293–307

implemented on a larger scale, however, it will first be necessary to lower the production costs involved, as well
as reducing the reliance on fossil fuels, since, at present, fossil fuels are the source of around 96% of hydrogen.
Approximately half of the world’s hydrogen is produced via the steam reforming of natural gas (NG) [1,2]. If it
is possible to obtain the energy required for hydrogen production from renewable sources, then “green hydrogen”
will become a reality. The related researches that produce hydrogen such as [3,4].
One way to generate green hydrogen is through biomass and the processes of pyrolysis or gasification, although
cost can be an issue with these techniques [5]. Another approach, which involves even higher costs, is water
electrolysis, which uses wind energy or photovoltaics [5–7]. However, there is a less costly method with significant
potential: the steam reform of raw biogas [8], comprising predominantly carbon dioxide and methane. The
production process is very similar to that used with natural gas, with the caveat that biogas plants are typically
much smaller in size, and therefore it would be necessary to scale back the production levels [9].
Methane is a renewable form of energy obtained through biogas since it is generated when organic matter
is anaerobically digested. Along with methane (CH4 ), biogas also contains carbon dioxide (CO2 ), as well as
much smaller quantities of nitrogen (N2 ), ammonia (NH3 ), and hydrogen sulphide (H2 S) [8]. While biogas’ direct
combustion is possible, it is not incredibly efficient to produce heat since the gas’s calorific value is reduced due to
the high carbon dioxide content and the humidity levels [9,10]. Instead, it is possible to use a catalytic reform process
suitable for fuel cells to convert biogas to hydrogen-rich syngas [9]. The resulting hydrogen offers high energy
capacity while carbon content is wholly absent [11–13]. Several techniques can be employed in hydrogen production,
and these include steam reforming (SR), dry reforming (DR), auto thermal reforming (ATR), and catalytic partial
oxidation (CPOX).
Renewable biogas is of particular interest since it will allow the generation of power while serving as a
replacement for fossil fuels. Within the European Union, biogas energy production stood at 181 TWh by 2015,
but it is anticipated that this figure will climb as high as 472 TWh by 2030 [14–16]. Its use has been predominantly
in power production or, once upgraded, as fuel for transportation. However, the fact that there is relatively high
CO2 content in biogas has limited its use to a certain extent since the heating value is somewhat constrained and
the flame stability from the gas mixture is low. The literature indicates that conventional steam reforming offers
one means of synthesizing gas production from biogas [17–22].
The damaging effects of CO2 emissions on the natural environment have become well-understood in recent years.
Consequently, reducing such emissions has become an essential political objective worldwide to improve human
life quality over the longer term [23]. This study proposes a means of CO2 capture using a carbonation reaction
since this is a process that will not have adverse consequences for the environment. In particular, useful sources in
which this study has its theoretical basis include [24–28].
For the process of CO2 capture, the Ca(OH)2 carbonation method is employed since this generates CaCO3 ,
which is harmless in the environmental context while offering further advantages in the field of medical science.
For example, CaCO3 is involved in hydroxyapatite production when prepared as the source of calcium as Ca(NO3 )2
solution, whereas the solution of (NH4 )3 PO4 acts as a source of phosphatase and ammonia solution as an agent to
adjust pH values for the synthesis conditions. In this manner, hydroxyapatite can be produced along with β-TCP
phases using a simple precipitation technique [29].
The demand for hydrogen gas is steadily increasing since it is involved in the supply of methanol and ammonia
and being used in space transport. This has directly resulted in the growing interest in developing production
techniques for the gas. Natural gas is a significant hydrogen source since the reformation process releases hydrogen.
Therefore, it is apparent that if current reformers can be optimized for efficient operation, this will prove highly
beneficial. To achieve such optimization, various procedural factors must be examined, some of which operate in
a manner that results in adverse outcomes for the others, so achieving the optimal balance is essential. Managing
this process requires a multi-objective study that will allow the procedure’s conflicting aspects to be addressed to
achieve the optimal overall result [30–34].
Furthermore, engineers responsible for the process must consider both the process dynamics and control of
the simulation system equipment to manage the manufacturing process. This can be accomplished by using
simulation and control studies, which have been a widely used approach in the study of chemical processes for
both batch and continuous operations in recent years [35,36]. Since the turn of the century, the implementation of
computational approaches to assist engineers in this context has become commonplace [37], and engineers thus have
the tools to hand, allowing more rigorous analysis and synthesis techniques. While future advances may be made
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in mathematical modelling, the study of system dynamics can now offer sufficient insights to satisfy engineers’
practical needs [38].
The production of green hydrogen and electric power from biogas and CO2 capture via Ca(OH)2 described
in this research paper requires steam optimization to carbon ratios and the SR and water gas shift (WGS)
reactions’ temperature and pressure. These factors will serve as independent variables by Box–Behnken design. The
objective functions are designated as green hydrogen production and electric power production. Control structures
were constructed and operated to control the reactors’ temperature and maintain the correct temperatures during
production.

2. Process simulation description

This section describes the simulation processes of green hydrogen production and electric power production from
biogas using Aspen Plus software version 8.8 to simulate the process.
The simulation process, as shown in Fig. 1, consists of two mains processes: the SR process and WGS. At
first, the biogas is produced in an anaerobic digestion plant, consisting of 70% CH4 , 27% CO2 , 2% N2 , and 1%
O2 [39], and is then sent to the SR section for the syngas production. The biogas feed into the compressor (CP-01)
of isentropic type is followed by preheating by the heater (HX-01) to serve as the feed biogas in the SR reaction,
and the water (H2O-1) feeds into the pump (P-01). The SR reaction uses the RGibbs reactor type by calculating
phase equilibrium and chemical equilibrium and considering all components when operating at a temperature of
600–800 ◦ C and pressure of 1–3 bar [40]. The green hydrogen gas that occurs after the SR reaction will be separated
from other gases with the separator equipment (SEP-01). Green hydrogen gas is collected in-stream no.8 and sent to
the mixer (MIXER-01). Then, stream no.10 and water (H2O-2) will flow into the WGS reactor. The water (H2O-2)
feeds into the heater (HX-02) for preheating before feeding into the WGS reaction. The WGS reaction uses the
RGibbs reactor type operating at a temperature of 200–400 ◦ C and pressure of 1–3 bar [41]. Then, stream no.15 is
cooled by the cooler (COOLER-1). The green hydrogen gas that occurred after the WGS reaction is separated by
a separator (SEP-02). The green hydrogen gas is collected in-stream no.18, sent to a mixer (MIXER-01) combined
with stream no.8 to obtain the product (green hydrogen). CO2 , CO, and N2 are separated to stream no.23 from stream
no.21, and water is separated and sent to the electric power generation process. The remaining CH4 will be used as a
precursor for further production as CO2 is separated to CO2 capture by stream no.24. Other gases are emitted to the
atmosphere at SEP-04 by the EXH-G1 stream. This plant is necessary to destroy CO2 for environmental friendliness
and zero emissions, so CO2 capture by the carbonation reaction is used. The advantage of CO2 capture is that zero
CO2 emissions were observed from the production process. Before the CO2 capture process, about 2,260 kg of CO2
gas was released into the atmosphere per hour, but after the CO2 capture process, there was only a trace of CO2 gas
released into the atmosphere, or zero. For this production, the CO2 capture uses slack lime carbonation operating in
the RGibbs reactor to get CaCO3 as solid waste (SOLID-W) and water after the reaction is flashed and sent to the
electric power generation process. Stream no.30 is water combined with a small number of other impurities such
as Ca(OH)2 and CO2 . Therefore, it is taken through a separator (SEP-05) to separate unwanted substances via the
EXH-02 stream into the atmosphere for the water’s purity. The water in stream no.31 is heated until the water is
vaporized through the heater (HX-05), which gets heat duty (Q-01) from COOLER-01. After that, steam is used to
generate power by using a turbine (TB-01). Steam is necessary to generate power. In the last stage, green hydrogen
is compressed to 10 bar. The properties of the mainstream are as shown in Table 1.
It is assumed that the SR and WGS reactions and CO2 capture via slack lime carbonation would attain a state
of chemical equilibrium in line with Gibbs free energy minimization. The SR, WGS, and carbonation reactions are
described in Eq. (1) to Eq. (4) as follows:
SR reaction:
0
CH4 + H2 O ↔ CO + 3H2 ∆H298 K = 206 kJ/mol (1)
Reverse methanation reaction:
0
CH4 + H2 O ↔ CO2 + 4H2 ∆H298K = 165 kJ/mol (2)
WGS reaction:
0
CO + H2 O ↔ 2CO2 + 2H2 ∆H298K = −41 kJ/mol (3)
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Fig. 1. The process flow diagram of green hydrogen and electrical power production integrating with CO2 capture from biogas.

Carbonation reaction of slack lime:

0
Ca(OH)2 + CO2 ↔ CaCO3 + H2 O ∆H298K = −109 kJ/mol (4)
At the reactor inlet, the ratio of steam to carbon (S/C) can be defined as Eq. (5):
ṅH2 O
S/C = (5)
ṅCH4

3. Optimization design
3.1. Box-Behnken design (BBD)

The response parameters’ principal and interactive effects were estimated using Box–Behnken design (BBD)
based on RSM [42]. BBD was chosen due to its effectiveness in developing second-order response surface models
for environmental processes; such models can generate relatively accurate predictions of interaction outcomes
without the need for a large number of experimental trials [43].
This research carried out the RSM optimization using Design Expert software version 13 (trial) software, while
BBD involved five factors three-levels design which had the S/C mole ratio (γ ), SR pressure (Ps ), SR temperature
(Ts ), WGS pressure (Pw ), and WGS temperature (Tw ). Table 2 presents the independent variable range as well as
the coded levels; these were determined using initial experimental findings and the results reported in the literature.
Green hydrogen production was represented by the dependent variable f 1 measured in kg/h while f 2 indicated the
production of electrical power in kWh using a process of biogas integrated with CO2 capture.
The experiment’s repeated repeatability was ensured by controlling the centre point replication, which could also
manage the model fit’s suitability and allow the pure error to be determined [44]. To keep systematic errors to a
minimum, the trial runs were carried out randomly.
Analysis of the results was carried out using least-squares regression, allowing predictions of the process response
to be generated [45]. The quadratic equation (Eq. (6)) explained the dynamics of the system and thus could be
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Table 1. Properties of the mainstream.

Stream Composition Mass flow Temperature Pressure
(%mass fraction) (kmol/h) (◦ C) (bar)
BIOGAS 70 CH4 , 27 CO2 , 2 N2 , 1 O2 100 25 1
H2O-1 100 H2 O 70 25 1
6 20.7 CH4 , 14.3 H2 O, 37.1 CO, 18.4 CO2 , 8.3 H2 , 1.2 N2 257.817 700 3
8 100 H2 132.812 700 2.99
10 22.6 CH4 , 15.6 H2 O, 40.5 CO, 20 CO2 , 1.3 N2 124.998 700 2.99
H2O-2 100 H2 O 200 25 1
14 11.3 CH4 , 52.8 H2 O, 0.1 CO, 34.4 CO2 , 0.7 H2 , 0.6 N2 315.746 360 1
18 100 H2 23.976 24.3 0.9
20 11.4 CH4 , 53.2 H2 O, 0.1 CO, 34.7 CO2 , 0.6 N2 291.77 24.3 0.9
22 17.7 CH4 , 82.3 H2 O 238.697 24.2 0.89
23 0.4 CO, 97.9 CO2 , 1.7 N2 53.074 24.2 0.89
EXH-G1 19.3 CO, 80.7 N2 48.763 24.2 0.89
24 100 CO2 51.333 24.2 0.89
CAOH2 100 Ca(OH)2 200 25 1
25 5.4 H2 O, 64.5 Ca(OH)2 , 30.1 CaCO3 251.333 25 1
SOLID-W 0.2 H2 O, 68.1 Ca(OH)2 , 31.7 CaCO3 201.75 300 1
27 100 H2 O 49.583 300 1
CH4 100 CH4 46.311 24.2 0.89
28 100 H2 O 192.385 24.2 0.89
30 100 H2 O 241.968 300 1
EXH-G2 100 CO2 <0.001 300 1
31 100 H2 O 241.968 300 1
STEAM 100 H2 O 241.968 763.9 0.01
33 100 H2 156.795 598.4 0.89
GREEN H2 100 H2 156.795 1679.4 10

Table 2. The coded levels of variables used for BBD.

Decision variables, unit Factor Coded level
−1 0 1
S/C mole ratio γ 0.8/1 1.1/1 1.4/1
SR temp. (◦ C) Ts 600 700 800
SR pressure, bar Ps 1 2 3
WGS temp. (◦ C) Tw 200 300 400
WGS pressure, bar Pw 1 2 3

applied as the standard model [46].

k
∑ k
∑ k ∑
∑ k
f k = β0 + βi X i + βii X i2 + βi j X i X j + Φ (6)
i=1 i=1 i=1 j=1

Which f k indicates the response which the model predicts, or the objective function at kth, X i , X j serve as the
decision variables, β0 is a constant, and βi , β j and βi j are used to represent the respective coefficients of the linear,
square, and interaction effects. Finally, Φ is the random error [47].

3.2. Objective function

Which f k indicates the response which the model predicts, or the objective function at kth, X i , X j serve as the
decision variables, β0 is a constant, and βi , β j and βi j are used to represent the respective coefficients of the linear,
square, and interaction effects. Finally, Φ is the random error [47].
Once the quadratic polynomial has been fitted between the response functions and investigation factors, it is
possible to formulate the biogas process as a multi-objective optimization problem that integrates CO2 capture with
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the production of green hydrogen and electrical power using the mathematical format given as Eq. (7):
Maximize f 1 = f (γ , Ts , Ps , Tw , Pw )
Maximize f 2 = f (γ , Ts , Ps , Tw , Pw )
Subject to: 0.8 ≤ γ ≤ 1.4,
600 ≤ Ts ≤ 800, (7)
1 ≤ Ps ≤ 3,
200 ≤ Tw ≤ 400,
1 ≤ Pw ≤ 3

4. Result and discussion

4.1. The sensitivity of hydrogen production and electric power production

Fig. 2 shows the green hydrogen production and electric power production with temperatures at various operating
pressures when the S/C mole ratio = 1, the reaction temperature and pressure of WGS was 360 ◦ C and 1 bar, the
carbonation of slack lime temperature and pressure were 25 ◦ C and 1 bar, and the water flow rate and slack lime
flow rate of H2O-2 stream and in the slack lime stream are 200 kmol/h.

Fig. 2. Effect of SR temperature and pressure on (a) hydrogen producing; (b) electric power generating.

Fig. 2(a) shows that pressure was only noticeable in the temperature range of 200–1,200 ◦ C as green hydrogen
production decreases inversely with increasing pressure while green hydrogen production increases directly with a
temperature increase. The graph shows that in the temperature range of 1,000–1,200 ◦ C, green hydrogen production
has begun to be stable because the quantity of reactants is reduced until the reactants are exhausted, resulting in
the maximum green hydrogen production and a constant value.
Fig. 2(b) shows that electric power production increases directly with pressure while the electric power production
decreases inversely with temperature. From the figure, it can be seen that electric power production is lower because
the electric power production depends on the amount of water remaining from the steam reforming reaction, the
amount of water produced by the water gas shift reaction, and the carbon capture reaction, so from the graph it
makes sense. The electric power production is lower as the SR reaction temperature is higher because there is less
water in the flow reaction, static water flow inlet of WGS reaction, water occurrence of the WGS reaction, and CO2
capture carbonation reaction of slack lime.
For the sensitivity, the green hydrogen production and electric power production of WGS with temperatures at
various operating pressures (0.5–5 bar), the S/C mole ratio was set to 1, the reaction temperature and pressure of
SR set to 700 ◦ C and 3 bar, and the carbonation temperature and pressure were 25 ◦ C and 1 bar. Simultaneously,
the water flow rate and slack lime flow rate of the H2O-2 stream and the Ca(OH)2 stream were 200 kmol/h., as
shown in Fig. 3. Green hydrogen production has the same result with the sensitivity of SR. Nevertheless, electric
power production increases directly with increases in temperature and pressure.
From Fig. 3(a), the electric power produced increases because the electric power production depends on the
amount of water remaining from the SR reaction, the amount of water produced by the WGS reaction, and the CO2
capture via the carbonation reaction of slack lime. Therefore, it that electric power production becomes substantial
as the temperature of the WGS increases. That is because the higher the amount of water it produces, the higher
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Fig. 3. Effect of WGS temperature and pressure on (a) electrical power generating; (b) hydrogen producing.

the electric power production. But it is noteworthy that during the 700–1,000 ◦ C temperature range of the graph in
Fig. 3(b), green hydrogen production decreased. As a consequence of the reverse reaction, because WGS is usually
exothermic, it performs well at low temperatures.
The S/C mole ratio is significant in the SR reaction, especially concerning the isobaric temperature (1 bar) at
the set reaction temperature and pressure of WGS of 360 ◦ C and 1 bar, the carbonation temperature and pressure
of 25 ◦ C and 1 bar, and the water flow rate and slack lime flow rate of H2O-2 stream and in CAOH2 stream of
200 kmol/h. The green hydrogen produced with temperature distribution at different S/C mole ratios is depicted in
Fig. 4(a).

Fig. 4. Effect of S/C ratio and temperature on (a) hydrogen producing; (b) electrical power generating.

Fig. 4(a) shows the increasing S/C mole ratio, and temperature favours green hydrogen production while the
electric power production increases directly with S/C mole ratio, but the electric power production decreases
inversely as shown in Fig. 4(b).
Fig. 5 shows the temperature of the CO2 capture reaction sensitivity under non-isothermal conditions at isobaric
pressure (1 bar) at the set reaction temperature and pressure of SR of 700 ◦ C and 3 bar, the reaction temperature
and pressure of WGS of 360 ◦ C and 1 bar, and the water flow rate of H2O-1 stream and H2O-2 stream of 70
kmol/h and 200 kmol/h. Since the reaction is exothermic, the reaction can occur at low temperatures. According
to the curves, the temperature below about 1,000 ◦ C resulted in high carbonation according to the CaCO3 curves
and had a low amount of CO2 . At temperatures above approximately 1,000 ◦ C, the reaction will be reversed. The
CO2 content will increase. This has a negative effect when CO2 capture is performed at high temperatures. This
shows that the absorption of energy does not need to be performed at a high temperature. The room temperature
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Fig. 5. Effect of slack lime carbonation temperature on CO2 capture via Ca(OH)2 carbonation.

Table 3. Correlation coefficients of f 1 and f 2 .

f1 f2 f1 f2
A −457.65608 +3232.61910 L −0.000322 −0.000206
B +25.41016 +525.85023 M +0.005225 −0.016292
C +1.24147 −4.43943 N +0.012945 +0.010001
D −47.34363 +168.60309 O −0.208750 +0.650713
E −0.023907 +1.86447 P −0.033532 +0.099352
F −0.548438 +4.17801 Q −27.62384 +108.48101
G +0.187867 −0.748339 R −0.000614 +0.002400
H −8.88417 +35.42281 S +5.05127 −20.18774
I −0.008392 +0.158811 T +0.000712 −0.001784
G +0.130833 −0.392358 U +1.20702 −4.01336
K +0.017540 −0.067288

can cause chemical reactions. Therefore, this research was conducted at room temperature, which reduces energy
consumption in the green hydrogen production process.

4.2. The sensitivity of hydrogen production and electric power production

On the basis of the 45 cases derived from the BBD, the quadratic polynomial was employed to fit between the
two output responses and the five factors investigated, which served as input. Using RSM, the quadratic polynomial
is given as Eq. (8):
f 1 or f 2 = A + Bγ + CTs + DPs + ETw + FPw + Gγ Ts + Hγ Ps + Iγ Tw + Jγ Pw + KTs Ps
+ LTs Tw + MTs Pw + NPs Tw + OPs Pw + Iγ Tw + Jγ Pw + KTs Ps + LTs Tw (8)
2 2 2 2 2
+ MTs Pw + NPs Tw + OPs Pw + PTw Pw + Qγ + RTs + SPs + TTw + UPw
In this case, the letters A–U are used to show the correlation coefficients (CC) for the quadratic polynomial,
which can be seen in Table 3. The results of the design point calculation derived from the BBD can be explained
through ANOVA, showing each factor’s statistical significance in the responses’ context.
Fig. 6 presents the predicted levels of green hydrogen production along with the production of electrical power.
When the 45 cases were tested, it was confirmed that the predictions were relatively close to the simulation outcomes
for each of the objective functions, thus indicating that the experimental design based on BBD was able to indicate
the optimal conditions for green hydrogen and electricity production using biogas with the effective integration of
CO2 capture.
Table 4 reveals a Fisher’s F-value of 585.35, thus indicating the suitability of the proposed model in the context
of data analysis (Prob > F < 0.0001) when using a significance level of 0.05.
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Fig. 6. Comparison between simulation and the predicted value of green hydrogen production and electrical power production.

Table 4. ANOVA of the green hydrogen produces for the quadratic response model.
Source Sum of Squares df Mean Square F-value p-value
Model 66075.30 20 3303.77 585.35 <0.0001
Residual 135.46 24 5.64
Lack of Fit 135.46 20 6.77
Pure Error 0.0000 4 0.0000
Cor Total 66210.76 44

R2 = 0.9980; Adjusted R2 = 0.9962; Predicted R2 = 0.9918; Adequate precision =

94.3521.

It is usually appropriate to employ coefficients of determination (R2 ) to assess the validity and suitability of a
model [48–51]. In the case of this model and the quadratic polynomial, the values for R2 and R2 adj respectively
were 0.9980 and 0.9962, indicating a high degree of accuracy for the model and a good fit. In particular, the R2
value of 0.9980 can be interpreted as an indication that the interactions among independent factors can account for
99.80% of the variation observed in green hydrogen production. Furthermore, R2 and R2 adjusted values were very
similar, suggesting that the model did not include unnecessary variables [52].
The quadratic model can also be approved based on the adequate precision ratio measured to be 94.3521, and the
model is suitable for the navigation of the design space. In general, the ANOVA findings showed reliability in the
optimization and determination of each of the factors affecting green hydrogen production using biogas integrated
with the CO2 capture system.
The results are shown in Table 5 are similar to those in Table 4, with Fisher’s F-value equal to 701.06. The
proposed model displays suitable efficiency levels in data analysis, as indicated via the relatively low value: Prob
> F < 0.0001, considered at a significance level of 0.05. When conducting response surface regression for the
quadratic polynomial model, the respective R2 and the R2 adj, which were obtained, measured at a level of 0.9983
and 0.9969, indicating a good fit and accuracy level, the R2 value of 0.9983 can be interpreted to show that the
model explains 99.83% of the variation arising in electric power production, while the quadratic model had an
adequate precision ratio of 107.6972, suggesting it is appropriate to use this model to navigate the design space.
In general, the ANOVA findings showed reliability in the optimization and determination of each of the factors
affecting electric power production.

4.3. The sensitivity of hydrogen production and electric power production

Additional analysis of the interactions between dependent and independent variables was carried out using 3D
response surface plots. In Fig. 7, the outcomes for the SR reaction temperature and the S/C mole ratio can
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Table 5. ANOVA of the electric power production for the quadratic response model.
Source Sum of Squares df Mean Square F-value p-value
Model 1.220E+06 20 60992.00 701.26 <0.0001
Residual 2087.40 24 86.98
Lack of Fit 2087.40 20 104.37
Pure Error 0.0000 4 0.0000
Cor Total 1.222E+06 44

R2 = 0.9983; Adjusted R2 = 0.9969; Predicted R2 = 0.9932; Adequate precision =

107.6972.

be observed. Fig. 7 also shows the coloured bars showing the amount of green hydrogen production from the
underproduction shown in blue to red on the colour bar. The three independent variables which were kept constant
at the centre coded level are Ps , Tw , and Pw . It can be seen that there was a significant influence from reaction
temperature upon the S/C mole ratio in the production of green hydrogen, with a notable increase occurring when
the SR reaction temperature rose from 600 to 800 ◦ C. There was an enhanced result for the S/C mole ratio to green
hydrogen production due to the endothermic SR reaction. The S/C mole ratio to green hydrogen production changed
significantly when the temperature remained constant, but there was a change in the flow rate or mole ratio.

Fig. 7. 3D response surface diagrams showing the mutual interaction effects of the SR temperature and S/C mole ratio with green hydrogen
production.

For the response surface analysis of electric power production considering the effects of interaction from the WGS
reaction temperature and the S/C mole ratio, the three independent variables Ts , Ps , and Pw were kept constant at
the centre coded level. Fig. 8 indicates that when the temperature was increased at more excellent S/C mole ratios,
electric power production was also significantly higher, with an immediate increase observed as the WGS reaction
temperature rose from 200 to 400 ◦ C. The Fig. 8 colour bars indicate the descending electricity generation, as shown
in a gradient from blue to red.

4.4. Process optimization

The optimization of temperature, pressure, and the S/C mole ratio of the SR reaction and WGS reaction allows
comparison of the initial value and the optimal value’s operating parameters and optimal value, as shown in Table 6.
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Fig. 8. 3D response surface diagrams showing the mutual interaction effects of the WGS temperature and S/C mole ratio with electrical
power production.

Table 6. Initial value and optimize value operating parameters.

Initial value Optimize value
S/C = 1 S/C = 1.4
Flow rate (kmol/h) Temp. (◦ C) Pressure (bar) Flow rate (kmol/h) Temp. (◦ C) Pressure (bar)
Stream
-BIOGAS 100 25 1 100 25 1
-H2O-1 70 25 1 89.7288 25 1
-H2O-2 200 25 1 200 25 1
-CAOH2 200 25 1 200 25 1
Equipment
-Compressor (CP-01) 3 3
-Compressor (CP-02) 820 820
-Compressor (TB-01) 0.01 0.01
-Pump (P-01) 3 3
-Heater (HX-01) 200 1 200 1
-Heater (HX-02) 200 1 200 1
-Heater (HX-03) 25 1 25 1
-Heater (HX-04) 300 1 300 1
-Heater (COOLER-1) 25 1 25 1
-Flash (FLASH) 300 1 300 1
-Reactor (SR) 700 3 648.966 1.0077
-Reactor (WGS) 360 1 400 1.0003
-Reactor (CO2 -CAP) 25 1 25 1
Product
-Green hydrogen (kmol/h) 156.795 211.46
-Electric power (kWh) 2,188.70553 2,311.68

As a result, the green hydrogen production and electric power production values from the optimal use of the
optimal values were 211.46 kmol/h and 2,311.68 kWh, respectively. Green hydrogen production was superior to
the initial value of 54.67 kmol/h, and electric power production was more significant than the initial value of
122.97 kWh. To demonstrate the validity of RSM-Aspen Plus integration in terms of experimental data predictions,
random experiments were performed independently outside the model. The results can be seen in Table 7, allowing
comparisons to be drawn with the data simulations. The predicted data and the experimental data show strong
similarities to the values derived from the RSM-Aspen Plus integration, thus confirming the latter approach’s validity
and accuracy in the context of predictions concerning green hydrogen production and electrical production power.
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Table 7. Comparisons of simulation data with the predictions using RSM-Aspen Plus
integration.
Objective function Green hydrogen production Electric power production
(kg/h) (kWh)
Simulation 211.46 2,311.68
Predicted 209.75 2,315.93
% Precision 99.19% 99.82%

4.5. Process dynamics and control

The control structure plays an essential role in the simulation, while the controller can ensure that failures do
not occur during the actual production process.
Initially, Aspen Plus was used to perform the steady-state design before undergoing exportation to Aspen Plus
Dynamic to carry out a flow driven simulation. The control structure allowed the reactor temperatures to be
managed. High temperatures are required for both the SR and WGS reactors, and these can be controlled using a
proportional–integral controller.
It can be seen from the controller graph shown in Fig. 9(a), before turning the controller, that the SR reactor ran
dynamically for 5 h, and thus it can be determined that after starting to run, the control system of the reactor can
ensure the system is maintained in around 5 h. In the WGS reactor control system, it is possible to maintain the
system in around 10 h, which can be observed from Fig. 9(b).

Fig. 9. Temperature control result plot: (a) SR reactor before tuning; (b) WGS reactor before tuning; (c) SR reactor after tuning; (d) WGS
reactor after tuning..

In order to drive the steady-state within the correct timeframe, it is suggested to use the tuning parameters
algorithm based on the internal model control (IMC) tuning rule. These determine the appropriate gain, integral
time, and action of the control system. It is then possible to use Aspen Plus Dynamic software version 8.8 to
calculate the optimal tuning parameters shown in Table 8.
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Table 8. Tuning parameter of the controller.

Controller Gain Integral time Action
(%/%) (min)
SR control 5.242439 0.600064 Reverse
WGS control 24.57989 0.600155 Reverse

After tuning the SR reactor and WGS reactor controller, it was found that the reactor can maintain the system
faster than before tuning the controller. The control systems of the SR reactor and WGS reactor can maintain the
system in approximately 0.29 (Fig. 9(c)) and 0.32 (Fig. 9(d)) hours, respectively.

5. Conclusion
The study results found that green hydrogen production and electric power production from biogas of 100 kmol/h
are environmentally friendly and result in zero emissions when using slack lime for CO2 capture, reducing carbon
dioxide emissions by up to 95% through simulation synthesis via Aspen Plus software. Also, the solid waste products
(CaCO3 ) obtained from the reaction are not harmful to the environment and can be further used in various fields.
The sensitivity results for independent and dependent variables show that a higher S/C mole ratio will lead to a
higher hydrogen yield and electrical power production, which is more pronounced at high temperatures than at
low temperatures in terms of the SR reaction. However, in the WGS reaction, electric power production directly
increases when the temperature increases. This research uses temperature, pressure, and the S/C mole ratio as
independent variables for green hydrogen and electric power production for optimizing sections. The quadratic
equation of green hydrogen production and electric power production has precision (%) of 99.19% and 99.82%,
respectively. Therefore, optimizing the value of temperature, pressure, and the S/C mole ratio in the study gives
higher green hydrogen production and electric power production at around 54.67 kmol/h and 122.97 kWh with
superior performance compared to the initial value.
Moreover, the SR reactor and WGS reactor are controlled in the dynamic and control sections, causing a high
operating temperature. Both reactors are reverse action. Gain (%/%) of the SR reactor is 5.242439, and for the
WGS reactor, it is 24.57989. The integral time (min) of the SR reactor is 0.600064, and for the WGS reactor, it is
0.600155. After using tuning parameters, the SR reactor and WGS reactor can maintain the system faster.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could
have appeared to influence the work reported in this paper.

Acknowledgement
This work is supported by the Rajamangala University of Technology Thanyaburi (RMUTT).

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