Case Studies in Thermal Engineering 54 (2024) 103975

Contents lists available at ScienceDirect

Case Studies in Thermal Engineering

journal homepage: www.elsevier.com/locate/csite

Process simulation of methanol production via carbon dioxide

hydrogenation
Jinfeng Fu a, *, Mohammed Sh Majid b, Farag M.A. Altalbawy c, d,
Radhwan M. Hussein e, Ibrahem Waleed f, Ibrahim Mourad Mohammed g,
Rahman S. Zabibah h, Kadhum Al-Majdi i, Abdul Malik j
a School of Chemical and Environmental Engineering, Jiaozuo University, Jiaozuo, Henan, 454000, China
b Computer Techniques Engineering Department, Al-Mustaqbal University College, Babylon, 51001, Iraq
c National Institute of Laser Enhanced Sciences (NILES), University of Cairo, Giza, 12613, Egypt
d Department of Chemistry, University College of Duba, University of Tabuk, Tabuk, Saudi Arabia
e College of Pharmacy, Ahl Al Bayt University, Kerbala, Iraq
f Medical Technical College, Al-Farahidi University, Iraq
g Al-Nisour University College, Baghdad, Iraq
h Medical Laboratory Technology Department, College of Medical Technology, The Islamic University, Najaf, Iraq
i Department of Biomedical Engineering, Ashur University College, Baghdad, Iraq
j Department of Pharmaceutics, College of Pharmacy, King Saud University, Saudi Arabia

ARTICLE INFO ABSTRACT

Handling Editor: Huihe Qiu The performance of a packed bed reactor for CO2 conversion to methanol was investigated. Be-
cause of the exothermic reaction, temperature and concentration gradients happen along the re-
Keywords:
actor. A 2D packed-bed reactor model was applied for numerical investigations, coupled with de-
Carbon dioxide
tailed reaction kinetics and transport phenomena. The effect of feed inlet pressure and tempera-
Heat transfer
Hydrogen
ture on CO2 conversion and temperature profiles along the reactor was evaluated. The results
Mass transfer showed that firstly increase in the temperature in the reactor because of the presence of exother-
Methanol mic reactions and then slight decrease in the temperature at top section of the reactor. Pressure
Modelling was decrease from 55 bar to around 54 bar along the reactor. It was found that the CO2 conver-
sion at outlet of reactor was 18.18 % at T = 475 K and it was increased to 23 % at temperature of
498 K and 555 K. The CO2 conversion was reached its maximum at short distance from the reac-
tor entrance at T = 555 K. Also, the outlet temperature of gas mixture was increased from
522.53 K to 534.56 K with increasing feed inlet pressure from 35 bar to 55 bar. The CO2 conver-
sion was 18.12 %, 20.77 %, and 22.96 % at pressures equal to 35, 45, and 55 bar respectively.

1. Introduction
Emissions of carbon dioxide, which are mostly produced by heavy industries and traditional power plants, constitute a danger to
the environment and significantly contribute to global warming. Effective actions to reduce climate change and manage air pollution
are urgently needed as a result of rising CO2 levels in the atmosphere [1]. About 81 % of the total amount of greenhouse gases comes
from CO2 [2]. One novel strategy uses CO2 as a chemical feedstock to produce methanol [3]. Methanol is an important C1 chemical
that is used to produce a variety of other compounds, such as formaldehyde, methyl tert-butyl ether, olefin, and others [4]. Methanol

* Corresponding author.
E-mail address: [email protected] (J. Fu).

https://doi.org/10.1016/j.csite.2024.103975
Received 16 October 2023; Received in revised form 22 December 2023; Accepted 2 January 2024
Available online 3 January 2024
2214-157X/© 2024 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
J. Fu et al. Case Studies in Thermal Engineering 54 (2024) 103975

has potential as a car fuel and is less harmful to the environment than conventional fossil fuels [5]. Methanol production capacity is
now estimated to be over 100 million tonnes per year, and it is predicted to rise by 10 % per year [6].
There are several methods for methanol production on commercial scale. The common method for methanol production is per-
formed through multiple main steps: generation of syngas from coal gasification or natural gas reforming; conditioning of syngas; and
methanol synthesis and purification. Around 80 % of methanol is made using steam reforming technology [7]. In recent years,
methanol generation in Kraft pulp mills has drawn a lot of attention. It provides some advantages, including sustainable development,
less waste, and revenue stream diversification [8]. Another technique to produce methanol is CO2 hydrogenation. Green hydrogen
combined with CO2 hydrogenation to methanol offers a workable process approach that lowers CO2 emissions while increasing the
ability to use renewable energy [9]. CO2 Hydrogenation by ZrO2/Cu(111) was investigated and it was found that ZrO2/Cu(111) is
better than ZnO/Cu(111) due to the different sizes of the oxide islands as well as in the strength of oxide-metal bonds [10].
Due to the chemical stability and inertness of carbon dioxide, an effective catalyst is one of the essential components in the CO2
hydrogenation to methanol process. The selectivity of methanol and the rate of carbon dioxide conversion are significantly influenced
by the catalysts. In general, three categories may be made out of the catalysts depending on the different active ingredients. Cu-base
catalysts including Cu/ZnO/Al2O3 and Cu/ZnO/ZrO2 are the most common catalytic systems used for carbon dioxide hydrogenation
[9,11]. Conventional coprecipitation, reduction-deposition, lame-combustion, or parallel-slurry-mixing methods are used for the
preparation of the Cu-base catalysts [12]. Fang et al. [13] used Cu/ZnO/Al2O3 catalyst for dehydrogenation of 2-butanol. Pd-modified
(Pd-modified) CuO–ZnO–Al2O3 catalysts were used for methanol synthesis from CO2 hydrogenation and it was found that Pd en-
hanced the CZA catalyst's performance at low temperatures [14]. Plasma-catalytic CO2 hydrogenation to methanol was performed us-
ing CuO–MgO/Beta catalyst. The conversion and selectivity of CO2 hydrogenation to methanol was obtained 8.5 % and 72 % [15].
Different aspects of CO2 hydrogenation to methanol over various catalysts have been investigated recently [16–20]. However, it
should be mentioned that the carbon dioxide conversion ranges from 1.5 % to 25.9 % because of the thermodynamic equilibrium
limit [21] and it is a high-pressure system. Also, the production of water during the reaction can cause the inactivation of the catalyst
[22]. Heracleous et al. [23] investigated the use of zeolite 13X as a water adsorbent in CO2 hydrogenation reactions to increase the
performance of processes. It led to a significant enhancement in the carbon dioxide conversion and methanol yield (115 %).
Due to the importance of the carbon dioxide hydrogenation process, the theoretical approach could provide valuable information
to understand and optimise the process [24]. In recent years, mostly methanol steam reforming was modelled and simulated. Model-
ling and simulation of the H2 production and CH3OH steam reforming in a double-jacketed membrane reactor were performed. H2 re-
covery, methanol conversion, and production rate were better in a double-jacketed membrane reactor than in an auto-thermal reactor
[25,26]. CH3OH production using carbon dioxide hydrogenation was theoretically investigated with zeolite's catalyst in a pressure
swing adsorption reactor. It was proposed that the highest conversion can be obtained at the temperature and pressure of 250 °C and
50 bar in a step. The selectivity and productivity were 83–96 % and 0.023–0.13 mol m3 s−1 [27]. There are few research studies to in-
vestigate methanol production by carbon dioxide hydrogenation in more detail. Three methanol reactor configurations were simu-
lated to predict the process performance. It was observed that axial dispersion does not play a significant role and it was ignored and
the reactor with recycled showed the best performance [28]. Leonzio and Foscolo [29] studied methanol production the structured as
well as non-structured catalyst packing and it was found the carbon dioxide selectivity to CH3OH and methanol yield were 28 % and
4 % higher in structured packing. A 1D model was used to study CO2 hydrogenation in a fixed-bed reactor. Maximum methanol yield
is observed to be limited by 1D solution [30]. As can be seen, most of the developed models are 1D, therefore, it will be valuable to in-
vestigate the system in 2D as it is possible to get more accurate results. The important point of this study is focusing on the analysis of
the system performance for a wide range of operating conditions. Also, previously developed model, the hydrogenation of carbon
monoxide was not considered in the kinetic of the developed model [29], however, the model in the current study considers this reac-
tion which can improve the accuracy of the model.
In the current study, the emphasis is on the development of a 2D comprehensive mathematical model to predict the synthesis of
methanol by catalyst (CuO/ZnO/Al2O3) in the multi-tubular reactor. The effect of different operating parameters on methanol pro-
duction in the reactor was investigated.

2. Model development
Fig. 1 represents the domains of Lurgi type multi-tubular reactor. The gas mixture enters from the bottom of the reactor into the
tube side while the boiling water passes through the shell side of the reactor counter-currently. The tube side of the reactor is packed
with CuO/ZnO/Al2O3 catalyst [29].
The kinetic mechanism considered in the current work was suggested by some researchers previously. It was suggested the hydro-
genation of CO2 and CO disregarding the water-gas shift [31,32]. In the current study, 3 reactions including hydrogenation of CO2 as
well as CO, and reverse water-gas shift were considered as follows [33,34]:

kJ
CO + 2H2 ↔ CH3 OH ΔH 0298 = −90.55 (1)
mol
kJ
CO2 + H2 ↔ CO + H2 O ΔH 0298 = 41.12 (2)
mol
kJ
CO2 + 3H2 ↔ CH3 OH + H2 O ΔH 0298 = −49.43 (3)
mol

2
J. Fu et al. Case Studies in Thermal Engineering 54 (2024) 103975

Fig. 1. Lurgi type multi-tubular reactor for CO2 hydrogenation.

It should be noted that side reactions and by-products were ignored as they are quantitatively negligible [35]. The reaction rate for
the reactions of (1), (2), and (3) can be written as follows [34]:
  
k1 KCO pCO p1.5
H2
− pCH3OH ∕ p0.5 K0
H2 p1
r1 =   0.5 𝜌 (4)
1 + KCO pCO + K CO2 pCO2 p0.5

H2
+ KH2O ∕KH2 pH 2 O
  
0
k2 KCO2 pCO2 pH2 − pH2O pCO ∕ Kp2
r2 =   0.5 𝜌 (5)
1 + KCO pCO + K CO2 pCO2 p0.5
 
H2
+ KH2O ∕KH2 pH 2 O
  
k3 KCO2 pCO2 p1.5
H2
− pCH3OH pH2O ∕ p1.5 K0
H2 p3
r3 =   0.5 𝜌 (6)
1 + KCO pCO + K CO2 pCO2 p0.5

H2
+ KH2O ∕KH2 pH 2 O

Kinetic constants in the reactions are provided in Table 1.

The proposed model was simplified according to the assumptions that follow [28,29].
• Axial dissuion and catalyst deactivation is negligible.
• The components were assumed as ideal gas
• A steady temperature and pressure distribution inside the catalyst particles

Table 1
Kinetic constants of methanol production by CO2 hydrogenation [34,36].

Rate constants

k = Aexp(B/RT) A [mol/s.kg.bar] B [J/mol]

7
k1 4.89 × 10 −113000
11
k2 9.64 × 10 −152900
5
k3 1.09 × 10 −87500

Equilibrium constants

Log10K = A/T-B A [K] B [−]

Keq,1 5139 12.61

Keq,2 −2073 −2.029
Keq,3 3066 10.5

Adsorption equilibrium constants

k = Aexp(B/RT) A (1/bar) B [J/mol]

−5
KCO 2.16 × 10 46800
−7
KCO2 7.05 × 10 61700
0.5 −9
(KH2O/KH2) 6.37 × 10 84000

3
J. Fu et al. Case Studies in Thermal Engineering 54 (2024) 103975

The mass transfer of components in the packed reactor is determined using the following equation [28]:
( ) 2
Uz rtot 2
ri,o rtot
1 𝜕 𝜕C 𝜕Ci r
r i − + i =0 (7)
r 𝜕r 𝜕r Ltot De 𝜕z ri,o DrCin,CO2

where r and z denote radial and axial coordinates, Ci refers to the molar concentration of component i, and Uz and rtot are the superfi-
cial gas velocity and the radius of the tube in the reactor. The symbol Dr means the dispersion coefficient in r-direction. In addition, ri
is the reaction rate of i component in mol/m3s. The superficial gas velocity was calculated based on the following equation [28]:
∑
Fi
Pin T i (8)
Uz = Uin
P Tin Ftot,in

The heat transfer equation in the reactor is presented as follows [29]:

∑
2 ΔH Dr C 2 2
1 𝜕 z in,CO2 rtot Ri,o Ri,o
Uz Cp,i Ci rtot
(9)
𝜕T j 𝜕T
( ) ∑
r − − =0
r 𝜕r 𝜕r j=1
KeT in DeC in,CO2 Ri Ltot Ke 𝜕z

The T is the temperature, ΔHj denotes the heat of the reaction. Dr and Ke are calculated using the following equations [29]:

⎛ ⎞
⎜ 𝜀 1−𝜀 ⎟
Ke = Kg ⎜ + Kg ⎟ (10)
⎜ 1.5 0.312𝜀2.32 + 2
⎟
⎝ Kcat 3⎠

(11)
( −3
)
Kg = 0.01234 × 10 + 1.84375 × 10−7 T

dp 𝜇
8
Dr =   d 2  (12)
1 + 19.4 dp
t

Pin 𝜕P ) [ 150 (1 − 𝜀) 𝜇 ]
G 1−𝜀
(
=− + 1.75G (13)
Ltot 𝜕z 𝜌gc dp 𝜀3 dp

Pad is the dimensionless pressure, Pad ¼ P/Pin, Pin is the feed pressure at the entrance of the reactor in Pa, G refers velocity sym-
bol in kgs−1m−2, ρ defines the density of gas in kg/m3. Boundary conditions for the developed model are provided in Table 2. Further-
more, a list of the values of parameters used in the developed model is given in Table 3.

3. Results and discussion

The molar flow of components as a function of the length of the reactor is shown in Fig. 2. The results are quite similar to other
previous studies [28,29]. The carbon monoxide content in the feed was 0.07 mol/s. According to Fig. 2, as expected, the molar flow
rate of hydrogen and carbon dioxide decreased along the packed bed reactor. On the other hand, the molar flow rate of water,
methanol, and CO increased along the reactor. The rate of increase in the products is higher in the first 5 m of the rector but after that,
it reaches a plateau. Table 4 shows the outlet molar flowrate of components. The hydrogen and CO2 molar flowrates decreased from
1.88 to 0.58 mol/s to 1.58 and 0.47 mol/s respectively. Furthermore, the molar flowrate of methanol, carbon monoxide, and water
was increased from 0, 0.07, 0 to 0.09, 0.08, and, 0.11 mol/s.
Fig. 3 shows the change in temperature and pressure along the packed bed reactor. The temperature was increased along the re-
actor due to the presence of exothermic reactions and reached the maximum of 537.65 K, then, the temperature was dropped to
534.73 K. Also, there was a decrease in pressure from 55 bar to 54.01 bar along the packed bed reactor. Similar temperature and
pressure profiles were observed in previous studies [36].
Fig. 4 provides the molar flow rate of components along the packed bed reactor without the presence of carbon monoxide in the
feed gas mixture. 25 % of the feed is CO2 and the rest of them is hydrogen. The absence of CO in feed improved a bit H2 and CO2 con-

Table 2
Boundary conditions of the developed model [29].

Boundary Mass transfer Heat Transfer Pressure drop

z=0 Ci,in Tin Pin

r=0 ∂C/∂r ∂T/∂r Axial Symmetry
z=L Outlet Outlet Outlet
r = r1 ∂C/∂r Ke×Tin
× 𝜕T (
= U × Tin − Tref
) wall
rtot 𝜕r

4
J. Fu et al. Case Studies in Thermal Engineering 54 (2024) 103975

Table 3
Simulation parameters for the model [28,29].

Parameter Value unit

Entrance feed temperature 498 K

Temperature of coolant 523 K
Entrance pressure of feed 55 Bar
Diameter of tube 0.058 m
Length of tube 8 m
Flow rate 100 mol/s
Number of tube 150 –
3
Density of packed bed 1050 kg/m
Inlet carbon monoxide molar fraction 0 %
Inlet carbon dioxide molar fraction 25 %
Inlet hydrogen molar fraction 75 %
H2O molar fraction, inlet 0 %
CH3OH molar fraction, inlet 0 %

Fig. 2. The molar flow of components as a function of the length of the reactor, inlet components provided in Table 1, inlet pressure = 55 bar, inlet tempera-
ture = 498 K.

Table 4
The outlet molar flowrate of components in the current work and previous studies [28].

Gas species Inlet Conc. (mol/s) Outlet Conc. (mol/s) Outlet Conc. (mol/s) [28]

Carbon monoxide 0.070 0.090 0.080

Hydrogen 1.880 1.600 1.590
Carbon dioxide 0.580 0.470 0.470
CH3OH 0.000 0.090 0.090
H2O 0.000 0.110 0.110

Fig. 3. Change in temperature and pressure along the packed bed reactor, inlet components provided in Table 1, inlet pressure = 55 bar, inlet temperature = 498 K.

5
J. Fu et al. Case Studies in Thermal Engineering 54 (2024) 103975

Fig. 4. Gaseous flow rates inside the methanol reactor as a function of tube length, no CO presence in the feed, CO2 inlet flowrate = 25 %, H2 inlet flowrate = 75 %.

sumption and enhanced the product's molar flowrate at the outlet of the reactor. The methanol content at the outlet of the gas stream
was increased from 0.088 mol/s to 0.094 mol/s.

3.1. Effect of feed inlet temperature

Fig. 5 shows carbon dioxide profiles inside the CH3OH reactor with various values of feed inlet temperature. The global heat ex-
change temperature was equal to 523 K. At the outlet of the reactor, carbon dioxide conversion is equal to 18.18 %, 22.97 %, and
23.02 %, for values of feed inlet temperature equal to 475 K, 498 K, and 555 K, respectively. It was observed that the change in feed
temperature from 498 K to 555 K did not have a considerable effect on the outlet conversion of CO2 in the reactor. However, it
reached the highest value at a short distance from the entrance of the reactor. It means the shorter packed bed reactor is needed for
the same conversion of CO2. Changes in temperature along the packed bed reactor at different feed inlet temperatures have been
compared in Fig. 6. Fig. 6 depicts that there is a slight increase in temperature until 4 m from the bottom of the reactor, but, after
that, the rate of increase in temperature increased and it has reached 534.49 K when the inlet temperature was 475 K. At inlet tem-
perature of 498 K, the temperature was reached a maximum of 537.65 K at distance of 5 m from entrance, then, it was decreased

Fig. 5. CO2 conversion as a function of reactor length at different feed inlet temperature.

Fig. 6. Temperature profile as a function of reactor length at different feed inlet temperature.

6
J. Fu et al. Case Studies in Thermal Engineering 54 (2024) 103975

Fig. 7. CO2 conversion as a function of reactor length at different feed inlet pressure.

Fig. 8. Temperature profile as a function of reactor length at different feed inlet temperatures.

around 534 K at the outlet of the reactor. As shown in Fig. 6, there is a quick increase in temperature and then a gradual decrease in
temperature until the end of the reactor at an inlet temperature of 555 K.

3.2. Effect of feed inlet pressure

The comparisons of carbon dioxide conversion rates along the packed bed reactor in different feed inlet pressures are presented in
Fig.7. It is obvious that the rise in feed inlet pressure led to the CO2 conversion increment. The CO2 conversion becomes better with
the increase of the inlet pressure. The conversion of CO2 can reach up to 17.81 %, 20.52 %, and 22.81 % when the feed inlet pressure
values are equal to 35 bar, 45 bar, and 55 bar respectively. Fig. 7 points out in fact that the packed bed reactor performance was im-
proved in terms of conversion of CO2 with the increasing of feed inlet pressure. Firstly, the increase in CO2 conversion is linear, then
there is a sharp rise especially in higher pressure, finally, the rate of increase was decreased until the end of the reactor. Fig. 8 pro-
vides temperature profiles as a function of reactor length at different pressures. The highest temperature observed in the reactor was
equal to 523 K, 530 K, and 538 K at pressures of 35 bar, 45 bar, and 55 bar.

3.3. Effect of length of reactor

Fig. 9 indicates the influence of the length of the reactor on temperature profiles along the packed bed reactor. The performances
of the PB reactor were affected when changing the reactor tube length. It can be seen that for all the rector lengths the same typical
profile of temperature and it confirms the presence of exothermic reactions, showing a hot spot after the same distance from the re-
actor inlet. The temperature reaches its highest values after the same distance from the entrance for different sizes of reactor length.

4. Conclusion
To improve the process of methanol production from carbon dioxide and hydrogen and decrease its cost, a numerical simulation
tool was provided in the current study. The effects of operating conditions including the presence of CO in feed, feed inlet pressure
and temperature, and the length of the reactor on performance of system were systematically investigated. It was seen a decrease in
H2 and CO2 from 1.88 to 1.58 mol/s to 0.58 and 0.47 mol/s but an increase in the molar flowrate of CH3OH, CO, and H2O from 0,
0.07, 0 to 0.09, 0.08, and, 0.11 mol/s respectively. The results showed that carbon dioxide conversion is equal to 18.18 %, 22.97 %,
and 23.02 %, for values of feed inlet temperature equal to 475 K, 498 K, and 555 K, respectively. It was also found that the changing
feed temperature from 498 K to 555 K did not have a significant influence on the outlet conversion of CO2 in the reactor. Further-
more, the conversion of CO2 and maximum temperature in the reactor was increased from 18.13 % to 22.97 and 523 K–538 K with

7
J. Fu et al. Case Studies in Thermal Engineering 54 (2024) 103975

Fig. 9. Temperature profile as a function of reactor length at different lengths of the reactor.

the enhancement of feed inlet pressure from 35 bar to 55 bar. The 6 m reactor was enough for the CO2 hydrogenation to reach its
maximum temperature along the reactor.

CRediT authorship contribution statement

Jinfeng Fu: Conceptualization, Investigation, Methodology, Writing – original draft, Funding acquisition, Project administra-
tion, Supervision. Mohammed Sh Majid: Conceptualization, Methodology, Writing – original draft, Funding acquisition, Investi-
gation, Project administration, Supervision. Farag M.A. Altalbawy: Conceptualization, Methodology, Writing – original draft,
Funding acquisition, Investigation, Project administration, Supervision. Radhwan M. Hussein: Conceptualization, Data curation,
Resources, Writing – review & editing. Ibrahem Waleed: Conceptualization, Data curation, Resources, Writing – review & edit-
ing. Ibrahim Mourad Mohammed: Conceptualization, Data curation, Resources, Writing – review & editing. Rahman S.
Zabibah: Validation, Writing – review & editing. Kadhum Al-Majdi: Validation, Writing – review & editing. Abdul Malik: Visu-
alization, Writing – review & editing.

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.

Data availability
Data will be made available on request.

Acknowledgement
The authors extend their appreciation to King Saud University for funding this work through research supporting project
(RSP2024R376), Riyadh, Saudi Arabia.

Nomenclature
2D 2-dimensional
1D 1-dimensional
A Pre-exponential factor
CO2 Carbon dioxide
CH3OH Methanol
Cp Gas species heat capacity at constant pressure [J/(mol K)]
Ci Molar concentration of component i
De Effective intraporous diffusion coefficient [m2/s]
Dr Dispersion coefficient in r-direction
dp Catalyst nominal diameter [m]
dt Internal reactor tube diameter [m]
Fi Gas species molar flow rate [mol/s]
G Superficial flow velocity [kgs−1m−2)]
gc Conversion factor parameter [kg/m/s2N]
H2 Hydrogen
Kcat Catalyst thermal conductivity symbol [J(m s K)−1]
Kg Gas species thermal conductivity [kW/mK]
k1,k2,k3 Reaction rate kinetic constants of methanol synthesis

8
J. Fu et al. Case Studies in Thermal Engineering 54 (2024) 103975

Kp10 Equilibrium constant of reaction 1

Kp20 Equilibrium constant of reaction 2
Kp30 Equilibrium constant of reaction 3
KCO Adsorption equilibrium constant of CO (1/bar)
KCO2 Adsorption equilibrium constant of CO2 (1/bar)
KH2 Adsorption equilibrium constant of H2 (1/bar)
KH2O Adsorption equilibrium constant of H2O (1/bar)
Ke Thermal conductivity in radial [J/(m sK)]
Ltot Length of reactor [m]
p Pressure (bar)
pCH3OH Partial pressure of CH3OH [bar]
pCO Partial pressure of CO [bar]
pCO2 Partial pressure of CO2 [bar]
pH2 Partial pressure of H2 [bar]
pH2O Partial pressure of H2O [bar]
rtot Radius of tube in the reactor
r Radial direction (m)
ri Reaction i (1–3) reaction rate [mol/(m3s)]
T Temperature (K)
Uz Superficial gas velocity
Z Veridical direction
ρ Gas species density [kg m−3]
ε Packed bed reactor void fraction
μ Viscosity of gases [Pa s]
ΔHj reaction i (1–3) heat of reaction [kJ/mol]

References
[1] A. Asgari, J. Jannatkhah, M. Yari, B. Najafi, Multi-aspect assessment and multi-objective optimization of sustainable power, heating, and cooling tri-generation
system driven by experimentally-produced biodiesels, Energy 263 (2023) 125887.
[2] K. Qadeer, A. Al-Hinai, L.F. Chuah, N.R. Sial, A.a.H. Al-Muhtaseb, R. Al-Abri, M.A. Qyyum, M. Lee, Methanol production and purification via membrane-based
technology: recent advancements, challenges and the way forward, Chemosphere 335 (2023) 139007.
[3] Y. Yang, G. Li, T. Luo, J. Pan, Y. Song, Q. Qian, Multi-aspect comparative analyses of two innovative methanol and power cogeneration systems from two
different sources, Int. J. Hydrogen Energy 48 (2023) 1120–1135.
[4] X. Xu, Y. Liu, F. Zhang, W. Di, Y. Zhang, Clean coal technologies in China based on methanol platform, Catal. Today 298 (2017) 61–68.
[5] M. Matzen, Y. Demirel, Methanol and dimethyl ether from renewable hydrogen and carbon dioxide: alternative fuels production and life-cycle assessment, J.
Clean. Prod. 139 (2016) 1068–1077.
[6] E. Alper, O. Yuksel Orhan, CO2 utilization: developments in conversion processes, Petroleum 3 (2017) 109–126.
[7] G. Iaquaniello, G. Centi, A. Salladini, E. Palo, S. Perathoner, L. Spadaccini, Waste-to-methanol: process and economics assessment, Bioresour. Technol. 243
(2017) 611–619.
[8] A. Saleem, S. Ali, I. Liaqat, Methanol Production from the Pulp Mills and Paper Industry, Reference Module in Chemistry, Molecular Sciences and Chemical
Engineering, Elsevier, 2023.
[9] D. Wang, J. Li, W. Meng, Z. Liao, S. Yang, X. Hong, H. Zhou, Y. Yang, G. Li, A near-zero carbon emission methanol production through CO2 hydrogenation
integrated with renewable hydrogen: process analysis, modification and evaluation, J. Clean. Prod. 412 (2023) 137388.
[10] N. Rui, R. Shi, R.A. Gutiérrez, R. Rosales, J. Kang, M. Mahapatra, P.J. Ramírez, S.D. Senanayake, J.A. Rodriguez, CO2 hydrogenation on ZrO2/Cu(111) surfaces:
production of methane and methanol, Ind. Eng. Chem. Res. 60 (2021) 18900–18906.
[11] A. Pavlišič, M. Huš, A. Prašnikar, B. Likozar, Multiscale modelling of CO2 reduction to methanol over industrial Cu/ZnO/Al2O3 heterogeneous catalyst: linking
ab initio surface reaction kinetics with reactor fluid dynamics, J. Clean. Prod. 275 (2020) 122958.
[12] X.-j. Guo, L.-m. Li, S.-m. Liu, G.-l. Bao, W.-h. Hou, Preparation of CuO/ZnO/Al2O3 catalysts for methanol synthesis using parallel-slurry-mixing method, J. Fuel
Chem. Technol. 35 (2007) 329–333.
[13] D. Fang, W. Ren, Z. Liu, X. Xu, L. Xu, H. Lü, W. Liao, H. Zhang, Synthesis and applications of mesoporous Cu-Zn-Al2O3 catalyst for dehydrogenation of 2-butanol,
J. Nat. Gas Chem. 18 (2009) 179–182.
[14] X. Fan, K. Wang, X. He, S. Li, M. Yu, X. Liang, Pd-modified CuO-ZnO-Al2O3 catalysts via mixed-phases-containing precursor for methanol synthesis from CO2
hydrogenation under mild conditions, Carbon Resources Conversion 7 (2024) 100184.
[15] Q. Chen, S. Meng, R. Liu, X. Zhai, X. Wang, L. Wang, H. Guo, Y. Yi, Plasma-catalytic CO2 hydrogenation to methanol over CuO-MgO/Beta catalyst with high
selectivity, Appl. Catal. B Environ. 342 (2024) 123422.
[16] L. Proaño, C.W. Jones, CO2 hydrogenation to methanol over ceria-zirconia NiGa alloy catalysts, Appl. Catal. Gen. 669 (2024) 119485.
[17] Z. He, Y. Liu, S. Luo, T. Wang, Mechanistic study of CO2 hydrogenation to C1 products on molybdenum step site, Surf. Sci. 739 (2024) 122394.
[18] L. Vaquerizo, A.A. Kiss, Thermally self-sufficient process for cleaner production of e-methanol by CO2 hydrogenation, J. Clean. Prod. 433 (2023) 139845.
[19] I. Hussain, U. Mustapha, A.T. Al-Qathmi, Z.O. Malaibari, S. Alotaibi, Samia, K. Alhooshani, S.A. Ganiyu, The critical role of intrinsic physicochemical properties
of catalysts for CO2 hydrogenation to methanol: a state of the art review, J. Ind. Eng. Chem. 128 (2023) 95–126.
[20] Z. Yang, D. Guo, S. Dong, J. Wu, M. Zhu, Y.-F. Han, Z.-W. Liu, Catalysis for CO2 hydrogenation—what we have learned/should learn from the hydrogenation of
syngas to methanol, Catalysts 13 (2023) 1452.
[21] S. Saeidi, N.A.S. Amin, M.R. Rahimpour, Hydrogenation of CO2 to value-added products—a review and potential future developments, J. CO2 Util. 5 (2014)
66–81.
[22] K. Ahmad, S. Upadhyayula, Selective conversion of CO2 to methanol over intermetallic Ga-Ni catalyst: microkinetic modeling, Fuel 278 (2020) 118296.
[23] E. Heracleous, V. Koidi, A.A. Lappas, Experimental investigation of sorption-enhanced CO2 hydrogenation to methanol, ACS Sustain. Chem. Eng. 11 (2023)
9684–9695.
[24] F. Moradi, M. Kazemeini, M. Fattahi, A three dimensional CFD simulation and optimization of direct DME synthesis in a fixed bed reactor, Petrol. Sci. 11 (2014)
323–330.
[25] C.-H. Fu, J.C.S. Wu, Mathematical simulation of hydrogen production via methanol steam reforming using double-jacketed membrane reactor, Int. J. Hydrogen
Energy 32 (2007) 4830–4839.

9
J. Fu et al. Case Studies in Thermal Engineering 54 (2024) 103975

[26] K. Ghasemzadeh, P. Morrone, A.A. Babalou, A. Basile, A simulation study on methanol steam reforming in the silica membrane reactor for hydrogen production,
Int. J. Hydrogen Energy 40 (2015) 3909–3918.
[27] J.A.D. Dobladez, V.I.Á. Maté, S.Á. Torrellas, M. Larriba, G. Pascual Muñoz, R. Alberola Sánchez, Comparative simulation study of methanol production by CO2
hydrogenation with 3A, 4A and 5A zeolites as adsorbents in a PSA reactor, Separ. Purif. Technol. 262 (2021) 118292.
[28] G. Leonzio, E. Zondervan, P.U. Foscolo, Methanol production by CO2 hydrogenation: analysis and simulation of reactor performance, Int. J. Hydrogen Energy 44
(2019) 7915–7933.
[29] G. Leonzio, P.U. Foscolo, Analysis of a 2-D model of a packed bed reactor for methanol production by means of CO2 hydrogenation, Int. J. Hydrogen Energy 45
(2020) 10648–10663.
[30] D. Izbassarov, J. Nyári, B. Tekgül, E. Laurila, T. Kallio, A. Santasalo-Aarnio, O. Kaario, V. Vuorinen, A numerical performance study of a fixed-bed reactor for
methanol synthesis by CO2 hydrogenation, Int. J. Hydrogen Energy 46 (2021) 15635–15648.
[31] K. Klier, V. Chatikavanij, R.G. Herman, G.W. Simmons, Catalytic synthesis of methanol from COH2: IV. The effects of carbon dioxide, J. Catal. 74 (1982)
343–360.
[32] M.A. McNeil, C.J. Schack, R.G. Rinker, Methanol synthesis from hydrogen, carbon monoxide and carbon dioxide over a CuO/ZnO/Al2O3 catalyst: II.
Development of a phenomenological rate expression, Appl. Catal. 50 (1989) 265–285.
[33] G.H. Graaf, E.J. Stamhuis, A.A.C.M. Beenackers, Kinetics of low-pressure methanol synthesis, Chem. Eng. Sci. 43 (1988) 3185–3195.
[34] F. Hartig, F.J. Keil, Large-scale spherical fixed bed reactors: modeling and optimization, Ind. Eng. Chem. Res. 32 (1993) 424–437.
[35] K.M. Vanden Bussche, G.F. Froment, A steady-state kinetic model for methanol synthesis and the water gas shift reaction on a commercial Cu/ZnO/Al2O3
catalyst, J. Catal. 161 (1996) 1–10.
[36] A. Montebelli, C.G. Visconti, G. Groppi, E. Tronconi, C. Ferreira, S. Kohler, Enabling small-scale methanol synthesis reactors through the adoption of highly
conductive structured catalysts, Catal. Today 215 (2013) 176–185.

10