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Journal of the Taiwan Institute of Chemical Engineers

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Modeling and assessment of novel configurations to enhance

methanol production in industrial mega-methanol synthesis plant
A. Mirvakili a,∗, S. Chahibakhsh a, M. Ebrahimzadehsarvestani b, E. Soroush b,
M.R. Rahimpour b
a
Chemical Engineering Department, Faculty of Petroleum, Gas and Petrochemical Engineering, Persian Gulf University, Bushehr 75169-13817, Iran
b
Department of Chemical Engineering, School of Chemical and Petroleum Engineering, Shiraz University, Shiraz 71345, Iran

a r t i c l e i n f o a b s t r a c t

Article history: In the current study, the utilization of parallel reactors instead of series configurations in the mega
Received 18 February 2019 methanol plants is investigated. In the conventional reactor (CR), two parallel fixed bed water-cooled
Revised 26 August 2019
reactors are in series with a gas-cooled reactor. In this study, three novel configurations are proposed
Accepted 21 September 2019
in which the gas-cooled is in parallel with two water-cooled reactors and the feed is divided in differ-
Available online xxx
ent manners between the reactors. There is almost 31% fresh feed included in the feed and the rest is
Keywords: composed of recycled stream. In the first configuration, named “Equal Parallel (EP)”, the feed is divided
Parallel reactors equally between the reactors. In the second configuration, named “Recycled gas to the gas-cooled (RG)”,
Mega methanol plants the total recycled gas is sent the gas-cooled reactor and the fresh synthesis gas is sent to the water-
Recycled gas cooled reactors. The last configuration, named “Recycled gas to the water-cooled (RW)”, is in contrast to
Methanol synthesis the RG. These systems are simulated to find the superior configuration. The simulation results showed
Simulation
that the produced methanol in RG system was about 21.7% more than the CR configuration, and 7.4% and
10.6% more than EP and RW configurations, respectively. Moreover, CO2 emission in RG system was 18.9%
less than CR configuration.
© 2019 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction efficiency was presented by Lurgi for large-scale applications.

1.1. Methanol
Methanol is one of the most important products of petro-
chemical industries, which has numerous applications in different
fields including plastic manufacturing and production of chemicals
such as formaldehyde, dimethyl ether, methyl tertiary–butyl ether
(MTBE), and methylamine. This important alcoholic substance can
mainly be produced from natural gas, wood, and charcoal. Among
the mentioned sources, the natural gas is the most common one.
It is estimated that around 90% of the total produced methanol in
the world is manufactured from natural gas [1]. In this process,
natural gas is converted to synthesis gas (CO, H2 ) which is used to
produce methanol.
1.2. Dual type mega-methanol reactor
With the progress in technology and the increasing demand
for methanol in the global market, a dual type reactor with high
∗
Corresponding author.
E-mail address: mirvakili@pgu.ac.ir (A. Mirvakili).
Compared with other large-scale systems, Lurgi process with the
recycle/syngas ratio of 3.5 consumes less energy. The reactor
design and the heat removal method employed in the dual type
reactor are the main differences with the single type one [2].
Methanol is produced from syngas composed from CO, H2 and
small amount of CO2 , in two stages by dual type reactor. The
process is comprised of two parallel water-cooled reactors that are
in series with a gas-cooled reactor. In both reactors, the catalyst of
CuO/ZnO/Al2 O3 is utilized. The tubes of the water-cooled reactor
and the shell of the gas-cooled reactor are packed with the men-
tioned catalyst. As a result, the conversion of syngas to methanol
in the dual type reactor is 11% for each pass, which is only 7% in
the single type reactor [3,4].
Low investment cost and high rate of methanol production
(higher than 50 0 0 tons per day) can be mentioned as the most
significant advantages of mega-methanol unit [5]. In a study, Mir-
vakili and Rahimpour [6] increased methanol production by using
the mega-methanol reactor in the industrial scale and introduced
different strategies to tackle the gas condensate issues in the gas-
cooled industrial reactor. Then, the best strategy was selected. The
results showed an increase of 7.9% in methanol production and a
decrease of 2.6% in CO2 production compared with the single type

https://doi.org/10.1016/j.jtice.2019.09.018
1876-1070/© 2019 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Please cite this article as: A. Mirvakili, S. Chahibakhsh and M. Ebrahimzadehsarvestani et al., Modeling and assessment of novel con-
figurations to enhance methanol production in industrial mega-methanol synthesis plant, Journal of the Taiwan Institute of Chemical
Engineers, https://doi.org/10.1016/j.jtice.2019.09.018
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1.3. CO2 emission

Nomenclature
CO2 emission is known as a usual problem in the chemical
av specific surface area of catalyst pellet (m2 m−3 ) industries. In methanol plants, CO2 is produced in the reform-
Ac cross section area of each tube (m2 ) ers of synthesis gas unit and is not completely consumed in
Cp specific heat of the gas at constant pressure the methanol reactors. For instance, 40 0 0 Sm3 /h (Standard cubic
(J mol−1 K−1 ) meter/ hr, volumetric flow rate in the standard condition (1 atm,
dp particle diameter (m) 25 °C)) CO2 is emitted to atmosphere in an industrial mega
Ei activation energy for elementary reaction step i, methanol plant of Iran. The different methods have been applied
kJ/kmol in industrial plants to reduce CO2 emission. One of the simplest
F total molar flow rate (mol s−1 ) procedures is recycling of the purge gas containing CO2 . For this
hf gas-solid heat transfer coefficient (W m−2 K−1 ) purpose in mind, Agahzamin et al. [8] showed that approximately
Hf,i enthalpy of formation of component i (J mol−1 ) 50,106 m3 of the purge gas is burnt per hour though it can be
kg mass transfer coefficient for component i (m s−1 ) recycled to the unit and increase the methanol production rate [8].
K conductivity of gas phase (W m−1 K−1 ) In addition, syngas production can be boosted and carbon dioxide
ki reaction rate coefficient, (mol kg−1 s−1 bar−1/2 ) equivalent emission can be reduced (26.7 tons) by recycling purge
L reactor length (m) gas without nitrogen to the auto-thermal reactor (ATR). Accord-
Mi molecular weight of component i (g mol−1 ) ing to the calculations, if the methanol synthesis reactor works
P total pressure (for exothermic side: bar; for en- with its maximum capacity, 30,0 0 0 m3 /h of the purge gas can be
dothermic side: Pa) recycled to the reactor.
Pl liquid pressure (kPa) Comprehensive studies have been carried out on the purge gas
Pv vapor pressure (kPa) and its recycling to the Mega-methanol unit. There are inert gasses
R universal gas constant (J mol−1 K−1 ) of N2 and CH4 in addition to unreacted gas of H2 , CO and CO2
Rp particle radius (m) included in the purge gas. Generally, recycling the total purge gas
ri reaction rate of component i (mol kg−1 s−1 ) to the reactor leads to the accumulation of inert gas in the system
T Temperature (K) and a reduction in the reactor efficiency. In order to prevent this
U overall heat transfer coefficient between exothermic phenomenon, a portion of purge gas (which is about 5%) is burnt
and endothermic sides (W m−2 K−1 ) in the flare and therefore, the inert content of the recycled gas is
Xi conversion of component i almost constant. However, it is possible to separate the inert gas
yi molar fraction of component i (mol−1 ) from the purge gas and recycle all the residuals to the reactor.
yis molar fraction of component i in the solid One of the approaches which can be employed for this purpose is
phase(mo .mol−1 ) utilization of membrane. Our previous study showed that the best
Z compressibility factor way for the separation of N2 and CH4 is utilization of zeolite mem-
branes [9]. The simulation results indicated that the best mem-
Greek letters brane for separation of the gas mixtures is Matrimid5218, which
࢞Hi enthalpy of reaction can remove 95% of N2 from the gas mixture and prevent the emis-
εs void fraction of catalyst sion of 300 tons of CO2 per day to the environment. Furthermore,
ε porosity of bed methanol production capacity increased by 4.6%, which is very
γi activity coefficient of component i important at industrial scale. Another approach for carbon capture
μi viscosity of fluid phase (kg m−1 s−1 ) (CC) which is comprehensively investigated in the literature is
ν ci critical volume of component i (cm3 mol−1 ) post-combustion carbon capture (PCC). PCC is the only commercial
ρ density of fluid phase (kg m−3 ) method of carbon capture. Two commercial plants utilizing PCC to
ρs density of catalyst (kg m−3 ) reduce CO2 emission are investigated in this study. One of them is
η catalyst effectiveness factor the TMC Mongstad in Norway which captures 30 0,0 0 0 tons of CO2
Superscripts per year and the other one is BD3 SaskPower in Canada which cap-
g in bulk gas phase tures 1 million tons of CO2 per year [10]. Liang et al. [10] presented
s at the surface of the catalyst a comprehensive review of the most recent information available
on all aspects of the PCC processes. Moreover, Bui et al. [11] re-
Subscripts viewed the current techniques of CO2 capture, transport, utilization
0 inlet conditions and storage. They concluded that the most important way to re-
k reaction number index duce CO2 emission is carbon capture and storage (CCS). However,
l liquid phase more researches are required to make this method economical.
v vapor phase
1.4. Literature review

As it was mentioned before, the main stage of methanol pro-

reactor. The gas condensate formation in the gas-cooled reactor
leads to reduction of catalyst activity and an increase of pressure
drop in the bed. Mirvakili et al. [7] investigated the reasons of
gas condensate formation in the gas cooled reactor with compu-
tational fluid dynamics (CFD) model. Two important parameters
of gas velocity and temperature distribution around the shell and
tubes were considered. The results indicated that the non-uniform
temperature distribution in the shell can be attributed to the
non-uniform flow distribution in both shell and tubes [7].
duction process takes place in the methanol reactor. Therefore,
comprehensive studies have been conducted on methanol synthe-
sis reactors to enhance the methanol production efficiency as well
as reduce the effects of greenhouse gasses on the environment
[12–24]. These studies revealed that the temperature, composition
and flow rates of feed play the key roles in the reactor efficiency.
In order to simulate a Lurgi reactor, Yusup et al. [25] intro-
duced a mathematical model in steady state condition. In their
study, effects of the operating parameters such as coolant inlet
temperature, coolant velocity and feed inlet temperatures on

Please cite this article as: A. Mirvakili, S. Chahibakhsh and M. Ebrahimzadehsarvestani et al., Modeling and assessment of novel con-
figurations to enhance methanol production in industrial mega-methanol synthesis plant, Journal of the Taiwan Institute of Chemical
Engineers, https://doi.org/10.1016/j.jtice.2019.09.018
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Fig. 1. Schematic of the conventional two-stage reactor for methanol synthesis (CR).

the reactor performance were analyzed. The simulation results
showed good agreement with the plant data. Farsi and Jahanmiri
[26] also simulated and optimized methanol production in a dual
membrane reactor through genetic algorithm. The Pd/Ag and
alumina-silica membranes were utilized for the H2 permeation
and water vapor removal, respectively. Utilization of membrane
results in several advantages such as more CO2 conversion and
a 13.2% increase in the pure methanol synthesis compared with
the industrial methanol production reactor. Various mathematical
models have been proposed with MATLAB software in which the
methanol production can be assessed through simulation. In this
regard, Alarifi et al. [27] applied a dynamic optimization of a Lurgi
type reactor in the presence of catalyst deactivation to obtain the
optimum percentage of recycled CO2 and the coolant temperature.
A combination of genetic algorithm (GA) and generalized pattern
search (GPS) has been utilized in their mathematical model to
provide a suitable approach for the dynamic optimization. Results
of this simulation revealed that substitution of the optimum con-
ditions for the existing operating conditions causes a 2.5% increase
in the methanol production.
1.5. Objective
As it is explained before, the conventional dual-type reactor for
methanol synthesis consists of series reactors which the fresh syn-
gas in addition to the recycled gas are utilized as a feed normally.
Besides, the methanol production can experience a significant im-
prove through some simple changes in the reactors arrangement
and feed division. In order to investigate the effect of arranging
reactors in parallel, three parallel configurations are substituted for
conventional series arrangement. In this regard, a one-dimensional
homogeneous model is proposed for steady state condition using
MATLAB software. The results of four models are compared with
each other and the superior configuration is then selected.
2. Process description
2.1. The conventional two-stage reactor for methanol synthesis
The mega methanol reactor is a vertical shell and tube heat ex-
changer which has different steps as follows to produce methanol.
First, the fresh syngas and the recycled gas are mixed together
and preheated in the tubes of the gas-cooled reactor. Then, the
warmed mixed gas stream is sent to the tubes of two parallel
water-cooled reactors. The exothermic methanol synthesis reaction
takes place on the commercial catalyst of CuO/ZnO/Al2 O3 in the
tubes and the gas in the water-cooled tubes is cooled by the
steam in the shell side. The outlet gas is sent to the shell side
of the gas-cooled reactor filled with catalyst. There is always
enough equilibrium driving force on the entire catalyst bed of the
gas-cooled reactor to synthesis methanol regarding to the counter
current flow of the coolant (in the tubes side) and the reactants
(in the shell side). This is because of the continuous temperature
reduction of reactant along the reaction path. Water-cooled reactor
has higher temperature and therefore, its catalysts deactivate more
quickly compared with the gas-cooled reactor. In order to separate
the purge gas from the liquid products via condensation, the
temperature of the gas-cooled reactor outlet stream is decreased
to 40 °C. About 95% of the purge gas is recycled to methanol
synthesis unit. These steps are shown in Fig. 1. In addition,
Tables 1–3 present the catalyst input data and industrial design
for the conventional dual-type methanol synthesis reactor.
2.2. Equal parallel (EP) configuration
There are two series reactors in the CR configuration with a
combination of fresh syngas and recycled steam as their feed.
In the EP configuration, the feed is equally divided between
gas-cooled and water-cooled reactors. Similar to previous config-
uration, first step is merging the fresh syngas with the recycled

Please cite this article as: A. Mirvakili, S. Chahibakhsh and M. Ebrahimzadehsarvestani et al., Modeling and assessment of novel con-
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Table 3
Table 1 Operating data of conventional dual-type reactor for methanol synthesis.
Properties of conventional dual-type reactor for methanol synthesis and its cata-
lysts. Feed conditions Operation value

Water cooled reactor Gas cooled reactor Feed composition (mol%)

CO 8.61
Parameter Value Value unit CO2 9.87
D 4.5 5.5 [m] H2 64.02
t 13 13 [mm] CH4 8.35
dp 5.4 5.4 [mm] N2 8.45
lp 3.6 3.6 [mm] H2 O 0.09
ρs 1.46 1.46 [kg/m3 ] CH3 OH 0.43
Cps 2.81 2.75 [kJ/kg °C] Argon 0.18
Kc 0.004 0.004 [W/mK] Inlet temperature (K) 407.4
av 625.7 625.7 [m2 /m3 ] Total molar flow rate per tube (mol/s) 1.87
ε 0.34 0.34 – Pressure (bar) 78
Tube length 8.4 10.5 [m]
Number of tubes 5922 3026 –
Shell side pressure – 71.2 [bar]
Tube side pressure 75 76.98 [bar]
steam. Following that, the mentioned stream is sent to the tubes
of the gas-cooled reactor to preheat. Next, the stream of the gas-
cooled reactor was equally divided into two sub streams which
Table 2
are sent to the tubes of the water-cooled reactor and the shell
Input design of conventional dual-type reactor for methanol synthesis. of the gas-cooled reactor simultaneously. Eventually, the outputs
of both reactors are merged and after a temperature reduction,
Feed conditions Design value
methanol and water are separated as liquid from the purge gas.
Feed composition (mol%) The aforementioned steps are shown schematically in Fig. 2.
CO 8.68
CO2 8.49
H2 64.61 2.3. The configuration of “recycled gas to the gas-cooled reactor (RG)”
CH4 9.47
N2 8.2 This model is named “RG” or “Recycled gas to the gas-cooled”
H2 O 0.1 because the entire recycled gas is heated via a heat exchanger
CH3 OH 0.37
Argon 0.24
and when the temperature increased to 510 K, it is directed to the
Inlet temperature (K) 401 shell side of the gas-cooled reactor. On the other hand, the fresh
Total molar flow rate per tube (mol/s) 1.80 syngas is sent to the tubes of the gas-cooled reactor. The directed
Pressure (bar) 76 syngas is flowed counter-currently with the reacting gas. The
syngas at 510 K, it is sent to the tubes of the water-cooled reactor.

Fig. 2. Schematic of the EP configuration.

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Fig. 3. Schematic of the RG configuration.

Eventually, the output gasses of both reactors are mixed and sent 3. Mathematical model
to the next unit. Another point worth mentioning is about the
high-pressure super-heated steam produced in the shell side of 3.1. Kinetic model
the water-cooled reactors which could be utilized for preheating
the recycled gas in RG. The utilization of the produced steam in As it is shown in reactions 1 and 2, methanol is produced from
the water-cooled reactor was performed in our previous work [8]. carbon monoxide and carbon dioxide in hydrogenation reactions.
The explained path is shown in Fig. 3.
CO + 2H2 ↔ CH3 OH H298 = −90.55 kJ/mol (1)

2.4. The configuration of “recycled gas to the water-cooled reactor CO2 +3H2 ↔ CH3 OH+H2 O H298 = −49.43 kJ/mol (2)
(RW)”
Water gas shift reaction shown in Eq. (3) is a side reaction of
the methanol production,
This model is named “RW” or “Recycled gas to the water-
cooled” because in this model, the entire recycled gas is heated CO2 +H2 ↔ CO+H2 O H298 = +41.12 kJ/mol (3)
via a heat exchanger and when the temperature increased to 510 K,
The reaction rates utilized in this study have been suggested
it is directed to the tubes of the water-cooled reactor. In the other
by Graaf et al. [28,29] and they are listed below as Eqs. (4)–(6).
part of this configuration, the fresh syngas is directed to the tubes
Furthermore, the constants of the reaction rates are shown in
of the gas-cooled reactor. After the syngas temperature reaches to
Table 4.
528 K, it is sent to the shell side of the gas-cooled reactor. Exactly  
like other explained processes, the streams from both reactors are k1 KCO fCO fH3/2 2 − fCH3 OH / fH1/2 2 KP1
mixed together and sent to next units for temperature reduction r1 =     (4)
(1 + KCO fCO + KCO2 fCO2 ) fH1/2 2 + KH2 O /KH1/22 fH2 O
and purification. Similar to RG configuration, the produced steam
 3/2 3/2

in the shell of the water-cooled reactors could be applied for k2 KCO2 fCO2 fH2 − fCH3 OH fH2 O / fH2 KP2
preheating the recycled gas. r2 =     (5)
A scheme of this configuration is shown in Fig. 4. (1 + KCO fCO + KCO2 fCO2 ) fH1/2 2 + KH2 O /KH1/22 fH2 O

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Fig. 4. Schematic of the RW configuration.

Table 4 Table 5
Constants of the reaction rate, the adsorption equilibrium and the reaction equilib- Mass and energy balance equations of solid and fluid phases, pressure drop equa-
rium equations of methanol synthesis. tion, and boundary conditions.

A B Definition Equation

K = Aexp(B/RT) Mass and energy balances for av c j kgi,g (ygi − ysi ) + ηri ρb = 0
k1 (4.89 ± 0.029) × 107 −63,000 ± 300 solid phase
(1.09 ± 0.07) × 105 −87,500 ± 300 N
k2 av h f (Tig − Ti s ) + ρb i−1 ηri (−H f,i ) = 0
k3 (9.64 ± 7.30) × 106 −152,900 ± 6800 F ∂y
g

K = Aexp(B/RT) Mass and energy balances for − Ajc ∂ zj + av c j kgi,g (ysi − ygi ) = 0
KCO (2.16 ± 0.44) × 10−5 46,800 ± 800 fluid phase F ∂Tg
− Ajc C pg j ∂ zj + av h f (T js − T jg ) ±
KCO2 (7.05 ± 1.39) × 10−7 61,700 ± 800 π Di
U1−2 (T shell
− T1tube
)=0
(KH2 O /KH1/22 ) (6.37 ± 2.88) × 10−9 84,000 ± 1400 Ac
dP (1−ε )2 μu (1−ε )u2g ρ
KP = 10(A/T − B) Pressure drop (Ergun dz
= 150 ε3 d2 g + 1.75 ε3 d p
p
KP 1 5139 12.621 momentum balance)
KP 2 3066 10.592 Boundary conditions z = 0, ygi, j = ygi0, j , T jg = T j0
g
, Pjg = Pj0
g

KP 3 −2073 −2.029

of all aforesaid configurations. All of the explained models are

k3 KCO2 [ fCO2 fH2 − fH2 O fCO /KP3 ]
r3 =    
(1 + KCO fCO + KCO2 fCO2 ) fH1/2 2 + KH2 O /KH1/22 fH2 O
3.2. The equations of the mathematical model
As shown in Table 5, the utilized equations of mass, heat and
heterogeneous kinetic rates are considered one-dimensionally to
specify the profiles of composition and temperature in the reactors
fixed bed reactor models. The mentioned model has been applied
(6) broadly in our earlier studies [6,30]. The differential-algebraic
equations presented in Table 5 are provided for modeling the
methanol reactors.
3.3. Numerical solution
The presented energy and mass balance equations were com-
bined with a kinetic model, which there are non-linear algebraic

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Table 6
Comparison between the CR simulation results with the commercial data.
Model validation with an operation data
Product condition Plant Predicted
Composition (mol%)
CH3 OH 0.0987 0.0964
CO 0.0266 0.0245
CO2 0.0718 0.0771
H2 O 0.0183 0.0179
H2 0.5558 0.5423
N2 /Ar 0.1008 0.1068
CH4 0.128 0.135
Temperature (K) 493.5 487.6
equations, transport characteristics and also some other auxillary
correlations included in it. In order to solve this collection of equa-
tions, a backward finite difference approximation was employed.
To perform this, the dimensions of reactors were separated to
200 discrete parts which guaranteed the precision and numerical
stability of solution. To develop the method of numerical solution,
a MATLAB® programming code was generated.
3.4. Model validation
A validation of CR simulation results with the commercial
data is carried out and the comparison is presented in Table 6.
The comparison shows that the resemblance between the CR and
the commercial data is acceptable. As a consequence, the pre-
sented mathematical model agrees very well with the operating
conditions.
4. Results and discussion
4.1. Methanol production rate
Methanol molar flow rates in a single tube of the water-cooled
reactor and an equivalent single tube of a gas-cooled reactor for
all explained configurations are shown in Fig. 5(a) and (b), respec-
tively. Methanol molar flow rates are small because simulations
are performed for a single tube in the water-cooled and gas-cooled
reactors. In CR configuration, the water-cooled and gas-cooled re-
actors are in series and have the same flow rates. Therefore, both
reactors have the maximum methanol flow rate compared with
the reactors of the other configurations. It means that, as it can be
seen in Fig. 5(a) and (b), a single tube of a reactor in the CR system
has the maximum methanol flow rate compared with the tubes of
other reactors. However, in the proposed parallel configurations,
the maximum molar flow rate is regarded to a hypothetical tube
in the gas-cooled reactor of RG configuration. In this configuration,
the recycled gas is sent to the gas-cooled reactor and all the fresh
synthesis gas is sent to the water-cooled reactor. Thus, the feed
of the water-cooled reactor in RG configuration is fresh synthesis
gas, which produces the maximum amount of methanol. As it is
depicted in Fig. 5(a), the water-cooled reactor of RW configuration
produces the minimum methanol molar flow rate due to the fact
that all the recycled gas is sent to the water-cooled reactor. In EP
configuration, the total feed flow rate is divided into two equal
parts. One part is sent to the water-cooled reactor and the other
one is directed to the gas-cooled reactor. Therefore, the amount of
methanol molar flow rate in the water-cooled reactor of EP system
is a value between the methanol molar flow rates of RG and RW
configurations. As it can be seen in Fig. 5(b), the methanol produc-
tion in the gas-cooled reactors is almost equal for all the parallel
configurations. Although it was expected that methanol production
in the gas-cooled reactor of the RW system is higher than the RG
configuration arising from its feed content which is totally fresh
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7
syngas; however the results showed that it is almost equal in both
reactors. This can be attributed to the low feed rate of the gas-
cooled reactor in RW configuration compared with the RG system.
Error%
Fig. 5(c) shows the effects of the fresh feed fraction changes
on the total molar flow rate of methanol. The figure signifies
that in RW configuration, no fresh feed have entered to the
−2.33
−7.89 water-cooled reactor. In fact, its feed is the recycled gas. The total
7.38 fresh synthesis gas is sent to the gas-cooled reactor. Whereas, in
−2.18 RG system all the fresh feed is sent to the water-cooled reactor
−2.42 and all the recycled gas is sent to gas-cooled reactor. The gas
5.95
5.46
flow rate in the gas-cooled reactor of RG system is much higher
−1.19 than RW configuration. Nevertheless, the produced methanol in
both systems is nearly the same regarded to that the feed of the
gas-cooled reactor in RG system is recycled gas. Although the gas
flow rate of water-cooled reactor in RG configuration is less than
RW system, the RG system has the maximum produced methanol
among water-cooled reactors in the parallel configurations. This is
because of that the fresh synthesis gas is entered the water-cooled
reactor in RG configuration. Finally, it is interesting to note that EP
system has the minimum methanol production.
The molar fractions of methanol in both water-cooled and
gas-cooled reactors of all configurations are demonstrated in
Fig. 5(d). As shown in Fig. 5(d), the molar fraction of methanol in
the water-cooled reactors of RG and EP parallel configurations are
higher than CR. However, the outlet molar fractions of methanol
in all the parallel configurations (RG, RW, and EP) are higher than
CR. The maximum methanol molar fraction in the water-cooled
reactors has been regarded to the RG system and the maximum
methanol molar fraction in the gas-cooled reactors is regarded
to RW configuration. These results are expected because the feed
of the water-cooled reactors in RG system and the feed of the
gas-cooled reactor in RW configuration are fresh synthesis gasses.
However, the molar flow rates of the feeds are different for RG
and RW systems. The feed of gas-cooled reactor in the CR system
is the outlet gas of water-cooled reactor, thus the diagrams of
methanol molar fractions of the water-cooled and the gas-cooled
reactors are connected.
Fig. 5(a)–(d) do not specify the best configuration; because they
are plotted for a single tube in the water-cooled and an equivalent
tube in the gas-cooled reactors. Therefore, for assessing all the
configurations, the results of a single tube in each reactor were
multiplied by the number of tubes in that reactor. The water-
cooled reactor is in fact two parallel reactors with 5955 tubes
in total and the gas-cooled reactor has 3026 tubes, considered
3026 tubes with the equivalent shell around it in the simulation.
Fig. 5(e) depicts the molar flow rates of methanol in the scale
of a reactor for all the configurations. The maximum methanol
molar flow rate is regarded to the RG system and the minimum is
regarded to the CR. Therefore, it can be concluded that the parallel
configurations are better than the conventional series system.
4.2. The effect of temperature
The temperature profiles of the water-cooled and gas-cooled
reactors are illustrated in Fig. 6 for all the configurations. The
reactor length can be divided into two hypothetical segments,
upper section controlled by the reaction kinetics and the lower
section controlled by thermodynamic equilibrium. In the upper
section, an exothermic reaction takes place and generates heat.
Therefore, a temperature peak is observed in the beginning of the
reactor. The temperature peaks are seen in the beginning of both
gas-cooled and the water-cooled reactors of all the parallel config-
urations (RG, EP, and RW). However, in the CR system it can only
be seen in the beginning of the water-cooled reactor. The feed of
the gas-cooled reactor in the CR configuration has been reached to
the thermodynamic equilibrium state in the lower section of the
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8 A. Mirvakili, S. Chahibakhsh and M. Ebrahimzadehsarvestani et al. / Journal of the Taiwan Institute of Chemical Engineers xxx (xxxx) xxx

Fig. 5. (a) Molar flow rate of methanol in a single tube of water-cooled reactor (b) Molar flow rate of methanol in a single equivalent tube gas-cooled reactor (c) The effects
of the fresh feed fraction changes on the total methanol molar flow rate (d) Methanol molar fractions of water-cooled and gas-cooled reactors in all various configurations
(e) Total methanol flow rates of various configurations.

Please cite this article as: A. Mirvakili, S. Chahibakhsh and M. Ebrahimzadehsarvestani et al., Modeling and assessment of novel con-
figurations to enhance methanol production in industrial mega-methanol synthesis plant, Journal of the Taiwan Institute of Chemical
Engineers, https://doi.org/10.1016/j.jtice.2019.09.018
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Fig. 6. Temperature profiles of water-cooled and gas-cooled reactors in various con-
figurations.
Fig. 7. (a) Hydrogen molar fractions of a single tube of each water-cooled and gas-
cooled reactors in various configurations (b) Total hydrogen molar flow rates in var-
ious configurations.
water-cooled reactor. Therefore, it does not tend to participate in
the exothermic reactions of methanol synthesis in the beginning
of the gas-cooled reactor and there is no temperature peak in
this part. The methanol synthesis reaction which is significantly
exothermic, contributes to stronger temperature peaks. Therefore,
the maximum reaction rates are observed in the tubes of the
Please cite this article as: A. Mirvakili, S. Chahibakhsh and M. Ebrahimzadehsarvestani et al., Modeling and assessment of novel con-
figurations to enhance methanol production in industrial mega-methanol synthesis plant, Journal of the Taiwan Institute of Chemical
Engineers, https://doi.org/10.1016/j.jtice.2019.09.018
[m5G;October 4, 2019;7:29]
9
Fig. 8. (a) Carbon monoxide conversions in a single tube of various configurations’
water-cooled and gas-cooled reactors (b) H2 conversions in a single tube of various
configurations’ water-cooled and gas-cooled reactors.
water-cooled reactor of RG system. Comparisons of temperature
profiles of the gas-cooled reactors in different configurations
showed that the maximum temperature peak and maximum
reaction rate occur in RW system. However, this configuration has
a hot spot. In this system, the temperature reduced to less than
450 K, which is near the dew point temperature of the gas.
4.3. H2 consumption rate
The molar fractions of hydrogen along a single tube of each
water-cooled and gas-cooled reactors of different configurations
are shown in Fig. 7(a). Hydrogen is a reactant, and consequently it
is consumed along the reactor. In CR configuration, molar fraction
of H2 along the water-cooled reactor has been reduced more than
through the gas-cooled reactor arising from the fact that the feed
of gas-cooled reactor is the outlet gas of the water-cooled reactor
which is reached to equilibrium. The gas-cooled reactor in CR
system has two duties. The first one is preheating the feed of
the water-cooled reactor and the second one is the reduction of
gas temperature in the shell side, which leads to deviation from
the thermodynamic equilibrium. However, the molar flow rates of
different components (Figs. 5, 9, 10) illustrate that the gas-cooled
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10 A. Mirvakili, S. Chahibakhsh and M. Ebrahimzadehsarvestani et al. / Journal of the Taiwan Institute of Chemical Engineers xxx (xxxx) xxx

Fig. 9. (a) Carbon dioxide molar flow rates of a single tube of water-cooled reactors in various configurations (b) Carbon dioxide molar flow rates of a single equivalent tube
of gas-cooled reactors in various configurations (c) Various configurations total CO2 flow rates.

reactor in CR system does not have a significant effect on the
methanol production. In the other hand, parallel configurations
have higher methanol molar flow rates and lower hydrogen molar
flow rates compared with CR system. Total hydrogen molar flow
rates are depicted in Fig. 7(b) for all configurations. The figure
clearly shows that hydrogen molar flow rate in RG configuration is
20% less than CR system.
4.4. Conversion assessment
Fig. 8(a) and (b) show CO and H2 conversion in a single tube
of water-cooled and gas-cooled reactors of all the configurations.
The maximum CO conversion is in the water-cooled reactor of
RG system, which could be attributed to its fresh feed. The CO
conversion rates in the water-cooled reactor of the RG and EP
configurations are higher than in CR system. The maximum con-
version is observed in the gas-cooled reactor of RW configuration
since its fresh feed. The CO conversion in RG system is less than
other configurations, because the feed of the gas-cooled reactor
is the recycled stream composed with high concentration of
CO2 . Thus, CO2 conversion is dominant in this reactor and CO
conversion is low. Even CO conversion decreases about 3% in the
beginning of the reactor due to the conversion of CO2 to CO in
the reverse water-gas shift reaction. The reverse water-gas shift
reaction takes place because of the high CO2 content in the feed
gas of the gas-cooled reactor in the RG configuration. As it can be
seen in Fig. 8(b), the results for H2 conversion are similar to the
results for CO conversion, except in the gas-cooled reactor of the
RG system. Unlike CO, H2 conversion in the gas-cooled reactor of
the RG is higher than the gas-cooled reactor of CR configuration
which can be attributed to more CO2 hydrogenation in this reactor.
4.5. CO2 consumption rate
CO2 molar flow rates in a single tube of the water-cooled re-
actors are depicted in Fig. 9(a) for all configurations. As expected,
CO2 molar flow rate in CR system is higher than other configu-
rations because of the higher feed flow rate in its water-cooled
reactor. The RG system has the minimum CO2 molar flow rate
owing to that the feed of its water-cooled reactor is fresh synthe-

Please cite this article as: A. Mirvakili, S. Chahibakhsh and M. Ebrahimzadehsarvestani et al., Modeling and assessment of novel con-
figurations to enhance methanol production in industrial mega-methanol synthesis plant, Journal of the Taiwan Institute of Chemical
Engineers, https://doi.org/10.1016/j.jtice.2019.09.018
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Fig. 10. (a) Carbon monoxide molar fractions of a single tube of various configurations’ water-cooled and gas-cooled reactors (b) Various configurations’ carbon monoxide
total molar flow rates (c) Carbon monoxide flow rates in a single tube of various configurations’ water-cooled reactors (d) Carbon monoxide flow rates in a single tube of
various configurations’ gas-cooled reactor.

sis gas. CO2 molar flow rates in a single tube of the gas-cooled
reactors are shown in Fig. 9(b) for all the configurations. The
maximum and minimum molar flow rates of carbon dioxide are
observed in the CR and RW configurations, respectively. These
results are expected as consequences of the maximum and min-
imum feed flow rates in an equivalent tube of these systems.
Fig. 9(c) demonstrates the total carbon dioxide flow rates in all the
configurations. The minimum CO2 molar flow rate is regarded to
RG system. As it is obvious, more consumption of CO2 contributes
to more methanol production. Therefore, the RG is the best
configuration. An interesting point is that the proposed parallel
configurations produce more methanol and less carbon dioxide. In
addition, the molar flow rate of CO2 in the outlet stream of the
RG configuration is about 19% less than CR system.
4.6. CO consumption rate
The CO molar fractions in a single tube of water-cooled reactor
and a single tube of gas-cooled reactor for CR, RG, EP, and RW
configurations are illustrated in Fig. 10(a). Carbon monoxide is an
important reactant and it is consumed along the reactor for all
the configurations. Fig. 10(a) shows that the higher molar fraction
of carbon monoxide in the feed leads to an increase in the slope
of the CO consumption along the reactors. In addition, the molar
fractions of CO in the outlet of these configurations are higher
than others. Fig. 10(b) illustrates the total molar flow rates of CO
in all the configurations. The maximum CO molar flow rate is
regarded to the RG system and the minimum one is regarded to
the CR configuration. Fig. 10(b) indicates that the outlet gas in
RG system has 31% more carbon monoxide compared with the CR
system. Figs. 10(b) and 9(c) show that the outlet gas in the RG
system has higher content of CO and lower concentration of CO2
compared with the other configurations which arises from the
feed gas arrangement in RG configuration. The fresh synthesis gas
with high content of CO and low content of CO2 is sent to the two
parallel water-cooled reactors and as a result of low conversion,
the outlet stream contains high amount of CO. On the other hand,
the recycled stream which has high CO2 content is sent to the
gas-cooled reactor and as a result of high conversion, the outlet
stream contains low concentration of CO2 .
CO flow rates in a single tube of each water-cooled and gas-
cooled reactors are depicted, respectively, in Fig. 10(c) and 10(d)

Please cite this article as: A. Mirvakili, S. Chahibakhsh and M. Ebrahimzadehsarvestani et al., Modeling and assessment of novel con-
figurations to enhance methanol production in industrial mega-methanol synthesis plant, Journal of the Taiwan Institute of Chemical
Engineers, https://doi.org/10.1016/j.jtice.2019.09.018
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12 A. Mirvakili, S. Chahibakhsh and M. Ebrahimzadehsarvestani et al. / Journal of the Taiwan Institute of Chemical Engineers xxx (xxxx) xxx
Fig. 11. (a) The effect of the fresh feed fraction changes on the methanol molar flow
rate along the water-cooled reactor (b) The effect of recycled feed fraction changes
on the methanol molar flow rate along the gas-cooled reactor.
for all configurations. As mentioned earlier, in RG configuration
the recycled gas is sent to the gas-cooled reactor which has high
content of CO2 and low content of CO. Therefore, CO2 is converted
to methanol in a high rate and CO is consumed slowly in the gas-
cooled reactor. Higher ratios of CO/CO2 in the feed of the reactors
lead to an enhancement of methanol production. The highest ratio
of CO/CO2 is 2.87 and it is regarded to the water-cooled of RG
system. The maximum CO/CO2 ratio in CR configuration is 1.02 for
the feed of the water-cooled reactor. Thus, the maximum methanol
production occurs in the water-cooled reactor of RG system.
4.7. Finding optimum parallel configuration
The effects of changing the feed flow rates in the reactors on
the products are depicted for all the parallel configurations in
Figs. 11–13. The feed of conventional series configuration com-
prised of two parts, one is the fresh synthesis gas with a flow rate
of 6758.25 mol/s and the other is the recycled gas with a flow
rate of 14,868.11 mol per second. However, this feed stream must
be divided in parallel configuration. In order to find the optimum
fresh feed fraction in the parallel configuration, methanol produc-
Please cite this article as: A. Mirvakili, S. Chahibakhsh and M. Ebrahimzadehsarvestani et al., Modeling and assessment of novel con-
figurations to enhance methanol production in industrial mega-methanol synthesis plant, Journal of the Taiwan Institute of Chemical
Engineers, https://doi.org/10.1016/j.jtice.2019.09.018
[m5G;October 4, 2019;7:29]
tion, carbon dioxide consumption, and operating temperature are
important factors.
The effect of changing the fresh feed fraction on the methanol
molar flow rate along the water-cooled reactor is shown in
Fig. 11(a). As the figure clearly indicates, the methanol production
has increased via the increase in the fraction. The optimum case is
the RG configuration, which has the highest fresh syngas fraction
entering to the water-cooled reactor equal to one, and the worst
case is the RW system with the lowest fresh syngas fraction
equal to zero. The RG configuration produces methanol 1.2 times
more than RW configuration, which is equal to seven tons per
second.
The effect of changing recycled feed fraction on the methanol
molar flow rate along the gas-cooled reactor is shown in
Fig. 11(b). When the fraction of the recycled gas in the feed
is equal to one, it means that all recycled gas is sent to the gas-
cooled reactor or in other words, it indicates the RG system. When
the fraction of the recycled gas is equal to zero, it indicates the RW
configuration. As shown in Fig. 11(b), methanol molar flow rate do
not vary significantly between different configurations. The highest
methanol molar flow rate in RG configuration is only 2% more than
the highest methanol molar flow rate in RW system. However, this
2 percent is estimated to be about 1.3 tons per second. Increase in
the recycled gas fraction in the reactor feed leads to an increase
in methanol production. This expected result arises from increase
in the feed flow rate and CO2 concentration. When fresh syngas
is fed to the gas-cooled reactor, which means the fraction of the
recycled gas is zero, methanol is produced considerably in the
beginning of the reactor. Following that, its production rate is
gradually decreased along the length of the reactor.
Fig. 12(a) demonstrates the effect of fresh feed fraction on CO2
molar fraction along the water-cooled reactor. Increase in the frac-
tion of fresh syngas reduces the content of CO2 in the feed, which
induces the enhancement of CO2 production. However, when the
fraction of the fresh syngas is almost zero, CO2 composition is
high and plays the role of a reactant and is consumed at first.
Then, CO2 composition decreases along the reactor until it starts
to be produced in the end of the reactor.
The effect of changing the recycled gas fraction in the feed on
the CO2 molar fraction along the gas-cooled reactor is depicted
in Fig. 12(b). The minimum CO2 emission is regarded to the RG
system in which all the recycled gas is sent to the gas-cooled
reactor. Therefore, the feed is composed with high concentration
of CO2 and low CO content. CO2 is regarded as the main reactant
and converts to methanol. CO2 emission in the gas-cooled reactor
of the RG system is 21.3% less than the emission in the RW
configuration. As shown in Fig. 12(a), although CO2 molar fraction
in the outlet gas of the RG system is about 27.3% more than RW
configuration, the feed molar flow rate in the water-cooled reactor
of the RG system is 54.4% less than the water-cooled reactor of the
RW configuration. Generally, CO2 emission in RG system is 11.2
tons per second less than in RW configuration and it is 12.7 tons
per second less than CR system.
Fig. 13(a) shows the effect of fresh feed fraction on the temper-
ature profile in the water-cooled reactor. Increase in the fraction
of the fresh synthesis gas in the feed of the water-cooled reactor
induces a higher temperate peak in the beginning of the reactor
and make it a possible place for hot spot. Temperature profile
for different feed rates of the gas-cooled reactor is presented in
Fig. 13(b). Again, the maximum temperature peak happens in
the case where the feed is fresh synthesis gas. More temperature
drops are observed where the feed has lower fractions of the recy-
cled gas. It is a destructive phenomenon, because the temperature
is near to the dew point temperature of the gas (about 430 K) in
the bottom of the reactor. In this condition, methanol and water
may be condensed, which damage the catalysts. Therefore, the RG
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A. Mirvakili, S. Chahibakhsh and M. Ebrahimzadehsarvestani et al. / Journal of the Taiwan Institute of Chemical Engineers xxx (xxxx) xxx 13

Fig. 12. (a) The effect of fresh feed fraction on CO2 molar fraction along the water-
cooled reactor (b) The effect of the feed’s recycled gas fraction changes on the CO2
molar fraction along the gas-cooled reactor.

Fig. 13. (a) The effect of fresh feed fraction on the temperature profile in the water-
cooled reactor (b) Temperature profiles of gas-cooled reactor for different flow rates.
configuration is the superior case from the viewpoint of product
composition and temperature.
the catalytic packed bed compared with CR system. The three
parallel configurations are different in the reactor feeds. These
5. Conclusion
configurations have been simulated in order to compare and select
the superior configuration. The maximum and minimum amount
In the conventional mega-methanol synthesis configuration,
of methanol is produced in RG and CR configurations, respectively.
fixed bed shell and tubes reactors are connected in series. The feed
Methanol molar flow rate in RG system is 12 times greater than CR
is a mixture of fresh synthesis gas and a recycled stream, after
configuration. Furthermore, RG system is an environmental friendly
preheating in the gas-cooled tubes, it is sent to the tubes of the
configuration because of the minimum CO2 emission. In fact, the
water-cooled reactor and the exothermic methanol synthesis takes
CO2 molar flow rate in the purge stream of RG configuration is 0.8
place on catalytic bed. The reacted gas is sent to the gas-cooled
times of CO2 molar flow rate in the purge stream of CR system.
shell side and it does not have the tendency to react in the begin-
ning of the gas-cooled reactor. Therefore carbon oxides conversion
is low in the gas-cooled, however changing the feed of the reactors Acknowledgements
can increase the gas-cooled efficiency and produce more methanol.
In this study, alternative parallel configurations were proposed in The authors are grateful to the Persian Gulf University for
which the feed gas is divided into two parts and each part is sent supporting this research.
to a different type of reactors, gas-cooled and water-cooled, as
their feed. Thus, the feed of the reactors in the parallel configura- References
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Please cite this article as: A. Mirvakili, S. Chahibakhsh and M. Ebrahimzadehsarvestani et al., Modeling and assessment of novel con-
figurations to enhance methanol production in industrial mega-methanol synthesis plant, Journal of the Taiwan Institute of Chemical
Engineers, https://doi.org/10.1016/j.jtice.2019.09.018
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