Fuel Processing Technology 193 (2019) 159–179

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Fuel Processing Technology

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

Research article

Introducing a novel process to enhance the syngas conversion to methanol T

over Cu/ZnO/Al2O3 catalyst
⁎
Behnaz Rahmatmand, Mohammad Reza Rahimpour , Peyman Keshavarz
Department of Chemical Engineering, Shiraz University, Shiraz 71345, Iran

A R T I C LE I N FO A B S T R A C T

Keywords: In this study, a novel configuration, Adiabatic and Plate Water-cooled Reactors, which called APW is introduced
Adiabatic as an alternative for a two stage conventional methanol process consisting of gas-cooled and water-cooled re-
Water-cooled actors. In the APW configuration, the gas-cooled reactor is replaced with two adiabatic reactors with the opti-
CO2 conversion mized basic design. A water-cooled reactor is like a plate heat exchanger with three sections by the different
H2 conversion
number of plates. The gas flow rate through each section is optimized, so that pressure and temperature changes
Methanol
along these sections are almost identical. Mathematical modeling indicates that, temperature rise within the
adiabatic reactor precludes gas condensate formation, consequently improves the catalyst durability. Moreover,
the small length to cross section ratio of the adiabatic bed results in low pressure drop. Also, high average
temperature and low pressure drop along the adiabatic beds enhance methanol production. The proposed
configuration, provides different advantages than the conventional process, e.g. low pressure drop, high cooling
efficiency of the water-cooled reactor and higher H2 and CO2 conversions. The APW configuration enhances the
methanol production rate 12.2% in comparison with conventional configuration. Other advantages in this
configuration are, eliminating condensate formation, preventing greenhouse gas emissions and improving cat-
alyst durability.

1. Introduction
Energy plays a vital role in the world. Thus, recently, the alternative
source of energy, e.g. methanol has received much attention because of
its excellent combustion properties [1,2]. Although the energy density
of gasoline is greater than that of methanol, conventional fossil fuels are
more polluting than methanol [2]. In addition, methanol is used to
produce chemicals including methyl formate, dimethyl ether, acetic
acid, and formaldehyde and also to store and transport hydrogen [3,4].
Industrially, methanol is synthesized from syngas in two stages. In the
first stage, syngas including carbon dioxide, hydrogen and carbon
monoxide is produced by natural gas reforming or gasification of solid
fuels and then syngas is converted to methanol.
Since the first commercialized execution of the methanol synthesis
process from 1923, it has undergone many advancements [5]. In the
first technology, introduced by BASF in 1923, CO was hydrogenated to
methanol on a ZnO–Cr2O3 catalyst at 623–673 K and 240–300 bar [6].
A significant advancement was attained in the 1960s by ICI that me-
thanol was produced using more active Cu/ZnO catalyst at lower
pressure and temperature of 523–553 K and 60–80 bar, respectively [6].
The most important section of the methanol synthesis process is the
reactor that is commonly separated into two categories including gas
and liquid phases technologies [7]. Gas phase technologies are com-
posed of two phases (solid-gas) reactors offered by a range of manu-
factures including Haldor Topsøe collect-mix-distribute converter,
Kellogg, Brown and Root's (now Halliburton) methanol converter, Toyo
Engineering Corporation's MRF-Z® reactor, Linde isothermal reactor,
Lurgi's Mega-Methanol process and etc. [7]. For high methanol capa-
cities, Lurgi developed a two-stage converter system using two Lurgi
methanol reactors in combination [7]. The structure of these two re-
actors called water-cooled and gas-cooled reactors is like a shell and
tube heat exchanger [8,9]. The shell in the gas-cooled reactor and the
tubes in the water-cooled reactor are filled with the appropriate catalyst
(i.e., Cu/ZnO/Al2O3 catalyst). Firstly, methanol production from syngas
is carried out in the water-cooled reactor. The temperature of coolant in
the water-cooled reactor (i.e., initial reactor) remains constant. The
stream out from the first reactor flows to the next reactor (i.e., gas-
cooled reactor) in which water-cooled reactor fresh feed is flowing
through tubes to remove heat from the shell of the gas-cooled reactor.
Therefore, the reacting gas temperature at shell side decreases as it
approaches the lower part of the gas-cooled reactor [9].
Regarding the economic value of methanol, it is highly beneficial to

⁎
Corresponding author.
E-mail address: rahimpor@shirazu.ac.ir (M.R. Rahimpour).

https://doi.org/10.1016/j.fuproc.2019.05.014
Received 21 November 2018; Received in revised form 16 April 2019; Accepted 11 May 2019
Available online 22 May 2019
0378-3820/ © 2019 Elsevier B.V. All rights reserved.
B. Rahmatmand, et al. Fuel Processing Technology 193 (2019) 159–179

Nomenclature z indicator of axial direction (m)

Ac cross-section of reaction area (m2) Greek letter

Cp gas specific heat (J mol−1 K−1)
dp catalyst diameter (m) θ angle between two plates in the water-cooled reactor of
fi fugacity (Pa) the APW configuration
Fi molar flow rate of species “i” (mol/ s) ΔH heat of reaction (J mol−1)
Ft total molar flow rate (mol/ s) η catalyst effectiveness factor
hi heat transfer coefficient of reacting side (W m−2 k−1) μ viscosity (Pa s)
ho heat transfer coefficient of cooling side (W m−2 k−1) ε bed void fraction
Kpi equilibrium constant ρb catalyst bed density (kg m−3)
Ki equilibrium constant of adsorption (bar−1) ρ gas phase density (kg m−3)
Ki k value νi,j stoichiometric coefficient of component in reaction
ki reaction rate constant (mol kg−1 s−1 bar-1/2) φi fugacity coefficient
Kw thermal conductivity of wall (W m−1 k−1) Δx wall thickness (m)
ΔHf,i enthalpy of formation for component “i” (J mol−1)
L reactor length (m) Subscript and superscripts
Mi molecular weight of each component (gr mol−1)
P pressure (Pa) j reaction index
Pa atmospheric pressure (pa) i component index
ri reaction rate (mol kg−1 s−1) v vapor phase
Ri inner diameter of each of water-cooled bed sections in the 0 input condition
APW configuration (m) l liquid phase
Ro outer diameter of each of water-cooled bed sections in the g gas phase bulk
APW configuration (m)
R universal gas constant (J K−1 mol−1) Abbreviations
T temperature (K)
ug gas flow velocity (m s−1) DAE differential-algebraic equations
U overall coefficient of heat transfer between reaction and DME dimethyl ether
cooling sides (W K−1 m−2) APW adiabatic & plate water-cooled reactors (abbreviated name
Wp plate width in the water-cooled reactor of the APW con- of the proposed configuration)
figuration (m) CR conventional methanol synthesis reactors
xi component mole fraction in liquid phase CFD computational fluid dynamics
yi component mole fraction of in gas phase RWGS reverse water gas shift reaction
Z compressibility factor SRK Soave-Redlich-Kwong

enhance the performance of the conventional methanol synthesis pro-
cess [10]. Wagialla et al. [11] used the fluidized-bed reactor to synth-
esis methanol and they achieved 30% improvement in the methanol
production rate. Lovik et al. [12] proposed a model in which the de-
activation of catalyst was considered and the presented method can be
applied to fixed bed reactor systems. Rahimpour [13] confirmed the
higher conversion and longer catalyst life time of two stage methanol
production process consisting of the water-cooled and gas-cooled re-
actors comparing to one stage process composed of the water-cooled
reactor. In another study by Rahimpour et al. [14], the wall of gas-
cooled reactor tubes was covered by hydrogen perm-selective mem-
brane to improve the process performance and they found that there are
optimum values of coolants and reacting gas temperatures to enhance
the methanol production rate. Also, dynamic modeling of fixed-bed
methanol synthesis reactors was carried out by some researchers to
compare with the steady state model [15,16]. Abrol et al. [17] devel-
oped a methanol synthesis recycle-loop model using dynamic and
steady-state models to analyze the process performance. Kordabadi
et al. [18] developed a heterogeneous model to optimize a methanol
synthesis reactor using genetic algorithms. Fuad et al. [19] applied a
repeated process estimation–optimization strategy in the presence of
methanol synthesis catalyst deactivation to find the optimum values of
control variables of a methanol synthesis reactor system. Luyben [20]
utilized three gas recycle streams in a methanol reactor/distillation
column system and developed an economically optimum design to
produce highly pure methanol. Santangelo et al. [21] optimized
synthesis loops with quench reactors to maximize methanol production.
Chen et al. [22] carried out an optimization study using Aspen Plus
simulation software along with steady-state modeling of the methanol
synthesis reactor to maximize methanol production by optimization of
cooling water volumetric flow rate, steam drum pressure and syngas
inlet temperature. Holmgren et al. [23] assessed the energy balance of a
methanol synthesis system including biomass gasification. Also, Park
et al. [24] developed kinetic models for methanol synthesis process
using a mixed reforming reactor to analyze the process.
In addition, thermally coupled reactors were proposed by some
researchers in which endothermic and exothermic reactions were car-
ried out in two different sides of the reactor simultaneously to achieve
appropriate in-situ energy integration between exothermic and en-
dothermic reactions [25]. Moreover, a membrane was applied within
these type of reactors to separate a favorable product and to improve
the driving force of the forward reactions [25–27]. Hence, different
categories of thermally coupled methanol synthesis reactors were in-
troduced including one-membrane or two-membrane reactors, dual
methanol reactors and fluidized-bed membrane reactors [25]. Ra-
himpour et al. [28] presented a reactor that dimethyl ether (DME) and
methanol synthesis reactions, either endothermic and exothermic, were
carried out inside the reactor simultaneously. In another study, Farniaei
et al. [29] investigated a two-membrane reactor in which two hydrogen
and water perm selective membranes were applied in the structure of
the reactor. Rahimpour et al. [30] introduced a fluidized-bed mem-
brane reactor to produce methanol, benzene, and hydrogen. Also,
Abashar et al. carried out the modeling of circulating fast fluidized bed
reactor along with water removal from the reaction environment using
zeolite-4A to methanol synthesis [31].
Mirvakili et al. [9] investigated the gas-cooled reactor of

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B. Rahmatmand, et al. Fuel Processing Technology 193 (2019) 159–179

conventional methanol synthesis process to investigate condensate Table 1

formation within this reactor. In another study, Mirvakili et al. [10] The rate constants of the model [36].
estimated the distribution of temperature and flow all over the gas- Constants of adsorption equilibrium
cooled reactor using computational fluid dynamics (CFD). Results in-
dicated that unsuitable distribution of flow followed by inappropriate K= A exp ( )B A B
TR
distribution of temperature within the shell side of the gas-cooled re- KCO2 (7.050 ± 1.390) ∗ 10 −7
61700 ± 800
actor results in condensate formation [10]. Consequently, catalyst de- K H2 O (6.370 ± 2.880) ∗ 10−9 84000 ± 1400
1/2
activation was occurred due to the condensate formation of methanol KH
2
and water. In fact, alumina support of catalyst adsorbs water in the KCO (2.160 ± 0.440) ∗ 10−5 46800 ± 800
stream. Hence, ZnO and Cu crystallization is promoted by water fol-
lowed by reduction in active sites of the catalyst [32–36]. Based on this,
Constants of equilibrium
the gas-cooled reactor is facing the condensate formation drawback
which leads to the catalyst loss and less process efficiency [9,10]. A B
Kp = 10( T − B )
A
According to the methanol synthesis reactions scheme, carbon
Kp1 5139 12.621
monoxide and carbon dioxide are converted to methanol during the Kp2 3066 10.592
process. Regarding the fact that carbon dioxide and carbon monoxide Kp3 −2073 −2.029
gases cause the greenhouse effect that is harmful to the environment,
recycling unreacted carbon dioxide and carbon monoxide gases con-
Constants of rate
tributes to preventing greenhouse gas emissions and to improving re-
actants conversions to methanol [2,37,38]. In the current research, a A B
methanol synthesis process is presented to improve the conversions of
k= A exp ( )
B
RT
k1 (4.890 ± 0.029) ∗ 10 7
−63000 ± 300
reactants including carbon monoxide, carbon dioxide and hydrogen to k2 (9.640 ± 7.300) ∗ 1011 −152900 ± 6800
methanol in addition to eliminating the problem of the conventional k3 (1.090 ± 0.070) ∗ 105 −87500 ± 300
process including the loss of catalyst.
In the present investigation, a novel configuration is introduced fH2 O fCO
called APW in which two adiabatic reactors with optimized design and k2 K CO2 ⎡fCO2 fH2 − Kp2
⎤
r2 = ⎣ ⎦
dimensions are applied instead of the gas-cooled reactor. Also, in the
K H2 O ⎞
proposed configuration, the structure of the water-cooled bed is mod- (1 + K CO fCO + K CO2 fH2O ) ⎡f H1/2 + ⎛ 1/2 ⎜ fH2 O ⎤ ⎟
⎢ 2 ⎥
ified to improve the methanol synthesis process efficiency. Considering ⎣ ⎝ K H2 ⎠ ⎦ (5)
the water-cooled reactor structure, water-cooled reactor design is like a
fCH3 OH fH2 O
plate heat exchanger which consists of three sections with different k3 K CO2 ⎡fCO2 f H3/2 − 1/2 K
⎤
⎢ 2 fH ⎥
cross sectional area and number of plates. Therefore, the gas flow rate r3 = ⎣ 2 p3
⎦
that enters each section has been optimized so that the pressure, tem- K H2 O ⎞
(1 + K CO fCO + K CO2 fCO2 ) ⎡f H1/2 + ⎛ 1/2 ⎜ fH2 O ⎤ ⎟
perature and gas flow rate along these three sections are almost iden- ⎢ 2
⎣ ⎝ K H2 ⎠
⎥
⎦ (6)
tical. The performance of the proposed configuration is evaluated by
the modeling and optimization and the modeling results are compared where f is the fugacity of each component. The rate constants are
with that of conventional configuration called CR (Conventional presented in Table 1.
Reactors) composed of water-cooled and gas-cooled reactors. Moreover,
an energy saving method is carried out for the APW configuration to 3. Process description
reduce the energy consumption by this process.
In this section, two different configurations are explained, the
2. Reaction schemes and kinetics conventional methanol production reactors (CR) and the novel pro-
posed configuration called APW.
In this study, the reaction mechanism of methanol synthesis, con-
tains two different type of reactions. The first one, is the reverse water 3.1. Conventional methanol production reactors (CR)
gas shift reaction (RWGS), in which the carbon dioxide is converted to
carbon monoxide and water. The second one, involves the hydrogena- The conventional Lurgi's technology, for high methanol capacities,
tion conversion of carbon monoxide and carbon dioxide into methanol. contains a two-stage converter system using two Lurgi methanol re-
It should be mentioned that, these reactions, are occurred as a single actors in combination [7]. Fig. 1 shows the conventional two-stage
reaction mechanism, simultaneously [39]: converter system (CR), developed by Lurgi's technology.
As shown in Fig. 1, the CR configuration is composed of water-
0
CO + 2H2 ↔ CH3 OH⋅ΔH298 = −90.7 KJ/molCO (1) cooled and gas-cooled reactors. Within these reactors, with shell and
tube inside the structure, reaction and heat transfer are accomplished
0
CO2 + H2 ↔ CO + H2 O⋅ΔH298 = +41.2 KJ/molCO2 (2) simultaneously. The first step of methanol synthesis is performed in the
water-cooled reactor in which reactions are accomplished inside tubes
0
CO2 + 3H2 ↔ CH3 OH + H2 O⋅ΔH298 = −49.5 KJ/molCO2 (3) over Cu/ZnO/Al2O3 catalyst and water flows through shell to remove
heat from the reaction side. The cooling side temperature of the water-
The kinetic rate model of the reaction mechanism, was introduced
cooled reactor is constant. The product from the first reactor (stream
by Graaf et al. [40] in 1988. In this model the reactions occurred over
VII) enters the gas-cooled reactor shell (i.e., second reactor) to perform
the Cu/ZnO/Al2O3 catalyst. The rate model is presented in Eq. (4) to Eq.
the second step of methanol synthesis. In this reactor, reaction is per-
(6):
formed inside shell over Cu/ZnO/Al2O3 catalyst. Feed stream (stream I)
fCH3 OH enters the tubes of the gas-cooled reactor to pre-heat the first reactor
k1 K CO ⎡fCO f H3/2 − ⎤
⎢
⎣
2 1/2 K ⎥
fH
2 p1
⎦ feedstock (stream IV). The preheating mechanism of the feedstock is
r1 = performed by removing heat from the reaction side of the gas-cooled
K H2 O ⎞
(1 + K CO fCO + K CO2 fCO2 ) ⎡f H1/2 + ⎛ 1/2
⎜ fH2 O ⎤
⎟ reactor. Afterward, stream IV is separated into two streams, streams VI
⎢ 2 ⎥
⎣ ⎝ K H2 ⎠ ⎦ (4) and V to enter water-cooled reactors. Eventually, the product stream

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Fig. 1. CR configuration diagram.

(stream VIII) leaves the gas-cooled reactor shell [9]. Methanol and
water (stream IX) are separated from the product stream (stream VIII).
The major portion (i.e. about 95%) of the separated gaseous stream
(purge gas) is recycled (recycle stream (III)) and reused as the feedstock
of methanol synthesis reactors, and the rest is sent to the flare [3].
Afterward, the recycle stream (stream III) is combined with the fresh
feed (stream II) to form the feed stream (stream I) that enters the tube
side of the gas-cooled reactor. The characteristics of catalyst, reactors
and feed stream (stream I) are mentioned in Table 2.
In this configuration, undesirable distribution of flow inside the gas-
cooled reactor leads to undesirable temperature distribution.
Consequently, gas condensation takes place within the gas-cooled re-
actor shell with the negative effect on the efficiency of the catalyst
[9,10,32].
3.2. APW configuration
separator (stream XI) is heated up to the desired temperature and then
it is introduced into the second adiabatic reactor as the feedstock. The
product of the second adiabatic reactor (stream V) is separated to two
streams (streams VI and VII) and then each stream is separated into
three streams (i.e., streams No. 1, 2 and 3). The flow rate of these
streams are different but with the same composition. Inside the water-
cooled bed, there are three sections including inner, middle and outer
sections. Streams No. 1, 2 and 3, enter to the outer, middle and inner
sections respectively. Within each section, there are number of plates so
that the number of plates in these three sections is different. Fluid
which is flowing upward within these plates is boiling water to remove
heat from the reaction side. In water-cooled bed, reactions take place
between plates of inner, middle and outer sections loaded with catalyst.
In fact, gas flows downward between plates over the catalyst and water
flows within plates counter-currently. Finally, the product leaves the
reactor at the bottom of the water-cooled reactors (stream VIII). The

In the current investigation, a novel configuration called APW is Table 2

introduced. The schematic diagram of the APW configuration is shown Specifications of the catalyst, reactors and feed stream in the CR configuration.
in Fig. 2 (a). Also, the structure of the water-cooled reactor in Fig. 2 (b) Design specifications Gas-cooled Water-cooled reactor
is like a plate heat exchanger that consists of three sections with dif- reactor
ferent cross section area and number of plates.
Value Value
The gas flow rate flowing through each section has been optimized
so that the pressure, temperature and gas flow rate along these three Length of reactor (m) 10.5000 8.4000
sections are almost identical. In fact, the APW configuration is com- Diameter of tube (m) 0.0254 0.0380
posed of two adiabatic reactors in series and each adiabatic reactor is Diameter of shell (m) 5.5000 4.5000
composed of two adiabatic catalyst beds in parallel. In the first step, Number of tubes 3026 5955
Temperature along shell (K) – 513
feed stream (stream I) is separated into two streams to enter two cat- Feed flow rate in one tube (mol/s) – 1.4000
alyst beds of the first adiabatic reactor. Design of the adiabatic reactors Pressure at tube inlet (bar) 76.9800 75
and dimensions of catalyst beds are optimized to maximize methanol Pressure at shell inlet (bar) 72.2000 –
production. So, pressure drop along adiabatic catalyst bed tends to zero Mass flowing through shell (kg/s) – 42.0600
Void proportion of bed 0.3900 0.3900
because of small length to cross section ratio of the bed [41]. Moreover,
Density of bed (kg/m3) 1140 1140
temperature increase along the adiabatic bed caused by exothermic Diameter of particle (m) 0.0057 0.0057
reactions precludes condensate formation. On the other hand, it should
Feed constituents (stream I) Mole ratio
be noted that excessive temperature increase along adiabatic bed has H2O 0.00039
negative impact on catalyst and performs the reactions in the reverse CH4 0.10060
direction. Consequently, the dimensions and number of adiabatic cat- CO 0.08500
alyst beds are optimized to preclude excessive temperature increase H2 0.63340
CO2 0.08320
within the reactor. In the next step, the stream from the first adiabatic
CH3OH 0.00490
reactor (stream IV) enters a cooling device to segregate a portion of N2 0.09300
methanol and water (stream X). Then, the gas stream exiting the

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B. Rahmatmand, et al. Fuel Processing Technology 193 (2019) 159–179

Fig. 2. The diagram of (a) the APW configuration, (b) water-cooled reactor cross section in the APW configuration.

product is passed through the condenser and separator to separate 4. Mathematical model
water and methanol (stream IX). The major portion (i.e. about 95%) of
the separated gaseous stream (purge gas) is recycled (recycle stream In this section, mathematical and thermodynamic models applied in
(III)) and reused as the feedstock of the first adiabatic methanol developing the process model are explained completely.
synthesis reactor, and the rest is sent to the flare [3]. Afterward, the
recycle stream (stream III) is combined with fresh feed (stream II) to
4.1. Reactor model
form the feed stream (stream I) that enters the first adiabatic reactor.
Characteristics of reactors and condenser located between two adia-
The model applied in the present investigation is the homogenous
batic reactors are shown in Tables 3–5, respectively.
model in axial direction [42]. In this approach, behaviors of gas and
solid phases within the reactor are similar, so the model is developed

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Table 3 laminar plug flow pattern, is assumed for the gas flow within the re-
Characteristics of the catalyst, reactor and feed stream of the adiabatic reactors actor [9,36]. In order to attain mass and energy equations within the
in the APW configuration. reactors of the CR configuration, a cylindrical element is assumed in the
Parameters First adiabatic bed Second adiabatic bed axis direction with length Δz. With considering the discussed pre-
suppositions, the governing mass equation of reactors in the CR process
Values Values is:
Diameter of reactor (m) 5 5 1 dFi
Length of reactor (m) 6.5000 6.5000 −
Ac dz
+ ∑ ηνij rj ρb = 0
Number of adiabatic beds 2 2 j (7)
Length of each adiabatic bed (m) 1.7000 1.7000
Diameter of particle (m) 0.0057 0.0057 where i is the counter of component and j is the counter of reaction,
Density of catalyst bed (kg/m3) 1140 1140
catalyst bed density is demonstrated by ρb, the rate of reaction is no-
Void fraction of bed 0.3900 0.3900
Pressure at bed inlet (bar) 75 74.83 minated by rj, νij is the representative of every component stoichio-
Feed stream rate (mol/s) 16,674 14,422 metric coefficient in every reaction, reaction side cross section area is
Temperature at bed inlet (K) 513 513 shown by Ac, and η (i.e., effectiveness factor) is calculated by dusty gas
Feed constituents (stream I) Mole ratio approach [43].
H2O 0.00039 The governing energy equation of water-cooled and gas-cooled re-
CH4 0.10060 actors is:
CO 0.08500
H2 0.63340 Cp d (Ft T ) πDi
CO2 0.08320 −
Ac dz
+ ρb ∑ ηri .j (−ΔHf .i) ± Ac
U (T shell − T tube ) = 0
CH3OH 0.00490 j (8)
N2 0.09300
where reaction side temperature and gas heat capacity are shown by T
and Cp respectively, tube and shell temperatures are exhibited by Ttube
Table 4 and Tshell, and reaction heat is demonstrated by ΔHi.
Characteristics of catalyst, reactor and inlet stream to the water-cooled reactor The molar flow along the tubes of the gas-cooled reactor (cooling
in the APW configuration.
side) does not change. Also, in water-cooled bed, the cooling side
Parameters Water-cooled bed temperature is constant at 513 K.
In order to attain the governing mass and energy equations of the
Values
APW reactor, a differential element is considered for each of adiabatic
Number of sections inside the shell 3 and water-cooled reactors. The differential element of the adiabatic bed
Fraction of inlet stream routed to inner section (stream 3) 0.2020 is a cylindrical element along the axis with length Δz, while the dif-
Fraction of inlet stream routed to middle section (stream 2) 0.3330 ferential element of the water-cooled bed is located between two
Fraction of inlet stream routed to outer section (stream 1) 0.4640
cooling plates which its length in axial direction is Δz. With the aim of
Number of plates of inner section 144
Number of plates of middle section 240 estimating the temperature, pressure and compostion along each sec-
Number of plates of outer section 336 tion (including inner, middle and outer sections) of the water-cooled
Plate width (m) 0.7000 reactor, this differential element is considred within each section se-
Plate thickness (m) 0.0026 parately to develop the model. The differential element considered for
Diameter of central tube (m) 1.4680
Catalyst bed length (m) 8.4000
water-cooled reactor is shown in Fig. 3 in which Ri and Ro are inner and
Diameter of particle (m) 0.0057 outer diameters of the element respectively, θ is the angle between two
Density of catalyst bed (kg/m3) 1140 plates, and Wp is the width of the plate.
Void fraction of bed 0.3900 The cross section of the element is computed as below:
Inlet reaction side pressure (bar) 74.7700
Temperature along cooling side (K) 513
Total mass flow rate of the cooling side (kg/h) 151,437

Table 5
Characteristics of inlet and outlet streams and energy requirement of the con-
denser located between two adiabatic reactors in the APW configuration.
Parameters Inlet stream Outlet stream Outlet stream
(stream IV) (stream X) (stream XI)

Molar flow (kmol/h) 55,450 3549 51,901

Mole ratio
H2O 0.0137 0.2062 0.0006
CH4 0.1086 0.0031 0.1157
CO 0.0648 0.0007 0.0692
H2 0.5800 0.0017 0.6194
CO2 0.0792 0.0306 0.0825
CH3OH 0.0535 0.7556 0.0057
N2 0.1002 0.0021 0.1069

Duty of condenser (KJ/h) 5.783 × 108

based on gas phase behavior to shorten calculations [42]. Presumptions

considered in the model are: the ideal gas phase, the steady state con-
dition, negligible radial heat and mass variation, negligible axial heat Fig. 3. The differential element considered in each insid section of the water-
penetration, uniform bed porosity in all directions. Moreover, the cooled bed.

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B. Rahmatmand, et al. Fuel Processing Technology 193 (2019) 159–179

θ to calculate the fugacity coefficient of each component [36]:

Ac = π (Ro2 − Ri2 )
360 (9)
b Z+B
The governing mass equation of water-cooled bed and adiabatic bed φi = exp ⎛ i (Z − 1) − q ln ⎛ ⎞ − ln(Z − B ) ⎞
⎝b ⎝ Z ⎠ ⎠ (18)
in APW configuration reactor is:
1 dFi b= ∑ yi bi
−
Ac dz
+ ∑ ηνij rj ρb = 0 i (19)
j (10)
a= ∑ ∑ yi yj (1 − kij ) ai aj
The governing energy equation of the water-cooled bed is: i j (20)
Cp d (Ft T ) πwp
−
Ac dz
+ ρb ∑ ηri .j (−ΔHf .i) ± Ac
U (T shell − T tube ) = 0
B=b
P
j (11) RT (21)
where width of the plate is indicated by Wp, and Ac is differential ele- a
q=
ment cross section area in water-cooled reactor. The cooling side tem- bRT (22)
perature of the water-cooled reactor is constant at 513 K.
The governing energy equation of the adiabatic bed is presented in
q = q⎜
(
⎛ 2 ∑j yj (1 − kij ) ai aj ) − b⎞ i
Eq. (12): ⎟
⎜ a b⎟
⎝ ⎠ (23)
Cp d (Ft T )
−
Ac dz
+ ρb ∑ ηri .j (−ΔHf .i) = 0 which R, T, and Z are representative of universal gas constant, tem-
j (12)
perature, and compressibility factor respectively. The parameters of
The equation of pressure drop (Ergun equation) is [44]: pure component in the gas phase are shown by a and b (computed by
using [36,49–51]) and binary interaction coefficient (ki,j) are available
dp (1 − ε )2μug (1 − ε ) ug2 ρ
= 150 2
+ 1.75 in other researches [36,52]. Compressibility factors of gas and liquid
dz 3
ε dp ε 3dp (13) phases applied in Eq. (18) are computed as follows [53]:
The governing equations are solved by considering the following 1 + B − Zl ⎞
initial conditions: Zl = B + Zl (Zl + B ) ⎜⎛ ⎟

⎝ qB ⎠ (24)
z = 0 P = P0 T = T0 yi = y0i i = 1∙2…∙N (14)
Zv − B ⎞
These equations are solved simultaneously by applying other Z v = 1 + B − qB ⎛ ⎜ ⎟

⎝ (Z v + B ) Z v ⎠ (25)
equations including kinetic and axillary equations. The axillary equa-
tions are mentioned in Table 6.
Modeling was carried out by MATLAB software, using the backward 4.2.2. Flash calculation
difference method to solve the set of differential algebraic equations The separator performance was calculated by the flash calculation.
(DAE). It is assumed that gas and liquid phases are in equilibrium within the
separator. Thus, the fraction of vapor and the composition of liquid and
4.2. Thermodynamic model gas phases are computed by applying temperature, pressure and total
composition inside the separator. This approach is based on the fol-
In this section, the method and equations applied for dew point lowing equation [9]:
calculation and flash calculation are explained in detail. zi
xi =
1 + Vfrac (Ki − 1) (26)
4.2.1. Dew point calculation
Dew point calculation is carried out to find the conditions in which where Vfrac is the fraction of vapor within the separator. The k value is
the first liquid droplet appears within the reactor [9]. At this condition, computed at condition inside separator by using Eq. (17) with the fol-
the undermentioned equation is confirmed: lowing auxiliary constrains [9]:

∑ xi = ∑ (yi /Ki) = 1 Table 6

i i (15)
Axillary equations.
where the k value for every component is demonstrated by ki and xi and Definition Equation Reference
yi are the component composition in liquid and gas phases respectively.
Consequently, in order to find the dew point temperature, the tem- Heat transfer Cp μ 2/3 ρudp −0.407 [45]
perature should be find in which the aforementioned equation is coefficient of
hi
Cp ρu ( )
kw
=
0.458
ε ( ) μ
reaction side
equivalent to unit. According to the equilibrium condition between gas Heat transfer P [46]
ho = 7.96(T − Tsat )3
and liquid phases at dew point condition, the fugacity of every com- coefficient of Pa

ponent in the liquid phase is equal to that of every component in the gas cooling side
phase [36]: Overall heat transfer U=
1 [46]
1 Δx 1
coefficient + +
hi kw ho
v
fi = yi φiv = x i φil = fil (16) (plate water-
cooled reactor)
where φ is the fugacity coefficient and f is the fugacity, and i is counter Heat capacity of
Cpi = C1 + C2 ⎡ 3 C /T
2
⎤ + C4 ⎡ C5 / T ⎤
2 [47]
of every component. Moreover, superscripts of l and v are re- each component ⎣ sinh (C3 / T ) ⎦ ⎣ sinh (C5 / T ) ⎦
Heat capacity of gas Based on composition
presentative of liquid and gas phases. So, the following equation is
flow
applied to compute k value [36]: Viscosity of gas flow ∑i yi μi Mi [48]
μ=
∑i yi Mi
yi φil
Ki = = v Thermal Based on composition
xi φi (17) conductivity of
gas flow
The modified Soave-Redlich-Kwong (SRK) equation of state is used

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∑ xi = 1 plate water-cooled reactor of the APW configuration are optimized to

i (27)
∑ Ki xi = ∑ yi = 1
i i (28)
The Vfrac is computed by the Rachford-Rice equation [9].
z i (Ki − 1)
∑ 1 + Vfrac (Ki − 1)
=0
i (29)
4.3. Optimization of reactors design in APW configuration
In order to maximize the efficiency of the proposed configuration,
the adiabatic reactor structure and the inlet stream flow rate to the
plate water-cooled reactor are optimized. The optimization procedure is
described in this section.
4.3.1. Adiabatic reactor
In the proposed configuration, each adiabatic reactor contains two
adiabatic catalyst beds with high cross section to length ratio. Since the
conversions of carbon dioxide and carbon monoxide to methanol, are
exothermic, the excessive temperature increase (i.e., temperature
higher than 555 K), forces the reactions to be performed in the reverse
direction. Consequently, the methanol production efficiency of the
process decreases. Hence, in this research, the number of adiabatic
beds, and cross section area and length of each adiabatic bed are op-
timized. The optimization procedure was performed based on two
parameters including pressure drop and temperature increase along
each adiabatic catalyst bed. For this purpose, the number of beds, and
the catalyst bed cross section area and bed length are used as inlet in-
formation to optimize temperature increase and pressure drop of the
catalyst bed.
4.3.2. Water-cooled reactor
The design of water-cooled reactor in APW configuration is like a
plate heat exchanger which consists of three sections (i.e., inner, middle
and outer sections). The cross section area and number of plates in these
three sections are different. So, the number of plates in each section and
the inlet gas flow rate introduced to each section has been optimized so
that the pressure, temperature and gas flow rate along the reaction side
of three sections are almost identical.
5. Model validation
It is indispensable to validate the capability of the presented model
to estimate the performance of an industrial plant. In this section, the
model for the CR configuration is only validated as there is not any
industrial data for the APW configuration. So, the results for the overall
APW configuration are presented based on the mathematical model.
Therefore, the CR configuration modeling results are compared with
industrial data reported by a domestic petrochemical company in
Table 7 [9]. As exhibited, modeling results of the CR configuration and
industrial data have suitable conformity.
6. Results and discussion
achieve the maximized methanol production. In this section, the opti-
mizing procedure and the modeling results are presented.
6.1.1. Adiabatic reactor
The APW configuration is composed of two adiabatic reactors in
series and the structure of each adiabatic reactor is optimized based on
comparing the modeling results at different conditions. The results are
presented in Table 8. As shown, the number of catalyst beds located
within an adiabatic reactor and dimensions of each bed have determi-
nant effect on temperature and pressure changes along the bed which
finally affect the methanol production. In order to decrease the pressure
drop through the bed and the overall cost of the plant, the length to
diameter ratio of the catalyst bed, should be kept less than unit [41].
Excessive temperature increase along the bed, has two disadvantages in
the methanol production process. Since the methanol production re-
actions are exothermic, excessive increase in temperature, pushes the
reactions toward the backward direction. Consequently, the methanol
production rate decreases. Also, excessive temperature increase reduces
the catalyst activity as a result of enhancing the sintering phenomenon
through the catalyst bed. Moreover, high pressure drop along the bed
has negative impact on the driving force of the CO and CO2 hydro-
genation reactions in the forward direction. With the aim of optimizing
adiabatic reactor design, two cases (i.e., cases (1) and (2)) are in-
vestigated. In cases (1) and (2), each adiabatic reactor includes one and
two adiabatic catalyst beds, respectively. In comparison between cases
(1) and (2), methanol produced by case (2) is greater than that of case
(1). The reason is that temperature changes along the catalyst bed of
case (2) is sharper than that of case (1) which means that greater
portion of catalyst can be operated under higher temperature in case (2)
(see Fig. 4). Moreover, it is not cost effective to increase the number of
beds more than two because it can increase the vessel and catalyst costs.
As shown in Table 8, methanol production increases by increasing the
bed diameter from 3 m to 5 m. Also, Fig. 5 shows the effect of bed
diameter, in case (2), on temperature distribution through the bed.
Since the maximum bed length needed for the bed with 5 m diameter is
less than that of beds with 3 or 4 m diameters, the rate of temperature
changes along the bed with 5 m diameter is greater than that of the bed
with 4 m diameter which results in reaction rate increase (see Fig. 5).
On the other hand, increasing diameter more than 5 m has not con-
siderable effect on methanol production, while it makes vessel cost and
catalyst volume increase. As a result, the optimum design of the adia-
batic reactor is composed of two catalyst beds which dimensions of
each bed are 5 m diameter and 1.7 m length.
Table 7
Comparing the modeling outcome and industrial data of the CR configuration
(Fig. 1).
Variables Modeling Actual Plant Data Error %
Conclusion
Output of Input to Output of
Reactor Reactor Reactor
(stream VIII) (stream I) (stream VIII)

In the current research, the new configuration is proposed to en- Temperature (K) 490.46 401 495 −0.9200
hance the performance of the conventional process of methanol pro-
duction. Therefore, with the aim of investigating the performance of Constituent Mole ratio Mole ratio Mole ratio

proposed configuration comparing with the CR configuration, different H2O 0.0211 0.0010 0.0234 −9.6300
parameters are evaluated in the following sections. CH4 0.1143 0.0947 0.1140 0.2500
CO 0.0211 0.0868 0.0251 −15.8800
6.1. Optimization results of APW configuration H2 0.5556 0.6461 0.5519 0.6600
CO2 0.0809 0.0849 0.0709 14.0500
CH3OH 0.1071 0.0037 0.1040 2.9900
The main goal in this research, is maximizing methanol production. N2 0.1019 0.0828 0.1107 −7.9900
Consequently, design of the adiabatic reactor and inlet streams to the

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Table 8
Adiabatic reactor optimization results.
Bed diameter (m) Bed length Maximum temperature of the adiabatic Pressure drop of the adiabatic Total methanol Total volume of catalyst inside
(m) reactor catalyst bed (K) reactor catalyst bed (bar) production (mol/s) adiabatic reactor (m3)

Adiabatic reactor design with one catalyst bed (case 1)

3 6.20 552.32 7.98 1743.20 43.80
4 4.30 555.06 1.71 1882.20 54.00
5 2.80 555.49 0.45 1918.80 54.95
6 2.40 555.59 0.19 1925.20 67.82
8 1.60 555.63 0.04 1929.00 80.38

Adiabatic reactor design with two catalyst beds(case 2)

3 3.50 555.24 1.09 1906.70 49.45
4 2.50 555.56 0.25 1923.70 62.80
5 1.70 555.64 0.07 1929.10 66.72
6 1.20 555.65 0.02 1929.60 67.82
8 0.96 555.65 0.01 1930.00 96.46

6.1.2. Water-cooled reactor
In this section, the optimization results of the water-cooled reactor
are presented. Water-cooled reactor design optimization is carried out
based on information presented in Table 9. It is necessary to have the
same pressure drop and temperature changes along the three sections of
the water-cooled reactor. Consequently, the velocity and molar flow
rate of gas between two plates of three sections must be identical. In
order to optimize the flow rate of the inlet stream into each section, two
ratios are defined in Eq. (30) and Eq. (31).
cross section area of each section
Ratio (1) =
total cross section area
inlet gas flow rate to each section
Ratio (2) =
total gas flow rate
The inlet gas flow rate to the water-cooled reactor is divided to three
streams with equal ratios (1) and (2). On the other hand, the number of
plates inside sections has to be optimized to attain equal molar flow of
gas and cross section area between two plates of three sections. As
shown in Table 9, ratios (1) and (2) are equal for inner, middle and
outer sections. Moreover, molar flow of gas and cross section area be-
tween two plates of three sections are identical (see Table 9). As a re-
sult, it is shown in Figs. 6 and 7 that velocity and molar flow of gas
flowing between two plates of three sections are almost identical.
However, velocity of gas flowing between two plates of inner section is
slightly less than that of two other sections due to the slightly greater
(30)
cross section area between two plate of inner section comparing to two
other sections.
(31)

Fig. 4. Temperature changes along adiabatic catalyst beds of cases (1) and (2) with 5 m diameter.

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Fig. 5. Temperature changes along adiabatic catalyst beds of case (2) with 4 and 5 m diameters.

Table 9
Water-cooled reactor design optimization data.
Sections Cross section area Ratio (1) Inlet gas flow rate to each Ratio (2) Number of cooling Cross section area between Inlet gas flow rate to space between
(m2) section (mol/s) plates two plates (m2) two plates (mol/s)

Inner 4.765 0.202 1354.200 0.202 144 0.033 9.404

(stream 3)
Middle 7.842 0.333 2232.500 0.333 240 0.033 9.302
(stream 2)
Outer 10.919 0.464 3110.800 0.464 336 0.032 9.258
(stream 1)
total 23.526 1 6697.500 1 – – –

6.2. Temperature changes within reactors of APW and CR configurations
Temperature profile of the gas through the reactors in the APW and
CR configurations are shown in Fig. 8. As it was mentioned, gas con-
densate formation within the gas-cooled reactor of the CR configuration
is followed by catalyst deactivation and reduction of methanol pro-
duction [10]. As shown in Fig. 8a, in the CR configuration, heat pro-
duction by the exothermic hydrogenation reactions results in tem-
perature increase inside the water-cooled reactor to hit a peak, while,
removing heat from the reaction environment, leads to reduction of
temperature after the peak. In addition, temperature decreases along
the gas-cooled reactor due to the low driving force of forward reactions
and heat transfer from the reaction side to the cooling side (see Fig. 8
(a)). In the APW configuration, as shown in Fig. 8 (b), gas temperature
increases through the adiabatic bed due to the exothermic hydrogena-
tion reactions and the adiabatic condition of the bed. So, it precludes
condensate formation within the adiabatic reactors which has positive
impact on catalyst lifetime and methanol production. One other ad-
vantage of the APW configuration is improvement of the reactions rates
as a result of temperature rise within the adiabatic bed [41]. Therefore,
methanol produced by the APW configuration is greater than the CR
configuration.
It should be noticed that, excessive temperature increase has de-
structive effect on the catalyst structure and also reduces the driving
force of the exothermic reactions (i.e., Eqs. (1) and (3)). Actually,
copper based catalyst should be operated below 573 K to prevent
thermal sintering [54]. In addition, at operating temperature higher
than 555 K, the reverse reactions of carbon dioxide and carbon mon-
oxide hydrogenation take place (see Eqs. (1) and (3)). Therefore, as it
was mentioned in Section 6.1.1, the adiabatic reactor design is opti-
mized to prevent temperature from exceeding 555 K (see Fig. 8 (b)).
As exhibited in Fig. 8 (b), the initial temperature of both adiabatic
reactors of the APW configuration are same at 513 K because a part of
methanol and water are segregated from the gas flow and gas stream is
heated up to 513 K before the second adiabatic reactor. In addition,
temperature increase along the second adiabatic reactor is less than the
first one because a part of feedstock is converted to methanol in the first
adiabatic reactor. Moreover, temperature decreases along the water-

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Fig. 6. Molar flow rate of gas flowing between two plates of inner, middle and outer sections of the water-cooled reactor of the APW configuration.

cooled reactor as a result of removing heat from the reaction side using
cooling plates (see Fig. 8 (b)).
The results in Fig. 8 (b) show that the temperature profiles along the
inner, middle and outer sections of the water-cooled bed in the APW
configuration are identical. Since the flow rate of gas between two
plates of inner section is slightly greater than that of two other sections,
temperature along the inner section is a little greater than middle and
outer sections. Regarding Fig. 8b, the cooling efficiency of the water-
cooled bed of the APW configuration is sufficient as temperature of gas
stream leaving the water-cooled reactor approaches the cooling side
temperature (i.e., 513 K).
In the current research, dew point temperature and temperature of

Fig. 7. Velocity profiles along the inner, middle and outer sections of the water-cooled reactor of the APW configuration.

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Fig. 8. Temperature changes along the reactors of (a) CR configuration, (b) APW configuration.

the gas flowing through the water-cooled reactor of the APW config- the reactor is higher than dew point temperature of the gas stream
uration are estimated and the results are shown in Fig. 9. As shown, gas which precludes formation of condensate and improves catalyst dur-
dew point temperature rises with increasing reactor length due to in- ability [32–36].
crease in the methanol molar flow rate. Obviously, temperature inside

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Fig. 9. Temperature changes and dew point temperature of gas stream flowing through the water-cooled reactor of APW configuration.
6.3. Pressure changes along reactors of CR and APW configurations
The pressure changes of gas streams flowing through the reactors of
the CR and APW configurations are demonstrated in Fig. 10. As shown
in Fig. 10 (b), the small length to diameter ratio of the adiabatic bed
results in small pressure drop of the gas stream [41]. However, the
condenser, separator and heater applied between first and second
adiabatic reactors causes an additional small pressure drop. In addition,
the pressure drop of gas flowing in the water-cooled bed of APW con-
figuration is low due to the large cross section area of the reaction side
(see Fig. 10 (b)). The total pressure drop of the APW configuration is
0.4 bar. On the other hand, the total pressure drop along the reactors of
the CR configuration is 4 bar which is ten times greater than that of the
APW configuration. The less pressure drop along the reactors of the
APW configuration leads to greater methanol production. The reason is
that equilibrium reactions (1) and (3) are carried out in the gas phase
and the summation of stoichiometric coefficients of reactants is greater
than that of products in each of these two reactions. So, regarding the
equilibrium reaction law in the gas phase, higher pressure improves the
tendency of reactions (1) and (3) toward products. Consequently,
comparing to the CR configuration, higher pressure of gas stream inside
the reactors of the APW configuration brings many benefits, e.g. me-
thanol production increase and lower operating cost.
Moreover, it is demonstrated in Fig. 10 (b) that pressure profiles of
inner, middle and outer sections of the water-cooled reactor are iden-
tical because of the same flow rate of gas flowing between two plates of
those sections. However, pressure along the inner section is slightly
greater than that of two other sections due to the less velocity of gas
between two plates of inner section comparing to that of two other
sections (see Figs. 6 and 7).
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6.4. Reactants and products concentration changes along reactors of the
APW and CR configurations
The conversions of CO, CO2, and H2 by the reactors of the CR and
APW configurations are shown in Figs. 11 and 12, respectively. Con-
versions of CO2, CO and H2 are calculated using Eq. (32) to Eq. (34).
FCO2. in − FCO2. out
CO2 conversion (%) = × 100
FCO2. in (32)
FCO . in − FCO . out
CO conversion (%) = × 100
FCO . in (33)
FH2 . in − FH2 . out
H2 conversion (%) = × 100
FH2 . in (34)
In comparison between the APW and CR configurations, CO2 and
CO conversions with the APW configuration is greater than the CR
configuration. Segregating a portion of water and methanol (stream X)
before the second adiabatic reactor improves the driving force of for-
ward hydrogenation reactions. Reaction 1 and reaction 3 show that the
stoichiometric coefficients of the gaseous reactants are greater than the
products in those two hydrogenation reactions. Hence, high pressure of
gas stream flowing within the reactors of the APW configuration com-
paring to the CR configuration has positive effect on driving force of
abovementioned reactions. In addition, high average temperature along
the adiabatic catalyst beds improves the rate of reactions. However,
temperature increase along adiabatic catalyst beds enhances the driving
force of forward RWGS reaction to convert a part of CO2 to CO and then
those components are converted to methanol inside the water-cooled
reactor. In fact, high cooling efficiency and low pressure drop along the
water-cooled reactor of the APW configuration increase the conversions
of CO and CO2 to methanol. In addition to the economic benefit of
increasing methanol production, increase in CO and CO2 conversions to
B. Rahmatmand, et al.
Fig. 10. Pressure changes of gas stream flowing inside the reactors of (a) CR configuration, (b) APW configuration.
methanol is highly beneficial from environmental aspect due to the
harmful effect of such greenhouse gases to the environment [37]. As it
was expected, H2 conversion along APW configuration is higher than
that of CR configuration as a result of higher conversions of CO and
CO2.
Furthermore, optimization of adiabatic reactor dimensions in the
APW configuration results in chemical equilibrium inside that reactor
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as conversions of reactants remain constant at the end of the adiabatic
catalyst bed (see Fig. 12). Therefore, further increase in length of the
adiabatic catalyst bed leads to temperature increase that forces CO and
CO2 hydrogenation reactions to be performed in the reverse direction.
Because CO and CO2 hydrogenation reactions (i.e., Eq. (1) and Eq. (3))
are exothermic reactions in the forward direction. Also, reactants con-
versions within the water-cooled reactor of the APW configuration
B. Rahmatmand, et al. Fuel Processing Technology 193 (2019) 159–179

Fig. 11. CO2, CO and H2 conversions along reactors of the CR configuration.

Fig. 12. CO2, CO and H2 conversions along reactors of the APW configuration.

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remain constant at the end of the reactor (see Fig. 12). The reason is
that temperature profile along the water-cooled reactor in the APW
configuration approaches the constant value at 513 K (i.e., temperature
of the cooling side) at the end of the reactor (see Fig. 8b).
The H2O concentration changes along the reactors of CR and APW
configurations are exhibited in Fig. 13. Although, a part of CO2 is
converted to CO and H2O inside the adiabatic reactors (i.e., Eq. (2)), the
maximum water concentration along the reactors of the APW config-
uration is equal to the maximum value of this parameter inside the
reactors of the CR configuration. Because applying condenser between
first and second adiabatic reactors of the APW configuration reduces
the inlet water mole fraction to the second adiabatic reactor (stream

Fig. 13. H2O concentration changes along reactors of (a) CR configuration, (b) APW configuration.

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B. Rahmatmand, et al.
XI). Water produced within the water-cooled bed of the APW config-
uration is slightly higher than water produced inside the second reactor
of the CR configuration. Because, the greater amount of CO2 is con-
verted to water and methanol (i.e., Eq. (3)) within the water-cooled bed
of the APW configuration due to the high cooling efficiency and low
pressure drop of this reactor. Nevertheless, it is not followed by water
condensation inside this reactor because the minimum achievable
temperature inside the water-cooled reactor is 513 K (i.e., cooling side
temperature) that is much greater than gas flow dew point temperature
(see Fig. 9).
As shown in Fig. 13 (b), the mole fraction of water within the second
adiabatic reactor is greater than that of the first one in the APW con-
figuration. The reason is that total mole flow of gas inside the second
adiabatic reactor is less than the first adiabatic reactor due to separating
a part of methanol and water between the first and second adiabatic
reactors (stream X). As a result, the mole fraction of water (i.e., the ratio
of water mole flow to the total mole flow of gas) within the second
adiabatic reactor is greater than the first adiabatic reactor.
Flow rate of methanol produced by reactors of the CR configuration
is demonstrated in Fig. 14. As shown, the flow rate of methanol in-
creases along the reactors because of heat removal from the reaction
side inside the water-cooled and gas-cooled reactors. In addition, the
molar flow rate of methanol along the catalyst bed of the adiabatic
reactor and water-cooled reactor of the APW configuration are pre-
sented in Fig. 15. As shown in Fig. 15 (a), the flow rate of methanol
produced along the adiabatic reactor catalyst bed in the APW config-
uration increases due to the positive effect of temperature increase on
methanol synthesis reactions rates. Furthermore, the methanol molar
flow rate approaches the maximum constant value at the end of the
adiabatic catalyst bed. The reason is that the adiabatic reactor design is
optimized to prevent temperature from exceeding the onset tempera-
ture of the reverse CO and CO2 hydrogenation reactions. Also, the
methanol produced by the first adiabatic reactor is greater than the
Fig. 14. Methanol molar flow produced along the reactors of the CR configuration.
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second adiabatic reactor in the APW configuration because of the
higher driving force of the reactions inside the first reactor than the
second one as a result of the greater inlet flow to the first reactor
(stream I) comparing to the second reactor (stream XI).
Furthermore, as exhibited in Fig. 15 (b), flow rate of methanol in-
creases along the water-cooled reactor of the APW configuration be-
cause of heat removal from the reaction side and finally it approaches a
constant value as the gas flow temperature approaches cooling side
temperature at the end of the water-cooled catalyst bed. Also, the
methanol molar flow rates within three sections of the water-cooled bed
increase in the order of outer section > middle section > inner sec-
tion. The reason is that the inlet gas flow rate to the outer section
(stream 1) is greater than that of two other sections (streams 2 and 3)
(see Table 9).
The total methanol molar flow rate produced by the reactors of the
APW and CR configurations is shown in Fig. 16. As exhibited, in the
APW configuration, the greatest amount of methanol is produced by the
first adiabatic reactor due to the greatest inlet flow to this reactor
(stream I). Moreover, the APW configuration increases methanol pro-
duction by 12.2% comparing to the CR configuration. Segregating a
portion of methanol between two adiabatic reactors and temperature
increase along the adiabatic reactors improve the driving force and rate
of methanol synthesis reactions, respectively. Also, high cooling effi-
ciency of the water-cooled bed of the APW configuration contributes to
improving methanol production by exothermic reactions (1) and (3). In
addition, low pressure drop along the reactors of the APW configuration
increases the driving force of hydrogenation reactions in the forward
direction (i.e., Eqs. (1) and (3)) to produce methanol. It should be no-
ticed that the CR configuration faces the condensate formation draw-
back inside the gas-cooled reactor which results in decreasing the ef-
ficiency of the main reactions as well as the reactor performance [9,10].
Therefore, in the absence of the gas-cooled reactor, methanol produc-
tion by the APW configuration is 68% greater than that of the CR
B. Rahmatmand, et al. Fuel Processing Technology 193 (2019) 159–179

Table 10
The composition of the APW configuration product streams.
Parameters Stream X Stream IX
(Liquid product of the first (Liquid product of the
condenser) second condenser)

Molar flow (kmol/h) 3549 4752

Temperature (K) 317 331
Mole ratio
H2O 0.2062 0.1773
CH4 0.0031 0.0051
CO 0.0007 0.0003
H2 0.0017 0.0022
CO2 0.0306 0.0286
CH3OH 0.7556 0.7834
N2 0.0021 0.0029

configuration. Also, the APW configuration does not face the con-
densate formation drawback as a results of temperature increase along
the adiabatic reactors. Moreover, pressure drop along the reactors of
the APW configuration is one tenth of the CR configuration. Obviously,
less pressure drop is one of the major aspirations of methanol synthesis
reactors design as it results in reducing overall cost of the plant, as well
as reducing compression duty of overhead streams.
The composition of the methanol streams produced by the APW
configuration (streams IX and X) is shown in Table 10. As shown,
streams X and IX mainly consist of methanol and water which shows the
product streams are of high methanol purity. Furthermore, a small
amount of CO2 and CO is released to the atmosphere as the great
portion of the gaseous stream leaving the condenser (purge gas) returns
to the process to be converted to methanol.
Furthermore, the effect of feed composition (stream I) on methanol
production by the APW configuration is demonstrated in Fig. 17. In
order to investigate CO and CO2 concentrations effect on methanol
production, various molar ratios of CO to CO2 have been considered
(i.e. from 0 to 10). As shown, methanol production increases by in-
creasing the CO to CO2 molar ratio. Because enthalpy of the CO2 hy-
drogenation reaction is less than that of the CO hydrogenation reaction.
Thus, increasing the CO to CO2 molar ratio contributes to improving
temperature along the methanol synthesis reactors which improves
rates of reactions.
Fig. 15. Methanol molar flow rate profile along (a) adiabatic, and (b) water-
cooled reactors of the APW configuration.

Fig. 16. Total flow of methanol produced by the APW and CR configurations.

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Fig. 17. The effect of the CO to CO2 molar ratio on methanol production by the
APW configuration.
6.5. Heat integration
In the APW configuration, energy is required for cooling by the
condensers and heating by the heater located before the second adia-
batic reactor. While, in the CR configuration, energy is needed for
cooling the product stream leaving the gas-cooled reactor to condense
methanol and water. Energy consumption by the APW and CR config-
urations is compared in Fig. 18 (a) in which Qh and Qc are energy re-
quired for heating and cooling in the APW configuration respectively.
Moreover, energy consumption by the CR configuration is shown by
QCR in Fig. 18 (a). Therefore, energy consumption by the APW con-
figuration is greater than the CR configuration.
In order to reduce energy consumption by the APW configuration, a
method of saving energy is carried out which is shown in Fig. 18 (b). In
this process, energy required for heating is supplied by energy released
by cooling [9]. For this purpose, heat is absorbed from the reaction side
of the water-cooled bed by boiling water which is converted to steam
within plates and then steam is separated from water in the drum to be
sent to the utility unit. The product stream leaving the first adiabatic
reactor at 555 K is separated to two streams (i.e., the molar flow ratio of
those two streams is 0.6 to 0.4) to heat up cold streams. Afterward, the
stream with the larger flow rate enters a heat-exchanger to heat up a
stream from 483 K to 513 K and then it leaves the heat-exchanger at
510 K to be mixed with a stream at 555 K to make a stream at 529 K.
The stream at 529 K is applied to heat up the recycle stream from 363 K
to 513 K and then the hot stream leaves the heat-exchanger at 419 K.
This stream needs to be further cooled to 316 K using boiling water and
sea water to separate its methanol and water (stream X) from the gas-
eous stream (i.e., purge gas at 316 K located at the top of the flow
diagram). The gaseous stream at 316 K is heated up to 467 k using the
hot stream leaving the water-cooled reactor at 513 K and the hot stream
is cooled to 318 k. Moreover, the stream leaving the heat-exchanger at
467 K is heated up to 483 k by cooling down the stream leaving the
water-cooled reactor at 513 K to 482 K. The stream that leaves the heat-
exchanger at 483 K is heated up to 513 K as mentioned before to enter
the second adiabatic reactor as the feedstock. The product stream at
550 K exits the second adiabatic reactor to enter the water-cooled re-
actors. Furthermore, the stream at 482 K is further cooled to 343 K
using boiling water and sea water and then it is added to the stream at
318 k to create a stream at 331 K that is partially condensed. Therefore,
methanol and water (stream IX) are separated from the gaseous stream
(i.e., purge gas located at the bottom of the flow diagram) at 331 k. A
part of these gaseous stream (i.e., around 95%) is recycled and reused
as the feed of the first adiabatic reactor and the rest is used as the flare
gas. The gaseous stream at 331 K, in other words the recycle stream, is
177
Fuel Processing Technology 193 (2019) 159–179
heated up to 363 K using boiling water and then it is heated up to 513 K.
Finally, the fresh feed stream is added up to the recycle stream at 513 K
to create the feedstock of the first adiabatic reactor. Thus, although the
APW configuration requires more energy comparing to the CR config-
uration, the total energy requirement for the APW configuration is
provided by the self-heat recuperation method. Consequently, the APW
configuration is an energy efficient process that increases methanol
production comparing to the CR configuration in addition to over-
coming the methanol condensation drawback.
7. Conclusion
In the present investigation, a novel configuration called APW is
represented to eliminate the drawback of the CR configuration.
According to the problems associated with CR configuration, con-
densate is formed within the gas-cooled reactor as a result of unsuitable
distribution of flow and temperature within the shell of the gas-cooled
reactor followed by catalyst loss and efficiency reduction [10]. In the
APW configuration, the gas-cooled reactor has been replaced with two
adiabatic reactors. Also, the separator and condenser are located be-
tween the adiabatic reactors. In addition, water-cooled reactor design is
a plate heat exchanger which consists of three sections with different
number of plates. In the current research, water-cooled reactor design
and also the molar flow of inlet streams to the water-cooled reactor are
optimized to achieve the same pressure, temperature and gas velocity
profiles along three sections of the water-cooled reactor. Moreover,
adiabatic reactor design is optimized to prevent temperature from ex-
ceeding the onset temperature of CO and CO2 hydrogenation reverse
reactions and also to reduce the pressure drop along the catalyst bed.
According to the design of the APW configuration in which the gas-
cooled reactor has been replaced with two adiabatic reactors, methanol
and water are not condensed inside the adiabatic reactors because of
temperature increase along those reactors. Also, the modeling results
indicate that CO and CO2 conversions by the APW configuration are
greater than the CR configuration. In fact, separating a portion of water
and methanol between the first and second adiabatic reactors improves
conversion of hydrogenation forward reactions (i.e., Eqs. (1) and (3)).
Moreover, the small length to cross section ratio of the adiabatic cata-
lyst beds results in low pressure drop along the adiabatic reactors which
has positive impact on conversions of hydrogenation reactions in the
forward direction. Also, high temperature within the adiabatic beds
plays a significant role in increasing the rates of reactions. However,
temperature increase along adiabatic catalyst beds enhances the con-
version of RWGS forward reaction to convert a part of CO2 to CO and
then those components are converted to methanol within the water-
cooled reactor. In addition, high cooling efficiency and low pressure
drop along the water-cooled bed of the APW configuration contribute to
increase in conversions of CO, CO2 and H2 to methanol which is highly
beneficial from the economic perspective. Therefore, pressure drop
along reactors of the APW configuration is less than that of the CR
configuration. Obviously, low pressure drop is one of the major as-
pirations of methanol synthesis reactors design as it results in less
compression duty [5]. In addition, unreacted CO and CO2 are recycled
and reused as the feed of the methanol synthesis reactors to improve
methanol productivity. Also, from an environmental standpoint, re-
cycling unreacted CO and CO2 contributes to preventing greenhouse gas
emissions. Thus, the APW configuration improves CO2 and H2 conver-
sions 57% and 37% comparing to the CR configuration, respectively. In
terms of the feed composition effect, increasing the CO to CO2 molar
ratio in the feed stream results in improving methanol production as
enthalpy of the CO hydrogenation reaction is greater than that of the
CO2 hydrogenation reaction. Although the APW configuration requires
more energy rather than the CR configuration, the total energy re-
quirement for the APW configuration is provided using the energy
saving method. In this method, energy required to heat up cold streams
is provided by energy released through cooling of hot streams that need
B. Rahmatmand, et al. Fuel Processing Technology 193 (2019) 159–179

Fig. 18. (a) Comparison of energy consumption by the APW and CR configurations, (b) the schematic diagram of the APW configuration heating process.

to get cool. Thus, no more energy is required to be supplied from
outside of the process, while, methanol produced by the APW config-
uration increases 12.2% comparing to the conventional process. Con-
sequently, the APW configuration brings some benefits including
overcoming the condensate formation drawback and catalyst deacti-
vation, less pressure drop, improving reactions rates as a result of high
temperature within the adiabatic reactors, the higher cooling efficiency
of the water-cooled reactor, improving CO2 and H2 conversions to
methanol, preventing greenhouse gas emissions, and improving
methanol production without increase in energy consumption of the
process as the energy requirement for the APW configuration is pro-
vided by the self-heat recuperation method.
Funding sources
This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors.

178
B. Rahmatmand, et al.
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