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Reaktor, Vol. 19 No. 3, September Year 2019, pp. 131-135

Simulation of CO2 Conversion into Methanol in Fixed-bed Reactors:

Comparison of Isothermal and Adiabatic Configurations

Fadilla Noor Rahma *)

Department of Chemical Engineering, Faculty of Industrial Technology

Universitas Islam Indonesia, Yogyakarta 55584, INDONESIA
Phone: (+62274) 895287

*) Corresponding author: [email protected]

(Received: September 23, 2019 Accepted: October 25, 2019)

Abstract

CO2 capture and utilization (CCU) has been widely considered as a potential solution to overcome global warming.
Conversion of CO2 into methanol is an interesting option to transform waste into value-added chemical while also
reducing greenhouse gases emissions in the atmosphere. In this paper, utilization of CO2 into methanol was simulated
using Aspen Plus software. The reaction between CO2 and H2 to produce methanol and water was carried out in a
simulated fixed-bed reactor with Cu/ZnO/Al2O3 commercial catalyst, following LHHW (Langmuir – Hinshelwood –
Hougen – Watson) kinetic model. Isothermal and adiabatic reactor configurations were compared under similar feed
conditions and the concentration profile along the reactor was observed. The result showed that isothermal
configuration converted 3.23% more CO2 and provided 16.34% higher methanol yield compared to the adiabatic
reactor. Feed inlet temperature variation was applied and the effect to methanol production on both configurations
was studied. The highest methanol yield for adiabatic and isothermal reactor was obtained at 200 oC and 240 oC
respectively.

Keywords: Aspen Plus simulation; carbon capture and utilization; CO2 hydrogenation; methanol reactor

How to Cite This Article: Rahma, F.N. (2019), Simulation of CO2 Conversion into Methanol in Fixed-bed Reactors:
Comparison of Isothermal and Adiabatic Configurations, Reaktor, 19(3), 131-135,
http://dx.doi.org/10.14710/reaktor.19.3.131-135.

INTRODUCTION
The awareness of global warming issue has to IEA (2012), the 2 oC target can be achieved given
driven rigorous mitigation actions worldwide. that the atmospheric CO2 concentration is kept at 450
Evidences suggested that CO2 gives over 60% ppm, which means that 43 Gt of CO2 should be
contributions to global warming due to its huge reduced. Mitigation strategies have been implemented
emission which exceeds 30 Gt a year (IEA, 2012). to reach this goal, including energy efficiency
Copenhagen Accord has requested that by 2100, the improvement, utilization of low-carbon fuels, and
global temperature raise should be limited to 2 oC above replacement of fossil fuel with renewable energy
pre-industrial level (Huang and Tan, 2014). According sources (Leung et al., 2014). However, the majority of

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Simulation of CO2 Conversion into Methanol in … (Rahma, F.N.)

the world is still predicted to depend on fossil fuels for field. Several studies have discussed about CO2
the next couple of decades (Kenarsari et al., 2013). hydrogenation into methanol in catalytic reactors (Van
Carbon capture and storage (CCS) is often der Ham et al., 2012; Tidona et al., 2013, Milani et al.,
considered as a potential solution for reducing CO2 2015). However, none of them provided a comparison
emissions while fossil fuel is still utilized as the main between different reactor configurations. This study
energy source. This technology involves capturing CO2 provides new information by comparing adiabatic and
from the large point emission sources and injecting it to isothermal reactor configurations in methanol
underground and ocean storage. According to production from CO2.
Haszeldine (2009), CCS has the potential to reduce
20% of world energy emissions in the future. However, RESEARCH METHOD
public concern regarding the safety of the storage sites The reaction between CO2 and H2 to produce
has shifted the attention to CO2 utilization instead of methanol was carried out in a simulated fixed-bed
storage. CO2 capture and utilization (CCU) is reactor with Cu/ZnO/Al2O3 catalyst. The rate equation
increasingly becoming more popular as it also gives follows LHHW (Langmuir – Hinshelwood – Hougen –
additional value to the captured CO2 (Huang and Tan, Watson) kinetic model including three independent
2014). reactions occurring in parallel:
Among the various CO2 utilization pathways,
CO(g) + 2H2(g) ↔ CH3OH(l)
CO2 conversion into methanol is an interesting option
ΔH = -128 kJ/mol (298 K) (1)
which produces a chemical with wide application in
industries. Methanol is conventionally produced from
CO2(g) + 3H2(g) ↔ CH3OH(l) + H2O(g)
synthesis gas (a mixture of CO, CO2, and H2) via
ΔH = -87 kJ/mol (298 K) (2)
catalytic conversion. Most of synthesis gas produced
today comes from natural gas, making conventional
CO2(g) + H2(g) ↔ CO(g) + H2O(g)
methanol production another fossil fuel dependent
ΔH = +41 kJ/mol (298 K) (3)
process. According to Van-Dal and Bouallou (2013),
around 29 to 33 GJ of natural gas is consumed to
Reaction (1) and (2) are exothermic reactions
produce one metric ton of methanol. This number can
which produce methanol, while reaction (3) is
be significantly reduced by switching to the captured
endothermic Reverse Water Gas Shift (RWGS)
CO2 from carbon capture technology.
reaction. Aspen Plus software requires kinetic
Methanol is characterized by its excellent
equations to be arranged in certain form. For this
combustion properties, making it a strong candidate for
reason, Van Dal and Bouallou (2013) has proposed a
alternative vehicles fuel. Although the energy density
kinetic model for reactions (1) to (3) and calculated the
is only half compared to that of gasoline, it produces
parameters which match Aspen Plus specifications.
less pollution compared to conventional fossil fuels
The kinetic rate equations are shown in equation (4) and
(Van-Dal and Bouallou, 2013). Methanol can be used
(5), and the kinetic parameters are displayed in Table 1.
as an additive to gasoline or in its pure form, although
the latter one possesses a toxicity hazard which restricts 𝑘1 𝑃𝐶𝑂2 𝑃𝐻2 − 𝑘6 𝑃𝐻2𝑂 𝑃𝐶𝐻3𝑂𝐻 𝑃H2 −2
its use as vehicle fuel. Another scenario is to dehydrate 𝑟𝐶𝐻3𝑂𝐻 = (4)
(1 + 𝑘2 𝑃𝐻2𝑂 𝑃H2 −1 + 𝑘3 𝑃H2 0.5 + 𝑘4 𝑃𝐻2𝑂)3
methanol, producing DME (dimethyl ether) that can be
used to substitute conventional diesel. Therefore, 𝑘5 𝑃𝐶𝑂2 − 𝑘7 𝑃𝐻2𝑂 𝑃𝐶𝑂 𝑃H2 −1
𝑟𝑅𝑊𝐺𝑆 = 1 + 𝑘 −1 + 𝑘 𝑃 0.5 + 𝑘 𝑃 (5)
conversion of captured CO2 into methanol will allow 2 𝑃𝐻2𝑂 𝑃H2 3 H2 4 𝐻2𝑂

CO2 recycle, reduce the amount of CO2 released to the 𝐵𝑖

ln 𝑘𝑖 = 𝐴𝑖 + (6)
atmosphere, and cut down the amount of fossil fuel 𝑇

consumption in the future. Table 1. Parameters of the LHHW Kinetic Model

According to Chen et al. (2011), one of the key (Van Dal and Bouallou, 2013)
parts in methanol production is the methanol synthesis Parameters Value
reactor. The reactors existing in conventional methanol A1 -29.87
production plants generally can be classified into k1
B1 4,811.2
adiabatic and isothermal reactor. This paper intends to A2 8.147
explore the performance of CO2 conversion into k2
B2 0
methanol in both reactor types under similar feed A3 -6.452
condition. Aspen Plus software was employed to k3
B3 2,068.4
simulate the reactors, where the captured CO2 is reacted A4 -34.95
with hydrogen to produce methanol. The concentration k4
B4 14,928.9
profile along the reactor was observed, and the feed A5 4.804
inlet temperature was varied to determine its effect on k5
B5 -11,797.5
methanol production. A6 17.55
Even though commercial methanol production k6
B6 -2,249.8
has been established since early 1900s, methanol A7 0.1310
generation from captured CO2 is still relative new in the k7
B7 -7,023.5

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Table 2. Properties of the feed stream

Properties Value
Mass flow (kg/s) 2.8 x 10-5
Pressure (bar) 50
Temperature (oC) 220
Composition (% molar)
CO 4.00
CO2 3.00
H2O 0.00
Methanol 0.00
H2 82.00
Argon 11.00

Table 3. Properties of the catalyst Figure 1. Molar Fraction of Reactants and Products
Catalyst along Adiabatic Reactor
Density (kg/m3) 1775
Fixed bed porosity 0.5 methanol at this point. To explain this drop of methanol
Mass (g) 34.8 production, it should be noted that methanol is
generated via reversible exothermic reaction (1) and
Table 4. Reactor configuration (2), which benefits from low temperature. High
Reactor Configuration temperature shifts the equilibrium to the left, therefore
Tube diameter (m) 0.016 promoting deformation of the methanol. A quick check
Length (m) 0.15 at the temperature profile (Figure 2) shows a significant
temperature rise at the beginning of the adiabatic
Properties of the feed stream, catalyst, and reactor, caused by the heat released from the
reactor configurations are displayed in Table 2, 3, and exothermic reactions. In adiabatic configuration, this
4 respectively (Van Dal and Bouallou, 2013). These released heat accumulates inside the reactor, as there is
data was based on their adiabatic reactor simulation, no cooling system available to take the heat out of the
which then becomes the base case simulation in this reactor. Consequently, the temperature increase
study. The results obtained from our base case inhibits the exothermic reactions and eventually
simulation were compared to Van Dal and Bouallou’s suppresses the methanol production. As the exothermic
result in order to ensure validity of our simulation. reaction dwindles, the heat production decreases,
The validated model was then employed to causing the temperature to level off as illustrated on
simulate isothermal reactor configuration using similar Figure 2.
feed, catalyst, and reactor condition. The obtained In contrary to the adiabatic trends, the methanol
result was analysed in comparison with the base case molar fraction consistently increases through the length
adiabatic reactor. Lastly, temperature variation was of the isothermal reactor (Figure 3), which is an
simulated on both adiabatic and isothermal advantage of having constant temperature along the
configurations by changing the feed temperature reactor. The constant temperature can be achieved by
entering the reactors. providing a cooling system which takes out the heat
produced from the exothermic reaction, keeping the
RESULTS AND DISCUSSIONS temperature constant. This maintains the reaction
This study conducted reactor simulations by equilibrium in favour of the methanol production,
employing reaction conditions and rate equation similar eventually leading to a higher methanol yield at the end
to the previous work by Van Dal and Bouallou (2013). of the isothermal reactor. The methanol concentration
Therefore, the first thing to check was the validity of
the simulation result compared to their work. Figure 1,
which describes molar fractions of the species in the
adiabatic reactor, shows a strong resemblance with the
profile obtained by Van Dal and Bouallou. This
indicates the validity of the model used this study, and
confirms that it can be used for other simulations of the
methanol reactor.
The molar fractions of CO2, CO, H2O, and
methanol as the reaction progresses along the adiabatic
reactor are plotted on Figure 1. The graph shows a steep
increase of methanol molar fraction at the first 0.02 m
of the reactor. However, the methanol molar fraction
levels off at the remaining length of the reactor,
indicating that the reactions no longer produce Figure 2. Temperature Profile along Adiabatic Reactor

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Simulation of CO2 Conversion into Methanol in … (Rahma, F.N.)

Figure 3. Molar Fraction of Reactants and Products Figure 5. Feed Temperature Effect on Temperature
along Isothermal Reactor Profile in Adiabatic Reactor

is 16.34% higher and CO2 conversion being 3.23% shifting the equilibrium even more to the left side and
more compared to those of adiabatic reactor. This result causing methanol production to diminish faster. This
demonstrates the advantage of using isothermal theory is confirmed by the adiabatic temperature profile
configuration for CO2 conversion to methanol. It is also as shown on Figure 5, where the reactor temperature
worth noting that methanol production in isothermal reaches above 260 oC for all feed temperature variation.
reactor does not level off until the end of the reactor In the isothermal reactor, as displayed on Figure
length, indicating possibility of obtaining even higher 6, the effect of the temperature rise is quite the opposite:
methanol yield when the length of the reactor is added. although high temperature shifts the methanol
According to Chen et al. (2011), temperature production equilibrium to the left, it is compensated by
profile is a significant factor contributing to the the promotion of methanol production rate. Moreover,
operation of methanol synthesis reactor. Among other the reaction equilibrium can be maintained along the
factors that can influence the temperature profile, inlet reactor as the cooling system keeps the temperature
feed temperature is considerably easy to modify. constant. The overall result is the higher methanol
Therefore, the effect of inlet feed temperature on molar fraction as the feed temperature is increased. This
methanol production was also observed in this study. explanation applies for feed temperature of 200, 220,
Temperature variation of 200, 220, 240, and 260 oC was and 240 oC. However, when the feed temperature is
employed on the adiabatic and isothermal reactors, increased to 260 oC, the higher reaction rate can no
resulting in Figure 4 and Figure 5 respectively. longer compensate the shifted equilibrium, causing the
Figure 4 shows how feed temperature affects methanol production to drop.
methanol production in the adiabatic reactor. It clearly In summary, the effect of feed inlet temperature
indicates that as the feed temperature goes up, the on methanol molar fraction is presented on Figure 7.
methanol production decreases, and the reaction rate The highest methanol production was obtained using
levels off at shorter reactor length. In this case, similar isothermal reactor at feed temperature of 240 oC. At the
explanation as the previous simulation applies: high lowest feed temperature of 200 oC, methanol
temperature inhibits the exothermic reaction. As the production in adiabatic reactor is higher than
adiabatic configuration does not take out any heat isothermal reactor; however it decreases as the feed
produced in the reaction, a higher feed temperature
means even higher temperature along the reactor,

Figure 6. Feed Temperature Effect on Methanol

’ Figure 4. Feed Temperature Effect on Methanol Production in Isothermal Reactor
Production in Adiabatic Reactor

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component i
T Temperature K

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