Acta Scientiarum

http://www.uem.br/acta
ISSN printed: 1806-2563
ISSN on-line: 1807-8664
Doi: 10.4025/actascitechnol.v36i2.18850

Modeling and simulation of an isothermal reactor for methanol

steam reforming
Raphael Menechini Neto, Onelia Aparecida Andreo dos Santos and Luiz Mario de Matos Jorge*

Departmento de Engenharia Química, Universidade Estadual de Maringá, Av. Colombo 5790, 87020-900, Maringá, Paraná, Brazil. *Author for
correspondence. E-mail: lmmj@deq.uem.br

ABSTRACT. Due to growing electricity demand, cheap renewable energy sources are needed. Fuel cells
are an interesting alternative for generating electricity since they use hydrogen as their main fuel and release
only water and heat to the environment. Although fuel cells show great flexibility in size and operating
temperature (some models even operate at low temperatures), the technology has the drawback for
hydrogen transportation and storage. However, hydrogen may be produced from methanol steam
reforming obtained from renewable sources such as biomass. The use of methanol as raw material in
hydrogen production process by steam reforming is highly interesting owing to the fact that alcohol has the
best hydrogen carbon-1 ratio (4:1) and may be processed at low temperatures and atmospheric pressures.
They are features which are desirable for its use in autonomous fuel cells. Current research develops a
mathematical model of an isothermal methanol steam reforming reactor and validates it against
experimental data from the literature. The mathematical model was solved numerically by MATLAB® and
the comparison of its predictions for different experimental conditions indicated that the developed model
and the methodology for its numerical solution were adequate. Further, a preliminary analysis was
undertaken on methanol steam reforming reactor project for autonomous fuel cell.
Keywords: mathematical modelling, methanol, steam reforming, hydrogen.

Modelagem e simulação de um reator isotérmico de reforma a vapor de metanol

RESUMO. A demanda por energia elétrica é crescente e fontes baratas e renováveis de energia são
necessárias, com este propósito as células a combustível são uma alternativa interessante para a geração de
energia elétrica, pois utilizam hidrogênio como principal combustível e apenas liberam água e calor ao meio
ambiente. As células a combustível apresentam grande flexibilidade quanto ao seu tamanho e também
quanto a sua temperatura de operação sendo que alguns modelos operam a baixas temperaturas, porém essa
tecnologia esbarra na necessidade de transporte e armazenamento do seu principal combustível: o
hidrogênio. No entanto, o hidrogênio pode ser produzido a partir da reação de reforma a vapor de
metanol, o qual pode ser obtido a partir de fontes renováveis como a biomassa. A utilização do metanol
como matéria-prima no processo de reforma a vapor para produção de hidrogênio é muito interessante,
pois este álcool é o que apresenta a melhor proporção entre hidrogênio e carbono (4:1), além de poder ser
processado a baixas temperaturas e pressão atmosférica o que é desejável na utilização em célula autônoma a
combustível. Neste contexto, o objetivo desse trabalho foi desenvolver um modelo matemático de um
reator isotérmico de reforma a vapor de metanol e convalidá-lo frente a dados experimentais de literatura.
O modelo matemático proposto foi resolvido numericamente no MATLAB® e as comparações das suas
previsões em diversas condições experimentais indicam que tanto o modelo desenvolvido como a
metodologia empregada para a sua solução numérica foram adequados. Adicionalmente é feita uma análise
preliminar sobre o projeto de reatores de reforma a vapor de metanol para células autônomas a
combustível.
Palavras-chave: modelagem matemática, metanol, reforma a vapor, hidrogênio.

Introduction the hydrogen-oxygen reaction. However, the

Hydrogen is not only widely used in chemical production, transportation and storage of hydrogen
industry but has been underscored as a promising increase the cost of this technology and hinder its
energy source owing to the increasing search for availability (KIM; KWON, 1998; OUZOUNIDOU
renewable energy sources necessary for the et al., 2009; PETERS et al., 2000).
development of human society. Hydrogen may be An alternative to difficulties presented by the
used as fuel in fuel cells which produce electricity from direct use of hydrogen is the use of a less reactive
Acta Scientiarum. Technology Maringá, v. 36, n. 2, p. 295-301, Apr.-June, 2014
296 Menechini Neto et al.

precursor source of hydrogen that may be easily kinetic equations and data presented by Purnama
stored. Methanol has been widely studied as a et al. (2004) and validates the model by experimental
source of hydrogen and it has been shown to be an data from the literature.
attractive alternative, as hydrogen is made available
via steam reforming reaction. Methyl alcohol with Material and methods
its high concentration of hydrogen (4 hydrogen Research by Purnama et al. (2004), which
atoms for each carbon atom) may be obtained from demonstrated methanol steam reforming at
biomass. It may therefore be characterizes as a atmospheric pressure in a tubular stainless steel
biofuel. Methanol steam reforming reaction is very reactor (10 mm i.d.), was the main source for the
convenient for hydrogen production since it occurs development of current study. The commercial
at relatively low temperatures (200-350°C) when catalyst used by Purnama et al. (2004) in all
compared with other reform reactions. Further, it experiments consisted of CuO/ZnO/Al2O3 with a
exhibits good conversion at atmospheric pressure copper mass fraction of approximately 50%. The
reactor was placed in an aluminium heating block
warranting its use as a source of hydrogen for
with six 125W cartridge heaters for better heat
autonomous fuel cells, especially on a small scale.
transfer. The reactor temperature was adjusted by a
Methanol steam reforming is the chemical reaction PID controller connected to the cartridge heaters.
of water and methanol in the presence of a catalyst, Two type J thermocouples (Fe versus
usually CuO, ZnO and Al2O3 (JONES et al., 2008). (Cu+43%Ni)) were used, or rather, one was placed
The reaction produces hydrogen, carbon dioxide, in the aluminium block and the other in the catalyst
water and carbon monoxide. However, the presence bed. Purnama et al. (2004) used a stainless steel grid
of carbon monoxide in the reactor production to support the catalyst. For gas flow conditioning,
stream is an obstacle to the direct use of the inert Pyrex® beads with the same size as the catalyst
hydrogen from the reactor by the fuel cell, as carbon were placed on top of and below the catalyst bed.
monoxide is a contaminant to the fuel cell anode In their studies Purnama et al. (2004) used the
(NARUSAWA et al., 2003; TRIMM, 2005). The mechanism of methanol steam reforming taking
poisoning of the platinum anode of the fuel cell into consideration two reactions, namely, the steam
impairs and in some cases impedes its operation reforming reaction (SR), Equation 1, and the reverse
(FISHTIK et al., 2000; PEÑA et al., 1996; water-gas shift reaction (WGS), Equation 2.
According to the above kinetic model, CO
TAKEZAWA; IWAZA, 1997).
production occurred as a side product due to the
Modelling and simulation are powerful tools in
the analysis and synthesis of autonomous systems of water-gas shift reaction (AGRELL et al., 2002;
electricity production using fuel cells coupled to BREEN; ROSS, 1999; JIANG et al., 1993;
reforming reactors. The development of a LEDJEFF-HEY et al., 1998; PEPPLEY et al., 1999;
mathematical model that represents the process of PETERS et al., 2000; WIESE et al., 1999).
methanol steam reforming in a fixed bed reactor is a
k1
key step in the design of an autonomous fuel cell. CH 3 OH  H 2 O
k 1
3 H 2  CO 2 (1)
This is due to the possibility of achieving rapid
results that provide time and resource savings and k2

studying different operating conditions that CO 2  H2 CO  H 2 O (2)

k 2

minimize CO production (AVCI et al., 2001;

LENZI et al., 2010; SHAHROKHI; From the treatment of experimental data,
BAGHMISHEH, 2005). Purnama et al. (2004) assumed that the kinetic
An important development of a mathematical equation of methanol steam reforming could be
model is its validation by experimentally obtained approximated by a power law equation and that the
data. It is thus possible to design a system capable of water-gas shift reaction was elementary, thus
feeding an autonomous fuel cell from a methanol obtaining kinetic equations 3 and 4, where: rSR is the
steam reforming reactor and to evaluate optimum SR reaction rate; rrWGS is the reverse WGS reaction
operating conditions (IPSAKIS et al., 2012; rate; k1 is the SR reaction rate constant; k2 is the
SECANELL et al., 2011; WANG; WANG, 2008; direct WGS reaction rate constant; k-2 is the reverse
ZERVAS et al., 2008). WGS reaction rate constant, and PCH3OH, PCO, PCO2,
Current research develops a simple and realistic PH2O, and PH2 are the partial pressures of methanol,
mathematical model of an isothermal methanol carbon monoxide, carbon dioxide, water and
reforming reactor using an industrial catalyst and the hydrogen, respectively.
Acta Scientiarum. Technology Maringá, v. 36, n. 2, p. 295-301, Apr.-June, 2014
Isothermal reactor for methanol steam reforming 297

rSR  k1PCH 3OH PH 2 O

0.6 0.4 dFH 2
(3)  3  rSR  rrWGS   Ac  b (7)
dZ
dFCO2
rrWGS  k2 PCO2 PH 2  k 2 PH 2 O PCO (4)  rSR  rrWGS   Ac  b (8)
dZ
The reaction enthalpies ΔHo298 for the SR
dFCO
reaction and for the reverse WGS reaction are +49  rrWGS  Ac  b (9)
dZ
and +41 kJ mol-1; the reaction entropies are +177
and +42 kJ mol-1; and the Gibbs free energies ΔGo298
In these equations, FCH3OH, FH2O, FH2, FCO2, and
are -3.8 and +28.6 kJ mol-1, respectively (ATKINS,
FCO were the molar fractions of methanol, water,
1987).
hydrogen, carbon dioxide and carbon monoxide;
The kinetic parameters of the methanol steam
Z was the reactor length; Ac was the cross-sectional
reforming reaction obtained by Purnama et al.
area; ρb was the catalytic bed density.
(2004) were 76 kJ mol-1 and 8.8 x 108 s-1gcat-1 for
The partial pressure of CH3OH, H20, H2, CO2
apparent activation energy and pre-exponential and CO was obtained by Equation (10)
factor, respectively. The kinetic parameters of the
reverse water-gas shift reaction were 108 kJ mol-1
pi  xi  P (10)
and 6.5 x 109 bar-1 s-1 gcat-1 for apparent activation
energy and pre-exponential factor, respectively.
where pi, was the partial pressure to component i; xi
The same kinetic mechanism for Equations 3
was mole fraction of component i in the mixture of
and 4 was adopted in current assay for the
gas; P was total pressure.
development of the mathematical model of the
The bulk density ρb comprised the porosity of
methanol steam reforming reactor in a fixed bed.
the material and represented the catalyst mass that
The mathematical model used a pseudo-
filled a unit volume of the reactor. In this case, the
homogeneous, one-dimensional approach, without
bulk density was calculated from the rates of particle
axial dispersion. It consisted of five differential
density (ρp ) of the industrial CuO/ZnO/Al2O3
equations (Equations 5 to 9) obtained from
catalyst and bed porosity ( ), using Equation 11 to
component mass balances (for CH3OH, H2O, H2,
CO2 and CO) in a differential volume element of obtain a rate of 1426.55 kg m-3 used in the
the reactor. simulations.

dFCH 3OH b   p (1   ) (11)

 rSR  Ac  b (5)
dZ
The mathematical model represented by
dFH 2O Equations 1 - 8 was numerically solved with solver
 rrWGS  rSR   Ac  b (6) ODE23TB from software MATLAB®. Figure 1
dZ shows the flowchart of the simulation routine.

Figure 1. Flowchart for the solution of the developed mathematical model using MATLAB.

Acta Scientiarum. Technology Maringá, v. 36, n. 2, p. 295-301, Apr.-June, 2014

298 Menechini Neto et al.

Results and discussion duly adjusted and represented the process´s main
trends. It may be observed that only the partial
Figures 2 to 5 illustrate the simulation results of the
pressures of H2 at 230oC (Figure 2) could not be well
mathematical model compared with the experimental
represented by the model for low contact times
data obtained by Purnama et al. (2004). It might be
(< 0.70). This fact suggested the possibility that
observed that the reactor behaviour in the four
measurement errors had occurred to H2 concentration
operational conditions showed experimentally by in this range contact time.
Purnama et al. (2004) was well represented by the The adjustment quality quantification might be
model proposed in which one of the main objectives of carried out by inspecting Table 1 as a function of the
a methanol steam reforming was to produce hydrogen relative deviation means for component i (RDMC)
for use in a fuel cell. However some aspects must be and the global mean deviation (GMD) respectively
taken into consideration, such as the 10 part per defined by Equations 12 and 13. As Table 1 shows,
million (ppm) of carbon monoxide in the feed of fuel the relative deviation mean for component, ranging
cells, because it contaminated the anode of proton from 2 to 29%, failed to demonstrate a clear trend
exchange membrane fuel cell (PEM) (KIM; CHA, due to temperature. However, the global mean
2003; KIM; LIM, 2002; LEE et al., 2004). deviation indicated that as the temperature rose,
Figure 2 shows that contact time, obtained from there was an improvement in the fitness quality of
the ratio of the mass of catalyst by the input flow of the the model, or rather, from 19.8% DMG at 230oC to
reactants in the reactor, affected the trend in hydrogen 9.6% DMG at 300oC.
production profile. Experimental data were virtually
linear, 0.5s to 0.6 seconds, after which there was a n
j
Pexp  Pcalc
j

significant increase in hydrogen production. The  j

Pexp
x100
(12)
proposed mathematical model used an equation of the RDMC i 
j 1

type of law powers for the rate law of the steam n

reforming reaction. The mathematical model employs
a power law equation to represent the reform of steam
c

reaction rate. Due to this choice, the model’s

 DRMC i (13)
GMD  i 1
intermediate points show a significant deviation with c
regard to the experimental data by Purnama et al.
(2004). The model adjusts itself to the total production where:
of hydrogen and other compounds and to temperature c is all components; n is all points; Pexpj is experimental
conversion at 230ºC. When experimental data by
partial pressure of component i and Pcalc j is the
Purnama et al. (2004) and the model given in Figures 3
to 5 were compared, the fact revealed that the latter was calculated partial pressure of component i.

0.8 0.8
Simulated H2 H2
0.7 Experimental 0.7

0.6 0.6
CH3OH
0.5 H2O 0.5
P [kPa]

P [kPa]

Simulated
0.4 0.4 Experimental

0.3 CO2 0.3 CO2

0.2 0.2
CH3OH
H2O
0.1 CO 0.1 CO

0 0
0 0.2 0.4 0.6 0.8 1 0 0.12 0.24 0.36 0.48 0.6
Contact Time (s) Contact Time (s)
Figure 2. Model predictions and experimental data at 230ºC. ….. Figure 3. Model predictions and experimental data at 250ºC.

Acta Scientiarum. Technology Maringá, v. 36, n. 2, p. 295-301, Apr.-June, 2014

Isothermal reactor for methanol steam reforming 299

0.8 0.8
H2
0.7 0.7 H2

0.6 0.6

0.5 0.5
Simulated Simulated
P [kPa]

P [kPa]
Experimental
0.4 Experimental
0.4

0.3 CO2 0.3 CO2

0.2 CH3OH 0.2

H2O CH3OH
H2O
0.1 CO 0.1
CO
0 0
0 0.06 0.12 0.18 0.24 0.3 0 0.03 0.06 0.09 0.12 0.15
Contact Time (s) Contact Time (s)
Figure 4. Model predictions and experimental data at 270ºC. ……. Figure 5. Model predictions and experimental data at 300ºC.

Table 1. Mathematical simulation of global error compared to First, the design of a reactor operating at high
experimental data.
temperature: it implies the use of small amounts of
Temperature DRMC (%)
(oC)
DMG (%) catalyst (low contact time) and consequently a
CH3OH H2O H2 CO2 CO
230 19.8 16 16 29 18 - reduced size reactor to achieve high conversions of
250 15.8 22 22 13 12 10 methanol (approximately 100%, Figure 6); however,
270 13.2 16 16 14 15 5
300 9.6 8 8 2 2 28 there is a need for subsequent purification steps in
CO was not detected at 230oC, which made impossible the calculation of DRMC. the hydrogen stream to compensate for a large
amount of CO in the effluent stream (Figure 7).
Methanol steam reforming occurred at lower
temperatures for copper-based catalysts (230 to 300oC),
generating mostly hydrogen and carbon dioxide and a
small amount of CO, usually less than 1% (LEDJEFF-
HEY et al. 1998; PETERS et al. 2000; WIESE et al.
1999). The mathematical model used in this study may
100%
be used to determine the condition of operating a 90%
reactor of autonomous fuel cell that produces low level 80%

carbon monoxide (contaminant). The process of 70%

0.00

producing hydrogen from methanol is simple and it is

0.10

60%
Conversion
0.20

50%
possible to build compact reformers for adequate
0.30

0.40

40%
hydrogen production on-board. Figure 6 shows the
0.50

30%
0.60

dependence of methanol conversion by temperature 20%

0.70

0.81

and length of catalyst bed (contact time). Temperatures

10%
0.91

90%-100% 80%-90% 0%
above 270°C favor a high conversion, which tends
300
1.01

70%-80% 60%-70%
270
250

50%-60% 40%-50%
230

towards equilibrium with low contact time, 30%-40% 20%-30%

10%-20% 0%-10%
corresponding to the use of a small amount of catalyst.
The above is desirable because of deployment costs and Figure 6. The simulation of conversion methanol at a
temperature range between 230 and 270°C, with a contact time of
volume of the autonomous fuel cell. 7.1 seconds.
Therefore, the project of a methanol steam
reforming reactor attached to a fuel cell and Second, the design of a reactor operating at low
separation or purification units, which comprises the temperatures: in this case, the effluent stream from
platform for an autonomous fuel cell, implies a the reactor would present a low concentration of
reflection on two distinct possibilities. CO, less than 10 ppm (Figure 7). The
Acta Scientiarum. Technology Maringá, v. 36, n. 2, p. 295-301, Apr.-June, 2014
300 Menechini Neto et al.

inconvenience of low conversions of methanol Results point to the possibility of designing two
(approximately 70%, Figure 6) is that they require types of autonomous fuel cell which depend on the
subsequent operations for the separation of the operating temperature. High temperature will be
residual methanol, possibly by condensation, employed in small reactors with high methanol
followed by re-feeding of the reactor. conversion and high CO concentration in the
effluent stream. The above requires the
implementation of further steps to remove CO to
acceptable levels (< 10 ppm) to the perfect
operation of the PEM fuel cell. Moreover, low
temperature reactor will be larger and it will present
16000
low conversion and a significant amount of residual
14000 methanol. The above requires subsequent stages for
12000 the separation and recycling of the reagent at levels
10000 below 10 ppm of CO, which makes the removal of
0.00

PPM
this contaminant unnecessary.
0.10

8000
0.20

0.30

6000
0.40

Acknowledgements
0.50

14000-16000 4000
0.60

12000-14000
0.70

10000-12000 2000
Current research was funded by the
0.81

8000-10000 0
Coordination for the Updating of Higher Education
0.91

300

6000-8000
270
1.01

Personnel (CAPES-Brazil) and by the Institute of

250

4000-6000
230

2000-4000
0-2000 Technology for Development (LACTEC).
Figure 7. Simulation of the concentration of carbon monoxide
(PPM) to a temperature range between 230 and 270°C, with a
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