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Energy Procedia
Energy Procedia 00
156(2017)
(2019)000–000
38–42
www.elsevier.com/locate/procedia
2018 5th International Conference on Power and Energy Systems Engineering, CPESE 2018,
2018 5th International Conference on Power 2018,
19–21 September and Energy Systems
Nagoya, Japan Engineering, CPESE 2018,
19–21 September 2018, Nagoya, Japan
Simulations of Hydrogen Production by Methanol Steam Reforming
SimulationsThe
of15th
Hydrogen Production
International byDistrict
Symposium on Methanol Steam
Heating and Reforming
Cooling
Yu-Jen Chiua,a,*, Han-Chieh Chiuaa, Ren-Horn Hsiehaa, Jer-Huan Jangbb, Bo-Yi Jiangaa
a Assessing
Yu-Jen the feasibility
Chiu *, Han-Chieh of usingHsieh
Chiu , Ren-Horn the ,heat demand-outdoor
Jer-Huan Jang , Bo-Yi Jiang
Department of Mechanical Engineering, Taipei City University of Science and Technology, Pei-Tou, Taipei 112, Taiwan, R.O.C.
b

b
temperature function for a long-term district heat demand forecast
Department
a of Mechanical
Department Engineering/Battery
of Mechanical Research
Engineering, Taipei City Center of Green
University
Department of Mechanical Engineering/Battery ResearchCity
Energy,
of Science
243,ofTaiwan,
Center
andMing Chi University
Technology, of Taipei
Pei-Tou, Technology, Taishan,R.O.C.
112, Taiwan, New Taipei
R.O.C. Ming Chi University of Technology, Taishan, New Taipei
Green Energy,
City 243, Taiwan, R.O.C.
I. Andrića,b,c*, A. Pinaa, P. Ferrãoa, J. Fournierb., B. Lacarrièrec, O. Le Correc
Abstract
a
AbstractIN+ Center for Innovation, Technology and Policy Research - Instituto Superior Técnico, Av. Rovisco Pais 1, 1049-001 Lisbon, Portugal
b
Methanol is regarded as an Veolia Recherche
important & Innovation,
feedstock for 291 Avenue production
hydrogen Dreyfous Daniel,due78520
to itsLimay,
highFrance
energy density and superior
c
transportability.
Methanol Département
A tubular
is regarded Systèmes
as an Énergétiques
packed-bed
importantreactor et
feedstockEnvironnement
performing - IMT Atlantique,
the methanol
for hydrogen production 4
steam rue Alfred Kastler,
duereforming
to its high(MSR)44300 Nantes,
process
energy France
was
density modeled
and by
superior
adopting computational
transportability. A tubularfluidpacked-bed
dynamics (CFD)
reactor software
performingto analyze
the methanolits performance. Kinetic (MSR)
steam reforming parameters of the
process wasreactions
modeledwereby
adjusted according
adopting computationalto thefluid
literatures
dynamicsand (CFD)
our previous
softwareexperimental
to analyze results. The methanol
its performance. conversion,
Kinetic parameters theofhydrogen production
the reactions were
rate, andaccording
adjusted the CO concentration
to the literaturesin the
and produced
our previous mixture were evaluated
experimental by considering
results. The different levels
methanol conversion, of the length
the hydrogen and
production
Abstract
temperature
rate, and theofCO the concentration
catalyst bed, the steam-to-carbon
in the produced mixture ratio and
weretheevaluated
space velocity of the feedstocks.
by considering different Moreover, the length
levels of the correlation
and
between the dimensionless
temperature of the catalystparameter, Damköhler number,
bed, the steam-to-carbon ratioand
andthe themethanol conversion
space velocity wasfeedstocks.
of the also investigated.
Moreover, the correlation
District heating networks are commonly addressed in the literature as one of the most effective solutions for decreasing the
between the dimensionless parameter, Damköhler number, and the methanol conversion was also investigated.
greenhouse gas emissions from the building sector. These systems require high investments which are returned through the heat
© 2018 The Authors. Published by Elsevier Ltd.
© sales.
2019 Due
The to the changed
Authors. climate conditions and building renovation policies, heat demand in the future could decrease,
This
© is an
2018 Theopen accessPublished
Authors. article under
Published by
by Elsevier Ltd.
the CC BY-NC-ND
Elsevier Ltd. license (https://creativecommons.org/licenses/by-nc-nd/4.0/)
prolonging
This is an openthe access
investment return
article underperiod.
the CC BY-NC-ND license (https://creativecommons.org/licenses/by-nc-nd/4.0/)
Selection
This and peer-review
is an open access articleunder
under responsibility
the CC BY-NC-ND of thelicense
2018 (https://creativecommons.org/licenses/by-nc-nd/4.0/)
5th International Conference on Power and Energy Systems
Selection
The mainand peer-review
scope underisresponsibility
of this paper to assess the of the 2018of5thusing
feasibility International Conference
the heat demand on Power
– outdoor and Energy
temperature Systems
function forEngineering,
heat demand
Engineering,
Selection and CPESE 2018, 19–21
peer-review under September 2018,ofNagoya,
responsibility the Japan.
2018 5th International Conference on Power and Energy Systems
CPESE
forecast.2018,
The19–21 September
district 2018, Nagoya,
of Alvalade, located inJapan.
Lisbon (Portugal), was used as a case study. The district is consisted of 665
Engineering, CPESE 2018, 19–21 September 2018, Nagoya, Japan.
buildings that vary in both construction period and typology. Three weather scenarios (low, medium, high) and three district
Keywords: methanol steam reforming (MSR), hydrogen production, packed-bed reactor, simulation
renovation scenarios were developed (shallow, intermediate, deep). To estimate the error, obtained heat demand values were
Keywords: methanol steam reforming (MSR), hydrogen production, packed-bed reactor, simulation
compared with results from a dynamic heat demand model, previously developed and validated by the authors.
The results showed that when only weather change is considered, the margin of error could be acceptable for some applications
1. Introduction
(the error in annual demand was lower than 20% for all weather scenarios considered). However, after introducing renovation
1. Introduction
scenarios, the error value increased up to 59.5% (depending on the weather and renovation scenarios combination considered).
TheMethanol
value of steam reforming increased
slope coefficient (MSR) ison considered one ofthetherange
average within potential
of 3.8%processes
up to 8% to per
acquire hydrogen
decade, [1]. Methanol
that corresponds to the
Methanol
isdecrease
regarded steam
as
in the an reforming
important
number of heating (MSR)
hoursisofconsidered
feedstock for hydrogen
22-139h one of
during the potential
production
the heating dueprocesses
season to to acquire
its high
(depending onenergy hydrogen
density [1].
the combination and Methanol
superior
of weather and
is regardedscenarios
transportability,
renovation as an important
especially for feedstock
considered). small-scaled
On the otherforand hydrogen
hand, functionproduction
portable fuel due to for
cell applications.
intercept increased its 7.8-12.7%
high
A energy
variety density
of decade
per chemical and
and superior
(dependingphysical
on the
transportability,
coupled scenarios). especially
The values for suggested
small-scaledcouldand be portable fuel cell
used to modify the applications. A variety
function parameters of scenarios
for the chemicalconsidered,
and physical and
improve the accuracy of heat demand estimations.

© 2017 The Authors. Published by Elsevier Ltd.

* Corresponding author. Tel.: +886-2-28927154; fax: +886-2-28935295.
Peer-review under responsibility of the Scientific Committee of The 15th International Symposium on District Heating and
yjchiu@tpcu.edu.tw
* E-mail address:
Corresponding author. Tel.: +886-2-28927154; fax: +886-2-28935295.
Cooling.
E-mail address: yjchiu@tpcu.edu.tw
1876-6102 © 2018 The Authors. Published by Elsevier Ltd.
Keywords:
This Heat
is an open demand;
access Forecast; Climate change license (https://creativecommons.org/licenses/by-nc-nd/4.0/)
1876-6102 © 2018 Thearticle under
Authors. the CC BY-NC-ND
Published by Elsevier Ltd.
Selection and peer-review under responsibility of the 2018
This is an open access article under the CC BY-NC-ND 5th International
license Conference on Power and Energy Systems Engineering, CPESE
(https://creativecommons.org/licenses/by-nc-nd/4.0/)
2018, 19–21
Selection andSeptember
peer-review2018,
underNagoya, Japan. of the 2018 5th International Conference on Power and Energy Systems Engineering, CPESE
responsibility
2018, 19–21 September 2018, Nagoya, Japan.
1876-6102 © 2017 The Authors. Published by Elsevier Ltd.
1876-6102 © 2019 The Authors. Published by Elsevier Ltd.
Peer-review under responsibility of the Scientific Committee of The 15th International Symposium on District Heating and Cooling.
This is an open access article under the CC BY-NC-ND license (https://creativecommons.org/licenses/by-nc-nd/4.0/)
Selection and peer-review under responsibility of the 2018 5th International Conference on Power and Energy Systems Engineering,
CPESE 2018, 19–21 September 2018, Nagoya, Japan.
10.1016/j.egypro.2018.11.081
 Yu-Jen Chiu et al. / Energy Procedia 156 (2019) 38–42 39
Yu-Jen Chiu et al. / Energy Procedia 00 (2018) 000–000

Table 1. Kinetic parameters adopted in the simulation model.

Reaction MR rWGS WGS
6 1 8 3 1 1
Pre-Exponential Factor, Ai 4.5  10 (s ) 7.0  10 (m kmol s ) 4.0  107 (m3 kmol1 s 1 )
Activation Energy, Ei ( J kmol 1 ) 8.45  107 1.08  108 6.7  107

parameters, as well as operating variables, dominate the performance of an MSR reactor. Lee et al. studied and
reviewed the MSR mechanism, the rate laws, and the relevant kinetic parameters [2]. An investigation into CO
formation on a commercial copper based catalyst was performed by Purnama et al. The kinetic parameters of the
reaction mechanism were fitted according to experimental results [3]. Dusterwald et al. indicated the steam-to-
carbon ratio ranging between 1.0 and 2.0 is preferable to an MSR process [4]. Dixon studied the ratio of the catalyst
particle size to the diameter of the packed-bed reactor and suggested it as an important design parameter [5]. Besides,
the dimensionless Damköhler number was discussed with the methanol conversion by Wijaya et al. [6]. Since the
effects of individual parameters and variables on an MSR process are complex, numerical and software models are
employed as effective approaches to the study. Jang et al. established a 3D numerical model for a small MSR reactor
to predict the influences of the flow channel types, reactant flow rate, and reactor temperature on the methanol
conversion [7]. Peksen designed an optimized SOFC pre-reformer by an experimentally validated computational
fluid dynamics (CFD) model [8]. Moreover, in our previous work, design-of-experiment (DOE) techniques are also
considered practical approaches to analyze the significance of parameters and variables regarding a MSR process [9].
In this paper, a tubular packed-bed reactor performing the MSR process was modeled by adopting commercial
CFD software, ANSYS Fluent, to analyze its performance. Kinetic parameters of the reactions were adjusted
according to the literatures and our previous experimental results. The factors in the study included the length and
temperature of the catalyst bed, the steam-to-carbon (S/C) ratio, the volumetric flow rate of the feedstocks, as well as
the catalyst loading. The resulting methanol conversion, hydrogen production rate, and CO concentration in the
outflow mixture were evaluated. Furthermore, based on a dispersion model of methanol conversion derived in our
previous work [10], the effect of Damköhler number (Da) on the methanol conversion was analyzed by the present
simulation model.

2. Model descriptions

Methanol steam reforming (MR) is best carried out over a copper based catalyst [11]:
CH 3OH (g)  H 2 O(g)  3H 2  CO2 , h 49.6 kJ mol 1 ; (1)

accompanying the reverse water-gas shift reaction (rWGS) [3]:

H 2  CO2  CO  H 2 O(g) , h 41.2 kJ mol 1 . (2)

Both the MR and rWGS reactions are endothermic. By referring Purnama’s work [3] and meeting the requirement of
the software simulation, the reverse reaction in (1) is neglected while the reaction rate is represented as

 E  0.6 0.4
rMR  AMR exp  MR  CM CW , (3)
 RT 
where CM and CW are the molar concentrations of methanol and water steam, respectively. The reaction rate of the
reverse water-gas shift reaction is

 E    EWGS 
rrWGS ArWGS exp  rWGS  CCO2 CH 2  AWGS exp  RT  CH 2O CCO , (4)
 RT   
where Ci denote the molar concentrations of species i . The kinetic parameters listed in Table 1 were used in the
simulation model that had been adjusted according to the literature [3] and our previous experiment. A tubular
40 Yu-Jen Chiu et al. / Energy Procedia 156 (2019) 38–42
Yu-Jen Chiu et al. / Energy Procedia 00 (2018) 000–000

(a) (b) (c)

Fig. 1. (a)The tubular packed-bed reactor; (b)the velocity field within the reactor; (c)the distribution of the hydrogen mole fraction.

Table 2. Operating variables used for model simulation

Sets Temperature (K) Steam to Carbon Ratio Flow Rate ( L min 1 )

A 483, 503, 523, 543, 563 1.0 2.0
B 563 0.5, 0.67, 1.0, 1.5, 2.0 2.0
C 563 1.0 1.5, 2.0, 2.5, 3.0, 3.5

packed-bed reactor model consisting of an inlet chamber, a packed catalyst section (porous media region), and an
outlet chamber was shown in Fig. 1(a). Taking the copper based commercial catalyst (ALFA HiFUEL R120) for
example, the packed catalyst pellets led to a porosity of 35%. The permeability and inertia loss coefficient in each
component direction were 1.37  108 m 2 and 1.18  104 m 1 , respectively. The thermal and flow field, as well as the
species distribution within the reactor can be achieved, as were shown in Fig. 1(b) and (c). The assigned operating
variables (boundary conditions) were listed in Table 2. All the simulation sets were performed for the length of the
catalyst bed being 0.05 and 0.1 m. The performance indices of the MSR reactor are defined as the followings. The
methanol conversion is the ratio of the methanol reacting rate (quantitatively evaluated by means of the generated
CO and CO 2 , mmol min 1 ) to methanol supplying rate ( mmol min 1 ) in the feedstock. The hydrogen to carbon
ratio (H/C) is the ratio of the hydrogen production rate ( mmol min 1 ) to the methanol feed rate ( mmol min 1 ). It
was considered an efficiency index based on the feedstock consumption. Similarly, the hydrogen to steam ratio (H/S)
is the ratio of the hydrogen production rate ( mmol min 1 ) to the water steam feed rate ( mmol min 1 ).

3. Results and discussions

First, the kinetic parameters of the reactions were adjusted according to the literatures and our previous
experimental results [10]. The methanol conversions achieved by simulation and experiment were depicted in Fig.
2(a). It revealed well fitted results with a root mean square deviation of 3.99%. Based on simulation set A and the
catalyst bed length of 0.05 m, the temperature effects on the species mole fraction (concentration) were also shown
in Fig. 2(b). Since the MR and rWGS reactions are endothermic, the mole fractions of hydrogen and CO revealed an
increase tendency progressively with the temperature rise. Nonetheless, temperature had little influence on the mole
fraction of CO 2 . A hydrogen production rate of 43.7 mmol min 1 can be obtained when the temperature was 563 K,
meanwhile the CO concentration in the outflow mixture was 6.8 vol.%. The methanol conversion raised from 38.5%
to 72.4% when the temperature increased from 483 K to 563 K.
Based on simulation set B and the catalyst bed length of 0.05 m, the effect of the S/C ratio on the methanol
conversion was shown in Fig. 3(a). It was observed that the methanol conversion was significantly confined by an
S/C ratio lower than 1.0. The hydrogen production efficiency (H/C ratio) enhanced with the increasing S/C ratio, as
was shown in Fig. 3(b). The observation was consistent with Dusterwald’s study in literature [4].
In the aspect of hydrogen production efficiency, a positive correlation between the methanol conversion and the
H/C ratio was shown in Fig. 4. It suggested that a high methanol conversion level leads to high hydrogen production
 Yu-Jen Chiu et al. / Energy Procedia 00 (2018) 000–000
Yu-Jen Chiu et al. / Energy Procedia 156 (2019) 38–42 41

(a) (a)

(b) (b)

Fig. 2. Simulation set A: the effects of temperature on (a)mole Fig. 3. Simulation set B: the effects of steam to carbon ratio on
fraction of the products; (b)methanol conversion. (a)methanol conversion; (b)H/S and H/C ratios.

(a)

(b)

Fig. 4. The correlation between the hydrogen to carbon ratio (H/C) Fig. 5. Simulation set C: the effects of (a)volumetric flow rate, (b)
and the methanol conversion. Damköhler number on the methanol conversion.

efficiency. A dispersion model of methanol conversion was therefore derived to analyze the performance of a MSR
reactor in our previous work [10]. The model incorporated two dimensionless parameter groups, Bodenstein number
( Bo  uL De ) and Damköhler number ( Da   k ). The effect of Damköhler number on the methanol conversion
was investigated by adopting different lengths of the catalyst beds and various volumetric flow rates of the
feedstocks (simulation set C), as was presented in Fig. 5. It was observed from Fig. 5(a) that the methanol
conversion decreased with an increase in the flow rates of the feedstocks. Besides, a longer catalyst bed led to higher
42 Yu-Jen Chiu et al. / Energy Procedia 156 (2019) 38–42
Yu-Jen Chiu et al. / Energy Procedia 00 (2018) 000–000

methanol conversion. It implies an increase in the residence time is beneficial to enhancing the hydrogen production
efficiency. The Damköhler number correlates the reaction rate (chemical aspect) with the convective mass transfer
rate (physical aspect). For a first order reaction, the Damköhler number is the product of the residence time and rate
constant, Da   k . Figure 5(b) revealed a regular positive correlation between Da and methanol conversion, where
the rate constant was 0.42 s 1 while Da ranged from 0.25 to 1.17. It was therefore suggested that the Damköhler
number can serve as an effective measure of hydrogen production efficiency. It also provided a design reference for
a tubular MSR reactor.

4. Conclusions

A tubular packed-bed MSR reactor was modeled by introducing computational fluid dynamics (CFD) software,
which had been verified to be an effective tool for analyzing the reactor performance. The model comprising
chemical and physical parameters, as well as operating variables, was conducted to investigate the individual
influences on the hydrogen production efficiency. Moreover, the dimensionless Damköhler number was suggested
to be an important index that quantitatively measured the performance of an MSR process. Further tasks regarding
the experimental data fitting and model validation are in progress.

Acknowledgements

This work was financially supported by Ministry of Science and Technology, Taiwan, R.O.C. (MOST 106-2622-
E-149-001-CC3).

References

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