Applied Energy 94 (2012) 141–147

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Applied Energy
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Damköhler number as a descriptive parameter in methanol steam reforming

and its integration with absorption heat pump system
Willy Yanto Wijaya ⇑, Shunsuke Kawasaki, Hirotatsu Watanabe, Ken Okazaki
Department of Mechanical and Control Engineering, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo, Japan

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

Article history: Studies on the kinetics of methanol steam reforming (MSR) reaction have been extensively carried out in
Received 26 October 2011 these past decades. However, in order to get a more thorough understanding of the MSR performance, it
Received in revised form 11 January 2012 is necessary to integrate the reaction kinetics of MSR with the reactor design/operating parameters. This
Accepted 15 January 2012
paper presents such works and employs Damköhler number (Da) to conveniently describe the trade-off
Available online 14 February 2012
between kinetics (reaction time scale) and operating parameters (residence time scale) of the MSR sys-
tem. The correlation of Da and methanol conversion was also experimentally verified. Furthermore, fea-
Keywords:
sibility criterion as a parameter to describe energy gain obtained by MSR reaction over the energy
Damköhler number
Methanol steam reforming
required by absorption heat pump (AHP) system was viewed, and its correlation with Da was investi-
Reaction kinetics gated. Some results showed that even at various combinations of GHSV and MSR reaction temperature,
Absorption heat pump the Da – methanol conversion empirically have a similar typical curve. On the other hand, for the com-
bined AHP–MSR system, changing the value of Da, either by changing the GHSV or MSR reaction temper-
ature, results in different profiles of feasibility criterion and hydrogen production rate.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction discarded annually in Japan [13]. Through its endothermic nature,

Depletion of fossil fuel and environmental problems have forced
efforts to realize future clean energy systems. Hydrogen energy is
one strong candidate due to its abundance in nature, possibility
to be produced from various other forms of energy, as well as its
versatile utilization in energy devices such as fuel cells and gas
turbine [1–3]. In the far future, renewable energy will be used to
produce hydrogen fuel. However, since the contribution of renew-
able energy is significantly small at present, in this short and
middle-term future, hydrogen production still relies heavily on
hydrocarbon processing [4–6], where carbon capture and seques-
tration technologies can be simultaneously employed to minimize
the CO2 emission [7–9].
Methanol steam reforming (MSR) is regarded as one of potential
hydrocarbon processing methods for hydrogen production. This is
due to its advantageous characteristics, such as: stability and high
volumetric energy density of methanol [10], possibility of metha-
nol production from biomass [11,12], lowest reaction temperature
compared to other hydrocarbon steam reforming, and its potential
utilization of waste heat as the endothermic heat supply [13,14].
There is a huge potential of the industrial waste heat to serve as
the endothermic energy supply for MSR. For example, more than
800 PJ waste heat in the temperature range around 100 °C is being
⇑ Corresponding author. Tel./fax: +81 3 57342179.
E-mail address: wijaya.w.aa@m.titech.ac.jp (W.Y. Wijaya).
three moles of hydrogen produced by MSR reaction will have high-
er energy content compared to one mole of methanol:

CH3 OHðgÞ þ H2 OðgÞ $ CO2ðgÞ þ 3H2ðgÞ DHMSR ¼ þ49:5kJ=mol CH3 OH
ðR1Þ
Thermodynamic analysis of MSR reaction has been carried out
as early as two decades ago by Amphlett et al. [15]. Further evalu-
ations were conducted again by Lwin et al. [16] and Faungnawakij
et al. [17] using Gibbs free minimization method. Principle results
from these thermodynamic studies showed that methanol conver-
sion could be well achieved at temperature less than 200 °C by
adjusting appropriate steam–carbon molar ratio (S/C) and reaction
pressure. Nevertheless, thermodynamic analysis alone does not
suffice to describe the actual MSR process due to its exclusion of
the chemical reaction time-scale (kinetics).
Studies on the kinetics of MSR have also been extensively car-
ried out in these past two decades [18–22]. Reaction mechanism
and kinetics of MSR depend considerably on the types of catalysts
used, and so far copper-based catalysts are the most commonly
employed for MSR due to its high activity at lower temperature
[18]. Nevertheless, even though employing same types of catalysts,
the overall kinetics expressions of MSR reaction proposed by
various research groups were different, as summarized by Lee
et al. [23]. These differences indicate that detailed specifications
of reactors, such as reactor types and geometries can result in
different profiles of the actual energy and mass transfer inside

0306-2619/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.apenergy.2012.01.041
142 W.Y. Wijaya et al. / Applied Energy 94 (2012) 141–147
Nomenclature
Da Damköhler number
Ea activation energy (J mol1)
F molar flow rate (mol s1)
GHSV gas hourly space velocity (h1)
k rate constant (mol s1 m3 atm0.23)
k0 pre-exponential factor (mol s1 m3 atm0.23)
m reaction order with respect to methanol
n reaction order with respect to hydrogen
r reaction rate (mol s1 m3)
R universal gas constant (8.314 kJ kmol1 K1)
S/C steam–carbon (methanol) molar ratio
TA output temperature from the AHP (K)
TD temperature of waste heat (K)
V volume of the reactor (m3)
W_ AHP internal work of absorption heat pump (J s1)
the reactors [24,25]. Besides, the different operating conditions
such as the measurement range of temperature, concentration of
each species, reaction pressure, flow rate and pattern, as well as
each research group’s approach in formulating the reaction rate
law will eventually lead to varying forms of kinetics expressions.
Therefore, in this work, experimental investigation on the MSR
kinetics was conducted using our own experimental set-up.
Studies of MSR kinetics has provided clues for better tailoring of
catalysts, as well as understanding of the detailed reaction mecha-
nism and interactions. However, in order to put it into practical
applicability, reaction kinetics has to be coupled with concepts of
reactor design/operating parameters. Few papers have addressed
this issue in their analysis. Liao and Erickson [26] proposed charac-
teristic time, which is the reciprocal of reaction rate constant, as a
scaling parameter to quantify reactor performance. They showed
that two extremely different configurations of MSR reactors with
the same characteristic time will give relatively similar conversion
of methanol. However, in order to get a more thorough under-
standing of the MSR performance, it is necessary to integrate the
reaction kinetics of MSR with each of the reactor design/operating
parameters such as the gas hourly space velocity (GHSV) and
temperature.
Furthermore, the fact that MSR requires lower operating tem-
perature compared to other hydrocarbon steam reforming has
not been much emphasized in the related literature. This charac-
teristic of MSR enables a wide range of options of integrating the
MSR reactor with other energy systems to supply the endothermic
heat required by the MSR reaction. Liu and Hong et al. [27,28] sug-
gested integrating the MSR reactor with middle-temperature solar
thermal energy. They obtained interesting correlations between
solar flux and the thermochemical efficiency. In our previous work,
we proposed using absorption heat pump (AHP) to enhance the
temperature level of industrial waste heat to be used as the endo-
thermic heat for MSR [14]. In our evaluation of this combined
AHP–MSR system, it was found that there is potential to obtain
net energy gain from this combined energy system by finding
out optimized operating conditions, such as how GHSV, S/C, and
temperature level of AHP output could affect the profile of the
net energy gain. However, further investigation is still required
to understand the correlation between kinetics of MSR reaction,
MSR reactor design/operating parameters, and potential energy
gain (recovery) obtained when MSR reactor is combined with
AHP system.
Therefore, this work comprises of three main objectives. First
objective is the experimental measurement of the reaction kinetics
[CH3OH] molar concentration of methanol
[H2] molar concentration of hydrogen
a methanol conversion
DH enthalpy change of reaction (kJ mol1)
/ feasibility criterion
Subscript
AHP absorption heat pump
CH3OH methanol
in reactor inlet
MSR methanol steam reforming
Superscript
° standard reference state (298.15 K, 1 atm)
parameters, to find out rate expression and kinetics parameters
values representative to the actual mass and energy transfer occur-
ring inside the reactor. The second objective is to propose a useful
dimensionless parameter to analyze the MSR system, where the
dimensionless parameter employed is Damköhler number which
can describe well the performance of MSR reaction even at differ-
ent GHSV and temperature. The third objective is to correlate the
MSR reaction and the concept of net energy gain when combined
with AHP system. In particular, focus of this work will be on
examining the correlation between Damköhler number, energy
gain of the combined AHP–MSR system, and the hydrogen
production rate.
2. Experiments of MSR kinetics
2.1. Experiments to measure reaction kinetics parameters
Schematic of the experimental set-up is shown in Fig. 1, and the
details have been described in our previous paper [14]. To obtain a
proper description of MSR kinetics, it is necessary to find out the
reaction rate law of the MSR reaction. Reaction rate law describes
how changes of temperature and partial pressure (concentration)
of each chemical species involved in the reaction might influence
the rate of the reaction.
Based on (R1), in overall reaction of MSR, four main chemical
species are involved. Partial pressure of each species can be
adjusted by adding feed input of the respective species to the
inlet of the reactor. In particular, partial pressure of methanol
was adjusted by feeding more input of inert gas (nitrogen).
The results indicated that partial pressure increase of hydrogen
species gave significant influence on the methanol conversion
decrease. Meanwhile, partial pressure changes of other species,
i.e. CO2 and additional H2O resulted in the relatively same effect
as the partial pressure change of methanol (by adding inert gas
N2) [29,30]. Since inert gas has no influence to the reaction
kinetics, the changes of the methanol conversion rate is regarded
as due to the changes of the methanol partial pressure. Consid-
ering that increasing CO2 and H2O partial pressure resulted in
the same effect as the increasing N2 partial pressure, then it
can be inferred that the decrease of methanol conversion (reac-
tion rate) is in fact due to the decrease of the methanol partial
pressure. Therefore, the reaction rate law of overall MSR reaction
can be expressed as:
r ¼ k½CH3 OHm ½H2 n ; ð1Þ
 W.Y. Wijaya et al. / Applied Energy 94 (2012) 141–147 143

Fig. 1. Schematic of the methanol steam reforming experimental set-up.

Ea=RT
k ¼ k0 e ; ð2Þ
where r is the reaction rate of methanol conversion, k is the rate
constant, [CH3OH] and [H2] are the molar concentration (in the
gas form) of methanol and hydrogen respectively, m is the reaction
order with respect to methanol, n is the reaction order with respect
to H2, k0 is the pre-exponential factor, Ea is the activation energy,
and T is the MSR reaction temperature.

2.2. Determination of reaction order

After obtaining the reaction rate law as expressed in Eq. (1), the
reaction order m and n can be determined. By maintaining a low
conversion of methanol into hydrogen, Eq. (1) becomes:
0
r ¼ k ½CH3 OHm ; ð3Þ
which can be subsequently derived into the form:
Fig. 2. MSR reaction rate as a function of methanol partial pressure.
0
ln r ¼ ln k þ m ln½CH3 OH: ð4Þ
Partial pressure (concentration) of methanol can be adjusted by
flowing additional N2 input into the reactor, with the total GHSV
set to 4000 h1. GHSV is defined as:

1 F Total;in
GHSV ½h  ¼ ; ð5Þ
V
where FTotal,in is the total flow rate of the reactants and inert gas at
the inlet of the reactor, and V is the volume of the reactor. On the
other hand, the reaction rate (r) can be determined from the
measured amount of methanol conversion. Temperature was kept
constant at about 435 K to enable a conversion of methanol lower
than 10%. The result is shown in Fig. 2, which gives value of m
around 0.219.
In the same way, the reaction order with respect to H2 can be
determined from:
ln r0 ¼ ln k þ n ln½H2 ; where ð6Þ

r 0 ¼ r=½CH3 OHm : ð7Þ

Fig. 3. MSR reaction rate as a function of hydrogen partial pressure.
144 W.Y. Wijaya et al. / Applied Energy 94 (2012) 141–147

The value of n obtained experimentally is around 0.447, as By substituting Eqs. (8) and (9) into the denominator of the
shown in Fig. 3. integrand in Eq. (12), and re-arranging, following equation can be
obtained:
2.3. Arrhenius plot and activation energy of MSR
V 1
¼
½CH3 OHin F Total;in k½CH3 OHm in ð3½CH3 OHin Þ
n
After obtaining the values of m and n, the activation energy of Z a
the MSR reaction can be determined by using Eq. (2). The MSR ð1 þ 2a½CH3 OHin Þmþn da
 ; ð13Þ
reaction temperature was adjusted in the range from 443 to 0 ð1  aÞm an
495 K, with 0.1 atm partial pressure of N2 at reactor inlet, and
which describes the correlation between reaction kinetics and
0.45 atm for each partial pressure of methanol and steam at the
reactor design (operating) parameters. In this Eq. (13), reaction
reactor inlet. Total GHSV for all the feed at the inlet was kept at
kinetics is mainly represented by k, m, and n; while reactor design
4000 h1. The Arrhenius plot of the measurement results is shown
(operating) parameters such as S/C is implicitly represented by
in Fig. 4, and the value of activation energy (Ea) obtained is around
[CH3OH]in, and GHSV is the reciprocal of part of the left-hand side
98.6 kJ/mol.
of Eq. (13). The trade-off of all these parameters (kinetics and
reactor design) will determine the value of a (methanol conversion)
3. Calculation method of the MSR system.

3.1. Correlation of MSR kinetics and reactor design/operating 3.2. Damköhler number of MSR
parameters
The correlation between reaction kinetics and reactor design
From the stoichiometric balance of chemical species involved in parameters as described in Eq. (13) can be simplified by employing
MSR reaction as shown in (R1), the molar concentration of metha- Damköhler number. Damköhler number is the dimensionless
nol and hydrogen can be described as: number that describes the ratio of characteristic fluid flow time
½CH3 OHin ð1  aÞ over the characteristic chemical reaction time, which in general
½CH3 OH ¼ ; and ð8Þ can be written as:
ð1 þ 2a½CH3 OHin Þ
characteristic fluid time
3a½CH3 OHin Da ¼
½H2  ¼ : ð9Þ characteristic chemical reaction time
ð1 þ 2a½CH3 OHin Þ chemical reaction rate
¼ : ð14Þ
The subscript ‘‘in’’ denotes the condition at reactor inlet, and a conv ectiv e mass transport rate
indicates the amount of converted methanol, which can be de-
In the case of this MSR reaction system, the Damköhler number
scribed as:
can be defined as:
F CH3OH;in  F CH3OH
a¼ ; ð10Þ k½CH3 OHm n
in ð3½CH3 OHin Þ V
F CH3OH;in Da ¼ : ð15Þ
½CH3 OHin F Total;in
where F is the flow rate of certain chemical species. Based on kinet-
By combining Eqs. (15) and (13), methanol conversion rate can
ics of reaction, the reaction rate of methanol conversion can also be
be correlated to Da as following equation:
expressed as:
Z a
ð1 þ 2a½CH3 OHin Þmþn da
dF CH3OH Da ¼ : ð16Þ
r CH3OH ¼ ; ð11Þ 0 ð1  aÞm an
dV
where V is the volume of the reactor. By integrating Eq. (11) and
combining with Eqs. (1) and (10), following equation can be 4. Results and discussions
obtained:
Z a Z V 4.1. Damköhler number of MSR
da
F CH3OH;in ¼ dV: ð12Þ
0 k½CH3 OHm ½H2 n 0 Fig. 5 shows the measurement results of methanol conversion
with respect to the Damköhler number and comparison with the

Fig. 5. Experimental data plot and calculated result of Da and methanol conversion
Fig. 4. Arrhenius plot to determine the activation energy of MSR reaction. at various combinations of GHSV and temperature, at S/C = 1.
 W.Y. Wijaya et al. / Applied Energy 94 (2012) 141–147
Fig. 6. Correlation of Damköhler number, methanol conversion, GHSV, and reaction
temperature of MSR.
calculation results obtained from Eq. (16). As can be seen, even
though operated at various GHSV and temperature conditions,
the profile of the MSR experimental data distribution follows a
certain curve similar to the profile suggested from calculation. In
particular, at lower Da, different combinations of GHSV and
temperature overlap well one another, for example three combina-
tion points of 4000 h1, 444 K; 2000 h1, 436 K; and 1333 h1,
435 K. This is due to the fact that the combinations of these
different GHSV and temperature translate into relatively similar
value of Da. Therefore, Da is an effective parameter to describe
the MSR kinetics. These experimental results also support the
validity of Eq. (16).
Fig. 6 shows the correlation of Damköhler number, methanol
conversion, GHSV, and reaction temperature, calculated from Eqs.
(15) and (16). It is found that when the value of Da is less than
0.02, the methanol conversion rate will be less than 10%. The
conversion rate will reach unity when the Da approaching value
about 0.84. It can also be seen that Eq. (15) has taken into account
both the characteristic reaction time and flow (residence) time of
MSR and therefore knowing the value of Da of MSR can give quick
idea upon to what extent the conversion of the methanol into
hydrogen will proceed. As expressed in Eq. (15), the value of Da
can be changed by changing k (rate constant) which depends on
temperature, or by changing the residence time which is the
reciprocal of GHSV. Therefore, at higher reaction temperature, to
Fig. 7. Schematic of combined AHP and MSR systems.
145
achieve equal value of Da which corresponds to equal conversion
of methanol, higher GHSV can be carried out. It is interesting to
notice that as the value of Da becomes larger, the GHSV difference
of two temperature level (473 K and 493 K) to achieve equal
methanol conversion ratio also decreases. The reason is that at
larger Da or higher methanol conversion, the rate at which meth-
anol molecules get converted into hydrogen molecules will slow
down due to the increased hydrogen partial pressure, and thus
changing the GHSV or molar flow rate of methanol molecules af-
fects the methanol conversion more significantly. In other words,
the strong effect of temperature on the kinetics is becoming less
significant at higher methanol conversion (higher Da) in compari-
son to the residence time. This characteristic can be viewed as the
balancing effect between kinetics (reaction time) and residence
time.
4.2. Correlation of Damköhler number and feasibility criterion of AHP
Details of absorption heat pump (AHP) system have been de-
scribed in our previous paper [14]. Basically, AHP system functions
to enhance the low temperature waste steam to a higher temper-
ature level sufficient enough to be used for the MSR reaction, as de-
scribed in Fig. 7. Waste heat in the form of steam with temperature
TD is enhanced by AHP system to become high temperature steam
with temperature TA, then to be mixed with the evaporated meth-
anol in the MSR reactor. Through the MSR reactor, each mole of
methanol will be converted into three moles of hydrogen, giving
a net energy gain FCH3OH a DHMSR for each mole of converted meth-
anol, where FCH3OH [mol s1] is the molar flow rate of methanol, a
is the amount of methanol conversion, and DHMSR (+49.5 kJ/mol
CH3OH) is the enthalpy change of MSR reaction. However, since
AHP needs some work input (W _ AHP ) to enhance the temperature le-
vel of waste heat, a feasibility criterion (/) of this combined AHP–
MSR system was proposed:
Energy gain by MSR F CH3OH aDHMSR
/¼ ¼ ; ð17Þ
Work required for AHP W_ AHP
which measures the net energy gain via the MSR system in compar-
ison to the work required for the AHP system. The internal work re-
quired for the AHP system (W _ AHP ) particularly depends on the input
waste heat temperature (TD), output temperature from the AHP sys-
tem (TA), and the flow rate of the steam to be supplied to the MSR
system. These parameters can be calculated when Da and either
reaction temperature or GHSV are defined [14].
146 W.Y. Wijaya et al. / Applied Energy 94 (2012) 141–147

Fig. 8. Feasibility criterion (/) as a function of Damköhler number (Da) (two cases).

Fig. 9. Hydrogen production rate as a function of Damköhler number (Da) (two

For a certain MSR operating condition (certain reacting temper-
ature, GHSV, S/C), the feasibility criterion (/) of AHP–MSR system
and the MSR Damköhler number (Da) can be determined, and
the result is shown in Fig. 8. Since there are two possible ways to
change the value of Da, either by changing the reaction tempera-
ture or by changing the residence time (GHSV), Fig. 8 shows the
comparison of both cases with respect to the obtained /. It is inter-
esting to notice that at lower values of Da, both cases result in rel-
atively similar value of /. After the intersection at T = 473 K and
GHSV = 4000 h1, changing Da by increasing the temperature gives
less favorable / compared to changing Da by decreasing the GHSV.
It means that the feasibility criterion (/) is changed even when the
methanol conversion or Da is same. This is actually in line with our
previous discussions that at higher Da, the effect of temperature on
the reaction kinetics becomes less significant. Besides, another rea-
son is that after the peak of the graph which corresponds to the
methanol conversion around unity, keeping increasing the MSR
_ AHP , while the en-
reaction temperature will cause the increase of W
ergy gain by MSR (the numerator of Eq. (17)) is already stagnant,
thus the value of / starts to decrease. On the other hand, for the
case of decreasing the GHSV, after the peak value, decreasing the
flow rate (GHSV) causes the drop of the energy gain by MSR (the
numerator of Eq. (17)), however simultaneously, the ideal pump
work required (W _ AHP ) also drops accordingly, and these are bal-
anced, thus the value of / becomes constant.
Then, it seems that to obtain the best net energy gain over the
required pump work (/), it is best to increase the Da of the MSR
system by decreasing the flow rate of the input reactants (GHSV).
However, it should be noted that decreasing GHSV also means
the lower production rate of hydrogen:
H2 production rate ¼ 3aF CH3OH;in ;
especially after methanol conversion (a) has reached its maximum
value. Thus, in term of hydrogen production rate, both cases
(decreasing GHSV or increasing temperature) result in significantly
different profiles as shown in Fig. 9. Fig. 9 shows that increasing Da
by keeping GHSV constant and increasing the reaction temperature,
will give approximately three times higher production rate com-
pared to the case where reaction temperature is kept constant
and GHSV is decreased. Therefore, both aspects (energy gain and
production rate) need to be carefully considered when implement-
ing this combined AHP–MSR system.
cases).
Results from Figs. 8 and 9 imply that desirable amount of
hydrogen production as well as feasibility criterion must be used
as the starting criteria in designing a reforming reactor and its
accompanying AHP system. From the view point of industrial pro-
cess, feasibility criterion must be well over than unity. Our results
show that this combined AHP–MSR system is feasible for industrial
applications. Furthermore, Da is useful non-dimensional parameter
in designing reactor parameters such as flow rate, temperature,
and reactor volume. Da changes not only the feasibility criterion
corresponding to reactor performance but also the amount of
hydrogen production corresponding to reactor scale as shown in
Figs. 8 and 9.
Fig. 8 shows desired Da is around unity to achieve high perfor-
mance of reaction. Meanwhile, Fig. 9 shows that amount of hydro-
gen production is another criterion in determining reactor scale.
The scale-up of the MSR reactor is another important issue, where
non-uniform temperature distribution inside reactor, non-uniform
catalysts size and density, pressure drops, and changing flow pat-
terns are crucial issues that have to be analyzed further in the ac-
tual implementation of this combined system for industrial
applications.
5. Conclusions
To achieve an optimized hydrogen production system through
MSR process, it is necessary to incorporate reaction kinetics and
reactor design (operating) parameters. In this work, reaction kinet-
ics was experimentally investigated to get a proper description of
the actual mass and energy transfer inside the MSR reactor. Then
ð18Þ the obtained kinetics parameters and reactor design (operating)
parameters of the MSR were correlated, deriving a complex equa-
tion which is then further simplified by employing Damköhler
number. Further, the correlation of Damköhler number with feasi-
bility criterion of AHP–MSR system was also investigated and dis-
cussed. From this research, some interesting results to be
summarized are:
a. Damköhler number is a useful dimensionless parameter to
describe reaction performance of MSR. Even for the empiri-
cal measurement, various combinations of GHSV and tem-
perature translate into a typical Da – methanol conversion
 W.Y. Wijaya et al. / Applied Energy 94 (2012) 141–147
curve, which can be used to quickly determine to what
extent the MSR reaction will proceed given a specified oper-
ating condition.
b. By keeping a constant Da, changing the reaction temperature
or GHSV results in different value of /, where decreasing
GHSV gives better off in term of energy gain, but worse in
term of hydrogen production rate.
Acknowledgment
Financial support from GCOE Energy – Tokyo Tech is gratefully
acknowledged.
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