Transient Behaviour of A Small Methanol Reformer For Fuel Cell During Hydrogen Production After Cold Start

Energy Conversion and Management 46 (2005) 1193–1207
www.elsevier.com/locate/enconman
Transient behaviour of a small methanol reformer for fuel

cell during hydrogen production after cold start
Rong-Fang Horng *
Department of Mechanical Engineering, Kun Shan University of Technology, 949, Da-Wan Road,
Yung-Kung City, Tainan County, Taiwan 710, ROC
Received 13 February 2004; received in revised form 28 May 2004; accepted 13 June 2004
Available online 26 August 2004
Abstract
The cold start transient characteristics of a small methanol reformer for a fuel cell were investigated. The
main parameters studied were the oxygen to methanol mol ratio (O/C), fuel supply rate, heating power and
heating temperature. The composition of the gas produced by the reformer was analysed. The main aim of
this paper was to determine a favorable combination of the parameters for obtaining rapid hydrogen pro-
duction during the transient behaviour of the reformer.
A small methanol reformer with fuel, air and water injectors, heaters and a catalyst was constructed. Vapor-
ised methanol was injected into the reformer, which then flowed into the catalyst. For the purpose of enhanc-
ing the response of the cold start transient reaction, eight glow plugs were mounted at the inlet of the catalyst to
control the flow temperature together with the adjustment of the oxygen to methanol mol ratio.
The best response from cold start was obtained with 960 W heating power, 80 C heating temperature,
14 mL/min methanol and 70 L/min air supply rates among the experimented parameters. Under this oper-
ation setting, hydrogen was produced after 220 s from cold start with the production rate stabilising after
4–5 min and eventually reaching the highest concentration at 350 C. Generally, hydrogen commenced pro-
duction at a catalyst outlet temperature of 100 C and stabilised at 350 C.
2004 Elsevier Ltd. All rights reserved.
Keywords: Methanol reformer; Partial oxidation; Cold start; Transient performance; Hydrogen production
*
Corresponding author. Tel.: +886 6 205 0496; fax: +886 6 205 0509.
E-mail address: [email protected] (R.-F. Horng).
0196-8904/$ - see front matter 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.enconman.2004.06.018
1194 R.-F. Horng / Energy Conversion and Management 46 (2005) 1193–1207
Nomenclature
B bias limit
N repeated measurements
S standard deviation
S x average precision
t a parameter; a function of measurement times and average precision
U measurement uncertainty
URSS measurement uncertainty derived by root sum square method
b bias error
dk total measurement bias
ek precision error
Subscripts
k source of error
RSS root sum square
x average value of total measurements
1. Introduction
Severe air pollution in cities is a common problem faced by countries worldwide. Although it is
generally accepted that electrifying vehicles is one of the most efficient methods in reducing this
problem, this method has never quite been popularised due to the difficulties in maintaining a con-
stant supply of electricity such as battery lives, battery recharging times etc., while the vehicle is in
transit.
The fuel cell, which uses hydrogen to generate electricity, is generally regarded as the most pro-
spective method of powering vehicles. The main consideration is, thus, the source of the hydrogen
and the method of storing it. The traditional method of storing gas in pressurised metal cylinders
is not ideal as hydrogen is highly combustible. It is only very recently that a hydrogen storage can-
ister was developed, which enabled safe storage of hydrogen and, therefore, the usage of fuel cells
in electrical cars. Alternatively, if a small reformer that can produce hydrogen on board a car were
available, this would undoubtedly be a more efficient and safer method of powering electrical cars.
With a reformer, the main design considerations are its physical dimensions, its response rate after
cold start and its transient response during acceleration.
Hydrogen can be extracted by the reforming process from methanol, natural gas, fossil fuel etc.
The methods of reforming include partial oxidation, auto-thermal, steam reforming and so on [1].
Hydrogen obtained from methanol possesses the desirable characteristics of ease of decomposi-
tion and a low reaction temperature of approximately 250 C and is, thus, a suitable method
for steam reforming [2].
The Energy and Resources Laboratories of the Industrial Technology Research Institute of
Taiwan has published some papers since 1993 on research of reformers for fuel cells. Cheng [3]
proposed a set of design criteria and did a literature review of the development of the reformer.
R.-F. Horng / Energy Conversion and Management 46 (2005) 1193–1207 1195
Sung [4] conducted a theoretical and experimental investigation on a methanol reformer and re-
vealed that the conversion efficiency of methanol increased with the temperature of the reformer
as did the CO level. He recommended the outlet temperature of the reformer be controlled be-
tween 180 and 310 C. Sung [5] also investigated a methane steam reformer and discovered that
the CO concentration from the reformer fulfilled the level of the fuel cell. He further suggested
that the water to methane ratio should not be too high in order to reduce the heat lost to heat
the water and proposed that further research be conducted to characterise the behaviour of the
reformer at the start and during changes in load. Chen [6] manufactured a small methanol refor-
mer with a metallic substrate combined with a Cu–ZnO/Al2O3 catalyst and performed a paramet-
ric study from which it was concluded that the reformer performed optimally with a water to
methanol mol ratio of 1.8 and an oxygen to methanol mol ratio of 0.2.
Recent years have seen the rapid development of methanol reformers in particular applications
involving cars. Numerous papers have been published by many researchers investigating the effect
of cold start and the dynamic characteristics of methanol reformers. Hohlein et al. [7] manufac-
tured a methanol steam reformer system operated at 240, 260 and 280 C, respectively, and noted
the intimate relationship between the heating mode and the concentration of the emitted CO.
They also found that the characteristics of the starting process were less than expectation. Using
their newly constructed methanol reformer, Emonts et al. [8] discovered that under low load, the
conversion rate of methanol was significantly improved when the operating temperature was in-
creased from 260 to 280 C, with 100% conversion efficiency of methanol. Further increase in tem-
perature, however, resulted in less evident improvement. They further revealed that the higher the
temperature, the higher was the concentration of the emitted CO, the level of which was reduced
as the load was increased. Wiese et al. [9] investigated the quasi-static and dynamic behaviour as
well as the start up condition of a methanol reformer and noted that reaction first occurred after
10 min from start up. As the reaction rate of the fuel supply system was found to influence the
dynamic response of the reformer significantly, they recommended that an injection method be
adopted to enhance performance. Han et al. [2] built a 3 kW methanol reformer, which provided
a thermal efficiency beyond 89% and attained maximum hydrogen production after 15 min from
cold start up. Nagano et al. [10] investigated catalytic methanol steam reforming by simulation
and experiment. They found that there was a trade off relationship between methanol conversion
and CO concentration. The trade off relationship was improved by using an internal corrugated
metal heater and an external catalytic combustion heater to enhance the heat transfer. Optimal
reaction parameters were also obtained. Takeda et al. [11] used a steam reforming method to-
gether with fuel oxidation in a methanol reformer to enhance the vapourisation effect of the heater
on the liquid fuel and water to accelerate the reaction of the catalyst. With a Cu–ZnO/Al2O3 cat-
alyst, Choi et al. [12] studied the hydrogen emission characteristics with and without adding water
to a methanol reformer. When no water was added, 100% reaction efficiency of the methanol
could be achieved, while the presence of water resulted in a high concentration of hydrogen
and a low level of CO. Holladay et al. [13] fabricated a micro scale methanol reformer and dis-
covered that the temperature of 360 C resulted in a conversion efficiency of 99% using the steam
reforming method for a O/C ratio of 1.8. Lindstrom and Pettersson [14] developed a methanol
reformer fitted in cars for Volvo. The catalyst in the reformer under a combined partial oxidation
and steam reforming method commenced operation after 4–6 min. Loffler et al. [15] included a
pre-reformer in their reformer system, which promoted achieving the activation temperature of
the catalyst through fuel oxygenation and the main reformer attained the reaction condition by
the steam reforming method. This system resulted in a high thermal efficiency and a high purity
of the hydrogen produced.
From the above review, it is evident that the methanol reformer has a desirable fast response to
achieve the reaction temperature and is highly suitable for use with fuel cells to power automo-
biles. However, more efforts are still needed on the cold start and transient characteristics of
the reformer if it is to be used as an on board vehicle fuel processor. The study on the cold start
behaviour of the methanol reformer to find the parameters for shortening the start up time is the
main aim of this paper.
2. Experimental method and procedure
2.1. Experimental set up
The main apparatus was a purposely designed reformer with a catalyst supplied by the Het-
erogeneous Catalysis Department in the Union Chemical Laboratories of the Industrial Tech-
nology Research Institute of Taiwan. The experimental set up is shown in Fig. 1, and the
specifications of the reformer are listed in Table 1. Other equipment included a fuel supply sys-
tem, a temperature controlling unit, a gas sampling system and a gas chromatographer (Agilent
Model 6850). The catalyst was coated with a layer of honeycombed ceramic whose main com-
ponents were Pt and the mixed oxide of Cu–ZnO/Al2O3. The fuel supply system consisted of a
liquid and an air injection sub-system, each equipped with a pressure regulator and a flow meter.
Fig. 1. Experimental arrangement of the methanol reformer.

Table 1
Specifications of the reformer
Main body
Reaction chamber 124B mm stainless steel
Height 510 mm
Nozzle Fuel, water, air
Heater 120 W · 8 glow plugs
Power supply for heater 12 VDC
Catalyst
Substrate Ceramic
Diameter 117B mm
Length 50 mm
Composition Pt and Cu–ZnO/Al2O3
Mesh 64 cells/cm2
The liquid fuel system had an additional electrical fuel pump and a fuel injector, which injected
vapourised liquid methanol fuel, while the air injection system had a single and a multi hole
injector. The fuel was well vaporised as it came into the catalyst. The flow temperature control
system consisted of glow plugs, a temperature controller and a temperature logger. Each glow
plug supplied a heating power of 120 W with a 12 V d.c. battery and a total of eight glow plugs,
providing 960 W were employed to control the temperature of the flow entering the catalyst.
Five K-type thermocouples were positioned at the front and the back of the fuel spray, the inlet
and the outlet of the catalyst and at the smallest radius of the tapered pipe. The temperature at
the outlet of the catalyst acted as the feedback to the temperature controller. The flow sampling
and analyzing system consisted of a condenser, a sampling pump, sampling bags, a micro syringe
and a gas chromatographer.
2.2. Experimental method
As the main objective of the paper is to investigate the characteristics of the methanol reformer
after cold start, the method of partial oxidation was employed to determine the best experimental
parameters and operating procedure. The parameters included O/C ratio, heating power, heating
temperature, methanol supply rate and air flow rate. For each transient test, the gas chromatog-
rapher was first warmed up before initiating the data logger. Next, the heating system was acti-
vated, and air heated by the glow plugs was then directed into the catalyst for pre-heating.
After 10 s, the liquid fuel unit commenced supply, and simultaneously, the emitted gas was sam-
pled, and the sample injected into the gas chromatographer for analysing its transient character-
istics. This process continued until the composition of the gas achieved stability. To ensure no gas
contamination, the sample bag must be vacuumed to remove any gas after each sampling. Be-
tween each cold start test, the entire system was shut down for at least six hours so that the tem-
perature of the reformer system returned to room temperature. As mentioned, partial oxidation
was used to investigate the stable characteristics of the reformer, and the methanol supply rate
was used as the base line for calculating the required air flow using the O/C ratio. The supply rate
was fixed as 14, 10 and 6 mL/min, while the O/C ratio was set between 0.12 and 0.97.
Table 2
Measurement uncertainties
H2: ±1.01%
CO: ±0.51%
CO2: ±0.51%
Temperature: ±2.5 C
Current: ±0.4 A
Voltage: ±0.2 V
One of the main measuring instruments was the gas chromatographer, which gave a calibration
line that determined the measurement accuracy of the gas composition. The calibration line was
obtained by feeding three different concentrations of standard gas samples into the gas chroma-
tographer and solving through linear regression for a R2 (regression coefficient) that was above
0.999. Subsequent gas concentration produced from the reformer was thus determined based
on this line. This system used argon as the carrier gas and the column used was SUPELCO 1-
2390-U. The setting of the gas chromatographer was a carrier gas flow rate of 10 mL/min, an inlet
temperature of 100 C, an oven temperature of 160 C and a detector temperature of 200 C.
2.3. Measurement error analysis
The total measurement error (dk) includes a bias error (b) and a precision error (ek) such that
[16]
dk ¼ b þ ek ð1Þ
The precision error is determined by taking N repeated measurements. The precision index of
the average of a set of measurements is always less than that of an individual measurement
according to
S
S x ¼ pffiffiffiffi ð2Þ
N
where S is the standard deviation of the N repeated measurements. The bias error is the systematic
error, which is considered to remain constant during a given test. The measurement uncertainty
(U) with 95% confidence can be given by the followed model:
1
U RSS ¼ ½B2 þ ðtS x Þ2 2 ð3Þ
where URSS is the measurement uncertainty derived by the root sum square (RSS) method, B is
the bias limit, and t is set equal to 2 for large samples (N > 30).
According to the above analysis, the measurement uncertainties are estimated and shown in
Table 2.
3. Results and discussion
In the experiment, different heating powers, coupled with different heating temperatures was
studied to establish an operating procedure of the reformer from cold start. From this procedure,
the best experimental parameters, such as the methanol supply rate and air flow rate were then
determined. Figs. 2–4 compare the time taken for the outlet temperature of the catalyst to reach
200 C, the self initiation temperature of the catalyst, under different heating powers coupled with
different heating temperatures. It is noted that the shorter the time taken, the more efficient is the
operation.
Fig. 2 shows the results for a heating power of 960 W. It is evident from the figure that when the
pre-set heating temperature is 80 C, the methanol supply rate is 14 mL/min and the air flow rate
is 70 L/min, the best cold start condition is achieved in 220 s. This is followed closely by the setting
conditions of 60 C and 40 C heating temperatures coupled with the same air flow rate of 70
L/min, which give 230 and 257 s, respectively. Further, under the same heating temperature of
80 C, but coupled with a methanol supply rate of 10 mL/min and a air flow rate of 60 L/min,
an efficient cold start operating condition of 260 s, approximately, can be obtained. Good oper-
ating results are also obtained under the conditions of 60 and 40 C heating temperatures coupled
with an air flow rate of 60 L/min to give the time taken for the temperature at the outlet of the
catalyst to reach 200 C as 270 and 275 s, respectively. However, when the methanol supply rate
is 6 mL/min, the time taken after cold start to reach the required temperature is above 380 s,
clearly much slower than the former two settings. Nevertheless, when a heating temperature of
80, 60 or 40 C is coupled with any of the above settings, the temperatures at the catalyst outlet
all reached 200 C. In other words, the self initiation conditions can be achieved for any of the
three heating temperatures.
Fig. 3 shows the results for a heating power of 720 W. From the figure, it is clear that the com-
bination of 80 C heating temperature, 14 mL/min methanol supply rate and 70 L/min air flow
rate results in the best cold start response, i.e. a total time of 235 s. Other desirable combinations
include heating temperatures of 60 and 40 C with an air flow rate of 70 L/min, which result in
600
Heating power: 960W
550
Time for T4 to reach 200oC(sec)
Methanol supply
500 14mL/min 10mL/min 6mL/min
80oC 80oC 80oC
450 60oC 60oC 60oC
o
o
40 C 40 C 40oC
400
350
300
250
200
150
30 35 40 45 50 55 60 65 70 75 80 85 90
Air supply (L/min)
Fig. 2. Comparison of the effect of air supply rate on the time taken for the outlet temperature of the catalyst to reach
200 C under different methanol supply rates and different heating temperatures at a heating power of 960 W.
600
Heating power: 720W
550

Methanol supply
80oC 80oC 80oC
450 60oC 60oC 60oC
o o
40 C 40 C
400
350
300
250
200
150
30 35 40 45 50 55 60 65 70 75 80 85 90
Air supply (L/min)
600
Heating power: 480W
550
Methanol supply
80oC 80oC 80oC
450
o
60 C 60oC 60oC
40oC 40oC 40oC
400
350
300
250
200
150
30 35 40 45 50 55 60 65 70 75 80 85 90
Air supply (L/min)
times of 250 and 265 s, respectively. When the methanol supply rate is reduced to 10 mL/min and
the air flow rate is 60 L/min, the time taken to reach 200 C is between 270 and 280 s. The longest
time taken is when the methanol supply rate is 6 mL/min.
Fig. 4 shows the results for a heating power of 480 W. The shortest time taken is between 245
and 280 s for the test condition of 80 C heating temperature, 70 L/min air flow rate and 14 mL/
min methanol supply rate. When the methanol supply rate is reduced to 10 mL/min and the air
flow rate is 60 L/min a good cold start condition is also achieved and the time taken for this case
is between 280 and 300 s. As with Figs. 2 and 3, a methanol supply rate of 6 mL/min results in the
longest time taken to achieve 200 C.
From the above experimental results, it is clear that the best setting of those tested is with the
combination of a heating power of 960 W, a heating temperature of 80 C, a methanol supply rate
of 14 mL/min and an air flow rate of 70 L/min, which resulted in the shortest time of 220 s to
achieve the 200 C requirement at the catalyst outlet. This is followed by the combination of a
heating power of 960 W, heating temperature of 60 C, methanol supply rate of 14 mL/min
and air flow rate of 70 L/min, giving the time required as 230 s.
Figs. 5–7 present the temperature distribution at the reformer under the test conditions of 80 C
heating temperature, a methanol supply rate of 14 mL/min, an air flow rate of 70 L/min for heat-
ing powers of 480, 720 and 960 W, respectively. Simultaneously, the reformer temperature devel-
opment of previously published work [14] was compared with this study in these figures. T1 and T2
are the temperatures in front and behind the fuel spray, respectively, while T3 and T4 are the tem-
peratures at the inlet and outlet of the catalyst. From the temperature variations of T1, T2 and T3,
it is evident that after cold start, the methanol immediately comes into contact with the high tem-
perature air and the heaters to produce significant oxidation, which causes its temperature to rise
rapidly. It is noted that the experiment was designed such that the catalyst is heated by the heat in
the air flow until the outlet temperature reaches the pre-set 80 C. As soon as the heaters are
turned off, the air flow before the catalyst cools down, and therefore, the methanol would not
be oxidised in this region. It is activated instead in the catalyst as the elevated temperature of
the catalyst reduces the air flow rate. At the same time, T1, T2 and T3 decrease rapidly due to
the reduced heat supply from the heaters and the oxidation of the methanol, results from turning
Set heating power: 480 W

500 T3 Set heating temp.: 80oC
Methanol supply: 14 mL/min
T2 Air supply: 70 L/min
400
T4
Temperature (oC)
T1
300
200 Reformer
temperature
of Ref.14
100
0 T4=80 oC
0 100 200 300 400 500

Time from cold start (sec)
Fig. 5. Temperature–time histories at various positions of the reformer during the transient condition after cold start of
a reformer for heating powers of 480 W.

500 T3
Set heating temp.: 80oC
Methanol supply: 14 mL/min
T2 Air supply: 70 L/min
400
Temperature (oC) T1 T4
300
200
Reformer
temperature
of Ref. 14
100
0 T4=80 oC
0 100 200 300 400 500

the reformer for a heating power of 720 W.
600
T3 Set heating temp.: 80oC
500 Methanol supply: 14 mL/min
Air supply: 70 L/min
T2
400 T1
Temperature (oC)
T4
300
200
Reformer
temperature
100 of Ref. 14
0 T4=80 oC
0 100 200 300 400 500

the reformer for a heating power of 960 W.
off the heaters and the reduced air flow rate. The rapid increase of T4 is attributed to the achieve-
ment of the catalyst light-off temperature. From Fig. 5 it is evident that when the heating power is
480 W, the rate of increase of T1 and T2 are similar, while that of T3 is more gradual. The time
taken for T4 to reach the pre-set 80 C is approximately 179 s, to reach 200 C is approximately
237 s and to reach the maximum temperature is approximately 360 s. Fig. 6 presents the results for
the case where the heating power is 720 W. As with the previous case, the rate of increase of T1
and T2 are the same. The difference is that T3 also increases at a similar rate. With the higher heat-
ing power, the time taken for T4 to reach 80 C is shorter at about 173 s, to reach 200 C is
approximately 231 s and the time to reach the maximum temperature is approximately 355 s.
When the heating power is further increased to 960 W as shown in Fig. 7, the rate of increase
of T1, T2 and T3 are almost identical. In this case, the time taken for T4 to reach 80 C is an even
shorter 165 s, to reach 200 C is about 220 s and that to reach the maximum temperature is 345 s,
approximately. As compared with the results of the previous work, as shown in the figures, the
reformer temperatures of this study exceed those of Lindstrom et al. [14] at approximately
210–220 s. Furthermore, the time for their reformer temperature to reach 200 C is approximately
270 s. However, as discussed above, the times for reaching the same temperature in our study are
237, 231 and 220 s for heating powers of 480, 720 and 960 W, respectively. That is, the cold start
response of this study is comparable to that of LindstromÕs. From the above analysis, it is appar-
ent that heating power significantly affects the rise rate of the inlet and outlet temperatures of the
catalyst. In other words, the higher the heating power, the faster is the temperature rise rate in the
studied settings, which essentially means that the catalyst reaches its self initiation temperature in
a shorter time.
Fig. 8 shows the catalyst outlet temperature variation and the concentration of H2, CO and
CO2 emitted during the transient condition after cold start with a heating power of 960 W and
the best settings of those experimented, i.e. a heating temperature of 80 C, a methanol supply
rate of 14 mL/min and a gas supply rate of 70 L/min. It is clear that no hydrogen is produced
when the outlet temperature is under 80 C. The reason attributed to the increase in the rise rate
of the temperature of the catalyst due to the release of a significant amount of heat energy, which
occurs when the methanol to air ratio approaches the theoretical air–fuel ratio, for heating the
45 500
Temperature of catalyst outlet, T4 (oC)
40 o
Set heating temp.: 80 C
Methanol supply: 14 mL/min H2
35 Air supply: 70 L/min 400
T4
H2, CO, CO2 (Vol%)
30
25 300
20
15 CO 200
10
5 CO2 100
-5 0
0 100 200 300 400 500
Fig. 8. Gas composition and outlet temperature of the catalyst with time during the transient condition after cold start
of the reformer for a heating power of 960 W.
catalyst and the main body of the reformer. Consequently, the majority of the methanol will com-
bust due to oxidation. Therefore, an initial level of 5% CO2 appears, and the concentration of CO
and H2 remains zero until the heaters stop operating and the air supply rate reduces to a suitable
level such that the severe oxidation of methanol shifts to partial oxidation to start producing H2.
The outlet temperature of the catalyst at this instance is 100 C, approximately and rapidly in-
creases as does the concentration of H2. The increase in concentration of the CO and CO2 is, how-
ever, more gradual. When the outlet temperature reaches approximately 350 C, the production
rate of H2 stabilises and the hydrogen concentration remains at approximately 37%.
Figs. 9 and 10 show the gas composition of the emission from the reformer and the temperature
variation at the catalyst outlet for heating powers of 720 and 480 W, respectively, during the tran-
sient condition after cold start. In general, the outlet temperature of the catalyst and the variations
of the concentrations of H2, CO and CO2 are similar to those when the heating power was 960 W.
The main disparities are the more gradual overall temperature rise, which delayed the reaction of
the catalyst, and the slower reaction rate of the catalyst.
Fig. 11 compares the effect of different heating powers on the outlet temperature of the catalyst
and the H2 concentration during the transient condition of the reformer after cold start. It is clear
that under a heating power of 960 W, the temperature rise at the outlet of the catalyst is the fastest
as is the rise in the concentration of hydrogen. This is followed by the heating temperature of 720
W and then by 480 W. It is evident that under the three different conditions, the higher the heating
power, the higher is the rise rate of the temperature and the production of H2. Despite this differ-
ence, the times taken to achieve stable production of hydrogen for the three cases are almost iden-
tical and the concentration of H2 produced are also similar.
Fig. 12 shows the relation between the outlet temperature of the catalyst and the hydrogen
concentration under the different methanol supply rates and O/C ratios when the reformer sta-
bilises. Because of the methanol supply rates and the limit of the operating temperature of the
45 500
40 o

H2, CO, CO2 (Vol%)
30 T4
25 300
20
15 CO 200
10
5 CO2 100
-5 0
0 100 200 300 400 500
45 500
40 o

H2, CO, CO2 (Vol%) 30 T4

25 300
20
15 CO 200
10
5 CO2 100
-5 0
0 100 200 300 400 500
500
40 Set heating temp.: 80oC

Methanol supply: 14 cc/min
35
Air supply: 70 L/min H2
Hydrogen 400
30 960W
720W
T4
Hydrogen (Vol%)
25 480W
300
Temperature
20 960W
720W
15 480W
200
10
5 100
-5 0
0 100 200 300 400 500
Fig. 11. Comparison of the effect of heating power on the outlet temperature of the catalyst and the H2 concentration
during the transient condition after cold start of the reformer.
catalyst, different methanol supply rates would produce different limiting values of the O/C ratio.
Further, it is clear from the figure that under different methanol supply rates, the outlet temper-
ature of the catalyst and the concentration of H2 produced reveal similar trends. In other words,
as the O/C ratio increases, the outlet temperature of the catalyst and the H2 concentration in-
crease simultaneously. When the methanol supply rate is 14 mL/min and the O/C ratio is
0.46, the best H2 produced was 41% in volume. The corresponding outlet temperature of the cat-
alyst is 355 C. If the supply rate is reduced to 10 mL/min and the O/C ratio is increased slightly
45 550
Methanol supply

40 14ml/min
10ml/min 500
35
6 ml/min
30 450
Hydrogen (Vol%)
25
400
20 H2
15
350
10
5 300
T4 Methanol supply
0 14ml/min 250
-5 10ml/min
6 ml/min
-10 200
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
O/C ratio
Fig. 12. The relationship between the outlet temperature and the H2 concentration under different methanol supply
rates and O/C ratios during the stable condition of the reformer.
to 0.58, the peak value of H2 concentration produced is 36.5% in volume, and the corresponding
outlet temperature of the catalyst is 352 C. At an even lower methanol supply rate of 6 mL/min
and a O/C ratio of 0.74, the highest H2 concentration produced falls to a mere 29.3% in volume,
and the associated outlet temperature of the catalyst is 320 C, approximately. Beyond this peak
value of the curve, even though the outlet temperature continues to rise, the H2 concentration
appears to fall.
4. Conclusions
A series of experiments were conducted to investigate the transient characteristics of a methanol

reformer and the following conclusions were drawn. After cold start, the higher the heating power
and the methanol supply rate, the quicker was the cold start reaction. The best operating condi-
tion of these tested for the reformer was a heating power of 960 W, a heating temperature of 80
C, a methanol supply rate of 14 mL/min and an air supply rate of 70 L/min. This operating com-
bination required only 220 s until hydrogen was being produced, and the production stabilised
between 4 and 5 min. The outlet temperature of the catalyst when hydrogen commenced produc-
tion was approximately 100 C, and at maximum hydrogen production, the temperature was 350
C, approximately. By combining different heating powers with different heating temperatures,
methanol supply rates and air supply rates, the reformer can eventually achieve the state of stable
hydrogen production.
During the stable condition, it was found that the higher the methanol supply rate, the higher
was the outlet temperature of the catalyst as well as the H2 production concentration. Further,
with a change of O/C ratio, a peak existed in the concentration of H2 produced. Therefore, a spec-
ified O/C ratio must be combined with appropriate methanol supply rates in order to achieve a
satisfactory production efficiency of H2 by the catalyst.
Acknowledgement
The author gratefully acknowledges the support of the National Science Council of Taiwan,
ROC, under grant NSC 91-2212-E-168-015. Thanks are also due to the Heterogeneous Catalysis
Department in the Union Chemical Laboratories of the Industrial Technology Research Institute
for providing the catalyst in the experiments and technical support.
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Transient Behaviour of A Small Methanol Reformer For Fuel Cell During Hydrogen Production After Cold Start

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Energy Conversion and Management 46 (2005) 1193–1207

Transient behaviour of a small methanol reformer for fuel

2. Experimental method and procedure

2.1. Experimental set up

Fig. 1. Experimental arrangement of the methanol reformer.

2.2. Experimental method

2.3. Measurement error analysis

3. Results and discussion

Time for T4 to reach 200oC(sec)

Set heating power: 480 W

0 100 200 300 400 500

Set heating power: 720 W

0 100 200 300 400 500

0 100 200 300 400 500

Set heating temp.: 80 C

Temperature of catalyst outlet, T4 (oC)

H2, CO, CO2 (Vol%) 30 T4

Temperature of catalyst outlet, T4 (oC)

Temperature of catalyst outlet, T4 (oC)

A series of experiments were conducted to investigate the transient characteristics of a methanol

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