8906 Ind. Eng. Chem. Res.

2007, 46, 8906-8909

Methanol Conversion for the Production of Hydrogen

Charles E. Taylor,* Bret H. Howard, and Christina R. Myers
U.S. Department of Energy, National Energy Technology Laboratory, P.O. Box 10940,
Pittsburgh, PennsylVania 15236-0940

The production of methanol from a variety of biomass sources is gaining favor. Several facilities exist or are
under construction throughout the world to convert biogenerated methane from the decomposition of biomass
into methanol using conventional steam reforming. Methanol is an excellent liquid-hydrogen-transport medium.
When powered by hydrogen, fuel cells have the potential to be the cleanest and most efficient source of
electricity for use by the automotive industry. On-board reforming of liquid hydrocarbon fuels is a viable
alternative to the storage of compressed hydrogen. A problem in current reforming processes is the quantity
of carbon monoxide (CO) produced. Our research is geared toward circumventing the production of carbon
monoxide in methanol reforming through the development of novel reforming catalysts. By modifying a
copper-based catalyst, we have produced several catalysts that retain their activity and high surface area after
extended methanol reforming runs both with and without the addition of steam.

Introduction Experimental Section

Our goal is to develop an efficient and cost-effective process
that uses methanol as the hydrogen source for an on-board fuel
cell. Methanol has the highest weight percent (12.5%) of
hydrogen of any liquid hydrocarbon. This is nearly double the
U.S. Department of Energy’s goal for using hydrogen as a fuel
for automobiles.1 One major drawback to current reforming
catalysts is the production of carbon monoxide. Carbon mon-
oxide acts a poison upon contact with the proton-exchange-
membrane (PEM) fuel-cell (Pt-based) catalyst.2,3
The objective of our research is to reduce the quantity of
carbon monoxide produced during reforming to near-zero levels.
Current investigations favor methanol as the liquid hydrocarbon
that acts as the chemical carrier for hydrogen for fuel cells. The
reasons are its ready availability, its compatibility with the
current liquid-fuel-based infrastructure, and its high energy
density. These characteristics allow easier storage and trans-
portation. To eliminate the CO poisoning of the PEM fuel cell,
a catalyst must be developed that operates at moderate temper-
atures (330-400 °C) and that has hydrogen and carbon dioxide
as its primary products. Most reforming processes require high
temperatures and produce a high CO yield. High operating
temperatures are neither cost-effective nor considered safe by
the public for on-board fuel cells.
We reviewed investigations of various catalysts used in the
reforming of liquid hydrocarbons, such as methanol and
petroleum-based fuels. On the basis of our literature search, we
selected various copper-based catalysts that are active for the
steam reforming of methanol.4-8 These catalysts operate at
temperatures low enough that carbon monoxide is not a
significant product, and they are stable under our selected
operating conditions. A copper-based catalyst that has shown
much promise is the Cu/Zn/Zr/Al/Y-based catalyst.9,10 We
synthesized this catalyst in our laboratory and compared its
performance to that reported in the literature. This catalyst’s
performance was used as a baseline for our catalyst development
effort. Investigative research and testing has begun on several
novel copper-based catalyst variations. The variants are Cu/Zn
on Zr/Al/Y, Cu/Zr on γ-Al2O3, Cu/Zn/Zr on γ-Al2O3, and Cu/
Zn/Ce on γ-Al2O3.
10.1021/ie061307v This article not subject to U.S. Copyright. Published 2007 by the American Chemical Society
Published on Web 06/01/2007
The catalysts were prepared using three different methods:
sequential precipitation, coprecipitation, and incipient wetness.
Table 1 lists the various catalysts prepared for this study, along
with the method of preparation and the BET surface areas of
the catalyst as prepared and after reaction. An example of the
catalyst preparation method for sequential precipitation is as
follows: Appropriate amounts of Zr(NO3)2O, Al(NO3)3‚9H2O,
and Y(NO3)3‚6H2O were dissolved in 125 mL of distilled water
and heated to 70 °C. This solution was added dropwise into a
1500 mL beaker containing 200 mL of water at 70 °C on a
hotplate with stirring. The pH was maintained at 7. A pH meter
was used to monitor the pH of the solution, and adjustments
were made by adding Na2CO3 solution as needed. After a 10-
min aging period, a solution of Cu(NO3)2 in 250 mL of distilled
water at 70 °C was added dropwise to the suspension. After
approximately 20 min of aging, a solution of Zn(NO3)2 dissolved
in 125 mL of distilled water at 70 °C was added dropwise to
the existing suspension. The pH was maintained at 7 during all
additions using Na2CO3 solution as above. The product was
recovered by vacuum filtration using a Büchner funnel and
washed with distilled water. The sample was dried at 120 °C
overnight and then calcined in air at 350 °C for 6 h.
A typical incipient wetness preparation was used for the
synthesis of supported catalysts. A solution containing the metals
of interest as nitrate salts was prepared in a volume of water
previously determined to just wet the predried support material.
The solution was added slowly, with mixing, to the support.
The mixture was dried at 120 °C overnight and then calcined
in air at 350 °C for 6 h.
All reforming reactions were conducted in a 0.5 in. o.d. ×
0.375 in. i.d. (1.27 cm o.d. × 0.95 cm i.d.) × 10 in. (25.4 cm)
304 stainless steel reactor. The inside wall of the reactor was
coated with Restek Corporation’s Silcosteel coating for surface
passivation. The catalyst was supported in the reactor between
deactivated quartz wool plugs, and the reactor was operated in
an upflow configuration. A gold-plated thermocouple in the
center of the catalyst bed was used to control the temperature
of reaction to (0.5 °C. Brooks proportional ratio mass-flow
controllers were used to control the gas feed to the reactor, and
an Isco high-pressure syringe pump provided liquid feed control.
The feed streams were preheated to approximately 130 °C prior
 Ind. Eng. Chem. Res., Vol. 46, No. 26, 2007 8907

Table 1. Reforming Catalyst Composition, Preparation Method, and Table 2. Methanol Conversion and Product Yield for the Reactions
Surface Area without Co-fed Water
surface area (m2/g) temperature time on CH3OH H2 CO2 CO
sample (°C) stream (h) conversion (%) (%) (%)
composition preparation as- after
sample (mol %) method prepared reaction BH5-2 150 1.17 21.78 1.92 98.08 a
literature9 150 b 5 4 1 0
BH5-2 Cu/Zn/Zr/Al/Y sequential 92 55
BH5-2 255 1.05 83.20 90.09 9.01 a
69:17:10:2:2 precipitation
literature9 255 b 80 55 12 0
BH5-3 Cu/Zn/Zr/Al/ coprecipitation/ 21 16
BH5-2 255 51.00 61.53 92.98 7.02 a
8:2:64:13:13 incipient wetness
BH5-3 255 1.00 100.00 29.41 70.59 a
BH5-4 Cu/Zr/γ-Al2O incipient wetness 200 188
BH5-3 255 3.00 49.09 77.65 5.78 16.57
12:5:83
BH5-4 255 2.58 99.89 48.01 21.35 30.64
BH5-10 Cu/Zn/Zr/γ-Al2O incipient wetness 198 187
BH5-10 250 1.00 79.04 51.73 38.84 9.43
12:2.5:25:83
BH5-12 250 1.08 94.25 44.08 16.19 39.73
BH5-12 Cu/Zn/Ce/γ-Al2O incipient wetness 194 195
12:2.5:2.5:83 a Not detected. b Not given.

to entering the reactor, and the reaction products were held at
approximately 150 °C between the exit of the reactor and the
cold trap. The cold trap was maintained at -4 °C using a
temperature-controlled chiller.
Typical reaction conditions were as follows: Exactly 1.0000
g of catalyst was placed in the reactor supported between the
quartz wool plugs such that the tip of the gold-plated thermo-
couple was located in the middle of the catalyst bed. The reactor
was purged at ambient temperature with helium at 5 mL/min
for at least 2 h prior to reaction. The temperature of the reactor
was increased to either 150 or 255 °C under a helium flow.
The methanol flow was begun, at a weight hourly space velocity
of 1.0 h-1, after the catalyst had reached the selected reaction
temperature.
Reaction conditions for the methanol/water reforming reac-
tions were identical to those for the pure methanol reforming
reactions with the exception that the feed was an equimolar
mixture of methanol and distilled-deionized water.
Reaction products were directly sampled and analyzed by an
online dual-column gas chromatograph (GC). The GC, a
Hewlett-Packard 5890 Series II instrument, was equipped with
a 6 ft × 0.0125 o.d. 80/100 Porapak Q column and a 20 ft ×
0.0125 o.d. 60/80 Molecular Sieve 5 Å column (both obtained
from Supelco). The GC was held at a constant temperature of
100 °C during elution. Argon was used as the carrier gas at an
average flow rate of 30 mL/min for the Molecular Sieve column
and 50 mL/min for the Porapak Q column at 30 °C. The
Molecular Sieve column was used to separate the light gaseous
products, whereas the Porapak Q column was used to identify
liquid hydrocarbons. Both columns were equipped with back-
flushing capability. Dual thermal conductivity detectors (TCDs)
were employed to detect the separated components.
Results and Discussion
Methanol Reforming Reactions without Water. Five
catalysts were prepared and tested for their ability to reform
methanol without water in the reactant feed. The majority of
methanol reforming catalysts require mixtures of methanol and
water to function at high conversions and selectivities. The water
is used to convert the byproduct carbon monoxide to hydrogen
and carbon dioxide by the water-gas shift reaction. In this study,
we chose to initially study the reforming ability of the catalysts
without co-feeding water with the methanol. After determining
performance under these conditions, performance in a system
that included co-fed water was evaluated.
The first catalyst tested was our preparation of the catalyst
that had been reported in the literature9 to have the best overall
methanol conversion and product distribution, Cu/Zn/Zr/Al/Y.
The catalyst, prepared according the method described in the
literature9 (BH5-2), exhibited an as-prepared surface area of 92
m2/g. This value agrees with the value reported in the literature
of 92 m2/g. Reforming of methanol was performed at various
reaction temperatures. Table 2 lists the data from a series of
reforming reactions performed in our laboratory and those for
the Cu/Zn/Zr/Al/Y catalyst as reported by Breen and Ross.9
Conversion of methanol with our preparation of the literature
catalyst produced results similar to those reported in the
literature. As shown in Table 2, methanol conversion increases
with reaction temperature. At 150 °C, methanol conversion for
BH5-2 was approximately 25%. The majority of product
detected by the gas chromatograph was carbon dioxide. When
the reaction temperature was increased to 255 °C, conversion
of methanol increased initially to 83%. The product distribution
also changed, with hydrogen comprising approximately one-
half of the detected product. Of importance is the fact that carbon
monoxide was not detected at either reaction temperature in
our investigation (without water as a reactant) or in the literature
results.
Conversion of methanol at 255 °C decreases with time on
stream (Figure 1). This decrease in performance is most likely
due to coke formation during the reaction. Even though the
catalyst exhibits a rapid decrease in conversion over the first
20 h on stream, conversion and product selectivity ultimately
stabilize to constant values (Figure 1). As listed in Table 2,
conversion decreases to approximately 60% as the product
selectivity improves slightly. These experiments were conducted
up to 250 h with no change in conversion or selectivity after
the initial drop. After reaction, the catalyst was removed from
the reactor and examined. The appearance and consistency of
the used catalyst suggested that coke had formed during the
reaction. The catalyst also exhibited a 40% decrease in surface
area during the reaction. This decrease might result from the
coke formation and/or sintering of the unsupported metals in
the catalyst.
According to the literature,9 zirconium/aluminum/yttrium acts
as a support for the copper/zinc catalyst. The literature results
also suggest a synergy between copper and zirconium that is
not evident between copper and aluminum. However, as shown
in Table 1, the copper and zinc comprise 86 mol % of the
catalyst composition. In an effort to produce a more effective
supported copper/zinc catalyst, we synthesized a catalyst (BH5-
3) by first coprecipitating the zirconium/aluminum/yttrium
support and then adding the copper and zinc by incipient
wetness. This resulted in a catalyst with copper and zinc
comprising only 10 mol % of the catalyst. However, this also
resulted in a catalyst with a very low surface area of 21 m2/g
(Table 1).
Initial conversions of methanol on BH5-3 were high (ap-
proximately 100%), and product selectivity was poor. As time
8908 Ind. Eng. Chem. Res., Vol. 46, No. 26, 2007
Figure 1. Results of methanol conversion over the Cu/Zn/Zr/Al/Y (BH5-
2) catalyst as a function of time.
Figure 2. Results of methanol conversion over Cu/Zr on γ-Al2O3 (BH5-
4) at 255 °C.
Figure 3. Methanol conversion as a function of time on stream at 255 °C
for catalysts with different surface areas (refer to Table 1).
on stream increased, methanol conversion decreased (to ap-
proximately 40%), whereas product selectivity improved
(Table 2).
In an effort to improve the conversion and selectivity of the
reforming catalyst, we prepared several new catalysts. Catalysts
BH5-4, BH5-10, and BH5-12 were all prepared by addition of
the metals to γ-alumina by incipient wetness. The support was
changed to γ-alumina in an effort to increase the catalyst’s
surface area. These catalysts exhibited the highest surface areas
of any catalysts we prepared (Table 1). After reaction, these
catalysts retained >94% of their original surface areas.
The first catalyst synthesized in this series was BH5-4, copper
and zirconium on γ-alumina. This combination was chosen on
the basis of a literature9 report that a 2.4:1 molar ratio of copper
Figure 4. Results of methanol/water conversion over Cu/Zn/Zr on γ-Al2O3
catalyst as a function of time.
to zirconium produced the highest turnover number per copper
atom. Figure 2 shows the results of methanol reforming over
Cu/Zr on γ-Al2O3.
The catalyst exhibited high methanol conversion (>80%);
however, hydrogen production was <50 mol % because of a
large (30 mol %) production of carbon monoxide.
Zinc was added to copper and zirconium on γ-alumina (BH5-
10) to improve the dispersion of copper on the support. This
resulted in approximately the same methanol conversion (79%);
however, hydrogen production increased to >50 mol %, and
carbon monoxide production decreased to 9 mol %.
Catalyst BH5-12 was synthesized by replacing zirconium with
cerium. Cerium was chosen because it is chemically similar to
zirconium and has an additional oxidation state, thus providing
the possibility of increasing the turnover number. We observed
that methanol conversion decreases to a value less than that of
BH5-4 (copper/zirconium only) and the production of carbon
dioxide decreases as the production of carbon monoxide
increases.
The true test of any catalyst is its ability to perform for long
periods of time with minimal changes in the product slate. Figure
3 shows the results of methanol reforming on all of the catalysts
synthesized in this study over a 150-h period. As shown, all of
the catalysts perform well at the 1-h mark. After 50 h of
reforming, the BH5-2 and BH5-3 catalysts exhibited marked
decreases in methanol conversion. After 150 h of reforming,
only BH5-4, BH5-10, and BH5-12 still exhibited catalytic
activity. As listed in Table 1, these are the catalyst compositions
that exhibited the highest surface area (∼200 m2/g) after
synthesis. These catalysts also kept their high surface areas after
150 h on stream.
Methanol Reforming Reactions with Water. The main
byproduct from a hydrogen-fueled PEM fuel cell is water. This
water could be used as a co-feed in the methanol reforming
reactor to increase the conversion of methanol to hydrogen and
to reduce the amount of carbon monoxide produced by means
of a water-gas shift reaction on the catalyst. As reported in
the literature,9 methanol reforming reactions were carried out
using a sequentially precipitated Cu/ZnO/ZrO2/Al2O3 catalyst
and 1.3:1 H2O/CH3OH reactant mixture. In addition, the catalyst
was pretreated with a 5% H2/N2 mixture starting at room,
increasing the temperature at 5 °C/min to 240 °C and holding
at 240 °C for 4 h before reaction. In our experiments, the
catalysts prepared for the reforming experiments using only
methanol as the feed were tested, as-synthesized without
 Ind. Eng. Chem. Res., Vol. 46, No. 26, 2007 8909

Table 3. Methanol Conversion and Product Yield with the Addition The addition of cerium to the catalyst decreases methanol
of Steam (1:1) conversion and increases the production of carbon monoxide.
composition temperature CH3OH H2 CO2 CO Increased methanol conversion and hydrogen production was
sample (mol %) (°C) conversion (%) (%) (%) observed in experiments when we added water the reactant
BH5-2 Cu/Zn/Zr/Al/ 250 100.0 59.0 38.5 4.30 stream to facilitate the water-gas shift reaction. The addition
Y 69:17:10:2:2 of water to the feed also reduced the amount of carbon monoxide
BH5-3 Cu/Zn/Zr/Al/ 250 21.2 7.90 4.80 0.00 produced and enhanced the long-term stability of the catalysts.
Y 8:2:64:13:13
BH5-4 Cu/Zr/γ-Al2O3 250 99.4 43.2 30.4 1.10
12:5:83 Acknowledgment
BH5-10 Cu/Zn/Zr/γ-Al2O3 250 99.7 60.9 38.0 0.98 The authors acknowledge the technical assistance of Richard
12:2.5:25:83
BH5-12 Cu/Zn/Ce/γ-Al2O3 250 99.0 57.6 38.5 3.70 R. Anderson, Heather Elsen, Kris Howard, Edward P. Ladner,
12:2.5:2.5:83 Dirk D. Link, and Parsons Project Services, Inc. Reference in
this report to any specific commercial product, process, or
pretreatment, for their reforming and water-gas shift abilities. service is to facilitate understanding and does not necessarily
The feed consisted of an equimolar methanol/water mixture. imply its endorsement or favoring by the United States
Figure 4 displays the methanol reforming results for BH5- Department of Energy.
10 (Cu/Zn/Zr on γ-Al2O3), the catalyst that exhibited the highest Literature Cited
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They also maintained consistent levels of methanol conversion ReVised manuscript receiVed April 13, 2007
Accepted April 13, 2007
and hydrogen production during the extended reforming reac-
tions. IE061307V