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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 The catalysts were prepared using three different methods:
that uses methanol as the hydrogen source for an on-board fuel sequential precipitation, coprecipitation, and incipient wetness.
cell. Methanol has the highest weight percent (12.5%) of Table 1 lists the various catalysts prepared for this study, along
hydrogen of any liquid hydrocarbon. This is nearly double the with the method of preparation and the BET surface areas of
U.S. Department of Energy’s goal for using hydrogen as a fuel the catalyst as prepared and after reaction. An example of the
catalyst preparation method for sequential precipitation is as
for automobiles.1 One major drawback to current reforming
follows: Appropriate amounts of Zr(NO3)2O, Al(NO3)3‚9H2O,
catalysts is the production of carbon monoxide. Carbon mon-
and Y(NO3)3‚6H2O were dissolved in 125 mL of distilled water
oxide acts a poison upon contact with the proton-exchange-
and heated to 70 °C. This solution was added dropwise into a
membrane (PEM) fuel-cell (Pt-based) catalyst.2,3
1500 mL beaker containing 200 mL of water at 70 °C on a
The objective of our research is to reduce the quantity of hotplate with stirring. The pH was maintained at 7. A pH meter
carbon monoxide produced during reforming to near-zero levels. was used to monitor the pH of the solution, and adjustments
Current investigations favor methanol as the liquid hydrocarbon were made by adding Na2CO3 solution as needed. After a 10-
that acts as the chemical carrier for hydrogen for fuel cells. The min aging period, a solution of Cu(NO3)2 in 250 mL of distilled
reasons are its ready availability, its compatibility with the water at 70 °C was added dropwise to the suspension. After
current liquid-fuel-based infrastructure, and its high energy approximately 20 min of aging, a solution of Zn(NO3)2 dissolved
density. These characteristics allow easier storage and trans- in 125 mL of distilled water at 70 °C was added dropwise to
portation. To eliminate the CO poisoning of the PEM fuel cell, the existing suspension. The pH was maintained at 7 during all
a catalyst must be developed that operates at moderate temper- additions using Na2CO3 solution as above. The product was
atures (330-400 °C) and that has hydrogen and carbon dioxide recovered by vacuum filtration using a Büchner funnel and
as its primary products. Most reforming processes require high washed with distilled water. The sample was dried at 120 °C
temperatures and produce a high CO yield. High operating overnight and then calcined in air at 350 °C for 6 h.
temperatures are neither cost-effective nor considered safe by A typical incipient wetness preparation was used for the
the public for on-board fuel cells. synthesis of supported catalysts. A solution containing the metals
of interest as nitrate salts was prepared in a volume of water
We reviewed investigations of various catalysts used in the
previously determined to just wet the predried support material.
reforming of liquid hydrocarbons, such as methanol and
The solution was added slowly, with mixing, to the support.
petroleum-based fuels. On the basis of our literature search, we
The mixture was dried at 120 °C overnight and then calcined
selected various copper-based catalysts that are active for the in air at 350 °C for 6 h.
steam reforming of methanol.4-8 These catalysts operate at All reforming reactions were conducted in a 0.5 in. o.d. ×
temperatures low enough that carbon monoxide is not a 0.375 in. i.d. (1.27 cm o.d. × 0.95 cm i.d.) × 10 in. (25.4 cm)
significant product, and they are stable under our selected 304 stainless steel reactor. The inside wall of the reactor was
operating conditions. A copper-based catalyst that has shown coated with Restek Corporation’s Silcosteel coating for surface
much promise is the Cu/Zn/Zr/Al/Y-based catalyst.9,10 We passivation. The catalyst was supported in the reactor between
synthesized this catalyst in our laboratory and compared its deactivated quartz wool plugs, and the reactor was operated in
performance to that reported in the literature. This catalyst’s an upflow configuration. A gold-plated thermocouple in the
performance was used as a baseline for our catalyst development center of the catalyst bed was used to control the temperature
effort. Investigative research and testing has begun on several of reaction to (0.5 °C. Brooks proportional ratio mass-flow
novel copper-based catalyst variations. The variants are Cu/Zn controllers were used to control the gas feed to the reactor, and
on Zr/Al/Y, Cu/Zr on γ-Al2O3, Cu/Zn/Zr on γ-Al2O3, and Cu/ an Isco high-pressure syringe pump provided liquid feed control.
Zn/Ce on γ-Al2O3. The feed streams were preheated to approximately 130 °C prior
10.1021/ie061307v This article not subject to U.S. Copyright. Published 2007 by the American Chemical Society
Published on Web 06/01/2007
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 literature9 (BH5-2), exhibited an as-prepared surface area of 92
approximately 150 °C between the exit of the reactor and the m2/g. This value agrees with the value reported in the literature
cold trap. The cold trap was maintained at -4 °C using a of 92 m2/g. Reforming of methanol was performed at various
temperature-controlled chiller. reaction temperatures. Table 2 lists the data from a series of
Typical reaction conditions were as follows: Exactly 1.0000 reforming reactions performed in our laboratory and those for
g of catalyst was placed in the reactor supported between the the Cu/Zn/Zr/Al/Y catalyst as reported by Breen and Ross.9
quartz wool plugs such that the tip of the gold-plated thermo- Conversion of methanol with our preparation of the literature
couple was located in the middle of the catalyst bed. The reactor catalyst produced results similar to those reported in the
was purged at ambient temperature with helium at 5 mL/min literature. As shown in Table 2, methanol conversion increases
for at least 2 h prior to reaction. The temperature of the reactor with reaction temperature. At 150 °C, methanol conversion for
was increased to either 150 or 255 °C under a helium flow. BH5-2 was approximately 25%. The majority of product
The methanol flow was begun, at a weight hourly space velocity detected by the gas chromatograph was carbon dioxide. When
of 1.0 h-1, after the catalyst had reached the selected reaction the reaction temperature was increased to 255 °C, conversion
temperature. of methanol increased initially to 83%. The product distribution
Reaction conditions for the methanol/water reforming reac- also changed, with hydrogen comprising approximately one-
tions were identical to those for the pure methanol reforming half of the detected product. Of importance is the fact that carbon
reactions with the exception that the feed was an equimolar monoxide was not detected at either reaction temperature in
mixture of methanol and distilled-deionized water. our investigation (without water as a reactant) or in the literature
Reaction products were directly sampled and analyzed by an results.
online dual-column gas chromatograph (GC). The GC, a Conversion of methanol at 255 °C decreases with time on
Hewlett-Packard 5890 Series II instrument, was equipped with stream (Figure 1). This decrease in performance is most likely
a 6 ft × 0.0125 o.d. 80/100 Porapak Q column and a 20 ft × due to coke formation during the reaction. Even though the
0.0125 o.d. 60/80 Molecular Sieve 5 Å column (both obtained catalyst exhibits a rapid decrease in conversion over the first
from Supelco). The GC was held at a constant temperature of 20 h on stream, conversion and product selectivity ultimately
100 °C during elution. Argon was used as the carrier gas at an stabilize to constant values (Figure 1). As listed in Table 2,
average flow rate of 30 mL/min for the Molecular Sieve column conversion decreases to approximately 60% as the product
and 50 mL/min for the Porapak Q column at 30 °C. The selectivity improves slightly. These experiments were conducted
Molecular Sieve column was used to separate the light gaseous up to 250 h with no change in conversion or selectivity after
products, whereas the Porapak Q column was used to identify the initial drop. After reaction, the catalyst was removed from
liquid hydrocarbons. Both columns were equipped with back- the reactor and examined. The appearance and consistency of
flushing capability. Dual thermal conductivity detectors (TCDs) the used catalyst suggested that coke had formed during the
were employed to detect the separated components. reaction. The catalyst also exhibited a 40% decrease in surface
area during the reaction. This decrease might result from the
Results and Discussion coke formation and/or sintering of the unsupported metals in
the catalyst.
Methanol Reforming Reactions without Water. Five According to the literature,9 zirconium/aluminum/yttrium acts
catalysts were prepared and tested for their ability to reform as a support for the copper/zinc catalyst. The literature results
methanol without water in the reactant feed. The majority of also suggest a synergy between copper and zirconium that is
methanol reforming catalysts require mixtures of methanol and not evident between copper and aluminum. However, as shown
water to function at high conversions and selectivities. The water in Table 1, the copper and zinc comprise 86 mol % of the
is used to convert the byproduct carbon monoxide to hydrogen catalyst composition. In an effort to produce a more effective
and carbon dioxide by the water-gas shift reaction. In this study, supported copper/zinc catalyst, we synthesized a catalyst (BH5-
we chose to initially study the reforming ability of the catalysts 3) by first coprecipitating the zirconium/aluminum/yttrium
without co-feeding water with the methanol. After determining support and then adding the copper and zinc by incipient
performance under these conditions, performance in a system wetness. This resulted in a catalyst with copper and zinc
that included co-fed water was evaluated. comprising only 10 mol % of the catalyst. However, this also
The first catalyst tested was our preparation of the catalyst resulted in a catalyst with a very low surface area of 21 m2/g
that had been reported in the literature9 to have the best overall (Table 1).
methanol conversion and product distribution, Cu/Zn/Zr/Al/Y. Initial conversions of methanol on BH5-3 were high (ap-
The catalyst, prepared according the method described in the 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 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
Figure 2. Results of methanol conversion over Cu/Zr on γ-Al2O3 (BH5- resulted in approximately the same methanol conversion (79%);
4) at 255 °C. 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
Figure 3. Methanol conversion as a function of time on stream at 255 °C that exhibited the highest surface area (∼200 m2/g) after
for catalysts with different surface areas (refer to Table 1). synthesis. These catalysts also kept their high surface areas after
150 h on stream.
on stream increased, methanol conversion decreased (to ap- Methanol Reforming Reactions with Water. The main
proximately 40%), whereas product selectivity improved byproduct from a hydrogen-fueled PEM fuel cell is water. This
(Table 2). water could be used as a co-feed in the methanol reforming
In an effort to improve the conversion and selectivity of the reactor to increase the conversion of methanol to hydrogen and
reforming catalyst, we prepared several new catalysts. Catalysts to reduce the amount of carbon monoxide produced by means
BH5-4, BH5-10, and BH5-12 were all prepared by addition of of a water-gas shift reaction on the catalyst. As reported in
the metals to γ-alumina by incipient wetness. The support was the literature,9 methanol reforming reactions were carried out
changed to γ-alumina in an effort to increase the catalyst’s using a sequentially precipitated Cu/ZnO/ZrO2/Al2O3 catalyst
surface area. These catalysts exhibited the highest surface areas and 1.3:1 H2O/CH3OH reactant mixture. In addition, the catalyst
of any catalysts we prepared (Table 1). After reaction, these was pretreated with a 5% H2/N2 mixture starting at room,
catalysts retained >94% of their original surface areas. increasing the temperature at 5 °C/min to 240 °C and holding
The first catalyst synthesized in this series was BH5-4, copper at 240 °C for 4 h before reaction. In our experiments, the
and zirconium on γ-alumina. This combination was chosen on catalysts prepared for the reforming experiments using only
the basis of a literature9 report that a 2.4:1 molar ratio of copper 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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highest surface areas. These catalysts also retained >94% of
their initial surface area after extended (>100 h) time on stream. ReceiVed for reView October 12, 2006
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