Proceedings of the 5th International Conference on Microreaction Technology (IMRET 5),

Strasbourg, France, May 27-30, 2001

A microreactor for in-situ hydrogen production by

catalytic methanol reforming

Ashish V. Pattekar and Mayuresh V. Kothare∗

Department of Chemical Engineering, Lehigh University, Bethlehem, PA18015, USA.
Sooraj V. Karnik and Miltiadis K. Hatalis
Department of Electrical Engineering, Lehigh University, Bethlehem, PA18015, USA.

Abstract
A detailed study of the theoretical and experimental issues involved in the design
and operation of a silicon-based methanol microreformer is presented in this paper.
Thermal simulations for heat loss from the reformer chip and calculations
involving the endothermic heat effect of the reforming reaction were carried out to
estimate the total power requirement for continuous operation of the reformer.
Micromachining technology was utilized to fabricate a prototype silicon
microchannel based reformer of channel cross-section 1000µm x 230µm with a
copper layer of thickness ~ 33nm as catalyst. The reactor chip was interfaced with
the tubing for reactant and product transport using a stainless steel housing
machined to exact dimensions and flexible graphite pads to provide gas-tight seals
and excellent thermal contact between the chip and the housing for external
heating of the reformer. Runs of this prototype microreformer were carried out
using a custom made experimental setup for generation of the reactant mixtures,
temperature control of the microreactor and online measurement of the product gas
composition. Results from test runs of the microreformer are presented and
strategies for improving the hydrogen yield are discussed.

1. Introduction

The use of microreactors for in-situ and on-demand chemical production is

gaining increasing importance as the field of microreaction engineering matures
from the stage of being a regarded as a theoretical concept to a technology with
significant industrial applications. Various research groups have successfully
developed microreactors for chemical processing applications such as partial
oxidation of ammonia [10], nitration [2] and chemical detection [4]. The objective
of the research effort at the Integrated Microchemical Systems Laboratory at
Lehigh University’s Chemical Engineering Department is to demonstrate a
working microreaction system for use as a sustained source of hydrogen fuel for
proton exchange membrane (PEM) fuel cells through catalytic steam reforming of
methanol. The complete reformer-fuel cell unit is proposed as an alternative to

∗
Corresponding author. Phone: (610)-758-6654; Fax: (610)-758-5057; E-mail:
mayuresh.kothare@lehigh.edu
conventional portable sources of electricity such as batteries for laptop computers
and mobile phones due to its ability to provide an uninterrupted supply of
electricity as long as a supply of methanol and water can be provided. Though
considerable work already exists in literature on the catalytic steam reforming of
methanol for production of hydrogen using conventional reactors [1,7,8], the use
of microreactors for in-situ methanol reforming is a relatively new idea
[3,6,11,12]. Literature on the macro-scale steam reforming of methanol includes
analysis of the reaction thermodynamics [1] for prediction of optimum reactor
temperature and feed compositions, catalyst characterization studies [7], and
experimental studies on macro-scale pilot reactors [8]. Results obtained in the
study of methanol reforming in these conventional reactors form a good
background for the development of microreactors for this purpose. Silicon is
considered a good material for fabrication of microreactors due to the high
strength of the Si-Si bonds which results in the chemical inertness and thermal
stability of silicon. Well established silicon micromachining techniques commonly
used in the microelectronics industry facilitate easy fabrication of microchannels
and other desired features on silicon substrates thus making silicon the ‘material of
choice’ for microreactor fabrication.
In the following sections we discuss the theoretical and experimental issues in
the development of a prototype silicon chip based microreformer. Preliminary
calculations giving an idea of the power required to operate the microreformer are
presented followed by a description of the microreformer fabrication procedure.
The experimental setup for carrying out test runs of the microreformer is described
and results from the test runs are presented.

2. Preliminary Simulations

Preliminary simulations on a Silicon chip of size 2cm x 2cm were carried out using
the MEMCAD design and simulation software [9] to study the effects of fluid flow
and heat loss from a Silicon chip operating at the reforming temperature of 500K.
Figure 1a shows the velocity profile (velocity units: µm/sec) of the fluid (water)
flowing through microchannels of cross section 1000µm x 500µm. The channel
geometry is such that the fluid enters along the negative z axis direction through
the two inlets, mixes at the intersection of the two inlets and leaves along the
positive z axis direction at the outlet. The boundary condition used for the flow
simulation was a constant flow rate of 0.1 cc/sec at each inlet with the outlet being
at atmospheric pressure, with no slip at the channel walls. Figure 1b shows the
results of a thermal simulation on the same chip with a temperature boundary
condition of 500K at the bottom wall of the microchannels in addition to the flow
boundary conditions described above. The fluid inlet temperature was taken as the
room temperature (300K) and the heat loss from the rest of the chip surface was
governed by natural convection to ambient air at 300K.
Figure 1(a): Figure 1(b):
Flow through a simple microchannel Temperature gradients within bulk Si

As can be seen in Figure 1b, most of the chip surface reaches a temperature
very close to the maximum of 500K within a short distance from the inlets, which
are at 300K due to the incoming fluid being at room temperature. The excellent
thermal conductivity of bulk silicon results in close to uniform temperature
distributions within the bulk with most of the chip temperature being very close to
the maximum (500K for this calculation) when the heat loss from the chip to the
surrounding is governed by relatively weaker modes of heat transfer such as
natural convection. This conclusion is especially relevant for the operation of high
temperature microreactors since this means that Silicon based microreactors for
high temperature reactions will have most of their surface at the high reaction
temperature resulting in significant heat losses to the surrounding unless sufficient
thermal isolation from the ambient is provided. Since the optimum temperature for
the methanol reforming reaction is about 250 oC [1], it follows that heat integration
and thermal isolation issues will be extremely important for efficient operation of
the microreformer. For example, the heat loss from a Silicon chip of size 2cm x
2cm operating at 250 0C is about 4.5 Watt as governed by natural convection to air
at 25 0C with a natural convection heat transfer coefficient of 25 W/m2K. A
hydrogen flow rate of 0.3721 gmol/hr is needed for a 20-Watt fuel cell assuming
80% hydrogen utilization, which translates into a methanol flow rate of 0.1536
gmol/hr at 85% conversion inside the reformer with a selectivity of 95% towards
the reforming reaction. Then the power required for the endothermic reforming
reaction (with the reformer operating at 250 oC) at this flow rate is about 2.038
Watt as shown in the calculations below using data on the heat of reaction and
specific heats of the components of the reaction mixture[5].
The steam reforming of methanol for hydrogen production in the presence of
Cu/ZnO catalyst involves the following reactions at 250 oC:
Primary reactions:

CH3OH + H2O ⇔ CO2 + 3H2 (∆H298K = 48.96 KJ/mol) (1)

CH3OH ⇔ CO + 2H2 (∆H298K = 90.13 KJ/mol) (2)

Secondary Reaction:

CO2 + H2 ⇔ CO + H2O (∆H298K = 41.17 KJ/mol) (3)

Considering only the main reforming reaction,

∆H298K = 48.96 KJ/mol

523
⇒ ∆H250C = ∆H523K = ∆H298K + ∫
298
∆Cp(T)dT = 59.17 KJ/mol

⇒ Heat of reaction requirement for endothermic reforming reaction

= 59.17 x 0.1536 x 0.85 x 0.95 /3600 KJ/sec = 2.038 Watt

Thus a large part of the power required to run the reformer is due to heat loss
from the reformer chip to the surrounding and can be reduced by effective
packaging and insulation of the microreformer.

3. Microreformer Fabrication

Fabrication of reactor microchannels of cross sectional dimensions 1000µm x

230µm on the prototype silicon reformer chips was carried out using standard
silicon micromachining techniques such as Photolithography and KOH etching.
We used a single mask process to get four identical microreformers from a single
100mm silicon wafer polished on both the sides. Silicon nitride was deposited by
plasma enhanced chemical vapor deposition (PECVD) on both sides of the wafer.
Photolithography was done on the back side of the wafer to obtain the
microchannel pattern. Silicon nitride on the back side was then etched by plasma
etch to get pattened nitride which acts as an etch stop during KOH etching of
silicon. Bulk silicon was etched in KOH from the back side to obtain
microchannels of desired depths. About 33 nm of copper (catalyst layer) was then
sputter deposited. Figure 2 illustrates the major steps involved in the fabrication of
the microreformer chips. As will be discussed in the section on the experimental
set-up and external interfacing of the microreformer, one end of the channel needs
to have a hole in the silicon substrate for the dosing of reactants into the channels.
This hole was made after fabrication of the channels by etching through the wafer
with KOH. A protective coating of black wax prevented etching of the rest of the
wafer. This technique exposes only one end of the channel (an area of
approximately 1mm2) to the etchant, which results in the desired hole after
completion of the etching process. This step is illustrated in Figure 2(d). Figure 3
shows a schematic of the final reformer chip.

Figure 2: Microreformer fabrication steps

( a) Si wafer with nitride ( b) Plasma etch to expose Si ( c) KOH etching of bulk Si

( d) Formation of inlet hole

Unprotected channel end Inlet Hole

KOH etch
Removal of
black wax

Black Wax

( e) Copper deposition by sputtering

Cu layer

Figure 3: The fabricated microreformer

36 mm

Inlet hole

36 mm
Channel width 1000 µm,
depth 230 µm,
Copper layer 33 nm
 4. External Interfacing

The interfacing of the microreformer chip to tubing for reactant and product gas
transport was done using a custom made stainless steel housing shown in Figures 4
and 5. The steel housing blocks have ridges of appropriate length connecting the
central bore to appropriate points on the reformer. The ridge on one of the steel
blocks was machined to face the reactant inlet hole on the reformer chip when the
chip was properly aligned with the housing. Similarly, the product gases exit from
the other end of the channel through a similar ridge in the housing block machined
to face the other end of the channel when aligned correctly.
Figure 4: Schematic of microreformer housing

Flexible graphite pads with holes aligned to microreformer inlet/outlet

Microreformer Ridges for gas flow

inlet in housing

Swagelok connector Exhaust tubing

(To gas analyzer)

Feed tubing Microchannels

Microreformer
Reactor housing outlet

Microreformer

Leak-proof sealing between the reformer chip and the steel housing was ensured
by using flexible graphite pads acting as gaskets with holes drilled at the right
positions for reactant and product transport. Thus the reformer chip was covered
from either side by a graphite covering pad to provide a leak-proof conduit for
reactant and product gas transport between the housing and the reformer. The
tubing for gas transport was connected to both sides of the housing via standard
Swagelok connectors so that the reactants entered the housing-microreformer
assembly from one side, passed to the microreformer through the hole in the
silicon substrate and exited the reformer through a similar hole in the covering
graphite pad at the other end of the microchannel after flowing over the deposited
catalyst. The advantage of using flexible graphite pads for sealing purposes was
that graphite being a good conductor of heat, the reactor temperature could be
maintained at 250 oC by heating the steel housing using heating tapes and suitable
temperature controllers. This allowed testing of the reformer chip without having
to fabricate on-chip resistive heaters and temperature sensors, which will be
integrated with the microreformer in future.
 Figure 5: Microreformer housing

Reactor housing

Reformer Chip

5. Experimental set-up
The operation of the microreformer involved:
1. Setting up of the methanol vapor and steam source
2. Interfacing of the microreformer chip to external tubing for transport of
reactants and products as discussed in Section 4, and
3. Connection of the reactor exhaust tubing to the gas analysis equipment (a
quadrupole mass spectrometer) for online analysis of the product gas composition.

A gas-tight sample cylinder containing a liquid methanol-water mixture

immersed in a constant temperature hot water bath maintained at temperatures in
the range 80 oC – 95 oC was used for generation of methanol vapor-steam mixtures
of desired compositions by manipulating the composition of the liquid mixture in
the sample cylinder on the basis of methanol-water vapor-liquid equilibrium
(VLE) data. Analysis of the VLE data for the mixture and pressure drop
calculations from simulations using MEMCAD confirmed that enough pressures
could be generated in this set-up to drive the flow of the reactants through the
reformer. The product gas tubing coming from the microreformer housing
connected to the mass spectrometer, which gave an online analysis of the
composition of the product gases. Figure 6 shows a schematic of this set-up.
Electric heating tapes and simple on-off controllers with thermocouple probes
were used to maintain the temperature of the connecting tubing above 100 oC to
avoid condensation of the vapors during flow. A pressure transducer-strain gage
meter combination was used to continuously monitor the pressure in the sample
cylinder. The reactor housing was also maintained at the temperature required for
the reforming reaction (around 250 oC) using electric heating tapes and an auto-
tuning PID controller with a thermocouple sensor which maintained the reactor
temperature to within 1 oC of the setpoint.
 Figure 6: Schematic of experimental set-up

Pressure sensor Flow control valve Microreformer Reactor exhaust

housing

o
Release valve 250 C using
heating tape
o
Hot water bath (90 C)

Sample cylinder
Mass Spectrometer

The gas analyzer used for analysis of the product gas composition was a
quadrupole ion-trap mass spectrometer based residual gas analyzer (RGA) with a
pressure-reducing inlet allowing the sampling of gases at atmospheric pressure.
The pressure reducing inlet capillary of the analyzer was also maintained at above
100 oC using heating tapes to avoid any condensation before the pressure was
sufficiently reduced to obviate condensation of water and methanol at room
temperature inside the capillary. The mass spectra were collected at short intervals
and the peak amplitudes were converted to mole fraction data for conversion
calculations.

6. Results and Discussion

I. Test Runs
Test runs of the microreformer were carried out to verify hydrogen production
capability inside the microreformer and to get an idea of the conversion possible
using this set-up. Though the reformer design wasn’t optimized from the point of
view of conversion or hydrogen yield, the preliminary runs gave important insights
into the operation of the microreformer in this set-up. For the test run reported here
a 50:50 mixture of methanol and water was fed into the sample cylinder
maintained at 85 oC using the hot water bath shown in Figure 6. Using methanol-
water VLE data at 85 oC obtained using the UNIFAC method in Aspen Plus, the
vapor mixture at equilibrium with this liquid will have methanol vapor mole
fraction (Ymethanol) of about 0.76. The methanol vapor-steam mixtures generated in
this manner were passed through the reformer maintained at 250 oC and the
product gas mass spectra were obtained at regular intervals during the run. The
mass spectra were converted to mole fraction data using the library for molecule
fragmentation inside the mass spectrometer ionizer. A plot of the exit gas
composition (mole fraction) v/s time (sec.) for a microreformer test run of 500 sec
is shown in Figure 7. As can be seen from the plot, sufficient amount of hydrogen
was detected at the reactor exit to confirm that reforming was indeed taking place
in the microreactor.
 Figure 7: Microreformer product gas composition (mole fraction) v/s time (sec)

Looking at

Average values of the mole fraction of each component in the product gas for
this run can be used to get a crude estimate of the hydrogen yield. These values
were 0.755 for methanol, 0.21 for water, 0.070 for hydrogen, 0.00129 for carbon
dioxide and 0.017 for carbon monoxide. Though the hydrogen yield obtained in
this prototype unoptimized microreactor was not significant (approximately about
0.092 moles H2 produced per mole CH3OH fed into the reformer with an average
flow rate of about 2.36 x 10-3 gm/sec of methanol-steam mixture at the
microreformer inlet with inlet methanol mole fraction of 0.76) these results
demonstrate the capability to carry out methanol reforming in a microreactor and
to test the microreactor operation at different operating conditions. Future work
will involve attempts to improve the hydrogen yield by increasing the catalyst
contact area per unit channel length and optimizing microchannel geometries for
more efficient utilization of available total chip area. Experimental runs with
reformer chips having the composite copper-zinc oxide catalyst instead of using
only a copper layer will also be carried out to study the effect of catalyst properties
on reaction extent.

II. Catalyst Deactivation

Referring to the chemical reactions (equations 1, 2 and 3 in Section 2) it should be
noted that the amount of CO and CO2 produced in the test runs as obtained from
the mass spectra was less than what would be expected from the reaction
stoichiometry for the observed production of H2. One possible reason for this
could be the deposition of minute quantities of carbon during the reaction in the
microchannels which would reduce the amount of CO and CO2 present in the exit
gases [1]. Carbon deposition on the catalyst surface can have several undesirable
effects affecting the product purity. It was also observed that the copper layer in
the microreformer degraded and turned blue (as shown in Figure 8) after several
test runs probably due to the formation of some compound of copper in the
presence of the reaction mixture at the high reforming temperature of 250 oC.
These issues will be important in refining the design of the microreformer since
catalyst deactivation will lead to lower yields and some form of catalyst
regeneration will have to be incorporated for restoring good efficiency of the
reformer operation.
Figure 8: Degradation of copper layer in the microreformer

Inlet hole

Degraded copper layer

Channel width 1000 µm,
(blue)
depth 230 µm

III. Conclusion
The main contribution of this work is the demonstration of a microchannel based
methanol reformer for small-scale hydrogen production and the development of a
set-up for carrying out experimental runs of the microreformer. A prototype silicon
based microreformer was successfully fabricated and tested using a setup designed
for easy operation and replacement of microreformer chips and testing of different
microreformer designs. Preliminary results from the test runs confirmed the
presence of hydrogen at the reformer exit and revealed the need for extensive
optimization of the reformer design for obtaining good hydrogen yields. Catalyst
degradation in the microchannels was also observed. The optimization of the
reformer design and methods to deal with catalyst deactivation issues will be an
important part of future work in this project.

Acknowledgment: Financial support for this project from the U.S. National
Science Foundation under the ‘XYZ-on-a-chip’ grant CTS-9980781, the
Pittsburgh Digital Greenhouse and Sandia National Laboratories is gratefully
acknowledged.
We also acknowledge the assistance of undergraduate Chemical Engineering
student Joshua Tilghman in machining of the microreactor housing and setting up
of the experimental apparatus for testing the microreformer.
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