1018 Ind. Eng. Chem. Res.

2010, 49, 1018–1026

Kinetics of Hydrogen Uptake and Release from Heteroaromatic Compounds for

Hydrogen Storage
Farnaz Sotoodeh and Kevin J. Smith*
Department of Chemical & Biological Engineering, UniVersity of British Columbia, 2360 East Mall,
VancouVer, BC, Canada V6T 1Z3

The kinetics of hydrogen uptake by N-ethylcarbazole and carbazole, and the kinetics of H2 release from their
hydrogenated products, is reported. The hydrogenation of N-ethylcarbazole at 130-150 °C on Ru was well
described by a network of first-order stepwise hydrogenation reactions. The hydrogenation of N-ethylcarbazole
was significantly faster than the hydrogenation of carbazole, and in both cases, >95% selectivity to the
completely hydrogenated products, dodecahydro-N-ethylcarbazole and dodecahydrocarbazole, was achieved.
The dehydrogenation of dodecahydro-N-ethylcarbazole at 101 kPa and 150-170 °C, proceeded to 100%
conversion of the reactant over a Pd catalyst within 1 h. However, only 69% of the stored H2 was recovered
due to a low selectivity to N-ethylcarbazole. In the case of dodecahydrocarbazole dehydrogenation at 101
kPa and 170 °C over the same Pd catalyst, 28% H2 recovery was obtained due to the strong adsorption of the
product carbazole on the catalyst surface that also resulted in a slower rate of dodecahydrocarbazole
dehydrogenation compared to dodecahydro-N-ethylcarbazole.

1. Introduction present work, the complete hydrogenation-dehydrogenation

One approach to hydrogen storage for fuel-cell vehicles is to
use organic compounds that have a high capacity to bind
hydrogen covalently. Storage and release of the hydrogen is
achieved by hydrogenation and dehydrogenation of the organic
compounds, and these reactions are done in the presence of a
catalyst. For transportation applications, the H2 storage (hydro-
genation) would be done off-board the vehicle. Also, the
candidate compounds must have high hydrogen release rates,
more than 5.5 wt % H2 storage capacity (calculated as the mass
of H2 liberated divided by the mass of hydrogenated compound),
melting points below -40 °C and boiling points above 200 °C.1,2
Organic heteroaromatic compounds such as carbazole have
attracted attention because they meet the storage capacity targets
and the boiling point criteria.
Although some results have been reported for H2 storage on
heteroaromatic compounds, limited data are available on the
kinetics of the reactions involved in H2 uptake and release.3-7
Carbazole and N-ethylcarbazole, when hydrogenated to dodecahy-
drocarbazole and dodecahydro-N-ethylcarbazole, have hydrogen
storage capacities of 6.7 and 5.8 wt %,5,8,9 respectively. They
are, therefore, potential candidates for hydrogen storage ap-
plications. However, the hydrogenation-dehydrogenation kinet-
ics of these compounds are not well established, especially at
the low temperature (<200 °C) conditions required for on-board
dehydrogenation reactions. In addition, although platinum group
metals are widely used for hydrogenation and dehydrogenation
reactions, the influence of the heteroatom present in these
compounds on the reaction kinetics needs to be understood,
given that strong heteroatom adsorption can lead to a loss in
catalyst activity. The N heteroatom associated with N-ethylcar-
bazole and dodecahydro-N-ethylcarbazole is bound to an ethyl
group, whereas in the corresponding carbazole compounds, the
N heteroatom is free to interact with the catalyst surface through
the lone pair of electrons associated with the N.
In previous work, hydrogen recovery from dodecahydro-N-
ethylcarbazole was demonstrated over a Pd catalyst.10 In the
* To whom correspondence should be addressed. E-mail: kjs@
interchange.ubc.ca.
10.1021/ie9007002  2010 American Chemical Society
Published on Web 09/16/2009
cycle needed for hydrogen storage and release has been
investigated for both carbazole and N-ethylcarbazole. The
kinetics of the hydrogenation reactions needed for hydrogen
storage on N-ethylcarbazole and carbazole, and the kinetics of
the dehydrogenation reactions needed for hydrogen release from
the corresponding hydrogenation products, are reported. N-
Ethylcarbazole was hydrogenated over a supported Ru catalyst
in an autoclave batch reactor at 7 MPa and 130-150 °C. The
hydrogenated compound, dodecahydro-N-ethylcarbazole, was
then dehydrogenated over a supported Pd catalyst at 150-170
°C and 101 kPa. Kinetic models of the hydrogenation and
dehydrogenation reactions, as well as the activation energies
of the reactions, are reported. For comparison, carbazole was
hydrogenated at 7 MPa and 170 °C, using the same catalyst
and experimental setup used for the hydrogenation of N-
ethylcarbazole. The hydrogenated product, dodecahydrocarba-
zole, was subsequently dehydrogenated at 170 °C and 101 kPa
over a supported Pd catalyst.
2. Experimental Section
2.1. Catalyst Preparation and Characterization. A 5 wt
% Pd on silica catalyst was prepared by wet impregnation and
used as the dehydrogenation catalyst. Details of the catalyst
preparation method have been reported previously by the
authors.10 A commercial 5 wt % Ru on alumina catalyst
(Aldrich, 5 wt % Ru, reduced), received in a reduced state, was
used as the hydrogenation catalyst and was rereduced prior to
use. Both catalysts were characterized to determine BET surface
area, pore volume, and pore size using a Micromeritics ASAP
2020 analyzer. A Micromeritics Autochem II 2920 was used
for temperature programmed reduction (TPR) analysis of the
catalysts and to determine the metal dispersion by CO pulse
chemisorption.10
2.2. Catalyst Activity. The hydrogenation of N-ethylcarba-
zole was carried out at 130, 140, and 150 °C and a H2 pressure
of 7 MPa, in a 300 cm3 autoclave batch reactor with continuous
monitoring and control of stirrer speed, temperature, and
pressure. Approximately 100 cm3 of a 6 wt % solution of

Table 1. Catalyst Properties
catalyst BET, m2/g pore volume, cm3/g
Pd/silica (calcined) 311.5 0.9
Pd/silica (reduced) 325.6 1.1
Ru/alumina (reduced) 76.5 0.2
a
The commercial catalyst was supplied in a prereduced state.
N-ethylcarbazole (Aldrich, 97%) in decalin (Sigma-Aldrich,
98%) and 1 g of the 5 wt % reduced Ru/alumina catalyst, with
a particle size <150 µm, were loaded into the reactor. The reactor
was first purged in a 55 cm3(STP) · min-1 flow of N2 for about
1 h and then heated to the desired temperature while purging
with ultra high purity (UHP) hydrogen at a 55 cm3(STP) · min-1
flow and low pressure (<35 kPa) to ensure that no reaction
occurred. After the desired temperature was reached, the reactor
was pressurized to 7 MPa, corresponding to more than 2.5 times
the amount needed for complete hydrogenation of the N-
ethylcarbazole reactant, while stirring at a speed of 600 rpm.
The H2 pressure was monitored continuously during the experi-
ment. Small volumes (<0.5 cm3) of liquid sample were removed
from the reactor periodically for analysis by gas chromatogra-
phy. Hydrogenation of carbazole was carried out using the same
autoclave reactor at 7 MPa and 150 °C. In this case, a 1 wt %
solution of carbazole (Aldrich, 95%) in decalin (Sigma-Aldrich,
98%) and 1 g of the 5 wt % reduced Ru/alumina catalyst with
a particle size <150 µm were loaded into the reactor. The same
start-up and sampling procedure used for the hydrogenation of
N-ethylcarbazole was used for the hydrogenation of carbazole.
However, due to the extremely low solubility of carbazole in
decalin at room temperature, liquid samples were only taken at
the end of the experiment and the identity of the final product
was confirmed by GC/MS analysis with a Shimadzu QP-2010S
GC/MS using a Restek RTX5 30 M × 0.25 mm capillary
column.
The recovered product from the hydrogenation of the N-
ethylcarbazole was subsequently used as a reactant for the
dehydrogenation experiments. These reactions were carried out
in a 50 cm3 glass flask reactor using 0.3 g of 5 wt % Pd/silica
at 150, 160, and 170 °C and 101 kPa. The reactor was sealed,
Figure 1. Hydrogenation reaction pathway of N-ethylcarbazole obtained from GC/MS analysis: (a) N-ethylcarbazole, (b) tetrahydro-N-ethylcarbazole, (c)
octahydro-N-ethylcarbazole, (d) hexahydro-N-ethylcarbazole, (e) decahydro-N-ethylcarbazole, (f) dodecahydro-N-ethylcarbazole.
Ind. Eng. Chem. Res., Vol. 49, No. 3, 2010 1019
average pore size, nm degree of reduction, % metal dispersion, %
9.6
9.5 78.0 4.2
8.4 3.3a 6.2
stirred, and heated to the desired temperature. Helium, at a flow
of 170 cm3(STP) · min-1, was used as a carrier gas for continuous
removal of the produced H2. The exit gas composition was
continuously monitored using a quadrupole mass spectrometer
(SRC Residual Gas Analyzer, 200 amu) so that the produced
H2 could be quantified. Liquid samples were also withdrawn
from the reactor for analysis by gas chromatography using a
14-A Shimadzu gas chromatograph equipped with a flame
ionization detector (FID) and an AT-5 25 M × 0.53 mm
capillary column. Product identities were also confirmed by the
Shimadzu QP-2010S GC/MS. The product from the hydrogena-
tion of carbazole was also dehydrogenated in the same reactor
at 101 kPa and 170 °C. In this case, 0.17 g of the reduced 5 wt
% Pd/silica was used as the dehydrogenation catalyst. The same
experimental procedure was used for both dehydrogenations.
The absence of internal and external mass transfer effects on
the measured reaction kinetics was confirmed experimentally
and by theoretical analysis. For the hydrogenation reactions,
the gas-to-liquid mass transfer rates, estimated according to
Zievernek et al.,11 were at least 2 orders of magnitude higher
than the observed reaction rate. Furthermore, repeating the
reactions at stirrer speeds of 600 and 1000 rpm showed that, in
both cases, the measured reaction rates were within (10% of
the average values. Internal mass transfer effects were minimal
because of the small catalyst particle size and confirmed by the
calculated Weisz-Prater criterion of Φ < 1.0 at the highest
reaction temperature. Similarly, both internal and external mass
transfer effects were shown to be minimal during the dehydro-
genation reactions.
1020 Ind. Eng. Chem. Res., Vol. 49, No. 3, 2010
 Ind. Eng. Chem. Res., Vol. 49, No. 3, 2010 1021

Figure 2. (A) Product distribution over time for N-ethylcarbazole hydrogenation at 150 °C: (a) N-ethylcarbazole, (b) tetrahydro-N-ethylcarbazole, (c) octahydro-
N-ethylcarbazole, (d) hexahydro-N-ethylcarbazole, (e) decahydro-N-ethylcarbazole, (f) dodecahydro-N-ethylcarbazole. Note the different scale of each plot.
(B) Product distribution over time for N-ethylcarbazole hydrogenation at 140 °C: (a) N-ethylcarbazole, (b) tetrahydro-N-ethylcarbazole, (c) octahydro-N-
ethylcarbazole, (d) hexahydro-N-ethylcarbazole, (e) decahydro-N-ethylcarbazole, (f) dodecahydro-N-ethylcarbazole. Note the different scale of each plot.
(C) Product distribution over time for N-ethylcarbazole hydrogenation at 130 °C: (a) N-ethylcarbazole, (b) tetrahydro-N-ethylcarbazole, (c) octahydro-N-
ethylcarbazole, (d) hexahydro-N-ethylcarbazole, (e) decahydro-N-ethylcarbazole, (f) dodecahydro-N-ethylcarbazole. Note the different scale of each plot.
3. Results and Discussion showed that N-ethylcarbazole hydrogenation proceeded through
the stepwise saturation of double bonds, leading to the parallel
3.1. Catalyst Properties. Table 1 summarizes the charac-
production of tetrahydro-N-ethylcarbazole and octahydro-N-
terization data for both catalysts of the present study. BET
ethylcarbazole as the primary reaction products. Rapid con-
surface area, pore volume, and average pore size were measured
sumption of tetrahydro-N-ethylcarbazole and subsequent pro-
for the 5 wt % Pd/silica after calcination and reduction and for
duction of hexahydro-N-ethylcarbazole suggested that the
the 5 wt % reduced Ru/alumina catalyst.
reaction proceeded to the production of hexahydro-N-ethylcar-
Temperature programmed reduction (TPR) of the calcined
bazole from tetrahydro-N-ethylcarbazole. The product distribu-
Pd/silica catalyst precursor showed a 78% degree of reduction
tion showed slower consumption of hexahydro-N-ethylcarbazole
of PdO to Pd. The commercial Ru/alumina was received in a
reduced state, and the low degree of reduction for this catalyst compared to tetrahydro-N-ethylcarbazole. Octahydro-N-ethyl-
reflects the stability of the reduced Ru in air. CO pulse carbazole, one of the main intermediates, can undergo saturation
chemisorption data were used to determine that the Pd dispersion of the double bonds through two parallel paths to produce
on the reduced Pd/silica catalyst was 4.2%, whereas the Ru decahydro-N-ethylcarbazole, as well as dodecahydro-N-ethyl-
dispersion was 6.2% on the rereduced Ru/alumina catalyst. Even carbazole, the major final product. The reaction completed with
though the BET area of the Pd/silica dehydrogenation catalyst more than 95% selectivity to the desired dodecahydro-N-
was about 4 times that of the Ru/alumina hydrogenation catalyst, ethylcarbazole, and less than 5% selectivity to the product
both catalysts had similar metal dispersions. octahydro-N-ethylcarbazole. The total amount of hydrogen
3.2. Catalyst Activity and Kinetics. Hydrogenation. When consumed during hydrogenation corresponded to approximately
N-ethylcarbazole was hydrogenated at an H2 pressure of 7 MPa 5.3 wt % of the reactant. This is very close to the storage
and temperature of 150 °C, the conversion of N-ethylcarbazole criterion of Department of Energy (DOE) and confirms that
proceeded to 98% after 1 h, with an initial rate of H2 N-ethylcarbazole is a promising compound for hydrogen storage.
consumption of 58.4 mM · min-1 · gcat-1. Analysis of the liquid The experimental product distribution data measured over
samples by GC/MS confirmed the production of partially and time at three reaction temperatures were used to model the
completely hydrogenated compounds during the reaction, as reaction kinetics. The kinetic model based on the reaction
represented in Figure 1. The reaction pathway in Figure 1 was network shown in Figure 1 assumed that reactions were first-
suggested from the product distributions measured over time order in the concentration of the heteroaromatic organic
at three temperatures as shown in Figure 2a-c. These data compounds and zero-order in hydrogen. The parameters (rate
1022 Ind. Eng. Chem. Res., Vol. 49, No. 3, 2010
Table 2. First-Order Rate Constants and Activation Energies for the Hydrogenation of N-Ethylcarbazole over Ru/Alumina Catalyst
temperature, °C k1, h-1 k2, h-1
130 0.021 ( 0.012a 0.444 ( 0.018
140 0.042 ( 0.018 1.020 ( 0.018
150 0.096 ( 0.012 1.764 ( 0.018
activation 107.6 ( 7.0 97.9 ( 10.3
energy, kJ/mol (R2 ) 0.99) (R2 ) 0.98)
a
Standard error of estimated parameters.
Table 3. Initial Reaction Rates, Rate Constants, and Turnover Frequencies (TOFs) for Hydrogenation of N-Ethylcarbazole and Carbazole at
150 °C over Ru/Alumina Catalyst
reactant catalyst/reactant ratio, g · g-1
N-ethylcarbazole 0.17
carbazole 1.00
a
Reaction rate with respect to H2 consumption. b
With respect to N-ethylcarbazole and carbazole consumption.
atom-1. d Reaction time for 100% conversion.
constants) of the kinetic model were estimated by minimizing
an objective function, defined as the sum of squares of the
difference between the experimental component concentrations
and those calculated by the kinetic model, using a weighted
least-squares method. The objective function was minimized
using a Nelder-Mead simplex (direct search) method. At each
iteration on the parameter values, the concentration of each
compound as a function of time was calculated by numerical
integration of the five ordinary differential equations that
described the time rate-of-change of the hydrogenated product
concentrations. In addition, the mole balance constraint was used
to calculate the reactant concentration at each time step.
Although reaction orders from 0 to 2 in increments of 0.5 were
examined for all heteroaromatic organic compounds as well as
hydrogen, the assumed first-order kinetics for reactant and
hydrogenated products and zero-order kinetics for hydrogen gave
the best fit of the experimental data based on a minimum
magnitude of the residual sum of squares. A zero-order reaction
in hydrogen likely reflects the excess hydrogen at high pressure
present during the hydrogenation reactions, and the relatively
narrow range of H2 pressures investigated herein, that results
in an approximate constant concentration of H2 in the liquid
phase as the reaction proceeded.
The activation energies for the reactions were determined by
linear regression according to the Arrhenius equation. Individual
first-order rate constants estimated at 130, 140, and 150 °C, as
well as the activation energies are reported in Table 2. The
model results calculated using the obtained rate constants are
plotted against the experimental product concentrations in Figure
2a-c. The standard error of the parameter estimates reported
in Table 2 are considered acceptable given that a simple power
law model with fixed exponents has been used to fit the kinetics
of a complex reaction network over a relatively wide range of
reaction temperatures.
The model results confirmed that the production of intermedi-
ates and the final product were well described by the simplified
first-order kinetic model shown in Figure 1. The data for the
concentration of tetrahydro-N-ethylcarbazole showed the largest
difference between the measured and calculated concentrations,
but the concentration of this compound was the lowest among
all compounds by approximately 1 order of magnitude. Table
2 summarizes the obtained rate constants for the individual
reactions of the model (Figure 1), as well as the activation
energies estimated from the rate constants. The rate constants
for reaction 4 (k4) and reaction 7 (k7) of Figure 1, corresponding
to the conversion of hexahydro-N-ethylcarbazole and decahydro-
N-ethylcarbazole, were zero at 130 °C, confirming the higher
activation barrier for the consumption of these two intermediates
k3, h-1 k4, h-1 k5, h-1 k6, h-1 k7, h-1
0.840 ( 0.462 0.006 ( 0.006 1.140 ( 0.060
2.034 ( 0.600 0.606 ( 0.672 0.012 ( 0.012 2.964 ( 0.528 0.048 ( 0.024
5.646 ( 1.188 2.538 ( 0.414 0.024 ( 0.006 3.300 ( 0.024 0.252 ( 0.084
134.9 ( 7.5 208.0 (R2 ) 1) 98.2 ( 1.4 75.8 ( 33.6 240.9 (R2 ) 1)
(R2 ) 0.99) (R2 ) 0.99) (R2 ) 0.83)
initial rate,a mM · min-1 · gcat-1 rate constant,b k, h-1 TOF,c s-1 reaction time,d h
58.36 2.952 ( 0.122 0.223 1.16
18.44 0.318 ( 0.034 0.108 13.33
c
Molecule reactant · s-1 · Ru surface
compared to the other products. The estimated rate constants
for the conversion of tetrahydro-N-ethylcarbazole (k3) and
hexahydro-N-ethylcarbazole (k4) were consistent with the ob-
served slower consumption of hexahydro-N-ethylcarbazole
compared to the more rapid consumption of tetrahydro-N-
ethylcarbazole in the first 10 min of the reaction (Figure 2a).
Comparing the apparent activation energies of Table 2, it is
seen that the production of octahydro-N-ethylcarbazole from
hexahydro-N-ethylcarbazole (reaction 4) and the production of
dodecahydro-N-ethylcarbazole from decahydro-N-ethylcarbazole
(reaction 7) have the highest activation energies, in agreement
with the experimental observation of low consumption rates of
hexahydro-N-ethylcarbazole and decahydro-N-ethylcarbazole.
Carbazole was hydrogenated using the same autoclave reactor
and catalyst to produce the reactant for the dehydrogenation
reaction. At a H2 pressure of 7 MPa and a temperature of 150
°C, 100% conversion of carbazole was achieved after about 13 h.
Due to the extremely low solubility of carbazole in decalin,
only a few liquid samples were withdrawn after a reaction time
of 10 h. Liquid sample analysis by GC/MS confirmed the
production of dodecahydrocarbazole as the main product.
The reaction proceeded with more than 97% selectivity to the
completely hydrogenated product, dodecahydrocarbazole, after
about 13 h. The initial rate of H2 consumption by carbazole
was 18.44 mM · min-1 · gcat-1 at 150 °C. Since the intermediate
products could not be monitored as a function of time in this
case, the kinetics of carbazole consumption were described by
a first-order rate equation in carbazole concentration and zero-
order in H2 concentration. The same mathematical procedure
used to model the kinetics of N-ethylcarbazole hydrogenation
was used to model carbazole hydrogenation. Different reaction
orders for the organic heteroaromatic compounds as well as
hydrogen were examined in the model. The chosen orders are
based on the best fit of experimental data.
A comparison between the initial rates, the first-order rate
constants, and turnover frequencies for the consumption of
carbazole and N-ethylcarbazole at 150 °C is presented in Table
3. N-ethylcarbazole hydrogenation showed a higher initial
reaction rate and proceeded to 100% conversion in a signifi-
cantly shorter reaction time with lower metal loading of the
catalyst, compared to carbazole. The slower hydrogenation rate
of carbazole compared to N-ethylcarbazole can be attributed to
the strong adsorption of the carbazole molecule through the N
heteroatom to the metal surface. The inhibiting effects of basic
N in organic compounds on precious metal catalysts, due to
the unshared pair of electrons on N, is well-known.12 The steric
hindrance associated with the ethyl group of N-ethylcarbazole
prevents the adsorption of the molecule on the metal surface

Figure 3. Product distribution over time for dehydrogenation of dodecahydro-N-ethylcarbazole obtained by GC/MS: (a) 150, (b) 160, and (c) 170 °C; (O)
experimental data, (solid line) fitted model. The rate constants are reported in Table 4.
through the N, as has been previously reported for similar
geometries.13 Therefore, although carbazole has a higher
theoretical H2 storage capacity than N-ethylcarbazole, the
inhibiting effect of the N atom slowed the hydrogenation
reaction and complete H2 saturation of carbazole was obtained
in a much longer reaction time compared to N-ethylcarbazole,
making carbazole a less practical candidate for H2 storage.
Dehydrogenation. The products from N-ethylcarbazole hy-
drogenation in decalin at 150 °C, containing octahydro-N-
ethylcarbazole (3%) and dodecahydro-N-ethylcarbazole (97%),
were transferred to the 50 cm3 reactor for dehydrogenation at
150, 160, and 170 °C over the 5 wt % reduced Pd/silica catalyst.
The product distribution over time at temperatures of 150, 160,
and 170 °C is presented in Figure 3. Previous studies showed
that decalin dehydrogenation occurs at temperatures above 200
°C,14-17 and our own tests confirmed that decalin dehydroge-
nation did not occur at temperatures below 180 °C on the Pd/
silica catalyst. Consequently, it was possible to use decalin as
a solvent for the dehydrogenation reactions. The GC/MS
analysis of liquid samples confirmed the production of tetrahy-
dro-N-ethylcarbazole and octahydro-N-ethylcarbazole at all three
temperatures, with a relatively slow conversion of octahydro-
N-ethylcarbazole to tetrahydro-N-ethylcarbazole. However, no
significant amounts of N-ethylcarbazole were produced. The
experimental product distribution data measured over time at
three temperatures were used to model the dehydrogenation
reaction kinetics based on the reaction network shown in Figure
4A. The kinetic model assumed first-order reactions in the
concentration of dodecahydro-N-ethylcarbazole. A weighted
least-squares method was used to minimize the sum of squares
of the difference between the experimental component concen-
Ind. Eng. Chem. Res., Vol. 49, No. 3, 2010 1023
trations and those calculated from the kinetic model. Individual
first-order rate constants were obtained at 150, 160, and 170
°C and these are reported in Table 4, together with the apparent
activation energies of each reaction. The model results calculated
using the obtained rate constants are plotted against the
experimental product concentrations in Figure 3. Clearly, the
simplified kinetic scheme describes the product distribution from
dodecahydro-N-ethylcarbazole dehydrogenation on Pd/silica
satisfactorily. The kinetics of dodecahydro-N-ethylcarbazole
consumption was also well described by a first-order rate
equation, confirmed by testing the model with different reaction
orders, and the corresponding rate constants and activation
energy estimated from the experimental data are provided in
Table 4.10
Table 4 summarizes the reaction rates and rate constants, as
well as the percent hydrogen recovered at each temperature.
One hundred percent of the reactant, dodecahydro-N-ethylcar-
bazole, was converted at the three temperatures, resulting in 2
wt % H2 recovery after 2 h and 4 wt % H2 recovery after 17 h
at 170 °C. This is comparable to results reported for the
dehydrogenation of another candidate compound, 1,2,3,4-
tetrahydrocarbazole at 140 °C over 5 wt % Pd/Al2O3, where
81% of the reactant was converted after 27 h.18,19 However,
although 100% conversion of dodecahydro-N-ethylcarbazole
was achieved in the present study, only 69% of the total stored
H2 was recovered because the dehydrogenation proceeded to
tetrahydro-N-ethylcarbazole and octahydro-N-ethylcarbazole,
and not to the completely dehydrogenated product, N-ethylcar-
bazole. The lack of selectvity to N-ethylcarbazole is likely
related to the adsorption geometries associated with tetrahydro-
N-ethylcarbazole and octahydro-N-ethylcarbazole.
1024 Ind. Eng. Chem. Res., Vol. 49, No. 3, 2010
Figure 4. Comparison between the reaction pathways of (A) dodecahydro-N-ethylcarbazole dehydrogenation (a) dodecahydro-N-ethylcarbazole, (b) octahydro-
N-ethylcarbazole, (c) tetrahydro-N-ethylcarbazole; (B) dodecahydrocarbazole dehydrogenation (a) dodecahydrocarbazole, (b) octahydrocarbazole, (c)
tetrahydrocarbazole, (d) carbazole.
Table 4. Initial Reaction Rates, Rate Constants, Activation Energies, and H2 Recovery in Dehydrogenation of Dodecahydro-N-ethylcarbazole
over Pd/Silica Catalyst
initial reaction rate,
temperature, °C mM · min-1 · gcat-1 rate constant, k, h-1
150 3.00 0.096 ( 0.000a
160 8.51 0.264 ( 0.000
170 12.11 0.450 ( 0.050
activation energy, kJ/mol 126.8 ( 24.3
a
Standard error of mean of estimated parameters.
The product from the carbazole hydrogenation reaction,
containing isomers of dodecahydrocarbazole, was also loaded
into the 50 cm3 dehydrogenation reactor. Dehydrogenation was
performed at 101 kPa and 170 °C, to provide a comparison with
dodecahydro-N-ethylcarbazole dehydrogenation. Figure 4A and
B compares the suggested reaction pathway for the dehydro-
genation of dodecahydro-N-ethylcarbazole and dodecahydro-
carbazole, respectively, obtained from the experimental product
distribution data over time. Dodecahydrocarbazole conversion
proceeded through two parallel reactions leading to the produc-
tion of octahydrocarbazole and tetrahydrocarbazole. Production
of small amounts of carbazole, after nearly 4 h, was confirmed
by analyzing the liquid samples as well as by quantifying the
produced H2.
The experimental data obtained by the analysis of the liquid
samples were used to model the dehydrogenation kinetics of
dodecahydrocarbazole. A first-order rate equation was fitted to
the experimental data obtained for the production of octahy-
drocarbazole and tetrahydrocarbazole, whereas a zero-order rate
equation was considered for the conversion of tetrahydrocar-
bazole to the final product, carbazole, as previously reported.10,18,19
Figure 5 illustrates the experimental data for the dehydrogenation
of carbazole at 170 °C and the fitted model. From the obtained
H2 recovery
rate constant, k1, h-1 rate constant, k2, h-1 after 17 h, wt %
0.072 ( 0.000 0.036 ( 0.000 2.10
0.078 ( 0.002 0.162 ( 0.001 3.30
0.162 ( 0.036 0.210 ( 0.037 4.00
67.1 ( 30.1 144.3 ( 61.0
results, it was confirmed that the production of octahydrocar-
bazole and tetrahydrocarbazole were well described by first-
order kinetics. Previous studies on the dehydrogenation of
tetrahydrocarbazole10,18,19 indicated that the reaction was zero-
order with respect to tetrahydrocarbazole consumption. How-
ever, because of the poisoning of Pd by the strong adsorption
of the product carbazole on the Pd surface, the reaction rate
decreased, as shown in Figure 5d, where the dashed line shows
the predicted zero-order carbazole production and the experi-
mental data show a decrease in reaction rate because of product
catalyst poisoning. The first-order rate constants for the produc-
tion of octahydrocarbazole and tetrahydrocarbazole, and the
zero-order rate constant for the production of carbazole obtained
from the model fit to the experimental data, are summarized in
Table 5.
The experimental data show that only 1.9 wt % H2 recovery
was achieved from the dehydrogenation of dodecahydrocarba-
zole after 17 h, which is smaller than the amount of H2 recovered
from the dehydrogenation of dodecahydro-N-ethylcarbazole at
170 °C for the same reaction time. A comparison between the
dehydrogenation of dodecahydro-N-ethylcarbazole and dodecahy-
drocarbazole at 170 °C is provided in Table 6. This comparison
shows that 100% conversion of dodecahydro-N-ethylcarbazole
 Ind. Eng. Chem. Res., Vol. 49, No. 3, 2010 1025

Figure 5. Product distribution over time for dehydrogenation of dodecahydrocarbazole obtained by GC/MS at 170 °C: (a) dodecahydrocarbazole, (b)
octahydrocarbazole, (c) tetrahydrocarbazole, (d) carbazole; (O) experimental data, (solid line) fitted model. The dashed line in part d corresponds to the
predicted carbazole concentration without catalyst poisoning. The rate constants are reported in Table 5.

Table 5. Initial Reaction Rate and Rate Constants for Dehydrogenation of Dodecahydrocarbazole at 170 °C
initial reaction rate, mM · min-1 · gcat-1 rate constant,a k, h-1 k1, h-1 k2, h-1 k3, mM · h-1 · gcat-1 H2 recovery, wt %
4.13 0.042 ( 0.000b 0.024 ( 0.000 0.018 ( 0.001 0.0003 ( 0.0000 0.64,c 1.90d
a b c d
First-order rate constant for dodecahydrocarbazole consumption. Standard error of mean of estimated parameters. After 2 h. After 17 h.

Table 6. Comparison between the Initial Reaction Rates, Rate Constants, and H2 Recovery for the Dehydrogenation of
Dodecahydro-N-ethylcarbazole and Dodecahydrocarbazole at 170 °C over 5 wt % Pd/SiO2
reactant initial rate, mM · min-1 · gcat-1 rate constant,a k, h-1 conversion,b % H2 recovery,b,c wt %
dodecahydro-N-ethylcarbazole 12.00 0.450 ( 0.050d 100 4.00
dodecahydrocarbazole 4.13 0.042 ( 0.001 52.6 1.90
a
With respect to reactant consumption. b After 17 h. c
The ratio of H2 liberated in grams to the weight of the starting reactant in grams (×100).
d
Standard error of mean of estimated parameters.

was obtained after 17 h, while only 52.6% of the dodecahy-
drocarbazole was converted to the dehydrogenated products
during the specified reaction time. The lower reaction rate and
rate constant for the dehydrogenation of dodecahydrocarbazole
compared to dodecahydro-N-ethylcarbazole is likely because of
the strong adsorption of the dehydrogenated products to the
metal surface through the N atom. For the case of dodecahydro-
N-ethylcarbazole, the steric hindrance of the ethyl group prevents
the molecules from being adsorbed through N, and thus, a higher
reaction rate was observed.
4. Conclusion
N-Ethylcarbazole hydrogenation was faster than the hydro-
genation of carbazole over a supported Ru catalyst in the
temperature range 130-150 °C, whereas the selectivity to the
completely hydrogenated products, dodecahydro-N-ethylcarba-
zole and dodecahydrocarbazole was 95% and 97%, respectively.
Both N-ethylcarbazole and carbazole hydrogenation reactions
followed first-order kinetics. Dehydrogenation of the dodecahy-
dro-N-ethylcarbazole was also faster than the dehydrogenation
of dodecahydrocarbazole over a Pd/silica catalyst at 150-170
°C. However, only 69% of the stored hydrogen was recovered
from dodecahydro-N-ethylcarbazole at 170 °C, due to a high
selectivity to tetrahydro-N-ethylcarbazole and octahydro-N-
ethylcarbazole. H2 recovery from dodecahydrocarbazole was
28%. By comparing the obtained results from the dehydroge-
nation reaction, it is concluded that N-ethylcarbazole and its
hydrogenated product, dodecahydro-N-ethylcarbazole, are more
practical candidates for H2 storage and release than carbazole
and dodecahydrocarbazole.
Acknowledgment
Funding for the present study from Natural Sciences and
EngineeringResearchCouncilofCanadaisgratefullyacknowledged.
1026 Ind. Eng. Chem. Res., Vol. 49, No. 3, 2010
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ReceiVed for reView April 30, 2009
ReVised manuscript receiVed August 20, 2009
Accepted August 28, 2009
IE9007002