Energy Sources, Part A, 30:149–156, 2008

Copyright © Taylor & Francis Group, LLC

ISSN: 1556-7036 print/1556-7230 online
DOI: 10.1080/00908310600712315

Hydrogen Storage in the Form of

Methylcyclohexane

S. YOLCULAR1 and Ö. OLGUN1

1
Ege University, Eng. Fac., Chemical Engineering Department, Izmir, Turkey

Abstract The use of compounds, such as toluene, that can store hydrogen with a spe-
cific volume of 46 kgH2/m3 in the form of methylcyclohexane, has been already shown
to be potentially feasible for both mobile and stationary applications. Thus, produced
hydrogen by the dehydrogenation of methylcyclohexane to toluene could be a very
attractive option to be adopted for these applications. In this study, dehydrogenation
of methylcyclohexane reaction for hydrogen production was investigated. The catalytic
experiments were made in a tubular pyrex glass fixed bed reactor. The experiments
were performed between 380ıC and 440ı C under the total pressure of about 1 atm
with a Pt/Re/Al2 O3 (sulfided) catalyst (UOP) (UK). Power law rate models were tested
for the experimental data. r D k:PMCH m was found as an appropriate model for the
experimental data of this study.

Keywords dehydrogenation, fixed bed reactor, hydrogen production, methylcyclo-

hexane

Introduction
Although great concern has been concentrated on hydrogen as a clean secondary energy,
there are problems in its transportability and storability. The main problem for the use
of hydrogen is the difficulty in the creation of a distribution infrastructure for safe and
cost effective transport and storage. Storage methods currently used are too expensive
and do not meet the performance requirements of future applications. New technologies
will need to be developed on the basis of production and storage systems that come into
use as the hydrogen economy advances (Itoh et al., 2003; Demirbaş, 2005; Balat and
Özdemir, 2005).
Zero-emission energy systems require the development of reversible hydrogen stor-
age processes. There are several possibilities for hydrogen storage: in the form of
liquid H2 ; as gaseous hydrogen at high pressure; in the form of metallic hydrides; by
adsorption in carbon nanotubes, graphite nanofibers, or glass microspheres; or in the
form of organic hydrides. This last option, in which reversible chemical reactions are
used to incorporate gaseous hydrogen into a liquid compound from which it can be
released again by dehydrogenation, seems to be one of the alternatives that could be
introduced on a local scale under economically acceptable conditions (Aparacio et al.,
2002).

Address correspondence to Sevim Yolcular, Ege University, Eng. Fac. Chemical Engineering
Dept., Bormova-Izmir, 35100, Turkey. E-mail: sevim.yolcular@ege.edu.tr

149
150 S. Yolcular and Ö. Olgun

In this sense, chemical carriers such as cyclohexane, methylcyclohexane (MCH),

etc., are considered suitable for hydrogen storage and transmission from the following
viewpoints. First, a higher hydrogen content (e.g., 7.1 wt% of cyclohexane) is very
attractive compared with metal hydrides (at most 3 wt%). The dehydrogenated products,
benzene and toluene (TOL), can be reversibly hydrogenated and reused, and those are all
liquids at ordinary temperatures; these are technically important factors for establishing a
hydrogen storage and transmission system. An additional advantage that there is no CO2
emission in the dehydrogenation process will be rated highly in terms of environmental
issues, whereas the steam reforming process of methanol produces not only hydrogen,
but also CO2 .
When a comparison of energy storage media for carbon free systems was made on a
cost and weight basis for application with renewable energy sources such as hydropower,
on a seasonal timescale (summer to winter), storage of hydrogen in liquid organic hydrides
was equivalent to other carbon free alternatives and superior to zero emission systems
like batteries.
Hydrogen storage in the form of liquid organic hydrides, e.g., MCH, was proposed
for the seasonal storage of electricity. H2 is released from seasonal (summer to winter)
storage in MCH by catalytic dehydrogenation recovering TOL, the H2 carrier. For use
in transportation, hydrogen when stored as MCH needs to be liberated by hydrogenation
(endothermic reaction) in a compact catalytic reactor. By coupling the reactor with the
engine, the waste heat could be utilized to run the reaction. The use of hydrogen for
automotive power has been studied for many years. Hydrogen that can be produced by
water electrolysis is highly attractive not only as a clean fuel (no CO2 produced), but also
for its potentially unlimited availability. In places with abundant electricity (for example,
Quebec) electrolytic hydrogen could also be an economical fuel (Lindfors and Salmi,
1993).
There were different studies about the dehydrogenation of MCH to TOL by different
researchers such as Chaouki et al., 1994; Klvana et al., 1991; Jawad et al. 1994; Jawad
and Baiker, 1997; Touzani et al., 1984, 1987; Grünenfelder and Schucan, 1989; Chai and
Kawakami, 1990; Belskaya et al., 1997; and Smirniotis et al., 1993. They investigated
this reaction in some different reactors and on some different catalysts. Their experiments
were performed at different temperature ranges and at different pressure ranges.
The strong increase in the demand for lower olefins during the last decade has initi-
ated the development of new alternative processes in addition to traditional petrochemical
or refinery processes, where lower olefins are obtained as by-products. The increased
availability of lower alkanes resulting from more strict environmental legislation has
made dehydrogenation processes economically attractive. Dehydrogenation reactions of
lower alkanes are highly endothermic and are carried out at high temperatures because
of thermodynamic constraints (Annaland et al., 2001).
Combining reaction with separation into multi-functional reactors becomes more and
more an interesting concept to both academic and industrial research. Among various
potential advantages of such concepts above all is the perspective to circumvent existing
thermodynamic limits on the yield of the desired reaction products. This is also the central
motivation for applying membrane reactors to hydrocarbon dehydrogenation. Given the
removal of hydrogen produced by dehydrogenation, the reaction can be continued beyond
equilibrium conversion. However, the use under typically harsh conditions of industrial
dehydrogenation processes not only calls for high permeability and high selectivity of the
membranes employed, but also for sufficient thermal, mechanical, and chemical stability
(Aparicio et al., 2002; Itoh et al., 2003; Kariya et al., 2003; Dittmeyer et al., 1999).
 Hydrogen Storage in the Form of Methylcyclohexane 151

Moreover, the dehydrogenation of MCH reaction has a considerable interest to extract

the hydrogen stored in toluene in the form of MCH as a safe way for hydrogen storage and
transportation. In general, dehydrogenation of MCH, takes place on Pt-based catalysts.

Experimental Study
R-50 (UOP) (UK) catalyst was used in the dehydrogenation experiments. 0.25% Pt,
0.25% Re, 0.9–1.0% Cl, sulphided catalyst, which had particle shape as extrusions,
with 0.16/0.32/0.45 cm nominal diameter, 832.82 kg/m3 shock loaded density, 171 m2 /g
surface area.
The experiments were made in a tubular pyrex glass fixed bed catalytic reactor
(with a 20 mm diameter). The temperature range was between 380ıC and 440ıC under
the total pressure of about 1 atm. The amount of catalyst was 1 g for dehydrogenation
experiments. The range of flow rates for MCH and hydrogen were between 0.8–1.5 
10 5 mole/s and 4.5–8.2  10 7 mole/s, respectively.
The reactor was set to the temperature of the reaction after the activation period. As
the temperature was stabilized, the flow rates of the MCH, and also H2 and nitrogen,
were adjusted to their values, and the gases were fed to the reactor section. MCH was fed
to the reactor as a mixture of MCH and hydrogen. The steady-state reaction conditions
took 30 minutes. After this period, the exit-condensed product was analyzed with HP
5890 Gas Chromatography Series 2.

Results
For the kinetic analysis of the results, power law rate model was tested for the experi-
mental data. The model was analyzed with Analysis ToolPack Lineer Regression Method
for the results.
The results of this experimental study fit the following rate equation.

Model:
m
r D k:PMCH D >lnr D lnk C m:l nPMCH (1)

Error analysis of this model was made and this model fitted to the experimental results.
Table 1 gives results of reaction rate constant (k) and the values of upper power of
PMCH (m). W=FMCH vs. XMCH graph is given in Figure 1. FMCH vs. rExp graph is given in
Figure 2. The rExp vs. rmod graphs are given for each reaction temperature at Figures 3–6.

Table 1
k, lnk, m, and n values of the model

k  106 ,
T, C
ı
T, K 1000/T, 1000/K atm m mol/(g.s) lnk, m,

380 653 1.531 1.240 13.597 10.23

400 673 1.486 1.910 13.168 7.04
420 693 1.443 2.250 13.006 6.26
440 713 1.403 3.830 12.474 2.71
152 S. Yolcular and Ö. Olgun

Figure 1. W =FMCH vs. XMCH graph.

Figure 2. FMCH vs. rExp graph.

Figure 3. rExp vs. rmod graph at 380ıC.

 Hydrogen Storage in the Form of Methylcyclohexane 153

Figure 4. rExp vs. rmod graph at 400ıC.

Figure 5. rExp vs. rmod graph at 420ıC.

Figure 6. rExp vs. rmod graph at 440ıC.

Discussion and Conclusions

The reduction of CO2 emissions is an urgent requirement to avoid global warming, and
exploiting alternative energy resources of petroleum is an important topic for the sustain-
able development of the society. Many research groups are refining the technology for
development and utilization of clean energy systems; one example is the PEM fuel cell for
power generation in high efficiency without CO2 emission. Accordingly, much attention
has been focused on the investigation of efficient methods to store and supply hydrogen
for the PEM system safely, so that the resulting system might be comparable to the
present fossil fuel-based energy system. The reversible dehydrogenation-hydrogenation
154 S. Yolcular and Ö. Olgun

system of cycloalkanes, such as cyclohexane, methylcyclohexane, and decalin, is one of

the potential systems to store and transport hydrogen (Kariya et al., 2003).
MCH is a liquid at ambient pressure and temperature, and, given that its consistence
and specific weight are very similar to crude oil, it can be stored and transported in
existing oil tanks and ships. Thus, it could be a more attractive option to be adopted in
the medium term in view of a smooth energy system infrastructure transition (Aparacio
et al., 2002).
The dehydrogenation of MCH experiments were performed between 380ıC–440ıC.
Flow rates of TOL and hydrogen were changed separately while one was kept constant
in the dehydrogenation experiments. R-50, (UOP) (UK) Pt=Re=Al2O3 catalyst was used
in the dehydrogenation experiments. 1 gram of fresh catalyst was used in each experi-
ment. Kinetic parameters of dehydrogenation experiments were determined by using this
catalyst.
MCH dehydrogenation was a convenient model reaction to study the dehydrogenation
function, because it occurred only on metal centers.
Platinum surface atoms in Pt=Al2 O3 catalysts are responsible for the dehydrogenation
function as well as for hydrogen activation. The latter ensured catalyst self-regeneration
by means of coke precursor hydrogenation (Belskaya et al., 1997).
In the dehydrogenation experiments, MCH was fed to the reactor as a mixture of
MCH and hydrogen. In spite of longer lifetime, this catalyst may be deactivated during the
reaction when no hydrogen was present in the feed. This could be a result of increasing
temperature. While the reaction temperature increased, then the coke deposit on the
catalyst surface increased. Also, the coke deposit on the catalyst surface increases the
deactivation of the catalyst. As Butt and Peterson (1988), and Chaouki et al. (1991) found
a reaction mechanism gives these results, too.
Reaction rate model for dehydrogenation experiments depended only on partial
pressure of MCH. Thus, the amount of hydrogen fed to the reactor with MCH did
not have any effect on the reaction rate and conversion. The presence of hydrogen in the
feed is required only to assure a constant catalyst activity. This result is in accordance
with the previous studies.
In order to prevent deactivation of the catalyst, the reactions should be made at low
temperatures. However, then the conversions would be low at these temperatures. Con-
sequently, membrane reactors could be used to increase the conversions. If experiments
were carried at high temperatures, then partial recycling of hydrogen could give high
conversions.
However, the kinetics followed a first order law for cyclohexane under commercial
conditions and under model conditions at T > 320ı C: r  kPCH . Since the dehydro-
genation experiments were performed between 380ıC–440ıC, then r D kPMCH reaction
m
model was used. But, the experimental results of this study showed that r D kPMCH .
The reaction order, m increased with temperature, but it has a minus sign. When the
flow rate of MCH and its partial pressure increased to a value higher than best operating
conditions, then conversion and reaction rate decreased.
W=FMCH 0 vs. XMCH graph and FMCH 0 vs. rExp graph at each reaction temperature
were plotted. These results were in agreement with the results of the other researchers
who investigated the same reaction.
This model was analyzed with Office ToolPack Linear Regression analysis. Then, k
and m values were found for each reaction temperature. Error analysis of this model
and experimental rates were performed. This model had a small average error and
fitted the experimental results. The kinetic analyses were made according to this model.
 Hydrogen Storage in the Form of Methylcyclohexane 155

rExp vs. rmod graphs were plotted showing that this model was appropriate for this
experiment.
The recommendations for future studies are mechanisms and rate expressions of
the experiments could be investigated with different catalysts and at a wide range of
reactant rates. The kinetic rate equations can be investigated by making some adsorp-
tion experiments. The reactor can be coupled by direct connection to PC, and to GC
analyzer in order to obtain perfect results. Conversions in the membrane reactor are
up to four times higher than those obtained at equilibrium without removal of product
hydrogen. Membrane reactor can be used for the future studies in the dehydrogenation
experiments.

References
Annaland, M. V. S., Kuipers, J. A. M., and Swaaij, W. P. M. V. 2001. A kinetic rate expression
for the time-dependent coke formation rate during propane dehydrogenation over a platinum
alumina monolithic catalyst. Catal. Today 66:427–436.
Aparicio, F. P., Rodriguez-Ramos, I., and Guerrero-Ruiz, A. 2002. On the performance of porous
vycor membranes for conversion enhancement in the dehydrogenation of methylcyclohexane
to toluene. J. Catal. 212:182–192.
Balat, M., and Özdemir, N. 2005. New and renewable hydrogen production processes. Energy
Sources 27:1285–1298.
Belskaya, O. B., Ostrovskii, N. M., and Demanow, Y. K. 1996. Specific properties of dehydro-
genation centers in supported platinum catalysts. React. Kinet. Catal. Lett. 60:119–126.
Butt, J. B., and Petersen, E. E. 1988. Activation, deactivation and poisoning of catalysts. Academic
Press, Inc., New York.
Chai, M. R., and Kawakami, K. 1990. Kinetic model and simulation for catalyst deactivation
during dehydrogenation of methylcyclohexane over commercial Pt-, PtRe- and presulfided
PtRe Al2 O3 catalysts. J. Chem. Tech. Biotechnol. 51:335–345.
Chaouki, J., and Klvana, D. 1994. Influence of the deactivation of an industrial Pt-Sn/Al2O3
catalyst on the performance of the dehydrogenation reactor. Chem. Eng. Sci. 49:4639–4646.
Demirbaş, A. 2005. Hydrogen and boron as recent alternative motor fuels. Energy Sources 27:
741–748.
Dittmeyer, R., Höllein, V., Quicker, P., Emig, G., Hausinger, G., and Schmidt, F. 1999. Factors con-
trolling the performance of catalytic dehydrogenation of ethylbenzene in palladium membrane
reactors. Chem. Eng. Sci. 54:1431–1439.
Gruenenfelder, N. F., and Schucan, T. H. 1989. Seaonal storage of hydrogen in liquid organic
hydrides: Description of the second prototype vehicle. Int. J. Hydrogen Energy 14:579–586.
Itoh, N., Tamura, E., Hara, S., Takahashi, T., Shono, A., Satoh, K., and Namba, T. 2003. Hydrogen
recovery from cyclohexane as a chemical hydrogen carrier using a palladium membrane
reactor. Catal. Today 82:119–125.
Jawad, K. A., Newson, E. J., and Rippin, D. W. 1994. Exceeding equilibrium conversion with a
catalytic membrane reactor for the dehydrogenation of methylcyclohexane. Chem. Eng. Sci.
49:2129–2134.
Jawad, K. A., and Baiker, A. 1997. Palladium black as model catalyst in the hydrogenolysis of
CCl2 F2 (CFC-12) into CH2 F2 (HFC-32). Appl. Catal. A: General 155:41–57.
Kariya, N., Fukuoka, A., Utagawa, T., Sakuramoto, M., Goto, Y., and Ichikawa, M. 2003. Efficient
hydrogen production using cyclohexane and decalin by pulse-spray mode reactor with Pt
catalysts. Appl. Catal. A: General 247:247–259.
Klvana, D., Touzani, A., Chaouki, J., and Bélanger, G. 1991. Dehydrogenation of methylcyclohex-
ane in a reactor coupled to a hydrogen engine. Int. J. Hydrogen Energy 16:55–60.
Lindfors, L. P., and Salmi, T. 1993. Kinetics of toluene hydrogenation on a supported Ni catalyst.
Ind. Eng. Chem. Res. 32:34–42.
156 S. Yolcular and Ö. Olgun

Smirniotis, P. G., and Ruckenstein, E. 1993. The performance of Pt/ˇ zeolite and Pt/ -Al2 O3
composite pellets in the reforming of methylcyclopentane and methylcyclohexane. Chem.
Eng. Science 48:3263–3272.
Touzani, A., Klvana, D., and Bélanger, G. 1984. Dehydrogenation reactor for a vehicle equipped
with a hydrogen engine: A simulation study. Int. J. Hydrogen Energy 9:929–936.
Touzani, A., Klvana, D., and Bélanger, G. 1987. A mathematical model for the dehydrogenation
of the methylcyclohexane in a packed bed reactor. Can. J. Chem. Engng. 65:56–63.
Tschudin, S., Shido, T., Prince, R., and Wokaun, A. 1999. Characterization of catalysts used in
wall reactors for the catalytic dehydrogenation of methylcyclohexane. J. Catal. 181:113–123.

Nomenclature
atm atmosphere
Exp experimental
k reaction rate constant, (atm m mol/(g.s))
K Kelvin
m the values of upper power of PMCH , ( )
MCH methylcyclohexane
mod model
MTH methylcyclohexane, toluene, hydrogen
PCH partial pressure of cyclohexane, (atm)
PMCH partial pressure of methylcyclohexane, (atm)
TOL toluene
r reaction rate, (mol/g.s)
T temperature (ı C, K)
wt% weight %