Chemical Engineering Science 134 (2015) 721726

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Chemical Engineering Science

journal homepage: www.elsevier.com/locate/ces

Remote control of reaction rate by radiofrequency heating of

composite catalyst pellets
Ale Zadrail, Frantiek tpnek

Department of Chemical Engineering, University of Chemistry and Technology Prague, Technicka 5, 166 28 Prague 6, Czech Republic

HIGHLIGHTS

G R AP H I C AL AB S T R AC T

1 Composite catalyst pellets suscepti-ble to radiofrequency

heating were fabricated.

2 Effect

of

temperature

and

flowrate

on reaction

conversion was investi-gated.

3

Transient ON/OFF control of reaction rate was achieved.

4 The concept of reaction on demand was demonstrated.

article info
Article history:
Received 12 March 2015 Received in revised form 11
May 2015
Accepted 12 May 2015 Available online 6 June 2015
Keywords:
Ethanol dehydration
Induction heating
Alumina
Heat transfer
Reaction on-demand

abs
tra
ct
The
vapo
urphase
dehy
dratio
n of
ethan
ol
over
alumi
na
has
been
consi
dered
as a
mode
l
syste
m for
demo
nstrat
ing a
novel

concept for the remote control of an

endothermic catalytic reaction. Control of the
reaction rate was achieved by forming
composite catalyst pellets consisting of
porous alumina with embedded metal (Fe)
microparticles. Exposing such composite
catalyst pellets to alternating magnetic field in
the radiofrequency range (900 kHz) resulted
in localised heat generation within the catalyst
pellets due to induction heating of the iron
particles. The effect of the magnetic field
power output and reactant flowrate on the
steady-state conversion over a differential
catalyst bed was systematically investigated.
Transient On/Off operation of the reaction
was then demonstrated by periodically
changing the intensity of the magnetic field
and thus controlling the local temperature of
the catalyst. This concept enables the reaction
product to be formed locally in short bursts,
which provides opportunity for process
intensification and on-demand synthesis.

& 2015 Elsevier Ltd. All rights

reserved.

1. Introduction

t
r

The concept of chemical

reaction on demand is quite
com-mon in living systems,
where various biomolecules are
produced by cells only when
and where they are needed. The
control mechanism is usually
based either on controlling the
supply
of
the
reactants
(substrates), which is regulated
by trans-membrane

14

Tel.: 420Corresponding
220 443 236.
E-mail address:
tpnek).

htt
p://
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doi
.or
g/1
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016
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es.
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5.0
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Els
evi
er
Ltd
.
All
rig
hts
res
erv
ed.

author.

Frantisek.Stepanek@vscht.cz (F.

A. Zadrail, F. tpnek / Chemical Engineering Science 134 (2015) 721726

722

explore the potential to control

pellet or a catalyst bed can be a limiting step. local reaction rate by means of
Alternative means of energy supply that wouldRF induction heating for the
facilitate rapid and uniform volumetric heating, energy supply directly to the
interior of individual catalyst
are therefore of interest.
As
a
model
One possibility is the use of microwave pellets.
endothermic reaction, the
heating ( Perry et al., 2002), which was found catalytic
dehydration
of
to have several advantages over tradi-tionalethanol to ethylene over
methods of catalyst heating ( Bhattacharya andalumina was chosen ( Zhang
Basak, 2013; Komorowska et al., 2009). Theand Yu, 2013). This process
main advantage is the ability to supply preciselyrequires temperatures in the
defined quantities of energy into the catalyst range

of 300500 1C (
Sundaram
et al., 2010) and is
bed or reaction vessel at defined time intervals (
strongly
temperatureConner et al., 2004). A potential limitation is
the risk of forming hot spots due to non-dependent. The present work
uniform absorption of the microwaves. Another demonstrates that flexible
approach is the coupling of endothermic andOn/Off modulation of the
reaction rate via RF catalyst
exothermic reactions ( Frauhammer et al.,heating enables on-demand
1999). In that case the endothermic andproduct formation.
exothermic reactants are fed sequentially to the
same catalyst bed ( van Sint Annaland et al.,
2002), which effectively acts as a recuperative
heat exchanger. Such autothermal setup,
however, limits the type of reaction and the
purity of products.

Another method capable of heating up

complex objects rapidly and uniformly is
induction heating. Here the energy is provided
to the system by an alternating magnetic field in
the radiofrequency range (RF heating). RF
heating is based on generating Foucault
currents in conductors (Joule heating), or in the
case of magnetic materials or nanoparticles, on
the Nel and Brownian relaxation processes
associated with energy dissipation ( Schmid,
2010). RF heating is a scalable method proven
at both laboratory and industrial conditions, for
example in metallurgy. In the context of
chemical engineering applications, the use of
RF heating is still relatively limited. Its
application

for

catalyst

regeneration

Bhowmick et al., 2012), fluidised bed drying (

Stresing et al., 2011) or catalyst testing ( Latifi
et al., 2014) has been reported. In our recent
work, RF heating has been used for the local
control of temperature-dependent processes at
the small scale by forming composites with
micro- or nano-particles that dissipate heat
when exposed to RF magnetic field. Thus,
remotely controlled release of a chemical
payload from stimuli-responsive hydrogels (
Zadrazil et al., 2012), composite hollow silica
microspheres ( Kovak et al., 2012) or

2. Materials and methods

2.1. Materials
The following chemicals
were used. Ethanol for uv/vis
spectro-scopy (Penta, Czech
Republic),
aluminium
hydroxide (Lach-ner, Czech
Republic), LUDOX AM-30
colloidal silica 30 wt%
suspension in water (Sigma
Aldrich) and iron (Fe)
microparticles (mean particle
diameter
25
mm). All
chemicals were used as
received.
2.2. Composite catalyst
fabrication
The catalytic pellets were
prepared by mixing aluminium
hydroxide (10.0 g) with Fe
microparticles (2.5 g) and
adding a colloidal silica
dispersion (2.5 ml) as a binder.
After homogenisa-tion, the
suspension was poured into
rectangular moulds (fabricated from ABS using a 3D
printer)
with
internal
dimensions 4 4 57 mm and
placed into an oven for 3 h at
120 1C. In the next step the
dried blocks were removed
from the moulds and broken
into
smaller
pellets
approximately 4 4 5 mm,
slowly heated in an oven to
500 1C (5 1C/min, air
atmosphere) and kept at the
final temperature for another 6
h in order to dehydrate the
aluminium hydroxide and
form aluminium oxide with a
porous structure. To increase
the mechanical stability of
alumina compo-site pellets,
the pellets were soaked for a
short time (1 s) in a 10% w/w
solution of colloidal silica and
dried again. The porous
structure of the pellets was
analysed by scanning electron
micro-scopy (SEM, Jeol JCM5700).

liposomes ( Hanu et al., 2013), as well as RF

controlled desorption from a composite
adsorbent pellet ( Zadrail and tpnek,
2013) were demonstrated. However, in all the
above cases, the process that was controlled by
RF heating was diffusion, not reaction.

Therefore, the aim of the present work is to

2.3. Radiofrequency heating

set-up
The catalyst pellets were
placed into a glass tube
(internal diameter 22 mm) to

form a loosely packed bed, which was kept in turn, water-cooled copper coil
position by a support grid. The height of the(26 mm ID) and a cylindrical
packed bed was 50 mm and the total mass of copper extension (CEIA, Italy)
pellets used was 18.75 g. The glass tube was used. The induction head
containing the packed bed was covered by a was connected to a 900 kHz
knitted fibreglass insulation sleeve and placed RF generator (PowerCube 64/
into the axis of an induction coil as shown in900, CEIA, Italy).
Fig. 1. In order to achieve a uniform magnetic
field in the entire catalyst bed (22 50 mm) a
special induction head consist-ing of single-

Fig. 1. The apparatus for endothermic

catalytic reaction controlled by induction
heating.

2.4. Characterisation of the

catalyst bed
Temperature of the catalyst
during RF heating was
monitored by a fibre optic
thermometer with a protective
Teflon cup, which enabled
direct
temperature
measurement
up
to
approximately

A. Zadrail, F. tpnek / Chemical Engineering Science 134 (2015) 721726

Fig. 3. Example of experimentally

measured ethylene volume as a
function of time and evaluation of the
reaction
rate.
Experimental
conditions: power output 70%, water
bath temperature 88 1C.

Fig. 2. Principle of the evaluation of heating rate from the

linear section of the temperature rise during induction
heating of a packed bed. The power unit output was set to
10% of maximum in this case.

heating rate is
250 1C. The power input intolinear (cf. also
the packed bed can be
Zadrail
and
calculated from the initial rate
tpnek, 2013),
of temperature rise during the
the
catalyst
induction heating of a dry
temperature for
catalyst
(i.e.,
without
higher
power
reaction) using the enthalpy
outputs
was
balance:
calculated
by
extrapolation. The
Q in mcpdT=dt kqAT
heat-transfer
Tamb
1
coefficient (kqA)
was
evaluated
where Qin is the rate of heat
from
the
generation within the pellets
due to the RF inductionasymptotic
heating, m is mass of thetemperature (cf.
pellets, cp is the mean specificFig. 2), when
heat capacity of the pelletsdT/dt was zero
(calculated from the pelletand the Q was
in
composition as a weighted
known from the
average), dT/dt is the rate of
tempera-ture
changeinitial slope when
evaluated from the measured(T Tamb) was
heating curve (see Fig. 2),small.
kqA is the product of the
overall
heat
transfer
coefficient and the catalyst2.5. Reaction
bed surface, T is actualprogress
temperature of the pellets andmonitoring
Tamb is ambient temperature
in the laboratory during the
The
measurement (24 1C).
dehydration
of
ethanol
over
The rate of temperature
alumina
was
rise of the catalytic bed was
chosen as a model
initially measured only for
endothermic
lower power output settings
of the RF generator (up toreaction ( Zhang
25% of maximum) due to the and Yu, 2013).
operating
temperatureThe dehydra-tion
limitations of the fibreopticto ethylene is
thermometer. Once it has beenknown to start at
established
that
thetemperatures
around 300 1C
relationship between the RF
and
yields
generator output and catalyst
ethylene
and

723

water accordingis very small

to the following(approximately
stoichio-metric 0.131 g/l at 20 1C
reaction scheme:
(
Verschueren,
2008)), hence the
CH3CH2OH2CH2 contribution of its
into
CH2 H2O r absorption
water
was
H;298:15
neglected.
Water
45952 J=mol
vapour as well as
2
any
unreacted
When the reactionethanol that may
temperature
is
below 300 1C (
de Morais et al.,
2011), the main
by-product of the
reaction
is
ethylether
(solubility
of
ether in water is
60.5 g/l at 25 1C (
Windholz, 1983)).
The
schematic
drawing of the
apparatus used for
carrying out the
reaction is shown
in Fig. 1. The
ethylene
gas
evolved
during
the reaction was
led by Teflon
tubing to a graded
burette and the
ethylene volume
as function of
time was recorded
and converted to
molar
quantity
using the ideal gas
equation of state.
The solubility of
ethylene in water

pass through the

catalyst bed will
condense at the
temperature of the
water
bath
through which the
product
stream
was bubbled (24
1C), thus the
volume change in
the graded burette
can be attributed
purely to the
evolved ethylene.
The feed flowrate
of the ethanol
vapours into the
catalyst bed was
adjusted
by
controlling
its
evaporation rate
from a sealed
Erlenmeyer flask
reservoir, which
was placed into a
water bath with
controlled
temperature ( Fig.

1).
To carry out a
reaction kinetics
experiment, the
Erlenmeyer flask
was filled with 10
ml (7.89 g, 0.171
mol) of ethanol,
placed in the
water bath and
connected by a
glass tube to the
catalyst bed ( Fig.
1).
The
radiofrequency
magnetic
field

was switched on at theX n

required intensity and theEthyleneout =n
volume of produced ethylene
EtOHin 3
as func-tion of time was
recorded. The reaction time where X is the
was defined as the timeconversion,
elapsed from the onset ofn(EtOH)in is the
ethanol boiling until itsmolar quantity of
being
complete evaporation, atethanol
evaporated
and
which point there was no
more volume change ofn(Ethylene)out is
the molar quantity
evolved
ethylene.
The
of
produced
reaction rate was evaluatedethylene.
The
from the slope of themean flowrate of
dependence of the molarthe
reactant
the
quantity of produced ethyleneduring
experiment
is
on time ( Fig. 3) and thesimply
integral conversion of ethanol
was calculated according to
qEtOH
the equation:

n EtOH in=
tr

where
tr is the balance according
total reaction time ( to the following
Fig. 3).

equation:

2.6. Temperature
of the catalytic Q in kqA T
bed during

reaction
Tamb
Since it was
not possible torHXqEtOH
monitor
the

temperature of the micp;i T Tin

catalyst
bed

5
directly
under
reaction
where Qin is the
conditions due torate of heat supply
the tem-peratureby RF heating
limitations of the(known from the
fibre-optic probe,dry case), rH is
reaction
the temperaturethe
of
was
calculatedenthalpy
ethanol
from the steady-dehydration
at
state
enthalpyreference

temperature (25
1C), mi and cp,i
are
the
mass
flowrate and the
mean specific heat
capacity,
respectively,
of
the
reaction
components
leaving
the
reactor (water and
ethanol product as
well
as
any
unreacted
ethanol), and Tin
is
the
inlet
temperature,
assumed to be
equal
to
the
boiling point of
ethanol (78 1C).
Eq. (5) is based
on a lumpedparameter
description of the
catalyst bed,

724

A. Zadrail, F. tpnek / Chemical Engineering Science 134 (2015) 721726

Fig. 4. BEI micrographs of the porous composite catalyst. The light regions of the micrographs represent iron microparticles.

Table 2
Temperature of the catalyst bed and achieved ethanol conversion to ethylene during
endothermic reaction.

Water bath temperature

No reaction case

distributed inside the porous alumina

Fig. 5. Power input into the catalyst as function of the relative power output setting of the RF structure.
generator and corresponding maximum catalyst temperature, without reaction.

Table 1
Molar flow rates of ethanol through the catalyst bed during radiofrequency heating and calculated
mean residence times.
Power unit output
50%
Water bath temperature 801C 0.042 mmol/s
12.7 s
841C 0.086 mmol/s
6.2 s
881C 0.121 mmol/s
4.4 s

60%

70%

0.046 mmol/s
11.6 s
0.100 mmol/s
4.9 s
0.166 mmol/s
3.2 s

0.051 mmol/s
10.4 s
0.116 mmol/s
4.6 s
0.190 mmol/s
2.8 s

which is considered for the purpose of this work (i.e., neglecting axial or radial
temperature variations).

The specific power input into the

catalytic bed evaluated according to
Eq. (1) for the RF generator outputs
up to 25% of maximum is shown in
Fig. 5. Since the relationship between
the catalyst power input Qin and the
RF generator output setting was
found to be linear ( Zadrail and
tpnek, 2013), the specific power
input could be calculated as qin
0.36 W/g for each 10% points of
the RF unit output setting. It should
be noted here that the specific power
input is a combined property of the
catalyst composition and geometry,
the induction head design, and the
RF generator setting, and therefore
the most reliable way of finding its
value is empirical measurement as
described above. The value of the
overall heat-transfer coefficient,
evaluated from from Eq.
1

3. Results and discussion

(1), was kqA 0.072070.0005 WK

for a bed containing 18.75 g of the
pellets.

3.1. Catalyst structure and RF heating properties

3.2. Steady-state reaction

The electron micrographs of the composite catalyst pellet, obtained by the

back-scatter electron imaging (BEI) mode, are shown in Fig. 4. The iron
microparticles appear as light-grey spots in the BEI image due to their different
elemental composition and it can be seen that they are relatively uniformly

The experimentally measured

flow rates and the calculated mean
residence times in the catalyst bed
during the reaction are summarised

in Table 1. The ethanol vapour flow rate through the bed was found to be increase of the ethanol vapour flow
rate.
increasing not only with increasing water bath temperature (which controls the
ethanol evaporation rate) but also due to increased RF heating rate. The latter
From the known flow rates of
factor is caused by heating of the passing vapours followed by condensation of
ethanol and ethylene it is possible to
water (product of the reaction) as well as any unreacted ethanol in the outlet
evaluate the reaction conversion. The
tubes, which creates a pressure difference and thus suction that leads to an
ethanol conversion as a function of

power unit output is summarised in

Table 2 and plotted in Fig. 6 as
function of bed temperature. The
temperature of the packed bed during
the catalytic reaction was lower
compared to the

A. Zadrail, F. tpnek / Chemical Engineering Science 134 (2015) 721726

725

mixture.
For the low ethanol flow rates through
the packed bed (0.0420.051 mmol/s) high
conversion rates can be achieved (87%)
even for the lowest power unit outputs
(50%). With

increasing power unit output (above 60%) it

can be considered that, within the
experimental error, all ethanol has been
converted to ethylene. With increasing
ethanol flow rates for lower power unit
outputs, conversions of less than 50% are
achieved but with increasing power unit
output (70%) the conversion increases to
80% for ehtanol flow rates of 0.190 mmol/s,
and even to 100% for the lower flowrate of
0.116 mmol/s.
It is interesting to note that while the
relationship between the RF heating rate,
the ethanol evaporation temperature, and the
resulting flowrate (thus residence time) is
non-trivial ( Tables 1 and 2), the ethanol
conversion appears to be only a function of
bed temperature regardless of how the
temperature was achieved ( Fig. 6a). When
the same data were plotted in form of the
van't Hoff equation

d ln K=d 1=T r H=R

where,
K p Ethyleneout =pEtOHout 1= 1=X1
is the equilibrium constant, a linear trend
was observed, suggest-ing that the reaction
is limited by equilibrium rather than
kinetics.

Fig. 6. a) The overall conversion of ethanol to ethylene as function of bed

temperature for different ethanol evaporation temperatures as indicated. The error
bars were calculated from three experiments. b) The same data plotted in the
format of van't Hoff equation, where the equilibrium constant was calculated from
conversion using reaction stoichiometry.

Fig. 7. Demonstration of the on/off control of the reaction by periodic switching

of the RF magnetic field.

dry RF heating case at the same power unit output ( Table 2).
This was caused by the utilisation of the energy delivered to the
bed not only for its heating and heat losses to the surrounding but
also for the endothermic reaction and heating of the reaction

3.3. Transient RF control of reaction

The control of the endothermic reaction
progress by temperature modulation of the
catalyst bed is shown in Fig. 7. Here we
demon-strate the possibility of remote
control of the reaction by switching the
magnetic field on and off, whereby the On
state represents a power unit output setting
of 60% in this case. From Fig. 7 it can be
seen that the production rate of ethylene
responds almost without delay and stops as
soon as the magnetic field is turned off.
When the magnetic field is turned on again,
the ethylene formation is restarted once the
catalyst reaches the reaction temperature.
The quantity of produced ethylene is
directly proportional to the duration of the
On state. Combined with the results from
Section 3.2 that relates the power output of
the RF unit to catalyst temperature and
conversion, any arbitrary sequence of
ethylene production could in principle be
realised on demand as long as some
reactant (ethanol) is available.

4. Conclusions

Remotely controlled vapour-phase endothermic catalytic reaction products not only in a packed bed
reaction (dehydration of ethanol over alumina) has been studied. configuration as demonstrated in this work,
The remote control of the reaction progress was achieved by but also in stand-alone particles that
introducing iron microparticles into the alumina catalyst and
combine reactant storage ( Kovak et al.,
placing the composite catalyst inside a radiofrequency magnetic
2013) with catalytic conversion. This may
field that caused heating of the catalyst. It was shown
be interesting in applications such as
experimentally that the reaction can be turned on/off by changing
controlled release and delivery of gaseous
the intensity of the applied alternating magnetic field and thus
substances produced in situ by reaction
controlling the temperature of the catalyst. This concept could be
from liquid or solid precursors.
applicable to on-demand synthesis of controlled quantities of

Acknowledgement
This work has been supported by the
Grant Agency of the Czech Republic (grant
no. 13-37055S).

726

A. Zadrail, F. tpnek / Chemical Engineering Science 134 (2015) 721726

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