education for chemical engineers 8 ( 2 0 1 3 ) e94e104

Contents lists available at ScienceDirect

Education for Chemical Engineers
j our nal homepage: www. el sevi er . com/ l ocat e/ ece
Gas solute movement in packed columnsA remote
control experiment
Hugo Silva
a
, Sandra S
a
, Lcia Brando
a
, J.M. Loureiro
b
, Joaquim Gabriel
c
,
Adlio Mendes
a,
a
LEPAE-Departamento de Engenharia Qumica, Faculdade de Engenharia da Universidade do Porto, Rua Dr. Roberto Frias,
4200-465 Porto, Portugal
b
LSRE-Departamento de Engenharia Qumica, Faculdade de Engenharia da Universidade do Porto, Rua Dr. Roberto Frias,
4200-465 Porto, Portugal
c
IDMEC Plo FEUP, Departamento de Engenharia Mecnica, Faculdade de Engenharia da Universidade do Porto, Rua Dr. Roberto Frias,
4200-465 Porto, Portugal
a b s t r a c t
A novel teaching remote controlled experiment is described concerning the solute movement through an adsorption
column. A packed-bed column lled with 5A zeolite was inserted in a thermostatic oven and connected to a TCD
detector. The complete set-up can be remotely controlled and visualized alive using an internet connected camera
to improve the sense of reality. The experiment purpose was to assist and motivate students regarding a topic that
usually they demonstrate difculty to assimilate, which is the prediction of concentration fronts behavior by using
the solute movement theory (SMT). The set-up is versatile to study breakthrough curves and feed pulses. Two loops of
2 cm
3
and 5cm
3
allowthe injectionof O
2
or N
2
adsorbate species that have different isotherms type and consequently
concentration fronts history. Interaction between shock and diffuse waves is addressed for the narrow pulse case
of 2cm
3
. Also, students are able to obtain the nitrogen and oxygen isotherms at different temperatures for the 5A
zeolite (chromatographic method) and compare those isotherms with those obtained by the volumetric method; the
latter is used as reference method.
2013 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Keywords: Gas adsorption; Solute movement theory; Remote control experiment
1. Introduction
Educational laboratories are an important part of the
undergraduate chemical engineering study plan. With the
development of computers and the worldwide internet com-
munications network, the laboratory pedagogical approach
has been changing. Since the late 1990s, a new concept
is emerging in engineering education institutions: remotely
controlled laboratories (Selmer et al., 2007). Remote labs
are systems based on real equipment, which allow stu-
dents to perform experimental work through an internet
connection (Coito and Palma, 2008). Although remotely con-
trolled laboratories are in a maturation process, there are
some advantages pointed in the literature when compared

Corresponding author. Tel.: +351 22 508 1695; fax: +351 22 508 1449.
E-mail address: mendes@fe.up.pt (A. Mendes).
Received23 July2012; Receivedinrevisedform25 June 2013; Accepted30 June 2013
to traditional hands-on laboratories. Engineering education
institutions face budget restrictions to create and maintain
traditional hands-on laboratories, due to an increasing need
of space, staff, availability andsafety (Ogot et al., 2003; Wiesner
and Lan, 2004; Abu-El Humos et al., 2005; Azad, 2007; Jing et al.,
2007; Rafael et al., 2007; Selmer et al., 2007; Murray et al., 2008;
Wiseman et al., 2008; Gravier et al., 2009). On the other hand,
remotely controlled experiments are available fromanywhere
at anytime which facilitates the scheduling process. In addi-
tion, students safety is guaranteed, minimum supervision
is involved and more users can perform the experiment in
comparison with hands-on. Finally, it opens the possibility of
sharing experiments among different institutions, increasing
the number and variety available (Bourne et al., 2005; Azad,
1749-7728/$ see front matter 2013 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.ece.2013.06.002
education for chemical engineers 8 ( 2 0 1 3 ) e94e104 e95
Nomenclature
L column length
K
d
fraction of intraparticle volume species can
penetrate
p
A
partial pressure of solute
p
H
higher value of partial pressure
q
A
amount of solute adsorbed
gas constant
T operation temperature
t time
t
r
retention time
t
F
pulse input time
t
shock
retention time of a shock wave
u
s
solute wave velocity
u
shock
shock wave velocity
u
i
interstitial velocity
U carrier gas ow rate
V
inj
volume of the loop for pulse injection
z axial distance in the column
Greek letters
L variation
interparticle porosity

p
intraparticle porosity
, apparent density
2007; Lang et al., 2007; Selmer et al., 2007; Gravier et al., 2009).
The learning effectiveness and students opinion regarding
remotely controlled laboratories is also evaluated in the lit-
erature (Azad, 2007; Selmer et al., 2007; Rojko et al., 2009).
Students are generally pleased with the convenience of dis-
tance learning; however, they usually point out as a main
disadvantage the loss of sense of reality (Abu-El Humos et al.,
2005; Selmer et al., 2007).
Among the several topics in chemical engineering pro-
grams, the solute movement in gas adsorption processes are
sometimes taught in unit operations courses or in special-
ized courses. Adsorption columns, pressure swing adsorption,
thermal swing adsorption and simulated moving beds, exem-
plify the wide range and importance of commercial processes
based on gas adsorption. In lectures and in the literature,
the solute movement through a packed bed column is usu-
ally represented by diagrams that are not easy to interpret.
The retention of a concentration-front in an adsorbent bed,
the formation of shock waves, and the dispersive phenomena
are difcult concepts for students to promptly assimilate and
visualize mentally. Students should develop a rm grasp of
these concepts, andnot simply manipulate phenomenological
equations. With this mindset, examples of educational lab-
oratory experiments related to the solute movement theory
(SMT) are reported in the literature (Cruz et al., 2001; Becnel
et al., 2002; Fernandes et al., 2005); also computer simulations
could be a useful tool for improving the learning effectiveness
of students since they can visualise what happens inside a
chromatographic column (Cruz et al., 2001).
In our senior undergraduate laboratory of Chemical Engi-
neering Practices, we have developed a novel kind of remotely
controlled experiment to assist students learning about gas
adsorption in solids. This experiment is applied for differ-
ent teaching/learning strategies, such as practical laboratory
classes, improve conceptual demonstration in lecture classes
of separations processes and allowself-learning opportunities
to students. The remote control interface to the experimental
setup is available at: http://elabs.fe.up.pt. Since, students usu-
ally mention the loss of sense of reality of remotely controlled
laboratories as a main disadvantage, to improve the realism
the interface is complemented with live video through an
internet surveillance type camera. Remote users are allowed
to move the camera according to their will, in pan and tilt
directions, as well as to use the zoom function. This way,
students can followthe experiment and have a better percep-
tion of the equipment that they are controlling. The students
opinion about the developed experiment was discussed and
evaluated through questionnaires.
2. Experimental
The main purpose of this remotely controlled experiment
is to provide the students with an opportunity to test and
evaluate the effects of a variety of control variables on the
formation of concentration fronts and to determine adsorp-
tion equilibrium isotherms by using the solute movement
theory (SMT). Accordingly, the user is able to: (i) analyze the
inuence of the volume loop (inlet concentration) on the chro-
matographic response to nitrogen and oxygen pulses fed to
a 5A zeolite column; (ii) analyze the inuence of tempera-
ture on the chromatographic response to nitrogen and oxygen
pulses fed to the same column; (iii) obtain the adsorption
isotherms of nitrogen and oxygen on a 5A zeolite at dif-
ferent temperatures and compare with those obtained from
the volumetric method; (iv) analyze the inuence of differ-
ent feed perturbation types, namely feed pulse and feed
step, on the chromatographic response when nitrogen and
oxygen are fed to the 5A zeolite packed-bed column; (v) ana-
lyze the inuence of the interstitial velocity on the system
response; and (vi) study and predict the inuence of these
different variables on the formation of shock waves. The the-
oretical support and the experimental procedure to guide
students before performing the experiment are available at:
http://elabs.fe.up.pt/Chemical.htm.
The experimental set-up, shown in Fig. 1, comprises essen-
tially a GCTCD equipped with a packed column loaded with
a zeolite adsorbent. The GC and the feed gas systemare con-
trolled by a computer connected to the internet. Aweb camera
and automatic light allowvisualizing the experimental set-up
that can be remotely controlled through the computer. The
details of the experimental set-up are given below:
Gas chromatograph an old GC Pye UnicamChromatograph
equipped with a TCD was used; the manual control of the
oven temperature was modied to allow remote control by
the LabView based program.
Adsorption column a stainless-steel tube, 115cm long and
with 4mminternal diameter, was carefully packed with 10.4g
of adsorbent zeolite 5A (Supelco, 6080 mesh particle size).
For improving the packing quality, one side of the column was
connected to a vacuum pump while being loaded from the
opposite side; on the other hand, the column was continu-
ously hit/shaked with a small hammer. A glass woolen plug
was tted to both columns ends to keep the adsorbent inside
the column. The interparticular porosity, =0.36, was deter-
mined based on the geometric volume of the column. The
adsorbent intraparticle porosity andapparent density,
p
=0.55
and , =1.16gcm
3
, respectively, were determined by mercury
porosimetry.
e96 education for chemical engineers 8 ( 2 0 1 3 ) e94e104
Fig. 1 Experimental setup for the gas adsorption experiment on a porous adsorbent.
Gas feed system two gases can be supplied to the GC,
nitrogen and oxygen, following two feeding modes, step per-
turbation and conventional injection (pulse perturbation). For
the conventional injection, an automatic injection valve (A,
VICI E36) is used. Three-way electric valve (B), Fig. 1, is used
to select the gas and three-way electric valve (C) is used to
select the injectionvolume loop (either 2cm
3
or 5cm
3
). Athird
three way electric valve (D) allows the selection of the exit
position (from2cm
3
to 5cm
3
loops) of the automatic injection
valve to the packed bed column. The carrier gas, helium, is
supplied to the GC by a mass ow controller (E, Bronkhorst,
100cm
3
min
1
). For step perturbations, electric on/off vales F,
G and H are used. The mass ow controller is then used to
control the owrate. At the adsorption column top, a pressure
sensor (I) reads the feeding pressure.
Power supply and acquisition board a standard 12 VDCpower
supply is used to power the mass ow controller, pressure
sensor and electric valves. The valves are controlled using
two in-house built relay boards (with 4 relays each). The relay
boards, mass ow controller, pressure sensor and GC oven
temperature controller (West 8100 PID) are connected to an
acquisition board (Advantech, PLCD-8710).
Web camera an internet surveillance IP camera (PIV-6732,
IP PZT network camera) was connected to a switch (Asus
GX-100SB) together with the computer and the switch was
connected to an internet socket. Computer software allows
using the camera that is capable of zoomand directional con-
trol, giving a sharp view of the experimental set-up.
Controlling software a comprehensive controlling program
was developed in LabVIEW7.1 (National Instruments) Fig. 2.
It allows setting (a) the carrier gas ow rate, (b) the solute
species, (c) the pulse injection volume (selectable 2cm
3
or
5cm
3
), (d) the perturbation type, (e) the adsorption temper-
ature (temperature of the oven) and (f) to trigger the injection
valve. This interface plots on-line the TCD response (related
to the exiting stream concentration), shows the status of all
setting variables and displays the pressure at the columns
top. The variables carrier gas ow rate, TCD response, pres-
sure entrance and retention time can be saved in a text le.
The LabVIEW software has a built-in web server facility to
allow easy internet access, thus providing the option of pub-
lishing the graphical user interface (GUI). This GUI is available
at http://elabs.fe.up.pt and students can access and control
the experiment by using a standard web browser, preferably
Internet Explorer 6. Fig. 3 shows a schematic representation of
the installation set-up.
The experimental set-up was developed mostly by a gradu-
ate student, during his master thesis, and took advantage of a
very old GC obtained at a low price. The whole set-up is quite
inexpensive and it was a great opportunity of learning some
different and relevant competences.
3. Solute movement theory
This section presents a brief description of the underlying
theory to help the student in understanding and analysing
the experiment. Reference books (Wankat, 1990; Seader and
Henley, 1998) could be used to help in a deeper understanding
of the solute movement theory (SMT).
When a pulse gas enters the packed-bed column, it either
moves at the interstitial velocity dened by the carrier gas
ow rate, or is immobilized inside the adsorbent (adsorbed or
in the uid stagnant phase). Accordingly, the average veloc-
ity depends on the time that the solute is retained inside the
adsorbent. This is quite effortless to understand and explain.
However, complexity is present when it is necessary to inter-
pret the formation of different concentration-front waves and
how they interact. This is when the solute movement theory
is helpful since, despite being a mathematical model based
on simple physical phenomena, it can be used to analyze and
understand rather complex processes.
The SMT establishes that an innitesimal element of a sin-
gle gas solute, with partial pressure p
A
, will migrate through
the packed-bed column at a velocity u
s
, which inversely
depends on the slope of the adsorption isotherm (dq
A
,dp
A
),
u
s
(p
A
) =

z
t

p
A
=
u
i
1 +((1 ),)
p
K
d
+((1 ),),T(dq
A
,dp
A
)
(1)
where u
i
is the interstitial velocity of the carrier gas in the
column, p
A
is the solute partial pressure in the uid phase,
q
A
is the solute concentration in the solid phase, , is the
education for chemical engineers 8 ( 2 0 1 3 ) e94e104 e97
Fig. 2 Experiment user interface developed in LabVIEW7.1, with a nitrogen chromatogramresponse.
Fig. 3 Schematic representation of the experiment.
solid apparent density, is the gas constant, T is the abso-
lute temperature, z is the column axial position, t is time,
is the packing (interparticle) porosity,
p
is the intraparticle
porosity (within the particle) and K
d
is the fraction of intra-
particle volume the species can penetrate; K
d
= 1 for small
solute molecules (present case). As it can be seen from Eq.
(1), the solute movement is retarded since the solute is in
the adsorbed phase, ([(1 ),],T(dq
A
,dp
A
)) or in gas phase
inside the porosity of the adsorbent ([(1 ),]
p
K
d
).
The DeVault (SMT) equation can be derived from a solute
mass balance to the absorbent column:
u
i
p
A
z
+
p
A
t
+
1

p
K
d
p
A
t
+
1

,T
q
A
t
= 0 (2)
considering the mathematical relations (3) and (4):

dp
A
dt

p
A
= 0 =

p
A
z

z
t

p
A
+

p
A
t

z
(3)

z
t

p
A
=
(p
A
,t)
z
(p
A
,z)
t
(4)
since p
A
= (z. t), one obtains Eq. (1).
The solute mass balance is based on the following main
assumptions (Wankat, 1990):
(i) Instantaneous equilibrium between the gas and solid phase;
(ii) Plug ow of the gas phase;
(iii) No pressure drop along the column;
(iv) Isothermal operation;
(v) Ideal gas behavior.
Among these assumptions, the least likely to be valid
concerns the local equilibrium. This assumption states that
q relates to p through the adsorption isotherm, neglect-
ing intraparticle mass transport limitations. The model also
assumes plug owwith no axial dispersion, which is not likely
e98 education for chemical engineers 8 ( 2 0 1 3 ) e94e104
q
1
q
2
p
1
p
2
Fig. 4 Two-segment discretized favorable adsorption
isotherm.
to happen. However, for favorable isotherms (with negative
second derivative Fig. 4) and when equilibriumis the domi-
nant phenomenon, normally the SMT approximates well the
adsorption experimental data.
3.1. SMT applied to Langmuir type isotherms
Eq. (3) shows that in order to correctly predict the velocity
of the solute inside the column, the adsorption equilibrium
isotherm for the solute in the adsorbent should be known.
Following, the formation of shock waves and concentration
fronts when the solute adsorbs in the adsorbent phase with a
Langmuir type isotherm (Fig. 4) will be considered. This type
of isothermis usually called favorable isotherm(with negative
second derivative).
The adsorption solute movement of species with a favor-
able isotherm can be more easily conceptualized discretizing
the isotherminto two segments Fig. 4.
For a feed concentration p
1
the solute velocity would be
u
1
; on the other hand, for an adsorption column initially in
equilibriumwith a feed streamof concentration p
1
, when the
feed concentration is changed to p
2
, the solute velocity would
be u
2
and u
2
>u
1
, since the adsorption column retains (delays)
more the solute up to concentration p
1
. When feeding a clean
column with a stream of concentration p
2
, the solute front
would be as sketched in Fig. 5. The higher concentrations (that
could travel at higher velocities, according to Eq. (3)) cannot
move faster than the lower concentrations like when a car at
a higher speedcannot overcome a lower speedcar infront of it.
The following link shows the described analogy, http://chelta.
fe.up.pt/chelta/student/animations/road.swf. Because of this
limitation in the velocity of the higher concentrations, a mass
balance is established at the solute front and a shock wave is
formedthat averages the solute velocity for all concentrations,
as it is presented in Eq. (5):
u
snock
=
u
i
1 +((1 ),)
p
K
d
+((1 ),),T(Zq
A
,Zp
A
)
(5)
For the desorption of a column initially saturated in equi-
libriumwith p
2
, a dispersive wave front is formed; as is shown
in Fig. 6, the lower concentration moves more slowly.
The solute movement is usually explained based on solute
movement diagrams, graphical expression of the mathe-
matical method of characteristics used in the solution of
(hyperbolic) partial differential equations Fig. 7. In Fig. 7, it is
represented the shock wave velocity slope u
shock
, and the gen-
eration of the spreading zone, for the response to a feed pulse
p
2
p
1
z
Shock
Wave
Fig. 5 Conceptual adsorption solute front movement for the isothermdepicted in Fig. 4; a shock wave front is formed.
p
2
p
1
z
Fig. 6 Conceptual desorption solute front movement for the isothermdepicted in Fig. 4; a dispersive wave is formed.
education for chemical engineers 8 ( 2 0 1 3 ) e94e104 e99
u
shock
(p
H
)
L
Z
p
out
p
in
Time
p
H
Time
Time
0
0
0
p
H
Fig. 7 Feed pulse diagrams according to the solute
movement theory: (a) inlet concentration; (b) shock and
diffuse waves formation and; (c) outlet concentration.
of a solute with favorable isotherm. In this case, the shock and
diffuse waves for the highest concentrations exit the column
at the same time, without intersection during their migra-
tion. Fig. 8 sketches the pulse shape as it progresses along the
adsorption column.
For favorable isotherms the following relation between
velocity and concentration is of great importance: u
s
(C
nign
) >
u
snock
> u
s
(C
lou
). Therefore, for a feed pulse perturbation the
leading shock wave is intersected by the high concentration
solute movement if the adsorption column is long enough, as
it can be deduced fromFigs. 7 and 8. Consequently, the solute
elutes at lower concentrations when compared to the original
feedpulse. Regarding the concentrationcurves, students often
have difculty to mentally visualize that the prole shown
in Fig. 8 (t =5), where concentration is represented as a func-
tion of the axial position inside the column, is symmetrical to
the representation of the concentration-fronts as a function
of time (histories), shown in Fig. 7.
For the case of linear isotherms, the solute waves travel all
at the same velocity and the waves formed are usually named
simple. The student should refer to known reference books
on SMT to a better understanding of these concepts (Wankat,
1990; Seader and Henley, 1998).
3.2. Adsorption isotherms determined by the SMT
The adsorptionisothermof the solute species inthe adsorbent
packed in the column can be obtained if the concentration
history to a feed pulse is obtained at the exit of the column.
Fig. 8 Sketch of the solute pulse progress along an adsorption column.
e100 education for chemical engineers 8 ( 2 0 1 3 ) e94e104
Fig. 9 Chromatograph response to a solute feed pulse
with favorable isotherm.
The adsorption isothermcan be obtained fromthe desorp-
tion response to a feed perturbation (diffuse wave). This
happens because the shape of the diffuse wave is related to
solute velocity as a functionof the solute concentration(Fig. 9):
u
i
u(p
A
)
=
t
r
t
0
(6)
where t
0
is the carrier gas retentiontime andt
r
(p
A
) is the solute
retention time, which is a function of solute partial pressure.
Replacing Eq. (1) in (6), it becomes:
t
r
t
0
= 1 +
1

,T

(p
A
) +
1

p
(7)
and expressing the isothermderivative it becomes:
dq
A
dp
A
=
1
(1 ),T

t
r
t
0
[(1 )
p
+]

(8)
Integrating now Eq. (8) one obtains:
q
A
=
1
(1 ),T

p
A
0
0
t
r
t
0
[(1 )
p
+]dp
A
(9)
Eq. (9) can be solved based on the TCD response obtained
for the solute concentration as a function of the retention
time, p
A
= ((t
r
,t
0
) [(1 )
p
+]). However, the TCD used
is old and has a large dead volume, acting as a stirring
tank at the end of the adsorption column that originates the
peak to exhibit a shape similar to the case of a favorable
isotherm (Wankat, 1990). This is a common source of devi-
ations between experimental and model results.
The partial pressure values onthe ordinate axis of the chro-
matogram, h, do not represent the solute partial pressure, but
the h values of ordinate axes are directly proportional to the
solute partial pressure, according to Eq. (10):
p
A
= k n (10)
where h is the arbitrary scale chosen for the ordinate axis (e.g.
the electrical signal from the GC in mV) and k the propor-
tionality factor. This way, the solute partial pressure can be
obtained since the product between the total pressure (p
A
0
)
Time / s
0 50 100 150 200 250 300
N
o
r
m
a
l
i
z
e
d

A
m
p
l
i
t
u
d
e
0.0
0.2
0.4
0.6
0.8
1.0
N
2
-5 cm
3
Fig. 10 Response to a nitrogen feed pulse, at 60

C and
20cm
3
N
min
1
heliumow rate for the injection loops of
5cm
3
.
and the injection time t
inj
is equal to the chromatogramtotal
area, according to:
p
A
0
t
inj
=

0
p
A
dt = k

0
ndt (11)
where:
t
inj
=
V
inj
U
(12)
V
inj
is the loop injected volume and U is the carrier gas ow
rate.
The proportionality factor is obtained from:
k =
p
A
0
t
inj

0
ndt
(13)
After obtaining the partial pressure p
A
value, the next step
is the integration of Eq. (9) to obtain the adsorption isotherm,
q
A
= (p
A
).
4. Observations and discussion
4.1. Determination of adsorption isotherms
In this experimental section, students can determine the
adsorption isotherms of nitrogen and oxygen using the chro-
matographic method. Fig. 10 shows the chromatographic
experimental response to a nitrogen feed pulse of 5cm
3
in the
packed bed column, at 60

C and 20cm
3
N
min
1
helium ow
rate. Students can determine the nitrogen adsorption equilib-
riumisothermfor these conditions, as described in the solute
movement theory section.
Fig. 11 reveals that nitrogen follows a Langmuir type
isotherm on the 5A zeolite; also it compares the adsorption
isotherm obtained from the volumetric method (reference
method) with the chromatographic response for a 5cm
3
feed pulse of nitrogen at 60

C and for a carrier ow rate

of 20cm
3
N
min
1
. Students can conclude that the nitrogen
equilibrium isotherms determined by both methods are very
similar. Other main conclusion that can be taken in this
education for chemical engineers 8 ( 2 0 1 3 ) e94e104 e101
Pressure / bar
0.0 0.1 0.2 0.3 0.4 0.5 0.6
q

/

m
o
l
.
k
g
-
1
0.00
0.05
0.10
0.15
0.20
Chromatographic method
Volumetric method
Fig. 11 Comparison of the adsorption equilibrium
isotherms for nitrogen in the 5A zeolite obtained by the
volumetric method and fromapplying the SMT for a
nitrogen feed pulse, at 60

C.
procedure is that temperature strongly affects the equilibrium
and consequently the determined isotherms.
In order to apply the SMT, Eq. (1), in the following sections,
students can use the adsorption equilibrium isotherms for
oxygenandnitrogeninthe 5Azeolite obtainedby the so-called
volumetric method at 40

C and 60

C. These adsorption equi-

librium isotherms are illustrated in Fig. 12. Nitrogen shows a
typical favorable shape isotherm Langmuir type (represented
by Eq. (15)) as observed above, while oxygen displays a linear
behavior (represented by Eq. (14)).
q
O
2
= HP
O
2
(14)
q
N
2
=
QK
L
P
N
2
1 +K
L
P
N
2
(15)
Students should use the adsorption isotherms parame-
ters represented in Eq. (14) or (15) obtained by the volumetric
method (Table 1) when they are applying the SMT mathemat-
ical model.
Table 1 Nitrogen and oxygen equilibriumparameters
isotherms on the 5A zeolite at 40

C and 60

C.
T (

C) N
2
O
2
Q (mol kg
1
) K
L
(bar
1
) H (mol kg
1
bar
1
)
40 2.42 0.117 0.094
60 2.27 0.077 0.069
Time / s
0 50 100 150 200 250 300
N
o
r
m
a
l
i
z
e
d

A
m
p
l
i
t
u
d
e
0.0
0.2
0.4
0.6
0.8
1.0
Step at 60 C
Step at 40 C
Fig. 13 Response to a nitrogen feed step at 40

C and 60

C
column temperature and heliumowrate of 20cm
3
N
min
1
.
4.2. Determination of concentration fronts by the SMT
With the equilibrium isotherms, it is now possible for stu-
dents to use the SMT and compare the model predictions
with the results obtained experimentally. With this set of
experiments, students can evaluate which variables affect the
velocity of a concentration-front. The experimental procedure
allows to analyze the inuence of the following variables: feed
perturbations, injection volumes (for feed pulse), adsorption
temperature (T) and interstitial velocity (u
i
).
4.2.1. Feed step
Fig. 13 shows the normalized experimental response for a
nitrogen positive feed step into the packed bed column, with
pressure / bar
0.0 0.5 1.0 1.5 2.0
q

/

m
o
l
.
k
g
-
1
0.0
0.1
0.2
0.3
0.4
0.5
O
2
at 40 C
O
2
at 60 C
pressure / bar
0.0 0.5 1.0 1.5 2.0
q

/

m
o
l
.
k
g
-
1
0.0
0.1
0.2
0.3
0.4
0.5
N
2
at 40 C
N
2
at 60 C
Fig. 12 Adsorption equilibriumisotherms on zeolite 5A of (a) oxygen and (b) nitrogen at 40

C and 60

C, determined by the
volumetric method.
e102 education for chemical engineers 8 ( 2 0 1 3 ) e94e104
a feed owrate of 20cm
3
N
min
1
(average column pressure of
1.17bar) at 40

C and 60

C. According to the SMT, this pertur-

bation leads exclusively to the formation of a shock wave; it
is expected that nitrogen exits the column at t
snock
= L,u
snock
,
where L is the length of the adsorption column and Eq. (5)
is used to obtain the velocity of the shock wave. Consider-
ing the column temperature at 60

C, the exit time of the

shock wave for the data presented in Fig. 13 is ca. 163s
and the SMT predicts an exit time of 156s. The SMT was
expected to approximate much more closely the experimen-
tal data since the dominant phenomenon during nitrogen
migration through the packed-bed column should be adsorp-
tion. Actually, for favorable isotherms andwhenequilibriumis
the dominant phenomenon the SMT normally approximates
well the adsorption experimental data (Wankat, 1990). As the
temperature increases the adsorption isothermbecomes less
favorable and the concentration front becomes more disper-
sive (Wankat, 1990) (see Fig. 13). Finally, it was assumed that
the column was operating at an average value between the
outlet and inlet pressures (for this particular case, an average
column pressure of 1.17bar was used in the calculations).
4.2.1.1. Effect of temperature. Inorder to illustrate the temper-
ature inuence in the adsorption process, Fig. 13 presents the
experimental results for nitrogen feed steps performed at two
different temperatures, 40

C and 60

C, and for a carrier gas

and nitrogen feed ow rate of 20cm
3
N
min
1
.
Nitrogen retention time is higher at 40

C, since the
adsorptioncapacityof the adsorbent decreases for higher tem-
peratures. This happens because adsorption is an exothermic
process and the equilibrium constants follow the Vant Hoff
equation. In this way, students can verify that adsorption
equilibriumis strongly affected by temperature. Additionally,
the dispersion phenomenon can be compared for both step
results. The front shape of a breakthroughcurve is the result of
dispersion and compression actions. The dispersion is mostly
related to the axial dispersion and to the intraparticle mass
transport while the compression results fromthe nonlinearity
of the adsorption isotherm as well as the adsorption capac-
ity. Both dispersion and compression forces decrease with the
temperature but the compression forces decrease normally
more. Fig. 13 indicates that in the present case the concen-
tration front at 60

C shows indeed a higher dispersion.

4.2.2. Feed pulse
Students can realize with this set of experiments that com-
plexity of the SMT is increased for a feed pulse mainly when
the shock wave, originated due to the positive concentration
step of the pulse, interacts with the diffuse wave, originated
due to the negative concentration step of the pulse Fig. 8.
4.2.2.1. Inuence of solute species and concentration.
Figs. 14 and 15 show the response of the chromatographic
system at different feed pulses. Two volumes of nitrogen
and oxygen were injected: 5cm
3
and 2cm
3
. The carrier gas
velocity and temperature were 20cm
3
N
min
1
and 60

C,
respectively.
Students can take several conclusions from these exper-
imental observations. The injection of different volumes
of nitrogen (different inlet concentrations) into the column
results in different retention times (Fig. 14). According to the
SMT predictions, the retention time of a shock wave for both
volumes injectedinthe nitrogenfeedpulse is 156s (see above).
Fig. 14 shows that the 5cm
3
pulse retention time corresponds
Time / s
0 50 100 150 200 250 300
N
o
r
m
a
l
i
z
e
d

A
m
p
l
i
t
u
d
e
0.0
0.2
0.4
0.6
0.8
1.0
N
2
pulse of 2 cm
3
N
2
pulse of 5 cm
3
Fig. 14 Response to nitrogen feed pulse, at 60

C and
20cm
3
N
min
1
heliumow rate and for two injection loops:
5cm
3
and 2cm
3
.
Time / s
0 50 100 150 200 250 300
N
o
r
m
a
l
i
z
e
d

A
m
p
l
i
t
u
d
e
0.0
0.2
0.4
0.6
0.8
1.0
O
2
pulse of 2 cm
3
O
2
pulse of 5 cm
3
Fig. 15 Response to oxygen feed pulse, at 60

C and
20cm
3
N
min
1
heliumow rate and for two injection
loops: 5cm
3
and 2cm
3
.
to this value. However, the retention time for the 2cm
3
feed
pulse is higher, ca. 170s, suggesting that the shock wave was
intercepted by the higher concentrations of the diffuse wave.
To conrm this hypothesis, the expected intersection time
(t
1
) of the concentration-waves was determined. The shock
wave and the diffuse wave at the highest concentration inter-
sect at z = z
1
when, u
snock
t
1
= u
s
(t
1
t
F
) where t
F
= V
inj
,Uis the
injection pulse time and u
s
is the diffuse wave velocity at the
highest concentration. Students should obtain u
s
by using Eq.
(3) where dq
A
,dp
A
should be evaluated at the average column
pressure (in this case ca. 1.17bar, see above). The computed
time for the nitrogen 5cm
3
injection volume is 234s, which
corresponds to the column axial position (z
1
= u
snock
t
1
) of
172cm. Since the packed-bed column is only 115cmlong, the
shock and diffuse waves for the 5cm
3
nitrogen pulse never
intercept. In the 2cm
3
nitrogen feed pulse, where the pulse
is narrower, the interception time is at t =94s, which corre-
sponds to the columnaxial positionof 69cm. Therefore, inthis
case the shock wave is intersected by the higher concentra-
tions of the nitrogen diffuse wave before exiting the column.
Taking in to account this interception, the SMT predicts a
retention time of 164s for the 2cm
3
feed pulse, comparing
quite well with the experimental result.
Concerning the oxygen feed pulse, experimental observa-
tions show that the retention time is similar for both injected
education for chemical engineers 8 ( 2 0 1 3 ) e94e104 e103
Time / s
0 20 40 60 80 100 120 140 160 180
N
o
r
m
a
l
i
z
e
d

A
m
p
l
i
t
u
d
e
0.0
0.2
0.4
0.6
0.8
1.0
Fig. 16 Response to a feed pulse of 5cm
3
of nitrogen at
60

C and 40cm
3
N
min
1
heliumow rate.
volumes (Fig. 15). Students can realize this as a consequence
of the oxygen linear type isotherm. In this case, all the oxygen
concentrations travel through the column at same velocity,
forming a simple concentration front wave. The experimen-
tal retention time is around 90s, while SMT prediction is 83s.
However, the asymmetric shape of the peaks might indicate
a favorable isotherm, forming a shock front and a dispersive
wave on the backward. This is not the case and the shape
is partially related to the dead volume of the TCD, ca. 3cm
3
,
which behaves like a perfectly mixed tank.
Figs. 13 and 14 show normalized responses to respectively
step and pulse nitrogen perturbations. The adsorption dis-
persion to the step perturbation is larger than to the pulse
perturbation but it should be noted that the maximum pres-
sure for the step perturbation is ca. 1bar and for the pulse
perturbation is just ca. 0.35bar.
4.2.2.2. Inuence of the carrier ow rate. The inuence of the
carrier gas ow rate was observed by performing a 5cm
3
nitrogen feed pulse at 40cm
3
N
min
1
and 60

C. The obtained
chromatogramis presented in Fig. 16. Students can showthat
the SMT predicts a retention time of 91s, considering an aver-
age column pressure of 1.33bar (higher ow rate than before)
and compare with the experimental retention time. Fig. 16
shows that the retention time is approximately 81s. This 10s
difference between the SMT prediction and the experimental
result can be related to the higher pressure drop in the packed
bed column. In the literature, it is reported that premature
breakthrough curves can be obtained due to velocity devia-
tions, which result from high pressure drop effects (Zwiebel,
1969). Finally, by comparing these experimental results with
the ones for the carrier ow rate at 20cm
3
N
min
1
(Fig. 14),
students can conclude that higher carrier ow rates simply
decrease the exit time of the concentration front.
5. Students opinion
This experiment is available to students that enroll Separation
Processes II subject, third year of the Chemical Engineering
program at Faculty of Engineering of Porto University (FEUP),
when the traveling concentration wave topic is taught. For
performing an experimental run, students must book a time
window. The booking process is currently available by e-mail
but soon will also be possible to book directly from the web-
site of the experiment. 23 students that contacted with this
Table 2 Responses of the students to the inquire.
# Question Fraction of
positive
answers (%)
1 Since remote controlled experiments are
available at anytime, in your opinion would
they be suitable for learning consolidation
through repetition?
82.6
2 Would you prefer to performthe experiments
during the class time or at anytime using the
remote control facility?
73.9
3 During tutorial classes do you prefer to use
experimental data acquired using a remote
controlled experiment or to use assumed
data?
91.3
4 Do you consider that the live camera
improves the really sense when using the
remote controlled experiment?
100
5 Are you familiar with shock waves and
dispersive front?
82.6
experiment were inquired and questions and answers orga-
nized in Table 2.
Students generally prefer to use this remotely controlled
experiment to generate the data needed for solving train-
ing problems than to use assumed data. Though they think
this experiment can be used to consolidate their knowledge
because, theyprefer toperformit during the labclasses, proba-
blydue tosome independent learning insecurity. The presence
of the live camera is unanimously viewed as very relevant to
give a sense of reality to the experiment. Finally, the students
state that the shock wave and dispersive fronts are familiar
concepts, showing a relevant assimilation of critical concepts.
6. Conclusions
A remotely controlled educational experiment was developed
to support students acknowledgment of a quite complex topic
inchemical engineering: gas adsorptionthrougha packed-bed
column. From anywhere, at any time, students can comple-
ment the theoretical knowledge gathered about this topic,
withreal experiments performedonline (http://elabs.fe.up.pt).
The solute movement theory, as oversimplied model, is
the ideal tool for students rst contact with gas adsorp-
tionphenomena. While performing the experiments, students
should critically discuss the results with the model predic-
tions. This way, it is expected that students consolidate their
knowledge on adsorption and on solute movement in an
adsorption column and understand the model limitations and
all the inuence factors inherent to this kind of separation
processes. Regarding students opinion, it was asked if they
preferred to use the remote controlled experiment with a
virtual interface or a real set-up during class time. A sig-
nicant percentage (73.9%) stated a preference for making
experiments in the laboratory class, using real equipment.
The experiment targets both laboratory classes as well as lec-
tures/tutorials classes. The greatest novelty is, however, its use
to assist teaching lecture/tutorial classes and namely Sepa-
ration Processes courses. This experiment can be used, for
example, to obtain the real solution for a problem ques-
tioned to a group of students in a tutorial class. Comparing
their result with real result, students can learn more and
deeper since they are also involving more their emotion.
Finally, students seem to be motivated with this learning
e104 education for chemical engineers 8 ( 2 0 1 3 ) e94e104
strategy, since they expressed their preference of using real
experimental data instead of assumed data.
Acknowledgments
The authors would like to acknowledge the Chemical Engi-
neering Department of the Faculty of Engineering at the
University of Porto and paint company CIN SA for supporting
this work. The authors are also grateful to Eng. Luis Matos for
collaborating assembling the experimental set-up.
References
Abu-El Humos, A., Alhalabi, B., et al., 2005. Remote labs
environments (RLE): a constructivist online experimentation
in science, engineering, and information technology. In: 31st
Annual Conference of IEEE, Industrial Electronics Society
2005, IECON 2005.
Azad, A.K.M., 2007. Delivering a remote laboratory course within
an undergraduate program. Int. J. Online Eng. 3, 7.
Becnel, J.M., Holland, C.E., et al., 2002. Fundamentals of Fixed Bed
Adsorption Processes: Analysis of Adsorption Breakthrough
and desorption Elution Curves. American Society for
Engineering Education, Montreal, Quebec, Canada.
Bourne, J., Harris, D., et al., 2005. Online engineering education:
learning anywhere, anytime. J. Eng. Educ. 94,
131145.
Coito, F., Palma, L.B., 2008. A remote laboratory environment for
blended learning. In: First International Conference on
Pervasive Technologies Related to Assistive Environments,
PETRA 2008, July 16, 2008July 18, 2008. Athens, Greece,
Association for Computing Machinery.
Cruz, P., Mendes, A., et al., 2001. Using in-bed temperature
proles for visualizing the concentration-front movement.
Chem. Eng. Educ. 35, 122127.
Fernandes, D.L.A., Xavier, A.M.R.B., et al., 2005. Dynamic and
equilibriumadsorption experiments. J. Chem. Educ. 82,
919923.
Gravier, C., Fayolle, J., et al., 2009. State of the art about remote
laboratories paradigms: foundations of ongoing mutations.
Int. J. Online Eng. 4, 1925 (Copyright 2009, The Institution of
Engineering and Technology).
Jing, G., Kettler, D., et al., 2007. A chemical engineering laboratory
over distributed control and measurement systems. Comput.
Appl. Eng. Educ. 15, 174184 (Copyright 2007, The Institution
of Engineering and Technology).
Lang, D., Mengelkamp, C., et al., 2007. Pedagogical evaluation of
remote laboratories in eMerge project. Eur. J. Eng. Educ. 32,
5772.
Murray, S., Lowe, D., et al., 2008. Experiences with a hybrid
architecture for remote laboratories. In: 38th ASEE/IEEE
Frontiers in Education Conference, FIE 2008, October 22,
2008October 25, 2008. Institute of Electrical and Electronics
Engineers Inc., Saratoga Springs, NY, United States.
Ogot, M., Elliott, G., et al., 2003. An assessment of in-person and
remotely operated laboratories. J. Eng. Educ. 92, 5764.
Rafael, A.C., Bernardo, F., et al., 2007. Virtual applications using a
web platformto teach chemical engineering: the distillation
case. Educ. Chem. Eng. 2, 2028.
Rojko, A., Debevc, M., et al., 2009. Implementation, effectiveness
and experience with remote laboratory in engineering
education. Organizacija 42 (1), 2333.
Seader, J.D., Henley, E.J., 1998. Separation Process Principles.
Wiley, New York.
Selmer, A., Kraft, M., et al., 2007. Weblabs in chemical
engineering education. Educ. Chem. Eng. 2, 3845.
Wankat, P.C., 1990. Rate-Controlled Separations. Elsevier Science
Publishers, New York.
Wiesner, T.F., Lan, W., 2004. Comparison of student learning in
physical and simulated unit operations experiments. J. Eng.
Educ. 93, 195204.
Wiseman, C., Wong, K., et al., 2008. Operational experience with a
virtual networking laboratory. In: 39th ACM Technical
Symposiumon Computer Science Education, SIGCSE 2008,
March 12, 2008March 15, 2008. Association for Computing
Machinery, Portland, OR, United States.
Zwiebel, I., 1969. Fixed bed adsorption with variable gas velocity
due to pressure drop. Ind. Eng. Chem. Fundam. 8, 803807.