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Printed in Great Britain. # 2006 TEMPUS Publications.
NOMENCLATURE Subscripts
CV crystal violet
C concentration of tracer, reactant or in inlet conditions
product (mol.mÿ3) out outflow conditions
Cout average exit concentration of the reactant batch batch reactor
(mol.mÿ3)
Ea activation energy (J.molÿ1) Greek symbols
ei
exponential integral function space-time (s)
E
t residence time distribution function (sÿ1) kL k
F
t Danckwerts' F curve
umax 2
H
t Heaviside function
k0 pseudo first-order rate constant (sÿ1)
k second-order rate constant (m3 molÿ1 sÿ1)
ko pre-exponential factor (m3 molÿ1sÿ1) INTRODUCTION
L length of the reactor (m)
Q volumetric flow rate (m3sÿ1) REACTION BETWEEN CRYSTAL violet and
r radial position in the tubular reactor (m) sodium hydroxide has been widely used for peda-
(ÿr) reaction rate (mol.mÿ3sÿ1) gogical purposes. Some important reasons are the
R internal radius of the reactor (m) change in colour as the reaction progresses, which
t time (s) is a visual reinforcement of the measured results,
u
r fluid velocity at the radial position r and also the fact of being operable at room
(m.sÿ1) temperature, thus reducing the complexity and
umax maximum fluid velocity (m.sÿ1) cost of the experimental apparatus [1, 2]. It is
umean mean fluid velocity (m.sÿ1) well known that this hydrolysis reaction is
V reactor volume (m3) second-order (first-order towards each reactant)
X conversion [1, 2], but, if sodium hydroxide is present in great
X average conversion excess, it can be assumed to be pseudo first-order:
Xoverall overall experimental conversion (consid-
ering both reactor and tube)
ÿrCV kCNaOH CCV k0 CCV
1
Xtube experimental conversion reached in the where k0 is the pseudo rate constant.
connection tube Crystal violet is a highly coloured dye with a
z axial position in the tubular reactor (m) maximum absorbance at a wavelength of 588 nm.
On the other hand, both sodium hydroxide and
the hydrolysis product (carbinol derivative) are
* Accepted 26 September 2004. colourless, the corresponding aqueous solution
188
Teaching Laminar-Flow Reactors: From Experimentation to CFD Simulation 189
having an absorbance similar to that of water. So, that sufficient retention time is provided for the
it is possible to follow this reaction by spectro- reaction mixture. Otherwise, low conversion values
photometry. Direct visualization is also of interest, are obtained. To avoid this, operation is frequently
as it provides an intuitive qualitative description of done at low flow rates (in some cases under a
the hydrolysis progression. laminar regime), as such rates allow a greater
This reaction was conducted by Hudgins and reaction time for a given reactor, or allow the
Cayrol [2] in a tubular reactor. The authors design of a shorter reactor to perform a desired
reported that students were very interested in the conversion. Apart from the recognized industrial
experiment, which led us to adopt it. However, we interest of LFTRs, particularly in processing poly-
have incorporated tracer experiments for flow mer, food or other types of viscous fluids [8, 9], or
pattern characterization in the laminar-flow tubu- in emerging areas such as monolith reactors or
lar reactor (LFTR). The idea is to obtain an micro-process engineering (because flow in the
integrated chemical reaction engineering lab channels is laminar) [10], this type of reactor has
experiment [3]. Indeed, during the first semester been widely used for instructional purposes [2].
of the fourth academic year, in the current curri- In this section we present the main equations
cula of our ChE study plan, students have a that students need to use in order to: (i) verify if the
laboratory course where they operate, among flow pattern in the tubular reactor can be modelled
other experimental projects, batch and continu- as a laminar-flow tubular reactor (LFTR) and (ii)
ous-flow reactors. Using conventional tracer predict the steady-state conversion in the real
experiments, they characterize the flow pattern in reactor.
the open reactors. The residence time distribution In an LFTR with radius R, the velocity profile is
(RTD) then determined is used in a subsequent lab parabolic and can be mathematically described by
class, together with reaction kinetics data collected the well-known Hagen-Poiseuille equation:
in a batch reactor, to predict the theoretical r 2
conversion in the same reactor, which is compared
u
r umax 1 ÿ
2
to experiment results. This experiment work is R
performed in three consecutive lab classes, each
three hours long (one for the kinetic analysis, the where umax is the fluid velocity at the centre of the
second for RTD determination, and the final one pipe (umax 2umean ). From this profile, and assum-
for measurement of steady-state conversion). ing negligible molecular diffusion of the species,
The following semester, students deal with the residence time distribution in an LFTR can be
another kind of experimental set-ups, some of easily deduced [11, 12]:
them at a pilot-scale, and handle some software
tools that might be used in industrial practice. In 2
this respect, the use of computational fluid E
t H t ÿ
3
2t3 2
dynamics (CFD) codes has been implemented,
because these have been successfully used in prac- where is the space-time and H
t the Heaviside
tice to design commercial-sized reactors, usually function. Integration of this equation provides the
with complex flow processes [4], and have a well-known Danckwerts' F curve, which is the
significant pedagogical potential [5, 6]. However, normalized reactor response to a step change at
CFD cannot be adequately used without contin- the entrance:
ued reference to experimental and/or analytical
t
validation of numerical results [7]. Therefore, we Cout
t
F
t E
t dt
propose that students use a CFD code to simulate Cin 0
the laminar-flow reactor that they studied in the 2
previous lab course, and compare the simulated 1ÿ H tÿ
data with their experiment results (both flow 2t 2
pattern characterization and steady-state conver- 8
sion data). Since analytical solutions are available <0
> t < =2
for either the RTD or the steady-state conversion, 2
4
>
: 1ÿ t =2
these are an important tool for students to check the 2t
validity of their simulation results. Most of the
computational work is carried out in two classes, In the pure convection regime (negligible mole-
each one being three hours long. Additional simula- cular diffusion), each element of fluid follows its
tions can, however, be performed at home, or using streamline with no intermixing with neighbouring
the computers in the faculty computing rooms. elements. In essence this gives macrofluid beha-
viour, for which the average conversion
X can be
predicted by the total segregation model [11, 13].
LAMINAR-FLOW TUBULAR REACTORS: This model assumes that fluid elements having the
THEORETICAL BACKGROUND same age (residence time) `travel together' in the
reactor and do not mix with elements of different
Operation of tubular reactors at high flow rates ages until they exit the reactor. Because no mass
may necessitate the use of long vessels to ensure interchange occurs between fluid elements, each
190 L. Madeira et al.
EXPERIMENT SET-UP
The experiment set-up used for the tracer and Fig. 1. Sketch of the tubular reactor.
conversion experiments is basically composed of a
transparent acrylic jacketed tubular reactor
(length 1.01 m; internal diameter (ID) 2.2 For the flow pattern experiments, a tracer step
10ÿ2 m), which is connected to a thermostatic input is made at the reactor inlet. The tubular
bath with heating and cooling system (Huber, reactor is first filled with distilled water and then
Polystat cc1). Solutions are fed to the reactor one switches to the tracer solution (crystal violet at
using a peristaltic pump with eight rolls and two a concentration of about 1 10ÿ5 M), which is fed
channels, from Ismatec (model Reglo-Analog until absorbance at the reactor outlet approaches
MS-2/8-160), and the exit stream is directed to a the value previously recorded for that solution.
flow-through cell of a Jenway 6300 spectrophot- Students' attention is drawn to the fact that a
ometer, operating at 588 nm. Connection of the much diluted tracer solution must be used, so
RS232 port of the spectrophotometer to a compu- that its density is close to that of water and there-
ter allows for absorbance data to be collected, fore does not affect the reactor hydrodynamics.
saved and displayed in the monitor, at a frequency Otherwise, the expected laminar profile will not be
of 0.5 Hz. A simple data acquisition program was obtained, due to the action of gravity. Another
developed for this purpose in LabVIEW (National crucial point is that the temperature of both
Instruments). It is noteworthy that a static mixer solutions and that of the reactor's wall must not
was introduced at the reactor's inlet (bottom) for differ by more than about 0.5ëC. Higher differ-
homogenization of the reactant streams and to ences will lead to natural convection streams
ensure a good distribution of the feed through induced by the temperature gradients, which
the entire reactor cross-section (Fig. 1). This would also significantly affect the parabolic
mixer consists of a small cylinder (20 mm length velocity profile.
and 8 mm ID) filled with small glass beads (with During the tracer experiment the outlet flow rate
diameters in the range of 850±1230 m), followed must be determined at least three times. For the
by a conical tube (with internal diameters of 3 mm data herein provided, Q 0.879 10ÿ6 m3/s. The
and 22 mm and a length of 10 cm), containing glass time required for the tracer solution to reach the
beads with dp 3 mm. At the reactor outlet, an reactor inlet (i.e., the time spent along the path
identical conical tube containing glass beads vessel ! reactor), as well as the time spent between
ensures good mixing of the exiting streamlines. the reactor outlet and the detector, must be known
Teaching Laminar-Flow Reactors: From Experimentation to CFD Simulation 191
to correct the F
t curve. These values are about time (several hours with a 2.00 GHz Pentium IV
48.8 s and 18.4 s, respectively. Moreover, this last processor), this can easily be decreased to
value is also crucial to rectify the steady-state about 15±20 minutes if students use less elaborate
conversion, once reaction progresses in the connec- meshes, without significantly affecting the preci-
tion tubes. This issue will be discussed further sion of their results. Such less refined meshes are
below. provided for students, who use them in the simula-
For determination of the steady-state conver- tions performed in the class. Refining of the
sion in the continuous-flow tubular reactor, the meshes is only advisable if students wish to
two reactant solutions (sodium hydroxide 0.05 M obtain a higher precision in their simulations,
and crystal violet 2.0 10ÿ5 M) are fed to the and this can be performed outside class time.
bottom until a constant absorbance is recorded It is noteworthy that, since the problem under
at the reactor outlet. The solutions were fed at a study is axis-symmetric, only one half of the tube
total flow rate of 0.849 10ÿ6 m3/s ( 452.2 s, has to be considered in the geometric domain
which includes the time spent by fluid elements in (L 1.01 m, ID 1.1 10ÿ2 m). One face (upper,
the reactor and in the inlet and outlet static mixers/ in the figures shown below) is defined in the
diffusers; see Fig. 1). The ratio between the two boundary conditions as a wall (no-slip conditions
individual volume flow rates is slightly different and null fluxes), while the other is an axis (the
from unity, since the two heads of the peristaltic symmetry axis, which corresponds to the center
pump are not absolutely identical (for the data line of the cylindrical reactor). At the inlet, a
herein presented, QNaOH =QCV 1:124). Students perfectly developed parabolic profile was imposed,
are warned about this, so they should correct the computed using the Hagen-Poiseuille equation
absorbance of the fed crystal violet solution and (equation (2) ).
the inlet sodium hydroxide concentration. It The components considered were water and a
should be noticed that the basic solution is present tracer solution, both having identical properties,
in a concentration about 2500-fold in excess, so so that there is no interference with the reactor
that equation (1) applies; i.e., the reaction can be hydrodynamics. Mixture properties were computed
considered as pseudo first-order. The jacket of the based on fluid characteristics, using mixing-law
reactor is filled with water at a temperature close to (mass-weighted or volume-weighted) formulations.
room temperature. In the present case, the experi- To simulate the tracer experiments, the system is
ment was performed at 19.45ëC. initialized imposing a null tracer concentration
throughout the domain. At time t 0 a step
change is introduced at the reactor inlet, with
CFD SIMULATIONS uniform tracer concentration. The tracer concen-
tration history at the reactor outlet (obtained from
Simulations of both the hydrodynamics and a mass-weighted average formulation) is then
chemical reaction were run with the commercial computed and saved in an ASCII file, allowing
package Fluent 6.0, from Fluent Inc. Although the subsequent manipulation with any spreadsheet
software is quite user-friendly, it is advisable that a software, such as Microsoft ExcelTM.
brief tutorial is provided so that students can For simulation of the reaction process, Fluent's
quickly familiarize themselves with the program. steady scheme was adopted. In addition, the volu-
In this tutorial, the essential steps that must be metric reaction menu was activated, requiring
followed for any simulation should be outlined, introduction of the reaction rate parameters (reac-
preferably giving an example. Then different tion order, stoichiometric coefficients, frequency
exercises can be provided for groups of two or factor and activation energy). The new compounds
three students, who should finally compile their (reactants and products) and their properties were
results into a written report (usually of less than also included in the materials database, as well as
10 pages), or they could discuss them in an oral the operating temperature (but an isothermal
presentation of no longer than 15 minutes. In any process was considered). Obviously, the mass frac-
case, students should include simulations of the tion of each compound was introduced in the inlet
hydrodynamics, RTD and reaction experiments, boundary conditions.
using experimental conditions chosen by them- Finally, it should be noted that all the simulation
selves (for instance, similar to those used in the results presented here required a preliminary
previous lab course). Some groups also perform analysis in order to choose the best conditions
nice CFD animations, particularly for other and numerical algorithms to adopt, so that
systems/geometries. higher accuracy could be achieved. Students are
To simulate the flow pattern in the experimental warned about this, and to obtain smaller computa-
tubular reactor, a laminar 2D model was adopted, tional times the numerical algorithms that should
this being the system geometry (mesh) previously be adopted are explained in their CFD tutorial.
constructed with a pre-processing software The simulations discussed below were run using
(Gambit, in our case). For better accuracy, a the QUICK scheme, convergence criterion of
computational grid containing 10,000 elements 1 10ÿ4 (although residuals were frequently
was adopted in the results presented below. much smaller). In the specific case of unsteady
Although this involves a somewhat long simulation state simulations, the second order-implicit
192 L. Madeira et al.
formulation was adopted with a time step of 1 s. In by-passes. This difference is most probably a
this manner, the results are independent of the consequence of experimental errors, particularly
time-step size. The same criterion was used for those associated with V and Q determination.
the selection of the mesh size (grid with 10,000 Students are asked to analyze and discuss this in
elements). more detail.
When using the CFD software to characterize
the hydrodynamics in the reactor, students can
RESULTS AND DISCUSSION start by analyzing the steady-state contours of
the stream function, which illustrate the trajec-
Flow pattern characterization in the tubular tories of the fluid elements. The streamlines
reactor obtained must be absolutely parallel, as expected
The data shown in Fig. 2 illustrate the history of for laminar flow, so that no intermixing occurs
the normalized absorbance data at the reactor with neighbouring elements.
outlet after performing a step change in the The simulated velocity profiles at any axial
tracer concentration at the feed. That is, it repre- position are also interesting to observe. Fig. 3
sents the experimentally recorded Danckwerts' illustrates a typical profile, after the convergence
F curve (F
t Cout
t=Cin ), which shows the criteria are satisfied. In this case the tube's outlet
expected shape, only reaching the asymptotic boundary was chosen to build the velocity plot,
value of 1 for very long times. In addition, the although any other position may be created for
tracer reaches the reactor outlet at about t 216 s, that purpose. Data obtained show the expected
which is practically half the space-time, as is to be parabolic profile, with the higher velocities at the
expected for a laminar velocity profile (fluid centre of the tube and with null velocities near the
elements in the centre of the pipe have the highest wall. The simulated data are very well described by
velocity, umax 2umean , thus reaching the exit at the Hagen-Poiseuille law (equation (2) ).
t /2). While recording the data, students should After performing steady-state simulations,
pay particular attention to the parabolic velocity students may proceed to transient runs. After
profile that can be seen travelling along the reac- defining the tracer step input at the inlet boundary,
tor, since its wall is transparent and the tracer the software code solves the convection-diffusion
solution coloured. equation that describes the tracer transport and
Because one is dealing with laminar flow in a the student obtains the concentration field of
tube, an analytical solution exists for both the tracer under transient regime. The contours of
residence time distribution and the Danckwerts' tracer concentration throughout the reactor
F curve, as shown above (equations (3±4) ). In along time are quite interesting to observe because
order to fit the theoretical model to their experi- they provide a good perspective of how the
ment results and therefore determine the value of concentration front evolves. The frames recorded
the single model parameter (), students can use and shown in Fig. 4 show that it is only for t / 2
the `Solver' add-in available in Microsoft ExcelTM that one starts `seeing' tracer at the reactor outlet,
and perform a nonlinear fitting. In this case, as expected for laminar flow in pipes (see equation
optimization of the least-squares provided the (4) ). In addition, even for very long times
following value: 483.3 s. The corresponding (about five times the space-time) the tube is not
fitting curve is also shown in Fig. 2. Although completely full of tracer, due to the very low
some discrepancy exists between the experimental velocities near the walls.
space-time value ( V/Q 436.8 s, where V is the As mentioned above, during unsteady simula-
total volume of the reactor and Q the volumetric tions the student may save the tracer concentration
flow rate) and that obtained from the fitting at the outflow boundary in an ASCII file, so that
process, this is certainly not due to irregularities the Danckwerts' F curve can be subsequently
in the reactor's operation, like stagnant regions or computed. Figure 5a shows the F
t curve
Fig. 4. Transient tracer concentration contours at the inlet and outlet sections of the tubular reactor ( 483.3 s). The entire reactor
length cannot be shown because of the high L/D ratio.
obtained from Fluent simulation. It is noteworthy segregation model (compare equation (5) ). Indeed,
that the simulated data practically coincide with due to the very long tail Rof the E
t curve, the
1
the analytical solution (equation (4) ), the differ- normalization condition ( 0 E
tdt 1) is only
ence being more evident at times around 240 s (see satisfied if experiments/simulations are performed
detail of Fig. 5a); i.e., when the tracer concentra- for very protracted times (typically about five
tion front reaches the reactor outlet. Figure 5b times the space-time, such that relative errors are
shows the E
t curve, obtained by derivation of the below 1±2%). Therefore, conversion is predicted
F
t data, which exhibits the typical very long tail. using the analytical RTD equation, since the flow
It should be pointed out that, although more pattern corresponds to that of an LFTR.
accurate data could be obtained with CFD simula-
tion (for instance with a more refined mesh), this is
completely unnecessary. Indeed, with the numer- Determination of steady-state conversion in the
ical algorithms used and the time-step and grid laminar-flow tubular reactor
adopted, the steady-state conversion prediction Although it is beyond the scope of the present
leads to a relative error below 1%, when comparing paper, it should be noted that in a previous lab
the Fluent simulation with the analytical solution session students determined the rate constant for
(as mentioned below). the reaction between crystal violet and sodium
Students are also warned that the E
t curve hydroxide. This is done in a batch reactor, at
does not need to be obtained from their experiment three different temperatures, so that the activation
data. First, one introduces too much numerical energy can also be obtained. Experiments
noise when computing the derivative of the F
t performed in the range 15±25ëC provided the
curve. Second, to accurately predict the steady- following results for the frequency factor and
state conversion directly from the RTD data, activation energy: ko 1:193 107 m3 molÿ1sÿ1
tracer experiments should be performed for very and Ea 6.195 104 J molÿ1 [14]. These values
long times. Otherwise, the area under the E
t will subsequently be used for prediction of the
curve is not duly taken into account in the total theoretical conversion.
194 L. Madeira et al.
* 452.2 s, T 19.45ëC.
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CatalõÂticos, SeparacËoÄes naÄo Convencionais e Tecnologia dos SoÂlidos Divididos (Chemical Engineer-
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laboratories, separation processes and numerical methods. His main research interests
include membrane and sorption gas separations, catalytic membrane reactors and fuel cells.