Article

A MATLAB-Based Application for Modeling

and Simulation of Solar Slurry Photocatalytic
Reactors for Environmental Applications
Raúl Acosta-Herazo 1,*, Briyith Cañaveral-Velásquez 2, Katrin Pérez-Giraldo 2,
Miguel A. Mueses 2, María H. Pinzón-Cárdenas 1 and Fiderman Machuca-Martínez 1
1 School of Chemical Engineering, Universidad del Valle, Cali A.A. 25360, Colombia;
[email protected] (M.H.P.-C.); [email protected] (F.M.-M.)
2 Modeling and Applications of Advanced Oxidation Technologies Research Group,

Photocatalysis and Solar Photoreactors Engineering, Department of Chemical Engineering,

Universidad de Cartagena, Cartagena A.A. 1382-195, Colombia; [email protected] (B.C.-V.);
[email protected] (K.P.-G.); [email protected] (M.A.M.)
* Correspondence: [email protected]

Received: 2 July 2020; Accepted: 27 July 2020; Published: 4 August 2020

Abstract: Because of the complexity caused by photochemical reactions and radiation transport,
accomplishing photoreactor modeling usually poses a barrier for young researchers or research
works that focus on experimental developments, although it may be a crucial tool for reducing
experimental efforts and carrying out a more comprehensive analysis of the results. This work
presents PHOTOREAC, an open-access application developed in the graphical user interface of
Matlab, which allows a user-friendly evaluation of the solar photoreactors operation. The app
includes several solar photoreactor configurations and kinetics models as well as two variants of a
radiation absorption-scattering model. Moreover, PHOTOREAC incorporates a database of 26 of
experimental solar photodegradation datasets with a variety of operational conditions (model
pollutants, photocatalyst concentrations, initial pollutant concentrations); additionally, users can
introduce their new experimental data. The implementation of PHOTOREAC is presented using
three example cases of solar photoreactor operation in which the impact of the operational
parameters is explored, kinetic constants are estimated according to experimental data, and
comparisons are made between the available models. Finally, the impact of the application on young
researchers’ projects in photocatalysis at the University of Cartagena was investigated.
PHOTOREAC is available upon request from Professor Miguel Mueses.

Keywords: computer-based learning; solar photocatalysis; water contaminants; kinetic modeling;

photoreactor design

1. Introduction
Heterogeneous photocatalysis is an example of an emerging environmental technology with a
variety of promising applications, such as air and water disinfection and decontamination, clean fuel
production and green product manufacturing [1–3].
Modeling and computer simulation of photoreactors are crucial for their design, scale-up and
technology transfer; since they allow engineers and researchers to understand the role of the design
parameters and operational conditions without performing an excessive number of experiments.
However, modeling a solar photoreactor is a very complicated task, because it requires a combination
of knowledge in applied solar energy, geometric optics, radiative transfer, materials science and
photochemical reaction engineering.

Water 2020, 12, 2196; doi:10.3390/w12082196 www.mdpi.com/journal/water

Water 2020, 12, 2196 2 of 17

The implementation of commercial packages for photoreactor simulations is limited. Simulation

packages for chemical plants, such as Aspen HYSYS® (Aspen Technology, Inc., Bedford, MA, USA)
or Aspen plus® (Aspen Technology, Inc., Bedford, MA, USA), do not incorporate photocatalytic
reactors. On the other hand, modeling and simulation of photoreactors can be carried out in
Computational Fluid Dynamics (CFD) packages, such as COMSOL Multiphysics® (COMSOL, Inc.,
Burlington, MA, USA) and ANSYS® Fluent (ANSYS, Inc., Southpointe, PA, USA). However, they do
not have modules dedicated to photoreactor engineering. Therefore, the simulations are performed
by adapting the existing simulation modules for the simulation of photocatalytic reactors. This
configuration of the CFD modules must be carried out manually by the user, which may result in an
approach not intuitive enough for non-experts in photoreactor engineering. Another alternative is to
perform the direct coding of the photoreactor model in a programming language. Still, this may result
in a challenge for researchers that have not taken advanced courses in programming and numerical
methods.
For the above reasons, the direct coding or the use of CFD simulators to implement a
photoreactor model could be found inconvenient by non-expert researchers in photoreactors
engineering, such as young researchers or those focused on experimental developments. However,
implementing a photoreactor model may be a crucial tool for reducing the experimental efforts and
carrying out a more comprehensive analysis of the results.
In this work, we present PHOTOREAC, an open-access computational application developed in
the graphical user interface of Matlab wholly dedicated to the modeling and simulation of large-scale
slurry solar photocatalytic reactors for environmental applications. It is based on the experience
gathered by our research groups at Cartagena University (Cartagena de Indias, Colombia) and the
Universidad del Valle (Cali, Colombia) during the last twenty years of research in heterogeneous
solar photocatalysis, and also on extensive literature research in photoreactor engineering.
The application aims to provide non-expert researchers in photoreactors engineering a user-
friendly, dedicated and efficient tool for the modeling and simulation of solar photoreactors,
providing them with valuable information without implementing very sophisticated methods.
By employing PHOTOREAC, the users will be able to explore the role of critical parameters of
the system on the radiation absorption performance of the photoreactor and the overall kinetic
behavior of the photocatalytic process; parameters include the photoreactor geometry, the
photoreactor dimensions, the model pollutant, the kinetic expression, the photocatalyst
concentration, the photocatalysts optical properties, the initial pollutant concentration, the volume of
treated water and the incident radiation. Additionally, PHOTOREAC incorporates a database of
experimental information collected in our laboratory regarding the solar photodegradation of a
variety of model pollutants under different operational conditions. Therefore, users will have
empirical data available to carry out analyses and comparisons with their data.

2. Solar Photoreactors Modeling by PHOTOREAC

PHOTOREAC performs the modeling and simulation of the photoreactors following the general
algorithm described in Figure 1. The algorithm considers mathematical simplifications to maintain
the approach as rigorously and computationally efficient as possible, and thus it provides the users
with valuable information without implementing sophisticated numerical methods that, although
they can improve the quantitative results, may not affect the qualitative analysis. These assumptions
and simplifications will be described and discussed in the upcoming sections.
The basis of the PHOTOREAC approach is that the radiation field modeling can be carried out
independently of the photocatalytic kinetics modeling since the radiation balance in the photoreactor
is not a function of the concentration of the chemical species. Therefore, the radiation balance is
decoupled from the mass and momentum balances of the system. Besides, the radiation field
described by the local volumetric rate of photon absorption (LVRPA) profile inside the photoreactor
is considered to be in a steady-state, i.e., it does not vary along the reaction rime its reaction time does
not change [4,5]. On the other hand, to carry out a kinetic analysis independent of the radiation
Water 2020, 12, 2196 3 of 17

absorption effects, i.e., the optimized kinetic parameters are not a function of the irradiation
conditions, it is mandatory to know the radiation field in the photoreactor beforehand [6,7].
Thus, PHOTOREAC considers two modules: (i) the photon absorption-scattering module, in
which the user will be able to determine the radiation field of the available photoreactor
configurations by following the procedure described by the red box in Figure 1; and (ii) the kinetic
modeling module, in which the user will be able to estimate the radiation-independent kinetic
parameters for the four available kinetics expressions following the procedure described in the blue
box in Figure 1.

Figure 1. General algorithm for the modeling and simulation of solar slurry photoreactors in
PHOTOREAC. ODE: Ordinary Differential Equation; SFM: Six Flux Model.

2.1. The Photoreactors Set-Up in PHOTOREAC

PHOTOREAC includes three configurations of pilot-scale solar photoreactors: a flat plate
photoreactor (FPP), a compound parabolic collector photoreactor (CPCP) and a tubular-type
photoreactor (TTP). These are the most common configurations for solar-pilot applications of
heterogeneous photocatalysis; a detailed description of them can be found in the literature [3,8,9]. For
the TTP, a novel prototype is also included, the offset multi-tubular photoreactor (OMTP) [10]. All of
the photoreactors operate in recirculation, a flow-through mode with the water passing through an
external tank, as shown in Figure 2. The photoreactor is exposed to the sunlight, facing the sun, while
the reservoir tank is in the dark. The flow consists of an aqueous suspension of photocatalyst powder
and the dissolved contaminant. The Evonik TiO2 P25 was selected as the model photocatalyst in
PHOTOREAC because it is considered the most promising alternative for commercial applications
due to its low cost, photochemical stability, and high oxidation power [3]. Therefore, it is widely
studied, and its physicochemical and optical properties are well known in the literature [11].
Water 2020, 12, 2196 4 of 17

Figure 2. Scheme of a solar pilot photoreactor set-up.

2.2. The Input Data for the Use of PHOTOREAC

The availability and reliability of the input data provided to PHOTOREAC are crucial for good
results. Table 1 shows a summary of the input information that is required to simulate the
photoreactors in PHOTOREAC. Additionally, it is indicated in which module is the information used.
At the same time, the experimental photodegradation data for kinetic analysis in PHOTOREAC
deserves special attention. The effects of the adsorption must be carefully considered in the solar
photocatalytic experimental test. The photodegradation data used to feed PHOTOREAC must be
reported at the zero-point of photodegradation, where adsorption has already been allowed to
homogenize, which is usually achieved by allowing the system to recirculate under darkness for 30
min to establish adsorption–desorption equilibrium conditions before being exposed to solar light.
Thus, although the kinetic models in PHOTOREAC do not contemplate the competitive effects of
molecular adsorption, the data used will already be corrected with that effect. Therefore, there is no
problem with the application of the models [10,12].
During the exposure time to sunlight, the data should be reported as the pollutant concentration
Ci against the accumulated ultraviolet (UV) energy ξAE. The experiments finish when the desired
accumulated UV total energy in J/m2 is reached. Additionally, it is required to record the
corresponding standard time for each sample.

Table 1. Summary of the input information for the PHOTOREAC modules.

Belonging to PHOTOREAC
Parameter Symbol Units
Module a
Photoreactor radius (CPCP and OMTP) R m PASM
Water film thickness (FFP) δ m PASM
Photoreactor length L m PASM
Solar incident radiation I0 W/m2 PASM
Reaction volume VR L PASM/KMM
Photocatalyst concentration Ccat g/L PASM/KMM
Total volume VT L KMM
Number of experimental
N Dimensionless KMM
photodegradation data
Concentration vs. accumulated energy
Ci vs. ξAE ppm vs. J/m2 KMM
data b
Concentration vs. standard time data b Ci vs. t ppm vs. min KMM
aPASM: photon absorption-scattering module; KMM: kinetic modeling module. b If it is a multicomponent
mixture, Ci is replaced by TOC.
Water 2020, 12, 2196 5 of 17

2.3. The PHOTOREAC Photon Absorption-Scattering Module

The PHOTOREAC photon absorption-scattering module performs the radiation field modeling
of the three available configurations of solar photoreactors: FPP, CPCP and OMTP. It provides the
LVRPA spatial distribution inside the photoreactor and the overall volumetric rate of photon
absorption (OVRPA), which corresponds to the LVRPA averaged over the entire volume of the
reactor. The latter is a critical magnitude for the kinetic assessment [12].
The PHOTOREAC modeling approach is focused on the six-flux absorption-scattering model
(SFM). SFM is an analytical equation in which the leading hypothesis is that scattering only occurs in
the six Cartesian directions [5]. Despite being a simplified model, it retains the key aspects of the
radiation field modeling in photoreactors and has been implemented successfully at the solar pilot
scale [13,14]. Other modeling approaches for solar photoreactors, such as the discrete ordinate
method (DOM) or the Monte Carlo simulation, offer a more accurate description of the radiation
transport phenomena. However, they are more time-consuming in the computations and their
mathematical formulation is of high complexity. The SFM short computation times are ideal for
exploring the impact of operational parameters, including the photocatalyst concentration,
photoreactor dimensions and incident radiation, in particular for users that are dabbling in
photoreactor engineering, to which PHOTOREAC is oriented. Independently of the photoreactor
configuration, the central equation of SFM is given by [14]:

 rp rp

I0
( ) ( )
−
λ λ
=LVRPA  ωcorr − 1 + 1 − ωcorr
2
e ωcorr + γ ωcorr − 1 − 1 − ωcorr
2
e ωcorr  (1)
λωcorr ωcorr (1 − γ )  
 
where I0 is the incident solar radiation in W/m2 and rp is a spatial coordinate in the reactor domain
whose definition depends on the reactor geometry. Finally, the corrected photon path length λωcorr in
m, the dimensionless corrected scattering albedo ωcorr and the dimensionless parameter γ are all
parameters derived from the SFM formulation. PHOTOREAC also includes a more recent variant of
the SFM , the Six Flux Model coupled to the Henyey-Greenstein scattering phase function (SFM-HG).
In it, the Henyey–Greenstein (HG) scattering phase function is used to describe the optical properties
of the TiO2 P25 photocatalyst. By contrast, the SFM describes TiO2 based on a diffuse reflectance
scattering phase function [15]. By incorporating both variants of SFM, the users will be able to observe
the role of the scattering phase function. The parameters and implementation of Equation (1) are
detailed in the literature, and the modeling details for the FFP are given in previous work [16].
On the other hand, for the CPCP and the OMTP, a ray-tracing technique together with Equation
(1) must be implemented, since, besides the incident radiation, the direction with which solar rays
impact the photoreactor is crucial. A complete description of the SFM implementation for CPCP and
OMTP is reported elsewhere [10,13,14].

2.4. The PHOTOREAC Kinetic Modeling Module

The PHOTOREAC kinetic modeling module estimates the kinetic parameters from the
photodegradation experimental data provided. Table 2 shows the photocatalytic kinetic models in
PHOTOREAC. These models explicitly consider the effect of the radiation absorption on the average
reaction rate in −ri VR
by including the Eg, and the overall rate of photon absorption (OVRPA) in
W/m3, which corresponds to the LVRPA averaged over the entire volume of the reactor. Additionally,
Ci is the concentration of the water contaminant in mol/m3, κP = 2/Sg Ccat is the particle constant in
m3/m2, Sg is the catalyst specific surface area m2/kg, CCat is the photocatalyst concentration kg/m3, CO2
is the oxygen concentration in mol/m3 and φgeff is the effective quantum yield in mol/(s watts).
Finally, kL-H, Kkin, 𝛼𝛼1 and 𝛼𝛼2 are the kinetic constants of the models, which are independent of the
irradiation conditions.
Water 2020, 12, 2196 6 of 17

Table 2. Photocatalytic kinetic models in PHOTOREAC.

Kinetic Model Mathematical Expression Fitting Parameters Refs.

L− H
K k C
− Kin L − H i ( Eg )
Langmuir– 0.5 kL-H (L/mol), Kkin
−ri = [13]
Hinshelwood VR
1 + k Ci (mol L−1 s−1 W−0.5)

φgeff Eg
−ri VR
=
− 0.5
φgeff (mol s−1
Zalazar et al. 1 1 φgeff Eg  watts−1), Kkin (mole s [17]
+  + K kin 2  kg2 m−9)
2  4 2Ccat Ci CO2 

α1  α 2 Eg  𝛼𝛼1 (cm s−1), 𝛼𝛼2 (mol

Ballari et al. −ri =−2  −1 + 1 + κ P  Ci [18]
VR
κp  Ci 
watts−1 cm−1)

𝛼𝛼1 (mol m−2 s−1),

α1  κ p eff  k Ci L− H
φgeff (mol s−1
Mueses et al. −ri =−2  −1 + 1 + φg Eg  [12]
VR
κ P  α1  1 + k Ci
L−H
watts−1), kL-H(m3
mol−1)

Each of these previous expressions has its features and limitations, from either a
phenomenological or a numerical point of view. For instance, the Langmuir–Hinshelwood
expression is a semi-empirical model. By contrast, the other models were deduced from a detailed
reaction mechanism. Zalazar et al. and Mueses et al.’s kinetic expressions consider the effect of the
effective quantum yield φgeff explicitly, a critical parameter to evaluate photocatalytic reactions.
However, the expression proposed by Mueses et al. is the only one with three fitting parameters,
unless the effective quantum yield of the system is previously known [12].
To determine the kinetics parameters, it is necessary to follow a rigorous approach to account
for the effects of the diffusion and convection in the material balance of the photoreactor. Although
the inclusion of these effects will provide more accurate results for the kinetic parameters (such
parameters will be independent of the diffusion and convection), it also implies the implementation
of more advanced numerical techniques, e.g., finite differences and orthogonal collocation [7,19].
PHOTOREAC considers the photoreactor-tank system as a batch mode reactor; therefore, the effects
of the diffusion and convection are lumped in the kinetic parameters, which simplifies the numerical
approach.
The following assumptions are established for the mass balance of the system (represented by
Figure 2): (i) the system is perfectly mixed; (ii) there are no mass transport limitations; (iii) the
conversion per pass in the reactor is differential; and (iv) parallel dark reactions can be neglected. The
mass balance in the reservoir tank can then be expressed as follows [7,18]:

dCi VR
= −ri (2)
dt VT VR

where Ci is the concentration of the water contaminant in mol/m3 at time t, t is time in s, −ri VR
is
the average reaction rate in (mol m3 s−1), and VR and VT are the volumes of the photoreactor and the
total reaction volume in m3, respectively. However, for solar photoreactors, the standard time may
not be the more appropriate magnitude for following the concentration of the water pollutant due to
the fluctuation of the incident solar irradiance because of the atmospheric phenomena and the time
of day. Therefore, a change of variable is proposed as follows [10]:

dCi  dCi   d ξ AE 
=   (3)
dt  d ξ AE   dt 
Water 2020, 12, 2196 7 of 17

dCi β
= −ri (4)
d ξ AE ξt VR

With the initial condition, Ci ( ξ AE = 0) = Ci,0, where Ci is the water contaminant concentration for
 dξ 
a given ξAE is the accumulated energy in J/m2, ξt =  AE  in J/m2s is the slope of the straight line
 dt 
resulting from the experimental data relationship of the accumulative incident solar radiation vs.
time for each experimental test, and the dimensionless factor β = VR/VT.
The search for the best values for the kinetic parameters of the model is carried out using a non-
linear regression procedure, as is shown in Figure 1. It starts with an initial guess and follows an
optimization criterion until the required convergence is reached. The error function is given by the
sum of the squared errors of the experimental water contaminant concentration Ci,exp and the value
determined from the numerical solution of Equation (4) Ci,calc:
N

∑ (C − Ci ,calc )
2
=Fobj i ,exp (5)
i =1

where N is the number of experimental data. The Matlab function fminsearch, which uses the Nelder–
Mead algorithm, is implemented as the optimization solver together with the Matlab function ode 45
for solving the ordinary differential equation (ODE) given by Equation (4).
For the photodegradation of multicomponent mixtures, the concentration Ci may be replaced by
a global concentration parameter such as total organic carbon (TOC) [12]. Therefore, Equation (4) is
written as:

dTOC β
= −rTOC (6)
d ξ AE ξt VR

with the initial condition TOC ( ξ AE = 0) = TOC0, where TOC is the total organic carbon of the mixture
mol/m3 for a given ξAE, ξAE is the accumulated energy in J/m2, TOC0 is TOC of the mixture measured
at the starting point of the experiment, and VR and VT are the volumes of the photoreactor and the
total reaction volume in m3, respectively. −rTOC VR
is the average reaction rate of the TOC of the

mixture in (mol m3 s−1). The mathematical expressions for −rTOC VR

are the same given in Table 2,

replacing −ri VR
by −rTOC VR
and Ci by TOC.

Similarly, Equation (5) is rewritten as:

N

∑ (TOC − TOCi ,calc )

2
=Fobj i ,exp (7)
i =1

Then, for multicomponent mixtures, the TOC of the mixture must be provided to PHOTOREAC
as a function of the accumulated energy instead of the concentration of a pure component water
contaminant. This approach is particularly useful in real environmental applications because in such
cases the most usual situation is that the content of the wastewater is unknown, and it would be
tough and resource-consuming to determine it. Therefore, it is easier to establish a global parameter
such as the TOC, which shows the mineralization of both intermediates and the precursor
compounds in the wastewater. By contrast, the monitoring of each initial pure component in the
mixture does not consider the formation of intermediates.

2.4.1. The Kinetic Modeling Module Database

In the kinetic modeling module, PHOTOREAC incorporates a database that consists of 26
datasets of the solar photocatalytic degradation of water contaminants using TiO2 P25 Evonik as a
Water 2020, 12, 2196 8 of 17

photocatalyst. The information was collected by the Modeling and Applications of Advanced
Oxidation Technologies Research Group at Cartagena University (Cartagena de Indias, Colombia)
and the Research Group on Advanced Processes for Biological and Chemical Treatments (GAOX) at
the Universidad del Valle (Cali, Colombia). Table 3 details the information available in the database:
two solar photoreactor configurations (CPCP and OMTP) and five model pollutants at different
initial concentrations and photocatalyst concentrations. By selecting the dataset to perform the kinetic
analysis, PHOTOREAC loads the information about the experimental test: the pollutant
concentration vs. accumulated energy data, the OVRPA and the β = VR/VT factor.

Table 3. PHOTOREAC database of the solar photodegradation of water contaminants.

Photoreactor Initial Concentration of the Photocatalyst

Water Contaminant
Configuration Contaminant, ppm Concentration, g/L
30 0.1, 0.5
CPCP 60 0.1, 0.35
Dichloroacetic acid
120 0.1, 0.35, 0.5
(DCA)
60 0.35
OMTP
120 0.35
60 0.1
CPCP
120 0.1
Phenol (PH)
60 0.1
OMTP
120 0.1
60 0.5
CPCP
4-chlorophenol (4- 120 0.5
CP) 60 0.5
OMTP
120 0.5
Methylene Blue CPCP 10 0.25
(MB) OMTP 10 0.2, 0.25, 0.3, 0.35
Amoxicillin (AMX) CPCP 20 0.3, 0.6, 0.9, 1.0

3. Implementation of PHOTOREAC in Solar Photoreactors

In this section, three example cases to demonstrate the use of the PHOTOREAC application are
presented. All of the cases are based on an experimental test already performed in the solar
photoreactor platforms of our research groups in Cartagena, Colombia (10°25′25″ N, 75°31′31″ W)
and Cali, Colombia (3°27′00″ N, 76°32′00″ W). Further information about the set-up and operation of
the experimental solar tests can be found in previous works [10,12].

3.1. Example Case I: Solar Photodegradation of Dichloroacetic Acid (DCA) in a CPCP

This example shows the implementation of PHOTOREAC for an analysis of the solar
photocatalytic degradation of DCA in a CPCP. The photoreactor consists of ten borosilicate tubes
with radius R = 0.016 m and length L = 1.2 m providing a reaction volume of VR = 9.7 L. The DCA
initial concentration was Ci = 30 ppm using a TiO2 P25 Evonik concentration of Ccat = 0.5 g/L. The main
objective of the example case was to determine the radiation-independent kinetic parameters of the
system from the experimental data provided to the application using the SFM as the radiative model.
First, the radiation field is determined by the photon absorption-scattering module. Figure 3
shows the main screen of the PHOTOREAC GUI: (1) the photoreactor panel, where the photoreactor
configuration was selected; (2) the system properties panel, where the input data were introduced
for the simulation; (3) the SFM model panel, where the SFM variant for the simulation is selected; (4)
the SFM scattering phase function probabilities are displayed according to the SFM variant that was
selected, in this case, the SFM; (5) the resulting LVRPA spatial distribution in the cross-section of the
CPCP tube is plotted; (6) the resulting OVRPA of the system is displayed; (7) the options menu.
Together with the main screen shown in Figure 3, PHOTOREAC generates a secondary screen with
the results of the ray-tracing simulation (Figure 4).
Water 2020, 12, 2196 9 of 17

From the results presented by the photon absorption-scattering module, the user will be able to
extract essential findings regarding the impact of variables on the photocatalyst concentration. For
instance, for this example case, in the LVRPA distribution plot shown in Figure 3, it is observed that
the highest values of the LVRPA are around y = −0.015 m and y = −0.005 m. This result is due to the
fact that at these coordinates there is a high concentration of rays that come from the CPCP reflectors,
as can be observed in Figure 4. Additionally, it is observed that the LVRPA is concentrated near to
the CPCP wall, and the center of the tube shows very low LVRPA values, as a result of the relatively
high photocatalyst concentration used in the simulation (Ccat = 0.5 g/L). This behavior is well-known
in the literature: at high concentrations of the photocatalyst, the photons cannot penetrate deeply into
the tube and the absorbed energy is concentrated around the boundary wall [14].

Figure 3. Radiation field simulation for a CPCP in the photon absorption-scattering module. (1)
photoreactor panel; (2) system properties panel; (3) the SFM panel; (4) display the corresponding SFM
scattering probabilities used in the simulation; (5) LVRPA spatial distribution plot; (6) OVRPA; (7)
options menu.

Figure 4. Ray-tracing simulation for the CPCP.

Water 2020, 12, 2196 10 of 17

Once the radiation field for the CPCP is determined, the application proceeds to the kinetic
modeling module. Figure 5 shows the input panel displayed by PHOTOREAC. The application loads
the system parameters determined previously, such as the TiO2 concentration and the OVRPA. The
remaining system parameters must be provided manually by the user. Similarly, the
photodegradation vs. accumulated energy data should be introduced in the experimental data panel.
Finally, the user may proceed to the kinetic modeling module’s main screen.

Figure 5. Input panel for the kinetic modeling module. (1) System parameters panel; (2) experimental
data panel.

Figure 6 shows the main screen of the PHOTOREAC GUI at the kinetic modeling module: (1)
kinetic models panel, where the user can choose the kinetic models to be fitted; (2) experimental data
and models simulations plot, where the experimental data and the fitting curves of the models that
were previously selected are displayed; (3) fitted kinetic parameters panel, where the values of the
fitting parameters of each model chosen are displayed; (4) the x-axis magnitude panel, where the user
can determine if the displayed data are presented in accumulated energy or standard time as the x-
axis magnitude; (5) correlation coefficient panel, which displays the higher R2 among the selected
kinetic models; (6) correlation coefficient panel, which shows the kinetic model with the highest R2
value among the chosen ones; (7) export data button, which exports the results of the fitting curve to
a Microsoft Excel file; (8) options menu panel.
From the PHOTOREAC kinetic modeling module screen in Figure 6, it is observed that the best
fitting is achieved for the Ballari et al. model with R2 = 0.97392. The other models reported R2 = 0.97365
for Mueses et al., R2 = 0.63843 for Langmuir–Hinshelwood and R2 = 0. 63585 for Zalasar et al. Due to
PHOTOREAC only displaying the model with the higher value for the correlation coefficient R2, it
selected the Ballari et al. model. However, Mueses et al.’s expression showed an almost identical R2,
and it should not be discarded without further analysis. From Table 2, it is observed that the
mathematical structure of the Ballari et al. and Mueses et al. expressions are very similar; indeed, the
Ballari et al. expression is considered a particular case of the Mueses et al. model for systems with
high molecular adsorption [12]. Therefore, it is expected that both models performed similarly, as is
the case for the DCA photodegradation. The Langmuir–Hinshelwood and Zalasar et al. expressions
may not lead to successful results due to the fact that they do not describe the effects of the absorbed
radiation (OVRPA) accurately. On the other hand, Ballari at al. and Mueses et al. may perform better
since they include an OVRPA squared root correction factor. the same can be said for Ballari et al.
and Mueses et al. regarding the OVRPA squared root correction factor.
Water 2020, 12, 2196 11 of 17

Figure 6. DCA fitting for the available kinetics models in the kinetics modeling module. (1) Kinetic
models panel; (2) experimental data and models simulations plot; (3) fitted kinetic parameters panel;
(4) x-axis magnitude panel; (5) correlation coefficient panel; (6) display of the kinetic model with the
highest R2 value among the ones selected; (7) export data button; (8) options menu panel.

3.2. Example Case II: Solar Photodegradation of Methylene Blue in an OMTP

In the previous example case, the user must provide all the required information to perform the
computations. In this example, the use of the database incorporated in the PHOTOREAC kinetic
modeling module is shown. Figure 7 shows the PHOTOREAC screen of the kinetic modeling module:
(1) the photoreactor configuration panel, for selecting the photoreactor to be studied; (2) the model
pollutant panel, for choosing the water contaminants from the five available options in the database;
(3) the photocatalyst-pollutant panel, for choosing the photocatalyst concentration-initial pollutant
concentration combination from the available options in the database; (4) the experimental data
panel, for loading the pollutant concentration vs. accumulated energy (or standard time); (5) the
system parameters panel, which displays the OVRPA and the β = VR/VT factor charged.

Figure 7. Database in the kinetic modeling module. (1) photoreactor configuration panel; (2) model
pollutants panel; (3) photocatalyst-pollutant panel; (4) experimental data panel; (5) system parameters
panel.

In this case, an OMTP with methylene blue (MB) was selected as a model pollutant with an initial
concentration of Ci = 10 ppm and a photocatalyst concentration of Ccat = 0.2 g/L. Figure 8 shows the
Water 2020, 12, 2196 12 of 17

results obtained by PHOTOREAC. It is observed that the best fitting is achieved for the Mueses et al.
and Ballari et al. models with R2 = 0.99737 for both. The other models reported R2 = 0.001. As the
Ballari et al. model is a particular case of the Mueses et al. model, the first is considered the more
appropriate option since it is more specific for this case. These results agree with the discussion
presented in the previous section.

Figure 8. Methylene blue solar photodegradation fitting in an offset multi-tubular photoreactor

(OMTP) for the four available kinetics models in the kinetic modeling module.

3.3. Example Case III: Radiation Field Modeling in a Flat Plate Photoreactor (FPP)
In this case, the objective was to compare the radiation field simulation for an FPP using SFM
and SFM-HG. The photoreactor consists of a titled squared flat plate of length L = 1 m, which is placed
facing the sun and uniformly irradiated. A water film of 1 cm thickness flows over its surface,
providing a reaction volume of VR = 10 L. The TiO2 P25 Evonik concentration is Ccat = 0.2 g/L. Figures
9 and S1 show the LVRPA profile in the FPP calculated with the SFM-HG and the SFM, respectively.
In both cases, the highest LVRPA values are found near to the surface of the water film (thickness =
0–0.2 cm) because this is the boundary that the solar light irradiates. After 0.2 cm, exponential decay
in the LVRPA occurs as a result of the absorption and scattering of photons by the suspended
photocatalyst. Due to the photoreactor being considered as uniformly irradiated, the changes in the
LVRPA profile are only significant along with the water film thickness.
In Figure S1, which uses the SFM, a shaper exponential LVRPA profile is observed, with higher
values near the irradiated boundary (at thickness = 0–0.2 cm) when comparing to values in Figure 9,
which uses the SFM-HG. These results are due to the difference in the scattering phase function; the
SFM-HG uses a predominantly forward scattering phase function, which causes photons to penetrate
deeper into the water film. By contrast, the SFM uses a predominantly backward phase function,
which causes that photons to be redirected toward the irradiated boundary and be mostly absorbed
in the beginning of the film or escape from the system [15].
Water 2020, 12, 2196 13 of 17

Figure 9. Radiation field simulation of a flat plate photoreactor (FPP) with SFM-HG.

4. PHOTOREAC Implementation in Research Projects in Heterogeneous Photocatalysis and

Photoreactor Engineering by Chemical Engineering Undergraduates
Since the year 2015, different versions of PHOTOREAC have supported the final degree projects
of chemical engineering students belonging to the Modeling and Applications of Advanced
Oxidation Technologies Research Group at Cartagena University. The students developed research
on heterogeneous photocatalysis and photoreactor engineering. A survey was done amongst them to
determine the perceived impact of PHOTOREAC on their final degree projects. Table 4 shows the
results of the survey. Between 2015–2018, ten final degree projects were developed in the research
group, with an average impact of 37.5% perceived by the students. The use of PHOTOREAC can be
summarized as follows: in four of the degree projects, both modules of PHOTOREAC were
implemented since they performed the radiation field simulation and kinetic modeling of model
pollutants; in two other projects, the photon-scattering module was used to determine the radiation
field in photoreactors; finally, in four projects, the application was used in the learning process for
modeling solar photoreactors. As a relevant outcome, two of the degree projects supported
publications in high-impact journals. In all of the projects, the authors highlighted the use of
PHOTOREAC as a user-friendly tool that allows them to reach the main objective of the projects or
to achieve a fast advance in the learning curve, therefore allowing them to focus on more complex
research.
Water 2020, 12, 2196 14 of 17

Table 4. PHOTOREAC impact on final degree projects in chemical engineering.

PHOTOREAC
PHOTOREAC
Title of the Final Impact on the
Year Related Publication/Ref. Implementation in
Degree Project Project Perceived
the Project
by the Students
A Novel Prototype Offset
Modeling the
Design and evaluation Multi Tubular Photoreactor
radiation field and
of a modified (OMTP) for solar
2015 30% kinetics of methylene
compound parabolic photocatalytic degradation
blue for both the
collector solar reactor of water contaminants/ref.
CPCP and OMTP
[10]
Effect of oxygen
Modeling the
transfer from the air on
radiation field and
the photocatalytic
2015 -- 50% kinetics of
degradation of
dichloroacetic acid in
dichloroacetic acid
an FFP
using a flat plate reactor
Radiant field modeling Coupling the Six Flux
in heterogeneous Absorption-Scattering Model
photoreactors to the Henyey– Greenstein
Modeling the
implementing Monte scattering phase function:
2016 60% radiation field for the
Carlo simulation: Evaluation and optimization
FFP and a CPCP
Modification of the Six of radiation absorption in
Flux Model to new solar heterogeneous
phase functions photoreactors/ref. [15]
Modeling and experimental
Evaluation of the
evaluation of a non-
temperature effect on
isothermal photocatalytic The learning process
2016 the heterogeneous 20%
solar reactor: temperature for modeling CPCP
photocatalytic
effect on the reaction rate
degradation kinetics
kinetics/ref. [20]
Solar heterogeneous A Novel Prototype Offset
Modeling the
photocatalytic Multi Tubular Photoreactor
radiation field and
degradation of organic (OMTP) for solar
2016 50% kinetics of DCA, PH
pollutants in a pilot- photocatalytic degradation
and 4-CP for both
scale modified tubular of water contaminants/ref.
the CPCP and OMTP
collector [10]
Simulation of in series
and in parallel
The learning process
2016 arrangements of solar -- 30%
for modeling CPCP
reactors (CPCP) for
wastewater treatment
Experimental
evaluation and
mathematical modeling
of the performance of
The learning process
2016 TiO2-P25 reuse in -- 30%
for modeling CPCP
heterogeneous solar
photocatalytic
degradation of
acetaminophen
Solar photocatalytic
ozonation applied to
The learning process
2017 amoxicillin degradation -- 30%
for modeling CPCP
in wastewater at pilot-
plant scale
Water 2020, 12, 2196 15 of 17

Mathematical modeling
and simulation of Radiation field
2018 -- 35%
photocatalytic modeling of an FFP
hydrogen production
Experimental
evaluation and
Modeling the
mathematical modeling
radiation field and
of the regeneration of
2018 -- 40% the kinetics
commercial TiO2 by the
glyphosate in a
photocatalytic
CPCP
degradation of
glyphosate

5. Analysis of the Overall Performance of PHOTOREAC

PHOTOREAC was shown to be a useful tool for modeling and simulation of solar photoreactors,
and in particular for a non-expert public. Its user-friendly interface developed in the graphical user
interface of Matlab proved to be intuitive enough to be used successfully by chemical engineering
undergraduates, which develop research in heterogeneous photocatalysis.
In Section 3, the application was evaluated for disparate operational conditions, showing that it
can fit and simulate the photodegradation experimental data provided for the two cases evaluated:
CPCP-DCA (example case I) and OMTP-MB (example case II). These example cases were very
different from each other, mainly because of the different photoreactor geometries: CPCP can capture
more solar radiation per length than the OMTP as a result of being equipped with reflectors.
However, OMTP has more volume than the CPCP [10]. Additionally, the employed model pollutant,
its initial concentration, and the photocatalyst concentration were different. In both examples,
PHOTOREAC performed successfully, allowing the user to evaluate different kinetic expressions and
extract relevant findings from it. Finally, example case III focused on the photon absorption-scattering
module, in which the impact of the radiation model was evaluated and discussed for an FFP. In this
case, PHOTOREAC shows its versatility for researchers with an interest in studying the energy
absorption behaviors of photoreactors.
The dedicated interface of PHOTOREAC for photoreaction engineering, together with its
numerical algorithm, allowed the evaluation of the performance of large scale solar photoreactors
without time-consuming computations and a complex mathematical formulation. The time invested
in preparing and launching a simulation in PHOTOREAC is between 5–10 min, and the calculation
time does not exceed 45 s. In contrast to commercial CFD simulators in which preparing and starting
a first-time simulation may take a couple of hours needed for generating the photoreactor geometry
in the system (or it importing it from CAD software), preparing the simulation modules and their
models and selecting the proper meshing and numerical algorithms; besides, the computational time
for each simulation is, generally, measured in hours [21–23]. Nevertheless, the results obtained by
CFD simulators are much more complete and accurate than the results that PHOTOREAC may offer;
for instance, CFD simulators provide detailed flow patterns for studying the hydrodynamics in the
photoreactor. However, its high computational time may result in a barrier when exploring the
impact of numerous parameters on a wide range of values.
Moreover, the most common CFD commercial simulators used in modeling photoreactors are
very expensive licensed software. At the same time, PHOTOREAC is an open-access application that
is available on-demand, by email to one of the authors of the paper, professor Miguel A. Mueses
([email protected]).
In conclusion, PHOTOREAC is recommended for the following cases: (i) for an introduction to
photoreactor engineering; (ii) when a quantitative margin of error is still acceptable in the
calculations; (iii) when qualitative results are the main objective of the work; and (iv) when the
parametric space in the study is extensive, i.e., it is required to study the impact of numerous variables
in broad ranges. In this case, PHOTOREAC may be employed to reduce the parametric space and
then to implement a CFD simulator.
Water 2020, 12, 2196 16 of 17

6. Limitations and Future Work

As with every modeling software, PHOTOREAC is limited by the availability and reliability of
the input data provided by the users. Additionally, the computational application is limited to
Titanium Dioxide P25 Evonik as photocatalyst. Although TiO2 P25 is the most common photocatalyst,
the capability of performing simulations for any photocatalyst will be crucial for the software, since
an area of intensive research in heterogeneous photocatalysis is the development and testing of new
photoactive materials. On the other hand, expanding the available kinetic models would also be a
considerable improvement, because it will allow users to make a more comprehensive analysis by
comparing the results of the kinetic models’ fitting. Moreover, it is necessary to implement the option
that users introduces their own kinetic expression, since some pollutants will require concrete
mathematical expression because their kinetic mechanism may not follow the most common
postulates. These drawbacks are expected to be overcome in the upcoming version of PHOTOREAC.
In the authors’ opinion, some important challenges for PHOTOREAC and, in general, for
photoreaction engineering at the pilot-solar scale are that the models account for the variability of the
incident radiation on the solar photoreactor caused by fluctuations in atmospheric conditions. This
improvement will allow more accurate quantification of the energy absorbed by the suspended
photocatalyst, and therefore better quantification of the chemical species produced by the
photoactivation of the photocatalyst.

Supplementary Materials: The following are available online at www.mdpi.com/2073-4441/12/8/2196/s1, Figure

S1: Radiation field simulation of a flat plate photoreactor (FPP) with SFM.

Author Contributions: Conceptualization, B.C.-V., K.P.-G. and M.A.M.; data curation, B.C.-V., and K.P.-G.;
formal analysis, R.A.-H.; funding acquisition, M.H.P.-C. and F.M.-M.; investigation, B.C.-V. and K.P.-G.;
methodology, B.C.-V. and K.P.-G.; project administration, M.H.P.-C. and F.M.-M.; supervision, R.A.-H. and
M.A.M.; validation, B.C.-V. and K.P.-G.; writing—original draft, R.A.-H.; writing—review and editing, R.A.-H.,
M.H.P.-C., M.A.M. and F.M.-M. All authors have read and agreed to the published version of the manuscript.

Funding: This research was funded by Universidad del Valle, grant number C.I. 21022.

Acknowledgments: The authors gratefully thank Universidad de Cartagena (Cartagena, Colombia) with the
project 017-2018: “Plan de Fortalecimiento del Grupo de Investigación Modelado y Aplicación de Procesos
Avanzados de Oxidación” and Universidad del Valle (Cali, Colombia) with the Project CI. 21022 “Estudio del
efecto hidrodinámico y de transporte de energía radiante en el diseño y optimización de reactores fotocatalíticos
heterogéneos solares. CI 21022.” for financial support. Acosta-Herazo thanks the CEIBA foundation with the
program “Bolivar Gana con Ciencia” for financing his doctoral studies.

Conflicts of Interest: The authors declare no conflict of interest.

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