HETEROGENEOUS PHOTOCATALYSIS

Heterogeneous photocatalysis is a process that is based on the direct or indirect absorption

of radiant energy (visible or UV) by a solid (the heterogeneous photocatalyst) [1]. Irradiation
of the catalyst with radiation of energy greater than its activation energy, allows the transfer
of an electronic from the valence band of the catalyst to the conduction band, forming an
electronic-hollow pair, whose half-life is in the range of the 30 nanoseconds, on the surface
of the semiconductor, in which they are carried out at the end of the reduction and oxidation
reactions [1], [2].

Ilustración 1. Representation of the photocatalysis process using TiO2 as a photocatalyst. [3]

𝑆𝑒𝑚𝑖𝑐𝑜𝑛𝑑𝑢𝑐𝑡𝑜𝑟 ℎ𝑣 → 𝑒 − + ℎ+ (1)
They are captured by adsorbed receptor agents such as oxygen or dissociated water, and
highly oxidizing species such as hydroxyl or superoxide radicals capable of mineralizing
organic compounds are obtained.[4]
𝑂2 + 𝑒 − → 𝑂2− (2)
𝐻2 𝑂 + ℎ+ → 𝐻2+ (3)
The two compounds are highly oxidizing and attack emerging pollutants forming carbon
dioxide and water.
𝑂𝐻 + 𝑅 → 𝑠𝑢𝑏𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑜𝑠 → 𝐶𝑂2 + 𝐻2 𝑂 (4)

MAIN COMPONENTS OF PHOTOCATALYSIS

 Radiation source: it can be visible and / or natural such as sunlight, and UV lamps.
The solar radiation that descends to the reactor can be direct, which corresponds to
the solid angle limited by the solar disk without taking into account atmospheric
scattering, or diffuse when the solar radiation that reaches the surface of the Earth's
atmosphere is scattered from its original direction due to molecules in the atmosphere,
depending on whether the day is clear or cloudy [1], [5].
 Photocatalyst: it is the basis of the process, since the reactions necessary for the
degradation of pollutants will be carried out on its surface. The semiconductor must
fulfill requirements such as being capable of absorbing UV rays, harmless,
photostable and must have a wide gap band so that its conductivity increases with
temperature. When used as a catalyst, it must comply with a high surface area,
maintaining its uniform particle size and without internal porosity. [1].
- Titanium dioxide (TiO2): the most widely used photocatalyst is TiO2
produced by Evonik under the trade name of P-25, since until now it has
shown greater effectiveness [6]. It has a high chemical stability which allows
its correct operation in a wide pH range, and at the same time it is capable of
producing electronic transitions by absorption of light in the near ultraviolet
(UV-A) [1]. Other options with other optical properties are also handled, such
as Aldrich TiO2 and Hombitak TiO2, which are included in the Photoreact
2.0 database.
 Solar reactors: the degradation capacity of a pollutant depends a lot on the selected
reactor, since not all of them capture the radiation from the radiant source in the same
way or in the same quantities.
- Compound Parabolic Cylinder Reactor (CPC): CPC reactors are the most
widely used, and it has turned out to be one of the best technological options for
photocatalysis solar applications. They have proven to have a very efficient
configuration, since they are formed by a surface with an enveloping shape around
a cylindrical reactor, which translates into one of the best optics for low
concentration systems. Compound Parabolic-Cylinder reactors are generally
made of polished aluminum and the structure can be a simple photoreactor
support frame with connected tubes [6].

Ilustración 2. CPC reactor illustration.

- Offset Multi Tubular Photoreactor (OMTP): It is a modification of the CPC

reactor, it arises due to the needs of a process when it is desired to treat larger
volumes and with greater efficiency, since a CPC covers more physical space.
OMTP volume is up to 80% higher compared to CPC for the same footprint and
increases residence time by up to 1.8 times. The OMTP has two rows of tubes,
thus obtaining more flow capacity and equal or greater efficiency than a tubular
reactor, since it takes advantage of solar radiation in the same way [7].
 Ilustración 3. OMTP reactor structure. [7]

- Flat Plate: formed by a plate inclined towards the sun, the effluent to be treated
circulates over it. This type of reactor receives radiation directly since it is
exposed to the atmosphere, the catalyst is located on the surface of the plate[8].

Ilustración 4. Estructura del reactor placa plana. [8]

MODELING THE RADIATION ABSORPTION OF SOLAR PHOTOREACTORS

 Ray-Tracing technique: It is a model of solar radiation emission used to calculate the

coordinates and direction of the photon flux, both of direct and diffuse radiation that reaches
the surface of the reactor [9].

𝑥𝐶𝑃𝐶 = ±𝑅𝑅 (sin 𝑡 − 𝑡 cos 𝑡) 𝑦𝐶𝑃𝐶 = −𝑅𝑅 (cos 𝑡 + 𝑡 sin 𝑡)

𝑁𝑦 𝜋 𝜋
𝛽 = arcsin ( ) 𝛼𝑖 = 2𝛽𝑖 + 𝜃1 − 𝑚𝑖 = tan 𝛼𝑖 𝜃1 = − 𝛼𝑖
‖𝑁‖ 2 2
𝑦𝐶𝑃𝐶,𝑒𝑠𝑡𝑖𝑚𝑎𝑑𝑎 = 𝑦𝑖−1 + 𝑚1 (𝑥𝐶𝑃𝐶 − 𝑥𝑖−1 )

(5) 𝛿 = √(𝑥𝑖+1 − 𝑥𝑖 )2 + (𝑦𝑖+1 − 𝑦𝑖 )2 𝑟𝑝 = √(𝑥 − 𝑥𝑖 ) + (𝑦 − 𝑦𝑖 ) (6)

𝑊
𝐼0,𝑟𝑒𝑓𝑙𝑒𝑗𝑎𝑑𝑜 = 𝐼0 𝛹 𝑛 𝐼0,𝑟𝑒𝑓𝑙𝑒𝑗𝑎𝑑𝑜 =
𝑚2
Where the subscript i corresponds to the number of direction changes that a photon
undergoes before reaching the reactor wall.
 Ilustración 5. Ray Tracing. [9]

 Local Volumetric Rate of Photon Absortion (LVRPA): Photocatalytic reactions

start when the catalyst particle absorbs a photon capable of generating charge carriers
within it. For this reason, it is essential to quantify the local volumetric rate of photon
absorption (LVRPA), which necessarily participates in the expression of the reaction
rate through the activation step [10]. The LVRPA calculation represents one of the
most complex tasks in the modeling of photocatalytic reactors, which depends on the
spatial distribution of the radiant field in the photoreactor, the radiant source and the
optical properties of the system [2].

One of the options for calculating the LVRPA is the solution of the Radiative Transfer
Equation. RTE is an integral differential equation and requires appropriate and well-
defined limits and optical properties of the medium. This equation is the result of a
radiation balance through an immobilized material or one dispersed in a fluid, taking
into account Out-scattering and absorption, in the same way that it can win if In-
scattering occurs, creating a delta. radiant energy, considered in a steady state [11].
𝑑𝐼𝜆 (𝑠, 𝛺) 𝜎𝜆
= −𝑘𝜆 𝐼𝜆 (𝑠, 𝛺) − 𝜎𝜆 𝐼𝜆 (𝑠, 𝛺) + ∫ 𝑝 (𝛺 ′ → 𝛺)𝐼𝜆 (𝑠, 𝛺 ′ )𝑑𝛺 ′ (7)
𝑑𝑠 4𝜋 𝛺→4𝜋

To solve this equation there are several options: (i) applying numerical solutions
mainly based on the method of the discrete ordinate, however, its integro-
differential nature makes it very complex. (ii) Using Monte Carlo techniques, which
implements a simpler model but often results in a very large computational effort.
(iii) The simplest way to calculate LVRPA is to develop simplified radiation field
models, which provide a physical understanding of the role that key parameters play
throughout the process, which is often what is actually needed to the design and
 development of industrial equipment [12]. The following models are included in
Photoreact 2.0:
Model Equation Observation
𝐺0 (1)
Six Flux 𝐿𝑉𝑅𝑃𝐴 = The six-flow absorption model
𝜆𝑅𝑐𝑜𝑟𝑟 𝑅(1 − 𝛾)
Model ∗ [(𝑅𝑐𝑜𝑟𝑟 − 1 (SFM) has been presented for the
2
+ √1 − 𝑅𝑐𝑜𝑟𝑟 )𝑒
−
𝑥
𝜆𝑅𝑐𝑜𝑟𝑟
calculation of the LVRPA,
+ 𝛾 (𝑅𝑐𝑜𝑟𝑟 − 1
offering efficiency and
2
𝑥 subtracting complexity. This
− √1 − 𝑅𝑐𝑜𝑟𝑟 ) 𝑒 𝜆𝑅𝑐𝑜𝑟𝑟
model is based on establishing
𝑎 probabilities for 6 different
𝜔𝑐𝑜𝑟𝑟 =
𝑏 directions in the Cartesian plane.
4𝜔 2𝑝𝑠2 [2]
𝑎 = 1 − 𝜔𝑝𝑓 −
1 − 𝜔𝑝𝑓 − 𝜔𝑝𝑏 − 2𝜔𝑝𝑠
4𝜔 2 𝑝𝑠2
𝑏 = 𝜔𝑝𝑏 +
1 − 𝜔𝑝𝑓 − 𝜔𝑝𝑏 − 2𝜔𝑝𝑠
2
1 − √1 − 𝜔𝑐𝑜𝑟𝑟
𝛾= 𝑒 −2𝜏𝑎𝑝𝑝
2
1 + √1 − 𝜔𝑐𝑜𝑟𝑟
1
𝜆𝜔𝑐𝑜𝑟𝑟 =
2
𝑎𝛽√1 − 𝜔𝑐𝑜𝑟𝑟
𝑝𝑓 + 𝑝𝑏 + 4𝑝𝑠 = 1

Six Flux 1 1 − 𝑔2 (2) The main contribution of the HG

𝑝(𝜑) =
Model – 2 (1 + 𝑔 − 2𝑔𝑐𝑜𝑠𝜑)3/2
2
function is that it eliminates the
Henyey 𝐿𝑉𝑅𝑃𝐴 assumption about the dispersion
= 𝑓𝑆𝐹𝑀−𝐻𝐺 (𝑝𝑓 , 𝑝𝑏 , 𝑝𝑠 )
Greenstein 𝐼𝑜 behavior of implicitly made
particles when implementing a
𝑝𝑓 = 𝑓1 (𝑔) theoretical phase function, since
𝑝𝑏 = 𝑓2 (𝑔)
it allows a previous experimental
characterization of the dispersion
thanks to its adjustable
dispersion parameter. [13]

KINETIC EQUATIONS OF REACTION RATE

The development of kinetic models is essential when sizing and expanding the scale of
photocatalytic reactors, it helps to optimize operating conditions for greater photodegradation
[14].
This software uses the following generalized models for the quantification of reaction
kinetics for heterogeneous photocatalytic systems:
Model Equation Observation
Pseudo Order 𝑟𝑖 = −𝑘𝑐𝑖𝑚 (1) The kinetic constant depends on the
m luminous flux.
The model is independent on
photocatalytic mechanism but does not
 consider the phenomenological
performance [15]-[18].
Langmuir- 𝑘2 𝑐𝑖 (2) The model is not consistent with the
Hinshelwood, −𝑟𝑖 = 𝑘1 photocatalytic mechanism. There are not
1 + 𝑘2 𝑐𝑖
L-H intrinsic kinetic constants and it do not
include the absorption energy effect flux
[19] [20][21].
Modified L-H 𝑘2 𝑐𝑖 (3) It fits well with lowest reaction rates
−𝑟𝑖 = 𝑘1 (𝐿𝑉𝑅𝑃𝐴)𝑚 (first order) and shows high dependency
1 + 𝑘2 𝑐𝑖
on the luminous flux. The overall
reaction rate controls the process.
Kinetic constants are independent on
energy absorption. The m parameter is
between 0.5 and 1.0 [19] [20][21].
Modified ̂𝑔 𝑎 (4) M. Ballari et al. Propose a new kinetic
𝛼1 𝑘𝑝 ∗ 𝛼2 ∗ 𝐸
pseudo first (𝜆→𝜆′ ) model independent of the photon
𝑟𝑖 = −2 [1 − √1 + ] 𝐶𝑖
order 𝑘𝑝 𝐶𝑖 absorption variables, thus neglecting the
Langmuir-Hinshelwood constants and
based on their net study of the kinetics
dependent on the concentration of
catalyst and its surface area. specifies
(typical value: 50m2g-1), also
intrinsically to LVRPA [22]
Generalized (5) The kinetic constants are independent on
𝛼1 𝜅𝑃 𝑘2 𝑐𝑖
model −𝑟𝑖 = 2 [−1 + √1 + Φ𝑔 𝑉𝑅𝑃𝐴] the luminous flux. The model can be
𝜅𝑃 𝛼1 1 + 𝑘2 𝑐𝑖 adapted to the models (1) to (4)
depending of the consideration. The
quantum yield is independent of the
model [23], [24][25][26].

Mass Balance

Since it is considered a Batch reactor, the fluid dynamics is not taken into account, therefore, the
mass balance is expressed as [27]:
𝜕 𝜐𝑅
𝐶 (𝑡) = ( ) 〈𝑅𝑖 〉(𝑡)
𝜕𝑡 𝑖 𝜐𝑇

𝜕 𝜐𝑅
𝐶𝑖 (𝑡) = 𝑄∗ (𝑡) ( ) 〈𝑅𝑖 〉(𝑡)
𝜕𝑄𝑎𝑐𝑢𝑚 𝜐𝑇

𝜕𝑄𝑎𝑐𝑢𝑚 −1
𝑄 ∗ (𝑡) = [ ]
𝜕𝑡

𝐽
𝑄𝑎𝑐𝑢𝑚 = 𝐶𝑖 = 𝑝𝑝𝑚 𝑡 = 𝑠𝑒𝑔
𝑚2
MATHEMATICAL MODELING OF THE PROCESS

Ilustración 6. Methodological structure of mathematical modeling of the process.[28]

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