DOI: 10.

53660/CONJ-1071-Q11

Photocatalytic reactors and their scale up: literature review

Reatores fotocatalíticos e sua ampliação de escala: revisão bibliográfica

Amanda Eduarda de Oliveira¹, Luiz Jardel Visioli¹ e Heveline Enzweiler¹*

RESUMO

As reações de fotocatálise tem sido muito estudadas para a degradação de substâncias recalcitrantes. Sabe-
se que a ativação do fotocatalisador ocorre com a absorção de fótons de energia maior ou igual ao band
gap, fazendo com que elétrons da banda de valência sejam transferidos para a banda de condução, surgindo
então uma lacuna na banda de valência. Em escala laboratorial muitos trabalhos já foram desenvolvidos. A
configuração mais utilizada é o reator cilíndrico, onde a fonte de iluminação é colocada ao centro,
mergulhado no meio reacional, protegida por uma célula de quartzo. As lâmpadas de Xenônio, LED e
mercúrio são as mais utilizadas devido ao comprimento de onda no qual emitem radiação eletromagnética.
Também são utilizados catalisadores heterogêneos para melhorar a eficiência do processo, porém quando
utilizados dispersos no meio, há uma dificuldade em separá-los após a operação, e quando utilizados
imobilizados, existem barreiras relacionadas à sua fixação no sistema. Para o aumento de escala, observou-
se alteração na fonte de iluminação para a luz solar, substituição do quartzo pelo vidro, e diferentes formas
de reutilizar os catalisadores para uma maior economia.

Palavras-chave: Fotocatálise heterogênea; Reator fotocatalítico; Aumento de escala.

ABSTRACT

Photocatalysis reactions have been extensively studied for the degradation of recalcitrant substances. It is
known that the activation of the photocatalyst occurs with the absorption of photons of energy greater than
or equal to the band gap, causing electrons from the valence band to be transferred to the conduction band,
resulting in a gap in the valence band. On a laboratory scale, many works have already been developed.
The most used configuration is the cylindrical reactor, where the light source is placed in the center,
immersed in the reaction medium, protected by a quartz cell. Xenon, LED and mercury lamps are the most
used due to the wavelength at which they emit electromagnetic radiation. Heterogeneous catalysts are also
used to improve the efficiency of the process, but when used dispersed in the medium, there is a difficulty
in separating them after the operation, and when used immobilized, there are barriers related to their fixation
in the system. For the scale up, a change in the lighting source to sunlight, replacement of quartz by glass,
and different ways of reusing the catalysts for greater economy were observed.

Keywords: Heterogeneous photocatalysis; Photocatalytic reactor; Scale up.

1
Universidade do Estado de Santa Catarina.
*E-mail: [email protected]

Conjecturas, ISSN: 1657-5830, Vol. 22, Nº 6

INTRODUCTION
It is known that water is an abundant natural resource on planet Earth, however
only a limited amount is viable for use, since much of it is salt water. A major concern
that has been discussed is the progressive decrease of this resource, since urbanization,
industrialization, agriculture, inadequate pollutant disposal techniques and changes in
climatic conditions have drastically affected the physical-chemical and microbiological
conditions of the water (Kaur, Umar e Kansal 2016; Hoang, et al., 2021). Therefore, the
conscious use of this resource, as well as the appropriate application of treatments are
essential for its good quality and removal of organic, inorganic and mineral substances in
water courses.
The term “emerging contaminants” refers to products with toxic potential that are
not removed or eliminated by traditional processes for treating water for human
consumption, and the effects of these substances are still poorly understood in the long
term. Among them, endogenous hormones, synthetic hormones, contraceptives, drugs of
various compositions, caffeine, sucralose, nanomaterials, bactericides, insecticides,
algaecides, herbicides, cleaning and personal hygiene products, sunscreens, chlorination
and water ozonation products stand out, among others.
With the rapid pace of industrial and urban growth, the number of contaminants
has increased significantly, and it demands for new treatment methods. With the aim of
eliminating these pollutants from water, techniques such as advanced oxidation processes
(AOP) have been developed, which include photocatalysis (Kaur, Umar and Kansal,
2016). Photocatalysis, in turn, is based on the process of generating reactive oxygen
species that are not selective and have the ability to oxidize recalcitrant compounds by
dehydrogenation or hydroxylation, and which are finally mineralized into final products
(Ahmad et al. 2016).
Due to its efficiency and great potential for removing contaminants, this technique
has attracted a lot of interest from researchers, with a focus on overcoming challenges
such as light intensity distribution, catalyst doping to increase the reach of the process to
visible light and recovery of catalysts for large-scale photocatalysis systems. Other
alternatives related to the materials used, the lighting source and reactor design have also
been evaluated.
Photocatalytic reactors can be separated into two classifications, for production
and for degradation. The first ones have been applied mainly for the generation of H2 for

510
energy production. Degradation reactors aim to degrade recalcitrant substances, which
often do not receive adequate treatment.
Different reactor geometries have been studied, both in the case of production and
degradation. However, these studies are advanced on a laboratory scale. Many variables
that change the results have been used, such as the reactor material, the lighting source,
the hetogeneous catalyst and the way it will be used, directly affect the efficiency of the
process.
The expansion of scale must receive great attention since for its applicability it is
necessary that all obstacles are corrected for a good functioning, so that companies and
the population in general can enjoy this technology. Technical feasibility and economic
feasibility are the two main factors that must be considered when talking about scaling
up (Piriyah and Knmani, 2020). As well as on a laboratory scale, all operational variables
must be considered and adapted so that there is feasibility in the application of the project.
This work aims to present a review of the literature on used photocatalytic
reactors. It is also proposed to review approaches to scale up the laboratory scale to a pilot
scale of photocatalytic reactors for the degradation of emerging pollutants.

METHODOLOGY
This study is theoretical and based on a bibliographic review about the
photocatalysis process, laboratory projects of photocatalytic reactors and projects to scale
up these reactors. The presentation of photocatalytic reactors was divided into laboratory
scale and pilot scale, highlighting the most frequently used projects.
The data collection consists of a range of approximately 50 articles covering the
mentioned subjects. The articles were selected prioritizing the most recent (years 2020,
2021 and 2022), but there are also some older works due to their relevance. The keywords
used were photocatalysis, photodegradation, photoreactor and photocatalytic reactor. The
work has several images adapted from the reviewed articles and the Canva website was
used as a tool to create these illustrations.
.
RESULTS AND DISCUSSION
Photocatalytic Reactors
Photocatalysis

511
 According to Bora and Mewada (2017), the basic mechanism of heterogeneous
catalyst activation begins with the absorption of photons of energy greater than or equal
to the band gap of a photocatalyst, causing electrons (e-) in its valence band (VB) to be
transferred to the conduction band (CB), then a gap (h+) appears in the VC, as illustrated
in Figure 1. One of the accepted mechanisms suggests that the photogenerated electrons
and holes react with the available oxidants and reductants, forming radicals that later react
with the pollutant, forming a series of intermediate species and resulting in the complete
mineralization of the pollutants.
Figure 1 - Mechanism of action of photocatalysts

Source: Adapted from Bora and Mewada (2017).

Ahmad et al. (2016) state that a wide variety of materials have been identified as
photocatalysts, each of which has a different band gap energy. The author also cites
another accepted mechanism for the process, in which the charged components (e-)
formed by the absorption of light photons can migrate to the surface of the catalyst and
initiate redox reactions with the adsorbed pollutants or can recombine dissipating energy.
The process still has some problems to be solved, such as the more efficient use
of visible light, the rapid recombination of the charged species and the separation of the
catalyst from the aqueous medium after the process. When talking about recombination,
Bora and Mewada (2017) explain that after the electron migrates to the conduction band
and leaves the hole in the valence band, if this is not eliminated quickly, it will result in
reduced efficiency. This recombination can be avoided through techniques applied to
catalyst synthesis, such as the addition of dopants, co-catalysts or by heterogeneous
coupling. In some cases, the use of sacrificial reagents in the reaction medium is still
indicated to reduce the rate of recombination of the charged species through reactions
with the gap, reducing their availability.

512
 Ohtani (2010) states that any photocatalyst can be active under visible light
irradiation if it is modified through metallic or non-metallic elements. As an example, the
TiO2 is cited, which is widely used as a catalyst, but which would need a wavelength in
the ultraviolet region (greater than 400 nm) for its activation with maximum efficiency.
To solve this problem, nitrogen doping has been studied, among other strategies, since
this element is very stable, has an atomic size compatible with oxygen and needs a low
ionization energy to be introduced. Methylene blue, methyl orange and rhodamine have
been proven to be effectively degraded by nitrogen-doped TiO2 (Ahmad et al. 2016).
Another way to improve the efficiency of the process is to increase the contact
surface of the heterogeneous catalyst with the medium, for which slurry reactors have
been used, in which the catalyst is dispersed in the liquid reaction medium. However, in
this configuration it is necessary to consider a system to separate the catalyst particles at
the end of the process (Ahmad et al., 2016). As a possible solution, the immobilization
of the catalyst is pointed out. In this context, membrane technology consists of the
immobilization of solid particles, being an efficient process. It has a simultaneous
separation process of the photocatalyst and the product of the reaction system, separates
the photocatalyst from the treated water and keeps the solid particles confined in the
reaction system.
When referring to laboratory photocatalytic reactors, the light used can be
artificial, using one of the types of lamps, and the wavelength can be chosen according to
the catalyst used for a better reactor performance. However, with the increase in scale,
seeking energy savings, the objective becomes the use of sunlight.
Regarding the classification, they can be separated into production and
degradation reactors. Production reactors are characterized by the production of gases,
like as hydrogen, for conversion into clean energy. Degradation processes aim to remove
recalcitrant substances that remain in the water. The production ones have the difference
in the design that concentrate the gases inside, while the degradation ones do not have
this concern. Next, both will be explored.

Laboratory reactors for gas production

The photocatalysis process has been applied for the production of gases of interest,
especially for the generation of clean energy. In this context, the photocatalytic
production of hydrogen from the photolysis of water stands out with great potential. The

513
reactors and operating conditions developed for these processes, despite having
peculiarities inherent to the application, can also be successfully used in systems for the
degradation of emerging pollutants.
Vincentini et al. (2020) studied the efficiency of two photocatalytic reactors. The
first is an Annular reactor, using an 18 W UVC lamp as a source of radiation protected
by a quartz tube and positioned on the axis of the reactor. The second is called a quartz
reactor. This system can combine up to three 18W UVC lamps simultaneously, arranged
in an Aluminum refractory arc. The author observed that the quartz reactor has a hydrogen
generation rate approximately 7 times higher than that of the annular reactor, so this
reactor has a better use of the emitted photons.
Jing et al. (2010) studied a photocatalytic reactor for hydrogen production based
on a parabolic concentrator. One of the main objectives is to demonstrate the efficiency
of using direct sunlight. The most important challenges to be solved are uniform lighting,
more efficient catalysts under sunlight, as well as their low cost. The reactor consists of
glass, reflective surface, flow meters and the Compound Parabolic Concentrator (CPC),
which has an inclination of 35°, Xi'an latitude, China, and was operated between 12 and
13 h at maximum power, and until 15:00 there was a small decrease.
Enzweiler and colleagues (2020) analyzed the effect of catalyst concentration Pd-
TiO2/ZSM-5, ethanol content and pH of the solution on the rate of hydrogen production
under ultraviolet light irradiation. Using a stainless steel cylindrical reactor with a quartz
tube immersed in solution, the light source was a UVC lamp (ʎ=254nm and 7W). The
catalyst was kept dispersed in solution.
The generation of hydrogen, as well as other gases of interest, through the
photocatalytic process compared to the application of the technique for the degradation
of emerging effluents presents two fundamental differences. The first is the
thermodynamic conditions for the reaction, since the generation of compounds is an up-
hill process and photodegradations are classified as down-hill. Another difference is in
the reactor design, as the production of gases requires closed reactors, to allow the
accumulation and collection of products of interest, and photodegradation does not have
this restriction, since the objective is the mineralization of the reagent usually in solution.

Laboratory reactors for photodegradation

514
 Taking into account that the application of photocatalysis for the degradation of
contaminants is a relatively new process, much has been studied so that the operational
variables and the reactor design are improved and thus reach optimal efficiency. For this,
several authors have developed different designs for reactors, with changes in geometry,
material, light source and catalyst, in search of this improvement.
Jamali et al. (2013) studied the degradation of phenol with LED light using TiO2
as a catalyst. The photoreactor consisted of a cylindrical reaction cell with a diameter of
20 mm and a height of 50 mm, a polyoxymethylene (POM) cell holder to prevent the
absorption of ambient light by the photocatalyst, as shown in Figure 2. The UV-LED was
positioned vertically in the center of the support, it has a peak wavelength of 375 nm,
temperature range between 30 and 80 °C. The highest percentage of degradation was 87%
within 4 h of the experiment, the catalyst concentration varied between 0.17 to 1.8 gL -1.
A disadvantage is still the non-uniform distribution of light.
Figure 2 - Schematic representation of a photoreactor with LED light.

Source: Adapted from Jamali et al. (2013).

Fogaça et al. (2021) used a UV-LED mini-reactor for the degradation of
methylene blue dye and tartrazine. The reactor had a volume of 3.0 mL and a radiation
source with a power of 5 W and maximum emission at 365 nm. Graphene oxide was
supported on TiO2 and used as a catalyst. The reactor layout had a heat sink and fan and
a magnetic bar inside a quartz cuvette (reactor) to disperse the catalyst particles. The
entire reaction system was mounted inside a spectrophotometer.
Martín-Sómer and collaborators (2017) studied the efficiency of different lighting
sources for methanol oxidation. Comparing three different sources of UVA (a mercury
fluorescent lamp, a system based on 8 LEDs and a system based on 40 LEDs) with
different light distributions. The photoreactor used was an annular model, operating in a

515
closed recirculation circuit, with a reservoir tank as shown in Figure 3. The experiments
were carried out using TiO2 free in the concentration of 0.1 g/L.
Figure 3 - Schematic representation of annular photoreactor

Source: adapted from Martín-Sómer et al. (2017).

The results of Martín-Sómer and collaborators (2017) point out that the mercury
lamp promotes a more homogeneous distribution of light, however for the 8 LEDs, the
place where the LED is is highly irradiated, while other areas do not receive radiation
homogeneously. When the experiment was carried out with 40 LED points, an
improvement in the distribution homogeneity was obtained, however the mercury lamp
still promoted better results.
Fernandez et al. (2014) performed experiments with a set of 33 drug compounds
simultaneously. The photoreactor system used had a cylindrical shape of borosilicate
glass, with a total volume of 4 L. The membranes were hollow fiber polyvinylidene
fluoride (PVDF). Ultrafiltration membranes have pores of 0.04 um. The membrane
module was placed in the center of the reactor and has the role of separating the catalyst
and a selective barrier for the molecules to be degraded. UV radiation was provided by 7
lamps (blue black light, 8W). The author also cite having used aeration through a system
installed at the bottom of the reactor. This was used in order to increase the photo-
oxidation of molecules (reducing the sacrificial recombination of electrons), fluidize the
system to ensure a homogeneous mixture and provide turbulence along the submerged
membrane. Figure 4 illustrates the reactor. With the results, the author stated that
compounds with reaction rate constants greater than 0.0544 min-1 are effectively removed
in the photoreactor under the operating conditions used.

516
 Figure 4 - Schematic representation of a submerged membrane photocatalytic
reactor

Source: adapted from Fernandez et al. (2014).

Wang and colleagues (2021) also studied a submerged membrane photocatalytic
reactor for the removal of residual p-nitrophenol (PNP). The reactor had a volume of 9
L, being composed of a quartz tube, a light source and the membrane module. The light
source used was a 500 W Xenon lamp, as it resembles natural sunlight. The hollow fiber
microfiltration membrane module made of PVDF was attached to the inner wall of the
reactor. The catalyst used was Fe(III)-ZnS /gC3N4. Under optimal operating conditions, a
high percentage of PNP removal was obtained through photo-fenton reactions under
simulated sunlight irradiation. Membrane filtration quickly and effectively separated the
catalyst inside the reactor, preventing its loss.
Powder photocatalysts are being widely used for photocatalysis, however their
recovery is difficult. Ashar et al. (2020) suggest that the catalyst can be adhered to a
substrate, in their case they used polyester fabric added with nano-ZnO and doped with
Fe3+. After the tissue was prepared, the reactor was structured with a glass container with
a volume of 1.6 L. Illumination was provided by artificial daylight tubes, with 72 W,
according to the schematic diagram in Figure 7. Finally, the author concluded that the
doping of ZnO with Fe3+ can make the acid capable of capturing high content of sunlight.
The use of catalyst immobilization on polyester decreased the agglomeration of the
particles and acted as a new reusable material for the photocatalytic treatment of the
studied RB5 dye.

517
 Figure 5 - Schematic diagram of photocatalytic reactor with polyester supported photocatalyst

Fonte: adaptado de Ashar et al. (2020).

Table 1 presents information on laboratory scale photocatalytic reactors used in
scientific works published in the literature. The compound to be degraded, the irradiation
source and some observations made during the review are highlighted in order to facilitate
the comparison of different laboratory scale photocatalytic reactors.

Table 1 - Laboratory reactors for photodegradation

(to be continued)
DEGRADED IRRADIATION
REACTOR CATALYST OBSERVATIONS REFERENCE
COMPOUND SOURCE
Cylindrical reaction Radiation source Jamali et al.
cell (glass) UV-LED lamp positioned vertically in (2013)
Phenol ---
photoreactor with (ʎmax =375nm) the center of the
membrane module reactor.
Membrane module Mozia et al.
UV-C germicidal
Photoreactor with Municipal separate from the (2014)
lamp (16W, ʎmax = ---
membrane module sewage reactor for
254 nm)
ultrafiltration
UVA lamps Mercury lamp has a Martín-Sómer
Annular photoreactor Methanol (mercury lamp, 8 --- more homogeneous et al. (2017)
LED's and 40 LED's) distribution of light.
Submerged 33 drug Use of aeration to Fernandez et al.
membrane compounds 7 UV lamps (8W) --- increase reactor (2014)
photoreactor simultaneously efficiency
Wang et al.
Membrane filtration (2021)
Submerged Residual p- Xenon lamp (500W) quickly and effectively
TiO2 used in
membrane nitrophenol simulating solar separated the catalyst
powder (free)
photoreactor (PNP) irradiation inside the reactor,
preventing its loss.
UVC lamp (16 W,
365 nm)
UV lamp (UVA, 12 Ag/TiO2 coated
Cylindrical glass Formaldehyde Gaseous reaction Shie et al.
W) on plate holders
photoreactor in indoor air medium (2008)
30 or 40 UV-LEDs or glass rods
(20 mW per
UVLED, λ =383nm)
Use of a composite
Photocatalytic
Hydrogen parabolic concentrator Jing,et al.
hydrogen production direct sunlight TiO2 (free)
production in the reactor and pilot (2010)
reactor
scale reactor proposal.

518
 Table 1 - Laboratory reactors for photodegradation
(to be continued)
DEGRADED IRRADIATION
REACTOR CATALYST OBSERVATIONS REFERENCE
COMPOUND SOURCE
ZnO undoped
Fe3+@ZnO/polyeste
D65 artificial and in ZnO Illumination tubes
r based solar RB5 dye Ashar et al.
daylight tubes (72 doped with positioned above the
photocatalytic reduction (2020)
W) Fe3+ polyester reactor horizontally
membrane reactor
fabric support
Degradation in 50 mL
of solution
Xenon Lamp contaminated with Calza et al.
Quartz UV Reactor Diclofenac drug TiO2 (free)
(1500W) different (2006)
concentrations of
diclofenac and catalyst
Reactor volume of 0.7
Photocatalytic L, made of aluminum
membrane reactor, due to the higher
Four 24W black light
with hybrid reflectance of UV Sarasidis et al.
Diclofenac drug bulbs, encased in TiO2. (Free)
catalysis- irradiation and the (2014)
acrylic containers
ultrafiltration system inner surface was
with TiO2/UVA anodized for corrosion
protection
Methylene blue
Polymethylmethacryl dye, Orange II
Bismuth
ate (PMMA) dye and the
UV-A lamp titanate coated --- Grao et al. 2022
cylindrical antibiotic
glass rods
photoreactor levofloxacin
(Separately)
Presence of zinc oxide
coated with
ZnO covered
Membrane polyethylene glycol
Industrial Ultraviolet lamp with
photocatalytic nanoparticles and Desa et al. (2019)
textile effluent (UVC) λ =253.70 nm Polyethylene
reactor polypiperazine-amide
Glycol particles
(PPA) ultrafiltration
membrane
Photocatalytic Sodium Total system volume is Sarasidis, Patisios
Three 30W blue light
reactor with alginate TiO2 (Free) 9 L, light intensity is e karabelas
bulbs λ=365nm
ultrafiltration polysaccharides 8.3 mW/cm2 (2011)
Photoreaction system
Methylene blue UV-LED lamp (5 W, Fogaça et al.
Mini reactor TiO2 (Free) coupled to a
and tartrazine λ=365 nm) (2021)
spectrophotometer

Three levels of
irradiance (18, 32 and
pyrimethanil Xenon lamp (λ=300– Reina et al.
Channel reactor Fe(II) (free) 46 W/m2) and three
drug 800 nm) (2017)
concentrations of iron
(8, 20 and 32 mg/L)
The reactor consisted
of a PVC cylinder with
Dodecylbenzen 180 LEDs TiO2 (Free) in
Cylindrical reactor LED strips adhered Dominguez et al.
esulfonate (λ=375nm) in 10 different
with LED light directly to this vessel. (2014)
Surfactants strips with 18 units concentrations
Inside it fits a glass
reaction vessel.

519
 Table 1 - Laboratory reactors for photodegradation

DEGRADED IRRADIATION
REACTOR CATALYST OBSERVATIONS REFERENCE
COMPOUND SOURCE
The reactor consisted
Photodegradation by of a cylindrical glass
Propranolol Xenon Lamp 150 W Fe(III)-citrate
Fe(III)-citrate vessel being irradiated Chen et al. (2011)
drug (λ > 300nm) complexes
complexes laterally, the glass
acted as a filter.
Consisting of a tank
with rotating quartz
cylinders, being open
TiO2 coated rotary sunlight and/or to receive sunlight and
Aniline TiO2 (Free) Dúran et al. (2018)
drum reactor artificial UV light at the same time
having UV lamps
inside the drums along
the axis.
Reactor made of
Methylene blue TiO2-coated quartz with two
Reactor with side Barton, Matejec e
and methyl Mercury lamp (30W) glass sheets and configurations, one
and top light source Matousek (2016)
orange dye optical fibers with side lighting and
one above the sample
Reactor composed of a
quartz cylinder, with a
Secondary
lamp positioned
Submerged wastewater
UV-A lamp Suspension laterally and a Gupta, Gomma e
photocatalytic from the
(λ=365nm, 13W) nanosized TiO2 membrane module Ray (2021)
membrane reactor municipality of
immersed in the
London
solution. The system is
aerated.
Source: author, 2022.
Through the table it is possible to observe that different reactor configurations
have been studied for better efficiency of laboratory scale photocatalytic processes, as
well as changes in the lighting source and changes in the catalyst. It is observed that the
most used sources of irradiation in bench scale are Xenon lamps, LED's and mercury.
Many experiments use wavelengths (λ) greater than 300 nm aiming at the development
of systems for application under visible light.
The material used in the reactors mostly consists of quartz cells, which leads to
high costs, especially for scaling-up. An alternative found would be the use of borosilicate
glass, however this material only applies to visible light wavelengths. Another significant
factor to be considered in a possible scale expansion is that the systems are all operated
in batch, restricting the volume of the effluent to be treated.
Regarding the catalysts used, TiO2 stands out, being used suspended and
immobilized. However, other catalysts are also used in the published works. Reactors
with dispersed catalysts have a simpler configuration and those with immobilized
catalysts stand out for being easier to separate the solid later.

520
 Table 1 also shows the application of the photocatalytic process for the
degradation of different emerging pollutants. Among the main substances are dyes and
pharmaceuticals. They cause great concern in removal, as dyes cause color change in the
environment and drugs, in the long term, may be responsible for mutations to the affected
fauna and flora.

Scale up of photocatalytic reactors

Fundamentals
For a photocatalytic reactor to be deployed for larger scale operation, two factors
must be taken into account: technical feasibility and economic feasibility. There must be
a balance between these characteristics and one must consider the limitations of mass and
photon transfer, as well as efficient performance (Piriyah and Knman, 2020). These
authors mention that the heterogeneity of photocatalysis makes the reactor design involve
significant interdisciplinary knowledge.
The need to scale up comes from an economic bias and for that it is necessary that
the entire process is initially developed and operated on a small scale. There are
phenomena that directly interfere with the amplification, being the mass and heat transfers
the main ones. The problems related to these phenomena arise from the fact that these
mechanisms need time to occur satisfactorily, and this time increases with increasing
scale.
It is worth nothing that for scale expansion, the materials used must be carefully
considered. In the case of photocatalytic reactors, the piping must be made of material
that allows good penetration of light, and has good mechanical and chemical resistance.
The inlet flow and velocity must be in accordance with the residence time of the substance
in the reactor, and valves, pumps and recycle must support the effluent demand. In
addition to all the technical factors, economic viability is very important, both for the
construction of the reactor and for the maintenance and operation of the system.
In photocatalytic reactors, another challenge in scaling up is how the catalyst will
be used, suspended or immobilized. Being suspended, it is necessary to develop a way to
separate it from the effluent, so that it can be reused. With immobilized catalysts, it is
necessary to properly select the support material, analyze the best form of immobilization
and develop a methodology for fixation in the reaction system.

521
 Pilot scale photocatalytic reactors
The studies with laboratory scale photocatalytic reactors allowed some important
conclusions, such as the most promising catalysts as well as their supports and the
configurations that allow good light dispersion. In view of this, researchers have
developed photocatalytic reactors on a pilot scale, testing their applicability and
efficiency.
Plakas et al. (2016) developed a reactor in which the main components are the UV
treatment system and the membrane vessel. The membrane vessel has a working volume
of 10 L. The UV treatment system is made up of a chamber with a working volume of
15 L. The membrane module made with hollow fibers, for ultrafiltration, has a surface
area of 4.19 m2 and is submerged in the membrane vessel. UVC germicidal lamps were
used, with a power of 52W and a wavelength of 253.7 nm, wrapped in quartz gloves and
immersed in the UV camera. The total volume of the system is 25 L with an operating
capacity of 1.2 m3 of effluent per day.
Marculan et al. (2016) developed a pilot scale reactor for the degradation of dairy
effluent using TiO2 and solar radiation as shown in Figure 6. The system was composed
of a metal plate with an area of 2160 m2 coated with polyurethane resin and the catalyst.
The effluent was stored in a tank, pumped evenly under the plate and exposed to sunlight.
Afterwards, the effluent was collected in another container with a capacity of 5 L and
redirected to the raw effluent tank. This cycle was repeated for 2 h.
Figure 6 - Schematic diagram of photocatalytic reactor with flat plate.

Source: Adapted from Marculan et al. (2016).

The author (Marculan et al., 2016) obtained good results since the treatment time
is considered small when compared to a conventional effluent treatment plant. The
parameters of the treated effluent complied with the legislation with a reduction in the

522
content of organic matter measured in chemical oxygen demand (66.5%) and biochemical
oxygen demand (66.1%).
Durán et al (2018) comment that many researchers use reactors with parabolic
concentrators. Generally, reactors are composed of borosilicate glass tubes with polished
aluminum as a reflector, mounted on a fixed platform inclined at the local latitude, as in
Figure 7. The plants also have storage tanks, pumps, filters and operating parameter
controls. UV lamps can also be installed for use on cloudy days and even improve reactor
efficiency.
Figure 7 - Schematic diagram of photocatalytic reactor with com parabolic concentrator

Source: Adapted from Durán et al. (2018).

Carra et al. (2014) cite a pilot scale flat-channel reactor made of glass fibers. In
the proposed configuration, there is a tank with a length of 3.85 m, 0.64 m wide and
approximately 0.15 m high, with a central wall, forming two channels. It also has a paddle
wheel in one of the channels, to obtain a homogeneous system. The reactor has a total
volume of 360 L. A schematic can be seen in Figure 8.
Figure 8 – Schematic diagram of a channel photocatalytic reactor.

Source: Adapted from Carra et al. (2014).

Table 2 lists works in which pilot scale photocatalytic reactors were proposed.
Information such as the compound to be degraded and some observations made during

523
 the review are presented in order to facilitate the comparison of different photocatalytic
reactors on a pilot scale.
Table 2 – Pilot scale photocatalytic reactors.
DEGRADED
REACTOR CATALYST OBSERVATIONS REFERENCE
COMPOUND
Non- The total volume of the reactor is
concentrating Pentoxifylline Fe-TiO2 composite in the 5L, recirculating for 6h. The Bansal e Verma
solar fixed-bed (PEN) drug form of free granules reactor was closed with plastic (2018)
reactor film to avoid evaporation losses.
Continuously Antipyrine in
A Composite Parabolic
stirred tank solar municipal Ferrioxalate. Durán et al. (2014)
Concentrator (CPC) was used
reactor effluent
Photoreactor with
Composite TiO2 was sensitized with Diaz-Ângulo et al.
diclofenac ---
Parabolic methyl red dye. (2020)
Concentrator
H2O2 and K2S2O8, used
Photoreactor with Oil refinery as oxidants; FeSO4 Pourehie e Saien,
---
CPC wastewater heptahydrate, for (2020)
supplying ferrous ions.
Cylindrical H2O2 used as oxidants;
The maximum reactor volume Jiménez et al.
stirred reactor Residual waters FeSO4 heptahydrate, for
was 18 L. (2019)
made of PVC supplying ferrous ions.
Total irradiated volume is 10 L,
Effluent from TiO2, TiO2/ H2O2, and
has by-pass and 2 independent
CPC solar reactor textile photo-Fenton with Castro et al. (2014)
tanks, allowing the use of 2 and 3
industries ferrioxalate
reaction tubes.
Continuous flow The material of the tubes is glass,
Methyl orange TiO2 -SiO2 and glycerol
photocatalytic with a composite parabolic Hoang et al. (2021)
dye film.
reactor concentrator.
Micro
pollutants
Photocatalytic H2O2 used as oxidants;
(acetamiprid
reactor in FeSO4 for supplying Glass fibers as reactor material. Carra et al. (2014)
and
channels ferrous ions.
thiabendazole
pesticides)
Source: author, 2022.
In all the works presented in the table it was found that the lighting source used
was sunlight. Aiming at energy savings and taking into account the observations of the
consulted authors, it appears that this is the option that best suits these pilot-scale projects.
Compound Parabolic Concentrators (CPC) are widely used in order to obtain a better use
of this lighting. For a more uniform irradiation, an inclination according to the latitude of
the city where the equipment is installed is also used.
It is known that tubular reactors have a hydraulic flow regime that, preferably,
must be turbulent. This avoids the deposition of compounds in the equipment, enables
homogenization and thus favors the reaction. In cylindrical reactors, a form of agitation
is added to the system to achieve these benefits.

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 In order to reduce equipment costs, it appears that quartz is little used compared
to bench scale reactors, being replaced by different types of glass. Some options indicated
in the literature are borosilicate glass and glass with iron reduction in its composition.
All reactors studied showed good performance in the degradation of effluents,
which confirms the feasibility of using this process as a treatment. It is mainly observed
the degradation of dyes and medicines, and there is a variation in the percentage of
removal of the compounds between 75% and 94%, which correspond to changes in the
reaction medium, such as changes in the catalyst or effluent concentration, changes in pH
and period of solar irradiation.

Scale up Gaps
According to Ahmad et al. (2016), one of the main challenges for scale up and
manufacturing photocatalytic reactors is in reactor configuration and lighting efficiency.
The author states that there are two major restrictions, the first would be the distribution
of light within the reactor through the absorption and scattering of liquid to the
photocatalyst and the second is the large specific area for catalyst coating per unit volume
of the reactor.
The same author comments that an efficient design must have uniform irradiation
of the entire catalyst surface and almost complete elimination of mass transfer resistance.
Therefore, when talking about increasing the scale, it is necessary to pay attention to the
opacity of the effluent, consequently, with the penetration of radiation, dispersion of light
in the medium.
The material in which the wall will be built is also considered, as it needs to allow
the passage of the chosen radiation. Another concern is how the material behaves
receiving sunlight for long periods of time. Generally, glass is used, bringing limitations
such as size, problems with sealing and breakage, but on the other hand, it has good
weather resistance, chemical resistance and does not wear out easily.
Plakas et al. (2016) cite many advantages with the use of photocatalytic reactors
in pilot scale, such as ambient temperature and pressure, almost complete mineralization
of the compounds, and low operating cost. However, they mention heterogeneous catalyst
separation as a major challenge in this process.
One of the main obstacles found in this literature review is the way of using the
catalyst (free or immobilized), since in the dispersed form there is difficulty in separating

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at the end of the process and when using a material for immobilization there are
difficulties in the application. Many researches are still carried out to improve the
efficiency of catalysts, both modifications with supports (use of zeolite, polymers, metals)
and their use in the process (use in paints, coatings and membranes) as mentioned by
Marculan et al.(2016).
Considering the scale up, another difficulty is the material used in the reactor and
the lighting source. On a laboratory scale, there is the possibility of using quartz tubes in
which light passes through the material and also the use of lamps as a source of artificial
lighting. Considering an increase in scale, quartz becomes unfeasible due to its cost, as
well as lamps and their energy expenditure. In this sense, the use of natural sunlight
becomes the focus of studies.

CONCLUSION
Photocatalysis is a highlighted advanced oxidation process. Much research have
been developed to improve this method. The development of reactors of different
configurations has been much discussed, as well as the lighting source and the catalyst.
Seeking improvements in process yield, researchers change many process variables, such
as different lighting sources with variation in wavelength and power. Heterogeneous
catalysts are used in dispersed and immobilized ways, varying the way they are
immobilized and the material used, as well as the concentration in the medium.
When discussing projects on a laboratory scale, the published works are in greater
numbers. In bench scale, the use of artificial light, batch operation, the materials used
have higher acquisition costs and greater energy expenditure. Taking into account that
these researches aim to verify the functionality of the process and that the equipment is
small, little attention is paid to the somewhat high costs.
For scale up, technical feasibility and economic feasibility are highly evaluated.
So, the exchange of equipment materials, use of sunlight as a source of lighting and reuse
of catalysts are actions taken to improve the performance of the process with reduced
costs. Considering that all these factors influence the efficiency of the process, all
variables must be analyzed.
These advances in research related to photocatalysis are very important since this
process is excellent both for the production of potential clean energy and for the removal
of pollutants that are of great concern to the population. Therefore, with investments for

526
better yields, better treatment efficiency, energy efficiency and cost reduction, this
process becomes much more viable and can greatly contribute to important environmental
issues.

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Recebido em: 03/05/2022

Aprovado em: 05/06/2022
Publicado em: 08/06/2022

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