catalysts

Article
Heterogeneous Photo-Fenton Reaction for Olive Mill
Wastewater Treatment—Case of Reusable Catalyst
Cristina Agabo-García 1,2 , Naima Calderón 2 and Gassan Hodaifa 2, *

1 Chemical Engineering and Food Technology Department, Faculty of Science, University of Cádiz,
ES-11510 Puerto Real, Spain; [email protected]
2 Molecular Biology and Biochemical Engineering Department, Chemical Engineering Area,
Faculty of Experimental Sciences, University of Pablo de Olavide, ES-41013 Seville, Spain;
[email protected]
* Correspondence: [email protected]; Tel.: +34-954-978-206

Abstract: Heterogeneous catalysts can be an efficient and economical option for olive mill wastewater
(OMW) treatment by an advanced oxidation process if they could be reused. In this work, OMW was
treated using a heterogeneous photo-Fenton reaction (artificial ultraviolet light/H2 O2 /HFeO2 ). For
this purpose, different concentrations of HFeO2 were tested: 0.04; 0.3; 0.8; 5.0; 10.0; 20.0; 30.0, and
50.0 g/L. The following operational conditions were chosen: pH = 3.0, temperature = 20 ◦ C, agitation
rate = 700 rpm. The experimental results showed high removal percentages of the main OMW
characterization parameters at 50 g/L of HFeO2 : %CODremoval = 62.8%; %total phenolic compounds
(TPCs) = 88.9%. These results were also compared with those of other control oxidation systems, i.e.,





 UV, H2 O2 , and UV/H2 O2 , which provided 35.5 and 56.1%; 46.2 and 74.0%; 48.0 and 76.8% removal,
respectively. In addition, the catalyst was reused three times, recovering more than 90.5% of it.
Citation: Agabo-García, C.;
Calderón, N.; Hodaifa, G.
Heterogeneous Photo-Fenton Keywords: olive mill wastewater; photo-fenton reaction; artificial UV light; heterogeneous reaction;
Reaction for Olive Mill Wastewater catalyst recycling
Treatment—Case of Reusable
Catalyst. Catalysts 2021, 11, 557.
https://doi.org/10.3390/
catal11050557 1. Introduction
Olive oil is produced in olive mills either by the discontinuous method (press) or
Academic Editor: Narmina
by the continuous centrifugation method. The continuous centrifugation methods may
O. Balayeva
involve a decanter with three exits (olive oil, pomace, and wastewater) or a decanter with
two exits (olive oil and pomace). There are about 25,000 olive mills worldwide. Wastewater
Received: 6 April 2021
arising from olive processing is one of the strongest industrial effluents. In this sense, for
Accepted: 27 April 2021
press and three-exit continuous centrifugation processes, the COD and BOD5 values of
Published: 27 April 2021
wastewater are equal to 40–220 g O2 /L and 35–110 g O2 /L, respectively [1–4]. However, for
the two-exit continuous centrifugation process, the COD and BOD5 values of wastewater
Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in
are equal to 0.5–65 g O2 /L and 8.5–19 g O2 /L, respectively [5–7]. These values for the COD
published maps and institutional affil-
and BOD5 parameters are higher than that those registered for wastewaters generated by
iations.
other food industries, such as potato chips (5940–7058 mg O2 /L and 2729–3415 mg O2 /L)
and potato starch plants (900–1400 mg O2 /L and 1100–1500 mg O2 /L) [8].
The management of OMW consists of its controlled or uncontrolled spreading in soils.
This practice has led to severe environmental problems. In fact, the Spanish Government
forbid the direct discharge to soils in 1981 and obligate to collect OMW in evaporation reser-
Copyright: © 2021 by the authors.
voirs [1]. This wastewater management method has a few maintenance requirements and
Licensee MDPI, Basel, Switzerland.
is enhanced under Mediterranean conditions. However, this method has some drawbacks
This article is an open access article
distributed under the terms and
such as the need of large areas to collect the large amounts of OMW generated, bad odors
conditions of the Creative Commons
due to the evaporation of volatile organic acids such as butyric, acetic, or propionic acids
Attribution (CC BY) license (https:// and insect plagues, fermentation processes with the subsequent emission of greenhouse
creativecommons.org/licenses/by/ gasses such as CH4 or H2 S. Besides, OMW (acidic pH and organic content) persists and, by
4.0/).

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Catalysts 2021, 11, 557 2 of 13

floods and infiltrations, may lead to higher problems such as contamination of aquifers,
soils, and the air [2,9].
To perceive the magnitude of the OMW problem, a medium-sized olive mill (the
most widespread type of mills) generates between 10 and 15 m3 of OMW per day and,
during the olive harvesting period (November–February), the OMW volume production
is higher. As a consequence of this environmental situation, new research is focusing on
different low-cost OMW treatments with the aim to regenerate OMW and recycle them
in the proper process of olive oil production or for irrigation purposes [6]. In this sense,
different conventional (such as aerobic/anaerobic digestion treatments, composting, or
co-digestion) and non-conventional (such as filtration, flocculation, advanced process
technologies, or membrane technologies) technologies have been proposed alone or in
combination to regenerate OMW [10].
Aerobic treatments are commonly used when the organic load is not very high such
as in the case of olive washing wastewater [11]. On the other hand, in the case of anaerobic
digestion, in spite of producing a high-value product (biogas), the high organic load is
not completely eliminated [12], and a dilution step is desirable for reducing the toxicity of
some compounds (i.e., phenolic compounds) on microorganisms’ growth. The composting
technic has been also checked for OMW treatment [13] in order to generate another high-
values products (fertilizers). However, this operation requires a long period of time (several
weeks) for a complete composting and the subsequent evaluation of the resulting products,
especially from the point of view of their phytotoxicity.
Physical simple treatments such as dilution, evaporation, centrifugation, or sedimen-
tation have a great potential for the decontamination of OMW but are usually integrated
in a complete process. As an example, assisted sedimentation (by flocculation) has been
studied using common chemical agents such as ferric chloride, aluminum chloride, ferrous
sulphate, among others [1]. On the other hand, the membrane technology has been deeply
investigated in OMW treatment. However, the high organic load in OMW prevents this
technology from working efficiently; moreover, it presents several disadvantages such as
(i) the fractionation of OMW, generating solid waste that requires further treatment, (ii)
separation phases in concentrate and permeate but not organic matter degradation, (iii)
continuous membrane fouling, (iv) short life shift of the membrane, and (v) high costs [14].
In the last years, advanced oxidation processes (AOPs) have emerged as a promising
technology due to the simplicity of the techniques and the high organic removal efficiencies
obtained. Especially, different authors have highlighted the benefits of using this technology
for OMW [15–17] instead of the conventional biological treatment. Different AOPs have
been used for OMW treatment during the last years including photolysis, photo-oxidation,
Fenton’s, and photo-Fenton reaction. Photo-Fenton-like oxidation and ozonation are used
alone or in combination with UV-light. In this sense, Hodaifa et al. [17,18] obtained 25–35%
conversion of TOC for photolysis and 38–43% for a UV/H2 O2 system during the first
30 min. In addition, 57.9% of TOC conversion was obtained in a photo-Fenton test by using
FeCl3 as a catalyst [17] and 47.6% of TOC conversion during a photo-Fenton-like oxidation
using TiO2 as a catalyst [18], with a catalyst concentration of 3 g/L and an operation time
of 5 min, respectively. Ozonation has been applied to OMW alone and in combination with
UV light [19] and in the presence of different catalysts such as BiFeO3 [20], obtaining a
maximum COD conversion of 98% for O3 /BiFeO3 /S2 O82 during 40 min.
These methods are based on the use of strong oxidant agents such as ozone, hydrogen
peroxide, sodium hypochlorite, potassium permanganate [2], which oxide a wide range of
compounds, irrespective of their chemical structures, including recalcitrant compounds,
without the generation of secondary pollutants. These oxidants generate hydroxyl radicals
(OH• ), which are highly reactive and unstable species that transform complex organic
structures into final simple inorganic compounds such as CO2 and H2 O [21,22]. The
oxidants can be used in combination with other enhancers of the reaction such as a source
of energy (UV lamps, solar light) or catalysts [23]. Having high efficiency for organic matter
elimination, AOPs also involve simple processes and mild operational conditions [22].
Catalysts 2021, 11, 557 3 of 13

However, the main challenges are the costs of the process (especially, the chemicals
costs) and the recovery of the catalyst during and after treatment. Hence, it is suggested
to use this technology as the main process, integrating it with other physicochemical pre-
treatments in order to reduce the initial organic load before proceeding with the AOP step
(for catalyst cost reduction). In addition to include a post-physical treatment method in
order to eliminate the residual catalyst [24,25]. In this sense, Benitez et al. [19] studied
the combination of ozonation and aerobic treatment for OMW treatment obtaining a total
conversion of TOC of 84.6%. On the other hand, in previous studies by our group, OMW
was treated by a combination of photo-Fenton and sedimentation operations, obtaining a
total conversion of TOC of 96.1% [23]. Another option to reduce costs would be using a
catalyst that can be reused to avoid the continuous removal of the catalyst. In this sense,
solid catalysts have emerged as promising reusable catalysts due to their easy separation
from wastewater, avoiding secondary pollution with metallic ions, as it happens in liquid
catalysts [26].
In a heterogeneous photo-Fenton-like reaction, UV activates the catalyst to react with
H2 O2 , generating hydroxyl radicals (OH• ). The heterogeneous catalyst is usually based on
micro- or nanoparticles and/or other organic frameworks to have a large specific surface
area enhancing the adsorption of reactants and improving the degradation efficiency of
organic pollutants [27]. They are based on different components such as iron metals [28],
titanium [27], cesium [29], or non-metal catalysts such as sulphate or N-and S-co-doped
biomass carbon, activated carbon, graphene oxide, or sulphate [30]. Among the different
heterogeneous catalysts, metal catalysts exhibit high activity in AOPs, owing to their excel-
lent electron transfer capability. Specifically, iron-based materials have been successfully
used for the photo-Fenton treatment of different compounds. Luo et al. [31] reviewed the
different iron-based heterogeneous catalysts. HFeO2 has not been previously evaluated as
a catalyst for organic load degradation in wastewater. In this work, HFeO2 was proposed
and tested as an efficient catalyst in OMW treatment by a photo-Fenton like reaction. In
addition, the catalyst was recovered several times, and its efficiency after reuse was checked
and determined.

2. Results and Discussions

2.1. OMW Characterization
The raw wastewaters used in this work were directly collected from olive mills in
Seville province (Spain), which operated with a continuous two-outlet decanter process.
Table 1 shows the characterization of the crude mixture (1:1 v/v) of olive mill wastewaters
from olive washing and olive oil washing.
From Table 1, it is clear the high organic load of this kind of wastewater (COD up to
16586 mg O2/L and total carbon up to 4431.2 mg/L) and the non-biodegradable organic
matter contained in this OMW (COD/BOD5 ratio = 8.2) in comparison to the registered
parameters for urban wastewater (COD/BOD5 ratio = 2), [6].

2.2. pH and Conductivity Variations

Figure 1a,b shows the behavior of pH and electric conductivity for control systems
(air, UV, H2 O2 , and UV/H2 O2 ) and photo-Fenton like reactions at different catalyst con-
centrations. In general, there was no variation in pH and electrical conductivity values
throughout time. Only a slight increase in pH (<0.5) appeared in experiments with higher
amounts of catalyst, specifically, in those where the concentration of HFeO2 was above
10 g/L. Because not all reactions taking place during the oxidation time are known exactly,
it is possible that some compounds of basic character are produced in the medium due to
incomplete degradation of the organic matter (Equation (1)).

Organic matter + oxidant → simple products + CO2 + H2 O (1)

Simple products → CO2 + H2 O (2)

Catalysts 2021, 11, 557 4 of 13

Table 1. Characterization of a mixture of OMW used as the initial sample and the Spanish maximum
values allowed for discharge into the public domain (Royal Decree 849/1986).

Spanish Maximum Values Allowed for Discharge

Parameters Values
into the Public Domain
pH 4.37 5.5–9.5
Electric conductivity (mS/cm) 3.47 -
Turbidity (FTU) 3453 -
Total solids (%) 0.775 -
Total suspended solids (%) 0.699 30
Organic matter (%) 0.571 -
Ashes (%) 0.204 -
Total phenolic compounds
288 1
(mg/L)
Fat content (%) 0.00360 40
Dissolved O2 (mg/L) 0.79 -
BOD5 (mg O2 /L) 2030 300
COD (mg O2/L) 16586 500
Total carbon (mg/L) 4431.2 -
Total organic carbon (mg/L) 4252 -
Inorganic carbon (mg/L) 179 -
Total nitrogen (mg/L) 72.8 -
Iron (mg/L) 28.1 10
Chlorides (mg/L) 1132 -
Sulphates (mg/L) 29 -
Na+ (mg/L) 2.73 -
NH4 + (mg/L) 2.02 -
K+ (mg/L) 195 -
Ca2+ (mg/L) 8.00 -

Figure 1. pH (a) and conductivity (b) variation throughout of the experiments for different chemical oxidation sys-
tems: air, UV, H2 O2 , UV/H2 O2 , and UV/catalyst/H2 O2 , with different catalysts doses. Common operating conditions:
CODinitial = 16586 mg O2 /L, H2 O2 = 35.3 g/L, T = 20 ◦ C, agitation speed = 700 rpm, and pH = 3.

These behaviors are important to detect two phenomena: (i) the possible transfer of
ions from the surface of the catalyst to the medium and (ii) intermediary compounds with
basic characteristics during organic matter degradation that could modify the conditions
of the reaction.
As for the conductivity recorded (Figure 1b), it can be observed that it remain virtually
constant throughout the 3 h of experimentation and only in the oxidation experiment using
50 g/L of HFeO2 , we recorded conductivity values higher than those of the experiments
with lower catalyst concentrations, which could be due to the catalyst itself or to the partial
solubilization of the catalyst surface and the release of iron ions into the medium. However,
these conductivity values did not exceed the initial values. The experiment evaluating
oxidation by air showed higher conductivity levels than the other experiments, due to the
Catalysts 2021, 11, 557 5 of 13

lack of pH modification of the wastewater at the beginning of the experiments as in the

other experiments.

2.3. Organic Matter Degradation

Figure 2a presents all the chemical oxidation systems referred to the removal per-
centage of COD during the experiments. The treatments with the lowest efficiencies are
clearly air (average %COD removal = 11.6 ± 3.54%) and UV/light with 35.5 ± 2.48%. These
results are similar to those obtained previously by our research group [23]. In fact, these
results highlight the potential of hydrogen peroxide as an oxidant. For this reason, the
oxidation systems based on H2 O2 and UV/H2 O2 showed higher values, i.e., 46.1 ± 3.03%
and 48.3 ± 1.53% of COD removal. On the other hand, when the catalyst was introduced
into the oxidation system, the %COD removal also increased with the augmentation of
the catalyst concentration, being optimal (62.8 ± 0.454%) when 50 g/L of catalyst was
used. The difference in the percentage of elimination with respect to the H2 O2 /UV system
was around 10%; however, it is necessary to consider that the use of a catalyst adds more
turbidity to the system, which can interfere with the projection of light from the lamp. In
this sense, at a concentration below 1 g/L of catalyst, the system showed COD removal
around 48.6 ± 0.859%. Only when the catalyst concentration was ≥5 g/L, the %CODremoval
was >50% (corresponding XTC and XTOC ≈ 0.47, Figure 2b,c).

Figure 2. Variation of organic matter degradation of OMW throughout the experiment time for different chemical oxidation
systems: air, UV, H2 O2 , UV/H2 O2 , and UV/catalyst/H2 O2 with different catalysts doses. (a) Removal percentages of
COD, (b) conversion degree of total carbon, (c) conversion degree of total organic carbon, (d) removal percentages of
total phenolic carbon. Common operating conditions: CODinitial = 16586 mg O2 /L, H2 O2 = 35.3 g/L, T = 20 ◦ C, agitation
speed = 700 rpm, and pH = 3.
Catalysts 2021, 11, 557 6 of 13

The OMW photodegradation profiles by heterogeneous photo-Fenton reaction using

HFeO2 as a catalyst are similar to those obtained by Agabo and Hodaifa [23], Hodaifa
et al. [17], and Martínez-Nieto [22,32] for homogenous photo-Fenton reaction. In fact,
Figure 3 shows the degradation capacity of the system UV/HFeO2 /H2 O2 , in which the
degradation is increased with the reaction time.

Figure 3. OMW samples after centrifugation taken at different times of photo-Fenton treatment
(UV/ HFeO2 /H2 O2 ). Common operating conditions: CODinitial = 16586 mg O2 /L, H2 O2 = 35.3 g/L,
[HFeO2 ] = 30 g/L, T = 20 ◦ C, agitation speed = 700 rpm, and pH = 3.

Figure 2d shows that it is possible to degrade the included phenolic compounds,

%TOCs removal, of OMW with all oxidation systems evaluated; air and UV appeared to
be the least powerful oxidation treatments. In contrast, the photo-Fenton system with
50 g/L catalyst degraded about 90% of the total phenolic content in the samples. In
general, when the HFeO2 concentration was increased, the %TPCs removal was also
slightly increased. However, it can be seen that even for air and UV systems, TPCs removal
was equal to 52.3 ± 3.53% and 56.7 ± 0.542%, respectively. The H2 O2 system registered
%TPCsremoval = 75.0 ± 3.05%, and the UV/H2 O2 system provided a slightly higher value
equal to 76.8 ± 1.73%. This fact indicates the susceptibility of phenolic compounds to be
oxidized, which gives them a perfect buffering capacity of oxidation of other important
compounds such as lipids, proteins, vitamins, dyes, carbohydrates, and pigments of
the food industry [33]. The majority of phenolic compounds (5% of organic matter) are
transferred to wastewater in olive oil production [34] and eliminated (75–80%) in a short
period of time (few minutes, Figure 2d). Evidently, this treatment is more efficient for the
degradation of phenolic compounds than for COD, despite the fact that both reflect the
organic matter content. This advantage in the degradation of phenolic compounds could
be due to the fact that these molecules are found in simpler forms and are therefore easier
to attack, while COD may involve molecules with high molecular weight such as lignin
and cellulose, among others [35].

2.4. Catalyst and Oxidant Agent Residue

In all chemical oxidation processes, the elimination of chemical agents after treatment
must be a priority in order to avoid a new problem in the wastewater target. In this sense,
the residual content of both agents (H2 O2 and iron) was measured, as well as turbidity
values. The initial iron value was 28.1 mg/L, and the final residual iron value was between
2.05 and 3.40 mg/L for photo-Fenton like reactions at any concentration and UV/Fe–
catalyst/H2 O2 systems, removing between 87.9 and 92.7% of iron. These results are similar
to those determined for other homogenous photocatalysis reactions (using catalysts such
Catalysts 2021, 11, 557 7 of 13

as FeCl3 , Fe2 (SO4 )3 ·H2 O, and FeSO4 ·7H2 O) after performing a catalyst separation step,
normally by natural sedimentation or sedimentation–flocculation [17].
Meantime, the initial iron on OMW was 0.516 mg/L, and the residual total iron
determined for air, H2 O2 , photolysis, and UV/H2 O2 systems were lower than that value.
This was due to the possible complex formation of iron ions with the organic matter
present in OMW. For the heterogeneous photocatalysis, the concentration of iron in the
final treated water was detected in the range of 2.05 to 3.20 mg/L (average value and
standard deviation = 2.63 ± 0.389 mg/L), (Table 2). In general, the heterogeneous catalysts
should avoid residual iron generation, but during the photooxidation some iron species
are generated as residual iron, which can be removed by centrifugation or sedimentation
because it generates flocculent aggregates that tend to sediment. This effect can be also
appreciated in the turbidity values. The initial turbidity values (3453 FTU) were reduced to
67.8% and 73.0% for UV and H2 O2 , respectively. However, for photolysis and photo-Fenton
like reactions, the turbidity removal percentages were increased to 83.7–89.1%.

Table 2. Final values of parameter (turbidity, residual oxidant agent, and total iron) determined for
treated water at the end of the experiments and after sample centrifugation.

Residual
Residual
Oxidation HFeO2 Turbidity Total-Fe
H2 O2
System (g/L) (FTU) (on OMW)
(g/L)
(mg/L)
Air - 1469.5 - 0.431
H2 O2 - 930 4.58 0.199
UV - 1111 1.06 0.368
UV/H2 O2 - 556 3.80 0.0650
0.04 562 5.00 2.93
0.25 544 5.02 2.32
0.75 569 4.99 2.66
5.00 437 4.97 2.05
UV/H2 O2 /HFeO2
10.0 469 4.78 2.32
20.0 385 5.09 2.47
30.0 447 4.94 3.12
50.0 376 5.14 3.20

Regarding the residual H2 O2 concentrations after the use of each oxidation system,
it can be observed that no residual H2 O2 was found after air oxidation, which is normal
since no oxygen peroxide was added to the wastewater. After wastewater photolysis with
artificial UV light, a concentration of 1.06 g/L of H2 O2 was detected (Table 2). This was
due to the production of hydrogen peroxide via UV-photolysis in the presence of some
catalyst such as that contained in the OMW used (Table 1). In this sense, the UV light lamp
used had a nominal level of emission intensity in the range of 200–280 nm and a power
equal to 150 W. To confirm the hydrogen peroxide production, a control experiment was
performed using tap water, HFeO2 as catalyst, and under UV lamp exposure. The results
showed the generation of 0.106 g/L of H2 O2 after 160 min (Figure 4). Similar results were
reported by other authors as Campos-Martin et al. [36] and Hayes et al. [37].
Catalysts 2021, 11, 557 8 of 13

Figure 4. H2 O2 production using tap water in presence of catalyst (HFeO2 ) and UV-light generated
by the lamp used in this work.

2.5. Catalyst Reuse

In this work, the catalyst was recovered and reused in photocatalysis up to three
consecutive times to compare the efficient loss after each reuse. After each round of
recovery (catalyst separation from OMW, treated, and then dried in an oven at 105 ◦ C),
the catalyst quantity recovered was around 90% (w/w). The separation of the catalyst was
instantaneous by natural sedimentation due to its high density.
Table 3 shows the catalyst (HFeO2 ) quantities recuperated after each reutilization.
As can be seen in Table 3, it was possible to recover a high percentage of the catalyst
used, which represents an advantage compared to homogeneous catalysis, in which the
catalyst can be used only once. Recovery was possible because this catalyst can precipitate
instantaneously, thus facilitating its separation from the other components in the water. In
addition, it is important to indicate the lower percentage in the first recovery (87.6%) of the
commercial catalyst used, which was associated with a small percentage of fine particles
that were difficult to separate from the water by gravity.

Table 3. Recovery percentage of the catalyst after use in the photo-Fenton oxidation for OMW treatment.

Reutilization Number % Amount Recovered After Each Use of HFeO2

First 87.6
Second 92.9
Third 91.0

In the reuse experiments, a final pH adjustment to around the value of 7 of the

treated water was carried out, which is between the levels stipulated by the legislation
(Spanish Royal Decree 849/1986, pH between 5.5 and 9), and this adjustment also favored
the precipitation of colloidal organic matter and iron in the form of iron hydroxide that
remained in suspension after oxidation. Table 4 shows how the levels of all parameters
were considerably reduced (after natural OMW sedimentation for 24h and photooxidation),
even after the third reuse of HFeO2 .
Catalysts 2021, 11, 557 9 of 13

Table 4. Final values of main characterization parameters after natural OMW sedimentation (sedimented OMW) and
photo-Fenton-like treatment in different rounds, reusing the heterogeneous HFeO2 catalyst.

Catalyst Reuse Number %Average

Parameter Crude OMW Sedimented OMW Final
1 2 3 Removal
COD (mg O2 /L) 16,586 14,098 4913 4965 4666 65.6
Total carbon (mg/L) 4431.2 3776.5 1578 1333 1305 62.7
TPCs (mg/L) 288.0 279.4 30.4 16.4 20.1 92.0
Turbidity (FTU) 3453 3108 27.9 4.7 67.5 98.9
Total iron (mg/L) 28.1 26.9 1.9 2.0 1.6 93.2

In general, no variation of the values of the removal percentage of the parame-

ters COD (70.8 ± 0.786 mg O2 /L, TC (68.3 ± 0.738 mg/L), total phenolic compounds
(92.3 ± 0.0357 mg/L), turbidity (99.0 ± 0.156 FTU), and total iron (93.5 ± 0.00102 mg/L)
were determined after the three reutilizations. However, the value of two parameters, COD
and total phenolic compounds, did not comply with the national recommendation for
wastewater discharge into sewage systems (COD = 500 mg/L and 1 mg/L) according to
the Spanish Royal Decree 849/1986 for “olive oil production industry”. However, the limit
for iron values (10 mg/L) was reached after the third round of recovery. As the competency
of regulation discharge belongs to Local Authorities in Spain, the government of Seville
established other limits, i.e., total phenolic compounds, 3 mg/L, and iron, 10 mg/L, in its
Regulating Ordinance published on the official Gazette No. 117. Therefore, the reuse of this
catalyst can make this process more economical and efficient. In this sense, it is interesting
to indicate that for a real process for OMW treatment, the process does not contain only
the photooxidation step, which means that the addition to other separation units before
and after photooxidation makes it possible to achieve the legislation limits established by
the authorities.

3. Materials and Methods

3.1. Chemicals
For the photo-Fenton oxidation, the catalyst used in this study was HFeO2 from
Sigma-Aldrich (Madrid, Spain).
Hydrogen peroxide solution (30% w/v) in stable form, Manganese IV oxide, and
potassium dichromate, 99.5%, were purchased from Fisher Scientific (Barcelona, Spain). Hy-
drochloric acid 37% was purchased from Acro organics (Spain). Titanium (IV) oxysulphate–
sulphuric acid solution 27–31% H2 SO4 was supplied by Fluka Analytical (Barcelona, Spain).

3.2. Methodology
The oxidation reaction was performed in a photo-reactor with 1 L total capacity. In all
experiments, 500 mL of wastewater was used, and HFeO2 in solid state with a size particle
of 30–50 mesh was used as a catalyst. Two sets of experiments were developed: the first
with different catalyst concentrations (0.04; 0.25; 0.75; 5.00; 10.0; 20.0; 30.0; 50.0 g/L), and
the second with reusable catalysts at 50 g/L of concentration. For the reusing experiments,
after any round of treatment, natural sedimentation was developed, separating the liquid
phase from the catalyst. After that, the catalyst was washed with distilled water and dried
in an oven at 105 ◦ C.
Four control experiments were also carried out as follows:
• Oxidation with only air.
• Oxidation with UV alone (photolysis).
• Oxidation with only H2 O2 .
• Oxidation with the system UV/H2 O2 .
In all experiments, the pH value was adjusted to 3.0 by 1 M HCl. Subsequently, in
the experiments including H2 O2 , a solution of H2 O2 was diluted to reach 7.5% (w/v) of
concentration as the optimal concentration. The initial hydrogen peroxide amount neces-
sary for the complete degradation of the organic matter (COD) of OMW was calculated
Catalysts 2021, 11, 557 10 of 13

according to the reaction stoichiometry [17]. Finally, an immersion ultraviolet lamp was
switched on. The UV lamp in the photo-reactor was covered by a quartz immersion tube
and a quartz cooling jacket where the cooled water was pumped by a portable chiller (Mod.
PolyScience, Niles, IL, USA).
A magnetic stirrer inside the photo-reactor to increase the degree of mixing of catalyst
and OMW was used, allowing greater access to the UV light. The UV lamp used was
an immersion lamp, model TQ 150 (standard), No 5600 1725, brand HNG Germany G4.
The dimensions of the UV lamp were total immersion 384 mm, luminous part 303 mm,
emission center at 44 mm, and power of 150 W. The power of the UV lamp per surface
unit was 10,000 W/m2 , higher than the maximum power of the sun for an average day
(146 W/m2 ), [38]. Inner photo-reactor temperature was controlled through a quartz-cooling
jacket located around the UV lamp.
The common operating conditions were pH = 3, temperature = 20 ◦ C, and stirring
rate = 700 rpm. The temperature and pH conditions were selected according to our previ-
ous work [17]. The stirring rate used was the minimum rate, which kept all the catalyst in
suspension, so that it would be available at any point in the photoreactor to approximate to
the degree of perfect mixing in the reactor. We started from 60 rpm up to the best stirring
rate for this heterogeneous catalyst. These experiments were realized with catalyst and tap
water. For the photoreaction monitoring, 40 mL of effluent were sampled at 3, 10, 20, 30, 60,
120, and 180 min. In this sense, after each sample was taken, the catalyst was separated by
natural sedimentation, as the separation was instantaneous.

3.3. Analytical Methods

Real OMWs were characterized by measuring the following parameters: pH value,
electric conductivity, turbidity, moisture and volatile materials, total solids, organic matter,
ashes, chemical oxygen demand (COD), total carbon (TC), total organic carbon (TOC),
inorganic carbon (IC), total nitrogen (TN), total phenolic compounds (TPCs), total iron, chlo-
ride, sulphates, sodium, ammonium, potassium, calcium, zinc, magnesium, manganese,
and iron.
The value of pH was measured using a CRISON pH meter, mod. LPG 22 (Barcelona, Spain).
Electric conductivity was determined directly by a CRISON conductivity meter,
GLP31 model.
Turbidity was measured by a Turbidimeter Hanna, mod. HI93703 (Barcelona, Spain).
The total solids and moisture and volatile materials were determined according to
the weight loss of the sample after being placed in an oven, type Memmert mod. UF110
Memmert GmbH+Co KG (Schwabach, Germany) at 105 ± 1 ◦ C.
Ashes were determined by using an oven, type CARBOLITE mod. ELF14 of Gero
Ovens (Chelmsford, United Kingdom) at 575 ± 5 ◦ C.
The percentage of organic matter was calculated as the percentage of total solid minus
the percentage of ashes.
Chemical oxygen demand (COD) was measured by photo-metric determination,
by using a UV–Visible Spectrophotometer, type Evolution 201 (Thermo Scientific) at
620 nm, of the concentration of chromium (III) after 2 h of oxidation with potassium
dichromate/sulphuric acid/silver sulphate at 148 ◦ C [39].
Total carbon (TC) represents all the carbon contained in a sample, which includes
organic and inorganic carbon (TC = TOC + IC); total organic carbon (TOC) is the organic car-
bon that is converted into carbon dioxide after oxidation (TOC = TC − IC), inorganic carbon
(IC) is the inorganic carbon in a sample that, after acidification, turns into carbon dioxide. IC
includes all carbonates, bicarbonate, and dissolved carbon dioxide (IC = TC − TOC), and
total nitrogen (TN) is all nitrogen in the sample, which includes organic and inorganic ni-
trogen. Total Carbon and Nitrogen were determined using an analyzer provided by Skalar
Analytical B.V Company, mod. FormacsHT and FormacsTN (Breda, The Netherlands).
Total phenolic compounds (TPCs) were determined by making them react with a
derivative thiazole, producing a purple azo dye, which was measured photometrically at
Catalysts 2021, 11, 557 11 of 13

475 nm by using a UV–Visible spectrophotometer, type Evolution 201 of Thermo Scientific

(Barcelona, Spain) [40,41].
Total iron ions were determined by reduction of all iron ions to iron ion (II) in a
thioglycolate medium with a derivative of triazine. This reaction results in a reddish-purple
complex that was determined photometrically by the using UV–Visible spectrophotometer,
type Evolution 201 (Thermo Scientific) at 565 nm [40,41].
Sulfates and chloride were determined photometrically at 420 nm and 450 nm by using the
UV–Visible spectrophotometer, type Evolution 201 (Thermo Scientific), respectively [40,41].
The ions of Na, NH4 , K, Ca, Cu, Zn, Mg, Mn were determined by using selective
electrodes supplied by Crison, mod. GLP22 (Barcelona, Spain) and Hatch mod. HQ40d
(Madrid, Spain).

3.4. Calculations and Kinetics

Removal percentages for each parameter were calculated as follows:

(Parametero − Parameteri )
%Removal of the parameter = (3)
Parametero

where ‘Parametero ’ is the value of the parameter at the time equal to 0 (at the beginning of
the experiment), and ‘Parameteri ’ corresponds to the value of the parameter at any time
during the experiment.
For the kinetic study of organic matter degradation by photo-Fenton reaction, the TOC
parameter was selected due to its high selectivity and sensibility to any change in organic
matter [42]. In this sense, taking into account that the reaction was developed in a batch
stirred tank reactor and considering a constant density of the mixture, TOC conversion
could be calculated as follows:
(TOCo − TOCi )
XTOC = (4)
TOCo

where ‘TOC0 ’ is the TOC value at t = 0 h (at the beginning of the experiment), ‘TOCi ’ is the
TOC value at any time during the photoreaction, and ‘XTOC ’ is the degree of conversion of
the organic matter represented on TOC base.
The mathematical calculation and graphics were made by using the Excel program.

4. Conclusions
For the degradation of OMW, different oxidation systems (air injection, artificial UV
light, hydrogen peroxide addition, UV/H2 O2 , and HFeO2 /UV/H2 O2 ) were used. In the
case of air injection, the following removal percentages were achieved: %COD = 35.5%;
%TOC = 15.0%; %TPCs = 57.0 %, and %turbidity = 72.5%. Artificial UV light degraded
OMW but to a lesser extent than hydrogen peroxide. All oxidation systems used in this
work recorded removal percentages above 50% for total phenolic compounds, except
for the air injection system, and the highest percentage (88.8%) was recorded for the
UV/H2 O2 /HFeO2 system when 50 g/L of HFeO2 was used as catalyst. This fact makes
it possible to extrapolate this treatment system to other industrial wastewaters. The use
of heterogeneous oxidation systems allows treatment without catalyst contamination and
reduces overall treatment costs. Finally, it can be indicated that the oxidation system by
heterogeneous catalysis, studied in this work, could be complemented with other upstream
or downstream separation units to achieve a higher percentage of degradation in order
to comply with the legal standards established for the quality of treated water for use in
irrigation or in the process itself.

5. Patents
Hodaifa, G.; Agabo-García, C. Method for wastewater treatment based on photo-
oxidation by ultraviolet light. Patent ES-2673673-B1, 2019.
Catalysts 2021, 11, 557 12 of 13

Author Contributions: Conceptualization, G.H.; methodology, G.H.; software, G.H. and C.A.-G.;
validation, G.H., N.C., and C.A.-G.; formal analysis, G.H. and N.C.; investigation, N.C. and G.H.;
resources, G.H.; data curation, G.H., N.C., and C.A.-G.; writing—original draft preparation, C.A.-G.;
N.C and G.H.; writing—review and editing, G.H.; visualization, G.H.; supervision, G.H.; project
administration, G.H.; funding acquisition, G.H. All authors have read and agreed to the published
version of the manuscript.
Funding: This research was funded by Junta of Andalusia and Ministry of Economy and Competi-
tiveness (Spain) “Project: Application of advanced oxidation technologies for treating of washing
wastewaters of olive oil and olives, grant number AGR-7092”.
Data Availability Statement: The data presented in this study are available on request from the
corresponding author.
Acknowledgments: The Junta of Andalusia and Ministry of Economy and Competitiveness (Spain)
are acknowledged for financial support through Project Ref.: AGR-7092 “Application of advanced
oxidation technologies for treating of washing wastewaters of olive oil and olives”. Authors also
thank the University of Pablo de Olavide for its “Financing of the Bridge Projects” charged to the
Strengthening Plan for R+D+i funded by the Ministry of Economy and Knowledge of the Junta of
Andalucía, Ref.: CTM2016-78950-C2-1-R.
Conflicts of Interest: The authors declare no conflict of interest.

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