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Science of the Total Environment 648 (2019) 601–608

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Science of the Total Environment

journal homepage: www.elsevier.com/locate/scitotenv

Comparison of different detoxification pilot plants for the treatment of


industrial wastewater by solar photo-Fenton: Are raceway pond reactors
a feasible option?
A. Cabrera-Reina a,⁎, S. Miralles-Cuevas a, G. Rivas b,c, J.A. Sánchez Pérez b,c
a
University School of Mechanical Engineering (EUDIM), University of Tarapacá, Avda. General Velásquez 1775, Arica, Chile
b
Chemical Engineering Department, University of Almería, Ctra. Sacramento s/n, Almería, Spain
c
Centro de Investigaciones de Energía Solar (CIESOL), Joint centre University of Almería – CIEMAT, Ctra. Sacramento s/n, Almería, Spain

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Treatment capacities of different pilot


plants for solar photo-Fenton are com-
pared.
• Raceway pond is used to treat industrial
wastewater at different liquid depths.
• Flat collector and CPC photoreactor are
used to treat industrial wastewater.
• Economic treatment capacity is defined
for photoreactor comparison.

a r t i c l e i n f o a b s t r a c t

Article history: This paper represents a first approach in the study of photoreactor selection to treat industrial wastewater
Received 25 April 2018 using solar photo-Fenton. In this context, simulated textile industry effluent containing a mixture of four
Received in revised form 24 July 2018 dyes at different initial dissolved organic carbon (DOC) concentrations (45, 90, 180 and 270 mg/L) was
Accepted 10 August 2018
treated by using three different solar reactor geometries: (i) tubular (5 cm diameter) provided with com-
Available online 15 August 2018
pound parabolic collector (ii) tubular (5 cm diameter) provided with flat collector and (iii) open channels
Editor: Paola Verlicchi forming raceway ponds with two liquid depths (5 and 15 cm). For comparison purposes, mineralisation
percentages over 75% and chronic toxicity reduction were set as treatment goals. Regardless of the initial
Keywords: DOC concentration, negligible differences in terms of treatment time and hydrogen peroxide consumptions
Solar photoreactor were found between the flat collector and compound parabolic collector photoreactors. Conversely, the
Photo-Fenton treatment in the raceway pond reactors always resulted in higher values. In spite of this, when the
Dye wastewater photoreactors were compared in terms of treatment capacity (mg of DOC removed/m2 min) the raceway
CPC pond reactor at 15 cm of liquid depth presented the best results, with values as much as two or three
Raceway
times higher than those of the tubular reactors, except for the wastewater with 270 mg of DOC/L for
which the raceway pond reactor at 5 cm liquid depth became the best option. When the treatment capacity
is modified to include the photoreactor investment (mg of DOC removed/€ m2) the differences between the

⁎ Corresponding author.
E-mail address: acabrera@limza.cl (A. Cabrera-Reina).

https://doi.org/10.1016/j.scitotenv.2018.08.143
0048-9697/© 2018 Elsevier B.V. All rights reserved.
602 A. Cabrera-Reina et al. / Science of the Total Environment 648 (2019) 601–608

raceway pond reactor at both liquid depths and the photoreactors with solar collectors increased by as
much as two orders of magnitude, which demonstrates the potential application of the former for the treatment
of industrial wastewater by solar photo-Fenton.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction simpler solar collectors, for instance the flat collector (FC), remain
almost unexplored.
Any industrial application of a photocatalytic process requires a This paper represents a first step in the study of photoreactor
photoreactor, which is distinctive from classic reactors because the selection to treat industrial wastewater using solar photo-Fenton. In
rates of photochemical reactions are functions of the position in the this context, simulated textile industry effluent containing a mixture
reaction zone. This is due to the unavoidable non-uniformity of the of four dyes at different initial DOC concentrations (45, 90, 180 and
radiation field caused by photon absorption (homogeneous media) or 270 mg/L) was treated using three different solar detoxification pilot
absorption and scattering (heterogeneous media) (Alfano et al., 2009). plants: (i) CPC photoreactor (ii) FC photoreactor and (iii) RPR. Two liq-
Water treatment photoreactors can essentially be divided into two uid depths (5 and 15 cm) were used for RPR while 5 cm tube diameter
different types: (i) Concentrating reactors (ii) Non-concentrating was used for tubular reactors. With the aim of achieving mineralisation
reactors (Malato et al., 2007). Within the first category, the most used percentages over 75% and reducing chronic toxicity, at least, to slight
photoreactors were probably parabolic-trough collector (PTCs), which levels, the photoreactor performances were compared in terms of treat-
consist of a structure that supports a reflective concentrating parabolic ment time, hydrogen peroxide consumption, accumulated energy (QUV)
surface. Although the PTC has been proved effective for wastewater and treatment capacity (TC) expressed as the mass of mineralised DOC
treatment (Spasiano et al., 2015), its use has been neglected due to per unit of time and photoreactor surface unit. Also a new parameter,
high cost. On the other hand, Compound Parabolic Collectors (CPC) the economic treatment capacity (TCE) was defined.
considered non-concentrating devices or low concentrating devices
(1–1.5 sun), are the most extensively used photoreactors in this field. 2. Materials and methods
CPCs present two connected parabolic mirrors and an absorber tube in
the axis. Thanks to the design of the reflector surface most of the 2.1. Reagents and analytical methods
incident radiation, including the diffuse component, can be used so
that the light is reflected through the upper part of the tube, favouring Textile industry effluent was simulated by dissolving a mixture of
the complete illumination of the system (Goswami et al., 1997). four dyes with each compound providing equal DOC concentration to
In spite of the importance of radiation distribution in the tubes, it has wastewater. The dyes were purchased from Sigma-Aldrich, in tap
been reported that the photo-Fenton process can reach photosaturation water: (i) Acid Red 1 (CAS Number 3734-67-6, Molecular Weight
from a certain UV radiation level (Carra et al., 2014a) and also that the (MW) 509.42 g/mol), (ii) Acid Yellow 17 (CAS Number 6359-98-4,
production of radical excess can be counter-productive for the process MW 551.29 g/mol), (iii) Reactive Black 5 (CAS Number 17095–24-8,
(Cabrera Reina et al., 2017). These statements are extremely important MW 991.82 g/mol) and (iv) Reactive Orange 16 (CAS Number 12225-
as photo-Fenton could be also efficiently run with more simple 83-1, MW 617.54 g/mol). Their chemical structures are shown in
photoreactors selecting adequate operation conditions. In this sense, Fig. 1. The catalyst, Fe(II), was added in the reaction bulk as FeSO4⋅7H2O
very interesting works have been recently carried out using non- (99%), which was obtained from Fluka. The oxidant agent, hydrogen
concentrating low cost raceway pond reactors (RPR) for the treatment peroxide (H2O2; 33% w/v), was provided by Sigma-Aldrich. Sulphuric
of contaminants of emerging concern (μg/L–ng/L) (De Obra et al., acid (95–97%), used for pH adjustment, was purchased from J.T. Baker.
2017; Arzate et al., 2017; Carra et al., 2014b). The results have proved The decontamination process was followed measuring the DOC con-
that, for micropollutant removal by solar photo-Fenton, UV light excess centration using a Shimadzu-VCHP TOC analyser fitted with an auto-
likely occurs when using tubular reactors and, therefore, increasing the sampler system. The hydrogen peroxide concentration was determined
path length could be a good solution to improve process efficiency. with the ammonium metavanadate colorimetric method proposed by
Industrial wastewater treatment requires a much higher amount of Nogueira et al. 2005 (Nogueira et al., 2005) while iron species concen-
radicals as the pollutants are present in the order of mg/L and, conse- tration in water was measured by means of the o-phenanthroline
quently, the above-explained considerations are not valid for this par- standardised spectrometric method (ISO 6332). Absorbance measure-
ticular case. So far, the CPC photoreactor is considered the best choice ments were carried out with a Hach Lange DR 5000 spectrophotometer.
when treating industrial (toxic and non-biodegradable) wastewater
by solar photo-Fenton although some key points could also support 2.2. Solar detoxification pilot plants
the use of different detoxification plants. Industrial wastewater is
characterised by its important variability. A wide range of characteris- The experiments were carried out in three types of photoreactors
tics accounting for inorganic salts, dissolved organic carbon (DOC) con- installed at CIESOL, Centro de Investigaciones de la Energía Solar,
centration, volatile compounds, suspended solids, or colour, among Almería (Spain):
many others can be found depending, mainly, on the industry sector
(Doumic et al., 2015; Chatzisymeon et al., 2006). a) CPC photoreactor: this solar detoxification plant consist of two twin
Although major efforts are being made to study new photoreactor loops each containing two Pyrex glass tubes fitted onto the focus of
configurations, this research field seems to be still in its infancy, two CPC mirrors, tilted 37° (local latitude). The total illuminated sur-
especially considering that most of the photoreactor development face per loop is 0.42 m2, the illuminated volume is 4.77 L and total
carried out in the 90s was done based on heterogeneous (TiO2) volume is 7 L. The simulated industrial effluent is recirculated
photocatalysis experiments. While 333 scientific papers can be found through the system (reservoir tank, piping and glass tubes) by
when searching for the terms “photo-Fenton + CPC” in a specific means of a centrifugal pump.
search engine (www.sciencedirect.com), only 24 were found when b) FC photoreactor: this solar detoxification plant follows exactly the
searching for “photo-Fenton + Raceway”. Furthermore, intermediate same scheme as the previous one but using a flat mirror, also tilted
configurations between RPRs and CPC photoreactors like the use of 37° (local latitude), instead of CPCs.
A. Cabrera-Reina et al. / Science of the Total Environment 648 (2019) 601–608 603

Fig. 1. Chemical structures of Acid Red 1, Acid Yellow 17, Reactive Black 5 and Reactive Orange 16. (For interpretation of the references to colour in this figure legend, the reader is referred
to the web version of this article.)

c) RPR: these pilot plants consist of two Polyvinyl Chloride (PVC) RPRs decontamination process. On the other hand, the initial DOC was
whose total volumes are 18 L (5 cm liquid depth) and 80 L (15 cm selected between 45 and 270 mg/L based on two studies found in the
liquid depth). The illuminated surfaces are 0.36 m2 for 5 cm liquid bibliography (Doumic et al., 2015; Chatzisymeon et al., 2006). Both
depth and 0.53 m2 for 15 cm liquid depth. Each RPR includes a Doumic et al., 2015 and Chatzisymeon et al., 2006 use simulated textile
paddlewheel connected to an engine to obtain good mixing condi- effluent according to the information obtained from textile dyeing
tions and homogeneous flow during the treatment. companies, Erfoc-Acabamentos Texteis S.A. (Portugal) and EPILEKTOS
S.A. (Greece), respectively. The sampling times were: 0, 5, 10 min and,
from that moment, every 10 min until the end of the assays. The
experiments were carried out during the end of July and the beginning
As photochemical processes depend on the accumulated energy of August (2017) and each experiment was started between 12:00 noon
arriving at the reactor surface instead of treatment time, the solar UV ra- and 1:00 pm so that most of them can be directly compared in terms of
diation (W/m2) was measured using a Delta Ohm radiometer (model LP treatment time as negligible differences between average UV radiation
UVA 02 AV) with a 327–384 nm spectral response range. This device values during the experiments were found (see Table 1). The operation
was mounted on a horizontal platform when the RPRs reactors were temperatures were also very similar in all the assays, although slightly
used while for the CPC and FC photoreactors it was mounted on a plat- lower in the RPRs experiments (2–3 °C). In any case, the accumulated
form tilted 37°. The pH and temperature were monitored by means of energy received at the photoreactor surface (QUV) was also calculated
CRISON 5335 sensor. These instruments, sensor and UV radiometer, (Eq. (1)) for each sample:
were connected to a data acquisition card (Labjack U12) to allow the
measurements to be stored on a computer. Ai
Q UV;nþ1 ¼ Q UV þ ðtnþ1 −tn Þ∙UV∙ ð1Þ
V
2.3. Experimental procedure
Where the subscript “n” refers to the sample number, UV (W/m2) is
In a typical run, the corresponding treatment volume (7 L for the CPC the average UV solar radiation measured between treatment times
and FC photoreactors, 18 L for the RPR with 5 cm liquid depth and 80 L tn and tn+1, Ai (m2) is the irradiated surface of the photoreactor and
for the RPR with 15 cm liquid depth) containing the four-dye mixture V (L) corresponds to the total volume of wastewater loaded in the
and the catalyst was loaded in the corresponding pilot plant. Notice pilot plant.
that before iron addition, the pH was adjusted to 2.8 in order to avoid
its precipitation. After 5 min of dark recirculation in the photoreactor, 2.4. Chronic toxicity bioassay
the initial amount of H2O2 was added to the reaction bulk and, immedi-
ately afterwards, the photoreactor was uncovered initiating the experi- Simulated textile effluents were tested before and after photo-
ment and data acquisition. Fenton treatment in a concentration series of 100, 50, 25, 12.5 and
The selected initial iron concentration -Fe(II)- was 20 mg/L, as this is 6.25% (v/v) to evaluate chronic toxicity. Each test was repeated at
considered the optimal concentration when using the solar photo- least two times. The pH was adjusted to pH ~ 7, and the remaining
Fenton process in CPC photoreactors with a 5 cm tube diameter hydrogen peroxide was removed with bovine liver catalase. Toxicity re-
(Malato et al., 2004; Malato et al., 2009). The initial H2O2 concentration sults were expressed as a percentage of toxic effect (inhibition).
was established at 600 mg/L and, afterwards, the remaining concentra- Chronic toxicity was evaluated using the commercial Protoxkit F™
tion in solution was determined in each sample adding 400 mg/L every toxicity test. The growth inhibition of the ciliate protozoo Tetrahynema
time this value was below 200 mg/L. In this way, the assays were always termophila after 24 h exposure was performed following the Protoxkit
run under H2O2 excess assuring that this factor never limited the F (1998) standard operational procedure. The test is based on the
604 A. Cabrera-Reina et al. / Science of the Total Environment 648 (2019) 601–608

Table 1
Average UV radiation values during the experiments.

Wastewater initial DOC concentration

45 mg/L 90 mg/L 180 mg/L 270 mg/L

CPC photoreactor 27.9 ± 1.1 W/m2 27.7 ± 1.3 W/m2 26.1 ± 1.7 W/m2 26.1 ± 2.3 W/m2
FC photoreactor 26.4 ± 0.9 W/m2 26.6 ± 1.5 W/m2 25.6 ± 2.5 W/m2 21.1 ± 2.7 W/m2
RPR at 5 cm liquid depth 24.1 ± 1.7 W/m2 24.1 ± 1.7 W/m2 25.8 ± 1.9 W/m2 26.8 ± 2.6 W/m2
RPR at 15 cm liquid depth 24.3 ± 0.9 W/m2 24.7 ± 1.4 W/m2 26.0 ± 1.9 W/m2 26.4 ± 2.3 W/m2

turnover of substrate into ciliate biomass. While normal proliferating wastewater. This comparison is evaluated in terms of: (i) treatment
cell cultures clear the substrate suspension in 24 h, inhibited culture time, H2O2 consumption and QUV (ii) TC and (iii) TCE.
growth is reflected by the remaining turbidity. Optical density measure-
ments of the turbidity quantify the degree of inhibition. Freshwater 3.2. Chronic toxicity and treatment goal selection
was used as negative control and K2Cr2O7 (56 mg/L Cr6+) was used as
positive control (Freitas et al., 2017). The objective mineralisation percentages used for the photoreactor
comparison were selected based on the results obtained in the CPC
3. Results and discussion photoreactor, which included chronic toxicity analysis. An initial and
final screening was performed to elucidate possible risks of long-term
3.1. Evaluation of the Fenton reaction toxicity. The samples were evaluated at least twice, but only for the
CPC photoreactor, as toxicity is independent of photoreactor geometry.
The Fenton contribution for each industrial wastewater (45, 90, 180 According to the effluent classification proposed by Persoone et al.,
and 270 mg of DOC/L) was evaluated prior to the solar photo-Fenton 2003 the toxicity can be represented by the percentage of inhibition
decontamination assays. As this process occurs in the dark, the and immobilisation (percentage effect, PE). The hazard classification
experiments were only carried out in the CPC photoreactor. In all the system for natural waters defines Class I for PE b 20%, Class II for
cases, 20 mg of Fe/L and 600 mg of H2O2/L were selected as initial 20 b PE b 50%, Class III for 50 b PE b 100%, Class IV when PE = 100%
reagent concentrations while (ambient) temperature was almost in at least one test and Class V when PE = 100% in all tests. All classes
constant (30–32 °C) during each experiment. are accompanied by a concise judgment: Class I: no chronic toxicity,
Independent of the wastewater type, there was an important DOC Class II: slight chronic toxicity, Class III: chronic toxicity, Class IV: high
initial decrease and, afterwards, the DOC concentration remained con- chronic toxicity and Class V: very high chronic toxicity.
stant for the next 25 min (Fig. 2). At that time, the experiments were In this sense, in Table 2 the percentages of inhibition/immobilisation
concluded resulting in 24.3%, 22.7%, 21.2% and 17.1% final for initial and final samples as well as their classification are shown.
mineralisation percentages for the 45, 90, 180 and 270 mg of DOC/L Despite most of the toxicity tests in scientific works being performed
wastewaters, respectively. The mineralisation profiles responded to with Algae sp., the use of decomposers such as the ciliate protozoo se-
typical Fenton behaviour in which, initially, Fe(II) reacts with H2O2 lected for this study (Tetrahynema termophila) represent excellent eco-
yielding hydroxyl radicals and Fe(III). Then, the process was stopped toxicological test species due to their important role in the microbial
due to the extremely low reaction rate between Fe(III) and H2O2 foodweb, wide distribution and abundance (Gerhardt et al., 2010). The
(Pignatello et al., 2006). A linear increase of the DOC removed in relation initial simulated textile effluent with 45 DOC mg/L presented chronic
to the wastewater initial DOC concentration was observed (inset Fig. 2), toxicity (Class III) while, for the rest of initial concentrations, the efflu-
which indicates that the selected H2O2:iron ratio provided enough ents presented high chronic toxicity (Class IV). The photo-Fenton treat-
initial radicals not to limit the mineralisation process. ment decreased the chronic toxicity in each case although it could only
From this point, this work is focused on the comparison of the differ- be completely removed (Class I) for the simulated effluent with the
ent pilot plants for each level of initial DOC in the simulated industrial lowest initial concentration (45 mg of DOC/L). When the initial DOC
concentration was equal to or higher than 90 mg of DOC/L, the solar
treatment could reduce the toxicity to Class II, i.e., slight chronic toxicity.
Based on these results, the treatment goals for the photoreactors com-
1 parison were established in 75% mineralisation for the 45 mg of DOC/L
wastewater, 80% mineralisation for the 90 mg of DOC/L wastewater
and 85% mineralisation for the 180 and 270 mg of DOC/L wastewaters.
0.8 Colour was also measured in each assay; nevertheless, as complete
colour removal was achieved at low mineralisation levels this variable
50
was not used for the comparison of the photoreactors. These results
DOC removed (mg/L)

45
0.6
DOC/DOC0

40 also show that the inner filter effect, typically found on textile wastewa-
35
30 45 mg/L ters, can be considered a minor factor.
0.4 25 90 mg/L
20
15
180 mg/L
Table 2
10 270 mg/L
5 Percentages of inhibition (Chronic; T. thermophila) and toxicity classification.
0.2 0
0 200 Wastewater initial DOC Chronic toxicity Hazard classification
Wastewater initial DOC (mg/L) (mg/L) (%Inhibition of T. termophila) (S0/SF)
0 (S0/SF)a
0 10 20 30 45 86.3/7.3 III-I
time (min) 90 100.0/29.2 IV-II
180 100.0/38.2 IV-II
270 100.0/43.6 IV-II
Fig. 2. Fenton degradation profiles of the simulated industrial wastewater at the different
a
initial DOC concentrations studied. S0: initial sample, SF: final sample.
A. Cabrera-Reina et al. / Science of the Total Environment 648 (2019) 601–608 605

3.3. Comparison of the photoreactors in terms of treatment time and QUV

Average solar UV radiation (W/m2)


7
The degradation of the industrial wastewater with 45 mg of DOC/L 25
CPC and FC
showed no relevant difference when using the CPC or FC photoreactor. 6
The treatments reached the 75% mineralisation level after 14 min and RW 5cm 20
17 min, respectively, with equivalent degradation profiles and similar 5

QUV (kJ/L)
RW 15cm
H2O2 consumptions, 1096 and 972 mg/L, respectively. QUV was higher 4 15
for the FC photoreactor (1.71 kJ/L) than for the CPC photoreactor Solar UV
(1.44 kJ/L). The treatments in the RPR resulted in higher treatment 3
10
times, increasing to 27 and 39 min for the 5 cm and 15 cm liquid depths,
respectively, although this increase cannot be considered significant 2
taking into account sampling times. Indeed, in Fig. 3 where the compar- 5
1
ison of the different degradation profiles for this wastewater is shown, it
can be seen how the degradation curve of the RPR at 5 cm liquid depth is 0 0
just slightly delayed with respect to the CPC and FC photoreactors. On 0 20 40 60
the other hand, at 15 cm liquid depth, this delay becomes more impor- time (min)
tant. In a similar way, the H2O2 consumption in the RPR at 5 cm of liquid
depth was almost equivalent to those of the CPC and FC photoreactors; Fig. 4. Evolution of QUV in the different pilot plants during a typical summer day at noon.
however, the consumption increased more than 40% when the RPR at
15 cm of liquid depth was used. Notice that these consumptions should
only be considered as reference values because the treatments were excess as the extra 0.32 kJ/L arriving at the photoreactor surface did
carried out under H2O2 excess. This favours side reactions not related not represent any improvement of the decontamination process.
to mineralisation but with dissolved oxygen generation increasing Furthermore, as the CPC mirror provides better radiation distribution
H2O2 consumption (Santos-Juanes et al., 2011); consequently, these than the FC mirror, this difference in the energy available between the
values can be optimized. QUV in the RPRs resulted in much lower values, photoreactors was actually higher than 0.32 kJ/L. Conversely, the
0.82 kJ/L and 0.31 kJ/L for the 5 cm and 15 cm liquid depths, respectively. treatment time needed to achieve the objective mineralisation level in
It must be taken into account that QUV represents the energy arriving at the RPRs increased to 37 min when using 5 cm of liquid depth and to
the photoreactor surface per unit of liquid volume. Under the same solar 46 min when using 15 cm of liquid depth. Only the H2O2 consumption
conditions, photoreactors with different geometries and configurations of the 15 cm liquid depth experiment increased slightly to 1344 mg/L.
receive different amounts of energy per photoreactor surface unit. The consumption for the 5 cm of liquid depth assay resulted in
This is represented in Fig. 4 where the variation of QUV in each type 1277 mg/L, which is equivalent to that obtained in the CPC photoreactor.
of photoreactor during the same summer day at noon in Almería is In the case of the 180 mg of DOC/L industrial wastewater (Fig. 6), the
shown. This highlights a problem with using QUV as a variable to track performances of the CPC and FC photoreactors were also very similar.
treatment advance because, although it is very useful to compare exper- The treatment times to reach 85% mineralisation were 67 and 68 min
iments carried out in different days in the same photoreactor, it does not and the H2O2 consumptions were 1875 and 1892 mg/L, respectively.
appear to be a good option for comparing the performance of different The QUV value in the CPC photoreactor (6.82 kJ/L) was again higher
photoreactors. Thus, this particular case of photoreactor comparison en- than in the FC photoreactor (5.72 kJ/L), therefore, it can be concluded
courages the necessity of exploring new reference variables. that the process was carried out under clear UV radiation excess in the
The results corresponding to the treatment of the industrial waste- CPC. The RPR assays presented much higher treatment times. When
water with 90 mg of DOC/L (Fig. 5) were very similar to those of the the liquid depth was 5 cm, the treatment time needed was 97 min
45 mg of DOC/L industrial wastewater. No difference was found while, for the 15 cm liquid depth, this time was 250 min. This was the
between the CPC and the FC photoreactors in terms of treatment time first time in which the process was actually affected by the lower radia-
(24 and 22 min, respectively) and just a minor variation in H2O2 tion level and worse radiation distribution in the RPR reactors respect to
consumption (1247 and 1097 mg/L, respectively). QUV was higher in the photoreactors with solar collectors as the treatment times increased
the CPC photoreactor (2.48 kJ/L) than in the FC photoreactor 45% and 273%, respectively. The low radical production rate for the
(2.16 kJ/L), which means that the process was carried out under light

CPC CPC
1 1 FC
FC
RW 5 cm
0.8 RW 5 cm 0.8
DOC/DOC0

RW 15 cm
DOC/DOC0

RW 15 cm 0.6
0.6

0.4 0.4

0.2 0.2

0 0
0 20 40 60 0 20 40 60 80
time (min) time (min)

Fig. 3. Degradation profiles of the wastewater at 45 mg of DOC/L in the CPC, FC and RPR Fig. 5. Degradation profiles of the wastewater at 90 mg of DOC/L in the CPC, FC and RPR
(5 cm and 15 cm). (5 cm and 15 cm).
606 A. Cabrera-Reina et al. / Science of the Total Environment 648 (2019) 601–608

148 min at 5 cm of liquid depth, which is 59 min more than the treat-
CPC ment in the CPC photoreactor. In this case it is clear that the lower radi-
1 FC ation level arriving at the photoreactor surface together with the worse
RW 5 cm radiation distribution in the RPR is significantly affecting the photo-
0.8 Fenton cycle, diminishing the amount of radicals produced and limiting
RW 15 cm
the organic matter mineralisation. This important difference in terms of
DOC/DOC0

treatment time also affected the H2O2 consumption, which at the end of
0.6
the process was also higher, 2923 mg/L. Nevertheless, QUV was still
much lower (3.10 kJ/L) than in the CPC and the FC photoreactors. On
0.4 the other hand, the experiment with 15 cm of liquid depth did not
reach the objective mineralisation level after 250 min. At that illumina-
0.2 tion time only 30% of the initial DOC could be degraded and half of this
percentage was degraded within the first 5 min when the Fenton (dark)
0 reaction took place. Thus, the feasibility of the RPR application to indus-
0 50 100 150 200 250 trial wastewater treatment seems to be limited at this point, although
time (min) diminishing the catalyst concentration could be a possible solution in
order to expand this limit of application at high liquid depths.
Fig. 6. Degradation profiles of the wastewater at 180 mg of DOC/L in the CPC, FC and RPR
(5 cm and 15 cm). 3.4. Comparison of the photoreactors in terms of treatment capacity

Treatment capacity (TC), which can be calculated using Eq. 2, is a


15 cm liquid depth allows two stages to be distinguished in the degra- useful variable for the comparison of different photoreactors as it repre-
dation profile, which is in accordance with the results published by sents the amount of DOC removed per photoreactor surface unit and
Casas López et al. 2010 (Casas López et al., 2010). In a first step, the rad- time unit.
icals attack the dyes molecules but without mineralisation while, in a
second stage, these attacks result in DOC decrease because of the higher Om ∙½DOC0 ∙VR
TC ¼ ð2Þ
simplicity of the generated organic matter. On the other hand, the dif- Ai ∙t
ferences in H2O2 consumptions were very similar to the above-
commented experimental sets. For the 5 cm liquid depth assay the Where Om is the objective mineralisation level (expressed as a decimal),
H2O2 consumption was 2030 mg/L while it increased to 2821 mg/L for [DOC]0 is the initial concentration of the wastewater (mg/L), VR is the
the 15 cm liquid depth assay. treatment volume (L) and t is the treatment time needed to achieve
The experimental set with wastewater at 270 mg of DOC/L pre- the objective mineralisation (min).
sented the most important differences of the whole study (Fig. 7). The The TC variation in the different pilot plants with the wastewater ini-
treatment time needed to achieve the objective mineralisation percent- tial DOC concentration is shown in Fig. 8. The TC was always higher in
age in the FC photoreactor was slightly higher than in the CPC the RPRs than in the CPC and the FC photoreactors. In spite of the higher
photoreactor, resulting in 15 min of additional treatment time. Never- treatment times needed when the process was carried out without solar
theless, taking into account that the experiment in the FC photoreactor collectors, this increase was not high enough to compensate for the
was carried out under an average UV solar radiation of 21.1 W/m2 higher volume to surface ratios of the RPRs (50 and 150 L/m2 for the
which is considerably lower than the average UV solar radiation of the 5 cm and 15 cm liquid depths, respectively) compared with that of the
experiment in the CPC photoreactor, 26.1 W/m2, the increase in the CPC and FC photoreactors (16.7 L/m2). The 15 cm liquid depth always
treatment time was probably caused by the different solar light levels resulted in the best option, except for the treatment of the 270 mg of
instead of the photoreactor characteristics. The H2O2 consumption in DOC/L wastewater where the objective mineralisation could not be
the FC photoreactor was not affected, resulting in 2304 mg/L, which is achieved after 250 min. For the 45 mg of DOC/L wastewater, the TC in
equivalent to the 2260 mg/L needed in the CPC photoreactor. With re- the RPR at 15 cm of liquid depth was twice the TC of the RPR at 5 cm
spect to the treatment in the RPRs, the illumination time increased to of liquid depth and more than three and four times the TCs of the CPC

CPC
CPC
FC
1 FC
(mg of DOC removed/m2 min)

RW 5 cm 200.0 RW 5cm
RW 15cm
Treatment capacity

0.8 RW 15 cm
DOC/DOC0

150.0
0.6
100.0
0.4

0.2 50.0

0 0.0
0 50 100 150 200 250 45 90 180 270
time (min) Wasterwater initial DOC concentration (mg/L)

Fig. 7. Degradation profiles of the wastewater at 270 mg of DOC/L in the CPC, FC and RPR Fig. 8. Comparison of treatment capability (TC) achieved in each pilot plant for the
(5 cm and 15 cm). different simulated industrial wastewaters.
A. Cabrera-Reina et al. / Science of the Total Environment 648 (2019) 601–608 607

and FC photoreactors, respectively. These differences were even higher Table 3


when treating the 90 mg of DOC/L wastewater as the TCs in the RPRs in- Economic treatment capacity of each photoreactor type.

creased considerably at both liquid depths while it slightly increased in Economic treatment capacity (TCE)
the CPC and FC photoreactors. The effect of Fenton is so important to (mg of DOC removed/€·min)
this initial wastewater concentration that increasing RPR depth is an ad- Wastewater initial DOC concentration (mg/L) 45 90 180 270
vantage instead of a disadvantage. For the next wastewater concentration, 2
Installation surface: 10,000 m
180 mg of DOC/L, the TC of the RPR at 15 cm liquid depth was 81.0 mg of CPC photoreactor 0.32 0.37 0.26 0.30
DOC removed/m2·min, which is very similar to the TC of the RPR at 5 cm FC photoreactor 0.31 0.50 0.32 0.32
liquid depth, 69.4 mg of DOC removed/m2·min. The process efficiency in RPR at 5 cm liquid depth 8.30 12.26 9.26 9.15
the deepest RPR is being negatively affected by the higher amount of ini- RPR at 15 cm liquid depth 11.48 19.78 7.20 –
tial organic matter, however, the TC values in the RPRs are still much Installation surface: 1000 m2
higher than the TCs of the CPC and FC photoreactors, 33.4 and 33.3 mg CPC photoreactor 0.08 0.09 0.07 0.08
of DOC removed/m2·min, respectively. Consequently, the use of RPR for FC photoreactor 0.08 0.13 0.08 0.08
RPR at 5 cm liquid depth 2.08 3.07 2.31 2.29
the treatment is still justified under these conditions even though an
RPR at 15 cm liquid depth 2.87 4.95 1.80 –
application limit can be expected from this point due to the important ef-
ficiency loss in the RPR at 15 cm liquid depth. Indeed, for the highest
wastewater initial DOC concentration, the use of the RPR at 5 cm of liquid
depth resulted in the best option as the treatment at 15 cm liquid depth wastewater by solar photo-Fenton. It should be taken into account that
could not be completed. There was almost no change of the TC the whole study was carried out in summer around noon so that light
(68.6 mg of DOC removed/m2 min) with respect to the previous waste- availability was always high, which was favourable for the FC
water DOC concentration, therefore, as the TCs of the CPC and the FC photoreactor and especially for the RPRs. Performance in the morning
photoreactors were also very similar to those of the 180 mg of DOC/L and during winter should be also studied in order to determine whether
wastewater, 38.1 and 33.1 mg of DOC removed/m2 min respectively, or not the CPC photoreactor can compensate the important TC differ-
the differences in photoreactor performance remained unchanged. The ences with respect to RPR or if the FC still presents negligible differences
low TC variation in the RPR at 5 cm is probably an indication that its ap- against the CPC under these conditions. Additional studies should also
plication limit is still a long way from being reached. Further studies in optimise reagent consumptions in each pilot plant so that this effect
order to find the initial wastewater DOC concentration for which the TC can be included in the economic treatment capacity. It is well known
of the RW at 5 cm matches the TC of the CPC and FC photoreactors that H2O2 consumption represents a very important percentage of
could be very interesting. The use of intermediate liquid depths within photo-Fenton total cost (Sánchez Pérez et al., 2013) and also that iron
the range used in this work could also provide useful information. In concentration should be optimized depending on RPR liquid depth.
any case, these results suggest the potential application of the RPR to
treat industrial wastewater. 4. Conclusions

3.5. Comparison of the photoreactors in terms of economic treatment Simulated textile industrial effluent at different DOC initial concen-
capacity trations has been treated by solar photo-Fenton in CPC photoreactor,
FC photoreactor (5 cm diameter tubes both) and RPR at 5 cm and
The reported price of CPC photoreactor is about 500 €/m2 for an in- 15 cm liquid depths.
stallation of 1000 m2 (Miralles-Cuevas et al., 2016) while this value can For the simulated wastewaters with 45 and 90 mg of DOC/L, the rel-
be diminished to 129 €/m2 if the size of the treatment plant is increased ative importance of the Fenton reaction together with the low treat-
to 10,000 m2 (Tânia et al., 2016). Based on these costs and the informa- ment times needed to achieve the mineralisation goals made the RPR
tion given by different suppliers, it has been estimated that the best option in terms of TC, in spite of the slightly higher treatment
photoreactor cost can be reduced by 20% due to the use of a FC instead times obtained with respect to the tubular photoreactors. As the impor-
of a CPC, i.e. the cost is 400 €/m2 and 103 €/m2 for the 1000 and tance of the solar UV radiation is limited, increasing the liquid depth
10,000 m2 plants, respectively. The cost of the RPR has been reported from 5 cm to 15 cm allowed, approximately, doubling the TC that
as 10 €/m2 for an installation of 10,000 m2 (Carra et al., 2015) and this reached 129.1 and 222.5 mg of DOC removed/m2 min in the latter for
is the price considered for the 5 cm RPR. The same scaling-up factor of the 45 and 90 mg of DOC/L wastewaters, respectively.
the CPC plant was considered to obtain the RPR cost for the 1000 m2 sys- The same trend was found when the wastewater initial DOC was in-
tem resulting in 40 €/m2. In order to be conservative and due to the creased to 180 mg/L. However, the TC of the RPR at 15 cm liquid depth
higher size of the RPR at 15 cm liquid depth, 20 €/m2 and 60 €/m2 was significantly reduced so that the differences with the rest of the
have been considered for the 10,000 and 1000 m2 plants. Taking this in- pilot plants were lower. The higher amount of organic matter in the
formation into account a new variable was defined, the economic treat- simulated effluent increased the relative importance of photo-Fenton
ment capacity (TCE), which represents the amount of DOC removed per in the global decontamination process so that the radiation level and
time unit and photoreactor investment monetary unit (Eq. 3): its distribution in the photoreactor started to take on greater impor-
tance, but not enough to compensate for the higher volume to surface
TCE ¼ TC=Cphotoreactor ð3Þ ratio of the RPR.
In the case of the highest polluted wastewater, the treatment in the
Where Cphotoreactor is the acquisition cost of the different photoreactors RPR at 15 cm liquid depth could not be finished; indeed, only 30%
(€/m2). mineralisation was achieved after 250 min. The treatment time needed
The TCE values for each pilot plant and wastewater treated are to reach the mineralisation goal in the RPR at 5 cm was almost 1 h higher
presented in Table 3. Due to the RPRs low cost, the important differences than in the CPC photoreactor. Nevertheless, the TC of the RPR was still
already observed between the RPRs and the CPC and FC photoreactors significantly higher than those of the tubular reactors, 68.6 mg of DOC re-
in terms of TC are even increased when the photoreactor investment moved/m2 min vs 38.1 and 33.1 mg of DOC removed/m2 min for the CPC
is included in the comparison varying by as much as two orders of photoreactor and the FC photoreactor, respectively. These results showed
magnitude. the feasibility of using the RPR to treat industrial wastewater but also that
In spite of these promising results, further studies are needed to de- it presents an application limit, which depends on wastewater character-
termine the most adequate photoreactor for the treatment of industrial istics among other variables.
608 A. Cabrera-Reina et al. / Science of the Total Environment 648 (2019) 601–608

During the whole study, negligible differences were found between Chatzisymeon, E., Xekoukoulotakis, N.P., Coz, A., Kalogerakis, N., Mantzavinos, D., 2006.
Electrochemical treatment of textile dyes and dyehouse effluents. J. Hazard. Mater.
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the treatment capacity was defined (TCE –mg of DOC removed/€ min-). Enhancement of a solar photo-Fenton reaction by using ferrioxalate complexes for
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neering of solar photocatalytic collectors. Sol. Energy 77, 513–524.
Malato, S., Blanco, J., Alarcon, C.D., Maldonado, M.I., Fernandez-Ibanez, P., 2007. Photo-
This work was funded by CONICYT (FONDECYT/INICIACIÓN catalytic decontamination and disinfection of water with solar collectors. Catal.
11160680). The authors want to thank the Solar Energy Research Center Today 49, 122–137.
(CONICYT/FONDAP/15110019), Junta de Andalucía (Andalusian Malato, S., Fernández-Ibáñez, P., Maldonado, M.I., Blanco, J., Gernjak, W., 2009. Decontam-
ination and disinfection of water by solar photocatalysis: recent overview and trends.
Regional Government, P12-RNM-1437) and European Regional Devel- Catal. Today 147, 1–59.
opment Fund (ERDF). Miralles-Cuevas, S., Oller, I., Agüera, A., Sánchez Pérez, J.A., Sánchez-Moreno, R., Malato, S.,
2016. Is the combination of nanofiltration membranes and AOPs for removing
microcontaminants cost effective in real municipal wastewater effluents? Environ.
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