Journal of Industrial and Engineering Chemistry 62 (2018) 291–301

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Journal of Industrial and Engineering Chemistry

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Enhanced photocatalytic degradation of furfural and a real wastewater

using UVC/TiO2 nanoparticles immobilized on white concrete in a
fixed-bed reactor
Nazanin Gholamia , Bahram Ghasemia , Bagher Anvaripoura,* , Sahand Jorfib,c
a
Abadan Faculty of Petroleum Engineering, Petroleum University of Technology, Abadan, Iran
b
Environmental Technologies Research Center, Ahvaz Jundishapur University of Medical Sciences, Ahvaz, Iran
c
Department of Environmental Health Engineering, School of Health, Ahvaz Jundishapur University of Medical Sciences, Ahvaz, Iran

A R T I C L E I N F O A B S T R A C T

Article history:
Received 30 September 2017 TiO2 nanoparticles were immobilized on a concrete surface of fixed-bed reactor and used for furfural
Received in revised form 1 January 2018 photocatalytic degradation of real and synthetic wastewater. At optimum conditions of initial pH 9, TiO2
Accepted 5 January 2018 loading density 50 g/m2 and UV irradiation intensity 24 W, the furfural and COD removal were 98.3% and
84.2% respectively for synthetic wastewater after 5 h, while for real wastewater, COD and TOC removal
Keywords: reached 59.53% and 86.65%, respectively after 8 h. The composite reused for four consecutive cycles with
Furfural maximum 4.4% reduction in efficiency for both cases. Moreover, pseudo-first-order kinetics were best
Refinery wastewater fitted to experimental data in both cases.
Photocatalytic degradation
© 2018 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
TiO2–concrete composite
reserved.
Fixed-bed reactor

Introduction contaminants from aquatic media, including conventional treat-

ments such as with biological systems and adsorption methods
Nowadays, many industries face problems caused by wastewa- (which are generally done by activated carbon) [18–30]. The
ter containing organic compounds, some of which are known to be presence of non-biodegradable and toxic hydrocarbon compounds
major environmental contaminants. The discharge of these in aquatic media can be intractable for biological systems or may
materials in aqueous systems reduces the level of dissolved increase reaction time to remove these compounds [31–34]. Since
oxygen and disrupts the ecosystem balance [1–12]. Some of these furfural has biological toxicity, its high concentration diminishes
contaminants such as furfural and phenols are very toxic and the efficiency of biological treatment systems [35]. In the
stable. Over the long-term, these aromatic compounds can have a adsorption method, the use of expensive commercially active
negative impact and serious harmful effects on the environment carbon is not economical because of its high price and, hence, it is
[13–15]. Currently, the most widely used furfural serves as raw necessary to prepare an activated carbon having a lower price but
material to produce other chemical substances. In the refinery and the same characteristics of commercially active carbon. In addition,
petrochemical industry, it is also used as an extractant and, in activated carbon can only transfer pollutants from one phase to
recent years, has been introduced as a precursor to the production another, and, due to its removal mechanism, its ability to remove
of biofuels [16]. Owing to its high toxicity, furfural has harmful polar contaminants such as furfural is limited [36–41]. Refinery
health effects and can cause irritation when it comes into contact wastewater contains a variety of complex contaminants. Some of
with the eyes, and respiratory and gastrointestinal tracts. It is very them exist primarily in crude oil and others enter the wastewater
harmful for the skin and is easily absorbed by it, and, therefore, during the refining process. A large part of these pollutants
should be prevented from entering the environment [17]. So far, includes hydrocarbon components and toxic compounds. Owing to
different methods have been evolved to eliminate organic the high organic load of refinery wastewater and the effects of
these pollutants on the aquatic environment, most studies
consider wastewater pollutants mainly due to the presence of
hydrocarbons and offer solutions to reduce COD to an acceptable
* Corresponding author.
E-mail addresses: [email protected] (N. Gholami), [email protected]
level of environmental standards before discharging it into the
(B. Ghasemi), [email protected] (B. Anvaripour), jorfi[email protected] (S. Jorfi). environment [42–44].

https://doi.org/10.1016/j.jiec.2018.01.007
1226-086X/© 2018 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
292 N. Gholami et al. / Journal of Industrial and Engineering Chemistry 62 (2018) 291–301

Nowadays, because of an increasing presence of organic

compounds that are hard to biodegrade and are resistant to
H2 O2 þ hn ! 2OH
ð8Þ
microorganisms in wastewater streams (such as furfural), conven-
tional biological methods cannot be used for complete treatment
of the effluent, and consequently, the introduction of newer
technologies to degrade these refractory organic matter has Organic matter þ OH
! H2 O þ CO2
þ other degradation products ð9Þ
become imperative [45–47]. Therefore, upgrading WWTPs with
more advanced technologies as a pretreatment or tertiary
treatment is required for the treatment of refractory organic
matter in wastewater from refining industries [48–50]. In recent Organic matter þ O

2 ! H2 O þ CO2

years, the use of Advanced Oxidation Processes (AOPs) to remove þ other degradation products ð10Þ
organic compounds such as furfural from the aquatic environment According to the studies done, generally two types of reactors
is considered due to their high efficiencies [51–56]. are considered for the photocatalytic process: fluidized-bed and
In these processes, hydroxyl radicals are produced by a series of fixed-bed reactors [83]. A fixed-bed reactor can be used as an
reactions. Hydroxyl radicals are highly oxidative and can remove a appropriate process in water purification and wastewater treat-
wide range of organic compounds, eventually converting them into ment [84]. This method has numerous advantages and some
carbon dioxide and water [57,58]. Among all AOPs, the homoge- disadvantages. When TiO2 particles are immobilized on a suitable
neous photocatalyst method has several advantages, the main one substrate, the effective surface of TiO2 is reduced. Besides, the
being the complete mineralization of organic matter. In addition, reaction only occurs in the liquid-solid interface and, thus, the
this method does not produce any sludge and the reaction speed is mass transfer from the liquid bulk to the catalyst surface does not
greater than those of other methods. The cost of operation is less have a great impact on the reaction rate [85], as the efficiency of
compared to methods such as UV/O3 and UV/H2O2. On the other this type of reactor is lower than that of the fluidized-bed reactor
hand, this method is efficient at the ambient temperature and [86]. But it should be noted that, in this method, because TiO2 is
atmospheric pressure [59–66]. The hydroxyl radical (OH
) is immobilized on the substrate, no catalyst is able to go into the
generated by the interaction of photons having a certain energy liquid bulk during the process. Therefore, by eliminating the
with the surface of a semiconductor [54,67–70]. TiO2 is the most filtration step, costs related to the separation of catalyst from
common semiconductor, but TiO2, for reasons such as being non- solution is saved, whereas this stage is required for fluidized-bed
toxic, reasonably priced, easily available, environmentally friendly, reactors. On the other hand, TiO2 emission is prevented and the
highly photostable and chemically inert, is the most studied operators are less exposed to TiO2 particles [87,88]. The photo-
photocatalytic process [54,71–75]. TiO2, because of its high band catalyst could also be used for a longer period of time [89]. Today,
gap (3–3.2 eV), can be activated by UV illumination and completely researchers in their studies related to TiO2 photocatalytic
mineralize recalcitrant contaminants [76–78]. In the photocatalyst degradation tend to use fixed-bed reactors. This technique is
process, the electron-hole pair is formed when the catalyst is more preferred for its benefits, and it is more appropriate for use on
exposed to UV irradiation. An electron with the negative charge in an industrial scale [90,91]. The substrate used for the photo-
the conduction band and the hole with a positive charge in the catalytic process must be inert, resistant to wear and corrosion, and
valance band are formed. Each of them, by a series of reactions, have a good surface contact with the catalyst. The selected method
ensures the production of hydroxyl radicals that are expressed in for making the bed must be commensurate with the substrate
the following. Furthermore, the radical superoxide, which is type, as the catalysts have the greatest adhesion to the surface in
produced during these reactions, also has oxidizing properties and order to avoid comminution and/or detachment of catalyst
degrades the organic pollutant into intermediates and the particles from the support. Otherwise, the reactor operates as a
intermediates can be further degraded into CO2 and H2O. In some fluidized-bed reactor [92,93]. So far, a variety of substrate types
studies, the degradation of furfural is proposed to follow this path and methods for immobilizing TiO2 have been proposed including
[79–82]: flat, curved, corrugated and reticulated plates, which can be made
þ of glass, quartz, stainless steel, fiberglass, concrete, etc. [94–98].
TiO2 þ hn ! h þ e ð1Þ
Other studies also suggest the use of packed-bed reactors, while
TiO2 particles are immobilized on different forms of packs after
immersion in a solution of TiO2 [88,99–102]. The use of
H2 O þ hn ! Hþ þ OH ð2Þ
immobilized TiO2 in photocatalytic reactors have also been
suggested for the treatment of industrial wastewater [103–107].
þ
The methods used for immobilizing TiO2 include spin coating
OH þ h ! OH
ð3Þ [108], spray coating [109], sol gel dip coating [110], electrophoretic
deposition [111], and sputtering [112] have been introduced for
substrate coating. But the use of these methods is typically time
e þ O2 ! O

2 ð4Þ and energy-consuming, and each method requires special and
costly equipment [113]. Concrete is a mineral matter and a major
structural building material. The concrete, due to it porous surface,
O
þ

2 þ H ! HO2 ð5Þ will have a better adhesion with TiO2 particles [114,115]. In a recent
research, this type of substrate has been used for the removal of
organic contaminants in aquatic environments [116–119]. The use
HO
2 þ Hþ þ e ! H2 O2 ð6Þ of white cement is more appropriate because of its higher adhesion
properties than that of conventional cement, as compounds of iron
and other heavy metals in its composition is less than 0.15% [120].
H2 O2 þ e ! OH þ OH
ð7Þ Therefore, in this research, the application of white cement
substrate was tried out. The novelty of this study was to investigate
the photocatalytic property of nano-TiO2, which was immobilized
 N. Gholami et al. / Journal of Industrial and Engineering Chemistry 62 (2018) 291–301 293

on a white concrete surface to treat a refractory real refinery Reactor setup

wastewater. The experimental investigations were divided in two
parts. First, the experiment was carried out for furfural as a In each run, 400 mL of synthetic or real wastewater containing
synthetic wastewater and the influence of initial pH, catalyst furfural was poured into the reactor and then placed in a glass
loading, furfural concentration, radiation intensity and reaction chamber. The light source comprised three 8W UV-C lamps
time were examined on the removal rate of furfural in an aqueous installed over the chamber at a distance of about 4 cm from the
phase. Second, a real refinery wastewater sample was used under substrate at the bottom of the reactor and 1 cm from the surface of
selected conditions obtained from a synthetic wastewater study, the solution. Based on the Eqs. (4)–(8), the dissolved oxygen played
and the effect of the reaction time was examined on the an important role in the production of hydroxyl radicals [122,123].
degradation rate of its COD and TOC. Mineralization of synthetic However, because a fixed bed was used with no possibility of
wastewater, reusability and kinetics study of both real refinery using a magnetic stirrer, an aeration system could also help mix the
wastewater and synthetic wastewater were also examined. solution. The aeration system had four holes for air bubbles on the
floor of the reactor. A simplified schematic diagram of the
Materials and methods experimental setup is shown in Fig. 1.

Materials and instruments Photocatalytic degradation

Titanium dioxide was used as a catalyst from TitraChem All experiments were performed at atmospheric pressure and
Company (Iran). All other chemicals, furfural, hydrochloric acid, ambient temperature. The synthetic wastewater was prepared by
sodium hydroxide, and ethanol were supplied by Merck (Darm- the addition of the desired amounts of furfural to the distilled
stadt Germany). Concrete sealer ATROSIVE K50 was purchased water. The initial pH was adjusted by the addition of 0.1N HCl and/
from Atropat ChemiCompany (Iran). For the photocatalytic or 0.1N NaOH. The desired conditions for initial pH (3, 5, 7, 9, 11),
process, three 8 W UV-C lamps were purchased from Philips TiO2 loading density (10, 30, 50, 70 g/m2), reaction time (60, 120,
Company (Poland). Ultrasonic homogenizer (UIP1000hdT) from 180, 240, 300 min), radiation intensity (8, 16 and 24 W) and furfural
Heilscher Company (Germany) was used for dispersing nano-TiO2 concentration (400, 600, and 800 mg/L) were studied consecutive-
powder in slurry. The pH of wastewater was adjusted by a 3510 pH ly. The initial COD of real wastewater for all experiment was
meter from the Jenway Company (UK), and aeration of the reactor adjusted at 1200 ppm. The treatment of real wastewater was
was done by using an AP-5800 air pump from the Yamano performed under selected conditions obtained for synthetic
Company (China). The sample used for this experiment was wastewater, except for the reaction time (2–12 h). Analysis was
provided by a local refinery in Iran. The characteristics of this based on the removal efficiency using Eq. (11):
sample are described in Table 1.  
Removal ¼ ðconcentrationÞ0  ðconcentrationÞt =ðconcentrationÞ0
 100
Immobilization of TiO2 nanoparticles
ð11Þ
The substrate was prepared by mixing white cement powder where (concentration)0 and (concentration)t denote furfural and
with distilled water (1:2 w/w) and was allowed to dry for 3 days. COD concentrations before and after the photocatalytic reaction,
Thereafter, the floor of a cubic glass reactor was covered with the respectively.
white concrete substrate. The walls were coated with the substrate
using the adhesive seal. For the immobilization of TiO2 on Analytical methods
substrates, slurry was prepared by mixing nano-TiO2 powder in
55 mL of distilled water and, then, placed for 35 min in ultrasonic After each experiment, a 10 mL sample was withdrawn and
homogenizers, operated at 70 Hz frequency so that the TiO2 centrifuged for 5 min at 4000 rpm in order to separate the possible
particles were uniformly dispersed and evenly distributed on the solid phase. Then, the residual furfural concentration was
slurry. After that, 15 mL of pure methanol was added to the slurry, measured via a UV–vis spectrophotometer (DR 5000; Hach,
which was again sonicated for 5 min at 70 Hz frequency. Methanol USA) at the maximum wavelength of 277 nm [81]. COD, TSS and
enhances the adhesion strength between particles and the surface BOD5 were determined according to the standard methods for the
and also helps the substrate to dry fast. Afterwards, an epoxy sealer examination of water and wastewater [124]. Total organic carbon
was spread on the concrete surface with a brush and, after 5 min, (TOC) was measured using a TOC analyzer (Shimadzu, TOC-VCSH,
the prepared slurry was sprayed on it with a laboratory spray gun. Japan) to determine the mineralization. All the experimental data
The time required for drying each substrate was three days. After were expressed in terms of arithmetic averages obtained from at
the drying time was over, each substrate was washed with distilled least three replicates. The micrographs of the substrate surface,
water in order to remove excess TiO2 particles that had not with and without TiO2 were examined by field emission scanning
completely stuck to the surface [113,114,116,121]. electron microscopy (FESEM; Mira 3, Tescan).

Table 1
Results and discussion
The characteristics of raw refinery wastewater.

Test Results Units Characterization of TiO2–concrete composite

pH 6.5 –
TDS 22000  2440 mg/L To investigate the surface features and the mesoporous
TSS 350  37 mg/L
structure of the particles, a magnified FESEM image was analyzed.
Turbidity 31  5 NTU
TOC 700  130 mg/L The surface morphologies of the white concrete coated with and
COD 1200  368 mg/L without TiO2 are shown in Fig. 2. Fig. 2A shows the surface of the
BOD 234  104 mg/L raw concrete without the TiO2 coating, indicating that the surface
Oil 30  14 mg/L of the white concrete is heterogeneous and grainy. High-
Furfural 200 mg/L
magnification images showed high surface porosity of concrete
294 N. Gholami et al. / Journal of Industrial and Engineering Chemistry 62 (2018) 291–301

Fig. 1. Schematic of photoreactor: (1) UV lamps, (2) air pump, (3) white concrete, (4) epoxy sealer, (5) immobilized TiO2, (6) glass chamber.

Fig. 2. A) Electron micrograph of the surface of white concrete without TiO2 and B) electron micrograph of the surface of white concrete with TiO2.

as a good support for TiO2. From Fig. 2B, it is clear that the nano at a lower TiO2 loading density, the amount of TiO2 was low
TiO2 particles are uniformly coated on the concrete surface and compared to the surface area of the concrete substrate. As a result,
immobilized on it. Images with additional magnification show that fewer electrons and positive holes were produced and hydroxyl
the small nanoparticles are aggregated randomly. radical production was also reduced. Increasing the TiO2 loading
density and using greater amounts of TiO2 per unit area,
Furfural photo-degradation proportionally increased hydroxyl radical production and en-
hanced the photocatalytic degradation, whereas, for catalysts with
Effect of TiO2 loading density high TiO2 loading (>50 g/m2), the efficiency enhancement
The effects of TiO2 loading density including 10, 30, 50 and 70 g/ increased slowly. After this amount, the increase of the catalyst
m2 were studied. Experiments were carried out under the same did not much impact the removal efficiency. This phenomenon
conditions (pH = 7, UV = 16 W and reaction time = 300 min and the occurred due to the overlapping of particles at a TiO2 loading
initial concentration of furfural = 400 mg/L). The removal efficiency density greater than 50 g/m2. An increase of the TiO2 loading
increased with TiO2 loading quantity in the range 10–50 g/m2; increased the surface coverage of TiO2 on the concrete; the
whereas a further increase in the catalyst amount (above 50 g/m2) thickness of the TiO2 layer on the concrete surface was increased
resulted in a slight removal improvement (Fig. 3A). Fig. 3B shows and, finally, eliminated the effect of particles in the lower layers in
the pseudo-first-order kinetics modeling of furfural degradation, the photocatalytic process [116]. Consequently, the selected
as the TiO2 loading density was variable. It could be concluded that, amount of TiO2 had to be investigated in order to limit the
 N. Gholami et al. / Journal of Industrial and Engineering Chemistry 62 (2018) 291–301 295

Fig. 3. A) Effect of TiO2 loading on the efficiency of furfural degradation and B) Fig. 4. A) Effect of pH values on the efficiency of furfural degradation and B) pseudo
pseudo first order kinetics modeling (pH = 7, UV = 16 W and initial concentration of first order kinetics modeling (TiO2 loading density = 50 g/m2, UV = 16 W and initial
furfural = 400 mg/L). concentration of furfural = 400 mg/L).

amount of consumed catalyst and to reduce the cost as much as TiO2 surface leads to the generation of hydroxyl radicals oxidants
possible [125]. This result is in agreement with a similar work done [129,130]. On the other hand, at a higher pH (more than 9), an
by Zulfakar et al. dealing with phenol removal from water using increase in the amount of NaOH in the environment, there is
immobilized TiO2 on quartz sand [126]. practically no hydrogen ions (H+). This limits some photocatalytic
reactions (Eqs. (5)–(8)) and resulting in a reduced formation of
Effect of pH H2O2 and OH
and, consequently, lesser the degradation of organic
The influence of the initial pH level on the photocatalytic matters [130]. Similar results were obtained by Veisi et al. for
degradation was investigated by the adjustment the solution with furfural degradation in aqueous solution by N-doped titanium
NaOH and HCl. The result is shown in Fig. 4A and demonstrates dioxide nanoparticles [131].
that the rate of photocatalytic degradation depends on the initial
pH. Pseudo-first-order reactions for the degradation of furfural Effect of UV irradiation intensity
have also been observed in Fig. 4B. In the initial acidic pHs, when The greater effectiveness of UV-C compared to UV-A in
the acidity of the environment increased by the adding of HCl, the photocatalytic reactions has been proven for the degradation of
anion Cl could absorb UV radiation and react with hydroxyl certain organic material, first, because of its greater ability to direct
radicals, finally producing inorganic radical ions of hypochlorite photolysis of organic matters and, second, the higher probability of
(ClO). These inorganic radical anions were less active compared trapping electrons at an oxygen vacancy, when the photocatalyst
tohydroxyl radicals, so they did not play a significant role in the surface is exposed to photons with this energy which leads to
degradation process. There was also a drastic competition between generation of highly oxidative hydroxyl radicals [132]. The effect of
organic matters and Cl with respect to OH
[127]. Moreover, the UV-C intensity on the photocatalytic efficiency was investigated by
presence of Cl could decrease the photocatalytic rate of the TiO2 in changing the power of the UV source lamps with three different
an acidic medium. When the pH level of the aqueous media was intensities: 8 W, 16 W and 24 W. The results, given in Fig. 5Ashow
lower than the point of zero charge of the TiO2 (about 6.3), the TiO2 that furfural degradation efficiency increases when the UV
surface was positively charged (whereas it was negatively charged irradiation intensity is increased and the photocatalytic efficiency
in alkaline conditions). So anions such as Cl accumulated near the at 24 W intensity is about twice the 8W intensity. This result is also
positively charged TiO2 particles and could hinder the access of confirmed by Fig. 5B, which shows pseudo-first-order kinetics
other target compounds to the surface. Therefore, the adsorption of modeling of furfural degradation. Photons emitted from UV rays
Cl on the positively charged TiO2 surface could be another reason provide the amount of energy needed to transfer electrons from
for the resulting the lower efficiency. Hence, an increase in pH the valence band to the conduction band of a semiconductor
(reduce the amount of Cl) shows an increase in degradation photocatalyst. The energy of these photons is directly related to the
efficiency [128,129]. Fig. 4A shows that as the pH rises to 9, the UV radiation. Higher intensity of the radiation produces more
efficiency rate also increases. This can be due to the presence of photons with greater energy. Radiation of these photons on the
hydroxide ions (OH) in the environment at alkaline pH, in which semiconductor surface increases the probability of radical
the production of hydroxyl radicals (OH
) subsequently increases. hydroxyl generation in the series of photocatalytic reactions,
In other words, photooxidation of OH by positive holes on the increasing the rate of removal efficiency [67]. Borghei and Hosseini
296 N. Gholami et al. / Journal of Industrial and Engineering Chemistry 62 (2018) 291–301

Fig. 5. A) Effect of UV irradiation intensity values on the efficiency of furfural

degradation and B) pseudo first order kinetics modeling (TiO2 loading density =
50 g/m2, pH = 9 and initial concentration of furfural = 400 mg/L). Fig. 6. A) Effect of initial furfural concentration values on the efficiency of furfural
degradation and B) pseudo first order kinetics modeling (TiO2 loading density =
50 g/m2, pH = 9, UV = 24 W).

Mineralization and metabolites photocatalytic degradation of furfural

observed similar results for the degradation of furfural using UV/
To determine the potential of the TiO2–concrete composite as a
H2O2 [13]. Similar results were also revealed for photocatalytic
photocatalyst in mineralization of furfural molecules, the reduc-
degradation of 4-chlorophenol (4-CP) in a study by Venkatachalam
tion in COD values was checked against furfural during the
et al., proving that the degradation rate increased with increases in
the light intensity [133].

Effect of initial furfural concentration

As showed in Fig. 6A, furfural removal efficiency decreased as
initial furfural concentration increased from 400 to 800 mg/L. The
pseudo-first-order kinetics model of furfural degradation is shown
in Fig. 6B. This reduction in the removal efficiency of furfural could
have been caused by an increase in the number of furfural
molecules in the solution, which absorbed the photons, resulting in
lesser photon absorption on the catalyst surface. Thus, the
production of electron-hole pairs and, consequently, hydroxyl
radicals was limited, ultimately leading to a reduced efficiency in
furfural removal [81,92]. Nikazar et al. observed a similar result for
photodegradation of azo dye acid red 114 in water with TiO2
supported on clinoptilolite [134].

Kinetics study
The kinetics parameters of pseudo-first and second-order
kinetics models for furfural degradation were determined by
plotting ln (C0/Ct) against time and 1/Ct against time respectively
(Fig. 7) in selected conditions including TiO2 loading density of
50 g/m2, pH value of 9, UV irradiation intensity = 24 W, furfural
concentration of 400 mg/L and irradiation time = 300 min. The
chemical equations and the correlation coefficients (R2), along
with the other parameters for two different models, were
calculated and listed in Table 2 [135,136]. According to Table 2,
it can be concluded that the reaction kinetics of furfural removal
was best fitted for a pseudo-first-order reaction with a regression Fig. 7. A) Pseudo first order kinetics modeling and B) second order kinetics
coefficient of 0.95 and a rate constant of 0.0152 min1. modeling (TiO2 loading density = 50 g/m2, pH = 9, UV = 24 W and initial concentra-
tion of furfural = 400 mg/L).
 N. Gholami et al. / Journal of Industrial and Engineering Chemistry 62 (2018) 291–301 297

Table 2
The kinetics parameters of photocatalytic degradation of furfural.
1
Kinetics model Reaction Correlation coefficient Rate constant (k, min )
Pseudo first order ln½CODt ¼ kt þ ln½COD0 0.95 0.0152
Second order 1
¼ kt þ ½COD
1 0.7744 0.0006
½CODt 
0

photocatalytic reaction under the same selected conditions. removal) by increasing the reaction time but after a certain time
Although a furfural removal of 98.3% was obtained within a the kinetics of COD and TOC removal becomes limited. This can be
reaction time of 300 min, the COD removal reached 84.2% under attributed to the presence of some short-chain aromatics, which
the same operational conditions (Fig. 8). In fact, some furfural react with radical hydroxyl slowly. The production of some strong
molecules could be degraded into water and carbon dioxide during intermediates can also influence the kinetics of the reaction, as
the photocatalysis, while some molecules decomposed into these compounds precipitate on the surface of the photocatalyst
intermediate byproducts such as benzoic acid (Table 3). These throughout the process and reduce the active sites of the catalyst
organic byproducts are difficult to further degrade than furfural (carbon, etc.) [140]. This indicates that photocatalytic degradation
molecules; thus, the removal of COD was much more difficult than with catalysts for 8 h is the optimum reaction time. Beltran et al.
furfural [137]. These results are consistent with the results of Ghaly obtained similar results for photodegradation of industrial
et al., who observed, under optimum operating conditions, the dye wastewater by UV/H2O2 [141].
was decolorized about 99% by the addition of hydrogen peroxide
under solar photocatalytic oxidation within a 90 min irradiation Kinetics study of real wastewater
time, while TOC removal reached 60% within the same period of The kinetics of adsorption was investigated because of its
time. They attributed this to the formation of organic intermedi- importance in wastewater treatment processes, and kinetics
ates derived from the dye [138]. A GC–MS analysis was performed model analysis of the photodegradation process was studied using
as a qualitative experiment to determine the intermediates of the pseudo-first-order and second-order [135,142]. According to
furfural photodegradation (Fig. 9). The main products are Table 4, the reaction kinetics of COD removal through real
presented in Table 3. As can be seen from the results, some wastewater was best suited for pseudo-first-order reaction with
aromatic and aliphatic hydrocarbons are still present in the a regression coefficient of 0.9657 and a rate constant of
solution that indicates the cleavage of parent organic to simpler 0.0944 min1.
intermediates.
Reusability of the TiO2–concrete composite
Real wastewater treatment
The reusability of a photocatalyst is of high importance to
Effect of reaction time for COD and TOC removal reduce costs associated with this process. In order to test the
To determine the effect of time on the removal of COD and TOC, feasibility of the cyclic use of TiO2–concrete composite, it was
the experiment was carried out under selected conditions and at 2, reused in photocatalytic reaction through four sequencing cycles
4, 6, 8, 10 and 12 h. The COD and TOC removal data as a function of under selected conditions (TiO2 loading density = 50 g/m2, pH = 9,
reaction time are shown in Fig. 10. It is observed that increasing the UV irradiation intensity = 24 W and irradiation time = 300 min) for
reaction time, increases the percentage of degradation. This is the removal of furfural in synthetic wastewater and (TiO2 loading
because of the fact that with an increase in the irradiation time, the density = 50 g/m2, pH = 9, UV irradiation intensity = 24 W and
photons absorbed by the TiO2 surface increase, too, producing irradiation time = 8 h) for COD reduction of a real refinery
more free electrons and OH, which, ultimately, participate in the wastewater sample. According to the results, which are shown
reduction of COD and TOC [139]. As shown in Fig. 10, the efficiency in Table 5, it was found that the photocatalyst obtained by the
increased significantly with an increase of the reaction time up to TiO2–concrete composite could be reused at least four times with a
8 h (59.53% COD removal and 86.65% TOC removal). Thereafter, the negligible loss in photoactivity (98.3%–93.86% in furfural degrada-
efficiency increases slightly (64.80% COD removal and 93.11% TOC tion) in the case of synthetic wastewater and (59.53%–56.18% in
COD removal) for real wastewater. These results proved that nano-
TiO2 particles quite firmly attached themselves to the concrete
surface. In the first and second cycles, the furfural removal
efficiency decreased by about 2% but, in the next cycles, just less
than 1% reduction in efficiency was observed. According to this
result, it could be concluded that this reduction was because, after
each run, the color of the supported catalyst turned to dark brown.
The change in color of the photocatalyst was due to the
accumulation of intermediates on the active sites of the TiO2
surface [125,143]. The results obtained from a study by Teixeira
et al. showed that the photoactivity decreased by 13% after three
utilizations of TiO2 and ZnO nanoparticles immobilized in poly
(vinylidene difluoride)-co-trifluoroethylene by 15 wt.% TiO2 [144].
The stability and reusability of the synthesized catalysts (Fe-TiO2-
Ag nano-sphere) were also studied by Shojaei et al. and
demonstrated only a 3% decrease in photocatalytic degradation
efficiency of 4-chlorophenolafter five cycles [145].
The reusability of the TiO2–concrete composite was also
Fig. 8. Comparison of COD and furfural removal through photocatalytic degrada- investigated for COD removal from real refinery wastewater.
tion (TiO2 loading density = 50 g/m2, pH = 9, UV = 24 W and initial concentration of
Results demonstrated the reusability of the prepared TiO2–
furfural = 400 mg/L).
298 N. Gholami et al. / Journal of Industrial and Engineering Chemistry 62 (2018) 291–301

Table 3
Metabolites of furfural photocatalytic degradation in selected conditions and reaction time of 300 min.

Peak RT (min) Substance Chemical formula Chemical structure

1 7.064 4-Ethylbenzoic acid C9H10O2

2 13.301 3-Hydroxymandelic acid C8H8O4

3 22.910 1-Dodecanol C12H26O

4 27.608 Cyclotetradecane C14H28

5 28.492 Ethanol C2H6O

6 30.787 Isopropyl myristate C17H34O2

The first three studies investigated the photocatalytic activity of

immobilized TiO2 by removal efficiency of single pollutant from
synthetic waste water. In these cases, only one contaminant exists
in the liquid without any additional materials that interferes in the
process of degradation. For this reason, the reported removal
efficiencies as anticipated are higher than the other studies done
on real wastewater in Table 6. Furthermore, the study carried out
by Hosseini et al. was at much higher UV intensity than the two
other studies and also this study [95,121,146].
The fourth and fifth investigations examined photocatalytic
degradation of pollutants in a real wastewater. In these cases the
removal efficiency are highly dependent on the initial COD, used
UV intensity, and other parameters such as wastewater composi-
tion. As shown in Table 6, Zayani et al. [116] employed solar
photocatalytic reactor and 63% efficiency was observed after 8 h
while working with a higher intensity of UV that probably resulted
in a better removal efficiency. According to Beltran et al. studies it
can be concluded that by decreasing initial COD, the efficiency will
Fig. 9. GC–MS chromatogram of furfural photocatalytic degradation in selected
conditions (TiO2 loading density = 50 g/m2, pH = 9, UV = 24 W and initial concentra-
increase [141].
tion of furfural = 400 mg/L). In the present study the initial COD was about 1200 mg/L which
was higher than previous studies. Additional advantages of this
concrete composite under optimum experimental conditions research was COD removal efficiency of refractory industrial
obtained after four experimental runs. The results of reusability wastewater which was 60% only under 24 W UV intensity.
of the TiO2–concrete composite for the real wastewater were in Considering the significant influence of UV irradiation intensity
accordance with the results obtained for synthetic wastewater on COD decrease in this study and the related research done, the
(Table 5). effect of UV irradiation intensity on COD disappearance is
important. As experimental results indicated, while the reaction
Comparison with previous studies time increases, the COD decreases, thus for a given final (required)
COD, by increasing the UV intensity the needed reaction time will
In this section the experimental results are compared with decrease. Since the UV intensity and reaction time are inversely
those of the literature as shown in Table 6. proportional to each other, the optimum amount of each one is
 N. Gholami et al. / Journal of Industrial and Engineering Chemistry 62 (2018) 291–301 299

able compounds by the photocatalytic process, and suitable

wastewater is prepared to enter the biological treatment plant
at a considerably lower cost. Thus, it is likely that experimental
studies on the combination of this treatment with biological
oxidation are of greater interest, since chemical oxidation usually
improves water biodegradability. In this study commercial nano
TiO2 was successfully immobilized on a white concrete surface and
during the tests; catalyst nanoparticles showed a good adhesion to
the surface. Concrete is a mineral matter and is a major structural
building material in wastewater treatment units. So using of this
material as substrate is more suitable. Therefore, immobilized
nano-TiO2 on concrete seems to be economical and easy to use for
industrial applications. Furfural removal efficiency under selected
conditions (TiO2 loading density = 50 g/m2, UV = 24 W, pH = 9,
Fig. 10. Effect of reaction time on COD and TOC removal efficiency (TiO2 loading initial concentration = 400 mg/L) after 4 h was 98.3%. According
density = 50 g/m2, pH = 9, UV = 24 W, initial COD = 1200 mg/L). to this result, the reduction of COD in real wastewater can be
recommended at a reaction time of 8 h, during which time up to
related and depends on the criteria defined for that particular 60% COD removal can be achieved. Corresponding to an initial COD
industrial unit. (1200 mg/L), the final COD (about 500 mg/L) after 8 h was in an
acceptable and logical level. Moreover, the nano TiO2–concrete
Conclusion composite could be reused at least for four consecutive times.
During these four cycles, there was no significant change in
This work shows that the photocatalytic process using nano- efficiency (maximum about 4.4%), which means nano TiO2
TiO2/UV is one of the efficient methods with significant potential particles were quite firmly attached to the concrete surface.
not only for degradation of furfural in simulated wastewater but
also in real wastewater to reduce its COD. As demonstrated in this References
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Table 4
The kinetics parameters of COD removal of wastewater.

Kinetics model Reaction Correlation coefficient Rate constant (k, min1)

Pseudo first order ln½CODt ¼ kt þ ln½COD0 0.9652 0.0944
Second order 1
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Table 5
The cyclic photocatalytic performance of TiO2–concrete composite for COD removal.

Removal efficiency %

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Synthetic wastewater 98.3 95.91 95.43 93.86
Real refinery wastewater 59.53 57.65 57.48 56.18

Table 6
The comparison of the results of this study with previous studies.

Pollutants Initial COD (mg/ Initial TOC (mg/ Initial UV Reaction Removal efficiency (%)
L) L) concentration intensity time
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Furfural – – 400 mg/L 24 W 4h 98.3%
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wastewater
Tomato process wastewater 200 – – 15 W 2h 60%
300 N. Gholami et al. / Journal of Industrial and Engineering Chemistry 62 (2018) 291–301

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