Journal of Environmental Chemical Engineering 7 (2019) 103397

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Journal of Environmental Chemical Engineering

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

Photocatalytic treatment of a multicomponent petrochemical wastewater by T

floatable ZnO/Oak charcoal composite: Optimization of operating
parameters
N. Tafreshia, S. Sharifniab, , S. Moradi Dehaghia
⁎

a
Department of Chemistry, Tehran North Branch, Islamic Azad University, Tehran, Iran
b
Catal. Res. Cen., Dept. Chem. Eng., Razi Univ., Kermanshah 67149-67246, Iran

ARTICLE INFO ABSTRACT

Keywords: This paper aims to investigate the potential of photocatalytic processes for the degradation of multicomponent
Photocatalyst industrial wastewaters. Commercial ZnO nanoparticles were immobilized on pieces of carbonized Oak as a
Industrial ammonia wastewater floatable support and it was applied for the decontamination of industrial ammonia wastewater from a petro-
Floating support chemical plant under UV irradiation. Wastewater characterization confirmed the presence of ammonia, BOD,
Box-Behnken
COD, CaCO3, Cl− and SO42−. Box-Behnken experimental design was used to find out the best experimental
conditions and the maximum ammonia removal. A second-order polynomial model in terms of pH, catalyst
dosage and light intensity was suggested for prediction of the maximum efficiency of ammonia removal.
Accuracy of the model was verified by p-value of the model (< 0.0001), p-value of lack of fit (0.3987), R2
(0.9854) and adjusted R2 (0.9666). This model suggested that light intensity is the most effective parameter
maximizing the ammonia removal. The optimum conditions under which the maximum ammonia removal of
86.7% was observed are as follows: pH 9, catalyst dosage of 2 g/L, and light intensity of 250 W. This efficiency is
close to the predicted value of 93%. The other contaminants present in the wastewater were also decomposed
significantly by ZnO/Oak charcoal composite. This study can be useful for who are working on the real appli-
cations of photocatalysis processes.

1. Introduction
Ammonia wastewater is one of the main destructive sewage and has
the detrimental impacts on the communities and ecosystems. This ni-
trogen contaminant must be removed from wastewaters prior to the
reuse or release into the environment. Most of quality standards of the
treated wastewater specified the maximum ammonia concentration of
0.5 mg/L for the environment safety purpose [1]. Depending on the pH
and temperature of the water, two forms of inorganic nitrogen species,
NH3 (free ammonia) and NH4+ (ionized ammonia), are in equilibrium
in an ammonia wastewater. The free ammonia species is gaseous and
can be stripped completely above pH 12, while its ionized form is so-
luble in water and remains as soluble ammonia ions entirely below pH 7
[2,3]. In the real ammonia wastewaters, nitrogen is also oxidized bio-
logically by nitrifying bacteria, so the biochemical oxygen demand
(BOD) is expected to have a high value. Other expectable constituents
of real ammonia wastewaters are chemical oxygen demand (COD), total
suspense solid (TSS), CaCO3, SO42−, etc. [4]. Thus, the raw industrial
ammonia wastewater poses a great threat to the aquatic organisms and
must be treated before discharging to the environment.
Wastewater treatment refers to any type of physical, chemical and
biological methods that reduce the concentration of hazardous com-
pounds in aqueous media either by separation of them (like adsorption
[5] and membrane based [6] methods) or by the breakdown of complex
organics into simpler compounds that are stable and safer such as ad-
vanced oxidation processes (AOPs) [7–9]. The most widely being used
remediation processes of ammonia wastewater in high concentration
are air or steam stripping [10–12], ionic exchange [13,14], breakpoint
chlorination [15,16], electrodialysis [17,18] and nitrification-deni-
trification [19,20] processes. However, these processes cannot com-
pletely remove ammonia from aqueous media. Among these processes,
ammonia stripping technique is a highly efficient way of treating am-
monia wastewater. It was reported that ammonia stripping method
could remove ammonia with the efficiency as much as 90% [21]. Al-
though ammonia stripping is a low-cost and effective procedure, it has
some disadvantages like fouling problems [22], sludge production [23]

⁎
Corresponding author.
E-mail address: sharif@razi.ac.ir (S. Sharifnia).

https://doi.org/10.1016/j.jece.2019.103397
Received 24 May 2019; Received in revised form 7 August 2019; Accepted 30 August 2019
Available online 11 September 2019
2213-3437/ © 2019 Elsevier Ltd. All rights reserved.
N. Tafreshi, et al. Journal of Environmental Chemical Engineering 7 (2019) 103397

Scheme 1. Schematic diagram of photocatalyst preparation, the rectangles show the catalyst preparation steps and the ellipses show the final products.

Table 1 processes for the decontamination of effluents generated from various

Factors and levels in Box-Behnken design. types of industry sectors like petrochemical plants [25–27]. One ad-
Factor Coded Levles vantage of photocatalytic degradation of ammonia wastewater is the
capability of this process to be scaled up from the laboratory scale to
Low (-1.000) Medium (0.000) High (1.000) practical applications [28]. Apart from photogenerated holes, free hy-
droxyl and superoxide radicals are powerful oxidizing agents capable of
pH (X1) 4 8 12
Catalyst dosage (g/L) (X2) 0.5 1.25 2
degradation of ammonia and other organic and inorganic contaminants
Light intensity (w) (X3) 80 125 250 [29]. ZnO is a wide band gap photocatalyst with n-type conductivity
and high electron mobility of 205 cm2/V s at room temperature [30].
ZnO have shown good stability and photocatalytic activity in various
and needing to NH3 absorption unit as a secondary process [24] to aqueous media [31,32]. The redox potential of its valence band holes is
prevent additional environmental issues caused by NH3 releasing to the + 2.57 V (vs. SHE) which completely meets the potential required for
environment. All the other methods have their own favorable char- oxidizing the pollutants while also producing %OH species (Eº =
acteristics, but each has its limitations like formation of secondary +2.81 V vs. SHE). Similarly, the redox potential of its conduction band
pollutants, needing to high cost equipment and limitation of applic- electrons is -0.53 V (vs. SHE) which is completely in accordance to the
ability, especially when a real wastewater is targeted [10]. For these potential needed to form %O2− (Eº = +0.89 V vs SHE) [27].
reasons, AOPs have been emerged as alternative to or auxiliary process One of the main limitations of the photocatalytic processes in liquid
of the traditional methods since they are able to deal with the problem systems is the ineffective penetration of light through the wastewater
of ammonia degradation with high efficiency. for activating the settled photocatalyst particles by photon absorption.
Photocatalytic wastewater treatment is one of the oxidation For the real wastewaters which have inherently turbidity, the

2
N. Tafreshi, et al. Journal of Environmental Chemical Engineering 7 (2019) 103397

Table 2 impregnation and exposed to UV light irradiation to decompose the

The plan of experiments along with the experimental and predicted values for pollutants of industrial ammonia wastewater discharged from Ker-
Ammomia photodegradation %. manshah Petrochemical Company, Iran. The main parameters of pH,
Run Coded Levles Ammonia photodegradation (%) catalyst dosage, and light intensity were optimized by Box-Behnken
approach, which is an affordable and time-saving design [42,43], to
X1 X2 X3 Experimental Predicted maximize the ammonia removal efficiency. This study can be con-
sidered for the researchers who focus on the actual usages of photo-
1 0.000 0.000 0.000 84.00 84.64
2 1.000 −1.000 0.000 78.00 78.44 catalytic processes since there have been only a few reports dealing
3 1.000 0.000 −1.000 71.50 70.68 with the photocatalytic treatment of real ammonia effluents.
4 0.000 0.000 0.000 85.50 84.64
5 1.000 0.000 1.000 89.70 90.90
2. Material & method
6 0.000 0.000 0.000 85.90 84.64
7 0.000 0.000 0.000 85.30 84.64
8 −1.000 0.000 −1.000 65.00 67.55 2.1. Material
9 1.000 1.000 0.000 86.00 85.19
10 0.000 1.000 −1.000 76.00 75.01 ZnO powder, ethanol, and nitric acid were prepared from Merck Co.
11 −1.000 1.000 0.000 82.00 82.06
The Oak wood was obtained from Kermanshah’s forests, Iran, as the
12 −1.000 0.000 1.000 90.70 87.78
13 0.000 −1.000 −1.000 69.00 68.26 source of Oak charcoal. The used double distilled water was produced
14 0.000 1.000 1.000 93.50 92.24 in our lab. We applied industrial ammonia wastewater obtained from
15 −1.000 −1.000 0.000 75.00 75.31 Kermanshah Petrochemical Co., Iran.
16 0.000 0.000 0.000 82.50 84.64
17 0.000 −1.000 1.000 88.50 88.48
2.2. Photocatalyst preparation

The chopped Oak wood with average size of

(6 mm × 4 mm × 2 mm) first was soaked in 2 mol/L HNO3 at 60 °C to
remove the likely metal ions for 12 h. To clean up the support pieces
from the pigments inside its tissues, they were plunged into absolute
alcohol and deionized water at 60 °C for 12 h. Finally, they were dried
at 60 °C for 12 h. The dried wood pieces were heated up to 450 °C for
carbonization. A slurry composed of zinc oxide powder, ethanol, and
dilute nitric acid was prepared and sonicated for 30 min. ZnO nano-
particles were impregnated on the support surface by soaking the dried
support pieces into the prepared slurry and agitation until ethanol was
completely evaporated. The products then were dried at 120 °C for 12 h,
followed by calcination at 450 °C for 2 h under an inert atmosphere of
nitrogen. Scheme 1 shows the tutorial of the preparation of photo-
catalyst composites.

2.3. Methods of characterization

Fig. 1. XRD patterns of ZnO and ZnO/Oak charcoal samples.
penetration of light is even more expected. In the laboratory scale, this
issue can be addressed by agitation which is not recommended for the
real applications. The use of floatable supports on which the photo-
catalyst particles are loaded is a suitable way for the practical appli-
cations of photocatalytic wastewater treatment [4,33]. Some floatable
supports of photocatalysts are minerals like LECA [4,34] and perlite
[27,35], exfoliated vermiculite (EV) [36], hollow glass microbeads
[37], foams and polymers such as polyurethane foams [38], polystyrene
[39,40], etc.
Using low-cost, achievable photocatalyst supports with simple
synthesis procedure is essential and must be considered for the photo-
catalytic remediation of large scale wastewaters. In the previous study
[41] we investigated the positive role of the Oak charcoal as support of
commercial ZnO for the degradation of model ammonia wastewater.
The photocatalytic efficiency of 43% was obtained by ZnO nano-
particles without using the support which was considerably lower than
80% efficiency observed by ZnO supported on the Oak charcoal. This
indicates that floating of photocatalysts is a key way of boosting pho-
tocatalytic activity. Therefore, the importance of the study presented
here is: (I) the assessment of floating effect of photocatalyst particles in
the photocatalytic application using low-cost, available materials and
(II) investigation of potential of photocatalytic process for the decom-
position of real ammonia wastewater. To this purpose, commercial ZnO
nanoparticles were loaded on the low-density Oak charcoal by
The prepared samples was characterized by XRD (XRD, PHILIPS
PW1140) to study the structure of the samples. The morphology, shape
and size of the samples were found by FESEM analysis (FESEM, MIRA3-
TESCAN). The optical property of the samples was measured by UV–vis
DRS spectroscopy (Jasco V-670 spectrophotometer, Japan). The texture
properties of the photocatalysts were measured by BET method. And
the pore size distribution was investigated by BJH method.
The concentration of ammonia before and after photocatalysis was
measured by UV spectrophotometer. Using an American public health
association standards (APHA, 1998), the concentration of other com-
ponent present in the industrial wastewater was measured as follows.
The concentration of COD was determined by a Hach-2000 spectro-
photometer using a dichromate solution as the oxidant in strong acid
media via closed reflux, colorimetric method through APHA, 1995
section 5220-D. Total suspended solids (TSS) were measured by the
gravimetric method via APHA, 1995 section 2540-D. BOD5 was ana-
lyzed by using a respiremetry system by 5-day BOD test based on APHA,
1995 section 5210-B. Sulfate (SO4−2) and chloride anions were mea-
sured by ion exchange chromatography (Dionex, Model: DX-120) after
filtering the samples through a 0.45 mm filter.
2.4. Photoreactor tests
The photodegradation process was carried out in a Pyrex glass
vessel with the inner volume of 1.5 L which was top-irradiated by an Hg
lamp (maximum wavelength of 254 nm). The inside of the experimental
set-up was completely shielded by a metal foil to avoid losing light.

3
N. Tafreshi, et al.
Fig. 2. FESEM images of (a) commercial ZnO nanoparticles, (b) and (c) Oak charcoal, and (d) a piece of Oak charcoal coated by ZnO.
ZnO/Oak charcoal composite (10 wt.% ZnO) was floated on 1.0 L of real
ammonia wastewater and then irradiated by UV light for 4 h. pH of the
solution was adjusted by 0.1 N HCl and/or NaOH solutions. An air
diffuser on the bottom of the reactor supplied the oxygen needed for the
photocatalytic reactions. The temperature of reactor was kept constant
at 20 °C by circulating cooling water. Prior to the photocatalysis tests,
the adsorption capacity of the composite photocatalysts was measured
by a blank test, a non-irradiated test for 120 min. After irradiation, the
content of the photoreactor was sampled to determine the concentra-
tion of ammonia and other contaminant based on the measurement
methods mentioned in the previous section.
2.5. Experimental design and statistical analysis
Experimental design systematically examines the importance of the
independent variables (inputs) and their interactions and finally max-
imizes or minimizes the dependent variables (outputs) in the
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Journal of Environmental Chemical Engineering 7 (2019) 103397
determined range of the input variables. In the work presented here, by
applying Box-Behnken experimental design (Design Expert software
(Ver. 7.0.0)), the removal efficiency of ammonia from real wastewater
as the output variable by ZnO/Oak charcoal was modeled mathemati-
cally in terms of three main factors of pH (X1), catalyst dosage (X2), and
light intensity (X3). Three levels of the input variables are given in
Table 1. A set of 17 experiments in three levels (with three times re-
plication of the center point) were designed to compare the differences
between the observed and predicted values. Table 2 presents the
schedule of experiments and the predicted and observed responses. The
experimental data were fitted well by a second-order polynomial
mathematic model which is shown in Eq. (1).
k k k k
Y = b0 + bi x i + bii x i2 + bij x i xj +
i=1 i=1 i=1 j> 1 (1)
where Y is the modeled output, b0 is the offset term. bi, bii, and bij are
the coefficient of linear, squared, and interaction effects, respectively. ε
N. Tafreshi, et al. Journal of Environmental Chemical Engineering 7 (2019) 103397

Fig. 3. N2 adsorption-desorption isotherms and pore size distributions of Oak charcoal and ZnO/charcoal samples.

Table 3 Table 4
The textural properties of the Oak charcoal and ZnO/charcoal. Results of ANOVA.
Sample Surface areaa (m2/g) Pore volumeb (cm3/g) Pore diameterc (nm) Source Sum of Degree of Mean F-value p-value
squares freedom square prob > F
Oak charcoal 5.233 0.074637 21.21
ZnO/charcoal 15.063 0.002775 1.98 Model 1020.17 9 113.35 52.51 < 0.0001
X1 19.53 1 19.53 9.05 0.0197
a
BET specific surface area. X2 91.13 1 91.13 42.22 0.0003
b
measured at P/Pº = 0.990. X3 818.10 1 818.10 379.01 < 0.0001
c
calculated from the desorption branch of the isotherm using the BJH X1 X2 0.25 1 0.25 0.12 0.7436
X1 X3 14.06 1 14.06 6.51 0.0380
method.
X2 X3 1.00 1 1.00 0.46 0.5180
X12 50.33 1 50.33 23.32 0.0019
X22 3.66 1 3.66 1.70 0.2340
X32 16.13 1 16.13 7.47 0.0292
Lack of Fit 7.36 3 2.45 1.27 0.3987
Pure Error 7.75 4 1.94
Residual 15.11 7 2.16
Total 1035.28 16

R2 = 0.9854, Adj-R2 = 0.9666, Adeq precision = 25.792, Std. Dev. = 1.47, C.V.
% = 1.8.

Table 5
Characterization of various contaminants in the industrial ammonia wastewater
before and after photocatalytic treatment.
Component Unite Initial value Final value Conversion (%)

pH − 9.8 10.2 −
Total hardness ppm 440 205 53.4
CaCO3 ppm 75 21 72.0
Ammonia ppm 310 41 86.7
Chloride ppm 1280 915 28.5
Fig. 4. Room temperature UV–vis spectra of ZnO and ZnO/Oak charcoal sam- Sulfate ppm 320 168 46.0
ples. BOD ppm 75 48 36.0
COD ppm 1610 674 58.0

is the random error.Also, i and j are the index number, and xi stands for
the dimensionless codded variable of Xi. several groups are equal. By ANOVA, the impact of linear, interactive,
The analysis of variance (ANOVA), used in the paper presented, is a and quadratic effects of variables can be determine. Regression coeffi-
powerful statistical method revealing whether or not the means of cients of adjusted and predicted (R2-adj and R2), lack of fit (LOF), and

5
N. Tafreshi, et al. Journal of Environmental Chemical Engineering 7 (2019) 103397

Fig. 5. (a) Residual plot of the predicted and actual values, (b) normal probability of internally studentized residuals.

degrees of freedom are other statistical tools measuring the significance this property also make it an appealing support for the actual waste-
of the model applied. water treatment because of the possibility of adsorbing pollutant mo-
lecules inside the pores and cavities. Fig. 2 (d) shows a piece of Oak
charcoal coated with ZnO particles. As can be seen, the larger pores
3. Results & discussion
were not completely blocked by the photocatalyst.
Fig. 3 shows N2 adsorption-desorption analysis and pore size dis-
3.1. Results of photocatalyst characterization
tribution of the Oak charcoal and ZnO/charcoal samples. The isotherm
of the Oak charcoal may be classified as type II, meanwhile the ZnO/
Fig. 1 shows the XRD patterns of ZnO and ZnO/charcoal samples.
charcoal exhibited a type I isotherm. Both samples showed H3 type
The main characteristic peaks at scattering angles of 32, 34, 36, 47, 56,
hysteresis loops. The H3 hysteresis loop is usually appears on solids
62 and 68° can clearly be seen from the pattern of ZnO, relating to the
having aggregated or agglomerated particles with slit-shaped, nonuni-
(100), (002), (101), (102), (110), (103) and (112) facets in the wurtzite
form size pores [44]. Type II isotherm with H3 hysteresis loop is the
structure of ZnO with hexagonal phase, respectively (JCPDS card no.0-
characteristic of nonporous solids or mesoporous and macroporous
3-0888). All the diffraction peaks of ZnO are detected from XRD pattern
powders [45]. This type of isotherm also indicates unrestricted mono-
of the ZnO/charcoal, confirming the presence of ZnO nanoparticles on
layer-multilayer adsorption, multilayer adsorption takes place at high
the support. The broad peak centered at 24° is attributed to the support
P/Pº [46]. The broad hysteresis loop of the Oak charcoal is located at a
which indicates that the Oak charcoal had an amorphous nature.
high relative pressure region (0.79-0.96), which means that there were
To understand the morphology and particle size of the samples,
large pores on it. This result is definitely in agreement with the results
FESEM analysis was applied and the results are given in Fig. 2. There
obtained from FESEM analysis. For the ZnO/charcoal composite, a
are ZnO particles with rod-like shape and particle size distribution of
small hysteresis loop is observed at lower relative pressure (0.34-0.97)
50–200 nm (Fig. 2(a)). According to Fig. 2(b) and (c), Oak charcoal is a
compared to the Oak charcoal sample, indicating the mesoporous fea-
porous support, having a lot of surface spherical cavities with diameters
ture of this catalyst [47]. It is follows that the addition of ZnO leads to
of 5–15 μm. Other than affordability and floatability of Oak charcoal,

6
N. Tafreshi, et al.
Fig. 6. Perturbation plots of pH (A), catalyst dosage (B), and light intensity (C) on the photocatalytic performance of ammonia degradation.
the decrease of pore volume due to the incomplete blockage of cavities
on the support structure. This assumption was investigated by BJH
analysis. From BJH plot of the Oak charcoal, the high peak at 14.18 nm
indicates the size of mesoporous, and the low and broad peak centered
at 51.36 nm is ascribed to the larger pores. The BJH plot of the ZnO/
charcoal shows two weak peak at 9.18 and 29.76 nm, proving that this
sample had a mesoporous nature with a narrow pore size distribution.
Table 3 gives the BET parameters of the samples. With loading ZnO
over the Oak charcoal, the pore size and pore volume decreased from
21.21 to 1.98 nm and 0.074637 to 0.002775 cm3/g while specific sur-
face area increased from 5.233 to 15.063 m2/g.
For the photocatalysis purposes, optical characterization is im-
portant, and thus UV–vis DRS was taken from ZnO and ZnO/charcoal
samples in the wavelength range of 300 to 600 nm (Fig. 4). ZnO is an
excellent UV absorbent mainly in 390 nm. The composite samples
showed better light absorption performance because it can be activated
by photons with lower energy (∼ 460 nm) in visible region. Based on
Eg = 1245/λa, where Eg and λa respectively are the band gap energy
and the activating wavelength of light, the corresponding band gaps of
ZnO and ZnO/charcoal are estimated to be 3.19 and 2.70 eV, respec-
tively.
3.2. Nonlinear modeling
pH, catalyst dosage, and light intensity were selected as three key
parameters affecting the photocatalytic efficiency of industrial am-
monia degradation. The experimental matrix design based upon Box-
Behnken method, and the real and predicted responses are tabulated in
Table 2. On the basis of the experimental design, the photocatalytic
ammonia degradation as an output is a function of pH (X1), catalyst
dosage (X2), and light intensity (X3) by a second-order polynomial
equation in terms of coded factors (Eq. (2)).
Y = 84.25 + 1.56 X1 + 3.38 X2 + 10.11 X3 – 1.88 X1X3 – 3.51 X12 –
2.01 X32 (2)
where Y, X1, X2, and X3 stand for efficiency of ammonia removal, pH,
catalyst dosage, and light intensity, respectively. Tables 4 and 5 in-
dicates the results of ANOVA. The independent variables, their inter-
actions, and the regression coefficients can be statistically considered
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Journal of Environmental Chemical Engineering 7 (2019) 103397
significant for p-value lower than 0.05. Accordingly, a prediction model
is suitable provided that LOF is greater than 0.05. Herein, LOF p-value
of the model proposed is 0.3987 which is large enough, so the model
can successfully predict the dependent variable. The p-value of the
model is < 0.0001, indicating that the model is highly significant. The
predicted R2 (0.9854) and adjusted R2 (0.9666) agree with each other
and are very close to 1, demonstrating goodness of fitting the predicted
model curve on the experimental data. Indeed, the proposed model is
unable to explain only 2% of the total variations. The accuracy of the
model is also confirmed by the predicted versus actual value plot de-
picted in Fig. 5(a). Moreover, Fig. 5(b) indicates that the studentized
residuals lie between -2 and +2 without any outliner and the devia-
tions of them with the diagonal line are small. The mutual interactions
of X1X2 and X2X3, and quadratic interaction of X22 are insignificant and
can be eliminated from the prediction model. On the other hand, F-
value of 52.51 also revealed the significance of the model. LOF F-value
of 1.27 implies that the LOF is not significant relative to the pure error.
Among the significant variables, the highest F-value and lowest p-value
belong to X3, which means that light intensity is the most important
parameter affecting the photocatalytic efficiency of ammonia de-
gradation. The significant variables have the effectiveness order of light
intensity > catalyst dosage > pH. Other diagnostic tool confirming
the results of ANOVA is perturbation analysis which remarks the effects
of significant input variables on the predicted response. From Fig. 6, it
is apparent that the light intensity (C) is the most effective parameter,
and ammonia degradation would increase with the increment of the
light intensity. The two other variables have a negligible effect on the
response when they change in the vicinity of the centre point. However,
the effect of catalyst dosage (B) is slightly higher than that of pH (A) as
confirmed by p and F tests. Adequate precision, or signal to noise ratio,
is a tool for comparison of the range of the predicted values and the
average variance at the design points. Adequate precision greater than
4 indicates adequate model discrimination. In this particular case it is
25.792, well greater than 4. Very low value of the coefficient of var-
iation, 1.8%, indicates a good reliability of the experimental data.
3.3. Response surface analysis
The 3D and contour plots showing the effect of mutual interactions
on the response are given in Fig. 7. Fig. 7 (a) and (b) signify that the
N. Tafreshi, et al.
Fig. 7. 3D and cotour plots showing interaction of (a)-(b) pH and catalyst dosage, (c)-(d) pH and light intensity, and (e)-(f) catalyst dosage and light intensity.
photocatalytic efficiency of ammonia degradation can be maximized by
controlling pH and catalyst dosage, the former must be in the basic
range (8–10) and the latter at 2 g/L. It is reasonable that the photo-
catalytic degradation of ammonia is favorable in basic pH. The presence
of OH− species from a basic source like NaOH helps more hydroxyl
radicals to be form by electron capturing from photocatalyst’ CB. Also,
in basic medium, the adsorption of ammonia molecules on photo-
catalyst surface increases, for the negatively charged photocatalyst
surface possesses a great affinity with the NH4+ species. Increasing
catalyst dosage corresponds to the increase of both adsorption site and
charge carriers participating in the photocatalytic reactions thus in-
creasing the efficiency of ammonia removal. From Fig. 7 (c) and (d), the
effect of concurrent changes in pH and light intensity on the response is
seen. Clearly, light intensity is the most influential parameter
8
Journal of Environmental Chemical Engineering 7 (2019) 103397
maximizing the photocatalytic degradation of ammonia. Promoting
light intensity accelerates the surface photocatalytic reactions because
the number of activating photons per unite area of the photocatalyst
would increase. In the case of this study, the light intensity of 250 W is
recommended to maximize the response. Fig. 7 (e) and (f), including
the effect of light intensity and catalyst dosage, also verifies the results
interpreted above.
3.4. Model validation
Based on the results obtained from the modeling of photocatalytic
performance of ZnO/Oak charcoal, we carried out an experiment in
triplicate in the optimum condition, pH 9, catalyst dosage of 2 g/L, and
light intensity of 250 W, to verify the reliability of the model. The
N. Tafreshi, et al. Journal of Environmental Chemical Engineering 7 (2019) 103397

This study
Ref.

[4]
Removal efficiency

86.7%
96%
Final ammonia concentration

Fig. 8. Results of three times recycling ZnO/charcoal for the photocatalytic

treatment of petrochemical ammonia wastewater.
41
39
250 W high-pressure Hg lamp with maximum wavelength of 254 nm
A comparison between the results of photocatalytic treatment of industrial ammonia wastewater obtained from the present study and our previous work.

Solar light with the mean UV/visible wavelength of 280-390 nm

Light source
Process time (h)

72
4
Catalyst dosage (g/L)

Fig. 9. (a) XRD patterns and (b) FTIR spectra of ZnO/Charcoal before and after
25
2

three times recycling.

pH

11
9

ammonia degradation efficiency of 86.7% was obtained, which is close

Initial ammonia concentration (ppm)

to the predicted value (93%). Other than ammonia, the other con-
taminants were also degraded considerably. The results are tabulated in
Tables 4A and 4B. As can be seen, the photocatalytic treatment sig-
nificantly reduced the concentration of dissolved CaCO3 (72.0%) which
is a main reason of temporary hardness. A comparison between the best
result of ammonia removal obtained here with the result from our
previous work is shown in Table 6.
310
975

3.5. Evaluation of ammonia removal via non-photocatalytic processes

ZnO/charcoal
Photocatalyst

A series of experiments were done at the optimum conditions to

TiO2/LECA

reveal the floating effect of the photocatalyst as well as the participa-

Table 6

tion of other processes in the removal of ammonia from the wastewater.

The quantities of ammonia removal by adsorption (the Oak charcoal in

9
N. Tafreshi, et al.
darkness without both ZnO and air diffuser), photolysis (UV without
both the photocatalyst and air diffuser), and stripping (via air diffuser
(2.0 L/min) without the photocatalyst in darkness) were obtained to be
18, 4, and 7%, respectively. These results show that photocatalysis is
the prevailing process of ammonia removal from real wastewater.
Besides, ZnO nanoparticles showed the ammonia photodegradation of
37% under UV irradiation, demonstrating the considerable effect of
floating the photocatalyst in increasing the photocatalytic performance.
3.6. Reusability of photocatalyst
It is often found that photocatalytic reactions are completely sup-
pressed after a while, possibly because of backward reactions and
poisoning effect that is a result of compounds chemically bounded on
the catalyst surface [27]. Herein, to study the reusability, the ZnO/
charcoal particles were filtered and washed by deionized water three
times. Then, they were poured into an aqueous HCl solution (pH 6)
under stirring for 30 min to remove the likely deposited CaCO3 particles
on the photocatalyst surface based on Eq. (3). The likely SO42+ ions are
also expected to be removed. At the next step, the photocatalyst par-
ticles were washed by an aqueous NaOH solution (pH 10.5) to remove
the remained HCl/Cl− based on Eq. (4). The surface remained NH4+
can be converted to NH3 in basic media according to Eq. (5). Since NH3
can be easily removed from photocatalyst surface by steam regenera-
tion, the photocatalyst particles were exposed to air steam by an air
diffuser in a Teflon vessel for 30 min (flow rate 2 L/min, temperature
120 °C). Finally, the photocatalyst particles were dried at 80 °C for 24 h
followed by calcination at 300 °C for 1 h under nitrogen atmosphere.
CaCO3 (s) + 2 HCl CaCl2 (aq) + H2 O (l) + CO2 (g) (3)
−1 −
HCl (aq)/Cl + NaOH (aq) → NaCl (aq) + H2O (l)/OH (4)
NH+4 + OH NH3 + H2 O (5)
Fig. 8 shows the results of three times recycling the ZnO/charcoal
photocatalyst for the photocatalytic treatment of industrial ammonia
wastewater. As can be seen, the photocatalytic performance was di-
minished obviously in second and third runs. Fig. 9 indicates the XRD
and FTIR patterns of the fresh and three times recycled ZnO/charcoal.
From Fig. 9(a), it is obvious that the phase and structure of the used
samples remained the same. However, the intensity of ZnO’s peaks
decreased slightly due to catalyst losing. FTIR gives us more informa-
tion on the possible changes in the surface chemical properties of
photocatalysts. As can be seen from Fig. 9(b), IR spectrum of the fresh
ZnO/charcoals includes six main characteristic bands at 480, 620, 749,
862, 1622 and 3410 cm−1. The band located at 480 cm−1 indicates the
stretching metal-oxide bond in ZnO structure. The bands at 620, 749
and 862 cm−1 are attributed to an aromatic network produced upon
carbonization process [48]. The bands located at 1622 and 3410 cm−1
are ascribed to the bending and stretching surface hydroxide groups.
Although, stretching vibration of the non-saturated C]C bonds may
also the origin of absorption band at 1622 cm−1 [49]. The IR spectrum
of the used sample exhibits additional peaks at 781, 787 and
1407 cm−1, the two formers may be assigned to the vibration modes of
NO2− and NO3− surface bonds [41] and/or chemisorbed Cl− on the
charcoal (stretching C-Cl bond) [50] and the latter can be ascribed to
the presence of calcite deposited on the photocatalyst surface [51].
Therefore, it can be said that the declined catalytic performance after
three times recycling is due to the loss of catalyst as well as the poi-
soning effect caused by accumulated of the reactants on catalyst sur-
face.
4. Conclusion
This study deals with the photocatalytic decontamination of
10
Journal of Environmental Chemical Engineering 7 (2019) 103397
industrial ammonia wastewater obtained from a petrochemical plant.
ZnO immobilized on Oak charcoal was used as a floatable photocatalyst
under UV irradiation. Box-Behnken optimization indicated that among
three parameters of pH, catalyst dosage, and light intensity, light in-
tensity is the most effective parameter on the photodegradation of
ammonia. The prediction model suggested the optimum conditions of
pH 9, catalyst dosage of 2 g/L, and light intensity of 250 W, which
provided the best conversion of 86.7%. Other contaminants were also
decomposed and/or removed by the photocatalytic treatment, CaCO3,
COD, SO42−, BOD, and Cl− with the efficiency of 72.0, 56.0, 46.0, and
36.0, 28.5%, respectively. Also, the total hardness was diminished with
the efficiency of 53.4%. It was observed that floating the photocatalyst
caused to enhance the photocatalytic activity from 37% by pure ZnO to
86.7% by the floatable ZnO/Oak charcoal composite. The FTIR spectra
of the ZnO/charcoal before and after three times recycling reveal the
poisoning of the photocatalyst because of accumulation of the reactants
on the photocatalyst surface.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgement
We thank the Kermanshah Petrochemical Co. Iran, for providing the
real ammonia wastewater and for assistance in some experimental
analyses.
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