water

Article
Removal of COD and SO42− from Oil Refinery
Wastewater Using a Photo-Catalytic
System—Comparing TiO2 and Zeolite Efficiencies
Emmanuel K. Tetteh * , Elorm Obotey Ezugbe , Sudesh Rathilal and Dennis Asante-Sackey
Faculty of Engineering and the Built Environment, Department of Chemical Engineering,
Durban University of Technology, Durban 4000, South Africa; elormezugbe.ee6@gmail.com (E.O.E.);
rathilals@dut.ac.za (S.R.); ingsackey@gmail.com (D.A.-S.)
* Correspondence: ektetteh34@gmail.com




Received: 29 November 2019; Accepted: 9 January 2020; Published: 12 January 2020


Abstract: Advanced oxidation processes (AOPs) have many prospects in water and wastewater
treatment. In recent years, AOPs are gaining attention as having potentials for the removal of
different ranges of contaminants from industrial wastewater towards water reclamation. In this study,
the treatability efficiencies of two photo-catalysts (TiO2 and zeolite) were compared on the basis
of the removal of chemical oxygen demand (COD) and SO4 2− from oil refinery wastewater (ORW)
using photo-catalytic system. The effects of three operating parameters: catalyst dosage (0.5–1.5 g/L),
reaction time (15–45 min), mixing rate (30–90 rpm) and their interactive effects on the removal of
the aforementioned contaminants were studied using the Box–Behnken design (BBD) of response
surface methodology (RSM). Statistical models were developed and used to optimize the operating
conditions. An 18 W UV light was incident on the system to excite the catalysts to trigger a reaction
that led to the degradation and subsequent removal of contaminants. The results obtained showed
that for almost the same desirability (92% for zeolite and 91% for TiO2 ), TiO2 exhibited more efficiency
in terms of mixing rate and reaction time requirements. At the 95% confidence level, the model’s
predicted results were in good agreement with experimental data obtained.

Keywords: chemical oxygen demand; oily wastewater; response surface methodology (RSM); TiO2
photo-catalyst; zeolite

1. Introduction
Issues of water scarcity and how it can be curbed continues to be a challenge to the world.
There is continuous aggravation of water pollution due to population growth and its corresponding
effects on industrialization, agriculture, and domestic activities. This has led to radical exploration
of alternative and sustainable means of obtaining water from unconventional means, such as water
re-use through wastewater treatment [1]. Because wastewater production is inevitable, wastewater
treatment for re-use has become the most convenient way of stemming water scarcity. One of the major
industrial water pollution sources is the oil refinery industry. Reports indicate that for every 1 barrel
of oil processed, about 10 barrels of oily wastewater is produced. In addition, large volumes of oily
wastewater is generated during transport and refinery of oil [2]. Apart from salts being the highest in
concentration (1000–3500 mg/L) of oily wastewater, organic compounds follow with a concentration
range of 15–1500 mg/L, then oil and grease ranging from 2 to 565 mg/L [3]. Consequently, high levels
of chemical oxygen demand (COD), total suspended solids (TSS), total dissolved solids (TDS), soap oil
and grease (SOG), and traces of metals are found in the oily waste streams, which make their treatment
problematic and cause huge pollution problems [4].

Water 2020, 12, 214; doi:10.3390/w12010214 www.mdpi.com/journal/water

Water 2020, 12, 214 2 of 14

Over the years, several treatment methods have been employed to treat oily wastewater. These
Water 2020, 12, 214 2 of 13
include membrane filtration, coagulation-flocculation, hydro-cyclones, and biological treatment
systems, among Overothers [5,6].
the years, Withtreatment
several a focus methods
on organic
have component
been employed removal,
to treatbiological systems
oily wastewater. have been
These
preferred due to
include their lowfiltration,
membrane cost of operation and eco friendliness
coagulation-flocculation, [7]. However,
hydro-cyclones, biological
and biological treatmenttreatment
processessystems, among others
have shown [5,6]. With
limitations a focus
at high on organic component
contaminant removal,
concentration. Inbiological
addition,systems
some have
recalcitrant
been preferred due to their low cost of operation and eco friendliness [7]. However, biological
organic pollutants (such as inert COD) show high resistance to biological degradation processes [8].
treatment processes have shown limitations at high contaminant concentration. In addition, some
With advancements in research, advanced oxidation processes (AOPs) are being explored for
recalcitrant organic pollutants (such as inert COD) show high resistance to biological degradation
many wastewater
processes [8].treatment applications and to fill the gaps left by conventional treatment processes.
AOPs are chemical processesinthat
With advancements makeadvanced
research, use of hydroxyl radicals(AOPs)
oxidation processes to effectare oxidation
being explored[9]. forFigure 1
shows amany
briefwastewater
description treatment applications
of contaminant and to fill the in
degradation gapsanleft by conventional
AOP treatment
(photo-catalysis). processes.
Photo-catalysis is
AOPs are chemical processes that make use of hydroxyl radicals to effect oxidation
essentially the activity that occurs when a light source interacts with a semiconductor metal oxide [9]. [9]. Figure 1
shows a brief description of contaminant degradation in an AOP (photo-catalysis). Photo-catalysis is
During photo-catalysis, an incident light (UV) causes excitation on the surface of a photo-catalyst. This
essentially the activity that occurs when a light source interacts with a semiconductor metal oxide [9].
happensDuring
whenphoto-catalysis,
electrons in the valencelight
an incident band absorb
(UV) causesenergy higher
excitation on thethan their
surface of band gap energy and
a photo-catalyst.
therefore move intowhenthe conduction band. When +
This happens electrons in the valence bandthisabsorbhappens, a holethan
energy higher (h their
in the
bandvalance band) and
gap energy
(e− therefore
electronand in the conduction
move into the band) are produced
conduction band. Whensimultaneously. These
this happens, a hole (h+ two
in thespecies
valance (e − and
band) and h+ ) then
electron (e−later
either recombine in theorconduction
they reactband)withare produced
oxygen simultaneously.
molecules to formThese two species
peroxide or with (e−water
and h+molecules
) then to
either recombine later or they react with oxygen molecules to form peroxide
form hydroxyl species. The peroxide and hydroxyl formed then attack and degrade organic pollutants or with water molecules
to form hydroxyl species. The peroxide and hydroxyl formed then attack and degrade organic
into more manageable compounds such as water or carbon dioxide [10,11].
pollutants into more manageable compounds such as water or carbon dioxide [10,11].

FigureFigure 1. Stages
1. Stages in organic
in organic pollutant (O.P)
pollutant (O.P) degradation
degradationin photo-catalysis.
in photo-catalysis.

Photo-catalysts such as TiO2 have been used extensively in wastewater treatment due to their
Photo-catalysts such as TiO2 have been used extensively in wastewater treatment due to their
ability to function at ambient temperature, their accessibility, cost effectiveness, and their ability to
ability to function at ambient temperature, their accessibility, cost effectiveness, and their ability
oxidize most organic contaminants to safer and more manageable compounds such as CO2 and H2O
to oxidize[12].most
In anorganic
experimentcontaminants to safer
to treat olive mill and more
wastewater, manageable
El Hajjouji et al. [13] compounds
used a TiO2/UV such as CO
system to 2 and
H2 O [12]. In an experiment to treat olive mill wastewater, El Hajjouji et al. [13] used
degrade 94% phenol over a 24 h period with 1 g/L of the catalyst. In a similar study, Chatzisymeon a TiO 2 /UV system
et al. [14] studied the effects of operating parameters, including initial organic load
to degrade 94% phenol over a 24 h period with 1 g/L of the catalyst. In a similar study, Chatzisymeon of influent, contact
time,
et al. [14] and concentration
studied the effects of of operating
TiO2 in media on the removal
parameters, of COD,initial
including total phenols,
organicand color
load of from black contact
influent,
table olive processing wastewater. The findings showed that the efficiency of the TiO2 photo-catalysis
time, and concentration of TiO2 in media on the removal of COD, total phenols, and color from black
increased with increasing contact time, catalyst dosage, and decreasing initial organic load.
table olive processing wastewater. The findings showed that the efficiency of the TiO2 photo-catalysis
Zeolites are mainly known for their peculiar ion-exchange, molecular sieving, and adsorption
increased with increasing contact
abilities [15,16]. Zeolites have time, catalystindosage,
been applied and decreasing
diverse ways initial organic
in water purification. They have load.been
Zeolites
appliedare in mainly known
heavy metal for their
removal peculiar ion-exchange,
from wastewater [17,18] and for molecular
dye removalsieving,
for textileand adsorption
effluent
abilities[19,20].
[15,16]. Zeolites act ashave
Zeolites photo-catalysts
been appliedwhen in
thediverse
zeolite framework
ways in is photo-activated
water or incorporated
purification. They have been
applied with other metal
in heavy materials such asfrom
removal semiconductors
wastewater [21]. Their and
[17,18] unique
forability of promoting
dye removal stabilization
for textile of [19,20].
effluent
photochemically generated redox species and controlling charge transfer and electron transfer
Zeolites act as photo-catalysts when the zeolite framework is photo-activated or incorporated with
processes makes them worth exploring for many photo-catalytic applications [22,23].
other materials such as semiconductors [21]. Their unique ability of promoting stabilization of
photochemically generated redox species and controlling charge transfer and electron transfer processes
makes them worth exploring for many photo-catalytic applications [22,23].
Water 2020, 12, 214 3 of 14

In this study, the efficiencies of zeolite (photo-activated) and TiO2 were studied and compared on
the basis of the removal of COD and SO4 2− from oily wastewater in a photo-catalytic system. These
two contaminants are higher than the permitted discharge limits of 1000 ppm (COD) and 500 ppm
(SO4 2− ), respectively [1–3,24]. Three operating parameters were varied catalyst dosage (0.5–1.5 g/L),
reaction time (15–45 min), and mixing rate (30–90 rpm). Response surface methodology (RSM) was
used to optimize and study the interactions between the operating parameters. The effluent used for
the experiment was collected from a local oil refinery effluent treatment plant in South Africa.

2. Materials and Methods

2.1. Effluent Sample and Analytical Methods

Effluents for the experiment were collected from the sewer of the effluent treatment plant of a
local oil refinery. Before getting to the sewer, the effluent passes through some preliminary treatment
processes. Residual oil is recovered at the oil–water separator and dissolved air floatation units.
Other contaminants such as suspended solids are removed using coagulation-flocculation systems.
Characterization of the effluent for SOG and COD was performed according to standard methods,
as used by [24]. Sulphate determination was done using a HI 83099 COD meter and multi-parameter
photometer from Hanna Instruments (Limean, Vaneto, Italy). Conductivity was measured using a TDS
meter, model C7 from HJM electronics (Edenval, Gauteng, South Africa). Sulphide and pH analysis
was done using HI 4222 research grade bench pH and ion specific (ISE) meter from Hanna Instruments
at ambient temperature. Table 1 gives the properties of the effluent.

Table 1. Properties of oily wastewater before treatment. COD: chemical oxygen demand, SOG: soap oil
and grease.

Component Value
pH 8.09
Conductivity (mg/L) 613.38
Sulphates (mg/L) 895.00
Sulphide (mg/L) 1.26
COD (mg/L) 1226.8
SOG (mg/L) 33.23

2.2. Chemicals Used

TiO2 nanomaterial used in this study was supplied by Huntsman Tioxide, South Africa (Pty).
The SACHTLEBEN R-KB-6 is a micronized rutile titanium dioxide pigment treated with alumina and
zirconia compounds. Detailed properties of the TiO2 nanomaterial can be found in Table 2. Commercial
zeolite powder (95–98% clinoptilolite balance opaline silica) used in this study was supplied by
Sigma-Aldrich,
Water 2020,South
12, 214 Africa. 1M H PO (analytical grade) was used to regulate the pH of 4the
3 4 of 13influent

at 6. Figure 2 shows the flow diagram for this study.

Chemical Abstract Service (CAS) Number 13463-67-7

Figure 2. Process flow diagram for this study.

Figure 2. Process flow diagram for this study.

2.3. Experimental Setup

The experiment was carried out in a six-place jar testing apparatus (JLT 6, flocculation tester,
Velp Scientifica, New York, NY, USA) as shown in Figure 3. The setup consist of six identical beakers
of 1 L, all equipped with a stirrer. Two 1 inch-diameter radiant fluorescent T8 black light blue bulbs,
Water 2020, 12, 214 4 of 13
Water 2020, 12, 214 4 of 14
Chemical Abstract Service (CAS) Number 13463-67-7

Table 2. Properties of TiO2 nanomaterial.

Properties Value
White powder content 94% purity
Phase mixture Rutile 94%, anatase 6%
Surface treatment Alumina, zirconia
Organic treatment Present
Surface gravity 4.1 g/cm3
Crystal size 10 nm
Loss at 105 ◦ C 0.60%
Bulk density 1.1 g/cm3
Oil absorption 18 cm3 /100 g pigment
Durability Highly durable
ISO 591 classification R2
Chemical Abstract Service (CAS) Number
Figure 2. Process flow diagram for this study. 13463-67-7

2.3. Experimental
2.3. Setup
Experimental Setup
The
Theexperiment
experimentwas wascarried
carriedoutout in
in a six-place
six-place jar
jartesting
testingapparatus
apparatus(JLT(JLT6, 6, flocculation
flocculation tester,
tester, Velp
Velp Scientifica, New York, NY, USA) as shown in Figure 3. The setup consist of six
Scientifica, New York, NY, USA) as shown in Figure 3. The setup consist of six identical beakers of identical beakers
of11L,
L,all
all equipped
equipped with a stirrer. Two Two 11inch-diameter
inch-diameterradiant
radiantfluorescent
fluorescentT8 T8black
blacklight
lightblue bulbs,
blue bulbs,
wavelength
wavelength (400
(400nm),
nm),with a power
with a power rating
ratingofof1818WW were
wereused
usedasas
the
theUVUV light
light source
sourcetotoexcite
excitethe
the
catalysts
catalystsininorder
ordertototrigger
triggera areaction.
reaction.The Thelight was
light wasincident
incidentononthethebeakers
beakersequally
equallytotoensure
ensure
uniformity
uniformity ofoflight distribution,
light distribution, asas
shown
shown ininFigure
Figure1.1.

Stirrer
knob Timer

Stirrer

18W UV
source

Beaker

Figure 3. 3.
Figure Experimental setset
Experimental up;up;
jarjar
testing apparatus.
testing apparatus.

AsAsperper the
the experimental
experimental design,
design, thethe three
three operating
operating parameters
parameters (catalyst
(catalyst dosage,
dosage, mixing
mixing speed,
speed,
and
and reaction
reaction time)
time) were
were varied,
varied, and
and their
their interactive
interactive effects
effects onon contaminant
contaminant removal
removal werewere analyzed.
analyzed.
Catalyst dosage was varied at 0.5, 1.0, and 1.5 g/L. Mixing speed was varied at 30, 60, and 9090
Catalyst dosage was varied at 0.5, 1.0, and 1.5 g/L. Mixing speed was varied at 30, 60, and rpm,
rpm,
whereas
whereas reaction
reaction time
time was
was varied
varied atat15,15,
30,30, and
and 4545min.
min. The
The volume
volume ofof effluent
effluent used
used forfor each
each beaker
beaker
was1 1L.L.After
was Aftereach
eachexperimental
experimental run,
run, the
the mixer
mixer was
was turned
turned off,and
off, andthe
thecontents
contents were
were allowed
allowed toto
settle for 30 min. After settling, 10 mL samples of each supernatant were analyzed of COD and SO42−.
Contaminant removal efficiency was calculated using Equation (1).
Water 2020, 12, 214 5 of 14

settle for 30 min. After settling, 10 mL samples of each supernatant were analyzed of COD and SO4 2− .
Contaminant removal efficiency was calculated using Equation (1).

Ao − A
η= × 100% (1)
Ao

where η is contaminant removal efficiency, and Ao and A are the initial and final concentrations (mg/L)
before and after treatment, respectively.

2.4. Response Surface Methodology (RSM)

Response surface methodology (RSM) was used in this study. RSM is a useful optimization tool in
developing and studying the impact of independent and interactive factors of a process. These include
process optimization, enhancement, and development of products [25]. Basically, RSM establishes
the relationship between a variable and its effect (response), with the advantage of producing a
mathematical model. In this experiment, the Box–Behnken design (BBD) was used. BBD is one of
the response surface designs that is widely used apart from the central composite design (CCD).
Even though CCD provides high prediction over the entire design space, BBD was preferred for this
experiment because with the same number of factors, it generates a smaller number of experimental
runs, which translates into less time and resource requirements without compromising accuracy [25].

3. Results and Discussion

By utilizing the BBD (Design Expert software V.11.1.0.1, Stat-Ease Inc., Minneapolis, MA, USA),
15 experimental runs were generated for each catalyst, including three replications. The three different
normalized central levels were coded as −1, 0, +1, corresponding to the minimum, central point,
and maximum for the factors considered. These experimental runs were randomized in order to
eliminate bias. Tables 3 and 4 show the experimental results for zeolite and TiO2 , respectively. Analysis
of variance (ANOVA) was carried out to check the validity and accuracy of the fitted model.

Table 3. Coded matrix and response values for zeolite.

Factor A Factor B Factor C

Response 1 (COD) % Response 2 (SO4 2− ) %
(Coded) (Coded) (Coded)
Catalyst Reaction Mixing
Run Actual Predicted Actual Predicted
Dosage (g/L) Time (min) Rate (rpm)
1 −1 1 0 90.1 90.07 82.87 82.89
2 −1 −1 0 90.28 90.31 82.87 82.81
3 −1 0 −1 91.38 91.35 84.26 84.24
4 0 0 0 88.84 88.84 82.87 82.89
5 0 −1 1 87.07 87.07 84.26 84.33
6 1 1 0 90.1 90.01 82.87 82.81
7 1 0 1 89.08 89.11 87.06 87.12
8 1 −1 0 90.04 90.01 83.2 83.06
9 0 −1 −1 93.24 93.24 81.47 81.54
10 0 1 1 91 91.06 84.26 84.25
11 0 1 −1 88.94 89.01 81.47 81.45
12 1 0 −1 88.37 88.4 78.68 78.74
13 −1 0 1 86.55 86.52 81.47 81.45
14 0 0 0 88.84 88.84 82.87 82.89
15 0 0 0 88.84 88.84 82.87 82.89
Water 2020, 12, 214 6 of 14

Table 4. Coded matrix and response values for TiO2 .

Factor A Factor B Factor C

Response 1 (COD) % Response 2 (SO4 ) %
(Coded) (Coded) (Coded)
Catalyst Reaction Mixing
Run Actual Predicted Actual Predicted
Dosage (g/L) Time (min) Rate (rpm)
1 0 −1 1 90.59 90.59 80.45 80.42
2 −1 0 −1 91.51 91.57 81.14 81.11
3 1 0 −1 90.41 90.47 83.94 83.97
4 −1 0 1 91.17 91.11 82.54 82.51
5 0 0 0 88.51 88.51 81.38 81.38
6 0 1 1 89.63 89.76 79.05 79.08
7 1 0 1 90.88 90.82 79.75 79.78
8 −1 1 0 91.25 91.19 82.54 82.54
9 0 0 0 88.51 88.51 81.38 81.38
10 −1 −1 0 89.96 90.02 81.14 81.21
11 0 −1 −1 90.01 89.88 81.84 81.81
12 1 −1 0 90.49 90.55 83.94 83.94
13 0 0 0 88.51 88.51 81.38 81.38
14 1 1 0 89.33 89.27 80.01 79.94
15 0 1 −1 90.59 90.59 80.44 80.47

3.1. Model Fitting and Statistical Analysis

The reduced form of the models generated by the Design Expert software for contaminant removal
in coded form is represented by Equations (2)–(5). Equations (2), (3), and (5) are quadratic models,
whereas Equation (4) is a two-factor interaction (2FI) model. The model reduction and modification
was necessary to enhance the predictability of the response variables. The models’ automatic selection
and modification was based on Akaike information criterion (AICc) with a correction for a small
design. AICc is multiple-model selection method and criteria used to choose the best model required.
The models present a direct relationship between the dependent variables (COD and SO4 2− removal)
and the independent variables (catalyst dosage (A), reaction time (B), and mixing rate (C)). With these
models, COD and SO4 2− removal can be predicted within the designed space.

COD (Z) = 88.84 − 0.09A − 0.06B − 1.03C + 0.06AB + 1.39AC + 2.06BC + 1.25B2 , (2)

COD (TiO2 ) = 88.51 − 0.35A − 0.03B − 0.03C − 0.61AB + 0.20AC − 0.39BC + 1.27A2 + 0.48B2 + 1.22C2 , (3)

SO4 (Z) = 82.89 + 0.04A − 0.04B + 1.40C − 0.08AB + 2.79AC, (4)

SO4 (TiO2 ) = 81.38 + 0.03A − 0.67B − 0.70C − 1.33AB − 1.40AC + 0.96A2 − 0.43B2 − 0.50C2 . (5)

The extent to which terms of the models can affect the response or contaminant removal are
associated with the positive and negative coefficient of the terms. Negative coefficients specify
undesirable effects of the factors, whereas positive coefficients show that a factor or combination of
factors contribute favorably to the contaminant removal. Again, the magnitudes of the coefficients
correlate with the degree to which the response variable is affected.
To check the statistical accuracy and validity of the model, analysis of variance (ANOVA) was
performed for each model, as shown by Tables 5–8. Typical features of ANOVA are the F-values,
p-values, R2 , and predicted R2 values. These values show whether the model is statistically valid or
not. As shown in the tables, for all models, the F-values were greater than their respective p-values
for each term in the model, indicating the significance of each interaction term in the model. In all
instances, the probability for the F-value occurring due to noise was 0.01%. Furthermore, the p-values
for all model terms were less than 0.05, which showed the significance of these model terms and can
therefore be generalized to a broader range of interest.
Water 2020, 12, 214 7 of 14

The correlation coefficient (R2 ) defines how close a set of data are to the fitted regression line. This
value is of immense statistical significance, as it gives a clear indication of how good a dataset fits a
model [26]. The closer the R2 value is to 1, the more meaningful the model. As seen from the tables,
the R2 values (0.9994, 0.999, 0.9954, and 0.9994) and their respective adjusted R2 values (0.9988, 0.9984,
0.9872, and 0.9985) are close to 1, suggesting that the developed statistical model fitted well with the
data obtained.

Table 5. ANOVA for COD removal by zeolite—reduced quadratic model. CV: coefficient of variation.

Sum of Degree of Mean

Source F-Value p-Value
Squares Freedom Square
Model 39.05 7 5.58 1614.82 <0.0001 significant
A—Catalyst
0.0648 1 0.0648 18.76 0.0034
dosage
B—Reaction
0.03 1 0.03 8.69 0.0215
time
C—Mixing
8.47 1 8.47 2451.01 <0.0001
rate
AB 0.0144 1 0.0144 4.17 0.0805
AC 7.67 1 7.67 2221.24 <0.0001
BC 16.93 1 16.93 4902.02 <0.0001
B2 5.87 1 5.87 1697.88 <0.0001
Residual 0.0242 7 0.0035
Lack of fit 0.0242 5 0.0048
Pure error 0 2 0
Cor total 39.07 14
Adjusted R2 Predicted R2 Adeq. Pr SD
R2 0.9994 CV% 0.0657 Mean 89.51
0.9988 0.9955 156.67 0.0588

Table 6. ANOVA for SO4 2− removal by zeolite—reduced two-factor interaction (2FI) model.

Sum of Degree of Mean

Source F-Value p-Value
Squares Dreedom Square
Model 46.84 5 9.37 1764.91 <0.0001 significant
A—Catalyst
0.0144 1 0.0144 2.72 0.1334
dosage
B—Reaction
0.0136 1 0.0136 2.56 0.1438
time
C—Mixing
15.6 1 15.6 2938.04 <0.0001
rate
AB 0.0272 1 0.0272 5.13 0.0498
AC 31.19 1 31.19 5876.09 <0.0001
Residual 0.0478 9 0.0053
Lack of fit 0.0478 7 0.0068
Pure error 0 2 0
Cor total 46.89 14
Adjusted R2 Predicted R2 Adeq. Pr SD
R2 0.999 CV% 0.0879 Mean 82.89
0.9984 0.9953 181.80 0.0729
Water 2020, 12, 214 8 of 14

Table 7. ANOVA for COD removal by TiO2 —quadratic model.

Sum of Degree of Mean

Source F-Value p-Value
Squares Freedom Square
Model 14.15 9 1.57 120.91 <0.0001 significant
A—Catalyst
0.9661 1 0.9661 74.28 0.0003
dosage
B—Reaction
0.0078 1 0.0078 0.6007 0.4733
time
C—Mixing
0.0078 1 0.0078 0.6007 0.4733
rate
AB 1.5 1 1.5 115.39 0.0001
AC 0.164 1 0.164 12.61 0.0164
BC 0.5929 1 0.5929 45.59 0.0011
A2 5.93 1 5.93 456.12 <0.0001
B2 0.8507 1 0.8507 65.41 0.0005
C2 5.45 1 5.45 419.12 <0.0001
Residual 0.065 5 0.013
Lack of fit 0.065 3 0.0217
Pure error 0 2 0
Cor total 14.22 14
Adjusted R2 Predicted R2 Adeq. Pr SD
R2 0.9954 CV% 0.1266 Mean 90.09
0.9872 0.9268 32.9036 0.114

Table 8. ANOVA for SO4 2− removal by TiO2 —reduced quadratic model.

Sum of Degree of Mean

Source F-Value p-Value
Squares Freedom Square
Model 27.82 8 3.48 1187.01 <0.0001 significant
A—Catalyst
0.0098 1 0.0098 3.35 0.1171
dosage
B—Reaction
3.55 1 3.55 1212.33 <0.0001
time
C—Mixing
3.88 1 3.88 1323.96 <0.0001
rate
AB 7.1 1 7.1 2424.66 <0.0001
AC 7.81 1 7.81 2666.98 <0.0001
A2 3.42 1 3.42 1167.76 <0.0001
B2 0.6987 1 0.6987 238.52 <0.0001
C2 0.9231 1 0.9231 315.13 <0.0001
Residual 0.0176 6 0.0029
Lack of fit 0.0176 4 0.0044
Pure error 0 2 0
Cor total 27.83 14
Adjusted R2 Predicted R2 Adeq. Pr SD
R2 0.9994 CV% 0.0665 Mean 81.39
0.9985 0.9919 116.61 0.054

Another way to determine the significance of a model is by measuring its adequate precision
(Adeq. Pr) and coefficient of variation (CV). Adequate precision is the signal-to-noise ratio which
measures the range of the predicted response relative to its associated error. An adequate precision
of greater than 4 is generally desired [26]. From the tables above, the values obtained for adequate
precision prove the adequacy of the model. The CV is the ratio of the standard deviation to the mean.
This value, expressed as a percentage, shows the level of dispersion around the mean. Lower values
of CV suggest more precise models [27]. Evidently, the CV values given in the tables above are low
enough to ensure significant models.
Water 2020, 12, 214 9 of 14

3.2. Interactive Effects of Parameters

The cross-factor interactive effects of the factors (catalyst dosage, reaction time, and mixing rate)
on the response (COD and SO4 2− removal) were studied. Figures 4–7 represent the 2D (contour)
and 3D (surface) plots resulting from the cross factor interactions on the contaminant removal by
the photo-catalysts.

Figure 4. 2D and 3D plots representing the cross factor interactive effects of the interaction between
reaction time and mixing rate (BC) on COD removal by zeolite.

Figure 5. 2D and 3D plots representing the cross factor interactive effects of the interactions between
catalyst dosage and mixing rate (AC) on COD removal by TiO2 .
Water 2020, 12, 214 10 of 14

Figure 6. 2D and 3D plots representing the cross factor interactive effects of AC on SO4 2− removal
by zeolite. 1

Figure 7. 2D and 3D plots representing the cross factor interactive effects of catalyst dosage and reaction
time (AB) on SO4 2− removal by TiO2 .

Figure 4 represents the interaction between reaction time and mixing rate (BC). The combined
effects of these two parameters have the greatest effect in the COD removal by zeolite. It can be seen,
that with a reaction time of 15 to 21 min and mixing rate of 30–50 rpm, an optimum removal efficiency
of 93% was achieved with minimum catalyst dosage. As catalyst dosage increased, removal efficiency
reduced. This can be explained by the fact that higher catalyst dosage causes lumping of particles,
consequently leading to poor light penetration into the system [28]. In Figure 5, the effect of the
interactions between catalyst dosage and mixing rate (AC) on COD removal by TiO2 is shown. AC
was proven to have the highest effect on this system, as shown by the quadratic model in Equation (2).
It can be inferred from the figure that as catalyst dosage increased, mixing rate also increased. This
corresponding increase in mixing rate was needed in order to enhance proper homogenizing of the
catalyst in the reacting media.
Figures 6 and 7 represent the plots for cross factor interactive effects on SO4 2− removal by zeolite
and TiO2 , respectively. As shown in Figure 6, AC had the highest influence on SO4 2− removal by
Water 2020, 12, 214 11 of 14

zeolite, whereas catalyst dosage and reaction time (AB) had the highest influence on SO4 2− removal by
TiO2 , as shown in Figure 7.

4. Optimum Conditions
Numerical optimization was done to determine the optimum conditions of the three parameters
for contaminant removal. The numerical optimization technique explores the entire design space
on the basis of the developed models to detect the optimum factor conditions for the given range.
Equations (2)–(5) served as the objective functions, whereas the three independent variables served as
constrains. These constrains were set within the given range. The goal for the optimization was to
achieve maximum contaminant removal.
Figure 8 represents a ramp graph showing the optimum conditions for the operating parameters
and the desirability obtained from the zeolite experiment. As can be inferred from the graph, to achieve
maximum COD removal of 92% and SO4 2− removal of 87%, all operating parameters were at the
maximum with a desirability of 91.7% contaminant removal. This translates into maximum time and
energy requirements to achieve the set goal of contaminant removal for the given range of factors.

Figure 8 Figure 8. Optimum operating conditions for zeolite.

Figure 9 shows the ramp graph for the optimum conditions of the operating parameters for the
TiO2 experiment. Unlike zeolite, a catalyst dosage of 1.5 g/L, reaction time of 15 min, and mixing rate
of 30 rpm achieved a removal efficiency of 91.21% of COD and 85.5% removal efficiency of SO4 2− ,
leading to a desirability of 91%, which translates into lesser energy and time requirements for achieving
maximum contaminant removal for the given range of factors.

Figure 9
Water 2020, 12, 214 12 of 14
Figure 8

Figure 9. Optimum operating conditions for TiO2 .

Figure 9

Table 9 shows a comparative study of work done by other authors in photo-catalytic degradation
of petroleum refinery effluent. It can be seen that much focus was given to only the organic (COD)
aspects of the petroleum refinery effluent without consideration for the possibility of removing other
inorganics such as salts simultaneously. This study however considered the possibility of removing
both organics (COD) and inorganics (SO4 2− ) simultaneously from oil refinery effluent. The conditions
of the experiment and the results obtained in each case are shown in the table.

Table 9. Comparative studies on photo-catalytic degradation of petroleum refinery effluent.

Photo-Catalytic Degradation of Petroleum Refinery Effluent

Contaminant
Conditions Results (Removal %) Reference
Investigated
pH (4), catalyst concentration
(100 mg/L), temperature (45
* TCOD ◦ C), and reaction time (120 Over 83 [29]
min)
Catalyst concentration (0.2 1
** DOC g/L), reaction time (60 min), 21 [30]
reactor volume (100 mL)
Temperature (45 ◦ C), catalyst
COD concentration (100 mg/L), pH 90 [31]
(3), reaction time (240 min)
Catalyst concentration (1 g/L),
COD 60 [32]
pH (3), temperature (50 ◦ C)
Catalyst concentration (1.5
g/L), pH (6), reaction time (15
COD 92
min), temperature (25 ± 2 ◦ C), * This study
mixing rate (30 rpm)
Catalyst concentration (1.5
g/L), pH (6), reaction time (45
SO4 2− 87
min), temperature (25 ± 2 ◦ C),
mixing rate (90 rpm)
* Total chemical oxygen demand, ** dissolved organic carbon.
Water 2020, 12, 214 13 of 14

5. Conclusions
This study compared COD and SO4 2− (contaminants) removal efficiencies of zeolite and TiO2
from oily wastewater in a photo-catalytic system. A 2FI model and a quadratic model were developed
for SO4 2− and COD removal by zeolite, respectively, whereas quadratic models were developed for
SO4 2− and COD removal by TiO2 . The optimum conditions for zeolite were found to be a mixing rate
of 90 rpm, reaction time of 45 min, and catalyst dosage of 1.5 g/L. For TiO2 the optimum conditions
were found to be a mixing rate of 30 rpm, reaction time of 15 min, and catalyst dosage of 1.5 g/L.
Validity of the models were demonstrated by analysis of variance (ANOVA) and were found to be in
agreement with predicted values. The desirability of using zeolite and TiO2 were almost the same
(92% and 91% respectively). Between the two photo-catalysts, TiO2 was found to be more promising in
the treatment of oily wastewater than the zeolite. Therefore, incorporating TiO2 in a photo-catalytic
system optimized with RSM has a bright future in the water and wastewater setting for both organic
and inorganic contaminant removal.

Author Contributions: Conceptualization: E.K.T. and E.O.E.; methodology: E.K.T. and E.O.E.; software: D.A.-S.,
E.K.T., and E.O.E.; validation, E.K.T. and D.A.-S.; formal analysis E.K.T. and E.O.E.; investigation: E.K.T. and
E.O.E.; resources: S.R. and E.K.T.; data curation: E.O.E. and D.A.-S.; writing—E.O.E.; writing—review and editing:
E.K.T., D.A.-S., and S.R.; visualization: E.K.T. and E.O.E.; supervision: S.R. and E.K.T.; project administration: S.R.
and E.K.T. All authors have read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Acknowledgments: The authors are thankful to the Department of Chemical Engineering, Durban University of
Technology (DUT) and FFS Refiners for their support.
Conflicts of Interest: The authors declare no conflict of interest.

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