membranes

Article
Adsorption-Enhanced Ceramic Membrane Filtration Using
Fenton Oxidation for Advanced Treatment of Refinery
Wastewater: Treatment Efficiency and
Membrane-Fouling Control
Haotian Mu 1 , Qi Qiu 2 , Renzhen Cheng 1 , Liping Qiu 1,3, *, Kang Xie 1,3 , Mingchang Gao 1 and Guicai Liu 1,3, *

1 School of Civil Engineering and Architecture, University of Jinan, Jinan 250022, China;
[email protected] (H.M.); [email protected] (R.C.); [email protected] (K.X.);
[email protected] (M.G.)
2 School of Water Conservancy and Environment, University of Jinan, Jinan 250022, China;
[email protected]
3 Research Center for Functional Material & Water Purification Engineering of Shandong Province,
Jinan 250022, China
* Correspondence: [email protected] (L.Q.); [email protected] (G.L.)

Abstract: With the development of the refining industry, the treatment of refinery wastewater
has become an urgent problem. In this study, a ceramic membrane (CM) was combined with



Fenton-activated carbon (AC) adsorption to dispose of refinery wastewater. The effect of the com-


bined process was analyzed using excitation–emission matrix (EEM), ultraviolet-visible (UV-vis)
Citation: Mu, H.; Qiu, Q.; Cheng, R.; and Fourier transform infrared spectroscopies (FTIR). Compared with direct filtration, the combined
Qiu, L.; Xie, K.; Gao, M.; Liu, G. process could significantly improve the removal of organic pollution, where the removal rate of
Adsorption-Enhanced Ceramic the COD and TOC could be 70% and the turbidity removal rate was above 97%. It was found that
Membrane Filtration Using Fenton
the effluent could meet the local standards. In this study, the membrane fouling was analyzed for
Oxidation for Advanced Treatment of
the impact of the pretreatment on the membrane direction. The results showed that Fenton-AC
Refinery Wastewater: Treatment
absorption could effectively alleviate membrane fouling. The optimal critical flux of the combined
Efficiency and Membrane-Fouling
Control. Membranes 2021, 11, 651.
process was increased from 60 to 82 L/(m2 ·h) compared with direct filtration. After running for
https://doi.org/10.3390/ about 20 d, the flux remained at about 55 L/(m2 ·h) and the membrane-fouling resistance was only
membranes11090651 1.2 × 1012 m−1 . The Hermia model revealed that cake filtration was present in the early stages of
the combined process. These results could be of great use in improving the treatment efficiency and
Academic Editor: Yingchao Dong operation cycle of refinery wastewater.

Received: 24 June 2021 Keywords: refinery wastewater; ceramic membrane; combined process; membrane-fouling model;
Accepted: 21 August 2021 membrane-fouling control
Published: 25 August 2021

Publisher’s Note: MDPI stays neutral

with regard to jurisdictional claims in 1. Introduction
published maps and institutional affil-
With the development of the refining industry, the threat to the environment caused by
iations.
pollutants [1,2] contained in refinery wastewater has attracted more and more attention [3].
It is difficult for conventional treatments [4,5] to remove pollutants in wastewater such that
the local standards are met; therefore, deep treatment processes are essential. Membrane
filtration [6–8], activated carbon (AC) adsorption [9–11] and advanced oxidation processes
Copyright: © 2021 by the authors.
(AOPs) [12–14] have a wide range of applications in deep treatment processes of refinery
Licensee MDPI, Basel, Switzerland.
wastewater due to their unique advantages. However, the treatment efficiency of a single
This article is an open access article
technology is limited [15]. Based on these, it is necessary to design suitable combined
distributed under the terms and
processes for the treatment of refinery wastewater.
conditions of the Creative Commons
Compared with a single process, a combined process can remove pollutants in wastew-
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
ater more effectively and make full use of the advantages of various methods and make
4.0/).
up for their shortcomings [16]. After several years of research, some processes [17–24]

Membranes 2021, 11, 651. https://doi.org/10.3390/membranes11090651 https://www.mdpi.com/journal/membranes

Membranes 2021, 11, 651 2 of 16

were designed and researched for the treatment of refinery wastewater. According to the
previous research, a combined process that consists of an AOP and AC absorption dis-
played a great effect in the treatment of wastewater [25,26]. An AOP has a strong capacity to
degrade refractory macromolecular substances into small molecular substances with a fast
reaction speed. AC adsorption could be used to remove the pollutants at very low concen-
tration levels in wastewater [27]. Based on these methods, the combined process of AOPs
and AC adsorption has great potential in the treatment of refinery wastewater. However,
the application of AOPs and AC would introduce new colloidal substances into the wa-
ter after processing, and these substances are difficult to separate. To solve this issue,
a membrane was introduced.
Membrane separation is one of the most commonly used methods for the deep treat-
ment of refinery wastewater due to its many advantages [28–32]. Through previous re-
search, combining other processes with a membrane in the treatment of refinery wastewater
is an effective method for improving the quality of effluent and output [33–35]. However,
membrane fouling is the main reason that restricts the application of membranes in wastew-
ater treatment [36]; therefore, controlling membrane fouling is the key to improving the
efficiency of membrane filtration [28,32,37,38]. It was found from previous studies [39]
that pollutants in wastewater could be removed effectively via pretreatment so that the
operating pressure of the subsequent membrane system would be decreased and then
membrane fouling was alleviated. Among the possible membranes, it is feasible to combine
a ceramic membrane (CM) with an AOP and AC adsorption to improve treatment efficiency
and reduce membrane fouling [40–45]. The simultaneous combination of CM with an AOP
and AC adsorption is rarely applied in the deep treatment of refinery wastewater; as such,
the synergistic effect and membrane-fouling behavior are still unclear, which need further
research and verification.
In this study, Fenton oxidation, AC adsorption and CM filtration were selected as the
main components of a combined process for the deep treatment of refinery wastewater.
Single-membrane filtration and a combined process were simultaneously operated to
compare and analyze the treatment efficiency and membrane fouling. The model of
membrane fouling was built for revealing the mechanism of membrane fouling. This study
aimed to provide new insights to improve the efficiency of membrane processes for treating
refinery wastewater and alleviate membrane fouling.

2. Material and Methods

2.1. Material and Reagents
In this study, the CM was provided by the Advanced Ceramic Research Institute of the
Zibo High-tech Industrial Development Zone. Its structure is shown in Figure S1. There
are channels inside the framework of the membrane module. The feed entered the internal
channel through the pores on the membrane’s surface and moved to the low-pressure area
in the channel due to the suction from the pump. The liquid flowed out of the membrane
module assembly through its water outlet and was finally collected. The size was 240 mm
× 250 mm × 6 mm, the pore size was 100 nm and the mechanical strength was ≥15 MPa.
The pure water flux could reach 500 L/(m2 ·h) under a pressure of 0.03 MPa, which showed
a good permeability.
The adsorbent was granular activated carbon with a porosity of >70. Fe(NH4)2(SO4)2 ·6H2O
and H2O2 were the ARs used for the Fenton oxidation and K2Cr2O7 used for the analysis of COD
was GR. The water used in the experiment was taken from an oil refinery in Shandong.
The feed was from the secondary biochemical effluent of a refinery, where the turbidity
of the feed was about 1.78 NTU and the COD was 36~40 mg/L.

2.2. The Design of the Experiment

2.2.1. Direct CM Filtration Experiment
The CM was directly used to treat the refinery wastewater and was operated under
the condition of constant pressure filtration. The effluent was collected in a tank to test
Membranes 2021, 11, x FOR PEER REVIEW 3 of 18

Membranes 2021, 11, 651 3 of 16

The CM was directly used to treat the refinery wastewater and was operated under
the condition of constant pressure filtration. The effluent was collected in a tank to test its
quality for analysis of the treatment effect. During the operation, the critical flux of the
its quality for analysis of the treatment effect. During the operation, the critical flux of
CM was measured using the flow ladder method and the speed of the pump was con-
the CM was measured using the flow ladder method and the speed of the pump was con-
trolled to adjust the pressure on both sides of the membrane. The flux was changed every
trolled to adjust the pressure on both sides of the membrane. The flux was changed every
30
30min,
min,and
andthe
thedata
data of
of the
the flux and TMP
flux and TMP was
was recorded
recordedevery
every55min.
min.Three
Threeinitial
initialfluxes
fluxesof
of30,
30,6060 and 90 L/(m 2·h) during the operation of the filtration were selected and the vari-
and 90 L/(m2 ·h) during the operation of the filtration were selected and the variation
ation of the and
of the flux flux TMP
and TMP was noted
was noted to analyze
to analyze the membrane-fouling
the membrane-fouling behavior.
behavior.

2.2.2.
2.2.2.Experimental
ExperimentalSetup Setupofofthe theCombined
CombinedProcessProcess
The
Theexperimental
experimentalsetup setupofofthe thecombined
combinedprocess
processisisshown
shownininFigure
Figure1.1.The
Thefeed
feedfirst
first
entered
enteredintointo aa regulating tank tankequipped
equippedwith witha astirring
stirring blade,
blade, acidacid addition
addition equipment
equipment and
and a real-time
a real-time online online pH control
pH control device,device,
which waswhich usedwas used to
to adjust theadjust
pH of the pH of the
the wastewater
wastewater
to suitable to suitable conditions
conditions for Fentonfor Fenton oxidation.
oxidation. The effluent
The effluent stayed for stayed for became
5 min, 5 min, be- an
came an outflow and entered into the Fenton reaction tank. The
outflow and entered into the Fenton reaction tank. The tank was equipped with agitating tank was equipped with
agitating
equipment equipment that maintained
that maintained 120 r/min 120 to
r/min to increase
increase the reaction
the reaction efficiency.
efficiency. The dos-
The dosage of
age
theof the regents
regents was controlled
was controlled by metering
by metering pumps. pumps.
The pH Thecondition
pH condition was controlled
was controlled at 4.1
atand
4.1 the
andretention
the retention
timetime
waswas 30 min.
30 min. After
After thethe oxidation,
oxidation, thethe water’s
water’s pHpH was
was adjusted
adjusted to
to7 7by
byadding
addingNaOHNaOHin inthe
thepipe
pipebetween
between the the Fenton reaction tank tank and
and the
thesedimentation
sedimentation
tank,and
tank, andthethewater
waterentered
enteredthe thesedimentation
sedimentationtank tankfor
forprecipitating
precipitatingthe thesludge
sludgeeffectively.
effectively.
The water stayed in the tank for 45 min and then flowed into the membrane pool ininwhich
The water stayed in the tank for 45 min and then flowed into the membrane pool which
theactivated
the activatedcarbon
carbonwas wasdirectly
directlyaddedaddedtotothethemembrane
membranetank tankandandthetheconcentration
concentrationwas was
4040g/L.
g/L.After
Afterrunning
runningfor for1212d,d, the
the activated
activated carbon was was changed
changedatataacarboncarbonchange
changeraterateof
of4%/d.
4%/d.Continuous
Continuousaerationaerationatatthe thebottom
bottom of of
thethe
pool ensured
pool ensured thatthat
thethe
activated carbon
activated was
carbon
suspended
was suspended in the water,
in the andand
water, agitation waswas
agitation usedused
on the
on surface
the surfaceof the
of ceramic membrane
the ceramic mem-
to reduce
brane the deposition
to reduce the deposition of activated
of activatedcarbon andand
carbon pollutants
pollutantson the membrane’s
on the membrane’s surface.
sur-
Finally, the water was filtered using the CM and collected in a tank
face. Finally, the water was filtered using the CM and collected in a tank for the analysis for the analysis of the
oftreatment
the treatmentefficiency, wherewhere
efficiency, the run thetime
run was
timeabout 40 min.
was about The changes
40 min. in flux
The changes flux TMP
in and and
werewere
TMP noted everyevery
noted day todaystudy the membrane-fouling
to study the membrane-fouling behavior.
behavior.

Schematicdiagram
Figure1.1.Schematic
Figure diagramofof the
the combined
combined process:
process: 1. regulating
1. regulating tank;
tank; 2. Fenton
2. Fenton reaction
reaction tank;
tank; 3.
3. sedimentation
sedimentation tank;tank; 4. ceramic
4. ceramic membrane;
membrane; 5. membrane
5. membrane pool; 6.pool; 6. activated
activated carbon powder;
carbon powder; 7. pro-
7. production
duction water pump;
water pump; 8. blower.
8. blower.

2.3.The
2.3. TheMethod
MethodofofAnalysis
Analysis
TheCOD
The CODand andTOC
TOCinin the
the feed
feed were
were analyzed
analyzed using
using the
the potassium
potassium dichromate
dichromate
method and total organic carbon analysis (multi N/C ® 3100, Jena, Germany), respectively.
method and total organic carbon analysis (multi N/C® 3100, Jena, Jena, Germany), respec-
The turbidity and chromaticity were measured using a turbidity chromaticity meter
tively. The turbidity and chromaticity were measured using a turbidity chromaticity me-
(2100AN, Hach, CO, USA). The conductivity and pH were determined using a conductivity
ter (2100AN, Hach, Colorado, USA). The conductivity and pH were determined using a
analyzer (DDS-307, Lei Ci, Shanghai, China) and a pH meter (S220, Sedrwas, Goettin-
conductivity analyzer (DDS-307, Lei Ci, Shanghai, China) and a pH meter (S220, Sedrwas,
gen, Germany), respectively. A dual-beam UV-visible spectrophotometer (TU-1901, Gen-
Goettingen,Germany), respectively. A dual-beam UV-visible spectrophotometer (TU-
eral Analysis of Beijing, China) was used to scan and analyze the pollutants in the feed.
1901, General Analysis of Beijing, China) was used to scan and analyze the pollutants in
The wavelength range was 190~600 nm, the scanning step was 0.25 nm and the optical
path of the quartz colorimeter was 10 mm. FTIR (NICOLET WAS10, Seymour, Waltham,
Membranes 2021, 11, 651 4 of 16

MA, USA) was used to analyze the pollutant categories and organic functional groups in
each sample. The resolution was 4 cm−1 , the number of scans was 32 and the scanning
interval was 4000~550 cm−1 .
A three-dimensional fluorescence spectrum (EEM) was determined using a syn-
chronous absorption three-dimensional fluorescence spectrometer (HORIBA Aqualog® ,
British HORIBA) for the qualitative analysis of each water sample. The excitation spectra
(EX) were scanned from 200 to 450 nm and the emission spectra (EM) were scanned from
240 to 600 nm. The scanning velocity was 50 nm/s.

2.4. Membrane-Fouling Analysis

In the experiment, the membrane pressure on both sides was adjusted according to
the speed of the pump and the flux of clear water collected during a certain period was
calculated using a stopwatch and a measuring cylinder. The flux was calculated under
different pressures according to the following Equation (1):

V
J= (1)
tS

where J was the permeate flux (L/(m2 ·h)), V was the filtration volume (L), S was the
membrane area (m2 ) and t was the filtration time (h).
The inherent resistance of the CM was a basic indicator to measure the membrane
performance. The TMP and flux were used as calculation parameters of the inherent
resistance. Equation (2) was used for this calculation:

TMP
Rm = (2)
µJ0

where Rm was the intrinsic membrane resistance, the value of TMP was equal to the
membrane pressure on both sides, J0 was pure water flux (m3 /(m2 ·s)) and µ was assumed
to be the viscosity of water at 25 ◦ C (0.8937 × 10−3 N·s/m2 ).
Based on Darcy’s law, the membrane-fouling resistance was calculated:

TMP
J=   (3)
µ Rm + R f

R = Rm + Rf (4)

where R was the total membrane resistance (m−1 ) and Rf was the membrane-fouling
resistance (m−1 ).
The critical flux was an important indicator for analyzing the rate of membrane fouling.
In the experiment, the critical flux of membrane filtration was measured using the flow
ladder method. The flux was changed every 30 min, and the flux and TMP were recorded
every 5 min. The critical flux was determined by analyzing the TMP and flux.

2.5. Membrane-Fouling Model

The Hermia model was used to fit the membrane-fouling model during the experi-
ment and analyze the type of membrane fouling. The Hermia model contains four types:
complete blockage, intermediate blockage, standard blockage and cake filtration. Complete
blockage, intermediate blockage and standard blockage can be classified into a block filter
and are produced by membrane pore blocking. The cake filtration model is based on
the screening effect that particle pollutants carry via a filtrate cake that is formed on the
membrane surface. The thickness of the cake and resistance increased with the running
time. The specific equation is shown in Table 1.
 (kPa), P0 represented the initial TMP data when the filtration begins (kPa), Vs was the cumulative
filtrate volume and k’ was the model constant.

Model Equations Model Equations

Membranes 2021, 11, 651 Cake filtration 1 Standard blockage 𝑘 5 of 16

=1+𝑘 𝑉 𝐽 =1− 𝑉
𝐽′ 2
Intermediate block-
Complete blockage
age ln𝐽 = −𝑘 𝑉 𝐽 =1−𝑘 𝑉
Table 1. The equations of the Hermia model: J 0 s = p0 /p, p represented the TMP data at a given time
(kPa), p0 represented the initial TMP data when the filtration begins (kPa), Vs was the cumulative
3. Results and Discussion
filtrate volume and k0 was the model constant.
Separate membrane filtration and combined processes were adopted to` treat
Model Equations Model
the feed. By analyzing the removal effect of pollutants in the wastewater and membrane- Equations
fouling behavior, the treatment
filtration mechanism 1 of the 0combined process and the reason2 for
0 1 0
Cake Js 0
= 1 + k Vs Standard blockage Js = 1 − k2 Vs
the membrane fouling were obtained.
Intermediate blockage 0
ln J = −k V 0 Complete blockage 0
J = 1−k V0
S s s s

3.1. Treatment Efficiency

3. Results and Discussion
3.1.1. The Removal of Organic Pollutants and the Turbidity
Separate membrane filtration and combined processes were adopted to treat the
The removal
feed. Byeffect of organic
analyzing thepollutants in theof
removal effect refinery wastewater
pollutants can be reflected
in the wastewater and membrane-
using the TOC fouling behavior, the treatment mechanism of the combined process rate
and COD. Under the condition of direct filtration, the removal and of
thethe
reason for the
COD and TOC was about
membrane 20% were
fouling and 14%, respectively, and the concentrations of the COD
obtained.
and TOC were 28~30 mg/L and about 8.5 mg/L in the effluent, respectively (as shown in
Figure 2). It 3.1.
wasTreatment
found that the removal rate of organisms using direct membrane filtra-
Efficiency
tion was stable but
3.1.1. relatively
The Removal low. This might
of Organic have been
Pollutants andbecause the organics in refinery
the Turbidity
wastewater wereThe mostly dissolved [28]. After the filtration, the suspended
removal effect of organic pollutants in the refinery wastewater particles can
andbe reflected
oil with small grains
using thewere
TOC retained
and COD. but a large
Under thenumber
conditionof organics
of direct could go through
filtration, the rate of the
the removal
pores, whichCOD resulted in the low removal rate observed.
and TOC was about 20% and 14%, respectively, and the concentrations of the COD
and TOC were 28~30 mg/L and about 8.5 mg/L in the effluent, respectively (as shown in
Figure 2). It was found that the removal rate of organisms using direct membrane filtration
was stable but relatively low. This might have been because the organics in refinery
wastewater were mostly dissolved [28]. After the filtration, the suspended particles and oil
with small grains were retained but a large number of organics could go through the pores,
which resulted in the low removal rate observed.

Membranes 2021, 11, x FOR PEER REVIEW 6 of 1

Figure
Figure 2. Removal of organic pollutants 2. Removal
and turbidity of organic
using pollutants
direct filtration andand turbidity
combined using direct
processes: filtration
(a) the removal and
of combined pro
cesses: (a) the removal of TOC from the refinery wastewater; (b) the removal
TOC from the refinery wastewater; (b) the removal of COD from the refinery wastewater; (c) the removal of turbidity from of COD from the re
the refinery wastewater. finery wastewater; (c) the removal of turbidity from the refinery wastewater.

Compared with direct filtration, although the treatment effect of the organics using
the combined process fluctuated slightly, the removal rate of the COD and TOC remained
above 70% under the combined process. The system operated stably and the COD and
TOC in the effluent were lower than 10 mg/L and 2~3 mg/L, respectively. The result me
the quality requirements. It was speculated that the process of Fenton oxidation and AC
Membranes 2021, 11, 651 6 of 16

Compared with direct filtration, although the treatment effect of the organics using
the combined process fluctuated slightly, the removal rate of the COD and TOC remained
above 70% under the combined process. The system operated stably and the COD and
TOC in the effluent were lower than 10 mg/L and 2~3 mg/L, respectively. The result met
the quality requirements. It was speculated that the process of Fenton oxidation and AC
adsorption could effectively improve the removal effect of CM on organic pollutants in
refinery wastewater.
The turbidity in the refinery wastewater was high; therefore, it should be further
analyzed. The turbidity removal effect is shown in Figure 2c. It can be seen that the direct
filtration using the CM had a good effect on removing the turbidity, where the removal rate
could reach about 90%. The turbidity in the feed could be reduced from 1.9 to 0.2 (NTU)
after the filtration and the effluent could meet the local standard. The result showed that
the concentration of the turbidity in the refinery wastewater could be effectively reduced
by the direct filtration of the CM. Some research [41] revealed the treatment effect of CM
on wastewater with different turbidity levels. It was indicated that more than 98% of
the turbidity was removed during the filtration of CM under all the tested conditions.
Meanwhile, the removal effect of turbidity using the combined system showed that the
turbidity removal rate was above 97% and the turbidity in the effluent was lower than
0.05 NTU under the tested conditions. Therefore, compared with direct filtration,
the removal of turbidity could be further improved using the combined process.

3.1.2. Fluorescence EEM Spectra

EEM was widely used as a useful method for the analysis of pollutant composition
in water [46–50]. In this study, EEM was used to analyze the composition in the refinery
wastewater at different stages. It was found that the EEM spectra could be divided into
two regions: λEX /λEM = 245 nm/385 nm and λEX /λEM = 305 nm/385 nm (as shown in
Figure 3a). According to previous studies [51,52], the peaks might be related to alkanes and
polycyclic aromatic hydrocarbons, such as tyrosine and tryptophan. As shown in Figure 3b,
the peak intensities of the two regions showed no obvious change. It was noted that most
organic matter, such as aromatic compounds, was rarely intercepted using direct mem-
brane filtration. The organic pollutants in the refinery wastewater could be significantly
reduced using Fenton oxidation (shown from Figure 3c), where the peak removal rates at
245 nm/385 nm and 305 nm/385 nm were above 95% and 94%, respectively. The locations
of the peaks drifted, which meant that macromolecular substances, such as polycyclic
aromatic hydrocarbons, turned into substances with a lower molecular weight, such as
fulvic acid. To further explore the removal mechanism, the removal effect was researched
via dosing with PFS for flocculation alone (as shown in Figure 3d). The result indicated
that the removal of fluorescent substances in the refinery wastewater using the Fenton
system was a synergistic process of flocculation and oxidation, and the removal rate
was relatively low when using flocculation alone, which indicated that the oxidation
played a leading role. The area of the peak was further decreased after the AC absorption
(as shown in Figure 3e), where the peak was below 50 and the removal rate was above 96%
after the absorption. It was supposed that some small molecules, such as fulvic acid and
humic acid, were thoroughly adsorbed on the surface or in the pores of AC during the
process [53]. After the pretreatment of Fenton oxidation and AC absorption, the water was
filtrated using CM and, as a result, the pollutants in the feed were completely removed
using the combined process (as shown in Figure 3f). Therefore, compared with the result
of direct filtration, the treatment effect of refinery wastewater using the combined process
was better.
 trated using CM and, as a result, the pollutants in the feed were completely removed using
the combined process (as shown in Figure 3f). Therefore, compared with the result of di-
rect filtration, the treatment effect of refinery wastewater using the combined process was
better.
Membranes 2021, 11, 651 7 of 16

Figure 3. EEM diagram of water: (a) feed; (b) single TCM; (c) after Fenton oxidation; (d) dosing Fe2+ for coagulation;
(e) absorbed by AC; (f) effluent. The excitation spectra (EX) were scanned from 200 to 450 nm and the emission spectra (EM)
were scanned from 240 to 600 nm. The scanning velocity was 50 nm/s.
 Figure 3. EEM diagram of water: (a) feed; (b) single TCM; (c) after Fenton oxidation; (d) dosing Fe2
for coagulation; (e) absorbed by AC; (f) effluent. The excitation spectra (EX) were scanned from 200
to 450 nm and the emission spectra (EM) were scanned from 240 to 600 nm. The scanning velocity
was 50 nm/s.
Membranes 2021, 11, 651 8 of 16
3.1.3. The UV-vis and FTIR Analyses
UV-vis is an important method for the analysis of dissolved organic matter in
wastewater.
3.1.3. The UV-vis Theandmethod was used in many studies to analyze the concentration of COD
FTIR Analyses
in wastewater
UV-vis is anand the transformation
important method for theof organic
analysis of matter
dissolved[54,55].
organicAs shown
matter in Figure 4, the
in wastew-
change
ater. The ofmethod
organics wasin used
the refinery
in many wastewater after filtration
studies to analyze was not of
the concentration obvious
COD infrom the
UV-vis,
wastewater indicating
and the that direct membrane
transformation of organicfiltration
matter was not ideal
[54,55]. for removing
As shown in Figure the
4, pollu-
the change of organics in the refinery wastewater after filtration was not
tants in the refinery wastewater. After the Fenton oxidization, the absorbance for wave- obvious from the
UV-vis, indicating
lengths ranging fromthat direct
190 tomembrane
230 nm was filtration was notreduced,
effectively ideal for removing
while thethe pollutants
location of the peak
in the refinery wastewater. After the Fenton oxidization, the absorbance
at 220 nm changed a little and the peak at 202 nm was red-shifted to 210 nm. This indicated for wavelengths
ranging from 190 to 230 nm was effectively reduced, while the location of the peak at
that aromatic compounds could be effectively reduced using Fenton oxidation. It can be
220 nm changed a little and the peak at 202 nm was red-shifted to 210 nm. This indicated
seen from Figure
that aromatic 4 that the
compounds absorbance
could (Abs)
be effectively valuesusing
reduced at allFenton
wavelengths
oxidation.decreased
It can beafter the
absorption by the AC, indicating that the small pollutants
seen from Figure 4 that the absorbance (Abs) values at all wavelengths decreased produced after theafter
Fenton oxi-
dation could be
the absorption by removed by the AC.
the AC, indicating that In
thethe end,
small the absorbance
pollutants of the
produced after theeffluent
Fenton treated
using
oxidationthecould
combined process
be removed wasAC.
by the significantly
In the end, thereduced compared
absorbance with the
of the effluent direct mem-
treated
using the combined process was significantly reduced compared with
brane filtration, which indicates that the pretreatment of Fenton oxidation and AC ad- the direct membrane
filtration, which
sorption could indicates
promotethat thetheremoval
pretreatmenteffectof Fenton
of the oxidation
CM for and AC adsorption
organics in the refinery
could promote
wastewater. the removal effect of the CM for organics in the refinery wastewater.

3.6
3.6 (a) (b)

3.0
3.0
Feed
Feed 2.4 Fenton oxidation
2.4
Filtrate PAC adsorption
1.8 Effluent
Abs

Abs

1.8

1.2
1.2

0.6
0.6

0.0
0.0
200 220 240 260 280 300 190 200 210 220 230 240 250 260 270 280

Wavelength(nm) Wavelength(nm)

Figure 4. The changes in UV-vis for varied effluents: (a) the changes in UV-vis during the direct
filtration using the ceramic membrane; (b) the changes of UV-vis in each phase of the combined
process. The wavelength range was 190~600 nm, the scanning step was 0.25 nm and the optical path
of the quartz colorimeter was 10 mm.

FTIR is an effective method for analyzing the categories of pollutants and functional
groups of organic compounds in water [56]. Through FTIR analysis, pollutants in water
can be effectively identified and the rules of transformation about organic compounds
under different treatment conditions can be analyzed. The feed and effluent of the different
stages, including Fenton oxidation, AC absorption and the membrane, were each analyzed
using FTIR (Figure 5). As shown in Figure 5, after the Fenton oxidation, the peak in the
range from 1640 cm−1 to 1141 cm−1 decreased, which indicated that the Fenton oxidization
could effectively reduce the concentration of sulfonic acid ester, amines and aromatic
pollutants, and the result was consistent with the results of the EEM, where the peaks at
1384 cm−1 and 1141 cm−1 were also significantly lower compared with the feed. We found
that a good treatment effect on sulfate lipids and amines could be achieved by Fenton
Figure 4. The
oxidation. Thechanges in1640
peaks at UV-vis
cm−for varied
1 and 3416effluents: (a) the changes
cm−1 significantly in UV-vis
decreased afterduring
the ACthe direc
filtration using the ceramic membrane; (b) the changes of UV-vis in each phase of
absorption, where fulvic acid and other small molecule substances in the refinery wastewa- the combined
process.
ter couldThebe wavelength range wasthe
removed. Moreover, 190~600 nm, the scanning
concentration of aminestep was 0.25 nm
compounds andeffluent
in the the optical path
of the quartz colorimeter was 10 mm.
was further reduced by the combined process of Fenton oxidation and AC absorption.
However, after oxidation, a new peak appeared at 1270 cm−1 , which might have been the
anti-symmetric stretching vibration of the SO3 of the sulfate RO-SO2 -O-. After the analysis,
it was determined that the R groups in R1 O-SO2 -OR2 in the sulfate were oxidized to
form the sulfate, and the sulfate was difficult to completely remove using the process
 sorption. However, after oxidation, a new peak appeared at 1270 cm−1, whic
been the anti-symmetric stretching vibration of the SO3 of the sulfate RO-SO2
analysis, it was determined that the R groups in R1O-SO2-OR2 in the sulfate w
Membranes 2021, 11, 651 to form the sulfate, and the sulfate was difficult to completely remove 9 of 16 usin
of AC adsorption. It can be seen from Figure 5 that the sulfate was mainly re
CM filtration. It was confirmed from the FTIR result that the molecular sub
asofaromatic
AC adsorption. It can be
pollutants, seen from
could Figure 5 that the
be decomposed to sulfate was mainly removed organ
low-molecular-weight
using CM filtration. It was confirmed from the FTIR result that the molecular substances,
inorganic matter, which was further removed using AC absorption and CM f
such as aromatic pollutants, could be decomposed to low-molecular-weight organic matter
the
andtreatment effect
inorganic matter, whichof the combined
was further process
removed using AC was betterand
absorption than
CMthe direct mem
filtration,
and
tion. the treatment effect of the combined process was better than the direct membrane filtration.

Figure 5.5.The changes in FTIR −1

Figure The changes infor varied
FTIR effluents:
for variedtheeffluents:
resolution was
the 4resolution
cm , the number
was of scans
4 cm −1, the nu
was 32 and the scanning interval was 4000–550 cm−1 .
was 32 and the scanning interval was 4000-550 cm−1.
3.2. Membrane-Fouling Behavior
3.2.1. Critical Flux
3.2. Membrane-Fouling Behavior
The proper critical flux can ensure the stable operation of the membrane system.
3.2.1.
In thisCritical
study, theFlux
critical flux was used to measure the operating efficiency [57] and reflect
membrane fouling.
The proper critical flux can ensure the stable operation of the membran
The TMP was gradually improved by changing the speed of the pump to con-
this
firmstudy, theflux
the critical critical flux wasofused
in the operations to measure
the direct thethe
filtration and operating efficiency [5
combined process.
membrane fouling.
The result is shown in Figure 6. During the operation of direct filtration, the flux and
TMP both increased when the speed of the pump increased. In the initial stage of the
operation, they remained relatively stable after being changed. When the speed increased
to 80 r/min, the flux had a small downtrend (80 to 76 L/(m2 ·h)) within a short time. As the
speed increased, the downtrend became more and more obvious with the faster growth of
the TMP. It was seen that the flux increased first and then decreased with the continuous
increase in TMP after the speed exceeded 60 r/min. According to the definition in [58],
it was indicated that when the CM was used alone for filtration, the critical flux was
60 L/(m2 ·h) and the corresponding TMP was 15 kPa.
 seen that the flux increased first and then decreased with the continuous increase in
after the speed exceeded 60 r/min. According to the definition in [58], it was indicate
when the CM was used alone for filtration, the critical flux was 60 L/(m2·h) and the
sponding TMP was 15 kPa .
Membranes 2021, 11, 651 10 of 16

Figure
Figure 6. The
6. The changes
changes in thein the critical
critical flux andflux and
TMP: theTMP:
criticalthe
fluxcritical flux of thefiltration
of the membrane membrane was filtratio
measured
measured usingusing the flow
the flow ladderladder
method. method.
The fluxThe
was flux wasevery
changed changed every
30 min, 30 min,
and the andTMP
flux and the flux and
difference
difference in this
in this period
period were recorded
were recorded every 5 min.
every 5 min.

As for the combined process (shown in Figure 6), when the TMP was 14 kPa,
As for the combined process (shown in Figure 6), when the TMP was 14 kP
the critical flux could reach 57 L/(m2 ·h) and the flux and TMP were relatively stable.
critical
When the flux
TMPcould reach
increased 57kPa
to 16 L/(m 2·h) and the flux and TMP were relatively stable.
with the increase in speed, the critical flux reached
82the
L/(mTMP increased
2 ·h). As the speedto 16 kPatowith
continued the the
increase, increase in speed,
TMP began the critical
to rise within flux reach
a short time
L/(m
and the ·h).
2 flux As the speed
decreased continued
gradually. to increase,
Therefore, the
the critical TMP
flux began
of the CM intothe
rise within a shor
combined
process was 82 L/(m 2 ·h) and the corresponding TMP was 16 kPa.
and the flux decreased gradually. Therefore, the critical flux of the CM in the com
Compared with the direct filtration, the critical flux during the combined process was
process was 82 L/(m2·h) and the corresponding TMP was 16 kPa.
increased by about 37%, which meant that a greater water yield was created using the
Compared with the direct filtration, the critical flux during the combined proces
combined process. The reason for this might have been that the large molecules of organic
increased
matter by about 37%,
in the wastewater which meant
were decomposed that
by the a greater of
pretreatment water
Fentonyield was created
adsorption into usin
combined
small molecules, process.
such as The reason
sulfate. for were
These this might havetobeen
more likely passthat the large
through molecules of or
the membrane
pores, which
matter could
in the effectively alleviate
wastewater membrane fouling.
were decomposed by the Therefore,
pretreatmentthe pretreatment of
of Fenton adsorptio
Fenton absorption improved the flux, reduced the pollution in the water
small molecules, such as sulfate. These were more likely to pass through the mem and effectively
slowed membrane fouling.
pores, which could effectively alleviate membrane fouling. Therefore, the pretreatm
Fenton
3.2.2. Flux absorption improvedResistance
Decline and Membrane the flux, reduced the pollution in the water and effec
slowed
Duringmembrane
operation, fouling.
membrane fouling can appear due to concentration polarization,
cake layering and pore blocking [59], and it is inevitable. In this study, the reason for the
3.2.2. Flux Decline
membrane-fouling and Membrane
behavior Resistance
during operation was further analyzed and the influences of
pretreatment for membrane filtration were researched.
During operation, membrane fouling can appear due to concentration polariz
In order to further analyze the membrane-fouling behavior during direct filtration,
cake layering
the changes and
in flux pore
and TMP blocking [59], and
under different it is inevitable.
conditions of initial In this
flux study,
(Figure 7) the
werereason f
membrane-fouling
analyzed. behavior
As shown in Figure 7a,b,during operation
when the was
initial flux wasfurther
30 L/(manalyzed andofthe
2 ·h), the flux the influen
2
CMpretreatment
and the TMPfor membrane
changed rapidly.filtration were researched.
The flux decreased from 30 to 18 L/(m ·h) during the
first 500 min of operation and the TMP increased from 17 to 51 kPa. Therefore, the CM was
polluted rapidly during this time and the same phenomenon occurred in the conditions
where the initial fluxes of 60 and 90 L/(m2 ·h) were used. When the initial flux was higher,
the decrease in flux was more obvious. During the operation, intermittent operation mode
(operating for 12 h and intermission for 12 h) was adopted, where the flux increased and
the TMP decreased synchronously after the intermission.
 the decrease in flux was more obvious. During the operation, intermittent ope
(operating for 12 h and intermission for 12 h) was adopted, where the flux in
the TMP decreased synchronously after the intermission.
Membranes 2021, 11, 651 11 of 16

Figure
Figure 7. 7. Changes
Changes influx
in the the and
fluxTMP
andofTMP of the membrane:
the ceramic ceramic membrane: (a) flux
(a) flux changes changes
during the dur
membrane filtration and combined processes with different initial fluxes; (b)
brane filtration and combined processes with different initial fluxes; (b) changes in thchanges in the TMP in
the membrane filtration
membrane filtration andand
combined processes
combined with different
processes withinitial fluxes:initial
different during fluxes:
the process of
during the
direct filtration, the data was obtained by adjusting the peristaltic pump speed (60, 80 or 140 r/min)
rect filtration, the data was obtained by adjusting the peristaltic pump speed (60, 80 or
to adjust the bilateral membrane pressure and a stopwatch and measuring cylinder were used to
adjust the bilateral membrane pressure and a stopwatch and measuring cylinder wer
calculate the flux of water passing through the membrane during a certain time, where the flux was
culate the
calculated flux
using of water
Equation passing
(1). The initial through
flux of thethe membrane
combined process during a certain
was selected time,
according to where
Section 3.2.1 and the calculation method during the process was the same as for direct filtration.

The observed phenomena might have been caused by cake filtration and concen-
tration polarization on the membrane’s surface in the initial phase of operation. When
Membranes 2021, 11, 651 12 of 16

membrane fouling was mainly a cake layer, intermittent operation mode could reduce the
accumulation of cake on the membrane surface and improve the operating flux. With the
extension of the running time, the change in the flux and TMP tended toward being stable.
This might have been because the membrane fouling was dominated by membrane hole
obstruction. When the reason for the membrane fouling was membrane hole obstruction,
the intermittent operation mode had little influence on the TMP and flux. When the initial
flux was 60 L/(m2 ·h), the final flux fluctuated in the range from 25 to 30 L/(m2 ·h) and the
TMP varied from 45 to 55 kPa, which was higher than in the other condition. This result
shows that the membrane fouling was controlled the best under these conditions. This was
because the initial flux of 60 L/(m2 ·h) was the critical flux of the CM [60].
For the combined process, the changes in the flux and TMP are shown in Figure 7a,b.
It can be seen that in the first 5 days, the flux decreased rapidly but the TMP increased rela-
tively slowly, where it was only 6 kPa higher than the initial operation pressure. Eventually,
the TMP stabilized at about 19 kPa. At the later stage of operation, the flux decline also
slowed down gradually. After 20 days, the flux remained at about 55 L/(m2 ·h). By compar-
ing this with the result of the FTIR, membrane fouling was further analyzed. According to
the analysis, we concluded that Fenton oxidation could effectively reduce the amount of aro-
matic compounds in the water, which were considered to be the main reason for the mem-
brane fouling [61]. These were removed or oxidized into molecules with smaller molecular
weights [62–64]. Therefore, compared with direct filtration, the combined process could
slow down the phenomenon of flux decline and extended the operating cycle.
To further analyze the flux and TMP under three different initial fluxes
(30, 60 and 90 L/(m2 ·h)), the membrane resistance under three working conditions was
analyzed (Figure S1). At the beginning of the operation, the membrane resistance under
the three working conditions showed a large increase immediately and then tended to be
stable, which was similar to the results shown above. When the initial flux was 60 L/(m2 ·h),
the membrane resistance rose the slowest and the final membrane resistance was the lowest.
This result further showed that the CM was polluted quickly at the beginning, and under
operating conditions with a critical flux, the membrane life cycle could be extended [65,66].
As for the combined process (Figure S2), in the early stage, the membrane resistance
was only 4.5 × 1011 m−1 , and with the increase in running time, the membrane resistance
increased slowly. After 20 days, the membrane resistance increased to only 1.2 × 1012 m−1 ,
which was far lower than the resistance found for direct filtration. This means that the
membrane in the operation of the combined process had a better anti-pollution performance.

3.3. Membrane-Fouling Model

Membrane fouling is the main reason to restrict the operation of a membrane system,
which can be further understood using model fitting. According to the conclusion above,
different types of membrane fouling were created by different initial fluxes during the
operating conditions when using direct filtration. The Hermia model was used to fit the
model of membrane fouling and the result can be seen in Figure 8. The result showed
that when the initial flux was 30, 60 and 90 L/(m2 ·h), the types of membrane fouling were
more consistent with the models of cake filtration, complete blocking and cake filtration,
respectively. This indicated that the cake layer on the membrane surface gradually formed
in the stage of critical flux [67,68]. For the combined process, the result can be seen in
Figure 8d. The result was more consistent with the cake layer model in the initial stage
of operation, meaning that the cake layer was formed on the surface of the CM during
this stage. This phenomenon might have been caused by the AC that was absorbed on the
membrane surface because of the pumping action of the pump. In the subsequent stage of
constant pressure filtration, although the cake layer had been formed, the fitting degree of
the model of cake filtration was poor. It was speculated that the membrane fouling was
dominated by various types of membrane fouling. This might have been because the small
molecules that were created due to the decomposition of the pollutants in the wastewater
by AOPs entered into the holes of the membrane.
Membranes 2021,
Membranes 11,11,
2021, x FOR
651 PEER REVIEW 13 of 16

0.6
（a） （ b）
2.0
0.5
cake filtration complete blocking

1.5 0.4

Js -1 -1

1-Js
0.3
1.0

0.2 y = 0.015x - 0.012

y = 0.039x + 0.119
R² = 0.9635 R² = 0.9820
0.5
0.1

0.0 0.0
0 5 10 15 20 25 30 35 40 45 50 0 5 10 15 20 25 30 35 40
Vs Vs

1.4
（c）

1.2
cake filtration
1.0
y = 0.009x + 0.9793
0.8 R² = 0.8264
Js -1 -1

0.6

0.4
y = 0.074x - 0.025
R² = 0.9977
0.2

0.0
0 5 10 15 20 25 30 35 40 45 50
Vs

Figure 8. The membrane-fouling models with different initial fluxes were fitted with separate
membrane filtration conditions: (a) the model with an initial flux of 30 L/(m2 ·h); (b) the model with
an initial flux of 60 L/(m2 ·h); (c) the model with an initial flux of 90 L/(m2 ·h); (d) membrane-fouling
model fitting for the combined process.

4. Conclusions
Figure 8. The membrane-fouling models with different initial fluxes were fitted with separ
braneIn filtration
this study,conditions:
a combined process
(a) the involving
model withan AOP, AC absorption
an initial flux of 30and CM
L/(m filtration
2·h); (b) the mode
for the treatment of refinery wastewater was systematically built. The treatment
initial flux of 60 L/(m ·h); (c) the model with an initial flux of 90 L/(m ·h); (d)
2 2 effect
membran
and membrane-fouling behavior of direct filtration and the combined process on refin-
model fitting for the combined process.
ery wastewater were compared and analyzed. According to the results, the following
conclusions were found:
4. Conclusions
1. The TOC, COD and turbidity could be significantly improved using the combined
In thisThis
process. study, a combined
was because process
some organic involving an
macromolecular AOP,
matter, AC
such absorption
as aromatic com- and C
tionpounds
for thein the wastewater,
treatment was effectively
of refinery wastewater decomposed using Fenton oxidationand
was systematically built. The treatme
finally removed using the AC and CM.
and membrane-fouling behavior of direct filtration and the combined process on
2. Compared with direct membrane filtration, it was found that the optimal critical
wastewater
flux of thewere compared
CM could and analyzed.
be significantly According
increased to the results,
and the membrane foulingthe following
could
sionsbewere found:
effectively alleviated using the combined process. According to the analysis,
the AOP and AC absorption could decompose the macromolecular substances in the
1. The TOC, COD and turbidity could be significantly improved using the co
wastewater into small molecular substances, which passed through the pores of the
process. easier.
membrane This was because some organic macromolecular matter, such as a
3. compounds in the wastewater,
The model of membrane was effectively
fouling in the combined decomposed
process was using
more consistent with Fenton
the cake layer
tionand model
finally in the initial
removed stagethe
using andACthe and
membrane
CM. fouling might have been
2. Compared with direct membrane filtration,the
dominated by various types of membrane fouling in subsequent
it was foundstages.
that the optimal crit
of the CM could be significantly increased and the membrane fouling could
tively alleviated using the combined process. According to the analysis, the A
AC absorption could decompose the macromolecular substances in the was
into small molecular substances, which passed through the pores of the me
easier.
3. The model of membrane fouling in the combined process was more consist
the cake layer model in the initial stage and the membrane fouling might ha
Membranes 2021, 11, 651 14 of 16

Supplementary Materials: The following are available online at https://www.mdpi.com/article/

10.3390/membranes11090651/s1, Figure S1: The structure of the membrane module, Figure S2:
Membrane resistance of CM in the operation of direct filtration and combined process: The membrane
fouling resistance was calculated by Equations (1)–(4).
Author Contributions: Conceptualization, H.M., L.Q. and G.L.; methodology, H.M. and G.L.; soft-
ware, H.M. and Q.Q.; validation, H.M., L.Q. and G.L.; formal analysis, H.M. and R.C.; investigation,
K.X. and M.G.; resources, H.M. and Q.Q.; data curation, G.L. and R.C.; writing—original draft
preparation, H.M.; writing—review and editing, L.Q. and G.L.; visualization, H.M.; supervision, L.Q.
and G.L.; project administration, L.Q. and G.L.; funding acquisition, L.Q. and G.L. All authors read
and agreed to the published version of the manuscript.
Funding: This study was financially supported by the National Natural Science Foundation of China
(grant Nos. 51678276 and 51808257), the funding program of 20 policies for universities in Jinan
(2018GXRC020), Natural Science Foundation of Shandong Province (ZR2020ME227), the Scientific
and Technological Research Project of Science and Technology Department of Shandong Province
(2019GSF109083), the National Natural Science Foundation of China (no. 51808257) and the Scientific
and Technological Research Project of Science and Technology Department of Shandong Province
(2019GSF109083).
Institutional Review Board Statement: The study did not involve humans or animals.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: We are grateful to the National Natural Science Foundation of China and the
Shandong Science and Technology Department for their strong support.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Liu, Y.; Han, F.; Liu, W.; Cui, X.; Luan, X.; Cui, Z. Process-based volatile organic compound emission inventory establishment
method for the petroleum refining industry. J. Clean. Prod. 2020, 263, 121609. [CrossRef]
2. Santos, B.; Galinha, C.F.; Crespo, J.G.; Santos, M.A.; Velizarov, S. Prediction of polar oil and grease contamination levels in refinery
wastewater through multivariate statistical modeling. Sep. Purif. Technol. 2013, 119, 51–57. [CrossRef]
3. Osin, O.A.; Yu, T.Y.; Lin, S.J. Oil refinery wastewater treatment in the Niger Delta, Nigeria: Current practices, challenges,
and recommendations. Environ. Sci. Pollut. Res. 2017, 24, 22730–22740. [CrossRef]
4. Yu, L.; Han, M.; He, F. A review of treating oily wastewater. Arab. J. Chem. 2017, 10, S1913–S1922. [CrossRef]
5. Kriipsalu, M.; Marques, M.; Nammari, D.R.; Hogland, W. Bio-treatment of oily sludge: The contribution of amendment material to
the content of target contaminants, and the biodegradation dynamics. J. Hazard. Mater. 2007, 148, 616–622. [CrossRef] [PubMed]
6. Abadi, S.R.H.; Sebzari, M.R.; Hemati, M.; Rekabdar, F.; Mohammadi, T. Ceramic membrane performance in microfiltration of oily
wastewater. Desalination 2011, 265, 222–228. [CrossRef]
7. Abbasi, M.; Mirfendereski, M.; Nikbakht, M.; Golshenas, M.; Mohammadi, T. Performance study of mullite and mullite–alumina
ceramic MF membranes for oily wastewaters treatment. Desalination 2010, 259, 169–178. [CrossRef]
8. Zhu, X.; Tu, W.; Wee, K.-H.; Bai, R. Effective and low fouling oil/water separation by a novel hollow fiber membrane with both
hydrophilic and oleophobic surface properties. J. Membr. Sci. 2014, 466, 36–44. [CrossRef]
9. Boehler, M.; Zwickenpflug, B.; Hollender, J.; Ternes, T.; Joss, A.; Siegrist, H. Removal of micropollutants in municipal wastewater
treatment plants by powder-activated carbon. Water Sci. Technol. 2012, 66, 2115–2121. [CrossRef] [PubMed]
10. Ben Hariz, I.; Al Ayni, F.; Monser, L. Removal of sulfur compounds from petroleum refinery wastewater through adsorption on
modified activated carbon. Water Sci. Technol. 2014, 70, 1376–1382. [CrossRef]
11. Hami, M.L.; Al-Hashimi, M.A.; Al-Doori, M.M. Effect of activated carbon on BOD and COD removal in a dissolved air flotation
unit treating refinery wastewater. Desalination 2007, 216, 116–122. [CrossRef]
12. Candido, L.; Ponciano Gomes, J.A.C.; Medaber Jambo, H.C. Electrochemical Treatment of Oil Refinery Wastewater for NH3 -N
and COD Removal. Int. J. Electrochem. Sci. 2013, 8, 9187–9200.
13. Aljuboury, D.a.d.A.; Al-Abri, M.; Shaik, F.; Al-Sabahi, J.N.; Alkhadori, A.N. Assessment of TiO2 /ZnO/H2 O2 Photocatalyst to
treat wastewater from oil refinery within visible light circumstances. S. Afr. J. Chem. Eng. 2020, 35, 69–77. [CrossRef]
14. Coelho, A.; Castro, A.V.; Dezotti, M.; Sant’Anna, G.L. Treatment of petroleum refinery sourwater by advanced oxidation processes.
J. Hazard. Mater. 2006, 137, 178–184. [CrossRef] [PubMed]
15. Estrada-Arriaga, E.B.; Zepeda-Aviles, J.A.; García-Sánchez, L. Post-treatment of real oil refinery effluent with high concentrations
of phenols using photo-ferrioxalate and Fenton’s reactions with membrane process step. Chem. Eng. J. 2016, 285, 508–516.
[CrossRef]
Membranes 2021, 11, 651 15 of 16

16. Li, H.; Yu, P.; Luo, Y. Fouling mechanisms and primary foulant constituents in reverse osmosis membrane reclamation of a
petrochemical secondary effluent. Desalination Water Treat. 2015, 54, 3200–3210. [CrossRef]
17. Bhagawan, D.; Poodari, S.; Golla, S.; Himabindu, V.; Vidyavathi, S. Treatment of the petroleum refinery wastewater using
combined electrochemical methods. Desalination Water Treat. 2016, 57, 3387–3394. [CrossRef]
18. Diya’uddeen, B.H.; Rahim Pouran, S.; Abdul Aziz, A.R.; Nashwan, S.M.; Wan Daud, W.M.A.; Shaaban, M.G. Hybrid of Fenton
and sequencing batch reactor for petroleum refinery wastewater treatment. J. Ind. Eng. Chem. 2015, 25, 186–191. [CrossRef]
19. Souza, B.M.; Cerqueira, A.C.; Sant’Anna, G.L.; Dezotti, M. Oil-Refinery Wastewater Treatment Aiming Reuse by Advanced
Oxidation Processes (AOPs) Combined with Biological Activated Carbon (BAC). Ozone Sci. Eng. 2011, 33, 403–409. [CrossRef]
20. Rueda-Márquez, J.J.; Levchuk, I.; Salcedo, I.; Acevedo-Merino, A.; Manzano, M.A. Post-treatment of refinery wastewater effluent
using a combination of AOPs (H2 O2 photolysis and catalytic wet peroxide oxidation) for possible water reuse. Comparison of
low and medium pressure lamp performance. Water Res. 2016, 91, 86–96. [CrossRef]
21. Nogueira, A.A.; Bassin, J.P.; Cerqueira, A.C.; Dezotti, M. Integration of biofiltration and advanced oxidation processes for tertiary
treatment of an oil refinery wastewater aiming at water reuse. Environ. Sci. Pollut. Res. 2016, 23, 9730–9741. [CrossRef]
22. Zhang, S.; Zheng, J.; Chen, Z. Combination of ozonation and biological aerated filter (BAF) for bio-treated coking wastewater.
Sep. Purif. Technol. 2014, 132, 610–615. [CrossRef]
23. Hernández-Francisco, E.; Peral, J.; Blanco-Jerez, L.M. Removal of phenolic compounds from oil refinery wastewater by electroco-
agulation and Fenton/photo-Fenton processes. J. Water Process Eng. 2017, 19, 96–100. [CrossRef]
24. Saber, A.; Mortazavian, S.; James, D.E.; Hasheminejad, H. Optimization of Collaborative Photo-Fenton Oxidation and Coagulation
for the Treatment of Petroleum Refinery Wastewater with Scrap Iron. Water Air Soil Pollut. 2017, 228, 312. [CrossRef]
25. GilPavas, E.; Dobrosz-Gómez, I.; Gómez-García, M.-Á. Optimization and toxicity assessment of a combined electrocoagulation,
H2 O2 /Fe2+ /UV and activated carbon adsorption for textile wastewater treatment. Sci. Total Environ. 2019, 651, 551–560.
[CrossRef] [PubMed]
26. Yin, R.; Shang, C. Removal of micropollutants in drinking water using UV-LED/chlorine advanced oxidation process followed
by activated carbon adsorption. Water Res. 2020, 185, 116297. [CrossRef] [PubMed]
27. Lemus, J.; Martin-Martinez, M.; Palomar, J.; Gomez-Sainero, L.; Gilarranz, M.A.; Rodriguez, J.J. Removal of chlorinated organic
volatile compounds by gas phase adsorption with activated carbon. Chem. Eng. J. 2012, 211–212, 246–254. [CrossRef]
28. Ebrahimi, M.; Schmitz, O.; Kerker, S.; Liebermann, F.; Czermak, P. Dynamic cross-flow filtration of oilfield produced water by
rotating ceramic filter discs. Desalination Water Treat. 2013, 51, 1762–1768. [CrossRef]
29. Yuliwati, E.; Ismail, A.F.; Matsuura, T.; Kassim, M.A.; Abdullah, M.S. Effect of modified PVDF hollow fiber submerged
ultrafiltration membrane for refinery wastewater treatment. Desalination 2011, 283, 214–220. [CrossRef]
30. Madaeni, S.S.; Ahmadi Monfared, H.; Vatanpour, V.; Arabi Shamsabadi, A.; Salehi, E.; Daraei, P.; Laki, S.; Khatami, S.M. Coke
removal from petrochemical oily wastewater using γ-Al2 O3 based ceramic microfiltration membrane. Desalination 2012, 293,
87–93. [CrossRef]
31. Ebrahimi, M.; Willershausen, D.; Ashaghi, K.S.; Engel, L.; Placido, L.; Mund, P.; Bolduan, P.; Czermak, P. Investigations on the use
of different ceramic membranes for efficient oil-field produced water treatment. Desalination 2010, 250, 991–996. [CrossRef]
32. Elmaleh, S.; Ghaffor, N. Cross-flow ultrafiltration of hydrocarbon and biological solid mixed suspensions. J. Membr. Sci. 1996, 118,
111–120. [CrossRef]
33. Moslehyani, A.; Ismail, A.F.; Othman, M.H.D.; Matsuura, T. Design and performance study of hybrid photocatalytic reactor-
PVDF/MWCNT nanocomposite membrane system for treatment of petroleum refinery wastewater. Desalination 2015, 363, 99–111.
[CrossRef]
34. Freeman, S.; Shorney-Darby, H. What’s the Buzz about Ceramic Membranes? J. AWWA 2011, 103, 12–13. [CrossRef]
35. Valdés, H.; Zaror, C.A. Heterogeneous and homogeneous catalytic ozonation of benzothiazole promoted by activated carbon:
Kinetic approach. Chemosphere 2006, 65, 1131–1136. [CrossRef]
36. Munirasu, S.; Haija, M.A.; Banat, F. Use of membrane technology for oil field and refinery produced water treatment—A review.
Process Saf. Environ. Prot. 2016, 100, 183–202. [CrossRef]
37. Asatekin, A.; Mayes, A.M. Oil Industry Wastewater Treatment with Fouling Resistant Membranes Containing Amphiphilic Comb
Copolymers. Environ. Sci. Technol. 2009, 43, 4487–4492. [CrossRef]
38. Howe, K.J.; Clark, M.M. Fouling of Microfiltration and Ultrafiltration Membranes by Natural Waters. Environ. Sci. Technol. 2002,
36, 3571–3576. [CrossRef]
39. Song, J.; Zhang, Z.; Zhang, X. A comparative study of pre-ozonation and in-situ ozonation on mitigation of ceramic UF membrane
fouling caused by alginate. J. Membr. Sci. 2017, 538, 50–57. [CrossRef]
40. Song, J.; Zhang, Z.; Tang, S.; Tan, Y.; Zhang, X. Does pre-ozonation or in-situ ozonation really mitigate the protein-based ceramic
membrane fouling in the integrated process of ozonation coupled with ceramic membrane filtration? J. Membr. Sci. 2018, 548,
254–262. [CrossRef]
41. Park, W.-I.; Jeong, S.; Im, S.-J.; Jang, A. High turbidity water treatment by ceramic microfiltration membrane: Fouling identification
and process optimization. Environ. Technol. Innov. 2020, 17, 100578. [CrossRef]
42. Fan, X.; Tao, Y.; Wang, L.; Zhang, X.; Lei, Y.; Wang, Z.; Noguchi, H. Performance of an integrated process combining ozonation
with ceramic membrane ultra-filtration for advanced treatment of drinking water. Desalination 2014, 335, 47–54. [CrossRef]
Membranes 2021, 11, 651 16 of 16

43. Liu, J.; He, K.; Zhang, J.; Li, C.; Zhang, Z. Coupling ferrate pretreatment and in-situ ozonation/ceramic membrane filtration for
wastewater reclamation: Water quality and membrane fouling. J. Membr. Sci. 2019, 590, 117310. [CrossRef]
44. Ahmad, R.; Guo, J.; Kim, J. Structural characteristics of hazardous organic dyes and relationship between membrane fouling and
organic removal efficiency in fluidized ceramic membrane reactor. J. Clean. Prod. 2019, 232, 608–616. [CrossRef]
45. Liu, F.; Yao, H.; Sun, S.; Tao, W.; Wei, T.; Sun, P. Photo-Fenton activation mechanism and antifouling performance of an
FeOCl-coated ceramic membrane. Chem. Eng. J. 2020, 402, 125477. [CrossRef]
46. Tang, S.; Zhang, L.; Peng, Y.; Liu, J.; Zhang, Z. Fenton cleaning strategy for ceramic membrane fouling in wastewater treatment.
J. Environ. Sci. 2019, 85, 189–199. [CrossRef] [PubMed]
47. Baker, A.; Inverarity, R.; Charlton, M.; Richmond, S. Detecting river pollution using fluorescence spectrophotometry: Case studies
from the Ouseburn, NE England. Environ. Pollut. 2003, 124, 57–70. [CrossRef]
48. Coble, P.G. Characterization of marine and terrestrial DOM in seawater using excitation-emission matrix spectroscopy.
Mar. Chem. 1996, 51, 325–346. [CrossRef]
49. Zhang, J.; Song, F.; Li, T.; Xie, K.; Yao, H.; Xing, B.; Li, Z.; Bai, Y. Simulated photo-degradation of dissolved organic matter in lakes
revealed by three-dimensional excitation-emission matrix with regional integration and parallel factor analysis. J. Environ. Sci.
2020, 90, 310–320. [CrossRef]
50. Divya, O.; Mishra, A.K. Understanding the concept of concentration-dependent red-shift in synchronous fluorescence spectra:
Prediction of λSFSmax and optimization of ∆λ for synchronous fluorescence scan. Anal. Chim. Acta 2008, 630, 47–56. [CrossRef]
[PubMed]
51. Wang, Z.-P.; Zhang, T. Characterization of soluble microbial products (SMP) under stressful conditions. Water Res. 2010, 44,
5499–5509. [CrossRef]
52. Smith, G.C.; Sinski, J.F. The Red-Shift Cascade: Investigations into the Concentration-Dependent Wavelength Shifts in
Three-Dimensional Fluorescence Spectra of Petroleum Samples. Appl. Spectrosc. 1999, 53, 1459–1469. [CrossRef]
53. Abouleish, M.Y.Z.; Wells, M.J.M. Trihalomethane formation potential of aquatic and terrestrial fulvic and humic acids: Sorption
on activated carbon. Sci. Total Environ. 2015, 521–522, 293–304. [CrossRef]
54. Huang, S.; Gan, W.; Yan, M.; Zhang, X.; Zhong, Y.; Yang, X. Differential UV–vis absorbance can characterize the reaction of
organic matter with ClO2 . Water Res. 2018, 139, 442–449. [CrossRef]
55. Li, J.; Tong, Y.; Guan, L.; Wu, S.; Li, D. Optimization of COD determination by UV–vis spectroscopy using PLS chemometrics
algorithms. Optik 2018, 174, 591–599. [CrossRef]
56. Chen, J.; Mu, L.; Jiang, B.; Yin, H.; Song, X.; Li, A. TG/DSC-FTIR and Py-GC investigation on pyrolysis characteristics of
petrochemical wastewater sludge. Bioresour. Technol. 2015, 192, 1–10. [CrossRef]
57. Ratman, I.; Kusworo, T.D.; Utomo, D.P.; Azizah, D.A.; Ayodyasena, W.A. Petroleum Refinery Wastewater Treatment using
Three Steps Modified Nanohybrid Membrane Coupled with Ozonation as Integrated Pre-treatment. J. Environ. Chem. Eng. 2020,
8, 103978. [CrossRef]
58. Lehman, S.G.; Liu, L. Application of ceramic membranes with pre-ozonation for treatment of secondary wastewater effluent.
Water Res. 2009, 43, 2020–2028. [CrossRef]
59. Zhang, W.; Luo, J.; Ding, L.; Jaffrin, M.Y. A Review on Flux Decline Control Strategies in Pressure-Driven Membrane Processes.
Ind. Eng. Chem. Res. 2015, 54, 2843–2861. [CrossRef]
60. Cui, Z.; Peng, W.; Fan, Y.; Xing, W.; Xu, N. Effect of Cross-flow Velocity on the Critical Flux of Ceramic Membrane Filtration as a
Pre-treatment for Seawater Desalination. Chin. J. Chem. Eng. 2013, 21, 341–347. [CrossRef]
61. Her, N.; Amy, G.; Chung, J.; Yoon, J.; Yoon, Y. Characterizing dissolved organic matter and evaluating associated nanofiltration
membrane fouling. Chemosphere 2008, 70, 495–502. [CrossRef]
62. Li, C.; Li, X.; Qin, L.; Wu, W.; Meng, Q.; Shen, C.; Zhang, G. Membrane photo-bioreactor coupled with heterogeneous Fenton
fluidized bed for high salinity wastewater treatment: Pollutant removal, photosynthetic bacteria harvest and membrane anti-
fouling analysis. Sci. Total Environ. 2019, 696, 133953. [CrossRef]
63. Peres, J.A.; Beltrán de Heredia, J.; Domínguez, J.N.R. Integrated Fenton’s reagent—Coagulation/flocculation process for the
treatment of cork processing wastewaters. J. Hazard. Mater. 2004, 107, 115–121. [CrossRef]
64. Teng, C.; Zhou, K.; Zhang, Z.; Peng, C.; Chen, W. Elucidating the structural variation of membrane concentrated landfill leachate
during Fenton oxidation process using spectroscopic analyses. Environ. Pollut. 2020, 256, 113467. [CrossRef] [PubMed]
65. Field, R.W.; Pearce, G.K. Critical, sustainable and threshold fluxes for membrane filtration with water industry applications.
Adv. Colloid Interface Sci. 2011, 164, 38–44. [CrossRef]
66. Field, R.W.; Wu, D.; Howell, J.A.; Gupta, B.B. Critical flux concept for microfiltration fouling. J. Membr. Sci. 1995, 100, 259–272.
[CrossRef]
67. Kumar, R.V.; Goswami, L.; Pakshirajan, K.; Pugazhenthi, G. Dairy wastewater treatment using a novel low cost tubular ceramic
membrane and membrane fouling mechanism using pore blocking models. J. Water Process Eng. 2016, 13, 168–175. [CrossRef]
68. Lee, S.-J.; Dilaver, M.; Park, P.-K.; Kim, J.-H. Comparative analysis of fouling characteristics of ceramic and polymeric microfiltra-
tion membranes using filtration models. J. Membr. Sci. 2013, 432, 97–105. [CrossRef]