sustainability

Article
Cotton Spinning Waste as a Microporous Activated Carbon:
Application to Remove Sulfur Compounds in a Tunisian
Refinery Company
Bechir Wannassi 1 , Mohammad Kanan 2, *, Ichrak Ben Hariz 3 , Ramiz Assaf 4 , Zaher Abusaq 2 ,
Mohamed Ben Hassen 1 , Salem Aljazzar 2 , Siraj Zahran 2 , Mohammed T. Khouj 2 and Ahmad S. Barham 5

1 Textile Laboratory Engineering ‘LGTex’, University of Monastir, Ksar Hellal, Monastir 5078, Tunisia
2 Jeddah College of Engineering, University of Business and Technology, Jeddah 21448, Saudi Arabia
3 Tunisian Society of Refinery Industries, Bizerte 7021, Tunisia
4 Industrial Engineering Department, An-Najah National University, Nablus 00970, Palestine
5 Department of Chemistry, The University of Jordan, Amman 11942, Jordan
* Correspondence: [email protected]

Abstract: The petroleum industry plays a vital role in the economies of developing countries. Refinery
wastewater pollution has increased in recent years due to the increase in the industrial and urban
use of petroleum products. The present work demonstrates how textile waste can be modified into
a material that can effectively remove sulfur pollutants from refinery wastewater. An economic
activated carbon (AC) material was developed by using cotton spinning waste from a textile company.
The chemical activation was carried out using nitric acid (HNO3 ), hydrogen peroxide (H2 O2 ), and
potassium hydroxide (KOH). The characterization of the obtained activated carbons was performed
using the SEM, BET, and FTIR techniques. The effect of the experimental adsorption condition was
investigated using both bed and batch isotherms. The results show that effluent flow has the highest
Citation: Wannassi, B.; Kanan, M.; effect on sulfur compound adsorption. The greatest adsorption capacity of the sulfur compounds
Hariz, I.B.; Assaf, R.; Abusaq, Z.; Ben was found to be around 168.4 mg·g−1 . The equilibrium data were investigated using the Freundlich,
Hassen, M.; Aljazzar, S.; Zahran, S.; Langmuir, Dubinin–Radushkevich, Tóth, and Sips isotherm models. The Langmuir model exhibited
Khouj, M.T.; Barham, A.S. Cotton the best fit (R2 = 0.98) for the sulfur compounds’ adsorption, which implies that their adsorption
Spinning Waste as a Microporous onto the synthesized AC was homogeneous. The kinetic data were tested with pseudo-first-order,
Activated Carbon: Application to pseudo-second-order, and intraparticular diffusion equations. The pseudo-second-order equation
Remove Sulfur Compounds in a
described the kinetic data well (R2 = 0.99), indicating that this adsorption may be restricted by the
Tunisian Refinery Company.
chemisorption process. These properties under optimal conditions make the obtained ACs suitable
Sustainability 2023, 15, 654. https://
for use in refinery wastewater treatment.
doi.org/10.3390/su15010654

Academic Editors: Gassan Hodaifa, Keywords: cotton waste; activated carbon; kinetic study; bed adsorption; chemical activation;
Mounia Achak, Khaoula Khaless and removal; refinery wastewater
Edvina Lamy

Received: 18 November 2022

Revised: 16 December 2022
Accepted: 27 December 2022 1. Introduction
Published: 30 December 2022 Environmental pollution has increased in recent years with the increase in industrial
and urban development. The petroleum industry plays a vital role in the economies
of developing countries across the world. Oil refining is an essential operation during
petroleum processing, and it uses a huge quantity of chemical products and generates both
Copyright: © 2022 by the authors.
solid waste and wastewater [1], which are considered hazardous waste. In fact, refinery
Licensee MDPI, Basel, Switzerland.
This article is an open access article
wastewater has high quantities of heavy metals (more than 50 mg·dm−3 ), phenols (more
distributed under the terms and
than 150 mg·dm−3 ), benzene (more than 75 mg·dm−3 ), and Chemical Oxygen Demand
conditions of the Creative Commons
(COD) (between 280 and 1100 mg·dm−3 ) [2–6].
Attribution (CC BY) license (https:// The removal of hazardous components is a requirement before the discharge of this
creativecommons.org/licenses/by/ type of wastewater and before its reuse [7,8]. Therefore, treating effluent is required in
4.0/).

Sustainability 2023, 15, 654. https://doi.org/10.3390/su15010654 https://www.mdpi.com/journal/sustainability

Sustainability 2023, 15, 654 2 of 16

order to eliminate hazardous contaminants [9]. Several methods have been investigated for
the treatment of refinery wastewater, including physical, chemical, and biological methods.
A membrane bioreactor has been successfully used to remove pollutants from
petroleum industry wastewater. Rahman et al. evaluated the use of a cross-flow membrane
bioreactor for the treatment of refinery wastewater. Their results showed that this technique
can remove more than 93% of COD from refinery effluents and that its efficiency does not
depend on the hydraulic retention time [10]. Razavi et al. studied the use of a hollow-
fiber membrane bioreactor to treat refinery wastewater. The effects of flux, temperature,
and hydraulic retention parameters were evaluated. According to the findings of this
investigation, COD elimination can reach 82% [11]. However, this method comes with
several specific precautions. Membrane fouling is a major problem that can frequently
occur. Moreover, this seriously affects the quality of the reclaimed water and the efficiency
of the membrane. However, its use was only recently tested in a pilot test [12–14].
Yan et al. [15] investigated the use of electrochemical processes in the treatment of
petroleum refinery wastewater. These processes introduce air and a few particles of iron
into classical two-dimensional reactors. In optimal experimental conditions, the salinity
and COD removal efficiency were 84 µS cm−1 and 92.8%, respectively. However, the use of
the electrochemical method is limited for organic material removal [16,17]. Its higher cost
and lower efficiency also limit its industrial application [18–20].
The microbiological treatment of industrial refinery wastewater has also been inves-
tigated using several types of microorganisms [21,22]. This method has been used to
oxidize organic matter existing in refinery effluent into simple products, such as CH4 , H2 O,
and CO2 , under aerobic, anaerobic, and semi-aerobic conditions [23,24]. Ebrahimi et al.
investigated the use of this kind of treatment in an experimental pilot plant. He demon-
strated, in suitable experimental conditions, a COD removal efficiency of around 78% and
a biomass production of 1420 g daily [25]. Hayat et al. carried out an investigation of a
microbiological approach to treat refinery wastewater. The interaction between metals and
the functional groups of microorganisms was analyzed. The quantitative results revealed
that the bacteria had developed a new level of metal resistance [22]. However, firstly, the
use of a biological approach for refinery effluent treatment can cause serious problems
due to the excessive production of sludge [26]. Secondly, these methods generate diverse
operational problems, such as the generation of residual sludge and toxic gases, the partial
elimination of refractory compounds, and the need for a large land area.
Many researchers have successfully used the adsorption approach to treat refinery
wastewater [27–31]. The selection of this method is based on its high potential to remove
toxic compounds and its cost-effective nature. El-Naas evaluated the use of activated carbon
using local material prepared from date pits as a precursor in the treatment of refinery
wastewater. Several kinetic and isotherm models were tested with batch adsorption. The
Sips isotherm was proved to be the best model to describe the equilibrium isotherm,
whereas the pseudo-second-order model gave the best fit for the kinetics data. More than
85% regeneration efficiency was found after four cycles of regeneration [32]. Qinxuan et al.
investigated the use of prepared activated carbon in the treatment of refinery wastewater.
Their results showed that the activated carbon experimental conditions (the calcination
time and temperature, chemical reagent concentration, and weight ratio of AC) have an
important effect on the COD removal efficiency. Their results also showed that the COD
efficiency increases with a decrease in the weight ratio of effluent [33]. Several researchers
have used biomass as a precursor of activated carbon in the treatment of refinery wastewater.
Lagerstroemia speciosa has been used as a precursor of activated carbon and showed potential
to recover platinum from refinery wastewater [34]. Rice husk activated carbon has been
successfully evaluated as an effective adsorbent of phenolic compound content in refinery
wastewater using a column approach [35]. Date activated carbon has also been evaluated
as an effective adsorbent that can reduce COD in refinery effluent [36–38].
The growth of the textile industry has resulted in massive amounts of solid waste.
Indeed, 106 M tons of textile solid waste is produced annually worldwide [39]. This amount
 and showed potential to recover platinum from refinery wastewater [34]. Rice husk acti-
vated carbon has been successfully evaluated as an effective adsorbent of phenolic com-
pound content in refinery wastewater using a column approach [35]. Date activated car-
bon has also been evaluated as an effective adsorbent that can reduce COD in refinery
Sustainability 2023, 15, 654 effluent [36–38]. 3 of 16
The growth of the textile industry has resulted in massive amounts of solid waste.
Indeed, 106 M tons of textile solid waste is produced annually worldwide [39]. This
amount increases
increases from one from year to onetheyear
nexttodue
the to
next
thedue
boomto the boom
of the of the
fashion fashion[40].
industry industry
Around[40].
Around the world, cotton is used the most. Cotton waste can
the world, cotton is used the most. Cotton waste can be used as a low-cost lignocellulosic be used as a low-cost ligno-
cellulosic
material material [41–43].
[41–43].
Notonly
Not onlycan cancotton
cottonwastewastecancanbebeused
usedtotoproduce
produceyarnsyarnsand andnonwovens
nonwovens[44–48],[44–48],butbut
ititcan
canalso
alsobebeusedusedasasa areinforcement
reinforcementfor forcomposite
compositematerials
materials[49,50].
[49,50].
Someresearchers
Some researchershave havestudied
studiedthethepossibility
possibilityofoftransforming
transformingcotton cottonwaste
wasteinto
intoacti-
acti-
vated carbon. Zhao et al. [51] studied the production of activated
vated carbon. Zhao et al. [51] studied the production of activated carbon by using cotton carbon by using cotton
wovenwaste.
woven waste.The Thewaste
wastewas wasfirst
firstdissolved
dissolvedusing
using80%
80%HH 3PO
3 PO andpre-soaked
4 4and pre-soakedininaasolution
solution
ofof7.5%
7.5%(NH(NH 4 )42)HPO
2HPO44.. In In the
the optimum
optimum conditions
conditions of 700–800◦°C,
of700–800 C, 30
30min
minof ofcarbonization,
carbonization,
and
and3030min
minofofactivation,
activation,good goodadsorption
adsorptionresults
resultswere
wereobtained.
obtained.
Sartova
Sartova[52] [52]utilized
utilizedthe theboiling
boilinglayer
layermethod
methodtotoprepare
prepareAC ACfrom
fromcotton
cottonbiomass
biomass
(stems and balls from cotton plants boiled at 800 to 850 ◦ C for 8 min), and he demonstrated
(stems and balls from cotton plants boiled at 800 to 850 °C for 8 min), and he demonstrated
that
thatthe
theACACobtained
obtainedhad hadadsorption
adsorptionproperties
propertieshigher
higherthanthanthose
thoseofofindustrial
industrialAC ACmade
made
from
fromwood.
wood.Wanassi
Wanassi[53] [53]employed
employedcotton
cottonwastewastetotoproduce
produceactivated
activatedcarbon
carbonthrough
through
carbonization
carbonizationusing using zinc
zincchloride
chloridechemical
chemicalactivation. The The
activation. obtained product
obtained enabled
product a higha
enabled
removal of anionic
high removal dye from
of anionic dyetextile wastewater.
from textile wastewater.
XuXu[54,55]
[54,55]optimized
optimizedthe theproduction
productionofofactivated
activatedmagnetic
magneticcarbon carbonfromfromtextile
textilewaste
waste
yarn using FeCl
yarn using FeCl 3 3. The results proved that this treatment is able to change thepyrolysis
. The results proved that this treatment is able to change the pyrolysis
process
processof ofcotton textile waste,
cotton textile waste,decrease
decreasethe thepyrolytic
pyrolytic carbonization
carbonization temperature,
temperature, andandpre-
prevent the production of volatiles.
vent the production of volatiles. Fe2O23 and Fe O and Fe O resulting
3 Fe3O43 resulting
4 from FeCl
from FeCl3 could 3 could help
help porepore
for-
formation
mation ononthe theobtained
obtainedactivated
activatedcarbon.
carbon.
Most
Mostofofthese
theseprevious
previousstudies
studieswere
wereconducted
conductedatatthe thelaboratory
laboratoryscalescalewithwithnonofocus
focus
on a specific application. The main objective of our work, realized
on a specific application. The main objective of our work, realized with the collaboration with the collaboration
ofofaabig
bigrefinery
refinerycompany
companyininTunisia, Tunisia,was
wastotosynthesize
synthesizeactivated
activatedcarboncarbonfrom
fromcotton
cottonfiber
fiber
spinning
spinning waste and to use it to remove sulfur compounds from refinery wastewater.The
waste and to use it to remove sulfur compounds from refinery wastewater. The
whole
wholeprocess
processisisillustrated
illustratedininFigure
Figure1.1.

Figure1.1.Process
Figure Processofofthe
thepreparation
preparationand
anduse
useofofactivated
activatedcarbon.
carbon.

2. Materials and Methods

2.1. Materials and Chemicals
The raw material used was recycled spinning cotton fiber waste obtained from Tunisian
Textile Industries Company (SITEX) in Tunisia. In a previous study, we optimized the
fraying process of spinning yarn waste using a mechanical machine [46]. Approximately
20% of the obtained fibers were judged to be non-reusable for another cycle of the spinning
process because of their bad quality (bad mechanical properties and a high ratio of short
Sustainability 2023, 15, 654 4 of 16

fibers). So, in reality, we used the waste of the waste of a low-quality and low-cost cotton
fiber to produce our activated carbon (AC).
H2 O2 , KOH, and HNO3 were purchased from Chimitex, Sousse 4000, Tunisia,
Ltd. (Sousse, Tunisia). All the chemical reagents were used as received without
additional treatment.

2.2. Preparation of Activated Carbon

Cotton waste fiber was washed with distilled water for the removal of impurities.
Then, it was oven-dried at 85 ◦ C until a 7–10% moisture content was obtained.
About 40 g of the dried fibers was heated to 700 ◦ C at a heating rate of 5 ◦ C/min
in a horizontal furnace under a purified N2 flow (10 NL/min). After the calcination
process, the char was cooled under N2 flow to room temperature. Afterward, the char was
chemically activated using nitric acid (HNO3 ), hydrogen peroxide (H2 O2 ), and potassium
hydroxide (KOH).
For HNO3 activation, the char was impregnated with HNO3 at a ratio of 3:1 (g HNO3 /g
char). For H2 O2 activation, 50 mL of commercial H2 O2 solution (110 vol.; 33% w/v) was
used. For KOH activation, the char was impregnated with OH solution at a ratio of 3:1 (g
KOH/g char). For all samples, the reaction was kept at ambient temperature (25 ◦ C) for
24 h. Then, the mix was dried at 85 ◦ C for 12 h. After drying, each sample was heated to
700 ◦ C at a heating rate of 5 ◦ C/min in a horizontal furnace under purified N2 flow.
After cooling down, the activated carbon (AC) was washed in hot distilled water to
remove any unused activating agent and then oven-dried at 85 ◦ C for 24 h for further
utilization. The resulting ACs were denoted as HNAC, HOAC, and KAC.

2.3. Characterization Methods

Various techniques were explored to characterize the raw materials and their derived
activated carbon.

2.3.1. Morphologies of ACs

The morphologies of the raw materials and their derived activated carbon were ana-
lyzed using scanning electron microscopy (FEI model Quanta 400 SEM, Philips, Andover,
MA, USA).
The FEI Quanta 400 is a high-resolution field-emission scanning electron microscope.
It is equipped with SE, backscatter, and energy-dispersive spectroscopy detectors, and it can
operate in high vac, low vac, and Wet modes. It is also equipped with a cooling stage. The
FEI Quanta 400 is an environmental SEM (ESEM). The major advantage of ESEM modes is
that any material, dry non-conductive up to extreme conditions, for example, wet specimens
and those containing volatile components, such as oil, can be viewed and analyzed. So,
no treatment or preparation is needed to view the specimen. The magnification number
is 1200.

2.3.2. Textural Characterization

HNAC, HOAC, and KAC activated carbon textural characterization were performed
using N2 adsorption isotherms at 77 K with an ASAP 2020 instrument (Micromeritics,
Atlanta, GA, USA). Before the analyses, carbon was outgassed overnight under a vacuum
at 623 K. The BET surface areas (SBET) of the samples were determined using N2 adsorption
isotherms in a relative pressure (P/P0) range of 0.05–0.30. The micropore surface (Smic)
area and micropore volume (Vmicro) were investigated using the t-plot method. The
average pore diameter (Dp) was determined according to the Density Functional Theory
(DFT) method.

2.4. Fourier Transform Infrared Spectra (FTIR)

The surface chemistries of the activated carbon samples were characterized using
an FTIR analysis. The samples were blended with KBr and then tabulated. The infrared
 area and micropore volume (Vmicro) were investigated using the t-plot method. The av-
erage pore diameter (Dp) was determined according to the Density Functional Theory
(DFT) method.

2.4. Fourier Transform Infrared Spectra (FTIR)

Sustainability 2023, 15, 654 The surface chemistries of the activated carbon samples were characterized using5 of an16
FTIR analysis. The samples were blended with KBr and then tabulated. The infrared spec-
tra of the samples were recorded using a Perkin Elmer model to detect the surface func-
spectra
tional of theThe
groups. samples were
infrared recorded
spectra wereusing a Perkin
recorded in theElmer
wave model
range ofto600–4000
detect the
cmsurface
−1.

functional groups. The infrared spectra were recorded in the wave range of 600–4000 cm−1 .
2.5. Adsorption Experiment
2.5. Adsorption Experiment
2.5.1. Bed Adsorption
2.5.1. Bed Adsorption
A schematic of the device used for the bed adsorption experiment is shown in Figure
A schematic of the device used for the bed adsorption experiment is shown in Figure 2.
2. Carbonized fibers (5) were packed into a glass column (4) to study their adsorption
Carbonized fibers (5) were packed into a glass column (4) to study their adsorption capacity.
capacity. The wastewater (2) was introduced in a funnel (1) and passed through an input
The wastewater (2) was introduced in a3 funnel (1) and passed through an input valve (3) to
valve (3) to adjust the flow3at −4–5.10 m ·h−1. First, the bed adsorption device was wetted
adjust the flow at 4–5.10 m ·h 1 . First, the bed adsorption device was wetted using distilled
using distilled water flowing through the column in order to improve the wetting charac-
water flowing through the column in order to improve the wetting characteristics of the
teristics of the activated carbon fibers. Second, the refinery wastewater sample (2) content
activated carbon fibers. Second, the refinery wastewater sample (2) content in the funnel (1)
in the funnel (1) was allowed to drain through the activated carbon bed (5) to the received
was allowed to drain through the activated carbon bed (5) to the received reservoir (6) by
reservoir (6) by gravity. Treated water was reclaimed every hour.
gravity. Treated water was reclaimed every hour.

Figure 2. Bed adsorption experiment.

Figure 2. Bed adsorption experiment.
2.5.2. Batch Adsorption
2.5.2. Batch Adsorptionsamples were collected from a local petroleum refinery (Tunisian
The wastewater
Society
The wastewaterIndustry
of Refining samples(STIR)) and preserved
were collected from in dark-colored
a local plastic
petroleum containers
refinery at RT.
(Tunisian
Table 1 shows the main characteristics of the refinery wastewater.
Society of Refining Industry (STIR)) and preserved in dark-colored plastic containers at
RT. Table 1 shows the main characteristics of the refinery wastewater.
Table 1. Refinery wastewater characteristics.
Table 1. Refinery wastewater characteristics.
Characteristic Value
Characteristic
pH 12.9 Value
(ms·cm−1 )
pHConductivity − 126.7
12.9
Sulfide (mg·L 1 ) 3476
Conductivity
NaOH (wt%)(ms·cm−1) 7.5 126.7
Sulfide (mg·L )−1 3476
NaOHBatch
(wt%)adsorption equilibrium experiments were 7.5carried out by reacting a known
amount (4.0 g) of CA with 50 mL of a real wastewater sample in a sealed glass bottle. Five
samples with different initial sulfur concentrations (100, 300, 500, 800, and 1000 mg·L−1 )
were tested. The bottles were kept on a shaker at a constant temperature for 24 h until they
reached equilibrium (final pH: 10.5).
The adsorption capacity Qt at contact time t was calculated as follows [56]:

(C0 − Ct )·V
Qt = (1)
M
Sustainability 2023, 15, 654 6 of 16

where Ct is the sulfur solution concentration at time t (mg/L), Ci is the initial sulfur
concentration (mg/L) at time 0, M is the weight of the adsorbent (g), and V is the volume
of the solution (L).

2.5.3. Determination of COD

The determination of COD was performed using potassium dichromate based on the
American Public Health Association (APHA) standard method [57]. COD in mg·L−1 was
calculated using the following equation:

n·(a − b)
COD = ·8000 (2)
V
where a (mL) is the ferrous ammonium sulfate required for the titration of the blank, b (mL)
is the ferrous ammonium sulfate required for the titration of the sample, n is the normality
of the ferrous ammonium sulphate, and V (mL) is the sample volume.

2.6. Kinetic Models

The kinetics of the adsorption was investigated to evaluate the potential of using
synthesized activated carbon as an adsorbent of sulfur compounds in refinery wastewater.
In this study, several experimental conditions were explored to determine the factors that
can affect the adsorption speed. The obtained experimental results were tested with three
mathematical models that can describe the kinetics of interaction between synthesized
activated carbon and sulfur compounds. Three of the most widely used kinetic models
were investigated: pseudo-first-order, pseudo-second-order, and intra-particular diffusion
models. Table 2 illustrates the mathematical forms of each model, where k1 represents
the pseudo-first-order rate constant (min−1 ), k2 represents the pseudo-second-order rate
constant (L·mg−1 ·min−1 ), and kid is the diffusion intraparticular constant (mL−1 ·min−1/2 ).

Table 2. Kinetic models.

Model Equation Reference

Pseudo-first-order


k1 [58]
log qe − qt = log qe − 2.303 t
Pseudo-second-order t 1 1 [59]
qt = k2 q2 eq
+ q2 eq
t
1
Intraparticular diffusion qt = Kid ·t + C 2 [60]

2.7. Adsorption Isotherm Studies

Equilibrium parameters and sulfur compound adsorption were tested using several
isotherm models. This investigation was performed to evaluate the nature of the interac-
tions that may exist between the obtained carbon and sulfur compounds. The Langmuir,
Freundlich, Dubinin–Radushkevich, Tóth, and Sips models were used as isotherm models.
Table 3 presents the linear forms of each model studied.

Table 3. Isotherm models.

Model Equation Linear Form Reference

qm ·KL ·Ce Ce 1
Langmuir qe = 1 + KL · C e qe = ·Ce + KL1·q
qm
[61]
m
1
Freundlich qe = KF ·Ce n log(qe ) = log(KF ) + n1 · log(Ce ) [62]
Dubinin– qe 2


RT 2
 2
= exp −βε ln(qe ) = ln(qmDR ) − E ·(ln C [63]
S


Radushkevich qmDR )
qe n
n  n Ce
KL ·Ce

Tóth qm = 1/n ( Cq e ) = q 1·K + q1 ·(Ce )n [64]
[1+(KL ·Ce )n ] e m L m
qe n
Sips qm = 1+KKS CS Ce e n 1
qe = 1
qm + 1
KL qm Ce n
[65]
 ch
·
Tóth = ( ) ] ⁄
( ) = + · (C ) [64]
[ · ·

Sips = = + [65]
Sustainability 2023, 15, 654 7 of 16

3. Results and Discussion

3.1. Activated Carbon Characterization
3. Results and Discussion
Through
3.1. Activated calcination
Carbon and HNO3, H2O2, and KOH activation, the waste of cotton fiber
Characterization
wasThrough
successfully transferred
calcination and HNOinto activated carbon with different structures. Figure
3 , H2 O2 , and KOH activation, the waste of cotton fibers
shows the SEM images of the HNAC,
was successfully transferred into activated carbon HOAC, withand KAC activated
different structures. carbons. It can be see
Figure 3 shows
that
the theimages
SEM chemical activation
of the contributed
HNAC, HOAC, and KAC to the formation
activated of macroporosity.
carbons. A hollow
It can be seen that the cor
can be observed
chemical activationthroughout
contributed theto thelength of theoffiber,
formation with a diameter
macroporosity. A hollow of core
around
can be0.5–5.0 μM
observed throughout
and an almost the length
circular shape.of Thetheactivated
fiber, withcarbon
a diameter
has aofhighly
aroundporous
0.5–5.0 structure,
µM and with
an almost
core circularbetween
diameter shape. The activated carbon
approximately 0.5has
and a highly
5 μM porous
(Figurestructure, with macroporosit
3b,d). This a core
diameter between approximately 0.5 and 5 µM (Figure 3b,d). This macroporosity
may be related to the chemical destruction of lignin in the internal wall of the cotton may be fibers
related to the chemical destruction of lignin in the internal wall of the cotton fibers. The
The reference activated carbon (Figure 3a) presents macroporosity, while the morpholog
reference activated carbon (Figure 3a) presents macroporosity, while the morphology is
is characterized by the appearance of the core in the fiber, whose diameter depends on th
characterized by the appearance of the core in the fiber, whose diameter depends on the
activatingagent.
activating agent.
TheThe largest
largest diameter
diameter is obtained
is obtained with
with the usethe use of hydrogen
of hydrogen peroxideperoxide
as a
anactivated
an activated reagent
reagent (Figure
(Figure 3b).3b). As shown
As shown in Figure
in Figure 3b–d,
3b–d, the the structure
structure of the precurso
of the precursor
(initially with a clean surface) is destroyed after each chemical treatment.
(initially with a clean surface) is destroyed after each chemical treatment. Interestingly, Interestingly
the
surface of theof
the surface HOAC activated
the HOAC carbon changes
activated obviouslyobviously
carbon changes under the under
influence
theofinfluence
chemical of chem
activation (compared
ical activation with thewith
(compared othertheactivated carbons). carbons).
other activated

Figure3.3.SEM
Figure SEM images
images of activated
of activated carbon:
carbon: (a) reference
(a) reference activated
activated carbon,carbon, (b) (c)
(b) HNAC, HNAC, (c)and
HOAC, HOAC, an
(d)KAC.
(d) KAC.

The infrared spectra of the different activated carbons are shown in Figure 4. The FTIR
spectrum of HOAC is shown in Figure 4c. It can be seen that the main spectral changes are
restricted to between 1300 and 900 cm−1 . This indicates that the oxidation of the obtained
char with the H2 O2 solutions contributes to the increase in the number of OH surface
groups. More precisely, these hydroxyl groups (OH) absorb radiation at 1195 cm−1 .
At 1300 cm−1 , there was a slight deviation in intensity. In fact, oxygen groups (C=O,
−
CO2 or C=O) formed at very low concentrations. Moreover, for that reason, the oxidation
state of the activated carbon surface did not improve because of the reaction with H2 O2 .
Therefore, H2 O2 was able to oxidize the material, and, hence, the surface chemistry of the
AC was significantly altered
 The infrared spectra of the different activated carbons are shown in Figure 4. The
FTIR spectrum of HOAC is shown in Figure 4c. It can be seen that the main spectral
changes are restricted to between 1300 and 900 cm−1. This indicates that the oxidation of
Sustainability 2023, 15, 654 8 of 16
the obtained char with the H2O2 solutions contributes to the increase in the number of OH
surface groups. More precisely, these hydroxyl groups (OH) absorb radiation at 1195 cm−1.

Figure 4. Infrared spectrum of different activated carbons: red line—reference activated carbons,
Figure
blue4. Infrared spectrum
line—HNAC, of different and
black line—HOAC, activated
purplecarbons: (a) reference activated carbons, (b)
line—KAC.
HNAC, (c) HOAC, and (d) KAC.
HNO3 is a dehydrating agent that reduces the release of volatile matter and produces
At 1300
a high cmof
yield −1, there was a slight deviation in intensity. In fact, oxygen groups (C=O,
carbon content in activated carbon.
CO2 or According
− C=O) formed to at very low
Figure 4, weconcentrations.
can conclude Moreover,
that there for wasthata newreason, the oxidation
modification of the
state of the activated carbon surface did not improve because
FTIR spectrum of the HNAC sample and that new bands appeared. In fact, a new band of the reaction with H 2 O 2. at

Therefore, H−
1460 cm 2 was O
1 2 was able to oxidize the material, and, hence, the surface chemistry
detected; this may be due to the vibrations of carboxyl groups (O–H). The of the AC
wasincrease
significantly intensity of the band at 1720 cm−l can be assigned to the C=O stretching
in thealtered
HNO3 is aThe
vibration. dehydrating
band at 3400 agent −1 , due
cmthat reduces theO–H
to the release of volatile
stretching matter and
vibration, can produces
be assigned
a high yield of acid
to carboxyl carbon content
groups. Theinexistence
activatedof carbon.
nitrate and nitro surface groups was confirmed
byAccording
the appearance to Figure 4, webands
of new can conclude that there
in the region wascm
of 1538 −l . In
a new modification
conclusion,ofthe thechemical
FTIR
activation
spectrum of theusing
HNAC HNO sample
3 fixed carboxyl
and that groups
new bands and likely
appeared. fixed
In nitro
fact, a and
new nitrate
band at groups.
1460
cmHowever,
−1 the activation
was detected; this mayusingbe due H2 O andvibrations
to2 the KOH probably fixed carboxyl,
of carboxyl ketone,The
groups (O–H). andin-ether
groups.
crease in theThis was due
intensity to the
of the bandnature
at 1720 of the
cm−lactivation using HNO
can be assigned to the3 ,C=O
which can break
stretching vi-the
porous
bration. texture
The bandofatthe activated
3400 cm−1, due carbons
to thecompared with thevibration,
O–H stretching other twocan oxidizing treatments.
be assigned to
However,
carboxyl acidactivation
groups. The using H2 O2 and
existence KOHand
of nitrate doesnitro
not support the formation
surface groups of ketonebyand
was confirmed
theether groups.of new bands in the region of 1538 cm−l. In conclusion, the chemical acti-
appearance
vation usingpore
The HNO structure of the samples
3 fixed carboxyl groups was and determined usingand
likely fixed nitro nitrogen
nitrateadsorption
groups. How- at 77 K.
ever, the activation using H2O2 and KOH probably fixed carboxyl, ketone, and etherThe
The specific surface area was calculated using the Brunauer–Emmett–Teller equation.
micropore
groups. This wasvolume due andto thesurface
nature area
of were calculated
the activation usingHNO
using a t-plot. According
3, which can breakto Table
the 4,
the maximal
porous texture of values of the pore
the activated volume
carbons size and with
compared specific
thesurface
other two areaoxidizing
were identified
treat- in
the chemical
ments. However,activation
activationusing usingH H22OO22. and
ThisKOHwasdoes
because oxidation
not support thetreatment
formationfavors
of ke-the
dehydrogenation
tone and ether groups. that was observed for this type of activation.
The pore structure of the samples was determined using nitrogen adsorption at 77 K.
4. Textural properties of the studied ACs, calculated using the data of N2 adsorption isotherms.
TheTable
specific surface area was calculated using the Brunauer–Emmett–Teller equation. The
micropore volume andS surface 2 area
−1 were Vtcalculated
(cm3 ·g−1 ) usingVaDR
t-plot. According
(cm3 ·g −1 ) to Table
(cm3 ·g4,
−1 )
BET (m ·g ) VMES
the maximal values of the pore volume size and specific surface area were identified in
HOAC 1230 1.20 0.51 0.62
the chemical
HNAC
activation842
using H2O2. This1.03 was because oxidation
0.48
treatment favors
0.59
the de-
hydrogenation
KAC that was observed
915 for this type
1.08 of activation.
0.49 0.60

As can be seen in the BJH pore size distribution, there was an obvious change in the
distribution after carrying out the different chemical activation methods. The pore volume
of HOAC was much larger than that of KAC and HNAC.
After the chemical activation, the BET surface areas of HOAC, HNAC, and KAC
were 1230 m2 ·g−1 , 840 m2 ·g−1 , and 915 m2 ·g−1 , respectively. Moreover, the mesopore
Sustainability 2023, 15, 654 9 of 16

volume ratio of HOAC was higher than that of HNAC and KAC, providing more chan-
nels for ions to penetrate into the interior micropore surface area and leading to a good
rate performance.
SBET is the BET surface area calculated from the N2 adsorption, Vt is the total pore
volume of N2 , VDR is the micropore volume determined using the Dubinin–Raduskevich
equation, and VMES is the volume of mesopores [63].
The lowest nitrogen uptake occurred for HNAC, which indicates a low specific surface
Sustainability 2023,area
15, x (840
FOR PEER
m2 ·gREVIEW
−1 ). The profiles of the isotherms of HOAC, HNAC, and KAC were close

to a type I isotherm with a H4 type of loop (Figure 5). The branches of adsorption and
desorption were nearly horizontal and parallel in the relative pressure range between 0.4
and 0.8.

Figure 5. Effect of activated carbon dosage and wastewater flow on COD of reclaimed effluent.
Figure 5. Effect of activated carbon dosage and wastewater flow on COD of reclaimed efflu
The wider H4 hysteresis loop of HOAC compared to that of HNAC and KAC indicates
the domination of a mesoporous structure. However, this type of hysteresis corresponds
Table 5. Summary of experimental design parameters.
to the existence of both micro- and meso-porous structures, which correspond to a large
Flowadsorbed
amount of N2 being Rate (L/h)inDosage Rate
the entire (mg/L)
relative CODHNAC
pressure (mg/L)
range. As isCOD HOAC (mg/L)
well-known, theCODKAC
effect of chemical
1 activation is to5 open the pores of 1585activated carbon 1180
wider in order to1870
improve the chemical
1 reagent efficacy.
10 644 485 778
As can be observed,
1 nitric acid
15 treatment can modify
252 the porous structure
183 of activated304
carbon, but the1 effect of peroxide
25 oxidation is more60pronounced. In4the case of KOH68
activation, KOH diffused into the activated carbon and reacted both inside and outside
2 5 1841 1375 2202
simultaneously, leading to a developed pore structure.
2 10 756 560 907
To describe the adsorption isotherm of sulfur content by the synthesized activated
2 15 348 255 420
carbons, mathematical models were investigated. In this experiment, the Freundlich and
Langmuir models 2 were used as the25most common isotherms.89 65 parameters (k108
The Freundlich f
3 5 2105 1563 parameters2515
and n) were determined from the linear plot of log Qe vs. log Ce . The Langmuir
(Q0 and b) were 3 calculated from10the plot of Ce /Qe vs. 912Ce . All parameters
674 are listed in1084
Table 5. 3 15 420 311 524
3 25 114 82 134
4 5 2340 1735 2811
4 10 1140 844 1352
4 15 530 375 621
4 25 135 105 163
Sustainability 2023, 15, 654 10 of 16

Table 5. Summary of experimental design parameters.

Flow Rate (L/h) Dosage Rate (mg/L) CODHNAC (mg/L) CODHOAC (mg/L) CODKAC (mg/L)
1 5 1585 1180 1870
1 10 644 485 778
1 15 252 183 304
1 25 60 4 68
2 5 1841 1375 2202
2 10 756 560 907
2 15 348 255 420
2 25 89 65 108
3 5 2105 1563 2515
3 10 912 674 1084
3 15 420 311 524
3 25 114 82 134
4 5 2340 1735 2811
4 10 1140 844 1352
4 15 530 375 621
4 25 135 105 163

The calculated RL values were between 0 and 1, which indicates favorable sulfur
compound adsorption by the synthesized activated carbon.
As can be seen from the correlation coefficient (R2 ), the Freundlich and Langmuir
isotherms were able to describe the adsorption data obtained regarding the adsorption of
the sulfur content onto the HOAC, HNAC, and KAC activated carbons. As summarized, the
adsorption isotherms followed the Langmuir isotherm. This suggests that the homogenous
surface and the adsorption follow the physisorption of monolayer adsorption patterns.
The better fit of the Langmuir model to the adsorption of the sulfur compounds onto
both activated carbons shows that adsorption was found on the heterogeneous surface.
Furthermore, there was an interaction between the adsorbed molecules and sulfur contents.

3.2. The Results of Fixed-Bed Adsorption

The adsorption bed column was installed as shown in Figure 1, and the refinery
wastewater was allowed to flow under gravity. The diameter and the height of the bed
column were 5.4 cm and 90 cm, respectively. The optimum adsorption conditions were
determined for several parameters influencing the bed experiment, including the activated
carbon dosage ratio and effluent flow. The experiments were designed using the response
surface method. The results were analyzed using the analysis of variance method (ANOVA)
to examine the effect of the parameters on the COD of the treated wastewater. Table 5
shows the 16 levels of the experimental design parameters and their results. For each of
the 16 experiments, the COD was calculated. Figure 6 shows the effect of both activated
carbon dosage and wastewater flow on the COD of the reclaimed effluent. For all samples
of activated carbon at a high rate of wastewater flow, the COD was enhanced by an increase
in the dosage mass. However, at a low flow rate, the COD was reduced. In summary,
OHAC was the most effective adsorbent (compared with the HNAC and KAC activated
carbons) in reducing the COD value of the refinery wastewater.
According to the contour plot (Figure 6), the COD value decreased with the flow rate
of the effluent at a given saturation of each AC, and the decrease was nonlinear, particularly
at low flow rates. This may be due to the combined effect of AC residence time. The lowest
value of COD was obtained with the use of OHAC. This result was correlated with the
activated carbon characteristics.
It can be concluded that the characteristic properties of activated carbon, such as the
specific surface area, perfectly correlate with the decrease in COD. In fact, the highest value
of the specific surface area (1230 g·m−2 ) was attributed to OHAC, which had the lowest
value of COD.
 the activated carbon characteristics.
It can be concluded that the characteristic properties of activated carbon, such as the
specific surface area, perfectly correlate with the decrease in COD. In fact, the highest
value of the specific surface area (1230 g·m−2) was attributed to OHAC, which had the
Sustainability 2023, 15, 654 11 of 16
lowest value of COD.

Figure 6. Contour plots of COD, (a) OHAC, (b) HNAC, and (c) KAC.
Figure 6. Contour plots of COD, (a) OHAC, (b) HNAC, and (c) KAC.
3.3. Adsorption Kinetics
Table 6 displays the kinetic parameters. To assess the relationship between the com-
puted and experimental data, the correlation coefficient (R2 ) was utilized. The pseudo-
second-order model had the greatest R2 value, as shown in Table 6. This indicates that
the experimental data and the calculation for the pseudo-second-order kinetic model
were well-correlated. As a result, the pseudo-second-order model can be considered a
suitable kinetic model that fits the kinetic adsorption of sulfur compounds on HOAC
activated carbon.

Table 6. Kinetic parameters of sulfur compound adsorption.

Kinetic Model Model Parameters R2

qe (mg·g−1 ) K1 (min−1 )
Pseudo-first-order 0.94
120 0.003
qe (mg·g−1 ) K2 (L·mg−1 ·min−1 )
Pseudo-second-order 0.99
135 11.10−4
Kid (mg·g−1 ·min−0.5 ) C
Intraparticular diffusion 0.91
11.20 0.13

The agreement between the experimental data and the model-predicted data was
investigated by calculating correlation coefficients (R2 values closer to 1 means a greater ap-
plicability of the model) and by observing the extent to which the experimental adsorption
capacity is close to the theoretical value.
Sustainability 2023, 15, 654 12 of 16

According to Table 6, there was an excellent connection between the experimental

value and the pseudo-second-order calculated kinetic model. This result was determined
due to the pseudo-second-order calculated kinetic model having the highest correlation
coefficient R2 value (0.99). Consequently, the pseudo-second-order model can be con-
sidered a suitable kinetic model that fits the kinetic adsorption of sulfur compounds on
the HOAC. The electron exchange between the sulfur compounds and HOAC generated
by the chemical adsorption resulted in a high valence liaison. As can be seen in Table 6,
the pseudo-first-order and intraparticular diffusion models had low regression coefficient
values (R2 < 0.94). For the used kinetic model, a statistically significant difference was
observed between the experimental and calculated adsorption capacities.

3.4. Modeling of Adsorption Isotherm

From the aqueous solutions, the equilibrium adsorption isotherms of the sulfur com-
pounds were modeled and investigated on HOAC activated carbon. Five mathematical
models were used in order to describe the experimental data of the adsorption isotherms.
The main purpose of this work was to select the most suitable models that can describe
the experimental results of the adsorption isotherms, determine the theoretical adsorp-
tion isotherm, and give the parameters. The initial goal was to develop a two-parameter
equation in order to simulate the adsorption of sulfur compounds by HOAC. The experi-
mental conditions were as follows: an initial sulfur concentration in a range between 5 and
300 mg·L−1 , agitation of 150 rpm, and a controlled temperature of 25 ◦ C. For all isotherm
models, the linear equation was investigated to determine its linear parameters with the
use of experimental values of Qe and Ce . The linear correlation coefficient (R2 ) was used to
evaluate the correlation between the theoretical and experimental values.
According to Table 7, we can conclude that the isotherm parameters were different.
The Langmuir model has highest value of the correlation coefficient (R2 = 0.98). This
shows that the adsorption of the sulfur compounds on synthesized activated carbon fol-
lows the Langmuir isotherm. Both the Dubinin–Radushkevich and Tóth isotherms have
the lowest correlation coefficient values (0.79 and 0.89, respectively), which suggests that
these isotherms are not appropriate for this type of adsorption. However, the monolayer
adsorption capacity obtained using the Langmuir isotherm is higher than that obtained
using the other isotherm models. This indicates that all the active sites of the synthe-
sized activated carbon (HOAC) are similar and that there is no interaction between the
sulfur compounds.

Table 7. Linear isotherm parameters.

Model n KL qm (mg·g−1 ) R2
Langmuir 0.84 0.02 168.4 0.98
Freundlich 0.84 0.01 17 0.96
Dubinin–Radushkevich E0.16 - - 0.79
Tóth 0.14 5.95 × 10−6 115 0.89
Sips 0.79 0.01 241 0.97

4. Conclusions
In this study, solid waste from the spinning industry was investigated as a precursor
of carbon materials. An ecofriendly activated carbon was successfully synthesized as an
adsorbent of sulfur compounds in refinery wastewater. Kinetic and equilibrium data for
the adsorption of sulfur compounds were obtained and fitted to Langmuir and pseudo-
second-order models, respectively. The results show that introducing hydrogen peroxide,
nitric acid, and potassium hydroxide can successfully increase the pore size distribution,
pore volume, and surface area of carbon derived from cotton waste. In addition, HOAC
(SBET = 1230 m2 ·g−1 and Vt = 1.20 cm3 ·g−1 ) had the best capacity to remove sulfur com-
pounds compared to HNAC and KAC. It was found that, during fixed-bed adsorption, the
Sustainability 2023, 15, 654 13 of 16

flow rate of effluent was the factor most effective at decreasing the COD of the refinery
wastewater according to the responses and the ANOVA process.
The Langmuir model exhibited the best fit (R2 = 0.98) for the sulfur compounds’
adsorption, which implies that their adsorption onto the synthesized AC was homogeneous.
The kinetic data were tested with pseudo-first-order, pseudo-second, and intraparticular
diffusion equations. The pseudo-second-order equation showed the best description
for the kinetic data (R2 = 0.99), which means that this adsorption can be limited by the
chemisorption process.
Several methods have been investigated for the treatment of refinery wastewater,
including physical, chemical, and biological methods.
As a physical method, membrane bioreactors have been successfully used to remove
pollutants from petroleum industry wastewater. However, membrane fouling is a major
problem that can frequently occur. Moreover, this seriously affects the quality of the
reclaimed water and the efficiency of the membrane. Its use has only been tested in a
pilot test.
Electrochemical processes can also be utilized for the treatment of petroleum refinery
wastewater. Their higher cost and lower efficiency also limit their industrial application.
The microbiological treatment of industrial refiner wastewater has also been investi-
gated using several types of microorganisms. However, the use of a biological approach
for refinery effluent treatment can cause serious problems due to the excessive production
of sludge.
Many researchers have demonstrated that adsorption is a high-potential and cost-
effective approach for the treatment of refinery wastewater. AC has previously been
developed from biomass, such as date pits.
Most of these studies were conducted at the laboratory scale, with no focus on a
specific application.
The main purpose of our work, realized with the collaboration of a big refinery
company in Tunisia, was to synthesize activated carbon from low-quality cotton fiber
spinning waste with and to use it to remove sulfur compounds from refinery wastewater.
The results demonstrate the high efficiency of the obtained AC.
In comparison with other biomasses, cotton spinning waste can be used directly and
does not need any selection or chemical treatment. This makes the management of this
waste utilized directly as activated carbon easier.

Author Contributions: Conceptualization, B.W., M.K., I.B.H., R.A., Z.A., M.B.H., S.A., S.Z., M.T.K.
and A.S.B.; Methodology, B.W., M.K., I.B.H. and A.S.B.; Validation, B.W., M.K., I.B.H. and A.S.B.;
Data curation, B.W., M.K. and I.B.H.; Supervision, M.K. and M.B.H.; Visualization, M.K. and M.B.H.;
Writing—original draft, M.K. and M.B.H.; Writing—review and editing, B.W., M.K., I.B.H., R.A., Z.A.,
M.B.H., S.A., S.Z., M.T.K. and A.S.B.; All authors have read and agreed to the published version of
the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: This study did not report any data.
Conflicts of Interest: The authors declare no conflict of interest.

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